Di-μ-hydroxido-bis­[aqua­trichlorido­tin(IV)] diethyl ether disolvate

Yang, M.; Yin, H.; Quan, L.; Cui, L.; Wang, D.

doi:10.1107/S1600536808032832

metal-organic compounds

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ISSN: 2056-9890

Volume 64| Part 11| November 2008| Page m1430

doi:10.1107/S1600536808032832

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Di-μ-hydroxido-bis[aquatrichloridotin(IV)] diethyl ether disolvate

Minglei Yang,^a Handong Yin,^a ^* Li Quan,^a Liansheng Cui ^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 15 September 2008; accepted 10 October 2008; online 18 October 2008)

The title compound, [Sn₂Cl₆(OH)₂(H₂O)₂]·2C₄H₁₀O, consists of a centrosymmetric molecule and two additional solvent molecules and has an infinite two-dimensional network extending parallel to (101). The Sn atom is six-coordinate with a distorted octahedral geometry. Additional O—H⋯O hydrogen bonding leads to stabilization of the crystal structure.

Related literature

For a related structure, see: Janas et al. (1991 )

Experimental

Crystal data

[Sn₂Cl₆(OH)₂(H₂O)₂]·2C₄H₁₀O
M_r = 668.36
Monoclinic, P 2₁ /n
a = 10.1171 (15) Å
b = 10.0212 (15) Å
c = 11.2641 (18) Å
β = 103.536 (1)°
V = 1110.3 (3) Å³
Z = 2
Mo Kα radiation
μ = 2.99 mm⁻¹
T = 298 (2) K
0.46 × 0.32 × 0.30 mm

Data collection

Siemens SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.340, T_max = 0.468 (expected range = 0.297–0.408)
5168 measured reflections
1909 independent reflections
1685 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.023
wR(F²) = 0.063
S = 0.84
1909 reflections
102 parameters
H-atom parameters constrained
Δρ_max = 1.05 e Å⁻³
Δρ_min = −0.68 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.93	1.88	2.799 (3)	169
O2—H2D⋯O3ⁱⁱ	0.85	1.89	2.736 (3)	176
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

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/S1600536808032832/sg2266sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808032832/sg2266Isup2.hkl

checkCIF report

Comment top

We have synthesized the title compound unexpectedly, (I), and present its crystal structure here. The title compound consist of a centrosymmetric dimer (Fig. 1) in which the tin atoms have a distorted octahedral arrangement formed by three chlorine atoms, two hydroxy oxygen bridges and one water molecule. A further two water molecules are hydrogen-bonded to the hydroxyl oxygen atoms of the µ-OH bridges. The Sn—O distances in (I) (Table 1), are similar to those in related organotin carboxylates. The Sn—Cl bond lengths and the interbond angles lie within the ranges observed for other related complexes. The Sn1—O1 (2.072 (2) Å) and Sn1—O2 distance (2.183 (2) Å), (Table 1), are close to those reported for organotin carboxylates (Janas et al., 1991).

Related literature top

For a related structure, see: Janas et al. (1991)

Experimental top

The reaction was carried out under nitrogen atmosphere. 3-Thiophenemalonic acid (1 mmol) and sodium ethoxide (2.2 mmol) were added to the solution of benzene (30 ml) in a Schlenk flask and stirred for 0.5 h. Phenyltin trichloride (1 mmol) was then added to the reactor and the mixture was stirred for 12 h at 338 K.The resulting clear solution was evaporated under vacuum. The product was crystallized from a mixture of diethylether/petroleum ether (1:1).Unexpectedly,a dimeric complex, was isolated from the filtrate. (yield 52%; m.p. 446 K). Analysis calculated (%) for C₄H₁₃Cl₃O₃Sn (Mr = 334.18): C,46.72; H, 4.49; O, 9.57. found: C, 46.52; H, 4.55; O, 9.62.

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 (I), showing 50% probability displacement ellipsoids and the atom-numbering scheme. H atoms have been omitted for clarity.
	Fig. 2. The infinite two-dimensional network structure of (I), H atoms have been omitted for clarity.

Di-µ-hydroxido-bis[aquatrichloridotin(IV)] diethyl ether disolvate top

Crystal data top

[Sn₂Cl₆(OH)₂(H₂O)₂]·2C₄H₁₀O	F(000) = 648
M_r = 668.36	D_x = 1.999 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 10.1171 (15) Å	Cell parameters from 4261 reflections
b = 10.0212 (15) Å	θ = 2.4–28.2°
c = 11.2641 (18) Å	µ = 2.99 mm⁻¹
β = 103.536 (1)°	T = 298 K
V = 1110.3 (3) Å³	Block, colorless
Z = 2	0.46 × 0.32 × 0.30 mm

Data collection top

Siemens SMART CCD area-detector diffractometer	1909 independent reflections
Radiation source: fine-focus sealed tube	1685 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
ϕ and ω scans	θ_max = 25.0°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −11→12
T_min = 0.340, T_max = 0.468	k = −11→11
5168 measured reflections	l = −7→13

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)] = 0.023	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.063	H-atom parameters constrained
S = 0.84	w = 1/[σ²(F_o²) + (0.0489P)² + 0.9726P] where P = (F_o² + 2F_c²)/3
1909 reflections	(Δ/σ)_max = 0.001
102 parameters	Δρ_max = 1.05 e Å⁻³
0 restraints	Δρ_min = −0.68 e Å⁻³

Crystal data top

[Sn₂Cl₆(OH)₂(H₂O)₂]·2C₄H₁₀O	V = 1110.3 (3) Å³
M_r = 668.36	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 10.1171 (15) Å	µ = 2.99 mm⁻¹
b = 10.0212 (15) Å	T = 298 K
c = 11.2641 (18) Å	0.46 × 0.32 × 0.30 mm
β = 103.536 (1)°

Data collection top

Siemens SMART CCD area-detector diffractometer	1909 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1685 reflections with I > 2σ(I)
T_min = 0.340, T_max = 0.468	R_int = 0.027
5168 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.023	0 restraints
wR(F²) = 0.063	H-atom parameters constrained
S = 0.84	Δρ_max = 1.05 e Å⁻³
1909 reflections	Δρ_min = −0.68 e Å⁻³
102 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	0.53184 (2)	0.46950 (2)	0.361848 (19)	0.02338 (10)
Cl1	0.66543 (10)	0.58991 (10)	0.25532 (9)	0.0421 (2)
Cl2	0.70089 (10)	0.30829 (10)	0.44565 (9)	0.0434 (2)
Cl3	0.41097 (10)	0.33403 (10)	0.20324 (9)	0.0470 (2)
O1	0.4121 (2)	0.4148 (2)	0.48000 (19)	0.0261 (5)
H1	0.3447	0.3497	0.4651	0.031*
O2	0.3762 (3)	0.6222 (3)	0.3036 (2)	0.0402 (6)
H2D	0.3543	0.6636	0.2360	0.048*
H2E	0.3425	0.6644	0.3549	0.048*
O3	0.8141 (2)	0.7541 (2)	0.5809 (2)	0.0367 (6)
C1	0.7894 (5)	0.8615 (4)	0.4926 (4)	0.0518 (11)
H1A	0.7798	0.8260	0.4109	0.062*
H1B	0.8653	0.9233	0.5091	0.062*
C2	0.6621 (6)	0.9321 (5)	0.5016 (5)	0.0660 (14)
H2A	0.5884	0.8694	0.4895	0.099*
H2B	0.6415	1.0003	0.4402	0.099*
H2C	0.6746	0.9720	0.5810	0.099*
C3	0.9279 (4)	0.6715 (5)	0.5690 (4)	0.0537 (12)
H3A	1.0075	0.7267	0.5730	0.064*
H3B	0.9066	0.6263	0.4907	0.064*
C4	0.9561 (5)	0.5717 (6)	0.6692 (5)	0.0720 (15)
H4A	0.9715	0.6168	0.7464	0.108*
H4B	1.0355	0.5210	0.6650	0.108*
H4C	0.8797	0.5128	0.6610	0.108*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.02419 (15)	0.02519 (15)	0.02104 (15)	0.00006 (8)	0.00583 (10)	−0.00080 (8)
Cl1	0.0446 (5)	0.0476 (5)	0.0398 (5)	−0.0069 (4)	0.0216 (4)	0.0052 (4)
Cl2	0.0438 (5)	0.0454 (5)	0.0423 (5)	0.0216 (4)	0.0127 (4)	0.0053 (4)
Cl3	0.0515 (6)	0.0523 (6)	0.0348 (5)	−0.0129 (5)	0.0053 (4)	−0.0163 (4)
O1	0.0273 (12)	0.0281 (12)	0.0234 (12)	−0.0074 (10)	0.0069 (9)	−0.0028 (9)
O2	0.0460 (15)	0.0483 (15)	0.0274 (13)	0.0203 (12)	0.0108 (11)	0.0104 (11)
O3	0.0334 (13)	0.0435 (14)	0.0355 (14)	−0.0047 (11)	0.0125 (11)	−0.0029 (11)
C1	0.071 (3)	0.047 (2)	0.037 (2)	−0.023 (2)	0.013 (2)	−0.0013 (19)
C2	0.076 (4)	0.048 (2)	0.063 (3)	0.002 (2)	−0.008 (3)	0.011 (2)
C3	0.034 (2)	0.074 (3)	0.056 (3)	−0.002 (2)	0.015 (2)	−0.025 (2)
C4	0.056 (3)	0.064 (3)	0.088 (4)	0.020 (3)	0.003 (3)	−0.012 (3)

Geometric parameters (Å, º) top

Sn1—O1	2.072 (2)	C1—C2	1.493 (7)
Sn1—O1ⁱ	2.090 (2)	C1—H1A	0.9700
Sn1—O2	2.183 (2)	C1—H1B	0.9700
Sn1—Cl1	2.3413 (9)	C2—H2A	0.9600
Sn1—Cl3	2.3469 (9)	C2—H2B	0.9600
Sn1—Cl2	2.3813 (9)	C2—H2C	0.9600
O1—Sn1ⁱ	2.090 (2)	C3—C4	1.485 (7)
O1—H1	0.9300	C3—H3A	0.9700
O2—H2D	0.8500	C3—H3B	0.9700
O2—H2E	0.8500	C4—H4A	0.9600
O3—C1	1.447 (5)	C4—H4B	0.9600
O3—C3	1.449 (5)	C4—H4C	0.9600

O1—Sn1—O1ⁱ	71.48 (9)	O3—C1—H1A	110.0
O1—Sn1—O2	83.66 (9)	C2—C1—H1A	110.0
O1ⁱ—Sn1—O2	84.28 (9)	O3—C1—H1B	110.0
O1—Sn1—Cl1	163.72 (7)	C2—C1—H1B	110.0
O1ⁱ—Sn1—Cl1	94.40 (6)	H1A—C1—H1B	108.4
O2—Sn1—Cl1	86.96 (7)	C1—C2—H2A	109.5
O1—Sn1—Cl3	93.27 (6)	C1—C2—H2B	109.5
O1ⁱ—Sn1—Cl3	163.56 (6)	H2A—C2—H2B	109.5
O2—Sn1—Cl3	88.04 (8)	C1—C2—H2C	109.5
Cl1—Sn1—Cl3	99.69 (4)	H2A—C2—H2C	109.5
O1—Sn1—Cl2	92.27 (7)	H2B—C2—H2C	109.5
O1ⁱ—Sn1—Cl2	90.68 (7)	O3—C3—C4	109.3 (4)
O2—Sn1—Cl2	174.32 (7)	O3—C3—H3A	109.8
Cl1—Sn1—Cl2	96.06 (4)	C4—C3—H3A	109.8
Cl3—Sn1—Cl2	96.16 (4)	O3—C3—H3B	109.8
Sn1—O1—Sn1ⁱ	108.52 (9)	C4—C3—H3B	109.8
Sn1—O1—H1	125.7	H3A—C3—H3B	108.3
Sn1ⁱ—O1—H1	125.7	C3—C4—H4A	109.5
Sn1—O2—H2D	129.1	C3—C4—H4B	109.5
Sn1—O2—H2E	121.4	H4A—C4—H4B	109.5
H2D—O2—H2E	107.7	C3—C4—H4C	109.5
C1—O3—C3	112.0 (3)	H4A—C4—H4C	109.5
O3—C1—C2	108.6 (3)	H4B—C4—H4C	109.5

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.93	1.88	2.799 (3)	169
O2—H2D···O3ⁱⁱ	0.85	1.89	2.736 (3)	176
O2—H2E···Cl2ⁱ	0.85	2.40	3.179 (3)	152

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

Experimental details

Crystal data
Chemical formula	[Sn₂Cl₆(OH)₂(H₂O)₂]·2C₄H₁₀O
M_r	668.36
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	10.1171 (15), 10.0212 (15), 11.2641 (18)
β (°)	103.536 (1)
V (Å³)	1110.3 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	2.99
Crystal size (mm)	0.46 × 0.32 × 0.30

Data collection
Diffractometer	Siemens SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.340, 0.468
No. of measured, independent and observed [I > 2σ(I)] reflections	5168, 1909, 1685
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.023, 0.063, 0.84
No. of reflections	1909
No. of parameters	102
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	1.05, −0.68

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.93	1.88	2.799 (3)	168.5
O2—H2D···O3ⁱⁱ	0.85	1.89	2.736 (3)	175.5
O2—H2E···Cl2ⁱ	0.85	2.40	3.179 (3)	152.0

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

Acknowledgements

We thank the National Natural Science Foundation of China (grant No. 20771053) for financial support.

References

Janas, Z., Sobota, P. & Lis, T. (1991). J. Chem. Soc. Dalton Trans. pp. 2429–2434. CSD CrossRef Web of Science 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