In recent years, there is a significant interest from the crystallographic and materials science communities to have access to raw diffraction data. The effort in archiving raw data for access by the user community is spearheaded by the International Union of Crystallography (IUCr) Committee on Data. In materials science, where powder diffraction is extensively used, the challenge in archiving raw data is different to that from single crystal data, owing to the very nature of the contributions involved. Powder diffraction (X-ray or neutron) data consist of contributions from the material under study as well as instrument specific parameters. Having raw powder diffraction data can be essential in cases of analysing materials with poor crystallinity, disorder, micro structure (size/strain) etc. Here, the initiative and progress made by the International Centre for Diffraction Data (ICDDR) in archiving powder X-ray diffraction raw data in the Powder Diffraction FileTM (PDFR) database is outlined. The upcoming 2025 release of the PDF-5+ database will have more than 20 800 raw powder diffraction patterns that are available for reference.

Organic–inorganic hybrid crystals have diverse functionalities, for example in energy storage and luminescence, due to their versatile structures. The synthesis and structural characterization of a new cobalt–vanadium-containing compound, 2[Co(en)3]3+(V4O13)6−·4H2O (1) is presented. The crystal structure of 1, consisting of [Co(en)3]3+ complexes and chains of corner-sharing (VO4) tetrahedra, was solved by single-crystal X-ray diffraction in the centrosymmetric space group P1. Phase purity of the bulk material was confirmed by infrared spectroscopy, scanning electron microscopy, elemental analysis and powder X-ray diffraction. The volume expansion of 1 was found to be close to 1% in the reported temperature range from 100 to 300 K, with a volume thermal expansion coefficient of 56 (2) × 10−6 K−1. The electronic band gap of 1 is 2.30 (1) eV, and magnetic susceptibility measurements showed that the compound exhibits a weak paramagnetic response down to 1.8 K, probably due to minor CoII impurities (<1%) on the CoIII site.

Thio­phosgene is one of the principal C=S building blocks in synthetic chemistry. At room temperature, thio­phosgene is a red liquid. While its properties in the liquid and gaseous states are well known, a comprehensive characterization of thio­phosgene in its solid state is presented here. Differential scanning calorimetry shows that thio­phosgene forms a supercooled melt before rapidly crystallizing. Its melting point is 231.85 K (−41.3 °C). At 80 K, thio­phosgene crystallizes in space group P63/m [No. 174, a = b = 5.9645 (2), c = 6.2835 (3) Å, V = 193.59 (2) Å3]. The molecule shows a distinct rotational disorder: all S and Cl positions are of mixed occupancy and the disorder does not resolve at temperatures as low as 10 K, as was shown by neutron powder diffraction. Infrared, Raman and inelastic neutron scattering spectra were collected and assigned with the aid of quantum chemical calculations. A larger ordered structural model allowed for better agreement between the measured and calculated spectra, further indicating that disorder is an inherent feature of solid-state thio­phosgene.

The embedded call to a special version of the web-based Bilbao Crystallographic Server tool k-SUBGROUPSMAG from within GSAS-II to form a list of all possible commensurate magnetic subgroups of a parent magnetic grey group is described. It facilitates the selection and refinement of the best commensurate magnetic structure model by having all the analysis tools including Rietveld refinement in one place as part of GSAS-II. It also provides the chosen magnetic space group as one of the 1421 possible standard Belov–Neronova–Smirnova forms or equivalent non-standard versions.

Onchocerca volvulus causes blindness, onchocerciasis, skin infections and devastating neurological diseases such as nodding syndrome. New treatments are needed because the currently used drug, ivermectin, is contraindicated in pregnant women and those co-infected with Loa loa. The Seattle Structural Genomics Center for Infectious Disease (SSGCID) produced, crystallized and determined the apo structure of N-terminally hexahistidine-tagged O. volvulus macrophage migration inhibitory factor-1 (His-OvMIF-1). OvMIF-1 is a possible drug target. His-OvMIF-1 has a unique jellyfish-like structure with a prototypical macrophage migration inhibitory factor (MIF) trimer as the `head' and a unique C-terminal `tail'. Deleting the N-terminal tag reveals an OvMIF-1 structure with a larger cavity than that observed in human MIF that can be targeted for drug repurposing and discovery. Removal of the tag will be necessary to determine the actual biological oligomer of OvMIF-1 because size-exclusion chomatographic analysis of His-OvMIF-1 suggests a monomer, while PISA analysis suggests a hexamer stabilized by the unique C-terminal tails.

The title compound, C5H5NO2, is a hy­droxy­lated pyridine ring that has been studied for its involvement in microbial degradation of nicotinic acid. Here we describe its synthesis as a formic acid salt, rather than the standard hydro­chloride salt that is commercially available, and its spectroscopic and crystallographic characterization.

In the title mol­ecule, C7H7N3O, the pyrimidine ring is essentially planar, with the propynyl group rotated out of this plane by 15.31 (4)°. In the crystal, a tri-periodic network is formed by N—H⋯O, N—H⋯N and C—H⋯O hydrogen-bonding and slipped π–π stacking inter­actions, leading to narrow channels extending parallel to the c axis. Hirshfeld surface analysis of the crystal structure reveals that the most important contributions for the crystal packing are from H⋯H (36.2%), H⋯C/C⋯H (20.9%), H⋯O/O⋯H (17.8%) and H⋯N/N⋯H (12.2%) inter­actions, showing that hydrogen-bonding and van der Waals inter­actions are the dominant inter­actions in the crystal packing. Evaluation of the electrostatic, dispersion and total energy frameworks indicates that the stabilization is dominated by the electrostatic energy contributions. The mol­ecular structure optimized by density functional theory (DFT) calculations at the B3LYP/6–311 G(d,p) level is compared with the experimentally determined structure in the solid state. The HOMO–LUMO behaviour was also elucidated to determine the energy gap.

The mol­ecular and crystal structure of a discrete [Ni8(μ4-OH)6(μ-4-Rpz)12]2− (R = H; pz = pyrazolate anion, C3H3N2−) cluster with an unprecedented, perfectly cubic arrangement of its eight Ni centers is reported, along with its lower-symmetry alkyl-functionalized (R = methyl and n-oct­yl) derivatives. Crystals of the latter two were obtained with two identical counter-ions (Bu4N+), whereas the crystal of the complex with the parent pyrazole ligand has one Me4N+ and one Bu4N+ counter-ion. The methyl derivative incorporates 1,2-di­chloro­ethane solvent mol­ecules in its crystal structure, whereas the other two are solvent-free. The compounds are tetra­butyl­aza­nium tetra­methyl­aza­nium hexa-μ4-hydroxido-dodeca-μ2-pyrazolato-hexa­hedro-octa­nickel, (C16H36N)(C4H12N)[Ni8(C3H3N2)12(OH)6] or (Bu4N)(Me4N)[Ni8(μ4-OH)6(μ-pz)12] (1), bis­(tetra­butyl­aza­nium) hexa-μ4-hydroxido-dodeca-μ2-(4-methyl­pyrazolato)-hexa­hedro-octa­nickel 1,2-di­chloro­ethane 7.196-solvate, (C16H36N)2[Ni8(C4H5N2)12(OH)6]·7.196C2H4Cl2 or (Bu4N)2[Ni8(μ4-OH)6(μ-4-Mepz)12]·7.196(ClCH2CH2Cl) (2), and bis­(tetra­butyl­aza­nium) hexa-μ4-hydroxido-dodeca-μ2-(4-octylpyrazolato)-hexa­hedro-octa­nickel, (C16H36N)2[Ni8(C11H19N2)12(OH)6] or (Bu4N)2[Ni8(μ4-OH)6(μ-4-nOctpz)12] (3). All counter-ions are disordered (with the exception of one Bu4N+ in 3). Some of the octyl chains of 3 (the crystal is twinned by non-merohedry) are also disordered. Various structural features are discussed and contrasted with those of other known [Ni8(μ4-OH)6(μ-4-Rpz)12]2− complexes, including extended three-dimensional metal–organic frameworks. In all three structures, the Ni8 units are lined up in columns.

The title compound, C15H15F3N2O3S, crystallizes in the monoclinic system, space group I2/a, with Z = 8. As expected, the nine-membered heterobicyclic system is virtually planar and the cyclo­hexyl group adopts a chair conformation. There is structural evidence for intra­molecular N—S⋯O chalcogen bonding between the benziso­thia­zolinone S atom and one O atom of the nitro group, approximately aligned along the extension of the covalent N—S bond [N—S⋯O = 162.7 (1)°]. In the crystal, the mol­ecules form centrosymmetric dimers through C—H⋯O weak hydrogen bonding between a C—H group of the electron-deficient benzene ring and the benzo­thia­zolinone carbonyl O atom with an R22(10) motif. In contrast to the previously described N-acyl 7-nitro-5-(tri­fluoro­meth­yl)benzo[d]iso­thia­zol-3(2H)-ones, the title N-cyclo­hexyl­methyl analogue does not inhibit growth of Mycobacterium aurum and Mycobacterium smegmatis in vitro.

Single crystals of NbF5, niobium(V) fluoride, have been obtained by the reaction of niobium metal in a stream of dilute elemental fluorine at 473 K and subsequent sublimation. The as-obtained bulk phase compound was shown to be pure by powder X-ray diffraction at 293 K and by IR and Raman spectroscopy. A single-crystal X-ray analysis was conducted at 100 K. In comparison to the previously reported structure model [Edwards (1964). J. Chem. Soc. pp. 3714–3718], the lattice parameters and fractional atom coordinates were determined to much higher precision and individual, anisotropic displacement parameters were refined for all atoms.

Two new copper dimers, namely, bis­(dimethyl sulfoxide)­tetra­kis­(μ-pyrene-1-carboxyl­ato)dicopper(Cu—Cu), [Cu2(C17H9O2)4(C2H6OS)2] or [Cu2(pyr-COO−)4(DMSO)2] (1), and bis­(di­methyl­formamide)­tetra­kis­(μ-pyrene-1-carboxyl­ato)dicopper(Cu—Cu), [Cu2(C17H9O2)4(C3H7NO)2] or [Cu2(pyr-COO−)4(DMF)2] (2) (pyr = pyrene), were synthesized from the reaction of pyrene-1-carb­oxy­lic acid, copper(II) nitrate and tri­ethyl­amine from solvents DMSO and DMF, respectively. While 1 crystallized in the space group Poverline{1}, the crystal structure of 2 is in space group P21/n. The Cu atoms have octa­hedral geometries, with four oxygen atoms from carboxyl­ate pyrene ligands occupying the equatorial positions, a solvent mol­ecule coordinating at one of the axial positions, and a Cu⋯Cu contact in the opposite position. The packing in the crystal structures exhibits π–π stacking inter­actions and short contacts through the solvent mol­ecules. The Hirshfeld surfaces and two-dimensional fingerprint plots were generated for both compounds to better understand the inter­molecular inter­actions and the contribution of heteroatoms from the solvent ligands to the crystal packing. In addition, a Cu2+/Cu1+ quasi-reversible redox process was identified for compound 2 using cyclic voltammetry that accounts for a diffusion-controlled electron-donation process to the Cu dimer.

The synthetic availability of mol­ecular water oxidation catalysts containing high-valent ions of 3d metals in the active site is a prerequisite to enabling photo- and electrochemical water splitting on a large scale. Herein, the synthesis and crystal structure of di­ammonium {μ-1,3,4,7,8,10,12,13,16,17,19,22-dodeca­aza­tetra­cyclo­[8.8.4.13,17.18,12]tetra­cosane-5,6,14,15,20,21-hexa­onato}ferrate(IV) acetic acid tris­olvate, (NH4)2[FeIV(C12H12N12O6)]·3CH3COOH or (NH4)2[FeIV(L–6H)]·3CH3COOH is reported. The FeIV ion is encapsulated by the macropolycyclic ligand, which can be described as a dodeca-aza-quadricyclic cage with two capping tri­aza­cyclo­hexane fragments making three five- and six six-membered alternating chelate rings with the central FeIV ion. The local coord­ination environment of FeIV is formed by six deprotonated hydrazide nitro­gen atoms, which stabilize the unusual oxidation state. The FeIV ion lies on a twofold rotation axis (multiplicity 4, Wyckoff letter e) of the space group C2/c. Its coordination geometry is inter­mediate between a trigonal prism (distortion angle φ = 0°) and an anti­prism (φ = 60°) with φ = 31.1°. The Fe—N bond lengths lie in the range 1.9376 (13)–1.9617 (13) Å, as expected for tetra­valent iron. Structure analysis revealed that three acetic acid mol­ecules additionally co-crystallize per one iron(IV) complex, and one of them is positionally disordered over four positions. In the crystal structure, the ammonium cations, complex dianions and acetic acid mol­ecules are inter­connected by an intricate system of hydrogen bonds, mainly via the oxamide oxygen atoms acting as acceptors.

JUAMI, the joint undertaking for an African materials institute, is a project to build collaborations and materials research capabilities between PhD researchers in Africa, the United States, and the world. Focusing on research-active universities in the East African countries of Kenya, Ethiopia, Tanzania and Uganda, the effort has run a series of schools focused on materials for sustainable energy and materials for sustainable development. These bring together early-career researchers from Africa, the US, and beyond, for two weeks in a close-knit environment. The program includes lectures on cutting-edge research from internationally renowned speakers, highly interactive tutorial lectures on the science behind the research, also from internationally known researchers, and hands-on practicals and team-building exercises that culminate in group proposals from self-formed student teams. The schools have benefited more than 300 early-career students and led to proposals that have received funding and have led to research collaborations and educational non-profits. JUAMI continues and has an ongoing community of alumni who share resources and expertise, and is open to like-minded people who want to join and develop contacts and collaborations internationally.

In the title compound, C20H18O4, the dihedral angle between the 2H-chromen-2-one ring system and the phenyl ring is 89.12 (5)°. In the crystal, the mol­ecules are connected through C—H⋯O hydrogen bonds to generate [010] double chains that are reinforced by weak aromatic π–π stacking inter­actions. The unit-cell packing can be described as a tilted herringbone motif. The H⋯H, H⋯O/O⋯H, H⋯C/C⋯H and C⋯C contacts contribute 46.7, 24.2, 16.7 and 7.6%, respectively, to its Hirshfeld surface.

The title compound, C16H17N3O3, is racemic as it crystallizes in a centrosymmetric space group (Poverline{1}), although the trans disposition of substituents about the central C—C bond is established. The five- and six-membered rings are oriented at a dihedral angle of 75.88 (8)°. In the crystal, N—H⋯N hydrogen bonds form chains of mol­ecules extending along the c-axis direction that are connected by inversion-related pairs of O—H⋯N into ribbons. The ribbons are linked by C—H⋯π(ring) inter­actions, forming layers parallel to the ab plane. A Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H⋯H (45.9%), H⋯N/N⋯H (23.3%), H⋯C/C⋯H (16.2%) and H⋯O/O⋯H (12.3%) inter­actions. Hydrogen bonding and van der Waals inter­actions are the dominant inter­actions in the crystal packing. The volume of the crystal voids and the percentage of free space were calculated to be 100.94 Å3 and 13.20%, showing that there is no large cavity in the crystal packing. Evaluation of the electrostatic, dispersion and total energy frameworks indicates that the stabilization is dominated by the electrostatic energy contributions in the title compound. Moreover, the DFT-optimized structure at the B3LYP/6–311 G(d,p) level is compared with the experimentally determined mol­ecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.

The in­do­line portion of the title mol­ecule, C16H13NO2, is planar. In the crystal, a layer structure is generated by C—H⋯O hydrogen bonds and C—H⋯π(ring), π-stacking and C=O⋯π(ring) inter­actions. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (43.0%), H⋯C/C⋯H (25.0%) and H⋯O/O⋯H (22.8%) inter­actions. Hydrogen bonding and van der Waals inter­actions are the dominant inter­actions in the crystal packing. The volume of the crystal voids and the percentage of free space were calculated to be 120.52 Å3 and 9.64%, respectively, showing that there is no large cavity in the crystal packing. Evaluation of the electrostatic, dispersion and total energy frameworks indicate that the stabilization is dominated by the dispersion energy contributions in the title compound. Moreover, the DFT-optimized structure at the B3LYP/6-311G(d,p) level is compared with the experimentally determined mol­ecular structure in the solid state.

A new lanthanide coordination polymer, poly[[tri­aqua­bis­(μ4-phthalato)(μ3-pyridine-2,5-di­carboxyl­ato)dipraseodymium] monohydrate], {[Pr2(C7H3NO4)2(C8H4O4)(H2O)3]·H2O}n or {[Pr2(phth)2(pydc)(H2O)3]·H2O}n, (pydc2− = pyridine-2,5-di­carboxyl­ate and phth2− = phthalate) was synthesized and characterized, revealing the structure to be an assembly of di-periodic {Pr2(pydc)(phth)2(H2O)3}n layers. Each layer is built up by edge-sharing {Pr2N2O14} and {Pr2O16} dimers, which are connected through a new coordin­ation mode of pydc2− and phth2−. These layers are stabilized by inter­nal hydrogen bonds and π–π inter­actions. In addition, a three-dimensional supra­molecular framework is built by inter­layer hydrogen-bonding inter­actions involving the non-coordinated water mol­ecule. Thermogravimetric analysis shows that the title compound is thermally stable up to 400°C.

Lanthanide-containing materials are of inter­est in the field of crystal engin­eering because of their unique properties and distinct structure types. In this context, a new samarium–sodium heterometallic coordination polymer, poly[tetra­kis­(μ2-2-formyl-6-meth­oxy­phenolato)samarium(III)sodium(I)], {[SmNa(C8H7O3)4]·solvent}n (Sm-1), was synthesized and crystallized via slow evaporation from a mixture of ethanol and aceto­nitrile. The compound features alternating SmIII and NaI ions, which are linked by ortho-vanillin (o-vanillin) ligands to form a mono-periodic chain-like coordination polymer. The chains propagate along the [001] direction. Residual electron density of disordered solvent mol­ecules in the void space could not be reasonably modeled, thus the SQUEEZE function was applied. The structural, vibrational, and optical properties are reported.

Two compounds, (S)-8-{[(tert-butyl­dimethyl­sil­yl)­oxy]meth­yl}-1-[(2,2,4,6,7-penta­methyl-2,3-di­hydro­benzo­furan-5-yl)sulfon­yl]-1,3,4,6,7,8-hexa­hydro-2H-pyrimido[1,2-a]pyrimidin-1-ium tri­fluoro­methane­sulfonate, C27H46N3O4SSi+·CF3O3S−, (1) and (S)-8-(iodo­meth­yl)-1-tosyl-1,3,4,6,7,8-hexa­hydro-2H-pyrimido[1,2-a]pyrimidin-1-ium iodide, C15H21IN3O2S+·I−, (2), have been synthesized and characterized. They are bicyclic guanidinium salts and were synthesized from N-(tert-but­oxy­carbon­yl)-l-me­thio­nine (Boc-l-Met-OH). The guanidine is protected by a 2,2,4,6,7-penta­methyl­dihydro­benzo­furan-5-sulfonyl (Pbf, 1) or a tosyl (2) group. In the crystals of both compounds, the guanidinium group is almost planar and the N–H forms an intra­molecular hydrogen bond in a six-membered ring to the oxygen atom of the sulfonamide protecting group.

The crystal structures and Hirshfeld surface analyses of three similar compounds are reported. Methyl 4-[4-(di­fluoro­meth­oxy)phen­yl]-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate, (C21H23F2NO4), (I), crystallizes in the monoclinic space group C2/c with Z = 8, while isopropyl 4-[4-(di­fluoro­meth­oxy)phen­yl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carb­oxyl­ate, (C23H27F2NO4), (II) and tert-butyl 4-[4-(di­fluoro­meth­oxy)phen­yl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexa­hydro­quinoline-3-carboxyl­ate, (C24H29F2NO4), (III) crystallize in the ortho­rhom­bic space group Pbca with Z = 8. In the crystal structure of (I), mol­ecules are linked by N—H⋯O and C—H⋯O inter­actions, forming a tri-periodic network, while mol­ecules of (II) and (III) are linked by N—H⋯O, C—H⋯F and C—H⋯π inter­actions, forming layers parallel to (002). The cohesion of the mol­ecular packing is ensured by van der Waals forces between these layers. In (I), the atoms of the 4-di­fluoro­meth­oxy­phenyl group are disordered over two sets of sites in a 0.647 (3): 0.353 (3) ratio. In (III), the atoms of the dimethyl group attached to the cyclo­hexane ring, and the two carbon atoms of the cyclo­hexane ring are disordered over two sets of sites in a 0.646 (3):0.354 (3) ratio.

The crystal structure of the tetra­ethyl­ammonium salt of the non-steroidal anti-inflammatory drug nimesulide (polymorph II) (systematic name: tetra­ethyl­ammonium N-methane­sulfonyl-4-nitro-2-phen­oxy­anilinide), C8H20N+·C13H11N2O5S−, was determined using single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic space group P21/c with one tetra­ethyl­ammonium cation and one nimesulide anion in the asymmetric unit. In the crystal, the ions are linked by C—H⋯N and C—H⋯O hydrogen bonds and C—H⋯π inter­actions. There are differences in the geometry of both the nimesulide anion and the tetra­ethyl­ammonium cation in polymorphs I [Rybczyńska & Sikorski (2023). Sci. Rep. 13, 17268] and II of the title compound.

A CuII coordination polymer, catena-poly[[[aqua­copper(II)]-bis­(μ-4-amino­benz­o­ato)-κ2N:O;κ2O:N] monohydrate], {[Cu(pABA)2(H2O)]·H2O}n (pABA = p-amino­benzoate, C7H4NO2−), was synthesized and characterized. It exhibits a one-dimensional chain structure extended into a three-dimensional supra­molecular assembly through hydrogen bonds and π–π inter­actions. While the twinned crystal shows a metrically ortho­rhom­bic lattice and an apparent space group Pbcm, the true symmetry is monoclinic (space group P2/c), with disordered Cu atoms and mixed roles of water mol­ecules (aqua ligand/crystallization water). The luminescence spectrum of the complex shows an emission at 345 nm, cf. 349 nm for pABAH.

An attempt to explore the reactivity of the nitro group in the presence of gold catalysis in comparison to the azide group yielded intriguing results. Surprisingly, only the nitro group exhibited reactivity, ultimately giving rise to the formation of the title isatogen, C14H8N4O2. In the crystal structure, weak C—H⋯O hydrogen bonds and π–π stacking inter­actions link the mol­ecules. The structure exhibits disorder of the mol­ecule.

The complex, tri­chlorido­(1,4,11-tri­aza-8-azonia­tetra­cyclo­[6.6.2.04,16.011,15]hexa­decane 1-oxide-κO)zinc(II) monohydrate, [ZnCl3(C12H23N4O)]·H2O, (I), has monoclinic symmetry (space group P21/n) at 120 K. The zinc(II) center adopts a slightly distorted tetra­hedral coordination geometry and is coordinated by three chlorine atoms and the oxygen atom of the oxidized tertiary amine of the tetra­cycle. The amine nitro­gen atom, inside the ligand cleft, is protonated and forms a hydrogen bond to the oxygen of the amine oxide. Additional hydrogen-bonding inter­actions involve the protonated amine, the water solvate oxygen atom, and one of the chloro ligands.

In the title mol­ecule, C21H23N3O3, the imidazolidine ring slightly deviates from planarity and the morpholine ring exhibits the chair conformation. In the crystal, N—H⋯O and C—H⋯O hydrogen bonds form helical chains of mol­ecules extending parallel to the c axis that are connected by C—H⋯π(ring) inter­actions. A Hirshfeld surface analysis reveals that the most important contributions for the crystal packing are from H⋯H (55.2%), H⋯C/C⋯H (22.6%) and H⋯O/O⋯H (20.5%) inter­actions. The volume of the crystal voids and the percentage of free space were calculated to be 236.78 Å3 and 12.71%, respectively. Evaluation of the electrostatic, dispersion and total energy frameworks indicates that the stabilization is dominated by the nearly equal electrostatic and dispersion energy contributions. The DFT-optimized mol­ecular structure at the B3LYP/6-311 G(d,p) level is compared with the experimentally determined mol­ecular structure in the solid state. Moreover, the HOMO–LUMO behaviour was elucidated to determine the energy gap.

In the structure of the title compound, C22H22N4O4·C3H7NO·H2O, the entire tricyclic system is approximately planar except for the carbon atom bearing the two methyl groups; the meth­oxy­phenyl ring is approximately perpendicular to the tricycle. All seven potential hydrogen-bond donors take part in classical hydrogen bonds. The main mol­ecule and the DMF combine to form broad ribbons parallel to the a axis and roughly parallel to the ab plane; the water mol­ecules connect the residues in the third dimension.

The title compound, C8H7NO2, crystallizes as prismatic colourless crystals in space group Poverline{1}, with one mol­ecule in the asymmetric unit. The pyridine ring is fused to acrylic acid, forming an almost planar structure with an E-configuration about the double bond with a torsion angle of −6.1 (2)°. In the crystal, strong O—H⋯N inter­actions link the mol­ecules, forming chains along the [101] direction. Weak C—H⋯O inter­actions link adjacent chains along the [100] direction, generating an R22(14) homosynthon. Finally, π–π stacking inter­actions lead to the formation of the three-dimensional structure. The supra­molecular analysis was supported by Hirshfeld surface and two-dimensional fingerprint plot analysis, indicating that the most abundant contacts are associated with H⋯H, O⋯H/H⋯O, N⋯H/H⋯N and C⋯H/H⋯C inter­actions.

The title compound, C12H10N2O3, was obtained by the de­acetyl­ation reaction of 1-(6-amino-5-nitro­naphthalen-2-yl)ethanone in a concentrated sulfuric acid methanol solution. The mol­ecule comprises a naphthalene ring system bearing an acetyl group (C-3), an amino group (C-7), and a nitro group (C-8). In the crystal, the mol­ecules are assembled into a two-dimensional network by N⋯H/H⋯N and O⋯H/H⋯O hydrogen-bonding inter­actions. n–π and π–π stacking inter­actions are the dominant inter­actions in the three-dimensional crystal packing. Hirshfeld surface analysis indicates that the most important contributions are from O⋯H/H⋯O (34.9%), H⋯H (33.7%), and C⋯H/H⋯C (11.0%) contacts. The energies of the frontier mol­ecular orbitals were computed using density functional theory (DFT) calculations at the B3LYP-D3BJ/def2-TZVP level of theory and the LUMO–HOMO energy gap of the mol­ecule is 3.765 eV.

The benzimidazole entity of the title mol­ecule, C17H21N5O, is almost planar (r.m.s. deviation = 0.0262 Å). In the crystal, bifurcated C—H⋯O hydrogen bonds link individual mol­ecules into layers extending parallel to the ac plane. Two weak C—H⋯π(ring) inter­actions may also be effective in the stabilization of the crystal structure. Hirshfeld surface analysis of the crystal structure reveals that the most important contributions for the crystal packing are from H⋯H (57.9%), H⋯C/C⋯H (18.1%) and H⋯O/O⋯H (14.9%) inter­actions. Hydrogen bonding and van der Waals inter­actions are the most dominant forces in the crystal packing. Evaluation of the electrostatic, dispersion and total energy frameworks indicate that the stabilization of the title compound is dominated via dispersion energy contributions. The mol­ecular structure optimized by density functional theory (DFT) at the B3LYP/6–311 G(d,p) level is compared with the experimentally determined mol­ecular structure in the solid state.

The title compound, C12H16N2O, is a hy­droxy-substituted mono­amine alkaloid, and the primary metabolite of the naturally occurring psychedelic compound psilocybin. Crystalline forms of psilocin are known, but their characterization by single-crystal structure analysis is limited. Herein, two anhydrous polymorphic forms (I and II) of psilocin are described. The crystal structure of polymorphic Form I, in space group P21/c, was first reported in 1974. Along with the redeterm­ination to modern standards and unambiguous location of the acidic H atom and variable-temperature single-crystal unit-cell determinations for Form I, the Form II polymorph of the title compound, which crystallizes in the monoclinic space group P21/n, is described for the first time. The psilocin mol­ecules are present in both forms in their phenol–amine tautomeric forms (not resolved in the 1974 report). The mol­ecules in Forms I and II, however, feature different conformations of their N,N-dimethyl ethyl­ene substituent, with the N—C—C—C link in Form I being trans and in Form II being gauche, allowing the latter to bend back to the hydroxyl group of the same mol­ecule, leading to the formation of a strong intra­molecular O—H⋯N hydrogen bond between the hydroxyl moiety and ethyl­amino-nitro­gen group. In the extended structure of Form II, the mol­ecules form one-dimensional strands through N—H⋯O hydrogen bonds from the indole group to the oxygen atom of the hydroxyl moiety of an adjacent mol­ecule. Form II exhibits whole-mol­ecule disorder due to a pseudo-mirror operation, with an occupancy ratio of 0.689 (5):0.311 (5) for the two components. In contrast, Form I does not feature intra­molecular hydrogen bonds but forms a layered structure through inter­molecular N—H⋯O and O—H⋯N hydrogen bonds.

Crystal formation of penta­sodium nona­deca­cesium tetra­cosa­tungstate(VI) heneikosahydrate, Na5Cs19[W24O84]·21H2O, was successfully achieved by the conversion of [H2W12O42]10− through the addition of excess Cs+. The crystal structure comprising the toroidal isopolyoxidometalate is presented, as well as its Raman spectrum. Na5Cs19(H2O)21W24O84 crystallizes in the rhombohedral space group Roverline{3} with an obverse centering. The title compound represents the addition of a new member to the isopolytungstate family with mixed alkali counter-ions and contains rarely observed five-coordinate tungsten(VI) atoms in the [W24O84]24− anion (site symmetry C3i) arising from the conversion mediated by Cs+ counter-ions.

The structural characterization is reported of the supra­molecular complex between the tetra­quinoxaline-based cavitand 2,8,14,20-tetra­hexyl-6,10:12,16:18,22:24,4-O,O'-tetra­kis­(quinoxaline-2,3-di­yl)calix[4]resorcinarene (QxCav) with benzo­nitrile. The complex, of general formula C84H80N8O8·2C7H5N, crystallizes in the space group Poverline{1} with two independent mol­ecules in the asymmetric unit, displaying very similar geometrical parameters. For each complex, one of the benzo­nitrile mol­ecules is engulfed inside the cavity, while the other is located among the alkyl legs at the lower rim. The host and the guests mainly inter­act through weak C—H⋯π, C—H⋯N and dispersion inter­actions. These inter­actions help to consolidate the formation of supra­molecular chains running along the crystallographic b-axis direction.

The title compound, tetra­ethyl­ammonium tri­azido­tri-μ3-sulfido-[μ3-(tri­methyl­sil­yl)aza­nediido][tris­(3,5-di­methyl­pyrazol-1-yl)hydro­borato]triiron(+2.33)molybdenum(IV), (C8H20N)[Fe3MoS3(C15H22BN6)(C3H9NSi)(N3)3] or (Et4N)[(Tp*)MoFe3S3(μ3-NSiMe3)(N3)3] [Tp* = tris­(3,5-di­methyl­pyrazol-1-yl)hydro­bor­ate(1−)], crystallizes as needle-like black crystals in space group Poverline{1}. In this cluster, the Mo site is in a distorted octa­hedral coordination model, coordinating three N atoms on the Tp* ligand and three μ3-bridging S atoms in the core. The Fe sites are in a distorted tetra­hedral coordination model, coordinating two μ3-bridging S atoms, one μ3-bridging N atom from Me3SiN2−, and another N atom on the terminal azide ligand. This type of heterometallic and heteroleptic single cubane cluster represents a typical example within the Mo–Fe–S cluster family, which may be a good reference for understanding the structure and function of the nitro­genase FeMo cofactor. The residual electron density of disordered solvent mol­ecules in the void space could not be reasonably modeled, thus the SQUEEZE [Spek (2015). Acta Cryst. C71, 9–18] function was applied. The solvent contribution is not included in the reported mol­ecular weight and density.

This title compound, C20H26O2, was isolated from the benzene fraction of the stem bark of Staudtia kamerunensis Warb. (Myristicaceae) using column chromatography techniques over silica gel. The compound was fully characterized by single-crystal X-ray diffraction, one and two-dimensional NMR spectroscopy, IR and MS spectrometry. The compound has two fused cyclo­hexane rings attached to a benzene ring, with a carb­oxy­lic acid on C-4. This cyclo­hexene ring has a chair conformation while the other adopts a half-chair conformation. The benzene ring is substituted with a propenyl moiety. The structure is characterized by inter­molecular O—H⋯O hydrogen bonds, two C—H⋯O intra­molecular hydrogen bonds and two C—H⋯π inter­actions. The mol­ecular structure confirms previous studies carried out by spectroscopic techniques.

3-Phenyl-2-(thio­phen-3-yl)-2,3-di­hydro-4H-pyrido[3,2-e][1,3]thia­zin-4-one (C17H12N2OS2, 1) and 2-(1H-indol-3-yl)-3-phenyl-2,3-di­hydro-4H-pyrido[3,2-e][1,3]thia­zin-4-one 0.438-hydrate (C21H15N3OS·0.438H2O, 2) crystallize in space groups P21/n and C2/c, respectively. The asymmetric unit in each case is comprised of two parent mol­ecules, albeit of mixed chirality in the case of 1 and of similar chirality in 2 with the enanti­omers occupying the neighboring asymmetric units. Structure 2 also has water mol­ecules (partial occupancies) that form continuous channels along the b-axis direction. The thia­zine rings in both structures exhibit an envelope conformation. Inter­molecular inter­actions in 1 are defined only by C—H⋯O and C—H⋯N hydrogen bonds between crystallographically independent mol­ecules. In 2, hydrogen bonds of the type N—H⋯O between independent mol­ecules and C—H⋯N(π) type, and π–π stacking inter­actions between the pyridine rings of symmetry-related mol­ecules are observed.

Tetra­kis(μ-acetato-κ2O:O')bis­{[1,3-bis­(2,6-diiso­propyl­phen­yl)imidazol-2-yl­idene-κC2]chromium(II)} tetra­hydro­furan disolvate, [Cr2(C2H3O2)4(C27H36N4)2]·2C4H8O or [Cr2(OAc)4(IDipp)2]·2C4H8O (1), and tetra­kis­(μ-acetato-κ2O:O')bis­{[1,3-bis­(2,4,6-tri­methyl­phen­yl)imidazol-2-yl­idene-κC2]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 Poverline{1}. The mol­ecular 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.

The title compound, [Ni(NCS)2(C6H7N)2]n, was prepared by the reaction of Ni(NCS)2 with 4-methyl­pyridine in water. Its asymmetric unit consists of two crystallographically independent NiII cations, of which one is located on a twofold rotational axis whereas the second occupies a center of inversion, two independent thio­cyanate anions and two independent 4-methyl­pyridine co­ligands in general positions. Each NiII cation is octa­hedrally coordinated by two 4-methyl­pyridine coligands as well as two N- and two S-bonded thio­cyanate anions. One of the cations shows an all-trans, the other a cis–cis–trans configuration. The metal centers are linked by pairs of μ-1,3-bridging thio­cyanate anions into [101] chains. X-ray powder diffraction shows that a pure crystalline phase has been obtained and thermogravimetry coupled to differential thermoanalysis reveals that the title compound loses half of the 4-methyl­pyridine coligands and transforms into Ni(NCS)2(C6H7N). Nearly pure samples of this compound can be obtained by thermal annealing and a Rietveld refinement demonstrated that it is isotypic to its recently reported Cd analog [Neumann et al., (2020). CrystEngComm. 22, 184–194] In its crystal structure, the metal cations are linked by one μ-1,3(N,S)- and one μ-1,3,3(N,S,S)-bridging thio­cyanate anion into single chains that condense via the μ-1,3,3(N,S,S)-bridging anionic ligands into double chains.

The pyrazolo­pyrimidine moiety in the title mol­ecule, C13H12N4S, is planar with the methyl­sulfanyl substituent lying essentially in the same plane. The benzyl group is rotated well out of this plane by 73.64 (6)°, giving the mol­ecule an approximate L shape. In the crystal, C—H⋯π(ring) inter­actions and C—H⋯S hydrogen bonds form tubes extending along the a axis. Furthermore, there are π–π inter­actions between parallel phenyl rings with centroid-to-centroid distances of 3.8418 (12) Å. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (47.0%), H⋯N/N⋯H (17.6%) and H⋯C/C⋯H (17.0%) inter­actions. The volume of the crystal voids and the percentage of free space were calculated to be 76.45 Å3 and 6.39%, showing that there is no large cavity in the crystal packing. Evaluation of the electrostatic, dispersion and total energy frameworks indicate that the cohesion of the crystal structure is dominated by the dispersion energy contributions.

The X-ray crystal structure data of 12-α-fluoro-3β-hy­droxy­olean-28,13β-olide methanol hemisolvate, 2C30H47FO3·CH3OH, (1), and 12-α-fluoro-3β-hy­droxy­taraxer-28,14β-olide methanol hemisolvate, 2C30H47FO3·CH3OH, (2), are described. The fluoro­lactonization of oleanolic acid using SelectfluorTM yielded a mixture of the six-membered δ-lactone (1) and the unusual seven-membered γ-lactone (2) following a 1,2-shift of methyl C-27 from C-14 to C-13.

Two new [1-(phenyl­sulfon­yl)-1H-indol-2-yl]methanamine derivatives, namely, N-(3-meth­oxy­phen­yl)-N-{[1-(phenyl­sulfon­yl)-1H-indol-2-yl]meth­yl}acetamide, C24H22N2O4S, (I), and N-(2,5-di­meth­oxy­phen­yl)-N-{[1-(phenyl­sulfon­yl)-1H-indol-2-yl]meth­yl}benzene­sulfonamide, C29H26N2O6S2, (II), reveal a nearly orthogonal orientation of their indole ring systems and sulfonyl-bound phenyl rings. The sulfonyl moieties adopt the anti-periplanar conformation. For both compounds, the crystal packing is dominated by C—H⋯O bonding [C⋯O = 3.312 (4)–3.788 (8) Å], with the structure of II exhibiting a larger number, but weaker bonds of this type. Slipped π–π inter­actions of anti­parallel indole systems are specific for I, whereas the structure of II delivers two kinds of C—H⋯π inter­actions at both axial sides of the indole moiety. These findings agree with the results of Hirshfeld surface analysis. The primary contributions to the surface areas are associated with the contacts involving H atoms. Although II manifests a larger fraction of the O⋯H/H⋯O contacts (25.8 versus 22.4%), most of them are relatively distal and agree with the corresponding van der Waals separations.

The dinuclear mol­ecule of the title compound, [Mo2(C9H13)2(CO)6] or [Mo(tBuCp)(CO)3]2 where tBu and Cp are tert-butyl and cyclo­penta­dienyl, is centrosymmetric and is characterized by an Mo—Mo bond length of 3.2323 (3) Å. Imposed by inversion symmetry, the tBuCp and the carbonyl ligands are in a transoid arrangement to each other. In the crystal, inter­molecular C—H⋯O contacts lead to the formation of layers parallel to the bc plane.

Single crystals of the mol­ecular compound, {Cu20Ir6Cl8(C21H24N2)6(C4H4N2)3]·3.18CH3OH or [({Cu10Ir3}Cl4(IMes)3(pyrazine))2(pyrazine)]·3.18CH3OH [where IMes is 1,3-bis­(2,4,6-trimethylphen­yl)imidazol-2-yl­idene], with a unique heterometallic cluster have been prepared and the structure revealed using single-crystal X-ray diffraction. The mol­ecule is centrosymmetric with two {Cu10Ir3} cores bridged by a pyrazine ligand. The polymetallic cluster contains three stabilizing N-heterocyclic carbenes, four Cl ligands, and a non-bridging pyrazine ligand. Notably, the Cu—Ir core is arranged in an unusual shape containing 13 vertices, 22 faces, and 32 sides. The atoms within the trideca­metallic cluster are arranged in four planes, with 2, 4, 4, 3 metals in each plane. Ir atoms are present in alternate planes with an Ir atom featuring in the peripheral bimetallic plane, and two Ir atoms featuring on opposite sides of the non-adjacent tetra­metallic plane. The crystal contains two disordered methanol solvent mol­ecules with an additional region of non-modelled electron density corrected for using the SQUEEZE routine in PLATON [Spek (2015). Acta Cryst. C71, 9–18]. The given chemical formula and other crystal data do not take into account the unmodelled methanol solvent mol­ecule(s).

The benzimidazole moiety in the title mol­ecule, C19H25N5O, is almost planar and oriented nearly perpendicular to the triazole ring. In the crystal, C—H⋯O hydrogen bonds link the mol­ecules into a network structure. There are no π–π inter­actions present but two weak C—H⋯π(ring) inter­actions are observed. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (62.0%), H⋯C/C⋯H (16.1%), H⋯N/N⋯H (13.7%) and H⋯O/O⋯H (7.5%) inter­actions. Evaluation of the electrostatic, dispersion and total energy frameworks indicate that the stabilization is dominated via the dispersion energy contributions in the title compound.

This work describes the X-ray structure of orange–red crystals of 2-meth­oxy-5-nitro­aniline, C7H8N2O3. The compound displays concentration-dependent UV-Vis spectra, which is attributed to dipole-induced aggregation, and light absorption arising from an inter­molecular charge-transfer process that decreases in energy as the degree of aggregation increases. The crystals display π-stacking where the dipole moments align anti­parallel. Stacked mol­ecules inter­act with the next stack via hydrogen bonds, which is a state of maximum aggregation. Light absorption by charge transfer can be compared to colored inorganic semiconductors such as orange–red CdS, with a band gap of 2.0–2.5 eV.

The synthesis of the title compound, [Zn(C4H6N2)6](NO3)2, is described. This complex consists of a central zinc metal ion surrounded by six 1-methyl­imidazole ligands, charge balanced by two nitrate anions. The complex crystallizes in the space group Poverline{3}. In the crystal, the nitrate ions are situated within the cavities created by the [Zn(N-Melm)6]2+ cations, serving as counter-ions. The three oxygen atoms of the nitrate ion engage in weak C—H⋯O inter­actions. In addition to single-crystal X-ray diffraction analysis, the complex was characterized using elemental analysis, 1H NMR, 13C NMR, and FTIR spectroscopy.

A new pyridine-fused seleno­diazo­lium salt, 3-(phenyl­selan­yl)[1,2,4]selena­diazolo[4,5-a]pyridin-4-ylium chloride di­chloro­methane 0.352-solvate, C12H9N2Se2+·Cl−·0.352CH2Cl2, was obtained from the reaction between 2-pyridyl­selenenyl chloride and phenyl­seleno­cyanate. Single-crystal structural analysis revealed the presence of C—H⋯N, C—H⋯Cl−, C—H⋯Se hydrogen bonds as well as chalcogen–chalcogen (Se⋯Se) and chalcogen–halogen (Se⋯Cl−) inter­actions. Non-covalent inter­actions were explored by DFT calculations followed by topological analysis of the electron density distribution (QTAIM analysis). The structure consists of pairs of seleno­diazo­lium moieties arranged in a head-to-tail fashion surrounding disordered di­chloro­methane mol­ecules. The assemblies are connected by C—H⋯Cl− and C—H⋯N hydrogen bonds, forming layers, which stack along the c-axis direction connected by bifurcated Se⋯Cl−⋯H—C inter­actions.

During our studies of the oxidation of gold(I) complexes of tri­alkyl­phosphane chalcogenides, general formula R1R2R3PEAuX, (R = tert-butyl or isopropyl, E = S or Se, X = Cl or Br) with PhICl2 or elemental bromine, we have isolated a set of seven mixed-valence by-products, the bis­(tri­alkyl­phosphane chalcogenido)gold(I) tetra­halogenidoaurates(III) [(R1R2R3PE)2Au]+[AuX4]−. These corres­pond to the addition of one halogen atom per gold atom of the AuI precursor. Com­pound 1, bis­(triiso­propyl­phosphane sulfide)­gold(I) tetra­chlorido­aur­ate(III), [Au(C9H21PS)2][AuCl4] or [(iPr3PS)2Au][AuCl4], crystallizes in space group P21/n with Z = 4; the gold(I) atoms of the two cations lie on twofold rotation axes, and the gold(III) atoms of the two anions lie on inversion centres. Compound 2, bis­(tert-butyl­diiso­propyl­phosphane sulfide)­gold(I) tetra­chlorido­aurate(III), [Au(C10H23PS)2][AuCl4] or [(tBuiPr2PS)2Au][AuCl4], crystallizes in space group P1 with Z = 4; the asymmetric unit contains two cations and two anions with no imposed symmetry. A least-squares fit of the two cations gave an r.m.s. deviation of 0.19 Å. Compound 3, bis­(tri-tert-butyl­phosphane sulfide)­gold(I) tetra­chlorido­aurate(III), [Au(C12H27PS)2][AuCl4] or [(tBu3PS)2Au][AuCl4], crystallizes in space group P1 with Z = 1; both gold atoms lie on inversion centres. Compound 4a, bis­(tert-butyl­diiso­propyl­phosphane sulfide)­gold(I) tetra­bromi­doaurate(III), [Au(C10H23PS)2][AuBr4] or [(tBuiPr2PS)2Au][AuBr4], crystallizes in space group P21/c with Z = 4; the cation lies on a general position, whereas the gold(III) atoms of the two anions lie on inversion centres. Compound 4b, bis­(tert-butyl­diiso­propyl­phosphane selenide)gold(I) tetra­bromido­aurate(III), [Au(C10H23PSe)2][AuBr4] or [(tBuiPr2PSe)2Au][AuBr4], is isotypic with 4a. Compound 5a, bis­(tri-tert-butyl­phosphane sulfide)­gold(I) tetra­bromido­aurate(III), [Au(C12H27PS)2][AuBr4] or [(tBu3PS)2Au][AuBr4], is isotypic with compound 4a. Compound 5a, bis­(tri-tert-butyl­phosphane sulfide)­gold(I) tetra­bromido­aurate(III), [Au(C12H27PS)2][AuBr4] or [(tBu3PS)2Au][AuBr4], crystallizes in space group P1 with Z = 1; both gold atoms lie on inversion centres. Compound 5b, bis­(tri-tert-butyl­phosphane selenide)gold(I) tetra­bromido­aurate(III), [Au(C12H27PSe)2][AuBr4] or [(tBu3PSe)2Au][AuBr4], is isotypic with 5a. All AuI atoms are linearly coordinated and all AuIII atoms exhibit a square-planar coordination environment. The ligands at the AuI atoms are anti­periplanar to each other across the S⋯S vectors. There are several short intra­molecular H⋯Au and H⋯E contacts. Average bond lengths (Å) are: P—S = 2.0322, P—Se = 2.1933, S—Au = 2.2915, and Se—Au = 2.4037. The complex three-dimensional packing of 1 involves two short C—Hmethine⋯Cl contacts (and some slightly longer contacts). For 2, four C—Hmethine⋯Cl inter­actions combine to produce zigzag chains of residues parallel to the c axis. Additionally, an S⋯Cl contact is observed that might qualify as a ‘chalcogen bond’. The packing of 3 is three-dimensional, but can be broken down into two layer structures, each involving an S⋯Cl and an H⋯Cl contact. For the bromido derivatives 4a/b and 5a/b, loose associations of the anions form part of the packing patterns. For all four compounds, these combine with an E⋯Br contact to form layers parallel to the ab plane.

The title mol­ecule, C25H23BrN2O2, adopts a cup shaped conformation with the distinctly ruffled imidazolidine ring as the base. In the crystal, weak C—H⋯O hydrogen bonds and C—H⋯π(ring) inter­actions form helical chains of mol­ecules extending along the b-axis direction that are linked by additional weak C—H⋯π(ring) inter­actions across inversion centres. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (51.0%), C⋯H/H⋯C (21.3%), Br⋯H/H⋯Br (12.8%) and O⋯H/H⋯O (12.4%) inter­actions. The volume of the crystal voids and the percentage of free space were calculated to be 251.24 Å3 and 11.71%, respectively, showing that there is no large cavity in the crystal packing. Evaluation of the electrostatic, dispersion and total energy frameworks indicate that the stabilization is dominated by the dispersion energy.

A host–guest supra­molecular inclusion complex was obtained from the co-crystallization of A1/A2-bromo­but­oxy-hy­droxy difunctionalized pillar[5]arene (PilButBrOH) with adipo­nitrile (ADN), C47H53.18Br0.82O10·C6H8N2. The adipo­nitrile guest is stabilized within the electron-rich cavity of the pillar[5]arene host via multiple C—H⋯O and C—H⋯π inter­actions. Both functional groups on the macrocyclic rim are engaged in supra­molecular inter­actions with an adjacent inclusion complex via hydrogen-bonding (O—H⋯N or C—H⋯Br) inter­actions, resulting in the formation of a supra­molecular dimer in the crystal structure.

Two new phenyl­sulfonyl­indole derivatives, namely, N-{[3-bromo-1-(phenyl­sulfon­yl)-1H-indol-2-yl]meth­yl}-N-(4-bromo-3-meth­oxy­phen­yl)benzene­sulfonamide, C28H22Br2N2O5S2, (I), and N,N-bis­{[3-bromo-1-(phenyl­sulfon­yl)-1H-indol-2-yl]meth­yl}benzene­sulfonamide, C36H27Br2N3O6S3, (II), reveal the impact of intra­molecular π–π inter­actions of the indole moieties as a factor not only governing the conformation of N,N-bis­(1H-indol-2-yl)meth­yl)amines, but also significantly influencing the crystal patterns. For I, the crystal packing is dominated by C—H⋯π and π–π bonding, with a particular significance of mutual indole–indole inter­actions. In the case of II, the mol­ecules adopt short intra­molecular π–π inter­actions between two nearly parallel indole ring systems [with the centroids of their pyrrole rings separated by 3.267 (2) Å] accompanied by a set of forced Br⋯O contacts. This provides suppression of similar inter­actions between the mol­ecules, while the importance of weak C—H⋯O hydrogen bonding to the packing naturally increases. Short contacts of the latter type [C⋯O = 3.389 (6) Å] assemble pairs of mol­ecules into centrosymmetric dimers with a cyclic R22(13) ring motif. These findings are consistent with the results of a Hirshfeld surface analysis and together they suggest a tool for modulating the supra­molecular behavior of phenyl­sulfonyl­ated indoles.