metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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[Duboy, S. K. & Roy, U. (2003). Appl. Organomet. Chem. 17, 3-8.]). For related trimethyl carboxyl­ates with similar structures, see: Tiekink, (1994[Tiekink, E. R. T. (1994). J. Organomet. Chem. 1, 71-116.]).

[Scheme 1]

Experimental

Crystal data
  • [Sn(CH3)3(C7H3F2O2)]

  • Mr = 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[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.422, Tmax = 0.490

  • 5945 measured reflections

  • 2165 independent reflections

  • 1725 reflections with I > 2σ(I)

  • Rint = 0.034

Refinement
  • R[F2 > 2σ(F2)] = 0.032

  • wR(F2) = 0.073

  • S = 1.17

  • 2165 reflections

  • 140 parameters

  • H-atom parameters constrained

  • Δρmax = 0.76 e Å−3

  • Δρmin = −0.69 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Siemens, 1996[Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

The H atoms were positioned geometrically and refined using the riding model with C–H = 0.93 Å, for aromatic H, 0.96 Å for methyl H atoms. The Uiso parameters for H atoms were constraned to be 1.5Ueq of the carrier atom for the methyl H atoms and 1.2Ueq of the carrier atom for the remaining H atoms

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. ORTEP diagram of the title compound, with 50% probability displacement ellipsoids.
[Figure 2] 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
Mr = 320.89Dx = 1.734 Mg m3
Monoclinic, C2/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2ycCell parameters from 3905 reflections
a = 13.1371 (12) Åθ = 2.7–26.3°
b = 10.0847 (11) ŵ = 2.08 mm1
c = 18.9643 (19) ÅT = 298 K
β = 101.864 (1)°Block, colorless
V = 2458.8 (4) Å30.50 × 0.42 × 0.40 mm
Z = 8
Data collection top
Siemens SMART CCD area-detector
diffractometer
2165 independent reflections
Radiation source: fine-focus sealed tube1725 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.034
ϕ and ω scansθmax = 25.0°, θmin = 2.7°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1415
Tmin = 0.422, Tmax = 0.490k = 912
5945 measured reflectionsl = 2222
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)] = 0.032H-atom parameters constrained
wR(F2) = 0.073 w = 1/[σ2(Fo2) + (0.0148P)2 + 7.4343P]
where P = (Fo2 + 2Fc2)/3
S = 1.17(Δ/σ)max = 0.008
2165 reflectionsΔρmax = 0.76 e Å3
140 parametersΔρmin = 0.69 e Å3
0 restraintsExtinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.00219 (15)
Crystal data top
[Sn(CH3)3(C7H3F2O2)]V = 2458.8 (4) Å3
Mr = 320.89Z = 8
Monoclinic, C2/cMo Kα radiation
a = 13.1371 (12) ŵ = 2.08 mm1
b = 10.0847 (11) ÅT = 298 K
c = 18.9643 (19) Å0.50 × 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)
Tmin = 0.422, Tmax = 0.490Rint = 0.034
5945 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.073H-atom parameters constrained
S = 1.17Δρmax = 0.76 e Å3
2165 reflectionsΔρmin = 0.69 e Å3
140 parameters
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
Sn10.21709 (3)0.11988 (3)0.275296 (18)0.04976 (17)
O10.1757 (3)0.0218 (3)0.34840 (19)0.0620 (10)
O20.2446 (3)0.2018 (4)0.3102 (2)0.0664 (10)
F10.0238 (3)0.1709 (4)0.5259 (2)0.0939 (12)
F20.1732 (3)0.5409 (3)0.4910 (2)0.0944 (12)
C10.1945 (4)0.1461 (5)0.3495 (3)0.0483 (12)
C20.1503 (3)0.2219 (5)0.4043 (2)0.0431 (11)
C30.0816 (4)0.1598 (5)0.4403 (3)0.0523 (12)
H30.06130.07240.43000.063*
C40.0443 (4)0.2301 (6)0.4913 (3)0.0587 (14)
C50.0744 (4)0.3574 (6)0.5100 (3)0.0658 (15)
H50.04970.40240.54590.079*
C60.1422 (5)0.4153 (5)0.4736 (3)0.0623 (15)
C70.1796 (4)0.3514 (5)0.4209 (3)0.0539 (13)
H70.22430.39470.39640.065*
C80.1543 (6)0.2738 (6)0.3291 (4)0.094 (2)
H8A0.13350.34610.29640.141*
H8B0.09490.24120.34590.141*
H8C0.20590.30390.36930.141*
C90.1173 (4)0.0367 (6)0.1847 (3)0.0685 (16)
H9A0.15430.02920.16350.103*
H9B0.05870.00360.19940.103*
H9C0.09330.10510.15010.103*
C100.3794 (4)0.0930 (6)0.2996 (3)0.0766 (18)
H10A0.40730.11370.25800.115*
H10B0.40980.15050.33860.115*
H10C0.39510.00250.31340.115*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0557 (2)0.0429 (2)0.0565 (2)0.00350 (16)0.02496 (16)0.00374 (17)
O10.085 (3)0.044 (2)0.068 (2)0.0015 (18)0.040 (2)0.0038 (17)
O20.087 (3)0.059 (2)0.066 (2)0.0043 (19)0.046 (2)0.0052 (19)
F10.101 (3)0.099 (3)0.102 (3)0.009 (2)0.070 (2)0.014 (2)
F20.130 (3)0.058 (2)0.100 (3)0.002 (2)0.033 (2)0.0238 (19)
C10.055 (3)0.044 (3)0.048 (3)0.007 (2)0.017 (2)0.004 (2)
C20.042 (3)0.047 (3)0.042 (3)0.007 (2)0.013 (2)0.004 (2)
C30.056 (3)0.051 (3)0.053 (3)0.004 (2)0.018 (2)0.006 (2)
C40.058 (3)0.067 (4)0.056 (3)0.013 (3)0.025 (3)0.013 (3)
C50.077 (4)0.073 (4)0.052 (3)0.031 (3)0.023 (3)0.004 (3)
C60.075 (4)0.048 (3)0.062 (3)0.016 (3)0.011 (3)0.006 (3)
C70.060 (3)0.051 (3)0.054 (3)0.004 (2)0.018 (2)0.003 (2)
C80.145 (6)0.049 (3)0.118 (5)0.007 (4)0.097 (5)0.008 (4)
C90.056 (3)0.083 (4)0.066 (4)0.011 (3)0.013 (3)0.002 (3)
C100.058 (3)0.091 (5)0.078 (4)0.011 (3)0.007 (3)0.007 (3)
Geometric parameters (Å, º) top
Sn1—C102.104 (5)C4—C51.368 (7)
Sn1—C92.109 (5)C5—C61.365 (8)
Sn1—C82.115 (6)C5—H50.9300
Sn1—O12.137 (3)C6—C71.363 (7)
Sn1—O2i2.540 (4)C7—H70.9300
O1—C11.278 (6)C8—H8A0.9600
O2—C11.227 (6)C8—H8B0.9600
O2—Sn1ii2.540 (4)C8—H8C0.9600
F1—C41.353 (6)C9—H9A0.9600
F2—C61.351 (6)C9—H9B0.9600
C1—C21.500 (6)C9—H9C0.9600
C2—C71.379 (6)C10—H10A0.9600
C2—C31.389 (6)C10—H10B0.9600
C3—C41.368 (7)C10—H10C0.9600
C3—H30.9300
C10—Sn1—C9124.0 (2)C4—C5—H5121.5
C10—Sn1—C8117.8 (3)F2—C6—C7119.1 (6)
C9—Sn1—C8116.5 (3)F2—C6—C5118.3 (5)
C10—Sn1—O198.80 (19)C7—C6—C5122.7 (5)
C9—Sn1—O193.67 (19)C6—C7—C2119.3 (5)
C8—Sn1—O190.07 (19)C6—C7—H7120.3
C10—Sn1—O2i84.63 (19)C2—C7—H7120.3
C9—Sn1—O2i86.19 (18)Sn1—C8—H8A109.5
C8—Sn1—O2i86.33 (19)Sn1—C8—H8B109.5
O1—Sn1—O2i175.91 (13)H8A—C8—H8B109.5
C1—O1—Sn1126.3 (3)Sn1—C8—H8C109.5
C1—O2—Sn1ii155.9 (3)H8A—C8—H8C109.5
O2—C1—O1124.4 (5)H8B—C8—H8C109.5
O2—C1—C2121.4 (4)Sn1—C9—H9A109.5
O1—C1—C2114.2 (4)Sn1—C9—H9B109.5
C7—C2—C3119.5 (5)H9A—C9—H9B109.5
C7—C2—C1120.8 (4)Sn1—C9—H9C109.5
C3—C2—C1119.7 (4)H9A—C9—H9C109.5
C4—C3—C2118.5 (5)H9B—C9—H9C109.5
C4—C3—H3120.7Sn1—C10—H10A109.5
C2—C3—H3120.7Sn1—C10—H10B109.5
F1—C4—C3118.9 (5)H10A—C10—H10B109.5
F1—C4—C5118.2 (5)Sn1—C10—H10C109.5
C3—C4—C5122.9 (5)H10A—C10—H10C109.5
C6—C5—C4117.0 (5)H10B—C10—H10C109.5
C6—C5—H5121.5
C10—Sn1—O1—C159.5 (4)C1—C2—C3—C4178.5 (4)
C9—Sn1—O1—C165.8 (4)C2—C3—C4—F1179.1 (4)
C8—Sn1—O1—C1177.7 (4)C2—C3—C4—C52.2 (8)
Sn1ii—O2—C1—O1133.6 (7)F1—C4—C5—C6179.2 (5)
Sn1ii—O2—C1—C246.9 (11)C3—C4—C5—C62.0 (8)
Sn1—O1—C1—O24.0 (7)C4—C5—C6—F2180.0 (5)
Sn1—O1—C1—C2176.5 (3)C4—C5—C6—C70.1 (8)
O2—C1—C2—C711.4 (7)F2—C6—C7—C2178.3 (4)
O1—C1—C2—C7168.2 (4)C5—C6—C7—C21.6 (8)
O2—C1—C2—C3170.6 (5)C3—C2—C7—C61.5 (7)
O1—C1—C2—C39.9 (6)C1—C2—C7—C6176.6 (4)
C7—C2—C3—C40.4 (7)
Symmetry codes: (i) x+1/2, y1/2, z+1/2; (ii) x+1/2, y+1/2, z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C9—H9C···F1iii0.962.623.470 (7)148
Symmetry code: (iii) x, y, z1/2.

Experimental details

Crystal data
Chemical formula[Sn(CH3)3(C7H3F2O2)]
Mr320.89
Crystal system, space groupMonoclinic, C2/c
Temperature (K)298
a, b, c (Å)13.1371 (12), 10.0847 (11), 18.9643 (19)
β (°) 101.864 (1)
V3)2458.8 (4)
Z8
Radiation typeMo Kα
µ (mm1)2.08
Crystal size (mm)0.50 × 0.42 × 0.40
Data collection
DiffractometerSiemens SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.422, 0.490
No. of measured, independent and
observed [I > 2σ(I)] reflections
5945, 2165, 1725
Rint0.034
(sin θ/λ)max1)0.595
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.073, 1.17
No. of reflections2165
No. of parameters140
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
C9—H9C···F1i0.962.623.470 (7)148
Symmetry code: (i) x, y, z1/2.
 

Acknowledgements

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

References

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

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