Bis(1‐ferrocenylbutane‐1,3‐dionato‐κ2O,O′)copper(II) and bis­(1,3‐diferrocenylpropane‐1,3‐dionato‐κ2O,O′)­copper(II)

The title compounds, [CuFe₂(C₅H₅)₂(C₉H₈O₂)₂], (I), and [CuFe₄(C₅H₅)₄(C₁₃H₉O₂)₂], (II), are four‐coordinate square‐planar copper(II) complexes with two bidentate 1‐ferrocenylbutane‐1,3‐dionate or 1,3‐diferrocenylpropane‐1,3‐dionate ligands, respectively. The copper ion in (I) lies on an inversion centre, with one‐half of the mol­ecule in the asymmetric unit, while in (II), there are two independent half mol­ecules in the asymmetric unit, with the copper ions also situated on inversion centres. The ferrocene substituents in (I) are in an anti arrangement. The mol­ecules assemble in the crystal structure in layers with ferrocene groups at the surface. The pairs of ferrocene substituents on each ligand in complex (II) are syn and these adopt an anti arrangement with respect to the pair on the other diketonate ligand. As found in (I), complexes assemble in a layered structure with ferrocene‐coated surfaces.     

Bis(μ‐succinato‐O,O′:O′′,O′′′)bis[bis(2‐amino‐1,3‐benzothiazole‐N3)copper(II)]

In the title dimeric complex, [Cu₂(C₄H₄O₄)₂(C₇H₆N₂S)₄], which possesses a centre of symmetry, the Cu atoms are enclosed in a 14‐membered ring. They adopt a distorted square‐bipyramidal (4+2) coordination. The four closest donor atoms are two N atoms of 2‐amino­benzo­thiazole ligands and two O atoms of the succinate carboxylate groups. They form a square‐planar cis arrangement, with an average Cu—N distance of 2.003 (3) Å and Cu—O distances of 1.949 (3) and 1.965 (3) Å. Two longer Cu—O bonds of 2.709 (3) and 2.613 (3) Å involving the remaining O atoms of the carboxylate groups complete the sixfold coordination of the Cu atoms. The H atoms of each amino group of the 2‐amino­benzo­thiazole molecules form intra‐ and inter­molecular N—H?O hydrogen bonds. A nearly perpendicular inter­molecular C—H?Cg interaction (Cg is the centroid of the imidazole ring) is observed. The intramolecular Cu?Cu distance is 6.384 (2) Å.     

Bis(dimethyl sulfoxide‐S)tetrakis(μ‐p‐hydroxybenzoato‐O:O′)dirhodium(II)–tetrakis(μ‐butyrato‐O:O′)bis(dimethyl sulfoxide‐S)dirhodium(II) cocrystal ethanol disolvate

The title structure, [Rh₂(C₇H₅O₃)₄(C₂H₆OS)₂]·[Rh₂(C₄H₇­O₂)₄(C₂H₆OS)₂]·2C₂H₆O, contains two discrete neutral Rh–Rh dimers cocrystallized as the ethanol disolvate. Each dimer is situated on an inversion center. The butyrate chain displays disorder in one C‐atom position. In each dimer, the di­methyl sulfoxide ligand (dmso) is bound via S, as expected. The ethanol is a hydrogen‐bond acceptor for one p‐hydroxy­benzoate hydroxyl group and acts as a hydrogen‐bond donor to the dmso O atom of a neighboring p‐hydroxy­benzoate dirhodium complex. A third hydrogen bond is formed from the other p‐hydroxy­benzoate hydroxyl group to the dmso O atom of a butyrate–dirhodium complex.     

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.     

Poly[[[(1,2‐η)‐benzene]silver(I)]‐μ‐trifluoromethanesulfonate‐O;O′;O′′:O′′]

The title compound, [Ag(CF₃O₃S)(C₆H₆)], has been synthesized and characterized by low‐temperature single‐crystal X‐ray diffraction. The complex is polymeric, with a network of tri­fluoro­methane­sulfonate anions bridging the silver cations. The terminal planar benzene ligand is asymmetrically η²‐coordinated to the Ag.     

Bis(2,6‐diamino‐1H‐purin‐3‐ium) di‐μ‐croconato‐κ3O,O′:O′′;κ3O:O′,O′′‐bis[tetraaqua(croconato‐κ2O,O′)neodymium(III)]

The structure of the ionic title compound, (C₅H₇N₆)₂[Nd₂(C₅O₅)₄(H₂O)₈], consists of anionic dimers built around an inversion centre and is made up of an Nd^III cation, two croconate (croco) dianions and four water molecules (plus their inversion images), with two noncoordinated symmetry‐related 2,6‐diamino‐1H‐purin‐3‐ium (Hdap⁺) cations providing charge balance. Each Nd^III atom is bound to nine O atoms from four water and three croco units. The coordination polyhedron has the form of a rather regular monocapped square antiprism. The croconate anions are regular and the Hdap⁺ cation presents a unique, thus far unreported, protonation state. The abundance of hydrogen‐bonding donors and acceptors gives rise to a complex packing scheme consisting of dimers interlinked along the three crystallographic directions and defining anionic `cages' where the unbound Hdap⁺ cations lodge, linking to the mainframe via (N—H)_Hdap...O_water/croco and (O—H)_water...N_Hdap interactions.     

Bis(2,2′‐bipyridyl‐N,N′)­tris­(nitrato‐O,O′)­neodymium

The title compound, [Nd(bipy‐N,N′)₂(NO₃–O,O′)₃], is found to be isomorphous with the La and Lu analogues having three bidentate nitrate and two bipyridyl ligands giving a ten co‐ordinate environment.     

Di‐μ‐acetato‐O:O′‐di‐μ‐acetato‐O,O′:O′‐bis­{[(cyclo­penta­dienyl)tris­(di­methyl­phosphito‐P)­cobalt‐O,O′,O′′]neodymium(III)}

In the title compound, [{η⁵‐CpCo[P(O)(OMe)₂]₃}Nd(O₂CCH₃)₂]₂, with a centrosymmetric mol­ecule, each Nd atom has an eight‐coordination environment, surrounded by a tripodal {L_OMe = CpCo[P(O)(OMe)₂]₃} and four bridging acetato ligands. The coordination geometry around each Nd centre is described as a distorted square‐antiprism and the two different types of acetato ligands have μ‐O:O′‐ and μ‐O,O′:O′‐acetato coordination modes. The Nd—O distances are in the range 2.378 (4)–2.594 (5) Å and the Nd?Nd distance is 3.9913 (6) Å.     

Bis(μ‐diphenyl­phosphinato‐κ2O:O′)bis­[aqua­(diphenyl­phosphinato‐κO)bis­(pyridine‐κN)cobalt(II)]

In the centrosymmetric title compound, [Co₂(C₁₂H₁₀O₂P)₄(C₅H₅N)₄(H₂O)₂], each approximately octa­hedral Co atom features two trans‐coordinated pyridine mol­ecules, one water mol­ecule, a terminally coordinated monodentate diphenyl­phosphinate ligand, and two bidentate diphenyl­phosphinate ligands that bridge the two Co atoms across a centre of inversion to form a dimeric binuclear complex. The discrete mol­ecules are linked by double hydrogen bonds between the terminally coordinated diphenyl­phosphinate ligand and the water mol­ecule to form a continuous chain along the crystallographic b axis.     

Potassium,rubidium and ammonium salts of μ‐(formato‐κ2O:O′)‐μ‐oxido‐bis[oxidobis(peroxido‐κ2O,O′)molybdate(VI)]

The unit‐cell parameters of the three title salts, namely, tripotassium, K₃[Mo₂(CHO₂)O₃(O₂)₄], trirubidium, Rb₃[Mo₂(CHO₂)O₃(O₂)₄], and triammonium μ‐(formato‐κ²O:O′)‐μ‐oxido‐bis[oxidobis(peroxido‐κ²O,O′)molybdate(VI)], (NH₄)₃[Mo₂(CHO₂)O₃(O₂)₄], which were all crystallized at pH 3, are quite similar, but the potassium and rubidium salt structures are noncentrosymmetric, whereas that of the ammonium salt is centrosymmetric. Formate acts as an O:O′‐bridging ligand in the complex anion and is bound to a μ‐oxido‐bis(oxidodiperoxidomolybdate) unit.     

catena‐Poly[[(acetato‐κ2O,O′)triaquabarium(II)]‐μ3‐acetato‐κ4O:O,O′:O′]

The present form of barium acetate, formulated as [Ba(C₂H₃O₂)₂(H₂O)₃]_n, is the largest reported hydrate of the salt and this leads to a distinct structural behaviour setting it apart from the rest of the family. The compound is a linear polymer with a nine‐coordinate Ba(O_aqua)₃(O_acetate)₆ monomer unit. The non‐H part of the structure is ordered according to C2/m symmetry, while the disordered water H atoms only abide by this symmetry in a statistical sense. Each molecule is halved by a mirror plane bisecting the Ba centre, one water molecule and one acetate ligand, while containing the other acetate ligand. The chains are interconnected by a disordered water–water/acetate O—H...O hydrogen‐bonding network involving all water H atoms. The structure and stability of this phase are compared with the other known acetates of barium which differ in the degree of hydration.     

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).     

(μ‐1,2‐Dimethoxyethane‐κ2O:O′)bis[(1,2‐dimethoxyethane‐κ2O,O′)tris(1,1,1,5,5,5‐hexafluoro‐4‐oxopent‐2‐en‐2‐olato‐κ2O,O′)cerium(III)]

A previous analysis [Fatila et al. (2012). Dalton Trans. 41 , 1352–1362] of the title complex, [Ce₂(C₅HF₆O₂)₆(C₄H₁₀O₂)₃], had identified it as Ce(hfac)₃(dme)_1.5 according to the ¹H NMR integration [hfac = 1,1,1,5,5,5‐hexafluoroacetylacetonate (1,1,1,5,5,5‐hexafluoro‐4‐oxopent‐2‐en‐2‐olate) and dme = 1,2‐dimethoxyethane]; however, it was not possible to determine the coordination environment unambiguously. The structural data presented here reveal that the complex is a binuclear species located on a crystallographic inversion center. Each Ce^III ion is coordinated to three hfac ligands, one bidentate dme ligand and one monodentate (bridging) dme ligand, thus giving a coordination number of nine (CN = 9) to each Ce^III ion. The atoms of the bridging dme ligand are unequally disordered over two sets of sites. In addition, in two of the –CF₃ groups, the F atoms are rotationally disordered over two sets of sites. This is the first crystal structure of a binuclear lanthanide β‐diketonate with a bridging dme ligand.     

A novel titanium–μ‐O–zirconium complex: bis(μ‐methyliminodiethanolato‐1κ3O,N,O′;1:2κ2O)(methyliminodiethanolato‐2κ3O,N,O′)dipropanolato‐1κO,2κO‐titanium(IV)zirconium(IV)

The title compound, [TiZr(C₅H₁₁NO₂)₃(C₃H₇O)₂], contains three methyl­imino­diethano­late ligands, two in different μ‐oxo bridging coordination modes and one bound only to the Ti atom. The Ti and Zr atoms have distorted octahedral and pentagonal–bipyramidal coordinations, respectively, which share edges. As well as some conformational disorder in the carbon chains, there is chemical disorder at one Ti site, with a mix of n‐ and isopropanolate ligands.     

Poly[triaqua(μ4‐4‐carboxybenzenesulfonato‐κ4O:O′:O′′:O′′′)(4‐carboxybenzenesulfonato‐κO)strontium(II)]

This study presents the coordination modes and two‐dimensional network of a novel strontium(II) coordination polymer, [Sr(C₇H₅O₅S)₂(H₂O)₃]_n. The eight‐coordinate Sr²⁺ ion is in a distorted bis‐disphenoidal coordination environment, surrounded by four sulfonate and one carboxyl O atom from five benzenesulfonate ligands, two of which are symmetry unique, and by three O atoms from three independent aqua ligands. The compound exhibits a monolayer structure with coordination bonds within and hydrogen bonds between the layers. The μ₄ acid ligand bridges the metal ions in two dimensions to form a thick undulating monolayer with a hydrophobic interior and hydrophilic surfaces. A second independent monoanion is arranged outward from both sides of the monolayer and serves to link adjacent monolayers via carboxyl–water and water–carboxyl 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.     

catena‐Poly­[[di­aqua­(isonicotinato‐O,O′)­europium(III)]‐di‐μ‐isonicotin­ato‐O:O′]

The title complex, [Eu(C₆H₄O₂)₃(H₂O)₂], has a double carboxyl­ate‐bridged infinite‐chain structure, with one chelating carboxyl­ate group on each Eu ion centre, which also binds to two water mol­ecules to yield an eight‐coordinate square‐antiprismatic geometry, with Eu—O bond lengths in the range 2.338 (3)–2.594 (3) Å. The pyridine N atoms of the isonicotinate groups do not coordinate to the Eu ions; instead, they direct the formation of Eu^III coordination polymers via hydrogen bonding with coordinated water mol­ecules.     

Poly[(μ4‐adamantane‐1,3‐dicarboxylato‐κ5O1:O1′:O3,O3′:O3′)(μ3‐adamantane‐1,3‐dicarboxylato‐κ5O1,O1′:O3,O3′:O3′)dimagnesium]: a layered coordination polymer

The title compound, [Mg₂(C₁₂H₁₄O₄)₂]_n, is the first example of an s‐block metal adamantanedicarboxylate coordination polymer. The asymmetric unit comprises two crystallographically unique Mg^II centers and two adamantane‐1,3‐dicarboxylate ligands. The compound is constructed from a combination of chains of corner‐sharing magnesium‐centered polyhedra, parallel to the a axis, connected by organic linkers to form a layered polymer. The two Mg^II centers are present in distorted tetrahedral and octahedral coordination environments derived from carboxylate O atoms. Tetrahedrally coordinated Mg^II centers have been reported in organometallic compounds, but this is the first time that such coordination has been observed in a magnesium‐based coordination polymer. The bond valance sums of the two Mg^II centers are 2.05 and 2.11 valence units, matching well with the expected value of 2.     

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.     

Semisynthesis of 3′(2′)‐O‐(Aminoacyl)‐tRNA Derivatives as Ribosomal Substrate

An efficient synthesis of (3′‐terminally) 3′(2′)‐O‐aminoacylated pCpA derivatives is described, which could lead to the production of (aminoacyl)‐tRNAs following T4 RNA ligase mediated ligation. The tetrahydrofuranyl (thf) group was used as a permanent protective group for the 2′‐OH of the cytidine moiety which can be removed during the purification of the 3′(2′)‐O‐aminoacylated‐pCpA. This approach allowed for a general synthesis of (3′‐terminally) 3′(2′)‐O‐aminoacylated oligonucleotides. The fully protected pCpA 14 was synthesized by phosphoramidite chemistry and treated with NH₃ solution to remove the 2‐cyanoethyl and benzoyl groups (→ 15 ; Schemes 1 and 2). The 2′‐O‐thf‐protected‐pCpA 15 was coupled with α‐amino acid cyanomethyl esters, and the products 20a – c were deprotected and purified with AcOH buffer to afford 3′(2′)‐O‐aminoacylated pCpA 21a – c in high yields. The 3′(2′)‐O‐aminoacylated pCpA were efficiently ligated with tRNA(? CA) to yield (aminoacyl)‐tRNA which was an active substrate for the ribosome.