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

Jiang, J.-H.

doi:10.1107/S1600536810010615

organic compounds

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ISSN: 2056-9890

Volume 66| Part 4| April 2010| Page o923

doi:10.1107/S1600536810010615

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

Jin-He Jiang ^a ^*

^aMicroscale Science Institute, Department of Chemistry and Chemical Engineering, Weifang University, Weifang 261061, People's Republic of China
^*Correspondence e-mail: weifangjjh@126.com

(Received 19 March 2010; accepted 22 March 2010; online 27 March 2010)

In the title compound, C₁₂H₉ClN₂OS, the dihedral angle between the aromatic rings is 9.78 (11)°. In the crystal structure, inversion dimers linked by pairs of N—H⋯O hydrogen bonds occur, generating R₂²(8) loops. Weak aromatic π–π stacking [centroid–centroid separations = 3.7210 (15) and 3.8706 (15) Å] also occurs.

Related literature

For the isostructural bromo-compound and background information, see the preceding paper: Jiang (2010 ).

Experimental

Crystal data

C₁₂H₉ClN₂OS
M_r = 264.72
Monoclinic, P 2₁ /n
a = 6.0040 (12) Å
b = 16.831 (3) Å
c = 11.557 (2) Å
β = 94.38 (3)°
V = 1164.5 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.49 mm⁻¹
T = 293 K
0.21 × 0.19 × 0.18 mm

Data collection

Bruker SMART CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1997 ) T_min = 0.491, T_max = 0.728
11069 measured reflections
2660 independent reflections
1778 reflections with I > 2σ(I)
R_int = 0.115

Refinement

R[F² > 2σ(F²)] = 0.054
wR(F²) = 0.141
S = 0.94
2660 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.52 e Å⁻³
Δρ_min = −0.33 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	2.01	2.825 (2)	158
Symmetry code: (i) -x, -y, -z+1.

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: 10.1107/S1600536810010615/hb5369sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536810010615/hb5369Isup2.hkl

checkCIF report

Comment top

As part of our search for new Schiff base compounds (Jiang, 2010) we synthesized the title compound (I), and describe its structure here.

The molcular structure of (I) is shown in Fig. 1. In the crystal structure, molecules are linked by intermolecular N—H···O hydrogen bonds.

Related literature top

For the isostructural bromo-compound and background information, see the preceding paper: Jiang (2010).

Experimental top

A mixture of thiophene-2-carbohydrazide (0.05 mol), and 4-chlorobenzaldehyde (0.05 mol) was stirred in refluxing ethanol (10 ml) for 4 h to afford the title compound (0.084 mol, yield 84%). Colourless blocks of (I) were obtained by recrystallization from ethanol at room temperature.

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 molecular structure of (I) showing 30% probability displacement ellipsoids.

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

Crystal data top

C₁₂H₉ClN₂OS	F(000) = 544
M_r = 264.72	D_x = 1.510 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 1778 reflections
a = 6.0040 (12) Å	θ = 3–27.5°
b = 16.831 (3) Å	µ = 0.49 mm⁻¹
c = 11.557 (2) Å	T = 293 K
β = 94.38 (3)°	Block, colorless
V = 1164.5 (4) Å³	0.21 × 0.19 × 0.18 mm
Z = 4

Data collection top

Bruker SMART CCD diffractometer	2660 independent reflections
Radiation source: fine-focus sealed tube	1778 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.115
ω scans	θ_max = 27.5°, θ_min = 3.0°
Absorption correction: multi-scan (SADABS; Bruker, 1997)	h = −7→7
T_min = 0.491, T_max = 0.728	k = −21→21
11069 measured 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)] = 0.054	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.141	H-atom parameters constrained
S = 0.94	w = 1/[σ²(F_o²) + (0.061P)²] where P = (F_o² + 2F_c²)/3
2660 reflections	(Δ/σ)_max < 0.001
154 parameters	Δρ_max = 0.52 e Å⁻³
0 restraints	Δρ_min = −0.33 e Å⁻³

Crystal data top

C₁₂H₉ClN₂OS	V = 1164.5 (4) Å³
M_r = 264.72	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 6.0040 (12) Å	µ = 0.49 mm⁻¹
b = 16.831 (3) Å	T = 293 K
c = 11.557 (2) Å	0.21 × 0.19 × 0.18 mm
β = 94.38 (3)°

Data collection top

Bruker SMART CCD diffractometer	2660 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1997)	1778 reflections with I > 2σ(I)
T_min = 0.491, T_max = 0.728	R_int = 0.115
11069 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.054	0 restraints
wR(F²) = 0.141	H-atom parameters constrained
S = 0.94	Δρ_max = 0.52 e Å⁻³
2660 reflections	Δρ_min = −0.33 e Å⁻³
154 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
S1	0.13248 (10)	0.11796 (4)	0.87758 (5)	0.0454 (2)
Cl11	1.14308 (10)	0.37422 (4)	0.75642 (6)	0.0564 (2)
C6	0.4682 (4)	0.12975 (13)	0.5974 (2)	0.0415 (5)
H6A	0.4793	0.1052	0.5260	0.050*
N1	0.3130 (3)	0.10929 (11)	0.66045 (16)	0.0405 (5)
O1	−0.1503 (3)	−0.01594 (11)	0.62318 (14)	0.0543 (5)
N2	0.1660 (3)	0.05312 (11)	0.61567 (15)	0.0435 (5)
H2A	0.1869	0.0321	0.5495	0.052*
C4	−0.0422 (3)	0.05737 (13)	0.79080 (18)	0.0371 (5)
C10	0.9430 (3)	0.30429 (13)	0.7075 (2)	0.0419 (5)
C5	−0.0117 (3)	0.02976 (13)	0.67292 (19)	0.0409 (5)
C12	0.6114 (4)	0.23305 (15)	0.7390 (2)	0.0462 (6)
H12A	0.4937	0.2222	0.7844	0.055*
C3	−0.2281 (4)	0.03656 (14)	0.8471 (2)	0.0448 (5)
H3A	−0.3420	0.0043	0.8145	0.054*
C1	−0.0417 (4)	0.11356 (14)	0.9866 (2)	0.0474 (6)
H1A	−0.0129	0.1389	1.0577	0.057*
C7	0.6284 (3)	0.19098 (13)	0.63533 (18)	0.0385 (5)
C8	0.8067 (4)	0.20886 (14)	0.5689 (2)	0.0452 (6)
H8A	0.8200	0.1823	0.4992	0.054*
C11	0.7646 (4)	0.28965 (15)	0.7745 (2)	0.0499 (6)
H11A	0.7498	0.3180	0.8426	0.060*
C9	0.9633 (4)	0.26525 (15)	0.6049 (2)	0.0465 (6)
H9A	1.0814	0.2767	0.5601	0.056*
C2	−0.2269 (4)	0.06935 (15)	0.9593 (2)	0.0482 (6)
H2B	−0.3401	0.0616	1.0088	0.058*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
S1	0.0461 (4)	0.0519 (4)	0.0386 (4)	−0.0061 (3)	0.0064 (3)	−0.0075 (2)
Cl11	0.0523 (4)	0.0568 (5)	0.0598 (4)	−0.0115 (3)	0.0023 (3)	0.0021 (3)
C6	0.0449 (12)	0.0451 (14)	0.0355 (11)	0.0036 (10)	0.0087 (10)	−0.0003 (9)
N1	0.0414 (10)	0.0429 (11)	0.0375 (10)	−0.0030 (8)	0.0046 (8)	−0.0026 (8)
O1	0.0608 (10)	0.0597 (11)	0.0433 (9)	−0.0207 (9)	0.0103 (8)	−0.0127 (8)
N2	0.0453 (10)	0.0479 (12)	0.0381 (10)	−0.0055 (9)	0.0082 (8)	−0.0093 (9)
C4	0.0402 (10)	0.0361 (12)	0.0349 (11)	0.0006 (9)	0.0020 (9)	−0.0009 (9)
C10	0.0396 (11)	0.0387 (13)	0.0470 (13)	−0.0025 (9)	0.0017 (10)	0.0067 (10)
C5	0.0434 (11)	0.0403 (13)	0.0387 (12)	−0.0006 (10)	0.0022 (9)	−0.0013 (10)
C12	0.0448 (12)	0.0498 (15)	0.0458 (13)	−0.0024 (11)	0.0156 (10)	−0.0004 (11)
C3	0.0450 (12)	0.0451 (14)	0.0447 (13)	−0.0039 (10)	0.0056 (10)	−0.0021 (10)
C1	0.0563 (14)	0.0494 (15)	0.0373 (13)	−0.0001 (11)	0.0079 (11)	−0.0047 (10)
C7	0.0388 (11)	0.0399 (13)	0.0370 (11)	0.0033 (9)	0.0046 (9)	0.0054 (9)
C8	0.0467 (12)	0.0491 (14)	0.0413 (13)	0.0022 (11)	0.0127 (10)	0.0000 (10)
C11	0.0550 (13)	0.0530 (15)	0.0426 (13)	−0.0033 (12)	0.0102 (11)	−0.0072 (11)
C9	0.0430 (12)	0.0514 (15)	0.0465 (13)	−0.0026 (11)	0.0132 (10)	0.0059 (11)
C2	0.0498 (13)	0.0535 (15)	0.0426 (13)	0.0012 (11)	0.0129 (10)	−0.0008 (11)

Geometric parameters (Å, º) top

S1—C1	1.699 (3)	C12—C11	1.365 (3)
S1—C4	1.728 (2)	C12—C7	1.402 (3)
Cl11—C10	1.745 (2)	C12—H12A	0.9300
C6—N1	1.273 (3)	C3—C2	1.408 (3)
C6—C7	1.454 (3)	C3—H3A	0.9300
C6—H6A	0.9300	C1—C2	1.355 (3)
N1—N2	1.368 (2)	C1—H1A	0.9300
O1—C5	1.242 (3)	C7—C8	1.397 (3)
N2—C5	1.356 (3)	C8—C9	1.378 (3)
N2—H2A	0.8600	C8—H8A	0.9300
C4—C3	1.379 (3)	C11—H11A	0.9300
C4—C5	1.464 (3)	C9—H9A	0.9300
C10—C9	1.369 (3)	C2—H2B	0.9300
C10—C11	1.392 (3)

C1—S1—C4	91.38 (11)	C4—C3—H3A	123.6
N1—C6—C7	121.0 (2)	C2—C3—H3A	123.6
N1—C6—H6A	119.5	C2—C1—S1	113.05 (18)
C7—C6—H6A	119.5	C2—C1—H1A	123.5
C6—N1—N2	116.72 (19)	S1—C1—H1A	123.5
C5—N2—N1	121.65 (18)	C8—C7—C12	118.0 (2)
C5—N2—H2A	119.2	C8—C7—C6	120.3 (2)
N1—N2—H2A	119.2	C12—C7—C6	121.7 (2)
C3—C4—C5	121.4 (2)	C9—C8—C7	121.1 (2)
C3—C4—S1	110.67 (16)	C9—C8—H8A	119.5
C5—C4—S1	127.88 (17)	C7—C8—H8A	119.5
C9—C10—C11	121.4 (2)	C12—C11—C10	119.1 (2)
C9—C10—Cl11	120.03 (18)	C12—C11—H11A	120.5
C11—C10—Cl11	118.62 (18)	C10—C11—H11A	120.5
O1—C5—N2	118.6 (2)	C10—C9—C8	119.3 (2)
O1—C5—C4	120.0 (2)	C10—C9—H9A	120.4
N2—C5—C4	121.4 (2)	C8—C9—H9A	120.4
C11—C12—C7	121.2 (2)	C1—C2—C3	112.1 (2)
C11—C12—H12A	119.4	C1—C2—H2B	124.0
C7—C12—H12A	119.4	C3—C2—H2B	124.0
C4—C3—C2	112.8 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···O1ⁱ	0.86	2.01	2.825 (2)	158

Symmetry code: (i) −x, −y, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₂H₉ClN₂OS
M_r	264.72
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	293
a, b, c (Å)	6.0040 (12), 16.831 (3), 11.557 (2)
β (°)	94.38 (3)
V (Å³)	1164.5 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.49
Crystal size (mm)	0.21 × 0.19 × 0.18

Data collection
Diffractometer	Bruker SMART CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1997)
T_min, T_max	0.491, 0.728
No. of measured, independent and observed [I > 2σ(I)] reflections	11069, 2660, 1778
R_int	0.115
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.054, 0.141, 0.94
No. of reflections	2660
No. of parameters	154
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.52, −0.33

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	2.01	2.825 (2)	158

Symmetry code: (i) −x, −y, −z+1.

Acknowledgements

The authors would like to thank the Natural Science Foundation of Shandong Province (No·Y2008B23) for support.

References

Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA. 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