Piperazinediium tetra-chloridozincate(II).

In the title compound, (C(4)H(12)N(2))[ZnCl(4)], the Zn atom adopts a slightly distorted tetra-hedral geometry. In the crystal, the dication and dianion inter-act by way of N-H⋯Cl and N-H⋯(Cl,Cl) hydrogen bonds to result in a layered network propagating in (010). The hydrogen-bonding network is unbalanced, with three Cl atoms accepting two hydrogen bonds each and one Cl atom not accepting any hydrogen bonds: the latter shows the shortest Zn-Cl bond length. The crystal studied was found to be an inversion twin.

Related literature

For related structures, see: Bremner & Harrison (2003 ▶); Kefi & Nasr (2005 ▶); Wilkinson & Harrison (2007 ▶). For reference structural data, see: Allen et al. (1995 ▶). For details of graph-set theory, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

(C4H12N2)[ZnCl4]

M = 295.33

Orthorhombic,

a = 8.2309 (3) Å

b = 11.0845 (3) Å

c = 11.8443 (4) Å

V = 1080.62 (6) Å3

Z = 4

Mo Kα radiation

μ = 3.21 mm−1

T = 120 K

0.13 × 0.09 × 0.04 mm

Data collection

Nonius KappaCCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T min = 0.681, T max = 0.882

8838 measured reflections

2388 independent reflections

2194 reflections with I > 2σ(I)

R int = 0.058

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.094

S = 1.08

2388 reflections

101 parameters

H-atom parameters constrained

Δρmax = 0.92 e Å−3

Δρmin = −0.77 e Å−3

Absolute structure: Flack (1983 ▶), 946 Friedel pairs

Flack parameter: 0.44 (2)

Data collection: COLLECT (Nonius, 1998 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK, and SORTAV (Blessing, 1995 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809013981/bg2253sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013981/bg2253Isup2.hkl

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

(C4H12N2)[ZnCl4]	F(000) = 592
Mr = 295.33	Dx = 1.815 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 8676 reflections
a = 8.2309 (3) Å	θ = 2.9–27.5°
b = 11.0845 (3) Å	µ = 3.21 mm−1
c = 11.8443 (4) Å	T = 120 K
V = 1080.62 (6) Å3	Slab, colourless
Z = 4	0.13 × 0.09 × 0.04 mm

Nonius KappaCCD diffractometer	2388 independent reflections
Radiation source: fine-focus sealed tube	2194 reflections with I > 2σ(I)
graphite	Rint = 0.058
ω and φ scans	θmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 2003)	h = −9→10
Tmin = 0.681, Tmax = 0.882	k = −12→14
8838 measured reflections	l = −15→15

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)] = 0.042	H-atom parameters constrained
wR(F2) = 0.094	w = 1/[σ2(Fo2) + (0.0219P)2 + 3.2663P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max < 0.001
2388 reflections	Δρmax = 0.92 e Å−3
101 parameters	Δρmin = −0.77 e Å−3
0 restraints	Absolute structure: Flack (1983), 946 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.44 (2)

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	0.27149 (6)	0.46334 (5)	0.09228 (5)	0.01746 (15)
Cl1	0.06341 (13)	0.59864 (10)	0.09534 (11)	0.0192 (2)
Cl2	0.51483 (13)	0.56726 (10)	0.09893 (11)	0.0193 (2)
Cl3	0.24980 (15)	0.34993 (10)	−0.06487 (9)	0.0212 (3)
Cl4	0.26367 (15)	0.35675 (9)	0.25519 (9)	0.0182 (3)
C1	0.6765 (6)	0.3608 (4)	0.3437 (5)	0.0211 (11)
H1A	0.6095	0.2999	0.3040	0.025*
H1B	0.7022	0.3292	0.4198	0.025*
C2	0.8319 (6)	0.3817 (4)	0.2790 (4)	0.0189 (10)
H2A	0.8947	0.3057	0.2747	0.023*
H2B	0.8062	0.4078	0.2010	0.023*
C3	0.8383 (6)	0.5925 (5)	0.3449 (4)	0.0196 (10)
H3A	0.8136	0.6227	0.2681	0.024*
H3B	0.9052	0.6539	0.3839	0.024*
C4	0.6815 (6)	0.5734 (4)	0.4092 (5)	0.0189 (9)
H4A	0.7063	0.5505	0.4881	0.023*
H4B	0.6185	0.6495	0.4106	0.023*
N1	0.5828 (5)	0.4761 (4)	0.3544 (4)	0.0180 (9)
H1	0.5509	0.5014	0.2839	0.022*
H2	0.4907	0.4625	0.3966	0.022*
N2	0.9310 (5)	0.4768 (4)	0.3369 (4)	0.0189 (9)
H3	0.9583	0.4509	0.4082	0.023*
H4	1.0256	0.4894	0.2972	0.023*

	U11	U22	U33	U12	U13	U23
Zn1	0.0130 (3)	0.0212 (3)	0.0182 (3)	−0.0007 (2)	−0.0003 (3)	−0.0015 (2)
Cl1	0.0164 (5)	0.0221 (5)	0.0191 (5)	0.0024 (4)	−0.0007 (5)	−0.0019 (5)
Cl2	0.0142 (5)	0.0253 (5)	0.0183 (5)	−0.0030 (4)	0.0008 (5)	0.0002 (5)
Cl3	0.0181 (6)	0.0240 (6)	0.0214 (6)	−0.0006 (5)	−0.0002 (5)	−0.0045 (4)
Cl4	0.0151 (6)	0.0188 (5)	0.0205 (5)	−0.0014 (5)	−0.0001 (5)	−0.0003 (4)
C1	0.016 (3)	0.017 (2)	0.030 (3)	−0.001 (2)	0.002 (2)	0.000 (2)
C2	0.019 (2)	0.019 (2)	0.019 (2)	0.0003 (19)	−0.001 (2)	−0.002 (2)
C3	0.013 (2)	0.021 (2)	0.024 (3)	0.001 (2)	0.000 (2)	0.001 (2)
C4	0.013 (2)	0.023 (2)	0.021 (2)	−0.0004 (17)	0.002 (2)	−0.002 (2)
N1	0.0091 (19)	0.025 (2)	0.020 (2)	−0.0019 (18)	0.0000 (16)	0.0001 (18)
N2	0.013 (2)	0.024 (2)	0.020 (2)	0.0030 (19)	0.0031 (17)	−0.0008 (18)

Zn1—Cl1	2.2768 (12)	C3—N2	1.496 (6)
Zn1—Cl2	2.3119 (12)	C3—C4	1.513 (7)
Zn1—Cl3	2.2532 (12)	C3—H3A	0.9900
Zn1—Cl4	2.2634 (12)	C3—H3B	0.9900
C1—N1	1.499 (7)	C4—N1	1.498 (6)
C1—C2	1.510 (7)	C4—H4A	0.9900
C1—H1A	0.9900	C4—H4B	0.9900
C1—H1B	0.9900	N1—H1	0.9200
C2—N2	1.498 (6)	N1—H2	0.9200
C2—H2A	0.9900	N2—H3	0.9200
C2—H2B	0.9900	N2—H4	0.9200
Cl3—Zn1—Cl4	114.25 (4)	N2—C3—H3B	109.6
Cl3—Zn1—Cl1	108.73 (5)	C4—C3—H3B	109.6
Cl4—Zn1—Cl1	107.99 (5)	H3A—C3—H3B	108.1
Cl3—Zn1—Cl2	112.01 (5)	N1—C4—C3	110.2 (4)
Cl4—Zn1—Cl2	104.82 (5)	N1—C4—H4A	109.6
Cl1—Zn1—Cl2	108.84 (5)	C3—C4—H4A	109.6
N1—C1—C2	110.4 (4)	N1—C4—H4B	109.6
N1—C1—H1A	109.6	C3—C4—H4B	109.6
C2—C1—H1A	109.6	H4A—C4—H4B	108.1
N1—C1—H1B	109.6	C4—N1—C1	111.8 (4)
C2—C1—H1B	109.6	C4—N1—H1	109.2
H1A—C1—H1B	108.1	C1—N1—H1	109.2
N2—C2—C1	109.7 (4)	C4—N1—H2	109.2
N2—C2—H2A	109.7	C1—N1—H2	109.2
C1—C2—H2A	109.7	H1—N1—H2	107.9
N2—C2—H2B	109.7	C3—N2—C2	110.8 (4)
C1—C2—H2B	109.7	C3—N2—H3	109.5
H2A—C2—H2B	108.2	C2—N2—H3	109.5
N2—C3—C4	110.3 (4)	C3—N2—H4	109.5
N2—C3—H3A	109.6	C2—N2—H4	109.5
C4—C3—H3A	109.6	H3—N2—H4	108.1
N1—C1—C2—N2	57.4 (5)	C2—C1—N1—C4	−56.6 (5)
N2—C3—C4—N1	−56.4 (5)	C4—C3—N2—C2	58.8 (5)
C3—C4—N1—C1	55.8 (5)	C1—C2—N2—C3	−59.1 (5)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl2	0.92	2.33	3.239 (5)	171
N1—H2···Cl4	0.92	2.77	3.168 (4)	107
N1—H2···Cl1i	0.92	2.49	3.206 (4)	135
N2—H3···Cl2ii	0.92	2.28	3.174 (4)	164
N2—H4···Cl4iii	0.92	2.50	3.194 (5)	133
N2—H4···Cl1iii	0.92	2.70	3.346 (4)	128

Table 1

Selected bond lengths (Å)

Zn1—Cl1	2.2768 (12)
Zn1—Cl2	2.3119 (12)
Zn1—Cl3	2.2532 (12)
Zn1—Cl4	2.2634 (12)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl2	0.92	2.33	3.239 (5)	171
N1—H2⋯Cl4	0.92	2.77	3.168 (4)	107
N1—H2⋯Cl1i	0.92	2.49	3.206 (4)	135
N2—H3⋯Cl2ii	0.92	2.28	3.174 (4)	164
N2—H4⋯Cl4iii	0.92	2.50	3.194 (5)	133
N2—H4⋯Cl1iii	0.92	2.70	3.346 (4)	128

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