Crystal structure of 4-methyl-N-[(4-methyl­pyridin-2-yl)carbamo­thioyl]­benzamide

Adam, F.; Ameram, N.; Eltayeb, N.E.

doi:10.1107/S2056989015003412

Crystal structure of 4-methyl-N-[(4-methylpyridin-2-yl)carbamothioyl]benzamide

F. Adam, N. Ameram and N. E. Eltayeb

In the title compound, C₁₅H₁₅N₃OS, intramolecular 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 molecule. In the crystal, inversion dimers linked by pairs of N—H

S hydrogen bonds generate $R_{2}^{2}$ (8) loops.

Keywords: crystal structure; thiourea compounds; thiocarbonyl groups; benzamide; hydrogen bonding.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S2056989015003412/hb7367sup1.cif Contains datablock I
	Structure factor file (CIF format) https://doi.org/10.1107/S2056989015003412/hb7367Isup2.hkl Contains datablock I
	Chemical Markup Language (CML) file https://doi.org/10.1107/S2056989015003412/hb7367Isup3.cml Supplementary material

CCDC reference: 1050132

checkCIF report

checkCIF/PLATON results

No syntax errors found



Datablock: I


Alert level C
PLAT911_ALERT_3_C Missing # FCF Refl Between THmin & STh/L=  0.600         10 Report

Alert level G
PLAT066_ALERT_1_G Predicted and Reported Tmin&Tmax Range Identical          ? Check
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          2 Note
PLAT899_ALERT_4_G SHELXL97   is Deprecated and Succeeded by SHELXL       2014 Note
PLAT912_ALERT_4_G Missing # of FCF Reflections Above STh/L=  0.600         16 Note
PLAT955_ALERT_1_G Reported (CIF) and Actual (FCF) Lmax Differ by .          1 Units

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   1 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   5 ALERT level G = General information/check it is not something unexpected

   2 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   3 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Chemical context top

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 top

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 longer than the average C=O bond length (1.200 Å) and 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.

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).

Supramolecular features top

In the crystal of (I), inversion dimers linked by pairs of N—H···S hydrogen bonds (Table 1, Fig. 2) generate R₂²(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.

Synthesis and crystallization top

Freshly prepared substituted 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 (Hassan et al., 2008b) as colourless plates (yield 61%).

Refinement top

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 fully 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).

Related literature top

For related literature, see: Adam et al. (2014); Hassan et al. (2008a, 2008b); Saeed et al. (2010a, 2010b); Xu et al. (2003).

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXTL (Sheldrick, 2008); program(s) used to refine structure: SHELXTL (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009).

Figures top

	Fig. 1. The molecular structure of the title compound, with 50% probability displacement ellipsoids. Hydrogen bonds are shown as dashed lines.
	Fig. 2. The crystal packing of the title compound viewed down the c axis. Hydrogen bonds are shown as dashed lines.

4-Methyl-N-[(4-methylpyridin-2-yl)carbamothioyl]benzamide top

Crystal data top

C₁₅H₁₅N₃OS	F(000) = 600
M_r = 285.36	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0866P)² + 0.1249P] where P = (F_o² + 2F_c²)/3
4233 reflections	(Δ/σ)_max < 0.001
191 parameters	Δρ_max = 0.27 e Å⁻³
0 restraints	Δρ_min = −0.19 e Å⁻³

Crystal data top

C₁₅H₁₅N₃OS	V = 1444.1 (3) Å³
M_r = 285.36	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 11.5297 (12) Å	µ = 0.22 mm⁻¹
b = 6.1860 (6) Å	T = 294 K
c = 20.657 (2) Å	0.38 × 0.34 × 0.09 mm
β = 101.431 (2)°

Data collection top

Bruker APEXII CCD diffractometer	4233 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	2790 reflections with I > 2σ(I)
T_min = 0.920, T_max = 0.981	R_int = 0.028
15813 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.164	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	Δρ_max = 0.27 e Å⁻³
4233 reflections	Δρ_min = −0.19 e Å⁻³
191 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)*

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) −x+1, −y+2, −z+1.

Hydrogen-bond geometry (Å, º) top

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

Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₅N₃OS
M_r	285.36
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	294
a, b, c (Å)	11.5297 (12), 6.1860 (6), 20.657 (2)
β (°)	101.431 (2)
V (Å³)	1444.1 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.22
Crystal size (mm)	0.38 × 0.34 × 0.09

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.920, 0.981
No. of measured, independent and observed [I > 2σ(I)] reflections	15813, 4233, 2790
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.706

Refinement
R[F² > 2σ(F²)], wR(F²), 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
Δρ_max, Δρ_min (e Å⁻³)	0.27, −0.19

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

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Crystal structure of 4-methyl-N-[(4-methyl­pyridin-2-yl)carbamo­thioyl]­benzamide

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Crystal structure of 4-methyl-N-[(4-methylpyridin-2-yl)carbamothioyl]benzamide