1-(2,3-Di-methyl-phen-yl)piperazine-1,4-diium tetra-chlorido-cuprate(II).

In the title salt, (C12H20N2)[CuCl4], the Cu(II) atom occupies a general position in a flattened tetra-hedral environment by Cl ligands, characterized by Cl-Cu-Cl angles of 134.04 (3) and 137.18 (4)°. The six-membered piperazinediium ring adopts a chair conformation. The organic cation and inorganic anion inter-act through N-H⋯Cl and C-H⋯Cl hydrogen bonds, forming a three-dimensional network.

Related literature

For general background to the properties of tetra­halido­cuprate(II) compounds, see: Solomon et al. (1992 ▶); Kim et al. (2001 ▶); Panja et al. (2005 ▶); Lee et al. (2004 ▶); Turnbull et al. (2005 ▶); Shapiro et al. (2007 ▶). For general background to the geometry of the tetra­halidocuprate(II) species, see: Halvorson et al. (1990 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

(C12H20N2)[CuCl4]

M = 397.64

Triclinic,

a = 7.1986 (15) Å

b = 7.7611 (11) Å

c = 15.635 (4) Å

α = 77.035 (16)°

β = 79.311 (19)°

γ = 81.845 (14)°

V = 831.9 (3) Å3

Z = 2

Ag Kα radiation

λ = 0.56087 Å

μ = 1.01 mm−1

T = 293 K

0.25 × 0.20 × 0.15 mm

Data collection

Nonius MACH-3 diffractometer

Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983 ▶) T min = 0.786, T max = 0.863

9228 measured reflections

8079 independent reflections

4600 reflections with I > 2σ(I)

R int = 0.020

2 standard reflections every 120 min intensity decay: 7%

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.129

S = 1.00

8079 reflections

172 parameters

H-atom parameters constrained

Δρmax = 0.87 e Å−3

Δρmin = −0.68 e Å−3

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ▶); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1996 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶).

Crystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S1600536813021454/ru2053sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813021454/ru2053Isup2.hkl

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

(C12H20N2)[CuCl4]	Z = 2
Mr = 397.64	F(000) = 406
Triclinic, P1	Dx = 1.588 Mg m−3
Hall symbol: -P 1	Ag Kα radiation, λ = 0.56087 Å
a = 7.1986 (15) Å	Cell parameters from 25 reflections
b = 7.7611 (11) Å	θ = 9.0–10.7°
c = 15.635 (4) Å	µ = 1.01 mm−1
α = 77.035 (16)°	T = 293 K
β = 79.311 (19)°	Prism, yellow
γ = 81.845 (14)°	0.25 × 0.20 × 0.15 mm
V = 831.9 (3) Å3

Nonius MACH-3 diffractometer	4600 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.020
Graphite monochromator	θmax = 28.0°, θmin = 2.1°
non–profiled ω scans	h = −12→11
Absorption correction: part of the refinement model (ΔF) (Walker & Stuart, 1983)	k = −12→12
Tmin = 0.786, Tmax = 0.863	l = −26→2
9228 measured reflections	2 standard reflections every 120 min
8079 independent reflections	intensity decay: 7%

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.129	H-atom parameters constrained
S = 1.00	w = 1/[σ2(Fo2) + (0.0614P)2 + 0.0435P] where P = (Fo2 + 2Fc2)/3
8079 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.87 e Å−3
0 restraints	Δρmin = −0.68 e Å−3
0 constraints

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
Cu1	0.28980 (4)	0.31174 (4)	0.166012 (19)	0.03259 (8)
Cl3	0.56150 (8)	0.21183 (7)	0.22023 (4)	0.03825 (13)
Cl2	0.20878 (9)	0.53035 (8)	0.05406 (4)	0.04152 (14)
Cl1	0.27357 (11)	0.07141 (8)	0.10849 (5)	0.04717 (16)
Cl4	0.13588 (11)	0.43179 (10)	0.27862 (5)	0.05472 (19)
N1	0.6470 (2)	0.7932 (2)	0.25996 (11)	0.0256 (3)
H1	0.5611	0.8853	0.2411	0.031*
C5	0.6198 (3)	0.7639 (3)	0.35900 (14)	0.0287 (4)
C10	0.4411 (3)	0.8116 (3)	0.40409 (15)	0.0307 (4)
C4	0.8414 (3)	0.8412 (3)	0.21292 (15)	0.0298 (4)
H4A	0.8718	0.9435	0.2317	0.036*
H4B	0.9365	0.7426	0.2283	0.036*
N2	0.7973 (3)	0.7293 (3)	0.08360 (13)	0.0342 (4)
H2A	0.8894	0.6389	0.0928	0.041*
H2B	0.7938	0.7594	0.0248	0.041*
C9	0.4213 (3)	0.7840 (3)	0.49714 (16)	0.0342 (5)
C1	0.6039 (3)	0.6330 (3)	0.23052 (15)	0.0337 (4)
H1A	0.4785	0.6019	0.2598	0.040*
H1B	0.6956	0.5328	0.2479	0.040*
C2	0.6112 (3)	0.6693 (3)	0.13116 (16)	0.0359 (5)
H2C	0.5914	0.5621	0.1135	0.043*
H2D	0.5098	0.7603	0.1146	0.043*
C6	0.7721 (3)	0.6850 (3)	0.40122 (16)	0.0365 (5)
H6	0.8884	0.6514	0.3688	0.044*
C3	0.8434 (3)	0.8834 (3)	0.11406 (15)	0.0337 (4)
H3A	0.7513	0.9847	0.0988	0.040*
H3B	0.9680	0.9148	0.0839	0.040*
C7	0.7467 (4)	0.6570 (4)	0.49343 (17)	0.0436 (6)
H7	0.8462	0.6033	0.5238	0.052*
C8	0.5736 (4)	0.7093 (3)	0.53963 (17)	0.0420 (5)
H8	0.5590	0.6937	0.6012	0.050*
C11	0.2342 (4)	0.8368 (4)	0.55160 (19)	0.0506 (7)
H70	0.2526	0.8319	0.6114	0.076*
H72	0.1441	0.7564	0.5520	0.076*
H71	0.1871	0.9556	0.5260	0.076*
C12	0.2729 (3)	0.8866 (4)	0.35844 (18)	0.0450 (6)
H12A	0.1645	0.9099	0.4019	0.067*
H12B	0.2459	0.8026	0.3269	0.067*
H12C	0.3005	0.9953	0.3173	0.067*

	U11	U22	U33	U12	U13	U23
Cu1	0.03341 (14)	0.03084 (14)	0.03585 (16)	0.00481 (10)	−0.01015 (11)	−0.01292 (11)
Cl3	0.0377 (3)	0.0295 (2)	0.0513 (3)	0.0060 (2)	−0.0183 (2)	−0.0128 (2)
Cl2	0.0450 (3)	0.0395 (3)	0.0405 (3)	0.0100 (2)	−0.0159 (3)	−0.0105 (2)
Cl1	0.0676 (4)	0.0333 (3)	0.0480 (4)	−0.0068 (3)	−0.0224 (3)	−0.0121 (3)
Cl4	0.0545 (4)	0.0622 (4)	0.0416 (3)	0.0228 (3)	−0.0035 (3)	−0.0199 (3)
N1	0.0264 (8)	0.0238 (7)	0.0260 (8)	0.0000 (6)	−0.0036 (6)	−0.0058 (6)
C5	0.0346 (10)	0.0263 (9)	0.0254 (9)	−0.0014 (7)	−0.0033 (8)	−0.0081 (7)
C10	0.0313 (10)	0.0303 (10)	0.0301 (10)	−0.0023 (8)	−0.0025 (8)	−0.0078 (8)
C4	0.0278 (9)	0.0309 (10)	0.0312 (10)	−0.0033 (7)	−0.0045 (8)	−0.0072 (8)
N2	0.0353 (9)	0.0381 (10)	0.0304 (9)	0.0012 (7)	−0.0043 (8)	−0.0129 (8)
C9	0.0373 (11)	0.0330 (10)	0.0309 (11)	−0.0076 (9)	0.0033 (9)	−0.0082 (9)
C1	0.0394 (11)	0.0300 (10)	0.0345 (11)	−0.0097 (8)	−0.0031 (9)	−0.0109 (9)
C2	0.0376 (11)	0.0412 (12)	0.0325 (11)	−0.0069 (9)	−0.0060 (9)	−0.0130 (9)
C6	0.0361 (11)	0.0398 (12)	0.0335 (11)	0.0076 (9)	−0.0078 (9)	−0.0123 (9)
C3	0.0345 (11)	0.0351 (11)	0.0314 (11)	−0.0086 (9)	−0.0004 (9)	−0.0072 (9)
C7	0.0475 (14)	0.0492 (14)	0.0334 (12)	0.0070 (11)	−0.0133 (11)	−0.0090 (11)
C8	0.0550 (15)	0.0419 (13)	0.0290 (11)	−0.0022 (11)	−0.0065 (10)	−0.0092 (10)
C11	0.0481 (15)	0.0613 (17)	0.0385 (14)	−0.0070 (13)	0.0094 (12)	−0.0145 (13)
C12	0.0295 (11)	0.0605 (16)	0.0396 (13)	−0.0013 (11)	−0.0021 (10)	−0.0040 (12)

Cu1—Cl4	2.2170 (9)	C9—C11	1.510 (3)
Cu1—Cl3	2.2439 (8)	C1—C2	1.508 (3)
Cu1—Cl2	2.2467 (8)	C1—H1A	0.9700
Cu1—Cl1	2.2704 (7)	C1—H1B	0.9700
N1—C5	1.493 (3)	C2—H2C	0.9700
N1—C1	1.507 (3)	C2—H2D	0.9700
N1—C4	1.511 (3)	C6—C7	1.390 (3)
N1—H1	0.9100	C6—H6	0.9300
C5—C6	1.382 (3)	C3—H3A	0.9700
C5—C10	1.391 (3)	C3—H3B	0.9700
C10—C9	1.405 (3)	C7—C8	1.376 (4)
C10—C12	1.499 (3)	C7—H7	0.9300
C4—C3	1.504 (3)	C8—H8	0.9300
C4—H4A	0.9700	C11—H70	0.9600
C4—H4B	0.9700	C11—H72	0.9600
N2—C3	1.481 (3)	C11—H71	0.9600
N2—C2	1.488 (3)	C12—H12A	0.9600
N2—H2A	0.9000	C12—H12B	0.9600
N2—H2B	0.9000	C12—H12C	0.9600
C9—C8	1.377 (4)
Cl4—Cu1—Cl3	97.87 (3)	N1—C1—H1B	109.4
Cl4—Cu1—Cl2	98.37 (3)	C2—C1—H1B	109.4
Cl3—Cu1—Cl2	134.04 (3)	H1A—C1—H1B	108.0
Cl4—Cu1—Cl1	137.18 (4)	N2—C2—C1	111.22 (19)
Cl3—Cu1—Cl1	96.67 (3)	N2—C2—H2C	109.4
Cl2—Cu1—Cl1	99.83 (3)	C1—C2—H2C	109.4
C5—N1—C1	111.00 (16)	N2—C2—H2D	109.4
C5—N1—C4	115.08 (16)	C1—C2—H2D	109.4
C1—N1—C4	108.77 (16)	H2C—C2—H2D	108.0
C5—N1—H1	107.2	C5—C6—C7	118.2 (2)
C1—N1—H1	107.2	C5—C6—H6	120.9
C4—N1—H1	107.2	C7—C6—H6	120.9
C6—C5—C10	123.4 (2)	N2—C3—C4	110.92 (18)
C6—C5—N1	118.13 (19)	N2—C3—H3A	109.5
C10—C5—N1	118.40 (19)	C4—C3—H3A	109.5
C5—C10—C9	116.8 (2)	N2—C3—H3B	109.5
C5—C10—C12	123.3 (2)	C4—C3—H3B	109.5
C9—C10—C12	119.9 (2)	H3A—C3—H3B	108.0
C3—C4—N1	109.47 (17)	C8—C7—C6	119.7 (2)
C3—C4—H4A	109.8	C8—C7—H7	120.1
N1—C4—H4A	109.8	C6—C7—H7	120.1
C3—C4—H4B	109.8	C7—C8—C9	121.7 (2)
N1—C4—H4B	109.8	C7—C8—H8	119.1
H4A—C4—H4B	108.2	C9—C8—H8	119.1
C3—N2—C2	111.79 (17)	C9—C11—H70	109.5
C3—N2—H2A	109.3	C9—C11—H72	109.5
C2—N2—H2A	109.3	H70—C11—H72	109.5
C3—N2—H2B	109.3	C9—C11—H71	109.5
C2—N2—H2B	109.3	H70—C11—H71	109.5
H2A—N2—H2B	107.9	H72—C11—H71	109.5
C8—C9—C10	120.1 (2)	C10—C12—H12A	109.5
C8—C9—C11	119.2 (2)	C10—C12—H12B	109.5
C10—C9—C11	120.6 (2)	H12A—C12—H12B	109.5
N1—C1—C2	111.01 (18)	C10—C12—H12C	109.5
N1—C1—H1A	109.4	H12A—C12—H12C	109.5
C2—C1—H1A	109.4	H12B—C12—H12C	109.5
C1—N1—C5—C6	88.3 (2)	C12—C10—C9—C11	−2.8 (4)
C4—N1—C5—C6	−35.8 (3)	C5—N1—C1—C2	174.05 (18)
C1—N1—C5—C10	−89.5 (2)	C4—N1—C1—C2	−58.4 (2)
C4—N1—C5—C10	146.48 (19)	C3—N2—C2—C1	−53.9 (3)
C6—C5—C10—C9	3.1 (3)	N1—C1—C2—N2	55.3 (3)
N1—C5—C10—C9	−179.34 (19)	C10—C5—C6—C7	−2.1 (4)
C6—C5—C10—C12	−176.0 (2)	N1—C5—C6—C7	−179.7 (2)
N1—C5—C10—C12	1.6 (3)	C2—N2—C3—C4	56.3 (2)
C5—N1—C4—C3	−174.74 (17)	N1—C4—C3—N2	−59.4 (2)
C1—N1—C4—C3	60.0 (2)	C5—C6—C7—C8	−0.5 (4)
C5—C10—C9—C8	−1.4 (3)	C6—C7—C8—C9	2.1 (4)
C12—C10—C9—C8	177.7 (2)	C10—C9—C8—C7	−1.1 (4)
C5—C10—C9—C11	178.2 (2)	C11—C9—C8—C7	179.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···Cl3i	0.91	2.48	3.1610 (18)	132
N2—H2A···Cl2ii	0.90	2.35	3.144 (2)	147
N2—H2B···Cl1iii	0.90	2.30	3.152 (2)	159
N2—H2B···Cl2iii	0.90	2.80	3.271 (2)	114
C2—H2D···Cl1i	0.97	2.74	3.666 (3)	159
C3—H3B···Cl1iv	0.97	2.78	3.585 (2)	141
C4—H4B···Cl4ii	0.97	2.66	3.616 (2)	168
C6—H6···Cl4ii	0.93	2.71	3.572 (2)	154
C12—H12C···Cl3i	0.96	2.71	3.568 (3)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯Cl3i	0.91	2.48	3.1610 (18)	132
N2—H2A⋯Cl2ii	0.90	2.35	3.144 (2)	147
N2—H2B⋯Cl1iii	0.90	2.30	3.152 (2)	159
N2—H2B⋯Cl2iii	0.90	2.80	3.271 (2)	114
C2—H2D⋯Cl1i	0.97	2.74	3.666 (3)	159
C3—H3B⋯Cl1iv	0.97	2.78	3.585 (2)	141
C4—H4B⋯Cl4ii	0.97	2.66	3.616 (2)	168
C6—H6⋯Cl4ii	0.93	2.71	3.572 (2)	154
C12—H12C⋯Cl3i	0.96	2.71	3.568 (3)	149

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