Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807034587/at2340sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S1600536807034587/at2340Isup2.hkl |
CCDC reference: 657805
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%.
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 Uiso(H) = 1.2Ueq(C). The H atoms bonded to N were freely refined.
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).
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).
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.
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. |
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) Å3 | 0.36 × 0.35 × 0.33 mm |
Z = 4 |
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 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)] = 0.034 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0429P)2 + 0.4301P] where P = (Fo2 + 2Fc2)/3 |
2552 reflections | (Δ/σ)max = 0.001 |
198 parameters | Δρmax = 0.18 e Å−3 |
0 restraints | Δρmin = −0.27 e Å−3 |
C14H11N3O3S | V = 1370.8 (3) Å3 |
Mr = 301.32 | Z = 4 |
Monoclinic, P21/c | Mo Kα radiation |
a = 8.266 (1) Å | µ = 0.25 mm−1 |
b = 12.1458 (9) Å | T = 173 K |
c = 13.6687 (16) Å | 0.36 × 0.35 × 0.33 mm |
β = 92.651 (10)° |
Stoe IPDSII two-circle diffractometer | 2552 independent reflections |
Absorption correction: multi-scan (MULABS; Spek, 2003; Blessing, 1995) | 2189 reflections with I > 2σ(I) |
Tmin = 0.915, Tmax = 0.922 | Rint = 0.035 |
7976 measured reflections |
R[F2 > 2σ(F2)] = 0.034 | 0 restraints |
wR(F2) = 0.086 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.18 e Å−3 |
2552 reflections | Δρmin = −0.27 e Å−3 |
198 parameters |
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. |
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* |
U11 | U22 | U33 | U12 | U13 | U23 | |
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) |
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) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 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. |
Experimental details
Crystal data | |
Chemical formula | C14H11N3O3S |
Mr | 301.32 |
Crystal system, space group | Monoclinic, P21/c |
Temperature (K) | 173 |
a, b, c (Å) | 8.266 (1), 12.1458 (9), 13.6687 (16) |
β (°) | 92.651 (10) |
V (Å3) | 1370.8 (3) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.25 |
Crystal size (mm) | 0.36 × 0.35 × 0.33 |
Data collection | |
Diffractometer | Stoe IPDSII two-circle |
Absorption correction | Multi-scan (MULABS; Spek, 2003; Blessing, 1995) |
Tmin, Tmax | 0.915, 0.922 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7976, 2552, 2189 |
Rint | 0.035 |
(sin θ/λ)max (Å−1) | 0.610 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.034, 0.086, 1.02 |
No. of reflections | 2552 |
No. of parameters | 198 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.18, −0.27 |
Computer programs: X-AREA (Stoe & Cie, 2001), X-AREA, SHELXS97 (Sheldrick, 1990), SHELXL97 (Sheldrick, 1997), PLATON (Spek, 2003) and XP (Sheldrick, 1991), SHELXL97.
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 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. |
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).