Sulfanilamide-containing coordination compounds of Cu(II) with isatin and N-methylisatin thiosemicarbazones

Isatin (L¹) and N-methylisatin (L²) β-thiosemicarbazones react in ethanol with Cu(II) chloride and bromide in the presence of sulfanilamide (Streptocid, Sf¹), N-acetylsulfanilamide (Sulfacyl, Sf²), Norsulfazole (Sf³), Aethazolum (Sf⁴), and Sulfadimesine (Sf⁵) to form coordination compounds Cu(Sf^1–5)L^1–2X₂ · nH₂O (X = Cl, Br; n = 2–5). All the complexes have a monomeric structure. Thiosemicarbazones L¹ and L² in these complexes are tridentate O,N,S ligands, and sulfanilamides Sf^1–5 are monodentate ligands. Thermolysis of the substances involves the steps of dehydration (70–95°C) and complete decomposition (410–530°C).     

Coordination compounds of copper and nickel with N,N′-[4,4′-(perfluoro-1,4-phenylene)bis(oxy)bis(4,1-phenylene)]-bis[2-(pyridin-2-ylmethylidene)hydrazinecarbothioamide] and its derivatives

N,N′-[4,4′-(Perfluoro-1,4-phenylene)bis(oxy)bis(4,1-phenylene)]bis[2-(pyridin-2-ylmethylidene)-hydrazinecarbothioamide] as well as its methyl and phenyl derivatives react with copper and nickel chlorides in ethanol to form coordination compounds. In the products, the hydrazinecarbothioamides act as doubly deprotonated bridging ligands. The prepared complexes have been found to inhibit in vitro the growth and propagation of the myeloid human leukemia HL-60 cancer cells at the 10^?5–10^?7 mol/L concentration.     

CRYSTAL STRUCTURES OF [N′-(2- OXIDOBENZYLIDENE)-N-(PROP-2-EN-1-YL)- CARBAMOHYDRAZONOTHIOATO(2-)](1,10- PHENANTHROLINE)COPPER AND [N′-(2- OXIDOBENZYLIDENE)-N-(PROP-2-EN-1-YL)- CARBAMOHYDRAZONOTHIOATO(2-)](2,2′- BIPYRIDINE)COPPER HEMIHYDRATES

Journal of Structural Chemistry - The crystal structures and biological properties of [N′-(2-oxidobenzylidene)-N-(prop-2-en-1-yl)-carbamohydrazonothioato(2-)](1,10-phenanthroline)copper...     

Coordination compounds of cobalt,nickel, copper,and zinc with 2-bromo-3-phenylpropenal benzoylhydrazone and thiosemicarbazone

By X-ray structural analysis the crystal structure of 2-bromo-3-phenylpropenal benzoylhydrazone (HL) was determined. The molecule is not flat. In the crystal the HL molecules form infinite chains with reciprocal van der Waals interaction. 2-Bromo-3-phenylpropenal hydrazone (HL) and thiosemicarbazone (HL′) react with cobalt, nickel, copper and zinc chlorides, nitrates and acetates to form coordination compounds of the composition Cu(HL)(L)₂ [HL = C₆H₅-CH=CBr-CH=N-NH-C(O)-C₆H₅], MX₂·2 HL′·nH₂O [M = Co, Ni, Cu, Zn; X = Cl, NO₃, HL′ = C₆H₅-CH=CBr-CH=N-NH-C(S)-NH₂; n = 0–3], MX₂·HL·n H₂O [M = Ni, Cu; n = 0, 1], and ML′₂·nH₂O [M = Co, Ni, Zn; n = 0–3]. The same reactions in the presence of amines (A = C₅H₅N, 2-CH₃C₅H₄N, 3-CH₃C₅H₄N, 4-CH₃C₅H₄N) afford complexes of the composition CuALCl and MALX·n H₂O [M = Cu, Ni; X = Cl, NO₃; n = 0–2]. Structure of the coordination node in the amine-containing copper derivatives is polynuclear, in complexes Cu(HL)(L)₂ is octahedral, in other compounds it is tetrahedral. The azomethines (HL and HL′) in these complexes behave as bidentate N,O and N,S ligands. Thermolysis of the complexes includes a step of dehydration (60–90°C) and complete thermal decomposition (430–590°C).     

Crystal structures of 3-phenylpropenal thiosemicarbazone and its nickel and zinc chelates

3-Phenylpropenal thiosemicarbazone hydrate C₆H₅-HC=CH-CH=N-NH-C(S)-NH₂ · H₂O (HL · H₂O, I) and two chelates [Ni(L)₂] · nCH₃OH (II) and [Zn(L)₂] (III) are studied by X-ray diffraction. The crystals of I are orthorhombic: a = 6.227(1) Å, b = 7.763(2) Å, c = 25.585(5) Å, β = 90°, space group P2₁2₁2₁, Z = 4, R = 0.0426. A nonplanar molecule of I has an E conformation. The crystals of II are triclinic: a = 6.551(2) Å, b = 10.752(3) Å, c = 10.885(3) Å, α = 64.751(5)°, β = 82.753(5)°, γ = 89.857(5)°, space group, Z = 1, R = 0.0661. In a centrosymmetric molecule of II, the central atom coordinates two deprotonated ligands L through the immine nitrogen atom and thioamide sulfur atom at the vertices of a distorted square. The crystals of III are monoclinic: a = 25.342(2) Å, b = 9.150(2) Å, c = 21.340(3) Å, α = 90°, β = 111.84(2)°, γ = 90°, space group C2/c, Z = 8, R = 0.0556. In a molecule of complex III, two deprotonated bidentate ligands L are coordinated by the zinc ion through the immine nitrogen atoms and thioamide sulfur atoms to form a distorted tetrahedron at the central atom. In both II and III, ligand L after coordination by the metal ion changes the E conformation with respect to the N(1)-C(2) bond for the Z conformation. In crystals I-III, molecules are packed to form infinite layers parallel to the planes (001) and (010).     

Crystal structures of salicylideneguanylhydrazinium chloride and its copper(II) and cobalt(III) chloride complexes

The crystal structures of salicylideneguanylhydrazinium chloride hydrate hemiethanol solvate (I), salicylideneguanylhydrazinium trichloroaquacuprate(II) (II), and bis(salicylideneguanylhydrazino)cobalt(III) chloride trihydrate (III) are determined using X-ray diffraction. The structures of compounds I, II, and III are solved by direct methods and refined using the least-squares procedure in the anisotropic approximation for the non-hydrogen atoms to the final factors R = 0.0597, 0.0212, and 0.0283, respectively. In the structure of compound I, the monoprotonated molecules and chlorine ions linked by hydrogen bonds form layers aligned parallel to the (010) plane. In the structure of compound II, the salicylaldehyde guanylhydrazone cations and polymer chains consisting of trichloroaquacuprate(II) anions are joined by an extended three-dimensional network of hydrogen bonds. In the structure of compound III, the [Co(LH)₂]⁺ cations, chloride ions, and molecules of crystallization water are linked together by a similar network.     

Crystal structures of 6-[(2-hydroxy-1,1-bishydroxymethylethylamino)methylene]-2,4-dinitrocyclohexa-2,4-dienone hydrate and complexes of copper(II) chloride and copper(II) nitrate with this ligand

The crystal structures of 6-[(2-hydroxy-1,1-bishydroxymethylethylamino)methylene]-2,4-dinitrocyclohexa-2,4-dienone hydrate L · H₂O (I), chloro-(2-hydroxymethyl-2-methylpropane-1,3-diol-2-iminomethyl-4,6-dinitrophenolo)aquacopper hydrate [Cu(H₂O)(L-H)Cl] · H₂O (II), and (2-hydroxymethyl-2-methylpropane-1,3-diol-2-iminomethyl-4,6-dinitrophenolo)aquacopper nitrate [Cu(H₂O)(L-H)]NO₃ (III) are determined using X-ray diffraction. It is established that the salicylidene fragment of azomethine L in the structure of compound I is in a quinoid tautomeric form. In the crystal, molecules L and water molecules are joined together by hydrogen bonds into two-dimensional layers aligned parallel to the (010) plane. The copper atom in the structure of compound II coordinates the singly deprotonated tridentate molecule L (whose salicylidene fragment is in a benzenoid form), the chlorine ion, and the water molecule. The coordination polyhedron of the central copper atom is a distorted tetragonal pyramid. In the structure of compound III, the polymer chains are formed through the coordination bonds of the copper atom with two oxygen atoms of the amino alcohol fragment of azomethine L of the neighboring complex, which is related to the initial complex by the translation along the x axis. The coordination polyhedron of the central atom is an elongated tetragonal bipyramid. Polymers and nitro groups form a three-dimensional framework through hydrogen bonds.     

Cobalt, nickel, and copper coordination compounds with 3-phenylpropenal benzoylhydrazone

3-Phenylpropenal benzoylhydrazone (HL) reacts with cobalt, nickel, and copper chlorides, nitrates, and acetates to give coordination compounds MX₂ · nH₂O [M = Co, Ni, Cu; X = Cl, NO₃, HL = C₆H₅CH=CHCH=NNHC(O)C₆H₅; n = 0, 2] and ML₂ · nH₂O (M = Co, Ni, Cu; n = 1–3). Complexes MALCI (M = Co, Ni, Cu) were obtained by these reactions in the presence of amines (A = C₅H₅N, 2-CH₃C₅H₄N, 3-CH₃C₅H₄N, 4-CH₃C₅H₄N). All the compounds have a monomeric structure. Azomethine (HL) in them behaves as a bidentate N,O-ligand. Thermolysis of the complexes involves the stages of dehydration (70–90°C), deaquation (145–155°C) or deamination (145–185°C), and complete thermal decomposition (330–490°C).     

Coordination compounds of copper(II) with substituted 3-{[(2-hydroxyphenyl)methylidene]amino}propane-1,2-diols

3-{[(2-Hydroxyphenyl)methylidene]amino}propane-1,2-diol, its 5-chloro-,5-bromo-, 5-nitro-, 3-methoxy derivatives, and 3-{[(2-hydroxynaphthyl-1)methylidene]amino}propane-1,2-diol react with hydrates of copper(II) chloride, bromide and nitrate in ethanol to form coordination compounds Cu(L)X·nH₂O. Template condensation reaction between 3-aminopropane-1,2-diol and 2,3-, 2,4- or 2,5-dihydroxybenzaldehyde in the presence of copper(II) nitrate trihydrate results in similar compounds Cu(L)NO₃·nH₂O. Structure of some of the condensation products was identified by X-ray analysis. Thermolysis of the substances obtained occurs through the dehydration step (70–90°C) and complete thermal decomposition (290–560°C).