Nguyen-Huy Dung

Low-temperature (180 K) crystal structure, electron paramagnetic resonance spectroscopy, and propitious anticonvulsant activities of CuII2(aspirinate)4(DMF)2 and other CuII2(aspirinate)4 chelates.

The purpose of this research was to characterize by X-ray crystallography the ternary dimethylformamide (DMF) Cu(II) complex of acetylsalicylic acid (aspirin), in an effort to compare the structure-activity relationships for the anticonvulsant activity of this and other Cu(II)aspirinate chelates. The ternary DMF Cu(II) complex of aspirin was synthesized and crystals grown from a DMF solution were characterized by single crystal X-ray diffraction. This crystalline material was analyzed for anticonvulsant activity in the Maximal Electroshock (MES) Grand Mal and subcutaneous Metrazol (scMET) Petit Mal models of seizure used to detect anticonvulsant activity. The ternary DMF complex was found to be a monomolecular binuclear complex, tetrakis-mu-(acetylsalicylato)bis(dimethylformamido)dicopper(II) [Cu(II)(2)(aspirinate)(4)(DMF)(2)] with the following parameters: monoclinic, space group P2(1)/n, a=12.259 (1), b=10.228 (1), c=16.987 (1) A, beta=92.07 (1) degrees; V=2128.5 (3) A(3); Z=2. The structure was determined at 180 K from 2903 unique reflections (I>1sigma(I)) to the final values of R=0.030 and wR=0.033 using F. This binuclear complex contains four acetylsalicylate bridging ligands which are related to each other in a two by two symmetry center. The four nearest O atoms around each Cu atom form a closely square planar arrangement with the square pyramidal coordination completed by the dimethylformamide oxygen atom occupying an apical position at a distance of 2.154 (1) A. Each Cu atom is displaced towards the DMF ligand by 0.187 A from the plane of the four O atoms. Electron paramagnetic resonance (EPR) spectra of [Cu(II)(2)(aspirinate)(4)(DMF)(2)] crystals show a strong antiferromagnetic coupling of the copper atoms, similar to that observed with other binuclear copper(II)salicylate compounds. Studies used to detect anticonvulsant activity revealed that [Cu(II)(2)(aspirinate)(4)(DMF)(2)] was an effective anticonvulsant in the MES model of seizure but ineffective against scMET-induced seizures. The monomolecular ternary binuclear [Cu(II)(2)(aspirinate)(4)(DMF)(2)] complex is more effective in inhibiting MES-induced seizures than other binuclear or mononuclear Cu(II) chelates of aspirin including: binuclear polymeric [Cu(II)(2)(aspirinate)(4)], [Cu(II)(2)(aspirinate)(4)(H(2)O)], which is anticipated to be less polymeric, and monomolecular ternary [Cu(II)(2)(aspirinate)(4)(DMSO)(2)] and [Cu(II)(aspirinate)(2)(Pyr)(2)]. These and other chelates appear to be more effective in the scMET model of seizure than [Cu(II)(2)(aspirinate)(4)(DMF)(2)]. These structure-activity relationships support the potential efficacy of Cu chelates of aspirin in treating epilepsies.

Low-temperature crystal structures of Tetrakis-μ-3,5-diisopropylsalicylatobis-dimethylformamidodicopper(II) and Tetrakis-μ-3,5-diisopropylsalicylatobis-diethyletheratodicopper(II) and their role in modulating polymorphonuclear leukocyte activity in overcoming seizures

Two binuclear copper(II) complexes of 3,5-diisopropylsalicylic acid were characterized by single crystal X-ray diffraction methods and examined for anti-inflammatory activity using activated polymorphonuclear leukocytes and for anticonvulsant activities using electroshock and metrazol models of seizures. These complexes were crystallized from dimethylformamide (DMF) or diethylether. Tetrakis-mu-3,5-diisopropylsalicylatobis-dimethylformamidodicop per(II) [Cu(II)2(3,5-DIPS)4(DMF)2] I is in space group P 1; a = 10.393 (2), b = 11.258 (2), c = 12.734 (2) A, alpha = 96.64 (2), beta = 92.95 (2), gamma = 94.90 (2) degrees; V = 1471.7 (4) A3; Z = 1. Tetrakis-mu-3,5-diisopropylsalicylatobis-etheratodicopper(II ) [Cu(II)2(3,5-DIPS)4(ether)2] II is in space group P 1; a = 10.409 (3), b = 11.901 (4), c = 12.687 (6) A, alpha = 91.12 (5), beta = 90.84 (5), gamma = 100.90 (4) degrees; V = 1542 (1) A3; Z = 1. The structure of I was determined at 140 K from 4361 unique reflections (I > 2sigma(1)) and refined on F2 to R1 = 0.04 and wR2 = 0.09. The structure of II was determined at 180 K from 4605 unique reflections (I > 2sigma(I)) and refined on F2 to R1 = 0.05 and wR2 = 0.13. Each compound is a crystallographically centrosymmetric binuclear complex with Cu atoms bridged by four 3,5-diisopropylsalicylate ligands related by a symmetry center [Cu-Cu(i): 2.6139 (9) A in I and 2.613 (1) in II]. The four nearest O atoms around each Cu atom form a nearly rectangular planar arrangement with the square pyramidal coordination completed by the dimethylformamide (or diethylether) oxygen atom occupying an apical position, at a distance of 2.129 (2) A in I and 2.230 (3) A in II. Each Cu atom is displaced towards the DMF (or diethylether) ligand, by 0.189 A in I and 0.184 A in II, from the plane of the four O atoms. The crystal structures of I and II are essentially similar to each other, except for the DMF or diethylether accommodation. Many disorder phenomena were found in the crystal structure of I. Copper(II)2(3,5-DIPS)4(DMF)2 inhibited polymorphonuclear leukocyte (PMNL) oxidative metabolism in vitro. This effect was concentration related and significant for concentrations higher than 10 microg or 0.68 nmol/ml. Copper(II)2(3,5-DIPS)4(DMF)2 was more active than the parent ligand, 3,5-DIPS, as has been demonstrated with copper complexes of other non-steroidal anti-inflammatory drugs. The DMF and diethylether ternary complexes of Cu(II)2(3,5-DIPS)4 were found to have anticonvulsant activity in the maximal electroshock model of grand mal epilepsy in doses ranging from 26 to 258 micromol/kg of body mass following intraperitoneal, subcutaneous, or oral treatment. The DMF ternary complex was also found to be effective in the subcutaneous injection of metrazol model of petit mal epilepsy. We conclude that both ternary copper complexes are lipophilic and bioavailable, capable of facilitating the inflammatory response to brain injury and causing the subsidence of this response in bringing about remission of these disease states.

Macle et structure cristalline de Mn0,75Ga2,17S4

Abstract Twins of Mn 1− x Ga 2+ 2 3 x S 4 were used for crystal structure determination. Twinning is explained by a reticular pseudomerihedry. Axis, plane and obliquity of the twin have been determined. Cell dimensions are: a = b = 5.456(2) A ; c = 10.220(4) A ; α = β = γ = 90°; space group 14; Z = 2. The final R value is 0.059. The material is isostructural with CdGa 2 S 4 .

Synthesis, crystal structure and IR spectroscopy of MnII(2-IC)2(NC)(DMSO) and [MnII(2-IC)2(phen)(H2O)]·DMA; (2-HIC, indole-2-carboxylic acid; phen, 1,10-phenanthroline; NC, 2,9-dimethyl-1,10-phenanthroline; DMSO, dimethyl sulfoxide; DMA, dimethyl acetamide); catalysts for the disproportionation of hydrogen peroxide

Abstract Two ternary complexes of manganese(II) indole-2-carboxylate (2-IC) with 2,9-dimethyl-1,10-phenanthroline (NC) and 1,10-phenanthroline (phen) in dimethyl sulfoxide (DMSO) or dimethylacetamide (DMA) were synthesized, their X-ray crystal structure and IR spectroscopy characteristics were determined. In compound MnII(2-IC)2(NC)(DMSO) (1), Mn(II) is six-coordinate by one bidentate NC ligand and two bidentate 2-IC anionic ligands. The crystal structure has revealed a seven-coordinate Mn(II) when a moderately long contact distance MnO (DMSO 2.643(2) A) is included in the coordination list: the Mn(II) configuration can be described as a distorted capped octahedron. Individual molecules are linked into chains running parallel to the a axis by intermolecular hydrogen bonding. In compound MnII(2-IC)2(phen)(H2O)]·DMA (2), the manganese atom is six-coordinate by one bidentate phen ligand and two 2-IC anionic ligands one of which is monodentate, and the other is bidentate. The coordination sphere is completed by one water molecule, the Mn(II) environment can be described as a very distorted octahedron. The individual molecules are associated in dimmer structure by intermolecular hydrogen bonding. The crystal structure of 2 is completed by a disordered DMA solvate molecule. These two complexes are catalysts for the disproportionation of H2O2 in the presence of added imidazole.

Contribution a l'etude du polymorphisme de Ga2S3: Structure cristalline de Mn0,23Ga1,85S3

Abstract The Mn0.23Ga1.85S3 phase belongs to the solid solution ф 0 , stable at low temperature in the Ga2S3MnS system. It is hexagonal superstructure of the wurtzite, with the Ga2S3α′ type ( a = 6.397 A ; c = 18.027 A Z = 6; space groupe P61 or P65). Its crystal structure has been refined by the least squares method to a final R = 0.06 with 323 independant reflections. This structure is closely related to Ga2S3 α described by Hahn and Frank, and differs only by the partial occupation of the vacant metal site of Ga2S3 by Mn atoms in statistical disorder.

Etude Structurale d'un Analogue de L'Ellipticine a Visée Antineoplasique le Dihydro-1, 4 oxo-4 Trimethy1-2, 5, 11-6H-pyrido [3, 2-b] carbazole par Diffraction de Rayons. X

The synthesis of 1, 4-dihydro-4-oxo-2, 5, 11-trimethy1-6H-pyrido [3, 2-2b] carbazole was described and the lactam-lactim tauromerism was discussed.C18H16N2O crystallizes in space group P21/c with Dm=1.30 (2) Mg·m-3 in acetonitrile with a=16.179 (4), b=14.900 (3). c=12.702 (3) A, β=112.28 (2), V=2833.6 A3, Z=8. The crystalstructure was investigated by X-ray diffraction method with final R=0.04 for 2355 independent reflections. In the two molecules, the lactam form was observed while the lactim for was found with many derivatives as well in solid state as in solution. The carbazole ring is planar while the 1, 4- dihydro-4-oxo-pyridine deviates from planarity. The molecules have rather small overlapping and the molecular packing involves many hydrogen bonds.

Ternary Copper(II) Complexes With Indomethacin, a Potent Non-Steroidal Antiinflammatory Drug. Crystal Structure of Bis (Dimethylformamide)-Tetrakis[1-(4-Chlorobenzoyl)-5-Methoxy-2-Methyl-1-H-Indole-3-Acetato]Dicopper(II). Antiinflammatory Properties and Prevention of Gastrointestinal Side Effects by Nanocapsules.

Two ternary copper(ll) complexes of indomethacin [1-(4-chlorobenzoyl)-5-methoxy-2- methyl-1-H-indole-3-acetic acid] called hereafter lndo, were prepared and characterized by single crystal X-ray diffraction. The first complex Cu2(Indo)4(DMF)2 I crystallizes in space group P-1 (a = 10.829(2), b = 13.379(2), c = 16.491(3) Å; α = 105.58(2), β = 101.06(2), γ = 106.96(2)°; V= 2104.6(6) Å3, Z= 1). The title molecule is a centrosymmetric binuclear complex, with Cu atoms bridged by the carboxylate moieties of four indomethacinate ligands. The four nearest O atoms around each Cu atom form a square planar arrangement with the square pyramidal coordination completed by the O atom of N,N′-dimethylformamide. Daily administration for seven days of 1 mg/kg of indomethacin, I and I encapsulated into liposomes induces a weak inflammation of rat gastrointestinal tract. I was less inflammatory than indomethacin but the better protection was brought by encapsulation of the compound. This might be of interest in sustained therapies of chronic inflammatory diseases.

A COPPER(II) COMPLEX CONTAINING THE PROTONATED FORM OF A DIAMINOPENTACARBOXYLIC ACID WITH AN UNSYMMETRICAL SKELETON

Abstract Crystalline samples of CuH3L · 3.5H2O (L = anion of N,N,N′,N′-tetrakis(carboxymethyl)-2,4-diamino-butyric acid; H5TDB = H5L) have been characterized by X-ray diffraction and other methods. The compound crystallizes in the monoclinic system, space group P21/n (a = 6.260(2), b = 18.505(5) c = 15.659(3) A, β = 91.78(3)° and Z = 4). Final R = 0.049 and Rw = 0.054 for 1400 independent observed reflections. The structure consists of one-dimensional chains of CuH3L complex units and non-coordinated water molecules linked together in a network of hydrogen bonds. Only two [H(062) and H(N2)] of the three “acid” hydrogen atoms of the ligand (H3L2−) have been located in the structure. Each H3L2− anion acts as a tetradentate chelating agent for a Cu(II) ion by means of the C-substituted hydrogen nitrilotriacetato (NTA) group (Cu-N(1) 2.026(9), Cu-O(11) 1.971(8), Cu-O(81) 2.003(8) and Cu-O(61) 2.186(6)A. The O(11) and O(61) atoms are part of carboxylato and carboxylic groups, respectively. The distorted five c...