1,4-Bis(benzimidazol-2-yl)benzene dimethyl­formamide disolvate

Wu, D.-H.; Hu, L.

doi:10.1107/S1600536809004759

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 3| March 2009| Page o522

doi:10.1107/S1600536809004759

Open

access

1,4-Bis(benzimidazol-2-yl)benzene dimethylformamide disolvate

De-Hong Wu ^a ^* and Ling Hu ^a

^aOrdered Matter Science Research Center, College of Chemistry and Chemical Engineering, Southeast University, Nanjing 210096, People's Republic of China
^*Correspondence e-mail: wudh1971@sohu.com

(Received 21 January 2009; accepted 10 February 2009; online 13 February 2009)

The aromatic molecule of the title compound, C₂₀H₁₄N₄·2C₃H₇NO, occupies a special position on an inversion center. The benzimidazole unit (planar to within 0.008 Å) forms a dihedral angle of 9.1 (2)° with the central benzene ring. The benzimidazole H atom participates in a hydrogen bond with the dimethylformamide solvent molecule, thus giving rise to the title 1:2 aggregate. These aggregates are further linked in the crystal structure by aromatic π–π stacking interactions [centroid–centroid distance = 6.356 (2) Å].

Related literature

For background literature concerning benzimidazole compounds, see: Zarrinmayeh et al. (1998 ); Gallagher et al. (2001 ); Howarth & Hanlon (2001 ). For the unsolvated structure, see: Bei et al. (2000 ); Dudd et al. (2003 ).

Experimental

Crystal data

C₂₀H₁₄N₄·2C₃H₇NO
M_r = 456.54
Monoclinic, P 2₁ /n
a = 6.3556 (13) Å
b = 20.931 (2) Å
c = 9.0097 (18) Å
β = 98.26 (2)°
V = 1186.1 (4) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 291 K
0.32 × 0.26 × 0.24 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.970, T_max = 0.990
12310 measured reflections
2723 independent reflections
1718 reflections with I > 2σ(I)
R_int = 0.054

Refinement

R[F² > 2σ(F²)] = 0.057
wR(F²) = 0.158
S = 1.00
2723 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.24 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.86	1.95	2.787 (3)	165
Symmetry code: (i) -x+2, -y+1, -z+1.

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear; data reduction: CrystalClear; 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: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809004759/ya2086sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809004759/ya2086Isup2.hkl

checkCIF report

Comment top

Benzimidazole systems continue to attract considerable attention in chemical synthesis, structural science and applied medicinal research (Zarrinmayeh et al., 1998; Gallagher et al., 2001; Howarth & Hanlon, 2001). Here we report the crystal structure of the title compound, 1,4-bis(2-benzimidazolyl)benzene bis(dimethylformamide) solvate.

The 1,4-bis(2-benzimidazolyl)benzene molecule occupies a special position on the inversion center, and benzimidazole moiety (planar within 0.0078 Å) forms dihedral angle of 9.1 (2)° with the plane of the central benzene ring (Fig. 1). This shows that 1,4-(2-benzimidazolyl)benzene molecule in the structure of the title compound deviates from planarity to a much lesser degree than in the unsolvated structure, wherein the corresponding dihedral angle is equal to 31.0° (Bei et al., 2000; Dudd et al., 2003).

The only `active' hydrogen atom H2 participates in the H-bond with the carbonyl atom of the dimethylformamide molecule (H2···O1 1.95 Å, N2—H2···O1 165.1°) thus giving rise to the 1,4-bis(2-benzimidazolyl)benzene:DMFA (1:2) complexes, which are further linked in crystal through the π—π stacking interactions.

Related literature top

For background literature concerning benzimidazole compounds, see: Zarrinmayeh et al. (1998); Gallagher et al. (2001); Howarth & Hanlon (2001). For the unsolvated structure, see: Bei et al. (2000); Dudd et al. (2003).

Experimental top

The title compound was synthesized by refluxing terephthalaldehyde (0.53 g, 4 mmol) and benzene-1,2-diamine (0.86 g, 8 mmol) in absolute methanol (50 ml) for 8 h. After cooling to room temperature, the yellow solid thus formed was isolated and dried under vacuum (1.13 g, yield 80 %). Single crystals suitable for X-ray structure analysis were obtained by the slow evaporation of a dimethylformamide solution in air.

Computing details top

Data collection: CrystalClear (Rigaku, 2005); cell refinement: CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of 1,4-bis(2-benzimidazolyl)benzene and dimethylformamide molecules in the crystal of the title compound, showing the atomic numbering scheme and 30% probability displacement ellipsoids. Unlabelled atoms are related to the labelled atoms by the (1 - x, -y, 1 - z) symmetry transformation.

1,4-Bis(benzimidazol-2-yl)benzene dimethylformamide disolvate top

Crystal data top

C₂₀H₁₄N₄·2C₃H₇NO	F(000) = 484
M_r = 456.54	D_x = 1.278 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 9216 reflections
a = 6.3556 (13) Å	θ = 3.0–27.7°
b = 20.931 (2) Å	µ = 0.08 mm⁻¹
c = 9.0097 (18) Å	T = 291 K
β = 98.26 (2)°	Block, yellow
V = 1186.1 (4) Å³	0.32 × 0.26 × 0.24 mm
Z = 2

Data collection top

Rigaku Mercury2 diffractometer	2723 independent reflections
Radiation source: fine-focus sealed tube	1718 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.054
Detector resolution: 13.6612 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
CCD profile fitting scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −27→27
T_min = 0.970, T_max = 0.990	l = −11→11
12310 measured reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.057	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H-atom parameters constrained
S = 1.00	w = 1/[σ²(F_o²) + (0.0615P)² + 0.4757P] where P = (F_o² + 2F_c²)/3
2723 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.24 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₂₀H₁₄N₄·2C₃H₇NO	V = 1186.1 (4) Å³
M_r = 456.54	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.3556 (13) Å	µ = 0.08 mm⁻¹
b = 20.931 (2) Å	T = 291 K
c = 9.0097 (18) Å	0.32 × 0.26 × 0.24 mm
β = 98.26 (2)°

Data collection top

Rigaku Mercury2 diffractometer	2723 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1718 reflections with I > 2σ(I)
T_min = 0.970, T_max = 0.990	R_int = 0.054
12310 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.057	0 restraints
wR(F²) = 0.158	H-atom parameters constrained
S = 1.00	Δρ_max = 0.24 e Å⁻³
2723 reflections	Δρ_min = −0.21 e Å⁻³
154 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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

	x	y	z	U_iso*/U_eq
C1	0.4424 (3)	0.03145 (10)	0.6222 (2)	0.0442 (5)
H1A	0.4027	0.0527	0.7045	0.053*
C2	0.6334 (3)	0.04722 (9)	0.5722 (2)	0.0394 (5)
C3	0.6877 (3)	0.01491 (10)	0.4482 (2)	0.0454 (5)
H3A	0.8140	0.0249	0.4126	0.054*
C4	0.7705 (3)	0.09548 (9)	0.6530 (2)	0.0396 (5)
C5	0.9076 (3)	0.16201 (10)	0.8206 (2)	0.0431 (5)
C6	1.0397 (3)	0.16157 (9)	0.7099 (2)	0.0425 (5)
C7	1.2235 (4)	0.19770 (11)	0.7212 (3)	0.0563 (6)
H7A	1.3119	0.1966	0.6474	0.068*
C8	1.2694 (4)	0.23526 (12)	0.8464 (3)	0.0655 (7)
H8A	1.3914	0.2604	0.8575	0.079*
C9	1.1379 (4)	0.23673 (12)	0.9574 (3)	0.0638 (7)
H9A	1.1734	0.2630	1.0404	0.077*
C10	0.9577 (4)	0.20035 (11)	0.9471 (3)	0.0578 (6)
H10A	0.8713	0.2012	1.0221	0.069*
C11	0.7511 (4)	0.87860 (14)	0.7174 (3)	0.0663 (7)
H11A	0.6668	0.8486	0.6607	0.080*
C12	0.7988 (5)	0.95068 (16)	0.9240 (3)	0.0905 (10)
H12A	0.9305	0.9584	0.8865	0.136*
H12B	0.8277	0.9357	1.0255	0.136*
H12C	0.7187	0.9897	0.9210	0.136*
C13	0.4746 (5)	0.88579 (18)	0.8728 (4)	0.0984 (11)
H13A	0.4093	0.8540	0.8042	0.148*
H13B	0.3850	0.9229	0.8681	0.148*
H13C	0.4937	0.8689	0.9728	0.148*
N1	0.7398 (3)	0.12012 (9)	0.78322 (19)	0.0470 (5)
N2	0.9489 (3)	0.11884 (8)	0.60413 (19)	0.0442 (4)
H2A	0.9957	0.1087	0.5223	0.053*
N3	0.6781 (3)	0.90317 (9)	0.8324 (2)	0.0526 (5)
O1	0.9230 (3)	0.89199 (11)	0.6780 (2)	0.0845 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0431 (11)	0.0534 (13)	0.0382 (11)	0.0016 (10)	0.0135 (9)	−0.0061 (9)
C2	0.0390 (11)	0.0442 (11)	0.0355 (10)	0.0044 (9)	0.0071 (8)	0.0028 (8)
C3	0.0397 (11)	0.0537 (12)	0.0451 (12)	−0.0003 (10)	0.0144 (9)	−0.0011 (10)
C4	0.0386 (11)	0.0425 (11)	0.0385 (10)	0.0033 (9)	0.0088 (9)	0.0043 (9)
C5	0.0431 (11)	0.0414 (11)	0.0457 (12)	0.0015 (9)	0.0088 (9)	0.0011 (9)
C6	0.0441 (11)	0.0398 (11)	0.0440 (11)	0.0015 (9)	0.0080 (9)	0.0061 (9)
C7	0.0494 (13)	0.0570 (14)	0.0655 (15)	−0.0081 (11)	0.0183 (11)	0.0020 (12)
C8	0.0543 (15)	0.0584 (15)	0.0827 (19)	−0.0146 (12)	0.0066 (13)	−0.0018 (13)
C9	0.0672 (16)	0.0582 (15)	0.0649 (16)	−0.0106 (13)	0.0052 (13)	−0.0125 (12)
C10	0.0635 (15)	0.0580 (14)	0.0537 (14)	−0.0070 (12)	0.0146 (12)	−0.0107 (11)
C11	0.0706 (17)	0.0797 (18)	0.0501 (14)	0.0029 (14)	0.0129 (13)	−0.0001 (13)
C12	0.112 (3)	0.085 (2)	0.0701 (19)	0.0047 (19)	−0.0020 (18)	−0.0122 (16)
C13	0.078 (2)	0.126 (3)	0.101 (2)	−0.001 (2)	0.0443 (19)	0.023 (2)
N1	0.0467 (10)	0.0530 (10)	0.0439 (10)	−0.0042 (8)	0.0158 (8)	−0.0052 (8)
N2	0.0454 (10)	0.0488 (10)	0.0414 (9)	−0.0018 (8)	0.0166 (8)	−0.0012 (8)
N3	0.0540 (11)	0.0625 (12)	0.0438 (10)	0.0004 (9)	0.0153 (9)	0.0007 (9)
O1	0.0695 (12)	0.1293 (18)	0.0613 (12)	0.0077 (12)	0.0318 (10)	0.0092 (11)

Geometric parameters (Å, º) top

C1—C3ⁱ	1.370 (3)	C8—H8A	0.9300
C1—C2	1.394 (3)	C9—C10	1.367 (3)
C1—H1A	0.9300	C9—H9A	0.9300
C2—C3	1.391 (3)	C10—H10A	0.9300
C2—C4	1.459 (3)	C11—O1	1.229 (3)
C3—C1ⁱ	1.370 (3)	C11—N3	1.300 (3)
C3—H3A	0.9300	C11—H11A	0.9300
C4—N1	1.322 (2)	C12—N3	1.441 (3)
C4—N2	1.364 (2)	C12—H12A	0.9600
C5—N1	1.384 (3)	C12—H12B	0.9600
C5—C10	1.393 (3)	C12—H12C	0.9600
C5—C6	1.393 (3)	C13—N3	1.440 (3)
C6—N2	1.372 (3)	C13—H13A	0.9600
C6—C7	1.383 (3)	C13—H13B	0.9600
C7—C8	1.372 (4)	C13—H13C	0.9600
C7—H7A	0.9300	N2—H2A	0.8600
C8—C9	1.393 (4)

C3ⁱ—C1—C2	120.91 (18)	C8—C9—H9A	119.3
C3ⁱ—C1—H1A	119.5	C9—C10—C5	117.9 (2)
C2—C1—H1A	119.5	C9—C10—H10A	121.1
C3—C2—C1	118.20 (19)	C5—C10—H10A	121.1
C3—C2—C4	122.55 (18)	O1—C11—N3	125.0 (3)
C1—C2—C4	119.23 (17)	O1—C11—H11A	117.5
C1ⁱ—C3—C2	120.89 (19)	N3—C11—H11A	117.5
C1ⁱ—C3—H3A	119.6	N3—C12—H12A	109.5
C2—C3—H3A	119.6	N3—C12—H12B	109.5
N1—C4—N2	112.48 (18)	H12A—C12—H12B	109.5
N1—C4—C2	124.01 (18)	N3—C12—H12C	109.5
N2—C4—C2	123.48 (17)	H12A—C12—H12C	109.5
N1—C5—C10	129.9 (2)	H12B—C12—H12C	109.5
N1—C5—C6	110.11 (18)	N3—C13—H13A	109.5
C10—C5—C6	120.0 (2)	N3—C13—H13B	109.5
N2—C6—C7	132.4 (2)	H13A—C13—H13B	109.5
N2—C6—C5	105.38 (17)	N3—C13—H13C	109.5
C7—C6—C5	122.2 (2)	H13A—C13—H13C	109.5
C8—C7—C6	116.9 (2)	H13B—C13—H13C	109.5
C8—C7—H7A	121.6	C4—N1—C5	104.84 (16)
C6—C7—H7A	121.6	C4—N2—C6	107.19 (16)
C7—C8—C9	121.6 (2)	C4—N2—H2A	126.4
C7—C8—H8A	119.2	C6—N2—H2A	126.4
C9—C8—H8A	119.2	C11—N3—C13	122.5 (3)
C10—C9—C8	121.5 (2)	C11—N3—C12	120.5 (2)
C10—C9—H9A	119.3	C13—N3—C12	117.0 (2)

Symmetry code: (i) −x+1, −y, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱⁱ	0.86	1.95	2.787 (3)	165

Symmetry code: (ii) −x+2, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₄N₄·2C₃H₇NO
M_r	456.54
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	291
a, b, c (Å)	6.3556 (13), 20.931 (2), 9.0097 (18)
β (°)	98.26 (2)
V (Å³)	1186.1 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.26 × 0.24

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.970, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	12310, 2723, 1718
R_int	0.054
(sin θ/λ)_max (Å⁻¹)	0.650

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.057, 0.158, 1.00
No. of reflections	2723
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.24, −0.21

Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86	1.95	2.787 (3)	165.1

Symmetry code: (i) −x+2, −y+1, −z+1.

Acknowledgements

The authors appreciate the help of Professor Dr Rengen Xiong and the financial support of Jiangsu Planned Projects for Postdoctoral Research Funds (grant No. 0802003B).

References

Bei, F., Jian, F., Yang, X., Lu, L., Wang, X., Shanmuga Sundara Raj, S. & Fun, H.-K. (2000). Acta Cryst. C56, 718–719. CSD CrossRef CAS IUCr Journals Google Scholar
Dudd, L. M., Venardou, E., Garcia-Verdugo, E., Licence, P., Blake, A. J., Wilson, C. & Poliakoff, M. (2003). Green Chem. 5, 187–192. Web of Science CSD CrossRef CAS Google Scholar
Gallagher, J. F., Hanlon, K. & Howarth, J. (2001). Acta Cryst. C57, 1410–1414. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
Howarth, J. & Hanlon, K. (2001). Tetrahedron Lett. 42, 271–274. Google Scholar
Rigaku (2005). CrystalClear. Rigaku Corporation, Tokyo, Japan. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Zarrinmayeh, H., Nunes, A. M., Ornstein, P. L., Zimmerman, D. A., Gackenheimer, S. L., Bruns, R. F., Hipskind, P. A., Britton, T. C., Cantrell, B. E. & Gehlert, D. R. (1998). J. Med. Chem. 41, 2709–2719. Web of Science CSD CrossRef CAS PubMed Google Scholar