Di-μ-methanolato-κ4O:O-bis[tri­chlorido(dimethyl­formamide-κO)tin(IV)]

Zhang, Q.; Yin, H.; Wang, D.

doi:10.1107/S1600536810053997

metal-organic compounds

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Volume 67| Part 2| February 2011| Page m146

doi:10.1107/S1600536810053997

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Di-μ-methanolato-κ⁴O:O-bis[trichlorido(dimethylformamide-κO)tin(IV)]

Qijun Zhang,^a Handong Yin ^a ^* and Daqi Wang ^a

^aCollege of Chemistry and Chemical Engineering, Liaocheng University, Shandong 252059, People's Republic of China
^*Correspondence e-mail: handongyin@163.com

(Received 14 December 2010; accepted 24 December 2010; online 8 January 2011)

The title compound, [Sn₂(CH₃O)₂Cl₆(C₃H₇NO)₂], contains two hexacoordinated Sn^IV atoms symmetrically bridged by two deprotonated methanol ligands, with an inversion center in the middle of the planar Sn₂O₂ ring. The other sites of the distorted octahedral coordination geometry of the Sn^IV atom are occupied by three Cl atoms and one O atom from a dimethylformamide molecule. The complex molecules are connected by weak C—H⋯Cl hydrogen bonds into a two-dimensional supramolecular network parallel to (10 $[\overline{1}]$ ).

Related literature

For related tin(IV) compounds, see: Mao & You (1990 ); Reuter & Schröder (1992 ).

Experimental

Crystal data

[Sn₂(CH₃O)₂Cl₆(C₃H₇NO)₂]
M_r = 658.34
Monoclinic, P 2₁ /n
a = 8.589 (8) Å
b = 11.4444 (13) Å
c = 11.8453 (10) Å
β = 111.155 (1)°
V = 1085.9 (10) Å³
Z = 2
Mo Kα radiation
μ = 3.05 mm⁻¹
T = 298 K
0.22 × 0.17 × 0.16 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.553, T_max = 0.641
5512 measured reflections
1903 independent reflections
1554 reflections with I > 2σ(I)
R_int = 0.063

Refinement

R[F² > 2σ(F²)] = 0.044
wR(F²) = 0.117
S = 1.14
1903 reflections
103 parameters
13 restraints
H-atom parameters constrained
Δρ_max = 1.54 e Å⁻³
Δρ_min = −2.07 e Å⁻³

Table 1
Selected bond lengths (Å)

Sn1—O1	2.106 (5)
Sn1—O1ⁱ	2.101 (5)
Sn1—O2	2.108 (4)
Sn1—Cl1	2.372 (2)
Sn1—Cl2	2.3743 (18)
Sn1—Cl3	2.368 (2)
Symmetry code: (i) -x+2, -y, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1C⋯Cl3	0.96	2.72	3.356 (8)	124
C3—H3A⋯Cl3ⁱⁱ	0.96	2.95	3.895 (11)	170
C4—H4B⋯Cl1ⁱⁱⁱ	0.96	2.90	3.837 (9)	164
Symmetry codes: (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{3\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2007 ); cell refinement: SAINT (Bruker, 2007); 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) and X-SEED (Barbour, 2001 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810053997/hy2391sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810053997/hy2391Isup2.hkl

checkCIF report

Comment top

The title compound (Fig.1) consists of six Cl anions, two methoxo anions, two Sn^IV ions and two dimethylformamide molecules. The molecule has an inversion center in the middle of the Sn₂O₂ ring. This ring is planar and can be described as rhombic, with the endocyclic angles at the O atoms larger than those at the Sn atoms [Sn1ⁱ—O1—Sn1 = 106.9 (2), O1ⁱ—Sn1—O1 = 73.1 (2)°. Symmetry code: (i) -x+2, -y, -z+1]. The Sn1—O1 distance [2.106 (5) Å] is very close to the Sn1—O1ⁱ distance [2.101 (5) Å] (Table 1). Each Sn^IV atom is hexacoordinated with two methoxo anions, three Cl anions and one dimethylformamide molecule in a distorted octahedral geometry.

As is indicated from Fig. 2 and Table 2, the intramolecular interactions, C1—H1C···Cl3, strengthen the dimeric unit and the intermolecular ones, C3—H3A···Cl3ⁱⁱ and C4—H4B···Cl1ⁱⁱⁱ [symmetry codes: (ii) x+1/2, -y+1/2, z+1/2; (iii) -x+3/2, y+1/2, -z+1/2], give rise to a two-dimensional polymer-like supramolecular network.

Related literature top

For related tin(IV) compounds, see: Mao & You (1990); Reuter & Schröder (1992).

Experimental top

Stannic chloride hydrate (0.4 mmol, 0.14 g) was dissolved in methanol (20 ml) and dimethylformamide (5 ml) was added with stirring at room temperature. The mixture was allowed to react for 6 h and was then filtered. Colorless crystals suitable for X-ray analysis were obtained by slow evaporation of methanol over a period of two weeks (yield: 60%). Analysis, calculated for C₈H₂₀Cl₆N₂O₄Sn₂: C 14.59, H 3.06, N 4.25%; found: C 14.58, H 3.04, N 4.27%.

Computing details top

Data collection: SMART (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and X-SEED (Barbour, 2001); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound, with 50% probability displacement ellipsoids. [Symmetry code: (i) -x+2, -y, -z+1.]
	Fig. 2. A view of the two-dimensional polymer-like supramolecular network in the title compound.

Di-µ-methanolato-κ⁴O:O-bis[trichlorido(dimethylformamide- κO)tin(IV)] top

Crystal data top

[Sn₂(CH₃O)₂Cl₆(C₃H₇NO)₂]	F(000) = 632
M_r = 658.34	D_x = 2.013 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2694 reflections
a = 8.589 (8) Å	θ = 2.6–27.0°
b = 11.4444 (13) Å	µ = 3.05 mm⁻¹
c = 11.8453 (10) Å	T = 298 K
β = 111.155 (1)°	Block, colourless
V = 1085.9 (10) Å³	0.22 × 0.17 × 0.16 mm
Z = 2

Data collection top

Bruker APEX CCD diffractometer	1903 independent reflections
Radiation source: fine-focus sealed tube	1554 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.063
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→10
T_min = 0.553, T_max = 0.641	k = −13→12
5512 measured reflections	l = −14→14

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.117	H-atom parameters constrained
S = 1.14	w = 1/[σ²(F_o²) + (0.065P)²] where P = (F_o² + 2F_c²)/3
1903 reflections	(Δ/σ)_max = 0.012
103 parameters	Δρ_max = 1.54 e Å⁻³
13 restraints	Δρ_min = −2.07 e Å⁻³

Crystal data top

[Sn₂(CH₃O)₂Cl₆(C₃H₇NO)₂]	V = 1085.9 (10) Å³
M_r = 658.34	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 8.589 (8) Å	µ = 3.05 mm⁻¹
b = 11.4444 (13) Å	T = 298 K
c = 11.8453 (10) Å	0.22 × 0.17 × 0.16 mm
β = 111.155 (1)°

Data collection top

Bruker APEX CCD diffractometer	1903 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1554 reflections with I > 2σ(I)
T_min = 0.553, T_max = 0.641	R_int = 0.063
5512 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	13 restraints
wR(F²) = 0.117	H-atom parameters constrained
S = 1.14	Δρ_max = 1.54 e Å⁻³
1903 reflections	Δρ_min = −2.07 e Å⁻³
103 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Sn1	0.99552 (5)	0.07346 (3)	0.37511 (4)	0.0383 (2)
Cl1	1.1769 (3)	−0.06088 (15)	0.3320 (2)	0.0619 (5)
Cl2	1.1500 (2)	0.24014 (15)	0.35788 (19)	0.0586 (5)
Cl3	0.7989 (3)	0.07190 (15)	0.17440 (19)	0.0629 (5)
N1	0.7652 (7)	0.3252 (5)	0.5241 (5)	0.0498 (14)
O1	0.8762 (6)	−0.0591 (4)	0.4372 (5)	0.0511 (10)
O2	0.8269 (5)	0.1862 (4)	0.4134 (4)	0.0461 (10)
C1	0.7018 (10)	−0.0904 (6)	0.3757 (7)	0.0556 (11)
H1A	0.6323	−0.0359	0.3974	0.083*
H1B	0.6828	−0.1677	0.3993	0.083*
H1C	0.6750	−0.0881	0.2897	0.083*
C2	0.8701 (8)	0.2657 (5)	0.4921 (6)	0.0438 (15)
H2	0.9832	0.2824	0.5290	0.053*
C3	0.8233 (14)	0.4147 (7)	0.6175 (10)	0.078 (3)
H3A	0.9420	0.4236	0.6411	0.117*
H3B	0.7968	0.3919	0.6864	0.117*
H3C	0.7696	0.4876	0.5864	0.117*
C4	0.5869 (9)	0.3028 (7)	0.4732 (9)	0.072 (2)
H4A	0.5679	0.2218	0.4517	0.109*
H4B	0.5372	0.3501	0.4023	0.109*
H4C	0.5377	0.3217	0.5319	0.109*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0438 (3)	0.0350 (3)	0.0425 (3)	0.00087 (17)	0.0231 (2)	0.00141 (16)
Cl1	0.0809 (14)	0.0551 (10)	0.0707 (13)	0.0188 (9)	0.0527 (11)	0.0088 (8)
Cl2	0.0610 (11)	0.0488 (9)	0.0764 (13)	−0.0084 (8)	0.0371 (10)	0.0094 (8)
Cl3	0.0709 (13)	0.0691 (12)	0.0452 (10)	0.0061 (9)	0.0165 (9)	0.0006 (8)
N1	0.056 (4)	0.044 (3)	0.059 (4)	0.008 (3)	0.032 (3)	0.000 (3)
O1	0.0531 (15)	0.0515 (15)	0.0514 (15)	−0.0033 (12)	0.0221 (12)	0.0004 (12)
O2	0.043 (2)	0.044 (2)	0.056 (3)	−0.001 (2)	0.023 (2)	−0.008 (2)
C1	0.0560 (14)	0.0550 (13)	0.0553 (14)	−0.0025 (9)	0.0195 (9)	0.0009 (9)
C2	0.048 (4)	0.044 (3)	0.044 (3)	0.003 (3)	0.022 (3)	−0.004 (3)
C3	0.097 (7)	0.065 (5)	0.083 (7)	0.001 (4)	0.046 (6)	−0.030 (4)
C4	0.051 (5)	0.071 (5)	0.099 (7)	0.016 (4)	0.031 (4)	0.000 (5)

Geometric parameters (Å, º) top

Sn1—O1	2.106 (5)	O2—C2	1.259 (7)
Sn1—O1ⁱ	2.101 (5)	C1—H1A	0.9600
Sn1—O2	2.108 (4)	C1—H1B	0.9600
Sn1—Cl1	2.372 (2)	C1—H1C	0.9600
Sn1—Cl2	2.3743 (18)	C2—H2	0.9300
Sn1—Cl3	2.368 (2)	C3—H3A	0.9600
N1—C2	1.291 (8)	C3—H3B	0.9600
N1—C4	1.452 (9)	C3—H3C	0.9600
N1—C3	1.457 (10)	C4—H4A	0.9600
O1—C1	1.455 (9)	C4—H4B	0.9600
O1—Sn1ⁱ	2.101 (5)	C4—H4C	0.9600

O1ⁱ—Sn1—O2	87.65 (18)	O1—C1—H1A	109.5
O1ⁱ—Sn1—O1	73.1 (2)	O1—C1—H1B	109.5
O2—Sn1—O1	84.69 (19)	H1A—C1—H1B	109.5
O1ⁱ—Sn1—Cl3	166.73 (15)	O1—C1—H1C	109.5
O2—Sn1—Cl3	85.64 (14)	H1A—C1—H1C	109.5
O1—Sn1—Cl3	94.86 (16)	H1B—C1—H1C	109.5
O1ⁱ—Sn1—Cl1	92.45 (15)	O2—C2—N1	123.2 (6)
O2—Sn1—Cl1	177.31 (12)	O2—C2—H2	118.4
O1—Sn1—Cl1	92.76 (15)	N1—C2—H2	118.4
Cl3—Sn1—Cl1	93.72 (9)	N1—C3—H3A	109.5
O1ⁱ—Sn1—Cl2	93.32 (14)	N1—C3—H3B	109.5
O2—Sn1—Cl2	88.59 (13)	H3A—C3—H3B	109.5
O1—Sn1—Cl2	165.05 (15)	N1—C3—H3C	109.5
Cl3—Sn1—Cl2	97.94 (8)	H3A—C3—H3C	109.5
Cl1—Sn1—Cl2	94.09 (8)	H3B—C3—H3C	109.5
C2—N1—C4	121.9 (6)	N1—C4—H4A	109.5
C2—N1—C3	120.6 (7)	N1—C4—H4B	109.5
C4—N1—C3	117.4 (6)	H4A—C4—H4B	109.5
C1—O1—Sn1ⁱ	124.2 (4)	N1—C4—H4C	109.5
C1—O1—Sn1	123.0 (4)	H4A—C4—H4C	109.5
Sn1ⁱ—O1—Sn1	106.9 (2)	H4B—C4—H4C	109.5
C2—O2—Sn1	124.0 (4)

O1ⁱ—Sn1—O1—C1	154.0 (6)	Cl2—Sn1—O1—Sn1ⁱ	−25.5 (7)
O2—Sn1—O1—C1	64.8 (5)	O1ⁱ—Sn1—O2—C2	42.9 (5)
Cl3—Sn1—O1—C1	−20.3 (5)	O1—Sn1—O2—C2	116.2 (5)
Cl1—Sn1—O1—C1	−114.3 (5)	Cl3—Sn1—O2—C2	−148.5 (5)
Cl2—Sn1—O1—C1	128.5 (6)	Cl2—Sn1—O2—C2	−50.4 (5)
O1ⁱ—Sn1—O1—Sn1ⁱ	0.0	Sn1—O2—C2—N1	−171.9 (5)
O2—Sn1—O1—Sn1ⁱ	−89.1 (2)	C4—N1—C2—O2	1.6 (10)
Cl3—Sn1—O1—Sn1ⁱ	−174.30 (17)	C3—N1—C2—O2	178.8 (7)
Cl1—Sn1—O1—Sn1ⁱ	91.72 (19)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···Cl3	0.96	2.72	3.356 (8)	124
C3—H3A···Cl3ⁱⁱ	0.96	2.95	3.895 (11)	170
C4—H4B···Cl1ⁱⁱⁱ	0.96	2.90	3.837 (9)	164

Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+3/2, y+1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	[Sn₂(CH₃O)₂Cl₆(C₃H₇NO)₂]
M_r	658.34
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	8.589 (8), 11.4444 (13), 11.8453 (10)
β (°)	111.155 (1)
V (Å³)	1085.9 (10)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	3.05
Crystal size (mm)	0.22 × 0.17 × 0.16

Data collection
Diffractometer	Bruker APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.553, 0.641
No. of measured, independent and observed [I > 2σ(I)] reflections	5512, 1903, 1554
R_int	0.063
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.117, 1.14
No. of reflections	1903
No. of parameters	103
No. of restraints	13
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.54, −2.07

Computer programs: SMART (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and X-SEED (Barbour, 2001), SHELXTL (Sheldrick, 2008).

Selected bond lengths (Å) top

Sn1—O1	2.106 (5)	Sn1—Cl1	2.372 (2)
Sn1—O1ⁱ	2.101 (5)	Sn1—Cl2	2.3743 (18)
Sn1—O2	2.108 (4)	Sn1—Cl3	2.368 (2)

Symmetry code: (i) −x+2, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1C···Cl3	0.96	2.72	3.356 (8)	124
C3—H3A···Cl3ⁱⁱ	0.96	2.95	3.895 (11)	170
C4—H4B···Cl1ⁱⁱⁱ	0.96	2.90	3.837 (9)	164

Symmetry codes: (ii) x+1/2, −y+1/2, z+1/2; (iii) −x+3/2, y+1/2, −z+1/2.

Acknowledgements

We acknowledge the National Natural Science Foundation of China (grant No. 20771053), the National Basic Research Program (grant No. 2010CB234601) and the Natural Science Foundation of Shandong Province (Y2008B48) for financial support. This work was also supported by the Shandong Tai-Shan Scholar Research Fund.

References

Barbour, L. J. (2001). J. Supramol. Chem. 1, 189–191. CrossRef CAS Google Scholar
Bruker (2007). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Mao, X.-A. & You, X.-Z. (1990). Acta Physico-Chimica Sinica, 6, 743–746. CAS Google Scholar
Reuter, H. & Schröder, D. (1992). Acta Cryst. C48, 1112–1114. CSD CrossRef CAS Web of Science 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