(S)-1,2,4-Trimethyl-piperazine-1,4-diium tetra-chloridozincate(II).

In the title compound, (C(7)H(18)N(2))[ZnCl(4)], the Zn atom adopts a slightly distorted tetra-hedral geometry. The diprotonated piperazine ring adopts a chair conformation. In the crystal structure, the cations and anions are linked by inter-molecular N-H⋯Cl hydrogen bonds into a chain along [001].

Related literature

For the ferroelectric behavior of chiral coordination compounds, see: Fu et al. (2007 ▶). For non-linear optical second harmonic generation of chiral coordination compounds, see: Qu et al. (2003 ▶). For transition-metal complexes of (S)-2-methyl­piperazine, see: Ye et al. (2009 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

(C7H18N2)[ZnCl4]

M = 337.40

Orthorhombic,

a = 8.5197 (17) Å

b = 9.7036 (19) Å

c = 17.013 (3) Å

V = 1406.5 (5) Å3

Z = 4

Mo Kα radiation

μ = 2.48 mm−1

T = 293 K

0.30 × 0.28 × 0.26 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005 ▶) T min = 0.80, T max = 0.90

14785 measured reflections

3217 independent reflections

2802 reflections with I > 2σ(I)

R int = 0.038

Refinement

R[F 2 > 2σ(F 2)] = 0.032

wR(F 2) = 0.067

S = 1.08

3217 reflections

138 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.36 e Å−3

Δρmin = −0.36 e Å−3

Absolute structure: Flack (1983 ▶), 1355 Friedel pairs

Flack parameter: 0.046 (14)

Data collection: CrystalClear (Rigaku/MSC, 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: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810028631/bx2289sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028631/bx2289Isup2.hkl

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

(C7H18N2)[ZnCl4]	F(000) = 688
Mr = 337.40	Dx = 1.593 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2802 reflections
a = 8.5197 (17) Å	θ = 3.2–27.5°
b = 9.7036 (19) Å	µ = 2.48 mm−1
c = 17.013 (3) Å	T = 293 K
V = 1406.5 (5) Å3	Block, colourless
Z = 4	0.30 × 0.28 × 0.26 mm

Rigaku SCXmini diffractometer	3217 independent reflections
Radiation source: fine-focus sealed tube	2802 reflections with I > 2σ(I)
graphite	Rint = 0.038
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.2°
ω scans	h = −11→10
Absorption correction: multi-scan (CrystalClear; Rigaku/MSC, 2005)	k = −12→12
Tmin = 0.80, Tmax = 0.90	l = −22→22
14785 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)] = 0.032	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.067	w = 1/[σ2(Fo2) + (0.0257P)2 + 0.2767P] where P = (Fo2 + 2Fc2)/3
S = 1.08	(Δ/σ)max = 0.001
3217 reflections	Δρmax = 0.36 e Å−3
138 parameters	Δρmin = −0.36 e Å−3
0 restraints	Absolute structure: Flack (1983), 1355 Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.046 (14)

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	0.59768 (3)	0.49854 (3)	0.125016 (17)	0.03377 (9)
C1	0.2131 (4)	0.8709 (3)	0.14589 (17)	0.0359 (7)
H1	0.2576	0.8595	0.1986	0.043*
C2	0.3442 (3)	0.8994 (3)	0.08782 (17)	0.0368 (7)
H2A	0.4167	0.8223	0.0882	0.044*
H2B	0.3000	0.9060	0.0354	0.044*
C3	0.3220 (4)	1.1457 (3)	0.10626 (19)	0.0481 (9)
H3A	0.2799	1.1599	0.0539	0.058*
H3B	0.3791	1.2281	0.1212	0.058*
C4	0.1875 (4)	1.1231 (3)	0.16346 (19)	0.0449 (8)
H4A	0.2283	1.1194	0.2166	0.054*
H4B	0.1151	1.2000	0.1602	0.054*
C5	−0.0354 (4)	0.9767 (4)	0.19972 (18)	0.0491 (8)
H5A	0.0010	0.9678	0.2529	0.074*
H5B	−0.0935	0.8958	0.1853	0.074*
H5C	−0.1019	1.0562	0.1955	0.074*
C6	0.5641 (4)	1.0490 (4)	0.0483 (2)	0.0628 (11)
H6A	0.6305	0.9691	0.0477	0.094*
H6B	0.6241	1.1279	0.0643	0.094*
H6C	0.5224	1.0643	−0.0034	0.094*
C7	0.1282 (4)	0.7396 (3)	0.1223 (2)	0.0580 (9)
H7A	0.0840	0.7508	0.0708	0.087*
H7B	0.0458	0.7209	0.1593	0.087*
H7C	0.2011	0.6642	0.1219	0.087*
Cl1	0.44725 (9)	0.46036 (8)	0.01637 (4)	0.0479 (2)
Cl2	0.42671 (10)	0.48120 (12)	0.22655 (4)	0.0642 (3)
Cl3	0.70714 (11)	0.70748 (9)	0.11735 (6)	0.0600 (2)
Cl4	0.79167 (12)	0.34029 (10)	0.13266 (5)	0.0606 (2)
N1	0.1024 (2)	0.9929 (3)	0.14575 (12)	0.0334 (5)
N2	0.4314 (3)	1.0266 (3)	0.10512 (14)	0.0390 (6)
H1A	0.054 (3)	1.003 (3)	0.0967 (16)	0.033 (7)*
H2C	0.477 (4)	1.023 (3)	0.1532 (18)	0.046 (9)*

	U11	U22	U33	U12	U13	U23
Zn1	0.03299 (15)	0.04154 (17)	0.02676 (15)	−0.00188 (15)	−0.00155 (14)	−0.00045 (16)
C1	0.0323 (14)	0.0395 (17)	0.0359 (16)	0.0029 (14)	−0.0043 (14)	0.0082 (12)
C2	0.0345 (16)	0.0368 (17)	0.0390 (15)	0.0024 (13)	0.0001 (13)	−0.0014 (13)
C3	0.055 (2)	0.0371 (18)	0.052 (2)	−0.0065 (15)	0.0007 (17)	0.0019 (14)
C4	0.048 (2)	0.0392 (19)	0.0472 (17)	−0.0059 (15)	−0.0009 (17)	−0.0108 (14)
C5	0.0387 (16)	0.064 (2)	0.0445 (17)	0.0051 (17)	0.0090 (14)	0.0016 (15)
C6	0.045 (2)	0.084 (3)	0.059 (2)	−0.0144 (19)	0.0148 (18)	0.0118 (19)
C7	0.0445 (18)	0.0365 (17)	0.093 (3)	−0.0038 (13)	0.009 (2)	0.008 (2)
Cl1	0.0417 (4)	0.0762 (6)	0.0259 (3)	−0.0185 (4)	−0.0051 (3)	0.0063 (3)
Cl2	0.0424 (4)	0.1219 (9)	0.0283 (4)	−0.0064 (6)	0.0046 (3)	0.0013 (4)
Cl3	0.0541 (4)	0.0453 (5)	0.0806 (6)	−0.0143 (4)	−0.0084 (6)	−0.0038 (5)
Cl4	0.0641 (5)	0.0642 (6)	0.0536 (5)	0.0256 (5)	−0.0113 (5)	−0.0086 (4)
N1	0.0325 (11)	0.0402 (13)	0.0274 (11)	0.0026 (14)	−0.0013 (9)	0.0007 (10)
N2	0.0331 (13)	0.0481 (17)	0.0357 (13)	−0.0095 (11)	−0.0032 (10)	0.0030 (10)

Zn1—Cl3	2.2355 (9)	C4—H4A	0.9700
Zn1—Cl4	2.2597 (9)	C4—H4B	0.9700
Zn1—Cl2	2.2658 (8)	C5—N1	1.499 (3)
Zn1—Cl1	2.2795 (8)	C5—H5A	0.9600
C1—N1	1.513 (4)	C5—H5B	0.9600
C1—C2	1.517 (4)	C5—H5C	0.9600
C1—C7	1.519 (4)	C6—N2	1.504 (4)
C1—H1	0.9800	C6—H6A	0.9600
C2—N2	1.470 (4)	C6—H6B	0.9600
C2—H2A	0.9700	C6—H6C	0.9600
C2—H2B	0.9700	C7—H7A	0.9600
C3—N2	1.485 (4)	C7—H7B	0.9600
C3—C4	1.519 (5)	C7—H7C	0.9600
C3—H3A	0.9700	N1—H1A	0.93 (3)
C3—H3B	0.9700	N2—H2C	0.91 (3)
C4—N1	1.487 (4)
Cl3—Zn1—Cl4	108.34 (5)	N1—C5—H5A	109.5
Cl3—Zn1—Cl2	112.33 (4)	N1—C5—H5B	109.5
Cl4—Zn1—Cl2	112.08 (4)	H5A—C5—H5B	109.5
Cl3—Zn1—Cl1	109.55 (3)	N1—C5—H5C	109.5
Cl4—Zn1—Cl1	110.33 (4)	H5A—C5—H5C	109.5
Cl2—Zn1—Cl1	104.16 (3)	H5B—C5—H5C	109.5
N1—C1—C2	108.4 (2)	N2—C6—H6A	109.5
N1—C1—C7	111.1 (3)	N2—C6—H6B	109.5
C2—C1—C7	109.3 (3)	H6A—C6—H6B	109.5
N1—C1—H1	109.3	N2—C6—H6C	109.5
C2—C1—H1	109.3	H6A—C6—H6C	109.5
C7—C1—H1	109.3	H6B—C6—H6C	109.5
N2—C2—C1	113.2 (2)	C1—C7—H7A	109.5
N2—C2—H2A	108.9	C1—C7—H7B	109.5
C1—C2—H2A	108.9	H7A—C7—H7B	109.5
N2—C2—H2B	108.9	C1—C7—H7C	109.5
C1—C2—H2B	108.9	H7A—C7—H7C	109.5
H2A—C2—H2B	107.7	H7B—C7—H7C	109.5
N2—C3—C4	111.7 (3)	C4—N1—C5	110.3 (2)
N2—C3—H3A	109.3	C4—N1—C1	111.1 (2)
C4—C3—H3A	109.3	C5—N1—C1	113.9 (2)
N2—C3—H3B	109.3	C4—N1—H1A	107.7 (19)
C4—C3—H3B	109.3	C5—N1—H1A	102.4 (16)
H3A—C3—H3B	107.9	C1—N1—H1A	111.0 (18)
N1—C4—C3	111.1 (2)	C2—N2—C3	109.8 (2)
N1—C4—H4A	109.4	C2—N2—C6	111.9 (2)
C3—C4—H4A	109.4	C3—N2—C6	111.6 (3)
N1—C4—H4B	109.4	C2—N2—H2C	111 (2)
C3—C4—H4B	109.4	C3—N2—H2C	107 (2)
H4A—C4—H4B	108.0	C6—N2—H2C	105.5 (19)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1i	0.93 (3)	2.16 (3)	3.092 (2)	177 (3)
N2—H2C···Cl2ii	0.91 (3)	2.24 (3)	3.140 (3)	171 (3)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1i	0.93 (3)	2.16 (3)	3.092 (2)	177 (3)
N2—H2C⋯Cl2ii	0.91 (3)	2.24 (3)	3.140 (3)	171 (3)

Symmetry codes: (i) ; (ii) .