The re-investigation of [Bi2O2(OH)](NO3), dioxidodibismuth(III) hydroxide nitrate, on the basis of single-crystal X-ray diffraction data revealed an apparent structural phase transition of a crystal structure determined previously (space group Cmc21 at 173 K) to a crystal structure with lower symmetry (space group Pna21 at 100 K). The Cmc21 → Pna21 group–subgroup relationship between the two crystal structures is klassengleiche with index 2. In contrast to the crystal structure in Cmc21 with orientational disorder of the nitrate anion, disorder does not occur in the Pna21 structure. Apart from the disorder of the nitrate anion, the general structural set-up in the two crystal structures is very similar: [Bi2O2]2+ layers extend parallel to (001) and alternate with layers of (OH)− anions above and (NO3)− anions below the cationic layer. Whereas the (OH)− anion shows strong bonds to the BiIII cations, the (NO3)− anion weakly binds to the BiIII cations of the cationic layer. A rather weak O—H⋯O hydrogen-bonding inter­action between the (OH)− anion and the (NO3)− anion links adjacent sheets along [001].

In the structure of the title compound, C19H19N3O5S·C4H8O2, the two independent dioxane mol­ecules each display inversion symmetry. The pyrazole ring is approximately parallel to the aromatic ring of the oxy-ethanone group and approximately perpendicular to the tolyl ring of the sulfonyl substituent. An extensive system of classical and `weak' hydrogen bonds connects the residues to form a layer structure parallel to (201), within which dimeric subunits are conspicuous; neighbouring layers are connected by classical hydrogen bonds to dioxanes and by `weak' hydrogen bonds from Htol­yl donors.

The title compound dipotassium gadolinium(III) phosphate(V) molybdate(VI), K2Gd(PO4)(MoO4), was synthesized from a high-temperature melt starting from GdF3 as a source of gadolinium. Its structure is isotypic with other MI2MIII(MVIO4)(PO4) compounds, where MI = Na, K or Cs, and MIII = rare-earth cation, MVI = Mo or W. The three-dimensional framework is built up from [Gd(PO4)(MoO4)] anionic sheets, which are organized by adhesion of [GdPO4] layers and [MoO4] tetra­hedra stacked above and below these layers. The inter­stitial space is occupied by K cations having eightfold oxygen coordination. The polyhedron of GdO8 was estimated to be a triangular dodeca­hedron by the continuous shape measurement method.

In the title compound, C10H8N4O3·C3H7NO, the asymmetric unit contains two crystallographically independent mol­ecules A and B, each of which has one DMF solvate mol­ecule. Mol­ecules A and B both feature intra­molecular N—H⋯O hydrogen bonds, forming S(6) ring motifs and consolidating the mol­ecular configuration. In the crystal, N—H⋯O and O—H⋯O hydrogen bonds connect mol­ecules A and B, forming R22(8) ring motifs. Weak C—H⋯O inter­actions link the mol­ecules, forming layers parallel to the (overline{2}12) plane. The DMF solvent mol­ecules are also connected to the main mol­ecules (A and B) by N—H⋯O hydrogen bonds. π–π stacking inter­actions [centroid-to-centroid distance = 3.8702 (17) Å] between the layers also increase the stability of the mol­ecular structure in the third dimension. According to the Hirshfeld surface study, O⋯H/H⋯O inter­actions are the most significant contributors to the crystal packing (27.5% for mol­ecule A and 25.1% for mol­ecule B).

The crystal structure of the new triclinic polymorph of miconazole {MIC; C18H14Cl4N2O; systematic name: (RS)-1-[2-(2,4-di­chloro­benz­yloxy)-2-(2,4-di­chloro­phen­yl)eth­yl]-1H-imidazole} is reported and compared with the monoclinic form of solvent-free miconazole previously reported [Kaspiaruk & Chęcińska (2022). Acta Cryst. C78, 343–350]. A comparison shows a different orientation of imidazole and one di­chloro­phenyl ring between polymorphic mol­ecules. In the crystal structure of the title compound, only weak halogen bonds and C—H⋯π(arene) inter­actions are found. Hirshfeld surface analysis and energy framework calculations complement the comparison of the two polymorphic forms of the miconazole drug.

In the title salt, poly[aqua­[μ4-bis­(malonato)borato]sodium], {[Na(C6H4BO8)]·H2O}n or Na+·[B(C3H2O4)2]−·H2O, the sodium cation exhibits fivefold coordination by four carbonyl O atoms of the bis­(malonato)borate anions and a water O atom. The tetra­hedral B atom at the centre of the anion leads to the formation of a polymeric three-dimensional framework, which is consolidated by C—H⋯O and O—H⋯O hydrogen bonds. A Hirshfeld surface analysis indicates that the most significant contacts in the crystal packing are H⋯O/O⋯H (49.7%), Na⋯O/O⋯Na (16.1%), O⋯O (12.6%), H⋯H (10.7%) and C⋯O/O⋯C (7.3%).

The (S)-(+)-1-(4-bromo­phen­yl)-N-[(4-methoxyphen­yl)methyl­idene]ethyl­amine ligand, C16H16BrNO, (I), was synthesized through the reaction of 4-meth­oxy­anisaldehyde with (S)-(−)-1-(4-bromo­phen­yl)ethyl­amine. It crystallizes in the ortho­rhom­bic space group P212121 belonging to the Sohncke group, featuring a single mol­ecule in the asymmetric unit. The refinement converged successfully, achieving an R factor of 0.0508. The PdII com­plex bis­{(S)-(+)-1-(4-bromo­phen­yl)-N-[(4-methoxyphen­yl)methyl­idene]ethyl­amine-κN}di­chlorido­pal­ladium(II), [PdCl2(C16H16BrNO)2], (II), crystallizes in the monoclinic space group P21 belonging to the Sohncke group, with two mol­ecules in the asymmetric unit. The central atom is tetra­coordinated by two N atoms and two Cl atoms, resulting in a square-planar configuration. The imine moieties exhibit a trans configuration around the PdII centre, with average Cl—Pd—N angles of approximately 89.95 and 90°. The average distances within the palladium com­plex for the two mol­ecules are ∼2.031 Å for Pd—N and ∼2.309 Å for Pd—Cl.

The title compound, [CdBr2(C6H14N2O)], was synthesized upon complexation of 4-(2-aminoethyl)morpholine and cadmium(II) bromide tetra­hydrate at 303 K. It crystallizes as a centrosymmetric dimer, with one cadmium atom, two bromine atoms and one N,N'-bidentate 4-(2-aminoethyl)morpholine ligand in the asymmetric unit. The metal atom is six-coordinated and has a distorted octa­hedral geometry. In the crystal, O⋯Cd inter­actions link the dimers into a polymeric double chain and inter­molecular C—H⋯O hydrogen bonds form R22(6) ring motifs. Further C—H⋯Br and N—H⋯Br hydrogen bonds link the components into a three-dimensional network. As the N—H⋯Br hydrogen bonds are shorter than the C—H⋯Br inter­actions, they have a larger effect on the packing. A Hirshfeld surface analysis reveals that the largest contributions to the packing are from H⋯H (46.1%) and Br⋯H/H⋯Br (38.9%) inter­actions with smaller contributions from the O⋯H/H⋯O (4.7%), Br⋯Cd/Cd⋯Br (4.4%), O⋯Cd/Cd⋯O (3.5%), Br⋯Br (1.1%), Cd⋯H/H⋯Cd (0.9%), Br⋯O/O⋯Br (0.3%) and O⋯N/N⋯O (0.1%) contacts.

The title mol­ecule, [Fe2(C5H5)2(C23H17ClN2)]·C3H7NO, is twisted end to end and the central N/C/N unit is disordered. In the crystal, several C—H⋯π(ring) inter­actions lead to the formation of layers, which are connected by further C—H⋯π(ring) inter­actions. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (60.2%) and H⋯C/C⋯H (27.0%) inter­actions. Hydrogen bonding, C—H⋯π(ring) inter­actions and van der Waals inter­actions dominate the crystal packing.

The title compound, (C4H12N)[V(C12H8N4O2)O2]·H2O, was synthesized via aerial oxidation on refluxing picolinohydrazide with ethyl picolinate followed by addition of VIVO(acac)2 and di­ethyl­amine in methanol. It crystallizes in the triclinic crystal system in space group Poverline{1}. In the complex anion, the dioxidovanadium(V) moiety exhibits a distorted square-pyramidal geometry. In the crystal, extensive hydrogen bonding links the water mol­ecule to two complex anions and one di­ethyl­ammonium ion. One of the CH2 groups in the di­ethyl­amine is disordered over two sets of sites in a 0.7:0.3 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.

The title compound, C14H12N4O2·0.5HCl·H2O or H(C14H12N4O2)2+·Cl−·2H2O, arose from the unexpected cyclization of isonicotinoyl-N-phenyl hydrazine carbo­thio­amide catalysed by cobalt(II) acetate. The organic mol­ecule is almost planar and a symmetric N⋯H+⋯N hydrogen bond links two of them together, with the H atom lying on a crystallographic twofold axis. The extended structure features N—H⋯O and O—H⋯Cl hydrogen bonds, which generate [001] chains. Weak C—H⋯Cl inter­actions cross-link the chains. The chloride ion has site symmetry 2. The major contributions to the Hirshfeld surface are from H⋯H (47.1%), Cl⋯H/H⋯Cl (total 10.8%), O⋯H/H⋯O (7.4%) and N⋯H/H⋯N (6.7%) inter­actions.

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.

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.

In the structure of the title co-crystal, C3H3N3O2·C5H8N2, the components are linked by a set of directional O—H⋯N, N—H⋯O, N—H⋯N and C—H⋯O hydrogen bonds to yield a two-dimensional mono-periodic arrangement. The structure propagates in the third dimension by extensive π–π stacking inter­actions of nearly parallel mol­ecules of the two components, following an alternating sequence. The primary structure-defining inter­action is very strong oxime-OH donor to pyrazole-N acceptor hydrogen bond [O⋯N = 2.587 (2) Å], while the significance of weaker hydrogen bonds and π–π stacking inter­actions is comparable. The distinct structural roles of different kinds of inter­actions agree with the results of a Hirshfeld surface analysis and calculated inter­action energies. The title compound provides insights into co-crystals of active agrochemical mol­ecules and features the rational integration in one structure of a fungicide, C3H3N3O2, and a second active component, C5H8N2, known for alleviation the toxic effects of fungicides on plants. The material appears to be well suited for practical uses, being non-volatile, air-stable, water-soluble, but neither hygroscopic nor efflorescent.

Tri­chlorido­(4-methyl­piperidine)­gold(III), [AuCl3(C6H13N)], 1, crystallizes in Pbca with Z = 8. Tri­bromido­(4-methyl­piperidine)­gold(III), [AuBr3(C6H13N)], 2, crystallizes as two polymorphs, 2a in Pnma with Z = 4 (imposed mirror symmetry) and 2b, which is isotypic to 1. The Au—N bonds trans to Cl are somewhat shorter than those trans to Br, and the Au—Cl bonds trans to N are longer than those cis to N, whereas the Au—Br bonds trans to N are slightly shorter than the cis bonds. The methyl and AuX3 groups (X = halogen) occupy equatorial positions at the six-membered ring. The packing of all three structures involves chains of mol­ecules with offset stacking of the AuX3 moieties associated with short Au⋯X contacts; for 1 and 2b these are reinforced by N—H⋯X hydrogen bonds, whereas for 2a there are no classical hydrogen bonds and the chains are inter­connected by Br⋯Br contacts.

In the title compound, C20H17BrO5S, mol­ecules are connected by inter­molecular C—H⋯S hydrogen bonds with R22(10) ring motifs, forming ribbons along the b-axis direction. C—H⋯π inter­actions consolidate the ribbon structure while van der Waals forces between the ribbons ensure the cohesion of the crystal structure. According to a Hirshfeld surface analysis, H⋯H (40.5%), O⋯H/H⋯O (27.0%), C⋯H/H⋯C (13.9%) and Br⋯H/H⋯Br (11.7%) inter­actions are the most significant contributors to the crystal packing. The thio­phene ring and its adjacent di­carboxyl­ate group and the three adjacent carbon atoms of the central hexene ring to which they are attached were refined as disordered over two sets of sites having occupancies of 0.8378 (15) and 0.1622 (15). The thio­phene group is disordered by a rotation of 180° around one bond.

The title compound, [Mo3(C9H18NS2)3(S2)3S]2S, crystallizes on a general position in the monoclinic space group P21/n (No. 14). The cationic [Mo3S7(S2CNiBu2)3]+ fragments are joined by a mono­sulfide dianion that forms close S⋯S contacts to each of the di­sulfide ligands on the side of the Mo3 plane opposite the μ32− ligand. The two Mo3 planes are inclined at an angle of 40.637 (15)°, which gives the assembly an open clamshell-like appearance. One μ6-S2−⋯S22− contact, at 2.4849 (14) Å, is appreciably shorter than the remaining five, which are in the range 2.7252 (13)–2.8077 (14) Å.

The asymmetric unit of the title compound, C25H18N6·H2O, comproses two mol­ecules (I and II), together with a water mol­ecule. The terminal phenyl groups attached to the methyl groups of the mol­ecules I and II do not overlap completely, but are approximately perpendicular. In the crystal, the mol­ecules are connected by N—H⋯N, C—H⋯N, O—H⋯N and N—H⋯O hydrogen bonds with each other directly and through water mol­ecules, forming layers parallel to the (001) plane. C—H⋯π inter­actions between these layers ensure the cohesion of the crystal structure. A Hirshfeld surface analysis indicates that H⋯H (39.1% for mol­ecule I; 40.0% for mol­ecule II), C⋯H/H⋯C (26.6% for mol­ecule I and 25.8% for mol­ecule II) and N⋯H/H⋯N (24.3% for mol­ecules I and II) inter­actions are the most important contributors to the crystal packing.

The structure of the title compound, C23H21BrN4O, contains two independent mol­ecules connected by hydrogen bonds of the type Namide—H⋯N≡C to form a dimer. The configuration at the exocyclic C=C double bond is E. The mol­ecules are roughly planar except for the isopropyl groups. There are minor differences in the orientations of these groups and the phenyl rings at N1. The dimers are further linked by ‘weak’ hydrogen bonds, two each of the types Hphen­yl⋯O=C (H⋯O = 2.50, 2.51 Å) and Hphen­yl⋯Br (H⋯Br = 2.89, 2.91 Å), to form ribbons parallel to the b and c axes, respectively. The studied crystal was a non-merohedral twin.

The title compound, C12H15N3O2S, adopts an E configuration with respect to the C=N bond. The propionate group adopts an anti­periplanar (ap) conformation. There are short intra­molecular N—H⋯N and C—H⋯O contacts, forming S(5) and S(6) ring motifs, respectively. In the crystal, mol­ecules are connected into ribbons extending parallel to [010] by pairs of N—H⋯S inter­actions, forming rings with R22(8) graph-set motifs, and by pairs of C—H⋯S inter­actions, where rings with the graph-set motif R21(7) are observed. The O atom of the carbonyl group is disordered over two positions, with a refined occupancy ratio of 0.27 (2):0.73 (2). The studied crystal consisted of two domains.

The calixarenes, 5,17-di­bromo-26,28-dihy­droxy-25,27-dipropynyloxycalix[4]arene (C34H26Br2O4, 1), 5,17-di­bromo-26,28-dipropoxy-25,27-dipropynyloxycalix[4]arene (C40H38Br2O4, 2) and 25,27-bis­(2-azido­eth­oxy)-5,17-di­bromo-26,28-di­hydroxy­calix[4]arene (C32H28Br2N6O4, 3) possess a pinched cone mol­ecular shape for 1 and 3, and a 1,3-alternate shape for compound 2. In calixarenes 1 and 3, the cone conformations are additionally stabilized by intra­molecular O—H⋯O hydrogen bonds, while in calixarene 2 intra­molecular Br⋯Br inter­actions consolidate the 1,3-alternate mol­ecular conformation. The dense crystal packing of the cone dialkyne 1 is a consequence of π–π, C—H⋯π and C—H⋯O inter­actions. In the crystal of the diazide 3, there are large channels extending parallel to the c axis, which are filled by highly disordered CH2Cl2 solvent mol­ecules. Their contribution to the intensity data was removed by the SQUEEZE procedure that showed an accessible void volume of 585 Å3 where there is room for 4.5 CH2Cl2 solvent mol­ecules per unit cell. Rigid mol­ecules of the 1,3-alternate calixarene 2 form a columnar head-to-tail packing parallel to [010] via van der Waals inter­actions, and the resulting columns are held together by weak C—H⋯π contacts.

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.

In the title compound, C6H4BrF3N4O2, the oxa­diazole ring is essentially planar with a maximum deviation of 0.003 (2) Å. In the crystal, mol­ecular pairs are connected by N—H⋯N hydrogen bonds, forming dimers with an R22(8) motif. The dimers are linked into layers parallel to the (10overline{4}) plane by N—H⋯O hydrogen bonds. In addition, C—O⋯π and C—Br⋯π inter­actions connect the mol­ecules, forming a three-dimensional network. The F atoms of the tri­fluoro­methyl group are disordered over two sites in a 0.515 (6): 0.485 (6) ratio. The inter­molecular inter­actions in the crystal structure were investigated and qu­anti­fied using Hirshfeld surface analysis.

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.

The reaction of lithium hexa­methyl­disilyl­amide, [Li{N(Si(CH3)3)2}] (LiHMDS), with 4,4-dimethyl-2-phenyl-2-oxazoline (Phox, C11H13NO) in hexane produced colourless crystals of bis­(4,4-dimethyl-2-phenyl-2-oxazoline-κN)(hexa­methyl­disilyl­amido-κN)lithium, [Li(C6H18NSi2)(C11H13NO)2] or [Li{N(Si(CH3)3)2}(Phox)2] in high yield (89%). Despite the 1:1 proportion of the starting materials in the reaction mixture, the product formed with a 1:2 amide:oxazoline ratio. In the unit cell of the C2/c space group, the neutral mol­ecules lie on twofold rotation axes coinciding with the Li—N(amide) bonds. The lithium(I) centre adopts a trigonal–planar coordination geometry with three nitro­gen donor atoms, one from the HMDS anion and two from the oxazolines. All ligands are monodentate. In the phenyl­oxazoline units, the dihedral angle defined by the five-membered heterocyclic rings is 35.81 (5)°, while the phenyl substituents are approximately face-to-face, separated by 3.908 (5) Å. In the amide, the methyl groups assume a nearly eclipsed arrangement to minimize steric repulsion with the analogous substituents on the oxazoline rings. The non-covalent inter­actions in the solid-state structure of [Li{N(Si(CH3)3)2}(Phox)2] were assessed by Hirshfeld surface analysis and fingerprint plots. This new compound is attractive for catalysis due to its unique structural features.

Coarse colorless single crystals of lithium lutetium bis­[orthomolybdate(VI)], LiLu[MoO4]2, were obtained as a by-product from a reaction aimed at lithium derivatives of lutetium molybdate. The title compound crystallizes in the scheelite structure type (tetra­gonal, space group I41/a) with two formula units per unit cell. The Wyckoff position 4b (site symmetry overline{4}) comprises a mixed occupancy of Li+ and Lu3+ cations in a 1:1 ratio. In comparison with a previous powder X-ray study [Cheng et al. (2015). Dalton Trans. 44, 18078–18089.] all atoms were refined with anisotropic displacement parameters.

The chemical reaction of 4-bromo­benzoyl­chloride and 2-amino­thia­zole in the presence of potassium thio­cyanate yielded a white solid formulated as C15H10BrN3OS2, which consists of 4-bromo­benzamido and 2-benzo­thia­zolyl moieties connected by a thio­urea group. The 4-bromo­benzamido and 2-benzo­thia­zolyl moieties are in a trans conformtion (sometimes also called s-trans due to the single bond) with respect to the N—C bond. The dihedral angle between the mean planes of the 4-bromo­phenyl and the 2-benzo­thia­zolyl units is 10.45 (11)°. The thio­urea moiety, —C—NH—C(=S) —NH— fragment forms a dihedral angle of 8.64 (12)° with the 4-bromo­phenyl ring and is almost coplanar with the 2-benzo­thia­zolyl moiety, with a dihedral angle of 1.94 (11)°. The mol­ecular structure is stabilized by intra­molecular N—H⋯O hydrogen bonds, resulting in the formation of an S(6) ring. In the crystal, pairs of adjacent mol­ecules inter­act via inter­molecular hydrogen bonds of type C—H⋯N, C—H⋯S and N—H⋯S, resulting in mol­ecular layers parallel to the ac plane.

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.

Three new 1H-indole derivatives, namely, 2-(bromo­meth­yl)-3-methyl-1-(phenyl­sulfon­yl)-1H-indole, C16H14BrNO2S, (I), 2-[(E)-2-(2-bromo-5-meth­oxy­phen­yl)ethen­yl]-3-methyl-1-(phenyl­sulfon­yl)-1H-indole, C24H20BrNO3S, (II), and 2-[(E)-2-(2-bromo­phen­yl)ethen­yl]-3-methyl-1-(phenyl­sulfon­yl)-1H-indole, C23H18BrNO2S, (III), exhibit nearly orthogonal orientations of their indole ring systems and sulfonyl-bound phenyl rings. Such conformations are favourable for inter­molecular bonding involving sets of slipped π–π inter­actions between the indole systems and mutual C—H⋯π hydrogen bonds, with the generation of two-dimensional monoperiodic patterns. The latter are found in all three structures, in the form of supra­molecular columns with every pair of successive mol­ecules related by inversion. The crystal packing of the compounds is additionally stabilized by weaker slipped π–π inter­actions between the outer phenyl rings (in II and III) and by weak C—H⋯O, C—H⋯Br and C—H⋯π hydrogen bonds. The structural significance of the different kinds of inter­actions agree with the results of a Hirshfeld surface analysis and the calculated inter­action energies. In particular, the largest inter­action energies (up to −60.8 kJ mol−1) are associated with pairing of anti­parallel indole systems, while the energetics of weak hydrogen bonds and phenyl π–π inter­actions are comparable and account for 13–34 kJ mol−1.

The title compound, [Co(NCS)2(C6H7N)4] or Co(NCS)2(4-methyl­pyridine)4, was prepared by the reaction of Co(NCS)2 with 4-methyl­pyridine in water and is isotypic to one of the polymorphs of Ni(NCS)2(4-methyl­pyridine)4 [Kerr & Williams (1977). Acta Cryst. B33, 3589–3592 and Soldatov et al. (2004). Cryst. Growth Des. 4, 1185–1194]. Comparison of the experimental X-ray powder pattern with that calculated from the single-crystal data proves that a pure phase has been obtained. The asymmetric unit consists of one CoII cation, two crystallographically independent thio­cyanate anions and four independent 4-meth­yl­pyridine ligands, all located in general positions. The CoII cations are sixfold coordinated to two terminally N-bonded thio­cyanate anions and four 4-methyl­pyridine coligands within slightly distorted octa­hedra. Between the complexes, a number of weak C—H⋯N and C—H⋯S contacts are found. This structure represent a polymorphic modification of Co(NCS)2(4-methyl­pyridine)4 already reported in the CCD [Harris et al. (2003). NASA Technical Reports, 211890]. In contrast to this form, the crystal structure of the new polymorph shows a denser packing, indicating that it is thermodynamically stable at least at low temperatures. Thermogravimetric and differential thermoanalysis reveal that the title compound starts to decomposes at about 100°C and that the coligands are removed in separate steps without any sign of a polymorphic transition before decomposition.

This study presents the synthesis, characterization and Hirshfeld surface analysis of a small organic ammonium salt, C2H7BrN+·Br−. Small cations like the one in the title compound are considered promising components of hybrid perovskites, crucial for optoelectronic and photovoltaic applications. While the incorporation of this organic cation into various hybrid perovskite structures has been explored, its halide salt counterpart remains largely uninvestigated. The obtained structural results are valuable for the synthesis and phase analysis of hybrid perovskites. The title compound crystallizes in the solvent-free form in the centrosymmetric monoclinic space group P21/c, featuring one organic cation and one bromide anion in its asymmetric unit, with a torsion angle of −64.8 (2)° between the ammonium group and the bromine substituent, positioned in a gauche conformation. The crystal packing is predominantly governed by Br⋯H inter­actions, which constitute 62.6% of the overall close atom contacts.

The crystal structure of 1,2,3,4-tetra­hydro­isoquinolin-2-ium (2S,3S)-3-carb­oxy-2,3-di­hydroxy­propano­ate monohydrate, C9H12N+·C4H5O6−·H2O, at 115 K shows ortho­rhom­bic symmetry (space group P212121). The hydrogen tartrate anions and solvent water mol­ecules form an intricate diperiodic O—H⋯O hydrogen-bond network parallel to (001). The tetra­hydro­isoquinolinium cations are tethered to the anionic hydrogen-bonded layers through N—H⋯O hydrogen bonds. The crystal packing in the third direction is achieved through van der Waals contacts between the hydro­carbon tails of the tetra­hydro­isoquinolinium cations, resulting in hydro­phobic and hydro­philic regions in the crystal structure.

In the title compound, C19H18BrFN2O, the pyrrolidine ring adopts an envelope conformation. In the crystal, mol­ecules are linked by inter­molecular N—H⋯O, C—H⋯O, C—H⋯F and C—H⋯Br hydrogen bonds, forming a three-dimensional network. In addition, C—H⋯π inter­actions connect mol­ecules into ribbons along the b-axis direction, consolidating the mol­ecular packing. The inter­molecular inter­actions in the crystal structure were qu­anti­fied and analysed using Hirshfeld surface analysis.

A new mononuclear complex, penta­aqua­(cucurbit[6]uril-κ2O,O')(nitrato-κ2O,O')praseodymium(III) dinitrate 9.56-hydrate, [Pr(NO3)(CB6)(H2O)5](NO3)2·9.56H2O (1), was obtained as outcome of the hydro­thermal reaction between the macrocyclic ligand cucurbit[6]uril (CB6, C36H36N24O12) with a tenfold excess of Pr(NO3)3·6H2O. Complex 1 crystallizes in the P21/n space group with two crystallographically independent but chemically identical [Pr(CB6)(NO3)(H2O)5]2+ complex cations, four nitrate counter-anions and 19.12 inter­stitial water mol­ecules per asymmetric unit. The nona­coordinated PrIII in 1 are located in the PrO9 coordination environment formed by two carbonyl O atoms from bidentate cucurbit[6]uril units, two oxygen atoms from the bidentate nitrate anion and five water mol­ecules. Considering the differences in Pr—O bond distances and O—Pr—O angles in the coordination spheres, the coordination polyhedrons of the two PrIII atoms can be described as distorted spherical capped square anti­prismatic and muffin polyhedral.

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.

A new polymorph of the diuretic chloro­thia­zide, 6-chloro-1,1-dioxo-2H-1,2,4-benzo­thia­zine-7-sulfonamide, C7H6ClN3O4S2, is described. Crystallized from basic aqueous solution, this monoclinic polymorph is found to be less thermodynamically favoured than the known triclinic polymorph and to feature only N—H⋯O type inter­molecular hydrogen bonds as opposed to the N—H⋯O and N—H⋯N type hydrogen bonds found in the P1 form.

In the title mol­ecule, C11H11BrO3, the di­hydro­indene moiety is essentially planar but with a slight twist in the saturated portion of the five-membered ring. The meth­oxy groups lie close to the above plane. In the crystal, π-stacking inter­actions between six-membered rings form stacks of mol­ecules extending along the a-axis direction, which are linked by weak C—H⋯O and C—H⋯Br hydrogen bonds. A Hirshfeld surface analysis was performed showing H⋯H, O⋯H/H⋯O and Br⋯H/H⋯Br contacts make the largest contributions to inter­molecular inter­actions in the crystal.

The aryl diester compound, 2-methyl-1,4-phenyl­ene bis­(3,5-di­bromo­benzoate), C21H12Br4O4, was synthesized by esterification of methyl hydro­quinone with 3,5-di­bromo­benzoic acid. A crystalline sample was obtained by cooling a sample of the melt (m.p. = 502 K/DSC) to room temperature. The mol­ecular structure consists of a central benzene ring with anti-3,5-di­bromo­benzoate groups symmetrically attached at the 1 and 4 positions and a methyl group attached at the 2 position of the central ring. In the crystal structure (space group Poverline{1}), mol­ecules of the title aryl diester are located on inversion centers imposing disorder of the methyl group and H atom across the central benzene ring. The crystal structure is consolidated by a network of C—H⋯Br hydrogen bonds in addition to weaker and offset π–π inter­actions involving the central benzene rings as well as the rings of the attached 3,5-di­bromo­benzoate groups.

The crystal structures of two inter­mediates, 4-amino-3,5-di­fluoro­benzo­nitrile, C7H4F2N2 (I), and ethyl 4-amino-3,5-di­fluoro­benzoate, C9H9F2NO2 (II), along with a visible-light-responsive azo­benzene derivative, diethyl 4,4'-(diazene-1,2-di­yl)bis­(3,5-di­fluoro­benzoate), C18H14F4N2O4 (III), obtained by four-step synthetic procedure, were studied using single-crystal X-ray diffraction. The mol­ecules of I and II demonstrate the quinoid character of phenyl rings accompanied by the distortion of bond angles related to the presence of fluorine substituents in the 3 and 5 (ortho) positions. In the crystals of I and II, the mol­ecules are connected by N—H⋯N, N—H⋯F and N—H⋯O hydrogen bonds, C—H⋯F short contacts, and π-stacking inter­actions. In crystal of III, only stacking inter­actions between the mol­ecules are found.

The title compound, bis­[di­thio­bis­(formamidinium)] hexa­bromido­ruthenium dibromide trihydrate, [(NH2)2CSSC(NH2)2]2[RuBr6]Br2·3H2O, crystallizes in the ortho­rhom­bic system, space group Cmcm, Z = 4. The [RuBr6]2− anionic complex has an octa­hedral structure. The Ru—Br distances fall in the range 2.4779 (4)–2.4890 (4) Å. The S—S and C—S distances are 2.0282 (12) and 1.783 (2) Å, respectively. The H2O mol­ecules, Br− ions, and NH2 groups of the cation are linked by hydrogen bonds. The conformation of the cation is consolidated by intra­molecular O—H⋯Br, O—H⋯O, N—H⋯Br and N—H⋯O hydrogen bonds. The [(NH2)2CSSC(NH2)2]2+ cations form a hydrogen-bonded system involving the Br − ions and the water mol­ecules. Two Br − anions form four hydrogen bonds, each with the NH2 groups of two cations, thus linking the cations into a ring. The rings are connected by water mol­ecules, forming N—H⋯O—H⋯Br hydrogen bonds.

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.

The title compound, C17H13BrN4O5, was synthesized by a Cu2Br2-catalysed Meldal–Sharpless reaction between 4-nitro­phen­oxy­acetic acid propargyl ether and para-bromo­phenyl­azide, and characterized by X-ray structure determination and 1H NMR spectroscopy. The mol­ecules, with a near-perpendicular orientation of the bromo­phenyl-triazole and nitro­phen­oxy­acetate fragments, are connected into a three-dimensional network by inter­molecular C—H⋯O and C—H⋯N hydrogen bonds (confirmed by Hirshfeld surface analysis), π–π and Br–π inter­actions.

This study presents the synthesis, characterization and Hirshfeld surface analysis of the title mononuclear complex, [PdCl2(C12H14N4)]·C3H7NO. The compound crystalizes in the P21/c space group of the monoclinic system. The asymmetric unit contains one neutral complex Pd(HLc-Pe)Cl2 [HLc-Pe is 2-(3-cyclo­pentyl-1,2,4-triazol-5-yl)pyridine] and one mol­ecule of DMF as a solvate. The Pd atom has a square-planar coordination. In the crystal, mol­ecules are linked by inter­molecular N—H⋯O and C—H⋯N hydrogen bonds, forming layers parallel to the bc plane. A Hirshfeld surface analysis showed that the H⋯H contacts dominate the crystal packing with a contribution of 41.4%. The contribution of the N⋯H/H⋯N and H⋯O/O⋯H inter­actions is somewhat smaller, amounting to 12.4% and 5%, respectively.

This study presents the synthesis, characterization and Hirshfeld surface analysis of 1-[6-bromo-2-(3-bromo­phen­yl)-1,2,3,4-tetra­hydro­quinolin-4-yl]pyrrolidin-2-one, C19H18Br2N2O. In the title compound, the pyrrolidine ring adopts a distorted envelope configuration. In the crystal, mol­ecules are linked by inter­molecular N—H⋯O, C—H⋯O and C—H⋯Br hydrogen bonds, forming a three-dimensional network. In addition, pairs of mol­ecules along the c axis are connected by C—H⋯π inter­actions. According to a Hirshfeld surface study, H⋯H (36.9%), Br⋯H/H⋯Br (28.2%) and C⋯H/H⋯C (24.3%) inter­actions are the most significant contributors to the crystal packing.

In the title compound, C33H29ClN2O2, the two piperidine rings of the di­aza­bicyclo moiety adopt distorted-chair conformations. Inter­molecular C—H⋯π inter­actions are mainly responsible for the crystal packing. The inter­molecular inter­actions were qu­anti­fied and analysed using Hirshfeld surface analysis, revealing that H⋯H inter­actions contribute most to the crystal packing (52.3%). The mol­ecular structure was further optimized by density functional theory (DFT) at the B3LYP/6–31 G(d,p) level and is compared with the experimentally determined mol­ecular structure in the solid state.

In the structure of the title salt, {[Ba(μ3-C3H2N3O2)2(μ-H2O)(H2O)]·H2O}n, the barium ion and all three oxygen atoms of the water mol­ecules reside on a mirror plane. The hydrogen atoms of the bridging water and the solvate water mol­ecules are arranged across a mirror plane whereas all atoms of the monodentate aqua ligand are situated on this mirror plane. The distorted ninefold coord­ination of the Ba ions is completed with four nitroso-, two carbonyl- and three aqua-O atoms at the distances of 2.763 (3)–2.961 (4) Å and it is best described as tricapped trigonal prism. The three-dimensional framework structure is formed by face-sharing of the trigonal prisms, via μ-nitroso- and μ-aqua-O atoms, and also by the bridging coordination of the anions via carbonyl-O atoms occupying two out of the three cap positions. The solvate water mol­ecules populate the crystal channels and facilitate a set of four directional hydrogen bonds. The principal Ba–carbamoyl­cyano­nitro­somethanido linkage reveals a rare example of the inherently polar binodal six- and three-coordinated bipartite topology (three-letter notation sit). It suggests that small resonance-stabilized cyano­nitroso anions can be utilized as bridging ligands for the supra­molecular synthesis of MOF solids. Such an outcome may be anti­cipated for a broader range of hard Lewis acidic alkaline earth metal ions, which perfectly match the coordination preferences of highly nucleophilic nitroso-O atoms. Thermal analysis reveals two-stage dehydration of the title compound (383 and 473 K) followed by decomposition with release of CO2, HCN and H2O at 558 K.

The mol­ecular structure of the tripodal carbamoyl­methyl­phosphine oxide compound diethyl {[(5-[2-(di­eth­oxy­phosphor­yl)acetamido]-3-{2-[2-(di­eth­oxy­phos­phor­yl)acetamido]­eth­yl}pent­yl)carbamo­yl]meth­yl}phospho­nate, C25H52N3O12P3, features six intra­molecular hydrogen-bonding inter­actions. The phospho­nate groups have key bond lengths ranging from 1.4696 (12) to 1.4729 (12) Å (P=O), 1.5681 (11) to 1.5811 (12) Å (P—O) and 1.7881 (16) to 1.7936 (16) Å (P—C). Each amide group adopts a nearly perfect trans geometry, and the geometry around each phophorus atom resembles a slightly distorted tetra­hedron.

The two mol­ecules in the asymmetric unit of the title compound, C23H24N2O2S, have a structural overlap with an r.m.s. deviation of 0.82 Å. The piperidine rings adopt a distorted boat conformation. Intra- and inter­molecular C—H⋯O hydrogen bonds are responsible for the cohesion of the crystal packing. The inter­molecular inter­actions were qu­anti­fied and analysed using Hirshfeld surface analysis. 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.