2-Meth-oxy-anilinium trichlorido-stannate(II).

The title compound, (C7H10NO)[SnCl3], is a new compound with non-linear optical (NLO) properties. The structure is pseudocentrosymmetric; the absence of an inversion centre was proved by the Kurtz and Perry method showing a significant second harmonic generation (SHG) signal about ten times lower than that from potassium dihydrogenphosphate. The crystal structure exhibits alternating organic and inorganic layers parallel to the ab plane, which are stabilized by inter-molecular N-H⋯Cl inter-actions.

Related literature

For related structures, see: Zhang et al. (2009 ▶). For the effects of substituents on the inter­nal angles of the benzene ring, see: Domenicano & Murray-Rust (1979 ▶). For NLO and SHG, see: Kurtz & Perry (1968 ▶); Kamoun et al. (1995 ▶). For ferroelectricity of related compounds, see: Ben Gozlen et al. (1994 ▶). For electric and dielectric properties of related compounds, see: Karoui et al. (2013 ▶).

Experimental

Crystal data

(C7H10NO)[SnCl3]

M = 349.20

Orthorhombic,

a = 7.2030 (2) Å

b = 8.3341 (3) Å

c = 19.5436 (6) Å

V = 1173.21 (6) Å3

Z = 4

Mo Kα radiation

μ = 2.82 mm−1

T = 296 K

0.41 × 0.34 × 0.10 mm

Data collection

Agilent Xcalibur (Sapphire2) diffractometer

Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012 ▶) T min = 0.391, T max = 0.765

8969 measured reflections

2392 independent reflections

2236 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.026

wR(F 2) = 0.064

S = 1.14

2392 reflections

120 parameters

H-atom parameters constrained

Δρmax = 0.89 e Å−3

Δρmin = −0.69 e Å−3

Absolute structure: Flack (1983 ▶), 986 Friedel pairs

Flack parameter: 0.03 (5)

Data collection: CrysAlis PRO (Agilent, 2012 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis RED (Agilent, 2012 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg et al., 1999 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶) and publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813005096/vn2066sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813005096/vn2066Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536813005096/vn2066Isup3.cdx

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

(C7H10NO)[SnCl3]	Cell parameters from 8969 reflections
Mr = 349.20	Dx = 1.977 Mg m−3Dm = 2.010 Mg m−3Dm measured by Flotation
Orthorhombic, P212121	Melting point: 413 K
Hall symbol: P 2ac 2ab	Mo Kα radiation, λ = 0.71073 Å
a = 7.2030 (2) Å	Cell parameters from 8969 reflections
b = 8.3341 (3) Å	θ = 2.1–27.0°
c = 19.5436 (6) Å	µ = 2.82 mm−1
V = 1173.21 (6) Å3	T = 296 K
Z = 4	Square, yellow
F(000) = 672	0.41 × 0.34 × 0.10 mm

Agilent Xcalibur (Sapphire2) diffractometer	2392 independent reflections
Radiation source: Enhance (Mo) X-ray Source	2236 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.019
Detector resolution: 8.3622 pixels mm-1	θmax = 26.4°, θmin = 3.0°
ω scans	h = −8→9
Absorption correction: multi-scan (CrysAlis RED; Agilent, 2012)	k = −10→9
Tmin = 0.391, Tmax = 0.765	l = −24→24
8969 measured reflections

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)] = 0.026	H-atom parameters constrained
wR(F2) = 0.064	w = 1/[σ2(Fo2) + (0.0195P)2 + 2.2881P] where P = (Fo2 + 2Fc2)/3
S = 1.14	(Δ/σ)max = 0.001
2392 reflections	Δρmax = 0.89 e Å−3
120 parameters	Δρmin = −0.69 e Å−3
0 restraints	Absolute structure: Flack (1983), 986 Friedel pairs
0 constraints	Flack parameter: 0.03 (5)
Primary atom site location: structure-invariant direct methods

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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.

	x	y	z	Uiso*/Ueq
Sn1	0.99329 (6)	0.71816 (4)	0.264736 (15)	0.03985 (10)
Cl1	0.74503 (19)	0.88251 (18)	0.20427 (10)	0.0480 (4)
Cl2	0.9729 (2)	0.52707 (13)	0.15669 (5)	0.0476 (3)
Cl3	1.2567 (2)	0.85165 (18)	0.20246 (10)	0.0462 (3)
C1	0.4660 (8)	0.4713 (7)	0.0448 (2)	0.0460 (13)
C2	0.4807 (8)	0.4108 (5)	0.1105 (2)	0.0391 (10)
C3	0.4722 (9)	0.2504 (6)	0.1238 (3)	0.0514 (13)
H3	0.4823	0.2135	0.1686	0.062*
C4	0.4489 (10)	0.1437 (8)	0.0712 (3)	0.068 (2)
H4	0.4431	0.0339	0.0795	0.082*
C5	0.4343 (11)	0.2026 (10)	0.0061 (4)	0.084 (2)
H5	0.4185	0.1308	−0.0298	0.101*
C6	0.4420 (10)	0.3637 (9)	−0.0081 (3)	0.070 (2)
H6	0.4312	0.3999	−0.0529	0.084*
C7	0.4756 (17)	0.7027 (9)	−0.0271 (3)	0.099 (3)
H7A	0.4865	0.8172	−0.0234	0.148*
H7B	0.3612	0.6763	−0.0496	0.148*
H7C	0.5779	0.6615	−0.0533	0.148*
N1	0.5056 (8)	0.5263 (4)	0.16573 (16)	0.0447 (8)
H1A	0.4333	0.6112	0.1584	0.067*
H1B	0.6237	0.5574	0.1672	0.067*
H1C	0.4749	0.4809	0.2054	0.067*
O1	0.4774 (9)	0.6327 (5)	0.03995 (17)	0.0666 (12)

	U11	U22	U33	U12	U13	U23
Sn1	0.03921 (16)	0.03849 (15)	0.04186 (16)	−0.00094 (18)	0.0010 (2)	0.00600 (12)
Cl1	0.0361 (6)	0.0544 (8)	0.0536 (9)	0.0062 (6)	−0.0035 (6)	−0.0039 (8)
Cl2	0.0745 (10)	0.0346 (5)	0.0337 (5)	−0.0027 (7)	0.0002 (7)	0.0003 (4)
Cl3	0.0350 (6)	0.0483 (7)	0.0551 (9)	−0.0056 (6)	0.0058 (6)	−0.0033 (7)
C1	0.042 (4)	0.060 (3)	0.036 (2)	0.003 (3)	−0.002 (2)	0.000 (2)
C2	0.035 (3)	0.048 (2)	0.034 (2)	−0.001 (3)	0.006 (2)	−0.0062 (17)
C3	0.057 (4)	0.046 (3)	0.051 (3)	−0.002 (3)	0.010 (3)	−0.003 (2)
C4	0.086 (6)	0.053 (3)	0.067 (4)	−0.011 (3)	0.009 (3)	−0.015 (3)
C5	0.100 (6)	0.093 (6)	0.060 (4)	−0.016 (4)	0.001 (4)	−0.036 (4)
C6	0.083 (5)	0.090 (5)	0.036 (3)	−0.004 (4)	−0.007 (3)	−0.009 (3)
C7	0.151 (8)	0.094 (5)	0.052 (3)	0.018 (8)	−0.002 (6)	0.031 (3)
N1	0.060 (2)	0.0428 (19)	0.0314 (17)	0.004 (3)	0.000 (3)	0.0015 (14)
O1	0.100 (4)	0.061 (2)	0.0394 (18)	0.012 (3)	0.003 (3)	0.0159 (16)

Sn1—Cl1	2.5437 (15)	C4—H4	0.9300
Sn1—Cl2	2.6489 (11)	C5—C6	1.372 (10)
Sn1—Cl3	2.5139 (15)	C5—H5	0.9300
C1—O1	1.351 (6)	C6—H6	0.9300
C1—C6	1.379 (8)	C7—O1	1.435 (6)
C1—C2	1.384 (6)	C7—H7A	0.9600
C2—C3	1.363 (6)	C7—H7B	0.9600
C2—N1	1.458 (5)	C7—H7C	0.9600
C3—C4	1.370 (8)	N1—H1A	0.8900
C3—H3	0.9300	N1—H1B	0.8900
C4—C5	1.367 (10)	N1—H1C	0.8900
Cl3—Sn1—Cl1	93.87 (4)	C6—C5—H5	118.8
Cl3—Sn1—Cl2	85.52 (5)	C5—C6—C1	119.4 (6)
Cl1—Sn1—Cl2	85.10 (5)	C5—C6—H6	120.3
O1—C1—C6	127.1 (5)	C1—C6—H6	120.3
O1—C1—C2	115.0 (4)	O1—C7—H7A	109.5
C6—C1—C2	117.9 (5)	O1—C7—H7B	109.5
C3—C2—C1	122.1 (5)	H7A—C7—H7B	109.5
C3—C2—N1	120.7 (4)	O1—C7—H7C	109.5
C1—C2—N1	117.2 (4)	H7A—C7—H7C	109.5
C2—C3—C4	119.9 (5)	H7B—C7—H7C	109.5
C2—C3—H3	120.1	C2—N1—H1A	109.5
C4—C3—H3	120.1	C2—N1—H1B	109.5
C5—C4—C3	118.3 (6)	H1A—N1—H1B	109.5
C5—C4—H4	120.8	C2—N1—H1C	109.5
C3—C4—H4	120.8	H1A—N1—H1C	109.5
C4—C5—C6	122.4 (6)	H1B—N1—H1C	109.5
C4—C5—H5	118.8	C1—O1—C7	117.9 (5)
O1—C1—C2—C3	−179.9 (6)	C3—C4—C5—C6	0.0 (12)
C6—C1—C2—C3	0.0 (9)	C4—C5—C6—C1	0.2 (12)
O1—C1—C2—N1	0.2 (8)	O1—C1—C6—C5	179.7 (7)
C6—C1—C2—N1	−179.8 (5)	C2—C1—C6—C5	−0.2 (10)
C1—C2—C3—C4	0.2 (10)	C6—C1—O1—C7	−4.0 (12)
N1—C2—C3—C4	−180.0 (6)	C2—C1—O1—C7	176.0 (7)
C2—C3—C4—C5	−0.1 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1C···Cl1i	0.89	2.51	3.339 (4)	155
N1—H1C···Cl3ii	0.89	2.85	3.418 (4)	123
N1—H1A···Cl3iii	0.89	2.53	3.329 (4)	151
N1—H1B···Cl2	0.89	2.54	3.371 (6)	157
N1—H1B···Cl1	0.89	2.94	3.515 (4)	124
N1—H1A···O1	0.89	2.34	2.621 (5)	98

Table 1

Selected bond lengths (Å)

Sn1—Cl1	2.5437 (15)
Sn1—Cl2	2.6489 (11)
Sn1—Cl3	2.5139 (15)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1C⋯Cl1i	0.89	2.51	3.339 (4)	155
N1—H1C⋯Cl3ii	0.89	2.85	3.418 (4)	123
N1—H1A⋯Cl3iii	0.89	2.53	3.329 (4)	151
N1—H1B⋯Cl2	0.89	2.54	3.371 (6)	157
N1—H1B⋯Cl1	0.89	2.94	3.515 (4)	124

Symmetry codes: (i) ; (ii) ; (iii) .