SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II)
The synthesis and characterization of mononuclear Co(II) complex based on 3,5-dimethyl-4-amino-1H-pyrazole are reported. IR and UV/Vis spectroscopy characterization of the complex are described. The synthesis, results of IR, NMR spectroscopy and elemental analysis of 3,5-dimethyl-4-amino-1H-pyrazole...
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V.I.Vernadsky Institute of General and Inorganic Chemistry
2022
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Репозитарії
Ukrainian Chemistry Journal| _version_ | 1871465843670384640 |
|---|---|
| author | Davydenko , Yuliya Pavlenko, Vadim Fritsky, Igor Vynohradov , Oleksandr |
| author_facet | Davydenko , Yuliya Pavlenko, Vadim Fritsky, Igor Vynohradov , Oleksandr |
| author_institution_txt_mv | [
{
"author": "Yuliya Davydenko ",
"institution": "Taras Shevchenko National University of Kyiv, Volodymyrska Street, 64\/13, Kyiv 01601, Ukraine "
},
{
"author": "Vadim Pavlenko",
"institution": "Taras Shevchenko National University of Kyiv, Volodymyrska Street, 64\/13, Kyiv 01601, Ukraine "
},
{
"author": "Igor Fritsky",
"institution": "Taras Shevchenko National University of Kyiv, Volodymyrska Street, 64\/13, Kyiv 01601, Ukraine "
},
{
"author": "Oleksandr Vynohradov ",
"institution": "Taras Shevchenko National University of Kyiv, Volodymyrska Street, 64\/13, Kyiv 01601, Ukraine "
}
] |
| author_sort | Davydenko , Yuliya |
| baseUrl_str | https://ucj.org.ua/index.php/journal/oai |
| collection | OJS |
| datestamp_date | 2026-07-22T08:23:49Z |
| description | The synthesis and characterization of mononuclear Co(II) complex based on 3,5-dimethyl-4-amino-1H-pyrazole are reported. IR and UV/Vis spectroscopy characterization of the complex are described. The synthesis, results of IR, NMR spectroscopy and elemental analysis of 3,5-dimethyl-4-amino-1H-pyrazole are also reported. X-ray analysis of [Co(C5H9N3)2Cl2] complex reveals that the cobalt atom has a tetrahedral coordination environment formed by two nitrogen atoms belonging to the two 3,5-dimethyl-4-amino-1H-pyrazole ligands [Co1–N1 = 2.005(3) and Co1–N5 = 2.006(3)Å] and two chlorine atoms [Co1–Cl2 = 2.2400(11) and Co1–Cl1 2.2863(12) Å]. In the crystal structure the molecules are linked through intermolecular (N–H···N, N–H···Cl) and intramolecular non-classical (С–H···Cl) hydrogen bonds. Hirshfeld surface analysis of the intermolecular contacts reveals that the most important contributions for the crystal packing are from H···H (47.1%) and H···Cl/Cl···H (28.5%) contacts. |
| doi_str_mv | 10.33609/2708-129X.88.06.2022.127-136 |
| first_indexed | 2025-09-24T17:43:45Z |
| format | Article |
| fulltext |
127
UDC 546.73 + 547.77 doi: 10.33609/2708-129X.88.06.2022.127-136
SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC
CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS
OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE)
COBALT(II)
Y.M. Davydenko, V.O. Pavlenko, O.S. Vynohradov, I.O. Fritsky
Department of Chemistry, Taras Shevchenko National University of Kyiv, Volodymyrska Street,
64/13, Kyiv 01601, Ukraine
e-mail: davydenko300808@gmail.com
The synthesis and characterization of mononuclear Co(II) complex based on 3,5-dime-
thyl-4-amino-1H-pyrazole are reported. IR and UV/Vis spectroscopy characterization of the
complex are described. The synthesis, results of IR, NMR spectroscopy and elemental analysis
of 3,5-dimethyl-4-amino-1H-pyrazole are also reported. X-ray analysis of [Co(C5H9N3)2Cl2]
complex reveals that the cobalt atom has a tetrahedral coordination environment formed by
two nitrogen atoms belonging to the two 3,5-dimethyl-4-amino-1H-pyrazole ligands [Co1–
N1 = 2.005(3) and Co1–N5 = 2.006(3)Å] and two chlorine atoms [Co1–Cl2 = 2.2400(11) and
Co1–Cl1 2.2863(12) Å]. In the crystal structure the molecules are linked through intermo-
lecular (N–H···N, N–H···Cl) and intramolecular non-classical (С–H···Cl) hydrogen bonds.
Hirshfeld surface analysis of the intermolecular contacts reveals that the most important con-
tributions for the crystal packing are from H···H (47.1%) and H···Cl/Cl···H (28.5%) contacts.
Keywords: pyrazole, cobalt complexes, crystal structure, X-ray crystallography, Hirshfeld
surface analysis.
INTRODUCTION. Pyrazole ligands are
widely used in different areas of coordina-
tion, bioinorganic, supramolecular chemistry
and in molecular electronics because of their
marked tendency to form high nuclearity spe-
cies exhibiting specific magnetic properties
which also can be used for the development of
structural and functional models of active sites
of some metalloenzymes [1–2].
Transition metal complexes containing the
pyrazole heterocycle are well studied [3–5].
Due to the presence of N-N bridging function
in the pyrazole ring, these ligands can form
polynuclear complexes with specific mole
cular topology. In this case, triangular azame
tallacrowns have been a much more common
structure type [6–10]. The neutral pyrazole li-
gands usually bind to metal ions via the pyri-
dine-type nitrogen atom and provide to form
of the mononuclear complexes [11–14]. De-
spite the considerable amount of available data
on the 3,5-substituted pyrazole compounds,
128 ISSN 2708-129X. Укр. хім. журн., 2022
SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS
OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) COMPLEXINORGANIC CHEMISTRY
3,4,5-substituted pyrazole-based complexes
have been studied very unevenly. We have been
interested in how the steric factors, namely the
presence of NH2 substitute in the fourth posi-
tion of the 3,5-dimethyl-1Н-pyrazole, can in-
fluence the final crystal structure.
In this regard, in this work, we performed
the synthesis of 3,5-dimethyl-4-amino-1H-
pyrazole and Co(II) complex with it was also
studied.
Although the X-ray structure of the ti-
tle compound was previously reported [15],
we used another solvent for the preparation
of [Co(C5H9N3)2Cl2]. Additionally, IR and
UV/Vis spectroscopic characterization of the
complex are described. The synthesis, results
of IR, NMR spectroscopy and elemental ana
lysis of 3,5-dimethyl-4-amino-1H-pyrazole are
also reported. Hirshfeld surface analysis of the
intermolecular contacts of the title compound
was also performed.
EXPERIMENT AND DISCUSSION OF
THE RESULTS. All chemicals and solvents
were commercial products of reagent grade
and used without further purification. Micro
analyses were performed with a Perkin – Elmer
2400 CHN. IR spectra (KBr pellets) were record-
ed with a Perkin – Elmer Spectrum BX FT-IR
in the range of 400–4000 cm–1. Absorbance UV/
Vis spectra were registered with a Varian Cary
50 spectrophotometer in the range of 200–
1000 nm at room temperature. 1H NMR spect
ra were recorded on a Bruker AC-400 spect
rometer (400 MHz) at room temperature. For
X-ray structure determination, single crystals of
[Co(C5H9N3)2Cl2] were mounted on a Nonius
four circle diffractometer equipped with a CCD
camera and a graphite monochromated Mo Кα
radiation source (λ = 0.71073 Å). Data were col-
lected at 293K. Effective absorption correction
was performed (SCALEPACK [16]). The struc-
ture of the complex was solved with the direct
method using SIR-97 [17] software and was re-
fined with full matrix least squares method on
F2 using SHELXL-97 program [18]. H atoms
were treated by a riding model. Crystallogra
phic data are summarized in Table 1.
Table 1.
Crystal data and structure refinement for
[Co(C5H9N3)2Cl2].
Chemical formula C10H18Cl2CoN6
Mr 352.13
Crystal system,
space group
Triclinic,
P -1
Temperature (K) 293
a (Å) 9.2036(7)
b (Å) 9.2100(8)
c (Å) 10.0872(8)
α (o) 94.738(5)
β (o) 106.089(5)
γ (o) 107.844(5)
V (Å3) 768.81(11)
Z 2
Density (Mg/m3) 1.521
Radiation type Mo Kα
µ (mm-1) 1.46
Crystal size (mm) 0.15 × 0.15 × 0.1
F(000) 362
Theta range θ, (o) 0.998–27.485
Reflections collected 3365
G.O.F. 1.007
Final R indices
R1 та wR2 [I > 2σ (I)]
R1 = 0.0951
wR2 = 0.0471
R indices
R1 та wR2 (all data)
R1 = 0.1298
wR2 = 0.1075
Largest diff. peak and hole (е. Å -3) 0.396, -0.561
129https://ucj.org.ua
Y.M. Davydenko, V.O. Pavlenko, O.S. Vynohradov, I.O. Fritsky UCJ № 6 / Vol. 88
The synthesis of 3,5-dimethyl-4-amino-1H-
pyrazole (L) was carried out according to the
following method. 50 g (0.50 mol) of freshly
distilled acetylacetone, 45 mL of concentrat-
ed HCl and 250 mL of water were placed into
a four-neck 1L round bottom flask equipped
with a stirrer, reflux condenser, thermometer,
and addition funnel. The mixture was cooled
with stirring in an ice bath to 5 oC and a solution
of NaNO2 (36 g; 0.52 mol) in 100 mL of water
was dropwise added to it over 10–15 minutes.
After consecutive stirring for 20 min, 27.5 g
(0.55 mol) of 85% hydrazine hydrate was added
to the reaction mixture. After that 85 g of NaCl
was added to the reaction flask to precipitate
the product and the mixture was stirred for
1.5 hours at r.t. The obtained blue crystals were
filtered off and air-dried. Subsequent treatment
of the isolated product by refluxing of its mix-
ture with anhydrous benzene (800 mL) during
5–7 min allowed to selectively dissolve 3,5-di-
methyl-4-nitroso-1H-pyrazole (1), in Scheme 1,
whereas NaCl was insoluble in these conditions
and was filtered off from the hot solution. Slow
cooling of the filtrate to 10 oC led to the crys-
tallization of 3,5-dimethyl-4-nitroso-1H-pyra-
zole (m.p. 128–129 oC), which turned green in
the air. To increase the yield of the product, the
filtered off (on the first purification step) solid
was mixed with the filtrate and obtained mix-
ture was refluxed, filtered and the new filtrate
was cooled to 10 oC, which led to the second
portion of the product. Yield: 62.5 g; 90%.
Scheme 1. Synthesis of 3,5-dimethyl-4-amino-1H-pyrazole.
Hydrazine hydrate (90%, 93 mL; 0.5 mol) was
added to 3,5-dimethyl-4-nitroso-1H-pyrazole
(62.5 g; 0.5 mol) in ethanol (650 mL) and placed
into a three-neck round-bottom flask equipped
with a stirrer, reflux condenser, and thermome-
ter. At that temperature of reaction mixture in-
creased to 60–65 oC. The mixture was refluxed
under constant stirring for 3 hours, which was
accompanied by its color change from green to
yellow-brown. The solvent was completely dis-
tilled off and the resulting crystalline residue
was washed with cold ethanol (20–25 mL) and
air-dried. The yield of the crystalline product
(2), in Scheme 1, was 52.0 g (93%). 1H NMR
(DMSO-d6), δ: 2.11 (s., 6H; 2CH3), 6.10 (s., 2H;
NH2), 12.55 (br. s., 1H; NH). Elemental analysis:
calculated (%): C 54.05; H 8.11; N 37.83. Found:
C 54.04; H 8.10; N 37.85.
130 ISSN 2708-129X. Укр. хім. журн., 2022
SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS
OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) COMPLEXINORGANIC CHEMISTRY
The preparation of the title compound was
carried out according to the following method.
Cobalt (II) chloride hexahydrate (0,0071 g,
3·10-5 mol) and 3,5-dimethyl-4-amino-1H-py
razole (0,0033 g, 3·10-5 mol) were dissolved in
methanol (1 mL). The blue mixture was stirred
for 15 min at ambient temperature. The result-
ing blue solution was left to stand at room tem-
perature. Slow evaporation of the solvent in
2 days yielded the blue crystals of the mononu-
clear complex (Scheme 2). Yield 93%. Elemen-
tal analysis: calculated (%): C 34.09; H 5.11;
N 23.86. Found: C 34.03; H 5.10; N 23.85.
The synthesis of coordination compounds
with 3,5-dimethyl-4-amino-1H-pyrazole (L)
was performed with various salts (MX2) of dif-
ferent 3d-metals, but crystals suitable for X-ray
were obtained only in the case of interaction of
L with CoCl2∙6H2O.
MX2 + L + Solvent
M = Cu, Co, Ni, Zn, Mn
X = NO3
-, Cl-, ClO4
-, СН3СОО-
Solvents = H2O, CH3OH, DMF
The formation of the title compound pro-
ceeds according to the following reaction
Scheme 2.
CoCl2∙6H2O + L + CH3OH → [CoL2Cl2]
Scheme 2. Formation of the title compound
[Co(C5H9N3)2Cl2].
To confirm the fact of coordination of the
ligand to the metal ion, an IR study of the ob-
tained complex [Co(C5H9N3)2Cl2] was com-
pared with the spectra of the ligand. (Figure 1).
Fig. 1. IR spectra of complex [Co(C5H9N3)2Cl2] (1) and 3,5-dimethyl-4-amino-1H-pyrazole (2).
131https://ucj.org.ua
Y.M. Davydenko, V.O. Pavlenko, O.S. Vynohradov, I.O. Fritsky UCJ № 6 / Vol. 88
In the comparative analysis of the IR spec-
tra of the synthesized complex and ligand,
the main attention was paid to the absorption
bands corresponding to the oscillations of the
functional groups of the ligand. According-
ly, in the IR spectra of [Co(C5H9N3)2Cl2] and
3,5-dimethyl-4-amino-1H-pyrazole observed
an intense sharp band of the valence oscilla-
tions of ν(NH) in the region of 3350 cm-1 (for
complex), 3347 cm-1 (for L). Both spectra have
several bands in the region of 2880–3280 cm-1
corresponding to the asymmetric and sym-
metric stretch of ν(NH2); scissoring oscilla-
tions of (NH2) for complex 1561 cm-1, for 3,5-
dimethyl-4-amino-1H-pyrazole – 1537 cm-1.
There are several bands in the region of 2700–
2900 cm-1 corresponding to the oscillations of
ν(СH3) asymmetric and symmetric stretch, in
the region of 1386–1427 cm-1 of ρ(СH3) asym-
metric and symmetric stretch. A rather intense
and sharp peak in the region of 1232 cm-1 (for
complex) and 1299 cm-1 (for L) indicates the
presence of ν(С-N) oscillations. A band is pre
sent in the absorption region of ν(С=N) oscil-
lations: 1609 cm-1 (for complex) and 1607 cm-1
(for L) [19]. In view of the above facts, it can be
stated indicating the presence of a coordinated
but not deprotonated ligand.
The electronic spectra of the title compound
(Figure 2, B) and CоCl2·6H2O (Figure 2, A)
in the same solvent (methanol solution) indi-
cate absorption maxima at 600 and 670 nm for
CоCl2·H2O, and at 600 and 650 nm for the com-
plex. The first of these bands in each case appear
as shoulders and may be attributed to charge
transfer from the ligand to cobalt, and the se
cond can be assigned as the d–d transitions of
cobalt(II) ions. During complex formation, the
most intense band is shifted to the short-wave-
length region by 20 nm in comparison with Cо-
Cl2·6H2O. Since the expected data for octahedral
cobalt complexes are 400–500 nm (chromo-
phore CoO6 - CoN6), and for tetrahedral com-
plexes are 600–700 nm (chromophore CoN4),
the results suggest the tetrahedral structure of
the obtained complex [20].
Fig. 2. Absorbance (methanol solution) electronic spectra of the title compound (B) and CоCl2·6H2O (A).
132 ISSN 2708-129X. Укр. хім. журн., 2022
SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS
OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) COMPLEXINORGANIC CHEMISTRY
In the title compound, 3,5-dimethyl-4-ami-
no-1H-pyrazole is a neutral ligand bound to
cobalt ion via the pyridine-type nitrogen atom
thus providing the formation of the mononu-
clear complex (Figure 3).
Fig. 3. The molecular structure of [Co(C5H9N3)2Cl2],
shows the atom-numbering scheme and the cobalt
coordination environment. Displacement ellip-
soids are drawn at the 50% probability level.
The Co as the central atom has a tetrahed
ral coordination environment formed by two
nitrogen atoms belonging to the two 3,5-dime-
thyl-4-amino-1H-pyrazole ligands [Co1–N1 =
2.005(3) and Co1–N5 = 2.006(3)Å] and two
chlorine atoms [Co1–Cl2 = 2.2400(11) and
Co1–Cl1 2.2863(12) Å] (Table 2). The bond
lengths Co–N (varying in the range of 2.001(0) –
2.049(0) Å) and Co–Cl (varying in the range of
2.222(0) – 2.252(0) Å) for similar compounds
were found in the literature [21, 22]. Hence, the
distances Co–N and Co–Cl of the title complex
are typical.
Table 2.
Selected bond lengths (A) and bond an-
gles (deg) of [Co(C5H9N3)2Cl2]. Symmetry
codes: (i: -1+x, y, z; ii: -1-x, 1-y, 2-z).
Cо1–N1 2.007(3)
Cо1–N5 2.008(3)
Cо1–Сl1 2.2861(13)
Cо1–Сl2 2.2404(12)
N2іі–H2іі···N6 2.859(14)
N4і–H4і···N3іі 2.942(7)
N6–H6A···Cl1 2.736(6)
N3–H3B···Cl1 2.791(11)
C6–H6С···Cl2 2.713(4)
Cl1–Co1– N5 103.65(11)
Cl1–Co1–N1 104.88(11)
Cl1–Co1–Cl2 114.21(5)
N1–Co1–N5 116.00(14)
∠N2іі–H2іі···N6 175.09(27)
∠N4і–H4і···N3ii 163.51(23)
∠N6–H6A···Cl1 171.14(26)
∠N3–H3B···Cl1 133.02(26)
∠C6–H6С···Cl2 148.61(36)
In the crystal packing (Figure 4) the mo
lecules of complex [Co(C5H9N3)2Cl2] are con-
nected through intermolecular (N2-H2···N6,
N4-H4···N3, N3-H3B···Cl1, N6-H6A···Cl1)
hydrogen bonds in the two-dimensional poly-
mer. The hydrogen bonds N-H···N are formed
by N, H atoms of NH- and NH2-groups from
3,5-dimethyl-4-amino-1H-pyrazole. Addi-
tionally, NH2-group forms the intermolecular
hydrogen bonds with the chlorine atoms (N6–
H6A···Cl1, N3–H3B···Cl1). The non-classical
intramolecular hydrogen bonds between the
chloride anions and CH3-groups of the ligand
(C6–H6С···Cl2) are also present in the crystal
packing of the complex [Co(C5H9N3)2Cl2].
Due to such organization of crystal packing
the intermolecular hydrogen bonds N-H···N
take part in forming the sixteen- and twen-
ty-membered cycles, which are interchange-
able in the molecular structure. The four mo
133https://ucj.org.ua
Y.M. Davydenko, V.O. Pavlenko, O.S. Vynohradov, I.O. Fritsky UCJ № 6 / Vol. 88
lecules of the ligand with two Co atoms are
connected by hydrogen bonds N4-H4···N3
and take part in forming the sixteen-mem-
bered cycle. The interchangeable hydrogen
bonds N2-H2···N6 and N4-H4···N3 from four
molecules of the ligand take part in the for-
mation of the twenty-membered cycle. In the
crystal packing the shortest intrachain Co...
Co separations are 7.407(27) Å).
Fig. 4. A crystal packing diagram of the complex [Co(C5H9N3)2Cl2] shows hydrogen bonds as
underlined dotted lines and shaded black, which link the molecules of the title compound in the
two-dimensional polymer.
[Symmetry codes: (i) -1+x, y, z; (ii) -1-x, 1-y, 2-z; (iii) -x, 1-y, 2-z; (iv) -2+x, y, z].
The Hirshfeld surface analysis and the as-
sociated two-dimensional fingerprint plots
were performed using Crystal Explorer 17.5
software [23], with a standard resolution of the
three-dimensional dnorm surfaces plotted over
a fixed color scale of -0.6232 (red) to 1.6217
(blue) a.u. There are 12 red spots on the dnorm
surface (Figure 5).
Fig. 5. Two projections of Hirshfeld surfaces
mapped over dnorm showing the intermolecular in-
teractions within the molecule.
The dark-red spots arise as a result, of short
interatomic contacts and represent negative
dnorm values on the surface, while the other
weaker intermolecular interactions appear as
light-red spots. The Hirshfeld surfaces mapped
over dnorm are shown for the H···H, H···Cl/Cl···H,
H···N/N···H and H···C/C···H contacts, the
overall two-dimensional fingerprint plot and
the decomposed two-dimensional fingerprint
plots are given in Figure 6.
All short interatomic contacts are in the
range of 1.829–2.782 Å. The shortest contacts
are NH···N and the longest contacts are NH···Cl.
The most significant contributions to the over-
all crystal packing are from H···H (47.1%),
H···Cl/Cl···H (28.5%), H···N/N···H (12.9%) and
134 ISSN 2708-129X. Укр. хім. журн., 2022
SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS
OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) COMPLEXINORGANIC CHEMISTRY
H···C/C···H (9.7%) contacts. The small con-
tribution of the other weak intermolecular
C···Cl/Cl···C (0.7%), C···C (0.4%), H···Co/Co···H
(0.3%), C···N/N···C (0.2%), C···Co/Co···C (0.1%)
and Cl···Cl (0.1%) contacts has a negligible ef-
fect on the packing. Also, quantitative physical
properties of the Hirshfeld surface for this com-
pound were obtained, such as molecular volume
(377.18 Å3), surface area (345.22 Å2), globulari-
ty (0.731), as well as asphericity (0.154).
Fig. 6. The overall two-dimensional fingerprint plot and those delineated into specified interactions. Hir-
shfeld surface representations with the function dnorm plotted onto the surface for the different interactions.
CONCLUSIONS. The present work de-
scribes the synthesis and characterization of
the mononuclear coordination compound
[Co(C5H9N3)2Cl2]. X-ray analysis of the com-
plex reveals that the cobalt atom has a tetrahe-
dral coordination environment formed by two
nitrogen atoms belonging to the two 3,5-dime-
thyl-4-amino-1H-pyrazole and two chlorine
atoms. In the crystal structure the molecules
are linked through intermolecular hydrogen
bonds (N–H···N, N–H···Cl) and non-classical
intramolecular hydrogen bonds (С–H···Cl).
It was found that the introduction to the 4th
position of the 3,5-dimethyl-1H-pyrazole NH2
group does not contribute to the participation
of the latter in coordination. The reason for this
135https://ucj.org.ua
Y.M. Davydenko, V.O. Pavlenko, O.S. Vynohradov, I.O. Fritsky UCJ № 6 / Vol. 88
fact may be the weak σ-donor capacity of the
NH2 group in the pyrazole cycle. Hirshfeld sur-
face analysis was used to study intermolecular
interactions in the crystal. The 2D-fingerprint
plot calculations displayed the H⋯H and H···-
Cl/Cl···H contacts that were the most signifi-
cant interaction with the Hirshfeld surface.
ACKNOWLEDGEMENTS. This work
was supported by the Ministry of Edu
cation and Science of Ukraine grant
number 22BF037-09.
СИНТЕЗ, КРИСТАЛІЧНА СТРУКТУРА, СПЕКТ
РАЛЬНІ ХАРАКТЕРИСТИКИ ТА АНАЛІЗ ПО-
ВЕРХНІ ХІРШФЕЛЬДА КОМПЛЕКСУ ДИХЛО-
РО-БІС(3,5-ДИМЕТИЛ-4-АМІНО-1H-ПІРАЗОЛ)
КОБАЛЬТУ(II)
Ю. М. Давиденко, В. О. Павленко,
О. С. Виноградов, І. О. Фрицький
Київський національний університет ім. Та
раса Шевченка, вул. Володимирська, 64/13,
Київ 01601, Україна
e-mail: davydenko300808@gmail.com
Синтезовано та охарактеризовано ме-
тодами ЕСП, ІЧ-спектроскопії моноядер
ний комплекс Co(II) на основі 3,5-диме
тил-4-аміно-1H-піразолу. Методом РСтА
встановлено молекулярну будову отри-
маної в кристалічному стані сполуки
[Co(C5H9N3)2Cl2], в якій атом кобальту
знаходиться у викривленому тетраедрич-
ному оточенні N2Сl2, що сформоване зав-
дяки координації атомів хлору [Co1–Cl2 =
2.2400(11) і Co1–Cl1 2.2863(12) Å] та піри-
динових атомів азоту від двох недепротоно-
ваних монодентатно координованих моле-
кул ліганду [Co1–N1 = 2.005(3) і Co1–N5 =
2.006(3)Å]. Наведено синтез 3,5-диметил-4-
аміно-1H-піразолу, а також характеристику
ліганду за допомогою ЯМР, ІЧ-спектроско-
пії та елементного аналізу. Кристалічна
структура моноядерного комплексу додат-
ково застабілізована міжмолекулярними
водневими зв’язками (N–H···N, N–H···Cl) та
некласичними внутрішньомолекулярними
водневими зв’язками (С–H···Cl). Аналіз по-
верхні Хіршфельда показав, що найбільш
важливий внесок у кристалічну упаковку
вносять міжмолекулярні H···H (47.1%) та
H···Cl/Cl···H (28.5%) контакти.
Ключові слова: піразол, комплекс ко-
бальту, кристалічна структура, РСтА, ана-
ліз поверхні Хіршфельда.
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Стаття надійшла 08.07.2022.
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| id | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-460 |
| institution | Ukrainian Chemistry Journal |
| keywords_txt_mv | keywords |
| language | English |
| last_indexed | 2026-07-23T01:08:29Z |
| publishDate | 2022 |
| publisher | V.I.Vernadsky Institute of General and Inorganic Chemistry |
| record_format | ojs |
| resource_txt_mv | ucjorgua/83/ea104521b13a67ec15ffcdd3c188a983.pdf |
| spelling | oai:ojs2.1444248.nisspano.web.hosting-test.net:article-4602026-07-22T08:23:49Z SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) Davydenko , Yuliya Pavlenko, Vadim Fritsky, Igor Vynohradov , Oleksandr pyrazole, cobalt complexes, crystal structure, X-ray crystallography, Hirshfeld surface analysis. The synthesis and characterization of mononuclear Co(II) complex based on 3,5-dimethyl-4-amino-1H-pyrazole are reported. IR and UV/Vis spectroscopy characterization of the complex are described. The synthesis, results of IR, NMR spectroscopy and elemental analysis of 3,5-dimethyl-4-amino-1H-pyrazole are also reported. X-ray analysis of [Co(C5H9N3)2Cl2] complex reveals that the cobalt atom has a tetrahedral coordination environment formed by two nitrogen atoms belonging to the two 3,5-dimethyl-4-amino-1H-pyrazole ligands [Co1–N1 = 2.005(3) and Co1–N5 = 2.006(3)Å] and two chlorine atoms [Co1–Cl2 = 2.2400(11) and Co1–Cl1 2.2863(12) Å]. In the crystal structure the molecules are linked through intermolecular (N–H···N, N–H···Cl) and intramolecular non-classical (С–H···Cl) hydrogen bonds. Hirshfeld surface analysis of the intermolecular contacts reveals that the most important contributions for the crystal packing are from H···H (47.1%) and H···Cl/Cl···H (28.5%) contacts. V.I.Vernadsky Institute of General and Inorganic Chemistry 2022-07-27 Article Article Inorganic Chemistry Неорганическая химия Неорганічна хімія application/pdf https://ucj.org.ua/index.php/journal/article/view/460 10.33609/2708-129X.88.06.2022.127-136 Ukrainian Chemistry Journal; Vol. 88 No. 6 (2022): Ukrainian Chemistry Journal; 127-136 Украинский химический журнал; ##issue.vol## 88 ##issue.no## 6 (2022): Ukrainian Chemistry Journal; 127-136 Український хімічний журнал; Том 88 № 6 (2022): Український хімічний журнал; 127-136 2708-129X 2708-1281 en https://ucj.org.ua/index.php/journal/article/view/460/236 Copyright (c) 2022 Yuliya Davydenko , Vadim Pavlenko, Igor Fritsky, Oleksandr Vynohradov https://creativecommons.org/licenses/by-nc/4.0 |
| spellingShingle | Davydenko , Yuliya Pavlenko, Vadim Fritsky, Igor Vynohradov , Oleksandr SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) |
| title | SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) |
| title_full | SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) |
| title_fullStr | SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) |
| title_full_unstemmed | SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) |
| title_short | SYNTHESIS, X-RAY CRYSTAL STRUCTURE, SPECTROSCOPIC CHARACTERIZATION AND HIRSHFELD SURFACE ANALYSIS OF DICHLORO-BIS(3,5-DIMETHYL-4-AMINO-1H-PYRAZOLE) COBALT(II) |
| title_sort | synthesis, x-ray crystal structure, spectroscopic characterization and hirshfeld surface analysis of dichloro-bis(3,5-dimethyl-4-amino-1h-pyrazole) cobalt(ii) |
| topic_facet | pyrazole cobalt complexes crystal structure X-ray crystallography Hirshfeld surface analysis. |
| url | https://ucj.org.ua/index.php/journal/article/view/460 |
| work_keys_str_mv | AT davydenkoyuliya synthesisxraycrystalstructurespectroscopiccharacterizationandhirshfeldsurfaceanalysisofdichlorobis35dimethyl4amino1hpyrazolecobaltii AT pavlenkovadim synthesisxraycrystalstructurespectroscopiccharacterizationandhirshfeldsurfaceanalysisofdichlorobis35dimethyl4amino1hpyrazolecobaltii AT fritskyigor synthesisxraycrystalstructurespectroscopiccharacterizationandhirshfeldsurfaceanalysisofdichlorobis35dimethyl4amino1hpyrazolecobaltii AT vynohradovoleksandr synthesisxraycrystalstructurespectroscopiccharacterizationandhirshfeldsurfaceanalysisofdichlorobis35dimethyl4amino1hpyrazolecobaltii |