catena-Poly[[trimethyl­tin(IV)]-μ-3,5-difluoro­benzoato-κ2O:O′]

Liu, H.; Yin, H.

doi:10.1107/S1600536811025608

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 8| August 2011| Page m1030

doi:10.1107/S1600536811025608

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catena-Poly[[trimethyltin(IV)]-μ-3,5-difluorobenzoato-κ²O:O′]

Hong Liu ^a and Handong Yin ^a ^*

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

(Received 5 June 2011; accepted 29 June 2011; online 6 July 2011)

In the title compound, [Sn(CH₃)₃(C₇H₃F₂O₂)]_n, the central Sn atom is coordinated by two O atoms from the anion and three methyl C atoms in a polymeric fashion owing to the presence of bidentate bridging carboxylate ligands. The five-coordinate Sn atom exists in a distorted trigonal–bipyramidal geometry with the molecules connected by weak C—H⋯F intermoleclar interactions, forming supramolecular chains parallel to [010].

Related literature

For industrial applications and the biological activity of organotin compounds, see: Duboy & Roy (2003 ). For related trimethyl carboxylates with similar structures, see: Tiekink, (1994 ).

Experimental

Crystal data

[Sn(CH₃)₃(C₇H₃F₂O₂)]
M_r = 320.89
Monoclinic, C 2/c
a = 13.1371 (12) Å
b = 10.0847 (11) Å
c = 18.9643 (19) Å
β = 101.864 (1)°
V = 2458.8 (4) Å³
Z = 8
Mo Kα radiation
μ = 2.08 mm⁻¹
T = 298 K
0.50 × 0.42 × 0.40 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.422, T_max = 0.490
5945 measured reflections
2165 independent reflections
1725 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.032
wR(F²) = 0.073
S = 1.17
2165 reflections
140 parameters
H-atom parameters constrained
Δρ_max = 0.76 e Å⁻³
Δρ_min = −0.69 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C9—H9C⋯F1ⁱ	0.96	2.62	3.470 (7)	148
Symmetry code: (i) $[x, -y, z-{\script{1\over 2}}]$ .

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

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811025608/jj2092sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811025608/jj2092Isup2.hkl

checkCIF report

Comment top

In recent years, organotin compounds have attracted increasing attention owing to their wide industrial applications and biological activities (Duboy and Roy, 2003). In continuation of our work in this area, we present the crystal structure of a new compound, (I), C₁₀H₁₂F₂O₂Sn. Similar structures for related trimethyl carboxylates have been reported. (Tiekink, 1994).

In the title compound, (I), the central Sn atom is coordinated by two oxygen atoms from the ligand and three carbon methyl atoms in a polymeric fashion owing to the presence of bidentate bridging carboxylate ligands (Fig. 1). The Sn(1)—O(1) and Sn(1)—O(2)#1 (#1 = -x + 1/2,y - 1/2,-z + 1/2) distances are 2.137 (3)Å and 2.540 (4) Å, respectively. The angle of the axial O(1)—Sn(1)—O(2)#1 is 175.92 (13)°, which deviates slightly from linearity. The five-coordinate Sn atom exists in a distorted trigonal bipyramidal geometry with the molecules connected by weak C—H···F intermoleclar interactions, forming one-dimensional supramolecular chains along the (101) plane (Fig. 2).

Related literature top

For industrial applications and the biological activity of organotin compounds, see: Duboy & Roy (2003). For related trimethyl carboxylates with similar structures, see: Tiekink, (1994).

Experimental top

3,5-difluorobenzoic acid (0.4 mmol) was added to a methanol solution of sodium ethoxide (0.4 mmol) and heated at reflux for 0.5 h. To this solution was added trimethyltin chloride (0.8 mmol) in benzene and the mixture was refluxed for 8 h, cooled and filtered. The filtrate was evaporated in vacuo. The obtained solid was recrystallized from dichloromethane-petroleum ether. Anal. Calcd (%) for C₁₀H₁₂F₂O₂Sn (Mr = 320.89): C, 37.43; H, 3.77; Found (%): C, 38.21; H, 3.92.

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

	Fig. 1. ORTEP diagram of the title compound, with 50% probability displacement ellipsoids.
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. H atoms have been omitted for clarity.

catena-Poly[[trimethyltin(IV)]-µ-3,5-difluorobenzoato- κ²O:O'] top

Crystal data top

[Sn(CH₃)₃(C₇H₃F₂O₂)]	F(000) = 1248
M_r = 320.89	D_x = 1.734 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 3905 reflections
a = 13.1371 (12) Å	θ = 2.7–26.3°
b = 10.0847 (11) Å	µ = 2.08 mm⁻¹
c = 18.9643 (19) Å	T = 298 K
β = 101.864 (1)°	Block, colorless
V = 2458.8 (4) Å³	0.50 × 0.42 × 0.40 mm
Z = 8

Data collection top

Siemens SMART CCD area-detector diffractometer	2165 independent reflections
Radiation source: fine-focus sealed tube	1725 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −14→15
T_min = 0.422, T_max = 0.490	k = −9→12
5945 measured reflections	l = −22→22

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.032	H-atom parameters constrained
wR(F²) = 0.073	w = 1/[σ²(F_o²) + (0.0148P)² + 7.4343P] where P = (F_o² + 2F_c²)/3
S = 1.17	(Δ/σ)_max = 0.008
2165 reflections	Δρ_max = 0.76 e Å⁻³
140 parameters	Δρ_min = −0.69 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.00219 (15)

Crystal data top

[Sn(CH₃)₃(C₇H₃F₂O₂)]	V = 2458.8 (4) Å³
M_r = 320.89	Z = 8
Monoclinic, C2/c	Mo Kα radiation
a = 13.1371 (12) Å	µ = 2.08 mm⁻¹
b = 10.0847 (11) Å	T = 298 K
c = 18.9643 (19) Å	0.50 × 0.42 × 0.40 mm
β = 101.864 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2165 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1725 reflections with I > 2σ(I)
T_min = 0.422, T_max = 0.490	R_int = 0.034
5945 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.073	H-atom parameters constrained
S = 1.17	Δρ_max = 0.76 e Å⁻³
2165 reflections	Δρ_min = −0.69 e Å⁻³
140 parameters

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

	x	y	z	U_iso*/U_eq
Sn1	0.21709 (3)	−0.11988 (3)	0.275296 (18)	0.04976 (17)
O1	0.1757 (3)	0.0218 (3)	0.34840 (19)	0.0620 (10)
O2	0.2446 (3)	0.2018 (4)	0.3102 (2)	0.0664 (10)
F1	−0.0238 (3)	0.1709 (4)	0.5259 (2)	0.0939 (12)
F2	0.1732 (3)	0.5409 (3)	0.4910 (2)	0.0944 (12)
C1	0.1945 (4)	0.1461 (5)	0.3495 (3)	0.0483 (12)
C2	0.1503 (3)	0.2219 (5)	0.4043 (2)	0.0431 (11)
C3	0.0816 (4)	0.1598 (5)	0.4403 (3)	0.0523 (12)
H3	0.0613	0.0724	0.4300	0.063*
C4	0.0443 (4)	0.2301 (6)	0.4913 (3)	0.0587 (14)
C5	0.0744 (4)	0.3574 (6)	0.5100 (3)	0.0658 (15)
H5	0.0497	0.4024	0.5459	0.079*
C6	0.1422 (5)	0.4153 (5)	0.4736 (3)	0.0623 (15)
C7	0.1796 (4)	0.3514 (5)	0.4209 (3)	0.0539 (13)
H7	0.2243	0.3947	0.3964	0.065*
C8	0.1543 (6)	−0.2738 (6)	0.3291 (4)	0.094 (2)
H8A	0.1335	−0.3461	0.2964	0.141*
H8B	0.0949	−0.2412	0.3459	0.141*
H8C	0.2059	−0.3039	0.3693	0.141*
C9	0.1173 (4)	−0.0367 (6)	0.1847 (3)	0.0685 (16)
H9A	0.1543	0.0292	0.1635	0.103*
H9B	0.0587	0.0036	0.1994	0.103*
H9C	0.0933	−0.1051	0.1501	0.103*
C10	0.3794 (4)	−0.0930 (6)	0.2996 (3)	0.0766 (18)
H10A	0.4073	−0.1137	0.2580	0.115*
H10B	0.4098	−0.1505	0.3386	0.115*
H10C	0.3951	−0.0025	0.3134	0.115*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0557 (2)	0.0429 (2)	0.0565 (2)	0.00350 (16)	0.02496 (16)	0.00374 (17)
O1	0.085 (3)	0.044 (2)	0.068 (2)	0.0015 (18)	0.040 (2)	−0.0038 (17)
O2	0.087 (3)	0.059 (2)	0.066 (2)	−0.0043 (19)	0.046 (2)	0.0052 (19)
F1	0.101 (3)	0.099 (3)	0.102 (3)	0.009 (2)	0.070 (2)	0.014 (2)
F2	0.130 (3)	0.058 (2)	0.100 (3)	0.002 (2)	0.033 (2)	−0.0238 (19)
C1	0.055 (3)	0.044 (3)	0.048 (3)	0.007 (2)	0.017 (2)	0.004 (2)
C2	0.042 (3)	0.047 (3)	0.042 (3)	0.007 (2)	0.013 (2)	0.004 (2)
C3	0.056 (3)	0.051 (3)	0.053 (3)	0.004 (2)	0.018 (2)	0.006 (2)
C4	0.058 (3)	0.067 (4)	0.056 (3)	0.013 (3)	0.025 (3)	0.013 (3)
C5	0.077 (4)	0.073 (4)	0.052 (3)	0.031 (3)	0.023 (3)	0.004 (3)
C6	0.075 (4)	0.048 (3)	0.062 (3)	0.016 (3)	0.011 (3)	−0.006 (3)
C7	0.060 (3)	0.051 (3)	0.054 (3)	0.004 (2)	0.018 (2)	0.003 (2)
C8	0.145 (6)	0.049 (3)	0.118 (5)	0.007 (4)	0.097 (5)	0.008 (4)
C9	0.056 (3)	0.083 (4)	0.066 (4)	0.011 (3)	0.013 (3)	−0.002 (3)
C10	0.058 (3)	0.091 (5)	0.078 (4)	0.011 (3)	0.007 (3)	−0.007 (3)

Geometric parameters (Å, º) top

Sn1—C10	2.104 (5)	C4—C5	1.368 (7)
Sn1—C9	2.109 (5)	C5—C6	1.365 (8)
Sn1—C8	2.115 (6)	C5—H5	0.9300
Sn1—O1	2.137 (3)	C6—C7	1.363 (7)
Sn1—O2ⁱ	2.540 (4)	C7—H7	0.9300
O1—C1	1.278 (6)	C8—H8A	0.9600
O2—C1	1.227 (6)	C8—H8B	0.9600
O2—Sn1ⁱⁱ	2.540 (4)	C8—H8C	0.9600
F1—C4	1.353 (6)	C9—H9A	0.9600
F2—C6	1.351 (6)	C9—H9B	0.9600
C1—C2	1.500 (6)	C9—H9C	0.9600
C2—C7	1.379 (6)	C10—H10A	0.9600
C2—C3	1.389 (6)	C10—H10B	0.9600
C3—C4	1.368 (7)	C10—H10C	0.9600
C3—H3	0.9300

C10—Sn1—C9	124.0 (2)	C4—C5—H5	121.5
C10—Sn1—C8	117.8 (3)	F2—C6—C7	119.1 (6)
C9—Sn1—C8	116.5 (3)	F2—C6—C5	118.3 (5)
C10—Sn1—O1	98.80 (19)	C7—C6—C5	122.7 (5)
C9—Sn1—O1	93.67 (19)	C6—C7—C2	119.3 (5)
C8—Sn1—O1	90.07 (19)	C6—C7—H7	120.3
C10—Sn1—O2ⁱ	84.63 (19)	C2—C7—H7	120.3
C9—Sn1—O2ⁱ	86.19 (18)	Sn1—C8—H8A	109.5
C8—Sn1—O2ⁱ	86.33 (19)	Sn1—C8—H8B	109.5
O1—Sn1—O2ⁱ	175.91 (13)	H8A—C8—H8B	109.5
C1—O1—Sn1	126.3 (3)	Sn1—C8—H8C	109.5
C1—O2—Sn1ⁱⁱ	155.9 (3)	H8A—C8—H8C	109.5
O2—C1—O1	124.4 (5)	H8B—C8—H8C	109.5
O2—C1—C2	121.4 (4)	Sn1—C9—H9A	109.5
O1—C1—C2	114.2 (4)	Sn1—C9—H9B	109.5
C7—C2—C3	119.5 (5)	H9A—C9—H9B	109.5
C7—C2—C1	120.8 (4)	Sn1—C9—H9C	109.5
C3—C2—C1	119.7 (4)	H9A—C9—H9C	109.5
C4—C3—C2	118.5 (5)	H9B—C9—H9C	109.5
C4—C3—H3	120.7	Sn1—C10—H10A	109.5
C2—C3—H3	120.7	Sn1—C10—H10B	109.5
F1—C4—C3	118.9 (5)	H10A—C10—H10B	109.5
F1—C4—C5	118.2 (5)	Sn1—C10—H10C	109.5
C3—C4—C5	122.9 (5)	H10A—C10—H10C	109.5
C6—C5—C4	117.0 (5)	H10B—C10—H10C	109.5
C6—C5—H5	121.5

C10—Sn1—O1—C1	59.5 (4)	C1—C2—C3—C4	178.5 (4)
C9—Sn1—O1—C1	−65.8 (4)	C2—C3—C4—F1	179.1 (4)
C8—Sn1—O1—C1	177.7 (4)	C2—C3—C4—C5	−2.2 (8)
Sn1ⁱⁱ—O2—C1—O1	133.6 (7)	F1—C4—C5—C6	−179.2 (5)
Sn1ⁱⁱ—O2—C1—C2	−46.9 (11)	C3—C4—C5—C6	2.0 (8)
Sn1—O1—C1—O2	−4.0 (7)	C4—C5—C6—F2	180.0 (5)
Sn1—O1—C1—C2	176.5 (3)	C4—C5—C6—C7	−0.1 (8)
O2—C1—C2—C7	−11.4 (7)	F2—C6—C7—C2	178.3 (4)
O1—C1—C2—C7	168.2 (4)	C5—C6—C7—C2	−1.6 (8)
O2—C1—C2—C3	170.6 (5)	C3—C2—C7—C6	1.5 (7)
O1—C1—C2—C3	−9.9 (6)	C1—C2—C7—C6	−176.6 (4)
C7—C2—C3—C4	0.4 (7)

Symmetry codes: (i) −x+1/2, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9C···F1ⁱⁱⁱ	0.96	2.62	3.470 (7)	148

Symmetry code: (iii) x, −y, z−1/2.

Experimental details

Crystal data
Chemical formula	[Sn(CH₃)₃(C₇H₃F₂O₂)]
M_r	320.89
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	298
a, b, c (Å)	13.1371 (12), 10.0847 (11), 18.9643 (19)
β (°)	101.864 (1)
V (Å³)	2458.8 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.08
Crystal size (mm)	0.50 × 0.42 × 0.40

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.422, 0.490
No. of measured, independent and observed [I > 2σ(I)] reflections	5945, 2165, 1725
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.073, 1.17
No. of reflections	2165
No. of parameters	140
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.76, −0.69

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C9—H9C···F1ⁱ	0.96	2.62	3.470 (7)	148

Symmetry code: (i) x, −y, z−1/2.

Acknowledgements

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

References

Duboy, S. K. & Roy, U. (2003). Appl. Organomet. Chem. 17, 3–8. Web of Science CrossRef Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar
Tiekink, E. R. T. (1994). J. Organomet. Chem. 1, 71–116. Google Scholar