Bis[μ-2-(pyridin-2-yl)ethano­lato]bis­[bromidocopper(II)]

The title compound, [Cu2Br2(C7H8NO)2], was synthesized by reaction of CuBr2 with 2-(pyridin-2-yl)ethanol (hep-H) in methanol. The asymmetric unit consists of one hep ligand and a CuBr unit. The Cu2+ ion is thereby coordinated by the N atom and the deprotonated hydroxy O atom in a distorted square-planar geometry that is completed by another O atom. The latter acts as bridging ligand towards the second, symmetry-equivalent, Cu atom, thus generating a centrosymmetric dimeric unit, with the inversion centre halfway between the Cu atoms. These units are linked via C—H⋯Br and C—H⋯O hydrogen bonds, leading to the formation of a hydrogen-bonded one-dimensional-polymeric chain along a.

Reversible single-crystal to single-crystal transformations in a Hg(II) derivative. 1D-polymeric chain ⇋ 2D-networking as a function of temperature

Reactions of HgX2 (X = Cl-, Br-, l-) with the ligand hep-H (hep-H = 2-(2-hydroxyethyl)pyridine) in methanol at 298 K result in 1D-polymeric chains of [(X)Hg(μ-X)2(hep-H)]∞, 1-3, respectively, where hep-H binds to the Hg(II) ions in a monodentate fashion exclusively with the pyridine nitrogen donor and the suitably ortho-positioned -(CH2)2OH group of hep-H remains pendant. The packing diagrams of 1-3 exhibit extensive intramolecular and intermolecular hydrogen bonding interactions leading to hydrogen bonded 2D network arrangement in each case. Though the single crystal of either 2 (X = Br) or 3 (X = I) loses crystallinity upon heating, the single crystal of 1 selectively transforms to a 2D-polymeric network, 4 on heating at 383 K for 1.5 h. The polymeric 4 consists of central dimeric [Hg(μ3-Cl)(hep-H)Cl]2 units, which are covalently linked with the upper and lower layers of [-(μ-Cl)2-Hg-(μ-Cl)2-Hg(μ-Cl)2-]n. The packing diagram of 4 reveals the presence of O-H-Cl and C-H-Cl hydrogen bonding interactions which in effect yields hydrogen bonded 3D-network. Remarkably, the single crystals of 4 convert back to the single crystals of parent 1 on standing at 298 K for three days

5,10,15,20-Tetra-2-furylporphyrin

Mol­ecules of the title macrocycle, C36H22N4O4, are located on an inversion center. The porphyrin ring shows a wave-like conformation with adjacent pyrrole rings tilted above the porphyrin plane and the inter­porphyrin distance is 3.584 (3) Å. The dihedral angles between the meso-furyl groups and the porphyrin plane are 38.87 (7) and 48.29 (7)°; these are much smaller than those observed for meso-tetra­phenyl­porphyrin, indicating that the meso-furyl groups are more inclined towards the porphyrin plane. The decrease in the dihedral angle is due to the presence of intra­molecular hydro­den bonding between the meso-fury O atom and the β-pyrrole CH group. Intra­molecular N—H⋯N hydrogen bonds are also present

Strong metal–metal coupling in mixed-valent intermediates [Cl(L)Ru(μ-tppz)Ru(L)Cl]+, L = β-diketonato ligands, tppz = 2,3,5,6-tetrakis(2-pyridyl)pyrazine

Five diruthenium(II) complexes [Cl(L)Ru(μ-tppz)Ru(L)Cl] (1–5) containing differently substituted β-diketonato derivatives (1: L = 2,4-pentanedionato; 2: L = 3,5-heptanedionato; 3: L = 2,2,6,6-tetramethyl-3,5-heptanedionato; 4: L = 3-methyl-2,4-pentanedionato; 5: L = 3-ethyl-2,4-pentanedionato) as ancillary ligands (L) were synthesized and studied by spectroelectrochemistry (UV-Vis- NIR, electron paramagnetic resonance (EPR)). X-ray structural characterisation revealed anti (1, 2, 5) or syn (3) configuration as well as non-planarity of the bis-tridentate tppz bridge and strong dπ(RuII) → π*(pyrazine, tppz) back- bonding. The widely separated one-electron oxidation steps, RuIIRuII/RuIIRuIII and RuIIRuIII/RuIIIRuIII, result in large comproportionation constants (Kc) of ≥1010 for the mixed-valent intermediates. The syn-configurated 3n exhibits a particularly high Kc of 1012 for n = 1+, accompanied by density functional theory (DFT)-calculated minimum Ru–N bond lengths for this RuIIRuIII intermediate. The electrogenerated mixed-valent states 1+–5+ exhibit anisotropic EPR spectra at 110 K with average values of 2.304–2.234 and g anisotropies Δg = g1–g3 of 0.82–0.99. Metal-to-metal charge transfer (MMCT) absorptions occur for 1+–5+ in the NIR region at 1660 nm–1750 nm (ε ≈ 2700 dm3 mol−1 cm−1, Δν1/2 ≈ 1800 cm−1). DFT calculations of 1+ and 3+ yield comparable Mulliken spin densities of about 0.60 for the metal ions, corresponding to valence-delocalised situations (Ru2.5)2. Rather large spin densities of about −0.4 were calculated for the tppz bridges in 1+ and 3+. The calculated electronic interaction values (VAB) for 1+–5+ are about 3000 cm−1, comparable to that for the Creutz–Taube ion at 3185 cm−1. The DFT calculations predict that the RuIIIRuIII forms in 12+–52+ prefer a triplet (S = 1) ground state with ΔE (S = 0 − S = 1) [similar]5000 cm−1. One-electron reduction takes place at the tppz bridge which results in species [Cl(L)RuII(μ-tppz˙−)RuII(L)Cl]− (1˙−–3˙−, 5˙−) which exhibit free radical-type EPR signals and NIR transitions typical of the tppz radical anion. The system 4n is distinguished by lability of the Ru–Cl bonds

Valence and spin situations in isomeric [(bpy)Ru(Q′)2]n (Q′ = 3,5-di-tert- butyl-N-aryl-1,2-benzoquinonemonoimine). An experimental and DFT analysis

The article deals with the ruthenium complexes, [(bpy)Ru(Q′)2] (1–3) incorporating two unsymmetrical redox-noninnocent iminoquinone moieties [bpy = 2,2′-bipyridine; Q′ = 3,5-di-tert-butyl-N-aryl-1,2-benzoquinonemonoimine, aryl = C6H5 (Q′1), 1; m-Cl2C6H3 (Q′2), 2; m-(OCH3)2C6H3 (Q′3), 3]. 1 and 3 have been preferentially stabilised in the cc-isomeric form while both the ct- and cc-isomeric forms of 2 are isolated [ct: cis and trans and cc: cis and cis with respect to the mutual orientations of O and N donors of two Q′]. The isomeric identities of 1–3 have been authenticated by their single-crystal X-ray structures. The collective consideration of crystallographic and DFT data along with other analytical events reveals that 1–3 exhibit the valence configuration of [(bpy)RuII(Q′Sq)2]. The magnetization studies reveal a ferromagnetic response at 300 K and virtual diamagnetic behaviour at 2 K. DFT calculations on representative 2a and 2b predict that the excited triplet (S = 1) state is lying close to the singlet (S = 0) ground state with singlet–triplet separation of 0.038 eV and 0.075 eV, respectively. In corroboration with the paramagnetic features the complexes exhibit free radical EPR signals with g [similar]2 and 1HNMR spectra with broad aromatic proton signals associated with the Q′ at 300 K. Experimental results in conjunction with the DFT (for representative 2a and 2b) reveal iminoquinone based preferential electron-transfer processes leaving the ruthenium(II) ion mostly as a redox insensitive entity: [(bpy)RuII(Q′Q)2]2+ (12+–32+) [leftrightharpoons] [(bpy)RuII(Q′Sq)(Q′Q)]+ (1+–3+) [leftrightharpoons] [(bpy)RuII(Q′Sq)2] (1–3) [leftrightharpoons] [(bpy)RuII(Q′Sq)(Q′Cat)]−/[(bpy)RuIII(Q′Cat)2]− (1−–3−). The diamagnetic doubly oxidised state, [(bpy)RuII(Q′Q)2]2+ in 12+–32+ has been authenticated further by the crystal structure determination of the representative [(bpy)RuII(Q′3)2](ClO4)2 [3](ClO4)2 as well as by its sharp 1H NMR spectrum. The key electronic transitions in each redox state of 1n–3n have been assigned by TD–DFT calculations on representative 2a and 2b

Hydrothermal synthesis and crystal structure of aqua(pyridine-2,6-dicarboxylato)(1,10-phenanthroline)cobalt(II) dihydrate

1635-1638Hydrothermal reaction of cobalt(II) acetate with pyridine-2,6-dicarboxylato)(1,10-phenanthroline) has afforded aqua(pyridine-2,6-dicarboxylato)(1,10-phenanthroline)cobalt(II) dehydrate (1). X-ray structure determination shows that complex 1 crystallized in the triclinic space group P-1. A one-dimensional assembly has been formed by the intermolecular π-π interactions between the 1,10-phenanthroline units

Crystal structure and phase transition of diglycine perchlorate

Diglycine perchlorate (DGPCl), a new 2:1 adduct formed between glycine and perchloric acid has been obtained and studied using differential scanning calorimetry and single crystal X-ray diffraction. DGPCl undergoes a reversible first-order phase transition at 261.5 K. The crystal structures at 150 and 293 K have been determined to be triclinic, space group P-1, Z = 2, suggesting the first-order phase transition to be an isostructural phase transition. The DGPCl crystal consists of five glycinium-monoprotonated glycinium dimers and five perchlorate anions in an asymmetric unit. The glycine moieties in the glycinium-monoprotonated glycinium dimers are non-planar. Two types of hydrogen bonds are present in the crystal, strong O-H···O hydrogen bonds and a weak N-H···O hydrogen bonds. The short, strong O-H···O hydrogen bond connects the glycinium ion and mono protonated glycinium ion. In four of the dimers, the O-H and H···O bond lengths are different, indicating the hydrogen atom to be located more close to the monoprotonated glycinium ion. However, in one of the glycinium-monoprotonated glycinium dimer the O··H and H··O bond lengths are nearly equal, suggesting the hydrogen atom (O···H···O) to be attached to the oxygen atoms of both glycine moieties. On thermal transition some of these hydrogen bonds are weakened and in all dimers the hydrogen atom seems to be located more close to the mono protonated glycinium ion

Cycloaddition between electron deficient partners: an efficient regio- and stereoselective synthesis of functionalised bicyclo[2.2.2]octenones. A tandem alkylation, stereochemical inversion and aldol condensation

A novel one step regio- and stereoselective synthesis of functionalised bicyclo[2.2.2]octenones from readily available aromatic precursors is described. The methodology involved in situ generation of reactive spiroepoxycyclohexadienones and π4s+π2s cycloaddition with methyl vinyl ketone. Study on π-facial alkylation that led to the formation of homobrendane derivatives as a result of stereochemical inversion and aldol condensation in tandem, is also presented. The crystal structure of 6-acetyl-1-methoxy-bicyclo[2.2.2]oct-7-en-2-one-spiro[3,2′]oxirane and 3-methoxy-4,6,9-trimethyltricyclo[4.3.1.03,7]decan-8-en-5-one-spiro[2,2′]oxirane is also reported.© Elsevie