Three 1,2,4‐triazole derivatives containing subtituted benzyl and benzyl­amino groups

The title compounds, 4‐benzyl­amino‐3‐(4‐methyl­benzyl)‐1H‐1,2,4‐triazol‐5(4H)‐one, C₁₇H₁₈N₄O, (I), 3‐(4‐methyl­benzyl)‐4‐(4‐methyl­benzyl­amino)‐1H‐1,2,4‐tri­azol‐5(4H)‐one, C₁₈H₂₀N₄O, (II), and 3‐(4‐chloro­benzyl)‐4‐(4‐methyl­benzyl­amino)‐1H‐1,2,4‐triazol‐5(4H)‐one, C₁₇H₁₇ClN₄O, (III), were obtained from the corresponding Schiff base in the presence of diglyme and NaBH₄. Each compound contains a 1,2,4‐triazole ring and two benzene rings, which are essentially planar. The molecules are linked by a combination of intermolecular N—H⋯O and N—H⋯N hydrogen bonds. Additionally, there is a weak π–π stacking interaction in (I), involving the benzene ring of the amino­benzyl group and the partially aromatic 1,2,4‐triazole moiety, with a centroid–centroid distance of 3.7397 (10) Å.     

4,4′‐Bis(4‐iodo­phenyl­amino­methyl)­azoxy­benzene: hydrogen‐bonded sheets built from C—H⃛O and C—H⃛π(arene) hydrogen bonds

Borohydride reduction of N‐(4‐nitro­benzyl­idene)‐4‐iodo­aniline has yielded the title compound, 1,2‐bis­[4‐(4‐iodo­phenyl­amino­methyl)­phenyl]­diazene 1‐oxide, C₂₆H₂₂I₂N₄O. The mol­ecules lie across centres of inversion in P2₁/c, with the azoxy O atom disordered over two sites, each having an occupancy of 0.5. The mol­ecules are linked into sheets by a combination of C—H⃛O and C—H⃛π(arene) hydrogen bonds.     

Ethyl N‐[2‐(hydroxy­acetyl)­phenyl]­carbamate,ethyl N‐[2‐(hydroxy­acetyl)‐4‐iodo­phenyl]­carbamate and ethyl N‐[2‐(hydroxy­acetyl)‐4‐methyl­phenyl]­carbamate

In ethyl N‐[2‐(hydroxy­acetyl)phenyl]carbamate, C₁₁H₁₃NO₄, all of the non‐H atoms lie on a mirror plane in the space group Pnma; the mol­ecules are linked into simple chains by a single C—H⋯O hydrogen bond. The mol­ecules of ethyl N‐[2‐(hydroxy­acetyl)‐4‐iodo­phenyl]carbamate, C₁₁H₁₂INO₄, are linked into sheets by a combination of O—H⋯I and C—H⋯O hydrogen bonds and a dipolar I⋯O contact. Ethyl N‐­[2‐(hydroxy­acetyl)‐4‐methyl­phenyl]carbamate, C₁₂H₁₅NO₄, crystallizes with Z′ = 2 in the space group P; pairs of mol­ecules are weakly linked by an O—H⋯O hydrogen bond and these aggregates are linked into chains by two independent aromatic π–π stacking inter­actions.     

Four (E,Z,E)‐1‐(4‐alkoxy­phen­yl)‐6‐(4‐nitro­phen­yl)hexa‐1,3,5‐trienes

The crystal structures of the four E,Z,E isomers of 1‐(4‐alk­oxy­phen­yl)‐6‐(4‐nitro­phen­yl)hexa‐1,3,5‐triene, namely (E,Z,E)‐1‐(4‐methoxy­phen­yl)‐6‐(4‐nitro­phen­yl)hexa‐1,3,5‐triene, C₁₉H₁₇NO₃, (E,Z,E)‐1‐(4‐ethoxy­phen­yl)‐6‐(4‐nitro­phen­yl)hexa‐1,3,5‐triene, C₂₀H₁₉NO₃, (E,Z,E)‐1‐(4‐nitro­phen­yl)‐6‐(4‐n‐propoxyphen­yl)hexa‐1,3,5‐triene, C₂₁H₂₁NO₃, and (E,Z,E)‐1‐(4‐n‐butoxy­phen­yl)‐6‐(4‐nitro­phen­yl)hexa‐1,3,5‐triene, C₂₂H₂₃NO₃, have been determined. Inter­molecular N⋯O dipole inter­actions between the nitro groups are observed for the meth­oxy derivative, while for the eth­oxy derivative, two adjacent mol­ecules are linked at both ends through N⋯O dipole–dipole inter­actions between the N atom of the nitro group and the O atom of the eth­oxy group to form a supra­molecular ring‐like structure. In the crystal structures of the n‐prop­oxy and n‐but­oxy derivatives, the shortest inter­molecular distances are those between the two O atoms of the alk­oxy groups. Thus, the nearest two mol­ecules form an S‐shaped supra­molecular dimer in these crystal structures.     

Pomiferin

The crystal structure of pomiferin, 3‐(3,4‐di­hydroxy­phenyl)‐5‐hydroxy‐8,8‐di­methyl‐6‐(3‐methyl­but‐2‐enyl)‐4H,8H‐pyrano[2,3‐h]­chromen‐4‐one, C₂₅H₂₄O₆, has been determined. The benzo­pyran­one ring system is nearly planar and the dihedral angle between the phenyl ring and the benzo­pyran­one moiety is 40.85 (4)°. The crystal structure is stabilized by a one‐dimensional chain of inter‐ and intramolecular O—H⃛O hydrogen bonds, with O⃛O distances in the range 2.5546 (15)–2.7999 (16) Å.     

4‐(4‐Hydro­xy­benzyl­idene­amino)‐4H‐1,2,4‐triazole hemihydrate

In the title compound, 4‐(4H‐1,2,4‐triazol‐4‐yl­imino­methyl)­phenol hemi­hydrate, C₉H₈N₄O·0.5H₂O or (I)·0.5H₂O, mol­ecules of (I) are arranged as layers running along the b axis through intermolecular O—H?N and C—H?O hydrogen bonds. These layers are stabilized by hydrogen‐bonded water mol­ecules to form three‐dimensional networks.     

The gold(III) tetra­chloride salt of L‐cocaine

The title salt, methyl (1R,2R,3S,5S,8S)‐3‐benzoyl­oxy‐8‐methyl‐8‐aza­bicyclo­[3.2.1]octane‐2‐carboxyl­ate tetra­chloro­aurate(III), (C₁₇H₂₂NO₄)[AuCl₄], has its protonated N atom intra­molecularly hydrogen bonded to the O atom of the methoxy­carbonyl group [N⋯O = 2.755 (6) Å and N—H⋯O = 136°]. Two close inter­molecular C—H⋯O contacts exist, as well as five C—H⋯Cl close contacts. The [AuCl₄]⁻ anion was found to be distorted square planar.     

1,3‐Thia­zolidine derivatives from regioselective [2+3]‐cyclo­additions of azomethine yl­ides with thio­ketones

The title compounds, namely di­methyl (2RS)‐2,3‐di­phenyl‐1,3‐thia­zolidine‐5‐spiro‐2′‐adam­antane‐4,4‐di­carboxyl­ate methanol sol­vate, C₂₈H₃₁NO₄S·0.275CH₄O, and di­methyl (4RS)‐3,4‐di­phenyl‐1,3‐thia­zolidine‐5‐spiro‐9′‐(9′H‐fluorene)‐2,2‐di­car­box­ylate, C₃₁H₂₅NO₄S, were obtained from dipolar [2+3]‐cyclo­additions of an azo­methine yl­ide with adamantane­thione and thio­fluorenone, respectively. The structures show that the choice of thio­ketone affects the regioselectivity of the cyclo­addition. The asymmetric unit of the former structure contains two mol­ecules of the thia­zolidine derivative plus a site for a partial occupancy (55%) methanol mol­ecule. O—H⋯O and C—H⋯O interactions link two of each of these entities into closed centrosymmetric hexamers. The five‐membered ring in each structure has an envelope conformation.     

Four copper(II) complexes with potentially tetradentate tripodal ligands

The four title Cu^II compounds are chloro­[(2‐furyl­methyl)­bis(2‐pyridyl­methyl)­amine‐N,N′,N′′]copper(II) perchlorate, [CuCl(C₁₇H₁₇N₃O)]ClO₄, (I), chloro{2‐[bis(2‐pyridyl­methyl)­amino]­ethano­lato‐N,N′,N′′,O}­copper(II) hemi­[tetra­chloro­copper(II)], [CuCl(C₁₄H₁₇N₃O)][CuCl₄]_1/2, (II), chloro­[(2‐morpholino­ethyl)­bis(2‐pyridyl­methyl)­amine‐N,N′,N′′,N′′′]copper(II) perchlorate, [CuCl(C₁₈H₂₄N₄O)]ClO₄, (III), and chloro­[(2‐piperidinyl­ethyl)­bis(2‐pyridyl­methyl)­amine‐N,N′,N′′,N′′′]­copper(II) hexa­fluoro­phosphate, [CuCl(C₁₉H₂₆N₄)]­PF₆, (IV). They have tripodal potentially tetradentate ligands. In (I), the O atom of the furan moiety weakly coordinates to the Cu atom at a distance of 2.750 (3) Å.     

3‐(4‐Cyano­phenyl)­pentane‐2,4‐dione and its copper(II) complex

The β‐diketone 3‐(4‐cyano­phenyl)­pentane‐2,4‐dione crystallizes as the enol tautomer 4‐(2‐hydroxy‐4‐oxopent‐2‐en‐3‐yl)­benzo­nitrile, C₁₂H₁₁NO₂, (I), with an intramolecular O—H⋯O hydrogen bond [O⋯O = 2.456 (2) Å]. Reaction of (I) with copper acetate monohydrate in the presence of triethyl­amine leads to the formation of the copper(II) complexbis­[3‐(4‐cyano­phenyl)­pentane‐2,4‐dionato‐κ²O,O]copper(II), [Cu(C₁₂H₁₀NO₂)₂], (II). In the structure of (II), the Cu atom is coordinated by four β‐diketonate O atoms in a slightly distorted square‐planar geometry, with Cu—O distances in the range 1.8946 (11)–1.9092 (11) Å. The nitrile moieties in (II) make it a candidate for reaction with other metal ions to produce supramolecular structures.     

Copper(II) and zinc(II) complexes of pyridine‐2,6‐di­carboxyl­ic acid

The title compounds, bis­(pyridine‐2,6‐di­carboxyl­ato‐N,O,O′)copper(II) monohydrate, [Cu(C₇H₄NO₄)₂]·H₂O, andbis(pyridine‐2,6‐dicarboxylato‐N,O,O′)zinc(II) trihydrate, [Zn(C₇H₄NO₄)₂]·3H₂O, have distorted octahedral geometries about the metal centres. Both metal ions are bonded to four O atoms and two pyridyl‐N atoms from the two terdentate ligand mol­ecules, which are nearly perpendicular to each other. The copper(II) complex has twofold crystallographic symmetry and contains two different ligand mol­ecules, one of which is neutral and another doubly ionized. In contrast, the zinc(II) complex contains two identical singly ionized ligand mol­ecules. Both crystal structures are stabilized by O—H?O intermolecular hydrogen bonds between the complex and the water mol­ecules.     

Berberine formate–succinic acid (1/1)

The title compound [systematic name: 9,10‐di­methoxy‐2,3‐methyl­ene­dioxy‐5,6‐di­hydro­dibenzo­[a,g]­quinolizinium form­ate–succinic acid (1/1)], C₂₀H₁₈NO₄⁺·CHO₂⁻·C₄H₆O₄, con­tains centrosymmetric pairs of almost planar berberine cations, and hydrogen‐bonded (C₄H₆O₄⋯HCOO⁻)₂ rings of succinic acid with formate anions, bonded by O—H⋯O hydrogen bonds with O⋯O distances of 2.4886 (15) and 2.5652 (16) Å. Pairs of cations and mol­ecules of succinic acid are connected by non‐conventional weak C—H⋯O hydrogen bonds, with C⋯O distances of 3.082 (2) and 3.178 (2) Å.     

Supramolecular structures of three isomeric 4‐(methyl­phenylamino)­pyridine‐3‐sulfonamides

The structures of the three title isomers, namely 4‐(2‐methyl­anilino)pyridine‐3‐sulfonamide, (I), 4‐(3‐methyl­anilino)pyridine‐3‐sulfonamide, (II), and 4‐(4‐methyl­anilino)pyridine‐3‐sulfonamide, (III), all C₁₂H₁₃N₃O₂S, differ in their hydrogen‐bonding arrangements. In all three mol­ecules, the conformation of the 4‐amino­pyridine‐3‐sulfon­amide moiety is conserved by an intra­molecular N—H⋯O hydrogen bond and a C—H⋯O inter­action. In the supra­mol­ecular structures of all three isomers, similar C(6) chains are formed via inter­molecular N—H⋯N hydrogen bonds. N—H⋯O hydrogen bonds lead to C(4) chains in (I), and to R₂²(8) centrosymmetric dimers in (II) and (III). In each isomer, the overall effect of all hydrogen bonds is to form layer structures.     

The 1:1 adduct of Kemp's triacid with 2‐aminopyridine

The crystal structure determination of the molecular proton‐transfer adduct of Kemp's triacid (cis‐cis‐1,3,5‐tri­methyl­cyclo­hexane‐1,3,5‐tri­carboxylic acid, KTA) with 2‐amino­pyridine (2‐APY), namely 2‐amino­pyridinium 3,5‐di­carboxy‐1,3,5‐tri­methyl­cyclo­hexane­carboxyl­ate, 2‐APY⁺·KTA^? or C₅H₇N₂⁺·C₁₂H₁₇O₆^?, has revealed a centrosymmetric hydrogen‐bonded cyclic KTA homodimer repeating unit [O?O 2.524 (4) Å] linked into a polymer structure through the pyridinium and amino groups of the 2‐APY mol­ecule [O?N 2.736 (4), 2.989 (4) and 2.999 (4) Å].     

Bis(acesulfamato‐κO4)diaqua­bis­(3‐methyl­pyridine‐κN)nickel(II)

In the crystal structure of the title compound [systematic name: diaqua­bis(6‐methyl‐2,2‐dioxo‐1,2,3‐oxathia­zin‐4‐olato‐κO⁴)bis­(3‐methyl­pyridine‐κN)nickel(II)], [Ni(C₄H₄NO₄S)₂(C₆H₇N)₂(H₂O)₂], the Ni^II centre resides on a centre of symmetry and has a distorted octa­hedral geometry. The basal plane is formed by two carbonyl O atoms of two monodentate trans‐oriented acesulfamate ligands and two trans aqua ligands. The axial positions in the octa­hedron are occupied by two N atoms of two trans pyridine ligands. Mol­ecules are stacked in columns running along the a axis. There are π–π stacking inter­actions between the mol­ecules in each column, with a distance of 3.623 (2) Å between the centroids of the pyridine rings. There are also O—H⋯O inter­actions between the columns.     

Adducts of 1,1,1‐tris(4‐hydroxy­phenyl)­ethane with 1,2‐bis(4‐pyridyl)­ethane and 1,2‐bis(4‐pyridyl)­ethene: continuously interwoven structures in three dimensions

In the adduct 1,2‐bis(4‐pyridyl)­ethane–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2), C₁₂H₁₂N₂·2C₂₀H₁₈O₃, the bipyridyl component lies across an inversion centre in P. The tris‐phenol mol­ecules [systematic name: 4,4′,4′′‐(ethane‐1,1,1‐triyl)­triphenol] are linked by O—H?O hydrogen bonds to form sheets built from R(38) rings, and symmetry‐related pairs of sheets are linked by the bipyridyl mol­ecules via O—H?N hydrogen bonds to form open bilayers. Each bilayer is interwoven with two adjacent bilayers, forming a continuous three‐dimensional structure. In the adduct 1,2‐bis(4‐pyridyl)­ethene–1,1,1‐tris(4‐hydroxy­phenyl)­ethane–methanol (1/1/1), C₁₂H₁₀N₂·C₂₀H₁₈O₃·CH₄O, the mol­ecules are linked by O—H?O and O—H?N hydrogen bonds into three interwoven three‐dimensional frameworks, generated by single spiral chains along [010] and [001] and a triple‐helical spiral along [100].     

Compositional disorder in trans‐[RhBr0.26Cl0.74H(PMe3)4][B(1,2‐O2C6Br4)]·CH2Cl2

The structure of trans‐(bromo/­chloro)­hy­drido­tetra­kis­(tri‐me­thyl­phos­phine)­rhod­ium(III) bis­(tetra­bromo­pyro­catechol‐ato‐O,O′)­borate dichloromethane solvate, [RhCl_0·74Br_0·26H‐(C₃­H₉­P)₄]­(C₁₂­BBr₈­O₄)·­CH₂Cl₂, is reported. The Rh^III com­plex shows bromine/chlorine compositional disorder with a trans arrangement of the hydride and halide ligands. The anion has approximate D_2d symmetry, with a central spiro‐B atom distorted from regular tetrahedral geometry by the small chelating O—B—O angles.     

N‐Benzyl­tetra­hydro­pyrido‐anellated thio­phene derivatives: new anti­cholinesterases

The title compounds, tert‐butyl 6‐benzyl‐2‐(3,3‐diethyl­ureido)‐4,5,6,7‐tetra­hydro­thieno[2,3‐c]pyridine‐3‐carboxyl­ate, C₂₄H₃₃N₃O₃S, (I), 7‐benzyl‐2‐diethyl­amino‐5,6,7,8‐tetra­hydro‐3‐oxa‐9‐thia‐1,7‐diaza­fluoren‐4‐one, C₂₀H₂₃N₃O₂S, (II), and N‐(7‐benzyl‐4‐oxo‐5,6,7,8‐tetra­hydro‐4H‐3,9‐dithia‐1,7‐diaza­fluoren‐2‐yl)benzamide, C₂₃H₁₉N₃O₂S₂, (III), form monoclinic crystal systems. In (I) and (II), the mol­ecules are linked into a three‐dimensional framework by weak inter­molecular C—H⋯O=C hydrogen bonds, whereas in (III) stronger inter­molecular N—H⋯O=C inter­actions are observed. The conformation of (I) is further stabilized by an intra­molecular N—H⋯O=C hydrogen bond, which effects the planarity of the ureido­thio­phene­carboxyl­ate moiety.     

A novel one‐dimensional coordination polymer with Cd2+ and diethylenetriaminepentaacetic acid

catena‐Poly­[[[bis­[di­aqua(4,4′‐bi­pyridine)­cadmium(II)]‐bis­[μ‐(N′′‐carboxy­methyl­diethyl­enetri­amine‐N,N,N′,N′′‐tetra­ace­ta­to)­cadmium(II)]]‐μ‐4,4′‐bi­pyridine] tetradecahydrate], [Cd₄­(C₁₄H₁₉N₃O₁₀)₂(C₁₀H₈N₂)₃(H₂O)₄]·14H₂O or [Cd₄(HD­TPA)₂(BPY)₃(H₂O)₄]·14H₂O, where BPY is 4,4′‐bi­pyridine and HDTPA^4? is N′′‐carboxy­methyl­diethyl­enetri­amine‐N,N,N′,N′′‐tetra­acetate, consists of a one‐dimensional coordination polymer formed from a secondary building unit which comprises four Cd centres. The chain structure of the title compound was obtained by the use of a multidentate organic ligand, N,N,N′,N′′,N′′‐diethyl­enetri­amine­penta­acetic acid (H₅DTPA), which forms multiple chelate rings with the Cd metal centres. An extended network is formed via hydrogen bonds.     

Tetrameric triphenylsilanol, (Ph3SiOH)4, and the adduct (Ph3SiOH)2–di­methyl sulfoxide,both at 120 K,and the adduct (Ph3SiOH)4–1,4‐dioxan at 150 K: interplay of O—H⋯O and C—H⋯π(arene) interactions

The structure of tetrameric tri­phenyl­silanol, C₁₈H₁₆OSi, (I), has been re‐investigated at 120 (2) K. The hydroxyl H atoms were readily located and one of the arene rings is disordered over two closely positioned sets of sites. The mol­ecules are linked into cyclic tetramers, having approximate (S₄) symmetry, via O—H?O hydrogen bonds [H?O 1.81–1.85 Å, O?O 2.634 (3)–2.693 (3) Å and O—H?O 156–166°]. At ambient temperature, there are indications of multiple disorder of the phenyl‐ring sites. In bis­(tri­phenyl­silanol) di­methyl sulfoxide solvate, 2C₁₈H₁₆OSi·C₂H₆OS, (II), the di­methyl sulfoxide component is disordered across a twofold rotation axis in C2/c, and the molecular components are linked by a single O—H?O hydrogen bond [H?O 1.85 Å, O?O 2.732 (2) Å and O—H?O 172°] into three‐mol­ecule aggregates, which are themselves linked into a single three‐dimensional framework by two C—H?π(arene) interactions. In tetrakis­(tri­phenyl­silanol) 1,4‐dioxan solvate, 4C₁₈H₁₆OSi·C₄H₈O₂, (III), the 1,4‐dioxan component lies across an inversion centre in space group P and centrosymmetric five‐mol­ecule aggregates are linked by paired C—H?π(arene) interactions to form molecular ladders.