1-(2,5-Dimethyl-phen-yl)piperazine-1,4-diium tetra-chloridozincate monohydrate.

In the title compound, (C(12)H(20)N(2))[ZnCl(4)]·H(2)O, the two piperazine N atoms are protonated and the [ZnCl(4)](2-) anions adopt a slightly distorted tetra-hedral configuration. In the crystal, O-H⋯Cl hydrogen bonds link the tetra-chloridozincate anions and the water mol-ecules into corrugated inorganic chains parallel to [010]. The crystal structure is stabilized by N-H⋯Cl, N-H⋯O and O-H⋯Cl hydrogen bonds, with the N-H hydrogen bond originating from one of the two N atoms being trifurcated.

Related literature

For common applications of organic–inorganic hybrid materials, see: Dai et al. (2002 ▶); Tao et al. (2003 ▶). For a related structure and discussion of geometrical features, see: Ben Gharbia et al. (2007 ▶). For the geometry around the zinc atom, see: Harrison (2005 ▶).

Experimental

Crystal data

(C12H20N2)[ZnCl4]·H2O

M = 417.49

Monoclinic,

a = 7.0999 (8) Å

b = 8.0679 (8) Å

c = 29.933 (3) Å

β = 95.314 (2)°

V = 1707.2 (3) Å3

Z = 4

Mo Kα radiation

μ = 2.06 mm−1

T = 100 K

0.45 × 0.39 × 0.31 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.589, T max = 0.746

10440 measured reflections

4995 independent reflections

4738 reflections with I > 2σ(I)

R int = 0.016

Refinement

R[F 2 > 2σ(F 2)] = 0.027

wR(F 2) = 0.064

S = 1.13

4995 reflections

194 parameters

3 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.56 e Å−3

Δρmin = −0.44 e Å−3

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811007562/vn2004sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811007562/vn2004Isup2.hkl

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

(C12H20N2)[ZnCl4]·H2O	F(000) = 856
Mr = 417.49	Dx = 1.624 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6435 reflections
a = 7.0999 (8) Å	θ = 2.6–31.0°
b = 8.0679 (8) Å	µ = 2.06 mm−1
c = 29.933 (3) Å	T = 100 K
β = 95.314 (2)°	Block, colourless
V = 1707.2 (3) Å3	0.45 × 0.39 × 0.31 mm
Z = 4

Bruker SMART APEX CCD diffractometer	4995 independent reflections
Radiation source: fine-focus sealed tube	4738 reflections with I > 2σ(I)
graphite	Rint = 0.016
ω scans	θmax = 31.0°, θmin = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −7→10
Tmin = 0.589, Tmax = 0.746	k = −11→9
10440 measured reflections	l = −43→35

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)] = 0.027	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.064	H atoms treated by a mixture of independent and constrained refinement
S = 1.13	w = 1/[σ2(Fo2) + (0.0258P)2 + 1.2487P] where P = (Fo2 + 2Fc2)/3
4995 reflections	(Δ/σ)max = 0.001
194 parameters	Δρmax = 0.56 e Å−3
3 restraints	Δρmin = −0.44 e Å−3

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
C1	0.8731 (2)	0.27945 (19)	0.07313 (5)	0.0113 (3)
C2	0.8347 (2)	0.4334 (2)	0.05374 (5)	0.0130 (3)
H2	0.8573	0.5314	0.0710	0.016*
C3	0.7627 (2)	0.4442 (2)	0.00884 (5)	0.0141 (3)
C4	0.7332 (2)	0.2967 (2)	−0.01512 (5)	0.0165 (3)
H4	0.6897	0.3009	−0.0461	0.020*
C5	0.7664 (2)	0.1440 (2)	0.00543 (5)	0.0167 (3)
H5	0.7415	0.0460	−0.0117	0.020*
C6	0.8351 (2)	0.1302 (2)	0.05048 (5)	0.0132 (3)
C7	0.7193 (2)	0.6104 (2)	−0.01244 (6)	0.0181 (3)
H7A	0.8379	0.6673	−0.0171	0.027*
H7B	0.6471	0.6773	0.0073	0.027*
H7C	0.6448	0.5950	−0.0414	0.027*
C8	0.8579 (2)	−0.0383 (2)	0.07188 (6)	0.0171 (3)
H8A	0.9591	−0.0345	0.0965	0.026*
H8B	0.8903	−0.1193	0.0494	0.026*
H8C	0.7391	−0.0709	0.0837	0.026*
C9	1.0911 (2)	0.4117 (2)	0.13428 (5)	0.0138 (3)
H9A	1.0178	0.5160	0.1349	0.017*
H9B	1.1859	0.4248	0.1123	0.017*
C10	1.1903 (2)	0.3783 (2)	0.18030 (5)	0.0134 (3)
H10A	1.2682	0.2768	0.1793	0.016*
H10B	1.2755	0.4719	0.1894	0.016*
C11	0.8135 (2)	0.2553 (2)	0.15357 (5)	0.0123 (3)
H11A	0.7264	0.1626	0.1448	0.015*
H11B	0.7382	0.3586	0.1535	0.015*
C12	0.9092 (2)	0.2244 (2)	0.20022 (5)	0.0136 (3)
H12A	0.8123	0.2206	0.2220	0.016*
H12B	0.9739	0.1156	0.2009	0.016*
Cl1	0.09333 (5)	0.80876 (5)	0.181490 (13)	0.01515 (8)
Cl2	0.52791 (5)	0.64529 (5)	0.132584 (12)	0.01449 (8)
Cl3	0.34586 (5)	1.07346 (5)	0.105858 (12)	0.01456 (8)
Cl4	0.55737 (5)	0.97161 (5)	0.219958 (12)	0.01489 (8)
N1	0.95988 (18)	0.27010 (16)	0.12030 (4)	0.0100 (2)
H1A	1.034 (3)	0.180 (2)	0.1220 (7)	0.012*
N2	1.04987 (18)	0.35667 (16)	0.21386 (4)	0.0115 (2)
H2A	0.9874	0.4552	0.2171	0.017*
H2B	1.1124	0.3297	0.2412	0.017*
O1	0.77955 (16)	0.59834 (15)	0.22753 (4)	0.0141 (2)
H1C	0.721 (3)	0.632 (3)	0.2039 (7)	0.037 (7)*
H1B	0.691 (3)	0.564 (3)	0.2421 (8)	0.033 (7)*
Zn1	0.38078 (2)	0.86992 (2)	0.158284 (6)	0.01076 (5)

	U11	U22	U33	U12	U13	U23
C1	0.0112 (6)	0.0153 (7)	0.0071 (6)	−0.0005 (5)	0.0002 (5)	−0.0015 (5)
C2	0.0120 (6)	0.0152 (7)	0.0118 (7)	−0.0001 (5)	0.0007 (5)	−0.0004 (5)
C3	0.0101 (6)	0.0200 (8)	0.0125 (7)	0.0021 (5)	0.0017 (5)	0.0024 (6)
C4	0.0137 (7)	0.0264 (8)	0.0094 (7)	0.0002 (6)	0.0001 (5)	−0.0008 (6)
C5	0.0168 (7)	0.0205 (8)	0.0123 (7)	−0.0009 (6)	−0.0010 (5)	−0.0051 (6)
C6	0.0122 (7)	0.0153 (7)	0.0119 (7)	−0.0006 (5)	0.0006 (5)	−0.0023 (5)
C7	0.0152 (7)	0.0236 (8)	0.0156 (7)	0.0042 (6)	0.0011 (6)	0.0058 (6)
C8	0.0211 (8)	0.0133 (7)	0.0166 (7)	−0.0024 (6)	−0.0002 (6)	−0.0032 (6)
C9	0.0160 (7)	0.0142 (7)	0.0106 (6)	−0.0057 (5)	−0.0021 (5)	−0.0001 (5)
C10	0.0121 (6)	0.0174 (7)	0.0104 (6)	−0.0028 (5)	−0.0003 (5)	−0.0005 (5)
C11	0.0114 (6)	0.0163 (7)	0.0092 (6)	−0.0015 (5)	0.0013 (5)	−0.0012 (5)
C12	0.0167 (7)	0.0137 (7)	0.0101 (6)	−0.0043 (5)	0.0005 (5)	0.0002 (5)
Cl1	0.01373 (16)	0.01711 (17)	0.01506 (17)	−0.00208 (13)	0.00366 (12)	−0.00155 (13)
Cl2	0.01657 (17)	0.01327 (16)	0.01348 (16)	0.00368 (13)	0.00053 (12)	−0.00140 (12)
Cl3	0.01723 (17)	0.01358 (16)	0.01277 (16)	0.00171 (13)	0.00079 (12)	0.00279 (12)
Cl4	0.01381 (16)	0.01768 (17)	0.01260 (16)	−0.00089 (13)	−0.00196 (12)	−0.00211 (13)
N1	0.0111 (5)	0.0108 (6)	0.0078 (5)	0.0000 (4)	−0.0004 (4)	−0.0009 (4)
N2	0.0139 (6)	0.0122 (6)	0.0083 (5)	0.0003 (4)	0.0003 (4)	−0.0007 (4)
O1	0.0130 (5)	0.0165 (5)	0.0126 (5)	0.0005 (4)	0.0006 (4)	0.0012 (4)
Zn1	0.01151 (9)	0.01048 (9)	0.01017 (9)	0.00058 (6)	0.00039 (6)	−0.00003 (6)

C1—C2	1.387 (2)	C9—H9B	0.9900
C1—C6	1.396 (2)	C10—N2	1.490 (2)
C1—N1	1.4892 (18)	C10—H10A	0.9900
C2—C3	1.396 (2)	C10—H10B	0.9900
C2—H2	0.9500	C11—N1	1.5096 (19)
C3—C4	1.395 (2)	C11—C12	1.516 (2)
C3—C7	1.504 (2)	C11—H11A	0.9900
C4—C5	1.387 (2)	C11—H11B	0.9900
C4—H4	0.9500	C12—N2	1.4923 (19)
C5—C6	1.395 (2)	C12—H12A	0.9900
C5—H5	0.9500	C12—H12B	0.9900
C6—C8	1.506 (2)	Cl1—Zn1	2.2702 (5)
C7—H7A	0.9800	Cl2—Zn1	2.2619 (4)
C7—H7B	0.9800	Cl3—Zn1	2.2690 (4)
C7—H7C	0.9800	Cl4—Zn1	2.2857 (4)
C8—H8A	0.9800	N1—H1A	0.901 (15)
C8—H8B	0.9800	N2—H2A	0.9200
C8—H8C	0.9800	N2—H2B	0.9200
C9—N1	1.5086 (19)	O1—H1C	0.832 (17)
C9—C10	1.512 (2)	O1—H1B	0.842 (16)
C9—H9A	0.9900
C2—C1—C6	123.19 (13)	N2—C10—H10A	109.5
C2—C1—N1	119.34 (13)	C9—C10—H10A	109.5
C6—C1—N1	117.47 (13)	N2—C10—H10B	109.5
C1—C2—C3	119.92 (15)	C9—C10—H10B	109.5
C1—C2—H2	120.0	H10A—C10—H10B	108.1
C3—C2—H2	120.0	N1—C11—C12	110.09 (12)
C4—C3—C2	117.78 (15)	N1—C11—H11A	109.6
C4—C3—C7	121.85 (14)	C12—C11—H11A	109.6
C2—C3—C7	120.37 (15)	N1—C11—H11B	109.6
C5—C4—C3	121.21 (14)	C12—C11—H11B	109.6
C5—C4—H4	119.4	H11A—C11—H11B	108.2
C3—C4—H4	119.4	N2—C12—C11	111.49 (12)
C4—C5—C6	121.95 (15)	N2—C12—H12A	109.3
C4—C5—H5	119.0	C11—C12—H12A	109.3
C6—C5—H5	119.0	N2—C12—H12B	109.3
C5—C6—C1	115.80 (14)	C11—C12—H12B	109.3
C5—C6—C8	119.83 (14)	H12A—C12—H12B	108.0
C1—C6—C8	124.34 (14)	C1—N1—C9	114.53 (12)
C3—C7—H7A	109.5	C1—N1—C11	112.33 (11)
C3—C7—H7B	109.5	C9—N1—C11	108.80 (11)
H7A—C7—H7B	109.5	C1—N1—H1A	106.4 (13)
C3—C7—H7C	109.5	C9—N1—H1A	104.7 (13)
H7A—C7—H7C	109.5	C11—N1—H1A	109.6 (13)
H7B—C7—H7C	109.5	C10—N2—C12	111.83 (12)
C6—C8—H8A	109.5	C10—N2—H2A	109.3
C6—C8—H8B	109.5	C12—N2—H2A	109.3
H8A—C8—H8B	109.5	C10—N2—H2B	109.3
C6—C8—H8C	109.5	C12—N2—H2B	109.3
H8A—C8—H8C	109.5	H2A—N2—H2B	107.9
H8B—C8—H8C	109.5	H1C—O1—H1B	102 (2)
N1—C9—C10	109.95 (12)	Cl2—Zn1—Cl3	111.651 (16)
N1—C9—H9A	109.7	Cl2—Zn1—Cl1	112.737 (17)
C10—C9—H9A	109.7	Cl3—Zn1—Cl1	108.974 (16)
N1—C9—H9B	109.7	Cl2—Zn1—Cl4	109.040 (16)
C10—C9—H9B	109.7	Cl3—Zn1—Cl4	108.388 (17)
H9A—C9—H9B	108.2	Cl1—Zn1—Cl4	105.803 (16)
N2—C10—C9	110.52 (12)
C6—C1—C2—C3	−3.1 (2)	N1—C9—C10—N2	−58.83 (17)
N1—C1—C2—C3	176.62 (13)	N1—C11—C12—N2	56.18 (17)
C1—C2—C3—C4	−0.4 (2)	C2—C1—N1—C9	−31.94 (19)
C1—C2—C3—C7	179.62 (14)	C6—C1—N1—C9	147.82 (14)
C2—C3—C4—C5	2.8 (2)	C2—C1—N1—C11	92.83 (16)
C7—C3—C4—C5	−177.28 (15)	C6—C1—N1—C11	−87.40 (16)
C3—C4—C5—C6	−1.7 (3)	C10—C9—N1—C1	−172.56 (12)
C4—C5—C6—C1	−1.7 (2)	C10—C9—N1—C11	60.82 (16)
C4—C5—C6—C8	176.45 (15)	C12—C11—N1—C1	172.87 (12)
C2—C1—C6—C5	4.1 (2)	C12—C11—N1—C9	−59.25 (16)
N1—C1—C6—C5	−175.63 (13)	C9—C10—N2—C12	55.24 (17)
C2—C1—C6—C8	−173.91 (15)	C11—C12—N2—C10	−54.17 (17)
N1—C1—C6—C8	6.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl3i	0.90 (2)	2.46 (2)	3.2300 (14)	144 (2)
N2—H2A···O1	0.92	1.92	2.7925 (17)	157
N2—H2B···O1ii	0.92	2.19	2.9145 (17)	135
N2—H2B···Cl4ii	0.92	2.77	3.3965 (14)	127
N2—H2B···Cl1iii	0.92	2.85	3.4036 (14)	120
O1—H1C···Cl2	0.83 (2)	2.43 (2)	3.2361 (12)	164 (2)
O1—H1B···Cl4iii	0.84 (2)	2.31 (2)	3.1518 (13)	178 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl3i	0.90 (2)	2.46 (2)	3.2300 (14)	144 (2)
N2—H2A⋯O1	0.92	1.92	2.7925 (17)	157
N2—H2B⋯O1ii	0.92	2.19	2.9145 (17)	135
N2—H2B⋯Cl4ii	0.92	2.77	3.3965 (14)	127
N2—H2B⋯Cl1iii	0.92	2.85	3.4036 (14)	120
O1—H1C⋯Cl2	0.83 (2)	2.43 (2)	3.2361 (12)	164 (2)
O1—H1B⋯Cl4iii	0.84 (2)	2.31 (2)	3.1518 (13)	178 (3)

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