Tris(3-methyl-anilinium) tetra-chlorido-zincate chloride hemihydrate.

The asymmetric unit of the title compound, (C(7)H(10)N)(3)[ZnCl(4)]Cl·0.5H(2)O, consists of three 3-methyl-anilinium cations, one tetrahedral tetra-chloridozincate anion and one chloride anion and a water mol-ecule, which lies on a twofold axis. The components are linked into chains parallel to the a axis by N-H⋯Cl hydrogen bonds.

Related literature

For background to ferroelectric metal-organic complexes, see: Zhang et al. (2009 ▶, 2010 ▶); Ye et al. (2010 ▶). For a related structure, see: Rademeyer et al. (2005 ▶).

Experimental

Crystal data

(C7H10N)3[ZnCl4]Cl·0.5H2O

M = 576.13

Monoclinic,

a = 26.844 (5) Å

b = 7.7071 (15) Å

c = 28.605 (6) Å

β = 114.52 (3)°

V = 5385 (2) Å3

Z = 8

Mo Kα radiation

μ = 1.42 mm−1

T = 293 K

0.36 × 0.32 × 0.28 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.963, T max = 0.971

21123 measured reflections

4728 independent reflections

2941 reflections with I > 2σ(I)

R int = 0.114

Refinement

R[F 2 > 2σ(F 2)] = 0.060

wR(F 2) = 0.135

S = 0.99

4728 reflections

286 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.46 e Å−3

Δρmin = −0.34 e Å−3

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.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811044230/go2034sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811044230/go2034Isup2.hkl

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

(C7H10N)3[ZnCl4]Cl·0.5H2O	F(000) = 2376
Mr = 576.13	Dx = 1.421 Mg m−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 21123 reflections
a = 26.844 (5) Å	θ = 3.1–27.6°
b = 7.7071 (15) Å	µ = 1.42 mm−1
c = 28.605 (6) Å	T = 293 K
β = 114.52 (3)°	Block, colorless
V = 5385 (2) Å3	0.36 × 0.32 × 0.28 mm
Z = 8

Rigaku Mercury2 diffractometer	4728 independent reflections
Radiation source: fine-focus sealed tube	2941 reflections with I > 2σ(I)
graphite	Rint = 0.114
Detector resolution: 13.6612 pixels mm-1	θmax = 25.0°, θmin = 3.0°
CCD_Profile_fitting scans	h = −31→31
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −9→9
Tmin = 0.963, Tmax = 0.971	l = −34→34
21123 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)] = 0.060	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.135	w = 1/[σ2(Fo2) + (0.0496P)2 + 6.8371P] where P = (Fo2 + 2Fc2)/3
S = 0.99	(Δ/σ)max < 0.001
4728 reflections	Δρmax = 0.46 e Å−3
286 parameters	Δρmin = −0.34 e Å−3
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.038 (5)

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.

	x	y	z	Uiso*/Ueq
Zn1	0.05317 (2)	0.72394 (8)	0.18323 (2)	0.0439 (2)
Cl2	0.18258 (5)	0.19741 (18)	0.24934 (5)	0.0515 (4)
Cl3	0.12449 (6)	0.69858 (19)	0.15935 (5)	0.0573 (4)
Cl4	0.09197 (6)	0.67787 (17)	0.27015 (5)	0.0518 (4)
Cl5	−0.00605 (6)	0.50710 (18)	0.14357 (5)	0.0554 (4)
Cl6	0.01561 (6)	0.99087 (17)	0.16803 (5)	0.0538 (4)
C6	0.24123 (19)	0.6393 (7)	0.3266 (2)	0.0415 (13)
C13	0.12143 (19)	0.1269 (7)	0.34680 (18)	0.0373 (12)
C20	0.0782 (2)	0.2332 (7)	0.08050 (19)	0.0415 (13)
C19	0.0685 (2)	0.3746 (7)	0.0489 (2)	0.0461 (14)
H19	0.0684	0.4863	0.0612	0.055*
N1	0.21390 (17)	0.5968 (6)	0.27185 (15)	0.0522 (12)
H1A	0.2061	0.4841	0.2682	0.078*
H1B	0.2359	0.6226	0.2566	0.078*
H1C	0.1831	0.6580	0.2574	0.078*
C14	0.1301 (2)	0.2960 (7)	0.3638 (2)	0.0445 (13)
H14	0.1179	0.3863	0.3401	0.053*
N2	0.09265 (15)	0.0929 (5)	0.29173 (15)	0.0441 (11)
H2A	0.1139	0.1228	0.2761	0.066*
H2B	0.0619	0.1548	0.2789	0.066*
H2C	0.0846	−0.0195	0.2867	0.066*
C4	0.2855 (2)	0.5520 (8)	0.4130 (2)	0.0619 (17)
H4	0.2970	0.4652	0.4378	0.074*
C17	0.0593 (2)	0.1800 (7)	−0.0192 (2)	0.0509 (15)
H17	0.0529	0.1634	−0.0535	0.061*
N3	0.08751 (19)	0.2594 (6)	0.13476 (16)	0.0588 (13)
H3A	0.0663	0.1871	0.1427	0.088*
H3B	0.0793	0.3684	0.1392	0.088*
H3C	0.1225	0.2386	0.1551	0.088*
C21	0.07792 (19)	0.0668 (7)	0.0634 (2)	0.0455 (14)
H21	0.0839	−0.0262	0.0858	0.055*
C7	0.2497 (2)	0.8116 (7)	0.3409 (2)	0.0472 (14)
H7	0.2368	0.8979	0.3160	0.057*
C11	0.1671 (2)	0.0271 (8)	0.4321 (2)	0.0580 (16)
H11	0.1798	−0.0637	0.4555	0.070*
C12	0.1394 (2)	−0.0089 (7)	0.3806 (2)	0.0535 (15)
H12	0.1331	−0.1230	0.3690	0.064*
C5	0.2591 (2)	0.5088 (7)	0.3621 (2)	0.0536 (15)
H5	0.2533	0.3932	0.3520	0.064*
C16	0.0688 (2)	0.0374 (7)	0.0126 (2)	0.0437 (13)
C10	0.1761 (2)	0.1962 (8)	0.4495 (2)	0.0539 (15)
H10	0.1953	0.2179	0.4844	0.065*
C18	0.0590 (2)	0.3457 (7)	−0.0016 (2)	0.0525 (15)
H18	0.0524	0.4391	−0.0240	0.063*
C2	0.2773 (2)	0.8566 (7)	0.3922 (2)	0.0451 (13)
C3	0.2953 (2)	0.7245 (7)	0.4278 (2)	0.0524 (15)
H3	0.3145	0.7516	0.4624	0.063*
C9	0.1570 (2)	0.3331 (7)	0.4158 (2)	0.0474 (14)
C8	0.1640 (3)	0.5198 (7)	0.4342 (2)	0.0713 (19)
H8A	0.1715	0.5915	0.4104	0.107*
H8B	0.1940	0.5273	0.4675	0.107*
H8C	0.1310	0.5587	0.4363	0.107*
C1	0.2877 (2)	1.0442 (7)	0.4078 (2)	0.0629 (17)
H1D	0.3060	1.0990	0.3891	0.094*
H1E	0.3103	1.0516	0.4440	0.094*
H1F	0.2535	1.1016	0.4002	0.094*
C15	0.0684 (2)	−0.1441 (7)	−0.0068 (2)	0.0661 (18)
H15A	0.0415	−0.2119	−0.0010	0.099*
H15B	0.1038	−0.1955	0.0112	0.099*
H15C	0.0596	−0.1408	−0.0429	0.099*
O1W	0.0000	0.3163 (7)	0.2500	0.0475 (13)
H1WA	0.003 (3)	0.389 (6)	0.2295 (19)	0.09 (2)*

	U11	U22	U33	U12	U13	U23
Zn1	0.0477 (4)	0.0419 (4)	0.0403 (4)	0.0014 (3)	0.0166 (3)	0.0002 (3)
Cl2	0.0475 (8)	0.0584 (9)	0.0469 (8)	−0.0016 (7)	0.0178 (7)	0.0010 (7)
Cl3	0.0543 (9)	0.0729 (10)	0.0506 (9)	0.0074 (8)	0.0275 (8)	0.0081 (7)
Cl4	0.0631 (9)	0.0503 (9)	0.0382 (8)	0.0001 (7)	0.0172 (7)	0.0030 (6)
Cl5	0.0550 (9)	0.0537 (9)	0.0533 (9)	−0.0112 (7)	0.0183 (8)	−0.0056 (7)
Cl6	0.0585 (9)	0.0435 (8)	0.0567 (9)	0.0086 (7)	0.0212 (8)	0.0034 (7)
C6	0.029 (3)	0.047 (3)	0.044 (3)	0.000 (2)	0.012 (3)	0.000 (3)
C13	0.034 (3)	0.046 (3)	0.031 (3)	−0.003 (2)	0.013 (2)	−0.003 (3)
C20	0.041 (3)	0.048 (3)	0.032 (3)	0.000 (3)	0.012 (2)	0.002 (3)
C19	0.050 (3)	0.039 (3)	0.048 (3)	−0.002 (3)	0.019 (3)	−0.005 (3)
N1	0.050 (3)	0.055 (3)	0.044 (3)	−0.012 (2)	0.012 (2)	−0.004 (2)
C14	0.045 (3)	0.043 (3)	0.045 (3)	0.005 (3)	0.018 (3)	0.004 (3)
N2	0.042 (3)	0.044 (3)	0.044 (3)	0.000 (2)	0.014 (2)	−0.001 (2)
C4	0.066 (4)	0.061 (4)	0.047 (4)	0.007 (3)	0.011 (3)	0.017 (3)
C17	0.052 (4)	0.062 (4)	0.042 (3)	−0.006 (3)	0.023 (3)	−0.005 (3)
N3	0.060 (3)	0.069 (3)	0.041 (3)	0.006 (3)	0.014 (2)	0.002 (2)
C21	0.039 (3)	0.042 (3)	0.056 (4)	0.009 (3)	0.020 (3)	0.015 (3)
C7	0.053 (3)	0.046 (4)	0.044 (3)	0.011 (3)	0.022 (3)	0.018 (3)
C11	0.064 (4)	0.060 (4)	0.046 (4)	0.006 (3)	0.019 (3)	0.016 (3)
C12	0.069 (4)	0.040 (3)	0.052 (4)	0.000 (3)	0.026 (3)	0.002 (3)
C5	0.058 (4)	0.040 (3)	0.055 (4)	−0.003 (3)	0.016 (3)	0.002 (3)
C16	0.037 (3)	0.044 (3)	0.053 (4)	−0.007 (2)	0.021 (3)	−0.006 (3)
C10	0.049 (4)	0.070 (4)	0.041 (3)	−0.005 (3)	0.017 (3)	−0.005 (3)
C18	0.050 (4)	0.047 (4)	0.051 (4)	0.003 (3)	0.011 (3)	0.015 (3)
C2	0.039 (3)	0.047 (3)	0.055 (4)	0.002 (3)	0.025 (3)	0.002 (3)
C3	0.054 (4)	0.059 (4)	0.034 (3)	−0.003 (3)	0.008 (3)	−0.007 (3)
C9	0.042 (3)	0.056 (4)	0.044 (3)	0.001 (3)	0.017 (3)	−0.005 (3)
C8	0.083 (5)	0.062 (4)	0.067 (4)	−0.011 (3)	0.029 (4)	−0.022 (3)
C1	0.075 (4)	0.050 (4)	0.067 (4)	−0.005 (3)	0.032 (4)	−0.009 (3)
C15	0.066 (4)	0.054 (4)	0.090 (5)	−0.002 (3)	0.044 (4)	−0.014 (3)
O1W	0.051 (3)	0.039 (3)	0.055 (4)	0.000	0.024 (3)	0.000

Zn1—Cl6	2.2526 (14)	N3—H3B	0.8900
Zn1—Cl5	2.2607 (15)	N3—H3C	0.8900
Zn1—Cl4	2.2898 (16)	C21—C16	1.387 (7)
Zn1—Cl3	2.2924 (16)	C21—H21	0.9300
C6—C5	1.368 (7)	C7—C2	1.385 (7)
C6—C7	1.380 (7)	C7—H7	0.9300
C6—N1	1.464 (6)	C11—C12	1.375 (7)
C13—C12	1.370 (7)	C11—C10	1.380 (7)
C13—C14	1.376 (7)	C11—H11	0.9300
C13—N2	1.462 (6)	C12—H12	0.9300
C20—C19	1.370 (7)	C5—H5	0.9300
C20—C21	1.372 (7)	C16—C15	1.503 (7)
C20—N3	1.480 (6)	C10—C9	1.376 (7)
C19—C18	1.379 (7)	C10—H10	0.9300
C19—H19	0.9300	C18—H18	0.9300
N1—H1A	0.8900	C2—C3	1.378 (7)
N1—H1B	0.8900	C2—C1	1.504 (7)
N1—H1C	0.8900	C3—H3	0.9300
C14—C9	1.389 (7)	C9—C8	1.516 (7)
C14—H14	0.9300	C8—H8A	0.9600
N2—H2A	0.8900	C8—H8B	0.9600
N2—H2B	0.8900	C8—H8C	0.9600
N2—H2C	0.8900	C1—H1D	0.9600
C4—C5	1.370 (7)	C1—H1E	0.9600
C4—C3	1.386 (7)	C1—H1F	0.9600
C4—H4	0.9300	C15—H15A	0.9600
C17—C18	1.373 (7)	C15—H15B	0.9600
C17—C16	1.383 (7)	C15—H15C	0.9600
C17—H17	0.9300	O1W—H1WA	0.843 (10)
N3—H3A	0.8900
Cl6—Zn1—Cl5	114.39 (6)	C6—C7—C2	120.4 (5)
Cl6—Zn1—Cl4	108.46 (6)	C6—C7—H7	119.8
Cl5—Zn1—Cl4	109.79 (6)	C2—C7—H7	119.8
Cl6—Zn1—Cl3	112.49 (6)	C12—C11—C10	120.8 (5)
Cl5—Zn1—Cl3	106.73 (6)	C12—C11—H11	119.6
Cl4—Zn1—Cl3	104.52 (6)	C10—C11—H11	119.6
C5—C6—C7	121.5 (5)	C13—C12—C11	118.5 (5)
C5—C6—N1	119.7 (5)	C13—C12—H12	120.7
C7—C6—N1	118.7 (5)	C11—C12—H12	120.7
C12—C13—C14	121.1 (5)	C6—C5—C4	118.6 (5)
C12—C13—N2	119.9 (5)	C6—C5—H5	120.7
C14—C13—N2	119.0 (4)	C4—C5—H5	120.7
C19—C20—C21	122.5 (5)	C17—C16—C21	117.7 (5)
C19—C20—N3	119.1 (5)	C17—C16—C15	121.7 (5)
C21—C20—N3	118.4 (5)	C21—C16—C15	120.6 (5)
C20—C19—C18	117.7 (5)	C9—C10—C11	120.9 (5)
C20—C19—H19	121.2	C9—C10—H10	119.6
C18—C19—H19	121.2	C11—C10—H10	119.6
C6—N1—H1A	109.5	C17—C18—C19	120.5 (5)
C6—N1—H1B	109.5	C17—C18—H18	119.7
H1A—N1—H1B	109.5	C19—C18—H18	119.7
C6—N1—H1C	109.5	C3—C2—C7	117.8 (5)
H1A—N1—H1C	109.5	C3—C2—C1	121.7 (5)
H1B—N1—H1C	109.5	C7—C2—C1	120.4 (5)
C13—C14—C9	120.6 (5)	C2—C3—C4	121.3 (5)
C13—C14—H14	119.7	C2—C3—H3	119.3
C9—C14—H14	119.7	C4—C3—H3	119.3
C13—N2—H2A	109.5	C10—C9—C14	118.0 (5)
C13—N2—H2B	109.5	C10—C9—C8	121.9 (5)
H2A—N2—H2B	109.5	C14—C9—C8	120.1 (5)
C13—N2—H2C	109.5	C9—C8—H8A	109.5
H2A—N2—H2C	109.5	C9—C8—H8B	109.5
H2B—N2—H2C	109.5	H8A—C8—H8B	109.5
C5—C4—C3	120.4 (5)	C9—C8—H8C	109.5
C5—C4—H4	119.8	H8A—C8—H8C	109.5
C3—C4—H4	119.8	H8B—C8—H8C	109.5
C18—C17—C16	121.7 (5)	C2—C1—H1D	109.5
C18—C17—H17	119.2	C2—C1—H1E	109.5
C16—C17—H17	119.2	H1D—C1—H1E	109.5
C20—N3—H3A	109.5	C2—C1—H1F	109.5
C20—N3—H3B	109.5	H1D—C1—H1F	109.5
H3A—N3—H3B	109.5	H1E—C1—H1F	109.5
C20—N3—H3C	109.5	C16—C15—H15A	109.5
H3A—N3—H3C	109.5	C16—C15—H15B	109.5
H3B—N3—H3C	109.5	H15A—C15—H15B	109.5
C20—C21—C16	119.9 (5)	C16—C15—H15C	109.5
C20—C21—H21	120.0	H15A—C15—H15C	109.5
C16—C21—H21	120.0	H15B—C15—H15C	109.5
C21—C20—C19—C18	−0.8 (8)	C18—C17—C16—C15	179.3 (5)
N3—C20—C19—C18	−178.9 (5)	C20—C21—C16—C17	−1.0 (8)
C12—C13—C14—C9	−0.7 (8)	C20—C21—C16—C15	−180.0 (5)
N2—C13—C14—C9	179.6 (4)	C12—C11—C10—C9	0.9 (9)
C19—C20—C21—C16	1.3 (8)	C16—C17—C18—C19	0.2 (8)
N3—C20—C21—C16	179.4 (4)	C20—C19—C18—C17	0.1 (8)
C5—C6—C7—C2	0.8 (8)	C6—C7—C2—C3	−0.5 (8)
N1—C6—C7—C2	−177.4 (4)	C6—C7—C2—C1	178.6 (5)
C14—C13—C12—C11	−0.7 (8)	C7—C2—C3—C4	−0.9 (8)
N2—C13—C12—C11	179.1 (4)	C1—C2—C3—C4	−180.0 (5)
C10—C11—C12—C13	0.5 (8)	C5—C4—C3—C2	2.2 (9)
C7—C6—C5—C4	0.4 (8)	C11—C10—C9—C14	−2.2 (8)
N1—C6—C5—C4	178.6 (5)	C11—C10—C9—C8	177.0 (5)
C3—C4—C5—C6	−1.9 (9)	C13—C14—C9—C10	2.1 (8)
C18—C17—C16—C21	0.3 (8)	C13—C14—C9—C8	−177.2 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···Cl2i	0.89	2.34	3.176 (4)	157.
N2—H2C···Cl4ii	0.89	2.40	3.257 (4)	160.
N3—H3A···Cl6ii	0.89	2.34	3.231 (5)	176.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1B⋯Cl2i	0.89	2.34	3.176 (4)	157
N2—H2C⋯Cl4ii	0.89	2.40	3.257 (4)	160
N3—H3A⋯Cl6ii	0.89	2.34	3.231 (5)	176

Symmetry codes: (i) ; (ii) .