(E)-N′-[1-(Thio­phen-2-yl)ethyl­idene]benzohydrazide

Shan, S.; Huang, Y.-L.; Guo, H.-Q.; Li, D.-F.; Sun, J.

doi:10.1107/S1600536811033101

organic compounds

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ISSN: 2056-9890

Volume 67| Part 9| September 2011| Page o2498

doi:10.1107/S1600536811033101

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(E)-N′-[1-(Thiophen-2-yl)ethylidene]benzohydrazide

Shang Shan,^a ^* Yan-Lan Huang,^a Han-Qi Guo,^a Deng-Feng Li ^a and Jian Sun ^a

^aCollege of Chemical Engineering and Materials Science, Zhejiang University of Technology, People's Republic of China
^*Correspondence e-mail: shanshang@mail.hz.zj.cn

(Received 16 July 2011; accepted 15 August 2011; online 27 August 2011)

The title compound, C₁₃H₁₂N₂OS, was obtained from the condensation reaction of 2-acetylthiophene and benzohydrazide. In the molecule, the formohydrazide fragment is approximately planar (r.m.s deviation = 0.0146 Å) and the mean plane is oriented at dihedral angles of 24.47 (11) and 28.86 (13)°, respectively, to the phenyl and thiophene rings. The thiophene and phenyl rings make a dihedral angle of 53.21 (8)°. The benzamide fragment and thiophene ring are located on the opposite sides of the C=N bond, showing an E conformation. Classical intermolecular N—H⋯O hydrogen bonds and weak C—H⋯O interactions are present in the crystal structure: three such bonds occur to the same O-atom acceptor.

Related literature

For applications of hydrazone derivatives in the biological field, see: Okabe et al. (1993 ). For general background to this work, see: Qiang et al. (2007 ). For a related structures, see: Xia et al. (2009 ); Shan et al. (2011 )

Experimental

Crystal data

C₁₃H₁₂N₂OS
M_r = 244.31
Orthorhombic, P b c a
a = 9.906 (3) Å
b = 10.542 (5) Å
c = 22.870 (5) Å
V = 2388.3 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 294 K
0.32 × 0.29 × 0.28 mm

Data collection

Rigaku R-AXIS RAPID IP diffractometer
7859 measured reflections
2153 independent reflections
1552 reflections with I > 2σ(I)
R_int = 0.036

Refinement

R[F² > 2σ(F²)] = 0.041
wR(F²) = 0.101
S = 1.03
2153 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1ⁱ	0.86	2.50	3.340 (3)	166
C2—H2⋯O1ⁱ	0.93	2.43	3.251 (3)	147
C13—H13A⋯O1ⁱ	0.96	2.40	3.246 (3)	147
Symmetry code: (i) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: PROCESS-AUTO (Rigaku, 1998 ); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2002 ); program(s) used to solve structure: SIR92 (Altomare et al., 1993 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ); software used to prepare material for publication: WinGX (Farrugia, 1999 ).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536811033101/xu6116sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811033101/xu6116Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536811033101/xu6116Isup3.cml

checkCIF report

Comment top

The hydrazone derivatives has attracted our much attention because they have shown to be potential DNA damaging and mutagenic agents (Okabe et al., 1993). As part of the ongoing investigation on the relationship between structure and property of hydrazone derivatives (Qiang et al., 2007) the title compound has recently been prepared in our laboratory and its crystal structure is reported here.

The molecular structure of the title compound is shown in Fig. 1. In the molecule, the formohydrazide fragment is approximately co-planar [r.m.s deviation = 0.0146 Å] and the mean plane is oriented with respect to the phenyl ring and thiophene ring at 24.47 (11) and 28.86 (13)°, respectively. The N2—C8 bond length of 1.286 (2) Å shows a typical C═N double bond. The thiophene and benzamide units are located on the opposite sites of the C═N bond, showing an E configuration.

Intermolecular N—H···O and weak C—H···O hydrogen bonding is present in the crystal structure (Table 1).

Related literature top

For applications of hydrazone derivatives in the biological field, see: Okabe et al. (1993). For general background to this work, see: Qiang et al. (2007). For a related structure, see: Xia et al. (2009).

Experimental top

Benzohydrazide (0.68 g, 5 mmol) was dissolved in ethanol (25 ml), then acetic acid (0.2 ml) was added to the ethanol solution with stirring. The solution was heated at about 333 K for several minutes until it became clear. 2-Acetylthiophene (0.63 g, 5 mmol) was then added slowly into the solution, and the mixture solution was refluxed for 6 h. After cooling to room temperature, yellow microcrystals appeared. The microcrystals were separated from the solution and washed with cold water three times. Recrystallization was performed twice with absolute methanol to obtain single crystals of the title compound.

Computing details top

Data collection: PROCESS-AUTO (Rigaku, 1998); cell refinement: PROCESS-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SIR92 (Altomare et al., 1993); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

Fig. 1. The molecular structure of the title compound with 40% probability displacement (arbitrary spheres for H atoms).

(E)-N'-[1-(Thiophen-2-yl)ethylidene]benzohydrazide top

Crystal data top

C₁₃H₁₂N₂OS	F(000) = 1024
M_r = 244.31	D_x = 1.359 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2153 reflections
a = 9.906 (3) Å	θ = 3.3–25.2°
b = 10.542 (5) Å	µ = 0.26 mm⁻¹
c = 22.870 (5) Å	T = 294 K
V = 2388.3 (14) Å³	Block, yellow
Z = 8	0.32 × 0.29 × 0.28 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1552 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.036
Graphite monochromator	θ_max = 25.2°, θ_min = 3.3°
Detector resolution: 10.0 pixels mm^-1	h = −10→11
ω scans	k = −11→12
7859 measured reflections	l = −27→23
2153 independent reflections

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.041	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.101	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0465P)² + 0.4798P] where P = (F_o² + 2F_c²)/3
2153 reflections	(Δ/σ)_max = 0.001
155 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.17 e Å⁻³

Crystal data top

C₁₃H₁₂N₂OS	V = 2388.3 (14) Å³
M_r = 244.31	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 9.906 (3) Å	µ = 0.26 mm⁻¹
b = 10.542 (5) Å	T = 294 K
c = 22.870 (5) Å	0.32 × 0.29 × 0.28 mm

Data collection top

Rigaku R-AXIS RAPID IP diffractometer	1552 reflections with I > 2σ(I)
7859 measured reflections	R_int = 0.036
2153 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.041	0 restraints
wR(F²) = 0.101	H-atom parameters constrained
S = 1.03	Δρ_max = 0.20 e Å⁻³
2153 reflections	Δρ_min = −0.17 e Å⁻³
155 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) 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	0.61206 (5)	0.31374 (5)	0.02223 (3)	0.0507 (2)
N1	0.30582 (15)	0.50999 (16)	0.12073 (8)	0.0425 (5)
H1	0.3095	0.5895	0.1290	0.051*
N2	0.41317 (15)	0.45043 (16)	0.09296 (8)	0.0422 (4)
O1	0.19122 (15)	0.32660 (14)	0.12656 (9)	0.0679 (5)
C1	0.08229 (18)	0.51074 (18)	0.16290 (10)	0.0376 (5)
C2	0.0570 (2)	0.6393 (2)	0.15591 (10)	0.0462 (6)
H2	0.1126	0.6881	0.1321	0.055*
C3	−0.0508 (2)	0.6949 (2)	0.18432 (11)	0.0549 (6)
H3	−0.0675	0.7810	0.1794	0.066*
C4	−0.1335 (2)	0.6245 (3)	0.21977 (11)	0.0583 (7)
H4	−0.2050	0.6629	0.2393	0.070*
C5	−0.1101 (2)	0.4972 (2)	0.22631 (12)	0.0606 (7)
H5	−0.1664	0.4490	0.2501	0.073*
C6	−0.0040 (2)	0.4405 (2)	0.19801 (10)	0.0495 (6)
H6	0.0103	0.3538	0.2024	0.059*
C7	0.19588 (19)	0.4411 (2)	0.13447 (10)	0.0423 (5)
C8	0.5283 (2)	0.50629 (18)	0.09602 (10)	0.0377 (5)
C9	0.63941 (18)	0.44513 (18)	0.06501 (9)	0.0377 (5)
C10	0.7727 (2)	0.4768 (2)	0.06465 (11)	0.0488 (6)
H10	0.8080	0.5451	0.0853	0.059*
C11	0.8514 (2)	0.3953 (2)	0.02980 (11)	0.0549 (7)
H11	0.9441	0.4043	0.0249	0.066*
C12	0.7782 (2)	0.3029 (2)	0.00428 (11)	0.0509 (6)
H12	0.8141	0.2409	−0.0201	0.061*
C13	0.5569 (2)	0.6255 (2)	0.12900 (11)	0.0523 (6)
H13A	0.5023	0.6930	0.1137	0.078*
H13B	0.6506	0.6471	0.1249	0.078*
H13C	0.5362	0.6130	0.1696	0.078*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0387 (3)	0.0543 (4)	0.0590 (4)	−0.0030 (3)	−0.0008 (3)	−0.0143 (3)
N1	0.0321 (9)	0.0425 (9)	0.0529 (13)	0.0001 (8)	0.0042 (8)	−0.0043 (8)
N2	0.0328 (9)	0.0455 (9)	0.0484 (12)	0.0030 (8)	0.0026 (8)	−0.0031 (8)
O1	0.0465 (9)	0.0458 (9)	0.1112 (16)	−0.0032 (7)	0.0204 (9)	−0.0110 (9)
C1	0.0319 (10)	0.0441 (11)	0.0368 (13)	−0.0032 (9)	−0.0021 (9)	−0.0031 (9)
C2	0.0422 (12)	0.0472 (12)	0.0491 (16)	−0.0032 (10)	0.0022 (11)	0.0017 (10)
C3	0.0555 (14)	0.0501 (13)	0.0591 (17)	0.0100 (11)	0.0014 (12)	−0.0064 (12)
C4	0.0485 (13)	0.0730 (17)	0.0533 (17)	0.0060 (13)	0.0099 (12)	−0.0136 (13)
C5	0.0592 (15)	0.0688 (16)	0.0538 (18)	−0.0099 (13)	0.0207 (13)	−0.0064 (12)
C6	0.0537 (13)	0.0479 (12)	0.0470 (15)	−0.0034 (11)	0.0064 (11)	−0.0016 (11)
C7	0.0344 (11)	0.0441 (12)	0.0485 (15)	−0.0015 (10)	−0.0023 (10)	−0.0020 (10)
C8	0.0345 (10)	0.0393 (10)	0.0392 (13)	0.0005 (9)	−0.0022 (10)	0.0023 (9)
C9	0.0346 (10)	0.0382 (10)	0.0402 (13)	0.0003 (9)	−0.0007 (9)	0.0029 (9)
C10	0.0375 (11)	0.0448 (12)	0.0641 (17)	−0.0057 (10)	0.0032 (11)	−0.0064 (11)
C11	0.0354 (11)	0.0549 (13)	0.0744 (19)	0.0005 (10)	0.0097 (12)	−0.0043 (13)
C12	0.0437 (12)	0.0548 (14)	0.0542 (16)	0.0068 (11)	0.0061 (11)	−0.0068 (12)
C13	0.0389 (11)	0.0533 (13)	0.0646 (18)	−0.0006 (10)	0.0028 (11)	−0.0126 (12)

Geometric parameters (Å, º) top

S1—C12	1.700 (2)	C4—H4	0.9300
S1—C9	1.717 (2)	C5—C6	1.371 (3)
N1—C7	1.346 (2)	C5—H5	0.9300
N1—N2	1.389 (2)	C6—H6	0.9300
N1—H1	0.8600	C8—C9	1.459 (3)
N2—C8	1.286 (2)	C8—C13	1.493 (3)
O1—C7	1.222 (2)	C9—C10	1.361 (3)
C1—C6	1.387 (3)	C10—C11	1.407 (3)
C1—C2	1.388 (3)	C10—H10	0.9300
C1—C7	1.492 (3)	C11—C12	1.347 (3)
C2—C3	1.380 (3)	C11—H11	0.9300
C2—H2	0.9300	C12—H12	0.9300
C3—C4	1.371 (3)	C13—H13A	0.9600
C3—H3	0.9300	C13—H13B	0.9600
C4—C5	1.370 (3)	C13—H13C	0.9600

C12—S1—C9	92.23 (10)	O1—C7—C1	121.45 (18)
C7—N1—N2	118.85 (17)	N1—C7—C1	116.53 (18)
C7—N1—H1	120.6	N2—C8—C9	116.11 (18)
N2—N1—H1	120.6	N2—C8—C13	125.55 (19)
C8—N2—N1	116.57 (17)	C9—C8—C13	118.34 (17)
C6—C1—C2	118.51 (19)	C10—C9—C8	128.73 (19)
C6—C1—C7	117.01 (18)	C10—C9—S1	110.31 (16)
C2—C1—C7	124.48 (19)	C8—C9—S1	120.95 (14)
C3—C2—C1	120.0 (2)	C9—C10—C11	113.0 (2)
C3—C2—H2	120.0	C9—C10—H10	123.5
C1—C2—H2	120.0	C11—C10—H10	123.5
C4—C3—C2	120.7 (2)	C12—C11—C10	112.8 (2)
C4—C3—H3	119.6	C12—C11—H11	123.6
C2—C3—H3	119.6	C10—C11—H11	123.6
C5—C4—C3	119.6 (2)	C11—C12—S1	111.59 (17)
C5—C4—H4	120.2	C11—C12—H12	124.2
C3—C4—H4	120.2	S1—C12—H12	124.2
C4—C5—C6	120.3 (2)	C8—C13—H13A	109.5
C4—C5—H5	119.8	C8—C13—H13B	109.5
C6—C5—H5	119.8	H13A—C13—H13B	109.5
C5—C6—C1	120.8 (2)	C8—C13—H13C	109.5
C5—C6—H6	119.6	H13A—C13—H13C	109.5
C1—C6—H6	119.6	H13B—C13—H13C	109.5
O1—C7—N1	121.93 (19)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.50	3.340 (3)	166
C2—H2···O1ⁱ	0.93	2.43	3.251 (3)	147
C13—H13A···O1ⁱ	0.96	2.40	3.246 (3)	147

Symmetry code: (i) −x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₃H₁₂N₂OS
M_r	244.31
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	294
a, b, c (Å)	9.906 (3), 10.542 (5), 22.870 (5)
V (Å³)	2388.3 (14)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.32 × 0.29 × 0.28

Data collection
Diffractometer	Rigaku R-AXIS RAPID IP diffractometer
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7859, 2153, 1552
R_int	0.036
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.041, 0.101, 1.03
No. of reflections	2153
No. of parameters	155
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.17

Computer programs: PROCESS-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SIR92 (Altomare et al., 1993), SHELXL97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1ⁱ	0.86	2.50	3.340 (3)	166
C2—H2···O1ⁱ	0.93	2.43	3.251 (3)	147
C13—H13A···O1ⁱ	0.96	2.40	3.246 (3)	147

Symmetry code: (i) −x+1/2, y+1/2, z.

Acknowledgements

The work was supported by the Natural Science Foundation of Zhejiang Province, China (No. M203027).

References

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