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

Abstract

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,

• a = 6.3966 (13) Å

• b = 16.340 (3) Å

• c = 11.494 (2) Å

• β = 90.66 (3)°

• V = 1201.3 (4) ų

• 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[F ² > 2σ(F ²)] = 0.046

• wR(F ²) = 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

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.

Supplementary Material

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

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) .

supplementary crystallographic information

Comment

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.

Experimental

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.

Refinement

H atoms were fixed geometrically and allowed to ride on their attached atoms, with C—H distances = 0.93-0.97 Å; N—H = 0.86Å and with U_iso(H) = 1.2U_eq(C,N) or 1.5U_eq(C_methyl).

Figures

Fig. 1.

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

Crystal data

C13H9N3OS	F(000) = 528
Mr = 255.29	Dx = 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

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

Refinement

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(Fo2) + (0.0682P)2] where P = (Fo2 + 2Fc2)/3
2746 reflections	(Δ/σ)max < 0.001
163 parameters	Δρmax = 0.23 e Å−3
0 restraints	Δρmin = −0.31 e Å−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	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, °)

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, °)

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

Symmetry codes: (i) −x, −y+1, −z+2.