New cyano-bridged complexes based on tetrahedral rhenium chalcocyanide clusters,Cu<Superscript>2+</Superscript> cations,and polydentate amines

Three new cyano-bridged compounds, viz., [{Cu(en)}{Cu(NH₃)(en)}Re₄Se₄(CN)₁₂]·{5H₂O (1), [{Cu(dien)}₂Re₄Te₄(CN)₁₂]·9H₂O (2), and [{Cu(trien)}₂Re₄Se₄(CN)₁₂]··5H₂O (3), were synthesized by the reactions of the tetrahedral rhenium chalcocyanide cluster complexes K₄[Re₄Q₄(CN)₁₂] ((Q = Se or Te) with copper(II) cations in aqueous solutions containing ethylenediamine (en), diethylenetriamine (dien), or triethylenetetraamine (trien), respectively. Complex 1 has a ladder-tubular-like polymeric structure, in which two infinite chains are linked to each other by Re-CN-Cu bridges, compound 2 has a polymeric chain structure, and compound 3 has a molecular structure. The structures of all complexes were established by X-ray diffraction analysis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2040–2044, October, 2004.     

Electroneutral coordination frameworks based on octahedral [Re<Subscript>6</Subscript>(μ<Subscript>3</Subscript>-Q)<Subscript>8</Subscript>(CN)<Subscript>6</Subscript>]<Superscript>4−</Superscript> complexes (Q = S,Se, Te) and the Mn<Superscript>2+</Superscript> cations

The novel coordination polymers, [{Mn(DMF)₃}₂{Re₆S₈(CN)₆}] (I), [{Mn(DMF)₂(H₂O)}₂{Re₆S₈(CN)₆}] · 2DMF (II), [{Mn(DMF)₃}₂{Re₆Se₈(CN)₆}] (III), [{Mn(DMF)₂(H₂O)}₂{Re₆Se₈(CN)₆}] · 2DMF (IV), and [{Mn(DMF)₂(H₂O)}₂{Re₆Te₈(CN)₆}] · 2DMF (V), were synthesized by interaction of the octahedral cluster complexes [Re₆(μ₃-Q)₈(CN)₆]^4? (Q = S, Se, Te) with the Mn²⁺ cations in the H₂O-DMF mixture. The crystal structures of compounds I, II, IV, and V were determined by X-ray diffraction analysis. The structural analogies between mononuclear cyanometallates and the obtained cluster coordination polymers were discussed.     

Complexes based on the anionic octahedral rhenium chalcogenide clusters and [M(En)<Subscript>2</Subscript>]<Superscript>2+</Superscript> (M = Ni,Cu) cations

The compounds [Ni(H₂O)₂(En)₂][{Ni(En)₂}Re₆S₈(OH)₆] · 7H₂O (I), [{Cu(En)₂}Re₆S₈(H₂O)₂(OH)₄] · 4H₂O (II), and [Ni(H₂O)₂(En)₂]_0.5[Re₆Se₈(H₂O)₃(OH)₃] · 10H₂O (III) were synthesized by layering aqueous solutions of Ni(En)₂Cl₂ or Cu(En)₂Cl₂ (En is ethylenediamine) onto aqueous solutions of the potassium salts of the corresponding octahedral chalcohydroxo rhenium cluster complexes [Re₆Q₈(OH)₆]⁴⁻ (Q = S, Se). The structure of the obtained compounds was determined by X-ray diffraction analysis.     

Crystal Structure Of [Au(Dien)Cl]<Subscript>2</Subscript>[Re<Subscript>4</Subscript>Te<Subscript>4</Subscript>(Cn)<Subscript>12</Subscript>]Sd5H<Subscript>2</Subscript>O

The structure of the [Au(Dien)Cl]₂[Re₄Te₄(CN)₁₂]·5H₂O compound prepared in an aqueous medium by the reaction of a gold(III) complex [Au(Dien)Cl]Cl₂ with a tetranuclear tetrahedral tellurocyanide cluster complex of rhenium K₄[Re₄Te₄(CN)₁₂]·5H₂O is determined by single crystal X-ray diffraction.     

Chiral coordination polymers based on Re cluster complexes,Cu<Superscript>2+</Superscript> cations,and 1,2<Emphasis Type="Italic">S</Emphasis>,3<Emphasis Type="Italic">S</Emphasis>,4-tetraaminobutane

Reactions of octahedral and tetrahedral chalcocyanide cluster complexes of Re with Cu²⁺ cations and 1,2S,3S,4-tetraaminobutane (Threo-tab) were used to synthesize and study the structures of the following six novel chiral complexes: [{Cu₂(NH₃)(Threo-tab)₃}Re₆S₈(CN)₆] 3H₂O (I) (where Threo is 1,2S,3S,4-tetraaminobutane), [{Cu₂(NH₃)(Threo-tab)₃}Re₆Se₈(CN)₆] 2H₂O (II), [{Cu(Threo-tab)}₂Re₆Te₈(CN)₆] 13.5H₂O (III), [{Cu(Threo-tab)}₂Re₄Te₄(CN)₁₂] 6.5H₂O (IV), [{Cu₂(NH₃)(Threo-tab)₂}Re₄Te₄(CN)₁₂] 4H₂O (V), and [{Cu(NH₃)(Threo-tab)}]₂[Re₄S_3.4Te_0.6(CN)₁₂] 1.25H₂O (VI). The structures of complexes I–IV contain extended channels of sufficiently large size capable of including guest molecules.__________Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 4, 2005, pp. 289–301.Original Russian Text Copyright © 2005 by Mironov, Naumov, Brylev, Efremova, Fedorov, Hegetschweiler.     

Synthesis and structures of new compounds based on tetrahedral rhenium chalcocyanide cluster anions [Re4Q4(CN)12]4− (Q = S or Se) and [Cu(bipy)2]2+ cations

The reactions of the rhenium chalcocyanide cluster salts K₄[Re₄Q₄(CN)₁₂]·6H₂O (Q = S or Se) with Cu²⁺ cations coordinated by the bidentate ligand 2,2′-bipyridyl (bipy) produced two new cluster compounds, [Cu(NH₃)(bipy)₂]₂[Re₄S₄(CN)₁₂]·bipy·3.25H₂O (1) and [{Cu(bipy)₂}₂Re₄Se₄(CN)₁₂]·bipy·8.5H₂O (2). The structures of these complexes were solved by X-ray diffraction. Compound 1 is ionic. Compound 2 is molecular. In the structures of both compounds, there are staking interactions between the {Cu(bipy)₂}²⁺ cationic moieties and the solvate 2,2′-bipyridyl molecules. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1875–1878, November, 2006.     

Coordination compounds based on the cluster anion [Re4Te4(CN)12]4− and Zn2+ cation

Three new coordination compounds [{Zn(H₂O)₂} {Zn(H₂O)₄} Re₄Te₄(CN)₁₂] (1), [Zn(en)₂(NH₃)₂][{Zn(en)(NH₃)₂} Re₄Te₄(CN)₁₂]·H₂O (2), and [{Zn₂(dien)₃} Re₄Te₄(CN)₁₂]· ·₆H₂O (3) (dien is diethylenetriamine) were prepared by reactions of aqueous solutions of the tetrahedral cluster rhenium tellurocyanide complex K₄[Re₄Te₄(CN)₁₂]· 5H₂O with zinc dichloride in the presence of ammonia, ethylenediamine, and diethylenetriamine, respectively. Complex 1 has a three-dimensional structure with two types of the Zn atoms; complex 2 is ionic with the polymeric chain anion; complex 3 has a molecular structure. The structures of complexes 1–3 were determined by single-crystal X-ray diffraction analysis. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 718–721, April, 2006.     

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.     

Polymers based on anionic octahedral cluster chalcocyanohydroxorhenium complexes and cations [Cu(En)2]2+

Polymer compounds [Cu(En)₂(H₂O)₂][{Cu(En)₂}Re₆S₈(CN)₄(OH)₂] · 5.5H₂O (I) and [Cu(En)₂(H₂O)₂][{Cu(En)₂}Re₆Se₈(CN)₄(OH)₂] · 5H₂O (II) are synthesized by the layering of an ammonia solution of CuCl₂ with ethylenediamine (En) on aqueous solutions of the corresponding octahedral cluster chalcocyanohydroxorhenium complexes. The compounds are characterized by IR spectroscopy and elemental and X-ray diffraction analyses.     

Structure of a new molecular rhenium cluster complex: trans-{[Ni(NH3)5]2×[Re6Se8(CN)4(OH)2]}·6H2O

Counter-diffusion of the aqueous solution of Cs_2.75K_1.25[Re₆Se₈(CN)₄(OH)₂] and a water-ammonia solution of NiCl₂ afforded crystals of a rhenium cluster complex trans-{[Ni(NH₃)₅]₂[Re₆Se₈(CN)₄(OH)₂]}·6H₂O. The structure of the complex is determined by single crystal X-ray diffraction. In the structure, nickel atoms have an octahedral coordination environment involving nitrogen atoms of five NH₃ ligands and one CN ligand of the cluster anion. The anion has two bridging CN ligands in the trans-positions     

Synthesis and structure of cluster compounds containing a novel cluster core {Re4STe3}

Three novel cluster compounds K₄[Re₄STe₃(CN)₁₂]·₄H₂O (I), [{Cu(en)₂}₂Re₄STe₃(CN)₁₂]·₅H₂O (II) and [{Cu(trien)}₂Re₄STe₃(CN)₁₂]·2H₂O (III) (en is ethylenediamine, trien is triethylenetetraamine) containing a new cluster core {Re₄STe₃} have been prepared and structurally characterized. According to single crystal X-ray diffraction data, compound I is ionic and represents the arrangement of ions K⁺ and [Re₄STe₃(CN)₁₂]^4?; compounds II and III are molecular and formed by two cationic moieties {Cu(en)₂}²⁺ and {Cu(trien)}²⁺, respectively, coordinated to one cluster anion. In the solid state, S atom positions in the tetrahedron Q₄ (Q = S, Te) are disordered for all three compounds: in I and III sulfur atoms are split over all four Q positions, while in II over two positions.     

A new cyanobridged one-dimensional coordination polymer based on the octahedral rhenium cluster [Re6Se8(CN)6]4−: Synthesis and crystal structure of [{Cu(H2O)0.5(en)2} {Cu(en)2}Re6Se8(CN)6]·3H2O

The rhenium cluster complex [{Cu(H₂O)_0.5(en)₂} {Cu(en)₂} Re₆Se₈(CN)₆]·3H₂O has been obtained by the reaction of an aqueous solution of K₄[Re₆Se₈(CN)₆]·3.5H₂O with an aqueous solution of Cu(en)₂Cl₂ using cross diffusion through a gel. The structure of the compound has been characterized by a single-crystal X-ray diffraction method (a = 10.690(3) Å, b = 15.035(5) Å, c = 25.847(8) Å, V = 4154(2) ų, Z = 4, space group P2₁2₁2₁, R = 0.0651). Cluster anions [Re₆Se₈(CN)₆]^4? in the complex are connected with Cu²⁺ cations by cyano bridges resulting in zigzag chains. Coordination environment of cations is completed by ethylenediamine molecules. Additionally each cluster anion is coordinated by one terminal fragment {Cu(H₂O)_0.5(en)₂}.     

New Layered Polymer [{Mn(H2O)3}2{Re6Se8(CN)6}] · 3.3H2O: Synthesis and Properties

The [{Mn(H₂O)₃}₂{Re₆Se₈(CN)₆}] · 3.3H₂O complex was produced on slow evaporation of an aqueous solution containing the salt of a cluster complex K₄Re₆Se₈(CN)₆ · 3.5H₂O and a 23-fold excess of Mn²⁺. The cluster complexes [Re₆Se₈(CN)₆]^4– are linked in a crystal into the charged coordination layers [{Mn(H₂O)₃}₄{Re₆Se₈(CN)₆}₃]^4– ₂ through the Mn²⁺ cations. The Mn²⁺ cations are coordinated in a layer by three cyano nitrogen atoms of the cluster complexes; the Mn–N bond lengths are 2.13(4) and 2.21(2) Å. Each [Re₆Se₈(CN)₆]^4– anion is bonded to three manganese cations Mn(1). The anions are bonded additionally to the Mn(2) cations disordered over two close positions.     

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.     

Synthesis,crystal structure,and thermal stability of ionic cluster compounds (phenH)4[Re4Q4(CN)12]·nH2O (Q = S,Se, n = 6; Q = Te,n = 10)

Three new salts of tetrahedral rhenium chalcocyanide cluster anions [Re₄Q₄(CN)₁₂]^4? (Q = S, Se, Te) and 1,10-phenanthroline-1-ium cations, (phenH)₄[Re₄S₄(CN)₁₂]·6H₂O (1), (phenH)₄[Re₄Se₄(CN)₁₂]·6H₂O (2), and (phenH)₄[Re₄Te₄(CN)₁₂]·10H₂O (3), have been synthesized by reactions of K₄[Re₄Q₄(CN)₁₂]·nH₂O with 1,10-phenanthroline in the presence of Nd³⁺ in an acidic aqueous medium (pH 4). 1 and 2 exhibit similar 2-D layered supramolecular architectures based on hydrogen bonds between water molecules, CN-groups of cluster anions, and phenH⁺ cations. The latter are involved in π–π and C–H?π stacking interactions, connecting the adjacent layers with each other. Complex 3 demonstrates a 3-D framework based on hydrogen bonds between water molecules and CN-groups, π–π and C–H?π interactions. Notably short O···Te contacts of 3.40 and 3.50 Å are found in the structure of 3. The thermal properties of 1–3 have been investigated by TG-DTG.     

Crystal structure of the ionic bioctahedral cluster complex [Ni(NH3)6]2.5NH4[Re12CS17(CN)6]·8.5H2O

A rhenium cluster complex [Ni(NH₃)₆]_2.5·NH₄[Re₁₂CS₁₇(CN)₆]·8.5H₂O is obtained and structurally described. The compound crystallizes in the triclinic space group P-1 with the unit cell parameters: a = 11.0856(13) Å, b = 15.242(2) Å, c = 21.232(3) Å, α = 90.158(4)°, β = 97.439(4)°, γ = 90.051(4)°, V = 3557.3(8) ų, Z = 2, d _calc = 3.287 g/cm³. The crystal structure represents a packing of [Ni(NH₃)₆]²⁺ and NH₄ ⁺ cations, [Re₁₂CS₁₇(CN)₆]^6? cluster anions, and crystallization water molecules bound by a system of hydrogen bonds.     

Two types of coordination polymers based on cluster anions [Re4Q4(CN)12] (Q = S, Se) and cations of rare-earth metals Ln: Syntheses and crystal structures

The reactions of aqueous solutions of the tetrahedral cluster anions [Re₄Q₄(CN)₁₂]⁴⁻ (Q = S, Se) with lanthanide chlorides resulted in the crystallization of the formed compounds into two main structural types [{Ln(H₂O)₄(H₂O)_2/3Cl_1/3}₃{Re₄Q₄(CN)₁₂}₂]·2H₂O (Ln = La-Gd, Q = S, Se) and K_0.5(H)_0.5[{Ln(H₂O)₄}{Re₄S₄(CN)₁₂}]·nH₂O or (H)[{Ln(H₂O)₄}{Re₄Se₄(CN)₁₂}]·nH₂O (Ln = Tb-Lu). Compounds of the first type crystallize in the hexagonal crystal system (space group Р6₃/m) and they have a three-dimensional polymeric structure; compounds of the second type crystallize in the orthorhombic crystal system (space group Cmcm) and they have a two-dimensional crystal structure due to the polymeric anion {[{Ln(H₂O)₄}{Re₄Q₄(CN)₁₂}]⁻}_∞∞.     

Novel inorganic ionic compounds based on Re6 chalcocyanide cluster complexes: synthesis and crystal structures of [CuNH3(trien)]2[Re6S8(CN)6] · 7H2O, [CuNH3(trien)]2[Re6Se8(CN)6] and [CuNH3(trien)]2[Re6Te8(CN)6] · H2O

Three new octahedral rhenium chalcocyanide cluster compounds [CuNH₃(trien)]₂[Re₆S₈(CN)₆] · 7H₂O (1), [CuNH₃(trien)]₂[Re₆Se₈(CN)₆] (2) and [CuNH₃(trien)]₂[Re₆Te₈(CN)₆] · H₂O (3) exhibiting ionic structures have been obtained by the diffusion of an ammonia solution of KCs₃[Re₆S₈(CN)₆] (for 1), K₄[Re₆Se₈(CN)₆] · 3.5H₂O (for 2) or Cs₄[Re₆Te₈(CN)₆] · 2H₂O (for 3) into a glycerol solution of CuCl₂ · 2H₂O in the presence of trien (trien=triethylenetetramine). The compounds have been characterized by single-crystal X-ray diffraction. All three compounds contain a cationic complex [CuNH₃(trien)]²⁺ which was not described previously.     

Synthesis, structures, and properties of molybdenum and tungsten chalcogenide cubane complexes (NH4)6[M4Q4(CN)12]·6H2O (M=Mo or W; Q=S or Se)

Four new chalcogenide molybdenum and tungsten cubane clusters (NH₄)₆[M₄Q₄(CN)₁₂]·6H₂O (M=Mo or W; Q=S or Se) were prepared by high-temperature reactions of the triangular M₃O₇Br₄ complexes with KCN at 430 °C followed by crystallization from aqueous solutions of ammonium acetate. The molecular and crystal structures of (NH₄)₆[Mo₄S₄(CN)₁₂]·6H₂O, (NH₄)₆[W₄S₄(CN)₁₂]·6H₂O, and (NH₄)₆[W₄Se₄(CN)₁₂]·6H₂O were established by X-ray diffraction analysis. The mixed-valence cubane clusters are diamagnetic and isostructural and have the symmetryT _d . The clusters were characterized by IR and electronic spectroscopy. The data of cyclic voltammetry demonstrated that the [M₄Q₄(CN)₁₂] ⁿ⁻ clusters exist in three oxidation states from the most oxidized (n=6; 10 cluster electrons) to the most reduced electron-precise 12-electron species (n=8). Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 18–24, January, 2000.