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.     

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.     

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.     

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%.     

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).     

Peroxide derivatives of heteropoly compounds with Keggin anions [PW<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Superscript>3−</Superscript> and [SiW<Subscript>12</Subscript>O<Subscript>40</Subscript>]<Superscript>4−</Superscript>: Synthesis and structure

Peroxide derivatives of heteropoly compounds with Keggin anions [PW₁₂O₄₀]^3? and [SiW₁₂O₄₀]^4? are isolated in an individual state from concentrated hydrogen peroxide solutions and characterized by physicochemical methods. The structure of Ba₂[SiW₁₂O₄₀] · 4H₂O₂ · 11H₂O (I) is solved by X-ray crystallography. Crystals of compound I (H₃₀Ba₂O₅₉Si₁W₁₂, FW = 3483.21) are monoclinic, space group C2/c, a = 24.981(2) Å, b = 12.2103(11) Å, c = 18.7142(17) Å, β = 122.620(2)^o, V = 4808.0(8) ų, Z = 4. The structure contains Keggin anions [SiW₁₂O₄₀]^4?; all hydrogen peroxide molecules are coordinated to Ba²⁺ cations.     

Crystal structure and thermal properties of [Au(en)<Subscript>2</Subscript>]<Subscript>2</Subscript>[Cu(C<Subscript>2</Subscript>O<Subscript>4</Subscript>)<Subscript>2</Subscript>]<Subscript>3</Subscript>·8H<Subscript>2</Subscript>O

The crystal structure of a double complex salt of the composition [Au(en)₂]₂[Cu(C₂O₄)₂]₃·8H₂O (en = ethylenediamine) at 150 K is determined by single crystal X-ray diffraction. The crystal data for C₂₀H₄₈Au₂Cu₃N₈O₃₂ are: a = 9.1761(3) Å, b = 16.9749(6) Å, c = 13.4475(5) Å, β = 104.333(1)°, V = 2029.43(12) ų, P2₁/c space group, Z = 2, d _x = 2.450 g/cm³. It is demonstrated that the thermal decomposition of the double complex salt in a helium or hydrogen atmosphere affords the solid solution Au_0.4Cu_0.6.     

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.     

Synthesis and structure of novel coordination compounds based on [Re<Subscript>6</Subscript>Q<Subscript>8</Subscript>(CN)<Subscript>6</Subscript>]<Superscript>4–</Superscript> (Q = S,Se) and (SnMe<Subscript>3</Subscript>)<Superscript>+</Superscript>

The reactions of SnMe₃Cl with salts of the cluster anionic complexes [Re₆Q₈(CN)₆]^4? (Q = S, Se) gave novel complexes [{(SnMe₃)₂(OH)}₂{SnMe₃}₂{Re₆S₈(CN)₆}] (I), (Me₄N)₂[{SnMe₃(H₂O)}₂{Re₆Se₈(CN)₆}] (II), [{(SnMe₂)₄(μ₃-O)}₂{Re₆Se₈(CN)₆}] (III), and [(SnMe₂)₄(μ₃-O)₂(μ₂-OH)₂(H₂O)₂][{SnMe_{3 2}{Re₆Se₈(CN)₆}] (IV). The structures of I–IV were determined by X-ray diffraction. Compounds I, IV have the chain structures with the CN-SnMe₃-NC bridges between the cluster anions [Re₆Q₈(CN)₆]^4?. Compound II contains isolated fragments {SnMe₃(H₂O)}₂{Re₆Se₈(CN)₆}^2?. In the polymer framework of compound III, the cluster anionic complexes [Re₆Se₈(CN)₆]^4? are bound by the complex cations [(SnMe₂)₄(μ₃-O)₂]⁴⁺ formed due to the hydrolysis of the initial (SnMe₃)Cl.     

Nickel(II) tetraaqua bis(benzoate) tris(phenylacethydrazide) complex [Ni(HL<Superscript>1</Superscript>)<Subscript>3</Subscript>](L<Superscript>2</Superscript>)<Subscript>2</Subscript> · 4H<Subscript>2</Subscript>O: Synthesis and crystal and molecular structure

The synthesis, IR and Raman spectroscopic study, and X-ray diffraction analysis of [Ni(HL¹)₃](L²)₂ · 4H₂O (I), where HL¹ is phenylacetic acid hydrazide and L² is the benzoate monoanion, have been performed. The structural units of a crystal of complex I are complex [Ni(HL¹)₃]²⁺ cations, (L²)^– anions, and crystallization water molecules. The nickel atom is coordinated to the three oxygen atoms at octahedron apices and the three nitrogen atoms of three bidentate chelate (О, N) ligands HL¹ in cis,trans-meredianal (fac) conformation. The structural units of a crystal of complex I are bonded by a branched network of О–Н···О and N–H···O hydrogen bonds.     

Framework coordination polymer based on the [Re<Subscript>3</Subscript>Mo<Subscript>3</Subscript>S<Subscript>8</Subscript>(CN)<Subscript>6</Subscript>]<Superscript>6–</Superscript>heterometallic cluster anions and Cd<Superscript>2+</Superscript> cations

A new coordination polymer, [Cd(NH₃)₄]₂{Cd[Re₃Mo₃S₈(CN)₆]}·1.5H₂O (I), was prepared by the reaction between solutions of Cd(CH₃COO)₂ · 2H₂O in aqueous ammonia and CaK₄[Re₃Mo₃S₈(CN)₆] · 8H₂O in water. The crystals are cubic, space group Fm3m (Prussian blue structural type); a = 15.0268(4) Å (CIF file CSD no. 431555). According to ESR data, compound I is paramagnetic, g-factor is 2.298. Thermal stability investigation by TGA and powder X-ray diffraction showed that elimination of coordinated NH₃ molecules is accompanied by sample amorphization.     

Synthesis and crystal structure of [Et<Subscript>4</Subscript>N] [Cr(PzTp)Cl<Subscript>3</Subscript>] [PzTp<Superscript>−</Superscript> = Tetra(pyrazolyl) Borate]

Treatment of CrCl₃(THF)₃ with KPzTp in THF affords of the compound K[Cr(PzTp)Cl₃], and the K⁺ in this complex can be replaced by Et₄N⁺ in CH₂Cl₂. Well-defined green crystals of [Et₄N]r(PzTp)Cl₃] (I) suitable for X-ray diffraction are obtained at −₂0°C. In the anion the metal center shows a distorted octahedral geometry with the tetra(pyrazolyl) borate bonded as three N-donor tripod ligands and three chloride atoms completing the coordination sphere.     

Synthesis and structure of the [Co(NioxH)<Subscript>2</Subscript>(Thio)<Subscript>2</Subscript>]<Subscript>2</Subscript>SO<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O complex compound

A new Co(III) complex of 1,2-cyclohexanedionedioxime and thiocarbamide with an SO ₄ ^2? anion and solvation water molecules in the outer sphere has been synthesized and its structure has been defined. Orthorhombic crystals, a = 11.659(2) Å, b = 26.448(5) Å, c = 30.142(6) Å, V = 9295(3) Å ³, Z = 8, d_calc = 1.599 g/cm³, space group Pbca; final R index is 0.0578 for 8221 reflections with I > 2σ(I). In the octahedral Co(III) complex, two 1,2-cyclohexanedionedioxime residues lie in the equatorial plane, while two thiocarbamide molecules are in the axial plane. Intramolecular bonds: N-H…O and O-H…O type hydrogen bonds and π-π interactions that stabilize the complex cations. In crystal, the components are linked by N-H…O and O-H…O hydrogen bonds into a 3D framework.     

Synthesis and Structure of [Co(NH<Subscript>3</Subscript>)<Subscript>6</Subscript>]<Subscript>2</Subscript>[W<Subscript>4</Subscript>Se<Subscript>4</Subscript>(CN)<Subscript>12</Subscript>]·8.5H<Subscript>2</Subscript>O

The compound [Co(NH₃)₆]₂[W₄Se₄(CN)₁₂]·8.5H₂O was obtained by evaporating an aqueous ammonia solution of K₆[W₄Se₄(CN)₁₂]·6H₂O and CoCl₂·6H₂O complexes. The starting Co(II) of CoCl₂·6H₂O transforms into [Co(NH₃)₆]³⁺ when exposed to air in a water-ammonia medium. Crystal data: triclinic crystal system, a = 10.7750(8) Å, b = 12.2843(9) Å, c = 19.6539(14) Å; α = 90.213(2)°, β = 99.910(2)°, γ = 114.737(1)°, V = 2319.1(3) ų, space group , Z = 2, D _x = 2.633 g/cm³.Original Russian Text Copyright © 2004 by I. V. Kalinina, Z. A. Starikova, F. M. Dolgushin, D. G. Samsonenko, and V. P. Fedin__________Translated from Zhurnal Strukturnoi Khimii, Vol. 45, No. 5, pp. 905–908, September–October, 2004.     

Crystal structure of Pb<Subscript>2</Subscript>[Fe(CN)<Subscript>6</Subscript>]NO<Superscript>3</Superscript>·5.5H<Subscript>2</Subscript>O

Synthesis of a mixed complex compound Pb₂[Fe(CN)₆]NO₃·5.5H₂O is described. The results of its X-ray structural investigation are presented. Crystal data: C₆H₁₁FeN₇O_8.50Pb₂: a = 7.2582(6) Å, b = 21.838(3) Å, c = 11.612(1) Å; β = 107.91(1)°, V = 1751.4(3) ų, Z = 4, d_calc = 2.986 g/cm³, space group P2₁/m, R = 0.038. The compound has a framework polymer structure.     

Supramolecular Adduct of γ-Cyclodextrin and [{Re<Subscript>6</Subscript>Q<Subscript>8</Subscript>}(H<Subscript>2</Subscript>O)<Subscript>6</Subscript>]<Superscript>2+</Superscript> (Q=S,Se)

Slow evaporation of water solution of [{Re₆S₈}(H₂O)₆]²⁺ generated in situ from [{Re₆S₈}(OH)₆]^4– in presence of γ-cyclodextrin (CD) leads to crystallization of {[{Re₆S₈}(H₂O)₆] ? [γ-CD]}(NO₃)₂·12H₂O (1·12H₂O) supramolecular complex, which was characterized by single-crystal X-ray diffraction crystallography, IR-spectroscopy, thermogravimetric and elemental analyses. X-ray analysis confirms the formation of 1:1 {[{Re₆S₈}(H₂O)₆] ? [γ-CD]}²⁺ inclusion compound in the solid state. However, no adduct formation was detected between [{Re₆S₈}(H₂O)₆]²⁺ and γ-cyclodextrin in solution, according to ¹H NMR spectroscopy. In the case of in situ generated [{Re₆Se₈}(H₂O)₆]²⁺ the reaction solution with γ-cyclodextrin is unstable and during the crystallization only amorphous precipitate has been obtained.     

Novel ladder-like structure motif assembled from edge-sharing rhombus and square of Mo<Subscript>2</Subscript>Dy<Subscript>2</Subscript> based on [Mo(CN)<Subscript>8</Subscript>]<Superscript>4−</Superscript> and Dy<Superscript>3+</Superscript> ions as building blocks

A novel bimetallic 4d–4f complex, “Cs[Dy(MeOH)₃(DMF)(H₂O)Mo(CN)₈] · H₂O” _n (I) (DMF = N,N′-dimethylformamide), has been synthesized and structurally characterized. The crystal analyses showed that complex I consists of a one-dimensional infinite chain, which adopts a 1D ladder-like structure motif assembled from an edge-sharing rhombus and square of Mo₂Dy₂. This is the first structurally characterized example of a 1D ladder structure based on the [Mo(CN)₈]^4? and Dy³⁺ building blocks. Complex I crystallizes in triclinic crystal system, \(P\bar 1\) space group, with a = 9.876(2), b = 10.300(2), c = 13.498(3) Å, α = 81.96(3)°, β = 86.68(3)°, γ = 65.42(3)°, V = 1236.4(4) ų, and Z = 2.     

Synthesis and crystal structures of [K(H<Subscript>2</Subscript>O)(Piv)]<Subscript>∞</Subscript> and [K<Subscript>2</Subscript>(Phen)(H<Subscript>2</Subscript>O)<Subscript>2</Subscript>(Piv)<Subscript>2</Subscript>]<Subscript>∞</Subscript>

A method for the synthesis of potassium pivalates (trimethylacetates) from potassium tert-butoxide and pivalic acid was proposed. The complexes of the formulas [K(H₂O)(Piv)]_∞(I) and [K₂(Phen)(H₂O)₂(Piv)₂]_∞ (II) (Piv denotes the pivalate anion and Phen denotes 1,10-phenanthroline) were obtained and characterized by elemental analysis and IR and ¹H NMR spectroscopy. The crystal structures of complexes I and II were determined using X-ray diffraction. Crystal structure I has a layered motif with two nonequivalent K atoms (C.N.s 5 + 2 and 6). The coordination of phenanthroline in II gives rise to a ribbon motif, the structure containing three nonequivalent K atoms (C.N.s 6, 6 + 1, and 8).     

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.