Synthesis, crystal structure, and spectroscopic studies of N-(4-bromobenzylidene)-N-(2-pyridyl) hydrazine schiff base molecule

Article abstract of DOI:10.1080/15421406.2011.591702

A new Schiff base complex N-(4-bromobenzylidene)-N-(2-pyridyl) hydrazine, C12_H10N₃Br, has been synthesized and characterized by elemental analyses, mass, ¹H NMR, ultraviolet-visible (UV-VIS), and IR spectroscopy and single-crystal X-ray determination. The p-Br-benzene and pyridine rings are almost planar and the dihedral angle between the planes is 11.1(3). The crystal structure is stabilized by intermolecular NHNPy hydrogen bonding interaction. X-ray diffraction analyses show that N-(4-bromobenzylidene) -N-(2-pyridyl) hydrazine Schiff base molecule crystallizes in the monoclinic system, P₂₁/c space group, a = 5.611(5) , b = 19.566(5) , c = 10.715(5) , = 98.766(5), and V = 1162.60(12) ³.

Full text of DOI:10.1080/15421406.2011.591702

This article was downloaded by: [National Sun Yat-Sen University]
On: 01 January 2015, At: 12:04
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Molecular Crystals and Liquid Crystals
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gmcl20
Synthesis, Crystal Structure, and
Spectroscopic Studies of N-(4-
Bromobenzylidene)-N′-(2-Pyridyl)
Hydrazine Schiff Base Molecule
Tuncay Tunç a , Habibe Tezcan b , Ertan Şahin c & Nefise Dilek d
a Department of Science Education, Faculty of Education , Aksaray
University , Aksaray , Turkey
b Department of Chemistry Education, Faculty of Education , Gazi
University , Ankara , Turkey
c Department of Chemistry, Faculty of Science and Arts , Ataturk
University , Erzurum , Turkey
d Department of Physics, Faculty of Science and Arts , Aksaray
University , Aksaray , Turkey
Published online: 27 Dec 2011.
To cite this article: Tuncay Tunç , Habibe Tezcan , Ertan Şahin & Nefise Dilek (2012) Synthesis, Crystal
Structure, and Spectroscopic Studies of N-(4-Bromobenzylidene)-N′-(2-Pyridyl) Hydrazine Schiff Base
Molecule, Molecular Crystals and Liquid Crystals, 552:1, 194-208, DOI: 10.1080/15421406.2011.591702
To link to this article: http://dx.doi.org/10.1080/15421406.2011.591702
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Mol. Cryst. Liq. Cryst., Vol. 552: pp. 194–208, 2012
Copyright © Taylor & Francis Group, LLC
ISSN: 1542-1406 print/1563-5287 online
DOI: 10.1080/15421406.2011.591702
Synthesis, Crystal Structure, and Spectroscopic
Studies of N-(4-Bromobenzylidene)-Nꢀ-(2-Pyridyl)
Hydrazine Schiff Base Molecule
TUNCAY TUNC¸ ,1,∗ HABIBE TEZCAN,2 ERTAN S¸AHIN,3
AND NEFISE DILEK4
1Department of Science Education, Faculty of Education, Aksaray University,
Aksaray, Turkey
2Department of Chemistry Education, Faculty of Education, Gazi University,
Ankara, Turkey
3Department of Chemistry, Faculty of Science and Arts, Ataturk University,
Erzurum, Turkey
4Department of Physics, Faculty of Science and Arts, Aksaray University,
Aksaray, Turkey
A
new Schiff base complex N-(4-bromobenzylidene)-Nꢀ-(2-pyridyl) hydrazine,
C12H10N3Br, has been synthesized and characterized by elemental analyses, mass, 1H
NMR, ultraviolet–visible (UV–VIS), and IR spectroscopy and single-crystal X-ray de-
termination. The p-Br-benzene and pyridine rings are almost planar and the dihedral
angle between the planes is 11.1(3)◦. The crystal structure is stabilized by intermolec-
ular N H . . . N Py hydrogen bonding interaction. X-ray diffraction analyses show
that N-(4-bromobenzylidene)-Nꢀ-(2-pyridyl) hydrazine Schiff base molecule crystallizes
in the monoclinic system, P21/c space group, a = 5.611(5) Å, b = 19.566(5) Å, c =
10.715(5) Å, β = 98.766(5)◦, and V = 1162.60(12) Å3.
Keywords Condensation reaction; crystal structure; hydrazone; Schiff base; X-ray
diffraction
Introduction
Schiff base complexes are often used as ligands in coordination chemistry related to catal-
ysis and enzymatic reactions. Schiff base ligands and their metal complexes have been
extensively studied over the past few decades. In particular, hydrazones are useful for the
synthesis of formazans. Formazans form tetrazolium salt when they are oxidized [1]. Tetra-
zolium salts are reduced back to formazans by the enzymes in the cell and stain the tissue.
The tetrazolium-formazan system is classified as a marker of vitality [2]. Hydrazones are
also useful for the synthesis of metal complexes as they easily form stable complexes
with most transition metal ions [3,4]. Hydrazones and their metal complexes have gained
a special attraction for widespread application in technology and analytical chemistry.
∗Address correspondence to Tuncay Tunc¸, Department of Science Education, Faculty of Edu-
cation, Aksaray University, 68100 Aksaray, Turkey. Tel: +90.3822802228; Fax: +90.382 2801180.
E-mail: tctunc@gmail.com
194

X-Ray Analysis and Spectroscopic Studies of (C12H10N3Br)
195
Hydrazones are formed when hydrazines condense with aldehydes and ketones by the
condensation of aldehydes (or substituted aldehydes) with phenylhydrazine (or substituted
phenylhydrazine) and typically are crystalline compounds with sharp melting points [5,6].
These compounds can therefore be used to identify the aldehydes and ketones from which
the hydrazones have been formed. Hydrazide and hydrazones’ ligands, owing to their
structural flexibility, are quite diverse in their chelating ability and can act as a neutral or
mononegative ligand and as a bidentate or tridentate unit, though they have the potential to
act as bridging tetradentate ligands [7]. Aroylhydrazone complexes of transition metal ions
are known to provide useful models for elucidation of the mechanism of enzyme inhibition
by hydrazine derivatives [8]. Hydrazone Schiff bases and their metal complexes exhibit a
wide variety of biological activities such as antimycobacterial, anticancer, antiviral, and
antifungal agents [9–12]. Moreover, they have been the subjects of extensive investiga-
tion due to their versatile chelating behavior, for which they are widely used in analytical
chemistry as a selective metal extracting agent, as well as in spectroscopic determination
of certain transition metals [13].
In our previous studies, the synthesis and characterization of aroylhydrazone
compounds were achieved [14,15]. In the present study, the compound N-(4-
bromobenzylidene)-Nꢀ-(2-pyridyl)hydrazine (BrPyH) Schiff base had been synthesized
and its structure was determined by the use of elemental analysis, IR spectroscopy, and
single-crystal X-ray diffraction techniques and characterized with spectroscopic techniques.
The goal of this study is to develop the spectral and crystal structure determination of
the new Schiff base for the using fields, which are medical, analytical, drug applications,
the dye industry, and new organic synthesis. It is also hoped that this compound will be
more suitable for using fields than the known other substituted Schiff bases.
Experimental Details
General Procedures and Materials
2-hydrazinopyridine and 4-bromobenzaldehyde were purchased from Aldrich and used
without further purification. Organic solvents and all the other chemical substances used
were purchased from Carlo Erba. The IR spectra were recorded on a Thermo Nicolet 6700
ATR spectrophotometer by using KBr disks in the range 4000–400 cm−1. The electronic
spectra in the range of 200–900 nm were obtained on a Shimadzu UV-1240 spectropho-
tometer. Elemental analyses for C, H, and N were performed using a LECO CHNS 932
elemental analyzer. 1H-NMR spectra were performed on a Bruker AVANCE DPX-300 MHz
and mass spectra were recorded using an Agilent 1100 MSD mass spectrometer.
Synthesis of BrPyH
The title compound, BrPyH, was prepared as shown in Scheme 1. A solution of 4-
bromobenzaldehyde (1) (4.623 g, 0.025 mol) in hot methanol (20 ml) was gradually added
Scheme 1. Synthetic pathway for the synthesis of BrPyH Schiff base.

196
T. Tunc¸ et al.
to a solution of 2-hydrazinopyridine (2) (2.72 g, 0.025 mol) in hot ethanol–dioxane mixture
(100:20 ml, 5% HCl) with constant stirring. Since condensation reaction is carried out in
acidic conditions, synthesis was made at about pH 4–5 [5]. The procedure was completed
in approximately 30 min. The resulting pale yellow Schiff base (3) was left on the bench
for 4 days and was then filtered. The pale yellow precipitate formed was dissolved in hot
methanol under the reflux for 3 hr and was kept in a cupboard for 2 days for recrystal-
lization and was then filtered [5,6]. Also, unsubstituted N-benzlidene-Nꢀ-phenyl hydrazine
(BPH) was synthesized in the same way for clarification of substituent effects of BrPyH.
Experimental data of Schiff base are given in Table 1.
X-Ray Diffraction Study
The crystal and instrumental parameters used in the unit cell determination and data col-
lection are summarized in Table 2. Diffraction measurements were performed at room
temperature on a four-circle Rigaku R-AXIS RAPID-S diffractometer [equipped with
a two-dimensional (2D) area image plate (IP) detector]. The graphite-monochromatized
MoKα radiation (λ = 0.71073 Å) and oscillation scans technique with ꢀω = 5◦ for one
image were used for data collection. The lattice parameters were determined by the least-
squares methods on the basis of all reflections with F2 > 2σ (F2). Integration of the
intensities, correction for Lorentz and polarization effects, and cell refinement were per-
formed using CrystalClear (Rigaku/MSC, Inc., The Woodlands, TX) software [16]. The
structures were solved by direct methods using SHELXS-97 [17] and refined by a full
matrix least-squares procedure using the program SHELXL-97 [18]. All nonhydrogen
atoms were refined using anisotropic displacement parameters and hydrogen atoms were
included in their idealized positions and refined isotropically, except for H7 and H2N. An
ORTEP (Oak Ridge Thermal-Ellipsoid Plot Program) [19] drawing of the molecule with
40% probability displacement thermal ellipsoids and atom-labeling scheme is shown in
Fig. 1. Except for H7 and H2N, the H atoms were positioned geometrically, with C H =
0.93 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.2 Ueq(C).
Figure 1. ORTEP drawing of the title compound, represented with displacement ellipsoids, is drawn
at 50% probability level and showing the labeling scheme.

197

198
T. Tunc¸ et al.
Table 2. Crystal data and structural refinement details for the complex
Chemical formula
C12H10Br N3
Formula weight
276.14
Crystal system
Monoclinic
Space group
P21/c
Z
4
Crystal color
Pale yellow
a, b, c
β
5.611(5), 19.566(5), 10.715(5) Å
98.766(5)◦
1162.60(12) Å3
1.58 g cm−3
V
Dx
Radiation, λ
µ
MoKα, 0.71073 Å
3.510 mm−1
T
293(2) K
Tmin, Tmax
0.496, 0.501
Scanning mode
ω/2θ
Scan range
Crystal size
θmin, θmax
−6 ≤ h ≤ 8, −27 ≤ k ≤ 27, −15 ≤ l ≤ 15
0.20 × 0.20 × 0.20 mm
2.19◦, 30.56◦
Number of measured/independent
reflections, Rint
31,939/3539, 0.1466
Number of reflections with I > 2σ(I)
Number of refined parameters
S
2774
151
1.422
Final R indices [I > 2σ(I)]
wR (I)
ꢀρmax, ꢀρmin
0.1131
0.1447
0.562, −0.315 e Å−3
Results and Discussion
Spectral Properties
The selected IR spectral data of Schiff base are given in Table 3 and the spectrum of BrPyH
is shown in Fig. 2(a). Pyridine and phenyl rings with Br substituent are attached to BrPyH
Schiff base. Owing to this structure, the IR spectrum of Schiff base BrPyH is different
according to BPH (Fig. 2(b)). In the IR bands of BrPyH, N H and aromatic C H bands
were observed at 3189–2850 cm−1 weak and broad bands. Stretching N H band exhibits
a great broadening and low frequency shift when it forms strong intermolecular bonds and
overlapped with aromatic C H bands [20,21]. Therefore, in this study, the multiplet bands
at 3189–2850 cm−1 could be N H stretching mode forming hydrogen bond, and aromatic
C H groups overlapped with the N H mode. The H of N H forms strong intermolecular
hydrogen bonds with unpaired electrons of N pyridine of other molecules. These values
confirmed X-ray results (Fig. 3). Furthermore, strong sharp bands were observed in the IR
spectrum of Schiff base for C C at 1436 cm−1 and at 1592 cm−1 for C N. The band in
the IR spectrum at approximately 811 cm−1 can be assigned to the C Br stretching mode
[21,22]. In the IR spectra, three intensity bands appear at 1539, 1087–1060, and 765 cm−1
which are assigned to vibration frequency v (Py ring), v (Py ring bending), and v (Py ring
,

199

200
T. Tunc¸ et al.
Figure 2. The experimental FTIR spectrum of the (a) BrPyH Schiff base (b) BPH Schiff base.
outside the plan), respectively (outside the plan is into fingerprint region [21–23]). These
values verified the structures of the synthesized Schiff base, which were elucidated by
elemental analysis and X-ray results.
As seen from Table 4 and Fig. 3, the 1H-NMR data showed that the δ values of BrPyH
shifted to a lower field compared with those of unsubstituted BPH. For instance, δ values for
C Harom (C6H5) appeared as a multiplet in the region of δ 6.91–7.70 ppm in BPH (Fig. 3(a)),
shifting to the lower field to the region of δ 6.79–8.17 ppm in BrPyH (Fig. 3(b)). Also, at

X-Ray Analysis and Spectroscopic Studies of (C12H10N3Br)
201
Figure 3. 1H-NMR spectrum of (a) BPH Schiff base (b) BrPyH Schiff base.
δ 7.62 ppm, the observed N H signal shifted to δ 8.17 ppm and at δ 7.13 ppm, the
observed HC N proton signal was observed at δ 8.15 ppm on the spectrum of BrPyH.
These results are justifiable because there are electron-withdrawing groups such as p-Br
(Hammett substituent coefficients for p-Br, σp = 0.26) and pyridine in the structure of
1
Table 4. H-NMR data of the hydrazones (in CDCl3)
Abbreviation
Harom, Hpyridine δ (ppm)
N H δ (ppm)
HC N δ (ppm)
BPH
BrPyH
7.70–6.91
8.17–6.79
7.62
8.17
7.13
8.15

202
T. Tunc¸ et al.
BrPyH. Also, the downfield shift of the N H signal indicates intermolecular hydrogen
bonding. Hydrogen bonding decreases electron density around the proton of amine group
and thus moves the proton absorption to a lower field. On the other hand, the assignment
of the Z-configuration to the HC N hydrazone double bond was performed considering
literature data [6]. In fact, the chemical shift due to the CH hydrogen atom in the
Z-isomer is usually upfield with respect to the E-isomer, appearing in substituted pyridine
hydrazone derivatives at the range 7.45–8.30 ppm in the 1H NMR spectrum [6].
UV–VIS Absorption λmax Values of the BrPyH
Substituent Effect. The ultraviolet–visible (UV–VIS) absorption λmax peaks values of Schiff
bases are generally observed at 250–450 nm depending upon the structures. These peaks
originate from the π–π∗and n–π∗ transitions that correspond to HC N and aromatic
C C groups in the molecule [3,23,24]. As seen in Table 5 and Fig. 4(a), in this study,
when UV–VIS absorption λmax values are observed 350 nm for BPH, it is 335 nm for
BrPyH in CH3OH. Therefore, the absorption λmax value of compound BrPyH shows a
slight shift toward the lower wavelength according to BPH. There is a total of two effects
shifting λmax value to the lower wavelength. The first one, Br, is inductively electron
withdrawing, but by the resonance, electron-donating effects impose opposing direction
effects on each other. As known, inductively electron-withdrawing effect is deflated from
o-position to p-position. Consequently, substitute Br at p-position to effect only a little
electron-withdrawing effect (Hammett substituent coefficients σp = 0.26). The second
one, i.e., on pyridine ring the unpaired electron of N atom, is not acted on as electron-
donating groups by the resonance. Because of unpaired electrons of N, pyridine forms
strong intermolecular hydrogen bonds, and the electron-donating effect is deflated at o-
position. Consequently, both p-Br and o-Py substituents in total exert a hypsochromic
effect on the λmax values, and hence, the λmax values shift toward the blue direction [24].
This result reveals that the energy difference between the highest-occupied molecular orbital
(HOMO) and the lowest-unoccupied molecular orbital (LUMO) is left over in the system.
Thereupon, absorption λmax value could be shifted to the lower λmax value (hypsochromic
effect).
Solvent Effect. Absorption spectra of the BrPyH were recorded in three different solvents
with the aim of clarifying the effects of solvents. For this purpose, solvents of different types
were selected: the polar nonprotic solvent, dimethyl sulfoxide (DMSO), the polar protic
solvent, methanol, and the apolar solvent, toluene. Generally, in many dye molecules, the
ground state is less polar than the excited state so that polar protic or aprotic solvents will
tend to stabilize the excited state more than the ground state. Therefore, λmax values shift
to the bathochromic region. This case is seen in solvent DMSO. However, this is not seen
in methanol. As seen from Table 6 and Fig. 4(b), in the apolar solvent toluene, λmax values
Table 5. UV–VIS absorption maxima λmax of the hydrazones (in methanol 10−6 M)
Abbreviation
λmax1 (nm)
Absorbance
λmax2 (nm)
Absorbance
BPH
BrPyH
350
335
0.473
2,554
245
240
1.363
1,694
Note: Between screen 780 nm and 200 nm.

X-Ray Analysis and Spectroscopic Studies of (C12H10N3Br)
203
Figure 4. (a) UV–VIS spectra of BPH and BrPyH Schiff bases (in CH3OH, 10−6 M) and (b) UV–VIS
spectra of BrPyH Schiff base in various solvents.
shifted more toward the bathochromic region (λmax 337 nm) than in the case of solvent
methanol (λmax 335 nm). This might be due to the formation of a strong hydrogen bond
between the dye BrPyH and methanol molecule. Thus, the ground state will tend to stabilize
more than the excited state. Consequently, the energy difference between the HOMO and
LUMO increases. Thereupon, absorption λmax value could be shifted to the lower λmax
value than toluene as ꢀλ = 2 nm. In addition, at around 320 nm, the absorbance decreases
with the increase of wavelength only in the case of toluene. This can be attributed to the
nonformation of hydrogen bond between dyes BrPyH with the nonprotic apolar molecule
toluene [22]. BrPyH in the excited state has basic hydrazo and imino nitrogen atoms. The

204
T. Tunc¸ et al.
Table 6. UV–VIS absorption maxima λmax of the BrPyH in various solvents
Toluene λmax (nm)
Methanol λmax (nm)
DMSO λmax (nm)
Abbreviation
BrPyH
absorbance
absorbance
absorbance
337 (1.937)
335 (2.554)
346 (1.788)
basic property of hydrazo and imino nitrogen is increased by successive introduction of
electron-donating groups by resonance and weak electron-withdrawing groups, such as
Br, at the p-position of the benzene ring. Furthermore, Br stabilizes the excited state by
donating nonbonding electrons [25]. Consequently, as seen from Table 6 and Fig. 4(b), the
more the solvent polarity increases, the more shifting happens to the absorption λmax value
to the bathochromic region/area.
Description of the Crystal Structure. The structure of BrPyH crystallizes into a monoclinic
lattice with space group P21/c. An ORTEP view of the asymmetric unit is shown in Fig. 5
and selected bond distances and angles are presented in Table 7. The asymmetric unit
contains one Schiff base molecule. In the molecule, the benzene and pyridine rings and
Figure 5. View of the crystal packing of the title compound, along the b-axis. Hydrogen bonds are
indicated by dashed lines.

X-Ray Analysis and Spectroscopic Studies of (C12H10N3Br)
205
Table 7. Selected bond distances (Å), angles (◦), and torsion angles
(◦)
Bond distance (Å)
Br C1
N2 N1
N2 C8
N1 C7
N3 C8
N3 C12
1.894(5)
1.393(5)
1.382(6)
1.272(6)
1.333(6)
1.356(7)
Bond angles (◦)
N1 C7 C4
C2 C1 Br
N1 N2 N8
C7 N1 N2
121.9(5)
120.3(4)
118.6(4)
116.9(4)
Torsion angles (◦)
C3 C4 C7 N1
N1 N2 C8 C9
11.0(8)
−4.5(7)
the hydrazone bridge are practically coplanar. Molecules of the title compound adopt an
E-configuration about the azomethine C N double bond, with an N2-N1-C7-C4 torsion
angle of 178.5(4)◦. For the molecule of BrPyH (Fig. 5), the benzene and pyridine rings
intersect at an 11.1(3)◦. The N2 C8 and N1 N2 bond distances are between 1.382(6) Å
and 1.393(5) Å, respectively. The N1 C7 double bond is 1.272(6) Å.
As shown in Fig. 5, each enantiomer forms head-to-tail molecular pairs. An inter-
molecular hydrogen bond was observed between the H atom attached to the N atom (N2)
of the hydrogen bridge and the N atom (N3) of the pyridine rings of the adjacent molecule
[N2 H2···N3]. Intermolecular hydrogen bond distances and bond angles are listed in Table
8. Also, π–π interactions can be seen from the packing diagram (Fig. 6). Intermolecular
π–π and hydrogen bonding interactions link the molecules and these interactions play an
important role in the stabilization of the crystal structure.
Similarly, the structure of BPH crystallizes into a monoclinic lattice with space group
P21/c [26,27]. The molecule of BPH takes up E-configuration and the angle between the
two benzene rings is 8.1(1)◦ [26]. In BPH molecule, the bond distances corresponding
to N2 C8 and N1 N2 bonds and C7 N1 double bond are 1.435(10), 1.330(8), and
1.312(9) Å, respectively [26]. While the C7 N1 N2 and N1 N2 C8 bond angles in
BrPyH molecule are 116.9(4)◦ and 118.6(4)◦, bond angles corresponding to them in BPH
Table 8. The hydrogen bond distances (Å) and angles (◦)
D H . . . A
d(D H) (Å)
d(H ··A) (Å)
d(D ··A) (Å)
3.066(2)
D H ··A (◦)
N2 H2N ··N3i
1.05
2.02
172
Note: Symmetry code: (i) = –x, –y, –z.

206
T. Tunc¸ et al.
Figure 6. The crystal packing of the compound viewed along a-axis. Intermolecular N—H···N
hydrogen bonds are shown as dashed lines.
are 114.9(7)◦ and 120.8(7)◦. Also, there is no intermolecular hydrogen bonding in BPH
molecule [26,27].
An interesting comparison can be made with the structure of N-(4-
methoxybenzylidene)-Nꢀ-(2-pyridyl) hydrazine (MtPyH) [28], which contain a methoxy
group different from BrPyH molecule. The structure of MtPyH crystallizes into a mon-
oclinic lattice with space group P21/c. The molecule of MtPyH takes up E-conformation
and the dihedral angle between the planes of the pyridine and methoxyphenyl rings is
6.19(12)◦ [28]. In MtPyH molecule, the bond distances corresponding to N2 C8, N1 N2
bonds, and C7 N1 double bond are 1.374(2), 1.367(2), and 1.270(2) Å, respectively. Also,
in MtPyH molecule, the bond angles corresponding to C7 N1 N2 and N1 N2 C8
are 118.18(18)◦ and 118.12(19)◦, respectively [28]. While C8 N2 N1 C7 torsion angle
of the hydrazone bridge in BrPyH molecule is 178.5(4)◦, it is −179.54(19)◦ in MtPyH
molecule. Moreover, centrosymmetrically related molecules are linked into discrete pairs
by pairwise N2 H2···N3i [symmetry code: (i) 2-x, 2-y, 2-z] hydrogen bonds in MtPyH
molecule. The bond distances, bond angles, and hydrogen bonding are comparable with
the literature [14,15,26–30].
Conclusions
In this study, BrPyH was synthesized by the condensation reaction of 4-bromobenzaldehyde
and 2-hydrazinopyridine. Also, unsubstituted BPH was synthesized for clarification of
substituents’ effects on BrPyH. Analysis of spectral data shows that both p-Br and o-Py
substituents in total exert a hypsochromic effect on the λmax values and thus the λmax values
shift toward the blue direction. Furthermore, solvent effect on the UV–VIS absorption
behavior was investigated and it was noted that the more the solvent polarity increases,
the more shifting happens to the absorption λmax value to the bathochromic region. On the
other hand, all the bond distances and bond angles are within normal ranges and comparable
with those of similar compounds. The crystal structure is stabilized by the intermolecular
N H···N hydrogen bonding interaction. This result is confirmed via both spectral and
X-ray values.

X-Ray Analysis and Spectroscopic Studies of (C12H10N3Br)
Supplementary Data
207
Crystallographic data for the structural analysis have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publication no. CCDC 798670. Copies
of this data can be obtained free of charge via www.ccdc.cam.ac.uk/data request/cif, by
emailing data request@ccdc.cam.ac.uk, or by contacting the Cambridge Crystallographic
Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033.
References
[1] Schiele, V. C. (1964). Ber., 30, 308.
[2] Mattson, A. M., Jensen, C. O., and Dutcher, R. A. (1947). Science, 5, 294.
[3] Karabocek, N., Kucukdumlu, A., Ekmekcıoglu, P., and Karabocek, S. (2009). J. Macromol. Sci.
A, 46(10), 1007.
[4] Despaigne, A. A. R., Da Silva, J. G., Do Carmo, A. C. M., Piro, O. E., Castellano, E. E., and
Beraldo, H. (2009). J. Mol. Struc., 920, 97.
[5] McMurry, J. E. (2004). Organic Chemistry, Brooks/Cole: Pacific Grove, CA.
[6] Todeschini, A. R., de Miranda, A. L. P., da Silva, K. C. M., Parrini, S. C., and Barreiro, E.
(1998). J. Eur. J. Med. Chem., 33, 189.
[7] Shit, S., Chakraborty, J., Samanta, B., Slawin, A. M. Z., Gramlich, V., and Mitra, S. (2009).
Struct. Chem., 20(4), 633.
[8] Sridhar, R. and Perumal, P. T. (2003). Synth. Commun., 33(9), 1483.
[9] Onnis, V., Cocco, M. T., Fadda, R., and Congiu, C. (2009). Bioorgan. Med. Chem., 17(17),
6158.
[10] Bottari, B., Maccari, R., Monforte, F., Ottana, R., Vigorita, M. G., Bruno, G., Nicolo, F.,
Rotondob, A., and Rotondob, E. (2001). Bioorgan. Med. Chem., 9(8), 2203.
[11] Filipovic, N., Borrmann, H., Todorovic, T., Borna, M., Spasojevic, V., Sladic, D., Novakovic,
I., and Andjelkovic, K. (2009). Inorg. Chim. Acta, 362(6), 1996.
[12] Argu¨elles, M. C. R., Cao, R., Garc´ıa-Deibe, A. M., Pelizzi, C., Matalobos, J. S., and Zani, F.
(2009). Polyhedron, 28(11), 2187.
[13] Barros-Garcia, F. J., Bernalte-Garcia, A., Luna-Giles, F., Maldonado-Rogado, M. A., and
Vinuelas-Zahinos, E. (2005). Polyhedron, 24(10), 1125.
[14] Tezcan, H., Tunc¸, T., S¸ahin, E., and Yag˘basan, R. (2004). Anal. Sci., 20, x137.
[15] Tunc¸, T., Tezcan, H., Sarı, M., Bu¨yu¨kgu¨ngo¨r, O., and Yag˘basan, R. (2003). Acta Cryst., C59,
o528.
[16] Rigaku Americas and Rigaku. (2005). Crystal-Clear Program for Integration of the Intensities,
Correction for Lorentz, and Polarization Effects, and Cell Refinement, Rigaku Americas: The
Woodlands, TX; Rigaku Corporation: Tokyo.
[17] Sheldrick, G. M. (1990). Acta Cryst., A46, 467.
[18] Sheldrick, G. M. (1997). SHELXL-97, University of Gottingen: Germany.
[19] Farrugia, L. J. (1997). J. Appl. Cryst., 30, 565.
[20] Gilli, P., Bertolasi, V., Pretto, L., and Gilli, G. (2006). J. Mol. Struc., 790, 40.
[21] Bellamy, L. J. (1962). The Infrared Spectra of Complex Molecules, Methuen: London.
[22] Williams, D. H., and Fleming, I. (1966). Spectroscopic Methods in Organic Chemistry, McGraw-
Hill: London.
[23] Ababei, L. V., Kriza, A., Musuc, A. M., Andronescu, C., and Rogozea, E. A. (2010). J. Therm.
Anal. Calorim., 101(3), 987.
[24] Tezcan, H. and Uzluk, E. (2007). Dyes Pigm., 75(3), 633.
[25] Ding, W. F. and Jiang, X. (1998). J. Phys. Org. Chem., 11, 809.
[26] Vickery, B. B. and Willey, G. R. (1985). Acta Cryst., C41, 1072.
[27] Gunes, B., Ozbey, S., and Tezcan, H. (2003). Anal. Sci., 19, 1091.
[28] Tunc¸, T., Sarı, M., Yag˘basan, R., Tezcan, H., and S¸ahin, E. (2003). Acta Cryst., C59, o192.

208
T. Tunc¸ et al.
[29] Shanmuga, S., Raj, S., Fun, H. K., Lu, Z. L., Xiao, W., Gong, X. Y., and Kang, B. Z. (1999).
Acta Cryst., C55, 942.
[30] Shanmuga, S., Raj, S., Fun, H. K., Lu, Z. L., Xiao, W., Gong, X. Y., and Gen, C. M. (2000).
Acta Cryst., C56, 1013.