2-[2-(3-Chloro­phen­yl)hydrazinyl­idene]-1,3-diphenyl­propane-1,3-dione

The mol­ecular structure of the title compound, C21H15ClN2O2, features one strong intra­molecular N—H⋯O resonance-assisted hydrogen bond (RAHB). In the crystal, mol­ecules form inversion-related dimers via pairs of weak inter­molecular N—H⋯O contacts. These dimers are further stabilized via three weak C—H⋯O contacts, developing the three-dimensional structure

Synthesis and characterization of palladacyclopentadiene complexes with N-heterocyclic carbene ligands

New palladacyclopentadiene compounds containing different chelate NHC-thioether and NHC-pyridine ligands have been prepared by transfer of the functionalized carbenes from the respective silver complexes to the polymeric precursors [PdC-COOR)4]n (R = Me, t-Bu). Their dynamic behaviour in solution was discussed and the solid-structure of 2c was determined by X-ray crystallography. The treatment of [Pd(C-COOCH3)4]n with two equivalents of the carbene silver complexes led to the (NHC)2Pd(C4-COOCH3)4 derivatives (3cei), a new class of compounds with only PdeC bonds. A serious limitation to this synthetic procedure is an excessive steric crowding around the metal centre. The complexes 3 are present in solution as a mixture of two atropoisomers, due to restricted rotation around the CarbeneePd bond. The kinetics of equilibration between the two configurational isomers was studied for complex 3c, which was also structurally defined by X-ray crystallography (anti isomer). Finally a synthetic protocol was set up for the synthesis of mixed NHC-Phosphine and NHC-Isocyanide palladacyclopentadiene complexes. In this procedure the order of addition of the reactants is of great importanc

2-[2-(4-Bromo­phen­yl)hydrazinyl­idene]-1,3-diphenyl­propane-1,3-dione

The conformation of the title mol­ecule, C21H15BrN2O2, is stabilized by a weak intra­molecular C—H⋯N hydrogen bond and a strong resonance-assisted N—H⋯O intra­molecular hydrogen bond. In the crystal, the mol­ecules are linked by weak inter­molecular C—H⋯O inter­actions, forming zigzag chains along the b axis

Brainstem Reflexes in Idiopathic Cervical Dystonia: Does Medullary Dysfunction Play a Role?

Background: Neurophysiological markers in dystonia have so far not been sistematically applied in clinical practice due to limited reproducibility of results and low correlations with clinical findings. Exceptions might be represented by the blink reflex (BR), including its recovery cycle (BRRC) and the trigemino-cervical reflex (TCR) which, compared to other neurophysiological methods, have shown more consistent alterations in cervical dystonia (CD). However, a comparison between the two techniques, and their possible correlation with disease symptoms, have not been thoroughly investigated. Objectives: To assess the role of BR, BRCC and TCR in the pathophysiology of idiopathic cervical dystonia. Methods: Fourteen patients and 14 age-matched healthy controls (HC) were recruited. Neurophysiological outcome measures included latency of R1 and R2 components of the BR, R2 amplitude, BRRC, latency and amplitude of P19/N31 complex of TCR. Clinical and demographic features of patients were also collected, including age at disease onset, disease duration, presence of tremor, sensory trick and pain. The Toronto Western Spasmodic Torticollis Rating Scale was used to characterize dystonia. Results: Compared to HC, CD patients showed increased latency of the BR R2 and decreased suppression of the BRRC. They also showed increased latency of the P19 and decreased amplitude of P19/N31 complex of TCR. The latency of P19 component of TCR was positively correlated with disease duration. Conclusions: We propose that the increased latency of R2 and P19 observed here might be reflective of brainstem dysfunction, mediated either by local interneuronal excitability changes or by subtle structural damage

DNA/protein binding and magnetic properties of a 1D Cu(II) complex containing fumarate and tridentate Schiff base ligands

ID copper(II) complex, [Cu2(L)2(fum)]∙H2O}n (1) has been synthesized using fumarate (fum2-) and a Schiff base (HL), derived from the condensation reaction of 2-amino-1-butanol and salicyldehyde. Complex 1 has been characterized by X-ray crystal structure, FT-IR, electronic absorption and fluorescence spectroscopic methods. The structural determination reveals that complex 1 crystallizes in the monoclinic system with space group P21/n and form 1D polymeric chain, built by bridging fum. Weak π¿π and C-H¿π interactions in 1, lead to a 3D supramolecular architecture. Complex 1 exhibits fluorescence at room temperature with a quantum yield (Φs) of 0.257. The interactions of complex 1 with bovine serum albumin (BSA) and human serum albumin (HSA) were studied using electronic absorption and fluorescence spectroscopic techniques and the analysis shows that complex 1 interaction with BSA / HSA occurs mainly with ground state association process. Calculated values of apparent association constants are 1.34 × 104 M-1 and 1.81 × 104 M-1 for BSA and HAS, respectively, at 300 K. The number of binding sites and binding constants were calculated using double logarithm regression equation. The interaction of complex 1 with the calf thymus DNA (CT-DNA) was also investigated using electronic absorption and fluorescence spectroscopic methods. The results show that complex 1 has binding affinity to CT-DNA in the order of 2.96×105 M-1. Low temperature magnetic measurements reveal existence of antiferromagnetic interaction in complex 1. The magnetic data have been fitted considering complex 1 as a pseudo-dinuclear system, with the two copper(II) atoms bridged by two carboxylate oxygen atoms, since the coupling through long fum bridge is almost nil. The best-fit parameters obtained with this model are J = - 60 cm-1, gCu = 2.20

Structural and magnetic characterization of three tetranuclear Cu(II) complexes with face-sharing-dicubane/double-open-cubane like core framework

Three novel tetranuclear copper(II) complexes namely [Cu4(L1)4]∙(dmf) (1), [Cu4(L1)4] (2) and [Cu4(L2)2(HL2)2(H2O)2]∙2(ClO4)∙6(H2O) (3) (H2L1, (E)-2-((1-hydroxybutan-2-ylimino)methyl)phenol; H2L2, (E)-2-((1-hydroxybutan-2-ylimino)methyl)-6-methoxyphenol)) were synthesised from the self-assembly of copper(II) perchlorate and the tridentate Schiff base ligands. The structural determination reveals that complex 1 crystallizes in the monoclinic system with space group C2/c, whereas both the complexes 2 and 3 crystallize in the triclinic system with space group P-1. Complexes 1 and 2 possess face-sharing dicubane core, on the other hand complex 3 has double open cubane core structure. The copper(II) ions in the cubane core are in distorted square planar geometries, and weak π¿π and C-H¿π interactions lead to formation of a 2D supramolecular architecture for complexes 1 and 2. At room temperature complexes 1, 2 and 3, exhibit fluorescence with a quantum yield (Φs) of 0.47, 0.49 and 0.38, respectively. Variable temperature magnetic susceptibility measurements in the range 2-300 K indicate an overall weak antiferromagnetic exchange coupling in all complexes. The PHI program was used to study their magnetic behaviour. In agreement with their face-sharing dicubane structure, a Hamiltonian of the type H = - J1(S1S2+S1S2'+S1'S2+S1'S2') - J2S1S1', where S1 = S1' = S2 = S2' = SCu = 1/2, was used for studying complexes 1 and 2. Simulations performed suggest magnetic exchange constants with values close to J1 = -20 cm-1 and J2 = 0 cm-1 for these complexes. On the other hand, the spin Hamiltonian H = - J1(S1S4+S2S3) - J2(S1S3+S2S4) - J3S1S2, where S1 = S2 = S3 = S4 = SCu = 1/2, was used to study the magnetic behaviour of the double open cubane core of complex 3 and a good agreement between the experimental and simulated results was found by using the parameters g1 = g2 = 2.20, g3 = g4 = 2.18, J1 = -36 cm-1, J2 = -44 cm-1 and J3 = 0 cm-1

Strategic synthesis of [Cu2], [Cu4] and [Cu5] complexes: inhibition and triggering of ligand arm hydrolysis and self-aggregation by chosen ancillary bridges

The Schiff base ligand HL1 ({2,6-bis(allylimino)methyl}-4-methylphenol) having no coordinating donor arm has been examined for its reaction medium and ancillary bridge dependent reactivity for hierarchical family of CuII complexes. The ligand showed unique reactivity pattern toward CuII in solution. The bridging nature of in situ generated HO− ions in absence and presence of externally added carboxylates (RCOO−; R= CF3, C6H5 and CH3) has been utilized to produce complexes {[Cu2(µ–L2)2(H2O)]2[Cu2(µ–L2)2(H2O)2](ClO4)6} (1) (HL2 = 3-{(allylimino)methyl}-2-hydroxy-5-methylbenzaldehyde), [Cu4(µ4–O)(µ–L1)2(µ1,3–O2CCF3)4] (2), [Cu4(µ4–O)(µ–L1)2(µ1,3–O2CC6H5)4]∙H2O (3), [Cu5(µ3–OH)2(µ–L1)2(µ1,3–OAc)2(OAc)2(H2O)4][Cu5(µ3–OH)2(µ–L1)2(µ1,3–OAc)2(OAc)3(H2O)](ClO4)3∙2C2H5OH (4). Absence of carboxylate anions did not yield HO− ions in situ and triggered single ligand arm hydrolysis. The formation of tetra- and pentanuclear aggregates as well as ligand hydrolyzed dinulcear products has been rationalized to identify the possible roles of carboxylate anions in solution. Detailed characterization of the complexes in the solid state and in solution have been carried out using spectroscopic measurements, X-ray crystallography, variable temperature magnetic measurements and functional behavior. In MeOH solutions at 298 K, the complexes 1-4 showed catalytic oxidation of 3,5-di-tert-butyl catechol (3,5-DTBCH2) saturated with O2 of air

2-Amino-5-chloro­pyrimidin-1-ium hydrogen maleate

In the title salt, C4H5ClN3 +·C4H3O4 −, the 2-amino-5-chloro­pyrimidinium cation is protonated at one of its pyrimidine N atoms. In the roughly planar (r.m.s. deviation = 0.026 Å) hydrogen malate anion, an intra­molecular O—H⋯O hydrogen bond generates an S(7) ring. In the crystal, the protonated N atom and the 2-amino group of the cation are hydrogen bonded to the carboxyl­ate O atoms of the anion via a pair of N—H⋯O hydrogen bonds, forming an R 2 2(8) ring motif. The ion pairs are connected via further N—H⋯O hydrogen bonds and a short C—H⋯O inter­action, forming layers lying parallel to the bc plane