Crystal packing, vibrational studies, DFT calculations of a new hybrid nickel (II)-complex and its application in Heck and Sonogashira cross- coupling reactions

Article abstract of DOI:10.1002/aoc.4366

We particularly investigate a new material [Ni(C₁₂H₁₂N₂)(H₂O)₄]SO₄ that it was hydrothermally synthesized by reaction of 5,5’-dimethyl-2,2’-bipyridne, denoted (dmbpy), metal salt and sulfuric acid. The large crystals are characterized by X-ray single crystal diffraction, infrared, Raman spectroscopy and DFT calculation. The thermogravimetric analysis indicated that the dehydration occurs in two steps, leading to an anhydrous compound. At room temperature, the complex crystallises in the centrosymmetric space group P2₁/c with the following parameters a = 9.492 (7) ?, b = 9.539 (7) ?, c = 18.411 (1) ?,. β =102.616 (1)°, V = 1626.8 (2) ?³ and Z = 4. The asymmetric unit contains one free SO₄ ^2-counter-ion and [Ni(dmbpy)(H₂O)₄]²⁺ complex cation. The crystal structure of the complex is built up from infinite parallel two-dimensional planes, containing all the components of the structure and perpendicular to the axis b. The aqua ligands are connected to the sulfate anion via O-H…O hydrogen bonds that stabilize the three-dimensional network. The catalytic activity of the complex was examined in the coupling reactions of Heck and Sonogashira in the presence of different bases in various organic solvents under ultrasonic irradiation. The obtained results show that this type of complex can be considered as an effective catalyst for these coupling reactions. The ultrasonic activation results the encouraging yields for a short period of time: 30-45?min.

Full text of DOI:10.1002/aoc.4366

Received: 14 January 2018
DOI: 10.1002/aoc.4366
Revised: 20 February 2018
Accepted: 24 February 2018
F U L L P A P E R
Crystal packing, vibrational studies, DFT calculations of a
new hybrid nickel (II)‐complex and its application in Heck
and Sonogashira cross‐ coupling reactions
Rim Jaballi1 | Wassim Maalej1
Zakaria Elaoud1
| Dhieb Atoui2 | Habib Feki3 | Ridha Ben Salem2 |
1 Laboratory of Physical and Chemistry of
Solid State, University of Sfax, Faculty of
Sciences of Sfax, Tunisia
2 Organic Chemistry Laboratory (LR17/
ES08), University of Sfax, Faculty of
Sciences of Sfax, Tunisia
3 Laboratory of Applied Physics (LAP),
University of Sfax, Faculty of Sciences of
Sfax, Tunisia
We particularly investigate a new material [Ni(C12H12N2)(H2O)4]SO4 that it
was hydrothermally synthesized by reaction of 5,5’‐dimethyl‐2,2’‐bipyridne,
denoted (dmbpy), metal salt and sulfuric acid. The large crystals are character-
ized by X‐ray single crystal diffraction, infrared, Raman spectroscopy and DFT
calculation. The thermogravimetric analysis indicated that the dehydration
occurs in two steps, leading to an anhydrous compound. At room temperature,
the complex crystallises in the centrosymmetric space group P21/c with the fol-
lowing parameters a = 9.492 (7) Å, b = 9.539 (7) Å, c = 18.411 (1) Å,
β =102.616 (1)°, V = 1626.8 (2) Å3 and Z = 4. The asymmetric unit contains one
free SO42‐counter‐ion and [Ni(dmbpy)(H2O)4]2+ complex cation. The crystal
structure of the complex is built up from infinite parallel two‐dimensional
planes, containing all the components of the structure and perpendicular to
the axis b. The aqua ligands are connected to the sulfate anion via O‐H…O
hydrogen bonds that stabilize the three‐dimensional network.
Correspondence
Wassim Maalej, Sfax Faculty of Sciences,
Chemistry Department, Soukra Road km
3,5 ‐ B.P. 1171, 3018 Sfax – Tunisia.
Email: maalej_wassim@yahoo.fr
The catalytic activity of the complex was examined in the coupling reactions of
Heck and Sonogashira in the presence of different bases in various organic sol-
vents under ultrasonic irradiation. The obtained results show that this type of
complex can be considered as an effective catalyst for these coupling reactions.
The ultrasonic activation results the encouraging yields for a short period of
time: 30‐45 min.
KEYWORDS
Catalyst, Coupling reaction, Crystal structure, Ultrasonic activation, X‐ray diffraction
1 | INTRODUCTION
number of these materials are prepared in the presence
of pyridine and their derivatives (5,5’‐dimethyle‐
Inorganic‐organic hybrid materials have recently received
much attention due to their fascinating structural diversi-
ties,[1–4] i.e. not only for the structures and properties of
coordination complexes, but also for their excellent phys-
ical properties, such as magnetic, ferroelastic, nonlinear
optical activity, and electrical proprieties.[5–7] A large
2,2’bipyridine,
phenantroline,
4,4’‐dimethyle‐
2,2’bipyridine...).[8–10] Particularly, studies of hybrid com-
pound based on nickel have become an active research
area in organic chemistry, biology and crystal.[2,11] Thus,
in recent years, certain catalytic processes have been
developed.[12,13] Among the different strategies, the uses
Appl Organometal Chem. 2018;e4366.
wileyonlinelibrary.com/journal/aoc
Copyright © 2018 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4366

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JABALLI ET AL.
of N,N’‐bidentate ligand complexes have been proposed.
Out of the ligands developed, several examples of 2, 2’‐
bipyridines,[14–16] 1, 10’‐ phenanthrolines[17,18] and
recently the iminopyridines[19] were examined. This type
of complex is currently attracting much attention for
industrial and academic research teams.[20] In fact, it acts
as a catalyst for various currently important chemical
reactions. The Kocovsky and Malkov groups have
reported that Cu (I) complexes of 2,2'‐bipyridines are
very efficient catalysts for the allylic oxidation of ole-
fins.[21] Similar results have recently displayed that the
O‐arylation of phenols and aliphatic alcohols with the
aryl halides can be carried out in good yield.[22] Other
studies have examined new complexes of nickel (II)
dibromide of N, N’‐bidentate ligands containing pyrazole
(pz), pyrimidine (μm) or pyridine (py) aromatic rings.[23]
These complexes were tested as catalysts for the polymer-
ization of ethylene resulting from moderate to high
activities.
FIGURE 1 The elemental analysis of the [Ni(C12H12N2)(H2O)4]
SO4
2.1.2 | General Procedure for Heck Cross‐
Coupling Reaction:
The reactor (beaker of 25 ml) was charged with
0.012 mmol of catalyst, 1.5 mmol of base, 1 mmol of aryl
halide, 1 mmol of styrene and 6 ml of the solvent were
finally added to the mixture obtained and subjected to
ultrasonic irradiation, at room temperature (25 °C). After
the reaction, the mixture was cooled and the organic
phase extracted with n‐hexane and then with the satu-
rated NaCl solution. The adduct obtained was then dried
using Na2SO4 and filtered. The solvent was evaporated
using a rotary evaporator.
In the present work, we describe the chemical prepa-
ration, the crystal structure, and the thermal analyses.
Moreover, we report the combined experimental and
theoretical vibration and the convergence between them
of
a
new compound. We also examined their
catalytic activity in Heck and Sonogashira coupling
reactions. The catalytic tests were studied using different
bases in various organic solvents under ultrasonic
irradiation although it is considered the best economical
and ecological alternative for the rapid activation of the
chemical reaction.
2.1.3 | General Procedure for Sonogashira
Cross‐Coupling Reaction:
2 | EXPERIMENTAL DETAILS
2.1 | Chemical preparation
The reactor (beaker of 25 ml) was charged with
0.012 mmol of catalyst, 1.5 mmol of base, 1 mmol of aryl
halide, 1 mmol of phenylacethylene and 6 ml of the sol-
vent were finally added. The mixture obtained was sub-
jected to ultrasonic irradiation, at room temperature
(25 °C). After the reaction, the mixture was cooled and
we followed the same procedure of extraction, filtration
and purification regarding Heck coupling reaction.
2.1.1 | Synthesis of [Ni(C12H12N2)(H2O)4]
SO4 crystal
The crystal was synthesized hydrothermally from a mix-
ture, nickel (II) nitrate hexahydrate (0.5 mmol, 0.14 g) dis-
solved in
5 ml water, 5,5’‐dimethyl‐2,2’‐bipyridine
(1 mmol, 0.18 g) dissolved in 7 ml MeCN and sulfuric acid
(0.13 ml, 2 M).
2.2 | X‐ray data collection
Single‐crystal X‐ray diffraction intensity data were col-
lected at 293(2) K with a Bruker smart sApex CCD diffrac-
tometer using Mo‐Kα radiation (λ = 0.71073 Å). The data
were collected at room temperature. Lorentz and polariz-
ing effect corrections were performed before proceeding
to the refinement of the structure. Besides, absorption cor-
rections were performed using the multi‐scan technique
and the atomic scattering factors were taken from the
International Tables for X‐ray Crystallography.[24] 3102
The mixture was transferred to a Teflon‐lined auto-
clave and heated at 413 K, for 3 days. A large and blue
sample of the dimensions 0.500 х 0.400 х 0.300 mm were
collected by filtration, washed with water before being
dried at room temperature, and then cut and selected
for single‐crystal X‐ray experiments. The percentages of
organic elemental analysis CHNOS of [Ni(dmbpy)
(H2O)4]SO4 are given in Figure 1.

JABALLI ET AL.
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TABLE 1 Crystal data and structure refinement
independent reflections were measured, 2551 of which
had an intensity of I >2σ(I). The structure analyses were
carried out with the monoclinic symmetry, P21/c space
group, according to the automated search for the space
group available in WINGX.[25] The sulfur atoms and
transition metal “Ni” were fixed using the Patterson
methods with SHELXS‐86 program.[26] Nitrogen, carbon
and oxygen atoms were found from successive Fourier
calculations using SHELXL‐97.[27] The water H atoms
were located in a difference map and refined with O‐H
distance restraints of 0.88(2) Å and H‐H restraints of
1.5(2) Å. H atoms bonded to C atoms were positioned
geometrically and allowed to ride on their parent atoms,
with C‐H bonds fixed at 0.97 Å. The final cycle of refine-
ment led to the final reliability factors R1 = 0.047 and
wR2 = 0.120. Moreover, the drawings were made with
Diamond.[28]
The Crystallographic data and structure refinement
details for [Ni(C12H12N2)(H2O)4]SO4 are summarized in
Table 1. The hydrogen bonds are listed in Table 2. The
Fractional atomic coordinates and isotropic or equivalent
isotropic displacement parameters, atomic displacement
parameters and the interatomic distances and bonds
angles are given in Tables 3, 4 and 5, respectively.
Color/Shape
Blue/Parallelipipedic
Formula
Mr (g mol−1
[Ni(C12H12N2)(H2O)4]SO4
411.05
)
Crystal system
Space group
Temperature (K)
a (Ǻ)
Monoclinic
P21/c
293(2)
9.4920 (7)
9.5392 (7)
18.4113 (11)
102.616 (4)
1626.8 (2)
4
b (Ǻ)
c (Ǻ)
β (°)
Volume(Ǻ3)
Z‐space group
F (000)
856
Crystal dimensions (mm3)
0.50 × 0.40 × 0.30
CCD area detector
2.3< θ <27.5
Diffractometer
θ range for data
collection (deg)
Radiation, λ(Å),
Mo Kα, 0,71073, graphite
monochromator
Observed reflections I > 2σ(I)
2551
Rint
0.031
2.3 | Differential scanning calorimetry
(DSC) and thermogravimetric analysis
(TGA)
Range of h, k, l
Refined parameters
goodness of fit
Final R
‐11/10, ‐12/11, ‐23/23
274
1.19
Thermogravimetric analysis and Differential scanning
calorimetry for [Ni(C12H12N2)(H2O)4]SO4 were carried
out with NETZSCH STA 449F1 instrument. The 27.5 mg
powdered sample was spread evenly in a large sample
holder to avoid mass effect, in the temperature range 20‐
500 °C. The TG run was performed in following air with
a heating rate of 5 °C/min‐1.
0.047
0.120
Rw
W
=1/[σ2(Fo2)+(0.0188P)2+6.1771P]
2
2
P = (Fo + 2Fc )/3
performed at room temperature using a LABRAM‐Jobin
Yvon set up. The excitation line was the 630 nm from a
Neon laser. The incident laser power was limited to
5 mW to avoid sample heating degradation. The laser
beam was focused onto the sample through a 50 x micro-
scope objective. Furthermore, Infrared measurements
were obtained using a Perkin‐Elmer FT‐IR Spectrum
and the samples were diluted with spectroscopic grade
KBr and pressed into a pellet. All the bonds were assigned
by comparison with the spectrum of other compounds, at
room temperature. The frequencies for the corresponding
bonds are given in Table 6.
2.4 | Powder X‐ray diffraction
Concerning the phase analysis, the X‐Ray powder pat-
terns were recorded in the 2THETA range 10‐80° using
a Siemens D5000 powder diffractometer with Cu‐Kα radi-
ation (λ (Kα) = 1.5406 A°) selected with a diffracted‐beam
graphite monochromator. Powder X‐ray diffraction was
employed to verify that the materials used for thermal
analyses were the same phase as the single crystal struc-
tures for the new complex.
The UV–Visible absorption spectrum was recorded at
room temperature using a Lambda 1050 UV/Vis/NIR
spectrometer within the range of 200–800 nm. BaSO4
was used as a reference material.
The 1H NMR and 13C NMR spectra of the synthesized
compounds were recorded on a Bruker AC 400 apparatus
2.5 | Spectroscopic measurements
The FT‐IR and FT‐Raman spectra of the compound
[Ni(C12H12N2)(H2O)4]SO4 were investigated in the fre-
quency range 400‐4000 cm‐1. Raman scattering was

4 of 15
JABALLI ET AL.
TABLE 2 Hydrogen‐bond geometry (Å, °)
D—H···A
D—H
H···A
D···A
D—H···A
174 (6)
175 (6)
164 (7)
168 (6)
174 (7)
171 (6)
177 (7)
177 (9)
O1W—H1WA···O3i
O1W—H1WB···O4
O2W—H2WA···O3
O2W—H2WB···O4ii
O3W—H3WA···O1iii
O3W—H3WB···O2i
O4W—H4WB···O1ii
O4W—H4WA···O2iii
0.80 (6)
0.77 (6)
0.70 (6)
0.84 (7)
0.69 (7)
0.86 (7)
0.86 (8)
0.65 (8)
1.89 (6)
1.95 (7)
2.12 (7)
1.92 (7)
2.08 (7)
1.97 (7)
1.91 (8)
2.06 (8)
2.688 (5)
2.723 (5)
2.798 (5)
2.744 (5)
2.769 (6)
2.824 (5)
2.761 (5)
2.711 (6)
Symmetry codes: (i) −x+2, y−1/2, −z+3/2; (ii) −x+2, y+1/2, −z+3/2; (iii) x−1, y, z; (iv) −x+2, −y, −z+2.
with Fourier transform and a nominal frequency of
100 MHz. Chemical shifts are expressed in parts per mil-
lion (ppm) relative to tetramethylsilane (TMS), used as
an internal reference.
The yields were measured by gas chromatography on
a Shimadzu 2014‐GC apparatus using dichloromethane
as solvent. The capillary column was DB‐5 and the carrier
gas was nitrogen.
prismatic crystal obtained was selected by optical exami-
nation using a polarized microscope. This complex crys-
tallises in the monoclinic P21/c system with the
following unit cell dimensions a = 9.492 (7) Å, b = 9.539
(7) Å, c = 18.411 (1) Å, β = 102.616° (1), V = 1626.8 (2)
Å3 and Z = 4.
Examination of the structure shows a layer arrange-
ment perpendicular to c axis: planes of Octahedron alter-
nate with planes of C12H12N2. The [Ni(dmbpy)(H2O)4]2+
unit possesses a configuration of distorted octahedral so
that the central Nickel (II) ion is surrounded by four oxy-
gen and two nitrogen atoms. The equatorial plane of the
octahedron is formed by a pair of nitrogen donor from
dmbpy ligand and two molecules of water (O2, O3), while
the two remaining water molecules (O1, O4) coordinate at
the axial sites. The Ni‐O and Ni‐N bond length are almost
equivalent (Ni‐N1 = 2.065(3), Ni‐N2 = 2.058(4), Ni‐
O2W = 2.063(3) and Ni‐O3W = 2.061(4) Å), but Ni‐O1W
(2.023(3)) and Ni‐O4W (2.032(4)) are shorter than the
others. This is one of the main factors accounting for the
distortion from the ideal octahedral geometry of the NiII
center; this is due to the heterogeneous environment
and the Jahn Teller effect. Bond lengths and angles within
the octahedron [Ni(C12H12N2)(H2O)4]2+ are comparable
to values observed in other homologous derives.[2,3]
Figure 3 displays a projection in the (a, b) plane of the
inorganic layer. In fact, it shows that the [SO4]2‐ groups
and the octahedron are connected by three strong hydro-
gen bonds such as O1W‐H1WA...O3i, O1W‐H1WB...O4
and O4W‐H4WA...O2iii and five weak hydrogen bonds
to form infinite parallel bidimensional chains. These data
reveal that each anion [SO4]2‐ is connected to four cations
via eight water molecules.
2.6 | Theoretical calculations
The vibrational wavenumber calculations and molecular
geometry optimization carried out in the present work
were recorded by DFT method employing the Gaussian
09 package. The Becke three‐parameter hybrid exchange
functional and the Lee‐Yang‐Parr correlation functional
(B3LYP) were used in the calculation with the LanL2DZ
basis set.[29]
2.7 | Ultrasonic activation:
Irradiation was guaranteed by using an ultrasonic probe
(Sonopuls HD 3200 model, 20 kHz, 200 W) with an ultra-
sonic generator (Sonics VC 505, 300 W). The ultrasonic
probe (Φ = 3 mm) was immersed directly in the reactor.
The sonication was carried out at a low frequency of
20 kHz (amplitude of 40%) at room temperature with a
3‐s pulsation.
3 | RESULTS AND DISCUSSION
3.1 | Structure description
A molecular view of complex [Ni(C12H12N2)(H2O)4]SO4 is
shown in Figure (2a).The basic unit of the studied mate-
rial is made up of one [Ni(dmbpy)(H2O)4]2+ cation and
one [SO4]2‐ anion. The corresponding optimized geometry
by the DFT calculation is shown in Figure (2b). A
In the organic molecule, there are π‐π interactions
between antiparallel cations, with face‐to‐face distances
of 3.070 Å.[30] Therefore, these interactions show a large
role in the structure cohesion since they link two organic
groups in the same layer (Figure 4). The examination of

JABALLI ET AL.
5 of 15
TABLE 3 Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)
x
y
Z
Uiso*/Ueq
0.021 (17)
0.022 (2)
0.033 (8)
0.034 (8)
0.030 (8)
0.031 (8)
0.044 (11)
0.030 (8)
0.032 (8)
0.054 (14)
0.026 (8)
0.026 (8)
0.029 (10)
0.034 (12)
0.036 (12)
0.033 (11)
0.027 (10)
0.026 (10)
0.034 (11)
0.034 (12)
0.033 (11)
0.030 (11)
0.048 (15)
0.037 (15)*
0.035 (16)*
0.038 (19)*
0.060 (2)*
0.040 (2)*
0.060 (2)*
0.060 (3)*
0.070 (2)*
0.021 (12)*
0.044 (15)*
0.041 (16)*
0.035 (14)*
0.033 (14)*
0.024 (12)*
0.073*
Ni
0.773 (6)
1.248 (12)
1.329 (4)
1.339 (4)
1.118 (4)
1.202 (4)
0.918 (4)
0.837 (4)
0.625 (5)
0.626 (5)
0.721 (4)
0.917 (4)
0.623 (6)
0.591 (6)
0.666 (6)
0.768 (6)
0.795 (5)
0.905 (5)
0.992 (6)
1.094 (6)
1.108 (6)
1.017 (6)
0.482 (7)
0.914 (7)
0.998 (7)
0.900 (8)
0.829 (8)
0.553 (8)
0.634 (8)
0.558 (9)
0.639 (8)
0.581 (6)
0.646 (7)
0.810 (7)
0.971 (6)
1.152 (7)
1.020 (6)
0.474
0.127 (5)
0.130 (10)
0.064 (3)
0.234 (3)
0.200 (3)
0.021 (3)
0.806 (3)
0.747 (6)
0.697 (19)
0.795 (2)
0.703 (19)
0.794 (18)
0.792 (3)
0.722 (2)
0.726 (2)
0.812 (3)
0.895 (2)
0.893(2)
0.891 (3)
0.953 (3)
1.022 (3)
1.027 (3)
0.962 (3)
0.962 (3)
1.025 (3)
1.020 (3)
0.950 (3)
0.889 (3)
0.944 (4)
0.795 (3)
0.791 (3)
0.711 (3)
0.724 (3)
0.719 (3)
0.714 (4)
0.810 (4)
0.807 (4)
0.844 (3)
1.062 (3)
1.070 (3)
1.071 (3)
1.062 (3)
0.840 (3)
0.992
S
O1
O2
O3
O4
O1W
O2W
O3W
O4W
N1
−0.020 (4)
0.237 (4)
0.024 (4)
0.279 (4)
0.021 (4)
0.220(4)
N2
C1
−0.079 (5)
−0.145 (5)
−0.096 (5)
0.006 (5)
0.065 (4)
0.175 (4)
0.230 (5)
0.332 (5)
0.376 (5)
0.316 (5)
−0.260 (6)
−0.104 (6)
−0.010 (6)
0.222 (6)
0.325 (7)
0.040 (6)
−0.062 (8)
0.268 (8)
0.368 (8)
−0.098 (5)
−0.144 (6)
0.035 (6)
0.194 (5)
0.361 (5)
0.341 (5)
−0.294
C2
C3
C4
C5
C6
C7
C8
C9
C10
C11
H1WA
H1WB
H2WA
H2WB
H3WA
H3WB
H4WA
H4WB
H1
H3
H4
H7
H8
H10
H11A
H11B
H11C
H12A
0.513
−0.336
0.916
0.073*
0.391
−0.226
0.917
0.073*
1.273
0.512
0.988
0.067*
(Continues)

6 of 15
JABALLI ET AL.
TABLE 3 (Continued)
x
y
Z
Uiso*/Ueq
H12B
H12C
1.172
0.561
0.440
0.913
0.067*
1.284
0.913
0.067*
TABLE 4 Atomic displacement parameters (Å2)
Atoms
Ni
U11
U22
U33
U12
U13
U23
0.015(3)
0.015(6)
0.025(3)
0.021(2)
0.028(2)
0.025(2)
0.017(2)
0.029(2)
0.023(2)
0.027(2)
0.027(2)
0.023(3)
0.022(3)
0.033(3)
0.037(4)
0.034(3)
0.022(3)
0.020(3)
0.032(3)
0.027(3)
0.025(3)
0.026(3)
0.044(4)
0.029(4)
0.014(3)
0.014(5)
0.019(2)
0.021(2)
0.028(2)
0.021(2)
0.024(2)
0.020(2)
0.015(2)
0.022(2)
0.022(2)
0.016(2)
0.029(2)
0.024(2)
0.037(3)
0.034(3)
0.024(2)
0.021(2)
0.038(3)
0.031(3)
0.025(2)
0.029(2)
0.040(3)
0.042(3)
0.033(3)
0.039(6)
0.036(2)
0.038(2)
0.049(2)
0.056(2)
0.049(2)
0.044(2)
0.100(3)
0.045(2)
0.045(2)
0.125(4)
0.038(3)
0.050(3)
0.041(3)
0.034(3)
0.037(2)
0.037(2)
0.032(2)
0.043(3)
0.048(3)
0.036(2)
0.067(4)
0.061(2)
‐0.0007(2)
‐0.0004(4)
‐0.0011(1)
‐0.0012(1)
0.0065(1)
‐0.0087(1)
0.0075(1)
‐0.0038(1)
0.0012(1)
‐0.0051(1)
‐0.0051(1)
0.0037(1)
‐0.0050(2)
0.0007(2)
0.000(2)
0.0063(2)
0.0092(5)
0.0069(2)
0.0037(2)
0.073(2)
0.0092(2)
0.0076(2)
0.0096(2)
0.028(2)
0.0121(2)
0.0121(2)
0.024(3)
0.007(2)
0.016(3)
0.017(3)
0.010(2)
0.009(2)
0.006(2)
0.005(2)
0.003(3)
0.006(6)
0.006(2)
0.022(3)
0.005(3)
0.0006(2)
0.0003(4)
0.0008(2)
0.0009(2)
‐0.0013(1)
‐0.0041(1)
0.0031(1)
0.0040(1)
‐0.0034(2)
0.0029(1)
0.0029(1)
0.001(2)
0.0004(2)
0.006(2)
0.008(2)
0.001(2)
0.0002(2)
0.0001(2)
‐0.002(2)
‐0.010(2)
‐0.004(2)
0.0022(2)
0.007(3)
‐0.005(3)
S
N1
N2
O1
O2
O3
O4
O1W
O2W
O3W
O4W
C1
C2
C3
C4
0.000(2)
C5
0.0026(2)
0.0051(2)
‐0.001(2)
‐0.0039(2)
0.0018(2)
‐0.0043(2)
‐0.013(2)
‐0.016(2)
C6
C7
C8
C9
C10
C11
C12
the geometrical features of the organic moiety indicates
that the distance C‐C and C‐N varies between [1.375(7)‐
1.505(7)], [1.331(6)‐1.360(6)], respectively. The mid‐
planes of organic groups are located at a z = 0 and z = 0.5
(Figure 5). These results are comparable to those similar
[Fe(C12H12N2)(H2O)4]SO4 and [Zn(C12H12N2)(H2O)4]SO4
compounds.[21,22]
sulfate groups are quoted in Table 5. The present geomet-
rical characteristics are usually comparable to those
observed in some sulfate compounds.[31,32]
3.2 | X‐ray powder diffraction (XRD) at
room temperature
All the oxygen atoms of the SO4 are hydrogen bonded
to water molecules. The S‐O distances vary from 1.473(3)
to 1.477(3) Å and the O‐S‐O angles range between
109.1(2) and 110.2(2). These values confirm the distortion
of the tetrahedron SO4. The distances and angles of the
The lattice parameter and space group of [Ni(C12H12N2)
(H2O)4]SO4 were investigated by Rietveld refinement
using Fullprof program integrated in WinPLOTR soft-
ware.[33,34] The material crystallises in the space group
P21/c with the following unit cell parameters a =

JABALLI ET AL.
7 of 15
TABLE 5 Geometric parameters (Å, °)
Ni—O1W
2.023 (3)
2.032 (4)
2.058 (4)
2.061 (4)
2.063 (3)
2.065 (3)
1.473 (3)
1.475 (3)
1.476 (3)
1.477 (3)
1.331 (6)
1.351 (6)
1.340 (6)
1.360 (6)
1.391 (6)
1.391(8)
C4—C3
C5—C4
1.375 (7)
1.387 (6)
1.475 (6)
1.387 (7)
1.382 (7)
1.390 (7)
1.376 (7)
1.505 (7)
0.840 (7)
0.700 (6)
0.800 (6)
0.770 (6)
0.860 (7)
0.690 (7)
0.860 (8)
0.650 (8)
Ni—O4W
Ni—N2
C5—C6
Ni—O3W
C7—C6
Ni—O2W
C8—C9
Ni—N1
C8—C7
S—O3
C9—C10
S—O4
C12—C9
S—O2
O2W—H2WB
O2W—H2WA
O1W—H1WA
O1W—H1WB
O3W—H3WB
O3W—H3WA
O4W—H4WB
O4W—H4WA
S—O1
N1—C1
N1—C5
N2—C10
N2—C6
C1—C2
C2—C3
C2— C11
1.493 (7)
92.80 (17)
86.98 (18)
86.84 (17)
92.67 (16)
176.58 (17)
95.23 (15)
88.12 (15)
90.08 (19)
89.33 (19)
90.40 (2)
91.30 (18)
175.42 (14)
96.44 (15)
80.20 (15)
120.30 (4)
115.50 (4)
124.30 (4)
120.30 (5)
116.20 (4)
124.40 (5)
109.10 (2)
109.70 (2)
O1W—Ni—N2
O1W—Ni—O3W
O1W—Ni—O2W
O1W—Ni—N1
O2W—Ni—N1
O3W—Ni—N1
O3W—Ni—O2W
O4W—Ni—N2
O4W—Ni—O2W
O4W—Ni—O3W
O4W—Ni—N1
N2—Ni—O3W
N2—Ni—O2W
N2—Ni—N1
N2—C6—C7
N2—C6—C5
N2—C10—C9
N1—C5—C4
N1—C5—C6
N1—C1—C2
O3—S—O4
O3—S—O2
O3—S—O1
O4—S—O1
109.60 (2)
109.21 (18)
110.20 (2)
119.10 (4)
127.00 (3)
120.70 (5)
115.70 (5)
123.60 (5)
119.80 (5)
120.70 (5)
123.50 (5)
113.90 (3)
114.20 (3)
120.20 (5)
124.20 (4)
121.80 (5)
119.20 (5)
117.60 (5)
120.50 (5)
118.40 (4)
127.50 (3)
O2—S—O1
C1—N1—C5
C1—N1—Ni
C1—C2—C11
C3—C2—C1
C3—C2—C11
C3—C4—C5
C4—C3—C2
C4—C5—C6
C5—N1—Ni
C6—N2—Ni
C6—C7—C8
C7—C6—C5
C8—C9—C12
C9—C8—C7
C10—C9—C8
C10—C9—C12
C10—N2—C6
C10—N2—Ni
9.552 Å, b = 9.591 Å, c = 18.525 Å and β =104.215°. The
calculated diagram is in good agreement with the
observed pattern. At room temperature, this result
exhibits the existence of a single phase and confirms its
purity. At room temperature, the X‐Ray diffractogram, of
the title compound is indicated in Figure 6.

8 of 15
JABALLI ET AL.
TABLE 6 Calculated vibrational wavenumbers, measured infrared and Raman band position (cm‐1) with the proposed assignments
IR
RAMAN
_
calculated
3517
3037
_
Attribution
υ(OH)+ υ(CH)
3424(vs)
2964(w)
2926(w)
2742(w)
2544(w)
1608(s)
1499(m)
1477(vs)
1454(m)
1393(s)
1312(m)
1250(m)
1234(m)
1141(w)
1077(vs)
997(w)
922(w)
842(s)
_
υ(OH) + υ(CH)
υas(CH3)
2919(w)
_
‐
υas(CH3)
_
‐
υs(CH3)
1592(vs)
1490(vs)
_
1623
1512
1494
1462
1408
1335
1267
1227
1163
1063
983
υ(C=C)
υ(C=N)
υ(C=C)
−
δas(CH3)
1372(m)
1308(s)
1274(s)
1220(s)
1152(m)
1037(w)
970(m)
_
δs(CH3)
δs(CH3) +δ(C − H)
δs(OH)
υ(C=N) + δ(C − H)
δ(C − C − H)+ υ3(SO4)
υ3(SO4) + ρ(CH3)
υ1(SO4) + γ(CH3)
γ(O‐H)
966
−
873
γ(C‐H)
731(s)
751(w)
_
770
γ(C‐H) +γ(C = C − C))
γC = C − C)
τ(CCCC) + υ4(SO4)
υ4(SO4)
700(s)
733
654(s)
685(w)
647(w)
_
689
619(s)
630
491(w)
419(s)
502
γ(C − C = N) + γ(C = C − C)
υ2(SO4)
420(w)
414
vs: very strong. s: strong. m: medium. w: weak. ν: stretching. νa: asymmetric stretching. νs: symmetric stretching. δ: in the plane bending. γ; out of plane bending.
τ: twisting. ρ: rocking.
curves, which indicates the decomposition of the amine
entity.
3.3 | Thermal behavior
The thermal decomposition of complex [Ni(C12H12N2)
(H2O)4]SO4 was studied using thermogravimetric mea-
surements and differential scanning calorimetric
(Figure 7). The TG curve exhibits two distinct steps, at
3.4 | Vibrational study
118 °C‐250 °C and from 400 °C to around 460 °C. The
first step corresponding to the dehydration of the precur-
sor occurs in two steps. The first loss, between 118 and
163 °C (observed weight loss, 4.28%; calculated weight
loss, 4.37%), is attributed to the elimination of one water
molecule. The second loss, between 163 °C and 250 °C
(observed weight loss, 13.02%; theoretical, 13.13%), is
ascribed to the departure of the remaining water mole-
cules leading to the formation of the anhydrous phase.
DTA curves display three endothermic peaks, at 154,
196 and 468 °C. The two first peaks corresponding to
the dehydration of [Ni(C12H12N2)(H2O)4]SO4 and the
third peak corresponding to the second step in the TG
In order to yield more information about this compound,
we have undertaken the Raman scattering and infrared
absorption between 400 and 4000 cm‐1, at room tempera-
ture. The experimental IR and Raman wavenumbers com-
pared to the calculated from DFT method are shown in
Table 6 along with detailed assignments.
For visual comparison, the observed and simulated IR
and Raman spectra of the [Ni(dmpy)(H2O)4]SO4 are given
in Figure 8 and Figure 9. All the bands observed were
assigned by comparison with the spectrum of other
compounds.[35–43] All the IR and Raman bands of this
crystal observed in the region below 300 cm‐1 must be
due to external vibrations.

JABALLI ET AL.
9 of 15
FIGURE 3 Two‐dimensional sheet in the ab plane where ions are
linked via classical O‐H...O hydrogen bonds in [Ni(C12H12N2)(H2O)4]SO4
FIGURE 4 Offset‐face‐to‐face interactions motifs in the cation‐
cation layer
FIGURE 2 (a) Asymmetric unit of the [Ni(C12H12N2)(H2O)4]SO4
crystal. (b) Optimized geometry of the [Ni(C12H12N2)(H2O)4]SO4
3.4.1 | Vibration of [SO4]2‐anion
According to the literature, we have attributed the vibra-
tional modes of the anion SO4 .
2‐ [35–39] The presence of sulfate
anions in the crystal structure of [Ni(C12H12N2)(H2O)4]SO4
is manifested in the IR spectrum by two bands of the asym-
metric stretching vibration ν3, the first weak one at
1141 cm‐1 and the second very strong peak at 1077 cm‐1,
and appeared in Raman around 1152 and 1037 cm‐1.
This mode appears in our DFT calculation at 1163 and
1063 cm‐1. In IR, there is a small band at 997 cm‐1 on the sym-
metric stretching vibration ν1 of SO4‐1, also detected in
Raman around 960 cm‐1. The symmetric ν2 and asymmetric
ν4 modes of deformation are noted as two bands at 491,
419 cm‐1 and 654, 619 cm‐1, respectively. The DFT calcula-
tions expected these modes at 414 and 630 cm‐1.
FIGURE 5 The atomic arrangement of [Ni(C12H12N2)(H2O)4]SO4
in projection along the b‐axis

10 of 15
JABALLI ET AL.
observed by two bands occurring at 3424 and 2964 cm‐1 in
the experimental infrared spectra, but they are not observed
in Raman spectra. The bands, which appear at 1308, and
1220 cm‐1 in Raman spectra, correspond to the in‐ plane
bending mode γ(C‐H).These vibrations are noted in IR at
1312, and 1234 cm‐1. The DFT calculations determined this
mode at 1335, and 1227 cm‐1. The very weak band, at 2926
and 2742 cm‐1 in IR spectra, is attributed to CH3
asymmetric stretching. This mode appears in Raman spectra
at 2919 cm‐1. The symmetric bands υs(CH3) are located at
2544 cm‐1 with weak intensity in FT‐IR spectrum. From the
theoretical calculations, the symmetric bending vibrations
δs(CH3) are predicted at 1408 and 1335 cm‐1. It shows excel-
lent correlation with the FT‐IR and FT‐Raman bands at1393
and 1312, and 1372 1308 cm‐1, respectively.
FIGURE 6 Rietveld refinement of the X‐ray diffraction powder
pattern of [Ni(C12H12N2)(H2O)4]SO4
According to our previous results,[40–43] the stretching
modes of the bands C=C and C=N of the pyridine ring are
observed in the region between 1650‐1400 cm‐1. In our
case, we noted a strong band in the FT‐IR spectrum at
1608 cm‐1and a very high intensity peak at 1477 cm‐1,
assigned to C=C stretching vibrations. In Raman spec-
trum, this mode is observed at 1592 cm‐1. The DFT com-
putation predicts this vibrational mode at 1623 cm‐1 and
1462 cm‐1. On the other hand, the stretching modes of
C=N is traced at 1499, 1234 cm‐1 and 1490, 1220 cm−1
in both IR and Raman, respectively. The computed DFT
frequencies for the ring vibrational modes indicate excel-
lent agreement with the experimental data of the title
compound.
3.5 | Optical properties
FIGURE 7 Thermogravimetric and differential thermal analysis
plot for [Ni(C12H12N2)(H2O)4]SO4
The UV‐Vis absorption spectra recorded in the 200‐800 nm
range are displayed in Figure 10. As expected, the spectra
exhibit four absorption bands; the two first absorption
bands are at 255 and 269 nm corresponding to π‐π* transi-
tions in dmbpy ligand. The last two absorption bands are
at 287 and 319 nm, which could be attributed to n‐ π* tran-
sition. The value of the optical band gap of the compound is
1.89 eV (Figure 11), which could be a sign of their semicon-
ductor nature (the values of Eg were obtained by the use of a
straightforward extrapolation method).
3.4.2 | The vibration of water molecule
The complex [Ni(dmpy)(H2O)4]SO4 exhibits a broad, struc-
tured, strong band ranging from 3100 to 3400 cm‐1.[35,36,38]
This band is in agreement with the presence of water mole-
cules, involved in the system of hydrogen bonds (as can be
seen from the hydrogen bonding table). The out‐of‐plane
bending mode γ(OH) appears in IR at 922 cm‐1, but it is not
observed in spectra Raman. This mode shows a good agree-
ment with predicted DFT calculation at 966 cm‐1. In IR, the
deformation modes in the plane δ(OH) appear around
1250 cm‐1, for DFT calculation, appear at 1308 cm‐1.
3.6 | Catalytic reactivity Study:
The [Ni(C12H12N2)(H2O)4] SO4 complex was tested as a
catalyst for the coupling reactions of Heck and copper‐
free Sonogashira under ultrasonic irradiation in the pres-
ence of different bases in various solvents. At a first stage,
we studied the effect of solvent on the reactivity of the
coupling reaction of styrene with chlorobenzene. The
results obtained are given in Table 7. It is noted that
the evolution of the reaction increases with the polarity
3.4.3 | The vibration of organic motif
Generally, in the cation, 5,5’‐dimethyl‐2,2’‐bipyridine the aro-
matic C‐H stretching vibration groups υ(C aromatic– H)
are detected in the region located between 3000 and
3450 cm‐1.[42] For the crystal under study, these modes are

JABALLI ET AL.
11 of 15
FIGURE 8 (a) Experimental IR spectrum and (b) simulated IR spectrum of the Ni(C12H12N2)(H2O)4]SO4
FIGURE 9 (a) Simulated Raman spectrum and (b) experimental Raman spectrum of the Ni(C12H12N2)(H2O)4]SO4
of the solvent. The use of DMSO, DMF and MeCN
induced good yields reaching 95%, 86% and 58%, respec-
tively (entry1, 3 and 7). However, the use of H2O and
THF results in low yields of 19% and 20% for longer time
duration: 45 min (entry 5 and 6). This can be explained
by the secondary reactions which may occur in an aque-
ous medium.[44] In addition, solvents having low boiling
temperatures, such as THF, involve rapid vaporization
during the reaction. Thus, the decrease in liquid level
minimizes the solvation of the reagents and increases
the cavitation threshold.[45] If we examine the influence
of the nature of the base, we find that NaCO3 is best
suited to affect the coupling of styrene with chloroben-
zene (entry 1 and 3). However, the addition of Bu3N
and NaOH induces much lower yields (entry 2 and 4).
In order to elucidate the formation of the different
products obtained, we suggest the reaction mechanism
proposed in Figure 12.

12 of 15
JABALLI ET AL.
the formation of a new unstable C‐C bond (3).[46] This
involves an internal rotation around this bond so that
the hydrogen in β of the metal center becomes in the
syn position relative to Ni and thus promotes a β‐elimina-
tion which generates the stilbene and the hydride (5).
Finally, the presence of the base decomposes this hydride
by regenerating the initial complex and trapping the HX
acid formed.
The study of the coupling reaction of chlorobenzene
with phenylacethylene in the presence of [Ni(C12H12N2)
(H2O)4]SO4 as catalyst displays moderate to high
yields (Table 8). The use of inorganic bases, such as
Na2CO3 (entry 1), induces a slightly lower reactivity than
that obtained in the presence of Bu3N and Et3N (entry 2
and 3). This is consistent with NaOH which induces
null results even after a period of 45 minutes (entry 4
and 7).
FIGURE 10 UV–Vis absorption spectrum of the [Ni(C12H12N2)
(H2O)4]SO4
Among the solvents examined, it appears that DMF is
most suitable for this type of coupling. Thus, the yield
reached 73% in a short time (30 min).
In order to interpret these results, we have explained
the phenomenon of cavitation due to ultrasonic irradia-
tion as indicated in Figure 13. Indeed, the creation of
the ultrasonic wave within the reaction medium
increases the possibility of contact between the
reagents.[47] This generates the pressure variation in the
reaction mixture. These differences in pressure imply dis-
tensions and approximations between the molecular
groups.[46,48] During the rarefaction cycle, the distance
between these groups increases the cohesive forces in the
liquid, which are overcome. The presence of the dissolved
gases and the liquid vapor generate the appearance of
microbubbles called cavitation bubbles. These bubbles
undergo compression and decompression forces implying
that by their enlargement at a maximum size these
FIGURE 11 Determination of the optical band gap of
[Ni(C12H12N2)(H2O)4]SO4 by UV–Vis absorption spectrum
The cycle begins with the oxidative addition of the aryl
halide to the initial complex; followed by the syn‐inser-
tion of styrene to the complex formed which generates
TABLE 7 Coupling of chlorobenzene with styrene in presence of [Ni(C12H12N2)(H2O)4]SO4
Entry
Solvent
DMSO
DMSO
DMF
Base
Time (min)
Yield (%)a E/Z
95/<1
35/3
1
2
3
4
5
6
7
Na2CO3
Bu3N
30
30
30
30
45
45
30
Na2CO3
NaOH
Na2CO3
Na2CO3
Na2CO3
86/9
DMF
37/11
H2O
19/12
THF
20/1
MeCN
58/5
0.012 mmol of catalyst, 1.5 mmol of base, 1 mmol of aryl halide, 1 mmol of styrene, 6 mL of solvent, US, 25 °C. a the yields were measured by GC using dichlo-
romethane as solvent

JABALLI ET AL.
13 of 15
FIGURE 12 Proposed catalytic mechanism of the Heck and Sonogashira coupling reaction catalysed by [Ni(C12H12N2)(H2O)4]SO4
TABLE 8 Coupling of chlorobenzene with phenylacethylene in presence of [Ni(C12H12N2)(H2O)4]SO4
Entry
Solvent
DMF
DMF
DMF
DMSO
DMSO
THF
Base
Time (min)
Yield (%)a
1
2
3
4
5
6
7
8
Na2CO3
Et3N
30
30
30
45
30
45
45
30
45
59
73
‐
Bu3N
NaOH
Bu3N
Bu3N
NaOH
Bu3N
65
60
‐
H2O
H2O
63
0.012 mmol of catalyst, 1.5 mmol of base, 1 mmol of aryl halid, 1 mmol of phenylacetylene, 6 mL of solvent, US, 25 °C. a the yields were measured by GC using
dichloromethane as solvent.
cavitations become unstable.[49] The pressure variation indi-
cates their collapse. All forces from the outside cause their
implosion. The internal pressures due to the gas result in
their explosion with enormous energy release within
reaction medium. The low boiling temperature of THF
conveys its rapid vaporization during the reaction. Hence,
the decrease in liquid level greatly increases the cavitation
rate in the medium which adversely affects the course of
the reaction.
suggested in Figure 12 is derived from a catalytic literature
cycle that has recently been proposed.[50,51] The formation
of the complex (1') by the oxidative addition of the aryl
halide to the initial complex generates its complexation
with phenylacethylene by the dissociation of one out of
two nitrogen ligands (L) (2'). This increases the acidity of
the phenylacetylene proton relative to its free state.[52]
Therefore, the presence of the base favors its deprotonation
which generates the complex (3'). This latter reduces the
reductive elimination by yielding the diphenylacetylene
and the regeneration of the initial state of the catalyst.
The catalytic cycle of the copper‐free sonogashira
reaction is not yet well known. The mechanism that we

14 of 15
JABALLI ET AL.
FIGURE 13 Ultrasonic irradiation: creation of bubbles followed by their implosion/explosion
study, determined by IR and Raman spectroscopy
recorded in the frequency range 400‐4000 cm‐1, is very sig-
nificant as it verifies the dependence of the entities consti-
tuting our compound. The computed DFT frequencies for
the [Ni(C12H12N2)(H2O)4]SO4 show excellent agreement
with the experimental data of the title compound. The
catalytic study was tested in Heck and Sonogashira cou-
pling reactions under ultrasonic irradiation. The results
obtained reveal that the sonochemical activation yields a
moderate to high yields for a short period of time, i.e. of
just a few minutes (30‐45 min).
3.6.1 | (E)‐1,2‐diphenylethylene
Mp: 124–126 °C; IR (KBr, cm−1) ν = 2887‐3000 (CH aro),
1
1594 (C=C ethyl), 1493 (C=C aro), 957 (CH ethyl); H
NMR (400 MHz, CDCl3) δ (ppm) = 7.55 (d, 4H, J =
7.54 Hz), 7.39 (t, 4H, J = 7.4 Hz), 7.32–7.26 (m, 2H), 7.15
(s, 2H); 13C NMR (100 MHz, CDCl3) δ (ppm) = 131.6,
128.3, 128.2, 123.3, 89.4.
3.6.2 | Diphenylacetylene
Mp: 60–62 °C; IR (KBr, cm−1) ν = 2989‐3121 (CH aro),
1
1853‐1967 (C≡C), 1487 (C=C aro); H NMR (400 MHz,
ACKNOWLEDGEMENTS
CDCl3)δ (ppm) = 7.60–7.56 (m, 6H), 7.41–7.36 (m, 4H);
13C NMR (100 MHz, CDCl3)δ (ppm) = 137.3, 128.7,
128.6, 127.6, 126.5.
We are grateful to Mr. Tarek GARGOURI for access to the
KAPPA CCD diffractometer. *H.
4 | CONCLUSIONS
ORCID
The nickel (II) sulfate templated by dmpy with the for-
mula [Ni(C12H12N2)(H2O)4]SO4 was prepared under
hydrothermal conditions, characterized and discussed in
this article. The crystal structure was resolved by X‐ray
single‐crystal diffraction data. It consists of Ni2+O4N2
octahedra, sulfate tetrahedra, and 5,5’‐dimethyl‐2, 2’‐
bipyridine cations. These entities are assembled by one
kind of hydrogen bonds O‐H...O to form a three‐dimen-
sional structure. The thermal behavior studiesare summa-
rized by the elimination of water molecules and the
decomposition of the anhydrous compound. Vibrational
Wassim Maalej http://orcid.org/0000-0002-8818-2085
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packing, vibrational studies, DFT calculations of a
new hybrid nickel (II)‐complex and its application
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