organic compounds
Ê
(Bolte & Dill, 1998). The N3ÐN4 bond distance of 1.374 (2) A
is appreciably shorter than a typical NÐN single bond, such as
Acta Crystallographica Section C
Crystal Structure
Ê
that found in free 2,4-dinitrophenylhydrazine [1.405 (6) A;
Communications
ISSN 0108-2701
Okabe et al., 1993], which suggests the existence of a deloca-
lized double bond in the hydrazone moiety.
Ê
The N3ÐC1 bond distance of 1.350 (2) A (Table 1) suggests
a partial double bond between the amine group and the
Ê
phenyl ring. It is notable that the C1ÐC2 [1.420 (3) A] and
Benzaldehyde 2,4-dinitrophenyl-
hydrazone
Ê
C1ÐC6 [1.414 (3) A] bonds are appreciably longer than the
Ê
average distance of 1.373 (3) A for the other CÐC bonds in
Ê
the same phenyl ring [range 1.356 (3)±1.387 (3) A]. The
Shang Shan,a Duan-Jun Xu,b* Chen-Hsiung Hung,c
Jing-Yun Wud and Michael Y. Chiangd
differences in ring bond lengths in (I) are comparable to the
situation in several derivatives of 2,4-dinitrophenylhydrazone
reported previously (Bolte & Dill, 1998; Ohba, 1996; Borwick
et al., 1997; Naidu et al., 1996; Shan et al., 2002) and are
presumably due to the overlap of the non-bonding orbital of
the imino N atom with the ꢀ orbitals of the arene. This overlap
contributes to the iminocyclohexadiene resonance structure.
Both intra- and intermolecular hydrogen bonding exists
between the imino and nitro groups (as shown in Fig. 1 and
aCollege of Chemical Engineering, Zhejiang University of Technology, Hangzhou,
Zhejiang, People's Republic of China, bDepartment of Chemistry, Zhejiang
University, Hangzhou, Zhejiang, People's Republic of China, cDepartment of
Chemistry, National Changhua University of Education, Changhua, Taiwan, and
dDepartment of Chemistry, National Sun Yat-Sen University, Kaohsiung, Taiwan
Correspondence e-mail: xudj@mail.hz.zj.cn
Received 9 December 2002
Accepted 28 January 2003
Online 18 February 2003
Ê
Table 2), which results in a short contact of 2.757 (3) A
between atoms O4 and O4(1 x, y, 1 z).
As the planar molecules are packed nearly perpendicular to
the crystallographic b axis, the molecules related by a screw
axis are nearly coplanar, with a dihedral angle of 5.03 (3)ꢀ. The
nearly coplanar molecules form a parallel-layered supramol-
ecular structure via the hydrogen bonding.
Crystals of the title compound, C13H10N4O4, were obtained
from a condensation reaction of benzaldehyde and 2,4-dinitro-
phenylhydrazine. The molecule assumes an approximately
planar E con®guration. Within the dinitrophenyl moiety, the
average distance for the aromatic CÐC bonds close to the
Fig. 2 shows the overlap arrangement of neighboring mol-
1
Ê
imino group [1.417 (3) A] is appreciably longer than the
average distance for the other aromatic CÐC bonds in the
ecules. The distances from atoms C2(1 x, 12 + y,
z) and
z) to the molecular plane that includes
2
1
C9(1 x, 12 + y,
Ê
same phenyl ring [1.373 (3) A]. This increased distance may be
2
a result of the overlap of the non-bonding orbital of the imino
N atom with the ꢀ orbitals of the arene. It is likely that ꢀ±ꢀ
stacking exists in the crystal structure.
Comment
As some phenylhydrazone derivatives have been shown to be
potential DNA-damaging or mutagenic agents (Okabe et al.,
1993), a series of new phenylhydrazone derivatives has been
synthesized in our laboratory in order to investigate their
structure±bioactivity relationship. The structure of the title
compound, (I), is reported here as an early result in our study
of this new series of compounds.
The molecular structure of (I) is shown in Fig. 1. The mol-
ecule assumes a ¯at planar structure, with a maximum devia-
Ê
tion of 0.066 (3) A for atom O2.
The title molecule crystallizes in the E conformation, with
the C8-phenyl group and the dinitrophenyl group on opposite
sides of the C7 N4 double bond. This con®guration agrees
with that commonly found in phenylhydrazone derivatives
Figure 1
The structure of (I) shown with 30% probability displacement ellipsoids.
Dashed lines show the hydrogen bonding. The symmetry code is as in
Table 2.
Acta Cryst. (2003). C59, o135±o136
DOI: 10.1107/S0108270103002464
# 2003 International Union of Crystallography o135
Shan, Shang
