Synthesis and structural features of tris(5-bromo-2-methoxyphenyl)antimony bis (cyclopropanecarboxylate)

Article abstract of DOI:10.1134/S1070363212100064

Reaction of tris(5-bromo-2-methoxyphenyl)antimony with cyclopropanecarboxylic acid in the presence of hydrogen peroxide (1:2:1 mol) results in tris(5-bromo-2-methoxyphenyl)antimony bis(cyclopropanecarboxylate) I. The structure of the resulting complex was

Full text of DOI:10.1134/S1070363212100064

ISSN 1070-3632, Russian Journal of General Chemistry, 2012, Vol. 82, No. 10, pp. 1665–1668. © Pleiades Publishing, Ltd., 2012.
Original Russian Text © V.V. Sharutin, O.K. Sharutina, V.S. Senchurin, O.V. Chagarova, 2012, published in Zhurnal Obshchei Khimii, 2012, Vol. 82,
No. 10, pp. 1646–1649.
Synthesis and Structural Features
of Tris(5-bromo-2-methoxyphenyl)antimony Bis
(cyclopropanecarboxylate)
V. V. Sharutin, O. K. Sharutina, V. S. Senchurin, and O. V. Chagarova
National Research Southern Ural State University, ul. Lenina 76, Chelyabinsk, 454080 Russia
e-mail: vvsharutin@rambler.ru
Received August 25, 2011
Abstract—Reaction of tris(5-bromo-2-methoxyphenyl)antimony with cyclopropanecarboxylic acid in the
presence of hydrogen peroxide (1:2:1 mol) results in tris(5-bromo-2-methoxyphenyl)antimony bis(cyclo-
propanecarboxylate) I. The structure of the resulting complex was proved by the XRD analysis.
DOI: 10.1134/S1070363212100064
The coordination sphere of the antimony atom is
known to be nonrigid. In the antimony(V) derivatives,
whose ligands contain the heteroatoms with lone
electron pairs the additional intra- and intermolecular
n,d-interactions are possible [1–3].
presence of hydrogen peroxide proceeds by the usual
route to form tris(5-bromo-2-methoxyphenyl)antimony
bis(cyclopropanecarboxylate) in 91% yield.
Owing to the n-donor substituents in all five ligands
of the molecule I surrounding the antimony atom, it is
of interest to determine how the possibility of the non-
valence intramolecular and intermolecular interactions
is implemented in the crystal.
According to the XRD data, in the molecule of I the
antimony atom has a distorted trigonal-bipyramidal
coordination (see Fig.). The planes of the aryl rings
have not “propeller” conformation relative to to the
equatorial plane, which is energetically the most
favorable, but are arranged in such a way that the
torsion angles O2SbC11C12, O2SbC21C22, O2SbC31C32
equal 125.62, –137.97 and 121.92°, respectively. In
this case, the methoxy groups of aryl ligands C11–C16
and C31–C36 are oriented towards the atom O2 and the
ligand C21–C26, towards the atom O3. The bromine
atom Br1 of one of the aryl ligands is disordered over
two positions with a weight of 0.75/0.25.
Triarylantimony dicarboxylates are the examples of
compounds that exhibit the non-valence interactions
between the central atom and the carbonyl oxygen
atom (Sb···O=C). The carboxylate ligands were found
to be usually cis-oriented relative to the SbC3 frag-
ment. This leads to an increase in the CSbC angle in
the equatorial plane from the contact side and to a
distortion of the trigonal-bipyramidal coordination of
the central atom [4].
We studied the reaction of tris(5-bromo-2-
methoxyphenyl)antimony with cyclopropanecarbo-
xylic acid in the presence of hydrogen peroxide giving
rise to tris(5-bromo-2-me-toxyphenyl)antimony bis(cyclo-
propanecarboxylate) I. As might be expected, in the
molecules of the structurally characterized reaction
product the additional contacts between the methoxy
groups and bromine atoms are possible along with the
Sb···O=C interactions.
The axial angle O2SbO3 is 173.59(17)°, the bond
angles in the equatorial plane CSbC are 115.1(2),
120.8(2), and 124.1(2)° (Σ 360°). The carbon atoms of
the aryl ligands and the antimony atom lie almost in
the same plane. The angles between the axial and
equatorial bonds O2,3SbC11,21,31 differ from the theo-
retical value of 90° [84.9(2)°–96.1 (2)°] (Table 1, 2).
One of the most effective methods of triaryl-
antimony dicarboxylates synthesis is the oxidative
addition reactions [5, 6], which have been well studied
for triphenyl- and tritolylantimony [7–13].
The bond lengths Sb–C11,21 are identical [2.133(5),
The reaction of tris(5-bromo-2-methoxyphenyl)
antimony with cyclopropanecarboxylic acid in the
2.133(6) Å] and longer than the bond length Sb–C31
1665

1666
SHARUTIN et al.
General view of the molecule of I by the XRD-data.
[2.127(5) Å]. In the molecule of tris(5-bromo-2-meth-
oxyphenyl)antimony the Sb–C distances are 2.1603(15),
2.1631(15) and 2.1569(16) Å [14]. The bond lengths
Sb–O2,3 are 2.079(4) and 2.125(4) Å. The first of them
is shorter, and the second is commensurate with the
length of the equatorial bonds Sb–C. In the triaryl-
antimony dicarboxylate molecule the range of the
average bond lengths Sb–O is 2.105–2.156 Å [4].
the equatorial plane vary in the range 120°±10° that is
usual for the compounds of the general formula
Ar3SbX2.
The similar unusual orientation of the carboxy
groups was also observed in the molecules of triphenyl-
antimony bis(trifluoroacetate) [15], bis(2-hydroxyben-
zoate) [16], and bis(3-niacinate) [9], where the values
of the equatorial angles are also a little different.
Along with the intramolecular interactions
Sb···O=C in the molecule I there are the Sb···OMe
contacts [the distances Sb···O5,6,7 are 3.192, 3.205,
3.067 Å, significantly shorter than the sum of van der
Waals radii of the antimony and oxygen atoms (3.70 Å)].
A similar intramolecular coordination of the methoxy
groups is observed in the molecule of tris(5-bromo-2-
methoxyphenyl)antimony (Sb···O 2.985, 3.051, 3.052 Å
[14]).
The carboxylate ligands in the molecule I are un-
symmetrically coordinated to the antimony atom as in
the other triarylantimony dicarboxylates: the distances
Sb···O1,4 are 3.076 and 2.953 Å (the average values of
these distances in triarylantimony dicarboxylates are in
the range of 2.664–3.219 Å [4]) . The dihedral angle
between the planes of carboxy groups has an unusually
large value of 123°; as a result the carbonyl oxygen
atoms are placed opposite different equatorial angles:
the O1 atom is opposite the angle C21SbC31, the atom
O4 is opposite the angle C11SbC21. The angles CSbC in
Obviously, the presence of the non-valence
interactions Sb···OMe in the crystal of I causes the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 10 2012

SYNTHESIS AND STRUCTURAL FEATURES
1667
Table 1. Crystallographic data and experimental parameters
of structure I
Table 2. The bond lengths (d) and bond angles (ω) in struc-
ture I
Bond
d, Å
2.079(4)
Angle
ω, deg
173.59(17)
Parameter
Value
Sb1–O2
O2Sb1O3
Sb1–O3
Sb1–C11
Sb1–C21
Sb1–C31
Br1A–C13
Br1B–C13
Br2–C25
Br3–C33
O1–C1
2.125(4)
2.133(6)
2.133(5)
2.127(5)
1.928(7)
1.951(8)
1.914(7)
1.903(7)
1.225(8)
1.326(8)
1.321(9)
1.211(9)
1.366(7)
1.432(8)
1.376(8)
1.418(9)
1.367(8)
1.387(9)
O2Sb1C11
O2Sb1C21
O2Sb1C31
O3Sb1C11
O3Sb1C21
O3Sb1C31
C21Sb1C11
C31Sb1C11
C31Sb1C21
C1O2Sb1
87.3(2)
89.9(2)
Formula
М
Т, K
Crystal system
Space group
a, Å
C29H28Br3O7Sb
849.99
123
Monoclinic
P21/c
12.2430(3)
16.5156(4)
15.9076(4)
105.876(2)
3093.83(13)
4
94.16(19)
87.3(2)
96.1(2)
84.9(2)
b, Å
c, Å
124.1(2)
115.1(2)
120.8(2)
117.8(4)
112.7(4)
117.0(6)
118.2(6)
118.5(6)
123.1(6)
21.90(15)
β, deg
V, Å3
O2–C1
Z
d
O3–C5
O4–C5
C5O3Sb1
calc, g cm–3
1.825
CuKα, λ 1.54184 Å
11.979
C16O5C1Me
C22O6C2Me
C36O7C3Me
O1C1O2
Radiation
μ, mm–1
O5–C16
O5–C1Me
O6–C22
O6–C2Me
O7–C36
O7–C3Me
F(000)
Crystal size, mm
Theta range for data collection,
deg
1656
(0.117×0.102×0.075)
3.75–72.77
Br1AC13Br1B
Index ranges
–13 ≤ h ≤ 14,
–18 ≤ k ≤ 19,
–19 ≤ l ≤ 13
Reflections collected
Independent reflections
Rint
9615
5867
0.0485
373
1.013
and C–Br···H–C (3.02 Å) and by π–π-interactions
between the parallel aromatic rings. The methoxy
oxygen atoms are not involved into the intermolecular
interactions.
Refinement parameters
GOOF
Thus, the features of the molecular structure of
compound I are as follows: the additional coordination
of the antimony atom with three oxygen atoms O5,6.7 of
the methoxy groups, along with the intramolecular
interactions Sb···O1,4=C; an unusual orientation of the
carboxy groups with respect to the fragment SbC3. The
presence of the carboxy groups and the bromine atoms
in the organic substituents leads to the formation of a
three-dimensional structure in the crystal.
R-Factors on F2 > 2σ(F2)
R- Factors on all reflections
R1 0.0537, wR2 0.1291
R1 0.0665, wR2 0.1412
–1.436/1.177
Residual electron density
(min/max), e Å–3
unusual orientation of the carboxylate groups and the
aryl rings with respect to the equatorial plane.
In the carboxylate ligands the angles between the
planes [C3] and the carboxy groups are 91° and 93°.
The carbonyl groups and the rings are trans-positioned
with respect to the ordinary C–C bond.
EXPERIMENTAL
The IR spectra were recorded on a 1201 FTIR-
spectrometer from KBr pellets.
According to the published data, the length of a
single bond C–O in the carboxylic acids equals 1.293–
1.308 Å, and the length of the double C=O bond is
1.214–1.229 Å [17]. The distance C1–O1 and C1–O2,
O4–C5 and C5–O3 in the carboxylate groups are equal
to 1.225(8) and 1.326(8) Å, 1.211(9) and 1.321(9) Å,
respectively.
The XRD structural analysis was carried out on a
SuperNova automatic four-circle diffractometer
equipped with a two-coordinate CCD-detector using a
Super Nova X-ray Source (Agilent Technologies) Cu-
anode radiation (λ 1.54178 Å) at 123 K. The intensity
of the reflections was measured by φ-scanning the
frames (1°) to 2θ 142.16°. An extinction was taken
The structural organization of the crystal is caused
by weak hydrogen bonds C=O···H–C (2.34–2.40 Å),
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 82 No. 10 2012

1668
SHARUTIN et al.
6. Gushchin, A.V., Doctoral Dissert. (Chem.), Nizhynii
into account analytically by cutting the crystal using a
CrysAlisPro software (Agilent Technologies, Version
1.171.34.49, release 20-01-2011 CrysAlis171.NET)
[18]. The structure was solved by the direct method
and refined by the full least squares method in the
anisotropic approximation for the non-hydrogen atoms
using a SHELXTL software [19]. The hydrogen atoms
were refined in the geometrically calculated positions.
The main crystallographic data and structure
refinement are given in Table 1, the main bond lengths
and angles, in Table 2.
Novgorod, 1998.
7. Sharutin, V.V., Sharutina, O.K., Bondar’, Е.А.,
Pakusina, A.P., Adonin, N.Yu., and Starichenko, V.F.,
Zh. Obshch. Khim., 2002, vol. 72, no. 3, p. 419.
8. Sharutin, V.V., Sharutina, O.K., Bondar’, Е.А.,
Pakusina, A.P., Gatilov, Yu.V., Adonin, N.Yu., and
Starichenko, V.F., Koord. Khim., 2002, vol. 28, no. 5,
p. 356.
9. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P.,
Platonova, T.P., Zhidkov, V.V., Pushilin, М.А., and
Gerasimenko, A.V., Koord. Khim., 2003, vol. 29, no. 10,
p. 750.
10. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P.,
Platonova, T.P., Smirnova, S.A., Pushilin, М.А., and
Gerasimenko, A.V., Koord. Khim., 2003, vol. 29,
no. 11, p. 843.
11. Sharutin, V.V., Pakusina, A.P., Platonova, T.P.,
Sharutina, O.K., Gerasimenko, A.V., Popov, D.Yu., and
Pushilin, М.А., Zh. Obshch. Khim., 2004, vol. 74, no. 2,
p. 234.
12. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P.,
Molokova, O.V., Nevmeshkina, L.А., and Senchurin, V.V.,
Zh. Neorg. Khim., 2008, vol. 53, no. 8, p. 1335.
13. Sharutin, V.V., Senchurin, V.V., Sharutina, O.K., and
Akulova, E.V., Zh. Obshch. Khim., 2008, vol. 78,
no. 12, p. 1999.
14. Sharutin, V.V. and Chagarova, O.V., Book of Abstracts,
Vserossiiskaya nauchnaya konferentsiya “Sovremennye
problemy estestvoznaniya” (All-Russian Scientific
Conference “Contemporary Problems of Natural
Science”), Cheboksary, 2011, p. 24.
Synthesis of complex (I). To a mixture of 0.318 g
(0.44 mmol) of [(5-Br)(2-MeO)C6H3]3Sb·0.5C6H6
solvate and 0.076 g (0.88 mmol) of cyclopropane-
carboxylic acid in 40 ml of diethyl ether was added
0.043 g (0.44 mmol) of 35% aqueous hydrogen
peroxide solution. The mixture was maintained for 24 h
at room temperature. The formed fine colorless powder
(0.38 g) was recrystallized from a benzene–heptane
mixture (3:1). Yield 0.34 g (91%), colorless crystals,
mp 220°С. IR spectrum, ν, cm–1: 404, 442, 488, 524,
50, 618, 678, 753, 808, 819, 887, 904, 938, 1017,
1050, 1072, 1093, 1147, 1180, 1193, 1231, 1256,
1294, 1356, 1374, 1390, 1439, 1474, 1573, 1646,
1658, 2836, 2938, 2971, 2999, 3008, 3068, 3090.
Found, %: С 40.62; Н 3.63. C29H28Br3O7Sb.
Calculated, %: С 40.97; Н 3.30.
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