catena-Poly[[diformatocopper(II)]-μ-1,4-bis­(imidazol-1-yl)benzene]

Abstract

In the title compound, [Cu(CHO₂)₂(C₁₂H₁₀N₄)], the Cu^II ion lies on an inversion center and is coordinated by two formate O atoms and two N atoms from two 1,4-bis­(imidazol-1-yl)phenyl ligands (L), forming a square-planar coordination environment. The linear mol­ecule L acts as a bidente bridging ligand, connecting the metal atoms into a chain along [101].

Related literature

For background to coordination polymers containing imidazole-derived ligands, see: Cui et al. (2005 ▶); Jin et al. (2008 ▶); Li et al. (2009 ▶).

Experimental

Crystal data

• [Cu(CHO₂)₂(C₁₂H₁₀N₄)]

• M _r = 363.82

• Monoclinic,

• a = 8.0971 (16) Å

• b = 10.426 (2) Å

• c = 8.5723 (17) Å

• β = 107.02 (3)°

• V = 692.0 (2) ų

• Z = 2

• Mo Kα radiation

• μ = 1.61 mm⁻¹

• T = 293 K

• 0.30 × 0.25 × 0.20 mm

Data collection

• Rigaku Mercury CCD area-detector diffractometer

• Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ▶) T _min = 0.624, T _max = 0.725

• 6003 measured reflections

• 1204 independent reflections

• 1108 reflections with I > 2σ(I)

• R _int = 0.026

Refinement

• R[F ² > 2σ(F ²)] = 0.025

• wR(F ²) = 0.075

• S = 1.11

• 1204 reflections

• 106 parameters

• H-atom parameters constrained

• Δρ_max = 0.40 e Å⁻³

• Δρ_min = −0.39 e Å⁻³

Data collection: CrystalClear (Rigaku/MSC, 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.

Supplementary Material

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

supplementary crystallographic information

Comment

Imidazole has been extensively used in crystal engineering, and a large number of imidazole-containing flexible ligands have been extensively studied (Cui et al., 2005; Jin et al., 2008). However, to our knowledge, the research on imidazole ligands bearing rigid spacers is still less developed (Li et al., 2009). For the title compound, the geometry of the Cu^II ion is bound by two imidazole rings of individual L ligands and two formate ions forming a square planar coordination environment (Fig. 1). Notably, as shown in Fig. 2, the four-coordinate Cu^II center is bridged by the linear ligand L to form an infinite one-dimensional chain along the [101] direction.

Experimental

A mixture of CH₃OH and H₂O (1:1, 8 ml), as a buffer layer, was carefully layered over a solution of Cu(HCO₂)₂ in H₂O (6 ml). Then a solution of 1,4-bis(imidazol-1-yl)phenyl (L, 0.06 mmol) in CH₃OH (6 ml) was layered over the buffer layer, and the resultant reaction was left to stand at room temperature. After ca. three weeks, blue block single crystals appeared at the boundary. Yield: ~25% (based on L).

Refinement

C-bound H atoms were positioned geometrically and refined in the riding-model approximation, with C—H = 0.93Å and U_iso(H) = 1.2U_eq (C).

Figures

Fig. 1.

The molecular structure of (I). Displacement ellipsoids are drawn at the 30% probability level and H atoms are shown as small spheres of arbitrary radius (symmetry codes: A = 1-x, 1-y, -z; B = 1+x, y, -1+z; C = -x, 1-y, 1-z.).

Fig. 2.

The crystal packing for (I).

Crystal data

[Cu(CHO2)2(C12H10N4)]	F(000) = 370
Mr = 363.82	Dx = 1.746 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 8.0971 (16) Å	Cell parameters from 2022 reflections
b = 10.426 (2) Å	θ = 2.0–27.9°
c = 8.5723 (17) Å	µ = 1.61 mm−1
β = 107.02 (3)°	T = 293 K
V = 692.0 (2) Å3	Block, blue
Z = 2	0.30 × 0.25 × 0.20 mm

Data collection

Rigaku Mercury CCD area-detector diffractometer	1204 independent reflections
Radiation source: fine-focus sealed tube	1108 reflections with I > 2σ(I)
graphite	Rint = 0.026
Detector resolution: 9 pixels mm-1	θmax = 25.0°, θmin = 3.3°
ω scans	h = −9→9
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −12→12
Tmin = 0.624, Tmax = 0.725	l = −10→10
6003 measured reflections

Refinement

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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.075	H-atom parameters constrained
S = 1.11	w = 1/[σ2(Fo2) + (0.0452P)2 + 0.4041P] where P = (Fo2 + 2Fc2)/3
1204 reflections	(Δ/σ)max < 0.001
106 parameters	Δρmax = 0.40 e Å−3
0 restraints	Δρmin = −0.39 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
Cu1	0.5000	0.5000	0.0000	0.01074 (16)
O2	0.3615 (2)	0.73953 (14)	−0.05814 (18)	0.0215 (4)
O1	0.55129 (17)	0.64376 (14)	0.15185 (16)	0.0154 (3)
N2	0.1326 (2)	0.44066 (17)	0.24042 (19)	0.0116 (4)
N1	0.3015 (2)	0.45187 (17)	0.0816 (2)	0.0128 (4)
C7	0.4602 (3)	0.73795 (19)	0.0823 (3)	0.0168 (4)
H7	0.4686	0.8130	0.1427	0.020*
C4	0.0645 (3)	0.4692 (2)	0.3731 (2)	0.0123 (4)
C3	0.0710 (2)	0.35192 (19)	0.1173 (2)	0.0142 (4)
H3	−0.0238	0.2981	0.1032	0.017*
C2	0.1769 (3)	0.35939 (19)	0.0218 (2)	0.0146 (4)
H2	0.1673	0.3097	−0.0706	0.018*
C6	−0.1121 (3)	0.4657 (2)	0.3490 (2)	0.0142 (4)
H6	−0.1864	0.4419	0.2482	0.017*
C1	0.2703 (3)	0.49981 (17)	0.2138 (3)	0.0112 (4)
H1	0.3340	0.5647	0.2786	0.013*
C5	0.1772 (3)	0.50202 (18)	0.5231 (3)	0.0144 (5)
H5	0.2957	0.5025	0.5382	0.017*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
Cu1	0.0110 (2)	0.0136 (2)	0.0095 (2)	0.00028 (12)	0.00592 (16)	−0.00072 (12)
O2	0.0258 (8)	0.0209 (8)	0.0175 (8)	0.0000 (7)	0.0058 (6)	0.0008 (6)
O1	0.0144 (7)	0.0196 (8)	0.0142 (7)	0.0003 (6)	0.0073 (6)	−0.0034 (6)
N2	0.0118 (8)	0.0144 (9)	0.0107 (8)	0.0009 (7)	0.0063 (7)	0.0008 (7)
N1	0.0144 (8)	0.0131 (8)	0.0123 (8)	0.0014 (7)	0.0062 (7)	0.0000 (7)
C7	0.0202 (10)	0.0138 (10)	0.0205 (11)	−0.0035 (8)	0.0124 (9)	−0.0034 (9)
C4	0.0158 (10)	0.0131 (9)	0.0104 (9)	0.0010 (8)	0.0077 (8)	0.0029 (8)
C3	0.0139 (9)	0.0150 (10)	0.0140 (9)	−0.0027 (8)	0.0045 (8)	−0.0008 (8)
C2	0.0181 (10)	0.0150 (10)	0.0117 (9)	−0.0005 (8)	0.0059 (8)	−0.0030 (8)
C6	0.0128 (10)	0.0216 (10)	0.0080 (9)	−0.0016 (8)	0.0028 (8)	−0.0006 (8)
C1	0.0115 (11)	0.0137 (10)	0.0098 (10)	0.0003 (7)	0.0050 (9)	0.0012 (7)
C5	0.0101 (10)	0.0201 (12)	0.0143 (11)	−0.0004 (7)	0.0055 (9)	0.0014 (7)

Geometric parameters (Å, °)

Cu1—O1i	1.9485 (14)	C7—H7	0.9300
Cu1—O1	1.9485 (14)	C4—C5	1.384 (3)
Cu1—N1i	1.9953 (17)	C4—C6	1.384 (3)
Cu1—N1	1.9953 (17)	C3—C2	1.350 (3)
O2—C7	1.235 (3)	C3—H3	0.9300
O1—C7	1.267 (3)	C2—H2	0.9300
N2—C1	1.351 (3)	C6—C5ii	1.390 (3)
N2—C3	1.382 (3)	C6—H6	0.9300
N2—C4	1.433 (3)	C1—H1	0.9300
N1—C1	1.329 (3)	C5—C6ii	1.390 (3)
N1—C2	1.381 (3)	C5—H5	0.9300
O1i—Cu1—O1	180.00 (8)	C5—C4—N2	119.09 (19)
O1i—Cu1—N1i	89.73 (7)	C6—C4—N2	119.75 (19)
O1—Cu1—N1i	90.27 (7)	C2—C3—N2	105.86 (17)
O1i—Cu1—N1	90.27 (7)	C2—C3—H3	127.1
O1—Cu1—N1	89.73 (7)	N2—C3—H3	127.1
N1i—Cu1—N1	180.0	C3—C2—N1	109.86 (17)
C7—O1—Cu1	107.51 (12)	C3—C2—H2	125.1
C1—N2—C3	107.92 (16)	N1—C2—H2	125.1
C1—N2—C4	124.60 (17)	C4—C6—C5ii	119.3 (2)
C3—N2—C4	127.48 (17)	C4—C6—H6	120.4
C1—N1—C2	106.15 (17)	C5ii—C6—H6	120.4
C1—N1—Cu1	125.33 (14)	N1—C1—N2	110.19 (18)
C2—N1—Cu1	128.41 (13)	N1—C1—H1	124.9
O2—C7—O1	126.19 (19)	N2—C1—H1	124.9
O2—C7—H7	116.9	C4—C5—C6ii	119.6 (2)
O1—C7—H7	116.9	C4—C5—H5	120.2
C5—C4—C6	121.1 (2)	C6ii—C5—H5	120.2
O1i—Cu1—O1—C7	−151.1 (3)	C1—N2—C3—C2	1.1 (2)
N1i—Cu1—O1—C7	93.37 (13)	C4—N2—C3—C2	−179.90 (19)
N1—Cu1—O1—C7	−86.63 (13)	N2—C3—C2—N1	−0.7 (2)
O1i—Cu1—N1—C1	168.60 (17)	C1—N1—C2—C3	0.1 (2)
O1—Cu1—N1—C1	−11.40 (17)	Cu1—N1—C2—C3	176.50 (14)
N1i—Cu1—N1—C1	−7(100)	C5—C4—C6—C5ii	1.2 (3)
O1i—Cu1—N1—C2	−7.16 (17)	N2—C4—C6—C5ii	−177.73 (18)
O1—Cu1—N1—C2	172.84 (17)	C2—N1—C1—N2	0.6 (2)
N1i—Cu1—N1—C2	177 (100)	Cu1—N1—C1—N2	−175.95 (12)
Cu1—O1—C7—O2	−2.2 (3)	C3—N2—C1—N1	−1.1 (2)
C1—N2—C4—C5	−35.7 (3)	C4—N2—C1—N1	179.88 (17)
C3—N2—C4—C5	145.4 (2)	C6—C4—C5—C6ii	−1.2 (3)
C1—N2—C4—C6	143.3 (2)	N2—C4—C5—C6ii	177.73 (18)
C3—N2—C4—C6	−35.6 (3)

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