organic compounds
by atoms N11 at (x, y, z), N17 and C13 both at ( 12 + x, 23 y,
(12 + x, 32 y, 12 + z), so forming a C(7) chain running parallel to
the [101] direction and generated by the n-glide plane at y = 34.
At the same time, pyridyl atom C12 in the molecule at (12 + x,
z), and N27 and C22 both at (12 x, y,
distances are within the sums of the van der Waals radii,
+ z). The HÁ Á ÁCl
1
2
3
2
although the interaction energies are probably small. Atoms
1
y, 12 + z) acts as a hydrogen-bond donor to carbonyl atom
Cl1, N17vii, N27viii and C22viii [symmetry codes: (vii) x
,
y
O2 in the molecule at (x, y, z), thereby forming a C(9) chain
along [101]. The combination of these two hydrogen bonds
then generates a C(7)C(9)[R22(8)] chain of rings along [101]
(Fig. 6).
2
+ 32, z; (viii) x + 21, y, z 12] are effectively coplanar, and the
overall coordination of atom Cl1 can be regarded as a
distorted trigonal bipyramid, with atoms N11 and C13vii
occupying the axial sites (Fig. 5).
The [101] chains of rings are linked into sheets by a simple
chain motif running parallel to the [001] direction. Pyridyl
atom C15 in the molecule at (x, y, z) acts as a donor to
carbonyl atom O2 in the molecule at (x, y, 1 + z) in a nearly
linear hydrogen bond, so generating by translation a C(8)
chain running parallel to the [001] direction. The combination
of the [101] chain of rings and the [001] chain generates a (010)
sheet, whose formation is further augmented by a single ꢀ±ꢀ
stacking interaction. The nitrated C21±C26 aryl rings in the
molecules at (x, y, z) and (2 x, 1 y, 2 z), which lie in
adjacent [101] chains offset along [100], are strictly parallel,
The molecules of compound (II) (Fig. 2) are linked into a
three-dimensional framework by a combination of one NÐ
HÁ Á ÁN hydrogen bond and three CÐHÁ Á ÁO hydrogen bonds
(Table 2), augmented by an aromatic ꢀ±ꢀ stacking interaction.
The formation of this rather complex framework can readily
be analysed in terms of two one-dimensional substructures,
each in the form of a chain of rings built from the co-operative
interaction of two hydrogen bonds.
Hydrazine atom N17 in the molecule at (x, y, z) acts as a
hydrogen-bond donor to the ring atom N11 in the molecule at
Ê
with an interplanar spacing of 3.342 (2) A; the ring-centroid
Ê
separation is 3.519 (2) A, corresponding to a ring offset of
Ê
1.102 (2) A.
Two (010) sheets pass through each unit cell; they are
related to one another by inversion and are generated by the
n-glide planes at y = 14 and y = 43, respectively. Adjacent sheets
are linked into a single continuous three-dimensional frame-
work structure by the ®nal CÐHÁ Á ÁO hydrogen bond. Pyridyl
atom C13 in the molecule at (x, y, z), which lies in the (010)
3
4
sheet generated by the n-glide plane at y = , acts as a
hydrogen-bond donor to nitro atom O51 in the molecule at
(1
x, 1
y, 2
generated by the n-glide plane at y = , so generating by
z), which forms part of the (010) sheet
1
4
inversion an R22(24) ring centred at (12, , 1). The combination
1
2
of the two hydrogen bonds having atoms C13 and C15 as the
donors then generates a chain of edge-fused centrosymmetric
Figure 6
1
rings having R22(24) rings centred at (21, , n) (n = zero or
Part of the crystal structure of (II), showing the formation of a
C(7)C(9)[R22(8)] chain of rings along [101]. For the sake of clarity, H
atoms not involved in the motif shown have been omitted. Atoms marked
with an asterisk (*) or a hash (#) are at the symmetry positions (12 + x, 21 y,
2
1
1
integer) and R44(24) rings centred at (12, , + n) (n = zero or
integer) (Fig. 7).
2
2
1
2
1
2
1
+ z) and ( + x, 12 y,
+ z), respectively.
2
Experimental
Substituted nitrobenzoyl chlorides were prepared by treating the
appropriate carboxylic acid (1 g) with thionyl chloride (3 equiva-
lents), N,N-dimethylformamide (0.1 equivalent) and dichloro-
methane (20 ml) at room temperature, under stirring and in a
dinitrogen atmosphere. After 6±8 h, the excess of thionyl chloride
was removed under reduced pressure to leave the crude acyl chloride,
which was used without puri®cation in a reaction with iso-
nicotinoylhydrazine (isoniazid, 1 equivalent) and, in the preparation
of (II) only, triethylamine (1 equivalent) in tetrahydrofuran (20 ml) at
340 K. Compound (I) was puri®ed by recrystallization from ethanol
(m.p. 510±511 K, yield 88%). MS m/z: 320 [M HCl]+. NMR
(DMSO-d6): ꢁ(H) 11.48 (1H, s, NH), 11.30 (1H, s, NH), 9.06 (2H, d,
J = 4.5 Hz, H2 and H6), 8.63 (1H, s, H20), 8.28 (1H, d, J = 5.5 Hz, H3
and H5), 8.27 (1H, d, J = 8.5 Hz, H60), 8.01 (1H, d, J = 8.5 Hz, H50);
ꢁ(C) 162.7, 162.6, 147.3, 145.8, 143.9, 132.5, 132.3, 132.0, 128.7, 124.8,
123.7. IR (KBr disk, cm 1): 3171 (NH), 1710 (CO), 1677 (CO).
Compound (II) was puri®ed by column chromatography on silica gel,
using as eluant a hexane/ethyl acetate gradient, followed by recrys-
Figure 7
A stereoview of part of the crystal structure of (II), showing the
formation of a chain of edge-fused R22(24) and R44(24) rings along [001].
For the sake of clarity, H atoms not involved in the motif shown have
been omitted.
+
ꢀ
o224 Vasconcelos et al.
C13H10ClN4O4 ÁCl and C13H9N5O6
Acta Cryst. (2006). C62, o222±o226