Synthesis and properties of some bismuth (III), manganese (II), yttrium (III), europium (III), and gadolinium (III) complexes

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Title:
Synthesis and properties of some bismuth (III), manganese (II), yttrium (III), europium (III), and gadolinium (III) complexes
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xiv, 142 leaves : ill. ; 29 cm.
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Summers, Stephen P
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Thesis:
Thesis (Ph. D.)--University of Florida, 1994.
Bibliography:
Includes bibliographical references (leaves 138-140).
Statement of Responsibility:
by Stephen P. Summers.
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Typescript.
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Vita.

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Full Text











SYNTHESIS AND PROPERTIES OF SOME
BISMUTH(III), MANGANESE(II), YTTRIUM(III),
EUROPIUM(III), AND GADOLINIUM(III) COMPLEXES

















BY

STEPHEN P. SUMMERS


A DISSERTATION PRESENTED TO THE GRADUATE SCHOOL
OF THE UNIVERSITY OF FLORIDA IN PARTIAL FULFILLMENT
OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY

UNIVERSITY OF FLORIDA


1994














ACKNOWLEDGEMENTS


Many thanks must first go to Dr. Gus Palenik and the

Inorganic Division for giving me a home, and to Ruth Palenik

and Kim Browning for helping me a great deal as I began my

graduate research. Special thanks go to Dr. Khalil Abboud

whose expertise in x-ray crystallography, and patience with

me, were above and beyond the call of duty, and to Dr. Sam

Farrah whose aid in determining antibacterial activities was

greatly appreciated.

I would like to thank my parents Don and Helen Summers,

and the rest of my family, Kim, Bob, Rachel, Rochelle, Lynn,

Brad, and David, for their continued support throughout my

schooling.

To Dewayne, my friend, roommate, and traveling

companion, Jason, my friend and confidant, and Jeff, my

friend and work-out partner, I pledge my friendship forever

and hope that we will all stay together in spirit, if not in

body. And to Eric, with many thanks for being there the

last nine months, I wish the best of luck in Seattle.
















TABLE OF CONTENTS

page

ACKNOWLEDGMENTS.................................. ii

LIST OF TABLES.................................... v

LIST OF FIGURES.................................. x

ABSTRACT......................................... xiii

CHAPTERS

1 INTRODUCTION........................... ..... 1

Bismuth Chemistry............................ 1
Manganese and Gadolinium Chemistry.......... 3

2 COMPLEXES OF BISMUTH(III):
A SYNTHETIC AND STRUCTURAL STUDY........... 6

Introduction................................ 6
Experimental............................... 11
Discussion........................ .......... 16

3 COMPLEXES OF BISMUTH(III): VALENCE
BOND SUMS AND COORDINATION POLYHEDRA........ 60

Introduction................................... 60
Discussion and Results...................... 62

4 BISMUTH COMPLEXES: A STUDY OF
ANTIBACTERIAL ACTIVITY..................... 76

Introduction................................ 76
Experimental................................ 77
Discussion........................... ...... 78

5 COMPLEXES OF BISMUTH(III) WITH PHOSPHONIC
ACIDS: A SYNTHETIC AND SPECTROSCOPIC
STUDY ........ .............................. 82

Introduction................. ............ .. 82
Experimental................................ 83
Discussion.................... ........... .. 88

iii









page

6 COMPLEXES OF MANGANESE(II), GADOLINIUM(III),
EUROPIUM(III), AND YTTRIUM(III) WITH
2,6-DIACETYLPYRIDINE BIS(ACETIC ACID
HYDRAZONE)................. ............... 93

Introduction............................... 93
Experimental................................ 96
Discussion ................................ 100

REFERENCES........................................ 138

BIOGRAPHICAL SKETCH .............................. 141














LIST OF TABLES


Table Pase

2-1: Fractional coordinates and equivalent
isotropic thermal parameters (A2) for
the non-H atoms of compound 1. ............... 19

2-2: Bond lengths (A) and angles (0) for the
non-H atoms of compound 1. ................... 20

2-3: Fractional coordinates and isotropic
thermal parameters (A2) for the
H atoms of compound 1. ......................... 22

2-4: Bond lengths (A) and angles (0) for the
H atoms of compound 1. ......................... 23

2-5: Crystallographic data for compound 1. ........ 24

2-6: Fractional coordinates and equivalent
isotropic thermal parameters (A2) for
the non-H atoms of compound 3. ............... 27

2-7: Bond lengths (A) and angles (0) for the
non-H atoms of compound 3. ................... 28

2-8: Fractional coordinates and isotropic
thermal parameters (A2) for the
H atoms of compound 3. ......................... 30

2-9: Bond lengths (A) and angles (0) for the
H atoms of compound 3. ........................ 30

2-10: Crystallographic data for compound 3. ........ 31

2-11: Fractional coordinates and equivalent
isotropic thermal parameters (A2) for
the non-H atoms of compound 4 ................ 34

2-12: Bond lengths (A) and angles (0) for the
non-H atoms of compound 4. .................... 35








Table Page

2-13: Fractional coordinates and isotropic
thermal parameters (A2) for the
H atoms of compound 4. ......................... 36

2-14: Bond lengths (A) and angles (0) for the
H atoms of compound 4. ......................... 36

2-15: Crystallographic data for compound 4. ........ 37

2-16: Fractional coordinates and equivalent
isotropic thermal parameters (A2) for
the non-H atoms of compound 5. ............... 40

2-17: Bond lengths (A) and angles (0) for the
non-H atoms of compound 5. ................... 41

2-18: Fractional coordinates and isotropic
thermal parameters (A2) for the
H atoms of compound 5. ......................... 42

2-19: Bond lengths (A) and angles (0) for the
H atoms of compound 5. ......................... 43

2-20: Crystallographic data for compound 5. ........ 44

2-21: Fractional coordinates and equivalent
isotropic thermal parameters (A2) for
the non-H atoms of compound 6. ............... 47

2-22: Bond lengths (A) and angles (0) for the
non-H atoms of compound 6. ................... 48

2-23: Fractional coordinates and isotropic
thermal parameters (A2) for the
H atoms of compound 6. ........................ 49

2-24: Bond lengths (A) and angles (0) for the
H atoms of compound 6. ......................... 50

2-25: Crystallographic data for compound 6. ........ 52

2-26: Fractional coordinates and equivalent
isotropic thermal parameters (A2) for
the non-H atoms of compound 7. ............... 55

2-27: Bond lengths (A) and angles (0) for the
non-H atoms of compound 7. ................... 55








Table Page

2-28: Fractional coordinates and isotropic
thermal parameters (A2) for the
H atoms of compound 7. ......................... 56

2-29: Bond lengths (A) and angles (0) for the
H atoms of compound 7. ......................... 57

2-30: H-bonding for compound 7. .................... 58

2-31: Crystallographic data for compound 7. ........ 59

3-1: Contributions to valency of each Bi-donor
atom bond and total VBS for the complex
Bi2 (DIPIC) 2 (HDIPIC) 2(HAc) 4H20. .... . .. 65

3-2: Contributions to valency of each Bi-donor
atom bond and total VBS for the complex
Bi(NTA) 2H2O. ................................ 65

3-3: Contributions to valency of each Bi-donor
atom bond and total VBS for the complex
Bi (HEDTA) *2H20. .............................. 65

3-4: Contributions to valency of each Bi-donor
atom bond and total VBS for the complex
(Guan) 2Bi(DTPA) 4H20. ........................... 66

3-5: Contributions to valency of each Bi-donor
atom bond and total VBS for the complex
Bi(DAPAAH) (Ac) 24H20. .................. ..... 66

4-1: Mass of complexes on filter papers after
soaking in saturated solutions. .............. 81

4-2: Diameters of inhibition for Bi(PIC)3,
Bi(NTA), and Bi(HEDTA) in each type
of bacteria. ................................. 81

6-1: Fractional coordinates and equivalent
isotropic thermal parameters (A2) for
the non-H atoms of compound 14. ............. 103

6-2: Bond lengths (A) and angles (0) for the
non-H atoms of compound 14. .................. 104

6-3: Fractional coordinates and isotropic
thermal parameters (A2) for the
H atoms of compound 14. ...................... 105


vii








Table Page

6-4: Bond lengths (A) and angles (0) for the
H atoms of compound 14. ....................... 106

6-5: Crystallographic data for compound 14. ....... 107

6-6: Fractional coordinates and equivalent
isotropic thermal parameters (A2) for
the non-H atoms of compound 15. .............. 110

6-7: Bond lengths (A) and angles (0) for the
non-H atoms of compound 15. .................. 111

6-8: Fractional coordinates and isotropic
thermal parameters (A2) for the
H atoms of compound 15. ....................... 113

6-9: Bond lengths (A) and angles (0) for the
H atoms of compound 15. ....................... 114

6-10: Crystallographic data for compound 15. ....... 115

6-11: Fractional coordinates and equivalent
isotropic thermal parameters (A2) for
the non-H atoms of compound 16. .............. 118

6-12: Bond lengths (A) and angles (0) for the
non-H atoms of compound 16. .................. 119

6-13: Fractional coordinates and isotropic
thermal parameters (A2) for the
H atoms of compound 16. ...................... 121

6-14: Bond lengths (A) and angles (0) for the
H atoms of compound 16. ....................... 122

6-15: Crystallographic data for compound 16. ....... 123

6-16: Fractional coordinates and equivalent
isotropic thermal parameters (A2) for
the non-H atoms of compound 17. .............. 125

6-17: Bond lengths (A) and angles (0) for the
non-H atoms of compound 17. .................. 126

6-18: Fractional coordinates and isotropic
thermal parameters (A2) for the
H atoms of compound 17. ....................... 128


viii








Table Page

6-19: Bond lengths (A) and angles (0) for the
H atoms of compound 17. ...................... 129

6-20: Crystallographic data for compound 17. ....... 130















LIST OF FIGURES


Figure Page

2-1: 2,6-diacetylpyridine bis(acetic acid
hydrazone)................................. 8

2-2: Salicylaldehyde Semicarbazone.............. 8

2-3: Picolinic Acid ............................ 9

2-4: Dipicolinic Acid .......................... 9

2-5: Nitrilotriacetic Acid ..................... 9

2-6: Ethylenediaminetetraacetic Acid............ 10

2-7: Diethylenetriaminepentaacetic Acid........ 10

2-8: View of 1 showing the thermal ellipsoids
and atomic numbering. Methyl hydrogens
are omitted for clarity. ................. 18

2-9: View of 3 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity. ...................... 26

2-10: View of 4 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity. ...................... 33

2-11: View of 5 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity. ...................... 39

2-12: View of 6 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity. ...................... 46

2-13: View of 7 showing the thermal ellipsoids
and atomic numbering. Methyl hydrogens
are omitted for clarity. ................. 54

3-1: View of the polyhedron for compound 1
showing the capped square antiprism
arrangement. ............................. 70

x









Figure Page

3-2: View of the polyhedron for compound 3
showing the bicapped trigonal prism
arrangement. ............................ 71

3-3: View of the polyhedron for compound 4
showing the bicapped trigonal prism
arrangement ............................. 72

3-4: View of the polyhedron for compound 5
showing the bicapped trigonal prism
arrangement ............................. 73

3-5: View of the polyhedron for compound 6
showing the capped square antiprism
arrangement. ...... ...................... 74

5-1: Nitrilotrismethylenetriphosphonic Acid.... 84

5-2: Ethylenediaminotetramethylenetetraphos-
phonic Acid.......................... ..... 84

5-3: Infrared spectrum of 9. ................... 90

5-4: Infrared spectrum of 10. ................. 91

5-5: Infrared spectrum of 11. ................. 91

5-6: Infrared spectrum of 12. .................. 92

5-7: Infrared spectrum of 13. ................. 92

6-1: 2,6-diacetylpyridine bis(acetic acid
hydrazone) ................................ 95

6-2: View of 14 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity. ....................... 102

6-3: View of 15 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity. ...................... 109

6-4: View of 16 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity. ....................... 117

6-5: View of 17 showing the thermal ellipsoids
and atomic numbering. Water hydrogens are
omitted for clarity. ....................... 124









Figure Pace

6-6: 'H NMR of 17 taken 3/22/94. ............... 132

6-7: 13C NMR of 17 taken 3/22/94. ............. 132

6-8: 'H NMR of 17 taken 3/24/94 ............... 133

6-9: 13C NMR of 17 taken 3/24/94. ............. 133

6-10: 1H NMR of 17 taken 3/29/94 ............... 134

6-11: 13C NMR of 17 taken 3/29/94. ............. 134

6-12: 89Y NMR of Y(NO3)3 (reference) ............ 135

6-13: 89Y NMR of Y(NO3)3, close-up of 9Y peak.... 135

6-14: 9Y NMR of 17. ........ .................... 136

6-15: 89Y NMR of 17, close-up of 89Y peak. ...... 136


xii















Abstract of Dissertation Presented to the Graduate School
of the University of Florida in Partial Fulfillment of the
Requirements for the Degree of Doctor of Philosophy

SYNTHESIS AND PROPERTIES OF SOME
BISMUTH(III), MANGANESE(II), YTTRIUM(III),
EUROPIUM(III), AND GADOLINIUM(III) COMPLEXES

By
STEPHEN P. SUMMERS

August, 1994


Chairman: Dr. Gus J. Palenik
Major Department: Chemistry

A series of bismuth (III) complexes has been

synthesized with the carboxylic acids picolinic acid,

dipicolinic acid, nitrilotriacetic acid, ethylene-

diaminetetraacetic acid, and diethylenetriaminepentaacetic

acid, along with the phosphonic acids nitrilotrismethylene-

triphosphonic acid and ethylenediaminotetramethylenetetra-

phosphonic acid. Where satisfactory crystalline samples

were obtained x-ray crystallographic studies were conducted.

Solid state structures of the carboxylic acid compounds

revealed several similarities between these complexes, and

the crystallographic data was used to calculate valence bond

sums and determine coordination polyhedra. Phosphonic acid

complexes were extremely insoluble and were characterized by

elemental analysis and infrared spectroscopy.


xiii








Antibacterial properties of the carboxylate complexes

were monitored against the bacteria Escherichia Coli,

Pseudomonas Aeruginosa, and Staphylococcus Aureus. Radii of

inhibition were measured, and a correlation to water

solubility was drawn.

Complexes of Bi(III), Mn(II), Eu(III), Gd(III), and

Y(III) were synthesized with the ligand 2,6-diacetylpyridine

bis(acetic acid hydrazone). Crystals obtained from these

procedures were analyzed by x-ray crystallography and their

solid state structures determined. A study of their

solution stability over time was conducted by means of

nuclear magnetic resonance spectroscopy. The 1H, "C, and 89Y

spectra were taken of the Y(III) complex in D20 over a

period of one week. The spectra showed no change over time,

and the presence of a single peak in the 89Y spectrum

suggests that Y(III) existed in only one stable environment.


xiv














CHAPTER 1


INTRODUCTION


Bismuth Chemistry


The element bismuth has been known for about five

hundred years but was not identified as such until 1530.1

In 1786, Odier touted the use of bismuth subnitrate,

(BiO)N03, as a gastric antispasmodic. Since then, a variety

of bismuth salts including bismuth subcarbonate, (BiO)2C03,

bismuth subsalicylate, (BiO) (HOC6H4COO), and ammonium

bismuth citrate dihydrate, (NHI)Bi(C6H4O,) 2H20, have been

used to treat a wide range of human ailments. Some of these

include peptic ulcers, syphilis, and the topical

disinfection of wounds.2

With the exception of some commercial products which

utilize bismuth subsalicylate as a treatment for the relief

of gastric disorders, the use of bismuth compounds has

steadily waned as heavy metal salts have fallen out of

favor.3 Interest in bismuth chemistry has been rekindled,

however, with the discovery of colloidal bismuth subcitrate

(CBS), and its effect on Helicobacter Pylori, a stomach

bacterium recently pinpointed as a causal factor in the

formation of peptic ulcers. The water solubility of CBS and
1








2

its stability in solution, due to the strongly coordinating

citrate, have rendered it useful as a medicinal treatment

for this ailment.27 Further stimuli for the study of

bismuth coordination chemistry have been questions of

possible relativistic effects in the heavy elements,8 and

the use of bismuth in high temperature superconductors.9

The compound CBS appears to be active against peptic

ulcers in several ways. First, it inhibits the action of

pepsins in the stomach, possibly by adsorption of these

enzymes onto tiny particles of the bismuth complex. Second,

the presence of bismuth in the stomach's mucosal membrane

inhibits proteolysis and proton diffusion as well as

increasing the secretion of bicarbonate anions into the

mucous. Finally, and most significantly, the CBS complex

has proven to be bactericidal to H. Pylori.2 These

developments in bismuth chemistry have been the impetus for

our study of bismuth coordination complexes and their

properties.

Recent studies of bismuth complexes have fallen into

two general categories. Several complexes have been

synthesized by Herrmann and coworkers,4'5 Reedijk and

coworkers,6-7 and Postel and coworkers10 which contain ligands

made predominantly of carboxylate groups. Herrmann and

Reedijk have focused mainly on complexes which are

variations of CBS, i.e. citrate containing salts. Postel

has synthesized bismuth complexes with such carboxylate








3

containing ligands as mandelic acid, glycolic acid, and

ethylene glycol.

A second group of bismuth complexes has been

synthesized by Palenik and coworkers, and Battaglia and

coworkers which contain planar pentadentate ligands. Work

by Palenik has included the syntheses of bismuth complexes

with the ligands 2,6-diacetylpyridine bis(semicarbazone),

(DAPSC), and 1,10-diformylphenanthroline bis(semicarbazone),

(PHENSC),11-3 which have shown surprising water solubility.

A similar complex with the ligand 2,6-diacetylpyridine

bis(2-thenoylhydrazone), (DAPT), was synthesized by

Battaglia.14

Our study of bismuth coordination compounds has focused

on the synthesis of complexes with both carboxylate

containing ligands and planar pentadentate ligands. A

subsequent investigation of antibacterial properties yielded

some surprising results as a correlation to water solubility

was drawn. The complexes were further characterized by a

variety of methods including x-ray crystallography, infrared

(IR) spectroscopy, elemental analyses, and through the

method of valence bond sums.


Manganese and Gadolinium Chemistry


The use of nuclear magnetic resonance imaging (MRI) as

a technique for the detection of diseased body tissue has

grown in recent years. While this method has proven its








4

usefulness, its success has depended on the availability of

imaging agents that possess several important characterist-

ics. First, the imaging agent must be sufficiently water

soluble and stable in vivo to facilitate thorough passage

through the body. Any decomposition of the agent could

leave toxic amounts of the free ligand or metal ion in the

body. Second, the agent must provide a sharp contrast

between normal and diseased tissue which is accomplished by

utilizing paramagnetic metal centers and maximizing the

degree of inner sphere waters of hydration. Finally, the

desired imaging agent must show a tendency to localize in a

specific target tissue, a property that is determined

empirically from trials on other organisms.

The most common imaging agents used for the purpose of

MRI are complexes of Mn(II) and Gd(III). The paramagnetism

of these metal centers, which are d5 and f7, respectively,

makes them ideal choices as imaging agents. The choice of

ligand is important in determining the usefulness of these

complexes, as it is the ligand that dictates where the

complex will localize in the body and determines the degree

of inner sphere hydration. Multidentate ligands usually

yield a strong, stable complex that will not dissociate in

vivo. 15

After documented success in producing water soluble

complexes of Bi(III) with planar pentadentate ligands,1-14

similar complexes were synthesized using Mn(II) and Gd(III).








5

Besides the obvious contribution a multidentate ligand

brings to the stability of a complex, the use of a planar

ligand also provides areas above and below the metal center

which can accommodate several waters of hydration, a

situation that is advantageous for imaging agents.

Variability in the structural characteristics of the ligands

may be a way to 'direct' the complex to a desired body

tissue.

Complexes of Mn(II), Eu(III), Gd(III), and Y(III),

containing planar pentadentate ligands, were synthesized and

characterized by x-ray crystallography and elemental

analyses. An investigation of their solution stability over

time was attempted via a study of the 'H, 3"C, and 9Y nuclear

magnetic resonance (NMR) spectra for the Y(III) complex.

The results reveal a series of complexes that are

surprisingly water soluble and stable in solution, and which

can accommodate at least four inner sphere waters of

hydration.















CHAPTER 2


COMPLEXES OF BISMUTH(III):
A SYNTHETIC AND STRUCTURAL STUDY


Introduction


Historically, bismuth compounds have been used as

medicinal agents for a variety of purposes including the

treatment of stomach disorders and wound disinfection.

Though the use of bismuth salts waned after World War II,

interest has increased with the emergence of CBS as a

treatment for peptic ulcers. The solubility of CBS in water

is uncharacteristic of bismuth salts and has facilitated its

medicinal use.

Recently bismuth (III) complexes with the planar

pentadentate ligands DAPSC, PHENSC and DAPT have been

prepared and characterized structurally. The use of these

strongly coordinating neutral ligands rendered their Bi(III)

complexes surprisingly water soluble, an unusual condition

in bismuth complexes. We have synthesized a similar complex

with the ligand 2,6-diacetylpyridine bis(acetic acid

hydrazone), (DAPAAH), which has shown water solubility as

well. The ligand is shown in Figure 2-1. Single crystals

of the complex were used in an x-ray diffraction study which








7

showed, as previously reported,16 the ability of ligands of

this type to adapt to a variety of coordination environments

and metal ion sizes.

Attempts to synthesize a series of Bi(III) complexes

with three 'one-arm' variations on the DAPSC ligand were met

with little success. These ligands, including

salicylaldehyde semicarbazone, (SASC), did not effectively

coordinate Bi(III). However, crystals obtained during the

unsuccessful synthesis of [Bi-SASC]3 (the ligand is given

in Figure 2-2) were shown, via an x-ray study, to be the

free ligand hydrogen bonded to a single acetic acid, (HAc),

molecule. This structure was previously unreported.

The use of carboxylate-containing ligands in the

synthesis of complexes with Bi(III) has been of great

interest recently.4-7"10 Several of these complexes have

shown, through the formation of charged complexes, an

impressive water solubility. We have undertaken the

synthesis of Bi(III) complexes with a series of ligands

including picolinic acid, (PIC), dipicolinic acid, (DIPIC),

nitrilotriacetic acid, (NTA), ethylenediaminetetraacetic

acid, (EDTA), and diethylenetriaminepentaacetic acid,

(DTPA). The syntheses of Bi(HEDTA)17 and guanidinium

Bi(EDTA)18 have been reported but no structural data are

available.19

The reactions of these ligands, shown in Figures 2-3 -

2-7, with bismuth subcarbonate, (BiO)2CO3, have produced
























CH3


Figure 2-1: 2,6-diacetylpyridine
bis(acetic acid hydrazone) (DAPAAH)









OH






H H


Salicylaldehyde Semicarbazone (SASC)


H3


H 3
Hz


Figure 2-2:



















O

Figure 2-3: Picolinic Acid (PIC)


HO>


OH


0


Figure 2-4: Dipicolinic Acid (DIPIC)



HC N CH

0=7 I H-OH


Figure 2-5: Nitrilotriacetic Acid (NTA)






















/CH CH2



0 /-C\


0


Ethylenediaminetetraacetic Acid (EDTA)


HO. CHa2 AH2 ^2
R H2C\
0A


HO, /CH2
FO
0


II
0


CH2 CH2\ /H / OH

- OH 0
N0


H2C- ,OH
0
0


Figure 2-7: Diethylenetriaminepentaacetic Acid (DTPA)


F-OH


CH2\
F-OH


Figure 2-6:


r


C








11

a series of Bi(III) complexes which show a wide range of

water solubility. Crystals obtained in complexes of Bi(III)

with DIPIC, NTA, EDTA, and DTPA were used in x-ray

structural studies which revealed a number of similarities

among the structures of these compounds, including their

coordination polyhedra and the tendency to form dimer-like

units in the solid state. The PIC complex was insoluble and

no x-ray quality crystals were obtained.

Herein we report the syntheses and x-ray crystal

structures of Bi(III) complexes with the ligands DAPAAH,

DIPIC, NTA, EDTA, and DTPA along with the free ligand SASC.

The PIC complex was characterized via elemental analysis.


Experimental


Materials

Bismuth subcarbonate (BiO)2C03, guanidine carbonate

(C(NH2)3)2CO3, bismuth nitrate Bi(NO3)3-5H20 (J.T. Baker);

PIC, DIPIC, NTA, DTPA, 2,6-diacetylpyridine and

acethydrazide (Aldrich); EDTA (LaPine); salicylaldehyde and

semicarbazide hydrochloride (Kodak); sodium acetate (NaAc)

and glacial acetic acid (HAc) (Fisher); were all commercial

products and used without further purification. The

procedure used for the complexes of DIPIC, NTA, EDTA, and

DTPA was similar to that reported for the synthesis of

Bi(HEDTA).17








12

Synthesis of Bi(DAPAAH)Ac,24HO (1)

To a solution of 20 mL HAc in 20 mL H20 was added 0.286

g (0.561 mmol) (BiO)2CO3. After boiling for several hours

all solid went into solution. A mixture of 0.101 g (1.36

mmol) acethydrazide dissolved in 10 mL H20, and 0.0933 g

2,6-diacetylpyridine stirred in 15 mL HO0 was added directly

to the solution. A clear yellow solution (pH = 4) was

obtained. The solution was filtered and allowed to

evaporate. A single recrystallization from H20 revealed

beautiful yellow x-ray quality crystals. Anal. Calc (found)

for C17H30N5O0Bi: C, 30.32(30.07); H, 4.49(4.19);

N, 10.40(10.28).

Synthesis of Bi(PIC), (2)

A picolinic acid solution was made by dissolving 0.208

g (1.69 mmol) of the acid in 14 mL H20. The pH was

approximately 4. Solid Bi(NO3)3-5H20 (0.273 g (0.563 mmol))

was added directly to the solution. A white solid appeared

immediately and the pH decreased to approximately 1. The

solid was filtered and allowed to dry. Recrystallizations

from a water/ethanol/pyridine mixture, nitric acid solution,

and hydrochloric acid solution did not yield x-ray quality

crystals. Mp for 2, 340-3500C (dec). Anal. Calc(found) for

C18H12N306Bi: C, 37.56(37.16); H, 2.09(2.09); N, 7.30(7.21).
Synthesis of Bi2 (DIPIC)2 (HDIPIC) 2(HAc), 4H2O (3)

To a heated solution of 0.188 g (1.12 mmol) of DIPIC in

25 mL H20 (pH 2-3) was added 0.143 g (0.280 mmol) (BiO)2C03.








13

All solid was in solution within 0.5 h. White solid

obtained upon evaporation was redissolved in a solution of 8

mL HAc and 2 mL H20. After slow evaporation colorless x-ray

quality crystals were obtained. Anal. Calc(found) for

C32H20N4020Bi2-4H20: C, 30.25(29.69); H, 2.22(2.13);

N, 4.41(4.26).

Synthesis of Bi(NTA)*2H.O (4)

To a boiling solution of 0.107 g (0.561 mmol) NTA in 60

mL of H20 was added 0.142 g (0.279 mmol) of (BiO)2CO3. After

12 h of boiling with stirring, all solids had dissolved.

The solution was filtered while hot, and the clear,

colorless filtrate was allowed to evaporate. The

crystalline product was recrystallized once from H20 and

crystals suitable for an x-ray analysis were obtained.

Anal. Calc (found) for C6HoNOBi: C, 16.64(17.16);

H, 2.33(1.99); N, 3.23(3.28).

Synthesis of Bi(HEDTA)*2HO (5)

To 100 mL of HO was added 1.25 g (4.29 mmol) of EDTA.

The solution was heated to boiling, and 1.20 g (2.36 mmol)

of (BiO)2CO3 was added in small increments. After 30 min of

boiling the mixture was filtered while hot, and the

colorless filtrate allowed to evaporate. Colorless crystals

suitable for an x-ray single crystal analysis were formed.

Anal. Calc (found) for CoH,1N2OoBi: C, 22.48(22.16);

H, 3.21(3.15); N, 5.24(5.19).








14

Synthesis of (Guan) 2Bi (DTPA) 4HO (6)

To a boiling solution of 50 mL of H20 and 0.928 g (2.36

mmol) of DTPA was added 0.600 g (1.18 mmol) of (BiO)2CO3.

After stirring for 1 h all solid was in solution. To the

cooled solution was added 0.425 g (2.36 mmol) of guanidine

carbonate ((C(NH2) 3)2C3) The reaction mixture was heated

slowly to boiling, and after 2 h, the solution was filtered

and the clear, colorless filtrate allowed to evaporate

slowly. The resulting white solid was recrystallized three

times from H20 to obtain crystals suitable for an x-ray

anaylsis. Anal. Calc (found) for C16H3,NgO,,Bi: C, 24.34

(24.90); H, 4.85(4.61); N, 15.97(16.53).

Synthesis of SASC-HAc (7)

The ligand was synthesized by adding 0.94 mL

salicylaldehyde to a solution of approximately 1 g

semicarbazide hydrochloride and 1.5 g sodium acetate in 8 mL

H20. The resulting white precipitate was recrystallized

once from H20. Anal. Calc (found) for CsHN302:

C, 53.63(53.43); H, 5.06(5.00); N, 23.45(23.85).

Crystals of 7 were obtained during a procedure in which

0.138 g (0.270 mmol) (BiO)2CO3 was dissolved in 30 mL

glacial HAc and combined with 0.232 g (1.29 mmol) SASC.

Large colorless crystals, obtained on evaporation of the

clear colorless solution, appeared to lose solvent molecules

after drying in air. Recrystallization from HAc produced








15

large colorless crystals which were submitted for a single

crystal x-ray analysis.

X-ray Structural Studies

Data for all of the crystals were collected at room

temperature on a Siemens R3m/V diffractometer equipped with

a graphite monochromator utilizing Mo K, radiation (X =

0.71073 A). Forty reflections with 20.00 28 s 22.00 were

used to refine the cell parameters. Full intensity

reflections were collected using the w-scan method. Four

reflections were measured every 96 reflections to monitor

instrument and crystal stability Absorption corrections

were applied based on measured crystal faces using SHELXTL

plus;20 absorption coefficient.

The structures were solved by the heavy-atom method in

SHELXTL plus from which the location of the heavy elements

were obtained. The rest of the non-hydrogen atoms were

obtained from subsequent difference Fourier maps. The

structures were refined in SHELXTL plus using full-matrix

least squares. The non-H atoms were treated

anisotropically, whereas the positions of the hydrogen atoms

were calculated in ideal positions and their isotropic

thermal parameters were fixed. All parameters were refined

and Y w ( IFo IFc )2 was minimized; w=1/(a Fo )2, a( F) =

0.5 kI-1/2{[( I )]2 + (0.021)2}1/2, I(intensity)= ( I peak -

Ibackground ) (scan rate ), and a(I) = ( I peak + I background) 1/2 (scan

rate), k is the correction due to decay and Lp effects, 0.02








16

is a factor used to down weight intense reflections and to

account for instrument instability. The linear absorption

coefficient was calculated from values from the

International Tables for X-ray Crystallography.21 Scattering

factors for non-hydrogen atoms were taken from Cromer &

Mann22 with anomalous-dispersion corrections from Cromer &

Liberman,23 while those of hydrogen atoms were from Stewart,

Davidson, and Simpson.24



Discussion



The reaction of bismuth salts, such as bismuth nitrate

and bismuth subcarbonate, with DAPAAH and the carboxylic

acids PIC, DIPIC, NTA, EDTA, and DTPA, has proven to be a

convenient method of synthesizing complexes of these

ligands. Bismuth subcarbonate appears to be most useful

when used with acids with a pK of about 5 or lower. An acid

with a pK of higher than 5 does not seem effective at

dissolving the subcarbonate and requires the use of bismuth

nitrate. Our results also show that complexes containing

both fully and partially deprotonated ligands are possible

when using these polyprotic acids. This suggests that the

choice of an appropriate cation may be a convenient way to

vary the solubility of such complexes.

A thermal ellipsoid drawing of 1 given in Figure 2-8

shows the full bismuth coordination sphere and atomic








17

numbering scheme including the DAPAAH ligand and the two

coordinating acetate counteranions. Atomic coordinates and

bond distances and angles for the non-hydrogen atoms are

given in Tables 2-1 and 2-2, respectively. Coordinates for

the hydrogen atoms are given in Table 2-3, and the hydrogen

atom bond distances and angles are given in Table 2-4. The

structure was refined to an R value of 5.3%. This and other

crystal data are given in Table 2-5.

The DAPAAH coordinates in a pentadentate fashion

through N2, N3, N4, and the two carbonyl oxygens 01 and 012.

Two bidentate acetates complete the coordination sphere

bringing the total coordination number to nine. Charge

balance is maintained by deprotonation of the ligand at N5,

a designation based on the lack of a refined hydrogen in

this position, and the 1110 C12-N5-N4 bond angle. The usual

planarity of the ligand is affected by the presence of the

two acetates. To minimize steric interactions between the

acetate oxygens and the DAPAAH ligand, and to accommodate the

large Bi3 ion, the hydrazone 'arms' are twisted in opposite

directions. Previous work with ligands of this type has

shown their remarkable ability to adapt to a variety of

coordination environments and metal ion sizes.16

The bismuth complex with PIC, 2, was isolated as a

fast-forming precipitate directly from the reaction mixture.

This is not surprising considering that PIC has the

possibility of only a -1 charge. Three coordinating PIC




















014a


014b


Cl N 012 C12 N C13


01 016a


016b C16


C17







Figure 2-8: View of 1 showing the thermal ellipsoids
and atomic numbering. Methyl hydrogens
are omitted for clarity.














Table 2-1: Fractional coordinates
thermal parameters (A2)
compound 1.


and equivalent isotropica
for the non-H atoms of


Atom x


Bi
01
012
014a
014b
016a
016b
N1
N2
N3
N4
N5
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
C12
C13
C14
C15
C16
C17
01'
02'
03'
04'


0.77999(4)
0.6166(9)
0.6264(8)
0.8514(9)
0.6265(10)
0.8625(9)
0.6291(10)
0.8084(9)
0.8980(9)
1.0474(8)
0.8987(8)
0.8156(9)
0.6651(11)
0.5678(12)
1.0350(11)
1.1043(13)
1.1213(11)
1.2718(12)
1.3454(14)
1.2727(14)
1.1198(10)
1.0374(11)
1.1157(13)
0.6776(10)
0.5715(12)
0.7368(13)
0.741(2)
0.7433(14)
0.751(2)
0.8745(9)
0.8713(10)
0.6340(12)
0.6367(12)


z

-0.25413(2)
-0.1075(6)
-0.3770(5)
-0.3387(6)
-0.2962(7)
-0.1726(6)
-0.2041(7)
-0.0545(6)
-0.1137(6)
-0.2426(5)
-0.3726(6)
-0.4353(6)
-0.0596(7)
-0.0009(9)
-0.1152(7)
-0.0607(11)
-0.1820(7)
-0.1806(10)
-0.2437(12)
-0.3019(10)
-0.3030(8)
-0.3696(8)
-0.4294(9)
-0.4291(6)
-0.4881(9)
-0.3383(8)
-0.3885(12)
-0.1724(8)
-0.1298(14)
0.0911(6)
-0.5984(7)
0.3136(11)
0.1871(11)


U

0.02912(11)
0.055(3)
0.045(2)
0.047(3)
0.057(3)
0.058(3)
0.062 (3)
0.036(3)
0.036(3)
0.035(2)
0.034(2)
0.035(2)
0.038(3)
0.053 (4)
0.040(3)
0.067(4)
0.040(3)
0.064(5)
0.081(5)
0.065(5)
0.040(3)
0.044(3)
0.061(4)
0.031(3)
0.050(4)
0.044(4)
0.093(8)
0.048(4)
0.090(7)
0.063(3)
0.073(4)
0.125(5)
0.118(5)


aFor anisotropic atoms, the U value
Ueq = 1/3 Ej U- a,* aj* Aij where Aij
of the ith and th direct space unit


is Ueq, calculated as
is the dot product
cell vectors.


0.50538(4)
0.4424(10)
0.5514(8)
0.2824(8)
0.2490(9)
0.7386(9)
0.7551(9)
0.3256(9)
0.3863(9)
0.4970(9)
0.6160(9)
0.6744(9)
0.3582(12)
0.2841(13)
0.3573(12)
0.256(2)
0.4291(12)
0.424(2)
0.494(2)
0.565(2)
0.5642(12)
0.6364(13)
0.728(2)
0.6378(10)
0.7049(13)
0.2092(12)
0.055 (2)
0.8122(12)
0.9683(15)
0.1646(10)
0.8163(12)
-0.0839(15)
0.093 (2)











Table 2-2:


Bond Lengths (A) and Angles (0) for the non-H
atoms of compound 1.


2 3


01
012
014a
014b
016a
016b
N2
N3
N4
01
01
01
01
01
01
01
012
012
012
012
012
012
012
014a
014a
014a
014a
014a
014a
014b
014b
014b
014b
014b
016a
016a
016a
016a
016b
016b
016b
N2
N2
N3
N4
C1


1-2

2.769(9)
2.373(8)
2.371(7)
2.758(8)
2.446(8)
2.732(8)
2.700(9)
2.468(8)
2.411(9)
2.769(9)






2.373(8)







2.371(7)





2.758(8)




2.446(8)



2.732(8)


2.700(9)

2.468(8)
2.411(9)
1.208(14)


1-2-3











110.5(2)
107.8(3)
68.3(3)
92.8(3)
76.6(3)
57.8(2)
118.8(3)
90.2(3)
76.7(3)
108.2(3)
70.5(3)
162.8(3)
130.6(3)
65.1(3)
50.1(3)
145.7(3)
160.3(3)
82.4(3)
73.5(3)
85.2(3)
160.8(3)
118.5(3)
86.6(3)
119.0(3)
120.6(3)
50.0(3)
86.1(3)
72.6(3)
77.4(3)
114.9(3)
122.0(3)
90.1(3)
62.0(3)
129.3 (3)
67.3(3)
166.6(3)
118.4(7)


012
014a
014b
016a
016b
N2
N3
014a
014b
016a
016b
N2
N3
N4
014b
016a
016b
N2
N3
N4
016a
016b
N2
N3
N4
016b
N2
N3
N4
N2
N3
N4
N3
N4
N4
01
Bi











Table 2-2 -- continued


1 2


C12
C14
C14
C16
C16
N2
C1
C3
C3
Bi
C5
C5
C9
N5
N5
C10
C12
C2
C2
01
C4
C4
C5
C6
C6
N3
C7
C8
C9
C10
C10
N3
C11
C11
N4
C13
C13
012
C15
C15
014a
C17
C17
016a


012
014a
014b
016a
016b
N1
N1
N2
N2
N2
N3
N3
N3
N4
N4
N4
N5
C1
C1
C1
C3
C3
C3
C5
C5
C5
C6
C7
C8
C9
C9
C9
C10
C10
C10
C12
C12
C12
C14
C14
C14
C16
C16
C16


3

Bi
Bi
Bi
Bi
Bi
C1

Bi
N1
N1
C9
Bi
Bi
C10
Bi
Bi
N4
01
N1
N1
C5
N2
N2
N3
C3
C3
C5
C6
C7
N3
C8
C8
N4
C9
C9
012
N5
N5
014a
014b
014b
016a
016b
016b


1-2


1.275(13)
1.252(14)
1.228(15)
1.30(2)
1.23(2)
1.379(12)
1.359(13)
1.292(13)


1.344(14)

1.337(14)
1.365(12)

1.289(13)
1.320(12)
1.48(2)


1.47(2)

1.49(2)
1.386(15)


1.38(2)
1.33(2)
1.41(2)
1.47(2)


1.49(2)


1.50(2)


1.52(2)


1.50(2)


1-2-3

115.7(6)
101.1(7)
83.4(7)
100.3(7)
88.4(7)
115.8(9)

118.9(7)
119.8(9)
119.4(6)
119.6(8)
124.7(7)
115.6(6)
120.3 (9)
118.9(6)
120.2(7)
111.0(8)
120.5(10)
115.6(10)
123.9(10)
120.5(9)
124.4(10)
115.0(10)
122.1(11)
120.4(11)
117.4(9)
117.7(13)
120.4(12)
120.3(14)
119.0(9)
121.2(11)
119.8(11)
123.5(11)
119.7(9)
116.9(10)
117.0(9)
116.9(9)
126.0(9)
116.5(12)
118.2(12)
125.1(10)
116.7(12)
122.1(12)
121.2(10)























Table 2-3: Fractional
parameters


coordinates and isotropic thermal
(A2) for the H atoms of compound 1.


x

0.84202
0.62397
0.49681
0.51958
1.2065
1.06205
1.08973
1.32307
1.44958
1.32486
1.21784
1.08001
1.0995
0.62238
0.502090
0.52192
0.64783
0.81414
0.76252
0.65715
0.82037
0.78027


0.24255
0.22155
0.22749
0.35513
0.251770
0.1609
0.28788
0.37458
0.49068
0.61766
0.72832
0.82585
0.68987
0.76739
0.76048
0.62988
0.00932
0.00118
0.05793
1.01168
1.01942
0.97338


z

-0.00337
0.03231
-0.03853
0.04148
-0.07308
-0.07658
0.0032
-0.13733
-0.24556
-0.34322
-0.41568
-0.41833
-0.49243
-0.52398
-0.45008
-0.52801
-0.38386
-0.36149
-0.45179
-0.13349
-0.16196
-0.06679


U


Atom

H1
H2a
H2b
H2c
H4a
H4b
H4c
H6
H7
H8
Hlla
Hllb
Hllc
H13a
H13b
H13c
H15a
H15b
H15c
H17a
H17b
H17c


0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08












Table 2-4: Bond Lengths (A) and Angles (0) for the H atoms
of compound 1.


1 2 3 1-2 1-2-3

H1 N1 N2 1.19(1) 127.0(7)
H1 N1 C1 117.1(8)
H2a C2 H2b 0.96(1) 109.5(12)
H2a C2 H2c 109.5(13)
H2a C2 C1 109.5(10)
H2b C2 H2c 0.96(1) 109.5(11)
H2b C2 C1 109.5(12)
H2c C2 C1 0.96(1) 109.5(11)
H4a C4 H4b 0.96(1) 109.5(13)
H4a C4 H4c 109.5(13)
H4a C4 C3 109.5(13)
H4b C4 H4c 0.96(1) 109.5(15)
H4b C4 C3 109.5(12)
H4c C4 C3 0.96(2) 109.5(12)
H6 C6 C7 0.96(1) 121.2(11)
H6 C6 C5 121.1(13)
H7 C7 C8 0.96(1) 120.(2)
H7 C7 C6 120.(2)
H8 C8 C9 0.96(2) 119.9(14)
H8 C8 C7 119.9(13)
Hlla C11 Hllb 0.96(1) 109.5(13)
Hlla C11 Hllc 109.5(12)
Hlla C11 C10 109.5(13)
Hllb C11 Hllc 0.96(1) 109.5(14)
Hllb C11 C10 109.5(11)
Hllc C11 C10 0.96(1) 109.5(12)
H13a C13 H13b 0.96(1) 109.5(11)
H13a C13 H13c 109.5(13)
H13a C13 C12 109.5(10)
H13b C13 H13c 0.96(1) 109.5(11)
H13b C13 C12 109.5(11)
H13c C13 C12 0.96(1) 109.5(10)
H15a C15 H15b 0.96(2) 109.(2)
H15a C15 H15c 109.(2)
H15a C15 C14 109.5(15)
H15b C15 H15c 0.96(2) 109.(2)
H15b C15 C14 109.5(15)
H15c C15 C14 0.96(2) 109.5(13)
H17a C17 H17b 0.96(2) 109.(2)
H17a C17 H17c 109.(2)
H17a C17 C16 109.5(14)
H17b C17 H17c 0.96(2) 109.(2)
H17b C17 C16 110.(2)
H17c C17 C16 0.96(2) 109.4(14)











Table 2-5: Crystallographic data for compound 1.


A. Crystal data (298 K)
a, A
b, A
c, A
a, deg.
P, deg.
7, deg.
V, A3
dcalc, g cm-3(298 K)
Empirical formula
Formula wt, g
Crystal system
Space group
Z
F(000), electrons
Crystal size (mm3)


1
9.206(3)
9.300(2)
14.741(4)
97.77(2)
90.53 (2)
90.37(2)
1250.4(6)
1.789
C17H22N50OBi
673.44
Triclinic
P -1


4H2,


2
660
0.23 x 0.20 x 0.18


B. Data collection (298 K)
Radiation, X (A) Mo-K 0.71073
Mode w-scan
Scan range Symmetrically over 1.20 about K ,2 maximum
Background offset 1.0 and -1.0 in w from K 1,2 maximum
Scan rate, deg. min.-l 3 -6
28 range, deg. 3 55
Range of h k 1 0 s h 11
-12 s k s 12
-19 s 1 s 19


Total reflections measured
Unique reflections
Absorption coeff. A (Mo-K0), cm-1
Min. & Max. Transmission

C. Structure refinement
S, Goodness-of-fit
Reflections used, I > 3u(I)
No. of variables
R, RW (%)
Rint (%)
Max. shift/esd
min. peak in diff. four. map (e A-3)
max. peak in diff. four. map (e A3)


6117
5616
7.11
0.265, 0.351


2.23
4685
298
5.26, 6.80
1.49
0.000
-1.34
1.51


* Relevant expressions are as follows, where in the footnote
Fo and Fc represent, respectively, the observed and
calculated structure-factor amplitudes.
Function minimized was w( Fo IFc)2, where w = (a(F))-2
R = IllFol IF ) / l Fo 1/2
R = [Zw( Fo IF )2 / ( ) 1/2.
S = [w( Fo- F)2 / (m-n)/2








25

anions would produce a complex that is electrically neutral

and unlikely to stay in aqueous solution. It seems clear,

based on excellent elemental analysis results, that a pure

sample of Bi(PIC)3 was indeed obtained. The complex has

defied attempts at crystal growth from several solvents and

solvent mixtures.

A view of the Bi(DIPIC)(HDIPIC) (HAc) complex, 3, along

with the atomic numbering scheme is given in Figure 2-9.

Atomic coordinates and bond distances and angles for the

non-hydrogen atoms are given in Tables 2-6 and 2-7,

respectively. Hydrogen atom coordinates and bond distances

and angles are given in Tables 2-8 and 2-9, respectively.

The structure was refined to an R value of 3.0 %. This and

other crystal data for 3 are given in Table 2-10.

The x-ray analysis reveals a structure in which each

bismuth is coordinated by two tridentate DIPIC anions and a

monodentate HAc molecule. The total coordination number of

eight is completed by a DIPIC oxygen from an adjacent ligand

which is shared by both bismuth centers. Ligand oxygen 01

is likewise shared with the neighboring bismuth center

creating a 'dimer-like' unit consisting of the two bismuth

complexes connected by shared oxygens. This feature

manifests itself consistently in bismuth complexes with

carboxylate containing ligands. The combination of a

Bi(III) center with two DIPIC ligands, both capable of a -2

charge, necessitates that one carboxylate group remain
















































Figure 2-9: View of 3 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity.














Table 2-6:


Fractional coordinates and equivalent isotropica
thermal parameters for the non-H atoms of
compound 3.


Atom


x

1.04930(2)
0.7899(5)
0.8679(5)
0.6299(5)
1.0201(5)
0.8758(6)
0.7265(6)
0.6792(6)
0.5294(7)
0.4949(7)
0.6085(7)
0.7563(6)
0.8922(7)
1.1704(5)
0.8700(4)
0.8031(6)
1.3639(5)
1.5664(6)
0.9013(7)
1.0740(7)
1.1266(8)
1.2873(8)
1.3837(7)
1.3240(6)
1.4209(6)
1.0979(12)
1.2554(13)
0.897(4)
0.744(4)
1.1192(14)
0.899(6)
0.992(2)
0.5039(8)
0.7383 (5)


z

1.16123(2)
1.0887(4)
0.9373 (3)
0.7775(3)
1.3177(3)
1.3802(4)
0.8846(5)
0.9704(4)
0.9309(5)
1.0165(6)
1.1388(6)
1.1710(5)
1.3004(5)
1.3581(3)
1.1781(3)
1.2732(5)
1.3293 (4)
1.5117(4)
1.2670(5)
1.3693(5)
1.4681(5)
1.5596(5)
1.5478(5)
1.4463 (4)
1.4240(5)
1.0417(10)
0.9854(9)
0.860(4)
0.809(3)
0.9616(10)
0.835(3)
0.8320(9)
0.7853(6)
0.4657(4)


U

0.02974(8)
0.028(2)
0.041(2)
0.055(2)
0.041(2)
0.055(2)
0.034(2)
0.029(2)
0.037(2)
0.044(3)
0.040(2)
0.031(2)
0.036(2)
0.030(2)
0.0383(15)
0.062(2)
0.046(2)
0.061(2)
0.038(2)
0.036(2)
0.044(2)
0.048(3)
0.044(2)
0.034(2)
0.036(2)
0.114(6)
0.125(6)
0.11(2)
0.08(2)
0.067(5)
0.07(2)
0.097(6)
0.097(4)
0.046(2)


aFor anisotropic atoms,
= 1/3 ZiL U.. ai* aj* Aij
ith and j direct space


the U value is Ueq, calculated as Ueq
where Aj is the dot product of the
unit cell vectors.


0.14229(2)
0.1797(4)
0.0349(4)
-0.0033(5)
0.2722(4)
0.3751(5)
0.0479(6)
0.1285(5)
0.1480(6)
0.2191(7)
0.2715(6)
0.2509(5)
0.3042(6)
0.0705(5)
-0.0418(4)
-0.2104(5)
0.3056(4)
0.3246(6)
-0.1070(6)
-0.0461(6)
-0.1091(7)
-0.0441(7)
0.0783(7)
0.1342(6)
0.2643(6)
0.3477(10)
0.5004(10)
0.567(4)
0.362(2)
0.4042(9)
0.446(4)
0.3811(12)
0.4382(7)
0.5369(4)


Bi
N
01
02
03
04
C1
C2
C3
C4
C5
C6
C7
N'
01'
02'
03'
04'
C1'
C2'
C3'
C4'
C5'
C6'
C7'
05
06
05'
06'
C8
C8'
C9
07
08











Bond Lengths (A) and Angles (0) for
atoms of compound 3.


2


N
N
N
N
N
N
01
01
01
01
01
01
Oli
Oli
Oli
Oli
Oli
03
03
03
03
N'
N'
N'
01'
01'
03'
05
C2
C2
C6
C1
C1
C7
C7
C2
C2
01
C3
C3
N
C4
C5
C6
C7
C7
N


3

01
Oli
03
N'
01'
03'
Oli
03
N'
01'
03'
05
03
N'
01'
03'
05
N'
01'
03'
05
01'
03'
05
03'
05
05
N
C6
Bi
Bi
Bi

Bi

01
02
02
N
C1
C1
C2
C3
C4
N
C5
C5


1-2

2.415(5)





2.489(3)





2.543(5)




2.325(5)



2.470(4)


2.206(4)

2.768(3)
2.672(11)
1.340(5)

1.343(8)
1.291(7)
1.209(5)
1.280(8)
1.221(9)
1.515(9)


1.383 (9)


1.378(10)
1.382(7)
1.375(9)
1.508(6)


Table 2-7:


the non-H


1-2-3

65.5(2)
129.03(12)
67.48(13)
125.6(2)
75.0(2)
132.40(14)
65.48(14)
132.99(15)
138.55(14)
78.61(13)
145.68(14)
75.6(2)
157.87(14)
85.04(15)
82.6(2)
96.84(13)
104.9(3)
72.8(2)
89.3(2)
72.87(14)
93.1(3)
68.83(13)
61.69(13)
143.0(2)
130.33(13)
146.8(2)
81.6(2)
75.5(3)
120.1(5)
121.5(4)
118.4(3)
121.6(4)

123.2(3)

114.9(4)
119.4(6)
125.7(6)
120.9(5)
122.6(4)
116.5(5)
118.6(5)
120.6(7)
117.7(7)
114.6(5)
123.3(6)
122.1(4)


















Table 2-7 -- continued.


1

03
03
04
C2'
C2'
C6'
C1'
C1'
C7'
C7'
C2'
C2'
01'
C3'
C3'
N'
C4'
C5'
C6'
C7'
C7'
N'
03'
03'
04'
C8
C8
C8'
C8'
C9
C9
05
C9
C9
05'
C8


1-2-3


124.4
116.2
119.4
119.9
114.2
125.7
125.1


2

C7
C7
C7
N'
N'
N'
01'
02'
03'
04'
C1'
C1'
C1'
C2'
C2'
C2'
C3'
C4'
C5'
C6'
C6'
C6'
C7'
C7'
C7'
05
06
05'
06'
C8
C8
C8
C8'
C8'
C8'
C9


3

04
C6
C6
C6'
Bi
Bi
Bi

Bi

01'
02'
02'
N'
C1'
C1'
C2'
C3'
C4'
N'
C5'
C5'
04'
C6'
C6'
Bi



05
06
06
05'
06'
06'
C8'


1-2




1.324(7)

1.344(5)
1.287(7)
1.211(8)
1.223(7)
1.292(6)
1.518(6)


1.390(9)


1.402(7)
1.372(10)
1.381(9)
1.487(8)





1.19(2)
1.273(14)
1.29(7)
1.34(6)
1.501(14)


1.25(6)


116.1(3)

115.8(5)
119.8(5)
124.4(5)
122.5(4)
121.8(5)
115.6(5)
117.9(6)
118.6(6)
120.3(5)
115.2(5)
124.1(4)
120.7(5)
125.2(6)
121.1(4)
113.6(5)
157.7(9)



125.6(10)
114.1(11)
120.1(10)
143. (4)
112. (3)
104. (5)
109. (2)















Table 2-8: Fractional coordinates and isotropic thermal
parameters (A2) for the H atoms of compound 3.


x

0.456(7)
0.422(8)
0.595(7)
1.629(11)
1.028(12)
1.332(6)
1.487(8)
0.44422
0.55951
0.78709
0.79786


0.111(6)
0.231(6)
0.328(6)
0.390(9)
-0.209(9)
-0.101(5)
0.120(7)
0.41557
0.40377
0.60287
0.49661


z

0.848(6)
0.993(5)
1.199(5)
1.497(8)
1.453 (8)
1.621(4)
1.589(6)
0.7097
0.81479
0.51898
0.44399


U

0.04(2)
0.03(2)
0.028(14)
0.08(3)
0.10(3)
0.015(11)
0.05(2)
0.08
0.08
0.08
0.08


Table 2-9:


Bond Lengths (A)
of compound 3.


and Angles (0) for the H atoms


1-2

0.93(5)


0.68(7)

0.94(7)

0.83(9)
1.11(9)

1.02(5)

0.85(6)

1.19(2)
0.827(6)
0.780(4)


1-2-3

123. (5)
103. (5)
118. (5)
124. (5)
116. (5)
118. (3)
124. (3)
116. (5)
133. (5)
109. (5)
124. (2)
116. (2)
111. (5)
127. (5)
157.7(9)
122.4(10)
116.1(5)


Atom


H3
H4
H5
H4 "
H3'
H4'
H5'
H7a
H7b
H8a
H8b


1

H3
H3
H3
H4
H4
H5
H5
H4"
H3'
H3'
H4'
H4'
H5'
H5'
C8
H7a
H8a


2

C3
C3
C3
C4
C4
C5
C5
04'
C3'
C3'
C4'
C4'
C5'
C5'
05
07
08


3

C4
H4
C2
C5
C3
C6
C4
C7'
C4'
C2'
C5'
C3'
C6'
C4'
Bi
H7b
H8b











Table 2-10: Crystallographic data for compound 3.


A. Crystal data (298 K)
a, A
b, A
c, A
a, deg.
3, deg.
7, deg.
V, A3
dcalc, g cm3(298 K)
Empirical formula
Formula wt, g
Crystal system
Space group
Z
F(000), electrons
Crystal size (mm3)


3
9.251(1)
10.478(1)
11.666(1)
94.87(1)
110.49(1)
107.63(1)
986.2(2)
2.140
C32H20N4020Bi2 4H20
1270.54
Triclinic
P -1
4

0.20 x 0.11 x 0.08


B. Data collection (298 K)
Radiation, X (A) Mo-K,, 0.71073
Mode w-scan
Scan range Symmetrically over 1.20 about K,,,2 maximum
Background offset 1.0 and -1.0 in w from Ka ,2 maximum
Scan rate, deg. min.-' 3 -6
28 range, deg. 3 55
Range of h k 1 0 s h < 12
-13 s k s 13
-15 s 1 s 14


Total reflections measured
Unique reflections
Absorption coeff. p (Mo-K,), cm-
Min. & Max. Transmission

C. Structure refinement
S, Goodness-of-fit
Reflections used, I > 2u(I)
No. of variables
R, Rw* (%)
Rint (%)
Max. shift/esd
min. peak in diff. four. map (e A-3)
max. peak in diff. four. map (e A-3)


4754
4402
9.01
0.266, 0.543


1.17
3877
336
3.02, 3.38
1.71
0.0002
-10
0.94


* Relevant expressions are as follows, where in the footnote
Fo and Fc represent, respectively, the observed and
calculated structure-factor amplitudes.
Function minimized was w(Foj IFcJ)2, where w= (a(F))-2
R = I ( IFo 1Fe ) / i IFo 1
Rw [Iw(IFo, IFc1)2 / IF 2]1/2
S = [w(!IFo IFJc)2 / (m-n)]11/2








32

protonated to maintain charge balance. The proton appears

to be located on 04' based on the carbon to oxygen bond

lengths.

The crystal structure of Bi(NTA), 4, along with the

atomic numbering scheme, is given in the thermal ellipsoid

drawing in Figure 2-10. Atomic coordinates and bond

distances and angles for the non-hydrogen atoms are given in

Tables 2-11 and 2-12, respectively. Hydrogen atom

coordinates, and bond distances and angles, are given in

Tables 2-13 and 2-14, respectively. The structure was

refined to an R value of 3.5 %. Crystal data are given in

Table 2-15.

The complex consists of a single Bi(III) coordinated to

a completely deprotonated NTA trianion. Complete

deprotonation of NTA is necessary to maintain charge balance

but produces a neutral complex that is only slightly more

soluble than the previously mentioned Bi(PIC)3. The NTA

ligand coordinates in a tetradentate fashion through the

single nitrogen, N, and singly through one 0 atom from each

of the three carboxylate groups. The coordination sphere of

eight donor atoms shown in Figure 2-10 is completed by two

water molecules, 04 and 05, and two carboxylate oxygens from

an adjacent ligand, 02i and 03'i. As in 3, the sharing of

carboxylate oxygens produces a 'dimer-like' unit.

A view of the Bi(HEDTA) complex, 5, is shown in Figure

2-11 along with the atomic numbering scheme. Atomic



























C2 r 02'

01' C1'

02


Bi 02i
04

03'i



05








Figure 2-10: View of 4 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity.























Table 2-11:


Fractional coordinates and equivalent
isotropica thermal parameters (A2) for the
non-H atoms of compound 4.


x

0.08221(5)
0.0602(12)
0.0532(12)
0.1090(13)
0.1018(11)
0.2339(12)
-0.2757(10)
-0.5332(10)
-0.0856(12)
0.3527(12)
0.0976(14)
0.131(2)
0.1781(13)
0.2058(15)
-0.3390(14)
-0.1708(14)


0.094810(10)
0.1436(3)
0.2020(3)
0.2974(3)
0.0164(3)
-0.0001(3)
0.1021(3)
0.1309(4)
0.1154(3)
0.0308(5)
0.2392(4)
0.2104(4)
0.0355(4)
0.1072(4)
0.1232(4)
0.1382(6)


z

0.43940(4)
0.7101(9)
0.4132(8)
0.5236(9)
0.6692(8)
0.9368(8)
0.4465(8)
0.5768(9)
0.1556(8)
0.2697(10)
0.5353(12)
0.7093(12)
0.8161(11)
0.8453(10)
0.5702(12)
0.7274(12)


U

0.01760(10)
0.020(2)
0.033 (3)
0.044(3)
0.026(2)
0.036 (3)
0.030(2)
0.039(2)
0.029(2)
0.053(3)
0.027(3)
0.029(3)
0.022(3)
0.023 (3)
0.025(3)
0.032(3)


aFor anisotropic atoms, the U value is Ueq, calculated as Ueq
= 1/3 iZ U.i ai* aj* Ai where Ai is the dot product of the
th and j direct space unit cell vectors.


Atom


Bi
N
01
01'
02
02'
03
03'
04
05
C1
C1'
C2
C2'
C3
C3'













Table 2-12: Bond Lengths (A) and Angles (0) for the non-H
atoms of compound 4.


2


1_

N
01
02
02i
03
03'i
04
05
C1'
C1'
C1'
C2'
C2'
C3'
C1
C1
C2
C2
C3
C3
Cl'
C1'
01
N
C2'
C2'
02
N
C3'
C3'
03
N


3










C2'
C3'
Bi
C3'
Bi
Bi
Bi

Bi

Bi

01
01'
01'
Cl
02
02'
02'
C2
03
03'
03'
C3


1-2

2.500(8)
2.258(6)
2.501(6)
2.665(6)
2.253(7)
2.435(6)
2.403 (6)
2.767(9)
1.468(11)


1.492(10)

1.484(12)
1.260(11)
1.225(11)
1.274(10)
1.238(11)
1.259(13)
1.235(11)
1.537(14)



1.524(12)



1.521(12)


Bi
Bi
Bi
Bi
Bi
Bi
Bi
Bi
N
N
N
N
N
N
01
01'
02
02'
03
03'
C1
C1
C1
CI'
C2
C2
C2
C2'
C3
C3
C3
C3'


1-2-3










110.8(6)
111.9(8)
108.0(6)
109.5(7)
109.0(5)
107.4(5)
122.4(6)

118.1(5)

122.2(5)

118.4(8)
117.7(9)
123.8(9)
113.4(7)
117.9(7)
117.5(7)
124.6(8)
110.7(6)
119.5(8)
115.9(9)
124.5 (8)
115.9(8)












Table 2-13: Fractional coordinates and isotropic thermal
parameters (A2) for the H atoms of compound 4.


x

-0.16908
-0.1467
0.44329
0.35049
0.04852
0.28421
0.35569
0.16862
-0.17754
-0.21109


z


0.14176
0.0791
0.05756
0.02926
0.23531
0.21268
0.1187
0.11778
0.10475
0.17805


0.1347
0.1132
0.29155
0.17215
0.77181
0.76044
0.84927
0.94839
0.80534
0.76975


U


0.01(2)
0.14(8)
0.09(6)
0.04(3)
0.08
0.08
0.08
0.08
0.08
0.08


Table 2-14: Bond Lengths (A) and Angles (0)
of compound 4.


1 2 3 1-2

H4a 04 H4b 0.752(7)
H4a 04 Bi
H4b 04 Bi 0.889(7)
H5a 05 H5b 0.788(9)
H5a 05 Bi
H5b 05 Bi 0.808(8)
H1'a C1' H1'b 0.960(10)
H1'a C1' N
H1'a C1' C1
H1'b C1' N 0.960(10)
H1'b C1' C1
H2'a C2' H2'b 0.960(9)
H2'a C2' N
H2'a C2' C2
H2'b C2' N 0.960(9)
H2'b C2' C2
H3'a C3' H3'b 0.960(11)
H3'a C3' N
H3'a C3' C3
H3'b C3' N 0.960(11)


for the H atoms



1-2-3

108.6(7)
119.4(6)
107.1(5)
96.6(10)
91.5(7)
130.6(7)
109.5(9)
108.5(9)
108.5(8)
108.5(8)
108.5(9)
109.5(8)
109.2(8)
109.2(8)
109.2(8)
109.2(8)
109.5(10)
107.8(8)
107.8(9)
107.8(9)
107.8(8)


Atom

H4a
H4b
H5a
H5b
H1'a
H1'b
H2'a
H2'b
H3'a
H3'b


C3


H3'b


C3'











Table 2-15: Crystallographic data for compound 4.


A. Crystal data (298 K)
a, A
b, A
c, A
3, deg.
V, A3
dcai, g cm-3 (298 K)
Empirical formula
Formula wt, g
Crystal system
Space group
Z
F(000), electrons
Crystal size (mm3)


4
6.242(1)
20.927(3)
8.307(1)
102.49(1)
1059.4(3)
2.716
C6H6NO6Bi- 2H20
433.13
Monoclinic
P 21/n
4
800
0.30 x 0.26 x 0.20


B. Data collection (298 K)
Radiation/ X, (A) Mo-K,/0.71073
Mode w-scan
Scan range Symmetrically over Xo about Kl,2 maximum
(X = 1.5)
Background offset 1.0 and -1.0 in w from Kal,2 maxima
Scan rate, deg. min.-1 3 -6
28 range, deg. 3 55
Range of h k 1 0 h < 8
0 s k < 27
-10 s 1 s 10


Total reflections measured
Unique reflections
Absorption coeff. /L (Mo-K~), mm-1
Minimum / maximum transmission

C. Structure refinement
S, Goodness-of-fit
Reflections used, I > 2o(I)
No. of variables
R, RJ (%)
Ri.t, (%)
Max. shift/esd
min. peak in diff. four. map (e A-3)
max. peak in diff. four. map (e A-3)


2744
2446
16.67
0.035


/ 0.105


1.44
1943
149
3.47, 4.09
3.54
0.001
-2.54
2.29


* Relevant expressions are as follows, where in the footnote
Fo and Fc represent, respectively, the observed and
calculated structure-factor amplitudes.
Function minimized was w(IFoI 1Fc)2, where w= (a(F))-2
R = Z(IIFol IFJ) / ZIF
R.= [w( IFoJ IFc )2 / F 1F,2]1/2
S = [yw(IFo IFj1)2 / (m-n)]1/2


im








38

coordinates and bond distances and angles for non-hydrogen

atoms are given in Tables 2-16 and 2-17, respectively.

Tables 2-18 and 2-19 contain the hydrogen atom coordinates

and bond distances and angles, respectively. The crystal

structure was refined to an R value of 2.2 %. This and

other relevant data regarding the crystal, data collection,

and structure refinement are given in Table 2-20.

The complex, 5, consists of a single EDTA molecule

coordinating in a hexadentate fashion through both

nitrogens, N1 and N2, and singly through one 0 atom from

each of the four carboxylate groups. The coordination

sphere, shown in Figure 2-11 containing eight donor atoms,

is completed by two carboxylate oxygens, 03'i and 04'i, from

a neighboring complex. There are no coordinated water

molecules. The ligand remains singly protonated in the

crystalline state to maintain a 3- charge, giving rise to

the notation HEDTA. The Bi(HEDTA) neutral molecule appears

to be more soluble than 4, possibly due to the presence of

the single ionizable proton. This proton has been assigned

to 01 on the basis of bond lengths in the carboxylate

groups. In carboxylates 2 to 4 the C-O bond distances are

statistically equivalent indicating conjugation of the

double bond after deprotonation. The C-O bond distances in

carboxylate 1 are not statistically equivalent, differing by

0.09 A, indicating a nonconjugated system.



















04'








C5 C1
C6
C0
N2 N1 C' 01'

03'i
02'


02 C3
03


04'I
03'











Figure 2-11: View of 5 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity.
















Table 2-16: Fractional coordinates and equivalent
isotropica thermal parameters (A2) for the
non-H atoms of compound 5.


x

0.0
0.1362(5)
0.2626(5)
-0.1514(5)
-0.2776(5)
-0.0415(5)
-0.0031(5)
0.0338(5)
0.0119(7)
0.0727(6)
-0.0930(5)
0.1544(6)
0.1892(7)
-0.1779(6)
-0.2032(7)
0.0780(6)
0.0032(9)
-0.0880(8)
-0.0092(8)
0.0298(7)
-0.0602(7)
0.1868(5)
0.3003(6)


0.12068(4)
0.1168(10)
0.1691(14)
0.0000(15)
0.0472(14)
0.4449(14)
0.7487(10)
-0.0447(11)
-0.1408(12)
0.3664(11)
0.2209(12)
0.287(2)
0.187(2)
0.244 (2)
0.082(2)
0.549(2)
0.5826(13)
0.061(2)
-0.0484(15)
0.4059(14)
0.4077(14)
0.2631(14)
-0.011(2)


z

0.0
0.0113(7)
0.1119(8)
-0.0637(9)
-0.0606(7)
-0.0609(7)
-0.0641(6)
0.1563(6)
0.3037(8)
0.1263(8)
0.1141(7)
0.1736(9)
0.0944(9)
0.0529(9)
-0.0284(9)
0.0652(9)
-0.0234(6)
0.1936(9)
0.2195(8)
0.2093(9)
0.1667(9)
-0.1826(8)
-0.1832(8)


U

0.02009(11)
0.033(3)
0.046(3)
0.056(3)
0.040(3)
0.033(3)
0.037(3)
0.033 (3)
0.049(4)
0.025(3)
0.023 (3)
0.031(3)
0.032(4)
0.033(4)
0.031(4)
0.027(3)
0.021(3)
0.033(4)
0.031(4)
0.027(3)
0.025(3)
0.050(3)
0.059(4)


aFor anisotropic atoms, the U value is Ueq, calculated as Ueq
= 1/3 i .1 Ui a* aj* A. where Ai. is the dot product of the
ith and j direct space unit cell vectors.


Atom


Bi
01
01'
02
02'
03
03'
04
04'
N1
N2
C1
C1'
C2
C2'
C3
C3'
C4
C4'
C5
C6
O
0'











Table 2-17:


Bond Lengths (A) and
atoms of compound 5.


Angles (0) for the non-H


2


1-2-3


01
02
03
03'i
04
04'ii
N1
N2
Cl'
Cl'
C2'
C2'
C3'
C3'
C4'
C4'
C1
C1
C1
C3
C3
C5
C2
C2
C2
C4
C4
C6
C1'
01
01
01'
C2'
02
02
02'
C3'
03
03
03'
C4'
04
04
04'
C6
N2


Bi
Bi
Bi
Bi
Bi
Bi
Bi
Bi
01
01'
02
02'
03
03'
04
04'
N1
N1
N1
N1
N1
N1
N2
N2
N2
N2
N2
N2
C1
C1'
C1'
C1'
C2
C2'
C2'
C2'
C3
C3'
C3'
C3'
C4
C4'
C4'
C4'
C5
C6


3


1-2

2.306(9)
2.642(9)
2.400(9)
2.678(7)
2.295(7)
2.673(11)
2.461(8)
2.577(9)
1.316(13)
1.226(14)
1.25(2)
1.256(14)
1.232(14)
1.249(11)
1.26(2)
1.248(14)
1.478(13)


1.504(15)

1.51(2)
1.474(12)


1.508(14)

1.491(12)
1.51(2)



1.52(2)



1.506(15)



1.50(2)



1.50(2)


120.7(8)

118.8(8)

118.3(7)

124.2(7)

110.1(9)
110.6(9)
106.8(6)
111.1(8)
107.0(6)
111.2(6)
108.9(9)
111.1(8)
112.6(7)
110.6(8)
106.9(7)
106.7(7)
112.4(9)
124.4(12)
115.8(10)
119.7(10)
111.3(9)
123.5(11)
119.8(10)
116.6(11)
112.6(9)
123.3(9)
120.3(9)
115.6(10)
113.5(11)
121.7(12)
119.5(9)
118.8(13)
112.7(9)
113.0(8)


Bi

Bi

Bi

Bi

C3
C5
Bi
C5
Bi
Bi
C4
C6
Bi
C6
Bi
Bi
N1
01'
C1
C1
N2
02'
C2
C2
N1
03'
C3
C3
N2
04'
C4
C4
N1
C5
























Table 2-18: Fractional coordinates and isotropic thermal
parameters (A2) for the H atoms of compound 5.


x

0.14727
0.18951
0.15154
-0.21196
-0.18399
0.08572
0.12351
-0.09457
-0.13093
0.04672
0.0445
-0.07499
-0.08375
0.14122
0.22294
0.19956
0.29878
0.30146
0.35154


-0.00462
0.39282
0.19419
0.23954
0.36805
0.65892
0.53723
0.11796
-0.03084
0.5312
0.30627
0.51185
0.43061
0.20214
0.15913
0.36556
-0.08576
0.11582
-0.02474


z

0.01393
0.20483
0.22668
0.09946
0.01793
0.11168
0.03666
0.25677
0.16643
0.24003
0.26199
0.11668
0.22348
-0.15042
-0.19136
-0.13863
-0.23989
-0.19979
-0.14366


Atom


H1
Hla
Hib
H2a
H2b
H3a
H3b
H4a
H4b
H5a
H5b
H6a
H7b
Ha
Hb
He
H'a
H'b
H'c


U

0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08
0.08















Table 2-19: Bond Lengths (A)
of compound 5.


for the H atoms


2


1

H1
H1
Hla
Hla
Hla
Hlb
Hlb
H2a
H2a
H2a
H2b
H2b
H3a
H3a
H3a
H3b
H3b
H4a
H4a
H4a
H4b
H4b
H5a
H5a
H5a
H5b
H5b
H6a
H6a
H6a
H7b
H7b
Ha
Ha
Hb
H'a
H'a
H'b
H'c


3

C1'
Bi
Hlb
C1'
N1
Cl'
N1
H2b
C2'
N2
C2'
N2
H3b
C3'
N1
C3'
N1
H4b
C4'
N2
C4'
N2
H5b
C6
N1
C6
N1
H7b
N2
C5
N2
C5
Hb
Hc
He
H'b
H'c
H'c
HOb


1-2

0.850(7)

0.960(10)


0.960(12)

0.960(13)


0.960(12)

0.960(11)


0.960 (13)

0.960(12)


0.960(12)

0.960(10)


0.960(10)

0.960(10)


0.960(13)

1.073(10)

0.972(9)
0.904(11)

0.895(12)
0.900(9)


1-2-3

103.1(8)
103.1(7)
109.5(10)
108.7(11)
108.8(9)
108.6(10)
108.8(10)
109.5(12)
109.1(10)
109.1(10)
109.0(10)
108.8(10)
109.5(11)
108.7(9)
108.7(10)
108.6(11)
108.6(10)
109.5(14)
108.4(9)
108.4(10)
108.5(10)
108.5(9)
109.5(10)
108.4(10)
108.6(10)
108.8(11)
108.8(10)
109.5(10)
108.4(9)
108.7(10)
108.7(10)
108.6(10)
108.9(9)
96.9(9)
126.6(9)
110.0(12)
103.2(11)
99.3 (10)
135.6(10)


and Angles (0)











Table 2-20: Crystallographic data for compound 5.


A. Crystal data (298 K)
a, A
b, A
c, A
3, deg.
V, A3
dcaic, g cm-3(298 K)
Empirical formula
Formula wt, g
Crystal system
Space group
Z
F(000), electrons
Crystal size (mm3)

B. Data collection (298 K)
Radiation/, X (A)
Mode w-scan


5
17.196(2)
6.837(1)
13.277(2)
105.74(1)
1502.4(4)
2.358
CloH,3N2OgBi' 2H20
534.24
Monoclinic
Cc
4
1016
0.39 x 0.22 x 0.16


Mo-Ka/ 0.71073


Scan range Symmetrically over Xo about K,,2 maximum
(X = 1.2)
Background offset 1.0 and -1.0 in a from K1,2 maxim
Scan rate, deg. min.-1 2 -4
28 range, deg. 3 50
Range of h k 1 0 < h < 20


Total reflections measured
Unique reflections
Absorption coeff. A (Mo-K,), mm-1
Minimum / maximum transmission

C. Structure refinement
S, Goodness-of-fit
Reflections used, I > 2a(I)
No. of variables
R, RW (%)
Rint (%)
Max. shift/esd
min. peak in diff. four. map (e A3)
max. peak in diff. four. map (e A-3)


0 < k < 8
-15 < 1 < 15


1495
1367
11.77
0.070


1.29
1288
206
2.24,
0.00
0.001
-1.49
1.52


/ 0.200





2.72


* Relevant expressions are as follows, where in the footnote
Fo and F, represent, respectively, the observed and
calculated structure-factor amplitudes.
Function minimized was w(IFol IFc)2, where w= (a(F))-2
R = I(IFol IFJ ) / I Fo
R = [w( Fo! IFJ)2 / XFo 121/2
S = [-w(IFol IF I)2 / (m-n)]1/2


um








45

Figure 2-12 shows a thermal ellipsoid plot of the

Bi(DTPA) complex, 6, including the atomic numbering scheme.

Atomic coordinates and selected bond distances and angles

for the non-hydrogen atoms are given in Tables 2-21 and 2-

22, respectively. Tables 2-23 and 2-24 give the hydrogen

atom coordinates and bond distances and angles,

respectively. The structure was refined to an R value of

3.8 %. This and other crystal data are given in Table 2-25.

The complex contains the octadentate ligand DTPA, which

coordinates through three nitrogens, N1 N3, and singly

through one 0 atom from each of the five carboxylate groups.

Complete deprotonation of the ligand produces a 5- charge,

which is balanced by the Bi3, and two guanidinium (1+)

cations. An attempt was made to synthesize the complex

without guanidinium countercations, but this did not yield a

crystalline product. The Bi(III) is nine-coordinate with

the ninth coordination position taken by a carboxylate

oxygen, Ol'i, from another Bi(DTPA), again yielding a

'dimer-like' arrangement. Of the four bismuth carboxylate

complexes, Bi(DTPA) is the most soluble due to the presence

of a net 2- charge on the complex.

A thermal ellipsoid plot and atomic numbering scheme

for SASC-HAc, 7, is shown in Figure 2-13. Atomic

coordinates and bond distances and angles for the non-

hydrogen atoms of 7 are given in Tables 2-26 and 2-27,

respectively. Hydrogen atom coordinates and bond distances






























NI Bi C8 C9 C5'
C1





C3'
0303'








Figure 2-12: View of 6 showing the thermal ellipsoids
and atomic numbering. Hydrogens are
omitted for clarity.











Table 2-21:


Fractional coordinates and equivalent
isotropica thermal parameters (A2) for the
non-H atoms of compound 6.


Atom


Bi
01
01'
02
02'
03
03'
04
04'
05
05'
N1
N2
N3
C1
C1'
C2
C2'
C3
C3'
C4
C4'
C5
C5'
C6
C7
C8
C9
C10
N11
N12
N13
C20
N21
N22
N23
011
012
013
014


x

0.95368(2)
0.9342 (4)
0.8917(4)
0.8528(4)
0.7321(4)
0.9271(4)
0.9018(4)
1.0428(4)
1.0651(4)
1.0667(4)
1.1834(4)
0.7923(4)
0.8432(4)
1.0014(4)
0.8103(6)
0.8846(5)
0.7465(6)
0.7791(5)
0.8717(6)
0.9017(6)
0.9950(6)
1.0369(5)
1.0966(7)
1.1165(5)
0.7396(6)
0.7489(6)
0.8477(6)
0.9429(6)
0.8902(6)
0.8505(5)
0.9518(4)
0.8675(5)
1.1985(6)
1.2283(5)
1.2520(5)
1.1175(5)
1.1255(13)
0.9927(14)
0.5554(11)
1.023(2)


-0.59373(3)
-0.6038(5)
-0.4767(6)
-0.7657(5)
-0.8683(6)
-0.3674(5)
-0.2220(6)
-0.7867(5)
-0.9856(5)
-0.4932(5)
-0.5205(6)
-0.5411(6)
-0.5505(6)
-0.7269(6)
-0.4639(8)
-0.5205(7)
-0.6589(8)
-0.7723(8)
-0.4301(7)
-0.3322(8)
-0.8584(7)
-0.8801(7)
-0.6956(8)
-0.5583(7)
-0.4761(8)
-0.5419(10)
-0.6560(9)
-0.6937(9)
-0.0948(8)
-0.0827(7)
-0.1811(6)
-0.0177(7)
-0.2021(8)
-0.0874(7)
-0.2842(7)
-0.2352(7)
-0.331(2)
-0.161(2)
-0.934 (3)
0.041(2)


aFor anisotropic atoms, the U value is Ueq, calculated as Ueq
= 1/3 i U ai* aj* ij where A. is the dot product of the
ith and j direct space unit cell vectors.


z

0.64925(2)
0.4966(3)
0.3911(3)
0.6306(3)
0.5647(4)
0.6630(3)
0.7482(4)
0.6395(3)
0.6739(3)
0.7694(3)
0.8721(3)
0.5598(4)
0.7381(4)
0.7808(4)
0.4935(5)
0.4578(5)
0.5276(5)
0.5775(5)
0.7789(5)
0.7260(5)
0.7577(5)
0.6845(5)
0.8203(6)
0.8215(5)
0.6104(5)
0.6907(6)
0.7965(5)
0.8376(5)
0.5375(5)
0.5988(4)
0.5374(4)
0.4752 (4)
0.7879(5)
0.7814(4)
0.8336(5)
0.7504(5)
0.9794(9)
0.9042(8)
0.5128(11)
0.9620(12)


U

0.02632(9)
0.039(2)
0.047(2)
0.039(2)
0.052(2)
0.035(2)
0.053(2)
0.036(2)
0.043(2)
0.040(2)
0.053(2)
0.031(2)
0.034(2)
0.032(2)
0.036 (3)
0.035(3)
0.037(3)
0.037(3)
0.038(3)
0.036(3)
0.032 (3)
0.033 (3)
0.039(3)
0.034(3)
0.037(3)
0.044 (3)
0.039(3)
0.041(3)
0.037(3)
0.046(3)
0.042(3)
0.047(3)
0.042(3)
0.048(3)
0.056(3)
0.055(2)
0.239(12)
0.29(2)
0.38(2)
0.142(13)











Table 2-22:


Bond Lengths (A) and
atoms of compound 6.


for the non-H


1


2


01
01'i
02
03
04
05
N1
N2
N3
C1'
C1'
C2'
C2'
C3'
C3'
C4'
C4'
C5'
C5'
C1
C1
C1
C2
C2
C6
C3
C3
C3
C7
C7
C8
C4
C4
C4
C5
C5
C9
C1'
01
01
01'
C2'
02
02
02'


Bi
Bi
Bi
Bi
Bi
Bi
Bi
Bi
Bi
01
01'
02
02'
03
03'
04
04'
05
05'
N1
N1
N1
N1
N1
N1
N2
N2
N2
N2
N2
N2
N3
N3
N3
N3
N3
N3
C1
C1'
Cl'
C1'
C2
C2'
C2'
C2'


3











Bi

Bi

Bi

Bi


1-2

2.562(5)
2.686(6)
2.368(5)
2.479(5)
2.494(5)
2.599(5)
2.639(6)
2.536(7)
2.626(6)
1.258(9)
1.260(10)
1.275(9)
1.242(10)
1.278(10)
1.240(10)
1.277(9)
1.235(9)
1.245(9)
1.246(9)
1.477(11)


1.486(11)

1.473(12)
1.484(10)


1.478(10)

1.500(11)
1.462(10)


1.487(11)

1.492(12)
1.518(13)



1.505(12)


1-2-3











115.4(5)

125.1(5)

117.0(5)

120.0(5)

121.3(5)

110.0(6)
113.6(6)
105.1(5)
110.6(7)
109.2(4)
108.1(4)
110.4(7)
112.2(6)
106.2(5)
108.0(7)
111.4(5)
108.7(5)
109.8(6)
113.1(7)
107.7(4)
107.7(6)
108.8(5)
109.7(5)
111.2(7)
125.7(8)
118.7(7)
115.7(7)
114.2(6)
123.2(8)
119.0(7)
117.9(7)


C2
C6
Bi
C6
Bi
Bi
C7
C8
Bi
C8
Bi
Bi
C5
C9
Bi
C9
Bi
Bi
N1
01'
Cl
C1
N1
02'
C2
C2


Angles ()














Table 2-22 -- continued.


1


2


Table 2-23:


Atom


Hla
Hib
H2a
H2b
H3a
H3b
H4a
H4b
H5a
H5b
H6a
H6b
H7a
H7b
H8a


Fractional coordinates and isotropic thermal
parameters (A2) for the H atoms of compound 6.


x

0.834(6)
0.753(6)
0.774(5)
0.684(6)
0.82143
0.92137
0.930(5)
1.019(5)
1.133(5)
1.108(5)
0.672(6)
0.766(6)
0.711(5)
0.723(7)
0.817(6)


-0.379(8)
-0.450(7)
-0.679(7)
-0.651(7)
-0.39704
-0.44615
-0.880(6)
-0.899(7)
-0.730(7)
-0.746(7)
-0.467(8)
-0.389(7)
-0.501(7)
-0.623(9)
-0.630(8)


z

0.520(6)
0.458(5)
0.473(5)
0.515(4)
0.79817
0.82343
0.742(4)
0.800(5)
0.800(4)
0.873(5)
0.582(5)
0.611(5)
0.722(4)
0.696(6)
0.836(5)


U


0.06(3)
0.04(2)
0.04(2)
0.04(2)
0.05
0.05
0.01(2)
0.02(2)
0.02(2)
0.04(2)
0.05
0.05
0.03(2)
0.08(4)
0.05(3)


3

N2
03'
C3
C3
N3
04'
C4
C4
N3
05'
C5
C5
N1
C6
N2
C8
N12
N13
N11
N22
N23
N21


1-2

1.518(12)



1.540(13)



1.501(12)



1.522(13)

1.509(12)

1.324(12)
1.311(11)
1.332(10)
1.323(12)
1.326(11)
1.301(10)


C3'
03
03
03'
C4'
04
04
04'
C5'
05
05
05'
C7
N2
C9
N3
N11
N12
N13
N21
N22
N23


C3
C3'
C3'
C3'
C4
C4'
C4'
C4'
C5
C5'
C5'
C5'
C6
C7
C8
C9
C10
C10
C10
C20
C20
C20


1-2-3

114.6(7)
124.0(8)
118.8(7)
117.2(8)
110.5(7)
124.0(8)
117.8(7)
118.2(7)
113.4(7)
125.7(7)
116.9(7)
117.3(7)
110.8(7)
114.2(8)
114.3(8)
113.7(7)
121.0(7)
119.7(8)
119.3(8)
119.5(7)
119.7(8)
120.8(8)











Table 2-23 -- continued


Atom

H8b
H9a
H9b
Hlla
Hllb
H12a
H12b
H13a
H13b
H21a
H21b
H22a
H22b
H23a
H23b


z

0.769(4)
0.869(5)
0.877(5)
0.59806
0.64101
0.496
0.57949
0.47426
0.43372
0.80774
0.75036
0.86001
0.83804
0.75546
0.71936


Table 2-24:


Bond Lengths (A)
of compound 6.


2


1


Hla
Hla
Hla
Hib
Hib
H2a
H2a
H2a
H2b
H2b
H3a
H3a
H3a
H3b
H3b
H4a
H4a
H4a
H4b
H4b
H5a
H5a
H5a


3

Hlb
C1'
N1
C1'
N1
H2b
C2'
N1
C2'
N1
H3b
C3'
N2
C3'
N2
H4b
C4'
N3
C4'
N3
H5b
C5'
N3


and Angles (o)


1-2

1.05(9)


0.95(8)

1.12(9)


0.93(8)

0.960(9)


0.960(8)

0.99(7)


0.85(7)

0.80(8)


for the H atoms


1-2-3

109. (7)
108. (6)
105. (5)
117. (5)
106. (5)
112. (6)
100. (4)
104. (4)
114. (5)
112. (5)
109.5(8)
108.2(7)
108.2(7)
108.2(8)
108.2(7)
109. (6)
108. (4)
108. (4)
116. (6)
106. (5)
98. (7)
108. (5)
112. (5)


x

0.816(5)
0.973(5)
0.938(5)
0.80846
0.86524
0.9794
0.96675
0.82551
0.89491
1.28432
1.19207
1.30808
1.23209
1.09744
1.08123


-0.738(7)
-0.635(8)
-0.766(7)
-0.02302
-0.13466
-0.18777
-0.23318
0.04209
-0.02582
-0.06482
-0.03163
-0.26192
-0.36238
-0.31315
-0.17939


U


0.03(2)
0.04(2)
0.04(2)
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05
0.05











Table 2-24 -- continued.


2


1

H5b
H5b
H6a
H6a
H6a
H6b
H6b
H7a
H7a
H7a
H7b
H7b
H8a
H8a
H8a
H8b
H8b
H9a
H9a
H9a
H9b
H9b
Hlla
Hlla
Hllb
H12a
H12a
H12b
H13a
H13a
H13b
H21a
H21a
H21b
H22a
H22a
H22b
H23a
H23a
H23b


C5
C5
C6
C6
C6
C6
C6
C7
C7
C7
C7
C7
C8
C8
C8
C8
C8
C9
C9
C9
C9
C9
N11
N11
N11
N12
N12
N12
N13
N13
N13
N21
N21
N21
N22
N22
N22
N23
N23
N23


3

C5'
N3
H6b
C7
N1
C7
N1
H7b
N2
C6
N2
C6
H8b
C9
N2
C9
N2
H9b
N3
C8
N3
C8
Hllb
C10
C10
H12b
C10
C10
H13b
C10
C10
H21b
C20
C20
H22b
C20
C20
H23b
C20
C20


1-2

1.03 (8)

1.03(8)


1.01(8)

0.97(8)


0.97(10)

0.95(10)


1.05(7)

0.88(8)


1.03(8)

0.900(7)

0.900(7)
0.900(8)

0.900(7)
0.900(7)

0.900(8)
0.900(7)

0.900(7)
0.900(7)

0.900(8)
0.900(7)

0.900(7)


1-2-3

121. (4)
104. (4)
106. (7)
111. (5)
111. (5)
118. (5)
100. (5)
93. (8)
110. (4)
110. (4)
105. (6)
123. (6)
108. (7)
109. (5)
107. (5)
106. (4)
113. (4)
104. (7)
105. (6)
114. (5)
112. (5)
108. (4)
120.0(9)
120.1(7)
119.9(8)
120.0(8)
120.6(7)
119.4(8)
120.0(8)
120.9(8)
119.1(8)
120.0(8)
120.5(7)
119.5(7)
120.0(8)
120.3(8)
119.7(7)
120.0(7)
120.4(8)
119.6(8)











Table 2-25: Crystallographic data for compound 6.


A. Crystal data (298 K)
a, A
b, A
c, A
3, deg.
V, A3
deai, g cm-3(298 K)
Empirical formula
Formula wt, g
Crystal system
Space group
Z
F(000), electrons
Crystal size (mm3)


B. Data collection (298 K)
Radiation/, X (A)
Mode
Scan range Symmetrically over X
(X = 1.2)
Background offset 1.0 and -1.0 in
Scan rate, deg. min.-1
28 range, deg.
Range of h k 1 0
0
-20

Total reflections measured
Unique reflections
Absorption coeff. p (Mo-K,), mm-1
Minimum / maximum transmission

C. Structure refinement
S, Goodness-of-fit
Reflections used, I > 2u(I)
No. of variables
R, R:* (%)
Rint (%)
Max. shift/esd
min. peak in diff. four. map (e A-3)
max. peak in diff. four. map (e A-3)


6
15.113(3)
10.720(2)
17.091(3)
102.72(2)
2701.0(9)
1.942
C,6H30NgO10Bi- 4H20
789.53
Monoclinic
P 21/n
4
1568
0.65 x 0.54 x 0.07


Mo-K,/ 0.71073
w-scan
about K1a,2 maximum

W from K.,2 maximum
3 6
3 55
s h 18
5 k s 12
5 1 s 20


5117
4640
6.61
0.331


1.38
3631
423
3.79,
2.03
0.001
-1.75
1.34


/ 0.669





4.09


* Relevant expressions are as follows, where in the footnote
Fo and F, represent, respectively, the observed and
calculated structure-factor amplitudes.
Function minimized was w(Fo IFF1)2, where w= (a(F))-2
R = I (I FoI IFcl ) / ZIF1o
R = [Zw( Fo IFJ)2 / I 1F21/2
S = [yw(IFo IFJ)2 / (m-n)] 12








53

and angles are given in Tables 2-28 and 2-29, respectively.

Table 2-30 details the hydrogen bonding interactions, and

the structure was refined to an R value of 4.2 %, which is

shown with other crystal data in Table 2-31.

The crystal structure of 7 reveals the ligand SASC

bonded to an acetic acid (HAc) molecule. Extensive hydrogen

bonding is observed in this structure both within the SASC

molecule, and between the SASC and HAc. The entire

semicarbazone 'arm' is rotated so as to maximize the

hydrogen bonding interaction between the ligand hydroxyl

hydrogen, H2, and N2. This leaves the molecule in a

position to interact with HAc. The N8b hydrogen, H8a, is

involved in hydrogen bonding through the HAc carbonyl oxygen

09a, while the ligand carbonyl oxygen, 08a, hydrogen bonds

with the HAc hydroxyl hydrogen. All hydrogen bonding

interactions, including those created by symmetry, are given

in Table 2-30.

The ability to synthesize a series of bismuth complexes

with widely varying solubilities comes at a time when more

attention is being focused on the solid state coordination

chemistry of bismuth(III) and its role as a therapeutic

agent. Subsequent studies of coordination polyhedra and

antibacterial activity have further served to characterize

this element. The positive results obtained herein warrant

further attempts at the synthesis and characterization of

bismuth complexes.































C7 N8b
80N7
C1 C8 *
09b
C6 080















Figure 2-13: View of 7 showing the thermal ellipsoids
and atomic numbering. Methyl hydrogens
are omitted for clarity.













Table 2-26: Fractional coordinates and equivalent
isotropica thermal parameters (A2) for the
non-H atoms of compound 7.


x

0.3581(3)
-0.0242(3)
0.1206(4)
0.0698(3)
-0.1086(3)
0.1864(3)
0.1075(3)
0.2754 (3)
0.3502(4)
0.4231(5)
0.4206(4)
0.3481(4)
0.2776(4)
0.1979(3)
0.0658(3)
-0.0372(4)
-0.0993(5)


0.4840(2)
-0.0740(2)
0.0580(3)
-0.2661(2)
-0.3203 (2)
0.2779(2)
0.1430(2)
0.5222(3)
0.5715(3)
0.7148(3)
0.8087(3)
0.7625(3)
0.6209(3)
0.3738(3)
0.0377(3)
-0.3490(3)
-0.4960(3)


z

0.33965(9)
0.40836(8)
0.32124(12)
0.24866(10)
0.34046(10)
0.42151(10)
0.43959(11)
0.46468(12)
0.39979(12)
0.3950(2)
0.4540(2)
0.5187(2)
0.5239(2)
0.47329(13)
0.38916(12)
0.27748(14)
0.2465(2)


U

0.0683(8)
0.0530(6)
0.0605(10)
0.0732(8)
0.0687(8)
0.0406(7)
0.0487(8)
0.0388(8)
0.0458(9)
0.0612(11)
0.0640(12)
0.0600(11)
0.0501(10)
0.0410(8)
0.0433(9)
0.0540(10)
0.087(2)


aFor anisotropic atoms, the U value is Ue calculated as Ueq
=1/3 ij U.i ai* aj* A where Aj is the dot product of the
ith and jt direct space unit cell vectors.


Table 2-27:


1


Bond Lengths (A) and Angles (0) for the non-H
atoms of compound 7.


2


02
08a
N8b
09a
09b
N7
N7
N8
C1
C1
C1
C2
C2


3






C7

N7
C6
C7
C2
02
C1


1-2

1.352(3)
1.247(3)
1.327(3)
1.202(3)
1.301(3)
1.378(3)
1.279(3)
1.345(3)
1.390(3)
1.397(3)
1.450(3)
1.389(4)


1-2-3






115.3 (2)

122.2(2)
117.8(2)
119.3(2)
122.9(2)
117.2(2)
120.3(2)


Atom


02
08a
N8b
09a
09b
N7
N8
C1
C2
C3
C4
C5
C6
C7
C8
C9
C10











Table 2-27 -- continued


1-2


1.368(4)
1.372(5)
1.369(4)





1.494 (4)


1-2-3

122.5(2)
120.1(3)
120.7(3)
119.4(3)
121.7(3)
123.4(2)
123.0(2)
118.3(2)
118.6(2)
124.3 (3)
112.8(3)
122.8(2)


Table 2-28:


Fractional
parameters


coordinates and isotropic thermal
(A2) for the H atoms of compound 7.


x

0.308(4)
0.096(5)
0.199(4)
-0.056(5)
0.075(3)
0.486(4)
0.473 (4)
0.354(3)
0.235(3)
0.153 (3)
-0.0903
-0.01873
-0.22551
-0.13561
-0.20237
0.00344


0.394 (4)
-0.016(4)
0.137(3)
-0.225(4)
0.130(3)
0.739(3)
0.905(3)
0.829(3)
0.585(2)
0.349(2)
-0.49235
-0.57295
-0.51729
-0.56193
-0.48178
-0.53889


z

0.348(2)
0.291(2)
0.3117(14)
0.362(2)
0.4845(14)
0.350(2)
0.4492(13)
0.5599(14)
0.5674(12)
0.5205(12)
0.19421
0.26591
0.2587
0.28489
0.21241
0.22152


U

0.105(13)
0.108(13)
0.068(9)
0.112(12)
0.054(7)
0.086(10)
0.066(8)
0.064(8)
0.047(7)
0.046(6)
0.08
0.08
0.08
0.08
0.08
0.08


2


1


02
C4
C5
C6
C1
N7
08a
08a
N8b
C10
C10
09a


3

C1
C2
C3
C4
C5
C1
N8b
N8
N8
09a
09b
09b


Atom

H2
H8a
H8b
H9b
H8
H3
H4
H5
H6
H7
H101
H102
H103
H104
H105
H106






















Table 2-29: Bond Lengths (A)
of compound 7.


1

H2
H8a
H8a
H8b
H9b
H8
H8
H3
H3
H4
H4
H5
H5
H6
H6
H7
H7
H101
H101
H101
H102
H102
H103
H104
H104
H104
H105
H105
H106


2

02
N8b
N8b
N8b
09b
N8
N8
C3
C3
C4
C4
C5
C5
C6
C6
C7
C7
C10
C10
C10
C10
C10
C10
C10
C10
C10
C10
C10
C10


3

C2
H8b
C8
C8
C9
C8
N7
C4
C2
C5
C3
C6
C4
C1
C5
N7
C1
H102
H103
C9
H103
C9
C9
H105
H106
C9
H106
C9
C9


(0) for the H atoms


1-2

0.90(3)
0.88(3)

0.92(3)
1.01(3)
0.87(2)

0.97(3)

0.95(3)

0.96(2)

0.92(2)

0.96(2)

0.960(3)


0.960(3)

0.960(4)
0.960(3)


0.960(4)

0.960(4)


1-2-3

110. (2)
125. (3)
115. (2)
119. (2)
111. (2)
120. (2)
118. (2)
123. (2)
116. (2)
121. (2)
118. (2)
122. (2)
119. (2)
117.0(14)
121.2(14)
119.6(13)
117.1(13)
109.5(3)
109.5(4)
108.6(3)
109.5(3)
108.8(3)
111.0(3)
109.5(4)
109.5(3)
110.4(3)
109.5(3)
110.1(3)
107.9(3)


and Angles





















Table 2-30: H-bonding for compound 7.


D


02
02
N8b
N8b
N8b
N8b
N8
09b


H


H2
H2
H8a
H8a
H8b
H8b
H8
H9b


A


N7
09a'
09a
02a"i
N7
09ai
08.ii
08a


D-H
(A)

0.90(3)

0.88(3)

0.92 (3)

0.87(2)
1.01(3)


H----A
(A)

1.93(3)
2.47(3)
2.37(3)
2.42(3)
2.38(3)
2.20(3)
2.07(2)
1.61(3)


D-H----A
(o)

143(3)
104 (2)
158(3)
126(3)
102(2)
151(2)
172 (2)
164(3)


Elements generated by symmetry operators: i 0.5-x, 0.5+y,
0.5-z; ii 0.5-x, -0.5+y, 0.5-z; iii iv -x, -y, l-x.











Table 2-31: Crystallographic data for compound 7.


A. Crystal data (298 K)
a, A
b, A
c, A
a, deg.
3, deg.
7, deg.
V, A3
dcal, g cm-3(298 K)
Empirical formula
Formula wt, g
Crystal system
Space group
Z
F(000), electrons
Crystal size (mm3)

B. Data collection (298 K)
Radiation, X (A)
Mode
Scan range Symmetrically over 1.2
Background offset 1.0 and -1.0 in w
Scan rate, deg. min.-
26 range, deg.
Range of h k 1 -9
0
0 s

Total reflections measured
Unique reflections
Absorption coeff. p (Mo-K~), cm-1
Min. & Max. Transmission

C. Structure refinement
S, Goodness-of-fit
Reflections used, I > 2(I)
No. of variables
R, RW (%)
Rint. (%)
Max. shift/esd
min. peak in diff. four. map (e A-3)
max. peak in diff. four. map (e A-3)


7
7.182(1)
8.947(1)
18.277(2)
90
91.89(1)
90
1173.8(2)
1.354
CloH3N304O
239.23
Monoclinic
P 21/n
4
504
0.36 x 0.23 x 0.19


Mo-K,, 0.71069
w-scan
about K,,2 maximum
from K,1,2 maximum
3 6
3 55
h s 9
k < 11
1 s 23


3115
2711
0.11
0.962,


1.19
1309
198
4.20%,
0%
0.0012
-0.19
0.12


0.986





4.08%


* Relevant expressions are as follows, where in the footnote
F, and Fc represent, respectively, the observed and
calculated structure-factor amplitudes.
Function minimized was w(IFo1 IFJ)2, where w= (a(F))-2
R = (I IFo IFc ) / ZIF
R = [Iw(IFo IFc )2 / I 2 1F1/2
S = [w(|IFj IFJ )2 / (m-n)]/2














CHAPTER 3


COMPLEXES OF BISMUTH(III):
VALENCE BOND SUMS AND COORDINATION POLYHEDRA


Introduction


Our studies of bismuth coordination chemistry have been

directed mainly toward the synthesis of satisfactory

crystalline samples with which to gain a clearer

understanding of bismuth complexes in the solid state. With

this goal comes the sometimes daunting task of evaluating

the nature both of the bismuth coordination environment in

terms of its geometry, and of the electronic nature of the

bismuth ion itself.

The formation of a complex of any metal ion with a

multidentate ligand represents a compromise between the

steric demands of the ligand, and the steric and electronic

requirements of the metal ion. The large size of the

Bi(III) ion facilitates coordination spheres containing up

to nine donor atoms, but can pose difficulties for ligands

that are either small or sterically hindered. Two features

that appear to be common to the bismuth carboxylato

complexes reported in chapter 2, together with the citrate

complexes reported earlier,7 are the tendency to form








61

dimerr like' subunits, and the presence of widely variable

metal-donor atom bond distances. These could be related

both to the coordination sphere geometry imposed by the

ligand, and to the possible stereochemical activity of the

bismuth (III) 6s2 lone pair.

Questions of the presence, or lack, of a

stereochemically active lone pair on the Bi(III) ion have

been raised in a variety of forums.2'26 Problems arise in

the determination of the correct oxidation state for the

bismuth ion if one considers that the only difference

between Bi(OH,)3, where Bi formally maintains a +3 formal

charge, and (BiO)3, in which Bi formally maintains a +5

formal charge, is the presence of two protons, which may or

may not be detectable in an x-ray crystal structure. As

water molecules often play a part in the inner coordination

spheres of bismuth complexes with sterically hindered

ligands, this distinction becomes an important one.

In order to assess the possible stereochemical activity

of a Bi(III) lone pair we have sought a means by which to

evaluate the inner coordination sphere geometries of

complexes 1, 3, 4, 5, and 6 to see if such a lone pair is

detectable via a 'vacant' coordination site. Coordination

polyhedra were analyzed by calculating the angles between

facial planes each consisting of three atoms bonded to the

central bismuth atom.27 Likewise, a method for determining

the metal ion valency consisted of utilizing the idea of








62

valence bond sums,28 henceforth VBS. This 'valence sum' is

obtained by adding the contributions to valency of each

metal-donor atom bond, which are calculated from standard

bond lengths. From these data we have gained a clearer

picture of the electronic nature of Bi(III) in the solid

state, as well as its common coordination geometries.


Discussion and Results


Questions regarding the existence and/or stereochemical

activity of a Bi3+ 6s2 lone pair of electrons have made the

use of VBS a desirable tool. We have utilized this method

to determine the overall valence of the Bi cation in each of

our bismuth complexes. The VBS method depends on the

empirical determination of a set of standard cation-anion

bond lengths, ro, from large sets of crystal data. A table

of such values has been reported by Brown and Altermatt,28

henceforth BA, along with an algorithm for predicting the ro

values of bonds not listed. A more recent method formulated

by O'Keeffe and Brese,29 henceforth OB, was also utilized.

In the BA method, the contribution, s, of any given

cation-anion bond to cation valence is given by the equation



s = exp[(ro-r)/B]



where r, and B are empirically determined parameters, and r

is the experimentally observed cation-anion bond length. In








63

this manner, the oxidation state, Vi, of any cation, i, may

be calculated via the equation



Vi= Sij


where sj are the valence contributions from bonds between

the cation i and each donor atom j. The parameter B was

determined empirically to be 0.37A.

In the OB method, a similar mathematical form is used.

For any given cation, i, the valence, Vi, is calculated by

summing the contributions to valency, vj, of each bond

between i, and its donor anions, j.



Svi, = V


Contributions to valence, vi, are calculated via


vi = exp[(Rij dij)/b]


where d.9 is the experimentally determined bond length

between i and j, and b is the "universal" constant taken to

be 0.37 A. The parameter R1i is the bond valence

parameter. In a general sense, this is the length of a

single bond between i and j, but is usually determined to be

the bond length in compounds that are stable at normal

temperatures and pressures. For example, Rij for the bond

between Na and F- is taken to be the bond distance in

crystalline NaF, not that observed in diatomic NaF.








64

Values of Rij for any given bond may be calculated by

using the expression


rrj, (/c vCj)2
Rj = ri + rj -
ciri + Cjrj


where r is a 'size' parameter, and c is a second parameter

for any element. Values of r and c were determined

empirically so as to minimize the squared deviation between

calculated and observed values of Rij. In some cases the

value of c for a particular element showed a strong

correlation to the Allred-Rochow electronegativity for that

element. These were fixed where appropriate.

Both the BA and OB methods were used to calculate the

Bi cation valency for each bismuth complex in which Bi-donor

atom distances were known. The VBS, utilizing each method,

for the complexes Bi(DIPIC), Bi(NTA), Bi(EDTA), Bi(DTPA),

and Bi(DAPAAH) along with the contributions from each donor

atom are given in Tables 3-1 to 3-5. Values of r, used in

the BA method were 2.094 A for Bi-O, and 2.184 A for Bi-N.

The values for Ri used in the OB method were 2.12 A for Bi-

0, and 2.23 A for Bi-N.

The calculated VBS values range from 2.89 to 3.29 for

the BA method, and from 3.16 to 3.59 for the OB method.

Values of 3.00 0.30, for the BA method, suggest that the

actual valence of the Bi cation is indeed 3+. Both VBS











Table 3-1: Contributions to valency of each Bi-donor
atom bond and total VBS for the complex
Bi2 (DIPIC), (HDIPIC)2(HAc) 2 4H20.


Bi-N
Bi-N'
Bi-O1
Bi-Ol'
Bi-Oli
Bi-03
Bi-03'
Bi-05


BA
0.536
0.462
0.344
0.739
0.297
0.536
0.162
0.210

3.286


OB
0.607
0.523
0.369
0.793
0.319
0.575
0.174
0.225

3.585


Table 3-2: Contributions to valency of each Bi-donor
atom bond and total VBS for the complex
Bi (NTA) 2H20.


Bi-N
Bi-Ol
Bi-02
Bi-03
Bi-04
Bi-05
Bi-02i
Bi-03'i


VBS


BA
0.426
0.642
0.333
0.651
0.434
0.162
0.214
0.398

3.260


OB
0.482
0.689
0.357
0.698
0.465
0.174
0.229
0.427

3.521


Table 3-3: Contributions to valency of each Bi-donor
atom bond and total VBS for the complex
Bi(HEDTA) 2H20.


BA


Bi-N1
Bi-N2
Bi-Ol
Bi-02
Bi-03
Bi-04
Bi-03'i
Bi-04'i


0.473
0.346
0.564
0.227
0.437
0.581
0.206
0.209


3.043


OB

0.536
0.391
0.605
0.244
0.469
0.623
0.221
0.224

3.313


VBS











Table 3-4: Contributions to valency of each Bi-donor
atom bond and total VBS for the complex
(Guan) 2Bi(DTPA) 4H20.


Bi-N1
Bi-N2
Bi-N3
Bi-O1
Bi-02
Bi-03
Bi-04
Bi-05
Bi-Ol' i


VBS


BA

0.292
0.386
0.303
0.282
0.477
0.353
0.339
0.255
0.202

2.889


OB

0.331
0.437
0.343
0.303
0.512
0.379
0.364
0.274
0.217

3.160


Table 3-5: Contributions to valency of each Bi-donor
atom bond and total VBS for the complex
Bi(DAPAAH) (Ac) 2H20.


BA


Bi-N2
Bi-N3
Bi-N4
Bi-Ol
Bi-012
Bi-014a
Bi-Ol4b
Bi-016a
Bi-016b


VBS


0.248
0.464
0.541
0.161
0.470
0.473
0.166
0.386
0.178


3.087


OB


0.281
0.526
0.613
0.173
0.505
0.505
0.178
0.414
0.191


3.386


methods are apparently useful in determining metal ion

valencies in coordination complexes, although the BA method

has produced values closer to what are predicted.30 This

concept may then be useful in distinguishing between Bi(III)

and Bi(V).

In assessing the coordination environment of any

particular cation, it is often useful to assign a specific








67

polyhedron that corresponds to the geometric arrangement of

donor atoms about the central metal ion. While this

assignment is important, it is by no means a trivial

process. Since many ligands are sterically hindered, both

by their own bulk and by the size of the metal ion to which

they are coordinated, the polyhedra are often not clearly

defined, and the assignment becomes somewhat arbitrary.

We have utilized a method by which the process of

polyhedron assignment may be made somewhat more quantitative

through the use of a computer program that analyzes the

positions of the metal and donor atoms. After inputing the

atomic coordinates of the metal and donors, three-atom

planes are chosen until all possible outside planes have

been located. An 'outside' plane is detected by determining

if all other donor atoms are on one side of this plane.

Once all of the outside planes have been located, the

program calculates the angles between all planes which share

an edge, as well as listing how many three-atom faces meet

at each donor atom.27

Once these data have been generated, the angles and

vertices of any compound may be compared to the angles and

vertices for all possible idealized polyhedra which

correspond to that particular coordination number. For

example, coordination numbers of eight normally show square

antiprism, dodecahedron, or bicapped trigonal prism

arrangements, the former two being the more common. The









68

most common polyhedra for nine-coordinate complexes are that

of the capped square antiprism and tricapped trigonal

prism.3 In looking for a polyhedron such as the square

antiprism, one would expect to find two square faces, with

each face consisting of two triangular faces with an angle

of 00(or 1800) between them. A bicapped trigonal prism

should show only one such square face, and the dodecahedron

would show none.

Polyhedra have been assigned for the complexes

Bi(DAPAAH) (Ac)2(1), Bi(DIPIC) (HDIPIC) (3), Bi(NTA) (4),

Bi(HEDTA)(5), and Bi(DTPA)2-(6). No determination was

possible for compound 2, as an x-ray structure was not

obtained. The polyhedra for the three eight-coordinate

complexes, 3, 4, and 5, appear to be best described as

bicapped trigonal prisms. The polyhedra for the nine-

coordinate complexes, 1 and 6, may be described as

monocapped square antiprisms. Compound 1, however, has a

geometry that might be better described as a distorted

monocapped square prism. In all cases the polyhedra show

distortions from the idealized geometries.

Compounds 3, 4, and 5 are shown in Figures 3-2, 3-3,

and 3-4, respectively. The designation of bicapped trigonal

prism is based on the presence of several characteristics.

In 4, a well-defined square face containing 01, 04, 03' and

05 is noted along with two triangular faces (01, 03, 04 and

02, 05, 03'). The capping atoms are N and 02'. In compound








69

5, the square face consists of the atoms 01, N1, 03, and 04'

with the two triangular faces defined by 02, 03, 04' and 04,

N1, 01. The capping atoms are 03' and N2.

Compound 3 represented somewhat of a problem in

assessing its coordination polyhedron. The lack of a

clearly defined square face (that containing two three-atom

faces with an angle of 00 between them) suggested that a

dodecahedron was the proper designation. Upon viewing the

coordination sphere, however, the lack of two clearly

defined perpendicular four-atom faces, necessary for a

dodecahedron, suggested that the designation of bicapped

trigonal prism was indeed proper. This distorted polyhedron

consists of a square face defined by 03', Ola, 01, Ac, and

two triangular faces containing 03', N', Ola, and 01, N, Ac,

respectively. The capping atoms are 03 and 01'. This

distortion may be caused both by the rigidity of the DIPIC

ligands, and by the presence of the Bi(III) lone pair, which

would reside in the third capping position in the trigonal

prism arrangement, but would not be evident in the

dodecahedron.

In compound 6, shown in Figure 3-5, the best

arrangement appears to be that of a monocapped square

antiprism. The complex shows two distinct square faces

which consist of N3, 04, 05, 01', and N2, 01, 02, 03. The

latter face is capped by atom N1. Compound 1, shown in

Figure 3-1, maintains a geometry intermediate between that




















S N(4) 0(12)















arrangement.
0016b)

0(16a) *

0(1)





Figure 3-1: View of the polyhedron for compound 1
showing the capped square antiprism
arrangement.
















03'












Ac


Figure 3-2: View of the polyhedron for compound 3
showing the bicapped trigonal prism
arrangement.


so100


LMMMS I
























0(20(1














0(1)





Figure 3-3: View of the polyhedron for compound 4
showing the bicapped trigonal prism
arrangement.















0(2)


0(') o 49j


0(3'i)00



N(2)




0(1)



0(4)






Figure 3-4: View of the polyhedron for compound 5
showing the bicapped trigonal prism
arrangement.

















0(2)


0(4)


N(1)














0(5)






Figure 3-5: View of the polyhedron for compound 6
showing the capped square antiprism
arrangement.
arrangement.








75

of a monocapped square antiprism and monocapped square

prism. The uncapped and capped square faces consist of 01,

014b, 012, 016b, and N2, 014a, N4, 016a, respectively. The

capping atom is N3.

The presence of the Bi(III) 6s2 lone pair appears to be

substantiated by the results of our valence bond sum

calculations. The fact that the VBS consistently showed

values near the predicted value of 3.0 in complexes of

different coordination numbers, suggests both that the

assignment of a 3+ charge to the bismuth ion is an

appropriate one, and that this method may be useful in

distinguishing between Bi(III) and Bi(V) in coordination

complexes. Values obtained using the BA method ranged from

2.89 to 3.29 and are in better agreement with the predicted

value than those obtained in the OB method.

In theory, a stereochemically active lone electron

pair, such as the Bi(III) 6s2 electrons, should manifest

itself as an open or 'vacant' coordination site. This would

lead, in the cases of our complexes, to the lone pair

occupying the third capping position in the bicapped

trigonal prisms, or the second capping position in the

monocapped square antiprisms. Neither of these situations

represent unusual or unreasonable polyhedra. Further

studies will continue to shed light on the question of lone

pair stereochemical activity.














CHAPTER 4


BISMUTH COMPLEXES:
A STUDY OF ANTIBACTERIAL ACTIVITY


Introduction


Bismuth compounds have been used over the years for a

number of medicinal purposes including the treatment of

gastric disorders, syphilis, and the topical disinfection of

wounds. Use of bismuth drugs waned for a number of years in

the mid twentieth century as medical doctors discouraged the

use of heavy-metal containing salts. Bismuth therapies have

made a comeback, however, with the continued use of bismuth

subsalicylate as a treatment for gastrointestinal disorders,

and the use of colloidal bismuth subcitrate (CBS) as a

treatment for peptic ulcers. It was found recently that CBS

is active against the stomach bacterium Helicobacter Pylori,

thought to be a causal factor in the development of peptic

ulcers.2 It is this activity that has prompted our

investigation of the antibacterial properties of the bismuth

complexes synthesized in this project.

We have utilized the bismuth complexes Bi(NTA),

Bi(HEDTA), and Bi(PIC)3 in a study of antibacterial

activity. The complexes were used to coat filter papers in








77

an attempt to simulate a bandage coating. These filter

papers were then immersed in agar solutions containing one

of several types of bacteria, including Escherichia Coli,

Pseudomonas Aeruginosa, and Staphylococcus Aureus. The

effect of the coated filter papers on bacterial growth was

observed and is reported herein.


Experimental


Materials

All bismuth complexes used were synthesized and

purified as outlined in Chapter 2. 'Blanks' included filter

papers dipped in H20, and solutions of NTA and (BiO)2CO3.

NTA and (BiO)2C03 were obtained commercially and used

without further purification. Filter papers used were

Whatman qualitative grade 4.25 cm circles.

Filter Paper Production

Filter papers were dried in dessicators and weighed

prior to use. For each compound, a saturated solution was

prepared by stirring an excess of the solid and 1-2 mL H20

in a vial at a constant temperature for 10-15 min. The

temperature was maintained by immersing the vial in an oil

bath heated to 900C. Filter papers were then soaked

thoroughly in the solutions, placed into dessicators until

dry, and reweighed to determine approximate amounts of solid

absorbed onto the filter paper. This procedure was used to








78

produce filter papers coated with Bi(PIC)3, Bi(NTA),

Bi(HEDTA), Bi(DTPA)2-, NTA, (BiO)2CO3, and H20 alone.

Bacterial Growth

Solutions containing Escherichia Coli were made by

combining melted plate-count agar (Difco) with 0.05 g/mL of

2,3,5-triphenyltetrazolium chloride (henceforth TTC) dye and

approximately 105 colony-forming units (CFU) of E. Coli C-

3000 per mL. Two solutions each of Pseudomonas Aeruginosa

(ATCC 10145), and Staphylococcus Aureus (FDA 209) were made,

one without TTC and one with only 0.01 g/mL of the dye.

Aliquots of about 20 mL were placed in sterile 100 mm

diameter petri plates along with 13 mm diameter circular

cutouts from the prepared filter papers. These were allowed

to incubate for 24 h and the bacterial growth monitored by

observing either the red color of the reduced TTC, or a

generally darker color in the plates without TTC. The

degree of bacterial inhibition was quantified by measuring

the radii of the colorless zones surrounding the filter

paper cutouts.32


Discussion


Bismuth compounds have been used in the past for the

topical disinfection of wounds. It was our hope that the

series of carboxylate complexes synthesized herein would

prove to be effective at inhibiting bacterial growth, and








79

would shed some light on the importance of water solubility.

On neither count were we disappointed.

Bacterial growth was evident in petri dishes containing

TTC by the red color of the reduced dye. Areas where

bacterial growth was inhibited remained colorless. Since

TTC has proven to be toxic to P. Aeruginosa, and S. Aureus,

runs were done with and without the dye. Where TTC was

used, only trace amounts were added to give a clearer

contrast between areas of bacterial growth and inhibition.

Without TTC, areas of inhibition were more difficult to

discern, the only difference between these and areas of

bacterial growth being a very slight change in color and

clarity of the solution.

The inhibition of bacterial growth occurred most

prominently in complexes of low to moderate water

solubility. These included the complexes of Bi(III) with

PIC, NTA, and EDTA. The NTA complex showed the most

consistently high levels of inhibition. Filter papers

coated with Bi(DTPA)2- and Bi(DIPIC)(HDIPIC), the most water

soluble of the complexes, showed little bacterial

inhibition. Table 4-1 shows the approximate amounts, of

several of the complexes, that were absorbed onto the filter

papers. These values were obtained by subtracting the

initial weight of the filter papers from their dry weights

after soaking in saturated solutions of the complexes.








80

Blanks were run by soaking filter papers in saturated

solutions of NTA, (BiO),CO3, and H20 alone, then repeating

the procedure for bacterial inhibition as outlined above.

NTA was chosen since the Bi(NTA) complex showed the most

consistent antibacterial activity, and (BiO)2CO3 because it

is extremely insoluble and was our source of Bi(III) in most

of the complex syntheses. In no case did these blanks show

any noticeable inhibition of bacterial growth. This was

done to establish three things: 1) that the ligand alone is

not responsible for any observed antibacterial activity, 2)

that our original source of the Bi(III) ion doesn't show

greater antibacterial activity than the subsequent complexes

made from it, and 3) that Bi(III) must be present in a

compound that shows at least a small degree of water

solubility.

In cases where the inhibition of bacterial growth was

significant, a radius of inhibition was measured. This was

done from the center of the 13 mm circular filter paper to

the edge of the colorless zones of inhibition. Measurements

were taken on several different trials to produce average

results. In several of the petri dishes where TTC was not

used, no area of inhibition could be discerned. These

results are outlined in Table 4-2.

The results of our antibacterial studies, outlined in

the previous tables, show that bismuth complexes of moderate

to low solubility may be used successfully to inhibit the









81

Table 4-1: Mass of complexes on filter papers after
soaking in saturated solutions.


Bi(PIC),

0.0008 g



Bi (DTPA) 2-

0.1907 g


Bi(NTA)

0.0006 g



NTA

0.0050 g


Bi(HEDTA)

0.0119 g



HO0

0.0001 g


Table 4-2: Diameters of inhibition for Bi(PIC)3, Bi(NTA),
and Bi(HEDTA) in each type of bacteria.


E. Coli

P. Aeruginosa
(with TTC)
(without TTC)

S. Aureus
(with TTC)
(without TTC)


Bi(PIC) 3

1.1 cm


1.1 cm
N/A*


1.0 cm
0.8 cm


Bi(NTA)

1.7 cm


1.3 cm
N/A*


1.3 cm
1.1 cm


Bi(HEDTA)

1.2 cm


2.3 cm
-2.6 cm


1.3 cm
N/A*


indicates areas of inhibition not discernible



growth of several types of bacteria. The effectiveness of

these compounds appears to require a balance between a level

of solubility that frees enough of the Bi(III) to inhibit

bacterial growth, and a level of insolubility that keeps the

Bi(III) localized in a small area. Our encouraging results

will warrant further investigations into the antibacterial

properties of these and other bismuth complexes.















CHAPTER 5


COMPLEXES OF BISMUTH (III) WITH PHOSPHONIC ACIDS:
A SYNTHETIC AND SPECTROSCOPIC STUDY


Introduction


Results outlined in chapter 4 show that bismuth

complexes with the ligands NTA and EDTA have demonstrated

considerable activity against Escherichia Coli,

Staphylococcus Aureus, and Pseudomonas Aeruginosa. These

activities appear to be related to the relative water

solubilities of the complexes. The least soluble complex,

Bi(NTA), showed the most consistently strong antibacterial

activity, while the more soluble Bi(DTPA)2-,

Bi(HDIPIC)(DIPIC), and Bi(DAPAAH)3 complexes showed little

to no observable activity. In Chapter 2 we showed that both

protonated and nonprotonated bismuth complexes could be

formed and that, as in (Guan),Bi(DTPA), that the solubility

of the resulting complex could be manipulated with the use

of appropriate countercations.

To further utilize this property, we have attempted the

synthesis of an analogous series of bismuth complexes with

ligands in which phosphonic acid groups replace the acetic

acid groups. The phosphonic acid functional group contains
82








83

two ionizable protons, which provides a greater opportunity

to manipulate the extent of deprotonation and, therefore,

the solubilities of these complexes. We have successfully

prepared the ligands nitrilotrismethylenetriphosphonic acid

(NTPA), and ethylenediaminotetramethylenetetraphosphonic

acid (EDTPA), analogous to their counterparts NTA and EDTA.

The ligands are shown in Figures 5-1 and 5-2. Attempts to

synthesize the phosphonic acid analogous to DTPA were not

met with success. The results from the syntheses of bismuth

complexes with NTPA and EDTPA, along with their infrared

spectra, are presented herein.


Experimental


Materials

All reagents, including phosphorous acid, H3PO3

(Aldrich); ethylenediamine, NH2 (CH2)2NH2, concentrated HC1,

concentrated HNO3, 37% aqueous formaldehyde, H2CO, and

acetone, CH3C(O)CH3 (Fisher); ethanol, CH3CH20H (Florida

Distillers); bismuth subcarbonate, (BiO)2CO3; bismuth

nitrate Bi(NO3)3-5H20, and ammonium chloride, NH4C1 (J.T.

Baker); were used without further purification. The

synthetic procedures for the NTPA and EDTPA ligands were

adapted from methods previously reported.33

Synthesis of NTPA (8)

To a solution of 8.211 g crystalline H3PO3 and 1.781 g

NH4Cl in 12 mL H20 was added 10 mL conc HC1. This solution














SCH/
HO7P H2
HO 1
Oa H O


PO
OH


HO O 0

OH


Figure 5-1: Nitrilotrismethylenetriphosphonic Acid
(NTPA)


/CH2 CH2-
HO /CH2-
HOC- HO CH2 H 2
0 Ha,/ HyC
O 2 2-


Ou
0


2NCH2 / OH


0OH
\ /OH O
%T_-<^T O-


0


Figure 5-2: Ethylenediaminotetramethylene-
tetraphosphonic Acid (EDTPA)


AAV








85

was heated to reflux in an oil bath. Over approx. 45 min,

16 mL of 37% H2CO was added dropwise to the solution. After

refluxing for an additional 1 h 20 min, the solution was

poured into a beaker and allowed to evaporate. The

resulting thick, syrupy solution was dissolved in 40 mL

CH3OH and allowed to evaporate. Over approx 1 month, very

slow crystallization yielded large star-like clumps of clear

colorless crystals. The crystals were separated from the

syrupy mother liquor and washed with ethanol/acetone, but

were still sticky and difficult to handle. Anal. Calc

(Found) for C3HI2NO9P3: C, 12.05(12.14); H, 4.04(4.95);

N, 4.68(5.12).

Synthesis of EDTPA (9)

To a solution of 8.212 g (0.100 mol) H3PO3 in 10 mL H20

was added 10 mL conc HC1 and 1.536 g (0.0250 mol)

NH2(CH2)2NH2. After heating to reflux, 16 mL 37% H2CO was

added dropwise over 1 h. The solution was heated for an

additional 40 min., then placed onto a roto-vac and the

volume reduced to approx 10 mL. Crystals were visible and

continued to form as the remaining solution evaporated.

Several harvests yielded colorless crystals which were

washed with H20 and stored for further use. The mp of 210-

2150 is consistent with the literature.33 Anal. Calc(Found)

for C6H20N2O12P4- 2H20: C, 15.26(15.08); H, 5.12(4.77);

N, 5.93(5.86).










Synthesis of Bi.(NTPA) (10)

A solution of the ligand was prepared by dissolving

0.172 g (0.575 mmol) in 20 mL H20. The pH was approximately

1-2. To this solution was added 0.147 g (0.288 mmol)

(BiO)2CO3. The volume was increased to 40 mL by the

addition of 20 mL H20 and refluxed for several days. A

white solid persisted throughout, which was subsequently

filtered off and allowed to dry. Anal. Calc(Found) for

C3H6NO9P3Bi2: C, 5.07(4.99); H, 0.85(0.91); N, 1.97(1.98).

Synthesis of Bi (HNTPA) (NTPA) (NO3) 6H2O (11)

To a solution of 0.0750 g (0.251 mmol) NTPA in 10 mL

H20 (pH approx 1) was added 0.234 g (0.503 mmol)

Bi(NO)3- 5H20. A fine white solid appeared immediately.

After stirring with heat for several hours the solid was

filtered off. Anal. Calc(Found) for CgH25N3027P6Bi4:

C, 4.52(4.28); H, 1.58(1.49); N, 2.64(2.45).

Synthesis of Bi. (EDTPA) 3 10H20 (12)

Solid (BiO)2CO3 (0.256 g (0.502 mmol)), was added

directly to a solution of 0.219 g (0.502 mmol) EDTPA in 20

mL H20. The reaction mixture was heated to boiling for 4 h,

during which 10 mL H20 were added. This mixture was allowed

to cool and the white solid filtered off and allowed to dry.

Anal. Calc(Found) for C8Hs56N604,P12Bi': C, 6.89(6.95); H,

1.79(1.85); N, 2.68(2.55).