Search

A supra­molecular two-dimensional polymer structure of caesium tetra­methyl­dithio­imidodiphosphinate is reported., In the title crystal, the salt [CsMe2P(S)NP(S)Me2] is self-assembled as an undulating supra­molecular two-dimensional polymeric structure, poly[(μ4-tetra­methyl­dithio­imidodiphosphinato)caesium], [Cs(C4H12NP2S2)]n, which is parallel to the bc plane. The Cs cations are hexa­coordinated, being chelated by two thio­imidophosphinate groups and two sulfur atoms from neighboring ligands. The anions are linked to the Cs cations by Cs⋯S and Cs⋯N electrostatic inter­actions.

The synthesis and characterization of two new 1,3,5-triazines containing 2-(aminomethyl)-1H-benzimidazole hydrochloride as a substituent are reported, namely, 2-{[(4,6-dichloro-1,3,5-triazin-2-yl)amino]methyl}-1H-benzimidazol-3-ium chloride, C11H9Cl2N6 +·Cl− (1), and bis(2,2′-{[(6-chloro-1,3,5-triazine-2,4-diyl)bis(azanediyl)]bis(methylene)}bis(1H-benzimidazol-3-ium)) tetrachloride heptahydrate, 2C19H18ClN9 2+·4Cl−·7H2O (2). Both salts were characterized using single-crystal X-ray diffraction analysis and IR spectroscopy. Moreover, the NMR (1H and 13C) spectra of 1 were obtained. Salts 1 and 2 have triclinic symmetry (space group P-1) and their supramolecular structures are stabilized by hydrogen bonding and offset π–π interactions. In hydrated salt 2, the noncovalent interactions yield pseudo-nanotubes filled with chloride anions and water molecules, which were modelled in the refinement with substitutional and positional disorder.

[1-(1H-benzimidazol-2-yl)-N-(propan-2-ylidene)methanamine-κ2,N2,N3]dichloridozinc(II) 1, [N-((1H-benzimidazole-2-yl-κN)methyl)-4-(((1H-benzimidazole-2-yl-κN)methyl)imino-κN)-2-methylpentan-2-amine-κN)]chloridozinc(II) chloride dihydrate 2, and tris [(E)-4-(((1H-benzimidazol-2-yl-κN3)methyl)amino)pent-3-en-2-one]chloridozinc(II) chloride hydrate 3 complexes were synthesized via condensation of ZnII complexes A-C with the corresponding ketone. Whereas compounds 1 and 2 were obtained by condensation of propan-2-one with complexes A-C, pentane-2,4-dione was used in the synthesis of 3. Vibrational and thermogravimetric studies showed that the chelate structure of 2 is stabilized by the presence of hydrogen bonds. Moreover, theoretical and experimental NMR studies confirmed that the metal ion is bonded to the ligand in chelate form. On the other hand, vibrational and crystallographic studies showed that 3 has a helicoidal geometry in which the metal ion is bonded to three ligands that act as blades. In solid state, the complex 3 is stabilized by the presence of weak interactions between each blade of the molecule. Additionally, NMR studies indicated that 3 preserves its C3 symmetry in methanolic solution.

The alkali metal (Li + , Na + , K + , Rb + , Cs + ) carboxylate-dithiocarbamate complexes of L -proline have been prepared from the reaction of L -proline with carbon disulfide in the presence of two equivalents of the corresponding alkali metal hydroxide. The resulting compounds have been characterized by FAB + mass spectrometry, IR spectroscopy, NMR ( 1 H, 13 C) spectroscopy. The X-ray single crystal crystallography analysis of the complexes of K + , Rb + and Cs + complexes showed that the coordination modes of dithiocarbamate and carboxylate groups to the alkali metal is modulated by the resonance effect, the ionic radius of the sulfur and oxygen atoms as well as the size, charge-density, and Lewis-acidity of the metal ions. In this way in the solid state polymeric structures in 2D for K + and Rb + complexes, and 3D in the case of Cs + are generated. The distances C···M, M···S1 and M···S2 suggest the existence of cation···π and van der Waals interactions that can be described as a η 3 coordination mode of the dtc group to the alkali metal ions.

Two new chlorodiorganotin(IV) dithiocarbamate complexes with general formula {(R2SnCl)dtc} (dtc = R1R2NCS2−, R1 = Bn, R2 = naphtylimide; 3, R = n-Bu; 4, R = Ph) have been prepared from sodium N-[2-(benzylamino)ethyl]naphthalene-1,8-dicarboximide dithiocarbamate 2. The bis-dithiocarbamete 3d (R2Sn(dtc)2, R = n-Bu) was obtained as the thermodynamic product during the titration process (vide infra). All compounds were characterized by mass spectrometry, IR, 1H and 13C NMR spectroscopy. The chlorodiorganotin(IV) dithiocarbamate complexes 3–4 also were characterized by 119Sn NMR spectroscopy and single crystal X-ray diffraction analysis. The crystallographic study of these complexes showed the existence of C H…π, S…π and π…π intramolecular interactions, indicating that the naphthylimide aromatic fragment stabilized the complexes. Complexes 3 and 4 were studied as host for anions (CH3CO2−, F−, H2PO4−) in CDCl3 by UV–Vis and 119Sn NMR spectrometric titrations. The tested anions cause the displacement of the chloride ligand of the metallic centre. The excess of F− or H2PO4− induce the self-assembly of diorganotin(IV) dithiocarbamate to bis-dithiocarbamates R2Sn(dtc)2 (3d) instead of the breaking of the S Sn covalent bond. Quantum mechanical calculations at DFT level (B3LYP/def2-TZVP) were performed to obtain the thermodynamic parameters of the reactions involved in the anion addition to the complexes.

In the structure of the title compound, cooperative C—H⋯O=C, C—H⋯π and offset π–π inter­actions generate supra­molecular nanotubes which accommodate the 2,3-di­chloro­benzene solvent mol­ecules., The asymmetric unit of the title compound, C56H50N6O8S2·3C6H4Cl2, contains two half-mol­ecules of the parent, A and B, which both have crystallographic inversion symmetry, together with three 2,3-di­chloro­benzene mol­ecules of solvation. Mol­ecules A and B are conformationally similar, with dihedral angles between the central naphthalenedi­imide ring and the peripheral naphthalene and benzyl rings of 2.43 (7), 81.87 (7)° (A) and 3.95 (7), 84.88 (7)° (B), respectively. The conformations are stabilized by the presence of intra­molecular π–π inter­actions between the naphthalene ring and the six-membered di­imide ring of the central naphthalenedi­imide moiety, with ring centroid-to-centroid distances of 3.5795 (8) Å (A) and 3.5640 (8) Å (B). In the crystal, C—H⋯O hydrogen bonds link the mol­ecules into infinite supra­molecular chains along the c axis. These chains are inter­connected through C—H⋯π and offset π–π inter­actions, generating supra­molecular nanotubes which are filled by 1,2-di­chloro­benzene mol­ecules.

The chlorodiphenyltin(IV) dithiocarbamate complexes 1–5 with general formula {(Ph2SnCl)dtc} (dtc = R1R2NCS2−; 1, R1 = Bn, R2 = 9-anthrylmethyl; 2, R1 = Bn, R2 = 9-phenanthrylmethyl; 3, R1 = Bn, R2 = 1-pyrenylmethyl; 4, R1 = 1-naphthylmethyl, R2 = 1-pyrenylmethyl; 5, R1 = R2 1-pyrenylmethyl) have been tested as host for anions and neutral amines in acetonitrile by spectrophotometric UV/Vis titrations. In addition, the titrations of the complexes 1 and 5 were studied in chloroform by 1H and 119Sn NMR spectroscopy. It was found that anions as acetate, benzoate, and dihydrogen phosphate cause a displacement of the dithiocarbamate ligands of metallic center independently of the aromatic nature of the substituents on the nitrogen atom functioning as chemodosimeters in which the indicator is displaced. However, some aliphatic amines and aromatic methylene amines and its aromatic analogs can act as guests with binding constants in the range of 103 to 106 M−1. Also, in these cases compound 5 functions as chemodosimeter without displacement of the indicator. According to 1H, 13C, 119Sn NMR data and using DFT (B3LYP) and Poisson–Boltzmann (PB) to model the solvent, structures of the complexes are proposed in which the hydrophobic and π–π interactions are suggested as the dominant interactions.

Four new bismuth(III) complexes; (CH2S)2Bi[S2CN(CH2)4] (2), CH2(CH2S)2Bi[S2CN(CH2)4] (3), S(CH2CH2S)2Bi[S2CN(CH2)4] (4), O(CH2CH2S)2Bi[S2CN(CH2)4] (5) were prepared from the reaction of the sodium salt of pyrrolidine-dithiocarbamate (1) with four chloro-dithia-bismuth(III) compounds containing five-, six- and eight-membered heterocycles. The complexes were characterized by elemental analyses, infrared, and 1H and 13C NMR spectroscopy. In addition, the single crystal X-ray structures of 2–4 were obtained, showing an asymmetric bidentate coordination mode of the dithiocarbamate ligand moiety. The metal center in 2 and 3 is tetracoordinated, while in 4 a pentacoordinate metal center is observed, the latter is achieved through the 1,5-transannular Bi⋯S interaction, which is common in these types of metallocane rings. Antibacterial assays showed that 2–5 were active in ATCC and clinical isolated strains. Antiploliferation assays were carried out showing high antiproliferative effect against breast cancer cell lines, in vitro. A QSAR model employing quantum global and local chemical descriptors was constructed to gain further insight into their antibacterial activity.

Four new homoditopic bis[chlorodiorganotin(IV) and triorganotin(IV) dithiocarbamate] complexes derived from naphthalene diimide (NDI) with general formula NDI-[(CH2)2-N(CH2Ph)(CS2SnR2X)]2, 3: R = n-Bu, X = Cl; 4: R = Me, X = Cl; 5: R = Ph, X = Cl; 6: R = X = Me; were prepared from triethylammonium ((1,3,6,8-tetraoxo-1,3,6,8-tetrahydrobenzo[lmn][3,8]phenanthroline-2,7-diyl)bis(ethane-2,1-diyl))bis(benzylcarbamodithioate) 2. All compounds were characterized by IR, as well as 1H and 13C NMR spectroscopy. The complexes 3–6 also were characterized by 119Sn NMR spectroscopy. In addition, complex 3 was further characterized by single-crystal X-ray diffraction analysis. The crystallographic study performed on complex 3 showed that the tin atom has a coordination geometry intermediate between square-pyramid and a trigonal-bipyramidal, with τ value of 0.69. In addition the presence of cooperative C H…π, C H…S, C H…O and S…π intramolecular interactions in the crystal structure of 3 was observed. The interaction of complexes 3–6 with anions (CH3CO2−, F−, H2PO4−) in CDCl3 was studied by UV/Vis, fluorescence and 119Sn NMR titrations. The addition of the foregoing anions to complexes 3-6 lead to the displacement of the chloride ligand at the tin(IV) atom. However, an the excess of F− or H2PO4− induced the self-assembly of complexes 3 and 5 in their corresponding binuclear metallomacrocycles.

Here, we report the synthesis of six organic-inorganic hybrid compounds from amino amides and tetrachlorozincate anions to study the processes underlying the modulation of hydrogen bonds and π∙∙∙π interactions in these salts. Thus, 2-((2-ammoniopropanamido)-methyl)-1H-benzimidazole-3-ium tetrachlorozincate 7, 2-(1-(2-ammoniopropanamido)-ethyl)-1H-benzimidazole-3-ium tetrachlorozincate 8, 2-((2-ammonio-3-methylbutanamido)methyl)-1H-benzimidazole-3-ium tetrachlorozincate 9, 2-(1-(2-ammonio-3-methylbutanamido)-2-methylpropyl)-1H-benzimidazole-3-ium tetrachlorozincate 10, 2-((2-ammonio-4-methylpentanamido)methyl)-1H-benzimidazole-3-ium tetrachlorozincate 11, and 2-(1-(2-ammonio-4-methylpentanamido)-3-methylbutyl)-1H-benzimidazoel-3-ium tetrachlorozincate 12 were obtained from the corresponding hydrochlorides (1–6). Crystallographic experiments using compounds 7–12 revealed that the presence of bulky substituents situated on C10 and C13 reduces the efficacy of stacking phenomena. Moreover, the ZnCl42− ∙∙∙H–N hydrogen bonds induce the polarization of the imidazole ring and the π∙∙∙π interactions occur through the “dipole-induced dipole” mechanism. In the case of N–H∙∙∙solvent interactions, the stacking phenomena occur preferentially through the “induced dipole-induced dipole” mechanism.

In this study, we synthesized five N-Boc-L-tyrosine-based analogues to glitazars. The in vitro effects of compounds 1–5 on protein tyrosine phosphatase 1B (PTP-1B), peroxisome proliferator-activated receptor alpha and gamma (PPARα/γ), glucose transporter type-4 (GLUT-4) and fatty acid transport protein-1 (FATP-1) activation are reported in this paper. Compounds 1 and 3 were the most active in the in vitro PTP-1B inhibition assay, showing IC50s of approximately 44 μM. Treatment of adipocytes with compound 1 increased the mRNA expression of PPARγ and GLUT-4 by 8- and 3-fold, respectively. Moreover, both compounds (1 and 3) also increased the relative mRNA expression of PPARα (by 8-fold) and FATP-1 (by 15-fold). Molecular docking studies were performed in order to elucidate the polypharmacological binding mode of the most active compounds on these targets. Finally, a murine model of hyperglycemia was used to evaluate the in vivo effectiveness of compounds 1 and 3. We found that both compounds are orally active using an exploratory dose of 100 mg/kg, decreasing the blood glucose concentration in an oral glucose tolerance test and a non-insulin-dependent diabetes mellitus murine model. In conclusion, we demonstrated that both molecules showed strong in vitro and in vivo effects and can be considered polypharmacological antidiabetic candidates.

2-{[(Ammoniumacetyl)amino]methyl}-1H-benzimidazol-3-ium dichloride 4, 2-{[(2-ammoniumpropanoyl)amino]methyl}-1H-benzimidazol-3-ium dichloride 5, and 2-{[(2-ammonium-3-phenylpropanoyl)amino]methyl}-1H-benzimidazol-3-ium dichloride 6 amino amides were synthesized via condensation of 2AMBZ dihydrochloride with the corresponding amino acid. Compounds 7–12 were obtained by replacing chloride ions (in salts 4–6) with nitrate or tetrachlorozincate ions. The results of X-ray diffraction crystallographic studies indicated that the geometries, charges and sizes of the anions are essential for the formation of the strong hydrogen bond interactions of compounds 4, 5, 9–12. Moreover, in most cases, the presence of water and solvent molecules stabilizes the supramolecular structures of these compounds. Nuclear magnetic resonance (NMR) and infrared (IR) spectroscopy indicated that the presence of chloride or tetrachlorozincate anions increases the acidity of the benzimidazolic and amide groups more significantly than the presence of nitrate anions. However, Quantum Theory of Atoms in Molecules (QTAIM) computations of the crystal structures demonstrate that amino amides interact more strongly with NO3− than with Cl− and ZnCl42− anions; this difference explains the spectroscopic results.

cis- and trans-1,2-chdcaH2, 1,3-chdcaH2, and 1,4-chdcaH2 (chdcaH2 = cyclohexanedicarboxylic acid) as well as cis,cis-1,3,5-chtcaH3 (chtcaH3 = cyclohexanetricarboxylic acid) have been treated with dimethyl- and di-n-butyltin reagents, and for the case of 1,4-chdcaH2 additionally with di-tert-butyltin dichloride, to determine whether macrocyclic or polymeric diorganotin dicarboxylates are formed dependent of the spatial orientation of the coordinating ligand functions and the organic substituents at the metal atom and to analyze conformational and topological variations in the resulting supramolecular aggregates. The single-crystal X-ray diffraction studies showed that besides the ligand geometry the substituents at the metal center are key elements for the formation of either monomeric, cyclo-oligomeric, or polymeric assemblies. Two of the compounds characterized by X-ray diffraction analysis exhibited macrocyclic ring structures, [{Me2Sn(cis-e,a-1,4-chdca)}2] and [{nBu2Sn(cis-e,a-1,4-chdca)}4]. For most o...

The combination of bis-dithiocarbamate ligands derived from N,N′-dibenzylcyclohexane-trans-1,4-diamine with dimethyl- and di-n-butyltin(IV) dichloride provided two discrete dinuclear complexes of the composition [(Me2SnCl)2(bis-dtc)]·2CHCl3 (1) and [(nBu2SnCl)2(bis-dtc)] (2) with bis-dtc = N,N′-dibenzylcyclohexane-trans-1,4-diamine-bisdithiocarbamate. Additionally, single crystals of the composition [(nBu2SnCl)(mono-dtc)]·[nBu2SnCl2]2 (3) with mono-dtc = N,N′-dibenzylcyclohexane-trans-1,4-diamine-monodithiocarbamate were isolated. Within the crystal structures of the three complexes, a varied number of common (C–H⋯S, C–H⋯Cl and N–H⋯Cl) and less common (S⋯S, S⋯Cl, Cl⋯Cl, Cl⋯N and Cl⋯Sn) secondary interactions were observed and analyzed. The supramolecular solid-state organization of [(Me2SnCl)2(bis-dtc)]·2CHCl3 revealed the presence of channels, which were filled with chloroform molecules. In the crystal structure of [(nBu2SnCl)(mono-dtc)]·[nBu2SnCl2]2, the di-n-butyltin dichloride units are arranged in form of a so far unknown dimeric aggregate of the composition [(nBu2SnCl)(μ-Cl)2(ClSnnBu2)]. The latter assembly represents thus a rare example for a two-component co-crystalline assembly, in which a relatively large non-solvent molecule with unusual molecular structure is stored and stabilized.

Compounds 1-10 were designed using a bioisosteric approach and were prepared using a short synthetic route. The in vitro inhibitory activity of the compounds against 11 beta-hydroxysteroid dehydrogenase type 1 (11 beta-HSD1) was evaluated. Compounds 5 (alpha-series) and 10 (beta-series) had a moderate inhibitory enzyme activity (55.26% and 67.03% inhibition at 10 mu M, respectively) and were as active as BVT.14225 (positive control). Both compounds have a piperidine ring in their structure, but the most active (10) was selected to establish its in vivo antidiabetic effect using a non insulin-dependent diabetes mellitus rat model. The antidiabetic activity of compound 10 was determined at 50 mg/kg single dose in an acute model, and also by short term sub-chronic administration for 5 days. The results indicated a significant decrease of plasma glucose levels, similar than BVT.14225. Additionally, a molecular docking of the most active compounds of each series into the ligand binding pocket of one subunit of human 11 beta-HSD1 was performed. In this model the oxygen atom of the sulfonamide make hydrogen bond interactions with the catalytic residues Ser170 and Ala172. We also observed important pi-pi interactions between the naphthyl group and Tyr177. (C) 2014 Elsevier Masson SAS. All rights reserved.

The crystal structure of the title compound shows that the 1,2-di­amino­cyclo­hexane fragment has a chair conformation with the N atoms in an anti­periplanar conformation. The packing is stabilized via N—H⋯Br, C—H⋯Br and C—H⋯π inter­actions., The cation of the title solvated salt, C42H42N2P2 2+·2Br−·2CH2Cl2, lies on a crystallographic twofold rotation axis. The 1,2-di­amino­cyclo­hexane fragment has a chair conformation with two N atoms in a transoid conformation [N—C—C—N = 163.4 (2)°]. In the crystal, the cations are linked to the anions by N—H⋯Br and C—H⋯Br hydrogen bonds, forming a chain structure along the c axis. The di­chloro­methane mol­ecule takes part in the hydrogen-bond network through C—H⋯π and C—H⋯Br inter­actions.

Nine mononuclear diorganotin(IV) dithiocarbamate complexes 1–9 with 19-, 20- and 21-membered macrocyclic structures were synthesized from dimethyl, di-n-butyl, and diphenyltin(IV) dichloride and three bis-dithiocarbamate ligands derived from secondary bis-amines having aromatic spacer groups. All compounds were characterized by elemental analysis, mass spectrometry, and spectroscopic methods (IR and 1H, 13C, and 119Sn NMR). Additionally, quantum chemical DFT calculations were performed for the dimethyltin(IV) derivatives in order to model the molecular structures. For one compound series the NMR spectra showed a concentration-dependent behavior in solution, which was analyzed in detail and permitted to postulate the existence of an equilibrium with the corresponding [2+2] macrocycles.

Five new chlorodiorganotin(IV) complexes derived from dithiocarbamate ligands have been prepared and structurally characterized. The complexes 1–5 with the general formula {(Ph2SnCl)dtc} (dtc = R1R2NCS2−; 1, R1 = Bn, R2 = 9-anthrylmethyl; 2, R1 = Bn, R2 = 9-phenanthrylmethyl; 3, R1 = Bn, R2 = 1-pyrenylmethyl; 4, R1 = 1-naphthylmethyl, R2 = 1-pyrenylmethyl; 5, R1 = R2 = 1-pyrenylmethyl) have been obtained from Ph2SnCl2 and the sodium dithiocarbamate salts of benzyl(9-anthrylmethyl)amine, benzyl(9-phenanthrylmethyl)amine, benzyl(1-pyrenylmethyl)amine, 1-naphthylmethyl(1-pyrenylmethyl)amine and di(1-pyrenylmethyl)amine. Compounds 1–5 have been analyzed as far as possible by elemental analysis, FAB+ mass spectrometry, IR, UV–Vis, fluorescence and NMR (1H, 13C, 119Sn) spectroscopy, and single-crystal X-ray diffraction analysis (1–3). The solid-state and solution studies showed that the dtc ligands are coordinated to the tin atoms in the anisobidentate manner. In all cases the metal centers are five-coordinate. The coordination geometry is intermediate between square-pyramidal and trigonal-bipyramidal coordination polyhedra with τ-values in the range of 0.49–0.55. The crystal structures show the presence of C–H···Cl, C–H···S, C–H···π, offset π–π and S···π contacts. The stability of the (Ph2SnCl)dtc complexes in the presence of the acetate anion has been examined in acetonitrile solutions. For all of these organotin(IV) complexes the displacement of the coordinated ligands (i.e., chloride and dtc) by the acetate anion was observed. The lability, as well as their intrinsic fluorescent properties of the polyaromatic moieties in these (Ph2SnCl)dtc compounds make them interesting candidates to detect the presence of O-donor anions at very low concentrations by displacement of the metal-coordinated dtc.

Two series of di and trinuclear chlorodiorganotin(IV) complexes derived from bis- and tris-dithiocarbamate ligands have been prepared and structurally characterized. The dinuclear complexes 1–2 of the composition {(R2SnCl)2(bis-dtc)} (1, R = Me; 2, R = nBu) have been obtained from R2SnCl2 (R = Me, nBu) and the triethylammonium salt of N,N′-dibenzyl-1,2-ethylene-bis(dithiocarbamate). The trinuclear complexes 3–9 with the general formula {(R2SnCl)3(tris-dtc)} 3, R = Me, tris-dtc = tris-dtc-Me; 4, R = Me, tris-dtc = tris-dtc-iPr; 5, R = Me, tris-dtc = tris-dtc-Bn; 6, R = nBu, tris-dtc = tris-dtc-Me; 7, R = nBu, tris-dtc = tris-dtc- iPr; 8, R = nBu, tris-dtc = tris-dtc-Bn; 9, R = tBu, tris-dtc = tris-dtc-Me) were prepared from R2SnCl2 (R = Me, nBu, tBu) and the potassium dithiocarbamate salts of (tris[2-(methylamino)ethyl]amine) (tris-dtc-Me), (tris[2-(isopropylamino)ethyl]amine) (=tris-dtc-iPr) and (tris[2-(benzylamino)ethyl]amine) (=tris-dtc-Bn). Compounds 1–9 have been analyzed as far as possible by elemental analysis, FAB+ mass spectrometry, IR and NMR (1H, 13C, 119Sn) spectroscopy, and single-crystal X-ray diffraction analysis. The solid state and solution studies showed that the dtc ligands are coordinated to the tin atoms in the anisobidentate manner. In all cases the metal centers are five-coordinate. The coordination geometry is intermediate between square-pyramidal and trigonal-bipyramidal coordination polyhedra with τ-values in the range of 0.32–0.53. For the members of each series characterized in the solid state by X-ray diffraction analysis, different molecular conformations were found. The crystal structures show the presence of C–H⋯Cl, C–H⋯S, C–H⋯π, S⋯Cl, S⋯S, Cl⋯Sn and S⋯Sn contacts.

The compound ethyl 2-(4-(acetylamino)phen- oxy)-2-methylpropanoate (acetamidofibrate) was prepared by reaction of paracetamol with ethyl 2-bromo-2-methyl- propionate. It was characterized by elemental analysis, NMR ( 1 H, 13 C) spectroscopy, and single-crystal X-ray diffraction. This compound is of interest with respect to its potential bioactivity as analgesic and antidyslipidemic agent. The compound crystallizes in the monoclinic space group P2(1)/c with unit cell dimensions a = 8.2435(8), b = 9.3390(9), c = 18.2823(18) A ˚ , b = 91.123(2) ,V = 1407.2(2) A ˚ 3 ,Z = 4, R1 = 0.0465, and wR2 = 0.1055. The crystal structure is stabilized by N-HO = C and C-HO hydrogen-bonding interactions that interconnect molecules into chains running along b axis. The pre- liminary in silico screening shown that title compound could posse's antidiabetic, anti-inflammatory, hypolipem- iant and anti-atherosclerosis effects.

Two new series of imidazole derivatives (acetamides: 1–8 and sulfonamides: 9–15) were synthesized using a short synthetic route. Compound 1 as well as the intermediate 16g were characterized by X-ray crystallography. Imidazole derivatives 1–15 were tested in vitro against three unicellular parasites (Giardia intestinalis, Trichomonas vaginalis and Entamoeba histolytica) in comparison with benznidazole (Bzn) and metronidazole. Compound 1 [N-benzyl-2-(2-methyl-4-nitro-1H-imidazol-1-yl)acetamide] was 2 times more active than Bzn against T. vaginalis and G. intestinalis and it was as active as Bzn against E. histolytica. Sulfonamides showed selective toxicity against E. histolytica over the other parasites. Toxicity assay showed that all compounds are non-cytotoxic against MDCK cell line. The results revealed that compounds 1–15 have antiparasitic bioactivity in the micromolar range against the parasites tested, and could be considered as benznidazole bioisosteres.

The reactivity of N-(2-aminophenyl)-d-glycero-d-gulo-heptonamide (adgha), with the group 12 cations, Zn(II), Cd(II), and Hg(II), was studied in DMSO-d(6) solution. The studied system showed a selective coordination to Hg(II), and the products formed were characterized by (1)H and (13)C NMR in DMSO-d(6) solution and fast atom bombardment (FAB(+)) mass spectra. The expected coordination compounds, [Hg(adgha)](NO(3))(2) and [Hg(adgha)(2)](NO(3))(2), were observed as unstable intermediates that decompose to bis-[2-(d-glycero-d-gulo-hexahydroxyhexyl)-benzimidazole-κN]mercury(II) dinitrate, [Hg(ghbz)(2)](NO(3))(2). The chemical transformation of the complexes was followed by NMR experiments, and the nature of the species formed is sustained by a theoretical study done using DFT methodology. From this study, we propose the structure of the complexes formed in solution, the relative stability of the species formed, and the possible role of the solvent in the observed transformations.

Two new dinuclear diorganotin(IV) dithiocarbamate (dtc) macrocycles, [Me2Sn(dtc)]2 (1) and [nBu2Sn(dtc)]2 (2), have been synthesized from R2SnCl2 (R = Me, nBu) and the bis(dithiocarbamate) derivative of N,N -dibenzylhexamethylene-1,6-diamine. These complexes have been characterized by elemental analysis, FAB mass spectrometry, IR and NMR (H, C, Sn) spectroscopy, as well as single crystal X-ray crystallography. The dtc ligands are coordinated to the tin atoms in the anisobidentate manner, both in solution and the solid state. The metal centers are hexacoordinated and the coordination polyhedron of the tin atoms can be described as bicapped tetrahedron or skew trapezoidal bipyramid. The cavities of the 26-membered macrocycles are hydrophobic with four sulfur atoms directed into the interior and have an inner diameter of approximately 4.1 x 5.6 A. The crystal structure of [Me2Sn(dtc)]2 (1) is stabilized by the presence of two chloroform molecules per asymmetric unit, which participate in intermolecular C-H⋅⋅⋅S, C-H⋅⋅⋅Cl hydrogen bonding and S⋅⋅⋅Cl donor acceptor interactions. On the other hand, the crystal structure of [nBu2Sn(dtc]2 (2) is stabilized additionally by intermolecular C-H⋅⋅⋅π interactions.

N-(p-Toluenesulfonyl)glycine o-phenolamide (3a) and the analogous derivatives of d,l-alanine (3b), L-valine (3c), L-leucine (3d), and L-phenylalanine (3e) were synthesized in yields >80% by condensation of N-(p-toluenesulfonyl)amino acyl chlorides with o-aminophenol. The structure and conformation of these amides were established by NMR spectroscopy and X-ray crystallography. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:247–253, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10135

The syntheses and structure determinations of a series of boron heterocycles derived from 2-guanidinobenzimidazole 1 are reported. Structures of new compounds, 2-guanidino-1-methyl-benzimidazole 2, diphenyl-(2-guanidinobenzimidazole-N,N′)-borate 3, diphenyl-(2-guanidino-1-methyl-benzimidazole-N,N′)borate 4, hydroxy-phenyl-(2-guanidino-benzimidazole-N,N′)borate 5, hydroxy-phenyl-(2-guanidino-1-methyl-benzimidazole-N,N′)borate 6,methoxy-phenyl-(2-guanidinobenzimidazole-N,N′)borate 7, isopropoxy-phenyl-(2-guanidinobenzimidazole-N,N′)borate 8, acetoxy-phenyl-(2-guanidinobenzimidazole-N,N′)borate 9, methoxy-phenyl-(2-guanidino-1-methyl-benzimidazole-N,N′)borate 10, dihy-droxy-(2-guanidino-1-methyl-benzimidazole-N,N′)borate 16, difluoro-(2-guanidinobenzimidazole-N,N′)borate, 17, dihydroxy-(2-guanidino-1-benzimidazole-N,N′)borate potassium salt 19, diphenyl-(2-guanidinium-10H-benzimidazole-N,N′)borate hydro-chloride 20, methoxy-phenyl-(2-guanidinobenzimidazole-N,N′)borate hydrochloride 21, and N10-borane-(diphenyl-2-guanidinobenzimidazole-N,N′)borate 22, were determined based on 1H, 13C, 15N, and 11B spectroscopy. The X-ray diffraction structures of 3–7, 19, and 20 were obtained. The formation of N3-borane adducts 11 and 12 derived from compounds 1 and 2, respectively, and the dihydride-(2-guanidinobenzimidazole-N,N′)borate 13 and dihydride-(2-guanidino-1-methyl-benzimidazole-N,N′)borate 14 were observed by 11B NMR. The results show that 2-guanidinobenzimidazole gives stable borate heterocycles with a delocalized π electronic system. A dynamic exchange of N–H protons was observed with preferred protonation at N-12. The new heterocycles are protonated at N-10 by acidic substances to give pyridinium-type heterocycles or can lose a proton to give iminium salts. © 1998 John Wiley & Sons, Inc. Heteroatom Chem 9:399–409, 1998

In the title salt, C23H21NOP+·Br−, the dihedral angles between the phenyl rings are 70.41 (18), 73.6 (2) and 80.85 (19)°. In the crystal, neighboring molecules are linked through an N—H...Br hydrogen bond and four weak C—H...Br contacts, forming a three-dimensional network.

1,3,2-Benzimidazaborole, 1,3,2-benzoxaborole, and 1,3,2-benzothiazaborole were synthesized from the corresponding 2-benzazole N(SINGLE BOND)BH3 and 2-benzazole S(SINGLE BOND)BH3 adducts through a reductive transposition from the isolobal fragment X(SINGLE BOND)C(sp2) (DOUBLE BOND) N(sp2) (SINGLE BOND) B(sp3) (X (DOUBLE BOND) N, O, S) to the fragment X(SINGLE BOND)B(sp2) (DOUBLE BOND) N(sp2) (SINGLE BOND) C(sp3). N(SINGLE BOND)BH3 substitution shifts to lower frequencies 4-H, C-3a, and C-7a resonances. The X-ray diffraction analysis of 2-(o-methoxyphenyl)benzothiazole N(SINGLE BOND)BH3 adduct is reported. Two new tetracyclic boron-bridged compounds were observed as by-products (6,9-(ethyl)-diaza-2-oxa-1-bora[3,4,7,8]-dibenzobycyclo[4.3.0]-nona-3,7-diene, 6d, and 8-aza-9-oxa-2-thia-1-bora-[3,4,7,8]dibenzobycyclo[3.4.0]nona-3,7-diene, 15d, when 2-(o-methoxyphenyl)-1-ethylbenzimidazole-BH36b and 2-(o-methoxyphenyl)-benzothiazole-BH315b adducts were heated. © 1996 John Wiley & Sons, Inc.

The asymmetric unit of the title compound, C20H16N2O, contains two molecules. The dihedral angles between the benzimidazole ring systems and the attached benzene rings are 10.6 (5) and 13.7 (5)°. The conformers are linked by bifurcated three-centre hydrogen bonds, forming chains along the diagonal of the ab plane. The packing is further stabilized by π–π and C—H...π interactions.

N-(p-Toluenesulfonyl)glycine o-phenolamide (3a) and the analogous derivatives of d,l-alanine (3b), L-valine (3c), L-leucine (3d), and L-phenylalanine (3e) were synthesized in yields >80% by condensation of N-(p-toluenesulfonyl)amino acyl chlorides with o-aminophenol. The structure and conformation of these amides were established by NMR spectroscopy and X-ray crystallography. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:247–253, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10135

The alkali metal (Na+, K+, Rb+, Cs+) bis-dithiocarbamate (bis-dtc) salts of N,N′-dibenzyl-1,2-ethylenediamine have been prepared from the reaction of N,N′-dibenzyl-1,2-ethylenediamine with carbon disulfide in the presence of two equivalents of the corresponding alkali metal hydroxide. Additionally, the analogous triethylammonium derivative has been obtained. The resulting compounds have been analyzed as far as possible by elemental analysis, FAB+ mass spectrometry, IR, UV-Vis and NMR (1H, 13C) spectroscopy, and single-crystal X-ray diffraction, showing that the composition of the metal salts can be described by the general formula [{[(H2O)xM-µ-(H2O)yM(H2O)x][bis-dtc]}n] (1, M = Na+, x = 3, y = 2; 2, M = K+, x = 1, y = 2; 3, M = Rb+, x = 0, y = 1; 4, M = Cs+, x = 0, y = 1; 5, M = Et3HN+, x = 0, y = 0). The solid-state and solution studies showed that all alkali metal ions participate in the formation of M–O and cation-π(arene) interactions, while M–S interactions are only observed for the larger alkali metals K+, Rb+ and Cs+. As expected, within the alkali metal group there is a clear tendency for a decreasing number of M–O bonds in favor of M–S and cation–π(arene) interactions, however, only K+ forms a semi-sandwich type complex with η6-coordination.

In the title salt, [K(C(10)H(9)O(4))](n), the K(+) ions are coordinated by six O atoms from three different anions, and there is a cation-π inter-action at ca 3.14 Å. The 2-[2-(carboxymethyl)phenyl]acetate anions are stabilized by intramolecular O-H⋯O hydrogen bonds, and the K(+) cations are linked into one-dimensional coordination polymers running along the b axis; these are further inter-connected by weak C-H⋯O hydrogen bonds.

Racemic trinuclear diphenyltin(IV) cavitands and capsules have been assembled from diphenyltin(IV) and tris-dithiocarbamate ligands.

The structure, dynamic behavior, protonation, methylation, and coordination sites of 2-guanidinobenzimidazole la were investigated. Structures of compounds [2-guanidinium-1,3,10-trihydrobenzimidazole]sulfate lb, [2-guanidinium-l,3-dihydro-benzimidazole]sulfate lc-ld, [2-guanidinium-l,3-dihydro-benzimidazole]tetrafluoroborate le, [2-guanidinium-l,3-dihydro-benzimidazole]chbride If, [2-guanidinium-1,3dihydro-benzimidazole] perchlorate 1% 2-guanidinoI-methyl-benzimidazole 2a, [2-guanidinium-l,3-dimethyl-benzimidazole]iodide 2b, [2-guanidinium-1methyl-3-hydro-benzimidazole]chloride 2c, [2