N,N′‐Bis(2‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide and N,N′‐bis­(3‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide

The mol­ecules of N,N′‐bis­(2‐pyridylmeth­yl)ferrocene‐1,1′‐diyl­dicarboxamide, [Fe(C₁₂H₁₁N₂O)₂], contain intra­molecular N—H⋯N hydrogen bonds and are linked into sheets by three independent C—H⋯O hydrogen bonds. The mol­ecules of the isomeric compound N,N′‐bis­(3‐pyridylmeth­yl)ferrocene‐1,1′‐diyldicarboxamide lie across inversion centres, and the mol­ecules are linked into sheets by a combination of N—H⋯N hydrogen bonds and π–π stacking inter­actions between pyridyl groups.     

C—H⋯O,C—H⋯π and π–π inter­actions in three benzofuran‐2‐yl ketone derivatives

The mol­ecules of 2‐benzoyl‐1‐benzofuran, C₁₅H₁₀O₂, (I), inter­act through double C—H⋯O hydrogen bonds, forming dimers that are further linked by C—H⋯O, C—H⋯π and π–π inter­actions, resulting in a three‐dimensional supramolecular network. The dihedral angle between the benzo­yl and benzofuran fragments in (I) is 46.15 (3)°. The mol­ecules of bis­(5‐bromo‐1‐benzofuran‐2‐yl) ketone, C₁₇H₈Br₂O₃, (II), exhibit C₂ symmetry, with the carbon­yl group (C=O) lying along the twofold rotation axis, and are linked by a combination of C—H⋯O and C—H⋯π inter­actions and Br⋯Br contacts to form sheets. The stability of the mol­ecular packing in 3‐mesit­yl‐3‐methyl­cyclo­but­yl 3‐methyl­naphtho[1,2‐b]furan‐2‐yl ketone, C₂₈H₂₈O₂, (III), arises from C—H⋯π and π–π stacking inter­actions. The fused naphthofuran moiety in (III) is essentially planar and makes a dihedral angle of 81.61 (3)° with the mean plane of the trimethyl­benzene ring.     

fac‐Bromo­tri­carbonyl­[2‐(2‐pyridylmethyl)‐2,3‐di­hydro‐1H‐isoindol‐1‐one]­rhenium(I) methanol solvate

The structure of the title compound, fac‐[ReBr(C₁₄H₁₂N₂O)(CO)₃]·CH₄O, consists of neutral mononuclear mol­ecular units of distorted octahedral geometry, with the three carbonyl donors in a facial orientation. The remaining coordination sites are occupied by the Br atom, the pyridine N atom and the ketone O‐atom donor of the ligand. The mol­ecules pack in stacks of antiparallel tapes, with a network of classical (O—H⋯Br) and non‐classical (C—H⋯O) hydrogen bonds between the methanol solvent mol­ecule and the complex mol­ecule.     

Secondary inter­actions in two related terphenyl derivatives: 2′,5′‐dimethyl‐p‐terphenyl and 2′,5′‐bis­(bromo­meth­yl)‐p‐terphen­yl

In 2′,5′‐dimethyl‐p‐terphenyl, C₂₀H₁₈, which displays pseudosymmetry (the true space group is Pna2₁, but less satisfactory refinement can also be achieved in Pbcn), the mol­ecules are linked into chains by two short C—H⋯π inter­actions to the centroid of the central ring. In 2′,5′‐bis­(bromo­meth­yl)‐p‐terphenyl, C₂₀H₁₆Br₂, the polar CH₂Br groups cause mol­ecules to aggregate via C—H⋯Br and Br⋯Br inter­actions, forming a layer structure, in which the phenyl rings project outwards from the central, more polar, region.     

Tris(1H‐benzimidazol‐2‐yl­meth­yl)­amine–solvent adducts

The tris­(1H‐benzimidazol‐2‐yl­meth­yl)­amine (ntb) mol­ecule crystallizes in different solvent systems, resulting in two kinds of adduct, namely the monohydrate, C₂₄H₂₁N₇·H₂O or ntb·H₂O, (I), and the acetonitrile–methanol–water (1/0.5/1.5) solvate, C₂₄H₂₁N₇·C₂H₃N·0.5CH₄O·1.5H₂O or ntb·1.5H₂O·0.5MeOH·MeCN, (II). In both cases, ntb adopts a tripodal mode to form hydrogen bonds with a solvent water mol­ecule via two N—H⋯O and one O—H⋯N hydrogen bond. In (I), the ntb·H₂O adduct is further assembled into a two‐dimensional network by N—H⋯N and O—H⋯N hydrogen bonds, while in (II), a double‐stranded one‐dimensional chain structure is assembled via N—H⋯O and O—H⋯O hydrogen bonds, with the acetonitrile mol­ecules located inside the cavities of the chain structure.     

Three structures containing (E)‐1,2‐bis­(benzimidazol‐2‐yl)ethene groups

Two of the title compounds, namely (E)‐1,2‐bis­(1‐methyl­benzimidazol‐2‐yl)ethene, C₁₈H₁₆N₄, (Ib), and (E)‐1,2‐bis­(1‐ethyl­benzimidazol‐2‐yl)ethene, C₂₀H₂₀N₄, (Ic), consist of centrosymmetric trans‐bis­(1‐alkyl­benzimidazol‐2‐yl)ethene mol­ecules, while 3‐eth­yl‐2‐[(E)‐2‐(1‐ethyl­benzimidazol‐2‐yl)­ethen­yl]benzimidazol‐1‐ium perchlorate, C₂₀H₂₁N₄⁺·ClO₄⁻, (II), contains the monoprotonated analogue of compound (Ic). In the three structures, the benzimidazole and benzimidazolium moieties are essentially planar; the geometric parameters for the ethene linkages and their bonds to the aromatic groups are consistent with double and single bonds, respectively, implying little, if any, conjugation of the central C=C bonds with the nitro­gen‐containing rings. The C—N bond lengths in the N=C—N part of the benzimidazole groups differ and are consistent with localized imine C=N and amine C—N linkages in (Ib) and (Ic); in contrast, the corresponding distances in the benzimidazolium cation are equal in (II), consistent with electron delocalization resulting from protonation of the amine N atom. Crystals of (Ib) and (Ic) contain columns of parallel mol­ecules, which are linked by edge‐over‐edge C—H⋯π overlap. The columns are linked to one another by C—H⋯π inter­actions and, in the case of (Ib), C—H⋯N hydrogen bonds. Crystals of (II) contain layers of monocations linked by π–π inter­actions and separated by both perchlorate anions and the protruding eth­yl groups; the cations and anions are linked by N—H⋯O hydrogen bonds.     

Dichloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]zinc(II) and di‐μ‐chloro‐bis­{chloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]cadmium(II)}

The Zn atom in dichloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)­methane]zinc(II), [ZnCl₂(C₁₁H₁₆N₄)], (I), is tetra­hedrally coordinated by two N atoms from one bis­(3,5‐dimethyl­pyrazol­yl)methane ligand and two terminal Cl atoms. The mol­ecule has no crystallographic symmetry. One H atom of the CH₂ group of the bis­(3,5‐dimethyl­pyrazol­yl)methane ligand inter­acts with a Cl atom of an adjacent mol­ecule to yield inter­molecular C—H⋯Cl contacts, thereby forming a one‐dimensional zigzag chain extending along the b axis. On the other hand, in di‐μ‐chloro‐bis­{chloro­[(3,5‐dimethyl‐1H‐pyrazol‐1‐yl)methane]cadmium(II)}, [Cd₂Cl₄(C₁₁H₁₆N₄)₂], (II), each of the two crystallographically equivalent Cd atoms is penta­coordinated by two N atoms from one bis­(3,5‐dimethyl­pyrazol­yl)methane ligand, and by one terminal and two bridging Cl⁻ anions. The mol­ecule has a crystallographic centre of symmetry located at the mid‐point of the Cd⋯Cd line. One H atom of the CH₂ group of the bis­(3,5‐dimethyl­pyrazolyl)­methane ligand inter­acts with a Cl atom of an adjacent mol­ecule to produce pairwise inter­molecular C—H⋯Cl contacts, thereby affording chains of mol­ecules running along the c axis.     

N‐(3H‐Thia­zol‐2‐yl­idene)­nitr­amine and N‐methyl‐N‐(thia­zol‐2‐yl)­nitr­amine

The geometries of the thia­zole ring and the nitr­amino groups in N‐(3H‐thia­zol‐2‐yl­idene)­nitr­amine, C₃H₃N₃O₂S, (I), and N‐­methyl‐N‐(thia­zol‐2‐yl)­nitr­amine, C₄H₅N₃O₂S, (II), are very similar. The nitr­amine group in (II) is planar and twisted along the C—N bond with respect to the thia­zole ring. In both structures, the asymmetric unit includes two practically equal mol­ecules. In (I), the mol­ecules are arranged in layers connected to each other by N—H⋯N and much weaker C—H⋯O hydrogen bonds. In the crystal structure of (II), the mol­ecules are arranged in layers bound to each other by both weak C—H⋯O hydrogen bonds and S⋯O dipolar interactions.     

{μ‐N,N′‐Bis[3‐(dimethyl­amino)prop­yl]­oxamidato(2–)‐κ6N,N′,O′:N′′,N′′′,O}­bis­[(1H‐imidazole‐κN3)(methanol‐κO)copper(II)] bis­(perchlorate)

The structure of the title compound, [Cu₂(C₁₂H₂₄N₄O₂)(C₃H₄N₂)₂(CH₄O)₂](ClO₄)₂ or [Cu₂(dmoxpn)(HIm)₂(CH₃OH)₂](ClO₄)₂, where dmoxpn is the dianion of N,N′‐bis­[3‐(dimethyl­amino)prop­yl]oxamide and HIm is imidazole, consists of a centrosymmetric trans‐oxamidate‐bridged copper(II) binuclear cation, having an inversion centre at the mid‐point of the central C—C bond, and two perchlorate anions. The Cu^II atom has square‐pyramidal coordination geometry involving two N atoms and an O atom from the dmoxpn ligand, an N atom from an imidazole ring, and an O atom from a methanol mol­ecule. The crystal structure is stabilized by O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds and imidazole π–π stacking inter­actions to form a three‐dimensional supra­molecular array.     

The perchlorate salt of the novel diprotonated dinucleating ligand 1,3‐bis­{[2‐(2‐pyridinio)eth­yl][2‐(2‐pyrid­yl)eth­yl]amino}benzene

In the title salt, 1,3‐bis­{[2‐(2‐pyridinio)eth­yl][2‐(2‐pyrid­yl)ethyl]amino}benzene diperchlorate dihydrate, C₃₄H₃₈N₆²⁺·2ClO₄⁻·2H₂O, the cation contains two ethyl­pyrid­yl and two ethyl­pyridinium pendant pairs anchored to the two N atoms of 1,3‐phenyl­enediamine. The pyrid­yl and pyridinium N atoms are flanked by a mol­ecule of water through strong hydrogen‐bonding inter­actions [N—H⋯O = 2.762 (6) and 2.758 (6) Å, and O—H⋯N = 2.834 (6) and 2.839 (6) Å]. The water mol­ecules have weak hydrogen‐bonding inter­actions with the perchlorate anions as well. One of the perchlorate anions is severely disordered.     

Two‐dimensional square‐grid frameworks formed by self‐associating copper(II) complexes with 1‐(3‐pyridyl)‐ and 1‐(4‐pyridyl)‐substituted butane‐1,3‐diones

In bis­[1‐(3‐pyridyl)butane‐1,3‐dionato]copper(II) (the Cu atom occupies a centre of inversion), [Cu(C₉H₈NO₂)₂], (I), and bis­[1‐(4‐pyridyl)butane‐1,3‐dionato]copper(II) methanol solvate, [Cu(C₉H₈NO₂)₂]·CH₃OH, (II), the O,O′‐chelating diketonate ligands support square‐planar coordination of the metal ions [Cu—O = 1.948 (1)–1.965 (1) Å]. Weaker Cu⋯N inter­actions [2.405 (2)–2.499 (2) Å], at both axial sides, occur between symmetry‐related bis­(1‐pyridylbutane‐1,3‐dion­ato)copper(II) mol­ecules. This causes their self‐organization into two‐dimensional square‐grid frameworks, with uniform [6.48 Å for (I)] or alternating [4.72 and 6.66 Å for (II)] inter­layer separations. Guest methanol mol­ecules in (II) reside between the distal layers and form weak hydrogen bonds to coordinated O atoms [O⋯O = 3.018 (4) Å].     

2′‐(4‐Fluoro­phenyl)‐[1,2,3]­triazolo[4′,5′:16,17]­androst‐5‐en‐3β‐ol methanol hemisolvate

The asymmetric unit of the title compound, C₂₅H₃₀FN₃O·0.5CH₃OH, contains four symmetry‐independent steroid and two methanol mol­ecules. The conformations of the independent steroid mol­ecules are very similar. Intermolecular O—H⋯O hydrogen bonds create two independent chains, each of which links two of the independent steroid mol­ecules plus one methanol mol­ecule via a co‐operative O—H⋯O—H⋯O—H pattern. Intermolecular C—H⋯O and C—H⋯F interactions are also observed.     

2‐Amino‐5‐nitro­thia­zole monoethanol solvate: triply‐interwoven hydrogen‐bonded sheets containing centrosymmetric R(8) and R(38) rings

2‐Amino‐5‐nitro­thia­zole crystallizes from solution in ethanol as a monosolvate, C₃H₃N₃O₂S·C₂H₆O, in which the thia­zole component has a strongly polarized molecular–electronic structure. The thia­zole mol­ecules are linked into centrosymmetric dimers by paired N—H⋯N hydrogen bonds [H⋯N = 2.09 Å, N⋯N = 2.960 (6) Å and N—H⋯N = 169°], and these dimers are linked by the ethanol mol­ecules, via a two‐centred N—H⋯O hydrogen bond [H⋯O = 1.98 Å, N⋯O = 2.838 (5) Å and N—H⋯O = 164°] and a planar asymmetric three‐centred O—H⋯(O)₂ hydrogen bond [H⋯O = 2.07 and 2.53 Å, O⋯O = 2.900 (5) and 3.188 (5) Å, O—H⋯O = 169 and 136°, and O⋯H⋯O = 55°], into sheets built from alternating (8) and (38) rings. These sheets are triply interwoven.     

Azin­yl sulfides. LXXXI. 14‐Phen­yl‐7‐thia­pyrano[2,3‐c;6,5‐c′]diquinoline‐14‐carbonitrile

The mol­ecules of the title compound, C₂₆H₁₅N₃S, have a penta­cyclic ring system which is almost planar, with the central ring in a flattened boat conformation. The folding angle between the two quinoline rings is 6.75 (7)°. The 14‐phen­yl substituent is in a quasi‐axial conformation, while the 14‐cyano substituent is in a quasi‐equatorial conformation with respect to the thio­pyran ring. The S⋯C—C_phen­yl and S⋯C—C_CN angles are 116.8 (2) and 129.3 (2)°, respectively. The plane of the phen­yl group is nearly coplanar with the plane bis­ecting the dihedral angle of the penta­cyclic ring system.     

Three isomeric forms of hydroxyphenyl‐2‐oxazoline: 2‐(2‐hydroxyphenyl)‐2‐oxazoline, 2‐(3‐hydroxyphenyl)‐2‐oxazoline and 2‐(4‐hydroxyphenyl)‐2‐oxazoline

Crystal structures are reported for three isomeric compounds, namely 2‐(2‐hydroxy­phenyl)‐2‐oxazoline, (I), 2‐(3‐hydroxy­phenyl)‐2‐oxazoline, (II), and 2‐(4‐hydroxy­phenyl)‐2‐oxazoline, (III), all C₉H₉NO₂ [systematic names: 2‐(4,5‐dihydro‐1,3‐oxazol‐2‐yl)phenol, (I), 3‐(4,5‐dihydro‐1,3‐oxazol‐2‐yl)phenol, (II), and 4‐(4,5‐dihydro‐1,3‐oxazol‐2‐yl)phenol, (III)]. In these compounds, the deviation from coplanarity of the oxazoline and benzene rings is dependent on the position of the hydroxy group on the benzene ring. The coplanar arrangement in (I) is stabilized by a strong intra­molecular O—H⋯N hydrogen bond. Surprisingly, the 2‐oxazoline ring in mol­ecule B of (II) adopts a ³T₄ (^C2T_C3) conformation, while the 2‐oxazoline ring in mol­ecule A, as well as that in (I) and (III), is nearly planar, as expected. Tetra­mers of mol­ecules of (II) are formed and they are bound together via weak C—H⋯N hydrogen bonds. In (III), strong inter­molecular O—H⋯N hydrogen bonds and weak intra­molecular C—H⋯O hydrogen bonds lead to the formation of an infinite chain of mol­ecules perpendicular to the b direction. This paper also reports a theoretical investigation of hydrogen bonds, based on density functional theory (DFT) employing periodic boundary conditions.     

ent‐7α,18‐Hydroxy­kaur‐16‐ene ethanol solvate

The ent‐kaurene diterpene in the title compound, 7‐epican­dicandiol ethanol solvate, C₂₀H₃₂O₂·C₂H₆O, was isolated from the aerial parts of Sideritis ozturkii Aytaç & Aksoy. The mol­ecule has the usual conformation and stereochemistry found in related ent‐kaurene derivatives. The methyl‐substituted ring junction has a trans arrangement and the other junction is cis. The six‐membered rings have chair or slightly distorted chair conformations and the five‐membered ring has an envelope conformation. Inter­molecular hydrogen bonds link the 7‐epicandicandiol and ethanol mol­ecules into two‐dimensional networks, part of which comprise co‐operative O—H⋯O—H⋯O—H⋯ chains.     

1‐(1‐Amino‐4‐bromo‐9,10‐dioxo‐9,10‐dihydro­anthracen‐2‐ylcarbon­yl)‐1,3‐dicyclo­hexyl­urea

In the title compound, C₂₈H₃₀BrN₃O₄, the mol­ecules are linked by C—H⋯Br and N—H⋯O hydrogen bonds into one‐dimensional chains, which are arranged into a three‐dimensional network through a combination of C—H⋯O hydrogen bonds and two kinds of π–π inter­actions between the benzene rings of the anthraquinone units.     

3,4‐Di‐2‐pyridyl‐1,2,5‐oxadiazole and its perchlorate salt

In 3,4‐di‐2‐pyridyl‐1,2,5‐oxadiazole (dpo), C₁₂H₈N₄O, each mol­ecule resides on a twofold axis and inter­acts with eight neighbours via four C—H⋯N and four C—H⋯O inter­actions to generate a three‐dimensional hydrogen‐bonded architecture. In the perchlorate analogue, 2‐[3‐(2‐pyrid­yl)‐1,2,5‐oxadiazol‐4‐yl]pyridinium perchlorate, C₁₂H₉N₄O⁺·ClO₄⁻ or [Hdpo]ClO₄, the [Hdpo]⁺ cation is bisected by a crystallographic mirror plane, and the additional H atom in the cation is shared by the two pyridyl N atoms to form a symmetrical intra­molecular N⋯H⋯N hydrogen bond. The cations and perchlorate anions are linked through C—H⋯O hydrogen bonds and π–π stacking inter­actions to form one‐dimensional tubes along the b‐axis direction.     

1‐Acetyl‐3‐ferrocenyl‐5‐methyl‐1H‐pyrazole and 1‐acetyl‐5‐ferrocenyl‐3‐(2‐pyrid­yl)‐1H‐pyrazole

Mol­ecules of 1‐acetyl‐3‐ferrocenyl‐5‐methyl‐1H‐pyrazole, [Fe(C₅H₅)(C₁₁H₁₁N₂O)], form a centrosymmetric dimer generated by a combination of one C—H⋯π(pyrazole) and one C—H⋯π(cyclo­penta­dienyl) inter­action. The dimers are linked by C—H⋯π inter­actions, involving the pyrazole rings as acceptors, into layers parallel to (10). Mol­ecules of 1‐acetyl‐5‐ferrocenyl‐3‐(2‐pyrid­yl)‐1H‐pyrazole, [Fe(C₅H₅)(C₁₅H₁₂N₃O)], are linked by C—H⋯O inter­actions into a chain running in the [010] direction. Two chains of this type passing through each unit cell are connected by O⋯π(pyridyl) inter­actions into an [010] double chain.     

Inter­actions of thia­mine with polymeric halogenocadmate anions in the organic–inorganic hybrid compound (thia­minium)[Cd3Br4.4Cl3.6]

The structure of poly[3‐[(4‐amino‐2‐methylpyrimidin‐1‐ium‐5‐yl)meth­yl]‐5‐(2‐hydroxy­ethyl)‐4‐methyl­thia­zolium octa‐μ‐bromo/chloro­(4.4/3.6)‐tricadmate(II)], {(C₁₂H₁₈N₄OS)[Cd₃ Br_4.41Cl_3.59]}_n consists of hydrogen‐bonded thia­mine mol­ecules and polymeric cadmium bromide/chloride anions in an organic–inorganic hybrid fashion. The one‐dimensional anion ribbons are formed by edge‐sharing octa­hedra and vertex‐sharing tetra­hedra. Thia­mine mol­ecules adopting the S conformation are linked to anions via three types of inter­actions, namely an N(amino)—H⋯anion⋯thia­zolium bridging inter­action, an N(pyrimidine)—H⋯anion hydrogen bond and an O(hydr­oxy)—H⋯anion hydrogen bond.