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Acta Cryst. (2007). E63, m2041    [ doi:10.1107/S1600536807031455 ]

catena-Poly[copper(I)-[mu]-[2-(3-pyridyl)benzimidazolato-[kappa]2N:N']]

X.-C. Huang, W. Luo, Y.-F. Shen and S. W. Ng

Abstract top

The Cu atom in the title compound, [Cu(C12H8N3)]n, is linked to adjacent benzimidazolate N atoms in an almost linear CuN2 geometry. The ligands link the Cu atoms into an infinite chain. The N atom and a C-H group of the pendant pyridine ring are disordered equally over two sites.

Comment top

Imidazolates function as monoanionc µ2-bridging ligands to copper(I) and silver(I), and the resulting compounds are single molecules or linear chains (Huang et al., 2006). The copper derivatives exhibit more complicated structures, and this is brought about by a choice of reaction conditions. Copper compounds with a polygon motif (Huang, Zhang & Chen, 2004) as well as with triple helical chain motifs (Huang et al., 2005) have been synthesized. The title compound is a pyridyl-substituted imidazolate; however, the pyridyl ring does not participate in bonding, so that the copper atom is linked only to the nitrogen atoms of two benzimidazolate anions in a linear geometry.

Related literature top

For the structures of some copper(I) imidazolates, see Huang, Zhang & Chen (2004); Huang et al. (2005, 2006). For the synthesis of the ligand, see Huang, Zeng & Ng (2004).

Experimental top

2-(3-Pyridyl)-1H-benzimidazole was synthesized using a reported procedure (Huang, Zeng & Ng, 2004). A mixture of Cu2(OH)2CO3 (0.110 g, 0.5 mmol), 2-(3-pyridyl)-1H-benzimidazole (0.195 g, 1.0 mmol), aqueous ammonia (25%, 5 ml) and methanol (2 ml) was placed in a 15-ml Teflon-lined bomb. The bomb was heated at 433 K for 80 h and then cooled to room temperature at a rate of 5 K h-1. Pale-yellow needles of (I) were obtained in about 60% yield (based on the ligand). CH&N elemental analysis (calc/found) for C12H8CuN3: C 56.03 (56.09), H 3.14(3.21), N 16.35% (16.28%).

Refinement top

The pyridyl ring is disordered in the atoms at the meta-positions. These were refined as a 50:50 mixture of carbon and nitrogen. The pair of C/N atoms were restrained to the same site and also to have the same Uij values. Hydrogen atoms were placed at calculated positions in the riding model approximation [C—H = 0.93 Å, U(H) = 1.2Ueq(C)].

Computing details top

Data collection: SMART (or APEX2?) (Bruker, 2002); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: X-SEED (Barbour, 2001); software used to prepare material for publication: publCIF (Westrip, 2007).

Figures top
[Figure 1] Fig. 1. View of a fragment of the chain motif in (I) showing 50% displacement ellipsoids for the non-hydrogen atoms. [Symmetry code (i): 3/2 + x, -1/2 -, z]
catena-Poly[copper(I)-µ-[2-(3-pyridyl)benzimidazolato- κ2N:N']] top
Crystal data top
[Cu(C12H8N3)]F(000) = 520
Mr = 257.75Dx = 1.774 Mg m−3
Orthorhombic, Pna21Mo Kα radiation, λ = 0.71073 Å
Hall symbol: P 2c -2nCell parameters from 1264 reflections
a = 22.940 (3) Åθ = 3.2–27.9°
b = 11.055 (1) ŵ = 2.23 mm−1
c = 3.8050 (4) ÅT = 295 K
V = 964.91 (18) Å3Rod, light yellow
Z = 40.20 × 0.15 × 0.11 mm
Data collection top
Bruker APEX CCD
diffractometer		1568 independent reflections
Radiation source: fine-focus sealed tube1306 reflections with I > 2σ(I)
graphiteRint = 0.020
φ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −25→25
Tmin = 0.623, Tmax = 0.791k = −13→8
3566 measured reflectionsl = −4→4
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)] = 0.032H-atom parameters constrained
wR(F2) = 0.087 w = 1/[σ2(Fo2) + (0.0531P)2]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max = 0.001
1568 reflectionsΔρmax = 0.48 e Å−3
145 parametersΔρmin = −0.23 e Å−3
1 restraintAbsolute structure: Flack (1983), 620 Friedel pairs
Primary atom site location: structure-invariant direct methodsFlack parameter: 0.04 (4)
Crystal data top
[Cu(C12H8N3)]V = 964.91 (18) Å3
Mr = 257.75Z = 4
Orthorhombic, Pna21Mo Kα radiation
a = 22.940 (3) ŵ = 2.23 mm−1
b = 11.055 (1) ÅT = 295 K
c = 3.8050 (4) Å0.20 × 0.15 × 0.11 mm
Data collection top
Bruker APEX CCD
diffractometer		1568 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1306 reflections with I > 2σ(I)
Tmin = 0.623, Tmax = 0.791Rint = 0.020
3566 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.087Δρmax = 0.48 e Å−3
S = 1.05Δρmin = −0.23 e Å−3
1568 reflectionsAbsolute structure: Flack (1983), 620 Friedel pairs
145 parametersFlack parameter: 0.04 (4)
1 restraint
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/UeqOcc. (<1)
Cu10.74935 (2)0.65062 (4)0.5000 (4)0.02952 (18)
N10.72737 (15)0.8039 (3)0.3434 (9)0.0286 (8)
N20.72837 (15)0.9975 (3)0.1567 (9)0.0261 (8)
N30.91461 (16)1.0027 (4)0.3531 (12)0.0364 (10)0.50
C3'0.91461 (16)1.0027 (4)0.3531 (12)0.0364 (10)0.50
H3'0.93451.07070.43260.044*0.50
C10.67013 (19)0.8423 (3)0.3150 (12)0.0289 (10)
C20.61824 (18)0.7842 (3)0.3838 (12)0.0345 (11)
H20.61770.70490.46560.041*
C30.5674 (2)0.8463 (4)0.3283 (15)0.0393 (12)
H30.53190.80840.37250.047*
C40.5677 (2)0.9649 (4)0.2074 (12)0.0369 (11)
H40.53251.00500.17320.044*
C50.61899 (19)1.0236 (4)0.1378 (11)0.0343 (10)
H50.61911.10250.05290.041*
C60.67062 (17)0.9626 (3)0.1972 (10)0.0259 (9)
C70.76014 (16)0.9008 (4)0.2484 (11)0.0259 (9)
C80.82406 (17)0.8993 (4)0.2412 (10)0.0274 (9)
C90.85672 (19)0.9970 (4)0.3604 (12)0.0371 (11)
H90.83671.06300.45180.045*
C100.9427 (2)0.9072 (4)0.2275 (14)0.0462 (12)
H100.98320.90920.22090.055*
C110.91465 (19)0.8052 (4)0.1062 (11)0.0478 (12)0.50
H110.93600.74020.01930.057*0.50
N11'0.91465 (19)0.8052 (4)0.1062 (11)0.0478 (12)0.50
C120.85523 (18)0.8008 (4)0.1152 (10)0.0328 (11)
H120.83570.73210.03730.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0323 (3)0.0143 (3)0.0419 (3)−0.00030 (17)−0.00202 (19)0.0096 (3)
N10.033 (2)0.0187 (18)0.0344 (18)0.0014 (16)0.0004 (17)0.0056 (17)
N20.0297 (19)0.0132 (17)0.0353 (16)0.0004 (15)−0.0029 (17)0.0038 (16)
N30.024 (2)0.025 (2)0.060 (3)−0.0050 (17)−0.008 (2)−0.002 (2)
C3'0.024 (2)0.025 (2)0.060 (3)−0.0050 (17)−0.008 (2)−0.002 (2)
C10.039 (3)0.018 (2)0.030 (2)0.0008 (17)0.000 (2)0.0029 (19)
C20.035 (3)0.019 (2)0.049 (3)−0.0057 (18)0.000 (2)0.0043 (18)
C30.033 (3)0.036 (3)0.048 (3)−0.012 (2)−0.006 (2)0.006 (2)
C40.034 (3)0.033 (3)0.044 (3)0.005 (2)−0.004 (2)−0.001 (2)
C50.044 (3)0.020 (2)0.039 (2)0.004 (2)−0.002 (2)0.0056 (18)
C60.033 (3)0.017 (2)0.028 (2)0.0013 (17)0.001 (2)0.0042 (18)
C70.034 (3)0.015 (2)0.0283 (17)−0.0012 (17)−0.001 (2)0.0076 (16)
C80.034 (3)0.020 (2)0.0291 (19)−0.0012 (19)0.002 (2)0.0063 (16)
C90.045 (3)0.021 (2)0.046 (2)0.001 (2)−0.002 (2)0.003 (2)
C100.032 (3)0.046 (3)0.061 (3)−0.008 (2)−0.005 (3)0.012 (3)
C110.050 (3)0.038 (2)0.055 (3)0.005 (2)0.000 (2)0.005 (2)
N11'0.050 (3)0.038 (2)0.055 (3)0.005 (2)0.000 (2)0.005 (2)
C120.028 (3)0.026 (2)0.044 (3)−0.0018 (18)−0.001 (2)0.0018 (19)
Geometric parameters (Å, °) top
Cu1—N11.866 (3)C3—H30.9300
Cu1—N2i1.866 (3)C4—C51.370 (5)
N1—C71.357 (6)C4—H40.9300
N1—C11.384 (5)C5—C61.382 (5)
N2—C71.340 (5)C5—H50.9300
N2—C61.388 (5)C7—C81.467 (5)
N2—Cu1ii1.866 (3)C8—C121.389 (6)
N3—C101.326 (6)C8—C91.390 (5)
N3—C91.330 (5)C9—H90.9300
C1—C21.378 (5)C10—C111.378 (6)
C1—C61.404 (4)C10—H100.9300
C2—C31.371 (6)C11—C121.364 (6)
C2—H20.9300C11—H110.9300
C3—C41.389 (5)C12—H120.9300
N1—Cu1—N2i179.78 (16)C6—C5—H5120.9
C7—N1—C1105.3 (3)C5—C6—N2131.6 (4)
C7—N1—Cu1130.7 (3)C5—C6—C1120.5 (4)
C1—N1—Cu1124.0 (3)N2—C6—C1107.8 (4)
C7—N2—C6105.6 (3)N2—C7—N1113.4 (4)
C7—N2—Cu1ii131.1 (3)N2—C7—C8123.2 (4)
C6—N2—Cu1ii123.3 (3)N1—C7—C8123.4 (4)
C10—N3—C9117.1 (4)C12—C8—C9116.4 (4)
C2—C1—N1131.5 (4)C12—C8—C7122.0 (4)
C2—C1—C6120.6 (4)C9—C8—C7121.6 (4)
N1—C1—C6107.9 (4)N3—C9—C8124.6 (4)
C3—C2—C1118.2 (4)N3—C9—H9117.7
C3—C2—H2120.9C8—C9—H9117.7
C1—C2—H2120.9N3—C10—C11123.0 (4)
C2—C3—C4121.3 (4)N3—C10—H10118.5
C2—C3—H3119.4C11—C10—H10118.5
C4—C3—H3119.4C12—C11—C10119.2 (4)
C5—C4—C3121.1 (4)C12—C11—H11120.4
C5—C4—H4119.5C10—C11—H11120.4
C3—C4—H4119.5C11—C12—C8119.7 (4)
C4—C5—C6118.3 (4)C11—C12—H12120.2
C4—C5—H5120.9C8—C12—H12120.2
C7—N1—C1—C2−178.5 (5)Cu1ii—N2—C7—N1−178.8 (3)
Cu1—N1—C1—C2−0.7 (7)C6—N2—C7—C8179.7 (4)
C7—N1—C1—C60.8 (5)Cu1ii—N2—C7—C80.2 (6)
Cu1—N1—C1—C6178.6 (3)C1—N1—C7—N2−0.9 (5)
N1—C1—C2—C3−179.7 (5)Cu1—N1—C7—N2−178.6 (3)
C6—C1—C2—C31.1 (6)C1—N1—C7—C8−180.0 (4)
C1—C2—C3—C4−0.2 (7)Cu1—N1—C7—C82.4 (6)
C2—C3—C4—C50.3 (7)N2—C7—C8—C12−137.8 (4)
C3—C4—C5—C6−1.2 (6)N1—C7—C8—C1241.1 (6)
C4—C5—C6—N2−179.2 (4)N2—C7—C8—C942.1 (6)
C4—C5—C6—C12.0 (6)N1—C7—C8—C9−138.9 (4)
C7—N2—C6—C5−179.0 (4)C10—N3—C9—C8−1.0 (8)
Cu1ii—N2—C6—C50.5 (6)C12—C8—C9—N31.7 (7)
C7—N2—C6—C1−0.1 (4)C7—C8—C9—N3−178.2 (4)
Cu1ii—N2—C6—C1179.4 (3)C9—N3—C10—C110.3 (8)
C2—C1—C6—C5−2.0 (6)N3—C10—C11—C12−0.2 (8)
N1—C1—C6—C5178.6 (4)C10—C11—C12—C80.9 (7)
C2—C1—C6—N2178.9 (4)C9—C8—C12—C11−1.6 (7)
N1—C1—C6—N2−0.4 (4)C7—C8—C12—C11178.4 (4)
C6—N2—C7—N10.7 (5)
Symmetry codes: (i) −x+3/2, y−1/2, z+1/2; (ii) −x+3/2, y+1/2, z−1/2.
Table 1
Selected geometric parameters (Å, °) top
Cu1—N11.866 (3)Cu1—N2i1.866 (3)
N1—Cu1—N2i179.78 (16)
Symmetry codes: (i) −x+3/2, y−1/2, z+1/2.
Acknowledgements top

The authors thank the Natural Science Foundation of Guangdong Province (No. 05300884 and 06027203), Shantou University and the University of Malaya for supporting this study.

references
References top

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