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Figure 1. IR spectrum of ketorolac


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Bog'liq
October 2022

Figure 1. IR spectrum of ketorolac


Figure 2. IR-spectrum of the coordination compound of Cu(II) with ketorolac and carbamide
In the spectra of the complexes, absorption lines were observed in the region of 412-452 cm-1 corresponding to M-N valence vibrations in the short wavelength range. Vibrations related to the -CH group of the benzene ring remained unchanged and appeared in the region of 2980-3100 cm-1. The carbonyl group in the complexes
shifted to shorter wavelengths and was observed in the region of 3313-3264 cm-1, which indicates that it is not involved in coordination. The X-ray structural analysis of the synthesized complex compound was also carried out and the parameters specific to the single crystal of the complex compound were determined.



Figure 3. Illustration of Cu(II) coordination compound with ketorolac and carbamide


Table 2. Crystallographic data and parameters clarifying the structure of the Cu-complex compound.




Cu-complex compound







Formula

C32H32CuN6O8

Crystal size, [mm]

0.18×0.15×0.12

Molecular mass

692

T, °K

312

Syngonia

monoclinic

θ,°grаd.

2,6; 52,4

Spatial group

P21/n

Intervаl h,k,l

999;-99 ; 999:-99 ; 999:-
99

a, Å

31.26 (9)

Reflex

10281

b, Å

32.36 (9)

Refractive index

7137

c, Å

32.54 (13)

Rint

1672

α, β, γ, deg

90(7);90(7);90(6)

F2≥2σ (F2) criterion

0.71073

V, Å3

30549.523

Parameter

3682

Z

4




Eligibility Criteria (F2)

322

Dx, g cm-3

0.165

R1, wR2(I>2σ (I))

1.04

μ(CuKα), mm-1

0.027









Table 3


Bond lengths of a complex compound

Bond

d, Å

Bog‘

d, Å

Cu(1)-O(1)

2.2739

C(7)-C(8)

1.3412

Cu(1)-O(2)

2.2726

C(8)-C(9)

1.4696

Cu(1)-O(3)

2.2712

C(10)-C(11)

1.5650

Cu(1)-O(4)

2.2575

C(11)-C(12)

1.5332

O(2)-C(1)

1.3585

C(12)-C(13)

1.5332

O(3)-C(2)

1.2011

C(13)-C(14)

1.5325

O(4)-C(3)

1.3622

C(14)-C(15)

1.5359

O(5)-C(1)

1.2236

C(15)-C(16)

1.5440

O(6)-C(3)

1.2221

C(16)-C(17)

1.5252

N(1)-C(2)

1.3365

C(17)-C(18)

1.3554

O(1)-H(1)

0.9900

C(18)-C(19)

1.5150

O(1)-H(2)

0.9900

C(19)-C(20)

1.5360

N(2)-C(6)

1.4299

C(20)-C(21)

1.5334

N(2)-C(9)

1.2879

C(21)-C(22)

1.5338

N(1)-H(3)

1.0300

C(22)-C(23)

1.5335

N(1)-H(4)

1.0300

C(23)-C(24)

1.5336

C(2)-C(6)

1.3347

C(24)-C(25)

1.5316

C(2)-C(7)

1.4727

C(25)-C(26)

1.5229

C(3)-C(4)

1.5313

C(27)-C(28)

1.5569

C(4)-C(10)

1.5907

C(28)-C(29)

1.5367

C(5)-C(27)

1.6136

C(29) –C(30)

1.5388



Table 4.


Bond angles of a complex compound

Angle

ω, degree

Angle

ω, degree

O(1)-Cu(1)-O(2)

91.20

C(14)-C(15)-C(16)

113.27

O(1)-Cu(1)-O(3)

178.34

C(15)-C(16)-C(17)

114.93

O(1)-Cu(1)-O(4)

89.26

C(16)-C(17)-C(18)

118.12

O(2)-Cu(1)-O(3)

89.91

C(17)-C(18)-C(19)

116.41

O(2)-Cu(1)-O(4)

176.52

N(1)-C(2)-C(7)

108.01

O(3)-Cu(1)-O(4)

89.70

O(6)-C(3)-C(4)

118.22

Cu(1)-O(2)-C(1)

124.36

O(4)-C(3)-C(4)

123.33

Cu(1)-O(3)-C(2)

123.39

O(4)-C(3)-O(6)

118.31

Cu(1)-O(4)-C(3)

116.88

C(3)-C(4)-C(10)

113.35

H(1)-O(1)-H(2)

105.00

C(1)-C(5)-C(27)

117.67

Cu(1)-O(1)-H(1)

105.00

N(2)-C(6)-C(2)

123.55

Cu(1)-O(1)-H(2)

106.00

C(2)-C(7)-C(8)

123.30

C(6)-N(2)-C(9)

121.61

C(7)-C(8)-C(9)

118.10

O(2)-C(1)-O(5)

118.67

N(2)-C(9)-C(8)

119.28

O(2)-C(1)-C(5)

122.12

C(4)-C(10)-C(11)

119.02

O(5)-C(1)-C(5)

119.08

C(10)-C(11)-C(12)

110.59

H(3)-N(1)-H(4)

117.00

C(11)-C(12)-C(13)

111.31

C(2)-N(1)-H(3)

122.00

C(12)-C(13)-C(14)

110.50

C(2)-N(1)-H(4)

121.00

C(13)-C(14)-C(15)

111.13

O(3)-C(2)-N(1)

109.36

C(23)-C(24)-C(25)

111.01

O(3)-C(2)-C(7)

108.08

C(24)-C(25)-C(26)

110.72

N(1)-C(2)-C(6)

108.44

C(5)-C(27)-C(28)

118.58



Table 5


Hydrogen bonds in the crystal structure (A˚)

Bond D−H···A

Distance, Å

Angle D−H···A,


grаd.

Atomic coordinates, А

D−H


N···A


D···A


[C32H32CuN6O8]

O(5)--H(5)…O(1)

1.1100

2.3400

3.2411(18)

138.00

-

O(6)--H(6)…O(2)

1.1000

2.3900

3.4445(17)

159.00

-



Also, differential thermal analysis was conducted in order to determine the properties of the obtained complex compounds. In the derivatograms of the studied compounds, endo- and exo-effects corresponding to various processes were observed: evaporation of crystallization water, phase transition and thermal oxidation and decomposition processes were observed. The analysis of the derivatograms of the complexes showed that the thermal decomposition of the organic part in all compounds ends in the temperature range of 100oC-700oC. In DTGA curves, this process is explained by endo- and exo-effects, which indicate the breaking of previous chemical bonds and the formation of new ones [12].

Figure 4. Derivatogram of a similar complex compound


A number of endothermic and exothermic effects were observed in the DTA curve of the [Cu(HL)2 (Kar)2] complex. Above 1000C, the endothermic effect refers to the decomposition of water of crystallization. As a result of the increase in temperature, the decomposition of the complex compound increases intensively. As a result, hydrazine begins to break down into components such as nitrogen oxides and carbon dioxide. Copper (II) oxide is formed as a thermolysis product. Based on the analysis of the research results, the thermal stability of the synthesized complex compounds is expressed by the nature of the central ion and the acid residue, as well as the absence of water molecules in the complex compounds. It was concluded that the complex compound synthesized on the basis of ketorolac is [Cu(HL)2(Kar)2] [13].
Conclusion. The complex [Cu(HL)2(Kar)2] is a mixed-ligand complex of Cu(II), ketorolac, and carbamide with a 2:1 composition. The complex molecule contains O(5)--H(5)...O(1) and O(6)--H(6)...O(2) groups that can participate as donors in hydrogen bonds [6]. The fact that the synthesized ketorolac complex is important for temporary pain relief and anti-inflammatory use in all living organisms was shown by studying using physico-chemical research methods [14]. The solubility of the newly synthesized ketorolac complex is 25 times higher than that of ketorolac itself. It was determined by analyzing the Hirshfeld surface using the Crystall Explorer 17.5 program. According to it, the percentage of OH/HO interactions in the structure is higher than 36% on average and the share of HH interactions was less than 26% [8]. Therefore, this result increased the solubility of the obtained compound [15].


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