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

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ISSN: 2056-9890

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

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 ππ 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[Jiang, J.-H. (2010). Acta Cryst. E66, o922.]).

[Scheme 1]

Experimental

Crystal data
  • C12H9ClN2OS

  • Mr = 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[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]) Tmin = 0.491, Tmax = 0.728

  • 11069 measured reflections

  • 2660 independent reflections

  • 1778 reflections with I > 2σ(I)

  • Rint = 0.115

Refinement
  • R[F2 > 2σ(F2)] = 0.054

  • wR(F2) = 0.141

  • S = 0.94

  • 2660 reflections

  • 154 parameters

  • H-atom parameters constrained

  • Δρmax = 0.52 e Å−3

  • Δρmin = −0.33 e Å−3

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A D—H H⋯A DA 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[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); cell refinement: SAINT (Bruker, 1997[Bruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.]); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); molecular graphics: SHELXTL (Sheldrick, 2008[Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.]); software used to prepare material for publication: SHELXTL.

Supporting information


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.

Refinement top

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 Uiso(H) = 1.2Ueq(C,N) or 1.5Ueq(Cmethyl).

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
[Figure 1] Fig. 1. The molecular structure of (I) showing 30% probability displacement ellipsoids.
N'-(4-Chlorobenzylidene)thiophene-2-carbohydrazide top
Crystal data top
C12H9ClN2OSF(000) = 544
Mr = 264.72Dx = 1.510 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 1778 reflections
a = 6.0040 (12) Åθ = 3–27.5°
b = 16.831 (3) ŵ = 0.49 mm1
c = 11.557 (2) ÅT = 293 K
β = 94.38 (3)°Block, colorless
V = 1164.5 (4) Å30.21 × 0.19 × 0.18 mm
Z = 4
Data collection top
Bruker SMART CCD
diffractometer
2660 independent reflections
Radiation source: fine-focus sealed tube1778 reflections with I > 2σ(I)
Graphite monochromatorRint = 0.115
ω scansθmax = 27.5°, θmin = 3.0°
Absorption correction: multi-scan
(SADABS; Bruker, 1997)
h = 77
Tmin = 0.491, Tmax = 0.728k = 2121
11069 measured reflectionsl = 1414
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.054Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.141H-atom parameters constrained
S = 0.94 w = 1/[σ2(Fo2) + (0.061P)2]
where P = (Fo2 + 2Fc2)/3
2660 reflections(Δ/σ)max < 0.001
154 parametersΔρmax = 0.52 e Å3
0 restraintsΔρmin = 0.33 e Å3
Crystal data top
C12H9ClN2OSV = 1164.5 (4) Å3
Mr = 264.72Z = 4
Monoclinic, P21/nMo Kα radiation
a = 6.0040 (12) ŵ = 0.49 mm1
b = 16.831 (3) ÅT = 293 K
c = 11.557 (2) Å0.21 × 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)
Tmin = 0.491, Tmax = 0.728Rint = 0.115
11069 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.0540 restraints
wR(F2) = 0.141H-atom parameters constrained
S = 0.94Δρmax = 0.52 e Å3
2660 reflectionsΔρmin = 0.33 e Å3
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
xyzUiso*/Ueq
S10.13248 (10)0.11796 (4)0.87758 (5)0.0454 (2)
Cl111.14308 (10)0.37422 (4)0.75642 (6)0.0564 (2)
C60.4682 (4)0.12975 (13)0.5974 (2)0.0415 (5)
H6A0.47930.10520.52600.050*
N10.3130 (3)0.10929 (11)0.66045 (16)0.0405 (5)
O10.1503 (3)0.01594 (11)0.62318 (14)0.0543 (5)
N20.1660 (3)0.05312 (11)0.61567 (15)0.0435 (5)
H2A0.18690.03210.54950.052*
C40.0422 (3)0.05737 (13)0.79080 (18)0.0371 (5)
C100.9430 (3)0.30429 (13)0.7075 (2)0.0419 (5)
C50.0117 (3)0.02976 (13)0.67292 (19)0.0409 (5)
C120.6114 (4)0.23305 (15)0.7390 (2)0.0462 (6)
H12A0.49370.22220.78440.055*
C30.2281 (4)0.03656 (14)0.8471 (2)0.0448 (5)
H3A0.34200.00430.81450.054*
C10.0417 (4)0.11356 (14)0.9866 (2)0.0474 (6)
H1A0.01290.13891.05770.057*
C70.6284 (3)0.19098 (13)0.63533 (18)0.0385 (5)
C80.8067 (4)0.20886 (14)0.5689 (2)0.0452 (6)
H8A0.82000.18230.49920.054*
C110.7646 (4)0.28965 (15)0.7745 (2)0.0499 (6)
H11A0.74980.31800.84260.060*
C90.9633 (4)0.26525 (15)0.6049 (2)0.0465 (6)
H9A1.08140.27670.56010.056*
C20.2269 (4)0.06935 (15)0.9593 (2)0.0482 (6)
H2B0.34010.06161.00880.058*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
S10.0461 (4)0.0519 (4)0.0386 (4)0.0061 (3)0.0064 (3)0.0075 (2)
Cl110.0523 (4)0.0568 (5)0.0598 (4)0.0115 (3)0.0023 (3)0.0021 (3)
C60.0449 (12)0.0451 (14)0.0355 (11)0.0036 (10)0.0087 (10)0.0003 (9)
N10.0414 (10)0.0429 (11)0.0375 (10)0.0030 (8)0.0046 (8)0.0026 (8)
O10.0608 (10)0.0597 (11)0.0433 (9)0.0207 (9)0.0103 (8)0.0127 (8)
N20.0453 (10)0.0479 (12)0.0381 (10)0.0055 (9)0.0082 (8)0.0093 (9)
C40.0402 (10)0.0361 (12)0.0349 (11)0.0006 (9)0.0020 (9)0.0009 (9)
C100.0396 (11)0.0387 (13)0.0470 (13)0.0025 (9)0.0017 (10)0.0067 (10)
C50.0434 (11)0.0403 (13)0.0387 (12)0.0006 (10)0.0022 (9)0.0013 (10)
C120.0448 (12)0.0498 (15)0.0458 (13)0.0024 (11)0.0156 (10)0.0004 (11)
C30.0450 (12)0.0451 (14)0.0447 (13)0.0039 (10)0.0056 (10)0.0021 (10)
C10.0563 (14)0.0494 (15)0.0373 (13)0.0001 (11)0.0079 (11)0.0047 (10)
C70.0388 (11)0.0399 (13)0.0370 (11)0.0033 (9)0.0046 (9)0.0054 (9)
C80.0467 (12)0.0491 (14)0.0413 (13)0.0022 (11)0.0127 (10)0.0000 (10)
C110.0550 (13)0.0530 (15)0.0426 (13)0.0033 (12)0.0102 (11)0.0072 (11)
C90.0430 (12)0.0514 (15)0.0465 (13)0.0026 (11)0.0132 (10)0.0059 (11)
C20.0498 (13)0.0535 (15)0.0426 (13)0.0012 (11)0.0129 (10)0.0008 (11)
Geometric parameters (Å, º) top
S1—C11.699 (3)C12—C111.365 (3)
S1—C41.728 (2)C12—C71.402 (3)
Cl11—C101.745 (2)C12—H12A0.9300
C6—N11.273 (3)C3—C21.408 (3)
C6—C71.454 (3)C3—H3A0.9300
C6—H6A0.9300C1—C21.355 (3)
N1—N21.368 (2)C1—H1A0.9300
O1—C51.242 (3)C7—C81.397 (3)
N2—C51.356 (3)C8—C91.378 (3)
N2—H2A0.8600C8—H8A0.9300
C4—C31.379 (3)C11—H11A0.9300
C4—C51.464 (3)C9—H9A0.9300
C10—C91.369 (3)C2—H2B0.9300
C10—C111.392 (3)
C1—S1—C491.38 (11)C4—C3—H3A123.6
N1—C6—C7121.0 (2)C2—C3—H3A123.6
N1—C6—H6A119.5C2—C1—S1113.05 (18)
C7—C6—H6A119.5C2—C1—H1A123.5
C6—N1—N2116.72 (19)S1—C1—H1A123.5
C5—N2—N1121.65 (18)C8—C7—C12118.0 (2)
C5—N2—H2A119.2C8—C7—C6120.3 (2)
N1—N2—H2A119.2C12—C7—C6121.7 (2)
C3—C4—C5121.4 (2)C9—C8—C7121.1 (2)
C3—C4—S1110.67 (16)C9—C8—H8A119.5
C5—C4—S1127.88 (17)C7—C8—H8A119.5
C9—C10—C11121.4 (2)C12—C11—C10119.1 (2)
C9—C10—Cl11120.03 (18)C12—C11—H11A120.5
C11—C10—Cl11118.62 (18)C10—C11—H11A120.5
O1—C5—N2118.6 (2)C10—C9—C8119.3 (2)
O1—C5—C4120.0 (2)C10—C9—H9A120.4
N2—C5—C4121.4 (2)C8—C9—H9A120.4
C11—C12—C7121.2 (2)C1—C2—C3112.1 (2)
C11—C12—H12A119.4C1—C2—H2B124.0
C7—C12—H12A119.4C3—C2—H2B124.0
C4—C3—C2112.8 (2)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N2—H2A···O1i0.862.012.825 (2)158
Symmetry code: (i) x, y, z+1.

Experimental details

Crystal data
Chemical formulaC12H9ClN2OS
Mr264.72
Crystal system, space groupMonoclinic, P21/n
Temperature (K)293
a, b, c (Å)6.0040 (12), 16.831 (3), 11.557 (2)
β (°) 94.38 (3)
V3)1164.5 (4)
Z4
Radiation typeMo Kα
µ (mm1)0.49
Crystal size (mm)0.21 × 0.19 × 0.18
Data collection
DiffractometerBruker SMART CCD
diffractometer
Absorption correctionMulti-scan
(SADABS; Bruker, 1997)
Tmin, Tmax0.491, 0.728
No. of measured, independent and
observed [I > 2σ(I)] reflections
11069, 2660, 1778
Rint0.115
(sin θ/λ)max1)0.649
Refinement
R[F2 > 2σ(F2)], wR(F2), S 0.054, 0.141, 0.94
No. of reflections2660
No. of parameters154
H-atom treatmentH-atom parameters constrained
Δρmax, Δρmin (e Å3)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···AD—HH···AD···AD—H···A
N2—H2A···O1i0.862.012.825 (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

First citationBruker (1997). SMART, SAINT and SADABS. Bruker AXS Inc., Madison, Wisconsin, USA.  Google Scholar
First citationJiang, J.-H. (2010). Acta Cryst. E66, o922.  Web of Science CrossRef IUCr Journals Google Scholar
First citationSheldrick, G. M. (2008). Acta Cryst. A64, 112–122.  Web of Science CrossRef CAS IUCr Journals Google Scholar

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ISSN: 2056-9890
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