Bis(2,3-dimethyl-anilinium) tetra-chlorido-zincate dihydrate.

In the title compound, (C(8)H(12)N)(2)[ZnCl(4)]·2H(2)O, the Zn atom is coordinated by four Cl atoms in a tetra-hedral geometry. The water mol-ecules and the organic cations inter-act with the [ZnCl(4)](2-) complex anions, building up a two-dimensional hydrogen-bonded network parallel to (100).

Related literature

For properties of aniline derivatives, see: Hirao & Fukuhara (1998 ▶); Linden et al. (1995 ▶); MacDiamid et al. (1998 ▶); Singh et al. (1995 ▶, 2002 ▶); Wang et al. (2002 ▶); Fábry et al. (2002 ▶). For structural comparison, see: Harrison (2005 ▶); Marouani et al. (2010 ▶).

Experimental

Crystal data

(C8H12N)2[n class="Chemical">ZnCl4]·2H2O

M = 487.57

Monoclinic,

a = 21.654 (2) Å

b = 7.432 (3) Å

c = 14.069 (2) Å

β = 90.30 (2)°

V = 2264.1 (10) Å3

Z = 4

Ag Kα radiation

λ = 0.56085 Å

μ = 0.82 mm−1

T = 293 K

0.35 × 0.30 × 0.25 mm

Data collection

Enraf–Nonius TurboCAD-4 diffractometer

16232 measured reflections

10928 independent reflections

5697 reflections with I > 2σ(I)

R int = 0.041

2 standard reflections every 120 min intensity decay: 5%

Refinement

R[F 2 > 2σ(F 2)] = 0.054

wR(F 2) = 0.151

S = 1.03

10363 reflections

232 parameters

H-atom parameters constrained

Δρmax = 0.77 e Å−3

Δρmin = −0.92 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ▶), ORTEP-3 for Windows (Farrugia, 1997 ▶) and PLATOn class="Chemical">N (Spek, 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811017478/dn2685sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811017478/dn2685Isup2.hkl

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

(C8H12N)2[ZnCl4]·2H2O	F(000) = 1008
Mr = 487.57	Dx = 1.430 Mg m−3
Monoclinic, P21/c	Ag Kα radiation, λ = 0.56085 Å
Hall symbol: -P 2ybc	Cell parameters from 25 reflections
a = 21.654 (2) Å	θ = 9–11°
b = 7.432 (3) Å	µ = 0.82 mm−1
c = 14.069 (2) Å	T = 293 K
β = 90.30 (2)°	Block, colourless
V = 2264.1 (10) Å3	0.35 × 0.30 × 0.25 mm
Z = 4

Enraf–Nonius TurboCAD-4 diffractometer	Rint = 0.041
Radiation source: fine-focus sealed tube	θmax = 28.0°, θmin = 2.3°
graphite	h = −36→2
non–profiled ω scans	k = −3→12
16232 measured reflections	l = −23→23
10928 independent reflections	2 standard reflections every 120 min
5697 reflections with I > 2σ(I)	intensity decay: 5%

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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.151	H-atom parameters constrained
S = 1.03	w = 1/[σ2(Fo2) + (0.0738P)2] where P = (Fo2 + 2Fc2)/3
10363 reflections	(Δ/σ)max = 0.005
232 parameters	Δρmax = 0.77 e Å−3
0 restraints	Δρmin = −0.92 e Å−3

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
Zn1	0.252371 (12)	−0.16993 (3)	0.528190 (18)	0.03788 (8)
Cl1	0.27972 (3)	0.07344 (10)	0.43474 (5)	0.05745 (18)
Cl2	0.21828 (3)	−0.39507 (9)	0.44011 (4)	0.04583 (14)
Cl3	0.33196 (3)	−0.28623 (10)	0.59834 (5)	0.05693 (18)
Cl4	0.18023 (3)	−0.07803 (10)	0.65412 (5)	0.05405 (16)
N1	0.15472 (9)	0.3472 (3)	0.62226 (15)	0.0432 (5)
H1A	0.1666	0.4037	0.5697	0.065*
H1B	0.1682	0.2341	0.6210	0.065*
H1C	0.1704	0.4032	0.6728	0.065*
C1	−0.00434 (11)	0.2889 (3)	0.55691 (16)	0.0390 (5)
C2	0.06097 (10)	0.2868 (3)	0.54830 (14)	0.0337 (4)
C3	0.08621 (10)	0.3481 (3)	0.62776 (15)	0.0352 (4)
C4	0.05039 (12)	0.4082 (4)	0.71143 (15)	0.0433 (5)
H4	0.0725	0.4497	0.7638	0.052*
C5	−0.01386 (13)	0.4076 (4)	0.71794 (18)	0.0496 (6)
H5	−0.0352	0.4463	0.7713	0.060*
C6	−0.04063 (11)	0.3476 (3)	0.64175 (18)	0.0455 (5)
H6	−0.0835	0.3408	0.6397	0.055*
C7	0.10203 (12)	0.2261 (4)	0.45764 (17)	0.0469 (5)
H7A	0.1423	0.1895	0.4790	0.070*
H7B	0.1059	0.3256	0.4145	0.070*
H7C	0.0822	0.1275	0.4258	0.070*
C8	−0.03606 (13)	0.2301 (4)	0.47333 (19)	0.0528 (7)
H8A	−0.0230	0.1104	0.4575	0.079*
H8B	−0.0268	0.3099	0.4217	0.079*
H8C	−0.0797	0.2304	0.4846	0.079*
N2	0.32690 (9)	0.0370 (3)	0.75104 (14)	0.0449 (5)
H2A	0.3019	0.0255	0.8007	0.067*
H2B	0.3236	−0.0597	0.7141	0.067*
H2C	0.3164	0.1345	0.7180	0.067*
C9	0.38814 (10)	0.0540 (3)	0.78301 (15)	0.0370 (4)
C10	0.44164 (11)	0.0658 (3)	0.71609 (16)	0.0392 (5)
C11	0.49906 (12)	0.0739 (3)	0.75038 (19)	0.0476 (6)
C12	0.49854 (14)	0.0754 (4)	0.8488 (2)	0.0633 (8)
H12	0.5369	0.0839	0.8783	0.076*
C13	0.44415 (15)	0.0651 (4)	0.9136 (2)	0.0618 (8)
H13	0.4507	0.0672	0.9789	0.074*
C14	0.38810 (12)	0.0534 (4)	0.88115 (16)	0.0458 (5)
H14	0.3529	0.0457	0.9186	0.055*
C15	0.44037 (14)	0.0705 (5)	0.60951 (17)	0.0584 (7)
H15A	0.4667	0.1654	0.5874	0.088*
H15B	0.3989	0.0917	0.5879	0.088*
H15C	0.4547	−0.0426	0.5851	0.088*
C16	0.56043 (13)	0.0778 (5)	0.6831 (3)	0.0686 (9)
H16A	0.5623	−0.0309	0.6463	0.103*
H16B	0.5967	0.0871	0.7223	0.103*
H16C	0.5583	0.1795	0.6411	0.103*
O1	0.18655 (11)	0.5435 (3)	0.77698 (15)	0.0708 (6)
H22	0.2147	0.4997	0.8063	0.106*
H23	0.1938	0.6349	0.7481	0.106*
O2	0.29296 (11)	0.2985 (3)	0.62872 (17)	0.0694 (6)
H20	0.3001	0.3971	0.6497	0.104*
H21	0.3001	0.2703	0.5757	0.104*

	U11	U22	U33	U12	U13	U23
Zn1	0.03496 (13)	0.03231 (13)	0.04624 (15)	−0.00035 (10)	−0.01116 (10)	−0.00039 (11)
Cl1	0.0599 (4)	0.0473 (4)	0.0651 (4)	−0.0146 (3)	−0.0099 (3)	0.0139 (3)
Cl2	0.0435 (3)	0.0433 (3)	0.0506 (3)	−0.0065 (2)	−0.0105 (2)	−0.0068 (2)
Cl3	0.0492 (3)	0.0477 (3)	0.0736 (4)	0.0098 (3)	−0.0305 (3)	−0.0102 (3)
Cl4	0.0570 (4)	0.0474 (4)	0.0578 (3)	0.0109 (3)	0.0097 (3)	0.0049 (3)
N1	0.0379 (9)	0.0407 (11)	0.0508 (10)	−0.0003 (8)	−0.0184 (8)	0.0025 (9)
C1	0.0378 (10)	0.0280 (9)	0.0511 (12)	−0.0022 (9)	−0.0153 (9)	0.0082 (9)
C2	0.0355 (10)	0.0258 (9)	0.0397 (10)	−0.0004 (8)	−0.0097 (8)	0.0028 (8)
C3	0.0343 (10)	0.0295 (10)	0.0416 (10)	0.0011 (8)	−0.0112 (8)	0.0040 (8)
C4	0.0494 (13)	0.0440 (13)	0.0363 (10)	0.0034 (11)	−0.0096 (9)	0.0023 (10)
C5	0.0523 (14)	0.0528 (16)	0.0439 (12)	0.0089 (12)	0.0023 (11)	0.0071 (11)
C6	0.0345 (11)	0.0441 (13)	0.0579 (14)	0.0004 (10)	−0.0052 (10)	0.0122 (11)
C7	0.0455 (12)	0.0456 (13)	0.0494 (12)	0.0001 (11)	−0.0075 (10)	−0.0090 (11)
C8	0.0521 (14)	0.0380 (12)	0.0680 (16)	−0.0076 (11)	−0.0301 (12)	0.0042 (12)
N2	0.0385 (10)	0.0503 (12)	0.0458 (10)	−0.0011 (9)	−0.0087 (8)	0.0019 (9)
C9	0.0386 (10)	0.0295 (10)	0.0427 (11)	0.0009 (9)	−0.0088 (9)	−0.0016 (9)
C10	0.0419 (11)	0.0317 (10)	0.0439 (11)	−0.0016 (9)	−0.0035 (9)	−0.0002 (9)
C11	0.0390 (11)	0.0336 (11)	0.0702 (16)	−0.0032 (10)	−0.0105 (11)	0.0016 (11)
C12	0.0550 (16)	0.0554 (17)	0.0791 (19)	−0.0041 (14)	−0.0303 (15)	−0.0023 (15)
C13	0.0702 (19)	0.0612 (18)	0.0537 (15)	−0.0002 (16)	−0.0254 (14)	−0.0045 (14)
C14	0.0497 (13)	0.0462 (14)	0.0414 (11)	0.0022 (11)	−0.0065 (10)	−0.0017 (10)
C15	0.0564 (16)	0.073 (2)	0.0455 (13)	−0.0108 (15)	−0.0007 (12)	0.0042 (13)
C16	0.0426 (14)	0.0590 (19)	0.104 (3)	−0.0093 (14)	−0.0012 (15)	0.0018 (18)
O1	0.0872 (16)	0.0537 (12)	0.0712 (12)	−0.0128 (12)	−0.0381 (11)	−0.0002 (10)
O2	0.0762 (15)	0.0501 (12)	0.0815 (14)	0.0020 (11)	−0.0265 (12)	0.0059 (10)

Zn1—Cl3	2.1618 (7)	N2—C9	1.404 (3)
Zn1—Cl2	2.2069 (8)	N2—H2A	0.8900
Zn1—Cl1	2.3149 (9)	N2—H2B	0.8900
Zn1—Cl4	2.4648 (8)	N2—H2C	0.8900
N1—C3	1.486 (3)	C9—C14	1.381 (3)
N1—H1A	0.8900	C9—C10	1.499 (3)
N1—H1B	0.8900	C10—C11	1.333 (3)
N1—H1C	0.8900	C10—C15	1.500 (3)
C1—C2	1.420 (3)	C11—C12	1.384 (4)
C1—C8	1.427 (3)	C11—C16	1.636 (4)
C1—C6	1.498 (4)	C12—C13	1.495 (5)
C2—C3	1.323 (3)	C12—H12	0.9300
C2—C7	1.623 (3)	C13—C14	1.297 (4)
C3—C4	1.482 (3)	C13—H13	0.9300
C4—C5	1.395 (4)	C14—H14	0.9300
C4—H4	0.9300	C15—H15A	0.9600
C5—C6	1.295 (4)	C15—H15B	0.9600
C5—H5	0.9300	C15—H15C	0.9600
C6—H6	0.9300	C16—H16A	0.9600
C7—H7A	0.9600	C16—H16B	0.9600
C7—H7B	0.9600	C16—H16C	0.9600
C7—H7C	0.9600	O1—H22	0.8041
C8—H8A	0.9600	O1—H23	0.8069
C8—H8B	0.9600	O2—H20	0.8042
C8—H8C	0.9600	O2—H21	0.7908
Cl3—Zn1—Cl2	102.52 (3)	H8A—C8—H8C	109.5
Cl3—Zn1—Cl1	111.47 (3)	H8B—C8—H8C	109.5
Cl2—Zn1—Cl1	111.06 (3)	C9—N2—H2A	109.5
Cl3—Zn1—Cl4	106.82 (3)	C9—N2—H2B	109.5
Cl2—Zn1—Cl4	113.72 (3)	H2A—N2—H2B	109.5
Cl1—Zn1—Cl4	110.90 (3)	C9—N2—H2C	109.5
C3—N1—H1A	109.5	H2A—N2—H2C	109.5
C3—N1—H1B	109.5	H2B—N2—H2C	109.5
H1A—N1—H1B	109.5	C14—C9—N2	108.3 (2)
C3—N1—H1C	109.5	C14—C9—C10	129.3 (2)
H1A—N1—H1C	109.5	N2—C9—C10	122.40 (19)
H1B—N1—H1C	109.5	C11—C10—C9	119.9 (2)
C2—C1—C8	113.7 (2)	C11—C10—C15	111.9 (2)
C2—C1—C6	126.7 (2)	C9—C10—C15	128.2 (2)
C8—C1—C6	119.6 (2)	C10—C11—C12	110.5 (3)
C3—C2—C1	109.4 (2)	C10—C11—C16	123.4 (2)
C3—C2—C7	122.3 (2)	C12—C11—C16	126.1 (2)
C1—C2—C7	128.32 (18)	C11—C12—C13	128.3 (2)
C2—C3—C4	124.0 (2)	C11—C12—H12	115.8
C2—C3—N1	111.3 (2)	C13—C12—H12	115.8
C4—C3—N1	124.71 (19)	C14—C13—C12	121.8 (2)
C5—C4—C3	125.3 (2)	C14—C13—H13	119.1
C5—C4—H4	117.4	C12—C13—H13	119.1
C3—C4—H4	117.4	C13—C14—C9	110.2 (3)
C6—C5—C4	112.9 (3)	C13—C14—H14	124.9
C6—C5—H5	123.6	C9—C14—H14	124.9
C4—C5—H5	123.6	C10—C15—H15A	109.5
C5—C6—C1	121.7 (2)	C10—C15—H15B	109.5
C5—C6—H6	119.1	H15A—C15—H15B	109.5
C1—C6—H6	119.1	C10—C15—H15C	109.5
C2—C7—H7A	109.5	H15A—C15—H15C	109.5
C2—C7—H7B	109.5	H15B—C15—H15C	109.5
H7A—C7—H7B	109.5	C11—C16—H16A	109.5
C2—C7—H7C	109.5	C11—C16—H16B	109.5
H7A—C7—H7C	109.5	H16A—C16—H16B	109.5
H7B—C7—H7C	109.5	C11—C16—H16C	109.5
C1—C8—H8A	109.5	H16A—C16—H16C	109.5
C1—C8—H8B	109.5	H16B—C16—H16C	109.5
H8A—C8—H8B	109.5	H22—O1—H23	116.7
C1—C8—H8C	109.5	H20—O2—H21	123.3

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl2i	0.89	2.61	3.488 (2)	168
N1—H1B···Cl4	0.89	2.38	3.239 (2)	162
N1—H1C···O1	0.89	1.83	2.707 (3)	168
N2—H2A···Cl2ii	0.89	2.85	3.713 (2)	165
N2—H2B···Cl3	0.89	2.35	3.225 (2)	168
N2—H2C···O2	0.89	1.82	2.696 (3)	167
O1—H22···Cl1iii	0.80	2.35	3.115 (2)	160
O1—H23···Cl4i	0.81	2.53	3.304 (3)	162
O2—H20···Cl3i	0.80	2.56	3.228 (3)	142
O2—H21···Cl1	0.79	2.50	3.213 (2)	150

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl2i	0.89	2.61	3.488 (2)	168
N1—H1B⋯Cl4	0.89	2.38	3.239 (2)	162
N1—H1C⋯O1	0.89	1.83	2.707 (3)	168
N2—H2A⋯Cl2ii	0.89	2.85	3.713 (2)	165
N2—H2B⋯Cl3	0.89	2.35	3.225 (2)	168
N2—H2C⋯O2	0.89	1.82	2.696 (3)	167
O1—H22⋯Cl1iii	0.80	2.35	3.115 (2)	160
O1—H23⋯Cl4i	0.81	2.53	3.304 (3)	162
O2—H20⋯Cl3i	0.80	2.56	3.228 (3)	142
O2—H21⋯Cl1	0.79	2.50	3.213 (2)	150

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