1-(4-Chloro­phen­yl)piperazine-1,4-diium tetra­chlorido­zincate(II) monohydrate

In the crystal structure of the title compound, (C₁₀H₁₅ClN₂)[ZnCl₄]·H₂O, the Zn atom is coordinated by four Cl atoms in a tetrahedral geometry. The water mol­ecules and the 1-(4-chloro­phen­yl)piperazine-1,4-diium cations inter­act with the [ZnCl₄]²⁻ anions through O—H...Cl, N—H...Cl, N—H...O and C—H...Cl hydrogen bonds (five simple and one bifurcated). Inter­molecular π–π stacking inter­actions are present between adjacent aromatic rings of 1-(4-chloro­phenyl)­piperazine-1,4-diium cations (the centroid–centroid distance is 3.453 Å).

Key indicators

• Single-crystal X-ray study
• T = 293 K
• Mean [sigma](C-C) = 0.006 Å
• R factor = 0.053
• wR factor = 0.063
• Data-to-parameter ratio = 18.5

checkCIF/PLATON results

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Alert level G
PLAT199_ALERT_1_G Check the Reported _cell_measurement_temperature        293 K
PLAT200_ALERT_1_G Check the Reported _diffrn_ambient_temperature .        293 K

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   0 ALERT level B = Potentially serious problem
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   2 ALERT level G = General alerts; check

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
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S1. Comment

The crystal structure of the title compound, (I), (Fig. 1), contains a [ZnCl₄]^2- tetrahedral anion, a 1-(4-chlorophenyl)piperazine-1,4-dium (2+) cation and a water molecule. Fig. 2 shows the atomic arrangement, which can be described as built up by [ZnCl₄] tetrahedra interconnected through water molecules via a O—H···Cl bond to form chains which evolve along the a direction. These [ZnCl₄].[H₂O] chains are interconnected into a three-dimensional network by the organic entities through N—H···Cl, C—H···Cl bonds and π-π interactions. Fig.3 shows the way in which two adjacent aromatic rings of the 1-(4-chlorophenyl)piperazine-1,4-dium cations run parallel in the opposite direction and stack each other by turns in a face-to-face mode. The nearest centroid-centroid distance is 3.453 (1) Å, less than 3.8 Å, the maximum value accepted for π-π interactions (Janiak, 2000). Generally, the Zn—Cl bond lengths and Cl—Zn—Cl bond angles in the [ZnCl₄]^2- anion are not equal to one another but vary with the environment around the Cl atoms (Valkonen et al., 2006). In the title compound, the four chlorine atoms of the [ZnCl₄]^2- anion are acting as acceptors of the hydrogen bonds. The bond angles Cl—Zn—Cl vary from 103.37 (5) to 115.30 (5)°, and the bond length of the Zn—Cl lie in the range 2.2420 (12) - 2.3036 (11) Å. Owing to these differences in Zn—Cl bond lengths and Cl—Zn—Cl angles, the coordination geometry of the Zn atom can be described as a slightly distorted tetrahedron (as in Guo et al., 2007). The nearst Zn···Zn intra-chain separation is 7.204 (1) Å, while the distance between adjacent chains is 6.370 (2) Å. Examination of the organic cation geometry shows that the piperazine-1,4-dium ring adopts a typical chair conformation and its geometric parameters [d_av(C—N) = 1.501 (4) and d_av(C—C) = 1.508 (4) Å] are in full agreement with those found in phenylpiperazinium tetrachlorozincate (Ben Gharbia et al., 2005).

Related literature

For related literature, see: Ben Gharbia et al. (2005); Guo et al. (2007); Valkonen et al. (2006); Janiak (2000).

S2. Experimental

ZnCl₂, aqueous 1M HCl solution and 1-(4-chlorophenyl)piperazine in a 1:2:1 molar ratio were mixed and dissolved in sufficient ethanol. Crystals of (I) grew as the ethanol evaporated at 293 K over the course of a few days.

S3. Refinement

The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularize their geometry (C—H in the range 0.93–0.98, N—H in the range 0.86–0.89 and O—H = 0.82 Å) and U_iso(H) (in the range 1.2–1.5 times U_eq of the parent atom), after which the positions were refined with riding constraints. The refinement was carried out with 3203 reflections with I>3σ(I). The R factors reported are those calculated for I>2σ(I) (3369 reflections)

Computing details

Data collection: COLLECT (Nonius, 2001); cell refinement: DENZO/SCALEPACK (Otwinowski & Minor, 1997); data reduction: DENZO/SCALEPACK (Otwinowski & Minor, 1997); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: CRYSTALS (Betteridge et al., 2003); molecular graphics: DIAMOND (Brandenburg, 1998); software used to prepare material for publication: CRYSTALS (Betteridge et al., 2003).

Figures

	Fig. 1. A view of (I), showing 40% probability displacement ellipsoids and arbitrary spheres for the H atoms.
	Fig. 2. A stereoview of part of the crystal structure showing the formation of (100) chains formed by [ZnCl4]^2- tetrahedral anions interconnected through the water molecules.
	Fig. 3. The packing of (I), viewed down the a axis, showing the N—H···Cl, C—H···Cl and O—H···Cl hydrogen bonds between the 1-(4-chlorophenyl)piperazine-1,4-dium cations, water molecules and [ZnCl4]^2- anions.

1-(4-chlorophenyl)piperazine-1,4-diium tetrachloridozincate(II) monohydrate

Crystal data

(C10H15ClN2)[ZnCl4]·H2O	F(000) = 856
Mr = 423.90	Dx = 1.709 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71069 Å
Hall symbol: -P 2ybc	Cell parameters from 19642 reflections
a = 7.2036 (2) Å	θ = 0.7–27.9°
b = 15.1575 (5) Å	µ = 2.29 mm^−1
c = 15.4870 (5) Å	T = 293 K
β = 103.012 (2)°	Plate, colorless
V = 1647.58 (9) Å^3	0.44 × 0.28 × 0.23 mm
Z = 4

Data collection

Nonius KappaCCD diffractometer	3369 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.085
ϕ and ω scans	θmax = 28.0°, θmin = 1.9°
Absorption correction: analytical (de Meulenaer & Tompa, 1965)	h = −9→9
Tmin = 0.34, Tmax = 0.59	k = −17→19
20612 measured reflections	l = −20→20
3901 independent reflections

Refinement

Refinement on F	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.053	H-atom parameters constrained
wR(F^2) = 0.063	weight = 1.0/[1.57 + 1.32*x + 0.866*(2x^2-1)] * [1-(deltaF/6*sigmaF)^2]^2 where x = F /Fmax
S = 0.90	(Δ/σ)max = 0.000411
3203 reflections	Δρmax = 0.41 e Å^−3
173 parameters	Δρmin = −0.69 e Å^−3
0 restraints

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
Zn1	0.58976 (7)	0.36124 (3)	0.65838 (3)	0.0375
Cl1	0.29500 (16)	0.42310 (8)	0.60275 (7)	0.0461
Cl2	0.75399 (15)	0.36476 (7)	0.54758 (6)	0.0415
Cl3	0.5442 (2)	0.22604 (8)	0.70986 (10)	0.0568
Cl4	0.7715 (2)	0.44230 (9)	0.76618 (7)	0.0560
Cl5	0.29277 (18)	−0.13523 (7)	0.48834 (10)	0.0558
C1	0.2020 (5)	0.1446 (2)	0.4005 (2)	0.0312
C2	0.2558 (6)	0.0844 (3)	0.3443 (3)	0.0410
C3	0.2866 (7)	−0.0026 (3)	0.3717 (3)	0.0442
C4	0.2642 (6)	−0.0255 (3)	0.4557 (3)	0.0404
C5	0.2183 (7)	0.0359 (3)	0.5131 (3)	0.0441
C6	0.1869 (7)	0.1230 (3)	0.4851 (3)	0.0399
C7	−0.0002 (6)	0.2802 (3)	0.3894 (3)	0.0404
C8	−0.0229 (6)	0.3724 (3)	0.3515 (3)	0.0433
C9	0.3249 (7)	0.3838 (3)	0.3692 (3)	0.0468
C10	0.3479 (6)	0.2911 (3)	0.4050 (3)	0.0406
N1	0.1724 (5)	0.2369 (2)	0.3687 (2)	0.0313
N2	0.1516 (6)	0.4259 (2)	0.3875 (3)	0.0466
O1	0.0861 (5)	0.2511 (3)	0.1875 (2)	0.0530
H1	−0.0199	0.2401	0.1574	0.0730*
H2	0.1897	0.2453	0.1746	0.0730*
H3	0.2669	0.1008	0.2869	0.0471*
H4	0.3213	−0.0443	0.3350	0.0503*
H5	0.2084	0.0191	0.5702	0.0511*
H6	0.1563	0.1671	0.5231	0.0473*
H7	−0.1133	0.2465	0.3632	0.0448*
H8	0.0133	0.2821	0.4533	0.0447*
H9	−0.0388	0.3688	0.2866	0.0492*
H10	−0.1329	0.4027	0.3654	0.0493*
H11	0.3148	0.3815	0.3047	0.0543*
H12	0.4375	0.4194	0.3985	0.0543*
H13	0.4580	0.2643	0.3887	0.0434*
H14	0.3750	0.2920	0.4706	0.0430*
H15	0.1556	0.2362	0.3097	0.0410*
H16	0.1361	0.4792	0.3623	0.0620*
H17	0.1605	0.4357	0.4450	0.0620*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Zn1	0.0394 (2)	0.0380 (2)	0.0350 (2)	−0.00079 (19)	0.00810 (19)	0.00223 (18)
Cl1	0.0445 (5)	0.0526 (6)	0.0407 (5)	0.0090 (5)	0.0082 (4)	0.0053 (4)
Cl2	0.0449 (5)	0.0428 (5)	0.0392 (5)	−0.0021 (4)	0.0146 (4)	−0.0012 (4)
Cl3	0.0650 (7)	0.0405 (6)	0.0698 (7)	0.0029 (5)	0.0255 (6)	0.0136 (5)
Cl4	0.0704 (7)	0.0562 (7)	0.0350 (5)	−0.0084 (6)	−0.0019 (5)	−0.0027 (4)
Cl5	0.0547 (6)	0.0338 (5)	0.0785 (8)	0.0044 (4)	0.0140 (6)	0.0126 (5)
C1	0.0360 (16)	0.0256 (15)	0.0309 (16)	−0.0002 (14)	0.0055 (14)	−0.0033 (13)
C2	0.048 (2)	0.039 (2)	0.0367 (19)	0.0017 (17)	0.0105 (16)	−0.0033 (16)
C3	0.050 (2)	0.034 (2)	0.047 (2)	0.0069 (17)	0.0085 (18)	−0.0077 (17)
C4	0.0367 (18)	0.0305 (18)	0.051 (2)	0.0021 (15)	0.0034 (16)	0.0003 (16)
C5	0.050 (2)	0.042 (2)	0.041 (2)	0.0025 (18)	0.0112 (17)	0.0089 (17)
C6	0.050 (2)	0.037 (2)	0.0339 (19)	0.0010 (16)	0.0124 (16)	−0.0005 (15)
C7	0.0351 (18)	0.037 (2)	0.051 (2)	0.0050 (15)	0.0128 (16)	0.0027 (17)
C8	0.042 (2)	0.039 (2)	0.049 (2)	0.0095 (17)	0.0085 (17)	0.0014 (17)
C9	0.047 (2)	0.035 (2)	0.054 (2)	−0.0055 (17)	0.0040 (18)	0.0071 (18)
C10	0.0354 (18)	0.033 (2)	0.049 (2)	−0.0031 (15)	0.0012 (16)	0.0045 (16)
N1	0.0391 (16)	0.0263 (14)	0.0274 (13)	0.0008 (12)	0.0055 (12)	0.0007 (11)
N2	0.065 (2)	0.0284 (16)	0.0424 (18)	0.0037 (15)	0.0030 (17)	−0.0020 (13)
O1	0.0519 (18)	0.067 (2)	0.0389 (15)	0.0008 (16)	0.0065 (14)	−0.0023 (14)

Geometric parameters (Å, º)

Zn1—Cl1	2.3036 (11)	C7—H7	0.970
Zn1—Cl2	2.2937 (11)	C8—N2	1.494 (6)
Zn1—Cl3	2.2495 (13)	C8—H10	0.980
Zn1—Cl4	2.2420 (12)	C8—H9	0.988
Cl5—C4	1.738 (4)	N2—C9	1.485 (7)
C4—C3	1.389 (7)	N2—H16	0.893
C4—C5	1.378 (6)	N2—H17	0.891
C3—C2	1.388 (6)	C9—C10	1.506 (6)
C3—H4	0.922	C9—H12	0.995
C2—C1	1.376 (5)	C9—H11	0.985
C2—H3	0.943	C10—H14	0.990
C1—N1	1.482 (5)	C10—H13	0.973
C1—C6	1.378 (5)	C6—C5	1.392 (6)
N1—C7	1.504 (5)	C6—H6	0.948
N1—C10	1.507 (5)	C5—H5	0.938
N1—H15	0.893	O1—H2	0.820
C7—C8	1.511 (6)	O1—H1	0.818
C7—H8	0.973
Cl1—Zn1—Cl2	107.34 (4)	C7—C8—H10	111.7
Cl1—Zn1—Cl3	107.92 (5)	N2—C8—H10	108.6
Cl2—Zn1—Cl3	115.30 (5)	C7—C8—H9	108.8
Cl1—Zn1—Cl4	112.95 (5)	N2—C8—H9	107.7
Cl2—Zn1—Cl4	103.37 (5)	H10—C8—H9	109.7
Cl3—Zn1—Cl4	110.04 (5)	C8—N2—C9	111.6 (3)
Cl5—C4—C3	118.7 (3)	C8—N2—H16	108.4
Cl5—C4—C5	119.2 (3)	C9—N2—H16	109.4
C3—C4—C5	122.1 (4)	C8—N2—H17	109.2
C4—C3—C2	118.6 (4)	C9—N2—H17	112.9
C4—C3—H4	120.8	H16—N2—H17	105.0
C2—C3—H4	120.6	N2—C9—C10	110.9 (4)
C3—C2—C1	119.0 (4)	N2—C9—H12	108.3
C3—C2—H3	119.7	C10—C9—H12	109.1
C1—C2—H3	121.2	N2—C9—H11	109.6
C2—C1—N1	117.1 (3)	C10—C9—H11	108.5
C2—C1—C6	122.5 (4)	H12—C9—H11	110.5
N1—C1—C6	120.3 (3)	N1—C10—C9	111.0 (3)
C1—N1—C7	113.9 (3)	N1—C10—H14	110.2
C1—N1—C10	110.1 (3)	C9—C10—H14	110.2
C7—N1—C10	110.3 (3)	N1—C10—H13	109.9
C1—N1—H15	107.8	C9—C10—H13	108.7
C7—N1—H15	107.2	H14—C10—H13	106.7
C10—N1—H15	107.3	C1—C6—C5	118.7 (4)
N1—C7—C8	110.1 (3)	C1—C6—H6	120.0
N1—C7—H8	109.4	C5—C6—H6	121.2
C8—C7—H8	110.2	C6—C5—C4	119.0 (4)
N1—C7—H7	109.7	C6—C5—H5	120.7
C8—C7—H7	108.5	C4—C5—H5	120.4
H8—C7—H7	108.9	H2—O1—H1	128.4
C7—C8—N2	110.4 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H15···O1	0.89	1.86	2.742 (6)	169
N2—H16···Cl4^i	0.89	2.53	3.249 (4)	137
N2—H16···Cl2^i	0.89	2.77	3.352 (3)	123
N2—H17···Cl1	0.89	2.42	3.261 (5)	156
O1—H1···Cl2^ii	0.81	2.61	3.342 (3)	149
O1—H2···Cl3^iii	0.82	2.52	3.258 (4)	149
C5—H5···Cl4^iv	0.93	2.76	3.686 (5)	168

Symmetry codes: (i) −x+1, −y+1, −z+1; (ii) x−1, −y+1/2, z−1/2; (iii) x, −y+1/2, z−1/2; (iv) −x+1, y−1/2, −z+3/2.