Coordinatively polymeric and monomeric bismuth(iii) complexes with pyridine carboxylic acids

Article abstract of DOI:10.1039/b920775a

Three crystalline compounds, [Bi(2-O₂C-C₅H ₄N)₃]_n (1), {Bi[(2,6-O₂C) ₂C₅H₃N)][(2-HO₂C-6-O ₂C)C₅H₃N]·H₂O}_n (2) and Bi(O₂CC₉H₆N)₂(O ₃N)(O₂CC₉H₆NH)·2H ₂O (3) have been prepared by simple reactions in aqueous medium using the readily available bismuth nitrate and the corresponding acids, picolinic acid, dipicolinic acid and quinaldic acid. While 1 and 2 are coordination polymers with bismuth in tricapped trigonal prismatic and dodecahedral environments, compound 3 is a monomeric species with dodecahedral geometry at bismuth. Compound 1 represents a second crystalline form of a recently reported structure with subtle differences in bond parameters, and highlights the flexibility in structural motifs during crystallization. Compound 2 involves skeletons with dimeric [Bi₂O₂] and trimeric [BiOCOBiOBiOCO] moieties. In 3, while the N-protonated carboxylate forms a four-membered chelate ring with bismuth, the other two carboxylates form five-membered ring chelates with the nitrate accounting for the remaining two sites again as a chelate. TGA studies are consistent with the presence of non-coordinated water in 2 and 3. Compounds 1 and 2, although insoluble in most of the organic solvents and water, are readily soluble in dilute hydrochloric acid.

Full text of DOI:10.1039/b920775a

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www.rsc.org/dalton | Dalton Transactions
Coordinatively polymeric and monomeric bismuth(III) complexes with pyridine
carboxylic acids†
O. Anjaneyulu, T. K. Prasad and K. C. Kumara Swamy*
Received 7th October 2009, Accepted 19th November 2009
First published as an Advance Article on the web 24th December 2009
DOI: 10.1039/b920775a
Three crystalline compounds, [Bi(2-O2C–C5H4N)3]n (1), {Bi[(2,6-O2C)2C5H3N)]-
[(2-HO2C-6-O2C)C5H3N]·H2O}n (2) and Bi(O2CC9H6N)2(O3N)(O2CC9H6NH)·2H2O (3) have been
prepared by simple reactions in aqueous medium using the readily available bismuth nitrate and the
corresponding acids, picolinic acid, dipicolinic acid and quinaldic acid. While 1 and 2 are coordination
polymers with bismuth in tricapped trigonal prismatic and dodecahedral environments, compound 3 is
a monomeric species with dodecahedral geometry at bismuth. Compound 1 represents a second
crystalline form of a recently reported structure with subtle differences in bond parameters, and
highlights the flexibility in structural motifs during crystallization. Compound 2 involves skeletons with
dimeric [Bi2O2] and trimeric [BiOCOBiOBiOCO] moieties. In 3, while the N-protonated carboxylate
forms a four-membered chelate ring with bismuth, the other two carboxylates form five-membered ring
chelates with the nitrate accounting for the remaining two sites again as a chelate. TGA studies are
consistent with the presence of non-coordinated water in 2 and 3. Compounds 1 and 2, although
insoluble in most of the organic solvents and water, are readily soluble in dilute hydrochloric acid.
Introduction
Despite being compounds of a heavy metal, several bis-
muth derivatives have been used for the treatment of various
gastrointestinal disorders, including gastric and duodenal ul-
cers, dyspepsia, diarrhoea, SARS and colitis.1,2 Among these,
bismuth carboxylates and their partially hydrolysed deriva-
tives have long been recognized as important compounds
in chemotherapy. In order to understand their activity, a
sizeable number of reports on structural as well as bio-
Fig. 1 [Bi(cit)2Bi]2- dinuclear subunit normally found in bismuth citrate
chemical aspects have emerged during the past couple of
compounds; O¢ represents an oxygen atom from citrate or a water molecule.
decades.1b,3 Bismuth subsalicylate (BSS) and colloidal bismuth
The terminal ‘O’ atoms of the citrate group are further connected to
form the coordination polymer chain. The bismuth centre can also have a
coordination number of 8 with one of the acyclic ligands being absent.
subcitrate (CBS) are two important pharmaceutical agents;
however, only [Bi38O44(Hsal)26(Me2CO)16(H2O)2]·(Me2CO)4 and
[Bi9O7(Hsal)13(Me2CO)5]·(Me2CO)1.5 are good structural models
for the former.4 Most of the subcitrate complexes contain the stable
[Bi(cit)2Bi]2- dimer/s with additional O2-, OH- and H2O ligands
[Fig. 1; note that cit = C6H4O74-].5 However, the acidity (pKa1 of
ca. 1.5 for Bi3+) and ability of the metal centre to readily expand the
coordination sphere makes rationalization of the biological action
quite challenging. These factors, in conjunction with the lability
of the ligands, often lead to difficulties in controlling hydrolysis
of molecular complexes. The net result is the formation of the
“BiO+” cation and/or coordination oligomers or polymers, which
are difficult to characterize.6 The sensitivity of bismuth carboxylate
complexes to water has been assuaged in many instances by
the incorporation of N, O or S donor atoms into the ligands,
which may mimic bismuth binding sites in biologically active
surroundings.1b,2 It is also known that bismuth binds to nitrogen
donor macrocycles even in strongly acidic solutions. As far as
the structural chemistry is concerned, we had some interest in
multinuclear antimony/tin caboxylate/phosphinate compounds7
and this part has been accentuated by recent initiatives in India by
funding bodies on metal based drugs. The present work deals with
the simple and efficient synthesis of bismuth carboxylates under
completely green conditions using water as the solvent and the
inexpensive, moisture tolerant and eco-friendly bismuth nitrate as
the bismuth source.8
Results and discussion
The three compounds [Bi(2-O2C–C5H4N)3]n (1), {Bi[(2,6-
O2C)2C5H3N)][(2-HO2C-6-O2C)C5H3N]·H2O}n
(2)
and
Bi(O2CC9H6N)2(O3N)(O2CC9H6NH)·2H2O (3) [Fig. 2] have
been synthesized by adding the corresponding carboxylic acid
to a boiling aqueous solution of bismuth nitrate pentahydrate.
Compound 1 has been obtained recently while exploring benzylic
oxidations by oxidizing Bi(0) in the presence of t-BuOOH
School of Chemistry, University of Hyderabad, Hyderabad, 500046, AP,
India. E-mail: kckssc@uohyd.ernet.in, kckssc@yahoo.com
† CCDC reference numbers 749253–749255. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/b920775a
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©

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Fig. 3 Drawings representing the X-ray structure of 1. Hydrogen atoms
are not shown for clarity. Top left: asymmetric unit + O(1¢), O(3¢) and
O(5¢) to show the coordination around bismuth. Top right: polyhedron
showing tricapped trigonal prismatic geometry around bismuth. Bottom:
coordination polymer motif in 1. Colour code: Bi = magenta, O = red,
N = blue and C = black. Symmetry operators: (i) 0.5-x, -0.5+y, 0.5-z;
(ii) 0.5-x, 0.5+y, 0.5-z.
with O(3¢), O(5), O(1¢), O(1), N(3) and O(3) forming the trigonal
prism and N(1), O(5¢¢) and N(2) capping the three sides; this is
also shown in Fig. 3. The lone pair of electrons on bismuth appear
to be stereochemically inactive. The bond distances are in the
normal range for the covalent as well as coordinately covalent
linkages involving bismuth, with one of the Bi–O bonds being the
Fig. 2 Structural drawings of 1–3 highlighting the coordination around
bismuth atoms [water molecules are not shown].
and then reacting with picolinic acid,9 but our route is more
straightforward and simpler. Although in both the cases an
aqueous medium was used, interestingly, the resulting complex
did not contain any water of crystallization. This was also shown
by the absence of the O–H band in the IR spectrum and the
correct elemental analyses. By contrast, in the structures of 2 and
3, non-coordinated water is present in the crystal lattice. In 3,
there is a sharper band at 3110 cm-1 ascribable to the protonated
quinoline N–H (see X-ray structure below). We have performed
similar reactions with nicotinic acid, 2-hydroxynicotinic acid,
3-hydroxypicolinic acid and pyridine 2,3-dicarboxylic acid and
obtained only water-insoluble materials. From the reaction of
bismuth nitrate with the amino acid L-proline, the only bismuth
compound that we could isolate in small quantities was its
oxonitrate cluster that does not contain proline residue.10
˚
longest, but within 0.8 A of the sum of the van der Waals radii.
Overall, the compound is a coordination polymeric chain with
three bridging oxygen atoms between adjacent bismuth centres.
Each pyridine carboxylate forms five-membered rings using the
nitrogen and one of the carboxylate oxygen atoms with the other
oxygen being free. This type of structure is different from the
tetrameric picolinate [PhBi(2-(C5H4N)CO2)2]4,3a perhaps due to
the presence of more oxygen atoms around bismuth in 1. It is also
worth noting that a normal carboxylate like [Bi(O2CC6H4CH3-
3)3]n is also coordinately polymeric but they are composed of
chelate carboxylates only.12
Compound 2 [Fig. 4, Table 2] is also a coordination polymer but
the structural motif is quite different from that observed in 1. There
is a fused dinuclear [Bi(1)–O(2)–Bi(2)–O(9)–] polyhedral unit
as well as a trinuclear [Bi(1)–O(9)–Bi(2)–O(4¢¢)–C(1¢¢)–O(1¢¢)–
Bi(1¢¢)–O(8)–C(8)–O(5)–] motif. These features lead to a branched,
rather than a linear, polymer. Since each bismuth is trivalent,
Compound 1 crystallized in the space group P21/n [Fig. 3].11
The relevant bond parameters are given in Table 1. We assign a
tricapped trigonal prismatic coordination sphere around bismuth
1936 | Dalton Trans., 2010, 39, 1935–1940
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◦
Table 1 Selected geometric parameters (A, ) in 1a
˚
Bi–O1
Bi–O3
Bi–O5
Bi–N1
2.446(4)
2.484(4)
2.315(4)
2.588(5)
Bi–N3
Bi–O1¢
Bi–O3¢
Bi–O5¢¢
2.425(5)
2.662(4)
2.636(4)
2.935(4)
Bi–N2
2.627(5)
O1–Bi–O3
O1–Bi–O5
O1–Bi–N1
O1–Bi–N2
O1–Bi–N3
O1–Bi–O1i
O1–Bi–O3¢
O1–Bi–O5¢¢
O3–Bi–O5
O3–Bi–N1
O3–Bi–N2
O3–Bi–N3
O3–Bi–O1¢
O3–Bi–O3¢
O3–Bi–O5¢¢
O5–Bi–N1
O5–Bi–N2
O5–Bi–N3
63.70(13)
136.49(14)
63.83(13)
121.99(14)
80.02(15)
150.78(7)
112.66(13)
63.57(12)
135.06(14)
123.34(14)
62.88(13)
80.12(15)
108.98(13)
150.89(6)
62.08(12)
77.28(15)
75.96(15)
69.26(15)
O5–Bi–O1¢
O5–Bi–O3¢
O5–Bi–O5¢¢
N1–Bi–N2
N1–Bi–N3
N1–Bi–O1¢
N1–Bi–O3¢
N1–Bi–O5¢¢
N2–Bi–N3
N2–Bi–O1¢
N2–Bi–O3¢
N2–Bi–O5¢¢
N3–Bi–O1¢
N3–Bi–O3¢
N3–Bi–O5¢¢
O1¢–Bi–O3¢
O1¢–Bi–O5¢¢
O3¢–Bi–O5¢¢
69.87(14)
69.13(13)
154.91(12)
138.89(16)
71.31(17)
127.28(13)
71.53(14)
109.90(14)
70.29(17)
69.91(14)
124.94(13)
107.58(14)
128.12(15)
128.76(15)
135.74(15)
58.83(13)
87.73(11)
89.91(12)
a Symmetry operators: (i) 0.5-x, -0.5+y, 0.5-z; (ii) 0.5-x, 0.5+y, 0.5-z.
Parameters involving O(5¢¢) were taken by the Diamond program.
between the two dipicolinates per bismuth, one free carboxylic acid
-OH residue is still present in the compound. Although there are
two distinct bismuth atoms in the asymmetric unit, both exhibit
eight coordination with dodecahedral geometry (cf. Fig. 4). A
major difference between the two bismuth atoms lies in the longest
bond length: While for Bi(1), it is the coordinate bond to the
=
carboxylic acid C O [i.e. Bi(1)–O(6)], for Bi(2) it is a bridging
oxygen of the [Bi2O2] skeleton [Bi(2)–O(2)]. Also, two Bi(1) and
only one Bi(2) form a larger ring as mentioned before. Primarily,
these bonds make the two bismuth centres different.
There are also two water molecules in the asymmetric unit of 2
[i.e. one per bismuth]. They form a clear “dimer” but are involved
in hydrogen bonding to other atoms also. The hydrogen atom
positions are not refined here; the relevant O ◊ ◊ ◊ O distances are
(i) O(15) ◊ ◊ ◊ O(17) [symm: x, y-1, z] 2.520(10), (ii) O(17) ◊ ◊ ◊ O(18)
2.714(17), (iii) O(18) ◊ ◊ ◊ O(16) 2.792(9) and (iv) O(18) ◊ ◊ ◊ O(13)
Fig. 4 Drawings representing the X-ray structure of 2. Water molecules
are not shown for clarity. Top: Asymmetric unit along with parts of
other units to show the overall skeleton. Only selected atoms are labelled.
Middle: Polyhedra showing dodecahedral geometry around the two
bismuth atoms of the asymmetric unit. Bi(1), N(1), N(2) as well as Bi(2).
Bottom: A representation showing the dinuclear (fused polyhedra) and
trinuclear units in 2; hydrogen atoms and water molecules are omitted.
Colour code: Bi = magenta, O = red, N = blue, C = black, H = light grey.
˚
symm: x, 1+y, z] 3.385(11) A. There is also one discernible
C(4)–H ◊ ◊ ◊ O interaction, with C ◊ ◊ ◊ O [symm: -x, y-0.5, 0.5-z]
˚
3.124(10) A.
Compound 3 is monomeric [Fig. 5, Table 3], most likely because
of the sterically bulkier quinoline carboxylate moiety not permit-
ting the oligomerization/polymerization. Under the conditions
employed, the third nitrate could not be exchanged for quinaldate
(qunioline 2-carboxylate). Overall, two quinoline carboxylates
coordinate via [N,O] five-membered chelate, while the nitrate and
the zwitterionic quinoline carboxylic acid coordinate via [O,O]
four-membered chelate rings. Thus three types of chelating ligands
surround the metal. Also, as can be seen from the diagram, the
quinoline carboxyl nitrogen N(3) is protonated. The distortion in
geometry from the more regular dodecahedron may, at least in
part, be due to the lone pair of electrons on bismuth. The two
water molecules in the asymmetric unit of 3 are hydrogen bonded
to each other, to other oxygen atoms and the protonated nitrogen
{N(3) ◊ ◊ ◊ O(10) 2.704(8), O(10) ◊ ◊ ◊ O(11) 2.749(6), O(10) ◊ ◊ ◊ O(4)
[sym: 0.5+x, 1.5-y, 0.5+z] 2.846(8), O(11) ◊ ◊ ◊ O(2) [symm: -0.5+x,
˚
0.5+y, z] 2.939(8), O(11) ◊ ◊ ◊ O(6) 2.928(9) A}. The water molecule
is retained at least up to 200 ◦C (as shown by TGA).
The TGA data [Fig. 6] show that compound 1 is perfectly
stable up to ~360 ◦C, after which decomposition occurs leading to
Bi2O3. Such a behaviour is observed for some other compounds
also.13 Compound 2 behaves differently, with the non-coordinated
water molecules coming off before the decomposition sets
in. Compound 3 shows a more interesting behaviour with its
melting point almost coinciding with decomposition/sublimation
consistent with its lower melting point. Foaming was also observed
during the melting of 3 that suggests the removal of water, but the
compound decomposed nearly at the same temperature leaving a
black residue. This derivative may be used as a precursor for further
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◦
Table 2 Selected geometric parameters (A, ) in 2a
Table 3 Selected geometric parameters (A, ◦) in 3
˚
˚
Bi1–O1
Bi1–O2
Bi1–O5
Bi1–O6
Bi1–O8¢
Bi1–O9
Bi1–N1
Bi1–N2
2.391(5)
2.483(4)
2.230(5)
2.793(5)
2.635(5)
2.524(5)
2.429(5)
2.478(5)
131.36(15)
91.1(2)
67.16(17)
101.6(2)
157.46(16)
65.72(17)
71.86(18)
75.57(18)
152.38(16)
68.58(17)
67.28(14)
66.13(16)
137.82(18)
129.35(16)
141.30(18)
81.23(18)
81.68(18)
68.56(18)
89.02(16)
101.55(16)
122.91(17)
61.37(17)
97.52(18)
71.04(18)
150.13(19)
132.99(16)
85.62(17)
126.96(18)
Bi2–O2
Bi2–O4¢¢
Bi2–O9
Bi2–O10
Bi2–O13
Bi2–O14
Bi2–N3
2.763(4)
2.625(5)
2.584(5)
2.268(5)
2.672(5)
2.239(5)
2.398(5)
2.449(5)
Bi–O1
Bi–O3
Bi–O5
Bi–N1
2.195(6)
2.250(7)
2.627(6)
2.407(8)
91.93(19)
82.5(2)
Bi–N2
Bi–O6
Bi–O7
Bi–O8
2.535(8)
2.654(7)
2.721(7)
2.671(7)
80.4(2)
121.0(2)
71.1(2)
140.1(2)
78.32(19)
89.0(2)
120.6(2
96.2(2)
O1–Bi–O3
O1–Bi–O5
O1–Bi–O6
O1–Bi–O7
O1–Bi–O8
O1–Bi–N1
O1–Bi–N2
O3–Bi–O5
O3–Bi–O6
O3–Bi–O7
O3–Bi–O8
O3–Bi–N1
O3–Bi–N2
O5–Bi–O6
O5–Bi–O7
O5–Bi–O8
O5–Bi–N1
O5–Bi–N2
O6–Bi–O7
O6–Bi–O8
O6–Bi–N1
O6–Bi–N2
O7–Bi–O8
O7–Bi–N1
O7–Bi–N2
O8–Bi–N1
O8–Bi–N2
N1–Bi–N2
92.3(3)
Bi2–N4
162.8(2)
148.3(2)
71.5(3)
O1–Bi1–O2
O1–Bi1–O5
O1–Bi1–O6
O1–Bi1–O8¢
O1–Bi1–O9
O1–Bi1–N1
O1–Bi1–N2
O2–Bi1–O5
O2–Bi1–O6
O2–Bi1–O8¢
O2–Bi1–O9
O2–Bi1–N1
O2–Bi1–N2
O5–Bi1–O6
O5–Bi1–O8¢
O5–Bi1–O9
O5–Bi1–N1
O5–Bi1–N2
O6–Bi1–O8¢
O6–Bi1–O9
O6–Bi1–N1
O6–Bi1–N2
O8¢–Bi1–O9
O8¢–Bi1–N1
O8¢–Bi1–N2
O9–Bi1–N1
O9–Bi1–N2
N1–Bi1–N2
O2–Bi2–O4¢¢
O2–Bi2–O9
O2–Bi2–O10
O2–Bi2–O13
O2–Bi2–O14
O2–Bi2–N3
O2–Bi2–N4
O4¢¢–Bi2–O9
O4¢¢–Bi2–O10
O4–Bi2–O13
O4¢¢–Bi2–O14
O4¢¢–Bi2–N3
O4¢¢–Bi2–N4
O9–Bi2–O10
O9–Bi2–O13
O9–Bi2–O14
O9–Bi2–N3
O9–Bi2–N4
O10–Bi2–O13
O10–Bi2–O14
O10–Bi2–N3
O10–Bi2–N4
O13–Bi2–O14
O13–Bi2–N3
O13–Bi2–N4
O14–Bi2–N3
O14–Bi2–N4
N3–Bi2–N4
121.13(15)
62.39(13)
155.67(16)
100.54(15)
79.01(16)
123.59(15)
81.83(16)
84.21(16)
81.87(16)
76.87(16)
145.27(16)
70.01(16)
137.51(18)
133.75(15)
142.37(17)
81.49(18)
64.72(16)
136.85(18)
75.56(17)
85.50(18)
69.06(17)
74.97(18)
130.61(17)
134.02(17)
63.20(18)
75.26(17)
67.96(18)
129.78(18)
78.1(2)
146.5(2)
163.5(2)
101.1(3)
79.1(2)
75.8(2)
69.1(2)
47.2(2)
100.7(2)
117.0(2)
133.4(2)
70.3(2)
49.92(19)
132.12(19)
a Symmetry operators: (i) -x+1, y+1/2, -z+1/2; (ii) -x+1, y-1/2, -z+1/2.
Fig. 6 Drawing showing the TGA behaviour of compounds 1–3.
work as it has a fairly low melting point; we are exploring
this aspect further.
Solubility is an important parameter for checking the biological
accessibility. Our target was to use the above compounds for
pharmaceutical purposes. Although compounds 1 and 2 are rather
insoluble in most of the solvents, the dissolution was quite fast in 2
N HCl. Even in 0.1 N HCl, compound 1 could be solubilized after
heating at 80 ◦C. However, no solid came out even after reducing
the volume to ca. 0.5 mL/100 mg of 1. This is interesting because
the compound as such is insoluble in water. Further studies are
required to learn the nature of the species present in dil. HCl.
Conclusion
By means of simple aqueous mediated reactions that are environ-
mentally benign, three structurally diverse pyridine carboxylates of
bismuth 1–3 have been synthesized and structurally characterized.
Using several other carboxylic acids including nicotinic acid,
mainly insoluble materials were obtained. Compounds 1–2 are
coordination polymers but while the former is a linear chain, the
latter is a branched polymer with dinuclear [Bi2O2] and trinuclear
[BiOCOBiOCOBi] structural units. They represent new structural
entities. These compounds are insoluble in water but undergo
dissolution in dilute HCl. TGA studies suggest decomposition to
Fig. 5 Drawings representing the X-ray structure of 3. Hydrogen atoms
are not shown for clarity. Top: asymmetric unit. Bottom: polyhedron
showing slightly distorted dodecahedral geometry. Colour code: Bi =
magenta, O = red, N = blue and C = grey-black.
1938 | Dalton Trans., 2010, 39, 1935–1940
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Bi2O3 in these two cases at temperatures >300 ◦C. Compound 3 is a
monomer that foams at ~210 ◦C with concomitant decomposition.
Table 4 Crystallographic data for compounds 1–3
Compound
1
2
3
Experimental
Emp. formula
Formula wt
C18H12BiN3O6 C28H18Bi2N4O18 C30H23BiN4O11
575.29
Monoclinic
P21/n
1116.42
Monoclinic
P21/c
824.50
Monoclinic
Cc
Crystal system
Space group
Chemicals were procured from Aldrich or local manufacturers. IR
spectra were recorded on a JASCO FT-IR 5400 spectrophotome-
ter. Elemental analyses were carried out on a Thermo Finnigan
EA1112 analyser. Thermogravimetric and differential thermal
analysis (TG-DTA) were carried out on a (Netzsch STA 409 Pc)
˚
a/A
11.822(3)
7.738(2)
18.931(6)
91.165(4)
1731.3(9)
4
12.341(3)
11.886(2)
21.485(4)
103.96(3)
3058.6(11)
4
9.6810(6)
18.5747(12)
16.5929(11)
100.585(1)
2933.0(3)
4
˚
b/A
˚
c/A
b (◦)
V/A
Z
◦
3
˚
TG-DTA instrument from 30 to 500 C with a scanning rate of
10 ◦C min-1 under nitrogen flow.
Dcalcd
m
F000
2.207
2.424
1.867
10.228
1088
11.587
2096
6.082
1608
Synthesis of compound 1
Data/restraints/
parameters
S
3371/0/253
6118/3/483
5182/8/427
To a boiling solution of Bi(NO3)3·5H2O (0.485 g, 1 mmol) in
water (50 cm3) was added the carboxylic acid (0.246 g, 3 mmol)
and the clear solution obtained was refluxed for a further 2 h.
The solution was filtered to remove any suspended impurities
and the clear, colourless filtrate allowed to cool slowly. After 2 d,
colourless crystals suitable for X-ray single crystal analysis were
formed. Yield: 0.320 g, 56%. Elemental analysis (calc): C, 37.45
1.116
0.0349
0.0852
1.101
0.0329
0.0815
1.091
0.0240
1.204
R1
wR2 (all data)
Max./min. residual
1.377/-2.032 1.965/-2.392
-0.420/0.106
-3
˚
elec. dens./e A
◦
(37.58); H, 2.17 (2.10); N, 7.41 (7.30); Mp: >320 C; IR (cm-1)
(b) Precipitate with 2-hydroxynicotinic acid: 3084(w), 2914(w),
1873(w), 1699(w), 1628(s), 1601(w), 1572(m), 1450(s), 1388(s),
1246(m), 1213(s), 1109(m), 677(s), 557(m), 445(s); (c) Precipitate
with 3-hydroxypicolinic acid: 3092(w), 2915(w), 1697(w), 1631(m),
1572(m), 1452(s), 1390(s), 1323(s), 1246(s), 1215(s), 1111(m),
883(s), 677(s), 580(m), 557(m); (d) Precipitate with pyridine-2,3-
dicarboxylic acid: 3447(br), 3090(w), 1728(s), 1657(w), 1616(w),
1575(s), 1448(m), 1383(s), 1278(m), 1228(w), 1149(m), 1099(s),
839(w), 698(s), 667(w), 555(m), 447(s).
3074(w), 2926(w), 1651(s), 1591(s), 1568(m), 1462(m), 1332(s),
1290(m), 1238(m), 1161(w), 1089(w), 1047(m), 1010(w), 833(s),
763(s), 694(s), 632(m). The compound was insoluble in common
organic solvents and hence NMR spectra were not recorded.
Synthesis of compound 2
The reaction was conducted at room temperature affording the
product in >75% yield, but the crystallinity was not great. In
a procedure similar to that for 1 better crystalline material was
obtained (40% yield). The IR spectra of the samples from the
two procedures were identical. Elemental analysis (calc): C, 30.21
X-ray crystal structural analysis
X-ray data were collected on a Bruker AXS SMART diffractome-
◦
(30.11); H, 1.56 (1.61); N, 5.11 (5.02); Mp: >320 C; IR (cm-1)
˚
ter using Mo-Ka (l = 0.71073 A) radiation. The structures were
solved by direct methods;14 all non-hydrogen atoms were refined
anisotropically. For the hydrogen atoms, the riding model was
used. The crystal data are summarized in Table 4.
3435(br), 3090(w), 2914(w), 1697(w), 1662(w), 1620(m), 1583(s),
1433(s), 1336(m), 1255(m), 11689(m), 1072(m), 1020(w), 908(w),
765(s). This compound was also insoluble in common organic
solvents, but soluble in 2 N HCl (ca. 50 mg in 5 cm3).
Acknowledgements
Synthesis of compound 3
We acknowledge the Department of Science and Technology
(DST), New Delhi for financial support under the Metal Based
Drugs program and for setting up a National Single Crystal
Diffractometer facility at the University of Hyderabad. Thanks
are also due to UPE program of UGC (New Delhi) for other
equipment. OA thanks CSIR (New Delhi) for a fellowship.
The procedure was similar to that for 1 except that the mixture
was refluxed for 12 h, using 100 mg (0.206 mmol) of bismuth
nitrate pentahydrate. Yield: 75 mg (44%). Elemental analysis
(calc): C, 43.85 (43.70); H, 2.79 (2.81); N, 6.86 (6.79); Mp: 210 ◦C:
IR (cm-1): 3450(br), 3110, 1749(w), 1732(w), 1628(s), 1595(m),
1539(m), 1454(s), 1350(m), 1222(m), 1157(w), 796(w), 536(m).
Other reactions
Notes and references
To a boiling solution of 0.206 mmol of Bi(NO3)3·5H2O in
60 cm3 of H2O was added 0.618 mmol of carboxylic (nico-
tinic, 2-hydroxynicotinic, 3-hydroxypicolinic and pyridine 2,3-
dicarboxylic) acid and the clear solution/precipitate obtained
was further refluxed for 12 h. The solution was filtered and
the precipitate washed with ◦water and dried in air. All of them
had melting points > 320 C. IR (cm-1): (a) Precipitate with
nicotinic acid: 3445(br), 3084(w), 2916(w), 1722(w), 1630(w),
1547(s), 1456(m), 1385(s), 1302(m), 1026(s), 814(s), 760(s), 553(m);
1 Some useful reviews: (a) Z. Guo and P. J. Sadler, Angew. Chem., Int.
Ed., 1999, 38, 1512; (b) G. G. Briand and N. Burford, Chem. Rev., 1999,
99, 2601; (c) R. Ge and H. Sun, Acc. Chem. Res., 2007, 40, 267; (d) N.
Yang and H. Sun, Coord. Chem. Rev., 2007, 251, 2354; (e) V. Stavila,
R. L. Davidovich, A. Gulea and K. H. Whitmire, Coord. Chem. Rev.,
2006, 250, 2782.
2 (a) N. Yang, J. A. Tanner, Z. Wang, J. D. Huang, B. J. Zheng, N.
Zhu and H. Sun, Chem. Commun., 2007, 4413; (b) M. J. Abrams and
B. A. Murrer, Science, 1993, 261, 725; (c) K. H. Thompson and C.
Orvig, Science, 2003, 300, 936; (d) J. H. Thurston, E. M. Marlier and
K. H. Whitmire, Chem. Commun., 2002, 2834; (e) P. C. Andrews, G. B.
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The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 1935–1940 | 1939
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Deacon, W. R. Jackson, M. Maguire, N. M. Scott, B. W. Skelton and
A. H. White, J. Chem. Soc., Dalton Trans., 2002, 4634; (f) G. G. Briand,
N. Burford, M. D. Eelman, N. Aumeerally, L. Chen, T. S. Cameron
and K. N. Robertson, Inorg. Chem., 2004, 43, 6495; (g) N. Burford,
M. D. Eelman and T. S. Cameron, Chem. Commun., 2002, 1402; (h) V.
Stavila, J. C. Fettinger and K. H. Whitmire, Organometallics, 2007, 26,
3321.
3 (a) P. C. Andrews, G. B. Deacon, P. C. Junk, I. Kumar and M.
Silberstein, Dalton Trans., 2006, 4852; (b) P. C. Andrews, G. B. Deacon,
R. L. Ferrero, P. C. Junk, A. Kurrar, I. Kumar and J. G. MacLellan,
Dalton Trans., 2009, 6377; (c) P. C. Andrews, G. B. Deacon, P. C.
Junk, I. Kumar and J. G. MacLellan, Organometallics, 2009, 28,
3999.
4 P. C. Andrews, G. B. Deacon, C. M. Forsyth, P. C. Junk, I. Kumar and
M. Maguire, Angew. Chem., Int. Ed., 2006, 45, 5638.
5 W. Li, L. Jin, N. Zhu, X. Hou, F. Deng and H. Sun, J. Am. Chem. Soc.,
2003, 125, 12408.
6 (a) G. G. Briand and N. Burford, Adv. Inorg. Chem., 2000, 50, 285;
(b) H. Suzuki and Y. Matano, ed. Organobismuth Chemistry, Elsevier,
Amsterdam, 2001.
8 For a report on green methodology in bismuth chemistry see: P. C.
Andrews, G. B. Deacon, P. C. Junk and N. F. Spiccia, Green Chem.,
2007, 9, 1319.
9 E. Callens, A. J. Burton, A. J. P. White and A. G. M. Barrett, Tetrahedron
Lett., 2008, 49, 3709.
10 The quality of data was not good enough to solve the structure
completely; however, it appears to contain interlinked Bi6O8 core
with both chelating and bridging nitrate ligands. Cell parameters:
˚
Monoclinic, P21/n; a = 15.342(5), b = 9.177(3), c = 17.132(6) A, b =
◦
3
˚
113.989 (5) , V = 2203.7(12) A . For other known bismuth oxonitrate
clusters, see the review 1(b).
11 The X-ray structure of crystals with the same molecular formula is
also reported in ref. 9: P21 (no. 4), a = 11.0098(8), b = 7.7495(6), c =
◦
3
˚
˚
11.2271(8) A, b = 116.361(7) , V = 858.29(11) A , Z = 2. Note that it
belongs to a chiral space group and thus the compound appears to be
dimorphic. The deposited data suggest isotropic refinement for non-
hydrogen atoms. The relevant bond distances for the assigned bicapped
trigonal prismatic coordination (taken from ref. 9) are: Bi–N 2.588(7),
˚
2.430(9), 2.633(7) A; Bi–O 2.473(6), Bi–2.531(6), 2.296(6), 2.648(6),
˚
2.574(6) A.
7 (a) M. A. Said, K. C. Kumara Swamy, D. M. Poojary, A. Clearfield,
M. Veith and V. Huch, Inorg. Chem., 1996, 35, 3235; (b) M. A. Said,
K. C. Kumara Swamy, Kamlesh Babu and M. Nethaji, J. Chem. Soc.,
Dalton Trans., 1995, 2151; (c) K. C. Kumara Swamy, M. A. Said, S.
Nagabrahmanandachari, D. M. Poojary and A. Clearfield, J. Chem.
Soc., Dalton Trans., 1998, 1645; (d) K. C. Kumara Swamy, M. A.
Said and M. Netaji, J. Chem. Crystallogr., 1999, 29, 1103; (e) K. C.
Kumara Swamy, S. Nagabrahmanandachari and K. Raghuraman,
J. Organomet. Chem., 1999, 587, 132; (f) A. Srinivasa Rao, E. Sunil
Babu, K. C. Kumara Swamy and Samar K. Das, submitted (bismuth
chemistry).
12 V. V. Sharutin, I. V. Egorova, T. K. Ivanenko, O. K. Sharutina, M. A.
Pushilin, A. V. Gerasimenko, N. A. Adonin and V. F. Starichenko,
Russ. J. Coord. Chem., 2004, 30, 309.
13 M. Wenkin, R. Touillaux and M. Devillers, New J. Chem., 1998, 22,
973.
14 (a) G. M. Sheldrick, SHELX-97- A program for crystal structure solution
and refinement, University of Go¨ttingen, 1997; (b) G. M. Sheldrick,
SADABS, Siemens Area Detector Absorption Correction, University of
Go¨ttingen, Germany, 1996; (c) G. M. Sheldrick, SHELXTL NT Crystal
Structure Analysis Package, Bruker AXS, Analytical X-ray System, WI,
USA, 1999, version 5.10.
1940 | Dalton Trans., 2010, 39, 1935–1940
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The Royal Society of Chemistry 2010
©