N-(3,5-Dinitrobenzoyl)-N0-phenylhydrazine: sheets built from N—H O and C—H O hydrogen bonds

Instituto de Tecnologia em Fármacos, FarManguinhos, FIOCRUZ, 21041-250 Rio de Janeiro, RJ, Brazil, Instituto de Quı́mica, Departamento de Quı́mica Inorgânica, Universidade Federal do Rio de Janeiro, CP 68563, 21945-970 Rio de Janeiro, RJ, Brazil, Department of Chemistry, University of Aberdeen, Meston Walk, Old Aberdeen AB24 3UE, Scotland, and School of Chemistry, University of St Andrews, Fife KY16 9ST, Scotland


Comment
We report here the molecular and supramolecular structure of the title compound, (I) (Fig. 1). The coordination of atom N1 is exactly planar, while that of N2 is markedly pyramidal. The overall molecular conformation is defined by six torsion angles (Table 1), which show that the -C( O)-NH-portion adopts the usual trans-planar conformation. While the nitrated aryl ring is nearly coplanar with the central amide unit, the torsion angle of nearly 90 around the N-N bond is a reflection of the mutually orthogonal orientation of the lone pairs on the two hydrazine N atoms. The molecules thus have no internal symmetry in the solid state and hence are chiral, but the centrosymmetric space group accommodates equal numbers of the two enantiomeric forms.
The molecules of (I) are linked into sheets by a combination of two N-HÁ Á ÁO hydrogen bonds and one C-HÁ Á ÁO hydrogen bond (Table 2), and the formation of the sheet is readily analysed in terms of two one-dimensional substructures. Atom N2 in the molecule at (x, y, z) acts as a hydrogenbond donor to nitro atom O31 in the molecule at (x, y, 1 + z), so generating by translation a C(9) (Bernstein et al., 1995) chain running parallel to the [001] direction (Fig. 2). Atoms N1 and C2 in the molecule at (x, y, z) both act as hydrogen-bond donors to carbonyl atom O7 in the molecule at (À 1 2 + x, 3 2 À y, À 1 2 + z), so forming a C(4)C(5)[R 1 2 (7)] chain of rings along [101] and generated by the n-glide plane at y = 3 4 (Fig. 3). The combination of the [001] and [101] chains then generates a sheet parallel to (010) (Fig. 4). Two such sheets, generated by the n-glide planes at y = 1 4 and y = 3 4 , pass through each unit cell, but there are no direction-specific interactions between adjacent sheets.

Experimental
A mixture of equimolar quantities (10 mmol of each component) of 3,5-dinitrobenzoyl chloride and phenylhydrazine in tetrahydrofuran (20 ml) was heated under reflux for 24 h in a dinitrogen atmosphere. The reaction mixture was cooled, and the solvent was removed under reduced pressure. The solid product was washed successively with cold ethanol and diethyl ether, and then recrystallized from ethanol (m. where P = (F o 2 + 2F c 2 )/3 (Á/) max < 0.001 Á max = 0.24 e Å À3 Á min = À0.28 e Å À3 Table 1 Selected torsion angles ( ).
All H atoms were located in difference maps and then treated as riding atoms with distances C-H = 0.95 Å and N-H = 0.88 Å , and with U iso (H) = 1.2U eq (C,N).

Figure 1
The molecular structure of (I), showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. ware used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999). X-ray data were collected at the EPSRC X-ray Crystallographic Service, University of Southampton, England; the authors thank the staff of the Service for all their help and advice. JLW thanks CNPq and FAPERJ for financial support.