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Acta Cryst. (2008). E64, m211    [ doi:10.1107/S1600536807066214 ]

Bis[2-(2-hydroxy-3-methoxyphenyl)benzimidazolium] tetrachloridocuprate(II) methanol disolvate

R. Xue, M. Niu, J. Dou and D. Wang

Abstract top

In the title compound, (C14H13N2O2)2[CuCl4]·2CH4O, the geometry of the CuC142- ions (Cu site symmetry 2) is intermediate between tetrahedral and square-planar. The dihedral angle between the benzimidazole and benzene ring systems is 8.74(14)°. A network of N-H...O, N-H...Cl and O-H...Cl hydrogen bonds helps to consoldiate the structure. Aromatic [pi]-[pi] stacking interactions involving the benzimidazole ring system, with a centroid-centroid distance of 3.785 (3) Å, also occur.

Comment top

2-(2-Hydroxyphenyl)benzimidazole complexes have potential applications in the fabrication of organic electroluminescent devices (e.g. Zhao et al., 2006). In the title compound, (I), the organic species is protonated and does not bind to the metal ion (Fig. 1). The copper(II) ion (site symmetry 2) adopts a geometry intermediate between square planar and tetrahedral (Table 1).

In the crystal, a network of hydrogen bonds (Table 2) link the component species into chains (Fig. 2) The adjacent chains are cross-linked by π–π stacking interactions involving the two benzimidazole rings, with a centroid···centroid distance of 3.785 (3) Å.

Related literature top

For background, see: Zhao et al. (2006).

Experimental top

To a solution of o-phenylenediamine (0.216 g, 2 mmol) in methanol (5 ml), o-vanillin (0.615 g, 4 mmol) was added. The mixture was refluxed for 1 h, then a solution of cupric chloride dihydrate (0.3408 g, 2 mmol) was added dropwise and the mixture stirred for another 3 h. Red blocks of (I) were grown by slow evaporation of the solvent after about two weeks.

Refinement top

All H atoms were placed in geometrically idealized positions (N—H = 0.86 Å, O—H = 0.82 Å, C—H = 0.93–0.96 Å) and refined as riding with Uiso(H) = 1.5Ueq(Cmethyl, O) or 1.2Ueq(C).

Computing details top

Data collection: SMART (Siemens, 1996); cell refinement: SAINT (Siemens, 1996); data reduction: SAINT (Siemens, 1996); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997a); molecular graphics: SHELXTL (Sheldrick, 1997b); software used to prepare material for publication: SHELXTL (Sheldrick, 1997b).

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing 50% probability displacement ellipsoids for the non-hydrogen atoms. Symmetry code: (i) 1 - x, y, 1/2 - z.
[Figure 2] Fig. 2. View of a hydrogen-bonded (dashed lines) chain in (I).
Bis[2-(2-hydroxy-3-methoxyphenyl)benzimidazolium] tetrachloridocuprate(II) methanol disolvate top
Crystal data top
(C14H13N2O2)2[CuCl4]·2CH4OF000 = 1548
Mr = 751.95Dx = 1.487 Mg m−3
Monoclinic, C2/cMo Kα radiation
λ = 0.71073 Å
a = 17.992 (2) ÅCell parameters from 3347 reflections
b = 9.9694 (16) Åθ = 2.4–26.5º
c = 19.849 (3) ŵ = 1.02 mm−1
β = 109.406 (2)ºT = 298 (2) K
V = 3358.1 (8) Å3Block, red
Z = 40.55 × 0.32 × 0.29 mm
Data collection top
Bruker SMART CCD
diffractometer		2968 independent reflections
Radiation source: fine-focus sealed tube2273 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.036
T = 298(2) Kθmax = 25.0º
ω scansθmin = 2.2º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −17→21
Tmin = 0.605, Tmax = 0.757k = −10→11
8468 measured reflectionsl = −23→23
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.035H-atom parameters constrained
wR(F2) = 0.099  w = 1/[σ2(Fo2) + (0.0475P)2 + 3.5756P]
where P = (Fo2 + 2Fc2)/3
S = 1.00(Δ/σ)max < 0.001
2968 reflectionsΔρmax = 0.46 e Å−3
204 parametersΔρmin = −0.20 e Å−3
Primary atom site location: structure-invariant direct methodsExtinction correction: none
Crystal data top
(C14H13N2O2)2[CuCl4]·2CH4OV = 3358.1 (8) Å3
Mr = 751.95Z = 4
Monoclinic, C2/cMo Kα
a = 17.992 (2) ŵ = 1.02 mm−1
b = 9.9694 (16) ÅT = 298 (2) K
c = 19.849 (3) Å0.55 × 0.32 × 0.29 mm
β = 109.406 (2)º
Data collection top
Bruker SMART CCD
diffractometer		2968 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		2273 reflections with I > 2σ(I)
Tmin = 0.605, Tmax = 0.757Rint = 0.036
8468 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.035204 parameters
wR(F2) = 0.099H-atom parameters constrained
S = 1.00Δρmax = 0.46 e Å−3
2968 reflectionsΔρmin = −0.20 e Å−3
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
xyzUiso*/Ueq
Cl10.43726 (4)1.01765 (8)0.16383 (4)0.0528 (2)
Cu10.50000.87387 (5)0.25000.03965 (16)
Cl20.40516 (4)0.72185 (8)0.24813 (5)0.0618 (2)
N10.77757 (12)0.5015 (2)0.52156 (11)0.0393 (5)
H10.80900.52660.56260.047*
N20.67538 (14)0.4895 (3)0.42615 (12)0.0476 (6)
H20.62980.50560.39530.057*
O10.76890 (12)0.6556 (2)0.62645 (10)0.0606 (6)
H1A0.78740.70340.66170.091*
O20.70083 (13)0.8504 (2)0.67617 (11)0.0651 (6)
O30.52158 (14)0.4866 (3)0.33663 (14)0.0859 (9)
H30.49810.55430.31740.129*
C10.66881 (15)0.6608 (3)0.51403 (14)0.0414 (7)
C20.70078 (15)0.7102 (3)0.58301 (15)0.0425 (7)
C30.66309 (17)0.8123 (3)0.60765 (16)0.0463 (7)
C40.59298 (18)0.8638 (3)0.56282 (18)0.0533 (8)
H40.56650.92960.57920.064*
C50.56225 (17)0.8174 (4)0.49376 (18)0.0585 (9)
H50.51590.85490.46330.070*
C60.59831 (17)0.7175 (3)0.46896 (16)0.0524 (8)
H60.57620.68700.42230.063*
C70.6671 (2)0.9575 (4)0.7043 (2)0.0764 (11)
H7A0.65831.03340.67290.115*
H7B0.70240.98230.75060.115*
H7C0.61780.92870.70840.115*
C80.70637 (15)0.5539 (3)0.48807 (14)0.0401 (6)
C90.72747 (17)0.3928 (3)0.41891 (15)0.0459 (7)
C100.79306 (16)0.4004 (3)0.48014 (14)0.0410 (7)
C110.85731 (17)0.3171 (3)0.49069 (16)0.0489 (7)
H110.90140.32260.53170.059*
C120.85291 (19)0.2254 (3)0.43757 (18)0.0586 (8)
H120.89480.16710.44280.070*
C130.7865 (2)0.2184 (4)0.37584 (19)0.0683 (10)
H130.78580.15630.34070.082*
C140.7228 (2)0.2999 (4)0.36564 (17)0.0635 (9)
H140.67850.29350.32500.076*
C150.4684 (3)0.3940 (5)0.3439 (3)0.121 (2)
H15A0.49130.34470.38750.182*
H15B0.45470.33330.30410.182*
H15C0.42180.43930.34530.182*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0484 (4)0.0576 (5)0.0422 (4)−0.0070 (4)0.0012 (3)0.0115 (3)
Cu10.0358 (3)0.0405 (3)0.0399 (3)0.0000.00888 (19)0.000
Cl20.0404 (4)0.0512 (5)0.0950 (6)0.0002 (4)0.0239 (4)0.0185 (4)
N10.0310 (12)0.0451 (14)0.0391 (12)−0.0005 (10)0.0081 (9)−0.0017 (10)
N20.0367 (13)0.0549 (16)0.0441 (13)−0.0022 (12)0.0038 (10)0.0026 (12)
O10.0499 (12)0.0718 (16)0.0491 (11)0.0258 (11)0.0017 (9)−0.0101 (11)
O20.0655 (14)0.0698 (16)0.0587 (13)0.0287 (12)0.0189 (11)−0.0032 (12)
O30.0605 (15)0.0776 (19)0.0928 (18)−0.0156 (14)−0.0105 (13)0.0301 (15)
C10.0307 (14)0.0445 (17)0.0493 (16)0.0024 (13)0.0137 (12)0.0110 (13)
C20.0321 (14)0.0440 (17)0.0526 (16)0.0068 (13)0.0158 (12)0.0106 (14)
C30.0418 (16)0.0472 (18)0.0556 (17)0.0088 (14)0.0239 (14)0.0096 (14)
C40.0452 (17)0.050 (2)0.072 (2)0.0142 (15)0.0293 (16)0.0159 (16)
C50.0334 (15)0.064 (2)0.074 (2)0.0134 (16)0.0128 (15)0.0193 (18)
C60.0396 (16)0.059 (2)0.0531 (17)0.0054 (15)0.0085 (13)0.0098 (15)
C70.092 (3)0.072 (3)0.074 (2)0.027 (2)0.038 (2)−0.003 (2)
C80.0306 (14)0.0449 (17)0.0442 (15)−0.0038 (13)0.0114 (12)0.0079 (13)
C90.0422 (16)0.0481 (18)0.0471 (16)−0.0071 (14)0.0142 (13)0.0013 (14)
C100.0385 (15)0.0423 (17)0.0436 (15)−0.0071 (13)0.0154 (12)−0.0010 (13)
C110.0428 (16)0.0501 (19)0.0564 (17)−0.0013 (15)0.0200 (13)−0.0040 (15)
C120.057 (2)0.052 (2)0.073 (2)−0.0023 (16)0.0303 (17)−0.0101 (17)
C130.074 (2)0.066 (2)0.070 (2)−0.013 (2)0.0302 (19)−0.0246 (19)
C140.060 (2)0.074 (3)0.0518 (18)−0.0150 (19)0.0126 (16)−0.0142 (18)
C150.082 (3)0.110 (4)0.149 (4)−0.029 (3)0.009 (3)0.055 (3)
Geometric parameters (Å, °) top
Cl1—Cu12.2297 (8)C4—C51.377 (5)
Cu1—Cl1i2.2297 (8)C4—H40.9300
Cu1—Cl22.2732 (8)C5—C61.366 (4)
Cu1—Cl2i2.2732 (8)C5—H50.9300
N1—C81.338 (3)C6—H60.9300
N1—C101.386 (3)C7—H7A0.9600
N1—H10.8600C7—H7B0.9600
N2—C81.334 (4)C7—H7C0.9600
N2—C91.385 (4)C9—C101.386 (4)
N2—H20.8600C9—C141.388 (4)
O1—C21.356 (3)C10—C111.382 (4)
O1—H1A0.8200C11—C121.377 (4)
O2—C31.357 (4)C11—H110.9300
O2—C71.431 (4)C12—C131.400 (5)
O3—C151.372 (5)C12—H120.9300
O3—H30.8200C13—C141.364 (5)
C1—C21.387 (4)C13—H130.9300
C1—C61.405 (4)C14—H140.9300
C1—C81.445 (4)C15—H15A0.9600
C2—C31.398 (4)C15—H15B0.9600
C3—C41.378 (4)C15—H15C0.9600
Cl1i—Cu1—Cl199.99 (5)O2—C7—H7A109.5
Cl1i—Cu1—Cl2128.83 (3)O2—C7—H7B109.5
Cl1—Cu1—Cl2103.30 (3)H7A—C7—H7B109.5
Cl1i—Cu1—Cl2i103.30 (3)O2—C7—H7C109.5
Cl1—Cu1—Cl2i128.83 (3)H7A—C7—H7C109.5
Cl2—Cu1—Cl2i96.38 (5)H7B—C7—H7C109.5
C8—N1—C10109.7 (2)N2—C8—N1107.9 (2)
C8—N1—H1125.1N2—C8—C1125.6 (2)
C10—N1—H1125.1N1—C8—C1126.5 (2)
C8—N2—C9109.9 (2)N2—C9—C10106.2 (3)
C8—N2—H2125.0N2—C9—C14132.3 (3)
C9—N2—H2125.0C10—C9—C14121.5 (3)
C2—O1—H1A109.5C11—C10—N1132.1 (3)
C3—O2—C7117.7 (2)C11—C10—C9121.7 (3)
C15—O3—H3109.5N1—C10—C9106.2 (2)
C2—C1—C6118.4 (3)C12—C11—C10116.8 (3)
C2—C1—C8121.6 (2)C12—C11—H11121.6
C6—C1—C8120.0 (3)C10—C11—H11121.6
O1—C2—C1118.4 (2)C11—C12—C13121.2 (3)
O1—C2—C3120.7 (3)C11—C12—H12119.4
C1—C2—C3120.9 (2)C13—C12—H12119.4
O2—C3—C4126.1 (3)C14—C13—C12122.1 (3)
O2—C3—C2114.5 (2)C14—C13—H13119.0
C4—C3—C2119.4 (3)C12—C13—H13119.0
C5—C4—C3119.8 (3)C13—C14—C9116.7 (3)
C5—C4—H4120.1C13—C14—H14121.6
C3—C4—H4120.1C9—C14—H14121.6
C6—C5—C4121.5 (3)O3—C15—H15A109.5
C6—C5—H5119.3O3—C15—H15B109.5
C4—C5—H5119.3H15A—C15—H15B109.5
C5—C6—C1120.0 (3)O3—C15—H15C109.5
C5—C6—H6120.0H15A—C15—H15C109.5
C1—C6—H6120.0H15B—C15—H15C109.5
Symmetry codes: (i) −x+1, y, −z+1/2.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.862.092.634 (3)120
N2—H2···O30.861.922.747 (3)162
O3—H3···Cl20.822.443.245 (3)168
N1—H1···Cl1ii0.862.553.298 (2)147
O1—H1A···Cl2ii0.822.363.066 (2)145
Symmetry codes: (ii) x+1/2, −y+3/2, z+1/2.
Table 1
Selected geometric parameters (Å, °) top
Cl1—Cu12.2297 (8)Cu1—Cl22.2732 (8)
Cl1i—Cu1—Cl199.99 (5)Cl1—Cu1—Cl2103.30 (3)
Cl1i—Cu1—Cl2128.83 (3)Cl2—Cu1—Cl2i96.38 (5)
Symmetry codes: (i) −x+1, y, −z+1/2.
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.862.092.634 (3)120
N2—H2···O30.861.922.747 (3)162
O3—H3···Cl20.822.443.245 (3)168
N1—H1···Cl1ii0.862.553.298 (2)147
O1—H1A···Cl2ii0.822.363.066 (2)145
Symmetry codes: (ii) x+1/2, −y+3/2, z+1/2.
Acknowledgements top

The authors acknowledge the financial support of the Shandong Province Science Foundation and the State Key Laboratory of Crystalline Materials, Shandong University, People's Republic of China.

references
References top

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (1997a). SHELXS97 and SHELXL97. University of Göttingen, Germany.

Sheldrick, G. M. (1997b). SHELXTL. Version 5.1. Bruker AXS Inc., Madison, Wisconsin, USA.

Siemens (1996). SMART and SAINT. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA

Zhao, Y.-H., Su, Z.-M., Wang, Y., Hao, X.-R. & Shao, K.-Z. (2006). Acta Cryst. E62, m2361–m2362.