N Phenyl N′ (2 thienyl­methyl­ene)­hydrazine

organic papers

o1552

Structure Reports Online

ISSN 1600-5368

N

-Phenyl-

N

_{-(2-thienylmethylene)hydrazine}

Suzan OÈ zcËelik,a_Muharrem DincËer,a_{* Memet SËekerci,}b Ayla Balabanc_{and UÈmmuÈhan} OÈ zdemirc

a_{Ondokuz Mayõs University, Arts and Sciences}

Faculty, Department of Physics, 55139 Samsun, Turkey,b_{Fõrat University, Arts and Sciences}

Faculty, Department of Chemistry, 23119- ElazõgÆ, Turkey, andc_{Gazi University,}

Arts and Sciences Faculty, Department of Chemistry, Ankara, Turkey

Correspondence e-mail: [email protected]

Key indicators

Single-crystal X-ray study T= 293 K

Mean(C±C) = 0.004 AÊ Rfactor = 0.038 wRfactor = 0.088

Data-to-parameter ratio = 13.7

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2004 International Union of Crystallography Printed in Great Britain ± all rights reserved

The title molecule, C11H10N2S, is almost planar with normal

bond lengths and angles. The crystal packing is stabilized by CÐH and van der Waals interactions.

Comment

Thiophene-containing compounds are known as materials with potential applications in the ¯avor (Bertramet al., 1993) and pharmaceutical industries (Press, 1991), in conducting polymer design (Bloor, 1995), as well as in non-linear optical materials (Nalwa, 1993). Moreover, thiophene derivatives are often used as intermediates in synthetic chemistry. The chemistry of hydrazones has been intensively investigated in recent years, owing to their coordinating capability, pharma-cological activity, antibacterial and antifungal properties, and their use in analytical chemistry as highly selective extractants (Dominoet al., 1984; Sakamotoet al., 1993; Liet al., 1998).

We report here the crystal structure of the title compound, (I) (Fig. 1), synthesized by a condensation reaction of thio-phene-2-carbaldehyde with phenylhydrazine. All bond lengths (Table 1) and angles in (I) are normal. The molecule is distorted from planarity; the dihedral angles of phenyl and thiophene rings with the plane formed by atoms C1/N1/N2/C7/ C11 are 9.6 (3) and 9.82 (3)_{, respectively. The crystal packing} (Fig. 2) is mainly stabilized by van der Waals interactions. However, there is a short C7ÐH7 Cg(Cgis the centroid of the phenyl ring) contact (Table 2), which may be attributed to a CÐH interaction.

Received 30 July 2004 Accepted 11 August 2004 Online 21 August 2004

Figure 1

Experimental

Compound (I) was prepared according to the method described in the literature by Sarõ & GuÈrkan (2003). A stirred mixture of phenylhydrazine (108 g, 1 mmol) and thiophene-2-carboxaldehyde (112 mg, 1 mmol) in methanolic media was re¯uxed for 6 h. After cooling, the precipitate was ®ltered off and was crystallized from methanol (yield 78%, m.p. 398 K).

Crystal data C11H10N2S Mr= 202.27

Orthorhombic,P212121 a= 6.0473 (6) AÊ b= 7.4417 (7) AÊ c= 22.376 (3) AÊ V= 1006.97 (19) AÊ3 Z= 4

Dx= 1.334 Mg mÿ3

MoKradiation

Cell parameters from 12 880 re¯ections

= 1.8±25.8

= 0.28 mmÿ1 T= 293 (2) K Plate, colorless 0.500.330.05 mm

Data collection

Stoe IPDS-2 diffractometer

!scans

Absorption correction: by integration (X-RED32; Stoe & Cie, 2002) Tmin= 0.892,Tmax= 0.986 5892 measured re¯ections

1738 independent re¯ections 1403 re¯ections withI> 2(I) Rint= 0.054

max= 25.0 h=ÿ6!7 k=ÿ8!8 l=ÿ26!26 Re®nement

Re®nement onF2 R[F2_{> 2(F}2_{)] = 0.038} wR(F2_{) = 0.088} S= 0.93 1738 re¯ections 127 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.052P)2]

whereP= (Fo2+ 2Fc2)/3

(/)max= 0.001

max= 0.37 e AÊÿ3

min=ÿ0.21 e AÊÿ3

Absolute structure: (Flack, 1983), 688 Friedel pairs

Flack parameter = 0.03 (12)

Table 1

Selected geometric parameters (AÊ,_). N1ÐN2 1.363 (3) S1ÐC8 1.709 (3) S1ÐC11 1.721 (3)

N1ÐC1 1.381 (4) N2ÐC7 1.272 (4) C7ÐC11 1.445 (4)

Table 2

Hydrogen-bonding geometry (AÊ,_).

DÐH A DÐH H A D A DÐH A

C7ÐH7 Cgi _{0.93 2.68 3.461 (3) 142}

Symmetry code: (i)ÿx;yÿ1

2;12ÿz.Cgis the centroid of the phenyl ring.

All H atoms were positioned geometrically (NÐH = 0.86, CÐH = 0.93 AÊ) and re®ned using a riding model. The Uiso values were

assigned to 1.2Ueq(C,N).

Data collection: X-AREA (Stoe & Cie, 2002); cell re®nement:

X-AREA; data reduction:X-RED32 (Stoe & Cie, 2002); program(s)

used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to re®ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics:ORTEP-3for Windows(Farrugia, 1997); software used to prepare material for publication:WinGX(Farrugia, 1999).

References

Bertram, H. J., Emberger, R., GuÈntrt, M., Sommer, H. & Werkhoff, P. (1993). Recent Dev. Flavor Fragrance Chem.11, 241±259.

Bloor, D. (1995).Chem. Ber.31, 385±387.

Domino, P., Pelizzi, C. & Predieri, G. (1984).Polyhedron,3, 281±286. Farrugia, L. J. (1997).J. Appl. Cryst.30, 565.

Farrugia, L. J. (1999).J. Appl. Cryst.32, 837±838. Flack, H. D. (1983).Acta Cryst.A39, 876±881.

Li, X. R., Sun, Z. M. & Chang, J. C. (1998).Synth. React.Inorg. Met. Org. Chem.18, 657±665.

Nalwa, H. S. (1993).Adv. Mater.5, 341±358.

Press, J. B. (1991).Chem. Heterocycl. Compd,44, 397±502.

Sakamoto, H., Goto, H., Yokoshima, M., Dobashi, M., Ishikawa, J., Doi, K. & Otomo, M. (1993).Bull. Chem. Soc. Jpn,66, 2907±1914.

Sarõ, N. & GuÈrkan, P. (2003).Transition Met. Chem.28, 687±693.

Sheldrick, G. M. (1997). SHELXL97 and SHELXS97. University of GoÈttingen, Germany.

Stoe & Cie (2002).X-AREA(Version 1.18) andX-RED32 (Version 1.04). Stoe & Cie, Darmstadt, Germany.

Figure 2

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Acta Cryst. (2004). E60, o1552–o1553

supporting information

Acta Cryst. (2004). E60, o1552–o1553 [https://doi.org/10.1107/S1600536804019932]

N

-Phenyl-

N

′

-(2-thienylmethylene)hydrazine

Suzan

Ö

z

ç

elik, Muharrem Din

ç

er, Memet

Ş

ekerci, Ayla Balaban and

Ü

mm

ü

han

Ö

zdemir

N-Phenyl-N′-(thiophen-2-ylmethylene)hydrazine

Crystal data C11H10N2S

Mr = 202.27

Orthorhombic, P212121

Hall symbol: P 2ac 2ab a = 6.0473 (6) Å b = 7.4417 (7) Å c = 22.376 (3) Å V = 1006.97 (19) Å3

Z = 4

F(000) = 424 Dx = 1.334 Mg m−3

Mo Kα radiation, λ = 0.71073 Å Cell parameters from 12880 reflections θ = 1.8–25.8°

µ = 0.28 mm−1

T = 293 K Plate, colorless 0.50 × 0.33 × 0.05 mm

Data collection Stoe IPDS-2

diffractometer

Radiation source: fine-focus sealed tube Plane graphite monochromator

Detector resolution: 6.67 pixels mm-1

ω rotation scans

Absorption correction: integration (X-RED; Stoe & Cie, 2002) Tmin = 0.892, Tmax = 0.986

5892 measured reflections 1738 independent reflections 1403 reflections with I > 2σ(I) Rint = 0.054

θmax = 25.0°, θmin = 1.8°

h = −6→7 k = −8→8 l = −26→26

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.038}

wR(F2_{) = 0.088}

S = 0.93 1738 reflections 127 parameters 0 restraints

Primary atom site location: structure-invariant direct methods

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.052P)2]

where P = (Fo2 + 2Fc2)/3

(Δ/σ)max = 0.001

Δρmax = 0.37 e Å−3

Δρmin = −0.21 e Å−3

Special details

Experimental. Melting points were determined in open capillary tubes on a digital Gallenkamp melting point apparatus and are uncorrected. The IR spectra were recorded for KBr disks with a Mattson 1000 F T—IR spectrometer. 1H-NMR spectra were recorded on a FX 90 Jeol 90 MHz NMR, spectrometer in CDCl3 + DMSO-d6 with TMS as an internal standard. Elemental analyses were done on a LECO-CHNS-938. Starting materials was obtained from Fluka or Aldrich. For (I): IR (KBr) ?: 3325 (N—H), 3100,3087,3082, (aromatic C—H), 1603 (C=N), 1579,1535 (C=C). cm-1. 1H NMR (Aceton-d6) ?: 9.23(s, 1H, NH), 8.03(s, 1H, CH=), 7.48–6.63 (m 8H, Aromatic protons). 13 C NMR (Aceton- d6, TMS, ? p.p.m.): 146.20, 142.40, 133.06, 131.94, 129.87, 126.91, 126.17, 120.13, 113.37. Anal calcd for C11H10N2S: C: 65.35, H: 4.95, N: 13.88, S:15.84%.

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 F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) 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₎

x y z Uiso*/Ueq

S1 0.64972 (13) 0.72536 (9) 0.15971 (3) 0.0366 (2) N1 0.0542 (4) 0.5413 (3) 0.25417 (11) 0.0322 (6) H1 −0.0396 0.4707 0.2373 0.039* N2 0.2345 (4) 0.5983 (3) 0.22289 (11) 0.0301 (6) C1 0.0196 (5) 0.5951 (3) 0.31248 (12) 0.0278 (6) C2 −0.1826 (5) 0.5552 (3) 0.33942 (13) 0.0329 (7) H2 −0.2926 0.4971 0.3177 0.040* C3 −0.2192 (5) 0.6017 (4) 0.39798 (14) 0.0379 (7) H3 −0.3534 0.5732 0.4159 0.045* C4 −0.0575 (6) 0.6911 (4) 0.43083 (13) 0.0387 (8) H4 −0.0825 0.7224 0.4705 0.046* C5 0.1417 (5) 0.7328 (4) 0.40332 (11) 0.0356 (6) H5 0.2503 0.7928 0.4250 0.043* C6 0.1818 (5) 0.6876 (3) 0.34499 (13) 0.0303 (6) H6 0.3155 0.7180 0.3271 0.036* C7 0.2451 (5) 0.5545 (3) 0.16801 (13) 0.0301 (7) H7 0.1329 0.4848 0.1516 0.036* C8 0.7673 (5) 0.7451 (4) 0.09058 (12) 0.0384 (7) H8 0.9016 0.8023 0.0836 0.046* C9 0.6436 (4) 0.6683 (2) 0.04706 (9) 0.0370 (7) H9 0.6836 0.6668 0.0069 0.044* C10 0.4461 (4) 0.5902 (2) 0.06955 (9) 0.0314 (7) H10 0.3417 0.5323 0.0459 0.038* C11 0.4273 (5) 0.6105 (3) 0.13064 (12) 0.0294 (7)

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

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Acta Cryst. (2004). E60, o1552–o1553

N1 0.0283 (16) 0.0303 (13) 0.0379 (13) −0.0091 (11) −0.0024 (12) −0.0024 (10) N2 0.0285 (14) 0.0273 (12) 0.0345 (13) 0.0008 (10) −0.0029 (11) 0.0034 (10) C1 0.0254 (17) 0.0209 (13) 0.0370 (16) 0.0006 (12) −0.0022 (12) 0.0055 (11) C2 0.0256 (17) 0.0298 (14) 0.0435 (16) 0.0001 (12) −0.0033 (15) 0.0051 (13) C3 0.0305 (19) 0.0356 (17) 0.0476 (18) 0.0028 (14) 0.0076 (14) 0.0130 (14) C4 0.052 (2) 0.0329 (16) 0.0315 (15) 0.0116 (15) 0.0020 (14) 0.0027 (13) C5 0.0407 (17) 0.0275 (15) 0.0385 (14) −0.0023 (17) −0.0102 (15) 0.0018 (12) C6 0.0220 (16) 0.0252 (13) 0.0436 (16) 0.0001 (11) −0.0030 (14) 0.0048 (12) C7 0.0272 (15) 0.0236 (13) 0.0395 (18) 0.0014 (11) −0.0054 (13) 0.0017 (12) C8 0.0390 (17) 0.0259 (16) 0.0502 (18) 0.0023 (14) 0.0050 (13) 0.0002 (13) C9 0.043 (2) 0.0307 (15) 0.0374 (15) −0.0015 (16) 0.0028 (17) 0.0003 (12) C10 0.0329 (18) 0.0266 (14) 0.0348 (15) 0.0020 (14) −0.0033 (13) 0.0032 (12) C11 0.0312 (18) 0.0180 (13) 0.0390 (16) 0.0023 (12) −0.0047 (13) 0.0022 (11)

Geometric parameters (Å, º)

S1—C8 1.709 (3) C4—H4 0.9300 S1—C11 1.721 (3) C5—C6 1.369 (4) N1—N2 1.363 (3) C5—H5 0.9300 N1—C1 1.381 (4) C6—H6 0.9300 N1—H1 0.8600 C7—C11 1.445 (4) N2—C7 1.272 (4) C7—H7 0.9300 C1—C2 1.395 (4) C8—C9 1.354 (4) C1—C6 1.402 (4) C8—H8 0.9300 C2—C3 1.373 (4) C9—C10 1.4205

C2—H2 0.9300 C9—H9 0.9300

C3—C4 1.393 (4) C10—C11 1.380 (3) C3—H3 0.9300 C10—H10 0.9300 C4—C5 1.388 (4)

C6—C5—H5 119.3 C7—C11—S1 121.4 (2)

Hydrogen-bond geometry (Å, º)

D—H···A D—H H···A D···A D—H···A C5—H5···Cg1i _{0.93 3.01 3.631 (3) 126}

C7—H7···Cgii _{0.93 2.68 3.461 (3) 142}

C8—H8···Cgi _{0.93 2.83 3.443 (3) 125}