organic compounds
1-(2-Chlorobenzoyl)-3-(3-methoxyphenyl)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: aminbadshah@yahoo.com, mkhawarrauf@yahoo.co.uk
The title compound, C15H13ClN2O2S, 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. In the crystal, N—H⋯S hydrogen bonds link the molecules into centrosymmetric dimers.
Related literature
For previous work on N,N′-disubstituted thioureas, see: Rauf et al. (2012). For a description of the Cambridge Structural Database, see: Allen (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
https://doi.org/10.1107/S1600536812048830/mw2100sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536812048830/mw2100Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536812048830/mw2100Isup3.cml
Freshly prepared 2-chlorobenzoyl isothiocyanate (1.98 g, 10 mmol) was stirred in acetone (50 mL) for 30 minutes. Distilled 3-methoxyaniline (1.23 g, 10 mmol)was then added and the resulting mixture was stirred for 1 h. The reaction mixture was then poured into acidified (pH 4) water and stirred. The solid product was separated and washed with deionized water and purified by recrystallization from methanol/dichloromethane (1:10 v/v) to give fine crystals of (I) with an overall yield of 93% (2.98 g). M.P; 109–109.5°C. Anal. calcd. for C15H13ClN2O2S; C, 56.16 H, 4.08 N, 8.73 S, 10.00 Found: C, 56.12 H, 4.07 N, 8.73 S, 9.98.
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.
The background to this study has been set out in our previous work on the structural and coordination chemistry of N,N'-disubstituted thioureas (Rauf et al., 2012). Herein, as a continuation of these studies, the structure of the title compound (I) is described. A depiction of the molecule is given in Fig. 1. Bond lengths and angles are comparable to those for other N,N'-disubstituted thioureas reported in the Cambridge Structural Database (Allen, 2002). The molecule exists in the thione form with typical thiourea C—S and C—O bonds as well as shortened C—N bond lengths. The molecule features an intramolecular N—H···O hydrogen bond and in the solid molecules associate via intermolecular N—H···S hydrogen bonds which link the molecules into centrosymmetric dimers (Table 1 and Fig. 2).
For previous work on N,N'-disubstituted thioureas, see: Rauf et al. (2012). For a description of the Cambridge Structural Database, see: Allen (2002).
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).C15H13ClN2O2S | Z = 2 |
Mr = 320.78 | F(000) = 332 |
Triclinic, P1 | Dx = 1.477 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71070 Å |
a = 6.276 (3) Å | Cell parameters from 2546 reflections |
b = 10.202 (5) Å | θ = 3.3–27.5° |
c = 11.411 (5) Å | µ = 0.41 mm−1 |
α = 94.541 (7)° | T = 123 K |
β = 93.305 (6)° | Block, colorless |
γ = 96.918 (7)° | 0.45 × 0.36 × 0.20 mm |
V = 721.3 (6) Å3 |
Rigaku/MSC Mercury CCD diffractometer | 3071 reflections with I > 2σ(I) |
Radiation source: Rotating Anode | Rint = 0.052 |
Graphite Monochromator monochromator | θmax = 27.5°, θmin = 3.3° |
Detector resolution: 14.62 pixels mm-1 | h = −8→5 |
ω scans | k = −13→13 |
5698 measured reflections | l = −14→14 |
3222 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)] = 0.035 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.09 | w = 1/[σ2(Fo2) + (0.0309P)2 + 0.5054P] where P = (Fo2 + 2Fc2)/3 |
3222 reflections | (Δ/σ)max = 0.001 |
191 parameters | Δρmax = 0.33 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
C15H13ClN2O2S | γ = 96.918 (7)° |
Mr = 320.78 | V = 721.3 (6) Å3 |
Triclinic, P1 | Z = 2 |
a = 6.276 (3) Å | Mo Kα radiation |
b = 10.202 (5) Å | µ = 0.41 mm−1 |
c = 11.411 (5) Å | T = 123 K |
α = 94.541 (7)° | 0.45 × 0.36 × 0.20 mm |
β = 93.305 (6)° |
Rigaku/MSC Mercury CCD diffractometer | 3071 reflections with I > 2σ(I) |
5698 measured reflections | Rint = 0.052 |
3222 independent reflections |
R[F2 > 2σ(F2)] = 0.035 | 0 restraints |
wR(F2) = 0.088 | H-atom parameters constrained |
S = 1.09 | Δρmax = 0.33 e Å−3 |
3222 reflections | Δρmin = −0.34 e Å−3 |
191 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 | 0.6542 (2) | 0.57142 (13) | 0.79707 (12) | 0.0144 (3) | |
O1 | 0.58303 (17) | 0.56062 (10) | 0.89370 (9) | 0.0186 (2) | |
N1 | 0.56572 (19) | 0.49567 (12) | 0.69582 (11) | 0.0155 (2) | |
H1 | 0.6364 | 0.5052 | 0.6320 | 0.019* | |
C2 | 0.3774 (2) | 0.40595 (13) | 0.68314 (13) | 0.0147 (3) | |
S1 | 0.28505 (7) | 0.34880 (4) | 0.54559 (3) | 0.02392 (12) | |
N2 | 0.28727 (18) | 0.37856 (12) | 0.78283 (10) | 0.0148 (2) | |
H2 | 0.3660 | 0.4085 | 0.8479 | 0.018* | |
C3 | 0.8470 (2) | 0.66726 (14) | 0.77733 (12) | 0.0149 (3) | |
C4 | 0.8823 (2) | 0.79519 (14) | 0.83489 (13) | 0.0168 (3) | |
C5 | 1.0642 (3) | 0.88129 (15) | 0.81696 (14) | 0.0217 (3) | |
H5 | 1.0863 | 0.9678 | 0.8566 | 0.026* | |
C6 | 1.2135 (2) | 0.84109 (16) | 0.74122 (15) | 0.0236 (3) | |
H6 | 1.3379 | 0.9001 | 0.7292 | 0.028* | |
C7 | 1.1816 (2) | 0.71488 (16) | 0.68298 (14) | 0.0219 (3) | |
H7 | 1.2837 | 0.6875 | 0.6309 | 0.026* | |
C8 | 0.9996 (2) | 0.62846 (15) | 0.70116 (13) | 0.0179 (3) | |
H8 | 0.9787 | 0.5420 | 0.6614 | 0.021* | |
Cl1 | 0.69817 (6) | 0.85411 (4) | 0.92737 (3) | 0.02243 (11) | |
C9 | 0.0829 (2) | 0.30814 (13) | 0.79995 (12) | 0.0141 (3) | |
C10 | −0.0238 (2) | 0.20764 (14) | 0.72013 (13) | 0.0166 (3) | |
H10 | 0.0399 | 0.1801 | 0.6503 | 0.020* | |
C11 | −0.2262 (2) | 0.14852 (14) | 0.74534 (13) | 0.0164 (3) | |
C12 | −0.3209 (2) | 0.18776 (14) | 0.84774 (13) | 0.0181 (3) | |
H12 | −0.4605 | 0.1482 | 0.8627 | 0.022* | |
C13 | −0.2092 (2) | 0.28502 (15) | 0.92748 (13) | 0.0186 (3) | |
H13 | −0.2712 | 0.3107 | 0.9984 | 0.022* | |
C14 | −0.0068 (2) | 0.34540 (14) | 0.90434 (13) | 0.0169 (3) | |
H14 | 0.0697 | 0.4116 | 0.9595 | 0.020* | |
O2 | −0.34498 (17) | 0.04884 (11) | 0.67328 (10) | 0.0236 (3) | |
C15 | −0.2488 (3) | 0.00094 (16) | 0.57046 (14) | 0.0243 (3) | |
H15C | −0.2194 | 0.0732 | 0.5197 | 0.037* | |
H15A | −0.3473 | −0.0710 | 0.5274 | 0.037* | |
H15B | −0.1138 | −0.0322 | 0.5937 | 0.037* |
U11 | U22 | U33 | U12 | U13 | U23 | |
C1 | 0.0126 (6) | 0.0132 (6) | 0.0166 (7) | −0.0001 (5) | −0.0020 (5) | 0.0008 (5) |
O1 | 0.0193 (5) | 0.0203 (5) | 0.0144 (5) | −0.0045 (4) | 0.0003 (4) | 0.0006 (4) |
N1 | 0.0148 (6) | 0.0161 (6) | 0.0139 (6) | −0.0037 (4) | 0.0018 (4) | −0.0010 (4) |
C2 | 0.0147 (6) | 0.0110 (6) | 0.0176 (7) | −0.0007 (5) | 0.0001 (5) | −0.0003 (5) |
S1 | 0.0298 (2) | 0.0236 (2) | 0.01342 (19) | −0.01405 (15) | 0.00077 (14) | −0.00207 (14) |
N2 | 0.0127 (5) | 0.0153 (6) | 0.0147 (6) | −0.0028 (4) | −0.0013 (4) | −0.0005 (4) |
C3 | 0.0137 (6) | 0.0156 (6) | 0.0141 (6) | −0.0021 (5) | −0.0029 (5) | 0.0029 (5) |
C4 | 0.0175 (7) | 0.0171 (7) | 0.0147 (6) | −0.0009 (5) | −0.0030 (5) | 0.0017 (5) |
C5 | 0.0230 (7) | 0.0183 (7) | 0.0207 (7) | −0.0069 (6) | −0.0058 (6) | 0.0030 (6) |
C6 | 0.0161 (7) | 0.0268 (8) | 0.0260 (8) | −0.0070 (6) | −0.0048 (6) | 0.0099 (6) |
C7 | 0.0136 (7) | 0.0283 (8) | 0.0239 (8) | 0.0003 (6) | 0.0003 (5) | 0.0071 (6) |
C8 | 0.0148 (6) | 0.0184 (7) | 0.0197 (7) | 0.0001 (5) | −0.0022 (5) | 0.0026 (5) |
Cl1 | 0.0263 (2) | 0.01867 (18) | 0.02099 (19) | 0.00013 (14) | 0.00284 (14) | −0.00308 (13) |
C9 | 0.0124 (6) | 0.0128 (6) | 0.0164 (7) | −0.0008 (5) | −0.0007 (5) | 0.0031 (5) |
C10 | 0.0163 (7) | 0.0162 (7) | 0.0163 (7) | −0.0011 (5) | 0.0027 (5) | −0.0015 (5) |
C11 | 0.0152 (6) | 0.0144 (6) | 0.0183 (7) | −0.0021 (5) | −0.0003 (5) | −0.0002 (5) |
C12 | 0.0144 (6) | 0.0178 (7) | 0.0220 (7) | −0.0003 (5) | 0.0042 (5) | 0.0033 (5) |
C13 | 0.0204 (7) | 0.0188 (7) | 0.0168 (7) | 0.0020 (5) | 0.0047 (5) | 0.0009 (5) |
C14 | 0.0186 (7) | 0.0150 (6) | 0.0159 (7) | −0.0002 (5) | −0.0004 (5) | −0.0005 (5) |
O2 | 0.0190 (5) | 0.0236 (6) | 0.0239 (6) | −0.0095 (4) | 0.0047 (4) | −0.0077 (4) |
C15 | 0.0230 (7) | 0.0252 (8) | 0.0220 (8) | −0.0020 (6) | 0.0012 (6) | −0.0074 (6) |
C1—O1 | 1.2213 (18) | C7—H7 | 0.9500 |
C1—N1 | 1.3862 (18) | C8—H8 | 0.9500 |
C1—C3 | 1.5007 (19) | C9—C14 | 1.392 (2) |
N1—C2 | 1.3981 (18) | C9—C10 | 1.3948 (19) |
N1—H1 | 0.8800 | C10—C11 | 1.394 (2) |
C2—N2 | 1.3334 (19) | C10—H10 | 0.9500 |
C2—S1 | 1.6758 (16) | C11—O2 | 1.3713 (17) |
N2—C9 | 1.4243 (18) | C11—C12 | 1.394 (2) |
N2—H2 | 0.8800 | C12—C13 | 1.385 (2) |
C3—C4 | 1.401 (2) | C12—H12 | 0.9500 |
C3—C8 | 1.401 (2) | C13—C14 | 1.393 (2) |
C4—C5 | 1.389 (2) | C13—H13 | 0.9500 |
C4—Cl1 | 1.7370 (16) | C14—H14 | 0.9500 |
C5—C6 | 1.387 (2) | O2—C15 | 1.4288 (19) |
C5—H5 | 0.9500 | C15—H15C | 0.9800 |
C6—C7 | 1.388 (2) | C15—H15A | 0.9800 |
C6—H6 | 0.9500 | C15—H15B | 0.9800 |
C7—C8 | 1.392 (2) | ||
O1—C1—N1 | 123.20 (13) | C7—C8—H8 | 119.6 |
O1—C1—C3 | 122.98 (12) | C3—C8—H8 | 119.6 |
N1—C1—C3 | 113.82 (12) | C14—C9—C10 | 120.87 (13) |
C1—N1—C2 | 127.64 (12) | C14—C9—N2 | 115.32 (12) |
C1—N1—H1 | 116.2 | C10—C9—N2 | 123.81 (13) |
C2—N1—H1 | 116.2 | C11—C10—C9 | 118.42 (13) |
N2—C2—N1 | 115.74 (12) | C11—C10—H10 | 120.8 |
N2—C2—S1 | 127.15 (11) | C9—C10—H10 | 120.8 |
N1—C2—S1 | 117.08 (11) | O2—C11—C12 | 115.39 (13) |
C2—N2—C9 | 129.80 (12) | O2—C11—C10 | 123.32 (13) |
C2—N2—H2 | 115.1 | C12—C11—C10 | 121.30 (13) |
C9—N2—H2 | 115.1 | C13—C12—C11 | 119.29 (13) |
C4—C3—C8 | 118.29 (13) | C13—C12—H12 | 120.4 |
C4—C3—C1 | 121.86 (13) | C11—C12—H12 | 120.4 |
C8—C3—C1 | 119.84 (13) | C12—C13—C14 | 120.44 (13) |
C5—C4—C3 | 120.81 (14) | C12—C13—H13 | 119.8 |
C5—C4—Cl1 | 117.49 (12) | C14—C13—H13 | 119.8 |
C3—C4—Cl1 | 121.67 (11) | C9—C14—C13 | 119.61 (13) |
C6—C5—C4 | 120.05 (14) | C9—C14—H14 | 120.2 |
C6—C5—H5 | 120.0 | C13—C14—H14 | 120.2 |
C4—C5—H5 | 120.0 | C11—O2—C15 | 117.13 (12) |
C5—C6—C7 | 120.15 (14) | O2—C15—H15C | 109.5 |
C5—C6—H6 | 119.9 | O2—C15—H15A | 109.5 |
C7—C6—H6 | 119.9 | H15C—C15—H15A | 109.5 |
C6—C7—C8 | 119.81 (15) | O2—C15—H15B | 109.5 |
C6—C7—H7 | 120.1 | H15C—C15—H15B | 109.5 |
C8—C7—H7 | 120.1 | H15A—C15—H15B | 109.5 |
C7—C8—C3 | 120.88 (14) | ||
O1—C1—N1—C2 | 6.0 (2) | C6—C7—C8—C3 | 0.3 (2) |
C3—C1—N1—C2 | −174.52 (13) | C4—C3—C8—C7 | −0.1 (2) |
C1—N1—C2—N2 | −8.8 (2) | C1—C3—C8—C7 | −178.91 (13) |
C1—N1—C2—S1 | 169.20 (12) | C2—N2—C9—C14 | −151.59 (15) |
N1—C2—N2—C9 | 169.91 (13) | C2—N2—C9—C10 | 28.9 (2) |
S1—C2—N2—C9 | −7.9 (2) | C14—C9—C10—C11 | 2.3 (2) |
O1—C1—C3—C4 | −39.5 (2) | N2—C9—C10—C11 | −178.27 (13) |
N1—C1—C3—C4 | 141.05 (14) | C9—C10—C11—O2 | −179.88 (14) |
O1—C1—C3—C8 | 139.31 (15) | C9—C10—C11—C12 | −0.2 (2) |
N1—C1—C3—C8 | −40.16 (18) | O2—C11—C12—C13 | 177.99 (13) |
C8—C3—C4—C5 | −0.1 (2) | C10—C11—C12—C13 | −1.7 (2) |
C1—C3—C4—C5 | 178.72 (13) | C11—C12—C13—C14 | 1.6 (2) |
C8—C3—C4—Cl1 | 177.95 (11) | C10—C9—C14—C13 | −2.4 (2) |
C1—C3—C4—Cl1 | −3.24 (19) | N2—C9—C14—C13 | 178.10 (13) |
C3—C4—C5—C6 | 0.1 (2) | C12—C13—C14—C9 | 0.4 (2) |
Cl1—C4—C5—C6 | −178.03 (12) | C12—C11—O2—C15 | −176.82 (14) |
C4—C5—C6—C7 | 0.1 (2) | C10—C11—O2—C15 | 2.9 (2) |
C5—C6—C7—C8 | −0.3 (2) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.88 | 1.95 | 2.6500 (17) | 135 |
N1—H1···S1i | 0.88 | 2.64 | 3.4080 (17) | 146 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C15H13ClN2O2S |
Mr | 320.78 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 123 |
a, b, c (Å) | 6.276 (3), 10.202 (5), 11.411 (5) |
α, β, γ (°) | 94.541 (7), 93.305 (6), 96.918 (7) |
V (Å3) | 721.3 (6) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.41 |
Crystal size (mm) | 0.45 × 0.36 × 0.20 |
Data collection | |
Diffractometer | Rigaku/MSC Mercury CCD |
Absorption correction | – |
No. of measured, independent and observed [I > 2σ(I)] reflections | 5698, 3222, 3071 |
Rint | 0.052 |
(sin θ/λ)max (Å−1) | 0.649 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.035, 0.088, 1.09 |
No. of reflections | 3222 |
No. of parameters | 191 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.33, −0.34 |
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 |
N2—H2···O1 | 0.88 | 1.95 | 2.6500 (17) | 135 |
N1—H1···S1i | 0.88 | 2.64 | 3.4080 (17) | 146 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
Acknowledgements
MKR is grateful to The Quaid-i-Azam University, Islamabad for financial support for a postdoctoral fellowship.
References
Allen, F. H. (2002). Acta Cryst. B58, 380–388. Web of Science CSD CrossRef CAS IUCr Journals Google Scholar
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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. Crystallogr. 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, o120. Google Scholar
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The background to this study has been set out in our previous work on the structural and coordination chemistry of N,N'-disubstituted thioureas (Rauf et al., 2012). Herein, as a continuation of these studies, the structure of the title compound (I) is described. A depiction of the molecule is given in Fig. 1. Bond lengths and angles are comparable to those for other N,N'-disubstituted thioureas reported in the Cambridge Structural Database (Allen, 2002). The molecule exists in the thione form with typical thiourea C—S and C—O bonds as well as shortened C—N bond lengths. The molecule features an intramolecular N—H···O hydrogen bond and in the solid molecules associate via intermolecular N—H···S hydrogen bonds which link the molecules into centrosymmetric dimers (Table 1 and Fig. 2).