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Acta Cryst. (2009). E65, m656-m657    [ doi:10.1107/S1600536809017449 ]

Triphenylbis[4-(trifluoromethyl)benzoato-[kappa]O]antimony(V)

L. Quan, H. Yin, L. Cui, M. Yang and D. Wang

Abstract top

The title complex, [Sb(C6H5)3(C8H4F3O2)2], is located on a twofold axis defined by the metal center and two C atoms of a coordinated phenyl group. The environment of the Sb atom approximates a trigonal-bipyramidal geometry, with the axial positions occupied by the O atoms of symmetry-related 4-(trifluoromethyl)benzoate ligands. In this ligand, the CF3 group is disordered by rotation about the C-C bond and the F atoms are distributed over two sets of sites with occupancies of 0.62 (3) and 0.38 (3). In the crystal, molecules are assembled in a three-dimensional framework through weak C-H...O hydrogen bonds.

Comment top

Some triorganoantimony(V) complexes with acetylferroceneoxime as ligand showed in vitro antitumor activity (Yin et al., 2008). The related title compound may show similar activity. The title complex is also related to triphenyl-bis(4-methylbenzoato-κO)-antimony(V), previously characterized (Sharutin et al., 2003), although both complexes are not isostructural and crystallize in different space groups.

The crystal structure of the title complex consists of isolated molecules which have C2 molecular symmetry. The 2-fold axis is defined by atoms Sb1/C15/C18. The coordination geometry around the antimony center is best described as a distorted trigonal bipyramid. Two carboxylate groups occupy the axial sites with O1—Sb1—-O1i angle being 176.0 (3)° [symmetry code: (i) 2 - x, 1 - y, z]. In the equatorial plane, the sum of angles C9—Sb1—C9i, C9—Sb1—C15 and C15—Sb1—C9i is 360.0°. The Sb1—O1 bond length, 2.150 (5) Å, is significantly different from the corresponding distance in [4-(C5H5FeC5H4)C6H4COO]2Sb(C6H4F-4)3, 2.087 (6) Å (Yu et al., 2004), but much shorter than the sum of the van der Waals radii for Sb and O, 3.2 Å. The Sb—C distances fall in the expected range found in the literature (Yu et al., 2004).

Related literature top

For related Sb(V) structures, see: Sharutin et al. (2003); Yin et al. (2008); Yu et al. (2004).

Experimental top

4-Trifluoromethylbenzoic acid (0.152 g, 0.8 mmol) and sodium methoxide (0.8 mmol) were added to a stirring solution containing dichlorotriphenylantimony (0.172 g, 0.4 mmol) in toluene (25 ml). After refluxing for 8 h., a colorless solution was obtained and then filtered. The solvent was gradually removed by evaporation under vacuum until a white solid was obtained. The solid was recrystallized from petroleum ether/dichoromethane (1:1) to give colorless crystals of the title complex.

Refinement top

H atoms were placed in calculated positions and refined as riding atoms with C—H = 0.93 Å and Uiso(H) = 1.2Ueq(carrier C). F atoms were found to be disordered over two positions: F1/F1', F2/F2' and F3/F3'. Their occupancies were refined with the sum constrained to unity, and converged to 0.62 (3) [F1/F2/F3] and 0.38 (3) [F1'/F2'/F3']. Geometry was restrained (restraints not given). The Flack parameter has been refined (1284 measured Friedel pairs), although not documented by authors.

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 (Farrugia, 1997) and DIAMOND (Brandenburg, 1998); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title complex, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. A chain of molecules linked by C3—H3···O2#1 intermolecular hydrogen bonds (dashed lines) (symmetry code #1: 1 - y, x-y, z - 1/3).
Triphenylbis[4-(trifluoromethyl)benzoato-κO]antimony(V) top
Crystal data top
[Sb(C6H5)3(C8H4F3O2)2]Z = 3
Mr = 731.27F000 = 1092
Hexagonal, P62Dx = 1.554 Mg m−3
Hall symbol: P 62Mo Kα radiation
λ = 0.71073 Å
a = 12.9879 (10) ÅCell parameters from 3513 reflections
b = 12.9879 (10) Åθ = 2.2–23.0º
c = 16.042 (2) ŵ = 0.96 mm−1
α = 90ºT = 298 K
β = 90ºBlock, colorless
γ = 120º0.44 × 0.31 × 0.24 mm
V = 2343.5 (4) Å3
Data collection top
Bruker SMART
diffractometer		2719 independent reflections
Radiation source: fine-focus sealed tube1962 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.053
T = 298 Kθmax = 25.0º
φ and ω scansθmin = 1.8º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→9
Tmin = 0.679, Tmax = 0.803k = −15→12
9708 measured reflectionsl = −19→18
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.058  w = 1/[σ2(Fo2) + (0.0684P)2 + 2.131P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.145(Δ/σ)max = 0.026
S = 1.08Δρmax = 0.90 e Å−3
2719 reflectionsΔρmin = −0.41 e Å−3
233 parametersExtinction correction: none
55 restraintsAbsolute structure: Flack (1983), 1284 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.04 (7)
Secondary atom site location: difference Fourier map
Crystal data top
[Sb(C6H5)3(C8H4F3O2)2]γ = 120º
Mr = 731.27V = 2343.5 (4) Å3
Hexagonal, P62Z = 3
a = 12.9879 (10) ÅMo Kα
b = 12.9879 (10) ŵ = 0.96 mm−1
c = 16.042 (2) ÅT = 298 K
α = 90º0.44 × 0.31 × 0.24 mm
β = 90º
Data collection top
Bruker SMART
diffractometer		2719 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1962 reflections with I > 2σ(I)
Tmin = 0.679, Tmax = 0.803Rint = 0.053
9708 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.058H-atom parameters constrained
wR(F2) = 0.145Δρmax = 0.90 e Å−3
S = 1.08Δρmin = −0.41 e Å−3
2719 reflectionsAbsolute structure: Flack (1983), 1284 Friedel pairs
233 parametersFlack parameter: 0.04 (7)
55 restraints
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Sb11.00000.50000.10910 (15)0.0641 (3)
F10.2113 (17)0.1590 (11)0.182 (2)0.26 (2)0.62 (3)
F20.241 (2)0.294 (3)0.2756 (10)0.25 (2)0.62 (3)
F30.2382 (14)0.3226 (13)0.1459 (10)0.127 (8)0.62 (3)
F1'0.242 (3)0.3496 (19)0.228 (3)0.23 (3)0.38 (3)
F2'0.209 (3)0.215 (3)0.1356 (11)0.24 (3)0.38 (3)
F3'0.2233 (18)0.1848 (16)0.2607 (10)0.096 (9)0.38 (3)
O10.8139 (5)0.4442 (5)0.1045 (4)0.0653 (16)
O20.8310 (6)0.4481 (7)0.2417 (4)0.092 (2)
C10.7700 (8)0.4310 (9)0.1798 (6)0.070 (3)
C20.6436 (8)0.3930 (8)0.1835 (6)0.065 (2)
C30.5766 (9)0.3813 (9)0.1133 (7)0.074 (3)
H30.61290.40110.06120.089*
C40.4582 (10)0.3412 (10)0.1200 (9)0.092 (3)
H40.41370.33210.07230.110*
C50.4034 (10)0.3138 (10)0.1967 (9)0.088 (3)
C60.4660 (10)0.3246 (12)0.2652 (8)0.102 (4)
H60.42870.30570.31700.122*
C70.5843 (9)0.3631 (12)0.2599 (7)0.098 (4)
H70.62660.36970.30820.117*
C80.2710 (11)0.2707 (11)0.2030 (8)0.136 (7)
C91.0390 (9)0.6667 (9)0.1536 (6)0.077 (3)
C101.0489 (11)0.6986 (11)0.2367 (6)0.108 (4)
H101.04000.64390.27760.130*
C111.0718 (14)0.8097 (13)0.2596 (12)0.157 (9)
H111.07780.83040.31560.189*
C121.0856 (16)0.8904 (16)0.1985 (12)0.159 (9)
H121.10020.96570.21340.191*
C131.0781 (13)0.8602 (11)0.1153 (12)0.146 (6)
H131.08880.91540.07440.176*
C141.0547 (11)0.7483 (10)0.0928 (8)0.102 (4)
H141.04960.72780.03680.122*
C151.00000.5000−0.0220 (6)0.053 (3)
C161.0867 (9)0.4904 (10)−0.0660 (7)0.090 (3)
H161.14700.4863−0.03770.108*
C171.0832 (12)0.4871 (14)−0.1517 (7)0.120 (5)
H171.13870.4757−0.18070.144*
C181.00000.5000−0.1948 (9)0.116 (7)
H181.00000.5000−0.25280.139*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb10.0578 (5)0.0795 (7)0.0433 (3)0.0256 (5)0.0000.000
F10.076 (11)0.068 (10)0.60 (7)0.003 (8)−0.06 (3)0.05 (2)
F20.15 (2)0.44 (6)0.22 (2)0.19 (3)0.083 (19)0.13 (3)
F30.065 (9)0.100 (11)0.22 (2)0.043 (8)−0.020 (10)−0.016 (11)
F1'0.11 (3)0.083 (18)0.50 (9)0.047 (16)0.09 (5)0.03 (4)
F2'0.074 (17)0.37 (7)0.20 (4)0.06 (3)−0.015 (17)0.15 (4)
F3'0.053 (11)0.092 (16)0.109 (16)0.011 (10)0.013 (10)−0.009 (11)
O10.053 (3)0.088 (4)0.048 (3)0.030 (3)0.003 (3)−0.003 (3)
O20.051 (4)0.144 (7)0.054 (4)0.029 (4)−0.005 (3)0.000 (4)
C10.053 (6)0.086 (7)0.057 (5)0.024 (5)−0.002 (4)−0.005 (4)
C20.058 (6)0.060 (6)0.062 (5)0.019 (5)0.000 (4)−0.004 (4)
C30.068 (6)0.084 (7)0.062 (5)0.033 (5)−0.003 (6)0.003 (6)
C40.075 (7)0.093 (8)0.105 (9)0.040 (6)−0.027 (7)0.010 (7)
C50.060 (7)0.071 (7)0.121 (10)0.024 (6)0.014 (7)0.024 (7)
C60.068 (7)0.141 (11)0.077 (8)0.037 (7)0.017 (6)0.020 (8)
C70.069 (7)0.154 (12)0.054 (6)0.044 (7)0.004 (5)0.000 (6)
C80.068 (10)0.116 (15)0.21 (2)0.032 (10)0.009 (12)0.062 (14)
C90.055 (6)0.082 (7)0.085 (7)0.027 (6)0.013 (5)−0.002 (6)
C100.086 (8)0.109 (10)0.100 (9)0.026 (7)0.016 (7)−0.040 (7)
C110.097 (11)0.147 (16)0.17 (2)0.019 (11)0.027 (12)−0.087 (15)
C120.108 (13)0.096 (13)0.23 (3)0.016 (11)0.036 (15)−0.056 (14)
C130.107 (11)0.098 (11)0.21 (2)0.030 (9)0.033 (14)0.001 (13)
C140.097 (9)0.074 (8)0.118 (11)0.031 (7)0.015 (8)−0.007 (8)
C150.048 (7)0.067 (8)0.032 (5)0.019 (6)0.0000.000
C160.079 (7)0.141 (9)0.056 (6)0.060 (7)−0.012 (5)−0.019 (7)
C170.115 (10)0.216 (16)0.061 (7)0.106 (11)−0.005 (6)−0.034 (8)
C180.097 (13)0.22 (2)0.037 (7)0.083 (14)0.0000.000
Geometric parameters (Å, °) top
Sb1—C92.087 (10)C6—C71.359 (15)
Sb1—C9i2.087 (10)C6—H60.9300
Sb1—C152.103 (10)C7—H70.9300
Sb1—O12.150 (5)C9—C141.377 (9)
Sb1—O1i2.150 (5)C9—C101.383 (9)
F1—C81.302 (9)C10—C111.370 (9)
F2—C81.310 (10)C10—H100.9300
F3—C81.328 (9)C11—C121.380 (10)
F1'—C81.317 (10)C11—H110.9300
F2'—C81.323 (10)C12—C131.380 (10)
F3'—C81.341 (10)C12—H120.9300
O1—C11.311 (11)C13—C141.376 (9)
O2—C11.219 (10)C13—H130.9300
C1—C21.459 (13)C14—H140.9300
C2—C31.386 (14)C15—C16i1.386 (12)
C2—C71.395 (13)C15—C161.386 (12)
C3—C41.359 (14)C16—C171.375 (16)
C3—H30.9300C16—H160.9300
C4—C51.375 (18)C17—C181.362 (16)
C4—H40.9300C17—H170.9300
C5—C61.333 (17)C18—C17i1.362 (16)
C5—C81.522 (16)C18—H180.9300
C9—Sb1—C9i140.0 (5)F2—C8—F2'133 (2)
C9—Sb1—C15110.0 (3)F1'—C8—F2'110.0 (16)
C9i—Sb1—C15110.0 (3)F3'—C8—F2'102.1 (13)
C9—Sb1—O190.6 (3)F1—C8—F2'47.2 (14)
C9i—Sb1—O190.8 (3)F3—C8—F2'56.8 (15)
C15—Sb1—O188.02 (16)F2—C8—C5112.6 (15)
C9—Sb1—O1i90.8 (3)F1'—C8—C5116.3 (18)
C9i—Sb1—O1i90.6 (3)F3'—C8—C5108.6 (13)
C15—Sb1—O1i88.02 (16)F1—C8—C5109.0 (13)
O1—Sb1—O1i176.0 (3)F3—C8—C5111.0 (11)
C1—O1—Sb1110.8 (6)F2'—C8—C5114.2 (18)
O2—C1—O1121.7 (9)C14—C9—C10119.7 (11)
O2—C1—C2123.2 (8)C14—C9—Sb1115.0 (7)
O1—C1—C2115.1 (8)C10—C9—Sb1125.3 (9)
C3—C2—C7117.0 (9)C11—C10—C9120.8 (13)
C3—C2—C1122.8 (9)C11—C10—H10119.6
C7—C2—C1120.1 (9)C9—C10—H10119.6
C4—C3—C2120.4 (11)C10—C11—C12119.1 (17)
C4—C3—H3119.8C10—C11—H11120.4
C2—C3—H3119.8C12—C11—H11120.4
C3—C4—C5120.7 (11)C13—C12—C11120.5 (18)
C3—C4—H4119.7C13—C12—H12119.8
C5—C4—H4119.7C11—C12—H12119.8
C6—C5—C4120.1 (11)C14—C13—C12120.0 (16)
C6—C5—C8120.1 (12)C14—C13—H13120.0
C4—C5—C8119.8 (12)C12—C13—H13120.0
C5—C6—C7120.2 (11)C9—C14—C13119.8 (13)
C5—C6—H6119.9C9—C14—H14120.1
C7—C6—H6119.9C13—C14—H14120.1
C6—C7—C2121.6 (11)C16i—C15—C16118.8 (12)
C6—C7—H7119.2C16i—C15—Sb1120.6 (6)
C2—C7—H7119.2C16—C15—Sb1120.6 (6)
F2—C8—F1'46.9 (16)C17—C16—C15119.7 (10)
F2—C8—F3'60.8 (14)C17—C16—H16120.1
F1'—C8—F3'104.1 (14)C15—C16—H16120.1
F2—C8—F1114.2 (14)C18—C17—C16121.3 (11)
F1'—C8—F1135 (2)C18—C17—H17119.3
F3'—C8—F158.8 (14)C16—C17—H17119.3
F2—C8—F3106.8 (13)C17—C18—C17i118.9 (15)
F1'—C8—F361.8 (19)C17—C18—H18120.5
F3'—C8—F3140.1 (15)C17i—C18—H18120.5
F1—C8—F3102.8 (12)
Symmetry codes: (i) −x+2, −y+1, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O2ii0.932.553.304 (13)138
Symmetry codes: (ii) −y+1, x−y, z−1/3.
Table 1
Selected geometric parameters (Å, °) top
Sb1—C92.087 (10)Sb1—O12.150 (5)
Sb1—C9i2.087 (10)Sb1—O1i2.150 (5)
Sb1—C152.103 (10)
C9—Sb1—C9i140.0 (5)C9i—Sb1—C15110.0 (3)
C9—Sb1—C15110.0 (3)O1—Sb1—O1i176.0 (3)
Symmetry codes: (i) −x+2, −y+1, z.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O2ii0.932.553.304 (13)138
Symmetry codes: (ii) −y+1, x−y, z−1/3.
Acknowledgements top

We acknowledge the National Natural Foundation of China (grant No. 20771053) and the Natural Science Foundation of Shandong Province (2005ZX09) for financial support.

references
References top

Brandenburg, K. (1998). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Farrugia, L. J. (1997). J. Appl. Cryst. 30, 565.

Flack, H. D. (1983). Acta Cryst. A39, 876–881.

Sharutin, V. V., Sharutina, O. K., Pakusina, A. P., Platonova, T. P., Smirnova, S. V., Pushilin, M. A. & Gerasimenko, A. V. (2003). Russ. J. Coord. Chem. 29, 780–789.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Yin, H. D., Quan, L. & Li, L. W. (2008). Inorg. Chem. Commun. 11, 1121–1124.

Yu, L., Ma, Y.-Q., Liu, R.-C., Wang, G.-C., Li, J.-S., Du, G.-H. & Hu, J.-J. (2004). Polyhedron, 23, 823–829.