Bis(2,2′-bi-1H-imidazole-κ2N3,N3′)bis­(4-methyl­benzoato-κO)copper(II)

Hui, Z.

doi:10.1107/S1600536809044262

metal-organic compounds

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Volume 65| Part 12| December 2009| Page m1498

doi:10.1107/S1600536809044262

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Bis(2,2′-bi-1H-imidazole-κ²N³,N^3′)bis(4-methylbenzoato-κO)copper(II)

Zhou Hui ^a ^*

^aCollege of Chemistry and Chemical Engineering, Henan University, Kaifeng 475001, People's Republic of China
^*Correspondence e-mail: zhouhui@163.com

(Received 5 October 2009; accepted 24 October 2009; online 4 November 2009)

In title compound, [Cu(C₈H₇O₂)₂(C₆H₆N₄)₂], the Cu^II atom (site symmetry $[\overline{1}]$ ) is coordinated by two N,N′-bidentate 2,2′-biimidazole ligands and two weakly bonded 4-methylbenzoate anions, resulting in a strongly elongated trans-CuO₂N₄ octahedral geometry. In the crystal, adjacent molecules are linked via pairs of N—H⋯O hydrogen bonds into chains propagating in [010].

Related literature

For a related structure, see: Yang et al. (2009 ).

Experimental

Crystal data

[Cu(C₈H₇O₂)₂(C₆H₆N₄)₂]
M_r = 602.11
Monoclinic, P 2₁ /n
a = 12.2839 (9) Å
b = 7.3150 (5) Å
c = 14.9755 (11) Å
β = 93.673 (1)°
V = 1342.89 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.87 mm⁻¹
T = 296 K
0.25 × 0.18 × 0.15 mm

Data collection

Bruker SMART APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2001 ) T_min = 0.813, T_max = 0.881
6459 measured reflections
2611 independent reflections
1807 reflections with I > 2σ(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.104
S = 1.02
2611 reflections
196 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Selected bond lengths (Å)

Cu1—N3	2.012 (2)
Cu1—N1	2.021 (2)
Cu1—O2	2.685 (2)

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯O1ⁱ	0.890 (10)	1.755 (11)	2.644 (3)	178 (3)
N2—H2A⋯O2ⁱ	0.894 (10)	1.755 (11)	2.647 (3)	176 (3)
Symmetry code: (i) x, y-1, z.

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009 ); software used to prepare material for publication: PLATON.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809044262/hb5128sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809044262/hb5128Isup2.hkl

checkCIF report

Comment top

2,2'-Biimidazole is an interesting ligand because it has two N atoms and two –NH donors. Both N-donors having the stronger coordination ability and flexible coordination modes. Additionally, two –NH donors can interact with other hydrogen bonding acceptors via hydrogen bonds (Yang et al., 2009). Herein, we report the title compound of bis(4-methyl-benzenecarboxylate-kN)bis(2,2'-biimidazole-N,N') copper, (I).

In the symmetric unit of (I), Cu²⁺ having an inversion centre was chelated by two 2,2'-biimidazole ligands through and weakly interacts with two 4-methyl benzenecarboxylate ligands acting as monodentate, which results in a elongated octahedron (Cu1—N1 2.021 (2) Å; Cu1—N3 2.012 (2) Å; Cu1—O2 2.685 (2) Å). Adjacent two Cu(C₈H₇O₂)(C₆H₃N₄) units are linked together by two pairs of N—H···O hydrogen bonds forming two R₂²(9) motifs, which are further arranged into a one-dimensional chain along the [010] direction.

Related literature top

For a related structure, see: Yang et al. (2009).

Experimental top

CuCl₂.2H₂O (0.17 g, 1.0 mmol) was added into an aqueous solution (15 ml) of 4-methyl-benzenecarboxylic acid (0.14 g, 1.0 mmol) and NaOH (0.04 g, 1.0 mmol) and refluxed for 30 min. Then an ethanol solution (10 ml) containing 2,2'-biimidazole (0.13 g, 1.0 mmol) was slowly added with continuous stirring. The resulting solution was refluxed for 3 h, filtered and kept for crystallization. After nine days, blue blocks of (I) were obtained.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsoids drawn at the 30% probability level. H-bonds are shown as dashed lines. Unlabeled atoms are related to labeled atoms by the symmetry transformation (2 - x, 2 - y, -z).
	Fig. 2. Part of the crystal structure of (I), showing the formation of the one-dimensional chain along the [010] direction. Weak contacts and hydrogen bonds are shown as thick and thin dashed lines, respectively. H atoms not involved in the hydrogen bonds have been omitted for the clarity.

Bis(2,2'-bi-1H-imidazole-κ²N³,N^3')bis(4- methylbenzoato-κO)copper(II) top

Crystal data top

[Cu(C₈H₇O₂)₂(C₆H₆N₄)₂]	F(000) = 622
M_r = 602.11	D_x = 1.489 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1035 reflections
a = 12.2839 (9) Å	θ = 2.7–22.3°
b = 7.3150 (5) Å	µ = 0.87 mm⁻¹
c = 14.9755 (11) Å	T = 296 K
β = 93.673 (1)°	Block, blue
V = 1342.89 (17) Å³	0.25 × 0.18 × 0.15 mm
Z = 2

Data collection top

Bruker SMART APEX CCD diffractometer	2611 independent reflections
Radiation source: fine-focus sealed tube	1807 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.043
0.3° wide ω exposures scans	θ_max = 26.0°, θ_min = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2001)	h = −13→15
T_min = 0.813, T_max = 0.881	k = −8→9
6459 measured reflections	l = −18→10

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0405P)² + 0.305P] where P = (F_o² + 2F_c²)/3
2611 reflections	(Δ/σ)_max < 0.001
196 parameters	Δρ_max = 0.26 e Å⁻³
2 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

[Cu(C₈H₇O₂)₂(C₆H₆N₄)₂]	V = 1342.89 (17) Å³
M_r = 602.11	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 12.2839 (9) Å	µ = 0.87 mm⁻¹
b = 7.3150 (5) Å	T = 296 K
c = 14.9755 (11) Å	0.25 × 0.18 × 0.15 mm
β = 93.673 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	2611 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2001)	1807 reflections with I > 2σ(I)
T_min = 0.813, T_max = 0.881	R_int = 0.043
6459 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	2 restraints
wR(F²) = 0.104	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.26 e Å⁻³
2611 reflections	Δρ_min = −0.29 e Å⁻³
196 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	1.0000	1.0000	0.0000	0.03766 (19)
N1	0.89630 (18)	0.7883 (3)	0.01223 (16)	0.0349 (6)
N2	0.8736 (2)	0.5161 (3)	0.07173 (18)	0.0397 (6)
H2A	0.895 (3)	0.410 (3)	0.096 (2)	0.067 (11)*
N3	1.09622 (18)	0.8469 (3)	0.08419 (16)	0.0347 (6)
N4	1.1064 (2)	0.5980 (4)	0.16805 (17)	0.0408 (6)
H4A	1.087 (2)	0.494 (3)	0.193 (2)	0.053 (10)*
C9	0.7954 (2)	0.7212 (4)	−0.0174 (2)	0.0417 (8)
H9	0.7454	0.7807	−0.0565	0.050*
C10	0.7809 (2)	0.5549 (4)	0.0195 (2)	0.0450 (8)
H10	0.7195	0.4809	0.0110	0.054*
C11	0.9395 (2)	0.6593 (4)	0.06569 (19)	0.0333 (7)
C12	1.0464 (2)	0.6939 (4)	0.10720 (19)	0.0342 (7)
C13	1.2008 (2)	0.6939 (4)	0.1851 (2)	0.0478 (8)
H13	1.2587	0.6610	0.2249	0.057*
C14	1.1944 (2)	0.8452 (4)	0.1337 (2)	0.0420 (8)
H14	1.2481	0.9346	0.1320	0.050*
O1	1.05155 (19)	1.2894 (3)	0.24540 (17)	0.0673 (8)
O2	0.93115 (18)	1.1925 (3)	0.13825 (16)	0.0527 (6)
C1	0.9823 (3)	1.1777 (4)	0.2138 (2)	0.0444 (8)
C2	0.9573 (2)	1.0140 (4)	0.2697 (2)	0.0379 (7)
C3	0.8761 (2)	0.8939 (4)	0.2408 (2)	0.0415 (8)
H3	0.8384	0.9127	0.1857	0.050*
C4	0.8499 (3)	0.7468 (5)	0.2923 (2)	0.0500 (9)
H4	0.7947	0.6676	0.2715	0.060*
C5	0.9039 (3)	0.7145 (5)	0.3741 (2)	0.0506 (9)
C6	0.9860 (3)	0.8328 (5)	0.4026 (2)	0.0566 (10)
H6	1.0242	0.8122	0.4573	0.068*
C7	1.0128 (3)	0.9816 (4)	0.3515 (2)	0.0507 (9)
H7	1.0683	1.0602	0.3722	0.061*
C8	0.8718 (3)	0.5549 (6)	0.4308 (3)	0.0838 (14)
H8A	0.8992	0.4436	0.4067	0.126*
H8B	0.7937	0.5485	0.4307	0.126*
H8C	0.9021	0.5710	0.4910	0.126*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cu1	0.0373 (3)	0.0273 (3)	0.0474 (4)	−0.0028 (2)	−0.0042 (2)	0.0112 (2)
N1	0.0373 (13)	0.0266 (13)	0.0404 (15)	0.0007 (11)	−0.0007 (11)	0.0035 (11)
N2	0.0399 (14)	0.0276 (15)	0.0512 (16)	−0.0012 (12)	−0.0003 (13)	0.0073 (12)
N3	0.0383 (13)	0.0242 (13)	0.0411 (15)	−0.0033 (11)	−0.0010 (12)	0.0036 (11)
N4	0.0411 (15)	0.0313 (15)	0.0488 (17)	−0.0016 (12)	−0.0071 (13)	0.0134 (13)
C9	0.0405 (17)	0.0315 (17)	0.052 (2)	0.0030 (14)	−0.0065 (15)	0.0054 (14)
C10	0.0370 (17)	0.0360 (18)	0.061 (2)	−0.0050 (14)	−0.0052 (16)	0.0028 (16)
C11	0.0381 (16)	0.0254 (16)	0.0364 (17)	−0.0013 (13)	0.0039 (14)	0.0040 (13)
C12	0.0375 (16)	0.0270 (16)	0.0378 (18)	0.0013 (13)	0.0007 (14)	0.0005 (13)
C13	0.0412 (18)	0.046 (2)	0.054 (2)	−0.0018 (15)	−0.0124 (16)	0.0117 (17)
C14	0.0429 (18)	0.0359 (18)	0.046 (2)	−0.0071 (14)	−0.0050 (16)	0.0042 (15)
O1	0.0665 (16)	0.0519 (16)	0.0802 (19)	−0.0196 (13)	−0.0211 (14)	0.0323 (14)
O2	0.0590 (14)	0.0433 (14)	0.0549 (15)	−0.0006 (11)	−0.0050 (12)	0.0187 (11)
C1	0.0415 (18)	0.0378 (19)	0.054 (2)	0.0051 (15)	0.0002 (17)	0.0120 (16)
C2	0.0374 (16)	0.0327 (17)	0.0437 (19)	0.0052 (14)	0.0023 (14)	0.0073 (14)
C3	0.0453 (18)	0.0395 (19)	0.0392 (19)	0.0028 (15)	−0.0010 (15)	0.0092 (15)
C4	0.0507 (19)	0.0427 (19)	0.056 (2)	−0.0127 (16)	−0.0030 (17)	0.0077 (17)
C5	0.0470 (19)	0.044 (2)	0.060 (2)	−0.0069 (16)	0.0045 (17)	0.0199 (17)
C6	0.057 (2)	0.058 (2)	0.053 (2)	−0.0043 (18)	−0.0108 (18)	0.0261 (18)
C7	0.0451 (18)	0.050 (2)	0.055 (2)	−0.0119 (16)	−0.0118 (16)	0.0160 (17)
C8	0.085 (3)	0.078 (3)	0.086 (3)	−0.029 (2)	−0.010 (2)	0.045 (3)

Geometric parameters (Å, º) top

Cu1—N3ⁱ	2.012 (2)	C13—C14	1.347 (4)
Cu1—N3	2.012 (2)	C13—H13	0.9300
Cu1—N1ⁱ	2.021 (2)	C14—H14	0.9300
Cu1—N1	2.021 (2)	O1—C1	1.251 (4)
Cu1—O2	2.685 (2)	O2—C1	1.263 (4)
Cu1—O2ⁱ	2.685 (2)	C1—C2	1.504 (4)
N1—C11	1.326 (3)	C2—C3	1.378 (4)
N1—C9	1.380 (3)	C2—C7	1.384 (4)
N2—C11	1.331 (3)	C3—C4	1.374 (4)
N2—C10	1.370 (4)	C3—H3	0.9300
N2—H2A	0.894 (10)	C4—C5	1.375 (4)
N3—C12	1.332 (3)	C4—H4	0.9300
N3—C14	1.375 (4)	C5—C6	1.376 (5)
N4—C12	1.334 (3)	C5—C8	1.510 (4)
N4—C13	1.365 (4)	C6—C7	1.382 (4)
N4—H4A	0.890 (10)	C6—H6	0.9300
C9—C10	1.353 (4)	C7—H7	0.9300
C9—H9	0.9300	C8—H8A	0.9600
C10—H10	0.9300	C8—H8B	0.9600
C11—C12	1.439 (4)	C8—H8C	0.9600

N3ⁱ—Cu1—N3	180.0	N4—C13—H13	126.3
N3ⁱ—Cu1—N1ⁱ	82.25 (9)	C13—C14—N3	109.4 (3)
N3—Cu1—N1ⁱ	97.75 (9)	C13—C14—H14	125.3
N3ⁱ—Cu1—N1	97.75 (9)	N3—C14—H14	125.3
N3—Cu1—N1	82.25 (9)	O1—C1—O2	124.8 (3)
N1ⁱ—Cu1—N1	180.0	O1—C1—C2	117.9 (3)
C11—N1—C9	104.9 (2)	O2—C1—C2	117.3 (3)
C11—N1—Cu1	111.68 (18)	C3—C2—C7	118.3 (3)
C9—N1—Cu1	143.3 (2)	C3—C2—C1	120.1 (3)
C11—N2—C10	106.6 (3)	C7—C2—C1	121.5 (3)
C11—N2—H2A	123 (2)	C4—C3—C2	120.9 (3)
C10—N2—H2A	129 (2)	C4—C3—H3	119.5
C12—N3—C14	104.7 (2)	C2—C3—H3	119.5
C12—N3—Cu1	111.65 (18)	C3—C4—C5	121.2 (3)
C14—N3—Cu1	143.40 (19)	C3—C4—H4	119.4
C12—N4—C13	106.5 (2)	C5—C4—H4	119.4
C12—N4—H4A	126 (2)	C4—C5—C6	118.0 (3)
C13—N4—H4A	128 (2)	C4—C5—C8	120.3 (3)
C10—C9—N1	109.2 (3)	C6—C5—C8	121.6 (3)
C10—C9—H9	125.4	C5—C6—C7	121.3 (3)
N1—C9—H9	125.4	C5—C6—H6	119.4
C9—C10—N2	107.0 (3)	C7—C6—H6	119.4
C9—C10—H10	126.5	C6—C7—C2	120.2 (3)
N2—C10—H10	126.5	C6—C7—H7	119.9
N1—C11—N2	112.3 (3)	C2—C7—H7	119.9
N1—C11—C12	117.1 (2)	C5—C8—H8A	109.5
N2—C11—C12	130.6 (3)	C5—C8—H8B	109.5
N3—C12—N4	112.1 (2)	H8A—C8—H8B	109.5
N3—C12—C11	117.2 (3)	C5—C8—H8C	109.5
N4—C12—C11	130.7 (3)	H8A—C8—H8C	109.5
C14—C13—N4	107.3 (3)	H8B—C8—H8C	109.5
C14—C13—H13	126.3

Symmetry code: (i) −x+2, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1ⁱⁱ	0.89 (1)	1.76 (1)	2.644 (3)	178 (3)
N2—H2A···O2ⁱⁱ	0.89 (1)	1.76 (1)	2.647 (3)	176 (3)

Symmetry code: (ii) x, y−1, z.

Experimental details

Crystal data
Chemical formula	[Cu(C₈H₇O₂)₂(C₆H₆N₄)₂]
M_r	602.11
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	12.2839 (9), 7.3150 (5), 14.9755 (11)
β (°)	93.673 (1)
V (Å³)	1342.89 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.87
Crystal size (mm)	0.25 × 0.18 × 0.15

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2001)
T_min, T_max	0.813, 0.881
No. of measured, independent and observed [I > 2σ(I)] reflections	6459, 2611, 1807
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.104, 1.02
No. of reflections	2611
No. of parameters	196
No. of restraints	2
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.26, −0.29

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), PLATON (Spek, 2009).

Selected bond lengths (Å) top

Cu1—N3	2.012 (2)	Cu1—O2	2.685 (2)
Cu1—N1	2.021 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···O1ⁱ	0.890 (10)	1.755 (11)	2.644 (3)	178 (3)
N2—H2A···O2ⁱ	0.894 (10)	1.755 (11)	2.647 (3)	176 (3)

Symmetry code: (i) x, y−1, z.

References

Bruker (2001). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yang, L. F., Cao, M. L., Mo, H. J., Hao, H. G., Wu, J. J., Zhang, J. P. & Ye, B. H. (2009). CrystEngComm, 11, 1114–1121. Web of Science CSD CrossRef CAS Google Scholar