The title mol­ecule, C16H15ClN2OS, exists in the solid state in its thione form with typical thio­urea C—S and C—O bonds lengths, as well as shortened C—N bonds. An intra­molecular N—H⋯O hydrogen bond stabilizes the mol­ecular conformation and inter­molecular N—H⋯S hydrogen bonds link the mol­ecules into centrosymmetric dimers. The dihedral angle  between the aromatic rings is 50.18 (5)°

Allen

Amin Badshah

Blessing

Khawar Rauf

M. Khawar Rauf

Michael Bolte

Sheldrick

Spek

Acta Crystallographica Section E

English

PubMed

The title molecule, C16H15ClN2OS, exists in the solid state in its thione form with typical thiourea C&#8212;S and C&#8212;O bonds lengths, as well as shortened C&#8212;N bonds. An intramolecular N&#8212;H...O hydrogen bond stabilizes the molecular conformation and intermolecular N&#8212;H...S hydrogen bonds link the molecules into centrosymmetric dimers. The dihedral angle  between the aromatic rings is 50.18&#8197;(5)&#176;

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Acta Crystallographica Section E Structure Reports Online

1-(3-Chlorobenzoyl)-3-(2,3-dimethylphenyl)thiourea

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The title molecule, C16H15ClN2OS, exists in the solid state in its thione form with typical thiourea C-S and C-O bonds lengths, as well as shortened C-N bonds. An intramolecular N-H...O hydrogen bond stabilizes the molecular conformation and intermolecular N-H...S hydrogen bonds link the molecules into centrosymmetric dimers. The dihedral angle between the aromatic rings is 50.18 (5)°. Key indicators: single-crystal X-ray study; T = 173 K; mean &#963;(C–C) = 0.002 Å; R factor = 0.032; wR factor = 0.085; data-to-parameter ratio = 15.3

Rauf, M. Khawar

Bolte, Michael

Badshah, Amin

Hochschulschriftenserver - Universität Frankfurt am Main

1-(3-Chlorobenzoyl)-3-(2,3-dimethyl-phenyl)thioureaM. Khawar Rauf,a Michael Bolteb and Amin Badshaha*aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan,andbInstitut fu ¨r Anorganische Chemie, J. W. Goethe-Universita ¨t Frankfurt, Max-von-Laue-Strasse 7, 60438 Frankfurt/Main, GermanyCorrespondence e-mail: aminbadshah@yahoo.comReceived 3 December 2008; accepted 1 January 2009Key indicators: single-crystal X-ray study; T = 173 K; mean  (C–C) = 0.002 A ˚;R factor = 0.032; wR factor = 0.085; data-to-parameter ratio = 15.3.The title molecule, C16H15ClN2OS, exists in the solid state inits thione form with typical thiourea C—S and C—O bondslengths, as well as shortened C—N bonds. An intramolecularN—H   O hydrogen bond stabilizes the molecular conforma-tion and intermolecular N—H   S hydrogen bonds link themolecules into centrosymmetric dimers. The dihedral anglebetween the aromatic rings is 50.18 (5) .Related literatureFor related compounds, see: Khawar Rauf et al. (2006a,b,c,d).For reference bond-length data, see: Allen (2002).ExperimentalCrystal dataC16H15ClN2OSMr = 318.81Triclinic, P1a = 8.1315 (9) A ˚b = 9.3906 (12) A ˚c = 10.5310 (12) A ˚  = 93.296 (8)   = 92.623 (8)   = 102.579 (9) V = 782.14 (16) A ˚ 3Z =2Mo K  radiation  = 0.38 mm 1T = 173 (2) K0.46   0.42   0.41 mmData collectionStoe IPDS II two-circlediffractometerAbsorption correction: multi-scan(MULABS; Spek, 2003; Blessing,1995)Tmin = 0.846, Tmax = 0.8618257 measured reﬂections3066 independent reﬂections2846 reﬂections with I >2  (I)Rint = 0.037ReﬁnementR[F2 >2  (F2)] = 0.032wR(F2) = 0.085S = 1.043066 reﬂections201 parametersH atoms treated by a mixture ofindependent and constrainedreﬁnement max = 0.27 e A ˚  3 min =  0.33 e A ˚  3Table 1Hydrogen-bond geometry (A ˚ ,  ).D—H   AD —H H   AD    AD —H   AN2—H2   O1 0.86 (2) 1.99 (2) 2.6840 (16) 137.7 (17)N1—H1   S1i 0.836 (19) 2.636 (19) 3.4376 (13) 161.2 (15)Symmetry code: (i)  x; y þ 1; z þ 1.Data collection: X-AREA (Stoe & Cie, 2001); cell reﬁnement:X-AREA; data reduction: X-AREA; program(s) used to solvestructure: SHELXS97 (Sheldrick, 2008); program(s) used to reﬁnestructure: SHELXL97 (Sheldrick, 2008); molecular graphics: XP inSHELXTL-Plus (Sheldrick, 2008); software used to prepare materialfor publication: SHELXL97.MKR is grateful to the HEC, Pakistan, for ﬁnancial supportfor a PhD programme under scholarship No. ILC-0363104.Supplementary data and ﬁgures for this paper are available from theIUCr electronic archives (Reference: BV2114).ReferencesAllen, F. H. (2002). Acta Cryst. B58, 380–388.Blessing, R. H. (1995). Acta Cryst. A51, 33–38.Khawar Rauf, M., Badshah, A. & Bolte, M. (2006a). Acta Cryst. E62, o1859–o1860.Khawar Rauf, M., Badshah, A. & Bolte, M. (2006b). Acta Cryst. E62, o2221–o2222.Khawar Rauf, M., Badshah, A. & Bolte, M. (2006c). Acta Cryst. E62, o2444–o2445.Khawar Rauf, M., Badshah, A., Bolte, M. & Zaeem Akhtar, M. (2006d). ActaCryst. E62, o1849–o1850.Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13.Stoe & Cie (2001). X-AREA. Stoe & Cie, Darmstadt, Germany.organic compoundso240 Khawar Rauf et al. doi:10.1107/S1600536809000063 Acta Cryst. (2009). E65, o240Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368supplementary materialssupplementary materialssup-1Acta Cryst. (2009). E65, o240    [ doi:10.1107/S1600536809000063 ]1-(3-Chlorobenzoyl)-3-(2,3-dimethylphenyl)thioureaM. Khawar Rauf, M. Bolte and A. BadshahCommentThe background to this study has been set out in our previous work on the structural chemistry of N,N'-disubstituted thioureas(Khawar Rauf et al., 2006a,b,c,d). Herein, as a continuation of these studies, the structure of the title compound (I) isdescribed. A depiction of the molecule is given in Fig. 1. Bond lengths and angles, see the table of selected geometricparameters, can be regarded as typical for N,N'-disubstituted thiourea compounds as found in the Cambridge StructuralDatabase v5.28 (Allen, 2002; Khawar Rauf et al., 2006a).The molecule exists in the thione form with typical thiourea C—Sand C—O bonds, as well as shortened C—N bond lengths. The thiocarbonyl and carbonyl groups are almost coplanar. Thedihedral angle between the aromatic rings is 50.18 (5)°. An intramolecular N—H···O hydrogen bond is present (Table 2),forming a six-membered ring commonly observed in this class of compounds (Khawar Rauf et al., 2006d). IntermolecularN—H···S hydrogen bonds link the molecules to form centrosymmetric dimers.ExperimentalFreshly prepared 3-chlorobenzoyl isothiocyanate (2.0 g, 10 mmol) was stirred in acetone (40 ml) for 20 min. Neat 2,3-di-methylaniline (1.62 g, 10 mmol) was then added and the resulting mixture was stirred for 1.5 h. The reaction mixture wasthen poured into acidified (pH 4) water and stirred well. The solid product was separated and washed with deionized waterand purified by recrystallization from methanol–1,1-dichloromethane (1:10 v/v) to give fine crystals of (I), with an overallyield of 90%. Full spectroscopic and physical characterization will be reported elsewhere.RefinementH atoms bonded to C were included in calculated positions and refined as riding on their parent C atom with C—H = 0.95Å Uiso(H) = 1.2Ueq(C) or C—H = 0.98 Å and Uiso(H) = 1.5Ueq(C), respectively, for aromatic and methyl C atoms. TheH atoms bonded to N were freely refined.FiguresFig. 1. Molecular structure of (I) showing atom numbering scheme. Displacement ellipsoidsare drawn at the 50% probability level.supplementary materialssup-2Fig. 2. Packing diagram. Hydrogen bonds are shown as dashed lines.1-(3-chlorobenzoyl)-3-(2,3-dimethylphenyl)thioureaCrystal dataC16H15ClN2OS Z = 2Mr = 318.81 F000 = 332Triclinic, P1 Dx = 1.354 Mg m−3Hall symbol: -P 1 Mo Kα radiationλ = 0.71073 Åa = 8.1315 (9) Å Cell parameters from 7706 reflectionsb = 9.3906 (12) Å θ = 3.7–26.1ºc = 10.5310 (12) Å µ = 0.38 mm−1α = 93.296 (8)º T = 173 (2) Kβ = 92.623 (8)º Block, colourlessγ = 102.579 (9)º 0.46 × 0.42 × 0.41 mmV = 782.14 (16) Å3Data collectionStoe IPDS II two-circlediffractometer 3066 independent reflectionsRadiation source: fine-focus sealed tube 2846 reflections with I > 2σ(I)Monochromator: graphite Rint = 0.037T = 173(2) K θmax = 26.1ºω scans θmin = 3.6ºAbsorption correction: multi-scan(MULABS; Spek, 2003; Blessing, 1995) h = −10→10Tmin = 0.846, Tmax = 0.861 k = −10→118257 measured reflections l = −12→12RefinementRefinement on F2 Hydrogen site location: inferred from neighbouringsitesLeast-squares matrix: fullH atoms treated by a mixture ofindependent and constrained refinementR[F2 > 2σ(F2)] = 0.032  w = 1/[σ2(Fo2) + (0.041P)2 + 0.3782P]where P = (Fo2 + 2Fc2)/3supplementary materialssup-3wR(F2) = 0.085 (Δ/σ)max < 0.001S = 1.04 Δρmax = 0.27 e Å−33066 reflections Δρmin = −0.32 e Å−3201 parametersExtinction correction: SHELXL97 (Sheldrick, 2008),Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4Primary atom site location: structure-invariant directmethodsExtinction coefficient: 0.097 (5)Secondary atom site location: difference Fourier mapSpecial detailsGeometry. 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 mat-rix. 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; correlationsbetween e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment ofcell 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, convention-al 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 largeas 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)x y z Uiso*/UeqS1 0.23509 (5) 0.60717 (4) 0.59551 (4) 0.02881 (14)Cl1 −0.24623 (5) −0.05881 (5) 0.30214 (4) 0.03438 (14)O1 −0.01441 (13) 0.25159 (11) 0.84778 (9) 0.0258 (2)N1 0.03004 (15) 0.36655 (13) 0.66166 (11) 0.0201 (3)H1 −0.014 (2) 0.3701 (19) 0.5889 (18) 0.025 (4)*N2 0.24161 (15) 0.47809 (13) 0.81460 (11) 0.0215 (3)H2 0.192 (2) 0.412 (2) 0.8612 (19) 0.034 (5)*C1 −0.04406 (17) 0.25179 (15) 0.73206 (13) 0.0192 (3)C2 0.16893 (17) 0.48027 (14) 0.69839 (13) 0.0190 (3)C11 −0.16148 (16) 0.12650 (14) 0.65810 (13) 0.0190 (3)C12 −0.15027 (17) 0.09819 (15) 0.52694 (13) 0.0203 (3)H12 −0.0703 0.1612 0.4809 0.024*C13 −0.25894 (18) −0.02426 (15) 0.46557 (14) 0.0232 (3)C14 −0.37636 (19) −0.11864 (16) 0.53128 (16) 0.0280 (3)H14 −0.4495 −0.2015 0.4877 0.034*C15 −0.38527 (18) −0.09009 (16) 0.66142 (16) 0.0280 (3)H15 −0.4650 −0.1538 0.7071 0.034*C16 −0.27787 (18) 0.03152 (16) 0.72518 (14) 0.0238 (3)H16 −0.2837 0.0499 0.8143 0.029*C21 0.39206 (17) 0.58278 (15) 0.86417 (13) 0.0194 (3)C22 0.55031 (18) 0.56849 (15) 0.82648 (13) 0.0213 (3)C23 0.69413 (18) 0.67134 (16) 0.88045 (14) 0.0240 (3)C24 0.67324 (19) 0.78059 (16) 0.96980 (14) 0.0255 (3)H24 0.7701 0.8486 1.0066 0.031*supplementary materialssup-4C25 0.5146 (2) 0.79247 (17) 1.00630 (14) 0.0280 (3)H25 0.5034 0.8679 1.0671 0.034*C26 0.37181 (18) 0.69272 (16) 0.95296 (14) 0.0243 (3)H26 0.2624 0.6996 0.9768 0.029*C27 0.5701 (2) 0.44874 (18) 0.73006 (16) 0.0325 (4)H27A 0.4650 0.3736 0.7199 0.049*H27B 0.6625 0.4049 0.7598 0.049*H27C 0.5956 0.4901 0.6480 0.049*C28 0.8687 (2) 0.6643 (2) 0.84115 (18) 0.0412 (4)H28A 0.9513 0.7479 0.8823 0.062*H28B 0.8720 0.6671 0.7484 0.062*H28C 0.8961 0.5732 0.8672 0.062*Atomic displacement parameters (Å2)U11 U22 U33 U12 U13 U23S1 0.0257 (2) 0.0279 (2) 0.0257 (2) −0.00979 (15) −0.00909 (14) 0.01144 (15)Cl1 0.0333 (2) 0.0398 (2) 0.0276 (2) 0.00868 (17) −0.00649 (16) −0.01303 (16)O1 0.0274 (5) 0.0271 (5) 0.0184 (5) −0.0040 (4) −0.0013 (4) 0.0031 (4)N1 0.0201 (6) 0.0193 (6) 0.0172 (6) −0.0028 (4) −0.0054 (5) 0.0021 (4)N2 0.0202 (6) 0.0212 (6) 0.0188 (6) −0.0040 (5) −0.0040 (5) 0.0030 (5)C1 0.0175 (6) 0.0190 (6) 0.0199 (7) 0.0015 (5) 0.0001 (5) 0.0016 (5)C2 0.0171 (6) 0.0180 (6) 0.0201 (7) 0.0008 (5) −0.0019 (5) 0.0007 (5)C11 0.0159 (6) 0.0166 (6) 0.0234 (7) 0.0020 (5) −0.0026 (5) 0.0019 (5)C12 0.0179 (6) 0.0182 (6) 0.0238 (7) 0.0026 (5) −0.0021 (5) 0.0008 (5)C13 0.0227 (7) 0.0216 (7) 0.0253 (7) 0.0078 (5) −0.0061 (6) −0.0046 (6)C14 0.0222 (7) 0.0184 (7) 0.0395 (9) −0.0007 (5) −0.0090 (6) −0.0025 (6)C15 0.0215 (7) 0.0211 (7) 0.0384 (9) −0.0023 (6) −0.0023 (6) 0.0078 (6)C16 0.0215 (7) 0.0226 (7) 0.0255 (7) 0.0009 (5) −0.0006 (6) 0.0046 (6)C21 0.0206 (7) 0.0189 (6) 0.0163 (6) 0.0002 (5) −0.0050 (5) 0.0023 (5)C22 0.0236 (7) 0.0211 (7) 0.0184 (7) 0.0041 (5) −0.0029 (5) 0.0011 (5)C23 0.0204 (7) 0.0285 (7) 0.0220 (7) 0.0032 (6) −0.0033 (5) 0.0038 (6)C24 0.0235 (7) 0.0249 (7) 0.0240 (7) −0.0014 (6) −0.0084 (6) 0.0014 (6)C25 0.0321 (8) 0.0252 (7) 0.0245 (7) 0.0056 (6) −0.0055 (6) −0.0073 (6)C26 0.0206 (7) 0.0286 (7) 0.0229 (7) 0.0053 (6) −0.0018 (5) −0.0021 (6)C27 0.0316 (8) 0.0343 (8) 0.0311 (8) 0.0092 (7) 0.0010 (6) −0.0083 (7)C28 0.0225 (8) 0.0568 (11) 0.0410 (10) 0.0047 (7) −0.0002 (7) −0.0057 (8)Geometric parameters (Å, °)S1—C2 1.6751 (14) C16—H16 0.9500Cl1—C13 1.7450 (15) C21—C26 1.394 (2)O1—C1 1.2315 (17) C21—C22 1.395 (2)N1—C1 1.3871 (18) C22—C23 1.417 (2)N1—C2 1.3974 (17) C22—C27 1.511 (2)N1—H1 0.836 (19) C23—C24 1.395 (2)N2—C2 1.3377 (18) C23—C28 1.511 (2)N2—C21 1.4472 (17) C24—C25 1.388 (2)N2—H2 0.86 (2) C24—H24 0.9500supplementary materialssup-5C1—C11 1.4966 (18) C25—C26 1.395 (2)C11—C16 1.3986 (19) C25—H25 0.9500C11—C12 1.402 (2) C26—H26 0.9500C12—C13 1.3930 (19) C27—H27A 0.9800C12—H12 0.9500 C27—H27B 0.9800C13—C14 1.392 (2) C27—H27C 0.9800C14—C15 1.390 (2) C28—H28A 0.9800C14—H14 0.9500 C28—H28B 0.9800C15—C16 1.393 (2) C28—H28C 0.9800C15—H15 0.9500C1—N1—C2 127.82 (12) C26—C21—C22 122.41 (13)C1—N1—H1 117.0 (12) C26—C21—N2 117.43 (13)C2—N1—H1 115.2 (12) C22—C21—N2 120.12 (12)C2—N2—C21 123.54 (12) C21—C22—C23 117.98 (13)C2—N2—H2 116.1 (13) C21—C22—C27 121.75 (13)C21—N2—H2 120.3 (13) C23—C22—C27 120.27 (13)O1—C1—N1 122.49 (12) C24—C23—C22 119.38 (13)O1—C1—C11 121.81 (12) C24—C23—C28 120.03 (14)N1—C1—C11 115.70 (12) C22—C23—C28 120.59 (14)N2—C2—N1 116.65 (12) C25—C24—C23 121.69 (13)N2—C2—S1 124.50 (10) C25—C24—H24 119.2N1—C2—S1 118.84 (10) C23—C24—H24 119.2C16—C11—C12 120.14 (12) C24—C25—C26 119.50 (14)C16—C11—C1 117.91 (12) C24—C25—H25 120.2C12—C11—C1 121.84 (12) C26—C25—H25 120.2C13—C12—C11 118.60 (13) C21—C26—C25 119.04 (13)C13—C12—H12 120.7 C21—C26—H26 120.5C11—C12—H12 120.7 C25—C26—H26 120.5C14—C13—C12 121.68 (14) C22—C27—H27A 109.5C14—C13—Cl1 119.67 (11) C22—C27—H27B 109.5C12—C13—Cl1 118.64 (12) H27A—C27—H27B 109.5C15—C14—C13 119.17 (13) C22—C27—H27C 109.5C15—C14—H14 120.4 H27A—C27—H27C 109.5C13—C14—H14 120.4 H27B—C27—H27C 109.5C14—C15—C16 120.31 (14) C23—C28—H28A 109.5C14—C15—H15 119.8 C23—C28—H28B 109.5C16—C15—H15 119.8 H28A—C28—H28B 109.5C15—C16—C11 120.08 (14) C23—C28—H28C 109.5C15—C16—H16 120.0 H28A—C28—H28C 109.5C11—C16—H16 120.0 H28B—C28—H28C 109.5C2—N1—C1—O1 14.4 (2) C12—C11—C16—C15 −1.2 (2)C2—N1—C1—C11 −164.92 (13) C1—C11—C16—C15 −177.41 (13)C21—N2—C2—N1 176.32 (12) C2—N2—C21—C26 103.83 (16)C21—N2—C2—S1 −2.7 (2) C2—N2—C21—C22 −78.45 (18)C1—N1—C2—N2 1.0 (2) C26—C21—C22—C23 −0.6 (2)C1—N1—C2—S1 −179.91 (11) N2—C21—C22—C23 −178.24 (12)O1—C1—C11—C16 20.3 (2) C26—C21—C22—C27 −179.96 (14)N1—C1—C11—C16 −160.43 (12) N2—C21—C22—C27 2.4 (2)supplementary materialssup-6O1—C1—C11—C12 −155.86 (13) C21—C22—C23—C24 1.0 (2)N1—C1—C11—C12 23.43 (19) C27—C22—C23—C24 −179.67 (14)C16—C11—C12—C13 1.1 (2) C21—C22—C23—C28 −178.42 (14)C1—C11—C12—C13 177.14 (12) C27—C22—C23—C28 0.9 (2)C11—C12—C13—C14 −0.5 (2) C22—C23—C24—C25 −0.8 (2)C11—C12—C13—Cl1 179.51 (10) C28—C23—C24—C25 178.63 (15)C12—C13—C14—C15 −0.1 (2) C23—C24—C25—C26 0.2 (2)Cl1—C13—C14—C15 179.96 (11) C22—C21—C26—C25 0.0 (2)C13—C14—C15—C16 0.0 (2) N2—C21—C26—C25 177.71 (13)C14—C15—C16—C11 0.7 (2) C24—C25—C26—C21 0.2 (2)Hydrogen-bond geometry (Å, °)D—H···A D—H H···A D···A D—H···AN2—H2···O1 0.86 (2) 1.99 (2) 2.6840 (16) 137.7 (17)N1—H1···S1i 0.836 (19) 2.636 (19) 3.4376 (13) 161.2 (15)Symmetry codes: (i) −x, −y+1, −z+1.supplementary materialssup-7Fig. 1supplementary materialssup-8Fig. 2

Acta Cryst.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) x y z Uiso*/Ueq

organic compounds o240 Khawar Rauf et al. doi:10.1107/S1600536809000063 Acta Cryst.

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1-(3-Chloro­benzo­yl)-3-(2,3-dimethyl­phen­yl)thio­urea

1-(3-Chlorobenzoyl)-3-(2,3-dimethylphenyl)thiourea

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Hochschulschriftenserver - Universität Frankfurt am Main

1-(3-Chloro­benzo­yl)-3-(2,3-dimethyl­phen­yl)thio­urea

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1-(3-Chlorobenzoyl)-3-(2,3-dimethylphenyl)thiourea