(E)-2-(5-Chloro-2-hy­droxy­benzyl­idene)-N-cyclo­hexyl­hydrazine-1-carbo­thio­amide

Arafath, M.A.; Adam, F.; Razali, M.R.

doi:10.1107/S2414314616019970

organic compounds

IUCrDATA

ISSN: 2414-3146

Volume 2| Part 1| January 2017| x161997

https://doi.org/10.1107/S2414314616019970

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(E)-2-(5-Chloro-2-hydroxybenzylidene)-N-cyclohexylhydrazine-1-carbothioamide

Md. Azharul Arafath,^a Farook Adam ^a ^* and Mohd. R. Razali ^a

^aThe School of Chemical Sciences, Universiti Sains Malaysia (USM), Penang 11800, Malaysia
^*Correspondence e-mail: farookdr@gmail.com

Edited by H. Stoeckli-Evans, University of Neuchâtel, Switzerland (Received 29 November 2016; accepted 15 December 2016; online 6 January 2017)

In the title compound, C₁₄H₁₈ClN₃OS, the phenol ring is almost coplanar with the hydrazinecarbothioamide moiety, making a dihedral angle of 6.92 (8)°. The cyclohexane ring has a chair conformation and the conformation about the C=N bond is E. In the crystal, molecules are linked by N—H⋯O and O—H⋯S hydrogen bonds, forming inversion dimers with an R₂²(14) ring motif flanked by two R₂²(6) ring motifs. The dimers are linked by short Cl⋯Cl interactions, forming layers parallel to the ab plane.

Keywords: crystal structure; carbothioamide Schiff base; hydrazine-1-carbothioamide; hydrogen bonding; Cl⋯Cl interaction.

CCDC reference: 1420417

Structure description

In the title compound, Fig. 1, the phenol ring (C1–C6) is almost coplanar with the hydrazinecarbothioamide moiety (N1–N3/C8/S1), making a dihedral angle of 6.92 (8)°. The cyclohexane ring (C9–C14) has a chair conformation and the conformation about the C7=N1 bond is E. This arrangement is close to that observed in the very similar compound, (E)-2-(5-bromo-2-hydroxy-3-methoxybenzylidene)-N– cyclohexylhydrazine-1-carbothioamide (Jacob & Kurup, 2012 ).

Figure 1
The molecular structure of the title compound, showing the atom labelling. Displacement ellipsoids are drawn at the 30% probability level.

In the crystal, molecules are linked by N—H⋯O and O—H⋯S hydrogen bonds, forming inversion dimers with an $[R_{2}^{2}]$ (14) ring motif flanked by two $[R_{2}^{2}]$ (6) ring motifs (Table 1 and Fig. 2). The dimers are linked by short Cl⋯Cl(−x + 3, −y + 1, −z + 1) contacts of 3.381 (1) Å, forming layers parallel to the ab plane (Fig. 2).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯O1ⁱ	0.84 (2)	2.13 (2)	2.915 (2)	156 (2)
O1—H1O1⋯S1ⁱ	0.73 (3)	2.48 (3)	3.128 (2)	150 (3)
Symmetry code: (i) -x+1, -y+2, -z+1.

Figure 2
A view along the a axis of the crystal packing of the title compound. The hydrogen bonds (see Table 1

) and short Cl⋯Cl contacts are shown as black and red dashed lines, respectively.

Synthesis and crystallization

The synthesis of the title compound is illustrated in Fig. 3. To 2-hydroxy-5-chlorobenzaldehyde (0.783 g, 5 mmol) dissolved in 20 ml of methanol, was added 0.2 ml glacial acetic acid and the mixture was refluxed for 30 min. N-cyclohexylhydrazinecarbothioamide (0.866 g, 5 mmol) in 20 ml methanol was added dropwise to the mixture and the resulting colourless solution was refluxed for 4 h with stirring. The solution was then dried under reduced pressure overnight and the product that formed was washed with 5 ml n-hexane. The recovered product was dissolved in methanol for purification by recrystallization. Colourless crystals of the title compound, suitable for X-ray diffraction analysis, were obtained by slow evaporation of the solvent (yield 98%, m.p. 447–448 K).

Figure 3
Synthesis of the title compound.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₁₄H₁₈ClN₃OS
M_r	311.82
Crystal system, space group	Triclinic, P $[\overline{1}]$
Temperature (K)	294
a, b, c (Å)	5.9923 (1), 11.0704 (2), 12.1128 (3)
α, β, γ (°)	107.9815 (9), 91.3414 (9), 97.2061 (9)
V (Å³)	756.60 (3)
Z	2
Radiation type	Mo Kα
μ (mm⁻¹)	0.39
Crystal size (mm)	0.38 × 0.30 × 0.17

Data collection
Diffractometer	Bruker APEXII CCD
Absorption correction	Multi-scan (SADABS; Bruker, 2009 )
T_min, T_max	0.786, 0.828
No. of measured, independent and observed [I > 2σ(I)] reflections	30649, 4824, 4127
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.727

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.053, 0.130, 1.12
No. of reflections	4824
No. of parameters	193
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.22
Computer programs: APEX2 and SAINT (Bruker, 2009), SHELXS2014 (Sheldrick, 2008 ), SHELXTL (Sheldrick, 2008), SHELXL2014 (Sheldrick, 2015 ), PLATON (Spek, 2009 ), and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1420417

Crystal structure: contains datablocks I, global. DOI: https://doi.org/10.1107/S2414314616019970/su4104sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314616019970/su4104Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314616019970/su4104Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXS2014 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL2014 (Sheldrick, 2015), PLATON (Spek, 2009), and publCIF (Westrip, 2010).

(E)-2-(5-Chloro-2-hydroxybenzylidene)-N-cyclohexylhydrazine-1-carbothioamide top

Crystal data top

C₁₄H₁₈ClN₃OS	Z = 2
M_r = 311.82	F(000) = 328
Triclinic, P1	D_x = 1.369 Mg m⁻³
a = 5.9923 (1) Å	Mo Kα radiation, λ = 0.71073 Å
b = 11.0704 (2) Å	Cell parameters from 9894 reflections
c = 12.1128 (3) Å	θ = 2.2–31.1°
α = 107.9815 (9)°	µ = 0.39 mm⁻¹
β = 91.3414 (9)°	T = 294 K
γ = 97.2061 (9)°	Block, colourless
V = 756.60 (3) Å³	0.38 × 0.30 × 0.17 mm

Data collection top

Bruker APEXII CCD diffractometer	4127 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.020
φ and ω scans	θ_max = 31.1°, θ_min = 1.8°
Absorption correction: multi-scan (SADABS; Bruker, 2009)	h = −8→8
T_min = 0.786, T_max = 0.828	k = −16→15
30649 measured reflections	l = −17→17
4824 independent reflections

Refinement top

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)] = 0.053	Hydrogen site location: mixed
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.12	w = 1/[σ²(F_o²) + (0.0404P)² + 0.4563P] where P = (F_o² + 2F_c²)/3
4824 reflections	(Δ/σ)_max = 0.001
193 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.22 e Å⁻³

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	1.32841 (10)	0.60273 (5)	0.57378 (5)	0.05951 (16)
S1	0.06031 (8)	0.65852 (5)	0.18924 (5)	0.04950 (15)
O1	0.8649 (3)	1.05436 (14)	0.65422 (15)	0.0584 (4)
N1	0.6106 (2)	0.73735 (13)	0.39402 (13)	0.0377 (3)
N2	0.4169 (3)	0.74695 (15)	0.33704 (14)	0.0439 (4)
N3	0.4146 (3)	0.54276 (14)	0.21687 (14)	0.0418 (3)
C1	1.0026 (3)	0.73197 (15)	0.53033 (15)	0.0380 (3)
H1A	0.9441	0.6553	0.4741	0.046*
C2	1.1981 (3)	0.73946 (17)	0.59555 (16)	0.0407 (4)
C3	1.2937 (3)	0.85327 (19)	0.67687 (17)	0.0454 (4)
H3A	1.4293	0.8577	0.7179	0.054*
C4	1.1854 (3)	0.96030 (18)	0.69645 (16)	0.0445 (4)
H4A	1.2482	1.0373	0.7510	0.053*
C5	0.9830 (3)	0.95343 (16)	0.63494 (15)	0.0391 (4)
C6	0.8924 (3)	0.83966 (15)	0.54870 (14)	0.0344 (3)
C7	0.6881 (3)	0.83640 (15)	0.47930 (15)	0.0374 (3)
H7A	0.6127	0.9078	0.4974	0.045*
C8	0.3097 (3)	0.64537 (16)	0.24909 (15)	0.0367 (3)
C9	0.3252 (3)	0.42105 (15)	0.12876 (15)	0.0374 (3)
H9A	0.2394	0.4398	0.0676	0.045*
C10	0.1685 (4)	0.3369 (2)	0.17991 (18)	0.0513 (5)
H10A	0.0424	0.3807	0.2111	0.062*
H10B	0.2486	0.3203	0.2431	0.062*
C11	0.0815 (4)	0.2101 (2)	0.0864 (2)	0.0643 (6)
H11A	−0.0138	0.1556	0.1206	0.077*
H11B	−0.0091	0.2265	0.0265	0.077*
C12	0.2755 (5)	0.14128 (19)	0.0318 (2)	0.0639 (6)
H12A	0.3584	0.1181	0.0902	0.077*
H12B	0.2162	0.0631	−0.0295	0.077*
C13	0.4329 (4)	0.22641 (19)	−0.01810 (19)	0.0550 (5)
H13A	0.3534	0.2429	−0.0815	0.066*
H13B	0.5591	0.1826	−0.0491	0.066*
C14	0.5210 (3)	0.35397 (18)	0.07495 (18)	0.0477 (4)
H14A	0.6126	0.3384	0.1349	0.057*
H14B	0.6149	0.4085	0.0402	0.057*
H1N3	0.535 (4)	0.548 (2)	0.253 (2)	0.051 (6)*
H1N2	0.351 (4)	0.812 (2)	0.361 (2)	0.053 (6)*
H1O1	0.923 (5)	1.112 (3)	0.697 (2)	0.067 (8)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0599 (3)	0.0476 (3)	0.0755 (4)	0.0236 (2)	−0.0016 (3)	0.0198 (2)
S1	0.0411 (2)	0.0433 (2)	0.0526 (3)	0.01215 (18)	−0.01336 (19)	−0.0029 (2)
O1	0.0620 (9)	0.0332 (6)	0.0643 (9)	0.0163 (6)	−0.0218 (7)	−0.0092 (6)
N1	0.0354 (7)	0.0336 (6)	0.0385 (7)	0.0079 (5)	−0.0034 (5)	0.0025 (5)
N2	0.0418 (8)	0.0345 (7)	0.0455 (8)	0.0131 (6)	−0.0099 (6)	−0.0037 (6)
N3	0.0386 (8)	0.0326 (7)	0.0442 (8)	0.0073 (6)	−0.0103 (6)	−0.0024 (6)
C1	0.0413 (9)	0.0304 (7)	0.0391 (8)	0.0071 (6)	−0.0004 (7)	0.0056 (6)
C2	0.0425 (9)	0.0381 (8)	0.0437 (9)	0.0122 (7)	0.0023 (7)	0.0135 (7)
C3	0.0428 (9)	0.0497 (10)	0.0425 (9)	0.0089 (8)	−0.0074 (7)	0.0125 (8)
C4	0.0482 (10)	0.0399 (9)	0.0374 (9)	0.0035 (7)	−0.0102 (7)	0.0025 (7)
C5	0.0438 (9)	0.0315 (7)	0.0375 (8)	0.0080 (6)	−0.0032 (7)	0.0039 (6)
C6	0.0352 (8)	0.0315 (7)	0.0331 (7)	0.0060 (6)	−0.0014 (6)	0.0048 (6)
C7	0.0373 (8)	0.0304 (7)	0.0397 (8)	0.0079 (6)	−0.0031 (6)	0.0031 (6)
C8	0.0343 (8)	0.0337 (7)	0.0359 (8)	0.0053 (6)	−0.0025 (6)	0.0022 (6)
C9	0.0380 (8)	0.0299 (7)	0.0375 (8)	0.0031 (6)	−0.0052 (6)	0.0017 (6)
C10	0.0534 (11)	0.0471 (10)	0.0459 (10)	−0.0019 (8)	0.0056 (8)	0.0068 (8)
C11	0.0676 (14)	0.0500 (12)	0.0622 (14)	−0.0190 (10)	0.0030 (11)	0.0095 (10)
C12	0.0915 (18)	0.0315 (9)	0.0574 (13)	−0.0017 (10)	−0.0096 (12)	0.0026 (8)
C13	0.0571 (12)	0.0421 (10)	0.0514 (11)	0.0067 (8)	0.0023 (9)	−0.0060 (8)
C14	0.0416 (9)	0.0368 (8)	0.0520 (11)	0.0021 (7)	0.0031 (8)	−0.0031 (8)

Geometric parameters (Å, º) top

Cl1—C2	1.7408 (18)	C6—C7	1.459 (2)
S1—C8	1.6880 (17)	C7—H7A	0.9300
O1—C5	1.360 (2)	C9—C10	1.516 (3)
O1—H1O1	0.72 (3)	C9—C14	1.520 (2)
N1—C7	1.279 (2)	C9—H9A	0.9800
N1—N2	1.369 (2)	C10—C11	1.527 (3)
N2—C8	1.363 (2)	C10—H10A	0.9700
N2—H1N2	0.84 (2)	C10—H10B	0.9700
N3—C8	1.324 (2)	C11—C12	1.522 (4)
N3—C9	1.465 (2)	C11—H11A	0.9700
N3—H1N3	0.82 (2)	C11—H11B	0.9700
C1—C2	1.377 (2)	C12—C13	1.516 (3)
C1—C6	1.395 (2)	C12—H12A	0.9700
C1—H1A	0.9300	C12—H12B	0.9700
C2—C3	1.383 (3)	C13—C14	1.532 (3)
C3—C4	1.381 (3)	C13—H13A	0.9700
C3—H3A	0.9300	C13—H13B	0.9700
C4—C5	1.390 (2)	C14—H14A	0.9700
C4—H4A	0.9300	C14—H14B	0.9700
C5—C6	1.401 (2)

C5—O1—H1O1	112 (2)	C10—C9—C14	111.40 (16)
C7—N1—N2	115.26 (14)	N3—C9—H9A	108.3
C8—N2—N1	121.03 (14)	C10—C9—H9A	108.3
C8—N2—H1N2	117.6 (16)	C14—C9—H9A	108.3
N1—N2—H1N2	120.8 (16)	C9—C10—C11	110.06 (17)
C8—N3—C9	125.07 (15)	C9—C10—H10A	109.6
C8—N3—H1N3	116.3 (16)	C11—C10—H10A	109.6
C9—N3—H1N3	118.5 (16)	C9—C10—H10B	109.6
C2—C1—C6	119.89 (15)	C11—C10—H10B	109.6
C2—C1—H1A	120.1	H10A—C10—H10B	108.2
C6—C1—H1A	120.1	C12—C11—C10	111.10 (19)
C1—C2—C3	121.44 (16)	C12—C11—H11A	109.4
C1—C2—Cl1	119.06 (14)	C10—C11—H11A	109.4
C3—C2—Cl1	119.50 (14)	C12—C11—H11B	109.4
C4—C3—C2	119.17 (17)	C10—C11—H11B	109.4
C4—C3—H3A	120.4	H11A—C11—H11B	108.0
C2—C3—H3A	120.4	C13—C12—C11	110.60 (18)
C3—C4—C5	120.28 (16)	C13—C12—H12A	109.5
C3—C4—H4A	119.9	C11—C12—H12A	109.5
C5—C4—H4A	119.9	C13—C12—H12B	109.5
O1—C5—C4	122.65 (16)	C11—C12—H12B	109.5
O1—C5—C6	117.04 (15)	H12A—C12—H12B	108.1
C4—C5—C6	120.31 (15)	C12—C13—C14	111.10 (18)
C1—C6—C5	118.78 (15)	C12—C13—H13A	109.4
C1—C6—C7	121.50 (14)	C14—C13—H13A	109.4
C5—C6—C7	119.72 (14)	C12—C13—H13B	109.4
N1—C7—C6	121.37 (15)	C14—C13—H13B	109.4
N1—C7—H7A	119.3	H13A—C13—H13B	108.0
C6—C7—H7A	119.3	C9—C14—C13	110.17 (16)
N3—C8—N2	115.86 (15)	C9—C14—H14A	109.6
N3—C8—S1	125.09 (13)	C13—C14—H14A	109.6
N2—C8—S1	119.05 (13)	C9—C14—H14B	109.6
N3—C9—C10	111.42 (15)	C13—C14—H14B	109.6
N3—C9—C14	108.90 (14)	H14A—C14—H14B	108.1

C7—N1—N2—C8	−176.04 (17)	C5—C6—C7—N1	174.53 (17)
C6—C1—C2—C3	−2.4 (3)	C9—N3—C8—N2	176.67 (17)
C6—C1—C2—Cl1	178.29 (14)	C9—N3—C8—S1	−3.9 (3)
C1—C2—C3—C4	2.8 (3)	N1—N2—C8—N3	−5.5 (3)
Cl1—C2—C3—C4	−177.85 (16)	N1—N2—C8—S1	175.02 (14)
C2—C3—C4—C5	−0.1 (3)	C8—N3—C9—C10	−83.7 (2)
C3—C4—C5—O1	177.23 (19)	C8—N3—C9—C14	153.00 (19)
C3—C4—C5—C6	−3.0 (3)	N3—C9—C10—C11	−179.08 (18)
C2—C1—C6—C5	−0.8 (3)	C14—C9—C10—C11	−57.2 (2)
C2—C1—C6—C7	178.40 (17)	C9—C10—C11—C12	56.9 (3)
O1—C5—C6—C1	−176.81 (17)	C10—C11—C12—C13	−56.7 (3)
C4—C5—C6—C1	3.4 (3)	C11—C12—C13—C14	56.4 (3)
O1—C5—C6—C7	4.0 (3)	N3—C9—C14—C13	−179.75 (17)
C4—C5—C6—C7	−175.77 (17)	C10—C9—C14—C13	57.0 (2)
N2—N1—C7—C6	179.48 (16)	C12—C13—C14—C9	−56.3 (3)
C1—C6—C7—N1	−4.6 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H1N2···O1ⁱ	0.84 (2)	2.13 (2)	2.915 (2)	156 (2)
O1—H1O1···S1ⁱ	0.73 (3)	2.48 (3)	3.128 (2)	150 (3)

Symmetry code: (i) −x+1, −y+2, −z+1.

Acknowledgements

This research was supported financially by the RU grant 1001/PKIMIA/811269 from University Sains Malaysia. The authors wish to thank Universiti Sains Malaysia and The World Academy of Science for a (TWAS–USM) fellowship to MAA who also wishes to acknowledge Shahjalal University of Science and Technology, Sylhet, Bangladesh, for study leave.

Funding information

Funding for this research was provided by: University Sains Malaysia (award No. 1001/PKIMIA/811269); The World Academy of Science

References

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