Synthesis and structure of bis(2,4,6-tribromophenoxy)triphenylantimony

Article abstract of DOI:10.1023/A:1016068409252

Bis(2,4,6-tribromophenoxy)triphenylantimony was synthesized by reacting triphenylstibine with 2,4,6-tribromophenol in ether in the presence of hydrogen peroxide. Its structure was determined by X-ray diffraction analysis. The coordination polyhedron of the Sb atom is a distorted trigonal bipyramid with the aroxy groups in the axial positions. The bond lengths are Sb(1)-C(Ph) 2.095(4)-2.106(4) A and Sb(1)-O(1,2) 2.099(3) and 2.092(3) A. The value of the O(1)SbO(2) axial angle is 177.3(1)°.

Full text of DOI:10.1023/A:1016068409252

Russian Journal of Coordination Chemistry, Vol. 28, No. 6, 2002, pp. 380–383. Translated from Koordinatsionnaya Khimiya, Vol. 28, No. 6, 2002, pp. 408–411.
Original Russian Text Copyright © 2002 by Sharutin, Pakusina, Pushilin, Subacheva, Bukvetskii, Popov.
Synthesis and Structure
of Bis(2,4,6-Tribromophenoxy)triphenylantimony
V. V. Sharutin, A. P. Pakusina, M. A. Pushilin, O. V. Subacheva,
B. V. Bukvetskii, and D. Yu. Popov
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 March 21, 2001
Abstract— Bis(2,4,6-tribromophenoxy)triphenylantimony was synthesized by reacting triphenylstibine with
2,4,6-tribromophenol in ether in the presence of hydrogen peroxide. Its structure was determined by X-ray dif-
fraction analysis. The coordination polyhedron of the Sb atom is a distorted trigonal bipyramid with the aroxy
groups in the axial positions. The bond lengths are Sb(1)–C(Ph) 2.095(4)–2.106(4) Å and Sb(1)–O(1,2)
2.099(3) and 2.092(3) Å. The value of the O(1)SbO(2) axial angle is 177.3(1)°.
It is known that reactions of triarylantimony with
Collection and processing of experimental data and
carboxylic or arenesulfonic acids in the presence of refinement of the unit cell parameters were performed
hydrogen peroxide result in the formation of triarylan- with the SMART and SAINT Plus programs [4]. All
timony diacylate or bis(arenesulfonate) [1–3]. Similar calculations for solution and refinement of the structure
reactions with phenols and structures of triarylanti- were performed by the SHELXTL/PC programs [5].
mony diphenolates were not studied. In this work, the
compound bis(2,4,6-tribromophenoxy)triphenylanti-
mony (I) was prepared by the reaction of oxidative
addition and its molecular and crystal structures were
studied.
Selected crystallographic data and results of the
refinement are given in Table 1. Coordinates of atoms
are listed in Table 2. Bond lengths and angles are given
in Table 3.
RESULTS AND DISCUSSION
EXPERIMENTAL
Compound I was prepared from triphenylstibine
and hydrogen peroxide in the presence of 2,4,6-tribro-
mophenol (1 : 1 : 2 molar ratio) in ether (20°ë, 12 h).
Synthesis of I was carried out by the following pro-
cedure. A 30% aqueous hydrogen peroxide (0.32 ml,
2.82 mmol) was added to a mixture of triphenylstibine
(1.00 g, 2.83 mmol) and 2,4,6-tribromophenol (1.88 g,
5.68 mmol) in 10 ml of ether. In 12 h, the resulting crys-
tals were filtered, recrystallized from toluene, and
dried. The yield of I was 1.35 g (47%), mp 168°C.
Ph3Sb + H2O2 + 2HOC6H2Br3
Ph3Sb(OC6H2Br3)2 + 2H2O.
The X-ray diffraction analysis of compound I shows
that the Sb(1) atom has a distorted trigonal-bipyramidal
coordination (figure) with the O atoms of the phenolate
ligands in the axial positions.
The sum of the C(Ph)SbC(Ph) angles in the equato-
rial plane is 360°. The O(1)SbO(2) axial angle is
177.3(1)°, indicating slight distortion of the trigonal-
bipyramidal configuration of the molecule. This is also
indicated by the close values of the C(Ph)SbC(Ph)
equatorial angles (117.3(2)°, 122.5(2)°, and 120.2(2)°).
X-ray diffraction analysis of crystals I was per-
formed on a SMART-1000 CCD (Bruker) diffractome-
ter (graphite monochromator, MoKα radiation, θ/2θ
scan mode). The sets of experimental data (606, 435,
230, and 606 exposures at ϕ = 0°, 90°, 180°, and 270°,
respectively) were collected at 23(2)°ë; scanning was
reformed with a 0.3° step and 10 s exposure. Integral
intensities were converted in squares of structural
amplitude moduli with account of X-ray absorption in
the sample.
The Sb(1)–O(1,2) distances, 2.099(3) and 2.092(3) Å,
respectively, are shorter than the corresponding bond
lengths in aroxytetraphenylantimony compounds,
The structure was solved by the direct method and where the Sb–O distances vary in the 2.132(6)–
refined by the least-squares method in anisotropic 2.221(4) Å range [6–8]. The Sb–O bond lengths in I are
approximation for non-hydrogen atoms. The H atoms close to the sum of the covalent radii of the O and Sb
were located geometrically and refined in the rider atoms (2.07 Å) [9]. Note that in the series of Ph3SbX2
model.
compounds, the shortest Sb–O bond lengths are
1070-3284/02/2806-0380$27.00 © 2002 åÄIä “Nauka /Interperiodica”

SYNTHESIS AND STRUCTURE
381
Table 1. Crystallographic parameters and details of the ex- Table 2. Atomic coordinates and equivalent isotropic ther-
periment and the refinement of structure I
mal parameters (Ueq) in structure I
Atom
Sb
x
y
z
Ueq, Å2
Parameter
Value
0.80192(3) 0.58214(3) 0.28315(2) 0.0434(1)
Empirical formula
Formula weight
Temperature
C30H19Br6O2Sb
1012.66
Br(1) 0.72185(9) 1.04053(8) –0.07219(5) 0.1107(3)
Br(2) 0.50693(6) 0.93205(5) 0.26492(4) 0.0759(2)
Br(3) 1.11114(6) 0.70218(6) 0.11242(5) 0.0953(2)
Br(4) 1.16217(8) –0.14672(6) 0.35523(5) 0.1101(3)
Br(5) 0.77076(7) 0.22208(6) 0.18237(4) 0.0828(2)
Br(6) 0.90760(7) 0.38887(5) 0.47490(3) 0.0765(2)
296(2) K
Wave length
MoKα (0.71073 Å)
Triclinic
Crystal group
Space group
P1
10.155(2)
10.963(2)
15.915(3)
88.859(3)
77.404(4)
67.729(3)
1596.3(5)
2
O(1) 0.7611(3)
O(2) 0.8327(3)
C(11) 0.7042(5)
C(12) 0.5623(6)
C(13) 0.4988(8)
C(14) 0.572(1)
C(15) 0.715(1)
C(16) 0.7817(7)
C(21) 0.6726(5)
C(22) 0.5602(6)
C(23) 0.4754(7)
C(24) 0.5076(8)
C(25) 0.6182(7)
C(26) 0.7023(6)
C(31) 1.0283(4)
C(32) 1.0930(5)
C(33) 1.2414(7)
C(34) 1.3214(7)
C(35) 1.2580(7)
C(36) 1.1102(6)
C(41) 0.8067(5)
C(42) 0.6676(5)
C(43) 0.6415(6)
C(44) 0.7571(7)
C(45) 0.8955(6)
C(46) 0.9197(5)
C(51) 0.8518(5)
C(52) 0.8712(5)
C(53) 0.9609(6)
C(54) 1.0364(6)
C(55) 1.0222(5)
C(56) 0.9297(5)
0.4129(3)
0.7563(3)
0.5841(4)
0.5970(6)
0.6066(8)
0.6063(7)
0.5918(6)
0.5803(5)
0.6783(4)
0.6445(5)
0.7070(6)
0.8021(6)
0.8369(6)
0.7768(5)
0.4780(4)
0.3642(5)
0.2926(6)
0.3372(7)
0.4498(7)
0.5219(5)
0.8229(4)
0.9085(4)
0.9744(4)
0.9556(5)
0.8788(5)
0.8131(4)
0.2902(4)
0.1852(5)
0.0561(5)
0.0281(5)
0.1268(5)
0.2557(4)
0.3210(2) 0.0512(8)
0.2491(2) 0.0497(8)
0.1790(3) 0.051(1)
0.1943(4) 0.085(2)
0.1261(6) 0.126(3)
0.0455(6) 0.137(4)
0.0300(4) 0.111(3)
0.0958(3) 0.073(2)
0.4034(3) 0.049(1)
0.4451(3) 0.068(1)
0.5236(4) 0.096(2)
0.5594(4) 0.097(2)
0.5179(4) 0.087(2)
0.4392(3) 0.063(1)
0.2622(3) 0.045(1)
0.2088(3) 0.060(1)
0.1979(4) 0.085(2)
0.2394(5) 0.100(2)
0.2909(4) 0.087(2)
0.3034(3) 0.065(1)
0.1796(3) 0.044(1)
0.1718(3) 0.051(1)
0.0996(3) 0.060(1)
0.0305(3) 0.064(1)
0.0345(3) 0.064(1)
0.1090(3) 0.054(1)
0.3290(3) 0.047(1)
0.2726(3) 0.054(1)
0.2803(3) 0.067(1)
0.3437(4) 0.069(2)
0.4019(3) 0.064(1)
0.3928(3) 0.053(1)
a, Å
b, Å
c, Å
α, deg
β, deg
γ, deg
V, Å3
Z
ρ(calcd), g/cm3
µ, mm–1
2.107
8.399
F(000)
952
Crystal shape
Range of data collection in θ
Sphere ( = 0.37 mm)
2.01°–30.03°
Intervals of reflection indices –13 ≤ h ≤ 14, –15 ≤ k ≤ 15,
–22 ≤ l ≤ 22
Measured reflections
Independent reflections
Reflections with I > 2σ(I)
Method of refinement
Refined parameters
GOOF
R factors for F2 > 2σ(F2)
R-factors for all reflections
Extinction coefficient
17963
9051 (Rint = 0.0377)
3959
Full-matrix for F2
353
0.753
R1 = 0.0375, wR2 = 0.0762
R1 = 0.0994, wR2 = 0.0837
Not refined
Residual electronic density
–0.790/1.045
(min/max), e/Å3
observed in the dimethoxytriphenylantimony molecule
(II) [10]. The shortening of the Sb–O distances in II
should be explained by the participation of lone
electron pairs of the oxygen atom in the formation of
the Sb–O bond, as in the antimony compounds of
the bridging type containing an Sb–O–Sb fragment
[11, 12].
We suppose that the lone electron pair of the oxygen
atom of the aroxy ligand in I interacts with π-electrons
of the aryl ring. This results in the appearance of a par-
tial positive charge on the oxygen atom, which is com-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 6 2002

382
SHARUTIN et al.
Table 3. Bond lengths and angles in structure I
Bond
Sb–O(2)
d, Å
Angle
ω, deg
Bond
d, Å
Angle
ω, deg
2.092(3)
2.095(4)
2.099(3)
2.105(4)
2.106(4)
1.900(5)
1.888(5)
1.874(5)
1.890(5)
1.889(5)
1.894(4)
1.334(5)
1.333(5)
O(2)SbC(31)
O(2)SbO(1)
90.6(1) C(41)–C(42)
177.3(1) C(42)–C(43)
91.8(1) C(43)–C(44)
91.9(1) C(44)–C(45)
117.3(2) C(45)–C(46)
88.1(1) C(51)–C(56)
88.9(1) C(51)–C(52)
122.5(2) C(52)–C(53)
88.8(1) C(53)–C(54)
120.2(2) C(54)–C(55)
131.2(3) C(55)–C(56)
127.9(2)
1.399(6) C(34)C(33)C(32)
1.367(6) C(35)C(34)C(33)
1.376(7) C(34)C(35)C(36)
1.352(7) C(35)C(36)C(31)
1.395(6) O(2)C(41)C(46)
1.382(6) O(2)C(41)C(42)
1.400(6) C(46)C(41)C(42)
1.383(6) C(43)C(42)C(41)
1.358(7) C(43)C(42)Br(2)
1.383(7) C(41)C(42)Br(2)
1.395(6) C(42)C(43)C(44)
C(45)C(44)C(43)
119.7(6)
121.2(6)
120.2(6)
119.2(5)
121.2(4)
123.7(4)
115.0(4)
123.4(4)
118.1(4)
118.5(3)
118.7(5)
121.3(5)
119.3(4)
119.4(4)
118.8(5)
122.6(4)
118.8(4)
118.5(4)
123.9(4)
121.0(4)
115.1(4)
122.7(4)
118.9(4)
118.5(4)
119.7(4)
120.8(5)
120.9(4)
118.3(4)
118.0(5)
123.6(4)
118.9(3)
117.5(4)
Sb–C(31)
Sb–O(1)
C(31)SbO(1)
O(2)SbC(11)
C(31)SbC(11)
O(1)SbC(11)
O(2)SbC(21)
C(31)SbC(21)
O(1)SbC(21)
C(11)SbC(21)
C(51)O(1)Sb
C(41)O(2)Sb
Sb–C(11)
Sb–C(21)
Br(1)–C(44)
Br(2)–C(42)
Br(3)–C(46)
Br(4)–C(54)
Br(5)–C(52)
Br(6)–C(56)
O(1)–C(51)
O(2)–C(41)
C(12)C(11)C(16) 120.2(5)
C(45)C(44)Br(1)
C(11)–C(12) 1.359(6)
C(11)–C(16) 1.378(7)
C(12)–C(13) 1.361(8)
C(12)C(11)Sb
C(16)C(11)Sb
120.0(4)
119.7(4)
C(43)C(44)Br(1)
C(44)C(45)C(46)
C(11)C(12)C(13) 118.8(6)
C(41)C(46)C(45)
C(13)–C(14) 1.335(11) C(14)C(13)C(12) 121.4(8)
C(14)–C(15) 1.367(11) C(13)C(14)C(15) 119.8(6)
C(41)C(46)Br(3)
C(45)C(46)Br(3)
C(15)–C(16) 1.346(7)
C(21)–C(22) 1.365(6)
C(21)–C(26) 1.388(6)
C(22)–C(23) 1.374(7)
C(23)–C(24) 1.372(8)
C(24)–C(25) 1.354(8)
C(25)–C(26) 1.368(7)
C(31)–C(32) 1.374(6)
C(31)–C(36) 1.382(6)
C(32)–C(33) 1.383(7)
C(33)–C(34) 1.373(8)
C(34)–C(35) 1.348(8)
C(35)–C(36) 1.376(7)
C(41)–C(46) 1.392(6)
C(16)C(15)C(14) 120.3(7)
C(15)C(16)C(11) 119.4(6)
C(22)C(21)C(26) 120.6(4)
O(1)C(51)C(56)
O(1)C(51)C(52)
C(56)C(51)C(52)
C(22)C(21)Sb
C(26)C(21)Sb
120.1(3)
119.3(3)
C(53)C(52)C(51)
C(53)C(52)Br(5)
C(21)C(22)C(23) 120.3(5)
C(24)C(23)C(22) 118.7(6)
C(25)C(24)C(23) 121.2(6)
C(24)C(25)C(26) 120.8(6)
C(25)C(26)C(21) 118.4(5)
C(32)C(31)C(36) 120.7(4)
C(51)C(52)Br(5)
C(54)C(53)C(52)
C(53)C(54)C(55)
C(53)C(54)Br(4)
C(55)C(54)Br(4)
C(54)C(55)C(56)
C(32)C(31)Sb
C(36)C(31)Sb
119.1(3)
120.1(4)
C(51)C(56)C(55)
C(51)C(56)Br(6)
C(31)C(32)C(33) 119.0(5)
C(55)C(56)Br(6)
pensated by shifting of the electronic density from the lone electron pair shift to the Sb atom, thus decreasing
the Sb–O bond polarization and length in II.
Sb atom to cause polarization of the Sb–O bond. The
bromine atoms in the aryl group strengthen its electron-
accepting properties and make the electronic density
shift from the aromatic ring. The stronger the electron-
accepting properties of the aryl group, the higher the
positive charge on the oxygen atom and the longer the
Sb–O bond, and vise versa.
Br
Sb
O
Me Sb
O
Br
Br
Actually, the O(1)–C(51) and O(2)–C(41) bonds in
I (1.334(5) and 1.333(5) Å) are shorter than the corre-
sponding bonds in II (1.42(1) and 1.41(1) Å). The
These conclusions are supported by an observed
regularity: an increase in the Sb–O distance is accom-
panied by a decrease in the O–C length. In compound I
donor methyl groups in the methoxy ligand make the with significant interaction of the lone electron pair of
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 6 2002

SYNTHESIS AND STRUCTURE
383
ACKNOWLEDGMENTS
Br(4)
The authors are grateful to the Russian Foundation
for Basic Research for support of the permit to use the
Cambridge Structural Database, project no. 99-07-
90133.
C(55)
C(56)
C(54)
C(53)
Br(6)
C(33)
C(34)
C(35)
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RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 28 No. 6 2002