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In the title mol­ecule, C15H12N4, the two essentially planar benzimidazolyl moieties make a dihedral angle of 63.53 (2)°. Inter­molecular N—H...N hydrogen bonds stabilize the crystal packing.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536805030229/cv6580sup1.cif
Contains datablocks global, I

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536805030229/cv6580Isup2.hkl
Contains datablock I

CCDC reference: 283811

Key indicators

  • Single-crystal X-ray study
  • T = 298 K
  • Mean [sigma](C-C) = 0.003 Å
  • R factor = 0.042
  • wR factor = 0.130
  • Data-to-parameter ratio = 13.4

checkCIF/PLATON results

No syntax errors found



Alert level C PLAT241_ALERT_2_C Check High Ueq as Compared to Neighbors for C5
0 ALERT level A = In general: serious problem 0 ALERT level B = Potentially serious problem 1 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Bis(benzimidazol-2-yl)methane and its derivatives are the subject of intensive study because they exhibit antimicrobial activities (Agh-Atabay et al., 2003), execute control of liver diseases (Kotomo et al., 1992), and may serve as inhibitors of cell death (Bitler et al., 2000) and HCV NS3 serine protease (Yeung et al., 2001). They are also employed as ligands (Gupta et al., 2001). In this paper, we report the crystal structure of the title compound, (I) (Fig. 1).

In (I), the bond lengths and angles of the benzimidazole moieties (Table 1) are in agreement with published values (Eryigit & Kendi, 1998; Chen et al., 2002). The benzimidazolyl moieties C1–C7/N1/N2 and C9–C15/N3/N4 are essentially planar, making a dihedral angle of 63.53 (2)°.

The crystal packing of (I) (Fig. 2) is stabilized by intermolecular N—H···N hydrogen-bond interactions (Table 2).

Experimental top

The title compound can be synthesized from 1,2-phenylenediamine and malonic acid in ethylene glycol as solvent at reflux for 24 h (Lane, 1953), in a yield of 56%, or in PPA (poly phosphorous acid) as solvent at 453 K for 2.5–4 h (Vyas et al., 1980), in a yield of 85%. However, we used 1,2-phenylenediamine (0.02 mol) and malonamide (0.01 mol) at 453–463 K under solvent-free conditions for 1 h, providing a convenient protocol for the preparation of this class of heterocycles. Purification was achieved by recrystallization from methanol in 92% isolated yield. Crystals of (I) suitable for X-ray diffraction analysis were obtained by slow evaporation from methanol at room temperature over two weeks.

Refinement top

All H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å and N—H = 0.86 Å, and were included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2Ueq of the parent atom.

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SAINT (Bruker, 1999); 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, 1999); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. A view of (I), with displacement ellipsoids drawn at the 40% probability level.
[Figure 2] Fig. 2. A packing diagram for the title compound. The intermolecular N—H···N hydrogen bonds are shown by dashed lines.
Bis(benzimidazol-2-yl)methane top
Crystal data top
C15H12N4Dx = 1.253 Mg m3
Mr = 248.29Mo Kα radiation, λ = 0.71073 Å
Tetragonal, I41/aCell parameters from 4441 reflections
Hall symbol: -I 4adθ = 2.2–25.8°
a = 18.296 (4) ŵ = 0.08 mm1
c = 15.728 (3) ÅT = 298 K
V = 5264.6 (18) Å3Block, orange
Z = 160.40 × 0.31 × 0.27 mm
F(000) = 2080
Data collection top
Bruker SMART CCD area-detector
diffractometer
2307 independent reflections
Radiation source: fine-focus sealed tube1798 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
ϕ and ω scansθmax = 25.1°, θmin = 2.8°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
h = 1521
Tmin = 0.950, Tmax = 0.979k = 1721
10662 measured reflectionsl = 1818
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)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.130H-atom parameters constrained
S = 1.00 w = 1/[σ2(Fo2) + (0.075P)2 + 1.5659P]
where P = (Fo2 + 2Fc2)/3
2307 reflections(Δ/σ)max < 0.001
172 parametersΔρmax = 0.20 e Å3
0 restraintsΔρmin = 0.16 e Å3
Crystal data top
C15H12N4Z = 16
Mr = 248.29Mo Kα radiation
Tetragonal, I41/aµ = 0.08 mm1
a = 18.296 (4) ÅT = 298 K
c = 15.728 (3) Å0.40 × 0.31 × 0.27 mm
V = 5264.6 (18) Å3
Data collection top
Bruker SMART CCD area-detector
diffractometer
2307 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)
1798 reflections with I > 2σ(I)
Tmin = 0.950, Tmax = 0.979Rint = 0.035
10662 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0420 restraints
wR(F2) = 0.130H-atom parameters constrained
S = 1.00Δρmax = 0.20 e Å3
2307 reflectionsΔρmin = 0.16 e Å3
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
N10.57166 (10)0.30536 (8)0.09757 (10)0.0708 (5)
N20.58129 (8)0.42431 (7)0.11565 (8)0.0560 (4)
H2A0.57900.47040.10490.067*
N30.41074 (8)0.42962 (7)0.06625 (8)0.0578 (4)
N40.41095 (8)0.32348 (7)0.00088 (8)0.0563 (4)
H4A0.42710.28560.02730.068*
C10.60520 (9)0.39271 (9)0.18957 (11)0.0563 (4)
C20.63143 (12)0.42248 (11)0.26529 (12)0.0767 (6)
H20.63540.47270.27280.092*
C30.65094 (15)0.37490 (13)0.32774 (14)0.0954 (8)
H30.66930.39310.37860.114*
C40.64421 (17)0.30066 (14)0.31753 (17)0.1144 (10)
H40.65750.26990.36200.137*
C50.61850 (17)0.27091 (12)0.24371 (17)0.1101 (10)
H50.61420.22060.23720.132*
C60.59899 (11)0.31847 (10)0.17871 (12)0.0669 (5)
C70.56216 (9)0.37014 (8)0.06352 (10)0.0514 (4)
C80.53220 (10)0.38310 (11)0.02331 (10)0.0635 (5)
H8A0.55260.34700.06170.076*
H8B0.54810.43090.04270.076*
C90.45082 (9)0.37953 (8)0.02848 (9)0.0511 (4)
C100.33919 (10)0.40476 (9)0.06135 (10)0.0557 (4)
C110.27477 (12)0.43470 (11)0.09232 (13)0.0752 (6)
H110.27450.47950.12030.090*
C120.21142 (12)0.39574 (13)0.08007 (14)0.0813 (6)
H120.16750.41460.10000.098*
C130.21165 (12)0.32914 (13)0.03878 (14)0.0782 (6)
H130.16790.30400.03210.094*
C140.27489 (11)0.29906 (11)0.00732 (12)0.0699 (5)
H140.27480.25440.02080.084*
C150.33900 (9)0.33830 (9)0.01940 (9)0.0538 (4)
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.1020 (12)0.0503 (8)0.0599 (9)0.0033 (8)0.0166 (8)0.0050 (7)
N20.0746 (9)0.0432 (7)0.0503 (8)0.0022 (6)0.0062 (6)0.0046 (6)
N30.0764 (10)0.0527 (8)0.0442 (7)0.0072 (7)0.0072 (6)0.0067 (6)
N40.0748 (9)0.0468 (7)0.0472 (8)0.0037 (6)0.0050 (6)0.0072 (6)
C10.0640 (10)0.0522 (9)0.0527 (10)0.0008 (7)0.0092 (8)0.0029 (7)
C20.0981 (15)0.0647 (11)0.0672 (12)0.0069 (10)0.0244 (11)0.0038 (9)
C30.126 (2)0.0895 (16)0.0703 (14)0.0084 (14)0.0436 (13)0.0050 (11)
C40.172 (3)0.0834 (16)0.0881 (17)0.0068 (16)0.0636 (18)0.0252 (13)
C50.173 (3)0.0557 (12)0.1017 (19)0.0041 (13)0.0560 (18)0.0158 (12)
C60.0873 (13)0.0515 (10)0.0618 (11)0.0012 (8)0.0199 (9)0.0017 (8)
C70.0573 (9)0.0510 (9)0.0460 (9)0.0001 (7)0.0037 (7)0.0005 (7)
C80.0739 (11)0.0769 (12)0.0398 (9)0.0046 (9)0.0032 (8)0.0018 (8)
C90.0706 (10)0.0504 (9)0.0324 (7)0.0023 (7)0.0006 (7)0.0002 (6)
C100.0725 (11)0.0548 (9)0.0397 (8)0.0040 (8)0.0025 (7)0.0037 (7)
C110.0876 (14)0.0743 (12)0.0639 (12)0.0041 (10)0.0142 (10)0.0057 (9)
C120.0713 (13)0.1036 (17)0.0690 (13)0.0044 (11)0.0093 (10)0.0094 (12)
C130.0715 (13)0.0945 (15)0.0686 (13)0.0101 (11)0.0116 (10)0.0168 (11)
C140.0827 (13)0.0652 (11)0.0618 (11)0.0112 (9)0.0167 (10)0.0051 (9)
C150.0702 (11)0.0519 (9)0.0393 (8)0.0007 (8)0.0067 (7)0.0075 (7)
Geometric parameters (Å, º) top
N1—C71.312 (2)C4—H40.9300
N1—C61.391 (2)C5—C61.389 (3)
N2—C71.333 (2)C5—H50.9300
N2—C11.370 (2)C7—C81.491 (2)
N2—H2A0.8600C8—C91.493 (2)
N3—C91.315 (2)C8—H8A0.9700
N3—C101.388 (2)C8—H8B0.9700
N4—C91.340 (2)C10—C151.384 (2)
N4—C151.381 (2)C10—C111.388 (3)
N4—H4A0.8600C11—C121.374 (3)
C1—C61.374 (2)C11—H110.9300
C1—C21.395 (2)C12—C131.381 (3)
C2—C31.360 (3)C12—H120.9300
C2—H20.9300C13—C141.373 (3)
C3—C41.373 (3)C13—H130.9300
C3—H30.9300C14—C151.388 (2)
C4—C51.366 (4)C14—H140.9300
C7—N1—C6105.43 (14)N2—C7—C8122.81 (15)
C7—N2—C1106.98 (13)C7—C8—C9114.19 (14)
C7—N2—H2A126.5C7—C8—H8A108.7
C1—N2—H2A126.5C9—C8—H8A108.7
C9—N3—C10105.81 (13)C7—C8—H8B108.7
C9—N4—C15106.79 (13)C9—C8—H8B108.7
C9—N4—H4A126.6H8A—C8—H8B107.6
C15—N4—H4A126.6N3—C9—N4112.65 (15)
N2—C1—C6106.58 (14)N3—C9—C8123.38 (14)
N2—C1—C2132.04 (16)N4—C9—C8123.89 (15)
C6—C1—C2121.38 (16)C15—C10—C11120.81 (17)
C3—C2—C1117.20 (19)C15—C10—N3108.47 (14)
C3—C2—H2121.4C11—C10—N3130.70 (16)
C1—C2—H2121.4C12—C11—C10117.53 (19)
C2—C3—C4121.7 (2)C12—C11—H11121.2
C2—C3—H3119.2C10—C11—H11121.2
C4—C3—H3119.2C11—C12—C13121.4 (2)
C5—C4—C3121.6 (2)C11—C12—H12119.3
C5—C4—H4119.2C13—C12—H12119.3
C3—C4—H4119.2C14—C13—C12121.72 (19)
C4—C5—C6117.7 (2)C14—C13—H13119.1
C4—C5—H5121.2C12—C13—H13119.1
C6—C5—H5121.2C13—C14—C15117.08 (19)
C1—C6—C5120.44 (18)C13—C14—H14121.5
C1—C6—N1108.32 (14)C15—C14—H14121.5
C5—C6—N1131.25 (18)N4—C15—C10106.27 (14)
N1—C7—N2112.69 (14)N4—C15—C14132.23 (17)
N1—C7—C8124.49 (15)C10—C15—C14121.46 (17)
C7—N2—C1—C60.26 (19)C10—N3—C9—N40.06 (17)
C7—N2—C1—C2179.9 (2)C10—N3—C9—C8176.91 (14)
N2—C1—C2—C3179.9 (2)C15—N4—C9—N30.03 (17)
C6—C1—C2—C30.3 (3)C15—N4—C9—C8176.87 (14)
C1—C2—C3—C41.0 (4)C7—C8—C9—N3131.44 (16)
C2—C3—C4—C50.9 (5)C7—C8—C9—N452.1 (2)
C3—C4—C5—C60.2 (5)C9—N3—C10—C150.06 (17)
N2—C1—C6—C5179.3 (2)C9—N3—C10—C11178.29 (18)
C2—C1—C6—C50.4 (3)C15—C10—C11—C120.3 (3)
N2—C1—C6—N10.4 (2)N3—C10—C11—C12177.74 (17)
C2—C1—C6—N1179.91 (18)C10—C11—C12—C130.2 (3)
C4—C5—C6—C10.4 (4)C11—C12—C13—C140.7 (3)
C4—C5—C6—N1179.9 (3)C12—C13—C14—C150.5 (3)
C7—N1—C6—C10.4 (2)C9—N4—C15—C100.01 (16)
C7—N1—C6—C5179.3 (3)C9—N4—C15—C14177.71 (17)
C6—N1—C7—N20.2 (2)C11—C10—C15—N4178.48 (15)
C6—N1—C7—C8178.84 (16)N3—C10—C15—N40.04 (17)
C1—N2—C7—N10.0 (2)C11—C10—C15—C140.5 (2)
C1—N2—C7—C8179.10 (15)N3—C10—C15—C14177.98 (14)
N1—C7—C8—C981.0 (2)C13—C14—C15—N4177.49 (17)
N2—C7—C8—C997.94 (19)C13—C14—C15—C100.1 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N3i0.861.942.7869 (18)169
N4—H4A···N1ii0.862.002.823 (2)160
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1/2, z.

Experimental details

Crystal data
Chemical formulaC15H12N4
Mr248.29
Crystal system, space groupTetragonal, I41/a
Temperature (K)298
a, c (Å)18.296 (4), 15.728 (3)
V3)5264.6 (18)
Z16
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.40 × 0.31 × 0.27
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.950, 0.979
No. of measured, independent and
observed [I > 2σ(I)] reflections
10662, 2307, 1798
Rint0.035
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.042, 0.130, 1.00
No. of reflections2307
No. of parameters172
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.20, 0.16

Computer programs: SMART (Bruker, 1998), SAINT (Bruker, 1999), SAINT, SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1999), SHELXTL.

Selected geometric parameters (Å, º) top
N1—C71.312 (2)N3—C101.388 (2)
N1—C61.391 (2)N4—C91.340 (2)
N2—C71.333 (2)N4—C151.381 (2)
N2—C11.370 (2)C7—C81.491 (2)
N3—C91.315 (2)C8—C91.493 (2)
C7—N1—C6105.43 (14)C9—N4—C15106.79 (13)
C7—N2—C1106.98 (13)C7—C8—C9114.19 (14)
C9—N3—C10105.81 (13)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···N3i0.861.942.7869 (18)169
N4—H4A···N1ii0.862.002.823 (2)160
Symmetry codes: (i) x+1, y+1, z; (ii) x+1, y+1/2, z.
 

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