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

Xu, H.; Wang, P.; Huang, W.-L.

doi:10.1107/S1600536807063532

organic compounds

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ISSN: 2056-9890

Volume 64| Part 1| January 2008| Page o149

https://doi.org/10.1107/S1600536807063532

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

Hao Xu,^a Peng Wang ^b and Wen-Long Huang ^b ^*

^aDepartment of Applied Chemistry, College of Sciences, Nanjing University of Technology, Xinmofan Road No.5, Nanjing 210009, People's Republic of China, and ^bCenter of Drug Discovery, China Pharmaceutical University, Nanjing 210009, People's Republic of China
^*Correspondence e-mail: wangpeng159@163.com

(Received 11 November 2007; accepted 26 November 2007; online 6 December 2007)

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 ); Ishikawa et al. (1998 ); Riden & Hopkins (1961 ).

Experimental

Crystal data

C₁₅H₁₇N₃O₄S
M_r = 335.38
Orthorhombic, P b c a
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 ) 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[F² > 2σ(F²)] = 0.086
wR(F²) = 0.217
S = 1.04
3241 reflections
184 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C2—H2C⋯O4ⁱ	0.96	2.58	3.493 (7)	159
Symmetry code: (i) -x, -y, -z+1.

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

Supporting information

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

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063532/bq2046Isup2.hkl

checkCIF report

Comment top

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.

Related literature top

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

Experimental top

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.

Structure description top

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.

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

Computing details top

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

Figures top

	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.

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

Crystal data top

C₁₅H₁₇N₃O₄S	D_x = 1.346 Mg m⁻³
M_r = 335.38	Melting point: 330(2) K
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 25 reflections
a = 12.250 (3) Å	θ = 9–12°
b = 10.876 (2) Å	µ = 0.22 mm⁻¹
c = 24.845 (5) Å	T = 298 K
V = 3310.1 (12) Å³	Block, colourless
Z = 8	0.30 × 0.20 × 0.10 mm
F(000) = 1408

Data collection top

Enraf–Nonius CAD-4 diffractometer	1335 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.072
Graphite monochromator	θ_max = 26.0°, θ_min = 1.6°
ω/2θ scans	h = 0→15
Absorption correction: ψ scan (North et al., 1968)	k = 0→13
T_min = 0.937, T_max = 0.979	l = 0→30
3281 measured reflections	3 standard reflections every 200 reflections
3241 independent reflections	intensity decay: none

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.086	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.217	H-atom parameters constrained
S = 1.04	w = 1/[σ²(F_o²) + (0.070P)² + 2.P] where P = (F_o² + 2F_c²)/3
3241 reflections	(Δ/σ)_max < 0.001
184 parameters	Δρ_max = 0.28 e Å⁻³
0 restraints	Δρ_min = −0.39 e Å⁻³

Crystal data top

C₁₅H₁₇N₃O₄S	V = 3310.1 (12) Å³
M_r = 335.38	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 12.250 (3) Å	µ = 0.22 mm⁻¹
b = 10.876 (2) Å	T = 298 K
c = 24.845 (5) Å	0.30 × 0.20 × 0.10 mm

Data collection top

Enraf–Nonius CAD-4 diffractometer	1335 reflections with I > 2σ(I)
Absorption correction: ψ scan (North et al., 1968)	R_int = 0.072
T_min = 0.937, T_max = 0.979	3 standard reflections every 200 reflections
3281 measured reflections	intensity decay: none
3241 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.086	0 restraints
wR(F²) = 0.217	H-atom parameters constrained
S = 1.04	Δρ_max = 0.28 e Å⁻³
3241 reflections	Δρ_min = −0.39 e Å⁻³
184 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
S	0.33658 (15)	0.04646 (16)	0.50156 (7)	0.089
N2	0.2887 (3)	−0.0166 (3)	0.68311 (16)	0.0430 (10)
O1	0.1531 (3)	−0.1308 (3)	0.71949 (15)	0.0610 (10)
C1	0.5582 (5)	0.2987 (6)	0.4986 (2)	0.084
H1A	0.5915	0.2283	0.5152	0.127*
H1B	0.5618	0.3675	0.5227	0.127*
H1C	0.5963	0.3182	0.4659	0.127*
O2	0.1198 (2)	0.0537 (3)	0.68088 (16)	0.0585 (10)
N3	−0.3347 (4)	0.0160 (5)	0.6666 (2)	0.0668 (14)
C2	0.3731 (4)	0.3175 (5)	0.4459 (2)	0.072
H2A	0.4102	0.3809	0.4262	0.108*
H2B	0.3087	0.3510	0.4623	0.108*
H2C	0.3529	0.2523	0.4218	0.108*
O3	−0.3851 (3)	0.1042 (4)	0.6861 (2)	0.1009 (16)
C3	0.4429 (5)	0.2710 (6)	0.4862 (3)	0.100 (2)
H3A	0.4661	0.2049	0.4619	0.120*
O4	−0.3738 (3)	−0.0692 (5)	0.6433 (2)	0.1038 (17)
C4	0.3950 (5)	0.1777 (6)	0.5238 (3)	0.0841 (19)
N1	0.3889 (4)	0.1941 (5)	0.5758 (2)	0.0771 (14)
C5	0.3383 (4)	0.0953 (4)	0.6001 (2)	0.0504 (13)
C6	0.3035 (5)	0.0073 (6)	0.5665 (2)	0.0785 (17)
H6A	0.2670	−0.0640	0.5767	0.094*
C7	0.3260 (4)	0.0983 (4)	0.6607 (2)	0.0491 (13)
H7A	0.3959	0.1191	0.6767	0.059*
H7B	0.2746	0.1625	0.6703	0.059*
C8	0.3718 (3)	−0.1137 (4)	0.6951 (2)	0.0547 (15)
H8A	0.3359	−0.1851	0.7094	0.082*
H8B	0.4231	−0.0830	0.7210	0.082*
H8C	0.4096	−0.1353	0.6626	0.082*
C9	0.1861 (4)	−0.0440 (5)	0.69588 (18)	0.0460 (12)
C10	0.0078 (3)	0.0370 (4)	0.6816 (2)	0.0448 (12)
C11	−0.0386 (4)	−0.0625 (4)	0.6552 (2)	0.0494 (12)
H11A	0.0058	−0.1238	0.6409	0.059*
C12	−0.1534 (4)	−0.0707 (5)	0.6500 (2)	0.0564 (13)
H12A	−0.1871	−0.1356	0.6322	0.068*
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	−0.2127	0.1839	0.7113	0.058*
C15	−0.0556 (3)	0.1265 (4)	0.70306 (18)	0.041
H15A	−0.0235	0.1918	0.7213	0.049*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S	0.089	0.089	0.089	0.000	0.000	0.000
N2	0.035 (2)	0.035 (2)	0.059 (3)	0.0008 (17)	−0.0029 (19)	0.009 (2)
O1	0.059 (2)	0.044 (2)	0.080 (3)	−0.0118 (18)	−0.006 (2)	0.019 (2)
C1	0.084	0.084	0.084	0.000	0.000	0.000
O2	0.0345 (17)	0.0361 (19)	0.105 (3)	0.0031 (15)	0.0086 (19)	0.008 (2)
N3	0.041 (3)	0.083 (4)	0.076 (4)	−0.009 (3)	0.014 (3)	0.024 (3)
C2	0.072	0.072	0.072	0.000	0.000	0.000
O3	0.049 (2)	0.095 (3)	0.159 (5)	0.014 (2)	−0.002 (3)	−0.009 (3)
C3	0.091 (5)	0.102 (6)	0.106 (6)	−0.012 (4)	0.000 (5)	0.016 (5)
O4	0.052 (2)	0.129 (4)	0.131 (4)	−0.030 (3)	−0.001 (3)	−0.026 (4)
C4	0.067 (4)	0.099 (4)	0.087 (4)	−0.016 (3)	−0.010 (4)	0.024 (4)
N1	0.067 (3)	0.081 (3)	0.083 (3)	−0.019 (3)	−0.014 (3)	0.033 (3)
C5	0.040 (3)	0.037 (3)	0.074 (3)	0.005 (2)	−0.001 (3)	0.003 (2)
C6	0.082 (4)	0.073 (4)	0.080 (4)	−0.011 (3)	0.000 (3)	0.010 (3)
C7	0.041 (3)	0.034 (3)	0.072 (4)	−0.007 (2)	−0.001 (3)	0.001 (3)
C8	0.043 (3)	0.030 (3)	0.092 (4)	0.015 (2)	0.001 (3)	0.003 (3)
C9	0.048 (3)	0.053 (3)	0.037 (3)	0.011 (3)	0.002 (2)	0.010 (3)
C10	0.041 (2)	0.040 (3)	0.054 (3)	−0.006 (2)	0.009 (2)	0.015 (2)
C11	0.045 (3)	0.043 (3)	0.060 (3)	0.003 (2)	0.007 (2)	0.002 (2)
C12	0.050 (3)	0.061 (3)	0.058 (3)	0.000 (3)	−0.017 (3)	−0.004 (3)
C13	0.031 (2)	0.055 (3)	0.051 (3)	−0.005 (2)	−0.002 (2)	0.000 (2)
C14	0.040 (2)	0.038 (3)	0.067 (3)	0.000 (2)	0.008 (3)	0.002 (2)
C15	0.041	0.026	0.055	−0.003	0.013	0.003

Geometric parameters (Å, º) top

S—C4	1.689 (7)	C4—N1	1.307 (7)
S—C6	1.716 (6)	N1—C5	1.379 (6)
N2—C9	1.330 (5)	C5—C6	1.341 (7)
N2—C7	1.442 (5)	C5—C7	1.513 (7)
N2—C8	1.496 (5)	C6—H6A	0.9300
O1—C9	1.183 (5)	C7—H7A	0.9700
C1—C3	1.477 (6)	C7—H7B	0.9700
C1—H1A	0.9600	C8—H8A	0.9600
C1—H1B	0.9600	C8—H8B	0.9600
C1—H1C	0.9600	C8—H8C	0.9600
O2—C10	1.384 (5)	C10—C15	1.355 (6)
O2—C9	1.388 (5)	C10—C11	1.387 (6)
N3—O4	1.193 (6)	C11—C12	1.415 (6)
N3—O3	1.239 (6)	C11—H11A	0.9300
N3—C13	1.502 (6)	C12—C13	1.409 (7)
C2—C3	1.411 (7)	C12—H12A	0.9300
C2—H2A	0.9600	C13—C14	1.314 (6)
C2—H2B	0.9600	C14—C15	1.398 (6)
C2—H2C	0.9600	C14—H14A	0.9300
C3—C4	1.498 (7)	C15—H15A	0.9300
C3—H3A	0.9800

C4—S—C6	90.2 (3)	S—C6—H6A	125.3
C9—N2—C7	125.8 (4)	N2—C7—C5	113.4 (4)
C9—N2—C8	115.9 (4)	N2—C7—H7A	108.9
C7—N2—C8	118.3 (4)	C5—C7—H7A	108.9
C3—C1—H1A	109.5	N2—C7—H7B	108.9
C3—C1—H1B	109.5	C5—C7—H7B	108.9
H1A—C1—H1B	109.5	H7A—C7—H7B	107.7
C3—C1—H1C	109.5	N2—C8—H8A	109.5
H1A—C1—H1C	109.5	N2—C8—H8B	109.5
H1B—C1—H1C	109.5	H8A—C8—H8B	109.5
C10—O2—C9	118.4 (4)	N2—C8—H8C	109.5
O4—N3—O3	126.3 (5)	H8A—C8—H8C	109.5
O4—N3—C13	120.6 (5)	H8B—C8—H8C	109.5
O3—N3—C13	113.1 (5)	O1—C9—N2	128.3 (5)
C3—C2—H2A	109.5	O1—C9—O2	123.0 (4)
C3—C2—H2B	109.5	N2—C9—O2	108.5 (4)
H2A—C2—H2B	109.5	C15—C10—O2	118.6 (4)
C3—C2—H2C	109.5	C15—C10—C11	120.8 (4)
H2A—C2—H2C	109.5	O2—C10—C11	120.2 (4)
H2B—C2—H2C	109.5	C10—C11—C12	119.9 (5)
C2—C3—C1	130.9 (6)	C10—C11—H11A	120.0
C2—C3—C4	116.5 (5)	C12—C11—H11A	120.0
C1—C3—C4	112.6 (6)	C13—C12—C11	115.6 (5)
C2—C3—H3A	90.1	C13—C12—H12A	122.2
C1—C3—H3A	90.1	C11—C12—H12A	122.2
C4—C3—H3A	90.1	C14—C13—C12	124.3 (4)
N1—C4—C3	123.1 (6)	C14—C13—N3	121.2 (5)
N1—C4—S	114.4 (5)	C12—C13—N3	114.4 (5)
C3—C4—S	122.3 (5)	C13—C14—C15	119.0 (5)
C4—N1—C5	110.7 (5)	C13—C14—H14A	120.5
C6—C5—N1	115.2 (5)	C15—C14—H14A	120.5
C6—C5—C7	127.1 (5)	C10—C15—C14	120.3 (5)
N1—C5—C7	117.6 (5)	C10—C15—H15A	119.9
C5—C6—S	109.5 (5)	C14—C15—H15A	119.9
C5—C6—H6A	125.3

C2—C3—C4—N1	−120.0 (7)	C8—N2—C9—O2	−178.4 (4)
C1—C3—C4—N1	59.8 (9)	C10—O2—C9—O1	−16.1 (7)
C2—C3—C4—S	55.9 (8)	C10—O2—C9—N2	168.8 (4)
C1—C3—C4—S	−124.4 (6)	C9—O2—C10—C15	135.6 (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—C12	0.5 (7)
C3—C4—N1—C5	178.2 (5)	O2—C10—C11—C12	−171.8 (4)
S—C4—N1—C5	2.1 (7)	C10—C11—C12—C13	−0.8 (7)
C4—N1—C5—C6	−2.0 (7)	C11—C12—C13—C14	2.1 (8)
C4—N1—C5—C7	179.1 (5)	C11—C12—C13—N3	178.8 (4)
N1—C5—C6—S	1.0 (6)	O4—N3—C13—C14	178.0 (5)
C7—C5—C6—S	179.8 (4)	O3—N3—C13—C14	−0.6 (7)
C4—S—C6—C5	0.1 (5)	O4—N3—C13—C12	1.1 (7)
C9—N2—C7—C5	−97.3 (5)	O3—N3—C13—C12	−177.5 (5)
C8—N2—C7—C5	84.9 (5)	C12—C13—C14—C15	−2.9 (8)
C6—C5—C7—N2	10.8 (7)	N3—C13—C14—C15	−179.5 (4)
N1—C5—C7—N2	−170.4 (4)	O2—C10—C15—C14	171.1 (4)
C7—N2—C9—O1	−171.1 (5)	C11—C10—C15—C14	−1.3 (7)
C8—N2—C9—O1	6.8 (8)	C13—C14—C15—C10	2.5 (7)
C7—N2—C9—O2	3.7 (7)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2C···O4ⁱ	0.96	2.58	3.493 (7)	159

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₇N₃O₄S
M_r	335.38
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	12.250 (3), 10.876 (2), 24.845 (5)
V (Å³)	3310.1 (12)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.30 × 0.20 × 0.10

Data collection
Diffractometer	Enraf–Nonius CAD-4
Absorption correction	ψ scan (North et al., 1968)
T_min, T_max	0.937, 0.979
No. of measured, independent and observed [I > 2σ(I)] reflections	3281, 3241, 1335
R_int	0.072
(sin θ/λ)_max (Å⁻¹)	0.616

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.086, 0.217, 1.04
No. of reflections	3241
No. of parameters	184
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.28, −0.39

Computer programs: CAD-4 Software (Enraf–Nonius, 1989), XCAD4 (Harms & Wocadlo,1995), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Siemens,1996).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C2—H2C···O4ⁱ	0.9600	2.5800	3.493 (7)	159.00

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

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

References

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