1-(4-Nitro­phen­yl)-3-pivaloylthio­urea

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.

Key indicators

• Single-crystal X-ray study
• T = 113 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.053
• wR factor = 0.102
• Data-to-parameter ratio = 16.6

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S1. Comment

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

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).

S2. Experimental

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%.

S3. Refinement

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

Computing details

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

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

Crystal data

C12H15N3O3S	F(000) = 592
Mr = 281.33	Dx = 1.394 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71070 Å
Hall symbol: -P 2yn	Cell parameters from 3440 reflections
a = 6.207 (3) Å	θ = 3.1–27.5°
b = 10.878 (5) Å	µ = 0.25 mm^−1
c = 19.990 (9) Å	T = 113 K
β = 96.706 (6)°	Block, light yellow
V = 1340.5 (10) Å^3	0.40 × 0.22 × 0.20 mm
Z = 4

Data collection

Rigaku/MSC Mercury CCD diffractometer	2622 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.043
Graphite monochromator	θmax = 27.5°, θmin = 3.3°
Detector resolution: 14.62 pixels mm^-1	h = −8→6
ω scans	k = −13→14
10513 measured reflections	l = −25→22
3029 independent reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.053	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.102	H atoms treated by a mixture of independent and constrained refinement
S = 1.19	w = 1/[σ^2(Fo^2) + (0.0315P)^2 + 0.6155P] where P = (Fo^2 + 2Fc^2)/3
3029 reflections	(Δ/σ)max < 0.001
183 parameters	Δρmax = 0.29 e Å^−3
0 restraints	Δρmin = −0.25 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
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)
N1	0.0525 (2)	0.01268 (16)	0.62050 (8)	0.0184 (3)
H1	0.088 (3)	−0.060 (2)	0.6322 (11)	0.022 (6)*
C2	−0.1402 (3)	−0.21796 (18)	0.59510 (9)	0.0179 (4)
O1	0.0266 (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)*
C3	0.1814 (3)	0.11237 (18)	0.64588 (9)	0.0175 (4)
C4	0.1056 (3)	0.23198 (19)	0.65144 (10)	0.0207 (4)
H4	−0.0403	0.2519	0.6353	0.025*
C5	0.2443 (3)	0.32160 (19)	0.68060 (10)	0.0211 (4)
H5	0.1947	0.4035	0.6848	0.025*
C6	0.4560 (3)	0.29053 (18)	0.70352 (10)	0.0185 (4)
C7	0.5339 (3)	0.17179 (19)	0.69980 (10)	0.0224 (4)
H7	0.6793	0.1522	0.7167	0.027*
C8	0.3949 (3)	0.08264 (19)	0.67092 (10)	0.0217 (4)
H8	0.4445	0.0004	0.6680	0.026*
N3	0.6011 (3)	0.38608 (16)	0.73402 (8)	0.0221 (4)
O2	0.5311 (2)	0.49171 (13)	0.73614 (7)	0.0281 (3)
O3	0.7875 (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	−0.2729	0.4768	0.037*
H10B	−0.3775	−0.4195	0.4837	0.037*
H10C	−0.1536	−0.3473	0.4819	0.037*
C11	−0.4969 (3)	−0.3203 (2)	0.60073 (11)	0.0232 (4)
H11A	−0.4758	−0.3102	0.6498	0.035*
H11B	−0.5824	−0.3947	0.5892	0.035*
H11C	−0.5740	−0.2486	0.5801	0.035*
C12	−0.1541 (3)	−0.44494 (19)	0.60566 (11)	0.0261 (5)
H12A	−0.0134	−0.4525	0.5883	0.039*
H12B	−0.2406	−0.5189	0.5940	0.039*
H12C	−0.1316	−0.4356	0.6547	0.039*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0178 (9)	0.0195 (10)	0.0159 (10)	−0.0011 (7)	0.0032 (7)	−0.0016 (8)
S1	0.0226 (2)	0.0190 (3)	0.0248 (3)	−0.00128 (19)	−0.00565 (18)	0.0035 (2)
N1	0.0184 (8)	0.0156 (9)	0.0202 (9)	0.0010 (6)	−0.0023 (6)	0.0008 (7)
C2	0.0172 (9)	0.0200 (10)	0.0172 (10)	0.0014 (7)	0.0045 (7)	0.0004 (8)
O1	0.0186 (7)	0.0219 (8)	0.0247 (8)	0.0006 (5)	−0.0035 (5)	0.0034 (6)
N2	0.0157 (8)	0.0180 (9)	0.0210 (9)	−0.0005 (6)	−0.0035 (6)	0.0015 (7)
C3	0.0176 (8)	0.0194 (10)	0.0152 (10)	−0.0021 (7)	0.0009 (7)	0.0011 (8)
C4	0.0181 (9)	0.0214 (11)	0.0218 (11)	0.0029 (7)	−0.0009 (7)	−0.0002 (8)
C5	0.0234 (9)	0.0190 (10)	0.0205 (11)	0.0007 (8)	0.0012 (8)	−0.0006 (8)
C6	0.0197 (9)	0.0213 (10)	0.0147 (10)	−0.0048 (7)	0.0018 (7)	−0.0004 (8)
C7	0.0183 (9)	0.0243 (11)	0.0238 (11)	−0.0001 (8)	−0.0014 (7)	0.0018 (9)
C8	0.0213 (9)	0.0197 (10)	0.0231 (11)	0.0027 (8)	−0.0010 (7)	0.0017 (8)
N3	0.0241 (8)	0.0240 (10)	0.0184 (9)	−0.0056 (7)	0.0026 (6)	−0.0001 (7)
O2	0.0351 (8)	0.0205 (8)	0.0284 (9)	−0.0052 (6)	0.0028 (6)	−0.0031 (6)
O3	0.0215 (7)	0.0356 (9)	0.0363 (9)	−0.0054 (6)	−0.0046 (6)	−0.0037 (7)
C9	0.0188 (9)	0.0189 (10)	0.0206 (10)	−0.0011 (7)	0.0013 (7)	0.0005 (8)
C10	0.0296 (10)	0.0192 (11)	0.0253 (12)	−0.0028 (8)	0.0026 (8)	−0.0033 (9)
C11	0.0198 (9)	0.0237 (11)	0.0264 (12)	−0.0026 (8)	0.0035 (8)	0.0020 (9)
C12	0.0257 (10)	0.0174 (11)	0.0347 (13)	0.0003 (8)	0.0010 (9)	0.0027 (9)

Geometric parameters (Å, º)

C1—N1	1.342 (2)	C7—C8	1.379 (3)
C1—N2	1.397 (2)	C7—H7	0.9500
C1—S1	1.662 (2)	C8—H8	0.9500
N1—C3	1.407 (2)	N3—O3	1.230 (2)
N1—H1	0.85 (2)	N3—O2	1.231 (2)
C2—O1	1.225 (2)	C9—C10	1.535 (3)
C2—N2	1.383 (3)	C9—C12	1.535 (3)
C2—C9	1.525 (3)	C9—C11	1.541 (3)
N2—H2	0.86 (2)	C10—H10A	0.9800
C3—C4	1.392 (3)	C10—H10B	0.9800
C3—C8	1.399 (3)	C10—H10C	0.9800
C4—C5	1.384 (3)	C11—H11A	0.9800
C4—H4	0.9500	C11—H11B	0.9800
C5—C6	1.382 (3)	C11—H11C	0.9800
C5—H5	0.9500	C12—H12A	0.9800
C6—C7	1.384 (3)	C12—H12B	0.9800
C6—N3	1.461 (2)	C12—H12C	0.9800
N1—C1—N2	113.70 (17)	C3—C8—H8	119.7
N1—C1—S1	127.24 (15)	O3—N3—O2	123.14 (17)
N2—C1—S1	119.06 (14)	O3—N3—C6	118.48 (17)
C1—N1—C3	130.83 (17)	O2—N3—C6	118.39 (16)
C1—N1—H1	109.0 (15)	C2—C9—C10	109.23 (16)
C3—N1—H1	120.2 (15)	C2—C9—C12	108.32 (15)
O1—C2—N2	121.93 (18)	C10—C9—C12	109.11 (17)
O1—C2—C9	122.04 (18)	C2—C9—C11	108.78 (16)
N2—C2—C9	116.02 (16)	C10—C9—C11	111.65 (16)
C2—N2—C1	128.37 (16)	C12—C9—C11	109.69 (17)
C2—N2—H2	118.1 (14)	C9—C10—H10A	109.5
C1—N2—H2	113.4 (14)	C9—C10—H10B	109.5
C4—C3—C8	120.16 (18)	H10A—C10—H10B	109.5
C4—C3—N1	124.45 (17)	C9—C10—H10C	109.5
C8—C3—N1	115.22 (17)	H10A—C10—H10C	109.5
C5—C4—C3	119.49 (18)	H10B—C10—H10C	109.5
C5—C4—H4	120.3	C9—C11—H11A	109.5
C3—C4—H4	120.3	C9—C11—H11B	109.5
C6—C5—C4	119.23 (19)	H11A—C11—H11B	109.5
C6—C5—H5	120.4	C9—C11—H11C	109.5
C4—C5—H5	120.4	H11A—C11—H11C	109.5
C5—C6—C7	122.34 (18)	H11B—C11—H11C	109.5
C5—C6—N3	118.71 (18)	C9—C12—H12A	109.5
C7—C6—N3	118.94 (17)	C9—C12—H12B	109.5
C8—C7—C6	118.25 (18)	H12A—C12—H12B	109.5
C8—C7—H7	120.9	C9—C12—H12C	109.5
C6—C7—H7	120.9	H12A—C12—H12C	109.5
C7—C8—C3	120.50 (19)	H12B—C12—H12C	109.5
C7—C8—H8	119.7
N2—C1—N1—C3	−175.10 (18)	N3—C6—C7—C8	179.96 (17)
S1—C1—N1—C3	6.2 (3)	C6—C7—C8—C3	0.3 (3)
O1—C2—N2—C1	3.1 (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—O3	177.85 (18)
S1—C1—N2—C2	173.91 (15)	C7—C6—N3—O3	−0.9 (3)
C1—N1—C3—C4	27.2 (3)	C5—C6—N3—O2	−2.3 (3)
C1—N1—C3—C8	−157.51 (19)	C7—C6—N3—O2	178.91 (18)
C8—C3—C4—C5	1.4 (3)	O1—C2—C9—C10	−123.10 (19)
N1—C3—C4—C5	176.48 (18)	N2—C2—C9—C10	57.8 (2)
C3—C4—C5—C6	0.2 (3)	O1—C2—C9—C12	−4.4 (2)
C4—C5—C6—C7	−1.5 (3)	N2—C2—C9—C12	176.48 (16)
C4—C5—C6—N3	179.80 (17)	O1—C2—C9—C11	114.8 (2)
C5—C6—C7—C8	1.3 (3)	N2—C2—C9—C11	−64.3 (2)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.85 (2)	1.82 (2)	2.590 (3)	150 (2)