(Z)-4-Chloro-N-(1-{2-[3-(4-chloro-benzoyl)ureido]eth-yl}imidazolidin-2-yl-idene)benzamide.

The title compound, C(20)H(19)Cl(2)N(5)O(2)S, was obtained from the reaction of 4-chloro-benzoyl isothio-cyanate with diethyl-ene-triamine. The imidazolidine ring is slightly twisted with an N-C-C-N torsion angle of 15.4 (4)°, while the thio-urea moiety maintains its trans-cis geometry. The mol-ecule is stabilized by intramolecular N-H⋯O hydrogen bonds. The crystal structure features N-H⋯O, N-H⋯S and C-H⋯O hydrogen bonds and π-π interactions between benzene rings with a centroid-centroid distance of 3.607 (3) Å.

Related literature

For the structures of bis­(N-benzoyl­thio­ureas) derived from aliphatic diamines, see: Ding et al. (2008 ▶). For those derived from cyclo­hexane diamine, see: Jumal et al. (2011 ▶). For those derived from aromatic diamines, see: Osman & Yamin (2011 ▶); Dong et al. (2008 ▶).

Experimental

Crystal data

C20H19Cl2N5O2S

M = 464.36

Monoclinic,

a = 24.488 (7) Å

b = 6.645 (2) Å

c = 13.108 (4) Å

β = 97.16 (2)°

V = 2116.2 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.43 mm−1

T = 296 K

0.22 × 0.08 × 0.07 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.911, T max = 0.970

8499 measured reflections

4165 independent reflections

2855 reflections with I > 2σ(I)

R int = 0.055

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.090

S = 0.93

4165 reflections

283 parameters

5 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.18 e Å−3

Δρmin = −0.28 e Å−3

Absolute structure: Flack (1983 ▶) 1987 Friedel pairs

Flack parameter: 0.06 (6)

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/S1600536812028218/go2061sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812028218/go2061Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536812028218/go2061Isup3.cml

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

C20H19Cl2N5O2S	F(000) = 960
Mr = 464.36	Dx = 1.457 Mg m−3
Monoclinic, Cc	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: C -2yc	Cell parameters from 2230 reflections
a = 24.488 (7) Å	θ = 3.1–26.4°
b = 6.645 (2) Å	µ = 0.43 mm−1
c = 13.108 (4) Å	T = 296 K
β = 97.16 (2)°	Slab, colourless
V = 2116.2 (11) Å3	0.22 × 0.08 × 0.07 mm
Z = 4

Bruker SMART APEX CCD area-detector diffractometer	4165 independent reflections
Radiation source: fine-focus sealed tube	2855 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.055
Detector resolution: 83.66 pixels mm-1	θmax = 26.4°, θmin = 3.1°
ω scan	h = −30→30
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −8→8
Tmin = 0.911, Tmax = 0.970	l = −16→16
8499 measured reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.040	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.090	w = 1/[σ2(Fo2) + (0.0374P)2] where P = (Fo2 + 2Fc2)/3
S = 0.93	(Δ/σ)max < 0.001
4165 reflections	Δρmax = 0.18 e Å−3
283 parameters	Δρmin = −0.28 e Å−3
5 restraints	Absolute structure: Flack (1983) ???? Friedel pairs
Primary atom site location: structure-invariant direct methods	Flack parameter: 0.06 (6)

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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	0.84274 (4)	0.3989 (2)	0.19364 (9)	0.0858 (4)
Cl2	0.83019 (4)	−0.17344 (19)	0.37999 (10)	0.0887 (4)
S1	0.47526 (3)	0.21472 (13)	0.36669 (7)	0.0574 (3)
O1	0.59035 (9)	0.0679 (4)	0.0292 (2)	0.0654 (7)
O2	0.63898 (9)	0.5325 (3)	0.35719 (19)	0.0536 (6)
N1	0.56767 (10)	0.3697 (4)	0.1039 (2)	0.0456 (7)
N2	0.48754 (11)	0.1718 (5)	0.0424 (2)	0.0564 (8)
H2A	0.5083 (15)	0.083 (5)	0.018 (3)	0.100 (16)*
N3	0.47666 (10)	0.4668 (4)	0.1099 (2)	0.0478 (7)
N4	0.53148 (11)	0.5442 (4)	0.3285 (2)	0.0479 (7)
H4A	0.5640 (7)	0.584 (5)	0.319 (3)	0.053 (10)*
N5	0.58290 (10)	0.2711 (4)	0.3890 (2)	0.0426 (6)
H5A	0.583 (2)	0.153 (3)	0.415 (4)	0.13 (2)*
C1	0.70080 (13)	0.1240 (6)	0.1077 (3)	0.0509 (9)
H1B	0.6892	−0.0066	0.0914	0.061*
C2	0.75617 (14)	0.1603 (6)	0.1344 (3)	0.0550 (9)
H2B	0.7817	0.0561	0.1368	0.066*
C3	0.77275 (14)	0.3549 (6)	0.1573 (3)	0.0566 (10)
C4	0.73592 (13)	0.5075 (5)	0.1551 (3)	0.0534 (9)
H4B	0.7481	0.6377	0.1710	0.064*
C5	0.68087 (14)	0.4709 (5)	0.1295 (2)	0.0496 (8)
H5B	0.6559	0.5764	0.1288	0.060*
C6	0.66193 (13)	0.2761 (5)	0.1045 (2)	0.0434 (8)
C7	0.60276 (13)	0.2283 (5)	0.0752 (2)	0.0444 (8)
C8	0.51449 (13)	0.3336 (5)	0.0849 (2)	0.0433 (8)
C9	0.42894 (14)	0.2020 (6)	0.0255 (3)	0.0606 (9)
H9A	0.4095	0.0871	0.0488	0.073*
H9B	0.4164	0.2259	−0.0466	0.073*
C10	0.42110 (14)	0.3873 (6)	0.0898 (3)	0.0624 (10)
H10A	0.3964	0.4832	0.0520	0.075*
H10B	0.4068	0.3519	0.1532	0.075*
C11	0.48875 (14)	0.6591 (5)	0.1608 (3)	0.0538 (9)
H11A	0.4633	0.7594	0.1294	0.065*
H11B	0.5256	0.7006	0.1504	0.065*
C12	0.48476 (14)	0.6519 (5)	0.2745 (3)	0.0516 (9)
H12A	0.4839	0.7878	0.3011	0.062*
H12B	0.4509	0.5851	0.2862	0.062*
C13	0.53131 (12)	0.3544 (5)	0.3597 (2)	0.0420 (7)
C14	0.63297 (12)	0.3540 (5)	0.3762 (2)	0.0412 (7)
C15	0.68047 (12)	0.2137 (5)	0.3839 (2)	0.0419 (7)
C16	0.67515 (12)	0.0123 (5)	0.3578 (2)	0.0443 (8)
H16A	0.6403	−0.0424	0.3402	0.053*
C17	0.72101 (13)	−0.1086 (5)	0.3576 (3)	0.0483 (8)
H17A	0.7173	−0.2439	0.3398	0.058*
C18	0.77199 (13)	−0.0256 (6)	0.3840 (3)	0.0516 (8)
C19	0.77881 (13)	0.1758 (5)	0.4111 (3)	0.0524 (8)
H19A	0.8137	0.2295	0.4294	0.063*
C20	0.73277 (12)	0.2930 (5)	0.4101 (2)	0.0473 (8)
H20A	0.7366	0.4285	0.4274	0.057*

	U11	U22	U33	U12	U13	U23
Cl1	0.0511 (5)	0.1137 (9)	0.0944 (8)	−0.0131 (6)	0.0161 (5)	−0.0142 (7)
Cl2	0.0558 (6)	0.0981 (9)	0.1106 (9)	0.0265 (6)	0.0045 (5)	−0.0239 (8)
S1	0.0419 (4)	0.0488 (5)	0.0824 (7)	0.0017 (4)	0.0109 (4)	0.0106 (5)
O1	0.0544 (13)	0.0527 (15)	0.0894 (19)	−0.0025 (11)	0.0106 (12)	−0.0293 (14)
O2	0.0536 (13)	0.0330 (13)	0.0734 (17)	−0.0069 (10)	0.0045 (11)	0.0035 (12)
N1	0.0427 (15)	0.0405 (16)	0.0538 (18)	0.0054 (12)	0.0067 (13)	−0.0050 (13)
N2	0.0456 (16)	0.0532 (19)	0.071 (2)	0.0027 (14)	0.0082 (14)	−0.0145 (16)
N3	0.0490 (15)	0.0394 (16)	0.0549 (18)	0.0093 (12)	0.0058 (13)	−0.0024 (14)
N4	0.0479 (16)	0.0333 (15)	0.0626 (19)	0.0049 (12)	0.0068 (14)	0.0006 (13)
N5	0.0381 (14)	0.0378 (15)	0.0518 (17)	0.0011 (12)	0.0055 (12)	0.0054 (14)
C1	0.054 (2)	0.050 (2)	0.049 (2)	0.0073 (16)	0.0064 (16)	−0.0063 (17)
C2	0.053 (2)	0.065 (2)	0.049 (2)	0.0126 (17)	0.0112 (16)	−0.0059 (19)
C3	0.050 (2)	0.074 (3)	0.047 (2)	−0.0066 (19)	0.0136 (17)	−0.004 (2)
C4	0.056 (2)	0.049 (2)	0.058 (2)	−0.0078 (17)	0.0134 (17)	−0.0080 (18)
C5	0.059 (2)	0.046 (2)	0.046 (2)	0.0006 (16)	0.0140 (16)	−0.0008 (16)
C6	0.0538 (19)	0.044 (2)	0.0344 (19)	0.0026 (15)	0.0130 (15)	−0.0008 (15)
C7	0.0492 (18)	0.0414 (19)	0.043 (2)	0.0021 (14)	0.0071 (15)	−0.0056 (16)
C8	0.0509 (19)	0.0421 (19)	0.0378 (18)	0.0025 (15)	0.0090 (15)	−0.0011 (15)
C9	0.0486 (19)	0.062 (2)	0.072 (3)	−0.0022 (16)	0.0121 (18)	−0.008 (2)
C10	0.048 (2)	0.068 (3)	0.070 (3)	0.0153 (17)	0.0064 (18)	−0.003 (2)
C11	0.061 (2)	0.0326 (18)	0.068 (3)	0.0122 (15)	0.0082 (18)	0.0048 (17)
C12	0.063 (2)	0.0361 (19)	0.055 (2)	0.0175 (15)	0.0035 (17)	−0.0065 (16)
C13	0.0421 (16)	0.0401 (19)	0.044 (2)	0.0069 (13)	0.0053 (14)	−0.0033 (15)
C14	0.0422 (17)	0.0419 (19)	0.0393 (19)	−0.0029 (14)	0.0041 (13)	−0.0008 (16)
C15	0.0432 (16)	0.0407 (18)	0.0420 (19)	−0.0046 (13)	0.0060 (14)	0.0014 (15)
C16	0.0411 (16)	0.0443 (19)	0.048 (2)	−0.0046 (14)	0.0074 (14)	0.0008 (16)
C17	0.0473 (18)	0.0401 (18)	0.058 (2)	−0.0011 (15)	0.0101 (16)	−0.0010 (17)
C18	0.0441 (17)	0.060 (2)	0.051 (2)	0.0098 (16)	0.0082 (15)	−0.0001 (18)
C19	0.0387 (17)	0.059 (2)	0.058 (2)	−0.0068 (16)	0.0023 (15)	−0.0031 (19)
C20	0.0448 (18)	0.0454 (19)	0.051 (2)	−0.0051 (15)	0.0033 (15)	−0.0003 (16)

Cl1—C3	1.745 (4)	C4—H4B	0.9300
Cl2—C18	1.737 (3)	C5—C6	1.400 (4)
S1—C13	1.669 (3)	C5—H5B	0.9300
O1—C7	1.243 (4)	C6—C7	1.486 (4)
O2—C14	1.224 (3)	C9—C10	1.518 (5)
N1—C8	1.317 (4)	C9—H9A	0.9700
N1—C7	1.358 (4)	C9—H9B	0.9700
N2—C8	1.346 (4)	C10—H10A	0.9700
N2—C9	1.438 (4)	C10—H10B	0.9700
N2—H2A	0.865 (10)	C11—C12	1.505 (5)
N3—C8	1.351 (4)	C11—H11A	0.9700
N3—C10	1.453 (4)	C11—H11B	0.9700
N3—C11	1.455 (4)	C12—H12A	0.9700
N4—C13	1.326 (4)	C12—H12B	0.9700
N4—C12	1.456 (4)	C14—C15	1.484 (4)
N4—H4A	0.864 (10)	C15—C16	1.384 (4)
N5—C14	1.374 (4)	C15—C20	1.388 (4)
N5—C13	1.389 (4)	C16—C17	1.381 (4)
N5—H5A	0.857 (10)	C16—H16A	0.9300
C1—C2	1.378 (5)	C17—C18	1.369 (4)
C1—C6	1.385 (4)	C17—H17A	0.9300
C1—H1B	0.9300	C18—C19	1.389 (5)
C2—C3	1.378 (5)	C19—C20	1.369 (4)
C2—H2B	0.9300	C19—H19A	0.9300
C3—C4	1.355 (5)	C20—H20A	0.9300
C4—C5	1.370 (4)
C8—N1—C7	117.8 (3)	N3—C10—C9	102.4 (3)
C8—N2—C9	112.4 (3)	N3—C10—H10A	111.3
C8—N2—H2A	115 (3)	C9—C10—H10A	111.3
C9—N2—H2A	131 (3)	N3—C10—H10B	111.3
C8—N3—C10	111.9 (3)	C9—C10—H10B	111.3
C8—N3—C11	125.5 (3)	H10A—C10—H10B	109.2
C10—N3—C11	122.3 (3)	N3—C11—C12	113.1 (3)
C13—N4—C12	125.8 (3)	N3—C11—H11A	109.0
C13—N4—H4A	112 (2)	C12—C11—H11A	109.0
C12—N4—H4A	118 (2)	N3—C11—H11B	109.0
C14—N5—C13	127.0 (3)	C12—C11—H11B	109.0
C14—N5—H5A	117 (3)	H11A—C11—H11B	107.8
C13—N5—H5A	116 (3)	N4—C12—C11	110.7 (3)
C2—C1—C6	122.1 (3)	N4—C12—H12A	109.5
C2—C1—H1B	119.0	C11—C12—H12A	109.5
C6—C1—H1B	119.0	N4—C12—H12B	109.5
C3—C2—C1	118.2 (3)	C11—C12—H12B	109.5
C3—C2—H2B	120.9	H12A—C12—H12B	108.1
C1—C2—H2B	120.9	N4—C13—N5	115.3 (3)
C4—C3—C2	121.4 (3)	N4—C13—S1	125.5 (2)
C4—C3—Cl1	120.6 (3)	N5—C13—S1	119.3 (2)
C2—C3—Cl1	118.0 (3)	O2—C14—N5	123.0 (3)
C3—C4—C5	120.3 (3)	O2—C14—C15	120.6 (3)
C3—C4—H4B	119.8	N5—C14—C15	116.3 (3)
C5—C4—H4B	119.8	C16—C15—C20	118.9 (3)
C4—C5—C6	120.6 (3)	C16—C15—C14	122.8 (3)
C4—C5—H5B	119.7	C20—C15—C14	118.0 (3)
C6—C5—H5B	119.7	C17—C16—C15	120.8 (3)
C1—C6—C5	117.4 (3)	C17—C16—H16A	119.6
C1—C6—C7	119.7 (3)	C15—C16—H16A	119.6
C5—C6—C7	122.8 (3)	C18—C17—C16	118.8 (3)
O1—C7—N1	127.1 (3)	C18—C17—H17A	120.6
O1—C7—C6	118.7 (3)	C16—C17—H17A	120.6
N1—C7—C6	114.2 (3)	C17—C18—C19	122.0 (3)
N1—C8—N2	130.2 (3)	C17—C18—Cl2	119.4 (3)
N1—C8—N3	121.8 (3)	C19—C18—Cl2	118.7 (3)
N2—C8—N3	107.9 (3)	C20—C19—C18	118.2 (3)
N2—C9—C10	102.7 (3)	C20—C19—H19A	120.9
N2—C9—H9A	111.2	C18—C19—H19A	120.9
C10—C9—H9A	111.2	C19—C20—C15	121.3 (3)
N2—C9—H9B	111.2	C19—C20—H20A	119.3
C10—C9—H9B	111.2	C15—C20—H20A	119.3
H9A—C9—H9B	109.1
C6—C1—C2—C3	−0.7 (5)	C11—N3—C10—C9	173.4 (3)
C1—C2—C3—C4	0.7 (5)	N2—C9—C10—N3	15.4 (4)
C1—C2—C3—Cl1	178.7 (3)	C8—N3—C11—C12	−99.4 (4)
C2—C3—C4—C5	−0.1 (5)	C10—N3—C11—C12	73.8 (4)
Cl1—C3—C4—C5	−178.0 (3)	C13—N4—C12—C11	−100.0 (4)
C3—C4—C5—C6	−0.6 (5)	N3—C11—C12—N4	73.6 (4)
C2—C1—C6—C5	0.0 (5)	C12—N4—C13—N5	166.5 (3)
C2—C1—C6—C7	180.0 (3)	C12—N4—C13—S1	−14.0 (5)
C4—C5—C6—C1	0.6 (4)	C14—N5—C13—N4	−9.4 (5)
C4—C5—C6—C7	−179.4 (3)	C14—N5—C13—S1	171.1 (3)
C8—N1—C7—O1	2.4 (5)	C13—N5—C14—O2	16.6 (5)
C8—N1—C7—C6	−176.9 (3)	C13—N5—C14—C15	−161.9 (3)
C1—C6—C7—O1	−18.3 (4)	O2—C14—C15—C16	−149.1 (3)
C5—C6—C7—O1	161.6 (3)	N5—C14—C15—C16	29.5 (5)
C1—C6—C7—N1	161.0 (3)	O2—C14—C15—C20	25.3 (5)
C5—C6—C7—N1	−19.0 (4)	N5—C14—C15—C20	−156.2 (3)
C7—N1—C8—N2	1.9 (5)	C20—C15—C16—C17	−0.1 (5)
C7—N1—C8—N3	−179.3 (3)	C14—C15—C16—C17	174.3 (3)
C9—N2—C8—N1	−173.8 (3)	C15—C16—C17—C18	0.1 (5)
C9—N2—C8—N3	7.3 (4)	C16—C17—C18—C19	0.2 (5)
C10—N3—C8—N1	−175.0 (3)	C16—C17—C18—Cl2	−177.9 (2)
C11—N3—C8—N1	−1.2 (5)	C17—C18—C19—C20	−0.6 (5)
C10—N3—C8—N2	4.0 (4)	Cl2—C18—C19—C20	177.5 (3)
C11—N3—C8—N2	177.8 (3)	C18—C19—C20—C15	0.7 (5)
C8—N2—C9—C10	−14.6 (4)	C16—C15—C20—C19	−0.4 (5)
C8—N3—C10—C9	−12.6 (4)	C14—C15—C20—C19	−174.9 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1	0.87 (1)	2.00 (4)	2.637 (4)	130 (4)
N2—H2A···S1i	0.87 (1)	2.85 (4)	3.438 (3)	127 (4)
N4—H4A···O2	0.86 (1)	1.87 (2)	2.614 (3)	143 (3)
N5—H5A···O1ii	0.86 (1)	2.09 (2)	2.898 (4)	157 (5)
C17—H17A···O2iii	0.93	2.46	3.118 (4)	128

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1	0.87 (1)	2.00 (4)	2.637 (4)	130 (4)
N2—H2A⋯S1i	0.87 (1)	2.85 (4)	3.438 (3)	127 (4)
N4—H4A⋯O2	0.86 (1)	1.87 (2)	2.614 (3)	143 (3)
N5—H5A⋯O1ii	0.86 (1)	2.09 (2)	2.898 (4)	157 (5)
C17—H17A⋯O2iii	0.93	2.46	3.118 (4)	128

Symmetry codes: (i) ; (ii) ; (iii) .