3,3'-Dibenzoyl-1,1'-dibenzyl-1,1'-(ethane-1,2-di-yl)-dithio-urea.

In the title compound, C(32)H(30)N(4)O(2)S(2), the carbonyl and thio-carbonyl groups are found in a rare synclinal conformation, with an S-C⋯C-O pseudo-torsion angle of 62.6 (2)°. The mol-ecule has C(i) = S(2) point-group symmetry with a crystallographic center of inversion located in the middle of the ethyl-ene bridge. One of the symmetry-independent phenyl rings is disordered over two orientations, with a site-occupation ratio of 70:30. The distances between the centroids of the nearest phenyl rings are equal to one of the lattice constants [a = 4.7767 (2) Å], so stacking inter-actions are extremely weak. Mol-ecules are joined by bifurcated hydrogen bonds (N-H⋯O and N-H⋯S), forming a ladder-like arrangement along [100]. van der Waals forces combine these ladders into a three-dimensional structure. The dependency between the S⋯O distance and the improper S=C⋯C=O torsion angle based on 739 structures containing the CC(=O)NC(=S)N moiety is discussed.

Related literature

For structures of bis­(N-benzoyl­thio­ureas) derived from aliphatic diamines, see: Ding et al. (2008 ▶); Dong et al. (2007 ▶); Sow et al. (2009 ▶). For those derived from o-cyclo­hexa­ne­diamine, see: Jumal et al. (2011 ▶). For those derived from aromatic diamines, see: Cao et al. (2007 ▶); Li et al. (2009 ▶); Thiam et al. (2008 ▶); Woei Hung & Kassim (2010 ▶); Yamin & Osman (2011 ▶). For other acyl derivaties obtained from o- and p-phenyl­enediamine (also solvates), see: Dong, Yan et al. (2008 ▶); Dong, Yang et al. (2008 ▶); Du & Du (2008 ▶); Du et al. (2008 ▶). For 1-benzoyl-3-phenyl­urea, see: Okuniewski et al. (2010 ▶). For the synthetic procedure, see: Douglass & Dains (1934 ▶). For a review on N-aroyl­thio­ureas, see: Aly et al. (2007 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C32H30N4O2S2

M = 566.72

Monoclinic,

a = 4.7767 (2) Å

b = 25.1653 (16) Å

c = 11.9998 (8) Å

β = 91.585 (5)°

V = 1441.91 (15) Å3

Z = 2

Mo Kα radiation

μ = 0.22 mm−1

T = 298 K

0.61 × 0.18 × 0.08 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire2 (large Be window) detector

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.780, T max = 1

7277 measured reflections

2685 independent reflections

2021 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.05

wR(F 2) = 0.123

S = 1.04

2685 reflections

231 parameters

163 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.30 e Å−3

Δρmin = −0.15 e Å−3

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: OLEX2 (Dolomanov et al., 2009 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶) and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812002954/im2351sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812002954/im2351Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812002954/im2351Isup3.smi

Supplementary material file. DOI: 10.1107/S1600536812002954/im2351Isup4.cml

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

C32H30N4O2S2	F(000) = 596
Mr = 566.72	Dx = 1.305 Mg m−3
Monoclinic, P21/c	Melting point: 438(1) K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 4.7767 (2) Å	Cell parameters from 2955 reflections
b = 25.1653 (16) Å	θ = 2.3–28.7°
c = 11.9998 (8) Å	µ = 0.22 mm−1
β = 91.585 (5)°	T = 298 K
V = 1441.91 (15) Å3	Needle, colourless
Z = 2	0.61 × 0.18 × 0.08 mm

Oxford Diffraction Xcalibur Sapphire2 (large Be window) diffractometer	2685 independent reflections
Graphite monochromator	2021 reflections with I > 2σ(I)
Detector resolution: 8.1883 pixels mm-1	Rint = 0.031
ω scans	θmax = 25.5°, θmin = 2.4°
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	h = −5→5
Tmin = 0.780, Tmax = 1	k = −26→30
7277 measured reflections	l = −14→14

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)] = 0.05	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.123	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0551P)2 + 0.2801P] where P = (Fo2 + 2Fc2)/3
2685 reflections	(Δ/σ)max = 0.016
231 parameters	Δρmax = 0.30 e Å−3
163 restraints	Δρmin = −0.15 e Å−3

Experimental. CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (Oxford Diffraction, 2010) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm.

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	Occ. (<1)
C1	1.1371 (4)	0.58001 (8)	0.64272 (17)	0.0356 (5)
C3	1.0855 (4)	0.49446 (8)	0.55324 (16)	0.0377 (5)
H3A	1.0468	0.4587	0.5788	0.045*
H3B	1.2835	0.4967	0.5379	0.045*
C10	1.2067 (5)	0.64605 (9)	0.7895 (2)	0.0458 (5)
C11	1.0914 (5)	0.69614 (9)	0.8323 (2)	0.0528 (6)
C12A	0.882 (3)	0.7252 (6)	0.7782 (14)	0.065 (3)	0.71 (3)
H12A	0.7981	0.713	0.7121	0.078*	0.71 (3)
C13A	0.800 (2)	0.7731 (4)	0.8256 (11)	0.077 (3)	0.71 (3)
H13A	0.6566	0.7927	0.7911	0.092*	0.71 (3)
C14A	0.924 (2)	0.7922 (3)	0.9218 (13)	0.078 (3)	0.71 (3)
H14A	0.8664	0.8244	0.9513	0.093*	0.71 (3)
C15A	1.138 (3)	0.7634 (4)	0.9756 (10)	0.078 (3)	0.71 (3)
H15A	1.2214	0.7762	1.0413	0.093*	0.71 (3)
C16A	1.225 (3)	0.7153 (5)	0.9299 (9)	0.065 (2)	0.71 (3)
H16A	1.3702	0.6961	0.9638	0.077*	0.71 (3)
C12B	0.873 (7)	0.7181 (15)	0.769 (3)	0.075 (7)	0.29 (3)
H12B	0.8008	0.6968	0.7118	0.091*	0.29 (3)
C13B	0.747 (7)	0.7674 (12)	0.780 (3)	0.097 (6)	0.29 (3)
H13B	0.6192	0.7814	0.7281	0.116*	0.29 (3)
C14B	0.831 (7)	0.7934 (10)	0.875 (2)	0.083 (6)	0.29 (3)
H14B	0.7374	0.8243	0.8941	0.099*	0.29 (3)
C15B	1.048 (7)	0.7760 (10)	0.943 (3)	0.080 (7)	0.29 (3)
H15B	1.1111	0.7964	1.0035	0.095*	0.29 (3)
C16B	1.168 (7)	0.7275 (11)	0.920 (2)	0.075 (7)	0.29 (3)
H16B	1.3107	0.7155	0.9683	0.09*	0.29 (3)
C20	0.8164 (4)	0.51283 (9)	0.72178 (18)	0.0410 (5)
H20A	0.6511	0.4995	0.6822	0.049*
H20B	0.7592	0.5421	0.7687	0.049*
C21	0.9395 (4)	0.46935 (9)	0.79385 (17)	0.0423 (5)
C22	1.1471 (6)	0.48056 (12)	0.8727 (2)	0.0678 (8)
H22	1.2159	0.515	0.8798	0.081*
C23	1.2529 (6)	0.44077 (16)	0.9412 (3)	0.0881 (10)
H23	1.395	0.4487	0.9931	0.106*
C24	1.1543 (7)	0.39089 (16)	0.9341 (3)	0.0861 (11)
H24	1.2225	0.3648	0.9826	0.103*
C25	0.9545 (8)	0.37876 (13)	0.8557 (3)	0.0920 (11)
H25	0.8906	0.344	0.8487	0.11*
C26	0.8446 (6)	0.41794 (11)	0.7858 (2)	0.0704 (8)
H26	0.7056	0.4093	0.733	0.085*
N1	1.0341 (4)	0.61630 (7)	0.72100 (16)	0.0442 (5)
N2	1.0180 (3)	0.53247 (7)	0.64038 (13)	0.0345 (4)
O1	1.4457 (3)	0.63131 (7)	0.81329 (15)	0.0619 (5)
S1	1.38677 (11)	0.59942 (2)	0.55656 (5)	0.0483 (2)
H1N	0.855 (2)	0.6203 (9)	0.7200 (19)	0.053 (7)*

	U11	U22	U33	U12	U13	U23
C1	0.0269 (10)	0.0383 (12)	0.0413 (12)	0.0072 (9)	−0.0054 (8)	−0.0019 (9)
C3	0.0358 (11)	0.0373 (12)	0.0398 (12)	0.0061 (9)	−0.0028 (9)	−0.0038 (9)
C10	0.0430 (13)	0.0431 (13)	0.0515 (14)	−0.0053 (10)	0.0050 (10)	−0.0062 (11)
C11	0.0496 (14)	0.0408 (14)	0.0692 (17)	−0.0103 (12)	0.0197 (12)	−0.0113 (12)
C12A	0.068 (5)	0.037 (6)	0.092 (5)	0.006 (4)	0.017 (4)	−0.010 (4)
C13A	0.081 (5)	0.040 (4)	0.109 (9)	0.008 (4)	0.015 (5)	−0.023 (4)
C14A	0.074 (7)	0.047 (4)	0.114 (9)	−0.003 (4)	0.021 (6)	−0.036 (5)
C15A	0.088 (5)	0.063 (5)	0.083 (5)	−0.008 (4)	0.018 (4)	−0.040 (4)
C16A	0.068 (4)	0.055 (5)	0.071 (4)	−0.005 (3)	0.010 (3)	−0.029 (3)
C12B	0.086 (12)	0.035 (9)	0.108 (14)	−0.010 (8)	0.051 (11)	−0.003 (9)
C13B	0.113 (13)	0.068 (9)	0.112 (15)	−0.028 (9)	0.029 (11)	−0.039 (11)
C14B	0.094 (13)	0.060 (10)	0.095 (15)	−0.015 (10)	0.016 (11)	−0.033 (10)
C15B	0.089 (18)	0.060 (13)	0.090 (12)	−0.012 (11)	0.015 (12)	−0.014 (11)
C16B	0.071 (12)	0.053 (11)	0.103 (11)	−0.020 (9)	0.024 (8)	−0.012 (9)
C20	0.0320 (10)	0.0471 (13)	0.0437 (12)	−0.0021 (10)	0.0012 (9)	−0.0005 (10)
C21	0.0395 (11)	0.0475 (13)	0.0403 (12)	0.0028 (10)	0.0078 (9)	0.0014 (10)
C22	0.0624 (16)	0.0777 (19)	0.0625 (17)	−0.0047 (14)	−0.0143 (13)	0.0092 (15)
C23	0.070 (2)	0.123 (3)	0.071 (2)	0.007 (2)	−0.0164 (15)	0.031 (2)
C24	0.082 (2)	0.102 (3)	0.076 (2)	0.029 (2)	0.0143 (18)	0.040 (2)
C25	0.122 (3)	0.0551 (19)	0.099 (3)	0.005 (2)	0.015 (2)	0.0219 (18)
C26	0.083 (2)	0.0545 (17)	0.073 (2)	−0.0065 (15)	−0.0062 (16)	0.0080 (14)
N1	0.0290 (9)	0.0431 (11)	0.0605 (12)	0.0037 (8)	0.0001 (8)	−0.0168 (9)
N2	0.0309 (8)	0.0370 (10)	0.0355 (9)	0.0025 (7)	0.0006 (7)	−0.0037 (7)
O1	0.0418 (9)	0.0742 (12)	0.0691 (12)	0.0019 (9)	−0.0104 (8)	−0.0170 (9)
S1	0.0406 (3)	0.0480 (4)	0.0568 (4)	0.0003 (3)	0.0084 (3)	0.0033 (3)

C1—N2	1.325 (3)	C12B—H12B	0.93
C1—N1	1.408 (3)	C13B—C14B	1.361 (15)
C1—S1	1.673 (2)	C13B—H13B	0.93
C3—N2	1.460 (2)	C14B—C15B	1.374 (17)
C3—C3i	1.523 (4)	C14B—H14B	0.93
C3—H3A	0.97	C15B—C16B	1.379 (16)
C3—H3B	0.97	C15B—H15B	0.93
C10—O1	1.227 (3)	C16B—H16B	0.93
C10—N1	1.370 (3)	C20—N2	1.476 (3)
C10—C11	1.474 (3)	C20—C21	1.504 (3)
C11—C16B	1.362 (16)	C20—H20A	0.97
C11—C12A	1.386 (7)	C20—H20B	0.97
C11—C12B	1.387 (18)	C21—C26	1.373 (3)
C11—C16A	1.403 (8)	C21—C22	1.381 (3)
C12A—C13A	1.395 (10)	C22—C23	1.382 (4)
C12A—H12A	0.93	C22—H22	0.93
C13A—C14A	1.371 (9)	C23—C24	1.343 (5)
C13A—H13A	0.93	C23—H23	0.93
C14A—C15A	1.394 (9)	C24—C25	1.356 (4)
C14A—H14A	0.93	C24—H24	0.93
C15A—C16A	1.399 (9)	C25—C26	1.388 (4)
C15A—H15A	0.93	C25—H25	0.93
C16A—H16A	0.93	C26—H26	0.93
C12B—C13B	1.388 (17)	N1—H1N	0.861 (10)
N2—C1—N1	116.24 (18)	C13B—C14B—C15B	123 (2)
N2—C1—S1	124.30 (16)	C13B—C14B—H14B	118.5
N1—C1—S1	119.40 (16)	C15B—C14B—H14B	118.5
N2—C3—C3i	110.9 (2)	C14B—C15B—C16B	118 (2)
N2—C3—H3A	109.5	C14B—C15B—H15B	120.9
C3i—C3—H3A	109.5	C16B—C15B—H15B	120.9
N2—C3—H3B	109.5	C11—C16B—C15B	124 (2)
C3i—C3—H3B	109.5	C11—C16B—H16B	117.9
H3A—C3—H3B	108	C15B—C16B—H16B	117.9
O1—C10—N1	121.0 (2)	N2—C20—C21	111.86 (16)
O1—C10—C11	122.1 (2)	N2—C20—H20A	109.2
N1—C10—C11	116.9 (2)	C21—C20—H20A	109.2
C16B—C11—C12B	112 (2)	N2—C20—H20B	109.2
C12A—C11—C16A	121.1 (8)	C21—C20—H20B	109.2
C16B—C11—C10	132.2 (14)	H20A—C20—H20B	107.9
C12A—C11—C10	124.0 (7)	C26—C21—C22	118.0 (2)
C12B—C11—C10	115.6 (18)	C26—C21—C20	121.4 (2)
C16A—C11—C10	114.7 (6)	C22—C21—C20	120.5 (2)
C11—C12A—C13A	118.2 (10)	C21—C22—C23	120.2 (3)
C11—C12A—H12A	120.9	C21—C22—H22	119.9
C13A—C12A—H12A	120.9	C23—C22—H22	119.9
C14A—C13A—C12A	121.7 (8)	C24—C23—C22	121.2 (3)
C14A—C13A—H13A	119.1	C24—C23—H23	119.4
C12A—C13A—H13A	119.1	C22—C23—H23	119.4
C13A—C14A—C15A	120.3 (7)	C23—C24—C25	119.5 (3)
C13A—C14A—H14A	119.9	C23—C24—H24	120.2
C15A—C14A—H14A	119.9	C25—C24—H24	120.2
C14A—C15A—C16A	119.3 (8)	C24—C25—C26	120.4 (3)
C14A—C15A—H15A	120.3	C24—C25—H25	119.8
C16A—C15A—H15A	120.3	C26—C25—H25	119.8
C15A—C16A—C11	119.4 (8)	C21—C26—C25	120.5 (3)
C15A—C16A—H16A	120.3	C21—C26—H26	119.7
C11—C16A—H16A	120.3	C25—C26—H26	119.7
C11—C12B—C13B	129 (4)	C10—N1—C1	122.61 (17)
C11—C12B—H12B	115.6	C10—N1—H1N	121.7 (16)
C13B—C12B—H12B	115.6	C1—N1—H1N	115.6 (16)
C14B—C13B—C12B	113 (3)	C1—N2—C3	120.25 (17)
C14B—C13B—H13B	123.5	C1—N2—C20	125.18 (17)
C12B—C13B—H13B	123.5	C3—N2—C20	114.56 (16)
O1—C10—C1—S1	−62.55 (17)	S1—C1—N1—C10	−49.1 (3)
O1—C10—N1—C1	−24.3 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1ii	0.86 (1)	2.30 (1)	3.073 (2)	150 (2)
N1—H1N···S1ii	0.86 (1)	2.98 (2)	3.647 (2)	136 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1i	0.86 (1)	2.30 (1)	3.073 (2)	150 (2)
N1—H1N⋯S1i	0.86 (1)	2.98 (2)	3.647 (2)	136 (2)

Symmetry code: (i) .