supplementary materials


HTML versionpdf versioncif file3d viewstructure factorssupplementary materialsCIF check reportsimilar papers Open access

zs2214 scheme

Acta Cryst. (2012). E68, o2618    [ doi:10.1107/S1600536812032485 ]

4-[4-(1H-Imidazol-4-yl)phenyl]-1H-imidazole

Q. Wang and X.-L. Zhao

Abstract top

In the molecule of the title compound, C12H10N4, the two imidazole substituents are related by inversion symmetry and each forms a dihedral angle of 25.02 (8)° with the benzene ring. In the crystal, molecules are linked through N-H...N hydrogen bonds, forming cyclic units [graph-set R44(28)], which generate a layered structure extending across (011).

Comment top

Intense interest in the chemistry of metal-organic frameworks stems from their intriguing structural features and potential applications in catalysis, adsorption, luminescence, etc. The title compound C12H10N4 was designed and synthesized to enable the construction of metal-organic frameworks because of its versatile coordination modes in respect to metal complexation. In the structure of this compound (Fig. 1), the molecule has inversion symmetry with the two imidazole moieties rotated slightly out of the plane of the benzene ring [dihedral angle, 25.02 (8)°]. In the crystal, the molecules are linked through N—H···N hydrogen bonds (Table 1), forming inter-associated cyclic units [graph set R44(28)] which generate a two-dimensional layered structure extending across (011) (Fig. 2).

Related literature top

For the synthesis of the title compound, see: Petersen (1950); Huisman (1997); Have (1997). For a similar structure, see: Gao & Duan (2012). For graph-set analysis, see: Etter et al. (1990).

Experimental top

The title compound was synthesized according to literature methods (Petersen, 1950; Huisman, 1997; Have, 1997). A single crystal suitable for the X-ray diffraction study was obtained serendipitously in an attempt to synthesize a LaIII complex. A mixture of 5-(4-(1H-imidazol-5-yl)phenyl)-1H-imidazole and lanthanum(III) nitrate hexahydrate in water was subjected to hydrothermal conditions at 85 °C for three days and then cooled to room temperature to give colorless crystals of the title compound.

Refinement top

The hydrogen atom on the N atom was located in a difference-Fourier map and refined isotropically. The other H atoms were positioned with idealized geometry (C—H = 0.93 Å) and allowed to ride, with Uiso(H) = 1.2 Ueq(C).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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) and local programs.

Figures top
[Figure 1] Fig. 1. Molecular conformation and atom-numbering scheme for the title compound, with probability ellipsoids drawn at the 50% level. For symmetry code (1): -x, -y + 2, -z.
[Figure 2] Fig. 2. The two-dimensional layered structure of the title compound viewed down a.
4-[4-(1H-Imidazol-4-yl)phenyl]-1H-imidazole top
Crystal data top
C12H10N4F(000) = 440
Mr = 210.24Dx = 1.307 Mg m−3
Orthorhombic, PbcaMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 2852 reflections
a = 6.8604 (2) Åθ = 2.5–23.0°
b = 9.4534 (3) ŵ = 0.08 mm−1
c = 16.4789 (6) ÅT = 296 K
V = 1068.72 (6) Å3Block, colorless
Z = 40.40 × 0.35 × 0.30 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		932 independent reflections
Radiation source: fine-focus sealed tube746 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.035
φ and ω scansθmax = 25.0°, θmin = 3.9°
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −8→8
Tmin = 0.967, Tmax = 0.975k = −11→11
11170 measured reflectionsl = −19→19
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)] = 0.032Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.096H atoms treated by a mixture of independent and constrained refinement
S = 1.07 w = 1/[σ2(Fo2) + (0.0539P)2 + 0.1236P]
where P = (Fo2 + 2Fc2)/3
932 reflections(Δ/σ)max < 0.001
77 parametersΔρmax = 0.11 e Å−3
0 restraintsΔρmin = −0.13 e Å−3
Crystal data top
C12H10N4V = 1068.72 (6) Å3
Mr = 210.24Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 6.8604 (2) ŵ = 0.08 mm−1
b = 9.4534 (3) ÅT = 296 K
c = 16.4789 (6) Å0.40 × 0.35 × 0.30 mm
Data collection top
Bruker SMART CCD area-detector
diffractometer		932 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		746 reflections with I > 2σ(I)
Tmin = 0.967, Tmax = 0.975Rint = 0.035
11170 measured reflectionsθmax = 25.0°
Refinement top
R[F2 > 2σ(F2)] = 0.032H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.096Δρmax = 0.11 e Å−3
S = 1.07Δρmin = −0.13 e Å−3
932 reflectionsAbsolute structure: ?
77 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
N1−0.04339 (18)0.62662 (12)0.21679 (8)0.0486 (4)
N20.03252 (17)0.85297 (11)0.21277 (7)0.0465 (3)
C10.0142 (2)0.74017 (14)0.25866 (10)0.0505 (4)
H1A0.03870.73940.31420.061*
C2−0.0646 (2)0.66854 (14)0.13827 (9)0.0459 (4)
H2A−0.10350.61250.09480.055*
C3−0.01772 (19)0.80895 (14)0.13570 (8)0.0402 (3)
C4−0.01031 (18)0.90577 (13)0.06630 (8)0.0398 (4)
C5−0.1213 (2)0.88440 (13)−0.00307 (8)0.0465 (4)
H5A−0.20380.8065−0.00590.056*
C60.1116 (2)1.02373 (13)0.06775 (8)0.0461 (4)
H6A0.18791.04070.11340.055*
H1B−0.054 (3)0.5309 (18)0.2395 (11)0.081 (5)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0551 (7)0.0350 (6)0.0558 (8)0.0034 (5)0.0020 (6)0.0067 (6)
N20.0532 (7)0.0382 (6)0.0483 (7)−0.0007 (5)−0.0064 (5)0.0016 (5)
C10.0568 (9)0.0458 (8)0.0490 (9)0.0034 (7)−0.0077 (6)0.0040 (7)
C20.0524 (8)0.0376 (7)0.0477 (9)−0.0004 (6)0.0043 (6)−0.0035 (6)
C30.0402 (7)0.0346 (7)0.0458 (8)0.0014 (5)0.0024 (6)−0.0020 (6)
C40.0423 (7)0.0327 (7)0.0442 (8)0.0004 (5)0.0044 (6)−0.0033 (5)
C50.0523 (8)0.0383 (7)0.0488 (8)−0.0125 (6)0.0001 (6)−0.0032 (6)
C60.0504 (8)0.0440 (7)0.0441 (8)−0.0093 (6)−0.0029 (6)−0.0017 (6)
Geometric parameters (Å, º) top
N1—C11.3359 (17)C2—H2A0.9300
N1—C21.3611 (19)C3—C41.4657 (18)
N1—H1B0.981 (17)C4—C51.3883 (19)
N2—C11.3133 (17)C4—C61.3940 (18)
N2—C31.3801 (18)C5—C6i1.3766 (17)
C1—H1A0.9300C5—H5A0.9300
C2—C31.3665 (19)C6—H6A0.9300
C1—N1—C2106.79 (12)C2—C3—C4129.71 (12)
C1—N1—H1B124.5 (11)N2—C3—C4121.40 (11)
C2—N1—H1B128.5 (11)C5—C4—C6117.36 (12)
C1—N2—C3105.14 (11)C5—C4—C3122.18 (12)
N2—C1—N1112.54 (14)C6—C4—C3120.46 (12)
N2—C1—H1A123.7C6i—C5—C4121.28 (12)
N1—C1—H1A123.7C6i—C5—H5A119.4
N1—C2—C3106.67 (12)C4—C5—H5A119.4
N1—C2—H2A126.7C5i—C6—C4121.36 (12)
C3—C2—H2A126.7C5i—C6—H6A119.3
C2—C3—N2108.86 (12)C4—C6—H6A119.3
C3—N2—C1—N10.22 (16)N2—C3—C4—C5−156.22 (12)
C2—N1—C1—N2−0.19 (16)C2—C3—C4—C6−153.60 (14)
C1—N1—C2—C30.07 (15)N2—C3—C4—C624.22 (18)
N1—C2—C3—N20.06 (15)C6—C4—C5—C6i−0.1 (2)
N1—C2—C3—C4178.10 (13)C3—C4—C5—C6i−179.71 (13)
C1—N2—C3—C2−0.17 (15)C5—C4—C6—C5i0.1 (2)
C1—N2—C3—C4−178.40 (12)C3—C4—C6—C5i179.72 (12)
C2—C3—C4—C526.0 (2)
Symmetry code: (i) −x, −y+2, −z.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···N2ii0.981 (17)1.863 (18)2.8364 (17)170.8 (17)
Symmetry code: (ii) −x, y−1/2, −z+1/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···N2i0.981 (17)1.863 (18)2.8364 (17)170.8 (17)
Symmetry code: (i) −x, y−1/2, −z+1/2.
Acknowledgements top

The authors thank the National Natural Science Foundation of China (NSFC No. 20801018), Shanghai Education Development Foundation (grant No. 2008 CG31) and the Shanghai Rising-Star Program (10QA1402000) for financial support.

references
References top

Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.

Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.

Gao, G.-R. & Duan, W.-H. (2012). Acta Cryst. E68, o1977.

Have, R. (1997). Tetrahedron, 53, 11355–11368.

Huisman, M. (1997). Synth. Commun. 27, 945–952

Petersen, S. (1950). Chem. Ber. 83, 551–558.

Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.