1,1′-(Butane-1,4-di­yl)bis­[2-(pyridin-2-yl)-1H-benzimidazole]

Zhou, S.-C.; Xie, H.-Z.

doi:10.1107/S1600536812015899

organic compounds

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Volume 68| Part 5| May 2012| Page o1434

doi:10.1107/S1600536812015899

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1,1′-(Butane-1,4-diyl)bis[2-(pyridin-2-yl)-1H-benzimidazole]

Shao-Chuan Zhou ^a and Hong-Zhen Xie ^a ^*

^aState Key Lab. Base of Novel Functional Materials and Preparation Science, Faculty of Materials Science and Chemical Engineering, Ningbo University, Ningbo, Zhejiang, 315211, People's Republic of China
^*Correspondence e-mail: xiehongzhen@nbu.edu.cn

(Received 9 April 2012; accepted 12 April 2012; online 18 April 2012)

The complete molecule of the title compound, C₂₈H₂₄N₆, is generated by inversion symmetry with the inversion centre located at the mid-point of the central C–C bond of the butanediyl unit. The benzimidazole and pyridine rings are almost coplanar, the dihedral angle between their mean planes being 6.86 (11)°.

Related literature

For the synthesis, see: Liu et al. (2010 ). For background to this study, see: Barnett & Champness (2003 ); Tong et al. (2009 ).

Experimental

Crystal data

C₂₈H₂₄N₆
M_r = 444.53
Monoclinic, P 2₁ /n
a = 6.5617 (7) Å
b = 13.9716 (13) Å
c = 12.3351 (8) Å
β = 96.466 (7)°
V = 1123.66 (17) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 298 K
0.42 × 0.18 × 0.15 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.695, T_max = 0.856
6268 measured reflections
2684 independent reflections
1314 reflections with I > 2σ(I)
R_int = 0.055

Refinement

R[F² > 2σ(F²)] = 0.064
wR(F²) = 0.146
S = 1.02
2684 reflections
162 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.34 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: RAPID-AUTO (Rigaku, 1998 ); cell refinement: RAPID-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536812015899/ff2063sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536812015899/ff2063Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536812015899/ff2063Isup3.cml

checkCIF report

Comment top

The long spacer ligands, particularly the flexible N-bridging donors have been investigated as auxiliary ligands for the construction of novel MOFs [Liu et al., 2010; Barnett et al., 2003; Tong et al., 2009]. As part of our ongoing studies, the title compound was synthesized and characterized by X-ray diffraction.

The complete molecule of the title compound, C₂₈H₂₄N₆, is generated by crystallographic inversion symmetry and the central C—C bond of the butanediyl unit is bisected by the inversion symmetry. The dihedral angle between the benzimidazole ring system and the pyridine ring is 6.86 (11)°, which indicates that they are almost coplanar.

Related literature top

For the synthesis, see: Liu et al. (2010). For background to this study, see: Barnett & Champness (2003); Tong et al. (2009).

Experimental top

According to the literature [Liu et al., 2010], 2-(2-pyridyl)benzimidazole (7.80 g) and NaOH (1.68 g) in DMSO (20 ml) were stirred at 60°C for 0.5 h, and then 1,4-dibromobutane (4.32 g) was added. The mixture was stirred at 60°C for 12 h, and then poured into 400 ml of ice water after being cooled to room temperature. The yellow solid was obtained and isolated by filtration after drying in air. The above products were recrystallized in methanol and yellow crystals of the title compounds were obtained.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

Fig. 1. ORTEP view of complex molecule of (I). Displacement ellipsoids are drawn at the 45% probability level. H atoms were omitted for clarity.

1,1'-(butane-1,4-diyl)bis[2-(pyridin-2-yl)-1H-benzimidazole] top

Crystal data top

C₂₈H₂₄N₆	F(000) = 468
M_r = 444.53	D_x = 1.314 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 6230 reflections
a = 6.5617 (7) Å	θ = 3.1–29.7°
b = 13.9716 (13) Å	µ = 0.08 mm⁻¹
c = 12.3351 (8) Å	T = 298 K
β = 96.466 (7)°	Block, yellow
V = 1123.66 (17) Å³	0.42 × 0.18 × 0.15 mm
Z = 2

Data collection top

Rigaku R-AXIS RAPID diffractometer	2684 independent reflections
Radiation source: fine-focus sealed tube	1314 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.055
ω scans	θ_max = 29.3°, θ_min = 2.9°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −7→8
T_min = 0.695, T_max = 0.856	k = −14→18
6268 measured reflections	l = −16→15

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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0451P)² + 0.0549P] where P = (F_o² + 2F_c²)/3
2684 reflections	(Δ/σ)_max < 0.001
162 parameters	Δρ_max = 0.34 e Å⁻³
0 restraints	Δρ_min = −0.20 e Å⁻³

Crystal data top

C₂₈H₂₄N₆	V = 1123.66 (17) Å³
M_r = 444.53	Z = 2
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.5617 (7) Å	µ = 0.08 mm⁻¹
b = 13.9716 (13) Å	T = 298 K
c = 12.3351 (8) Å	0.42 × 0.18 × 0.15 mm
β = 96.466 (7)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	2684 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1314 reflections with I > 2σ(I)
T_min = 0.695, T_max = 0.856	R_int = 0.055
6268 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.064	0 restraints
wR(F²) = 0.146	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.34 e Å⁻³
2684 reflections	Δρ_min = −0.20 e Å⁻³
162 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	−0.2449 (3)	0.71889 (16)	0.85672 (16)	0.0593 (6)
N2	−0.0037 (3)	0.59178 (15)	0.65051 (13)	0.0501 (6)
N3	0.1079 (3)	0.59573 (14)	0.82913 (13)	0.0436 (5)
C1	−0.2217 (4)	0.68146 (17)	0.75907 (18)	0.0465 (6)
C2	−0.3657 (4)	0.6937 (2)	0.6693 (2)	0.0572 (7)
H2	−0.3442	0.6675	0.6022	0.069*
C3	−0.5399 (4)	0.7445 (2)	0.6803 (2)	0.0663 (8)
H3	−0.6393	0.7525	0.6210	0.080*
C4	−0.5664 (5)	0.7834 (2)	0.7785 (3)	0.0693 (8)
H4	−0.6835	0.8186	0.7877	0.083*
C5	−0.4172 (5)	0.7695 (2)	0.8636 (2)	0.0702 (9)
H5	−0.4360	0.7968	0.9305	0.084*
C6	−0.0367 (4)	0.62376 (17)	0.74647 (17)	0.0442 (6)
C7	0.1763 (4)	0.53894 (18)	0.66954 (17)	0.0437 (6)
C8	0.2838 (4)	0.48915 (19)	0.59693 (18)	0.0534 (7)
H8	0.2371	0.4871	0.5229	0.064*
C9	0.4599 (4)	0.4432 (2)	0.6369 (2)	0.0567 (7)
H9	0.5342	0.4099	0.5893	0.068*
C10	0.5305 (4)	0.4451 (2)	0.7475 (2)	0.0580 (7)
H10	0.6509	0.4131	0.7725	0.070*
C11	0.4249 (4)	0.49381 (19)	0.82047 (18)	0.0525 (7)
H11	0.4713	0.4953	0.8945	0.063*
C12	0.2482 (4)	0.54014 (17)	0.77956 (16)	0.0415 (6)
C13	0.1227 (4)	0.61541 (18)	0.94648 (15)	0.0469 (7)
H13B	0.0880	0.6820	0.9573	0.056*
H13A	0.2633	0.6057	0.9782	0.056*
C14	−0.0179 (6)	0.5522 (2)	1.0057 (2)	0.0620 (9)
H14B	0.005 (3)	0.5697 (16)	1.0838 (18)	0.054 (7)*
H14A	−0.173 (5)	0.544 (2)	0.978 (2)	0.099 (11)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0668 (17)	0.0549 (15)	0.0575 (12)	0.0066 (13)	0.0128 (11)	−0.0001 (11)
N2	0.0581 (14)	0.0578 (14)	0.0344 (10)	−0.0035 (12)	0.0047 (9)	0.0026 (9)
N3	0.0506 (13)	0.0476 (12)	0.0328 (10)	−0.0050 (11)	0.0055 (9)	0.0015 (9)
C1	0.0516 (17)	0.0354 (14)	0.0543 (14)	−0.0035 (13)	0.0138 (12)	0.0039 (12)
C2	0.0607 (19)	0.0516 (17)	0.0591 (15)	0.0017 (15)	0.0058 (13)	0.0040 (14)
C3	0.061 (2)	0.0537 (18)	0.0818 (19)	0.0009 (16)	−0.0008 (16)	0.0112 (16)
C4	0.0522 (19)	0.0499 (18)	0.108 (2)	0.0101 (15)	0.0175 (17)	0.0112 (18)
C5	0.085 (2)	0.056 (2)	0.0748 (19)	0.0079 (18)	0.0293 (18)	−0.0059 (15)
C6	0.0505 (16)	0.0444 (15)	0.0381 (12)	−0.0069 (13)	0.0066 (11)	0.0047 (11)
C7	0.0423 (15)	0.0469 (15)	0.0423 (13)	−0.0043 (12)	0.0069 (11)	0.0043 (11)
C8	0.0600 (18)	0.0629 (19)	0.0387 (12)	−0.0069 (16)	0.0115 (12)	−0.0005 (12)
C9	0.0580 (19)	0.0595 (18)	0.0566 (15)	0.0009 (15)	0.0234 (13)	−0.0076 (14)
C10	0.0474 (17)	0.0620 (18)	0.0649 (16)	0.0016 (14)	0.0077 (13)	0.0059 (14)
C11	0.0534 (17)	0.0628 (18)	0.0399 (12)	−0.0063 (15)	−0.0005 (11)	0.0032 (13)
C12	0.0472 (15)	0.0411 (14)	0.0381 (12)	−0.0051 (13)	0.0129 (11)	0.0016 (11)
C13	0.0600 (16)	0.0503 (16)	0.0303 (11)	−0.0095 (13)	0.0046 (10)	−0.0044 (11)
C14	0.095 (3)	0.0579 (17)	0.0345 (13)	−0.0119 (19)	0.0139 (14)	−0.0042 (14)

Geometric parameters (Å, º) top

N1—C1	1.337 (3)	C7—C12	1.386 (3)
N1—C5	1.344 (3)	C7—C8	1.388 (3)
N2—C6	1.306 (3)	C8—C9	1.364 (3)
N2—C7	1.391 (3)	C8—H8	0.9300
N3—C6	1.370 (3)	C9—C10	1.390 (3)
N3—C12	1.397 (3)	C9—H9	0.9300
N3—C13	1.466 (2)	C10—C11	1.376 (3)
C1—C2	1.383 (3)	C10—H10	0.9300
C1—C6	1.480 (3)	C11—C12	1.373 (3)
C2—C3	1.365 (4)	C11—H11	0.9300
C2—H2	0.9300	C13—C14	1.523 (3)
C3—C4	1.357 (4)	C13—H13B	0.9700
C3—H3	0.9300	C13—H13A	0.9700
C4—C5	1.366 (4)	C14—C14ⁱ	1.486 (6)
C4—H4	0.9300	C14—H14B	0.99 (2)
C5—H5	0.9300	C14—H14A	1.04 (3)

C1—N1—C5	116.4 (2)	C9—C8—H8	120.9
C6—N2—C7	104.66 (19)	C7—C8—H8	120.9
C6—N3—C12	105.58 (17)	C8—C9—C10	121.4 (2)
C6—N3—C13	130.1 (2)	C8—C9—H9	119.3
C12—N3—C13	124.27 (19)	C10—C9—H9	119.3
N1—C1—C2	122.4 (2)	C11—C10—C9	121.0 (3)
N1—C1—C6	119.0 (2)	C11—C10—H10	119.5
C2—C1—C6	118.5 (2)	C9—C10—H10	119.5
C3—C2—C1	119.3 (3)	C12—C11—C10	117.3 (2)
C3—C2—H2	120.4	C12—C11—H11	121.3
C1—C2—H2	120.4	C10—C11—H11	121.3
C4—C3—C2	119.3 (3)	C11—C12—C7	122.3 (2)
C4—C3—H3	120.3	C11—C12—N3	132.2 (2)
C2—C3—H3	120.3	C7—C12—N3	105.5 (2)
C3—C4—C5	118.4 (3)	N3—C13—C14	112.9 (2)
C3—C4—H4	120.8	N3—C13—H13B	109.0
C5—C4—H4	120.8	C14—C13—H13B	109.0
N1—C5—C4	124.2 (3)	N3—C13—H13A	109.0
N1—C5—H5	117.9	C14—C13—H13A	109.0
C4—C5—H5	117.9	H13B—C13—H13A	107.8
N2—C6—N3	113.9 (2)	C14ⁱ—C14—C13	114.4 (3)
N2—C6—C1	120.2 (2)	C14ⁱ—C14—H14B	109.1 (14)
N3—C6—C1	125.8 (2)	C13—C14—H14B	106.8 (13)
C12—C7—C8	119.8 (2)	C14ⁱ—C14—H14A	90.9 (18)
C12—C7—N2	110.35 (19)	C13—C14—H14A	122.1 (16)
C8—C7—N2	129.9 (2)	H14B—C14—H14A	113 (2)
C9—C8—C7	118.3 (2)

Symmetry code: (i) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₂₈H₂₄N₆
M_r	444.53
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	298
a, b, c (Å)	6.5617 (7), 13.9716 (13), 12.3351 (8)
β (°)	96.466 (7)
V (Å³)	1123.66 (17)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.42 × 0.18 × 0.15

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.695, 0.856
No. of measured, independent and observed [I > 2σ(I)] reflections	6268, 2684, 1314
R_int	0.055
(sin θ/λ)_max (Å⁻¹)	0.688

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.064, 0.146, 1.02
No. of reflections	2684
No. of parameters	162
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.20

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976).

Acknowledgements

The paper was sponsored by the K. C. Wong Magna Fund in Ningbo University, the Project of Nonprofit Technology & Research in Zhejiang (2011 C37010), the Ningbo Municipal Natural Science Foundation (grant No. 2010 A610160), the Subject Object (No. xk1070) and the Foundation (No. XYL11009) of Ningbo University.

References

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