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metal-organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 12| December 2010| Page m1582
https://doi.org/10.1107/S1600536810046040

Bis[μ-3-(1H-benzimidazol-2-yl)benzoato]dicopper(I)

Ke-Wei Lei,a* Dong-Guo Xia,a Jie Lia and Zheng-Yu Sua

aState Key Laboratory Base of Novel Functional Materials and Preparation Science, Institute of Solid Materials Chemistry, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo 315211, People's Republic of China
*Correspondence e-mail: leikeweipublic@hotmail.com

(Received 19 September 2010; accepted 8 November 2010; online 17 November 2010)

The dimeric title complex, [Cu2(C14H9N2O2)2], resides on a center of symmetry. In the crystal, the mol­ecules are packed via π–π stacking inter­actions alternating between imidazole and benzene rings [mean inter­planar distances = 3.754 (3) and 3.624 (3) Å]. An inter­molecular N—H⋯O hydrogen bond links the dimers together. The two-coordinate CuI atom displays an O—Cu—N bond angle of 176.3 (2)°. The Cu⋯Cu distance within the dimer is 5.100 (2) Å.

Related literature

For background to complexes of benzimidazole with copper(I), see: Ruettimann et al. (1992[Ruettimann, S., Piguet, C., Bernardinelli, G., Bocquet, B. & Williams, A. F. (1992). J. Am. Chem. Soc. 114, 4230-4237.]).

[Scheme 1]

Experimental

Crystal data

  • [Cu2(C14H9N2O2)2]

  • Mr = 601.54

  • Monoclinic, P 21 /c

  • a = 4.875 (2) Å

  • b = 13.417 (7) Å

  • c = 18.130 (9) Å

  • β = 103.643 (12)°

  • V = 1152.4 (10) Å3

  • Z = 2

  • Mo Kα radiation

  • μ = 1.89 mm−1

  • T = 296 K

  • 0.52 × 0.44 × 0.40 mm
Data collection

  • Bruker SMART APEXII diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 2000[Sheldrick, G. M. (2000). SADABS. University of Göttingen, Germany.]) Tmin = 0.387, Tmax = 0.473

  • 7794 measured reflections

  • 2013 independent reflections

  • 1083 reflections with I > 2σ(I)

  • Rint = 0.107
Refinement

  • R[F2 > 2σ(F2)] = 0.056

  • wR(F2) = 0.148

  • S = 1.01

  • 2013 reflections

  • 172 parameters

  • H-atom parameters constrained

  • Δρmax = 0.69 e Å−3

  • Δρmin = −0.62 e Å−3

Table 1
Selected geometric parameters (Å, °)

Cu1—O2 1.823 (5)
Cu1—N2i  
O2—Cu1—N2i 176.3 (2)
Symmetry code: (i) -x+1, -y+1, -z+1.

Table 2
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A D⋯A D—H⋯A
N1—H1⋯O1ii 0.86 1.95 2.783 (7) 164
Symmetry code: (ii) [-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: APEX2 (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2007[Bruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810046040/om2365sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810046040/om2365Isup2.hkl

checkCIF report


Comment top

The title complex, [Cu(C14H9N2O2)]2, is a dimer and resides on a center of symmetry. The molecular structure is illustrated in Fig. 1. Due to the low coordination number of two for copper(I), the Cu(I)–N and Cu(I)–O bond lengths are somewhat shorter than typical values (Ruettimann et al., 1992).

The dihedral angle between the two planes of C1–C6 and C8–C13 benzene rings is 4.37 (3)°. In the title molecule there is an intermolecular hydrogen bond between N1 and O1 of an adjacent dimer (Table 2 and Fig. 2). The mean interplanar distance of 3.754 (3)Å and 3.624 (3)Å alternately between imidazole and benzene rings suggests that the ligands are engaged in π-π stacking interactions with an offset face-to-face style.

Related literature top

For background to complexes of benzimidazole with copper(I), see: Ruettimann et al. (1992).

Experimental top

Under microwave irradiation, 3-(1H-benzo[d]imidazol-2-yl) benzoic acid was synthesized by condensation of benzene-1,2-diamine and isophthalic acid(1:1) in polyphosphoric acid. The reaction time was 12 min. The yield was 74%. Then recrystallization from methanol gave pure chemical compound. A mixture of 3-(1H-benzo[d]imidazol-2-yl)benzoic acid (0.0476 g,0.2 mmol),Cu(NO3)2.3H2O (0.121 g, 0.5 mmol) and and water (l2 ml) was placed in a Teflon-lined stainless steel vessel (25 ml) and heated at 170 °C for 72 h, and then cooled to room temperature at a rate of 0.1 °C/min. The resulting brown single crystals were isolated by washing with DMF/methanol, and dried in vacuo. It can be seen from the crystal color that the Cu2+ ion was reduced from +2 to +1 oxidation state. The yield was about 37 mg (62 %). Calcd.for C28H18Cu2N4O4: C, 55.86; H, 2.99; N, 9.31; Found: C, 55.92;H, 2.93;N, 9.24%.

Refinement top

All H atoms were placed in geometrically idealized positions and treated as riding on their parent atoms, with C—H = 0.93–0.96 Å, and with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms.

Structure description top

The title complex, [Cu(C14H9N2O2)]2, is a dimer and resides on a center of symmetry. The molecular structure is illustrated in Fig. 1. Due to the low coordination number of two for copper(I), the Cu(I)–N and Cu(I)–O bond lengths are somewhat shorter than typical values (Ruettimann et al., 1992).

The dihedral angle between the two planes of C1–C6 and C8–C13 benzene rings is 4.37 (3)°. In the title molecule there is an intermolecular hydrogen bond between N1 and O1 of an adjacent dimer (Table 2 and Fig. 2). The mean interplanar distance of 3.754 (3)Å and 3.624 (3)Å alternately between imidazole and benzene rings suggests that the ligands are engaged in π-π stacking interactions with an offset face-to-face style.

For background to complexes of benzimidazole with copper(I), see: Ruettimann et al. (1992).

Computing details top

Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); 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: SHELXL97 (Sheldrick, 2008).

Figures top
[Figure 1] Fig. 1. The structure of the title compound, showing 30% probability displacement ellipsoids and the atom-numbering scheme.
[Figure 2] Fig. 2. Packing diagram of the title compound.
Bis[µ-3-(1H-benzimidazol-2-yl)benzoato]dicopper(I) top
Crystal data top
[Cu2(C14H9N2O2)2]F(000) = 608
Mr = 601.54Dx = 1.734 Mg m−3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 1146 reflections
a = 4.875 (2) Åθ = 2.3–21.7°
b = 13.417 (7) ŵ = 1.89 mm−1
c = 18.130 (9) ÅT = 296 K
β = 103.643 (12)°Block, brown
V = 1152.4 (10) Å30.52 × 0.44 × 0.40 mm
Z = 2
Data collection top
Bruker SMART APEXII
diffractometer		2013 independent reflections
Radiation source: fine-focus sealed tube1083 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.107
φ and ω scansθmax = 25.0°, θmin = 2.3°
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		h = −5→4
Tmin = 0.387, Tmax = 0.473k = −15→15
7794 measured reflectionsl = −21→21
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.056Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.148H-atom parameters constrained
S = 1.01 w = 1/[σ2(Fo2) + (0.0617P)2 + 0.5546P]
where P = (Fo2 + 2Fc2)/3
2013 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.69 e Å−3
0 restraintsΔρmin = −0.62 e Å−3
Crystal data top
[Cu2(C14H9N2O2)2]V = 1152.4 (10) Å3
Mr = 601.54Z = 2
Monoclinic, P21/cMo Kα radiation
a = 4.875 (2) ŵ = 1.89 mm−1
b = 13.417 (7) ÅT = 296 K
c = 18.130 (9) Å0.52 × 0.44 × 0.40 mm
β = 103.643 (12)°
Data collection top
Bruker SMART APEXII
diffractometer		2013 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 2000)		1083 reflections with I > 2σ(I)
Tmin = 0.387, Tmax = 0.473Rint = 0.107
7794 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0560 restraints
wR(F2) = 0.148H-atom parameters constrained
S = 1.01Δρmax = 0.69 e Å−3
2013 reflectionsΔρmin = −0.62 e Å−3
172 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
xyzUiso*/Ueq
Cu10.09380 (19)0.62278 (7)0.49047 (4)0.0455 (3)
O10.0431 (11)0.6329 (4)0.3136 (3)0.0546 (13)
O20.2212 (11)0.5488 (4)0.4211 (2)0.0528 (14)
N11.0395 (10)0.2257 (4)0.3273 (3)0.0336 (13)
H10.99890.20780.28040.040*
N21.0206 (11)0.3061 (4)0.4335 (3)0.0340 (13)
C11.4326 (14)0.2163 (5)0.5182 (4)0.0433 (18)
H1A1.42750.24970.56280.052*
C21.6298 (14)0.1429 (6)0.5170 (4)0.051 (2)
H21.75830.12630.56200.061*
C31.6418 (15)0.0926 (5)0.4499 (5)0.053 (2)
H31.77860.04380.45160.064*
C41.4583 (14)0.1134 (5)0.3825 (4)0.0433 (18)
H41.46640.08010.33810.052*
C51.2557 (13)0.1879 (5)0.3836 (4)0.0363 (16)
C61.2412 (13)0.2388 (5)0.4501 (4)0.0343 (16)
C70.9009 (13)0.2964 (5)0.3587 (3)0.0339 (16)
C80.6567 (13)0.3523 (4)0.3147 (3)0.0317 (16)
C90.5412 (14)0.3314 (5)0.2385 (4)0.0407 (17)
H90.61920.28120.21450.049*
C100.3124 (14)0.3844 (5)0.1981 (4)0.0472 (19)
H100.23450.36890.14750.057*
C110.1979 (14)0.4609 (5)0.2330 (4)0.0419 (18)
H110.04680.49780.20530.050*
C120.3074 (13)0.4824 (4)0.3086 (3)0.0311 (15)
C130.5339 (13)0.4285 (5)0.3486 (4)0.0347 (16)
H130.60730.44320.39960.042*
C140.1782 (14)0.5627 (5)0.3490 (4)0.0378 (17)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cu10.0639 (6)0.0446 (6)0.0288 (5)0.0096 (5)0.0128 (4)−0.0037 (4)
O10.075 (4)0.049 (3)0.042 (3)0.021 (3)0.018 (3)0.008 (2)
O20.083 (4)0.050 (3)0.026 (3)0.022 (3)0.014 (2)0.002 (2)
N10.035 (3)0.036 (3)0.031 (3)0.002 (3)0.009 (3)−0.002 (3)
N20.045 (3)0.032 (3)0.027 (3)0.000 (3)0.012 (3)0.000 (2)
C10.050 (4)0.042 (4)0.039 (4)−0.008 (4)0.012 (3)0.005 (3)
C20.039 (4)0.053 (5)0.054 (5)−0.005 (4)−0.002 (4)0.017 (4)
C30.046 (5)0.039 (5)0.077 (6)0.009 (4)0.019 (4)0.008 (4)
C40.048 (4)0.038 (4)0.047 (4)−0.002 (4)0.018 (3)−0.001 (4)
C50.034 (4)0.035 (4)0.043 (4)−0.002 (3)0.018 (3)0.004 (3)
C60.032 (4)0.040 (4)0.031 (4)0.003 (3)0.009 (3)0.003 (3)
C70.039 (4)0.033 (4)0.031 (4)−0.007 (3)0.012 (3)0.005 (3)
C80.035 (4)0.029 (4)0.032 (4)−0.003 (3)0.012 (3)0.004 (3)
C90.046 (4)0.046 (4)0.031 (4)0.006 (4)0.009 (3)−0.009 (3)
C100.054 (5)0.060 (5)0.026 (4)0.006 (4)0.009 (3)−0.013 (4)
C110.045 (4)0.048 (5)0.032 (4)0.002 (4)0.009 (3)0.003 (3)
C120.039 (4)0.031 (4)0.026 (3)0.001 (3)0.013 (3)−0.001 (3)
C130.044 (4)0.031 (4)0.029 (4)−0.002 (3)0.010 (3)−0.004 (3)
C140.048 (4)0.036 (4)0.031 (4)−0.001 (4)0.011 (3)0.001 (3)
Geometric parameters (Å, º) top
Cu1—O21.823 (5)C3—H30.9300
Cu1—N2i1.867 (5)C4—C51.408 (9)
O1—C141.239 (8)C4—H40.9300
O2—C141.287 (7)C5—C61.402 (9)
N1—C71.366 (8)C7—C81.472 (8)
N1—C51.379 (8)C8—C91.393 (9)
N1—H10.8600C8—C131.399 (9)
N2—C71.349 (8)C9—C101.378 (9)
N2—C61.382 (8)C9—H90.9300
N2—Cu1i1.867 (5)C10—C111.391 (9)
C1—C21.380 (9)C10—H100.9300
C1—C61.394 (9)C11—C121.378 (8)
C1—H1A0.9300C11—H110.9300
C2—C31.405 (11)C12—C131.375 (8)
C2—H20.9300C12—C141.520 (9)
C3—C41.363 (10)C13—H130.9300
O2—Cu1—N2i176.3 (2)C1—C6—C5119.8 (6)
C14—O2—Cu1128.4 (4)N2—C7—N1110.3 (5)
C7—N1—C5108.3 (5)N2—C7—C8126.8 (6)
C7—N1—H1125.9N1—C7—C8122.9 (5)
C5—N1—H1125.9C9—C8—C13117.9 (6)
C7—N2—C6106.6 (5)C9—C8—C7121.5 (6)
C7—N2—Cu1i131.1 (5)C13—C8—C7120.6 (6)
C6—N2—Cu1i121.7 (4)C10—C9—C8120.7 (6)
C2—C1—C6117.7 (7)C10—C9—H9119.7
C2—C1—H1A121.2C8—C9—H9119.7
C6—C1—H1A121.2C9—C10—C11120.1 (6)
C1—C2—C3121.8 (7)C9—C10—H10120.0
C1—C2—H2119.1C11—C10—H10120.0
C3—C2—H2119.1C12—C11—C10120.2 (6)
C4—C3—C2121.7 (7)C12—C11—H11119.9
C4—C3—H3119.1C10—C11—H11119.9
C2—C3—H3119.1C13—C12—C11119.3 (6)
C3—C4—C5116.6 (7)C13—C12—C14119.4 (5)
C3—C4—H4121.7C11—C12—C14121.3 (6)
C5—C4—H4121.7C12—C13—C8121.8 (6)
N1—C5—C6105.8 (6)C12—C13—H13119.1
N1—C5—C4131.8 (6)C8—C13—H13119.1
C6—C5—C4122.4 (6)O1—C14—O2125.2 (6)
N2—C6—C1131.2 (6)O1—C14—C12121.2 (6)
N2—C6—C5109.0 (5)O2—C14—C12113.6 (6)
N2i—Cu1—O2—C14−169 (3)C5—N1—C7—N20.2 (7)
C6—C1—C2—C30.6 (10)C5—N1—C7—C8−179.8 (5)
C1—C2—C3—C4−0.3 (11)N2—C7—C8—C9−176.0 (6)
C2—C3—C4—C5−0.1 (10)N1—C7—C8—C94.1 (9)
C7—N1—C5—C60.0 (7)N2—C7—C8—C134.1 (10)
C7—N1—C5—C4179.0 (7)N1—C7—C8—C13−175.8 (6)
C3—C4—C5—N1−178.7 (7)C13—C8—C9—C10−0.2 (10)
C3—C4—C5—C60.1 (10)C7—C8—C9—C10180.0 (6)
C7—N2—C6—C1−179.1 (7)C8—C9—C10—C111.3 (11)
Cu1i—N2—C6—C1−6.9 (10)C9—C10—C11—C12−1.8 (10)
C7—N2—C6—C50.4 (7)C10—C11—C12—C131.1 (10)
Cu1i—N2—C6—C5172.5 (4)C10—C11—C12—C14−177.3 (6)
C2—C1—C6—N2178.8 (6)C11—C12—C13—C80.0 (10)
C2—C1—C6—C5−0.6 (10)C14—C12—C13—C8178.5 (6)
N1—C5—C6—N2−0.2 (7)C9—C8—C13—C12−0.5 (9)
C4—C5—C6—N2−179.3 (5)C7—C8—C13—C12179.4 (6)
N1—C5—C6—C1179.3 (6)Cu1—O2—C14—O11.9 (11)
C4—C5—C6—C10.2 (10)Cu1—O2—C14—C12−177.3 (4)
C6—N2—C7—N1−0.4 (7)C13—C12—C14—O1156.2 (6)
Cu1i—N2—C7—N1−171.5 (4)C11—C12—C14—O1−25.4 (10)
C6—N2—C7—C8179.7 (6)C13—C12—C14—O2−24.5 (9)
Cu1i—N2—C7—C88.6 (10)C11—C12—C14—O2153.9 (7)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1ii0.861.952.783 (7)164
Symmetry code: (ii) −x+1, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula[Cu2(C14H9N2O2)2]
Mr601.54
Crystal system, space groupMonoclinic, P21/c
Temperature (K)296
a, b, c (Å)4.875 (2), 13.417 (7), 18.130 (9)
β (°) 103.643 (12)
V (Å3)1152.4 (10)
Z2
Radiation typeMo Kα
µ (mm−1)1.89
Crystal size (mm)0.52 × 0.44 × 0.40
Data collection
DiffractometerBruker SMART APEXII
Absorption correctionMulti-scan
(SADABS; Sheldrick, 2000)
Tmin, Tmax0.387, 0.473
No. of measured, independent and
observed [I > 2σ(I)] reflections		7794, 2013, 1083
Rint0.107
(sin θ/λ)max (Å−1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.056, 0.148, 1.01
No. of reflections2013
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å−3)0.69, −0.62

Computer programs: APEX2 (Bruker, 2007), SAINT (Bruker, 2007), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Selected geometric parameters (Å, º) top
Cu1—O21.823 (5)N1—C51.379 (8)
Cu1—N2i1.867 (5)N2—C71.349 (8)
N1—C71.366 (8)N2—C61.382 (8)
O2—Cu1—N2i176.3 (2)C14—O2—Cu1128.4 (4)
Symmetry code: (i) −x+1, −y+1, −z+1.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O1ii0.861.952.783 (7)164.0
Symmetry code: (ii) −x+1, y−1/2, −z+1/2.
 

Acknowledgements

This project was supported by the Talent Fund of Ningbo University (grant No. 2008087) and sponsored by the K. C. Wong Magna Fund of Ningbo University.

References

First citationBruker (2007). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
 First citationRuettimann, S., Piguet, C., Bernardinelli, G., Bocquet, B. & Williams, A. F. (1992). J. Am. Chem. Soc. 114, 4230–4237.  CSD CrossRef CAS Google Scholar
 First citationSheldrick, G. M. (2000). SADABS. University of Göttingen, Germany.  Google Scholar
 First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 66| Part 12| December 2010| Page m1582
https://doi.org/10.1107/S1600536810046040
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