Crystal structure and Hirshfeld surface analysis of a new mononuclear copper(II) complex: [bis-(pyridin-2-yl-κ)amine](formato-κ)(-hy-droxy-benzoato-κ,')copper(II).

A new mononuclear copper(II) complex, [Cu(CHO)(HCO)(CHN)], containing mixed - and -donor ligands, 2,2'-di-pyridyl-amine (dpyam) and -hy-droxy-benzoate (-OHbenz), has been obtained from a solvent mixture. The coordination environment of the Cu ion is distorted square-pyramidal with a [NO] coordination set originating from the chelating dpyam and -OHbenz ligands in the basal plane and the O atom of a formato ligand at the apical position. The crystal structure of the title complex is stabilized by N-H⋯O, O-H⋯O, C-H⋯O hydrogen-bonding, and C-H⋯ inter-molecular inter-actions, which were qu-anti-fied by Hirshfeld surface analysis.

Phlegcarines A-C, three Lycopodium alkaloids from Phlegmariurus carinatus (Desv. ex Poir.) Ching.

Three undescribed Lycopodium alkaloids, phlegcarines A-C, along with nine known alkaloids, were isolated from the aerial parts of a gardening clubmoss Phlegmariurus carinatus (Desv. ex Poir.) Ching.

Crystal structure of -poly[[[bis-(1-benzyl-imidazole-κ)copper(II)]-μ-sulfato-κ :'-[tetra-kis-(1-benzyl-imidazole-κ)copper(II)]-μ-sulfato-κ :'] ,-di-methyl-formamide disolvate dihydrate].

The title one-dimensional copper(II) coordination polymer, {[Cu(SO)(CHN)]·CHNO·HO} or {[Cu(bzi)(μ-OSO)]·HO·DMF} (bzi = 1-benz-yl-imidazole, CHN; DMF = ,-di-methyl-formamide, CHNO), is constructed by monodentate bzi ligands and bridging sulfate anions, leading to chains propagating parallel to the axis. Within a chain, there are two crystallographic independent Cu ions, each with site symmetry , which form [CuNO] and [CuNO] polyhedra alternating along the chain direction. The crystal structure is consolidated by weak hydrogen-bonding, C-H⋯π and π-π inter-actions, leading to the formation of a three-dimensional supra-molecular network.

Synthesis and crystal structure of poly[[bis-(aqua-κ)tetra-kis-(μ-4,4'-bi-pyridine-κ :')hexa-kis-(3-chloro-benzoato)-κ ;κ :'-tricobalt(II)] methanol disolvate].

A novel ladder-chain cobalt(II) coordination polymer, {[Co(CHClO)(CHN)(HO)]·2CHOH} , was synthesized and characterized. The structure contains two Co centres with different octa-hedral environments, [Co(1)NO] and [Co(2)NO]. The -donating 3-chloro-benzoate anions (3-Clbenz) act as the terminal ligands, while the -donating 4,4'-bipy mol-ecules play the role of linkers.

Highly Regioselective Tandem Reaction of Ene-Yne-Oxazolones Induced by -Phosphonates: Construction of Phosphinylindane Derivatives.

A highly regioselective divergent approach for the phosphine-containing indane/indene derivatives from the ene-yne-oxazolone precursors was reported. An insight into the reaction mechanism involving the phospha-1,4-addition followed by 5- ring closure with a concomitant C-P/C-C bond formation was also proposed. This promising protocol utilized -phosphonate as the phosphonating reagent in a silver-catalyzed or base-mediated cascade cyclization to construct the corresponding phosphorylated spiroindenoxazolones and amidoindenes, respectively, in good yields (up to 88% yield).

Crystal structure of a novel one-dimensional zigzag chain-like cobalt(II) coordination polymer constructed from 4,4'-bi-pyridine and 2-hy-droxy-benzoate ligands.

A novel one-dimensional zigzag chain-like Co coordination polymer constructed from 4,4'-bi-pyridine (4,4'-bpy) and 2-hy-droxy-benzoate (2-OHbenz) ligands, namely, -poly[[(4,4'-bi-pyridine-κ)-(μ-2-hy-droxy-benzoato-κ :')(2-hy-droxy-benzoato-κ ,')cobalt(II)]-μ-4,4'-bi-pyridine-κ :'-[aquahemi(μ-4,4'-bi-pyridine-κ :')(2-hy-droxy-benzoato-κ(2-hy-droxy-benzoato-κ :')cobalt(II)], [Co(CHO)(CHN)(HO)] , has been synthesized by reacting cobalt(II) nitrate trihydrate, 4,4'-bpy and 2-hy-droxy-benzoic acid in a mixture of water and methanol at room temperature. There are two independent Co centers, Co1 and Co2, in the asymmetric unit, revealing a distorted octa-hedral geometry with chromophore types of [CoNO] and [CoNOO'], respectively. The Co1 ions are doubly bridged by 2-OHbenz ligands with - coordination mode, generating a dinuclear unit.

Crystal structures and Hirshfeld surface analysis of -bis-(thio-cyanato-κ)bis-{2,4,6-trimethyl--[(pyridin-2-yl)methyl-idene]aniline-κ ,'}manganese(II) and -bis-(thio-cyanato-κ)bis-{2,4,6-trimethyl--[(pyridin-2-yl)methyl-idene]aniline- ,'}nickel(II)).

Two new mononuclear metal complexes involving the bidentate Schiff base ligand 2,4,6-trimethyl--[(pyridin-2-yl)methyl-idene]aniline (CHN or PM-TMA), [Mn(NCS)(PM-TMA)] () and [Ni(NCS)(PM-TMA)] (), were synthesized and their structures determined by single-crystal X-ray diffraction. Although the title compounds crystallize in different crystal systems [triclinic for () and monoclinic for ()], both asymmetric units consist of one-half of the complex mol-ecule, one metal(II) cation, one PM-TMA ligand, and one N-bound thio-cyanate anion. In both complexes, the metal(II) cation is located on a centre of inversion and adopts a distorted octa-hedral coordination environment defined by four N atoms from two symmetry-related PM-TMA ligands in the equatorial plane and two N atoms from two symmetry-related NCS anions in a axial arrangement.

Crystal structure and photoluminescence properties of -poly[[bis-(1-benzyl-1-imidazole-κ )cadmium(II)]-di-μ-azido-κ : ].

The new title one-dimensional Cd coordination polymer, [Cd(CHN)(μ-N)] , has been synthesized and structurally characterized by single-crystal X-ray diffraction. The asymmetric unit consists of a Cd ion, one azide and one 1-benzyl-imidazole (bzi) ligand. The Cd ion is located on an inversion centre and is surrounded in a distorted octa-hedral coordination sphere by six N atoms from four symmetry-related azide ligands and two symmetry-related bzi ligands.

Crystal structure and Hirshfeld surface analysis of bis-(benzoato-κ ,')[bis-(pyridin-2-yl-κ)amine]nickel(II).

A new mononuclear Ni complex with bis-(pyridin-2-yl)amine (dpyam) and benzoate (benz), [Ni(CHO)(CHN)], crystallizes in the monoclinic space group 2/. The Ni ion adopts a -distorted octa-hedral geometry with an [NiNO] chromophore. In the crystal, the complex mol-ecules are linked together into a one-dimensional chain by symmetry-related π-π stacking inter-actions [centroid-to-centroid distance = 3.

Crystal structure of poly[di-aqua-bis-(μ-benzene-1,3-di-carboxyl-ato)(,-di-methyl-formamide)-cadmium(II)disodium(I)].

The title compound, [CdNa(CHO)(CHNO)(HO)] or [CdNa(1,3-bdc)(DMF)(HO)] , is a new Cd-Na heterobimetallic coordination polymer. The asymmetric unit consists of one Cd atom, two Na atoms, two 1,3-bdc ligands, two coordinated water mol-ecules and one coordinated DMF mol-ecule. The Cd atom exhibits a seven-coordinate geometry, while the Na atoms can be considered to be penta-coordinate.

A novel one-dimensional double-chain-like Zn coordination polymer: poly[bis(1-benzyl-1H-imidazole-κN)tris(μ-cyanido-κC:N)(cyanido-κC)disilver(I)zinc(II)].

One of most interesting systems of coordination polymers constructed from the first-row transition metals is the porous Zn coordination polymer system, but the numbers of such polymers containing N-donor linkers are still limited. The title double-chain-like Zn coordination polymer, [AgZn(CN)(CHN)], presents a one-dimensional linear coordination polymer structure in which Zn ions are linked by bridging anionic dicyanidoargentate(I) units along the crystallographic b axis and each Zn ion is additionally coordinated by a terminal dicyanidoargentate(I) unit and two terminal 1-benzyl-1H-imidazole (BZI) ligands, giving a five-coordinated Zn ion. Interestingly, there are strong intermolecular Ag.

Crystal structure of a two-dimensional grid-type iron(II) coordination polymer: poly[[di-aqua-tetra-μ-cyanido-diargentate(I)iron(II)] trans-1,2-bis(pyridin-2-yl)ethyl-ene disolvate].

In the title compound, {[Ag2Fe(CN)4(H2O)2]·2C12H10N2} n , the asymmetric unit contains one Fe(II) cation, two water mol-ecules, two di-cyanido-argentate(I) anions and two uncoordinating 1,2-bis-(pyridin-2-yl)ethyl-ene (2,2'-bpe) mol-ecules. Each Fe(II) atom is six-coordinated in a nearly regular octa-hedral geometry by four N atoms from di-cyanido-argentate(I) bridges and two coordinating water mol-ecules. The Fe(II) atoms are bridged by di-cyanido-argentate(I) units to give a two-dimensional layer with square-grid spaces.

Drastic effect of lattice propionitrile molecules on the spin-transition temperature of a 2,2'-dipyridylamino/s-triazine-based iron(II) complex.

Reaction of iron(II) selenocyanate (obtained from Fe(ClO4)2 and KNCSe) with 2-(N,N-bis(2-pyridyl)amino)-4,6-bis(pentafluorophenoxy)-(1,3,5)triazine (L1(F)) in propionitrile produces the compound [Fe(L1(F))2(NCSe)2]·2CH3CH2CN (1(NCSe)·2PrCN), which shows spin-crossover (SCO) properties characterized by a T(1/2) of 283 K and a ΔT80 (i.e., temperature range within which 80% of the transition considered occurs) of about 65 K.

Di-μ-acetato-κ(4) O:O'-bis-[(1,10-phenanthroline-κ(2) N,N')(tri-fluoro-methane-sulfonato-κO)copper(II)].

The complete molecule of the title compound, [Cu2(C2H3O2)2(CF3O3S)2(C12H8N2)2], is completed by the application of a twofold rotation and comprises two Cu(II) ions, each of which is penta-coordinated by two N atoms from a bidentate 1,10-phenanthroline (phen) ligand, two O atoms from acetate ligands and an O atom from a tri-fluoro-methane-sulfonate anion, forming a (4 + 1) distorted square-pyramidal coordination geometry. The Cu(II) ions are connected by two acetate bridges in a syn-syn configuration. The F atoms of the tri-fluoro-methane-sulfonate ligands are disordered, with site-occupation factors of 70 and 30.

The heterometallic cadmium-silver complex cis-bis[dicyanidoargentato(I)-κN]bis(5,5'-dimethyl-2,2'-bipyridyl-κ(2)N,N')cadmium(II) monohydrate.

In the title complex, [Ag2Cd(CN)4(C12H12N2)2]·H2O or cis-[Cd{Ag(CN)2}2(5,5'-dmbpy)2]·H2O, where 5,5'-dmbpy is 5,5'-dimethyl-2,2'-bipyridyl, the asymmetric unit consists of a discrete neutral [Cd{Ag(CN)2}2(5,5'-dmbpy)2] unit and a solvent water molecule. The Cd(II) cation is coordinated by two bidentate chelate 5,5'-dmbpy ligands and two monodentate [Ag(I)(CN)2](-) anions, which are in a cis arrangement around the Cd(II) cation, leading to an octahedral CdN6 geometry. The overall structure is stabilized by a combination of intermolecular hydrogen bonding, and Ag(I)···Ag(I) and π-π interactions, forming a three-dimensional supramolecular network.

Influence of supramolecular bonding contacts on the spin crossover behaviour of iron(II) complexes from 2,2'-dipyridylamino/s-triazine ligands.

Reactions of the related ligands 2-(N,N-bis(2-pyridyl)amino)-4,6-bis(phenoxy)-(1,3,5)triazine (L1) and 2-(N,N-bis(2-pyridyl)amino)-4,6-bis(pentafluorophenoxy)-(1,3,5)triazine (L1(F)) with iron(II) thiocyanate produced two spin-crossover coordination compounds with distinct cooperative behaviours. trans-[Fe(L1)2(NCS)2]·2CH2Cl2 (1) displays a very gradual transition centred at T½ = 233 K, characterized by a ΔT80 (namely the temperature range within which 80% of the transition considered occurs) of 90 K, while that of fluorinated trans-[Fe(L1(F))2(NCS)2]·2CH3CN (3) is significantly more abrupt (and centred at T½ = 238 K), with a ΔT80 of 50 K, resulting from supramolecular contacts induced by the fluorinated phenol groups. The coordination compound equivalent to 1 with selenocyanate anions, namely trans-[Fe(L1)2(NCSe)2]·4CH2Cl2·4CH3OH (2), also exhibits SCO properties centred at T½ = 238 K, but the transition is very gradual (ΔT80 = 150 K).

Hetero triply-bridged dinuclear copper(II) compounds with ferromagnetic coupling: a challenge for current density functionals.

Seven new hetero triply-bridged dinuclear Cu(II) compounds have been synthesized and characterized corresponding to a series with general formula [Cu(2)(L)(2)(μ-OH)(μ-OH(2))(μ-O(2)CR)]X(2) (where L = bpy = 2,2'-bipyridine, 4,4'-dmbpy = 4,4'-dimethyl-2,2'-bipyridine and 5,5'-dmbpy = 5,5'-dimethyl-2,2'-bipyridine; R = H for formate, CH(3) for acetate, CH(2)CH(3) for propionate and C(CH(3))(3) for trimethylacetate and X = CF(3)SO(3)(-) and ClO(4)(-)). All compounds exhibit ferromagnetic behavior with the experimental J values derived from magnetic susceptibility measurements being in the 73-104 cm(-1) range. The overall qualitative behavior is reproduced by state of the art density functional theory based methods.

New series of triply bridged dinuclear Cu(II) compounds: synthesis, crystal structure, magnetic properties, and theoretical study.

Five new triply bridged dinuclear Cu(II) compounds have been synthesized, and their magnetic properties have been measured and characterized. The magnetic coupling constants (J) of these compounds plus a previously structurally characterized compound of the same type have been derived by appropriate fitting of the experimentally measured molar susceptibility variation with the temperature. Two of the compounds are ferromagnetically coupled, and three are antiferromagnetically coupled with J values in the [+150, -40] cm(-1) range.

Toward the design of ferromagnetic molecular complexes: magnetostructural correlations in ferromagnetic triply bridged dinuclear Cu(II) compounds containing carboxylato and hydroxo bridges.

In the present work we present a comprehensive study of the magneto-structural correlations of a series of ferromagnetic triply heterobridged Cu(II) dinuclear compounds containing [Cu(2)(mu-O(2)CR)(mu-OH)(mu-X)(L)(2)](2+) ions (where X = OH(2), Cl(-), OMe(-) and L = bpy, phen, dpyam) which have the particularity of being all ferromagnetic. The present theoretical study, based on hybrid density functional theory (DFT) calculations, leads to strong conclusions about the role of the pentacoordination geometry of the Cu(II) ions (square base pyramidal (SP) or trigonal bipyramidal (TBP) coordination) and the nature of the third bridging ligand in determining the final value of the magnetic coupling constants in this series of compounds. These investigations point toward the existence of a maximum value for the ferromagnetic interaction and may offer some useful information to synthetic chemists aiming at obtaining new compounds with enhanced ferromagnetism.