Synthesis, structure, and reactions of tris(4-fluorophenyl)antimony dibromide

Article abstract of DOI:10.1134/S1070363216080193

The interaction of tris(4-fluorophenyl)antimony with copper(II) bromide in acetone has afforded tris(4-fluorophenyl)antimony dibromide; recrystallization of the product from ethanol has yielded the (4-FC₆H₄)₃SbBr₂

Full text of DOI:10.1134/S1070363216080193

ISSN 1070-3632, Russian Journal of General Chemistry, 2016, Vol. 86, No. 8, pp. 1896–1901. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © V.V. Sharutin, O.K. Sharutina, 2016, published in Zhurnal Obshchei Khimii, 2016, Vol. 86, No. 8, pp. 1360–1365.
Synthesis, Structure, and Reactions
of Tris(4-fluorophenyl)antimony Dibromide
V. V. Sharutin* and O. K. Sharutina
South Ural State University, pr. Lenina 76, Chelyabinsk, 454080 Russia
*е-mail: vvsharutin@rambler.ru
Received February 8, 2016
Abstract—The interaction of tris(4-fluorophenyl)antimony with copper(II) bromide in acetone has afforded
tris(4-fluorophenyl)antimony dibromide; recrystallization of the product from ethanol has yielded the (4-
FC6H4)3SbBr2·[(4-FC6H4)3SbBr]2O adduct. [(4-FC6H4)3SbCNS]2O oxide has been prepared from tris(4-
fluorophenyl)antimony dibromide and potassium thiocyanate in aqueous-acetone solution. Antimony atoms in
the molecules of the prepared compounds exhibited the distorted trigonal bipyramid coordination with the
electron-accepting ligands in the axial positions.
Keywords: tris(4-fluorophenyl)antimony dibromide, μ-oxobis[bromotris(4-fluorophenyl)antimony], substitution
reaction, μ-oxobis[isothiocyanatotris(4-fluorophenyl)antimony], X-ray diffraction analysis
DOI: 10.1134/S1070363216080193
In contrast to fairly well studied phenyl derivatives
of antimony(V), structure and properties of the similar
compounds containing substituted aromatic rings have
not been comprehensively studied. On the other hand,
introduction of various atoms (for example, fluorine)
and functional groups in aryl ligands of organo-
antimony compounds is known to give rise to
important properties of the resulting compounds,
including biological activity [1–3].
oxo-bis-[isothiocyanatotris(4-fluorophenyl)antimony] 3,
thus demonstrating that the substitution reaction was
accompanied with hydrolysis as well.
2(4-FC6H4)3SbBr2 + 2 KCNS + H2О
→ [(4-FC6H4)3SbNСS]2O + 2 KBr + 2 HBr.
3
Structure of compounds 1‒3 was elucidated by means
of X-ray diffraction analysis (Tables 1 and 2). The
crystals of compound 1 contained two types of crystal-
lographycally independent molecules А and В. Anti-
mony atoms in the molecules exhibited distorted
trigonal bipyramid coordination with the electro-
negative substituents occupying the axial positions.
The BrSb1,2Br axial angles in the molecules А and
В were 179.22(4) and 176.86(6)°, respectively; sums
of the СSb1,2С equatorial angles [118.8(3)°–121.5(3)°
and 117.5(3)°–121.2(6)°] equaled 360° (Fig. 1). The
Sb–C bond lengths [2.107(8)–2.125(8) Å, 2.113(8) Å
at the average in A; 2.111(7)–2.127(7) Å, 2.119(7) Å
at the average in В] were marginally different. The
Sb1,2–Br distances were 2.6255(10), 2.6408(10) Å and
2.6133(9), 2.6236(9) Å. The crystal of analogous phenyl
derivative Ph3SbBr2 contained two types of molecules,
the Sb–C average bond length being 2.109(16) and
2.115(18) Å, and the Sb–Br distances being 2.629(2),
2.634(3) Å and 2.638(3), 2.652(2) Å [4].
In this work we synthesized tris(4-fluorophenyl)anti-
mony dibromide, studied its stability against hydrolysis
in aqueous-organic media, and elucidated the structure
of the prepared compounds by means of X-ray diffract-
tion analysis. Tris(4-fluorophenyl)antimony dibromide
1 was prepared via oxidation of tris(4-fluorophenyl)-
antimony with copper(II) bromide in acetone.
(4-FC6H4)3Sb + 2 CuBr2 → (4-FC6H4)3SbBr2 + Cu2Br2.
1
Treatment of compound 1 with ethanol resulted in
its partial hydrolysis to form μ-oxo-bis-[bromotris(4-
fluorophenyl)antimony]; the latter co-crystallized
with compound 1 to give the (4-FC6H4)3SbBr2·
[(4-FC6H4)3SbBr]2O adduct (2).
The interaction of compound 1 with potassium
thiocyanate in an aqueous-acetone solution yielded μ-
1896

SYNTHESIS, STRUCTURE, AND REACTIONS OF TRIS(4-FLUOROPHENYL)ANTIMONY
1897
Table 1. Crystallographic data, experimental and refinement parameters of structures of compounds 1–3
Parameter
1
C18H12Br2F3Sb
566.85
2
C54H36Br4F9OSb3
1556.72
3
Formula
М
C38H24F6N2OS2Sb2
946.21
Crystal system
Space group
a, Å
Rhombic
P212121
Monoclinic
C2/c
Monoclinic
P21/c
11.6652(6)
13.6490(9)
24.4326(16)
90.00
19.5375(6)
9.9295(3)
27.8121(9)
90.00
11.4625(4)
20.0629(6)
16.3956(5)
90.00
b, Å
c, Å
α, deg
β, deg
90.00
90.7370(10)
90.00
96.2390(10)
90.00
γ, deg
90.00
V, Å3
3890.1(4)
8
5395.0(3)
8
3748.2(2)
4
Z
dcalc, g/cm3
μ, mm–1
F(000)
Crystal size, mm
1.936
1.917
1.677
5.550
4.523
1.615
2144.0
2968.0
1848.0
0.73×0.33×0.2
6.1°–52.12°
0.28×0.18×0.07
6.34°–52.8°
0.35×0.33×0.1
6.12°–52.14°
Scanning range over 2θ, deg
Reflection indices
–14 ≤ h ≤ 13,
–16 ≤ k ≤ 16,
–30 ≤ l ≤ 30
–24 ≤ h ≤ 24,
–12 ≤ k ≤ 12,
–34 ≤ l ≤ 34
–14 ≤ h ≤ 14,
–24 ≤ k ≤ 24,
–20 ≤ l ≤ 20
Total reflections
Independent reflections
Rint
66589
7685
35266
5524
48965
7396
0.0614
433
0.0481
324
0.0456
460
Refinement variables
GOOF
1.077
1.054
1.035
R-Factors over F2 > 2σ(F2)
R1 0.0446,
wR2 0.0942
R1 0.0361,
wR2 0.0764
R1 0.0310,
wR2 0.0644
R-Factors over all reflections
R1 0.0790,
wR2 0.1101
R1 0.0630,
wR2 0.0859
R1 0.0515,
wR2 0.0726
Residual electron density (min/max), e/Å3
1.03/–0.41
0.66/–1.05
0.53/–0.63
Crystal packing of molecules of compound 1 was
determined by numerous short contacts between the
halogen atoms and ortho- or meta-hydrogen of the aryl
substituents F···HC and Br···НС (the Н···F and
Н···Br distances were 2.38–2.55 and 2.80–3.02 Å).
sion center) and [(4-FC6H4)3SbBr]2O (bridging oxygen
atom being the inversion center) molecules (Fig. 2).
Geometry parameters of the (4-FC6H4)3SbBr2 mole-
cules [angles BrSb1Br 178.63(4)°, СSb1С 114.52(12)°,
114.52(12)°, and 131.0(2)°; bonds Sb1–C 2.112(7),
2.129(5), 2.129(5) Å, and Sb1–Br 2.6241(6) Å] were
close to those found for compound 1. The only
parameter revealing noticeable difference was the bond
Crystal of compound 2 contained central-symmet-
rical (4-FC6H4)3SbBr2 (antimony atom being the inver-
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 8 2016

1898
SHARUTIN, SHARUTINA
Table 2. Bond angles and bond lengths in molecules of
compounds 1–3
angle between the equatorial bonds. The increase in
the С1Sb1С1а angle value to 131.0(2)° (with the other
two equatorial angles being decreased) in the crystal of
compound 2 could be likely explained by the
intramolecular contacts of each of the bromine atoms
with ortho-hydrogen atoms of the two aryl rings
Br1···HC6 and Br1···HC2 (the Br···H distances were
2.86 Å at the sum of van der Waals radii of the atoms
3.1 Å [5]). In the [(4-FC6H4)3SbBr]2O molecule, the
Sb2–O1–Sb2b fragment was linear, the aryl rings at the
Sb2 and Sb2b atoms being in the staggered conforma-
tion with respect to it. The axial BrSb2O and equatorial
CSb2C angles at the SbC3BrO coordination node were
175.04(2)° and 117.4(2)°, 118.9(2)°, 123.2(2)°, respec-
tively. The antimony atom was off the equatorial plane
[C3] by 0.09 Å towards the oxygen atom; hence, the
BrSb2С angles [85.23(12)–89.84(18)°] were less than
90°, and the ОSb2С angles [90.81(12)°–94.63(18)°] were
larger than 90°. The Sb2–С bonds in the equa-torial
plane [2.099(5), 2.106(5), and 2.111(4) Å] were
shorter than in the (4-FC6H4)3SbBr2 molecule. The
Sb2–Br bond length [2.7247(6) Å] exceeded those in
the (4-FC6H4)3SbBr2 molecule. The Sb2–O distance
[1.9439(3) Å] was shorter than the sum of covalent
radii of antimony and oxygen atoms (2.07 Å [5]).
Bond
d, Å
Angle
ω, deg
1
Sb1‒Br1
Sb1‒Br2
Sb1‒C21
Sb1‒C11
Sb1‒C1
Sb2‒Br3
Sb2‒Br4
Sb2‒C31
Sb2‒C51
Sb2‒C41
2.6255(10)
2.6408(10)
2.109(7)
2.107(8)
2.125(8)
2.6133(9)
2.6236(9)
2.111(7)
2.127(7)
2.120(8)
Br1Sb1Br2
C21Sb1C1
C11Sb1C21
C11Sb1C1
C21Sb1Br1
Br3Sb2Br4
C31Sb2C51
C31Sb2C41
C41Sb2C51
C31Sb2Br4
179.22(4)
118.8(3)
121.5(3)
119.7(3)
90.77(19)
176.86(6)
122.5(3)
117.5(3)
120.0(3)
89.5(2)
2
Sb1‒Br1
Sb1‒C11
Sb1‒C1a
Sb1‒C1
2.6241(6)
2.112(7)
2.129(5)
2.129(5)
Br1Sb1Br1a
C11Sb1C1
C1Sb1C1a
C11Sb1Br1
178.63(4)
114.52(12)
131.0(2)
90.685
(18)
The close interatomic distances were found for μ-
oxobis[bromotriphenyl)antimony] [(Ph3SbBr]2O mole-
cule, but the Sb–O–Sb angles in the latter were less
than 180° [6–8]. Weak F···HC interactions between
the (4-FC6H4)3SbBr2 molecules were observed, the
Br···НС interactions were observed between mole-
cules of different types.
Sb2‒Br2
Sb2‒C41
Sb2‒C21
Sb2‒O1
Sb2‒C31
O1‒Sb2b
2.7247(6)
2.099(5)
2.111(4)
1.9439(3)
2.106(5)
1.9440(3)
C1Sb1Br1
C41Sb2C21
C41Sb2C31
C31Sb2C21
C41Sb2Br2
Sb2O1Sb2b
89.05(13)
123.23(18)
117.4(2)
118.9(2)
85.23(12)
180.0
The binuclear molecule of compound 3 contained a
non-linear Sb1–О–Sb2 fragment [the angle at the
oxygen atom 143.52(13)°] (Fig. 3). The NCS ligand
was coordinated to the antimony atom via the nitrogen
one. Distortion of the trigonal bipyramid coordination
of the antimony atoms was reflected in the deviation of
the bond angles from the theoretical values and
deviation of the antimony atoms off the corresponding
equatorial planes towards the bridging oxygen atom
(Sb1 by 0.114 Å and Sb2 by 0.136 Å). The axial
NSb1,2O angles were 179.37(11)° and 177.96(11)°.
The equatorial angles СSb1,2С ranged 116.08(14)°–
125.94(14)° and 112.71(14)°–124.65(14)°. The Sb1,2–C
bond lengths [2.099(4)–2.104(3), 2.098(4)–2.106(3) Å]
were close to those found in the [(4-FC6H4)3SbBr]2O
molecule of adduct 2, and the Sb1,2–О distances [1.971(2),
1.963(2) Å] were longer than in [(4-FC6H4)3SbBr]2O,
due to the different structure of the Sb–О–Sb frag-
Symmetry operations: a) –x, y, 1/2 – z; b) –x, 1–y, –z
3
Sb1‒O1
Sb1‒C21
Sb1‒C11
Sb1‒C1
Sb1‒N1
Sb2‒O1
Sb2‒C31
Sb2‒C41
Sb2‒C51
Sb2‒N2
1.971(2)
2.109(3)
2.104(3)
2.099(4)
2.247(3)
1.963(2)
2.106(3)
2.101(3)
2.098(4)
2.292(3)
O1Sb1N1
C11Sb1C21
C1Sb1C21
C1Sb1C11
Sb2O1Sb1
O1Sb2N2
C41Sb2C31
C51Sb2C31
C51Sb2C41
O1Sb2C41
179.37(11)
125.94(14)
117.09(13)
116.08(14)
143.52(13)
177.96(11)
121.39(13)
112.71(14)
124.65(14)
92.38(11)
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 8 2016

SYNTHESIS, STRUCTURE, AND REACTIONS OF TRIS(4-FLUOROPHENYL)ANTIMONY
1899
Fig. 1. General view of molecule of compound 1 in the crystal.
Fig. 2. General view of molecule of compound 2 in the crystal.
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 8 2016

1900
SHARUTIN, SHARUTINA
Fig. 3. General view of molecule of compound 3 in the crystal.
ments. Shortening of the Sb–О bonds in the molecules
with linear SbОSb fragment are explained by the
increase in the corresponding bonds order due to the
possible additional π-interaction [9]. The Sb1,2–N
bonds [2.247(3) and 2.292(3) Å] were significantly
longer than those in triphenylantimony bis(isothio-
cyanate) (2.125–2.162 Å) [10].
λ 0.71073 Å, graphite monochromator) at 296(2) K.
Data collection and processing, refinement of the unit
cell parameters, and account for absorption were
performed using SMART and SAINT-Plus software
[11]. The structure refinement was performed using
SHELXL/PC [12] and OLEX2 [13] software.
Structures of compounds 1–3 was solved via the direct
method and refined using a least-squares method in
anisotropic approximation for non-hydrogen atoms.
Complete tables of atomic coordinates, bond angles,
and bond angles were deposited at the Cambridge
Crystallographic Data Centre [CCDC 999834 (1),
1443193 (2), and 999447(3)].
Crystal packing of compound 3 was determined by
the numerous F···HC and S···HC contacts.
In summary, the interaction of tris(4-fluorophenyl)-
antimony with copper(II) bromide has led to tris(4-
fluorophenyl)antimony dibromide, hydrolyzable in
aqueous-organic media. The substitution reaction
between (4-FC6H4)3SbBr2 and МХ salts in a water-
containing solvent has yielded a binuclear compound
with a bridging oxygen atom [(4-FC6H4)3SbХ]2O.
Tris(4-fluorophenyl)antimony dibromide (1). A
solution of 0.567 g (2.0 mmol) of copper(II) bromide
in acetone was added to a solution of 0.407 g
(1.0 mmol) of tris(4-fluorophenyl)antimony in 10 mL
of acetone. The reaction mixture was filtered, the
solvent was removed, and the solid residue was recrys-
tallized from a 3 : 1 benzene–heptane mixture. Yield
0.522 g (92%), mp 157°С (decomp.). IR spectrum, ν,
cm–1: 3096, 3059, 2365, 2345, 1576, 1485, 1393, 1302,
1236, 1165, 1107, 1090, 1049, 1007, 932, 818, 582,
505, 418. Found, %: С 37.96; Н 2.31. C18H12Br2F3Sb.
Calculated, %: С 38.09; Н 2.12.
EXPERIMENTAL
IR spectra were recorded using a Shimadzu
IRAffinity-1S spectrometer (KBr pellets, 4000–400
cm–1). Elemental analysis was performed using a Carlo
Erba CHNS-O EA 1108 instrument. Melting points
were determined using a Stuart SMP device.
X-ray diffraction analysis of crystals of compounds
1–3 was performed using a D8 QUEST Bruker
automated four-circle diffractometer (MoKα radiation,
Adduct of tris(4-fluorophenyl)antimony dibromide
with μ-oxo-bis-[bromotris(4-fluorophenyl)antimony]
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 86 No. 8 2016

SYNTHESIS, STRUCTURE, AND REACTIONS OF TRIS(4-FLUOROPHENYL)ANTIMONY
1901
3. Yu, L., Ma, Y.-Q., Liu, R.C., Wang, G.-C., Li, J.-S.,
Du, G.H., and Hu, J.J., Polyhedron, 2004, vol. 23, no. 5,
p. 823.
4. Webster, M., Acta Crystallogr. (C), 1998, vol. 54, no. 5,
p. 570. doi 10.1107/S0108270197018040.
5. Batsanov, S.S., Zh. Neorg. Khim., 1991, vol. 36, no. 12,
(2). Compound 1 (0.170 g, 0.1 mmol) was dissolved at
stirring and heating (40°С) in 50 mL of ethanol. After
the solution evaporation to 1 mL, colorless crystals
were formed; they were filtered off and dried. Yield
0.139 g (89%), mp 180°С (decomp). IR spectrum, ν,
cm–1: 3092, 3063, 2365, 2341, 1582, 1550, 1489, 1393,
1230, 1161, 827, 768, 719, 584, 507, 419, 397. Found,
%: С 41.56; H 2.42. C54H36Br4F9OSb3. Calculated, %:
С 41.62; Н 2.31.
p. 3015.
6. Sharutin, V.V., Pakusina, A.P., Nasonova, N.V.,
Sharutina, O.K., Gerasimenko, A.V., and Pushilin, M.A.,
Butlerovsk. Soobshch., 2002, no. 11, p. 13.
μ-Oxo-bis-[isothiocyanatotris(4-fluorophenyl)anti-
mony] (3). A solution of 0.567 g (1.0 mmol) of
compound 1 in 10 mL of acetone was mixed with a
solution of 0.194 g (2.0 mmol) of potassium thio-
cyanate in 100 mL of water. The formed colorless
precipitate was filtered off, dried, and recrystallized
from a 3 : 1 benzene–heptane mixture. Yield 0.460 g
(97%), mp 180°С (decomp). IR spectrum, ν, cm–1:
3055, 2363, 2345, 2021, 1585, 1492, 1395, 1302,
1233, 1159, 1065, 1011, 824, 733, 696, 509, 418, 399.
Found, %: С 48.01; H 2.59. C38H24F6ON2S2Sb2.
Calculated, %: С 48.20; Н 2.54.
7. Sharutin, V.V., Pakusina, A.P., Egorova,I.V., Sharutina, O.K.,
and Pushilin, M.A., Russ. J. Coord. Chem., 2008, vol. 34,
no. 3, p. 175. doi 10.1134/S1070328408030044.
8. Sharutin, V.V., Sharutina, O.K., Pakusina, A.P., and
Smirnova, S.A., Russ. J. Inorg. Chem., 2009, vol. 54,
no. 10, p. 1630. doi 10.1134/S0036023609100209.
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no. 2, p. 199. doi 10.1016/0022-328X(87)85152-5.
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doi 10.1016/0022-328X(95)05775-K.
11. SMART and SAINT-Plus. Versions 5.0. Data Collection
and Processing Software for the SMART System.
Madison (WI, USA): Bruker AXS Inc., 1998.
12. SHELXTL/PC. Versions 5.10. An Integrated System for
Solving, Refining and Displaying Crystal Structures
From Diffraction Data. Madison (WI, USA): Bruker
AXS Inc., 1998.
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