catena-Poly[[trimethyltin(IV)]-μ-2-methylbenzoato-κ2O:O′]

Danish, M.; Saleem, I.; Ahmad, N.; Starosta, W.; Leciejewicz, J.

doi:10.1107/S1600536809051587

metal-organic compounds

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Volume 66| Part 1| January 2010| Page m4

doi:10.1107/S1600536809051587

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catena-Poly[[trimethyltin(IV)]-μ-2-methylbenzoato-κ²O:O′]

Muhammad Danish,^a ^* Iram Saleem,^a Nazir Ahmad,^a Wojciech Starosta ^b and Janusz Leciejewicz ^b

^aDepartment of Chemistry, University of Sargodha, Sargodha 40100, Pakistan, and ^bInstitute of Nuclear Chemistry and Technology, ul. Dorodna 16, 03-195 Warszawa, Poland
^*Correspondence e-mail: drdanish62@gmail.com

(Received 26 November 2009; accepted 30 November 2009; online 4 December 2009)

The polymeric structure of the title compound, [Sn(CH₃)₃(C₈H₇O₂)]_n, is composed of zigzag chains in which the tin(IV) atoms, coordinated by three methyl groups, are bridged by toluene-2-carboxylate ligands via their O atoms. A slightly distorted trigonal-bipyramidal SnC₃O₂ coordination geometry arises for the metal, with the O atoms in the axial sites. Weak C—H⋯O hydrogen bonds help to stabilize the packing.

Related literature

For biological activity of tin complexes with carboxylate ligands, see, for example: Shahzadi et al. (2007 ). For a related structure, see: Danish et al. (2009 ). For a review of the structural chemistry of tin(IV) complexes with carboxylate ligands, see: Tiekink (1991 ).

Experimental

Crystal data

[Sn(CH₃)₃(C₈H₇O₂)]
M_r = 298.93
Monoclinic, P 2₁ /n
a = 10.618 (2) Å
b = 10.046 (2) Å
c = 12.833 (3) Å
β = 112.39 (3)°
V = 1265.7 (4) Å³
Z = 4
Mo Kα radiation
μ = 2.00 mm⁻¹
T = 293 K
0.42 × 0.12 × 0.09 mm

Data collection

Kuma KM-4 four circle diffractometer
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008 $[Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England]$ ) T_min = 0.838, T_max = 0.892
3389 measured reflections
3226 independent reflections
2090 reflections with I > 2σ(I)
R_int = 0.022
3 standard reflections every 200 reflections
intensity decay: 6.4%

Refinement

R[F² > 2σ(F²)] = 0.039
wR(F²) = 0.118
S = 1.04
3226 reflections
131 parameters
H-atom parameters constrained
Δρ_max = 1.37 e Å⁻³
Δρ_min = −1.69 e Å⁻³

Table 1
Selected bond lengths (Å)

Sn1—C11	2.108 (6)
Sn1—C12	2.112 (5)
Sn1—C13	2.116 (5)
Sn1—O2ⁱ	2.200 (3)
Sn1—O1	2.413 (3)
Symmetry code: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C13—H13C⋯O1ⁱ	0.96	2.66	3.271 (7)	122
C4—H4⋯O2ⁱⁱ	0.93	2.74	3.502 (6)	140
Symmetry codes: (i) $[-x+{\script{3\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{5\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: KM-4 Software (Kuma, 1996 $[Kuma (1996). KM-4 Software. Kuma Diffraction Ltd. Wrocław, Poland.]$ ); cell refinement: KM-4 Software; data reduction: DATAPROC (Kuma, 2001 $[Kuma (2001). DATAPROC. Kuma Diffraction Ltd. Wrocław, Poland.]$ ); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809051587/hb5258sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809051587/hb5258Isup2.hkl

checkCIF report

Comment top

The structure of the title compound (I) is built of zigzag molecular chains in which trimethyl-tin units are bridged by toluene-3-carboxylate ligand molecules via both their carboxylate O atoms (Fig.1). The toluene ring is planar [r.m.s. 0.0068 (2) Å]. The carboxylic group makes with it a dihedral angle of 77.8 (2)°. A catenated molecular pattern is formed as shown in Fig. 2. Three methyl groups and the tin ion are coplanar [r.m.s. 0.0459 (2) Å]. The metal ion is shifted from the plane by 0.0918 (2) Å. Methyl C atoms form an equatorial plane of a trigonal bipyramid with the bridging carboxylate O atoms at the apices above and below this plane. The chains are kept together by weak hydrogen bonds in which methyl C atoms act as donors and the carboxylate O atoms in the adjacent chains -as acceptors. Weak intra-chain hydrogen bonds are also observed. Geometrical parameters of hydrogen bonds are listed in Table 1.

Related literature top

For biological activity of tin complexes with carboxylate ligands, see, for example: Shahzadi et al. (2007). For a related structure, see: Danish et al. (2009). For a review of the structural chemistry of tin(IV) complexes with carboxylate ligands, see: Tiekink (1991).

Experimental top

0.01 mol of sodium ortho-toluate was suspended in 25 ml of dry chloroform contained in a round-bottom flask under argon; 0.01 mol of trimethyl-tin chloride was then added with constant stirring. The reacting mixtured was refluxed for 4 h under argon, cooled to room temperature and kept in an ice bath for 1 h. Sodium chloride formed during the reaction was removed by filtration. The filtrate was warmed with activated charcoal for 5 minutes, filtered through silica gel and concentrated to 10 ml. Crude crystals appeared in three days. Then, they were recrystalized from 3:1 chloroform/acetone mixture to yield colourless blocks of (I).

Computing details top

Data collection: KM-4 Software (Kuma, 1996); cell refinement: KM-4 Software (Kuma, 1996); data reduction: DATAPROC (Kuma, 2001); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. A structural unit of (1) with 50% probability displacement ellipsoids.
	Fig. 2. Packing diagram of the structure.

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

Crystal data top

[Sn(CH₃)₃(C₈H₇O₂)]	F(000) = 592
M_r = 298.93	D_x = 1.569 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 25 reflections
a = 10.618 (2) Å	θ = 6–15°
b = 10.046 (2) Å	µ = 2.00 mm⁻¹
c = 12.833 (3) Å	T = 293 K
β = 112.39 (3)°	Block, colourless
V = 1265.7 (4) Å³	0.42 × 0.12 × 0.09 mm
Z = 4

Data collection top

Kuma KM-4 four circle diffractometer	2090 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 30.1°, θ_min = 2.1°
profile data from ω/2θ scans	h = 0→13
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	k = −13→0
T_min = 0.838, T_max = 0.892	l = −17→15
3389 measured reflections	3 standard reflections every 200 reflections
3226 independent reflections	intensity decay: 6.4%

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)] = 0.039	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.0777P)² + 0.0604P] where P = (F_o² + 2F_c²)/3
3226 reflections	(Δ/σ)_max = 0.001
131 parameters	Δρ_max = 1.37 e Å⁻³
0 restraints	Δρ_min = −1.69 e Å⁻³

Crystal data top

[Sn(CH₃)₃(C₈H₇O₂)]	V = 1265.7 (4) Å³
M_r = 298.93	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.618 (2) Å	µ = 2.00 mm⁻¹
b = 10.046 (2) Å	T = 293 K
c = 12.833 (3) Å	0.42 × 0.12 × 0.09 mm
β = 112.39 (3)°

Data collection top

Kuma KM-4 four circle diffractometer	2090 reflections with I > 2σ(I)
Absorption correction: analytical (CrysAlis RED; Oxford Diffraction, 2008)	R_int = 0.022
T_min = 0.838, T_max = 0.892	3 standard reflections every 200 reflections
3389 measured reflections	intensity decay: 6.4%
3226 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.039	0 restraints
wR(F²) = 0.118	H-atom parameters constrained
S = 1.04	Δρ_max = 1.37 e Å⁻³
3226 reflections	Δρ_min = −1.69 e Å⁻³
131 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

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

	x	y	z	U_iso*/U_eq
Sn1	0.67213 (3)	0.58902 (3)	0.23186 (2)	0.04378 (12)
O1	0.8105 (3)	0.7804 (3)	0.2342 (4)	0.0645 (9)
C1	1.0203 (4)	0.7136 (4)	0.2204 (4)	0.0443 (8)
C7	0.9255 (4)	0.8130 (4)	0.2391 (3)	0.0429 (8)
C4	1.1974 (6)	0.5271 (6)	0.1924 (6)	0.0803 (17)
H4	1.2582	0.4665	0.1826	0.096*
C6	1.0906 (6)	0.6253 (6)	0.3062 (5)	0.0651 (13)
H6	1.0792	0.6290	0.3745	0.078*
C5	1.1780 (6)	0.5310 (7)	0.2904 (6)	0.0803 (17)
H5	1.2230	0.4707	0.3475	0.096*
C2	1.0385 (5)	0.7088 (5)	0.1204 (4)	0.0632 (12)
C3	1.1262 (7)	0.6142 (7)	0.1067 (6)	0.0825 (19)
H3	1.1374	0.6092	0.0383	0.099*
C8	0.9607 (9)	0.8037 (9)	0.0242 (6)	0.110 (3)
H8A	0.8646	0.7885	0.0011	0.165*
H8B	0.9873	0.7881	−0.0384	0.165*
H8C	0.9813	0.8940	0.0494	0.165*
O2	0.9682 (3)	0.9314 (3)	0.2610 (3)	0.0527 (7)
C12	0.5145 (5)	0.7309 (5)	0.1961 (6)	0.0780 (17)
H12A	0.5492	0.8098	0.2399	0.117*
H12B	0.4420	0.6947	0.2147	0.117*
H12C	0.4804	0.7529	0.1173	0.117*
C13	0.7115 (6)	0.5114 (6)	0.0940 (4)	0.0725 (15)
H13A	0.8034	0.5321	0.1031	0.109*
H13B	0.6495	0.5504	0.0253	0.109*
H13C	0.6994	0.4166	0.0909	0.109*
C11	0.7997 (7)	0.5631 (6)	0.4027 (5)	0.0814 (18)
H11A	0.8469	0.6448	0.4318	0.122*
H11B	0.8646	0.4940	0.4090	0.122*
H11C	0.7456	0.5388	0.4450	0.122*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.04404 (18)	0.03127 (16)	0.05657 (19)	0.00215 (11)	0.01979 (13)	−0.00013 (11)
O1	0.0526 (18)	0.0341 (15)	0.118 (3)	−0.0025 (13)	0.0456 (18)	−0.0094 (17)
C1	0.0366 (18)	0.0333 (18)	0.063 (2)	−0.0039 (15)	0.0193 (17)	−0.0053 (16)
C7	0.045 (2)	0.0317 (18)	0.053 (2)	0.0008 (15)	0.0201 (17)	−0.0006 (16)
C4	0.057 (3)	0.063 (4)	0.122 (5)	0.017 (3)	0.036 (3)	−0.016 (3)
C6	0.061 (3)	0.059 (3)	0.072 (3)	0.018 (2)	0.022 (2)	0.006 (2)
C5	0.063 (3)	0.062 (4)	0.108 (5)	0.024 (3)	0.024 (3)	0.009 (3)
C2	0.066 (3)	0.059 (3)	0.073 (3)	0.012 (2)	0.036 (3)	0.006 (2)
C3	0.079 (4)	0.088 (4)	0.100 (5)	0.011 (3)	0.056 (4)	−0.015 (4)
C8	0.146 (7)	0.121 (6)	0.083 (4)	0.050 (5)	0.067 (4)	0.033 (4)
O2	0.0473 (17)	0.0323 (15)	0.082 (2)	−0.0026 (11)	0.0282 (16)	−0.0035 (13)
C12	0.055 (3)	0.043 (2)	0.135 (5)	0.003 (2)	0.034 (3)	0.017 (3)
C13	0.099 (4)	0.063 (3)	0.067 (3)	−0.021 (3)	0.044 (3)	−0.015 (3)
C11	0.084 (4)	0.087 (4)	0.055 (3)	−0.026 (3)	0.006 (3)	0.001 (3)

Geometric parameters (Å, º) top

Sn1—C11	2.108 (6)	C2—C3	1.388 (7)
Sn1—C12	2.112 (5)	C2—C8	1.530 (8)
Sn1—C13	2.116 (5)	C3—H3	0.9300
Sn1—O2ⁱ	2.200 (3)	C8—H8A	0.9600
Sn1—O1	2.413 (3)	C8—H8B	0.9600
O1—C7	1.243 (5)	C8—H8C	0.9600
C1—C2	1.370 (7)	O2—Sn1ⁱⁱ	2.200 (3)
C1—C6	1.389 (7)	C12—H12A	0.9600
C1—C7	1.500 (5)	C12—H12B	0.9600
C7—O2	1.266 (5)	C12—H12C	0.9600
C4—C5	1.351 (10)	C13—H13A	0.9600
C4—C3	1.383 (10)	C13—H13B	0.9600
C4—H4	0.9300	C13—H13C	0.9600
C6—C5	1.394 (8)	C11—H11A	0.9600
C6—H6	0.9300	C11—H11B	0.9600
C5—H5	0.9300	C11—H11C	0.9600

C11—Sn1—C12	116.8 (3)	C4—C3—C2	121.5 (6)
C11—Sn1—C13	124.8 (3)	C4—C3—H3	119.3
C12—Sn1—C13	117.3 (3)	C2—C3—H3	119.3
C11—Sn1—O2ⁱ	92.6 (2)	C2—C8—H8A	109.5
C12—Sn1—O2ⁱ	90.09 (17)	C2—C8—H8B	109.5
C13—Sn1—O2ⁱ	97.02 (17)	H8A—C8—H8B	109.5
C11—Sn1—O1	86.5 (2)	C2—C8—H8C	109.5
C12—Sn1—O1	83.88 (17)	H8A—C8—H8C	109.5
C13—Sn1—O1	89.46 (17)	H8B—C8—H8C	109.5
O2ⁱ—Sn1—O1	172.68 (11)	C7—O2—Sn1ⁱⁱ	119.7 (3)
C7—O1—Sn1	142.4 (3)	Sn1—C12—H12A	109.5
C2—C1—C6	119.6 (4)	Sn1—C12—H12B	109.5
C2—C1—C7	121.0 (4)	H12A—C12—H12B	109.5
C6—C1—C7	119.3 (4)	Sn1—C12—H12C	109.5
O1—C7—O2	121.4 (4)	H12A—C12—H12C	109.5
O1—C7—C1	121.5 (3)	H12B—C12—H12C	109.5
O2—C7—C1	117.1 (4)	Sn1—C13—H13A	109.5
C5—C4—C3	119.4 (5)	Sn1—C13—H13B	109.5
C5—C4—H4	120.3	H13A—C13—H13B	109.5
C3—C4—H4	120.3	Sn1—C13—H13C	109.5
C1—C6—C5	120.4 (6)	H13A—C13—H13C	109.5
C1—C6—H6	119.8	H13B—C13—H13C	109.5
C5—C6—H6	119.8	Sn1—C11—H11A	109.5
C4—C5—C6	120.1 (6)	Sn1—C11—H11B	109.5
C4—C5—H5	120.0	H11A—C11—H11B	109.5
C6—C5—H5	120.0	Sn1—C11—H11C	109.5
C1—C2—C3	119.0 (5)	H11A—C11—H11C	109.5
C1—C2—C8	120.6 (5)	H11B—C11—H11C	109.5
C3—C2—C8	120.4 (6)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13C···O1ⁱ	0.96	2.66	3.271 (7)	122
C4—H4···O2ⁱⁱⁱ	0.93	2.74	3.502 (6)	140

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (iii) −x+5/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Sn(CH₃)₃(C₈H₇O₂)]
M_r	298.93
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	10.618 (2), 10.046 (2), 12.833 (3)
β (°)	112.39 (3)
V (Å³)	1265.7 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	2.00
Crystal size (mm)	0.42 × 0.12 × 0.09

Data collection
Diffractometer	Kuma KM-4 four circle diffractometer
Absorption correction	Analytical (CrysAlis RED; Oxford Diffraction, 2008)
T_min, T_max	0.838, 0.892
No. of measured, independent and observed [I > 2σ(I)] reflections	3389, 3226, 2090
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.705

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.039, 0.118, 1.04
No. of reflections	3226
No. of parameters	131
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.37, −1.69

Computer programs: KM-4 Software (Kuma, 1996), DATAPROC (Kuma, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Sn1—C11	2.108 (6)	Sn1—O2ⁱ	2.200 (3)
Sn1—C12	2.112 (5)	Sn1—O1	2.413 (3)
Sn1—C13	2.116 (5)

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C13—H13C···O1ⁱ	0.96	2.66	3.271 (7)	122
C4—H4···O2ⁱⁱ	0.93	2.74	3.502 (6)	140

Symmetry codes: (i) −x+3/2, y−1/2, −z+1/2; (ii) −x+5/2, y−1/2, −z+1/2.

References

Danish, M., Tahir, M. N., Ahmad, N., Raza, A. R. & Ibrahim, M. (2009). Acta Cryst. E65, m609–m610. Web of Science CSD CrossRef IUCr Journals Google Scholar
Kuma (1996). KM-4 Software. Kuma Diffraction Ltd. Wrocław, Poland. Google Scholar
Kuma (2001). DATAPROC. Kuma Diffraction Ltd. Wrocław, Poland. Google Scholar
Oxford Diffraction (2008). CrysAlis RED. Oxford Diffraction Ltd, Abingdon, Oxfordshire, England Google Scholar
Shahzadi, S., Shahid, K. & Ali, S. (2007). Russ. J. Coord. Chem. 33, 403–411. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tiekink, E. R. T. (1991). Appl. Organomet. Chem. 5, 1–23. CrossRef CAS Web of Science Google Scholar

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doi:10.1107/S1600536809051587

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