catena‐Poly[[[diaqua­bis(pyridine‐4‐carboxamide‐κN)copper(II)]‐μ2‐squarato‐κO1:O3] dihydrate]

The asymmetric unit of the title compound, {[Cu(C₄O₄)(C₆H₆N₂O)₂(H₂O)₂]·2H₂O}_n, consists of one pyridine‐4‐carbox­amide (isonicotinamide or ina) ligand, one‐half of a squarate dianion, a coordinated aqua ligand and a solvent water mol­ecule. Both the Cu^II and the squarate ions are located on inversion centers. The Cu^II ions are octa­hedrally surrounded by four O atoms of two water mol­ecules and two squarate anions, and by two N atoms of the isonicotinamide ligands. The crystal structure contains chains of squarate‐1,3‐bridged Cu^II ions. These chains are held together by N—H⋯O and O—H⋯O inter­molecular hydrogen‐bond inter­actions, forming an extensive three‐dimensional network.     

The first di‐μ‐hydro­xo‐bridged binuclear copper complex containing a bis‐guanidine ligand

The present structure determination of di‐μ‐hydroxo‐bis{[N,N′‐bis­(dipiperidino­methyl­ene)­propane‐1,3‐di­amine‐κ²N,N′]copper(II)} bis­(hexa­fluoro­phosphate), [Cu₂(OH)₂(C₂₅H₄₆N₆)₂](PF₆)₂, is the first to crystallographically characterize a Cu₂(μ‐OH)₂ complex with a bidentate guanidine ligand. The cation lies on a crystallographic inversion centre and shows planar fourfold coordination of the copper centres. The Cu₂(μ‐OH)₂ species can be distinguished from Cu₂(μ‐O)₂ by the Cu—O bond lengths. The packing is determined by strong intermolecular anion–cation hydrogen bonds.     

Poly[[aqua­tetra­imidazole­di‐μ‐phthalato‐dicopper(II)] monohydrate]

The title complex, {[Cu₂(C₈H₄O₄)₂(C₃H₄N₂)₄(H₂O)]·H₂O}_n, is a three‐dimensional polymer formed through bridging by phthalate dianions of two different Cu^II cations and a network of O(N)—H⋯O hydrogen bonds. The Cu—O and Cu—N inter­action distances are in the ranges 2.0020 (16)–2.4835 (17) and 1.968 (2)–1.9855 (19) Å, respectively. The structure is composed of alternating polymer chains parallel to the c axis, with a shortest Cu⋯Cu distance of 6.3000 (5) Å.     

Poly[[aqua­copper(II)]‐μ‐adamantane‐1,3‐diacetato]

In the title compound, [Cu(C₁₄H₁₈O₄)(H₂O)]_n, each Cu^II atom bonds to four O atoms of four adamantanediacetate (ada) ligands in equatorial positions and an O atom from a water mol­ecule in the apical position. Two adjacent Cu^II atoms form a paddle‐wheel unit with four ada ligands. The distance between the two Cu atoms is 2.5977 (3) Å. A crystallographic inversion center is located at the center of the Cu–Cu core. Each Cu₂(ada)₄ paddle‐wheel further bonds to four adjacent identical paddle‐wheel units, generating a two‐dimensional layered structure of Cu(ada)(H₂O) with a 4⁴ topology.     

μ‐Acetato‐1:2κ2O:O′‐diacetato‐1κ2O,O′;2κO‐bis(di‐2‐pyridylamine)‐1κ2N,N′;2κ2N,N′‐isothiocyanato‐2κN‐dicopper(II)

In the title dinuclear acetate‐bridged complex, [Cu₂(C₂H₃O₂)₃(NCS)(C₁₀H₉N₃)₂], the two Cu atoms are five‐coordinated, with a basal plane consisting of two N atoms of a di‐2‐pyridylamine (dpyam) ligand and two O atoms of two different acetate ligands. The axial positions of these Cu atoms are coordinated to N and O atoms from thio­cyanate and acetate mol­ecules, respectively, leading to a distorted square‐pyramidal geometry with τ values of 0.30 and 0.22. Both Cu^II ions are linked by an acetate group in the equatorial–equatorial positions and have syn–anti bridging configurations. Hydrogen‐bond inter­actions between the amine H atom and the coordinated and uncoordinated O atoms of the acetate anions generate an infinite one‐dimensional chain.     

Poly[[aqua‐μ3‐2,2‐dimethylmalonato‐copper(II)] monohydrate] and poly[aqua‐μ3‐2,2‐dimethylmalonato‐copper(II)]

The coordination mode of the dimethylmalonate ligand in the two title Cu^II complexes, {[Cu(C₅H₃O₄)(H₂O)]·H₂O}_n, (I), and [Cu(C₅H₃O₄)(H₂O)]_n, (II), is the same, with chelated six‐membered, bis‐monodentate and bridging bonding modes. However, the coordination environment of the Cu^II atoms, the connectivity of their metal–organic frameworks and their hydrogen‐bonding interactions are different. Complex (I) has a perfect square‐pyramidal Cu^II environment with the aqua ligand in the apical position, and only one type of square grid consisting of Cu^II atoms linked via carboxylate bridges to three dimethylmalonate ligands, with weak hydrogen‐bond interactions within and between its two‐dimensional layers. Complex (II) has a coordination geometry that is closer to square pyramidal than trigonal bipyramidal for its Cu^II atoms with the aqua ligand now in the basal plane. Its two‐dimensional layer structure comprises two alternating grids, which involve two and four different dimethylmalonate anions, respectively. There are strong hydrogen bonds only within its layers.     

Poly[diaquabis(μ‐4,4′‐bipyridine‐κ2N:N′)bis(ethane‐1,2‐diol)di‐μ‐sulfato‐dicopper(II)]

The title compound, [Cu₂(SO₄)₂(C₁₀H₈N₂)₂(C₂H₆O₂)₂(H₂O)₂]_n, contains two crystallographically unique Cu^II centres, each lying on a twofold axis and having a slightly distorted octahedral environment. One Cu^II centre is coordinated by two bridging 4,4′‐bipyridine (4,4′‐bipy) ligands, two sulfate anions and two aqua ligands. The second is surrounded by two 4,4′‐bipy N atoms and four O atoms, two from bridging sulfate anions and two from ethane‐1,2‐diol ligands. The sulfate anion bridges adjacent Cu^II centres, leading to the formation of linear ...Cu1–Cu2–Cu1–Cu2... chains. Adjacent chains are further bridged by 4,4′‐bipy ligands, which are also located on the twofold axis, resulting in a two‐dimensional layered polymer. In the crystal structure, extensive O—H...O hydrogen‐bonding interactions between water molecules, ethane‐1,2‐diol molecules and sulfate anions lead to the formation of a three‐dimensional supramolecular network structure.     

catena‐Poly[[(1,10‐phenanthroline‐κ2N,N′)copper(II)]‐μ‐(dihydrogen benzene‐1,2,4,5‐tetracarboxylato)‐κ2O1:O4]

In the title compound, [Cu(C₁₀H₄O₈)(C₁₂H₈N₂)]_n, the Cu^II cation has a four‐coordination environment completed by two N atoms from one 1,10‐phenanthroline (phen) ligand and two O atoms belonging to two di­hydrogen benzene‐1,2,4,5‐­tetra­carboxyl­ate anions (H₂TCB²⁻). There is a twofold axis passing through the Cu^II cation and the centre of the phen ligand. The [Cu(phen)]²⁺ moieties are bridged by H₂TCB²⁻ anions to form an infinite one‐dimensional coordination polymer with a zigzag chain structure along the c axis. A double‐chain structure is formed by hydrogen bonds between adjacent zigzag chains. Furthermore, there are π–π stacking inter­actions between the phen ligands, with an average distance of 3.64 Å, resulting in a two‐dimensional network structure.     

Di‐μ‐hydroxido‐bis{[bis(6‐methyl‐2‐pyridylmethyl)(2‐phenylethyl)amine‐κ3N′,N′′,N′′′]copper(II)} bis(perchlorate)

The title compund, [Cu₂(OH)₂(C₂₂H₂₅N₃)₂](ClO₄)₂, is a copper(II) dimer, with two [CuL]²⁺ units [L is bis(6‐methyl‐2‐pyridylmethyl)(2‐phenylethyl)amine] bridged by hydroxide groups to define the {[CuL](μ‐OH)₂[CuL]}²⁺ cation. Charge balance is provided by perchlorate counter‐anions. The cation has a crystallographic inversion centre halfway between the Cu^II ions, which are separated by 3.0161 (8) Å. The central core of the cation is an almost regular Cu₂O₂ parallelogram of sides 1.931 (2) and 1.935 (2) Å, with a Cu—O—Cu angle of 102.55 (11)°. The coordination geometry around each Cu^II centre can be best described as a square‐based pyramid, with three N atoms from L ligands and two hydroxide O atoms completing the coordination environment. Each cationic unit is hydrogen bonded to two perchlorate anions by means of hydroxide–perchlorate O—H...O interactions.     

Poly[[μ‐aqua‐bis­(μ‐2,4‐dichloro­phen­oxy­acetato)barium(II)] monohydrate]

In the title coordination polymer, {[Ba(C₈H₅Cl₂O₃)₂(H₂O)]·H₂O}_n, each Ba^II atom is nine‐coordinated by six carboxyl­ate O atoms and one ether O atom from five symmetry‐related 2,4‐dichloro­phenoxy­acetate ligands, and by two O atoms from water mol­ecules, thus defining a distorted tricapped trigonal prism. The Ba^II ions are bridged by bidentate water mol­ecules and by tridentate and tetra­dentate 2,4‐dichloro­phenoxy­acetate groups, leading to a two‐dimensional layer structure. The crystal structure is further stabilized by hydrogen‐bonding inter­actions within each layer.     

catena‐Poly[[[pyridinecopper(II)]bis[μ3‐4‐(2‐oxidobenzylideneamino)benzoato]] dimethylformamide disolvate], a polymer composed of dimeric dicopper building units

The title compound, {[Cu(C₁₄H₉NO₃)(C₅H₅N)]·C₃H₇NO}_n or {[Cu₂L₂(py)₂]·2DMF}_n [py is pyridine, L is 4‐(salicylideneamino)benzoate and DMF is dimethylformamide], is composed of dimeric dicopper [CuL(py)]₂ building units, which are interlinked into a one‐dimensional chain through the formation of Cu—O_COO bonds. The dimeric unit is centrosymmetric, containing two Cu^II atoms linked by bridging phenolate O atoms into a Cu₂O₂ plane with a chelating Cu—O bond length of 1.927 (2) Å and a bridging Cu—O bond length of 2.440 (2) Å. Interchain C—H...O and π–π stacking interactions are responsible for an extensive three‐dimensional structure in which the resulting channels are filled by DMF solvent molecules.     

Di‐μ‐chloro‐bis({2‐[N,N‐bis(2‐aminoethyl)amino‐κ3N]ethylaminium}copper(II)) bis(naphthalene‐1,5‐disulfonate) pentahydrate

The title compound, [Cu₂(C₆H₁₉N₄)₂Cl₂](C₁₀H₆O₆S₂)₂·5H₂O, is comprised of discrete [Cu₂(tren)₂Cl₂]²⁺ dimers {tren is 2‐[N,N‐bis(2‐amino­ethyl)­amino]­ethyl­aminium} and naphthalene‐1,5‐di­sulfonate anions. Two Cl^? anions bridge two Cu^II ions, each of which is also coordinated by two of the primary and the tertiary amino N atoms of the tren ligand, giving each metal atom a distorted square‐pyramidal coordination geometry. The cation lies about an inversion centre and the asymmetric unit also has two independent anions lying about inversion centres.     

Poly[[cobalt(II)‐di‐μ3‐3,5‐diamino­benzoato‐κ3N:N′:O] monohydrate]

In the title compound, {[Co(C₇H₇N₂O₂)₂]·H₂O}_n, the Co^II atom lies on an inversion centre and has octahedral geometry, defined by two O atoms in axial positions and four N atoms in equatorial sites from six different 3,5‐diamino­benzoate ligands. Each 3,5‐diamino­benzoate anion acts as a μ₃‐bridging ligand, linking three adjacent Co^II ions through one O atom and two N atoms to form a three‐dimensional coordination polymer.     

[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.     

A mixed‐valence CuII/CuI anion–cation complex: bis­[μ‐5‐sulfosali­cylato(3–)]bis­[(di‐2‐pyridylamine)­copper(II)] bis­[bis­(di‐2‐pyridyl­amine)copper(I)] dihydrate

The title compound, [Cu(C₇H₃O₆S)₂(C₁₀H₉N₃)₂][Cu^I(C₁₀H₉N₃)₂]₂·2H₂O, consists of anionic Cu^II moieties, cationic Cu^I species and uncoordinated water mol­ecules. The anionic dimeric unit consists of one crystallographically independent fully deprotonated 5‐sulfosalicylate (2‐oxido‐5‐sulfonatobenzoate) anion, a di‐2‐pyridylamine group and a Cu^II atom. Each Cu^II atom is five‐coordinate within a square‐pyramidal geometry. The anion lies on a special position of site symmetry. In the cationic monomer, the Cu^I atom adopts tetra­hedral geometry. The cations and anions are connected by O—H·O and N—H·O hydrogen bonds.     

Tetra‐μ‐acetato‐κ2O:O′‐bis[(4‐phenylpyridine‐κN)copper(II)]

The title compound, [Cu₂(C₂H₃O₂)₄(C₁₁H₉N)₂] or [Cu₂(MeCO₂)₄(phpy)₂] (phpy is 4‐phenyl­pyridine), consists of centrosymmetric dimers in which the Cu^II atoms display a square‐pyramidal CuO₄N coordination, with four acetate O atoms in the basal plane [Cu—O 1.975 (3)–1.987 (3) Å] and the phpy N atom in the apical position [Cu—N 2.150 (3) Å]. The Cu atoms are 2.654 (1) Å apart and are bridged by four acetate groups. The discrete dimers are extended into a three‐dimensional supramolecular array through intermolecular π–π‐stacking interactions.     

catena‐Poly­[[[aqua(2‐methyl‐4‐oxo‐4H‐pyran‐3‐olato‐κO3,O4)copper(II)]‐μ‐chloro] monohydrate]

In the title complex, {[Cu(C₆H₅O₃)Cl(H₂O)]·H₂O}_n, the Cu^II atom has a deformed square‐pyramidal coordination geometry formed by two O atoms of the maltolate ligand, two bridging Cl atoms and the coordinated water O atom. The Cu atoms are bridged by Cl atoms to form a polymeric chain. The deprotonated hydroxyl and ketone O atoms of the maltolate ligand form a five‐membered chelate ring with the Cu atom. Stacking interactions and hydrogen bonds exist in the crystal.     

Poly[[di‐μ2‐aqua‐di‐μ5‐croconato(2–)‐nickel(II)dipotassium(I)] tetra­hydrate]

In the title compound, {[K₂Ni(C₅O₅)₂(H₂O)₂]·4H₂O}_n, the Ni atom lies on an inversion centre. Two inversion‐related croconate [4,5‐dihydroxy‐4‐cyclo­pentene‐1,2,3‐trionate(2−)] ligands and an Ni^II ion form a near‐planar symmetrical [Ni(C₅O₅)₂]²⁻ moiety. The near‐square coordination centre of the moiety is then extended to an octa­hedral core by vertically bonding two water mol­ecules in the [Ni(C₅O₅)₂(H₂O)₂]²⁻ coordination anion. The crystal structure is characterized by a three‐dimensional network, involving strong K⋯O⋯K binding, K⋯O—Ni binding and hydrogen bonding.     

A novel mixed‐valence copper complex,poly[[μ2‐4,4′‐bipyridine‐μ3‐pyridine‐2,4,6‐tricarboxyl­ato‐di­copper(I,II)] monohydrate]

In the title novel mixed‐valence copper complex, {[Cu₂(C₈H₂NO₆)(C₁₀H₈N₂)]·H₂O}_n, the Cu^I and Cu^II ions are linked by 4,4′‐bipyridine (bpy) and pyridine‐2,4,6‐tricarboxyl­ate (ptc) ligands into corrugated layers, which are assembled via inter­layer C—H⋯O hydrogen bonds to give a three‐dimensional supra­molecular architecture.     

catena‐Poly[[[(di‐2‐pyridylamine‐κ2N2,N2′)copper(II)]‐μ‐benzene‐1,3‐dicarboxylato‐κ3O1,O1′:O3] monohydrate], a zigzag coordination polymer with strong π–π interactions

The novel title coordination polymer, {[Cu(C₈H₄O₄)(C₁₀H₉N₃)]·H₂O}_n, synthesized by the slow‐diffusion method, takes the form of one‐dimensional zigzag chains built up of Cu^II cations linked by benzene‐1,3‐dicarboxylate (ipht) anions. An exceptional characteristic of this structure is that it belongs to a small group of metal–organic polymers where ipht is coordinated as a bridging tridentate ligand with monodentate and chelate coordination of individual carboxylate groups. The Cu^II cation has a highly distorted square‐pyramidal geometry formed by three O atoms from two ipht anions and two N atoms from a di‐2‐pyridylamine (dipya) ligand. The zigzag chains, which run along the b axis, further construct a three‐dimensional metal–organic framework via strong face‐to‐face π–π interactions and hydrogen bonds. A solvent water molecule is linked to the different carboxylate groups via hydrogen bonds. Thermogravimetric and differential scanning calorimetric analyses confirm the strong hydrogen bonding.