Tetra- and triarylantimony pentafluoroand pentachlorophenoxides: Synthesis and structure

Article abstract of DOI:10.1134/S0036023617100163

2,3,4,5,6-Pentafluorophenoxytetraphenylantimony (I), 2,3,4,5,6-pentachlorophenoxytetraphenylantimony (_II), 2,3,4,5,6-pentafluorophenoxytetra-p-tolylantimony (III), and 2,3,4,5,6-pentachlorophenoxytetra-p-tolylantimony (IV) were synthesized by the reaction of pentaarylantimony (Ar = Ph, p-Tol) with pentafluoro- and pentachlorophenol in toluene. Compounds I–IV were also synthesized with yields of up to 95% from pentaarylantimony and triarylantimony diaroxides. Triarylantimony diaroxides Ph₃Sb(OC₆F₅)₂ (V), Ph₃Sb(OC₆Cl₅)₂ (VI), p-Tol₃Sb(OC₆F₅)₂ (VII), p-Tol₃Sb(OC₆Cl₅)₂ (VIII) were synthesized from triarylantimony, tert-butylhydroperoxide, and phenol in ether. The Sb atoms in compounds I–VIII had a distorted trigonal bipyramidal coordination with electronegative ligands in axial positions.

Full text of DOI:10.1134/S0036023617100163

ISSN 0036-0236, Russian Journal of Inorganic Chemistry, 2017, Vol. 62, No. 10, pp. 1320–1326. © Pleiades Publishing, Ltd., 2017.
Original Russian Text © V.V. Sharutin, O.K. Sharutina, A.N. Efremov, P.V. Andreev, 2017, published in Zhurnal Neorganicheskoi Khimii, 2017, Vol. 62, No. 10, pp. 1330–1336.
COORDINATION
COMPOUNDS
Tetra- and Triarylantimony Pentafluoro-
and Pentachlorophenoxides: Synthesis and Structure
V. V. Sharutina, *, O. K. Sharutinaa, A. N. Efremova, and P. V. Andreevb, **
aNational South Ural State Research University, Chelyabinsk, 454080 Russia
bLobachevskii National Research State University, Nizhny Novgorod, 603950 Russia
*e-mail: vvsharutin@rambler.ru
**e-mail: andreev@phys.unn.ru
Received June 29, 2016
Abstract⎯2,3,4,5,6-Pentafluorophenoxytetraphenylantimony (I), 2,3,4,5,6-pentachlorophenoxytetraphe-
nylantimony (II), 2,3,4,5,6-pentafluorophenoxytetra-p-tolylantimony (III), and 2,3,4,5,6-pentachlorophe-
noxytetra-p-tolylantimony (IV) were synthesized by the reaction of pentaarylantimony (Ar = Ph, p-Tol) with
pentafluoro- and pentachlorophenol in toluene. Compounds I–IV were also synthesized with yields of up to
95% from pentaarylantimony and triarylantimony diaroxides. Triarylantimony diaroxides Ph3Sb(OC6F5)2
(V), Ph3Sb(OC6Cl5)2 (VI), p-Tol3Sb(OC6F5)2 (VII), p-Tol3Sb(OC6Cl5)2 (VIII) were synthesized from triary-
lantimony, tert-butylhydroperoxide, and phenol in ether. The Sb atoms in compounds I–VIII had a distorted
trigonal bipyramidal coordination with electronegative ligands in axial positions.
DOI: 10.1134/S0036023617100163
The literature describes the synthesis of tetraphe- monitored by thin-layer chromatography. The solvent
nylantimony aroxides from pentaphenylantimony and was then removed. Colorless crystals of compound I
phenol [1–6] or triphenylantimony diaroxides and (0.300 g, 97%, Tm = 191°C) were synthesized.
pentaphenylantimony acting in the reaction as a phe-
IR spectrum (ν, cm–1): 3975, 3901, 3838, 3820,
nylating agent [5, 6]. No similar reactions with penta-
3801, 3689, 3649, 3140, 3103, 3066, 3055, 3030, 3012,
fluoro- and phentachlorophenols or their antimon-
2989, 2962, 2947, 2929, 2904, 2883, 2864, 2831, 2798,
yorganic derivatives have been studied earlier.
2763, 2736, 2698, 2654, 2621, 2594, 2571, 2544, 2532,
For continuing the study of synthesis of tetraary-
lantimony aroxides, four tetraarylantimony aroxides,
namely, Ph4SbOC6F5 (I), Ph4SbOC6Cl5 (II),
p-Tol4SbOC6F5 ⋅ 1/2TolH (III), and p-Tol4SbOC6Cl5
⋅ PhH (IV) were synthesized in this work by the reac-
tions of pentaphenylantimony and penta-para-
tolylantimony with pentafluorophenol, pentachloro-
phenol, or triarylantimony diaroxides. Triarylanti-
mony diaroxides Ph3Sb(OC6F5)2 (V), Ph3Sb(OC6Cl5)2
(VI), p-Tol3Sb(OC6F5)2 (VII), and p-Tol3Sb(OC6Cl5)2
(VIII) were synthesized by the oxidative addition reac-
tion from triarylantimony and phenol in the presence
of tert-butylhydroperoxide. The structures of com-
pounds I, III, IV, VI, VII, and VIII were determined
by X-ray diffraction.
2499, 2455, 2416, 2382, 2349, 2306, 2285, 2258, 2235,
2162, 2144, 2133, 2115, 2086, 2059, 2017, 1990, 1963,
1907, 1884, 1843, 1820, 1772, 1734, 1645, 1618, 1577,
1500, 1475, 1465, 1435, 1377, 1355, 1334, 1303, 1274,
1261, 1242, 1184, 1159, 1097, 1058, 1006, 981, 923,
852, 800, 734, 694, 653, 617, 470, 455, 445. For
C30H20F5OSb, anal. calcd. (%): С, 58.71; Н, 3.26.
Found (%): С, 58.48; Н 3.63.
Compounds II–IV were synthesized in a similar way.
Compound II (95%, Tm = 248°C).
IR spectrum (ν, cm–1): 3975, 3961, 3917, 3903,
3853, 3838, 3820, 3802, 3771, 3736, 3726, 3713, 3689,
3676, 3649, 3630, 3614, 3587, 3568, 3527, 3504, 3468,
3446, 3309, 3288, 3275, 3244, 3215, 3201, 3178, 3138,
3091, 3051, 3018, 2985, 2951, 2900, 2889, 2835, 2789,
2725, 2702, 2638, 2592, 2569, 2544, 2517, 2499, 2428,
2405, 2349, 2283, 2254, 2233, 2135, 2081, 2065, 2017,
1988, 1955, 1944, 1882, 1869, 1525, 1508, 1479, 1421,
1363, 1332, 1303, 1253, 1215, 1182, 1159, 1107, 1065,
988, 916, 768, 729, 711, 692, 468, 457, 447. For
C30H20Cl5OSb, anal. calcd. (%): С, 51.76; Н, 2.88.
EXPERIMENTAL
Synthesis of 2,3,4,5,6-pentafluorophenoxytetra-
phenylantimony (I). A mixture of pentaphenylanti-
mony (250 mg, 0.49 mmol), 2,3,4,5,6-pentafluoro-
phenol (92 mg, 0.49 mmol), and toluene (2 mL) was
allowed to stand at 24°C for 15 min. The reaction was Found (%): С, 51.63; Н, 3.03.
1320

TETRA- AND TRIARYLANTIMONY
1321
Compound III (96%, Tm = 152°C).
1192, 1161, 1072, 1014, 997, 985, 802, 773, 624, 588,
570, 484, 468, 422. For C33H21F10O2Sb, anal. calcd.
(%): С, 52.04; Н, 2.76. Found (%): С, 51.87; Н, 2.92.
IR spectrum (ν, cm–1): 3053, 3018, 2966, 2949,
2920, 2864, 2800, 2767, 2733, 2659, 2627, 2603, 2547,
2461, 2418, 2362, 2310, 2262, 2237, 1647, 1591, 1558,
1500, 1467, 1436, 1394, 1303, 1244, 1188, 1165, 1118,
1064, 1008, 993, 981, 798, 732, 696, 617, 574, 484, 457,
418.
Compound VIII (94%, Tm = 205°C).
IR spectrum (ν, cm–1): 3103, 3066, 3022, 2954,
2920, 2854, 2775, 2725, 2650, 2601, 2586, 2551, 2515,
2443, 2403, 2362, 2341, 2312, 2258, 2225, 2167, 2121,
2094, 2071, 2042, 1967, 1924, 1909, 1843, 1809, 1801,
1751, 1683, 1591, 1531, 1490, 1444, 1388, 1354, 1311,
1274, 1265, 1222, 1188, 1128, 1120, 1062, 1035, 1012,
983, 947, 881, 800, 771, 731, 715, 700, 634, 582, 507,
487, 478, 412. For C33H21F10O2Sb, anal. calcd. (%): С,
42.78; Н, 2.27. Found (%): С, 42.68; Н, 2.34.
For C75H64F10O2Sb2, anal. calcd. (%): С, 54.00; Н,
3.84. Found (%): С, 53.87; Н, 3.98.
Compound IV (93%, Tm = 210°C).
IR spectrum (ν, cm–1): 3994, 3975, 3961, 3917,
3901, 3880, 851, 3838, 3820, 3801, 3768, 3724, 3711,
3689, 3668, 3649, 3628, 3618, 3587, 3566, 3547, 3527,
3502, 3462, 3446, 3311, 3275, 3182, 3089, 3070, 3035,
2949, 2920, 2864, 2816, 2733, 2692, 2652, 2601, 2594,
2553, 2532, 2507, 2422, 2395, 2358, 2343, 2322, 2268,
2208, 2175, 2142, 2127, 2077, 2015, 1992, 1951, 1909,
1897, 1869, 1843, 1828, 1807, 1772, 1749, 1734, 1716,
1699, 1635, 1591, 1558, 1523, 1490, 1479, 1411, 1361,
1311, 1282, 1259, 1211, 1186, 1116, 1095, 1064, 1035,
1014, 987, 948, 896, 862, 842, 796, 763, 732, 713, 700,
673, 648, 630, 574, 486, 418. For C40H34Cl5OSb,
anal. calcd. (%): С, 57.85; Н, 4.10. Found (%): С,
57.75; Н, 4.22.
Reaction between pentaphenylantimony and
bis(pentafluorophenoxy)triphenylantimony. A mixture
of pentaphenylantimony (253 mg, 0.500 mmol),
bis(pentafluorophenoxy)triphenylantimony (359 mg,
0.500 mmol), and toluene (10 mL) was heated at
100°C for 5 min. The reaction mixture was cooled to –
30°C, and then the formed crystals were filtered out
and dried. Compound I (582 mg, 95%) with Tm
191°C was synthesized.
=
Compounds II (93%), III (90%), and IV (94%)
were synthesized in a similar way.
Synthesis of triphenylantimony bis(2,3,4,5,6-penta-
fluorophenoxide) (V). A mixture of triphenylantimony
(100 mg, 0.283 mmol), 2,3,4,5,6-pentafluorophenol
(104 mg, 0.566 mmol), and a 70-% tert-butylhydrop-
eroxide solution (36 mg, 0.283 mmol) in diethyl ether
(30 mL) was allowed to stand at 20°C for 24 h. After
the solvent was slowly removed, the solid precipitate
was recrystallized from a toluene–octane solvent mix-
ture (2 : 1). Colorless crystals of compound V (0.200 g,
98%, Tm = 171°C) were synthesized.
IR spectrum (ν, cm–1): 3838, 3799, 3649, 3153,
3061, 3003, 2972, 2954, 2929, 2887, 2873, 2812, 2767,
2659, 2628, 2600, 2574, 2547, 2532, 2503, 2455, 2430,
2378, 2349, 2310, 2254, 2137, 2073, 1982, 1965, 1888,
1653, 1629, 1577, 1506, 1481, 1465, 1436, 1384, 1361,
1338, 1305, 1269, 1246, 1184, 1157, 1074, 1016, 995,
921, 848, 731, 686, 657, 623, 569, 464, 447, 418. For
C30H15F10O2Sb, anal. calcd. (%): С, 50.07; Н, 2.09.
Found (%): С, 50.09; Н, 2.19.
IR spectra of compounds I–VIII were recorded on
a Shimadzu IRAffinity-1S IR-FT spectrometer as
KBr pellets in the region of 4000–400 cm–1.
X-ray diffraction analysis of crystals of compounds
I, III, IV, VI, VII, and VIII was performed on a Bruker
D8 QUEST diffractometer (MoKα radiation, λ =
0.71073 Å, graphite monochromator) at 296 K. The
collection and edition of data, the refinement of unit
cell parameters, and the application of absorption cor-
rections were performed using the SMART and
SAINT-Plus software [7]. All calculations on the solu-
tion and refinement of structures were performed
using the software SHELXL/PC [8] and OLEX2 [9].
The structures were solved by direct methods and
refined by the least-squares technique in the anisotro-
pic approximation for non-hydrogen atoms. Selected
crystallographic data and structure refinement results
are given in Table 1, and selected bond lengths and
bond angles are listed in Table 2.
Compounds VI–VIII were synthesized in a si-
milar way.
The complete tables of atomic coordinates, bond
lengths, and bond angles were deposited with the
Cambridge Structure Database (no. 1469676 for I,
no. 1470617 for III, no. 1473086 for IV, no. 1476218 for
VI, no. 1474591 for VII, and no. 1483785 for VIII;
deposit@ccdc.cam.ac.uk; http://www.ccdc.cam.ac.uk).
Compound VI (95%, Tm = 231°C).
IR spectrum (ν, cm–1): 3147, 3107, 3061, 2989,
2954, 2831, 2723, 2650, 2515, 2445, 2306, 2254, 2225,
2144, 1761, 1683, 1653, 1575,1531,1481, 1436, 1394,
1388, 1354, 1220, 985, 773, 731, 715, 688, 511, 459,
406. For C30H15Cl10O2Sb, anal. calcd. (%): С, 40.74;
Н, 1.70. Found (%): С, 40.67; Н, 1.83.
RESULTS AND DISCUSSION
It is known that tetraarylantimony aroxides can be
synthesized from pentaarylantimony and alkylphenols
Compound VII (97%, Tm = 138°C).
IR spectrum (ν, cm–1): 3153, 3059, 3026, 2972, in an aromatic hydrocarbon solution under heating
2929, 2870, 2733, 2663, 2625, 2463, 2434, 1917, 1651, [1–3]. At the same time, the reactions between pen-
1593, 1510, 1504, 1465, 1398, 1373, 1350, 1305, 1246, taphenylantimony and phenols containing electron-
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 62 No. 10 2017

1322
SHARUTIN et al.
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 62
No. 10
2017

TETRA- AND TRIARYLANTIMONY
1323
Table 2. Selected bond lengths (d) and bond angles (ω) in the structures of compounds I, III, IV, VI, VII, and VIII
Bond
d, Å
Angle
ω, deg
I
Sb(1)–O(1)
Sb(1)–С(11)
Sb(1)–С(31)
Sb(1)–С(21)
Sb(1)–С(1)
Sb(2)–С(61)
Sb(2)–O(2)
Sb(2)–С(51)
Sb(2)–С(81)
Sb(2)–С(71)
2.285(5)
2.101(6)
2.151(7)
2.115(7)
2.120(6)
2.125(6)
2.272(5)
2.115(7)
2.192(7)
2.118(6)
C(11)Sb(1)C(21)
C(11)Sb(1)C(1)
C(21)Sb(1)C(1)
C(31)Sb(1)O(1)
C(11)Sb(1)O(1)
C(51)Sb(2)C(61)
C(51)Sb(2)C(71)
C(71)Sb(2)C(61)
C(81)Sb(2)O(2)
C(71)Sb(2)O(2)
118.0(3)
120.5(2)
118.2(3)
177.5(3)
83.3(2)
116.5(3)
120.7(2)
118.6(3)
176.8(3)
82.5(2)
III
Sb(1)–O(1)
Sb(1)–C(21)
Sb(1)–C(11)
Sb(1)–C(1)
Sb(1)–C(31)
Sb(2)–O(2)
Sb(2)–C(81)
Sb(2)–C(51)
Sb(2)–C(71)
Sb(2)–C(61)
2.317(7)
2.126(11)
2.148(10)
2.119(10)
2.154(8)
2.271(8)
2.190(9)
2.090(9)
2.118(11)
2.127(11)
C(21)Sb(1)C(11)
C(1)Sb(1)C(21)
C(1)Sb(1)C(11)
C(31)Sb(1)O(1)
C(1)Sb(1)O(1)
C(51)Sb(2)C(71)
C(51)Sb(2)C(61)
C(71)Sb(2)C(61)
C(81)Sb(2)O(2)
C(71)Sb(2)O(2)
117.2(4)
119.0(4)
119.8(4)
177.3(4)
83.1(3)
117.3(4)
120.3(4)
118.3(4)
177.7(3)
83.8(4)
IV
VI
Sb(1)–C(15)
Sb(1)–C(22)
Sb(1)–C(8)
Sb(1)–C(1)
Sb(1)–O(1)
2.105(4)
2.112(4)
2.115(4)
2.169(4)
2.367(3)
C(15)Sb(1)C(22)
C(15)Sb(1)C(8)
C(22)Sb(1)C(8)
C(1)Sb(1)O(1)
C(8)Sb(1)O(1)
118.08(16)
121.85(15)
115.92(15)
177.03(12)
82.57(12)
Sb(1)–C(1)
Sb(1)–O(1)
Sb(1)–O(2)
Sb(1)–C(21)
Sb(1)–C(11)
2.103(6)
2.100(4)
2.100(4)
2.120(6)
2.109(6)
C(1)Sb(1)C(21)
C(1)Sb(1)C(11)
C(11)Sb(1)C(21)
O(1)Sb(1)O(2)
O(2)Sb(1)C(21)
114.4(2)
103.3(2)
142.3(2)
174.04(15)
87.37(19)
VII
Sb(1)–O(2)
Sb(1)–C(1)
Sb(1)–C(11)
Sb(1)–O(1)
Sb(1)–C(21)
Sb(2)–O(3)
Sb(2)–O(4)
Sb(2)–C(51)
Sb(2)–C(71)
Sb(2)–C(61)
2.103(10)
2.027(14)
2.076(15)
2.094(11)
2.066(15)
2.091(10)
2.057(11)
2.114(13)
2.109(13)
2.137(14)
C(21)Sb(1)C(11)
C(1)Sb(1)C(11)
C(1)Sb(1)C(21)
O(1)Sb(1)O(2)
C(11)Sb(1)O(1)
C(51)Sb(2)C(61)
C(71)Sb(2)C(51)
C(71)Sb(2)C(61)
O(4)Sb(2)O(3)
O(3)Sb(2)C(61)
117.6(6)
127.6(5)
114.8(6)
178.8(5)
87.3(5)
127.6(6)
117.8(6)
114.5(6)
179.2(5)
87.8(5)
VIII
Sb(1)–O(2)
Sb(1)–O(1)
Sb(1)–C(1)
Sb(1)–C(21)
Sb(1)–C(11)
Sb(2)–O(3)
Sb(2)–O(4)
Sb(2)–C(71)
Sb(2)–C(61)
Sb(2)–C(51)
2.085(12)
2.122(14)
2.124(17)
2.103(17)
2.101(19)
2.155(13)
2.095(11)
2.100(17)
2.135(15)
2.121(13)
C(11)Sb(1)C(1)
C(21)Sb(1)C(1)
C(21)Sb(1)C(11)
O(2)Sb(1)O(1)
C(21)Sb(1)O(1)
C(51)Sb(2)C(61)
C(71)Sb(2)C(61)
C(71)Sb(2)C(51)
O(4)Sb(2)O(3)
C(61)Sb(2)O(3)
101.8(7)
138.3(6)
119.9(5)
174.8(6)
86.8(6)
118.7(7)
138.6(7)
102.5(6)
174.8(5)
85.7(6)
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 62 No. 10 2017

1324
SHARUTIN et al.
C(34)
C(37)
C(34)
C(35)
C(36)
C(33)
C(33)
C(32)
C(35)
C(36)
C(6)
C(32)
C(26)
C(31)
C(3)
C(2)
C(22)
C(26)
C(31)
Sb(1)
C(23)
C(1)
C(11)
C(21)
C(11)
Sb(1)
C(16)
C(12)
C(15)
C(24)
C(25)
C(12)
C(41)
C(21)
C(14)
C(5)
C(4)
C(13)
C(1)
C(6)
C(16)
C(41)
C(2)
O(1)
C(105)
F(1)
C(14)
O(1)
F(1)
C(17)
F(5)
F(5)
C(3)
C(45)
C(45)
C(7)
C(104)
F(4)
F(3)
C(42) C(101)
C(43)
C(42)
C(43)
F(2)
F(4)
F(3)
C(103)
C(44)
F(2)
C(44)
C(107)
C(102)
Fig. 1. Molecular structure of pentafluorophenoxytetrap-
henylantimony (Ia).
Fig. 2. Molecular structure of pentafluorophenoxytetra-
para-tolylantimony solvate (IIIa).
drawing substituents in the aroxy group are completed
in 1–2 h and do not require the heating of a reaction
mixture [4, 6], in agreement with the pronounced
acidic properties of the above-mentioned phenols.
It may be expected that the reaction of pentaary-
lantimony with pentafluoro- and pentachlorophenol
will occur within a much shorter time interval. Actu-
ally, we have found that the reactions of pentaphe-
nylantimony and penta-para-tolylantimony with pen-
tahalidephenols in an aromatic hydrocarbon are com-
pleted in several minutes at room temperature with a
yield of up to 97%:
Ar3Sb + 2HOAr' + tert-BuOOH
→ Ar3Sb(OAr')2 + tert-BuOH + H2O
Ar = Ph, Hal = F (V), Cl (VI);
Ar = p-Tol, Hal = F (VII), Cl (VIII).
The structures of compounds I–VIII were studied
by IR spectroscopy and X-ray diffraction.
The IR spectra of compounds I–VIII contain the
absorption bands belonging to the vibrations of Sb–
C(Ph) bonds in the SbC3 moiety [13] at 450–478 cm–1
and the absorption bands characterizing С–О bonds
at 1220–1303 cm–1.
According to X-ray diffraction data, the antimony
atoms in molecules Iab, IIIab, IV, VI, VIIab, and VIIIab
have a distorted trigonal bipyramidal coordination to
axial aroxyl ligands and phenyl groups in the equato-
rial plane (Figs. 1–6).
Ar5Sb + HOС6Hal5 → Ar4SbOС6Hal5 + ArH
Ar = Ph, Hal = F (I), Cl (II);
Ar = p-Tol, Hal = F (III), Cl (IV).
We found that the method based on the ligand
redistribution reaction between pentaarylantimony
and triarylantimony diaroxides (toluene, 100°C, 5 min)
The axial OSbC and OSbO angles are 177.5(3)°
Ar5Sb + Ar3Sb(OAr')2 → 2Ar4SbOAr with a target (Ia), 176.8(3)° (Ib), 177.3(4)° (IIIa), 177.7(3)° (IIIb),
177.03(12)° (IV), and 174.04(15)° (VI), 178.8(5)°
(VIIa), 179.2(5)° (VIIb), 174.8(6)° (VIIIa), 174.8(5)°
(VIIIb). The sums of СeqvSbCeqv angles in the equato-
rial plane are 356.7(3)° (Ia), 355.8(3)° (Ib), 356.0(4)°
(IIIa), 355.9(4)° (IIIb), 355.85(15)° (IV), 360.0(2)°
(VI), 360.0(6)° (VIIa), 359.9(6)° (VIIb), 360.0(6)°
(VIIIa), and 359.8(7)° (VIIIb). The antimony atom in
compounds Iab, IIIab, and IV is out of the equatorial
plane towards an axial carbon atom, while the metal
atoms in molecules of compounds VI, VIIab, and VIIIab
lie in equatorial plane С3.
product yield of up to 99% is equally efficient for the
synthesis of compounds I–IV.
As follows from the literature data, the oxidative
addition reaction underlying the synthesis of many
organoantimony compounds with the general formula
Ar3SbX2 (Х is the residue of an Н-acid) [10] does not
always lead to the formation of triarylantimony diar-
oxides in the case of phenols when the target product
is obtained from triarylantimony and an acid in the
presence of a peroxide [11, 12].
However, we synthesized bis(pentahalidearoxy)tri-
The Sb–Ceqv bond lengths in the studied com-
arylantimony from triarylantimony and pentahalo-
phenols using tert-butylhydroperoxide as an oxidizer pounds variate within the following ranges: 2.101(6)–
(ether, 20°C, 12 h) with a yield of up to 98% as
2.192(7) Å (Iab), 2.090(10)–2.154(8) Å (IIIab),
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 62
No. 10
2017

TETRA- AND TRIARYLANTIMONY
1325
C(37)
C(36)
Cl(2)
C(38)
C(28)
C(24)
C(7)
Cl(3)
C(33)
C(32)
C(39)
C(40)
C(3)
Cl(1)
C(31)
O(1)
C(34)
Cl(4)
C(25)
C(4)
C(5)
C(35)
C(13)
C(6)
C(22)
C(12)
C(1)
C(26)
C(35)
C(36)
C(27)
C(16)
Cl(5)
C(6)
C(1)
C(11)
C(14)
C(26)
C(15)
C(17)
C(25)
Sb(1)
Sb(1)
C(21)
C(9)
C(15)
C(4)
C(21)
C(8)
Cl(5)
C(24)
C(18)
O(1)
Cl(6)
C(10)
C(11)
C(22)
C(23)
Cl(7)
C(29)
C(13)
C(2)
O(2)
C(41)
C(46)
C(3)
C(34)
C(43)
C(44)
Cl(1)
C(42)
C(12)
Cl(4)
C(30)
C(31)
C(14)
Cl(10)
C(33)
C(32)
Cl(8)
C(45)
Cl(9)
Cl(2)
Cl(3)
Fig. 4. Molecular structure of bis(pentachlorophe-
noxy)triphenylantimony (VI).
Fig. 3. Molecular structure of pentachlorophenoxytetra-
para-tolylantimony solvate with benzene (IV).
C(27)
F(7)
C(34)
Cl(8)
Cl(3)
Cl(4)
C(24)
C(43)
C(23)
C(43)
F(6)
C(25)
C(22)
Cl(2)
C(41)
C(44)
F(8)
Cl(9)
C(42)
Cl(7)
C(27)
C(24)
C(33)
C(25)
O(2)
C(26)
C(21)
Cl(1)
C(32)
C(44)
C(45)
C(35)
C(36)
Cl(5)
C(45)
C(46)
Cl(10)
C(21)
C(6)
C(42)
Cl(6)
F(9)
C(23)
F(10)
C(16)
Sb(1)
C(31)
O(1)
C(41)
O(2)
C(11)
C(5)
C(15)
C(14)
C(1)
C(3)
Sb(1)
C(11)
F(5)
C(1)
C(7)
C(12)
C(36)
C(17)
C(4)
C(12)
C(13)
C(2)
C(3)
C(13)
F(4)
O(1)
C(6)
C(31)
C(32)
C(15)
C(14)
C(2)
C(34)
F(1)
C(4)
C(5)
C(33)
F(2)
C(17)
F(3)
C(7)
Fig. 5. Molecular structure of bis(pentafluorophenoxy)tri-
para-tolylantimony (VIIa).
Fig. 6. Molecular structure of bis(pentachlorophe-
noxy)tri-para-tolylantimony (VIIIa).
2.105(4)–2.169(5) Å (IV), 2.103(6)–2.120(6) Å (VI), 2.057(11)–2.103(10) Å (VIIab), 2.085(12)–2.155(13) Å
(VIIIab)) indicate a covalent character of bonding
2.027(14)–2.137(14) Å (VII), 2.101(19)–2.135(15) Å
(VIII). The Sb–O distances in molecules Ia (2.285(5) Å),
Ib (2.272(5) Å), IIIa (2.317(7) Å), IIIb (2.271(8) Å),
and IV (2.367(3) Å) are much greater than the anti-
mony and oxygen covalent radii in sum (2.07 Å [14])
due to a higher polarity of the Sb–O bond in tetraaryl-
antimony aroxides. However, the Sb–O distances in
between antimony and oxygen atoms.
In a molecule of compound Ia, one C(11)–C(17)
phenyl ring, whose plane nearly coincides with equa-
torial plane С3 (the inclination angle of this ring to the
equatorial plane is 32.82°), screens the C(41)–C(47)
aroxy group, thus leading to the interaction between
the symmetric antimony compounds (2.100(4) Å (VI), their π systems. The ideal geometry for π–π-stacking
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY Vol. 62 No. 10 2017

1326
SHARUTIN et al.
5. V. V. Sharutin, O. K. Sharutina, P. E. Osipov, and
O. V. Subacheva, Russ. J. Gen. Chem. 71, 983 (2001).
doi 10.1023/A:1012368510207
interaction is distorted: the distance between the cen-
ters of the aryl and phenyl π systems is 3.00 Å, and the
interplanar angle is 23.43°. This, however, is fre-
quently encountered in such interactions [15, 16].
Similar π–π-stacking interactions are observed in the
other molecules of non-symmetric (Ib, IIIab, IV) and
symmetric (VI, VIIab, VIIIab) structures. Thus, the
same interplanar angle in compound VI is 35.47°, and
the distance between the centers of the aryl and phenyl
π-systems is 3.80 Å.
The structural organization in crystals is caused by
weak intermolecular hydrogen bonds H⋅⋅⋅Cl (2.51–
2.65 Å in I, 2.55–2.67 Å in III, 2.84 Å in VI, 2.45–2.56 Å
in VII, 2.87–2.95 Å in VIII), and H⋅⋅⋅О (2.41 Å in IV).
6. V. V. Sharutin, O. K. Sharutina, V. S. Senchurin, and
A. O. Shchelokov, Zh. Obshch. Khim. 86, 92 (2016).
7. Bruker (1998). SMART and SAINT-Plus. Versions 5.0.
Data Collection and Processing Software for the
SMART System (Bruker, Madison, WI, 1998).
8. Bruker (1998). SHELXTL/PC. Versions 5.10. An Inte-
grated System for Solving, Refining and Displaying
Crystal Structures From Diffraction Data (Bruker,
Madison, WI, 1998).
9. O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, et al.,
J. Appl. Crystallogr. 42, 339 (2009). doi
10.1107/S0021889808042726
10. V. V. Sharutin and V. S. Senchurin, Named Reactions in
the Chemistry of Organoelement Compounds (YuUrGU
Press, Chelyabinsk, 2011) [in Russian].
11. V. V. Sharutin, A. P. Pakusina, M. A. Pushilin, et al.,
Russ. J. Gen. Chem. 73, 541 (2003). doi
10.1023/A:1025628217346
12. V. V. Sharutin, A. P. Pakusina, O. V. Subacheva, et al.,
Russ. J. Coord. Chem. 29, 395 (2003). doi
10.1023/A:1024155926526
ACKNOWLEDGMENTS
This work was financially supported by the Ministry
of Education and Science of the Russian Federation
within the framework of state task no. 4.6151.2017/8.9
and the Russian Foundation for Basic Research (proj-
ect no. 16-33-00752 mol_a).
13. A. Gupta, R. K. Sharma, R. Bohra, et al., Polyhedron
REFERENCES
21, 2387 (2002). doi 10.1016/S0277-5387(02)01155-5
1. V. V. Sharutin, O. K. Sharutina, P. E. Osipov, et al.,
14. S. S. Batsanov, Zh. Neorg. Khim. 36, 3015 (1991).
Russ. J. Coord. Chem. 27, 483 (2001).
15. M. L. Glowka, D. Martynowski, and K. Kozlowska,
J. Mol. Struct. 474, 81 (1999). doi 10.1016/S0022-
2860(98)00562-6
2. V. V. Sharutin, O. K. Sharutina, P. E. Osipov, et al.,
Zh. Obshch. Khim. 67, 1528 (1997).
3. V. V. Sharutin, O. K. Sharutina, P. E. Osipov, et al., 16. S. Tsuzuki, K. Honda, T. Uchimaru, et al., J. Am.
Russ. J. Gen. Chem. 70, 867 (2000).
Chem. Soc. 124, 104 (2002). doi 10.1021/ja0105212
4. V. V. Sharutin, V. V. Zhidkov, D. V. Muslin, et al., Izv.
Akad. Nauk SSSR, Ser. Khim., No. 5, 958 (1995).
Translated by E. Glushachenkova
RUSSIAN JOURNAL OF INORGANIC CHEMISTRY
Vol. 62
No. 10
2017