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

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.

Key indicators

• Single-crystal X-ray study
• T = 298 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.029
• wR factor = 0.082
• Data-to-parameter ratio = 17.2

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT125_ALERT_4_C No '_symmetry_space_group_name_Hall' Given .....     Please Do !
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.595          2 Why ?
PLAT975_ALERT_2_C Check Calcd Residual Density  1.00A From      N1       0.54 eA-3
PLAT976_ALERT_2_C Check Calcd Residual Density  1.03A From      N2      -0.47 eA-3
PLAT976_ALERT_2_C Check Calcd Residual Density  0.96A From      N2      -0.41 eA-3

Alert level G
PLAT005_ALERT_5_G No _iucr_refine_instructions_details  in the CIF     Please Do !
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............          3 Why ?
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT380_ALERT_4_G Incorrectly? Oriented X(sp2)-Methyl Moiety .....         N2 Check
PLAT794_ALERT_5_G Tentative Bond Valency for Sn1     (IV)    .....       3.98 Note
PLAT909_ALERT_3_G Percentage of Observed Data at Theta(Max) still          76 %

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   5 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   6 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   3 ALERT type 2 Indicator that the structure model may be wrong or deficient
   2 ALERT type 3 Indicator that the structure quality may be low
   2 ALERT type 4 Improvement, methodology, query or suggestion
   3 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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.

S3. Refinement

All H-atoms were positioned geometrically and refined using a riding model, with C—H=0.93 Å (aromatic), N—H=0.89 Å (ammonium) and U_iso(H) =1.2U_eq(C), U_iso(H) =1.5U_eq(N)

Computing details

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

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)

Crystal data

(C3H5N2S)2[SnCl6]	F(000) = 516
Mr = 533.69	Dx = 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) Å^3	Block, yellow
Z = 2	0.43 × 0.41 × 0.40 mm

Data collection

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

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.082	H-atom parameters constrained
S = 1.01	w = 1/[σ^2(Fo^2) + (0.0447P)^2 + 0.6842P] where P = (Fo^2 + 2Fc^2)/3
1529 reflections	(Δ/σ)max = 0.006
89 parameters	Δρmax = 0.81 e Å^−3
0 restraints	Δρmin = −0.52 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Sn1—Cl3^i	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—Cl1^i	2.4238 (9)	N2—H2B	0.8900
Sn1—Cl2^i	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)
Cl3^i—Sn1—Cl3	180.0	C1—N1—C2	113.4 (3)
Cl3^i—Sn1—Cl1	89.33 (4)	C1—N2—H2A	109.5
Cl3—Sn1—Cl1	90.67 (4)	C1—N2—H2B	109.5
Cl3^i—Sn1—Cl1^i	90.67 (4)	H2A—N2—H2B	109.5
Cl3—Sn1—Cl1^i	89.33 (4)	C1—N2—H2C	109.5
Cl1—Sn1—Cl1^i	180.0	H2A—N2—H2C	109.5
Cl3^i—Sn1—Cl2^i	91.15 (4)	H2B—N2—H2C	109.5
Cl3—Sn1—Cl2^i	88.85 (4)	N2—C1—N1	124.1 (4)
Cl1—Sn1—Cl2^i	90.61 (3)	N2—C1—S1	124.6 (3)
Cl1^i—Sn1—Cl2^i	89.39 (3)	N1—C1—S1	111.3 (3)
Cl3^i—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
Cl1^i—Sn1—Cl2	90.61 (3)	C2—C3—S1	111.4 (4)
Cl2^i—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)

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···Cl3^i	0.89	2.78	3.337 (4)	122
N2—H2B···Cl2^ii	0.89	2.50	3.353 (4)	162
N2—H2C···S1^iii	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.