2,2′-(Ethane-1,2-di­yl)bis­(1H-benzimidazole)

Chen, X.; Wu, X.-Y.; Zhao, G.-L.

doi:10.1107/S1600536812013839

organic compounds

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Volume 68| Part 5| May 2012| Page o1321

doi:10.1107/S1600536812013839

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2,2′-(Ethane-1,2-diyl)bis(1H-benzimidazole)

Xu Chen,^a Xiao-Yong Wu ^b and Guo-Liang Zhao ^a,^b ^*

^aZhejiang Normal University Xingzhi College, Jinhua, Zhejiang 321004, People's Republic of China, and ^bCollege of Chemistry and Life Sciences, Zhejiang Normal University, Jinhua 321004, Zhejiang, People's Republic of China
^*Correspondence e-mail: sky53@zjnu.cn

(Received 16 March 2012; accepted 30 March 2012; online 6 April 2012)

The complete molecule of the title compound, C₁₆H₁₄N₄, is generated by crystallographic inversion symmetry. In the crystal, molecules are linked by N—H⋯N hydrogen bonds, generating (001) sheets. Weak aromatic π–π stacking interactions [centroid–centroid distances = 3.7383 (13) and 3.7935 (14) Å] are also observed.

Related literature

For background to metal-organic frameworks, see: van Albada et al. (2007 ). For the synthesis, see: Wang & Joulli (1957 ).

Experimental

Crystal data

C₁₆H₁₄N₄
M_r = 262.31
Orthorhombic, P b c a
a = 8.4295 (18) Å
b = 9.924 (2) Å
c = 15.351 (4) Å
V = 1284.2 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 296 K
0.32 × 0.25 × 0.19 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ) T_min = 0.975, T_max = 0.984
10702 measured reflections
1475 independent reflections
966 reflections with I > 2σ(I)
R_int = 0.052

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.122
S = 1.02
1475 reflections
91 parameters
H-atom parameters constrained
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2B⋯N1ⁱ	0.86	2.04	2.8568 (18)	159
Symmetry code: (i) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2006 ); cell refinement: SAINT (Bruker, 2006); 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: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536812013839/hb6688sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812013839/hb6688Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812013839/hb6688Isup3.cml

checkCIF report

Comment top

We present a polyaromatic compoud (1) that contains multiple functional groups that can develop a series of metal-organic frameworks with potential applications (e.g. van Albada et al. (2007)). The molecular struture of (1), shown in Fig.1, consists of two symmetrical benzimidazole rings. The two benzimidazolyl rings are nearly parallel, witha dihedral angle of 2.645 (6)° between them. Molecules are linked via a network of hydrogen bonds (N2—H2B···N1; Table 2). π–π stacking interactions are observed between nearly parallel benzimidazolyl benzene rings. The centroid-to-centroid distance between C1—C6 benzene rings is 3.7379 Å, while between C1A—C6A benzene rings it is 3.7944 Å (the symmetry operation: -x + 1,-y,-z). The hydrogen bonds and π–π weak non-covalent interactions lend stability to the structure. The stacking plot of this compound was shown in Fig. 2.

Related literature top

For background to metal-organic frameworks, see: van Albada et al. (2007). For the synthesis, see: Wang & Joulli (1957).

Experimental top

ο-Phenylenediamine (1.081 g, 10 mmol) and succinic acid (0.590 g, 5 mmol) were refluxed for 4 h in 30 ml of 10% hydrochloric acid solution. The reaction mixture was cooled to room temperature, the precipitation that formed was filtered and then recrystallized from water. The colourless crystals were obtained from water after a week (Wang et al., 1957).

Computing details top

Data collection: APEX2 (Bruker, 2006); cell refinement: SAINT (Bruker, 2006); data reduction: SAINT (Bruker, 2006); 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: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of the title compound with displacement ellipsoids drawn at the 30% probability level. Atoms with suffix A are at the symmetry position (1–x, 1–y, –z).
	Fig. 2. The stacking plot of the title compound, showing H-bond interactions (dashed lines) and π–π stacking interactions.

2,2'-(Ethane-1,2-diyl)bis(1H-benzimidazole) top

Crystal data top

C₁₆H₁₄N₄	F(000) = 552
M_r = 262.31	D_x = 1.357 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	θ = 2.7–27.6°
a = 8.4295 (18) Å	µ = 0.08 mm⁻¹
b = 9.924 (2) Å	T = 296 K
c = 15.351 (4) Å	Block, colourless
V = 1284.2 (5) Å³	0.32 × 0.25 × 0.19 mm
Z = 4

Data collection top

Bruker APEXII CCD diffractometer	1475 independent reflections
Radiation source: fine-focus sealed tube	966 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.052
phi and ω scans	θ_max = 27.6°, θ_min = 2.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −10→10
T_min = 0.975, T_max = 0.984	k = −12→12
10702 measured reflections	l = −19→16

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)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.122	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0554P)² + 0.2274P] where P = (F_o² + 2F_c²)/3
1475 reflections	(Δ/σ)_max < 0.001
91 parameters	Δρ_max = 0.15 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₆H₁₄N₄	V = 1284.2 (5) Å³
M_r = 262.31	Z = 4
Orthorhombic, Pbca	Mo Kα radiation
a = 8.4295 (18) Å	µ = 0.08 mm⁻¹
b = 9.924 (2) Å	T = 296 K
c = 15.351 (4) Å	0.32 × 0.25 × 0.19 mm

Data collection top

Bruker APEXII CCD diffractometer	1475 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	966 reflections with I > 2σ(I)
T_min = 0.975, T_max = 0.984	R_int = 0.052
10702 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.122	H-atom parameters constrained
S = 1.02	Δρ_max = 0.15 e Å⁻³
1475 reflections	Δρ_min = −0.21 e Å⁻³
91 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
N2	0.18376 (15)	0.39276 (12)	0.06131 (8)	0.0378 (4)
H2B	0.1935	0.3084	0.0498	0.045*
N1	0.23667 (16)	0.61293 (12)	0.06218 (9)	0.0402 (4)
C5	0.09915 (18)	0.58969 (15)	0.11024 (10)	0.0357 (4)
C8	0.28216 (19)	0.49246 (14)	0.03497 (11)	0.0375 (4)
C4	0.06495 (18)	0.45137 (15)	0.11012 (10)	0.0354 (4)
C7	0.42738 (19)	0.46475 (17)	−0.01726 (12)	0.0452 (4)
H7A	0.4092	0.4932	−0.0769	0.054*
H7B	0.4467	0.3684	−0.0178	0.054*
C3	−0.0631 (2)	0.39827 (18)	0.15503 (11)	0.0475 (5)
H3A	−0.0860	0.3066	0.1537	0.057*
C6	0.0040 (2)	0.67805 (16)	0.15747 (11)	0.0461 (5)
H6A	0.0247	0.7701	0.1581	0.055*
C2	−0.1552 (2)	0.48740 (18)	0.20187 (12)	0.0524 (5)
H2A	−0.2416	0.4551	0.2333	0.063*
C1	−0.1215 (2)	0.62512 (18)	0.20317 (12)	0.0520 (5)
H1A	−0.1856	0.6824	0.2357	0.062*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N2	0.0346 (8)	0.0281 (6)	0.0506 (8)	0.0003 (5)	0.0010 (6)	−0.0046 (6)
N1	0.0373 (8)	0.0317 (7)	0.0515 (8)	−0.0013 (5)	0.0053 (6)	−0.0039 (6)
C5	0.0323 (9)	0.0347 (8)	0.0402 (9)	0.0015 (7)	−0.0014 (7)	0.0005 (6)
C8	0.0328 (9)	0.0329 (8)	0.0469 (9)	−0.0014 (6)	−0.0024 (7)	−0.0044 (7)
C4	0.0326 (9)	0.0330 (8)	0.0407 (9)	0.0013 (6)	−0.0027 (7)	−0.0005 (6)
C7	0.0343 (9)	0.0450 (9)	0.0563 (11)	−0.0019 (7)	0.0050 (8)	−0.0102 (8)
C3	0.0458 (11)	0.0432 (9)	0.0537 (10)	−0.0071 (8)	0.0034 (9)	0.0023 (8)
C6	0.0473 (11)	0.0371 (9)	0.0541 (11)	0.0069 (8)	0.0020 (9)	−0.0036 (7)
C2	0.0435 (11)	0.0626 (12)	0.0512 (11)	−0.0013 (9)	0.0105 (9)	0.0027 (9)
C1	0.0458 (11)	0.0571 (11)	0.0529 (11)	0.0130 (9)	0.0083 (9)	−0.0057 (9)

Geometric parameters (Å, º) top

N2—C8	1.3530 (19)	C7—H7A	0.9700
N2—C4	1.3795 (19)	C7—H7B	0.9700
N2—H2B	0.8600	C3—C2	1.379 (2)
N1—C8	1.3233 (18)	C3—H3A	0.9300
N1—C5	1.393 (2)	C6—C1	1.374 (2)
C5—C6	1.392 (2)	C6—H6A	0.9300
C5—C4	1.403 (2)	C2—C1	1.396 (2)
C8—C7	1.489 (2)	C2—H2A	0.9300
C4—C3	1.385 (2)	C1—H1A	0.9300
C7—C7ⁱ	1.506 (3)

C8—N2—C4	107.40 (12)	C8—C7—H7B	109.0
C8—N2—H2B	126.3	C7ⁱ—C7—H7B	109.0
C4—N2—H2B	126.3	H7A—C7—H7B	107.8
C8—N1—C5	104.99 (12)	C2—C3—C4	117.01 (16)
C6—C5—N1	130.61 (14)	C2—C3—H3A	121.5
C6—C5—C4	119.91 (15)	C4—C3—H3A	121.5
N1—C5—C4	109.41 (13)	C1—C6—C5	117.96 (15)
N1—C8—N2	112.88 (14)	C1—C6—H6A	121.0
N1—C8—C7	125.11 (14)	C5—C6—H6A	121.0
N2—C8—C7	122.00 (13)	C3—C2—C1	121.40 (17)
N2—C4—C3	132.51 (15)	C3—C2—H2A	119.3
N2—C4—C5	105.32 (13)	C1—C2—H2A	119.3
C3—C4—C5	122.14 (15)	C6—C1—C2	121.57 (16)
C8—C7—C7ⁱ	113.14 (16)	C6—C1—H1A	119.2
C8—C7—H7A	109.0	C2—C1—H1A	119.2
C7ⁱ—C7—H7A	109.0

C8—N1—C5—C6	176.72 (17)	N1—C5—C4—C3	178.13 (14)
C8—N1—C5—C4	−0.20 (18)	N1—C8—C7—C7ⁱ	46.1 (3)
C5—N1—C8—N2	0.41 (18)	N2—C8—C7—C7ⁱ	−132.3 (2)
C5—N1—C8—C7	−178.13 (15)	N2—C4—C3—C2	176.40 (16)
C4—N2—C8—N1	−0.47 (19)	C5—C4—C3—C2	−1.2 (2)
C4—N2—C8—C7	178.12 (14)	N1—C5—C6—C1	−176.40 (16)
C8—N2—C4—C3	−177.62 (17)	C4—C5—C6—C1	0.2 (2)
C8—N2—C4—C5	0.31 (17)	C4—C3—C2—C1	0.6 (3)
C6—C5—C4—N2	−177.37 (14)	C5—C6—C1—C2	−0.9 (3)
N1—C5—C4—N2	−0.07 (17)	C3—C2—C1—C6	0.4 (3)
C6—C5—C4—C3	0.8 (2)

Symmetry code: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2B···N1ⁱⁱ	0.86	2.04	2.8568 (18)	159

Symmetry code: (ii) −x+1/2, y−1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₆H₁₄N₄
M_r	262.31
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	296
a, b, c (Å)	8.4295 (18), 9.924 (2), 15.351 (4)
V (Å³)	1284.2 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.32 × 0.25 × 0.19

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.975, 0.984
No. of measured, independent and observed [I > 2σ(I)] reflections	10702, 1475, 966
R_int	0.052
(sin θ/λ)_max (Å⁻¹)	0.651

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.122, 1.02
No. of reflections	1475
No. of parameters	91
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.15, −0.21

Computer programs: APEX2 (Bruker, 2006), SAINT (Bruker, 2006), 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
N2—H2B···N1ⁱ	0.86	2.04	2.8568 (18)	159

Symmetry code: (i) −x+1/2, y−1/2, z.

References

Albada, G. A. van, Mutikainen, I., Turpeinen, U. & Reedijk, J. (2007). J. Chem. Cryst. 37, 489–496. Web of Science CSD CrossRef Google Scholar
Bruker (2006). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Wang, L. L.-Y. & Joulli, M. M. (1957). J. Am. Chem. Soc. 79, 5706–5708. CrossRef CAS Web of Science Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 68| Part 5| May 2012| Page o1321

doi:10.1107/S1600536812013839

Open

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