(2R)-2-Methyl-piperazinediium tetra-chloridocuprate(II).

In the title compound, (C(5)H(14)N(2))[CuCl(4)], the copper(II) ion has a slightly tetra-hedrally distorted square-planar coordin-ation geometry and the diprotonated piperazine ring adopts a chair conformation. In the crystal structure, cations and anions are linked by inter-molecular N-H⋯Cl hydrogen bonds, forming a three-dimensional network.

Related literature

For the ferroelectric and non-linear optical properties of chiral organic ligands, see: Fu et al. (2007 ▶); Qu et al. (2003 ▶). For transition metal complexes of 2-methyl­piperazine, see: Ye et al. (2009 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

(C5H14N2)[CuCl4]

M = 307.53

Orthorhombic,

a = 6.0169 (12) Å

b = 12.985 (3) Å

c = 14.644 (3) Å

V = 1144.1 (4) Å3

Z = 4

Mo Kα radiation

μ = 2.80 mm−1

T = 293 K

0.30 × 0.25 × 0.22 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.87, T max = 0.90

11992 measured reflections

2627 independent reflections

2469 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.060

S = 1.10

2627 reflections

111 parameters

1 restraint

H-atom parameters constrained

Δρmax = 0.30 e Å−3

Δρmin = −0.53 e Å−3

Absolute structure: Flack (1983 ▶), 1091 Friedel pairs

Flack parameter: 0.00 (3)

Data collection: CrystalClear (Rigaku, 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/S1600536810007877/rz2412sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810007877/rz2412Isup2.hkl

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

(C5H14N2)[CuCl4]	F(000) = 620
Mr = 307.53	Dx = 1.785 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2469 reflections
a = 6.0169 (12) Å	θ = 3.1–27.5°
b = 12.985 (3) Å	µ = 2.80 mm−1
c = 14.644 (3) Å	T = 293 K
V = 1144.1 (4) Å3	Block, yellow
Z = 4	0.30 × 0.25 × 0.22 mm

Rigaku SCXmini diffractometer	2627 independent reflections
Radiation source: fine-focus sealed tube	2469 reflections with I > 2σ(I)
graphite	Rint = 0.051
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.1°
ω scans	h = −7→7
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −16→16
Tmin = 0.87, Tmax = 0.90	l = −18→18
11992 measured reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.025	w = 1/[σ2(Fo2) + (0.0239P)2 + 0.0175P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.060	(Δ/σ)max < 0.001
S = 1.10	Δρmax = 0.30 e Å−3
2627 reflections	Δρmin = −0.53 e Å−3
111 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
1 restraint	Extinction coefficient: 0.193 (9)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1091 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.00 (3)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
Cu1	0.82482 (13)	1.34903 (5)	0.01022 (5)	0.0237 (3)
Cl4	0.8203 (3)	1.32659 (11)	0.17172 (9)	0.0251 (4)
Cl3	0.8247 (3)	1.17476 (11)	−0.00811 (9)	0.0256 (4)
Cl2	0.8317 (3)	1.52141 (11)	0.02454 (12)	0.0365 (4)
Cl1	0.8196 (3)	1.36387 (11)	−0.14937 (10)	0.0250 (4)
N1	0.8224 (9)	1.0679 (4)	0.1788 (3)	0.0289 (11)
H1A	0.9338	1.1063	0.1559	0.035*
H1B	0.6932	1.0976	0.1626	0.035*
N2	0.6773 (9)	0.8919 (4)	0.2799 (3)	0.0263 (11)
H2A	0.8089	0.8638	0.2951	0.032*
H2B	0.5692	0.8523	0.3038	0.032*
C5	0.6696 (17)	0.7855 (5)	0.1398 (5)	0.055 (2)
H5C	0.5702	0.7410	0.1725	0.083*
H5B	0.8190	0.7603	0.1458	0.083*
H5A	0.6288	0.7867	0.0764	0.083*
C2	0.6553 (12)	0.8933 (5)	0.1786 (4)	0.0300 (14)
H2C	0.5097	0.9221	0.1630	0.036*
C4	0.8395 (11)	1.0661 (5)	0.2797 (4)	0.0309 (14)
H4B	0.8227	1.1354	0.3035	0.037*
H4A	0.9850	1.0408	0.2975	0.037*
C3	0.6623 (12)	0.9975 (5)	0.3195 (4)	0.0304 (13)
H3B	0.6801	0.9939	0.3853	0.036*
H3A	0.5170	1.0264	0.3067	0.036*
C1	0.8335 (12)	0.9624 (5)	0.1390 (4)	0.0323 (14)
H1D	0.9786	0.9329	0.1512	0.039*
H1C	0.8150	0.9666	0.0733	0.039*

	U11	U22	U33	U12	U13	U23
Cu1	0.0339 (4)	0.0198 (4)	0.0174 (4)	−0.0001 (3)	−0.0003 (3)	0.0000 (3)
Cl4	0.0236 (7)	0.0309 (8)	0.0209 (7)	−0.0006 (7)	−0.0001 (7)	−0.0035 (6)
Cl3	0.0392 (8)	0.0197 (7)	0.0178 (7)	−0.0004 (7)	0.0001 (7)	0.0001 (5)
Cl2	0.0540 (10)	0.0222 (8)	0.0333 (9)	−0.0006 (8)	−0.0017 (10)	−0.0016 (6)
Cl1	0.0238 (7)	0.0308 (8)	0.0205 (7)	−0.0010 (7)	−0.0001 (7)	0.0047 (6)
N1	0.025 (2)	0.034 (3)	0.028 (3)	−0.004 (3)	0.000 (3)	0.013 (2)
N2	0.026 (2)	0.028 (3)	0.024 (3)	−0.004 (3)	0.002 (3)	0.011 (2)
C5	0.090 (6)	0.035 (4)	0.041 (5)	−0.005 (5)	−0.005 (6)	0.000 (3)
C2	0.033 (3)	0.031 (3)	0.026 (3)	−0.001 (3)	−0.003 (3)	0.007 (3)
C4	0.037 (3)	0.031 (3)	0.025 (3)	−0.004 (3)	−0.003 (3)	0.009 (3)
C3	0.037 (3)	0.032 (3)	0.023 (3)	0.001 (3)	0.005 (3)	0.006 (3)
C1	0.037 (3)	0.039 (4)	0.022 (3)	0.000 (3)	0.005 (3)	0.007 (3)

Cu1—Cl2	2.2485 (16)	C5—H5C	0.9600
Cu1—Cl3	2.2788 (16)	C5—H5B	0.9600
Cu1—Cl1	2.3451 (15)	C5—H5A	0.9600
Cu1—Cl4	2.3831 (15)	C2—C1	1.514 (9)
N1—C4	1.482 (8)	C2—H2C	0.9800
N1—C1	1.490 (8)	C4—C3	1.506 (9)
N1—H1A	0.9000	C4—H4B	0.9700
N1—H1B	0.9000	C4—H4A	0.9700
N2—C2	1.489 (8)	C3—H3B	0.9700
N2—C3	1.492 (7)	C3—H3A	0.9700
N2—H2A	0.9000	C1—H1D	0.9700
N2—H2B	0.9000	C1—H1C	0.9700
C5—C2	1.513 (9)
Cl2—Cu1—Cl3	178.25 (7)	N2—C2—C5	111.0 (5)
Cl2—Cu1—Cl1	90.66 (6)	N2—C2—C1	109.0 (5)
Cl3—Cu1—Cl1	87.95 (5)	C5—C2—C1	111.4 (6)
Cl2—Cu1—Cl4	91.68 (6)	N2—C2—H2C	108.5
Cl3—Cu1—Cl4	89.74 (5)	C5—C2—H2C	108.5
Cl1—Cu1—Cl4	177.28 (6)	C1—C2—H2C	108.5
C4—N1—C1	111.9 (4)	N1—C4—C3	110.3 (6)
C4—N1—H1A	109.2	N1—C4—H4B	109.6
C1—N1—H1A	109.2	C3—C4—H4B	109.6
C4—N1—H1B	109.2	N1—C4—H4A	109.6
C1—N1—H1B	109.2	C3—C4—H4A	109.6
H1A—N1—H1B	107.9	H4B—C4—H4A	108.1
C2—N2—C3	111.8 (4)	N2—C3—C4	110.5 (5)
C2—N2—H2A	109.3	N2—C3—H3B	109.6
C3—N2—H2A	109.3	C4—C3—H3B	109.6
C2—N2—H2B	109.3	N2—C3—H3A	109.6
C3—N2—H2B	109.3	C4—C3—H3A	109.6
H2A—N2—H2B	107.9	H3B—C3—H3A	108.1
C2—C5—H5C	109.5	N1—C1—C2	111.3 (5)
C2—C5—H5B	109.5	N1—C1—H1D	109.4
H5C—C5—H5B	109.5	C2—C1—H1D	109.4
C2—C5—H5A	109.5	N1—C1—H1C	109.4
H5C—C5—H5A	109.5	C2—C1—H1C	109.4
H5B—C5—H5A	109.5	H1D—C1—H1C	108.0
C3—N2—C2—C5	−179.7 (7)	N1—C4—C3—N2	56.1 (7)
C3—N2—C2—C1	57.3 (7)	C4—N1—C1—C2	56.4 (7)
C1—N1—C4—C3	−55.8 (7)	N2—C2—C1—N1	−56.0 (7)
C2—N2—C3—C4	−58.1 (7)	C5—C2—C1—N1	−178.8 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1i	0.90	2.36	3.149 (6)	147
N1—H1B···Cl1ii	0.90	2.31	3.182 (6)	163
N2—H2A···Cl4iii	0.90	2.33	3.218 (6)	168
N2—H2B···Cl4iv	0.90	2.39	3.192 (6)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1i	0.90	2.36	3.149 (6)	147
N1—H1B⋯Cl1ii	0.90	2.31	3.182 (6)	163
N2—H2A⋯Cl4iii	0.90	2.33	3.218 (6)	168
N2—H2B⋯Cl4iv	0.90	2.39	3.192 (6)	148

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