3-[(E)-(4-Chloro-benzyl-idene)amino]-1-phenyl-thio-urea.

In the title compound, C(14)H(12)ClN(3)S, the dihedral angle between the terminal benzene rings is 56.6 (2)°; the benzene rings lie to the same side of the mol-ecule. The major twist in the mol-ecule occurs around the C(ar)-N bond (ar is aromatic) [C-N-C-C = 49.9 (5)°]. The configuration about the N=C bond [1.271 (4) Å] is E. The amine H atoms lie on opposite sides of the mol-ecule with one forming an intra-molecular N-H⋯N(imine) hydrogen bond and an S(5) ring. In the crystal, centrosymmetric dimers are formed via {⋯HNC=S}(2) synthons.

Related literature

For related structures, see: Cunha et al. (2007 ▶); Kayed et al. (2008 ▶).

Experimental

Crystal data

C14H12ClN3S

M = 289.78

Monoclinic,

a = 15.082 (5) Å

b = 6.560 (2) Å

c = 15.205 (5) Å

β = 110.272 (8)°

V = 1411.2 (8) Å3

Z = 4

Mo Kα radiation

μ = 0.41 mm−1

T = 293 K

0.39 × 0.21 × 0.02 mm

Data collection

Oxford Diffraction Xcaliber Eos Gemini diffractometer

Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T min = 0.857, T max = 0.992

8647 measured reflections

2905 independent reflections

1572 reflections with I > 2σ(I)

R int = 0.080

Refinement

R[F 2 > 2σ(F 2)] = 0.068

wR(F 2) = 0.137

S = 1.00

2905 reflections

178 parameters

2 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.32 e Å−3

Δρmin = −0.21 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: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811008920/hb5814sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811008920/hb5814Isup2.hkl

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

C14H12ClN3S	F(000) = 600
Mr = 289.78	Dx = 1.364 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 752 reflections
a = 15.082 (5) Å	θ = 2.4–19.2°
b = 6.560 (2) Å	µ = 0.41 mm−1
c = 15.205 (5) Å	T = 293 K
β = 110.272 (8)°	Plate, light-pink
V = 1411.2 (8) Å3	0.39 × 0.21 × 0.02 mm
Z = 4

Oxford Diffraction Xcaliber Eos Gemini diffractometer	2905 independent reflections
Radiation source: fine-focus sealed tube	1572 reflections with I > 2σ(I)
graphite	Rint = 0.080
Detector resolution: 16.1952 pixels mm-1	θmax = 26.5°, θmin = 1.6°
ω scans	h = −17→18
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −8→8
Tmin = 0.857, Tmax = 0.992	l = −17→19
8647 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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.137	H atoms treated by a mixture of independent and constrained refinement
S = 1.00	w = 1/[σ2(Fo2) + (0.0511P)2] where P = (Fo2 + 2Fc2)/3
2905 reflections	(Δ/σ)max < 0.001
178 parameters	Δρmax = 0.32 e Å−3
2 restraints	Δρmin = −0.21 e Å−3

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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	0.89088 (7)	1.20521 (16)	0.14891 (8)	0.0759 (4)
S1	0.43050 (7)	−0.03791 (15)	0.10962 (7)	0.0525 (3)
N1	0.4748 (2)	0.3287 (5)	0.1918 (2)	0.0506 (8)
H1n	0.503 (2)	0.441 (3)	0.192 (3)	0.061*
N2	0.5408 (2)	0.2474 (4)	0.0834 (2)	0.0440 (8)
H2n	0.548 (2)	0.170 (4)	0.0405 (18)	0.053*
N3	0.58808 (19)	0.4293 (4)	0.1032 (2)	0.0420 (7)
C1	0.4240 (2)	0.3118 (6)	0.2544 (3)	0.0466 (9)
C2	0.4352 (3)	0.1467 (6)	0.3130 (3)	0.0602 (11)
H2	0.4743	0.0395	0.3097	0.072*
C3	0.3891 (3)	0.1397 (7)	0.3761 (3)	0.0720 (13)
H3	0.3972	0.0284	0.4159	0.086*
C4	0.3307 (3)	0.2969 (8)	0.3807 (3)	0.0710 (13)
H4	0.2992	0.2918	0.4235	0.085*
C5	0.3189 (3)	0.4607 (8)	0.3223 (4)	0.0758 (13)
H5	0.2785	0.5661	0.3244	0.091*
C6	0.3670 (3)	0.4695 (6)	0.2603 (3)	0.0632 (11)
H6	0.3607	0.5833	0.2222	0.076*
C7	0.4841 (2)	0.1899 (5)	0.1310 (2)	0.0409 (8)
C8	0.6458 (2)	0.4670 (5)	0.0611 (3)	0.0433 (9)
H8	0.6524	0.3738	0.0177	0.052*
C9	0.7018 (2)	0.6534 (5)	0.0794 (2)	0.0396 (8)
C10	0.6886 (2)	0.8062 (5)	0.1361 (2)	0.0440 (9)
H10	0.6402	0.7943	0.1605	0.053*
C11	0.7458 (2)	0.9755 (6)	0.1570 (2)	0.0497 (10)
H11	0.7366	1.0773	0.1955	0.060*
C12	0.8168 (2)	0.9922 (5)	0.1201 (3)	0.0476 (9)
C13	0.8311 (3)	0.8459 (6)	0.0628 (3)	0.0549 (11)
H13	0.8791	0.8599	0.0380	0.066*
C14	0.7732 (2)	0.6764 (6)	0.0421 (3)	0.0529 (10)
H14	0.7821	0.5762	0.0027	0.063*

	U11	U22	U33	U12	U13	U23
Cl1	0.0720 (7)	0.0538 (7)	0.0900 (9)	−0.0255 (5)	0.0129 (6)	0.0056 (6)
S1	0.0613 (6)	0.0469 (6)	0.0554 (6)	−0.0150 (5)	0.0281 (5)	−0.0079 (5)
N1	0.056 (2)	0.045 (2)	0.062 (2)	−0.0107 (15)	0.0344 (17)	−0.0113 (18)
N2	0.0534 (18)	0.0379 (19)	0.048 (2)	−0.0114 (14)	0.0273 (16)	−0.0095 (14)
N3	0.0434 (16)	0.0386 (18)	0.0456 (18)	−0.0051 (14)	0.0173 (15)	−0.0023 (14)
C1	0.042 (2)	0.050 (2)	0.050 (2)	−0.0068 (18)	0.0194 (18)	−0.011 (2)
C2	0.068 (3)	0.061 (3)	0.060 (3)	0.009 (2)	0.032 (2)	0.004 (2)
C3	0.095 (3)	0.072 (3)	0.061 (3)	0.001 (3)	0.043 (3)	0.009 (2)
C4	0.073 (3)	0.092 (4)	0.061 (3)	−0.012 (3)	0.040 (2)	−0.012 (3)
C5	0.077 (3)	0.082 (4)	0.082 (3)	0.017 (3)	0.045 (3)	−0.011 (3)
C6	0.073 (3)	0.058 (3)	0.065 (3)	0.006 (2)	0.032 (2)	−0.005 (2)
C7	0.040 (2)	0.043 (2)	0.041 (2)	0.0024 (16)	0.0163 (17)	0.0000 (18)
C8	0.050 (2)	0.040 (2)	0.047 (2)	−0.0006 (18)	0.0249 (18)	−0.0053 (18)
C9	0.044 (2)	0.035 (2)	0.041 (2)	−0.0015 (16)	0.0162 (17)	0.0026 (17)
C10	0.044 (2)	0.044 (2)	0.046 (2)	−0.0034 (17)	0.0181 (18)	0.0005 (19)
C11	0.058 (2)	0.047 (2)	0.042 (2)	0.0007 (19)	0.0145 (19)	−0.0001 (19)
C12	0.047 (2)	0.037 (2)	0.052 (2)	−0.0047 (17)	0.0082 (19)	0.0098 (18)
C13	0.053 (2)	0.049 (3)	0.073 (3)	−0.0016 (19)	0.035 (2)	0.014 (2)
C14	0.062 (3)	0.041 (2)	0.065 (3)	−0.0015 (18)	0.034 (2)	−0.002 (2)

Cl1—C12	1.748 (4)	C4—H4	0.9300
S1—C7	1.676 (4)	C5—C6	1.374 (5)
N1—C7	1.339 (4)	C5—H5	0.9300
N1—C1	1.419 (4)	C6—H6	0.9300
N1—H1n	0.853 (10)	C8—C9	1.457 (4)
N2—C7	1.352 (4)	C8—H8	0.9300
N2—N3	1.369 (4)	C9—C10	1.381 (4)
N2—H2n	0.863 (10)	C9—C14	1.387 (4)
N3—C8	1.271 (4)	C10—C11	1.374 (4)
C1—C6	1.368 (5)	C10—H10	0.9300
C1—C2	1.375 (5)	C11—C12	1.375 (5)
C2—C3	1.366 (5)	C11—H11	0.9300
C2—H2	0.9300	C12—C13	1.363 (5)
C3—C4	1.374 (6)	C13—C14	1.381 (5)
C3—H3	0.9300	C13—H13	0.9300
C4—C5	1.366 (6)	C14—H14	0.9300
C7—N1—C1	128.3 (3)	N1—C7—N2	114.6 (3)
C7—N1—H1n	114 (3)	N1—C7—S1	125.6 (3)
C1—N1—H1n	117 (3)	N2—C7—S1	119.8 (3)
C7—N2—N3	120.2 (3)	N3—C8—C9	121.4 (3)
C7—N2—H2n	121 (2)	N3—C8—H8	119.3
N3—N2—H2n	119 (2)	C9—C8—H8	119.3
C8—N3—N2	117.1 (3)	C10—C9—C14	118.4 (3)
C6—C1—C2	119.5 (4)	C10—C9—C8	121.9 (3)
C6—C1—N1	118.9 (4)	C14—C9—C8	119.6 (3)
C2—C1—N1	121.5 (3)	C11—C10—C9	121.1 (3)
C3—C2—C1	120.2 (4)	C11—C10—H10	119.5
C3—C2—H2	119.9	C9—C10—H10	119.5
C1—C2—H2	119.9	C10—C11—C12	119.0 (4)
C2—C3—C4	120.1 (4)	C10—C11—H11	120.5
C2—C3—H3	119.9	C12—C11—H11	120.5
C4—C3—H3	119.9	C13—C12—C11	121.5 (3)
C5—C4—C3	119.9 (4)	C13—C12—Cl1	119.6 (3)
C5—C4—H4	120.0	C11—C12—Cl1	118.8 (3)
C3—C4—H4	120.0	C12—C13—C14	119.0 (3)
C4—C5—C6	119.9 (4)	C12—C13—H13	120.5
C4—C5—H5	120.1	C14—C13—H13	120.5
C6—C5—H5	120.1	C13—C14—C9	120.9 (4)
C1—C6—C5	120.4 (4)	C13—C14—H14	119.5
C1—C6—H6	119.8	C9—C14—H14	119.5
C5—C6—H6	119.8
C7—N2—N3—C8	174.7 (3)	N3—N2—C7—S1	−177.2 (2)
C7—N1—C1—C6	−134.1 (4)	N2—N3—C8—C9	−178.1 (3)
C7—N1—C1—C2	49.9 (5)	N3—C8—C9—C10	−6.3 (5)
C6—C1—C2—C3	0.5 (6)	N3—C8—C9—C14	171.1 (3)
N1—C1—C2—C3	176.5 (4)	C14—C9—C10—C11	−1.3 (5)
C1—C2—C3—C4	0.5 (6)	C8—C9—C10—C11	176.1 (3)
C2—C3—C4—C5	−0.2 (7)	C9—C10—C11—C12	0.4 (5)
C3—C4—C5—C6	−1.2 (7)	C10—C11—C12—C13	0.6 (5)
C2—C1—C6—C5	−2.0 (6)	C10—C11—C12—Cl1	−178.6 (3)
N1—C1—C6—C5	−178.1 (4)	C11—C12—C13—C14	−0.5 (6)
C4—C5—C6—C1	2.3 (6)	Cl1—C12—C13—C14	178.7 (3)
C1—N1—C7—N2	−177.2 (3)	C12—C13—C14—C9	−0.5 (6)
C1—N1—C7—S1	4.1 (5)	C10—C9—C14—C13	1.3 (5)
N3—N2—C7—N1	4.1 (4)	C8—C9—C14—C13	−176.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1n···N3	0.85 (2)	2.16 (4)	2.601 (4)	112 (3)
N2—H2n···S1i	0.86 (3)	2.57 (3)	3.401 (3)	164 (2)

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1n⋯N3	0.85 (2)	2.16 (4)	2.601 (4)	112 (3)
N2—H2n⋯S1i	0.86 (3)	2.57 (3)	3.401 (3)	164 (2)

Symmetry code: (i) .