Aqua(oxydiacetato‐κ3O,O′,O′′)(pyridine‐3‐carboxamide‐κN1)copper(II) sesquihydrate

In the monomeric title compound, [Cu(C₄H₄O₅)(C₆H₆N₂O)(H₂O)]·1.5H₂O, the Cu^II cation is bound in a square‐pyramidal coordination to a tridentate oxydiacetate (ODA) ligand, a monodentate pyridine‐3‐carboxamide (p3ca) ligand and one aqua ligand, where the two organic ligands form the basal plane and the water O atom occupies the unique apical site. The ODA ligand presents a slight out‐of‐plane puckering in its central ether O atom, while the p3ca ligand is essentially planar. The availability of efficient donors and acceptors for hydrogen bonding results in the formation of strongly linked hydrogen‐bonded bilayers parallel to (101), with an interplanar distance of 3.18 (1) Å and a stacking separation between the bilayers of 3.10 (1) Å, both of them governed by extended π–π interactions. The disordered nature of the solvent water molecules around inversion centres is discussed. The monoaqua compound is compared with the octahedral diaqua analogue, [Cu(C₄H₄O₅)(C₆H₆N₂O)(H₂O)₂], reported recently [Perec & Baggio (2009). Acta Cryst. C 65 , m296–m298].     

Poly­[[[(1,10‐phenanthroline‐κ2N,N′)­zinc(II)]‐μ3‐5‐hydroxy­isophthalato‐κ4O,O′:O′′:O′′′] monohydrate]

In the title compound, {[Zn(C₈H₄O₅)(C₁₂H₈N₂)]·H₂O}_n or {[Zn(OH‐BDC)(phen)]·H₂O}_n (where OH‐H₂BDC is 5‐hydroxy­isophthalic acid and phen is 1,10‐phenanthroline), the Zn atoms are coordinated by two N atoms from the phen ligands and by four O atoms from hydroxy­isophthalate ligands in a highly distorted octahedral geometry, with Zn—O distances in the range 2.042 (4)–2.085 (5) Å and Zn—N distances of 2.133 (5) and 2.137 (5) Å. The {[Zn(OH‐BDC)(phen)]·H₂O}_n infinite zigzag polymer forms a helical chain of [Zn₂(OH‐BDC)₂]_n units. Face‐to‐face π–π interactions (3.60–3.75 Å) occur between two phen rings belonging to the same helical chain. Consolidation of the packing structure is achieved by O—H⋯O hydrogen‐bonding interactions between the carboxyl­ate O atoms, the hydroxyl group and the water mol­ecule, forming two‐dimensional sheets.     

Aqua(dipicolinato‐κ3O,N,O′)(1H‐imidazole‐κN3)(1,10‐phenanthroline‐N,N′)manganese(II)

In the title compound, [Mn(C₇H₃NO₄)(C₃H₄N₂)(C₁₂H₈N₂)(H₂O)], the Mn^II centre is surrounded by one bidentate phenanthroline ligand [Mn—N = 2.383 (3) and 2.421 (3) Å], one tridentate dipicolinate ligand [Mn—N = 2.300 (3) Å, and Mn—O = 2.300 (2) and 2.357 (2) Å], one monodentate imidazole ligand [Mn—N = 2.238 (3) Å] and one water molecule [Mn—O = 2.157 (3) Å]. It displays a distorted pentagonal‐bipyramidal geometry, with neighbouring angles within the equatorial plane ranging from 68.05 (9) to 77.48 (10)°. Intermolecular O—H...O hydrogen bonds link the molecules into infinite chains. The chains are crosslinked by hydrogen bonds involving the carboxyl O atoms of the dipicolinate ligand and the protonated imidazole N atom, leading to an infinite two‐dimensional network sheet packing mode. The complete solid‐state structure can be described as a three‐dimensional supramolecular framework, stabilized by these intermolecular hydrogen‐bonding interactions and π–π stacking interactions involving the phenanthroline rings.     

(6‐Oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylato‐κ2O5,O6)bis[2‐(2‐pyridyl)‐1H‐benzimidazole‐κ2N2,N3]manganese(II) monohydrate

In the title compound, [Mn(C₅H₂N₂O₄)(C₁₂H₉N₃)₂]·H₂O, the Mn^II centre is surrounded by three bidentate chelating ligands, namely, one 6‐oxido‐2‐oxo‐1,2‐dihydropyrimidine‐5‐carboxylate (or uracil‐5‐carboxylate, Huca²⁻) ligand [Mn—O = 2.136 (2) and 2.156 (3) Å] and two 2‐(2‐pyridyl)‐1H‐benzimidazole (Hpybim) ligands [Mn—N = 2.213 (3)–2.331 (3) Å], and it displays a severely distorted octahedral geometry, with cis angles ranging from 73.05 (10) to 105.77 (10)°. Intermolecular N—H...O hydrogen bonds both between the Hpybim and the Huca²⁻ ligands and between the Huca²⁻ ligands link the molecules into infinite chains. The lattice water molecule acts as a hydrogen‐bond donor to form double O...H—O—H...O hydrogen bonds with the Huca²⁻ O atoms, crosslinking the chains to afford an infinite two‐dimensional sheet; a third hydrogen bond (N—H...O) formed by the water molecule as a hydrogen‐bond acceptor and a Hpybim N atom further links these sheets to yield a three‐dimensional supramolecular framework. Possible partial π–π stacking interactions involving the Hpybim rings are also observed in the crystal structure.     

(Acetato‐κ2O,O′)dihydroxidoytterbium(III) hemihydrate

The title compound, [Yb(C₂H₃O₂)(OH)₂]·0.5H₂O, was obtained via hydrothermal reaction of Yb(CH₃COO)₃·H₂O with NaOH at 443 K. The compound forms two‐dimensional layers with six crystallographically independent Yb^III atoms. Four of these form YbO₈ coordination polyhedra, while the coordination number of the remaining two Yb^III atoms is 7. Five of these coordination polyhedra are interconnected mainly via hydroxide groups, as they build a narrow inner layer that extends infinitely within the ab plane. The sixth Yb^III atom resides outside this inner layer and builds a terminal YbO₈ coordination polyhedron on the layer surface. Its coordination environment comprises four carboxylate O atoms belonging to three different acetate entities, three hydroxide groups and one water molecule. Adjacent layers experience weak interactions via hydrogen bonds. The Yb—O distances lie in the range 2.232 (4)–2.613 (5) Å.     

Bis(μ‐acetato‐κ3O,O′:O′)bis[bis(acetato‐κ2O,O′)diaquadysprosium(III)] tetrahydrate

The title compound, [Dy₂(C₂H₃O₂)₆(H₂O)₄]·4H₂O, crystallizes in the form of dimeric units related by an inversion centre. Each cation is nine‐coordinate, binding to two water mol­ecules and three acetate groups, two of which are bidentate and the third tridentate. This last acetate group acts as a bridge between neighbouring metal atoms, leading to an intradimer Dy?Dy separation of 4.170 (1) Å.     

catena‐Poly[[[triaquazinc(II)]‐μ‐2‐nitroterephthalato‐κO1:κ2O4,O4′] monohydrate]

The title complex, {[Zn(C₈H₃NO₆)(H₂O)₃]·H₂O}_n, has a one‐dimensional chain structure. The two carboxylate groups of the dianionic 2‐nitroterephthalate ligand adopt mono‐ and bidentate chelating modes. The Zn atom shows distorted octahedral coordination, bonded to three O atoms from two carboxylate groups and three O atoms of three non‐equivalent coordinated water molecules. The one‐dimensional chains are aggregated into two‐dimensional layers through inter‐chain hydrogen bonding. The whole three‐dimensional structure is further stabilized by inter‐layer hydrogen bonds.     

(Glycylglycinato‐κ3O,N,N′)(2‐methyl‐1H‐benzimidazole‐κN3)copper(II) trihydrate

In the title compound, [Cu(C₄H₆N₂O₃)(C₈H₈N₂)]·3H₂O, the Cu^II atom is coordinated in a square‐planar manner by one O atom and three N atoms from glycylglycinate and 2‐methyl­benzimidazole ligands. The ternary complexes assemble into one‐dimensional chains through C—H⋯π inter­actions and direct N—H⋯O hydrogen bonding, as well as into hydrogen‐bonded water helices with branches which also link the complex chains into a three‐dimensional supra­molecular structure.     

Bis(4,4′‐bi­pyridine‐κN)­bis­(hydrogen phthalato)‐κ2O,O′;κO‐zinc(II)

The title compound, [Zn(C₈H₅O₄)₂(C₁₀H₈N₂)₂], was obtained by the hydro­thermal reaction of ZnSO₄·7H₂O with phthalic acid (H₂pht) and 4,4′‐bi­pyridine (4,4′‐bipy). Crystallographic analysis shows that it has a one‐dimensional double‐chain structure via hydrogen‐bonding interactions. Each Zn^II atom, adopting a distorted tetrahedral geometry, is coordinated by two N atoms from two 4,4′‐bipy ligands, with Zn—N distances of 2.054 (4) and 2.104 (4) Å, and by two O atoms from symmetry‐related Hpht⁻ ligands, with Zn—O distances of 1.921 (4) and 2.019 (4) Å.     

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.     

Poly­[[bis(1H‐benz­imidazole‐κN3)cadmium(II)]‐μ‐aqua‐μ‐succinato‐κ2O1:O4]

The title compound, [Cd(C₄H₄O₄)(C₇H₆N₂)₂(H₂O)]_n, is a three‐dimensional polymeric complex. The Cd^II atom is located on an inversion centre and assumes an elongated octahedral coordination geometry, with a long Cd—O distance of 2.5381 (5) Å to the coordinated bridging water molecule. The succinate dianion, located on another inversion centre, bridges adjacent Cd atoms to form succinate‐bridged polymeric chains. The coordinated water mol­ecule is located on a twofold axis and links adjacent succinate‐bridged chains to form a water‐bridged polymeric chain.     

Bis(2,2′‐bi­pyridine‐κ2N,N′)(oxalato‐κ2O,O′)­cobalt(II) pentahydrate

The synthesis and crystal structure of the mononuclear title compound, [Co(C₂O₄)(C₁₀H₈N₂)₂]·5H₂O, is reported. The Co atom is six‐coordinated by two O atoms of a bidentate oxalate group and by four N atoms of two bi­pyridine ligands. The neutral [Co(C₂O₄)(C₁₀H₈N₂)₂] entities are connected by π–π stacking interactions of the aromatic systems into a two‐dimensional layer, interconnected through a ladder‐like hydrogen‐bonding pattern of solvate water mol­ecules.     

Aquabromo(6‐carboxypyridine‐2‐carboxylato‐O,N,O′)mercury(II)

The title compound, [HgBr(C₇H₄NO₄)(H₂O)], was obtained by the reaction of an aqueous solution of mercury(II) bromide and pyridine‐2,6‐di­carboxylic acid (picolinic acid, dipicH₂). The shortest bond distances to Hg are Hg—Br 2.412 (1) Å and Hg—N 2.208 (5) Å; the corresponding N—Hg—Br angle of 169.6 (1)° corresponds to a slightly distorted linear coordination. There are also four longer Hg—O interactions, three from dipicH^? [2.425 (4) and 2.599 (4) Å within the asymmetric unit, and 2.837 (4) Å from a symmetry‐related mol­ecule] and one from the bonded water mol­ecule [2.634 (4) Å]. The effective coordination of Hg can thus be described as 2+4. The mol­ecules are connected to form double‐layer chains parallel to the y axis by strong O—H?O hydrogen bonds between carboxylic acid groups of neighbouring mol­ecules, and by weaker hydrogen bonds involving both H atoms of the water mol­ecule and the O atoms of the carboxylic acid groups.     

catena‐Poly[[diaquabis(2‐chloronicotinato‐κ2O,O′)cadmium(II)]‐μ‐2‐chloronicotinato‐κ3O,O′:N]

In the title neutral coordination polymer, [Cd(C₆H₃ClNO₂)₂(H₂O)₂]_n, each Cd^II ion is coordinated by one N and four O atoms from three 2‐chloro­nicotinate ligands and by two aqua ligands, defining a distorted monocapped octahedral coordination geometry. Adjacent Cd atoms are linked by the pyridyl N atom and the bidentate carboxyl­ate functional group of a 2‐­chloro­nicotinate ligand, forming a one‐dimensional infinite chain along the b axis. The Cd⋯Cd distance is 8.112 (3) Å. These chains are linked by O—H⋯O and O—H⋯N hydrogen bonds into a three‐dimensional network structure.     

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.     

Poly[aqua[μ3‐(pyridin‐1‐ium‐3,5‐diyl)diphosphonato‐κ3O:O′:O′′][μ2‐(pyridin‐1‐ium‐3,5‐diyl)diphosphonato‐κ2O:O′]calcium(II)]

The rigid organic ligand (pyridine‐3,5‐diyl)diphosphonic acid has been used to create the title novel three‐dimensional coordination polymer, [Ca(C₅H₆NO₆P₂)₂(H₂O)]_n. The six‐coordinate calcium ion is in a distorted octahedral environment, formed by five phosphonate O atoms from five different (pyridin‐1‐ium‐3,5‐diyl)diphosphonate ligands, two of which are unique, and one water O atom. Two crystallographically independent acid monoanions, L1 and L2, serve to link metal centres using two different coordination modes, viz.η²μ₂ and η³μ₃, respectively. The latter ligand, L2, forms a strongly undulated two‐dimensional framework parallel to the crystallographic bc plane, whereas the former ligand, L1, is utilized in the formation of one‐dimensional helical chains in the [010] direction. The two sublattices of L1 and L2 interweave at the Ca²⁺ ions to form a three‐dimensional framework. In addition, multiple O—H...O and N—H...O hydrogen bonds stabilize the three‐dimensional coordination network. Topologically, the three‐dimensional framework can be simplified as a very unusual (2,3,5)‐connected three‐nodal net represented by the Schläfli symbol (4·8²)(4·8⁸·10)(8).     

Synthesis,crystal structure and magnetic properties of (acetato‐κ2O,O′)bis(5,5′‐dimethyl‐2,2′‐bipyridine‐κ2N,N′)nickel(II) perchlorate monohydrate

The title hydrated ionic complex, [Ni(CH₃COO)(C₁₂H₁₂N₂)₂]ClO₄·H₂O or [Ni(ac)(5,5′‐dmbpy)₂]ClO₄·H₂O (where 5,5′‐dmbpy is 5,5′‐dimethyl‐2,2′‐bipyridine and ac is acetate), (1), was isolated as violet crystals from the aqueous ethanolic nickel acetate–5,5′‐dmbpy–KClO₄ system. Within the complex cation, the Ni^II atom is hexacoordinated by two chelating 5,5′‐dmbpy ligands and one chelating ac ligand. The mean Ni—N and Ni—O bond lengths are 2.0628 (17) and 2.1341 (15) Å, respectively. The water solvent molecule is disordered over two partially occupied positions and links two complex cations and two perchlorate anions into hydrogen‐bonded centrosymmetric dimers, which are further connected by π–π interactions. The magnetic properties of (1) at low temperatures are governed by the action of single‐ion anisotropy, D, which arises from the reduced local symmetry of the cis‐NiO₂N₄ chromophore. The fitting of the variable‐temperature magnetic data (2–300 K) gives g_iso = 2.134 and D/hc = 3.13 cm⁻¹.     

Bis(μ‐3‐nitrobenzene‐1,2‐dicarboxyl­ato)‐κ8O1,O2:O2,O3;O3,O2:O2,O1‐bis­[triaqua­(2‐carboxy‐3‐nitro­benzoato‐κ2O,O′)lanthanum(III)] dihydrate

The title compound, [La₂(C₈H₃NO₆)₂(C₈H₄NO₆)₂(H₂O)₆]·2H₂O, consists of dimeric units related by an inversion center. The two La^III atoms are linked by two bridging bidentate carboxyl­ate groups and two monodentate carboxyl­ate groups. Each La^III atom is nine‐coordinated by six O atoms from five different carboxyl­ate groups and three from water mol­ecules. Hydrogen bonds between the water mol­ecules and between the solvent water and a carboxyl­ate O atom are observed in the structure. In the crystal packing, there are slipped π–π stacking inter­actions between the parallel benzene rings. Both hydrogen‐bonding and π–π inter­actions combine to stabilize the three‐dimensional supra­molecular network.     

Bis[(dihydrogen pyrophosphato‐κ2O,O′)(2,2′:6′,2′′‐terpyridine‐κ3N,N′,N′′)copper(II)] 4.5‐hydrate

The title copper complex, [Cu(H₂P₂O₇)(C₁₅H₁₁N₃)]₂·4.5H₂O, consists of two very similar independent Cu(Tpy)H₂P₂O₇ monomeric units (Tpy is 2,2′:6′,2′′‐terpyridine) plus four and a half water molecules of hydration, some of which are disordered. Tpy units bind through the usual triple bite via their N atoms, and the H₂P₂O₇²⁻ anions coordinate through two O atoms from two different phosphate units. Each independent CuN₃O₂ chromophore can be described as a slightly deformed square pyramid, with one of them having a sixth, semicoordinated, O atom from a centrosymmetrically related CuN₃O₂ unit in a weakly bound second apical position suggesting an octahedral environment for the cation and weak dimerization of the molecule. The two independent complex molecules are connected via two strong O—H...O interactions between the phosphate groups to form hydrogen‐bonded dinuclear units, further linked into [111] columns, resulting in a very complex three‐dimensional supramolecular structure through a variety of classical and nonclassical hydrogen bonds, as well as π–π interactions.     

catena‐Poly[[diaquazinc(II)]‐μ‐4,4′‐sulfonyldibenzoato‐κ2O:O′]

The title compound, [Zn(C₁₄H₈O₆S)(H₂O)₂]_n, is the first reported metal complex of the 4,4′‐sulfonyldibenzoate anion. The structure comprises zigzag chains of alternating [Zn(H₂O)₂]²⁺ and sulfonyldibenzoate units, the central Zn and S atoms of which lie on crystallographic twofold axes. The Zn^II centre occupies a strongly distorted tetrahedral environment [O—Zn—O = 83.30 (7)–136.19 (8)°], coordinated by the two water O atoms [Zn—O = 1.986 (2) Å] and one O atom from each of two carboxylate groups [Zn—O = 1.9942 (19) Å], with much longer contacts to the other O atoms of these carboxylates [Zn—O = 2.528 (2) Å]. Hydrogen bonds between carboxylate O atoms and coordinated water molecules in adjacent chains lead to the formation of a three‐dimensional network structure.