organic compounds
1-(2-Chlorobenzoyl)-3-(2,3-dimethylphenyl)thiourea
aDepartment of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan, and bDepartment of Chemistry, Faculty of Engineering, Gifu University Yanagido, Gifu 501-1193, Japan
*Correspondence e-mail: mkhawarrauf@yahoo.co.uk, aminbadshah@yahoo.com
The dihedral angle between the two phenyl groups in the title compound, C16H15ClN2OS, is 14.88 (4)°. An intramolecular N—H⋯O hydrogen bond occurs. In the crystal, pairs of N—H⋯S hydrogen bonds link the molecules into centrosymmetric dimers.
Related literature
For background and a related structure, see: Rauf et al. (2012). For a description of the Cambridge Structural Database, see: Allen et al. (2002).
Experimental
Crystal data
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Data collection
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Refinement
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Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: Yadokari-XG (Wakita, 2001; Kabuto et al., 2009).
Supporting information
10.1107/S1600536812048209/hg5274sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536812048209/hg5274Isup2.hkl
Supporting information file. DOI: 10.1107/S1600536812048209/hg5274Isup3.cml
Freshly prepared 2-chlorobenzoylisothiocyanate (1.98 g, 10 mmol) was dissolved in acetone (30 ml) and stirred for 30 minutes. Afterwards neat 2,3-dimethylaniline(1.21 g, 10 mmol) was added and the resulting mixture was stirred for 2 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 methanol/ 1,1-dichloromethane (1:1 v/v) to give fine crystals of the title compound (I), with an overall yield of 95% (3.02 g). M.P; 180–181°C Anal. calcd. for C16 H15Cl N2 O S; C, 60.28 H, 4.74 N, 8.79 S, 10.06 Found: C, 60.22 H, 4.73 N, 8.78 S, 10.01.
Hydrogen atoms were included in calculated positions and refined as riding on their parent atom with N—H = 0.88 Å and Uiso(H) = 1.2U(Neq), Caromatic—H = 0.95 Å and Uiso(H) = 1.2U(Ceq) or C—H = 0.98 Å and Uiso(H) = 1.5U(Ceq), for methyl C atoms.
Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); cell
CrystalClear (Molecular Structure Corporation & Rigaku, 2001); data reduction: CrystalClear (Molecular Structure Corporation & Rigaku, 2001); program(s) used to solve structure: SIR97 (Altomare et al., 1999); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: Yadokari-XG (Wakita, 2001; Kabuto et al., 2009).Fig. 1. ORTEP of (I). Displacement ellipsoids are drawn at the 50% probability level. Hydrogen bonds shown as dashed lines. | |
Fig. 2. Packing diagram of (I). Hydrogen bonds shown as dashed lines. |
C16H15ClN2OS | Z = 2 |
Mr = 318.81 | F(000) = 332 |
Triclinic, P1 | Dx = 1.351 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 7.489 (3) Å | Cell parameters from 2732 reflections |
b = 9.338 (4) Å | θ = 3.0–27.5° |
c = 13.274 (5) Å | µ = 0.38 mm−1 |
α = 65.674 (13)° | T = 123 K |
β = 69.975 (16)° | Prism, colorless |
γ = 73.639 (17)° | 0.50 × 0.35 × 0.28 mm |
V = 783.9 (5) Å3 |
Rigaku/MSC Mercury CCD diffractometer | 3373 reflections with I > 2σ(I) |
Radiation source: Rotating Anode | Rint = 0.062 |
Graphite Monochromator monochromator | θmax = 27.5°, θmin = 3.5° |
Detector resolution: 14.62 pixels mm-1 | h = −6→9 |
ω scans | k = −9→12 |
6180 measured reflections | l = −10→17 |
3506 independent reflections |
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)] = 0.036 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.08 | w = 1/[σ2(Fo2) + (0.0371P)2 + 0.4197P] where P = (Fo2 + 2Fc2)/3 |
3506 reflections | (Δ/σ)max < 0.001 |
192 parameters | Δρmax = 0.32 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
C16H15ClN2OS | γ = 73.639 (17)° |
Mr = 318.81 | V = 783.9 (5) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.489 (3) Å | Mo Kα radiation |
b = 9.338 (4) Å | µ = 0.38 mm−1 |
c = 13.274 (5) Å | T = 123 K |
α = 65.674 (13)° | 0.50 × 0.35 × 0.28 mm |
β = 69.975 (16)° |
Rigaku/MSC Mercury CCD diffractometer | 3373 reflections with I > 2σ(I) |
6180 measured reflections | Rint = 0.062 |
3506 independent reflections |
R[F2 > 2σ(F2)] = 0.036 | 0 restraints |
wR(F2) = 0.090 | H-atom parameters constrained |
S = 1.08 | Δρmax = 0.32 e Å−3 |
3506 reflections | Δρmin = −0.31 e Å−3 |
192 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 | ||
C1 | 0.38592 (19) | 0.07516 (15) | 0.27734 (11) | 0.0162 (3) | |
O1 | 0.44634 (15) | 0.17028 (13) | 0.18262 (9) | 0.0245 (2) | |
N1 | 0.20232 (16) | 0.09731 (13) | 0.34511 (9) | 0.0170 (2) | |
H1 | 0.1791 | 0.0275 | 0.4152 | 0.020* | |
C2 | 0.04854 (19) | 0.21635 (15) | 0.31664 (11) | 0.0151 (2) | |
S1 | −0.15915 (5) | 0.22091 (4) | 0.41821 (3) | 0.01758 (10) | |
N2 | 0.07877 (16) | 0.31921 (13) | 0.20967 (9) | 0.0172 (2) | |
H2 | 0.1972 | 0.3159 | 0.1655 | 0.021* | |
C3 | 0.51000 (18) | −0.07725 (15) | 0.32976 (11) | 0.0157 (3) | |
C4 | 0.48935 (19) | −0.22203 (16) | 0.33182 (11) | 0.0175 (3) | |
C5 | 0.6119 (2) | −0.36192 (17) | 0.37358 (12) | 0.0234 (3) | |
H5 | 0.5988 | −0.4597 | 0.3728 | 0.028* | |
C6 | 0.7535 (2) | −0.35614 (18) | 0.41627 (13) | 0.0269 (3) | |
H6 | 0.8371 | −0.4512 | 0.4460 | 0.032* | |
C7 | 0.7751 (2) | −0.21271 (19) | 0.41617 (13) | 0.0258 (3) | |
H7 | 0.8721 | −0.2102 | 0.4462 | 0.031* | |
C8 | 0.6538 (2) | −0.07287 (17) | 0.37186 (12) | 0.0211 (3) | |
H8 | 0.6695 | 0.0255 | 0.3704 | 0.025* | |
Cl1 | 0.30905 (5) | −0.22869 (5) | 0.28008 (3) | 0.02652 (11) | |
C9 | −0.07073 (18) | 0.43554 (16) | 0.16191 (10) | 0.0155 (3) | |
C10 | −0.06255 (19) | 0.59756 (16) | 0.12305 (11) | 0.0166 (3) | |
C11 | −0.2070 (2) | 0.70696 (16) | 0.07143 (11) | 0.0188 (3) | |
C12 | −0.3533 (2) | 0.65092 (18) | 0.06365 (11) | 0.0206 (3) | |
H12 | −0.4519 | 0.7251 | 0.0304 | 0.025* | |
C13 | −0.3589 (2) | 0.48910 (18) | 0.10335 (11) | 0.0213 (3) | |
H13 | −0.4604 | 0.4533 | 0.0973 | 0.026* | |
C14 | −0.2158 (2) | 0.38012 (17) | 0.15185 (11) | 0.0191 (3) | |
H14 | −0.2166 | 0.2690 | 0.1779 | 0.023* | |
C15 | 0.0930 (2) | 0.65647 (18) | 0.13585 (13) | 0.0236 (3) | |
H15C | 0.1687 | 0.5671 | 0.1833 | 0.035* | |
H15A | 0.0342 | 0.7369 | 0.1724 | 0.035* | |
H15B | 0.1773 | 0.7038 | 0.0602 | 0.035* | |
C16 | −0.2044 (2) | 0.88359 (18) | 0.02548 (14) | 0.0299 (3) | |
H16C | −0.3084 | 0.9405 | −0.0127 | 0.045* | |
H16A | −0.0802 | 0.9059 | −0.0295 | 0.045* | |
H16B | −0.2229 | 0.9192 | 0.0888 | 0.045* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0165 (6) | 0.0149 (6) | 0.0178 (6) | −0.0008 (5) | −0.0061 (5) | −0.0059 (5) |
O1 | 0.0191 (5) | 0.0235 (5) | 0.0202 (5) | −0.0012 (4) | −0.0032 (4) | −0.0004 (4) |
N1 | 0.0172 (5) | 0.0141 (5) | 0.0143 (5) | 0.0016 (4) | −0.0037 (4) | −0.0030 (4) |
C2 | 0.0173 (6) | 0.0126 (5) | 0.0161 (6) | −0.0001 (5) | −0.0061 (5) | −0.0059 (5) |
S1 | 0.01736 (17) | 0.01515 (16) | 0.01454 (16) | 0.00274 (11) | −0.00288 (12) | −0.00425 (12) |
N2 | 0.0138 (5) | 0.0177 (5) | 0.0152 (5) | 0.0010 (4) | −0.0040 (4) | −0.0031 (4) |
C3 | 0.0140 (6) | 0.0156 (6) | 0.0149 (6) | 0.0003 (5) | −0.0025 (5) | −0.0055 (5) |
C4 | 0.0149 (6) | 0.0193 (6) | 0.0183 (6) | −0.0020 (5) | −0.0018 (5) | −0.0092 (5) |
C5 | 0.0230 (7) | 0.0174 (6) | 0.0253 (7) | 0.0014 (5) | −0.0021 (6) | −0.0095 (5) |
C6 | 0.0234 (7) | 0.0227 (7) | 0.0270 (7) | 0.0076 (6) | −0.0087 (6) | −0.0070 (6) |
C7 | 0.0185 (7) | 0.0310 (8) | 0.0285 (7) | 0.0027 (6) | −0.0112 (6) | −0.0111 (6) |
C8 | 0.0191 (6) | 0.0216 (7) | 0.0245 (7) | −0.0018 (5) | −0.0078 (5) | −0.0094 (5) |
Cl1 | 0.02276 (19) | 0.0319 (2) | 0.0347 (2) | −0.00257 (14) | −0.00959 (15) | −0.02058 (16) |
C9 | 0.0147 (6) | 0.0169 (6) | 0.0111 (5) | 0.0013 (5) | −0.0037 (4) | −0.0037 (5) |
C10 | 0.0157 (6) | 0.0184 (6) | 0.0138 (5) | −0.0011 (5) | −0.0029 (5) | −0.0057 (5) |
C11 | 0.0184 (6) | 0.0181 (6) | 0.0153 (6) | 0.0013 (5) | −0.0038 (5) | −0.0046 (5) |
C12 | 0.0162 (6) | 0.0260 (7) | 0.0146 (6) | 0.0025 (5) | −0.0055 (5) | −0.0048 (5) |
C13 | 0.0167 (6) | 0.0297 (7) | 0.0170 (6) | −0.0045 (5) | −0.0050 (5) | −0.0069 (5) |
C14 | 0.0206 (6) | 0.0184 (6) | 0.0160 (6) | −0.0037 (5) | −0.0041 (5) | −0.0040 (5) |
C15 | 0.0229 (7) | 0.0225 (7) | 0.0283 (7) | −0.0031 (5) | −0.0097 (6) | −0.0096 (6) |
C16 | 0.0303 (8) | 0.0173 (7) | 0.0344 (8) | 0.0012 (6) | −0.0100 (7) | −0.0037 (6) |
C1—O1 | 1.2211 (17) | C8—H8 | 0.9500 |
C1—N1 | 1.3743 (17) | C9—C14 | 1.392 (2) |
C1—C3 | 1.5017 (18) | C9—C10 | 1.395 (2) |
N1—C2 | 1.3912 (17) | C10—C11 | 1.4115 (19) |
N1—H1 | 0.8800 | C10—C15 | 1.504 (2) |
C2—N2 | 1.3299 (17) | C11—C12 | 1.389 (2) |
C2—S1 | 1.6770 (14) | C11—C16 | 1.508 (2) |
N2—C9 | 1.4385 (17) | C12—C13 | 1.388 (2) |
N2—H2 | 0.8800 | C12—H12 | 0.9500 |
C3—C8 | 1.389 (2) | C13—C14 | 1.385 (2) |
C3—C4 | 1.3917 (19) | C13—H13 | 0.9500 |
C4—C5 | 1.390 (2) | C14—H14 | 0.9500 |
C4—Cl1 | 1.7367 (15) | C15—H15C | 0.9800 |
C5—C6 | 1.385 (2) | C15—H15A | 0.9800 |
C5—H5 | 0.9500 | C15—H15B | 0.9800 |
C6—C7 | 1.393 (2) | C16—H16C | 0.9800 |
C6—H6 | 0.9500 | C16—H16A | 0.9800 |
C7—C8 | 1.393 (2) | C16—H16B | 0.9800 |
C7—H7 | 0.9500 | ||
O1—C1—N1 | 123.81 (12) | C14—C9—C10 | 122.26 (13) |
O1—C1—C3 | 121.86 (12) | C14—C9—N2 | 117.73 (12) |
N1—C1—C3 | 114.33 (11) | C10—C9—N2 | 119.95 (12) |
C1—N1—C2 | 128.06 (11) | C9—C10—C11 | 117.91 (13) |
C1—N1—H1 | 116.0 | C9—C10—C15 | 121.91 (13) |
C2—N1—H1 | 116.0 | C11—C10—C15 | 120.18 (13) |
N2—C2—N1 | 116.79 (11) | C12—C11—C10 | 119.49 (13) |
N2—C2—S1 | 124.85 (10) | C12—C11—C16 | 119.89 (13) |
N1—C2—S1 | 118.37 (10) | C10—C11—C16 | 120.61 (13) |
C2—N2—C9 | 123.85 (11) | C13—C12—C11 | 121.55 (13) |
C2—N2—H2 | 118.1 | C13—C12—H12 | 119.2 |
C9—N2—H2 | 118.1 | C11—C12—H12 | 119.2 |
C8—C3—C4 | 119.39 (12) | C14—C13—C12 | 119.64 (13) |
C8—C3—C1 | 119.55 (12) | C14—C13—H13 | 120.2 |
C4—C3—C1 | 120.99 (12) | C12—C13—H13 | 120.2 |
C5—C4—C3 | 121.20 (13) | C13—C14—C9 | 119.12 (13) |
C5—C4—Cl1 | 119.12 (11) | C13—C14—H14 | 120.4 |
C3—C4—Cl1 | 119.67 (11) | C9—C14—H14 | 120.4 |
C6—C5—C4 | 118.81 (14) | C10—C15—H15C | 109.5 |
C6—C5—H5 | 120.6 | C10—C15—H15A | 109.5 |
C4—C5—H5 | 120.6 | H15C—C15—H15A | 109.5 |
C5—C6—C7 | 120.82 (14) | C10—C15—H15B | 109.5 |
C5—C6—H6 | 119.6 | H15C—C15—H15B | 109.5 |
C7—C6—H6 | 119.6 | H15A—C15—H15B | 109.5 |
C6—C7—C8 | 119.76 (14) | C11—C16—H16C | 109.5 |
C6—C7—H7 | 120.1 | C11—C16—H16A | 109.5 |
C8—C7—H7 | 120.1 | H16C—C16—H16A | 109.5 |
C3—C8—C7 | 119.99 (14) | C11—C16—H16B | 109.5 |
C3—C8—H8 | 120.0 | H16C—C16—H16B | 109.5 |
C7—C8—H8 | 120.0 | H16A—C16—H16B | 109.5 |
O1—C1—N1—C2 | 7.9 (2) | C1—C3—C8—C7 | −177.24 (12) |
C3—C1—N1—C2 | −172.60 (12) | C6—C7—C8—C3 | 1.1 (2) |
C1—N1—C2—N2 | 2.5 (2) | C2—N2—C9—C14 | −64.20 (17) |
C1—N1—C2—S1 | −177.20 (11) | C2—N2—C9—C10 | 118.53 (15) |
N1—C2—N2—C9 | 171.32 (12) | C14—C9—C10—C11 | −0.39 (19) |
S1—C2—N2—C9 | −8.96 (19) | N2—C9—C10—C11 | 176.76 (11) |
O1—C1—C3—C8 | 74.09 (18) | C14—C9—C10—C15 | 179.07 (12) |
N1—C1—C3—C8 | −105.46 (15) | N2—C9—C10—C15 | −3.78 (19) |
O1—C1—C3—C4 | −102.77 (16) | C9—C10—C11—C12 | 1.59 (19) |
N1—C1—C3—C4 | 77.68 (16) | C15—C10—C11—C12 | −177.88 (12) |
C8—C3—C4—C5 | −1.0 (2) | C9—C10—C11—C16 | −178.78 (12) |
C1—C3—C4—C5 | 175.84 (12) | C15—C10—C11—C16 | 1.75 (19) |
C8—C3—C4—Cl1 | 179.64 (10) | C10—C11—C12—C13 | −1.4 (2) |
C1—C3—C4—Cl1 | −3.49 (17) | C16—C11—C12—C13 | 178.98 (13) |
C3—C4—C5—C6 | 1.6 (2) | C11—C12—C13—C14 | −0.1 (2) |
Cl1—C4—C5—C6 | −179.05 (11) | C12—C13—C14—C9 | 1.29 (19) |
C4—C5—C6—C7 | −0.9 (2) | C10—C9—C14—C13 | −1.1 (2) |
C5—C6—C7—C8 | −0.5 (2) | N2—C9—C14—C13 | −178.27 (11) |
C4—C3—C8—C7 | −0.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.88 | 2.46 | 3.3104 (15) | 164 |
N2—H2···O1 | 0.88 | 2.00 | 2.6866 (17) | 134 |
Symmetry code: (i) −x, −y, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C16H15ClN2OS |
Mr | 318.81 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 123 |
a, b, c (Å) | 7.489 (3), 9.338 (4), 13.274 (5) |
α, β, γ (°) | 65.674 (13), 69.975 (16), 73.639 (17) |
V (Å3) | 783.9 (5) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.38 |
Crystal size (mm) | 0.50 × 0.35 × 0.28 |
Data collection | |
Diffractometer | Rigaku/MSC Mercury CCD diffractometer |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6180, 3506, 3373 |
Rint | 0.062 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.036, 0.090, 1.08 |
No. of reflections | 3506 |
No. of parameters | 192 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.32, −0.31 |
Computer programs: CrystalClear (Molecular Structure Corporation & Rigaku, 2001), SIR97 (Altomare et al., 1999), SHELXL97 (Sheldrick, 2008), ORTEPII (Johnson, 1976), Yadokari-XG (Wakita, 2001; Kabuto et al., 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1···S1i | 0.88 | 2.46 | 3.3104 (15) | 163.6 |
N2—H2···O1 | 0.88 | 2.00 | 2.6866 (17) | 134.3 |
Symmetry code: (i) −x, −y, −z+1. |
Acknowledgements
MR is grateful to The Quaid-i-Azam University, Islamabad, for financial support for a postdoctoral fellowship.
References
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Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA. Google Scholar
Kabuto, C., Akine, S., Nemoto, T. & Kwon, E. (2009). J. Cryst. Soc. Jpn, 51, 218–224. CrossRef Google Scholar
Molecular Structure Corporation & Rigaku (2001). CrystalClear. MSC, The Woodlands, Texas, USA, and Rigaku Corporation, Tokyo, Japan. Google Scholar
Rauf, M. K, Ebihara, M., Badshah, A. & Imtiaz-ud-Din, (2012). Acta Cryst. E68, o119. Google Scholar
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Wakita, K. (2001). Yadokari-XG. http://www.hat.hi-ho.ne .jp/k-wakita/yadokari Google Scholar
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The background to this study has been set out in our previous work for the structural chemistry of N,N'-disubstituted thiourea (Rauf et al., 2012) and their coordination chemistry. Herein, as a continuation of these crytallographic studies, the structure of the title compound (I) is described, Fig. 1. Compared to N-benzoyl-N'-phenylthioureas [Cambridge Structural Database (Mogul Version 1.7; Allen, 2002], the methyl substitutions at C(10) and C(11)on phenyl ring, implies no significant effect on these bond lengths. 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 dihedral angles to the O(1) C(1) N(1) C(2) N(2)S(1) plane are 79.89 (2)° for the ring formed by C(3) to C(8) and 65.32 (2)° for the ring formed by C(9) to C(14). An intramolecular N—H···O H–bond is present (Table 1), forming a six-membered ring commonly observed in this class of compounds (Rauf et al., 2012). In the crystal packing of (I), intermolecular N—H···S H–bonds link the molecules into centrosymmetric dimers (Fig.2).