Bis(1-methyl-piperazine-1,4-diium) tetra-chloridocuprate(II).

The title compound, (C(5)H(14)N(2))[CuCl(4)], was synthesized by hydro-thermal reaction of CuCl(2) with 1-methyl-piperazine in an HCl/water solution. Both amine N atoms are protonated. The piperazine ring adopts a chair conformation. The Cu-Cl distances in the tetrahedral anion are in the range 2.2360 (7)-2.2732 (7) Å. In the crystal, moderately strong and weak inter-molecular N-H⋯Cl hydrogen bonds link the anion and cation units into an infinite two-dimensional network parallel to the ab plane.

Related literature

For related amino coordination compounds, see: Fu et al. (2009 ▶); Aminabhavi et al. (1986 ▶); Dai & Fu (2008a ▶,b ▶). For halogen atoms as hydrogen-bond acceptors, see: Brammer et al. (2001 ▶). For the bromide analogue of the title compound, see: Peng (2011 ▶).

Experimental

Crystal data

(C5H14N2)[CuCl4]

M = 307.52

Orthorhombic,

a = 8.9717 (18) Å

b = 9.945 (2) Å

c = 13.753 (3) Å

V = 1227.1 (4) Å3

Z = 4

Mo Kα radiation

μ = 2.61 mm−1

T = 298 K

0.20 × 0.05 × 0.05 mm

Data collection

Rigaku Mercury2 diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.89, T max = 1.00

12813 measured reflections

2808 independent reflections

2616 reflections with I > 2σ(I)

R int = 0.036

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.059

S = 1.11

2808 reflections

111 parameters

H-atom parameters constrained

Δρmax = 0.35 e Å−3

Δρmin = −0.30 e Å−3

Absolute structure: Flack (1983 ▶), 1185 Friedel pairs

Flack parameter: 0.010 (11)

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: SHELXTL.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811024354/vn2015sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811024354/vn2015Isup2.hkl

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

(C5H14N2)[CuCl4]	F(000) = 620
Mr = 307.52	Dx = 1.665 Mg m−3
Orthorhombic, P212121	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2ac 2ab	Cell parameters from 2808 reflections
a = 8.9717 (18) Å	θ = 3.1–27.5°
b = 9.945 (2) Å	µ = 2.61 mm−1
c = 13.753 (3) Å	T = 298 K
V = 1227.1 (4) Å3	Block, blue
Z = 4	0.20 × 0.05 × 0.05 mm

Rigaku Mercury2 diffractometer	2808 independent reflections
Radiation source: fine-focus sealed tube	2616 reflections with I > 2σ(I)
graphite	Rint = 0.036
Detector resolution: 13.6612 pixels mm-1	θmax = 27.5°, θmin = 3.1°
profile data from φ scans	h = −11→11
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −12→12
Tmin = 0.89, Tmax = 1.00	l = −17→17
12813 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) + (0.022P)2 + 0.1621P] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.059	(Δ/σ)max < 0.001
S = 1.11	Δρmax = 0.35 e Å−3
2808 reflections	Δρmin = −0.30 e Å−3
111 parameters	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
0 restraints	Extinction coefficient: 0.0271 (9)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 1185 Friedel pairs
Secondary atom site location: difference Fourier map	Flack parameter: 0.010 (11)

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 > 2sigma(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	0.78864 (3)	0.56811 (3)	0.60180 (2)	0.03632 (10)
Cl2	0.98061 (8)	0.41919 (7)	0.59536 (5)	0.05205 (19)
Cl3	0.71852 (8)	0.71379 (6)	0.71940 (5)	0.04349 (16)
N2	0.6621 (2)	−0.0291 (2)	0.58707 (15)	0.0377 (5)
H2A	0.6784	−0.1116	0.6118	0.045*
H2B	0.6166	−0.0538	0.5316	0.045*
Cl4	0.60364 (7)	0.41742 (6)	0.61497 (6)	0.04956 (18)
N1	0.7864 (2)	0.17565 (17)	0.70981 (13)	0.0304 (4)
H1	0.7517	0.2466	0.6761	0.037*
Cl1	0.88660 (8)	0.71628 (6)	0.49755 (5)	0.04457 (17)
C4	0.7962 (3)	0.0489 (2)	0.55755 (18)	0.0401 (5)
H4A	0.7658	0.1277	0.5211	0.048*
H4B	0.8585	−0.0060	0.5158	0.048*
C5	0.8834 (3)	0.0914 (2)	0.64550 (18)	0.0361 (5)
H5A	0.9174	0.0126	0.6808	0.043*
H5B	0.9702	0.1426	0.6256	0.043*
C1	0.8693 (3)	0.2304 (3)	0.79610 (19)	0.0491 (7)
H1A	0.8080	0.2948	0.8292	0.074*
H1B	0.9594	0.2731	0.7746	0.074*
H1C	0.8935	0.1581	0.8396	0.074*
C2	0.6547 (3)	0.0954 (3)	0.74224 (18)	0.0383 (6)
H2C	0.5919	0.1502	0.7838	0.046*
H2D	0.6882	0.0184	0.7796	0.046*
C3	0.5663 (3)	0.0481 (3)	0.65572 (18)	0.0397 (6)
H3A	0.4848	−0.0083	0.6776	0.048*
H3B	0.5241	0.1252	0.6224	0.048*

	U11	U22	U33	U12	U13	U23
Cu1	0.03892 (17)	0.02711 (15)	0.04294 (17)	0.00232 (13)	0.00213 (13)	0.00148 (13)
Cl2	0.0549 (4)	0.0356 (3)	0.0656 (4)	0.0155 (3)	0.0214 (3)	0.0148 (4)
Cl3	0.0472 (3)	0.0367 (3)	0.0466 (3)	−0.0003 (3)	0.0106 (3)	−0.0032 (3)
N2	0.0397 (11)	0.0306 (10)	0.0428 (12)	−0.0029 (8)	−0.0008 (9)	−0.0038 (9)
Cl4	0.0380 (3)	0.0328 (3)	0.0779 (5)	−0.0016 (3)	−0.0067 (3)	0.0037 (3)
N1	0.0304 (9)	0.0270 (9)	0.0340 (10)	0.0017 (8)	−0.0019 (9)	−0.0003 (8)
Cl1	0.0558 (4)	0.0348 (3)	0.0431 (3)	0.0093 (3)	0.0080 (3)	0.0093 (3)
C4	0.0483 (14)	0.0315 (12)	0.0403 (13)	−0.0010 (12)	0.0147 (11)	−0.0016 (11)
C5	0.0288 (12)	0.0280 (12)	0.0516 (14)	0.0007 (10)	0.0079 (10)	0.0019 (11)
C1	0.0456 (15)	0.0592 (17)	0.0424 (14)	−0.0092 (13)	−0.0093 (12)	−0.0046 (13)
C2	0.0324 (13)	0.0435 (14)	0.0391 (13)	−0.0042 (10)	0.0070 (10)	−0.0004 (11)
C3	0.0316 (12)	0.0422 (14)	0.0454 (14)	−0.0038 (11)	−0.0004 (10)	−0.0057 (13)

Cu1—Cl1	2.2360 (7)	C4—H4A	0.9700
Cu1—Cl4	2.2435 (8)	C4—H4B	0.9700
Cu1—Cl3	2.2606 (7)	C5—H5A	0.9700
Cu1—Cl2	2.2732 (7)	C5—H5B	0.9700
N2—C4	1.488 (3)	C1—H1A	0.9600
N2—C3	1.490 (3)	C1—H1B	0.9600
N2—H2A	0.9001	C1—H1C	0.9600
N2—H2B	0.8999	C2—C3	1.505 (3)
N1—C2	1.494 (3)	C2—H2C	0.9700
N1—C5	1.497 (3)	C2—H2D	0.9700
N1—C1	1.502 (3)	C3—H3A	0.9700
N1—H1	0.8998	C3—H3B	0.9700
C4—C5	1.502 (4)
Cl1—Cu1—Cl4	141.52 (3)	N1—C5—C4	109.30 (19)
Cl1—Cu1—Cl3	98.38 (3)	N1—C5—H5A	109.8
Cl4—Cu1—Cl3	99.47 (3)	C4—C5—H5A	109.8
Cl1—Cu1—Cl2	96.12 (3)	N1—C5—H5B	109.8
Cl4—Cu1—Cl2	97.38 (3)	C4—C5—H5B	109.8
Cl3—Cu1—Cl2	131.02 (3)	H5A—C5—H5B	108.3
C4—N2—C3	111.74 (19)	N1—C1—H1A	109.5
C4—N2—H2A	116.6	N1—C1—H1B	109.5
C3—N2—H2A	108.9	H1A—C1—H1B	109.5
C4—N2—H2B	106.1	N1—C1—H1C	109.5
C3—N2—H2B	114.6	H1A—C1—H1C	109.5
H2A—N2—H2B	98.4	H1B—C1—H1C	109.5
C2—N1—C5	109.69 (17)	N1—C2—C3	110.34 (19)
C2—N1—C1	110.44 (19)	N1—C2—H2C	109.6
C5—N1—C1	112.44 (19)	C3—C2—H2C	109.6
C2—N1—H1	107.4	N1—C2—H2D	109.6
C5—N1—H1	109.6	C3—C2—H2D	109.6
C1—N1—H1	107.1	H2C—C2—H2D	108.1
N2—C4—C5	110.40 (19)	N2—C3—C2	110.97 (19)
N2—C4—H4A	109.6	N2—C3—H3A	109.4
C5—C4—H4A	109.6	C2—C3—H3A	109.4
N2—C4—H4B	109.6	N2—C3—H3B	109.4
C5—C4—H4B	109.6	C2—C3—H3B	109.4
H4A—C4—H4B	108.1	H3A—C3—H3B	108.0

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···Cl3i	0.90	2.31	3.179 (2)	162
N2—H2B···Cl2ii	0.90	2.52	3.185 (2)	132
N2—H2B···Cl1ii	0.90	2.65	3.306 (2)	130
N1—H1···Cl4	0.90	2.31	3.1895 (19)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯Cl3i	0.90	2.31	3.179 (2)	162
N2—H2B⋯Cl2ii	0.90	2.52	3.185 (2)	132
N2—H2B⋯Cl1ii	0.90	2.65	3.306 (2)	130
N1—H1⋯Cl4	0.90	2.31	3.1895 (19)	164

Symmetry codes: (i) ; (ii) .