Bis(bicyclo­[2.2.1]hept-5-ene-2-carboxyl­ato)-1κ2O,O′;4κ2O,O′-di-μ2-chlorido-1:2κ2Cl;3:4κ2Cl-octa­methyl-1κ2C,2κ2C,3κ2C,4κ2C-di-μ3-oxido-1:2:3κ3O;2:3:4κ3O-tetra­tin(IV)

Ren, Y.

doi:10.1107/S1600536811023452

metal-organic compounds

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ISSN: 2056-9890

Volume 67| Part 7| July 2011| Page m984

doi:10.1107/S1600536811023452

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Bis(bicyclo[2.2.1]hept-5-ene-2-carboxylato)-1κ²O,O′;4κ²O,O′-di-μ₂-chlorido-1:2κ²Cl;3:4κ²Cl-octamethyl-1κ²C,2κ²C,3κ²C,4κ²C-di-μ₃-oxido-1:2:3κ³O;2:3:4κ³O-tetratin(IV)

Yupo Ren ^a ^*

^aDepartment of Pathology, Liaocheng People's Hospital, Liaocheng, Shandong 252000, People's Republic of China
^*Correspondence e-mail: lh198854@163.com

(Received 6 June 2011; accepted 16 June 2011; online 25 June 2011)

In the title compound, [Sn₄(CH₃)₈(C₈H₉O₂)₂Cl₂O₂], the tetranuclear complex molecule has crystallographically imposed inversion symmetry. The coordination polyhedron about the two central Sn atoms is distorted trigonal–bipyramidal, whilst the two peripheral metal atoms bonded to the carboxylate groups have a distorted octahedral coordination geometry. In the crystal, molecules are connected by long Sn⋯O contacts [3.139 (11) Å], forming chains along [011].

Related literature

For the biological activity of organotin compounds, see: Dubey & Roy (2003 ). For a related structure, see: Li et al. (2006 ).

Experimental

Crystal data

[Sn₄(CH₃)₈(C₈H₉O₂)₂Cl₂O₂]
M_r = 972.24
Triclinic, $[P \overline 1]$
a = 9.3685 (12) Å
b = 9.8651 (13) Å
c = 9.9103 (15) Å
α = 109.779 (2)°
β = 96.340 (1)°
γ = 97.204 (1)°
V = 843.5 (2) Å³
Z = 1
Mo Kα radiation
μ = 3.12 mm⁻¹
T = 298 K
0.13 × 0.11 × 0.05 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.687, T_max = 0.860
4366 measured reflections
2915 independent reflections
1818 reflections with I > 2σ(I)
R_int = 0.024

Refinement

R[F² > 2σ(F²)] = 0.047
wR(F²) = 0.130
S = 1.02
2915 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.64 e Å⁻³

Data collection: SMART (Siemens, 1996 ); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT; 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811023452/rz2611sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811023452/rz2611Isup2.hkl

checkCIF report

Comment top

In recent years, organotin compounds have attracted more and more attention due to their wide range of industrial applications and biological activities (Dubey & Roy, 2003). As a part of our ongoing investigations in this field, we have synthesized the title compound and present its crystal structure here.

The tetranuclear complex molecule of the title compound (Fig. 1) has crystallographically imposed inversion symmetry. The tin atoms have two different coordination modes, one atom (Sn2) is coordinated in a distorted trigonal-bipyramidal geometry by one µ₃oxo oxygen atom and two methyl groups forming the equatorial plane, and by an µ₃oxo oxygen atom and the chloride anion at the apices; the other tin metal (Sn1) has a distorted octahedral coordination geometry, with three O atoms and one Cl atom in equatorial positions and the axial position occupied by two methyl groups. The Sn—O bond distances involving the carboxylate group (Sn1—O2 = 2.115 (8) Å; Sn1—O3 = 2.699 (9) Å) are comparable to those found in a related organotin carboxylate (Li et al., 2006). The shortest Sn···Sn separation within the Sn₄ core is 3.2898 (10) Å. In the crystal structure, complex molecules are connected by long Sn···O interaction (Sn1···O3ⁱ = 3.139 (11) Å; symmetry code: (i) 1-x, -y, 1-z) into one-dimensional chains parallel to the [011] direction (Fig. 2).

Related literature top

For the biological activity of organotin compounds, see: Dubey & Roy (2003). For a related structure, see: Li et al. (2006).

Experimental top

The reaction was carried out under a nitrogen atmosphere. Bicyclo[2.2.1]heptane-2-carboxylic acid (1 mmol) and sodium ethoxide (1 mmol) were added to a stirred solution of benzene (30 ml) in a Schlenk flask After stirring the solution for 30 min, dimethyltin dichloride (2 mmol) was added and the reaction mixture was stirred for 12 h at room temperature. The resulting clear solution was evaporated under vacuum. The product was crystallized from a solution of diethyl ether to yield colourless crystals of the title compound suitable for X-ray analysis (yield: 76%). Anal. Calcd (%) for C₂₄H₄₂Cl₂O₆Sn₄ (Mr = 972.33): C, 29.65; H, 4.35. Found (%): C, 29.47; H, 4.52.

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

	Fig. 1. The molecular structure of the title compound, showing 50% probability displacement ellipsoids. H atoms have been omitted for clarity. Symmetry code: (A) 1-x, 1-y, 2-z.
	Fig. 2. View of the one-dimensional chain structure in the title compound.

Bis(bicyclo[2.2.1]hept-5-ene-2-carboxylato)- 1κ²O,O';4κ²O,O'-di-µ₂-chlorido- 1:2κ²Cl;3:4κ²Cl-octamethyl- 1κ²C,2κ²C,3κ²C,4κ²C-di-µ₃-oxido- 1:2:3κ³O;2:3:4κ³O-tetratin(IV) top

Crystal data top

[Sn₄(CH₃)₈(C₈H₉O₂)₂Cl₂O₂]	Z = 1
M_r = 972.24	F(000) = 468
Triclinic, P1	D_x = 1.914 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 9.3685 (12) Å	Cell parameters from 1509 reflections
b = 9.8651 (13) Å	θ = 2.2–25.2°
c = 9.9103 (15) Å	µ = 3.12 mm⁻¹
α = 109.779 (2)°	T = 298 K
β = 96.340 (1)°	Block, colourless
γ = 97.204 (1)°	0.13 × 0.11 × 0.05 mm
V = 843.5 (2) Å³

Data collection top

Siemens SMART CCD area-detector diffractometer	2915 independent reflections
Radiation source: fine-focus sealed tube	1818 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.024
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→11
T_min = 0.687, T_max = 0.860	k = −11→10
4366 measured reflections	l = −11→11

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)] = 0.047	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0634P)²] where P = (F_o² + 2F_c²)/3
2915 reflections	(Δ/σ)_max = 0.001
163 parameters	Δρ_max = 0.86 e Å⁻³
0 restraints	Δρ_min = −0.64 e Å⁻³

Crystal data top

[Sn₄(CH₃)₈(C₈H₉O₂)₂Cl₂O₂]	γ = 97.204 (1)°
M_r = 972.24	V = 843.5 (2) Å³
Triclinic, P1	Z = 1
a = 9.3685 (12) Å	Mo Kα radiation
b = 9.8651 (13) Å	µ = 3.12 mm⁻¹
c = 9.9103 (15) Å	T = 298 K
α = 109.779 (2)°	0.13 × 0.11 × 0.05 mm
β = 96.340 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	2915 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1818 reflections with I > 2σ(I)
T_min = 0.687, T_max = 0.860	R_int = 0.024
4366 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.047	0 restraints
wR(F²) = 0.130	H-atom parameters constrained
S = 1.02	Δρ_max = 0.86 e Å⁻³
2915 reflections	Δρ_min = −0.64 e Å⁻³
163 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	0.52583 (8)	0.20738 (8)	0.72575 (8)	0.0642 (3)
Sn2	0.34860 (7)	0.52430 (7)	0.91708 (7)	0.0541 (2)
Cl1	0.2281 (3)	0.7487 (4)	1.0584 (3)	0.0893 (9)
O1	0.5103 (6)	0.3891 (6)	0.8952 (6)	0.0567 (16)
O2	0.3315 (9)	0.2563 (10)	0.6371 (9)	0.104 (3)
O3	0.3517 (12)	0.0621 (12)	0.4673 (11)	0.123 (3)
C1	0.2708 (19)	0.160 (2)	0.5170 (19)	0.126 (6)
C2	0.114 (2)	0.312 (2)	0.436 (2)	0.147 (7)
H2	0.1241	0.4026	0.5205	0.177*
C3	0.1132 (19)	0.168 (2)	0.4573 (18)	0.137 (6)
H3	0.0508	0.1632	0.5294	0.164*
C4	0.042 (2)	0.057 (2)	0.3123 (19)	0.152 (7)
H4A	0.1041	−0.0144	0.2773	0.183*
H4B	−0.0502	0.0065	0.3211	0.183*
C5	0.017 (2)	0.135 (2)	0.2080 (19)	0.139 (6)
H5	−0.0452	0.0854	0.1128	0.166*
C6	0.183 (2)	0.175 (2)	0.223 (2)	0.156 (7)
H6	0.2425	0.1242	0.1621	0.187*
C7	0.226 (2)	0.295 (2)	0.337 (2)	0.153 (7)
H7	0.3122	0.3604	0.3543	0.183*
C8	−0.0092 (18)	0.277 (2)	0.3130 (18)	0.140 (6)
H8A	−0.0047	0.3524	0.2702	0.168*
H8B	−0.1029	0.2657	0.3446	0.168*
C9	0.6728 (14)	0.2796 (14)	0.6114 (13)	0.101 (4)
H9A	0.7045	0.3833	0.6575	0.152*
H9B	0.6262	0.2576	0.5134	0.152*
H9C	0.7556	0.2311	0.6106	0.152*
C10	0.4421 (14)	0.0339 (13)	0.7839 (13)	0.095 (4)
H10A	0.4365	0.0689	0.8857	0.142*
H10B	0.5048	−0.0379	0.7639	0.142*
H10C	0.3464	−0.0094	0.7289	0.142*
C11	0.4013 (13)	0.6224 (13)	0.7674 (12)	0.086 (3)
H11A	0.3294	0.6805	0.7552	0.129*
H11B	0.4031	0.5479	0.6756	0.129*
H11C	0.4954	0.6837	0.8028	0.129*
C12	0.1694 (12)	0.3767 (14)	0.9197 (13)	0.098 (4)
H12A	0.1857	0.2786	0.8743	0.147*
H12B	0.0834	0.3910	0.8676	0.147*
H12C	0.1567	0.3928	1.0184	0.147*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0789 (5)	0.0509 (5)	0.0573 (5)	0.0212 (4)	0.0060 (4)	0.0105 (4)
Sn2	0.0483 (4)	0.0559 (5)	0.0558 (4)	0.0153 (3)	−0.0009 (3)	0.0177 (3)
Cl1	0.0721 (18)	0.088 (2)	0.092 (2)	0.0425 (15)	−0.0049 (15)	0.0080 (17)
O1	0.057 (4)	0.052 (4)	0.056 (4)	0.028 (3)	−0.001 (3)	0.009 (3)
O2	0.113 (7)	0.093 (7)	0.090 (6)	0.043 (5)	−0.023 (5)	0.013 (5)
O3	0.142 (9)	0.113 (9)	0.091 (7)	0.039 (7)	−0.028 (6)	0.016 (6)
C1	0.132 (14)	0.121 (14)	0.103 (12)	0.041 (11)	−0.031 (10)	0.023 (11)
C2	0.154 (17)	0.134 (17)	0.121 (15)	0.047 (13)	−0.017 (13)	0.009 (12)
C3	0.163 (16)	0.124 (15)	0.108 (13)	0.021 (12)	−0.021 (11)	0.036 (12)
C4	0.157 (16)	0.137 (16)	0.131 (15)	0.024 (12)	−0.027 (12)	0.022 (14)
C5	0.146 (16)	0.137 (16)	0.108 (13)	0.033 (12)	−0.038 (11)	0.028 (12)
C6	0.147 (17)	0.154 (18)	0.122 (15)	0.036 (13)	−0.005 (12)	−0.002 (13)
C7	0.150 (17)	0.141 (18)	0.132 (16)	0.020 (13)	−0.001 (14)	0.012 (14)
C8	0.141 (14)	0.138 (16)	0.124 (14)	0.065 (11)	−0.025 (11)	0.025 (12)
C9	0.125 (11)	0.091 (10)	0.084 (9)	0.025 (8)	0.029 (8)	0.019 (8)
C10	0.109 (10)	0.075 (9)	0.093 (9)	0.009 (7)	0.003 (7)	0.028 (7)
C11	0.105 (9)	0.084 (9)	0.086 (8)	0.034 (7)	0.019 (7)	0.044 (7)
C12	0.080 (8)	0.089 (9)	0.111 (10)	−0.002 (7)	0.009 (7)	0.026 (8)

Geometric parameters (Å, º) top

Sn1—O1	2.034 (6)	C4—C5	1.49 (2)
Sn1—C10	2.075 (11)	C4—H4A	0.9700
Sn1—C9	2.082 (11)	C4—H4B	0.9700
Sn1—O2	2.115 (8)	C5—C8	1.51 (2)
Sn1—O3	2.699 (9)	C5—C6	1.54 (2)
Sn1—Cl1ⁱ	2.848 (3)	C5—H5	0.9800
Sn2—O1ⁱ	2.010 (5)	C6—C7	1.31 (2)
Sn2—C12	2.088 (11)	C6—H6	0.9300
Sn2—C11	2.096 (10)	C7—H7	0.9300
Sn2—O1	2.122 (6)	C8—H8A	0.9700
Sn2—Cl1	2.649 (3)	C8—H8B	0.9700
Sn2—Sn2ⁱ	3.2898 (12)	C9—H9A	0.9600
Cl1—Sn1ⁱ	2.848 (3)	C9—H9B	0.9600
O1—Sn2ⁱ	2.010 (5)	C9—H9C	0.9600
O2—C1	1.262 (16)	C10—H10A	0.9600
O3—C1	1.300 (18)	C10—H10B	0.9600
C1—C3	1.55 (2)	C10—H10C	0.9600
C2—C8	1.494 (19)	C11—H11A	0.9600
C2—C7	1.50 (2)	C11—H11B	0.9600
C2—C3	1.51 (2)	C11—H11C	0.9600
C2—H2	0.9800	C12—H12A	0.9600
C3—C4	1.50 (2)	C12—H12B	0.9600
C3—H3	0.9800	C12—H12C	0.9600

O1—Sn1—C10	104.6 (4)	C1—C3—H3	108.7
O1—Sn1—C9	105.3 (4)	C5—C4—C3	108.8 (15)
C10—Sn1—C9	145.7 (5)	C5—C4—H4A	109.9
O1—Sn1—O2	81.2 (3)	C3—C4—H4A	109.9
C10—Sn1—O2	100.6 (4)	C5—C4—H4B	109.9
C9—Sn1—O2	100.3 (5)	C3—C4—H4B	109.9
O1—Sn1—O3	131.8 (3)	H4A—C4—H4B	108.3
C10—Sn1—O3	85.5 (4)	C4—C5—C8	98.8 (15)
C9—Sn1—O3	87.1 (4)	C4—C5—C6	88.3 (13)
O2—Sn1—O3	50.6 (3)	C8—C5—C6	97.7 (14)
O1—Sn1—Cl1ⁱ	74.13 (16)	C4—C5—H5	121.6
C10—Sn1—Cl1ⁱ	86.0 (3)	C8—C5—H5	121.6
C9—Sn1—Cl1ⁱ	86.2 (4)	C6—C5—H5	121.6
O2—Sn1—Cl1ⁱ	155.3 (3)	C7—C6—C5	107.2 (18)
O3—Sn1—Cl1ⁱ	154.0 (3)	C7—C6—H6	126.4
O1ⁱ—Sn2—C12	114.6 (4)	C5—C6—H6	126.4
O1ⁱ—Sn2—C11	111.7 (4)	C6—C7—C2	109.9 (18)
C12—Sn2—C11	133.2 (5)	C6—C7—H7	125.0
O1ⁱ—Sn2—O1	74.5 (3)	C2—C7—H7	125.0
C12—Sn2—O1	99.8 (4)	C2—C8—C5	102.3 (14)
C11—Sn2—O1	98.5 (4)	C2—C8—H8A	111.3
O1ⁱ—Sn2—Cl1	79.31 (17)	C5—C8—H8A	111.3
C12—Sn2—Cl1	91.0 (4)	C2—C8—H8B	111.3
C11—Sn2—Cl1	91.0 (3)	C5—C8—H8B	111.3
O1—Sn2—Cl1	153.80 (17)	H8A—C8—H8B	109.2
O1ⁱ—Sn2—Sn2ⁱ	38.43 (16)	Sn1—C9—H9A	109.5
C12—Sn2—Sn2ⁱ	111.3 (4)	Sn1—C9—H9B	109.5
C11—Sn2—Sn2ⁱ	108.8 (3)	H9A—C9—H9B	109.5
O1—Sn2—Sn2ⁱ	36.06 (15)	Sn1—C9—H9C	109.5
Cl1—Sn2—Sn2ⁱ	117.74 (7)	H9A—C9—H9C	109.5
Sn2—Cl1—Sn1ⁱ	81.42 (7)	H9B—C9—H9C	109.5
Sn2ⁱ—O1—Sn1	125.1 (3)	Sn1—C10—H10A	109.5
Sn2ⁱ—O1—Sn2	105.5 (3)	Sn1—C10—H10B	109.5
Sn1—O1—Sn2	129.3 (3)	H10A—C10—H10B	109.5
C1—O2—Sn1	113.3 (10)	Sn1—C10—H10C	109.5
C1—O3—Sn1	83.5 (8)	H10A—C10—H10C	109.5
O2—C1—O3	112.1 (13)	H10B—C10—H10C	109.5
O2—C1—C3	117.7 (16)	Sn2—C11—H11A	109.5
O3—C1—C3	130.1 (15)	Sn2—C11—H11B	109.5
C8—C2—C7	92.7 (16)	H11A—C11—H11B	109.5
C8—C2—C3	102.9 (15)	Sn2—C11—H11C	109.5
C7—C2—C3	96.9 (16)	H11A—C11—H11C	109.5
C8—C2—H2	119.7	H11B—C11—H11C	109.5
C7—C2—H2	119.7	Sn2—C12—H12A	109.5
C3—C2—H2	119.7	Sn2—C12—H12B	109.5
C4—C3—C2	103.5 (14)	H12A—C12—H12B	109.5
C4—C3—C1	118.3 (17)	Sn2—C12—H12C	109.5
C2—C3—C1	108.7 (15)	H12A—C12—H12C	109.5
C4—C3—H3	108.7	H12B—C12—H12C	109.5
C2—C3—H3	108.7

Symmetry code: (i) −x+1, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	[Sn₄(CH₃)₈(C₈H₉O₂)₂Cl₂O₂]
M_r	972.24
Crystal system, space group	Triclinic, P1
Temperature (K)	298
a, b, c (Å)	9.3685 (12), 9.8651 (13), 9.9103 (15)
α, β, γ (°)	109.779 (2), 96.340 (1), 97.204 (1)
V (Å³)	843.5 (2)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	3.12
Crystal size (mm)	0.13 × 0.11 × 0.05

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.687, 0.860
No. of measured, independent and observed [I > 2σ(I)] reflections	4366, 2915, 1818
R_int	0.024
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.047, 0.130, 1.02
No. of reflections	2915
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.86, −0.64

Computer programs: SMART (Siemens, 1996), SAINT (Siemens, 1996), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Acknowledgements

The author thanks the National Natural Science Foundation of China (20971096) for financial support.

References

Dubey, S. K. & Roy, U. (2003). Appl. Organomet. Chem. 17, 3–8. Web of Science CrossRef CAS Google Scholar
Li, F.-H., Yin, H.-D., Sun, L., Zhao, Q. & Liu, W.-L. (2006). Acta Cryst. E62, m1117–m1118. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA. Google Scholar

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