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Acta Cryst. (2007). E63, o2801    [ doi:10.1107/S1600536807020995 ]

1-(4-Nitrophenyl)-3-pivaloylthiourea

S. Sultana, M. Khawar Rauf, M. Ebihara and A. Badshah

Abstract top

In the title compound [systematic name: 1-(2,2-dimethylpropionyl)-3-(4-nitrophenyl)thiourea], C12H15N3O3S, the molecule exists in the thione form with typical thiourea C-S and C-O bonds, as well as shortened C-N bond lengths. The planes containing the thiourea N atoms form dihedral angles of 27.12 (7) and 1.6 (2)°, respectively, with the benzene ring. The molecule exhibits only an intramolecular N-H...O hydrogen bond and no intermolecular N-H...S hydrogen bonds. This is in contrast to the usual behaviour of this class of compounds.

Comment top

N-Aryl-N'-aroyl thiourea derivatives are very useful building blocks for the synthesis of a wide range of aliphatic macromolecular and heterocyclic compounds. Thus, benzothiazoles have been prepared from arylthioureas in the presence of bromine (Patil & Chedekel, 1984), and condensation of thiourea with α-halocarbonyl compounds form 2-aminothiazoles (Baily et al., 1996). 2-Methylaminothiazolines have been synthesized by cyclization of N-(2-hydroxyethyl)-N'-methylthioureas (Namgun et al., 2001). Thioureas are efficient guanylating agents (Maryanoff et al., 1986). N, N-dialkyl-N-aroylthioureas have been efficiently used for the extraction of nickel, palladium and platinum metals (Koch, 2001). Herein, as a continuation of these studies, the structure of the title compound (I) is described, Fig. 1 & Table 1. Bond lengths and angles can be regarded as normal (Allen, 2002; Shoukat et al., 2007) and show the molecule to exist in the thione form with typical thiourea C—S and C—O bonds, as well as shortened C—N bond lengths. The thiocarbonyl and carbonyl groups are almost coplanar, as reflected by the torsion angles of 3.1 (3)° for O(1)—C(2)—N(2)—C(1), -4.9 (3)° for N(1)—C(1)—N(2)—C(2). This is associated with the expected intramolecular N—H···O hydrogen bonds (Table 2)

Related literature top

The bond lengths and angles are quite typical for N,N'-disubstituted thiourea compounds found in the Cambridge Structural Database (Version 5.28, Allen, 2002; Khawar Rauf et al., 2006).

For related literature, see: Baily et al. (1996); Koch (2001); Maryanoff et al. (1986); Namgun et al. (2001); Patil & Chedekel (1984); Shoukat et al. (2007).

Experimental top

Freshly prepared pivaloylisothiocyanate (1.43 g, 10 mmol) was dissolved in acetone (30 ml) and stirred for 20 minutes. Neat 4-nitroaniline (1.38 g, 10 mmol) was then added and the resulting mixture was stirred for 1 h. The reaction mixture was then poured into acidified water and stirred well. The solid product was separated and washed with deionized water and purified by recrystallization from ethanol/1,1-dichloromethane (1:1 v/v) to give fine crystals of (I), with an overall yield 85%.

Refinement top

C-bound H atoms were included in the riding model approximation with C—H 0.95 - 0.98 Å, and with Uiso(H) = 1.2 Ueq(C) or Uiso(H) = 1.5 Ueq(Cmethyl). The N-bound H atoms were refined isotropically, see Table 2 for distances.

Computing details top

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell refinement: CrystalClear; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku, 2004); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: SHELXL97 and TEXSAN.

Figures top
[Figure 1] Fig. 1. Molecular structure of (I) showing atom labelling and displacement ellipsoids drawn at the 50% probability level. The hydrogen bond is shown as dashed lines.
1-(2,2-dimethylpropionyl)-3-(4-nitrophenyl)thiourea top
Crystal data top
C12H15N3O3SF(000) = 592
Mr = 281.33Dx = 1.394 Mg m−3
Monoclinic, P21/nMo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2ynCell parameters from 3440 reflections
a = 6.207 (3) Åθ = 3.1–27.5°
b = 10.878 (5) ŵ = 0.25 mm−1
c = 19.990 (9) ÅT = 113 K
β = 96.706 (6)°Block, light yellow
V = 1340.5 (10) Å30.40 × 0.22 × 0.20 mm
Z = 4
Data collection top
Rigaku/MSC Mercury CCD
diffractometer		2622 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.043
graphiteθmax = 27.5°, θmin = 3.3°
Detector resolution: 14.62 pixels mm-1h = −8→6
ω scansk = −13→14
10513 measured reflectionsl = −25→22
3029 independent reflections
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)] = 0.053Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.102H atoms treated by a mixture of independent and constrained refinement
S = 1.19 w = 1/[σ2(Fo2) + (0.0315P)2 + 0.6155P]
where P = (Fo2 + 2Fc2)/3
3029 reflections(Δ/σ)max < 0.001
183 parametersΔρmax = 0.29 e Å−3
0 restraintsΔρmin = −0.25 e Å−3
Crystal data top
C12H15N3O3SV = 1340.5 (10) Å3
Mr = 281.33Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.207 (3) ŵ = 0.25 mm−1
b = 10.878 (5) ÅT = 113 K
c = 19.990 (9) Å0.40 × 0.22 × 0.20 mm
β = 96.706 (6)°
Data collection top
Rigaku/MSC Mercury CCD
diffractometer		2622 reflections with I > 2σ(I)
10513 measured reflectionsRint = 0.043
3029 independent reflectionsθmax = 27.5°
Refinement top
R[F2 > 2σ(F2)] = 0.053H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.102Δρmax = 0.29 e Å−3
S = 1.19Δρmin = −0.25 e Å−3
3029 reflectionsAbsolute structure: ?
183 parametersFlack parameter: ?
0 restraintsRogers parameter: ?
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
C1−0.1277 (3)0.00927 (18)0.57635 (9)0.0176 (4)
S1−0.24312 (8)0.12580 (5)0.53185 (3)0.02278 (14)
N10.0525 (2)0.01268 (16)0.62050 (8)0.0184 (3)
H10.088 (3)−0.060 (2)0.6322 (11)0.022 (6)*
C2−0.1402 (3)−0.21796 (18)0.59510 (9)0.0179 (4)
O10.0266 (2)−0.22339 (13)0.63433 (7)0.0222 (3)
N2−0.2195 (2)−0.10775 (15)0.56787 (9)0.0187 (4)
H2−0.336 (3)−0.1095 (19)0.5394 (11)0.019 (5)*
C30.1814 (3)0.11237 (18)0.64588 (9)0.0175 (4)
C40.1056 (3)0.23198 (19)0.65144 (10)0.0207 (4)
H4−0.04030.25190.63530.025*
C50.2443 (3)0.32160 (19)0.68060 (10)0.0211 (4)
H50.19470.40350.68480.025*
C60.4560 (3)0.29053 (18)0.70352 (10)0.0185 (4)
C70.5339 (3)0.17179 (19)0.69980 (10)0.0224 (4)
H70.67930.15220.71670.027*
C80.3949 (3)0.08264 (19)0.67092 (10)0.0217 (4)
H80.44450.00040.66800.026*
N30.6011 (3)0.38608 (16)0.73402 (8)0.0221 (4)
O20.5311 (2)0.49171 (13)0.73614 (7)0.0281 (3)
O30.7875 (2)0.35722 (15)0.75618 (8)0.0318 (4)
C9−0.2745 (3)−0.33191 (18)0.57417 (10)0.0195 (4)
C10−0.2978 (3)−0.34397 (19)0.49716 (10)0.0248 (4)
H10A−0.3774−0.27290.47680.037*
H10B−0.3775−0.41950.48370.037*
H10C−0.1536−0.34730.48190.037*
C11−0.4969 (3)−0.3203 (2)0.60073 (11)0.0232 (4)
H11A−0.4758−0.31020.64980.035*
H11B−0.5824−0.39470.58920.035*
H11C−0.5740−0.24860.58010.035*
C12−0.1541 (3)−0.44494 (19)0.60566 (11)0.0261 (5)
H12A−0.0134−0.45250.58830.039*
H12B−0.2406−0.51890.59400.039*
H12C−0.1316−0.43560.65470.039*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
C10.0178 (9)0.0195 (10)0.0159 (10)−0.0011 (7)0.0032 (7)−0.0016 (8)
S10.0226 (2)0.0190 (3)0.0248 (3)−0.00128 (19)−0.00565 (18)0.0035 (2)
N10.0184 (8)0.0156 (9)0.0202 (9)0.0010 (6)−0.0023 (6)0.0008 (7)
C20.0172 (9)0.0200 (10)0.0172 (10)0.0014 (7)0.0045 (7)0.0004 (8)
O10.0186 (7)0.0219 (8)0.0247 (8)0.0006 (5)−0.0035 (5)0.0034 (6)
N20.0157 (8)0.0180 (9)0.0210 (9)−0.0005 (6)−0.0035 (6)0.0015 (7)
C30.0176 (8)0.0194 (10)0.0152 (10)−0.0021 (7)0.0009 (7)0.0011 (8)
C40.0181 (9)0.0214 (11)0.0218 (11)0.0029 (7)−0.0009 (7)−0.0002 (8)
C50.0234 (9)0.0190 (10)0.0205 (11)0.0007 (8)0.0012 (8)−0.0006 (8)
C60.0197 (9)0.0213 (10)0.0147 (10)−0.0048 (7)0.0018 (7)−0.0004 (8)
C70.0183 (9)0.0243 (11)0.0238 (11)−0.0001 (8)−0.0014 (7)0.0018 (9)
C80.0213 (9)0.0197 (10)0.0231 (11)0.0027 (8)−0.0010 (7)0.0017 (8)
N30.0241 (8)0.0240 (10)0.0184 (9)−0.0056 (7)0.0026 (6)−0.0001 (7)
O20.0351 (8)0.0205 (8)0.0284 (9)−0.0052 (6)0.0028 (6)−0.0031 (6)
O30.0215 (7)0.0356 (9)0.0363 (9)−0.0054 (6)−0.0046 (6)−0.0037 (7)
C90.0188 (9)0.0189 (10)0.0206 (10)−0.0011 (7)0.0013 (7)0.0005 (8)
C100.0296 (10)0.0192 (11)0.0253 (12)−0.0028 (8)0.0026 (8)−0.0033 (9)
C110.0198 (9)0.0237 (11)0.0264 (12)−0.0026 (8)0.0035 (8)0.0020 (9)
C120.0257 (10)0.0174 (11)0.0347 (13)0.0003 (8)0.0010 (9)0.0027 (9)
Geometric parameters (Å, °) top
C1—N11.342 (2)C7—C81.379 (3)
C1—N21.397 (2)C7—H70.9500
C1—S11.662 (2)C8—H80.9500
N1—C31.407 (2)N3—O31.230 (2)
N1—H10.85 (2)N3—O21.231 (2)
C2—O11.225 (2)C9—C101.535 (3)
C2—N21.383 (3)C9—C121.535 (3)
C2—C91.525 (3)C9—C111.541 (3)
N2—H20.86 (2)C10—H10A0.9800
C3—C41.392 (3)C10—H10B0.9800
C3—C81.399 (3)C10—H10C0.9800
C4—C51.384 (3)C11—H11A0.9800
C4—H40.9500C11—H11B0.9800
C5—C61.382 (3)C11—H11C0.9800
C5—H50.9500C12—H12A0.9800
C6—C71.384 (3)C12—H12B0.9800
C6—N31.461 (2)C12—H12C0.9800
N1—C1—N2113.70 (17)C3—C8—H8119.7
N1—C1—S1127.24 (15)O3—N3—O2123.14 (17)
N2—C1—S1119.06 (14)O3—N3—C6118.48 (17)
C1—N1—C3130.83 (17)O2—N3—C6118.39 (16)
C1—N1—H1109.0 (15)C2—C9—C10109.23 (16)
C3—N1—H1120.2 (15)C2—C9—C12108.32 (15)
O1—C2—N2121.93 (18)C10—C9—C12109.11 (17)
O1—C2—C9122.04 (18)C2—C9—C11108.78 (16)
N2—C2—C9116.02 (16)C10—C9—C11111.65 (16)
C2—N2—C1128.37 (16)C12—C9—C11109.69 (17)
C2—N2—H2118.1 (14)C9—C10—H10A109.5
C1—N2—H2113.4 (14)C9—C10—H10B109.5
C4—C3—C8120.16 (18)H10A—C10—H10B109.5
C4—C3—N1124.45 (17)C9—C10—H10C109.5
C8—C3—N1115.22 (17)H10A—C10—H10C109.5
C5—C4—C3119.49 (18)H10B—C10—H10C109.5
C5—C4—H4120.3C9—C11—H11A109.5
C3—C4—H4120.3C9—C11—H11B109.5
C6—C5—C4119.23 (19)H11A—C11—H11B109.5
C6—C5—H5120.4C9—C11—H11C109.5
C4—C5—H5120.4H11A—C11—H11C109.5
C5—C6—C7122.34 (18)H11B—C11—H11C109.5
C5—C6—N3118.71 (18)C9—C12—H12A109.5
C7—C6—N3118.94 (17)C9—C12—H12B109.5
C8—C7—C6118.25 (18)H12A—C12—H12B109.5
C8—C7—H7120.9C9—C12—H12C109.5
C6—C7—H7120.9H12A—C12—H12C109.5
C7—C8—C3120.50 (19)H12B—C12—H12C109.5
C7—C8—H8119.7
N2—C1—N1—C3−175.10 (18)N3—C6—C7—C8179.96 (17)
S1—C1—N1—C36.2 (3)C6—C7—C8—C30.3 (3)
O1—C2—N2—C13.1 (3)C4—C3—C8—C7−1.6 (3)
C9—C2—N2—C1−177.76 (18)N1—C3—C8—C7−177.15 (18)
N1—C1—N2—C2−4.9 (3)C5—C6—N3—O3177.85 (18)
S1—C1—N2—C2173.91 (15)C7—C6—N3—O3−0.9 (3)
C1—N1—C3—C427.2 (3)C5—C6—N3—O2−2.3 (3)
C1—N1—C3—C8−157.51 (19)C7—C6—N3—O2178.91 (18)
C8—C3—C4—C51.4 (3)O1—C2—C9—C10−123.10 (19)
N1—C3—C4—C5176.48 (18)N2—C2—C9—C1057.8 (2)
C3—C4—C5—C60.2 (3)O1—C2—C9—C12−4.4 (2)
C4—C5—C6—C7−1.5 (3)N2—C2—C9—C12176.48 (16)
C4—C5—C6—N3179.80 (17)O1—C2—C9—C11114.8 (2)
C5—C6—C7—C81.3 (3)N2—C2—C9—C11−64.3 (2)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.85 (2)1.82 (2)2.590 (3)150 (2)
Table 1
Selected geometric parameters (Å) top
C1—N11.342 (2)C2—O11.225 (2)
C1—N21.397 (2)C2—N21.383 (3)
C1—S11.662 (2)N3—O31.230 (2)
N1—C31.407 (2)N3—O21.231 (2)
Table 2
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1···O10.85 (2)1.82 (2)2.590 (3)150 (2)
Acknowledgements top

MKR is grateful to The HEC-Pakistan for financial support under the IRSIP program for Pre-doctoral Fellowship in Gifu University, Japan.

references
References top

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