Bis(2,2′-bi-1H-imidazole)­copper(II) bis­(1,1,3,3-tetra­cyano-2-eth­oxy­propenide)

Gaamoune, B.; Setifi, Z.; Beghidja, A.; El-Ghozzi, M.; Setifi, F.; Avignant, D.

doi:10.1107/S1600536810029752

metal-organic compounds

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ISSN: 2056-9890

Volume 66| Part 8| August 2010| Pages m1044-m1045

https://doi.org/10.1107/S1600536810029752

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Bis(2,2′-bi-1H-imidazole)copper(II) bis(1,1,3,3-tetracyano-2-ethoxypropenide)

Bachir Gaamoune,^a Zouaoui Setifi,^b Adel Beghidja,^b Malika El-Ghozzi,^c Fatima Setifi ^a ^* and Daniel Avignant ^c

^aFaculté des Sciences, Département de Chimie, Université Ferhat Abbas de Sétif, 19000 Sétif, Algeria, ^bUnité de Recherche de Chimie de l'Environnement et Moléculaire Structurale, CHEMS, Faculté des Sciences Exactes, Département de Chimie, Université Mentouri Constantine, 25000 Constantine, Algeria, and ^cLaboratoire des Matériaux Inorganiques, UMR CNRS 6002, Université Blaise Pascal, 24 Avenue des Landais, 63177 Aubière, France
^*Correspondence e-mail: fat_setifi@yahoo.fr

(Received 16 July 2010; accepted 26 July 2010; online 31 July 2010)

In the title compound, [Cu(C₆H₆N₄)₂](C₉H₅N₄O)₂, the Cu²⁺ ion (site symmetry $[\overline{1}]$ ) is coordinated by two N,N′-bidentate 2,2′-biimidazole (H₂biim) ligands, generating a square-planar CuN₄ geometry. The dihedral angle between the aromatic rings in the ligand is 0.70 (9)°. In the polynitrile 1,1,3,3-tetracyano-2-ethoxypropenide (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 CuN₆ octahedron, with two N-bonded tcnoet anions completing the coordination. In the crystal, the components are linked by N—H⋯N and C—H⋯N interactions.

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_r = 702.18
Monoclinic, P 2₁ /c
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 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ) 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[F² > 2σ(F²)] = 0.034
wR(F²) = 0.077
S = 0.93
3002 reflections
223 parameters
H-atom parameters constrained
Δρ_max = 0.38 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Selected geometric parameters (Å, °)

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) x-1, y, z; (ii) x, y, z-1.

Data collection: CrysAlis CCD (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); cell refinement: CrysAlis RED (Oxford Diffraction, 2007 $[Oxford Diffraction (2007). CrysAlis CCD and CrysAlis RED. Oxford Diffraction Ltd, Abingdon, England.]$ ); 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 ).

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810029752/hb5555Isup2.hkl

checkCIF report

Comment top

Polynitrile anions are known to be interesting ligands in coordination chemistry because of their high electronic delocalization and their cyano groups juxtaposed in such a way that they cannot all coordinate to the same metal ion. They adopt different bridging or nonbridging coordination modes wich afford discrete or extended molecular architectures (Atmani et al., 2008; Benmansour et al., 2007; Triki et al., 2005; Thétiot et al., 2003). Following these structural and electronic characteristics, several series of binary systems "polynitrile/M(II)" with only polynitrile bridges or ternary systems "polynitrile/co-ligand/M(II)" (M(II), transition metal ion) involving an additional bridging or chelate co-ligand have been reported. Most of them display one-dimensional, two-dimensional and three-dimensional polymeric assemblies, in which the polynitrile anions act as µ2-, µ3- and/or µ4- bridging ligands and exhibit unusual magnetic properties (Batten & Murray, 2003; Jones et al., 2006; Yuste et al., 2007; Setifi et al., 2006; Setifi et al., 2007).

In our case we have chosen to investigate the ternary system including 2,2'-biimidazole (H₂bim) selected as co-ligand because it is bifunctional: the imino moieties can be coordinated to a metal ion acting as the first coordination sphere and the amino N—H and C—H groups, as the second coordination sphere, may donate multifold hydrogen bonds to tcnoet anions, extending the structure into a high-dimensional network. In this contribution we report the synthesis and the crystal structure of a new copper(II) compound with neutral 2,2'-biimidazole, Cu(H₂biim)₂] (tcnoet)₂, (I).

The crystal of (I) is built of [Cu(H₂biim)₂]²⁺ cations and (tcnoet)^- anions interconnected by hydrogen bonds. As shown in Fig. 1, the Cu(II) ion has a square coordination geometry, it locates on a symmetry inversion center and relates four nitrogen atoms of two symmetry-related 2,2'-biimidazole molecules which bind bidentately arranged trans to each other in the square plane [Cu1—N1 = 1.973 (2) Å and Cu1—N2 = 2.040 (2) Å] and interacts with two nitrogen atoms belonging to tcnoet ligands occupying the apical coordination sites [Cu1—N7 = 2.821 (3) Å]. Selected interatomic distances and angles are listed in Table 1.

The Cu—N bond distances to H₂biim and inter-ring C1—C2 bond length in (I) present no unusual features and are consistent with the previous report in [Cu(H₂biim)₂]Cl₂ [Bencini & Mani, 1988], [Cu(Me₄biim)ONO₂]Cl [Bernarducci et al., 1983] and [VOCl(H₂Biim)₂]Cl [Cancela et al., 2001] complexes. In our case the principal coordination is planar and the Cu atom lies within that plane. Both imidazole rings are planar, with no atoms deviating by more than 0.007 A° from the least-squares plane. The two rings of H₂biim are nearly coplanar, making an angle of 0.70 (9)°. This value compares well with that found in the mononuclear copper(II) species [Cu(H₂biim)₂]²⁺ which are in a strictly planar environment (Bencini & Mani, 1988) and that observed in the free H₂biim molecule (Cromer et al., 1987), but it is smaller than that found for the mononuclear oxovanadium(IV) species [VOCl(H₂biim)₂]Cl (Cancela et al., 2001).

[Cu(H₂biim)₂](tcnoet)₂ units are connected to each other via hydrogen bonds N—H···N resulting in a one-dimensional chains as shown in Fig. 2. Furthermore these chains are maintained through van der Waals interactions on the (ab) plane and connect each other via C—H···N hydrogen bonds into a two-dimensional network (Fig. 3). Interestingly, each tcnoet^- anion help to sustain the one-dimensional assembly and at the same time the final two-dimensional array.

In this complex, the three central C atoms (C11, C12 and C13) of the anionic ligand present an sp² hybridization as indicated by the sum of the three angles around them (359.98° or 360.0°). Two additional facts support the idea of electron delocalization over the three central C atoms: (i) the six central C—C bond distances (1.389 A° -1.428 A°) are longer than a normal C═C double bond (1.340 A°) and close to those of benzene and (ii) the C11—O1 bond distance 1.352 A° is much shorter than tne normal C—O single bond, suggesting that the two central and the C11—O1 bond present a partial double character.

Related literature top

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 top

H₂biim and Ktcnoet ligands were synthesized with the published procedures respectively (Bernarducci et al., 1983; Middleton et al., 1958). To a methanolic suspension of H₂biim (0.025 g, 5 ml) was added drowpize a solution of CuCl₂.2H₂O (0.032 g, 5 ml) resulting in a green solution. Ktcnoet was dissolved in water (0.084 g, 10 ml) and was added quickly to the former solution. The final solution was filtred and allowed to evaporate for a week, giving green blocks of (I). X band EPR spectrum from a polycristalline powdred sample of (I) recorded at room temperature exhibits a well defined axial signal with g_parallel = 2.27 > g_{perpendicular} = 2.07 consistent with a Cu(II) monomer.

Structure description top

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.

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2007); cell refinement: CrysAlis RED (Oxford Diffraction, 2007); data reduction: CrysAlis RED (Oxford Diffraction, 2007); 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).

Figures top

	Fig. 1. The metal environnement in (I), with displacement ellipsoids drawn at the 50% probability level. Unlabelled atoms are related to labelled atoms by the symmetry operation 1 - x, 1 - y, 1 - z.
	Fig. 2. View of the one one-dimensional hydrogen bonded chain on the ab plane. Symmetry codes: i(-1 + x,y,z), ii(1 + x,y,z)
	Fig. 3. View of the hydrogen bonded maintaining the chains along the c axis. Symmetry codes i(1 - x,1 - y,1 - z), ii(1 - x,1 - y,-z), iii(x,y,1 + z), VIi(x,y,-1 +z), Vi(1 - x,1 - y,2 - z).

Bis(2,2'-bi-1H-imidazole)copper(II) bis(1,1,3,3-tetracyano-2-ethoxypropenide) top

Crystal data top

[Cu(C₆H₆N₄)₂](C₉H₅N₄O)₂	F(000) = 718
M_r = 702.18	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0371P)²] where P = (F_o² + 2F_c²)/3
3002 reflections	(Δ/σ)_max < 0.001
223 parameters	Δρ_max = 0.38 e Å⁻³
0 restraints	Δρ_min = −0.28 e Å⁻³

Crystal data top

[Cu(C₆H₆N₄)₂](C₉H₅N₄O)₂	V = 1551.9 (2) Å³
M_r = 702.18	Z = 2
Monoclinic, P2₁/c	Mo Kα radiation
a = 8.1001 (8) Å	µ = 0.76 mm⁻¹
b = 26.1834 (11) Å	T = 170 K
c = 8.2185 (7) Å	0.40 × 0.30 × 0.20 mm
β = 117.086 (11)°

Data collection top

Oxford Diffraction Xcalibur CCD diffractometer	3002 independent reflections
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2007)	1854 reflections with I > 2σ(I)
T_min = 0.750, T_max = 0.862	R_int = 0.037
8646 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.034	0 restraints
wR(F²) = 0.077	H-atom parameters constrained
S = 0.93	Δρ_max = 0.38 e Å⁻³
3002 reflections	Δρ_min = −0.28 e Å⁻³
223 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Symmetry code: (i) −x+1, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

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

Symmetry codes: (ii) x−1, y, z; (iii) x, y, z−1.

Experimental details

Crystal data
Chemical formula	[Cu(C₆H₆N₄)₂](C₉H₅N₄O)₂
M_r	702.18
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	170
a, b, c (Å)	8.1001 (8), 26.1834 (11), 8.2185 (7)
β (°)	117.086 (11)
V (Å³)	1551.9 (2)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.76
Crystal size (mm)	0.40 × 0.30 × 0.20

Data collection
Diffractometer	Oxford Diffraction Xcalibur CCD
Absorption correction	Multi-scan (CrysAlis RED; Oxford Diffraction, 2007)
T_min, T_max	0.750, 0.862
No. of measured, independent and observed [I > 2σ(I)] reflections	8646, 3002, 1854
R_int	0.037
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.034, 0.077, 0.93
No. of reflections	3002
No. of parameters	223
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.38, −0.28

Computer programs: CrysAlis CCD (Oxford Diffraction, 2007), CrysAlis RED (Oxford Diffraction, 2007), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1993), WinGX (Farrugia, 1999) and PLATON (Spek, 2009).

Selected geometric parameters (Å, º) top

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

N1—Cu1—N2	82.04 (8)

Hydrogen-bond geometry (Å, º) top

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) x−1, y, z; (ii) x, y, z−1.

Acknowledgements

The X-ray data were collected at the University of Bretagne Occidentale (UBO; UMR CNRS 6521). FS thanks Professor S. Triki for providing diffraction facilities and the Université Ferhat Abbas de Sétif, Algérie, for financial support.

References

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Volume 66| Part 8| August 2010| Pages m1044-m1045

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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Bis(2,2′-bi-1H-imidazole)­copper(II) bis­­(1,1,3,3-tetra­cyano-2-eth­­oxy­propenide)

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Experimental

Crystal data

Data collection

Refinement

Supporting information

Acknowledgements

References

metal-organic compounds

Bis(2,2′-bi-1H-imidazole)copper(II) bis(1,1,3,3-tetracyano-2-ethoxypropenide)