N′-[1-(2,4-Dioxo-3,4-dihydro-2H-1-benzopyran-3-yl­idene)eth­yl]thiophene-2-carbo­hydrazide

Helliwell, M.; Nasiopoulou, D.A.; Harris, P.A.; Kotali, A.; Joule, J.A.

doi:10.1107/S1600536811010907

Volume 67
Part 4
Page o1014
April 2011

Received 7 March 2011
Accepted 23 March 2011
Online 31 March 2011

Key indicators
Single-crystal X-ray study
T = 100 K
Mean (C-C) = 0.006 Å
R = 0.058
wR = 0.116
Data-to-parameter ratio = 11.2
Details

N'-[1-(2,4-Dioxo-3,4-dihydro-2H-1-benzopyran-3-ylidene)ethyl]thiophene-2-carbohydrazide

Madeleine Helliwell,^a Despina A. Nasiopoulou,^b Philip A. Harris,^c Antigoni Kotali ^b ^* and John A. Joule ^a

^aThe School of Chemistry, The University of Manchester, Manchester M13 9PL, England,^bLaboratory of Organic Chemistry, Department of Chemical Engineering, University of Thessaloniki, Thessaloniki 54124, Greece, and ^cGlaxoSmithKline, 1250 South Collegeville Road, P.O.Box 5089, Collegeville, PA 19426-0989, USA
Correspondence e-mail: kotali@eng.auth.gr

The title compound, C₁₆H₁₂N₂O₄S, was obtained by the condensation of 3-acetyl-4-hydroxycoumarin with thien-2-ylcarbonyl hydrazide. The pyran ring adopts a 2,4-dione tautomeric form. The benzopyran ring system is almost coplanar with the thiophene ring [dihedral angle 0.9 (2)°]. The exocyclic C=C double bond has an E geometry. The molecular conformation is stabilized by an intramolecular N-HO hydrogen bond. In the crystal, intermolecular N-HO hydrogen bonds link the molecules into chains along the a axis.

Related literature

For the synthesis, characterization and reactions of N-acyl hydrazones, see: Kotali (2009); Kotali et al., (2010).

Experimental

Crystal data

C₁₆H₁₂N₂O₄S
M_r = 328.34
Triclinic, $[P \overline 1]$
a = 4.8631 (11) Å
b = 11.833 (3) Å
c = 13.296 (3) Å
= 107.106 (5)°
= 100.376 (4)°
= 97.553 (4)°
V = 705.3 (3) Å³
Z = 2
Mo K radiation
= 0.25 mm^-1
T = 100 K
0.55 × 0.15 × 0.08 mm

Data collection

Bruker SMART APEX CCD diffractometer
3526 measured reflections
2441 independent reflections
1403 reflections with I > 2(I)
R_int = 0.072

Refinement

R[F² > 2(F²)] = 0.058
wR(F²) = 0.116
S = 0.87
2441 reflections
217 parameters
6 restraints
H atoms treated by a mixture of independent and constrained refinement
_max = 0.33 e Å^-3
_min = -0.36 e Å^-3

Table 1
Hydrogen-bond geometry (Å, °)

D-HA	D-H	HA	DA	D-HA
N2-H2NO4	1.00 (4)	1.64 (5)	2.481 (4)	140 (4)
N1-H1NO1ⁱ	0.92 (4)	1.93 (4)	2.841 (4)	177 (4)
Symmetry code: (i) x+1, y, z.

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2002); data reduction: SAINT; program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXTL and PLATON.

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: RZ2570 ).

Acknowledgements

The authors thank Royal Society of Chemistry for financial support of this work.

References

Bruker (2001). SMART. Bruker AXS Inc., Madison, Wisconsin, USA.
Bruker (2002). SAINT. Bruker AXS Inc., Madison, Wisconsin, USA.
Burla, M. C., Caliandro, R., Camalli, M., Carrozzini, B., Cascarano, G. L., De Caro, L., Giacovazzo, C., Polidori, G. & Spagna, R. (2005). J. Appl. Cryst. 38, 381-388.
Kotali, A. (2009). Arkivoc, i, 81-96.
Kotali, A., Kotali, E., Lafazanis, I. S. & Harris, P. A. (2010). Curr. Org. Synth. 7, 62-77.
Sheldrick, G. M. (2008). Acta Cryst. A64, 112-122.
Spek, A. L. (2009). Acta Cryst. D65, 148-155.

organic compounds