Crystal structure and properties of (Z)-N′-((E)-2-(hydroxyimino)-1-phenylethylidene) isonicotinohydrazide

Article abstract of DOI:10.1007/s10947-009-0171-3

Compound I contains in its molecule pyridyl, monoxime and hydrazone functions. A non-merohedral twin crystal of the compound with two reciprocal lattices differently oriented and giving rise to double diffraction spot sets with the 0.5:0.5 ratio of the tw

Full text of DOI:10.1007/s10947-009-0171-3

Journal of Structural Chemistry. Vol. 50, No. 6, pp. 1166-1170, 2009
Original Russian Text Copyright © 2009 by A. Zülfikaro÷lu, Ç. Yüksektepe, H. Bati, N. Çalıúkan, and O. Büyükgüngör
CRYSTAL STRUCTURE AND PROPERTIES OF
(Z)-Nc-((E)-2-(HYDROXYIMINO)-1-PHENYLETHYLIDENE)
ISONICOTINOHYDRAZIDE
A. Zülfikaro÷lu,1 Ç. Yüksektepe,2 H. Bati,1
N. Çalıúkan,2 and O. Büyükgüngör2
UDC 548.737
Compound I contains in its molecule pyridyl, monoxime and hydrazone functions. A non-merohedral twin
crystal of the compound with two reciprocal lattices differently oriented and giving rise to double
diffraction spot sets with the 0.5:0.5 ratio of the twin components was studied. The hydrazone and oxime
units are approximately planar. The dihedral angles between this plane and the planes of the pyridine and
phenyl rings are 30.79(19)q and 18.43(13)q, respectively. Both the oxime and hydrazone units in I have an
E configuration. The molecules of I are linked via C–H}O and O–H}N hydrogen bonds forming a 3D
framework. The compound was also characterized by IR, 1H NMR and elemental analyses.
Keywords: pyridine, oxime, hydrazone, twin crystal, isomerism.
INTRODUCTION
Oximes and hydrazones are interesting objects because of their wide application in medicine, industry and analytical
chemistry. These compounds are used as analytical reagents for the detection and determination of some metal ions [1, 2].
Hydrazones have been utilized for the determination of carbonyl compounds [2, 3]. Hydrazones and hydrazone oximes
exhibit biological activity. Hydrazone derivatives have been synthesized in order to investigate the relationship between
structure and biological activity [4-6]. In this study, we present the crystal structure of the title compound, I, which is a
product of the condensation reaction of isonicotinyl hydrazine and isonitrosoacetophenone.
RESULTS AND DISCUSSION
Spectroscopic characterization of 1. The structure of I was verified by means of IR (KBr), 1H NMR (DMSO), UV-
VIS spectral data and elemental analyses. In the IR spectrum of compound I characteristic bands are observed at 1690 cm–1,
1607 cm–1, 1536 cm–1, 1509 cm–1 assigned to the Q(C=O), Q(C=N) hydrazone, Q(C=N)oxime and Q(N–H) vibrations,
respectively. A strong band at 1007 cm–1 in the spectrum of I is mainly attributed to Q(N–O) vibration. The medium intensity
band at 1040 cm–1 is ascribed to Q(N–N) vibration. In addition, the band 3136 cm–1 is asigned to overlapping oxime NOH and
NH groups. In the 1H NMR spectra of I the resonance of the NH protons appears as a singlet at 12.68 ppm. The characteristic
oxime OH proton is observed at 13.16 ppm. The doublet around 8.82 ppm is assigned to the two protons of pyridine ring
1Department of Chemistry, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Kurupelit, Samsun,
2
Turkey. Department of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Kurupelit, Samsun,
Turkey; yuksekc@yahoo.com. The text was submitted by the authors in English. Zhurnal Strukturnoi Khimii, Vol. 50, No. 6,
pp. 1219-1222, November-December, 2009. Original article submitted September 5, 2008.
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0022-4766/09/5006-1166 © 2009 Springer Science+Business Media, Inc.

system (H10, H11). The other two protons of the pyridine ring appear at 7.80-7.46 ppm. A signal is also observed at
8.55 ppm for HC=N-group.
Crystallography. The molecular structure of I is shown in Fig. 1. Compound I comprises three functional groups:
pyridine, monoxime and hydrazone. The crystal is monoclinic, space group P21/c with a = 8.5235(5) Å, b = 7.7619(5) Å, c =
20.7354(13) Å, E = 109.089(5)q, V = 12.9639(15) Å3, Z = 4 (Table 1). The hydrazone and oxime units are approximately co-
planar. The dihedral angles between this plane and the planes of the pyridine and phenyl rings are 30.79(19) and 18.43(13)q,
respectively. The bond lengths and angles of the oxime and hydrazone are given in Table 2. Both the oxime and hydrazone
units in I have an E configuration (Dihedral angles O1–N3=C8–C7 = 176.1(2)q and N2–N1=C7–C1 = 178.3(2)q). The N1–
N2 bond distance of 1.372(3) Å is appreciably shorter than a typical N–N single bond, such as that found in free 2,4-
dinitrophenylhydrazone, 1.405(6) Å [7]; this suggests the existence of a delocalized double bond. The N3=C8 and N1=C7
distances of 1.276(3) Å and 1.291(3) Å, respectively, are typical of a double bond. The C=N and N–O distances of the free
oximes are close to those commonly found in oxime derivatives [C=N = 1.292(13) Å and N–O = 1.396(3) Å] [8]. The
molecules of I are linked via C–H}O and O–H}N hydrogen bonds (Table 3) forming a 3D framework. Atoms C13 at
(x, y, z) and (1–x, 1–y, –z) H-bond to atoms O1 at (x, 1/2–y, –1/2+z) and (2–x, 1/2+y, 1/2–z) producing two C(11) chains [9]
running parallel to the [00
and (1– , – , –
) act as donors to atoms N4 (Fig. 2) generating centrosymmetric R22 (24) rings centred at (1, 0, 0) and
(1, 1/2, 1/2). These rings are linked to each other by H atoms of the C13 atoms. The R22 (24) rings formed by hydrogen bonds
are centred at [1, 0, ] and [1, 1/2, +1/2] ( is zero or integer). Besides, C–H}S and interactions are also observed in
the crystal. Crystals of I were found to be twinned in approximate 0.5:0.5 ratio; the twinned cell can be obtained by the unit-
1 ], [001] direction. Atoms generated by c-glide plane at y = 1/4 and screw axis at z = 1/4 at (x, y, z)
x
y z
n
n
n
S–S
cell transformation atwinvector = –avector, btwinvector = –bvector, ctwinvector = cvector, indicating a two-fold twinning axis
along [001] direction.
EXPERIMENTAL
Preparation of I. Isonicotinic acid hydrazide (0.67 g, 5 mmol) was dissolved in hot anhydrous ethanol (40 ml).
To this solution was added dropwise isonitrosoacetephenone (0.75 g, 5 mmol) in anhydrous ethanol (30 ml) and few drops of
glacial acetic acid. The reaction mixture was refluxed for 7 h. A white product formed was separated by filtration and washed
Fig. 1. The molecular structure of I.
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TABLE 1. Crystallographic and Experimental Data for I
Formula
C14H12N4O2
268.28
M
Temperature (K)
296
0.71073
Monoclinic
O
, Å
Crystal system
Space group
P
21/c
Unit cell dimensions (Å, deg)
a
= 8.5235(5),
b
= 7.7619(5), c = 20.7354(13),
E
= 109.089(5)
1296.39(14)
4
V
, Å3
Z
Dcalc, g/cm3
Tmin Tmax
Crystal size, mm
, mm–1
max, deg
1.375
,
0.9563, 0.9903
0.77
u0.42u0.10
0.10
P
T
26.00
Index ranges
h
= –10o10,
k
= –9o
9,
l
= –26o26
Measured reflections
Independent reflections
12087
1307
1028
1.06
Observed reflections (I > 2V(I))
GOOF
0.039
0.093
R
(
I
> 2
V
V
(
I
))
wR
(
I
> 2
(
I))
CCDC deposition N
713706
TABLE 2. Selected Geometric Parameters for I (Å, deg)
O1–N3
O2–C9
N1–C7
N1–N2
N2–C9
N3–C8
N4–C13
N4–C12
C1–C7
C7–C8
C9–C10
1.370(3)
1.211(3)
1.291(3)
1.372(2)
1.356(3)
1.275(3)
1.321(3)
1.325(3)
1.488(3)
1.448(3)
1.511(3)
C7–N1–N2
C9–N2–N1
C8–N3–O1
N1–C7–C8
N1–C7–C1
N3–C8–C7
O2–C9–N2
O2–C9–C10
N2–C9–C10
N4–C13–C14
117.3(2)
119.7(2)
112.5(2)
127.1(2)
115.1(2)
123.9(3)
124.9(2)
121.3(3)
113.7(2)
124.1(3)
C7–N1–N2–C9
N2–N1–C7–C8
N2–N1–C7–C1
N1–C7–C8–N3
N1–N2–C9–O2
–176.2(2)
3.1(4)
178.3(2)
–4.2(4)
2.7(4)
N1–N2–C9–C10
C13–N4–C12–C11
C10–C11–C12–N4
C12–N4–C13–C14
–177.9(2)
–1.7(4)
2.3(4)
–1.3(4)
TABLE 3. Hydrogen Bonds Geometry of I (Å, deg)
D–H…A
D–H
H…A
D…A
N2–H2A…N3
O1–H1…N4 i
C13–H13…O1 ii
0.86
0.82
0.93
1.97
1.87
2.56
2.641(3)
2.692(3)
3.473(3)
134
176
169
Symmetry codes: i – ii x, –
x+2, –y, –z, y–1/2, z–3/2.
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Fig. 2. Crystal packing in I.
with ethanol. The solid product was recrystallized from hot ethanol to give crystals of the title compound. Yield 40%. Anal.
Calcd. for C14H12N4O2: C 62.68, H 4.51, N 20.88%. Found: C 62.63, H 4.58, N 20.81%.
Materials and measurements. Elemental analyses were performed using standard methods at TÜBI˙TAK (The
Turkish Scientific Research Centre). The IR spectrum was recorded on a Vertex 80v sample Compartment RT-DLaTGS
1
spectrophotometer operating within 4000-500 cm–1. H NMR spectra were recorded on BRUKER DPX-400, 400 MHz High
Performance Digital FT-NMR spectrometer utilizing deuterated dimethylsulfoxide as a solvent.
Crystallographic analysis. Data collection was performed on a STOE IPDSII image plate detector using MoKD
radiation. Details of the crystal structure are given in Table 1. Data collection: Stoe X-AREA [10]. Cell refinement: Stoe X-
AREA [10]. Data reduction: Stoe X-RED [10]. The structure was solved by direct methods using SHELXS-97 [11].
Anisotropic displacement parameters were applied to non-hydrogen atoms in a full-matrix least-squares refinement based on
F
2. H atoms were placed in calculated positions and constrained to ride on their parents atoms, with C–H = 0.93 Å, O–
H = 0.82 Å, and N–H = 0.86 Å. Uiso(H) = 1.2Ueq(C, N), Uiso(H) = 1.5Ueq(O). The crystal was twinned and the reflection data
were measured for the two twin domains, scaled and combined together. Overlapping reflections could not be satisfactorily
measured and were discarded, leading to a data completeness of only 57%. Molecular drawing was obtained using ORTEP-
III [12]. Full crystallographic data were deposited with Cambridge Crystallographic Database; CCDC deposition number
713706.
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