Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and polymeric adducts with 1,2‐bis(4‐pyridyl)­ethene and 1,6‐di­amino­hexane

In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,2‐bis(4‐pyridyl)­ethene (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₀N₂, there is an intramolecular O—H?O hydrogen bond in the ferro­cene­diol component and a single O—H?N hydrogen bond linking the diol to the di­amine, which is disordered over two sets of sites, so forming a finite monomeric adduct. In the adduct ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–1,6‐di­amino­hexane (2/1), 2[Fe(C₁₈H₁₅O)₂]·C₆H₁₆N₂, the amine lies across a centre of inversion in space group P. There is an intramolecular O—H?O hydrogen bond in the ferrocenediol, and the molecular components are linked by O—H?N and N—H?O hydrogen bonds, one of each type, into a C(13)[R(12)] chain of rings.     

6,7‐Dihydrodibenzo[e,g]azulen‐8(5H)‐one and 12,13‐dihydrobenzo[e]­napth­[2,1‐g]­azulen‐14(11H)‐one

In the structures of the title compounds, 6,7‐di­hydro­dibenzo[e,g]­azulen‐8(5H)‐one, C₁₈H₁₄O, (I), and 12,13‐di­hydro­benzo[e]­napth­[2,1‐g]­azulen‐14(11H)‐one, C₂₂H₁₆O, (II), the azulene group is in a boat‐envelope conformation. The structures are stabilized by weak C—H?O interactions.     

Three monoalkoxy‐substituted nido‐platinaboranes: [(PPh3)2PtB10H11‐8‐(OCH3)], [(PPh3)2PtB10H11‐8‐{OCH(CH3)2}] and [(PPh3)2PtB10H10‐9‐{OCH(CH3)2}]

Each of the title compounds, 8‐methoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane hemisolvate, [Pt(CH₁₄B₁₀O)(C₁₈H₁₅P)₂]·0.5CH₂Cl₂, (I), 8‐isopropoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane solvate, [Pt(C₃H₁₈B₁₀O)(C₁₈H₁₅P)₂]·CH₂Cl₂, (II), and 9‐isopropoxy‐7,7‐bis­(tri­phenyl­phosphine‐P)‐8,9:10,11‐di‐μH‐7‐platina‐nido‐undecaborane di­chloro­methane solvate, [Pt(C₃H₁₈B₁₀O)(C₁₈H₁₅P)₂]·CH₂Cl₂, (III), has an 11‐vertex nido polyhedral skeleton, with the 7‐platinum centre ligating to two exo‐polyhedral PPh₃ groups and an alkoxy‐substituted polyhedral borane ligand. Compounds (II) and (III) are isomers. The Pt—B distances are in the range 2.214 (7)–2.303 (7) Å for (I), 2.178 (16)–2.326 (16) Å for (II) and 2.205 (6)–2.327 (6) Å for (III).     

Two new conformationally restricted 4,5‐dihydroxynorvaline analogues with a norbornane skeleton

The structures of two conformationally restricted 4,5‐di­hydroxy­norvaline analogues with a norbornane skeleton, namely methyl (1S,2S,3R,4R)‐2‐benz­amido‐3‐(1,2‐di­hydroxy­ethyl)­bi­cyclo[2.2.1]­heptane‐2‐carboxyl­ate, C₁₈H₂₃NO₅, and methyl (1R,2S,3R,4S)‐2‐benz­amido‐3‐(1,2‐di­hydroxy­ethyl)­bi­cyclo[2.2.1]­heptane‐2‐carboxyl­ate, C₁₈H₂₃NO₅, exhibit a conformation in the helical region of the ?,ψ map but their handedness is opposite. In both cases, the torsion angles (χ^1,1) giving the relative orientation of the 1,2‐di­hydroxy­ethyl group of the amino acid side chain and the benz­amide group of the peptide chain indicate that these groups adopt a nearly eclipsed conformation. Both compounds show a complex hydrogen‐bonding pattern.     

Three different bonding modes of cyano groups in the coordination polymer [Cu(en)2(H2O)][Cu(en)2Ni2Cu2(CN)10]·2H2O (en is 1,2‐diaminoethane)

Partial reduction of the Cu^II ions in the aqueous system Cu^II–en–[Ni(CN)₄]^2? (1/1/1) (en is 1,2‐di­amino­ethane) yields a novel heterobimetallic mixed‐valence compound, poly­[[aqua­bis(1,2‐di­amino­ethane)copper(II)] [hexa‐μ‐cyano‐tetra­cyano­bis(1,2‐di­amino­ethane)­tricopper(I,II)­dinickel(II)] dihydrate], [Cu(C₂H₈N₂)₂(H₂O)][Ni₂Cu₃(CN)₁₀(C₂H₈N₂)₂]·2H₂O or [Cu(en)₂(H₂O)][Cu(en)₂Ni₂Cu₂(CN)₁₀]·2H₂O. The structure is formed by a negatively charged two‐dimensional array of the cyano complex [Cu(en)₂Ni₂Cu₂(CN)₁₀]_n^2n?, [Cu(en)₂(H₂O)]²⁺ complex cations and water mol­ecules of crystallization. These last are involved in a complicated hydrogen‐bonding system. The cyano groups act as terminal, μ₂‐bridging or μ₃‐bridging ligands.     

Hydro­gen‐bonded adducts of ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol): monomeric and dimeric 1:1 adducts with 1,2‐bis(4‐pyridyl)­ethane and 1,2‐­diamino­ethane

In ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–4,4′‐ethyl­enedi­pyridine (1/1), [Fe(C₁₈H₁₅O)₂]·C₁₂H₁₂N₂, there is an intra­molecular O—H?O hydrogen bond in the ferrocenediol component and a single O—H?N hydrogen bond linking the two components into a finite monomeric adduct. Ferrocene‐1,1′‐diyl­bis­(di­phenyl­methanol)–ethyl­enedi­amine (1/1), [Fe(C₁₈H₁₅O)₂]·C₂H₈N₂, crystallizes with Z′ = 2 in space group P, and there are two independent four‐component aggregates in the structure, both of which are centrosymmetric. In the first type of aggregate, the molecular components are linked by O—H?N and N—H?O hydrogen bonds, in which both di­amine N atoms participate; in the second type of aggregate, the di­amine component is disordered over two sets of sites, but only one N atom is involved in the hydrogen bonding.     

The sesquiterpenoid nootkatone and the absolute configuration of a di­bromo derivative

Nootkatone, or (4R,4aS,6R)‐4,4a,5,6,7,8‐hexa­hydro‐4,4a‐di­methyl‐6‐(1‐methyl­ethenyl)­naphthalen‐2(3H)‐one, C₁₅H₂₂O, a sesquiterpene with strong repellent properties against Formosan subterranean termites and other insects, has the valencene skeleton. The di­bromo derivative (1S,3R,4S,4aS,6R,8aR)‐1,3‐di­bromo‐6‐iso­propyl‐4,4a‐di­methyl‐1,2,3,4,5,6,7,8‐octa­hydro­naphthalen‐2‐one, C₁₅H₂₄Br₂O, has two independent mol­ecules in the asymmetric unit, which differ in the rotation of the iso­propyl group with respect to the main skeleton. The C—Br distances are in the range 1.950 (4)–1.960 (4) Å. Both independent molecules form zigzag chains, with very short intermolecular carbonyl–carbonyl interactions, having the perpendicular motif and O⋯C distances of 2.886 (6) and 2.898 (6) Å. These chains are flanked by intermolecular Br⋯Br interactions of distances in the range 4.067 (1)–4.218 (1) Å. The absolute configuration of the di­bromo derivative was determined, from which that of nootkatone was inferred.     

Cobalt(II) and nickel(II) complexes of quinoline‐2‐carboxyl­ate

The title complexes, trans‐di­aqua­bis­(quinoline‐2‐carboxyl­ato‐κ²N,O)­cobalt(II)–water–methanol (1/2/2), [Co(C₁₀H₆NO₂)₂(H₂O)₂]·2CH₄O·2H₂O, and trans‐di­aqua­bis­(quinoline‐2‐car­box­yl­ato‐κ²N,O)­nickel(II)–water–methanol (1/2/2), [Ni(C₁₀H₆NO₂)₂(H₂O)₂]·2CH₄O·2H₂O, are isomorphous and contain Co^II and Ni^II ions at centers of inversion. Both complexes have the same distorted octahedral coordination geometry, and each metal ion is coordinated by two quinoline N atoms, two carboxyl­ate O atoms and two water O atoms. The quinoline‐2‐carboxyl­ate ligands lie in trans positions with respect to one another, forming the equatorial plane, with the two water ligands occupying the axial positions. The complex mol­ecules are linked together by hydrogen bonding involving a series of ring patterns which include the uncoordinated water and methanol mol­ecules.     

Ribbons of hydrogen‐bonded rings in the 1:2 complex of pyromellitic acid and di­methyl sulfoxide

In the title complex, pyromellitic acid–di­methyl sulfoxide (1/­2), C₁₀H₆O₈·2C₂H₆OS, mol­ecules of pyromellitic acid (1,2,4,5‐benzene­tetra­car­box­ylic acid) and di­methyl sulfoxide, the latter being well ordered, are linked to each other by O—­H⃛O hydrogen bonds. The formula unit displays crystallographic inversion symmetry. The packing consists of ribbons of hydrogen‐bonded rings that can be described by graph set C(10)R(18).     

A one‐dimensional ladder‐like coordination polymer derived from chains formed via hydrogen bonds: catena‐poly­[[aqua­di­pyridine­nickel(II)]‐μ‐2,2′‐di­thio­dibenzoato‐κ3O,O′:O′′]

The title one‐dimensional chain nickel(II)–di­sulfide complex, [Ni(C₁₄H₈O₄S₂)(C₅H₅N)₂(H₂O)]_n, has each Ni^II cation coordinated by two N atoms from two pyridine ligands, three carboxyl­ate O atoms from two different di­thio­dibenzoate ligands and one O atom from a coordinated water mol­ecule, in a distorted octahedral coordination geometry. Each di­thio­dibenzoate ion links two Ni^II cations through its carboxyl­ate O atoms, making the structure polymeric. Hydro­gen‐bond interactions between two shoulder‐to‐shoulder chains lead to the formation of a ladder‐like structure.     

Investigations on benz­[1,2]­oxaphos­phinane derivatives

The structures of two compounds, 3‐[1‐(2‐hydroxy­ethyl­amino)­ethyl­idene]‐2‐methoxy‐3,4‐di­hydro‐1,2λ⁵‐benz­oxa­phosphinane‐2,4‐dione, C₁₃H₁₆NO₅P, and 3‐[1‐(2‐hydr­oxy‐­ethyl­amino)­ethyl­idene]‐2‐methoxy‐6‐methyl‐3,4‐di­hydro‐1,2λ⁵‐benz­oxaphosphinane‐2,4‐dione, C₁₄H₁₈NO₅P, have been studied and compared. The oxophosphinane rings have a half‐chair conformation and extra six‐ and five‐membered rings are formed by intramolecular N—H?O hydrogen bonds. An intermolecular O—H?O hydrogen bond is also observed.     

Adducts of 1,1,1‐tris(4‐hydroxyphenyl)ethane with diamines: three‐dimensional hydrogen‐bonded frameworks formed with 1,6‐diaminohexane and 2,2′‐bipyridyl

The adduct 1,6‐di­amino­hexane–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2) is a salt {hexane‐1,6‐diyldiammonium–4‐[1,1‐bis(4‐hydroxyphenyl)ethyl]phenolate (1/2)}, C₆H₁₈N₂²⁺·2C₂₀H₁₇O₃^?, in which the cation lies across a centre of inversion in space group P. The anions are linked by two short O—H?O hydrogen bonds [H?O 1.74 and 1.76 Å, O?O 2.5702 (12) and 2.5855 (12) Å, and O—H?O 168 and 169°] into a chain containing two types of R(24) ring. Each cation is linked to four different anion chains by three N—H?O hydrogen bonds [H?O 1.76–2.06 Å, N?O 2.6749 (14)–2.9159 (14) Å and N—H?O 156–172°]. In the adduct 2,2′‐bipyridyl–1,1,1‐tris(4‐hydroxy­phenyl)­ethane (1/2), C₁₀H₈N₂·2C₂₀H₁₈O₃, the neutral di­amine lies across a centre of inversion in space group P2₁/n. The tris­(phenol) mol­ecules are linked by two O—H?O hydrogen bonds [H?O both 1.90 Å, O?O 2.7303 (14) and 2.7415 (15) Å, and O—H?O 173 and 176°] into sheets built from R(38) rings. Pairs of tris­(phenol) sheets are linked via the di­amine by means of a single O—H?N hydrogen bond [H?N 1.97 Å, O?N 2.7833 (16) Å and O—H?N 163°].     

A bis­(acetyl­acetonato)­uranium(IV) complex of the Schiff base N,N′‐bis(3‐hydroxy­salicyl­idene)‐2‐methyl‐1,2‐propane­di­amine

The title complex, bis­(acetyl­acetonato‐κ²O,O′)[N,N′‐bis(3‐hydroxy‐2‐oxidobenzaldimino)‐2‐methyl‐1,2‐propane­di­amine‐κ⁴N,O,O′,N′]­uranium(IV) tetra­hydro­furan solvate, [U(C₁₈H₁₈N₂O₄)(C₅H₇O₂)₂]·C₄H₈O, is a rare example of a uranium(IV) complex with a compartmental Schiff base. The U atom is located in the N₂O₂ inner site of the hexadentate N,N′‐bis(3‐hydroxy‐2‐oxidobenzaldimino)‐2‐methyl‐1,2‐pro­pane­di­amine group and is bound also to the two O atoms of both acetyl­acetonate moieties, which results in a dodecahedral coordination environment. Centrosymmetric dimers are formed through intermolecular hydrogen bonds that link the terminal uncoordinated hydroxy groups to one another and to the O atoms of the acetyl­acetonate ligands.     

A host–guest complex of di­aqua­bis­[1‐hydroxy‐2(1H)‐pyridine­thionato‐O,S]­magnesium(II) and 2,2′‐di­thio­bis­(pyridine N‐oxide)

The title compound, [Mg(C₅H₄NOS)₂(H₂O)₂]·C₁₀H₈N₂O₂S₂, is a two‐component host–guest material. The 2,2′‐di­thio­bis(pyridine N‐oxide) molecule has crystallographic twofold symmetry. The metal complex lies on an inversion centre and associates via C—H?S interactions into chains which thread the 2,2′‐di­thio­bis­(pyridine N‐oxide) lattice in perpendicular directions. Hydro­gen bonds exist between the water mol­ecules of the di­aqua­magnesium units and the N—O groups of the host lattice.     

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.     

catena‐Poly­[[trans‐bis­(ethane‐1,2‐di­amine‐κ2N,N′)copper(II)]‐μ‐di­thion­ato‐κ2O:O′] and trans‐di­aqua­bis­(propane‐1,3‐di­amine‐κ2N,N′)copper(II) di­thionate

In title an­hydro­us catena‐poly­[[trans‐bis­(ethane‐1,2‐di­amine‐κ²N,N′)copper(II)]‐μ‐di­thionato‐κ²O:O′], [Cu(S₂O₆)(C₂H₈N₂)₂]_n or [{H₂N(CH₂)₂NH₂}₂Cu(O·O₂SSO₂·O)]_∞, successive Cu atoms are bridged by a single doubly charged di­thionate group, forming a one‐dimensional polymer with inversion centres at the metal atoms and the mid‐point of the S—S bond [Cu—O = 2.5744 (15) Å]. In title (hydrated) trans‐di­aqua­bis­(propane‐1,3‐di­amine‐κ²N,N′)copper(II) di­thionate, [Cu(C₃H₁₀N₂)₂(H₂O)₂](S₂O₆) or [{H₂N(CH₂)₃NH₂}₂Cu(OH₂)₂](S₂O₆), both ions have imposed 2/m symmetry. The `axial' anion components are displaced by a pair of water ligands [Cu—O = 2.439 (3) Å], the shorter Cu—O distance being compensated by the lengthened Cu—N distance [2.0443 (18), cf. 2.0100 (13) and 2.0122 (16) Å].     

2,8‐Di­hydroxy‐1,3,7,9‐tetra­methyl‐6,12‐di­hydro­dipyrido­[1,2‐a:1′,2′‐d]pyrazine­diyl­ium dichloride dihydrate

The 2,8‐di­hydroxy‐1,3,7,9‐tetra­methyl‐6,12‐di­hydro­di­pyrido[1,2‐a:1′,2′‐d]pyrazine­diyl­ium dication possesses 2/m symmetry and lies in the mirror plane together with a chloride anion and the water O atom. The dication also lies on an inversion centre, i.e. C₁₆H₂₀N₂O₂²⁺·2Cl^?·2H₂O. Due to these symmetry constrictions the dication adopts an unexpected planar conformation. Molecules are linked by O—H?O and O—H?Cl hydrogen bonds to form chains, which are cross‐connected by C—H?Cl attractive interactions forming a complex three‐dimensional hydrogen‐bond network.     

cis‐Bis(3,6‐di­hydro‐2H‐1,2‐oxazine‐N)­di­iodo­platinum(II) and cis‐bis(3,4,5,6‐tetra­hydro‐2H‐1,2‐oxazine‐N)­di­iodo­platinum(II)

The title complexes, [Pt(C₄H₇NO)₂I₂], (I), and [Pt(C₄H₉NO)₂I₂], (II), possess similar square‐planar coordination geometries with modest distortions from ideality. For (I), the cis‐L—Pt—L angles are in the range 87.0 (4)–94.2 (3)°, while the trans angles are 174.4 (3) and 176.4 (3)°. For (II), cis‐L—Pt—L are 86.1 (8)–94.2 (6)° and trans‐L—Pt—L are 174.4 (6) and 177.4 (5)°. One 3,6‐di­hydro‐2H‐1,2‐oxazine ligand in (I) is rotated so that the N—O bond is out of the square plane by approximately 70°, while the N—C bond is only ca 20° out of the plane. The other oxazine ligand is rotated so that the N—C bond is about 80° out of the plane, while the N—O bond is out of the plane by approximately 24°. In (II), the 3,4,5,6‐tetra­hydro‐2H‐1,2‐oxazine ligands are also positioned with one having the N—O bond further out of the plane and the other having the N—C bond positioned in that fashion. Both ligands, however, are rotated approximately 90° compared with their positions in (I). In both complexes, this results in an unsymmetrical distortion of the I—Pt—N bond angles in which one is expanded and the other contracted. These features are compared to those of reported cis‐di­amine­di­iodo­platinum(II) complexes.     

2‐(4‐Bromophenyl)‐1,2‐dihydropyrimido[1,2‐a]benzimidazol‐4(3H)‐one and 4‐(4‐methylphenyl)‐3,4‐dihydropyrimido[1,2‐a]benzimidazol‐2(1H)‐one form hydrogen‐bonded base‐paired dimers

The title compounds, 2‐(4‐bromo­phenyl)‐1,2‐di­hydro­pyrimido­[1,2‐a]­benzimidazol‐4‐(3H)‐one, C₁₆H₁₂Br­N₃O, (IVa), and 4‐(4‐methylphenyl)‐3,4‐dihydropyrimido[1,2‐a]benzimidazol‐2‐(1H)‐one, C₁₇H₁₅N₃O, (Vb), both form R(8) centrosymmetric dimers via N—H?N hydrogen bonds. The N?N distance is 2.943 (3) Å for (IVa) and 2.8481 (16) Å for (Vb), with the corresponding N—H?N angles being 129 and 167°, respectively. However, in other respects, the supra­molecular structures of the two compounds differ. Both compounds contain different C—H?π interactions, in which the C—H?π(centroid) distances are 2.59 and 2.47 Å for (IVa) and (Vb), respectively (the latter being a short distance), with C—H?π(centroid) angles of 158 and 159°, respectively. The supramolecular structures also differ, with a short Br?O distance of 3.117 (2) Å in bromo derivative (IVa), and a C—H?O interaction with a C?O distance of 3.2561 (19) Å and a C—H?O angle of 127° in tolyl system (Vb). The di­hydro­pyrimido part of (Vb) is disordered, with a ratio of the major and minor components of 0.9:0.1. The disorder consists of two non‐interchangeable envelope conformers, each with an equatorial tolyl group and an axial methine H atom.     

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.