3,3′-(2,2′-Bi-1H-imidazole-1,1′-di­yl)dipropanamide

Zhi, Y.-X.; Long, J.; Chen, J.-Y.; Ren, Y.-T.

doi:10.1107/S1600536809028955

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 65| Part 8| August 2009| Page o2008

doi:10.1107/S1600536809028955

Open

access

ADDENDA AND ERRATA

A correction has been published for this article. To view the correction, click here.

3,3′-(2,2′-Bi-1H-imidazole-1,1′-diyl)dipropanamide

Y.-X. Zhi,^a J. Long,^b J.-Y. Chen ^b and Y.-T. Ren ^b ^*

^aGemmological Institute, China University of Geosciences, Wuhan, Hubei 430074, People's Republic of China, and ^bChina University of Geosciences, Engineering Research Center of Nano-Geomaterials of the Ministry of Education, Wuhan, Hubei 430074, People's Republic of China
^*Correspondence e-mail: yingtaorencug@yahoo.cn

(Received 21 July 2009; accepted 22 July 2009; online 29 July 2009)

In the title compound, C₁₂H₁₆N₆O₂, the two imidazole rings are coplanar as a center of inversion exists midway along the C—C bond joining the two rings. In the crystal, intermolecular N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds link adjacent molecules into a two-dimensional layer structure parallel to (001).

Related literature

For the coordination chemistry and biological activity of bis-imidazoles, see: Kirchner & Krebs (1987 ); Tadokoro et al. (1999 ).

Experimental

Crystal data

C₁₂H₁₆N₆O₂
M_r = 276.31
Monoclinic, C 2/c
a = 18.445 (4) Å
b = 4.8622 (10) Å
c = 13.446 (3) Å
β = 93.38 (3)°
V = 1203.8 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 295 K
0.58 × 0.46 × 0.20 mm

Data collection

Rigaku R-AXIS RAPID diffractometer
Absorption correction: multi-scan (ABSCOR; Higashi, 1995 ) T_min = 0.936, T_max = 0.980
4987 measured reflections
1381 independent reflections
1237 reflections with I > 2σ(I)
R_int = 0.017

Refinement

R[F² > 2σ(F²)] = 0.045
wR(F²) = 0.111
S = 1.22
1381 reflections
92 parameters
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N3—H3A⋯N2ⁱ	0.86	2.22	3.055 (1)	164
N3—H3B⋯O1ⁱⁱ	0.86	2.13	2.967 (2)	165
C5—H5B⋯O1ⁱⁱ	0.97	2.58	3.293 (3)	130
Symmetry codes: (i) $[x+{\script{1\over 2}}, y-{\script{1\over 2}}, z]$ ; (ii) x, y+1, z.

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: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028955/ng2617sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809028955/ng2617Isup2.hkl

checkCIF report

Comment top

As part of our ongoing investigations, the title compound, L³, C₁₂H₁₆N₆O₂, as a derivative of 2,2'-bimidazole whose compounds were abstacted for their coordination chemistry and biological activity (Kirchner et al., 1987; Todokoro et al., 1999), has been synthesized and structurally characterized. The single imidazole ring exhibits nearly perfect coplanarity with the maximal deviation of 0.001 (1) Å and the two imidazole rings are coplanar. There are intermolecular N—H···N, N—H···O, C—H···O and C—H···N hydrogen bonds, which leads to two-dimensional layers parallel to (001). Eventually, the crystal packing is established by van der Waals forces.

Related literature top

For the coordination chemistry and biological activity of bis-imidazoles, see: Kirchner et al. (1987); Tadokoro et al. (1999).

Experimental top

A solution of acrylamide (14.2 g, 0.20 mol) in 50 ml DMF was dropwise added to a stirred suspension of 2,2'-biimidazole (13.4 g, 0.1 mol) and NaOH (0.8 g, 0.02 mol) in 100 ml DMF at 80°C, the colour of the resulting solution varied from colourless through green to orange. After the mixture was refluxed for six hours, the crude product was obtained by removement of DMF solvent under reduced pressure. The product was isolated,washed by 10 ml aether for three times, and then dried in vacuo to give the pure compound L³ in a 74.3% yield. Colourless single crystals of L³ suitable for single X-ray analysis were recrystallized by slow evaporation of a deionized aqueous solution.¹H NMR (400 MHz, D₂O, 25°C, TMS, p.p.m.) δ: 8.402(s, 4H), 7.306(s, 2H), 7.140(s, 2H), 4.374(s, 4H), 2.627(s, 4H). ¹³C NMR (400 MHz, D₂O, 25°C, TMS, p.p.m.) δ:171.53, 136.57, 128.15, 122.39, 42.96, 35.06. IR (KBr, cm^-1): 3388m, 1674 s, 1409 s, 1267 s, 769 s. Anal. Calcd for L³ (%): C, 52.17; H, 5.80; N, 30.22. Found: C, 52.12; H, 5.70; N, 29.89.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: Crystal Structure (Rigaku/MSC, 2002); 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. View of the molecular structure of the title compound, Displacement ellipsoids are drawn at the 45% probability level.[Symmetry codes: (i) -x + 1/2, -y + 3/2, -z + 1]

3,3'-(2,2'-Bi-1H-imidazole-1,1'-diyl)dipropanamide top

Crystal data top

C₁₂H₁₆N₆O₂	F(000) = 584
M_r = 276.31	D_x = 1.525 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 1381 reflections
a = 18.445 (4) Å	θ = 3.0–27.5°
b = 4.8622 (10) Å	µ = 0.11 mm⁻¹
c = 13.446 (3) Å	T = 295 K
β = 93.38 (3)°	Platelet, colorless
V = 1203.8 (5) Å³	0.58 × 0.46 × 0.20 mm
Z = 4

Data collection top

Rigaku R-AXIS RAPID diffractometer	1381 independent reflections
Radiation source: fine-focus sealed tube	1237 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.017
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −23→23
T_min = 0.936, T_max = 0.980	k = −6→6
4987 measured reflections	l = −15→17

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.045	H-atom parameters constrained
wR(F²) = 0.111	w = 1/[σ²(F_o²) + (0.0012P)² + 5.254P] where P = (F_o² + 2F_c²)/3
S = 1.22	(Δ/σ)_max < 0.001
1381 reflections	Δρ_max = 0.33 e Å⁻³
92 parameters	Δρ_min = −0.28 e Å⁻³
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.0061 (5)

Crystal data top

C₁₂H₁₆N₆O₂	V = 1203.8 (5) Å³
M_r = 276.31	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.445 (4) Å	µ = 0.11 mm⁻¹
b = 4.8622 (10) Å	T = 295 K
c = 13.446 (3) Å	0.58 × 0.46 × 0.20 mm
β = 93.38 (3)°

Data collection top

Rigaku R-AXIS RAPID diffractometer	1381 independent reflections
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	1237 reflections with I > 2σ(I)
T_min = 0.936, T_max = 0.980	R_int = 0.017
4987 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.045	0 restraints
wR(F²) = 0.111	H-atom parameters constrained
S = 1.22	Δρ_max = 0.33 e Å⁻³
1381 reflections	Δρ_min = −0.28 e Å⁻³
92 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
O1	0.47285 (8)	0.1364 (3)	0.37688 (12)	0.0174 (4)
N3	0.52500 (9)	0.5591 (4)	0.38322 (12)	0.0125 (4)
H3A	0.5683	0.4933	0.3846	0.015*
H3B	0.5184	0.7341	0.3846	0.015*
C3	0.21467 (11)	0.3911 (4)	0.33180 (15)	0.0120 (4)
H3C	0.2203	0.2520	0.2854	0.014*
C4	0.33714 (10)	0.3479 (4)	0.41994 (15)	0.0112 (4)
H4A	0.3370	0.1679	0.3888	0.013*
H4B	0.3497	0.3241	0.4905	0.013*
N1	0.26419 (9)	0.4700 (4)	0.40652 (12)	0.0100 (4)
C6	0.46787 (11)	0.3892 (4)	0.37902 (14)	0.0112 (4)
C2	0.15558 (10)	0.5566 (4)	0.33885 (15)	0.0119 (4)
H2A	0.1136	0.5477	0.2971	0.014*
C1	0.23297 (10)	0.6812 (4)	0.45616 (14)	0.0097 (4)
N2	0.16681 (9)	0.7385 (4)	0.41640 (13)	0.0117 (4)
C5	0.39394 (10)	0.5287 (4)	0.37442 (15)	0.0122 (4)
H5A	0.3789	0.5678	0.3055	0.015*
H5B	0.3976	0.7020	0.4101	0.015*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0133 (7)	0.0105 (7)	0.0283 (9)	0.0017 (6)	0.0008 (6)	−0.0010 (6)
N3	0.0091 (7)	0.0106 (8)	0.0179 (9)	0.0016 (6)	0.0007 (6)	0.0000 (7)
C3	0.0126 (9)	0.0118 (9)	0.0116 (9)	−0.0017 (8)	0.0006 (7)	−0.0008 (8)
C4	0.0085 (9)	0.0106 (9)	0.0147 (9)	0.0022 (7)	0.0011 (7)	−0.0001 (8)
N1	0.0082 (7)	0.0095 (8)	0.0124 (8)	0.0000 (6)	0.0008 (6)	−0.0003 (7)
C6	0.0107 (9)	0.0132 (10)	0.0095 (9)	0.0019 (8)	0.0004 (7)	0.0005 (8)
C2	0.0096 (9)	0.0132 (10)	0.0127 (9)	−0.0019 (7)	−0.0006 (7)	0.0005 (8)
C1	0.0094 (8)	0.0090 (9)	0.0109 (9)	0.0000 (7)	0.0020 (7)	0.0009 (7)
N2	0.0088 (8)	0.0113 (8)	0.0149 (8)	−0.0005 (6)	0.0005 (6)	0.0011 (7)
C5	0.0091 (9)	0.0114 (9)	0.0162 (10)	0.0010 (7)	0.0008 (7)	0.0018 (8)

Geometric parameters (Å, º) top

O1—C6	1.233 (3)	C4—H4B	0.9700
N3—C6	1.337 (3)	N1—C1	1.370 (3)
N3—H3A	0.8600	C6—C5	1.521 (3)
N3—H3B	0.8600	C2—N2	1.374 (3)
C3—C2	1.362 (3)	C2—H2A	0.9300
C3—N1	1.372 (3)	C1—N2	1.332 (2)
C3—H3C	0.9300	C1—C1ⁱ	1.465 (4)
C4—N1	1.472 (2)	C5—H5A	0.9700
C4—C5	1.523 (3)	C5—H5B	0.9700
C4—H4A	0.9700

C6—N3—H3A	120.0	O1—C6—C5	120.75 (19)
C6—N3—H3B	120.0	N3—C6—C5	115.39 (18)
H3A—N3—H3B	120.0	C3—C2—N2	110.33 (17)
C2—C3—N1	106.55 (18)	C3—C2—H2A	124.8
C2—C3—H3C	126.7	N2—C2—H2A	124.8
N1—C3—H3C	126.7	N2—C1—N1	111.26 (17)
N1—C4—C5	111.30 (16)	N2—C1—C1ⁱ	124.5 (2)
N1—C4—H4A	109.4	N1—C1—C1ⁱ	124.2 (2)
C5—C4—H4A	109.4	C1—N2—C2	105.28 (17)
N1—C4—H4B	109.4	C6—C5—C4	111.26 (17)
C5—C4—H4B	109.4	C6—C5—H5A	109.4
H4A—C4—H4B	108.0	C4—C5—H5A	109.4
C1—N1—C3	106.58 (16)	C6—C5—H5B	109.4
C1—N1—C4	130.54 (16)	C4—C5—H5B	109.4
C3—N1—C4	122.78 (17)	H5A—C5—H5B	108.0
O1—C6—N3	123.84 (19)

Symmetry code: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3A···N2ⁱⁱ	0.86	2.22	3.055 (1)	164
N3—H3B···O1ⁱⁱⁱ	0.86	2.13	2.967 (2)	165
C4—H4B···N2ⁱ	0.97	2.50	2.985 (2)	111
C5—H5B···O1ⁱⁱⁱ	0.97	2.58	3.293 (3)	130

Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) x+1/2, y−1/2, z; (iii) x, y+1, z.

Experimental details

Crystal data
Chemical formula	C₁₂H₁₆N₆O₂
M_r	276.31
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	295
a, b, c (Å)	18.445 (4), 4.8622 (10), 13.446 (3)
β (°)	93.38 (3)
V (Å³)	1203.8 (5)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.58 × 0.46 × 0.20

Data collection
Diffractometer	Rigaku R-AXIS RAPID diffractometer
Absorption correction	Multi-scan (ABSCOR; Higashi, 1995)
T_min, T_max	0.936, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	4987, 1381, 1237
R_int	0.017
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.045, 0.111, 1.22
No. of reflections	1381
No. of parameters	92
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.33, −0.28

Computer programs: RAPID-AUTO (Rigaku, 1998), Crystal Structure (Rigaku/MSC, 2002), 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
N3—H3A···N2ⁱ	0.860	2.219	3.055 (1)	163.89
N3—H3B···O1ⁱⁱ	0.860	2.129	2.967 (2)	164.58
C5—H5B···O1ⁱⁱ	0.970	2.581	3.293 (3)	130.36

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

Acknowledgements

We thank the China University of Geosciences for financial support. We are grateful to Mr Z.-F. Li for collecting the diffraction data.

References

Higashi, T. (1995). ABSCOR. Rigaku Corporation, Tokyo, Japan. Google Scholar
Kirchner, C. & Krebs, B. (1987). Inorg. Chem. 26, 3569–3576. CSD CrossRef CAS Web of Science Google Scholar
Rigaku (1998). RAPID-AUTO. Rigaku Corporation, Tokyo, Japan. Google Scholar
Rigaku/MSC (2002). CrystalStructure. Rigaku/MSC Inc., The Woodlands, Texas, USA. Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Tadokoro, M., Isobe, K., Uekusa, H., Ohashi, Y., Tovoda, J., Tashiro, K. & Nakasuji, K. (1999). Angew. Chem. Int. Ed. 38, 95–98. CrossRef CAS Google Scholar