Syntheses and structural characterizations of a new benzyl(4-methoxyphenyl)dithiophosphinic acid and its Ni(II), Co(II), Zn(II), Cd(II), and Ni–pyridine complexes

Benzyl(4-methoxyphenyl)dithiophosphinic acid (HL) was obtained as solid and was treated with the NiCl₂6H₂O, CoCl₂6H₂O, ZnCl_2, and CdCl₂ to prepare its Ni(II), Co(II), Zn(II), and Cd(II) complexes. The nickel complex was further treated with pyridine which led to the formation of octahedral dipyridine derivative. HL was obtained through the addition reaction of the perthiophosphonic acid anhydride Lawesson reagent, (LR), [2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide], with the corresponding Grignard compound (benzylmagnesium bromide) in diethyl ether medium.

The complexes were all of the stoichiometry of [M(L)₂]_x, with x = 1 for M = Ni²⁺ and x = 2 for M = Co²⁺, Cd²⁺ and Zn²⁺. The coordination geometry was square planar in the nickel(II) complex and tetrahedral in the others. Similar to many other nickel(II) complexes, the Ni(L)₂ reacts reversibly with pyridine to yield the octahedral complex ({(Py)₂Ni(L)₂}).

The compounds were characterized by elemental analysis; MS, FTIR, and Raman spectroscopies. The magnetic susceptibilities of the complexes were measured to confirm the hybridization patterns and the geometries. Single-crystal X-ray analyses of Ni(L)₂ and [Co(L)₂]₂ complexes were also carried out to prove the molecular topologies.     

Electric Field Enhancement of Donnan Dialysis

Abstract

Donnan dialysis of cations into simple receiver electrolytes such as NaNO₃ is inhibited by interaction between the fixed sulfonate exchange sites on the cation exchange membrane and the test cations. Application of a 5 V cm^?1 (peak-to-peak) sine wave at 1 MHz across the membrane diminishes the retardation and allows the Donnan dialysis rate to approach the diffusion limit with Cd, Cu, and Zn test metals and a 0.1 M NaNO₃ receiver. The transport to Pb is still retarded by about 25%. The use of 0.2 M Mg(II), 0.5 mM Al(III) receiver results in diffusion limited transport for all metals.     

Synthesis and crystal structures of Cd[AlCl4]2 and Cd2[AlCl4]2

Colorless single crystals of Cd[AlCl₄]₂ grow from the melt of CdCl₂ and AlCl₃ upon slow cooling from 250°C. The crystal structure [monoclinic, P1a1, Z = 2, a = 1288.7(2), b = 660.2(1), c = 705.1(1) pm, β = 92.89(1)º] may be derived from hexagonally closest packed layers of Cl^?. Octahedral and tetrahedral holes are filled with Cd²⁺ and Al³⁺ in a 1:2 ratio between all layers stacked in the [104] direction. Cd[GaCl₄]₂ and Cd[AlBr₄]₂ are isotypic. Reduction of Cd[AlCl₄]₂ with excess cadmium shot and slow cooling from 350°C yields plate-like very moisture-sensitive, colorless single crystals of Cd₂[AlCl₄]₂. The crystal structure [triclinic, C1 , Z = 2, a = 655.47(3), b = 1135.26(1), c = 935.23(6) pm, α = 89.70(2)º, β = 103.61(1)º, γ = 90.455(1)º] is built from slabs stacked in the [100] direction consisting of ethane-like [Cd₂Cl₆] units with a Cd? Cd distance of 256.1 pm sharing common vertices with [AlCl₄] tetrahedra.     

Coordination geometries and crystal structures of cadmium(II) complexes with a new amino alcohol (NN′O) ligand

The new ligand 2-(2-(2-hydroxyethylamino)ethylamino)cyclohexanol, (HEAC), was prepared under microwave conditions through ring opening of cyclohexene oxide with 2-(2-amino-ethylamino)ethanol. Its cadmium(II) complexes [Cd₂(HEAC)₂(μ-Cl)₂Cl₂] (1) and [Cd(HEAC)₂][CdI₄] (2) were identified by elemental analysis, FT-IR, Raman, ¹H NMR spectroscopies, and single-crystal X-ray diffraction. HEAC formed 1?:?1 M?:?L complexes with cadmium chloride and cadmium iodide. Complex 1 crystallized as a dimer with two asymmetrically bound bridging Cl^? and a terminally coordinated Cl^? on each metal. The geometry around the cadmiums in 1 with four five-membered chelate rings and four Cl^? ligands is distorted octahedral for each Cd(II). The cyclohexanol OH of each ligand forms intramolecular hydrogen bonds. In 2, the coordination numbers for cadmium in [Cd(HEAC)₂]²⁺ and [CdI₄]^2? moieties are six and four, respectively. In [Cd(HEAC)₂]²⁺ each ligand coordinates through two N- and one O-donors, leading to a distorted octahedral geometry. The geometry of [CdI₄]^2? in 2 is slightly distorted tetrahedral. The protonation equilibrium constants of the two secondary amino groups in HEAC, determined by pH-potentiometry, were 6.26 and 9.26, respectively, at 25°C. Stability constants for this ligand with Ni(II), Cu(II), and Zn(II) (1?:?1 M?:?L), determined by glass-electrode potentiometry, were 7.13, 10.50, and 5.42, respectively.     

Kinetic Study of the Reduction of Bromate Ion by Tris(1,10-Phenanthroline)Iron(II) and Aquoiron(II) Ions — Implication for the Bromate-Gallic Acid Oscillating Reaction

The kinetics of the bromate oxidation of tris(1,10-phenanthroline)iron(II) (Fe(phen)₃²⁺) and aquoiron(II) (Fe²⁺ (aq)) have been studied in aqueous sulfuric acid solutions at μ = 1.0M and with Fe(II) complexes in great excess. The rate laws for both reactions generally can be described as -d [Fe(II)]/6dt = d[Br^?]/dt = k[Fe(II)] [BrO^?₃] for [H⁺]₀ = 0.428–1.00M. For [BrO^?₃]₀ = 1.00 × 10^?4M. [Fe²⁺]₀ = (0.724–1.45)x 10^?2 M, and [H⁺]₀ = 1.00M, k = 3.34 ± 0.37 M^?1s^?1 at 25°. For [BrO^?₃]₀ = (1.00–1.50) × 10^?4M, [Fe²⁺]₀ = 7.24 × 10^?3M ([phen]₀ = 0.0353M), and [H⁺]₀ = 1.00M, k = (4.40 ± 0.16) × 10^?2 M^?1s^?1 at 25°. Kinetic results suggest that the BrO^?₃-Fe²⁺ reaction proceeds by an inner-sphere mechanism while the BrO^?₃-Fe(phen)₃²⁺ reaction by a dissociative mechanism. The implication of these results for the bromate-gallic acid and other bromate oscillators is also presented.     

Cadmium(II) iodide and thiocyanate complexes adopted by polycyclic 1,4‐bis(pyridazin‐4‐yl)benzene: interplay of coordination and π–π stacking interactions

New complexes containing the 1,4‐bis(pyridazin‐4‐yl)benzene ligand, namely diaquatetrakis[1,4‐bis(pyridazin‐4‐yl)benzene‐κN²]cadmium(II) hexaiodidodicadmate(II), [Cd(C₁₄H₁₀N₄)₄(H₂O)₂][Cd₂I₆], (I), and poly[[μ‐1,4‐bis(pyridazin‐4‐yl)benzene‐κ²N²:N^2′]bis(μ‐thiocyanato‐κ²N:S)cadmium(II)], [Cd(NCS)₂(C₁₄H₁₀N₄)]_n, (II), demonstrate the adaptability of the coordination geometries towards the demands of slipped π–π stacking interactions between the extended organic ligands. In (I), the discrete cationic [Cd—N = 2.408 (3) and 2.413 (3) Å] and anionic [Cd—I = 2.709 (2)–3.1201 (14) Å] entities are situated across centres of inversion. The cations associate via complementary O—H...N^2′ hydrogen bonding [O...N = 2.748 (4) and 2.765 (4) Å] and extensive triple π–π stacking interactions between pairs of pyridazine and phenylene rings [centroid–centroid distances (CCD) = 3.782 (4)–4.286 (3) Å] to yield two‐dimensional square nets. The [Cd₂I₆]²⁻ anions reside in channels generated by packing of successive nets. In (II), the Cd^II cation lies on a centre of inversion and the ligand is situated across a centre of inversion. A two‐dimensional coordination array is formed by crosslinking of linear [Cd(μ‐NCS)₂]_n chains [Cd—N = 2.3004 (14) Å and Cd—S = 2.7804 (5) Å] with N²:N^2′‐bidentate organic bridges [Cd—N = 2.3893 (12) Å], which generate π–π stacks by double‐slipped interactions between phenylene and pyridazine rings [CCD = 3.721 (2) Å].     

Metal Ion Buffer Systems for Ionometry in Water-Ethanol Mixtures and Micellar Medium of Sodium Dodecyl Sulfate

The concentration dissociation constants of nitrilotriacetic acid and the concentration stability constants of Cd(II) complexes with the nitrilotriacetic acid anion in water-ethanol mixtures and of Cu(II) and Cd(II) complexes with o-phenanthroline and 2,2′-bipyridine in micellar solutions of sodium dodecyl sulfate were determined potentiometrically. Based on the concentration constants determined, Cd²⁺ and Cu²⁺ buffer solutions were developed for calibration of a Cd²⁺-selective electrode in water-ethanol mixtures and Cd²⁺ and Cu²⁺-selective electrodes in micellar solutions of sodium dodecyl sulfate within the ranges pCu 9.7–13.5 and pCd 7.5–11.8.__________Translated from Zhurnal Prikladnoi Khimii, Vol. 78, No. 2, 2005, pp. 273–278.Original Russian Text Copyright © 2005 by Chernysheva, Loginova, Bazilyanskaya.     

Complexation in Binary Cd2[Fe(CN)6]–M(II) Systems (M = Mn,Co, Ni,Cu, Zn) in Gelatin-Immobilized Cadmium(II) Hexacyanoferrates(II)

Complexation processes that occur between cadmium(II) hexacyanoferrate(II) (Cd₂[Fe(CN)₆]) and 3d-metal ions M(II) (M = Mn, Co, Ni, Cu, Zn) in thin gelatin layers with the immobilized cadmium(II) hexacyanoferrates when brought in contact with aqueous solutions of d-metal chlorides are studied. Cd²⁺ ions were found to be replaced to some extent by M²⁺ ions of the indicated d metals (except for Mn(II)) and form binuclear (dd)-metal hexacyanoferrates(II). A complete replacement of Cd(II) and formation of M₂[Fe(CN)₆] was observed in none of the cases.     

EPR studies of copper(II) complexes with poly-2-methyl-5-vinyl-pyridine and poly-2-vinylpyridine

Cu(II) complexes of poly-2-vinylpyridine (P2VP) and poly-2-methyl-5-vinylpyridine (P2M5VP), partially quaternized by dimethylsulphate, and of the analogues (2-methyl-5-ethylpyridine, 2-ethylpyridine) were studied by EPR spectroscopy in a mixture of methanol and water. Peculiarities of the complex formation reaction were observed for the polymers compared to the analogues. At ratios of [Py]:[Cu²⁺] > 40, the predominant formation of tetrapyridinate-Cu(II) species [(CuL₄)]²⁺ was found for P2M5VP. However, differences were found between the parameters of EPR-spectra for the [CuL₄]²⁺ in the polymer from that of the [Cu(2M5EPy)₄]²⁺. It was suggested that, in the polymer, [CuL₄]²⁺ complexes with structure intermediate between square planar and tetrahedral are formed. Moreover, the maximum value of the pyridine fraction forming [CuL₄]²⁺ in P2M5VP was found to be about 10% and it is appreciably less the value of the fraction in P4VP (about 40%). For P2VP at [Py]:[Cu²⁺] > 40, an insignificant amount of [CuL₁]²⁺ and [CuL₂]²⁺ are formed in the solution. It follows that the main chain position relative to the ligand nitrogen atom in these polyvinylpyridines affects profoundly the complexation between the macromolecules and Cu(II) ions. The steric hindrances due to the chain are likely to change the [CuL₄]²⁺ structure and to prevent complex formation for P2VP.     

Cadmium iodide complexes with dimethylsulphoxide,and their crystal structures

The crystalline compounds [{CdI₂(dmso)}_n] ( 1 ,) and [Cd₂I₄(dmso)₄] ( 2 ,) provide a structural sequence illustrating the conversion of CdI₂ into the ionic derivatives [Cd(dmso)₆]²⁺ [Cd(dmso)I₃]₂^? · EtOH ( 3 ,) and [Cd(dmso)₆]²⁺ CdI₄^2? ( 4 ,), with increasing proportions of dmso. ( 1 ,) comprises polymeric chains with Cd centres linked by bridging iodide atoms, and alternately in four- and six-coordination. ( 2 ,) is a binuclear segment of the chains and can be seen as the structural forerunner of the ionic compounds ( 3 ,) and ( 4 ,). The ion packing in ( 3 ,) is loose, with lattice ethanol.     

Solubility of <Emphasis Type="Italic">d</Emphasis>-Element Salts in Organic and Aqueous–Organic Solvents: VI.<Superscript>1</Superscript> Structure and Thermal Stability of Cadmium Iodide and Bromide Solvates with Dimethylacetamide and Dimethylformamide

Five solvates, [CdBr₂(DMF)] _n , [CdBr₂(DMA)] _n , [CdI²(DMF)] ⁿ , [Cd(DMF)₆][Cd₂I₆], and {[Cd(DMA)₆][Cd₅I₁₂] _n } _m , were isolated from the ternary systems CdX₂–L–H₂O (X = Br, I; L = N,N-dimethylacetamide, N,N-dimethylformamide) and characterized by the X-ray single crystal analysis. The structures of the first three solvates is similar to each other in structures and represent a one-dimensional polymer chain, the fourth solvate has the discrete structure containing [Cd(DMF)₆]²⁺ and [Cd₂I₆]^2– ions, and the fifth solvate contains discrete [Cd(DMA)₆]²⁺ cations and the polymer anionic fragment [Cd₅I₁₂] _n ^2n–.     

Synthesis and Structural Characterization of One‐Dimensional Cadmium(II) Coordination Polymers Containing Polydentate Nitrogen Ligands

The reactions of Cd(NO₃)₂·4H₂O with NH₄SCN and 2,4‐dpa (2,4‐dpa = 2,4‐dipyridineamine) in CH₃OH afforded the one‐dimensional coordination polymer [Cd(NCS)₂(2,4‐dpa)₂]_n, 1 , while reaction of Cd(NO₃)₂·4H₂O with NH₄SCN and PmPa (PmPa = 2‐(1‐piperazinyl)pyrimidine) in CH₃OH gave complex of the type [Cd(NCS)₂(PmPa)₂]_n, 2. Each of the 2,4‐dpa ligand in complex 1 is coordinated to the Cd²⁺ metal center through pyridyl nitrogen atoms to form the one‐dimensional chain structures. The distorted {CdN4S2} octahedral coordination geometry around Cd²⁺ center is completed by pairs of bidentate thiocyanato ligands. Complex 2 has the 1‐D arrangement constructed through one‐dimensional double μ(N,S) end‐to‐end bridging thiocyanato groups bridged Cd(II) chains interconnected through PmPa ligands.     

Three Novel Mixed‐ligand Cadmium(II) Sulfonates with Aza‐aromatic Skeltons as Co‐ligands

To survey the influence of aza‐aromatic co‐ligands on the structure of Cadmium(II) sulfonates, three Cd(II) complexes with mixed‐ligand, [Cd^II(ANS)₂(phen)₂] ( 1 ), [Cd^II(ANS)₂(2,2′‐bipy)₂] ( 2 ) and [Cd^II(ANS)₂(4,4′‐bipy)₂]_n ( 3 ) (ANS = 2‐aminonaphthalene‐1‐sulfonate; phen = 1,10‐phenanthroline; 2,2′‐bipy = 2,2′‐bipyridine; 4,4′‐bipy = 4,4′‐bipyridine) were synthesized by hydrothermal methods and structurally characterized by elemental analyses, IR spectra, and single crystal X‐ray diffraction. Of the three complexes, ANS consistently coordinates to Cd²⁺ ion as a monodentate ligand. While phen in 1 and 2,2′‐bipy in 2 act as N,N‐bidentate chelating ligands, leading to the formation of a discrete mononuclear unit; 4,4′‐bipy in 3 bridges two Cd^II atoms in bis‐monodentate fashion to produce a 2‐D layered network, suggesting that the conjugate skeleton and the binding site of the co‐ligands have a moderate effect on molecular structure, crystal stacking pattern, and intramolecular weak interactions. In addition, the three complexes exhibit similar luminescent emissions originate from the transitions between the energy levels of sulfonate anions.     

Quality control of analyses of mercury in hair

Summary Flow injection analysis (FIA) has been combined with a dialysis unit in order to study the effect of interferences in the determination of free cyanide in waste water. Two kinds of interferences, metals and inorganic anions, were studied. In all the cases, solutions of constant cyanide concentration containing interferences were introduced in the FIA system and free cyanide was determined after hydrogen cyanide passes the dialysis membrane.Results reveal the advantages of this methodology for Zn(II), Cu(I), Cd(II), Nr ₄ ⁺ and inorganic anions. Fe(III), Co(II), Ni(II) and carbonate show different behaviour under these conditions.

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Entfernung von Störungen bei der spektralphotometrischen Cyanidbestimmung unter Verwendung von Dialyse und Fließinjektion

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Presented at Euroanalysis VI, Paris, September 8–11, 1987     

Preparation, structural characterisation, and magnetic properties of [Cu(men)2][Cu2Cd2Cl2(CN)6] (men = N-methylethane-1,2-diamine)

The novel complex [Cu(men)₂][Cu₂Cd₂Cl₂(CN)₆] (I) was isolated from the aqueous-ethanol system containing CuCl₂, men (men = N-methylethane-1,2-diamine) and K₂[Cd(CN)₄] in the presence of dilute hydrochloric acid and chemically and spectroscopically characterised. The crystal structure of I consists of [Cu ₂ ^I (CN)₆] and [Cd₂Cl₂(CN)₆] building units bridged by cyanide ligands and forms a three-dimensional skeleton with cavities. [Cu(men)₂]²⁺ cations in which two men ligands are chelated (mean Cu-N is 2.033(6) Å) are located in the cavities. The coordination polyhedron around the Cu(II) atoms is formed as a tetragonal bipyramidal by two weaker axial Cu-Cl bonds (2.8642(12) Å) with chlorido ligands from the skeleton. The Cu(I) and Cd(II) atoms in the skeleton exhibit tetra-(CuC₄ chromophore) and penta-coordination (CdN₃Cl₂), respectively. The temperature-dependent susceptibility measurements indicate a Curie-Weiss-like behaviour and the presence of weak anti-ferromagnetic interaction.     

Binary Polyazides of Cadmium and Mercury

Following our interest in binary element–nitrogen compounds we report here on the synthesis and comprehensive characterization (M.p., IR/Raman, elemental analysis, ¹⁴N/¹³³Cd/¹⁹⁹Hg NMR) of tri‐ and tetraazido cadmate and mercurate anions [E(N₃)_(2+n)]^n? (E=Cd, Hg; n=1, 2) in a series of [Ph₄P]⁺ and [PNP]⁺ ([PNP]⁺=bis(triphenylphosphine)iminium) salts. The azide/chloride exchange in CH₂Cl₂ as well as the formation of tetrazolate salts in CH₃CN solutions of the polyazido mercurates were investigated. Single crystal X‐ray structures of all new compounds, and for comparison [Ph₄P][Cd₂(N₃)₅(H₂O)], were determined. Moreover, the synthesis of anhydrous cadmium(II) azide and its DMSO adduct is presented for the first time. For a better understanding of structure and bonding in E(N₃)₂, [E(N₃)₃]^? and [E(N₃)₄]^2?, theoretical calculations at the M06‐2X/aug‐cc‐pVDZ level were carried out.     

Cadmium(II) chloride,bromide and iodide complexes with 4,4′‐bipyridazine: when are diazine and halide bridges (in)compatible?

In poly[di‐μ‐chlorido‐μ‐(4,4′‐bipyridazine)‐κ²N¹:N^1′‐cadmium(II)], [CdCl₂(C₈H₆N₄)]_n, (I), and its isomorphous bromide analogue, [CdBr₂(C₈H₆N₄)]_n, (II), the halide atom lies on a mirror plane and the Cd^II ion resides at the intersection of two perpendicular mirror planes with m2m site symmetry. The pyridazine rings of the ligand lie in a mirror plane and are related to each other by a second mirror plane perpendicular to the first. The compounds adopt the characteristic structure of the [M^IIX₂(bipy)] type (bipy is bipyridine) based on crosslinking of [Cd(μ‐X)₂]_n chains [Cd—Cl = 2.5955 (9) and 2.6688 (9) Å; Cd—Br = 2.7089 (4) and 2.8041 (3) Å] by bitopic rod‐like organic ligands [Cd—N = 2.368 (3)–2.380 (3) Å]. This feature is discussed in terms of supramolecular stabilization, implying that the periodicity of the inorganic chain [Cd...Cd = 3.7802 (4) Å in (I) and 3.9432 (3) Å in (II)] is favourable for extensive parallel π–π stacking of monodentate pyridazine rings, with centroid–centroid distances of 3.7751 (4) Å in (I) and 3.9359 (4) Å in (II). This is not the case for the longer iodide bridges, which cannot stabilize such a pattern. In poly[tetra‐μ‐iodido‐μ₄‐(4,4′‐bipyridazine)‐κ⁴N¹:N²:N^1′:N^2′‐dicadmium(II)], [Cd₂I₄(C₈H₆N₄)]_n, (III), the ligands are situated across a centre of inversion; they are tetradentate [Cd—N = 2.488 (2) and 2.516 (2) Å] and link successive [Cd(μ‐I)₂]_n chains [Cd—I = 2.8816 (3)–3.0069 (4) Å] into corrugated layers.     

Complex formation of Cu(II), Ni(II), Zn(II), Co(II), and Cd(II) acetates with 3,3′,4,4′,5,5′-hexamethyldipyrrolylmethene

The reactions of complex formation of Cu(II), Co(II), Zn(II), Ni(II), and Cd(II) acetates with 3,3′,4,4′5,5′-hexamethyl-2,2′-dipyrrolylmethene (HL) in DMF were studied by the electronic spectroscopy and calorimetric titration methods at 298.15 K. The main products of the above reactions are [ML₂] chelates. In the case of Cu and Ni salts, the process occurs through the spectrally recorded stage of formation of the heteroligand [ML(AcO)] complexes. The reaction with Cd acetate terminates at the stage of the heteroligand complex formation due to the large radius and decreasing electron affinity of the Cd²⁺ ion. The effect of the metal nature appears in the increasing thermodynamic stability of single-type complexes in the series [ML₂]: Ni(II) < Zn(II) < Co(II) < Cu(II) and [ML(AcO)]: Cd(II) < Ni(II) < Cu(II).     

A series of coordination polymers constructed from flexible bis(benzimidazole)ether ligands and different carboxylates

Six new coordination polymers constructed from two structurally related ligands, 2,2′-bis(2-methylbenzimidazole) ether (L1) and 2,2′-bis(2-ethylbenzimidazole)ether (L2), have been synthesized. They are [Cu(L1)(bz)₂] (1), [Cu(L2)(bz)₂] (2), [Zn₂(L1)(m-bdc)₂] (3), [Cd₂(L2)(m-bdc)₂(H₂O)]₂·H₂O (4), [Zn(L1)(OH-bdc)-(H₂O)] (5) and [Zn₂(L₂)(btca)] (6), where Hbz = benzoic acid, m-H₂bdc = 1,3-benzenedicarboxylic acid, OH-H₂bdc = 5-hydroxyisophthalic acid, and H₄btca = 1,2,4,5-benzenetetracarboxylic acid. In 1 and 2, the bidentate N-donor ligands (L1 and L2) bridge neighboring metal centers to form 1D single chains. The bz anions are attached on both sides of the chains. In 3 and 4, the N-donor ligands (L1 and L2) in cis conformations bridge two metal centers to generate a [M₂(L1)]⁴⁺ unit (M = Zn(II) and Cd(II)). The adjacent [M₂(L1)]⁴⁺ units are further linked via the dicarboxylate anions to form 1D double chain structures. In 5, the Zn(II) cations are bridged by OH-m-bdc anions to form an infinite polymeric chain. The L1 ligands are attached on one side of the chain in a monodentate mode. In 6, two Zn(II) cations are bridged by two L2 ligands to form a [ZnL2]₂ ⁴⁺ ring, which is further linked by btca anions to generate a 2D layer. The luminescent properties of the ligands and 3–6 in the solid state at room temperature were also studied.     

Cd2Cu(PO4)2

During an investigation of the insufficiently known system M1O–M2O–X₂O₅–H₂O (M1 = Cd²⁺, Sr²⁺ and Ba²⁺; M2 = Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺ and Mg²⁺; X = P⁵⁺, As⁵⁺ and V⁵⁺), single crystals of the novel compound dicadmium copper(II) bis[phosphate(V)], Cd₂Cu(PO₄)₂, were obtained. This compound belongs to a small group of compounds adopting a Cu₃(PO₄)₂‐type structure and having the general formula M1₂M2(XO₄)₂ (M1/M2 = Cd²⁺, Cu²⁺, Mg²⁺ and Zn²⁺; X = As⁵⁺, P⁵⁺ and V⁵⁺). The crystal structure is characterized by the interconnection of infinite [Cu(PO₄)₂]_n chains and [Cd₂O₁₀]_n double chains, both extending along the a axis. Exceptional characteristics of this structure are its novel chemical composition and the occurrence of double chains of CdO₆ polyhedra that were not found in related structures. In contrast to the isomorphous compounds, where the M1 cations are coordinated by five O atoms, the Cd atom is coordinated by six. The dissimilarity in the geometry of M1 coordination between Cd₂Cu(PO₄)₂ and the isomorphous compounds is mostly due to the larger ionic radius of the Cd cation in comparison with the Cu, Mg and Zn cations. Sharing a common edge, two CdO₆ polyhedra form Cd₂O₁₀ dimers. Each such dimer is bonded to another dimer sharing common vertices, forming [Cd₂O₁₀]_n double chains in the [100] direction. The Cu atoms, located on an inversion centre (site symmetry ), form isolated CuO₄ squares interconnected by PO₄ tetrahedra, forming [Cu(PO₄)₂]_n chains similar to those found in related structures. Conversely, the [Cd₂O₁₀]_n double chains, which were not found in related structures, are an exclusive feature of this structure.