Mo4(η3‐allyl)4Cl2(OH)2(CO)8: the first cubane‐type Mo2+ organometallic complex with μ3‐OH and μ3‐Cl bridges

The reaction between fluorenyllithium and Mo(η³‐C₃H₅)Cl(NCMe)₂(CO)₂ led to the isolation of di‐μ₃‐chlorido‐di‐μ₃‐hydroxido‐tetrakis[(η³‐allyl)dicarbonylmolybdenum(II)]–9‐fluorenone–tetrahydrofuran (1/1/1), [Mo₄(C₃H₅)₄Cl₂(OH)₂(CO)₈]·C₄H₈O·C₁₃H₈O. The tetrametallic Mo₄ unit constitutes the first example of a complex containing simultaneously two μ₃‐OH groups and two μ₃‐Cl anions capping the metallic trigonal prism. The four crystallographically independent Mo²⁺ centres exhibit distorted octahedral geometry with the η³‐allyl groups being trans‐coordinated to a μ₃‐OH group and the carbonyl groups occupying the equatorial plane. Space‐filling tetrahydrofuran and 9‐fluorenone molecules are engaged in strong O—H...O hydrogen‐bonding interactions with Mo₄(η³‐allyl)₄Cl₂(OH)₂(CO)₈ complexes.     

A three‐dimensional coordination polymer based on the Zn4(μ3‐OH)2 unit: poly[[(μ4‐benzene‐1,4‐dicarboxylato)bis(μ3‐benzene‐1,4‐dicarboxylato)bis(μ3‐hydroxido)bis(1,10‐phenanthroline‐5,6‐dione)tetrazinc] dihydrate]

The title compound, {[Zn₄(C₈H₄O₄)₃(OH)₂(C₁₂H₆N₂O₂)₂]·2H₂O}_n, has been prepared hydrothermally by the reaction of Zn(NO₃)₂·6H₂O with benzene‐1,4‐dicarboxylic acid (H₂bdc) and 1,10‐phenanthroline‐5,6‐dione (pdon) in H₂O. In the crystal structure, a tetranuclear Zn₄(OH)₂ fragment is located on a crystallographic inversion centre which relates two subunits, each containing a [ZnN₂O₄] octahedron and a [ZnO₄] tetrahedron bridged by a μ₃‐OH group. The pdon ligand chelates to zinc through its two N atoms to form part of the [ZnN₂O₄] octahedron. The two crystallographically independent bdc²⁻ ligands are fully deprotonated and adopt μ₃‐κO:κO′:κO′′ and μ₄‐κO:κO′:κO′′:κO′′′ coordination modes, bridging three or four Zn^II cations, respectively, from two Zn₄(OH)₂ units. The Zn₄(OH)₂ fragment connects six neighbouring tetranuclear units through four μ₃‐bdc²⁻ and two μ₄‐bdc²⁻ ligands, forming a three‐dimensional framework with uninodal 6‐connected α‐Po topology, in which the tetranuclear Zn₄(OH)₂ units are considered as 6‐connected nodes and the bdc²⁻ ligands act as linkers. The uncoordinated water molecules are located on opposite sides of the Zn₄(OH)₂ unit and are connected to it through hydrogen‐bonding interactions involving hydroxide and carboxylate groups. The structure is further stabilized by extensive π–π interactions between the pdon and μ₄‐bdc²⁻ ligands.     

Poly[hexaaquabis(μ4‐4‐carboxybenzenesulfonato)bis(μ3‐4‐carboxybenzenesulfonato)calcium(II)dipotassium(I)]

This study presents the coordination modes and crystal organization of a calcium–potassium coordination polymer, poly[hexaaquabis(μ₄‐4‐carboxybenzenesulfonato‐κ⁴O¹:O^1′:O^1′′:O⁴)bis(μ₃‐4‐carboxybenzenesulfonato‐κ²O¹:O^1′)calcium(II)dipotassium(I)], [CaK₂(C₇H₅O₅S)₄(H₂O)₆]_n, displaying a novel two‐dimensional framework. The potassium ion is seven‐coordinated by four sulfonate and one carboxyl O atom located on five different acid ligands, two of which are unique, and by two symmetry‐independent water O atoms. A pair of close potassium ions share two inversion‐related sulfonate O‐atom sites to form a dimeric K₂O₁₂ unit, which is extended into a one‐dimensional array along the a‐axis direction. The six‐coordinate Ca²⁺ ion occupies a special position () at (0, , ) and is surrounded by four sulfonate O atoms from two inversion‐related pairs of unique acid monoanions and by two O atoms from aqua ligands. The compound displays a layered structure, with K₂O₁₂ and CaO₆ polyhedra in the layers and aromatic linkers between the layers. The three‐dimensional scaffold is open, with nano‐sized channels along the c axis.     

“Cage‐like” Carboxyl Bridged Octaphenyltetraantimony Compounds (SbPh2)4(μ‐O)4(μ‐OH)2(μ‐O2CR)2: Synthesis and Structural Characterization

The metal‐directed self‐assembly of biphenylantimony trichloride and homocarboxylic acids LH [L = 2‐CHO‐C₆H₄COO^– ( 1 ), 2, 3‐2F‐C₆H₄COO^– ( 2 ), 4‐CF₃–C₆H₄COO^– ( 3 )] provided three novel tetranuclear organoantimony(V) complexes, which were characterized by elemental analysis, FT‐IR, ¹H, and ¹³C NMR spectroscopy as well as melting point, and X‐ray single crystal analysis. In the molecular structure, four hexacoordinate antimony atoms are linked into a [Sb₂(μ‐O)₂]₂(μ‐O)₂ “cage” architecture by oxo‐bridges which are terminally bridged by two carboxyl 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.     

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.     

The bimolecular structure of aquahexa‐μ‐chlorido‐μ4‐oxido‐tris(tetrahydrofuran‐κO)tetracopper(II)–hexa‐μ‐chlorido‐μ4‐oxido‐tetrakis(tetrahydrofuran‐κO)tetracopper(II)–tetrahydrofuran (2/1/4)

The title bimolecular structure, [Cu₄Cl₆O(C₄H₈O)₃(H₂O)]₂[Cu₄Cl₆O(C₄H₈O)₄]·4C₄H₈O, at 100 K has monoclinic (P2₁/c) symmetry. The structure contains nine symmetry‐independent molecules expressed in simplest molecular form as 6[Cu₄Cl₆O(C₄H₈O)₃(H₂O)·2(C₄H₈O)]:3Cu₄Cl₆O(C₄H₈O)₄. The compound exhibits a supercell (smaller than the unit cell based on weak reflections) structure due to pseudotranslational symmetry. The structure displays O—H...O hydrogen bonding between bound water ligands and tetrahydrofuran (THF) solvent molecules. The structure exhibits disorder for 12 of the THF molecules, of which seven are ligated to Cu and five are hydrogen bonded to H₂O ligands.     

Poly­[lead(II)‐μ2‐aqua‐μ4‐tereph­thalato]

The title compound, [Pb(C₈H₄O₄)(H₂O)]_n, forms as an insoluble product in the reaction of sodium terephthalate(2−) with Pb(NO₃)₂ in water. Analysis has shown that the crystal structure is centrosymmetric, with the asymmetric unit containing one formula unit. The lead geometry is hemidirected seven‐coordinate, with both monodentate and bidentate carboxyl­ate coordination modes present. The combination of hydrogen bonds and coordination bonds produces a three‐dimensional structure, including the first example, in a lead complex, of the common metal‐coordinated carboxyl­ate/water (6) graph‐set motif.     

Poly[bis(μ4‐benzene‐1,2‐dicarboxylato)di‐μ3‐isonicotinato‐dilanthanum(III)]

In the title compound, [La₂(C₈H₄O₄)₂(C₆H₄NO₂)₂]_n, there are two crystallographically independent La centres, both nine‐coordinated in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom. The La centres are linked by the carboxylate groups of isonicotinate (IN⁻) and benzene‐1,2‐dicarboxylate (BDC²⁻) ligands to form La–carboxylate chains, which are further expanded into a three‐dimensional framework with nanometre‐sized channels by La—N bonds. In the construction of the resultant architecture, in tricapped trigonal prismatic coordination geometries by eight carboxylate O atoms and one pyridyl N atom, while the BDC ligands link to four different cations each, displaying penta‐ and heptadentate chelating–bridging modes, respectively.     

Heterodinukleare Komplexe: Synthese und Kristallstrukturen von [RuRh(μ‐CO)(CO)4(μ‐PtBu2)(tBu2PH)], [RuRh(μ‐CO)(CO)3(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [CoRh(CO)4(μ‐H)(μ‐PtBu2)(tBu2PH)]

Heterobinuclear Complexes: Synthesis and X‐ray Crystal Structures of [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)], [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], and [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] [Ru₃Rh(CO)₇(μ₃‐H)(μ‐P^tBu₂)₂(^tBu₂PH)(μ‐Cl)₂] ( 2 ) yields by cluster degradation under CO pressure as main product the heterobinuclear complex [RuRh(μ‐CO)(CO)₄(μ‐P^tBu₂)(^tBu₂PH)] ( 4 ). The compound crystallizes in the orthorhombic space group Pcab with a = 15.6802(15), b = 28.953(3), c = 11.8419(19) Å and V = 5376.2(11) ų. The reaction of 4 with dppm (Ph₂PCH₂PPh₂) in THF at room temperature affords in good yields [RuRh(μ‐CO)(CO)₃(μ‐P^tBu₂)(μ‐dppm)] ( 7 ). 7 crystallizes in the triclinic space group P 1 with a = 9.7503(19), b = 13.399(3), c = 15.823(3) Å and V = 1854.6 ų. Moreover single crystals of [CoRh(CO)₄(μ‐H)(μ‐P^tBu₂)(^tBu₂PH)] ( 9 ) could be obtained and the single‐crystal X‐ray structure analysis revealed that 9 crystallizes in the monoclinic space group P2₁/a with a = 11.611(2), b = 13.333(2), c = 18.186(3) Å and V = 2693.0(8) ų.     

A New Preparative Route of the “Stepped‐Cubane” Tetranuclear Copper(II) Compound, [Cu4(μ2‐OH)2(μ3‐OH)2Cl2(bipy)4]Cl2 · 6H2O

The compound [Cu₄(μ₂‐OH)₂(μ₃‐OH)₂Cl₂(bipy)₄]Cl₂ · 6H₂O ( 1 ) was obtained by recrystallization of [Cu(HB)₂(2, 2′‐bipy)] · H₂O (H₂B = diphenylglycolic acid) from EtOH/CH₂Cl₂ and their structure has been determined by single‐crystal X‐ray analysis. The cationic complex may be described as based on a Cu₄(OH)₄ core with a “stepped cubane” structure. The coordination polyhedron around each copper is a distorted square pyramid. The tetranuclear units are linked in the crystal by C‐H…Cl hydrogen bonds and by π‐π interactions between bipyridine rings. IR data are also presented.     

Poly[[μ2‐1,3‐bis(pyridin‐4‐yl)propane](μ3‐1,4‐phenylenediacetato)cadmium]

Solvothermal reaction between Cd(NO₃)₂, 1,4‐phenylenediacetate (1,4‐PDA) and 1,3‐bis(pyridin‐4‐yl)propane (bpp) afforded the title complex, [Cd(C₁₀H₈O₄)(C₁₃H₁₄N₂)]_n. Adjacent carboxylate‐bridged Cd^II ions are related by an inversion centre. The 1,4‐PDA ligands adopt a cis conformation and connect the Cd^II ions to form a one‐dimensional chain extending along the c axis. These chains are in turn linked into a two‐dimensional network through bpp bridges. The bpp ligands adopt an anti–gauche conformation. From a topological point of view, each bpp ligand and each pair of 1,4‐PDA ligands can be considered as linkers, while the dinuclear Cd^II unit can be regarded as a 6‐connecting node. Thus, the structure can be simplified to a two‐dimensional 6‐connected network.     

Structure and Photocatalytic Property of a Cobalt(II) Compound Containing Pentanuclear [Co5(mtpo)2(μ3‐OH)2(μ2‐OH)2(COO)3] Clusters as Building Subunits

The cobalt(II) compound [Co₅(mtpo)₂(pdc)₃(μ₃‐OH)₂(μ₂‐OH)₂(H₂O)₂]_n ( 1 ) (mtpo = 7‐hydroxy‐5‐methyl‐1,3,4‐triazaindolizine, H₂pdc = terephthalic acid) was synthesized by hydrothermal reaction of Co(NO₃)₂, mtpo, and H₂pdc. X‐ray structural analysis shows that compound 1 features a 3D framework containing pentanuclear [Co₅(mtpo)₂(μ₃‐OH)₂(μ₂‐OH)₂(COO)₃] clusters as building subunits. Topological analysis reveals that compound 1 can be simplified into a 6‐connected pcu topological network. Notably, this compound can be used as visible‐light‐driven photocatalyst for photodegradation of MB.