Hexaaquacobalt(II) bis(hypophosphite) and hexaaquacobalt(II)/nickel(II) bis(hypophosphite)

The title compounds, hexa­aqua­cobalt(II) bis­(hypophosphite), [Co(H₂O)₆](H₂­PO₂)₂, and hexa­aqua­cobalt(II)/nickel(II) bis(hypophosphite), [Co_0.5Ni_0.5(H₂O)₆](H₂PO₂)₂, are shown to adopt the same structure as hexa­aqua­magnesium(II) bis­(hypophosphite). The packing of the Co(Ni) and P atoms is the same as in the structure of CaF₂. The Co^II(Ni^II) atoms have a pseudo‐face‐centred cubic cell, with a = b～ 10.3 Å, and the P atoms occupy the tetrahedral cavities. The central metal cation has a slightly distorted octahedral coordination sphere. The geometry of the hypophosphite anion in the structure is very close to ideal, with point symmetry mm2. Each O atom of the hypophosphite anion is hydrogen bonded to three water mol­ecules from different cation complexes, and each H atom of the hypophosphite anion is surrounded by three water mol­ecules from further different cation complexes.     

Hexa­aqua­nickel(II) bis­(hypophosphite)

The structure of hexa­aqua­nickel(II) bis­(hypophosphite), [Ni(H₂O)₆](H₂PO₂)₂, has been determined. The crystals are prismatic. The packing of the Ni and P atoms (not the entire hypophosphite anions) is the same as in the structures of [Co(H₂O)₆](H₂PO₂)₂ and [Co_0.5Ni_0.5(H₂O)₆](H₂PO₂)₂. The Ni^II cations have a pseudo‐face‐centered cubic cell, with cell parameter a 10.216 Å and tetrahedral cavities occupied by P atoms. The Ni^II cation has crystallographically imposed twofold symmetry and has an octahedral coordination sphere consisting of six water O atoms, two of which also lie on the twofold axis. The planes of oppositely coordinated water mol­ecules are in a cross conformation. The geometry of the hypophosphite anion is close to point symmetry mm2. The hypophosphite anions are hydrogen bonded to the coordinated water molecules.     

(BETS)2[Fe(tdas)2]2: a new metal in the molecular conductor family

The structure of bis­[4,5‐ethyl­enedi­thio‐2‐(4,5‐ethyl­enedi­thio‐1,3‐diselena­cyclo­pent‐4‐en‐2‐yl­idene)‐1,3‐diselena­cyclo­pent‐4‐enium] bis(μ‐1,2,5‐thia­diazo­le‐3,4‐di­thiol­ato‐κ³S⁴,S⁵:S⁴)bis[(1,2,5‐thia­diazo­le‐3,4‐di­thiol­ato‐κ²S⁴,S⁵)­iron(III)], (BETS)₂[Fe(tdas)₂]₂ [BETS is alternatively called bis­(ethyl­enedi­thio)­tetraselenafulvalenium] or (C₁₀H₈S₄Se₄)₂[{Fe(C₂N₂S₃)₂}₂], consists of segregated columns of dimers of BETS and columns of dimers of [Fe(tdas)₂]. Each dimer displays inversion symmetry. Numerous chalcogen–chalcogen contacts are observed within and between the columns, producing a network of interactions responsible for the metal‐like behaviour of the compound.     

Two new soluble iron–oxo complexes: [Fe2(μ‐O)(μ‐O2CCF3)2(O2CCF3)2(C10H8N2)2] and [Fe4(μ3‐O)2(μ‐O2CCF3)6(O2CCF3)2(C10H8N2)2]·CF3CO2H

Two new iron–oxo clusters, viz. di‐μ‐tri­fluoro­acetato‐μ‐oxo‐bis­[(2,2′‐bi­pyridine‐κ²N,N′)(tri­fluoro­acetato‐κO)­iron(III)], [Fe₂O(CF₃CO₂)₄(C₁₀H₈N₂)₂], and bis(2,2′‐bi­pyridine)­di‐μ₃‐oxo‐hexa‐μ‐tri­fluoro­acetato‐bis­(tri­fluoro­acetato)­tetrairon(III) tri­fluoro­acetic acid solvate, [Fe₄O₂(CF₃CO₂)₈(C₁₀H₈N₂)₂]·CF₃CO₂H, contain dinuclear and tetranuclear Fe^III cores, respectively. The Fe^III atoms are in distorted octahedral environments in both compounds and are linked by oxide and tri­fluoro­acetate ions. The tri­fluoro­acetate ions are either bridging (bidentate) or coordinated to the Fe^III atoms via one O atom only. The fluorinated peripheries enhance the solubility of these compounds. Formal charges for all the Fe centers were assigned by summing valences of the chemical bonds to the Fe^III atom.     

A mixed‐valence iron complex of the antitumour drug 6‐mercaptopurine: tris(6‐mercaptopurine)iron(II) tetrachloroferrate(III) chloride

Single crystals of the title complex, tris(1,6‐di­hydro‐9H‐purine‐6‐thione‐N⁷,S)­iron(II) tetra­chloro­ferrate(III) chloride, [Fe(C₅H₄N₄S)₃][FeCl₄]Cl, were grown on the surface of solid 6‐mercaptopurine monohydrate pellets in a solution of iron(III) chloride. The solution of the hexagonal structure required the application of twin refinement techniques. All the component ions lie on threefold rotation axes. The complex contains distorted octahedral [Fe(C₅H₄N₄S)₃]²⁺ cations with three N7/S6‐chelating neutral 6‐mercaptopurine ligands, tetrahedral [FeCl₄]^? anions with a mean Fe—Cl distance of 2.189 (1) Å, and free chloride ions.     

A urea complex of copper(II) hypophosphite at 293, 100 and 15 K

The crystal structure of poly­[copper(II)‐di‐μ‐hypophosphito‐μ‐urea], [Cu(H₂PO₂)₂(CH₄N₂O)]_n, has been determined at 293, 100 and 15 K. The geometry of the hypophosphite anion is very close to ideal, with point symmetry mm2. Each Cu atom lies on an inversion centre and is coordinated to six O atoms from four hypophosphite anions and two urea mol­ecules, forming a tetragonal bipyramid. The unique urea molecule lies on a twofold axis. Each hypophosphite anion in the structure is coordinated to two Cu atoms. The hypophosphite anions, urea mol­ecules and Cu^II cations form polymeric ribbons. The Cu^II cations in the ribbon are linked together by two hypophos­phite anions and a urea mol­ecule, which is coordinated to Cu via an O atom. The ribbons are linked to each other by N—­H?O hydrogen bonds and form polymeric layers.     

(12,17‐Diethoxy­carbonyl‐2,3,6,­7,11,­18‐hexa­methyl­corrphy­cenato‐­κ4N)iodoiron(III) chloro­form solvate

The title complex, (diethyl 3,4,8,15,19,20‐hexa­methyl‐21,22,23,24‐tetraazopenta­cyclo­[16.2.1.1^2,5.1^7,11.1^14,17]­tetracosa‐1(20),2(22),3,5,7,9,11,13(24),14,16,18‐undecaene‐9,14‐dicarb­oxyl­ate‐κ⁴N)­iodo­iron(III) chloro­form solvate, [Fe(C₃₂H₃₂­N₄O₄)I]·­CHCl₃, shows an almost planar arrangement of the corrphycene moiety with a slightly distorted trapezoid pyramidal core; the Fe^III atom is 0.416 (1) Å from the plane of the C₂₀N₄ system. The Fe—N distances are 2.049 (3), 2.044 (3), 2.079 (3) and 2.075 (3) Å. The solvated chloro­form forms a C—H?O hydrogen bond [C?O 3.107 (10) Å] to an adjacent carbonyl O atom. This is the first X‐ray structure analysis of a corrphycenatoiron(III) derivative.     

Tri­azido­cobalt(III) complexes with tridentate amine ligands

The title compounds, [N‐(2‐amino­ethyl)‐1,3‐propane­di­amine‐κ³N]­tri­azido­cobalt(III), [Co(N₃)₃(C₅H₁₅N₃)], [N‐(2‐amino­ethyl)‐N‐methyl‐1,3‐propane­di­amine‐κ³N]­tri­azido­cobalt(III), [Co(N₃)₃(C₆H₁₇N₃)], [N‐(2‐amino­propyl)‐1,3‐pro­pane­di­am­ine‐κ³N]­tri­azido­cobalt(III), [Co(N₃)₃(C₆H₁₇N₃)], and [N‐(2‐amino­propyl)‐N‐methyl‐1,3‐pro­pane­di­am­ine‐κ³N]triazidocobalt(III), [Co(N₃)₃­(C₇­H₁₉­N₃)], each consist of a Co^III atom, three azide ligands in a meridional configuration and a tridentate amine ligand, namely aepn [N‐(2‐amino­ethyl)‐1,3‐propane­di­amine] or dpt [N‐(3‐amino­propyl)‐1,3‐pro­pane­di­amine], or their N‐methyl­­ated analogs.     

5‐n‐Butylpyridine‐2‐carboxylate–copper(II) and –iron(III) complexes

In trans‐bis(5‐n‐butyl­pyridine‐2‐carboxyl­ato‐κ²N,O)­bis­(methanol‐κO)copper(II), [Cu(C₁₀H₁₂NO₂)₂(CH₄O)₂], the Cu atom lies on a centre of symmetry and has a distorted octahedral coordination. The Cu—O(methanol) bond length in the axial direction is 2.596 (3) Å, which is much longer than the Cu—­O(carboxylate) and Cu—N distances in the equatorial plane [1.952 (2) and 1.977 (2) Å, respectively]. In mer‐tris(5‐n‐bu­tyl­pyridine‐2‐carboxyl­ato‐κ²N,O)­iron(III), [Fe(C₁₀H₁₂NO₂)₃], the Fe atom also has a distorted octahedral geometry, with Fe—O and Fe—N bond‐length ranges of 1.949 (4)–1.970 (4) and 2.116 (5)–2.161 (5) Å, respectively. Both crystals are stabilized by stacking interactions of the 5‐n‐butyl­pyridine‐2‐carboxyl­ate ligand, although hydrogen bonds also contribute to the stabilization of the copper(II) complex.     

A mixed‐valence manganese(III)–manganese(IV) di‐μ‐oxo complex, [(cyclam)MnO]2(ClO4)2(NO3)

The title dinuclear di‐μ‐oxo‐bis­[(1,4,8,11‐tetra­aza­cyclo­tetra­decane‐κ⁴N)­manganese(III,IV)] diperchlorate nitrate complex, [Mn₂O₂(C₁₀H₂₄N₄)₂](ClO₄)₂(NO₃) or [(cyclam)Mn­O]₂(ClO₄)₂(NO₃), was self‐assembled by the reaction of Mn²⁺ with 1,4,8,11‐tetra­aza­cyclo­tetra­decane in aqueous media. The structure of this compound consists of a centrosymmetric binuclear [(cyclam)MnO]³⁺ unit, two perchlorate anions and one nitrate anion. While the low‐temperature electron paramagnetic resonance spectra show a typical 16‐line signal for a di‐μ‐oxo Mn^III/Mn^IV dimer, the magnetic susceptibility studies also confirm a characteristic antiferromagnetic coupling between the electronic spins of the Mn^IV and Mn^III ions.     

Azido­[1,1′‐bis­(di­phenyl­phosphino)­ferrocene](penta­methyl­cyclo­penta­dienyl)­rhodium(III) hexa­fluoro­phosphate

In the title compound, azido‐2κN‐bis­[μ‐(1η⁵:2κP)‐di­phenyl­phosphino­cyclo­penta­dienyl][2(η⁵)‐penta­methyl­cyclo­penta­di­enyl]­iron(III)­rhodium(III) hexa­fluoro­phosphate, [{Rh(C₁₀H₁₅)(N₃)}{Fe(μ‐C₁₇H₁₄P)₂}]PF₆ or [FeRh(C₁₀H₁₅)(μ‐C₁₇H₁₄P)₂(N₃)]PF₆, the coordination sphere of Rh^III can be described as pseudo‐tetrahedral, composed of two P atoms from a 1,1′‐bis­(di­phenyl­phosphino)­ferrocene (dppf) ligand, an azido N atom and the centroid of the ring of a C₅Me₅ (Cp*) ligand. The two cyclo­penta­dienyl rings in the dppf moiety adopt an eclipsed conformation. The Rh⋯Fe distance is 4.340 (2) Å.     

{Bis­[2‐(2‐oxido‐1‐naphthylmethylidene­amino)­phenyl] disulfide}chloroiron(III)

The crystal structure of the title compound, {bis­[2‐(2‐oxido‐2‐naphthyl­idene­amino)­phenyl] di­sulfide‐κ⁵O,N,S,N′,O′}chloroiron(III), [FeCl(C₃₄H₂₂N₂O₂S₂)], has been determined. The structure consists of monomeric iron(III) complexes with distorted octahedral coordination. The di­sulfide functions as a pentadentate ligand and the Fe^III atom is coordinated through two N, two O and one S atom, and one chloride ion. The distance between the second S atom and the Fe^III atom is a non‐bonding 3.8473 (14) Å.     

Bis[tris­(2,2′‐bipyridine)iron(II)] tetra­aqua­sodium(I) dodeca­tungsto­ferrate(III) dihydrate

The title compound, bis­[tris­(2,2′‐bipyridine)iron(II)] tetra­aqua­tetra‐μ₄‐oxo‐penta­cosa‐μ₂‐oxo‐undeca­oxo­iron(III)sodium(I)­dodeca­tungsten(VI) dihydrate, [Fe(C₁₀H₈N₂)₃]₂[NaFeW₁₂O₄₀(H₂O)₄]·2H₂O, consists of a dodeca­tungstoferrate(III) framework grafted on to an [Na(H₂O)₄]⁺ cation, two complex [Fe(2,2′‐bipy)₃]²⁺ cations (2,2′‐bipy is 2,2′‐bipyridine) and two uncoordinated water mol­ecules per formula unit.     

Three heterotrinuclear Schiff base complexes of nickel(II) with cobalt(II), copper(II) and manganese(II)

The title compounds, bis­(di­methyl­form­amide)‐1κO,3κO‐bis{μ‐2,2′‐[2,2′‐di­methyl­propane‐1,3‐diyl­bis­(nitrilo­methylidyne)]­diphenolato}‐1κ⁴N,N′,O,O′:2κ²O,O′;2κ²O,O′:3κ⁴N,N′,O,O′‐di‐μ‐nitrito‐1:2κ²N:O;2:3κ²O:N‐dinickel(II)­cobalt(II), [CoNi₂(NO₂)₂(C₁₉H₂₂N₂O₂)₂(C₃H₇NO)₂], (I), ‐copper(II), [CuNi₂(NO₂)₂(C₁₉H₂₂N₂O₂)₂(C₃H₇NO)₂], (II), and ‐manganese(II), [MnNi₂(NO₂)₂(C₁₉H₂₂N₂O₂)₂(C₃H₇NO)₂], (III), consist of centrosymmetric linear heterotrinuclear metal complexes. The three complexes are isostructural. There are three bridges across the Ni–M atom pairs (M is Co²⁺, Cu²⁺ or Mn²⁺) in each complex, involving two O atoms of a μ‐N,N′‐bis­(salicyl­idene)‐2,2′di­methyl‐1,3‐propane­diaminate ligand and an N—O moiety of a μ‐nitrito group. The coordination sphere around each metal atom, whether Co²⁺, Cu²⁺, Mn²⁺ or Ni²⁺, can be described as distorted octahedral. The Ni?M distances are 2.9988 (5) Å in (I), 2.9872 (5) Å in (II) and 3.0624 (8) Å in (III).     

(2‐Methyl­quinolin‐8‐olato)­iron(III) and ‐copper(II) complexes

The crystal structures of tris(2‐methyl­quinolin‐8‐olato‐N,O)­iron(III), [Fe­(C₁₀­H₈­NO)₃], (I), and aqua­bis(2‐methyl­quinolin‐8‐olato‐N,O)­copper(II), [Cu­(C₁₀­H₈NO)₂­(H₂O)], (II), have been determined. Compound (I) has a distorted octahedral configuration, in which the central Fe atom is coordinated by three N atoms and three O atoms from three 2‐methylquinolin‐8‐olate ligands. The three Fe—O bond distances are in the range 1.934 (2)–1.947 (2) Å, while the three Fe—N bond distances range from 2.204 (2) to 2.405 (2) Å. In compound (II), the central Cu^II atom and H₂O group lie on the crystallographic twofold axis and the coordination geometry of the Cu^II atom is close to trigonal bipyramidal, with the three O atoms in the basal plane and the two N atoms in apical positions. The Cu—N bond length is 2.018 (5) Å. The Cu—O bond length in the basal positions is 1.991 (4) Å, while the Cu—O bond length in the apical position is 2.273 (6) Å. There is an intermolecular OW—H?O hydrogen bond which links the mol­ecules into a linear chain along the b axis.     

Cu3(CN)4(NH3)2Hg(CN)2: a novel inter­penetrating framework formed from CuI,CuII, HgII and cyanide bridges

The title compound, poly[diammine­hexa‐μ‐cyano‐di­copper(I)­copper(II)­mercury(II)], [Cu₃Hg(CN)₆(NH₃)₂]_n, has a novel threefold‐inter­penetrating structure of three‐dimensional frameworks. This three‐dimensional framework consists of two‐dimensional network Cu₃(CN)₄(NH₃)₂ complexes and rod‐like Hg(CN)₂ complexes. The two‐dimensional network complex contains trigonal–planar Cu^I (site symmetry m) and octa­hedral Cu^II (site symmetry 2/m) in a 2:1 ratio. Two types of cyanide group form bridges between three coordination sites of Cu^I and two equatorial sites of Cu^II to form a two‐dimensional structure with large hexa­gonal windows. One type of CN⁻ group is disordered across a center of inversion, while the other resides on the mirror plane. Two NH₃ mol­ecules (site symmetry 2) are located in the hexa­gonal windows and coordinate to the remaining equatorial sites of Cu^II. Both N atoms of the rod‐like Hg(CN)₂ group (Hg site symmetry 2/m and CN⁻ site symmetry m) coordinate to the axial sites of Cu^II. This linkage completes the three‐dimensional framework and penetrates two hexa­gonal windows of two two‐dimensional network complexes to form the threefold‐inter­penetrating structure.     

[Fe(C12H8N3O2)Cl2(ROH)], with R = Me and Et

The title octahedral complexes, [bis(pyridine‐2‐carbonyl)­amin­ate]­di­chloro­(methanol)­iron(III), [Fe(C₁₂H₈N₃O₂)­Cl₂‐(CH₄O)], and [bis­(pyri­dine‐2‐carbonyl)­amin­ate]­di­chloro‐(ethanol)­iron(III), [Fe­(C₁₂H₈N₃O₂)Cl₂(C₂H₆O)], both crystallize in space group and have similar structures. Mono­anionic bpca^? [bis(pyridine‐2‐carbonyl)­amin­ate] acts as a planar tridentate ligand in both cases. Coordination bond distances are in the range typical of high‐spin Fe^III complexes. Carbon–oxygen distances are typical of a C=O double bond suggesting the negative charge of the bpca^? ligand is localized on the central N atom.     

(Z)‐2‐Methylbuten‐1‐yl(aryl)iodonium trifluoromethanesulfonates containing electron‐withdrawing groups on the aryl moiety

The crystal structures of [(Z)‐2‐methyl­but‐1‐en‐1‐yl]­[4‐(tri­fluoro­methyl)­phenyl]­iodo­nium tri­fluoro­methane­sulfonate, C₁₂H₁₃F₃I⁺·CF₃O₃S^?, (I), (3,5‐di­chloro­phenyl)­[(Z)‐2‐methyl­but‐1‐en‐1‐yl]­iodo­nium tri­fluoro­methane­sulfonate, C₁₁H₁₂­Cl₂I⁺·CF₃O₃S^?, (II), and bis{[3,5‐bis­(tri­fluoro­methyl)­phenyl][(Z)‐2‐methyl­but‐1‐en‐1‐yl]­iodo­nium} bis­(tri­fluoro­methane­sulfonate) di­chloro­methane solvate, 2C₁₃H₁₂F₆I⁺·­2CF₃­O₃S^?·CH₂Cl₂, (III), are described. Neither simple acyclic β,β‐di­alkyl‐substituted alkenyl­(aryl)­idonium salts nor a series containing electron‐deficient aryl rings have been described prior to this work. Compounds (I)–(III) were found to have distorted square‐planar geometries, with each I atom interacting with two tri­fluoro­methane­sulfonate counter‐ions.     

Molecular building blocks for solid‐state chalcogenides: solvothermal synthesis of [Mn(en)3]Te4 and [Fe(en)3]2(Sb2Se5)

Two new molecular metal chalcogenides, tris­(ethyl­enedi­amine‐N,N′)­manganese(II) tetratelluride, [Mn(C₂H₈N₂)₃]Te₄, (I), and bis­[tris­(ethyl­enedi­amine‐N,N′)­iron(II)] penta­seleno­diantimonate(III), [Fe(C₂H₈N₂)₃]₂(Sb₂Se₅), (II), containing the isolated molecular building blocks Te₄^2? and Sb₂Se₅^4?, have been synthesized by solvothermal reactions in an ethyl­enedi­amine solution at 433 K. The anion Te₄^2? in (I) is a zigzag oligometric chain with Te—Te bond lengths in the range 2.709–2.751 Å. There is a very short contact [3.329 (1) Å] between a pair of neighboring Te₄^2? anions. In (II), each Sb atom is surrounded by three Se atoms to give a tripodal coordination. One of the three independent Se atoms is a μ₂‐bridging ligand between two Sb atoms; the other two are terminal.     

Second‐sphere coordination in anion binding: sodium hexa­ammine­cobalt(III) tetra­kis­(4‐fluoro­benzoate) monohydrate

In sodium hexa­amminecobalt(III) tetra­kis­(4‐fluoro­benzoate) monohydrate, Na[Co(NH₃)₆](C₇H₄FO₂)₄·H₂O, determined at 180 K, [Co(NH₃)₆]³⁺ cations lie on centres of inversion and form layers in which their C₄ axes lie perpendicular to the layer planes. 4‐Fluoro­benzoate anions lie on twofold axes and general positions and adopt near‐planar geometries. Na⁺ cations and water mol­ecules lie on twofold axes, forming [NaO₅] square pyramids that lie between the [Co(NH₃)₆]³⁺ cations. The second‐sphere inter­actions between [Co(NH₃)₆]³⁺ cations and 4‐fluorobenzoate anions comprise edge‐to‐face and vertex‐to‐face arrangements. The structure is closely comparable with that of the benzoic acid salt, demonstrating that fluorination of the anion in the para position has no significant influence on the second‐sphere inter­actions and minimal influence on the gross crystal structure.