μ-Oxido-bis­[(chloro­acetato-κO)­triphenyl­anti­mony(V)]

Quan, L.; Yin, H.; Wang, D.

doi:10.1107/S1600536808000676

metal-organic compounds

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Volume 64| Part 2| February 2008| Page m349

doi:10.1107/S1600536808000676

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μ-Oxido-bis[(chloroacetato-κO)triphenylantimony(V)]

Li Quan,^a Handong Yin ^a ^* and Daqi Wang ^a

^aSchool of Chemistry and Chemical Engineering, Liaocheng University, Liaocheng 252059, People's Republic of China
^*Correspondence e-mail: handongyin@163.com

(Received 6 November 2007; accepted 8 January 2008; online 16 January 2008)

The Sb atom in the centrosymmetric title complex, [Sb₂(C₆H₅)₆(C₂H₂ClO₂)₂O], has a distorted trigonal–bipyramidal geometry. The bridging oxide O atom occupies one of the axial sites, while the O atom of the chloroacetate ligand occupies the other.

Related literature

For related literature, see: Gibbons & Sowerby (1998 ).

Experimental

Crystal data

[Sb₂(C₆H₅)₆(C₂H₂ClO₂)₂O]
M_r = 909.07
Monoclinic, P 2₁ /c
a = 10.4950 (12) Å
b = 19.416 (2) Å
c = 9.2584 (10) Å
β = 95.383 (2)°
V = 1878.3 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.62 mm⁻¹
T = 298 (2) K
0.41 × 0.18 × 0.11 mm

Data collection

Bruker SMART diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.556, T_max = 0.842
8838 measured reflections
3305 independent reflections
2465 reflections with I > 2σ(I)
R_int = 0.035

Refinement

R[F² > 2σ(F²)] = 0.040
wR(F²) = 0.109
S = 1.00
3305 reflections
223 parameters
6 restraints
H-atom parameters constrained
Δρ_max = 1.14 e Å⁻³
Δρ_min = −1.07 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

Sb1—O3	1.9503 (4)
Sb1—O1	2.197 (4)
O3—Sb1ⁱ	1.9503 (4)

O3—Sb1—O1	176.64 (11)
Sb1—O3—Sb1ⁱ	180
Symmetry code: (i) -x, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C17—H17⋯Cl1ⁱⁱ	0.93	2.93	3.592 (8)	130
Symmetry code: (ii) x-1, y, z.

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808000676/sg2199sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808000676/sg2199Isup2.hkl

checkCIF report

Comment top

Organoantimony esters of carboxylic acids are widely used as biocides, as fungicides and, in industry, as homogeneous catalysts. We have therefore synthesized the title compound, (I), and present its crystal structure here. The molecular structure of (I) is shown in Fig. 1. For a related structure see bis(triphenylantimony) trifluoroacetate [Sb(C₆H₅)₃(O₂C₂F₃)]₂O (M. N. Gibbons & Sowerby, 1998).

The title compound comprises two (chloroacetyl)tris triphenylantimony units bridged by an oxygen dianion. Centrosymmetrically molecules are linked by short intermolecular C17—H17···Cl1 contacts [symmetry codes: -1 + x, +y, +z], and one-dimensional polymeric chains run parallel to the a axis, (Fig. 2.). The O—Sb—O angle is 176.64 (11)°. The Sb—O distances vary with the role oxygen atoms play in the structure, the terminal Sb1—O1 [2.197 (4) Å] bond being longer than bridging Sb1—O3 [1.9503 (4) Å] bond. (Table 1, Table 2,).

Related literature top

For related literature, see: Gibbons & Sowerby (1998).

Experimental top

Chloroactic acid (0.02 g, 0.2 mmol) and sodium methoxide (0.4 ml, 0.2 mmol) was added to a stirred solution of oxygen bridged bis(chloro) tris triphenylantimony) (0.16 g, 0.2 mmol) and toluene (20 ml). The reaction mixture was stirred at room temperature for 24 h. Crystals suitable for X-ray analysis were obtained by slow evaporation of a petroleum/dichloromethane (1:2 v/v) solution over a period of a week (yield 85%. m.p. 470k). Anal. Calcd (%) for C₄₀H₃₄O₅Sb₂Cl₂(Mr = 909.08): C, 52.80; H, 3.72; O, 8.76; Cl, 7.76; Sb, 26.74. Found (%): C, 52.85; H, 3.77; O, 8.80; Cl, 7.80; Sb, 26.79

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, 1997); software used to prepare material for publication: SHELXTL (Sheldrick, 1997).

Figures top

	Fig. 1. The molecular structure, with atom labels and 50% probability displacement ellipsoids for non-H atoms.
	Fig. 2. Crystal packing, showing a extensity polymer chain, linked by C17—H17···Cl1 hydrogen bonds (dashed lines).

µ-Oxido-bis[(chloroacetato-κO)triphenylantimony(V)] top

Crystal data top

[Sb₂(C₆H₅)₆(C₂H₂ClO₂)₂O]	F(000) = 900
M_r = 909.07	D_x = 1.607 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.4950 (12) Å	Cell parameters from 3131 reflections
b = 19.416 (2) Å	θ = 2.1–24.7°
c = 9.2584 (10) Å	µ = 1.62 mm⁻¹
β = 95.383 (2)°	T = 298 K
V = 1878.3 (4) Å³	Block, colourless
Z = 2	0.41 × 0.18 × 0.11 mm

Data collection top

Bruker SMART diffractometer	3305 independent reflections
Radiation source: fine-focus sealed tube	2465 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.0°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→12
T_min = 0.556, T_max = 0.842	k = −23→21
8838 measured reflections	l = −10→11

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.109	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0489P)² + 4.2337P] where P = (F_o² + 2F_c²)/3
3305 reflections	(Δ/σ)_max < 0.001
223 parameters	Δρ_max = 1.14 e Å⁻³
6 restraints	Δρ_min = −1.07 e Å⁻³

Crystal data top

[Sb₂(C₆H₅)₆(C₂H₂ClO₂)₂O]	V = 1878.3 (4) Å³
M_r = 909.07	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 10.4950 (12) Å	µ = 1.62 mm⁻¹
b = 19.416 (2) Å	T = 298 K
c = 9.2584 (10) Å	0.41 × 0.18 × 0.11 mm
β = 95.383 (2)°

Data collection top

Bruker SMART diffractometer	3305 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	2465 reflections with I > 2σ(I)
T_min = 0.556, T_max = 0.842	R_int = 0.035
8838 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	6 restraints
wR(F²) = 0.109	H-atom parameters constrained
S = 1.00	Δρ_max = 1.14 e Å⁻³
3305 reflections	Δρ_min = −1.07 e Å⁻³
223 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sb1	0.14913 (3)	0.054058 (18)	0.45933 (4)	0.04187 (15)
Cl1	0.5107 (3)	0.17116 (18)	0.2357 (4)	0.1409 (11)
O1	0.3199 (4)	0.1102 (2)	0.4046 (5)	0.0581 (11)
O2	0.2708 (6)	0.2089 (3)	0.5109 (6)	0.0856 (16)
O3	0.0000	0.0000	0.5000	0.0530 (15)
C1	0.3341 (7)	0.1745 (4)	0.4368 (8)	0.0679 (19)
C2	0.4414 (10)	0.2112 (5)	0.3674 (12)	0.127 (4)
H2A	0.5079	0.2221	0.4440	0.152*
H2B	0.4076	0.2546	0.3286	0.152*
C3	0.2216 (5)	0.0580 (3)	0.6778 (6)	0.0455 (13)
C4	0.2782 (7)	−0.0004 (4)	0.7389 (8)	0.0693 (19)
H4	0.2832	−0.0400	0.6834	0.083*
C5	0.3272 (8)	−0.0002 (4)	0.8811 (9)	0.082 (2)
H5	0.3673	−0.0394	0.9211	0.099*
C6	0.3175 (8)	0.0574 (5)	0.9647 (8)	0.081 (2)
H6	0.3492	0.0569	1.0619	0.098*
C7	0.2617 (8)	0.1152 (4)	0.9058 (8)	0.076 (2)
H7	0.2561	0.1544	0.9625	0.092*
C8	0.2134 (7)	0.1160 (3)	0.7628 (7)	0.0642 (18)
H8	0.1751	0.1558	0.7230	0.077*
C9	0.2230 (6)	−0.0235 (3)	0.3337 (6)	0.0448 (14)
C10	0.3500 (7)	−0.0424 (4)	0.3467 (8)	0.0679 (19)
H10	0.4074	−0.0195	0.4127	0.082*
C11	0.3925 (9)	−0.0937 (4)	0.2649 (11)	0.093 (3)
H11	0.4781	−0.1067	0.2769	0.112*
C12	0.3100 (10)	−0.1264 (4)	0.1649 (10)	0.088 (3)
H12	0.3399	−0.1609	0.1071	0.106*
C13	0.1843 (9)	−0.1089 (4)	0.1497 (9)	0.088 (3)
H13	0.1280	−0.1316	0.0821	0.105*
C14	0.1402 (7)	−0.0574 (3)	0.2346 (7)	0.0609 (17)
H14	0.0539	−0.0456	0.2247	0.073*
C15	0.0381 (5)	0.1302 (3)	0.3458 (6)	0.0446 (13)
C16	−0.0780 (6)	0.1476 (3)	0.3891 (7)	0.0554 (16)
H16	−0.1081	0.1257	0.4686	0.066*
C17	−0.1512 (7)	0.1976 (3)	0.3149 (9)	0.070 (2)
H17	−0.2291	0.2106	0.3467	0.084*
C18	−0.1096 (8)	0.2278 (4)	0.1957 (9)	0.074 (2)
H18	−0.1608	0.2602	0.1441	0.088*
C19	0.0063 (8)	0.2112 (4)	0.1511 (8)	0.074 (2)
H19	0.0357	0.2328	0.0710	0.088*
C20	0.0798 (7)	0.1616 (3)	0.2265 (7)	0.0619 (17)
H20	0.1586	0.1494	0.1959	0.074*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sb1	0.0420 (2)	0.0387 (2)	0.0444 (2)	−0.00671 (18)	0.00144 (15)	−0.00121 (18)
Cl1	0.1011 (19)	0.184 (3)	0.144 (3)	−0.051 (2)	0.0457 (18)	−0.015 (2)
O1	0.059 (3)	0.048 (2)	0.068 (3)	−0.019 (2)	0.011 (2)	−0.002 (2)
O2	0.099 (4)	0.067 (3)	0.094 (4)	−0.022 (3)	0.029 (3)	−0.015 (3)
O3	0.041 (3)	0.052 (3)	0.066 (4)	−0.016 (3)	0.006 (3)	0.003 (3)
C1	0.062 (4)	0.068 (5)	0.075 (5)	−0.025 (4)	0.014 (4)	−0.007 (4)
C2	0.125 (7)	0.114 (6)	0.152 (8)	−0.045 (6)	0.065 (6)	−0.035 (6)
C3	0.047 (3)	0.046 (3)	0.043 (3)	−0.013 (3)	0.003 (3)	−0.001 (3)
C4	0.085 (5)	0.051 (4)	0.069 (5)	−0.003 (4)	−0.011 (4)	0.003 (3)
C5	0.095 (6)	0.078 (5)	0.070 (5)	0.004 (5)	−0.018 (4)	0.023 (4)
C6	0.089 (6)	0.104 (7)	0.049 (5)	−0.023 (5)	−0.008 (4)	0.007 (5)
C7	0.098 (6)	0.082 (5)	0.049 (5)	−0.007 (5)	0.008 (4)	−0.015 (4)
C8	0.079 (5)	0.056 (4)	0.058 (5)	0.005 (4)	0.010 (4)	−0.003 (3)
C9	0.051 (4)	0.041 (3)	0.044 (3)	−0.009 (3)	0.011 (3)	−0.003 (3)
C10	0.056 (4)	0.070 (5)	0.076 (5)	0.000 (4)	0.001 (4)	−0.010 (4)
C11	0.082 (6)	0.075 (6)	0.128 (8)	0.024 (5)	0.032 (6)	−0.006 (5)
C12	0.115 (7)	0.055 (4)	0.102 (7)	0.003 (5)	0.047 (6)	−0.018 (4)
C13	0.102 (7)	0.073 (5)	0.090 (6)	−0.029 (5)	0.020 (5)	−0.037 (5)
C14	0.059 (4)	0.060 (4)	0.064 (4)	−0.010 (3)	0.008 (3)	−0.010 (3)
C15	0.049 (3)	0.039 (3)	0.046 (4)	−0.003 (3)	−0.002 (3)	−0.002 (3)
C16	0.061 (4)	0.043 (3)	0.061 (4)	−0.006 (3)	0.000 (3)	0.003 (3)
C17	0.065 (5)	0.059 (4)	0.083 (6)	0.013 (4)	−0.007 (4)	−0.003 (4)
C18	0.089 (6)	0.055 (4)	0.072 (5)	0.011 (4)	−0.021 (4)	0.007 (4)
C19	0.095 (6)	0.069 (5)	0.055 (5)	−0.002 (4)	−0.002 (4)	0.014 (4)
C20	0.080 (5)	0.063 (4)	0.044 (4)	0.000 (4)	0.008 (3)	0.010 (3)

Geometric parameters (Å, º) top

Sb1—O3	1.9503 (4)	C9—C14	1.371 (9)
Sb1—C3	2.095 (6)	C9—C10	1.377 (9)
Sb1—C9	2.095 (6)	C10—C11	1.353 (10)
Sb1—C15	2.101 (6)	C10—H10	0.9300
Sb1—O1	2.197 (4)	C11—C12	1.364 (12)
Cl1—C2	1.670 (9)	C11—H11	0.9300
O1—C1	1.289 (8)	C12—C13	1.357 (11)
O2—C1	1.201 (8)	C12—H12	0.9300
O3—Sb1ⁱ	1.9503 (4)	C13—C14	1.379 (9)
C1—C2	1.525 (10)	C13—H13	0.9300
C2—H2A	0.9700	C14—H14	0.9300
C2—H2B	0.9700	C15—C16	1.361 (8)
C3—C4	1.377 (8)	C15—C20	1.368 (8)
C3—C8	1.382 (8)	C16—C17	1.381 (9)
C4—C5	1.367 (10)	C16—H16	0.9300
C4—H4	0.9300	C17—C18	1.358 (10)
C5—C6	1.370 (11)	C17—H17	0.9300
C5—H5	0.9300	C18—C19	1.360 (10)
C6—C7	1.357 (10)	C18—H18	0.9300
C6—H6	0.9300	C19—C20	1.382 (9)
C7—C8	1.372 (10)	C19—H19	0.9300
C7—H7	0.9300	C20—H20	0.9300
C8—H8	0.9300

O3—Sb1—C3	93.36 (15)	C3—C8—H8	119.9
O3—Sb1—C9	93.77 (15)	C14—C9—C10	118.6 (6)
C3—Sb1—C9	116.3 (2)	C14—C9—Sb1	118.2 (5)
O3—Sb1—C15	93.31 (15)	C10—C9—Sb1	123.3 (5)
C3—Sb1—C15	126.3 (2)	C11—C10—C9	121.0 (7)
C9—Sb1—C15	116.4 (2)	C11—C10—H10	119.5
O3—Sb1—O1	176.64 (11)	C9—C10—H10	119.5
C3—Sb1—O1	88.53 (19)	C10—C11—C12	120.1 (8)
C9—Sb1—O1	82.89 (19)	C10—C11—H11	120.0
C15—Sb1—O1	87.80 (19)	C12—C11—H11	120.0
C1—O1—Sb1	120.4 (4)	C13—C12—C11	120.2 (7)
Sb1—O3—Sb1ⁱ	180.00 (2)	C13—C12—H12	119.9
O2—C1—O1	127.7 (6)	C11—C12—H12	119.9
O2—C1—C2	116.8 (7)	C12—C13—C14	119.8 (8)
O1—C1—C2	115.4 (7)	C12—C13—H13	120.1
C1—C2—Cl1	118.7 (7)	C14—C13—H13	120.1
C1—C2—H2A	107.6	C9—C14—C13	120.3 (7)
Cl1—C2—H2A	107.6	C9—C14—H14	119.9
C1—C2—H2B	107.6	C13—C14—H14	119.9
Cl1—C2—H2B	107.6	C16—C15—C20	119.3 (6)
H2A—C2—H2B	107.1	C16—C15—Sb1	119.8 (4)
C4—C3—C8	119.0 (6)	C20—C15—Sb1	120.9 (5)
C4—C3—Sb1	118.1 (5)	C15—C16—C17	120.0 (6)
C8—C3—Sb1	122.9 (5)	C15—C16—H16	120.0
C5—C4—C3	120.2 (7)	C17—C16—H16	120.0
C5—C4—H4	119.9	C18—C17—C16	120.1 (7)
C3—C4—H4	119.9	C18—C17—H17	119.9
C4—C5—C6	120.3 (7)	C16—C17—H17	119.9
C4—C5—H5	119.8	C17—C18—C19	120.6 (7)
C6—C5—H5	119.8	C17—C18—H18	119.7
C7—C6—C5	120.1 (7)	C19—C18—H18	119.7
C7—C6—H6	120.0	C18—C19—C20	119.0 (7)
C5—C6—H6	120.0	C18—C19—H19	120.5
C6—C7—C8	120.2 (7)	C20—C19—H19	120.5
C6—C7—H7	119.9	C15—C20—C19	120.9 (7)
C8—C7—H7	119.9	C15—C20—H20	119.6
C7—C8—C3	120.2 (7)	C19—C20—H20	119.6
C7—C8—H8	119.9

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···Cl1ⁱⁱ	0.93	2.93	3.592 (8)	130

Symmetry code: (ii) x−1, y, z.

Experimental details

Crystal data
Chemical formula	[Sb₂(C₆H₅)₆(C₂H₂ClO₂)₂O]
M_r	909.07
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	10.4950 (12), 19.416 (2), 9.2584 (10)
β (°)	95.383 (2)
V (Å³)	1878.3 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.62
Crystal size (mm)	0.41 × 0.18 × 0.11

Data collection
Diffractometer	Bruker SMART diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.556, 0.842
No. of measured, independent and observed [I > 2σ(I)] reflections	8838, 3305, 2465
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.109, 1.00
No. of reflections	3305
No. of parameters	223
No. of restraints	6
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.14, −1.07

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 1997).

Selected geometric parameters (Å, º) top

Sb1—O3	1.9503 (4)	O3—Sb1ⁱ	1.9503 (4)
Sb1—O1	2.197 (4)

O3—Sb1—O1	176.64 (11)	Sb1—O3—Sb1ⁱ	180.00 (2)

Symmetry code: (i) −x, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C17—H17···Cl1ⁱⁱ	0.93	2.93	3.592 (8)	129.5

Symmetry code: (ii) x−1, y, z.

Acknowledgements

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

References

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