Bis(2-ethyl-1H-imidazol-3-ium) tetra-chloridocuprate(II).

In the crystal structure of the title salt, (C(5)H(9)N(2))(2)[CuCl(4)], the organic cations and the tetrahedral [CuCl(4)] anions are linked into a three-dimensional network by N-H⋯Cl hydrogen bonds. The two 2-ethyl imidazolium cations in the asymmetric unit differ in the orientation of the ethyl group, with N-C-C-C torsion angles of -170.0 (4) and -87.6 (5)°.

Related literature

For general background to ferroelectric metal-organic frameworks, see: Fu et al. (2009 ▶); Ye et al. (2006 ▶); Zhang et al. (2008 ▶, 2010 ▶).

Experimental

Crystal data

(C5H9N2)2[CuCl4]

M = 399.63

Triclinic,

a = 7.992 (4) Å

b = 9.003 (4) Å

c = 12.216 (6) Å

α = 79.641 (14)°

β = 84.646 (14)°

γ = 72.154 (12)°

V = 822.4 (7) Å3

Z = 2

Mo Kα radiation

μ = 1.97 mm−1

T = 293 K

0.30 × 0.25 × 0.20 mm

Data collection

Rigaku SCXmini diffractometer

Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T min = 0.559, T max = 0.674

9065 measured reflections

3775 independent reflections

3124 reflections with I > 2σ(I)

R int = 0.035

Refinement

R[F 2 > 2σ(F 2)] = 0.039

wR(F 2) = 0.123

S = 1.17

3775 reflections

174 parameters

H-atom parameters constrained

Δρmax = 0.59 e Å−3

Δρmin = −0.66 e Å−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/S160053681005261X/vm2067sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681005261X/vm2067Isup2.hkl

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

(C5H9N2)2[CuCl4]	Z = 2
Mr = 399.63	F(000) = 406
Triclinic, P1	Dx = 1.614 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.992 (4) Å	Cell parameters from 2088 reflections
b = 9.003 (4) Å	θ = 2.4–27.5°
c = 12.216 (6) Å	µ = 1.97 mm−1
α = 79.641 (14)°	T = 293 K
β = 84.646 (14)°	Block, yellow
γ = 72.154 (12)°	0.30 × 0.25 × 0.20 mm
V = 822.4 (7) Å3

Rigaku SCXmini diffractometer	3775 independent reflections
Radiation source: fine-focus sealed tube	3124 reflections with I > 2σ(I)
graphite	Rint = 0.035
CCD_Profile_fitting scans	θmax = 27.5°, θmin = 1.7°
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	h = −10→10
Tmin = 0.559, Tmax = 0.674	k = −11→11
9065 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)] = 0.039	H-atom parameters constrained
wR(F2) = 0.123	w = 1/[σ2(Fo2) + (0.0636P)2] where P = (Fo2 + 2Fc2)/3
S = 1.17	(Δ/σ)max = 0.001
3775 reflections	Δρmax = 0.59 e Å−3
174 parameters	Δρmin = −0.66 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008)
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0014 (1)

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	0.91120 (5)	0.05748 (5)	0.21071 (3)	0.01639 (14)
C1	0.8790 (5)	0.4965 (4)	−0.1245 (3)	0.0203 (7)
H1	0.9490	0.4905	−0.1897	0.024*
C2	0.8332 (5)	0.3759 (4)	−0.0584 (3)	0.0192 (7)
H2	0.8657	0.2709	−0.0691	0.023*
C3	0.7099 (4)	0.5947 (4)	0.0167 (3)	0.0183 (7)
C4	0.6042 (5)	0.7072 (4)	0.0911 (3)	0.0250 (8)
H4A	0.5023	0.7782	0.0523	0.030*
H4B	0.6747	0.7704	0.1076	0.030*
C5	0.5432 (5)	0.6239 (5)	0.1994 (3)	0.0285 (9)
H5A	0.4760	0.5588	0.1835	0.043*
H5B	0.4713	0.7010	0.2426	0.043*
H5C	0.6436	0.5591	0.2406	0.043*
C6	0.7322 (5)	0.0989 (4)	0.5488 (3)	0.0223 (8)
H6	0.8545	0.0669	0.5483	0.027*
C7	0.6228 (5)	0.0601 (4)	0.6319 (3)	0.0208 (7)
H7	0.6544	−0.0045	0.6998	0.025*
C8	0.4588 (5)	0.2168 (4)	0.4944 (3)	0.0177 (7)
C9	0.3058 (5)	0.3210 (4)	0.4307 (3)	0.0257 (8)
H9A	0.2071	0.2783	0.4487	0.031*
H9B	0.3347	0.3231	0.3517	0.031*
C10	0.2529 (6)	0.4888 (5)	0.4567 (4)	0.0397 (11)
H10A	0.2191	0.4877	0.5343	0.060*
H10B	0.1557	0.5535	0.4126	0.060*
H10C	0.3507	0.5311	0.4397	0.060*
Cl1	1.16150 (11)	0.01933 (9)	0.10773 (7)	0.01903 (19)
Cl2	0.61789 (11)	0.16204 (10)	0.18983 (7)	0.0194 (2)
Cl3	0.94259 (11)	0.24838 (10)	0.29860 (7)	0.0204 (2)
Cl4	0.91629 (11)	−0.19331 (10)	0.27848 (8)	0.0233 (2)
N1	0.8018 (4)	0.6294 (3)	−0.0763 (2)	0.0193 (6)
H1A	0.8113	0.7219	−0.1024	0.023*
N2	0.7279 (4)	0.4409 (3)	0.0285 (2)	0.0187 (6)
H2A	0.6811	0.3891	0.0823	0.022*
N3	0.6284 (4)	0.1948 (3)	0.4648 (2)	0.0201 (6)
H3A	0.6673	0.2350	0.4020	0.024*
N4	0.4552 (4)	0.1350 (3)	0.5963 (2)	0.0186 (6)
H4C	0.3608	0.1298	0.6347	0.022*

	U11	U22	U33	U12	U13	U23
Cu1	0.0145 (2)	0.0147 (2)	0.0195 (2)	−0.00468 (17)	0.00088 (16)	−0.00158 (16)
C1	0.0197 (18)	0.0200 (17)	0.0211 (18)	−0.0069 (14)	−0.0028 (14)	−0.0008 (14)
C2	0.0228 (18)	0.0141 (16)	0.0215 (18)	−0.0061 (14)	0.0004 (14)	−0.0046 (13)
C3	0.0176 (17)	0.0170 (16)	0.0219 (18)	−0.0063 (14)	−0.0059 (14)	−0.0029 (13)
C4	0.029 (2)	0.0196 (18)	0.027 (2)	−0.0036 (16)	−0.0039 (16)	−0.0077 (15)
C5	0.029 (2)	0.029 (2)	0.025 (2)	0.0003 (17)	−0.0018 (16)	−0.0111 (16)
C6	0.0176 (17)	0.0208 (18)	0.026 (2)	−0.0031 (14)	0.0002 (15)	−0.0040 (15)
C7	0.0209 (18)	0.0199 (17)	0.0191 (18)	−0.0021 (14)	−0.0051 (14)	−0.0012 (14)
C8	0.0213 (18)	0.0142 (16)	0.0181 (17)	−0.0053 (14)	0.0002 (14)	−0.0046 (13)
C9	0.0232 (19)	0.0235 (19)	0.028 (2)	0.0009 (16)	−0.0101 (16)	−0.0062 (16)
C10	0.042 (3)	0.023 (2)	0.048 (3)	0.0048 (19)	−0.020 (2)	−0.0072 (19)
Cl1	0.0178 (4)	0.0166 (4)	0.0227 (4)	−0.0061 (3)	0.0043 (3)	−0.0042 (3)
Cl2	0.0147 (4)	0.0207 (4)	0.0209 (4)	−0.0052 (3)	−0.0015 (3)	0.0019 (3)
Cl3	0.0213 (4)	0.0221 (4)	0.0206 (4)	−0.0103 (3)	0.0030 (3)	−0.0061 (3)
Cl4	0.0208 (4)	0.0152 (4)	0.0293 (5)	−0.0035 (3)	0.0054 (4)	0.0017 (3)
N1	0.0217 (15)	0.0157 (14)	0.0206 (15)	−0.0080 (12)	−0.0038 (12)	0.0027 (12)
N2	0.0195 (15)	0.0158 (14)	0.0195 (15)	−0.0052 (12)	−0.0007 (12)	0.0006 (11)
N3	0.0221 (16)	0.0188 (14)	0.0177 (15)	−0.0058 (12)	0.0012 (12)	0.0000 (12)
N4	0.0161 (14)	0.0221 (15)	0.0181 (15)	−0.0067 (12)	0.0034 (12)	−0.0048 (12)

Cu1—Cl1	2.2287 (13)	C6—C7	1.346 (5)
Cu1—Cl4	2.2501 (13)	C6—N3	1.374 (4)
Cu1—Cl2	2.2625 (14)	C6—H6	0.9300
Cu1—Cl3	2.2688 (12)	C7—N4	1.374 (4)
C1—C2	1.355 (5)	C7—H7	0.9300
C1—N1	1.375 (5)	C8—N4	1.330 (4)
C1—H1	0.9300	C8—N3	1.333 (4)
C2—N2	1.391 (4)	C8—C9	1.481 (5)
C2—H2	0.9300	C9—C10	1.523 (5)
C3—N2	1.330 (4)	C9—H9A	0.9700
C3—N1	1.335 (5)	C9—H9B	0.9700
C3—C4	1.493 (5)	C10—H10A	0.9600
C4—C5	1.516 (6)	C10—H10B	0.9600
C4—H4A	0.9700	C10—H10C	0.9600
C4—H4B	0.9700	N1—H1A	0.8600
C5—H5A	0.9600	N2—H2A	0.8600
C5—H5B	0.9600	N3—H3A	0.8600
C5—H5C	0.9600	N4—H4C	0.8600
Cl1—Cu1—Cl4	101.08 (4)	C6—C7—N4	106.2 (3)
Cl1—Cu1—Cl2	139.56 (4)	C6—C7—H7	126.9
Cl4—Cu1—Cl2	98.32 (4)	N4—C7—H7	126.9
Cl1—Cu1—Cl3	97.91 (4)	N4—C8—N3	105.9 (3)
Cl4—Cu1—Cl3	130.13 (5)	N4—C8—C9	126.9 (3)
Cl2—Cu1—Cl3	96.09 (4)	N3—C8—C9	127.0 (3)
C2—C1—N1	106.7 (3)	C8—C9—C10	111.8 (3)
C2—C1—H1	126.7	C8—C9—H9A	109.3
N1—C1—H1	126.7	C10—C9—H9A	109.3
C1—C2—N2	106.1 (3)	C8—C9—H9B	109.3
C1—C2—H2	127.0	C10—C9—H9B	109.3
N2—C2—H2	127.0	H9A—C9—H9B	107.9
N2—C3—N1	106.5 (3)	C9—C10—H10A	109.5
N2—C3—C4	126.7 (3)	C9—C10—H10B	109.5
N1—C3—C4	126.8 (3)	H10A—C10—H10B	109.5
C3—C4—C5	112.6 (3)	C9—C10—H10C	109.5
C3—C4—H4A	109.1	H10A—C10—H10C	109.5
C5—C4—H4A	109.1	H10B—C10—H10C	109.5
C3—C4—H4B	109.1	C3—N1—C1	110.5 (3)
C5—C4—H4B	109.1	C3—N1—H1A	124.7
H4A—C4—H4B	107.8	C1—N1—H1A	124.7
C4—C5—H5A	109.5	C3—N2—C2	110.3 (3)
C4—C5—H5B	109.5	C3—N2—H2A	124.9
H5A—C5—H5B	109.5	C2—N2—H2A	124.9
C4—C5—H5C	109.5	C8—N3—C6	110.3 (3)
H5A—C5—H5C	109.5	C8—N3—H3A	124.8
H5B—C5—H5C	109.5	C6—N3—H3A	124.8
C7—C6—N3	106.8 (3)	C8—N4—C7	110.8 (3)
C7—C6—H6	126.6	C8—N4—H4C	124.6
N3—C6—H6	126.6	C7—N4—H4C	124.6

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···Cl1i	0.86	2.39	3.217 (3)	160
N2—H2A···Cl2	0.86	2.39	3.195 (3)	157
N3—H3A···Cl3	0.86	2.46	3.178 (3)	142
N4—H4C···Cl4ii	0.86	2.32	3.149 (3)	164

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯Cl1i	0.86	2.39	3.217 (3)	160
N2—H2A⋯Cl2	0.86	2.39	3.195 (3)	157
N3—H3A⋯Cl3	0.86	2.46	3.178 (3)	142
N4—H4C⋯Cl4ii	0.86	2.32	3.149 (3)	164

Symmetry codes: (i) ; (ii) .