organic compounds
4,4′-Bis(benzimidazol-1-yl)biphenyl
aDepartment of Chemistry, Nankai University, Tianjin 300071, People's Republic of China
*Correspondence e-mail: tlhu@nankai.edu.cn
The molecule of the title compound, C26H18N4, resides on a crystallographic inversion centre with a dihedral angle of 44.94 (5)° between the benzimidazole ring system and the benzene ring. The primary hydrogen bond is C—H⋯N and inversion-related pairs of these generate a chain of rings along the c-axis direction; π⋯π stacking involving the benzimidazole groups with interplanar separations of ca 3.4 Å complete the interactions.
Related literature
For related literature, see: Bu et al. (2007); Buchwald et al. (2001); Cristau et al. (2004); Su et al. (2003).
Experimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 1998); cell SAINT (Bruker, 1998); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.
Supporting information
https://doi.org/10.1107/S1600536807063350/gg2046sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063350/gg2046Isup2.hkl
The ligand 4,4'-di(benzimidazol-1-yl)biphenyl was prepared by a modified method (Buchwald et al., 2001; Cristau et al., 2004). A mixture of 4,4'-dibromobiphenyl (3.75 g, 12.0 mmol), benzimidazole (7.08 g, 60.0 mmol), CuI (0.47 g, 2.5 mmol), 1,10-phenanthroline (1.19 g, 6.0 mmol), and K2CO3 (13.27 g, 96.0 mmol) was suspended in DMF (120 ml) and refluxed for 4 days to afford (I) as light-yellow powder, yield: 30% (based on 4,4'-dibromobiphenyl). M.p.: 566 K. MS (ESI): m/z=387.45. Anal calcd for C26H18N4: C, 80.81%; H, 4.69%; N, 14.50%. Found: C, 80.56%; H, 4.48%; N, 14.31%. Single crystals were obtained by recrystallizing from a mixture of CHCl3 and CH3OH (1:1).
C-bound H atoms were positioned geometrically and refined in the riding-model approximation, with C—H = 0.93Å and Uiso(H) = 1.2Ueq.
In recent years, benzimidazole derivatives have been found a wide range of application in the area of coordination chemistry, because they exhibit a strong networking ability (Bu et al., 2007; Su et al., 2003). The title compound has been designed for building polymer architectures. We report here the structure and conformation, towards an understanding of the ligand coordination. As shown in Fig. 1, the title compound has trans-conformation and therefore a tendency to trans-coordination. The molecule resides on an inversion centre, and the dihedral angle between the benzimidazole ring and the phenyl ring is 40.97 (17)°. There are weak H-bonding interactions in the
of (I) (C6—H6···N1B, 3.425 (17) Å, C—H···N of 146.82 (13)°, B= x,-y + 2,z + 1/2) (Fig. 2).For related literature, see: Bu et al. (2007); Buchwald et al. (2001); Cristau et al. (2004); Su et al. (2003).
Data collection: SMART (Bruker, 1998); cell
SAINT (Bruker, 1998); data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL (Bruker, 1998).C26H18N4 | F(000) = 808 |
Mr = 386.44 | Dx = 1.378 Mg m−3 |
Monoclinic, C2/c | Melting point: 566 K |
Hall symbol: -c 2yc | Mo Kα radiation, λ = 0.71073 Å |
a = 19.628 (4) Å | Cell parameters from 2932 reflections |
b = 6.8964 (14) Å | θ = 2.6–28.7° |
c = 13.760 (3) Å | µ = 0.08 mm−1 |
β = 90.74 (3)° | T = 293 K |
V = 1862.4 (7) Å3 | Block, colorless |
Z = 4 | 0.26 × 0.22 × 0.10 mm |
Bruker SMART 1000 CCD diffractometer | 1644 independent reflections |
Radiation source: fine-focus sealed tube | 1415 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.037 |
Detector resolution: 9 pixels mm-1 | θmax = 25.0°, θmin = 3.0° |
ω scans | h = −23→23 |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | k = −8→8 |
Tmin = 0.904, Tmax = 1.000 | l = −16→16 |
9091 measured reflections |
Refinement on F2 | Secondary atom site location: difference Fourier map |
Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
R[F2 > 2σ(F2)] = 0.037 | H-atom parameters constrained |
wR(F2) = 0.103 | w = 1/[σ2(Fo2) + (0.0718P)2 + 0.0391P] where P = (Fo2 + 2Fc2)/3 |
S = 1.10 | (Δ/σ)max = 0.001 |
1644 reflections | Δρmax = 0.18 e Å−3 |
137 parameters | Δρmin = −0.17 e Å−3 |
0 restraints | Extinction correction: SHELXL, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4 |
Primary atom site location: structure-invariant direct methods | Extinction coefficient: 0.032 (4) |
C26H18N4 | V = 1862.4 (7) Å3 |
Mr = 386.44 | Z = 4 |
Monoclinic, C2/c | Mo Kα radiation |
a = 19.628 (4) Å | µ = 0.08 mm−1 |
b = 6.8964 (14) Å | T = 293 K |
c = 13.760 (3) Å | 0.26 × 0.22 × 0.10 mm |
β = 90.74 (3)° |
Bruker SMART 1000 CCD diffractometer | 1644 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 1998) | 1415 reflections with I > 2σ(I) |
Tmin = 0.904, Tmax = 1.000 | Rint = 0.037 |
9091 measured reflections |
R[F2 > 2σ(F2)] = 0.037 | 0 restraints |
wR(F2) = 0.103 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.18 e Å−3 |
1644 reflections | Δρmin = −0.17 e Å−3 |
137 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
N1 | 0.22326 (5) | 0.98108 (14) | 0.82891 (7) | 0.0259 (3) | |
N2 | 0.28767 (5) | 0.99037 (13) | 0.69471 (7) | 0.0196 (3) | |
C1 | 0.28458 (6) | 0.99959 (16) | 0.79430 (8) | 0.0233 (3) | |
H1 | 0.3229 | 1.0175 | 0.8337 | 0.028* | |
C2 | 0.18197 (6) | 0.95587 (16) | 0.74690 (8) | 0.0217 (3) | |
C3 | 0.11196 (6) | 0.91962 (17) | 0.74020 (9) | 0.0271 (3) | |
H3 | 0.0854 | 0.9134 | 0.7956 | 0.033* | |
C4 | 0.08336 (6) | 0.89337 (17) | 0.64895 (9) | 0.0289 (4) | |
H4 | 0.0369 | 0.8694 | 0.6429 | 0.035* | |
C5 | 0.12330 (6) | 0.90221 (16) | 0.56532 (9) | 0.0269 (3) | |
H5 | 0.1025 | 0.8845 | 0.5049 | 0.032* | |
C6 | 0.19250 (6) | 0.93632 (16) | 0.56982 (8) | 0.0221 (3) | |
H6 | 0.2189 | 0.9410 | 0.5142 | 0.027* | |
C7 | 0.22077 (6) | 0.96335 (15) | 0.66211 (9) | 0.0197 (3) | |
C8 | 0.34804 (6) | 0.99569 (15) | 0.63884 (8) | 0.0191 (3) | |
C9 | 0.35123 (6) | 1.10302 (16) | 0.55419 (8) | 0.0239 (3) | |
H9 | 0.3136 | 1.1741 | 0.5331 | 0.029* | |
C10 | 0.41052 (6) | 1.10460 (16) | 0.50080 (9) | 0.0234 (3) | |
H10 | 0.4118 | 1.1770 | 0.4438 | 0.028* | |
C11 | 0.46851 (6) | 1.00092 (15) | 0.52969 (8) | 0.0195 (3) | |
C12 | 0.46409 (6) | 0.89818 (18) | 0.61685 (8) | 0.0268 (3) | |
H12 | 0.5021 | 0.8305 | 0.6396 | 0.032* | |
C13 | 0.40515 (6) | 0.89417 (18) | 0.67017 (8) | 0.0256 (3) | |
H13 | 0.4037 | 0.8229 | 0.7275 | 0.031* |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0289 (6) | 0.0284 (6) | 0.0204 (6) | −0.0051 (4) | 0.0060 (5) | −0.0016 (4) |
N2 | 0.0212 (6) | 0.0207 (5) | 0.0170 (6) | −0.0025 (4) | 0.0038 (4) | −0.0006 (4) |
C1 | 0.0271 (7) | 0.0255 (6) | 0.0172 (7) | −0.0033 (5) | 0.0019 (5) | −0.0006 (5) |
C2 | 0.0255 (6) | 0.0185 (6) | 0.0211 (7) | −0.0009 (5) | 0.0058 (5) | −0.0011 (5) |
C3 | 0.0249 (7) | 0.0249 (7) | 0.0318 (8) | −0.0006 (5) | 0.0103 (5) | −0.0007 (5) |
C4 | 0.0213 (6) | 0.0244 (7) | 0.0409 (8) | −0.0001 (5) | 0.0012 (6) | 0.0000 (5) |
C5 | 0.0279 (7) | 0.0235 (7) | 0.0292 (7) | 0.0013 (5) | −0.0044 (5) | −0.0002 (5) |
C6 | 0.0267 (6) | 0.0191 (6) | 0.0206 (7) | 0.0014 (5) | 0.0015 (5) | 0.0008 (5) |
C7 | 0.0212 (6) | 0.0155 (6) | 0.0226 (7) | −0.0004 (4) | 0.0025 (5) | 0.0011 (4) |
C8 | 0.0203 (6) | 0.0191 (6) | 0.0178 (6) | −0.0045 (4) | 0.0034 (5) | −0.0033 (4) |
C9 | 0.0256 (6) | 0.0217 (7) | 0.0245 (7) | 0.0049 (5) | 0.0046 (5) | 0.0031 (5) |
C10 | 0.0298 (7) | 0.0203 (6) | 0.0203 (6) | 0.0009 (5) | 0.0059 (5) | 0.0037 (5) |
C11 | 0.0196 (7) | 0.0204 (6) | 0.0185 (7) | −0.0070 (4) | 0.0003 (5) | −0.0025 (4) |
C12 | 0.0166 (6) | 0.0412 (8) | 0.0227 (7) | −0.0021 (5) | −0.0016 (5) | 0.0071 (5) |
C13 | 0.0218 (6) | 0.0369 (7) | 0.0181 (7) | −0.0055 (5) | −0.0012 (5) | 0.0078 (5) |
C9—C8 | 1.3822 (16) | C5—C6 | 1.3790 (17) |
C9—C10 | 1.3842 (16) | C5—C4 | 1.4021 (18) |
C9—H9 | 0.9300 | C5—H5 | 0.9300 |
N2—C1 | 1.3740 (15) | C4—C3 | 1.3806 (18) |
N2—C7 | 1.3945 (15) | C4—H4 | 0.9300 |
N2—C8 | 1.4212 (15) | C13—C12 | 1.3781 (16) |
C10—C11 | 1.3974 (17) | C13—C8 | 1.3856 (17) |
C10—H10 | 0.9300 | C13—H13 | 0.9300 |
N1—C1 | 1.3063 (16) | C12—H12 | 0.9300 |
N1—C2 | 1.3916 (16) | C2—C3 | 1.3986 (17) |
C11—C12 | 1.3967 (17) | C3—H3 | 0.9300 |
C11—C11i | 1.491 (2) | C6—H6 | 0.9300 |
C7—C6 | 1.3918 (17) | C1—H1 | 0.9300 |
C7—C2 | 1.4024 (17) | ||
C8—C9—C10 | 119.93 (11) | C12—C13—C8 | 120.37 (11) |
C8—C9—H9 | 120.0 | C12—C13—H13 | 119.8 |
C10—C9—H9 | 120.0 | C8—C13—H13 | 119.8 |
C1—N2—C7 | 105.87 (10) | C13—C12—C11 | 121.94 (11) |
C1—N2—C8 | 125.89 (11) | C13—C12—H12 | 119.0 |
C7—N2—C8 | 128.14 (10) | C11—C12—H12 | 119.0 |
C9—C10—C11 | 122.16 (11) | N1—C2—C3 | 129.57 (11) |
C9—C10—H10 | 118.9 | N1—C2—C7 | 110.69 (10) |
C11—C10—H10 | 118.9 | C3—C2—C7 | 119.70 (11) |
C1—N1—C2 | 104.25 (10) | C4—C3—C2 | 118.10 (12) |
C12—C11—C10 | 116.39 (11) | C4—C3—H3 | 120.9 |
C12—C11—C11i | 121.83 (13) | C2—C3—H3 | 120.9 |
C10—C11—C11i | 121.78 (13) | C9—C8—C13 | 119.18 (11) |
C6—C7—N2 | 132.38 (11) | C9—C8—N2 | 121.11 (10) |
C6—C7—C2 | 122.66 (11) | C13—C8—N2 | 119.70 (11) |
N2—C7—C2 | 104.86 (10) | C5—C6—C7 | 116.40 (11) |
C6—C5—C4 | 122.10 (12) | C5—C6—H6 | 121.8 |
C6—C5—H5 | 118.9 | C7—C6—H6 | 121.8 |
C4—C5—H5 | 118.9 | N1—C1—N2 | 114.33 (12) |
C3—C4—C5 | 121.03 (11) | N1—C1—H1 | 122.8 |
C3—C4—H4 | 119.5 | N2—C1—H1 | 122.8 |
C5—C4—H4 | 119.5 | ||
C8—C9—C10—C11 | −0.30 (18) | C5—C4—C3—C2 | 0.17 (17) |
C9—C10—C11—C12 | −1.33 (17) | N1—C2—C3—C4 | −177.73 (11) |
C9—C10—C11—C11i | 178.27 (12) | C7—C2—C3—C4 | −0.38 (16) |
C1—N2—C7—C6 | −177.15 (12) | C10—C9—C8—C13 | 1.41 (16) |
C8—N2—C7—C6 | −0.74 (18) | C10—C9—C8—N2 | −179.55 (10) |
C1—N2—C7—C2 | −0.74 (11) | C12—C13—C8—C9 | −0.85 (17) |
C8—N2—C7—C2 | 175.68 (10) | C12—C13—C8—N2 | −179.90 (10) |
C6—C5—C4—C3 | 0.30 (18) | C1—N2—C8—C9 | −138.05 (12) |
C8—C13—C12—C11 | −0.85 (18) | C7—N2—C8—C9 | 46.20 (15) |
C10—C11—C12—C13 | 1.90 (17) | C1—N2—C8—C13 | 40.98 (16) |
C11i—C11—C12—C13 | −177.70 (12) | C7—N2—C8—C13 | −134.76 (12) |
C1—N1—C2—C3 | 176.54 (12) | C4—C5—C6—C7 | −0.53 (17) |
C1—N1—C2—C7 | −1.00 (12) | N2—C7—C6—C5 | 176.21 (11) |
C6—C7—C2—N1 | 177.95 (10) | C2—C7—C6—C5 | 0.32 (16) |
N2—C7—C2—N1 | 1.09 (12) | C2—N1—C1—N2 | 0.52 (13) |
C6—C7—C2—C3 | 0.13 (17) | C7—N2—C1—N1 | 0.14 (13) |
N2—C7—C2—C3 | −176.73 (10) | C8—N2—C1—N1 | −176.38 (9) |
Symmetry code: (i) −x+1, −y+2, −z+1. |
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···N1ii | 0.93 | 2.61 | 3.425 (2) | 147 |
Symmetry code: (ii) x, −y+2, z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C26H18N4 |
Mr | 386.44 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 293 |
a, b, c (Å) | 19.628 (4), 6.8964 (14), 13.760 (3) |
β (°) | 90.74 (3) |
V (Å3) | 1862.4 (7) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.26 × 0.22 × 0.10 |
Data collection | |
Diffractometer | Bruker SMART 1000 CCD |
Absorption correction | Multi-scan (SADABS; Bruker, 1998) |
Tmin, Tmax | 0.904, 1.000 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 9091, 1644, 1415 |
Rint | 0.037 |
(sin θ/λ)max (Å−1) | 0.595 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.037, 0.103, 1.10 |
No. of reflections | 1644 |
No. of parameters | 137 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.18, −0.17 |
Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1998), SHELXTL (Bruker, 1998).
D—H···A | D—H | H···A | D···A | D—H···A |
C6—H6···N1i | 0.93 | 2.61 | 3.425 (2) | 147 |
Symmetry code: (i) x, −y+2, z+1/2. |
Acknowledgements
The authors thank Nankai University for supporting this work.
References
Bruker (1998). SMART (Version 5.051), SAINT (Version 5.01), SADABS (Version 2.03) and SHELXTL (Version 6.1). Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Bu, X. H., Li, L., Hu, T. L., Li, J. R., Wang, D. Z. & Zeng, Y. F. (2007). CrystEngComm, 9, 412–420. Google Scholar
Buchwald, S. L., Klapars, A., Antilla, J. C. & Huang, X. H. (2001). J. Am. Chem. Soc. 123, 7727–7729. Web of Science PubMed Google Scholar
Cristau, H. J., Cellier, P. P., Spindler, J. F. & Taillefer, M. (2004). Chem. Eur. J. 10, 5607–5622. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Göttingen, Germany. Google Scholar
Su, C. Y., Cai, Y. P., Chen, C. L., Smith, M. D., Kaim, W. & zur Loye, H. C. (2003). J. Am. Chem. Soc. 125, 8595–8613. Web of Science CSD CrossRef PubMed CAS 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.
In recent years, benzimidazole derivatives have been found a wide range of application in the area of coordination chemistry, because they exhibit a strong networking ability (Bu et al., 2007; Su et al., 2003). The title compound has been designed for building polymer architectures. We report here the structure and conformation, towards an understanding of the ligand coordination. As shown in Fig. 1, the title compound has trans-conformation and therefore a tendency to trans-coordination. The molecule resides on an inversion centre, and the dihedral angle between the benzimidazole ring and the phenyl ring is 40.97 (17)°. There are weak H-bonding interactions in the crystal structure of (I) (C6—H6···N1B, 3.425 (17) Å, C—H···N of 146.82 (13)°, B= x,-y + 2,z + 1/2) (Fig. 2).