1-Ethyl-1-methyl-3-(2-nitro­benzo­yl)thio­urea

Abstract

In the title compound, C₁₁H₁₃N₃O₃S, the benzene ring is twisted relative to the amidic fragment, forming a dihedral angle of 27.26 (9)°. The thiono and carbonyl groups are trans with respect to the C—N bond. Inter­molecular N—H⋯S and C—H⋯O hydrogen bonds link the mol­ecules in the crystal structure.

Related literature

For the synthesis, see: Al-abbasi et al. (2010 ▶). For related structures and background references, see: Shanmuga Sundara Raj et al. (1999 ▶); Arslan et al. (2003 ▶); Al-abbasi & Kassim (2011 ▶). For standard bond lengths, see: Allen et al. (1987 ▶) and for bond lengths in other substituted thio­ureas, see: Nasir et al. (2011 ▶); Pérez et al. (2011 ▶).

Experimental

Crystal data

• C₁₁H₁₃N₃O₃S

• M _r = 267.30

• Monoclinic,

• a = 11.447 (2) Å

• b = 7.8664 (15) Å

• c = 15.159 (3) Å

• β = 107.128 (4)°

• V = 1304.5 (4) ų

• Z = 4

• Mo Kα radiation

• μ = 0.25 mm⁻¹

• T = 298 K

• 0.55 × 0.38 × 0.21 mm

Data collection

• Bruker SMART APEX CCD area-detector diffractometer

• Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.874, T _max = 0.949

• 7105 measured reflections

• 2294 independent reflections

• 1971 reflections with I > 2σ(I)

• R _int = 0.020

Refinement

• R[F ² > 2σ(F ²)] = 0.043

• wR(F ²) = 0.124

• S = 1.06

• 2294 reflections

• 169 parameters

• 1 restraint

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.33 e Å⁻³

• Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536811024652/jh2299Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯S1i	0.85 (2)	2.55 (2)	3.3828 (18)	167 (2)
C6—H6⋯O3ii	0.93	2.41	3.317 (3)	164

Symmetry codes: (i) ; (ii) .

supplementary crystallographic information

Comment

The title compound, I, is a thiourea derivative analogous to our previously reported compounds (Al-abbasi & Kassim, 2011). Bond distances are similar to those usually found in other substituted thioureas [Nasir et al. (2011) & Pérez et al. (2011)]. The C–S and C–O exhibited the expected double-bond character. However, the C–N bond lengths are intermediate between a single and double, indicating a partial electron delocalization in the O1/C7/N1/C8/S1 fragment.

The phenyl ring is twisted due to the presence of the nitro group (O2O3N3) in ortho position. A rotation around C1—C7 bond makes the oxygen atom (O1) perpendicular to the phenyl ring mean planes and the torsion angles of C2C1C701 and C6C1C701 are -95.5 (2) and 86.5 (2)°, respectively. The dihedral angle between the mean planes of the thiourea (S1/N1/N2/C8/C9) and the phenyl ring (C1/C2/C3/C4/C5/C6/) plane is 27.56 (10)°. Other bond lengths and angles are in normal ranges (Allen et al. 1987).

The crystal structure is stabilized by the intermolecular N1—H1A···S1 and C5—H5A···O3 hydrogen bonds linking the molecules into a dimer resulting in a channel along [101] (Fig. 2).

Experimental

The title compound was prepared according to a previously reported procedure (Al-abbasi et al., 2010). A very pale browon colour crystal, suitable for X-ray crystallography, was obtained by a slow evaporation from ethanol solution at room temperature (yield 78%).

Refinement

Hydrogen atom of the amide group was determined from the diffrence Fourrier map and N—H was initially fixed at 0.86(0.01) Å and allowed to be refined on the parent N atom with U_iso(H) = 1.2U_eq(N). All other H atoms were postioned geometrically with C—H bond lengths in the range 0.93 - 0.97 Å and refined in the riding model approximation with U_iso(H)=1.2U_eq(C,N), except for methyl group where U_iso(H)= 1.5U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound with displacement ellipsoids drawn at the 50% probability level.

Fig. 2.

A packing diagram of the title compound viewed down the a-axis showing the intermolecular hydrogen bonds N1—H1A···S1 (-x + 1, -y, -z) and C6—H6···O3 (x, y + 1, z).

Crystal data

C11H13N3O3S	F(000) = 560
Mr = 267.30	Dx = 1.361 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4015 reflections
a = 11.447 (2) Å	θ = 2.0–25.0°
b = 7.8664 (15) Å	µ = 0.25 mm−1
c = 15.159 (3) Å	T = 298 K
β = 107.128 (4)°	Block, brown
V = 1304.5 (4) Å3	0.55 × 0.38 × 0.21 mm
Z = 4

Data collection

Bruker SMART APEX CCD area-detector diffractometer	2294 independent reflections
Radiation source: fine-focus sealed tube	1971 reflections with I > 2σ(I)
graphite	Rint = 0.020
ω scans	θmax = 25.0°, θmin = 2.0°
Absorption correction: multi-scan (SADABS; Bruker, 2000)	h = −13→13
Tmin = 0.874, Tmax = 0.949	k = −7→9
7105 measured reflections	l = −15→18

Refinement

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.124	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.065P)2 + 0.531P] where P = (Fo2 + 2Fc2)/3
2294 reflections	(Δ/σ)max < 0.001
169 parameters	Δρmax = 0.33 e Å−3
1 restraint	Δρmin = −0.19 e Å−3

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 (Ų)

	x	y	z	Uiso*/Ueq
S1	0.69163 (5)	0.06431 (8)	0.07382 (4)	0.0575 (2)
O1	0.49702 (13)	0.2128 (2)	0.24893 (10)	0.0608 (4)
O2	0.44396 (18)	−0.1541 (2)	0.17973 (16)	0.0811 (6)
O3	0.2858 (2)	−0.3156 (2)	0.14610 (17)	0.0984 (7)
N1	0.48480 (14)	0.1814 (2)	0.09706 (11)	0.0435 (4)
N2	0.65025 (15)	0.3643 (2)	0.14053 (13)	0.0528 (5)
N3	0.3344 (2)	−0.1771 (2)	0.15678 (14)	0.0612 (5)
C1	0.30487 (17)	0.1334 (2)	0.14682 (13)	0.0401 (4)
C2	0.25371 (19)	−0.0265 (3)	0.14295 (14)	0.0459 (5)
C3	0.1301 (2)	−0.0513 (4)	0.12710 (16)	0.0636 (7)
H3	0.0984	−0.1604	0.1258	0.076*
C4	0.0545 (2)	0.0879 (4)	0.11328 (18)	0.0731 (8)
H4	−0.0291	0.0735	0.1026	0.088*
C5	0.1024 (2)	0.2479 (4)	0.11526 (19)	0.0728 (8)
H5	0.0507	0.3418	0.1050	0.087*
C6	0.2264 (2)	0.2709 (3)	0.13230 (16)	0.0558 (6)
H6	0.2577	0.3803	0.1341	0.067*
C7	0.43942 (17)	0.1743 (2)	0.17127 (14)	0.0433 (5)
C8	0.60936 (17)	0.2138 (3)	0.10694 (13)	0.0441 (5)
C9	0.7795 (2)	0.4114 (3)	0.16004 (17)	0.0607 (6)
H9A	0.8292	0.3093	0.1710	0.073*
H9B	0.8039	0.4801	0.2156	0.073*
C10	0.8020 (3)	0.5099 (4)	0.0808 (2)	0.0793 (8)
H10A	0.7897	0.4366	0.0282	0.119*
H10B	0.8844	0.5518	0.0987	0.119*
H10C	0.7461	0.6038	0.0651	0.119*
C11	0.5729 (2)	0.5026 (3)	0.1556 (2)	0.0737 (8)
H11A	0.4905	0.4853	0.1175	0.111*
H11B	0.6028	0.6090	0.1400	0.111*
H11C	0.5747	0.5042	0.2193	0.111*
H1A	0.4498 (18)	0.123 (3)	0.0494 (11)	0.051 (6)*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
S1	0.0395 (3)	0.0708 (4)	0.0647 (4)	0.0004 (2)	0.0194 (3)	−0.0241 (3)
O1	0.0506 (9)	0.0857 (12)	0.0461 (9)	−0.0004 (8)	0.0142 (7)	−0.0123 (8)
O2	0.0695 (12)	0.0584 (11)	0.1181 (16)	0.0213 (9)	0.0318 (11)	0.0114 (10)
O3	0.134 (2)	0.0423 (10)	0.1218 (18)	−0.0117 (11)	0.0429 (15)	−0.0064 (10)
N1	0.0362 (8)	0.0513 (10)	0.0453 (9)	−0.0046 (7)	0.0156 (7)	−0.0126 (8)
N2	0.0415 (9)	0.0572 (11)	0.0618 (11)	−0.0084 (8)	0.0185 (8)	−0.0138 (9)
N3	0.0866 (15)	0.0377 (10)	0.0639 (12)	0.0017 (10)	0.0295 (11)	0.0017 (8)
C1	0.0402 (10)	0.0417 (10)	0.0428 (10)	0.0035 (8)	0.0190 (8)	−0.0007 (8)
C2	0.0504 (11)	0.0470 (11)	0.0449 (11)	0.0001 (9)	0.0209 (9)	0.0002 (8)
C3	0.0608 (14)	0.0764 (17)	0.0602 (14)	−0.0244 (13)	0.0279 (12)	−0.0070 (12)
C4	0.0389 (12)	0.118 (2)	0.0658 (16)	−0.0025 (14)	0.0213 (11)	−0.0029 (15)
C5	0.0510 (14)	0.090 (2)	0.0805 (18)	0.0280 (14)	0.0242 (12)	0.0086 (14)
C6	0.0536 (12)	0.0485 (12)	0.0698 (14)	0.0113 (10)	0.0252 (11)	0.0041 (10)
C7	0.0405 (10)	0.0429 (11)	0.0497 (11)	0.0049 (8)	0.0181 (9)	−0.0035 (8)
C8	0.0367 (10)	0.0560 (12)	0.0400 (10)	−0.0039 (9)	0.0122 (8)	−0.0071 (8)
C9	0.0448 (12)	0.0725 (15)	0.0638 (14)	−0.0165 (11)	0.0145 (10)	−0.0187 (12)
C10	0.0656 (16)	0.0856 (19)	0.090 (2)	−0.0134 (14)	0.0287 (14)	−0.0004 (16)
C11	0.0675 (16)	0.0533 (14)	0.107 (2)	−0.0033 (12)	0.0356 (15)	−0.0200 (14)

Geometric parameters (Å, °)

S1—C8	1.674 (2)	C3—H3	0.9300
O1—C7	1.206 (2)	C4—C5	1.370 (4)
O2—N3	1.212 (3)	C4—H4	0.9300
O3—N3	1.212 (3)	C5—C6	1.378 (3)
N1—C7	1.372 (2)	C5—H5	0.9300
N1—C8	1.412 (2)	C6—H6	0.9300
N1—H1A	0.849 (10)	C9—C10	1.514 (4)
N2—C8	1.319 (3)	C9—H9A	0.9700
N2—C11	1.462 (3)	C9—H9B	0.9700
N2—C9	1.469 (3)	C10—H10A	0.9600
N3—C2	1.479 (3)	C10—H10B	0.9600
C1—C2	1.381 (3)	C10—H10C	0.9600
C1—C6	1.382 (3)	C11—H11A	0.9600
C1—C7	1.509 (3)	C11—H11B	0.9600
C2—C3	1.378 (3)	C11—H11C	0.9600
C3—C4	1.372 (4)
C7—N1—C8	122.31 (16)	C1—C6—H6	119.6
C7—N1—H1A	118.6 (15)	O1—C7—N1	124.04 (18)
C8—N1—H1A	113.3 (15)	O1—C7—C1	121.22 (17)
C8—N2—C11	124.45 (18)	N1—C7—C1	114.38 (17)
C8—N2—C9	121.75 (18)	N2—C8—N1	115.81 (17)
C11—N2—C9	113.66 (19)	N2—C8—S1	125.42 (15)
O3—N3—O2	124.6 (2)	N1—C8—S1	118.75 (15)
O3—N3—C2	117.3 (2)	N2—C9—C10	111.5 (2)
O2—N3—C2	118.12 (18)	N2—C9—H9A	109.3
C2—C1—C6	117.29 (18)	C10—C9—H9A	109.3
C2—C1—C7	126.44 (17)	N2—C9—H9B	109.3
C6—C1—C7	116.16 (18)	C10—C9—H9B	109.3
C3—C2—C1	122.5 (2)	H9A—C9—H9B	108.0
C3—C2—N3	118.5 (2)	C9—C10—H10A	109.5
C1—C2—N3	118.97 (18)	C9—C10—H10B	109.5
C4—C3—C2	118.9 (2)	H10A—C10—H10B	109.5
C4—C3—H3	120.6	C9—C10—H10C	109.5
C2—C3—H3	120.6	H10A—C10—H10C	109.5
C5—C4—C3	120.0 (2)	H10B—C10—H10C	109.5
C5—C4—H4	120.0	N2—C11—H11A	109.5
C3—C4—H4	120.0	N2—C11—H11B	109.5
C4—C5—C6	120.5 (2)	H11A—C11—H11B	109.5
C4—C5—H5	119.8	N2—C11—H11C	109.5
C6—C5—H5	119.8	H11A—C11—H11C	109.5
C5—C6—C1	120.9 (2)	H11B—C11—H11C	109.5
C5—C6—H6	119.6
C6—C1—C2—C3	−1.2 (3)	C8—N1—C7—O1	8.5 (3)
C7—C1—C2—C3	174.71 (19)	C8—N1—C7—C1	−178.37 (17)
C6—C1—C2—N3	179.13 (19)	C2—C1—C7—O1	−95.5 (3)
C7—C1—C2—N3	−5.0 (3)	C6—C1—C7—O1	80.5 (3)
O3—N3—C2—C3	5.7 (3)	C2—C1—C7—N1	91.2 (2)
O2—N3—C2—C3	−172.8 (2)	C6—C1—C7—N1	−92.9 (2)
O3—N3—C2—C1	−174.6 (2)	C11—N2—C8—N1	−8.5 (3)
O2—N3—C2—C1	6.9 (3)	C9—N2—C8—N1	176.06 (19)
C1—C2—C3—C4	1.0 (3)	C11—N2—C8—S1	170.1 (2)
N3—C2—C3—C4	−179.3 (2)	C9—N2—C8—S1	−5.4 (3)
C2—C3—C4—C5	0.1 (4)	C7—N1—C8—N2	−63.8 (3)
C3—C4—C5—C6	−0.9 (4)	C7—N1—C8—S1	117.53 (18)
C4—C5—C6—C1	0.6 (4)	C8—N2—C9—C10	96.1 (3)
C2—C1—C6—C5	0.4 (3)	C11—N2—C9—C10	−79.8 (3)
C7—C1—C6—C5	−175.9 (2)

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···S1i	0.85 (2)	2.55 (2)	3.3828 (18)	167.(2)
C6—H6···O3ii	0.93	2.41	3.317 (3)	164

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