organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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ISSN: 2056-9890

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

aShanghai Key Laboratory of Green Chemistry and Chemical Processes, Department of Chemistry, East China Normal University, 3663 North Zhongshan Road, Shanghai 200062, People's Republic of China
*Correspondence e-mail: xlzhao@chem.ecnu.edu.cn

(Received 4 June 2012; accepted 17 July 2012; online 1 August 2012)

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).

Related literature

For the synthesis of the title compound, see: Petersen (1950[Petersen, S. (1950). Chem. Ber. 83, 551-558.]); Huisman (1997[Huisman, M. (1997). Synth. Commun. 27, 945-952.]); Have (1997[Have, R. (1997). Tetrahedron, 53, 11355-11368.]). For a similar structure, see: Gao & Duan (2012[Gao, G.-R. & Duan, W.-H. (2012). Acta Cryst. E68, o1977.]). For graph-set analysis, see: Etter et al. (1990[Etter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256-262.]).

[Scheme 1]

Experimental

Crystal data
  • C12H10N4

  • Mr = 210.24

  • Orthorhombic, P b c a

  • a = 6.8604 (2) Å

  • b = 9.4534 (3) Å

  • c = 16.4789 (6) Å

  • V = 1068.72 (6) Å3

  • Z = 4

  • Mo Kα radiation

  • μ = 0.08 mm−1

  • T = 296 K

  • 0.40 × 0.35 × 0.30 mm

Data collection
  • Bruker SMART CCD area-detector diffractometer

  • Absorption correction: multi-scan (SADABS; Sheldrick, 1996[Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.]) Tmin = 0.967, Tmax = 0.975

  • 11170 measured reflections

  • 932 independent reflections

  • 746 reflections with I > 2σ(I)

  • Rint = 0.035

Refinement
  • R[F2 > 2σ(F2)] = 0.032

  • wR(F2) = 0.096

  • S = 1.07

  • 932 reflections

  • 77 parameters

  • H atoms treated by a mixture of independent and constrained refinement

  • Δρmax = 0.11 e Å−3

  • Δρmin = −0.13 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
N1—H1B⋯N2i 0.981 (17) 1.863 (18) 2.8364 (17) 170.8 (17)
Symmetry code: (i) [-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}].

Data collection: SMART (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL and local programs.

Supporting information


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 m3
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 mm1
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 = 88
Tmin = 0.967, Tmax = 0.975k = 1111
11170 measured reflectionsl = 1919
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 Å3
0 restraintsΔρmin = 0.13 e Å3
Crystal data top
C12H10N4V = 1068.72 (6) Å3
Mr = 210.24Z = 4
Orthorhombic, PbcaMo Kα radiation
a = 6.8604 (2) ŵ = 0.08 mm1
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 reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0320 restraints
wR(F2) = 0.096H atoms treated by a mixture of independent and constrained refinement
S = 1.07Δρmax = 0.11 e Å3
932 reflectionsΔρmin = 0.13 e Å3
77 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
N10.04339 (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*
C20.0646 (2)0.66854 (14)0.13827 (9)0.0459 (4)
H2A0.10350.61250.09480.055*
C30.01772 (19)0.80895 (14)0.13570 (8)0.0402 (3)
C40.01031 (18)0.90577 (13)0.06630 (8)0.0398 (4)
C50.1213 (2)0.88440 (13)0.00307 (8)0.0465 (4)
H5A0.20380.80650.00590.056*
C60.1116 (2)1.02373 (13)0.06775 (8)0.0461 (4)
H6A0.18791.04070.11340.055*
H1B0.054 (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—C5156.22 (12)
C2—N1—C1—N20.19 (16)C2—C3—C4—C6153.60 (14)
C1—N1—C2—C30.07 (15)N2—C3—C4—C624.22 (18)
N1—C2—C3—N20.06 (15)C6—C4—C5—C6i0.1 (2)
N1—C2—C3—C4178.10 (13)C3—C4—C5—C6i179.71 (13)
C1—N2—C3—C20.17 (15)C5—C4—C6—C5i0.1 (2)
C1—N2—C3—C4178.40 (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, y1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC12H10N4
Mr210.24
Crystal system, space groupOrthorhombic, Pbca
Temperature (K)296
a, b, c (Å)6.8604 (2), 9.4534 (3), 16.4789 (6)
V3)1068.72 (6)
Z4
Radiation typeMo Kα
µ (mm1)0.08
Crystal size (mm)0.40 × 0.35 × 0.30
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correctionMulti-scan
(SADABS; Sheldrick, 1996)
Tmin, Tmax0.967, 0.975
No. of measured, independent and
observed [I > 2σ(I)] reflections
11170, 932, 746
Rint0.035
(sin θ/λ)max1)0.594
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.032, 0.096, 1.07
No. of reflections932
No. of parameters77
H-atom treatmentH atoms treated by a mixture of independent and constrained refinement
Δρmax, Δρmin (e Å3)0.11, 0.13

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008) and local programs.

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, y1/2, z+1/2.
 

Acknowledgements

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

First citationBruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
First citationEtter, M. C., MacDonald, J. C. & Bernstein, J. (1990). Acta Cryst. B46, 256–262.  CrossRef CAS Web of Science IUCr Journals
First citationGao, G.-R. & Duan, W.-H. (2012). Acta Cryst. E68, o1977.  CSD CrossRef IUCr Journals
First citationHave, R. (1997). Tetrahedron, 53, 11355–11368.
First citationHuisman, M. (1997). Synth. Commun. 27, 945–952.  CrossRef CAS Web of Science
First citationPetersen, S. (1950). Chem. Ber. 83, 551–558.  CrossRef CAS Web of Science
First citationSheldrick, G. M. (1996). SADABS. University of Göttingen, Germany.
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals

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ISSN: 2056-9890
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