Bis(1,3-thia­zol-2-aminium) hexa­chlorido­stannate(IV)

Xue, R.; Kong, L.

doi:10.1107/S1600536814014032

metal-organic compounds

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ISSN: 2056-9890

Volume 70| Part 7| July 2014| Page m269

https://doi.org/10.1107/S1600536814014032

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Bis(1,3-thiazol-2-aminium) hexachloridostannate(IV)

Ruiting Xue ^a and Lingmin Kong ^b ^*

^aZibo Environmental Protection Bureau, Shandong 255030, People's Republic of China, and ^bSchool of Marine Science and Technology, Zhejiang Ocean University, Zhoushan 316022, People's Republic of China
^*Correspondence e-mail: xuert@163.com

(Received 1 June 2014; accepted 15 June 2014; online 21 June 2014)

The asymmetric unit of the title compound, (C₃H₅N₂S)₂[SnCl₆], contains one cation in a general position and one-half of the dianion situated on an inversion center. The geometry of the [SnCl₆]²⁻ dianion is almost regular octahedral. In the crystal, weak N—H⋯Cl and N—H⋯S hydrogen bonds and electrostatic forces link cations and anions into a three-dimensional framework.

Keywords: crystal structure.

CCDC reference: 796768

Related literature

For general background to inorganic-organic hybrid compounds, see: Zhang et al. (2009 ); Descazo et al. (2006 ); Li et al. (2007 ); Sanchez et al. (2005 ).

Experimental

Crystal data

(C₃H₅N₂S)₂[SnCl₆]
M_r = 533.69
Monoclinic, P 2₁ /c
a = 7.9185 (7) Å
b = 8.6737 (10) Å
c = 12.8952 (14) Å
β = 101.629 (1)°
V = 867.50 (16) Å³
Z = 2
Mo Kα radiation
μ = 2.63 mm⁻¹
T = 298 K
0.43 × 0.41 × 0.40 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.398, T_max = 0.420
4171 measured reflections
1529 independent reflections
1311 reflections with I > 2σ(I)
R_int = 0.039

Refinement

R[F² > 2σ(F²)] = 0.029
wR(F²) = 0.082
S = 1.01
1529 reflections
89 parameters
H-atom parameters constrained
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl1	0.89	2.70	3.522 (4)	155
N2—H2C⋯Cl3ⁱ	0.89	2.78	3.337 (4)	122
N2—H2B⋯Cl2ⁱⁱ	0.89	2.50	3.353 (4)	162
N2—H2C⋯S1ⁱⁱⁱ	0.89	2.84	3.595 (4)	144
Symmetry codes: (i) -x+1, -y+1, -z+1; (ii) x+1, y, z; (iii) $[-x+2, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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); software used to prepare material for publication: SHELXTL.

Supporting information

CCDC reference: 796768

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536814014032/cv5462sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814014032/cv5462Isup2.hkl

checkCIF report

Comment top

Considerable attention has been devoted to inorganic-organic hybrid materials over recent years·[Zhang et al., 2009]. The supramolecular chemistry, the optical properties and the applications of this kind of hybrid materials have been reviewed in the literatures [Descazo et al., 2006; Li et al., 2007; Sanchez et al., 2005]. Recently, we have prepared the title compound and here its crystal structure is reported.

This title compound contains SnCl6 inorganic anions and organic cations. The SnCl6 inorganic anion adopts an octahedron geometry, with average Sn—Cl distance 2.4278 Å. The inorganic anion and organic cation are linked through N—H···Cl hydrogen bond.

In the crystal structure, intermolecular N—H···Cl and N—H···S hydrogen bonds link cations and anions into a three-dimensioal framework. There are π-π stacking interactions involving the two thiazole rings, with a centroid···centroid distance of 3.769 (3) Å.

Related literature top

For general background to inorganic-organic hybrid compounds, see: Zhang et al. (2009); Descazo et al. (2006); Li et al. (2007), Sanchez et al. (2005).

Experimental top

2-aminothiazole (10 mmol) was dissolved to acid methanol solution (10 ml). Ten minutes later, an methanol solution (10 ml) of stannic chloride (5 mmol) was added with stirring. The mixture was stirred for 4 h. The solution was held at room temperature for about two weeks, whereupon yellow crystals suitable for X-ray diffraction analysis were obtained.

Structure description top

For general background to inorganic-organic hybrid compounds, see: Zhang et al. (2009); Descazo et al. (2006); Li et al. (2007), Sanchez et al. (2005).

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); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme [symmetry code: (A) -x + 1, -y + 1, -z + 1]. Dashed lines denote weak N—H···Cl hydrogen bonds.

Bis(1,3-thiazol-2-aminium) hexachloridostannate(IV) top

Crystal data top

(C₃H₅N₂S)₂[SnCl₆]	F(000) = 516
M_r = 533.69	D_x = 2.043 Mg m⁻³
Monoclinic, P2₁/c	Mo Kα radiation, λ = 0.71073 Å
a = 7.9185 (7) Å	Cell parameters from 2903 reflections
b = 8.6737 (10) Å	θ = 2.6–28.3°
c = 12.8952 (14) Å	µ = 2.63 mm⁻¹
β = 101.629 (1)°	T = 298 K
V = 867.50 (16) Å³	Block, yellow
Z = 2	0.43 × 0.41 × 0.40 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	1529 independent reflections
Radiation source: fine-focus sealed tube	1311 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.039
phi and ω scans	θ_max = 25.0°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −9→8
T_min = 0.398, T_max = 0.420	k = −10→10
4171 measured reflections	l = −15→12

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)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.082	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0447P)² + 0.6842P] where P = (F_o² + 2F_c²)/3
1529 reflections	(Δ/σ)_max = 0.006
89 parameters	Δρ_max = 0.81 e Å⁻³
0 restraints	Δρ_min = −0.52 e Å⁻³

Crystal data top

(C₃H₅N₂S)₂[SnCl₆]	V = 867.50 (16) Å³
M_r = 533.69	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 7.9185 (7) Å	µ = 2.63 mm⁻¹
b = 8.6737 (10) Å	T = 298 K
c = 12.8952 (14) Å	0.43 × 0.41 × 0.40 mm
β = 101.629 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1529 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1311 reflections with I > 2σ(I)
T_min = 0.398, T_max = 0.420	R_int = 0.039
4171 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.029	0 restraints
wR(F²) = 0.082	H-atom parameters constrained
S = 1.01	Δρ_max = 0.81 e Å⁻³
1529 reflections	Δρ_min = −0.52 e Å⁻³
89 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	0.5000	0.5000	0.5000	0.02834 (16)
S1	1.05330 (13)	0.99651 (11)	0.36139 (10)	0.0395 (3)
Cl1	0.76310 (12)	0.61913 (12)	0.59476 (8)	0.0430 (3)
Cl2	0.40115 (11)	0.75120 (11)	0.42742 (9)	0.0422 (3)
Cl3	0.36409 (13)	0.53966 (14)	0.65020 (9)	0.0438 (3)
N1	0.7590 (4)	0.8875 (4)	0.3679 (3)	0.0398 (8)
N2	0.9732 (4)	0.6990 (4)	0.3846 (3)	0.0474 (9)
H2A	0.9521	0.6619	0.4451	0.071*
H2B	1.0858	0.6943	0.3858	0.071*
H2C	0.9167	0.6430	0.3308	0.071*
C1	0.9217 (5)	0.8423 (5)	0.3731 (3)	0.0338 (9)
C2	0.7362 (5)	1.0453 (6)	0.3548 (4)	0.0445 (10)
H2	0.6303	1.0939	0.3503	0.053*
C3	0.8803 (5)	1.1204 (5)	0.3493 (3)	0.0421 (10)
H3	0.8870	1.2264	0.3400	0.051*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0269 (2)	0.0288 (3)	0.0304 (2)	0.00006 (13)	0.00865 (16)	0.00225 (14)
S1	0.0343 (5)	0.0390 (7)	0.0467 (7)	−0.0025 (4)	0.0117 (5)	0.0049 (5)
Cl1	0.0382 (5)	0.0456 (6)	0.0431 (6)	−0.0105 (4)	0.0028 (4)	0.0016 (5)
Cl2	0.0375 (5)	0.0338 (6)	0.0569 (7)	0.0046 (4)	0.0136 (4)	0.0113 (5)
Cl3	0.0439 (5)	0.0513 (6)	0.0408 (6)	0.0007 (5)	0.0192 (4)	−0.0030 (5)
N1	0.0332 (16)	0.048 (2)	0.0395 (19)	−0.0017 (15)	0.0110 (14)	−0.0024 (18)
N2	0.0449 (19)	0.045 (2)	0.056 (2)	−0.0028 (16)	0.0174 (17)	−0.0019 (19)
C1	0.038 (2)	0.038 (2)	0.028 (2)	−0.0007 (17)	0.0108 (16)	−0.0004 (18)
C2	0.040 (2)	0.053 (3)	0.040 (2)	0.012 (2)	0.0048 (18)	−0.003 (3)
C3	0.045 (2)	0.038 (2)	0.044 (2)	0.0062 (18)	0.0099 (19)	0.003 (2)

Geometric parameters (Å, º) top

Sn1—Cl3ⁱ	2.4224 (10)	N1—C2	1.387 (6)
Sn1—Cl3	2.4224 (10)	N2—C1	1.307 (5)
Sn1—Cl1	2.4238 (9)	N2—H2A	0.8900
Sn1—Cl1ⁱ	2.4238 (9)	N2—H2B	0.8900
Sn1—Cl2ⁱ	2.4374 (10)	N2—H2C	0.8900
Sn1—Cl2	2.4374 (10)	C2—C3	1.328 (6)
S1—C1	1.721 (4)	C2—H2	0.9300
S1—C3	1.723 (4)	C3—H3	0.9300
N1—C1	1.335 (5)

Cl3ⁱ—Sn1—Cl3	180.0	C1—N1—C2	113.4 (3)
Cl3ⁱ—Sn1—Cl1	89.33 (4)	C1—N2—H2A	109.5
Cl3—Sn1—Cl1	90.67 (4)	C1—N2—H2B	109.5
Cl3ⁱ—Sn1—Cl1ⁱ	90.67 (4)	H2A—N2—H2B	109.5
Cl3—Sn1—Cl1ⁱ	89.33 (4)	C1—N2—H2C	109.5
Cl1—Sn1—Cl1ⁱ	180.0	H2A—N2—H2C	109.5
Cl3ⁱ—Sn1—Cl2ⁱ	91.15 (4)	H2B—N2—H2C	109.5
Cl3—Sn1—Cl2ⁱ	88.85 (4)	N2—C1—N1	124.1 (4)
Cl1—Sn1—Cl2ⁱ	90.61 (3)	N2—C1—S1	124.6 (3)
Cl1ⁱ—Sn1—Cl2ⁱ	89.39 (3)	N1—C1—S1	111.3 (3)
Cl3ⁱ—Sn1—Cl2	88.85 (4)	C3—C2—N1	113.5 (4)
Cl3—Sn1—Cl2	91.15 (4)	C3—C2—H2	123.3
Cl1—Sn1—Cl2	89.39 (3)	N1—C2—H2	123.3
Cl1ⁱ—Sn1—Cl2	90.61 (3)	C2—C3—S1	111.4 (4)
Cl2ⁱ—Sn1—Cl2	180.00 (5)	C2—C3—H3	124.3
C1—S1—C3	90.5 (2)	S1—C3—H3	124.3

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
N2—H2A···Cl1	0.89	2.70	3.522 (4)	155
N2—H2C···Cl3ⁱ	0.89	2.78	3.337 (4)	122
N2—H2B···Cl2ⁱⁱ	0.89	2.50	3.353 (4)	162
N2—H2C···S1ⁱⁱⁱ	0.89	2.84	3.595 (4)	144

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl1	0.89	2.70	3.522 (4)	155.0
N2—H2C···Cl3ⁱ	0.89	2.78	3.337 (4)	121.8
N2—H2B···Cl2ⁱⁱ	0.89	2.50	3.353 (4)	162.0
N2—H2C···S1ⁱⁱⁱ	0.89	2.84	3.595 (4)	143.9

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

Acknowledgements

The authors acknowledge the National Science Foundation of China for its financial support of this project (grant Nos. 50672090 and 50702053).

References

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