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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.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807031455/hb2460sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807031455/hb2460Isup2.hkl
Contains datablock I

CCDC reference: 657517

Key indicators

  • Single-crystal X-ray study
  • T = 295 K
  • Mean [sigma](C-C) = 0.006 Å
  • Disorder in main residue
  • R factor = 0.032
  • wR factor = 0.087
  • Data-to-parameter ratio = 10.8

checkCIF/PLATON results

No syntax errors found



Alert level B CHEMS01_ALERT_1_B The sum formula contains elements in the wrong order. N precedes Cu Sequence must be C, H, then alphabetical. PLAT027_ALERT_3_B _diffrn_reflns_theta_full (too) Low ............ 24.99 Deg. PLAT029_ALERT_3_B _diffrn_measured_fraction_theta_full Low ....... 0.95
Alert level C PLAT041_ALERT_1_C Calc. and Rep. SumFormula Strings Differ .... ? PLAT094_ALERT_2_C Ratio of Maximum / Minimum Residual Density .... 2.11 PLAT180_ALERT_3_C Check Cell Rounding: # of Values Ending with 0 = 3 PLAT301_ALERT_3_C Main Residue Disorder ......................... 8.00 Perc. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C8 - C9 ... 1.39 Ang. PLAT366_ALERT_2_C Short? C(sp?)-C(sp?) Bond C8 - C12 ... 1.39 Ang.
Alert level G REFLT03_ALERT_1_G ALERT: Expected hkl max differ from CIF values From the CIF: _diffrn_reflns_theta_max 24.99 From the CIF: _reflns_number_total 1568 From the CIF: _diffrn_reflns_limit_ max hkl 25. 8. 4. From the CIF: _diffrn_reflns_limit_ min hkl -25. -13. -4. TEST1: Expected hkl limits for theta max Calculated maximum hkl 27. 13. 4. Calculated minimum hkl -27. -13. -4. REFLT03_ALERT_4_G Please check that the estimate of the number of Friedel pairs is correct. If it is not, please give the correct count in the _publ_section_exptl_refinement section of the submitted CIF. From the CIF: _diffrn_reflns_theta_max 24.99 From the CIF: _reflns_number_total 1568 Count of symmetry unique reflns 993 Completeness (_total/calc) 157.91% TEST3: Check Friedels for noncentro structure Estimate of Friedel pairs measured 575 Fraction of Friedel pairs measured 0.579 Are heavy atom types Z>Si present yes PLAT860_ALERT_3_G Note: Number of Least-Squares Restraints ....... 1
0 ALERT level A = In general: serious problem 3 ALERT level B = Potentially serious problem 6 ALERT level C = Check and explain 3 ALERT level G = General alerts; check 3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 3 ALERT type 2 Indicator that the structure model may be wrong or deficient 5 ALERT type 3 Indicator that the structure quality may be low 1 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

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)].

Structure description 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.

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).

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 m3
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 mm1
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)
Graphite monochromatorRint = 0.020
φ and ω scansθmax = 25.0°, θmin = 2.1°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 2525
Tmin = 0.623, Tmax = 0.791k = 138
3566 measured reflectionsl = 44
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 Å3
145 parametersΔρmin = 0.23 e Å3
1 restraintAbsolute structure: Flack (1983), 620 Friedel pairs
Primary atom site location: structure-invariant direct methodsAbsolute structure 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 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.032H-atom parameters constrained
wR(F2) = 0.087Δρmax = 0.48 e Å3
S = 1.05Δρmin = 0.23 e Å3
1568 reflectionsAbsolute structure: Flack (1983), 620 Friedel pairs
145 parametersAbsolute structure 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, º) 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—C2178.5 (5)Cu1ii—N2—C7—N1178.8 (3)
Cu1—N1—C1—C20.7 (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—N20.9 (5)
N1—C1—C2—C3179.7 (5)Cu1—N1—C7—N2178.6 (3)
C6—C1—C2—C31.1 (6)C1—N1—C7—C8180.0 (4)
C1—C2—C3—C40.2 (7)Cu1—N1—C7—C82.4 (6)
C2—C3—C4—C50.3 (7)N2—C7—C8—C12137.8 (4)
C3—C4—C5—C61.2 (6)N1—C7—C8—C1241.1 (6)
C4—C5—C6—N2179.2 (4)N2—C7—C8—C942.1 (6)
C4—C5—C6—C12.0 (6)N1—C7—C8—C9138.9 (4)
C7—N2—C6—C5179.0 (4)C10—N3—C9—C81.0 (8)
Cu1ii—N2—C6—C50.5 (6)C12—C8—C9—N31.7 (7)
C7—N2—C6—C10.1 (4)C7—C8—C9—N3178.2 (4)
Cu1ii—N2—C6—C1179.4 (3)C9—N3—C10—C110.3 (8)
C2—C1—C6—C52.0 (6)N3—C10—C11—C120.2 (8)
N1—C1—C6—C5178.6 (4)C10—C11—C12—C80.9 (7)
C2—C1—C6—N2178.9 (4)C9—C8—C12—C111.6 (7)
N1—C1—C6—N20.4 (4)C7—C8—C12—C11178.4 (4)
C6—N2—C7—N10.7 (5)
Symmetry codes: (i) x+3/2, y1/2, z+1/2; (ii) x+3/2, y+1/2, z1/2.

Experimental details

Crystal data
Chemical formula[Cu(C12H8N3)]
Mr257.75
Crystal system, space groupOrthorhombic, Pna21
Temperature (K)295
a, b, c (Å)22.940 (3), 11.055 (1), 3.8050 (4)
V3)964.91 (18)
Z4
Radiation typeMo Kα
µ (mm1)2.23
Crystal size (mm)0.20 × 0.15 × 0.11
Data collection
DiffractometerBruker APEX CCD
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.623, 0.791
No. of measured, independent and
observed [I > 2σ(I)] reflections
3566, 1568, 1306
Rint0.020
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.087, 1.05
No. of reflections1568
No. of parameters145
No. of restraints1
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.48, 0.23
Absolute structureFlack (1983), 620 Friedel pairs
Absolute structure parameter0.04 (4)

Computer programs: SMART (or APEX2?) (Bruker, 2002), SAINT (Bruker, 2002), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), X-SEED (Barbour, 2001), publCIF (Westrip, 2007).

Selected geometric parameters (Å, º) top
Cu1—N11.866 (3)Cu1—N2i1.866 (3)
N1—Cu1—N2i179.78 (16)
Symmetry code: (i) x+3/2, y1/2, z+1/2.
 

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