Dichlorido{(2E)-2-[phen­yl(pyridin-2-yl)methyl­idene]hydrazinecarbo­thio­amide}cadmium(II) methanol monosolvate

Ambili A Aravindakshan; V Seena; M Sithambaresan; M R Prathapachandra Kurup

doi:10.1107/S1600536814015694

. 2014 Jul 17;70(Pt 8):m301–m302. doi: 10.1107/S1600536814015694

Dichlorido{(2E)-2-[phenyl(pyridin-2-yl)methylidene]hydrazinecarbothioamide}cadmium(II) methanol monosolvate

Ambili A Aravindakshan ^a, V Seena ^a, M Sithambaresan ^b,^*, M R Prathapachandra Kurup ^a

PMCID: PMC4158520 PMID: 25249883

Abstract

In the title compound, [CdCl₂(C₁₃H₁₂N₄S)]·CH₃OH, the coordination geometry of the Cd^II ion is slightly distorted square-pyramidal, as indicated by the τ index of 0.36 (8). The S atom, two N atoms from the pyridyl-azomethine moiety and one of the Cl atoms comprise the basal plane, while the other Cl atom occupies the apical position. The hydrazinecarbothioamide moiety adopts an E conformation with respect to the azomethine bond. The solvate molecule in the crystal lattice plays a major role in interconnecting adjacent molecules by means of O—H⋯Cl and N—H⋯O hydrogen-bonding interactions. A supramolecular three-dimensional architecture is sustained in terms of further N—H⋯Cl and C—H⋯Cl hydrogen-bonding interactions.

Keywords: crystal structure

Related literature

For metal complexes of hydrazinecarbothioamide and its derivatives, see: Sreekanth et al. (2004 ▶). For applications of hydrazinecarbothioamides, see: Joseph et al. (2004 ▶); Kumar et al. (2011 ▶, 2013 ▶). For the synthesis of related compounds, see: Philip et al. (2006 ▶). For related structures, see: Kunnath et al. (2012 ▶). For the calculation of the τ index, see: Addison et al. (1984 ▶).

Experimental

Crystal data

[CdCl₂(C₁₃H₁₂N₄S)]·CH₄O
M _r = 471.67
Monoclinic,
a = 7.7213 (4) Å
b = 12.9759 (8) Å
c = 18.3318 (11) Å
β = 95.248 (2)°
V = 1828.98 (18) Å³
Z = 4
Mo Kα radiation
μ = 1.61 mm⁻¹
T = 293 K
0.30 × 0.25 × 0.20 mm

Data collection

Bruker Kappa APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2004 ▶) T _min = 0.624, T _max = 0.725
13483 measured reflections
4392 independent reflections
3804 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.028
wR(F ²) = 0.074
S = 0.99
4392 reflections
226 parameters
5 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.60 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: SHELXL2008 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶) and DIAMOND (Brandenburg, 2010 ▶); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008 ▶) and publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536814015694/fj2677sup1.cif

e-70-0m301-sup1.cif^{(420.6KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814015694/fj2677Isup2.hkl

e-70-0m301-Isup2.hkl^{(215.2KB, hkl)}

CCDC reference: 1012335

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
N4—H4A⋯O1S	0.85 (1)	2.14 (2)	2.890 (3)	148 (2)
N4—H4B⋯Cl2ⁱ	0.84 (1)	2.43 (1)	3.253 (2)	167 (3)
N3—H3′⋯O1S	0.88 (1)	2.15 (2)	2.924 (3)	147 (3)
O1S—H1′⋯Cl1ⁱⁱ	0.85 (1)	2.40 (2)	3.201 (3)	158 (4)
C2—H2⋯Cl1ⁱⁱⁱ	0.93	2.80	3.680 (3)	159

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

Acknowledgments

AAA is grateful to the Council for Scientific and Industrial Research, New Delhi, India for the award of a Senior Research Fellowship. MRPK thanks the University Grants Commission, New Delhi, for a UGC–BSR one-time grant to faculty. We thank the Sophisticated Analytical Instruments Facility, Cochin University of S & T, Kochi-22, India, for the diffraction measurements and FT–IR studies.

supplementary crystallographic information

S1. Comment

The importance of hydrazinecarbothioamide is increasing in various fields due to its wide range of medicinal applications (Joseph et al., 2004) and structural diversity due to their variable coordinative abilities (Sreekanth et al., 2004) arising from thioamido-thioiminol tautomerism. Moreover it also found to serve as a corrosion inhibitor on mild steel in HCl (Kumar et al., 2011). Recently a new heterocyclic hydrazinecarbothioamide has been developed as colorimetric and turn on fluorescent sensors for fluoride anion (Kumar et al., 2013).

The title complex [C₁₃H₁₂CdCl₂N₄S]·(CH₄O) adopts an E configuration with respect to C6═N2 bond and the tridentate ligand has its coordinating entities disposed in a cis fashion to each other (Fig. 1). The Cd atom in the complex is N,N^',S chelated by the thioamido form of the hydrazinecarbothioamide ligand. The C6═N2 [1.278 (3) Å] and C13=S1 [1.690 (2) Å] bond distances, very close to the formal C═N and C═S bond lengths respectively confirm the azomethine bond formation and the coordination via thioamido form. The coordination geometry around Cd(II) ion is almost square pyramidal (Addison et al., 1984) with a slight distortion (τ = 0.36 (8)). The S1 atom of the hydrazinecarbothioamide moiety, the imino N2 atom, pyridine N1 atom and the Cl1 atom comprise the basal plane while the apical position is occupied by the Cl2 atom (Kunnath et al., 2012). However, the deviation from the ideal square pyramidal geometry is observed by the displacement of Cd atom from the basal plane and the trans angle of the basal atoms (Table 1).

There are four classical O–H···Cl, N–H···O and N–H···Cl and one non-classical C–H···Cl intermolecular hydrogen bonding interactions (Table 1, Fig. 2). Three of the classical interactions connect two neighbouring complexes through a solvate molecule with D···A distances of 3.201 (3), 2.924 (3) and 2.890 (3) Å. The other two classical and non-classical interactions directly connect two more neighbouring molecules directly to the main molecule with D···A distances of 3.253 (2) and 3.680 (3) Å respectively. These hydrogen bonding interactions build a double layer (Fig. 3) supramolecular chain along c axis. In addition to this, there are two very weak π···π interactions present with Cg···Cg distances of greater than 4 Å. Fig. 4 shows the packing diagram of the title compound along a axis.

S2. Experimental

The potentialy tridentate ligand (2E)-2-[phenyl(pyridin-2-yl)methylidene]hydrazinecarbothioamide was synthesized in situ by mixing equimolar methanolic solutions of phenyl(pyridin-2-yl)methanone (0.0916 g, 0.5 mmol), hydrazinecarbothioamide (0.0455 g, 0.5 mmol) and 5 drops of glacial acetic acid for 2 h. The title complex was prepared by adapting a reported procedure (Philip et al., 2006) by refluxing the above ligand solution and CdCl₂·2.5H₂O (0.1141 g, 0.5 mmol) for 3 h. The resulting solution was cooled at room temperature. Upon slow evaporation, yellow coloured product formed were collected, washed with few drops of methanol and dried over P₄O₁₀in vacuo. Yellow blocked shaped single crystals of the title compound suitable for X-ray analysis were obtained by recrystallization from methanol. The compound was obtained in 56%, yield (0.1320 g).

IR (KBr, \v in cm^-1): 3439, 3225, 3125, 1603, 1380, 1314, 1213, 1147, 780, 659, 560.