Synthesis and Crystal Structure of Solvated Complexes of Copper(II) with Serine and Phenanthroline and Their Solid-State-to-Solid-State Transformation into One Stable Solvate

Abstract

Reactions of copper­(II) sulfate with 1,10-phenanthroline, l-serine, and a base were investigated under different solution-based and mechanochemical synthetic procedures. Six complexes with serine were obtained: [Cu­(l-ser)­(H2O)­(phen)]2SO4­·xH2O (x = 4, 6, or 10; 1·4H 2 O, 1·6H 2 O, and 1·10H 2 O), [Cu­(l-ser)­(H2O)­(phen)]­[Cu­(l-ser)­(CH3OH)­(phen)]­SO4·3H2O­·CH3OH (1·2·3H 2 O­·CH 3 OH), [Cu­(l-ser)­(CH3OH)­(phen)]2SO4­·xCH3OH (x = 2 or 2.5; 2·2CH 3 OH and 2·2.5CH 3 OH), and two without serine: [Cu­(SO4)­(phen)2]­·xH2O (x = 4.5 or 6.75; 3·4.5H 2 O and 3·6.75H 2 O) (phen = 1,10-phenanthroline, l-ser = l-serinato). The X-ray crystal structure analysis of serine-containing complexes revealed extensive hydrogen bonding and π-interactions that link complex cations, sulfate anions, and solvent molecules into three-dimensional architectures. Most of the water/methanol solvent molecules in these porous compounds are found in channels, some in pockets connected to channels, and can be exchanged in vapors of the other solvent. Along with the solvent exchange, the solvent molecule apically coordinated to copper­(II) is also exchanged in some transformations. By neat grinding, all serine-containing complexes transform into 1·6H 2 O. Quantum chemical calculations were done for compounds 1·4H 2 O and 1·6H 2 O in the gas phase and an aqueous (or methanol) surrounding. 1·6H 2 O and 3·4.5H 2 O showed pronounced antiproliferative activity toward human breast and lung tumor cell lines.

Solvent effects on the crystallization and structure of ternary copper(ii) coordination compounds with l-threonine and 1,10-phenanthroline

“…Several Cu coordination compounds with amino acids and heterocyclic ligands have been prepared and some of them have been identified as potential drugs [ 2 , 3 , 4 , 5 , 6 , 7 ] or functional porous materials [ 8 , 9 , 10 ]. Ruiz-Azuara has invented a process to prepare ternary coordination compounds of the type [Cu(N–N)(N–O)]NO 3 , with the N–N ligand corresponding to 4,7-diphenyl-1,10-phenanthroline and the N–O ligand preferably being one of the aminocarboxylates (glycinate, alaninate, isoleucinate, leucinate, serinate and valinate) to be used as anticancerogenic agents for treatment of cancerogenic tumors [ 11 , 12 ].…”

“…In most of the ternary copper coordination compounds with amino acids and 1,10-phenanthroline the copper( ii ) atom is either five- or six-coordinated [ 14 ]. Depending on the amino acid and the presence of a heterocyclic base, different architectures can be formed and, among others, porous structures into which can be incorporated guest molecules such as solvents to produce different solvatomorphs [ 5 , 15 ]. In CSD there are 98 data sets of ternary copper coordination compounds involving aminoacidates and 1,10-phenanthroline.…”

Structural diversity in the coordination compounds of cobalt, nickel and copper with N-alkylglycinates: crystallographic and ESR study in the solid state

“…As a part of our ongoing research on synthesis, structural and magnetic characterization as well as biological activity of molybdenum, cobalt, nickel and copper coordination compounds with amino acids, amides and their derivatives [27][28][29][30][31][32][33][34][35][36][37][38][39] we report synthesis, structural and magnetic characterization of ten novel coordination compounds with N-alkylglycinates. We have performed the reactions of copper(II), nickel(II) and cobalt(II) compounds with N-methylglycine (HMeGly), Nethylglycine-hydrochloride (H 2 EtGlyCl) and N-propylglycinehydrochloride (H 2 PrGlyCl) in aqueous solutions, and characterized the obtained complexes by X-ray diffraction, IR and electron spin resonance (ESR)/electron paramagnetic resonance (EPR) spectroscopy, and thermoanalytical methods (TG/DTA).…”

Cobalt, nickel and copper complexes with glycinamide: structural insights and magnetic properties

“…10 Accurately determined structures of metal complexes with ligands analogous to those of amino acids side chains are useful in protein crystallography for interpretation and validation of protein structural data. [11][12][13][14][15] Amino acids/amino acid derivatives and their metal complexes possess various biological activities such as antiretroviral, 16 antibacterial and antifungal, [17][18][19][20] and antiproliferative effects on tumor cells, 21 with potential applications in biomedicine. Copper coordination compounds, especially those with mixed oxidation states, are also of special interest because of their magnetic properties.…”

“…As a part of our ongoing research on preparation and structural investigation of metal complexes with amino acids and their derivatives, 21,[36][37][38][39] we have prepared various copper(II) and nickel(II) complexes with N-alkyliminodiacetamide. 40 In order to expand our knowledge on the properties of amino acetamide complexes in the solid state, we report synthesis and solid-state characterization (X-ray structural analysis, IR and ESR spectroscopy, TG/DTA analysis) of cobalt, nickel and copper complexes with glycinamide.…”