Synthesis and structures of organoantimony and organobismuth derivatives of 4-sulfophenol and 2,4-disulfophenol

Article abstract of DOI:10.1134/S1070328407030037

Tetraphenylbismuth 4-hydroxybenzenesulfonate (I) and tetraphenylantimony 4-hydroxybenzenesulfonate (II) are synthesized in yields up to 80% by the reaction of pentaphenylbismuth and pentaphenylantimony, respectively, with 4-sulfophenol. Compounds I and II are also prepared by the ligand redistribution reaction from pentaphenyl compounds of bismuth and antimony and triphenylbismuth bis(4-hydroxybenzenesulfonate) and triphenylantimony bis(4-hydroxybenzenesulfonate), respectively, in yields up to 87%. The recrystallization of compounds I and II from water gives crystalline hydrates Ph₄BiOSO₂C₆H₄(OH-4) ? H ₂O (III) and Ph₄SbOSO₂C₆H ₄(OH-4) ? H₂O (IV). Pentaphenylbismuth and pentaphenylantimony react with 2,4-disulfophenol in acetone, regardless of the ratio of the starting reactants, to form bis(tetraphenylbismuth) 4-hydroxybenzene-1,3-disulfonate (V) and bis(tetraphenylantimony) 4-hydroxybenzene-1,3-disulfonate (VI) in yields up to 74%. According to X-ray diffraction data, coordination of the bismuth atoms in compound I is trigonal-bipyramidal with the axial oxygen atom of the 4-hydroxybenzenesulfonate group (Bi???O 2.764 A). In compound II, coordination of the Sb atom is tetrahedral (CSbC angles 106.2°-112.3°). In crystal III, the distances between the central atom and the nearest oxygen atoms of the arenesulfonate group and the hydrate water molecule are 3.094 and 3.125 A, respectively. Crystals V and VI consist of doubly charged anions of 2,4-disulfophenol and several distorted tetrahedral cations of tetraphenylbismuthonium (CBi(1)C, CBi(2)C angles and Bi(1)-C, Bi(2)-C bond lengths vary in the intervals 102.1°-122.7°, 105.4°-114.0° and 2.103-2.230, 2.187-2.209 A, respectively) and tetraphenylantimonium (CSb(1)C, CSb(2)C angles and Sb(1)-C, Sb(2)-C bond lengths 106.3°-112. 2°, 101.3°-122.4° and 2.095-2.110, 2.092-2.123 A, respectively). The Bi(1) and Sb(2) atoms are coordinated by one of the oxygen atoms of the 2,4-disulfophenol anions (distances Bi(1)???O(3) 2.803, Sb(2)???O(1), 2.704 A). Nauka/Interperiodica 2007.

Full text of DOI:10.1134/S1070328407030037

ISSN 1070-3284, Russian Journal of Coordination Chemistry, 2007, Vol. 33, No. 3, pp. 168–175. © Pleiades Publishing, Ltd., 2007.
Original Russian Text © V.V. Sharutin, I.V. Egorova, A.P. Pakusina, O.K. Sharutina, M.A. Pushilin, 2007, published in Koordinatsionnaya Khimiya, 2007, Vol. 33, No. 3,
pp. 176−183.
Synthesis and Structures of Organoantimony
and Organobismuth Derivatives of 4-Sulfophenol
and 2,4-Disulfophenol
V. V. Sharutina, I. V. Egorovaa, A. P. Pakusinaa, O. K. Sharutinaa, and M. A. Pushilinb
a Blagoveshchensk State Pedagogical University, Blagoveshchensk, Russia
b Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia
Received April 6, 2006
Abstract—Tetraphenylbismuth 4-hydroxybenzenesulfonate (I) and tetraphenylantimony 4-hydroxybenzene-
sulfonate (II) are synthesized in yields up to 80% by the reaction of pentaphenylbismuth and pentaphenylanti-
mony, respectively, with 4-sulfophenol. Compounds I and II are also prepared by the ligand redistribution reac-
tion from pentaphenyl compounds of bismuth and antimony and triphenylbismuth bis(4-hydroxybenzene-
sulfonate) and triphenylantimony bis(4-hydroxybenzenesulfonate), respectively, in yields up to 87%. The
recrystallization of compounds I and II from water gives crystalline hydrates Ph4BiOSO2C6H4(OH-4) · H2O
(III) and Ph4SbOSO2C6H4(OH-4) · H2O (IV). Pentaphenylbismuth and pentaphenylantimony react with
2,4-disulfophenol in acetone, regardless of the ratio of the starting reactants, to form bis(tetraphenylbismuth)
4-hydroxybenzene-1,3-disulfonate (V) and bis(tetraphenylantimony) 4-hydroxybenzene-1,3-disulfonate (VI)
in yields up to 74%. According to X-ray diffraction data, coordination of the bismuth atoms in compound I is
trigonal-bipyramidal with the axial oxygen atom of the 4-hydroxybenzenesulfonate group (Bi···O 2.764 Å). In
compound II, coordination of the Sb atom is tetrahedral (CSbC angles 106.2°–112.3°). In crystal III, the dis-
tances between the central atom and the nearest oxygen atoms of the arenesulfonate group and the hydrate water
molecule are 3.094 and 3.125 Å, respectively. Crystals V and VI consist of doubly charged anions of 2,4-dis-
ulfophenol and several distorted tetrahedral cations of tetraphenylbismuthonium (CBi(1)C, CBi(2)C angles and
Bi(1)–C, Bi(2)–C bond lengths vary in the intervals 102.1°–122.7°, 105.4°–114.0° and 2.103–2.230, 2.187–
2.209 Å, respectively) and tetraphenylantimonium (CSb(1)C, CSb(2)C angles and Sb(1)–C, Sb(2)–C bond
lengths 106.3°–112.2°, 101.3°–122.4° and 2.095–2.110, 2.092–2.123 Å, respectively). The Bi(1) and Sb(2)
atoms are coordinated by one of the oxygen atoms of the 2,4-disulfophenol anions (distances Bi(1)···O(3)
2.803, Sb(2)···é(1) 2.704 Å).
DOI: 10.1134/S1070328407030037
INTRODUCTION
mp 170°C. IR spectrum (ν, cm–1): 1220 m, 1150 vs (SO2),
1020 s (SO).
The structures of arenesulfonates of pentavalent bis-
muth and antimony, which were predominantly pre-
pared by the dephenylation of pentaphenyl compounds
with monofunctional arenesulfonic acids, have been
described in [1–11] and [12–22], respectively. In the
present work, the structures of the reaction products of
pentaphenylbismuth and pentaphenylantimony with
polyfunctional compounds such as 4-sulfophenol and
2,4-disylfophenol are studied by X-ray diffraction anal-
ysis.
For C30H25O4SBi
anal calcd. (%):
Found (%):
C, 52.17;
C, 52.02;
H, 3.62.
H, 3.70.
Synthesis of tetraphenylantimony 4-hydroxy-
benzenesulfonate (II). A mixture of pentaphenylanti-
mony (0.67 g), 4-sulfophenol (0.23 g), and benzene
(5 ml) was kept at 20°ë for 0.5 h. The solvent was
removed, and the residue was washed with hexane
(20 ml) and dried. The yield of compound II was 0.75 g
(90%), mp 199°C. IR spectrum (ν, cm–1): 1230 m,
1130 vs (SO2), 1060 s (SO).
EXPERIMENTAL
Synthesis of tetraphenylbismuth 4-hydroxyben-
zenesulfonate (I). A mixture of 4-sulfophenol (0.17 g),
pentaphenylbismuth (0.59 g), and benzene (5 ml) was
kept at 20°ë for 0.5 h. The solvent was removed, and
the residue was washed with hexane (20 ml) and dried.
The yield of the crystals of complex I was 0.62 g (90%);
For C30H25O4SSb
anal calcd. (%):
Found (%):
C, 59.70;
C, 59.54;
H, 4.15.
H, 3.89.
168

SYNTHESIS AND STRUCTURES OF ORGANOANTIMONY
169
Reaction of pentaphenylbismuth with triphenyl- temperature factors are available at vvsharutin@ram-
bismuth bis(4-hydroxybenzenesulfonate). A mixture bler.ru from the authors.
of Ph5Bi (1.00 g), Ph3Bi[(OSO2C6H4(OH-4)]2 (1.32 g),
and toluene (20 ml) was stirred for 30 min. The result-
ing solution was concentrated to 10 ml and cooled to
RESULTS AND DISCUSSION
−18°ë. The crystals formed were filtered off, washed
with hexane, and dried. The yield of compound I was
1.90 g (82%).
Compound II was synthesized using a similar pro-
cedure (87% yield, mp 199°C). After compounds I and
II were recrystallized from water, crystalline hydrates
Ph4BiOSO2C6H4(OH-4) · H2O (III) (mp 151°C) and
Ph4SbOSO2C6H4(OH-4) · H2O (IV) (mp 168°C),
respectively, were obtained.
Synthesis of bis(tetraphenylbismuth) 4-hydroxy-
benzene-1,3-disulfonate (V). A mixture of pentaphe-
nylbismuth (0.50 g), 2,4-disulfophenol (0.10 g), and
acetone (10 ml) was kept at 20°C for 10 min. The sol-
vent was removed, and the residue was recrystallized
from water. The yield of colorless crystals V was 0.32 g
(59% yield, mp 189°C). IR spectrum (ν, cm–1):
1225 vs, 1180 vs (SO2), 1025 vs (SO).
It is known that tetraphenylantimony (tetraphenyl-
bismuth) arenesulfonates containing methyl substitu-
ents in the aromatic ring of the arenesulfo group can be
synthesized by the ligand redistribution reaction from
pentaphenylantiimony (pentaphenylbismuth) and triph-
enylantimony bis(arenesulfonates) (triphenylbismuth
bis(arenesulfonates)) [1, 2, 6–9, 13, 15, 16, 22]:
Ph5E + Ph3E(OSO2Ar)2
2Ph4EOSO2Ar,
E = Sb, Bi; Ar = C6H4Me-4, C6H3Me2-2.4, C6H3Me2-2.5,
C6H3Me2-3.4.
We have shown that the introduction of a functional
group such as hydroxyl into the organic radical of the
arenesulfonate ligand does not prevent ligand redistri-
bution. For instance, the reaction of pentaphenylbis-
muth with triphenylbismuth bis(4-hydroxybenzene-
sulfonate) (toluene, 2 h, 20°ë) affords the only product:
tetraphenylbismuth 4-hydroxybenzenesulfonate (I)
For C54H44O7S2Bi
Ph5Bi + Ph3Bi[OSO2C6H4(OH-4)]2
2Ph4BiOSO2C6H4(OH-4).
anal calcd. (%):
Found (%):
C, 50.38;
C, 50.22;
H, 3.42.
H, 3.37.
Tetraphenylantimony 4-hydroxybenzenesulfonate (II)
was synthesized similarly (toluene, 1 h, 90°ë):
Bis(tetraphenylantimony) 4-hydroxybenzene-1,3-
disulfonate (VI) was synthesized by a similar proce-
dure (89% yield, mp 129°C). IR spectrum (ν, cm−1):
1250 vs, 1160 vs (SO2), 1015 vs (SO).
Ph5Sb + Ph3Sb[OSO2C6H4(OH-4)]2
2 Ph4SbOSO2C6H4(OH-4).
The IR spectra and melting points of compounds I
and II coincided with similar characteristics of the
compounds prepared from pentaphenylbismuth (pen-
taphenylantimony) and 4-sulfophenol
For C54H44O7S2Sb2
anal calcd. (%):
Found (%):
C, 58.27;
C, 58.55;
H, 3.96.
H, 3.90.
Ph5Ö + çOSO2C6H4(OH-4)
Ph4ÖOSO2C6H4(OH-4) + PhH,
IR spectra were recorded on a Hitachi-215 spec-
trometer as suspensions in Nujol between NaCl plates.
X-ray diffraction analyses of complexes I–III, V,
and VI were carried out on a SMART-1000 CCD dif-
fractometer (Bruker) using MoKα radiation (λ =
0.71073 Å, graphite monochromator).
E = Sb, Bi.
Note that the recrystallization of compounds I and II
from
water
gave
crystalline
· H2O
hydrates
(III) and
Ph4BiOSO2C6H4(OH-4)
Ph4SbOSO2C6H4(OH-4) · H2O (IV).
Pentaphenylbismuth and pentaphenylantimony
were found to react with 2,4-disulfophenol regardless
of the molar ratio of the starting reactants forming binu-
clear organic compounds of bismuth and antimony:
bis(tetraphenylbismuth) 4-hydroxybenzene-1,3-disul-
fonate (V) and bis(tetraphenylantimony) 4-hydroxy-
benzene-1,3-disulfonate (VI)
Data collection and edition and refinement of unit
cell parameters were performed using the SMART and
SAINT-Plus programs [23]. All calculations for struc-
ture determination and refinement were performed wiht
the SHELXTL/PC programs [24].
The structures were solved by a direct method and
refined by the least-squares method in the anisotropic
approximation for non-hydrogen atoms. Positions of
hydrogen atoms were calculated geometrically and
included in refinement in the riding model.
2 Ph5E + (4-HO)C6H3(SO2OH)2-1.3
(Ph4E)2(4-HO)C6H3(SO2O)2-1.3 + 2 PhH,
E = Bi, Sb.
The main crystallographic data and results of refine-
ment of structures I–III, V, and VI are presented in
Synthesized complexes I–VI are colorless crystal-
Table 1. Selected bond lengths and bond angles are line substances soluble in aromatic hydrocarbons,
given in Table 2. The coordinates of atoms and their water, and polar organic solvents.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 3 2007

170
SHARUTIN et al.
Table 1. Crystallographic data, experimental parameters, and details of refinement of the structures of compounds I–III, V,
and VI
Value
Parameter
I
II
III
V
VI
M
690.54
295(2)
603.31
203(1)
708.56
298(2)
1286.97
293(2)
1112.51
296(2)
T, K
Crystal system
Monoclinic
Monoclinic
Monoclinic
Triclinic
Triclinic
P21/n
P21/n
Space group
C2/c
P1
P1
a, Å
10.675(1)
14.476(2)
17.215(2)
11.2075(5)
14.7405(7)
15.5857(7)
21.373(2)
14.177(1)
19.214(2)
10.259(1)
10.960(1)
22.546(2)
76.714(2)
88.453(2)
78.256(2)
2415.1(4)
2
10.255(3)
10.925(2)
22.473(4)
76.65(2)
88.33(2)
78.02(1)
2396(1)
2
b, Å
c, Å
α, deg
β, deg
γ, deg
V, Å3
Z
92.408(2)
91.665(1)
108.817(2)
2657.8(5)
4
2573.7(2)
4
5511(1)
8
ρ
calcd, g/cm3
1.726
6.746
1344
1.557
1.188
1216
1.708
6.512
2768
Prism
1.770
1.542
µ, mm–1
7.415
1.267
F(000)
1244
1116
Crystal shape (size,
mm)
Sphere
(∅ = 0.27)
Prism
Prism
Prism
(0.45 × 0.23 × 0.20) (0.13 × 0.14 × 0.26) (0.15 × 0.10 × 0.08) (0.05 × 0.07 × 0.17)
θ range, deg
2.20–31.49
2.61–31.75
2.24–25.02
1.86–25.00
3.01–31.49
Intervals of reflec-
tion indices
–13 ≤ h ≤ 15,
–21 ≤ k ≤ 20,
–23 ≤ l ≤ 25
–16 ≤ h ≤ 16,
–19 ≤ k ≤ 21,
–18 ≤ l ≤ 23
–25 ≤ h ≤ 25,
–16 ≤ k ≤ 11,
–21 ≤ l ≤ 22
–12 ≤ h ≤ 12,
–13 ≤ k ≤ 13,
–26 ≤ l ≤ 26
–9 ≤ h ≤ 11,
–12 ≤ k ≤ 11,
–23 ≤ l ≤ 24
Measured reflec-
tions
21249
21455
14344
18565
10838
Independent reflec-
tions
8390
(Rint = 0.0417)
8394
(Rint = 0.0324)
4848
(Rint = 0.0469)
8435
(Rint = 0.0479)
6806
(Rint = 0.0468)
Refinement vari-
ables
329
328
337
587
587
GOOF
1.010
1.100
0.922
0.936
0.996
R factors for
F2 > 2σ(F2)
R1 = 0.0321,
wR2 = 0.0666
R1 = 0.0379,
wR2 = 0.0849
R1 = 0.0287,
wR2 = 0.0636
R1 = 0.0526,
wR2 = 0.1385
R1 = 0.0432,
wR2 = 0.0930
R factors for all re- R1 = 0.0563,
R1 = 0.0475,
wR2 = 0.0886
R1 = 0.0445,
wR2 = 0.0710
R1 = 0.0617,
wR2 = 0.1436
R1 = 0.0737,
wR2 = 0.1060
flections
wR2 = 0.0738
Extinction coeffi-
cient
0.00028(6)
Not refined
Not refined
Not refined
Not determined
Residual electron
density
–0.862/1.677
–0.862/1.384
–0.444/0.710
–1.798/3.459
–0.351/0.306
(min/max), e/Å3
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 3 2007

SYNTHESIS AND STRUCTURES OF ORGANOANTIMONY
Table 2. Bond lengths and bond angles in structures I–III, V, and VI
171
Bond
d, Å
Angle
ω, deg
Bond
d, Å
Angle
ω, deg
I
III
Bi–C(11)
Bi–C(41)
Bi–C(31)
Bi–C(21)
Bi–O(1)
S–O(2)
S–O(3)
S–O(1)
S–C(1)
O(4)–C(4)
O(4)–H(1)
C(1)–C(6)
C(1)–C(2)
2.203(2)
2.205(2)
2.207(2)
2.213(2)
2.764(2)
1.446(2)
1.447(2)
1.454(2)
1.779(2)
1.375(3)
0.91(4)
C(11)BiC(41)
C(11)BiC(31)
C(41)BiC(31)
C(11)BiC(21)
C(41)BiC(21)
C(31)BiC(21)
C(11)BiO(1)
C(41)BiO(1)
C(31)BiO(1)
C(21)BiO(1)
O(2)SO(3)
103.65(9)
111.90(9)
96.83(9)
111.70(9)
98.93(9)
128.11(9)
81.09(8)
175.01(7)
79.80(8)
80.50(7)
113.6(1)
112.2(1)
111.0(1)
S–C(11)
O(4)–C(14)
1.761(3)
1.368(4)
C(41)BiO(1)
C(51)BiO(5)
C(21)BiO(5)
C(31)BiO(5)
C(41)BiO(5)
O(1)BiO(5)
O(1)SO(2)
O(1)SO(3)
O(2)SO(3)
O(1)SC(11)
O(2)SC(11)
O(3)SC(11)
SO(1)Bi
172.2(1)
68.5(1)
70.2(1)
172.5(1)
84.2(1)
102.5(1)
113.8(2)
112.2(2)
111.9(2)
106.3(2)
106.3(2)
105.7(2)
158.4(2)
C(11)–C(12) 1.379(4)
C(11)–C(16) 1.384(5)
C(12)–C(13) 1.374(5)
C(13)–C(14) 1.374(5)
C(14)–C(15) 1.394(5)
C(15)–C(16) 1.364(5)
C(21)–C(22) 1.327(6)
C(21)–C(26) 1.347(5)
C(22)–C(23) 1.376(8)
C(23)–C(24) 1.336(8)
C(24)–C(25) 1.300(6)
1.368(3)
1.394(3)
O(2)SO(1)
O(3)SO(1)
C(2)–C(3)
C(3)–C(4)
1.394(4)
1.386(4)
O(2)SC(1)
O(3)SC(1)
106.0(1)
106.6(1)
V
Bi(1)–C(13) 2.180(8)
C(13)Bi(1)C(7)
112.4(3)
C(4)–C(5)
C(5)–C(6)
1.369(4)
1.390(4)
O(1)SC(1)
SO(1)Bi
C(4)O(4)H(1)
C(6)C(1)C(2)
C(6)C(1)S
106.9(1)
146.6(1)
115(2)
119.7(2)
120.9(2)
119.4(2)
119.4(2)
119.9(2)
123.1(3)
Bi(1)–C(7)
Bi(1)–C(19) 2.213(7)
2.203(7)
C(13)Bi(1)C(19) 111.5(3)
C(7)Bi(1)C(19)
C(13)Bi(1)ë(1)
C(7)Bi(1)ë(1)
C(19)Bi(1)ë(1)
é(4)S(1)O(2)
O(4)S(1)O(3)
O(2)S(1)O(3)
122.7(3)
103.4(3)
101.6(3)
102.1(3)
113.9(4)
112.8(3)
110.9(4)
C(11)–C(16) 1.374(4)
C(11)–C(12) 1.380(4)
C(12)–C(13) 1.373(4)
C(13)–C(14) 1.380(6)
C(14)–C(15) 1.375(5)
C(15)–C(16) 1.388(4)
C(21)–C(26) 1.371(4)
Bi(1)–C(1)
S(1)–O(4)
S(1)–O(2)
S(1)–O(3)
S(1)–C(49)
2.230(7)
1.441(6)
1.444(6)
1.454(5)
1.777(7)
C(2)C(1)S
C(3)C(2)C(1)
C(4)C(3)C(2)
C(5)C(4)O(4)
Bi(2)–C(37) 2.187(8)
Bi(2)–C(31) 2.196(6)
C(37)Bi(2)C(31) 109.6(3)
C(37)Bi(2)C(25) 108.1(3)
C(31)Bi(2)C(25) 106.9(3)
II
Bi(2)–C(25) 2.205(7)
Bi(2)–C(43) 2.209(8)
Sb–C(31)
Sb–C(41)
Sb–C(11)
Sb–C(21)
S–O(3)
2.095(1)
2.098(1)
2.101(1)
2.104(1)
1.442(1)
C(31)SbC(41)
C(31)SbC(11)
C(41)SbC(11)
C(31)SbC(21)
C(41)SbC(21)
106.16(5)
108.71(5)
111.48(5)
109.36(5)
112.34(5)
S(2)–O(5)
S(2)–O(6)
S(2)–O(7)
S(2)–C(51)
1.434(5)
1.446(5)
1.459(6)
1.778(7)
C(37)Bi(2)ë(43)
C(31)Bi(2)ë(43)
C(25)Bi(2)ë(43)
C(5)S(2)O(6)
105.4(3)
112.8(3)
114.0(3)
114.2(3)
S–O(1)
S–O(2)
1.442(1)
1.467(1)
C(11)SbC(21)
O(3)SO(1)
108.69(5)
113.61(7)
VI
Sb(1)–C(31) 2.095(4)
Sb(1)–C(11) 2.101(5)
Sb(1)–C(21) 2.104(3)
Sb(1)–C(41) 2.110(4)
Sb(2)–C(81) 2.092(4)
Sb(2)–C(61) 2.112(4)
Sb(2)–C(71) 2.113(5)
C(31)Sb(1)C(11) 108.9(2)
C(31)Sb(1)C(21) 109.9(2)
C(11)Sb(1)C(21) 107.6(2)
C(31)Sb(1)C(41) 106.3(2)
C(11)Sb(1)C(41) 112.2(2)
C(21)Sb(1)C(41) 111.9(2)
C(81)Sb(2)C(61) 113.0(2)
S–C(1)
1.769(1)
1.355(2)
1.389(2)
1.389(2)
1.386(2)
1.393(2)
O(3)SO(2)
O(1)SO(2)
O(3)SC(1)
O(1)SC(1)
O(2)SC(1)
C(4)O(4)H(4)
112.26(8)
112.67(8)
106.51(6)
105.99(6)
105.01(6)
106(2)
O(4)–C(4)
C(1)–C(6)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
III
Sb(2)–C(51) 2.123(4)
C(81)Sb(2)C(71) 112.3(2)
C(61)Sb(2)C(71) 122.4(2)
S(1)–O(3)
1.441(3)
Bi–C(51)
Bi–C(21)
Bi–C(31)
Bi–C(41)
Bi–O(1)
Bi–O(5)
S–O(1)
2.196(3)
2.196(4)
2.206(3)
2.213(3)
3.094(2)
3.125(3)
1.439(3)
1.443(3)
1.457(3)
C(51)BiC(21)
C(51)BiC(31)
C(21)BiC(31)
C(51)BiC(41)
C(21)BiC(41)
C(31)BiC(41)
C(51)BiO(1)
C(21)BiO(1)
C(31)BiO(1)
126.6(1)
111.2(1)
105.5(1)
105.4(1)
102.7(1)
102.9(1)
74.0(1)
S(1)–O(2)
S(1)–O(1)
S(1)–C(91)
S(2)–O(5)
S(2)–O(6)
S(2)–O(7)
S(2)–C(93)
O(4)–C(94)
1.442(3)
1.459(3)
1.783(4)
1.432(3)
1.448(3)
1.469(3)
1.789(4)
1.353(5)
C(81)Sb(2)C(51) 103.2(2)
C(61)Sb(2)C(51) 101.3(2)
C(71)Sb(2)C(51) 101.0(2)
O(3)S(1)O(2)
O(3)S(1)O(1)
O(2)S(1)O(1)
O(3)S(1)C(91)
O(2)S(1)C(91)
115.0(2)
112.2(2)
111.3(2)
106.7(2)
105.6(2)
S–O(2)
S–O(3)
83.5(1)
70.5(1)
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172
SHARUTIN et al.
C(33)
C(34)
C(35)
C(32)
C(44)
C(45)
C(43)
C(46)
C(41)
C(36)
C(31)
C(42)
C(12)
C(16)
C(3)
Bi
C(2)
O(4)
C(13)
C(14)
C(11)
C(22)
O(2)
O(1)
C(21)
S
C(4)
C(26)
H(1)
C(1)
C(6)
C(25)
C(5)
C(23)
C(15)
C(24)
O(3)
Fig. 1. Structure of complex I.
C(14)
C(15)
C(13)
C(12)
C(2)
O(3)
S
C(3)
O(1)
C(16)
C(26)
C(21)
O(4)
C(1)
C(11)
C(36)
C(31)
C(25)
C(35)
C(4)
Sb
C(24)
C(23)
H(4)
C(22)
C(6)
C(34)
C(33)
C(5)
C(32)
C(41)
O(2)
C(46)
C(42)
C(45)
C(43)
C(44)
Fig. 2. Structure of complex II.
The structures of complexes I–III, V, and VI were diate between trigonal-bipyramidal and tetrahedral as
in the structure of tetraphenylbismuth sulfosalicylate
(VII) [2]. The O(1) atom of the sulfonate group in com-
pound I lies opposite to the phenyl substituent C(41)–
C(46) (O(1)BiC(41) angle 175.01(7)°) at a distance of
2.764(2) Å from the Bi atom. Thus, the phenyl group
C(41)–C(46) lies in the pseudoaxial position, whereas
determined by X-ray diffraction.
A crystal of compound I consists of tetraphenylbis-
muthonium cations and 4-hydroxybenzenesulfonate
anions forming an ion pair (Fig. 1). An analysis of the
geometric parameters of the cation (Fig. 2) shows that
coordination of the Bi atom in compound I is interme- the phenyl substituents C(11)–C(16), C(21)–C(26), and
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SYNTHESIS AND STRUCTURES OF ORGANOANTIMONY
C(12)
173
H(1)'
O(3)
C(13)
O(5)'
O(2)
C(14)
O(4)
H(4)
H(2)'
S
C(11)
C(16)
C(55)
C(23)
C(54)
C(53)
O(2)'
C(15)
O(1)
C(56)
C(51)
C(22)
C(33)
C(52)
S'
O(3)'
O(1)'
H(2)
C(34)
C(32)
C(31)
O(5)
C(24)
Bi
C(35)
C(21)
C(26)
C(46)
C(36)
H(1)
C(41)
C(25)
C(42)
C(45)
C(44)
C(43)
Fig. 3. Structure of complex III.
C(31)–C(36) are pseudoequatorial. The angles between tively); however, other geometric parameters of the
the pseudoaxial bond (Bi–C(41)) and pseudoequatorial anions are very close to each other.
Bi–C bonds are 96.8°–103.6°, and the bond angles
The introduction of a water molecule into the com-
between the pseudoequatorial Bi–C bonds vary from
position of compound I by its recrystallization from
111.7° to 128.1°. The deviation of the Bi atom from the
water considerably changes the geometric parameters
C(11)C(21)C(31) plane is 0.35 Å, unlike the value
of the structure (Fig. 3). In crystal III, the distance
0.45 Å observed in crystal VII. The Bi–O(1) distance
between the central atom and the nearest oxygen atom
of the arenesulfonate ligand (Bi–O(1)) is 3.094 Å,
(2.764(2) Å) in structure I also differs from a similar
distance in moleculeVII (2.830(6) Å) and considerably
whereas a similar distance to the oxygen atom of the
exceeds the Bi–O distance in organic compounds of
hydrate water molecule (Bi–O(5)) is somewhat longer,
pentavalent bismuth (2.19–2.27 Å) [2]. Crystal I con-
tains intermolecular hydrogen bonds H(1A)···O(3B)
i.e., 3.125 Å (Table 2). Since the sum of the van der
Waals radii of bismuth and oxygen is equal to 3.5 Å
(1.82 Å) due to which the anions form an infinite one-
[25], the coordination number of the bismuth atom in
dimensional chain along the diagonal of the xz plane.
this compound can be considered to be increased to six.
Crystal II also contains similar intermolecular However, the octahedron of the bismuth atom in com-
hydrogen bonds (H(4A)···O(2B) 1.88 Å); however, no pound III is considerably distorted, which is indicated
coordination of the Sb atom with the O atom of the are- by the values of the axial angles C(31)BiO(5),
nesulfonate group is observed. The polyhedron of the C(41)BiO(1), and C(21)BIC(51) (172.5°, 172.2°, and
Sb atom is close to a tetrahedron (CSbC angles 106.2°– 126.6°, respectively). In crystal III, the 4-hydroxyben-
112.3°) (Fig. 2, Table 2). In the 4-hydroxybenzene- zenesulfonate anions are united into infinite chains
sulfonate anions of compounds I and II, the hydroxy involving the hydrate water molecule (the O(4)···H(1)'
groups somewhat shift from the plane of the aromatic and O(2)'···H(2)' distances are 1.98 and 1.96 Å, respec-
ring (HOCC torsion angles are 10.8° and 3.9°, respec- tively).
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 33 No. 3 2007

174
SHARUTIN et al.
O(1)
C(31)
C(52)
O(7)
C(37)
C(19)
C(51)
C(43)
Bi(2)
C(49)
Bi(1)
C(13)
C(1)
S(2)
O(6)
C(25)
O(2)
O(5)
O(3)
S(1)
C(7)
O(4)
Fig. 4. Structure of complex V.
C(75)
C(74)
O(2)
C(76)
C(71)
C(63)
C(52)
C(62)
C(73)
C(72)
S(1)
C(96)
C(61)
Sb(2)
C(64)
C(65)
C(53)
C(25)
C(95)
C(94)
O(1)
C(26)
O(3)
C(91)
C(92)
C(66)
C(55)
C(24)
C(23)
C(51)
C(56)
C(33)
O(4)
C(54)
C(32)
C(34)
C(81)
C(86)
C(93)
H(4)
C(31)
C(35)
C(82)
C(83)
C(22)
C(21)
S(2)
C(36)
C(16)
C(85)
O(6)
O(7)
C(84)
O(5)
Sb(1)
C(11)
C(12)
C(42)
C(43)
C(44)
C(41)
C(46)
C(15)
C(14)
C(13)
C(45)
Fig. 5. Structure of complex VI.
Crystal structure V consists of the doubly charged raphenylbismuthonium cations is characterized by
coordination of the central atom with one of the oxygen
atoms of the 2,4-disulfophenol anion (Bi(1)···O(3)
2.803 Å), but no similar coordination is observed for
the second type of the Ph4Bi+ cations.
anions of 2,4-disulfophenol and two types of several
distorted tetrahedral cations of tetraphenylbismutho-
nium (Fig. 4). The CBi(1)C, CBi(2)C angles and the
Bi(1)–C, Bi(2)–C bond lengths change in the intervals
102.1°–122.7°, 105.4°–114.0° and 2.103–2.230,
The CSbC bond angles in compound VI (Table 2,
2.187–2.209 2Å, respectively. The first type of the tet- Fig. 5) are close to similar angles in compound V; how-
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SYNTHESIS AND STRUCTURES OF ORGANOANTIMONY
175
12. Sharutin, V.V., Sharutina, O.K., Panova, L.P., and
ever, the Sb(2)···O(1) distance (2.704 Å), as should be
expected, is somewhat shorter. The interval of the
CSbC angles (101.0°–122.0°) in the Ph4Sb+ cation in
which the central atom is coordinated to the oxygen
atom of the arenesulfonate substituent, as in complexV,
is much larger than that for the noncoordinated tet-
raphenylantimonium cation (106.3°–112.2°).
Bel’skii, V.K., Koord. Khim., 1997, vol. 23, no. 7, p. 513.
13. Sharutin, V.V., Sharutina, O.K., Panova, L.P., and
Bel’skii, V.K., Zh. Obshch. Khim., 1997, vol. 67, no. 9,
p. 1531 [Russ. J. Gen. Chem. (Engl. Transl.), vol. 67,
no. 12, p. 1438].
14. Sharutin, V.V., Sharutina, O.K., Nasonova, N.V., et al.,
Izv. Akad. Nauk, Ser. Khim., 1999, no. 12, p. 2346.
15. Sharutin, V.V., Sharutina, O.K., Tarasova, T.A., et al., Zh.
Obshch. Khim., 1999, vol. 69, no. 12, p. 1979 [Russ.
J. Gen. Chem. (Engl. Transl.), vol. 72, no. 12, p. 1892].
16. Sharutin, V.V., Sharutina, O.K., Tarasova, T.A., et al., Zh.
Obshch. Khim., 2000, vol. 70, no. 8, p. 1311 [Russ.
J. Gen. Chem. (Engl. Transl.), vol. 70, no. 8, p. 1229].
17. Sharutin, V.V., Sharutina, O.K., Panova, L.P., et al., Zh.
Obshch. Khim., 2002, vol. 72, no. 2, p. 249 [Russ. J. Gen.
Chem. (Engl. Transl.), vol. 72, no. 2, p. 229].
18. Sharutin, V.V., Pakusina, A.P., Sharutina, O.K., et al.,
Khim. Komp. Model. Butlerov. Soobshch., 2002, no. 11,
p. 13.
REFERENCES
1. Sharutin, V.V., Sharutina, O.K., Egorova, I.V., et al., Zh.
Obshch. Khim., 1999, vol. 69, no. 9, p. 1470 [Russ.
J. Gen. Chem. (Engl. Transl.), vol. 69, no. 9, p. 1368].
2. Sharutin, V.V., Sharutina, O.K., Egorova, I.V., et al., Izv.
Akad. Nauk, Ser. Khim., 1999, no. 12, p. 2350.
3. Sharutin, V.V., Sharutina, O.K., Pavlushkina, I.I., et al.,
Zh. Obshch. Khim., 2000, vol. 70, no. 12, p. 2000 [Russ.
J. Gen. Chem. (Engl. Transl.), vol. 70, no. 12, p. 1872].
4. Sharutin, V.V., Egorova, I.V., and Ivanenko, T.K., Zh.
Obshch. Khim., 2002, vol. 72, no. 1, p. 162 [Russ. J. Gen.
Chem. (Engl. Transl.), vol. 72, no. 1, p. 153].
19. Sharutin, V.V., Egorova, I.V., Pavlushkina, I.I., et al.,
Koord. Khim., 2003, vol. 29, no. 2, p. 89.
5. Sharutin, V.V., Egorova, I.V., Ivanenko, T.K., et al., Zh.
Obshch. Khim., 2002, vol. 72, no. 12, p. 2060 [Russ.
J. Gen. Chem. (Engl. Transl.), vol. 72, no. 12, p. 1952].
20. Sharutin, V.V., Sharutina, O.K., Platonova, T.P., et al.,
Zh. Obshch. Khim., 2003, vol. 73, no. 3, p. 380 [Russ.
J. Gen. Chem. (Engl. Transl.), vol. 73, no. 3, p. 354].
21. Sharutin, V.V., Pakusina, A.P., Sharutina, O.K., et al.,
Khim. Komp. Model. Butlerov. Soobshch., 2003, no. 1,
p. 22.
6. Sharutin, V.V., Pakusina, A.P., Egorova, I.V., et al.,
Koord. Khim., 2003, vol. 29, no. 5, p. 336.
7. Sharutin, V.V., Egorova, I.V., Ivanenko, T.K., et al.,
Koord. Khim., 2003, vol. 29, no. 5, p. 341.
22. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P., et al.,
8. Sharutin, V.V., Egorova, I.V., Ivanenko, T.K., et al.,
Koord. Khim., 2004, vol. 30, no. 1, p. 15.
Koord. Khim., 2003, vol. 29, no. 7, p. 502.
23. SMART and SAINT-Plus. Versions 5.0. Data Collection
and Processing Software for the SMART System, Bruker
AXS Inc., Madison, WI, USA, 1998.
9. Sharutin, V.V., Egorova, I.V., Ivanenko, T.K., et al.,
Khim. Komp. Model. Butlerov. Soobshch., 2003, no. 2,
p. 13.
24. SHELXTL/PC. Versions 5.10. An Integrated System for
Solving, Refining and Displaying Crystal Structures
From Diffraction Data, Bruker AXS Inc., Madison, WI,
USA, 1998.
10. Sharutin, V.V., Egorova, I.V., Sharutina, O.K., et al.,
Khim. Komp. Model. Butlerov. Soobshch., 2004, no. 1,
p. 16.
11. Sharutin, V.V., Egorova, I.V., Sharutina, O.K., et al., Zh.
Obshch. Khim., 2004, vol. 74, no. 9, p. 1466 [Russ. 25. Batsanov, S.S., Zh. Neorg. Khim., 1991, vol. 36, no. 12,
J. Gen. Chem. (Engl. Transl.), vol. 74, no. 9, p. 1359].
p. 3015.
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