Crystal structure of 4-methyl-N-[(4-methyl-pyridin-2-yl)carbamo-thioyl]-benzamide.

In the title compound, C15H15N3OS, the dihedral angle between the planes of the benzene and pyridine rings is 26.86 (9)°. Intra-molecular N-H⋯O and C-H⋯S hydrogen bonds both generate S(6) rings. The C=O and C=S bonds lie to opposite sides of the mol-ecule. In the crystal, inversion dimers linked by pairs of N-H⋯S hydrogen bonds generate R 2 (2)(8) loops.

Chemical context

The role of benzoyl thio­urea derivatives in coordination chemistry has been extensively studied and quite satisfactorily elucidated. As benzoyl thio­ureas have suitable C=O and C=S functional groups, they can be considered as useful chelating agents due to their ability to encapsulate metal ions into their coordinating moiety. Thio­urea and its derivatives have found extensive applications in the fields of medicine, agriculture and analytical chemistry. Thio­ureas are also known to exhibit a wide range of biological activities including anti­cancer (Saeed et al., 2010a ▸), anti­fungal (Saeed et al., 2010b ▸) and as agrochemicals (Xu et al., 2003 ▸). As part of our studies in this area, we now describe the synthesis and structure of the title compound, (I).

Structural commentary

The title compound (Fig. 1 ▸) is a benzoyl thio­urea derivative and analogous to a compound recently reported by us (Adam et al., 2014 ▸), except that the other substituent is changed to methyl­pyridine and the thio­urea moiety is still in a para position. The dihedral angle between the planes of the benzene and pyridine rings is 26.86 (9)°. The C=O bond length of 1.225 (2) Å is comparable to that observed in N-benzoyl-N′-phenyl­thio­urea (Hassan et al., 2008a ▸). The C—N bond lengths are in the range 1.328 (2)–1.417 (2) Å, shorter than the normal single C—N bond length (1.469 Å), indicating partial double-bond character owing to the resonance effect at the carbonyl­thio­urea moiety.

Figure 1

The mol­ecular structure of the title compound, with 50% probability displacement ellipsoids. Hydrogen bonds are shown as dashed lines.

As in most benzoyl thio­urea derivatives, an intra­molecular N—H⋯O hydrogen bond leads to the formation of an S(6) ring, namely, C7/N1/C8/N2/H2/O1. An intra­molecular C—H⋯S inter­action (C9/N2/C8/S1/H10/C10) also generates an S(6) ring (Fig. 1 ▸, Table 1 ▸).

Table 1

Hydrogen-bond geometry (, )

DHA	DH	HA	D A	DHA
N2H1N2O1	0.82(2)	1.94(2)	2.644(2)	144(2)
N1H1N1S1i	0.81(2)	2.74(2)	3.511(2)	158(2)
C10H10AS1	0.93	2.57	3.221(2)	127

Symmetry code: (i) .

Supra­molecular features

In the crystal of (I), inversion dimers linked by pairs of N—H⋯S hydrogen bonds (Table 1 ▸, Fig. 2 ▸) generate (8) loops. As free rotation about the N1—C7 and N2—C8 single bonds is hindered, the C=O and C=S bonds are unlikely to align at the same side of the mol­ecule in order to form a chelate with a metal ion.

Figure 2

The crystal packing of the title compound viewed down the c axis. Hydrogen bonds are shown as dashed lines.

Synthesis and crystallization

The title compound was prepared according to a slight modification of the method described by Hassan et al. (2008b ▸). p-Benzoyl chloride (13 mmol) was added dropwise to a stirred acetone solution (30 ml) of ammonium thio­cyanate (13 mmol). The mixture was stirred for 10 min. A solution of 2-amino-4-picoline in acetone was added and the reaction mixture was refluxed for 3 h, after which the solution was poured into a beaker containing some ice cubes. The resulting precipitate was collected by filtration, washed several times with a cold ethanol/water mixture and purified by recrystallization from an ethanol solution.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2 ▸. The H-atoms on the N atoms were located in a difference-Fourier map and were freely refined. All other H atoms were positioned geometrically and refined using a riding model with C—H = 0.93–0.96 Å and U iso(H) = 1.2U eq(aromatic C) or 1.5U eq(methyl C).

Table 2

Experimental details

Crystal data
Chemical formula	C15H15N3OS
M r	285.36
Crystal system, space group	Monoclinic, P21/c
Temperature (K)	294
a, b, c ()	11.5297(12), 6.1860(6), 20.657(2)
()	101.431(2)
V (3)	1444.1(3)
Z	4
Radiation type	Mo K
(mm1)	0.22
Crystal size (mm)	0.38 0.34 0.09
Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2005 ▸)
T min, T max	0.920, 0.981
No. of measured, independent and observed [I > 2(I)] reflections	15813, 4233, 2790
R int	0.028
(sin /)max (1)	0.706
Refinement
R[F 2 > 2(F 2)], wR(F 2), S	0.048, 0.164, 1.05
No. of reflections	4233
No. of parameters	191
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
max, min (e 3)	0.27, 0.19

Computer programs: APEX2 and SAINT (Bruker, 2005 ▸), SHELXTL (Sheldrick, 2008 ▸) and PLATON (Spek, 2009 ▸).

Crystal structure: contains datablock(s) I. DOI: 10.1107/S2056989015003412/hb7367sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015003412/hb7367Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015003412/hb7367Isup3.cml

CCDC reference: 1050132

Additional supporting information: crystallographic information; 3D view; checkCIF report

C15H15N3OS	F(000) = 600
Mr = 285.36	Dx = 1.313 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 3960 reflections
a = 11.5297 (12) Å	θ = 2.4–25.9°
b = 6.1860 (6) Å	µ = 0.22 mm−1
c = 20.657 (2) Å	T = 294 K
β = 101.431 (2)°	Plate, colourless
V = 1444.1 (3) Å3	0.38 × 0.34 × 0.09 mm
Z = 4

Bruker APEXII CCD diffractometer	4233 independent reflections
Radiation source: fine-focus sealed tube	2790 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.028
φ and ω scans	θmax = 30.1°, θmin = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −16→16
Tmin = 0.920, Tmax = 0.981	k = −8→8
15813 measured reflections	l = −29→29

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0866P)2 + 0.1249P] where P = (Fo2 + 2Fc2)/3
4233 reflections	(Δ/σ)max < 0.001
191 parameters	Δρmax = 0.27 e Å−3
0 restraints	Δρmin = −0.19 e Å−3

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	0.47752 (4)	0.82687 (9)	0.41107 (2)	0.0655 (2)
O1	0.10758 (10)	1.0358 (2)	0.43058 (7)	0.0664 (4)
N1	0.30931 (13)	1.0520 (2)	0.44717 (7)	0.0489 (3)
N2	0.24183 (13)	0.7757 (3)	0.37524 (7)	0.0499 (3)
N3	0.11827 (13)	0.5315 (3)	0.31789 (8)	0.0656 (4)
C1	0.11290 (16)	1.3270 (3)	0.53813 (9)	0.0549 (4)
H1A	0.0514	1.2271	0.5317	0.066*
C2	0.11387 (17)	1.4947 (3)	0.58230 (9)	0.0618 (5)
H2A	0.0534	1.5049	0.6060	0.074*
C3	0.20271 (18)	1.6472 (3)	0.59200 (9)	0.0585 (5)
C4	0.29222 (18)	1.6283 (3)	0.55643 (9)	0.0595 (5)
H4A	0.3525	1.7306	0.5622	0.071*
C5	0.29362 (16)	1.4598 (3)	0.51247 (8)	0.0525 (4)
H5A	0.3547	1.4492	0.4892	0.063*
C6	0.20408 (14)	1.3073 (3)	0.50317 (8)	0.0463 (4)
C7	0.20039 (14)	1.1224 (3)	0.45721 (8)	0.0481 (4)
C8	0.33584 (14)	0.8813 (3)	0.40921 (7)	0.0456 (4)
C9	0.23136 (14)	0.5873 (3)	0.33544 (7)	0.0485 (4)
C10	0.32251 (15)	0.4763 (3)	0.31581 (8)	0.0546 (4)
H10A	0.4004	0.5224	0.3292	0.065*
C11	0.29672 (18)	0.2966 (3)	0.27621 (8)	0.0549 (4)
C12	0.18012 (19)	0.2358 (4)	0.25798 (10)	0.0673 (5)
H12A	0.1591	0.1146	0.2316	0.081*
C13	0.0953 (2)	0.3570 (4)	0.27931 (12)	0.0766 (6)
H13A	0.0167	0.3150	0.2661	0.092*
C14	0.2033 (3)	1.8322 (4)	0.64013 (11)	0.0836 (7)
H14A	0.2708	1.9228	0.6397	0.125*
H14B	0.2073	1.7754	0.6838	0.125*
H14C	0.1322	1.9156	0.6274	0.125*
C15	0.3924 (2)	0.1738 (4)	0.25264 (13)	0.0834 (7)
H15A	0.4636	0.1785	0.2858	0.125*
H15B	0.4068	0.2380	0.2126	0.125*
H15C	0.3682	0.0262	0.2443	0.125*
H1N2	0.181 (2)	0.810 (4)	0.3871 (12)	0.083 (7)*
H1N1	0.3673 (18)	1.100 (3)	0.4720 (10)	0.055 (5)*

	U11	U22	U33	U12	U13	U23
S1	0.0427 (3)	0.0886 (4)	0.0651 (3)	−0.0032 (2)	0.0107 (2)	−0.0266 (2)
O1	0.0437 (7)	0.0727 (10)	0.0793 (9)	0.0008 (6)	0.0035 (6)	−0.0220 (7)
N1	0.0440 (7)	0.0525 (9)	0.0488 (7)	−0.0028 (6)	0.0057 (6)	−0.0086 (6)
N2	0.0429 (7)	0.0548 (9)	0.0498 (7)	0.0016 (6)	0.0040 (6)	−0.0088 (6)
N3	0.0508 (8)	0.0691 (11)	0.0723 (10)	−0.0025 (8)	0.0012 (7)	−0.0189 (8)
C1	0.0478 (9)	0.0604 (11)	0.0555 (9)	0.0019 (8)	0.0083 (7)	−0.0018 (8)
C2	0.0624 (11)	0.0725 (13)	0.0510 (9)	0.0149 (10)	0.0124 (8)	−0.0027 (8)
C3	0.0731 (12)	0.0516 (11)	0.0464 (9)	0.0149 (9)	0.0011 (8)	0.0002 (7)
C4	0.0701 (12)	0.0457 (10)	0.0602 (10)	−0.0014 (9)	0.0066 (9)	0.0008 (8)
C5	0.0597 (10)	0.0466 (10)	0.0520 (9)	0.0011 (8)	0.0127 (7)	0.0038 (7)
C6	0.0475 (8)	0.0447 (9)	0.0452 (8)	0.0044 (7)	0.0053 (6)	0.0016 (6)
C7	0.0454 (8)	0.0494 (10)	0.0480 (8)	0.0005 (7)	0.0054 (7)	−0.0004 (7)
C8	0.0457 (8)	0.0501 (9)	0.0401 (7)	−0.0016 (7)	0.0064 (6)	−0.0001 (6)
C9	0.0495 (9)	0.0526 (10)	0.0407 (7)	−0.0004 (7)	0.0029 (6)	−0.0006 (7)
C10	0.0548 (10)	0.0566 (11)	0.0534 (9)	−0.0008 (8)	0.0131 (7)	−0.0033 (8)
C11	0.0730 (12)	0.0469 (10)	0.0460 (8)	0.0014 (8)	0.0148 (8)	0.0007 (7)
C12	0.0770 (13)	0.0601 (12)	0.0648 (11)	−0.0072 (10)	0.0138 (10)	−0.0136 (9)
C13	0.0624 (12)	0.0760 (15)	0.0862 (14)	−0.0093 (10)	0.0022 (10)	−0.0282 (12)
C14	0.114 (2)	0.0673 (15)	0.0669 (13)	0.0168 (12)	0.0112 (13)	−0.0144 (10)
C15	0.0940 (17)	0.0733 (16)	0.0907 (16)	0.0025 (12)	0.0374 (14)	−0.0172 (12)

S1—C8	1.6609 (16)	C4—H4A	0.9300
O1—C7	1.225 (2)	C5—C6	1.384 (2)
N1—C7	1.383 (2)	C5—H5A	0.9300
N1—C8	1.385 (2)	C6—C7	1.482 (2)
N1—H1N1	0.81 (2)	C9—C10	1.382 (2)
N2—C8	1.339 (2)	C10—C11	1.377 (3)
N2—C9	1.417 (2)	C10—H10A	0.9300
N2—H1N2	0.82 (2)	C11—C12	1.375 (3)
N3—C9	1.328 (2)	C11—C15	1.498 (3)
N3—C13	1.337 (3)	C12—C13	1.373 (3)
C1—C2	1.380 (3)	C12—H12A	0.9300
C1—C6	1.394 (2)	C13—H13A	0.9300
C1—H1A	0.9300	C14—H14A	0.9600
C2—C3	1.378 (3)	C14—H14B	0.9600
C2—H2A	0.9300	C14—H14C	0.9600
C3—C4	1.385 (3)	C15—H15A	0.9600
C3—C14	1.515 (3)	C15—H15B	0.9600
C4—C5	1.385 (3)	C15—H15C	0.9600
C7—N1—C8	129.34 (15)	N2—C8—S1	127.11 (13)
C7—N1—H1N1	116.6 (14)	N1—C8—S1	117.91 (12)
C8—N1—H1N1	112.9 (14)	N3—C9—C10	123.61 (16)
C8—N2—C9	132.25 (15)	N3—C9—N2	109.77 (15)
C8—N2—H1N2	111.7 (17)	C10—C9—N2	126.61 (15)
C9—N2—H1N2	114.2 (17)	C11—C10—C9	119.22 (17)
C9—N3—C13	116.14 (17)	C11—C10—H10A	120.4
C2—C1—C6	120.01 (18)	C9—C10—H10A	120.4
C2—C1—H1A	120.0	C12—C11—C10	117.90 (18)
C6—C1—H1A	120.0	C12—C11—C15	121.03 (18)
C3—C2—C1	121.29 (17)	C10—C11—C15	121.07 (19)
C3—C2—H2A	119.4	C13—C12—C11	118.87 (19)
C1—C2—H2A	119.4	C13—C12—H12A	120.6
C2—C3—C4	118.38 (17)	C11—C12—H12A	120.6
C2—C3—C14	121.3 (2)	N3—C13—C12	124.3 (2)
C4—C3—C14	120.3 (2)	N3—C13—H13A	117.9
C5—C4—C3	121.21 (18)	C12—C13—H13A	117.9
C5—C4—H4A	119.4	C3—C14—H14A	109.5
C3—C4—H4A	119.4	C3—C14—H14B	109.5
C6—C5—C4	119.94 (17)	H14A—C14—H14B	109.5
C6—C5—H5A	120.0	C3—C14—H14C	109.5
C4—C5—H5A	120.0	H14A—C14—H14C	109.5
C5—C6—C1	119.15 (16)	H14B—C14—H14C	109.5
C5—C6—C7	122.77 (15)	C11—C15—H15A	109.5
C1—C6—C7	118.08 (15)	C11—C15—H15B	109.5
O1—C7—N1	122.22 (16)	H15A—C15—H15B	109.5
O1—C7—C6	122.46 (15)	C11—C15—H15C	109.5
N1—C7—C6	115.31 (15)	H15A—C15—H15C	109.5
N2—C8—N1	114.97 (14)	H15B—C15—H15C	109.5
C6—C1—C2—C3	1.2 (3)	C9—N2—C8—N1	−174.80 (16)
C1—C2—C3—C4	−0.3 (3)	C9—N2—C8—S1	4.2 (3)
C1—C2—C3—C14	179.57 (18)	C7—N1—C8—N2	3.2 (3)
C2—C3—C4—C5	−0.5 (3)	C7—N1—C8—S1	−175.97 (14)
C14—C3—C4—C5	179.64 (17)	C13—N3—C9—C10	0.3 (3)
C3—C4—C5—C6	0.4 (3)	C13—N3—C9—N2	179.18 (18)
C4—C5—C6—C1	0.5 (3)	C8—N2—C9—N3	173.13 (18)
C4—C5—C6—C7	−179.68 (16)	C8—N2—C9—C10	−8.0 (3)
C2—C1—C6—C5	−1.2 (3)	N3—C9—C10—C11	−0.4 (3)
C2—C1—C6—C7	178.91 (16)	N2—C9—C10—C11	−179.18 (16)
C8—N1—C7—O1	−1.1 (3)	C9—C10—C11—C12	0.0 (3)
C8—N1—C7—C6	177.94 (15)	C9—C10—C11—C15	178.80 (19)
C5—C6—C7—O1	−152.85 (18)	C10—C11—C12—C13	0.7 (3)
C1—C6—C7—O1	27.0 (2)	C15—C11—C12—C13	−178.2 (2)
C5—C6—C7—N1	28.1 (2)	C9—N3—C13—C12	0.4 (4)
C1—C6—C7—N1	−152.03 (16)	C11—C12—C13—N3	−0.9 (4)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1	0.82 (2)	1.94 (2)	2.644 (2)	144 (2)
N1—H1N1···S1i	0.81 (2)	2.74 (2)	3.5106 (15)	157.8 (18)
C10—H10A···S1	0.93	2.57	3.2211 (19)	127