Crystal structure of (E)-N-phenyl-N′-[1-(thio­phen-2-yl)ethyl­idene]formo­hydrazide

C S Dileep; K R Raghavendra; N K Lokanath; K Ajay Kumar; M A Sridhar

doi:10.1107/S1600536814016511

. 2014 Aug 1;70(Pt 9):o928–o929. doi: 10.1107/S1600536814016511

Crystal structure of (E)-N-phenyl-N′-[1-(thiophen-2-yl)ethylidene]formohydrazide

C S Dileep ^a, K R Raghavendra ^b, N K Lokanath ^a, K Ajay Kumar ^c, M A Sridhar ^a,^*

PMCID: PMC4186119 PMID: 25309259

Abstract

In the title compound, C₁₃H₁₂N₂OS, the planes of the thiophene and phenyl rings are nearly perpendicular to each other, making a dihedral angle of 86.42 (12)°. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, forming a helical chain along the b-axis direction.

Keywords: crystal structure, thiophene derivative, hydrogen bonding

Related literature

For the biological activity of thiophene derivatives, see: Bondock et al. (2010 ▶); Bellina et al. (2007 ▶); Konstantinova et al. (2009 ▶); Al-Said et al. (2011 ▶). For the crystal structure of a similar compound, viz. (E)-N′-[1-(thiophen-2-yl)ethylidene]benzohydrazide, see: Shan et al. (2011 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₃H₁₂N₂OS
M _r = 244.32
Orthorhombic,
a = 5.4960 (7) Å
b = 11.0177 (13) Å
c = 20.249 (2) Å
V = 1226.1 (2) Å³
Z = 4
Cu Kα radiation
μ = 2.22 mm⁻¹
T = 296 K
0.25 × 0.22 × 0.20 mm

Data collection

Bruker X8 Proteum diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2013 ▶) T _min = 0.604, T _max = 0.662
6298 measured reflections
2010 independent reflections
1904 reflections with I > 2σ(I)
R _int = 0.042

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.102
S = 1.10
2010 reflections
165 parameters
H-atom parameters constrained
Δρ_max = 0.21 e Å⁻³
Δρ_min = −0.20 e Å⁻³
Absolute structure: Flack (1983 ▶), 805 Friedel pairs
Absolute structure parameter: 0.02 (2)

Data collection: APEX2 (Bruker, 2013 ▶); cell refinement: SAINT (Bruker, 2013 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814016511/is5369sup1.cif

e-70-0o928-sup1.cif^{(22KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814016511/is5369Isup2.hkl

e-70-0o928-Isup2.hkl^{(98.9KB, hkl)}

Click here for additional data file.^{(4.7KB, cml)}

Supporting information file. DOI: 10.1107/S1600536814016511/is5369Isup3.cml

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

ORTEP . DOI: 10.1107/S1600536814016511/is5369fig1.tif

ORTEP view of the molecule with the atom-labeling scheme. The displacement ellipsoids are drawn at the 50% probability level.

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

a . DOI: 10.1107/S1600536814016511/is5369fig2.tif

A molecular packing view of the title compound down the a-axis.

CCDC reference: 1014287

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
C1—H1⋯O1ⁱ	0.93	2.39	3.202 (3)	145

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The authors would like to thank the University of Mysore for providing the diffractometer facility under the Institution of Excellence. CSD would like to thank the University of Mysore for the award of an RFSMS fellowship under the head DV5/Physics/389/RFSMS/2009–2010/10.07.2012.

supplementary crystallographic information

S1. Comment

In medicinal chemistry, thiophene derivatives have been very well known for their therapeutic applications. Many thiophene derivatives have been developed as chemotherapeutic agents and are extensively used. Thiophene nucleus is one of the most important heterocycles exhibiting remarkable pharmacological activities. The great interest in the synthesis of thiophene derivatives due to their diverse biological and chemical properties. Thiophene, as a prominent structural motif, is found in numerous active compounds, which contain 5-membered heterocyclic structure have attracted a lot of interests in many fields, and its rich biological activity in medicinal chemistry owing to their biological properties. Thiophene and thiazole derivatives are known to possess interesting biological properties like anticancer (Bondock et al., 2010; Bellina et al., 2007; Konstantinova et al., 2009). Thiophene or benzothiophene moieties due to the well documented anti-cancer activity of these moieties to study their SAR and their anti-breast cancer activity (Al-Said et al., 2011). In view of their importance as discussed above, thiophene derivatives were taken for their conformational studies to get better structural activity correlation.

In the title compound (Fig. 1), the bond lengths do not show much variation in the core structure of the derivatives, and are similar to the standard values (Allen et al., 2002). The thiophene (S1/C1–C4) and phenyl (C8–C13) rings are nearly perpendicular with a dihedral angle of 86.42 (12)° between their mean planes. The bond lengths and bond angles do not show large deviations and are comparable with those reported for a similar structure (Shan et al., 2011). The conformation of the attachment of the thiophene and phenyl rings can also be characterized by torsion angles of (C4—C5—N1—N2), (C5—N1—N2—C8), (O1—C7—N2—C8) and (S1—C4—C5—C6) being 178.38, 127.73, 171.34 and -170.31°, respectively. The crystal structure has an intermolecular C—H···O hydrogen bond. The molecular packing viewed down the a axis is shown in Fig. 2.

S2. Experimental

A mixture of (E)-1-phenyl-2-[(1-thiophen-2-yl)ethylidene]hydrazine (0.176 mmol) were added to the Vilsmeier-Haack reagent prepared by drop-wise addition of POCl₃ (1.2 ml) in ice cooled DMF (5 ml). The mixture was stirred at 60–65 °C for 6 h. The progress of the reaction was monitored by TLC. After completion of the reaction, the mixture was poured into ice cold water, neutralized with NaHCO₃, the solid separated was filtered, washed with water and recrystallized from ethanol to get the compound in 93% yield.