Bis[3-(meth­oxy­carbon­yl)anilinium] hexa­chloridostannate(IV)

Xue, R.-T.; Song, X.-W.; Chen, S.-G.; Yin, Y.-S.

doi:10.1107/S1600536810054310

metal-organic compounds

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Volume 67| Part 2| February 2011| Page m188

doi:10.1107/S1600536810054310

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Bis[3-(methoxycarbonyl)anilinium] hexachloridostannate(IV)

Rui-Ting Xue,^a Xian-Wang Song,^a Shou-Gang Chen ^a and Yan-Sheng Yin ^a ^*

^aInstitute of Material Science and Engineering, Ocean University of China, Qingdao, Shandong 266100, People's Republic of China
^*Correspondence e-mail: yys2004@ouc.edu.cn

(Received 9 December 2010; accepted 26 December 2010; online 15 January 2011)

In the title compound, (NH₃C₆H₄CO₂CH₃)₂[SnCl₆], the anions are situated on inversion centers so the asymmetric unit contains one cation and one half-anion. In the crystal, intermolecular N—H⋯Cl and N—H⋯O hydrogen bonds link the cations and anions into layers parallel to the ac plane. The crystal packing exhibits voids of 37 Å³.

Related literature

For general background to inorganic–organic hybrid compounds, see: Cheetham et al. (1999 ); Descalzo et al. (2006 ); Sanchez et al. (2003 , 2005 ).

Experimental

Crystal data

(C₈H₁₀NO₂)₂[SnCl₆]
M_r = 635.73
Triclinic, $[P \overline 1]$
a = 7.2320 (7) Å
b = 8.2701 (9) Å
c = 11.2801 (12) Å
α = 86.980 (2)°
β = 81.970 (2)°
γ = 65.870 (1)°
V = 609.66 (11) Å³
Z = 1
Mo Kα radiation
μ = 1.73 mm⁻¹
T = 293 K
0.18 × 0.16 × 0.12 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.746, T_max = 0.819
3096 measured reflections
2084 independent reflections
1846 reflections with I > 2σ(I)
R_int = 0.032

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.156
S = 1.01
2084 reflections
135 parameters
H-atom parameters constrained
Δρ_max = 3.34 e Å⁻³
Δρ_min = −1.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O2ⁱ	0.89	1.99	2.832 (7)	157
N1—H1B⋯Cl1ⁱ	0.89	3.00	3.542 (6)	121
N1—H1C⋯Cl2ⁱⁱ	0.89	2.57	3.419 (6)	160
N1—H1B⋯Cl3ⁱⁱⁱ	0.89	2.42	3.267 (6)	159
Symmetry codes: (i) -x+1, -y, -z+1; (ii) -x+2, -y, -z+1; (iii) x-1, y, z+1.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810054310/cv5016sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810054310/cv5016Isup2.hkl

checkCIF report

Comment top

Inorganic-organic hybrid materials have been of great interest over recent years [Cheetham et al., 1999]. The supramolecular chemistry, the optical properties and the applications of the inorganic-organic nanocomposites have been reviewed in the literatures [Descalzo et al., 2006; Sanchez et al., 2003, 2005]. Recently, we have prepared the title compound. Here we present its crystal structure.

The title compound contains SnCl₆ inorganic anions and organic cations. The SnCl₆ inorganic anion displays regular octahedron, with average Sn—Cl distance of 2.4073 Å.The angles of Cl—Sn—Cl are 89.45 to 90.95° for the chlorine atoms in cis positions. In the organic cation, the dihedral angle between the ester group and the phenyl ring is 5.7(0.3)°.

In the crystal structure, intermolecular N—H···Cl and N—H···O hydrogen bonds (Table 1) link cations and anions into layers parallel to ac plane.

Related literature top

For general background to inorganic–organic hybrid compounds, see: Cheetham et al. (1999); Descalzo et al. (2006); Sanchez et al. (2003, 2005).

Experimental top

3-aminobenzoic acid (10 mmol) was dissolved to methanol (10 ml) and 5 ml hydrochloric acid was added. A few minutes later, an methanol solution (10 ml) of tin tetrachloride (5 mmol) was added with stirring. The reaction mixture was stirred for 4 h, a yellow solid then separated out. The precipitate formed was filtered off, washed several times with anhydrous methanol and dried under vacuum. Yellow block crystals of the title compound were obtained from methanol solution after four days by slow evaporation at room temperature.

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP in SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme [symmetry code: (A) -x + 2, -y, -z)

Bis[3-(methoxycarbonyl)anilinium] hexachloridostannate(IV) top

Crystal data top

(C₈H₁₀NO₂)₂[SnCl₆]	Z = 1
M_r = 635.73	F(000) = 314
Triclinic, P1	D_x = 1.732 Mg m⁻³
a = 7.2320 (7) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.2701 (9) Å	Cell parameters from 2281 reflections
c = 11.2801 (12) Å	θ = 2.7–27.6°
α = 86.980 (2)°	µ = 1.73 mm⁻¹
β = 81.970 (2)°	T = 293 K
γ = 65.870 (1)°	Block, colourless
V = 609.66 (11) Å³	0.18 × 0.16 × 0.12 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	2084 independent reflections
Radiation source: fine-focus sealed tube	1846 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.032
phi and ω scans	θ_max = 25.0°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.746, T_max = 0.819	k = −9→5
3096 measured reflections	l = −13→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)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.156	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.121P)²] where P = (F_o² + 2F_c²)/3
2084 reflections	(Δ/σ)_max < 0.001
135 parameters	Δρ_max = 3.34 e Å⁻³
0 restraints	Δρ_min = −1.32 e Å⁻³

Crystal data top

(C₈H₁₀NO₂)₂[SnCl₆]	γ = 65.870 (1)°
M_r = 635.73	V = 609.66 (11) Å³
Triclinic, P1	Z = 1
a = 7.2320 (7) Å	Mo Kα radiation
b = 8.2701 (9) Å	µ = 1.73 mm⁻¹
c = 11.2801 (12) Å	T = 293 K
α = 86.980 (2)°	0.18 × 0.16 × 0.12 mm
β = 81.970 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	2084 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1846 reflections with I > 2σ(I)
T_min = 0.746, T_max = 0.819	R_int = 0.032
3096 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.156	H-atom parameters constrained
S = 1.01	Δρ_max = 3.34 e Å⁻³
2084 reflections	Δρ_min = −1.32 e Å⁻³
135 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	1.0000	0.0000	0.0000	0.0328 (3)
Cl1	0.6515 (2)	0.2167 (2)	0.03141 (14)	0.0513 (5)
Cl2	0.9962 (3)	−0.0365 (2)	0.21342 (12)	0.0508 (4)
Cl3	1.1248 (3)	0.2268 (2)	0.00885 (15)	0.0552 (5)
N1	0.5099 (9)	0.0834 (7)	0.7957 (4)	0.0449 (13)
H1A	0.5244	−0.0115	0.7554	0.067*
H1B	0.4246	0.0948	0.8628	0.067*
H1C	0.6309	0.0709	0.8138	0.067*
O1	0.2054 (7)	0.4933 (6)	0.3593 (4)	0.0454 (10)
O2	0.3547 (9)	0.2009 (6)	0.3694 (4)	0.0652 (15)
C1	0.2955 (9)	0.3441 (8)	0.4139 (5)	0.0390 (13)
C2	0.3176 (9)	0.3708 (8)	0.5388 (5)	0.0374 (13)
C3	0.3979 (9)	0.2212 (8)	0.6087 (5)	0.0392 (13)
H3	0.4309	0.1090	0.5783	0.047*
C4	0.4274 (9)	0.2416 (8)	0.7219 (5)	0.0357 (12)
C5	0.3753 (10)	0.4048 (8)	0.7713 (5)	0.0426 (14)
H5	0.3942	0.4151	0.8500	0.051*
C6	0.2944 (11)	0.5536 (9)	0.7020 (6)	0.0473 (15)
H6	0.2596	0.6652	0.7339	0.057*
C7	0.2650 (9)	0.5377 (8)	0.5864 (6)	0.0424 (14)
H7	0.2100	0.6382	0.5400	0.051*
C8	0.1833 (12)	0.4799 (10)	0.2347 (6)	0.0552 (18)
H8A	0.3156	0.4360	0.1879	0.083*
H8B	0.1003	0.5948	0.2062	0.083*
H8C	0.1193	0.4000	0.2277	0.083*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Sn1	0.0336 (4)	0.0345 (4)	0.0272 (3)	−0.0093 (3)	−0.0072 (2)	−0.0035 (2)
Cl1	0.0371 (8)	0.0534 (10)	0.0467 (9)	0.0012 (7)	−0.0095 (6)	−0.0131 (7)
Cl2	0.0680 (11)	0.0481 (9)	0.0257 (8)	−0.0119 (8)	−0.0085 (6)	−0.0018 (6)
Cl3	0.0693 (11)	0.0552 (10)	0.0520 (9)	−0.0379 (9)	0.0033 (8)	−0.0157 (8)
N1	0.062 (3)	0.044 (3)	0.027 (2)	−0.019 (3)	−0.012 (2)	0.000 (2)
O1	0.056 (3)	0.040 (2)	0.032 (2)	−0.009 (2)	−0.0126 (18)	0.0018 (18)
O2	0.108 (4)	0.037 (3)	0.037 (2)	−0.011 (3)	−0.023 (3)	−0.003 (2)
C1	0.046 (3)	0.033 (3)	0.033 (3)	−0.010 (3)	−0.008 (2)	0.000 (3)
C2	0.037 (3)	0.040 (3)	0.032 (3)	−0.012 (3)	−0.003 (2)	−0.005 (2)
C3	0.044 (3)	0.036 (3)	0.032 (3)	−0.010 (3)	−0.003 (2)	−0.008 (2)
C4	0.038 (3)	0.039 (3)	0.027 (3)	−0.014 (3)	−0.002 (2)	−0.001 (2)
C5	0.047 (3)	0.046 (4)	0.033 (3)	−0.017 (3)	−0.004 (2)	−0.008 (3)
C6	0.060 (4)	0.039 (3)	0.040 (3)	−0.019 (3)	−0.001 (3)	−0.010 (3)
C7	0.045 (3)	0.034 (3)	0.043 (3)	−0.012 (3)	0.001 (3)	−0.003 (3)
C8	0.063 (4)	0.055 (4)	0.035 (3)	−0.010 (3)	−0.013 (3)	0.005 (3)

Geometric parameters (Å, º) top

Sn1—Cl3	2.4028 (16)	C2—C3	1.388 (9)
Sn1—Cl3ⁱ	2.4028 (16)	C2—C7	1.389 (9)
Sn1—Cl2ⁱ	2.4081 (14)	C3—C4	1.354 (8)
Sn1—Cl2	2.4081 (14)	C3—H3	0.9300
Sn1—Cl1ⁱ	2.4111 (15)	C4—C5	1.371 (9)
Sn1—Cl1	2.4111 (15)	C5—C6	1.381 (9)
N1—C4	1.465 (7)	C5—H5	0.9300
N1—H1A	0.8900	C6—C7	1.372 (9)
N1—H1B	0.8900	C6—H6	0.9300
N1—H1C	0.8900	C7—H7	0.9300
O1—C1	1.305 (7)	C8—H8A	0.9600
O1—C8	1.451 (7)	C8—H8B	0.9600
O2—C1	1.195 (7)	C8—H8C	0.9600
C1—C2	1.477 (8)

Cl3—Sn1—Cl3ⁱ	180.00 (3)	C3—C2—C7	119.9 (5)
Cl3—Sn1—Cl2ⁱ	90.55 (6)	C3—C2—C1	117.6 (5)
Cl3ⁱ—Sn1—Cl2ⁱ	89.45 (6)	C7—C2—C1	122.4 (6)
Cl3—Sn1—Cl2	89.45 (6)	C4—C3—C2	118.8 (5)
Cl3ⁱ—Sn1—Cl2	90.55 (6)	C4—C3—H3	120.6
Cl2ⁱ—Sn1—Cl2	180.00 (9)	C2—C3—H3	120.6
Cl3—Sn1—Cl1ⁱ	89.05 (7)	C3—C4—C5	122.5 (6)
Cl3ⁱ—Sn1—Cl1ⁱ	90.95 (7)	C3—C4—N1	118.5 (5)
Cl2ⁱ—Sn1—Cl1ⁱ	89.55 (6)	C5—C4—N1	119.0 (5)
Cl2—Sn1—Cl1ⁱ	90.45 (6)	C4—C5—C6	118.7 (5)
Cl3—Sn1—Cl1	90.95 (7)	C4—C5—H5	120.7
Cl3ⁱ—Sn1—Cl1	89.05 (7)	C6—C5—H5	120.7
Cl2ⁱ—Sn1—Cl1	90.45 (6)	C7—C6—C5	120.4 (6)
Cl2—Sn1—Cl1	89.55 (6)	C7—C6—H6	119.8
Cl1ⁱ—Sn1—Cl1	180.00 (6)	C5—C6—H6	119.8
C4—N1—H1A	109.5	C6—C7—C2	119.7 (6)
C4—N1—H1B	109.5	C6—C7—H7	120.1
H1A—N1—H1B	109.5	C2—C7—H7	120.1
C4—N1—H1C	109.5	O1—C8—H8A	109.5
H1A—N1—H1C	109.5	O1—C8—H8B	109.5
H1B—N1—H1C	109.5	H8A—C8—H8B	109.5
C1—O1—C8	116.2 (5)	O1—C8—H8C	109.5
O2—C1—O1	124.6 (5)	H8A—C8—H8C	109.5
O2—C1—C2	123.0 (5)	H8B—C8—H8C	109.5
O1—C1—C2	112.5 (5)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱⁱ	0.89	1.99	2.832 (7)	157
N1—H1B···Cl1ⁱⁱ	0.89	3.00	3.542 (6)	121
N1—H1C···Cl2ⁱⁱⁱ	0.89	2.57	3.419 (6)	160
N1—H1B···Cl3^iv	0.89	2.42	3.267 (6)	159

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

Experimental details

Crystal data
Chemical formula	(C₈H₁₀NO₂)₂[SnCl₆]
M_r	635.73
Crystal system, space group	Triclinic, P1
Temperature (K)	293
a, b, c (Å)	7.2320 (7), 8.2701 (9), 11.2801 (12)
α, β, γ (°)	86.980 (2), 81.970 (2), 65.870 (1)
V (Å³)	609.66 (11)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	1.73
Crystal size (mm)	0.18 × 0.16 × 0.12

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.746, 0.819
No. of measured, independent and observed [I > 2σ(I)] reflections	3096, 2084, 1846
R_int	0.032
(sin θ/λ)_max (Å⁻¹)	0.595

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.156, 1.01
No. of reflections	2084
No. of parameters	135
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	3.34, −1.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), XP in SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O2ⁱ	0.89	1.99	2.832 (7)	157.2
N1—H1B···Cl1ⁱ	0.89	3.00	3.542 (6)	120.9
N1—H1C···Cl2ⁱⁱ	0.89	2.57	3.419 (6)	160.1
N1—H1B···Cl3ⁱⁱⁱ	0.89	2.42	3.267 (6)	158.8

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

Acknowledgements

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

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