The title compound, [Na(μ-C6F5BH3)(C4H8O)2]2, represents a dimeric structure of sodium and organoborohydride, located about a centre of inversion. The Na⋯B distances of 2.7845 (19) and 2.7494 (18) Å were apparently longer than the Li⋯B distances (2.403–2.537 Å) of the lithium organotri­hydro­borates in the previous reports. Moreover, an inter­action between the sodium atom and one fluorine atom on the 2-position of the benzene ring is observed [Na—F = 2.6373 (12) Å]. In the crystal, the dimeric mol­ecules are stacked along the b-axis via a π–π inter­action between the benzene rings.

In the crystal structure of the title compound, C14H12ClNO, the mol­ecules are linked through C—H⋯O hydrogen bonds and C—H⋯π inter­actions, forming chains parallel to the [010] direction. π–π inter­actions and intra­molecular hydrogen bonds are also observed. The mol­ecular geometry of the title compound in the ground state has been calculated using density functional theory at the B3LYP level with the 6–311++G(2d,2p) basis set. Additionally, frontier mol­ecular orbital and mol­ecular electrostatic potential map analyses were performed.

Recrystallization of (E)-5-phenyl-1-(pyridin-2-yl)pent-2-en-4-yn-1-one at room temperature from ethyl­ene glycol in daylight afforded [3,4-bis­(phenyl­ethyn­yl)cyclo­butane-1,2-di­yl)bis­(pyridin-2-yl­methanone], C32H22N2O2 (3), while (E)-5-(4-methyl­phen­yl)-1-(pyridin-2-yl)pent-2-en-4-yn-1-one, C17H13NO (2), remained photoinert. This is the first experimental evidence that pentenynones can be photoreactive when fixed in nearly coplanar parallel positions. During the photoreaction, the bond lengths and angles along the pentenyne chain changed significantly, while the disposition of the pyridyl ring towards the keto group was almost unchanged. The cyclo­butane ring adopts an rctt conformation.

In the title compound, C18H19BrFN3S, the 1,2,4-triazole ring is nearly planar with a maximum deviation of −0.009 (3) and 0.009 (4) Å, respectively, for the S-bound C atom and the N atom bonded to the bromo­fluoro­phenyl ring. The phenyl and triazole rings are almost perpendicular to each other, forming a dihedral angle of 89.5 (2)°. In the crystal, the mol­ecules are linked by weak C—H⋯π(phen­yl) inter­actions, forming supra­molecular chains extending along the c-axis direction. The crystal packing is further consolidated by inter­molecular N—H⋯S hydrogen bonds and by weak C—H⋯S inter­actions, yielding double chains propagating along the a-axis direction. The crystal studied was refined as a racemic twin.

Crystals of the new compound, AgSr4Cu4.5(PO4)6, were grown successfully by the hydro­thermal process. The asymmetric unit of the crystal structure of the title compound contains 40 independent atoms (4 Sr, 4.5 Cu, 1 Ag, 6 P and 24 O), which are all in general positions except for one Cu atom, which is located on an inversion centre. The Cu atoms are arranged in CuOn (n = 4 or 5) polyhedra, linked through common oxygen corners to build a rigid three-dimensional motif. The connection of these copper units is assured by PO4 tetra­hedra. This arrangement allows the construction of layers extending parallel to the (100) plane and hosts suitable cavities in which Ag+ and Sr2+ cations are located. The crystal-structure cohesion is ensured by ionic bonds between the silver and strontium cations and the oxygen anions belonging to two adjacent sheets. Charge-distribution analysis and bond-valence-sum calculations were used to validate the structural model.

The crystal and mol­ecular structures of the title organotin di­thio­carbamate compounds, [Sn(C6H5)3(C7H10NS2)] (I) and [Sn(C6H5)2(C7H10NS2)2] (II), present very distinct tin atom coordination geometries. In (I), the di­thio­carbamate ligand is asymmetrically coordinating with the resulting C3S2 donor set defining a coordination geometry inter­mediate between square-pyramidal and trigonal–bipyramidal. In (II), two independent mol­ecules comprise the asymmetric unit, which differ in the conformations of the allyl substituents and in the relative orientations of the tin-bound phenyl rings. The di­thio­carbamate ligands in (II) coordinate in an asymmetric mode but the Sn—S bonds are more symmetric than observed in (I). The resulting C2S4 donor set approximates an octa­hedral coordination geometry with a cis-disposition of the ipso-carbon atoms and with the more tightly bound sulfur atoms approximately trans. The only directional inter­molecular contacts in the crystals of (I) and (II) are of the type phenyl-C—H⋯π(phen­yl) and vinyl­idene-C—H⋯π(phen­yl), respectively, with each leading to a supra­molecular chain propagating along the a-axis direction. The calculated Hirshfeld surfaces emphasize the importance of H⋯H contacts in the crystal of (I), i.e. contributing 62.2% to the overall surface. The only other two significant contacts also involve hydrogen, i.e. C⋯H/H⋯C (28.4%) and S⋯H/H⋯S (8.6%). Similar observations pertain to the individual mol­ecules of (II), which are clearly distinguishable in their surface contacts, with H⋯H being clearly dominant (59.9 and 64.9%, respectively) along with C⋯H/H⋯C (24.3 and 20.1%) and S⋯H/H⋯S (14.4 and 13.6%) contacts. The calculations of energies of inter­action suggest dispersive forces make a significant contribution to the stabilization of the crystals. The exception is for the C—H⋯π contacts in (II) where, in addition to the dispersive contribution, significant contributions are made by the electrostatic forces.

Deuterated potassium orthophosphate hepta­hydrate, K3PO4·7D2O, crystallizes in the Sohnke space group P21, and its absolute structure was determined from 2017 Friedel pairs [Flack parameter 0.004 (16)]. Each of the three crystallographically unique K+ cations is surrounded by six water mol­ecules and one oxygen atom from the orthophosphate group, using a threshold for K—O bonds of 3.10 Å. The highly irregular coordination polyhedra are linked by corner- and edge-sharing into a three-dimensional network that is consolidated by an intricate network of O—D⋯O hydrogen bonds of medium strength.

The structure of the title quinoline carboxamide derivative, C26H25N3O, is described. The quinoline moiety is not planar as a result of a slight puckering of the pyridine ring. The secondary amine has a slightly pyramidal geometry, certainly not planar. Both intra- and inter­molecular hydrogen bonds are present. Hirshfeld surface analysis and lattice energies were used to investigate the inter­molecular inter­actions.

The crystal structures of the title compounds, two solvates (CHCl3 and THF) of a symmetric and highly substituted porphyrin, C44H2Br8F20N4 or OBrTPFPP, are described. These structures each feature a non-planar porphyrin ring, exhibiting a similar conformation of the strained ring independent of solvent identity. These distorted porphyrins are able to form hydrogen bonds and sub-van der Waals halogen inter­actions with enclathrated solvent; supra­molecular inter­actions of proximal macrocycles are additionally affected by solvent choice. The crystal studied for compound 1·CHCl3 was refined as an inversion twin. One penta­fluoro­phenyl group was modelled as disordered over two sites [occupancy ratio = 0.462 (7):0.538 (7)]. The chloro­form solvate was also modelled as disordered over two orientations [occupancy ratio = 0.882 (7): 0.118 (7).

A peptide biphenyl hybrid compound {systematic name: dimethyl 2,2'-[((2S,2'S)-2,2'-{[(2S,2'S)-1,1'-([1,1'-biphen­yl]-2,2'-dicarbon­yl)bis­(pyrrolidine-1,2-diyl-2-carbon­yl)]bis­(aza­nedi­yl)}bis­(3-phenyl­propano­yl))bis­(aza­nedi­yl)](2S,2'S)-dipropionate hemihydrate}, C50H56N6O10·0.5H2O, was prepared by coupling of [1,1'-biphen­yl]-2,2'-dicarbonyl dichloride, tri­ethyl­amine and the tripeptide Pro–Phe–Ala in CH2Cl2 at 273 K under an N2 atmosphere. In the crystal, the asymmetric unit contains the peptide biphenyl hybrid accompanied by one-half of a water mol­ecule. A C atom of one of the proline rings is disordered between two positions in a 0.746 (11):0.254 (11) ratio. An important structural aspect of peptide compounds is their capacity to self-associate mediated by inter­molecular and intra­molecular hydrogen bonding. This characteristic can be useful in understanding the inter­actions between peptides and biomacromolecular targets, as well as to explain peptide properties.

A new pseudopolymorph of dodeca­chloro­penta­silane, namely a benzene monosolvate, Si5Cl12·C6H6, is described. There are two half mol­ecules of each kind in the asymmetric unit. Both Si5Cl12 mol­ecules are completed by crystallographic twofold symmetry. One of the benzene mol­ecules is located on a twofold rotation axis with two C—H groups located on this rotation axis. The second benzene mol­ecule has all atoms on a general position: it is disordered over two equally occupied orientations. No directional inter­actions beyond normal van der Waals contacts occur in the crystal.

In the title compound, [Zn(C50H36N6O5)], the ZnII cation is chelated by four pyrrole N atoms of the porphyrinate anion and coordinated by a symmetry-generated keto O atom of the diazo­ester group in a distorted square-pyramidal geometry. The mean Zn—N(pyrrole) bond length is 2.058 Å and the Zn—O(diazo­ester) bond length is 2.179 (4) Å. The zinc cation is displaced by 0.2202 (13) Å from the N4C20 mean plane of the porphyrinate anion toward the O atom; the involvement of this atom leads to a [100] polymeric chain in the crystal.

The asymmetric unit of the title compound, C23H28O4, comprises two half-mol­ecules, with the other half of each mol­ecule being completed by the application of twofold rotation symmetry. The two completed mol­ecules both have a V-shaped appearance but differ in their conformations. In the crystal, each independent mol­ecule forms chains extending parallel to the b axis with its symmetry-related counterparts through C—H⋯π(ring) inter­actions. Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (65.4%), H⋯C/C⋯H (21.8%) and H⋯O/O⋯H (12.3%) inter­actions. Optimized structures using density functional theory (DFT) at the B3LYP/6–311 G(d,p) level are compared with the experimentally determined mol­ecular structures in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.

The crystal structures of tris­[9,9-dihexyl-2-(5-meth­oxy­pyridin-2-yl-κN)-9H-fluoren-3-yl-κC3]iridium pentane monosolvate, [Ir(C31H38NO)3]·C5H12, (I), di-μ2-chlorido-bis­{bis­[2-(5-fluoro­pyridin-2-yl)-9,9-dihexyl-9H-fluoren-3-yl]iridium} pentane 0.3-solvate, [Ir2(C30H35FN)4Cl2]·0.3C5H12, (II), di-μ2-cyanato-bis­{bis­[9,9-dihexyl-2-(5-meth­oxy­pyridin-2-yl)-9H-fluoren-1-yl]iridium} pentane monosolvate, [Ir2(C31H38NO)4(NCO)2(NCO)2]·C5H12, (III), and {μ-N,N'-bis­[3,5-bis­(tri­fluoro­meth­yl)phen­yl]oxamidato}bis(bis{2-[4-(2,4,6-trimethylphenyl)pyridin-2-yl]phenyl-κ2C1,N'}iridium)–chloro­benzene–pentane (1/2.3/0.4), [Ir2(C20H19N)4(C18H6F12N2O2)]·2.3C6H5Cl·0.4C5H12, (IV), synthesized in the quest for organic light-emitting devices, were determined. The bis-μ2-chloro and bis-μ2-cyanato complexes have ΔΔ and ΛΛ configurations of the distorted octa­hedral Ir centres in racemic crystals, whereas the oxamido complex has a centrosymmetric (meso) structure with the ΔΛ configuration. The bridging oxamido moiety has a nearly planar anti geometry. All structures show substantial disorder of both host mol­ecules and solvents of crystallization.

The title compound, C13H16ClNO, contains a methyl­piperidine ring in the stable chair conformation. The mean plane of the twisted piperidine ring subtends a dihedral angle of 39.89 (7)° with that of the benzene ring. In the crystal, weak C—H⋯O inter­actions link the mol­ecules along the a-axis direction to form infinite mol­ecular chains. H⋯H inter­atomic inter­actions, C—H⋯O inter­molecular inter­actions and weak dispersive forces stabilize mol­ecular packing and form a supra­molecular network, as established by Hirshfeld surface analysis.

In the title compound, [Cu(C16H8Br3N2O)2]·C2H6OS, the CuII atom is tetra­coordinated in a square-planar coordination, being surrounded by two N atoms and two O atoms from two N,O-bidentate (E)-1-[(2,4,6-tri­bromo­phen­yl)diazen­yl]naphthalen-2-olate ligands. The two N atoms and two O atoms around the metal center are trans to each other, with an O—Cu—O bond angle of 177.90 (16)° and a N—Cu—N bond angle of 177.8 (2)°. The average distances between the CuII atom and the coordinated O and N atoms are 1.892 (4) and 1.976 (4) Å, respectively. In the crystal, complexes are linked by C—H⋯O hydrogen bonds and by π–π inter­actions involving adjacent naphthalene ring systems [centroid–centroid distance = 3.679 (4) Å]. The disordered DMSO mol­ecules inter­act weakly with the complex mol­ecules, being positioned in the voids left by the packing arrangement of the square-planar complexes. The DMSO solvent mol­ecule is disordered over two positions with occupancies of 0.70 and 0.30.

The central thia­zolidine ring of the title salt, C16H16N3S+·Br−, adopts an envelope conformation, with the C atom bearing the phenyl ring as the flap atom. In the crystal, the cations and anions are linked by N—H⋯Br hydrogen bonds, forming chains parallel to the b-axis direction. Hirshfeld surface analysis and two-dimensional fingerprint plots indicate that the most important contributions to the crystal packing are from H⋯H (46.4%), C⋯H/H⋯C (18.6%) and H⋯Br/Br⋯H (17.5%) inter­actions.

The title compound, C17H18ClNO2, was prepared and isolated as a pure diastereoisomer, using column chromatography followed by a succession of fractional crystallizations. Its exact structure was fully identified via 1H NMR and confirmed by X-ray diffraction. It is built up from a central five-membered di­hydro­isoxazole ring to which a p-chloro­phenyl group and a cyclo­hex-2-enone ring are attached in the 3 and 5 positions. The cyclo­hex-2-one and isoxazoline rings each exhibit an envelope conformation. The crystal packing features C—H⋯O, C—H⋯N and C—H⋯π inter­actions, which generate a three-dimensional network.

In the title compound, C22H27NO, the piperidine ring adopts a chair conformation. The dihedral angles between the mean plane of the piperidine ring and the phenyl rings are 89.78 (7) and 48.30 (8)°. In the crystal, mol­ecules are linked into chains along the b-axis direction by C—H⋯O hydrogen bonds. The DFT/B3LYP/6–311 G(d,p) method was used to determine the HOMO–LUMO energy levels. The mol­ecular electrostatic potential surfaces were investigated by Hirshfeld surface analysis and two-dimensional fingerprint plots were used to analyse the inter­molecular inter­actions in the mol­ecule.

The title compound, C22H22O2S2, 1, represents an example of an ortho-vanillin-based functionalized di­thio­ether, which could be useful as a potential chelating ligand or bridging ligand for coordination chemistry. This di­thio­acetal 1 crystallizes in the ortho­rhom­bic space group Pbca. The phenyl rings of the benzyl groups and that of the vanillin unit form dihedral angles of 35.38 (6) and 79.77 (6)°, respectively. The crystal structure, recorded at 100 K, displays both weak intra­molecular O—H⋯O and inter­molecular O—H⋯S hydrogen bonding.

Two new co-crystals, tetra­iodo­ethyl­ene–phenanthridine (1/2), 0.5C2I4·C13H9N (1) and tetra­iodo­ethyl­ene–benzo[f]quinoline (1/2), 0.5C2I4·C13H9N (2), were obtained from tetra­iodo­ethyl­ene and aza­phenanthrenes, and characterized by IR and fluorescence spectroscopy, elemental analysis and X-ray crystallography. In the crystal structures, C—I⋯π and C—I⋯N halogen bonds link the independent mol­ecules into one-dimensional chains and two-dimensional networks with subloops. In addition, the planar aza­phenanthrenes lend themselves to π–π stacking and C—H⋯π inter­actions, leading to a diversity of supra­molecular three-dimensional structural motifs being formed by these inter­actions. Luminescence studies show that co-crystals 1 and 2 exhibit distinctly different luminescence properties in the solid state at room temperature.

Two polymorphs of the title compound, C19H16N2O3, were obtained from ethano­lic (polymorph I) and methano­lic solutions (polymorph II), respectively. Both polymorphs crystallize in the monoclinic system with four formula units per cell and a complete mol­ecule in the asymmetric unit. The main difference between the mol­ecules of (I) and (II) is the reversed position of the hy­droxy group of the carb­oxy­lic function. All other conformational features are found to be similar in the two mol­ecules. The different orientation of the OH group results in different hydrogen-bonding schemes in the crystal structures of (I) and (II). Whereas in (I) inter­molecular O—H⋯O hydrogen bonds with the pyridazinone carbonyl O atom as acceptor generate chains with a C(7) motif extending parallel to the b-axis direction, in the crystal of (II) pairs of inversion-related O—H⋯O hydrogen bonds with an R22(8) ring motif between two carb­oxy­lic functions are found. The inter­molecular inter­actions in both crystal structures were analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots.

In the title compound, C18H18ClN3O2S, the dihedral angle between the fused pyrazole and pyridine rings is 3.81 (9)°. The benzene ring forms dihedral angles of 35.08 (10) and 36.26 (9)° with the pyrazole and pyridine rings, respectively. In the crystal, weak C—H⋯O hydrogen bonds connect mol­ecules along [100].

The title crystal structure is assembled from the superposition of two mol­ecular structures, (E)-1-(5-chloro­thio­phen-2-yl)-3-(3-methyl­thio­phen-2-yl)prop-2-en-1-one, C12H9ClOS2 (93%), and (Z)-1-(5-chloro­thio­phen-2-yl)-3-(3-methyl­thio­phen-2-yl)prop-1-en-1-ol, C12H11ClOS2 (7%), 0.93C12H9ClOS2·0.07C12H11ClOS2. Both were obtained from the reaction of 3-methyl­thio­phene-2-carbaldehyde and 1-(5-chloro­thio­phen-2-yl)ethanone. In the extended structure of the major chalcone component, mol­ecules are linked by a combination of C—H⋯O/S, Cl⋯Cl, Cl⋯π and π–π inter­actions, leading to a compact three-dimensional supra­molecular assembly.

The asymmetric unit of the title compound, C10H11NO4, which was synthesized via nitration reaction of eugenol (4-allyl-2-meth­oxy­phenol) with a mixture of nitric acid and sulfuric acid, consists of three independent mol­ecules of similar geometry. Each mol­ecule displays an intra­molecular hydrogen bond involving the hydroxide and the nitro group forming an S(6) motif. The crystal cohesion is ensured by inter­molecular C—H⋯O hydrogen bonds in addition to π–π stacking inter­actions between the aromatic rings [centroid–centroid distances = 3.6583 (17)–4.0624 (16) Å]. The Hirshfeld surface analysis and the two-dimensional fingerprint plots show that H⋯H (39.6%), O⋯H/H⋯O (37.7%), C⋯H/H⋯C (12.5%) and C⋯C (4%) are the most important contributors towards the crystal packing.

Crystal structures are reported for N-(4-meth­oxy­phen­yl)piperazine (MeOPP), (I), and for its 3,5-di­nitro­benzoate, 2,4,6-tri­nitro­phenolate (picrate) and 4-amino­benzoate salts, (II)–(IV), the last of which crystallizes as a monohydrate. In MeOPP, C11H16N2O, (I), the 4-meth­oxy­phenyl group is nearly planar and it occupies an equatorial site on the piperazine ring: the mol­ecules are linked into simple C(10) chains by N—H⋯O hydrogen bonds. In each of the salts, i.e., C11H17N2O+·C7H3N2O6−, (II), C11H17N2O+·C6H2N3O7−, (III), and C11H17N2O+·C7H6NO2−·H2O, (IV), the effectively planar 4-meth­oxy­phenyl substituent again occupies an equatorial site on the piperazine ring. In (II), two of the nitro groups are disordered over two sets of atomic sites and the bond distances in the anion indicate considerable delocalization of the negative charge over the C atoms of the ring. The ions in (II) are linked by two N—H⋯O hydrogen bonds to form a cyclic, centrosymmetric four-ion aggregate; those in (III) are linked by a combination of N—H⋯O and C—H⋯π(arene) hydrogen bonds to form sheets; and the components of (IV) are linked by N—H⋯O, O—H⋯O and C—H⋯π(arene) hydrogen bonds to form a three-dimensional framework structure. Comparisons are made with the structures of some related compounds.

In the title hydrated complex, [Co(C15H10ClN3)2]Cl2·4H2O, the complete dication is generated by overline{4} symmetry. The CoN6 moiety shows distortion from regular octa­hedral geometry with the trans bond angles of two N—Co—N units being 160.62 (9)°. In the crystal, O—H⋯Cl and C—H⋯O inter­actions link the components into (001) sheets. The title compound exhibits blue-light emission, as indicated by photoluminescence data, and a HOMO–LUMO energy separation of 2.23 eV was obtained from its diffuse reflectance spectrum.

In the title compound, C9H10ClNOS, the amide functional group –C(=O)NH– adopts a trans conformation with the four atoms nearly coplanar. This conformation promotes the formation of a C(4) hydrogen-bonded chain propagating along the [010] direction. The central part of the mol­ecule, including the six-membered ring, the S and N atoms, is fairly planar (r.m.s. deviation of 0.014). The terminal methyl group and the C(=O)CH2 group are slightly deviating out-of-plane while the terminal Cl atom is almost in-plane. Hirshfeld surface analysis of the title compound suggests that the most significant contacts in the crystal are H⋯H, H⋯Cl/Cl⋯H, H⋯C/C⋯H, H⋯O/O⋯H and H⋯S/S⋯H. π–π inter­actions between inversion-related mol­ecules also contribute to the crystal packing. DFT calculations have been performed to optimize the structure of the title compound using the CAM-B3LYP functional and the 6–311 G(d,p) basis set. The theoretical absorption spectrum of the title compound was calculated using the TD–DFT method. The analysis of frontier orbitals revealed that the π–π* electronic transition was the major contributor to the absorption peak in the electronic spectrum.

The title compound, C11H9N3OS, (I), crystallizes in the monoclinic space group P21/n. The mol­ecular conformation is nearly planar and features an intra­molecular chalcogen bond between the thio­phene S and the imine N atoms. Within the crystal, the strongest inter­actions between mol­ecules are the N—H⋯O hydrogen bonds, which organize them into inversion dimers. The dimers are linked through short C—H⋯N contacts and are stacked into layers propagating in the (001) plane. The crystal structure features π–π stacking between the pyridine aromatic ring and the azomethine double bond. The calculated energies of pairwise inter­molecular inter­actions within the stacks are considerably larger than those found for the inter­actions between the layers.

The two new pyrazine­ophanes, 5,7-di­hydro-1H,3H-dithieno[3,4-b:3',4'-e]pyrazine, C8H8N2S2, L1, and 3,4,8,10,11,13-hexa­hydro-1H,6H-bis­([1,4]di­thio­cino)[6,7-b:6',7'-e]pyrazine, C12H16N2S4, L2, both crystallize with half a mol­ecule in the asymmetric unit; the whole mol­ecules are generated by inversion symmetry. The mol­ecule of L1, which is planar (r.m.s. deviation = 0.008 Å), consists of two sulfur atoms linked by a rigid tetra-2,3,5,6-methyl­ene­pyrazine unit, forming planar five-membered rings. The mol­ecule of L2 is step-shaped and consists of two S–CH2–CH2–S chains linked by the central rigid tetra-2,3,5,6-methyl­ene­pyrazine unit, forming eight-membered rings that have twist-boat-chair con­fig­urations. In the crystals of both compounds, there are no significant inter­molecular inter­actions present. The reaction of L1 with silver nitrate leads to the formation of a two-dimensional coordination polymer, poly[(μ-5,7-di­hydro-1H,3H-dithieno[3,4-b;3',4'-e]pyrazine-κ2S:S')(μ-nitrato-κ2O:O')silver(I)], [Ag(NO3)(C8H8N2S2)]n, (I), with the nitrato anion bridging two equivalent silver atoms. The central pyrazine ring is situated about an inversion center and the silver atom lies on a twofold rotation axis that bis­ects the nitrato anion. The silver atom has a fourfold AgO2S2 coordination sphere with a distorted shape. The reaction of L2 with silver nitrate also leads to the formation of a two-dimensional coordination polymer, poly[[μ33,4,8,10,11,13-hexa­hydro-1H,6H-bis­([1,4]di­thio­cino)[6,7-b;6',7'-e]pyrazine-κ3S:S':S''](nitrato-κO)silver(I)], [Ag(NO3)(C12H16N2S4)]n, (II), with the nitrate anion coordinating in a monodentate manner to the silver atom. The silver atom has a fourfold AgOS3 coordination sphere with a distorted shape. In the crystals of both complexes, the networks are linked by C—H⋯O hydrogen bonds, forming supra­molecular frameworks. There are additional C—H⋯S contacts present in the supra­molecular framework of II.

The title compounds, [Mo(C5H5)(COCH3)(C6H12N3P)(CO)2], (1), and [Mo(C5H5)(COCH3)(C9H16N3O2P)(C6H5)2))(CO)2], (2), have been prepared by phosphine-induced migratory insertion from [Mo(C5H5)(CO)3(CH3)]. The mol­ecular structures of these complexes are quite similar, exhibiting a four-legged piano-stool geometry with trans-disposed carbonyl ligands. The extended structures of complexes (1) and (2) differ substanti­ally. For complex (1), the molybdenum acetyl unit plays a dominant role in the organization of the extended structure, joining the mol­ecules into centrosymmetrical dimers through C—H⋯O inter­actions with a cyclo­penta­dienyl ligand of a neighboring mol­ecule, and these dimers are linked into layers parallel to (100) by C—H⋯O inter­actions between the molybdenum acetyl and the cyclo­penta­dienyl ligand of another neighbor. The extended structure of (2) is dominated by C—H⋯O inter­actions involving the carbonyl groups of the acetamide groups of the DAPTA ligand, which join the mol­ecules into centrosymmetrical dimers and link them into chains along [010]. Additional C—H⋯O inter­actions between the molybdenum acetyl oxygen atom and an acetamide methyl group join the chains into layers parallel to (101).

The title compound, C24H18FNO3, crystallizes in the monoclinic centrosymmetric space group P21/n and its mol­ecular conformation is stabilized via C—H⋯O intra­molecular inter­actions. The supra­molecular network mainly comprises C—H⋯O, C—H⋯F and C—H⋯π inter­actions, which contribute towards the formation of the crystal structure. The different inter­molecular inter­actions have been further analysed via Hirshfeld surface analysis and fingerprint plots.

4-[(Morpholin-4-yl)carbothioyl]benzoic acid, C12H13NO3S, a novel phen­yl(morpholino)methane­thione derivative, crystallizes in the monoclinic space group P21/n. The morpholine ring adopts a chair conformation and the carb­oxy­lic acid group is bent out slightly from the benzene ring mean plane. The mol­ecular geometry of the carb­oxy­lic group is characterized by similar C—O bond lengths [1.266 (2) and 1.268 (2) Å] as the carboxyl­ate H atom is disordered over two positions. This mol­ecular arrangement leads to the formation of dimers through strong and centrosymmetric low barrier O—H⋯O hydrogen bonds between the carb­oxy­lic groups. In addition to these inter­molecular inter­actions, the crystal packing consists of two different mol­ecular sheets with an angle between their mean planes of 64.4 (2)°. The cohesion between the different layers is ensured by C—H⋯S and C—H⋯O inter­actions.

In the fused ring system of the title compound, C32H37NO4, the central di­hydro­pyridine ring adopts a flattened boat conformation, the mean and maximum deviations of the di­hydro­pyridine ring being 0.1429 (2) and 0.2621 (2) Å, respectively. The two cyclo­hexenone rings adopt envelope conformations with the tetra­substituted C atoms as flap atoms. The benzene and phenyl rings form dihedral angles of 85.81 (2) and 88.90 (2)°, respectively, with the mean plane of the di­hydro­pyridine ring. In the crystal, mol­ecules are linked via an O—H⋯O hydrogen bond, forming a helical chain along the b-axis direction. A Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H⋯H (65.2%), O⋯H/H⋯O (18.8%) and C⋯H/H⋯C (13.9%) contacts. Quantum chemical calculations for the frontier mol­ecular orbitals were undertake to determine the chemical reactivity of the title compound.

The title compound, C18H16N2O2, consists of perimidine and meth­oxy­phenol units, where the tricyclic perimidine unit contains a naphthalene ring system and a non-planar C4N2 ring adopting an envelope conformation with the NCN group hinged by 47.44 (7)° with respect to the best plane of the other five atoms. In the crystal, O—HPhnl⋯NPrmdn and N—HPrmdn⋯OPhnl (Phnl = phenol and Prmdn = perimidine) hydrogen bonds link the mol­ecules into infinite chains along the b-axis direction. Weak C—H⋯π inter­actions may further stabilize the crystal structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (49.0%), H⋯C/C⋯H (35.8%) and H⋯O/O⋯H (12.0%) inter­actions. Hydrogen bonding and van der Waals inter­actions are the dominant inter­actions in the crystal packing. Computational chemistry indicates that in the crystal, the O—HPhnl⋯NPrmdn and N—HPrmdn⋯OPhnl hydrogen-bond energies are 58.4 and 38.0 kJ mol−1, respectively. Density functional theory (DFT) optimized structures at the B3LYP/ 6–311 G(d,p) level are compared with the experimentally determined mol­ecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.

The title compound, C21H23F2NO, consists of two fluoro­phenyl groups and one butyl group equatorially oriented on a piperidine ring, which adopts a chair conformation. The dihedral angle between the mean planes of the phenyl rings is 72.1 (1)°. In the crystal, N—H⋯O and weak C—H⋯F inter­actions, which form R22[14] motifs, link the mol­ecules into infinite C(6) chains propagating along [001]. A weak C—H⋯π inter­action is also observed. A Hirshfeld surface analysis of the crystal structure indicates that the most significant contributions to the crystal packing are from H⋯H (53.3%), H⋯C/C⋯H (19.1%), H⋯F/F⋯H (15.7%) and H⋯O/O⋯H (7.7%) contacts. Density functional theory geometry-optimized calculations were compared to the experimentally determined structure in the solid state and used to determine the HOMO–LUMO energy gap and compare it to the UV–vis experimental spectrum.

The solid-state structure of bis­(1-mesityl-1H-imidazole-κN3)di­phenyl­boron tri­fluoro­methane­sulfonate, C36H38BN4+·CF3SO3− or (Ph2B(MesIm)2OTf), is reported. Bis(1-mesityl-1H-imidazole-κN3)di­phenyl­boron (Ph2B(MesIm)2+) is a bulky ligand that crystallizes in the ortho­rhom­bic space group Pbcn. The asymmetric unit contains one Ph2B(MesIm)2+ cationic ligand and one tri­fluoro­methane­sulfonate anion that balances the positive charge of the ligand. The tetra­hedral geometry around the boron center is distorted as a result of the steric bulk of the phenyl groups. Weak inter­actions, such as π–π stacking are present in the crystal structure.

The title compound, C18H16N2O3S, was synthesized by reaction of 2-mercapto-3-phenyl­quinazolin-4(3H)-one with ethyl chloro­acetate. The quinazoline ring forms a dihedral angle of 86.83 (5)° with the phenyl ring. The terminal methyl group is disordered by a rotation of about 60° in a 0.531 (13): 0.469 (13) ratio. In the crystal, C—H⋯O hydrogen-bonding inter­actions result in the formation of columns running in the [010] direction. Two parallel columns further inter­act by C—H⋯O hydrogen bonds. The most important contributions to the surface contacts are from H⋯H (48.4%), C⋯H/H⋯C (21.5%) and O⋯H/H⋯O (18.7%) inter­actions, as concluded from a Hirshfeld analysis.

Five examples each of 3-(5-ar­yloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)-1-[4-(prop-2-yn-1-yl­oxy)phen­yl]prop-2-en-1-ones and the corresponding 1-(4-azido­phen­yl)-3-(5-ar­yloxy-3-methyl-1-phenyl-1H-pyrazol-4-yl)prop-2-en-1-ones have been synthesized in a highly efficient manner, starting from a common source precursor, and structures have been determined for three examples of each type. In each of 3-[5-(2-chloro­phen­oxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl]-1-[4-(prop-2-yn-1-yl­oxy)phen­yl]prop-2-en-1-one, C28H21ClN2O3, (Ib), the isomeric 3-[5-(2-chloro­phen­oxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl]-1-[4-(prop-2-yn-1-yl­oxy)phen­yl]prop-2-en-1-one, (Ic), and 3-[3-methyl-5-(naphthalen-2-yl­oxy)-1-phenyl-1H-pyrazol-4-yl]-1-[4-(prop-2-yn­yloxy)phen­yl]prop-2-en-1-one, C32H24N2O3, (Ie), the mol­ecules are linked into chains of rings, formed by two independent C—H⋯O hydrogen bonds in (Ib) and by a combination of C—H⋯O and C—H⋯π(arene) hydrogen bonds in each of (Ic) and (Ie). There are no direction-specific inter­molecular inter­actions in the structure of 1-(4-azido­phen­yl)-3-[3-methyl-5-(2-methyl­phen­oxy)-1-phenyl-1H-pyrazol-4-yl]prop-2-en-1-one, C26H21N5O2, (IIa). In 1-(4-azido­phen­yl)-3-[5-(2,4-di­chloro­phen­oxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl]prop-2-en-1-one, C25H17Cl2N5O2, (IId), the di­chloro­phenyl group is disordered over two sets of atomic sites having occupancies 0.55 (4) and 0.45 (4), and the mol­ecules are linked by a single C—H⋯O hydrogen bond to form cyclic, centrosymmetric R22(20) dimers. Similar dimers are formed in 1-(4-azido­phen­yl)-3-[3-methyl-5-(naphthalen-2-yl­oxy)-1-phenyl-1H-pyrazol-4-yl]prop-2-en-1-one, C29H21N5O2, (IIe), but here the dimers are linked into a chain of rings by two independent C—H..π(arene) hydrogen bonds. Comparisons are made between the mol­ecular conformations within both series of compounds.

The X-ray crystal structure of the title phthalazin-1-one derivative, C17H16N2O3S {systematic name: 2-[(2,4,6-tri­methyl­benzene)­sulfon­yl]-1,2-di­hydro­phthalazin-1-one}, features a tetra­hedral sulfoxide-S atom, connected to phthalazin-1-one and mesityl residues. The dihedral angle [83.26 (4)°] between the organic substituents is consistent with the mol­ecule having the shape of the letter V. In the crystal, phthalazinone-C6-C—H⋯O(sulfoxide) and π(phthalazinone-N2C4)–π(phthalazinone-C6) stacking [inter-centroid distance = 3.5474 (9) Å] contacts lead to a linear supra­molecular tape along the a-axis direction; tapes assemble without directional inter­actions between them. The analysis of the calculated Hirshfeld surfaces confirm the importance of the C—H⋯O and π-stacking inter­actions but, also H⋯H and C—H⋯C contacts. The calculation of the inter­action energies indicate the importance of dispersion terms with the greatest energies calculated for the C—H⋯O and π-stacking inter­actions.

The title compound, C24H30Br2N4O2, consists of a 2-(4-nitro­phen­yl)-4H-imidazo[4,5-b]pyridine entity with a 12-bromo­dodecyl substituent attached to the pyridine N atom. The middle eight-carbon portion of the side chain is planar to within 0.09 (1) Å and makes a dihedral angle of 21.9 (8)° with the mean plane of the imidazolo­pyridine moiety, giving the mol­ecule a V-shape. In the crystal, the imidazolo­pyridine units are associated through slipped π–π stacking inter­actions together with weak C—HPyr⋯ONtr and C—HBrmdc­yl⋯ONtr (Pyr = pyridine, Ntr = nitro and Brmdcyl = bromo­dodec­yl) hydrogen bonds. The 12-bromo­dodecyl chains overlap with each other between the stacks. The terminal –CH2Br group of the side chain shows disorder over two resolved sites in a 0.902 (3):0.098 (3) ratio. Hirshfeld surface analysis indicates that the most important contributions for the crystal packing are from H⋯H (48.1%), H⋯Br/Br⋯H (15.0%) and H⋯O/O⋯H (12.8%) inter­actions. The optimized mol­ecular structure, using density functional theory 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 elucidated to determine the energy gap.

The title compound, C23H28F3NO, is an ortho-hy­droxy Schiff base compound, which adopts the enol–imine tautomeric form in the solid state. The mol­ecular structure is not planar and the dihedral angle between the planes of the aromatic rings is 85.52 (10)°. The tri­fluoro­methyl group shows rotational disorder over two sites, with occupancies of 0.798 (6) and 0.202 (6). An intra­molecular O—H⋯N hydrogen bonding generates an S(6) ring motif. The crystal structure is consolidated by C—H⋯π inter­actions. The mol­ecular structure was optimized via density functional theory (DFT) methods with the B3LYP functional and LanL2DZ basis set. The theoretical structure is in good agreement with the experimental data. The frontier orbitals and mol­ecular electrostatic potential map were also examined by DFT computations.

In the title compound, C21H15N2+·C7H5O2−, 2-phenyl-1H-phenanthro[9,10-d]imidazole and benzoic acid form an ion pair complex. The system is consolidated by hydrogen bonds along with π–π inter­actions and N—H⋯π inter­actions between the constituent units. For a better understanding of the crystal structure and inter­molecular inter­actions, a Hirshfeld surface analysis was performed.

In the title compound, C25H20O2, the central cyclo­hexenone ring adopts an envelope conformation. The mean plane of the cyclo­hexenone ring makes dihedral angles of 87.66 (11) and 23.76 (12)°, respectively, with the two attached phenyl rings, while it is inclined by 69.55 (11)° to the phenyl ring of the benzoyl group. In the crystal, the mol­ecules are linked by C—H⋯O and C—H⋯π inter­actions, forming a three-dimensional network.

The title compound, bis­(1,2-diphenyl-2-sulfanyl­idene­ethane­thiol­ato-κ2S,S')(1,3,5-tri­aza-7-phosphaadamantane-κP)cobalt(II) dichloromethane hemisolvate, [Co(pdt)2(PTA)]·0.5C2H4Cl2 or [Co(C14H10S2)2(C6H12N3P)]·0.5C2H4Cl2, contains two phenyl­dithiol­ene (pdt) ligands and a 1,3,5-tri­aza-7-phosphaadamantane (PTA) ligand bound to cobalt with the solvent 1,2-di­chloro­ethane mol­ecule located on an inversion center. The cobalt core exhibits an approximately square-pyramidal geometry with partially reduced thienyl radical monoanionic ligands. The supra­molecular network is consolidated by hydrogen-bonding inter­actions primarily with nitro­gen, sulfur and chlorine atoms, as well as parallel displaced π-stacking of the aryl rings. The UV–vis, IR, and CV data are also consistent with monoanionic di­thiol­ene ligands and an overall CoII oxidation state.

The crystal structures of two salt crystals of 2,2-bis­(4-methyl­phen­yl)hexa­fluoro­propane (Bmphfp) with amines, namely, dipyridinium 4,4'-(1,1,1,3,3,3-hexa­fluoro­propane-2,2-di­yl)dibenzoate 4,4'-(1,1,1,3,3,3-hexa­fluoro­propane-2,2-di­yl)di­benzoic acid, 2C5H6N+·C17H8F6O42−·C17H10F6O4, (1), and a monohydrated ethyl­enedi­ammonium salt ethane-1,2-diaminium 4,4'-(1,1,1,3,3,3-hexa­fluoro­propane-2,2-di­yl)dibenzoate monohydrate, C2H10N22+·C17H8F6O42−·H2O, (2), are reported. Compounds 1 and 2 crystallize, respectively, in space group P21/c with Z' = 2 and in space group Pbca with Z' = 1. The crystals of compound 1 contain neutral and anionic Bmphfp mol­ecules, and form a one-dimensional hydrogen-bonded chain motif. The crystals of compound 2 contain anionic Bmphfp mol­ecules, which form a complex three-dimensional hydrogen-bonded network with the ethyl­enedi­amine and water mol­ecules.

The title compound, C19H17ClN4O2, was obtained via a two-step synthesis involving the enol-mediated click Dimroth reaction of 4-azido­anisole with methyl 3-cyclo­propyl-3-oxo­propano­ate leading to the 5-cyclo­propyl-1-(4-meth­oxy­phen­yl)-1H-1,2,3-triazole-4-carb­oxy­lic acid and subsequent acid amidation with 4-chloro­aniline by 1,1'-carbonyl­diimidazole (CDI). It crystallizes in space group P21/n, with one mol­ecule in the asymmetric unit. In the extended structure, two mol­ecules arranged in a near coplanar fashion relative to the triazole ring planes are inter­connected by N—H⋯N and C—H⋯N hydrogen bonds into a homodimer. The formation of dimers is a consequence of the above inter­action and the edge-to-face stacking of aromatic rings, which are turned by 58.0 (3)° relative to each other. The dimers are linked by C—H⋯O inter­actions into ribbons. DFT calculations demonstrate that the frontier mol­ecular orbitals are well separated in energy and the HOMO is largely localized on the 4-chloro­phenyl amide motif while the LUMO is associated with aryl­triazole grouping. A Hirshfeld surface analysis was performed to further analyse the inter­molecular inter­actions.

The in meso in situ serial X-ray crystallography method was developed to ease the handling of small fragile crystals of membrane proteins and for rapid data collection on hundreds of microcrystals directly in the growth medium without the need for crystal harvesting. To facilitate mounting of these in situ samples on a goniometer at cryogenic or at room temperatures, two new 3D-printed holders have been developed. They provide for cubic and sponge phase sample stability in the X-ray beam and are compatible with sample-changing robots. The holders can accommodate a variety of window material types, as well as bespoke samples for diffraction screening and data collection at conventional macromolecular crystallography beamlines. They can be used for convenient post-crystallization treatments such as ligand and heavy-atom soaking. The design, assembly and application of the holders for in situ serial crystallography are described. Files for making the holders using a 3D printer are included as supporting information.

A furnace that covers the temperature range from room temperature up to 2000 K has been designed, built and implemented on the D2AM beamline at the ESRF. The QMAX furnace is devoted to the full exploration of the reciprocal hemispace located above the sample surface. It is well suited for symmetric and asymmetric 3D reciprocal space mapping. Owing to the hemispherical design of the furnace, 3D grazing-incidence small- and wide-angle scattering and diffraction measurements are possible. Inert and reactive experiments can be performed at atmospheric pressure under controlled gas flux. It is demonstrated that the QMAX furnace allows monitoring of structural phase transitions as well as microstructural evolution at the nanoscale, such as self-organization processes, crystal growth and strain relaxation. A time-resolved in situ oxidation experiment illustrates the capability to probe the high-temperature reactivity of materials.