The organic–inorganic hybrid material 1-cyclo­hexyl­piperazine-1,4-diium tetra­chlorido­zincate

In the crystal structure of the title organic–inorganic hybrid material, (C₁₀H₂₂N₂)[ZnCl₄], the tetra­chlorido­zincate anions and 1-cyclo­hexyl­piperazine-1,4-diium dications are inter­connected via N—H...Cl and C—H...Cl hydrogen bonds to form layers parallel to the (001) plane. The cyclohexyl groups from adjacent chains interdigitate, thus building the three-dimensional structure. The piperazinium and cyclo­hexyl rings exhibit regular spatial chair conformations. The title salt was also characterized by FT–IR and Raman spectroscopic analyses.

Computing details

Data collection: CrysAlis PRO (Agilent, 2012); cell refinement: CrysAlis PRO (Agilent, 2012); data reduction: CrysAlis PRO (Agilent, 2012); program(s) used to solve structure: SIR92 (Altomare et al., 1994); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008).

1-cyclohexylpiperazine-1,4-diium tetrachloridozincate

Crystal data

(C10H22N2)[ZnCl4]	F(000) = 1552
Mr = 377.47	Dx = 1.604 Mg m^−3
Orthorhombic, Pbca	Cu Kα radiation, λ = 1.54184 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 9435 reflections
a = 11.3673 (2) Å	θ = 3.1–76.4°
b = 9.5997 (2) Å	µ = 8.30 mm^−1
c = 28.6571 (5) Å	T = 110 K
V = 3127.14 (10) Å^3	Prism, colourless
Z = 8	0.26 × 0.22 × 0.15 mm

Data collection

Agilent SuperNova Dual diffractometer (Cu at zero) with Atlas detector	3263 independent reflections
Radiation source: SuperNova (Cu) X-ray Source	3154 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.030
Detector resolution: 10.4508 pixels mm^-1	θmax = 76.2°, θmin = 3.1°
ω scans	h = −14→10
Absorption correction: analytical [CrysAlisPro (Agilent, 2012); analytical numerical absorption correction using a multifaceted crystal model based on expressions derived by Clark & Reid (1995)]	k = −11→12
Tmin = 0.201, Tmax = 0.425	l = −36→35
17184 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.022	Hydrogen site location: difference Fourier map
wR(F^2) = 0.056	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0273P)^2 + 2.021P] where P = (Fo^2 + 2Fc^2)/3
3263 reflections	(Δ/σ)max = 0.001
166 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.27 e Å^−3

Special details

Experimental. CrysAlisPro, Agilent Technologies, Version 1.171.35.21 (release 20-01-2012 CrysAlis171 .NET) (compiled Jan 23 2012,18:06:46) Analytical numeric absorption correction using a multifaceted crystal model based on expressions derived by R.C. Clark & J.S. Reid. (Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)

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 (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.552127 (17)	0.837964 (19)	0.089690 (6)	0.01164 (7)
Cl3	0.44251 (3)	0.99531 (4)	0.130948 (12)	0.01701 (9)
Cl2	0.66233 (3)	0.69395 (4)	0.133374 (12)	0.01658 (8)
Cl1	0.41865 (3)	0.68822 (3)	0.053615 (12)	0.01533 (8)
Cl4	0.64732 (3)	0.95295 (3)	0.031959 (12)	0.01565 (8)
N1	0.46089 (11)	0.42781 (13)	0.12379 (4)	0.0116 (2)
N4	0.48467 (11)	0.22977 (13)	0.04818 (4)	0.0136 (2)
C7	0.44402 (12)	0.46430 (15)	0.17543 (5)	0.0129 (3)
H7	0.5235	0.4855	0.1885	0.015*
C3	0.59015 (13)	0.30339 (16)	0.06715 (5)	0.0150 (3)
H3B	0.6052	0.3888	0.0487	0.018*
H3A	0.6600	0.2423	0.0645	0.018*
C6	0.35583 (13)	0.35838 (15)	0.10184 (5)	0.0141 (3)
H6B	0.2873	0.4218	0.1036	0.017*
H6A	0.3364	0.2728	0.1195	0.017*
C2	0.57029 (13)	0.34155 (15)	0.11769 (5)	0.0142 (3)
H2A	0.5633	0.2554	0.1365	0.017*
H2B	0.6390	0.3945	0.1294	0.017*
C12	0.39402 (15)	0.34274 (16)	0.20329 (5)	0.0186 (3)
H12B	0.4429	0.2587	0.1983	0.022*
H12A	0.3130	0.3219	0.1926	0.022*
C9	0.36831 (15)	0.63142 (17)	0.23370 (5)	0.0202 (3)
H9B	0.4494	0.6538	0.2438	0.024*
H9A	0.3192	0.7153	0.2386	0.024*
C5	0.37872 (13)	0.32076 (15)	0.05119 (5)	0.0145 (3)
H5A	0.3097	0.2714	0.0382	0.017*
H5B	0.3915	0.4066	0.0327	0.017*
C8	0.36894 (13)	0.59428 (16)	0.18160 (5)	0.0164 (3)
H8A	0.2877	0.5765	0.1706	0.020*
H8B	0.4021	0.6722	0.1632	0.020*
C11	0.39285 (16)	0.38115 (18)	0.25525 (5)	0.0232 (3)
H11A	0.3588	0.3033	0.2735	0.028*
H11B	0.4745	0.3963	0.2662	0.028*
C10	0.32078 (16)	0.51264 (18)	0.26348 (6)	0.0244 (3)
H10B	0.3246	0.5388	0.2969	0.029*
H10A	0.2374	0.4950	0.2554	0.029*
H4B	0.4965 (18)	0.205 (2)	0.0185 (8)	0.021 (5)*
H1	0.4747 (17)	0.508 (2)	0.1084 (7)	0.016 (5)*
H4A	0.4746 (19)	0.150 (2)	0.0639 (8)	0.022 (5)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.01350 (11)	0.00970 (11)	0.01171 (11)	0.00094 (7)	0.00004 (7)	0.00002 (6)
Cl3	0.01859 (18)	0.01404 (17)	0.01840 (17)	0.00101 (13)	0.00349 (12)	−0.00108 (12)
Cl2	0.01603 (17)	0.01697 (16)	0.01674 (17)	−0.00007 (13)	−0.00065 (12)	0.00320 (12)
Cl1	0.01766 (17)	0.01406 (16)	0.01426 (16)	−0.00266 (13)	−0.00250 (12)	0.00128 (11)
Cl4	0.01613 (16)	0.01425 (16)	0.01657 (16)	0.00047 (12)	0.00054 (12)	0.00002 (12)
N1	0.0128 (6)	0.0115 (5)	0.0106 (5)	0.0003 (5)	0.0005 (4)	−0.0002 (4)
N4	0.0149 (6)	0.0134 (6)	0.0126 (6)	0.0000 (5)	0.0003 (5)	−0.0024 (5)
C7	0.0149 (7)	0.0140 (7)	0.0097 (6)	0.0006 (5)	−0.0007 (5)	−0.0022 (5)
C3	0.0117 (7)	0.0169 (7)	0.0164 (7)	−0.0016 (6)	0.0021 (5)	−0.0024 (5)
C6	0.0117 (6)	0.0160 (7)	0.0147 (7)	0.0002 (5)	−0.0013 (5)	−0.0018 (5)
C2	0.0126 (7)	0.0144 (7)	0.0154 (7)	0.0021 (5)	−0.0007 (5)	−0.0023 (5)
C12	0.0274 (8)	0.0165 (7)	0.0119 (7)	−0.0010 (6)	0.0014 (6)	0.0007 (5)
C9	0.0237 (8)	0.0202 (7)	0.0168 (7)	0.0049 (6)	−0.0013 (6)	−0.0059 (6)
C5	0.0138 (7)	0.0159 (7)	0.0137 (7)	0.0015 (6)	−0.0017 (5)	−0.0014 (5)
C8	0.0191 (7)	0.0156 (7)	0.0146 (7)	0.0022 (6)	0.0000 (5)	−0.0009 (5)
C11	0.0345 (9)	0.0237 (8)	0.0116 (7)	−0.0002 (7)	0.0019 (6)	0.0013 (6)
C10	0.0277 (8)	0.0319 (9)	0.0134 (7)	0.0028 (7)	0.0042 (6)	−0.0037 (6)

Geometric parameters (Å, º)

Zn1—Cl2	2.2467 (4)	C6—H6A	0.9900
Zn1—Cl4	2.2641 (4)	C2—H2A	0.9900
Zn1—Cl3	2.2874 (4)	C2—H2B	0.9900
Zn1—Cl1	2.3318 (4)	C12—C11	1.534 (2)
N1—C2	1.5043 (18)	C12—H12B	0.9900
N1—C6	1.5052 (18)	C12—H12A	0.9900
N1—C7	1.5328 (17)	C9—C10	1.523 (2)
N1—H1	0.90 (2)	C9—C8	1.535 (2)
N4—C5	1.4902 (19)	C9—H9B	0.9900
N4—C3	1.4942 (18)	C9—H9A	0.9900
N4—H4B	0.89 (2)	C5—H5A	0.9900
N4—H4A	0.90 (2)	C5—H5B	0.9900
C7—C8	1.522 (2)	C8—H8A	0.9900
C7—C12	1.524 (2)	C8—H8B	0.9900
C7—H7	1.0000	C11—C10	1.523 (2)
C3—C2	1.511 (2)	C11—H11A	0.9900
C3—H3B	0.9900	C11—H11B	0.9900
C3—H3A	0.9900	C10—H10B	0.9900
C6—C5	1.5183 (19)	C10—H10A	0.9900
C6—H6B	0.9900
Cl2—Zn1—Cl4	116.146 (15)	N1—C2—H2B	109.3
Cl2—Zn1—Cl3	114.966 (15)	C3—C2—H2B	109.3
Cl4—Zn1—Cl3	108.429 (14)	H2A—C2—H2B	108.0
Cl2—Zn1—Cl1	103.327 (14)	C7—C12—C11	109.13 (13)
Cl4—Zn1—Cl1	106.711 (14)	C7—C12—H12B	109.9
Cl3—Zn1—Cl1	106.366 (15)	C11—C12—H12B	109.9
C2—N1—C6	111.32 (11)	C7—C12—H12A	109.9
C2—N1—C7	109.96 (11)	C11—C12—H12A	109.9
C6—N1—C7	113.91 (11)	H12B—C12—H12A	108.3
C2—N1—H1	105.6 (13)	C10—C9—C8	111.88 (13)
C6—N1—H1	108.1 (13)	C10—C9—H9B	109.2
C7—N1—H1	107.5 (12)	C8—C9—H9B	109.2
C5—N4—C3	110.50 (11)	C10—C9—H9A	109.2
C5—N4—H4B	109.3 (13)	C8—C9—H9A	109.2
C3—N4—H4B	110.5 (13)	H9B—C9—H9A	107.9
C5—N4—H4A	111.6 (14)	N4—C5—C6	109.47 (11)
C3—N4—H4A	108.9 (14)	N4—C5—H5A	109.8
H4B—N4—H4A	105.9 (18)	C6—C5—H5A	109.8
C8—C7—C12	110.96 (12)	N4—C5—H5B	109.8
C8—C7—N1	111.70 (11)	C6—C5—H5B	109.8
C12—C7—N1	112.18 (12)	H5A—C5—H5B	108.2
C8—C7—H7	107.2	C7—C8—C9	107.83 (12)
C12—C7—H7	107.2	C7—C8—H8A	110.1
N1—C7—H7	107.2	C9—C8—H8A	110.1
N4—C3—C2	110.09 (12)	C7—C8—H8B	110.1
N4—C3—H3B	109.6	C9—C8—H8B	110.1
C2—C3—H3B	109.6	H8A—C8—H8B	108.5
N4—C3—H3A	109.6	C10—C11—C12	110.74 (13)
C2—C3—H3A	109.6	C10—C11—H11A	109.5
H3B—C3—H3A	108.2	C12—C11—H11A	109.5
N1—C6—C5	111.64 (12)	C10—C11—H11B	109.5
N1—C6—H6B	109.3	C12—C11—H11B	109.5
C5—C6—H6B	109.3	H11A—C11—H11B	108.1
N1—C6—H6A	109.3	C11—C10—C9	110.05 (13)
C5—C6—H6A	109.3	C11—C10—H10B	109.7
H6B—C6—H6A	108.0	C9—C10—H10B	109.7
N1—C2—C3	111.61 (12)	C11—C10—H10A	109.7
N1—C2—H2A	109.3	C9—C10—H10A	109.7
C3—C2—H2A	109.3	H10B—C10—H10A	108.2
C2—N1—C7—C8	156.71 (12)	C8—C7—C12—C11	−60.68 (17)
C6—N1—C7—C8	−77.55 (15)	N1—C7—C12—C11	173.60 (12)
C2—N1—C7—C12	−77.98 (14)	C3—N4—C5—C6	−60.15 (15)
C6—N1—C7—C12	47.76 (16)	N1—C6—C5—N4	56.76 (15)
C5—N4—C3—C2	60.08 (15)	C12—C7—C8—C9	60.11 (16)
C2—N1—C6—C5	−53.28 (15)	N1—C7—C8—C9	−173.91 (12)
C7—N1—C6—C5	−178.30 (11)	C10—C9—C8—C7	−58.33 (17)
C6—N1—C2—C3	52.84 (15)	C7—C12—C11—C10	57.94 (18)
C7—N1—C2—C3	−179.96 (11)	C12—C11—C10—C9	−56.23 (18)
N4—C3—C2—N1	−56.07 (16)	C8—C9—C10—C11	57.11 (18)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl1	0.90 (2)	2.42 (2)	3.2441 (13)	152 (2)
N4—H4A···Cl3^i	0.90 (2)	2.46 (2)	3.3050 (12)	158 (2)
C5—H5A···Cl1^ii	0.99	2.75	3.6125 (15)	146
N4—H4B···Cl1^iii	0.89 (2)	2.50 (2)	3.2153 (12)	138 (2)
N4—H4B···Cl4^iii	0.89 (2)	2.66 (2)	3.2561 (12)	125 (2)
C5—H5B···Cl1	0.99	2.79	3.5573 (15)	135

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