Chains of fused rings in the hydrogen‐bonded structure of meso‐­6,13‐di­amino‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane–2,2′‐biphenol (1/2)

The title compound is a salt, [C₁₂H₃₂N₆]²⁺·2[HOC₆H₄C₆H₄O]^?. The centrosymmetric cation contains two intramolecular N—H?N hydrogen bonds with an N?N distance of 2.8290 (13) Å, and the pendent amino groups are in axial sites; the anion contains an intramolecular O—H?O hydrogen bond with an O?O distance of 2.4656 (11) Å. The ions are linked into continuous chains by means of four types of N—H?O hydrogen bonds with N?O distances ranging from 2.7238 (12) Å to 3.3091 (13) Å, associated with N—H?O angles in the range 148–160°.     

5,7,7,12,14,14‐Hexamethyl‐4,11‐diaza‐1,8‐diazonia­cyclo­tetra­decane penta­cyano­nitroso­ferrate(II) dihydrate: a supramolecular compound constructed by hydrogen bonds

The title compound, (C₁₆H₃₈N₄)[Fe(CN)₅(NO)]·2H₂O, contains one [Fe(CN)₅(NO)]²⁻ dianion, two half [H₂teta]²⁺ dications (teta is 5,7,7,12,14,14‐hexa­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane), each lying about an independent inversion centre, and two solvent water mol­ecules, all of which are held together by hydrogen bonds to form a three‐dimensional supramolecular framework.     

NiII and ZnII complexes of the hexadentate macrocyclic ligand cis‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐di­amine

The title pendent‐arm macrocyclic hexa­amine ligand binds stereospecifically in a hexadentate manner, and we report here its isomorphous Ni^II and Zn^II complexes (both as perchlorate salts), namely (cis‐6,13‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐6,13‐di­amine‐κ⁶N)­nickel(II) di­per­chlorate, [Ni(C₁₂H₃₀N₆)]­­(ClO₄)₂, and (cis‐6,13‐di­methyl‐1,4,8,11‐tetraaza‐cyclo­tetra­decane‐6,13‐di­amine‐κ⁶N)­zinc(II) di­per­chlorate, [Zn(C₁₂H₃₀N₆)]­(ClO₄)₂. Distortion of the N—M—N valence angles from their ideal octahedral values becomes more pronounced with increasing metal‐ion size and the present results are compared with other structures of this ligand.     

(μ‐C‐meso‐5,5,7,12,12,14‐Hexa­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐N‐acetato‐1κ5N,N′,N′′,N′′′,O:2κO′)­tetra­chloro‐1κCl,2κ3Cl‐cobalt(III)­zinc(II)

The crystal structure of the title compound, [CoCl(C₁₈H₃₇N₄O₂){ZnCl₃}], has been determined by X‐ray diffraction.C‐meso‐5,5,7,12,12,14‐Hexa­methyl‐1,4,8,11‐tetra­aza­cyclotetradecane‐N‐acetate acts as a bridging ligand to coodinate with Co^III and Zn^II ions. The Co^III ion is six‐coordinate in a nearly octahedral environment provided by one Cl atom, four N atoms of the bridging ligand, and one O atom. The Zn^II ion is four‐coordinate in a distorted tetrahedral environment completed by three Cl atoms and an O atom of the bridging ligand.     

cis‐(6RS,13RS)‐3,3,10,10‐Tetra­methyl‐6,13‐diphenyl‐1,8‐dioxa‐4,11‐diaza­cyclo­tetra­decane‐2,5,9,12‐tetra­one and two of its precursors

The title macrocycle, C₂₆H₃₀N₂O₆, (VI), was obtained by `direct amide cyclization' from the linear precursor 3‐hydr­oxy‐N‐[1‐methyl‐1‐(N‐methyl‐N‐phenyl­carbamoyl)ethyl]‐2‐phenylpropanamide, the N‐methyl­anilide of rac‐2‐methyl‐2‐[(3‐hydroxy‐2‐phenyl­propanoyl)­amino]­propanoic acid, C₁₃H₁₇NO₄, (IV). The reaction proceeds via the inter­mediate rac‐2‐(2‐hydroxy‐1‐phenyl­ethyl)‐4,4‐dimethyl‐1,3‐oxazol‐5(4H)‐one, C₁₃H₁₅NO₃, (V), which was synthesized independently and whose structure was also established. Unlike all previously described analogues, the title macrocycle has the cis‐diphenyl configuration. The 14‐membered ring has a distorted rect­angular diamond‐based [3434] configuration and inter­molecular N—H⋯O hydrogen bonds link the mol­ecules into a three‐dimensional framework. The propanoic acid precursor forms a complex series of inter­molecular hydrogen bonds, each of which involves pairwise association of mol­ecules and which together result in the formation of extended two‐dimensional sheets. The oxazole inter­mediate forms centrosymmetric hydrogen‐bonded dimers in the solid state.     

Di‐μ‐hydro­xo‐bis­(diiso­propyl­gallium)–1,4,8,11‐tetra­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane (1/1)

The hydro­lysis product [Ga₂(C₃H₇)₄(OH)₂]·C₁₄H₃₂N₄, derived from the tetrakis­(triiso­propyl­gallium)–1,4,8,11‐tetra­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane (1/1) adduct, consists of a centrosymmetric [ⁱPr₂Ga(μ‐OH)]₂ unit hydrogen bonded through the hydroxyl group to a nitro­gen on an adjacent centrosymmetric 1,4,8,11‐tetra­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane molecule, resulting in the generation of a molecular chain through the crystal.     

N‐tert‐Butyl‐N′‐(5,7‐di­methyl‐1,8‐naphthyridin‐2‐yl)­urea

The title compound, C₁₅H₂₀N₄O, has been synthesized as an AADD recognition unit for quadruple hydrogen bonds. All non‐H atoms of the mol­ecule apart from two methyl groups of the tert‐butyl group lie in a common plane. An intramolecular hydrogen bond is formed connecting two N atoms. In the solid state, the title compound crystallizes as a centrosymmetric dimer connected by N—H?O=C interactions with an N?O distance of 2.824 (2) Å.     

The monoclinic polymorph of rac‐5,7,7,12,12,14‐hexa­methyl‐1,4,8,11‐tetraazonia­cyclo­tetra­decane bis­(hexa­fluoro­germanate) tetrahydrate

X‐ray data were obtained for the monoclinic polymorph of rac‐5,7,7,12,12,14‐hexa­methyl‐1,4,8,11‐tetraazonia­cyclo­tetra­decane bis­(hexa­fluoro­germanate) tetrahydrate, (C₁₆H₄₀N₄)[GeF₆]₂·4H₂O. The tetra­aza‐macrocyclic cations lie across inversion centers in space group P2₁/c. Water mol­ecules and [GeF₆]²⁻ anions form zigzag chains, which alternate in a three‐dimensional network with the macrocyclic cations. The structure is sustained by multiple hydrogen bonds.     

N‐(6‐Amino‐3,4‐di­hydro‐3‐methyl‐5‐nitro­so‐4‐oxopyrimidin‐2‐yl)‐(S)‐glutamic acid: a three‐dimensional framework structure built from O—H⃛O,N—H⃛O and O—H⃛N hydrogen bonds

The title compound, C₁₀H₁₃N₅O₆, exhibits a highly polarized molecular–electronic structure and the conformation is influenced by two intramolecular N—H⃛O hydrogen bonds. The mol­ecules are linked into a single framework by hydrogen bonds of types O—H⃛O [O—H = 1.22, H⃛O = 1.38, O⃛O = 2.558 (6) Å and O—H⃛O = 160°], N—H⃛O [H⃛O = 2.26, N⃛O = 2.866 (6) Å and N—H⃛O = 126°] and O—H⃛N [O—H = 1.26, H⃛N = 1.56, O⃛N = 2.811 (6) Å and O—H⃛N = 170°]. The substructure generated by the O—H⃛O and N—H⃛O hydrogen bonds takes the form of a double helix.     

trans‐Di­aqua(C‐meso‐5,12‐di­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐N,N′,N′′,N′′′)copper(II) dichloride dihydrate

The crystal structure of the title complex, [Cu(C₁₂H₂₈N₄)(H₂O)₂]Cl₂·2H₂O, has been determined. The Cu^II atom is octahedrally coordinated by the four N atoms of the tetradentate macrocyclic ligand in equatorial positions and by the O atoms of two water mol­ecules in axial positions. The crystal structure is stabilized by a three‐dimensional network of hydrogen bonds.     

meso‐5,5,7,12,12,14‐Hexamethyl‐1,4‐diaza‐8,11‐diazoniacyclotetradecane bis(2‐naphthoate) ethanol disolvate: centrosymmetric five‐component aggregates linked into sheets by C—H⃛π(arene) hydrogen bonding

The title compound is an ethanol‐solvated salt, C₁₆H₃₈N₄²⁺·2C₁₁H₇O₂⁻·2C₂H₆O, in which the cation lies across a centre of inversion in P2₁/c. The ions are linked by N—H⃛O hydrogen bonds [H⃛O = 1.70 and 2.30 Å, N⃛O = 2.624 (2) and 3.136 (2) Å, and N—H⃛O = 178 and 151°], and the ethanol mol­ecule is linked to the anion by an O—H⃛O hydrogen bond [H⃛O = 1.90 Å, O⃛O = 2.728 (2) Å and O—H⃛O = 171°], to form a centrosymmetric five‐component aggregate. C—H⃛O hydrogen bonds and aromatic π–π‐stacking interactions are absent, but the aggregates are linked into sheets by a single C—H⃛π(arene) hydrogen bond.     

Bis(3‐nitro­phenyl) di­sulfide forms no C—H⃛O hydrogen bonds

In the title compound, C₁₂H₈N₂O₄S₂, the mol­ecules lie across twofold rotation axes in the space group C2/c. There are no intermolecular C—H?O hydrogen bonds, but the mol­ecules are linked into chains along [001] by aromatic π?π stacking interactions.     

Difur­aza­no­[3,4‐b:3′,4′‐f]‐4,5‐di­aza‐1,8‐dioxa­cyclo­dodecine and an acyclic analogue

The novel title fur­azan‐containing macrocycle (systematic name: 6,9,14,17‐tetraoxa‐2,3,5,7,16,18‐hexa­aza­tri­cyclo­[13.3.0.0^4,8]­octadeca‐4,7,15,18‐tetraene), C₈H₁₀N₆O₄, (I), is the first macrocycle where the fur­azan rings are connected via a hydrazine group. In spite of the strain in the 12‐membered macrocycle of (I), the geometry of the fur­azan fragment is the same in (I) and in its acyclic analogue 1,8‐bis(5‐amino­fur­azan‐4‐yl­oxy)‐3,6‐dioxaoctane, C₁₀H₁₆N₆O₆, (II). In both compounds, the participation of the fur­azan rings in intermolecular hydrogen bonding equalizes the N—O bonds within the fur­azan rings, in contrast with rings which do not participate in such interactions.     

4‐Iodo‐N‐(2‐nitro­phenyl­sulfanyl)­aniline: π‐stacked sheets generated by a combination of N—H⃛O and C—H⃛O hydrogen bonds

Molecules of the title compound, C₁₂H₉IN₂O₂S, are linked by one N—H⃛O hydrogen bond [H⃛O = 2.16 Å, N⃛O = 2.935 (4) Å and N—H⃛O 147°] and two C—H⃛O hydrogen bonds [H⃛O both 2.49 Å, C⃛O = 3.231 (5) and 3.220 (5) Å, and C—H⃛O = 135 and 134°] into sheets which themselves are weakly linked by an aromatic π–π‐stacking interaction between iodinated rings in centrosymmetrically related mole­cules. There are no iodo–nitro interactions.     

Bis(4‐hydroxy­benzoato‐O)(1,4,8,11‐tetra­aza­cyclo­tetra­decane‐κ4N)nickel(II): a three‐dimensional framework built from O—H⋯O and N—H⋯O hydrogen bonds

The title compound, [Ni(C₇H₅O₃)₂(C₁₀H₂₄N₄)], contains octahedral Ni^II in a centrosymmetric trans configuration with Ni—N distances of 2.0637 (17) and 2.0699 (16) Å and an Ni—O distance of 2.1100 (14) Å. The mol­ecules are linked by a single type of O—H?O hydrogen bond [O?O 2.618 (2) Å and O—H?O 161°] into two‐dimensional sheets; a singletype of N—H?O hydrogen bond [N?O 2.991 (2) Å and N—H?O 139°] links these sheets into a three‐dimensional framework.     

(P,M)‐1,2,3,9,10,11‐Hexa­methoxy‐5,7‐di­hydro­dibenz­[c,e]­oxepine and (P,M)‐1,11‐di­methyl‐5,5,7,7‐tetra­phenyl‐5,7‐di­hydro­dibenz­[c,e]­oxepine

The title compounds, C₂₀H₂₄O₇ and C₄₀H₃₂O, respectively, are racemic oxepines, the mol­ecules of which contain a chiral axis. Both mol­ecules possess crystallographic C₂ symmetry and the seven‐membered ring adopts a twisted‐boat confor­mation.     

Aqua­(5,6‐di­methyl‐1,10‐phenanthroline‐N,N′)­(glycolato‐O,O′)­copper(II) nitrate

The title compound, [Cu(C₂H₃O₃)(C₁₄H₁₂N₂)(H₂O)]NO₃, is the first example of a mixed copper glycolate compound with a di­imine ligand. The copper(II) compound lies in a slightly distorted square‐pyramidal coordination environment with one water mol­ecule coordinated in the apical position. The glycolate ligand binds to the Cu atom as a chelate through a carboxyl­ate and the α‐OH O atom which, together with the N atoms of the substituted phenanthroline, constitute the base of the pyramid.     

[2,13‐Bis­(acet­amido)‐5,16‐di­methyl‐2,6,13,17‐tetra­aza­tri­cyclo­[16.4.0.07,12]­do­cosane]copper(II) dichloride octahydrate

The title compound, [Cu(C₂₄H₄₆N₆O₂)]Cl₂·8H₂O, contains a centrosymmetric cation, with the anions and water mol­ecules on general sites. The coordination geometry around the Cu^II ion is an axially elongated octahedron, with Cu—N distances of 2.0448 (17) and 2.0847 (17) Å, and a Cu—O1 distance of 2.3138 (16) Å.     

Ferrocene­carboxyl­ic acid–1,4‐di­aza­bi­cyclo­[2.2.2]­octane (2/1): sheets built from O—H⃛N and C—H⃛O hydrogen bonds

In the title compound, 2[Fe(C₅H₅)(C₆H₅O₂)]·C₆H₁₂N₂, the molecular components are linked into finite three‐component aggregates by strong O—H?N hydrogen bonds [O?N 2.578 (4) and 2.604 (5) Å; O—H?N 170 (5) and 174 (6)°]; these aggregates are further linked by C—H?O hydrogen bonds [C?O 3.327 (5)–3.401 (5) Å; C—H?O 149–157°] into continuous sheets in the form of (6,3) nets.     

Tri­carbonyl­[(6a,7,8,9,10a‐η)‐3,3‐di­methyl‐3H‐benzo­[f]­chromene]chromium

The title compound, [Cr(C₁₅H₁₄O)(CO)₃], is a chromene complexed with tri­carbonyl­chromium and it exhibits photochromic properties. The molecular geometry is compared to that of two similar complexes. The analysis results indicate that complexation has minor effects on the chromene structure.