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

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

doi:10.1107/S1600536814016511

organic compounds

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doi:10.1107/S1600536814016511

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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 and M. A. Sridhar ^a ^*

^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.

Keywords: crystal structure; thiophene derivative; hydrogen bonding.

CCDC reference: 1014287

1. 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 ).

2. Experimental

2.1. Crystal data

C₁₃H₁₂N₂OS
M_r = 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 ) T_min = 0.604, T_max = 0.662
6298 measured reflections
2010 independent reflections
1904 reflections with I > 2σ(I)
R_int = 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
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)

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
Symmetry code: (i) $[-x, y+{\script{1\over 2}}, -z+{\script{3\over 2}}]$ .

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 ).

Supporting information

CCDC reference: 1014287

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536814016511/is5369sup1.cif

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

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

checkCIF report

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.

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

	Fig. 1. ORTEP view of the molecule with the atom-labeling scheme. The displacement ellipsoids are drawn at the 50% probability level.
	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

C₁₃H₁₂N₂OS	F(000) = 512
M_r = 244.32	D_x = 1.324 Mg m⁻³
Orthorhombic, P2₁2₁2₁	Cu Kα radiation, λ = 1.54178 Å
Hall symbol: P 2ac 2ab	Cell parameters from 6298 reflections
a = 5.4960 (7) Å	θ = 4.4–64.6°
b = 11.0177 (13) Å	µ = 2.22 mm⁻¹
c = 20.249 (2) Å	T = 296 K
V = 1226.1 (2) Å³	Block, pale yellow
Z = 4	0.25 × 0.22 × 0.20 mm

Data collection top

Bruker X8 Proteum diffractometer	2010 independent reflections
Radiation source: Bruker MicroStar microfocus rotating anode	1904 reflections with I > 2σ(I)
Helios multilayer optics monochromator	R_int = 0.042
Detector resolution: 10.7 pixels mm^-1	θ_max = 64.6°, θ_min = 4.4°
ϕ and ω scans	h = −2→6
Absorption correction: multi-scan (SADABS; Bruker, 2013)	k = −12→12
T_min = 0.604, T_max = 0.662	l = −23→22
6298 measured reflections

Refinement top

Refinement on F²	Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: full	H-atom parameters constrained
R[F² > 2σ(F²)] = 0.038	w = 1/[σ²(F_o²) + (0.0605P)² + 0.0861P] where P = (F_o² + 2F_c²)/3
wR(F²) = 0.102	(Δ/σ)_max = 0.001
S = 1.10	Δρ_max = 0.21 e Å⁻³
2010 reflections	Δρ_min = −0.20 e Å⁻³
165 parameters	Extinction correction: SHELXL, FC^*=KFC[1+0.001XFC²Λ³/SIN(2Θ)]^-1/4
0 restraints	Extinction coefficient: 0.0158 (16)
Primary atom site location: structure-invariant direct methods	Absolute structure: Flack (1983), 805 Friedel pairs
Secondary atom site location: difference Fourier map	Absolute structure parameter: 0.02 (2)

Crystal data top

C₁₃H₁₂N₂OS	V = 1226.1 (2) Å³
M_r = 244.32	Z = 4
Orthorhombic, P2₁2₁2₁	Cu Kα radiation
a = 5.4960 (7) Å	µ = 2.22 mm⁻¹
b = 11.0177 (13) Å	T = 296 K
c = 20.249 (2) Å	0.25 × 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)
T_min = 0.604, T_max = 0.662	R_int = 0.042
6298 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	H-atom parameters constrained
wR(F²) = 0.102	Δρ_max = 0.21 e Å⁻³
S = 1.10	Δρ_min = −0.20 e Å⁻³
2010 reflections	Absolute structure: Flack (1983), 805 Friedel pairs
165 parameters	Absolute 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

	x	y	z	U_iso*/U_eq
S1	0.05502 (12)	0.12455 (6)	0.72104 (3)	0.0539 (2)
O1	0.0434 (4)	−0.24121 (15)	0.55887 (8)	0.0526 (6)
N1	0.0078 (3)	0.00557 (16)	0.59394 (8)	0.0348 (5)
N2	0.0086 (3)	−0.04249 (15)	0.52882 (8)	0.0344 (5)
C1	−0.0682 (6)	0.1399 (3)	0.79702 (12)	0.0623 (10)
C2	−0.2635 (6)	0.0712 (3)	0.80591 (13)	0.0648 (10)
C3	−0.3227 (5)	0.0016 (2)	0.74907 (11)	0.0513 (8)
C4	−0.1639 (4)	0.02325 (18)	0.69777 (10)	0.0358 (6)
C5	−0.1724 (4)	−0.02503 (18)	0.63061 (10)	0.0331 (6)
C6	−0.3905 (4)	−0.0972 (2)	0.61062 (13)	0.0509 (8)
C7	0.0373 (4)	−0.16179 (19)	0.51733 (10)	0.0410 (7)
C8	0.0373 (4)	0.04484 (17)	0.47710 (9)	0.0325 (6)
C9	0.2273 (4)	0.0366 (2)	0.43330 (11)	0.0397 (6)
C10	0.2429 (4)	0.1192 (2)	0.38203 (12)	0.0479 (7)
C11	0.0710 (5)	0.2091 (2)	0.37516 (11)	0.0469 (7)
C12	−0.1151 (5)	0.2185 (2)	0.41975 (12)	0.0463 (8)
C13	−0.1322 (4)	0.1365 (2)	0.47156 (11)	0.0413 (6)
H1	−0.00560	0.19130	0.82930	0.0750*
H2	−0.35200	0.06880	0.84500	0.0780*
H3	−0.45300	−0.05220	0.74680	0.0620*
H6A	−0.39060	−0.10770	0.56360	0.0760*
H6B	−0.53550	−0.05510	0.62380	0.0760*
H6C	−0.38540	−0.17530	0.63170	0.0760*
H7	0.05420	−0.18570	0.47350	0.0490*
H9	0.34410	−0.02390	0.43800	0.0480*
H10	0.37060	0.11400	0.35200	0.0570*
H11	0.08130	0.26340	0.34010	0.0560*
H12	−0.23010	0.27990	0.41530	0.0560*
H13	−0.25720	0.14340	0.50230	0.0500*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0546 (4)	0.0703 (5)	0.0368 (3)	−0.0147 (3)	−0.0029 (3)	−0.0071 (3)
O1	0.0729 (11)	0.0375 (9)	0.0474 (9)	0.0049 (8)	0.0049 (8)	0.0096 (7)
N1	0.0402 (10)	0.0379 (9)	0.0263 (8)	−0.0024 (8)	−0.0012 (7)	−0.0037 (6)
N2	0.0452 (10)	0.0313 (8)	0.0266 (8)	0.0006 (8)	−0.0005 (7)	−0.0022 (7)
C1	0.085 (2)	0.0689 (17)	0.0330 (12)	0.0037 (16)	−0.0059 (13)	−0.0095 (11)
C2	0.0757 (18)	0.0819 (19)	0.0368 (13)	0.0055 (16)	0.0152 (13)	0.0000 (13)
C3	0.0524 (14)	0.0590 (15)	0.0426 (13)	−0.0041 (12)	0.0127 (11)	−0.0022 (11)
C4	0.0373 (10)	0.0370 (11)	0.0332 (10)	0.0038 (9)	0.0009 (8)	0.0026 (8)
C5	0.0317 (10)	0.0314 (10)	0.0362 (11)	0.0037 (8)	−0.0030 (8)	0.0008 (8)
C6	0.0372 (12)	0.0564 (15)	0.0592 (14)	−0.0111 (10)	0.0008 (11)	−0.0119 (12)
C7	0.0511 (12)	0.0353 (11)	0.0366 (11)	0.0020 (9)	0.0024 (10)	−0.0018 (9)
C8	0.0388 (10)	0.0296 (10)	0.0291 (9)	−0.0017 (8)	−0.0051 (8)	−0.0012 (8)
C9	0.0355 (10)	0.0392 (11)	0.0444 (12)	0.0049 (9)	0.0011 (9)	0.0016 (10)
C10	0.0456 (12)	0.0511 (13)	0.0469 (13)	−0.0056 (11)	0.0089 (10)	0.0094 (11)
C11	0.0604 (14)	0.0365 (11)	0.0439 (12)	−0.0080 (11)	−0.0054 (11)	0.0088 (9)
C12	0.0536 (14)	0.0350 (12)	0.0503 (13)	0.0084 (11)	−0.0087 (11)	0.0024 (10)
C13	0.0429 (11)	0.0416 (11)	0.0395 (11)	0.0083 (10)	0.0012 (10)	−0.0035 (10)

Geometric parameters (Å, º) top

S1—C1	1.690 (3)	C10—C11	1.376 (3)
S1—C4	1.707 (2)	C11—C12	1.368 (4)
O1—C7	1.214 (3)	C12—C13	1.388 (3)
N1—N2	1.421 (2)	C1—H1	0.9300
N1—C5	1.283 (3)	C2—H2	0.9300
N2—C7	1.344 (3)	C3—H3	0.9300
N2—C8	1.431 (2)	C6—H6A	0.9600
C1—C2	1.326 (5)	C6—H6B	0.9600
C2—C3	1.421 (4)	C6—H6C	0.9600
C3—C4	1.378 (3)	C7—H7	0.9300
C4—C5	1.461 (3)	C9—H9	0.9300
C5—C6	1.494 (3)	C10—H10	0.9300
C8—C9	1.373 (3)	C11—H11	0.9300
C8—C13	1.379 (3)	C12—H12	0.9300
C9—C10	1.383 (3)	C13—H13	0.9300

C1—S1—C4	91.96 (13)	C2—C1—H1	123.00
N2—N1—C5	116.20 (17)	C1—C2—H2	124.00
N1—N2—C7	121.70 (16)	C3—C2—H2	124.00
N1—N2—C8	115.40 (15)	C2—C3—H3	124.00
C7—N2—C8	121.19 (16)	C4—C3—H3	124.00
S1—C1—C2	113.0 (2)	C5—C6—H6A	109.00
C1—C2—C3	112.6 (2)	C5—C6—H6B	109.00
C2—C3—C4	111.9 (2)	C5—C6—H6C	109.00
S1—C4—C3	110.58 (16)	H6A—C6—H6B	109.00
S1—C4—C5	121.16 (16)	H6A—C6—H6C	109.00
C3—C4—C5	128.2 (2)	H6B—C6—H6C	109.00
N1—C5—C4	114.73 (19)	O1—C7—H7	117.00
N1—C5—C6	127.04 (19)	N2—C7—H7	117.00
C4—C5—C6	118.13 (19)	C8—C9—H9	120.00
O1—C7—N2	126.02 (19)	C10—C9—H9	120.00
N2—C8—C9	120.81 (18)	C9—C10—H10	120.00
N2—C8—C13	118.53 (18)	C11—C10—H10	120.00
C9—C8—C13	120.65 (19)	C10—C11—H11	120.00
C8—C9—C10	119.2 (2)	C12—C11—H11	120.00
C9—C10—C11	120.5 (2)	C11—C12—H12	120.00
C10—C11—C12	120.1 (2)	C13—C12—H12	120.00
C11—C12—C13	120.0 (2)	C8—C13—H13	120.00
C8—C13—C12	119.5 (2)	C12—C13—H13	120.00
S1—C1—H1	124.00

C4—S1—C1—C2	0.9 (3)	C2—C3—C4—C5	−176.1 (2)
C1—S1—C4—C3	−1.3 (2)	C2—C3—C4—S1	1.4 (3)
C1—S1—C4—C5	176.4 (2)	S1—C4—C5—N1	6.3 (3)
C5—N1—N2—C7	−67.0 (2)	C3—C4—C5—N1	−176.4 (2)
C5—N1—N2—C8	127.7 (2)	C3—C4—C5—C6	7.0 (3)
N2—N1—C5—C4	178.38 (16)	S1—C4—C5—C6	−170.31 (16)
N2—N1—C5—C6	−5.3 (3)	N2—C8—C9—C10	176.94 (19)
C7—N2—C8—C13	135.3 (2)	C13—C8—C9—C10	−2.1 (3)
N1—N2—C7—O1	6.9 (3)	N2—C8—C13—C12	−176.7 (2)
C8—N2—C7—O1	171.3 (2)	C9—C8—C13—C12	2.3 (3)
N1—N2—C8—C9	121.6 (2)	C8—C9—C10—C11	0.4 (3)
C7—N2—C8—C9	−43.7 (3)	C9—C10—C11—C12	1.0 (4)
N1—N2—C8—C13	−59.4 (2)	C10—C11—C12—C13	−0.7 (4)
S1—C1—C2—C3	−0.3 (4)	C11—C12—C13—C8	−0.9 (3)
C1—C2—C3—C4	−0.7 (4)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.39	3.202 (3)	145

Symmetry code: (i) −x, y+1/2, −z+3/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C1—H1···O1ⁱ	0.93	2.39	3.202 (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

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

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

1. Related literature

2. Experimental

2.1. Crystal data

2.2. Data collection

2.3. Refinement

Supporting information

Acknowledgements

References

organic compounds

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