Complexes of 1,8-bis(hydrazidomethylsulfo­nyl)octane and 1,10-bis(hydrazidomethylsulfonyl)decane with copper(II)

V.V. Neklyudov ^a*, G.A. Boos ^a**, M.M. Shulaeva ^b***, O.A. Lodochnikova ^b****,

G.A. Chmutowa ^a*****, E.P. Bulavina ^a******, R.R. Amirov ^a*******

^aKazan Federal University, Kazan, 420008 Russia

^bArbuzov Institute of Organic and Physical Chemistry, FRC Kazan Scientific Center,

Russian Academy of Sciences, Kazan, 420088 Russia

E-mail: ^*sacredbox@hotmail.com, ^**anezka_93@mail.ru, ^***mshulaeva@iopc.ru, ^****lod_olga@mail.ru, ^*****lod_olga@mail.ru, ^******bulawinaelizaweta@yandex.ru, ^*******ramirov@kpfu.ru

Received September 13, 2019

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DOI: 10.26907/2542-064X.2020.1.33-51

For citation: Neklyudov V.V., Boos G.A., Shulaeva M.M., Lodochnikova O.A., Chmutowa G.A., Bulavina E.P., Amirov R.R. Complexes of 1,8-bis(hydrazidomethylsulfonyl)octane and 1,10-bis(hydrazidomethylsulfonyl)decane with copper(II). Uchenye Zapiski Kazanskogo Universiteta. Seriya Estestvennye Nauki, 2020, vol. 162, no. 1, pp. 33–51. doi: 10.26907/2542-064X.2020.1.33-51. (In Russian)

Abstract

1,8-bis(hydrazidomethylsulfonyl)octane and 1,10-bis(hydrazidomethylsulfonyl)decane differ by hydrocarbon spacer length, solubility in water, and polymerization tendencies. They and their amides are known to be new antitubercular agents. The substances act as polydentate ligands; in the pH range of 4.5–5.0 and with copper(II), they form cationic mono- and binuclear complexes. Preparatively isolated copper complexes with each of the two compounds have different compositions, which also differ from the composition of complexes in the solution.

Keywords: 1,8-bis(hydrazidomethylsulfonyl)octane, 1,10-bis(hydrazidomethylsulfonyl)decane, copper(II), acid-base properties, complexation, ligand denticity, three-dimensional structure, elemental analysis, X-Ray crystallography

Acknowledgments. We are grateful to the staff of Distributed Spectral-Analytical Center of Shared Facilities for Study of Structure, Composition and Properties of Substances and Materials of Federal Research Center of Kazan Scientific Center of Russian Academy of Sciences for their research with the help of the XRC method.

The study is performed according to the Russian Government Program of Competitive Growth of Kazan Federal University.

Figure Captions

Fig. 1. Absorption spectra of the aqueous solutions of L compound. Concentrations of C_L?10⁴, mol/L 1 – 0.10, 2 – 0.20, 3 – 0.30, 4 – 0.40, 5 – 0.50, 6 – 0.60, 7 – 0.70; 8 – 0.80; 9 – 0.90; 10  – 1.00; 11 – 1.20; 12 – 1.50; 13 – 2.00; 14 – 10.00. l = 1 cm. pH: 1 – 5.97, 2 – 5.98, 3 – 5.96, 4 – 5.94, 5 – 5.94, 6 – 6.97, 7 – 6.26; 8 – 5.94, 9 – 5.97, 10 – 5.94, 11 – 5.21, 12 – 6.21, 13 – 6.08.

Fig. 2. n – pH dependence (a). Concentrations, mol/L: C_L 1.036∙10^–3, C_HCl 4.0∙10^–3, C_NaOH 1.72.0∙10^–3. V₀ = 20.0 mL. Diagram of sharing (b) depending of the pH value of L compound of protonated and deprotonated particles in the aqueous solution. 0 – L; 1 – [LH]⁺; 2 – [LH₂]²⁺; 3 – [L¹H_–1]^–; 4 – [L¹H_–2]^2–; 5 – [L(L¹H_–1)]^–.

Fig. 3. Absorption spectra (а) of the aqueous solutions of Cu(NO₃)₂ (1), L compound without (2) and with copper(II) (3), additive absorption spectrum of Cu(NO₃)_2–L system (4). Concentrations, mol/L: С_L 2∙10^–4 (2, 3); С_Cu2+ 5∙10^–5 (1, 3). pH: 1 – 5.40; 2 – 5.55, 3 – 5.03. l = 1 cm. Sharing of complex forms (b) in Cu(NO₃)_2–L system. C_Cu2+ 1∙10^–4 mol/L. 0 – Cu²⁺, 1 – [CuL]²⁺, 2 – [CuL₂]²⁺.

Fig. 4. Absorption spectra (a) of copper(II) solutions  (2, 6), Z compound without (1, 4, 7) and with (3, 5) copper(II). Concentrations, mol/L: C_Z∙10⁴: 1 – 10, 4 – 4, 7 – 1, 3 – 10, 5 – 4. C_Cu2+ 10⁴: 2 – 10, 6 – 4, 3 – 10, 5 – 4. λ_max, nm: 1 – 195, 4 – 195–197, 7 – 193–195, 3 – 201, 5 – 198–200, 2 – 203, 6 – 199–204. ε, L/(mol?cm): 1 – ε₁₉₅ 6.48∙10³, 4 – ε₁₉₆ 8.94∙10³, 7 – ε₁₉₄ 9.96∙10³, 2 – ε₂₀₃ 1.75∙10⁴, 6 - 2.05∙10⁴, 3 – ε₂₀₁ 2.04∙10⁴, 5 – ε₁₉₉ 2.74∙10⁴. Absorption spectra of Z compound (b) in aqueous DMSO solution (60 vol. % DMSO). Concentrations, mol/L: C_Z∙10⁴. 1 – 0.5, 2 – 1.0, 3 – 1.5, 4 – 2.0, 5 – 4.5. Sharing of (c) monomeric and tetrameric forms (based on the analysis of experimental data for λ 255 nm). Experimental and theoretically calculated values of the molar absorptivity coefficients (d) for λ 255 nm (1) and 260 nm (2), R (λ 255 nm) 2.10%, R (λ 260 nm) 1.52%.

Fig. 5. A₂₄₈ – C_Z/C_Cu2+ dependence for the aqueous DMSO solution. С_DMSO 60 vol. %.

Fig. 6. Schematic structure of [Cu₂L₃](NO₃)₄∙2H₂O binuclear complex (a), molecular structure of the complex based on the data of X-ray crystallography (b). Nitrate anions and water molecules are not shown for simplification purposes.

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