Synthesis,characterization and in-vitro antitumour activity of dibutyltin carboxylates involving the perfluorophenyl moiety: Crystal structure of the dimeric bis[(4-fluoro- and pentafluoro-benzoato)di-n-butyltin] oxides

Crystal structure determinations of {[(F₅C₆COO)Bu₂Sn]₂O}₂ and {[(4-F-C₆H₄COO)-Bu₂Sn]₂O}₂ show that the structures are similar and feature central Bu₄Sn₂O₂ units with two Bu₂Sn groups connected by bridging oxygen atoms. Each pair of exo- and endo-cyclic tin atoms is linked by an almost symmetrically bridging carboxylate group, with the two remaining groups attached to the exocyclic tin atom only. Crystals of {[(F₅C₆COO)Bu₂Sn]₂O}₂ are triclinic, space group P1, with unit cell dimensions a = 12.425(3) Å, b = 13.090(5) Å, c = 11.697(3) Å, α = 95.31(3)°, β = 93.28(2)°, γ = 113.01(2)°, V = 1734(1) ų, Z = 1. Crystals of {[(4-F-C₆H₄COO)Bu₂Sn]₂O}₂, are also triclinic, space group PI, a = 12.599(6) Å, b= 25.359(4) Å, c = 11.480(4) Å, α = 91.44(3)°, β = 114.77(3)°, γ=97.43(3)°, V=3289(2) ų, Z=2. The structures were refined to final R= 0.046, R_w = 0.046 for 4312 reflections with I≥ 3.0 σ(l) for {[(F₅C₆COO)Bu₂Sn]₂O}₂ and R=0.061, R_w=0.068 for 4112 reflections with l≥3.0 σ(l for {[(4-F-C₆H₄COO)Bu₂Sn]₂O}₂.     

Crystal and molecular structure of the [Nd2(H2O)8(C6F5COO)6]·2H2O Compound

A compound with the composition Nd(C₆F₅COO)₃· H₂O (I) is prepared. Single crystals are grown, and their single crystal XRD analysis of the Nd₂(H₂O)₈(C₆F₅COO)₆]·2H₂O (II) compound is performed. The crystals are triclinic: a = 7.693(2) Å, b = 9.394(2) Å, c = 18.203(4) Å, α = 81.91(3)°, β = 84.41(3)°, γ = 88.97(3)°, Z = 1, d _x = 2.223 g/cm³. The structure is composed of symmetrical molecules of the binuclear [Nd₂(H₂O)₈(C₆F₅COO)₆] complex and crystallization water molecules. The C₆F₅COO^- ligands are monodentate and tridentate bridging- chelating, which results in a closure of two four-membered chelate cycles NdO₂C and a four-membered metal cycle Nd₂O₂. The NdO₉ polyhedron is a distorted one-capped tetragonal antiprism.     

The coordination properties of aminobenzoate ligands in complexes with alkali metals

The crystal structures of sodium 4-amino-2-hydroxybenzoate dihydrate [NaL·2H₂O, L?= C₆H₃(NH₂)(OH)COO] and potassium 2-aminobenzoate monohydrate [KL*·H₂O, L*?=?C₆H₄(NH₂)COO] were determined by X-ray diffraction methods. The compound NaL·2H₂O crystallizes in the monoclinic system, space group P2₁/c with a?=?8.820(2), b?=?14.632(3), c?=?6.948(2)?Å, β?=?97.88(3)°. The structure consists of sodium ion pairs joined together by tridentate 4-amino-2-hydroxybenzoate moieties creating a polymeric chain. In the metal centres, two water molecules bridge the sodium atoms. Five oxygen atoms and one nitrogen atom form a distorted octahedral environment. The compound KL*·H₂O crystallizes in the monoclinic system, space group P2₁/c with a?=?14.684(3), b?=?7.618(2), c?=?7.512(2)?Å, β?=?96.95(3)°. The structure consists of octacoordinated potassium atoms bonded with three water molecules and five carboxylate oxygen atoms. Water molecules appear as bridging ligands. The 2-aminobenzoate ligand acts as a pentadentate ligand with the molecular network stabilized by hydrogen bonds. Among the polymeric chains in both structures appear noncovalent interactions of type N?H···X.     

Synthesis,Crystal Structure,Luminescence and Thermal Stability of a New Coordination Polymer Constructed by Europium(III) and 2,4‐Dichlorophenoxyacetate

A new coordination polymer {[Eu₂(Cl₂C₆H₃OCH₂COO)₆(H₂O)₄]·(DMF)₄·(H₂O)₂}_n with 2,4‐dichlorophenoxy acetic acid as the ligand has been synthesized. The crystal data for this complex are as follows: monoclinic, space group P2(1)/n, a=0.86474(17) nm, b=3.2475(7) nm, c=1.3843(3) nm, β=92.81(3) °, V=3.8827(13) nm³, D_c=1.718 g/cm³, Z=2, µ(Mo Kα)=2.093 mm⁻¹, F(000) =2008, final discrepancy factors R₁=0.0454, wR₂=0.1165. The crystal structure shows that the title complex forms one‐dimensional chain structure by bridging 2,4‐dichlorophenoxy acetic acid anions. Every centric europium(III) ion is coordinated with ten oxygen atoms from five 2,4‐dichlorophenoxy acetic acid anions and two water molecules, giving a ten‐coordinated distorted bicapped square antiprism geometry. The luminescent property and thermal stability of the complex are also studied.     

Cupro(I)-π-complexes with 1-allyloxybenzotriazole: Synthesis and crystal structure of CuBF4 · 2C6H4N3(OC3H5) · H2O and CuCF3COO · C6H4N3(OC3H5)

The crystals of copper(I) π-complexes CuBF₄ · 2C₆H₄N₃(OC₃H₅) · H₂O (I) and CuCF₃COO · C₆H₄N₃(OC₃H₅) (II) were obtained by alternating-current electrosynthesis and studied by X-ray diffraction: I, space group P2₁/n, a = 10.226(8), b = 13.233(10), c = 16.30(1) Å, β = 98.13(1)°, V = 2249(2) ų, Z = 4, R = 0.0705, 577 reflections; I, space group P $ P\bar 1 The crystals of copper(I) π-complexes CuBF₄ · 2C₆H₄N₃(OC₃H₅) · H₂O (I) and CuCF₃COO · C₆H₄N₃(OC₃H₅) (II) were obtained by alternating-current electrosynthesis and studied by X-ray diffraction: I, space group P2₁/n, a = 10.226(8), b = 13.233(10), c = 16.30(1) ?, β = 98.13(1)°, V = 2249(2) ?³, Z = 4, R = 0.0705, 577 reflections; I, space group P , a = 8.8625(7), b = 9.0647(4), c = 9.1650(5) ?, α = 68.37(2)°, β = 85.31(3)°, γ = 69.86(2)°, V = 646(4) ?³, Z = 2, R = 0.1354, 2669 reflections. In compound I, the tetrahedrally distorted trigonal pyramidal environment of the copper atom comprises two nitrogen atoms of two organic molecules (L), the C=C bond of another L molecule, and the O atom of the water molecule. Due to the bridging function of L molecule, infinite chains [Cu · 2C₆H₄N₃(OC₃H₅) · H₂O] _n are formed in the structure along the y axis. The chains are, in turn, assembled into layers through strong O-H…F hydrogen bonds involving both hydrogen atoms of the water molecule and fluorine atoms of the BF₄⁻ anion. In compound II, two bridging oxygen atoms of two trifluoroacetate anions and two copper atoms form a centrosymmetric dimer. The nitrogen atom of the benzotriazole ring of one molecule L and the C=C double bond of the allyl group of the other molecule L complete the distorted coordination tetrahedron of the metal atom. Owing to the bridging function of the L molecule, the [CuCF₃COO · C₆H₄N₃(OC₃H₅)]₂ dimers are connected to form infinite double chains associated in a three-dimensional framework by only weak interactions. The replacement of the covalently bonded trifluoroacetate anion by an outer-sphere tetrafluoroborate ion opens up the possibility for metal atom binding to three L molecules simultaneously. Original Russian Text ? E.A. Goreshnik, M.G. Mys’kiv, 2008, published in Koordinatsionnaya Khimiya, 2008, Vol. 34, No. 11, pp. 826–830.     

New hydrophobic L‐amino acid salts: maleates of L‐leucine,L‐isoleucine and L‐norvaline

Crystals of maleates of three amino acids with hydrophobic side chains [L‐leucenium hydrogen maleate, C₆H₁₄NO₂⁺·C₄H₃O₄⁻, (I), L‐isoleucenium hydrogen maleate hemihydrate, C₆H₁₄NO₂⁺·C₄H₃O₄⁻·0.5H₂O, (II), and L‐norvalinium hydrogen maleate–L‐norvaline (1/1), C₅H₁₁NO₂⁺·C₄H₃O₄⁻·C₅H₁₂NO₂, (III)], were obtained. The new structures contain C₂²(12) chains, or variants thereof, that are a common feature in the crystal structures of amino acid maleates. The L‐leucenium salt is remarkable due to a large number of symmetrically non‐equivalent units (Z′ = 3). The L‐isoleucenium salt is a hydrate despite the fact that L‐isoleucine is a nonpolar hydrophobic amino acid (previously known amino acid maleates formed hydrates only with lysine and histidine, which are polar and hydrophilic). The L‐norvalinium salt provides the first example where the dimeric cation L‐Nva...L‐NvaH⁺ was observed. All three compounds have layered noncentrosymmetric structures. Preliminary tests have shown the presence of the second harmonic generation (SGH) effect for all three compounds.     

Bis(μ‐3,5‐di‐tert‐butylcatecholato‐O1:O1,O2)bis[tris(pyridine‐N)cadmium(II)] dipyridine solvate

X‐ray diffraction shows that the title cadmium(II) complex, [Cd₂(C₁₄H₂₀O₂)₂(C₅H₅N)₆]·2C₅H₅N, has a dimeric structure in which two (py)₃Cd(3,5‐di‐tert‐butylcatecholate) units (py is pyridine) are connected by two bridging O atoms, the coordination of the Cd atoms being distorted octahedral. There are two symmetrically independent dimers in the crystal structure; one is in a general position and the other lies about an inversion centre. In both cases, the bridging Cd—O distances between the Cd–catecholate units [2.224 (2)–2.237 (2) Å] are shorter than the bridging Cd—O distances within the catecholate cycle [2.273 (2)–2.281 (2) Å]. The Cd—N_py distances are 2.354 (2)–2.471 (2) Å. Besides the main mol­ecules, the crystal also contains pyridine solvate mol­ecules.     

pH Dependent Synthesis of NdIII Coordination Compounds Based on Bifunctional 5‐(4‐Pyridyl)tetrazole‐2‐acetic Acid

The Nd^III coordination compounds [Nd(4‐pytza)₃(H₂O)₂] · 2H₂O ( 1 ) and [Nd(4‐pytza)₂(H₂O)₄]Cl · 2H₂O ( 2 ) [H4‐pytza = 5‐(4‐pyridyl)tetrazole‐2‐acetic acid] were synthesized by reactions of K4‐pytza and NdCl₃ · 6H₂O at different pH values. Single crystal X‐ray diffraction analysis reveals that 4‐pytza ligands in 1 in a μ_1,3‐COO syn‐syn or μ_1,1,3‐COO bridging mode coordinate to two central Nd^III atoms to display a dinuclear unit, which is connected by one of these 4‐pytza ligands acting in end‐to‐end bridging mode to form a 1D ladder‐like chain. Different from 1 , each 4‐pytza in 2 with a μ_1,3‐COO syn‐anti bridging mode coordinates to two Nd^III atoms to display a 1D zigzag chain. Furthermore, the luminescence properties of 1 and 2 were investigated at room temperature in the solid state.     

catena‐Poly[[[pyridinecopper(II)]bis[μ3‐4‐(2‐oxidobenzylideneamino)benzoato]] dimethylformamide disolvate], a polymer composed of dimeric dicopper building units

The title compound, {[Cu(C₁₄H₉NO₃)(C₅H₅N)]·C₃H₇NO}_n or {[Cu₂L₂(py)₂]·2DMF}_n [py is pyridine, L is 4‐(salicylideneamino)benzoate and DMF is dimethylformamide], is composed of dimeric dicopper [CuL(py)]₂ building units, which are interlinked into a one‐dimensional chain through the formation of Cu—O_COO bonds. The dimeric unit is centrosymmetric, containing two Cu^II atoms linked by bridging phenolate O atoms into a Cu₂O₂ plane with a chelating Cu—O bond length of 1.927 (2) Å and a bridging Cu—O bond length of 2.440 (2) Å. Interchain C—H...O and π–π stacking interactions are responsible for an extensive three‐dimensional structure in which the resulting channels are filled by DMF solvent molecules.     

Syntheses,Crystal Structures,and Photophysical Properties of Heteronuclear Zinc(II)/Cadmium(II)‐Lanthanide(III) Coordination Complexes based on Benzoic Acid

The heteronuclear d‐f coordination complexes [Er₂Zn₂(C₆H₅COO)₁₀(phen)₂] (1), [Ho₂Zn₂(C₆H₅COO)₁₀(phen)₂] ( 2 ), [Pr₃Zn₆(C₆H₅COO)₂₁(phen)₃] ( 3 ), [ErCd(C₆H₅COO)₅(phen)·H₂O] ( 4 ), [Ho₂Cd₃(C₆H₅COO)₁₂(phen)₂] ( 5 ), [EuCd₂(C₆H₅COO)₇(phen)₂] ( 6 ) (C₆H₅COOH = benzoic acid;phen = 1,10‐phenanthroline) were synthesized by hydrothermal methods, and their structures were studied by single‐crystal X‐ray diffraction. Complexes 1 , 2 , 4 , and 5 crystallize in the triclinic space group P$\bar{1}$ and complexes 3 and 6 in the monoclinic space group C2/c. The room temperature IR, UV/Vis/NIR absorption, and emission spectra of the six complexes were determined and assigned. In the visible and NIR regions, the emission spectra of complexes show characteristic bands of corresponding Ln^III ions, which are attributed to the sensitization from the d block (Zn/Cd‐ligand section) and ligands. In comparison with isolated Ln^III ions, the NIR emission bands of complexes 1 – 5 exhibit shifting, broadening and splitting, which are also present in their UV/Vis/NIR absorption spectra. Thus, the two spectra of complexes can evidence each other.     

Transition-metal complexes with bidentate ligands spanning trans-positions. V. Crystal and molecular structures of complexes [RhCl(CO) (1)] and [PdCl2(1)]; 1 = 2,11-bis (diphenylphosphinomethyl)benzo [c]phenanthrene

The structures of [RhCl(CO) ( 1 )] and [PdCl₂ ( 1 )], where 1 is the bidentate ligand (C₆H₅)₂P·CH₂·C₁₈H₁₀· CH₂·P(C₆H₅)₂, have been determined from threedimensional X-ray counter data collected on single crystals of the C₆H₅·CN solvates. The two compounds are isomorphous and crystallize in the triclinic system, space group P 1 , Z = 2: a = 14.580 (8), b = 13.029 (10), c = 11.909 (6) Å, α = 106.33 (5), β = 100.47 (4), γ = 95.73 (5)° for the rhodium complex; a = 14.361 (5), b = 13.044 (7), c = 11.897 (4) Å, α = 105.97 (4), β = 100.27 (3), γ = 94.76 (4)°, for the palladium complex. In both complexes the metal atom is four-coordinate with slightly distorted square-planar configuration. In both cases the ligand 1 spans trans positions with M-P bond lengths in the ranges of the literature data. Also the other bond distances fall in regular ranges. Ligand 1 has almost the same conformation in both complexes and is characterized by a strong out-of-plane deformation of the benzophenanthrene system as a consequence of severe overcrowding.     

Synthesis and characterization of some metal(II) and sodium ions with cyclopentane-1,2,3,4-tetracarboxylate anion

New divalent metal cyclopentane-1,2,3,4-tetracarboxylate (CPTC) hydrates of empirical formula M₂C₅H₆(COO)₄ · nH₂O, where M = Ni, Co, Cu, or Zn and n = 3?6, and sodium CPTC Na₃C₅H₆COOH(COO)₃ · 7H₂O have been prepared and characterized by elemental analysis, magnetic measurements, thermal, and infrared spectral studies. For the sodium salt, a single crystal (Na₃C₅H₆COOH(COO)₃ · 8H₂O) was also obtained. IR spectra of the metal(II) complexes indicate the coordination of metal ions through all carboxylates. For the sodium compound, a band at 1681 cm^?1 indicates that some carboxylic groups have not been deprotonated. The presence of protonated carboxylic group was also confirmed by an X-ray single crystal analysis. On heating in air atmosphere, all complexes lose water molecules and next anhydrous compounds decompose to corresponding metal oxides and sodium carbonate.     

Synthesis, structure and characterization of binuclear copper(Ⅱ) complexes

At room temperature, dibenzoyl peroxide undergoes oxidative addition reaction with metallic copper powder and pyridine N-oxide (triphenylphosphine oxide or 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin) which affords the last products as binuclear copper(II) complexes, [Cu(C5H5NO)-(C6H5COO)2]2(1), [Cu(OPPh3)(C6H5COO)2]2(2) and [Cu(C6H5COO)(C26H2oN2)](3, C26H2oN2 is 2,9-dimethyl-4,7-diphenyl-1,10-phenanthrolin). The structure of the complexes were characterized by elemental analyses, IR spectra, TG-DTA and magnetic property. Crystals(1) are triclinic, space group P1,a=0.92617(36),b=1.06973(17), c=1.08813(29) nm, a=59.60(2)°, β=74.83(3)°,γ=72.80(2)°, V=0.880 nm3, Dc=1.520 g/cm3, Z=1, R=0.044, Rw=0.048, Mr=805.78, 3477 reflections with I > 3σ(I). Each copper(Ⅱ) ion is coordinated by two bridging bidentate benzoate ligands and one pyridine N-oxide or triphenylphosphine oxide to form dimeric binuclear molecules. The structure of the compound(1) shows a clear centre of symmetry.     

Mechanochemical syntheses,crystal structures,and photo-luminescent properties of a new hydrazone and its nickel and cadmium complexes

Abstract

A new hydrazone, ethyl Z-2-(pyridine-2yl-methylene)hydrazinecarboxylate (C₉H₁₁N₃O₂; Hpyec) and its metal complexes bis(ethyl Z-2-(pyridine-2yl-methylene)hydrazinecarboxylate)nickel(II) monohydrate, [Ni(pyec)₂]·H₂O (1) and bis(acetato)(ethyl Z-2-(pyridine-2yl-methylene)hydrazinecarboxylate)cadmium(II), [Cd(Hpyec)(CH₃COO)₂] (2), have been prepared by mechanochemical syntheses and characterized by elemental analysis, UV–vis, IR and NMR spectroscopies, TG-DTA, and solid state emission techniques. The X-ray single crystal structures of both complexes were determined. In 1, the Ni²⁺ ion is coordinated by two N,N,O-tridentate anionic ligands to generate a distorted cis-NiO₂N₄ octahedron. In 2, the cadmium ion is seven-coordinate by one neutral N,N,O-tridentate ligand and two chelating acetate ions to generate a very-distorted CdN₂O₅ pentagonal bipyramid with the Hpyec atoms occupying both axial and one equatorial site. Crystal data: 1, C₁₈H₂₂N₆NiO₅, M_r?=?461.12, monoclinic, P2₁/c, a?=?10.8759(3) Å, b?=?11.7055(4) Å, c?=?16.8424(5) Å, β?=?108.583(1)°, V?=?2032.38(11) ų, Z?=?4, R(F)?=?0.023, wR(F²)?=?0.065; 2, C₁₃H₁₇CdN₃O₆, M_r?=?423.69, monoclinic, Cc, a?=?13.0215(10) Å, b?=?15.8104(11) Å, c?=?7.99(6) Å, β?=?96.692(2)°, V?=?1621.7(2) ų, Z?=?4, R(F)?= 0.017, wR(F²)?=?0.038.     

Synthesis,characterization and crystal structure analysis of a novel oxo-centered mixed-metal complex containing unsaturated bridging carboxylates

A novel oxo-centered trinuclear mixed-metal carboxylate complex with unsaturated bridging ligands [Fe₂Cr(μ₃-O)(C₃H₃O₂)₆(H₂O)₃]·NO₃·4H₂O has been synthesized and characterized by means of Elemental analyses, Infrared spectroscopy and Crystal structure analysis. The compound crystallizes isotypically in the monoclinic space group type P2₁/c. In the compound, each M^(III) cation is coordinated by six O atoms from four unsaturated carboxylate groups as bridging ligands, one water molecule as the terminal ligand, and a μ₃-oxygen atom in the center of an equilateral triangle. The infrared spectra show resolved bands arising from ν_asym(COO) and ν_sym(COO) vibration of bridging carboxylate ligands along with those of ν_asym(M₂M′O) vibration in the complex. The difference between symmetrical and asymmetrical (COO) ligands indicate that the acrylate bridge is present in the structure of complex.      

Weak Antiferromagnetism in Carboxylato Copper(II) Complexes of Bipyridines

Three new members of the copper/carboxylato/heterocyclic diimine family, namely [Cu(GLYO)(2, 2′‐bipy)]₂ · nH₂O (n = 4 ( 1 ) or 6 ( 2 ), H₂GLYO = glycolic acid, 2, 2′‐bipy = 2, 2′‐bipyridine) and {[Cu(AcO)₂(4, 4′‐bipy)] · 3H₂O}_n ( 3 ) (AcO = acetato, 4, 4′‐bipy = 4, 4‐bipyridine), have been synthesized and characterized by IR and electronic absorption spectroscopy, and the crystal structures have been determined by single crystal X‐ray analysis. 1 and 2 are composed of discrete dinuclear units in which each Cu^II atom is coordinated in a square pyramidal arrangement to the two nitrogen atoms of a bipyridine ligand, to bridging non‐carboxy oxygen atoms belonging to two glycolato ligands, and to one of the carboxy oxygen atoms of one of these glycolato ligands. The Cu··Cu distance is 3.0666(5)Å. Compound 3 consists of linear chains of dinuclear units in which each Cu^II is coordinated to one non‐bridging monodentate acetato ligand, to two acetato ligands that each bridge via a single oxygen atom, and to one nitrogen atom of each of two mutually trans bis‐monodentate 4, 4′‐bipyridine ligands that link the repeat units of the polymer. The coordination polyhedra are square pyramids, and the Cu··Cu distance within each dimeric repeat unit is 3.502(2)Å. The temperature dependence of their magnetic susceptibilities shows there to be weak antiferromagnetic interaction between the metal atoms of each dimer in all three complexes, with fitting parameter values of —2J = 1.3 cm^—1 and g = 2.09 for 1 and 2 , and —2J = 1.4 cm^—1 and g = 2.15 for 3 . The X‐band EPR spectra show signals corresponding to the dinuclear units.     

Synthesis,Crystal Structures,and Magnetic Properties of Three New Iron Complexes Derived from 3,5‐Bis(pyridin‐2‐yl)‐1,2,4‐triazole

Two new iron(III) complexes and one iron(II) complex have been synthesized from the solvothermal reactions of FeCl₃·6H₂O with 3,5‐bis(pyridin‐2‐yl)‐1,2,4‐triazole (Hbpt) in methanol or acetonitrile. KSCN acted as the reducing agent in the synthesis of iron(II) complex of 3 . [FeCl₃(Hbpt)(H₂O)]·H₂O ( 1 ) crystallizes in the triclinic space group with a = 7.475(1), b = 9.468(2), c = 12.309(2) Å, α = 73.880(2), β = 74.746(2), γ = 81.849(2)°, V = 805.2(2) ų, Z = 2. [Fe₂(bpt)₂Cl₄] ( 2 ): orthorhombic space group Pnnm with a = 9.895(2), b = 10.632(2), c = 13.195(2) Å, V = 1388.1(4) ų, Z = 2. [Fe₂(bpt)₂(MeOH)₂Cl₂] ( 3 ): orthorhombic space group Pbca with a = 14.4204(16), b = 9.8737(11), c = 19.792(2) Å, V = 2818.1(5) ų, Z = 4. 1 features the first structurally characterized metal complex of the neutral Hbpt ligand in which the Hbpt ligand adopts an unprecedented zwitterionic form. 2 shows a neutral dinuclear iron(III) complex and the [Fe₂(bpt)₂]⁴⁺ unit is ideally planar. The two iron(III) ions separated by a distance of 4.408(2) Å are doubly triazolate‐bridged. Each dimeric unit is connected with six other dimeric ones via the bifurcated C‐H···Cl hydrogen bonds, these connections extend the dimeric moieties into a three‐dimensional molecular architecture. 3 is a neutral centrosymmetric dinuclear Fe^II complex, in which intermolecular moderate O‐H···N hydrogen bonding interactions between the methanol molecules and 4‐position nitrogen atoms of the triazolato groups extend the dinuclear species into a two‐dimensional supramolecular architecture of (4,4) topology. Magnetic studies indicate there exists an antiferromagnetic spin coupling in Fe^III₂ and Fe^II₂ units via the double triazolate bridges in 2 and 3 .     

K3[C3N3(COO)3]·2H2O – Crystal Structure of a New Alkali Derivative of the Multidentate Ligand Triazine Tricarboxylate

Potassium‐1,3,5‐triazine‐2,4,6‐tricarboxylate dihydrate K₃[C₃N₃(COO)₃] · 2H₂O was obtained by saponification of the respective ethyl ester in aqueous solution under mild conditions and subsequent crystallization at 4 °C. The crystal structure of the molecular salt was elucidated by single‐crystal X‐ray diffraction [P , a = 696.63(14), b = 1748.5(3), c = 1756.0(3) pm, α = 119.73(3), β = 91.96(3), γ = 93.84(3)°, V = 1847.6(6) · 10⁶ pm³, Z = 6, T = 200 K]. Perpendicular to [100] the triazine tricarboxylate and potassium ions are arranged in layers alternating with layers of crystal water molecules. Two thirds of the triazine tricarboxylate units form hexagonal channels being filled with the remaining triazine tricarboxylate molecules. K₃[C₃N₃(COO)₃] · 2H₂O was additionally investigated by means of FTIR spectroscopy, TG and DTA measurements.     

The Synthesis by Decarboxylation Reactions and Crystal Structures of 1, n–Bis(diphenylphosphino)alkane(pentafluorophenyl)‐platinum(II) Complexes

Decarboxylation reactions between the complexes cis–[PtCl₂L] (L = 1, n–bis(diphenylphosphino)–ethane (n = 2, dppe), –propane (n = 3, dppp) or –butane (n = 4, dppb)) and thallium(I) pentafluorobenzoate in pyridine give cis–[PtCl(C₆F₅)L] and cis–[Pt(C₆F₅)₂L] complexes in high yields with short reaction times. X–ray crystal structures of cis–[PtCl(C₆F₅)(dppe)] · 0.5 C₅H₅N, cis–[PtCl(C₆F₅)(dppp)], cis–[PtCl(C₆F₅)(dppb)] · C₃H₆O, cis–[Pt(C₆F₅)₂L] (L = dppe, dppp and dppb) and the reactants cis–[PtCl₂(dppp)] (as a CH₂Cl₂ solvate) and cis–[PtCl₂(dppb)] show monomeric structures with chelating diphosphine ligands in all cases rather than dimers with bridging diphosphines. ³¹P NMR data are consistent with these structures in solution.     

Dipyridylamide Donor Disposition and Isophthalate Substituent Steric Effect on the Dimensionality and Topology of Divalent Copper Coordination Polymers

Divalent copper coordination polymers containing an isophthalate ligand and a dipyridylamide ligand show different dimensionalities and topologies depending on pyridyl nitrogen donor disposition and the steric bulk of the substituent on the dicarboxylate aromatic ring. According to single‐crystal X‐ray diffraction, [Cu(ip)(3‐pna)]_n ( 1 , ip = isophthalate, 3‐pna = 3‐pyridylnicotinamide) shows a (4, 4) layered grid structure based on {Cu₂(OCO)₂} dimeric units. {[Cu(ip)(3‐pina)]·H₂O}_n ( 2 , 3‐pina = 3‐pyridylisonicotinamide) exhibits similar dimeric units, but in contrast to 1 these are connected into a non‐interpenetrated 3D 6⁵8 cds network. Both [Cu(mip)(3‐pina)]_n ( 3 , mip = 5‐methylisophthalate) and [Cu(meoip)(3‐pina)]_n ( 4 , mip = 5‐methoxyisophthalate) display dimer‐based 4¹²6³ pcu networks in contrast to 2 . Use of 5‐hydroxyisophthalate (H₂hip) as a precursor afforded a mixture of {[Cu₂(hip)₂(3‐pina)₄]·9.5H₂O}_n ( 5 ) and [Cu(hip)(3‐pina)]_n ( 6 ). Compound 5 shows a 2D interdigitated structure with [Cu(hip)]_n coordination polymer layers featuring {Cu₂(OCO)₂} dimeric units and pendant 3‐pina ligands, while 6 also showed a dimer‐based 4¹²6³ pcu network. Use of the very sterically bulky 5‐tert‐butylisophthalate (tbip) ligand afforded the 1D chain coordination polymer {[Cu(tbip)(3‐pina)₂(H₂O)]·H₂O}_n ( 7 ), which contains isolated copper ions in contrast to 1 – 6 , and has a curious “butterfly“ resemblance. Very weak antiferromagnetic coupling is seen within the {Cu₂(OCO)₂} dimeric units in 1 . Thermal decomposition behavior is also discussed.