DIAMIDE COMPLEX COMPOUNDS OF CALCIUM SUCCINATE WITH FORMAMIDE, ACETAMIDE, CARBAMIDE AND THIOCARBAMIDE

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1 Journal of Chemical Dilshod Technology M. Khaydarov, and Тokhir Metallurgy, A. Аzizov 51, 1, 2016, DIAMIDE COMPLEX COMPOUNDS OF CALCIUM SUCCINATE WITH FORMAMIDE, ACETAMIDE, CARBAMIDE AND THIOCARBAMIDE Dilshod M. Khaydarov, Тokhir A. Аzizov Institute of General and Inorganic Chemistry Academy of Sciences of Uzbekistan 77a, Mirzo-Ulugbek str , Tashkent, Uzbekistan Received 30 January 2015 Accepted 30 October 2015 ABSTRACT This study reports data referring to the synthesis of diamides coordination compounds of calcium succinate with formamide, acetamide, carbamide, and thiocarbamide. The composition and the formamide, acetamide, carbamide, and thiocarbamide and succinate fragment molecule coordination are elucidated with the application of oscillation spectroscopy methods. The comparative consideration of the interplanar space and relative intensity of monohydrate calcium succinate and those of formamide, acetamide, carbamide, thiocarbamide and complexed compounds of CaC 4 CH 3 O, CaC 4 CO(NH 2 O, CaC 4 CS(NH 2 O shows that the novel complex compounds differ from each other. The compounds have individual crystal lattices. Keywords: complex compounds with diamides, coordination, central atom, synthesis, element analyses, coordination methods, thermal behavior, individuality. INTRODUCTION One of the actual tasks of modern chemistry is the synthesis of novel chemical compounds possessing effective properties for agricultural application. Complex compounds of s-, p-, d- metals having a number of specific properties find wide application in different branches of the national economy. Substances whose compositions contain a donor atom, for example, amides of aliphatic, carboxylic, and pyridonecarboxylic acid, particularly formamide, acetamide, carbamide, nitrocarbamide, thiocarbamide, benzoamide, nicotinamide, and nicotinic acid promote the formation of complex compounds with metals ions. Anions of organic and inorganic acids (acetic, benzoic, stearic, oleic, palmitic, succinic, nicotinic, and nitric acids) display fully variable methods of coordination depending on the metal nature and the complexes composition. They participate actively in biological and catalytic processes and are mainly applied as selective complex formation agents and leaching of metals as well.. Therefore, these compounds have already attracted the inorganic chemists attention [1-7]. There are many studies referring to the complex compounds of p, d, and f-metals with acid amides using homogeneous ligands. However, there were no data on the synthesis of coordination compounds with metal diamides prior to studies. The ligands (the acid anions) coordination with the water molecule from the atom coordination environment is not treated either. This was the reason to select calcium succinate in this investigation. Besides, the organic ligands nature was varied as it affected their abilities to complex formation. The synthesis of complex compounds of calcium succinate with formamide, acetamide, thiocarbamide and carbamide, as well as the study of their composition and thermal behavior was aimed in the present study. EXPERIMENTAL Chemically pure formamide, acetamide, carbamide, and thiocarbamide were used. Anions of succinate acid (C 4 ) were introduced to promote the formation of complex compounds with metals ions. The mechanochemical method was selected as a synthesis method as it did not require deficient organic solvents. The procedure used was in correspondence with that described in ref. [8]. The cmplex compounds CaC 4 H CH 3 Н 2 О, CaC 4 53

2 Journal of Chemical Technology and Metallurgy, 51, 1, 2016 Table 1. Data referring to the elemental analysis of complex compounds of calcium succinate with diamides. Compounds Са, % N, % S, % C, % H, % Found Count Found Count Found Count Found Count Found Count CaC 4 14,21 14,41 9,98 10, ,79 30,20 4,99 5,07 CH 3 O CaC 4 14,27 14,35 14,97 15, ,01 25,81 4,76 4,69 CO(NH 2 O CaC 4 CS(NH 2 O 13,93 14,00 14,77 14,68 10,97 11,20 24,98 25,17 4,19 4,22 CO(NH 2 Н 2 О, CaC 4 CS(NH 2 Н 2 О were obtained by intensive mixing monohydrate calcium succinate with M of formamide and M of acetamide, M of monohydrate calcium succinate with M of formamide and M carbamide, as well as M of monohydrate calcium succinate with M formamide and M carbamide, M of monohydrate calcium succinate with M formamide and M thiocarbamide. This was done in an agathic mortar at room temperature (25ºC). The time required was 3 hours. The synthesized compounds were analyzed following the procedure described in ref. [9]. The nitrogen content was determined in accordance with the Dume method [10], while that of carbon and hydrogen was done by burning in presence of oxygen. The elemental analysis of the compounds synthesized is presented in Table 1. The identification of the compounds synthesized was carried out on the ground of skiagraphs taken by DRON-2 (Russia) with Cu anticathode [11]. The infrared absorption spectrum was recorded in the range of 400 cm cm -1 using the spectrometer module AVATAR-360 (Nicolet). The thermal analysis was performed with the application of a derivatographe with F.Paulik-J.Paulik-L.Erdey system [12] at velocity 9 degree/min, and a sensitivity galvanometer T-900, TG-200, DTA, DTG-1/10. Each sample was of a mass of 0.2 g. Platinum crucible of 10 mm diameter without a lid was used as a holder. Powder of Al 2 O 3 was used as an etalon. The data were obtained at ambient conditions. RESULTS AND DISCUSSION Values of the interplanar spacing (d, Å) and the relative intensity (I, %) of monohydrate calcium succinate, formamide, acetamide, carbamide, thiocarbamide, and the coordination compounds on their basis are shown in Table 2. It is evident that the novel complex compounds differ from each other and the original components. This provides the conclusion that these compounds have individual crystal lattices. Uncoordinated molecules of formamide are found by infrared spectrum absorption at frequencies (cm -1 ) of 3390, ν(nh 2 ), δ(NH 2 ), ν(cн), ν(со), δ(nh 2 ), δ(сн), ν(cn), ρ(nh 2 ), and δ(ocn). Free molecules of acetamide are characterized by infrared spectrum absorption vibrational bands at ν(nh 2 ), δ(NH 2 ), ν(co), δ(nh 2 ), ν(co), ν(cn), δ(ch 3 ), ρ(nh 2 ), ρ(ch 3 ), ν(cc), δ(nco), and δ(ccn). Free molecules of carbamide are found at infrared spectrum absorption frequencies of ν as (NH 2 ), ν s (NH 2 ), δ(NH 2 ), ν(co), δ(nh 2 ), δ(nh 2 ), ν(co), ν(cn), Table 2. Values referring to the interplanar space and the relative intensity lines of formamide, acetamide, thiocarbamide free molecules and their complexes with calcium succinate. Compound d, Å I, % d, Å I, % d, Å I, % d, Å I, % d, Å I, % [CaC 4 ]*3H 2 O 14,22 3 4,91 2 2,86 1 1, , ,77 3 4,82 2 2,84 2 1, ,

3 Dilshod M. Khaydarov, Тokhir A. Аzizov Table 2. Values referring to the interplanar space and the relative intensity lines of formamide, acetamide, thiocarbamide free molecules and their complexes with calcium succinate (continued). [CaC 4 ]*3H 2 O 13,04 3 4,76 1 2,82 2 1, , ,96 2 4,69 2 2,78 1 1, , ,59 5 4,57 9 2,76 2 1, , ,24 3 4,38 1 2,72 3 1, , ,36 3 4,33 2 2,52 4 1, , ,19 3 4,27 4 2, , , ,50 3 4,22 8 2,59 1 1, , ,07 3 4,17 2 2,54 4 1, , ,80 3 4,10 2 2,51 2 1, , ,00 1 4,07 2 2, , , ,86 2 4,01 2 2,46 4 1, , ,72 2 3,92 2 2,44 2 1, , ,48 2 3,88 2 2,43 1 1, , ,39 2 3,82 2 2, , , ,11 7 3,75 2 2,35 4 1, , ,88 2 3,67 2 2, , , ,50 2 3,62 3 2,30 2 1, , ,23 1 3,58 1 2,27 1 1, , ,12 1 3,51 3 2,25 6 1, , ,01 1 3,47 2 2,23 3 1, , ,81 2 3,44 2 2,21 2 1, , ,69 3 3,32 8 2,18 9 1, , , , , , , , , ,12 5 1, , ,89 3 3, ,10 3 1, , ,74 2 3, ,07 4 1, , ,61 2 3,09 1 2,07 4 1, , ,55 2 3,03 2 2,05 1 1, ,

4 Journal of Chemical Technology and Metallurgy, 51, 1, ,44 3 3,01 2 2,03 2 1, , ,33 2 2,99 3 2,03 1 1, , ,21 3 2,96 7 2,02 1 1, ,14 3 2, ,01 2 1, ,98 4 2,88 2 1, , , , , , ,02 29 H 16, , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , , ,21 6 4,51 4 2, ,05 1 1,581 6 CH 3 18,05 8 4,26 2 2, ,03 1 1,

5 Dilshod M. Khaydarov, Тokhir A. Аzizov 16, ,03 1 2,56 3 1, , ,69 9 3,95 1 2,52 2 1, , ,24 3 3,85 1 2,49 2 1, , ,42 2 3,70 1 2,36 1 1, , ,13 5 3,62 1 2,30 7 1, , , ,55 3 2,26 2 1, ,26 8 3, ,22 3 1, ,01 6 3, , , ,78 5 3,14 4 2,10 1 1, ,21 2 4,37 2 3, ,20 4 1,770 2 CO(NH 2 16,08 3 3, , ,15 2 1, ,29 3 3, , ,01 1 1, ,86 2 3,25 2 2,46 5 1, , ,59 1 3,14 3 2,33 1 1, ,8 1 3,0 37 2,3 5 1,8 8 1,6 8 CS(NH 2 4,4 6 2,9 13 2,2 2 1,8 15 1,55 6 4, ,8 14 2,1 8 1,8 8 1,5 3 4,1 17 2,7 9 2,1 3 1,7 11 1,4 2 3,7 54 2,5 8 2,0 2 1,7 6 1,36 3 3,4 59 2,4 33 1,9 2 1,7 2 1,3 3,1 52 2, ,9 4 1,6 5 11,9 7 4,5 5 2,9 12 2,0 14 1,6 3 CaC 4 CH 3 O 10,2 5 4,3 5 2,8 16 1, ,51 4 9,9 5 4,3 5 2,6 4 1,94 8 1,5 5 9,0 6 4,2 5 2,6 5 1,9 11 1,48 5 7,9 5 4,0 13 2,5 5 1,9 9 1,46 6 7,4 7 3,9 5 2,4 53 1,9 9 1,4 4 6,8 23 3,8 7 2,4 55 1, ,4 5 6,6 7 3,7 9 2,4 10 1,33 9 1,4 3 57

6 Journal of Chemical Technology and Metallurgy, 51, 1, ,4 5 3,6 10 2,3 4 1,8 5 1,4 4 6,2 5 3,6 7 2,3 6 1,8 6 1,35 4 5,6 10 3,5 6 2,3 6 1, ,34 4 5,5 10 3,4 75 2,2 12 1,7 12 1,3 4 5,4 6 3,3 6 2,2 17 1,7 15 1,3 3 5,1 6 3,2 4 2,2 8 1,6 7 5,0 7 3,1 18 2,2 20 1,6 5 4, ,1 40 2,1 4 1,6 6 4,6 3 2,9 13 2,0 11 1,6 4 19,2 13 4,7 8 2,8 13 2,0 22 1,57 11 CaC 4 CO(NH 2 O 17,6 13 4,4 22 2,8 11 1, , ,9 16 4,3 22 2,7 11 1,9 11 1, ,2 8 4,1 11 2,7 12 1,9 16 1,5 11 9,5 8 4,1 9 2,6 78 1,9 44 1,5 11 8,5 8 3,9 35 2,6 9 1, ,48 8 7,9 58 3,9 14 2,6 12 1,8 14 1,46 8 7,2 65 3,7 99 2,5 47 1, ,4 8 6, 7 9 3,6 34 2, ,7 16 1,4 11 6,5 9 3,5 10 2,4 56 1,7 14 1, ,4 11 3,5 9 2, , ,4 9 6,2 10 3,4 78 2,3 15 1,71 9 1,4 8 6,1 12 3,3 45 2,2 24 1,7 11 1,37 9 5,9 11 3,2 8 2,2 12 1,7 12 1,35 9 5,8 9 3,2 12 2,2 9 1,6 11 1,3 9 5,7 11 3,1 39 2,1 31 1, ,34 9 5,5 13 3,1 37 2,1 14 1,6 12 1, ,3 11 3,0 15 2,1 19 1, ,32 9 5,1 61 3,0 15 2,0 30 1,6 9 1,3 10 4,9 14 2,9 56 2,0 31 1,6 11 1, ,2 11 5,5 9 3,1 51 2,0 16 1,5 3 58

7 Dilshod M. Khaydarov, Тokhir A. Аzizov CaC 4 CS(NH 2 O 12,2 7 5,4 10 3,0 56 1, ,5 3 10,0 5 5,3 5 2,9 23 1, ,5 4 9,6 6 5,1 6 2,8 39 1, ,48 4 9,4 4 4,8 7 2,8 7 1,87 7 1,45 5 9,0 6 4,6 5 2,8 11 1, ,44 3 8,5 4 4,5 6 2,7 9 1,83 7 1,43 3 8,2 4 4,3 86 2,5 24 1, ,41 7 8,1 5 4, ,4 26 1,78 7 1,40 4 7,7 5 4,1 5 2,4 25 1, ,40 3 7,5 6 3,9 11 2,4 39 1,74 9 1,37 4 7,2 6 3,8 56 2,3 5 1,7 9 1,4 4 7,1 7 3,6 5 2,3 9 1, ,3 5 7,0 5 3,6 7 2,3 6 1,6 8 1,33 5 6,9 5 3,6 8 2,2 12 1,6 7 1,3 4 6,6 21 3,4 35 2,1 16 1,6 7 1,3 4 6,4 5 3,4 79 2,1 6 1,56 4 1,3 4 6,0 6 3,3 4 2,1 4 1,5 5 1,3 5 ρ(nh 2 ), ν(cn), δ(nh 2 ), δ(nco) and δ(nсn). Uncoordinated molecules of thiocarbamide have frequencies in the infrared absorption spectrum at ν as (NH 2 ), 3276-ν s (NH 2 ), δ(NH 2 ), 1619-δ(NH 2 ), δ(hnc), 1474-ν(CN),1413-ν(CS), ν(cn), 783- ρ(nh 2 ), 730-ν(CS), 631-δ(CS), δ(ncs), 487-δ(NCN), and 413- δ(ncs). The data presented show that the frequencies of amide molecules are essentially changed considerable due to transition into coordinated state. It is worth adding that some of the observed frequencies could not be assigned to the specific vibrations. Besides, the ν(c=о) frequency is outlined at 1690 сm -1, 1692 сm -1, 1693 сm -1, 1668 сm -1, 1671 сm -1 in CaC 4 CH 3 Н О and 2 CaC 4 CO(NH 2 Н О (Fig. 1 and Fig. 2). 2 Moreover, the frequencies of the valence vibrations of C-N in case of formamide, acetamide, and carbamide compounds are recorded at 12 сm сm -1, 37 сm -1 and 33 сm -1, respectively. Fig. 3 presents the frequencies of С=О and СN bonds displayed for formamide at 1693 сm -1 and 1328 сm -1 in CaC 4 H CS(NH 2 Н 2 О. The frequencies of thiocarbamide molecules at 730 сm -1 and 621 сm -1 are reduced to 40 сm -1 and 10 сm -1 in the low-frequency range. The changes observed could be explained by the thiocarbamide molecules coordination with the calcium ions through the sulfur atom. The difference of the values of ν as (СОО) and ν s (СОО) frequencies of all compounds is less than 150 cm -1. It corresponds to bidentate-cyclic coordination of each carbocyclic group of the succinate fragment. The central ion possesses six-axis points in the complex 59

8 Journal of Chemical Technology and Metallurgy, 51, 1, 2016 Fig. 1. Infrared absorption spectrum of the mixed ligands of CaC 4 CH 3 O. compounds. In this case the water molecules are held by hydrogen bonds. The thermal examination of the complex compounds synthesized shows endothermic effects corresponding to the removal and decomposition of the bonded and coordinated molecules of water, formamide, acetamide, carbamide, and thiocarbamide. 60 Fig. 2. Infrared absorption spectrum of the mixed ligands of CaC 4 CO(NH 2 O. Еxothermic effects are also observed. They are determined by the acetate fragments dissolution, by the products thermal decomposition and formation of calcium oxide or calcium sulphide. This is evidenced by the DTA curves obtained. The heating curve of CaC 4 CH 3 O are characterized

9 Dilshod M. Khaydarov, Тokhir A. Аzizov Fig. 3. Infrared absorption spectrum of the mixed ligands of CaC 4 CS(NH 2 O. Fig. 4. Thermogravimetric curves of: I-CaC 4 CH 3 O; II-CaC 4 CO(NH 2 O; III-CaC 4 CS(NH 2 O. 61

10 Journal of Chemical Technology and Metallurgy, 51, 1, 2016 by five endothermic effects at 117 C, 167 C, 233 C, 791 C, 805 C and six exothermic effects at 320 C, 404 C, 504 C, 600 C, 684 C, and 757 C (Fig. 4.I). The first endothermic effect is attributed to the removal of one water molecule. The second endothermic effect is determined by the formamide s coordinated molecule decomposition. The third endothermic effect is connected with the decomposition of the carbamide s coordinated molecule. The subsequent exothermic and endothermic effects are attributed to the decomposition of the succinate fragment, to the thermolysis products burning and the product formation. The total loss of mass is % in the temperature range of 60 C C. The DTA results of CaC 4 CO(NH 2 0.5H 2 O show five endothermic effects at 115 C, 156 C, 237 C, 598 C, 789 C and four exothermic effects at 314 C, 336 C, 480 C, and 698 C (Fig. 4.II). The first endothermic effect corresponds to 0.5 water molecules removal. The second endothermic effect is attributed to the formamide s coordinated molecule decomposition. The nature of further thermal effects can be explained by coordinated thiocarbamide decomposition, succinate fragment and thermolysis products burning, and calcium sulfide formation. The total loss of mass is % in the temperature range of 60 C C. The DTA curves of CaC 4 CS(NH 2 H 2 O show five endothermic effects and four exothermic effects at 120 C, 162 C, 210 C, 620 C, 783 C, and 325 C, 403 C, 458 C, 520 C (Fig. 4.III). The first endothermic effect is determined by one water molecule removal. The second and the third endothermic effect are connected with the decomposition of the coordinated molecules of formamide and acetamide. The subsequent thermal effects are connected with the succinate fragment decomposition, the thermolysis products burning, and the product formation. The total loss of mass is % in the temperature range of 55 C C. CONCLUSIONS Results referring to the synthesis of coordination compounds of calcium succinate with formamide, acetamide, carbamide, thiocarbamide are given in this study. The composition and the coordination observed are identified. The thermal behavior of complexes obtained is studied. REFERENCES 1. B.I. Imanakunov, Interaction of acetomide with inorganic salts, Bishkek, O.F. Khodjaev, T.A. Azizov, N.A. Parpiev, Examinations of complexed compounds of bivalent metals with acetomide, J. Coor. Chem., 3, 10, 1977, G.J. Mukumova, Synthesis and investigation of succinates coordinating compounds of some 3d metals with amides, Ph. D. thesis, Tashkent, T.A. Azizov, Pseudoamido-, amino- and aqua carboxylic coordinating groups of a number of metals, Ph. D. thesis, Tashkent, D.M. Khaydarov, T.A. Azizov, T.A. Ibadullaeva, J.U. Turakulov, Nitrocarbamide and nicotine amide complexed compounds of calcium succinate, Uzbek Chemical Journal, 2, 2014, D.M. Khaydarov, T.A Azizov, Mixed amides complex compounds of calcium cuccinate, 4 th European Conference on Innovations in Technical and Natural Sciences, Austria, Viena, 2014, S.U. Meldebekova, T.A. Azizov, Complexed compounds of nickel (II) acetate, Uzbek Chemical Journal, 5, 2002, V.V. Skopenko, Direct synthesis of coordinating compounds, Academy Science of Ukraine, Kiev, 1997, p P. Prishibil, Complexons in chemistry analysis, Moscow, 1960, (in Russian). 10. V.A. Klimova, Theory of micro methods for organic compounds analysis, Moscow, 1967, (in Russian). 11. P.M. Kovba, V.K. Trunov, X-ray phase analysis, Moskow, 1976, p. 232, (in Russian). 12. F. Paulik, J. Paulik, L. Erdey, Derivatograph. I Mittelung Ein automatish registriender Apparat zur gleichzeitigen Ausguchrund der Differential their moqravimetrichen Untersuchungen, Z.Anal. Chem., 160, 4,