Crystal structure of 1-{(Z)-[(2E)-3-(4-chloro-phen-yl)-1-phenyl-prop-2-en-1-yl-idene]amino}-3-ethyl-thio-urea.

In the title thio-semicarbazone compound, C18H18ClN3S, the CN3S residue is almost planar (r.m.s. deviation = 0.0031 Å) and forms dihedral angles of 65.99 (7) and 34.60 (10)° with the phenyl and chloro-benzene rings, respectively; the dihedral angle between the aromatic rings is 85.13 (8)°. The conformation about the C=N bond is Z, and that about the C=C bonds is E. The imine N and ethyl N atoms are syn and are linked by an eth-yl-imine N-H⋯N hydrogen bond. This H atom also forms an inter-molecular hydrogen bond to the thione S atom, resulting in a supra-molecular helical chain propagating along the b axis. The chains are consolidated into a three-dimensional architecture by phenyl-C-H⋯Cl contacts and weak π-π inter-actions between centrosymmetrically related chloro-benzene rings [inter-centroid distance = 3.9127 (15) Å].

Related literature

For background to the coordination chemistry and applications of metal thio­semicarbazones, see: Dilworth & Hueting (2012 ▸). For the structure of a closely related thio­semicarbazone compound, 1-benzo­thio­phene-2-carbaldehyde 4-ethyl­thio­semicarbazone, with almost planar semicarbazone units (two mol­ecules comprise the asymmetric unit) and E conformations for the C=N bonds, see: Kayed et al. (2009 ▸).

Experimental

Crystal data

C18H18ClN3S

M = 343.86

Monoclinic,

a = 10.580 (1) Å

b = 12.0438 (9) Å

c = 13.9561 (10) Å

β = 90.196 (8)°

V = 1778.3 (2) Å3

Z = 4

Mo Kα radiation

μ = 0.33 mm−1

T = 293 K

0.20 × 0.15 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector

Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013 ▸) T min = 0.800, T max = 1.000

11178 measured reflections

4078 independent reflections

1963 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.120

S = 1.00

4078 reflections

216 parameters

2 restraints

H-atom parameters constrained

Δρmax = 0.20 e Å−3

Δρmin = −0.25 e Å−3

Data collection: CrysAlis PRO (Agilent, 2013 ▸); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▸); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015 ▸); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▸) and DIAMOND (Brandenburg, 2006 ▸); software used to prepare material for publication: publCIF (Westrip, 2010 ▸).

Crystal structure: contains datablock(s) 1, I. DOI: 10.1107/S2056989015023531/hb7555sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S2056989015023531/hb7555Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S2056989015023531/hb7555Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S2056989015023531/hb7555fig1.tif

The mol­ecular structure of the title compound showing displacement ellipsoids at the 50% probability level.

Click here for additional data file.

b . DOI: 10.1107/S2056989015023531/hb7555fig2.tif

A view of the helical supra­molecular chain along the b axis and sustained by N—H⋯S hydrogen bonds shown as orange dashed lines.

Click here for additional data file.

a . DOI: 10.1107/S2056989015023531/hb7555fig3.tif

A view of the unit cell contents in projection down the a axis. The N—H⋯S (orange), C—H⋯Cl (blue) and π—π (purple) inter­actions are shown as dashed lines.

CCDC reference: 1441045

Additional supporting information: crystallographic information; 3D view; checkCIF report

C18H18ClN3S	F(000) = 720
Mr = 343.86	Dx = 1.284 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
a = 10.580 (1) Å	Cell parameters from 2181 reflections
b = 12.0438 (9) Å	θ = 2.9–27.5°
c = 13.9561 (10) Å	µ = 0.33 mm−1
β = 90.196 (8)°	T = 293 K
V = 1778.3 (2) Å3	Prism, light-brown
Z = 4	0.20 × 0.15 × 0.10 mm

Agilent SuperNova Dual diffractometer with an Atlas detector	4078 independent reflections
Radiation source: SuperNova (Mo) X-ray Source	1963 reflections with I > 2σ(I)
Mirror monochromator	Rint = 0.051
Detector resolution: 10.4041 pixels mm-1	θmax = 27.5°, θmin = 2.9°
ω scan	h = −13→12
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2013)	k = −14→15
Tmin = 0.800, Tmax = 1.000	l = −18→18
11178 measured reflections

Refinement on F2	Hydrogen site location: mixed
Least-squares matrix: full	H-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038	w = 1/[σ2(Fo2) + (0.0463P)2] where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.120	(Δ/σ)max = 0.001
S = 1.00	Δρmax = 0.20 e Å−3
4078 reflections	Δρmin = −0.25 e Å−3
216 parameters	Extinction correction: SHELXL2014 (Sheldrick, 2014), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
2 restraints	Extinction coefficient: 0.0044 (7)

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.

	x	y	z	Uiso*/Ueq
S1	1.05835 (7)	−0.02341 (6)	0.20649 (5)	0.0606 (2)
Cl1	0.48690 (8)	0.72659 (6)	0.71676 (5)	0.0754 (3)
N1	1.0584 (2)	0.19712 (18)	0.23053 (16)	0.0579 (6)
H1N	1.025 (2)	0.2566 (14)	0.2562 (18)	0.070*
N2	0.9246 (2)	0.09776 (16)	0.32430 (15)	0.0543 (6)
H2N	0.900 (2)	0.0320 (11)	0.3439 (17)	0.065*
N3	0.88627 (18)	0.19560 (15)	0.36594 (14)	0.0484 (5)
C1	1.0138 (2)	0.0979 (2)	0.25424 (18)	0.0470 (6)
C2	1.1491 (2)	0.2179 (2)	0.1541 (2)	0.0636 (8)
H2A	1.2065	0.1553	0.1494	0.076*
H2B	1.1986	0.2832	0.1699	0.076*
C3	1.0860 (3)	0.2351 (4)	0.0601 (2)	0.1085 (13)
H3A	1.0393	0.1696	0.0431	0.163*
H3B	1.1485	0.2497	0.0121	0.163*
H3C	1.0292	0.2971	0.0643	0.163*
C4	0.8004 (2)	0.18918 (18)	0.43172 (16)	0.0420 (6)
C5	0.7641 (2)	0.29357 (18)	0.47552 (16)	0.0443 (6)
H5	0.8101	0.3565	0.4592	0.053*
C6	0.6697 (2)	0.30579 (18)	0.53736 (16)	0.0434 (6)
H6	0.6254	0.2419	0.5537	0.052*
C7	0.6281 (2)	0.40943 (18)	0.58244 (16)	0.0409 (6)
C8	0.5030 (2)	0.42061 (19)	0.61122 (16)	0.0463 (6)
H8	0.4477	0.3614	0.6026	0.056*
C9	0.4589 (3)	0.5176 (2)	0.65233 (16)	0.0517 (7)
H9	0.3749	0.5240	0.6708	0.062*
C10	0.5415 (3)	0.60409 (19)	0.66531 (16)	0.0504 (7)
C11	0.6661 (3)	0.5955 (2)	0.63902 (18)	0.0576 (7)
H11	0.7209	0.6548	0.6489	0.069*
C12	0.7099 (3)	0.49840 (19)	0.59786 (18)	0.0529 (7)
H12	0.7943	0.4925	0.5804	0.063*
C41	0.7411 (2)	0.08309 (17)	0.46264 (17)	0.0391 (6)
C42	0.6659 (2)	0.02282 (19)	0.39972 (17)	0.0446 (6)
H42	0.6525	0.0488	0.3377	0.054*
C43	0.6108 (2)	−0.07542 (19)	0.42866 (19)	0.0506 (7)
H43	0.5608	−0.1156	0.3860	0.061*
C44	0.6294 (2)	−0.1139 (2)	0.5200 (2)	0.0550 (7)
H44	0.5916	−0.1799	0.5394	0.066*
C45	0.7037 (2)	−0.0552 (2)	0.58311 (19)	0.0553 (7)
H45	0.7163	−0.0817	0.6450	0.066*
C46	0.7597 (2)	0.0428 (2)	0.55490 (17)	0.0491 (6)
H46	0.8101	0.0821	0.5978	0.059*

	U11	U22	U33	U12	U13	U23
S1	0.0614 (5)	0.0544 (4)	0.0661 (5)	0.0084 (3)	0.0204 (4)	−0.0080 (4)
Cl1	0.1222 (7)	0.0502 (4)	0.0539 (4)	0.0289 (4)	0.0068 (4)	−0.0074 (3)
N1	0.0567 (14)	0.0503 (14)	0.0670 (15)	−0.0007 (11)	0.0263 (12)	0.0014 (12)
N2	0.0638 (14)	0.0380 (12)	0.0614 (13)	0.0005 (10)	0.0292 (11)	−0.0016 (11)
N3	0.0531 (12)	0.0375 (11)	0.0548 (12)	0.0017 (9)	0.0176 (11)	−0.0023 (10)
C1	0.0433 (14)	0.0470 (16)	0.0506 (14)	0.0010 (11)	0.0098 (12)	−0.0017 (13)
C2	0.0500 (16)	0.0699 (18)	0.0710 (19)	−0.0065 (13)	0.0207 (15)	0.0061 (16)
C3	0.078 (2)	0.172 (4)	0.076 (2)	−0.021 (2)	0.006 (2)	0.031 (3)
C4	0.0426 (14)	0.0386 (14)	0.0450 (14)	−0.0014 (10)	0.0090 (12)	−0.0001 (12)
C5	0.0482 (15)	0.0349 (13)	0.0500 (14)	−0.0011 (10)	0.0094 (12)	−0.0001 (11)
C6	0.0465 (14)	0.0378 (14)	0.0459 (14)	−0.0015 (10)	0.0062 (12)	−0.0017 (11)
C7	0.0491 (15)	0.0368 (13)	0.0368 (13)	0.0022 (11)	0.0066 (11)	0.0014 (11)
C8	0.0537 (16)	0.0411 (14)	0.0442 (14)	0.0000 (11)	0.0115 (12)	0.0051 (12)
C9	0.0611 (17)	0.0494 (16)	0.0448 (15)	0.0155 (13)	0.0141 (13)	0.0075 (13)
C10	0.079 (2)	0.0373 (14)	0.0348 (13)	0.0122 (13)	0.0034 (13)	−0.0021 (12)
C11	0.0728 (19)	0.0446 (16)	0.0555 (16)	−0.0044 (13)	−0.0035 (15)	−0.0065 (14)
C12	0.0543 (17)	0.0489 (16)	0.0555 (16)	−0.0019 (12)	0.0096 (13)	−0.0080 (13)
C41	0.0404 (13)	0.0342 (13)	0.0427 (14)	0.0028 (10)	0.0110 (11)	−0.0028 (11)
C42	0.0470 (15)	0.0450 (14)	0.0419 (13)	0.0016 (11)	0.0075 (12)	−0.0019 (12)
C43	0.0538 (16)	0.0433 (14)	0.0547 (17)	−0.0066 (12)	0.0098 (13)	−0.0102 (13)
C44	0.0603 (17)	0.0396 (14)	0.0652 (18)	−0.0061 (12)	0.0154 (15)	0.0042 (14)
C45	0.0653 (18)	0.0503 (16)	0.0502 (15)	0.0011 (13)	0.0076 (14)	0.0104 (14)
C46	0.0532 (16)	0.0472 (15)	0.0469 (15)	−0.0046 (12)	0.0003 (12)	−0.0003 (13)

S1—C1	1.674 (2)	C7—C8	1.392 (3)
Cl1—C10	1.740 (2)	C7—C12	1.393 (3)
N1—C1	1.327 (3)	C8—C9	1.383 (3)
N1—C2	1.459 (3)	C8—H8	0.9300
N1—H1N	0.874 (10)	C9—C10	1.372 (4)
N2—C1	1.361 (3)	C9—H9	0.9300
N2—N3	1.376 (2)	C10—C11	1.373 (4)
N2—H2N	0.878 (10)	C11—C12	1.384 (3)
N3—C4	1.296 (2)	C11—H11	0.9300
C2—C3	1.484 (4)	C12—H12	0.9300
C2—H2A	0.9700	C41—C42	1.388 (3)
C2—H2B	0.9700	C41—C46	1.389 (3)
C3—H3A	0.9600	C42—C43	1.380 (3)
C3—H3B	0.9600	C42—H42	0.9300
C3—H3C	0.9600	C43—C44	1.370 (3)
C4—C5	1.450 (3)	C43—H43	0.9300
C4—C41	1.488 (3)	C44—C45	1.375 (4)
C5—C6	1.330 (3)	C44—H44	0.9300
C5—H5	0.9300	C45—C46	1.379 (3)
C6—C7	1.466 (3)	C45—H45	0.9300
C6—H6	0.9300	C46—H46	0.9300
C1—N1—C2	124.9 (2)	C9—C8—C7	121.6 (2)
C1—N1—H1N	119.5 (17)	C9—C8—H8	119.2
C2—N1—H1N	115.1 (17)	C7—C8—H8	119.2
C1—N2—N3	120.56 (18)	C10—C9—C8	118.7 (2)
C1—N2—H2N	115.5 (16)	C10—C9—H9	120.6
N3—N2—H2N	123.6 (16)	C8—C9—H9	120.6
C4—N3—N2	117.15 (18)	C9—C10—C11	121.3 (2)
N1—C1—N2	115.3 (2)	C9—C10—Cl1	119.1 (2)
N1—C1—S1	125.86 (17)	C11—C10—Cl1	119.6 (2)
N2—C1—S1	118.80 (17)	C10—C11—C12	119.8 (2)
N1—C2—C3	112.0 (2)	C10—C11—H11	120.1
N1—C2—H2A	109.2	C12—C11—H11	120.1
C3—C2—H2A	109.2	C11—C12—C7	120.4 (2)
N1—C2—H2B	109.2	C11—C12—H12	119.8
C3—C2—H2B	109.2	C7—C12—H12	119.8
H2A—C2—H2B	107.9	C42—C41—C46	118.9 (2)
C2—C3—H3A	109.5	C42—C41—C4	120.5 (2)
C2—C3—H3B	109.5	C46—C41—C4	120.7 (2)
H3A—C3—H3B	109.5	C43—C42—C41	120.3 (2)
C2—C3—H3C	109.5	C43—C42—H42	119.8
H3A—C3—H3C	109.5	C41—C42—H42	119.8
H3B—C3—H3C	109.5	C44—C43—C42	120.2 (2)
N3—C4—C5	115.73 (19)	C44—C43—H43	119.9
N3—C4—C41	123.63 (19)	C42—C43—H43	119.9
C5—C4—C41	120.64 (18)	C43—C44—C45	120.1 (2)
C6—C5—C4	124.7 (2)	C43—C44—H44	119.9
C6—C5—H5	117.6	C45—C44—H44	119.9
C4—C5—H5	117.6	C44—C45—C46	120.2 (2)
C5—C6—C7	126.8 (2)	C44—C45—H45	119.9
C5—C6—H6	116.6	C46—C45—H45	119.9
C7—C6—H6	116.6	C45—C46—C41	120.2 (2)
C8—C7—C12	118.1 (2)	C45—C46—H46	119.9
C8—C7—C6	119.6 (2)	C41—C46—H46	119.9
C12—C7—C6	122.3 (2)
C1—N2—N3—C4	179.6 (2)	C9—C10—C11—C12	0.5 (4)
C2—N1—C1—N2	−176.5 (2)	Cl1—C10—C11—C12	−179.8 (2)
C2—N1—C1—S1	3.9 (4)	C10—C11—C12—C7	0.3 (4)
N3—N2—C1—N1	−0.2 (4)	C8—C7—C12—C11	−1.2 (4)
N3—N2—C1—S1	179.39 (19)	C6—C7—C12—C11	178.8 (2)
C1—N1—C2—C3	87.9 (4)	N3—C4—C41—C42	−65.7 (3)
N2—N3—C4—C5	178.8 (2)	C5—C4—C41—C42	114.7 (2)
N2—N3—C4—C41	−0.9 (4)	N3—C4—C41—C46	114.5 (3)
N3—C4—C5—C6	173.2 (2)	C5—C4—C41—C46	−65.2 (3)
C41—C4—C5—C6	−7.1 (4)	C46—C41—C42—C43	0.0 (3)
C4—C5—C6—C7	−179.0 (2)	C4—C41—C42—C43	−179.9 (2)
C5—C6—C7—C8	152.8 (2)	C41—C42—C43—C44	0.3 (3)
C5—C6—C7—C12	−27.2 (4)	C42—C43—C44—C45	−0.4 (4)
C12—C7—C8—C9	1.3 (3)	C43—C44—C45—C46	0.1 (4)
C6—C7—C8—C9	−178.7 (2)	C44—C45—C46—C41	0.2 (4)
C7—C8—C9—C10	−0.4 (4)	C42—C41—C46—C45	−0.2 (3)
C8—C9—C10—C11	−0.5 (4)	C4—C41—C46—C45	179.6 (2)
C8—C9—C10—Cl1	179.87 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···N3	0.88 (2)	2.25 (2)	2.629 (3)	106 (2)
N1—H1N···S1i	0.88 (2)	2.84 (2)	3.693 (2)	165 (2)
C43—H43···Cl1ii	0.93	2.82	3.708 (3)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯N3	0.88 (2)	2.25 (2)	2.629 (3)	106 (2)
N1—H1N⋯S1i	0.88 (2)	2.84 (2)	3.693 (2)	165 (2)
C43—H43⋯Cl1ii	0.93	2.82	3.708 (3)	160

Symmetry codes: (i) ; (ii) .