catena-Poly[[trimethyl­tin(IV)]-μ-2,5-difluoro­benzoato-κ2O:O′]

Wen, L.; Yin, H.; Li, W.; Wang, D.

doi:10.1107/S1600536808040774

metal-organic compounds

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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page m29

doi:10.1107/S1600536808040774

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catena-Poly[[trimethyltin(IV)]-μ-2,5-difluorobenzoato-κ²O:O′]

Liyuan Wen,^a Handong Yin,^a ^* Wenkuan Li ^a and Daqi Wang ^a

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

(Received 12 November 2008; accepted 3 December 2008; online 10 December 2008)

In the title polymeric coordination compound, [Sn(CH₃)₃(C₇H₃F₂O₂)]_n, the Sn atom exhibits a distorted trigonal-bipyramidal coordination geometry with the carboxylate O atoms in the axial positions and the equatorial positions occupied by the methyl groups. The two Sn—O bond lengths are 2.225 (5) and 2.410 (6) Å.

Related literature

For a related structure, see: Wang et al. (2007 ).

Experimental

Crystal data

[Sn(CH₃)₃(C₇H₃F₂O₂)]
M_r = 320.91
Tetragonal, P 4₃ 2₁ 2
a = 9.8857 (9) Å
c = 24.896 (2) Å
V = 2433.0 (4) Å³
Z = 8
Mo Kα radiation
μ = 2.11 mm⁻¹
T = 298 (2) K
0.38 × 0.29 × 0.27 mm

Data collection

Siemens SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.502, T_max = 0.600 (expected range = 0.474–0.566)
10078 measured reflections
2152 independent reflections
1996 reflections with I > 2σ(I)
R_int = 0.034

Refinement

R[F² > 2σ(F²)] = 0.036
wR(F²) = 0.107
S = 1.00
2152 reflections
136 parameters
H-atom parameters constrained
Δρ_max = 0.54 e Å⁻³
Δρ_min = −0.46 e Å⁻³
Absolute structure: Flack (1983 ), 830 Friedel pairs
Flack parameter: −0.01 (8)

Table 1
Selected geometric parameters (Å, °)

Sn1—C9	2.103 (9)
Sn1—C10	2.110 (8)
Sn1—C8	2.118 (7)
Sn1—O1	2.225 (5)
Sn1—O2ⁱ	2.410 (6)

O1—Sn1—O2ⁱ	174.15 (19)
Symmetry code: (i) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+{\script{1\over 4}}]$ .

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/S1600536808040774/gk2177sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808040774/gk2177Isup2.hkl

checkCIF report

Comment top

In recent years the organotin derivatives have attracted considerable attention due to a significant antimicrobial properties as well as antitumor activities. Studies on organotin complexes containing carboxylate ligands with an additional donor atom (e.g N, S or F) that is available for coordinating to Sn atom have revealed that new structural types may lead to different activities. 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 Sn atom, assumes a distorted trigonal bipyramidal coordination geometry, provided by three methyl groups at the equatorial positions and two carboxylate groups at the axial positions. The Sn—O bond lengths in the compound (Table 1), are similar to those found in related organotin carboxylates (Wang et al., 2007). In the crystal packing, molecules are linked by intermolecular C—H···F hydrogen bonds (Fig.2, Table 1,)

Related literature top

For a related structure, see: Wang et al. (2007).

Experimental top

The reaction was carried out under nitrogen atmosphere. 2,5-Difluorobenzoic acid (1 mmol) and sodium ethoxide (1.2 mmol) were added to a stirred solution of benzene (30 ml) in a Schlenk flask and stirred for 0.5 h. Trimethyltin chloride (1 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. The product was crystallized from dichloromethane/methanol (1:1) to yield colourless block crystals (yield 83%. m.p.393K). Anal. Calcd (%) for C₁₀H₁₂F₂O₂Sn(Mr = 320.91): C, 37.43; H, 3.77; F, 11.84; Sn, 36.99. Found (%): C, 37.39; H, 3.86; F, 11.78; Sn, 36.89.

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. The molecular structure of the compound, showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity. Symmetry codes: (A) = x - 1/2,-y + 3/2,-z + 1/4, (B) = x + 1/2,-y + 3/2,-z + 1/4

catena-Poly[[trimethyltin(IV)]-µ-2,5-difluorobenzoato-κ²O:O'] top

Crystal data top

[Sn(CH₃)₃(C₇H₃F₂O₂)]	D_x = 1.752 Mg m⁻³
M_r = 320.91	Mo Kα radiation, λ = 0.71073 Å
Tetragonal, P4₃2₁2	Cell parameters from 5675 reflections
Hall symbol: P 4nw 2abw	θ = 2.2–26.4°
a = 9.8857 (9) Å	µ = 2.11 mm⁻¹
c = 24.896 (2) Å	T = 298 K
V = 2433.0 (4) Å³	Block, colourless
Z = 8	0.38 × 0.29 × 0.27 mm
F(000) = 1248

Data collection top

Siemens SMART CCD diffractometer	2152 independent reflections
Radiation source: fine-focus sealed tube	1996 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.034
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→11
T_min = 0.502, T_max = 0.600	k = −11→7
10078 measured reflections	l = −16→29

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)] = 0.036	H-atom parameters constrained
wR(F²) = 0.107	w = 1/[σ²(F_o²) + (0.066P)² + 4.861P] where P = (F_o² + 2F_c²)/3
S = 1.00	(Δ/σ)_max < 0.001
2152 reflections	Δρ_max = 0.54 e Å⁻³
136 parameters	Δρ_min = −0.46 e Å⁻³
0 restraints	Absolute structure: Flack (1983)
Primary atom site location: structure-invariant direct methods	Absolute structure parameter: −0.01 (8)

Crystal data top

[Sn(CH₃)₃(C₇H₃F₂O₂)]	Z = 8
M_r = 320.91	Mo Kα radiation
Tetragonal, P4₃2₁2	µ = 2.11 mm⁻¹
a = 9.8857 (9) Å	T = 298 K
c = 24.896 (2) Å	0.38 × 0.29 × 0.27 mm
V = 2433.0 (4) Å³

Data collection top

Siemens SMART CCD diffractometer	2152 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1996 reflections with I > 2σ(I)
T_min = 0.502, T_max = 0.600	R_int = 0.034
10078 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.036	H-atom parameters constrained
wR(F²) = 0.107	Δρ_max = 0.54 e Å⁻³
S = 1.00	Δρ_min = −0.46 e Å⁻³
2152 reflections	Absolute structure: Flack (1983)
136 parameters	Absolute structure parameter: −0.01 (8)
0 restraints

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

	x	y	z	U_iso*/U_eq
Sn1	0.79786 (5)	0.82634 (5)	0.11522 (2)	0.05163 (18)
F1	1.1717 (7)	1.1333 (7)	0.1597 (3)	0.111 (2)
F2	1.4123 (8)	1.0943 (8)	−0.0335 (3)	0.131 (3)
O1	0.9583 (5)	0.9696 (5)	0.0890 (2)	0.0632 (14)
O2	1.1085 (6)	0.8095 (6)	0.1065 (3)	0.0786 (18)
C1	1.0763 (7)	0.9249 (7)	0.0922 (3)	0.0552 (19)
C2	1.1900 (8)	1.0242 (7)	0.0773 (3)	0.0561 (18)
C3	1.2313 (10)	1.1239 (11)	0.1101 (4)	0.080 (3)
C4	1.3367 (11)	1.2144 (9)	0.0992 (5)	0.089 (3)
H4	1.3649	1.2787	0.1240	0.107*
C5	1.3953 (9)	1.2021 (11)	0.0498 (5)	0.082 (3)
H5	1.4635	1.2615	0.0395	0.098*
C6	1.3539 (10)	1.1028 (11)	0.0153 (4)	0.081 (3)
C7	1.2516 (10)	1.0141 (11)	0.0269 (4)	0.078 (3)
H7	1.2240	0.9495	0.0020	0.093*
C8	0.6502 (9)	0.9694 (8)	0.0912 (3)	0.067 (2)
H8A	0.6849	1.0227	0.0621	0.100*
H8B	0.6287	1.0274	0.1210	0.100*
H8C	0.5700	0.9229	0.0797	0.100*
C9	0.8458 (10)	0.6721 (11)	0.0603 (4)	0.081 (3)
H9A	0.7645	0.6261	0.0497	0.122*
H9B	0.9065	0.6088	0.0769	0.122*
H9C	0.8882	0.7108	0.0292	0.122*
C10	0.8626 (9)	0.8328 (10)	0.1959 (3)	0.070 (2)
H10A	0.9112	0.7514	0.2043	0.105*
H10B	0.7854	0.8405	0.2191	0.105*
H10C	0.9207	0.9095	0.2011	0.105*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0368 (3)	0.0477 (3)	0.0704 (3)	0.0054 (2)	−0.0009 (2)	0.0029 (2)
F1	0.121 (6)	0.108 (5)	0.103 (4)	−0.027 (4)	0.039 (4)	−0.022 (4)
F2	0.138 (6)	0.136 (6)	0.120 (5)	0.010 (5)	0.067 (5)	0.039 (4)
O1	0.040 (3)	0.047 (3)	0.102 (4)	0.009 (2)	0.009 (3)	0.020 (3)
O2	0.054 (3)	0.054 (3)	0.128 (5)	0.005 (3)	−0.001 (3)	0.029 (4)
C1	0.031 (3)	0.047 (4)	0.087 (5)	−0.004 (3)	0.012 (3)	0.014 (4)
C2	0.033 (3)	0.046 (4)	0.089 (5)	0.005 (3)	0.003 (4)	0.015 (4)
C3	0.063 (6)	0.083 (7)	0.094 (7)	0.012 (5)	0.020 (5)	0.004 (6)
C4	0.100 (8)	0.048 (5)	0.119 (8)	−0.007 (5)	0.014 (6)	0.007 (5)
C5	0.046 (5)	0.067 (6)	0.133 (9)	0.001 (5)	0.013 (5)	0.035 (6)
C6	0.058 (5)	0.087 (7)	0.099 (7)	0.012 (5)	0.025 (5)	0.039 (6)
C7	0.067 (6)	0.089 (7)	0.077 (6)	0.006 (5)	0.011 (5)	0.026 (5)
C8	0.062 (5)	0.050 (5)	0.088 (5)	0.013 (4)	−0.004 (4)	0.007 (4)
C9	0.074 (6)	0.092 (7)	0.078 (6)	0.025 (6)	−0.012 (5)	−0.009 (5)
C10	0.068 (5)	0.074 (6)	0.068 (5)	0.008 (4)	−0.003 (4)	−0.004 (4)

Geometric parameters (Å, º) top

Sn1—C9	2.103 (9)	C4—H4	0.9300
Sn1—C10	2.110 (8)	C5—C6	1.366 (15)
Sn1—C8	2.118 (7)	C5—H5	0.9300
Sn1—O1	2.225 (5)	C6—C7	1.369 (14)
Sn1—O2ⁱ	2.410 (6)	C7—H7	0.9300
F1—C3	1.373 (11)	C8—H8A	0.9600
F2—C6	1.349 (11)	C8—H8B	0.9600
O1—C1	1.250 (9)	C8—H8C	0.9600
O2—C1	1.237 (9)	C9—H9A	0.9600
O2—Sn1ⁱⁱ	2.410 (6)	C9—H9B	0.9600
C1—C2	1.537 (10)	C9—H9C	0.9600
C2—C3	1.344 (13)	C10—H10A	0.9600
C2—C7	1.399 (12)	C10—H10B	0.9600
C3—C4	1.399 (14)	C10—H10C	0.9600
C4—C5	1.365 (14)

C9—Sn1—C10	125.0 (4)	C6—C5—H5	119.9
C9—Sn1—C8	117.1 (4)	F2—C6—C5	118.8 (10)
C10—Sn1—C8	117.2 (3)	F2—C6—C7	117.7 (11)
C9—Sn1—O1	96.3 (3)	C5—C6—C7	123.4 (10)
C10—Sn1—O1	92.5 (3)	C6—C7—C2	117.7 (11)
C8—Sn1—O1	89.1 (3)	C6—C7—H7	121.2
C9—Sn1—O2ⁱ	87.8 (3)	C2—C7—H7	121.2
C10—Sn1—O2ⁱ	88.5 (3)	Sn1—C8—H8A	109.5
C8—Sn1—O2ⁱ	85.4 (3)	Sn1—C8—H8B	109.5
O1—Sn1—O2ⁱ	174.15 (19)	H8A—C8—H8B	109.5
C1—O1—Sn1	114.9 (4)	Sn1—C8—H8C	109.5
C1—O2—Sn1ⁱⁱ	142.9 (5)	H8A—C8—H8C	109.5
O2—C1—O1	125.8 (6)	H8B—C8—H8C	109.5
O2—C1—C2	118.1 (6)	Sn1—C9—H9A	109.5
O1—C1—C2	116.2 (6)	Sn1—C9—H9B	109.5
C3—C2—C7	117.7 (8)	H9A—C9—H9B	109.5
C3—C2—C1	123.0 (8)	Sn1—C9—H9C	109.5
C7—C2—C1	119.3 (8)	H9A—C9—H9C	109.5
C2—C3—F1	117.8 (9)	H9B—C9—H9C	109.5
C2—C3—C4	125.3 (9)	Sn1—C10—H10A	109.5
F1—C3—C4	116.8 (10)	Sn1—C10—H10B	109.5
C5—C4—C3	115.7 (10)	H10A—C10—H10B	109.5
C5—C4—H4	122.1	Sn1—C10—H10C	109.5
C3—C4—H4	122.1	H10A—C10—H10C	109.5
C4—C5—C6	120.1 (9)	H10B—C10—H10C	109.5
C4—C5—H5	119.9

C9—Sn1—O1—C1	−58.5 (6)	C1—C2—C3—F1	2.4 (13)
C10—Sn1—O1—C1	67.1 (6)	C7—C2—C3—C4	−3.8 (15)
C8—Sn1—O1—C1	−175.6 (7)	C1—C2—C3—C4	178.1 (9)
Sn1ⁱⁱ—O2—C1—O1	−166.0 (7)	C2—C3—C4—C5	3.6 (16)
Sn1ⁱⁱ—O2—C1—C2	13.5 (15)	F1—C3—C4—C5	179.3 (8)
Sn1—O1—C1—O2	2.8 (12)	C3—C4—C5—C6	−2.5 (15)
Sn1—O1—C1—C2	−176.8 (5)	C4—C5—C6—F2	179.0 (9)
O2—C1—C2—C3	−103.1 (10)	C4—C5—C6—C7	2.0 (16)
O1—C1—C2—C3	76.4 (11)	F2—C6—C7—C2	−179.2 (8)
O2—C1—C2—C7	78.8 (11)	C5—C6—C7—C2	−2.1 (15)
O1—C1—C2—C7	−101.7 (9)	C3—C2—C7—C6	2.9 (13)
C7—C2—C3—F1	−179.5 (8)	C1—C2—C7—C6	−178.9 (8)

Symmetry codes: (i) x−1/2, −y+3/2, −z+1/4; (ii) x+1/2, −y+3/2, −z+1/4.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C5—H5···F1ⁱⁱⁱ	0.93	2.63	3.336 (13)	133

Symmetry code: (iii) x+1/2, −y+5/2, −z+1/4.

Experimental details

Crystal data
Chemical formula	[Sn(CH₃)₃(C₇H₃F₂O₂)]
M_r	320.91
Crystal system, space group	Tetragonal, P4₃2₁2
Temperature (K)	298
a, c (Å)	9.8857 (9), 24.896 (2)
V (Å³)	2433.0 (4)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	2.11
Crystal size (mm)	0.38 × 0.29 × 0.27

Data collection
Diffractometer	Siemens SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.502, 0.600
No. of measured, independent and observed [I > 2σ(I)] reflections	10078, 2152, 1996
R_int	0.034
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.036, 0.107, 1.00
No. of reflections	2152
No. of parameters	136
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.54, −0.46
Absolute structure	Flack (1983)
Absolute structure parameter	−0.01 (8)

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

Selected geometric parameters (Å, º) top

Sn1—C9	2.103 (9)	Sn1—O1	2.225 (5)
Sn1—C10	2.110 (8)	Sn1—O2ⁱ	2.410 (6)
Sn1—C8	2.118 (7)

O1—Sn1—O2ⁱ	174.15 (19)

Symmetry code: (i) x−1/2, −y+3/2, −z+1/4.

Acknowledgements

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

References

Flack, H. D. (1983). Acta Cryst. A39, 876–881. CrossRef CAS Web of Science IUCr Journals 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
Wang, H., Yin, H. & Wang, D. (2007). Acta Cryst. E63, m2958. Web of Science CSD CrossRef IUCr Journals Google Scholar