organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890

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

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 ππ stacking inter­actions [centroid–centroid distance = 3.894 (2) Å].

Related literature

For biological activity, see: Cina et al. (1996[Cina, S. J., Russell, R. A. & Conradi, S. E. (1996). Am. J. Foren. Med. Path. 17, 343-346.]); Karamanakos et al. (2007[Karamanakos, P. N., Pappas, P., Boumba, V. A., Thomas, C., Malamas, M., Vougiouklakis, T. & Marselos, M. (2007). Int. J. Toxicol. 26, 423-432.]). For bond-length data, see: Allen et al. (1987[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.]).

[Scheme 1]

Experimental

Crystal data
  • C8H12N4O4

  • Mr = 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)

  • Rint = 0.015

Refinement
  • R[F2 > 2σ(F2)] = 0.031

  • wR(F2) = 0.089

  • S = 1.05

  • 1921 reflections

  • 146 parameters

  • H-atom parameters constrained

  • Δρmax = 0.19 e Å−3

  • Δρmin = −0.14 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin.]); cell refinement: SAINT (Bruker, 2001[Bruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin.]); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

All H atoms were placed in calculated positions, with C—H = 0.93–0.97 Å, N—H = 0.86 Å, and included in the final cycles of refinement using a riding model, with Uiso(H) = 1.2 (1.5 for methyl) times Ueq(C, N).

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
[Figure 1] 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
C8H12N4O4F(000) = 480
Mr = 228.22Dx = 1.403 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2505 reflections
a = 9.6959 (12) Åθ = 2.7–27.1°
b = 7.2898 (9) ŵ = 0.11 mm1
c = 15.589 (2) ÅT = 273 K
β = 101.400 (2)°Block, yellow
V = 1080.1 (2) Å30.15 × 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 tubeRint = 0.015
Graphite monochromatorθmax = 25.0°, θmin = 2.3°
ϕ and ω scansh = 1111
5515 measured reflectionsk = 88
1921 independent reflectionsl = 918
Refinement top
Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.031H-atom parameters constrained
wR(F2) = 0.089 w = 1/[σ2(Fo2) + (0.0404P)2 + 0.2462P]
where P = (Fo2 + 2Fc2)/3
S = 1.05(Δ/σ)max < 0.001
1921 reflectionsΔρmax = 0.19 e Å3
146 parametersΔρmin = 0.14 e Å3
0 restraintsExtinction correction: SHELXTL (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.011 (2)
Crystal data top
C8H12N4O4V = 1080.1 (2) Å3
Mr = 228.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 9.6959 (12) ŵ = 0.11 mm1
b = 7.2898 (9) ÅT = 273 K
c = 15.589 (2) Å0.15 × 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 reflectionsRint = 0.015
1921 independent reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0310 restraints
wR(F2) = 0.089H-atom parameters constrained
S = 1.05Δρmax = 0.19 e Å3
1921 reflectionsΔρmin = 0.14 e Å3
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
xyzUiso*/Ueq
O10.41899 (13)0.31179 (19)0.60227 (7)0.0673 (4)
O20.62309 (12)0.35345 (19)0.56977 (8)0.0693 (4)
O30.06913 (10)0.38773 (15)0.39251 (7)0.0495 (3)
O40.13394 (10)0.24805 (16)0.40569 (7)0.0516 (3)
N10.45446 (13)0.11166 (19)0.33518 (8)0.0511 (3)
N20.32310 (11)0.14897 (15)0.43564 (7)0.0368 (3)
N30.50075 (13)0.29867 (17)0.55195 (8)0.0461 (3)
N40.11627 (13)0.41147 (18)0.28483 (8)0.0489 (3)
H40.06020.47390.25980.059*
C10.45604 (14)0.21818 (18)0.46825 (9)0.0374 (3)
C20.53355 (15)0.1938 (2)0.40604 (10)0.0456 (4)
H20.62720.22830.41110.055*
C30.32821 (15)0.0863 (2)0.35445 (9)0.0437 (4)
C40.20850 (19)0.0011 (3)0.29424 (12)0.0657 (5)
H4A0.23560.02870.23970.099*
H4B0.12970.08120.28410.099*
H4C0.18280.11250.32000.099*
C50.20058 (15)0.1428 (2)0.47777 (10)0.0453 (4)
H5A0.23010.09910.53730.054*
H5B0.13260.05620.44670.054*
C60.13134 (15)0.3268 (2)0.47920 (10)0.0489 (4)
H6A0.05910.31910.51410.059*
H6B0.20070.41590.50640.059*
C70.06789 (14)0.34081 (19)0.36319 (9)0.0390 (3)
C80.26021 (17)0.3868 (2)0.24023 (11)0.0564 (4)
H8A0.27340.26320.21900.085*
H8B0.28110.47050.19180.085*
H8C0.32190.41040.28010.085*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0660 (8)0.0934 (10)0.0442 (6)0.0052 (7)0.0153 (6)0.0090 (6)
O20.0506 (7)0.0844 (9)0.0671 (8)0.0186 (6)0.0026 (6)0.0062 (7)
O30.0351 (5)0.0590 (7)0.0568 (7)0.0004 (5)0.0146 (5)0.0064 (5)
O40.0431 (6)0.0645 (7)0.0486 (6)0.0100 (5)0.0123 (5)0.0118 (5)
N10.0494 (7)0.0567 (8)0.0504 (8)0.0087 (6)0.0176 (6)0.0046 (6)
N20.0346 (6)0.0373 (6)0.0394 (6)0.0021 (5)0.0091 (5)0.0027 (5)
N30.0447 (7)0.0477 (7)0.0436 (7)0.0008 (6)0.0029 (6)0.0050 (6)
N40.0441 (7)0.0564 (8)0.0491 (7)0.0010 (6)0.0162 (6)0.0130 (6)
C10.0350 (7)0.0356 (7)0.0410 (7)0.0018 (6)0.0062 (6)0.0040 (6)
C20.0364 (8)0.0477 (8)0.0547 (9)0.0043 (6)0.0141 (7)0.0042 (7)
C30.0459 (8)0.0405 (8)0.0439 (8)0.0073 (6)0.0071 (6)0.0020 (6)
C40.0633 (11)0.0710 (12)0.0582 (10)0.0002 (9)0.0007 (8)0.0172 (9)
C50.0378 (7)0.0522 (9)0.0481 (8)0.0052 (6)0.0138 (6)0.0045 (7)
C60.0361 (8)0.0641 (10)0.0478 (9)0.0024 (7)0.0112 (6)0.0061 (7)
C70.0359 (7)0.0385 (7)0.0460 (8)0.0023 (6)0.0162 (6)0.0017 (6)
C80.0554 (10)0.0609 (10)0.0512 (9)0.0011 (8)0.0062 (7)0.0107 (8)
Geometric parameters (Å, º) top
O1—N31.2241 (16)C1—C21.3509 (19)
O2—N31.2303 (16)C2—H20.9300
O3—C71.3605 (17)C3—C41.485 (2)
O3—C61.4370 (18)C4—H4A0.9600
O4—C71.2140 (16)C4—H4B0.9600
N1—C31.3297 (19)C4—H4C0.9600
N1—C21.354 (2)C5—C61.503 (2)
N2—C31.3555 (18)C5—H5A0.9700
N2—C11.3840 (17)C5—H5B0.9700
N2—C51.4673 (17)C6—H6A0.9700
N3—C11.4181 (18)C6—H6B0.9700
N4—C71.3233 (19)C8—H8A0.9600
N4—C81.442 (2)C8—H8B0.9600
N4—H40.8600C8—H8C0.9600
C7—O3—C6116.02 (11)H4A—C4—H4C109.5
C3—N1—C2105.99 (12)H4B—C4—H4C109.5
C3—N2—C1105.22 (11)N2—C5—C6112.52 (12)
C3—N2—C5126.14 (12)N2—C5—H5A109.1
C1—N2—C5128.64 (11)C6—C5—H5A109.1
O1—N3—O2123.20 (13)N2—C5—H5B109.1
O1—N3—C1120.20 (12)C6—C5—H5B109.1
O2—N3—C1116.60 (13)H5A—C5—H5B107.8
C7—N4—C8121.95 (12)O3—C6—C5111.56 (12)
C7—N4—H4119.0O3—C6—H6A109.3
C8—N4—H4119.0C5—C6—H6A109.3
C2—C1—N2107.35 (12)O3—C6—H6B109.3
C2—C1—N3127.06 (13)C5—C6—H6B109.3
N2—C1—N3125.59 (12)H6A—C6—H6B108.0
C1—C2—N1109.76 (13)O4—C7—N4126.27 (13)
C1—C2—H2125.1O4—C7—O3122.83 (13)
N1—C2—H2125.1N4—C7—O3110.89 (12)
N1—C3—N2111.67 (13)N4—C8—H8A109.5
N1—C3—C4123.81 (14)N4—C8—H8B109.5
N2—C3—C4124.52 (14)H8A—C8—H8B109.5
C3—C4—H4A109.5N4—C8—H8C109.5
C3—C4—H4B109.5H8A—C8—H8C109.5
H4A—C4—H4B109.5H8B—C8—H8C109.5
C3—C4—H4C109.5
C3—N2—C1—C20.11 (15)C1—N2—C3—N10.19 (16)
C5—N2—C1—C2179.97 (13)C5—N2—C3—N1179.95 (13)
C3—N2—C1—N3179.87 (13)C1—N2—C3—C4179.78 (15)
C5—N2—C1—N30.3 (2)C5—N2—C3—C40.4 (2)
O1—N3—C1—C2179.83 (15)C3—N2—C5—C6104.57 (16)
O2—N3—C1—C20.5 (2)C1—N2—C5—C675.25 (18)
O1—N3—C1—N20.1 (2)C7—O3—C6—C591.29 (14)
O2—N3—C1—N2179.77 (13)N2—C5—C6—O366.34 (16)
N2—C1—C2—N10.01 (16)C8—N4—C7—O41.1 (2)
N3—C1—C2—N1179.76 (13)C8—N4—C7—O3178.06 (13)
C3—N1—C2—C10.11 (17)C6—O3—C7—O42.3 (2)
C2—N1—C3—N20.19 (17)C6—O3—C7—N4176.83 (12)
C2—N1—C3—C4179.78 (15)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N1i0.862.203.0416 (17)165
C2—H2···O4ii0.932.343.2492 (18)166
C8—H8B···O4iii0.962.573.498 (2)164
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1, y, z; (iii) x1/2, y+1/2, z+1/2.

Experimental details

Crystal data
Chemical formulaC8H12N4O4
Mr228.22
Crystal system, space groupMonoclinic, P21/n
Temperature (K)273
a, b, c (Å)9.6959 (12), 7.2898 (9), 15.589 (2)
β (°) 101.400 (2)
V3)1080.1 (2)
Z4
Radiation typeMo Kα
µ (mm1)0.11
Crystal size (mm)0.15 × 0.12 × 0.10
Data collection
DiffractometerBruker SMART CCD area-detector
diffractometer
Absorption correction
No. of measured, independent and
observed [I > 2σ(I)] reflections
5515, 1921, 1622
Rint0.015
(sin θ/λ)max1)0.596
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.031, 0.089, 1.05
No. of reflections1921
No. of parameters146
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)0.19, 0.14

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

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N4—H4···N1i0.862.203.0416 (17)165.2
C2—H2···O4ii0.932.343.2492 (18)166.0
C8—H8B···O4iii0.962.573.498 (2)163.6
Symmetry codes: (i) x+1/2, y+1/2, z+1/2; (ii) x+1, y, z; (iii) x1/2, y+1/2, z+1/2.
 

References

First citationAllen, 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
First citationBruker (2001). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin.  Google Scholar
First citationCina, S. J., Russell, R. A. & Conradi, S. E. (1996). Am. J. Foren. Med. Path. 17, 343–346.  CrossRef CAS Web of Science Google Scholar
First citationKaramanakos, 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
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds