Bis(3-methyl­anilinium) hexa­chlorido­stannate(IV) dihydrate

Liu, M.-L.

doi:10.1107/S1600536812017618

metal-organic compounds

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ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page m681

doi:10.1107/S1600536812017618

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Bis(3-methylanilinium) hexachloridostannate(IV) dihydrate

Ming-Liang Liu ^a ^*

^aOrdered Matter Science Research Center, Southeast University, Nanjing 211189, People's Republic of China
^*Correspondence e-mail: jgsdxlml@163.com

(Received 11 April 2012; accepted 20 April 2012; online 28 April 2012)

In the title compound, (C₇H₁₀N)₂[SnCl₆]·2H₂O, the Sn^IV atom lies on a site with symmetry 2/m. One of the Cl atoms lies on a mirror plane and the 3-methylanilinium cation is also situated on a mirror plane. The water molecule is located on a twofold rotation axis. The H atoms of the methyl and ammonium groups and the solvent water molecule are disordered by symmetry. In the crystal, N—H⋯Cl, O—H⋯Cl and N—H⋯O hydrogen bonds connect the organic cations, the inorganic octahedrally shaped anions and the water molecules.

Related literature

For background to ferroelectric metal-organic complexes, see: Zhang et al. (2009 , 2010 ). For related structures, see: Liu (2011a ,b ,c ).

Experimental

Crystal data

(C₇H₁₀N)₂[SnCl₆]·2H₂O
M_r = 583.74
Monoclinic, C 2/m
a = 20.467 (4) Å
b = 7.1699 (14) Å
c = 7.7569 (16) Å
β = 93.83 (3)°
V = 1135.8 (4) Å³
Z = 2
Mo Kα radiation
μ = 1.84 mm⁻¹
T = 293 K
0.36 × 0.32 × 0.28 mm

Data collection

Rigaku Mercury2 CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.963, T_moax = 0.971
5833 measured reflections
1405 independent reflections
1370 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.030
wR(F²) = 0.096
S = 0.92
1405 reflections
74 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl2ⁱ	0.89	2.59	3.476 (4)	171
N1—H1B⋯O1ⁱⁱ	0.89	1.93	2.809 (5)	170
N1—H1C⋯Cl1ⁱⁱⁱ	0.89	2.75	3.5883 (7)	157
O1—H1D⋯Cl2	0.85	2.44	3.228 (2)	154
Symmetry codes: (i) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z-1]$ ; (ii) $[x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ ; (iii) $[-x+{\script{1\over 2}}, -y+{\script{3\over 2}}, -z+1]$ .

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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/S1600536812017618/hy2538sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812017618/hy2538Isup2.hkl

checkCIF report

Comment top

Recently much attention has been devoted to metal-organic compounds due to the tunability of their special structural features and their interesting physical properties (Zhang et al., 2009, 2010). As a continuation of our researches (Liu, 2011a,b,c), the title compound has been synthesized and its crystal structure is herein reported.

In the title compound, the Sn^IV atom lies on a 2/m symmetry site, and is coordinated by six Cl atoms (Fig. 1). One of the Cl atoms lies on a mirror plane and the 3-methylanilinium cation is also situated on a mirror plane. The water molecule is located on a twofold rotation axis. The H atoms of the methyl and amidogen groups and the water molecule are disordered induced by symmetry. N—H···Cl, O—H···Cl and N—H···O hydrogen-bonding interactions connect the [SnCl₆]^2- anions, the 3-methylanilinium cations and the water molecules (Table 1). The non-H atoms of the 3-methylanilinium cation are coplanar. The average Sn—Cl bond distances range from 2.4260 (13) to 2.4384 (9) Å and the cis Cl—Sn—Cl angles range from 88.78 (5) to 91.22 (5)°.

Related literature top

For background to ferroelectric metal-organic complexes, see: Zhang et al. (2009, 2010). For related structures, see: Liu (2011a,b,c).

Experimental top

3-Methylbenzenamine (3.21 g, 0.03 mol) was dissolved in 30 ml ethanol, to which hydrochloric acid (1.1 g, 0.03 mol) was then added. Stannous chloride (2.25 g, 0.01 mol) was dissolved in 20 ml ethanol, to which was added hydrochloric acid, then mixed with the above solution without any precipitation under stirring at ambient temperature. Single crystals suitable for X-ray structure analysis were obtained by slow evaporation after 4 days in air.

The dielectric constant of the compound as a function of temperature indicates that the permittivity is basically temperature-independent [ε = C/(T–T₀)], suggesting that this compound is not ferroelectric or there may be no distinct phase transition occurring within the measured temperature (below the melting point).

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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 the title compound. Displacement ellipsoids are drawn at the 30% probability level. H atoms on C7, N1 and O1 are disordered over two sets of sites. [Symmetry codes: (A) -x, -y, 2-z; (B) -x, y, 2-z; (C) x, -y, z.]

Bis(3-methylanilinium) hexachloridostannate(IV) dihydrate top

Crystal data top

(C₇H₁₀N)₂[SnCl₆]·2H₂O	F(000) = 580
M_r = 583.74	D_x = 1.707 Mg m⁻³
Monoclinic, C2/m	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2y	Cell parameters from 1370 reflections
a = 20.467 (4) Å	θ = 3.4–25.0°
b = 7.1699 (14) Å	µ = 1.84 mm⁻¹
c = 7.7569 (16) Å	T = 293 K
β = 93.83 (3)°	Block, colourless
V = 1135.8 (4) Å³	0.36 × 0.32 × 0.28 mm
Z = 2

Data collection top

Rigaku Mercury2 CCD diffractometer	1405 independent reflections
Radiation source: fine-focus sealed tube	1370 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.036
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −26→25
T_min = 0.963, T_max = 0.971	k = −9→9
5833 measured reflections	l = −10→10

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.030	H-atom parameters constrained
wR(F²) = 0.096	w = 1/[σ²(F_o²) + (0.0749P)² + 1.7826P] where P = (F_o² + 2F_c²)/3
S = 0.92	(Δ/σ)_max < 0.001
1405 reflections	Δρ_max = 0.38 e Å⁻³
74 parameters	Δρ_min = −0.73 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.041 (2)

Crystal data top

(C₇H₁₀N)₂[SnCl₆]·2H₂O	V = 1135.8 (4) Å³
M_r = 583.74	Z = 2
Monoclinic, C2/m	Mo Kα radiation
a = 20.467 (4) Å	µ = 1.84 mm⁻¹
b = 7.1699 (14) Å	T = 293 K
c = 7.7569 (16) Å	0.36 × 0.32 × 0.28 mm
β = 93.83 (3)°

Data collection top

Rigaku Mercury2 CCD diffractometer	1405 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1370 reflections with I > 2σ(I)
T_min = 0.963, T_max = 0.971	R_int = 0.036
5833 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.030	0 restraints
wR(F²) = 0.096	H-atom parameters constrained
S = 0.92	Δρ_max = 0.38 e Å⁻³
1405 reflections	Δρ_min = −0.73 e Å⁻³
74 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	Occ. (<1)
N1	0.4203 (2)	1.0000	0.2314 (5)	0.0565 (10)
H1A	0.4253	0.9464	0.1296	0.068*	0.50
H1B	0.4429	0.9367	0.3140	0.068*	0.50
H1C	0.4349	1.1169	0.2294	0.068*	0.50
C1	0.3335 (2)	1.0000	0.4366 (5)	0.0416 (8)
H1	0.3661	1.0000	0.5261	0.050*
C2	0.3501 (2)	1.0000	0.2664 (5)	0.0392 (8)
C3	0.3029 (2)	1.0000	0.1309 (5)	0.0537 (11)
H3	0.3147	1.0000	0.0171	0.064*
C4	0.2382 (2)	1.0000	0.1673 (6)	0.0618 (13)
H4	0.2058	1.0000	0.0774	0.074*
C5	0.2208 (2)	1.0000	0.3365 (7)	0.0542 (11)
H5	0.1767	1.0000	0.3588	0.065*
C6	0.2677 (2)	1.0000	0.4732 (5)	0.0429 (8)
C7	0.2496 (3)	1.0000	0.6588 (7)	0.0622 (13)
H7A	0.2819	1.0687	0.7285	0.075*	0.50
H7B	0.2481	0.8739	0.7000	0.075*	0.50
H7C	0.2075	1.0574	0.6659	0.075*	0.50
Sn1	0.0000	0.0000	1.0000	0.0370 (2)
Cl1	0.07220 (7)	0.0000	0.76437 (18)	0.0617 (3)
Cl2	−0.06652 (4)	0.24302 (12)	0.85527 (11)	0.0565 (3)
O1	0.0000	0.3385 (11)	0.5000	0.136 (3)
H1D	−0.0216	0.3511	0.5891	0.203*	0.50
H1E	0.0390	0.3062	0.5304	0.203*	0.50

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0412 (19)	0.081 (3)	0.0478 (19)	0.000	0.0093 (15)	0.000
C1	0.0394 (19)	0.050 (2)	0.0354 (17)	0.000	−0.0004 (14)	0.000
C2	0.0346 (18)	0.046 (2)	0.0368 (17)	0.000	0.0041 (14)	0.000
C3	0.054 (3)	0.072 (3)	0.0344 (18)	0.000	−0.0035 (17)	0.000
C4	0.045 (2)	0.085 (4)	0.053 (2)	0.000	−0.0157 (19)	0.000
C5	0.035 (2)	0.063 (3)	0.064 (3)	0.000	0.0028 (18)	0.000
C6	0.047 (2)	0.0370 (19)	0.0458 (19)	0.000	0.0089 (16)	0.000
C7	0.070 (3)	0.065 (3)	0.054 (2)	0.000	0.025 (2)	0.000
Sn1	0.0290 (2)	0.0291 (2)	0.0536 (3)	0.000	0.00791 (15)	0.000
Cl1	0.0550 (7)	0.0597 (7)	0.0742 (7)	0.000	0.0323 (6)	0.000
Cl2	0.0503 (4)	0.0477 (4)	0.0712 (5)	0.0134 (3)	0.0023 (3)	0.0088 (4)
O1	0.127 (5)	0.173 (7)	0.105 (4)	0.000	−0.009 (4)	0.000

Geometric parameters (Å, º) top

N1—C2	1.480 (5)	C5—H5	0.9300
N1—H1A	0.8900	C6—C7	1.511 (6)
N1—H1B	0.8899	C7—H7A	0.9602
N1—H1C	0.8901	C7—H7B	0.9600
C1—C2	1.385 (5)	C7—H7C	0.9600
C1—C6	1.395 (6)	Sn1—Cl1ⁱ	2.4260 (13)
C1—H1	0.9300	Sn1—Cl1	2.4260 (13)
C2—C3	1.380 (6)	Sn1—Cl2ⁱⁱ	2.4384 (9)
C3—C4	1.372 (7)	Sn1—Cl2ⁱⁱⁱ	2.4384 (9)
C3—H3	0.9300	Sn1—Cl2	2.4384 (9)
C4—C5	1.383 (7)	Sn1—Cl2ⁱ	2.4384 (9)
C4—H4	0.9300	O1—H1D	0.8500
C5—C6	1.383 (7)	O1—H1E	0.8499

C2—N1—H1A	109.5	C1—C6—C7	119.7 (4)
C2—N1—H1B	109.4	C6—C7—H7A	109.5
H1A—N1—H1B	109.5	C6—C7—H7B	109.5
C2—N1—H1C	109.5	H7A—C7—H7B	109.4
H1A—N1—H1C	109.5	C6—C7—H7C	109.4
H1B—N1—H1C	109.5	H7A—C7—H7C	109.5
C2—C1—C6	119.7 (4)	H7B—C7—H7C	109.5
C2—C1—H1	120.2	Cl1ⁱ—Sn1—Cl1	180.0
C6—C1—H1	120.2	Cl1ⁱ—Sn1—Cl2ⁱⁱ	89.85 (4)
C3—C2—C1	121.5 (4)	Cl1—Sn1—Cl2ⁱⁱ	90.15 (3)
C3—C2—N1	119.9 (4)	Cl1ⁱ—Sn1—Cl2ⁱⁱⁱ	90.15 (4)
C1—C2—N1	118.5 (4)	Cl1—Sn1—Cl2ⁱⁱⁱ	89.85 (4)
C2—C3—C4	118.6 (4)	Cl2ⁱⁱ—Sn1—Cl2ⁱⁱⁱ	180.0
C2—C3—H3	120.7	Cl1ⁱ—Sn1—Cl2	89.85 (3)
C4—C3—H3	120.7	Cl1—Sn1—Cl2	90.15 (3)
C5—C4—C3	120.7 (4)	Cl2ⁱⁱ—Sn1—Cl2	91.22 (5)
C5—C4—H4	119.7	Cl2ⁱⁱⁱ—Sn1—Cl2	88.78 (5)
C3—C4—H4	119.7	Cl1ⁱ—Sn1—Cl2ⁱ	90.15 (3)
C6—C5—C4	121.1 (4)	Cl1—Sn1—Cl2ⁱ	89.85 (3)
C6—C5—H5	119.5	Cl2ⁱⁱ—Sn1—Cl2ⁱ	88.78 (5)
C4—C5—H5	119.5	Cl2ⁱⁱⁱ—Sn1—Cl2ⁱ	91.22 (5)
C5—C6—C1	118.4 (4)	Cl2—Sn1—Cl2ⁱ	180.0
C5—C6—C7	121.9 (4)	H1D—O1—H1E	109.5

C6—C1—C2—C3	0.0	C3—C4—C5—C6	0.0
C6—C1—C2—N1	180.0	C4—C5—C6—C1	0.0
C1—C2—C3—C4	0.0	C4—C5—C6—C7	180.0
N1—C2—C3—C4	180.0	C2—C1—C6—C5	0.0
C2—C3—C4—C5	0.0	C2—C1—C6—C7	180.0

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2^iv	0.89	2.59	3.476 (4)	171
N1—H1B···O1^v	0.89	1.93	2.809 (5)	170
N1—H1C···Cl1^vi	0.89	2.75	3.5883 (7)	157
O1—H1D···Cl2	0.85	2.44	3.228 (2)	154

Symmetry codes: (iv) x+1/2, y+1/2, z−1; (v) x+1/2, y+1/2, z; (vi) −x+1/2, −y+3/2, −z+1.

Experimental details

Crystal data
Chemical formula	(C₇H₁₀N)₂[SnCl₆]·2H₂O
M_r	583.74
Crystal system, space group	Monoclinic, C2/m
Temperature (K)	293
a, b, c (Å)	20.467 (4), 7.1699 (14), 7.7569 (16)
β (°)	93.83 (3)
V (Å³)	1135.8 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	1.84
Crystal size (mm)	0.36 × 0.32 × 0.28

Data collection
Diffractometer	Rigaku Mercury2 CCD diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.963, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	5833, 1405, 1370
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.030, 0.096, 0.92
No. of reflections	1405
No. of parameters	74
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.73

Computer programs: CrystalClear (Rigaku, 2005), 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
N1—H1A···Cl2ⁱ	0.89	2.59	3.476 (4)	171.0
N1—H1B···O1ⁱⁱ	0.89	1.93	2.809 (5)	170.3
N1—H1C···Cl1ⁱⁱⁱ	0.89	2.75	3.5883 (7)	157.2
O1—H1D···Cl2	0.85	2.44	3.228 (2)	154.2

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

Acknowledgements

The author thanks an anonymous advisor from Ordered Matter Science Research Centre, Southeast University, for great help in the revision of this paper.

References

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