A novel one-dimensional thiocyanate-bridged cobalt(III) complex: synthesis, crystal structure characterization and Hirshfeld surface analysis.

A new one-dimensional thiocyanate-bridged cobalt(III) Schiff base complex, namely, catena-poly[[[4-bromo-2-((Z)-{[2-(thiophen-2-yl)ethyl]imino}methyl)phenolato-κ2N,O]cobalt(III)]-µ-thiocyanato-κ2N:S], [Co(SCN)(C13H11BrNOS)2]n or [Co(µ1,3-SCN)L2]n (1), where HL is 4-bromo-2-((Z)-{[2-(thiophene-2-yl)ethyl]imino}methyl)phenol, a bidentate Schiff base prepared from the condensation reaction of 5-bromosalicylaldehyde and 2-(thiophen-2-yl)ethylamine, has been synthesized by stirring Co(ClO4)2·6H2O, the Schiff base HL and ammonium thiocyanate (in a 1:2:1 molar ratio) in ethanol medium. The complex was characterized by FT-IR, electronic spectra and single-crystal X-ray diffraction (SC-XRD) studies. The SC-XRD data suggest that the compound crystallizes in the orthorhombic space group Pca21. The CoIII ion in 1 adopts a distorted octahedral geometry, the metal sites being six-coordinated by one thiocyanate N atom and one thiocyanate S atom in apical positions, and by two imine N atoms and two phenolate O atoms from two anionic L- ligands which form the basal plane. The thiocyanate ligand acts as a µ-1,3 bridge, joining neighbouring CoIII atoms and forming a uniform zigzag one-dimensional polymeric chain. The crystallographic data were also used in the Hirshfeld surface (HS) analysis, which aimed to investigate the nature and quantitative significance of any noncovalent intermolecular interactions inside the crystal lattice. The crystal void parameters have also been computed and show the molecules to be tightly packed.

A trinuclear Zn (II) schiff base dicyanamide complex attenuates bacterial biofilm formation by ROS generation and membrane damage and exhibits anticancer activity.

A trinuclear Zn (II) complex, [(ZnL{N(CN)2})2Zn], termed complex 1 has been synthesized by the reaction of an aqueous solution of sodium dicyanamide to the methanolic solution of Zn (CH3COO)2, 2H2O and corresponding Schiff base (H2L) which is derived from 1:2 condensation of 1, 4 butane diamine with 3-ethoxy salicylaldehyde. Complex 1 is characterized by elemental analysis, IR, UV and Single X-ray diffraction study. Drug resistance is a growing global public health concern that has prompted researchers to look into advanced alternative treatment modalities. In this context, complex 1 has shown promising antibacterial and antibiofilm efficacy against gram-positive Staphylococcus aureus and Methicillin-resistant Staphylococcus aureus strains. Complex 1 attenuated Staphylococcal biofilm formation by reducing several virulence factors including the formation of extracellular polysaccharide matrix, slime, haemolysin, staphyloxanthin, auto-aggregation, cell surface hydrophobicity, and motility. Notably, complex 1 mechanistically potentiated Reactive Oxygen Species (ROS) generation within the bacterial cells, leading to the damage of bacterial cell membrane followed by DNA leakage and thereby impeding the growth of Staphylococcus aureus. Furthermore, complex 1 significantly exhibited anticancer activity by reducing the growth of prostate adenocarcinoma cells. It obstructed the migration of cancer cells by potentiating apoptosis and arresting the cell cycle at the G2/M phase. In summary, complex 1 could act as a potent candidate for the generation of novel antibacterial, antibiofilm as well as anticancer treatment regimens for the management of drug-resistant biofilm-mediated Staphylococcus aureus infection and lethal prostate malignancy.

A mononuclear N,N,N,O donor schiff base Cu(II) complex inhibits bacterial biofilm formation and promotes apoptosis and cell cycle arrest in prostate cancer cells.

In this work, we report a distorted square pyramidal mononuclear copper(II) complex [Cu(L)(NCS)] (1) which was obtained by the reaction of the aqueous solution of ammonium thiocyanate to a methanolic solution of copper nitrate trihydrate and corresponding Schiff-base ligands. Schiff bases, HL (C12H19N3O) act as a tetradentate Schiff base, derived from 1:1 condensation of o-hydroxyacetophenone and diethylenetriamine. The synthesized complex has been successfully characterized based on elemental analysis and Infrared (IR) spectroscopy. The structure of complex 1 was confirmed by single-crystal X-ray diffraction study. In our study, we investigated synthesis, structural characterization, antimicrobial, anti-biofilm, and anti-cancer activity, and plausible mechanism of action of a novel mononuclear copper(II) schiff base complex. Increasing microbial resistance to several commercially available or traditional antimicrobial compounds has become a major global health concern at present time. The mononuclear copper(II) complex exhibited potential antibacterial activity against two strains of the gram-negative pathogen Pseudomonas aeruginosa. The copper compound dependent damage of bacterial cell membrane and inhibition of bacterial biofilm formation were also identified. Moreover, complex 1 inhibited prostate cancer cell growth, and migration by inducing apoptosis and arresting the cell cycle at the G2/M phase. Based on the results, we are suggesting our novel mononuclear copper(II) compound as a potential candidate for the development of new antibacterial and anti-cancer drugs.

Strategic Synthesis of Heptacoordinated FeIII Bifunctional Complexes for Efficient Water Electrolysis.

In this research, highly efficient heterogeneous bifunctional (BF) electrocatalysts (ECs) have been strategically designed by Fe coordination (CR ) complexes, [Fe2 L2 (H2 O)2 Cl2 ] (C1) and [Fe2 L2 (H2 O)2 (SO4 )].2(CH4 O) (C2) where the high seven CR number synergistically modifies the electronic environment of the Fe centre for facilitation of H2 O electrolysis. The electronic status of Fe and its adjacent atomic sites have been further modified by the replacement of -Cl- in C1 by -SO4 2- in C2. Interestingly, compared to C1, the O-S-O bridged C2 reveals superior BF activity with extremely low overpotential (η) at 10 mA cm-2 (140 mVOER , 62 mVHER ) and small Tafel slope (120.9 mV dec-1 OER , 45.8 mV dec-1 HER ). Additionally, C2 also facilitates a high-performance alkaline H2 O electrolyzer with cell voltage of 1.54 V at 10 mA cm-2 and exhibits remarkable long-term stability. Thus, exploration of the intrinsic properties of metal-organic framework (MOF)-based ECs opens up a new approach to the rational design of a wide range of molecular catalysts.

Bis(CBT)palladium(II) Derivatives (CBT = m-carborane-1-thiolate): Synthesis, Molecular Structure, and Physicochemical Properties of cis-[(bipy)Pd(CBT)2] and trans-[(py)2Pd(CBT)2].

The new synthesized PdII complex cis-[(bipy)Pd(CBT)2] (bipy = 2,2'-bipyridyl; CBT = m-carborane-1-thiolate anion), which is a potential BNCT (boron neutron capture therapy) agent and of structure elucidated by single-crystal X-ray work, has been studied by infrared (IR) and ultraviolet-visible light (UV-vis) spectra and its properties compared with those of the previously reported and also the structurally characterized analogue trans-[(py)2Pd(CBT)2]. This trans species, prepared via a direct method, was previously isolated from a pyridine solution, consequent to the occurring releasing of the external Pd(CBT)2 moieties of the porphyrazine macrocycle [{Pd(CBT)2}4LZn]·xH2O (L = tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazinato anion), which is an active photosensitizer in photodynamic therapy (PDT) and a potential bimodal PDT/BNCT agent. The UV-vis spectral behavior of both cis and trans species in CHCl3 solution and in the gas phase has been examined in detail by density functional theory (DFT) and time-dependent density functional theory (TDDFT) studies devoted to explain their distinct behavior observed in the region of 400-500 nm, as determined by the presence in the cis structure of a vicinal arrangement of the two CBT groups, an ensemble of results closely similar to those observed for the macrocycles [{Pd(CBT)2}4LM]·xH2O (M = MgII(H2O), ZnII, PdII). It has also been experimentally proved the tendency of the cis isomer in CHCl3/pyridine solution to be changed to the respective trans analogue, with conversion occurring in two steps, as interpreted by detailed DFT studies.

Palladium(II) and Platinum(II) Mononuclear Complexes and Tendency to Undergo Dehydrogenation of the Multiple N-Donor Ligand Di-(2-pyridyl)dihydropyrazine.

The already known di(2-pyridyl)dihydropyrazine (dhdpp) was prepared and isolated also in the form of a bis-hydrated species, i.e., dhdpp·2H2O. As established by X-ray work, a small amount of single crystals of di(2-pyridyl)-pyrazine (dpp) was also obtained from the mother liquors, this testifying the possibility of a dehydrogenation process dhdpp → dpp in the absence of a catalyst. Using dhdpp as a ligand, mononuclear metal derivatives of formula [(dhdpp)MCl2]·xH2O (M = PdII, PtII) were obtained as stable-to-air solids, studied by X-ray powder, IR, UV-visible, and 1H NMR spectra, and proved to exhibit a N2MCl2 coordination site involving one pyridine and one pyrazine N atom ("py-pyz" coordination). An interesting relationship has been established in terms of the observed types of coordination with the analogs of di(2-pyridyl)-pyrazine (dpp) formulated as [(dpp)MCl2]·3H2O, proved also by 1H NMR spectra to exhibit the "py-pyz" mode of coordination. Attempts to isolate from the reaction of dhdpp with Pd(OAc)2 the corresponding mononuclear derivatives were shown to lead, as definitely supported by 1H NMR spectral data and crystallographic work, to the exclusive formation of the corresponding dpp complex [(dpp)Pd(OAc)2]·5H2O ("py-pyz" coordination site), this proving the tendency of dhdpp to generate dpp under different reaction conditions. The promoted conversion of dhdpp into dpp in the complex was examined by sequential NMR analysis and established to be determined by Pd(OAc)2 which plays the role of catalyst. The new salt-like species [(CH3)(dhdpp)PdI2](I)·7H2O, prepared starting from [(dhdpp)PdCl2] in its reaction with CH3I, allowed the separation from the mother liquors of small brown crystals identified on the basis of X-ray analysis as the already known complex of formula [(dpp)PdI2] ("py-py" coordination), this result once again outlining the tendency of dhdpp to be dehydrogenated to dpp.

Tetra-2,3-pyrazinoporphyrazines with Peripherally Appended Pyridine Rings. 19. Pentanuclear Octa(2-pyridyl)tetrapyrazinoporphyrazines Carrying Externally Carboranthiolate Groups: Physicochemical Properties and Potentialities as Anticancer Drugs.

New pentanuclear porphyrazine complexes of formula [{Pd(CBT)2}4LM]· xH2O (L = tetrakis-2,3-[5,6-di(2-pyridyl)pyrazino]porphyrazinato anion, CBT = m-carborane-1-thiolate, and M = MgII(H2O), ZnII, PdII) were prepared in good yield as dark green hydrated amorphous solids by reaction of the respective pentanuclear species [(PdCl2)4LM] with m-carboran-1-thiol in CH3CN. Physicochemical characterization of the new species was carried out by elemental and thermogravimetric analysis along with IR and 1H/13C NMR measurements. UV-vis spectral characterization performed in DMSO, DMF, and pyridine solution provided information about the stability of the new homo/heteropentanuclear species and their tendency to undergo detachment of the peripheral Pd(CBT)2 groups. The data from NMR, UV-vis, and electrochemical experiments indicate that external coordination of the Pd(CBT)2 units to the mononuclear [LM] species affects only slightly the π electron distribution within the internal macrocyclic choromophore. The Pd(CBT)2 units are released in pyridine solution and in the case of the ZnII complex [{Pd(CBT)2}4LZn] give rise to a finely crystalline light-yellow solid identified by single-crystal X-ray work as the trans isomer of the bispyridine adduct [py2(CBT)2Pd]. The new pentanuclear macrocyclic complexes behave in DMF solution as active photosensitizers for singlet oxygen production, 1O2, the cytotoxic agent in anticancer photodynamic therapy, and have larger quantum yield values (ΦΔ = 0.6-0.7) than those found on average for the related tetrapyrazinoporphyrazine analogs (ΦΔ = 0.4-0.6). The presence of the CBT groups in the currently investigated complexes opens up the possibility for their use in boron neutron capture therapy, leading potentially to new bimodal anticancer curative drugs.

Tris-chelated complexes of nickel(II) with bipyridine derivatives: DNA binding and cleavage, BSA binding, molecular docking, and cytotoxicity.

Two nickel(II) complexes with substituted bipyridine ligand of the type [Ni(NN)3](ClO4)2, where NN is 4,4'-dimethyl-2,2'-bipyridine (dimethylbpy) (1) and 4,4'-dimethoxy-2,2'-bipyridine (dimethoxybpy) (2), have been synthesized, characterized, and their interaction with DNA and bovine serum albumin (BSA) studied by different physical methods. X-ray crystal structure of 1 shows a six-coordinate complex in a distorted octahedral geometry. DNA-binding studies of 1 and 2 reveal that both complexes sit in DNA groove and then interact with neighboring nucleotides differently; 2 undergoes a partial intercalation. This is supported by molecular-docking studies, where hydrophobic interactions are apparent between 1 and DNA as compared to hydrogen bonding, hydrophobic, and π-π interactions between 2 and DNA minor groove. Moreover, the two complexes exhibit oxidative cleavage of supercoiled plasmid DNA in the presence of hydrogen peroxide as an activator in the order of 1 > 2. In terms of interaction with BSA, the results of spectroscopic methods and molecular docking show that 1 binds with BSA only via hydrophobic contacts while 2 interacts through hydrophobic and hydrogen bonding. It has been extensively demonstrated that the nature of the methyl- and methoxy-groups in ligands is a strong determinant of the bioactivity of nickel(II) complexes. This may justify the above differences in biomolecular interactions. In addition, the in vitro cytotoxicity of the complexes on human carcinoma cells lines (MCF-7, HT-29, and U-87) has been examined by MTT assay. According to our observations, 1 and 2 display cytotoxicity activity against selected cell lines. Communicated by Ramaswamy H. Sarma.

A Cd(ii) based metal organic framework: a photosensitive current conductor.

A novel cadmium(ii) based metal organic framework, [Cd(3-bpd)(SCN)2]n () where 3-bpd = 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene has been synthesized and characterized by elemental analysis, various spectroscopic techniques, TGA and single crystal X-ray diffraction analysis. X-ray analysis shows the formation of an undulated polymeric two-dimensional network parallel to the (0 -1 1) plane. Current conduction properties of have been explored in the dark and in the presence of light. The study shows that current conduction of the complex increases with the increase of the incident light intensity. On progression of intensity of glancing radiation the photosensitivity of has been increased. The time dependent light response on charge carrier conduction reveals that complex may uncover new ground to explore in optoelectronic switching applications.

Organotin(IV) based anti-HCV drugs: synthesis, characterization and biochemical activity.

Three new organotin(iv) carboxylates () of 3,5-dimethylbenzoate, have been synthesized and characterized by elemental analysis, FT-IR, multinuclear NMR ((1)H, (13)C and (119)Sn), mass spectrometry and single crystal X-ray structural analysis. Crystallographic data show that in compounds and , the geometry at the central Sn atom is skew-trapezoidal bipyramidal while compound displays a distorted trigonal bipyramidal coordination geometry. In the case of compounds and , the asymmetric chelating mode of the carboxylate groups is reflected in the unequal C-O bond distances, those observed for the O1 and O3 oxygen atoms being significantly longer than those found in the O2 and O4 atoms. In the case of compound , the carboxylate groups bridge asymmetrically adjacent tin atoms in an anti-syn mode generating polymeric zigzag chains running parallel to the crystallographic c-axis. The compounds were screened for anti-HCV (hepatitis C virus) potency by the Gaussia luciferase assay using infected Huh 7.5 cells (human hepatocellular cell). Structure-activity relationship studies led to the identification of dibutyltin(iv)bis(3,5-dimethylbenzoic acid) (compound ) as a potent HCV inhibitor, with log IC50 values equal to 0.69 nM in the cell-based assay. Compound was further subjected to quantitative analysis using real-time PCR assays and viral RNA count vs. drug concentration confirmed the Gaussia luciferase assay results. The HCV RNA targeting mode of the compounds () was confirmed by a compound-DNA interaction study. The compounds ()-DNA interactions were investigated by UV-vis spectroscopy and viscometry. The hypochromic effect in spectroscopy evidenced an intercalative mode of interaction with the binding affinity in the order of > > .

Crystal structure of zwitterionic 3-(2-hy-droxy-2-phospho-nato-2-phosphono-eth-yl)imidazo[1,2-a]pyridin-1-ium monohydrate (minodronic acid monohydrate): a redetermination.

In a previous study, the X-ray structure of the title compound, C9H12N2O7P2·H2O, was reported [Takeuchi et al., (1998 ▶). Chem. Pharm. Bull. 46, 1703-1709], but neither atomic coordinates nor details of the geometry were published. The structure has been redetermined with high precision as its detailed knowledge is essential to elucidate the presumed polymorphism of minodronic acid monohydrate at room temperature. The mol-ecule crystallizes in a zwitterionic form with cationic imidazolium[1,2a]pyridine and anionic phospho-nate groups. The dihedral angle formed by the planes of the pyridine and imidazole rings is 3.55 (9)°. A short intra-molecular C-H⋯O contact is present. In the crystal, mol-ecules are linked by O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds and π-π inter-actions [centroid-to-centroid distance = 3.5822 (11) Å], forming a three-dimensional structure.

Reversible switching of electronic ground state in a pentacoordinated Cu(II) 1D cationic polymer and structural diversity.

Two copper(II) polymeric complexes {[Cu(HPymat)(MeOH)](NO3)}n (1) and {[Cu4(Pymab)4(H2O)4](NO3)4} (2) were synthesized with the carboxylate-containing Schiff-base ligands HPymat(-) and Pymab(-) [H2Pymat = (E)-2-(1-(pyridin-2-yl)methyleneamino)terephthalic acid, HPymab = (E)-2-((pyridine-2-yl)methyleneamino)benzoic acid]. Complex 1 is a one-dimensional Cu(II) cationic polymeric complex containing free protonated carboxylic groups and nitrate anions as counterions. Complex 2 is a zero-dimensional tetranuclear cationic Cu(II) complex containing nitrate anions as counterions. Complex 1 shows rhombic electron paramagnetic resonance (EPR) spectra in the solid state at room temperature (RT) and 77 K and tetragonal EPR spectra in dimethyl sulfoxide (DMSO) and dimethylformamide (DMF) and "inverse" EPR spectrum in CH3CN. Complex 2 shows rhombic EPR spectra in the solid state at RT and 77 K. But complex 2 shows tetragonal spectra in DMSO, DMF, and CH3CN. Thermogravimetric analysis was also performed for both complexes 1 and 2. Mean-square displacement amplitude analysis was carried out to detect librational disorder along the metal-ligand bonds in crystal structures.

Relevant and unprecedented C-H/σ supramolecular interactions involving σ-aromatic M2X2 cores.

A novel type of C-H/σ supramolecular interaction involving σ-aromatic M2X2 (M = Cu, Hg; X = Cl, Br, I, S) cores is reported for the first time. Three new polymeric coordination copper complexes, {[Cu(µ-Cl)(Cl)(µ-L)]2}n (1), {[Cu(µ-I)(µ-L)]2}n (2) and [Cu(Br)2(µ-L)(CH3CN)2]2 (3), have been synthesized with the organic ligand α,ω-bis(benzotriazoloxy)propane system (L) and halides as counterions. A very interesting C-H/σ supramolecular interaction has been observed in the solid state structure of compound 2, similar to a C-Hπ interaction, which has been confirmed by Bader's "atoms-in-molecules" AIM analysis. The Nucleus Independent Chemical Shift (NICs) method was used to evaluate the aromatic character of the different cores in this study. The influence of the nature of the metal ions, bridging atoms, oxidation states, and coordination environments around the metal centers on the strength of the aromaticity of the M2X2 cores was theoretically analyzed and explained. The binding ability of the 1-alkoxy-1,2,3-benzotriazole ring to establish π-π and C-H/π interactions and how its coordination to Cu(I) and Cu(II) ions affects the strength of the aforementioned interactions have been discussed. The electron deficient triazole ring and its π-acidity increases upon coordination of the Cu ion, leading to the formation of a lone pair (lp)-π interaction involving the five-membered ring of the ligand, which has also been analyzed. We have also analyzed the C-H/σ interactions of previously reported X-ray crystal structures of different coordination polymers based on a binuclear copper(I) complex and 2,3-dimethylpyrazine, dithioethers, and benzotriazol-1-yl-based pyridyl units as ligands using I- as a counter-ion. Complex 1 shows antiferromagnetic behavior with a magnetic coupling constant of J = -7.9 cm(-1). Moreover, photoluminescence and TGA studies of the complexes were also carried out.

Reactions of nitric oxide and nitrogen dioxide with coenzyme Q: involvement of the isoprenic chain.

The formation of a di-tert-alkyl nitroxide has been observed by Electron Spin Resonance during the exposure of coenzyme CoQ(10), in both the oxidized and reduced forms, to nitrogen dioxide (˙NO(2)) or to nitric oxide (˙NO) in the presence of oxygen. The same kind of nitroxide has been observed also with CoQ(1), CoQ(3) or with 1-phenyl-3-methyl-2-butene, chosen as model compounds. In all cases, the formation of the nitroxide may be justified only by admitting the involvement of the isoprenic chain of the coenzymes and in particular the addition of ˙NO(2) to the double bond. A mechanism which accounts for the formation of the nitroxide as well as the other compounds observed in the reactions is proposed and confirmed by a spectroscopic investigation (FT-IR, (1)H NMR, X-ray analysis) and by ESI-MS.

Framework solids based on copper(II) halides (Cl/Br) and methylene-bridged bis(1-hydroxybenzotriazole): synthesis, crystal structures, magneto-structural correlation, and density functional theory (DFT) studies.

A methylene-bridged 1-hydroxybenzotriazole derived ligand L [L = 1, 3-bis(benzotriazol-1-yl)-1,3-dioxapropane] has been synthesized and characterized by spectroscopic and structural methods. Reaction of L with two different copper(II) halides [CuX(2); X = Br, Cl] in an identical condition yields two different compounds of similar compositions, {[Cu(µ-Br)(Br)(µ-L)](2)}(n)·2nH(2)O (1) and {[Cu(µ-Cl)(Cl)(µ-L)](2)}(n)·2nH(2)O (2), both being characterized by various physicochemical techniques. Single crystal X-ray studies reveal that they appear as 2D coordination polymers with similar bridging fashion of L. Low temperature magnetic susceptibility measurements reveal antiferromagnetic and ferromagnetic behaviors for 1 and 2 with magnetic coupling constants J = -15.2 and +1.7 cm(-1), which are in a reasonable agreement with their calculated values (J = -9.79 and +0.68 cm(-1) respectively, for 1 and 2). The role of bridging halides in the structure and magnetic properties of the complexes are investigated, and a possible magneto-structural correlation has been established. Influence of spin density of bridging halides on the magnitude of coupling constants has been discussed with the help of density functional theory (DFT) calculations.

A novel mixed valent Cu(II)-Cu(I) 2D framework made of a hydrazone and µ-SCN bridged metallacyclic loops cross-linked by µ3-SCN chains.

A mixed valent copper complex [Cu(II)Cu(I)(L)(µ-SCN)(µ(3)-SCN)](n) (LH = N'-((pyridin-2-yl)methylene)acetohydrazide) has been synthesized and characterized. It is a unique example of a 2D mixed valent Cu(II)-Cu(I) interlinked molecular assembly with a very unusual bridging property of the hydrazone ligand. An extraordinary in situ partial Cu(II)→ Cu(I) reduction is observed in this system at room temperature.

Structural flexibility and role of vicinal 2-thienyl rings in 2,3-dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)2Th2Pyz], its palladium(II) complex [(CN)2Th2Pyz(PdCl2)2], and the related pentametallic pyrazinoporphyrazines [(PdCl2)4Th8TPyzPzM] (M = Mg(II)(H2O), Zn(II)).

The solid state and solution structure of 2,3-dicyano-5,6-di(2-thienyl)-1,4-pyrazine, [(CN)(2)Th(2)Pyz], and its Pd(II) derivative, [(CN)(2)Th(2)Pyz(PdCl(2))(2)]·H(2)O, formed by reaction of [(CN)(2)Th(2)Pyz] with [(C(6)H(5)CN)(2)PdCl(2)] were characterized by X-ray, UV-visible, (1)H and (13)C NMR, and extended X-ray absorption fine structure (EXAFS) spectral measurements. The X-ray crystal structure of [(CN)(2)Th(2)Pyz] shows the presence of one thienyl ring positioned orthogonal to the rest of the molecule, with the two vicinal thienyl rings lying orthogonal to each other in a rare arrangement. NMR studies of [(CN)(2)Th(2)Pyz] in the solid state and in solutions of dimethylformamide or dimethyl sulfoxide confirm a nonequivalence of the thienyl rings in the solid state and also in solution. EXAFS results indicate that two distinct Pd(II) coordination sites are formed at the di(2-thienyl)pyrazino moiety of [(CN)(2)Th(2)Pyz(PdCl(2))(2)]·H(2)O, with identical Pd-N(pyz) (2.03(3) Å) and Pd-Cl (2.36(3) Å) bond lengths but with different Pd-S1 (2.25(4) Å) and Pd-S2 (3.21(5) Å) bond distances in an overall asymmetric molecular framework. Density functional theory (DFT) and time-dependent DFT (TDDFT) theoretical studies also provide information about the structure and spectral behavior of the precursor and its metalated Pd(II) derivative. (1)H/(13)C NMR and UV-visible spectral measurements were also carried out on two heteropentametallic porphyrazine macrocycles which were prepared by a reaction of PdCl(2) with [Th(8)TPyzPzM] where Th(8)TPyzPz = tetrakis-2,3-[5,6-di-(2-thienyl)-pyrazino]porphyrazinato dianion and M = Mg(II)(H(2)O) or Zn(II). Spectroscopic data on the newly synthesized [(PdCl(2))(4)Th(8)TPyzPzM] compounds suggest that the binding of PdCl(2) involves coordination sites of the type S(2(th))PdCl(2) with the two thienyl rings of each di(2-thienyl)pyrazino fragment bound to Pd(II) in an equivalent manner ("th-th" coordination). This is similar to what was found for the corresponding octapyridinated analogues ("py-py" coordination).

2-(Naphthalen-1-yl-amino)-cyclo-hexa-nol.

The title compound, C(16)H(19)NO, was synthesized under solvent-free conditions by reaction of 7-oxa-bicyclo-[4.1.0]heptane and naphthalen-1-amine in the presence of Ca(CF(3)COO)(2) as catalyst. The cyclo-hexane ring adopts a chair conformation. In the crystal, mol-ecules are linked by inter-molecular N-H⋯O hydrogen bonds and C-H⋯π inter-actions into chains parallel to the c axis.

(5R)-5-[(1R)-2,2-Dichloro-1-methyl-cyclo-prop-yl]-2-methyl-cyclo-hex-2-en-1-one.

The title compound, C(11)H(14)Cl(2)O, was synthesized by the reaction of a dichloro-methane solution of (R)-carvone and potassium tert-butano-late in the presence of a catalytic amount of benzyl-triethyl-ammonium chloride in chloro-form. The cyclo-hexene ring adopts a half-boat conformation. The cyclo-propyl ring is unsymmetrical, the shortest C-C bond being distal to the alkyl-substituted C atom. The crystal packing is stabilized only by van der Waals inter-actions.

(Z)-4-(2-Naphthyl-amino)-pent-3-en-2-one.

The title compound, C(15)H(15)NO, which was synthesized under solvent-free conditions by the reaction of acetoacetone and 2-naphthyl-amine, adopts a Z conformation about the C=C bond. The enamine-ketone fragment is approximately planar [maximum deviation = 0.026 (3) Å] and forms a dihedral angle of 39.78 (3)° with the naphthalene ring system. An intra-molecular N-H⋯O hydrogen bond is observed.