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.     

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.     

Tetraaqua‐1κO,2κ3O‐(μ‐2,4‐dinitrophenolato‐1κ2O1,O2:2κO1)(2,4‐dinitrophenolato‐1κ2O1,O2)dilithium(I): a dinuclear lithium(I) complex

The title complex, [Li₂(C₆H₃N₂O₅)₂(H₂O)₄], contains two kinds of Li atoms, viz. five‐coordinated and four‐coordinated. The five‐coordinated Li ion has a tetragonal–pyramidal geometry, with a water molecule in the apical position and four O atoms from two 2,4‐dinitrophenolate (2,4‐DNP) ligands in the basal plane. The four‐coordinated Li ion has a tetrahedral geometry, with three water molecules and one phenolate O atom of a 2,4‐DNP ligand. The Li ions are bridged by a phenolate O atom, giving the complex a dinuclear structure. The crystal packing is stabilized by O—H...O hydrogen‐bonding interactions involving the water molecules and nitro O atoms.     

Poly[[bis(pyridin‐3‐ol)manganese(II)]‐di‐μ‐pyridin‐3‐olato]

In the title complex, [Mn(C₅H₄NO)₂(C₅H₅NO)₂]_n or [Mn(μ‐3‐PyO)₂(3‐PyOH)₂]_n (3‐PyO⁻ is the pyridin‐3‐olate anion and 3‐PyOH is pyridin‐3‐ol), the Mn^II atom lies on an inversion centre and has octahedral geometry, defined by two N atoms and two deprotonated exocyclic O atoms of symmetry‐related pyridin‐3‐olate ligands [Mn—N = 2.3559 (14) Å and Mn—O = 2.1703 (11) Å], as well as two N atoms of terminal 3‐PyOH ligands [Mn—N = 2.3482 (13) Å]. The Mn^II atoms are bridged by the deprotonated pyridin‐3‐olate anion into a layer structure, generating sheets in the (01) plane. These sheets are linked by O—H⋯O hydrogen bonds. There are also π–π and C—H⋯π interactions in the crystal structure.     

Tetra‐μ2‐acetato‐diacetatodi‐μ3‐hydroxido‐tetrakis[piperidinecopper(II)] dihydrate

The title complex, [Cu₄(C₂H₃O₂)₆(OH)₂(C₅H₁₁N)₄]·2H₂O, possesses an unusual inversion‐symmetric tetranuclear copper framework, with each Cu^II atom displaying a square‐pyramidal geometry and one additional long Cu...O contact. The four piperidine ligands are terminal, one at each Cu^II atom, and the two hydroxide ligands are triply bridging. The six acetate ligands exhibit two distinct coordination modes, namely as two monodentate acetates and four bridging acetates that bridge the two inequivalent copper centres. The noncoordinating acetate O atom is involved in intramolecular hydrogen bonding with H atoms from the hydroxide and one piperidine ligand. In addition, extensive intermolecular hydrogen bonding involving the solvent water molecules is observed.     

Poly[aqua(μ2‐benzene‐1,4‐dicarboxylato)(μ2‐4,4′‐bipyridine N,N′‐dioxide)cadmium(II)], a threefold interpenetrating diamond net

In the title compound, [Cd(C₈H₄O₄)(C₁₀H₈N₂O₂)(H₂O)]_n, (I), each Cd^II atom is seven‐coordinated in a distorted monocapped trigonal prismatic coordination geometry, surrounded by four carboxylate O atoms from two different benzene‐1,4‐dicarboxylate (1,4‐bdc) anions, two O atoms from two distinct 4,4′‐bipyridine N,N′‐dioxide (bpdo) ligands and one water O atom. The Cd^II atom and the water O atom are on a twofold rotation axis. The bpdo and 1,4‐bdc ligands are on centers of inversion. Each crystallographically unique Cd^II center is bridged by the 1,4‐bdc dianions and bpdo ligands to give a three‐dimensional diamond framework containing large adamantanoid cages. Three identical such nets are interlocked with each other, thus directly leading to the formation of a threefold interpenetrated three‐dimensional diamond architecture. To the best of our knowledge, (I) is the first example of a threefold interpenetrating diamond net based on both bpdo and carboxylate ligands. There are strong linear O—H...O hydrogen bonds between the water molecules and carboxylate O atoms within different diamond nets. Each diamond net is hydrogen bonded to its two neighbors through these hydrogen bonds, which further consolidates the threefold interpenetrating diamond framework.     

A novel heterometallic dinuclear compound: rac‐pentaaqua‐1κ5O‐(μ‐2‐sulfidoacetato‐1:2κ3O:O′,S)bis(2‐sulfidoacetato‐2κ2O,S)manganese(II)tin(IV)

The title racemic heterometallic dinuclear compound, [MnSn(C₂H₂O₂S)₃(H₂O)₅], (I), contains one main group Sn^IV metal centre and one transition metal Mn^II centre, and, by design, links the Mn^II centre to the building unit of the (Δ/Λ) [SnL₃]²⁻ complex anion (L is the 2‐sulfidoacetate dianion). In this cluster, the Sn^IV centre of the (Δ/Λ) [SnL₃]²⁻ unit is coordinated by three O atoms and three S atoms from three L ligands to form an [SnO₃S₃] octahedral coordination environment. The Mn^II centre is in an [MnO₆] octahedral coordination environment, with five O atoms from five water molecules and the sixth from the μ₂‐L ligand of the (Δ/Λ) [SnL₃]²⁻ unit. Between adjacent dinuclear molecules, there are many hydrogen‐bond interactions of O—H...O, O—H...S, C—H...O and C—H...S types. Of these, eight pairs of O—H...O hydrogen bonds fuse all the dinuclear molecules into two‐dimensional supramolecular sheets along the bc plane. Adjacent supramolecular sheets are further connected through O—H...S hydrogen bonds to give a three‐dimensional supramolecular network.     

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[μ‐aqua‐diaqua‐μ4‐malonato‐μ3‐malonato‐barium(II)nickel(II)]

The title complex, [BaNi(C₃H₂O₄)₂(H₂O)₃]_n, is polymeric, with two non‐equivalent malonate dianions bridging one Ni atom and five different Ba atoms. The Ni atoms have a distorted octahedral (NiO₆) environment, and are coordinated by four malonate O atoms in a planar arrangement and two water molecules in axial positions. The Ba atom may be described as a BaO₉ polyhedron in a monocapped square‐antiprismatic environment, which involves two water molecules and seven O atoms from different malonate ligands. The three‐dimensional structure is further maintained and stabilized by hydrogen bonds.     

Poly[bis(μ‐4‐benzoyl‐1‐isonicotinoylthiosemicarbazide‐κ2N:S)dichloridocadmium(II)]

The asymmetric unit of the title complex, [CdCl₂(C₁₄H₁₂N₄O₂S)₂]_n, consists of one Cd^II ion located on the crystallographic inversion centre, one 4‐benzoyl‐1‐isonicotinoylthiosemicarbazide ligand and one chloride ligand. The central Cd^II ion adopts a distorted octahedral coordination geometry formed by two pyridyl N atoms of two ligands, two S atoms of two other ligands and two chloride ligands. The thiosemicarbazide ligands act as bridges, linking the metal ions into a two‐dimensional layered structure parallel to the bc plane. Intermolecular N—H...O hydrogen bonds and C—H...π interactions exist between adjacent layers.     

catena‐Poly­[[(di‐2‐pyridyl­amine)­silver(I)]‐μ‐nicotinato] and catena‐poly­[[(di‐2‐pyridyl­amine)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato]

In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐nico­tinato‐κ²N:O], [Ag(C₆H₄NO₂)(C₁₀H₉N₃)]_n, the Ag^I atom is tetracoordinated by two N atoms from the di‐2‐pyridyl­amine (BPA) ligand [Ag—N = 2.3785 (18) and 2.3298 (18) Å] and by one N atom and one carboxyl­ate O atom from nicotinate ligands [Ag—N = 2.2827 (15) Å and Ag—O = 2.3636 (14) Å]. Bridging by nicotinate N and O atoms generates a polymeric chain structure, which extends along [100]. The carboxyl O atom not bonded to the Ag atom takes part in an intrachain C—H⋯O hydrogen bond, further stabilizing the chain. Pairs of chains are linked by N—H⋯O hydrogen bonds to generate ribbons. There are no π–π interactions in this complex. In catena‐poly­[[(di‐2‐pyridyl­amine‐κ²N,N′)silver(I)]‐μ‐2,6‐di­hydroxy­benzoato‐κ²O¹:O²], [Ag(C₇H₅O₄)(C₁₀H₉N₃)]_n, the Ag^I atom has a distorted tetrahedral coordination, with three strong bonds to two pyridine N atoms from the BPA ligand [Ag—N = 2.286 (5) and 2.320 (5) Å] and to one carboxyl­ate O atom from the 2,6‐di­hydroxy­benzoate ligand [Ag—O = 2.222 (4) Å]; the fourth, weaker, Ag‐atom coordination is to one of the phenol O atoms [Ag⋯O = 2.703 (4) Å] of an adjacent moiety, and this interaction generates a polymeric chain along [100]. Pairs of chains are linked about inversion centers by N—H⋯O hydrogen bonds to form ribbons, within which there are π–π interactions. The ribbons are linked about inversion centers by pairs of C—H⋯O hydrogen bonds and additional π–π interactions between inversion‐related pairs of 2,6‐di­hydroxy­benzoate ligands to generate a three‐dimensional network.     

catena‐Poly[[[(benzene‐1,3,5‐tricarboxylic acid)(1,10‐phenanthroline)cadmium(II)]‐μ‐oxalato] 1H‐benzotriazole solvate monohydrate]

In the title compound, [Cd(C₂O₄)(C₁₂H₈N₂)(C₉H₆O₆)]·C₆H₅N₃·H₂O, the Cd^II atom has a distorted pentagonal–bipyramidal geometry, defined by two N atoms and five O atoms from bidentate 1,10‐phenanthroline ligands, oxalate ligands and benzene‐1,3,5‐tricarboxylic acid ligands. The oxalate ligands in the asymmetric unit possess inversion symmetry. The triazole molecule is not coordinated to the Cd atom. The structure of the title compound features a one‐dimensional chain running along the crystallographic a axis, and a three‐dimensional supramolecular network is formed via aromatic π–π interactions and hydrogen‐bonding interactions.     

4,4′‐Bis(2,2,2‐trifluoroethoxymethyl)‐2,2′‐bipyridine

As part of a homologous series of novel polyfluorinated bipyridyl (bpy) ligands, the title compound, C₁₆H₁₄F₆N₂O₂, contains the smallest fluorinated group, viz. CF₃. The molecule resides on a crystallographic inversion centre at the mid‐point of the pyridine C_ipso—C_ipso bond. Therefore, the bpy skeleton lies in an anti conformation to avoid repulsion between the two pyridyl N atoms. Weak intramolecular C—H...N and C—H...O interactions are observed, similar to those in related polyfluorinated bpy–metal complexes. A π–π interaction is observed between the bpy rings of adjacent molecules and this is probably a primary driving force in crystallization. Weak intermolecular C—H...N hydrogen bonding is present between one of the CF₃CH₂– methylene H atoms and a pyridyl N atom related by translation along the [010] direction, in addition to weak benzyl‐type C—H...F interactions to atoms of the terminal CF₃ group. It is of note that the O—CH₂CF₃ bond is almost perpendicular to the bpy plane.     

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.     

(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.     

Poly­[[copper(II)‐di‐μ‐5‐amino­isophthalato(1–)‐κ4N:O] monohydrate]

The title compound, {[Cu(C₈H₆NO₄)₂]·H₂O}_n, was prepared by the hydro­thermal assembly of 5‐amino­isophthalic acid with copper nitrate. Single‐crystal X‐ray analysis shows that it has a two‐dimensional layer coordination framework, in which the unique Cu atom lies on an inversion centre and adopts a square‐planar geometry, coordinated to two N and two O atoms from symmetry‐related ligands. The water molecule lies on a twofold axis and there are hydrogen‐bonding interactions between the layers.     

Bis{μ‐2‐[(2,3‐dichloro­phenyl)­amino]­benzoato‐κO}di‐μ2‐ethoxo‐octa­methyl­di‐μ3‐oxo‐tetra­tin(IV)

The title compound, [Sn₄(CH₃)₈(C₁₃H₈Cl₂NO₂)₂(C₂H₅O)₂O₂], is a centrosymmetric dimer, with three linearly fused four‐membered Sn—O—Sn—O rings. The coordination poly­hedron of the Sn atom bonded to the carboxyl­ate can be described as trigonal–bipyramidal distorted toward square‐pyramidal. That of the second Sn atom is similar, but the distortion towards square‐pyramidal geometry is greater. The Sn—O and Sn—C distances are 2.020 (2)–2.226 (2) and 2.096 (4)–2.114 (4) Å, respectively. The benzene rings of the 2‐[(2,3‐dichloro­phenyl)­amino]benzoate ligand subtend an angle of 50.49 (17)°; the conformation of the ligand is stabilized by intra­molecular N—H⋯Cl and N—H⋯O hydrogen bonds. The structure is assembled viaπ–π stacking inter­actions to form chains parallel to [10].     

Bis(μ‐4‐chloro­benzoato‐κ2O:O)bis[(2‐aminopyridine‐κN)silver(I)]

The title compound, [Ag₂(C₇H₄ClO₂)₂(C₅H₆N₂)₂], lies about an inversion centre and the Ag atom is three‐coordinated by two O atoms and one N atom from three different ligands. The 4‐chloro­benzoate anion acts as a monodonor ligand, bridging two inversion‐related Ag atoms of the compound into a dimer. There are weak intermolecular N—H⋯O hydrogen bonds in the structure.     

Poly­[iron(II)‐di‐μ‐imidazole‐4,5‐di­carboxyl­ato‐κ3N3,O4:O5]

In the title compound, [Fe(C₅H₃N₂O₄)₂]_n, each Fe atom lies on a centre of symmetry, in an octahedral coordination environment consisting of two chelate rings [Fe—N = 2.154 (3) Å and Fe—O = 2.180 (3) Å] and two carboxyl­ate O atoms [Fe—O = 2.111 (2) Å] from imidazole‐4,5‐di­carboxyl­ate ligands. Extensive hydrogen‐bonding interactions exist between layers constructed of Fe₄ squares, forming tunnels along the a axis with large voids.     

Poly[aqua[μ2‐1,4‐bis(imidazol‐1‐ylmethyl)benzene‐κ2N3:N3′](μ2‐5‐hydroxybenzene‐1,3‐dicarboxylato‐κ4O1,O1′:O3,O3′)cadmium(II)], a twofold interpenetrated CdSO4‐like metal–organic polymer

In the title cadmium(II) complex, [Cd(C₈H₄O₅)(C₁₄H₁₄N₄)(H₂O)]_n, the 5‐hydroxybenzene‐1,3‐dicarboxylate (5‐OH‐1,3‐bdc) and 1,4‐bis(imidazol‐1‐ylmethyl)benzene (1,4,‐bix) ligands bridge water‐coordinated Cd^II atoms to generate a three‐dimensional network. Two carboxylate groups from different ligands function as O,O′‐chelates, while two imidazole N atoms from different ligands coordinate in a monodentate fashion, and one water molecule completes the seven‐coordinate pentagonal bipyramid around the Cd^II atom, in which the N atoms occupy the axial sites and the O atoms occupy the equatorial sites. The overall architecture is a twofold interpenetrated CdSO₄‐type framework. The two crystallographically equivalent frameworks are linked by O—H...O hydrogen bonds between the water, hydroxy and carboxylate groups.