Acta Cryst. (2008). E64, o832 [ doi:10.1107/S1600536808009501 ]
The title compound, C17H18N2OS, adopts a trans-cis geometry of the thiourea group which is stabilized by intramolecular hydrogen bonds between the O atom of the carbonyl group and the H atom of the thioamide group. A C-H
S intramolecular hydrogen bond is also present. In the crystal structure, molecules are linked by intermolecular N-HS hydrogen bonds to form centrosymmetric dimers.
The mixture of 2-methylbenzoyl chloride (9.720 g, 0.025 mol) with the equimolar amount of ammonium thiocyanate (1.903 g, 0.025 mol) and 2,3-dimethyl aniline (3.025 g, 0.025 mol) in 40 ml dry acetone was refluxed with stirring for 4 h. The solution was filtered and left to evaporate at room temperature. The colourless crystals obtained after a few days, was found suitable for X-ray investigations. The yield was 85% with melting point 413.2–415.7 K.
H atoms on the C and N parent atoms were positioned geomatrically, with C—H = 0.96, 0.93 and N—H = 0.86Å
and constrained to ride on their parent atoms with Uiso(H) = 1.2Ueq(CH and NH) and 1.5Ueq(CH3).
Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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 (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2003).
![[Figure 1]](./at2557fig1thm.gif)
| Fig. 1. The molecular sStructure of (I) with displacement ellipsoids drawn at 50% probability level. The dashed lines indicates the intramolecular hydrogen bonds. |
![[Figure 2]](./at2557fig2thm.gif)
| Fig. 2. A packing diagram of (I). Hydrogen bonds are shown by dashed lines. |
| C17H18N2OS | Z = 2 |
| Mr = 298.39 | F000 = 316 |
| Triclinic, P1 | Dx = 1.269 Mg m−3 |
| Hall symbol: -P 1 | Mo Kα radiation λ = 0.71073 Å |
| a = 6.2569 (15) Å | Cell parameters from 1377 reflections |
| b = 9.862 (2) Å | θ = 1.5–25.5º |
| c = 13.986 (3) Å | µ = 0.21 mm−1 |
| α = 69.461 (4)º | T = 298 (2) K |
| β = 86.199 (4)º | Slab, colourless |
| γ = 75.206 (4)º | 0.27 × 0.18 × 0.09 mm |
| V = 781.1 (3) Å3 |
| Bruker SMART APEX CCD area-detector diffractometer | 2904 independent reflections |
| Radiation source: fine-focus sealed tube | 2069 reflections with I > 2σ(I) |
| Monochromator: graphite | Rint = 0.034 |
| Detector resolution: 83.66 pixels mm-1 | θmax = 25.5º |
| T = 298(2) K | θmin = 1.5º |
| ω scans | h = −7→7 |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | k = −11→11 |
| Tmin = 0.946, Tmax = 0.982 | l = −16→16 |
| 7817 measured reflections |
| Refinement on F2 | Secondary atom site location: difference Fourier map |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.047 | H-atom parameters constrained |
| wR(F2) = 0.119 | w = 1/[σ2(Fo2) + (0.0567P)2 + 0.1084P] where P = (Fo2 + 2Fc2)/3 |
| S = 1.02 | (Δ/σ)max = 0.001 |
| 2904 reflections | Δρmax = 0.23 e Å−3 |
| 193 parameters | Δρmin = −0.17 e Å−3 |
| Primary atom site location: structure-invariant direct methods | Extinction correction: none |
| C17H18N2OS | γ = 75.206 (4)º |
| Mr = 298.39 | V = 781.1 (3) Å3 |
| Triclinic, P1 | Z = 2 |
| a = 6.2569 (15) Å | Mo Kα |
| b = 9.862 (2) Å | µ = 0.21 mm−1 |
| c = 13.986 (3) Å | T = 298 (2) K |
| α = 69.461 (4)º | 0.27 × 0.18 × 0.09 mm |
| β = 86.199 (4)º |
| Bruker SMART APEX CCD area-detector diffractometer | 2904 independent reflections |
| Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2069 reflections with I > 2σ(I) |
| Tmin = 0.946, Tmax = 0.982 | Rint = 0.034 |
| 7817 measured reflections |
| R[F2 > 2σ(F2)] = 0.047 | 193 parameters |
| wR(F2) = 0.119 | H-atom parameters constrained |
| S = 1.02 | Δρmax = 0.23 e Å−3 |
| 2904 reflections | Δρmin = −0.17 e Å−3 |
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 | 0.00124 (10) | 0.51524 (6) | 0.34145 (4) | 0.0441 (2) | |
| O1 | 0.2196 (3) | 0.02671 (18) | 0.54848 (13) | 0.0630 (5) | |
| N1 | 0.1412 (3) | 0.27939 (19) | 0.50519 (13) | 0.0374 (4) | |
| H1 | 0.1341 | 0.3473 | 0.5313 | 0.045* | |
| N2 | 0.0595 (3) | 0.22917 (19) | 0.36460 (13) | 0.0394 (5) | |
| H2 | 0.0883 | 0.1375 | 0.4048 | 0.047* | |
| C1 | 0.2131 (4) | 0.0521 (3) | 0.75752 (18) | 0.0519 (6) | |
| H1A | 0.1042 | 0.0051 | 0.7537 | 0.062* | |
| C2 | 0.2787 (5) | 0.0473 (3) | 0.85127 (19) | 0.0644 (8) | |
| H2A | 0.2120 | −0.0007 | 0.9105 | 0.077* | |
| C3 | 0.4424 (5) | 0.1138 (3) | 0.8562 (2) | 0.0639 (8) | |
| H3 | 0.4864 | 0.1112 | 0.9192 | 0.077* | |
| C4 | 0.5414 (4) | 0.1835 (3) | 0.77013 (19) | 0.0541 (7) | |
| H4 | 0.6543 | 0.2264 | 0.7754 | 0.065* | |
| C5 | 0.4783 (4) | 0.1923 (3) | 0.67457 (17) | 0.0430 (6) | |
| C6 | 0.3089 (3) | 0.1265 (2) | 0.66943 (16) | 0.0367 (5) | |
| C7 | 0.5968 (5) | 0.2679 (4) | 0.5822 (2) | 0.0696 (8) | |
| H7A | 0.5020 | 0.3625 | 0.5433 | 0.104* | |
| H7B | 0.6355 | 0.2060 | 0.5407 | 0.104* | |
| H7C | 0.7286 | 0.2835 | 0.6034 | 0.104* | |
| C8 | 0.2225 (4) | 0.1361 (2) | 0.56942 (17) | 0.0393 (5) | |
| C9 | 0.0679 (3) | 0.3321 (2) | 0.40383 (15) | 0.0334 (5) | |
| C10 | 0.0056 (4) | 0.2603 (2) | 0.25979 (16) | 0.0366 (5) | |
| C11 | 0.1738 (4) | 0.2193 (3) | 0.19879 (18) | 0.0473 (6) | |
| H11 | 0.3167 | 0.1740 | 0.2259 | 0.057* | |
| C12 | 0.1297 (4) | 0.2456 (3) | 0.09727 (19) | 0.0538 (7) | |
| H12 | 0.2440 | 0.2181 | 0.0565 | 0.065* | |
| C13 | −0.0810 (4) | 0.3119 (3) | 0.05573 (17) | 0.0499 (6) | |
| C14 | −0.2460 (4) | 0.3481 (3) | 0.11976 (17) | 0.0463 (6) | |
| H14 | −0.3895 | 0.3910 | 0.0929 | 0.056* | |
| C15 | −0.2098 (4) | 0.3239 (2) | 0.22153 (16) | 0.0394 (5) | |
| C16 | −0.1300 (5) | 0.3419 (3) | −0.05520 (19) | 0.0748 (9) | |
| H16A | −0.0953 | 0.4338 | −0.0968 | 0.112* | |
| H16B | −0.2839 | 0.3494 | −0.0643 | 0.112* | |
| H16C | −0.0420 | 0.2614 | −0.0750 | 0.112* | |
| C17 | −0.3997 (4) | 0.3598 (3) | 0.28774 (19) | 0.0564 (7) | |
| H17A | −0.5362 | 0.3917 | 0.2493 | 0.085* | |
| H17B | −0.3828 | 0.4383 | 0.3099 | 0.085* | |
| H17C | −0.4015 | 0.2723 | 0.3462 | 0.085* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| S1 | 0.0630 (4) | 0.0333 (3) | 0.0343 (3) | −0.0086 (3) | −0.0061 (3) | −0.0108 (2) |
| O1 | 0.1010 (14) | 0.0356 (9) | 0.0529 (11) | −0.0138 (9) | −0.0262 (10) | −0.0130 (8) |
| N1 | 0.0502 (11) | 0.0303 (9) | 0.0333 (10) | −0.0070 (8) | −0.0101 (8) | −0.0128 (8) |
| N2 | 0.0524 (12) | 0.0300 (9) | 0.0347 (10) | −0.0063 (8) | −0.0104 (8) | −0.0107 (8) |
| C1 | 0.0657 (16) | 0.0445 (14) | 0.0448 (15) | −0.0180 (12) | −0.0029 (12) | −0.0108 (12) |
| C2 | 0.092 (2) | 0.0591 (17) | 0.0327 (14) | −0.0153 (16) | 0.0040 (14) | −0.0072 (13) |
| C3 | 0.089 (2) | 0.0587 (17) | 0.0398 (16) | −0.0019 (16) | −0.0202 (15) | −0.0193 (13) |
| C4 | 0.0576 (16) | 0.0573 (16) | 0.0483 (16) | −0.0066 (13) | −0.0184 (13) | −0.0214 (13) |
| C5 | 0.0421 (13) | 0.0453 (14) | 0.0402 (14) | −0.0053 (11) | −0.0066 (11) | −0.0157 (11) |
| C6 | 0.0424 (13) | 0.0311 (11) | 0.0339 (12) | −0.0037 (10) | −0.0052 (10) | −0.0109 (10) |
| C7 | 0.0598 (17) | 0.101 (2) | 0.0598 (18) | −0.0409 (16) | 0.0074 (14) | −0.0278 (17) |
| C8 | 0.0450 (13) | 0.0363 (12) | 0.0380 (13) | −0.0111 (10) | −0.0058 (10) | −0.0127 (10) |
| C9 | 0.0319 (11) | 0.0387 (12) | 0.0313 (12) | −0.0077 (9) | −0.0019 (9) | −0.0144 (10) |
| C10 | 0.0494 (14) | 0.0326 (11) | 0.0315 (12) | −0.0110 (10) | −0.0056 (10) | −0.0135 (9) |
| C11 | 0.0478 (14) | 0.0472 (14) | 0.0487 (15) | −0.0026 (11) | −0.0052 (12) | −0.0239 (12) |
| C12 | 0.0579 (17) | 0.0569 (16) | 0.0475 (15) | −0.0036 (13) | 0.0052 (13) | −0.0274 (13) |
| C13 | 0.0694 (17) | 0.0452 (14) | 0.0338 (13) | −0.0083 (12) | −0.0056 (12) | −0.0152 (11) |
| C14 | 0.0504 (14) | 0.0455 (14) | 0.0404 (14) | −0.0049 (11) | −0.0128 (11) | −0.0143 (11) |
| C15 | 0.0428 (13) | 0.0400 (12) | 0.0361 (13) | −0.0090 (10) | −0.0031 (10) | −0.0141 (10) |
| C16 | 0.101 (2) | 0.080 (2) | 0.0370 (15) | −0.0053 (17) | −0.0084 (15) | −0.0226 (14) |
| C17 | 0.0470 (15) | 0.0767 (19) | 0.0493 (16) | −0.0126 (13) | −0.0008 (12) | −0.0279 (14) |
| S1—C9 | 1.660 (2) | C7—H7A | 0.9600 |
| O1—C8 | 1.218 (3) | C7—H7B | 0.9600 |
| N1—C8 | 1.366 (3) | C7—H7C | 0.9600 |
| N1—C9 | 1.392 (3) | C10—C11 | 1.380 (3) |
| N1—H1 | 0.8600 | C10—C15 | 1.387 (3) |
| N2—C9 | 1.325 (3) | C11—C12 | 1.384 (3) |
| N2—C10 | 1.433 (3) | C11—H11 | 0.9300 |
| N2—H2 | 0.8600 | C12—C13 | 1.378 (3) |
| C1—C6 | 1.381 (3) | C12—H12 | 0.9300 |
| C1—C2 | 1.381 (3) | C13—C14 | 1.381 (3) |
| C1—H1A | 0.9300 | C13—C16 | 1.511 (3) |
| C2—C3 | 1.367 (4) | C14—C15 | 1.383 (3) |
| C2—H2A | 0.9300 | C14—H14 | 0.9300 |
| C3—C4 | 1.358 (4) | C15—C17 | 1.505 (3) |
| C3—H3 | 0.9300 | C16—H16A | 0.9600 |
| C4—C5 | 1.386 (3) | C16—H16B | 0.9600 |
| C4—H4 | 0.9300 | C16—H16C | 0.9600 |
| C5—C6 | 1.395 (3) | C17—H17A | 0.9600 |
| C5—C7 | 1.501 (3) | C17—H17B | 0.9600 |
| C6—C8 | 1.496 (3) | C17—H17C | 0.9600 |
| C8—N1—C9 | 129.81 (17) | N2—C9—N1 | 116.13 (18) |
| C8—N1—H1 | 115.1 | N2—C9—S1 | 125.20 (16) |
| C9—N1—H1 | 115.1 | N1—C9—S1 | 118.67 (15) |
| C9—N2—C10 | 124.43 (18) | C11—C10—C15 | 120.8 (2) |
| C9—N2—H2 | 117.8 | C11—C10—N2 | 117.8 (2) |
| C10—N2—H2 | 117.8 | C15—C10—N2 | 121.3 (2) |
| C6—C1—C2 | 120.2 (2) | C10—C11—C12 | 120.0 (2) |
| C6—C1—H1A | 119.9 | C10—C11—H11 | 120.0 |
| C2—C1—H1A | 119.9 | C12—C11—H11 | 120.0 |
| C3—C2—C1 | 119.4 (2) | C13—C12—C11 | 121.0 (2) |
| C3—C2—H2A | 120.3 | C13—C12—H12 | 119.5 |
| C1—C2—H2A | 120.3 | C11—C12—H12 | 119.5 |
| C4—C3—C2 | 120.7 (2) | C12—C13—C14 | 117.4 (2) |
| C4—C3—H3 | 119.7 | C12—C13—C16 | 121.2 (2) |
| C2—C3—H3 | 119.7 | C14—C13—C16 | 121.4 (2) |
| C3—C4—C5 | 121.6 (2) | C13—C14—C15 | 123.6 (2) |
| C3—C4—H4 | 119.2 | C13—C14—H14 | 118.2 |
| C5—C4—H4 | 119.2 | C15—C14—H14 | 118.2 |
| C4—C5—C6 | 117.7 (2) | C14—C15—C10 | 117.2 (2) |
| C4—C5—C7 | 119.4 (2) | C14—C15—C17 | 120.6 (2) |
| C6—C5—C7 | 122.9 (2) | C10—C15—C17 | 122.2 (2) |
| C1—C6—C5 | 120.4 (2) | C13—C16—H16A | 109.5 |
| C1—C6—C8 | 118.0 (2) | C13—C16—H16B | 109.5 |
| C5—C6—C8 | 121.57 (19) | H16A—C16—H16B | 109.5 |
| C5—C7—H7A | 109.5 | C13—C16—H16C | 109.5 |
| C5—C7—H7B | 109.5 | H16A—C16—H16C | 109.5 |
| H7A—C7—H7B | 109.5 | H16B—C16—H16C | 109.5 |
| C5—C7—H7C | 109.5 | C15—C17—H17A | 109.5 |
| H7A—C7—H7C | 109.5 | C15—C17—H17B | 109.5 |
| H7B—C7—H7C | 109.5 | H17A—C17—H17B | 109.5 |
| O1—C8—N1 | 123.27 (19) | C15—C17—H17C | 109.5 |
| O1—C8—C6 | 123.18 (19) | H17A—C17—H17C | 109.5 |
| N1—C8—C6 | 113.52 (18) | H17B—C17—H17C | 109.5 |
| C6—C1—C2—C3 | −1.5 (4) | C10—N2—C9—S1 | 4.5 (3) |
| C1—C2—C3—C4 | −0.3 (4) | C8—N1—C9—N2 | 5.5 (3) |
| C2—C3—C4—C5 | 1.2 (4) | C8—N1—C9—S1 | −173.80 (17) |
| C3—C4—C5—C6 | −0.2 (3) | C9—N2—C10—C11 | 108.4 (2) |
| C3—C4—C5—C7 | −178.7 (3) | C9—N2—C10—C15 | −74.2 (3) |
| C2—C1—C6—C5 | 2.5 (3) | C15—C10—C11—C12 | 1.9 (3) |
| C2—C1—C6—C8 | −176.4 (2) | N2—C10—C11—C12 | 179.4 (2) |
| C4—C5—C6—C1 | −1.7 (3) | C10—C11—C12—C13 | −0.3 (4) |
| C7—C5—C6—C1 | 176.8 (2) | C11—C12—C13—C14 | −1.3 (4) |
| C4—C5—C6—C8 | 177.2 (2) | C11—C12—C13—C16 | 179.6 (2) |
| C7—C5—C6—C8 | −4.3 (3) | C12—C13—C14—C15 | 1.3 (4) |
| C9—N1—C8—O1 | −8.8 (4) | C16—C13—C14—C15 | −179.6 (2) |
| C9—N1—C8—C6 | 173.14 (19) | C13—C14—C15—C10 | 0.3 (3) |
| C1—C6—C8—O1 | −57.8 (3) | C13—C14—C15—C17 | −177.2 (2) |
| C5—C6—C8—O1 | 123.3 (3) | C11—C10—C15—C14 | −1.9 (3) |
| C1—C6—C8—N1 | 120.3 (2) | N2—C10—C15—C14 | −179.21 (19) |
| C5—C6—C8—N1 | −58.6 (3) | C11—C10—C15—C17 | 175.5 (2) |
| C10—N2—C9—N1 | −174.81 (18) | N2—C10—C15—C17 | −1.8 (3) |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O1 | 0.86 | 2.03 | 2.706 | 135 |
| C17—H17B···S1 | 0.96 | 2.80 | 3.496 | 130 |
| N1—H1···S1i | 0.86 | 2.57 | 3.372 | 155 |
| Symmetry codes: (i) −x, −y+1, −z+1. |
| D—H···A | D—H | H···A | D···A | D—H···A |
| N2—H2···O1 | 0.86 | 2.03 | 2.706 | 135 |
| C17—H17B···S1 | 0.96 | 2.80 | 3.496 | 130 |
| N1—H1···S1i | 0.86 | 2.57 | 3.372 | 155 |
| Symmetry codes: (i) −x, −y+1, −z+1. |
The authors thank the Ministry of Higher Education of Malaysia for Fundamental Research Grants OUP UKM-OUP-BIT-28/20076 and UMT-FRGS-59001 and Universiti Kebangsaan Malaysia and H.E.J. Research Institute of Chemistry, University of Karachi, for the research facilities.
Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19.
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Khawar Rauf, M., Badshah, A. & Bolte, M. (2007). Acta Cryst. E63, o1256–o1257.
Nardelli, M. (1995). J. Appl. Cryst. 28, 659.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.
The title compound, (I), is isomeric to the previously reported 1-(2,3-dimethylphenyl)-3-(2-methylbenzoyl)thiourea (II), (Khawar Rauf et al., 2007) with the difference that the 2,3-dimethylphenyl ring is replaced by 2,4-dimethylphenyl (Fig.1). The bond lengths and angles are in normal range (Allen et al., 1987) and in agreement with those in (II). The central thiourea moiety (S1/N1/N2/C9), 2-methylbenzoyl (C1—C8), and 2,3-dimethylphenyl (C10—C15) rings are each planar with a maximum deviation of 0.040 (2)Å for C8 atom from the least square plane. The dihedral angles between the thiourea moiety and the 2-methylbenzoyl and 2,3-dimethylphenyl rings are 52.96 (11) and 70.34 (12)°, respectively. The trans-cis geometry of the thiourea moiety is stabilized by N2—H2···O1 and C17—H17B···S1 intramolecular hydrogen bonds. In the crystal structure, the molecules are linked to form dimers by the N1—H1···S1 intermolecular hydrogen bond (symmtery codes as in Table 2) and arranged parallel to c axis (Fig.2).