Bis(2,2'-bi-1H-imidazole)-copper(II) bis-(1,1,3,3-tetra-cyano-2-eth-oxy-propenide).

In the title compound, [Cu(C(6)H(6)N(4))(2)](C(9)H(5)N(4)O)(2), the Cu(2+) ion (site symmetry ) is coordinated by two N,N'-bidentate 2,2'-biimidazole (H(2)biim) ligands, generating a square-planar CuN(4) geometry. The dihedral angle between the aromatic rings in the ligand is 0.70 (9)°. In the polynitrile 1,1,3,3-tetra-cyano-2-eth-oxy-propenide (tcnoet) anion, the C-N, C-C and C-O bond lengths indicate extensive electronic delocalization. An alternative description for the metal-ion geometry is an extremely distorted CuN(6) octa-hedron, with two N-bonded tcnoet anions completing the coordination. In the crystal, the components are linked by N-H⋯N and C-H⋯N inter-actions.

Related literature

For the structures and properties of related compounds containing polynitrile anions, see: Atmani et al. (2008 ▶); Batten & Murray (2003 ▶); Bencini & Mani (1988 ▶); Benmansour et al. (2007 ▶); Cancela et al. (2001 ▶); Cromer et al. (1987 ▶); Jones et al. (2006 ▶); Setifi et al. (2006 ▶, 2007 ▶); Thétiot et al. (2003 ▶); Triki et al. (2005 ▶); Yuste et al. (2007 ▶). For the synthesis of the H2biim and Ktcnoet ligands, see: Bernarducci et al. (1983 ▶) and Middleton & Engelhardt (1958 ▶), respecively.

Experimental

Crystal data

[Cu(C6H6N4)2](C9H5N4O)2

M = 702.18

Monoclinic,

a = 8.1001 (8) Å

b = 26.1834 (11) Å

c = 8.2185 (7) Å

β = 117.086 (11)°

V = 1551.9 (2) Å3

Z = 2

Mo Kα radiation

μ = 0.76 mm−1

T = 170 K

0.40 × 0.30 × 0.20 mm

Data collection

Oxford Diffraction Xcalibur CCD diffractometer

Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007 ▶) T min = 0.750, T max = 0.862

8646 measured reflections

3002 independent reflections

1854 reflections with I > 2σ(I)

R int = 0.037

Refinement

R[F 2 > 2σ(F 2)] = 0.034

wR(F 2) = 0.077

S = 0.93

3002 reflections

223 parameters

H-atom parameters constrained

Δρmax = 0.38 e Å−3

Δρmin = −0.28 e Å−3

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and CAMERON (Watkin et al., 1993 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810029752/hb5555sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810029752/hb5555Isup2.hkl

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

[Cu(C6H6N4)2](C9H5N4O)2	F(000) = 718
Mr = 702.18	Dx = 1.503 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3092 reflections
a = 8.1001 (8) Å	θ = 2.8–31.5°
b = 26.1834 (11) Å	µ = 0.76 mm−1
c = 8.2185 (7) Å	T = 170 K
β = 117.086 (11)°	Block, green
V = 1551.9 (2) Å3	0.40 × 0.30 × 0.20 mm
Z = 2

Oxford Diffraction Xcalibur CCD diffractometer	3002 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1854 reflections with I > 2σ(I)
graphite	Rint = 0.037
Detector resolution: 8.3622 pixels mm-1	θmax = 26.0°, θmin = 2.8°
ω and φ scans	h = −9→9
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	k = −30→32
Tmin = 0.750, Tmax = 0.862	l = −10→9
8646 measured reflections

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.077	H-atom parameters constrained
S = 0.93	w = 1/[σ2(Fo2) + (0.0371P)2] where P = (Fo2 + 2Fc2)/3
3002 reflections	(Δ/σ)max < 0.001
223 parameters	Δρmax = 0.38 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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	0.5000	0.5000	0.5000	0.02739 (14)
O1	0.5765 (2)	0.72753 (6)	0.7896 (2)	0.0279 (4)
N1	0.3433 (3)	0.55852 (7)	0.3669 (3)	0.0270 (5)
N2	0.3432 (3)	0.50383 (7)	0.6359 (2)	0.0250 (4)
N3	0.1123 (3)	0.54298 (7)	0.6550 (3)	0.0276 (5)
H3	0.0198	0.5642	0.6311	0.033*
N4	0.1107 (3)	0.60926 (7)	0.3218 (3)	0.0301 (5)
H4	0.0189	0.6235	0.3346	0.036*
N7	0.7829 (4)	0.55883 (8)	0.7720 (3)	0.0473 (7)
N8	0.3624 (4)	0.63047 (9)	0.8836 (3)	0.0523 (7)
N9	0.8650 (3)	0.63404 (8)	0.4902 (3)	0.0431 (6)
N10	0.9040 (3)	0.79164 (8)	0.6867 (3)	0.0388 (6)
C1	0.2179 (3)	0.57061 (8)	0.4219 (3)	0.0240 (6)
C2	0.2177 (3)	0.54105 (8)	0.5686 (3)	0.0235 (6)
C3	0.3131 (4)	0.59086 (9)	0.2255 (4)	0.0362 (7)
H3A	0.3820	0.5912	0.1579	0.043*
C4	0.1704 (4)	0.62228 (9)	0.1967 (4)	0.0365 (7)
H4A	0.1211	0.6484	0.1069	0.044*
C5	0.3157 (4)	0.48229 (9)	0.7740 (3)	0.0306 (6)
H5	0.3858	0.4548	0.8490	0.037*
C6	0.1746 (3)	0.50594 (9)	0.7877 (3)	0.0306 (6)
H6	0.1278	0.4985	0.8721	0.037*
C7	0.7098 (4)	0.59593 (10)	0.7744 (3)	0.0312 (7)
C8	0.4741 (4)	0.63526 (9)	0.8363 (3)	0.0335 (7)
C9	0.8243 (4)	0.66396 (10)	0.5669 (4)	0.0297 (6)
C10	0.8449 (3)	0.75144 (10)	0.6727 (3)	0.0286 (6)
C11	0.6541 (3)	0.68945 (8)	0.7366 (3)	0.0234 (6)
C12	0.6126 (3)	0.64089 (8)	0.7755 (3)	0.0255 (6)
C13	0.7714 (3)	0.70132 (8)	0.6596 (3)	0.0241 (6)
C14	0.4716 (3)	0.76732 (9)	0.6587 (3)	0.0303 (6)
H14A	0.5344	0.7762	0.5836	0.036*
H14B	0.4669	0.7984	0.7252	0.036*
C15	0.2811 (4)	0.74960 (11)	0.5388 (4)	0.0507 (8)
H15A	0.2125	0.7766	0.4517	0.076*
H15B	0.2185	0.7413	0.6132	0.076*
H15C	0.2860	0.7191	0.4720	0.076*

	U11	U22	U33	U12	U13	U23
Cu1	0.0314 (3)	0.0214 (2)	0.0359 (3)	0.0069 (2)	0.0209 (2)	0.0044 (2)
O1	0.0385 (11)	0.0222 (8)	0.0283 (9)	0.0026 (8)	0.0200 (9)	0.0005 (8)
N1	0.0270 (13)	0.0232 (11)	0.0362 (13)	0.0033 (10)	0.0191 (11)	0.0019 (10)
N2	0.0249 (12)	0.0226 (10)	0.0291 (11)	0.0045 (10)	0.0137 (9)	0.0026 (10)
N3	0.0281 (13)	0.0241 (11)	0.0352 (12)	0.0040 (10)	0.0183 (11)	−0.0030 (10)
N4	0.0303 (13)	0.0236 (11)	0.0426 (14)	0.0087 (10)	0.0221 (11)	0.0039 (10)
N7	0.0602 (18)	0.0228 (12)	0.0658 (17)	0.0040 (12)	0.0348 (14)	0.0053 (12)
N8	0.078 (2)	0.0439 (15)	0.0591 (17)	−0.0250 (14)	0.0521 (16)	−0.0141 (13)
N9	0.0543 (17)	0.0358 (13)	0.0539 (15)	0.0115 (12)	0.0376 (14)	0.0048 (12)
N10	0.0317 (14)	0.0336 (13)	0.0491 (15)	−0.0085 (12)	0.0165 (12)	0.0003 (12)
C1	0.0268 (16)	0.0156 (12)	0.0318 (15)	0.0018 (11)	0.0154 (13)	−0.0030 (11)
C2	0.0231 (15)	0.0173 (12)	0.0320 (15)	−0.0031 (11)	0.0141 (12)	−0.0067 (11)
C3	0.0447 (19)	0.0298 (15)	0.0478 (18)	0.0104 (14)	0.0330 (16)	0.0119 (14)
C4	0.0472 (19)	0.0245 (14)	0.0442 (18)	0.0081 (14)	0.0263 (15)	0.0093 (13)
C5	0.0335 (17)	0.0273 (14)	0.0319 (15)	0.0063 (12)	0.0156 (13)	0.0069 (11)
C6	0.0330 (16)	0.0345 (15)	0.0304 (14)	0.0003 (13)	0.0198 (12)	0.0007 (13)
C7	0.0423 (19)	0.0214 (14)	0.0312 (16)	−0.0089 (14)	0.0180 (14)	0.0014 (12)
C8	0.053 (2)	0.0215 (13)	0.0309 (15)	−0.0099 (13)	0.0231 (15)	−0.0060 (11)
C9	0.0281 (17)	0.0274 (14)	0.0380 (16)	0.0020 (12)	0.0187 (13)	0.0087 (13)
C10	0.0212 (16)	0.0343 (15)	0.0291 (15)	0.0023 (13)	0.0105 (12)	0.0035 (12)
C11	0.0257 (16)	0.0216 (13)	0.0184 (12)	−0.0003 (11)	0.0062 (11)	−0.0009 (10)
C12	0.0315 (16)	0.0198 (13)	0.0280 (14)	−0.0024 (12)	0.0160 (12)	−0.0011 (11)
C13	0.0257 (15)	0.0178 (12)	0.0309 (14)	0.0012 (11)	0.0147 (12)	0.0008 (11)
C14	0.0320 (17)	0.0243 (13)	0.0353 (16)	0.0066 (12)	0.0158 (13)	0.0033 (12)
C15	0.039 (2)	0.0549 (19)	0.048 (2)	−0.0006 (16)	0.0106 (16)	−0.0014 (16)

Cu1—N1	1.9727 (19)	N10—C10	1.140 (3)
Cu1—N1i	1.9727 (19)	C1—C2	1.433 (3)
Cu1—N2i	2.0397 (18)	C3—C4	1.349 (3)
Cu1—N2	2.0397 (18)	C3—H3A	0.9500
Cu1—N7	2.821 (2)	C4—H4A	0.9500
O1—C11	1.352 (3)	C5—C6	1.349 (3)
O1—C14	1.460 (3)	C5—H5	0.9500
N1—C1	1.324 (3)	C6—H6	0.9500
N1—C3	1.367 (3)	C7—C12	1.419 (3)
N2—C2	1.333 (3)	C8—C12	1.428 (4)
N2—C5	1.374 (3)	C9—C13	1.421 (3)
N3—C2	1.337 (3)	C10—C13	1.425 (3)
N3—C6	1.372 (3)	C11—C12	1.389 (3)
N3—H3	0.8800	C11—C13	1.395 (3)
N4—C1	1.343 (3)	C14—C15	1.477 (3)
N4—C4	1.364 (3)	C14—H14A	0.9900
N4—H4	0.8800	C14—H14B	0.9900
N7—C7	1.143 (3)	C15—H15A	0.9800
N8—C8	1.143 (3)	C15—H15B	0.9800
N9—C9	1.144 (3)	C15—H15C	0.9800
N1—Cu1—N1i	180.00	C3—C4—H4A	126.7
N1—Cu1—N2i	97.96 (8)	N4—C4—H4A	126.7
N1i—Cu1—N2i	82.04 (8)	C6—C5—N2	110.0 (2)
N1—Cu1—N2	82.04 (8)	C6—C5—H5	125.0
N1i—Cu1—N2	97.96 (8)	N2—C5—H5	125.0
N2i—Cu1—N2	180.0	C5—C6—N3	106.1 (2)
N1—Cu1—N7	95.79 (7)	C5—C6—H6	126.9
N1i—Cu1—N7	84.21 (7)	N3—C6—H6	126.9
N2i—Cu1—N7	88.69 (7)	N7—C7—C12	177.8 (3)
N2—Cu1—N7	91.31 (7)	N8—C8—C12	179.4 (3)
C11—O1—C14	119.25 (18)	N9—C9—C13	179.1 (3)
C1—N1—C3	105.9 (2)	N10—C10—C13	178.6 (3)
C1—N1—Cu1	113.35 (16)	O1—C11—C12	113.8 (2)
C3—N1—Cu1	140.66 (17)	O1—C11—C13	119.61 (19)
C2—N2—C5	105.23 (19)	C12—C11—C13	126.5 (2)
C2—N2—Cu1	110.87 (15)	C11—C12—C7	124.4 (2)
C5—N2—Cu1	143.89 (17)	C11—C12—C8	119.1 (2)
C2—N3—C6	107.6 (2)	C7—C12—C8	116.3 (2)
C2—N3—H3	126.2	C11—C13—C9	121.6 (2)
C6—N3—H3	126.2	C11—C13—C10	121.2 (2)
C1—N4—C4	107.3 (2)	C9—C13—C10	117.2 (2)
C1—N4—H4	126.3	O1—C14—C15	110.4 (2)
C4—N4—H4	126.3	O1—C14—H14A	109.6
C7—N7—Cu1	103.7 (2)	C15—C14—H14A	109.6
N1—C1—N4	110.7 (2)	O1—C14—H14B	109.6
N1—C1—C2	116.9 (2)	C15—C14—H14B	109.6
N4—C1—C2	132.4 (2)	H14A—C14—H14B	108.1
N2—C2—N3	111.0 (2)	C14—C15—H15A	109.5
N2—C2—C1	116.8 (2)	C14—C15—H15B	109.5
N3—C2—C1	132.2 (2)	H15A—C15—H15B	109.5
C4—C3—N1	109.5 (2)	C14—C15—H15C	109.5
C4—C3—H3A	125.2	H15A—C15—H15C	109.5
N1—C3—H3A	125.2	H15B—C15—H15C	109.5
C3—C4—N4	106.6 (2)
N2i—Cu1—N1—C1	178.54 (16)	C6—N3—C2—N2	1.3 (3)
N2—Cu1—N1—C1	−1.46 (16)	C6—N3—C2—C1	−179.2 (2)
N7—Cu1—N1—C1	−91.98 (17)	N1—C1—C2—N2	−0.4 (3)
N2i—Cu1—N1—C3	2.7 (3)	N4—C1—C2—N2	178.3 (2)
N2—Cu1—N1—C3	−177.3 (3)	N1—C1—C2—N3	−179.9 (2)
N7—Cu1—N1—C3	92.2 (3)	N4—C1—C2—N3	−1.2 (4)
N1i—Cu1—N2—C2	−178.76 (15)	C1—N1—C3—C4	0.2 (3)
N7—Cu1—N2—C2	96.90 (16)	Cu1—N1—C3—C4	176.3 (2)
N1—Cu1—N2—C5	−178.8 (3)	N1—C3—C4—N4	−0.1 (3)
N1i—Cu1—N2—C5	1.2 (3)	C1—N4—C4—C3	−0.1 (3)
N7—Cu1—N2—C5	−83.1 (3)	C2—N2—C5—C6	0.7 (3)
N1—Cu1—N7—C7	24.02 (19)	Cu1—N2—C5—C6	−179.3 (2)
N1i—Cu1—N7—C7	−155.98 (19)	N2—C5—C6—N3	0.1 (3)
N2i—Cu1—N7—C7	121.89 (19)	C2—N3—C6—C5	−0.9 (3)
N2—Cu1—N7—C7	−58.11 (19)	C14—O1—C11—C12	−129.2 (2)
C3—N1—C1—N4	−0.2 (3)	C14—O1—C11—C13	54.0 (3)
Cu1—N1—C1—N4	−177.52 (15)	O1—C11—C12—C7	−164.3 (2)
C3—N1—C1—C2	178.7 (2)	C13—C11—C12—C7	12.3 (4)
Cu1—N1—C1—C2	1.4 (3)	O1—C11—C12—C8	10.1 (3)
C4—N4—C1—N1	0.2 (3)	C13—C11—C12—C8	−173.3 (2)
C4—N4—C1—C2	−178.6 (2)	O1—C11—C13—C9	−166.3 (2)
C5—N2—C2—N3	−1.2 (3)	C12—C11—C13—C9	17.2 (4)
Cu1—N2—C2—N3	178.75 (15)	O1—C11—C13—C10	14.4 (4)
C5—N2—C2—C1	179.2 (2)	C12—C11—C13—C10	−162.0 (2)
Cu1—N2—C2—C1	−0.8 (2)	C11—O1—C14—C15	81.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N9ii	0.88	2.22	3.011 (3)	149
N4—H4···N9ii	0.88	2.17	2.967 (3)	150
C3—H3A···N8iii	0.95	2.42	3.187 (3)	138

Cu1—N1	1.9727 (19)
Cu1—N2	2.0397 (18)
Cu1—N7	2.821 (2)

N1—Cu1—N2

82.04 (8)

Table 2

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3⋯N9i	0.88	2.22	3.011 (3)	149
N4—H4⋯N9i	0.88	2.17	2.967 (3)	150
C3—H3A⋯N8ii	0.95	2.42	3.187 (3)	138

Symmetry codes: (i) ; (ii) .