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

Abstract

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,

• a = 18.445 (4) Å

• b = 4.8622 (10) Å

• c = 13.446 (3) Å

• β = 93.38 (3)°

• V = 1203.8 (5) ų

• 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[F ² > 2σ(F ²)] = 0.045

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) ; (ii) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms bonded to C atoms were palced in geometrically calculated position and were refined using a riding model, with U_iso(H) = 1.2 U_eq(C). H atoms attached to O atoms were found in a difference Fourier synthesis and were refined using a riding model, with the O—H distances fixed as initially found and with U_iso(H) values set at 1.2 Ueq(O).

Figures

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]

Crystal data

C12H16N6O2	F(000) = 584
Mr = 276.31	Dx = 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

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

Refinement

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(Fo2) + (0.0012P)2 + 5.254P] where P = (Fo2 + 2Fc2)/3
S = 1.22	(Δ/σ)max < 0.001
1381 reflections	Δρmax = 0.33 e Å−3
92 parameters	Δρmin = −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)

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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 codes: (i) −x+1/2, −y+3/2, −z+1.

Hydrogen-bond geometry (Å, °)

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