[2,6‐Bis(5‐methyl‐2‐pyridyl)phenyl‐κ3N,C1,N′]chloridoplatinum(II)

In the title compound, [Pt(C₁₈H₁₅N₂)Cl], the Pt^II centre adopts a distorted square‐planar coordination geometry due to the pincer‐type monoanionic N–C–N tridentate ligand. The planar complexes stack viaπ–π interactions to form two‐dimensional accumulated sheets. This packing pattern is in contrast to that in related pincer‐type N–C–N complexes, which exhibit a one‐dimensional columnar stacking.     

Polymorphism of mer‐μ‐oxalato‐bis[chloridotripyridinecobalt(II)] pyridine disolvate

Single crystals of a triclinic polymorphic form of mer‐μ‐oxalato‐bis[chloridotripyridinecobalt(II)] pyridine disolvate, [Co₂(C₂O₄)Cl₂(C₅H₅N)₆]·2C₅H₅N, have been prepared by solvothermal methods. The structure and geometric parameters strongly resemble those of the previously reported monoclinic polymorph [Bolte (2006). Acta Cryst. E 62 , m597–m598]. In both polymorphic forms, the dinuclear complex molecules are located on a crystallographic centre of inversion, with the Co^II cations in a distorted octahedral environment consisting of a chloride ligand, three pyridine ligands and a chelating bis‐bidentate oxalate ligand. This last serves as a bridging ligand between two Co^II cations. The polymorphs differ in the mutual orientation of their pyridine ligands in the dinuclear molecules and in their intermolecular connectivity. In the triclinic polymorph, C—H...O, C—H...Cl, C—H...π and π–π interactions link the dinuclear molecules into a three‐dimensional structure. Pyridine solvent molecules are attached to this structure via weak interactions.     

Bis{2‐[(phenylimino)ethyl]‐1H‐pyrrol‐1‐ido‐κ2N,N′}nickel(II): a supramolecular structure formed by C—H...π hydrogen bonds

In the title compound, [Ni(C₁₂H₁₁N₂)₂], the Ni^II cation lies on an inversion centre and has a square‐planar coordination geometry. This transition metal complex is composed of two deprotonated N,N′‐bidentate 2‐[(phenylimino)ethyl]‐1H‐pyrrol‐1‐ide ligands around a central Ni^II cation, with the pyrrolide rings and imine groups lying trans to each other. The Ni—N bond lengths range from 1.894 (3) to 1.939 (2) Å and the bite angle is 83.13 (11)°. The Ni—N(pyrrolide) bond is substantially shorter than the Ni—N(imino) bond. The planes of the phenyl rings make a dihedral angle of 78.79 (9)° with respect to the central NiN₄ plane. The molecules are linked into simple chains by an intermolecular C—H...π interaction involving a phenyl β‐C atom as donor. Intramolecular C—H...π interactions are also present.     

Disentangling steric and electronic factors in monomeric bis(2‐bromo‐4‐chloro‐6‐{[(2‐hydroxyethyl)imino]methyl}phenolato‐κ2N,O)copper(II)

The title compound, [Cu(C₉H₈BrClNO₂)₂], is a square‐planar complex. The potentially tridentate dibasic 2‐bromo‐4‐chloro‐6‐{[(2‐hydroxyethyl)imino]methyl}phenolate ligand coordinates in a trans‐bis fashion to the Cu^II centre via the imine N and phenolate O atoms. The Cu^II atom lies on the centre of inversion of the molecule. The potentially coordinating hydroxyethyl group remains protonated and uncoordinated, taking part in intermolecular hydrogen bonds with vicinal groups, leading to the formation of a two‐dimensional hydrogen‐bond network with sheets parallel to the (10) plane. Substituent effects on the crystal packing and coordination modes of the ligand are discussed.     

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.     

(Croconato‐κ2O,O′)bis­(1,10‐phenanthroline‐κ2N,N′)cobalt(II), and the nickel(II) and copper(II) analogues

The title complexes, [M(C₅O₅)(C₁₂H₈N₂)₂], with M = Co^II, Ni^II and Cu^II, all lie across twofold rotation axes, around which two 1,10‐phenanthroline ligands are arranged in a chiral propeller manner. The Co^II and Ni^II complexes are isostructural, with octa­hedral coordination geometry, while the local geometry of the Cu^II complex is severely distorted from octa­hedral.     

catena‐Poly[[nickel(II)‐μ2‐[1,3‐bis(imidazol‐1‐ylmethyl)benzene‐κ2N3:N3′]‐μ2‐(5‐carboxybenzene‐1,3‐dicarboxylato‐κ4O1,O1′:O3,O3′)] 0.41‐hydrate]

The title compound, {[Ni(C₉H₄O₆)(C₁₄H₁₄N₄)]·0.41H₂O}_n, exhibits a three‐dimensional hydrogen‐bonded supramolecular framework. The Ni^II cation is six‐coordinated in a distorted triangular prism defined by two N atoms from two 1,3‐bis(imidazol‐l‐ylmethyl)benzene (bix) ligands and four O atoms from two 5‐carboxybenzene‐1,3‐dicarboxylate (HBTC) dianions. The bix molecules and HBTC dianions both act as bidentate ligands, linking the Ni^II cations to form a one‐dimensional coordination polymer. A two‐dimensional wave‐like net is constructed by O—H...O hydrogen bonds linking adjacent chains. Partially occupied solvent water molecules fill the cavities and link these layers to form a three‐dimensional supramolecular structure via O—H...O hydrogen bonds. The title compound was also characterized by powder X‐ray diffraction and thermogravimetric analysis.     

Intramolecular hydrogen‐bond‐directed coordination: trans‐bis(N‐benzoyl‐N′‐propyl­thio­urea‐κS)di­iodo­platinum(II) and trans‐bis(N‐benzoyl‐N′‐propyl­thio­urea‐κS)di­bromo­platinum(II)

In the title compounds, trans‐[PtI₂(C₁₁H₁₄N₂OS)₂], (I), and trans‐[PtBr₂(C₁₁H₁₄N₂OS)₂], (II), respectively, intramolecular N—H⋯O (propyl­amine side) hydrogen bonds in the potentially bidentate thio­urea ligands lock the carbonyl O atoms into six‐membered rings, determining the S‐mono­dentate mode of coordination of these ligands. Intramolecular N—H⋯X (X is I or Br) interactions (benzoyl­amine side) lead to slight distortions of the Pt^II coordination spheres from ideal square‐planar geometry. The Pt^II ion is located on an inversion centre in both structures.     

A novel one‐dimensional double‐chain‐like ZnII coordination polymer: poly[bis(1‐benzyl‐1H‐imidazole‐κN3)tris(μ‐cyanido‐κ2C:N)(cyanido‐κC)disilver(I)zinc(II)]

One of most interesting systems of coordination polymers constructed from the first‐row transition metals is the porous Zn^II coordination polymer system, but the numbers of such polymers containing N‐donor linkers are still limited. The title double‐chain‐like Zn^II coordination polymer, [Ag₂Zn(CN)₄(C₁₀H₁₀N₂)₂]_n, presents a one‐dimensional linear coordination polymer structure in which Zn^II ions are linked by bridging anionic dicyanidoargentate(I) units along the crystallographic b axis and each Zn^II ion is additionally coordinated by a terminal dicyanidoargentate(I) unit and two terminal 1‐benzyl‐1H‐imidazole (BZI) ligands, giving a five‐coordinated Zn^II ion. Interestingly, there are strong intermolecular Ag^I…Ag^I interactions between terminal and bridging dicyanidoargentate(I) units and C—H…π interactions between the phenyl rings of BZI ligands of adjacent one‐dimensional linear chains, providing a one‐dimensional linear double‐chain‐like structure. The supramolecular three‐dimensional framework is stabilized by C—H…π interactions between the phenyl rings of BZI ligands and by Ag^I…Ag^I interactions between adjacent double chains. The photoluminescence properties have been studied.     

A novel two‐dimensional nickel(II) coordination polymer with 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene and azide ligands

The coordination geometry of the Ni^II atom in the title complex, poly[diazidobis[μ‐1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene‐κ²N⁴:N^4′]nickel(II)], [Ni(N₃)₂(C₁₂H₁₂N₆)₂]_n, is a distorted octahedron, in which the Ni^II atom lies on an inversion centre and is coordinated by four N atoms from the triazole rings of two symmetry‐related pairs of 1,4‐bis(1,2,4‐triazol‐1‐ylmethyl)benzene (bbtz) ligands and two N atoms from two symmetry‐related monodentate azide ligands. The Ni^II atoms are bridged by four bbtz ligands to form a two‐dimensional (4,4)‐network.     

(2‐Aminopyrimidine‐κN1)aqua(pyridine‐2,6‐dicarboxylato‐κ3O2,N,O6)copper(II): X‐ray and DFT calculated structure

In the title compound, [Cu(C₇H₃N₂O₄)(C₄H₅N₂)(H₂O)], (I), pyridine‐2,6‐dicarboxylate (pydc²⁻), 2‐aminopyrimidine and aqua ligands coordinate the Cu^II centre through two N atoms, two carboxylate O atoms and one water O atom, respectively, to give a nominally distorted square‐pyramidal coordination geometry, a common arrangement for copper complexes containing the pydc²⁻ ligand. Because of the presence of Cu...X_bridged contacts (X = N or O) between adjacent molecules in the crystal structures of (I) and three analogous previously reported compounds, and the corresponding uncertainty about the effective coordination number of the Cu^II centre, density functional theory (DFT) calculations were used to elucidate the degree of covalency in these contacts. The calculated Wiberg and Mayer bond‐order indices reveal that the Cu...O contact can be considered as a coordination bond, whereas the amine group forming a Cu...N contact is not an effective participant in the coordination environment.     

catena‐Poly[[aqua(11‐chloropyrido[2′,3′:2,3]pyrimidino[5,6‐f][1,10]phenanthroline‐κ2N4,N5)cadmium(II)]‐μ‐benzene‐1,4‐dicarboxylato‐κ3O1,O1′:O4]: an inclined interpenetrating (6,3) network

The asymmetric unit of the title compound, [Cd(C₈H₄O₄)(C₁₇H₈ClN₅)(H₂O)]_n, contains one Cd^II atom, two half benzene‐1,4‐dicarboxylate (1,4‐bdc) anions, one 11‐chloropyrido[2′,3′:2,3]pyrimidino[5,6‐f][1,10]phenanthroline (L) ligand and one coordination water molecule. The 1,4‐bdc ligands are on inversion centers at the centroids of the arene rings. The Cd^II atom is six‐coordinated by two N atoms from one L ligand, three carboxylate O atoms from two different 1,4‐bdc ligands and one water O atom in a distorted octahedral coordination sphere. Each Cd^II center is bridged by the 1,4‐bdc dianions to give a one‐dimensional chain. π–π stacking interactions between L ligands of neighboring chains extend adjacent chains into a two‐dimensional supramolecular (6,3) network. Neighboring (6,3) networks are interpenetrated in an unusual inclined mode, resulting in a three‐dimensional framework. Additionally, the water–carboxylate O—H...O hydrogen bonds observed in the network consolidate the interpenetrating nets.     

Tetrakis(2,2′‐bipyridine‐κ2N,N′)­tetrakis(μ‐salicyl­ato‐κ3O,O′:O′′)‐quadro‐tetrazinc(II) decahydrate

The title compound, [Zn₄(C₇H₄O₃)₄(C₁₀H₈N₂)₄]·10H₂O, crystallizes as a centrosymmetric tetranuclear cyclic complex containing four Zn^II atoms bridged by four carboxyl­ate groups from salicyl­ate ligands, with a syn–anti configuration. Each Zn^II atom has a distorted trigonal–bipyramidal coordination geometry, formed by two N atoms of a 2,2′‐bipyridine ligand and three O atoms from two salicyl­ate ligands. The complex is stabilized by intramolecular π–π interactions between pairs of bi­pyridine rings and a 16‐membered gear‐wheel‐shaped cyclic framework. The hydrogen‐bonding network is formed via the water mol­ecules.     

Interactions between dimers of {1,1′‐[o‐phenylenebis(nitrilomethylidyne)]di‐2‐naphtholato‐κ4O,N,N′,O′}nickel(II)

In the title compound, [Ni(C₂₈H₁₈N₂O₂)], the Ni^II centre has a square‐planar coordination geometry in which the Schiff base ligand acts as a cis‐O,N,N′,O′‐tetradentate ligand. The crystal structure is built up of centrosymmetric dimer units stacked into chains along the [010] direction. Adjacent chains associate via C—H...O hydrogen bonding only, leading to a two‐dimensional sheet‐like structure consisting of layers parallel to (10). The cofacial dimeric complex contains an Ni...Ni contact of 3.291 (4) Å.     

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[[tetraaquabis(μ2‐2‐nitroterephthalato‐κ3O1:O4,O4′)(μ2‐piperazine‐κ3N:N′)dicadmium(II)] dihydrate]

In the title complex, {[Cd₂(C₈H₃NO₆)₂(C₄H₁₀N₂)(H₂O)₄]·2H₂O}_n, the Cd^II atoms show distorted octahedral coordination. The two carboxylate groups of the dianionic 2‐nitroterephthalate ligand adopt monodentate and 1,2‐bridging modes. The piperazine molecule is in a chair conformation and lies on a crystallographic inversion centre. The Cd^II atoms are connected via three O atoms from two carboxylate groups and two N atoms from piperazine molecules to form a two‐dimensional macro‐ring layer structure. These layers are further aggregated to form a three‐dimensional structure via rich intra‐ and interlayer hydrogen‐bonding networks. This study illustrates that, by using the labile Cd^II salt and a combination of 2‐nitroterephthalate and piperazine as ligands, it is possible to generate interesting metal–organic frameworks with rich intra‐ and interlayer O—H...O hydrogen‐bonding networks.     

catena‐Poly[hexaaquamagnesium(II) [bis(μ3‐5‐nitro‐2‐oxidoisophthalato)dicopper(II)] dihydrate]

In the centrosymmetric dinuclear anions of the title bimetallic complex, {[Mg(H₂O)₆][Cu₂(C₈H₂NO₇)₂]·2H₂O}_n, each Cu^II ion is strongly coordinated by four O atoms in a distorted square‐planar geometry. Two of these O atoms belong to phenolate groups and the other two to carboxylate groups from 5‐nitro‐2‐oxidoisophthalate (L1) trianions, derived from 5‐nitrobenzene‐1,2,3‐tricarboxylic acid (O₂N–H₃L). The phenolate O atoms bridge the two Cu^II ions in the anion. In addition, each Cu^II cation interacts weakly with a symmetry‐related carboxylate O atom of an adjacent L1 ligand, giving a square‐pyramidal coordination geometry. The copper residue forms a ladder‐like linear coordination polymer via L1 ligands. The [Mg(H₂O)₆]²⁺ cations sit on centres of inversion. The polymeric anions, cations and free water molecules are self‐assembled into a three‐dimensional supramolecular network via O—H...O hydrogen bonds.     

(μ‐2,6‐Bis{[(2‐hydroxy­phenyl)­(2‐pyri­dyl­methyl)­amino]­methyl}‐4‐methyl­phenolato)­bis­[di­aqua­nickel(II)] ace­tate dimethyl­formamide 0.75‐hy­drate

The binuclear cation of the title compound, [Ni₂(C₃₃H₂₉­N₄O₃)(H₂O)₄]C₂H₃O₂·C₃H₇NO·0.75H₂O, was synthesized as a model for the active site of urease. Two tridentate halves of the symmetrical 2,6‐bis{[(2‐hydroxy­phenyl)(2‐pyridyl­methyl)­amino]­methyl}‐4‐methyl­phenolate (BPPMP^3?) ligand are arranged in a meridional fashion around the two Ni^II ions, with the phenoxo O atom bridging the Ni^II ions. The cation has an approximate twofold rotation axis running through the C—O bond of the bridging phenolate group. Four water mol­ecules complete the octahedral environment of each Ni^II ion.     

Bis(5‐aminotetrazole‐1‐acetato‐κO)tetraaquacobalt(II) and catena‐poly[[cadmium(II)]‐bis(μ‐5‐aminotetrazole‐1‐acetato‐κ3N4:O,O′)]

The Co^II atom in bis(5‐aminotetrazole‐1‐acetato)tetraaquacobalt(II), [Co(C₃H₄N₅O₂)₂(H₂O)₄], (I), is octahedrally coordinated by six O atoms from two 5‐aminotetrazole‐1‐acetate (atza) ligands and four water molecules. The molecule has a crystallographic centre of symmetry located at the Co^II atom. The molecules of (I) are interlinked by hydrogen‐bond interactions, forming a two‐dimensional supramolecular network structure in the ac plane. The Cd^II atom in catena‐poly[[cadmium(II)]‐bis(μ‐5‐aminotetrazole‐1‐acetato], [Cd(C₃H₄N₅O₂)₂]_n, (II), lies on a twofold axis and is coordinated by two N atoms and four O atoms from four atza ligands to form a distorted octahedral coordination environment. The Cd^II centres are connected through tridentate atza bridging ligands to form a two‐dimensional layered structure extending along the ab plane, which is further linked into a three‐dimensional structure through hydrogen‐bond interactions.     

catena‐Poly[[chloro­dipyridine­manganese(II)]‐μ3‐6‐oxo‐1,6‐dihydro­pyridine‐2‐carboxyl­ato]

The title one‐dimensional chain polymer complex, [Mn(C₆H₄NO₃)Cl(C₆H₅N)₂]_n, was isolated from the reaction of MnCl₂ with 6‐oxo‐1,6‐dihydro­pyridine‐2‐carboxylic acid (HpicOH) in pyridine. The asymmetric unit contains one [Mn(HPicO)Cl(py)₂] moiety (py is pyridine), with the (HpicO)⁻ ligand acting in a tridentate manner via the two carboxyl­ate O atoms and the pyridone O atom. The operation of inversion centres generates eight‐ and 14‐membered rings and, in conjunction with an a‐axis translation, leads to an infinite chain extending along [100]. The Mn⋯Mn separations in this chain are 5.1069 (6) and 7.1869 (6) Å. The Mn^II atom has a distorted octahedral coordination, with trans‐axial pyridine ligands and with three O atoms and the Cl atom in the equatorial plane. The conformation of the 14‐membered ring is stabilized by pairs of inversion‐related N—H⋯O hydrogen bonds.