Poly[tetrasodium(I)‐tetra‐μ2‐bis(butane‐1,4‐diyldioxy)borato‐μ2‐1,4‐butane­diol]

In the title compound, [Na₄(C₈H₁₆BO₄)₄(C₄H₁₀O₂)]_n, there are two coordination types for the four independent Na⁺ cations: two Na⁺ cations bond to six diolate O atoms [Na—O = 2.305 (2)–2.609 (2) Å], while the other two are five‐coordinate via one 1,4‐butane­diol [2.289 (2) and 2.349 (3) Å] and four diolate O atoms [2.295 (2)–2.408 (2) Å]. Corresponding to this, there are three‐ and four‐coordinate diolate O atoms, the latter bridging Na atoms. The 1,4‐butane­diol mol­ecules lie on inversion centres. The boron stereochemistry shows minor local perturbations from its usual tetrahedral state [B—O = 1.457 (4)–1.503 (4) Å]. The resulting polymer packs as sheets parallel to the (10) plane crosslinked by the butane­diol mol­ecules. The structure was solved using data from a multiple crystal.     

A novel one‐dimensional complex: catena‐poly­[[manganese(III)‐di‐μ‐2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolato‐κ2O1,N:κO2;κO2:κ2O1] chloride]

In the title one‐dimensional complex, {[Mn^III(C₉H₁₀NO₂)₂]Cl}_n, the Schiff base ligand 2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolate (Hsae⁻) functions as both a bridging and a chelating ligand. The Mn^III ion is six‐coordinated by two N and four O atoms from four different Hsae⁻ ligands, yielding a distorted MnO₄N₂ octahedral environment. Each [Mn^III(Hsae)₂]⁺ cationic unit has the Mn atom on an inversion centre and each [Mn^III(Hsae)₂]⁺ cation lies about another inversion centre. The chain‐like complex is further extended into a three‐dimensional network structure through Cl⋯H—O hydrogen bonds and C—H⋯π contacts involving the Hsae⁻ rings.     

catena‐Poly­[[heptakis­(di­methyl­form­amide‐κO)­di‐μ4‐oxo‐tetra‐μ3‐oxo‐hexa­deca‐μ2‐oxo‐tetra­oxo­lan­than­um(III)­octamolybdenum(IV)]‐μ‐sodium(I)]

The title compound, [NaLaMo₈O₂₆(C₃H₇NO)₇]_n, contains infinite chains of [Mo₈O₂₆]⁴⁻ units supporting di­methyl­form­amide‐coordinated La^III cations and linked by Na⁺ cations. The lanthanum center adopts a nine‐coordinate geometry and the Na atom is sandwiched between two β‐[Mo₈O₂₆]⁴⁻ units.     

catena‐Poly[[bis(μ‐2‐sulfonatobenzoato)bis[triaquagadolinium(III)]]‐μ‐oxalato]

The asymmetric unit of the title coordination polymer, [Gd₂(C₇H₄O₅S)₂(C₂O₄)(H₂O)₆]_n or [Gd(2‐SB)(ox)_0.5(H₂O)₃]_2n (2‐SB is 2‐sulfonatobenzoate and ox is oxalate), (I), consists of one Gd^III ion, one 2‐SB anion, three coordinated water molecules and one half of an ox ligand. The ox ligand is located on a crystallographic inversion centre. The Gd^III centre shows a distorted tricapped trigonal–prismatic coordination formed by nine O atoms from two 2‐SB anions, one ox ligand and three coordinated water molecules. The carboxylate and sulfonate groups of the 2‐SB anions adopt μ₂‐η¹:η² and μ₁‐η⁰:η⁰:η¹ coordination modes to link two Gd^III ions, generating a centrosymmetric binuclear [Gd₂(2‐SB)₂(H₂O)₆]²⁻ subunit. The ox ligand acts as a bridge, linking the binuclear [Gd₂(2‐SB)₂(H₂O)₆]²⁻ subunits into a one‐dimensional chain structure parallel to the b axis. Furthermore, extensive O—H...O hydrogen bonds connect the chains into a three‐dimensional supramolecular architecture.     

A three‐dimensional coordination polymer based on the Zn4(μ3‐OH)2 unit: poly[[(μ4‐benzene‐1,4‐dicarboxylato)bis(μ3‐benzene‐1,4‐dicarboxylato)bis(μ3‐hydroxido)bis(1,10‐phenanthroline‐5,6‐dione)tetrazinc] dihydrate]

The title compound, {[Zn₄(C₈H₄O₄)₃(OH)₂(C₁₂H₆N₂O₂)₂]·2H₂O}_n, has been prepared hydrothermally by the reaction of Zn(NO₃)₂·6H₂O with benzene‐1,4‐dicarboxylic acid (H₂bdc) and 1,10‐phenanthroline‐5,6‐dione (pdon) in H₂O. In the crystal structure, a tetranuclear Zn₄(OH)₂ fragment is located on a crystallographic inversion centre which relates two subunits, each containing a [ZnN₂O₄] octahedron and a [ZnO₄] tetrahedron bridged by a μ₃‐OH group. The pdon ligand chelates to zinc through its two N atoms to form part of the [ZnN₂O₄] octahedron. The two crystallographically independent bdc²⁻ ligands are fully deprotonated and adopt μ₃‐κO:κO′:κO′′ and μ₄‐κO:κO′:κO′′:κO′′′ coordination modes, bridging three or four Zn^II cations, respectively, from two Zn₄(OH)₂ units. The Zn₄(OH)₂ fragment connects six neighbouring tetranuclear units through four μ₃‐bdc²⁻ and two μ₄‐bdc²⁻ ligands, forming a three‐dimensional framework with uninodal 6‐connected α‐Po topology, in which the tetranuclear Zn₄(OH)₂ units are considered as 6‐connected nodes and the bdc²⁻ ligands act as linkers. The uncoordinated water molecules are located on opposite sides of the Zn₄(OH)₂ unit and are connected to it through hydrogen‐bonding interactions involving hydroxide and carboxylate groups. The structure is further stabilized by extensive π–π interactions between the pdon and μ₄‐bdc²⁻ ligands.     

A pentanuclear bimetallic complex of manganese(II) and aluminium(III) ions: tetra‐μ2‐iodido‐iodidobis(μ3‐2‐methoxyethanolato)bis(μ2‐2‐methoxyethanolato)dimethyl(tetrahydrofuran‐κO)aluminium(III)tetramanganese(II)

The molecule of the title compound, [Mn₄Al(CH₃)₂(C₃H₇O₂)₄I₅(C₄H₈O)], contains one Al^III and four Mn^II ions. Two Mn atoms are five‐coordinate in the form of a trigonal bipyramid or a square pyramid. The two other Mn atoms are six‐coordinate with an octahedral geometry. The fourcoordinate Al atom is linked to the manganese core by μ‐O_alkoxo bridges, forming an almost planar five‐membered ring.     

Investigation of commercial sodium cacodylate trihydrate: penta‐μ‐aqua‐disodium(I) bis(dimethylarsenate) and di‐μ‐aqua‐bis[triaquasodium(I)] bis(dimethylarsenate)

Crystals from commercial samples of sodium cacodylate trihydrate, NaO₂As(CH₃)₂·3H₂O, were analyzed by single‐crystal X‐ray diffraction and two phases were identified, viz. penta‐μ‐aqua‐disodium(I) bis(dimethylarsenate), {[Na₂(H₂O)₅](C₂H₆AsO₂)₂}_n, (I), and di‐μ‐aqua‐bis[triaquasodium(I)] bis(dimethylarsenate), [Na₂(H₂O)₈](C₂H₆AsO₂)₂, (II). Both (I) and (II) form layered structures in which hydrated Na⁺ ions form layers in the ab plane, the cacodylate ions being located in between the layers. In (I), the two non‐equivalent Na⁺ ions (located at twofold axes) and the three non‐equivalent aqua ligands (one of which also lies on a twofold axis) form infinite polymeric layers, but in (II), layers of discrete centrosymmetric [Na₂(H₂O)₈]²⁺ ions are present. One of the commercial samples analyzed contained almost exclusively crystals of the tetrahydrate (II), while another sample consisted of a mixture of the two phases.     

Bis(2‐amino‐1H‐benzimidazol‐3‐ium) tetrakis(μ‐but‐2‐enoato)‐κ4O:O′;κ3O,O′:O;κ3O:O,O′‐bis[bis(but‐2‐enoato‐κ2O,O′)holmium(III)]

The title ionic compound, (C₇H₈N₃)₂[Ho₂(C₄H₅O₂)₈], is constructed from two almost identical independent centrosymmetric anionic dimers balanced by two independent 2‐amino‐1H‐benzimidazol‐3‐ium (Habim⁺) cations. The asymmetric part of each dimer is made up of one Ho^III cation and four crotonate (crot or but‐2‐enoate) anions, two of them acting in a simple η²‐chelating mode and the remaining two acting in two different μ₂:η² fashions, viz. purely bridging and bridging–chelating. Symmetry‐related Ho^III cations are linked by two Ho—O—Ho and two Ho—O—C—O—Ho bridges which lead to rather short intracationic Ho...Ho distances [3.8418 (3) and 3.8246 (3) Å]. In addition to the obvious Coulombic interactions linking the cations and anions, the isolated [Ho₂(crot)₈]²⁻ and Habim⁺ ions are linked by a number of N—H...O hydrogen bonds, in which all N—H groups of the cation are involved as donors and all (simple chelating) crot O atoms are involved as acceptors. These interactions result in compact two‐dimensional structures parallel to (110), which are linked to each other by weaker π–π contacts between Habim⁺ benzene groups.     

Bis(μ‐6‐hydroxy­picolinato)‐μ‐oxo‐bis­[di­pyridine­manganese(III)] monohydrate

The title compound, [Mn₂(μ‐O)(C₆H₃NO₃)₂(C₅H₅N)₄]·H₂O, was isolated from the reaction of 2,6‐pyridine­di­carboxylic acid with [Mn₁₂O₁₂(CH₃COO)₁₆(H₂O)₄] in pyridine. The dimanganese complex has twofold symmetry; the Mn^III atoms are bridged by one oxo and two amidate ligands and show compressed octahedral Jahn–Teller distortion. The molecular packing comprises a three‐dimensional structure constructed by means of extensive intermolecular interactions, including three kinds of hydrogen bonds and π–π interactions.     

Tetrakis(μ‐triisopropylsilanethiolato)‐1:2κ4S:S;2:3κ4S:S‐bis(triisopropylsilanethiolato)‐1κS,3κS‐trizinc(II)

The title compound, [Zn₃(C₉H₂₁SiS)₆] or [(ⁱPr₃SiS)Zn(μ‐SSiⁱPr₃)₂Zn(μ‐SSiⁱPr₃)₂Zn(SSiⁱPr₃)], is the first structurally characterized homoleptic silanethiolate complex of zinc. A near‐linear arrangement of three Zn^II ions is observed, the metals at the ends being three‐coordinate with one terminally bound silanethiolate ligand. The central Zn^II ion is four‐coordinate and tetrahedral, with two bridging silanethiolate ligands joining it to each of the two peripheral Zn^II ions. The nonbonding intermetallic distances are 3.1344 (11) and 3.2288 (12) Å, while the Zn...Zn...Zn angle is 172.34 (2)°. A trimetallic silanethiolate species of this type has not been previously identified by X‐ray crystallography for any element.     

Synthesis and crystal structure of a two‐dimensional sodium coordination polymer of 4,4′‐(diazenediyl)bis(1H‐1,2,4‐triazol‐5‐one)

The crystal engineering of coordination polymers has aroused interest due to their structural versatility, unique properties and applications in different areas of science. The selection of appropriate ligands as building blocks is critical in order to afford a range of topologies. Alkali metal cations are known for their mainly ionic chemistry in aqueous media. Their coordination number varies depending on the size of the binding partners, and on the electrostatic interaction between the ligands and the metal ions. The two‐dimensional coordination polymer poly[tetra‐μ‐aqua‐[μ₄‐4,4′‐(diazenediyl)bis(5‐oxo‐1H‐1,2,4‐triazolido)]disodium(I)], [Na₂(C₄H₂N₈O₂)(H₂O)₄]_n, (I), was synthesized from 4‐amino‐1H‐1,2,4‐triazol‐5(4H)‐one (ATO) and its single‐crystal structure determined. The mid‐point of the imino N=N bond of the 4,4′‐(diazenediyl)bis(5‐oxo‐1H‐1,2,4‐triazolide) (ZTO²⁻) ligand is located on an inversion centre. The asymmetric unit consists of one Na⁺ cation, half a bridging ZTO²⁻ ligand and two bridging water ligands. Each Na⁺ cation is coordinated in a trigonal antiprismatic fashion by six O atoms, i.e. two from two ZTO²⁻ ligands and the remaining four from bridging water ligands. The Na⁺ cation is located near a glide plane, thus the two bridging O atoms from the two coordinating ZTO²⁻ ligands are on adjacent apices of the trigonal antiprism, rather than being in an anti configuration. All water and ZTO²⁻ ligands act as bridging ligands between metal centres. Each Na⁺ metal centre is bridged to a neigbouring Na⁺ cation by two water molecules to give a one‐dimensional [Na(H₂O)₂]_n chain. The organic ZTO²⁻ ligand, an O atom of which also bridges the same pair of Na⁺ cations, then crosslinks these [Na(H₂O)₂]_n chains to form two‐dimensional sheets. The two‐dimensional sheets are further connected by intermolecular hydrogen bonds, giving rise to a stabile hydrogen‐bonded network.     

Synthese und dynamisches Verhalten von [Rh2(μ-H)3H2(PiPr3)4]+. Beiträge zur Reaktivität des Tetrahydridodirhodium-Komplexes [Rh2H4(PiPr3)4]

Synthesis and Dynamic Behaviour of [Rh₂(μ-H)₃H₂(PiPr₃)₄]⁺. Contributions to the Reactivity of the Tetrahydridodirhodium Complex [Rh₂H₄(PiPr₃)₄] An improved synthesis of [Rh₂H₄(PiPr₃)₄] ( 2 ) from [Rh(η³-C₃H₅)(PiPr₃)₂] ( 1 ) or [Rh(η³-CH₂C₆H₅)(PiPr₃)₂] ( 3 ) and H₂ is described. Compound 2 reacts with CO or CH₃OH to give trans-[RhH(CO)(PiPr₃)₂] ( 4 ) and with ethene/acetone to yield a mixture of 4 and trans-[RhCH₃(CO)(PiPr₃)₂] ( 5 ). The carbonyl(methyl) complex 5 has also been prepared from trans-[RhCl(CO)(PiPr₃)₂] ( 6 ) and CH₃MgI. Whereas the reaction of 2 with two parts of CF₃CO₂H leads to [RhH₂(η²-O₂CCF₃) · (PiPr₃)₂] ( 8 ), treatment of 2 with one equivalent of CF₃CO₂H in presence of NH₄PF₆ gives the dinuclear compound [Rh₂H₅(PiPr₃)₄]PF₆ ( 9a ). The reactions of 2 with HBF₄ and [NO]BF₄ afford the complexes [Rh₂H₅(PiPr₃)₄]BF₄ ( 9b ) and trans-[RhF(NO)(PiPr₃)₂]BF₄ ( 11 ), respectively. In solution, the cation [Rh₂(μ-H)₃H₂(PiPr₃)₄]⁺ of the compounds 9a and 9b undergoes an intramolecular rearrangement in which the bridging hydrido and the phosphane ligands are involved.     

Poly[diaqua­(μ‐4,4′‐bipyridine)tetra­kis­(μ‐ferro­cenecarboxyl­ato)bis­(ferro­cenecarboxyl­ato)­tri­man­ganese(II)]

The title compound, [Mn₃Fe₆(C₅H₅)₆(C₆H₄O₂)₆(C₁₀H₈N₂)(H₂O)₂]_n, consists of two crystallographically unique Mn^II centers. One is situated on an inversion center and is octa­hedrally coordinated by two N atoms from two bridging 4,4′‐bipyridine (4,4′‐bipy) ligands and four O atoms, two from different bridging ferrocenecarboxyl­ate (μ₂‐FcCOO⁻; Fc is ferrocene) units and two from aqua ligands. The two halves of each 4,4′‐bipy ligand are related by a center of symmetry. The second Mn^II center is in a strongly distorted tetra­gonal–pyramidal geometry, coordinated by five O atoms, three from three μ₂‐FcCOO⁻ units and two from a fourth, chelating, η²‐FcCOO⁻ unit. The FcCOO⁻ units function as bridging ligands to adjacent Mn^II centers, leading to the formation of linear ⋯Mn1Mn2Mn2Mn1⋯ chains. Adjacent chains are further bridged by 4,4′‐bipy ligands, resulting in a two‐dimensional layered polymer.     

Hexaaquacobalt(II) and hexaaquanickel(II) bis(μ‐pyridine‐2,6‐dicarboxylato)bis[(pyridine‐2,6‐dicarboxylato)bismuthate(III)] dihydrate

The title complexes, hexaaquacobalt(II) bis(μ‐pyridine‐2,6‐dicarboxylato)bis[(pyridine‐2,6‐dicarboxylato)bismuthate(III)] dihydrate, [Co(H₂O)₆][Bi₂(C₇H₄NO₄)₄]·2H₂O, (I), and hexaaquanickel(II) bis(μ‐pyridine‐2,6‐dicarboxylato)bis[(pyridine‐2,6‐dicarboxylato)bismuthate(III)] dihydrate, [Ni(H₂O)₆][Bi₂(C₇H₄NO₄)₄]·2H₂O, (II), are isomorphous and crystallize in the triclinic space group P. The transition metal ions are located on the inversion centre and adopt slightly distorted MO₆ (M = Co or Ni) octahedral geometries. Two [Bi(pydc)₂]⁻ units (pydc is pyridine‐2,6‐dicarboxylate) are linked via bridging carboxylate groups into centrosymmetric [Bi₂(pydc)₄]²⁻ dianions. The crystal packing reveals that the [M(H₂O)₆]²⁺ cations, [Bi₂(pydc)₄]²⁻ anions and solvent water molecules form multiple hydrogen bonds to generate a supramolecular three‐dimensional network. The formation of secondary Bi...O bonds between adjacent [Bi₂(pydc)₄]²⁻ dimers provides an additional supramolecular synthon that directs and facilitates the crystal packing of both (I) and (II).     

The new one‐dimensional coordination polymer catena‐poly[[diaquasodium(I)]‐μ‐oxalato‐[diaquairon(III)]‐μ‐oxalato]

The oxalate dianion is one of the most studied ligands and is capable of bridging two or more metal centres and creating inorganic polymers based on the assembly of metal polyhedra with a wide variety of one‐, two‐ or three‐dimensional extended structures. Yellow single crystals of a new mixed‐metal oxalate, namely catena‐poly[[diaquasodium(I)]‐μ‐oxalato‐κ⁴O¹,O²:O^1′,O^2′‐[diaquairon(III)]‐μ‐oxalato‐κ⁴O¹,O²:O^1′,O^2′], [NaFe(C₂O₄)₂(H₂O)₄]_n, have been synthesized and the crystal structure elucidated by X‐ray diffraction analysis. The compound crystallizes in the noncentrosymmetric space group I4₁ (Z = 4). The asymmetric unit contains one Na^I and one Fe^III atom lying on a fourfold symmetry axis, one μ₂‐bridging oxalate ligand and two aqua ligands. Each metal atom is surrounded by two chelating oxalate ligands and two equivalent water molecules. The structure consists of infinite one‐dimensional chains of alternating FeO₄(H₂OW1)₂ and NaO₄(H₂OW2)₂ octahedra, bridged by oxalate ligands, parallel to the [100] and [010] directions, respectively. Because of the cis configuration and the μ₂‐coordination mode of the oxalate ligands, the chains run in a zigzag manner. This arrangement facilitates the formation of hydrogen bonds between neighbouring chains involving the H₂O and oxalate ligands, leading to a two‐dimensional framework. The structure of this new one‐dimensional coordination polymer is shown to be unique among the A^IM^III(C₂O₄)₂(H₂O)_n series. In addition, the absorption bands in the IR and UV–Visible regions and their assignments are in good agreement with the local symmetry of the oxalate ligand and the irregular environment of iron(III). The final product of the thermal decomposition of this precursor is the well‐known ternary oxide NaFeO₂.     

catena‐Poly[[aqua­bis(1H‐benzimidazole‐κN3)manganese(II)]‐μ‐adipato]

In the title polymeric complex, [Mn(C₆H₈O₄)(C₇H₆N₂)₂(H₂O)]_n, the Mn^II atom is surrounded by two adipate dianions, two benzimidazole mol­ecules and one coordinated water mol­ecule. The Mn atoms and coordinated water mol­ecule are located on a twofold axis, and the bridging adipate ligand is located on an inversion center. The adipate dianions bridge neighboring Mn^II atoms to form polymeric chains. Each Mn^II atom is seven‐coordinate, the longest Mn—O bond length being 2.5356 (16) Å.     

Poly[tetra‐μ2‐l‐lactato‐indium(III)sodium(I)]

The asymmetric unit of the title compound, [InNa(C₃H₅O₃)₄]_n, consists of one In^III ion, one Na^I ion and four crystallographically independent l ‐lactate monoanions. The coordination of the In^III ion is composed of five carboxylate O and two hydroxy O atoms in a distorted pentagonal–bipyramidal coordination geometry. The Na^I ion is six‐coordinated by four carboxylate O atoms and two hydroxy O atoms from four l ‐lactate ligands in a distorted octahedral geometry. Each In^III ion is coordinated by four surrounding l ‐lactate ligands to form an [In(l ‐lactate)₄]⁻ unit, which is further linked by Na^I ions through Na—O bonds to give a two‐dimensional layered structure. Hydrogen bonds between the hydroxy groups and carboxylate O atoms are observed between neighbouring layers.     

Bis[2‐(2‐hydroxyethyl)pyridinium] μ‐decavanadato‐bis[pentaaquamanganate(II)] tetrahydrate

The structure of the title compound, (C₇H₁₀NO)₂[Mn₂V₁₀O₂₈(H₂O)₁₀]·4H₂O or (C₅H₄NHCH₂CH₂OH)₂[{Mn(H₂O)₅}₂V₁₀O₂₈]·4H₂O, at 293 (2) K has triclinic (P) symmetry. The asymmetric unit consists of one half of a decavanadate anion of C_i symmetry, one [Mn(H₂O)₅]²⁺ group, one 2‐(2‐hydroxyethyl)pyridinium cation and two solvent water molecules. The decavanadate ion bridges between two [Mn(H₂O)₅]²⁺ groups, thus forming a dodecanuclear complex unit. Complex units are connected via a hydrogen‐bonding network, forming supramolecular layers lying in the (001) plane. Cations and solvent water molecules are located between these layers.     

Poly[bis(μ4‐benzene‐1,2‐dicarboxylato)di‐μ3‐isonicotinato‐dilanthanum(III)]

In the title compound, [La₂(C₈H₄O₄)₂(C₆H₄NO₂)₂]_n, there are two crystallographically independent La centres, both nine‐coordinated in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom. The La centres are linked by the carboxylate groups of isonicotinate (IN⁻) and benzene‐1,2‐dicarboxylate (BDC²⁻) ligands to form La–carboxylate chains, which are further expanded into a three‐dimensional framework with nanometre‐sized channels by La—N bonds. In the construction of the resultant architecture, in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom, while the BDC ligands link to four different cations each, displaying penta‐ and heptadentate chelating–bridging modes, respectively.     

Tetrakis(5‐tert‐butylpyrazole‐1κN2)tetrachloro‐1κCl,2κ3Cl‐μ‐oxo‐1:2κ2O‐diiron(III)

The title compound, [Fe₂Cl₄O(C₇H₁₂N₂)₄], contains vertex‐sharing distorted tetrahedral [FeOCl₃]^? and octahedral [FeOCl(Hpz^tBu)₄]⁺ moieties (Hpz^tBu is 5‐tert‐­butyl­pyrazole), linked by a bent oxo bridging ligand. The two Fe^III centres are also bridged by intramolecular hydrogen bonds between the pyrazole N—H groups and the O^2? and Cl^? ligands.