1-(1H-Benzimidazol-2-yl)-4-nitro­benzene dimethyl­formamide solvate

Wu, D.-H.

doi:10.1107/S1600536809005315

organic compounds

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Volume 65| Part 3| March 2009| Page o557

doi:10.1107/S1600536809005315

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1-(1H-Benzimidazol-2-yl)-4-nitrobenzene dimethylformamide solvate

De-Hong Wu ^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 4 February 2009; accepted 14 February 2009; online 21 February 2009)

In the title compound, C₁₃H₉N₃O₂·C₃H₇NO, the benzimidazole ring system and the benzene ring are essentially coplanar, forming a dihedral angle of 0.86 (5)°. The crystal packing is stabilized by an intermolecular N—H⋯O hydrogen bond and a π–π stacking interaction with a centroid–centroid separation of 3.685 (4) Å.

Related literature

For general background to benzimidazole compounds, see: Zarrinmayeh et al. (1998 ); Gallagher et al. (2001 ); Howarth & Hanlon (2001 ).

Experimental

Crystal data

C₁₃H₉N₃O₂·C₃H₇NO
M_r = 312.33
Triclinic, $[P \overline 1]$
a = 6.6228 (13) Å
b = 10.601 (2) Å
c = 11.886 (2) Å
α = 84.534 (10)°
β = 74.13 (2)°
γ = 81.53 (3)°
V = 792.6 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 291 K
0.30 × 0.26 × 0.24 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ) T_min = 0.96, T_max = 0.98
7352 measured reflections
3102 independent reflections
1567 reflections with I > 2σ(I)
R_int = 0.045

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.138
S = 1.01
3102 reflections
210 parameters
H-atom parameters constrained
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯O3ⁱ	0.90	1.89	2.753 (2)	161
Symmetry code: (i) -x+1, -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/S1600536809005315/rz2294sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809005315/rz2294Isup2.hkl

checkCIF report

Comment top

Benzimidazole systems continue to attract much 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-(2-benzimidazolyl)-4-nitrobenzene dimethylformamide solvate.

The structural analysis shows that in the title compound (Fig. 1) the benzimidazole ring system and the benzene ring are essentially coplanar forming a dihedral angle of 0.86 (5)°. In the imidazole ring, the C7–N2 bond length of 1.327 (2) Å conforms to the value expected for a double bond. The dimethylformamide molecule bridges the benzimidazole ring system, forming an intermolecular N—H···O hydrogen bond (Table 1). The crystal packing is stabilized by aromatic π–π stacking interactions: Cp1···Cp2ⁱ = 3.865 (4) Å; perpendicular interplanar distance: 3.374 (3) Å; Cp1···Cp2ⁱ offset: 1.481 (3) Å (Cp1 and Cp2 are the centroids of the C1—C7 and C8—C13 aromatic rings, respectively; symmetry code: (i) -1+x, y, z).

Related literature top

For general background to benzimidazole compounds, see: Zarrinmayeh et al. (1998); Gallagher et al. (2001); Howarth & Hanlon (2001).

Experimental top

The title compound was synthesized by refluxing 4-nitrobenzaldehyde (6.04 g, 4 mmol) and benzene-1,2-diamine (0.43 g, 4 mmol) in 40 ml absolute methanol for 10 h. After cooling to ambient temperature, the yellow solid formed was isolated and dried under vacuum (7.2 g, yield 75%). Single crystals suitable for X-ray structure analysis were obtained by 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 molecular structure of the title compound, showing the atomic numbering scheme and 30% probability displacement ellipsoids. The A suffix for atoms O3, N4, C14, C15 and C16 denotes a transformation of (1 - x, 1 - y, 1 - z). The intermolecular N—H···O hydrogen bond is shown as a dashed line.

1-(1H-Benzimidazol-2-yl)-4-nitrobenzene dimethylformamide solvate top

Crystal data top

C₁₃H₉N₃O₂·C₃H₇NO	Z = 2
M_r = 312.33	F(000) = 328
Triclinic, P1	D_x = 1.309 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.6228 (13) Å	Cell parameters from 5280 reflections
b = 10.601 (2) Å	θ = 3.2–27.4°
c = 11.886 (2) Å	µ = 0.09 mm⁻¹
α = 84.534 (10)°	T = 291 K
β = 74.13 (2)°	Block, yellow
γ = 81.53 (3)°	0.30 × 0.26 × 0.24 mm
V = 792.6 (3) Å³

Data collection top

Rigaku Mercury2 diffractometer	3102 independent reflections
Radiation source: fine-focus sealed tube	1567 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.045
Detector resolution: 13.6612 pixels mm^-1	θ_max = 26.0°, θ_min = 3.2°
CCD_Profile_fitting scans	h = −8→8
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	k = −13→12
T_min = 0.96, T_max = 0.98	l = −14→14
7352 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)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.138	H-atom parameters constrained
S = 1.01	w = 1/[σ²(F_o²) + (0.0586P)²] where P = (F_o² + 2F_c²)/3
3102 reflections	(Δ/σ)_max < 0.001
210 parameters	Δρ_max = 0.12 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₁₃H₉N₃O₂·C₃H₇NO	γ = 81.53 (3)°
M_r = 312.33	V = 792.6 (3) Å³
Triclinic, P1	Z = 2
a = 6.6228 (13) Å	Mo Kα radiation
b = 10.601 (2) Å	µ = 0.09 mm⁻¹
c = 11.886 (2) Å	T = 291 K
α = 84.534 (10)°	0.30 × 0.26 × 0.24 mm
β = 74.13 (2)°

Data collection top

Rigaku Mercury2 diffractometer	3102 independent reflections
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)	1567 reflections with I > 2σ(I)
T_min = 0.96, T_max = 0.98	R_int = 0.045
7352 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.138	H-atom parameters constrained
S = 1.01	Δρ_max = 0.12 e Å⁻³
3102 reflections	Δρ_min = −0.20 e Å⁻³
210 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

	x	y	z	U_iso*/U_eq
C1	−0.0895 (4)	0.3267 (2)	0.7884 (2)	0.0599 (6)
C2	−0.2701 (4)	0.3902 (2)	0.8605 (2)	0.0798 (8)
H2A	−0.2737	0.4732	0.8809	0.096*
C3	−0.4438 (5)	0.3249 (3)	0.9006 (2)	0.0857 (8)
H3A	−0.5668	0.3643	0.9497	0.103*
C4	−0.4385 (4)	0.2011 (2)	0.8689 (2)	0.0798 (8)
H4A	−0.5584	0.1597	0.8973	0.096*
C5	−0.2605 (4)	0.1383 (2)	0.7965 (2)	0.0658 (7)
H5A	−0.2587	0.0557	0.7756	0.079*
C6	−0.0832 (4)	0.20250 (19)	0.75577 (18)	0.0540 (6)
C7	0.2234 (4)	0.26232 (18)	0.67137 (18)	0.0535 (6)
C8	0.4421 (4)	0.26378 (18)	0.60121 (18)	0.0520 (6)
C9	0.5535 (4)	0.36846 (19)	0.5917 (2)	0.0605 (6)
H9A	0.4864	0.4414	0.6308	0.073*
C10	0.7583 (4)	0.3659 (2)	0.5264 (2)	0.0610 (6)
H10A	0.8299	0.4365	0.5202	0.073*
C11	0.8578 (4)	0.2568 (2)	0.46957 (19)	0.0564 (6)
C12	0.7539 (4)	0.1508 (2)	0.4773 (2)	0.0667 (7)
H12A	0.8226	0.0777	0.4389	0.080*
C13	0.5471 (4)	0.1560 (2)	0.5427 (2)	0.0670 (7)
H13A	0.4757	0.0855	0.5480	0.080*
C14	0.7196 (4)	0.3189 (2)	0.2083 (2)	0.0751 (7)
H14A	0.5807	0.3254	0.2545	0.090*
C15	1.0088 (5)	0.1989 (3)	0.0766 (3)	0.1051 (10)
H15A	1.0684	0.2774	0.0694	0.158*
H15B	1.0053	0.1771	0.0006	0.158*
H15C	1.0940	0.1320	0.1093	0.158*
C16	0.6700 (5)	0.1095 (2)	0.1649 (3)	0.1028 (10)
H16A	0.5303	0.1337	0.2136	0.154*
H16B	0.7355	0.0352	0.2002	0.154*
H16C	0.6612	0.0908	0.0891	0.154*
N1	0.1073 (3)	0.36303 (15)	0.73324 (16)	0.0621 (5)
H1A	0.1515	0.4383	0.7376	0.074*
N2	0.1147 (3)	0.16428 (15)	0.68163 (16)	0.0564 (5)
N3	1.0776 (3)	0.2533 (2)	0.39914 (18)	0.0720 (6)
N4	0.7958 (3)	0.21395 (17)	0.15256 (17)	0.0647 (6)
O1	1.1681 (3)	0.34815 (17)	0.39184 (17)	0.0937 (6)
O2	1.1653 (3)	0.15534 (18)	0.35180 (19)	0.1073 (7)
O3	0.8186 (3)	0.40844 (16)	0.20342 (19)	0.1109 (8)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0662 (17)	0.0574 (14)	0.0553 (15)	−0.0032 (13)	−0.0130 (13)	−0.0147 (12)
C2	0.086 (2)	0.0740 (17)	0.0737 (18)	−0.0067 (16)	−0.0048 (16)	−0.0276 (14)
C3	0.071 (2)	0.100 (2)	0.0763 (19)	−0.0065 (17)	0.0020 (15)	−0.0251 (16)
C4	0.076 (2)	0.0857 (19)	0.0749 (19)	−0.0169 (15)	−0.0098 (16)	−0.0081 (15)
C5	0.0683 (18)	0.0643 (15)	0.0641 (16)	−0.0103 (14)	−0.0141 (14)	−0.0081 (13)
C6	0.0637 (16)	0.0493 (12)	0.0487 (14)	−0.0006 (11)	−0.0159 (13)	−0.0085 (10)
C7	0.0644 (17)	0.0431 (12)	0.0561 (15)	0.0000 (11)	−0.0212 (13)	−0.0119 (11)
C8	0.0579 (15)	0.0467 (12)	0.0517 (14)	−0.0007 (11)	−0.0159 (12)	−0.0096 (10)
C9	0.0636 (17)	0.0448 (13)	0.0702 (16)	0.0021 (11)	−0.0139 (14)	−0.0144 (11)
C10	0.0647 (17)	0.0475 (12)	0.0715 (16)	−0.0054 (11)	−0.0179 (14)	−0.0103 (12)
C11	0.0571 (15)	0.0576 (14)	0.0540 (14)	−0.0015 (12)	−0.0149 (12)	−0.0094 (11)
C12	0.0693 (18)	0.0543 (14)	0.0756 (18)	−0.0022 (13)	−0.0139 (15)	−0.0237 (12)
C13	0.0667 (18)	0.0564 (14)	0.0773 (17)	−0.0107 (12)	−0.0098 (15)	−0.0243 (13)
C14	0.0786 (19)	0.0670 (16)	0.0733 (18)	0.0010 (15)	−0.0107 (15)	−0.0157 (14)
C15	0.086 (2)	0.116 (2)	0.097 (2)	0.0080 (18)	−0.0026 (19)	−0.0213 (18)
C16	0.126 (3)	0.0753 (18)	0.118 (3)	−0.0349 (19)	−0.041 (2)	−0.0015 (17)
N1	0.0643 (13)	0.0478 (10)	0.0726 (13)	−0.0072 (9)	−0.0103 (11)	−0.0195 (9)
N2	0.0595 (13)	0.0482 (10)	0.0629 (13)	−0.0041 (9)	−0.0176 (11)	−0.0098 (9)
N3	0.0658 (15)	0.0694 (14)	0.0772 (15)	−0.0028 (12)	−0.0122 (12)	−0.0158 (12)
N4	0.0693 (14)	0.0548 (11)	0.0672 (13)	−0.0039 (10)	−0.0117 (11)	−0.0145 (10)
O1	0.0768 (13)	0.0837 (12)	0.1160 (16)	−0.0240 (11)	−0.0070 (11)	−0.0164 (11)
O2	0.0802 (14)	0.0926 (14)	0.1324 (18)	−0.0057 (11)	0.0111 (12)	−0.0483 (13)
O3	0.1330 (19)	0.0708 (12)	0.1336 (18)	−0.0294 (12)	−0.0241 (14)	−0.0360 (12)

Geometric parameters (Å, º) top

C1—N1	1.381 (3)	C10—H10A	0.9300
C1—C2	1.389 (3)	C11—C12	1.385 (3)
C1—C6	1.400 (3)	C11—N3	1.464 (3)
C2—C3	1.379 (3)	C12—C13	1.374 (3)
C2—H2A	0.9300	C12—H12A	0.9300
C3—C4	1.393 (3)	C13—H13A	0.9300
C3—H3A	0.9300	C14—O3	1.219 (3)
C4—C5	1.377 (3)	C14—N4	1.313 (3)
C4—H4A	0.9300	C14—H14A	0.9300
C5—C6	1.392 (3)	C15—N4	1.448 (3)
C5—H5A	0.9300	C15—H15A	0.9600
C6—N2	1.392 (3)	C15—H15B	0.9600
C7—N2	1.327 (2)	C15—H15C	0.9600
C7—N1	1.368 (2)	C16—N4	1.454 (3)
C7—C8	1.462 (3)	C16—H16A	0.9600
C8—C13	1.387 (3)	C16—H16B	0.9600
C8—C9	1.400 (3)	C16—H16C	0.9600
C9—C10	1.364 (3)	N1—H1A	0.8998
C9—H9A	0.9300	N3—O2	1.220 (2)
C10—C11	1.381 (3)	N3—O1	1.229 (2)

N1—C1—C2	132.3 (2)	C12—C11—N3	119.2 (2)
N1—C1—C6	105.77 (19)	C13—C12—C11	118.5 (2)
C2—C1—C6	121.9 (2)	C13—C12—H12A	120.7
C3—C2—C1	117.2 (2)	C11—C12—H12A	120.7
C3—C2—H2A	121.4	C12—C13—C8	121.7 (2)
C1—C2—H2A	121.4	C12—C13—H13A	119.2
C2—C3—C4	121.3 (2)	C8—C13—H13A	119.2
C2—C3—H3A	119.4	O3—C14—N4	124.4 (3)
C4—C3—H3A	119.4	O3—C14—H14A	117.8
C5—C4—C3	121.8 (3)	N4—C14—H14A	117.8
C5—C4—H4A	119.1	N4—C15—H15A	109.5
C3—C4—H4A	119.1	N4—C15—H15B	109.5
C4—C5—C6	117.8 (2)	H15A—C15—H15B	109.5
C4—C5—H5A	121.1	N4—C15—H15C	109.5
C6—C5—H5A	121.1	H15A—C15—H15C	109.5
C5—C6—N2	130.4 (2)	H15B—C15—H15C	109.5
C5—C6—C1	120.1 (2)	N4—C16—H16A	109.5
N2—C6—C1	109.5 (2)	N4—C16—H16B	109.5
N2—C7—N1	112.44 (19)	H16A—C16—H16B	109.5
N2—C7—C8	124.12 (18)	N4—C16—H16C	109.5
N1—C7—C8	123.44 (19)	H16A—C16—H16C	109.5
C13—C8—C9	117.9 (2)	H16B—C16—H16C	109.5
C13—C8—C7	119.0 (2)	C7—N1—C1	107.00 (17)
C9—C8—C7	123.09 (19)	C7—N1—H1A	126.3
C10—C9—C8	121.5 (2)	C1—N1—H1A	126.7
C10—C9—H9A	119.3	C7—N2—C6	105.30 (17)
C8—C9—H9A	119.3	O2—N3—O1	122.4 (2)
C9—C10—C11	119.0 (2)	O2—N3—C11	118.7 (2)
C9—C10—H10A	120.5	O1—N3—C11	118.9 (2)
C11—C10—H10A	120.5	C14—N4—C15	120.7 (2)
C10—C11—C12	121.5 (2)	C14—N4—C16	121.4 (2)
C10—C11—N3	119.3 (2)	C15—N4—C16	117.9 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···O3ⁱ	0.90	1.89	2.753 (2)	161

Symmetry code: (i) −x+1, −y+1, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₃H₉N₃O₂·C₃H₇NO
M_r	312.33
Crystal system, space group	Triclinic, P1
Temperature (K)	291
a, b, c (Å)	6.6228 (13), 10.601 (2), 11.886 (2)
α, β, γ (°)	84.534 (10), 74.13 (2), 81.53 (3)
V (Å³)	792.6 (3)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.30 × 0.26 × 0.24

Data collection
Diffractometer	Rigaku Mercury2 diffractometer
Absorption correction	Multi-scan (CrystalClear; Rigaku, 2005)
T_min, T_max	0.96, 0.98
No. of measured, independent and observed [I > 2σ(I)] reflections	7352, 3102, 1567
R_int	0.045
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.060, 0.138, 1.01
No. of reflections	3102
No. of parameters	210
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.12, −0.20

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
N1—H1A···O3ⁱ	0.90	1.89	2.753 (2)	160.9

Symmetry code: (i) −x+1, −y+1, −z+1.

Acknowledgements

The author thanks Jiangsu Planned Projects for Postdoctoral Research Funds (grant No. 0802003B) and Professor Dr Rengen Xiong.

References

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