A new copper(II) basic sulfate: poly[3‐aminopyridinium μ3‐hydroxido‐di‐μ3‐sulfato‐bis[aquacopper(II)]]

The crystal structure of the title basic copper(II) sulfate, {(C₅H₇N₂)[Cu₂(OH)(SO₄)₂(H₂O)₂]}_n, shows an unprecedented structural arrangement of two distinct copper centres. CuO₆ and CuO₅ polyhedra are linked through bridging hydroxide and sulfate anions to form negatively charged infinite chains propagated along the a axis. The negative charge is balanced by 3‐aminopyridinium cations that are held in the structure by extensive hydrogen bonding to the inorganic chains. Additionally, the cationic arrangement features π–π stacking.     

From Small {Mo2O4}2+ Aggregates to Infinite Solids

Mononuclear oxohalomolybdates(V) readily generate in the mixtures of alcohols and pyridines through a series of substitution and dimerization reactions, still reactive dinuclear {Mo₂O₄}²⁺ fragments which assemble together into larger cluster species. In all, the {Mo₂O₄}²⁺ unit with the two molybdenum atoms connected by a single metal-metal bond, appears as a recurrent structural motif, either as a single {Mo₂O₄}²⁺ unit in dinuclear compounds or as assemblies of two, three, four or six units through bridging oxygen donor ligands in tetranuclear, hexanuclear, octanuclear and dodecanuclear compounds, respectively. Pyridine, halide, alkoxide and alcohol ligands occupy the peripheral positions of the molybdenum oxide cores. Their structures will be presented in terms of different arrangements and connectivities among the basic dinuclear building blocks. By using a suitable linker, an oxalate adopting a bisbidentate binding mode was shown to serve the purpose, the {Mo₂O₄}²⁺ units were connected into infinite chains.     

Reactions of Elemental Indium and Indium(I) Bromide with Nickel-Bromine Bonds: Structure of (eta(5)-C(5)H(5))(Ph(3)P)Ni-InBr(2)(O=PPh(3))

The reactions of elemental indium and In(I)Br with the carbonyl-free organonickel complexes (eta(5)-C(5)H(5))(PR(3))Ni-Br (R = CH(3), C(6)H(5)) have been studied in some detail. Either redox reactions to yield the ionic products [(eta(5)-C(5)H(5))(PR(3))(2)Ni][InBr(4)] (2a,b) occurred or the Ni-In bound systems (eta(5)-C(5)H(5))(PPh(3))Ni-InBr(2)(OPPh(3)) (3a) and [(eta(5)-C(5)H(5))(PPh(3))Ni](2)InBr (4) were obtained in good yields. The new compounds were characterized by elemental analysis, NMR, and mass spectrometry. A short Ni-In bond of 244.65(9) pm was found for 3a. Single crystal data for (eta(5)-C(5)H(5))(PPh(3))Ni-InBr(2)(OPPh(3)).THF (3a): triclinic, P1 with a = 1124.9(3), b = 1353.2(4), c = 1476.4(4) pm, alpha = 94.74(2) degrees, beta = 101.78(2) degrees, gamma = 109.64(1) degrees, V = 2044(1) x 10(6) pm(3), Z = 2, R = 0.053 (R(w) = 0.063).     

The synthesis of 5-substituted 3-benzoylamino-6-(2-substituted amino-1-ethenyl)-2H-pyran-2-ones and their transformations into 2H-pyrano[3,2-c]pyridine derivatives

A new approach to the 2H-pyrano[3,2-c]pyridine system is described. 5,6-Disubstituted 3-benzoylamino-2H-pyran-2-ones 3a,b , prepared from the corresponding 1,3-dicarbonyl compounds 1a,b and methyl (Z)-2-benzoylamino-3-dimethylaminopropenoate ( 2 ), were converted into 3-benzoylamino-6-(2-dimethylamino-1-ethenyl)-5-ethoxycarbonyl-2H-pyran-2-one ( 4a ) and 5-acetyl derivative 4b . The exchange of the dimethylamino group in 4a,b with aromatic amines 5a-f,m , héteroaromatic amines 5g-i , and benzylamines 5j-l produced 5-ethoxycarbonyl-3-benzoylamino-6-(2-arylamino- or heteroarylamino-or benzylamino-1-ethenyl)-2H-pyran-2-ones 6a-l , and its 5-acetyl analog 6m . The compounds 6 were cyclized in basic media into 2H-pyrano[3,2-c]pyridine derivatives 7a-h . Analogously react also α-amino acid derivatives 8a-c and 11 as nitrogen nucleophiles producing 9a-c, 10 and 12 .     

Unusually Stable Triazine‐based Organic Superstructures

Solid‐state reactions have been rapidly gaining popularity in organic chemistry owing to their simplicity, efficiency, and selectivity compared to liquid‐phase reactions. Herein, we describe the formation of superstructures through the solid‐state reaction of an organic single‐crystal. The superstructure of 5,5′,5′′‐(1,3,5‐triazine‐2,4,6‐triyl)triisophthalonitrile (TIPN) can be formed by cyclotrimerization of 1,3,5‐tricyanobenzene (TCB) single crystals. The TIPN superstructure was confirmed by single crystal X‐ray diffraction and visualized by transmission electron microscopy. The superstructure has hexagonally packed 1‐dimensional (1D) channels along the crystal axis. Furthermore, the superstructure arises from interdigitated nitrile interactions in the crystal lattice, and thus has electron‐beam tolerance and very high thermal stability.     

An anion receptor with NH and OH groups for hydrogen bonds

An anion receptor with NH and OH groups as hydrogen bond donors has been prepared, and both groups are simultaneously involved in hydrogen bonding with anions.     

Two dimeric CuII benzoate derivatives solvated with aceto­nitrile

The title compounds, tetrakis(μ‐benzoato‐O:O′)­bis(2,6‐di­amino­pyridine)‐1κN,2κN‐dicopper(II)–aceto­nitrile (1/2), [Cu₂(C₇H₅O₂)₄(C₅H₇N₃)₂]·2C₂H₃N, (I), and bis­(aceto­nitrile)‐1κN,2κN‐tetrakis(μ‐benzoato‐O:O′)­dicopper(II)–aceto­nitrile (1/1.5), [Cu₂(C₇H₅O₂)₄(C₂H₃N)₂]·1.5C₂H₃N, (II), crystallize as aceto­nitrile solvates exhibiting different stability. They have similar molecular structures with discrete dimeric units located at crystallographic inversion centres. The copper ions are bridged by four benzoate groups and neutral N‐donor ligands, viz. 2,6‐di­amino­pyridine in (I) and aceto­nitrile in (II), are coordinated at apical positions. The diverse stability is probably due to hydrogen‐bond interactions of the solvated aceto­nitrile mol­ecules with neighbouring dimers in compound (I).     

New heterometallic copper zinc alkoxides: synthesis, structure properties and pyrolysis to Cu/ZnO composites

The copper compound [(THF)KCu(O^tBu)₃]_∞ 1 was obtained by interaction of a 1:1 mixture of ZnCl₂/CuCl₂ with KO^tBu. Bi- and trifunctional aminoalcohols were used to synthesize the intramolecularly donor stabilized Cu(II) alkoxides Cu(OCH(R)CH₂NMe₂)₂ (3: R=Me, 4: =CH₂NMe₂) where 4 was structurally characterized. Lewis acid–base adduct formation with (Me₃Si)₃CZnCl gave the heterodinuclear compounds (Me₃Si)₃CZnCl · Cu(OCH(R)CH₂NMe₂)₂ (5: R=Me, 6: R=CH₂NMe₂), which were characterized by X-ray single-crystal structure analysis. The two metal centers Cu and Zn of 5 and 6 are bridged by two oxygen atoms to form a Cu–O–Zn core. Pyrolysis of compounds 5 and 6 in dry argon or a H₂/N₂ mixture at atmospheric pressure forms metallic copper and zinc oxide, whereas pyrolysis under O₂/Ar forms additionally oxidized copper species. Elemental analysis of the pyrolysis products showed carbon and nitrogen contamination. Scanning electron microscopy and energy dispersive X-ray analysis were performed to get information on the morphology and the chemical composition of the pyrolysis products.     

Methyl 2-benzoylamino-3-dimethylaminopropenoate in the synthesis of heterocyclic systems. An attempt to prepare benzoylamino substituted azolo- and azinopyrimidines with a bridgehead nitrogen atom

Methyl 2-benzoylamino-3-dimethylaminopropenoate ( 2 ) was introduced as a new reagent for the preparation of fused pyrimidinones 4 from heterocyclic α-amino compounds in acetic acid. In this manner, derivatives of pyrido[1,2-a]pyrimidine 4a,b,f , pyrimido[1,2-b]pyridazine 4g , pyrimido[1,2-c]pyrimidine 4j , pyrazino[1,2-a]pyrimidine 4k , thiazolo[2,3-b]pyrimidine 41 , pyrazolo[1,5-a]pyrimidine 4m , and 1,2,4-triazolo-[1,5-a]pyrimidine 4n were prepared.