Crystal structure of (E)-2-[(4-chloro-2H-chromen-3-yl)methyl-idene]-N-cyclo-hexyl-hydrazinecarbo-thio-amide.

In the title compound, C17H20ClN3OS, the mean plane of the central thio-urea core makes dihedral angles of 26.56 (9) and 47.62 (12)° with the mean planes of the chromene moiety and the cyclo-hexyl ring, respectively. The cyclo-hexyl ring adopts a chair conformation. The N-H atoms of the thio-urea unit adopt an anti conformation. The chromene group is positioned trans, whereas the cyclo-hexyl ring lies in the cis position to the thione S atom, with respect to the thio-urea C-N bond. In the crystal, mol-ecules are linked by N-H⋯S hydrogen bonds, forming inversion dimers enclosing R (2) 2(8) ring motifs. The dimers are linked by C-H⋯Cl hydrogen bonds, enclosing R (6) 6(44) ring motifs, forming sheets lying parallel to (010).

Related literature

For the biological properties of thio­semicarbazones, see: Prabhakaran et al. (2007 ▶); Kelly et al. (1996 ▶); West et al. (1993 ▶); Pérez et al. (1999 ▶). For their optical properties and applications, see: Tian et al. (1997 ▶); Uesugi et al. (1994 ▶). For a related structure, see: Jayakumar et al. (2011 ▶).

Experimental

Crystal data

C17H20ClN3OS

M = 349.87

Orthorhombic,

a = 12.2857 (12) Å

b = 15.3082 (16) Å

c = 18.5241 (18) Å

V = 3483.9 (6) Å3

Z = 8

Mo Kα radiation

μ = 0.35 mm−1

T = 296 K

0.30 × 0.25 × 0.20 mm

Data collection

Bruker SMART APEXII area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.901, T max = 0.933

18568 measured reflections

4291 independent reflections

2762 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.050

wR(F 2) = 0.152

S = 1.02

4291 reflections

208 parameters

H-atom parameters constrained

Δρmax = 0.32 e Å−3

Δρmin = −0.31 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814018509/su2769sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814018509/su2769Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814018509/su2769Isup3.cml

Click here for additional data file.

. DOI: 10.1107/S1600536814018509/su2769fig1.tif

The mol­ecular structure of the title mol­ecule, with atom labelling. The displacement ellipsoids are drawn at the 30% probability level.

Click here for additional data file.

a . DOI: 10.1107/S1600536814018509/su2769fig2.tif

The crystal packing of the title compound viewed along the a axis. The hydrogen bonds are shown as dashed lines (see Table 1 for details; H atoms not involved in hydrogen bonding have been omitted for clarity).

CCDC reference: 1016441

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

C17H20ClN3OS	F(000) = 1472
Mr = 349.87	Dx = 1.334 Mg m−3
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2762 reflections
a = 12.2857 (12) Å	θ = 2.2–28.3°
b = 15.3082 (16) Å	µ = 0.35 mm−1
c = 18.5241 (18) Å	T = 296 K
V = 3483.9 (6) Å3	Block, colourless
Z = 8	0.30 × 0.25 × 0.20 mm

Bruker SMART APEXII area-detector diffractometer	4291 independent reflections
Radiation source: fine-focus sealed tube	2762 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
ω and φ scans	θmax = 28.3°, θmin = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −15→16
Tmin = 0.901, Tmax = 0.933	k = −19→19
18568 measured reflections	l = −24→23

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)] = 0.050	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0745P)2 + 0.9377P] where P = (Fo2 + 2Fc2)/3
4291 reflections	(Δ/σ)max = 0.001
208 parameters	Δρmax = 0.32 e Å−3
0 restraints	Δρmin = −0.31 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
C1	1.1410 (2)	0.0421 (2)	0.35313 (15)	0.0735 (8)
H1	1.1134	0.0105	0.3144	0.088*
C2	1.2530 (2)	0.0541 (2)	0.36038 (19)	0.0835 (10)
H2	1.2997	0.0306	0.3259	0.100*
C3	1.2948 (2)	0.0990 (2)	0.41635 (19)	0.0824 (9)
H3	1.3698	0.1057	0.4205	0.099*
C4	1.2276 (2)	0.1348 (2)	0.46699 (17)	0.0790 (8)
H4	1.2568	0.1662	0.5054	0.095*
C5	1.11588 (18)	0.12440 (18)	0.46109 (13)	0.0600 (6)
C6	1.07055 (17)	0.07780 (15)	0.40441 (12)	0.0514 (5)
C7	0.95198 (17)	0.06950 (15)	0.40340 (11)	0.0485 (5)
C8	0.88960 (16)	0.10411 (14)	0.45507 (10)	0.0438 (5)
C9	0.94477 (19)	0.1572 (2)	0.51200 (14)	0.0712 (8)
H9A	0.9170	0.2164	0.5085	0.085*
H9B	0.9222	0.1345	0.5585	0.085*
C10	0.77399 (16)	0.08929 (15)	0.46230 (10)	0.0453 (5)
H10	0.7364	0.0579	0.4273	0.054*
C11	0.56710 (15)	0.10953 (15)	0.58999 (10)	0.0444 (5)
C12	0.59224 (15)	0.17836 (15)	0.71073 (10)	0.0423 (5)
H12	0.5665	0.1240	0.7327	0.051*
C13	0.50398 (19)	0.24676 (16)	0.71814 (12)	0.0563 (6)
H13A	0.4375	0.2255	0.6960	0.068*
H13B	0.5259	0.2995	0.6930	0.068*
C14	0.4829 (2)	0.2677 (2)	0.79728 (14)	0.0729 (8)
H14A	0.4279	0.3129	0.8007	0.087*
H14B	0.4555	0.2160	0.8215	0.087*
C15	0.5855 (2)	0.2981 (2)	0.83439 (14)	0.0733 (8)
H15A	0.6093	0.3527	0.8130	0.088*
H15B	0.5704	0.3087	0.8850	0.088*
C16	0.6747 (2)	0.2314 (2)	0.82767 (13)	0.0713 (8)
H16A	0.6547	0.1794	0.8546	0.086*
H16B	0.7410	0.2546	0.8486	0.086*
C17	0.69562 (17)	0.2068 (2)	0.74917 (12)	0.0645 (7)
H17A	0.7266	0.2566	0.7241	0.077*
H17B	0.7483	0.1597	0.7474	0.077*
N1	0.72378 (13)	0.11972 (13)	0.51739 (8)	0.0456 (4)
N2	0.61712 (13)	0.09549 (13)	0.52482 (8)	0.0481 (4)
H2A	0.5823	0.0721	0.4895	0.058*
N3	0.62011 (13)	0.16098 (12)	0.63520 (9)	0.0486 (4)
H3A	0.6769	0.1870	0.6185	0.058*
Cl1	0.89480 (7)	0.01105 (6)	0.33357 (4)	0.0936 (3)
O1	1.05307 (15)	0.16182 (18)	0.51223 (12)	0.1067 (9)
S1	0.44825 (4)	0.05982 (5)	0.60746 (3)	0.0645 (2)

	U11	U22	U33	U12	U13	U23
C1	0.0760 (17)	0.0745 (19)	0.0699 (15)	0.0181 (15)	0.0253 (13)	0.0081 (14)
C2	0.0698 (17)	0.086 (2)	0.095 (2)	0.0314 (16)	0.0410 (16)	0.0311 (19)
C3	0.0520 (14)	0.089 (2)	0.106 (2)	0.0117 (15)	0.0193 (15)	0.039 (2)
C4	0.0504 (13)	0.093 (2)	0.0933 (19)	−0.0055 (14)	0.0029 (13)	0.0141 (18)
C5	0.0483 (12)	0.0669 (16)	0.0649 (13)	−0.0009 (12)	0.0085 (10)	0.0079 (13)
C6	0.0532 (11)	0.0488 (13)	0.0523 (11)	0.0072 (10)	0.0149 (9)	0.0133 (10)
C7	0.0581 (12)	0.0446 (12)	0.0429 (10)	−0.0022 (10)	0.0071 (9)	−0.0021 (9)
C8	0.0481 (10)	0.0453 (12)	0.0381 (9)	−0.0035 (9)	0.0032 (8)	0.0006 (9)
C9	0.0466 (12)	0.100 (2)	0.0675 (15)	−0.0087 (13)	0.0033 (10)	−0.0310 (15)
C10	0.0467 (10)	0.0522 (13)	0.0370 (9)	−0.0054 (10)	0.0004 (8)	−0.0019 (9)
C11	0.0390 (9)	0.0516 (13)	0.0425 (9)	0.0002 (9)	0.0007 (7)	−0.0016 (10)
C12	0.0405 (9)	0.0481 (12)	0.0385 (9)	−0.0048 (9)	0.0027 (7)	−0.0014 (9)
C13	0.0556 (13)	0.0614 (16)	0.0519 (11)	0.0092 (12)	0.0019 (9)	−0.0019 (11)
C14	0.0633 (15)	0.092 (2)	0.0634 (14)	0.0143 (15)	0.0081 (12)	−0.0221 (15)
C15	0.0829 (18)	0.0764 (19)	0.0608 (14)	−0.0063 (16)	0.0083 (13)	−0.0251 (14)
C16	0.0611 (14)	0.097 (2)	0.0556 (13)	−0.0050 (15)	−0.0097 (11)	−0.0245 (14)
C17	0.0412 (11)	0.0898 (19)	0.0625 (13)	−0.0023 (12)	−0.0016 (10)	−0.0232 (14)
N1	0.0417 (8)	0.0540 (11)	0.0412 (8)	−0.0050 (8)	0.0034 (6)	0.0009 (8)
N2	0.0396 (8)	0.0637 (12)	0.0410 (8)	−0.0071 (8)	0.0016 (6)	−0.0058 (8)
N3	0.0423 (8)	0.0598 (12)	0.0436 (8)	−0.0144 (8)	0.0096 (7)	−0.0081 (8)
Cl1	0.0938 (6)	0.1186 (7)	0.0683 (4)	−0.0167 (5)	0.0133 (3)	−0.0505 (4)
O1	0.0485 (10)	0.173 (3)	0.0992 (15)	−0.0152 (12)	0.0062 (9)	−0.0721 (16)
S1	0.0446 (3)	0.0870 (5)	0.0621 (4)	−0.0208 (3)	0.0102 (2)	−0.0205 (3)

C1—C2	1.395 (4)	C11—S1	1.678 (2)
C1—C6	1.397 (3)	C12—N3	1.465 (2)
C1—H1	0.9300	C12—C13	1.514 (3)
C2—C3	1.346 (5)	C12—C17	1.520 (3)
C2—H2	0.9300	C12—H12	0.9800
C3—C4	1.364 (4)	C13—C14	1.523 (3)
C3—H3	0.9300	C13—H13A	0.9700
C4—C5	1.387 (3)	C13—H13B	0.9700
C4—H4	0.9300	C14—C15	1.510 (4)
C5—O1	1.349 (3)	C14—H14A	0.9700
C5—C6	1.386 (3)	C14—H14B	0.9700
C6—C7	1.462 (3)	C15—C16	1.503 (4)
C7—C8	1.336 (3)	C15—H15A	0.9700
C7—Cl1	1.723 (2)	C15—H15B	0.9700
C8—C10	1.445 (3)	C16—C17	1.524 (3)
C8—C9	1.494 (3)	C16—H16A	0.9700
C9—O1	1.332 (3)	C16—H16B	0.9700
C9—H9A	0.9700	C17—H17A	0.9700
C9—H9B	0.9700	C17—H17B	0.9700
C10—N1	1.280 (3)	N1—N2	1.369 (2)
C10—H10	0.9300	N2—H2A	0.8600
C11—N3	1.321 (3)	N3—H3A	0.8600
C11—N2	1.372 (2)
C2—C1—C6	119.7 (3)	C13—C12—H12	108.6
C2—C1—H1	120.2	C17—C12—H12	108.6
C6—C1—H1	120.2	C12—C13—C14	110.75 (19)
C3—C2—C1	121.2 (3)	C12—C13—H13A	109.5
C3—C2—H2	119.4	C14—C13—H13A	109.5
C1—C2—H2	119.4	C12—C13—H13B	109.5
C2—C3—C4	120.3 (3)	C14—C13—H13B	109.5
C2—C3—H3	119.9	H13A—C13—H13B	108.1
C4—C3—H3	119.9	C15—C14—C13	111.2 (2)
C3—C4—C5	119.9 (3)	C15—C14—H14A	109.4
C3—C4—H4	120.0	C13—C14—H14A	109.4
C5—C4—H4	120.0	C15—C14—H14B	109.4
O1—C5—C6	121.4 (2)	C13—C14—H14B	109.4
O1—C5—C4	117.5 (3)	H14A—C14—H14B	108.0
C6—C5—C4	121.1 (2)	C16—C15—C14	111.2 (2)
C5—C6—C1	117.9 (2)	C16—C15—H15A	109.4
C5—C6—C7	117.04 (19)	C14—C15—H15A	109.4
C1—C6—C7	125.1 (2)	C16—C15—H15B	109.4
C8—C7—C6	121.9 (2)	C14—C15—H15B	109.4
C8—C7—Cl1	120.68 (17)	H15A—C15—H15B	108.0
C6—C7—Cl1	117.45 (16)	C15—C16—C17	111.7 (2)
C7—C8—C10	124.63 (19)	C15—C16—H16A	109.3
C7—C8—C9	117.47 (19)	C17—C16—H16A	109.3
C10—C8—C9	117.78 (18)	C15—C16—H16B	109.3
O1—C9—C8	119.0 (2)	C17—C16—H16B	109.3
O1—C9—H9A	107.6	H16A—C16—H16B	107.9
C8—C9—H9A	107.6	C12—C17—C16	112.15 (18)
O1—C9—H9B	107.6	C12—C17—H17A	109.2
C8—C9—H9B	107.6	C16—C17—H17A	109.2
H9A—C9—H9B	107.0	C12—C17—H17B	109.2
N1—C10—C8	119.37 (18)	C16—C17—H17B	109.2
N1—C10—H10	120.3	H17A—C17—H17B	107.9
C8—C10—H10	120.3	C10—N1—N2	116.28 (17)
N3—C11—N2	115.49 (17)	N1—N2—C11	118.36 (16)
N3—C11—S1	125.24 (15)	N1—N2—H2A	120.8
N2—C11—S1	119.25 (15)	C11—N2—H2A	120.8
N3—C12—C13	112.32 (17)	C11—N3—C12	126.76 (17)
N3—C12—C17	107.71 (16)	C11—N3—H3A	116.6
C13—C12—C17	110.98 (19)	C12—N3—H3A	116.6
N3—C12—H12	108.6	C9—O1—C5	123.1 (2)
C6—C1—C2—C3	0.5 (4)	C7—C8—C10—N1	174.1 (2)
C1—C2—C3—C4	−0.7 (5)	C9—C8—C10—N1	−1.8 (3)
C2—C3—C4—C5	0.4 (5)	N3—C12—C13—C14	−176.0 (2)
C3—C4—C5—O1	−179.4 (3)	C17—C12—C13—C14	−55.4 (3)
C3—C4—C5—C6	0.1 (4)	C12—C13—C14—C15	57.3 (3)
O1—C5—C6—C1	179.1 (3)	C13—C14—C15—C16	−56.7 (3)
C4—C5—C6—C1	−0.4 (4)	C14—C15—C16—C17	54.5 (3)
O1—C5—C6—C7	−1.3 (4)	N3—C12—C17—C16	176.9 (2)
C4—C5—C6—C7	179.3 (2)	C13—C12—C17—C16	53.6 (3)
C2—C1—C6—C5	0.1 (4)	C15—C16—C17—C12	−53.2 (3)
C2—C1—C6—C7	−179.5 (2)	C8—C10—N1—N2	−173.26 (19)
C5—C6—C7—C8	−0.8 (3)	C10—N1—N2—C11	165.58 (19)
C1—C6—C7—C8	178.8 (2)	N3—C11—N2—N1	13.0 (3)
C5—C6—C7—Cl1	−179.54 (18)	S1—C11—N2—N1	−165.46 (16)
C1—C6—C7—Cl1	0.1 (3)	N2—C11—N3—C12	−172.13 (19)
C6—C7—C8—C10	−171.9 (2)	S1—C11—N3—C12	6.2 (3)
Cl1—C7—C8—C10	6.7 (3)	C13—C12—N3—C11	−81.4 (3)
C6—C7—C8—C9	4.0 (3)	C17—C12—N3—C11	156.1 (2)
Cl1—C7—C8—C9	−177.36 (19)	C8—C9—O1—C5	3.6 (5)
C7—C8—C9—O1	−5.4 (4)	C6—C5—O1—C9	−0.3 (5)
C10—C8—C9—O1	170.8 (3)	C4—C5—O1—C9	179.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···S1i	0.86	2.73	3.507 (2)	151
C12—H12···Cl1ii	0.98	2.83	3.689 (2)	147

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯S1i	0.86	2.73	3.507 (2)	151
C12—H12⋯Cl1ii	0.98	2.83	3.689 (2)	147

Symmetry codes: (i) ; (ii) .