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

Wang, Q.; Zhao, X.-L.

doi:10.1107/S1600536812032485

organic compounds

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ISSN: 2056-9890

Volume 68| Part 9| September 2012| Page o2618

doi:10.1107/S1600536812032485

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

Qian Wang ^a and Xiao-Li Zhao ^a ^*

^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 ); Huisman (1997 ); Have (1997 ). For a similar structure, see: Gao & Duan (2012 ). For graph-set analysis, see: Etter et al. (1990 ).

Experimental

Crystal data

C₁₂H₁₀N₄
M_r = 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 ) T_min = 0.967, T_max = 0.975
11170 measured reflections
932 independent reflections
746 reflections with I > 2σ(I)
R_int = 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
Δρ_max = 0.11 e Å⁻³
Δρ_min = −0.13 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	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 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; 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 and local programs.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812032485/zs2214sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812032485/zs2214Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812032485/zs2214Isup3.cml

checkCIF report

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 La^III 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.

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

	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.
	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

C₁₂H₁₀N₄	F(000) = 440
M_r = 210.24	D_x = 1.307 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2852 reflections
a = 6.8604 (2) Å	θ = 2.5–23.0°
b = 9.4534 (3) Å	µ = 0.08 mm⁻¹
c = 16.4789 (6) Å	T = 296 K
V = 1068.72 (6) Å³	Block, colorless
Z = 4	0.40 × 0.35 × 0.30 mm

Data collection top

Bruker SMART CCD area-detector diffractometer	932 independent reflections
Radiation source: fine-focus sealed tube	746 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.035
ϕ and ω scans	θ_max = 25.0°, θ_min = 3.9°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −8→8
T_min = 0.967, T_max = 0.975	k = −11→11
11170 measured reflections	l = −19→19

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)] = 0.032	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ²(F_o²) + (0.0539P)² + 0.1236P] where P = (F_o² + 2F_c²)/3
932 reflections	(Δ/σ)_max < 0.001
77 parameters	Δρ_max = 0.11 e Å⁻³
0 restraints	Δρ_min = −0.13 e Å⁻³

Crystal data top

C₁₂H₁₀N₄	V = 1068.72 (6) Å³
M_r = 210.24	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 6.8604 (2) Å	µ = 0.08 mm⁻¹
b = 9.4534 (3) Å	T = 296 K
c = 16.4789 (6) Å	0.40 × 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)
T_min = 0.967, T_max = 0.975	R_int = 0.035
11170 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.032	0 restraints
wR(F²) = 0.096	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	Δρ_max = 0.11 e Å⁻³
932 reflections	Δρ_min = −0.13 e Å⁻³
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

	x	y	z	U_iso*/U_eq
N1	−0.04339 (18)	0.62662 (12)	0.21679 (8)	0.0486 (4)
N2	0.03252 (17)	0.85297 (11)	0.21277 (7)	0.0465 (3)
C1	0.0142 (2)	0.74017 (14)	0.25866 (10)	0.0505 (4)
H1A	0.0387	0.7394	0.3142	0.061*
C2	−0.0646 (2)	0.66854 (14)	0.13827 (9)	0.0459 (4)
H2A	−0.1035	0.6125	0.0948	0.055*
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	−0.2038	0.8065	−0.0059	0.056*
C6	0.1116 (2)	1.02373 (13)	0.06775 (8)	0.0461 (4)
H6A	0.1879	1.0407	0.1134	0.055*
H1B	−0.054 (3)	0.5309 (18)	0.2395 (11)	0.081 (5)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0551 (7)	0.0350 (6)	0.0558 (8)	0.0034 (5)	0.0020 (6)	0.0067 (6)
N2	0.0532 (7)	0.0382 (6)	0.0483 (7)	−0.0007 (5)	−0.0064 (5)	0.0016 (5)
C1	0.0568 (9)	0.0458 (8)	0.0490 (9)	0.0034 (7)	−0.0077 (6)	0.0040 (7)
C2	0.0524 (8)	0.0376 (7)	0.0477 (9)	−0.0004 (6)	0.0043 (6)	−0.0035 (6)
C3	0.0402 (7)	0.0346 (7)	0.0458 (8)	0.0014 (5)	0.0024 (6)	−0.0020 (6)
C4	0.0423 (7)	0.0327 (7)	0.0442 (8)	0.0004 (5)	0.0044 (6)	−0.0033 (5)
C5	0.0523 (8)	0.0383 (7)	0.0488 (8)	−0.0125 (6)	0.0001 (6)	−0.0032 (6)
C6	0.0504 (8)	0.0440 (7)	0.0441 (8)	−0.0093 (6)	−0.0029 (6)	−0.0017 (6)

Geometric parameters (Å, º) top

N1—C1	1.3359 (17)	C2—H2A	0.9300
N1—C2	1.3611 (19)	C3—C4	1.4657 (18)
N1—H1B	0.981 (17)	C4—C5	1.3883 (19)
N2—C1	1.3133 (17)	C4—C6	1.3940 (18)
N2—C3	1.3801 (18)	C5—C6ⁱ	1.3766 (17)
C1—H1A	0.9300	C5—H5A	0.9300
C2—C3	1.3665 (19)	C6—H6A	0.9300

C1—N1—C2	106.79 (12)	C2—C3—C4	129.71 (12)
C1—N1—H1B	124.5 (11)	N2—C3—C4	121.40 (11)
C2—N1—H1B	128.5 (11)	C5—C4—C6	117.36 (12)
C1—N2—C3	105.14 (11)	C5—C4—C3	122.18 (12)
N2—C1—N1	112.54 (14)	C6—C4—C3	120.46 (12)
N2—C1—H1A	123.7	C6ⁱ—C5—C4	121.28 (12)
N1—C1—H1A	123.7	C6ⁱ—C5—H5A	119.4
N1—C2—C3	106.67 (12)	C4—C5—H5A	119.4
N1—C2—H2A	126.7	C5ⁱ—C6—C4	121.36 (12)
C3—C2—H2A	126.7	C5ⁱ—C6—H6A	119.3
C2—C3—N2	108.86 (12)	C4—C6—H6A	119.3

C3—N2—C1—N1	0.22 (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—C3	0.07 (15)	N2—C3—C4—C6	24.22 (18)
N1—C2—C3—N2	0.06 (15)	C6—C4—C5—C6ⁱ	−0.1 (2)
N1—C2—C3—C4	178.10 (13)	C3—C4—C5—C6ⁱ	−179.71 (13)
C1—N2—C3—C2	−0.17 (15)	C5—C4—C6—C5ⁱ	0.1 (2)
C1—N2—C3—C4	−178.40 (12)	C3—C4—C6—C5ⁱ	179.72 (12)
C2—C3—C4—C5	26.0 (2)

Symmetry code: (i) −x, −y+2, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···N2ⁱⁱ	0.981 (17)	1.863 (18)	2.8364 (17)	170.8 (17)

Symmetry code: (ii) −x, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₀N₄
M_r	210.24
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	6.8604 (2), 9.4534 (3), 16.4789 (6)
V (Å³)	1068.72 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.40 × 0.35 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.967, 0.975
No. of measured, independent and observed [I > 2σ(I)] reflections	11170, 932, 746
R_int	0.035
(sin θ/λ)_max (Å⁻¹)	0.594

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.032, 0.096, 1.07
No. of reflections	932
No. of parameters	77
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	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···A	D—H	H···A	D···A	D—H···A
N1—H1B···N2ⁱ	0.981 (17)	1.863 (18)	2.8364 (17)	170.8 (17)

Symmetry code: (i) −x, y−1/2, −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

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