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metal-impregnate surface complexes. The polyfunctional ligands adsorbed on the surface of the polymer matrix, and these ligands interacted with the polymer porous
structure fixing in large cavities on the polymer surface. The metal ions bonded with the ligand functional groups forming metal complexes during sorption.
References:
1. Alimarin I. P., Ivanov V. M. Extraction with thio and dithio phosphorus acids//Russian Chemical Reviews. -1989. - T. 58. - No. 9. - C. 863.
2. Strikovsky A. G., Jerabek K., Cortina J. L., Sastre A. M., Warshawsky A. Solvent impregnated resin (SIR) containing dialkyl dithiophosphoric acid on Amberlite XAD-2: extraction of copper and comparison to the liquid-liquid extraction//Reactive and Functional Polymers. - 1996. - T. 28. - No. 2. - C. 149-158.
3. Ying X., Fang Z. Experimental research on heavy metal wastewater treatment with dipropyl dithiophos-phate//Journal of hazardous materials. - 2006. - T. 137. - No. 3. - C. 1636-1642.
4. Jerabek K., Hankova L., Strikovsky A. G., Warshawsky A. Solvent impregnated resins: relation between impregnation process and polymer support morphology I. Di- (2-ethylhexyl) dithiophosphoric acid//Reactive and Functional Polymers. - 1996. - T. 28. - No. 2. - C. 201-207.
5. Rovira M., Hurtado L., Cortina J. L., Arnaldos J., Sastre A. M. Impregnated resins containing di (2-ethylhexyl) thiophosphoric acid for extraction of palladium (II). I. Preparation and study of the retention and distribution of the extractant on the resin//Solvent extraction and ion exchange. - 1998. - T. 16. - No. 2. - C. 545-564.
6. Sharipov K. T., Daminova S. S., Talipova L. L. Crystal and Molecular Structure of Rhodium (III) Diisopropyldi-thiophosphate//Journal of Structural Chemistry. - 2002. - T. 43. - No. 2. - C. 369-372.
D OI: http://dx.doi.org/10.20534/AJT-16-11.12-66-71
Daminova Shahlo Sharipovna, Tashkent Chemical Technological Institute, Department of «Technology of silicate materials and rare precious metals», Scientific Researcher E-mail: [email protected] Talipov Samat,
Institute of Bioorganic Chemistry, Academy of Sciences of Republic Uzbekistan, PhD in Chemistry, E-mail: [email protected] Kadirova Zukhra Chingizovna, Tashkent Chemical Technological Institute, Center of Excellence,
Dr. Engineering, PhD in Chemistry, E-mail: [email protected] Sharipov Khasan Turabovich Professor, Tashkent Chemical Technological Institute, Department of "Technology of silicate materials and rare precious metals",
E-mail: [email protected]
Synthesis and crystal structure of co, cd, bi mixed-ligand complexes of diisopropyldithiophosphate and 2-amino-1-methylbenzimidazole
Abstract: The crystal and molecular structures of the mixed-ligand ternary complexes [Cd (MAB)2 (iso-ProPS2)2], [Co (MAB) (iso-ProPS2)2], [Bi (MAB) (iso-ProPS2)3] were determined. The aminobenzimidazole ligands were monodentate coordinated via endo-cyclic N atom. The monodentate coordination in the Cd
complex and the bidentate coordination of the PSS-groups in the Co and Bi complexes were observed. The molecules interaction and packing in crystal structures were considered on the basis of structural data.
Keywords: synthesis, mixed-ligand complexes, the crystalline structure diizopropilditiofosfat, 2-amino- 1-methylbenzimidazole.
1. Introduction
Study of dialkyldithiophosphoric acids and their derivatives are very actual due to wide applications in industry, biology and medicine [1, 863]. The ability to form themixed-metal [2, 40] and the ternary mixed-li-gand coordination compounds can be explained by the ligand electronic structure [3, 28] and physicochemical properties [4, 674]. The aim of this work is synthesis and X-ray diffraction structural study of [Cd (MAB)2 (¿50-ProPS2)2], [Co (MAB) (¿50-ProPS2)2], [Bi (MAB) (iso-ProPS2)3] complexes with 2-amino-1-methylbenz-imidazole (MAB) and determination of interaction between molecules in crystal.
2. Experimental
Elemental analysis was performed by the atomic absorption spectrophotometer (Aanalyst-800, Perkin Elmer) and the CHNS-analyzer (EA-1108, Carlo-Erba). The ligand coordination was studied by FTIR absorption spectra in the range of400-4000 cm1 (FTIR 2000, Perkin-Elmer), KBr pellets.
Synthesis of [Cd (MAB)2 (iso-Pro2PS2)2]. The MAB solution (0.147 g (1 mmol) in 4 ml of ethanol) was added with stirring to the Cd (iso-Pro2PS2)2 solution (0.426 g (1 mmol) in 16 ml of ethanol). The mixture was kept at room temperature for one hour, and the precipitated white crystals were filtered with suction, washed with cold ethanol, dried in air. Found,%: C 39.8 H 4.9 N 7.2 Cd 12.8; Calculated%: C 40.4 H 5.3 N 7.5 Cd 13.5. FTIR spectra, KBr, cm-1: 450, 502, 531, 549, 631 (shoulder), 650 (PS2), 740, 756 (shoulder), 782, 887, 966, 992, 1105, 1141, 1178, 1246, 1298, 1324, 1350, 1372, 1423, 1467, 1510, 1553, 1600, 1637, 2874, 2932, 2976, 3230, 3337, 3420.
Synthesis of [Co (MAB) (iso-Pro2PS2)2]. The
CoCl2 6H2O solution (0,24 g (1 mmol) in 6 mL of the water-ethanol (1: 1) mixture) was added to the MAB solution (0.16 g (1 mmol) in 4 ml of ethanol). Resulting blue solution was added to 1 ml (2 mmol) of aqueous solution of potassium diisopropyldithiophosphate. The blue-green precipitate was vacuum-filtered, washed twice with water and cold ethanol, dried in air. Found%: C 43.07 H 5.85 N 10.72 7.51 Co; Calculated%: C 43.13 H 5.91 N 10.78 7.58 Co. FTIR spectra, KBr, cm-1: 449, 501, 539, 557 (shoulder), 627 (shoulder), 652 (PS2), 740, 756 (broad), 786, 888, 964, 1016, 1103, 1142, 1178, 1242,
1296, 1325, 1373, 1385, 1424, 1467, 1513, 1551, 1597, 1629, 2874, 2932, 2976, 3055, 3338, 3425.
Synthesis of [Bi (MAB) (iso-Pro2PS2)3]. The MAB solution (1 mmol in 4 ml of ethanol) added to the Bi (iso-Pro2PS2)3 solution (2 mmol in 15 ml of ethanol) by small portions under stirring. The yellow crystals were precipitated from solution after 25 hours at room temperature. The precipitated crystals were filtered with suction, washed with ethanol, dried in air. Found,%: C 31.26 H 5.08 4.27 N 20.93 Bi; Calculated,0/«: C 31.36 H 5.13 4.22 N 21.01 Bi. FTIR spectra, KBr, cm1: 429, 501, 527, 553, 613 (broad), 667 (pS2), 741, 884, 963, 1106, 1140, 1177, 1244, 1292, 1315, 1372, 1383, 1417, 1461, 1489, 1544, 1642 (shoulder), 1674, 2868 (shoulder), 2932, 2978, 3059, 3317.
Single crystals suitable for X-ray diffraction were grown by slow evaporation at room temperature in saturated alcohol solutions. The [Cd (MAB)2 (iso-Pro2PS2)2] compound was crystallized as colorless, transparent, stable well shaped needle crystals. The [Co (MAB) (iso-Pro2PS2)2] single crystals were blue needle-like crystals, and the [Bi (MAB) (iso-Pro2PS2)3] single crystals were yellow needles. The crystallographic parameters determined by single-crystal diffractometer (Crysalys Excalibur, Oxford Diffraction) (Table 1). Data processing was performed using SHELXS86 and SHELXL93 program [5, 112]. The structure was solved by direct methods and refined by full-least-squares method in the anisotropic approximation, the hydrogen atoms refined isotropically, and R factor was less than 0.5.
3. Results and discussion
The [Cd (MAB)2 (iso-Pro2PS2)2] crystal structure is constructed from mononuclear complex molecules. The crystallographically independent molecules located in the common position (Fig. 1a). The structure of the Cd complex has distorted tetrahedral N2S2-configuration around metal ion, the coordination sphere consists of two S atoms from two monodentate coordinated di-isopropyldithiophosphate ions and two nitrogen atoms from two aminobenzimidazole molecules. The bond lengths and angles (Table 2) do not differ from the normal values for Cd diisodithiophosphates [6, 2410]. An intramolecular bond between the sulphur atom and the exo-amino group hydrogens (distances: S... NH2 3.326, S... H — N 3.610 and 3.899 A; angles:
S-H-N 102.34 and 126.21°) promotes the formation of molecules in crystal along the direction [10] is shown in an electrically stable neutral monomer metal complex Fig. 1a. stabilized by n-stacking in crystal structure. Packing of
Figure 1. The structure (H atoms are not shown) and the packing of molecules: a) ^d (MAB)2 (iso-Pro2РS2)2]; b) [to (MAB) (iso-Pro2РS2)2], c) [Bi (MAB) (iso-Pro^y
c
Table 1. - Main crystallographic parameters and coordination polyhedra in the complexes [M (MAB)n (/so-Pro2PS2)m] (n, m=1,2; M=Cd, Co, Bi)
Crystal [Сd (MAB)2 (iso-Pro2 РS2)2] [ta (MAB) (iso-Pro2 РS2)2] [Bi (MAB) (iso-Pro2 РS2)3]
Parameters P21/c, a=14,032 (5), b=8,962 (5), c=31,502 (5) À; |=94,798 (5)°, V=3947,65À3, Z=4 P2p a=10.004 (1), b=10.7993 (9), c=15.0131 (14) À; a=105.702 (8), |3=90.254 (8), y=100.018 (8)°; V=1535.31À 3, Z=1 P21/c, a=11.389 (5), b=29.984 (5), c=12.898 (5) À; |3=101.063 (5)°, V=4322.66À 3, Z=4
M-S, À Cd1-S3 2.503(2) Co1-S1 2.6553(3) Bi1-S2 2.7198(4)
Cd1-S1 2.559(2) Co1-S2 2.3041(3) Bi1-S3 2.909(1)
Co1-S3 2.3327(2) Bi1-S6 2.9545(8)
Co1-S4 2.5878(2) Bi1-S8 2.8375(8)
Bi1-S9 2.798(1)
Bi1-S10 2.9977(8)
M-N, À Cd1-N1 2.255(5) Co1-N1 2.0167(2) Bi1-N16 2.6226(4)
Cd1-N1 2.210(5)
P-S, À P1-S1 2.010(3) P1- S1 1.9708(2) P4-S2 2.0083(6)
P1-S2 1.935(3) P1- S2 2.0042(2) P5-S3 1.9937(7)
P2-S3 2.015(3) P2- S3 2.0025(2) P4-S6 1.9827(4)
P2-S4 1.944(3) P2- S4 1.9715(2) P5-S10 1.9777(7)
P7-S8 1.9821(6)
P7-S9 1.9994(7)
S-M-S,° S3-Cd1-S1 108.72 (6) S1- Co1- S2 80.96 (8) S2-Bi1-S3 94.35
S3- Co1- S4 82.90 (9) S2-Bi1-S6 71.58
S1- Co1- S4 173.50 (8) S2-Bi1-S8 92.44
S1- Co1- S3 92.30 (9) S2-Bi1-S9 92.64
S2- Co1- S3 121.29 (8) S2-Bi1-S10 90.77
S2- Co1- S4 97.76 (9) S2-Bi1-S3 94.35
S3-Bi1-S9 71.02
S3-Bi1-S10 66.94
S6-Bi1-S8 76.79
S6-Bi1-S10 76.67
S8-Bi1-S9 70.96
N-M-N,° N4-Cd1-N1 111.64(18) — -
S-M-N,° N4-Cd1-S3 116.96(15) S2-Co1-N1 122.28(14) S2-Bi1-N16 169.92(15)
N1-Cd1-S3 114.41(14) S3-Co1-N1 115.90(15) S3-Bi1-N16 94.96(14)
N4-Cd1-S1 106.87(15) S4-Co1-N1 96.12(12) S6-Bi1-N16 98.66(15)
N1-Cd1-S 195.75(14) S1-Co1-N1 89.90(14) S8-Bi1-N16 82.62(14)
S9-Bi1-N16 94.02(14)
S10-Bi1-N16 89.34(15)
Bi-S-P,° P1-S1-Cd1 102.66(9) Co1-S1-P1 80.47(10) Bi1-S2-P4 90.40(10)
P2-S3-Cd1 99.74(8) Co1-S2-P1 89.23(9) Bi1-S3-P5 92.41(9)
Co1-S3-P2 86.38(9) Bi1-S6-P4 84.35(8)
Co1-S4-P2 80.29(8) Bi1-S8-P7 88.84(9)
Bi1-S9-P7 89.63(8)
Bi1-S10-P5 90.15(9)
S-P-S,° S4-P2-S3 115.45(11) S1-P1-S2 108.73(12) S2-P4-S6 112.79(8)
S2-P1-S1 114.51(12) S3-P2-S4 110.38(10) S8-P7-S9 110.48(8)
S3-P5-S10 110.26
M -N -C,° C21-N4-Cd1 127.3(4) Co1-N1-C1 127.14(15) Bi1-N16-C20 124.57(4)
C22-N4-Cd1 125.9(4) Co1-N1-C7 128.46(16) Bi1-N16-C21 127.36(4)
C13-N1-Cd1 125.7(4)
C14-N1-Cd1 128.2(4)
The [Co (MAB) (î50-Pro2RS2)2] structure has a five-coordinated distorted tetragonal pyramide polyhedron (Fig. 1b). The distorted N1S4-configuration consists of the two diisopropyldithiophosphates S-S-donor atoms of and the benzimidazole endo-cyclic nitrogen. In spite of the Co polyhedron in [Co (MAB)2 (Ac)2]H2O complex [7, 1373], where Co had a tetrahedron configuration with the monodentate coordinated acetate groups, the sulfur atoms lead to 5-coordinated polyhedron in the [Co (MAB) (iso-Pro2RS2)2] structure, and the SCoS angles within 4-membered chelate rings are deviated in range of 82.90-80.96°. The phosphorus atoms have distorted-tetrahedral configuration (the SPS and OPO angles are equal 110.4, 108.7 ° and 95.71,100.56 °, respectively, the P - S bonds are equal to 1.971 and 2.004 Á), the distance P - O (1.573-1.579 Á) corresponds to single bonds. The Co - N bond is localized via endo-cyclic N-atom. The bond length, angles in the benzimidazole ligand are similar to the 2-amino-1-methylbenzimidazole hydrochloride structure [8, 520] and 2-amine-1-methylbenzimidazole dichlo-rocobalt (II) [7, 1373]. Analysis of the bond lengths and angles of the molecules in the coordination compounds clearly indicates that the MAB molecule has amino-tauto-meric form. Amino group is coplanar with a methyl group (the C8- N2- C7- N3 torsion angle is equal to 3.14°), the Co - N bond length (2.017 Á), the Co - S bonds lie in the range of2.304-2.665 Á, which are comparable to known dithiophosphoric acid complexes containing ligand in a similar orientation [6, 2410].The intra- and intermolecular hydrogen bonds and crystallization water are absence in contrast to similar complex [7, 1373].
The structure of the synthesized mixed-ligand complex [Bi (MAB) (iso-Pro2RS2)3] characterized by distortion of the pentagonal bipyramidal N1S6-con-figuration observed in structures of frá-diisopropyldi-thiophosphate of bismuth (III) and gold (III) [9, 369] due to insertion of the 1-methyl-2 aminobenzimidazole molecule. Therefore, bismuth ion is coordinated with six sulfur atoms of bidentate diisopropyldithiophos-phate ions and an nitrogen atom of the aminobenzimidazole molecule (Fig.lc). The bond lengths and angles in the complex do not differ from the normal values. The hydrogen bonds are not observed, and the monomer complex particles combined with each other by n-stacking interactions. Packing of complex molecules is shown in Fig. 1c.
4. Conclusions
The [Cd(MAB)2(i-Pro2RS2)2], [Co (MAB) (i-Pro2RS2)2] and [Bi(MAB)(i-Pro2RS2)3] were synthesized and the crystal structures were determined. The structure of the Cd complex has distorted tetra-hedral N2S2-configuration. The Co complex molecule has distorted N1S4-tetragonal pyramid coordination structure. The structure of the Bi complex has N1S6-distorted pentagonal bipyramidal molecular geometry configuration. The diisopropyldithiophosphates are bi-dentate coordinated via S-S-donor atoms in the Co and Bi complexes, and S-monodentate coordinated in the Cd complex. The 2-amine-1-methylbenzimidazole coordinated via endo-cyclic nitrogen. Packing of molecules in crystal characterized by n-stacking interactions without strong intermolecular hydrogen bonds.
References:
1. Alimarin I. P., Ivanov V. M. Extraction with thio and dithio phosphorus acids//Russian Chemical Reviews. -1989. - T. 58. - №. 9. - C. 863.
2. Rakhmonova DS, Kadirova Z.Ch., Kadirova Sh.A., Parpiev N.A., Dzhorakulova N.H. Synthesis and study of complex compounds of mixed metal acetates of Co (II), Cu (II) with 2-amino-1-methylbenzimidazole//Chemistry and Chemical Technology. - 2015. - No 1. - P. 40-42.
3. Grundemann E., Graubaum H., Martin D., Schiewald E. NMR investigations on benzheteroazoles. 2—NMR investigations of N-acylated 2-aminobenzimidazoles//Magnetic resonance in chemistry. - 1986. - T. 24. - No. 1. - C. 21-30.
4. Daminova S. S., Talipova L. L., Sharipov K. T. The complex compounds of noble metals with diisopropyldithio-phosphoric acid //Abstracts of Papers of the American Chemical Society. - 1155 16th ST, NW, Washington, DC 20036 USA : Amer Chemical Soc, - 2002. - T. 224. - C. U674-U674.
5. Sheldrick G. M. A short history of SHELX//Acta Crystallographica Section A: Foundations of Crystallography. - 2008. - T. 64. - No 1. - C. 112-122.
6. Lawton S.L., Kokotailo G.T. Crystal and molecular structures of zinc and cadmium O, O-diisopropylphospho-rodithioates//Inorganic Chemistry. - 1969. - T. 8. - №. 11. - C. 2410-2421.
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Synthesis of fatty Acid amide by the sherbule reaction based distilled Fatty Acids
8. Borodkina I. G., Antsnshkina A. S., Sadikov G. G., Mistrnukov A. E., Garnovskii D. A., Uraev A. I., Borodkin G. S., Garnovskaya E. D., Sergienko V. S. & Garnovskii A. D. A model system for the study of competitive coordination in aminoheterocyclic complexes. Molecular and crystal structure of 2-amino-1-methyl-benzoimidazolium chloride hydrate //Russian Journal of Coordination Chemistry. - 2003. - T. 29. - No 7. - C. 519-523.
9. Sharipov K. T., Daminova S. S., Talipova L. L. Crystal and Molecular Structure of Rhodium (III) Diisopropyldi-thiophosphate //Journal of Structural Chemistry. - 2002. - T. 43. - No 2. - C. 369-372.
DOI: http://dx.doi.org/10.20534/AJT-16-11.12-71-75
Qurbanov Zufar, assistant,
Tashkent chemical-technological institute Ikromov Abduvaxob, professor,
Tashkent chemical-technological institute E-mail: [email protected]
Synthesis of fatty Acid amide by the sherbule reaction based distilled Fatty Acids
Abstract: Field of application of fatty acid amides because of their reactivity is various. Nitrites, primary amines, valuable flotation agents, additives for fuels based on fatty acid amides have been produced. The amides are obtained based on fatty acids. A fatty acid synthesized by oxidation of paraffins. Until recently, the raw material for the production of paraffin's are hydrocarbon sources, such as oil and natural gas, gas condensate, coal and others. It should be noted that, the content of higher hydrocarbons is low in these sources. Various oxidants are used to produce acids from them. The process is conducted under severe conditions at high temperatures and under high pressure. However, because of decreasing fossil fuel and oil reserves, other raw materials for the production of carboxylic acids have to be investigated from scientists. In this regard, distilled fatty acid (DFA) obtained from soapstock is perspective and the separation of individual components is considered as an actual task.
Keywords: amine, amide, sylvinite, fatty acids, chloride, acid.
The world population is growing rapidly, and the They are used in pharmacy, cosmetics, organic syn-fact that is expected to reach more than 9 billion by thesis and in the production of potassium chloride as 2050, it became evident that the world needs to pro- flotation reagent.
duce more food to keep up with the growing number The demand for amines in the "Dehkanabad potash
of mouths to feed. However, increasing number of plant" is 250 tons annually. Amines are not produced in people means further urbanization and therefore less Uzbekistan. Therefore, at the present time they buy farmland to work with, which means that farmers need from foreign countriesfor 3000 USD per ton. With-to increase productivity. It means, by increasing popu- the expansion of capacity of the plant the demands for lation, the demands for the production of potassium amines also increased.
fertilizer also increases. 200,000 tons of export-orient- Higheracid (intermediates of oil and fat industry),
ed import substitution potash annually produced in fuel alcohols (waste products of biochemical plants), Dehkanabad potash plant [1]. Potash fertilizer is pre- as well as urea and sodium hypochlorite can be used as pared from sylvinite. Uzbekistan occupies one of the raw materials for the synthesis of amines [2]. leading place in the world by sylvinite stocks. In the The synthesis of amines is carried out in three stag-
stock of Tyubegatana the sylvinite reserve is 215 mil- es. In a first step the fatty acid amides are synthesized lion tons. Separation of sylvinitefrom ore is carried out according to the following reaction: by flotation and amines can be used in this purpose. R - COOH + CO (NH2)2 = R - CONH2 + NH3 + CO2
