Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031030/gg2018sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031030/gg2018Isup2.hkl |
CCDC reference: 631570
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.
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.
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 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).
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.
Fig. 1. The molecular structure of (I) with atom numbering and with 30% probability displacement ellipsoids for non-H atoms. | |
Fig. 2. The unit cell of the molecular structure. |
[Sn4(CH3)8(C7HF4O2)4O2] | Z = 1 |
Mr = 1399.34 | F(000) = 668 |
Triclinic, P1 | Dx = 2.043 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.6590 (9) Å | Cell parameters from 2453 reflections |
b = 11.1358 (13) Å | θ = 2.8–26.7° |
c = 14.6746 (17) Å | µ = 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 |
Bruker SMART CCD diffractometer | 3908 independent reflections |
Radiation source: fine-focus sealed tube | 2795 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.034 |
φ and ω scans | θmax = 25.0°, θmin = 2.0° |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | h = −9→7 |
Tmin = 0.454, Tmax = 0.502 | k = −12→13 |
5695 measured reflections | l = −16→17 |
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)] = 0.052 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.159 | H-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 parameters | Δρmax = 2.05 e Å−3 |
49 restraints | Δρmin = −2.31 e Å−3 |
[Sn4(CH3)8(C7HF4O2)4O2] | γ = 100.185 (16)° |
Mr = 1399.34 | V = 1137.4 (3) Å3 |
Triclinic, P1 | Z = 1 |
a = 7.6590 (9) Å | Mo Kα radiation |
b = 11.1358 (13) Å | µ = 2.29 mm−1 |
c = 14.6746 (17) Å | T = 298 K |
α = 107.634 (15)° | 0.41 × 0.38 × 0.35 mm |
β = 100.296 (16)° |
Bruker SMART CCD diffractometer | 3908 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2004) | 2795 reflections with I > 2σ(I) |
Tmin = 0.454, Tmax = 0.502 | Rint = 0.034 |
5695 measured reflections |
R[F2 > 2σ(F2)] = 0.052 | 49 restraints |
wR(F2) = 0.159 | H-atom parameters constrained |
S = 1.01 | Δρmax = 2.05 e Å−3 |
3908 reflections | Δρmin = −2.31 e Å−3 |
286 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
Sn1 | 0.91008 (8) | 0.35427 (5) | 0.49974 (4) | 0.0401 (2) | |
Sn2 | 0.95074 (8) | 0.38429 (6) | 0.25786 (4) | 0.0410 (2) | |
O1 | 0.9747 (10) | 0.5044 (6) | 0.1239 (4) | 0.0672 (17) | |
O2 | 1.0227 (8) | 0.5943 (6) | 0.2837 (4) | 0.0514 (15) | |
O3 | 0.9703 (8) | 0.4488 (5) | 0.4047 (4) | 0.0435 (13) | |
O4 | 0.7690 (7) | 0.1671 (5) | 0.3715 (4) | 0.0401 (2) | |
O5 | 0.9078 (10) | 0.1726 (6) | 0.2520 (5) | 0.0646 (17) | |
F1 | 1.1574 (10) | 0.8538 (6) | 0.3612 (4) | 0.083 (2) | |
F2 | 1.2903 (10) | 1.0721 (6) | 0.3325 (5) | 0.093 (2) | |
F3 | 1.3077 (12) | 1.0710 (7) | 0.1490 (7) | 0.116 (3) | |
F4 | 1.1862 (14) | 0.8501 (8) | −0.0062 (6) | 0.122 (3) | |
F5 | 0.6430 (12) | −0.0636 (8) | 0.3815 (6) | 0.113 (3) | |
F6 | 0.5008 (9) | −0.3119 (6) | 0.2845 (5) | 0.0814 (19) | |
F7 | 0.5109 (11) | −0.4186 (6) | 0.0952 (6) | 0.104 (3) | |
F8 | 0.6718 (10) | −0.2728 (7) | 0.0024 (4) | 0.097 (2) | |
C1 | 1.0236 (16) | 0.6013 (10) | 0.1976 (7) | 0.0672 (17) | |
C2 | 1.0997 (12) | 0.7292 (9) | 0.1896 (6) | 0.045 (2) | |
C3 | 1.1112 (15) | 0.7308 (10) | 0.0985 (8) | 0.064 (3) | |
H3 | 1.0701 | 0.6538 | 0.0446 | 0.076* | |
C4 | 1.1825 (17) | 0.8445 (12) | 0.0850 (9) | 0.072 (3) | |
C5 | 1.2464 (15) | 0.9593 (11) | 0.1635 (11) | 0.077 (4) | |
C6 | 1.2274 (14) | 0.9605 (10) | 0.2543 (8) | 0.063 (3) | |
C7 | 1.1614 (13) | 0.8462 (9) | 0.2689 (7) | 0.055 (2) | |
C8 | 1.2081 (14) | 0.3590 (10) | 0.2339 (8) | 0.066 (3) | |
H8A | 1.3010 | 0.4031 | 0.2944 | 0.099* | |
H8B | 1.2354 | 0.3944 | 0.1845 | 0.099* | |
H8C | 1.2048 | 0.2680 | 0.2119 | 0.099* | |
C9 | 0.6708 (14) | 0.3455 (12) | 0.1955 (8) | 0.087 (4) | |
H9A | 0.6119 | 0.3854 | 0.2450 | 0.130* | |
H9B | 0.6196 | 0.2532 | 0.1699 | 0.130* | |
H9C | 0.6521 | 0.3799 | 0.1430 | 0.130* | |
C10 | 1.1306 (15) | 0.2745 (12) | 0.5321 (8) | 0.074 (3) | |
H10A | 1.2302 | 0.3099 | 0.5088 | 0.110* | |
H10B | 1.0937 | 0.1818 | 0.5000 | 0.110* | |
H10C | 1.1692 | 0.2951 | 0.6021 | 0.110* | |
C11 | 0.6381 (12) | 0.3513 (10) | 0.5138 (7) | 0.056 (2) | |
H11A | 0.5921 | 0.4102 | 0.4855 | 0.085* | |
H11B | 0.6375 | 0.3774 | 0.5823 | 0.085* | |
H11C | 0.5618 | 0.2649 | 0.4798 | 0.085* | |
C12 | 0.8051 (12) | 0.1130 (9) | 0.2903 (7) | 0.049 (2) | |
C13 | 0.7312 (11) | −0.0276 (8) | 0.2416 (6) | 0.041 (2) | |
C14 | 0.6521 (12) | −0.1085 (10) | 0.2872 (6) | 0.050 (2) | |
C15 | 0.5775 (13) | −0.2391 (9) | 0.2366 (8) | 0.056 (3) | |
C16 | 0.5824 (14) | −0.2943 (10) | 0.1427 (7) | 0.060 (3) | |
C17 | 0.6605 (15) | −0.2171 (11) | 0.0972 (7) | 0.067 (3) | |
C18 | 0.7351 (13) | −0.0850 (10) | 0.1422 (7) | 0.052 (2) | |
H18 | 0.7863 | −0.0356 | 0.1083 | 0.063* |
U11 | U22 | U33 | U12 | U13 | U23 | |
Sn1 | 0.0434 (4) | 0.0388 (4) | 0.0411 (3) | 0.0045 (3) | 0.0175 (3) | 0.0174 (3) |
Sn2 | 0.0461 (4) | 0.0405 (4) | 0.0351 (3) | 0.0027 (3) | 0.0139 (3) | 0.0134 (3) |
O1 | 0.093 (4) | 0.047 (3) | 0.052 (3) | −0.005 (3) | 0.018 (3) | 0.016 (3) |
O2 | 0.070 (4) | 0.049 (3) | 0.040 (3) | 0.009 (3) | 0.021 (3) | 0.020 (3) |
O3 | 0.053 (3) | 0.041 (3) | 0.038 (3) | 0.003 (2) | 0.020 (2) | 0.016 (2) |
O4 | 0.0434 (4) | 0.0388 (4) | 0.0411 (3) | 0.0045 (3) | 0.0175 (3) | 0.0174 (3) |
O5 | 0.086 (4) | 0.049 (3) | 0.056 (3) | 0.003 (3) | 0.029 (3) | 0.016 (3) |
F1 | 0.125 (6) | 0.064 (4) | 0.048 (3) | 0.008 (4) | 0.027 (3) | 0.008 (3) |
F2 | 0.103 (5) | 0.044 (4) | 0.110 (6) | 0.001 (3) | 0.025 (4) | 0.005 (4) |
F3 | 0.144 (7) | 0.058 (5) | 0.175 (8) | 0.015 (4) | 0.074 (6) | 0.066 (5) |
F4 | 0.214 (10) | 0.087 (6) | 0.094 (5) | 0.029 (6) | 0.080 (6) | 0.054 (5) |
F5 | 0.148 (8) | 0.101 (6) | 0.087 (5) | 0.009 (5) | 0.046 (5) | 0.030 (5) |
F6 | 0.085 (4) | 0.063 (4) | 0.096 (5) | −0.005 (3) | 0.022 (4) | 0.040 (4) |
F7 | 0.115 (6) | 0.045 (4) | 0.109 (6) | −0.008 (4) | 0.000 (4) | −0.002 (4) |
F8 | 0.109 (6) | 0.106 (6) | 0.053 (4) | 0.018 (4) | 0.021 (4) | −0.003 (4) |
C1 | 0.093 (4) | 0.047 (3) | 0.052 (3) | −0.005 (3) | 0.018 (3) | 0.016 (3) |
C2 | 0.046 (5) | 0.043 (5) | 0.044 (5) | 0.007 (4) | 0.010 (4) | 0.016 (4) |
C3 | 0.086 (8) | 0.046 (6) | 0.059 (6) | 0.009 (5) | 0.024 (6) | 0.018 (5) |
C4 | 0.094 (9) | 0.064 (8) | 0.082 (8) | 0.019 (6) | 0.047 (7) | 0.046 (7) |
C5 | 0.071 (7) | 0.051 (7) | 0.135 (11) | 0.023 (6) | 0.042 (8) | 0.055 (8) |
C6 | 0.066 (7) | 0.045 (6) | 0.081 (7) | 0.014 (5) | 0.032 (6) | 0.018 (6) |
C7 | 0.056 (6) | 0.048 (6) | 0.065 (6) | 0.014 (5) | 0.019 (5) | 0.022 (5) |
C8 | 0.068 (7) | 0.052 (6) | 0.090 (8) | 0.016 (5) | 0.044 (6) | 0.026 (6) |
C9 | 0.065 (7) | 0.096 (10) | 0.082 (8) | −0.013 (7) | −0.002 (6) | 0.037 (7) |
C10 | 0.077 (7) | 0.095 (9) | 0.080 (7) | 0.055 (7) | 0.035 (6) | 0.046 (7) |
C11 | 0.041 (5) | 0.066 (7) | 0.057 (6) | 0.006 (5) | 0.015 (4) | 0.016 (5) |
C12 | 0.043 (5) | 0.040 (5) | 0.073 (6) | 0.014 (4) | 0.028 (5) | 0.025 (5) |
C13 | 0.039 (5) | 0.036 (5) | 0.046 (5) | 0.004 (4) | 0.010 (4) | 0.016 (4) |
C14 | 0.048 (5) | 0.060 (6) | 0.040 (4) | 0.010 (4) | 0.007 (4) | 0.020 (4) |
C15 | 0.047 (6) | 0.044 (6) | 0.074 (7) | −0.001 (4) | 0.009 (5) | 0.025 (5) |
C16 | 0.066 (7) | 0.038 (6) | 0.053 (6) | 0.005 (5) | −0.006 (5) | 0.001 (5) |
C17 | 0.073 (7) | 0.073 (8) | 0.036 (5) | 0.008 (6) | 0.008 (5) | 0.001 (5) |
C18 | 0.056 (6) | 0.060 (6) | 0.043 (5) | 0.012 (5) | 0.011 (4) | 0.023 (5) |
Sn1—O3 | 2.053 (5) | C3—C4 | 1.373 (14) |
Sn1—O3i | 2.140 (6) | C3—H3 | 0.9300 |
Sn1—O4 | 2.270 (5) | C4—C5 | 1.374 (17) |
Sn1—C10 | 2.090 (9) | C5—C6 | 1.362 (15) |
Sn1—C11 | 2.125 (9) | C6—C7 | 1.378 (14) |
Sn2—O2 | 2.202 (6) | C8—H8A | 0.9600 |
Sn2—O3 | 2.022 (5) | C8—H8B | 0.9600 |
Sn2—O5 | 2.295 (7) | C8—H8C | 0.9600 |
Sn2—C8 | 2.115 (9) | C9—H9A | 0.9600 |
Sn2—C9 | 2.086 (10) | C9—H9B | 0.9600 |
O1—C1 | 1.216 (11) | C9—H9C | 0.9600 |
O2—C1 | 1.291 (11) | C10—H10A | 0.9600 |
O3—Sn1i | 2.140 (6) | C10—H10B | 0.9600 |
O4—C12 | 1.265 (10) | C10—H10C | 0.9600 |
O5—C12 | 1.255 (10) | C11—H11A | 0.9600 |
F1—C7 | 1.337 (11) | C11—H11B | 0.9600 |
F2—C6 | 1.350 (12) | C11—H11C | 0.9600 |
F3—C5 | 1.342 (11) | C12—C13 | 1.466 (12) |
F4—C4 | 1.363 (12) | C13—C14 | 1.394 (12) |
F5—C14 | 1.341 (11) | C13—C18 | 1.412 (12) |
F6—C15 | 1.348 (11) | C14—C15 | 1.376 (13) |
F7—C16 | 1.309 (12) | C15—C16 | 1.339 (14) |
F8—C17 | 1.366 (11) | C16—C17 | 1.361 (15) |
C1—C2 | 1.488 (13) | C17—C18 | 1.380 (14) |
C2—C3 | 1.359 (12) | C18—H18 | 0.9300 |
C2—C7 | 1.394 (13) | ||
O3—Sn1—C10 | 106.3 (3) | F1—C7—C6 | 117.1 (9) |
O3—Sn1—C11 | 110.2 (3) | F1—C7—C2 | 122.5 (8) |
C10—Sn1—C11 | 142.7 (4) | C6—C7—C2 | 120.4 (9) |
O3—Sn1—O3i | 76.6 (2) | Sn2—C8—H8A | 109.5 |
C10—Sn1—O3i | 98.8 (4) | Sn2—C8—H8B | 109.5 |
C11—Sn1—O3i | 96.5 (3) | H8A—C8—H8B | 109.5 |
O3—Sn1—O4 | 91.1 (2) | Sn2—C8—H8C | 109.5 |
C10—Sn1—O4 | 89.5 (4) | H8A—C8—H8C | 109.5 |
C11—Sn1—O4 | 82.8 (3) | H8B—C8—H8C | 109.5 |
O3i—Sn1—O4 | 166.7 (2) | Sn2—C9—H9A | 109.5 |
O3—Sn1—Sn1i | 39.25 (15) | Sn2—C9—H9B | 109.5 |
C10—Sn1—Sn1i | 106.0 (3) | H9A—C9—H9B | 109.5 |
C11—Sn1—Sn1i | 106.8 (3) | Sn2—C9—H9C | 109.5 |
O3i—Sn1—Sn1i | 37.36 (13) | H9A—C9—H9C | 109.5 |
O4—Sn1—Sn1i | 130.19 (13) | H9B—C9—H9C | 109.5 |
O3—Sn2—C9 | 103.5 (4) | Sn1—C10—H10A | 109.5 |
O3—Sn2—C8 | 109.1 (4) | Sn1—C10—H10B | 109.5 |
C8—Sn2—C9 | 146.4 (5) | H10A—C10—H10B | 109.5 |
O3—Sn2—O2 | 82.0 (2) | Sn1—C10—H10C | 109.5 |
C9—Sn2—O2 | 98.5 (4) | H10A—C10—H10C | 109.5 |
C8—Sn2—O2 | 93.8 (3) | H10B—C10—H10C | 109.5 |
O3—Sn2—O5 | 91.7 (2) | Sn1—C11—H11A | 109.5 |
C9—Sn2—O5 | 88.4 (4) | Sn1—C11—H11B | 109.5 |
C8—Sn2—O5 | 82.9 (3) | H11A—C11—H11B | 109.5 |
O2—Sn2—O5 | 171.6 (2) | Sn1—C11—H11C | 109.5 |
C1—O2—Sn2 | 104.4 (6) | H11A—C11—H11C | 109.5 |
Sn2—O3—Sn1 | 132.2 (3) | H11B—C11—H11C | 109.5 |
Sn2—O3—Sn1i | 124.2 (2) | O5—C12—O4 | 123.3 (8) |
Sn1—O3—Sn1i | 103.4 (2) | O5—C12—C13 | 118.5 (8) |
C12—O4—Sn1 | 132.8 (5) | O4—C12—C13 | 118.1 (7) |
C12—O5—Sn2 | 129.0 (6) | C14—C13—C18 | 117.6 (8) |
O1—C1—O2 | 121.3 (9) | C14—C13—C12 | 123.6 (8) |
O1—C1—C2 | 119.4 (9) | C18—C13—C12 | 118.8 (8) |
O2—C1—C2 | 119.1 (9) | F5—C14—C15 | 116.6 (9) |
C3—C2—C7 | 118.2 (8) | F5—C14—C13 | 122.2 (9) |
C3—C2—C1 | 117.3 (8) | C15—C14—C13 | 121.2 (8) |
C7—C2—C1 | 124.4 (8) | C16—C15—F6 | 120.2 (9) |
C2—C3—C4 | 121.0 (10) | C16—C15—C14 | 121.5 (9) |
C2—C3—H3 | 119.5 | F6—C15—C14 | 118.4 (9) |
C4—C3—H3 | 119.5 | F7—C16—C15 | 121.0 (11) |
F4—C4—C3 | 122.2 (11) | F7—C16—C17 | 120.8 (10) |
F4—C4—C5 | 117.1 (10) | C15—C16—C17 | 118.2 (9) |
C3—C4—C5 | 120.7 (10) | C16—C17—F8 | 118.8 (10) |
F3—C5—C6 | 120.3 (12) | C16—C17—C18 | 123.8 (9) |
F3—C5—C4 | 120.3 (12) | F8—C17—C18 | 117.4 (10) |
C6—C5—C4 | 118.9 (9) | C17—C18—C13 | 117.8 (9) |
F2—C6—C5 | 119.8 (10) | C17—C18—H18 | 121.1 |
F2—C6—C7 | 119.4 (10) | C13—C18—H18 | 121.1 |
C5—C6—C7 | 120.4 (10) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1ii | 0.93 | 2.49 | 3.375 (12) | 160 |
C8—H8C···F3iii | 0.96 | 2.44 | 3.347 (14) | 159 |
C11—H11B···F6iv | 0.96 | 2.61 | 3.441 (11) | 145 |
Symmetry codes: (ii) −x+2, −y+1, −z; (iii) x, y−1, z; (iv) −x+1, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | [Sn4(CH3)8(C7HF4O2)4O2] |
Mr | 1399.34 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 298 |
a, b, c (Å) | 7.6590 (9), 11.1358 (13), 14.6746 (17) |
α, β, γ (°) | 107.634 (15), 100.296 (16), 100.185 (16) |
V (Å3) | 1137.4 (3) |
Z | 1 |
Radiation type | Mo Kα |
µ (mm−1) | 2.29 |
Crystal size (mm) | 0.41 × 0.38 × 0.35 |
Data collection | |
Diffractometer | Bruker SMART CCD |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2004) |
Tmin, Tmax | 0.454, 0.502 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5695, 3908, 2795 |
Rint | 0.034 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.052, 0.159, 1.01 |
No. of reflections | 3908 |
No. of parameters | 286 |
No. of restraints | 49 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 2.05, −2.31 |
Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SAINT, SHELXTL (Sheldrick, 2001), SHELXL97 (Sheldrick, 1997), SHELXTL.
Sn1—O3 | 2.053 (5) | Sn2—O2 | 2.202 (6) |
Sn1—O3i | 2.140 (6) | Sn2—O3 | 2.022 (5) |
Sn1—O4 | 2.270 (5) | Sn2—O5 | 2.295 (7) |
C10—Sn1—C11 | 142.7 (4) | Sn2—O3—Sn1i | 124.2 (2) |
C8—Sn2—C9 | 146.4 (5) | Sn1—O3—Sn1i | 103.4 (2) |
Sn2—O3—Sn1 | 132.2 (3) |
Symmetry code: (i) −x+2, −y+1, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C3—H3···O1ii | 0.93 | 2.49 | 3.375 (12) | 160 |
C8—H8C···F3iii | 0.96 | 2.44 | 3.347 (14) | 159 |
C11—H11B···F6iv | 0.96 | 2.61 | 3.441 (11) | 145 |
Symmetry codes: (ii) −x+2, −y+1, −z; (iii) x, y−1, z; (iv) −x+1, −y, −z+1. |
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.