metal-organic papers Bis[1,1,3,3-tetramethyl-1,3-bis(dichloroacetato)distannoxane]

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1 metal-organic papers Acta Crystallographica Section E Structure Reports Online ISSN Bis[1,1,3,3-tetramethyl-1,3-bis(dichloroacetato)distannoxane] Mostafa M. Amini, a Shabnam Hossein Abadi, a Mahdi Mirzaee, a Shi-Yao Yang b and Seik Weng Ng c * a Department of Chemistry, Shahid Beheshti University, Tehran, Iran, b Department of Chemistry, Xiamen University, Xiamen , People's Republic of China, and c Department of Chemistry, University of Malaya, Kuala Lumpur, Malaysia Correspondence seikweng@um.edu.my Key indicators Single-crystal X-ray study T = 298 K Mean (C±C) = AÊ R factor = wr factor = Data-to-parameter ratio = 22.6 For details of how these key indicators were automatically derived from the article, see In centrosymmetric octamethyl-1 2 C,2 2 C,3 2 C,4 2 C- tetrakis--dichloroacetato-1:2 2 O,O 0 ;2:3 2 O,O 0 ;3:4 2 O,O 0 ;- 1:4-2 O-bis- 3 -oxo-1:2:3: 3 O;1:3:4 3 O-tetratin(IV), [[(CH 3 ) 2 - SnO 2 CCHCl 2 ] 2 O] 2, two Sn atoms are six-coordinate in a C 2 SnO 4 skew-trapezoidal bipyramidal geometry [CÐSnÐC (4) ]. The other two Sn atoms are ve-coordinate [CÐ SnÐC (4) ], but the geometry is better regarded as a trans-c 2 SnO 4 octahedron owing to a long intermolecular SnÐ O bond [SnÐO (6) A Ê ], which links the molecules into a linear chain. Comment An earlier study reported the synthesis of dimethylphenyltin tri uoroacetate by the reaction of dimethylphenyltin iodide with silver tri uoroacetate (Amini et al., 2002a). The analogous reaction with silver benzoate led to tin±phenyl cleavage, affording bis(1,1,3,3-tetramethyl-1,3-dibenzoatodistannoxane) (Amini et al., 2002b); a similar cleavage is invoked to account for the formation of the title distannoxane, (I) (Fig. 1), from the reaction with silver dichlorobenzoate. Received 29 August 2003 Accepted 3 September 2003 Online 11 September 2003 # 2003 International Union of Crystallography Printed in Great Britain ± all rights reserved The structures of tetraorganodicarboxylatodistannoxanes are classi ed into four types (Ng et al., 1991), with the type reported for bis(tetramethyldibenzoatodistannoxane) being the most common (Haiduc & Edelmann, 1999). In this centrosymmetric type, one carboxylato anion bridges the SnÐ OÐSn unit through its ÐCO 2 constituent. The other anion uses only one O atom, the single-bond carboxyl O atom, to bridge the second SnÐOÐSn unit. In contrast, the doublebonded carbonyl O atom in the title distannoxane is rotated about the carbon±carbon single bond in order to interact with the ve-coordinate Sn2 atom [CÐSnÐC (3) ] of an adjacent molecule, so that the geometry is instead better regarded as a trans-c 2 SnO 4 octahedron arising from this somewhat long [Sn2ÐO4 ii (6) A Ê ; symmetry code (ii) 2 x, 1 y, 2 z] interaction. This interaction leads to the formation of a chain structure. The other (CH 3 ) 2 Sn is more bent. The O5, O1, O1 i and O2 i [symmetry code (i) 1 x, m876 Mostafa M. Amini et al. [Sn 4 (C 2 HO 2 Cl 2 ) 4 (CH 3 ) 8 O 2 ] DOI: /S Acta Cryst. (2003). E59, m876±m877

2 metal-organic papers Table 1 Selected geometric parameters (A Ê, ). Sn1ÐC (8) Sn1ÐC (8) Sn1ÐO (4) Sn1ÐO1 i (5) Sn1ÐO (6) Sn1ÐO5 i (5) Sn2ÐC (8) Sn2ÐC (8) Sn2ÐO (4) Sn2ÐO (6) Sn2ÐO4 ii (6) Sn2ÐO (5) Figure 1 ORTEP (Johnson, 1976) plot of bis[1,1,3,3-tetramethyl-1,3-bis(dichloroacetato)distannoxane]; displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii. [Symmetry code: (i) 1 x, 1 y, 1 z.] 1 y, 1 z] atoms constitute an approximate trapezoid, and the methyl groups are skewed over the long (O5ÐO2 i ) edge [CÐSnÐC (4) ]. Experimental Dimethylphenyltin iodide was synthesized using iodine to cleave the tin±aryl bond of dimethyldiphenyltin (Davison & Rakita, 1970). The iodide (0.37 g, 1 mmol) and silver dichloroacetate (0.23 g, 1 mmol), when reacted in ethanol, gave a precipitate of silver iodide, which was removed by ltration. Evaporation of the solvent gave an oily material, which was puri ed by crystallization from chloroform to furnish colorless crystals, m.p. 548±550 K. C1ÐSn1ÐC (4) C1ÐSn1ÐO (3) C1ÐSn1ÐO1 i 98.7 (3) C1ÐSn1ÐO (3) C1ÐSn1ÐO5 i 80.6 (3) C2ÐSn1ÐO (3) C2ÐSn1ÐO1 i (3) C2ÐSn1ÐO (3) C2ÐSn1ÐO5 i 80.7 (3) O1ÐSn1ÐO1 i 77.2 (2) O1ÐSn1ÐO (2) O1ÐSn1ÐO5 i (2) O1 i ÐSn1ÐO (2) O1 i ÐSn1ÐO5 i 66.9 (2) O2ÐSn1ÐO5 i (2) C5ÐSn2ÐC (4) C5ÐSn2ÐO (3) Symmetry codes: (i) 1 x; 1 y; 1 z; (ii) 2 x; 1 y; 2 z. C5ÐSn2ÐO (3) C5ÐSn2ÐO4 ii 77.2 (3) C5ÐSn2ÐO (3) C6ÐSn2ÐO (3) C6ÐSn2ÐO (3) C6ÐSn2ÐO4 ii 77.2 (3) C6ÐSn2ÐO (3) O1ÐSn2ÐO (2) O1ÐSn2ÐO4 ii (2) O1ÐSn2ÐO (2) O3ÐSn2ÐO4 ii 76.5 (2) O3ÐSn2ÐO (2) O4 ii ÐSn2ÐO (2) Sn1ÐO1ÐSn1 i (2) Sn1ÐO1ÐSn (2) Sn1 i ÐO1ÐSn (2) Sn1 i ÐO5ÐSn (2) The H atoms were placed in calculated positions and were allowed to ride on their parent atoms [CÐH 0.96 A Ê and U(H) = 1.3U eq (C) for the methyl H atoms; CÐH 0.98 A Ê and U(H) = 1.5U eq (C) for the methine H atom]. The torsion angles were re ned for the methyl groups. The deepest hole is about 1 A Ê from atom H8. Data collection: SMART (Bruker, 2001); cell re nement: SMART; data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97. Crystal data [Sn 4 (C 2 HO 2 Cl 2 ) 4 (CH 3 ) 8 O 2 ] M r = Triclinic, P1 a = (5) A Ê b = (6) A Ê c = (7) A Ê = (1) = (1) = (1) V = (9) A Ê 3 Data collection Bruker SMART APEX areadetector diffractometer ' and! scans Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.540, T max = measured re ections Re nement Re nement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = re ections 176 parameters Z =1 D x = Mg m 3 Mo K radiation Cell parameters from 3478 re ections = 2.5±28.3 = 3.48 mm 1 T = 298 (2) K Parallelepiped, colorless mm 3977 independent re ections 3218 re ections with I > 2(I) R int = max = 28.3 h = 11! 11 k = 12! 12 l = 14! 14 H-atom parameters constrained w = 1/[ 2 (F o 2 ) + (0.0466P) 2 ] where P =(F o 2 +2F c 2 )/3 (/) max = max = 0.98 e A Ê 3 min = 1.07 e A Ê 3 The authors thank the Vice President's Of ce of Research Affairs of Shahid Beheshti University, Xiamen University and the University of Malaya for supporting this work. References Amini, M. M., Abadi, S. H., Mirzaee, M., LuÈ gger, T., Hahn, F. E. & Ng, S. W. (2002a). Acta Cryst. E58, m650±m652. Amini, M. M., Abadi, S. H., Mirzaee, M., LuÈ gger, T., Hahn, F. E. & Ng, S. W. (2002b). Acta Cryst. E58, m697±m699. Bruker (2001). SAINT and SMART. Bruker AXS Inc., Madison, Wisconsin, USA. Davison, A. & Rakita, P. E. (1970). J. Organomet. Chem. 23, 407±436. Haiduc, I. & Edelmann, F. T. (1999). Supramolecular Organometallic Chemistry. Weinheim: Wiley-VCH Verlag GmbH. Johnson, C. K. (1976). ORTEPII. Report ORNL Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. Ng, S. W., Chen, W. & Kumar Das, V. G. (1991). J. Organomet. Chem. 412, 39± 45. Sheldrick, G. M. (1996). SADABS. University of GoÈttingen, Germany. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈ ttingen, Germany. Acta Cryst. (2003). E59, m876±m877 Mostafa M. Amini et al. [Sn 4 (C 2 HO 2 Cl 2 ) 4 (CH 3 ) 8 O 2 ] m877

3 supporting information [doi: /s ] Bis[1,1,3,3-tetramethyl-1,3-bis(dichloroacetato)distannoxane] Mostafa M. Amini, Shabnam Hossein Abadi, Mahdi Mirzaee, Shi-Yao Yang and Seik Weng Ng S1. Comment An earlier study reported the synthesis of dimethylphenyltin trifluoroacetate by the reaction of dimethylphenyltin iodide with silver trifluoroacetate (Amini et al., 2002a). The analogous reaction with silver benzoate led to tin phenyl cleavage to afford bis(1,1,3,3-tetramethyl-1,3-dibenzoatodistannoxane) (Amini et al., 2002b); a similar cleavage is invoked to account for the formation of the title distannoxane, (I) (Fig. 1), from the reaction with silver dichlorobenzoate. The structures of tetraorganodicarboxylatodistannoxanes are classified into four types (Ng et al., 1991), with the type reported for bis(tetramethyldibenzoatodistannoxane) being the most common (Haiduc & Edelmann, 1999). In this centrosymmetric type, one carboxylato anion bridges the Sn O Sn unit through its CO 2 part. The other anion uses only one O atom, the single-bond carboxyl O atom, to bridge the second Sn O Sn unit. In contrast, the double-bond carbonyl O atom in the title distannoxane is rotated about the carbon carbon single bond in order to interact with the five-coordinate Sn2 atom [C Sn C (3) ] of an adjacent molecule, so that the geometry is instead better regarded as a trans-c 2 SnO 4 octahedron arising from this somewhat long [Sn2 O4 ii (6) Å; symmetry code (ii) 2 x, 1 y, 2 z] interaction. This interaction leads to the formation of a chain structure. The other (CH 3 ) 2 Sn is more bent. The O5, O1, O1 i and O2 i [symmetry code (i) 1 x, 1 y, 1 z] atoms constitute an approximate trapezoid, and its methyl groups are skewed over the long (O5 O2 i ) edge [C Sn C (4) ]. S2. Experimental Dimethylphenyltin iodide was synthesized using iodine to cleave the tin aryl bond of dimethyldiphenyltin (Davison & Rakita, 1970). The iodide (0.37 g, 1 mmol) and silver dichloroacetate (0.23 g, 1 mmol), when reacted in ethanol, gave a precipitate of silver iodide, which was removed by filtration. Evaporation of the solvent gave an oily material, which was purified by crystallization from chloroform to furnish colorless crystals, m.p K. S3. Refinement The H atoms were placed at calculated position and were allowed to ride on their parent C-atoms [C H 0.96 Å and U(H) = 1.3U eq (C) for the methyl H atoms; C H 98 Å and U(H) = 1.5U eq (C) for the methine H atom]. The torsion angles were refined for the methyl groups. sup-1

4 Figure 1 ORTEP (Johnson, 1976) plot of bis[1,1,3,3-tetramethyl-1,3-bis(dichloroacetato)distannoxane]; displacement ellipsoids are drawn at the 50% probability level. H atoms are drawn as spheres of arbitrary radii. [Symmetry code: (i) 1 x, 1 y, 1 z.] Bis[1,1,3,3-tetramethyl-1,3-bis(dichloroacetato)distannoxane] Crystal data [Sn 4 (C 2 HO 2 Cl 2 ) 4 (CH 3 ) 8 O 2 ] M r = Triclinic, P1 a = (5) Å b = (6) Å c = (7) Å α = (1) β = (1) γ = (1) V = (9) Å 3 Data collection Bruker APEX area-detector diffractometer Radiation source: fine-focus sealed tube Graphite monochromator φ and ω scan Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.540, T max = Z = 1 F(000) = 540 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 3478 reflections θ = µ = 3.48 mm 1 T = 298 K Parallelepiped, colorless mm 7696 measured reflections 3977 independent reflections 3218 reflections with I > 2σ(I) R int = θ max = 28.3, θ min = 2.0 h = k = l = sup-2

5 Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 176 parameters 0 restraints Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.0466P) 2 ] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.98 e Å 3 Δρ min = 1.07 e Å 3 Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Sn (6) (5) (5) (2) Sn (6) (5) (5) (2) Cl (4) (3) (3) (1) Cl (4) (4) (4) (1) Cl (4) (3) (3) (1) Cl (5) (4) (4) (1) O (6) (5) (4) (1) O (8) (6) (6) (2) O (8) (7) (6) (2) O (7) (6) (6) (2) O (6) (5) (5) (1) C (1) (9) (9) (2) C (1) (1) (9) (3) C (1) (9) (8) (2) C (1) (9) (9) (2) C (1) (1) (9) (2) C (1) (1) (9) (3) C (1) (7) (8) (1) C (1) (9) (8) (2) H1a * H1b * H1c * H2a * H2b * H2c * H * H5a * H5b * H5c * H6a * H6b * H6c * H * sup-3

6 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Sn (3) (3) (3) (2) (2) (2) Sn (3) (3) (3) (2) (2) (2) Cl (2) (2) (2) (2) (2) (2) Cl (2) (3) (3) (2) (2) (3) Cl (2) (2) (2) (1) (2) (2) Cl (3) (2) (3) (2) (3) (2) O (3) (3) (3) (2) (2) (2) O (4) (4) (4) (3) (3) (3) O (5) (4) (4) (3) (4) (3) O (4) (4) (4) (3) (3) (3) O (3) (3) (3) (2) (2) (2) C (6) (5) (6) (5) (5) (4) C (5) (7) (6) (5) (5) (5) C (5) (5) (5) (4) (4) (4) C (5) (5) (6) (4) (4) (4) C (5) (7) (6) (5) (4) (5) C (6) (6) (5) (5) (5) (4) C (5) (4) (5) (3) (4) (3) C (6) (6) (5) (5) (5) (4) Geometric parameters (Å, º) Sn1 C (8) O4 C (9) Sn1 C (8) O5 C (9) Sn1 O (4) C3 C (1) Sn1 O1 i (5) C7 C (1) Sn1 O (6) C1 H1a 0.96 Sn1 O5 i (5) C1 H1b 0.96 Sn2 C (8) C1 H1c 0.96 Sn2 C (8) C2 H2a 0.96 Sn2 O (4) C2 H2b 0.96 Sn2 O (6) C2 H2c 0.96 Sn2 O4 ii (6) C4 H Sn2 O (5) C5 H5a 0.96 Cl1 C (9) C5 H5b 0.96 Cl2 C (9) C5 H5c 0.96 Cl3 C (9) C6 H6a 0.96 Cl4 C (1) C6 H6b 0.96 O2 C (9) C6 H6c 0.96 O3 C (1) C8 H C1 Sn1 C (4) O3 C3 C (7) C1 Sn1 O (3) C3 C4 Cl (7) C1 Sn1 O1 i 98.7 (3) C3 C4 Cl (6) C1 Sn1 O (3) Cl1 C4 Cl (5) sup-4

7 C1 Sn1 O5 i 80.6 (3) O4 C7 O (8) C2 Sn1 O (3) O4 C7 C (8) C2 Sn1 O1 i (3) O5 C7 C (7) C2 Sn1 O (3) C7 C8 Cl (6) C2 Sn1 O5 i 80.7 (3) C7 C8 Cl (6) O1 Sn1 O1 i 77.2 (2) Cl3 C8 Cl (5) O1 Sn1 O (2) Sn1 C1 H1a O1 Sn1 O5 i (2) Sn1 C1 H1b O1 i Sn1 O (2) H1a C1 H1b O1 i Sn1 O5 i 66.9 (2) Sn1 C1 H1c O2 Sn1 O5 i (2) H1a C1 H1c C5 Sn2 C (4) H1b C1 H1c C5 Sn2 O (3) Sn1 C2 H2a C5 Sn2 O (3) Sn1 C2 H2b C5 Sn2 O4 ii 77.2 (3) H2a C2 H2b C5 Sn2 O (3) Sn1 C2 H2c C6 Sn2 O (3) H2a C2 H2c C6 Sn2 O (3) H2b C2 H2c C6 Sn2 O4 ii 77.2 (3) C3 C4 H C6 Sn2 O (3) Cl1 C4 H O1 Sn2 O (2) Cl2 C4 H O1 Sn2 O4 ii (2) Sn2 C5 H5a O1 Sn2 O (2) Sn2 C5 H5b O3 Sn2 O4 ii 76.5 (2) H5a C5 H5b O3 Sn2 O (2) Sn2 C5 H5c O4 ii Sn2 O (2) H5a C5 H5c Sn1 O1 Sn1 i (2) H5b C5 H5c Sn1 O1 Sn (2) Sn2 C6 H6a Sn1 i O1 Sn (2) Sn2 C6 H6b Sn1 i O5 Sn (2) H6a C6 H6b C3 O2 Sn (6) Sn2 C6 H6c C3 O3 Sn (6) H6a C6 H6c C7 O5 Sn (4) H6b C6 H6c C7 O5 Sn1 i (5) C7 C8 H O2 C3 O (8) Cl3 C8 H O2 C3 C (8) Cl4 C8 H C5 Sn2 O1 Sn (4) C6 Sn2 O3 C3 106 (1) C6 Sn2 O1 Sn (4) O4 ii Sn2 O3 C3 177 (1) O3 Sn2 O1 Sn1 0.3 (4) O1 Sn2 O5 C (6) O5 Sn2 O1 Sn (4) C5 Sn2 O5 C (6) C5 Sn2 O1 Sn1 i 89.5 (4) C6 Sn2 O5 C (6) C6 Sn2 O1 Sn1 i 92.0 (4) O4 ii Sn2 O5 C7 3.1 (6) O3 Sn2 O1 Sn1 i (3) O1 Sn2 O5 Sn1 i 1.9 (2) O5 Sn2 O1 Sn1 i 2.9 (3) C5 Sn2 O5 Sn1 i (3) O4 ii Sn2 O1 Sn1 i 179 (1) C6 Sn2 O5 Sn1 i (3) C2 Sn1 O1 Sn (5) O4 ii Sn2 O5 Sn1 i (2) C1 Sn1 O1 Sn (4) Sn1 O2 C3 O3 21 (2) sup-5

8 O1 i Sn1 O1 Sn (5) Sn1 O2 C3 C (6) O2 Sn1 O1 Sn2 2.9 (4) Sn2 O3 C3 O2 14 (2) O5 i Sn1 O1 Sn (2) Sn2 O3 C3 C (6) C2 Sn1 O1 Sn1 i 97.0 (3) O2 C3 C4 Cl (8) C1 Sn1 O1 Sn1 i 95.4 (3) O3 C3 C4 Cl1 50 (1) O1 i Sn1 O1 Sn1 i 0.0 O2 C3 C4 Cl (9) O2 Sn1 O1 Sn1 i (3) O3 C3 C4 Cl (9) O5 i Sn1 O1 Sn1 i 1.6 (4) Sn2 O5 C7 O4 9 (1) O1 Sn1 O2 C3 14 (1) Sn1 i O5 C7 O (9) C2 Sn1 O2 C3 92 (1) Sn2 O5 C7 C (6) C1 Sn1 O2 C3 121 (1) Sn1 i O5 C7 C8 5 (2) O1 i Sn1 O2 C3 19 (2) O4 C7 C8 Cl (7) O5 i Sn1 O2 C (9) O5 C7 C8 Cl3 36 (1) O1 Sn2 O3 C3 3 (1) O4 C7 C8 Cl (8) C5 Sn2 O3 C3 100 (1) O5 C7 C8 Cl (8) Symmetry codes: (i) x+1, y+1, z+1; (ii) x+2, y+1, z+2. sup-6