PMCCPMCCPMCC

Search tips
Search criteria 

Advanced

 
Logo of actaeInternational Union of Crystallographysearchopen accessarticle submissionjournal home pagethis article
 
Acta Crystallogr Sect E Struct Rep Online. 2008 January 1; 64(Pt 1): o149.
Published online 2007 December 6. doi:  10.1107/S1600536807063532
PMCID: PMC2915217

4-Nitro­phenyl N-(2-isopropyl­thia­zol-4-ylmeth­yl)-N-methyl­carbamate

Abstract

In the title compound, C15H17N3O4S, the benzene and thia­zole rings are oriented at a dihedral angle of 74.10 (3)°. In the crystal structure, inter­molecular C—H(...)O hydrogen bonds are found.

Related literature

For related literature, see: Allen et al. (1987 [triangle]); Ishikawa et al. (1998 [triangle]); Riden & Hopkins (1961 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-64-0o149-scheme1.jpg

Experimental

Crystal data

  • C15H17N3O4S
  • M r = 335.38
  • Orthorhombic, An external file that holds a picture, illustration, etc.
Object name is e-64-0o149-efi1.jpg
  • a = 12.250 (3) Å
  • b = 10.876 (2) Å
  • c = 24.845 (5) Å
  • V = 3310.1 (12) Å3
  • Z = 8
  • Mo Kα radiation
  • μ = 0.22 mm−1
  • T = 298 (2) K
  • 0.30 × 0.20 × 0.10 mm

Data collection

  • Enraf–Nonius CAD-4 diffractometer
  • Absorption correction: ψ scan (North et al., 1968 [triangle]) T min = 0.937, T max = 0.979
  • 3281 measured reflections
  • 3241 independent reflections
  • 1335 reflections with I > 2σ(I)
  • R int = 0.072
  • 3 standard reflections every 200 reflections intensity decay: none

Refinement

  • R[F 2 > 2σ(F 2)] = 0.086
  • wR(F 2) = 0.217
  • S = 1.04
  • 3241 reflections
  • 184 parameters
  • H-atom parameters constrained
  • Δρmax = 0.28 e Å−3
  • Δρmin = −0.39 e Å−3

Data collection: CAD-4 Software (Enraf–Nonius, 1989 [triangle]); cell refinement: CAD-4 Software; data reduction: XCAD4 (Harms & Wocadlo,1995 [triangle]); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997 [triangle]); molecular graphics: SHELXTL (Siemens,1996 [triangle]); software used to prepare material for publication: SHELXL97.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536807063532/bq2046sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536807063532/bq2046Isup2.hkl

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

Acknowledgments

The authors thank the Center of Testing and Analysis, Nanjing University for support.

supplementary crystallographic information

Comment

The title compound, C15H17N3O4S, is one of aromatic carbamates which are an important class of esters compounds and have widespread applications from pharmaceuticals (Ishikawa et al., 1998) to agronomy (Riden & Hopkins, 1961). As part of our studies in this area, we report herein the synthesis and crystal structure of the title compound, (I).

In the molecule of (I) (Fig. 1), the ligand bond lengths and angles are within normal ranges (Allen et al., 1987). Rings A (C4/N1/C5/C6/S) and B (C10—C15) are almost planar and they are oriented at a dihedral angle of 74.1°.

In the crystal structure, intermolecular C—H···O hydrogen bonds (Table 1) link the molecules (Fig.2), in which they seem to be effective in the stabilization of the structure.

Experimental

For the preparation of the title compound, (I), a solution of N-methyl-N-((2-isopropyl-4-thiazoyl)methyl)amine (3.7 g, 21.7 mmol) and excess N-methyl morpholine in methylene chloride (70 ml) was cooled to 273 K, and treated with 4-nitophenyl chloroformate (6.0 g, 30 mmol). After being stirred for 6 h, the reaction mixture was diluted with CHCl3, washed successively with 1 N HCl, saturated aqueous NaHCO3, and saturated bine, dried over NaSO4, and concentrated in vacuo. The residue was purified by silica gel chromatography with 100% CHCl3 to provide the title compound, (I) (yield: 6.5 g, 87%). Crystals of (I) suitable for x-ray analysis were obtained by slow evaporation of an ethanol solution.

Refinement

H atoms were positioned geometrically, with N—H = 0.86 Å (for NH) and C—H = 0.93, 0.98 and 0.96 Å for aromatic, methine and methyl H, and constrained to ride on their parent atoms, with Uiso(H) = xUeq(C,N), where x = 1.5 for methyl H, and x = 1.2 for all other H atoms.

Figures

Fig. 1.
The molecular structure of the title molecule, with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.
Fig. 2.
A packing diagram for (I). Hydrogen bonds are shown as dashed lines.

Crystal data

C15H17N3O4SDx = 1.346 Mg m3
Mr = 335.38Melting point: 330(2) K
Orthorhombic, PbcaMo Kα radiation λ = 0.71073 Å
Hall symbol: -P 2ac 2abCell parameters from 25 reflections
a = 12.250 (3) Åθ = 9–12º
b = 10.876 (2) ŵ = 0.22 mm1
c = 24.845 (5) ÅT = 298 (2) K
V = 3310.1 (12) Å3Block, colourless
Z = 80.30 × 0.20 × 0.10 mm
F000 = 1408

Data collection

Enraf–Nonius CAD-4 diffractometerRint = 0.072
Radiation source: fine-focus sealed tubeθmax = 26.0º
Monochromator: graphiteθmin = 1.6º
T = 298(2) Kh = 0→15
ω/2θ scansk = 0→13
Absorption correction: ψ scan(North et al., 1968)l = 0→30
Tmin = 0.937, Tmax = 0.9793 standard reflections
3281 measured reflections every 200 reflections
3241 independent reflections intensity decay: none
1335 reflections with I > 2σ(I)

Refinement

Refinement on F2Secondary atom site location: difference Fourier map
Least-squares matrix: fullHydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.086H-atom parameters constrained
wR(F2) = 0.217  w = 1/[σ2(Fo2) + (0.070P)2 + 2.P] where P = (Fo2 + 2Fc2)/3
S = 1.04(Δ/σ)max < 0.001
3241 reflectionsΔρmax = 0.28 e Å3
184 parametersΔρmin = −0.39 e Å3
Primary atom site location: structure-invariant direct methodsExtinction correction: none

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 (Å2)

xyzUiso*/Ueq
S0.33658 (15)0.04646 (16)0.50156 (7)0.089
N20.2887 (3)−0.0166 (3)0.68311 (16)0.0430 (10)
O10.1531 (3)−0.1308 (3)0.71949 (15)0.0610 (10)
C10.5582 (5)0.2987 (6)0.4986 (2)0.084
H1A0.59150.22830.51520.127*
H1B0.56180.36750.52270.127*
H1C0.59630.31820.46590.127*
O20.1198 (2)0.0537 (3)0.68088 (16)0.0585 (10)
N3−0.3347 (4)0.0160 (5)0.6666 (2)0.0668 (14)
C20.3731 (4)0.3175 (5)0.4459 (2)0.072
H2A0.41020.38090.42620.108*
H2B0.30870.35100.46230.108*
H2C0.35290.25230.42180.108*
O3−0.3851 (3)0.1042 (4)0.6861 (2)0.1009 (16)
C30.4429 (5)0.2710 (6)0.4862 (3)0.100 (2)
H3A0.46610.20490.46190.120*
O4−0.3738 (3)−0.0692 (5)0.6433 (2)0.1038 (17)
C40.3950 (5)0.1777 (6)0.5238 (3)0.0841 (19)
N10.3889 (4)0.1941 (5)0.5758 (2)0.0771 (14)
C50.3383 (4)0.0953 (4)0.6001 (2)0.0504 (13)
C60.3035 (5)0.0073 (6)0.5665 (2)0.0785 (17)
H6A0.2670−0.06400.57670.094*
C70.3260 (4)0.0983 (4)0.6607 (2)0.0491 (13)
H7A0.39590.11910.67670.059*
H7B0.27460.16250.67030.059*
C80.3718 (3)−0.1137 (4)0.6951 (2)0.0547 (15)
H8A0.3359−0.18510.70940.082*
H8B0.4231−0.08300.72100.082*
H8C0.4096−0.13530.66260.082*
C90.1861 (4)−0.0440 (5)0.69588 (18)0.0460 (12)
C100.0078 (3)0.0370 (4)0.6816 (2)0.0448 (12)
C11−0.0386 (4)−0.0625 (4)0.6552 (2)0.0494 (12)
H11A0.0058−0.12380.64090.059*
C12−0.1534 (4)−0.0707 (5)0.6500 (2)0.0564 (13)
H12A−0.1871−0.13560.63220.068*
C13−0.2133 (3)0.0258 (5)0.67368 (19)0.0457 (12)
C14−0.1691 (4)0.1211 (4)0.6979 (2)0.0483 (12)
H14A−0.21270.18390.71130.058*
C15−0.0556 (3)0.1265 (4)0.70306 (18)0.041
H15A−0.02350.19180.72130.049*

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
S0.0890.0890.0890.0000.0000.000
N20.035 (2)0.035 (2)0.059 (3)0.0008 (17)−0.0029 (19)0.009 (2)
O10.059 (2)0.044 (2)0.080 (3)−0.0118 (18)−0.006 (2)0.019 (2)
C10.0840.0840.0840.0000.0000.000
O20.0345 (17)0.0361 (19)0.105 (3)0.0031 (15)0.0086 (19)0.008 (2)
N30.041 (3)0.083 (4)0.076 (4)−0.009 (3)0.014 (3)0.024 (3)
C20.0720.0720.0720.0000.0000.000
O30.049 (2)0.095 (3)0.159 (5)0.014 (2)−0.002 (3)−0.009 (3)
C30.091 (5)0.102 (6)0.106 (6)−0.012 (4)0.000 (5)0.016 (5)
O40.052 (2)0.129 (4)0.131 (4)−0.030 (3)−0.001 (3)−0.026 (4)
C40.067 (4)0.099 (4)0.087 (4)−0.016 (3)−0.010 (4)0.024 (4)
N10.067 (3)0.081 (3)0.083 (3)−0.019 (3)−0.014 (3)0.033 (3)
C50.040 (3)0.037 (3)0.074 (3)0.005 (2)−0.001 (3)0.003 (2)
C60.082 (4)0.073 (4)0.080 (4)−0.011 (3)0.000 (3)0.010 (3)
C70.041 (3)0.034 (3)0.072 (4)−0.007 (2)−0.001 (3)0.001 (3)
C80.043 (3)0.030 (3)0.092 (4)0.015 (2)0.001 (3)0.003 (3)
C90.048 (3)0.053 (3)0.037 (3)0.011 (3)0.002 (2)0.010 (3)
C100.041 (2)0.040 (3)0.054 (3)−0.006 (2)0.009 (2)0.015 (2)
C110.045 (3)0.043 (3)0.060 (3)0.003 (2)0.007 (2)0.002 (2)
C120.050 (3)0.061 (3)0.058 (3)0.000 (3)−0.017 (3)−0.004 (3)
C130.031 (2)0.055 (3)0.051 (3)−0.005 (2)−0.002 (2)0.000 (2)
C140.040 (2)0.038 (3)0.067 (3)0.000 (2)0.008 (3)0.002 (2)
C150.0410.0260.055−0.0030.0130.003

Geometric parameters (Å, °)

S—C41.689 (7)C4—N11.307 (7)
S—C61.716 (6)N1—C51.379 (6)
N2—C91.330 (5)C5—C61.341 (7)
N2—C71.442 (5)C5—C71.513 (7)
N2—C81.496 (5)C6—H6A0.9300
O1—C91.183 (5)C7—H7A0.9700
C1—C31.477 (6)C7—H7B0.9700
C1—H1A0.9600C8—H8A0.9600
C1—H1B0.9600C8—H8B0.9600
C1—H1C0.9600C8—H8C0.9600
O2—C101.384 (5)C10—C151.355 (6)
O2—C91.388 (5)C10—C111.387 (6)
N3—O41.193 (6)C11—C121.415 (6)
N3—O31.239 (6)C11—H11A0.9300
N3—C131.502 (6)C12—C131.409 (7)
C2—C31.411 (7)C12—H12A0.9300
C2—H2A0.9600C13—C141.314 (6)
C2—H2B0.9600C14—C151.398 (6)
C2—H2C0.9600C14—H14A0.9300
C3—C41.498 (7)C15—H15A0.9300
C3—H3A0.9800
C4—S—C690.2 (3)S—C6—H6A125.3
C9—N2—C7125.8 (4)N2—C7—C5113.4 (4)
C9—N2—C8115.9 (4)N2—C7—H7A108.9
C7—N2—C8118.3 (4)C5—C7—H7A108.9
C3—C1—H1A109.5N2—C7—H7B108.9
C3—C1—H1B109.5C5—C7—H7B108.9
H1A—C1—H1B109.5H7A—C7—H7B107.7
C3—C1—H1C109.5N2—C8—H8A109.5
H1A—C1—H1C109.5N2—C8—H8B109.5
H1B—C1—H1C109.5H8A—C8—H8B109.5
C10—O2—C9118.4 (4)N2—C8—H8C109.5
O4—N3—O3126.3 (5)H8A—C8—H8C109.5
O4—N3—C13120.6 (5)H8B—C8—H8C109.5
O3—N3—C13113.1 (5)O1—C9—N2128.3 (5)
C3—C2—H2A109.5O1—C9—O2123.0 (4)
C3—C2—H2B109.5N2—C9—O2108.5 (4)
H2A—C2—H2B109.5C15—C10—O2118.6 (4)
C3—C2—H2C109.5C15—C10—C11120.8 (4)
H2A—C2—H2C109.5O2—C10—C11120.2 (4)
H2B—C2—H2C109.5C10—C11—C12119.9 (5)
C2—C3—C1130.9 (6)C10—C11—H11A120.0
C2—C3—C4116.5 (5)C12—C11—H11A120.0
C1—C3—C4112.6 (6)C13—C12—C11115.6 (5)
C2—C3—H3A90.1C13—C12—H12A122.2
C1—C3—H3A90.1C11—C12—H12A122.2
C4—C3—H3A90.1C14—C13—C12124.3 (4)
N1—C4—C3123.1 (6)C14—C13—N3121.2 (5)
N1—C4—S114.4 (5)C12—C13—N3114.4 (5)
C3—C4—S122.3 (5)C13—C14—C15119.0 (5)
C4—N1—C5110.7 (5)C13—C14—H14A120.5
C6—C5—N1115.2 (5)C15—C14—H14A120.5
C6—C5—C7127.1 (5)C10—C15—C14120.3 (5)
N1—C5—C7117.6 (5)C10—C15—H15A119.9
C5—C6—S109.5 (5)C14—C15—H15A119.9
C5—C6—H6A125.3
C2—C3—C4—N1−120.0 (7)C8—N2—C9—O2−178.4 (4)
C1—C3—C4—N159.8 (9)C10—O2—C9—O1−16.1 (7)
C2—C3—C4—S55.9 (8)C10—O2—C9—N2168.8 (4)
C1—C3—C4—S−124.4 (6)C9—O2—C10—C15135.6 (4)
C6—S—C4—N1−1.3 (5)C9—O2—C10—C11−51.9 (6)
C6—S—C4—C3−177.5 (6)C15—C10—C11—C120.5 (7)
C3—C4—N1—C5178.2 (5)O2—C10—C11—C12−171.8 (4)
S—C4—N1—C52.1 (7)C10—C11—C12—C13−0.8 (7)
C4—N1—C5—C6−2.0 (7)C11—C12—C13—C142.1 (8)
C4—N1—C5—C7179.1 (5)C11—C12—C13—N3178.8 (4)
N1—C5—C6—S1.0 (6)O4—N3—C13—C14178.0 (5)
C7—C5—C6—S179.8 (4)O3—N3—C13—C14−0.6 (7)
C4—S—C6—C50.1 (5)O4—N3—C13—C121.1 (7)
C9—N2—C7—C5−97.3 (5)O3—N3—C13—C12−177.5 (5)
C8—N2—C7—C584.9 (5)C12—C13—C14—C15−2.9 (8)
C6—C5—C7—N210.8 (7)N3—C13—C14—C15−179.5 (4)
N1—C5—C7—N2−170.4 (4)O2—C10—C15—C14171.1 (4)
C7—N2—C9—O1−171.1 (5)C11—C10—C15—C14−1.3 (7)
C8—N2—C9—O16.8 (8)C13—C14—C15—C102.5 (7)
C7—N2—C9—O23.7 (7)

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
C2—H2C···O4i0.962.583.493 (7)159

Symmetry codes: (i) −x, −y, −z+1.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: BQ2046).

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.
  • Enraf–Nonius (1989). CAD-4 Software. Version 5.0. Enraf–Nonius, Delft, The Netherlands.
  • Harms, K. & Wocadlo, S. (1995). XCAD4 University of Marburg, Germany.
  • Ishikawa,T., Utoh, M., Sawada, N., Nishida, N., Fukase, Y., Sekiguchi, F. & Ishitsuka, H. (1998). Biochem. Pharmacol.55, 1091–1097.. [PubMed]
  • North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351–359.
  • Riden, J. R. & Hopkins, T. R. (1961). J. Agric. Food. Chem.9, 47–48.
  • Sheldrick, G. M. (1997). SHELXS97 and SHELXL97 University of Göttingen, Germany.
  • Siemens (1996). SHELXTL Version 5.06. Siemens Analytical X-ray Instruments Inc., Madison, Wisconsin, USA.

Articles from Acta Crystallographica Section E: Structure Reports Online are provided here courtesy of International Union of Crystallography