N-(Diphenyl-carbamothio-yl)-3-methyl-benzamide.

The synthesis of the title compound, C(21)H(18)N(2)OS, involves the reaction of 3-methyl-benzoyl chloride with potassium thio-cyanate in dry acetone followed by condensation of the 3-methyl-benzoyl isothio-cyanate with diphenyl-amine. The carbonyl [C-O = 1.215 (2) Å] and thio-carbonyl [C-S = 1.6721 (17) Å] distances indicate that these correspond to double bonds. The short C-N bonds at the center of the mol-ecule reveal the effects of resonance in this part of the mol-ecule. The conformation of the mol-ecule with respect to the thio-carbonyl and carbonyl groups is twisted. The 3-methyl-phenyl and two phenyl rings are also twisted, with dihedral angles of 75.67 (9) and 14.91 (9)°. The phenyl rings are rotated out of the mean plane of the N-C-S-N atoms by 66.87 (8) and 78.40 (9)°. Pairs of mol-ecules are linked into centrosymmetric dimers via inter-molecular N-H⋯S inter-actions and a C-H⋯O link also occurs. The dimers are stacked along the a axis.

Related literature

For synthesis, see: Özer et al. (2009 ▶); Mansuroğlu et al. (2008 ▶); Uğur et al. (2006 ▶); Arslan et al. (2003a ▶, and references therein). For general background, see: Koch (2001 ▶); El Aamrani et al. (1998 ▶, 1999 ▶). For related compounds, see: Arslan et al. (2003b ▶,c ▶, 2004 ▶); Khawar Rauf et al. (2009a ▶,b ▶,c ▶,d ▶).

Experimental

Crystal data

C21H18N2OS

M = 346.43

Orthorhombic,

a = 10.6928 (12) Å

b = 16.7647 (17) Å

c = 19.865 (2) Å

V = 3561.0 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.19 mm−1

T = 120 (2) K

0.41 × 0.23 × 0.08 mm

Data collection

Bruker SMART APEX diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T min = 0.925, T max = 0.985

29957 measured reflections

4241 independent reflections

2955 reflections with I > 2σ(I)

R int = 0.098

Refinement

R[F 2 > 2σ(F 2)] = 0.047

wR(F 2) = 0.101

S = 0.95

4241 reflections

231 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.28 e Å−3

Δρmin = −0.38 e Å−3

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809002554/at2712sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809002554/at2712Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C21H18N2OS	F(000) = 1456
Mr = 346.43	Dx = 1.292 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 801 reflections
a = 10.6928 (12) Å	θ = 2.5–25.9°
b = 16.7647 (17) Å	µ = 0.19 mm−1
c = 19.865 (2) Å	T = 120 K
V = 3561.0 (6) Å3	Prism, colourless
Z = 8	0.41 × 0.23 × 0.08 mm

Bruker SMART APEX diffractometer	4241 independent reflections
Radiation source: sealed tube	2955 reflections with I > 2σ(I)
graphite	Rint = 0.098
φ and ω scans	θmax = 27.9°, θmin = 2.1°
Absorption correction: multi-scan (SADABS; Bruker, 2002)	h = −14→14
Tmin = 0.925, Tmax = 0.985	k = −22→19
29957 measured reflections	l = −26→26

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)] = 0.047	Hydrogen site location: difference Fourier map
wR(F2) = 0.101	H atoms treated by a mixture of independent and constrained refinement
S = 0.95	w = 1/[σ2(Fo2) + (0.0429P)2] where P = (Fo2 + 2Fc2)/3
4241 reflections	(Δ/σ)max = 0.001
231 parameters	Δρmax = 0.28 e Å−3
1 restraint	Δρmin = −0.38 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.49155 (4)	0.96594 (3)	0.60687 (2)	0.02357 (13)
O1	0.83581 (11)	0.88560 (8)	0.53805 (6)	0.0282 (3)
N1	0.63123 (14)	0.90441 (8)	0.50788 (7)	0.0194 (3)
H1	0.5892 (15)	0.9383 (8)	0.4811 (7)	0.029 (5)*
N2	0.61147 (13)	0.82693 (8)	0.60385 (7)	0.0198 (3)
C1	0.75893 (17)	0.89869 (10)	0.49441 (8)	0.0204 (4)
C2	0.79282 (16)	0.91117 (10)	0.42236 (8)	0.0201 (4)
C3	0.90683 (17)	0.94747 (10)	0.40766 (9)	0.0226 (4)
H3A	0.9603	0.9633	0.4434	0.027*
C4	0.94370 (18)	0.96101 (10)	0.34132 (9)	0.0252 (4)
C5	1.0663 (2)	1.00079 (12)	0.32634 (10)	0.0360 (5)
H5A	1.1349	0.9638	0.3362	0.054*
H5B	1.0750	1.0486	0.3543	0.054*
H5C	1.0692	1.0159	0.2787	0.054*
C6	0.86364 (18)	0.93615 (11)	0.29006 (9)	0.0283 (4)
H6A	0.8863	0.9456	0.2445	0.034*
C7	0.75192 (18)	0.89805 (11)	0.30421 (8)	0.0280 (4)
H7A	0.7001	0.8801	0.2685	0.034*
C8	0.71531 (17)	0.88605 (10)	0.37039 (9)	0.0237 (4)
H8A	0.6378	0.8608	0.3801	0.028*
C9	0.58249 (16)	0.89564 (10)	0.57267 (8)	0.0190 (4)
C10	0.65779 (16)	0.75696 (10)	0.56929 (8)	0.0200 (4)
C11	0.58848 (18)	0.72236 (10)	0.51815 (8)	0.0241 (4)
H11A	0.5118	0.7455	0.5040	0.029*
C12	0.63308 (19)	0.65307 (10)	0.48777 (9)	0.0307 (5)
H12A	0.5872	0.6291	0.4522	0.037*
C13	0.7437 (2)	0.61921 (11)	0.50926 (10)	0.0346 (5)
H13A	0.7741	0.5723	0.4881	0.042*
C14	0.81025 (19)	0.65320 (11)	0.56141 (11)	0.0360 (5)
H14A	0.8852	0.6289	0.5768	0.043*
C15	0.76792 (18)	0.72271 (11)	0.59126 (9)	0.0287 (4)
H15A	0.8143	0.7467	0.6267	0.034*
C16	0.59063 (16)	0.81692 (10)	0.67524 (8)	0.0191 (4)
C17	0.50108 (18)	0.76351 (11)	0.69656 (9)	0.0285 (4)
H17A	0.4504	0.7359	0.6649	0.034*
C18	0.4862 (2)	0.75071 (12)	0.76492 (9)	0.0371 (5)
H18A	0.4246	0.7143	0.7803	0.045*
C19	0.5600 (2)	0.79033 (11)	0.81074 (9)	0.0342 (5)
H19A	0.5486	0.7814	0.8576	0.041*
C20	0.65082 (19)	0.84305 (12)	0.78887 (9)	0.0317 (5)
H20A	0.7026	0.8697	0.8206	0.038*
C21	0.66613 (18)	0.85692 (11)	0.72048 (9)	0.0258 (4)
H21A	0.7277	0.8934	0.7050	0.031*

	U11	U22	U33	U12	U13	U23
S1	0.0282 (3)	0.0204 (2)	0.0221 (2)	0.00679 (19)	0.0028 (2)	0.00050 (19)
O1	0.0228 (7)	0.0371 (8)	0.0248 (7)	−0.0013 (6)	−0.0014 (6)	0.0050 (6)
N1	0.0203 (8)	0.0184 (8)	0.0197 (7)	0.0027 (6)	0.0013 (6)	0.0037 (6)
N2	0.0226 (8)	0.0181 (7)	0.0186 (7)	0.0038 (6)	0.0025 (6)	0.0010 (6)
C1	0.0207 (9)	0.0157 (9)	0.0246 (9)	−0.0010 (7)	0.0012 (8)	−0.0003 (7)
C2	0.0237 (10)	0.0155 (9)	0.0210 (9)	0.0059 (7)	0.0022 (7)	0.0008 (7)
C3	0.0225 (10)	0.0206 (9)	0.0248 (9)	0.0027 (8)	0.0010 (8)	−0.0007 (7)
C4	0.0290 (10)	0.0188 (9)	0.0278 (10)	0.0045 (8)	0.0068 (8)	0.0008 (8)
C5	0.0366 (12)	0.0390 (12)	0.0324 (11)	−0.0055 (10)	0.0126 (9)	−0.0003 (9)
C6	0.0384 (12)	0.0260 (10)	0.0204 (9)	0.0050 (9)	0.0079 (8)	0.0023 (8)
C7	0.0320 (11)	0.0291 (10)	0.0231 (9)	0.0031 (9)	−0.0026 (8)	−0.0032 (8)
C8	0.0221 (10)	0.0218 (10)	0.0271 (9)	0.0018 (8)	0.0018 (8)	−0.0010 (8)
C9	0.0177 (9)	0.0196 (9)	0.0196 (9)	−0.0018 (7)	−0.0022 (7)	−0.0003 (7)
C10	0.0228 (10)	0.0163 (9)	0.0208 (9)	0.0013 (7)	0.0055 (7)	0.0032 (7)
C11	0.0263 (11)	0.0214 (9)	0.0247 (9)	0.0010 (8)	0.0013 (8)	0.0025 (7)
C12	0.0389 (12)	0.0223 (10)	0.0310 (10)	−0.0028 (9)	0.0046 (9)	−0.0046 (8)
C13	0.0370 (12)	0.0186 (10)	0.0482 (12)	0.0033 (9)	0.0164 (10)	−0.0037 (9)
C14	0.0250 (11)	0.0288 (11)	0.0542 (13)	0.0104 (9)	0.0037 (10)	0.0050 (10)
C15	0.0264 (11)	0.0275 (11)	0.0322 (10)	0.0034 (8)	−0.0042 (8)	0.0007 (8)
C16	0.0222 (10)	0.0173 (8)	0.0178 (8)	0.0045 (7)	0.0025 (7)	0.0013 (7)
C17	0.0304 (11)	0.0289 (10)	0.0263 (10)	−0.0072 (9)	0.0060 (8)	−0.0042 (8)
C18	0.0515 (14)	0.0301 (11)	0.0297 (11)	−0.0106 (10)	0.0151 (10)	−0.0013 (9)
C19	0.0529 (14)	0.0291 (11)	0.0206 (10)	0.0054 (10)	0.0078 (9)	0.0029 (8)
C20	0.0378 (13)	0.0328 (11)	0.0243 (10)	0.0024 (9)	−0.0047 (9)	−0.0039 (8)
C21	0.0256 (11)	0.0259 (10)	0.0259 (9)	−0.0025 (8)	0.0002 (8)	0.0013 (8)

S1—C9	1.6721 (17)	C10—C15	1.381 (2)
O1—C1	1.215 (2)	C10—C11	1.385 (2)
N1—C1	1.395 (2)	C11—C12	1.393 (2)
N1—C9	1.396 (2)	C11—H11A	0.9500
N1—H1	0.899 (14)	C12—C13	1.379 (3)
N2—C9	1.344 (2)	C12—H12A	0.9500
N2—C16	1.445 (2)	C13—C14	1.380 (3)
N2—C10	1.447 (2)	C13—H13A	0.9500
C1—C2	1.491 (2)	C14—C15	1.384 (3)
C2—C8	1.389 (2)	C14—H14A	0.9500
C2—C3	1.393 (2)	C15—H15A	0.9500
C3—C4	1.394 (2)	C16—C17	1.378 (2)
C3—H3A	0.9500	C16—C21	1.382 (2)
C4—C6	1.394 (3)	C17—C18	1.384 (2)
C4—C5	1.501 (3)	C17—H17A	0.9500
C5—H5A	0.9800	C18—C19	1.375 (3)
C5—H5B	0.9800	C18—H18A	0.9500
C5—H5C	0.9800	C19—C20	1.383 (3)
C6—C7	1.383 (3)	C19—H19A	0.9500
C6—H6A	0.9500	C20—C21	1.388 (2)
C7—C8	1.386 (2)	C20—H20A	0.9500
C7—H7A	0.9500	C21—H21A	0.9500
C8—H8A	0.9500
C1—N1—C9	122.34 (14)	C15—C10—C11	120.93 (16)
C1—N1—H1	114.8 (12)	C15—C10—N2	118.63 (15)
C9—N1—H1	115.1 (12)	C11—C10—N2	120.30 (15)
C9—N2—C16	121.07 (14)	C10—C11—C12	118.94 (18)
C9—N2—C10	123.73 (14)	C10—C11—H11A	120.5
C16—N2—C10	115.11 (13)	C12—C11—H11A	120.5
O1—C1—N1	122.56 (16)	C13—C12—C11	120.17 (18)
O1—C1—C2	123.08 (16)	C13—C12—H12A	119.9
N1—C1—C2	114.35 (15)	C11—C12—H12A	119.9
C8—C2—C3	119.91 (16)	C12—C13—C14	120.30 (18)
C8—C2—C1	121.72 (16)	C12—C13—H13A	119.9
C3—C2—C1	118.36 (16)	C14—C13—H13A	119.9
C2—C3—C4	121.10 (17)	C13—C14—C15	120.05 (19)
C2—C3—H3A	119.5	C13—C14—H14A	120.0
C4—C3—H3A	119.5	C15—C14—H14A	120.0
C6—C4—C3	117.92 (17)	C10—C15—C14	119.59 (18)
C6—C4—C5	121.64 (17)	C10—C15—H15A	120.2
C3—C4—C5	120.44 (17)	C14—C15—H15A	120.2
C4—C5—H5A	109.5	C17—C16—C21	121.43 (16)
C4—C5—H5B	109.5	C17—C16—N2	118.97 (15)
H5A—C5—H5B	109.5	C21—C16—N2	119.46 (16)
C4—C5—H5C	109.5	C16—C17—C18	118.82 (18)
H5A—C5—H5C	109.5	C16—C17—H17A	120.6
H5B—C5—H5C	109.5	C18—C17—H17A	120.6
C7—C6—C4	121.31 (17)	C19—C18—C17	120.57 (18)
C7—C6—H6A	119.3	C19—C18—H18A	119.7
C4—C6—H6A	119.3	C17—C18—H18A	119.7
C6—C7—C8	120.24 (17)	C18—C19—C20	120.24 (17)
C6—C7—H7A	119.9	C18—C19—H19A	119.9
C8—C7—H7A	119.9	C20—C19—H19A	119.9
C7—C8—C2	119.48 (17)	C19—C20—C21	119.82 (18)
C7—C8—H8A	120.3	C19—C20—H20A	120.1
C2—C8—H8A	120.3	C21—C20—H20A	120.1
N2—C9—N1	115.40 (15)	C16—C21—C20	119.11 (18)
N2—C9—S1	123.43 (13)	C16—C21—H21A	120.4
N1—C9—S1	121.15 (12)	C20—C21—H21A	120.4
C9—N1—C1—O1	0.1 (2)	C16—N2—C10—C15	−57.2 (2)
C9—N1—C1—C2	−179.01 (15)	C9—N2—C10—C11	−57.8 (2)
O1—C1—C2—C8	146.21 (18)	C16—N2—C10—C11	118.63 (17)
N1—C1—C2—C8	−34.7 (2)	C15—C10—C11—C12	−1.6 (3)
O1—C1—C2—C3	−32.3 (2)	N2—C10—C11—C12	−177.31 (15)
N1—C1—C2—C3	146.80 (15)	C10—C11—C12—C13	0.9 (3)
C8—C2—C3—C4	1.6 (3)	C11—C12—C13—C14	0.7 (3)
C1—C2—C3—C4	−179.81 (15)	C12—C13—C14—C15	−1.7 (3)
C2—C3—C4—C6	−0.8 (3)	C11—C10—C15—C14	0.6 (3)
C2—C3—C4—C5	179.50 (16)	N2—C10—C15—C14	176.38 (16)
C3—C4—C6—C7	−1.0 (3)	C13—C14—C15—C10	1.1 (3)
C5—C4—C6—C7	178.66 (17)	C9—N2—C16—C17	112.65 (19)
C4—C6—C7—C8	2.1 (3)	C10—N2—C16—C17	−63.9 (2)
C6—C7—C8—C2	−1.2 (3)	C9—N2—C16—C21	−71.6 (2)
C3—C2—C8—C7	−0.6 (3)	C10—N2—C16—C21	111.85 (18)
C1—C2—C8—C7	−179.09 (16)	C21—C16—C17—C18	0.7 (3)
C16—N2—C9—N1	166.64 (14)	N2—C16—C17—C18	176.37 (16)
C10—N2—C9—N1	−17.1 (2)	C16—C17—C18—C19	−0.3 (3)
C16—N2—C9—S1	−14.9 (2)	C17—C18—C19—C20	−0.5 (3)
C10—N2—C9—S1	161.33 (13)	C18—C19—C20—C21	1.0 (3)
C1—N1—C9—N2	−56.1 (2)	C17—C16—C21—C20	−0.2 (3)
C1—N1—C9—S1	125.41 (15)	N2—C16—C21—C20	−175.88 (16)
C9—N2—C10—C15	126.34 (18)	C19—C20—C21—C16	−0.6 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···S1i	0.90 (1)	2.53 (1)	3.4123 (15)	169 (1)
C5—H5B···O1ii	0.98	2.59	3.461 (2)	148

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S1i	0.899 (14)	2.525 (14)	3.4123 (15)	169.3 (13)
C5—H5B⋯O1ii	0.98	2.59	3.461 (2)	148

Symmetry codes: (i) ; (ii) .