A novel three‐dimensional coordination polymer: poly[di‐μ3‐acetato‐di‐μ2‐acetato‐di‐μ3‐hydroxido‐octa‐μ3‐triazolato‐heptamanganese(II)]

The title compound, [Mn₇(C₂H₂N₃)₈(C₂H₃O₂)₄(OH)₂]_n, is composed of centrosymmetric heptanuclear building units with the central Mn atom on an inversion center. In the building block, three Mn^II ions are held together by one μ₃‐hydroxide group, two μ₂‐triazolate (trz) ligands and two μ₂‐acetate groups, forming an Mn₃ cluster. Two Mn₃ clusters are bridged by an Mn atom via two μ₂‐trz ligands and two μ₂‐O atoms from two acetate ions to construct a heptanuclear building block. The heptanuclear building units, lying parallel to each other along the b direction, form one‐dimensional ladder‐like chains and are further interlinked, resulting in a three‐dimensional framework through Mn—N_trz bonds.     

Poly[[tetra‐μ3‐acetato‐hexa‐μ2‐acetato‐diaqua‐μ2‐oxalato‐tetrapraseodymium(III)] dihydrate]

The title complex, {[Pr₄(C₂H₃O₂)₁₀(C₂O₄)(H₂O)₂]·2H₂O}_n, was synthesized under hydrothermal conditions from praseodymium acetate and the ionic liquid 1‐butyl‐3‐methylimidazolium chloride via an in situ oxalate‐ligand synthesis. The compound is a two‐dimensional polymer and in the structure presents tightly bound planes parallel to (100), which are in turn linked into a three‐dimensional network by hydrogen bonds involving both coordinated and solvent water molecules. The oxalate anion lies across an inversion centre and acts as a bridge between pairs of Pr atoms within a tetranuclear segment of the polymer.     

Poly[[di‐μ‐aqua‐tetraaquadi‐μ‐hydroxido‐bis(μ3‐3‐nitrophthalato)tricopper(II)] dihydrate]

The novel title complex, {[Cu₃(C₈H₃NO₆)₂(OH)₂(H₂O)₆]·2H₂O}_n, has a one‐dimensional polymeric double chain structure where the three Cu atoms are linked by μ₂‐OH and μ₂‐H₂O groups, and these trinuclear centres are bridged by two 3‐nitrophthalate ligands. The asymmetric unit contains one and a half crystallographically independent Cu atoms (one lying on a centre of inversion), both coordinated by six O atoms and exhibiting distorted octahedral coordination geometries, but with different coordination environments. Each 3‐nitrophthalate ligand connects to three Cu atoms through two O atoms of one carboxylate group and one O atom of the nitro group. The remaining carboxylate group is free and is involved in intrachain hydrogen bonds, reinforcing the chain linkage.     

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[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.     

Tetrakis(μ2‐4‐aminobenzoato)di‐μ3‐oxido‐tetrakis[dibutyltin(IV)]

The molecule of the title compound, [Sn₄(C₄H₉)₈(C₇H₆NO₂)₄O₂], lies about an inversion centre and is a tetranuclear bis(tetrabutyldicarboxylatodistannoxane) complex containing a planar Sn₄O₂ core in which two μ₃‐oxide O atoms connect an Sn₂O₂ ring to two exocyclic Sn atoms. Each Sn atom has a highly distorted octahedral coordination. In the molecule, the carboxylate groups of two aminobenzoate ligands bridge the central and exocyclic Sn atoms, while two further aminobenzoate ligands have highly asymmetric bidentate chelation to the exocyclic Sn atoms plus long O...Sn interactions with the central Sn atoms. Each Sn atom is also coordinated by two pendant n‐butyl ligands, which extend roughly perpendicular to the plane of the Sn₄O₁₀ core. Only one of the four unique hydrogen‐bond donor sites is involved in a classic N—H...O hydrogen bond, and the resulting supramolecular hydrogen‐bonded structure is an extended two‐dimensional network which lies parallel to the (100) plane and consists of a checkerboard pattern of four‐connected molecular cores acting as nodes. The amine groups not involved in the hydrogen‐bonding interactions have significant N—H...π interactions with neighbouring aminobenzene rings.     

A new copper(II) basic sulfate: poly[3‐aminopyridinium μ3‐hydroxido‐di‐μ3‐sulfato‐bis[aquacopper(II)]]

The crystal structure of the title basic copper(II) sulfate, {(C₅H₇N₂)[Cu₂(OH)(SO₄)₂(H₂O)₂]}_n, shows an unprecedented structural arrangement of two distinct copper centres. CuO₆ and CuO₅ polyhedra are linked through bridging hydroxide and sulfate anions to form negatively charged infinite chains propagated along the a axis. The negative charge is balanced by 3‐aminopyridinium cations that are held in the structure by extensive hydrogen bonding to the inorganic chains. Additionally, the cationic arrangement features π–π stacking.     

μ‐Acetato‐μ‐aqua‐μ‐hydroxido‐bis[(1,10‐phenanthroline)copper(II)] dinitrate monohydrate

The triply bridged title dinuclear copper(II) compound, [Cu₂(C₂H₃O₂)(OH)(C₁₂H₈N₂)₂(H₂O)](NO₃)₂·H₂O, (I), consists of a [Cu₂(μ₂‐CH₃COO)(μ₂‐OH)(phen)₂(μ₂‐OH₂)]²⁺ cation (phen is 1,10‐phenanthroline), two uncoordinated nitrate anions and one water molecule. The title cation contains a distorted square‐pyramidal arrangement around each metal centre with a CuN₂O₃ chromophore. In the dinuclear unit, both Cu^II ions are linked through a hydroxide bridge and a triatomic bridging carboxylate group, and at the axial positions through a water molecule. The phenanthroline groups in neighbouring dinuclear units interdigitate along the [010] direction, generating several π–π contacts which give rise to planar arrays parallel to (001). These are in turn connected by hydrogen bonds involving the aqua and hydroxide groups as donors with the nitrate anions as acceptors. Comparisons are made with isostructural compounds having similar cationic units but different counter‐ions; the role of hydrogen bonding in the overall three‐dimensional structure and its ultimate effect on the cell dimensions are discussed.     

Tetra‐μ‐acetato‐O:O′‐bis­[(7‐aza­indole‐N)­copper(II)]

The title complex, [Cu₂(C₂H₃O₂)₄(C₇H₆N₂)₂], shows a binuclear cage structure having an inversion centre. There are intramolecular N—H?O hydrogen bonds between the 7‐aza­indole ligands and the bridging acetate O atoms.     

Di‐μ‐acetato‐bis­[(2‐acetyl­pyridine thio­semicarbazonato)zinc(II)]

The title compound, [Zn₂(C₂H₃O₂)₂(C₈H₉N₄S)₂], is a centrosymmetric dinuclear mol­ecule with two acetate bridging ligands in a syn–syn arrangement. The Zn^II atom is five‐coordinated in a trigonal–bipyramidal configuration by three thio­semicarbazone atoms (two N and one S) and by an O atom from each of the two acetate groups.     

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[propane‐1,3‐diammonium [tetra‐μ3‐oxo‐hexaoxotrimolybdenum(VI)] dihydrate]

The crystal structure of the title compound, {(C₃H₁₂N₂)[Mo₃O₁₀]·2H₂O}_n, is composed of [Mo₃O₁₀]²⁻ anionic chains, propane‐1,3‐diammonium cations and solvent water molecules. The [Mo₃O₁₀]²⁻ chain is constructed from edge‐sharing MoO₆ octahedra. The protonated propane‐1,3‐diamine cations and solvent water molecules are located between the chains and are linked to the O atoms of the inorganic chains by hydrogen bonds.     

Hexa‐μ2‐chloro‐μ4‐oxo‐tetrakis[(2‐ethyl­tetrazole‐κN4)copper(II)]

In the title molecular complex, [Cu₄Cl₆O(2‐EtTz)₄], where 2‐EtTz is 2‐ethyl­tetrazole (C₃H₆N₄), the central O atom is located on the symmetry site and is tetrahedrally coordinated to four Cu atoms, with Cu—O distances of 1.8966 (4) Å. A very slight distortion of Cu₄O from a regular tetrahedron is observed [two Cu—O—Cu angles are 108.76 (3)° and four others are 109.828 (13)°]. Each Cu atom is connected to three others via the Cl atoms, forming a slightly distorted Cl octahedron around the O atom, with O⋯Cl distances of 2.9265 (7) Å for Cl atoms lying on the twofold axis and 2.9441 (13) Å for those in general positions. The Cu atom has a distorted trigonal–bipyramidal environment, with three Cl atoms in the equatorial plane, and with the N atom of the 2‐ethyl­tetrazole ligand and the μ₄‐O atom in axial positions. The Cu atom is displaced out of the equatorial plane by ca 0.91 Å towards the coordinated N atom of the 2‐­ethyl­tetrazole ligand.     

Bis(μ‐2‐sulfonatobenzoato)bis[(1,10‐phenanthroline)­lead(II)] dihydrate

In the title centrosymmetric dimer, [Pb₂(sbc)₂(phen)₂]·2H₂O [sbc is the 2‐sulfonatobenzoate dianion (C₇H₄O₅S) and phen is 1,10‐phenanthroline (C₁₂H₈N₂)], each Pb^II ion is six‐coordinated by four O atoms, viz. carboxyl­ate and sulfonate O atoms from two sbc anions, and two N atoms from a 1,10‐phenanthroline ligand. One 1,10‐phenanthroline ligand and the carboxyl­ate group of one sbc ligand are chelated to each Pb^II cation, and the sulfonate group of the other sbc unit is monodentate. One O atom of the chelated carboxyl­ate group also bridges to the other Pb^II cation, so that each pair of Pb^II ions is bridged by two sbc anions and has the same coordination environment, forming a dinuclear ring. Each pair of Pb^II ions is thus connected by two different kinds of bridges, namely a carboxyl­ate short bridge and a carboxyl­ate–sulfonate long bridge. There is also a special position of site symmetry at the centre of the two Pb^II cations.     

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[[[tetrakis(μ‐acetato‐κ2O:O′)dirhodium(II)]‐μ‐[1,3‐bis(dimethylamino)propan‐2‐ol‐κ2N:N′]] tetrahydrofuran hemisolvate]

In the structure of the title compound, {[Rh₂(C₂H₃O₂)₄(C₇H₁₈N₂O)]·0.5C₄H₈O}_n or {[Rh₂(O₂CMe)₄(Hbdmap)]·0.5C₄H₈O}_n, where Hbdmap is 1,3‐bis­(dimethyl­amino)propan‐2‐ol, each Hbdmap ligand is coordinated to two [Rh₂(O₂CMe)₄] units by two N atoms, resulting in a polymeric chain structure. The observed coordination mode of the Hbdmap mol­ecule is unprecedented.     

Poly[hexaaquaocta‐μ3‐hydroxido‐tetrakis(μ3‐methylenedisulfonato)‐μ6‐oxido‐hexaytterbium(III)]: the first lanthanide sulfonate containing a hexanuclear Ln–hydroxide/oxide cluster synthesized via `ligand‐controlled acidolysis' of lanthanide oxide

The combination of redox and acid sites in lanthanide sulfonate leads to a potentially multifunctional catalyst for oxidation reactions. The title lanthanide sulfonate compound, [Yb₆(CH₂O₆S₂)₄O(OH)₈(H₂O)₆]_n, exhibits a novel one‐dimensional columnar structure along the a direction. In the building unit of the columnar oligomer, a face‐capped lanthanide octahedron, viz. [Ln₆(μ₆‐O)(μ₃‐OH)₈]⁸⁺, is found with an interstitial μ₆‐oxide group lying on an inversion centre, reports of which are rare in the literature. Adjacent hexameric cations are connected via two pairs of O—S—O bridges, thus forming a neutral column. The three‐dimensional network is stabilized by an intricate pattern of intercolumnar hydrogen bonds.