N′-(4-Cyano­benzyl­idene)thio­phene-2-carbohydrazide

Li, Y.-F.; Zhang, F.-G.; Jian, F.-F.

doi:10.1107/S1600536810019215

organic compounds

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Volume 66| Part 6| June 2010| Page o1471

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N′-(4-Cyanobenzylidene)thiophene-2-carbohydrazide

Yu-Feng Li,^a Fu-Gong Zhang ^b and Fang-Fang Jian ^c ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China, ^bMinistry of Personnel, Weifang University, Weifang 261061, People's Republic of China, and ^cMicroscale Science Institute, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: liyufeng8111@163.com

(Received 12 May 2010; accepted 22 May 2010; online 26 May 2010)

The title compound, C₁₃H₉N₃OS, was prepared by the reaction of thiophene-2-carbohydrazide and 4-formylbenzonitrile. The dihedral angle between the benzene and thiophene rings is 11.9 (1)°. In the crystal structure, molecules are linked into centrosymmetric dimers by pairs of N—H⋯O hydrogen bonds.

Related literature

For related structures, see: Girgis (2006 ); Jiang (2010 ).

Experimental

Crystal data

C₁₃H₉N₃OS
M_r = 255.29
Monoclinic, P 2₁ /n
a = 6.3966 (13) Å
b = 16.340 (3) Å
c = 11.494 (2) Å
β = 90.66 (3)°
V = 1201.3 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.26 mm⁻¹
T = 293 K
0.21 × 0.20 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
11589 measured reflections
2746 independent reflections
1539 reflections with I > 2σ(I)
R_int = 0.066

Refinement

R[F² > 2σ(F²)] = 0.046
wR(F²) = 0.145
S = 1.03
2746 reflections
163 parameters
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.32 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯O1ⁱ	0.86	1.97	2.821 (2)	171
Symmetry code: (i) -x, -y+1, -z+2.

Data collection: SMART (Bruker, 1997 ); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536810019215/lh5046sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536810019215/lh5046Isup2.hkl

checkCIF report

Comment top

General background references for the title compound are included in the publication of a related structure (Jiang, 2010). As part of our search for new schiff base compounds we synthesized the title compound (I), and describe its structure here.

The molcular structure of (I) is shown in Fig. 1. The C8═N3 bond length of 1.272 (3)Å is comparable with reported values [1.281 (2) Å] (Girgis, 2006) and [1.273 (3)Å] (Jiang, 2010). In the crystal structure, molecules are linked by intermolecular N—H···O hydrogen bonds into centrosymmetric dimers.

Related literature top

For related structures, see: Girgis (2006); Jiang (2010).

Experimental top

A mixture of the thiophene-2-carbohydrazide (0.10 mol), and 4-formylbenzonitrile (0.10 mol) was stirred in refluxing ethanol (10 mL) for 4 h to afford the title compound (0.079 mol, yield 79%). Single crystals suitable for X-ray measurements were obtained by recrystallization from ethanol at room temperature.

Structure description top

For related structures, see: Girgis (2006); Jiang (2010).

Computing details top

Data collection: SMART (Bruker, 1997); cell refinement: SAINT (Bruker, 1997); data reduction: SAINT (Bruker, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXTL (Sheldrick, 2008).

Figures top

Fig. 1. The structure of the title compound showing 30% probability displacement ellipsoids and the atom-numbering scheme.

N'-(4-Cyanobenzylidene)thiophene-2-carbohydrazide top

Crystal data top

C₁₃H₉N₃OS	F(000) = 528
M_r = 255.29	D_x = 1.412 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1539 reflections
a = 6.3966 (13) Å	θ = 3.8–26.2°
b = 16.340 (3) Å	µ = 0.26 mm⁻¹
c = 11.494 (2) Å	T = 293 K
β = 90.66 (3)°	Block, colorless
V = 1201.3 (4) Å³	0.21 × 0.20 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	1539 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.066
Graphite monochromator	θ_max = 27.5°, θ_min = 3.1°
φ and ω scans	h = −8→8
11589 measured reflections	k = −21→21
2746 independent reflections	l = −14→14

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)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.145	H-atom parameters constrained
S = 1.03	w = 1/[σ²(F_o²) + (0.0682P)²] where P = (F_o² + 2F_c²)/3
2746 reflections	(Δ/σ)_max < 0.001
163 parameters	Δρ_max = 0.23 e Å⁻³
0 restraints	Δρ_min = −0.32 e Å⁻³

Crystal data top

C₁₃H₉N₃OS	V = 1201.3 (4) Å³
M_r = 255.29	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.3966 (13) Å	µ = 0.26 mm⁻¹
b = 16.340 (3) Å	T = 293 K
c = 11.494 (2) Å	0.21 × 0.20 × 0.18 mm
β = 90.66 (3)°

Data collection top

Bruker SMART CCD diffractometer	1539 reflections with I > 2σ(I)
11589 measured reflections	R_int = 0.066
2746 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.046	0 restraints
wR(F²) = 0.145	H-atom parameters constrained
S = 1.03	Δρ_max = 0.23 e Å⁻³
2746 reflections	Δρ_min = −0.32 e Å⁻³
163 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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
N3	0.2706 (3)	0.38738 (12)	0.84452 (15)	0.0428 (5)
N2	0.1294 (3)	0.44128 (12)	0.88894 (14)	0.0440 (5)
H2A	0.1499	0.4603	0.9579	0.053*
O1	−0.1694 (3)	0.51089 (11)	0.87605 (12)	0.0542 (5)
C2	0.8862 (4)	0.20156 (14)	0.79598 (18)	0.0444 (6)
C9	−0.0408 (4)	0.46559 (14)	0.82840 (17)	0.0421 (6)
C4	0.7596 (4)	0.29587 (15)	0.93785 (18)	0.0463 (6)
H4A	0.7759	0.3224	1.0089	0.056*
C8	0.4290 (4)	0.37040 (14)	0.90796 (18)	0.0430 (6)
H8A	0.4457	0.3960	0.9797	0.052*
C7	0.7082 (4)	0.21428 (16)	0.72907 (19)	0.0535 (7)
H7A	0.6895	0.1858	0.6597	0.064*
C5	0.5847 (4)	0.31123 (13)	0.86961 (17)	0.0408 (6)
C10	−0.0772 (4)	0.43914 (14)	0.70730 (17)	0.0431 (6)
C3	0.9102 (4)	0.24155 (15)	0.90156 (19)	0.0487 (6)
H3B	1.0278	0.2318	0.9479	0.058*
C13	−0.0822 (5)	0.38914 (16)	0.5070 (2)	0.0600 (8)
H13A	−0.0568	0.3664	0.4344	0.072*
C6	0.5585 (4)	0.26912 (15)	0.76500 (19)	0.0505 (6)
H6A	0.4397	0.2780	0.7193	0.061*
C11	−0.2581 (4)	0.45925 (15)	0.64795 (18)	0.0514 (7)
H11A	−0.3673	0.4888	0.6802	0.062*
C12	−0.2588 (5)	0.43005 (16)	0.5330 (2)	0.0595 (7)
H12A	−0.3688	0.4380	0.4806	0.071*
S1	0.08838 (11)	0.38350 (4)	0.62050 (5)	0.0558 (3)
N1	1.1789 (4)	0.10803 (16)	0.7206 (2)	0.0703 (7)
C1	1.0483 (4)	0.14800 (17)	0.7545 (2)	0.0516 (6)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N3	0.0461 (13)	0.0436 (12)	0.0388 (9)	0.0034 (10)	0.0026 (9)	−0.0032 (8)
N2	0.0477 (13)	0.0492 (12)	0.0351 (9)	0.0055 (10)	−0.0021 (9)	−0.0080 (8)
O1	0.0571 (12)	0.0630 (12)	0.0425 (8)	0.0186 (9)	−0.0023 (8)	−0.0126 (8)
C2	0.0460 (15)	0.0440 (14)	0.0432 (11)	0.0022 (11)	0.0034 (11)	0.0055 (10)
C9	0.0471 (15)	0.0414 (13)	0.0376 (11)	0.0018 (11)	−0.0021 (11)	−0.0001 (10)
C4	0.0514 (16)	0.0490 (14)	0.0384 (11)	−0.0003 (12)	−0.0013 (11)	−0.0017 (10)
C8	0.0459 (15)	0.0463 (14)	0.0369 (11)	−0.0016 (11)	−0.0012 (10)	0.0013 (10)
C7	0.0612 (18)	0.0539 (16)	0.0452 (12)	0.0049 (13)	−0.0047 (12)	−0.0094 (11)
C5	0.0435 (15)	0.0404 (13)	0.0385 (11)	−0.0002 (11)	0.0022 (10)	0.0036 (9)
C10	0.0507 (15)	0.0401 (13)	0.0386 (11)	0.0018 (11)	0.0006 (10)	−0.0024 (9)
C3	0.0464 (16)	0.0517 (15)	0.0478 (12)	0.0026 (12)	−0.0026 (11)	0.0065 (11)
C13	0.081 (2)	0.0600 (18)	0.0391 (12)	0.0101 (16)	−0.0040 (13)	−0.0079 (11)
C6	0.0496 (16)	0.0538 (16)	0.0478 (12)	0.0066 (13)	−0.0063 (11)	−0.0027 (11)
C11	0.0591 (18)	0.0528 (16)	0.0420 (12)	0.0071 (13)	−0.0077 (11)	−0.0061 (11)
C12	0.071 (2)	0.0596 (17)	0.0477 (13)	0.0082 (15)	−0.0166 (13)	−0.0056 (12)
S1	0.0620 (5)	0.0646 (5)	0.0407 (3)	0.0109 (3)	−0.0001 (3)	−0.0088 (3)
N1	0.0686 (18)	0.0765 (17)	0.0658 (14)	0.0177 (14)	0.0068 (13)	−0.0044 (12)
C1	0.0534 (17)	0.0544 (16)	0.0471 (13)	0.0029 (13)	0.0009 (12)	0.0027 (12)

Geometric parameters (Å, º) top

N3—C8	1.272 (3)	C7—C6	1.378 (3)
N3—N2	1.365 (2)	C7—H7A	0.9300
N2—C9	1.345 (3)	C5—C6	1.394 (3)
N2—H2A	0.8600	C10—C11	1.376 (3)
O1—C9	1.239 (3)	C10—S1	1.723 (2)
C2—C7	1.382 (3)	C3—H3B	0.9300
C2—C3	1.385 (3)	C13—C12	1.349 (4)
C2—C1	1.442 (4)	C13—S1	1.693 (3)
C9—C10	1.474 (3)	C13—H13A	0.9300
C4—C3	1.378 (3)	C6—H6A	0.9300
C4—C5	1.382 (3)	C11—C12	1.405 (3)
C4—H4A	0.9300	C11—H11A	0.9300
C8—C5	1.460 (3)	C12—H12A	0.9300
C8—H8A	0.9300	N1—C1	1.133 (3)

C8—N3—N2	116.90 (18)	C6—C5—C8	120.8 (2)
C9—N2—N3	122.15 (18)	C11—C10—C9	121.4 (2)
C9—N2—H2A	118.9	C11—C10—S1	110.98 (16)
N3—N2—H2A	118.9	C9—C10—S1	127.61 (19)
C7—C2—C3	119.9 (2)	C4—C3—C2	119.9 (2)
C7—C2—C1	119.9 (2)	C4—C3—H3B	120.1
C3—C2—C1	120.2 (2)	C2—C3—H3B	120.1
O1—C9—N2	119.03 (19)	C12—C13—S1	112.96 (18)
O1—C9—C10	119.6 (2)	C12—C13—H13A	123.5
N2—C9—C10	121.3 (2)	S1—C13—H13A	123.5
C3—C4—C5	120.6 (2)	C7—C6—C5	120.1 (2)
C3—C4—H4A	119.7	C7—C6—H6A	119.9
C5—C4—H4A	119.7	C5—C6—H6A	119.9
N3—C8—C5	120.9 (2)	C10—C11—C12	112.2 (2)
N3—C8—H8A	119.6	C10—C11—H11A	123.9
C5—C8—H8A	119.6	C12—C11—H11A	123.9
C6—C7—C2	120.1 (2)	C13—C12—C11	112.5 (3)
C6—C7—H7A	119.9	C13—C12—H12A	123.7
C2—C7—H7A	119.9	C11—C12—H12A	123.7
C4—C5—C6	119.2 (2)	C13—S1—C10	91.29 (13)
C4—C5—C8	120.0 (2)	N1—C1—C2	177.8 (3)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86	1.97	2.821 (2)	171

Symmetry code: (i) −x, −y+1, −z+2.

Experimental details

Crystal data
Chemical formula	C₁₃H₉N₃OS
M_r	255.29
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.3966 (13), 16.340 (3), 11.494 (2)
β (°)	90.66 (3)
V (Å³)	1201.3 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.26
Crystal size (mm)	0.21 × 0.20 × 0.18

Data collection
Diffractometer	Bruker SMART CCD
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	11589, 2746, 1539
R_int	0.066
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.046, 0.145, 1.03
No. of reflections	2746
No. of parameters	163
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.32

Computer programs: SMART (Bruker, 1997), SAINT (Bruker, 1997), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86	1.97	2.821 (2)	171

Symmetry code: (i) −x, −y+1, −z+2.

References

Bruker (1997). SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Girgis, A. S. (2006). J. Chem. Res. pp. 81–85. CrossRef Google Scholar
Jiang, J.-H. (2010). Acta Cryst. E66, o922. Web of Science CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar

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CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 66| Part 6| June 2010| Page o1471

https://doi.org/10.1107/S1600536810019215

Open

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