2-(2-Methyl-5-nitro-1H-imidazol-1-yl)ethyl N-methyl­carbamate

Duan, G.-Y.; Xia, C.-C.; Xiao, Y.-L.

doi:10.1107/S1600536808041676

organic compounds

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Volume 65| Part 1| January 2009| Page o116

doi:10.1107/S1600536808041676

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2-(2-Methyl-5-nitro-1H-imidazol-1-yl)ethyl N-methylcarbamate

Gui-Yun Duan,^a ^* Cheng-Cai Xia ^a and Yu-Liang Xiao ^a

^aCollege of Pharmaceutical Sciences, Taishan Medical University, Tai'an 271016, People's Republic of China
^*Correspondence e-mail: duanguiyun@yahoo.cn

(Received 30 November 2008; accepted 9 December 2008; online 13 December 2008)

In the title compound, C₈H₁₂N₄O₄, the essentially planar methylcarbamoyloxymethyl group [maximum deviation 0.038 (3) Å] and the imidazole ring make a dihedral angle of 48.47 (3)°. The crystal packing is stabilized by intermolecular N—H⋯N and C—H⋯O hydrogen bonds, which link the molecules into infinite ribbons running along the a axis, and by weak π–π stacking interactions [centroid–centroid distance = 3.894 (2) Å].

Related literature

For biological activity, see: Cina et al. (1996 ); Karamanakos et al. (2007 ). For bond-length data, see: Allen et al. (1987 ).

Experimental

Crystal data

C₈H₁₂N₄O₄
M_r = 228.22
Monoclinic, P 2₁ /n
a = 9.6959 (12) Å
b = 7.2898 (9) Å
c = 15.589 (2) Å
β = 101.400 (2)°
V = 1080.1 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.11 mm⁻¹
T = 273 (2) K
0.15 × 0.12 × 0.10 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
5515 measured reflections
1921 independent reflections
1622 reflections with I > 2σ(I)
R_int = 0.015

Refinement

R[F² > 2σ(F²)] = 0.031
wR(F²) = 0.089
S = 1.05
1921 reflections
146 parameters
H-atom parameters constrained
Δρ_max = 0.19 e Å⁻³
Δρ_min = −0.14 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4⋯N1ⁱ	0.86	2.20	3.0416 (17)	165
C2—H2⋯O4ⁱⁱ	0.93	2.34	3.2492 (18)	166
C8—H8B⋯O4ⁱⁱⁱ	0.96	2.57	3.498 (2)	164
Symmetry codes: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) x+1, y, z; (iii) $[-x-{\script{1\over 2}}, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808041676/hg2452sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536808041676/hg2452Isup2.hkl

checkCIF report

Comment top

2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethanol is an anti-anaerobic bacteria and anti-infusorium agent to treatment of infection which is called metronidazole (Cina et al., 1996; Karamanakos et al., 2007). The title compound is a derivative of it. In this paper, we report the crystal structure of the title compound.

In (I) (Fig. 1), all bond lengths are normal (Allen et al., 1987). Atoms C4, C5, N3, O1, O2 lie in the plane of the imidazole ring (C1/C2/C3/N1/N2) with maximum deviations 0.004 (2)Å for O1. The essentially planar methyl methylcarbamate moiety (C6—C8/N4/O3/O4) and the imidazole ring make a dihedral angle of 48.47 (3)°. The relatively short distance of 3.894 (2)Å between the centroids of imidazole ring C1/C2/C3/N1/N2 [at (1-X,-Y,1-Z)] indicates the presence of weak π-π interactions, which contribute to the stability of the crystal packing. The crystal packing is also stabilized by intermolecular N—H···N and C—H···O hydrogen bonds,

Related literature top

For biological activity, see: Cina et al. (1996); Karamanakos et al. (2007). For bond-length data, see: Allen et al. (1987).

Experimental top

The title compound was prepared by reaction of 1.71 g (0.01 mol) 2-(2-methyl-5-nitro-1H-imidazol-1-yl)ethanol with 0.68 g (0.12 mol) methyl isocyanate catalyzed by 1 g triethylamine in 20 ml toluene at room temperature, yield 86.4%. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a metanol solution at room temperature for two weeks.

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. View of the title compound (I), with displacement ellipsoids drawn at the 40% probability level.

2-(2-Methyl-5-nitro-1H-imidazol-1-yl)ethyl N-methylcarbamate top

Crystal data top

C₈H₁₂N₄O₄	F(000) = 480
M_r = 228.22	D_x = 1.403 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2505 reflections
a = 9.6959 (12) Å	θ = 2.7–27.1°
b = 7.2898 (9) Å	µ = 0.11 mm⁻¹
c = 15.589 (2) Å	T = 273 K
β = 101.400 (2)°	Block, yellow
V = 1080.1 (2) Å³	0.15 × 0.12 × 0.10 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1622 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.015
Graphite monochromator	θ_max = 25.0°, θ_min = 2.3°
ϕ and ω scans	h = −11→11
5515 measured reflections	k = −8→8
1921 independent reflections	l = −9→18

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)] = 0.031	H-atom parameters constrained
wR(F²) = 0.089	w = 1/[σ²(F_o²) + (0.0404P)² + 0.2462P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max < 0.001
1921 reflections	Δρ_max = 0.19 e Å⁻³
146 parameters	Δρ_min = −0.14 e Å⁻³
0 restraints	Extinction correction: SHELXTL (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

Crystal data top

C₈H₁₂N₄O₄	V = 1080.1 (2) Å³
M_r = 228.22	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 9.6959 (12) Å	µ = 0.11 mm⁻¹
b = 7.2898 (9) Å	T = 273 K
c = 15.589 (2) Å	0.15 × 0.12 × 0.10 mm
β = 101.400 (2)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1622 reflections with I > 2σ(I)
5515 measured reflections	R_int = 0.015
1921 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.031	0 restraints
wR(F²) = 0.089	H-atom parameters constrained
S = 1.05	Δρ_max = 0.19 e Å⁻³
1921 reflections	Δρ_min = −0.14 e Å⁻³
146 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	0.41899 (13)	0.31179 (19)	0.60227 (7)	0.0673 (4)
O2	0.62309 (12)	0.35345 (19)	0.56977 (8)	0.0693 (4)
O3	0.06913 (10)	0.38773 (15)	0.39251 (7)	0.0495 (3)
O4	−0.13394 (10)	0.24805 (16)	0.40569 (7)	0.0516 (3)
N1	0.45446 (13)	0.11166 (19)	0.33518 (8)	0.0511 (3)
N2	0.32310 (11)	0.14897 (15)	0.43564 (7)	0.0368 (3)
N3	0.50075 (13)	0.29867 (17)	0.55195 (8)	0.0461 (3)
N4	−0.11627 (13)	0.41147 (18)	0.28483 (8)	0.0489 (3)
H4	−0.0602	0.4739	0.2598	0.059*
C1	0.45604 (14)	0.21818 (18)	0.46825 (9)	0.0374 (3)
C2	0.53355 (15)	0.1938 (2)	0.40604 (10)	0.0456 (4)
H2	0.6272	0.2283	0.4111	0.055*
C3	0.32821 (15)	0.0863 (2)	0.35445 (9)	0.0437 (4)
C4	0.20850 (19)	−0.0011 (3)	0.29424 (12)	0.0657 (5)
H4A	0.2356	−0.0287	0.2397	0.099*
H4B	0.1297	0.0812	0.2841	0.099*
H4C	0.1828	−0.1125	0.3200	0.099*
C5	0.20058 (15)	0.1428 (2)	0.47777 (10)	0.0453 (4)
H5A	0.2301	0.0991	0.5373	0.054*
H5B	0.1326	0.0562	0.4467	0.054*
C6	0.13134 (15)	0.3268 (2)	0.47920 (10)	0.0489 (4)
H6A	0.0591	0.3191	0.5141	0.059*
H6B	0.2007	0.4159	0.5064	0.059*
C7	−0.06789 (14)	0.34081 (19)	0.36319 (9)	0.0390 (3)
C8	−0.26021 (17)	0.3868 (2)	0.24023 (11)	0.0564 (4)
H8A	−0.2734	0.2632	0.2190	0.085*
H8B	−0.2811	0.4705	0.1918	0.085*
H8C	−0.3219	0.4104	0.2801	0.085*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0660 (8)	0.0934 (10)	0.0442 (6)	−0.0052 (7)	0.0153 (6)	−0.0090 (6)
O2	0.0506 (7)	0.0844 (9)	0.0671 (8)	−0.0186 (6)	−0.0026 (6)	−0.0062 (7)
O3	0.0351 (5)	0.0590 (7)	0.0568 (7)	−0.0004 (5)	0.0146 (5)	0.0064 (5)
O4	0.0431 (6)	0.0645 (7)	0.0486 (6)	−0.0100 (5)	0.0123 (5)	0.0118 (5)
N1	0.0494 (7)	0.0567 (8)	0.0504 (8)	0.0087 (6)	0.0176 (6)	−0.0046 (6)
N2	0.0346 (6)	0.0373 (6)	0.0394 (6)	0.0021 (5)	0.0091 (5)	0.0027 (5)
N3	0.0447 (7)	0.0477 (7)	0.0436 (7)	−0.0008 (6)	0.0029 (6)	0.0050 (6)
N4	0.0441 (7)	0.0564 (8)	0.0491 (7)	−0.0010 (6)	0.0162 (6)	0.0130 (6)
C1	0.0350 (7)	0.0356 (7)	0.0410 (7)	0.0018 (6)	0.0062 (6)	0.0040 (6)
C2	0.0364 (8)	0.0477 (8)	0.0547 (9)	0.0043 (6)	0.0141 (7)	0.0042 (7)
C3	0.0459 (8)	0.0405 (8)	0.0439 (8)	0.0073 (6)	0.0071 (6)	−0.0020 (6)
C4	0.0633 (11)	0.0710 (12)	0.0582 (10)	−0.0002 (9)	0.0007 (8)	−0.0172 (9)
C5	0.0378 (7)	0.0522 (9)	0.0481 (8)	−0.0052 (6)	0.0138 (6)	0.0045 (7)
C6	0.0361 (8)	0.0641 (10)	0.0478 (9)	0.0024 (7)	0.0112 (6)	−0.0061 (7)
C7	0.0359 (7)	0.0385 (7)	0.0460 (8)	0.0023 (6)	0.0162 (6)	−0.0017 (6)
C8	0.0554 (10)	0.0609 (10)	0.0512 (9)	−0.0011 (8)	0.0062 (7)	0.0107 (8)

Geometric parameters (Å, º) top

O1—N3	1.2241 (16)	C1—C2	1.3509 (19)
O2—N3	1.2303 (16)	C2—H2	0.9300
O3—C7	1.3605 (17)	C3—C4	1.485 (2)
O3—C6	1.4370 (18)	C4—H4A	0.9600
O4—C7	1.2140 (16)	C4—H4B	0.9600
N1—C3	1.3297 (19)	C4—H4C	0.9600
N1—C2	1.354 (2)	C5—C6	1.503 (2)
N2—C3	1.3555 (18)	C5—H5A	0.9700
N2—C1	1.3840 (17)	C5—H5B	0.9700
N2—C5	1.4673 (17)	C6—H6A	0.9700
N3—C1	1.4181 (18)	C6—H6B	0.9700
N4—C7	1.3233 (19)	C8—H8A	0.9600
N4—C8	1.442 (2)	C8—H8B	0.9600
N4—H4	0.8600	C8—H8C	0.9600

C7—O3—C6	116.02 (11)	H4A—C4—H4C	109.5
C3—N1—C2	105.99 (12)	H4B—C4—H4C	109.5
C3—N2—C1	105.22 (11)	N2—C5—C6	112.52 (12)
C3—N2—C5	126.14 (12)	N2—C5—H5A	109.1
C1—N2—C5	128.64 (11)	C6—C5—H5A	109.1
O1—N3—O2	123.20 (13)	N2—C5—H5B	109.1
O1—N3—C1	120.20 (12)	C6—C5—H5B	109.1
O2—N3—C1	116.60 (13)	H5A—C5—H5B	107.8
C7—N4—C8	121.95 (12)	O3—C6—C5	111.56 (12)
C7—N4—H4	119.0	O3—C6—H6A	109.3
C8—N4—H4	119.0	C5—C6—H6A	109.3
C2—C1—N2	107.35 (12)	O3—C6—H6B	109.3
C2—C1—N3	127.06 (13)	C5—C6—H6B	109.3
N2—C1—N3	125.59 (12)	H6A—C6—H6B	108.0
C1—C2—N1	109.76 (13)	O4—C7—N4	126.27 (13)
C1—C2—H2	125.1	O4—C7—O3	122.83 (13)
N1—C2—H2	125.1	N4—C7—O3	110.89 (12)
N1—C3—N2	111.67 (13)	N4—C8—H8A	109.5
N1—C3—C4	123.81 (14)	N4—C8—H8B	109.5
N2—C3—C4	124.52 (14)	H8A—C8—H8B	109.5
C3—C4—H4A	109.5	N4—C8—H8C	109.5
C3—C4—H4B	109.5	H8A—C8—H8C	109.5
H4A—C4—H4B	109.5	H8B—C8—H8C	109.5
C3—C4—H4C	109.5

C3—N2—C1—C2	−0.11 (15)	C1—N2—C3—N1	0.19 (16)
C5—N2—C1—C2	−179.97 (13)	C5—N2—C3—N1	−179.95 (13)
C3—N2—C1—N3	−179.87 (13)	C1—N2—C3—C4	179.78 (15)
C5—N2—C1—N3	0.3 (2)	C5—N2—C3—C4	−0.4 (2)
O1—N3—C1—C2	−179.83 (15)	C3—N2—C5—C6	−104.57 (16)
O2—N3—C1—C2	0.5 (2)	C1—N2—C5—C6	75.25 (18)
O1—N3—C1—N2	−0.1 (2)	C7—O3—C6—C5	91.29 (14)
O2—N3—C1—N2	−179.77 (13)	N2—C5—C6—O3	66.34 (16)
N2—C1—C2—N1	0.01 (16)	C8—N4—C7—O4	1.1 (2)
N3—C1—C2—N1	179.76 (13)	C8—N4—C7—O3	−178.06 (13)
C3—N1—C2—C1	0.11 (17)	C6—O3—C7—O4	−2.3 (2)
C2—N1—C3—N2	−0.19 (17)	C6—O3—C7—N4	176.83 (12)
C2—N1—C3—C4	−179.78 (15)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N1ⁱ	0.86	2.20	3.0416 (17)	165
C2—H2···O4ⁱⁱ	0.93	2.34	3.2492 (18)	166
C8—H8B···O4ⁱⁱⁱ	0.96	2.57	3.498 (2)	164

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

Experimental details

Crystal data
Chemical formula	C₈H₁₂N₄O₄
M_r	228.22
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	273
a, b, c (Å)	9.6959 (12), 7.2898 (9), 15.589 (2)
β (°)	101.400 (2)
V (Å³)	1080.1 (2)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.11
Crystal size (mm)	0.15 × 0.12 × 0.10

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	5515, 1921, 1622
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.596

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.031, 0.089, 1.05
No. of reflections	1921
No. of parameters	146
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.19, −0.14

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4···N1ⁱ	0.86	2.20	3.0416 (17)	165.2
C2—H2···O4ⁱⁱ	0.93	2.34	3.2492 (18)	166.0
C8—H8B···O4ⁱⁱⁱ	0.96	2.57	3.498 (2)	163.6

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

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin. Google Scholar
Cina, S. J., Russell, R. A. & Conradi, S. E. (1996). Am. J. Foren. Med. Path. 17, 343–346. CrossRef CAS Web of Science Google Scholar
Karamanakos, P. N., Pappas, P., Boumba, V. A., Thomas, C., Malamas, M., Vougiouklakis, T. & Marselos, M. (2007). Int. J. Toxicol. 26, 423–432. Web of Science CrossRef PubMed CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
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ISSN: 2056-9890

Volume 65| Part 1| January 2009| Page o116

doi:10.1107/S1600536808041676

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