Dimethyl 2,2′-[2,2′-bi(1H-1,3-benzimidazole)-1,1′-di­yl]diacetate

Guo, H.-L.; Liu, J.-C.; Xiao, C.-H.; Pang, T.; Cao, P.

doi:10.1107/S1600536812032266

organic compounds

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ISSN: 2056-9890

Volume 68| Part 8| August 2012| Page o2512

https://doi.org/10.1107/S1600536812032266

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Dimethyl 2,2′-[2,2′-bi(1H-1,3-benzimidazole)-1,1′-diyl]diacetate

Huai-Ling Guo,^a Jia-Cheng Liu,^a ^* Chao-Hu Xiao,^a Ting Pang ^a and Ping Cao ^a

^aKey Laboratory of Polymer Materials of Gansu Province, Key Laboratory of Bioelectrochemistry & Environmental Analysis of Gansu College of Chemistry and Chemical Engineering, Northwest Normal University, Lanzhou 730070, People's Republic of China
^*Correspondence e-mail: jcliu8@163.com

(Received 12 July 2012; accepted 16 July 2012; online 21 July 2012)

The whole molecule of the title compound, C₂₀H₁₈N₄O₄, is generated by an inversion center. The benzimidazole ring mean plane make a dihedral angle of 89.4 (8)° with the plane passing through the acetate group (COO). In the crystal, molecules are linked via weak C—H⋯O hydrogen bonds and π–π interactions [centroid–centroid distance = 3.743 (3) Å] involving inversion-related benzimidazole groups.

Related literature

For related structures, see: Al-Mohammed et al. (2012 ); Fu & Xu (2009 ); Xu & Wang (2008 ). For the synthesis of 2,2′-bibenzimidazole, see: Tang et al. (2007 ).

Experimental

Crystal data

C₂₀H₁₈N₄O₄
M_r = 378.38
Triclinic, $[P \overline 1]$
a = 6.904 (4) Å
b = 8.494 (5) Å
c = 8.643 (5) Å
α = 67.191 (5)°
β = 70.360 (5)°
γ = 87.172 (5)°
V = 438.1 (4) Å³
Z = 1
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 296 K
0.33 × 0.31 × 0.29 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.967, T_max = 0.971
3034 measured reflections
1600 independent reflections
1172 reflections with I > 2σ(I)
R_int = 0.027

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.127
S = 1.06
1600 reflections
128 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C8—H8B⋯O1ⁱ	0.97	2.59	3.364 (3)	137
C10—H10C⋯O1ⁱⁱ	0.96	2.55	3.481 (4)	164
Symmetry codes: (i) -x+1, -y+2, -z; (ii) -x, -y+2, -z.

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); 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.

Supporting information

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S1600536812032266/su2479sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812032266/su2479Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S1600536812032266/su2479Isup3.cml

checkCIF report

Comment top

The whole molecule of the title compound (Fig.1) is generated by an inversion center. The benzimidazole system is essentially planar, with a dihedral angle of 0.8 (5)° between the planes of the benzene and imidazole rings. The benzimidazole ring make a dihedral angle of 89.4 (8)° with the plane passing through the acetate group (C9/O1/O2). This value is comparable to that observed in some similar structures (Al-Mohammed et al., 2012; Fu et al., 2009; Xu et al., 2008).

In the crystal, weak intermolecular C—H···O hydrogen bonds (Table 1 and Fig. 2) and π–π stacking interactions [Cg1···Cg2ⁱ = 3.743 (3) Å, where Cg1 is the centroid of ring N1/C1/C6/N2/C7; Cg2 is the centroid of ring C1-C6; symmetry code: (i) -x+1, -y+1, -z+1] stabilize the crystal structure.

Related literature top

For related structures, see: Al-Mohammed et al. (2012); Fu & Xu (2009); Xu & Wang (2008). For the synthesis of 2,2'-bibenzimidazole, see: Tang et al. (2007).

Experimental top

The synthesis of 2,2'-bibenzimidazole [systematic name: 1H,1'H-2,2'-bibenzo[d]imidazole] has been reported (Tang et al., 2007). A mixture of 2,2'-bibenzimidazole (11.71 g, 50 mmol) and NaOH (4.00 g, 100 mmol) in DMSO (40 mL) was stirred at 278 K for 2 h, and then methyl chloroacetate (10.85 g, 100 mmol) was added. The mixture was cooled to room temperature after stirring at 353 K for 24 h, and then poured into 200 mL of water. A yellow solid formed immediately, which was isolated by filtration. The crude product was then crystallized from methanol. Single crystals of the title compound, suitable for X-ray analysis, were obtained by slow evaporation of a solution in methanol.

Structure description top

For related structures, see: Al-Mohammed et al. (2012); Fu & Xu (2009); Xu & Wang (2008). For the synthesis of 2,2'-bibenzimidazole, see: Tang et al. (2007).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); 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).

Figures top

	Fig. 1. The molecular structure of the title molecule with the atom numbering [symmetry code for suffix A: -x, -y+1, -z+1]. Displacement ellipsoids are drawn at the 30% probability level
	Fig. 2. The crystal packing of the title compound, viewed along the b axis. Weak C—H···O interaction are shown as dashed lines.

Dimethyl 2,2'-[2,2'-bi(1H-1,3-benzimidazole)-1,1'-diyl]diacetate top

Crystal data top

C₂₀H₁₈N₄O₄	Z = 1
M_r = 378.38	F(000) = 198
Triclinic, P1	D_x = 1.434 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 6.904 (4) Å	Cell parameters from 853 reflections
b = 8.494 (5) Å	θ = 2.6–23.8°
c = 8.643 (5) Å	µ = 0.10 mm⁻¹
α = 67.191 (5)°	T = 296 K
β = 70.360 (5)°	Block, brown
γ = 87.172 (5)°	0.33 × 0.31 × 0.29 mm
V = 438.1 (4) Å³

Data collection top

Bruker APEXII CCD diffractometer	1600 independent reflections
Radiation source: fine-focus sealed tube	1172 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.027
φ and ω scans	θ_max = 25.5°, θ_min = 2.6°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −8→8
T_min = 0.967, T_max = 0.971	k = −9→10
3034 measured reflections	l = −10→10

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.127	H-atom parameters constrained
S = 1.06	w = 1/[σ²(F_o²) + (0.0656P)² + 0.0023P] where P = (F_o² + 2F_c²)/3
1600 reflections	(Δ/σ)_max < 0.001
128 parameters	Δρ_max = 0.14 e Å⁻³
0 restraints	Δρ_min = −0.25 e Å⁻³

Crystal data top

C₂₀H₁₈N₄O₄	γ = 87.172 (5)°
M_r = 378.38	V = 438.1 (4) Å³
Triclinic, P1	Z = 1
a = 6.904 (4) Å	Mo Kα radiation
b = 8.494 (5) Å	µ = 0.10 mm⁻¹
c = 8.643 (5) Å	T = 296 K
α = 67.191 (5)°	0.33 × 0.31 × 0.29 mm
β = 70.360 (5)°

Data collection top

Bruker APEXII CCD diffractometer	1600 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1172 reflections with I > 2σ(I)
T_min = 0.967, T_max = 0.971	R_int = 0.027
3034 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.127	H-atom parameters constrained
S = 1.06	Δρ_max = 0.14 e Å⁻³
1600 reflections	Δρ_min = −0.25 e Å⁻³
128 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
C1	0.3492 (3)	0.6658 (2)	0.5117 (2)	0.0382 (5)
C2	0.5275 (3)	0.7663 (3)	0.4646 (3)	0.0485 (6)
H2	0.6033	0.8332	0.3460	0.058*
C3	0.5865 (4)	0.7619 (3)	0.6022 (3)	0.0539 (6)
H3	0.7063	0.8271	0.5762	0.065*
C4	0.4722 (4)	0.6624 (3)	0.7808 (3)	0.0533 (6)
H4	0.5173	0.6635	0.8704	0.064*
C5	0.2955 (3)	0.5636 (3)	0.8265 (3)	0.0497 (6)
H5	0.2197	0.4979	0.9454	0.060*
C6	0.2327 (3)	0.5645 (2)	0.6892 (2)	0.0397 (5)
C7	0.0742 (3)	0.5291 (2)	0.5281 (2)	0.0385 (5)
C8	0.3089 (3)	0.7314 (2)	0.2179 (2)	0.0433 (5)
H8A	0.2674	0.6583	0.1696	0.052*
H8B	0.4585	0.7504	0.1691	0.052*
C9	0.2220 (3)	0.9010 (3)	0.1547 (3)	0.0435 (5)
C10	0.0081 (4)	1.1015 (3)	0.2334 (4)	0.0720 (8)
H10A	0.1162	1.1933	0.1612	0.108*
H10B	−0.0752	1.1195	0.3382	0.108*
H10C	−0.0764	1.0989	0.1659	0.108*
N1	0.2463 (2)	0.64117 (18)	0.41008 (19)	0.0388 (4)
N2	0.0622 (3)	0.4797 (2)	0.6961 (2)	0.0435 (5)
O1	0.2651 (3)	0.9897 (2)	−0.00051 (19)	0.0731 (6)
O2	0.0980 (2)	0.94015 (17)	0.28611 (18)	0.0535 (5)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0432 (12)	0.0319 (10)	0.0357 (10)	0.0078 (9)	−0.0109 (9)	−0.0122 (8)
C2	0.0521 (14)	0.0445 (12)	0.0380 (11)	−0.0018 (10)	−0.0083 (10)	−0.0104 (9)
C3	0.0519 (14)	0.0543 (13)	0.0493 (13)	−0.0041 (11)	−0.0148 (11)	−0.0153 (11)
C4	0.0571 (15)	0.0605 (14)	0.0434 (12)	0.0081 (12)	−0.0224 (11)	−0.0176 (11)
C5	0.0498 (14)	0.0542 (13)	0.0354 (11)	0.0099 (11)	−0.0134 (10)	−0.0094 (9)
C6	0.0429 (13)	0.0351 (10)	0.0329 (10)	0.0077 (9)	−0.0102 (9)	−0.0079 (8)
C7	0.0420 (12)	0.0299 (10)	0.0321 (10)	0.0035 (9)	−0.0063 (8)	−0.0059 (8)
C8	0.0497 (13)	0.0421 (11)	0.0280 (10)	−0.0052 (10)	−0.0030 (9)	−0.0110 (8)
C9	0.0431 (13)	0.0446 (12)	0.0335 (10)	−0.0084 (9)	−0.0131 (9)	−0.0044 (9)
C10	0.082 (2)	0.0443 (13)	0.0862 (18)	0.0167 (13)	−0.0383 (16)	−0.0158 (13)
N1	0.0442 (10)	0.0304 (8)	0.0302 (8)	0.0015 (7)	−0.0059 (7)	−0.0058 (7)
N2	0.0454 (11)	0.0396 (9)	0.0321 (9)	0.0036 (8)	−0.0079 (8)	−0.0049 (7)
O1	0.0739 (12)	0.0779 (12)	0.0375 (9)	0.0000 (10)	−0.0172 (8)	0.0073 (8)
O2	0.0684 (11)	0.0384 (8)	0.0470 (9)	0.0120 (7)	−0.0185 (8)	−0.0119 (7)

Geometric parameters (Å, º) top

C1—N1	1.377 (3)	C7—N1	1.379 (2)
C1—C2	1.381 (3)	C7—C7ⁱ	1.449 (4)
C1—C6	1.398 (3)	C8—N1	1.448 (2)
C2—C3	1.368 (3)	C8—C9	1.503 (3)
C2—H2	0.9300	C8—H8A	0.9700
C3—C4	1.398 (3)	C8—H8B	0.9700
C3—H3	0.9300	C9—O1	1.194 (2)
C4—C5	1.367 (3)	C9—O2	1.321 (2)
C4—H4	0.9300	C10—O2	1.447 (3)
C5—C6	1.391 (3)	C10—H10A	0.9600
C5—H5	0.9300	C10—H10B	0.9600
C6—N2	1.383 (3)	C10—H10C	0.9600
C7—N2	1.320 (2)

N1—C1—C2	131.59 (18)	N1—C8—C9	115.16 (16)
N1—C1—C6	105.60 (18)	N1—C8—H8A	108.5
C2—C1—C6	122.81 (19)	C9—C8—H8A	108.5
C3—C2—C1	116.29 (19)	N1—C8—H8B	108.5
C3—C2—H2	121.9	C9—C8—H8B	108.5
C1—C2—H2	121.9	H8A—C8—H8B	107.5
C2—C3—C4	122.0 (2)	O1—C9—O2	124.6 (2)
C2—C3—H3	119.0	O1—C9—C8	121.8 (2)
C4—C3—H3	119.0	O2—C9—C8	113.58 (15)
C5—C4—C3	121.4 (2)	O2—C10—H10A	109.5
C5—C4—H4	119.3	O2—C10—H10B	109.5
C3—C4—H4	119.3	H10A—C10—H10B	109.5
C4—C5—C6	117.83 (19)	O2—C10—H10C	109.5
C4—C5—H5	121.1	H10A—C10—H10C	109.5
C6—C5—H5	121.1	H10B—C10—H10C	109.5
N2—C6—C5	130.18 (18)	C1—N1—C7	106.58 (15)
N2—C6—C1	110.13 (17)	C1—N1—C8	123.60 (16)
C5—C6—C1	119.7 (2)	C7—N1—C8	129.65 (17)
N2—C7—N1	112.52 (18)	C7—N2—C6	105.16 (16)
N2—C7—C7ⁱ	124.2 (2)	C9—O2—C10	116.11 (17)
N1—C7—C7ⁱ	123.3 (2)

N1—C1—C2—C3	179.33 (19)	C2—C1—N1—C8	−3.2 (3)
C6—C1—C2—C3	0.1 (3)	C6—C1—N1—C8	176.12 (16)
C1—C2—C3—C4	−0.5 (3)	N2—C7—N1—C1	−0.7 (2)
C2—C3—C4—C5	0.3 (3)	C7ⁱ—C7—N1—C1	−179.9 (2)
C3—C4—C5—C6	0.2 (3)	N2—C7—N1—C8	−176.09 (18)
C4—C5—C6—N2	−179.3 (2)	C7ⁱ—C7—N1—C8	4.8 (3)
C4—C5—C6—C1	−0.5 (3)	C9—C8—N1—C1	−87.6 (2)
N1—C1—C6—N2	0.0 (2)	C9—C8—N1—C7	87.1 (2)
C2—C1—C6—N2	179.38 (19)	N1—C7—N2—C6	0.7 (2)
N1—C1—C6—C5	−179.02 (17)	C7ⁱ—C7—N2—C6	179.9 (2)
C2—C1—C6—C5	0.4 (3)	C5—C6—N2—C7	178.5 (2)
N1—C8—C9—O1	178.39 (19)	C1—C6—N2—C7	−0.4 (2)
N1—C8—C9—O2	−1.1 (3)	O1—C9—O2—C10	1.1 (3)
C2—C1—N1—C7	−178.9 (2)	C8—C9—O2—C10	−179.49 (17)
C6—C1—N1—C7	0.42 (19)

Symmetry code: (i) −x, −y+1, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C8—H8B···O1ⁱⁱ	0.97	2.59	3.364 (3)	137
C10—H10C···O1ⁱⁱⁱ	0.96	2.55	3.481 (4)	164

Symmetry codes: (ii) −x+1, −y+2, −z; (iii) −x, −y+2, −z.

Experimental details

Crystal data
Chemical formula	C₂₀H₁₈N₄O₄
M_r	378.38
Crystal system, space group	Triclinic, P1
Temperature (K)	296
a, b, c (Å)	6.904 (4), 8.494 (5), 8.643 (5)
α, β, γ (°)	67.191 (5), 70.360 (5), 87.172 (5)
V (Å³)	438.1 (4)
Z	1
Radiation type	Mo Kα
µ (mm⁻¹)	0.10
Crystal size (mm)	0.33 × 0.31 × 0.29

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.967, 0.971
No. of measured, independent and observed [I > 2σ(I)] reflections	3034, 1600, 1172
R_int	0.027
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.127, 1.06
No. of reflections	1600
No. of parameters	128
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.14, −0.25

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), 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
C8—H8B···O1ⁱ	0.97	2.59	3.364 (3)	137
C10—H10C···O1ⁱⁱ	0.96	2.55	3.481 (4)	164

Symmetry codes: (i) −x+1, −y+2, −z; (ii) −x, −y+2, −z.

Acknowledgements

This work was supported by the Natural Science Foundation of Gansu (No. 0710RJ ZA113).

References

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