Synthesis and Spectral Characterization of Hydrazone Schiff Bases

Derived from 2,4-Dinitrophenylhydrazine. Crystal Structure of

Salicylaldehyde-2,4-Dinitrophenylhydrazone
Hassan Hosseini Monfareda, Omid Pouralimardana, and Christoph Janiakb
a Department of Chemistry, Faculty of Sciences, Zanjan University, Zanjan 45195-313, Iran
b Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstraße 21,
79104 Freiburg, Germany
Reprint requests to Prof. Dr. H. H. Monfared. Fax: 0098-241-5283203.
E-mail: monfared [email protected]

Z. Naturforsch. 2007, 62b, 717 – 720; received November 12, 2006

Reactions of 2,4-dinitrophenylhydrazine with salicylaldehyde, pyridine-2-carbaldehyde and 2-

aminobenzophenone in methanol result in the hydrazone Schiff base ligands salicylaldehyde-, pyr-
idine-2-carbaldehyde-, and 2-aminobenzophenone-2,4-dinitrophenylhydrazone, respectively. Crys-
tals of salicylaldehyde-2,4-dinitrophenylhydrazone are monoclinic, space group P21 /c, a = 13.820(3),
b = 4.3515(9), c = 25.159(7) Å, β = 123.01(2)◦ with Z = 4. The molecular packing is mostly a zigzag
or herring-bone pattern.

Key words: Hydrazone, Schiff Base, 2,4-Dintrophenylhydrazine, Salicylaldehyde,

X-Ray Structure

Introduction
Hydrazones, RR C=N–NR R , are used as inter-
mediates in synthesis [1], as functional groups in metal
carbonyls [2], in organic compounds [3, 4] and in par-
ticular in hydrazone Schiff base ligands (Fig. 1) [5 – 8], Fig. 1. Hydrazone (a) and Schiff base (b) based on salicyl-
which are among others employed in dinuclear cata- aldehyde.
lysts [9]. Furthermore, hydrazones exhibit physiologi-
cal activities in the treatment of several diseases such
Results and Discussion
as tuberculosis. This activity is attributed to the forma-
tion of stable chelate complexes with transition met- Reaction of 2,4-dinitrophenylhydrazine with salic-
als which catalyze physiological processes [10 – 12]. ylaldehyde, pyridine-2-carbaldehyde and 2-amino-
They also act as herbicides, insecticides, nematocides, benzophenone readily yields the hydrazone Schiff base
rodenticides, plant growth regulators, sterilants for compounds 1 – 3 in high yield. IR and 1 H NMR spec-
houseflies, among other applications [10, 11, 13]. In tral features agree with the formula assignments. The
analytical chemistry hydrazones find applications as similar IR spectra of compounds 1 – 3 indicate the for-
multidentate ligands for transition metals in colorimet- mation of the Schiff base product by the absence of the
ric or fluorimetric determinations [14, 15]. carbonyl group (1700 cm−1 ) band and the appearance
We report here the synthesis and characterization of of a strong band in the region of 1610 – 1640 cm−1 ,
hydrazone Schiff base compounds 1 – 3. assignable to the ν (C=N)imine group [16]. The X-ray

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718 H. H. Monfared et al. · Crystal Structure of Salicylaldehyde-2,4-Dinitrophenylhydrazone

Table 1. Hydrogen bonding interactions in 1a .

D–H··· A D–H H··· A D··· A D–H··· A
(Å) (Å) (Å) (deg)
intramolecular:
O5–H5··· N3 0.94(3) 1.88(3) 2.688(3) 143(3)
N4–H4··· O2 0.88(3) 1.96(3) 2.618(3) 130(2)
intermolecular:
N4–H4··· O23 0.88(3) 2.58(3) 3.420(3) 158(2)
a
D = Donor, A = acceptor. For found and refined atoms the estimated
standard deviations are given in units of the last significant figure.
Symmetry transformation: 3 −x + 1, −y + 1, −z + 1.

Fig. 2. Molecular structure of 1 with intramolecular hydrogen

bonds (see Table 1). Displacement ellipsoids are drawn at the
50 % probability level.

structure of 1 (Fig. 2) shows the whole molecule to be Fig. 3. Packing of the molecules in 1 projected onto the
almost planar. The two aryl ring planes form an an- ac plane (top), and viewed along the ac diagonal perpen-
dicular to the b axis (bottom).
gle of 3.5(1)◦. The dihedral angle of the nitro groups
to the bound aryl group (C11-C16) is only 5.0(3)◦
(O1–N1–O2) and 1.7(3)◦ (O3–N2–O4), respectively.
The plane defined by the central C1=N3–N4 portion is
tilted by 4.0(3)◦ and 2.6(3)◦ to the planes of the aryl
groups (C11-C16 and C21-C26, respectively). Bond
lengths are within the expected range. Intramolecular
hydrogen bonds are observed between the salicyl-OH
group and the imine nitrogen atom and between the
hydrazone-NH and the ortho nitro group (Fig. 2 and
Table 1).
The molecular packing in 1 appears as an in-plane
arrangement of molecules when projected onto the ac
plane (Fig. 3, top). However, it turns out to be a zigzag
Fig. 4. Space-filling presentation of three adjacent molecules
or herring-bone pattern when viewed along the ac di- in the ac plane (cf. Fig. 3, top) and concomitant schematic
agonal (Fig. 3, bottom). There is a single classical in- formula drawing.
termolecular, albeit rather weak N–H· · · O hydrogen
bond (Table 1, not shown in Fig. 3) [17, 18]. Adja- of ring C11-C16 and C21-C26, respectively, with their
cent molecules stacked on top of each other along symmetry related counterparts with operation x, 1±y,
the b axis exhibit some medium to weak π -π inter- z [19 – 21]. The program PLATON, which was used for
actions between their exactly parallel (by symmetry) calculating the supramolecular interactions, did nei-
aryl planes. Centroid-centroid contacts are 4.35 Å, in- ther indicate the presence of strong intermolecular
terplanar distances 3.34 and 3.31 Å, slip angles (angle C–H· · · O hydrogen bonds [22, 23] nor the existence of
between centroid-centroid vector and normal to plane) C–H· · · π interactions [17, 20, 24, 25]. Instead, a space-
50.2 and 49.6◦, and vertical displacements (between filling presentation of adjacent molecules, shown in
ring centroids) 2.79 and 2.82 Å for the interactions Fig. 4, suggests that the shape of the van der Waals
H. H. Monfared et al. · Crystal Structure of Salicylaldehyde-2,4-Dinitrophenylhydrazone 719

surface of the molecules may be the main contribut- Table 2. Crystal data and structure refinement for 1.
ing factor for their packing in the solid-state struc- 1
ture of 1. Adjacent molecules along the ac diagonal, Formula C13 H10 N4 O5
Mr 302.26
which lie in the same plane, can turn to each other
Cryst. size [mm3 ] 0.53 × 0.14 × 0.06
with their ortho-nitro group facing the opposite sali- Crystal system monoclinic
cyl aryl ring (Fig. 4, upper two molecules). The re- Space group P21 /c
sulting (aryl-C)–H· · · O(nitro) contacts between 2.58 a [Å] 13.820(3)
and 2.72 Å lie to the long end of “normal” C–H· · · O b [Å] 4.3515(9)
c [Å] 25.159(7)
bonds [23]. Molecules along the ac diagonal, with their β [deg] 123.01(2)
planes tilted to each other, assemble through the in- V [Å3 ] 1268.7 (4)
dentation which is present in the molecule between Z 4
the salicyl-hydroxy group and the nitro-substituted aryl Dcalcd [g cm−3 ] 1.582
µ (MoKα ) [cm−1 ] 1.25
ring (Fig. 4, lower two molecules).
F(000) [e] 624
hkl range ±16, ±4, ±25
Experimental Section [(sin θ )/λ ]max [Å−1 ] 0.615
All chemicals were reagent grade and used without fur- Refl. measured 8424
Refl. unique 2324
ther purification. Melting points were determined on an Elec-
Rint 0.1048
trothermal 9100 apparatus. FT-IR spectra were collected on Param. refined 205
a Mattson 1000 spectrophotometer using KBr pellets in the R(F)/wR(F 2 )a (all reflexions) 0.0835/0.1132
range of 4000 – 450 cm−1 . Elemental analyses (CHN) were GoF (F 2 )a 1.016
performed using a Carlo ERBA model EA 1108 analyzer, ∆ ρfin (max/min) [e Å−3 ] 0.255/–0.236
1 H NMR spectra were obtained on a Bruker spectrometer a R(F) = [Σ(Fo | − |Fc )/Σ |Fo |]; wR(F 2 ) = [Σ[w(Fo 2 − Fc 2 )2 /
at 250 MHz in [D6 ]DMSO. Σ[w(Fo2 )2 ]]1/2 . – Goodness-of-fit = [Σ[w(Fo 2 − Fc 2 )2 /(n − p)]1/2 . –
Weight. scheme w; a/b = 0.0317/0.1922 with w = 1/[σ 2 (Fo 2 ) +
Salicylaldehyde-2,4-dinitrophenylhydrazone (1) (aP)2 + bP where P = (max(Fo 2 or 0) + 2Fc 2 )/3.
This compound was prepared according to the method
– 1 H NMR ([D6 ]DMSO): δ = 11.9 (s, 1H, NH), 8.1 (s,
given in the literature [26]. Salicylaldehyde (0.122 g,
1H, CH=N), 6.8 – 9 (m, 7H, aromatic CH). – C12 H9 N5 O4
1.0 mmol) was added slowly to a clear solution of 2,4-
(287.2): calcd. C 50.17, H 3.13, N 24.40; found C 50.00,
dinitrophenylhdrazine (0.198 g, 1.0 mmol) and 1 mL of con-
H 3.30, N 24.80.
centrated hydrochloric acid in 15 mL of methanol. After a
few minutes an orange yellow precipitate was obtained which 2-Aminobenzophenone-2,4-dinitrophenylhydrazone (3)
was filtered, washed with methanol and dried in air. Yield:
95 %, m. p. 255 ◦C. – IR (KBr): ν = 3456 (m, br, NH), To the clear solution of 2,4-dinitrophenylhdrazine
3270 (m, OH), 3101 (w), 2924 (m), 2854 (w), 1620 (vs, (0.198 g, 1.0 mmol), 1 mL of concentrated hydrochloric
C=N), 1512 (s, NO2 ), 1419 (m), 1334 (s, NO2 ), 1273 (vs, acid and 15 mL of methanol was added 2-aminobenzophen-
C–O), 1142 (s), 833 (w), 764 (w), 578 (m) cm−1 . – 1 H NMR one (0.197 g, 1.0 mmol). The mixture was heated at reflux
([D6 ]DMSO): δ = 11.7 (s, 1H, NH), 10.2 (s, 1H, OH), 8.1 (s, for 1 h, and allowed to stand overnight. The product precip-
1H, CH=N), 6.7 – 8.5 (m, 7H, aromatic CH). – C13 H10 N4 O5 itated as a red powder, was separated by filtration, washed
(302.3): calcd. C 51.65, H 3.30, N 18.54; found C 51.65, with methanol, and air dried. Yield: 61 %, m. p. 265 ◦C. – IR
H 3.80, N 18.00. (KBr): ν = 3432 (br, N–H), 3370 (br, NH2 ), 3324 (vs, NH2 ),
3085 (w), 2923 (w), 2854 (w), 1635 (vs, C=N), 1511 (m,
Pyridine-2-carbaldehyde-2,4-dinitrophenylhydrazone (2) NO2 ), 1411 (m), 1316 (vs, NO2 ), 1280 (s), 1126 (w), 1056
This compound was prepared using the same procedure as (w), 979 (w), 833 (w), 701 (w), 632(w) cm−1 . – 1 H NMR
for 1, from 2,4-dinitro-phenylhydrazine (0.198 g, 1.0 mmol), ([D6 ]DMSO): δ = 10.96 (s, 1H, NH), 6.69 (s, 2H, NH2 ),
1 mL of concentrated hydrochloric acid, 15 mL of methanol 6.5 – 8.5 (m, 12H, aromatic CH). – C19 H15 N5 O4 (377.4):
and pyridine-2-carbaldehyde (0.177 g, 1.0 mmol). The mix- calcd. C 60.47, H 4.01, N 18.56; found C 60.40, H 3.96,
ture was brought to boil and after a few minutes a yellow N 18.40.
solid precipitated, which was filtered, washed with methanol,
X-Ray structure determination
and air dried. Yield: 90 %, m. p. 239 ◦C. – IR (KBr): ν = 3424
(s, br, NH), 3209 (vs), 2931 (w), 2862 (w), 1612 (m, C=N), Single crystal X-ray diffraction data for salicylaldehyde-
1566 (w), 1501 (m, NO2 ), 1450 (vs), 1331 (s, NO2 ), 1195 2,4-dinitrophenylhydrazone (1) were collected at 293(2) K
(m), 1119 (m), 1110 (m), 779 (w), 655 (w), 548 (w) cm−1 . on a Bruker AXS Smart CCD diffractometer using graphite-
720 H. H. Monfared et al. · Crystal Structure of Salicylaldehyde-2,4-Dinitrophenylhydrazone

monochromated MoKα radiation (λ = 0.71073 Å). The struc- putations on the supramolecular interactions were carried out
ture was solved by Direct Methods using SHELXS -97, and with PLATON for Windows [29].
refined with full-matrix least-squares techniques on F 2 with CCDC 631452 contains the supplementary crystallo-
SHELXL -97 [27]. The crystal data, data collection and refine- graphic data for this paper. These data can be obtained free
ment parameters are presented in Table 2. All non-hydrogen of charge from The Cambridge Crystallographic Data Centre
positions were found and refined with anisotropic tempera- via www.ccdc.cam.ac.uk/data request/cif.
ture factors. Hydrogen atoms on oxygen (OH) and nitrogen
(–NH–) were found and refined with Ueq (H) = 1.5 Ueq (O/N). Acknowledgement
Hydrogen atoms on C (phenyl and CH=N) were calculated
with appropriate riding models ( AFIX 43) and Ueq (H) = Financial support from Zanjan University and the Univer-
1.2 Ueq (C). Graphics were drawn with DIAMOND [28]. Com- sity of Freiburg is gratefully acknowledged.

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