1,2-Bis(N'-benzoyl-thio-ureido)-4-chloro-benzene.

In the title compound, C(22)H(17)ClN(4)O(2)S(2), both benzoyl groups are trans to the thiono group across their C-N bonds. The two methyl-ene carbamothioyl formamide fragments of the benzoyl-thio-urea side arms make a dihedral angle of 87.00 (10)°. The mol-ecule is stabilized by intra-molecular N-H⋯O, N-H⋯S and C-H⋯·S hydrogen bonds. In the crystal, mol-ecules are linked by N-H⋯O and N-H⋯S inter-molecular hydrogen bonds into zigzag chains along the a axis.

Related literature

For the structure of related bis­carbomothioyl thio­urea compounds, see: Thiam et al. (2008 ▶); Yusof et al. (2008 ▶); Woei Hung & Kassim (2010 ▶). For bond length data, see: Allen (2002 ▶).

Experimental

Crystal data

C22H17ClN4O2S2

M = 468.97

Triclinic,

a = 9.637 (4) Å

b = 10.820 (4) Å

c = 11.370 (4) Å

α = 84.443 (8)°

β = 68.706 (8)°

γ = 86.551 (9)°

V = 1099.1 (7) Å3

Z = 2

Mo Kα radiation

μ = 0.39 mm−1

T = 298 K

0.49 × 0.16 × 0.09 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.928, T max = 0.965

12132 measured reflections

4083 independent reflections

3107 reflections with I > 2σ(I)

R int = 0.042

Refinement

R[F 2 > 2σ(F 2)] = 0.066

wR(F 2) = 0.173

S = 1.08

4083 reflections

280 parameters

H-atom parameters constrained

Δρmax = 0.79 e Å−3

Δρmin = −0.30 e Å−3

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

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811014954/ff2008sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811014954/ff2008Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811014954/ff2008Isup3.cml

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

C22H17ClN4O2S2	Z = 2
Mr = 468.97	F(000) = 484
Triclinic, P1	Dx = 1.417 Mg m−3
Hall symbol: -P 1	Melting point = 458.5–459.5 K
a = 9.637 (4) Å	Mo Kα radiation, λ = 0.71073 Å
b = 10.820 (4) Å	Cell parameters from 2481 reflections
c = 11.370 (4) Å	θ = 1.8–25.5°
α = 84.443 (8)°	µ = 0.39 mm−1
β = 68.706 (8)°	T = 298 K
γ = 86.551 (9)°	Plate, colourless
V = 1099.1 (7) Å3	0.49 × 0.16 × 0.09 mm

Bruker SMART APEX CCD area-detector diffractometer	4083 independent reflections
Radiation source: fine-focus sealed tube	3107 reflections with I > 2σ(I)
graphite	Rint = 0.042
Detector resolution: 83.66 pixels mm-1	θmax = 25.5°, θmin = 1.8°
ω scans	h = −11→11
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −13→13
Tmin = 0.928, Tmax = 0.965	l = −13→13
12132 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)] = 0.066	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.173	H-atom parameters constrained
S = 1.08	w = 1/[σ2(Fo2) + (0.0812P)2 + 0.6319P] where P = (Fo2 + 2Fc2)/3
4083 reflections	(Δ/σ)max < 0.001
280 parameters	Δρmax = 0.79 e Å−3
0 restraints	Δρmin = −0.30 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
Cl1	0.16623 (15)	0.60564 (10)	0.11914 (13)	0.0845 (4)
S1	−0.13518 (13)	0.32671 (13)	0.50891 (12)	0.0882 (5)
S2	0.50891 (11)	0.17508 (8)	0.38266 (10)	0.0524 (3)
O1	0.1820 (3)	0.0277 (3)	0.5716 (3)	0.0866 (11)
O2	0.3898 (3)	−0.1381 (2)	0.2029 (3)	0.0570 (7)
N1	−0.0285 (3)	0.1455 (3)	0.6212 (3)	0.0504 (7)
H1A	−0.1142	0.1557	0.6795	0.060*
N2	0.1368 (3)	0.2180 (3)	0.4276 (3)	0.0486 (7)
H2A	0.1939	0.1630	0.4482	0.058*
N3	0.3678 (3)	0.1001 (2)	0.2425 (2)	0.0400 (6)
H3A	0.3400	0.0403	0.2122	0.048*
N4	0.4966 (3)	−0.0519 (2)	0.3218 (3)	0.0439 (7)
H4A	0.5480	−0.0695	0.3695	0.053*
C1	0.0621 (5)	−0.1393 (4)	0.7813 (4)	0.0604 (10)
H1B	0.1408	−0.1673	0.7127	0.072*
C2	0.0101 (6)	−0.2134 (4)	0.8932 (5)	0.0743 (13)
H2B	0.0531	−0.2919	0.8994	0.089*
C3	−0.1036 (6)	−0.1724 (5)	0.9943 (5)	0.0819 (14)
H3B	−0.1391	−0.2234	1.0691	0.098*
C4	−0.1669 (5)	−0.0552 (5)	0.9864 (4)	0.0759 (13)
H4B	−0.2428	−0.0267	1.0567	0.091*
C5	−0.1177 (4)	0.0195 (4)	0.8750 (4)	0.0577 (10)
H5A	−0.1614	0.0978	0.8695	0.069*
C6	−0.0031 (4)	−0.0226 (3)	0.7712 (3)	0.0496 (9)
C7	0.0582 (4)	0.0508 (3)	0.6474 (3)	0.0497 (9)
C8	0.0013 (4)	0.2288 (3)	0.5134 (3)	0.0466 (8)
C9	0.2023 (4)	0.2824 (3)	0.3077 (3)	0.0415 (8)
C10	0.1586 (4)	0.4028 (3)	0.2774 (4)	0.0526 (9)
H10A	0.0848	0.4461	0.3378	0.063*
C11	0.2265 (4)	0.4562 (3)	0.1565 (4)	0.0530 (9)
C12	0.3378 (5)	0.3993 (3)	0.0662 (4)	0.0594 (10)
H12A	0.3811	0.4381	−0.0147	0.071*
C13	0.3855 (4)	0.2818 (3)	0.0974 (3)	0.0514 (9)
H13A	0.4631	0.2415	0.0371	0.062*
C14	0.3192 (4)	0.2239 (3)	0.2167 (3)	0.0394 (7)
C15	0.4541 (3)	0.0725 (3)	0.3110 (3)	0.0393 (7)
C16	0.4686 (4)	−0.1497 (3)	0.2677 (3)	0.0403 (7)
C17	0.5404 (3)	−0.2712 (3)	0.2888 (3)	0.0392 (7)
C22	0.6633 (4)	−0.2819 (3)	0.3250 (4)	0.0526 (9)
H18A	0.7052	−0.2112	0.3372	0.063*
C21	0.7232 (5)	−0.3984 (4)	0.3429 (4)	0.0673 (11)
H19A	0.8056	−0.4062	0.3675	0.081*
C20	0.6622 (5)	−0.5012 (4)	0.3248 (4)	0.0693 (12)
H20A	0.7035	−0.5791	0.3370	0.083*
C19	0.5408 (5)	−0.4921 (3)	0.2890 (4)	0.0642 (11)
H21A	0.4997	−0.5634	0.2773	0.077*
C18	0.4797 (4)	−0.3769 (3)	0.2702 (3)	0.0488 (8)
H22A	0.3978	−0.3702	0.2450	0.059*

	U11	U22	U33	U12	U13	U23
Cl1	0.1099 (10)	0.0483 (6)	0.0988 (9)	0.0119 (6)	−0.0510 (7)	0.0225 (6)
S1	0.0625 (7)	0.1060 (10)	0.0712 (7)	0.0420 (7)	−0.0088 (6)	0.0230 (7)
S2	0.0667 (6)	0.0323 (4)	0.0726 (6)	0.0039 (4)	−0.0429 (5)	−0.0049 (4)
O1	0.0605 (18)	0.0737 (19)	0.087 (2)	0.0224 (15)	0.0032 (16)	0.0421 (16)
O2	0.0740 (17)	0.0382 (13)	0.0780 (18)	0.0112 (12)	−0.0508 (15)	−0.0109 (12)
N1	0.0401 (15)	0.0577 (18)	0.0452 (16)	0.0099 (13)	−0.0098 (13)	0.0052 (14)
N2	0.0436 (16)	0.0429 (16)	0.0534 (17)	0.0123 (12)	−0.0160 (14)	0.0093 (13)
N3	0.0491 (16)	0.0318 (13)	0.0444 (15)	0.0029 (11)	−0.0241 (13)	−0.0024 (11)
N4	0.0546 (17)	0.0326 (14)	0.0528 (17)	0.0124 (12)	−0.0305 (14)	−0.0064 (12)
C1	0.066 (2)	0.054 (2)	0.065 (2)	−0.0002 (18)	−0.030 (2)	0.0100 (19)
C2	0.091 (3)	0.063 (3)	0.076 (3)	−0.015 (2)	−0.044 (3)	0.026 (2)
C3	0.089 (3)	0.101 (4)	0.060 (3)	−0.031 (3)	−0.038 (3)	0.032 (3)
C4	0.063 (3)	0.112 (4)	0.049 (2)	−0.011 (3)	−0.019 (2)	0.006 (2)
C5	0.051 (2)	0.075 (3)	0.051 (2)	−0.0052 (19)	−0.0231 (18)	0.0013 (19)
C6	0.046 (2)	0.054 (2)	0.054 (2)	−0.0110 (16)	−0.0269 (18)	0.0067 (17)
C7	0.045 (2)	0.046 (2)	0.055 (2)	0.0010 (15)	−0.0170 (17)	0.0080 (16)
C8	0.050 (2)	0.0447 (19)	0.0452 (19)	0.0094 (15)	−0.0195 (16)	−0.0017 (15)
C9	0.0456 (19)	0.0334 (16)	0.0503 (19)	0.0009 (14)	−0.0255 (16)	0.0061 (14)
C10	0.055 (2)	0.0405 (19)	0.064 (2)	0.0103 (16)	−0.0271 (19)	0.0000 (17)
C11	0.066 (2)	0.0375 (18)	0.063 (2)	−0.0026 (17)	−0.037 (2)	0.0152 (17)
C12	0.079 (3)	0.049 (2)	0.051 (2)	−0.0070 (19)	−0.028 (2)	0.0135 (18)
C13	0.064 (2)	0.047 (2)	0.043 (2)	0.0006 (17)	−0.0201 (17)	0.0017 (16)
C14	0.0483 (19)	0.0310 (15)	0.0449 (18)	0.0024 (14)	−0.0254 (15)	0.0014 (14)
C15	0.0402 (17)	0.0361 (17)	0.0398 (17)	0.0047 (13)	−0.0139 (14)	−0.0004 (13)
C16	0.0415 (18)	0.0323 (16)	0.0465 (18)	0.0039 (13)	−0.0158 (15)	−0.0037 (14)
C17	0.0429 (18)	0.0331 (16)	0.0410 (17)	0.0066 (13)	−0.0148 (14)	−0.0059 (13)
C22	0.052 (2)	0.0411 (19)	0.069 (2)	0.0076 (16)	−0.0261 (19)	−0.0121 (17)
C21	0.064 (3)	0.060 (2)	0.087 (3)	0.024 (2)	−0.040 (2)	−0.010 (2)
C20	0.094 (3)	0.036 (2)	0.085 (3)	0.020 (2)	−0.045 (3)	−0.0045 (19)
C19	0.086 (3)	0.0315 (18)	0.081 (3)	0.0004 (18)	−0.039 (2)	−0.0004 (18)
C18	0.053 (2)	0.0397 (18)	0.055 (2)	0.0037 (15)	−0.0214 (17)	−0.0054 (15)

Cl1—C11	1.750 (3)	C4—H4B	0.9300
S1—C8	1.651 (3)	C5—C6	1.385 (5)
S2—C15	1.653 (3)	C5—H5A	0.9300
O1—C7	1.220 (4)	C6—C7	1.482 (5)
O2—C16	1.229 (4)	C9—C14	1.391 (5)
N1—C7	1.363 (4)	C9—C10	1.395 (4)
N1—C8	1.399 (4)	C10—C11	1.375 (5)
N1—H1A	0.8600	C10—H10A	0.9300
N2—C8	1.322 (4)	C11—C12	1.351 (6)
N2—C9	1.409 (4)	C12—C13	1.384 (5)
N2—H2A	0.8600	C12—H12A	0.9300
N3—C15	1.335 (4)	C13—C14	1.376 (5)
N3—C14	1.431 (4)	C13—H13A	0.9300
N3—H3A	0.8600	C16—C17	1.488 (4)
N4—C16	1.361 (4)	C17—C18	1.382 (5)
N4—C15	1.390 (4)	C17—C22	1.384 (5)
N4—H4A	0.8600	C22—C21	1.383 (5)
C1—C2	1.379 (6)	C22—H18A	0.9300
C1—C6	1.390 (5)	C21—C20	1.355 (6)
C1—H1B	0.9300	C21—H19A	0.9300
C2—C3	1.358 (7)	C20—C19	1.367 (6)
C2—H2B	0.9300	C20—H20A	0.9300
C3—C4	1.383 (7)	C19—C18	1.377 (5)
C3—H3B	0.9300	C19—H21A	0.9300
C4—C5	1.376 (6)	C18—H22A	0.9300
C7—N1—C8	129.6 (3)	C11—C10—C9	118.8 (3)
C7—N1—H1A	115.2	C11—C10—H10A	120.6
C8—N1—H1A	115.2	C9—C10—H10A	120.6
C8—N2—C9	130.2 (3)	C12—C11—C10	123.1 (3)
C8—N2—H2A	114.9	C12—C11—Cl1	118.8 (3)
C9—N2—H2A	114.9	C10—C11—Cl1	118.0 (3)
C15—N3—C14	123.5 (3)	C11—C12—C13	118.3 (3)
C15—N3—H3A	118.2	C11—C12—H12A	120.9
C14—N3—H3A	118.2	C13—C12—H12A	120.9
C16—N4—C15	129.3 (3)	C14—C13—C12	120.6 (3)
C16—N4—H4A	115.4	C14—C13—H13A	119.7
C15—N4—H4A	115.4	C12—C13—H13A	119.7
C2—C1—C6	119.9 (4)	C13—C14—C9	120.5 (3)
C2—C1—H1B	120.0	C13—C14—N3	118.5 (3)
C6—C1—H1B	120.0	C9—C14—N3	120.9 (3)
C3—C2—C1	120.3 (4)	N3—C15—N4	115.9 (3)
C3—C2—H2B	119.8	N3—C15—S2	124.3 (2)
C1—C2—H2B	119.8	N4—C15—S2	119.8 (2)
C2—C3—C4	120.2 (4)	O2—C16—N4	121.8 (3)
C2—C3—H3B	119.9	O2—C16—C17	121.5 (3)
C4—C3—H3B	119.9	N4—C16—C17	116.7 (3)
C5—C4—C3	120.3 (4)	C18—C17—C22	119.6 (3)
C5—C4—H4B	119.9	C18—C17—C16	117.3 (3)
C3—C4—H4B	119.9	C22—C17—C16	123.1 (3)
C4—C5—C6	119.7 (4)	C21—C22—C17	119.4 (3)
C4—C5—H5A	120.2	C21—C22—H18A	120.3
C6—C5—H5A	120.2	C17—C22—H18A	120.3
C5—C6—C1	119.5 (4)	C20—C21—C22	120.3 (4)
C5—C6—C7	123.8 (3)	C20—C21—H19A	119.9
C1—C6—C7	116.6 (3)	C22—C21—H19A	119.9
O1—C7—N1	121.0 (3)	C21—C20—C19	120.9 (3)
O1—C7—C6	121.4 (3)	C21—C20—H20A	119.5
N1—C7—C6	117.6 (3)	C19—C20—H20A	119.5
N2—C8—N1	114.9 (3)	C20—C19—C18	119.7 (4)
N2—C8—S1	128.4 (3)	C20—C19—H21A	120.1
N1—C8—S1	116.7 (3)	C18—C19—H21A	120.1
C14—C9—C10	118.6 (3)	C19—C18—C17	120.0 (3)
C14—C9—N2	118.1 (3)	C19—C18—H22A	120.0
C10—C9—N2	123.2 (3)	C17—C18—H22A	120.0
C6—C1—C2—C3	−0.8 (6)	C12—C13—C14—C9	0.4 (5)
C1—C2—C3—C4	−0.9 (7)	C12—C13—C14—N3	177.1 (3)
C2—C3—C4—C5	1.8 (7)	C10—C9—C14—C13	−2.9 (5)
C3—C4—C5—C6	−1.0 (6)	N2—C9—C14—C13	178.9 (3)
C4—C5—C6—C1	−0.7 (5)	C10—C9—C14—N3	−179.5 (3)
C4—C5—C6—C7	−179.7 (3)	N2—C9—C14—N3	2.2 (4)
C2—C1—C6—C5	1.6 (6)	C15—N3—C14—C13	105.1 (4)
C2—C1—C6—C7	−179.4 (4)	C15—N3—C14—C9	−78.2 (4)
C8—N1—C7—O1	0.0 (6)	C14—N3—C15—N4	−177.1 (3)
C8—N1—C7—C6	179.8 (3)	C14—N3—C15—S2	3.7 (4)
C5—C6—C7—O1	159.2 (4)	C16—N4—C15—N3	3.3 (5)
C1—C6—C7—O1	−19.8 (5)	C16—N4—C15—S2	−177.5 (3)
C5—C6—C7—N1	−20.6 (5)	C15—N4—C16—O2	−3.9 (5)
C1—C6—C7—N1	160.4 (3)	C15—N4—C16—C17	175.0 (3)
C9—N2—C8—N1	177.6 (3)	O2—C16—C17—C18	−20.7 (5)
C9—N2—C8—S1	−2.3 (6)	N4—C16—C17—C18	160.4 (3)
C7—N1—C8—N2	−4.2 (5)	O2—C16—C17—C22	159.0 (3)
C7—N1—C8—S1	175.7 (3)	N4—C16—C17—C22	−19.8 (5)
C8—N2—C9—C14	−154.5 (3)	C18—C17—C22—C21	−0.4 (5)
C8—N2—C9—C10	27.3 (6)	C16—C17—C22—C21	179.9 (3)
C14—C9—C10—C11	3.8 (5)	C17—C22—C21—C20	0.2 (6)
N2—C9—C10—C11	−178.1 (3)	C22—C21—C20—C19	−0.1 (7)
C9—C10—C11—C12	−2.4 (6)	C21—C20—C19—C18	0.3 (7)
C9—C10—C11—Cl1	178.2 (3)	C20—C19—C18—C17	−0.6 (6)
C10—C11—C12—C13	−0.1 (6)	C22—C17—C18—C19	0.6 (5)
Cl1—C11—C12—C13	179.3 (3)	C16—C17—C18—C19	−179.6 (3)
C11—C12—C13—C14	1.1 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S2	0.86	2.86	3.443 (4)	127
N2—H2A···O1	0.86	1.91	2.621 (5)	140
N2—H2A···N3	0.86	2.46	2.791 (4)	103
N3—H3A···O2	0.86	1.96	2.642 (3)	135
C10—H10A···S1	0.93	2.61	3.173 (5)	120
N1—H1A···O2i	0.86	2.51	3.328 (5)	159
N4—H4A···S2ii	0.86	2.81	3.476 (4)	136

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S2	0.86	2.86	3.443 (4)	127
N2—H2A⋯O1	0.86	1.91	2.621 (5)	140
N3—H3A⋯O2	0.86	1.96	2.642 (3)	135
C10—H10A⋯S1	0.93	2.61	3.173 (5)	120
N1—H1A⋯O2i	0.86	2.51	3.328 (5)	159
N4—H4A⋯S2ii	0.86	2.81	3.476 (4)	136

Symmetry codes: (i) ; (ii) .