Synthesis and crystal structure of thiosemicarbazide complexes of nickel(II) and copper(II)

Thiosemicarbazide complexes of nickel(II) [Ni(TSC)₂](HSal)₂ (I) and copper(II) [Cu(TSC)₂](HSal)₂ (Ia) (TSC is thiosemicarbazide and HSal is a salycilate anion), as well as complexes [Ni(TSC)₂](SO₄) · 2H₂O (II) and [Ni(TSC)₃]Cl₂ · H₂O (III), are synthesized and characterized by IR spectroscopy and X-ray diffraction. Monoclinic crystals I and Ia are isostructural; space group P2₁/n, Z = 2. Crystals II are monoclinic, space group P2₁/m, Z = 2. Crystals III are orthorhombic, space group Pbca, Z = 8. In I and Ia, two planar salycilate anions sandwich a planar centrosymmetric [Ni(TSC)₂]²⁺ cation to form a supermolecule. The cation and anions are additionally bound by hydrogen bonds. Other hydrogen bonds connect supermolecules into planar layers. In structure II, centrosymmetric [Ni(TSC)₂]²⁺ cations are connected by ??-stacking interactions into supramolecular ensembles of a specific type. The ensembles, water molecules, and (SO₄)^2? anions are bound in the crystal via hydrogen bonds. In the [Ni(TSC)₃]²⁺ cation of structure III, ligands coordinate the Ni atom by the bidentate chelate pattern with the formation of five-membered metallocycles. These metallocycles have an envelope conformation unlike those in I and II, which are planar. In III (unlike in analogous complexes), a meridional isomer of the coordination octahedron of the Ni atom is formed. Together with Cl1^? and Cl2^? anions, cations form supermolecules, which are packed into planar layers with a square-cellular structure. The layers are linked by hydrogen bonds formed by crystallization water molecules that are located between the layers.     

Synthesis and crystal structure of a copper(II) 5-sulfosalicylate complex with thiosemicarbazide

The compound [Cu(TSC)₂](H₂SSal)₂ (I) has been synthesized (TSC is thiosemicarbazide, H₃SSal is 5-sulfosalicylic acid) and studied by IR spectroscopy and X-ray crystallography. The crystals of I are triclinic: a = 6.728(2) Å, b = 7.772(1)Å, c = 11.600(6)Å, α = 88.60°, β = 86.68(3)°, γ = 79.22(4)°, V = 594.8(4)ų, Z = 2, space group \(P\bar 1\). The structural units of the crystal are the centrosymmetric [Cu(TSC)₂]²⁺ cation, in which the Cu atom is in a square-planar coordination formed by the bidentate chelating (N,S) TSC ligands, and (H₂SSal)^? anions (Cu(1)-N(3), 2.013(3) Å; Cu(1)-S(1), 2.275(1) Å). The coordination polyhedron of the Cu(1) atom is completed to a prolate tetragonal bipyramid (4 + 2) by Cu-O bonds (2.810(3) Å) of the sulfate moieties of both anions, which form together with hydrogen bonds the [Cu(TSC)₂(H₂SSal)₂] supermolecule. The complex cations are packed in layers and alternate with anion-containing layers. Hydrogen bonding and π?π stacking interactions are responsible for formation of supramolecular layer ensembles.     

Reaction of copper(II) cysteinate with thiosemicarbazide: Crystal structure of a complex of copper(II) thiocyanate with thiosemicarbazide

The reaction of copper(II) cysteinate with thiosemicarbazide (TSC) in water was found to yield complex of copper(II) thiocyanate of the [Cu(TSC)₂(SCN)₂] composition, whose crystal structure was determined by X-ray crystallography. Crystals of the complex are triclinic with a = 6.040 Å, b = 7.112 Å, c = 8.276 Å, α = 91.34°, β = 101.72°, Γ = 114.83°, Z = 2, space group \(P\bar 1\). Structural units of the complex are [Cu(TSC)₂]²⁺ centrosymmetric cations and (SCN)^? anions linked by hydrogen bonds (HB), as well as by electrostatic and π-π stacking interactions. The coordination polyhedron of Cu atoms is a square completed to bipyramid; the bonds Cu(1)-N(3), Cu(1)-S(1), and Cu(1)-S(2) are 2.002 Å, 2.303 Å, and 3.015 Å, respectively.     

Coordination Compounds of 3d Metal Biurates with Thiosemicarbazide

Coordination compounds of biurates with thiosemicarbazide [Mn(HL)₂](Urat)₂(H₂O)₂, [Co(HL)₃](Urat)₃(H₂O)₃, [Ni(HL)₂](Urat)₂(H₂O)₂, and [Ni(HL)₂](Urat)₂(H₂O)₄, where HL is thiosemicarbazide, and Urat is the anion of uric acid dissociated by the first step, were synthesized. The physicochemical properties and structures of the compounds were studied by IR and diffuse reflection spectroscopies, magnetochemistry, and DTA.     

Complexation of <Emphasis Type="Italic">d</Emphasis>-Metal Glycinates and Glycylglycinates with 4-Phenylthiosemicarbazide

The complexation of cobalt(III), nickel(II), copper(II), and zinc(II) glycinates and glycylglycinates with 4-phenylthiosemicarbazide was studied.     

Synthesis and crystal structure of diaquadibenzoatobis(nicotinamide)nickel(II)

A coordination compound of nickel(II) benzoate with nicotinamide [Ni(C₆H₅COO)₂(L)₂(H₂O)₂] (I) (L is nicotinic acid amide) is synthesized and studied by IR spectroscopy. Its crystal structure is solved by X-ray crystallography. The crystals of compound I are monoclinic: a = 7.152 Å, b = 18.266 Å, c = 10.341 Å, β = 109.24°, V = 1275.4 ų, Z = 2, space group P2₁/c. Structural units of a crystal of I are centrosymmetric octahedral complex molecules. The coordination environment of the Ni atom contains two O atoms (Ni-O(1) 2.066(2) Å) and two N atoms (Ni-N(1) 2.091(2) Å) of the monodentate-coordinated benzoate anions and nicotinamide molecules, respectively, as well as two O atoms of the H₂O molecules (Ni-O(1w) 2.110(2) Å).     

Some properties of 1-oxo-4-hydroxypyridazino[4,5-b]quinoxaline

The dissociation constants of 1-oxo-4-hydroxypyridazino[4,5-b]quinoxaline were measured by potentiometric titration. It is shown that this compound is a dibasic acid. Its reaction with organic bases, acids, alkalis, and oxidizing agents was studied. Its aminomethylation, hydroxymethylation, and cyanoethylation were also investigated.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 402–406, March, 1977.     

Coordination Compounds of Cobalt(II), Nickel(II), and Zinc(II) Malonates and Phthalates with Benzohydrazide

Benzohydrazide complexes of cobalt(II), nickel(II), and zinc(II) malonates and phthalates were synthesized and characterized by chemical analysis, IR spectroscopy, diffuse reflectance spectroscopy, and thermogravimetry.     

Synthesis,Crystal, and Molecular Structure of bis(Thiosemicarbazide)Nickel(II) 1,5-Naphthalene Disulfonate Dihydrate Complex [Ni(Tsc)<Subscript>2</Subscript>](1,5-Nds) · 2H<Subscript>2</Subscript>O

Complex [Ni(Tsc)₂](1.5-Nds) · 2H₂O (I), where Tsc = thiosemicarbazide, NH₂NHC(=S)NH₂; 1,5-Nds^2– is double deprotonated anion of 1,5-naphthalene disulfonic acid \(\rm{CH_{10}H_6(SO_3)_2^{2-}}\) was synthesized, characterized by IR spectroscopy, and studied by thermogravimetry and X-ray diffraction. Crystal I is built of complex cations [Ni(Tsc)₂]²⁺, anions (Nds)^2–, and crystallization water molecules. The Ni atom is coordinated along the vertices of the trans-square by two sulfur atoms and two nitrogen atoms of two bidentate chelating ligands Tsc. The structural units of crystal I are joined by a branched network of N–H···O and O–H···O hydrogen bonds with the participation of donors, namely, the hydrogen atoms of two NH₂ groups and the NH group of complex cation [Cu(Tsc)]²⁺ and the H atoms of water molecules, and acceptors, namely, oxygen atoms of the sulfate group of anion 1,5-Nds^2– and solvate water molecules.     

Onium salts of sulfur-containing oxyanions resulting from reaction of sulfur(IV) oxide with aqueous solutions of 1,2-diamines and morpholine

Reaction products have been isolated from SO₂–L–H₂O–О2 systems (L = ethylenediamine, N,N,N′,N′-tetramethylethylenediamine, piperazine, and morpholine) as onium salts [H₃NCH₂CH₂NH₃]SO₄, [(CH₃)₂NHCH₂CH₂NH(CH₃)₂]SO₄, [(CH₃)₂NHCH₂CH₂NH(CH₃)₂]S₂O₆ ? H₂O, [C₄H₈N₂H₄]SO₃ ? H₂O, [C₄H₈N₂H₄]S₂O₆, [C₄H₈N₂H₄]SO₄ ? H₂O, [O(C₂H₄)₂NH₂]₂SO₄ ? H₂O. The prepared compounds have been characterized by X-ray diffraction analysis, X-ray powder diffraction, IR and mass spectroscopy.