fac‐Tri­carbonyl(4,4′‐di­methyl‐2,2′‐bi­pyridine)­tri­phenyl­tin(II)­rhenium(I)

The title organometallic compound, fac‐tri­carbonyl‐2κ³C‐(4,4′‐di­methyl‐2,2′‐bi­pyridine)‐2κ²N,N′‐tri­phenyl‐1κ³C¹‐tin(II)­rhenium(I)(Sn—Re), [ReSn(C₆H₅)₃(C₁₂H₁₂N₂)(CO)₃], con­tains three unique π–π stacking interactions. The result is an infinite chain of uninterrupted alternating intra‐ and intermolecular offset π–π stacking interactions throughout the crystal lattice. This extended π–π stacking arrangement, and an additional isolated intramolecular π–π interaction between the remaining 4,4′‐di­methyl‐2,2′‐bi­pyridine ring and a second phenyl group, impose geometric constraints on the Re and Sn atoms, yielding distorted octahedral and tetrahedral coordinations, respectively, for the metal centers.     

A one‐dimensional zigzag coordination polymer of di­aqua­(pyridine‐2,3‐di­carboxyl­ato)­cobalt(II)

The asymmetric unit of the title one‐dimensional coordination polymer, catena‐poly­[[μ‐pyridine‐2,3‐di­carb­oxyl­ato‐1κO:2κ²N,O′‐bis­[di­aqua­cobalt(II)]]‐μ‐pyridine‐2,3‐di­carboxyl­ato‐1κ²N,O:2κO′:1′κO′], [Co(C₇H₃NO₄)(H₂O)₂]_n, is composed of a cobalt(II) ion, a pyridine‐2,3‐di­carboxyl­ate dianion and two water mol­ecules. The polymer has a zigzag structure consisting of a chain of edge‐fused rings, and the polymer chains are linked by O—H⃛O hydrogen bonds into a three‐dimensional framework.     

(2,2′‐Bi­pyridine‐κ2N,N′)(2,3‐naph­tha­lene­diolato‐κ2O,O′)­palladium(II) and (2,2′‐bi­quinoline‐κ2N,N′)(2,3‐naph­thal­ene­diolato‐κ2O,O′)­palladium(II)

In the title compounds, [Pd(C₁₀H₆O₂)(C₁₀H₈N₂)], (I), and [Pd(C₁₀H₆O₂)(C₁₈H₁₂N₂)], (II), each Pd^II atom has a similar distorted cis‐planar four‐coordination geometry involving two O atoms of the 2,3‐­naphthalenediolate dianion and two N atoms of the 2,2′‐bi­pyridine or 2,2′‐bi­quinoline ligand. The overall structure of (I) is essentially planar, but that of (II) is not, as a result of intramolecular overcrowding leading to bowing of the bi­quinoline ligand.     

catena‐Poly­[europium(III)‐tri‐μ‐2,3‐di­methoxy­benzoato]

The title compound, [Eu(C₉H₉O₄)₃]_n or [Eu(2,3‐DMOBA)₃]_n, where 2,3‐DMOBA is 2,3‐di­methoxy­benzoate, is an infinite one‐dimensional non‐centrosymmetric coordination polymer. The unique Eu^III atom is bridged by six carboxyl­ate ligands; it is ennea‐coordinated and has a distorted tricapped trigonal prism geometry. The Eu—O distances are in the range 2.315 (3)–2.959 (5) Å.     

Tetra­aqua(2,2′‐bi­pyridine)­nickel(II) terephthalate

The reaction of nickel(II) nitrate with terephthalic acid and 2,2′‐bi­pyridine in di­methyl­form­amide solution gives the title complex, [Ni(C₁₀H₈N₂)(H₂O)₄](C₈H₄O₄). The Ni^II ion is octahedrally coordinated to one 2,2′‐bi­pyridine and four water mol­ecules and does not coordinate to the terephthalate anion. Hydro­gen bonds between the terephthalate anions and the [Ni(2,2′‐bipy)(H₂O)₄]²⁺ cations produce a two‐dimensional hydrogen‐bonding architecture with double sheets.     

A single‐strand helical coordination polymer: catena‐poly­[[[tri­aqua­nickel(II)]‐μ‐2,2′‐bi­pyridine‐3,3′‐di­carboxyl­ato‐κ3N,N′:O] monohydrate]

The asymmetric unit of the title compound, {[Ni(C₁₂H₆N₂O₄)(H₂O)₃]·H₂O}_n, is composed of a lattice water mol­ecule and a nickel(II) ion that is coordinated by three water mol­ecules and the two N atoms of a 2,2′‐bi­pyridine‐3,3′‐di­carboxyl­ate ligand. The twist of the 2,2′‐bi­pyridine‐3,3′‐di­carboxyl­ate unit and the coordination of one carboxyl­ate group to a symmetry‐related Ni^II atom generate a helical chain that runs along the b axis. Intrahelical hydrogen bonds participate in controlling the orientation of the helices, and both right‐handed and left‐handed helices are connected by interhelical hydrogen bonds into two‐dimensional sheets.     

Magnesium iodide–4,4′‐bipyridine–water (1/3/4) and strontium iodide–4,4′‐bipyridine–propan‐1‐ol (1/2.5/2)

Both of the title compounds, catena‐poly­[[[tetra­aqua­magnesium(I)]‐μ‐4,4′‐bi­pyridine‐κ²N:N′] diiodide bis(4,4′‐bi­pyridine) solvate], {[Mg(C₁₀H₈N₂)(H₂O)₄]I₂·2C₁₀H₈N₂}_n, (I), and catena‐poly­[[[μ‐4,4′‐bi­pyridine‐bis­[di­iodo­bis­(propan‐1‐ol)­strontium(I)]]‐di‐μ‐4,4′‐bi­pyridine‐κ⁴N:N′] bis(4,4′‐bi­pyri­dine) solvate], {[Sr₂I₄(C₁₀H₈N₂)₃(C₃H₈O)₄]·2C₁₀H₈N₂}_n, (II), are one‐dimensional polymers which are single‐ and double‐stranded, respectively, the metal atoms being linked by the 4,4′‐bi­pyridine moieties. The Mg complex, (I), is [cis‐{(H₂O)₄Mg(N‐4,4′‐bi­pyridine‐N′)_(2/2)}]_(∞|∞)I₂·4,4′‐bi­pyridine and Mg has a six‐coordinate quasi‐octahedral coordination environment. The Sr complex, (II), is isomorphous with its previously defined Ba counterpart [Kepert, Waters & White (1996). Aust. J. Chem. 49 , 117–135], being [(propan‐1‐ol)₂I₂Sr(N‐4,4′‐bi­pyridine‐N′)_(3/2)]_(∞|∞)·4,4′‐bi­pyridine, with the I atoms trans‐axial in a seven‐coordinate pentagonal–bipyramidal Sr environment.     

[N,N′‐Bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminato]­nickel(II) and [N,N′‐bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminato]copper(II)

In the title compounds, {2,2′‐[2,2‐di­methyl‐1,3‐propane­diyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴N,N′,O,O′}nickel(II), [Ni(C₁₉H₂₀N₂O₂)], and {2,2′‐[2,2‐di­methyl‐1,3‐propane­diyl­bis­(nitrilo­methyl­idyne)]­diphenolato‐κ⁴N,N′,O,O′}copper(II), [Cu(C₁₉H₂₀N₂O₂)], the Ni^II and Cu^II atoms are coordinated by two iminic N and two phenolic O atoms of the N,N′‐bis­(salicyl­idene)‐2,2‐di­methyl‐1,3‐propane­diaminate (SALPD^2?, C₁₇H₁₆N₂O₂^2?) ligand. The geometry of the coordination sphere is planar in the case of the Ni^II complex and distorted towards tetrahedral for the Cu^II complex. Both complexes have a cis configuration imposed by the chelate ligand. The dihedral angles between the N/Ni/O and N/Cu/O coordination planes are 17.20 (6) and 35.13 (7)°, respectively.     

N,N′‐Bis(2‐methoxy­benzyl­idene) adducts of ethane‐1,2‐di­amine,propane‐1,3‐di­amine and butane‐1,4‐di­amine

We have isolated and crystallographically characterized the three homologous compounds N,N′‐bis(2‐methoxy­benzyl­idene)­ethane‐1,2‐di­amine (MeSalen), C₁₈H₂₀N₂O₂, N,N′‐bis(2‐methoxy­benzyl­idene)­propane‐1,3‐di­amine (MeSalpr), C₁₉H₂₂N₂O₂, and N,N′‐bis(2‐methoxy­benzyl­idene)­butane‐1,4‐di­amine (MeSalbu), C₂₀H₂₄N₂O₂. In contrast with MeSalpr, the mol­ecules of MeSalen and MeSalbu, which have an even number of methyl­ene units, have crystallographic symmetry. Comparing these methoxy‐substituted species with their hydroxy equivalents shows that the aryl rings rotate upon removal of the O—H⋯N hydrogen bonds. The packing of MeSalen and MeSalpr is controlled by C—H⋯π interactions, whereas that of MeSalbu has only van der Waals contacts.     

Di‐μ‐sulfito‐bis­[(4,4′‐di­methyl‐2,2′‐bi­pyridine)­zinc(II)] dihydrate and poly­[[aqua(1,10‐phenanthroline)­zinc(II)]‐μ3‐sulfito‐zinc(II)‐μ3‐sulfito]

Two different zinc sulfite compounds have been prepared through the decomposition of pyrosulfite–­di­thionite ions in aqueous solution, viz. a dimeric complex, di‐μ‐sulfito‐κ³O,O′:O′′;κ³O:O′,O′′‐bis­[(4,4′‐di­methyl‐2,2′‐bi­pyridine‐κ²N,N′)­zinc(II)] dihydrate, [Zn₂(SO₃)₂(C₁₂H₁₂N₂)₂]·2H₂O, (I), which was solved and refined from a twinned sample, and an extended polymer, poly­[[aqua(1,10‐phenanthroline‐κ²N,N′)­zinc(II)]‐μ₃‐sulfito‐κ²O:O′:O′′‐zinc(II)‐μ₃‐sulfito‐κ³O:O:O′], [Zn₂(SO₃)₂(C₁₂H₁₀N₂)(H₂O)]_n, (II). In (I), the dinuclear Zn^II complex has a center of symmetry. The cation is five‐coordinate in a square‐pyramidal arrangement, the anion fulfilling a bridging chelating role. Compound (II) comprises two different zinc units, one being five‐coordinate (square pyramidal) and the other four‐coordinate (trigonal pyramidal), and two independent sulfite groups with different binding modes to the cationic centers.     

Packing effects in 4,4′‐bis(4‐hydroxy­butyl)‐2,2′‐bi­pyridine and 4,4′‐bis(4‐bromo­butyl)‐2,2′‐bi­pyridine

Structure analyses of 4,4′‐bis(4‐hydroxy­butyl)‐2,2′‐bi­pyridine, C₁₈H₂₄N₂O₂, (I), and 4,4′‐bis(4‐bromo­butyl)‐2,2′‐bi­pyridine, C₁₈H₂₂Br₂N₂, (II), reveal intermolecular hydrogen bonding in both compounds. For (I), O—H·N intermolecular hydrogen bonding leads to the formation of an infinite two‐dimensional polymer, and π stacking interactions are also observed. For (II), C—H·N intermolecular hydrogen bonding leads to the formation of a zigzag polymer. The two compounds crystallize in different crystal systems, but both mol­ecules possess C_i symmetry, with one half mol­ecule in the asymmetric unit.     

Tetra‐μ‐2‐fluoro­benzoato‐bis[aqua(4,4′‐bi­pyridine)(2‐fluorobenzoato)lanthanum(III)]

Each La³⁺ ion in the title complex, tetra‐μ‐2‐fluorobenzoato‐κ¹⁰O:O′;O:O,O′;O:O′;O,O′:O′‐bis[aqua(4,4′‐bipy­ridine‐κN)(2‐fluorobenzoato‐κO)lanthanum(II)], [La(C₇H₄FO₂)₆(C₁₀H₈N₂)₂(H₂O)₂], is coordinated by six O atoms from the carboxyl­ate groups of five 2‐fluoro­benzoate ligands, one O atom from a water mol­ecule and one N atom from a 4,4′‐bi­pyridine mol­ecule, thus forming a dimeric mol­ecule. An infinite one‐dimensional dimeric supramolecular chain is formed via intermolecular hydrogen bonds.     

Poly­[[di­aqua­cobalt(II)]‐μ‐4,4′‐bi­pyridine‐κ2N:N′‐μ‐p‐phenyl­enebis­(oxy­acetato)‐κ2O:O′]

The title compound, [Co^II(C₁₀H₈O₆)(C₁₀H₈N₂)(H₂O)₂]_n, was obtained by the hydro­thermal reaction of CoSO₄ with benzene‐1,4‐dioxy­di­acetate [systematic name: p‐phenyl­ene­bis­(oxy­acetate)] and 4,4′‐bi­pyridine (4,4′‐bpy). The Co atom lies at an inversion center and the benzene‐1,4‐dioxydiacetate and 4,4′‐bipyridine moieties lie about other inversion centers. The benzene‐1,4‐dioxydiacetate ligands bridge the octahedral Co^II coordination centers, forming a one‐dimensional zigzag chain. The chains are further bridged by 4,4′‐bpy ligands, forming a novel two‐dimensional supramolecular architecture. Hydro­gen‐bonding interactions between the coordinated water mol­ecules and the carboxyl­ate O atoms lead to the formation of a three‐dimensional network structure.     

Dimeric hexakis(4‐methyl­benzoato)­bis(1,10‐phenanthroline)didyspros­ium(III)

The title compound, [Dy₂(C₈H₇O₂)₆(C₁₂H₈N₂)₂], forms binuclear complexes, viz. di‐μ‐4‐methyl­benzoato‐κ⁴O:O′‐bis[bis(4‐methyl­benzoato‐κ²O,O′)(1,10‐phenanthroline‐κ²N,N′)dyspros­ium(III)] tetra‐μ‐4‐methyl­benzoato‐κ⁸O:O′‐bis[(4‐methyl­benzoato‐κ²O,O′)(1,10‐phenanthroline‐κ²N,N′)dyspros­ium(III)]. There are two independent binuclear com­plexes in the asymmetric unit, both of which are centrosymmetric. In one, the Dy^III ions are linked by two bridging 4‐­methyl­benzoate groups, while in the other, the Dy^III ions are linked by four bridging 4‐methyl­benzoate groups. The remaining 4‐methyl­benzoate groups and 1,10‐phenanthroline units coordinate to just one metal ion in bidentate modes.     

A one‐dimensional double‐chain coordination polymer: [Mn(C12H13NO6S)(C10H8N2)]n

In the title compound, poly­[[(2,2′‐bi­pyridine‐κ²N,N′)­manganese(II)]‐μ₃‐N‐tosyl‐l ‐glutamato‐κ⁴O,O′:O′′:O′′′], [Mn(tsgluo)(bipy)]_n, where tsgluo is N‐tosyl‐l ‐glutamate (C₁₂H₁₃NO₆S) and bipy is 2,2′‐bi­pyridine (C₁₀H₈N₂), the Mn atoms are octahedrally coordinated by two N atoms of one bipy ligand and by four O atoms of three tsgluo²⁻ anions. The γ‐carboxyl group coordinates to the Mn^II atom in a chelating mode, while the α‐carboxyl group coordinates in a bidentate–bridging mode. The complex displays a one‐dimensional double‐chain structure.     

(R)‐(+)‐2,2′‐Bis­(di­phenyl­phosphinoyl)‐1,1′‐bi­naphthyl

The title compound, BINAP oxide, C₄₄H₃₂O₂P₂, (I), was synthesized by direct oxidation of (R)‐(+)‐2,2′‐bis­(di­phenyl­phosphino)‐1,1′‐bi­naphthyl (BINAP) with tert‐butyl hydro­peroxide in toluene solution. The angle between the naphthyl planes of the bi­naphthyl group is 94.17 (3)°.     

Dichloro(2,2′‐diamino‐4,4′‐bi‐1,3‐thiazole‐N3,N3′)copper(II)

The title complex, [CuCl₂(C₆H₆N₄S₂)], has a flattened tetrahedral coordination. The Cu^II atom is located on a twofold rotation axis and is coordinated by two N atoms from a chelating 2,2′‐di­amino‐4,4′‐bi‐1,3‐thia­zole ligand and by two Cl atoms. Intramolecular hydrogen bonding exists between the amino groups of the 2,2′‐di­amino‐4,4′‐bi‐1,3‐thia­zole ligand and the Cl atoms. The intermolecular separation of 3.425 (1) Å between parallel bi­thia­zole rings suggests there is a π–π interaction between them.     

A host–guest complex of di­aqua­bis­[1‐hydroxy‐2(1H)‐pyridine­thionato‐O,S]­magnesium(II) and 2,2′‐di­thio­bis­(pyridine N‐oxide)

The title compound, [Mg(C₅H₄NOS)₂(H₂O)₂]·C₁₀H₈N₂O₂S₂, is a two‐component host–guest material. The 2,2′‐di­thio­bis(pyridine N‐oxide) molecule has crystallographic twofold symmetry. The metal complex lies on an inversion centre and associates via C—H?S interactions into chains which thread the 2,2′‐di­thio­bis­(pyridine N‐oxide) lattice in perpendicular directions. Hydro­gen bonds exist between the water mol­ecules of the di­aqua­magnesium units and the N—O groups of the host lattice.     

Poly­[[di­aqua­tris(μ6‐benzene‐1,2,4,5‐tetra­carboxyl­ato)­tris(μ2‐4,4′‐bi­pyridine)­hexacopper(II)] dihydrate]

The hydro­thermal reaction of an aqueous solution of Cu(CH₃COO)₂·H₂O, 1,2,4,5‐benzene­tetra­carboxylic acid and 4,4′‐bi­pyridine gave rise to the interesting title three‐dimensional polymer {[Cu₆(btec)₃(4,4′‐bpy)₃(H₂O)₂]·2H₂O}_n (btec is 1,2,4,5‐benzene­tetra­carboxyl­ate, C₁₀H₂O₈⁴⁻, and 4,4′‐bpy is 4,4′‐bi­pyridine, C₁₀H₈N₂), in which each btec ligand links six copper(II) cations into a lamellar [Cu₆(btec)₃(H₂O)₂]_n sub­polymer framework. There are two distinct diamine units and two distinct carboxylate units, with one of each lying across an inversion centre.     

trans‐Di­aqua­bis(5‐carboxy‐1H‐imidazole‐4‐carboxyl­ato‐κ2N3,O4)­cobalt(II) 4,4′‐bi­pyridine solvate

In the title compound, [Co(C₅H₃N₂O₄)₂(H₂O)₂]·C₁₀H₈N₂, the Co atom is trans‐coordinated by two pairs of N and O atoms from two monoanionic 4,5‐di­carboxy­imidazole ligands, and by two O atoms from two coordinated water mol­ecules, in a distorted octahedral geometry. The 4,4′‐bi­pyridine solvent molecule is not involved in coordination but is linked by an N—H⋯N hydrogen bond to the neutral [Co(C₅H₃N₂O₄)₂(H₂O)₂] mol­ecule. Both mol­ecules are located on inversion centers. The crystal packing is stabilized by N—H⋯N and O—H⋯O hydrogen bonds, which produce a three‐dimensional hydrogen‐bonded network. Offset π–π stacking interactions between the pyridine rings of adjacent 4,4′‐bi­pyridine molecules were observed, with a face‐to‐face distance of 3.345 (1) Å.