organic compounds
2-Methyl-N-[(3-methyl-2-pyridyl)carbamothioyl]benzamide
aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, UKM 43500 Bangi Selangor, Malaysia, bHEJ Research Institute of Chemistry, International Center for Chemical and Biological Sciences, University of Karachi, Karachi 75270, Pakistan, and cDepartment of Chemistry, Universiti Malaysia Terengganu, Manngabang Telipot, Terengganu, Malaysia
*Correspondence e-mail: sammer_yousuf@yahoo.com
In the title compound, C15H15N3OS, the thiourea group is stabilized by an intramolecular hydrogen bond between the carbonyl O atom and the thioamide group. A C—H⋯N intramolecular hydrogen bond is also present. Molecules are linked by intermolecular N—H⋯O and C—H⋯S hydrogen bonds.
Related literature
For the N-(3-iodophenyl)-N′-(2-methylbenzoyl)thiourea, see: Yusof et al. (2007). For bond-length data, see: Allen et al. (1987).
ofExperimental
Crystal data
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Refinement
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Data collection: SMART (Bruker, 2000); cell SAINT (Bruker, 2000); data reduction: SAINT; 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, PARST (Nardelli, 1995) and PLATON (Spek, 2003).
Supporting information
10.1107/S1600536808009513/sg2229sup1.cif
contains datablocks global, I. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536808009513/sg2229Isup2.hkl
The mixture of 2-methylbenzoyl chloride (9.720 g, 0.025mole) with the equimolar amount of ammonium thiocyanate (1.903 g, 0.025 mol) and 2-amino-3-methyl pyridine,(2.703 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% and the melting point is 412.3–413.8 K.
H atoms on the C of methyl, phenyl and pyridine were positioned geomatrically with C—H=0.96 Å and 0.93 Å respectively and constrained to ride on their parent atoms with Uiso(H)= 1.2Ueq(CH) and 1.5Ueq(CH3). The hydrogen atoms attached to the amino nitrogen atoms were located from the difference Fourier map and refined isotropically.
Data collection: SMART (Bruker, 2000); cell
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).C15H15N3OS | F(000) = 600 |
Mr = 285.36 | Dx = 1.303 Mg m−3 |
Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -P 2yn | Cell parameters from 2292 reflections |
a = 7.955 (3) Å | θ = 1.7–25.5° |
b = 7.811 (3) Å | µ = 0.22 mm−1 |
c = 23.414 (8) Å | T = 298 K |
β = 90.827 (6)° | Block, colourless |
V = 1454.6 (9) Å3 | 0.49 × 0.46 × 0.17 mm |
Z = 4 |
Bruker SMART APEX CCD area-detector diffractometer | 2710 independent reflections |
Radiation source: fine-focus sealed tube | 2099 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.019 |
Detector resolution: 83.66 pixels mm-1 | θmax = 25.5°, θmin = 1.7° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | k = −9→9 |
Tmin = 0.899, Tmax = 0.963 | l = −16→28 |
7524 measured 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)] = 0.041 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | w = 1/[σ2(Fo2) + (0.0591P)2 + 0.3029P] where P = (Fo2 + 2Fc2)/3 |
2710 reflections | (Δ/σ)max < 0.001 |
191 parameters | Δρmax = 0.24 e Å−3 |
1 restraint | Δρmin = −0.13 e Å−3 |
C15H15N3OS | V = 1454.6 (9) Å3 |
Mr = 285.36 | Z = 4 |
Monoclinic, P21/n | Mo Kα radiation |
a = 7.955 (3) Å | µ = 0.22 mm−1 |
b = 7.811 (3) Å | T = 298 K |
c = 23.414 (8) Å | 0.49 × 0.46 × 0.17 mm |
β = 90.827 (6)° |
Bruker SMART APEX CCD area-detector diffractometer | 2710 independent reflections |
Absorption correction: multi-scan (SADABS; Bruker, 2000) | 2099 reflections with I > 2σ(I) |
Tmin = 0.899, Tmax = 0.963 | Rint = 0.019 |
7524 measured reflections |
R[F2 > 2σ(F2)] = 0.041 | 1 restraint |
wR(F2) = 0.112 | H atoms treated by a mixture of independent and constrained refinement |
S = 1.02 | Δρmax = 0.24 e Å−3 |
2710 reflections | Δρmin = −0.13 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 | ||
S1 | 0.34243 (7) | 0.20705 (8) | 0.17685 (2) | 0.0662 (2) | |
O1 | 0.40058 (17) | 0.34898 (19) | −0.00872 (5) | 0.0599 (4) | |
N1 | 0.26335 (19) | 0.2529 (2) | 0.06915 (6) | 0.0485 (4) | |
H1 | 0.1847 (19) | 0.183 (2) | 0.0784 (8) | 0.056 (6)* | |
N2 | 0.49690 (18) | 0.4025 (2) | 0.10075 (6) | 0.0460 (4) | |
H2 | 0.513 (2) | 0.429 (3) | 0.0656 (9) | 0.057 (6)* | |
N3 | 0.77881 (19) | 0.3995 (2) | 0.12320 (7) | 0.0579 (4) | |
C1 | 0.1548 (2) | 0.1298 (2) | −0.07366 (8) | 0.0497 (5) | |
C2 | 0.0123 (3) | 0.0935 (3) | −0.10668 (9) | 0.0641 (6) | |
H2A | 0.0238 | 0.0305 | −0.1401 | 0.077* | |
C3 | −0.1439 (3) | 0.1477 (3) | −0.09150 (10) | 0.0707 (7) | |
H3 | −0.2358 | 0.1239 | −0.1152 | 0.085* | |
C4 | −0.1669 (3) | 0.2364 (3) | −0.04197 (11) | 0.0675 (6) | |
H4 | −0.2737 | 0.2720 | −0.0316 | 0.081* | |
C5 | −0.0286 (2) | 0.2727 (3) | −0.00736 (9) | 0.0537 (5) | |
H5 | −0.0430 | 0.3303 | 0.0270 | 0.064* | |
C6 | 0.1310 (2) | 0.2234 (2) | −0.02376 (7) | 0.0434 (4) | |
C7 | 0.3230 (3) | 0.0627 (3) | −0.09092 (10) | 0.0759 (7) | |
H7A | 0.3091 | −0.0141 | −0.1226 | 0.114* | |
H7B | 0.3742 | 0.0028 | −0.0594 | 0.114* | |
H7C | 0.3936 | 0.1565 | −0.1018 | 0.114* | |
C8 | 0.2781 (2) | 0.2805 (2) | 0.01149 (7) | 0.0433 (4) | |
C9 | 0.3749 (2) | 0.2940 (2) | 0.11353 (7) | 0.0457 (4) | |
C10 | 0.6291 (2) | 0.4528 (2) | 0.13916 (7) | 0.0437 (4) | |
C11 | 0.6000 (3) | 0.5570 (3) | 0.18580 (8) | 0.0554 (5) | |
C12 | 0.7424 (3) | 0.5988 (3) | 0.21814 (9) | 0.0688 (6) | |
H12 | 0.7315 | 0.6667 | 0.2505 | 0.083* | |
C13 | 0.8968 (3) | 0.5421 (3) | 0.20313 (10) | 0.0745 (7) | |
H13 | 0.9914 | 0.5683 | 0.2252 | 0.089* | |
C14 | 0.9096 (3) | 0.4468 (3) | 0.15529 (10) | 0.0732 (7) | |
H14 | 1.0162 | 0.4123 | 0.1442 | 0.088* | |
C15 | 0.4302 (3) | 0.6260 (4) | 0.20004 (11) | 0.0852 (8) | |
H15A | 0.3581 | 0.6201 | 0.1669 | 0.128* | |
H15B | 0.4408 | 0.7430 | 0.2121 | 0.128* | |
H15C | 0.3829 | 0.5593 | 0.2303 | 0.128* |
U11 | U22 | U33 | U12 | U13 | U23 | |
S1 | 0.0669 (4) | 0.0892 (4) | 0.0423 (3) | −0.0180 (3) | −0.0071 (2) | 0.0199 (3) |
O1 | 0.0565 (8) | 0.0822 (10) | 0.0411 (7) | −0.0295 (7) | 0.0001 (6) | 0.0024 (7) |
N1 | 0.0422 (9) | 0.0642 (10) | 0.0390 (8) | −0.0158 (7) | −0.0032 (6) | 0.0087 (7) |
N2 | 0.0425 (8) | 0.0628 (10) | 0.0325 (8) | −0.0091 (7) | −0.0020 (6) | 0.0037 (7) |
N3 | 0.0422 (9) | 0.0730 (11) | 0.0585 (10) | −0.0011 (8) | −0.0012 (7) | −0.0153 (8) |
C1 | 0.0598 (12) | 0.0452 (10) | 0.0441 (10) | −0.0082 (9) | −0.0028 (8) | 0.0020 (8) |
C2 | 0.0840 (16) | 0.0569 (13) | 0.0508 (11) | −0.0154 (12) | −0.0169 (11) | −0.0021 (10) |
C3 | 0.0697 (15) | 0.0612 (13) | 0.0801 (16) | −0.0157 (11) | −0.0364 (13) | 0.0138 (12) |
C4 | 0.0452 (12) | 0.0651 (14) | 0.0919 (17) | −0.0024 (10) | −0.0117 (11) | 0.0112 (13) |
C5 | 0.0485 (12) | 0.0559 (12) | 0.0567 (12) | −0.0043 (9) | −0.0023 (9) | 0.0011 (9) |
C6 | 0.0455 (10) | 0.0432 (9) | 0.0413 (9) | −0.0070 (8) | −0.0044 (7) | 0.0061 (8) |
C7 | 0.0810 (16) | 0.0757 (16) | 0.0713 (15) | 0.0002 (13) | 0.0119 (12) | −0.0179 (12) |
C8 | 0.0434 (10) | 0.0456 (10) | 0.0408 (9) | −0.0068 (8) | −0.0005 (7) | 0.0018 (8) |
C9 | 0.0387 (10) | 0.0565 (11) | 0.0418 (10) | −0.0005 (8) | −0.0014 (7) | 0.0026 (8) |
C10 | 0.0435 (10) | 0.0508 (10) | 0.0367 (9) | −0.0025 (8) | −0.0028 (7) | 0.0003 (8) |
C11 | 0.0634 (12) | 0.0592 (12) | 0.0435 (10) | 0.0039 (10) | 0.0008 (9) | −0.0035 (9) |
C12 | 0.0903 (17) | 0.0698 (15) | 0.0459 (11) | −0.0074 (13) | −0.0106 (11) | −0.0148 (10) |
C13 | 0.0637 (15) | 0.0915 (18) | 0.0675 (14) | −0.0146 (13) | −0.0233 (11) | −0.0064 (13) |
C14 | 0.0435 (12) | 0.0973 (18) | 0.0785 (15) | −0.0010 (11) | −0.0096 (10) | −0.0162 (13) |
C15 | 0.0838 (17) | 0.0948 (18) | 0.0774 (16) | 0.0215 (14) | 0.0110 (13) | −0.0214 (14) |
S1—C9 | 1.6545 (18) | C4—H4 | 0.9300 |
O1—C8 | 1.214 (2) | C5—C6 | 1.386 (3) |
N1—C8 | 1.374 (2) | C5—H5 | 0.9300 |
N1—C9 | 1.394 (2) | C6—C8 | 1.490 (2) |
N1—H1 | 0.860 (9) | C7—H7A | 0.9600 |
N2—C9 | 1.326 (2) | C7—H7B | 0.9600 |
N2—C10 | 1.429 (2) | C7—H7C | 0.9600 |
N2—H2 | 0.86 (2) | C10—C11 | 1.384 (3) |
N3—C10 | 1.321 (2) | C11—C12 | 1.392 (3) |
N3—C14 | 1.327 (3) | C11—C15 | 1.497 (3) |
C1—C2 | 1.392 (3) | C12—C13 | 1.357 (3) |
C1—C6 | 1.394 (3) | C12—H12 | 0.9300 |
C1—C7 | 1.498 (3) | C13—C14 | 1.350 (3) |
C2—C3 | 1.364 (3) | C13—H13 | 0.9300 |
C2—H2A | 0.9300 | C14—H14 | 0.9300 |
C3—C4 | 1.366 (3) | C15—H15A | 0.9600 |
C3—H3 | 0.9300 | C15—H15B | 0.9600 |
C4—C5 | 1.386 (3) | C15—H15C | 0.9600 |
C8—N1—C9 | 129.35 (15) | H7A—C7—H7C | 109.5 |
C8—N1—H1 | 114.8 (13) | H7B—C7—H7C | 109.5 |
C9—N1—H1 | 114.6 (13) | O1—C8—N1 | 122.17 (16) |
C9—N2—C10 | 124.63 (15) | O1—C8—C6 | 122.97 (16) |
C9—N2—H2 | 119.5 (13) | N1—C8—C6 | 114.85 (14) |
C10—N2—H2 | 114.5 (13) | N2—C9—N1 | 116.05 (15) |
C10—N3—C14 | 117.05 (18) | N2—C9—S1 | 126.06 (14) |
C2—C1—C6 | 116.94 (19) | N1—C9—S1 | 117.88 (13) |
C2—C1—C7 | 120.18 (19) | N3—C10—C11 | 124.77 (17) |
C6—C1—C7 | 122.84 (18) | N3—C10—N2 | 113.16 (15) |
C3—C2—C1 | 122.0 (2) | C11—C10—N2 | 121.92 (16) |
C3—C2—H2A | 119.0 | C10—C11—C12 | 115.06 (19) |
C1—C2—H2A | 119.0 | C10—C11—C15 | 123.32 (19) |
C2—C3—C4 | 120.8 (2) | C12—C11—C15 | 121.6 (2) |
C2—C3—H3 | 119.6 | C13—C12—C11 | 121.0 (2) |
C4—C3—H3 | 119.6 | C13—C12—H12 | 119.5 |
C3—C4—C5 | 119.1 (2) | C11—C12—H12 | 119.5 |
C3—C4—H4 | 120.5 | C14—C13—C12 | 118.4 (2) |
C5—C4—H4 | 120.5 | C14—C13—H13 | 120.8 |
C4—C5—C6 | 120.2 (2) | C12—C13—H13 | 120.8 |
C4—C5—H5 | 119.9 | N3—C14—C13 | 123.7 (2) |
C6—C5—H5 | 119.9 | N3—C14—H14 | 118.1 |
C5—C6—C1 | 120.92 (17) | C13—C14—H14 | 118.1 |
C5—C6—C8 | 118.59 (16) | C11—C15—H15A | 109.5 |
C1—C6—C8 | 120.42 (16) | C11—C15—H15B | 109.5 |
C1—C7—H7A | 109.5 | H15A—C15—H15B | 109.5 |
C1—C7—H7B | 109.5 | C11—C15—H15C | 109.5 |
H7A—C7—H7B | 109.5 | H15A—C15—H15C | 109.5 |
C1—C7—H7C | 109.5 | H15B—C15—H15C | 109.5 |
C6—C1—C2—C3 | 0.5 (3) | C10—N2—C9—N1 | −176.19 (16) |
C7—C1—C2—C3 | 177.9 (2) | C10—N2—C9—S1 | 4.8 (3) |
C1—C2—C3—C4 | −1.8 (3) | C8—N1—C9—N2 | 14.3 (3) |
C2—C3—C4—C5 | 0.7 (3) | C8—N1—C9—S1 | −166.69 (16) |
C3—C4—C5—C6 | 1.8 (3) | C14—N3—C10—C11 | 1.6 (3) |
C4—C5—C6—C1 | −3.1 (3) | C14—N3—C10—N2 | 177.29 (19) |
C4—C5—C6—C8 | 173.72 (17) | C9—N2—C10—N3 | 113.7 (2) |
C2—C1—C6—C5 | 2.0 (3) | C9—N2—C10—C11 | −70.4 (3) |
C7—C1—C6—C5 | −175.40 (18) | N3—C10—C11—C12 | −2.8 (3) |
C2—C1—C6—C8 | −174.81 (17) | N2—C10—C11—C12 | −178.13 (18) |
C7—C1—C6—C8 | 7.8 (3) | N3—C10—C11—C15 | 175.1 (2) |
C9—N1—C8—O1 | 0.3 (3) | N2—C10—C11—C15 | −0.2 (3) |
C9—N1—C8—C6 | −178.45 (18) | C10—C11—C12—C13 | 1.2 (3) |
C5—C6—C8—O1 | −129.5 (2) | C15—C11—C12—C13 | −176.7 (2) |
C1—C6—C8—O1 | 47.3 (3) | C11—C12—C13—C14 | 1.3 (4) |
C5—C6—C8—N1 | 49.2 (2) | C10—N3—C14—C13 | 1.3 (4) |
C1—C6—C8—N1 | −133.98 (18) | C12—C13—C14—N3 | −2.8 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.86 (2) | 2.04 (2) | 2.697 (2) | 132.2 (18) |
C15—H15A···N2 | 0.96 | 2.56 | 2.961 | 105 |
N2—H2···O1i | 0.86 (2) | 2.30 (2) | 3.021 (2) | 142 (2) |
C13—H13···S1ii | 0.93 | 2.85 | 3.700 | 154 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, y+1/2, −z+1/2. |
Experimental details
Crystal data | |
Chemical formula | C15H15N3OS |
Mr | 285.36 |
Crystal system, space group | Monoclinic, P21/n |
Temperature (K) | 298 |
a, b, c (Å) | 7.955 (3), 7.811 (3), 23.414 (8) |
β (°) | 90.827 (6) |
V (Å3) | 1454.6 (9) |
Z | 4 |
Radiation type | Mo Kα |
µ (mm−1) | 0.22 |
Crystal size (mm) | 0.49 × 0.46 × 0.17 |
Data collection | |
Diffractometer | Bruker SMART APEX CCD area-detector diffractometer |
Absorption correction | Multi-scan (SADABS; Bruker, 2000) |
Tmin, Tmax | 0.899, 0.963 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 7524, 2710, 2099 |
Rint | 0.019 |
(sin θ/λ)max (Å−1) | 0.606 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.041, 0.112, 1.02 |
No. of reflections | 2710 |
No. of parameters | 191 |
No. of restraints | 1 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement |
Δρmax, Δρmin (e Å−3) | 0.24, −0.13 |
Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), PARST (Nardelli, 1995) and PLATON (Spek, 2003).
D—H···A | D—H | H···A | D···A | D—H···A |
N2—H2···O1 | 0.86 (2) | 2.04 (2) | 2.697 (2) | 132.2 (18) |
C15—H15A···N2 | 0.96 | 2.56 | 2.961 | 105 |
N2—H2···O1i | 0.86 (2) | 2.30 (2) | 3.021 (2) | 142 (2) |
C13—H13···S1ii | 0.93 | 2.85 | 3.700 | 154 |
Symmetry codes: (i) −x+1, −y+1, −z; (ii) −x+3/2, y+1/2, −z+1/2. |
Acknowledgements
The authors thank the Ministry of Higher Education of Malaysia for Fundamental Research Grants UKM-ST-01-FRGS-0003-2006 and UMT-FRGS-59001, and Universiti Kebangsaan Malaysia and HEJ Research Institute of Chemistry, University of Karachi, for research facilities.
References
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. CrossRef Web of Science Google Scholar
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Nardelli, M. (1995). J. Appl. Cryst. 28, 659. CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2003). J. Appl. Cryst. 36, 7–13. Web of Science CrossRef CAS IUCr Journals Google Scholar
Yusof, M. S. M., Ahmad Mushtari, N. & Yamin, B. M. (2007). Acta Cryst. E63, o4709. Web of Science CSD CrossRef IUCr Journals Google Scholar
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The title compound, (I), is analogous to N-(3-iodophenyl)-N'-(2-methylbenzoyl) thiourea (II), (Yusof et al., 2007) except that the iodophenyl group is replaced by the 3-methylpyridine group (Fig.1). The bond lengths and angles are in normal range (Allen et al., 1987). The central thiourea moiety, S1/N1/N2/C9, pyridine, N3/(C10—C14), and benzene,(C1—C6) rings are each planar with maximum deviation of 0.033 (2)Å for N2 atom from the least square plane. The central thiourea moiety makes dihedral angle with the pyridine and benzene rings of 64.58 (8) and 62.03 (8)° respectively. The dihedral angle between the pyridine and benzene rings (4.03 (10)°) is smaller compared to that in (II) of 31.88 (9)°. The molecule maintains the trans-cis geometry of the thiourea moiety which is stabilized by the intrahydrogen bond between the carbonyl oxygen atom O1 and the thioamide hydrogen atom, H15A. In the crystal structure, the molecules are linked by the N2—H2···O1 and C13—H13···S1 intermolecular hydrogen bonds (symmtery codes as in Table 2).