Synthesis and spectral characterization of hydrazone schiff bases derived from 2,4-dinitrophenylhydrazine. Crystal structure of salicylaldehyde-2,4- dinitrophenylhydrazone

Article abstract of DOI:10.1515/znb-2007-0515

Reactions of 2,4-dinitrophenylhydrazine with salicylaldehyde, pyridine-2-carbaldehyde and 2-aminobenzophenone in methanol result in the hydrazone Schiff base ligands salicylaldehyde-, pyridine-2-carbaldehyde-, and 2-aminobenzophenone-2,4-dinitrophenylhydrazone, respectively. Crystals of salicylaldehyde-2,4-dinitrophenylhydrazone are monoclinic, space group P2 ₁/c, a = 13.820(3), b = 4.3515(9), c = 25.159(7) ?, β= 123.01(2)° with Z = 4. The molecular packing is mostly a zigzag or herring-bone pattern. 2007 Verlag der Zeitschrift für Naturforschung.

Full text of DOI:10.1515/znb-2007-0515

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 fu¨r Anorganische und Analytische Chemie, Universita¨t Freiburg, Albertstraße 21,
79104 Freiburg, Germany
Reprint requests to Prof. Dr. H. H. Monfared. Fax: 0098-241-5283203.
E-mail: monfared 2@yahoo.com
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-dinitrophenylhydra◦zone are monoclinic, space group P21/c, a = 13.820(3),
˚
b = 4.3515(9), c = 25.159(7) A, 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, RRꢀC=N–NRꢀꢀRꢀꢀꢀ, 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],
which are among others employed in dinuclear cata-
lysts [9]. Furthermore, hydrazones exhibit physiologi-
cal activities in the treatment of several diseases such
as tuberculosis. This activity is attributed to the forma-
tion of stable chelate complexes with transition met-
als which catalyze physiological processes [10– 12].
They also act as herbicides, insecticides, nematocides,
rodenticides, plant growth regulators, sterilants for
houseflies, among other applications [10, 11, 13]. In
analytical chemistry hydrazones find applications as
multidentate ligands for transition metals in colorimet-
ric or fluorimetric determinations [14, 15].
Fig. 1. Hydrazone (a) and Schiff base (b) based on salicyl-
aldehyde.
Results and Discussion
Reaction of 2,4-dinitrophenylhydrazine with salic-
ylaldehyde, pyridine-2-carbaldehyde and 2-amino-
benzophenone readily yields the hydrazone Schiff base
compounds 1 – 3 in high yield. IR and 1H NMR spec-
tral features agree with the formula assignments. The
similar IR spectra of compounds 1 – 3 indicate the for-
mation of the Schiff base product by the absence of the
carbonyl group (1700 cm−1) band and the appearance
of a strong band in the region of 1610 – 1640 cm−1
assignable to the ν(C=N)imine group [16]. The X-ray
,
We report here the synthesis and characterization of
hydrazone Schiff base compounds 1 – 3.
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H. H. Monfared et al. · Crystal Structure of Salicylaldehyde-2,4-Dinitrophenylhydrazone
Table 1. Hydrogen bonding interactions in 1a.
D–H···A
D–H
(A)
H···A
D···A
D–H···A
˚
˚
˚
(A)
(A)
(deg)
intramolecular:
O5–H5···N3
N4–H4···O2
intermolecular:
N4–H4···O23
0.94(3)
0.88(3)
1.88(3)
1.96(3)
2.688(3)
2.618(3)
143(3)
130(2)
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.
Fig. 3. Packing of the molecules in 1 projected onto the
ac plane (top), and viewed along the ac diagonal perpen-
dicular to the b axis (bottom).
structure of 1 (Fig. 2) shows the whole molecule to be
almost planar. The two aryl ring planes form an an-
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
or herring-bone pattern when viewed along the ac di-
agonal (Fig. 3, bottom). There is a single classical in-
termolecular, albeit rather weak N–H···O hydrogen
Fig. 4. Space-filling presentation of three adjacent molecules
in the ac plane (cf. Fig. 3, top) and concomitant schematic
formula drawing.
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 A, in- ther indicate the presence of strong intermolecular
˚
terplanar distances 3.34 and 3.31 A, 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 A for the interactions Fig. 4, suggests that the shape of the van der Waals
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H. H. Monfared et al. · Crystal Structure of Salicylaldehyde-2,4-Dinitrophenylhydrazone
719
Table 2. Crystal data and structure refinement for 1.
surface of the molecules may be the main contribut-
ing factor for their packing in the solid-state struc-
ture of 1. Adjacent molecules along the ac diagonal,
which lie in the same plane, can turn to each other
with their ortho-nitro group facing the opposite sali-
cyl aryl ring (Fig. 4, upper two molecules). The re-
sulting (aryl-C)–H···O(nitro) contacts between 2.58
1
Formula
C13H10N4O5
302.26
0.53×0.14×0.06
monoclinic
P21/c
13.820(3)
4.3515(9)
25.159(7)
123.01(2)
1268.7 (4)
4
Mr
Cryst. size [mm3]
Crystal system
Space group
˚
a [A]
b [A]
c [A]
β [deg]
V [A ]
˚
˚
˚
and 2.72 A lie to the long end of “normal” C–H···O
bonds [23]. Molecules along the ac diagonal, with their
planes tilted to each other, assemble through the in-
dentation which is present in the molecule between
the salicyl-hydroxygroup and the nitro-substituted aryl
ring (Fig. 4, lower two molecules).
3
˚
Z
Dcalcd [g cm−3
]
1.582
1.25
624
µ(MoKα ) [cm−1
F(000) [e]
]
hkl range
16, 4, 25
0.615
8424
2324
0.1048
205
0.0835/0.1132
1.016
0.255/–0.236
2
Experimental Section
−1
˚
[(sinθ)/λ]max [A
Refl. measured
Refl. unique
Rint
]
All chemicals were reagent grade and used without fur-
ther purification. Melting points were determined on an Elec-
trothermal 9100 apparatus. FT-IR spectra were collected on
a Mattson 1000 spectrophotometer using KBr pellets in the
range of 4000 – 450 cm−1. Elemental analyses (CHN) were
performed using a Carlo ERBA model EA 1108 analyzer,
1H NMR spectra were obtained on a Bruker spectrometer
at 250 MHz in [D6]DMSO.
Param. refined
R(F)/wR(F2)a (all reflexions)
GoF (F2)a
−3
˚
∆ρfin (max/min) [e A
]
a
R(F) = [Σ(ꢁFo| − |Fcꢁ)/Σ|Fo|]; wR(F2) = [Σ[w(Fo − Fc2)2/
Σ[w(Fo2)2]]1/2. – Goodness-of-fit = [Σ[w(Fo − Fc2)2/(n− p)]1/2. –
2
Weight. scheme w; a/b = 0.0317/0.1922 with w = 1/[σ2(Fo2) +
(aP)2 +bP where P = (max(Fo or 0)+2Fc2)/3.
2
Salicylaldehyde-2,4-dinitrophenylhydrazone (1)
This compound was prepared according to the method
given in the literature [26]. Salicylaldehyde (0.122 g,
1.0 mmol) was added slowly to a clear solution of 2,4-
dinitrophenylhdrazine (0.198 g, 1.0 mmol) and 1 mL of con-
centrated hydrochloric acid in 15 mL of methanol. After a
few minutes an orange yellow precipitate was obtained which
was filtered, washed with methanol and dried in air. Yield:
95 %, m. p. 255 ◦C. – IR (KBr): ν = 3456 (m, br, NH),
3270 (m, OH), 3101 (w), 2924 (m), 2854 (w), 1620 (vs,
C=N), 1512 (s, NO2), 1419 (m), 1334 (s, NO2), 1273 (vs,
C–O), 1142 (s), 833 (w), 764 (w), 578 (m) cm−1. – 1H NMR
([D6]DMSO): δ = 11.7 (s, 1H, NH), 10.2 (s, 1H, OH), 8.1 (s,
1H, CH=N), 6.7 – 8.5 (m, 7H, aromatic CH). – C13H10N4O5
(302.3): calcd. C 51.65, H 3.30, N 18.54; found C 51.65,
H 3.80, N 18.00.
–
1H NMR ([D6]DMSO): δ = 11.9 (s, 1H, NH), 8.1 (s,
1H, CH=N), 6.8 – 9 (m, 7H, aromatic CH). – C12H9N5O4
(287.2): calcd. C 50.17, H 3.13, N 24.40; found C 50.00,
H 3.30, N 24.80.
2-Aminobenzophenone-2,4-dinitrophenylhydrazone (3)
To the clear solution of 2,4-dinitrophenylhdrazine
(0.198 g, 1.0 mmol), 1 mL of concentrated hydrochloric
acid and 15 mL of methanol was added 2-aminobenzophen-
one (0.197 g, 1.0 mmol). The mixture was heated at reflux
for 1 h, and allowed to stand overnight. The product precip-
itated as a red powder, was separated by filtration, washed
with methanol, and air dried. Yield: 61 %, m. p. 265 ◦C. – IR
(KBr): ν = 3432 (br, N–H), 3370 (br, NH2), 3324 (vs, NH2),
3085 (w), 2923 (w), 2854 (w), 1635 (vs, C=N), 1511 (m,
NO2), 1411 (m), 1316 (vs, NO2), 1280 (s), 1126 (w), 1056
(w), 979 (w), 833 (w), 701 (w), 632(w) cm−1. – 1H NMR
([D6]DMSO): δ = 10.96 (s, 1H, NH), 6.69 (s, 2H, NH2),
6.5 – 8.5 (m, 12H, aromatic CH). – C19H15N5O4 (377.4):
calcd. C 60.47, H 4.01, N 18.56; found C 60.40, H 3.96,
N 18.40.
Pyridine-2-carbaldehyde-2,4-dinitrophenylhydrazone (2)
This compound was prepared using the same procedure as
for 1, from 2,4-dinitro-phenylhydrazine (0.198 g, 1.0 mmol),
1 mL of concentrated hydrochloric acid, 15 mL of methanol
and pyridine-2-carbaldehyde (0.177 g, 1.0 mmol). The mix-
ture was brought to boil and after a few minutes a yellow
solid precipitated, which was filtered, washed with methanol,
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),
X-Ray structure determination
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-
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H. H. Monfared et al. · Crystal Structure of Salicylaldehyde-2,4-Dinitrophenylhydrazone
˚
monochromated MoKα radiation (λ = 0.71073 A). 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 F2 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).
Hydrogen atoms on C (phenyl and CH=N) were calculated
Acknowledgement
with appropriate riding models (AFIX 43) and Ueq(H) =
1.2 Ueq(C). Graphics were drawn with DIAMOND [28]. Com-
Financial support from Zanjan University and the Univer-
sity of Freiburg is gratefully acknowledged.
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