Crystal structure of 2-[(E)-4-benz­yloxy-2-hy­droxy­benzyl­idene]-N-cyclo­hexyl­hydrazinecarbo­thio­amide aceto­nitrile hemisolvate

N R Sajitha; M Sithambaresan; M R Prathapachandra Kurup

doi:10.1107/S1600536814017905

. 2014 Aug 9;70(Pt 9):o987–o988. doi: 10.1107/S1600536814017905

Crystal structure of 2-[(E)-4-benzyloxy-2-hydroxybenzylidene]-N-cyclohexylhydrazinecarbothioamide acetonitrile hemisolvate

N R Sajitha ^a, M Sithambaresan ^b,^*, M R Prathapachandra Kurup ^a

PMCID: PMC4186196 PMID: 25309295

Abstract

The asymmetric unit of the title compound, C₂₁H₂₅N₃O₂S·0.5C₂H₃N, contains two independent molecules with almost similar structural properties along with a solvent molecule of acetonitrile. The compound exists in the E conformation with respect to the azomethine C=N double bond. The hydrazinecarbothioamide moieties in both independent molecules are almost planar [maximum deviations of 0.013 (2) and 0.007 (2) Å]. The molecular conformation is stabilized in each case by an intramolecular N—H⋯N hydrogen bond. In the crystal, pairs of N—H⋯S hydrogen bonds link each of the independent molecules into inversion dimers. The dimers are interconnected by means of three C—H⋯π interactions.

Keywords: crystal structure, hydrazinecarbothioamide, hydrogen bonding, C—H⋯π interactions, antimicrobial applications

Related literature

For antimicrobial application, see: Joseph et al. (2004 ▶). For fluorescence activity, see: Kumar et al. (2013 ▶). For versatile coordination ability, see: Sreekanth et al. (2004 ▶). For the synthesis of related compounds, see: Jacob & Kurup (2012 ▶). For related structures, see: Seena et al. (2006 ▶); Jacob & Kurup (2012 ▶). graphic file with name e-70-0o987-scheme1.jpg

Experimental

Crystal data

2C₂₁H₂₅N₃O₂S·C₂H₃N
M _r = 808.07
Triclinic,
a = 10.5345 (4) Å
b = 10.8341 (4) Å
c = 21.8169 (10) Å
α = 97.241 (2)°
β = 92.120 (2)°
γ = 118.901 (2)°
V = 2148.72 (15) Å³
Z = 2
Mo Kα radiation
μ = 0.17 mm⁻¹
T = 296 K
0.50 × 0.20 × 0.18 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan SADABS (Bruker, 2004 ▶) T _min = 0.918, T _max = 0.942
15933 measured reflections
9260 independent reflections
6918 reflections with I > 2σ(I)
R _int = 0.018

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.136
S = 1.03
9260 reflections
540 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: APEX2 and SAINT (Bruker, 2004 ▶); data reduction: SAINT and XPREP (Bruker, 2004 ▶); 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 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97 and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) Global, I. DOI: 10.1107/S1600536814017905/bv2235sup1.cif

e-70-0o987-sup1.cif^{(45KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814017905/bv2235Isup2.hkl

e-70-0o987-Isup2.hkl^{(452.9KB, hkl)}

Click here for additional data file.^{(8.2KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814017905/bv2235Isup3.cml

Click here for additional data file.^{(1.7MB, tif)}

ORTEP E N . DOI: 10.1107/S1600536814017905/bv2235fig1.tif

ORTEP diagram of (E)-2-(4-benzyloxy-2-hydroxybenzylidene)-N-cyclohexylhydrazinecarbothioamide with 50% probability ellipsoids.

Click here for additional data file.^{(1.4MB, tif)}

21 25 3 2 2 3 . DOI: 10.1107/S1600536814017905/bv2235fig2.tif

Hydrogen-bond interactions of the title compound, [C₂₁H₂₅N₃O₂S]·0.5C₂H₃N.

Click here for additional data file.^{(2.4MB, tif)}

. DOI: 10.1107/S1600536814017905/bv2235fig3.tif

C—H⋯π interactions of the title compound.

Click here for additional data file.^{(2.9MB, tif)}

a . DOI: 10.1107/S1600536814017905/bv2235fig4.tif

Packing diagram of the title compound along a axis.

CCDC reference: 1017712

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N5—H5′⋯S2ⁱ	0.88 (1)	2.48 (1)	3.3495 (17)	173 (2)
N2—H2′⋯S1ⁱⁱ	0.87 (1)	2.44 (1)	3.3047 (16)	171 (2)
O2—H2A⋯N1	0.84 (1)	1.96 (2)	2.696 (2)	146 (3)
O4—H4′⋯N4	0.84 (1)	1.94 (2)	2.680 (2)	146 (2)
C12—H12⋯Cg1ⁱⁱⁱ	0.93	2.95	3.811 (2)	154
C20—H20B⋯Cg2^iv	0.96	2.87	3.715 (2)	146
C31—H31⋯Cg4^v	0.93	2.84	3.714 (2)	157

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

NRS thanks the Council of Scientific and Industrial Research (India) for a Junior Research Fellowship. MRPK thanks the University Grants Commission, New Delhi, India, for a UGC–BSR one-time grant to faculty. The authors thank the Sophisticated Analytical Instruments Facility, Cochin University of S & T, for the diffraction measurements and IR data.

supplementary crystallographic information

S1. Comment

Thiosemicarbazones are important class of compounds due to their antimicrobial activity (Joseph et al., 2004). They are also found to act as turn on fluorescent sensors for fluoride anion (Kumar et al., 2013). These compounds are important due to their ability to show versatile coordination abilities in complexes (Sreekanth et al., 2004). Here we present a new N4-substituted thioemicarbazone with interesting structural properties.

The asymmetric unit of the title compound consists of two independent molecules of the thiosemicarbazone and one acetonitrile molecule giving an overall ratio of thiosemicarbazone to acetonitrile to 2:1. The compound crystallizes into triclinic space group P-1. The geometric parameters of each molecule are almost identical. The molecules adopt E configuration with respect to C14—N1 and C35—N4 bonds which is confirmed by the C14/N1/N2/C15 and C35/N4/N5/C36 torsion angles of -177.55 (17)° and 175.50 (18)° respectively (Fig.1). The N1/N2/C15/S1 and N4/N5/C36/S2 torsion angles of 171.78 (3)° and -173.54 (4)° suggest that the thionyl atom S1 of the first molecule and S2 of the second molecule are located trans to azomethine nitrogens N1 and N4 respectively. The torsion angles -6.0 (3)° and 5.2 (3)° for N1/N2/C15/N3 and N4/N5/C36/N6 respectively confirm the cis configuration of N1 with respect to N3 and N4 with respect to N6.

The C14—N1 and C35—N4 bond distances [1.281 (2) and 1.278 (2) Å] are close to that of formal C═N bond [1.284 (3) Å] (Seena et al., 2006). Similarly the C15—S1 and C36—S2 bond distances [1.6835 (17) Å and 1.6824 (17) Å] are also close to that of formal C═S bond [1.68 (3) Å] (Jacob & Kurup, 2012). The hydrazine carbothioamide moieties in both molecules are almost planar with maximum deviation of 0.013 (2) Å for atom C15 and 0.007 (2) Å for C36 respectively from their least square planes. The cyclohexyl rings in both the molecules adopt chair conformation. The least square plane calculations show that the rings C1–C6/C8–C13 in one molecule and C22–C27/C29–C34 in the other molecule are twisted with a dihedral angles of 82.93 (120)° and 88.59 (12)° respectively.

Whilst one the molecules in the asymmetric unit has only one intramolecular hydrogen bond of the type O—H···N with D···A distance 2.696 (2) Å and one N—H···S type intermolecular hydrogen bonding interaction with D···A distance 3.3046 (18) Å, the other molecule has two types of intramolecular hydrogen bonds of O—H···N and N—H···N with D···A distances 2.680 (2) and 2.655 (3) Å respectively along with one type of N—H···S intermolecular hydrogen bonding with D···A distance 3.3495 (18) Å (Table 1). All these intermolecular interactions present in two asymmetric molecules build two centrosymmetric dimers in the crystal lattice (Fig 2). These dimers are interconnected by means of three C—H···π interactions with H···π distances of 2.95, 2.87 and 2.84 Å (Fig. 3). Fig 4 shows the packing of molecules along crystallographic a axis.

S2. Experimental

The preparation of the compound involves a two step process (Jacob & Kurup, 2012). In the first step, cyclohexylisothiocyanate (15 mmol, 2 ml) in 15 ml methanol and hydrazine hydrate (90 mmol, 4.3 ml) in 15 ml methanol were mixed and the resulting solution was stirred for an hour when the colourless product, N(4)-cyclohexylthiosemicarbazide formed was filtered, washed with methanol and dried in vacuo. In the second step, 4-benzyloxy-2-hydroxybenzaldehyde (0.2283 g, 1 mmol), dissolved in 15 ml acetonitrile was added to a solution of N(4)-cyclohexylthiosemicarbazide in 10 ml acetonitrile and the reaction mixture was refluxed for 3 hrs in acidic medium. The resultant solution was kept for one week to give yellow crystals of the compound (yield 51.59%, 0.1978 g)

IR (KBr, ν in cm^-1): 3400, 3130, 2985, 2929, 2851, 1627, 1599, 1540, 1505, 1224.