Complexes of a tridentate ONS Schiff base. Synthesis and biological properties

Several new complexes of a tridentate ONS Schiff base derived from the condensation of S-benzyldithiocarbazate with salicylaldehyde have been characterised by elemental analyses, molar conductivity measurements and by i.r. and electronic spectra. The Schiff base (HONSH) behaves as a dinegatively charged ligand coordinating through the thiolo sulphur, the azomethine nitrogen and the hydroxyl oxygen. It forms mono-ligand complexes: [M(ONS)X], [M=Ni^II, Cu^II, Cr^III, Sb^III, Zn^II, Zr^IV or U^VI with X = H₂O, Cl]. The ligand produced a bis-chelated complex of composition [Th(ONS)₂] with Th^IV. Square-planar structures are proposed for the Ni^II and Cu^II complexes. Antimicrobial tests indicate that the Schiff base and five of the metal complexes of Cu^II, Ni^II, U^VI, Zn^II and Sb^III are strongly active against bacteria. Ni^II and Sb^III complexes were the most effective against Pseudomonas aeruginosa (gram negative), while the Cu^II complex proved to be best against Bacillus cereus (gram positive bacteria). Antifungal activities were also noted with the Schiff base and the U^VI complex. These compounds showed positive results against Candida albicans fungi, however, none of them were effective against Aspergillus ochraceous fungi. The Schiff base and its zinc and antimony complexes are strongly active against leukemic cells (CD₅₀ = 2.3–4.3 μg cm⁻³) while the copper, uranium and thorium complexes are moderately active (CD₅₀ = 6.9–9.5 μg cm⁻³). The nickel, zirconium and chromium complexes were found to be inactive. This revised version was published online in June 2006 with corrections to the Cover Date.     

The preparation and characterization of some new nickel(II), copper(II), zinc(II) and cadmium(II) complexes of the pyrrole-2-carboxaldehyde Schiff bases ofS-alkyl esters of dithiocarbazic acid

Summary New complexes of general formulae [Ni(HL)₂], [ML]·H₂O and [Cu(HL)X] (H₂L = pyrrole-2-aldehyde Schiff bases ofS-methyl- andS-benzyldithiocarbazates; X = Cl or Br; M = Ni^II, Cu^II, Zn^II or Cd^II) were prepared and characterized by a variety of physicochemical techniques. The Schiff bases coordinate as NS bidentate chelating agents in [Ni(HL)₂] and [Cu(HL)X], and as tridentate NNS chelates in [ML] (M = Ni^II, Cu^II, Zn^II or Cd^II). Both the [Ni(HL)₂] and [NiL] complexes are diamagnetic and square-planar. Based on magnetic and spectroscopic evidence, thiolate sulphur-bridged dimeric square-planar structures are assigned to the [Cu(HL)X] and [ML] (M = Ni^II or Cu^II) complexes. The complexes ML (M = Zn^II or Cd^II) are polymeric and octahedral.     

Synthesis and spectral studies of copper(II), nickel(II), cobalt(II) and vanadyl(II) complexes of tridentate Schiff bases of 1,2,3,5,6,7,8,8a-octahydro-3-oxo-N,1-diphenyl-5-(phenylmethylene)-2-naphthalenecarboxamide

Summary Metal(II) chelates of Schiff bases derived from the condensation of 1,2,3,5,6,7,8,8a-octahydro-3-oxo-N,1-diphenyl-5-(phenylmethylene)-2-naphthalenecarboxamide with o-aminophenol (KAAP), o-aminothiophenol (KAAT) or o-aminobenzoic acid (KAAB) have been prepared and characterized. The complexes are of the type [M(N₂X)]₂ for M = Cu^II and M(NX)₂·nH₂O for M = Ni^II, Co^II and VO^II (X = phenolic oxygen, thiophenolic sulphur or carboxylic oxygen; n = 0 or 2). Conductivity data indicate that the complexes are non-ionic. The Schiff bases behave as dibasic tridentate ligands in their copper(II) complexes and as monobasic bidentate ligands in their nickel(II), cobalt(II) and vanadyl(II) complexes. The subnormal magnetic moments of the copper(II) complexes are ascribed to an antiferromagnetic exchange interaction arising from dimerization. Nickel(II) and cobalt(II) complexes are trans octahedral whereas vanadyl(II) complexes are square pyramidal     

New complexes of iron(III), cobalt(II), nickel(II) and copper(II) with 2-phenyl-1,2,3-triazole-4-carboxalidene-2-aminophenol

Summary Fe^III, Co^II, Ni^II and Cu^II complexes of a new Schiff base, 2-phenyl-1,2,3-triazole-4-carboxalidene-2-aminophenol (PTCAP), have been synthesized and characterized by elemental analyses, molar conductance and magnetic susceptibility measurements, and by u.v.-vis., i.r. and e.p.r. spectral observations. The studies indicate an octahedral structure for the complexes with the general formula [ML₂] (M = Co^II, Ni^II or Cu^II.; L = PTCAP) or [M′(OH)L₂] (M′ = Fe^III). The i.r. spectra suggest that the ligand acts as a tridentate (NNO) donor towards Co^II, Ni^II and Cu^II, and, in the Fe^III complex, one of the two ligand molecules acts as a bidentate (NO) donor and the other as a tridentate donor. The M?ssbauer spectrum of the Fe^III complex suggests the presence of a spin equilibrium at room temperature. Cyclic voltammograms are also recorded for the Cu^II and Fe^III complexes.     

Synthesis, structural characterization and electrochemical studies of nickel(II), copper(II) and cobalt(III) complexes of some ONS donor ligands derived from thiosemicarbazide and S-alkyl/aryl dithiocarbazates

Four tridentate ONS ligands, namely 2-hydroxyacetophenonethiosemicarbazone (H₂L¹), the 2-hydroxyacetophenone Schiff base of S-methyldithiocarbazate (H₂L²), the 2-hydroxy-5-nitrobenzaldehyde Schiff base of S-methyldithiocarbazate (H₂L³), and the 2-hydroxy-5-nitrobenzaldehyde Schiff base of S-benzyldithiocarbazate (H₂L⁴), and their complexes of general formula [Ni(HL¹)₂], [ML] (M?=?Ni^II or Cu^II; L?=?L¹, L², L³ and L⁴), [Co(HL)(L); L?=?L¹, L², L³ and L⁴] and [ML(B)] (M?=?Ni^II or Cu^II; L?=?L² and L⁴; B?=?py, PPh₃) have been prepared and characterized by physico-chemical techniques. Spectroscopic evidence indicates that the Schiff bases behave as ONS tridentate chelating agents. X-ray crystallographic structure determination of [NiL²(PPh₃)] and [CuL⁴(py)] indicates that these complexes have an approximately square-planar structure with the Schiff bases acting as dinegatively charged ONS tridentate ligands coordinating via the phenoxide oxygen, azomethine nitrogen and thiolate sulfur atoms. The electrochemical properties of the complexes have been studied by cyclic voltammetry.     

Coordination chemistry and biological activity of two tridentate ONS and NNS Schiff bases derived from S-benzyldithiocarbazate

Two tridentate Schiff bases having ONS and NNS donor sequences were prepared by condensing S-benzyldithiocarbazate (NH₂NHCSSCH₂Ph) (SBDTC) with pyridine-2-carboxaldehyde and salicylaldehyde, respectively. Complexes of these ligands with Ni^II, Zn^II, Cr^III, Co^II, Cu^II, and Sn^II were studied and characterized by elemental analyses and various physico-chemical techniques. Ni^II, Cu^II, Zn^II and Sn^II complexes were four-coordinate while the Cr^III, Sr^III and Co^III complexes were six-coordinate. The ONS Schiff base was moderately active against leukemia, while its zinc, antimony and cobalt complexes were strongly active against leukemic cells with DC₅₀ = 0.35–5.00.     

The coordination chemistry ofN,N′-ethylenebis(2-acetylpyridine imine) andN,N′-ethylenebis(2-benzoylpyridine imine); two potentially tetradentate ligands containing four nitrogen atoms

Summary New complexes of the general formulae [ML_A(H₂O)₂]-Cl₂ (M=Ni or Cu), [ML_AX₂] (M=Co or Cu; X=Cl or Br), [NiL_ABr₂]·H₂O, [ML_A] [MCl₄] (M=Pd or Pt), [NiL_B(H₂O)₂]Cl₂·2H₂O, [ML_BCl₂] (M=Co, Ni, Cu, Pd or Pt; X=Cl or Br) and [ML_B] [MCl₄] (M=Pd or Pt), where L_A=N,N-ethylenebis(2-acetylpyridine imine) and L_B=N, N-ethylenebis(2-benzoylpyridine imine), have been isolated. The complexes were characterized by elemental analyses, conductivity measurements, t.g./d.t.g. methods, magnetic susceptibilities and spectroscopic (i.r., far-i.r., ligand field,¹Hn.m.r.) studies. Monomeric pseudo-octahedral stereochemistries for the Co^II, Ni^II and Cu^II complexes andcis square planar structures for the compounds [ML_BX₂] (M=Pd or Pt; X=Cl or Br) are assigned in the solid state. The molecules L_A and L_B behave as tetradentate chelate ligands in the Co^II, Ni^II, Cu^II and Magnus-type Pd^II and Pt^II complexes, bonding through both the pyridine and methine nitrogen atoms. A bidentateN-methine coordination of the Schiff base L_B is assigned in the [ML_BX₂] complexes (M=Pd or Pt; X=Cl or Br). The anomalous magnetic moment values of the Co^II complexes are discussed.     

Preparation,characterization and antifungal properties of transition metal ion complexes of quadridentate N3S ligands

Summary New metal complexes [M(NNNS)X] (M = Ni^II, Cu^II, Zn^II and Cd^II; NNNS^– = anion of the quadridentate ligands formed from S-methyl--N-(2-aminophenyl)-methylenedithiocarbazate and pyridine-2-aldehyde or 6-methylpyridine-2-aldehyde; X = Cl, NCS, NO₃ or I) and [Co(NNNS)Cl₂]·2H₂O have been prepared and characterized by elemental analysis and conductance measurements. Magnetic and spectroscopic evidence support a five-coordinate structure for [M(NNNS)X] (M = Ni^II, Cu^II, Zn^II and Cd^II; X = Cl, NCS) and a squareplanar structure for [Ni(NNNS)]X (X = NO₃ or I). The [Co(NNNS)Cl₃]·2H₂O complex is low-spin and octahedral. The Schiff bases and some of their metal complexes were tested against three pathogenic fungi, Alternaria alternata, Curvularia geniculata and Fusarium palidoroseum. The metal complexes are less fungitoxic than the free ligands.     

Nickel(II), copper(II), palladium(II) and platinum(II) complexes of bidentate SN ligands derived from S-alkyldithiocarbazates and the X-ray crystal structures of the [Ni(tasbz)2] and [Cu(tasbz)2] · CHCl3 complexes

New complexes of general empirical formula, [M(NS)₂] · nCHCl₃ (M = Ni^II, Cu^II, Pd^II or Pt^II; NS = anionic form of the thiophene-2-aldehyde Schiff bases of S-methyl- and S-benzyldithiocarbazate; n = 0, 1) have been synthesized and characterized by physico-chemical techniques. Magnetic and spectroscopic evidence support a square-planar structure for these complexes. The crystal structures of the [Ni(tasbz)₂] and [Cu(tasbz)₂] · CHCl₃ complexes (tasbz = anionic form of the thiophene-2-aldehyde Schiff base of S-benzyldithiocarbazate) have been determined by X-ray diffraction. Both complexes have a trans-planar structure in which the two Schiff base ligands are coordinated to the metal(II) ion as uninegatively charged bidentate ligands via the thiolate sulfur and the azomethine nitrogen atoms. This revised version was published online in June 2006 with corrections to the Cover Date.     

Palladium(II) and platinum(II) complexes of Schiff bases derived from 2,6-diacetylpyridine and S-methyldithiocarbazate and the X-ray crystal structure of the [Pd(mdapsme)Cl] complex

Condensation of 2,6-diacetylpyridine (dap) with S-methyldithiocarbazate (smdtc) in a 1:2 molar ratio yields a bicondensed pentadentate Schiff base (H₂dapsme) which reacts with K₂MCl₄ (M = Pd^II, Pt^II) giving stable complexes of empirical formula, [M(dapsme)] · 0.5Me₂CO. These complexes have been characterized by a variety of physico-chemical techniques. Condensation of dap with smdtc in a 1:1 molar ratio also yields the bicondensed Schiff base (H₂dapsme) as the major product, but a mono-condensed one-armed Schiff base (Hmdapsme) is also obtained as a minor product. The latter reacts with K₂PdCl₄ in an EtOH–H₂O mixture yielding a crystalline complex of empirical formula, [Pd(mdapsme)Cl], the crystal structure of which has been determined by X-ray diffraction. The complex has a distorted square-planar structure in which the ligand is coordinated to the palladium(II) ion as a uninegatively charged tridentate chelating agent via the pyridine nitrogen atom, the azomethine nitrogen atom and the thiolate sulfur atom; the oxygen atom of the acetyl group does not participate in coordination.     

Transition metal ion complexes of thiosemicarbazones derived from 2-acetylpyridineN-oxide. I. The 4-methyl derivative

Summary TheN-methyl-2-[1-(2-pyridinyl-1-oxide)ethylidene]hydrazinecarbothioamide, HLO4M, has been used to prepare a series of Co^III, Ni^II and Cu^II complexes. Species with two deprotonated LO4M ligands, one LO4M and one HLO4M ligand, two HLO4M ligands and one HLO4M ligand with two small anionic ligands have been isolated. The deprotonated LO4M bonds as a tridentate ligandvia theN-oxide oxygen, the imine nitrogen (N¹ and the sulphur while the HLO4M ligand coordinates primarily as a bidentate ligandvia only the first two atoms listed above. I.r., electronic, mass and e.s.r. spectra have been used to determine the nature of these complexes. One of the more striking differences between these compounds and those prepared with other thiosemicarbazones of 2-acetylpyridine and 2-acetylpyridineN-oxide is that tetrahedral yellow [Ni(HL)X₂] rather than planar brown [NiLX] (X=Cl or Br) solids have been isolated with this ligand. Other differences in the nature of the coordination spheres of the various metal ions occur with this particular ligand when compared to previously studied thiosemicarbazone complexes.NATO Fellow, on leave from Medical Faculty, Istanbul University.     

Metal complexes of 2-acetylpyridine N(4)-dihexyl- and N(4)-dicyclohexylthiosemicarbazones

Summary 2-Acetylpyridine N(4)-dihexyl- and N(4)-dicyclohexylthiosemicarbazone, HAc4DHex and HAc4DCHex, respectively, and Fe^III, Co^II, Co^III, Ni^II, Cu^II and Zn^II complexes have been prepared and characterized by molar conductivities, magnetic susceptibilities and spectroscopic techniques. For many of the complexes, loss of the N(2)H hydrogen occurs, and the ligands coordinate to the metal centres as NNS monoanionic, tridentate ligands, e.g., [M(NNS)X] (M = Co^II, Ni^II, Cu^II, NNS = Ac4DHex or Ac4DCHex and X = Cl or Br), [Fe(NNS)₂]ClO₄, [Co(NNS)₂]BF₄, [Cu(NNS)NO₃] and [Zn(NNS)OAc]. Zn^II ion is also chelated by neutral ligands in [Zn(HNNS)X₂] (X = Cl, Br). In addition, [Ni(Ac4DHex)-(HAc4DHex)]X (X = BF₄, ClO₄) and [Ni(HAc4DCHex)₂]-(BF₄)₂ are reported where the neutral thiosemicarbazone is coordinated via the pyridyl nitrogen, azomethine nitrogen and thione sulfur. Crystal structure determinations of HAc4DCHex and [Cu(Ac4DHex)Br] show the former to contain the bifurcated hydrogen bonded form and the latter to be planar with no significant interaction between neighbouring centres.     

N-Phthaloylglycinate ternary complexes with cobalt(II), nickel(II), copper(II), zinc(II) and cadmium(II) metal ions and aromatic mono,bi and tridentate amines

Complexes of N-phthaloylglycinate (N-phthgly) and Co^II, Ni^II, Cu^II, Zn^II and Cd^II containing imidazole (imi), N-methylimidazole (mimi), 2,2-bipyridyl (bipy) and 1,10-phenanthroline (phen), and tridentate amines such as 2,2,2-terpyridine (terpy) and 2,4,6-(2-pyridyl)s-triazine (tptz), were prepared and characterized by conventional methods, i.r. spectra and by thermogravimetric analysis. For imi and mimi ternary complexes, the general formula [M(imi/mimi)₂(N-phthgly)₂]·nH₂O, where M = Co^II, Ni^II, Cu^II and Zn^II applies. For Cd^II ternary complexes with imi, [Cd(imi)₃(N-phthgly)₂]·2H₂O applies. For the bi and tridentate ligands, ternary complexes of the formula [M(L)(N-phthgly)₂]·nH₂O were obtained, where M = Co^II, Ni^II, Cu^II and Zn^II; L = bipy, phen, tptz and terpy. In all complexes, N-phthgly acts as a monodentate ligand, coordinating metal ions through the carboxylate oxygen, except for the ternary complexes of Co^II, Ni^II and Cu^II with mimi and Cu^II and Zn^II with imi, where the N-phthgly acts as a bidentate ligand, coordinating the metal ions through both carboxylate oxygen atoms.     

Synthesis,characterization and X-ray crystal structures of the bis–ligand zinc(II) and cadmium(II) complexes of the methylpyruvate Schiff base of <Emphasis Type="Italic">S</Emphasis>-methyldithiocarbazate

New bis-chelated Zn^II and Cd^II complexes of empirical formula, [M(mpsme)₂] (mpsme=the anionic form of the tridentate ONS donor ligand formed from methylpyruvate and S-methyldithiocarbazate) have been prepared and characterized by conductance, i.r., electronic and n.m.r. spectroscopic techniques. Spectral evidence supports a six-coordinate distorted octahedral structure for these complexes. X-ray crystallographic structural analysis also confirms that, in both the [Zn(mpsme)₂] and [Cd(mpsme)₂] complexes, the methylpyruvate Schiff base of S-methyldithiocarbazate is coordinated to the metal ions as a uninegatively charged tridentate ONS chelating agent via the carbonyl oxygen atom, the azomethine nitrogen atom and the thiolate sulfur atom. Both complexes are assigned a distorted octahedral geometry in which the ligands are arranged meridionally around the metal ions. The distortion from regular octahedral geometry is attributable to the restricted bite angles of the ligand.     

Preparation of some nickel(II) and copper(II) complexes of the SCHIFF-Base derived from Acetophenone and Ethylenediamine

Preparation and properties of the following Ni^II and Cu^II complexes of the Schiff base derived from acetophenone and ethylenediamine (BAPE) and also of the mixed Ni^II and Cu^II chelates with BAPE and acetylacetone (acac-H) are described: In each case the Schiff base, BAPE, acts as a neutral bidentate ligand. The complexes are characterised by electronic spectra, magnetic susceptibilities, conductivities and elemental analyses. Pseudotetrahedral structure is proposed for M(BAPE)C1₂, while tetragonal structure for [M(BAPE)(acac)(H₂O)₂]C_lO₄ (M = Ni and Cu). The complex [Ni(BAPE) (acac)]ClO₄ has been found to be square planar.     

Synthesis and structural characterization of 3d-metal complexes of pyridine-4-carboxaldehyde thionicotinoyl hydrazone

Summary Pyridine-4-carboxaldehyde thionicotinoyl hydrazone (4-PTNH) forms 1:1 adducts with metal(II) halides and 1:2 complexes (metal to ligand) with metal(II) thiocyanates. Magnetic and spectral studies indicate polymeric octahedral geometry for M(4-PTNH)X₂ (M=Co^II or Cu^II, X=Cl; M=Ni^II, X=Cl, Br or I), five coordinate geometry for Co(4-PTNH)X₂ (X=Br or I) and octahederal geometry for [M(4-PTNH)₂(NCS)₂] (M=Co^II or Ni^II). I.r. spectral studies show that 4-PTNH acts as a neutral bidentate ligand in all the complexes, the bonding sites being the thione sulphur and azomethine nitrogen.     

Synthesis,characterization and antimicrobial studies on 13-membered-N6-macrocyclic transition metal complexes containing trimethoprim

Asymmetrical macrocyclic complexes of Mn^II, Co^II, Ni^II, Cu^II and Zn^II have been synthesized by the template process using bis(benzil)ethylenediamine as precursor. Bis(benzil)ethylenediamine reacts with transition metal chlorides and trimethoprim in a 1:1:1 molar ratio in methanol to give several solid metal complexes of the general composition [M(L)X₂] (M = Mn^II, Co^II, Ni^II, Cu^II and Zn^II, L = ligand and X = Cl^?). They were characterized by physicochemical and spectroscopic techniques. Based on analytical, spectral and magnetic moments, all the complexes are identified as distorted octahedral structures. All the complexes are of the [M(L)X₂] type. The shifts of the ν(CN) (azomethine) stretches have been monitored. To find out the donor sites of the ligands, the activity data show that the metal complexes are more potent than the parent ligand. The [M(L)X₂] complexes showed a broad spectrum of antimicrobial activity in vitro against both gram-positive and gram-negative human pathogenic bacterial isolates and the antimicrobial spectrum enhanced only with a combination of metal chlorides and trimethoprim complex. From the results it is imperative that the synthesized macrocyclic [M(L)X₂] complexes exhibit potent broad spectrum antibacterial activity.     

Metal chelates of ligands containing the ONS donor grouping,part I. Metal chelates of Schiff bases derived from fluorinatedβ-diketones and thiosemicarbazide

Summary The Schiff bases RC(OFl)=CFlC(CF₃)=NNlJC(S)NH₂ (R = 2-thienyl, Ph,p-BrC₆H₄,p-MeC₆H₄,p-MeOC₆H₄,m-McOC₆H₄, -naphthy], Prⁱ) have been prepared by condensation of fluorinated -diketones with thiosemicarbazide. By the loss of one or two protons from their tautomeric iminothiol form RC(OH)=CHC(CF₃)=NN=C(SH)NH₂ the Schiff bases act as (i) doubly negatively charged ONS tridentate or (ii) singly negatively charged NS bidentate ligands, respectively. The Schiff bases give dimeric µ₂-dithiolo-bridged complexes M(ONS)₂ (M = Ni, Pd, and Pt). The thiolo-bridges in the nickel complexes can be split by reaction with pyridine to give the monomeric compounds Ni(ONS)py, whereas the palladium and platinum complexes are unreactive towards pyridine. When R = 2-thienyl orp-BrC₆H₄, 1:2 complexes of the type M(HONS)₂ (M = Pd or Pt) were isolated. With copper(II) the Schiff bases yield the complexes Cu^II(ONS). Cu^I(HONS) which are considered to have a polymeric structure involving -thiolo-bridges.     

New complexes of iron(III), cobalt(II), nickel(II) and copper(II) with Schiff bases derived from 2-aminocyclopent-1-ene-1-dithiocarboxylic acid

Summary Fe^III, Co^II, Ni^II and Cu^II, complexes of a new Schiff base ligand, prepared by condensing 2-aminocyclopent-1-ene-1-dithiocarboxylic acid with benzaldehyde (ACB), and also Cu^II and Ni^II complexes of a second Schiff base ligand prepared by condensing 2-aminocyclopent-1-ene-1-dithiocarboxylic acid with salicylaldehyde (ACS), have been prepared and characterized by elemental analyses, conductivity measurements, magnetic and spectral (electronic, i.r. and e.p.r.) studies. The i.r. spectra suggest that both ACB and ACS are acting as bidentate ligands, coordinating through one of the sulphur atoms and through the azomethine nitrogen atom. The magnetic moment of the Fe^III complex indicates spin crossover behaviour. Square planar structures have been assigned to the Cu^II and Ni^II complexes and a tetrahedral structure to the Co^II complex. The e.p.r. spectra of the Cu^II complexes suggest a square planar environment with rhombic distortion around the Cu^II ion.     

Coordination compounds derived from transition metal salts and bis(3,5-dimethylpyrazolyl)methane

Summary The preparation of transition metal complexes containing the sterically hindered ligand, bis(3,5-dimethylpyrazolyl)methane (LL) is described. Compounds of formula M(LL)X₂ (M = Co^II, Ni^II or Zn^II and X = Cl^– or Br^–) or M(LL)₂X₂ (M = Mn^II, Fe^II, Co^II, Ni^II, Cu^II, Zn^II or Cd^II and X = ClO ₄ ^– ; M = Co^II, Ni^II, Cu^II or Zn^II and X = NO ₃ ^– ; M = Ni^II or Cu^II and X = Cl^– or Br^–) have been isolated. In addition, an apparently trimeric Cu₃(LL)₄Cl₆ · EtOH compound is reported. For Ni(LL)Cl₂ a five-coordinated chloro-bridged dimer is found. The perchlorato compounds, M(LL)₂(ClO₄)₂, appear to have one bidentate ClO ₄ ^– and one ionic ClO ₄ ^– group. The M(LL)₂ species appears to occur either in octahedral geometry, leaving twocis-positions free, or in a tetrahedral geometry without space for other ligands, and probably also in a five-coordinate geometry with one free ligand position.Structural conclusions are drawn from i.r., far-i.r. and ligand-field spectra, x-ray powder patterns, magnetic susceptibility data, e.s.r. spectra and conductivity data.