1-(4-Methyl-benzo-yl)-3-{2-[3-(4-methyl-benzo-yl)thio-ureido]phen-yl}thio-urea.

In the title compound, C(24)H(22)N(4)O(2)S(2), the dihedral angles formed by the thio-ureido groups with the attached benzene ring are 43.81 (13) and 75.25 (13)°. The dihedral angle between the thio-ureido groups is 85.48 (10)°. The mol-ecule is stabilized by intra-molecular 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 inter-actions.

Related literature

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

Experimental

Crystal data

C24H22N4O2S2

M = 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

Δρmax = 0.32 e Å−3

Δρmin = −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 ▶).

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

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

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

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

C24H22N4O2S2	Z = 2
Mr = 462.58	F(000) = 484
Triclinic, P1	Dx = 1.345 Mg m−3
Hall symbol: -P 1	Melting point = 475.4–476.6 K
a = 7.1565 (18) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.394 (3) Å	Cell parameters from 1550 reflections
c = 14.332 (4) Å	θ = 1.8–26.0°
α = 96.414 (5)°	µ = 0.26 mm−1
β = 99.066 (6)°	T = 298 K
γ = 94.085 (6)°	Slab, colourless
V = 1142.1 (5) Å3	0.50 × 0.12 × 0.06 mm

Bruker SMART APEX CCD area-detector diffractometer	4472 independent reflections
Radiation source: fine-focus sealed tube	2810 reflections with I > 2σ(I)
graphite	Rint = 0.053
Detector resolution: 83.66 pixels mm-1	θmax = 26.0°, θmin = 1.8°
ω scans	h = −8→8
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −14→14
Tmin = 0.880, Tmax = 0.984	l = −17→17
13125 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)] = 0.064	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.143	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ2(Fo2) + (0.0601P)2 + 0.1876P] where P = (Fo2 + 2Fc2)/3
4472 reflections	(Δ/σ)max < 0.001
294 parameters	Δρmax = 0.32 e Å−3
1 restraint	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	1.23642 (15)	1.02145 (9)	0.41453 (8)	0.0810 (4)
S2	1.21023 (12)	0.60423 (7)	0.10031 (6)	0.0488 (3)
O1	0.9229 (3)	0.6795 (2)	0.25909 (17)	0.0661 (7)
O2	0.9013 (3)	0.87729 (19)	−0.05615 (16)	0.0638 (7)
N1	1.2155 (3)	0.8412 (2)	0.27623 (17)	0.0438 (6)
H1	1.1524	0.7764	0.2483	0.053*
N2	1.0044 (4)	0.8279 (2)	0.38102 (18)	0.0457 (6)
H2	0.968 (4)	0.868 (2)	0.4283 (14)	0.055*
N3	1.1759 (3)	0.8295 (2)	0.07633 (17)	0.0467 (6)
H3	1.1088	0.8820	0.0526	0.056*
N4	0.9377 (3)	0.6947 (2)	−0.00916 (17)	0.0447 (6)
H4	0.8882	0.6224	−0.0191	0.054*
C1	1.3716 (4)	0.8820 (2)	0.2346 (2)	0.0403 (7)
C2	1.5444 (4)	0.9285 (3)	0.2888 (2)	0.0489 (8)
H2A	1.5595	0.9358	0.3549	0.059*
C3	1.6929 (5)	0.9638 (3)	0.2455 (3)	0.0566 (9)
H3A	1.8068	0.9970	0.2826	0.068*
C4	1.6755 (5)	0.9508 (3)	0.1478 (3)	0.0598 (9)
H4A	1.7777	0.9736	0.1190	0.072*
C5	1.5054 (5)	0.9036 (3)	0.0931 (2)	0.0534 (8)
H5	1.4926	0.8943	0.0270	0.064*
C6	1.3535 (4)	0.8699 (2)	0.1363 (2)	0.0418 (7)
C7	1.1550 (4)	0.8911 (3)	0.3530 (2)	0.0456 (8)
C8	0.8930 (4)	0.7289 (3)	0.3340 (2)	0.0454 (8)
C9	0.7318 (4)	0.6900 (2)	0.3800 (2)	0.0416 (7)
C10	0.5718 (4)	0.6305 (3)	0.3223 (2)	0.0509 (8)
H10	0.5712	0.6124	0.2573	0.061*
C11	0.4137 (5)	0.5981 (3)	0.3605 (2)	0.0557 (9)
H11	0.3079	0.5575	0.3209	0.067*
C12	0.4092 (4)	0.6245 (3)	0.4563 (2)	0.0475 (8)
C13	0.5708 (5)	0.6804 (3)	0.5143 (2)	0.0541 (9)
H13	0.5722	0.6965	0.5795	0.065*
C14	0.7305 (4)	0.7125 (3)	0.4766 (2)	0.0492 (8)
H14	0.8382	0.7498	0.5167	0.059*
C15	0.2339 (5)	0.5942 (3)	0.4979 (3)	0.0646 (10)
H15A	0.1803	0.6658	0.5178	0.097*
H15B	0.2671	0.5523	0.5517	0.097*
H15C	0.1425	0.5452	0.4506	0.097*
C16	1.1071 (4)	0.7164 (3)	0.05479 (19)	0.0409 (7)
C17	0.8385 (5)	0.7739 (3)	−0.0587 (2)	0.0466 (8)
C18	0.6482 (4)	0.7287 (3)	−0.1130 (2)	0.0442 (7)
C19	0.5775 (5)	0.7814 (3)	−0.1920 (2)	0.0528 (9)
H19	0.6531	0.8397	−0.2126	0.063*
C20	0.3966 (5)	0.7482 (3)	−0.2401 (2)	0.0578 (9)
H20	0.3527	0.7835	−0.2939	0.069*
C21	0.2779 (5)	0.6637 (3)	−0.2106 (2)	0.0513 (8)
C22	0.3506 (5)	0.6101 (3)	−0.1326 (2)	0.0547 (9)
H22	0.2750	0.5515	−0.1123	0.066*
C23	0.5325 (5)	0.6415 (3)	−0.0843 (2)	0.0503 (8)
H23	0.5782	0.6039	−0.0320	0.060*
C24	0.0761 (5)	0.6314 (4)	−0.2600 (3)	0.0761 (11)
H24A	0.0074	0.5885	−0.2203	0.114*
H24B	0.0755	0.5828	−0.3193	0.114*
H24C	0.0167	0.7024	−0.2721	0.114*

	U11	U22	U33	U12	U13	U23
S1	0.0742 (7)	0.0602 (6)	0.1025 (8)	−0.0252 (5)	0.0373 (6)	−0.0290 (6)
S2	0.0552 (5)	0.0405 (5)	0.0473 (5)	0.0033 (4)	−0.0002 (4)	0.0039 (4)
O1	0.0648 (16)	0.0619 (15)	0.0678 (16)	−0.0208 (12)	0.0280 (13)	−0.0159 (13)
O2	0.0678 (16)	0.0420 (13)	0.0732 (16)	−0.0071 (12)	−0.0106 (13)	0.0107 (11)
N1	0.0438 (15)	0.0411 (14)	0.0438 (15)	−0.0100 (12)	0.0060 (12)	0.0034 (12)
N2	0.0462 (16)	0.0428 (15)	0.0469 (16)	−0.0064 (12)	0.0118 (13)	0.0008 (12)
N3	0.0494 (16)	0.0390 (15)	0.0488 (16)	−0.0002 (12)	0.0002 (13)	0.0070 (12)
N4	0.0502 (16)	0.0328 (13)	0.0467 (15)	−0.0025 (12)	−0.0009 (13)	0.0022 (11)
C1	0.0391 (18)	0.0312 (15)	0.0496 (19)	−0.0006 (13)	0.0049 (15)	0.0065 (13)
C2	0.0435 (19)	0.0444 (18)	0.055 (2)	−0.0012 (15)	−0.0011 (16)	0.0055 (15)
C3	0.0372 (19)	0.0426 (19)	0.088 (3)	0.0026 (15)	0.0047 (19)	0.0097 (18)
C4	0.046 (2)	0.054 (2)	0.085 (3)	0.0001 (17)	0.026 (2)	0.0114 (19)
C5	0.058 (2)	0.0463 (19)	0.059 (2)	0.0030 (17)	0.0173 (18)	0.0077 (16)
C6	0.0395 (18)	0.0321 (16)	0.052 (2)	−0.0014 (13)	0.0055 (15)	0.0043 (14)
C7	0.0423 (18)	0.0441 (18)	0.049 (2)	−0.0020 (15)	0.0043 (15)	0.0058 (15)
C8	0.0479 (19)	0.0369 (17)	0.050 (2)	0.0011 (15)	0.0086 (16)	0.0014 (15)
C9	0.0405 (18)	0.0346 (16)	0.0495 (19)	0.0004 (14)	0.0083 (15)	0.0059 (14)
C10	0.053 (2)	0.0518 (19)	0.0471 (19)	−0.0055 (16)	0.0095 (17)	0.0091 (15)
C11	0.046 (2)	0.059 (2)	0.058 (2)	−0.0091 (17)	0.0009 (17)	0.0098 (17)
C12	0.0408 (19)	0.0436 (18)	0.062 (2)	0.0070 (15)	0.0136 (16)	0.0132 (16)
C13	0.057 (2)	0.056 (2)	0.051 (2)	−0.0006 (17)	0.0200 (18)	0.0030 (16)
C14	0.0460 (19)	0.0492 (19)	0.049 (2)	−0.0034 (15)	0.0070 (16)	−0.0034 (15)
C15	0.050 (2)	0.072 (2)	0.078 (3)	0.0047 (18)	0.0217 (19)	0.022 (2)
C16	0.0430 (18)	0.0446 (18)	0.0347 (17)	−0.0015 (14)	0.0105 (14)	0.0012 (14)
C17	0.054 (2)	0.0427 (19)	0.0406 (18)	0.0033 (16)	0.0030 (15)	0.0030 (15)
C18	0.0486 (19)	0.0390 (17)	0.0423 (18)	0.0040 (15)	0.0038 (15)	−0.0015 (14)
C19	0.065 (2)	0.0398 (18)	0.050 (2)	−0.0036 (16)	0.0046 (18)	0.0063 (15)
C20	0.068 (2)	0.049 (2)	0.051 (2)	0.0066 (18)	−0.0066 (18)	0.0041 (16)
C21	0.050 (2)	0.054 (2)	0.046 (2)	0.0082 (17)	0.0033 (16)	−0.0092 (16)
C22	0.052 (2)	0.060 (2)	0.052 (2)	−0.0020 (17)	0.0153 (17)	0.0035 (17)
C23	0.050 (2)	0.056 (2)	0.0448 (19)	0.0074 (17)	0.0068 (16)	0.0087 (15)
C24	0.059 (2)	0.101 (3)	0.063 (2)	0.002 (2)	0.0022 (19)	−0.001 (2)

S1—C7	1.656 (3)	C9—C10	1.386 (4)
S2—C16	1.665 (3)	C10—C11	1.378 (4)
O1—C8	1.213 (3)	C10—H10	0.9300
O2—C17	1.225 (3)	C11—C12	1.377 (4)
N1—C7	1.329 (4)	C11—H11	0.9300
N1—C1	1.421 (4)	C12—C13	1.382 (4)
N1—H1	0.8600	C12—C15	1.506 (4)
N2—C8	1.377 (4)	C13—C14	1.383 (4)
N2—C7	1.390 (4)	C13—H13	0.9300
N2—H2	0.859 (10)	C14—H14	0.9300
N3—C16	1.331 (3)	C15—H15A	0.9600
N3—C6	1.432 (4)	C15—H15B	0.9600
N3—H3	0.8600	C15—H15C	0.9600
N4—C17	1.378 (4)	C17—C18	1.484 (4)
N4—C16	1.389 (4)	C18—C19	1.382 (4)
N4—H4	0.8600	C18—C23	1.387 (4)
C1—C6	1.385 (4)	C19—C20	1.373 (4)
C1—C2	1.387 (4)	C19—H19	0.9300
C2—C3	1.371 (4)	C20—C21	1.384 (5)
C2—H2A	0.9300	C20—H20	0.9300
C3—C4	1.376 (5)	C21—C22	1.380 (4)
C3—H3A	0.9300	C21—C24	1.506 (4)
C4—C5	1.378 (4)	C22—C23	1.378 (4)
C4—H4A	0.9300	C22—H22	0.9300
C5—C6	1.385 (4)	C23—H23	0.9300
C5—H5	0.9300	C24—H24A	0.9600
C8—C9	1.481 (4)	C24—H24B	0.9600
C9—C14	1.381 (4)	C24—H24C	0.9600
C7—N1—C1	127.9 (2)	C11—C12—C13	118.3 (3)
C7—N1—H1	116.1	C11—C12—C15	121.6 (3)
C1—N1—H1	116.1	C13—C12—C15	120.1 (3)
C8—N2—C7	129.1 (3)	C12—C13—C14	120.7 (3)
C8—N2—H2	120 (2)	C12—C13—H13	119.6
C7—N2—H2	110 (2)	C14—C13—H13	119.6
C16—N3—C6	124.7 (3)	C9—C14—C13	120.8 (3)
C16—N3—H3	117.7	C9—C14—H14	119.6
C6—N3—H3	117.7	C13—C14—H14	119.6
C17—N4—C16	128.4 (3)	C12—C15—H15A	109.5
C17—N4—H4	115.8	C12—C15—H15B	109.5
C16—N4—H4	115.8	H15A—C15—H15B	109.5
C6—C1—C2	118.8 (3)	C12—C15—H15C	109.5
C6—C1—N1	118.7 (3)	H15A—C15—H15C	109.5
C2—C1—N1	122.4 (3)	H15B—C15—H15C	109.5
C3—C2—C1	120.4 (3)	N3—C16—N4	115.9 (3)
C3—C2—H2A	119.8	N3—C16—S2	124.1 (2)
C1—C2—H2A	119.8	N4—C16—S2	120.0 (2)
C2—C3—C4	120.8 (3)	O2—C17—N4	121.9 (3)
C2—C3—H3A	119.6	O2—C17—C18	121.5 (3)
C4—C3—H3A	119.6	N4—C17—C18	116.6 (3)
C3—C4—C5	119.4 (3)	C19—C18—C23	118.4 (3)
C3—C4—H4A	120.3	C19—C18—C17	118.6 (3)
C5—C4—H4A	120.3	C23—C18—C17	122.8 (3)
C4—C5—C6	120.1 (3)	C20—C19—C18	120.5 (3)
C4—C5—H5	119.9	C20—C19—H19	119.7
C6—C5—H5	119.9	C18—C19—H19	119.7
C5—C6—C1	120.4 (3)	C19—C20—C21	121.6 (3)
C5—C6—N3	117.9 (3)	C19—C20—H20	119.2
C1—C6—N3	121.5 (3)	C21—C20—H20	119.2
N1—C7—N2	115.5 (3)	C22—C21—C20	117.5 (3)
N1—C7—S1	126.3 (2)	C22—C21—C24	120.6 (3)
N2—C7—S1	118.1 (2)	C20—C21—C24	121.9 (3)
O1—C8—N2	121.9 (3)	C23—C22—C21	121.5 (3)
O1—C8—C9	122.9 (3)	C23—C22—H22	119.3
N2—C8—C9	115.2 (3)	C21—C22—H22	119.3
C14—C9—C10	118.4 (3)	C22—C23—C18	120.4 (3)
C14—C9—C8	123.6 (3)	C22—C23—H23	119.8
C10—C9—C8	117.9 (3)	C18—C23—H23	119.8
C11—C10—C9	120.4 (3)	C21—C24—H24A	109.5
C11—C10—H10	119.8	C21—C24—H24B	109.5
C9—C10—H10	119.8	H24A—C24—H24B	109.5
C12—C11—C10	121.3 (3)	C21—C24—H24C	109.5
C12—C11—H11	119.3	H24A—C24—H24C	109.5
C10—C11—H11	119.3	H24B—C24—H24C	109.5
C7—N1—C1—C6	−141.4 (3)	C10—C11—C12—C13	−2.6 (5)
C7—N1—C1—C2	41.6 (4)	C10—C11—C12—C15	177.2 (3)
C6—C1—C2—C3	1.3 (4)	C11—C12—C13—C14	2.2 (5)
N1—C1—C2—C3	178.2 (3)	C15—C12—C13—C14	−177.6 (3)
C1—C2—C3—C4	−1.9 (5)	C10—C9—C14—C13	−2.3 (4)
C2—C3—C4—C5	1.1 (5)	C8—C9—C14—C13	175.9 (3)
C3—C4—C5—C6	0.1 (5)	C12—C13—C14—C9	0.3 (5)
C4—C5—C6—C1	−0.7 (5)	C6—N3—C16—N4	−176.2 (3)
C4—C5—C6—N3	175.5 (3)	C6—N3—C16—S2	4.4 (4)
C2—C1—C6—C5	0.0 (4)	C17—N4—C16—N3	5.3 (4)
N1—C1—C6—C5	−177.0 (3)	C17—N4—C16—S2	−175.3 (2)
C2—C1—C6—N3	−176.1 (3)	C16—N4—C17—O2	5.6 (5)
N1—C1—C6—N3	6.9 (4)	C16—N4—C17—C18	−172.4 (3)
C16—N3—C6—C5	103.2 (3)	O2—C17—C18—C19	28.5 (5)
C16—N3—C6—C1	−80.6 (4)	N4—C17—C18—C19	−153.4 (3)
C1—N1—C7—N2	−176.4 (3)	O2—C17—C18—C23	−146.9 (3)
C1—N1—C7—S1	5.9 (5)	N4—C17—C18—C23	31.1 (4)
C8—N2—C7—N1	−9.3 (5)	C23—C18—C19—C20	0.4 (5)
C8—N2—C7—S1	168.5 (3)	C17—C18—C19—C20	−175.2 (3)
C7—N2—C8—O1	3.7 (5)	C18—C19—C20—C21	1.4 (5)
C7—N2—C8—C9	−174.4 (3)	C19—C20—C21—C22	−2.4 (5)
O1—C8—C9—C14	155.4 (3)	C19—C20—C21—C24	176.8 (3)
N2—C8—C9—C14	−26.5 (4)	C20—C21—C22—C23	1.7 (5)
O1—C8—C9—C10	−26.4 (4)	C24—C21—C22—C23	−177.6 (3)
N2—C8—C9—C10	151.7 (3)	C21—C22—C23—C18	0.1 (5)
C14—C9—C10—C11	1.9 (5)	C19—C18—C23—C22	−1.1 (5)
C8—C9—C10—C11	−176.4 (3)	C17—C18—C23—C22	174.3 (3)
C9—C10—C11—C12	0.6 (5)

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···O1i	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

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

Symmetry codes: (i) ; (ii) .