Structures of the complex ions [CuCl<Subscript>4</Subscript>]<Superscript>2−</Superscript> and [CuCl<Subscript>5</Subscript>]<Superscript>3−</Superscript>

The electronic structures of the complex ions [CuCl₄]^2? and [CuCl₅]^3? were analyzed in terms of the extended angular overlap model (AOM) with consideration to sd and pd mixing. The total antibonding orbital energies of these ions show no anomalies in the transition from a tetrahedron to a planar square [CuCl₄]^2? and from a trigonal bipyramid to a tetragonal pyramid [CuCl₅]^3?. Presumably, the existence of numerous intermediate forms of these complexes is mainly due to the packing effects rather than the electronic factors.     

Organic-inorganic hybrid supramolecular architecture constructed from Keggin-type [PMo<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Superscript>3−</Superscript> clusters and transition metal complexes

A Keggin organic-inorganic hybrid polyoxometalate combined with nickel complex [Ni (Dmf)₃(H₂O)][HPMo₁₂O₄₀] · (Dmf) · 2H₂O (I) has been synthesized and structurally characterized by elemental analysis, IR spectrum, TG analysis, cyclic voltammetry, and single-crystal X-ray diffraction. Interestingly, a two-dimensional supramolecular network is constructed by the [PMo₁₂O₄₀]³⁻ polyanions, [Ni(Dmf)₃(H₂O)]²⁺ cations, and water molecules via hydrogen-bonding interactions. The cyclic voltammetric measurements illustrate that the [PMo₁₂O₄₀]³⁻ polyanion is the electrochemical redox active center of I in the solution.     

Structural characterization of two lanthanide complexes attached to [H<Subscript>2</Subscript>W<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Superscript>6−</Superscript>

In this article, two compounds [H₂bpy][Ln(DMF)₄(H₂O)₃(Hbpy)][H₂W₁₂O₄₀] (Ln = La,Ce; DMF = N,N-dimethylformamide, bpy = 4,4′-bipyridine) have been synthesized and characterized by single-crystal X-ray diffraction, IR spectra, and TG analysis. X-Ray analysis showed that the [Ln(DMF)₄(H₂O)₃(Hbpy)]⁴⁺ unit is supported on the α-Keggin polyoxoanion [H₂W₁₂O₄₀]⁶⁻ via the surface bridging oxygen atom. The [H₂bpy][Ln(DMF)₄(H₂O)₃(Hbpy)][H₂W₁₂O₄₀] entity is further extended into 2D supramolecular networks with 1-D channels by hydrogen-bonding interactions, in which 4,4′-bipy ligands reside. To the best of our knowledge, these complexes represent the first examples of rare earth metal-organic complex-decorated α-metatungstate clusters. Furthermore, the electrochemical properties of these compounds have been studied via the method of bulk-modified carbon paste electrodes.     

Interaction of [В<Subscript>10</Subscript>H<Subscript>10</Subscript>]<Superscript>2–</Superscript> and [В<Subscript>12</Subscript>H<Subscript>12</Subscript>]<Superscript>2–</Superscript> with nitro compounds

The interaction of the [B₁₀H₁₀]^2– and [B₁₂H₁₂]^2– anions with aliphatic and aromatic nitro compounds (RNO₂, where R = Et, n-Pr, i-Pr, tert-Bu, Ph) has been studied under irradiation with visible and UV light. It has been shown that, depending on the reaction conditions, both mono- and disubstituted nitro-closo-decaborates can be selectively obtained in yields up to 50%.     

Structure of sulfanilamide-containing cobalt(III) dioximates with the [ZrF<Subscript>6</Subscript>]<Superscript>2−</Superscript> and [BF<Subscript>4</Subscript>]<Superscript>−</Superscript> anions

The complexes [Co(DH)₂(Sam)₂]₂[ZrF₆]·5H₂O (I) and [Co(DH)₂(Sam)₂][BF₄]·H₂O (II), where DH^? is the dimethylglyoxime monoanion, and Sam is para-aminobenzenesulfamide (sulfanilamide, white streptocid), were synthesized, and their crystal structures were determined by X-ray diffraction analysis. The coordination polyhedron of the Co³⁺ atom is an N₆ octahedron formed by four nitrogen atoms of the two dimethylglyoxime residues and two nitrogen atoms of the Sam fragments. The latter are realized in virtually parallel orientation relative to the polyhedron of the metal atom and its equatorial plane; the average value of the dihedral angles is 26.8(1)°, and there is π-π interaction between the benzene rings of the Sam fragments and the π delocalized equatorial metallocycle. The deviation of the cobalt atom from the four-angle plane is up to 0.009(1) Å. The (Co-N)_DH? and (Co-N)_Sam distances in the [Co(DH)₂(Sam)₂]⁺ complex cations vary from 1.892(2) Å to 1.907(3) Å and from 2.000(2) Å to 2.012(2) Å, respectively. The [ZrF₆]^2? and [BF₄]^? complex anions play the major role in crystal formation; they produce a substantial effect on the formation of a complex system of hydrogen bonds.     

Syntheses,Structures and Properties of Three Heteonuclear Complexes Containing [V<Subscript>10</Subscript>O<Subscript>28</Subscript>]<Superscript>6−</Superscript> Units

Three heteonuclear complexes containing [V₁₀O₂₈]⁶⁻ units, {[Cu(pyr)(H₂O)₄]₂(H₃O)₂[V₁₀O₂₈] · 13.5H₂O}_n (1), {[Ni(pyr)(H₂O)₄]₂(H₃O)₂[V₁₀O₂₈] · 9.5H₂O}_n (2) and [Zn₂(H₂O)₁₄(V₁₀O₂₈)] · H₂PPZ (3) are synthesized and characterized by elemental analyses, IR, single crystal X-ray analyses. The complex 1 and 2 have the similar structures which are composed of the [V₁₀O₂₈]⁶⁻ cluster anion and 1D chain {[M (pyr)(H₂O)₄]²⁺}_n (M = Cu Ni) cations bridged by pyrazine. In the complex 3, Zn²⁺ with two coordination modes is bridged by water molecules to build 1D zigzag chains, and then is linked to the bridging oxygen atoms from [V₁₀O₂₈]⁶⁻ to generate a 2D grid architecture filled with the protoned piperazine (PPZ) molecules. In this paper, the magnetic properties of complex 2 are characterized.     

Structural investigation of salts containing ions [Pd(NH<Subscript>3</Subscript>)<Subscript>4</Subscript>]<Superscript>2+</Superscript> and [IrF<Subscript>6</Subscript>]<Superscript>2–</Superscript>

Double complex salts (DCS) α-[Pd(NH₃)₄][IrF₆]·H₂O (P2₁/m, a = 6.3181(3) Å, b = 10.8718(5) Å, с = 7.4526(4) Å, β = 103.568(2)°), β-[Pd(NH₃)₄][IrF₆]·H₂O (P2₁/с, a = 8.5773(3) Å, b = 10.8791(4) Å, с = = 12.6741(3) Å, β = 122.497(2)°), [Pd(NH₃)₄]₃[IrF₆]₂Cl₂·H₂O (P-1, a = 7.6080(2) Å, b = 7.6274(2) Å, с = 11.8070(3) Å, β = 122.497(2)°), and [Pd(NH₃)₄]₂[IrF₆]NO₃ (Fm-3m, a = 11.21210(10) Å) have been synthesized and structurally characterized for the first time. The existence of polymorphs for the DCS has been revealed. The influence of the chemical composition of the initial reagents on the reaction course and, respectively, the products, has been demonstrated. A hypothesis on the influence of the second coordination sphere on the formation of one or the other polymorph of the DCS has been suggested. It has been shown that the series α-[Pd(NH₃)₄][МF₆]·H₂O (M = Pt, Pd) exhibits isostructurality.     

Bond variations in the complexes [CuCl<Subscript>6</Subscript>]<Superscript>4−</Superscript>

An extended version of the angular overlap model developed from the fourth-order variational perturbation theory was used to explain why sd mixing for [CuCl₆]^4? and other pseudooctahedral complexes [CuL₆]^n? with the split ground state ² E is responsible for strong softening of the vibrational E mode, which results in lengthening and even cleavage of the bonds between the metal atom and the axial ligands.     

Mercury complex [(HOCH<Subscript>2</Subscript>)<Subscript>3</Subscript>CNH<Subscript>3</Subscript>]<Stack><Subscript>2</Subscript><Superscript>+</Superscript></Stack> [HgI<Subscript>4</Subscript>]<Superscript>2−</Superscript>: Synthesis and structure

The complex [(HOCH₂)₃CNH₃] ₂ ⁺ [HgI₄]^2? (I) was synthesized by reacting (trioxymethyl)methylammonium iodide with mercury dioide (2: 1 mol/mol) in acetone. X-ray crystallography shows that the complex consists of two types of crystallographically independent [(HOCH₂)₃CNH₃]⁺ cations and tetrahedral anions [HgI₄]^2? (IHgI, 106.49(2)°–113.99(4)°; Hg-I, 2.7849(8)-2.8105(8) Å. [(HOCH₂)₃CNH₃]⁺ cations are linked via hydrogen bonds O…H-N and O-H…N (O…N, 2.84–2.92 Å) to form polymer chains, which are cross-linked with one another via anions (I…H, 2.81, 2.82 Å).     

Synthesis,Crystal Structure,and Electrochemical Properties of One Polyoxometalate-Based Silver(I) Compound with Keggin-Type [PW<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Superscript>3−</Superscript> Anions

One polyoxometalate-based silver(I) compound [Ag(2,2'-Bipy)₂]₃(PW₁₂O₄₀) (I) (2,2'-Bipy = 2,2'- bipyridine) has been synthesized and structurally characterized by IR spectroscopy, elemental analysis, XRPD and X-ray single-crystal structure analysis (CIF file CCDC no. 1572216). Compound I exhibits a crystalline three-dimentional supramolecular framework constructed by Ag-2,2'-Bipy coordination units and [PW₁₂O₄0]^3? template anions, in which there are multiform π...π interactions and hydrogen bonds. The cyclic voltammetric experiments show that compound I displays a good electrocatalytic activity toward the reduction of nitrite.     

A New Sandwich Polyoxometalate Constructed from a Zn<Stack><Subscript>6</Subscript><Superscript>12+</Superscript></Stack> Hexagon Cluster Sandwiched by Two B-α-[BiW<Subscript>9</Subscript>O<Subscript>33</Subscript>]<Superscript>9−</Superscript>

A new sandwich polyoxometalate Na₄Zn₂[Zn₂(H₂O)₁₀(ZnCl)₆(B-α- BiW₉O₃₃)₂] · 40.5H₂O (1) has been obtained in aqueous solution and characterized by IR, UV, element analysis, TG and single-crystal X-ray analysis. Polyoxoanion 1 is composed of a Zn ₆ ¹²⁺ hexagon sandwiched by two [BiW₉O₃₃]^9? units, which is firstly observed in tungstobismutate. The crystal data for compound 1: Triclinic, space group P–1, a = 15.426(3) Å, b = 15.467(3) Å, c = 15.526(3) Å, α = 74.24(3)°, β = 64.37(3)°, γ = 60.73(3)°, V = 2905.3(1) ų, Z = 1.     

Cobalt—Sandwiched lindqvist hexaniobate dimer [Co(III)H<Subscript>5</Subscript>(Nb<Subscript>6</Subscript>O<Subscript>19</Subscript>)<Subscript>2</Subscript>]<Superscript>8− 1</Superscript>

A new polyoxoniobate K₆Na₂[Co_IIIH₅(Nb₆O₁₉)₂] · 26.5H₂O (I) has been synthesized by a diffusion strategy and structurally characterized by IR spectrum, UV spectroscopy, TG analysis, and single crystal X-ray diffraction. Compound I crystallizes in the cubic Pa \(\bar 3\) space group with a = 17.969(8)Å V = 5802.6(4) ų, Z = 4, R ₁ = 0.0383 and wR ₂ = 0.1187. Compound I consists of the Lindqvist hexaniobate dimer [Co_IIIH₅(Nb₆O₁₉)₂]^8? in which the Co³⁺ cations sare andwiched between and face-shared with two Lindqvist-type [Nb₆O₁₉]^8? subunits. In situ UV spectra display that compound I can stably exist in an aqueous solution.     

Synthesis and Structure of the bismuth complex [Ph<Subscript>3</Subscript>PrP]<Stack><Subscript>4</Subscript><Superscript>+</Superscript></Stack>[Bi<Subscript>4</Subscript>I<Subscript>16</Subscript>]<Superscript>4−</Superscript>

The complex [Ph₃P] ₄ ⁺ [Bi₄I₁₆]^4? · 2 Me₂C=O (I) was synthesized by the reaction of triphenyl(propyl)phosphonium iodide with bismuth iodide in acetone. The crystal structure of complex I was determined by X-ray crystallography. It contains, in addition to solvent molecules, two types of crystallographically independent tetrahedral tetraphenyl(propyl)phosphonium cations and tetranuclear anions [Bi₄I₁₆]^4? in a chair conformation with the bismuth atoms being in an octahedral coordination. The Bi-I distances in the anion vary within 2.8768(4)–3.2524(4) Å.     

First examples of cyano-bridged complexes based on a novel cluster anion [Re<Subscript>12</Subscript>C<Subscript>17</Subscript>(CN)<Subscript>6</Subscript>]<Superscript>6−</Superscript>

Two cyano-bridged compounds of novel dodecanuclear cluster anion [Re₁₂CS₁₇(CN)₆] with Ni²⁺ cations were synthesized, namely, one-dimensional polymer of the composition [{Ni(NH₃)₄} {Ni(NH₃)₅}₂Re₁₂CS₁₇(CN)₆] · 7H₂O (I) with a chain structure and [Ni(NH₃)₆]₃[{Ni(NH₃)₄}₃ {Re₁₂CS₁₇(CN)₆}₂] · 21H₂O (II), containing the anionic dimeric complex [{Ni(NH₃)₄}₃ {Re₁₂CS₁₇(CN)₆}₂]^6?. The structures of both compounds were established by X-ray diffraction analysis. Crystals I are monoclinic, space group P2/n, a = 15.321(3), b = 12.635(2), c = 15.448(3) Å, β = 100.242(3)°, V = 2942.8(8) ų, Z = 2. Crystals II are trigonal, space group R3, a = b = 19.7987(14), c = 28.8642(18) Å, V = 9798.6(12) ų, Z = 3.     

Reaction of the [B<Subscript>10</Subscript>H<Subscript>9</Subscript>O<Subscript>2</Subscript>C<Subscript>4</Subscript>H<Subscript>8</Subscript>]<Superscript>–</Superscript> anion with C-nucleophiles

The reactions of 1,4-dioxane-substituted closo-decaborate anion ([B₁₀H₉O₂C₄H₈]^–) with metal acetylenides, diethyl malonate, ethyl acetoacetate, triethyl orthoformate, acetylacetone, and malonodinitrile were studied. The reactions were shown to be accompanied with substituent ring opening and attachment of the corresponding pendant functional group. The obtained compounds were characterized by various physicochemical methods (IR and polynuclear NMR spectroscopy, ESI mass spectrometry).     

Synthesis and crystal structure of a cyanide-bridged one-dimensional nickel(II) complex with alternating [Ni(En)<Superscript>2</Superscript>]<Superscript>2+</Superscript> and [Ni(CN)<Subscript>4</Subscript>]<Superscript>2−</Superscript> ions

The complex [Ni(En)₂][Ni(CN)₄] · 3.5H₂O (I) (En = ethylenediamine) was synthesized by the reaction of [Ni(En)₂](ClO₄)₂ and K₂[Ni(CN)₄] in an H-shaped tube. The crystal structure of I has been determined by single-crystal X-ray analysis. The crystal of complex I is orthorhombic, space group Pnna with a = 28.151(3), b = 8.3946(8), c = 14.5441(13)Å, M =404.76, Z = 8, V = 3437.0(5)ų. The structure of complex I reveals infinite zigzag chains shaped structure are formed by cis-Ni(En)₂-μ-(NC)₂, cis-μ-(NC)₂Ni(CN)₂, and trans-μ-(CN)₂Ni(En)₂.     

Synthesis and characterization of a pure inorganic 3D network based on the [Sr<Subscript>2</Subscript>P<Subscript>9</Subscript>HMo<Subscript>12</Subscript>O<Subscript>71</Subscript>]<Superscript>20</Superscript>–cluster and strontium(II) linkers

Novel supramolecular networks based on an anionic polymolybdophosphate cluster Sr₁₀(H₂O)₁₂[Sr₂P₉HMo₁₂O₇₁] is hydrothermally synthesized and structurally characterized by single crystal X-ray diffraction, thermogravimetric analysis, infrared, ultraviolet spectroscopy, and cyclic voltammetry in an aqueous solution. It crystallizes in the orthorhombic space group Pnmm (No. 59) with a = 12.699(1) Å, b = 14.914(1) Å, c = 23.851(2) Å and Z = 2. The compound is made up of unusual shaped-cage [Sr₂P₉HMo₁₂O₇₁]^20?. The strontium cations are divided in two kinds. The first occupy vacant sites in the [P₉Mo1_{2O 68}]^n– polyoxoanions unit and the second [Sr(H₂O)₆]²⁺, [Sr(H₂O)₄]²⁺, and [Sr(H₂O)₂]²⁺ serve to bridge together the adjacent polymolybdophosphate clusters to yield unprecedented three-dimensional pure inorganic assemblies of the shaped-cage polymolybdophosphate clusters.     

Synthesis and structure of cobalt(III) α-dimethylglyoximates containing thiourea and [ZrF<Subscript>6</Subscript>]<Superscript>2−</Superscript> anion

Two novel coordination compounds of thiourea-containing trans-octahedral trans-dioximates of trivalent cobalt [Co(DH)₂(Tu)₂]₂[ZrF₆]·H₂O and [Co(NioxH)₂(Tu)₂]₂[ZrF₆]·3H²O, where DH^? is the monoanion of dimethylglyoxime, NioxH^? is the monoanion of 1,2-cyclohexanone dioxime, Tu is thiourea, are prepared and characterized by single crystal X-ray diffraction. The structures manifest pairwise an almost parallel and perpendicular arrangement of the Tu fragment in respect to the equatorial plane of the coordination core, accompanied by a development of non-bonding intramolecular π-π-and N-H...O-interactions affecting the structures of the compounds in question. The formation of the crystal structures is primarily governed by outer-sphere [ZrF₆]^2? anions and crystallization water molecules.     

Hydrothermal Synthesis,Structural and Optical Elucidation with Hirshfeld Surface Analysis of a Bioactive Hybrid Compound Based Mixed-Metal Cluster Anion [V<Subscript>2</Subscript>W<Subscript>4</Subscript>O<Subscript>19</Subscript>]<Superscript>4−</Superscript>

A mixed-metal Lindqvist-type heteropolyanion of organic cation; (C₈H₁₄N₂)₂[V₂W₄O₁₉]?2H₂O (m-XDAV2W4) has been synthesized hydrothermally and characterized by means ICP and elemental analysis, X-ray diffraction, IR, UV–Vis, luminescence and biological analyses. The X-ray structural analysis supported by a detailed Hirshfeld surface analysis and fingerprint plots has been elucidated the different inter-contacts in the crystal structure mainly associated with O…H/H…O close contacts between [V₂W₄O₁₉]^4? (V2W4) clusters, water molecules and m-xylylenediammonium entities so stabilizing the 3D-supramolecular structure. The optical survey reveals an important HOMO–LUMO band gap indicating stability and blue luminescent behavior of reported material. Moreover, the biological trials indicated that this compound displays promising antibacterial and antifungal activities.     

A novel bimetallic chain based on [Mo(Cn)<Subscript>8</Subscript>]<Superscript>3−</Superscript> and Eu<Superscript>3+</Superscript> ions as building blocks

A novel Mo^V-Eu^III bimetallic chain, {[Eu^III(Phen)(DMF)₄][Mo^V(CN)₈] · i-C₃H₇OH · 3H₂O} _n (I) (DMF = N,N′-dimethylformamide; Phen = phenanthroline), has been constructed by the reaction of [Mo(CN)₈]^3? with Eu³⁺ and phenanthroline in mixed solvent DMF/i-C₃H₇OH. Complex I is confirmed as a chain structure by X-ray structural analysis. The neighboring chains interact with each other by one type of face-to-face π…π stack with the distance of 3.5522(10) Å. Thus complex I has been extended to a 2D network.