First-principles calculations of the structural and electronic properties of Cu3MN compounds with M = Ni,Cu, Zn,Pd, Ag,and Cd

We have performed accurate ab initio total energy calculations using the full-potential linearized augmented plane wave (FP-LAPW) method to investigate the structural and electronic properties of copper-transition metal nitrides. In its ground state, Cu₃N crystallizes in an anti-ReO₃ type cell and it is a semiconductor material with a small indirect gap. In this paper, we report a study of Cu₃MN compounds with M = Ni, Cu, Zn, Pd, Ag, and Cd. In the calculations, we have used the same anti-ReO₃ type cell of Cu₃N, but with the extra transition metal atom at the center of the cube. In particular, our calculated lattice parameters for copper nitride (a = 3.82 Å) and copper palladium nitride (a = 3.89 Å) are in excellent agreement with the experimental values of a = 3.807 Å and a = 3.86 Å, respectively. In all the cases we have studied, the addition of the transition metal atom modifies the electronic structure of Cu₃N, turning all copper-transition metal nitrides into metals.     

Copper(II)–malonato coordination frameworks with ethanolammonium cations. Synthesis,spectral, thermal and structural characterization of trans-[Cu(mal)2(meaH)2] and {(deaH)2[Cu(μ-mal)2]·H2O}∞ (meaH=monoethanolammonium,deaH=diethanolammonium and mal=malonate)

Two isomorphous malonato–copper(II) complexes, [Cu(mal)₂(meaH)₂] and {(deaH)₂[Cu(μ-mal)₂]·H₂O}_∞ (meaH=monoethanolammonium, deaH=diethanolammonium and mal=malonate), have been prepared and characterized by elemental analyses, IR, UV–vis, magnetic measurements and single crystal X-ray diffraction. The mononuclear complex crystallizes in the monoclinic space group P2₁/n, with a=8.6630(8) Å, b=7.5122(5) Å, c=11.4390(10) Å, β=95.530(7) and Z=2. The polymeric malonato-bridged copper(II) complex crystallizes in the monoclinic space group P2₁/c, with a=26.5169(14) Å, b=8.2544(5) Å, c=9.5243(5) Å, β=96.256(4) and Z=4. The monomeric complex consists of individual units in which copper(II) sits on the inversion center and is octahedrally coordinated by two bidentate mal and two monodendate meaH ligands. The structural units are joined into the framework by the system of hydrogen bonds. The polymeric complex composed of two-dimensional chains containing the mal bridged [Cu(mal)₂]²⁻ ions and each mal ligand simultaneously exhibits chelating bidentate (at one copper atom) and bridging (at the adjacent copper atom) coordination modes. The intrachain Cu1⋯Cu2 separation is 6.302(4) Å. The deaH cations are not coordinated to copper(II) and occupy the voids of the frame work, together with the lattice water molecules. The IR spectra and thermal decompositions of both complexes are described in detail.     

Crystal and molecular structure of complex compound (C5H5)2Re(H)Cu(μ-I)2CuRe(H)(C5H5)2: A first direct proof of the formation of the Cu(I)Cu(I) bond

The structure of the bimetallic dimer complex [(η⁵-C₅H₅)₂Re(H)CuI]₂ has been investigated. The crystals are monoclinic: a = 16.070(4) Å, b = 7.788(2)Å, c = 17.439(5) Å; b = 96.62(2)°; the space group I2/a; z = 4. The bond between rhenium and copper atoms (2.60 Å) is of the donor-acceptor type; dimerization occurs by the way of formation of the double bridge CuI₂Cu and the direct inter-metal bond CuCu(2.55 Å). The hydride hydrogen atom is the terminal one. The cyclopentadienyl rings form a bent sandwich with the angle between the ring centres and rhenium atom being equal to 158°. It is suggested that the CuCu inter-metal bonding takes place on account of the transition of the non-bonding d-electrons of copper atoms to a high-spin state.     

The synthesis and crystal structure of α-perthionaphthoatopyridinecopper(I) dimer Cu2(α-C10H7CSS2)2(Py)2

The title compound has been synthesized by the reaction of α-dithionaphthoic acid with CuCl₂ in pyridine or by recrystallizing Cu₄(α-C₁₀H₇CSS₂)₄ ? 1/2CS₂ in a mixture of pyridine and alcohol. The structure of the title compound is determined by a single-crystal X-ray diffraction analysis. The crystal belongs to triclinic space group with unit cell parameters: a=7.085(2)Å, b= 8.672(3)Å and c=13.598(5)Å; a=92.40(3)°, β=102.59(4)° and γ=105.67(4)°; V=780.6Ų; Z=1. The structure was refined to R=0.058 for 2390 reflections. The molecule of the title compound sits on a center of symmetry. The shorter Cu—Cu bond length (2.606Å) shows considerable interaction between copper atoms. If the Cu—Cu interaction is ignored, the neighbouring S and N atoms are coordinated to copper atom in a configuration of distorted tetrahedron.     

Über ein Mangan-Quecksilber-Nitrid mit Perowskitstruktur

A complex nitride with a perovskite-type structure has been prepared by reacting ammonia with manganese amalgam. The composition was found to be Mn_3+xHg_1?xN with an appreciable range of homogeneity. At the composition forx=0,10 the lattice parameter isa=4,069 Å.     

Synthesis and crystal structure of the copper(II) valerate complex with nicotinamide

A coordination compound of copper(II) valerate with nicotinamide, [CuL(C₄H₉COO)₂]₂ (I), has been synthesized, and its crystal structure has been determined by X-ray crystallography. The crystals of I are triclinic: a = 9.1245(9) Å, b = 9.8572(6) Å, c = 11.0944(9) Å, α = 73.51(1)°, β = 79.917(6)°, γ = 72.161(7)°, Z = 2, space group $P\bar 1$ . In the centrosymmetric binuclear molecule of I, the copper atoms (Cu...Cu′, 2.621 Å) are linked through four bidentate chelating valerate ligands (av., Cu-O 1.969 Å). The coordination polyhedron of the Cu atom is a tetragonal pyramid with the nitrogen atom of the pyridine ring in the apical position at a longer distance (Cu-N, 2.190 Å).     

Synthesis and structure of Cu3PO4[1,2,4-triazole]2OH with a hybrid layered structure: A new organically templated copper (II) hydroxyphosphate

A new layered copper hydroxyphosphate Cu₃PO₄(1,2,4-triazole)₂OH was synthesized by the mild hydrothermal route and the crystal structure was solved by the single crystal X-ray diffraction method. This compound crystallizes in the monoclinic space group P2₁/a with: a = 10.1456(5) Å, b = 7.8756(4) Å, c = 12.9008(6) Å, β = 111.64(2)°, V = 960.86(8) Å³, Z = 4, D_x = 3.033 g cm^?3. The Cu(II) atoms are embedded in deformed square-pyramidal (Cu1 and Cu3) or octahedral (Cu2) sites made of N and O (or OH) atoms. Both Cu1 and Cu2 polyhedra form dimers connected one to each other, via OH groups, in ribbons which built a bidimensional (001) layer through PO₄ connections. The Cu3 polyhedra built a (001) double-sheet layer through triazol connections. These layers are bridged by triazole and PO₄ groups along the c-direction yielding a lamellar arrangement. Its structural analysis evidences a two-dimensional character for this copper hybrid material which could begin a new series of MOF compounds.     

Distorted tetrahedral copper(I)′complexes of 2,2′bi-4,5-dihydrothiazine and 2,2′-bi-2-thiazoline

The copper(I) complexes [Cu(btz)₂](BPh]₄(I) and [Cu₂(bt)₄][ClO₄]₂ (II) have been prepared (btz = 2,2′-bi-4,5-dihydrothiazine and bt = 2,2′-bi-2-thiazoline). Crystals of (I) are orthorhombic with a = 10.927(8), b = 11.743(8), c = 15.000(6) A, Z = 2, spacegroup P2₁2₁2. Crystals of (II) are monoclinic with a = 21.928(11), b = 11.925(8), c = 14.716(11) A, β = 103.6(1), Z = 8, spacegroup C2/c. 2121 and 2204 independent reflections have been measured on a diffractometer and the structures refined R 0.061 to R 0.063 respectively. In the cation of (I) the two btz ligands are coordinated via the α-di-imine groups (Cu-N 2.010(6), 2.024(6)Å). The resulting CuN₄ coordination geometry is a flattened tetrahedron with a dihedral angle of 68.9° between the two “CuN₂” planes. It is suggested that this distortion is an intrinsic property of the molecule associated with metal-to-ligand d_π-p_π* charge transfer rather than a consequence of lattice packing effects. In the dimeric cation (II), each copper(I) ion is bonded to the α-di-imine group of one bt molecule (A) but with appreciably different CuN bond lengths (2.277(6), 1.999(5)Å), to one nitrogen atom of a second ligand molecule (B) in the trans configuration (CuN 1.961(5)Å) and to one sulphur atom (CuS 2.428(2)Å) of a third ligand molecule (C). The coordination geometry is a very distorted tetrahedron if a very weak interaction (Cu…S 3.039(2)Å) with a sulphur atom of ligand B is discounted. It is suggested that the different structure arise from the different “bites” of the two ligands.     

Structural chemistry of Sr3Cr2WO9, Ca3Cr2WO9, and Ba3Cr2WO9

We have studied the preparation and crystallographic structure of three perovskite-type compounds: Sr₃Cr₂WO₉, cubic, the lattice parameter of which is a = 7.812Å; Ca₃Cr₂WO₉, tetragonal, the lattice parameters of which are a = 5.408 Å and c = 7.635Å; and Ba₃Cr₂WO₉, hexagonal, the lattice parameters of which are a = 5.691 Å and c = 13.957Å. We have compared these three structures and shown the relationship between the dimensions of the alkaline-earth metal and the existence of the different structures.     

A new binuclear germanium(IV) and copper(II) complex with 1,3-diamino-2-propanoltetraacetic acid: Crystal and molecular structure of [(H2O)(OH)Ge(μ-Hpdta)Cu(H2O)] · 3H2O

A heteronuclear germanium(IV) and copper(II) complex with 1,3-diamino-2-propanoltetraacetic acid (H₅Hpdta) has been synthesized for the first time. The compound has been characterized by elemental analysis, X-ray diffraction, thermogravimetry, and IR spectroscopy. The structure of the complex [(H₂O)(OH)Ge(μ-Hpdta)Cu(H₂O)] · 3H₂O (I) has been determined by single-crystal X-ray diffraction. The crystals of I are monoclinic, a = 1 5.327(4) Å, b = 11.626(3) Å, c =21.058(3) Å, β = 96.35(2)°, V = 3729.2(2) ų, Z = 8, space group C2/c, R1 = 0.0551 on 3090 reflections with I > 2σ(I). The structural units of the crystal of I are binuclear complex molecules [(H₂O)(OH)Ge(μ-Hpdta)Cu(H₂O)] and crystal water molecules. The germanium and copper atoms are linked by the bridging oxygen atom of the deprotonated isopropanol group of the Hpdta^5? ligand (Ge-O, 1.843(3) Å; Cu-O, 2.221(3) Å). The coordination spheres of the Ge and Cu atoms contain each one nitrogen atom (Ge-N, 2.090(4) Å; Cu-N, 2.000(4) Å) and two carboxyl oxygen atoms from four acetate arms of the heptadentate Hpdta^5? ligand (av. Ge-O, 1.909(3) Å; Cu-O, 1.948(3) Å). The coordination polyhedron of the Ge atom is completed to a distorted octahedron by the oxygen atoms of the terminal hydroxy group (Ge-O, 1.786(3) Å) and a water molecule (Ge-O, 1.904(3)Å). The coordination polyhedron of the copper atom is completed to a prolate tetragonal pyramid (4 + 1) by the oxygen atom of a water molecule in the equatorial position (Cu-O, 1.955(4) Å) and the bridging O(11) atom (Hpdta^5?) in the apical position. Binuclear molecules are linked pairwise in a head-to-head manner via double Cu-O(2) bridges to form the centrosymmetric tetranuclear supramolecule {[(H₂O)(OH)Ge(μ-Hpdta)Cu(H₂O)]}₂. The coordination of the Cu atom is completed by the weak Cu-O(2A) contact (3.303 Å) to an asymmetrically elongated tetragonal bipyramid (4 + 1 +1). In the crystal, the complex molecules and crystal water molecules are combined by a system of hydrogen bonds into a three-dimensional framework.     

Study of the molecular and crystal structure of a new coordination polymer of copper(II) nitrate with 4,4,10,10-tetramethyl-1,3,7,9-tetraazospiro[5.5]undecane-2,8-dione

A coordination polymer {[Cu(C₁₁H₂₀N₄O₂)₂(H₂O)]²⁺·2(NO ₃ ^? )} _n (I) is synthesized and analyzed using single-crystal XRD. The crystals are monoclinic: space group P2/c, a = 12.5237(6) Å, b = 7.3310(3) Å, c = 16.8926(8) Å, β = 92.569(4)°, V = 1549.38(13) ų, ρ_calc = 1.47 g/cm³, and Z = 2. The copper atom is in a special position in the second-order axis. The coordination polyhedron of the metal is a trigonal bipyramid. In the axial direction, it is coordinated by two oxygen atoms O(1) of the organic ligand molecules connected by the symmetry operation [?x, y, 0.5-z]; the angle O(1)Cu(1)O(1) ⁱ is 175.16(15)°. In the equatorial direction, the copper atom is coordinated by oxygen atoms O(2) of two ligand molecules connected with the reference molecule by the symmetry operations [?x, y, 0.5-z] and [x, 1-y, ?0.5+z] and the water molecule O(6) in a special position on the twofold axis. The OCuO angles between the equatorial oxygen atoms are 96.80(16)–131.60(8)°, and those between the axial and equatorial atoms are 87.58(8)-91.60(10)°. It is noteworthy that the length of the Cu-O(1) bond (1.955(2) Å) with the axial carbonyl oxygen atom is somewhat shorter than the bond (2.060(3) Å) with the equatorial atom. Nitrate anions are outside the coordination sphere of the metal. The Cu…Cu distance in the polymer is 8.33 Å. To confirm the purity of the sample of I, the powder X-ray pattern is refined by the Rietveld method; the lattice parameters at room temperature are: a = 12.535(4) Å, b = 7.3161(13) Å, c = 16.841(5) Å, β = 92.11(2)°, and V = 1543.4(7) ų.     

Structure and EPR spectra of binuclear copper(II) complexes with acyldihydrazones of benzenedicarboxylic acids and 5-substituted 2-hydroxyacetophenones

Binuclear copper(II) complexes with acyldihydrazones of 1,3- or 1,4 benzenedicarboxylic acid and 5-methyl- or 5-bromo-2-hydroxyacetophenone in which coordination polyhedra are connected by an aromatic bridge have been synthesized and studied. The structure of the copper(II) complex with diacylhydrazone of isophthalic acid and 2-hydroxy-5-methylacetophenone (H₄L) of composition [Cu₂L · 3Py] was studied by X-ray diffraction. The crystals are monoclinic: a = 12.1996(12) Å, b = 17.7295(17) Å, c = 17.9339(17) Å, β = 109.7450(10)°, space group P2₁/n, Z = 4. The complex is of the “dimer of dimers” type and contains two binuclear subunits that bind together into a centrosymmetric dimer owing to the coordination of the copper cation to the phenoxyl oxygen atom of a neighboring binuclear molecule to form the Cu₂O₂ moiety, in which the copper atoms are 3.409 Å apart. The distance between the copper(II) cations in the binuclear subunit is 8.56 atoms (2N + O) of the doubly deprotonated acylhydrazone moiety and the nitrogen atom of the pyridine molecule. One of the copper cation is additionally coordinated to an extra pyridine molecule so that its coordination sphere is completed to a tetragonal pyramid. The second copper atom is involved in additional interaction with the phenoxyl oxygen atom of the neighboring molecule. The EPR spectra of solutions of the binuclear complexes show an isotropic signal of four HFS lines (g _o = 2.065–2.143, a _Cu = 52.1–66.5 × 10^?4 cm^?1) typical of mononuclear copper(II) complexes.     

Structure of A Coordination Polymer [Cu(En)<Subscript>2</Subscript>CrO<Subscript>4</Subscript>]<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>

The crystal structure of [Cu(En)₂CrO₄]_n (En is ethylenediamine) is determined: a = 14.7359(4) Å, b = 9.8083(3) Å, c = 14.2664(4) Å, V = 2061.98(10) ų, space group Cmce, Z = 8, d_x = 1.931 g/cm³. It is demonstrated that the studied phase is isostructural with [Сu(Еn)₂SO₄]_n. A pseudotetragonal copper atom coordination (Cu–N 2.0204 Å and 2.0244 Å, ∠N–Cu–N 84.73°) is completed to distorted octahedral by two oxygen atoms of chromate anions (Cu–O 2.433 Å and 2.380 Å).     

Crystal structure of [Cu2(Edta)(Py)2(H2O)2] · 2H2O and [Cu(Im)6]{;Cu(Im)4[Cu(Edta)(Im)]2} · 6H2O, Products of the interaction of (Ethylenediaminetetraacetato)diaquadicopper(II) with pyridine and imidazole

The crystals of [Cu₂(Edta)(Py)₂(H₂O)₂] · 2H₂O (I) and [Cu(Im)₆]{;Cu(Im)₄[Cu(Edta)(Im)]₂} · 6H₂O (II) were isolated as a result of the reaction of an aqueous solutions of Cu₂(Edta) · 4H₂O with pyridine or imidazole, respectively. The crystals were studied by X-ray diffraction. The crystals of I are monoclinic, a = 12.682 Å, b = 6.788 Å, c = 14.834 Å, β = 91.44°, Z = 2, space group P2₁/n. The crystals of II are triclinic, a = 9.118 Å, b = 14.889 Å, c = 15.130 Å, α = 72.59°, β = 72.94°, γ = 82.54°, Z = 1, space group P{ie241-1}. In the centrosymmetric binuclear complex molecule of I, an N atom and two O atoms of the Edta ligand are coordinated to each Cu atom (Cu-N, 2.046 Å; Cu-O, 1.941 and 1.954 Å). The N atom of the pyridine molecule (Cu-N, 1.993 Å) completes the base of an elongated tetragonal pyramid (4 + 1) with the O atom of the H₂O molecule in the apex (Cu-O(w), 2.244 Å). The crystals of II are built of centrosymmetric complex cations [Cu(Im)₆]²⁺ (Cu(1)-N, 2.469, 2.021, and 2.056 Å), centrosymmetric trinuclear complex anions {;Cu(Im)₄[Cu(Edta)(Im)]₂}^2?, and crystal water molecules. In the anion, the central fragment [Cu(Im)₄]²⁺ (Cu(2)-N, 1.985 and 2.023 Å) is bonded to two peripheral complexes [Cu(Edta)(Im)]^2? through atoms O of the Edta ligand (Cu(2)-O, 2.615 Å). In the [Cu(Edta)(Im)]^2? fragment of the complex anion, the Cu(3) atom is bonded to the Edta ligand through the two N atoms and three O atoms (Cu(3)-N, 1.970 and 2.071 Å; Cu(3)-O, 1.966, 1.969, and 2.238 Å) and with the imidazole molecule, through an N atom (Cu(3)-N, 2.397 Å). The coordination polyhedra of the three copper atoms (Cu(1)-Cu(3)) in the structure of II are elongated tetragonal bipyramids (4 + 2). In the structures studied, Edta^4? is a hexadentate chelating/bridging ligand. However, the coordination mode of the ligand in these structures is different: in the binuclear complex I, the Edta ligand is coordinated to each Cu atom through an N atom and two O atoms with the formation of two chelate rings (symmetric (trans) coordination mode), whereas, in the trinuclear complex II, the Edta ligand is coordinated to the Cu(2) atom through an O atom and to the Cu(3) atom through the two N atoms and three O atoms with the formation of three chelate rings (asymmetric (cis) coordination mode).     

Crystal structure oftrans-bis-(2,2,6-trimethyl-6-methoxy-5-iminoheptan-3-onato)copper(II)

A new volatile N,O-chelate complex of Cu(II) containing a methoxy group was studied by X-ray diffractometry (KUMA automatic diffractometer, MoK_a radiation for single crystals and DRON-UM1, CuK_a radiation for polycrystals). The structure is molecular and consists of transcomplexes of bis-(2,2,6-trimethyl-6-methoxy-5-iminoheptan-3-onato)copper(II). The structure was refined in an anisotropic approximation using 2426 independent reflections to R = 0.048. Crystal data: a = 13.426(2), b = 9.566(2), c = 19.562(4) Å, Β = 90.72?, space group F2₁ /n, V = 2512.2(8) ų, Z = 4, d_calc = 1216 g/cm³. The squareplanar environment of the copper atom with distances Cu-O = 1.938 and Cu-N = 1.912 Å is completed to pyramidal by interaction with the oxygen atom of one methoxy group of the neighboring molecule at a distance of Cu...O = 2.81 Å.     

Single crystal growth and structural characterization of four complex uranium oxides: CaUO4, β-Ca3UO6, K4CaU3O12, and K4SrU3O12

Single crystals of complex uranium oxides, CaUO₄, β-Ca₃UO₆, K₄CaU₃O₁₂ and K₄SrU₃O₁₂ were grown from carbonate melts. The crystal structures of the four uranates were determined by single crystal X-ray diffraction. CaUO₄ crystallizes in the hexagonal space group R-3m, with lattice parameters a = 6.2570(7) Å and α = 36.04(2)°. The U⁶⁺ atom in CaUO₄ is 8-coordinate and exhibits hexagonal bipyramidal geometry with six long and two short U–O bonds, typical of a uranyl species. β-Ca₃UO₆ forms in the monoclinic space group P2₁/n, with lattice parameters a = 5.728(1) Å, b = 5.956(1) Å, c = 8.298(2) Å, and β = 90.55(3)°, and adopts a distorted double perovskite structure. K₄CaU₃O₁₂ and K₄SrU₃O₁₂ crystallize in the cubic space group Im-3m with lattice parameters a = 8.483(1) Å and a = 8.582(1) Å, respectively. In all three perovskite-type oxides, the U(VI) cation is located in an octahedral coordination environment and exhibits typical uranyl geometry with four long and two short U–O bonds.     

Die Struktur der Komplexnitride NbCrN und Ta1−x Cr1+x N

The crystal structure of the isotypic compounds NbCrN and Ta_1?x Cr_1+x N has been determined from X-ray powder patterns. The tetragonal unit cell contains 12 atoms and belongs to the space group P4bm. The lattice parameters are for NbCrN:a=4.283 Å,c=7.360 Å, for Ta_0.8Cr_1.2Na=4.249 Å,c=7.334 Å. The structure is characterized by relatively close packed double layers of Nb(Ta)-atoms and Cr-atoms parallel to the base plane. The nitrogen atoms are within the octahedral interstitial sites of the niobium(tantalum) double layer.     

Synthesis and crystal structures of two Schiff base copper(II) complexes derived from 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol

A centrosymmetric mononuclear copper(II) complex, [Cu(L¹)₂] (I), and a phenolate oxygen-bridged dinuclear copper(II) complex, [Cu₂(L²)₄] (II) (HL¹ = 4-chloro-2-[(2-morpholin-4-ylethylimino)methyl]phenol, HL² = 4-chloro-2-(cyclohexylimino-methyl)phenol), were synthesized and characterized by elemental analyses, IR, and single crystal X-ray diffraction. The crystal of I is monoclinic: space group {ITP}2₁/n, a = 13.396(3), b = 5.339(1), c = 19.740(4) Å, β = 108.64(3), V = 1337.8(5) ų, {ITZ} = 2. The crystal of II is monoclinic: space group P2₁, a = 9.157(2), b = 22.715(4), c = 12.169(2) Å, = 95.28(3), {ITV} = 2520.4(8) Å3, {ITZ}= 2. The Cu atom in I, lying on the inversion center, is four-coordinate in a square planar geometry with two phenolate oxygen and two imine nitrogen atoms. Each Cu atom in II is five-coordinate in a square pyramidal geometry with two phenolate oxygen and two imine nitrogen atoms from two L² ligands defining the basal plane and with one phenolate oxygen atom of another L² ligand occupying the apical position.     

Crystal structure and thermal decomposition mechanism of a 5-aminotetrazole copper(II) complex

A novel 5-aminotetrazole mixed ligands complex of formula [Cu(PTS)₂(ATZ)₂(H₂O)₂] (C₁₆H₂₄CuN₁₀O₈S₂, PTS = p-toluenesulfonate, ATZ = 5-aminotetrazole) has been obtained by the reaction of 5-aminotetrazole with copper acetate and p-toluenesulfonic acid on heating in water. It was characterized by elemental analysis, FT-IR spectroscopy, and X-ray single crystal diffraction. The compound crystallizes in monoclinic system, space group P2₁/c, Z = 2, a = 14.079(4) Å, b = 6.088(3) Å, c = 14.632(4) Å, β = 105.268(4)°, V = 1209.8(5) Å³. The central copper(II) cation is coordinated by two N atoms and four O atoms from two ATZ ligands, two water molecules and two p-toluenesulfonate ions to form a six-coordinated and distorted octahedral structure. Neutral ATZ is coordinated in the monodentate mode by the N(4) atom. The sulfonate group of the PTS ligand remains weak-coordinated modes and forms a number of hydrogen bonds with water molecule ligands and ATZ ligands. A supramolecular framework is connected by electrostatic interaction, weak coordinated bonding, hydrogen-bonding, and π–π interaction. The thermal decomposition mechanism of the title compound was predicted based on DSC, TG-DTG, and FT-IR analyses. Thermolysis of ATZ and its several derivatives is compared.     

A study of the structure and properties of mixed-ligand Cu(II) complexes with hexafluoroacetylacetone and methyl-, phenyl-ketoimines

The synthesis and X-ray single crystal study of two mixed-ligand Cu(II) complexes are performed: (CH₃C(NCH₃)CHC(O)CH₃)(CF₃C(O)CHC(O)CF₃)Cu (1) (space group P2₁/c, a = 7.0848(12) Å, b = 17.854(3) Å, c = 11.837(2) Å, β = 100.495(6)°, V = 1472.4(4) ų, Z = 4), (CH₃C(NC₆H₅)CHC(O)CH₃)· (CF₃C(O)CHC(O)CF₃)Cu (2) (space group P-1, a = 9.1119(4) Å, b = 9.6954(4) Å, c = 11.1447(6) Å, α = 113.784(2)°, β = 92.383(2)°, γ = 95.402(2)°, V = 893.52(7) ų, Z = 2). The structures are molecular, formed from neutral mixed-ligand copper complexes. The central copper atom has the (3O+N) coordination environment with average Cu-O distances of 1.948 Å and Cu-N of 1.932 Å; the chelate O-Cu-N angle (average) is 94.0°. In the structures, the complexes are linked into dimeric associates with Cu…Cu distances of 3.197 Å (for 1) and 3.246 Å (for 2). The volatility of mixed-ligand complexes 1 and 2 is in between of that of the starting homo-ligand complexes.