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Acta Cryst. (2007). E63, m2035-m2036    [ doi:10.1107/S1600536807031030 ]

Di-[mu]3-oxo-bis([mu]2-2,3,4,5-tetrafluorobenzoato-[kappa]2O:O')bis(2,3,4,5-tetrafluorobenzoato-[kappa]O)tetrakis[dimethyltin(IV)]

L.-L. Qiu, J.-S. Sun, J.-K. Li and R.-F. Zhang

Abstract top

The title compound, [Sn4(CH3)8(C7HF4O2)4O2], was obtained from the reaction of the ligand 2,3,4,5-tetrafluorobenzoic acid and dimethyltin(IV) oxide. The Sn atom is five-coordinate and displays trigonal-bipyramidal geometry. The molecule is centrosymmetric about the Me4Sn2O2 core and molecules are linked by C-H...O and C-H...F intermolecular interactions.

Comment top

Organotin(IV) carboxylates form an important class of compounds and have received much interest in recent years, not only due to their intrinsic interest but owing to their varied applications. Some examples have found wide use as catalysts and stabilizers, and certain derivatives are used as biocides, as antifouling agents and as wood preservatives (Davies, 1997). In order to explore the impact of the structure on the properties of the complexes, as well as to analyze structure-activity relationships, a large number of organotin carboxylate complexes have been prepared and studied (Gielen, 2002). However, only few fluorinated ligands have been used in organotin complexes (Gielen et al., 1995). The 2,3,4,5-tetrafluorobenzoic acid is one of the most common ligands of this type, and herein, we report the structure of the title complex, {[(F4C6HCO2)(CH3)2Sn]2O]}2.

The molecule structure and the unit cell of the title complex is shown in Figs 1 and 2, respectively. The structure is centrosymmetric about a Me4Sn2O2 core. Two oxygen atoms of this unit are tridentate as they link three Sn centres, two endo-cyclic and one exo-cyclic. Pairs of Sn atoms are bridged by bidentate carboxylate ligands and the external Sn atoms have their coordination geometry completed by a monodentate carboxylate ligand.The tin atom geometries are similar and are based on a five-coordinated trigonal bipyramidal arrangement. The Sn—O bond lengths are Sn(1)—O(4) 2.275 (6) Å, Sn(1)—O(5) 2.293 (6)Å and Sn(2)—O(2) 2.200 (5) Å, which are close to the covalent radii of Sn and O (2.13 Å) (Bondi, 1964), showing the strong coordination interaction. The axis angles for the geometry are C(10)—Sn(1)—C(11) 142.9 (3)° and C(9)—Sn(2)—C(8) 146.5 (4)°, showing a large deviation.

Related literature top

Related examples have wide-ranging applications (Davies, 1997), and a large number of organotin carboxylate complexes have been reported (Gielen, 2002), though only a few fluorinated ligands have been used in organotin complexes (Gielen et al., 1995; Sun et al., 2007).

For related literature, see: Bondi (1964); Burrow et al. (1997).

Experimental top

All reagents and solvents were used as obtained without further purification. The reaction was carried out under N2 atmosphere. The 2,3,4,5-tetrafluorobenzoic acid (0.239 g, 1 mmol) and dimethyltin oxide (0.165 g, 1 mmol) were added to a solution of dry benzene (30 ml) in a Schlenk flash and stirred under reflux conditions 12 h at 353 K; then dimethyltin oxide (0.220 g, 1 mmol) was added. After cooling to the room temperature, the solution was filtered. The solvent was removed from the filtrate under vacuum, and the solid residue was recrystallized from diethyl ether; colorless crystals suitable for an X-ray diffraction study were obtained. Yield, 81%. m.p. 134–136 °C. Analysis, calculated for C36H28O10F16Sn4: C 30.90, H 2.02; found: C 30.72, H 2.26. The elemental analyses were performed with PERKIN ELMER MODEL 2400 SERIES II. The number of CCDC: 631570.

Refinement top

All H atoms were placed in idealized positions and constrained to ride on their parent atoms, with aromatic and methyl C—H distances of 0.93 Å and 0.96 Å, respectively. The Uiso(H) values were set at 1.2Ueq(C) for the aromatic and 1.5Ueq(C) for the methyl H atoms.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2001); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I) with atom numbering and with 30% probability displacement ellipsoids for non-H atoms.
[Figure 2] Fig. 2. The unit cell of the molecular structure.
Di-µ3-oxo-bis(µ2-2,3,4,5-tetrafluorobenzoato-κ2O:O')bis(2,3,4,5- tetrafluorobenzoato-κO)tetrakis[dimethyltin(IV)] top
Crystal data top
[Sn4(CH3)8(C7HF4O2)4O2]Z = 1
Mr = 1399.34F(000) = 668
Triclinic, P1Dx = 2.043 Mg m−3
Hall symbol: -P 1Mo Kα radiation, λ = 0.71073 Å
a = 7.6590 (9) ÅCell parameters from 2453 reflections
b = 11.1358 (13) Åθ = 2.8–26.7°
c = 14.6746 (17) ŵ = 2.29 mm−1
α = 107.634 (15)°T = 298 K
β = 100.296 (16)°Block, colourless
γ = 100.185 (16)°0.41 × 0.38 × 0.35 mm
V = 1137.4 (3) Å3
Data collection top
Bruker SMART CCD
diffractometer		3908 independent reflections
Radiation source: fine-focus sealed tube2795 reflections with I > 2σ(I)
graphiteRint = 0.034
φ and ω scansθmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		h = −9→7
Tmin = 0.454, Tmax = 0.502k = −12→13
5695 measured reflectionsl = −16→17
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.052Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.159H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0982P)2]
where P = (Fo2 + 2Fc2)/3
3908 reflections(Δ/σ)max < 0.001
286 parametersΔρmax = 2.05 e Å−3
49 restraintsΔρmin = −2.31 e Å−3
Crystal data top
[Sn4(CH3)8(C7HF4O2)4O2]γ = 100.185 (16)°
Mr = 1399.34V = 1137.4 (3) Å3
Triclinic, P1Z = 1
a = 7.6590 (9) ÅMo Kα radiation
b = 11.1358 (13) ŵ = 2.29 mm−1
c = 14.6746 (17) ÅT = 298 K
α = 107.634 (15)°0.41 × 0.38 × 0.35 mm
β = 100.296 (16)°
Data collection top
Bruker SMART CCD
diffractometer		3908 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2004)		2795 reflections with I > 2σ(I)
Tmin = 0.454, Tmax = 0.502Rint = 0.034
5695 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.052H-atom parameters constrained
wR(F2) = 0.159Δρmax = 2.05 e Å−3
S = 1.01Δρmin = −2.31 e Å−3
3908 reflectionsAbsolute structure: ?
286 parametersFlack parameter: ?
49 restraintsRogers parameter: ?
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
xyzUiso*/Ueq
Sn10.91008 (8)0.35427 (5)0.49974 (4)0.0401 (2)
Sn20.95074 (8)0.38429 (6)0.25786 (4)0.0410 (2)
O10.9747 (10)0.5044 (6)0.1239 (4)0.0672 (17)
O21.0227 (8)0.5943 (6)0.2837 (4)0.0514 (15)
O30.9703 (8)0.4488 (5)0.4047 (4)0.0435 (13)
O40.7690 (7)0.1671 (5)0.3715 (4)0.0401 (2)
O50.9078 (10)0.1726 (6)0.2520 (5)0.0646 (17)
F11.1574 (10)0.8538 (6)0.3612 (4)0.083 (2)
F21.2903 (10)1.0721 (6)0.3325 (5)0.093 (2)
F31.3077 (12)1.0710 (7)0.1490 (7)0.116 (3)
F41.1862 (14)0.8501 (8)−0.0062 (6)0.122 (3)
F50.6430 (12)−0.0636 (8)0.3815 (6)0.113 (3)
F60.5008 (9)−0.3119 (6)0.2845 (5)0.0814 (19)
F70.5109 (11)−0.4186 (6)0.0952 (6)0.104 (3)
F80.6718 (10)−0.2728 (7)0.0024 (4)0.097 (2)
C11.0236 (16)0.6013 (10)0.1976 (7)0.0672 (17)
C21.0997 (12)0.7292 (9)0.1896 (6)0.045 (2)
C31.1112 (15)0.7308 (10)0.0985 (8)0.064 (3)
H31.07010.65380.04460.076*
C41.1825 (17)0.8445 (12)0.0850 (9)0.072 (3)
C51.2464 (15)0.9593 (11)0.1635 (11)0.077 (4)
C61.2274 (14)0.9605 (10)0.2543 (8)0.063 (3)
C71.1614 (13)0.8462 (9)0.2689 (7)0.055 (2)
C81.2081 (14)0.3590 (10)0.2339 (8)0.066 (3)
H8A1.30100.40310.29440.099*
H8B1.23540.39440.18450.099*
H8C1.20480.26800.21190.099*
C90.6708 (14)0.3455 (12)0.1955 (8)0.087 (4)
H9A0.61190.38540.24500.130*
H9B0.61960.25320.16990.130*
H9C0.65210.37990.14300.130*
C101.1306 (15)0.2745 (12)0.5321 (8)0.074 (3)
H10A1.23020.30990.50880.110*
H10B1.09370.18180.50000.110*
H10C1.16920.29510.60210.110*
C110.6381 (12)0.3513 (10)0.5138 (7)0.056 (2)
H11A0.59210.41020.48550.085*
H11B0.63750.37740.58230.085*
H11C0.56180.26490.47980.085*
C120.8051 (12)0.1130 (9)0.2903 (7)0.049 (2)
C130.7312 (11)−0.0276 (8)0.2416 (6)0.041 (2)
C140.6521 (12)−0.1085 (10)0.2872 (6)0.050 (2)
C150.5775 (13)−0.2391 (9)0.2366 (8)0.056 (3)
C160.5824 (14)−0.2943 (10)0.1427 (7)0.060 (3)
C170.6605 (15)−0.2171 (11)0.0972 (7)0.067 (3)
C180.7351 (13)−0.0850 (10)0.1422 (7)0.052 (2)
H180.7863−0.03560.10830.063*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Sn10.0434 (4)0.0388 (4)0.0411 (3)0.0045 (3)0.0175 (3)0.0174 (3)
Sn20.0461 (4)0.0405 (4)0.0351 (3)0.0027 (3)0.0139 (3)0.0134 (3)
O10.093 (4)0.047 (3)0.052 (3)−0.005 (3)0.018 (3)0.016 (3)
O20.070 (4)0.049 (3)0.040 (3)0.009 (3)0.021 (3)0.020 (3)
O30.053 (3)0.041 (3)0.038 (3)0.003 (2)0.020 (2)0.016 (2)
O40.0434 (4)0.0388 (4)0.0411 (3)0.0045 (3)0.0175 (3)0.0174 (3)
O50.086 (4)0.049 (3)0.056 (3)0.003 (3)0.029 (3)0.016 (3)
F10.125 (6)0.064 (4)0.048 (3)0.008 (4)0.027 (3)0.008 (3)
F20.103 (5)0.044 (4)0.110 (6)0.001 (3)0.025 (4)0.005 (4)
F30.144 (7)0.058 (5)0.175 (8)0.015 (4)0.074 (6)0.066 (5)
F40.214 (10)0.087 (6)0.094 (5)0.029 (6)0.080 (6)0.054 (5)
F50.148 (8)0.101 (6)0.087 (5)0.009 (5)0.046 (5)0.030 (5)
F60.085 (4)0.063 (4)0.096 (5)−0.005 (3)0.022 (4)0.040 (4)
F70.115 (6)0.045 (4)0.109 (6)−0.008 (4)0.000 (4)−0.002 (4)
F80.109 (6)0.106 (6)0.053 (4)0.018 (4)0.021 (4)−0.003 (4)
C10.093 (4)0.047 (3)0.052 (3)−0.005 (3)0.018 (3)0.016 (3)
C20.046 (5)0.043 (5)0.044 (5)0.007 (4)0.010 (4)0.016 (4)
C30.086 (8)0.046 (6)0.059 (6)0.009 (5)0.024 (6)0.018 (5)
C40.094 (9)0.064 (8)0.082 (8)0.019 (6)0.047 (7)0.046 (7)
C50.071 (7)0.051 (7)0.135 (11)0.023 (6)0.042 (8)0.055 (8)
C60.066 (7)0.045 (6)0.081 (7)0.014 (5)0.032 (6)0.018 (6)
C70.056 (6)0.048 (6)0.065 (6)0.014 (5)0.019 (5)0.022 (5)
C80.068 (7)0.052 (6)0.090 (8)0.016 (5)0.044 (6)0.026 (6)
C90.065 (7)0.096 (10)0.082 (8)−0.013 (7)−0.002 (6)0.037 (7)
C100.077 (7)0.095 (9)0.080 (7)0.055 (7)0.035 (6)0.046 (7)
C110.041 (5)0.066 (7)0.057 (6)0.006 (5)0.015 (4)0.016 (5)
C120.043 (5)0.040 (5)0.073 (6)0.014 (4)0.028 (5)0.025 (5)
C130.039 (5)0.036 (5)0.046 (5)0.004 (4)0.010 (4)0.016 (4)
C140.048 (5)0.060 (6)0.040 (4)0.010 (4)0.007 (4)0.020 (4)
C150.047 (6)0.044 (6)0.074 (7)−0.001 (4)0.009 (5)0.025 (5)
C160.066 (7)0.038 (6)0.053 (6)0.005 (5)−0.006 (5)0.001 (5)
C170.073 (7)0.073 (8)0.036 (5)0.008 (6)0.008 (5)0.001 (5)
C180.056 (6)0.060 (6)0.043 (5)0.012 (5)0.011 (4)0.023 (5)
Geometric parameters (Å, °) top
Sn1—O32.053 (5)C3—C41.373 (14)
Sn1—O3i2.140 (6)C3—H30.9300
Sn1—O42.270 (5)C4—C51.374 (17)
Sn1—C102.090 (9)C5—C61.362 (15)
Sn1—C112.125 (9)C6—C71.378 (14)
Sn2—O22.202 (6)C8—H8A0.9600
Sn2—O32.022 (5)C8—H8B0.9600
Sn2—O52.295 (7)C8—H8C0.9600
Sn2—C82.115 (9)C9—H9A0.9600
Sn2—C92.086 (10)C9—H9B0.9600
O1—C11.216 (11)C9—H9C0.9600
O2—C11.291 (11)C10—H10A0.9600
O3—Sn1i2.140 (6)C10—H10B0.9600
O4—C121.265 (10)C10—H10C0.9600
O5—C121.255 (10)C11—H11A0.9600
F1—C71.337 (11)C11—H11B0.9600
F2—C61.350 (12)C11—H11C0.9600
F3—C51.342 (11)C12—C131.466 (12)
F4—C41.363 (12)C13—C141.394 (12)
F5—C141.341 (11)C13—C181.412 (12)
F6—C151.348 (11)C14—C151.376 (13)
F7—C161.309 (12)C15—C161.339 (14)
F8—C171.366 (11)C16—C171.361 (15)
C1—C21.488 (13)C17—C181.380 (14)
C2—C31.359 (12)C18—H180.9300
C2—C71.394 (13)
O3—Sn1—C10106.3 (3)F1—C7—C6117.1 (9)
O3—Sn1—C11110.2 (3)F1—C7—C2122.5 (8)
C10—Sn1—C11142.7 (4)C6—C7—C2120.4 (9)
O3—Sn1—O3i76.6 (2)Sn2—C8—H8A109.5
C10—Sn1—O3i98.8 (4)Sn2—C8—H8B109.5
C11—Sn1—O3i96.5 (3)H8A—C8—H8B109.5
O3—Sn1—O491.1 (2)Sn2—C8—H8C109.5
C10—Sn1—O489.5 (4)H8A—C8—H8C109.5
C11—Sn1—O482.8 (3)H8B—C8—H8C109.5
O3i—Sn1—O4166.7 (2)Sn2—C9—H9A109.5
O3—Sn1—Sn1i39.25 (15)Sn2—C9—H9B109.5
C10—Sn1—Sn1i106.0 (3)H9A—C9—H9B109.5
C11—Sn1—Sn1i106.8 (3)Sn2—C9—H9C109.5
O3i—Sn1—Sn1i37.36 (13)H9A—C9—H9C109.5
O4—Sn1—Sn1i130.19 (13)H9B—C9—H9C109.5
O3—Sn2—C9103.5 (4)Sn1—C10—H10A109.5
O3—Sn2—C8109.1 (4)Sn1—C10—H10B109.5
C8—Sn2—C9146.4 (5)H10A—C10—H10B109.5
O3—Sn2—O282.0 (2)Sn1—C10—H10C109.5
C9—Sn2—O298.5 (4)H10A—C10—H10C109.5
C8—Sn2—O293.8 (3)H10B—C10—H10C109.5
O3—Sn2—O591.7 (2)Sn1—C11—H11A109.5
C9—Sn2—O588.4 (4)Sn1—C11—H11B109.5
C8—Sn2—O582.9 (3)H11A—C11—H11B109.5
O2—Sn2—O5171.6 (2)Sn1—C11—H11C109.5
C1—O2—Sn2104.4 (6)H11A—C11—H11C109.5
Sn2—O3—Sn1132.2 (3)H11B—C11—H11C109.5
Sn2—O3—Sn1i124.2 (2)O5—C12—O4123.3 (8)
Sn1—O3—Sn1i103.4 (2)O5—C12—C13118.5 (8)
C12—O4—Sn1132.8 (5)O4—C12—C13118.1 (7)
C12—O5—Sn2129.0 (6)C14—C13—C18117.6 (8)
O1—C1—O2121.3 (9)C14—C13—C12123.6 (8)
O1—C1—C2119.4 (9)C18—C13—C12118.8 (8)
O2—C1—C2119.1 (9)F5—C14—C15116.6 (9)
C3—C2—C7118.2 (8)F5—C14—C13122.2 (9)
C3—C2—C1117.3 (8)C15—C14—C13121.2 (8)
C7—C2—C1124.4 (8)C16—C15—F6120.2 (9)
C2—C3—C4121.0 (10)C16—C15—C14121.5 (9)
C2—C3—H3119.5F6—C15—C14118.4 (9)
C4—C3—H3119.5F7—C16—C15121.0 (11)
F4—C4—C3122.2 (11)F7—C16—C17120.8 (10)
F4—C4—C5117.1 (10)C15—C16—C17118.2 (9)
C3—C4—C5120.7 (10)C16—C17—F8118.8 (10)
F3—C5—C6120.3 (12)C16—C17—C18123.8 (9)
F3—C5—C4120.3 (12)F8—C17—C18117.4 (10)
C6—C5—C4118.9 (9)C17—C18—C13117.8 (9)
F2—C6—C5119.8 (10)C17—C18—H18121.1
F2—C6—C7119.4 (10)C13—C18—H18121.1
C5—C6—C7120.4 (10)
Symmetry codes: (i) −x+2, −y+1, −z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1ii0.932.493.375 (12)160
C8—H8C···F3iii0.962.443.347 (14)159
C11—H11B···F6iv0.962.613.441 (11)145
Symmetry codes: (ii) −x+2, −y+1, −z; (iii) x, y−1, z; (iv) −x+1, −y, −z+1.
Table 1
Selected geometric parameters (Å, °) top
Sn1—O32.053 (5)Sn2—O22.202 (6)
Sn1—O3i2.140 (6)Sn2—O32.022 (5)
Sn1—O42.270 (5)Sn2—O52.295 (7)
C10—Sn1—C11142.7 (4)Sn2—O3—Sn1i124.2 (2)
C8—Sn2—C9146.4 (5)Sn1—O3—Sn1i103.4 (2)
Sn2—O3—Sn1132.2 (3)
Symmetry codes: (i) −x+2, −y+1, −z+1.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
C3—H3···O1ii0.932.493.375 (12)160
C8—H8C···F3iii0.962.443.347 (14)159
C11—H11B···F6iv0.962.613.441 (11)145
Symmetry codes: (ii) −x+2, −y+1, −z; (iii) x, y−1, z; (iv) −x+1, −y, −z+1.
Acknowledgements top

The authors thank the National Natural Science Foundation of China (20271025) for financial support.

references
References top

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