1-(4-Nitro­benzo­yl)-3-phenyl­thio­urea

Geometric parameters of the title compound, C₁₄H₁₁N₃O₃S, are in the usual ranges. The mol­ecular conformation is stabilized by an N—H...O hydrogen bond. In the crystal structure, the mol­ecules form centrosymmetric dimers connected by N—H...S hydrogen bonds. The molecule is almost planar (r.m.s. deviation for all atoms = 0.268 Å); only the torsion angles about the C—C bond between the carbonyl group and the nitrophenyl ring [O—C—C—C = −157.92 (16)°] and about the C—N bond between the phenyl ring and the amide group [C—N—C—C = 15.9 (3)°] differ significantly from 0 or 180°.

Key indicators

• Single-crystal X-ray study
• T = 173 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.034
• wR factor = 0.086
• Data-to-parameter ratio = 12.9

checkCIF/PLATON results

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Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    N3     -   C14     ..       5.05 su

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   0 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

1-Aroyl-3-arylthioureas are extremely versatile building blocks for the synthesis of a diversity of heterocyclic compounds: imidazole-2-thiones (Zeng et al., 2003) and 1,3-thiazolines (Saeed & Pervez, 2006) and 2-aroylimino-3-aryl-thiazolidin-4-ones (Saeed et al., 2007). N,N-Dialkyl-N-aroylthioureas are efficient ligands for the separation of platinum group metals (Koch, 2001). 1,3-Dialkyl- or diarylthioureas have shown significant antifungal activity against plant pathogens Pyricularia oryzae and Drechslera oryzae (Krishnamurthy et al., 1999) and 1-benzoyl-3-(4,6-disubstituted-pyrimidine-2-yl)thioureas have shown excellent herbicidal activity (Sijia et al., 2003).

Geometric parameters of the title compound in Fig. 1 are in the usual ranges. The molecular conformation is stabilized by an N—H···O hydrogen bond. In the crystal of the title compound, the molecules form centrosymmetric dimers connected by N—H···S hydrogen bonds (Fig. 2).

Related literature

For related literature, see: Koch (2001); Krishnamurthy et al. (1999); Saeed et al. (2007); Saeed & Pervez (2006); Sijia et al. (2003); Zeng et al. (2003).

S2. Experimental

To a suspension of potassium thiocyanate (0.97 g, 10 mmol) in acetone (30 ml) a solution of 4-nitrobenzoyl chloride (1.85 g, 10 mmol) in acetone (40 ml) was added dropwise and the reaction mixture was refluxed for 45 min. After cooling to room temperature, a solution of aniline (0.93 g, 10 mmol) in acetone (10 ml) was added and the resulting was mixture refluxed for 2 h. The reaction mixture was poured into cold water when the thiourea was precipitated as a solid. Recrystallized from ethanol as colourless crystals (2.7 g, 9.0 mmol, 90%). m.p. 433 K. IR (KBr) cm^-1: 3351 (free NH), 3200 (assoc. NH), 1667 (CO), 1610 (arom.), 1529 (thioureido I) 1325 II, 1160 III, 744, 762; ¹H NMR (CDCl₃) δ: 7.31–7.75 (aromatic), 9.19 (1H, s, broad, NH); 12.76` (1H, s, broad, NH); ¹³C NMR (CDCl₃) 126.2 (4 CH), 129.0 (2 CH), 129.20 (2CH), 130.7 (C), 132.1 (C),134.8 (C) 142.3 (C), 168.1 (C═O), 178.4 (C═S). EIMS m/e: 301, 168.9,126, 119, 91, 64.9. Analysis calculated for C₁₄H₁₁N₃O₃S: C 55.80, H 3.68, N 13.95, S 10.64%. Found: C 55.32, H 3.63, N 14.05, O 15.83, S 10.69%.

S3. Refinement

H atoms were found in a difference map, but those bonded to C were refined using a riding model with C—H = 0.95Å and U_iso(H) = 1.2U_eq(C). The H atoms bonded to N were freely refined.

Computing details

Data collection: X-AREA (Stoe & Cie, 2001); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003) and XP (Sheldrick, 1991); software used to prepare material for publication: SHELXL97.

Figures

	Fig. 1. Molecular structure of title compound.
	Fig. 2. Crystal packing, view onto the bc plane. H-atoms not involved in hydrogen bonds are omitted. Hydrogen bonds are shown as dashed lines.

1-(4-Nitrobenzoyl)-3-phenylthiourea

Crystal data

C14H11N3O3S	F(000) = 624
Mr = 301.32	Dx = 1.460 Mg m^−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3023 reflections
a = 8.266 (1) Å	θ = 3.5–25.7°
b = 12.1458 (9) Å	µ = 0.25 mm^−1
c = 13.6687 (16) Å	T = 173 K
β = 92.651 (10)°	Plate, light brown
V = 1370.8 (3) Å^3	0.36 × 0.35 × 0.33 mm
Z = 4

Data collection

Stoe IPDSII two-circle diffractometer	2552 independent reflections
Radiation source: fine-focus sealed tube	2189 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.035
ω scans	θmax = 25.7°, θmin = 3.7°
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995)	h = −10→9
Tmin = 0.915, Tmax = 0.922	k = −14→14
7976 measured reflections	l = −16→16

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)] = 0.034	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.086	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ^2(Fo^2) + (0.0429P)^2 + 0.4301P] where P = (Fo^2 + 2Fc^2)/3
2552 reflections	(Δ/σ)max = 0.001
198 parameters	Δρmax = 0.18 e Å^−3
0 restraints	Δρmin = −0.27 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	0.28377 (6)	0.03643 (3)	0.56649 (4)	0.04069 (15)
O1	0.43815 (14)	0.35452 (9)	0.41816 (8)	0.0331 (3)
N1	0.43245 (16)	0.16919 (11)	0.44820 (10)	0.0276 (3)
H1	0.468 (2)	0.1061 (18)	0.4329 (14)	0.041 (5)*
N2	0.28612 (16)	0.25938 (11)	0.56390 (10)	0.0272 (3)
H2	0.318 (3)	0.3148 (19)	0.5309 (15)	0.048 (6)*
N3	0.80042 (19)	0.19139 (16)	0.03823 (11)	0.0458 (4)
O3	0.8597 (2)	0.27153 (16)	0.00061 (11)	0.0732 (5)
O4	0.8076 (2)	0.09774 (16)	0.00561 (11)	0.0710 (5)
C1	0.47242 (18)	0.25966 (12)	0.39415 (11)	0.0249 (3)
C2	0.33267 (18)	0.16213 (12)	0.52899 (11)	0.0264 (3)
C11	0.55951 (18)	0.23703 (12)	0.30229 (11)	0.0246 (3)
C12	0.5533 (2)	0.13494 (13)	0.25513 (11)	0.0297 (3)
H12	0.4948	0.0760	0.2823	0.036*
C13	0.6324 (2)	0.11912 (15)	0.16862 (12)	0.0347 (4)
H13	0.6300	0.0497	0.1366	0.042*
C14	0.71447 (19)	0.20733 (15)	0.13050 (11)	0.0320 (4)
C15	0.7210 (2)	0.30996 (15)	0.17389 (12)	0.0336 (4)
H15	0.7772	0.3691	0.1451	0.040*
C16	0.64315 (19)	0.32438 (13)	0.26103 (11)	0.0293 (3)
H16	0.6468	0.3940	0.2927	0.035*
C21	0.19553 (18)	0.28671 (13)	0.64695 (11)	0.0256 (3)
C22	0.1432 (2)	0.39581 (14)	0.65039 (12)	0.0334 (4)
H22	0.1616	0.4443	0.5975	0.040*
C23	0.0637 (2)	0.43343 (15)	0.73191 (14)	0.0399 (4)
H23	0.0287	0.5078	0.7343	0.048*
C24	0.0352 (2)	0.36344 (16)	0.80929 (13)	0.0389 (4)
H24	−0.0188	0.3895	0.8646	0.047*
C25	0.0864 (2)	0.25506 (16)	0.80501 (12)	0.0360 (4)
H25	0.0666	0.2068	0.8578	0.043*
C26	0.16682 (19)	0.21546 (14)	0.72428 (11)	0.0313 (4)
H26	0.2014	0.1409	0.7222	0.038*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
S1	0.0497 (3)	0.0230 (2)	0.0519 (3)	0.00346 (18)	0.0294 (2)	0.00788 (19)
O1	0.0479 (7)	0.0208 (6)	0.0321 (6)	−0.0008 (5)	0.0179 (5)	−0.0017 (5)
N1	0.0356 (7)	0.0207 (7)	0.0276 (7)	0.0039 (5)	0.0134 (5)	0.0024 (5)
N2	0.0341 (7)	0.0226 (7)	0.0261 (7)	−0.0001 (5)	0.0120 (5)	0.0010 (6)
N3	0.0408 (8)	0.0710 (12)	0.0259 (7)	0.0174 (8)	0.0050 (6)	−0.0059 (8)
O3	0.0937 (13)	0.0830 (12)	0.0467 (9)	0.0268 (10)	0.0450 (9)	0.0214 (9)
O4	0.0732 (11)	0.0910 (13)	0.0504 (9)	0.0029 (9)	0.0198 (8)	−0.0404 (9)
C1	0.0283 (8)	0.0229 (8)	0.0240 (7)	−0.0011 (6)	0.0054 (6)	0.0000 (6)
C2	0.0273 (7)	0.0254 (8)	0.0271 (7)	0.0016 (6)	0.0074 (6)	0.0026 (6)
C11	0.0273 (7)	0.0243 (8)	0.0224 (7)	0.0023 (6)	0.0038 (6)	0.0006 (6)
C12	0.0370 (8)	0.0261 (8)	0.0260 (7)	0.0001 (6)	0.0023 (6)	−0.0015 (6)
C13	0.0434 (9)	0.0336 (9)	0.0269 (8)	0.0076 (7)	−0.0003 (7)	−0.0088 (7)
C14	0.0324 (8)	0.0455 (10)	0.0184 (7)	0.0116 (7)	0.0045 (6)	−0.0012 (7)
C15	0.0352 (8)	0.0380 (9)	0.0284 (8)	0.0009 (7)	0.0104 (7)	0.0053 (7)
C16	0.0368 (8)	0.0249 (8)	0.0270 (8)	−0.0002 (6)	0.0092 (6)	−0.0012 (6)
C21	0.0248 (7)	0.0281 (8)	0.0244 (7)	−0.0015 (6)	0.0064 (6)	−0.0023 (6)
C22	0.0382 (9)	0.0284 (8)	0.0343 (8)	−0.0008 (7)	0.0093 (7)	−0.0017 (7)
C23	0.0400 (9)	0.0352 (9)	0.0456 (10)	0.0029 (7)	0.0125 (8)	−0.0114 (8)
C24	0.0334 (9)	0.0512 (11)	0.0331 (9)	−0.0017 (8)	0.0119 (7)	−0.0128 (8)
C25	0.0345 (9)	0.0482 (10)	0.0261 (8)	−0.0041 (7)	0.0097 (7)	0.0007 (7)
C26	0.0321 (8)	0.0344 (9)	0.0283 (8)	0.0002 (7)	0.0092 (6)	0.0019 (7)

Geometric parameters (Å, º)

S1—C2	1.6661 (15)	C13—H13	0.9500
O1—C1	1.2345 (18)	C14—C15	1.380 (3)
N1—C1	1.373 (2)	C15—C16	1.391 (2)
N1—C2	1.4111 (18)	C15—H15	0.9500
N1—H1	0.85 (2)	C16—H16	0.9500
N2—C2	1.3373 (19)	C21—C26	1.395 (2)
N2—C21	1.4276 (19)	C21—C22	1.395 (2)
N2—H2	0.86 (2)	C22—C23	1.397 (2)
N3—O3	1.215 (2)	C22—H22	0.9500
N3—O4	1.224 (2)	C23—C24	1.386 (3)
N3—C14	1.489 (2)	C23—H23	0.9500
C1—C11	1.501 (2)	C24—C25	1.385 (3)
C11—C12	1.397 (2)	C24—H24	0.9500
C11—C16	1.399 (2)	C25—C26	1.399 (2)
C12—C13	1.390 (2)	C25—H25	0.9500
C12—H12	0.9500	C26—H26	0.9500
C13—C14	1.383 (3)
C1—N1—C2	129.32 (13)	C13—C14—N3	118.70 (16)
C1—N1—H1	119.7 (13)	C14—C15—C16	118.10 (15)
C2—N1—H1	111.0 (13)	C14—C15—H15	120.9
C2—N2—C21	131.25 (14)	C16—C15—H15	120.9
C2—N2—H2	114.0 (14)	C15—C16—C11	120.43 (15)
C21—N2—H2	114.8 (14)	C15—C16—H16	119.8
O3—N3—O4	124.27 (16)	C11—C16—H16	119.8
O3—N3—C14	118.18 (17)	C26—C21—C22	119.99 (14)
O4—N3—C14	117.55 (18)	C26—C21—N2	124.90 (14)
O1—C1—N1	122.69 (13)	C22—C21—N2	114.98 (14)
O1—C1—C11	121.20 (13)	C21—C22—C23	119.72 (16)
N1—C1—C11	116.11 (13)	C21—C22—H22	120.1
N2—C2—N1	114.45 (13)	C23—C22—H22	120.1
N2—C2—S1	128.43 (11)	C24—C23—C22	120.73 (17)
N1—C2—S1	117.09 (11)	C24—C23—H23	119.6
C12—C11—C16	119.68 (14)	C22—C23—H23	119.6
C12—C11—C1	122.65 (13)	C25—C24—C23	119.20 (15)
C16—C11—C1	117.59 (13)	C25—C24—H24	120.4
C13—C12—C11	120.42 (15)	C23—C24—H24	120.4
C13—C12—H12	119.8	C24—C25—C26	121.15 (16)
C11—C12—H12	119.8	C24—C25—H25	119.4
C14—C13—C12	118.12 (15)	C26—C25—H25	119.4
C14—C13—H13	120.9	C21—C26—C25	119.20 (16)
C12—C13—H13	120.9	C21—C26—H26	120.4
C15—C14—C13	123.22 (14)	C25—C26—H26	120.4
C15—C14—N3	118.07 (16)
C2—N1—C1—O1	9.0 (3)	O3—N3—C14—C13	173.47 (17)
C2—N1—C1—C11	−170.27 (15)	O4—N3—C14—C13	−7.1 (2)
C21—N2—C2—N1	−175.45 (15)	C13—C14—C15—C16	1.0 (3)
C21—N2—C2—S1	6.5 (3)	N3—C14—C15—C16	−178.89 (14)
C1—N1—C2—N2	−8.4 (2)	C14—C15—C16—C11	−0.6 (2)
C1—N1—C2—S1	169.96 (13)	C12—C11—C16—C15	−0.5 (2)
O1—C1—C11—C12	−157.92 (16)	C1—C11—C16—C15	−177.50 (15)
N1—C1—C11—C12	21.4 (2)	C2—N2—C21—C26	15.9 (3)
O1—C1—C11—C16	19.0 (2)	C2—N2—C21—C22	−168.24 (16)
N1—C1—C11—C16	−161.71 (14)	C26—C21—C22—C23	0.7 (3)
C16—C11—C12—C13	1.3 (2)	N2—C21—C22—C23	−175.42 (15)
C1—C11—C12—C13	178.13 (15)	C21—C22—C23—C24	−0.4 (3)
C11—C12—C13—C14	−0.9 (2)	C22—C23—C24—C25	−0.1 (3)
C12—C13—C14—C15	−0.3 (3)	C23—C24—C25—C26	0.3 (3)
C12—C13—C14—N3	179.65 (15)	C22—C21—C26—C25	−0.5 (2)
O3—N3—C14—C15	−6.6 (2)	N2—C21—C26—C25	175.20 (15)
O4—N3—C14—C15	172.86 (17)	C24—C25—C26—C21	0.0 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1^i	0.85 (2)	2.68 (2)	3.4386 (14)	148.6 (17)
N2—H2···O1	0.86 (2)	1.93 (2)	2.6673 (16)	143 (2)

Symmetry code: (i) −x+1, −y, −z+1.