μ-Oxo-bis[(bromo)tri-m-tolylantimony]: Synthesis and structure

Article abstract of DOI:10.1023/A:1016297110877

μ-Oxo-bis[(bromo)tri-m-tolylantimony] was synthesized by the reaction of tri-m-tolylstibine with hydrobromic acid in ether in the presence of hydrogen peroxide. The complex was structurally characterized by X-ray diffraction analysis. The coordination polyhedron of the Sb atoms is a distorted trigonal bipyramid with the bromine and the bridging O atoms in the axial positions. The Sb(1)-C(Ph) distances vary from 2.085(9) to 2.111(8) A. The Sb(1)-Br(1) and Sb(2)-Br(2) bond lengths are 2.739(2) and 2.735(2) A, respectively; the Sb-O_br distances measure 1.949(1) A.

Full text of DOI:10.1023/A:1016297110877

Russian Journal of Coordination Chemistry, Vol. 28, No. 7, 2002, pp. 473–476. Translated from Koordinatsionnaya Khimiya, Vol. 28, No. 7, 2002, pp. 506–509.
Original Russian Text Copyright © 2002 by Sharutin, Pakusina, Nasonova, Fukin, Zakharov.
m-Oxo-Bis[(Bromo)Tri-m-Tolylantimony]:
Synthesis and Structure
V. V. Sharutin, A. P. Pakusina, N. V. Nasonova, G. K. Fukin, and L. N. Zakharov
Blagoveshchensk State Pedagogical University, ul. Lenina 104, Blagoveshchensk, 675000 Russia
Received March 24, 2001
Abstract—µ-Oxo-bis[(bromo)tri-m-tolylantimony] was synthesized by the reaction of tri-m-tolylstibine with
hydrobromic acid in ether in the presence of hydrogen peroxide. The complex was structurally characterized
by X-ray diffraction analysis. The coordination polyhedron of the Sb atoms is a distorted trigonal bipyramid
with the bromine and the bridging O atoms in the axial positions. The Sb(1)–C(Ph) distances vary from 2.085(9)
to 2.111(8) Å. The Sb(1)–Br(1) and Sb(2)–Br(2) bond lengths are 2.739(2) and 2.735(2) Å, respectively; the
Sb–Obr distances measure 1.949(1) Å.
About 20 compounds of the general formula anisotropic approximation for all non-hydrogen atoms
(Ar3SbX)2O have been structurally characterized to to R = 0.0580, Rw = 0.1430, and S = 1.016 from 6937
date [1–15]. The SbOSb fragment in these compounds reflections with I > 2σ(I ). The H atoms were located
may be either nearly linear or curved (the SbOSb angle geometrically and refined in the rider model with fixed
ranges from 139.0° to 160.0°). Apparently, the geome- Uiso values.
try of this fragment is determined by substituents at the
All computations were performed with the
Sb atoms (in particular, by their steric and electron
SHELX97 programs [16] using an IBM PC.
effects) or by the molecular packing in the crystal.
Atomic coordinates and equivalent isotropic ther-
In this study, the molecular and crystal structures of
mal parameters are given in Table 1. Bond lengths and
µ-oxo-bis[(bromo)tri-m-tolylantimony]
(I)
with
angles are presented in Table 2.
ligands more bulky than phenyl were investigated.
RESULTS AND DISCUSSION
EXPERIMENTAL
It is known that triarylstibine can be oxidized with
hydrogen peroxide in the presence of arenesulfonic
acids into µ-oxo-bis[(arenesulfonato)triarylantimony]
[15]. We found that the use of hydrobromic acid instead
of arenesulfonic acid does not change the reaction
scheme. In this way, µ-oxo-bis[(bromo)tri-m-tolylanti-
mony(V)] (I) was obtained from tri-m-tolylstibine,
hydrogen peroxide, and hydrobromic acid:
Complex I was synthesized as follows. A 31% solu-
tion of H2O2 (0.15 ml, 1.38 mmol) was added to a mix-
ture of tri-m-tolylantimony (1.00 g, 2.78 mmol) and
aqueous 40% HBr (0.50 ml, 2.72 mmol) in 20 ml of
ether. After 12 h, the colorless crystals that formed were
filtered off and dried. The yield of I was 1.06 g (87%);
mp 210°C.
For C42H42OBr2Sb2
2(m-MeC6H4)3Sb + 2HBr + 2H2O2
anal. calcd. (%): C, 57.17;
Found (%): C, 57.48;
H, 4.35;
H, 4.53;
Br, 16.56.
Br, 16.04.
ether
[(m-MeC6H4)3SbBr]2O.
–3H2O
X-ray diffraction analysis of crystals I was carried
out using a Siemens P3/CP four-circle diffractometer
(MoKα radiation, graphite monochromator, θ/2θ scan
mode).
The crystals of I are triclinic: at 20°ë, a = 9.921(3) Å,
b = 10.259(5) Å, c = 19.834(13) Å, α = 95.12(5)°, β =
95.08(4)°, γ = 99.39(4)°, V = 1973(2) Å3, space group
The structural units of crystal I are two types of
crystallographically nonequivalent binuclear Sb(V)
complexes in which two (m-MeC6H4)3SbBr fragments
are united through the bridging O atom (figure) lying in
the center of inversion.
The Sb(1) and Sb(2) atoms have a slightly distorted
trigonal-bipyramidal coordination; the equatorial
CSbC angles range from 115.7(3)° to 124.1(1)° for
Sb(1) and from 119.8(4)° to 121.6(3)° for Sb(2), and
P1, ρcalcd = 1.626 g/cm3, µ = 3.425 mm–1, Z = 4 (two
independent molecules).
The structure was solved by the direct method and the axial BrSbO angle is equal to 175.52(4)° and
refined by the full-matrix least squares method in the 176.30(4)°, respectively.
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474
SHARUTIN et al.
Table 1. Atomic coordinates (×104) and equivalent isotropic thermal parameters (×103) for structure I
Atom
x
y
z
Uequiv, Å2
Sb(1)
O(1)
Br(1)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
C(7)
–5707(1)
–5000
–6688(1)
1333(1)
0
4495(1)
5000
34(1)
45(2)
65(1)
44(2)
65(3)
85(4)
76(4)
60(3)
47(2)
91(4)
44(2)
66(3)
78(4)
81(4)
70(3)
54(2)
124(7)
38(2)
63(3)
83(4)
67(3)
51(2)
42(2)
71(3)
37(1)
50(2)
65(1)
41(2)
55(3)
73(3)
81(4)
69(3)
55(3)
146(8)
54(3)
102(5)
143(8)
99(5)
65(3)
54(3)
91(4)
40(2)
55(3)
67(3)
66(3)
57(3)
47(2)
98(5)
3328(1)
2276(9)
3620(10)
4168(12)
3413(13)
2129(11)
1538(10)
1320(15)
1889(8)
1689(12)
1997(14)
2509(13)
2707(12)
2374(10)
3290(19)
–66(8)
218(11)
–774(12)
–2035(11)
–2325(9)
–1328(8)
–3678(10)
3983(1)
5000
2705(1)
5420(9)
5117(11)
6117(13)
7360(14)
7641(11)
6646(9)
8984(13)
2325(9)
1065(11)
3(12)
233(13)
1511(11)
2548(10)
1730(14)
4022(8)
4461(10)
4493(12)
4011(11)
3553(11)
3580(9)
2996(15)
3880(1)
4348(4)
4587(6)
4495(7)
4141(6)
3886(5)
4007(4)
3460(7)
5299(4)
5220(12)
5771(7)
6387(7)
6482(6)
5922(5)
7149(7)
3690(4)
3029(5)
2509(5)
2677(5)
3330(5)
3855(5)
3508(6)
–279(1)
0
–665(1)
–910(4)
–1601(5)
–2011(6)
–1709(7)
–1026(6)
–619(5)
–699(10)
–726(5)
–704(9)
–994(10)
–1287(8)
–1327(5)
–1034(5)
–1648(7)
742(4)
–3716(9)
–3248(13)
–1924(15)
–1112(13)
–1582(11)
–2903(10)
–757(13)
–6785(10)
–8218(11)
–8896(12)
–8167(14)
–6759(14)
–6084(11)
–5923(16)
–6720(9)
–6751(12)
–7341(14)
–7910(13)
–7896(10)
–7281(9)
–8451(12)
–13613(1)
–15000
–11548(1)
–12868(9)
–13061(11)
–12674(13)
–12020(14)
–11779(12)
–12 217(11)
–11023(20)
–15069(11)
–14810(16)
–15817(21)
–17041(16)
–17314(13)
–16302(11)
–18647(13)
–12731(9)
–11368(11)
–10843(12)
–11676(13)
–13039(12)
–13550(10)
–13961(15)
C(8)
C(9)
C(10)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(17)
C(18)
C(19)
C(20)
C(21)
Sb(2)
O(2)
Br(2)
C(22)
C(23)
C(24)
C(25)
C(26)
C(27)
C(28)
C(29)
C(30)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(37)
C(38)
C(39)
C(40)
C(41)
C(42)
912(5)
1579(6)
2054(5)
1891(5)
1207(5)
2392(7)
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 7 2002

µ-OXO-BIS[(BROMO)TRI-m-TOLYLANTIMONY]: SYNTHESIS AND STRUCTURE
475
tances (2.693–2.750 Å) found for similar molecules [7,
11]. The Sb–C(Ph) distances in I (2.085(9)–2.127(9) Å)
are typical of organoantimony(V) compounds.
C(21)
C(19)
C(10)
C(9)
C(11)
With the aim of elucidating the reasons for the broad
range of the SbOSb angles in (Ar3SbX)2O complexes,
we analyzed two series of analogous compounds,
namely, (Ph3Sbï)2é (where X = Cl [6, 10], Br [7, 11],
and I [8, 9]) and (Ar3SbBr)2O (whereAr = Ph [7], o-Tol
[11], and p-Tol [11]). In the former series, the SbOSb
angle ranges from 139° to 180°, being independent of
the nature of the X atom (139.0° [6] and 173.1° [10] for
Cl, 170.3° [7] for Br, and 180° [8, 9] and 144.6° [8] for
I). The same situation is observed in the latter series:
the SbOSb angle ranges from 161° to 180° and is inde-
pendent of the Ar structure (170.3° [7] for Ph, 161.0°
[11] for o-Tol, 180° [11] for p-Tol, and 180° (this study)
for m-Tol).
C(18)
C(17)
C(1A)
C(15) C(20)
C(8)
Sb(1A) C(16)
Br(1A)
Sb(1)
C(12)
Br(1)
C(13)
C(14)
O(1)
C(8A)
C(15A)
C(1)
C(6)
C(2)
C(5)
Thus, the SbOSb angle in (Ar3Sbï)2O complexes
depends neither on the electron-accepting properties
of the X atoms nor on the presence of substituents in
the aryl groups. Hence, one can assume that the
SbOSb angle value in (Ar3Sbï)2O complexes is
mainly influenced by the molecular packing in the
crystal.
C(3)
C(7)
C(4)
Structure of one of the two independent dimers I.
The Sb–O and Sb–Br distances in the independent
molecules of I are 1.949(1) and 2.739(2) Å for Sb(1)
and 1.946(1) and 2.735(2) Å for Sb(2), which are close
to the analogous Sb–O (1.930–1.965 Å) and Sb–Br dis-
ACKNOWLEDGMENTS
The authors are grateful to the Russian Founda-
tion for Basic Research for financial support pro-
vided to us to acquire a license for the use of the
Cambridge Crystallographic Database, project no.
99-07-90133.
Table 2. Selected bond lengths and angles in structure I
Bond
d, Å
Bond
d, Å
Sb(1)–O(1)
Sb(1)–C(8)
Sb(1)–C(1)
Sb(1)–C(15)
Sb(1)–Br(1)
1.949(1) Sb(2)–O(2)
2.085(9) Sb(2)–C(22)
2.110(9) Sb(2)–C(29)
2.111(8) Sb(2)–C(36)
2.739(2) Sb(2)–Br(2)
1.946(1)
2.104(9)
2.113(9)
2.127(9)
2.735(2)
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