Synthesis and structure of new crystal modification of tetraphenylantimony 4-methylbenzenesulfonate

Article abstract of DOI:10.1023/A:1019749427770

Tetraphenylantimony arenesulfonates were synthesized by the reaction of pentaphenylantimony with arenesulfonyl chlorides in toluene taken in a molar ratio of 1:1:2 in air. The structure of tetraphenylantimony 4- methylbenzenesulfonate was determined by X-ray diffraction analysis. The Sb atom has a distorted trigonal-bipyramidal coordination with phenyl and arenesulfonate groups in the axial positions. The Sb-C(Ph)_eq bond lengths vary in the 2.099(2)-2.123(2) A range, and the Sb-C(41) and Sb-O(1) distances are 2.136(2) and 2.499(1) A, respectively. The O(1)SbC(4) axial angle is 175.77(5)°.

Full text of DOI:10.1023/A:1019749427770

Russian Journal of Coordination Chemistry, Vol. 28, No. 8, 2002, pp. 540–543. Translated from Koordinatsionnaya Khimiya, Vol. 28, No. 8, 2002, pp. 577–580.
Original Russian Text Copyright © 2002 by Sharutin, Pakusina, Senchurin, A. Gerasimenko, E. Gerasimenko.
Synthesis and Structure of New Crystal Modification
of Tetraphenylantimony 4-Methylbenzenesulfonate
V. V. Sharutin, A. P. Pakusina, V. S. Senchurin, A. V. Gerasimenko, and E. A. Gerasimenko
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
Institute of Chemistry, Far East Division, Russian Academy of Sciences,
pr. Stoletiya Vladivostoka 159, Vladivostok, 690022 Russia
Received May 3, 2001
Abstract—Tetraphenylantimony arenesulfonates were synthesized by the reaction of pentaphenylantimony
with arenesulfonyl chlorides in toluene taken in a molar ratio of 1 : 1 : 2 in air. The structure of tetraphenylan-
timony 4-methylbenzenesulfonate was determined by X-ray diffraction analysis. The Sb atom has a distorted
trigonal-bipyramidal coordination with phenyl and arenesulfonate groups in the axial positions. The Sb–
C(Ph)eq bond lengths vary in the 2.099(2)–2.123(2) Å range, and the Sb–C(41) and Sb–O(1) distances are
2.136(2) and 2.499(1) Å, respectively. The O(1)SbC(4) axial angle is 175.77(5)°.
The structure of tetraphenylantimony 4-methylben-
zenesulfonate prepared from pentaphenylantimony and
triphenylantimony bis(2-methylbenzenesulfonate) was
described earlier [1]. In this work, the synthesis of the
new crystal modification of tetraphenylantimony
4-methylbenzenesulfonate is described and its molecu-
lar and crystal structure is investigated.
EXPERIMENTAL
Synthesis of tetraphenylantimony 4-methylbenze-
nesulfonate (I) was carried out by the following proce-
dure. A mixture of 1.00 g of pentaphenylantimony
(1.97 mmol), 0.38 g of 4-methylbenzenesulfonyl chlo-
ride (1.97 mmol), and 10 ml of toluene was heated at
90°ë for 1 h. Cooling of the reaction mixture led to the
C(34)
C(33)
C(35)
C(32)
O(2)
C(36)
O(3)
C(31)
C(56)
C(51)
S
C(55)
C(54)
C(26)
C(21)
C(25)
O(1)
C(46)
C(43)
C(41)
C(42)
C(45)
C(44)
C(52)
C(24)
C(57)
Sb
C(22)
C(53)
C(23)
C(2)
C(3)
C(1)
C(6)
C(4)
C(5)
Molecular structure of complex I.
1070-3284/02/2808-0540$27.00 © 2002 åÄIä “Nauka /Interperiodica”

SYNTHESIS AND STRUCTURE OF NEW CRYSTAL MODIFICATION
541
Table 1. Crystallographic data and details of the experiment and refinement of structure I and II
Value
Parameter
I
II [1]
Empirical formula
Formula weight
Temperature, K
Wave length
C31H27O3SSb
C31H27O3SSb
601.34
295(2)
åÓKα (0.71073 Å)
601.34
293(2)
åÓKα (0.71073 Å)
Crystal system
Space group
Monoclinic
Monoclinic
P21/n
C2/c
a, Å
10.166(1)
21.018(4)
b, Å
18.626(2)
15.512(3)
c, Å
14.705(1)
17.382(3)
β, deg
90.972(2)
2783.8(4)
109.10(3)
5355(2)
V, Å3
Z
4
8
ρ(calcd), g/cm3
µ, mm–1
1.435
1.095
1.492
1.139
F(000)
1216
Prism (0.21 × 0.17 × 0.15 mm)
2.19–28.00
2432
–
Crystal shape (size)
Region of data collection (θ), deg
Ranges of reflection indexes
Measured reflections
Independent reflections
Reflections with I > 2σ(I)
Refinement method
Refined parameters
GOOF
1.67–22.47
–22 ≤ h ≤ 20, –16 ≤ k ≤ 0, 0 ≤ l ≤ 16
–12 ≤ h ≤ 13, –24 ≤ k ≤ 24, –15 ≤ l ≤ 19
18145
2274
2183 (Rint = 0.0346)
1823
6692 (Rint = 0.0370)
4817
Full-matrix least-squares method for F2
327
Full-matrix least-squares method for F2
327
1.049
0.913
R factors for F2 > 2σ(F2)
R factors for all reflections
Extinction coefficient
R1 = 0.0288, wR2 = 0.0654
R1 = 0.0457, wR2 = 0.0706
Not refined
R1 = 0.0209, wR2 = 0.0531
R1 = 0.0209, wR2 = 0.0531
0.00000(5)
Residual electronic density
–0.380/0.726
–0.227/0.469
(min/max), e/Å3
Table 2. Atomic coordinates and isotropic equivalent thermal parameters (Ueq) in structure I
Atom
x
y
z
Ueq, Å2 Atom
0.78800(1) 0.136880(6) 0.415909(7) 0.04480(3) C(32) 0.5649(2) 0.2171(1)
x
y
z
Ueq, Å2
Sb
S
0.5021(1) 0.0605(5)
0.5021(1) 0.0605(5)
0.5198(2) 0.0736(6)
0.4728(2) 0.0806(7)
0.4071(2) 0.0754(7)
0.3882(1) 0.0600(5)
0.5553(1) 0.0450(4)
0.5849(1) 0.0508(4)
0.6748(1) 0.0557(5)
0.7365(1) 0.0603(5)
0.7082(1) 0.0647(6)
0.6190(1) 0.0575(5)
0.0943(1) 0.0484(4)
0.1159(1) 0.0758(6)
0.0473(2) 0.0861(7)
0.64456(4) 0.18638(2)
0.18123(3) 0.0496(1) C(32) 0.5649(2)
0.25274(9) 0.0773(4) C(33) 0.4814(2)
0.2171(1)
0.2733(1)
0.3363(1)
0.3436(1)
0.2868(1)
0.1092(1)
0.0387(1)
0.0215(1)
0.0749(1)
0.1450(1)
0.1628(1)
0.1206(1)
0.0519(1)
0.0001(1)
O(1) 0.7344(2)
O(2) 0.5115(1)
O(3) 0.6868(2)
C(1) 0.9828(2)
C(2) 1.0167(2)
C(3) 1.1488(2)
C(4) 1.2436(2)
C(5) 1.2100(2)
C(6) 1.0804(2)
C(21) 0.7121(2)
C(22) 0.7992(2) –0.0166(1)
C(23) 0.7538(2) –0.0838(1)
C(24) 0.6226(2) –0.0960(1)
C(25) 0.5352(2) –0.0414(1)
C(26) 0.5786(2)
C(31) 0.6587(2)
C(32) 0.5649(2)
0.16286(8)
0.18525(9)
0.25268(7)
0.16009(9)
0.1784(1)
0.1893(1)
0.1840(1)
0.1659(1)
0.1538(1)
0.0383(1)
0.2091(1)
0.1434(1)
0.3752(1)
0.2884(2)
0.2684(2)
0.3337(2)
0.4203(2)
0.4415(1)
0.3699(1)
0.3538(1)
0.3280(1)
0.3189(1)
0.3349(2)
0.3602(1)
0.4360(1)
0.5021(1)
0.0948(5) C(34) 0.4933(2)
0.0930(5) C(35) 0.5876(2)
0.0487(4) C(36) 0.6703(2)
0.0808(7) C(41) 0.8220(2)
0.0988(8) C(42) 0.8153(2)
0.0811(7) C(43) 0.8370(2)
0.0742(6) C(44) 0.8665(2)
0.0590(5) C(45) 0.8749(2)
0.0442(4) C(46) 0.8531(2)
0.0543(5) C(51) 0.6591(2)
0.0636(5) C(52) 0.6925(2)
0.0712(6) C(53) 0.6966(2)
0.0784(7) C(54) 0.6692(2)
0.0619(5) C(55) 0.6351(2)
0.0467(4) C(56) 0.6301(2)
0.0161(1) –0.0408(1) 0.0664(6)
0.0851(1) –0.0607(1) 0.0770(7)
0.1374(1)
0.0262(1)
0.2238(1)
0.2171(1)
0.0059(1) 0.0656(6)
0.0605(5) C(57) 0.6745(2) –0.0426(1) –0.1128(2) 0.0991(8)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 8 2002

542
SHARUTIN et al.
Table 3. Selected bond lengths and angles in structure I
Bond
Sb–C(21)
d, Å
Bond
d, Å
Angle
ω, deg
2.099(2)
2.109(2)
2.123(2)
2.136(2)
2.499(1)
1.420(1)
1.423(1)
1.449(1)
1.778(2)
1.372(3)
1.384(2)
1.394(3)
1.352(3)
1.367(3)
1.378(3)
1.376(2)
1.381(2)
1.386(2)
1.357(3)
1.373(3)
C(25)–C(26)
C(31)–C(36)
C(31)–C(32)
C(32)–C(33)
C(33)–C(34)
C(34)–C(35)
C(35)–C(36)
C(41)–C(42)
C(41)–C(46)
C(42)–C(43)
C(43)–C(44)
C(44)–C(45)
C(45)–C(46)
C(51)–C(52)
C(51)–C(56)
C(52)–C(53)
C(53)–C(54)
C(54)–C(55)
C(54)–C(57)
C(55)–C(56)
1.383(3)
1.374(2)
1.379(2)
1.376(3)
1.368(3)
1.380(3)
1.383(3)
1.385(2)
1.401(2)
1.374(2)
1.375(3)
1.375(3)
1.368(3)
1.361(3)
1.365(3)
1.396(3)
1.354(3)
1.362(3)
1.523(3)
1.383(3)
C(22)C(21)Sb
118.1(1)
122.1(1)
120.4(2)
120.0(2)
119.9(2)
121.0(2)
119.0(2)
120.3(2)
121.7(1)
118.0(1)
120.1(2)
119.8(2)
120.5(2)
119.8(2)
119.6(2)
118.4(2)
121.5(1)
120.0(1)
121.1(2)
119.7(2)
Sb–C(31)
Sb–C(1)
C(26)C(21)Sb
C(21)C(22)C(23)
C(24)C(23)C(22)
C(23)C(24)C(25)
C(24)C(25)C(26)
C(21)C(26)C(25)
C(36)C(31)C(32)
C(36)C(31)Sb
Sb–C(41)
Sb–O(1)
S–O(2)
S–O(3)
S–O(1)
S–C(51)
C(1)–C(2)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(5)–C(6)
C(21)–C(22)
C(21)–C(26)
C(22)–C(23)
C(23)–C(24)
C(24)–C(25)
C(32)C(31)Sb
C(33)C(32)C(31)
C(34)C(33)C(32)
C(33)C(34)C(35)
C(34)C(35)C(36)
C(31)C(36)C(35)
C(42)C(41)C(46)
C(42)C(41)Sb
C(46)C(41)Sb
C(43)C(42)C(41)
C(42)C(43)C(44)
Angle
ω, deg
Angle
ω, deg
C(43)C(44)C(45)
120.1(2)
C(21)SbC(31)
C(21)SbC(1)
C(31)SbC(1)
C(21)SbC(41)
C(31)SbC(41)
C(1)SbC(41)
C(21)SbO(1)
C(31)SbO(1)
C(1)SbO(1)
C(41)SbO(1)
O(2)SO(3)
119.33(6)
115.28(6)
118.01(6)
98.66(6)
98.16(6)
100.56(6)
77.71(6)
81.92(6)
83.06(6)
175.77(5)
114.9(1)
112.2(1)
110.8(1)
O(2)SC(51)
O(3)SC(51)
O(1)SC(51)
SO(1)Sb
106.77(9)
106.71(8)
104.73(8)
151.63(9)
119.3(2)
124.3(1)
116.4(1)
119.3(2)
121.1(2)
119.6(2)
120.4(2)
120.2(2)
119.7(2)
C(46)C(45)C(44)
C(45)C(46)C(41)
C(52)C(51)C(56)
C(52)C(51)S
120.6(2)
120.1(2)
119.1(2)
120.3(1)
120.6(1)
119.5(2)
122.1(2)
117.4(2)
119.9(2)
122.7(2)
121.6(2)
120.3(2)
C(2)C(1)C(6)
C(2)C(1)Sb
C(6)C(1)Sb
C(1)C(2)C(3)
C(4)C(3)C(2)
C(3)C(4)C(5)
C(4)C(5)C(6)
C(5)C(6)C(1)
C(22)C(21)C(26)
C(56)C(51)S
C(51)C(52)C(53)
C(54)C(53)C(52)
C(53)C(54)C(55)
C(53)C(54)C(57)
C(55)C(54)C(57)
C(54)C(55)C(56)
C(51)C(56)C(55)
O(2)SO(1)
O(3)SO(1)
formation of crystals; they were filtered off and dried.
The structure was solved by the direct method and
refined by the least-squares method in the anisotropic
approximation for non-hydrogen atoms. The hydrogen
atoms were placed in the geometrically calculated posi-
tions and refined in the rider model.
The yield was 0.85 g (72%), mp 163°C (164°C [1]).
X-ray diffraction analysis of crystals I was carried
out using a SMART-1000 CCD (Bruker) spectrometer
(graphite monochromator, MoKα radiation, ω scan
mode). The data were collected in sets of 906, 620, and
360 frames at ϕ = 0°, 90°, and 180°, respectively, with a
0.2° step and 15 s exposure per frame; the crystal was
placed at a distance of 45 mm from the detector. Cor-
rection for absorption of X-rays by the sample was
applied using face indices.
Collection and editing of the data and refinement of
the unit cell parameters were carried out with the
SMART and SAINT Plus programs [2]. All calcula-
tions for solution and refinement of the structure were
performed with the SHELXTL/PC programs [3].
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 8 2002

SYNTHESIS AND STRUCTURE OF NEW CRYSTAL MODIFICATION
543
Selected crystallographic data and results of the prepared from Ph5Sb and 4-methylbenzene sulfonic
structure refinement are given in Table 1. Atomic coor- acid [1] mainly differ in the Sb–O and Sb–Cax bond
dinates are listed in Table 2. Bond lengths and angles lengths, which are equal to 2.499(1) and 2.136(2) Å in
are given in Table 3.
I and to 2.588(4) and 2.129(4) Å in II, respectively.
Differences in the symmetry groups (P21/n and C2/c),
number of molecules in the unit cell (4 and 8), and den-
sity (1.435 and 1.492 g/cm3, respectively) suggest the
occurrence of two polymorphic modifications of tet-
raphenylantimony 4-methylbenzenesulfonate which
form in different chemical reactions (Table 1).
RESULTS AND DISCUSSION
Compound I was prepared from pentaphenylanti-
mony and 4-methylbenzenesulfonyl chloride in toluene
in the presence of atmospheric moisture (90°C, 1 h).
After cooling the reaction mixture, crystals I formed
(along with benzene and hydrochloride):
REFERENCES
Ph5Sb + ClSO2C6H4Me-4 + H2O
1. Sharutin, V.V., Sharutina, O.K., Panova, L.P., and
Bel’skii, V.K., Zh. Obshch. Khim., 1997, vol. 67, no. 9,
p. 1531.
Ph4SbOSO2C6H4Me-4 + HCl + PhH.
Note that the reactions of Ph5Sb with 3,4-, 2,4-, or
2,5-dimethylbenzenesulfonyl chloride occur in a simi-
lar fashion.
The X-ray diffraction analysis of I shows that the Sb
atom has a distorted trigonal-bipyramidal coordination
(figure) with the 4-methybenzenesulfonate and phenyl
ligands in the axial positions. The structures of I and of
tetraphenylantimony 4-methylbenzenesulfonate (II)
2. SMART and SAINT-Plus. Versions 5.0. Data Collection
and Processing Software for the SMART System, Madi-
son: Bruker AXS Inc., 1998.
3. Sheldrick, G.M., SHELXTL/PC, Versions 5.10: An Inte-
grated System for Solving, Refining and Displaying
Crystal Structures from Diffraction Data, Madison:
Bruker AXS Inc., 1998.
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 8 2002