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

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 9| September 2014| Pages o928-o929

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

aDepartment of Studies in Physics, Manasagangotri, University of Mysore, Mysore 570 006, India, bDepartment of Chemistry, SBRR Mahajana College, Mysore 570 006, India, and cPost Graduate Department of Chemistry, Yuvaraja College, University of Mysore, Mysore 570 005, India
*Correspondence e-mail: mas@physics.uni-mysore.ac.in

Edited by H. Ishida, Okayama University, Japan (Received 9 July 2014; accepted 16 July 2014; online 1 August 2014)

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.

1. Related literature

For the biological activity of thio­phene derivatives, see: Bondock et al. (2010[Bondock, S., Fadaly, W. & Metwally, M. A. (2010). Eur. J. Med. Chem. 45, 3692-3701.]); Bellina et al. (2007[Bellina, F., Cauteruccio, S. & Rossi, R. (2007). Tetrahedron, 63, 4571-4624.]); Konstanti­nova et al. (2009[Konstantinova, L. S., Bolshakov, O. I., Obruchnikova, N. V., Laborie, H., Tanga, A., Sopena, V., Lanneluc, I., Picot, L., Sable, S., Thiery, V. & Rakitin, O. A. (2009). Bioorg. Med. Chem. Lett. 19, 136-141.]); Al-Said et al. (2011[Al-Said, M. S., Bashandy, M. S., Al-qasoumi, S. I. & Ghorab, M. M. (2011). Eur. J. Med. Chem. 46, 137-141.]). For the crystal structure of a similar compound, viz. (E)-N′-[1-(thio­phen-2-yl)ethyl­idene]benzohydrazide, see: Shan et al. (2011[Shan, S., Huang, Y.-L., Guo, H.-Q., Li, D.-F. & Sun, J. (2011). Acta Cryst. E67, o2498.]). For a description of the Cambridge Structural Database, see: Allen (2002[Allen, F. H. (2002). Acta Cryst. B58, 380-388.]).

[Scheme 1]

2. Experimental

2.1. Crystal data

  • C13H12N2OS

  • Mr = 244.32

  • Orthorhombic, P 21 21 21

  • 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

2.2. Data collection

  • Bruker X8 Proteum diffractometer

  • Absorption correction: multi-scan (SADABS; Bruker, 2013[Bruker (2013). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.604, Tmax = 0.662

  • 6298 measured reflections

  • 2010 independent reflections

  • 1904 reflections with I > 2σ(I)

  • Rint = 0.042

2.3. Refinement

  • R[F2 > 2σ(F2)] = 0.038

  • wR(F2) = 0.102

  • S = 1.10

  • 2010 reflections

  • 165 parameters

  • H-atom parameters constrained

  • Δρmax = 0.21 e Å−3

  • Δρmin = −0.20 e Å−3

  • Absolute structure: Flack (1983[Flack, H. D. (1983). Acta Cryst. A39, 876-881.]), 805 Friedel pairs

  • Absolute structure parameter: 0.02 (2)

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA D—H⋯A
C1—H1⋯O1i 0.93 2.39 3.202 (3) 145
Symmetry code: (i) [-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}].

Data collection: APEX2 (Bruker, 2013[Bruker (2013). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 2013[Bruker (2013). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: Mercury (Macrae et al., 2006[Macrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453-457.]); software used to prepare material for publication: PLATON (Spek, 2009[Spek, A. L. (2009). Acta Cryst. D65, 148-155.]).

Supporting information


Comment top

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.

Related literature top

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 top

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.

Refinement top

All H atoms were located from difference maps and were positioned geometrically and refined using a riding model with C—H = 0.93–0.96 Å and Uiso(H) = 1.2Ueq(C).

Computing details top

Data collection: APEX2 (Bruker, 2013); cell refinement: SAINT (Bruker, 2013); data reduction: SAINT (Bruker, 2013); 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).

Figures top
[Figure 1] Fig. 1. ORTEP view of the molecule with the atom-labeling scheme. The displacement ellipsoids are drawn at the 50% probability level.
[Figure 2] Fig. 2. A molecular packing view of the title compound down the a-axis.
(E)-N-Phenyl-N'-[1-(thiophen-2-yl)ethylidene]formohydrazide. top
Crystal data top
C13H12N2OSF(000) = 512
Mr = 244.32Dx = 1.324 Mg m3
Orthorhombic, P212121Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2abCell parameters from 6298 reflections
a = 5.4960 (7) Åθ = 4.4–64.6°
b = 11.0177 (13) ŵ = 2.22 mm1
c = 20.249 (2) ÅT = 296 K
V = 1226.1 (2) Å3Block, pale yellow
Z = 40.25 × 0.22 × 0.20 mm
Data collection top
Bruker X8 Proteum
diffractometer
2010 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode1904 reflections with I > 2σ(I)
Helios multilayer optics monochromatorRint = 0.042
Detector resolution: 10.7 pixels mm-1θmax = 64.6°, θmin = 4.4°
ϕ and ω scansh = 26
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
k = 1212
Tmin = 0.604, Tmax = 0.662l = 2322
6298 measured reflections
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.038 w = 1/[σ2(Fo2) + (0.0605P)2 + 0.0861P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.102(Δ/σ)max = 0.001
S = 1.10Δρmax = 0.21 e Å3
2010 reflectionsΔρmin = 0.20 e Å3
165 parametersExtinction correction: SHELXL, FC*=KFC[1+0.001XFC2Λ3/SIN(2Θ)]-1/4
0 restraintsExtinction coefficient: 0.0158 (16)
Primary atom site location: structure-invariant direct methodsAbsolute structure: Flack (1983), 805 Friedel pairs
Secondary atom site location: difference Fourier mapAbsolute structure parameter: 0.02 (2)
Crystal data top
C13H12N2OSV = 1226.1 (2) Å3
Mr = 244.32Z = 4
Orthorhombic, P212121Cu Kα radiation
a = 5.4960 (7) ŵ = 2.22 mm1
b = 11.0177 (13) ÅT = 296 K
c = 20.249 (2) Å0.25 × 0.22 × 0.20 mm
Data collection top
Bruker X8 Proteum
diffractometer
2010 independent reflections
Absorption correction: multi-scan
(SADABS; Bruker, 2013)
1904 reflections with I > 2σ(I)
Tmin = 0.604, Tmax = 0.662Rint = 0.042
6298 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.038H-atom parameters constrained
wR(F2) = 0.102Δρmax = 0.21 e Å3
S = 1.10Δρmin = 0.20 e Å3
2010 reflectionsAbsolute structure: Flack (1983), 805 Friedel pairs
165 parametersAbsolute structure parameter: 0.02 (2)
0 restraints
Special details top

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top
xyzUiso*/Ueq
S10.05502 (12)0.12455 (6)0.72104 (3)0.0539 (2)
O10.0434 (4)0.24121 (15)0.55887 (8)0.0526 (6)
N10.0078 (3)0.00557 (16)0.59394 (8)0.0348 (5)
N20.0086 (3)0.04249 (15)0.52882 (8)0.0344 (5)
C10.0682 (6)0.1399 (3)0.79702 (12)0.0623 (10)
C20.2635 (6)0.0712 (3)0.80591 (13)0.0648 (10)
C30.3227 (5)0.0016 (2)0.74907 (11)0.0513 (8)
C40.1639 (4)0.02325 (18)0.69777 (10)0.0358 (6)
C50.1724 (4)0.02503 (18)0.63061 (10)0.0331 (6)
C60.3905 (4)0.0972 (2)0.61062 (13)0.0509 (8)
C70.0373 (4)0.16179 (19)0.51733 (10)0.0410 (7)
C80.0373 (4)0.04484 (17)0.47710 (9)0.0325 (6)
C90.2273 (4)0.0366 (2)0.43330 (11)0.0397 (6)
C100.2429 (4)0.1192 (2)0.38203 (12)0.0479 (7)
C110.0710 (5)0.2091 (2)0.37516 (11)0.0469 (7)
C120.1151 (5)0.2185 (2)0.41975 (12)0.0463 (8)
C130.1322 (4)0.1365 (2)0.47156 (11)0.0413 (6)
H10.005600.191300.829300.0750*
H20.352000.068800.845000.0780*
H30.453000.052200.746800.0620*
H6A0.390600.107700.563600.0760*
H6B0.535500.055100.623800.0760*
H6C0.385400.175300.631700.0760*
H70.054200.185700.473500.0490*
H90.344100.023900.438000.0480*
H100.370600.114000.352000.0570*
H110.081300.263400.340100.0560*
H120.230100.279900.415300.0560*
H130.257200.143400.502300.0500*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0546 (4)0.0703 (5)0.0368 (3)0.0147 (3)0.0029 (3)0.0071 (3)
O10.0729 (11)0.0375 (9)0.0474 (9)0.0049 (8)0.0049 (8)0.0096 (7)
N10.0402 (10)0.0379 (9)0.0263 (8)0.0024 (8)0.0012 (7)0.0037 (6)
N20.0452 (10)0.0313 (8)0.0266 (8)0.0006 (8)0.0005 (7)0.0022 (7)
C10.085 (2)0.0689 (17)0.0330 (12)0.0037 (16)0.0059 (13)0.0095 (11)
C20.0757 (18)0.0819 (19)0.0368 (13)0.0055 (16)0.0152 (13)0.0000 (13)
C30.0524 (14)0.0590 (15)0.0426 (13)0.0041 (12)0.0127 (11)0.0022 (11)
C40.0373 (10)0.0370 (11)0.0332 (10)0.0038 (9)0.0009 (8)0.0026 (8)
C50.0317 (10)0.0314 (10)0.0362 (11)0.0037 (8)0.0030 (8)0.0008 (8)
C60.0372 (12)0.0564 (15)0.0592 (14)0.0111 (10)0.0008 (11)0.0119 (12)
C70.0511 (12)0.0353 (11)0.0366 (11)0.0020 (9)0.0024 (10)0.0018 (9)
C80.0388 (10)0.0296 (10)0.0291 (9)0.0017 (8)0.0051 (8)0.0012 (8)
C90.0355 (10)0.0392 (11)0.0444 (12)0.0049 (9)0.0011 (9)0.0016 (10)
C100.0456 (12)0.0511 (13)0.0469 (13)0.0056 (11)0.0089 (10)0.0094 (11)
C110.0604 (14)0.0365 (11)0.0439 (12)0.0080 (11)0.0054 (11)0.0088 (9)
C120.0536 (14)0.0350 (12)0.0503 (13)0.0084 (11)0.0087 (11)0.0024 (10)
C130.0429 (11)0.0416 (11)0.0395 (11)0.0083 (10)0.0012 (10)0.0035 (10)
Geometric parameters (Å, º) top
S1—C11.690 (3)C10—C111.376 (3)
S1—C41.707 (2)C11—C121.368 (4)
O1—C71.214 (3)C12—C131.388 (3)
N1—N21.421 (2)C1—H10.9300
N1—C51.283 (3)C2—H20.9300
N2—C71.344 (3)C3—H30.9300
N2—C81.431 (2)C6—H6A0.9600
C1—C21.326 (5)C6—H6B0.9600
C2—C31.421 (4)C6—H6C0.9600
C3—C41.378 (3)C7—H70.9300
C4—C51.461 (3)C9—H90.9300
C5—C61.494 (3)C10—H100.9300
C8—C91.373 (3)C11—H110.9300
C8—C131.379 (3)C12—H120.9300
C9—C101.383 (3)C13—H130.9300
C1—S1—C491.96 (13)C2—C1—H1123.00
N2—N1—C5116.20 (17)C1—C2—H2124.00
N1—N2—C7121.70 (16)C3—C2—H2124.00
N1—N2—C8115.40 (15)C2—C3—H3124.00
C7—N2—C8121.19 (16)C4—C3—H3124.00
S1—C1—C2113.0 (2)C5—C6—H6A109.00
C1—C2—C3112.6 (2)C5—C6—H6B109.00
C2—C3—C4111.9 (2)C5—C6—H6C109.00
S1—C4—C3110.58 (16)H6A—C6—H6B109.00
S1—C4—C5121.16 (16)H6A—C6—H6C109.00
C3—C4—C5128.2 (2)H6B—C6—H6C109.00
N1—C5—C4114.73 (19)O1—C7—H7117.00
N1—C5—C6127.04 (19)N2—C7—H7117.00
C4—C5—C6118.13 (19)C8—C9—H9120.00
O1—C7—N2126.02 (19)C10—C9—H9120.00
N2—C8—C9120.81 (18)C9—C10—H10120.00
N2—C8—C13118.53 (18)C11—C10—H10120.00
C9—C8—C13120.65 (19)C10—C11—H11120.00
C8—C9—C10119.2 (2)C12—C11—H11120.00
C9—C10—C11120.5 (2)C11—C12—H12120.00
C10—C11—C12120.1 (2)C13—C12—H12120.00
C11—C12—C13120.0 (2)C8—C13—H13120.00
C8—C13—C12119.5 (2)C12—C13—H13120.00
S1—C1—H1124.00
C4—S1—C1—C20.9 (3)C2—C3—C4—C5176.1 (2)
C1—S1—C4—C31.3 (2)C2—C3—C4—S11.4 (3)
C1—S1—C4—C5176.4 (2)S1—C4—C5—N16.3 (3)
C5—N1—N2—C767.0 (2)C3—C4—C5—N1176.4 (2)
C5—N1—N2—C8127.7 (2)C3—C4—C5—C67.0 (3)
N2—N1—C5—C4178.38 (16)S1—C4—C5—C6170.31 (16)
N2—N1—C5—C65.3 (3)N2—C8—C9—C10176.94 (19)
C7—N2—C8—C13135.3 (2)C13—C8—C9—C102.1 (3)
N1—N2—C7—O16.9 (3)N2—C8—C13—C12176.7 (2)
C8—N2—C7—O1171.3 (2)C9—C8—C13—C122.3 (3)
N1—N2—C8—C9121.6 (2)C8—C9—C10—C110.4 (3)
C7—N2—C8—C943.7 (3)C9—C10—C11—C121.0 (4)
N1—N2—C8—C1359.4 (2)C10—C11—C12—C130.7 (4)
S1—C1—C2—C30.3 (4)C11—C12—C13—C80.9 (3)
C1—C2—C3—C40.7 (4)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O1i0.932.393.202 (3)145
Symmetry code: (i) x, y+1/2, z+3/2.
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
C1—H1···O1i0.932.393.202 (3)145
Symmetry code: (i) x, y+1/2, z+3/2.
 

Acknowledgements

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.

References

First citationAllen, F. H. (2002). Acta Cryst. B58, 380–388.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationAl-Said, M. S., Bashandy, M. S., Al-qasoumi, S. I. & Ghorab, M. M. (2011). Eur. J. Med. Chem. 46, 137–141.  Web of Science CAS PubMed Google Scholar
First citationBellina, F., Cauteruccio, S. & Rossi, R. (2007). Tetrahedron, 63, 4571–4624.  Web of Science CrossRef CAS Google Scholar
First citationBondock, S., Fadaly, W. & Metwally, M. A. (2010). Eur. J. Med. Chem. 45, 3692–3701.  Web of Science CrossRef CAS PubMed Google Scholar
First citationBruker (2013). APEX2, SADABS and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationFlack, H. D. (1983). Acta Cryst. A39, 876–881.  CrossRef CAS Web of Science IUCr Journals Google Scholar
First citationKonstantinova, L. S., Bolshakov, O. I., Obruchnikova, N. V., Laborie, H., Tanga, A., Sopena, V., Lanneluc, I., Picot, L., Sable, S., Thiery, V. & Rakitin, O. A. (2009). Bioorg. Med. Chem. Lett. 19, 136–141.  Web of Science CrossRef PubMed CAS Google Scholar
First citationMacrae, C. F., Edgington, P. R., McCabe, P., Pidcock, E., Shields, G. P., Taylor, R., Towler, M. & van de Streek, J. (2006). J. Appl. Cryst. 39, 453–457.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationShan, S., Huang, Y.-L., Guo, H.-Q., Li, D.-F. & Sun, J. (2011). Acta Cryst. E67, o2498.  Web of Science CSD CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar
First citationSpek, A. L. (2009). Acta Cryst. D65, 148–155.  Web of Science CrossRef CAS IUCr Journals Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

Journal logoCRYSTALLOGRAPHIC
COMMUNICATIONS
ISSN: 2056-9890
Volume 70| Part 9| September 2014| Pages o928-o929
Follow Acta Cryst. E
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds