The superiority of the classical synthesis compared to the hydrothermal synthesis upon the structural, optical absorption and fluorescent properties of new Cd(II) 3-fluorobenzoate complexes with Pyridine-3-carboxamide/Pyridine-3-carboxylate

Article abstract of DOI:10.1016/j.ica.2020.119694

Three new cadmium–3-fluorobenzoate complexes with pyridine-3-carboxamide/pyridine-3-carboxylate complexes, namely, [Cd₂(C₇H₄FO₂)₄(C₆H₆N₂O)₂(H₂O)<

Full text of DOI:10.1016/j.ica.2020.119694

InorganicaChimicaActa509(2020)119694
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Inorganica Chimica Acta
journal homepage: www.elsevier.com/locate/ica
Research paper
The superiority of the classical synthesis compared to the hydrothermal
synthesis upon the structural, optical absorption and fluorescent properties
of new Cd(II) 3-fluorobenzoate complexes with Pyridine-3-carboxamide/
Pyridine-3-carboxylate
⁎
⁎
Füreya Elif Öztürkkan Özbeka, , Mustafa Sertçelika, Mustafa Yüksekb, Ayhan Elmalıc,
,
Ertan Şahind
a Kafkas University, Department of Chemical Engineering, Faculty of Engineering and Architecture, 36100 Kars, Turkey
b Kafkas University, Department of Electrical and Electronic Engineering, Faculty of Engineering and Architecture, 36100 Kars, Turkey
d Ankara University, Department of Physical Engineering, Faculty of Engineering, 06100 Ankara, Turkey
c Atatürk University, Department of Chemistry, Faculty of Sciences, 25240 Erzurum, Turkey
A R T I C L E I N F O
A B S T R A C T
Keywords:
Three new cadmium–3-fluorobenzoate complexes with pyridine-3-carboxamide/pyridine-3-carboxylate com-
plexes, namely, [Cd2(C7H4FO2)4(C6H6N2O)2(H2O)2] (1), [Cd2(C7H4FO2)4(C6H6N2O)2(H2O)2] (2), [Cd(C7H4FO2)
(C6H4NO2)(H2O)] (3) were obtained under classical and two different hydrothermal conditions, respectively.
The structures of all prepared complexes were characterized by elemental analysis, FT-IR and 1H NMR spec-
troscopy, TGA/DTA and single crystal X-ray analyses. In addition, the structural features of the complexes were
studied theoretically by Hirshfeld surface analysis and the X-ray diffraction analyses were supported. It was
determined that the carboxylate groups of 3-fluorobenzoate and pyridine-3-carboxylate behaved as chelating
bidentate ligands. Hirshfeld surface analysis indicated that H⋯H, H⋯O/O⋯H, H⋯C/C⋯H, H⋯F/F⋯H and C⋯C
interactions are the significant contributors to the crystal packing of the synthesized complexes. The thermal
stabilities of the synthesized complexes have been investigated and the results showed that the complexes
display thermal stability about 100 °C and the decomposition product of anhydrous complexes was CdO. The
linear absorption and fluorescence (emission) properties of the complexes were investigated by using UV–Vis
and Fluorescence spectroscopic techniques, respectively. It was found that the complex 1 which is synthesized by
classical method has got very good emission intensity compared to the materials reported in the literature. This
makes the complex 1 potential member for image acquisition without lens and filter, security printing, data
recording and storage and laser applications, if its solid form can be done. In addition, it was determined that the
classical synthesis has superiority according to the hydrothermal synthesis on the structural, optical absorption
and fluorescence properties of the complex.
3-Fluorobenzoic acid
Pyridine derivatives
Cd(II)
Hydrothermal synthesis
Linear absorption
Fluorescence
1. Introduction
efforts to develop new synthesis methods are underway. Synthesis made
heating by stirring at room temperature and under reflux are conven-
Continuous development of technology increases the need for the
materials that can be used in many application fields. The branch of
supramolecular chemistry, which has made a significant contribution to
material science, goes on to expand day by day to synthesize these
materials and to bring out many its chemical, physical and biological
properties [1,2]. One of the most important problems encountered in
the synthesis of materials is to obtain crystals of high purity whose
structure suitable for characterization. In accordance with this aim,
tional methods. Hydrothermal/solvothermal and microwave synthesis
methods, which are alternative methods to the classical method, are
now applied in coordination chemistry laboratories. In addition to
classical synthesis, the hydrothermal synthesis is a method with many
advantages [3–6]. The hydrothermal reaction is generally defined as a
heterogeneous reaction with aqueous solvents at high pressure and
temperature to dissolve and crystallize relatively insoluble materials
under normal conditions. Hydrothermal synthesis is known reactions
⁎ Corresponding authors.
E-mail addresses: elif@kafkas.edu.tr (F.E. Öztürkkan Özbek), ayhan.elmali@eng.ankara.edu.tr (A. Elmalı).
https://doi.org/10.1016/j.ica.2020.119694
Received 2 March 2020; Received in revised form 20 April 2020; Accepted 20 April 2020
Availableonline22April2020
0020-1693/©2020ElsevierB.V.Allrightsreserved.

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
Table 1
Crystal and structure refinement data of the compounds 1–3.
1
2
3
Empirical formula
Formula weight
Temperature (K)
Wavelength (Å)
Crystal system
C
40H32N4O12F4Cd2
C40H32N4O12F4Cd2
C13H10NO5FCd
391.6
1061.9
1061.5
293(2)
293(2)
293(2)
0.71073
0.71073
0.71073
triclinic
triclinic
triclinic
Space group
P-1
P-1
P-1
Unit cell dimensions
a = 10.0315(8) Å
α = 117.167(7)°
b = 10.537(2) Å
β = 91.324(8)°
c = 10.919(4) Å
γ = 104.706(8)°
980.2(4)
a = 7.617(4) Å
α = 62.91(3)°
b = 12.324(6) Å
β = 82.87(3)°
c = 12.354(8) Å
γ = 79.41(3)°
1013.8(11)
a = 7.859(2)
α = 81.994(6)°
b = 8.201(3) Å
β = 72.138(5)°
c = 11.475(2) Å
γ = 75.628(4)°
680.28(13)
2
Volume (Å3)
Z
1
1
Density (calculated) (g/cm3)
Absorption coefficient (mm− 1
F(0 0 0)
1.798
1.739
1.91
)
1.175
1.136
1.637
528
528
384
Theta range for data collection
Index ranges
2.8 to 28.4°
3.0 to 32.1°
2.8 to 28.3°
−10 ≤ h ≤ 10, −10 ≤ k ≤ 10,
−15 ≤ l ≤ 15
26,337
−13 ≤ h ≤ 13, −14 ≤ k ≤ 14,
−14 ≤ l ≤ 14
43,619
−11 ≤ h ≤ 11, −18 ≤ k ≤ 18,
−18 ≤ l8 ≤ 16
24,952
Reflections collected
Independent reflections
Data Completeness (%)
Refinement method
4840 [R(int) = 0.084]
98.0
5557 [R(int) = 0.051]
98.9
3356 [R(int) = 0.034]
99.6
Full-matrix least-squares on F2
4514/0/283
Full-matrix least-squares on F2
4046/0/286
Full-matrix least-squares on F2
3134/0/193
1.206
Data/restraints/parameters
Goodness-of-fit on F2
1.212
1.069
Final R indices [I > 2sigma(I)]
R1 = 0.037, wR2 = 0.041
R1 = 0.059, wR2 = 0.109
R1 = 0.029
wR2 = 0.073
R1 = 0.032
wR2 = 0.075
1.350 and 0.510
1962338
R indices (all data)
R1 = 0.091, wR2 = 0.094
R1 = 0.147, wR2 = 0.176
Largest diff. peak and hole
CCDC Number
1.44and 1.036
1956914
2.31 and 1.15
1960810
under high temperature and high pressure (> 100 °C and > 1 atm), in
closed systems where water is used as the solvent [3,7,8]. Metal-Or-
ganic Frameworks (MOFs), which are intriguing with their various
molecular architectures, are used in many fields due to their magnetic,
optical, ion exchange and catalysis properties. The structural and
physical properties of the synthesized complexes are influenced by
many factors such as the organic ligands, reaction conditions, metal/
ligand ratio, solvent and synthesis method etc [9–11].
FT-IR, 1H NMR, UV–Vis and Fluorescence spectroscopic techniques, re-
spectively.
2. Experimental
2.1. Materials and physical measurements
3-Fluorobenzoic acid (Merck), pyridine-3-carboxamide (Fluka),
Cadmium sulfate 8/3 hydrate (Sigma-Aldrich), Sodium bicarbonate
(Merck) and Sodium Hydroxide (Merck) were purchased commercially
available and used without further purification. The microanalyses of C,
N and H were carried out using an LECO, CHNS-932 analyzer. FT-IR
spectra (solid samples) were recorded in the range of 600–4000 cm−1
with a Perkin Elmer FrontierTM FT-IR Spectrometer using a Diamond
ATR accessory. 1H NMR spectra (DMSO‑d6) were recorded on an
AGILENT NMR 400 MHz instrument. Thermal stability studies (TGA)
were carried out on a ShimadzuTG-50 analyzer at a heating rate of
10 °C min−1 in a N2 atmosphere (25–1000 °C temperature range) and
highly sintered α-Al2O3 was used as a reference material.
Ligands with at least one carboxylate group and a large conjugated
π system have an important role in the formation of (MOFs). The
structural architecture of coordination compounds containing these li-
gands and transition metals becomes stable with weak non-covalent
interactions such as intramolecular and intermolecular hydrogen bonds
and π-π stacking interactions. Among these ligands, while benzoic acid
derivatives are widely used as the primer ligand, pyridine derivatives
are also used as auxiliary co-ligands. In addition to the π-π interactions
on the phenyl and pyridine rings, the strong bonds that the oxygen
atom/atoms of carboxylate group and nitrogen atom of pyridine ring
build with the metal atoms construct a strong conjugate unit, which
significantly affects the severity of the emission [9,10,12–14].
Numerous studies on the fluorescence properties of mixed-ligand
complexes of Cd(II) that exhibit different coordination numbers and
geometries and being a d10 metal are in the literature [11,15–19]. The
complexes obtained from these studies are considered to be used as
luminescence-, nitroaromatic explosive detector-, and OLED- materials.
To contribute to the richness of the supramolecular chemistry field, we
have synthesized Cd(II) 3-fluorobenzoic acid with pyridine-3-carboxamide/
pyridine-3-carboxylate as co-ligand and three new complexes which their
general formulas are given as: [Cd2(3-FC6H4COO)4(C6H6N2O)2(H2O)2 (1)
Cd2(3-FC6H4COO)4(C6H6N2O)2(H2O)2 (2), Cd2(3-FC6H4COO)2(C6H6NO2)2
(H2O)2 (3). However, we analyzed the structural features, thermal behavior,
optical absorption and emission features of the synthesized complexes, by
using elemental analysis, single crystal X-ray diffraction, TGA/DTA analysis,
2.2. Preparation of aqua(μ-3-fluorobenzoato-κ2-O:O)(μ-3-fluorobenzoate-
κ3-O:O:O)(pyridine-3-carboxamide-κ-N) cadmium(II) (1)
Sodium bicarbonate (0.84, 10 mmol) and 3-fluorobenzoic acid (1.40,
10 mmol) were mixed in 100 mL deionized water and stirring at 60 °C until
CO2 gas was removed. Pyridine-3-carboxamide (1.22 g, 10 mmol) was
dissolved in 50 mL water. The prepared pyridine-3-carboxamide and so-
dium 3-fluorobenzoate solutions were added in containing cadmium sul-
fate solution (1.04 g, 5 mmol) in 20 mL distilled water, respectively. The
clear solution was allowed to stand at room temperature for slow eva-
poration. After two weeks, colorless crystals (1) afforded and the product
was filtered and washed with deionized water. Elem. anal. calcd (%):C
45.26; H 3.04; N 5.28. Found: C 45.44; H 3.28; N 5.17.
2

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
Fig. 1. a) Molecular structure of Cd(II) complex 1. b) Coordination environment around Cd(II) ions in complex 1. c) Hydrogen bond geometry in asymmetric unit. d)
Stacking of the Cd(II) molecules 1 with the unit cell viewed down along the a-axis. e) The two dimensional H-bonding network in complex 1. Symmetry (i) 1-x,1-y,1-
z.
3

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
Fig. 2. a) Molecular structure of Cd(II) complex 2. b) Coordination environment around Cd(II) ions in complex 2. c) 1D-Hydrogen bond geometry. d) The two
dimensional H-bonding network in complex 2. Stacking motif of the Cd(II) molecules 2 with the unit cell viewed down along the c-axis. e) Stacking motif of the Cd(II)
molecules 2 with the unit cell viewed down along the b-axis. f) Stacking motif of the Cd(II) molecules 2 with the unit cell viewed down along the a-axis. Symmetry (i)
1-x,1-y,1-z.
4

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
acid (0.56 g, 4 mmol), pyridine-3-carboxamide (0.48 g, 4 mmol), NaOH
(0.16 g, 4 mmol) and 15 mL deionized water was stirred in beaker and
then sealed in a 50 mL Teflon-lined autoclave. The autoclave was he-
ated to 140 °C and held at that temperature for 96 h, then slowly cooled
to room temperature. Colorless crystals of 3 were filtered and washed
deionized water and dried in air. Elem. anal. calcd (%): C 39.87; H 3.06;
N 3.44. Found: C 38.97; H 2.57; N 3.58. 1H NMR (400 MHz, DMSO‑d6)
δ 7.28 (t, 4H, ArH; J = 8.40 Hz), 7.43 (d, 4H, ArH; J = 7.60 Hz), 7.64
(d, 4H, ArH; J = 9.60 Hz), 7.78 (d, 4H, ArH; J = 7.20 Hz) (3-fluor-
obenzoate moiety); 7.53 (t, 4H, ArH; J = 7.20 Hz), 8.35 (d, 4H, ArH;
J = 7.60 Hz), 8.74 (s, 4H, ArH), 9.24 (s, 4H, ArH) (pyridine-3-car-
boxylate moiety).
Under hydrothermal synthesis conditions, there are some studies
suggesting that pyridine derivatives were oxidized to another pyridine
derivatives such as 4-pyridinecarboxylate and pyridine-3-carboxylic
acid at high temperatures [20,21]. In this context, it was determined
that there was no pyridine-3-carboxamide ligand in structure of this
complex and pyridine-3-carboxamide ligand was converted to pyridine-
3-carboxylate at 140 °C by using different methods.
2.5. Optical absorption and emission measurements
Before recording of the optical absorption and emission properties
of the complexes their solutions were prepared. All of the complexes
were dissolved in dimethylformamide (DMF) solvent at 0.01 g/mL
concentration. The optical absorption spectra of the complexes were
measured by using a UV–Vis spectrophotometer (Shimadzu UV-1800)
at room temperature. The optical emission (fluorescence) spectra of the
complexes were recorded with help a fluorescence spectrophotometer
(Perkin Elmer LS55) under different excitation wavelengths among
200 nm and 780 nm, to obtain the maximum emission intensities. The
maximum emission intensities for 1, 2, and 3 were obtained while the
complexes were excited with 320, 200 and 310 nm wavelengths, re-
spectively.
Fig. 2. (continued)
2.6. Crystal structure determination
1H NMR (400 MHz, DMSO‑d6) δ 7.26 (t, 4H, ArH; J = 8.40 Hz),
7.41 (d, 4H, ArH; J = 8.00 Hz), 7.63–7.66 (m, 4H, ArH), 7.79 (d, 4H,
ArH; J = 7.60 Hz) (3-fluorobenzoate moiety); 7.51 (t, 2H, ArH;
J = 7.60 Hz), 7.63–7.66 (m, 2H, NH), 8.20 (s, 2H, NH), 8.25 (d, 2H,
ArH; J = 8.00 Hz), 8.73 (s, 2H, ArH), 9.08 (s, 2H, ArH) (pyridine-3-
carboxamide moiety).
The intensity data of complexes 1–3 was collected at 293(2) K on a
Rigaku R-Axis Rapid-S diffractometer with graphite monochromatic
Mo-Kα radiation (λ = 0.71073 Å). A suitable single crystal for X-ray
diffraction was mounted on a glass fiber. The structure was solved by
direct methods and was refined on F2 by full-matrix least-squares
technique. All calculations were completed with the SHELXL-97 crys-
tallographic software package [34]. All non-hydrogen atoms were re-
fined anisotropically. The hydrogen atoms were assigned with common
isotropic displacement factors and included in the final refinement by
using geometrical restrains. Crystallographic crystal data and proces-
sing parameters for 1–3 are given and summarized in Table 1.
2.3. Preparation of di-μ-pyridine-3-carboxamide-κ2-N1:O;κ2-O:N1 bis
[aquabis(3-fluorobenzoate-κ2 O,O′)cadmium(II)] (2)
A mixture of cadmium sulfate (0.42 g, 2 mmol), 3-fluorobenzoic
acid (0.56 g, 4 mmol), pyridine-3-carboxamide (0.48 g, 4 mmol), NaOH
(0.16 g, 4 mmol) and 15 mL deionized water was stirred in beaker and
then sealed in a 50 mL Teflon-lined autoclave. The autoclave was he-
ated to 120 °C and held at that temperature for 96 h, then slowly cooled
to room temperature. Colorless crystals of 2 were filtered and washed
deionized water and dried in air. Elem. anal. calcd (%): C 45.26; H 3.04;
N 5.28. Found: C 44.79; H 3.32; N 5.10. 1H NMR (400 MHz, DMSO‑d6)
δ 7.27 (t, 4H, ArH; J = 8.40 Hz), 7.42 (d, 4H, ArH; J = 7.20 Hz),
7.63–7.65 (m, 4H, ArH), 7.78 (d, 4H, ArH; J = 8.40 Hz) (3-fluor-
obenzoatemoiety); 7.51 (t, 2H, ArH; J = 7.60 Hz), 7.63–7.65 (m, 2H,
NH), 8.18 (s, 2H, NH), 8.23 (d, 2H, ArH; J = 8.00 Hz), 8.72 (s, 2H,
ArH), 9.07 (s, 2H, ArH) (pyridine-3-carboxamide moiety).
2.7. Hirshfeld surface analysis
To obtain visualization of intermolecular interactions of the syn-
thesized complexes, Hirshfeld surface analysis [22,23] was performed.
Both the Hirshfeld surface [24] and 2D fingerprint [23] plots were
obtained using CrystalExplorer Version 17.5 program [25].
3. Results and discussion
3.1. Crystal structure description
Single crystal X-ray data revealed that, Cd(II) complexes 1–3 crys-
tallized in the triclinic space group P-1. The molecular structures and
atom numbering of 1–3 are shown in Figs. 1-3 respectively. They differ
slightly in the geometric parameters and coordinations are similar in all
complex units. The Cd(II) 1–3 complexes have the hepta-coordinated
environment with a distorted pentagonal bipyramidal geometry. The
2.4. Preparation of aqua(μ-3-fluorobenzoate-κ2-O:O)(pyridine-3-
carboxylate-κ-N:O) (pyridine-3-carboxylate-κ2-O:O)cadmium(II) (3)
A mixture of cadmium sulfate (0.42 g, 2 mmol), 3-fluorobenzoic
5

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
Fig. 3. a) Molecular structure of the Cd(II) complex 3. b) Coordination environment around Cd(II) ions in complex 2. c) 1D-polymeric coordination geometry of 3. d)
Stacking motif of the Cd(II) molecules 3 with the unit cell viewed down along the b-axis. Symmetry (i) 1 + x,y,z.
most important bond distances (Å) and angles (°) for 1–3 are listed in
Table 2.
the axial position showed significant deviation from linearity with O5-
Cd1-O1 angle of 156.4(3)°. The major reason for the deviation is that
the Cd(II) ions were bridged over the oxygen atoms of the two different
3-fluorobenzoate ligands. Such situation leads to further repulsion
among the planar 3-fluorobenzoate and pyridine-3-carboxamide moi-
eties, hence found more twisted from one another to minimize the steric
repulsion.
For the complex 1, Cd(II) is coordinated by five chelated oxygen
atoms from 3-fluorobenzoate anions and one nitrogen (N1) atom from
pyridine-3-carboxamide and one oxygen (O5) atom from aqua ligand
leading to a pentagonal bipyramidal geometry. Two adjacent Cd(II)
ions are connected by 3-fluorobenzoate oxygen atoms creating a bi-
nuclear unit, in which the Cd/Cd distance is 4.078(3) Å (Fig. 1). The
coordinated O1 atom of the 3-fluorobenzoate and aqua ligand found in
The packing of complex 1 is controlled by a series of NeH⋯O and
OeH⋯O hydrogen bridges summarized in Table 3. The NH-groups from
6

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
Table 2
Selected geometric parameters for the Cd(II) complexes 1–3 (Å, °).
1
Cd1-O3
2.198(2)
Cd1-N1
2.249(2)
2.585(3)
91.71(10)
89.86(9)
86.83(8)
84.15(9)
156.40(8)
Cd1-O2
2.285(3)
2.591(3)
124.88(10)
85.26(10)
53.09(9)
77.40(8)
76.05(8)
Cd1-O5
2.383(3)
Cd1-O1
Cd1-O1i
O3-Cd1-N1
O3-Cd1-O5
O3-Cd1-O1
O5-Cd1-O1
O2-Cd1-O1i
143.38(9)
95.12(9)
O3-Cd1-O2
N1-Cd1-O5
N1-Cd1-O1
O3-Cd1-O1i
O5-Cd1-O1i
N1-Cd1-O2
O2-Cd1-O5
O2-Cd1-O1
N1-Cd1-O1i
O1-Cd1-O1i
119.14(8)
123.54(8)
118.32(10)
Symmetry code (i) 1-x,1-y,1-z.
2
Cd-O1
2.302(6)
Cd-O3
2.315(4)
2.342(4)
2.745(6)
87.7(2)
Cd-O2
2.330(4)
Cd-N1i
2.341(4)
Cd O5
Cd-O6
2.442(4)
Cd-O4
2.533(5)
Cd-C14
Cd-C7
2.755(6)
O1-Cd O3
91.3(2)
O1-Cd O2
O3-Cd-N1i
O3-Cd-O5
O1-Cd-O6
O3-Cd-C14
O5-Cd-C14
O1-Cd-C7
O3-Cd-O2
O2-Cd-N1i
O2-Cd-O5
O6-Cd-O4
O2-Cd-C14
O6-Cd-C14
O3-Cd-C7
176.98(12)
90.93(14)
90.28(15)
138.38(14)
88.42(16)
27.45(14)
87.95(17)
O1-Cd-N1i
O1-Cd-O5
85.20(19)
137.10(18)
137.68(14)
163.83(19)
110.55(15)
110.96(15)
91.84(14)
88.48(15)
167.71(18)
91.73(15)
27.23(14)
26.5(2)
N1-Cd-O5i
O1-Cd-C14
N1-Cd-C14i
O4-Cd-C14
Symmetry code (i) 1-x,1-y,1-
3
Cd-O1
2.214(3)
2.349(2)
2.623(3)
1.264(4)
1.248(4)
101.48(10)
133.87(9)
86.09(8)
83.64(9)
Cd-N1
2.273(2)
2.456(2)
2.741(3)
2.456(2)
2.349(2)
O3
Cd-O3
2.340(3)
2.575(2)
2.756(3)
2.575(2)
142.28(10)
Cd-O4i
Cd-O5i
Cd-O5ii
Cd-O2
Cd-C13i
O5-Cdiii
O4-Cdiii
N1-Cd
Cd-C7
O5-C13
O4-C13
O1-Cd-O3
N1-Cd-O4i
N1-Cd-O5i
O1-Cd O5ii
O5-Cdii
O1-Cd-N1
87.91(8)
O1-Cd-O5i
O4-Cd-O5i
O1-Cd-O4i
123.68(9)
54.47(8)
83.72(10)
O3-Cd-O4i
O3-Cd-O5i
N1-Cd-O5ii
84.02(9) .
108.54(9)
82.57(8)
Symmetry code (i) 1 + x,y,z. (ii) 1-x,-y,1-z. (iii) −1 + x,y,z
from pyridine-3-carboxamide ligands and one oxygen (O5) atom from
aqua ligand leading to a pentagonal bipyramidal geometry. Adjacent Cd
(II) ions are connected by two pyridine-3-carboxamide ligands and
create binuclear structural unit, for this complex the Cd/Cd distance is
7.204 (3) Å. The coordinated water molecules make hydrogen bonds
(Table 3) to two neighboring molecules; to O4 (2.733(4) Å under
symmetry operation (1-x,1-y,-z) and to O5 (2.859 (4) Å under sym-
metry operation (1-x,1-y,-z) (Fig. 3). This results in hydrogen-bonded
1D polymeric structure parallel to the c- axis. N2-H⋯O6 bonds connect
these one-dimensional structures in two dimensions (Fig. 2).
Table 3
Hydrogen-bond geometry for the Cd(II) complexes 1–3 (Å, °).
D-H…A
D-H
H⋯A
D⋯A (Å)
< D-H⋯A
Symmetry (i)
1
N2-H∙∙∙O7i
N2-H⋯O2i
O5-H⋯O7i
O5-H⋯O4
2
0.86
0.86
0.92
0.91
2.19
2.16
1.95
1.89
2.972(5)
2.889(5)
2.854(5)
2.790(5)
150
142
166
169
1-x,-y,1-z
x,-1 + y,z
1-x,1-y,1-z
1-x,1-y,1-z
N2-H∙∙∙O6i
O3-H∙∙∙O4i
O3-H∙∙∙O5i
3
0.86
1.00
0.81
2.06
1.84
2.10
2.903(7)
2.732(7)
2.863(5)
166
146
155
1 + x,y,z
1-x,1-y,-z
1-x,1-y,-z
Finally, in complex 3, the asymmetric unit contains a Cd(II) ion,
pyridine-3-carboxylate, aqua ligand and 3-fluorobenzoate anion. Cd(II)
is coordinated by two chelated oxygen atoms from 3-fluorobenzoate,
one nitrogen (N1) and three oxygen atoms from pyridine-3-carboxylate
and one oxygen (O5) atom from aqua ligand leading to again a pen-
tagonal bipyramidal geometry. Adjacent Cd(II) ions are connected by
oxygen atoms of the pyridine-3-carboxylate ligands and create bi-
nuclear structural unit, the Cd/Cd distance is 3.984(3) Å. These dual-
core units consist of polymeric structure with the same pyridine-3-
carboxylate ligands. OeH⋯O hydrogen bonds between chelated
oxygen atoms and aqua ligands leads to the formation of new 2-D
O3-H∙∙∙O2i
O3-H∙∙∙O4
0.92
0.91
1.92
2.04
2.835(4)
2.938(4)
173
169
1-x,1-y,1-z
2-x,1-y,1-z
pyridine-3-carboxamide and the crystal water molecules connect the
complex units via N2-H⋯O2, N2-H⋯O7, O5-H⋯O7 and O5-H⋯O4
hydrogen bonds forming the 2D polymeric structure defined in Fig. 1.
In complex 2, Cd(II) is coordinated by four chelated oxygen atoms
from 3-fluorobenzoate anions, nitrogen (N1) and oxygen (O2) atoms
Fig. 4. View of the three-dimensional Hirshfeld surface of the complex 1, 2 and 3 plotted over dnorm in the range −0.6103 to 1.2686, −0.5799 to 1.3270 and
−0.5823 to 1.5717 a.u.
7

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
Fig. 5. Hirshfeld surface of the complex 1–3 plotted over shape-index.
Fig. 6. The full two-dimensional fingerprint plots for the complex 1, showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯O/O⋯H, (d) H⋯C/C⋯H, (e)
H⋯F/F⋯H and (f) C⋯C interactions. The di and de values are the closest internal and external distances (in Å) from given points on the Hirshfeld surface contacts.
lattices in two dimensions (Fig. 3).
3.2. Hirshfeld surface analysis
All the bond lengths of Cd-N, Cd-O are in the normal range observed
in other Cd(II) compounds [26–30]. The Cd-Npy bond lengths, Cd1-N1
2.249(3), Cd-N1 2.341(3), Cd-N1 2.273(3) Å, for the 1–3 complexes,
respectively are comparable to the corresponding values in similar
systems [26,27]. Furthermore, the Cd–Ocarboxylate distances found for
the studied cadmium complexes, Cd1-O 2.284(5)-2.697(3) (1), Cd-O
2.302(3)-2.533(3)(2), Cd-O 2.215(5)-2.623(3) Å (3), bond ranges are
close to the existing reported complexes [26–30]. The bite angles, N1-
Cd1-O1 77.4(2)° (1), O1-Cd1-O3 84.1(2)° (1), O5-Cd-O1 83.6(2)° (3),
N1-Cd-O5 82.6(2)° (3) for the studied cadmium complex show sig-
nificant variation from the ideal value 90°. Similarly, O1-Cd1-O5
156.4(2)° (1) and O3-Cd-O5 169.5(2)° (3) angles are quite far away
from the ideal value of 180°. Since complex 2 coordinates on two se-
parate pyridine-3-carboxamide ligands, these angles are much closer to
ideal values (O2-Cd-O3 = 176.9°) (Table 2). The tension in this
structure is generally lower.
Hirshfeld surfaces allow intermolecular interactions to be displayed
with different colors and color intensity, representing short or long
contacts and the strength of interactions [31]. The dnorm maps of the
complexes were shown in Fig. 4. Red spots represent signifying close
contacts attributed to the NeH⋯O and OeH⋯O on the dnorm maps
[32].
On the shape-index for complex 1–3, convex blue regions and
concave red regions represent donor groups and acceptor groups, re-
spectively Fig. 5. As can be seen from the inspection of adjacent red and
blue triangles there are π-π stacking interactions in crystal structures of
complex 1–3 (in Fig. 5).
Significant intermolecular interactions of the complex 1–3 were
mapped in Figs. 6-8. On the Hirshfeld surfaces of the complex 1, 2 and
3, the H⋯H interactions were observed in the largest region (30.0% for
1; 33.5% for 2 and 27.0% for 3) of the fingerprint plot with a high
8

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
Fig. 7. The full two-dimensional fingerprint plots for the complex 2, showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯O/O⋯H, (d) H⋯C/C⋯H, (e)
H⋯F/F⋯H, (f) C⋯C and (g) C⋯F/F⋯C interactions. The di and de values are the closest internal and external distances (in Å) from given points on the Hirshfeld
surface contacts.
Fig. 8. The full two-dimensional fingerprint plots for the complex 3, showing (a) all interactions, and delineated into (b) H⋯H, (c) H⋯O/O⋯H, (d) H⋯F/F⋯H, (e)
C⋯C, (e) H⋯C/C⋯H and (g) O⋯Cd/Cd⋯O interactions. The di and de values are the closest internal and external distances (in Å) from given points on the Hirshfeld
surface contacts.
concentration at di + de ~ 2.2 Å, 2.2 Å and 2.3 Å, respectively. H⋯O/
O⋯H interactions were determined as second significant inter-
molecular interactions of the complex 1–3 (21.7% and di + de ~ 1.8 Å
for 1; 19.5% and di + de ~ 1.7 Å for 2 and 26.0% and di + de ~ 1.8 Å
for 3). These interactions appear as two spikes. The H⋯C/C⋯H inter-
actions contribute to 16.6%, 13.5% and 9.4% of the Hirshfeld surface of
complex 1, 2 and 3, respectively. These interactions were had as the
largest region and highly concentrated at the edges of the fingerprint
plot (di + de ~ 2.6–2.8 Å). For complex 1, 2 and 3, The H⋯F/F⋯H
contacts on the fingerprint plot, which contribute 8.7%, 10.3% and
12.2% of the total Hirshfeld surface, respectively. These contacts were
observed as two symmetrical narrow pointed wings. The C⋯C inter-
actions of complex 1, 2 and 3 covered 7.9%, 8.6% and 9.8% of the
surface, respectively. These interactions were attributed to π- π stacking
interactions. These weak interactions contribute the most to the crystal
packing of the complexes. The percentage of these intermolecular
contacts from obtained Hirshfeld Surface analysis were given in Figs. 9-
11.
9

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
at about 3386–3214 cm−1, 3377–3152 cm−1 respectively. The IR dif-
ference, Δν(COO−), between the asymmetric carboxylate, (COO−
)
as
and the symmetric carboxylate, (COO−
) vibrations which are the
s
characteristic strong stretching frequencies in the carboxylate com-
plexes are given to information about the different binding modes of the
ligands. These values for 1, 2 and 3 complexes are 140, 149 and
157 cm−1, respectively. The lower Δν(COO−) values than the ionic
values indicate that the carboxylate group of the 3-fluorobenzoate and
pyridine-3-carboxylate (for 3) ligand coordinates to the cadmium ion in
a chelating bidentate coordination mode. ν(C]O) stretching for 1 and 2
complexes are observed at 1694 and 1669 cm−1, respectively. A sharp
band at 1228, 1228 and 1224 cm−1 in spectra of 1, 2 and 3, respec-
tively are assigned to aromatic C-F stretching vibration (Supplemental
Figs. 1-3) [33–37].
3.4. 1H NMR spectra
The structures of the complexes were characterized by using 1H
NMR spectroscopy and the obtained data supported the results of single
crystal X-ray analysis and FT-IR spectroscopy. The 1H NMR spectra of
the complexes were recorded in DMSO‑d6. The aromatic protons of
phenyl and pyridine rings are distinguished. Resonances of the aromatic
protons for 3-fluorobenzoic acid showed signals at 7.26, 7.41,
7.63–7.66 and 7.79 ppm (for complex 1), 7.27, 7.42, 7.63–7.65 and
7.78 ppm (for complex 2) and 7.28, 7.43, 7.64 and 7.78 ppm (for
complex 3). Resonances of the aromatic protons for pyridine 3-car-
boxamide showed signals at 7.51, 8.25, 8.73 and 9.08 ppm (for complex
1) and 7.51, 8.23, 8.72 and 9.07 ppm (for complex 2). Resonances of
the aromatic protons for pyridine 3-carboxylate appeared signals at
7.53, 8.35, 8.74 and 9.24 ppm. In addition, NH protons of pyridine-3-
carboxamide in spectra of the complex 1 and 2 were observed at
7.63–7.66 and 8.20 ppm and 7.63–7.65 and 8.18 ppm, respectively
[38]. The signals at δ 3.49, δ3.45 and δ3.73 are related to proton of
coordinated water molecules for complexes 1–3, respectively
(Supplemental Figs. 4-6) [39].
Fig. 9. The percentages of the intermolecular interactions from obtained
Hirshfeld Surface analysis of complex 1.
Fig. 10. The percentages of the intermolecular interactions from obtained
Hirshfeld Surface analysis of complex 2.
3.5. Thermogravimetric analysis (TGA/DTA)
Thermogravimetric analysis results were given in Supplemental
Figs. 7-9. For 1, decomposition of the complex occurred in three steps.
At the temperature range of 90–155 °C, the coordinated water mole-
cules were released (exp. 3.92%, calc. 39%). The pyridine-3-carbox-
amide ligand was removed from the complex 1 in the second step at a
temperature range of 155–325 °C (exp. 23.93%, calc. 23.80%). In the
third step, organic ligands continue to decompose. The residual weight
of 11.68% could be attributed to the CdO product (calc. 12.6%). For 2,
the coordinated water molecules were removed between 100 and
200 °C (exp. 3.54%, calc. 3.39%). The weight loss of 23.93% (calc.
23.80%) corresponds to the loss of the pyridine-3-carboxamide ligand
in the temperature range of 200–350 °C. The final product of thermal
decomposition was CdO (exp. 11.87%, calc. 12.06%). The complex 3
was decomposed in two steps. The first weight loss of 4.89% (calc.
4.49%) in the temperature range 120–200 °C is attributed to the loss of
coordinate water molecules. In the ongoing steps between 200 and
670 °C is accompanied by a mass loss 67.13% for the organic ligands
and the CdO is formed as a final product of thermal decomposition
process (exp. 32.87%, calc. 32.68%).
Fig. 11. The percentages of the intermolecular interactions from obtained
Hirshfeld Surface analysis of complex 3.
3.6. Linear absorption and emission properties of complexes
3.3. FT-IR spectra
Linear absorption spectra are useful for providing information on
energy band structures and band gap energy of the studied materials.
The linear optical absorption spectra of the studied complexes are given
in Fig. 13. As seen from the figure, complex 1 and complex 3 are
showing weak optical absorption peaks around 680 nm wavelength.
These peaks are called as Q bands and they are formed from the linear
The FT-IR spectra of the bands in the region 3600–3100 cm−1 in 1,
2 and 3 are assigned to ν(OH) vibrations of water. Particularly, in the
FT-IR spectra of 3 are seen a broad band of OeH stretching vibrations in
this region because of there are no NH2 stretching vibrations. Primary
amide NH2 asymmetric and symmetric bands 1 and 2 complexes appear
10

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
Fig. 12. Comparison of the most contributed interactions to the crystal packing of the complexes.
Fig. 14. The fluorescence spectra of the complexes under 330 nm excitation
Fig. 13. Linear optical absorption traces of the Cd(II) complexes which are
wavelength.
synthesized with classical and two hydrothermal methods.
exhibiting emission peaks between 349 nm and 469 nm and
365 nm–504 nm, respectively. On the other hand, complex 2 doesn’t
show notable emission peak. These emission peaks cause from the
π* → π and π* → n transitions in the ligands which are formed from the
phenyl and pyridine rings, and carboxylate, carboxamide, fluoro and
phenyl functional groups [47]. The fluorescence peaks of the Cd(II)
complexes were reported among 435 nm and 595 nm [42,43,48,49]
and these differences among the fluorescence peaks were attributed to
the electronic interaction between coordination environment and Cd
(II). In earlier studies, it was reported that the Cd(II) complex is a more
fluorescent material than Zn(II) and Cu(II) complexes [42,43]. This
superiority of the Cd(II) complex was attributed to the existence of the
extensive parallel co-facial π-stacking among the phenanthroline rings
and the two neutral complexes were held in the lattice together by
CeH⋯O interactions [43]. In addition, the electronic affinities of the
metal ions impress the fluorescence properties of the complexes. As it is
well known that the phenyl and pyridine rings act as donor like phe-
nanthroline ring. The theoretical Hirshfeld surface analysis results are
the evidence the possibility of these transitions (Figs. 9 -12). The ma-
terials with fluorescence property have potential application area such
as biosensor in immunology, detection of the nitroaromatic explosives,
combination of atomic orbital coefficients in the highest filled mole-
cular orbital [40,41]. n → π* or π → π* transitions cause to these bands
in the linear absorption spectra. Same figure shows that all of the
complexes have got sharp absorption peaks nearly below of 350 nm
wavelength. In the linear absorption spectra, the electron transporta-
tion from the carrier rich metals to the carrier poor metals induces to
the peaks. The peaks are named as B bands and they are result of n → σ*
or σ → σ* transitions which are occurring between Cd(II) ions and
coordination groups such as: phenyl- and pyridine-rings, carboxylate,
carboxamide, fluoro and phenyl functional groups. The similar linear
optical absorption behaviors for Cd(II) complexes were reported in the
literature [42–46]. The red or blue shift in optical absorption edges of
the Cd(II) complexes had been explained with the existence of different
electronic interaction between coordination environment and metal ion
(Cd(II)) of the complexes.
In addition, the emission properties of the complexes were studied
and the recorded emission spectra are given in Fig. 14. The maximum
emission intensities of complex 1, complex 2 and complex 3 were ob-
tained under 320 nm, 200 nm and 310 nm wavelengths excitations,
respectively. As seen from the Fig. 14, complex 1 and complex 3 are
11

F.E. Öztürkkan Özbek, et al.
InorganicaChimicaActa509(2020)119694
optical and chemical sensors, DNA analysis by fluorescence quenching
detection, image acquisition without lens and filter, security printing,
data recording and storage and laser applications [41,42,48–53]. While
the emission intensity of the complex 1 is compared with the emission
intensities of previous studied materials [54,55], it can be said that this
material is very suitable for the technological applications of the
fluorescent materials.
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D. Valigura, Synthesis, spectral and magnetical characterization of monomeric [Cu
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org/10.1016/j.poly.2016.07.003.
In conclusion, three cadmium-3-fluorobenzoate-pyridine-3-carbox-
amide/pyridine-3-carboxylate supramolecular structures with three
different crystal structures were synthesized also using the hydro-
thermal method as an alternative to the classical method. In particular,
it is attracted that these complexes, synthesized by different methods
using the same chemicals, have different structures. According to
Hirshfeld surface analysis results, H…H, H⋯O/O⋯H, H⋯C/C⋯H,
H⋯F/F⋯H and C⋯C interactions are the primary contributors to the
crystal packing of the complexes. The COO− groups in all synthesized
complexes are coordinated to the Cd center in chelating bidentate
modes. Thermal decomposition of the synthesized complexes consists of
two general steps. The first one is attributed to dehydration whereas the
second step is related with decompose of anhydrous complexes. The
final product of thermal decomposition of the complexes is CdO. The
complex 1 and complex 3 materials have exhibited emission peaks with
about 2535 and 400 intensities, respectively. From these results, it can
be said that especially complex 1 has very good application potential in
the field of the fluorescent materials.
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CRediT authorship contribution statement
Füreya Elif Öztürkkan Özbek: Writing - review & editing. Mustafa
Sertçelik: Investigation. Mustafa Yüksek: Writing - review & editing,
Investigation. Ayhan Elmali: Writing - review & editing, Investigation.
Ertan Şahin: Writing - review & editing.
[18] C.-H. Zeng, Y.-Y. Yang, Y.-M. Zhu, H.-M. Wang, T.-S. Chu, S.W. Ng, A new lumi-
nescent terbium 4-methylsalicylate complex as a novel sensor for detecting the
purity of methanol, Photochem. Photobiol. 88 (2012) 860–866, https://doi.org/10.
1111/j.1751-1097.2012.01123.x.
[19] M.-Q. Zha, X. Li, Y. Bing, Syntheses, structures, and fluorescence of two cadmium
compounds [Cd 2 (pqc) 4 (phen) 2 (H 2 O) 2 ] · 2H 2 O and [Cd(pqc) 2 (bpy)(H 2 O)
2 ] · 2H 2 O n, J. Coord. Chem. 64 (2011) 473–482, https://doi.org/10.1080/
00958972.2010.547577.
Acknowledgement
[20] M.-L. Tong, L.-J. Li, K. Mochizuki, H.-C. Chang, X.-M. Chen, Y. Li, S. Kitagawa, A
novel three-dimensional coordination polymer constructed with mixed-valence di-
meric copper(i, ii) unitsElectronic supplementary information (ESI) available:
synthesis and data for 1. See, Chem. Commun. (2003) 428–429, https://doi.org/10.
1039/b210914j.
We gratefully acknowledge the financial support of the Kafkas
University Research Fund (Project No. 2015-FM-26).
Appendix A. Supplementary data
[21] M. Sertçelik, N. Çaylak Delibaş, S. Çevik, H. Necefoğlu, T. Hökelek, Poly[(μ 5 -2,2′-
bipyridine-5,5′-dicarboxylato)lead(II)], Acta Crystallogr. Sect. E Struct. Rep. Online
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[22] F.L. Hirshfeld, Bonded-atom fragments for describing molecular charge densities,
Theor. Chim. Acta 44 (1977) 129–138, https://doi.org/10.1007/BF00549096.
[23] M.A. Spackman, D. Jayatilaka, Hirshfeld surface analysis, CrystEngComm. 11
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Supplementary data to this article can be found online at https://
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