Download citation
Download citation
link to html
The mol­ecule of the title compound, C5H7N3O3, is approximately planar. The maximum deviation from the least-squares plane calculated for all non-H atoms is 0.054 (2) Å. The dihedral angles between the mean plane of the imidazole ring [planar within 0.0017 (6) Å] and the planes of the nitro and meth­oxy groups are 2.9 (1) and 1.2 (1)°, respectively. The mol­ecules are held together by weak C—H...N and C—H...O inter­actions and by van der Waals forces.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807027201/fb2054sup1.cif
Contains datablocks I, global

hkl

Structure factor file (CIF format) https://doi.org/10.1107/S1600536807027201/fb2054Isup2.hkl
Contains datablock I

CCDC reference: 258085

Key indicators

  • Single-crystal X-ray study
  • T = 90 K
  • Mean [sigma](C-C) = 0.001 Å
  • R factor = 0.033
  • wR factor = 0.091
  • Data-to-parameter ratio = 14.0

checkCIF/PLATON results

No syntax errors found



Alert level B PLAT432_ALERT_2_B Short Inter X...Y Contact O42 .. C21 .. 2.90 Ang.
Alert level C PLAT480_ALERT_4_C Long H...A H-Bond Reported H11A .. O42 .. 2.71 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H11C .. O41 .. 2.63 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H5 .. N3 .. 2.67 Ang. PLAT480_ALERT_4_C Long H...A H-Bond Reported H21C .. O2 .. 2.72 Ang.
0 ALERT level A = In general: serious problem 1 ALERT level B = Potentially serious problem 4 ALERT level C = Check and explain 0 ALERT level G = General alerts; check 0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data 1 ALERT type 2 Indicator that the structure model may be wrong or deficient 0 ALERT type 3 Indicator that the structure quality may be low 4 ALERT type 4 Improvement, methodology, query or suggestion 0 ALERT type 5 Informative message, check

Comment top

The molecule of 1-methyl-2-methoxy-4-nitroimidazole, (I), (Fig. 1, Scheme 1) is almost planar, contrary to its analogue 1-methyl-4-nitro-5-methoxyimidazole, (II), that was determined at 100 K (Kulkarni et al., 1987; CCDC-258086). In (II) the methoxy and and the nitro groups are twisted by 57.55 (14) and by 7.90 (12)°, respectively. These larger twists are obviously concomitant to the steric interactions that have a profound effect on the crystal packing.

In (I), there are weak hydrogen bonds that interconnect molecules into layers (Fig. 2). In (II), on the other hand, the C—H···A interactions (A = O or N) are somewhat stronger (the H···O distances are in the range 2.38 Å - 2.57 Å, H···N is 2.54 Å. Additionally, a π-π interaction with the interplanar distance of 3.275 (2) Å (the distance between the ring centroids is 3.629 (2) Å) is also present in the structure of (II).

Related literature top

This is a part of our studies of intermolecular interactions in 4-nitroimidazole derivatives (e.g. Kubicki, 2004, and references therein). Related literature: Kulkarni et al. (1987); Suwiński & Wagner (2007).

Experimental top

The title compound was synthesized by ipso nucleophilic replacement of nitro group from 2,4-dinitro-1-methyl imidazole in methanol-sodium methoxide solution with a yield (ca. 54%). The detailed synthesis will be described elsewhere (Suwiński & Wagner, 2007).

Refinement top

All the hydrogen atoms were discernible in the difference Fourier maps and were freely refined.

Structure description top

The molecule of 1-methyl-2-methoxy-4-nitroimidazole, (I), (Fig. 1, Scheme 1) is almost planar, contrary to its analogue 1-methyl-4-nitro-5-methoxyimidazole, (II), that was determined at 100 K (Kulkarni et al., 1987; CCDC-258086). In (II) the methoxy and and the nitro groups are twisted by 57.55 (14) and by 7.90 (12)°, respectively. These larger twists are obviously concomitant to the steric interactions that have a profound effect on the crystal packing.

In (I), there are weak hydrogen bonds that interconnect molecules into layers (Fig. 2). In (II), on the other hand, the C—H···A interactions (A = O or N) are somewhat stronger (the H···O distances are in the range 2.38 Å - 2.57 Å, H···N is 2.54 Å. Additionally, a π-π interaction with the interplanar distance of 3.275 (2) Å (the distance between the ring centroids is 3.629 (2) Å) is also present in the structure of (II).

This is a part of our studies of intermolecular interactions in 4-nitroimidazole derivatives (e.g. Kubicki, 2004, and references therein). Related literature: Kulkarni et al. (1987); Suwiński & Wagner (2007).

Computing details top

Data collection: CrysAlis CCD (Oxford Diffraction, 2002); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: Stereochemical Workstation Operation Manual (Siemens, 1989); software used to prepare material for publication: SHELXL97.

Figures top
[Figure 1] Fig. 1. Title molecule with anisotropic displacement parameters at the 50% probability level. The hydrogen atoms are drawn as spheres with arbitrary radii.
[Figure 2] Fig. 2. The layer of the title molecules with C—H···O and C—H···N hydrogen bonds depicted as dashed lines. The view is approximately along the direction [100]. Symmetry codes: (i) x,y,z; (ii): x,3/2 - y,1/2 + z; (iii) x,3/2 - y,-1/2 + z; (iv) 1 - x,-1/2 + y,3/2 - z; (v) 1 - x,1 - y,1 - z; (vi) 1 - x,-1/2 + y,1/2 - z.
2-Methoxy-1-methyl-4-nitro-1H-imidazole top
Crystal data top
C5H7N3O3F(000) = 328
Mr = 157.14Dx = 1.539 Mg m3
Monoclinic, P21/cMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybcCell parameters from 5503 reflections
a = 3.9935 (4) Åθ = 3–24°
b = 15.4223 (13) ŵ = 0.13 mm1
c = 11.1724 (8) ÅT = 90 K
β = 99.710 (7)°Prism, colourless
V = 678.24 (10) Å30.15 × 0.1 × 0.1 mm
Z = 4
Data collection top
Kuma KM-4 CCD four-circle
diffractometer
1791 independent reflections
Radiation source: fine-focus sealed tube1514 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.019
ω scansθmax = 30.0°, θmin = 3.2°
Absorption correction: multi-scan
(SORTAV; Blessing, 1989)
h = 55
Tmin = 0.988, Tmax = 0.991k = 2120
6537 measured reflectionsl = 715
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.033Hydrogen site location: difference Fourier map
wR(F2) = 0.091All H-atom parameters refined
S = 1.08 w = 1/[σ2(Fo2) + (0.0584P)2 + 0.0288P]
where P = (Fo2 + 2Fc2)/3
1791 reflections(Δ/σ)max = 0.001
128 parametersΔρmax = 0.25 e Å3
0 restraintsΔρmin = 0.32 e Å3
0 constraints
Crystal data top
C5H7N3O3V = 678.24 (10) Å3
Mr = 157.14Z = 4
Monoclinic, P21/cMo Kα radiation
a = 3.9935 (4) ŵ = 0.13 mm1
b = 15.4223 (13) ÅT = 90 K
c = 11.1724 (8) Å0.15 × 0.1 × 0.1 mm
β = 99.710 (7)°
Data collection top
Kuma KM-4 CCD four-circle
diffractometer
1791 independent reflections
Absorption correction: multi-scan
(SORTAV; Blessing, 1989)
1514 reflections with I > 2σ(I)
Tmin = 0.988, Tmax = 0.991Rint = 0.019
6537 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0330 restraints
wR(F2) = 0.091All H-atom parameters refined
S = 1.08Δρmax = 0.25 e Å3
1791 reflectionsΔρmin = 0.32 e Å3
128 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
N10.9835 (2)0.86207 (6)0.74562 (7)0.01581 (19)
C111.0726 (3)0.93772 (7)0.82410 (9)0.0195 (2)
H11A0.915 (4)0.9850 (9)0.8026 (12)0.028 (3)*
H11B1.295 (4)0.9564 (10)0.8185 (13)0.034 (4)*
H11C1.060 (4)0.9218 (11)0.9051 (15)0.037 (4)*
C21.0365 (2)0.85322 (6)0.62825 (8)0.0154 (2)
O21.19492 (18)0.91689 (5)0.57922 (6)0.01867 (18)
C211.2306 (3)0.90098 (7)0.45370 (9)0.0183 (2)
H21A1.008 (3)0.8990 (9)0.4044 (12)0.024 (3)*
H21B1.356 (3)0.8470 (9)0.4504 (12)0.021 (3)*
H21C1.361 (4)0.9506 (10)0.4307 (13)0.029 (3)*
N30.9215 (2)0.78040 (5)0.57663 (7)0.01595 (19)
C40.7856 (2)0.74043 (6)0.66772 (8)0.0159 (2)
N40.6282 (2)0.65768 (6)0.64766 (7)0.01753 (19)
O410.6293 (2)0.62136 (5)0.54923 (7)0.0250 (2)
O420.49664 (19)0.62600 (5)0.73091 (7)0.02218 (19)
C50.8197 (2)0.78822 (6)0.77259 (8)0.0162 (2)
H50.760 (3)0.7775 (9)0.8489 (12)0.022 (3)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
N10.0179 (4)0.0188 (4)0.0110 (4)0.0008 (3)0.0032 (3)0.0002 (3)
C110.0241 (5)0.0215 (5)0.0130 (5)0.0015 (4)0.0036 (4)0.0034 (4)
C20.0159 (4)0.0199 (5)0.0109 (4)0.0023 (3)0.0033 (3)0.0017 (3)
O20.0245 (4)0.0205 (4)0.0122 (3)0.0035 (3)0.0065 (3)0.0002 (2)
C210.0218 (5)0.0232 (5)0.0107 (4)0.0008 (4)0.0050 (3)0.0006 (3)
N30.0180 (4)0.0185 (4)0.0116 (4)0.0011 (3)0.0034 (3)0.0013 (3)
C40.0171 (4)0.0187 (4)0.0122 (4)0.0009 (3)0.0031 (3)0.0011 (3)
N40.0199 (4)0.0205 (4)0.0125 (4)0.0007 (3)0.0035 (3)0.0004 (3)
O410.0360 (4)0.0250 (4)0.0150 (4)0.0049 (3)0.0073 (3)0.0058 (3)
O420.0279 (4)0.0240 (4)0.0162 (4)0.0036 (3)0.0082 (3)0.0031 (3)
C50.0180 (4)0.0192 (5)0.0117 (4)0.0009 (3)0.0035 (3)0.0013 (3)
Geometric parameters (Å, º) top
N1—C21.3699 (12)C21—H21A0.965 (14)
N1—C51.3722 (13)C21—H21B0.975 (14)
N1—C111.4668 (12)C21—H21C0.984 (15)
C11—H11A0.967 (15)N3—C41.3771 (12)
C11—H11B0.946 (17)C4—C51.3714 (13)
C11—H11C0.947 (17)C4—N41.4234 (13)
C2—N31.3097 (13)N4—O411.2348 (11)
C2—O21.3347 (12)N4—O421.2428 (11)
O2—C211.4542 (11)C5—H50.938 (14)
C2—N1—C5106.49 (8)H21A—C21—H21B112.4 (11)
C2—N1—C11126.19 (8)O2—C21—H21C105.2 (8)
C5—N1—C11127.27 (8)H21A—C21—H21C110.7 (12)
N1—C11—H11A111.6 (8)H21B—C21—H21C110.9 (11)
N1—C11—H11B109.8 (9)C2—N3—C4102.19 (8)
H11A—C11—H11B109.6 (13)C5—C4—N3113.33 (9)
N1—C11—H11C108.6 (10)C5—C4—N4126.43 (9)
H11A—C11—H11C107.2 (13)N3—C4—N4120.23 (8)
H11B—C11—H11C110.0 (13)O41—N4—O42123.61 (9)
N3—C2—O2127.27 (8)O41—N4—C4118.63 (8)
N3—C2—N1114.05 (8)O42—N4—C4117.76 (8)
O2—C2—N1118.68 (8)C4—C5—N1103.93 (8)
C2—O2—C21113.70 (7)C4—C5—H5132.7 (9)
O2—C21—H21A109.0 (8)N1—C5—H5123.3 (9)
O2—C21—H21B108.3 (8)
C5—N1—C2—N30.10 (11)C2—N3—C4—N4179.52 (8)
C11—N1—C2—N3177.50 (9)C5—C4—N4—O41177.26 (9)
C5—N1—C2—O2179.74 (8)N3—C4—N4—O412.98 (13)
C11—N1—C2—O22.67 (14)C5—C4—N4—O422.78 (14)
N3—C2—O2—C211.33 (13)N3—C4—N4—O42176.99 (8)
N1—C2—O2—C21178.86 (8)N3—C4—C5—N10.34 (11)
O2—C2—N3—C4179.92 (9)N4—C4—C5—N1179.44 (9)
N1—C2—N3—C40.10 (10)C2—N1—C5—C40.25 (10)
C2—N3—C4—C50.28 (11)C11—N1—C5—C4177.31 (9)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11A···O42i0.967 (15)2.713 (15)3.6751 (13)173.0 (11)
C11—H11C···O41ii0.947 (17)2.633 (17)3.4342 (13)142.6 (12)
C5—H5···N3ii0.938 (14)2.670 (14)3.5154 (12)150.2 (11)
C21—H21C···O2iii0.984 (15)2.720 (15)3.6841 (13)166.5 (11)
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y+3/2, z+1/2; (iii) x+3, y+2, z+1.

Experimental details

Crystal data
Chemical formulaC5H7N3O3
Mr157.14
Crystal system, space groupMonoclinic, P21/c
Temperature (K)90
a, b, c (Å)3.9935 (4), 15.4223 (13), 11.1724 (8)
β (°) 99.710 (7)
V3)678.24 (10)
Z4
Radiation typeMo Kα
µ (mm1)0.13
Crystal size (mm)0.15 × 0.1 × 0.1
Data collection
DiffractometerKuma KM-4 CCD four-circle
Absorption correctionMulti-scan
(SORTAV; Blessing, 1989)
Tmin, Tmax0.988, 0.991
No. of measured, independent and
observed [I > 2σ(I)] reflections
6537, 1791, 1514
Rint0.019
(sin θ/λ)max1)0.704
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.033, 0.091, 1.08
No. of reflections1791
No. of parameters128
H-atom treatmentAll H-atom parameters refined
Δρmax, Δρmin (e Å3)0.25, 0.32

Computer programs: CrysAlis CCD (Oxford Diffraction, 2002), CrysAlis CCD, CrysAlis RED (Oxford Diffraction, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), Stereochemical Workstation Operation Manual (Siemens, 1989), SHELXL97.

Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C11—H11A···O42i0.967 (15)2.713 (15)3.6751 (13)173.0 (11)
C11—H11C···O41ii0.947 (17)2.633 (17)3.4342 (13)142.6 (12)
C5—H5···N3ii0.938 (14)2.670 (14)3.5154 (12)150.2 (11)
C21—H21C···O2iii0.984 (15)2.720 (15)3.6841 (13)166.5 (11)
Symmetry codes: (i) x+1, y+1/2, z+3/2; (ii) x, y+3/2, z+1/2; (iii) x+3, y+2, z+1.
 

Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds