Two chromium(II) acetate complexes with N-heterocyclic carbene (NHC) coligands.

Tetra-kis(µ-acetato-κ2 O:O')bis-{[1,3-bis-(2,6-diiso-propyl-phen-yl)imidazol-2-yl-idene-κC 2]chromium(II)} tetra-hydro-furan disolvate, [Cr2(C2H3O2)4(C27H36N4)2]·2C4H8O or [Cr2(OAc)4(IDipp)2]·2C4H8O (1), and tetra-kis-(µ-acetato-κ2 O:O')bis-{[1,3-bis-(2,4,6-tri-methyl-phen-yl)imidazol-2-yl-idene-κC 2]chromium(II)},{Cr2(C2H3O2)4(C21H24N2)2] or [Cr2(OAc)4(IMes)2] (2), were synthesized from anhydrous chromium(II) acetate [Cr2(OAc)4] and the corresponding NHC (NHC = N-heterocyclic carbene) in toluene as solvent. Both complexes crystallize in the triclinic system, space group P. The mol-ecular structures consist of Cr2(OAc)4 paddle-wheels that carry two terminal NHC ligands. This leads to a square-pyramidal coordination of the chromium atoms.

Tetra-kis(2,4,6-tri-methyl-anilido)tin(IV).

Transamination of Sn(NMe2)4 with H2NMes (Mes is 2,4,6-tri-methyl-phenyl, C9H11) led to the formation of the title compound, [Sn(C9H12N)4] or Sn(NHMes)4, which crystallizes in the tetra-gonal space group P 21 c, with four formula units per unit cell. The mol-ecular structure consists of a central tin(IV) atom, which is surrounded by four NHMes groups. Sn(NHMes)4 possesses crystallographically imposed symmetry. The SnN4 coordination polyhedron is best described as a compressed bis-phenoid.

Lithium and sodium 3-(3,4-di-hydroxy-phen-yl)propenoate hydrate.

Treatment of 3-(3,4-di-hydroxy-phen-yl)propenoic acid (caffeic acid or 3,4-di-hydroxy-cinnamic acid) with the alkali hydroxides MOH (M = Li, Na) in aqueous solution led to the formation of poly[aqua-[µ-3-(3,4-di-hydroxy-phen-yl)propenoato]lithium], [Li(C9H7O4)(H2O)]n, 1, and poly[aqua-[µ-3-(3,4-di-hydroxy-phen-yl)propenoato]sodium], [Na(C9H7O4)(H2O)]n, 2. The crystal structure of 1 consists of a lithium cation that is coordinated nearly tetra-hedrally by three carboxyl-ate oxygen atoms and a water mol-ecule. The carboxyl-ate groups adopt a µ3-κ3 O:O':O' coordination mode that leads to a chain-like catenation of Li cations and carboxyl-ate units parallel to the b axis. Moreover, the lithium carboxyl-ate chains are connected by hydrogen bonds between water mol-ecules attached to lithium and catechol OH groups. The crystal structure of 2 shows a sevenfold coordination of the sodium cation by one water mol-ecule, two monodentately binding carboxyl-ate groups and four oxygen atoms from two catechol groups. The coordination polyhedra are linked by face- and edge-sharing into chains extending parallel to the b axis. The chains are inter-linked by the bridging 3-(3,4-di-hydroxy-phen-yl)propenoate units and by inter-molecular hydrogen bonds to form the tri-periodic network.

Tetra-kis(µ-acetato-κ2O:O')bis-[(tetra-hydro-furan-κO)chromium(II)].

The title compound, [Cr2(C2H3O2)4(C4H8O)2] or [Cr2(OAc)4(THF)2] (OAc is acetate, THF is tetra-hydro-furan), was obtained by recrystallization of anhydrous chromium(II) acetate [Cr2(OAc)4] from hot tetra-hydro-furan. The centrosymmetric complex forms monoclinic crystals, space group C2/c, and consists of two CrII atoms bridged by four acetate ligands. Additionally, each CrII atom is coordinated by a terminal THF ligand, which leads to a square-pyramidal coordination.

Synthesis and crystal structures of three Schiff bases derived from 3-formyl-acetyl-acetone and benzyl-, tert-butyl- and (S)-methyl-benzyl-amine.

Treatment of 3-formyl-acetyl-acetone with the amines benzyl-amine, tert-butyl-amine and (S)-methyl-benzyl-amine led to the formation of the corresponding Schiff bases 3-[(benzyl-amino)-methyl-idene]pentane-2,4-dione, C13H15NO2 (1), 3-[(tert-butyl-amino)-methyl-idene]pentan-2,4-dione, C10H17NO2 (2) and 3-{[(S)-benz-yl(meth-yl)amino]-methyl-idene}pentane-2,4-dione, C14H17NO2 (3). The mol-ecules of all three compounds exist as enamine tautomers that contain a nearly planar amino-methyl-ene-pentane-2,4-dione core with a strong intra-molecular N-H⋯O hydrogen bridge. The R group attached to the enamine N atom has no significant influence on the bond lengths and angles of the amino-methyl-ene-pentane-2,4-dione core. The supra-molecular structures in 1-3 are mainly based on weak C-H⋯O hydrogen bonds.

Synthesis and crystal structures of three Schiff bases derived from 3-formyl-acetyl-acetone and o-, m- and p-amino-benzoic acid.

Treatment of 3-formyl-acetyl-acetone with the isomeric o-, m- and p-amino-benzoic acids led to the formation of the corresponding Schiff bases, namely, 3-[(2-carb-oxy-phenyl-amino)-methyl-idene]pentane-2,4-dione, 1, 3-[(3-carb-oxy-phenyl-amino)-methyl-idene]pentane-2,4-dione, 2, and 3-[(4-carb-oxy-phenyl-amino)-methyl-idene]pentane-2,4-dione, 3, all C13H13NO4, that contain a planar amino-methyl-ene-pentane-2,4-dione core with a strong intra-molecular N-H⋯O hydrogen bridge. The carb-oxy-phenyl groups attached to the nitro-gen atom are almost coplanar to the central mol-ecular fragment. Depending on the position of the carboxyl unit, different supra-molecular structures with hydrogen-bonding networks are formed in the three title structures.

Concise Synthesis of Both Enantiomers of Pilocarpine.

Furan-2-carboxylic acid was used as a starting material for the synthesis of dehydro-homopilopic acid. Esterification, hydrogenation and enzymatic hydrolysis followed by the reduction of Weinreb amides and a single-step attachment of a 1-methyl-imidazole residue allowed for the concise synthesis of both enantiomers of pilocarpine.

cyclo-Tetra-kis-(µ-2,4,6-tri-methyl-phenyl-κC 1:κC 1)bis-(tri-methyl-phosphane)-1κP,3κP-tetra-copper(I).

The title compound, [Cu4(C9H11)4(C3H9P)2] or [Cu4(Mes)4(PMe3)2] (Mes = 2,4,6-tri-methyl-phenyl), was synthesized from copper(I) mesityl and tri-methyl-phosphane in THF as solvent. The mol-ecular structure of the complex has C 2 symmetry and consists of four copper(I) atoms bridged by four µ-mesityl groups, giving an eight-membered puckered {Cu4C4} ring. Additionally, two copper(I) atoms at opposite corners of the Cu4 rhomb are each linked to a terminal PMe3 ligand. The PMe3-bearing copper(I) atoms exhibit a distorted trigonal-planar coordination mode whereas the remaining Cu atoms linked to two mesityl groups are nearly linearly coordinated.

Syntheses and crystal structures of three [M(acac)2(TMEDA)] complexes (M = Mn, Fe and Zn).

The complexes bis-(acetyl-acetonato-κ2 O,O')(N,N,N',N'-tetra-methyl-ethylenedi-amine-κ2 N,N')manganese(II), [Mn(C5H7O2)2(C6H16N2)], bis-(acetyl-acetonato-κ2 O,O')(N,N,N',N'-tetra-methyl-ethylenedi-amine-κ2 N,N')iron(II), [Fe(C5H7O2)2(C6H16N2)], and bis-(acetyl-acetonato-κ2 O,O')(N,N,N',N'-tetra-methyl-ethylenedi-amine-κ2 N,N')zinc(II), [Zn(C5H7O2)2(C6H16N2)], were synthesized from the reaction of the corresponding metal acetyl-acetonates [M(acac)2(H2O)2] with N,N,N',N'-tetra-methyl-ethylenedi-amine (TMEDA) in toluene. Each of the complexes displays a central metal atom which is nearly octa-hedrally surrounded by two chelating acac and one chelating TMEDA ligand, resulting in an N2O4 coordination set. Despite the chemical similarity of the complex units, the packing patterns for compounds 1-3 are different and thus the crystal structures are not isotypic.

Nor-guanacastepene pigments from the Chilean mushroom Cortinarius pyromyxa.

For the first time, the pigment composition of basidiocarps from the Chilean mushroom Cortinarius pyromyxa was studied under various aspects like phylogeny, chemistry and antibiotic activity. A molecular biological study supports the monotypic position of C. pyromyxa in subgenus Myxacium, genus Cortinarius. Four undescribed diterpenoids, named pyromyxones A-D, were isolated from fruiting bodies of C. pyromyxa. Their chemical structures were elucidated based on comprehensive one- and two-dimensional NMR spectroscopic analysis, ESI-HRMS measurements, as well as X-ray crystallography. In addition, the absolute configurations of pyromyxones A-D were established with the aid of JH,H, NOESY spectra and quantum chemical CD calculation. The pyromyxones A-D possess the undescribed nor-guanacastane skeleton. Tested pyromyxones A, B, and D exhibit only weak activity against gram-positive Bacillus subtilis and gram-negative Aliivibrio fischeri as well as the phytopathogenic fungi Botrytis cinerea, Septoria tritici and Phytophthora infestans.

Pyrofomins A-D, polyoxygenated sesquiterpenoids from Pyrofomes demidoffii.

Pyrofomins A-D, four polyoxygenated sesquiterpenoids have been isolated from the methanolic extract of the fruit bodies of Pyrofomes demidoffii. Their structures are elucidated by IR, HR-FTICR-MS, and 2D NMR spectroscopy. Furthermore, the cedrane carbon skeleton of pyrofomin A (1) is confirmed by X-ray crystallographic analysis. The sesquiterpenoids 1-4 show neither cytotoxicity against KB cells nor antimicrobial activity.

Formation of ortho-cyano-aminothiophenolate ligands with versatile binding modes via facile carbon-sulfur bond cleavage of 2-aminobenzothiazoles at mercury(II) centres.

Addition of 2-aminobenzothiazole and substituted derivatives to mercuric acetate in warm ethanol leads to the high yield formation of [Hg{SC6H3XN(C[triple bond, length as m-dash]N)}]n resulting from loss of hydrogen and sulfur-carbon bond cleavage. Addition of phosphines affords a series of complexes in which the new ortho-cyano-aminothiophenolate ligands adopt three different binding modes.

catena-Poly[[[diaqua-(tetra-methyl-ethylenediamine-κ(2) N,N')nickel(II)]-µ-sulfato-κ(2) O:O'] monohydrate].

The title compound, {[Ni(SO4)(C6H16N2)(H2O)2]·H2O} n , contains a Ni(II) atom that is coordinated nearly octa-hedrally by a chelating tetra-ethyl-enediamine (tmeda) ligand, two water mol-ecules in a cis arrangement and two O atoms of two sulfate anions in a trans arrangement. The sulfate anions act as µ2-bridging ligands leading to a chain structure of alternating NiO4N2 octa-hedra and SO4 tetra-hedra parallel to [001]. The polymeric chains are linked by O-H⋯O hydrogen bonds between coordinating water mol-ecules and sulfate anions to give double strands. There is a lattice water mol-ecule which is also involved in O-H⋯O hydrogen bonding between adjacent [Ni(SO4)(tmeda)(H2O)2] chains.

catena-Poly[(µ-anilido)(µ-1,2-dimeth-oxy-ethane-κ(3)-O,O':O)sodium].

In the title compound, [Na(C(6)H(5)NH)(C(4)H(10)O(2))], the Na(+) cation is coordinated by the N atoms of two anilide anions, two O atoms of a chelating 1,2-dimeth-oxy-ethane (dme) ligand and one O atom of an adjacent dme ligand. The coordination polyhedron around Na(+) corresponds to a distorted square pyramid with the N atoms of the anilide groups and the O atoms of the chelating dme unit at the base and a third O atom at the apical position. The anilide anions act as µ-bridging ligands and the 1,2-dimeth-oxy-ethane mol-ecules display a µ(2)-κ(3)-O,O' coordination mode. As a result of this connectivity, a polymeric chain structure parallel to [100] is formed, consisting of Na(2)O(2) and Na(2)N(2) four-membered rings. It should be noted that the remaining H atom of the anilide NH group is not involved in hydrogen bonding.

catena-Poly[[tricarbonyl-1κ³C-(1η5-cyclo-penta-dien-yl)lead(II)molyb-denum(0)](Mo-Pb)-µ3-acetato-2':2:2''κ4O:O,O':O'].

In the title compound, [MoPb(C5H5)(CH3COO)(CO)3], the Pb(II) atom is coordinated pyramidally via the Mo(0) atom of a {Cp(CO)3Mo} (Cp = cyclo-penta-dien-yl) fragment [Pb-Mo = 3.0589 (5) Å] and a chelating acetate (Ac) group. Additionally, the [{Cp(CO)3Mo}PbAc] units are linked along [100] by Pb-O(acetate) inter-actions, giving a ladder-type polymeric structure composed of PbCO2 and Pb2O2 four-membered rings. The {Cp(CO)3Mo} units attached to the Pb(II) atom occupy terminal positions at opposite sides of the slightly puckered lead acetate chain. The angle between the Pb-Mo bond vector and the central chain plane is 67.8 (2)°.

Hydrogen 4-ammonio-phenyl-phospho-n-ate.

The title compound, C(6)H(8)NO(3)P, is isostructural with p-arsanilic acid. It exists as the zwitterion H(3)N(+)C(6)H(4)PO(3)H(-). In the crystal, mol-ecules are linked by O-H⋯O and N-H⋯O hydrogen-bond bridges, giving a three-dimensional network structure. The strongest hydrogen bonds are formed between adjacent PO(3)H groups with O⋯O distances of 2.577 (2) Å.

Bis(hydrogen l-glutamato)palladium(II).

In the title compound, [Pd(C(5)H(8)NO(4))(2)], the Pd(II) atom is coordinated by two O atoms and two N atoms of two N,O-chelating hydrogen l-glutatmate ligands in a square-planar geometry with the N and O atoms in a mutually trans arrangement. The complex units are embedded in a network of N-H⋯O and O-H⋯O hydrogen-bonding inter-actions that stabilize the three-dimensional crystal structure. The strongest hydrogen bonds are formed between the γ-COOH untis of adjacent glutamate ligands, leading to dimers of the type R(2) (2)(8) with O⋯O separations of 2.640 (6) Å.

Tetra-carbonyl-1κC,3κC-bis[1,3(η)-cyclo-penta-dien-yl]dihydroxido-2κO-diirontin(2 Fe-Sn) monohydrate.

In the title hydrate, [Fe(2)Sn(C(5)H(5))(2)(OH)(2)(CO)(4)]·H(2)O, the central Sn atom is tetra-hedrally coordinated by two {Cp(CO)(2)Fe} fragments and two hydroxide groups. The [{Cp(CO)(2)Fe}(2)Sn(OH)(2)] and water mol-ecules are linked by O-H⋯O hydrogen bridges, giving two-dimensional arrays with 4.8(2) topology that stack along the c axis.

(1,4,7,10-Tetra-aza-cyclo-dodecane-κN,N,N,N)(tetra-oxidomolybdato-κO)copper(II) monohydrate.

In the title compound, [CuMoO(4)(C(8)H(20)N(4))]·H(2)O, the Cu(II) atom is coordinated by four N atoms of the 1,4,7,10-tetra-aza-cyclo-dodecane (cyclen) ligand and one O atom of the molybdate unit in a distorted square-pyramidal environment. The water mol-ecules are linked to the complex unit to form centrosymmetric dimers [R(4) (4)(12) and R(4) (4)(16)] and discrete D(3) (2)(9), D(3) (3)(11) and D(3) (3)(13) chains by O-H⋯O and N-H⋯O inter-actions. Additionally, the complex mol-ecules are linked into C(4) (4)(18) chain motifs by N-H⋯O inter-actions. As a result [(cyclen)CuMoO(4)] units and water molecules are linked to layers that are oriented parallel to the ac plane. The stacking of the layers in the b-axis direction is supported by weak C-H⋯O hydrogen bridges.

N,N'-Dicyclo-hexyl-ethyl-enediammonium dichloride.

In the title compound, C(14)H(30)N(2) (2+)·2Cl(-), the N,N'-dicyclo-hexyl-ethyl-enediammonium cation posseses crystallographic symmetry, and thus the compound crystallizes with two formula units per unit cell. In the crystal, the cations and anions are linked by N-H⋯Cl hydrogen bonds, giving a two-dimensional network with {6,3} topology.