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Acta Cryst. (2009). E65, m1442    [ doi:10.1107/S160053680904358X ]

Bis(2-amino-4-chlorobenzoato)triphenylantimony(V)

L. Wen, H. Yin and C. Wang

Abstract top

The title complex molecule, [Sb(C6H5)3(C7H5ClNO2)2], possesses crystallographically imposed C2 symmetry. The Sb atom exhibits a trigonal-bipyramidal geometry with the axial positions occupied by the O atoms of two carboxylate groups and the equatorial positions by the C atoms of the phenyl groups. Intramolecular N-H...O and C-H...O hydrogen bonds occur.

Comment top

Organoantimony(V) complexes have been intensively studied owing to their versatile bonding modes (Yin et al., 2009) and biological applications. We have therefore synthesized the title compound, and present its crystal structure here.

The molecular structure of the compound is shown in Fig.1. The complex molecule possesses crystallographically imposed C2 symmetry, the rotation axis passing through the Sb atom and bisecting the C14–C17/C15'/C16' phenyl ring. The coordination geometry around the five-coordinate antimony atom can be described as slightly distorted trigonal bipyramidal, with three C atoms of the phenyl groups occupying the equatorial positions and two O atoms of carboxylate groups at the axial positions. The average Sb—O bond length of 2.122 (2) Å is approximately equal to the sum of the covalent radii of Sb and O (2.07 Å), and lies within the range from 1.935 Å observed in triphenylstibine oxide (Ferguson et al., 1987) to 2.506 Å found in tetraphenylstibonium benzenesulphonate hydrate (Rüther et al., 1985). The Sb—C bond distances (Sb1—C8 = 2.101 (3) Å; Sb1—C8A = 2.101 (3) Å; Sb1—C14 = 2.122 (4) Å) fall in the normal range for Sb—C(phenyl) bonds (2.10–2.13 Å). The conformation of the complex molecule is enforced by intramolecular N—H···O and C—H···O hydrogen bonds (Table 1). The crystal packing (Fig. 2) is stabilized only by van der Waals interactions.

Related literature top

For the related structures, see: Yin et al. (2009); Ferguson et al. (1987); Rüther et al. (1985).

Experimental top

The reaction was carried out under nitrogen atmosphere. 2-amino-4-chlorobenzoic acid (1 mmol) and sodium ethoxide (1.2 mmol) were added to a stirred solution of methanol (30 ml) in a Schlenk flask and stirred for 0.5 h. Triphenylantimony dichloride (0.5 mmol) was then added to the reactor and the reaction mixture was stirred for 12 h at room temperature. The resulting clear solution was evaporated under vacuum. Colourless crystals suitable for X-ray analysis were obtained by slow evaporation of a ether/n-hexane (1:1 v/v) solution (yield 87%). Anal. Calcd (%) for C32H25Cl2N2O4Sb (Mr = 694.19): C, 55.37; H, 3.63; Cl, 10.21; N, 4.04. Found (%): C, 55.30; H, 3.74; Cl, 10.33; N, 4.16.

Refinement top

The C—H and N—H H atoms were positioned with idealized geometry and were refined isotropically using a riding model with N—H = 0.86 Å and C—H = 0.93 Å and with Uiso(H) = 1.2 Ueq(C, N).

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. H atoms are omitted for clarity. Symmetry code: (A) = -x, -y, z.
[Figure 2] Fig. 2. The crystal packing of the title compound.
Bis(2-amino-4-chlorobenzoato)triphenylantimony(V) top
Crystal data top
[Sb(C6H5)3(C7H5ClNO2)2]F(000) = 2784
Mr = 694.20Dx = 1.597 Mg m−3
Orthorhombic, Fdd2Mo Kα radiation, λ = 0.71073 Å
Hall symbol: F 2 -2dCell parameters from 3849 reflections
a = 13.0168 (13) Åθ = 2.7–26.8°
b = 20.298 (2) ŵ = 1.18 mm−1
c = 21.849 (3) ÅT = 298 K
V = 5772.8 (11) Å3Block, colourless
Z = 80.39 × 0.38 × 0.37 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer		2493 independent reflections
Radiation source: fine-focus sealed tube2222 reflections with I > 2σ(I)
graphiteRint = 0.019
φ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −15→11
Tmin = 0.656, Tmax = 0.669k = −24→22
5819 measured reflectionsl = −25→24
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.021H-atom parameters constrained
wR(F2) = 0.051 w = 1/[σ2(Fo2) + (0.0236P)2 + 0.2508P]
where P = (Fo2 + 2Fc2)/3
S = 1.11(Δ/σ)max < 0.001
2493 reflectionsΔρmax = 0.35 e Å−3
187 parametersΔρmin = −0.25 e Å−3
1 restraintAbsolute structure: Flack (1983), 1181 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: −0.02 (2)
Crystal data top
[Sb(C6H5)3(C7H5ClNO2)2]V = 5772.8 (11) Å3
Mr = 694.20Z = 8
Orthorhombic, Fdd2Mo Kα radiation
a = 13.0168 (13) ŵ = 1.18 mm−1
b = 20.298 (2) ÅT = 298 K
c = 21.849 (3) Å0.39 × 0.38 × 0.37 mm
Data collection top
Siemens SMART CCD area-detector
diffractometer		2493 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2222 reflections with I > 2σ(I)
Tmin = 0.656, Tmax = 0.669Rint = 0.019
5819 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.021H-atom parameters constrained
wR(F2) = 0.051Δρmax = 0.35 e Å−3
S = 1.11Δρmin = −0.25 e Å−3
2493 reflectionsAbsolute structure: Flack (1983), 1181 Friedel pairs
187 parametersFlack parameter: −0.02 (2)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sb10.00000.00000.024065 (19)0.03974 (9)
Cl10.64382 (7)0.11557 (6)0.05169 (7)0.0943 (4)
N10.3358 (3)0.0520 (3)0.17751 (19)0.0964 (16)
H1A0.27330.03950.18280.116*
H1B0.37620.05590.20840.116*
O10.15241 (14)0.03663 (11)0.01894 (11)0.0483 (5)
O20.15456 (18)0.03090 (13)0.12027 (11)0.0561 (6)
C10.1992 (2)0.04151 (16)0.07150 (17)0.0450 (8)
C20.3091 (2)0.06030 (15)0.06822 (16)0.0448 (8)
C30.3705 (3)0.06552 (19)0.12053 (19)0.0576 (9)
C40.4750 (3)0.0831 (2)0.1132 (2)0.0675 (12)
H40.51730.08620.14740.081*
C50.5136 (3)0.0953 (2)0.0574 (3)0.0626 (13)
C60.4552 (4)0.0923 (2)0.0053 (2)0.0665 (14)
H60.48270.1026−0.03290.080*
C70.3533 (3)0.0734 (2)0.01176 (19)0.0613 (10)
H70.31300.0693−0.02320.074*
C8−0.0531 (2)0.09057 (16)0.05826 (17)0.0436 (8)
C9−0.0934 (2)0.13384 (17)0.01584 (19)0.0552 (9)
H9−0.09850.1214−0.02500.066*
C10−0.1264 (3)0.19567 (18)0.0339 (2)0.0695 (11)
H10−0.15190.22510.00510.083*
C11−0.1215 (3)0.2135 (2)0.0937 (3)0.0705 (12)
H11−0.14430.25490.10580.085*
C12−0.0830 (3)0.1705 (2)0.1366 (2)0.0671 (13)
H12−0.07980.18320.17740.081*
C13−0.0492 (3)0.10877 (18)0.11947 (17)0.0549 (9)
H13−0.02410.07960.14870.066*
C140.00000.0000−0.07304 (19)0.0384 (10)
C150.0908 (2)0.0031 (2)−0.10502 (17)0.0586 (10)
H150.15270.0057−0.08390.070*
C160.0907 (3)0.0024 (2)−0.16793 (18)0.0699 (12)
H160.15250.0036−0.18930.084*
C170.00000.0000−0.1989 (2)0.0627 (15)
H170.00000.0000−0.24150.075*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sb10.03262 (12)0.04916 (15)0.03746 (14)0.00228 (16)0.0000.000
Cl10.0427 (5)0.0907 (8)0.1495 (13)−0.0156 (5)0.0057 (6)−0.0279 (9)
N10.059 (2)0.183 (5)0.048 (3)0.000 (3)−0.0108 (18)0.003 (3)
O10.0361 (10)0.0658 (13)0.0429 (13)−0.0046 (10)−0.0065 (11)−0.0040 (13)
O20.0472 (13)0.0755 (16)0.0455 (14)−0.0046 (12)0.0037 (11)0.0019 (13)
C10.0366 (16)0.049 (2)0.049 (2)0.0028 (14)−0.0051 (16)−0.0044 (17)
C20.0375 (17)0.0476 (19)0.049 (2)0.0028 (13)−0.0048 (15)−0.0028 (16)
C30.045 (2)0.072 (2)0.056 (2)0.0052 (17)−0.0088 (18)−0.008 (2)
C40.048 (2)0.072 (3)0.082 (3)0.0027 (18)−0.021 (2)−0.016 (2)
C50.044 (2)0.057 (2)0.087 (4)−0.0050 (16)0.005 (2)−0.015 (2)
C60.048 (3)0.085 (3)0.067 (3)−0.010 (2)0.010 (2)−0.008 (2)
C70.047 (2)0.075 (3)0.063 (3)−0.0070 (18)0.0008 (18)−0.009 (2)
C80.0297 (15)0.050 (2)0.051 (2)0.0031 (14)0.0057 (15)−0.0010 (17)
C90.0478 (18)0.058 (2)0.059 (2)0.0043 (15)−0.0086 (17)−0.0025 (19)
C100.056 (2)0.055 (2)0.098 (4)0.0121 (16)−0.006 (2)0.002 (3)
C110.052 (2)0.057 (3)0.103 (4)0.0004 (19)0.010 (2)−0.013 (3)
C120.061 (2)0.072 (3)0.067 (3)−0.005 (2)0.012 (2)−0.024 (3)
C130.053 (2)0.059 (2)0.053 (2)0.0042 (16)0.0027 (18)−0.0049 (19)
C140.038 (2)0.046 (2)0.031 (2)0.0020 (19)0.0000.000
C150.0319 (17)0.099 (3)0.045 (2)−0.0012 (18)−0.0007 (15)−0.009 (2)
C160.046 (2)0.119 (4)0.045 (2)0.004 (2)0.0090 (17)−0.003 (2)
C170.062 (3)0.095 (4)0.031 (3)0.013 (3)0.0000.000
Geometric parameters (Å, °) top
Sb1—C8i2.101 (3)C7—H70.9300
Sb1—C82.101 (3)C8—C91.381 (5)
Sb1—C142.122 (4)C8—C131.388 (5)
Sb1—O12.1217 (19)C9—C101.384 (5)
Sb1—O1i2.1217 (19)C9—H90.9300
Cl1—C51.749 (4)C10—C111.357 (6)
N1—C31.352 (5)C10—H100.9300
N1—H1A0.8600C11—C121.373 (6)
N1—H1B0.8600C11—H110.9300
O1—C11.304 (4)C12—C131.380 (5)
O2—C11.233 (4)C12—H120.9300
C1—C21.482 (4)C13—H130.9300
C2—C71.387 (5)C14—C15i1.374 (4)
C2—C31.399 (5)C14—C151.374 (4)
C3—C41.416 (5)C15—C161.375 (5)
C4—C51.341 (7)C15—H150.9300
C4—H40.9300C16—C171.362 (5)
C5—C61.372 (6)C16—H160.9300
C6—C71.389 (6)C17—C16i1.362 (5)
C6—H60.9300C17—H170.9300
C8i—Sb1—C8138.3 (2)C2—C7—H7118.6
C8i—Sb1—C14110.83 (10)C6—C7—H7118.6
C8—Sb1—C14110.83 (10)C9—C8—C13119.4 (3)
C8i—Sb1—O191.03 (10)C9—C8—Sb1116.3 (3)
C8—Sb1—O191.12 (10)C13—C8—Sb1124.3 (3)
C14—Sb1—O186.98 (6)C8—C9—C10120.2 (4)
C8i—Sb1—O1i91.12 (10)C8—C9—H9119.9
C8—Sb1—O1i91.03 (10)C10—C9—H9119.9
C14—Sb1—O1i86.98 (6)C11—C10—C9120.1 (4)
O1—Sb1—O1i173.95 (13)C11—C10—H10119.9
C3—N1—H1A120.0C9—C10—H10119.9
C3—N1—H1B120.0C10—C11—C12120.2 (4)
H1A—N1—H1B120.0C10—C11—H11119.9
C1—O1—Sb1114.6 (2)C12—C11—H11119.9
O2—C1—O1121.9 (3)C11—C12—C13120.6 (4)
O2—C1—C2122.8 (3)C11—C12—H12119.7
O1—C1—C2115.3 (3)C13—C12—H12119.7
C7—C2—C3118.4 (3)C12—C13—C8119.4 (4)
C7—C2—C1119.5 (3)C12—C13—H13120.3
C3—C2—C1122.1 (3)C8—C13—H13120.3
N1—C3—C2123.1 (3)C15i—C14—C15118.9 (4)
N1—C3—C4118.4 (4)C15i—C14—Sb1120.6 (2)
C2—C3—C4118.4 (4)C15—C14—Sb1120.6 (2)
C5—C4—C3120.6 (4)C14—C15—C16120.5 (3)
C5—C4—H4119.7C14—C15—H15119.8
C3—C4—H4119.7C16—C15—H15119.8
C4—C5—C6122.7 (4)C17—C16—C15119.9 (4)
C4—C5—Cl1118.1 (4)C17—C16—H16120.1
C6—C5—Cl1119.2 (4)C15—C16—H16120.1
C5—C6—C7117.2 (4)C16—C17—C16i120.4 (5)
C5—C6—H6121.4C16—C17—H17119.8
C7—C6—H6121.4C16i—C17—H17119.8
C2—C7—C6122.7 (4)
Symmetry codes: (i) −x, −y, z.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.862.072.704 (5)130
C15—H15···O10.932.332.905 (4)119
Table 1
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1A···O20.862.072.704 (5)130
C15—H15···O10.932.332.905 (4)119
Acknowledgements top

We acknowledge the National Natural Science Foundation of China (20771053) and the Natural Science Foundation of Shandong Province (Y2008B48) for financial support.

references
References top

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

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

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Yin, H. D., Wen, L. Y., Cui, J. C. & Li, W. K. (2009). Polyhedron, 28, 2919–2926.