Poly[tetraaquadi‐μ4‐malonato‐barium(II)zinc(II)]

The title complex, [BaZn(C₃H₂O₄)₂(H₂O)₄]_n, is polymeric, due to the connectivity brought about by each malonate dianion bonding to two different Zn^II cations and two different Ba^II cations. The Ba^II cations, on crystallographic twofold axes, have slightly distorted square‐anti­prismic coordination, with Ba—O distances ranging from 2.795 (2) to 2.848 (2) Å. The Zn^II cations, which lie on crystallographic centres of symmetry, have distorted octa­hedral coordination, with Zn—O bonds in the range 2.0364 (19)–2.3248 (18) Å. The water mol­ecules participate in extensive O—H⋯O hydrogen bonding. The structure comprises alternating layers along [100], with one type containing Zn^II cations and malonate dianions, while the other is primarily composed of Ba^II cations and water mol­ecules.     

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.     

Di‐μ‐aqua‐bis­[(N‐salicyl­idene‐β‐alaninato‐κ3O,N,O′)copper(II)] urea disolvate

Crystals of the title compound, [Cu₂(C₁₀H₉NO₃)₂(H₂O)₂]·2CH₄N₂O, consist of two (N‐salicyl­idene‐β‐alaninato‐κ³O,N,O′)copper(II) coordination units bridged by two water moieties to form a dimer residing on a crystallographic inversion center, along with two uncoordinated urea mol­ecules. The Cu^II atom has square‐pyramidal coordination, with three donor atoms of the tridentate Schiff base and an O atom of the bridging aqua ligand in the basal plane. The axial position is occupied by the second bridging water ligand at a distance of 2.5941 (18) Å. Hydro­gen bonds between mol­ecules of urea and the neighboring dimer units lead to the formation of a two‐dimensional grid of mol­ecules parallel to [101]. The superposition of the normals of the pyramidal base planes in the direction [100] indicates possible π–π interactions between the neighboring units.     

Poly[tetra­aqua­di‐μ3‐malonato‐calcium(II)­zinc(II)]

The title complex, [CaZn(C₃H₂O₄)₂(H₂O)₄]_n, is a two‐dimensional polymer and consists of CaO₈ and ZnO₆ polyhedra linked together by malonate ligands. The Ca^II cation, lying on a twofold axis, is coordinated by two water mol­ecules and six malonate O atoms. The Zn^II cation, which lies on an inversion center in an octa­hedral environment, is coordinated by four malonate O atoms in an equatorial arrangement and two water mol­ecules in axial positions. The Zn—O and Ca—O bond lengths are in the ranges 2.0445 (12)–2.1346 (16) and 2.3831 (13)–2.6630 (13) Å, respectively. The structure comprises alternating layers along the [101] plane, the shortest Zn⋯Zn distance being 6.8172 (8) Å. The whole three‐dimensional structure is maintained and stabilized by the presence of hydrogen bonds.     

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.     

Poly­[[[aqua­manganese(II)]‐μ2‐4,4′‐bi­pyridine‐μ3‐succinato] 4,4′‐bi­pyridine hemisolvate]

The polymeric title complex, {[Mn(C₄H₄O₄)(C₁₀H₈N₂)(H₂O)]·0.5C₁₀H₈N₂}_n, possesses a three‐dimensional open‐framework structure, with the solvate 4,4′‐bi­pyridine (bipy) mol­ecules, which lie around centers of inversion, clathrated in the channels of the framework. The Mn^II center is surrounded by three succinate (succ) ligands, one water mol­ecule and two bipy ligands, and displays a slightly distorted octahedral coordination environment, with cis angles ranging from 84.14 (12) to 96.56 (11)°. Each succ dianion coordinates to three Mn^II atoms, thus acting as a bridging tridentate ligand; in turn, the Mn^II atoms are bridged by three succ ligands, thus forming a two‐dimensional Mn–succ sheet pillared by the bridging bipy ligands. Two hydrogen‐bonding interactions, involving the water mol­ecules and the carboxy O atoms of the succ ligands, are present in the crystal structure.     

A one‐dimensional coordination polymer with metal–metal inter­actions: catena‐poly­[[tri­aqua­barium(II)]‐μ‐aqua‐κ2O:O‐di‐μ‐thio­salicyl­ato‐κ4O:O]

In the title compound, [Ba(C₇H₅O₂S)₂(H₂O)₄]_n, the Ba^II atom lies on a mirror plane and is nine‐coordinated by four bridging carboxylate O atoms of the thio­salicyl­ate ligands, two bridging water mol­ecules and three terminal water mol­ecules. There is an intramolecular S—H⋯O hydrogen bond between the S and O atoms in the thio­salicyl­ate ligand. A one‐dimensional coordination polymer is formed via weak metal–metal interactions along polymeric zigzag chains.     

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.     

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.     

Diaqua­bis[2′‐(4,5‐diaza­fluoren‐9‐yl­idene)picolinohydrazidato‐κ2N,O]zinc(II) tetra­hydrate: a metal–water chain complex containing cyclic water hexa­mers

In the title compound, [Zn(C₁₇H₁₀N₅O)₂(H₂O)₂]·4H₂O, cyclic water hexa­mers forming one‐dimensional metal–water chains are observed. The water clusters are trapped by the co‐operative association of coordination inter­actions and hydrogen bonds. The Zn^II ion resides on a centre of symmetry and is in an octa­hedral coordination environment comprising two O atoms and two N atoms from two 2′‐(4,5‐diaza­fluoren‐9‐yl­idene)picolinohydrazidate ligands and two water mol­ecules.     

A two‐dimensional manganese(II) coordination polymer: poly­[[di­aqua­manganese(II)]‐μ‐4,4‐bi­pyridine‐κ2N:N′‐μ‐(p‐phenyl­ene­dioxy­diacetato)‐κ2O:O′]

In the title two‐dimensional coordination polymer, [Mn(1,4‐BDOA)(4,4‐bipy)(H₂O)₂]_n [1,4‐BDOA²⁻ is the p‐phenyl­ene­dioxy­di­acetate dianion (C₁₀H₈O₆) and 4,4‐bipy is 4,4‐bi­pyridine (C₁₀H₈N₂)], each Mn^II atom displays octahedral coordination by two O atoms of the 1,4‐BDOA²⁻ groups, two N atoms of the 4,4‐bipy ligands and two solvent water mol­ecules. The Mn^II atom, 4,4‐bipy ligand and 1,4‐BDOA²⁻ group occupy different inversion centres. Adjacent Mn^II atoms are bridged by 1,4‐BDOA²⁻ groups and 4,4‐bipy ligands, forming a two‐dimensional network with Mn⋯Mn separations of 11.592 (2) and 11.699 (2) Å. Hydro­gen bonds from a water O—H group link the layers in the third dimension.     

catena‐Poly[[[cis‐aqua­bis(4‐carboxy­cyclo­hexane‐1‐carboxyl­ato‐κ2O,O′)cadmium(II)]‐μ‐4,4′‐bipyridine‐κ2N:N] monohydrate]

The title complex, {[Cd(C₈H₁₁O₄)₂(C₁₀H₈N₂)(H₂O)]·H₂O}_n, consists of linear chains formed through 4,4′‐bipyridine ligands linking seven‐coordinated Cd^II ions. Each Cd^II ion is in a distorted penta­gonal–bipyramidal environment, coordinated by one water ligand, two 4‐carboxy­cyclo­hexane‐1‐carboxyl­ate ligands and one bridging 4,4′‐bipyridine ligand to generate linear chains. The water mol­ecules and the Cd atom on one side, and the 4,4′‐bipyridine unit on the other, are bisected by two sets of twofold axes. The carboxylate group of the 4‐carboxy­cyclo­hexane‐1‐carboxyl ligand chelates a Cd^II ion, while the (protonated) carboxyl group forms hydrogen bonds with adjacent chains, resulting in a layered structure. This is the first reported occurrence of a dicarboxycyclo­hexane ligand exhibiting a non‐bridging coordination mode.     

catena‐Poly[[tetra­kis(μ‐propionato‐κ2O:O′)dicopper(II)]‐μ‐3‐pyridylmethanol‐κ2N:O‐[bis­(propionato‐κO)bis­(3‐pyridylmethanol‐κN)copper(II)]‐μ‐3‐pyridylmethanol‐κO:N]

The title compound, [Cu₃(C₃H₅O₂)₆(C₆H₇NO)₄]_n, is composed of polymeric chains formed by alternating centrosymmetric Cu₂(μ‐CH₃CH₂CO₂)₄ and Cu(C₃H₅O₂)₂(C₆H₇NO)₂ units. These elemental units are linked by two bridging 3‐pyridylmethanol (3PM) ligands. The Cu₂(μ‐CH₃CH₂CO₂)₄ group presents a centrosymmetric tetra­bridged structure with four syn–syn bridging propionate ligands to which two 3PM mol­ecules are bonded (through N), occupying the apical positions of each square‐pyramidal polyhedron around the Cu^II ions. The remaining mononuclear group is centred around a third Cu^II ion, which lies on a symmetry centre and is bound to two monodentate propionate groups (through O), two monodentate 3PM mol­ecules (through N) and two bridging 3PM mol­ecules (through O), thus completing a square‐bipyramidal CuO₂N₂O₂ coordination.     

catena‐Poly[[[tetra­aqua­zinc(II)]‐μ‐4,4′‐bipyridine] bis­(4‐hydroxy­benzene­sulfonate) trihydrate]

In the title compound, {[Zn(C₁₀H₈N₂)(H₂O)₄](C₆H₅O₄S)₂·3H₂O}_n, the Zn atom, the bipyridine ligand and one of water mol­ecules are located on twofold rotation axes. The Zn atom is coordinated by four O atoms from four water mol­ecules and two N atoms from two 4,4′‐bipyridine mol­ecules in a distorted octa­hedral geometry. The Zn²⁺ ions are linked by the 4,4′‐bipyridine mol­ecules to form a one‐dimensional straight chain propagating along the c axis. The 4‐hydroxy­benzene­sulfonate counter‐ions are bridged by the solvent water mol­ecules through hydrogen bonds to generate a two‐dimensional layer featuring large pores. In the crystal packing, the intra­layer pores form one‐dimensional channels along the c axis, in which the one‐dimensional [Zn(C₁₀H₈N₂)(H₂O)₄]²⁺ chains are encapsulated. Electrostatic inter­actions between cations and anions and extensive hydrogen bonds result in a three‐dimensional supra­molecular structure.     

Bis­[tris(2,2′‐bi­pyridine‐κ2N,N′)­ruthenium(II)] hexa­cyano­ferrate(III) chloride octahydrate

In the title compound, [Ru^II(C₁₀H₈N₂)₃]₂[Fe^III(CN)₆]Cl·8H₂O, the [Ru(bpy)₃]²⁺ (bpy is 2,2′‐bi­pyridine) cations and water mol­ecules afford intriguing microporous honeycomb layers, while the [Fe(CN)₆]³⁻ anions and the remainder of the water mol­ecules form anionic sheets based on extensive hydrogen‐bonding networks. The cationic and anionic layers alternate along the c axis. The Fe atom in [Fe(CN)₆]³⁻ lies on an inversion centre and the axial cyano ligands are hydrogen bonded to the water mol­ecules encapsulated within the micropores [N⋯O = 2.788 (5) Å], giving an unusual interpenetration between the cationic and anionic layers. On the other hand, the in‐plane cyano ligands are relatively weakly hydrogen bonded to the water mol­ecules [N⋯O = 2.855 (7) and 2.881 (8) Å] within the anionic sheets.     

A zinc–lithium complex of 4,7‐bis(2‐aminoethyl)‐1,4,7‐triazacyclononane‐1‐acetate

The asymmetric unit of {[4,7‐bis(2‐amino­ethyl)‐1,4,7‐tri­aza­cyclo­nonan‐1‐yl]acetato}zinc(II) triaqua{μ‐[4,7‐bis(2‐amino­ethyl)‐1,4,7‐tri­aza­cyclo­nonan‐1‐yl]acetato}lithium(I)zinc(II) chloride diperchlorate, [Zn(C₁₂H₂₆N₅O₂)][LiZn(C₁₂H₂₆N₅O₂)(H₂O)₃]Cl(ClO₄)₂, obtained from the reaction between the lithium salt of 4,7‐bis(2‐amino­ethyl)‐1,4,7‐tri­aza­cyclo­nonane‐1‐acetate and Zn(ClO₄)₂, contains two Zn^II complexes in which each Zn^II ion is six‐coordinated by five N‐atom donors and one O‐­atom donor from the ligand. One carboxyl­ate O‐atom donor is not involved in coordination to a Zn^II atom, but coordinates to an Li⁺ ion, the tetrahedral geometry of Li⁺ being completed by three water mol­ecules. The two complexes are linked via a hydrogen bond between a primary amine N—H group and the carboxyl­ate‐O atom not involved in coordination to a metal.     

Di‐μ‐sulfido‐bis[diaqua(18‐crown‐6)­barium(II)]–saccharin (1/2)

The mol­ecule of the title compound {systematic name: di‐μ‐sulfido‐bis[di­aqua(1,4,7,10,13,16‐hexaoxa­cyclo­octade­cane‐κ⁶O)barium(II)] bis­[1,2‐benzisothiazol‐3(2H)‐one 1,1‐dioxide]}, [Ba₂S₂(C₁₂H₂₄O₆)₂(H₂O)₄](C₇H₅NO₃S)₂, lies on an inversion centre. The Ba^II atom encapsulated by the 18‐crown‐6 ring is coordinated by the six O atoms of the crown, two water O atoms and two bridging S atoms. The four‐membered ring composed of the Ba^II atoms and the bridging S atoms makes a dihedral angle of 67.1 (1)° with the crown‐ether ring. The aromatic ring system of the saccharin moiety is essentially planar. The packing is built up from layers of the mol­ecules and is stabilized by three intermolecular O—H?O hydrogen bonds.     

Diaqua­malonato(1,10‐phenanthro­line)­zinc(II)

In the crystal structure of the title complex, [Zn(C₃H₂O₄)(C₁₂H₈N₂)(H₂O)₂], the Zn^II atom displays a distorted octa­hedral geometry, being coordinated by two N atoms from the 1,10‐phenanthroline ligand, two O atoms from different carboxyl­ate groups of the chelating malonate dianion and two O atoms of cis water mol­ecules. The complex mol­ecules are linked to form a three‐dimensional supramolecular array by both hydrogen‐bonding inter­actions between coordinated water molecules and the uncoordinated carboxyl­ate O atoms of neighboring mol­ecules, and aromatic π–π stacking inter­actions between neighboring phenanthroline rings.     

trans‐Di­aqua­bis(6‐hydroxy­picolinato‐κ2N,O2)copper(II)

In the title compound, [Cu(C₆H₄NO₃)₂(H₂O)₂], the Cu^II ion lies on an inversion centre and has an elongated octahedral environment, equatorially trans‐coordinated by two N,O‐bidentate picolinate ligands and axially coordinated by two water O atoms. The complex mol­ecules form layers, which are linked by O—H⋯O hydrogen bonds between the aqua ligands and neighbouring carboxyl­ate groups. An intramolecular hydrogen bond between the coordinated carboxyl­ate O atom and the hydroxy H atom is also observed.     

Tris(ethyl­ene­diamine)­nickel(II) bis­[2‐cyano‐2‐(oxidoimino)­acetamidato]­nickelate(II) monohydrate

The title compound, [Ni(C₂H₈N₂)₃][Ni(C₃HN₃O₂)₂]·H₂O, appears to be a modular associate consisting of two complex counter‐ions, containing bivalent nickel as the central atom in both cases, and a solvent water mol­ecule. The Ni^II ion in the complex cation lies on the C₂ crystallographic axis. Its coordination environment is formed by six N atoms of three ethyl­ene­diamine (en) mol­ecules, representing a distorted octa­hedral geometry. The Ni^II ion in the complex anion occupies a position at the center of inversion. It exhibits a distorted square‐planar coordination geometry formed by four N atoms belonging to the deprotonated oxidoimine and amide groups of the two doubly charged 2‐cyano‐2‐(oxidoimino)acetamidate anions, situated in trans positions with respect to each other. In the crystal packing, the complex anions are linked by water mol­ecules via hydrogen bonds between the amide O atoms and water H atoms, forming chains translated along the a direction. The [Ni(en)₃]²⁺ cations fill empty spaces between the translational chains, connecting them by hydrogen bonds between the oxime and amide O atoms of the anions and the amine H atoms of the cations, forming layers along the ac plane. The water mol­ecules provide connection between layers through N atoms of the cations, thus forming a three‐dimensional modular structure.