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ISSN 2522-1841 (Online) AZERBAIJAN CHEMICAL JOURNAL № 2 2023 111
ISSN 0005-2531 (Print) 111
UDC 546.41+547.326.327
SYNTHESIS AND PROPERTIES OF THE COORDINATION COMPOUND OF CALCIUM
STEARATE WITH THIOCARBAMIDE
Sh.B.Khasanov, T.A.Ibodullaeva*, Z.Sh.Abdullaeva, O.I.Khudoyberganov
Khorezm Mamun Academy, Khiva, Uzbekistan *Institute of General and Inorganic Chemistry, Tashkent, Uzbekistan
Received 26.08.2022 Accepted 29.11.2022
The compkx compound of cakium stearate saft with thiourea was synthesized by mechanochemical method. The composition of the resulting compound was studied using the method of elemental analysis. For the first time, crystaHographic data of the compound were obtained using X-ray phase analysis. The stability of the compiex compound was determined using the method of differential thermai anafysis.
Keywords: calcium stearate, thiourea, mechanochemical method, X-ray phase analysis, elemental analysis, differential thermal analysis, IR spectrum, FULLPROF, VESTA.
doi.org/10.32737/0005-2531-2023-2-m-115
Introduction
Mixed-ligand coordination compounds are increasingly used in many branches of science and industry, as well as in environmental protection measures. For example, in analytical chemistry, using mixed-ligand coordination compounds, one can lower the detection limit and increase the selectivity of the determination of a large number of elements and substances. In biochemical systems, the synthesis of certain mixed-ligand coordination compounds can serve as models of processes occurring in living organisms.In [1], in order to study the complexing ability and biological activity, systematic series of new polyfunctional ligand systems - glyoxalic acid derivatives -were synthesized for the first time. The composition and structure of heterocyclic hydrazones were established on the basis of elemental analysis, IR, 1H NMR, and electron spectroscopy. In [2-7], the author considered coordination compounds of oleates of a number of 3d-metals with acetamide, carbamide, thiocarbamide, nic-otinamide, and nicotinic acid. For the first time, 33 new mixed-ligand coordination compounds of cobalt (II), nickel (II), copper (II) and zinc oleates were synthesized, the structure and properties of the obtained compounds were established.
This article describes the synthesis, structure and properties of the mechanoche-mically obtained coordination compound of calcium stearate with nicotinamide.
Experimental part
Material and methodology
All chemicals and reagents were of pure grade for chemical analysis and were used without any purification.
The amount of metals in the synthesized compounds was determined according to [8, 9]. Nitrogen was determined by the Dumas micro-method [10, 11], carbon, hydrogen and sulfur were determined by combustion in an oxygen flow.
The IR spectra of the samples were recorded in the 400-4000 cm-1 range using a MIRacle-10 diamond/ZnSe prism on the IRTracer-100 (SHIMADZU CORP., Japan, 2017) spectrum. Absorption spectra were confirmed according to literature data.
Thermal analysis was carried out on a derivatograph of the Paulik-Paulik-Erdey system [12-14] at a rate of 9 deg/min and a sam-ple0.1 g. with the sensitivity of galvanometers T-900, TG-200, DTA-1/10, DTG-1/10. Recording was carried out under atmospheric conditions with constant removal of the gaseous me-
dium using a water jet pump. The holder was a platinum crucible with a diameter7 mmwithout cover. Al2O3 was used as a reference.
The determination of the structure of the compounds was carried out using a Malvern Panalytical Empyrean diffractometer. XRD data were recorded using CuKa radiation (X = 1.54 A). In this experiment, the accelerating voltage of the radiation generator was set to 45 kV, and the current emission was set to 40 mA. X-ray diffraction radiographs were recorded at 2Th = 200-1200 in a Bregga-Brentano beam geometry with a continuous scanning speed of 0.33 degrees/min [15]. Analysis of the obtained results was carried out using FULLPROF and VESTA programs.
Synthesis methodology
Ca(OH)2, TK, stearic acid were measured in 1:1:2 mole ratio, appropriate masses, and the mixture was placed in a porcelain cup and heated to 18000C using a muffle furnace. The TK contained in the heated mixture changes to a liquid state at this time. Using this, the mass in the porcelain bowl is stirred at high speed. When the temperature cools down to 8000C, the mixture is finely ground using a porcelain mortar while dripping 1 ml of water to ensure a homogeneous mass. Grinding interval is carried out 10-12 times for 10 minutes to 2 hours. The resulting white powder was dissolved in a 1:1 water-acetonitrile mixture and left at room temperature until crystals formed.
[C37H76CaN2O5S] white crystalline substance, Ts=104. Calculated by mass fraction (%): Ca 6.89, N 4.82, C 76.55, S 5.51, H 12.41,
O 13.79. Found (%): Ca 6.83, N 4.79, C 76.51, S 5.48, H 12.42, O 13.77 [16] .
In the IR spectra of the synthesized compound, absorption bands are observed at 652 cm-1, the corresponding bonds 5(Me-O), the difference between the asymmetric and symmetric stretching vibrations of the carboxyl group is 203 cm-1, which indicates the mono-dentate coordination of the carboxyl group, the presence of a coordinated water molecule in the complex is detected at 1833 cm-1.
On the heating curve of the [Ca(C17H35COO)2-CS(NH2VH2O] compound, five endothermic effects appear at 75, 140, 242, 3870C and five exothermic effects at 120, 340, 460, 502, 5830C. The first endoeffect is accompanied by no change in mass. The appearance of the second and third endoeffects is due to the removal of one water molecule. The nature of subsequent thermal effects is accompanied by a stepwise decomposition of the complex. In the temperature ranges 60-122, 122-165, 165-200, 200-280, 280-370, 370-420, 420-460, 460540, 540-700, 700-8000C, the weight loss, respectively, is 0; 2.20; 0.10; 2.45; 12.25; 12.75; 5.88; 9.31; 38.24; 3.16; 5.26%. The total weight loss in the temperature range of 40-8000C according to the TG curve is 91.60%.
For the first time, on the basis of diffractograms obtained as a result of X-ray phase analysis, structural analysis was carried out using FULLPROF and VESTA software. characterizations of hydrogen bonds were determined [17-19].
Table 1. [C37H76CaN2O5S] parameters clarifying the crystallographic data and structure of the complex compound.
Molecular mass 701.14 Crystal size, [mm] 0.16x0.12x0.07
Syngonia Orthorhombic T, K 298
Spatial group Pna21 th,°grad. 2.6; 52.4
a, A 22.26(9) Interval h,k,l 999;-99; 999:-99; 999:-99
b, A 22.49(9) Reflex 10281
c, A 22.61(13) Refractive index 7137
a, b, g, deg 103.269(7) 100.862(7) 101.685(6) Rint 2138
V, A3 11319.186 F2>2s (F2) criterion 0.032
Z 4 Parameter 3862
Dx, g cm-3 0.411 Eligibility Criteria (F2) 324
m(CuKa), mm-1 0.088 R1, wR2(I>2s (I)) 1.02
SYNTHESIS AND PROPERTIES OF THE COORDINATION COMPOUND..... 113
Fig. 1. The arrangement of the complex compound [C37H76CaN2O5S] in the crystal cell.
Table 2. Bond lengths of a complex compound
garden d, Ä Garden d, Ä
Ca1-S1 2.732(16) C12-C13 1.531(9)
Ca1-O1 2.240(13) C13-C14 1.558(9)
Ca1-O2 2.270(13) C14-C15 1.551(9)
Ca1-O3 2.296(13) C15-C16 1.546(9)
S1-C1 1.615(9) C16-C17 1.544(9)
O1-C2 1.352(8) C17-C18 1.536(9)
O2-C3 1.349(8) C18-C19 1.537(9)
O4-C2 1.212(7) C20-C21 1.536(9)
O5-C3 1.219(7) C21-C22 1.527(9)
N1-C1 1.415(8) C23-C24 1.543(9)
N2-C1 1.420(8) C24-C25 1.543(9)
O3-H1 0.9800 C25-C26 1.543(9)
O3-H2 0.9900 C26-C27 1.640(9)
N1-H3 1.0200 C27-C28 1.640(9)
N1-H4 1.0300 C28-C29 1.561(9)
N2-H6 1.0300 C29-C30 1.568(9)
C2-C6 1.515(9) C30-C31 1.537(9)
N2-H5 1.0200 C31-C32 1.525(9)
C3-C4 1.498(9) C32-C33 1.555(9)
C4-C5 1.549(9) C33-C34 1.521(9)
C5-C23 1.544(9) C34-C35 1.550(9)
C6-C7 1.551(9) C35-C36 1.522(9)
C7-C8 1.535(9) C36-C37 1.537(9)
C8-C9 1.537(9) C4-H7 1.1200
C9-C10 1.533(9) C4-H8 1.1000
C10-C11 1.533(9) C5-H9 1.1000
C11-C12 1.538(9) C5-H10 1.1100
Fig. 2. Coordination bond lengths formed by the central atom.
дР, МГ
20
40
60
80
100
120
140
160
180
200
ТГ
t, с
502
'340 ;"• ■; t ;
\jj 46?'
324 Г;! / fte...........
; ! $ £ ; Ч/> f ¿263 Г V 242 / ДТА 120/205225 У - 65,v<V140 Г _ / 95 / 603 680 752'--, • 870"- m=87,5 мг
I/ ' 1
900
800
700
600
500
400
300
200
100
25
50
75
100
время, мин
Fig. 3. Derivatogram of the compound [CaCCnHssCOO^CSCNHb^O].
The resulting complex compound thermal decomposition is the simultaneous burning of the molecule, oxidation of decomposition products and the formation of metal oxides.
For assistance in determining the crystallographic parameters of the complex structure of the compound, thanks to a scientific worker of the Institute of Nuclear physics of the Academy of Sciences of Uzbekistan F.K.Khallokov.
References
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15. Tashmetov M.Yu., Khallokov F.K., Ismatov N.B., Yuldashova I.I., Umarov S.Kh. Electronic irradiation of TlInSxSe2-x (x = 1): Morphology, structure and raman scattering. Intern. J. Modern Physics B. 2021. DOI: 10.1142/S0217979221502891
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KALSiUM STEARATIN TiOKARBAMiDLO KOORDiNASiYA BiRLO^MOSiNiN SiNTEZi УЭ
XASSOLORi
§.B.Has3nov, T.O.ibadullayeva, Z.§.Abdullayeva, A.i.Xudoyberqanov
Mexanokimyavi üsulla kalsium stearat duzunun tiokarbamid ila kompleks birla§masi sintez edilmi§dir. Alinan bir-la§manin tarkibi element tahlili metodundan istifada etmakla öyranilmi§dir. Kristalloqrafik malumatlar ilk dafa rentgenstruktur tahlili vasitasila alda edilmi§dir. Diferensial termik analiz üsulu ila kompleks birla§manin sabitliyi müayyan edilmi§dir.
Agar sözlzr: kalsium stearati, tiokarbamid, mexanokimyavi metod, rentgen-struktur analizi, element analizi, Diferensial termiki analiz, IQ spektr, FULLPROF, VESTA.
СИНТЕЗ И СВОЙСТВА КООРДИНАЦИОННОГО СОЕДИНЕНИЯ СТЕАРАТА КАЛЬЦИЯ С
ТИОКАРБАМИДОМ
Ш.Б.Хасанов, Т.А.Ибадуллаева, З.Ш.Абдуллаева, О.И.Худойберганов
Механохимическим методом синтезировано комплексное соединение соли стеарата кальция с тиомочевиной. Состав полученного соединения был изучен с использованием метода элементного анализа. Впервые кристаллографические данные соединения были получены с помощью рентгенофазового анализа. Стабильность комплексного соединения определяли с использованием метода дифференциального термического анализа.
Ключевые слова: стеарат кальция, тиомочевина, механохимический метод, рентгенофазовый анализ, элементный анализ, дифференциальный термический анализ, ИК-спектр, FULLPROF, VESTA.
