1-(4-Methyl­benzo­yl)-3-{2-[3-(4-methyl­benzo­yl)thio­ureido]phen­yl}thio­urea

Uwaisulqarni M Osman; Bohari M Yamin

doi:10.1107/S1600536811035586

. 2011 Sep 14;67(Pt 10):o2583. doi: 10.1107/S1600536811035586

1-(4-Methylbenzoyl)-3-{2-[3-(4-methylbenzoyl)thioureido]phenyl}thiourea

Uwaisulqarni M Osman ^a, Bohari M Yamin ^a,^*

PMCID: PMC3201486 PMID: 22058744

Abstract

In the title compound, C₂₄H₂₂N₄O₂S₂, the dihedral angles formed by the thioureido groups with the attached benzene ring are 43.81 (13) and 75.25 (13)°. The dihedral angle between the thioureido groups is 85.48 (10)°. The molecule is stabilized by intramolecular N—H⋯S, N—H⋯O and C—H⋯S hydrogen bonds. In the crystal, molecules are linked by intermolecular N—H⋯S hydrogen bonds together with C—H⋯π interactions.

Related literature

For the structure of related bis-carbomothioyl thioureas, see: Yamin & Osman (2011 ▶); Thiam et al. (2008 ▶).

Experimental

Crystal data

C₂₄H₂₂N₄O₂S₂
M _r = 462.58
Triclinic,
a = 7.1565 (18) Å
b = 11.394 (3) Å
c = 14.332 (4) Å
α = 96.414 (5)°
β = 99.066 (6)°
γ = 94.085 (6)°
V = 1142.1 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 298 K
0.50 × 0.12 × 0.06 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T _min = 0.880, T _max = 0.984
13125 measured reflections
4472 independent reflections
2810 reflections with I > 2σ(I)
R _int = 0.053

Refinement

R[F ² > 2σ(F ²)] = 0.064
wR(F ²) = 0.143
S = 1.02
4472 reflections
294 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.19 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); 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, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811035586/rz2633sup1.cif

e-67-o2583-sup1.cif^{(22.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811035586/rz2633Isup2.hkl

e-67-o2583-Isup2.hkl^{(219.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811035586/rz2633Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C9–C14 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯S2	0.86	2.83	3.476 (3)	134
N1—H1⋯O1	0.86	1.95	2.651 (3)	138
N3—H3⋯O2	0.86	1.97	2.640 (3)	134
C2—H2A⋯S1	0.93	2.79	3.223 (3)	110
N4—H4⋯S2ⁱ	0.86	2.71	3.533 (3)	161
C15—H15B⋯Cg1ⁱⁱ	0.96	2.76	3.509 (4)	136

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank Universiti Kebangsaan Malaysia and the Ministry of Higher Education, Malaysia, for financial support (grant No. UKM-GUP-NBT-08-27-110) and research facilities. Study leave granted to UMO from Universiti Malaysia Terengganu is very much appreciated.

supplementary crystallographic information

Comment

The title compound, 1,2-bis(N'-4-methylbenzoylthioureido)benzene (systematic name: 1-(4-methylbenzoyl)-3-{2-[3-(4-methylbenzoyl)thioureido]phenyl}thiourea), is similar to 1,2-bis(N'-benzoylthioureido)benzene (Thiam et al., 2008) except for the presence of methyl groups at para position of the benzoyl group (Fig. 1). Both thioureido groups S1/N1/N2/C7/C1 and S2/N3/N4/C16/C6 are planar with maximum deviation from the least square planes of 0.033 (2)Å for the N1 atom. The thioureido groups form dihedral angles of 43.81 (13) and 75.25 (13) Å, respectively, with the central benzene ring. The dihedral between the two thioureido groups is 85.58 (10)°. There are four intramolecular hydrogen bonds forming three six-membered ring [O1···H1—N1—C7—N2—C8], [O2···H3A—N3—C16—N4—C17] and [H2A···S1—C7—N1—C1—C2], and one seven-membered ring [H1···S2—C16—N3—C6—C1—N1] as compared to two intramolecular hydrogen bonds observed in 1,2-bis(N'-benzoylthioureido) benzene. The introduction of chloro atom to the bridging benzene ring in 1,2-bis(N'-benzoylthioureido)-4-chlorobenzene (Yamin & Osman, 2011) allowed four intramolecular hydrogen bonds. In the crystal structure, the molecules are linked by N1—H1A···S1 intermolecular hydrogen bonds (symmetry codes as in Table 1) to form centrosymmetric dimers (Fig. 2). In addition, a C—H···π interaction with distance of 2.760Å and an angle of 136° is also present.

Experimental

To a stirred acetone solution (75 ml) of para-benzoyl chloride (0.04 mol) and ammonium thiocyanate (0.04 mol) 1,2-phenylenediamine (0.02 mol) in 40 ml of acetone was added dropwise. The solution mixture was refluxed for 1 h. The resulting solution was poured into a beaker containing some ice cubes. The white precipitate formed was filtered off, washed with distilled water and cold ethanol and then dried under vacuum. Good quality crystals were obtained by recrystallization from ethanol.