organic compounds\(\def\hfill{\hskip 5em}\def\hfil{\hskip 3em}\def\eqno#1{\hfil {#1}}\)

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

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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.

3D view (loading...)
[Scheme 3D1]
Chemical scheme
[Scheme 1]

Structure description

In the title compound, Fig. 1[link], 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[Jacob, J. M. & Kurup, M. R. P. (2012). Acta Cryst. E68, o836-o837.]).

[Figure 1]
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[link] and Fig. 2[link]). 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[link]).

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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]
Figure 2
A view along the a axis of the crystal packing of the title compound. The hydrogen bonds (see Table 1[link]) 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[link]. 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]
Figure 3
Synthesis of the title compound.

Refinement

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

Table 2
Experimental details

Crystal data
Chemical formula C14H18ClN3OS
Mr 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)
V3) 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[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.])
Tmin, Tmax 0.786, 0.828
No. of measured, independent and observed [I > 2σ(I)] reflections 30649, 4824, 4127
Rint 0.020
(sin θ/λ)max−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
Δρmax, Δρmin (e Å−3) 0.39, −0.22
Computer programs: APEX2 and SAINT (Bruker, 2009[Bruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]), SHELXS2014 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]), SHELXL2014 (Sheldrick, 2015[Sheldrick, G. M. (2015). Acta Cryst. C71, 3-8.]), PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]), and publCIF (Westrip, 2010[Westrip, S. P. (2010). J. Appl. Cryst. 43, 920-925.]).

Structural data


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
C14H18ClN3OSZ = 2
Mr = 311.82F(000) = 328
Triclinic, P1Dx = 1.369 Mg m3
a = 5.9923 (1) ÅMo Kα radiation, λ = 0.71073 Å
b = 11.0704 (2) ÅCell parameters from 9894 reflections
c = 12.1128 (3) Åθ = 2.2–31.1°
α = 107.9815 (9)°µ = 0.39 mm1
β = 91.3414 (9)°T = 294 K
γ = 97.2061 (9)°Block, colourless
V = 756.60 (3) Å30.38 × 0.30 × 0.17 mm
Data collection top
Bruker APEXII CCD
diffractometer
4127 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tubeRint = 0.020
φ and ω scansθmax = 31.1°, θmin = 1.8°
Absorption correction: multi-scan
(SADABS; Bruker, 2009)
h = 88
Tmin = 0.786, Tmax = 0.828k = 1615
30649 measured reflectionsl = 1717
4824 independent reflections
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.053Hydrogen site location: mixed
wR(F2) = 0.130H atoms treated by a mixture of independent and constrained refinement
S = 1.12 w = 1/[σ2(Fo2) + (0.0404P)2 + 0.4563P]
where P = (Fo2 + 2Fc2)/3
4824 reflections(Δ/σ)max = 0.001
193 parametersΔρmax = 0.39 e Å3
0 restraintsΔρmin = 0.22 e Å3
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
xyzUiso*/Ueq
Cl11.32841 (10)0.60273 (5)0.57378 (5)0.05951 (16)
S10.06031 (8)0.65852 (5)0.18924 (5)0.04950 (15)
O10.8649 (3)1.05436 (14)0.65422 (15)0.0584 (4)
N10.6106 (2)0.73735 (13)0.39402 (13)0.0377 (3)
N20.4169 (3)0.74695 (15)0.33704 (14)0.0439 (4)
N30.4146 (3)0.54276 (14)0.21687 (14)0.0418 (3)
C11.0026 (3)0.73197 (15)0.53033 (15)0.0380 (3)
H1A0.94410.65530.47410.046*
C21.1981 (3)0.73946 (17)0.59555 (16)0.0407 (4)
C31.2937 (3)0.85327 (19)0.67687 (17)0.0454 (4)
H3A1.42930.85770.71790.054*
C41.1854 (3)0.96030 (18)0.69645 (16)0.0445 (4)
H4A1.24821.03730.75100.053*
C50.9830 (3)0.95343 (16)0.63494 (15)0.0391 (4)
C60.8924 (3)0.83966 (15)0.54870 (14)0.0344 (3)
C70.6881 (3)0.83640 (15)0.47930 (15)0.0374 (3)
H7A0.61270.90780.49740.045*
C80.3097 (3)0.64537 (16)0.24909 (15)0.0367 (3)
C90.3252 (3)0.42105 (15)0.12876 (15)0.0374 (3)
H9A0.23940.43980.06760.045*
C100.1685 (4)0.3369 (2)0.17991 (18)0.0513 (5)
H10A0.04240.38070.21110.062*
H10B0.24860.32030.24310.062*
C110.0815 (4)0.2101 (2)0.0864 (2)0.0643 (6)
H11A0.01380.15560.12060.077*
H11B0.00910.22650.02650.077*
C120.2755 (5)0.14128 (19)0.0318 (2)0.0639 (6)
H12A0.35840.11810.09020.077*
H12B0.21620.06310.02950.077*
C130.4329 (4)0.22641 (19)0.01810 (19)0.0550 (5)
H13A0.35340.24290.08150.066*
H13B0.55910.18260.04910.066*
C140.5210 (3)0.35397 (18)0.07495 (18)0.0477 (4)
H14A0.61260.33840.13490.057*
H14B0.61490.40850.04020.057*
H1N30.535 (4)0.548 (2)0.253 (2)0.051 (6)*
H1N20.351 (4)0.812 (2)0.361 (2)0.053 (6)*
H1O10.923 (5)1.112 (3)0.697 (2)0.067 (8)*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0599 (3)0.0476 (3)0.0755 (4)0.0236 (2)0.0016 (3)0.0198 (2)
S10.0411 (2)0.0433 (2)0.0526 (3)0.01215 (18)0.01336 (19)0.0029 (2)
O10.0620 (9)0.0332 (6)0.0643 (9)0.0163 (6)0.0218 (7)0.0092 (6)
N10.0354 (7)0.0336 (6)0.0385 (7)0.0079 (5)0.0034 (5)0.0025 (5)
N20.0418 (8)0.0345 (7)0.0455 (8)0.0131 (6)0.0099 (6)0.0037 (6)
N30.0386 (8)0.0326 (7)0.0442 (8)0.0073 (6)0.0103 (6)0.0024 (6)
C10.0413 (9)0.0304 (7)0.0391 (8)0.0071 (6)0.0004 (7)0.0056 (6)
C20.0425 (9)0.0381 (8)0.0437 (9)0.0122 (7)0.0023 (7)0.0135 (7)
C30.0428 (9)0.0497 (10)0.0425 (9)0.0089 (8)0.0074 (7)0.0125 (8)
C40.0482 (10)0.0399 (9)0.0374 (9)0.0035 (7)0.0102 (7)0.0025 (7)
C50.0438 (9)0.0315 (7)0.0375 (8)0.0080 (6)0.0032 (7)0.0039 (6)
C60.0352 (8)0.0315 (7)0.0331 (7)0.0060 (6)0.0014 (6)0.0048 (6)
C70.0373 (8)0.0304 (7)0.0397 (8)0.0079 (6)0.0031 (6)0.0031 (6)
C80.0343 (8)0.0337 (7)0.0359 (8)0.0053 (6)0.0025 (6)0.0022 (6)
C90.0380 (8)0.0299 (7)0.0375 (8)0.0031 (6)0.0052 (6)0.0017 (6)
C100.0534 (11)0.0471 (10)0.0459 (10)0.0019 (8)0.0056 (8)0.0068 (8)
C110.0676 (14)0.0500 (12)0.0622 (14)0.0190 (10)0.0030 (11)0.0095 (10)
C120.0915 (18)0.0315 (9)0.0574 (13)0.0017 (10)0.0096 (12)0.0026 (8)
C130.0571 (12)0.0421 (10)0.0514 (11)0.0067 (8)0.0023 (9)0.0060 (8)
C140.0416 (9)0.0368 (8)0.0520 (11)0.0021 (7)0.0031 (8)0.0031 (8)
Geometric parameters (Å, º) top
Cl1—C21.7408 (18)C6—C71.459 (2)
S1—C81.6880 (17)C7—H7A0.9300
O1—C51.360 (2)C9—C101.516 (3)
O1—H1O10.72 (3)C9—C141.520 (2)
N1—C71.279 (2)C9—H9A0.9800
N1—N21.369 (2)C10—C111.527 (3)
N2—C81.363 (2)C10—H10A0.9700
N2—H1N20.84 (2)C10—H10B0.9700
N3—C81.324 (2)C11—C121.522 (4)
N3—C91.465 (2)C11—H11A0.9700
N3—H1N30.82 (2)C11—H11B0.9700
C1—C21.377 (2)C12—C131.516 (3)
C1—C61.395 (2)C12—H12A0.9700
C1—H1A0.9300C12—H12B0.9700
C2—C31.383 (3)C13—C141.532 (3)
C3—C41.381 (3)C13—H13A0.9700
C3—H3A0.9300C13—H13B0.9700
C4—C51.390 (2)C14—H14A0.9700
C4—H4A0.9300C14—H14B0.9700
C5—C61.401 (2)
C5—O1—H1O1112 (2)C10—C9—C14111.40 (16)
C7—N1—N2115.26 (14)N3—C9—H9A108.3
C8—N2—N1121.03 (14)C10—C9—H9A108.3
C8—N2—H1N2117.6 (16)C14—C9—H9A108.3
N1—N2—H1N2120.8 (16)C9—C10—C11110.06 (17)
C8—N3—C9125.07 (15)C9—C10—H10A109.6
C8—N3—H1N3116.3 (16)C11—C10—H10A109.6
C9—N3—H1N3118.5 (16)C9—C10—H10B109.6
C2—C1—C6119.89 (15)C11—C10—H10B109.6
C2—C1—H1A120.1H10A—C10—H10B108.2
C6—C1—H1A120.1C12—C11—C10111.10 (19)
C1—C2—C3121.44 (16)C12—C11—H11A109.4
C1—C2—Cl1119.06 (14)C10—C11—H11A109.4
C3—C2—Cl1119.50 (14)C12—C11—H11B109.4
C4—C3—C2119.17 (17)C10—C11—H11B109.4
C4—C3—H3A120.4H11A—C11—H11B108.0
C2—C3—H3A120.4C13—C12—C11110.60 (18)
C3—C4—C5120.28 (16)C13—C12—H12A109.5
C3—C4—H4A119.9C11—C12—H12A109.5
C5—C4—H4A119.9C13—C12—H12B109.5
O1—C5—C4122.65 (16)C11—C12—H12B109.5
O1—C5—C6117.04 (15)H12A—C12—H12B108.1
C4—C5—C6120.31 (15)C12—C13—C14111.10 (18)
C1—C6—C5118.78 (15)C12—C13—H13A109.4
C1—C6—C7121.50 (14)C14—C13—H13A109.4
C5—C6—C7119.72 (14)C12—C13—H13B109.4
N1—C7—C6121.37 (15)C14—C13—H13B109.4
N1—C7—H7A119.3H13A—C13—H13B108.0
C6—C7—H7A119.3C9—C14—C13110.17 (16)
N3—C8—N2115.86 (15)C9—C14—H14A109.6
N3—C8—S1125.09 (13)C13—C14—H14A109.6
N2—C8—S1119.05 (13)C9—C14—H14B109.6
N3—C9—C10111.42 (15)C13—C14—H14B109.6
N3—C9—C14108.90 (14)H14A—C14—H14B108.1
C7—N1—N2—C8176.04 (17)C5—C6—C7—N1174.53 (17)
C6—C1—C2—C32.4 (3)C9—N3—C8—N2176.67 (17)
C6—C1—C2—Cl1178.29 (14)C9—N3—C8—S13.9 (3)
C1—C2—C3—C42.8 (3)N1—N2—C8—N35.5 (3)
Cl1—C2—C3—C4177.85 (16)N1—N2—C8—S1175.02 (14)
C2—C3—C4—C50.1 (3)C8—N3—C9—C1083.7 (2)
C3—C4—C5—O1177.23 (19)C8—N3—C9—C14153.00 (19)
C3—C4—C5—C63.0 (3)N3—C9—C10—C11179.08 (18)
C2—C1—C6—C50.8 (3)C14—C9—C10—C1157.2 (2)
C2—C1—C6—C7178.40 (17)C9—C10—C11—C1256.9 (3)
O1—C5—C6—C1176.81 (17)C10—C11—C12—C1356.7 (3)
C4—C5—C6—C13.4 (3)C11—C12—C13—C1456.4 (3)
O1—C5—C6—C74.0 (3)N3—C9—C14—C13179.75 (17)
C4—C5—C6—C7175.77 (17)C10—C9—C14—C1357.0 (2)
N2—N1—C7—C6179.48 (16)C12—C13—C14—C956.3 (3)
C1—C6—C7—N14.6 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H1N2···O1i0.84 (2)2.13 (2)2.915 (2)156 (2)
O1—H1O1···S1i0.73 (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

First citationBruker (2009). APEX2, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationJacob, J. M. & Kurup, M. R. P. (2012). Acta Cryst. E68, o836–o837.  CSD CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSheldrick, G. M. (2015). Acta Cryst. C71, 3–8.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationWestrip, S. P. (2010). J. Appl. Cryst. 43, 920–925.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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