A new supramolecular zinc(II) complex containing 4-biphenylcarbaldehyde isonicotinoylhydrazone ligand: Nanostructure synthesis, catalytic activities and Hirshfeld surface analysis

Article abstract of DOI:10.1002/aoc.4141

A new potentially tridentate hydrazone ligand, 4-biphenylcarbaldehyde isonicotinoylhydrazone (4-bpinh), was prepared by the condensation of biphenyl-4-carboxaldehyde with isonicotinic acid hydrazide. Then, its nano-sized and single crystal of zinc complex were synthesized using sonochemical and heat gradient methods, respectively. The structure of complex, [Zn(4-bpinh)₂ Br₂] (1), was determined by single-crystal X-ray diffraction, FT-IR, and elemental analysis, and the nano-structure of complex was characterized by FT-IR, XRD, and SEM. The single crystal X-ray structure of complex showed that the metal center has a distorted tetrahedral geometry and the hydrazone ligand acts as monodentate trough the pyridyl N atom. Moreover, the analysis of crystal structures indicates the existence of intermolecular interactions such as N/C–H?Br/O, N/C–H?π, and π?π stacking in the stabilization of complex structure which finally led to the formation of the three-dimensional supramolecular structure. Also, the impact of this interactions was more studied using Hirshfeld surface analysis and corresponding 2D fingerprint plots. Furthermore, the catalytic activity of 1 was studied in the selective oxidation of various sulfides to corresponding sulfoxides using hydrogen peroxide as the oxidative agent.

Full text of DOI:10.1002/aoc.4141

Received: 24 May 2017
DOI: 10.1002/aoc.4141
Revised: 19 September 2017
Accepted: 23 September 2017
F U L L P A P E R
A new supramolecular zinc(II) complex containing 4‐
biphenylcarbaldehyde isonicotinoylhydrazone ligand:
Nanostructure synthesis, catalytic activities and Hirshfeld
surface analysis
Yunes Abbasi Tyula1
Michal Dusek3
| Abedien Zabardasti1 | Hamid Goudarziafshar2 | Monika Kucerakova3 |
1 Department of Chemistry, Lorestan
University, Khorramabad, Iran
2 Department of Chemistry, Faculty of
Science, Sayyed Jamaleddinasadabadi
University, Asadabad, Iran
3 Institute of Physics of ASCR, v.v.i, Na
Slovance 2, 18221 Prague 8, Czech
Republic
A new potentially tridentate hydrazone ligand, 4‐biphenylcarbaldehyde
isonicotinoylhydrazone (4‐bpinh), was prepared by the condensation of biphe-
nyl‐4‐carboxaldehyde with isonicotinic acid hydrazide. Then, its nano‐sized
and single crystal of zinc complex were synthesized using sonochemical and
heat gradient methods, respectively. The structure of complex, [Zn(4‐bpinh)2
Br2] (1), was determined by single‐crystal X‐ray diffraction, FT‐IR, and elemen-
tal analysis, and the nano‐structure of complex was characterized by FT‐IR,
XRD, and SEM. The single crystal X‐ray structure of complex showed that the
metal center has a distorted tetrahedral geometry and the hydrazone ligand acts
as monodentate trough the pyridyl N atom. Moreover, the analysis of crystal
structures indicates the existence of intermolecular interactions such as N/C–
H⋯Br/O, N/C–H⋯π, and π⋯π stacking in the stabilization of complex
structure which finally led to the formation of the three‐dimensional supramo-
lecular structure. Also, the impact of this interactions was more studied using
Hirshfeld surface analysis and corresponding 2D fingerprint plots. Further-
more, the catalytic activity of 1 was studied in the selective oxidation of
various sulfides to corresponding sulfoxides using hydrogen peroxide as the
oxidative agent.
Correspondence
Abedin Zabardasti, Department of
Chemistry, Lorestan University,
Khorramabad, Iran.
Email: zebardasti@yahoo.com
KEYWORDS
catalytic activities, Hirshfeld surface analysis, hydrazone, sonochemical synthesis, sulfoxides
1 | INTRODUCTION
supramolecular compounds such as coordination bond-
ing interactions, ligand geometry, intermolecular inter-
In recent decades, the design and synthesis of supramo-
lecular metal–organic coordination compounds have
attracted great attention because of their potential appli-
cations in various fields such as catalysis, anticancer
agents, gas storage, crystal engineering, magnetism, lumi-
nescence, molecular transport and molecular sensing.[1–6]
Several factors can contribute to the designing
actions, solvent molecules, counter ions, metal ions
and the synthetic conditions.[7–10] Among all of them,
intermolecular interactions play the most important role
in the formation of supramolecular compounds so that
it can be said that supramolecular chemistry is the
chemistry of weak interactions. The most significant of
these interactions are as follows: comparatively strong
Appl Organometal Chem. 2017;e4141.
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Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4141

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TYULA ET AL.
hydrogen bonding, halogen bonding, π–π stacking inter-
actions, CH···π interactions, anion/cation···π interac-
tions and van der Waals interactions.[11–14] Supple
isonicotinic hydrazide Schiff base ligands (hydrazones,
R‐CO–NH–N = CH‐R´) and their derivatives with multi-
farious coordination modes are good candidates for cre-
ating supramolecular compounds[15,16] because they
often acting as chelating/bridging ligands through their
N and O atoms.[17–19] In addition, the aromatic portion
of aroyl hydrazones is good candidates for spacer part
of organic‐inorganic materials, because not only they
can act as hydrogen bond acceptors or donors, but
can also provide identification sites for π‐π stacking
interactions as appealing supramolecular structure
when coordinating to the metal ions. Moreover,
hydrazones and their coordination complexes have
attracted a lot of research attention because of their
various applications such as molecular sensors,[20]
2 | EXPERIMENTAL
2.1 | Materials and equipment
All reagents for the synthesis and analysis were commer-
cially available and used as received. Microanalyses were
carried out using a Heraeus CHN‐O‐Rapid analyzer.
Melting points were measured on an Electro thermal
9100 apparatus and are uncorrected. IR spectra were
recorded using Perkin‐Elmer 597 and Nicolet 510P
spectrophotometers. X‐ray powder diffraction (XRD)
measurements were performed using an X’pert diffrac-
tometer (Panalytical) with monochromatized CuKα
radiation. The samples were characterized with a
scanning electron microscope (SEM) (Philips XL 30) with
gold coating.
2.2 | X‐ray crystallography
catalysts,[21,22] magnetic properties,[23] and
a wide
spectrum of biological activities (antimicrobial,[24,25]
anti‐cariogenic,[26] anticonvulsant,[27] antitubercular
and anticancer,[28,29] anti‐inflammatory[30]). Recently,
ligands of hydrazone type and their metal complexes
have been synthesized which studied by DFT calcula-
tions and Hirshfeld surface analysis.[31–35] During the
last two decades, synthesis of nanostructures is of great
importance because of their application in various fields
such as catalysis, magnetic, optical, biology, and
medicinal chemistry.[36–39] In addition, there is a great
interest in the synthesis of nanostructures by using
sonochemical method.[40–43] In this work, we prepared
the single crystal (bulk) and nanostructure of zinc
The crystallographic parameters and selected bond dis-
tances and angles around the metal center are listed in
Tables 1 and 2, respectively. Single crystal X‐ray diffrac-
tion data were obtained with a Gemini four circle diffrac-
tometer manufactured by Oxford Diffraction equipped
with an Atlas CCD detector, using graphite monochro-
mator and Mo Kα radiation (λ = 0.71073 Å). Standard
data collection strategy of CrysAlis[58] was used for data
collection; the same program was used for integration
of CCD images and absorption correction. The crystal
structure was solved by direct methods with program
SIR2002[59] and refined with Jana2006[60] by full‐matrix
least‐squares technique on F2. All hydrogen atoms
were discernible in difference Fourier maps and could
be refined to reasonable geometry. According to com-
mon practice H atoms bonded to C were kept in ideal
positions with C–H = 0.96 Å while positions of H
atom bonded to N was refined with distance restrains
(N–H = 0.80 Å). In both cases, Uiso(H) was set to
1.2Ueq(C, N). All non‐hydrogen atoms were refined
using harmonic refinement.
complex
with
4‐biphenylcarbaldehyde
isonicotinoylhydrazone (4‐bpinh) ligand and characteri-
zation by various methods. After that, the catalytic
activity of complex for selective oxidation of sulfides
to the corresponding sulfoxides was studied, because
sulfoxides are applied as catalysts, reagents, final prod-
ucts and especially as synthetic intermediates in the
synthesis of biological and medicinal materials.[44–46]
Therefore, there is a great interest of researchers for
selective oxidation of sulfides to the corresponding sulf-
oxides.[47–50] On the other hand, various oxidants such
as selenium oxide (SeO2), nitric acid, permanganates,
hydrogen peroxide, and oxygen are used for the oxida-
tion of sulfides.[51–54] Among them, aqueous hydrogen
peroxide (H2O2) is the most attractive because of safety
with the low expense, the high content of effective
oxygen, being environment‐friendly, easily available
reagent, and also it generates water as the only by‐
product.[55–57] We have also examined the close inter-
molecular contacts between the molecules in the crystal
packing of 1 using Hirshfeld surface analysis.
2.3 | Hirshfeld surfaces analysis
Hirshfeld surfaces analysis (HS) and the associated 2D
fingerprint plots (FP) were generated using
CrystalExplorer 3.0 program.[61] When the structure input
file in the CIF format uploaded into the CrystalExplorer
software, all bond lengths to hydrogen were automati-
cally modified to typical standard neutron values[62]
(C–H = 1.083 A, N–H = 1.009 A and O–H = 0.983
A). The 2D fingerprint plots represented by using the
standard 0.6–2.4 Å view with the de and di distance
scales displayed on the graph axes, where de is the

TYULA ET AL.
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TABLE 1 Crystal data and structure refinement of [Zn(4‐bpinh)2
Br2] (1)
distance (dnorm), based on both de, di and the van der
Waals radii (rvdW) of the atom, were mapped into the
Hirshfeld surfaces. The dnorm values were mapped onto
the Hirshfeld surface using a red‐blue‐white colour
scheme as follows: red regions with the negative values
of dnorm represent the intermolecular contacts shorter
than the sum of the van der Waals radii; blue regions
with positive values of dnorm represent the intermolec-
ular contacts longer than the sum of the van der Waals
radii; white regions denotes the distance of contacts
exactly corresponding to the van der Waals separation
with a dnorm values of zero.[63] The shape index is
highly sensitive to very subtle changes in the surface
shape; the information conveyed by the shape index
are in agreement with 2D fingerprint plots. The
curvedness is the measurement of ‘how much shape’,
the flat areas of the surface correspond to low values
of curvedness, while sharp curvature areas correspond
to high values of curvedness and usually tend to divide
the surface into patches, indicating interactions between
neighboring molecules.[64]
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system, space group
a, b, c (Å)
C38H30Br2N6O2Zn
827.9
120
1.5418
Monoclinic, P21/c
11.0589, 11.2946, 26.7096
99.205
(°)
V (Å3)
3293.22
Z,Dcalc/ (mg/m3)
Radiation type
(mm‐1)
4, 1.670
Mo K
3.22
Crystal size (mm)
Crystal shape/colour
F(000)
0.25 × 0.23 × 0.17
Polygon shape, yellow
1664
θ range for data collection/(°)
3.1–27.2
Limiting index
‐1414/‐1415/‐36,36
No. of measured, independent and 42316, 8089, 5857
observed I > 3(I) reflections
2.4 | Synthesis of 4‐biphenylcarbaldehyde
isonicotinoylhydrazone (4‐bpinh)
Rint
0.063
Data/restraints/parameters
Goodness‐of‐fit on F2
Final R indices [I > 3σ (I)]
R indices (all data)
Largest diff. Peak, hole (e Å‐3)
CCDC no.
8089, 1, 448
1.07
As shown in Scheme 1, the 4‐bpinh ligand was prepared
by the condensation of the equimolar ratio of biphenyl‐
4‐carboxaldehyde with isonicotinic acid hydrazide accord-
ing to the following procedure. A hot solution of
isonicotinic acid hydrazide (0.411 g, 3 mmol), in methanol
(30 ml) was added dropwise with stirring to a solution of
biphenyl‐4‐carboxaldehyde (0.546 g, 3 mmol) in methanol
(20 ml). About 3‐4 drops of glacial acetic acid were also
added to it as a catalyst and refluxed for 4 h. The resulting
white precipitate was filtered off, washed with methanol,
and dried in air. Yield: 0.822 g (91%), Elemental analysis
(%): calc. for C19H15N3O (MW = 301.34): C, 75.73; H,
5.02; N, 13.94. found: C, 75.67; H, 5.10; N, 13.98. FT‐IR
R1 = 0.036, wR2 = 0.091
R1 = 0.0632, wR2 = 0.0768
0.87 and ‐0.58
1534114
TABLE 2 Selected bond lengths (Å) and angles (°) for [Zn(4‐
bpinh)2 Br2] (1)
Bond lengths (Å) Exp. (1)
Bond lengths (Å) Exp. (1)
Br1–Zn1
2.378 (4)
2.340(4)
Zn1–N1
2.051 (2)
2.065 (2)
Br2–Zn1
Zn1–N2
Bond angle (°)
Br1–Zn1–Br2
Br1–Zn1–N1
Br1–Zn1–N2
Bond angle (°)
121.56 (17) Br2–Zn1–N1
108.09 (6) Br2–Zn1–N2
101.90 (6) N1–Zn1–N2
104.30 (6)
116.14 (6)
103.34 (9)
distance from the Hirshfeld surface to the nearest
nucleus outside the surface and di is the corresponding
distance to the nearest nucleus inside the surface. For
identification of the regions of particular importance to
intermolecular interactions and comparison of these
interactions in the crystal lattice, the normalized contact
SCHEME 1 Reaction scheme for the synthesis of 1

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TYULA ET AL.
(KBr) cm‐1: ν(NH) 3284 m; ν(CH)aromatic; 3056w, 3035w;
ν(C = O) 1653vs; ν(C = N) 1607; ν(NN) 1057s.
3 | RESULTS AND DISCUSSIONS
3.1 | Synthesis
2.5 | Preparation of [Zn(4‐bpinh)2Br2] (1)
The new hydrazone Schiff base ligand, ‘4‐bpinh’, was
synthesized by the condensation reaction of biphenyl‐4‐
carboxaldehyde with the equimolar amount of
isonicotinic acid hydrazide in a methanol medium, as
described later (Scheme 1). Then, the reaction of the ‘4‐
bpinh’ ligand with zinc(II) bromide was performed using
two different routes (Scheme 2), which produced crystal-
line materials of the general formula [Zn(4‐bpinh)2Br2]
(1) in the form of either single crystals or nanostructures.
Moreover, the zinc(II) complex was used as catalyzed to
oxidation of various sulfides to corresponding sulfoxides
(Scheme 3).
Single crystals of compound 1 suitable for X‐ray diffrac-
tion were prepared by a thermal gradient method in a
branched tube. The ligand 4‐bpinh (0.301 g, 1 mmol)
and zinc(II) bromide (0.225 g, 1 mmol) were placed in
the main arm of a branched tube to be heated. Methanol
was carefully added to fill both arms. The tube was sealed
and the ligand‐containing arm immersed in an oil bath at
60 °C, while the other arm was left at ambient tempera-
ture. After 8 days, yellow polygon shape crystals deposited
in the branched arm which were isolated, filtered off,
washed with acetone and ether and dried in air. Yield:
0.721
g (87%). Elemental analysis (%), calc. for
C38H30Br2N6O2Zn: C, 55.13; H, 3.65; N 10.15; found: C,
55.26; H, 3.72; N 10.09. FT‐IR (KBr) cm‐1: ν(NH)
3246 m, 3301 m; ν(CH)aromatic; 3061w; ν(C = O) 1669vs;
ν(C = N) 1604s; ν(NN) 1061 m.
3.2 | Infrared spectra
The IR spectrum of hydrazone Schiff base ‘4‐bpinh’
exhibit medium absorption band at 1607 cm‐1 attributable
to the azomethine (C = N) group. It shows also medium
2.6 | Preparation of [Zn(4‐bpinh)2Br2]
nanostructure by a sonochemical process
To prepare the nano‐sized of [Zn(4‐bpinh)2 Br2], 20 ml
solution of zinc(II) bromide (0.1 M) in water was placed
in a high‐density ultrasonic probe, operating at 20 kHz
with a maximum power output of 600 W. Into this
aqueous solution 20 ml of a 0.1 M solution of the ligand
‘4‐bpinh’ was added dropwise. After the end of the titra-
tion, the solution remained in the bath for a selected aging
time at a selected temperature. The obtained precipitates
were filtered off, washed with water and then dried in
air. Elemental analysis (%), calc. for C38H30Br2N6O2Zn:
C, 55.13; H, 3.65; N 10.15; found: C, 55.21; H, 3.69; N
10.11. FT‐IR (KBr) cm‐1: ν(NH) 3292 m, 3243 m;
ν(CH)aromatic; 3058w, 3037w; ν(C = O) 1659vs; ν(C = N)
1605; ν(NN) 1054s.
SCHEME 2 Materials produced and synthetic methods
SCHEME 3 Oxidation of sulfides to sulfoxides in the presence of
[Zn(4‐bpinh)2Br2]
TABLE 3 Selected intermolecular non‐covalent interactions in
the crystal structure of compound 1
D–HA
C3–H1c3O1i
D–H(Å) HA (Å) DA (Å)
<D–HA (°)
3.091 (3) 132.35 (2)
2.761 (4) 97.68 (2)
0.96 (3)
0.96 (3)
0.80 (3)
0.96 (3)
0.96 (3)
0.96 (3)
0.80 (3)
0.96 (3)
0.96 (3)
2.36 (2)
2.46 (2)
2.25 (3)
2.56 (2)
2.62 (2)
2.69 (2)
2.79 (3)
2.98 (3)
3.00 (3)
2.7 | General procedure for the oxidation
of sulfides catalyzed by [Zn(4‐bpinh)2Br2]
(1)
C24–H1c24O1
N5–H1n5O2ii
C17–H1c17O2
C30–H1c30O2
C31–H1c31O2
N3–H1n3Br1iii
C9–H1c9Br1iii
C2–H1c2Br1iii
3.006 (3) 157.57 (3)
3.347 (4) 139.31(2)
3.503 (4) 152.60 (2)
3.258 (4) 118.61 (2)
3.584 (2) 169.50 (3)
3.885 (3) 156.41 (2)
3.570 (2) 119.42 (14)
ii
ii
ii
A mixture of sulfide (1 mmol), H2O2 (0.5 ml) and 1
(0.03 mmol) was stirred under a solvent‐free condition
at room temperature and the progress of the reaction
was monitored by TLC. After completion of the reaction,
the products were obtained and washed with ethyl ace-
tate. Then, the products were extracted with ethyl acetate.
The organic layer was dried using 1.5 g of anhydrous
Na2SO4. Finally, the organic solvents were evaporated,
and products were obtained in good yields.
Symmetry codes: (i) ‐x, y‐1/2, ‐z + 1/2; (ii) x, ‐y + 1/2, z + 1/2; (iii) 1‐x, ½ + y,
½‐z.

TYULA ET AL.
5 of 15
and very strong bonds at the 3284 and 1653 cm‐1 due to
the stretching vibrations of the N‐H and C = O groups,
respectively. Moreover, the absence of NH2 bands at
3430 and 3304 cm‐1 and also aldehyde C‐H and C = O
stretching bands at 2854 and 1697 cm‐1 in the IR spectra
confirms the condensation reaction of isonicotinic hydra-
zide with biphenyl‐4‐carboxaldehyde. The IR spectrum of
zinc complex displays no significant shifting in the vibra-
tional frequency of azomethine group (C = N, 1606 cm‐1)
toward free ligand, indicating disaffiliation of azomethine
nitrogen atom in bonding with zinc(II) ion. The most
interesting thing that observed in the IR spectrum of the
complex is the existence of two peaks at 3246 and
3301 cm‐1 instead of one peak at 3284 cm‐1 in free ligand
corresponding to the N‐H stretching frequency. This is
due to the formation of the N–H⋯O2/Br1 hydrogen
bonds which are accordance with the crystal structure of
zinc complex. The crystal structure of 1 show the N5–
H1n5⋯O2 2.25 Å and N3–H1n3⋯Br1 2.79 Å hydrogen
bonds. Because of the O2 atom is stronger acceptor than
the Br1 atom, thus the formerly forms stronger HB than
the later. As a result, this gives rise to the shifting the
N–H vibrational frequency of complex with respect to
the free ligand (1284 cm‐1) towards higher (3301 cm‐1,
blue shift) and lower (3246 cm‐1, red shift) wave numbers
for weak H1n3Br1 and strong H1n5O2 HBs, respectively.
In addition, in a D‐HA HB system, it is now well
established that there exist weak HBs which shorten
D‐H bonds, showing blue shifts in IR spectra that named
as ‘improper blue‐shifting HBs’.[65] The C = O band
appeared at 1669 cm‐1 which show a blue shift with
respect to the free ligand. The crystal structure of the
complex clearly shows that the blue shift occurs due to
the participation of C = O group in hydrogen bonds
(Table 3). The shift of the pyridyl C = N stretching
frequency of the free ligand at 1537 cm‐1 to higher wave
number (1544 cm‐1) is due to the coordination of the
pyridyl nitrogen atom to zinc(II) ion.
FIGURE 1 The molecular structure of 1 with the atomic
numbering scheme
FIGURE 2 Part of the crystal structure of 1, showing the formation of 1D extended chain along b axis constructed by N/C–HBr1, and H⋯H
interactions

6 of 15
TYULA ET AL.
of N2O (Scheme 1), while it acts as monodentate via
pyridyl N atom.
3.3 | Structural description of [Zn(4‐
bpinh)2 Br2] (1)
As shown in Figure 1, zinc atom is four‐coordinated
by two Br atoms and two pyridyl nitrogen atoms of two
‘4‐bpinh’ ligands (ZnN2Br2) to form a slightly distorted
tetrahedral geometry exemplified by its τ4 parameter
equal to 0.87 (τ4= [360 ‐ (a + b)]/141), where a and b are
the two largest bond angles around the metal center).
The value of τ4 for the perfect square planar and tetrahe-
dral geometries is zero and unity, respectively. In the
crystal structure of 1, the [Zn(4‐bpinh)2Br2] monomers
The molecular structure of zinc(II) complex is shown in
Figure 1. Selected bond distances and bond angles are
listed in Table 2. Single crystal X‐ray analysis reveals that
the compound 1 is neutral and crystallizes in a mono-
clinic P21/c space group with the asymmetric unit of 1
containing one zinc(II) cation, two bromine anions and
two ‘4‐bpinh’ ligands, all in general positions. The Schiff
base ligand (4‐bpinh) is potentially tridentate in the form
FIGURE 3 The perspective view of the 2D structure of (1) via intermolecular N/C–H⋯O interactions which shown as blue dashed lines
FIGURE 4 Molecular packing of (1), viewed along a axis, showing the molecules are linked into a 3D supramolecular network

TYULA ET AL.
7 of 15
are linked via trifurcated acceptor (Four‐Center acceptor)
hydrogen bonds, N/C–H⋯Br1, and HH interactions to
form 1D chain running along the b axis direction
(Figure 2, Table 3). Simultaneously, these monomers are
connected together by the N/C–H⋯O interactions to
form 2D supramolecular structure parallel to the ac plane
(Figure 3), which are further assembled into the 3D supra-
stacking interactions including face‐to‐face π stacking,
C–H⋯π and N–H⋯π interactions (Figure 4, 5).
The interplanar distance of the pyridyl rings is 3.712 Å
and the N–H⋯π distance is 3.597 Å. The C–H⋯π dis-
tances are in the range of 3.653–3.892 Å. The most consid-
erable structural feature of 1 is the existence of tow 1D
helical chain structures. One is along the c axis via the
C–H⋯π and H⋯H interactions (C–H⋯π 3.838 Å and
molecular framework through the non‐covalent
π
FIGURE 5 The face‐to‐face π⋯π
stacking, C–H⋯π and N–H⋯π
interactions in complex 1
FIGURE 6 (Left) Space‐filling view of
the 1D left‐ (L) and right‐handed (R)
helical chains along c axis. (Right) The
C–H⋯π, H⋯H and N/C–H⋯O
interactions network

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TYULA ET AL.
H⋯H 2.327 Å) with the Zn1⋯Zn1 distance of 26.710 Å,
which consists of two left‐ and right‐handed helical
chains that the neighboring helical chains (left‐ and
right‐handed helical) contact together by N/C–H⋯O
hydrogen bonds (C17–H1c17⋯O2 2.56 Å, C30–H1c30⋯O2
2.62 Å, N5–H1n5⋯O2 2.25 Å) (Figure 6).
FIGURE 7 (Left) Space‐filling view of
the 1D right‐handed (R) helical chains
along a* axis. (Right) The π⋯π stacking,
C–H⋯π and C–H⋯O interactions
network
FIGURE 8 The IR spectra of (a) nano‐
sized of compound 1 prepared by
sonochemical method and (b) bulk
materials of compound 1 synthesized by
heat gradient method

TYULA ET AL.
9 of 15
The other is the 1D left‐handed helical chain along the
the simulated and experimental XRD patterns are
matching together, with very slight differences in peak
positions.
Thus, this matching XRD patterns accompanied by
the results of elemental analysis and FT‐IR spectroscopy
are good evidence to confirm the same structure of both
compounds. The morphology and size of the nanoplate
structure prepared by the sonochemical method were
characterized by scanning electron microscopy (SEM),
Figure 10.
perpendicular to bc plane (a* axis), which formed by the
non‐covalent interactions, such as π⋯π stacking and C–-
H⋯π interactions (π⋯π 3.712 Å and C–H⋯π 3.678 Å)
(Figure 7). The Zn1⋯Zn1 distance of this helix is
18.664 Å.
3.4 | Nanostructure of [Zn(4‐bpinh)2 Br2] (1)
Nanostructures of compound 1 were obtained by ultra-
sonic irradiation in an aqueous solution of zinc(II) bro-
mide and the ‘4‐bpinh’ ligand. A comparison of the IR
spectra, elemental analysis, and XRD patterns of the
nanostructure and the single‐crystalline material of com-
pound 1, clearly confirms that the synthesized nanostruc-
ture and compound 1 are structurally the same. The IR
spectra of the nanostructures and the single‐crystal
materials show characteristic absorption bands of the
‘4‐bpinh’ ligand (Figure 8).
The IR spectra of the nano‐compound show two
absorption bands at the 1663 and 1605 cm‐1 corre-
spond to the C = O and C = N stretching vibrations
of the ‘4‐bpinh’ ligand. The pyridyl C = N stretching
frequency observed at 1543 cm‐1. Moreover, weak
intensity bands in the range 3037–3058 cm‐1 can be
assigned to the stretching vibrations of the aromatic
C–H groups. Figure 9 shows the XRD pattern of the
nanostructure sample prepared by the sonochemical
process in comparison with the XRD pattern calculated
from the single crystal X‐ray data of 1 produced by the
branched tube method. This comparison reveals that
FIGURE 10 SEM photograph of [Zn(4‐bpinh)2Br2] (1) nano‐size
structure prepared by sonochemical process
FIGURE 9 XRD patterns of (a)
simulated pattern based on single crystal
data of compound 1, (b) nanostructure of
compound 1 prepared by sonochemical
process

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TYULA ET AL.
FIGURE 11 Hirshfeld surfaces mapped with (a) dnorm, (b) shape index and (c) curvedness for [Zn(4‐bpinh)2Br2]
interactions and the blue areas are devoid of such
close contacts.
3.5 | Hirshfeld surface analysis of [Zn(4‐
bpinh)2 Br2] (1)
Figure 13 display the intermolecular interactions of 1
as 2D fingerprint plots (FP), which are mainly responsible
for the assembly of a 3D supramolecular network. More-
over, this plots can be decomposed to quantify particular
contributions of intermolecular interactions in the molec-
ular packing of a solid network. Complementary regions
are evident in the fingerprint plots which indicate a
molecule acts as a donor (de > di) and another one is
found as an acceptor (de < di). The 2D fingerprint plots
of 1 demonstrate the existence of H···H, H···Br, H···N,
H···O, H···C, C···C, and N···C intermolecular interactions
between its molecules (Figure 14). Besides, the
O···H/H···O, Br···H/H···Br, C···N/N···C, and N···H/H···N
interactions are represented by a spike in the bottom right
(acceptor) area (OH 4.8%, Br···H 9.2%, C···N 2.7%, N···H
2.3%) and a spike at the top left (donor) area (HO 4.1%,
The Hirshfeld surface is an attractive and growing tech-
nique for the study of the nature and type of intermolecu-
lar interactions in the crystal structures. The molecular
Hirshfeld surfaces (dnorm, Shape index, and Curvedness)
of the title complex are shown in Figure 11, which
mapped over dnorm ranges ‐0.419 (red) to 1.364 (blue)
Å, shape index ranges ‐1 to 1.0 Å, and curvedness ranges
‐4.0 to 0.4 Å. The molecular surfaces of 1 are shown to
form of transparent for visualization of the molecular
moieties around which they were calculated.
The red spots on the dnorm surface of 1 indicate the
intermolecular close contacts involved in the hydrogen
bonds such as, C/N–H···O (Figure 12), C/N–H···Br
(Figure 13), while the white regions represent contacts
around the van der Waals separation looking like HH
FIGURE 12 The Hirshfeld surfaces mapped with dnorm function (left) and corresponding 2D fingerprint (right) for the C/N–H···O
interactions in 1

TYULA ET AL.
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FIGURE 13 The Hirshfeld surfaces mapped with dnorm function (right) and corresponding 2D fingerprint (left) for the C/N–H···Br
interactions in 1
FIGURE 14 The 2D fingerprint plots for all interactions present in [Zn(4‐bpinh)2Br2]
H···Br 5.3%, N···C 2.6%, H···N 1.6%) of the 2D fingerprint
plot. The H···C/C···H intermolecular interactions com-
prise 5.9% of the total Hirshfeld surface area which
emerge as very short spike at the top left (H···C 6.1%)
and bottom right (C···H 8.5%) of the 2D fingerprint plot.
The H···H contacts is observed as the blue regions on
the dnorm surface and exhibited by the largest region
accompanied by short and tenuous spike at the middle

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TYULA ET AL.
FIGURE 15 The Hirshfeld surfaces mapped with (a) shape index (b) curvedness for the C···C (π···π) stacking interactions in 1
of fingerprint plot which has the most significant contri-
3.6 | Catalytic activity of [Zn(4‐bpinh)2Br2](1)
bution to the total Hirshfeld surfaces (39.7%), and the
shortest close‐contact distance (di + de) is ca. 1.9 Å. The
2D fingerprint plots of 1 shows that the π···π (C···C)
stacking interactions comprise 11.1% of the total Hirshfeld
surface area.
After synthesis and characterization of 1, its catalytic
activity was studied in the selective oxidation of sulfides
to corresponding sulfoxides (Scheme 3). In order to obtain
of best reaction conditions, oxidation of methyl phenyl
sulfide using hydrogen peroxide in the presence of 1,
selected as a model reaction. In this study, various solvent
and different amounts of catalyst were examined which
summarized in Table 4. As shown in Table 4, 0.03 mmol
of 1 under solvent‐free conditions at room temperature
was found to be best reaction conditions for the oxidation
of sulfides to sulfoxides.
The generality of this study was extended by oxidation
of various aromatic and aliphatic sulfides to correspond-
ing sulfoxides (Table 5). As shown in Table 5, all products
were obtained in good yields in short reaction times. The
chemo selectivity of oxidation of sulfides in the present of
1 was studied using oxidation of 2‐(methylthio)ethanol
and 2‐(phenylthio)ethanol containing hydroxyl groups
which hydroxyl functional groups remained intact in
the conversion of sulfides to corresponding sulfoxides
(Scheme 4).
Furthermore, the presence of π···π (C···C) stacking
interactions in the crystal packing of 1 are clearly con-
firmed by two their characteristic signs, i.e. the shape
index and curvedness surfaces (Figure 15). In the shape
index, the highlighted red and blue triangles (highlighted
circles in Figure 15) proved the presence of the π···π
stacking interactions in the crystal structure of 1, which
the red triangle denotes the aromatic ring atoms of the
molecule outside the surface, while blue represents the
aromatic ring atoms inside the surface. Moreover, the
large flat green area in curvedness surface is another evi-
dence for the existence of the π···π stacking interactions.
The quantities of interactions with percentages are shown
as a histogram in Figure 16. From Figure 16 can be seen
that the H···H and N···H contacts provide the highest
and lowest share of the total intermolecular interactions
in the title complex.
FIGURE 16 Relative contributions of
various intermolecular interactions
contributing to the Hirshfeld surfaces of 1

TYULA ET AL.
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TABLE 4 Optimization of reaction conditions for the oxidation of methyl phenyl sulfide to methyl phenyl sulfoxide in the presence of 1
using H2O2
Entry
Solvent
Catalyst (mmol)
Time (min)
Yield (%)a
1
Solvent‐free
0.04
25
98
2
3
4
5
6
Solvent‐free
Solvent‐free
Ethanol
0.03
0.02
0.03
0.03
0.03
30
30
35
40
40
98
64
96
90
69
Ethyl acetate
Acetonitrile
aIsolated yield.
contributions of 37.7%. Moreover, the H···C (H···π) and
H···Br interactions show the second and third largest con-
tribution of the total Hirshfeld surfaces with 14.6 % and
14.5%, respectively. The shape index and curvedness sur-
faces accompanied by its 2D fingerprint plot indicate the
presence of the π···π interactions (11.1%) in the crystal lat-
tice of compound 1. Moreover, the nanostructure of zinc
complex was synthesized by a sonochemical method and
confirmed by IR spectra, elemental analysis, XRD pattern,
and SEM. Finally, this compound indicated superior
catalytic activity and selectivity for oxidation of various
sulfides to the corresponding sulfoxides in the presence
of hydrogen peroxide as an oxidizing agent.
TABLE 5 Oxidation of sulfides catalyzed by [Zn(4‐bpinh)2 Br2]
using H2O2
Entry
Substrate
Time (min)
Yield (%)a
1
30
98
2
3
15
40
90
88
4
25
15
94
90
5
ACKNOWLEDGEMENTS
aIsolated yield.
We are grateful to Lorestan University Research Council
for the financial support of this research. The crystallo-
graphic part was supported by the project GACR
14–03276S of the Grant Agency of the Czech Republic.
ORCID
SCHEME 4 Chemoselective oxidation of 2‐(methylthio)ethanol
and 2‐(phenylthio)ethanol in the presence [Zn(4‐bpinh)2Br2]
Yunes Abbasi Tyula
1967
http://orcid.org/0000-0001-8705-
4 | CONCLUSIONS
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How to cite this article: Tyula YA, Zabardasti A,
Goudarziafshar H, Kucerakova M, Dusek M. A new
supramolecular zinc(II) complex containing 4‐
biphenylcarbaldehyde isonicotinoylhydrazone
ligand: Nanostructure synthesis, catalytic activities
and Hirshfeld surface analysis. Appl Organometal
Chem. 2017;e4141. https://doi.org/10.1002/aoc.4141
SUPPORTING INFORMATION
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CCDC number: 1534114 for 1. The data can be obtained
free of charge via http://www.ccdc.cam.ac.uk/deposit (or