(E)-4-(Benz­yloxy)benzaldehyde thio­semicarbazone

M T H Tarafder; M A A A A Islam; K A Crouse; Suchada Chantrapromma; Hoong-Kun Fun

doi:10.1107/S1600536808012671

. 2008 May 3;64(Pt 6):o988–o989. doi: 10.1107/S1600536808012671

(E)-4-(Benzyloxy)benzaldehyde thiosemicarbazone

M T H Tarafder ^a,^*, M A A A A Islam ^b, K A Crouse ^c, Suchada Chantrapromma ^d,^‡, Hoong-Kun Fun ^e,^§

PMCID: PMC2961576 PMID: 21202714

Abstract

In the title compound, C₁₅H₁₅N₃OS, the thiosemicarbazone group adopts an E configuration with respect to the C=N bond. The benzaldehyde thiosemicarbazone fragment is almost planar [maximum deviation = 0.012 (1) Å], while the dihedral angle between the benzyloxy and phenyl rings is 72.48 (5)°. In the crystal structure, molecules are interconnected by N—H⋯N and N—H⋯S hydrogen bonds, forming a two-dimensional network parallel to the bc plane and are further stacked along the a axis by π–π interactions [centroid–centroid separation 3.9043 (7) Å]. The crystal structure is also stabilized by C—H⋯π interactions.

Related literature

For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For bond-length data, see: Allen et al. (1987 ▶). For related structures of thiosemicarbazones, see, for example: John et al. (2003 ▶); Joseph et al. (2004 ▶). For applications and bioactivities of thiosemicarbazones, see, for example: Al-Awadi et al. (2008 ▶); Amoedo et al. (2006 ▶); Chandra et al., (2001 ▶); Demertzi et al. (2007 ▶); Kizilcikli et al. (2004 ▶); Mirsha et al. (2006 ▶); Offiong & Martelli (1997 ▶); Sing et al. (2001 ▶).

Experimental

Crystal data

C₁₅H₁₅N₃OS
M _r = 285.37
Monoclinic,
a = 11.0269 (1) Å
b = 12.6668 (2) Å
c = 10.8774 (1) Å
β = 116.099 (1)°
V = 1364.39 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 100.0 (1) K
0.42 × 0.31 × 0.23 mm

Data collection

Bruker SMART APEX2 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.792, T _max = 0.947
20710 measured reflections
3983 independent reflections
3517 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.096
S = 1.03
3983 reflections
193 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: APEX2 ; data reduction: SAINT (Bruker, 2005 ▶); program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808012671/sj2492sup1.cif

e-64-0o988-sup1.cif^{(18.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808012671/sj2492Isup2.hkl

e-64-0o988-Isup2.hkl^{(195.3KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H1N2⋯S1ⁱ	0.880 (16)	2.467 (16)	3.3403 (10)	171.9 (14)
N3—H1N3⋯N1	0.895 (19)	2.229 (18)	2.6104 (16)	105.2 (13)
N3—H1N3⋯S1ⁱⁱ	0.895 (19)	2.815 (17)	3.5285 (11)	137.7 (14)
C10—H10A⋯Cg1ⁱⁱⁱ	0.93	2.97	3.8325 (13)	154

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) . Cg1 is the centroid of the the C1–C6 ring.

Acknowledgments

KAC thanks Universiti Putra Malaysia for financial help. MTHT thanks the University of Rajshahi for the provision of laboratory facilities. The authors also thank Universiti Sains Malaysia for the Research University Golden Goose grant No. 1001/PFIZIK/811012.

supplementary crystallographic information

Comment

The chemistry of thiosemicarbazones have been of immense interest because these compounds provide intriguing chelating patterns, profound biomedical properties, structural diversity and ion-sensing abilities (Al-Awadi et al., 2008; Amoedo et al., 2006; Demertzi et al., 2007; Mirsha et al., 2006; Kizilcikli et al., 2004). Compounds of this type have been used as antibacterial, antifungal and antitumor agents (Sing et al., 2001; Offiong et al., 1997). Due to their long chain structure, they are very flexible and form linkages with a variety of metal ions (Chandra et al., 2001). It was advocated that their flexibility and bioactivity arise because of the presence of the imino group (–N=CH–) in addition to thioamino moities present in the skeleton of the molecule. The title thiosemicarbazone derivative (I) was synthesized and its crystal structure is reported here. (I) is likely to have biomedical properties similar to other nitrogen-sulfur donor ligands studied by our group.

In the title compound (Fig. 1), the thiosemicarbazone adopts an E conformation with a trans configuration observed about the C═N bond. The benzaldehydethiosemicarbazone fragment is almost planar, maximum deviation 0.012 (1) Å, with the dihedral angle between the hydrazinecarbothioamide unit (S1/N1/N2/N3/C15) and the C8–C13 phenyl ring being 6.59 (5)°. The orientation of the 4-benzyloxy group is indicated by the dihedral angle between the 4-benzyloxy and the C8–C13 phenyl rings being 72.48 (5)Å and the torsion angle C8–O1–C7–C6 of 165.49 (9)°. The C15═S1 and C15—N2 bond distances are typical of a C/db S double bond and a C—N single bond, respectively. The bond lengths and angles in (I) are within normal ranges (Allen et al., 1987) and show similar trends to those of previously reported thiosemicarbazones (John et al., 2003; Joseph et al., 2004). An intramolecular N3-H1N3···N1 hydrogen bond forms a five-membered N3-H1N3-N1—N2—C15 ring, producing an S(5) ring motif (Bernstein et al., 1995).

In the crystal packing (Fig. 2), molecules are interconnected by N—H···N and N—H···S hydrogen bonds (Table 1) into a two-dimensional network parallel to the bc plane and are further stacked along the a-axis by π···π interactions with the distances of Cg₁···Cg₂ = 3.9043 (7) Å: symmetry code x, 1/2 - y, -1/2 + z; Cg₁ and Cg₂ are the centroids of the C1–C6 and C8–C13 phenyl rings, respectively. The crystal also stabilized by C—H···π interactions (Table 1) involving the C1–C6 phenyl ring (centroid Cg₁).

Experimental

The title compound was synthesized by adding a solution of 4-benzyloxybenzaldehyde (2.12 g, 10 mmol) in ethanol (30 ml) to a hot solution of thiosemicarbazide (0.91 g, 10 mmol) in ethanol (100 ml). The mixture was refluxed for 2 hrs and subsequently cooled to room temperature. The light yellow precipitate of the title compound was separated by filtration, washed with ethanol and dried in vacuo over anhydrous CaCl₂. (Yield: 1.75 g, 61%), and was then dissolved in chloroform (0.11 g in 50 ml) and allowed to stand at room temperature (288–293 K) for 20 days. Yellow single crystals of the title compound were obtained after recrystallization from a solution of chloroform/toluene (30:7 v/v) after 12 days at room temperature, M.p 446 K.