The two independent cations are conformationally similar with the comparative dihedral angles between the central pyridine ring and the three benzene substituent rings being 3.0 (2), 36.4 (1) and 24.2 (1)°, and 3.7 (2), 36.5 (1) and 24.8 (1)°, respectively. In the crystal, the cations, anions and water molecules are linked through O—H⋯O and O—H⋯Br hydrogen bonds, forming an insular unit. Within the cations there are also intramolecular N—H⋯O hydrogen bonds. Adjacent centrosymmetrically related aggregates are linked by π–π stacking interactions between the pyridine ring and a benzene ring in both cations [ring-centroid separations = 3.525 (3) and 3.668 (3) Å], forming chains extending across the ac diagonal. Voids between these chains are filled by dichloromethane molecules.The asymmetric unit in the structure of the title compound, C DOI: 10.1107/S2056989015021386/zs2352Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989015021386/zs2352Isup3.molSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015021386/zs2352Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989015021386/zs2352fig1.tif. DOI: The asymmetric unit in the structure of the title compound, with displacement ellipsoids shown at the 50% probability level. Hydrogen bonds are shown as dashed lines.Click here for additional data file.10.1107/S2056989015021386/zs2352fig2.tifx y z . DOI: x + y + z operation.The result of superposition of one independent cation with another shifted by an Click here for additional data file.10.1107/S2056989015021386/zs2352fig3.tifA x y z . DOI: A indicates the symmetry operator −x + 1, y − z + Insular hydrogen bonded aggregates in the structure. Hydrogen bonds are shown as dashed lines. Suffix Click here for additional data file.10.1107/S2056989015021386/zs2352fig4.tif. DOI: Chains formed by π–π stacking interactions between aromatic ring systems in adjacent H-bonded frameworks.1436252CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The mononuclear complex exhibits a distorted tetrahedral coordination geometry about the metal atom, arising from one S atom of the benzenecarbothioamide ligand, two P atoms of two triphenylphosphane molecules and one bromide ion. An intramolecular N—H⋯Br hydrogen bond is observed and in the crystal structure, inversion dimers linked by pairs of N—H⋯Br and C—H⋯Br hydrogen bonds are observed. In addition, C—H⋯π interactions occur, leading to [101] chains. 7H7NS)(C18H15P)2], was obtained from the reaction of silver(I) bromide with benzenecarbothioamide (C7H7NS) and triphenylphosphane (C18H15P) in the mixed solvent of acetonitrile and ethanol. The mononuclear complex exhibits a distorted tetrahedral coordination geometry about the metal atom, arising from one S atom of a benzenecarbothioamide ligand, two P atoms of two triphenylphosphane molecules and one bromide ion. An intramolecular N—H⋯Br hydrogen bond is observed and in the crystal structure, inversion dimers linked by pairs of N—H⋯Br and C—H⋯Br hydrogen bonds are observed. In addition, C—H⋯π interactions occur, leading to [101] chains. Hirshfeld-surface analyses are presented and discussed.The title complex, [AgBr(C I-containing phosphorus and sulfur donor ligands have been studied and published extensively in recent years (C18H15P)2] previously synthesized by us (C18H15P)2], 2.5580 (5) Å. The Ag—P bond lengths of 2.4682 (7) and 2.4671 (6) Å for Ag1—P1 and Ag1—P2, respectively, are similar to those of the Ag—P bond lengths in [AgCl(C7H7NS)(C18H15P)2] [2.4529 (5) and 2.4578 (5) Å], and similar to the Ag—P distances of analogous tetrahedrally coordinated AgI complexes such as [Ag(NO3)(C2H3N3S)(C18H15P)2]  ·2NO3  and C17—H17⋯Br1i [3.789 (3) Å]  hydrogen bonds between a pair of adjacent complex molecules; these are similar to the those in the above-mentioned complex [AgCl(C7H7NS)(C18H15P)2]  Å].In the crystal, the dimeric intermolecular interactions are generated through a crystallographic inversion center by linking through the N1—H1et al., 2004Crystal Explorer 3.1  and outside (de) of the Hirshfeld surface analyse the intermolecular interactions via the mapping of normd, as depicted in Fig. 4a–d) for Hirshfeld surfaces of the complex are shown with characteristic pseudo-symmetry wings in the upper left and lower right sides of the de and di diagonal axes that represent the overall 2D fingerprint plot and those delineated into H⋯H, H⋯Br/Br⋯H, and C⋯H/H⋯C contacts are shown in Fig. 5a–d, respectively. The fingerprint plot of H⋯H contacts represented by the largest contribution within the Hirshfeld surfaces (60.8%) are shown as one distinct pattern with a minimum value of de + id ∼2.6 Å. The reciprocal H⋯Br/Br⋯H contacts consist of 5.4% of the total Hirshfeld surface with de + id ∼3.3 Å, exhibited by two symmetrical narrow pointed wings indicating the intermolecular hydrogen-bond interactions N1—H1A⋯Br1 and C17—H17⋯Br1 in the crystal packing. The presence of C—H⋯π interactions on the fingerprint plot, which contribute 29.7% of overall Hirshfeld surface, are indicated by de + id ∼3.0 Å.For the title complex, the Hirshfeld-surfaces analysis  bromide  was dissolved in the mixed solvent of 15 ml of acetonitrile and 15 ml of ethanol and then triphenylphosphane  was added. The mixture was refluxed for 2 h at 343 K and a white precipitate was formed. After that, benzenecarbothioamide  was added and continually refluxed for 5 h. At that time, the white precipitate dissolved. The clear yellow solution was filtered and left to evaporate at room temperature. After a day, pale-yellow blocks of the title compound were filtered off and dried Uiso(H) = 1.2 Ueq(C). N-bound H atoms were found from difference maps and refined isotropically with distance restraint N—H = 0.85–0.86 Å.Crystal data and details of structure determination are summarized in Table 210.1107/S2056989016009518/hb7592sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016009518/hb7592Isup2.hklStructure factors: contains datablock(s) I. DOI: 1484796CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The PH 21H21O5PS·H2O·CH2Cl2, the phosphonium–sulfonate zwitterion has the acidic H atom located on the P atom rather than the sulfonate group. The S—O bond lengths [1.4453 (15)–1.4521 (14) Å] are essentially equal. In the crystal, the water molecules bridge two zwitterions via Owater—H⋯Osulfonate hydrogen bonds into a centrosymmetric dimer. The dimers are further linked by weak CAryl—H⋯Osulfonate hydrogen bonds into chains extending along [100]. The PH+ group is not involved in intermolecular interactions.In the title compound, C Addition of an H+ at phosphorous should not add significant steric congestion and therefore it is not surprising that 1 also adopts the exo3 conformation. The Omethoxy⋯P distances, 2.7691 (14) and 2.7940 (14) Å, are shorter than the sum of the O and P van der Waals radii (3.35 Å). The O3⋯H1(P1) distance is 2.44 (2) Å.Compound up Fig. 1. The S—Oexo3 conformation versus alternative exo2 and exo1 conformations was investigated by DFT calculations using the hybrid exchange-correlation functional PBE0  or two (exo1) methoxy groups were rotated away from the PH+ group. The exo2 and exo1 conformers were calculated to be 1.2 and 2.5 kcal mol−1 less stable than the exo3 isomer, respectively. The HOMO of the exo3 conformer is comprised of p orbitals of the sulfonate O atoms, while the LUMO is delocalized over the phenyl rings and P—Caromatic bonds  and 1.98 (3) Å (H2O)][2-{(o-CF3-Ph)2P}-4-Me-benzenesulfonate] . The structure of the triethylammonium salt of 2-[bis(2-methoxyphenyl)phosphanyl]benzenesulfonate has also been reported . The product was purified by recrystallization . Crystals of 1·H2O·CH2Cl2 (I) suitable for the X-ray diffraction analysis were obtained by layering Et2O on a CH2Cl2 solution of 1 at 277 K.Compound Uiso(H) set to 1.2–1.5Ueq(C). The P- and O-bound H atoms were located in a difference Fourier map and refined isotropically.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016000669/cv5502sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016000669/cv5502Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016000669/cv5502Isup3.cmlSupporting information file. DOI: 1447138CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Melting points of compounds Cu3V2O8 and Cu2V2O7 are 780°C and 790°C, respectively. The addition of small amounts of Mg (II), MgxCu3-xV2O8 (x < 1.0) and MgyCu2-yV2O7 (y < 0.5) fused compositions, was not sufficient to stabilize structures at 800°C. For the Mg2CuV2O8 (x = 2.0) composition fired at 800°C, Mg (II) incorporated into the monoclinic Cu3V2O8 structure stabilizes this crystalline phase. At 1000°C, orthorhombic Mg3V2O8 structure from this composition was obtained. Solid solutions with orthorhombic symmetry were detected from the prepared compositions fired at 1000°C when 1.0 ≤ x ≤ 3.0. The difference of coloration of Cu, Mg vanadates might be explained by the presence of a strong charge transfer band in visible spectra.In this study, MgThe online version of this article (doi:10.1186/s40064-015-0908-8) contains supplementary material, which is available to authorized users. Charge transfer effects in which an electron is transferred between an anion and a cation are often responsible for intense colours as in, for example, permanganate (purple) and chromates (yellow). In solids, there is an additional source of colour; it involves the transition of electrons between energy bands. Colour may be measured in a quantitative way by spectroscopic techniques. At higher frequencies than the infrared, electronic transitions associated with d-level splitting, impurity ions, crystal defects, etc., are possible. Many of these occur in the visible region and are responsible for colour.3V2O8 compound with monoclinic symmetry and space group P121/c1 is similar to the orthorhombic structure of Mg3V2O8 compound with space group Cmca  and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions was made to investigate the possible formation of solid solutions with orthovanadate or divanadate structure. Coloration of these materials was also measured and related with structure in prepared compositions. A partial substitution of Cu (II) by Mg (II) ions might increase the melting point of materials with orthovanadates and divanadates structures. These potential solid solutions could be applied in ceramic industry.In this study, structural characterization of MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions were synthesized by the chemical coprecipitation method. The starting materials were Cu(NO3)2 · 2.5H2O , MgCl2.6H2O (Panreac) of reagent grade chemical quality, and NH4VO3 . The stoichiometric amount of NH4VO3, Cu(NO3)2 · 2.5H2O and MgCl2 · 6H2O was added on 200 mL of water with vigorous stirring at room temperature. These starting materials were added in solid state and the concentration of the various cations is different in each prepared composition. After that, a solution of ammonium hydroxide was added dropwise until pH = 8. The obtained precipitates were dried by an infrared lamp and dry samples were fired at 300°C for 12 hours, 600°C for 12 hours, 800°C for 1 hour and 1000°C for 1 hour.MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) fired compositions to investigate the possibility of formation of solid solution in these synthetic conditions. The diffraction patterns were collected running from 5 to 110 o2θ, using monochromatic CuKα radiation, a step size of 0.02 o2θ and a sampling time of 10 s. The initial structural information was obtained of the Inorganic Crystal Structure Database  Rietveld . Unit ceUV–vis-NIR spectroscopy (diffuse reflectance) allows the Cu (II) site and the V (V)-O and Cu (II)-O charge bands in samples to be studied. A Jasco V-670 spectrophotometer was used to obtain the UV–vis-NIR (ultraviolet visible near infrared) spectra in the 200 to 2500 nm range. X-Rite spectrophotometer  was used to obtain CIEL*a*b* colour parameters on fired samples: L* is the lightness axis (black (0) → white (100)), a* the green (−) → red (+) axis, and b* is the blue (−) → yellow (+) axis CIE .xCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions. XRD patterns from MgxCu3-xV2O8 and MgyCu2-yV2O7 compositions are shown in Additional files Tables xCu3-xV2O8 (0 ≤ x < 1.0) compositions the major crystalline phase is the triclinic Cu3V2O8 polymorph at 600°C. Cu3V2O8 compound melts incongruently at 780°C. This fact can explain the melting of samples with a presence higher than 50% in Cu3V2O8 triclinic crystalline phase . This crystalline phase with triclinic structure is not detected in samples fired at 800 and 1000°C.In Mg3V2O8 structure and monoclinic symmetry was obtained at 300 and 600°C in compositions with 1.0 ≤ x ≤ 2.0. This crystalline phase with monoclinic Cu3V2O8 structure is also present when 1.5 ≤ x ≤ 2.0 at 800°C. The crystalline phase with the structure of MgCu2V2O8 compound (β = 90.44 (2) and Z = 4) is detected when 1.0 ≤ x ≤ 2.0 at 800°C but the crystalline phase with the ordered metal distributions in Mg2CuV2O8 compound (β = 116.22 (3), Z = 2, Cu1 in 2a sites and Mg1 in 4e sites, ICSD-404851) is not detected in conditions of this study. In the prepared Mg2CuV2O8 composition (MgxCu3-xV2O8 with x =2.0), crystalline phase with Cu3V2O8 structure and monoclinic symmetry  in 2b sites and M2  in 4e sites) is the only crystalline phase detected at 800°C. Figure 2V2O8 (x = 1.0), Mg2CuV2O8 (x = 2.0) and Mg2.5Cu0.5V2O8 (x = 2.5) compositions fired at 800°C.A crystalline phase with Cu3V2O8 structure is obtained when 2.0 ≤ x ≤ 3.0 at 600°C and when 2.5 ≤ x ≤ 3.0 at 800°C. At 1000°C, this phase is the major crystalline phase in the unfused samples (x ≥ 1.0). Figure xCu3-xV2O8 compositions with x = 1.0, x = 2.0 and x = 2.5 fired at 1000°C. The orthorhombic Mg3V2O8 crystalline phase is the major phase in them.Crystalline phase with orthorhombic MgCu divanadates and Mg divanadates are present together with Cu and Mg orthovanadates in some samples.2V2O7 structure (orthorhombic symmetry) is only present in MgyCu2-yV2O7 compositions when y < 0.5 at 600°C. These compositions melt at 800°C. Diffraction peak intensity associated with this crystalline phase is weak or very weak at 300°C.Crystalline phase with α-Cu2V2O7 structure (monoclinic symmetry) is more extended than the crystalline phase with α-Cu2V2O7 structure in the prepared compositions. At 300°C, crystalline phase with β-Cu2V2O7 structure is present when y < 0.5 with diffraction peaks of medium intensity. This crystalline phase is present when 0.25 ≤ y < 1.50 at 600°C and when 0.50 ≤ y ≤ 0.75 with diffraction peak of strong or medium intensity. Figure 0.25Cu1.75V2O7 composition fired at 600°C.Presence of crystalline phase with β-Cu2V2O7 structure (triclinic symmetry) is present in compositions when 0.25 ≤ y ≤ 0.50 at 300°C but its intensity of diffraction peak is weak at 600 and 800°C  is detected in a compositional range more extended than the crystalline phase with triclinic Mg2V2O7 structure from MgyCu2-yV2O7 prepared compositions. Crystalline phase with monoclinic α-Mg2V2O7 structure is identified when 0.75 ≤ y ≤ 2.00 at 600°C, when 0.50 ≤ y ≤ 2.00 at 800°C, and when 1.50 ≤ y ≤ 2.00 at 1000°C.Crystalline phase with α-Mg2V2O7 structure is observed when 1.5 ≤ y ≤ 2.00 in compositions fired at 800°C and only when y = 2.0 at 300°C.Crystalline phase with triclinic MgTables xCu3-xV2O8 compositions solid solutions with triclinic Cu3V2O8 structure are obtained when 0.0 ≤ x ≤ 1.0 at 600°C. At this temperature, the c unit cell parameter increases slightly with the replacement of Cu (II) ion by a slightly smaller one (Mg (II)) from MgxCu3-xV2O8 compositions when 0.0 ≤ x ≤ 1.0. Ionic radii values do not explain this fact. A slight contraction of unit cell is expected. Structural distortion might explain the c increase with incorporation of Mg (II) ions in a structure (Tena From Mgure Tena .xCu3-xV2O8 (x ≥ 1.0) compositions fired at 800°C is noticeable in monoclinic Cu3V2O8 structure (detected when 1.5 ≤ x ≤ 2.0) and it indicates the formation of solid solutions with monoclinic Cu3V2O8 structure in 1.5 ≤ x ≤ 2 compositional range at 600°C and 800°C.Variation of unit cell parameters obtained from Mg3V2O8 structure are also obtained when 2.5 ≤ x ≤ 3.0 at 600, 800°C and when 1.0 ≤ x ≤ 3.0 at 1000°C. Figure xCu3-xV2O8 samples fired at 1000°C/1 h. At 1000°C, the a and b unit cell parameters decrease with the replacement of Cu (II) ion by a slightly smaller one (Mg (II)). Average changes of interatomic distances are very slight. Changes in intensities with composition  are detected in some samples  is slightly different at 600 and 800°C in the conditions of this study. This slight difference between the two crystalline phases with the same structure is evidenced with differences in unit cell parameters values obtained. In MgyCu2-yV2O7 compositions fired at 600°C, the values of a and β parameters decrease when y increases in β-Cu2V2O7 structure . At 800°C this crystalline phase is obtained with a weight fraction > 35% only when 0.5 ≤ y ≤ 0.75. In crystalline phase with α-Mg2V2O7 structure, β angle value is close to 100° at 300°C and it is close to 90° at 800°C. When two crystalline phases with this structure are detected in the same sample, unit cell parameters are 0.2 Å  or 8 degrees (β parameter) longer and wider in one of them. This fact is in accordance with the formation of solid solutions in this monoclinic α-Mg2V2O7 structure with the replacement of Mg (II) ion by Cu (II) and with an important distortion structural in these formed solid solutions. Solid solutions with monoclinic α-Mg2V2O7 structure are obtained when 0.5 ≤ y ≤ 2.0 at 600 and 800°C. At 1000°C, these last solid solutions are obtained when y ≥ 1.5, including all unmelted samples  and Mg (II) ions are also six.Coordination number of V (V) ion in Cu and Mg orthovanadate and divanadate structures is four. Coordination number of Cu (II) ion is four and five and coordination number of Mg (II) ion is six in these structures. Values obtained from samples are in accordance with literature about these structures. In distorted monoclinic structure of CuyCu2-yV2O7 compositions considering all the crystalline phases in each composition and its weight fraction in samples fired at 600, 800 and 1000°C. These M-O  interatomic distances increase with magnesium amount (y) when 0 ≤ y ≤ 1.25. This increased average M-O distance is coincident with destabilization of structures of Cu divanadate and a change is observed when y > 1.25. Structures of Cu divanadate are unstable with temperature and structures of Mg divanadates are stable at 1000°C when 1.5 ≤ y ≤ 2.0  and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions fired at 600, 800 and 1000°C. Visible spectra obtained from MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions fired at 800°C/1 h and MgxCu2-xP2O7 (0 ≤ x ≤ 1.5) compositions fired at 800°C/5d (Tena 9) a transition d-d is allowed. Experimentally electronic spectra of Cu (II) ion are often characterized by a single highly asymmetric band. In this study spectra show a strong absorbance in 700–1400 nm wavelength range with the absorption maximum at 800–900 nm. It can be associated with Cu (II) d-d transition. Bands due to d-d transitions are not expected from V (V) ion. Strong absorbance in 430–600 nm wavelength range (in visible wavelength range) with the absorption maximum depending of copper amount in the sample  is detected in MgxCu3-xV2O8 (0 ≤ x ≤ 3) and MgyCu2-yV2O7 (0 ≤ y ≤ 2) compositions at 300°C/12 h, 600°C/12 h, 800°C/1 h and 1000°C/1 h. The strong absorbance in 350–600 nm wavelength range is not observed in MgxCu2-xP2O7 compositions  and MgyCu2-yV2O7 (y = 2) compositions. It is associated with charge transfer between Cu-O in orthovanadates and divanadates when 0 ≤ x < 3 or when 0 ≤ y < 2. When x = 3 or y = 2, the charge transfer is associated with V-O charge transfer (λ < 430 nm in studied temperature range). Maximum of this band is observed at higher wavelength when copper amount is hight than when the copper amount is low. This strong absorbance in visible wavelength range explains the colour of these materials. At 600 and 800°C, coloration from samples with vanadate structures is red-brown, orange and yellow and is very different to the weak blue coloration obtained from samples with phosphate structures (Tena xCu3-xV2O8 (x ≠ 3) compositions and in MgxCu2-yV2O7 (y ≠ 2) compositions with different crystalline phases detected by XRD  and MgyCu2-yV2O7 (0 ≤ y ≤ 2) samples fired at 600, 800 and 1000°C are shown in Table CIE L*, a* and b* parameters of Mg3V2O8 structure is detected. The best yellow colour is obtained from Mg2CuV2O8 (x = 2.0) solid solution with monoclinic Cu3V2O8 structure. This is the only crystalline phase detected at 800°C in conditions of this study. The Mg (II) incorporated into this structure stabilizes this crystalline phase at temperatures higher than 780°C (melting point of Cu3V2O8). In Mg2CuV2O8 composition fired at 800°C, average distances of M1-O  = 1.9587 Å and M2-O  = 2.1129 Å are obtained. Yellow colorations are not obtained from Cu, Mg divanadates.Interesting yellow colorations are obtained when x = 1.5 and 2.0 at 600°C/12 and when x = 2.0 at 800°C/1 h. In these samples that development yellow colorations, crystalline phase with monoclinic Cu0.5Cu1.5V2O7 (y = 0.5) fired at 600°C /12 h is the most noticeable colour but it is unstable at 800°C /1 h. Dark brown colour is obtained from this composition at 800°C. The major crystalline phase detected by XRD is the crystalline phase with β-Cu2V2O7 structure in this sample fired at 600°C.The colour red-brown obtained from Mg2V2O7 and Cu3V2O8 or β-Cu2V2O7 and α-Mg2V2O7 structures is detected by XRD.Orange colour is obtained when y = 0.75, 1.00 and 1.25 at 600°C/12 h and when y = 1.25 and 1.50 at 800°C/1 h. In these orange materials, a mixture of monoclinic crystalline phases with β-CuyCu2-yV2O7 compositions fired at 600°C/12 h  are obtained. These solid solutions with monoclinic Cu3V2O8 structure are obtained when 1.5 ≤ x ≤ 2.0 at 600°C and 800°C. Solid solutions with orthorhombic Mg3V2O8 structure are obtained when 2.5 ≤ x ≤ 3.0 at 600, 800°C and when 1.0 ≤ x ≤ 3.0 at 1000°C. In this study, the most stable solid solutions are obtained with Mg orthovanadate structure (orthorhombic).From MgyCu2-yV2O7 compositions, the formation of two kind of solid solutions with β-Cu2V2O7 and α-Mg2V2O7 structures is detected. Solid solutions with monoclinic β-Cu2V2O7 structure are obtained when 0.25 ≤ y ≤ 1.50 at 600°C and when 0.50 ≤ y ≤ 0.75 at 800°C. Solid solutions with monoclinic α-Mg2V2O7 structure are obtained when 0.5 ≤ y ≤ 2.0 at 600 and 800°C and showing an important structural distortion. At 1000°C, solid solutions with α-Mg2V2O7 structure are obtained in 1.5 ≤ y ≤ 2.0 compositional range. It is proposed the existence of a new polymorph of Mg2V2O7 compound with α-Mn2V2O7 structure detected when y ≥ 1.25 at 300°C.From MgxCu3-xV2O8 (0 ≤ x < 3) and MgyCu2-yV2O7 (0 ≤ y < 2) compositions which is associated with charge transfer between Cu-O in orthovanadates and divanadates. Wavelength of the abrupt change in absorbance is in accordance with Cu-O interatomic distances in these structures. In this study, the best yellow colour is obtained from Mg2CuV2O8 (x = 2.0) solid solution with monoclinic Cu3V2O8 structure. The colour red-brown is obtained from Mg0.5Cu1.5V2O7 (y = 0.5) fired at 600°C /12 h and it is unstable at 800°C /1 h. This red-brown colour is obtained when the average M-O distances are the shortest from divanadates. Orange colour is also obtained from some divanadates when average M-O distance is long.Strong absorbance in visible spectra is detected in MgStructural changes must be also considered to explain the colour of these materials. Thus, yellow colorations are obtained from orthovanadates and red-brown and orange colorations are obtained from divanadates.


The cationic diruthenium tetraacetate core lies on a crystallographic inversion center with Ru—Ru and Ru—N bond lengths of 2.2738 (3) and 2.2920 (17) Å, respectively. The Ru—Ru—N bond angle is close to linear at 176.48 (4)°, and a significant π-stacking interaction of 3.5649 (16) Å is seen between overlapping pyridine rings of adjacent cations.The title compound, [Ru Then, 3-chloropyridine  was added and the solution allowed to stir for 5 min at room temperature. The volume of the solution was then reduced to 5 ml under vacuum and allowed to cool to 278 K overnight. The crystalline product was collected via suction filtration. Yield = 0.098 g (63%). Crystals suitable for X-ray diffraction were obtained by slow diffusion of diethyl ether into a 1,2-dichloroethane solution of the complex. IR (cm−1): 2947 (νC—H), 1447 (asym. νCOO), 1396 (sym. νCOO), 841, (νPF6), 766 (νC—Cl), 692 (δC—CH3). UV–vis ): 427 (2.95), 263 (4.05), 210 (4.33).Synthesis of the title compound followed an earlier method developed in our lab (Vamvounis F2(obs) and F2, PLATON  I. DOI: 10.1107/S2414314622002498/wm4161Isup2.hklStructure factors: contains datablock(s) I. DOI: 2156199CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Calophyllum gracilentum, is reported. The molecule is characterized by a xanthone skeleton of three fused six-membered rings plus an additional fused pyrano ring and one 3-methylbut-2-enyl side chain.The crystal structure of brasixanthone B, a naturally occurring xanthone isolated from the stem bark of  23H22O5, isolated from Calophyllum gracilentum, is characterized by a xanthone skeleton of three fused six-membered rings plus an additional fused pyrano ring and one 3-methylbut-2-enyl side chain. The core xanthone moiety is almost planar, with a maximum deviation 0.057 (4) Å from the mean plane. In the molecule, an intramolecular O—H⋯O hydrogen bond forms an S(6) ring motif. The crystal structure features intermolecular O—H⋯O and C—H⋯O interactions.The title compound , C Calophyllum, frequently referred as ‘bintangor’ or ‘penaga’ in Malay is a part of the Calophyllaceae family  and 94.2 (4)°, respectively, suggesting a synclinal conformation  Å, θ = 65.4 (7)° and φ = 38.2 (7)°. The core xanthone moiety  is almost planar, with maximum deviation of 0.057 (4) Å from the mean plane for C16. The dihedral angles between xanthone rings are: 2.29 (19)° for B and C, 2.94 (19)° for B and D, and 0.75 (19)° between C and D. There are two methyl groups attached to atom C1 in ring A with C—C distances of 1.488 (6) and 1.483 (6) Å.The orientation of the 3-methylbut-2-enyl side chain attached to ring O3⋯O4, forms an S(6) ring motif. In the crystal, the molecules are linked by intermolecular hydrogen bonds O5—H1O5⋯O4, C11—H11A⋯O3 and C12—H12A⋯O5  molecules are stacked by π–π interactions with an interplanar spacing of 3.319 (4) Å between corresponding xanthone rings.In the title compound Fig. 1, an intr5 Table 1, forming5 Table 1. Inversicalophyllum gracilentum was ground and extracted with n-hexane, chloroform, ethyl acetate and methanol. Fractionation of the hexane extract by gravity column chromatography over (Merck Kieselgel No. 1.09385.1000) silica gel with elution of n-hexane: ethyl acetate and ethyl acetate: methanol in a step-wise gradual increment in polarity. This produced 28 fractions, which were combined and pooled together as 10 sub-fractions based on the TLC profile. Fraction 5 was subjected to further isolation by column chromatography over Sephadex LH20 eluted with methanol and several more purification steps using radial chromatography over silica (Merck Kieselgel No. 1.07749.1000), eluting with an n-hexane:ethyl acetate (8:2) mixture. Yellow needle-like crystals were obtained. The melting point was found to be 500–502 K  of Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314622011981/pk4037sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622011981/pk4037Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622011981/pk4037Isup3.cmlSupporting information file. DOI: 2227328CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


H-1,2,3-triazol-1-yl)ethyl]phosphonate ester, which was then hydrolyzed under acidic conditions (HCl) to give the ‘free’ phosphonic acid. The use of HCl for the hydrolysis caused protonation of the triazole ring, rendering the compound cationic, charged-balanced by a Cl− anion.This new triazole-functionalized phosphonic acid, PTEPHCl, was synthesized by the ‘click’ reaction of the alkyl azide diethyl-(2-azidoethyl)phosphonate with phenylacetylene to give the diethylphosphonate ester, which was then hydrolyzed under acidic conditions (HCl) to give the ‘free’ phosphonic acid. The use of HCl for the hydrolysis caused protonation of the triazole ring, rendering the compound cationic, charged-balanced by a Cl− anion. There are extensive hydrogen-bonding interactions in the structure of PTEPHCl, involving the phosphonic acid (–PO3H2) group, the triazolium ring and the Cl− anion.The new triazole-functionalized phosphonic acid 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride, C This ester was then hydrolyzed in acidic conditions to give 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride (PTEPHCl). In the present work, we report the crystal structure of the above-mentioned triazole-functionalized phosphonic acid PTEPHCl.The reaction of an organic azide with an alkyne to give a triazole is a well-known process  and P1—O2 = 1.5513 (16) Å] and one ‘short’ P—O bond [P1—O3 = 1.4805 (14) Å]. The ‘long’ P—O bonds correspond to the P—O—H moieties and the ‘short’ P—O bond corresponds to the phosphoryl P=O moiety. All P—O bond lengths have the expected values  Å and O2⋯Cl1 = 2.9422 (17) Å. The phosphoryl P=O group forms a hydrogen bond with the N—H portion of the triazolium ring [O3⋯N3 2.610 (2) Å]. Finally, the benzene ring interacts with a phosphonate oxygen through a weak C—H⋯O contact at 3.476 (3) Å (C6⋯O2).The phosphonic acid moiety forms four hydrogen-bonding interactions Fig. 2. Specifiπ–π stacking interactionsThere is only one type of very weak π–π stacking interaction in the structure of 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride. The centroid-to-centroid distance is 4.0423 (15) Å, with the rings being ‘shifted’ from one another (slippage distance between the rings: 2.222 Å) and parallel.Crystal packingb axis. The chloride anions form corrugated sheets [‘short’ Cl⋯Cl distances at 4.9455 (12) Å and ‘long’ Cl⋯Cl distances at 6.4564 (9) Å] that are parallel to the bc plane.Fig. 3Reagents and materialsl-ascorbic acid were from Serva. Sodium sulfate was from Merck. Dichloromethane, tetrahydrofuran (THF), hydrochloric acid (37%) and nitric acid (70%) were from Scharlau. Ion-exchange-column deionized water was used.All starting materials were obtained from commercial sources and used without further purification. The reagents diethyl 2-bromoethylphosphonate (97%), phenylacetylene (98+%), copper sulfate pentahydrate (99%), zinc nitrate hexahydrate (98%) and ethylenediaminetetraacetic acid (98%) were from Alfa Aesar. Sodium azide and Synthesis of 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride (PTEPHCl)et al., 2018l-ascorbic acid  to produce diethyl[2-ethyl]phosphonate ester. The reaction mixture was heated at 313 K under vigorous stirring for 48 h. After filtration, the filtrate was mixed with dichloromethane (50 mL) and an aqueous solution of the Cu2+ chelant ethylenediaminetetraacetic acid  and the mixture was stirred for ∼1 h. After extraction with dichloromethane (4 × 50 mL) and evaporation, diethyl[2-ethyl]phosphonate ester was obtained in solid form. Finally, the latter (0.5 g) was hydrolyzed with 25 mL of H2O and 30 mL of HCl at 373 K for 48 h, giving 5-phenyl-3-(2-phosphonoethyl)-1,2,3-triazol-1-ium chloride in crystalline form . The crystal used for the data collection was handled under inert conditions. It was manipulated while immersed in a perfluoropolyether protecting oil and mounted on a MiTeGen Micromount™.Three distinct steps were followed for the syntheses of the ligand PTEP. The first step was the synthesis of diethyl-(2-azidoethyl)phosphonate, following a properly adapted published procedure  δ 8.51 , 7.93 , 7.67 , 4.82 , 2.52 . 13C NMR  δ 146.71, 131.27, 129.38, 128.28, 125.53, 121.87, 45.42, 30.45 . 31P NMR  δ 20.17.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314622001894/tx4001sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622001894/tx4001Isup4.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622001894/tx4001Isup5.molSupporting information file. DOI: Click here for additional data file.10.1107/S2414314622001894/tx4001Isup4.cmlSupporting information file. DOI: 2145106CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title salt, all O—H and N—H groups in the cations (metforminium and ammonium) and lattice water molecules are donor groups for hydrogen bonds, giving a highly compact crystal structure. 4)4(C4H12N5)2[V10O28]·6H2O, crystallizes with the decavanadate anion placed on an inversion centre in space group PThe title compound, (NH The HMetf+ monocation has its charge located mainly on N2. Furthermore, this cation is characterized by a dihedral angle of 54.85 (5)° between planes C2–C4/N3–N5 and C1/N1–N3. This twisted geometry is observed in several other compounds of metforminium(1+). Indeed, metformin and its cations HMetf+ and H2Metf2+ are highly flexible entities: the twist angle for 93 structures recovered from the CSD  −x + 1, −y + 2, −z + 1], as well as between the anion and a water molecule ·8H2O and [H2Metf]2[NH4]2(V10O28)·10H2O ·6H2O (ca. 5% yield). These yields are poorly reproducible, and no powder diffraction was performed on the solid phases obtained by fractional crystallization to check their purity. Therefore, we cannot rule out the presence of other crystallized compounds in this reaction.Good-quality single crystals of the title compound were obtained during the reaction between ammonium metavanadate  I. DOI: 10.1107/S2414314621006349/im4012Isup2.hklStructure factors: contains datablock(s) I. DOI: 2090930CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the dihedral angle between the mean planes of the cyclohexane and 1,3-dithietane rings is 9.1 (3)°. A short S⋯O contact is observed in the crystal. 8H8O2S2, contains a cyclohexane-1,3-dione ring, which has a twist-boat conformation. The C2S2 ring is close to planar (r.m.s. deviation = 0.023 Å) and the dihedral angle between the mean planes of the cyclohexane and 1,3-dithietane rings is 9.1 (3)°. Short intramolecular S⋯O contacts occur [2.719 (5) and 2.740 (5) Å]. In the crystal, the molecules are linked by weak C—H⋯S hydrogen bonds and short [3.165 (5) Å] S⋯O contacts, forming (010) layers. The prevalence of these interactions is illustrated by an analysis of the three-dimensional Hirshfeld surface and by two-dimensional fingerprint plots.The title compound, C Ketene dithioacetals are useful intermediates in organic synthesis and have been used for the preparation of heterocyclic compounds  Å whereas the C8—S1 and C8—S2 bond lengths differ slightly . The molecule has local sC symmetry with a non-crystallographic mirror plane passing through atoms C8, C1, C2 and C5. The dihedral angle between the cyclohexane  and dithietane rings is 9.1 (3)° and short intramolecular S1⋯O2 [2.719 (5) Å] and S2⋯O1 [2.740 (5) Å] contacts are observed ed Fig. 1.3.b-axis direction. The molecules are linked by C5—H5A⋯S2 hydrogen bonds (Table 1ii  contacts, forming (010) layers a. A contribution of 30.7% was found for the H⋯O/O⋯H interactions, representing the largest contribution; these contacts are represented by the spikes in the top left  and bottom right  of Fig. 4b. Interactions of the type H⋯H appear in the middle of the scattered points in the fingerprint plots with a pair of spikes at de + di = 2.5 Å and comprise 25.9% of the entire surface ; the van der Waals radius for this interaction is 2.4 Å, which means it is a weak interaction. The S⋯H/H⋯S contacts , which account for 23.8% of the Hirshfeld surface, are displayed on the fingerprint plot as a pair of long spikes at de + di = 2.7Å. This distance differs by 0.3 Å from the sum of the van der Waals radii, which means it is the strongest interaction present. The S⋯C/C⋯S  and S⋯O/O ⋯S  contacts are seen as pairs of spikes at de + di = 3.2 and 3.05 Å, respectively. These distances are shorter than the sums of the van der Waals radii of 3.5 and 3.32 Å, respectively. The C⋯O/O⋯C interactions make a contribution of 0.7% to the Hirshfeld surface , their interatomic distances (de + di = 3.3 Å) being larger than the sum of the van der Waals radius (3.22 Å), so this interaction is very weak in this structure. The fingerprint plot corresponding to C⋯H/H⋯C contacts  shows a fin-like distribution of points with the edges at de + di = 2.8 Å.The nature of the intermolecular interactions in (I)ot Fig. 3 shows rece Fig. 4c; the vts Fig. 4d, whichce Fig. 4h, theirts Fig. 4e shows 5.et al., 2016et al., 2002trans-2,4-bis(isopropyl)-2,4-bis[(2-methyl-1-thioxo)propylsulfanyl]-1,3-dithietane cyclohexane-1,3-dione -5,5-dimethyl-2- [3-(4- nitrophenyl)allylidene]cyclohexane-1,3-dione -2-[(E)-amino]cyclohexyl}isoindoline-1,3-dione  λmax, 335 nm (ɛ 18760); IR : 1640 (C=O), 1H NMR (CDCl3) δ (ppm): 4.35 , 2.52 , 1.97 ; 13C NMR (CDCl3) δ (ppm): 197.28 (CO),189.73 (C=C—S), 119.93 (C=C—S), 37.31 (CH2—CH2—CH2), 33.39 (CH2—S), 18.62 (CH2—CH2—CH2).Potassium carbonate  in DMF (50 ml) was well stirred at room temperature. To this mixture, cyclohexane-1,3-dione (0.1 mol) was added and the resultant solution stirred at room temperature for 20 min. Carbon disulfide  was then added in one lot. The reaction mixture was stirred and kept for 10 min at room temperature. Diiodomethane (0.12 mol) was added dropwise over 20 min and the reaction mixture stirred for 7 h at room temperature. Ice–water (500 ml) was added to the reaction mass, the solid was filtered and washed with water, dried and recrystallized from ethanol solution to give (I)7.Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details for the title compound are summarized in Table 310.1107/S2056989022009872/hb8028sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022009872/hb8028Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022009872/hb8028Isup3.cmlSupporting information file. DOI: 2211891CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


One hydronium ion is complexed with an ordered 18-crown-6 molecule with H2OH⋯OC distances of 1.90–2.19 Å, and another hydronium ion with a disordered 18-crown-6 molecule with distances of 1.85–2.36 Å.The structure of the title compound, [H 3O+·C2F6NO4S2−·C12H24O6 or [H3O+·C12H24O6][N(SO2CF3)2−], which is an ionic liquid with a melting point of 341–343 K, has been determined at 113 K. The asymmetric unit consists of two crystallographically independent 18-crown-6 molecules, two hydronium ions and two bis(trifluoromethanesulfonyl)amide anions; each 18-crown-6 molecule complexes with a hydronium ion. In one 18-crown-6 molecule, a part of the ring exhibits conformational disorder over two sets of sites with an occupancy ratio of 0.533 (13):0.467 (13). One hydronium ion is complexed with the ordered 18-crown-6 molecule via O—H⋯O hydrogen bonds with H2OH⋯OC distances of 1.90 (6)–2.19 (7) Å, and the other hydronium ion with the disordered crown molecule with distances of 1.85 (6)–2.36 (6) Å. The hydronium ions are also linked to the anions via O—H⋯F hydrogen bonds. The crystal studied was found to be a racemic twin with a component ratio of 0.55 (13):0.45 (13).The structure of the title compound, H The asymmetric unit contains two crystallographically independent ion-pairs –2.19 (7) Å, and the other hydronium ion with the disordered 18-crown-6 molecule with 1.85 (6)–2.36 (6) Å distances (Table 1via O—H⋯F hydrogen bonds with H2OH⋯F3C distances of 2.12 (4)–2.14 (6) Å, while the hydronium ion with the disordered crown exhibits a weak O—H⋯F interaction [H⋯F = 2.50 (4) Å].Hydronium·18-crown-6 bis(trifluoromethanesulfonyl)amide is an ionized form of ternary equimolar mixture of 18-crown-6, imide superacid and water, the molten salt of which is known as a hydronium solvate ionic liquid (m.p. 341 −343 K) with very strong Brønsted acidity  were used to correct the geometry of the disordered crown ether molecule and hydronium ion, and the displacement parameters of the disordered crown ether molecule.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314620001625/is4042sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314620001625/is4042Isup2.hklStructure factors: contains datablock(s) I. DOI: 1982024CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


R(8)22 geometry.Pairs of molecules related by inversion symmetry are linked by intermolecular C—H⋯F contacts with  25H18ClF2N5S, comprises almost co-planar fluorophenyl, methylthiazolyl, pyrazolyl and chlorophenyl rings with the second fluorophenyl ring almost perpendicular to this plane. One fluorophenyl group is disordered over two components of occupancy ratio 0.767 (10):0.233 (10) related by a 24.2 (8)° twist. In the crystal, two molecules related by inversion symmetry are linked by a pair of C—H⋯F contacts in an R(8)22 geometry.The molecule of the title compound, C Fluorophenyl group E is disordered over two components with an occupancy ratio of 0.767 (10):0.233 (10) and related by a twist of 24.2 (8)°.The molecule of the title compound Fig. 1 includesA–D are close to coplanar with twist angles A/B, B/C and C/D of 4.76 (10)°, 6.51 (11)° and 10.46 (11)° respectively. Ring E is almost perpendicular to A–D with a C/E twist angle of 72.66 (3)° for the major component of E.Rings R(8)22 geometry to form a dimer. The pyrazolyl and fluorophenyl rings of neighbouring molecules are almost parallel with a centroid-to-centroid distance of 3.6510 (13) Å.In the crystal structure, two molecules related by inversion symmetry are linked by a pair of C—H⋯F contacts Table 1 with R, N′-(4-fluorophenyl)-2-oxopropanehydrazonoyl bromide , and triethylamine  in anhydrous ethanol (20 ml) was stirred for 2 h under reflux. The solid obtained on cooling was collected by filtration, washed with ethanol, dried and recrystallized from dimethylformamide solution to give colourless crystals of the title compound in 86% yield , m.p. 243°C, IR : 1590 (N=N), 1625 (C=C), 1650 (C=N).A mixture of 3-(4-chlorophenyl)-5-(4-fluorophenyl)-4,5-dihydro-1SHELXL, e.s.d. = 0.01 and 0.02 Å) and Uij components of disordered atoms’ ADPs were restrained to be similar to each other if within 2.0 Å distance . Refinement gave an occupancy ratio of 0.767 (10):0.233 (10) for the two components related by a twist of 24.2 (8)°.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314620007002/zl4041sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314620007002/zl4041Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620007002/zl4041Isup3.cmlSupporting information file. DOI: 2005280CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compounds show different packing motifs including chains mediated by N—H⋯N and N—H⋯O hydrogen bonds. viz. N′-[(E)-pyridin-3-ylmethylidene]thiophene-2-carbohydrazide, C11H9N3OS, (I), N′-[(E)-pyridin-2-ylmethylidene]thiophene-2-carbohydrazide, C11H9N3OS, (II), N-methyl-N′-[(E)-pyridin-2-ylmethylidene]thiophene-2-carbohydrazide, C12H11N3OS, (III) and N′-[(E)-pyridin-2-ylmethylidene]-2-(thiophen-2-yl)ethanohydrazide, C12H11N3OS, (IV) are described. The dihedral angles between the thiophene ring and the pyridine ring are 21.4 (2), 15.42 (14), 4.97 (8) and 83.52 (13)° for (I)–(IV), respectively. The thiophene ring in (IV) is disordered over two orientations in a 0.851 (2):0.149 (2) ratio. Key features of the packing include N—H⋯Np (p = pyridine) hydrogen bonds in (I), which generate C(7) chains propagating in the [001] direction; N—H⋯Np links also feature in (II), but in this case they lead to C(6) [001] chains; in (IV), classical amide (C4) N—H⋯O links result in [010] chains; in every case adjacent molecules in the chains are related by 21 screw axes. There are no classical hydrogen bonds in the extended structure of (III). Various weak C—H⋯X  interactions occur in each structure, but no aromatic π–π stacking is evident. The Hirshfeld surfaces and fingerprint plots for (I)–(IV) are compared.The crystal structures of four thiophene–carbohydrazide–pyridine derivatives,  The oxygen atom of the carbonyl group and the sulfur atom of the thiophene ring lie on the same side of the molecule [S1—C4—C5—O1 = −4.9 (6)°] whereas atom N3 of the pyridine ring lies on the opposite side. The dihedral angle between the thiophene and pyridine rings is 21.4 (2)° and the largest twist in the molecule occurs about the C6—C7 bond [N2—C6—C7—C8 = −11.8 (7)°]. The N1—N2 bond length of 1.384 (5) Å in (I)et al., 2016cIn (I)E configuration and C5—N1—N2—C6 = 173.74 (19)° but unlike (I)In (II)N-methylated derivative of (II)E configuration and C5—N1—N2—C7 = 179.40 (12)°. As with (II)et al., 2020Compound (III)et al., 2016cE and C6 and C7 are close to anti about the N—N bond [C6—N1—N2—C7 = −177.90 (14)°]. The dihedral angle between the aromatic rings (major disorder conformation for the thiophene moiety) in (IV)In (IV)3.p (p = pyridine) hydrogen bonds: in the former, these links generate [001] C(7) chains 1 screw axis but here the graph-set motif is C(6). The packing for (IV)C(4) amide N—H⋯O hydrogen bonds p link arising from the N-methyl group. The structures of (I)X  interactions although these are presumably very weak, given their H⋯X lengths.Geometrical data for the directional intermolecular interactions in (I)–(IV) are listed in Tables 1ns Fig. 5, with adds Fig. 7 leading t⋯πp  = 4.046 (2) Å (slippage = 1.546 Å) for (I)t⋯πp = 4.0509 (12) Å (slippage = 1.929 Å) for (II)t⋯πp = 4.7831 (9) Å for (III)t⋯πp = 4.643 (2) Å for (IV)The shortest aromatic ring centroid–centroid separations in these structures are πCrystalExplorer  show the expected red spots (close contacts) in the vicinities of the various donor and acceptor atoms.In order to gain more insight into these different packing motifs, the Hirshfeld surfaces and fingerprint plots for (I)–(IV) were calculated using  al. 2019. The HirThe fingerprint plots for (I)–(IV) decomposed into the different percentage contact types Table 5 show tha4.et al., 20162—C(=O)—NH—N=CH—Q sequence. None of these structures features a pyridine ring in the ‘Q’ position.A survey of the Cambridge Structural Database l. 2016a and Card al. 2014, respect6.SHELXL were used for the Uij values of equivalent atom pairs  and a SAME card was used to restrain the nearest-neighbour and next-nearest-neighbour bond distances in the two disorder components to be equal with standard deviations of 0.02 and 0.04 Å, respectively. The N-bound H atoms in (I)Uiso(H) = 1.2Ueq(N). All C-bound H atoms were located geometrically (C—H = 0.95–0.99 Å) and refined as riding atoms with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(methyl C). The methyl group in (III)Crystal data, data collection and structure refinement details are summarized in Table 610.1107/S2056989022005151/zl5030sup1.cifCrystal structure: contains datablock(s) I, II, III, IV, global. DOI: 10.1107/S2056989022005151/zl5030Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022005151/zl5030IIsup3.hklStructure factors: contains datablock(s) II. DOI: 10.1107/S2056989022005151/zl5030IIIsup4.hklStructure factors: contains datablock(s) III. DOI: 10.1107/S2056989022005151/zl5030IVsup5.hklStructure factors: contains datablock(s) IV. DOI: Click here for additional data file.10.1107/S2056989022005151/zl5030Isup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022005151/zl5030IIsup7.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022005151/zl5030IIIsup8.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022005151/zl5030IVsup9.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989022005151/zl5030sup10.docxHirshfeld surfaces. DOI: 2172437, 2172436, 2172435, 2172434CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound is an diiodo Schiff base molecule under investigation for possible antimicrobial activity as well as for a ligand for medicinal activity. 20H14I2N2O2, a diiodo-Schiff base, crystallizes in space group Pbca with one molecule per asymmetric unit. The molecular structure reveals two intramolecular O—H⋯N hydrogen bonds that give the molecule a twisted structure with non-coplanar rings. In the crystal structure, the molecular packing is stabilized by π–π stacking, hydrogen- and halogen-bonding  interactions.The title compound, C E,1′E)-bis(methanylylidene)}bis(4-iodophenol) (I)  covalently bound through the imine C atoms, C7 and C14 respectively, to I1—Ar(O1—H1) and I2—Ar(O2—H2) rings , and 39.37 (5)° versus I2—Ar(O2—H2)] phenyl]salicylaldimine  to I2—Ar(O2—H2) ring interactions  to T  repeating pattern with the I1 and I2 atoms of the I1—Ar(O1—H1) and I2—Ar(O2—H2) rings interdigitated along the c-axis direction  consists of a central ring (C8–C13) with gs Fig. 1. Two intgs Fig. 1, O1—H1⋯N)] Fig. 1. The intns Fig. 2. This rens Fig. 2. The addns Fig. 2. Along ton Fig. 3.o-phenylenediamine , and the reaction mixture brought to reflux with vigorous stirring for 2 h. Upon cooling, the title compound (I) precipitated as an orange solid, and was filtered, washed with ethanol and dried under vacuum. Crystals of (I) suitable for single-crystal X-ray diffraction were grown from acetone layered with hexane. Yield: 4.37 g (83%), m.p. 212–214°C. 1H NMR  δ 8.54 , 7.73–7.54 , 7.37 , 7.22 , 6.84 . +: 568.9; observed: 568.8.To a solution of 2-hydroxy-5-iodobenzaldehyde  in ethanol (200 ml) was added an ethanol (10 ml) solution of Crystal data, data collection and structure refinement details of (I) are summarized in Table 210.1107/S2414314622008951/gg4010sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622008951/gg4010Isup2.hklStructure factors: contains datablock(s) I. DOI: 2205660CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


It crystallizes in the monoclinic space group P21/n.A dual emissive fluorescent substituted benzocarbazole moieties and carbonyl–carbonyl interactions between the two acetyl groups.The crystal of the title compound, C We obtained N-acetyl carbazole 2 in quantitative yield utilizing Buchwalds’ method by treatment of diphenylphenanthrene 1 as a substrate in the presence of Pd(OAc)2 (10 mol %), NaOAc (1.0 equiv.), Cu(OAc)2 (2.0 equiv.) and powdered molecular sieves in toluene under oxygen at 393 K for 24 h. Single crystals of 2 were grown from the a mixture of hexanes and DCM (v/v = 1:1) at room temperature by slow thermal evaporation.In order to obtain the benzocarbazole, which are 22.2 (1), 25.7 (2)° and 50.8 (2), 59.7 (2)°, respectively.In the structure of 3.2  to 4.553 (1) Å , acetyl–acetyl dipolar interactions of 3.459 (3) to 3.689 (3) Å , C—H⋯π interactions of 2.935 (2) to 3.314 (3) Å , and π–π interactions with centroid–centroid distances of 3.801 (2) to 5.672 (2) Å  between phenyl alkynyl moieties. Specifically, the crystal is stabilized by the phenyl groups of the alkynyl moiety, which interacts weakly with each other  through π–π stacking. Furthermore, the phenyl group also interacts with another neighboring phenyl moiety and with the phenyl alkynyl moiety through C—H⋯π interactions benzo[def]carbazoledichloromethane solvate , Pd(OAc)2 , Cu(OAc)2 , NaOAc  and powdered molecular sieves  were added under air and covered with a septum. The tube was evacuated and refilled with N2. Under a positive N2 pressure, toluene (2 mL) was added via a syringe followed by degassing under a weak vacuum to this tube, and it was refilled with O2 three times. The reaction mixture was sealed and stirred at 293 K for 24 h under an O2 atmosphere. After completion of the reaction, the solution was cooled to room temperature and diluted with ethyl acetate followed by filtration through a thin pad of Celite. The crude product was purified by flash chromatography (hexanes/EtOAc) on silica gel to afford N-acetyl benzo[def]carbazole 2. Crystals of the title compound were obtained by thermal evaporation of the pure compound from a 1:1 solution of dichloromethane and hexanes.To a dried reaction tube, phenanthrene 6.Uiso(H) = 1.2 or 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989022004509/ex2054sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022004509/ex2054Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022004509/ex2054Isup3.cmlSupporting information file. DOI: 2101657CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Z)-ethene-1,2-bis(diphenylphosphine) as well as its complex with PtII are described here. The structure of the phosphine sulfide features intramolecular π–π interactions and C—H⋯S hydrogen bonds, as well as intermolecular π–π and C—H⋯π interactions. The structure of the platinum(II) complex features intermolecular C—H⋯Cl and C—H⋯S hydrogen bonds.The crystal structures of the disulfide derivative of ( Z)-bis(diphenylphosphine sulfide), C26H22P2S2 (I), along with its complex with PtII dichloride, dichloridoplatinum(II), [PtCl2(C26H22P2S2)] (II), are described here. Compound I features P=S bond lengths of 1.9571 (15) and 1.9529 (15) Å, with a torsion angle of 166.24 (7)° between the two phosphine sulfide groups. The crystal of compound I features both intramolecular C—H⋯S hydrogen bonds and π–π interactions. Molecules of compound I are held together with intermolecular π–π and C—H⋯π interactions to form chains that run parallel to the z-axis. The intermolecular C—H⋯π interaction has a H⋯Cg distance of 2.63 Å, a D⋯Cg distance of 3.573 (5) Å and a D—H⋯Cg angle of 171° (where Cg refers to the centroid of one of the phenyl rings). These chains are linked by relatively long C—H⋯S hydrogen bonds with D⋯A distances of 3.367 (4) and 3.394 (4) Å with D—H⋯A angles of 113 and 115°. Compound II features Pt—Cl and Pt—S bond lengths of 2.3226 (19) and 2.2712 (19) Å, with a P=S bond length of 2.012 (3) Å. The PtII center adopts a square-planar geometry, with Cl—Pt—Cl and S—Pt—S bond angles of 90.34 (10) and 97.19 (10)°, respectively. Molecules of compound II are linked in the crystal by intermolecular C—H⋯Cl and C—H⋯S hydrogen bonds.The crystal structures of ( Unfortu2.I was solved in the orthorhombic space group P212121. The molecular structure of this compound is shown in Fig. 2I has P=S bond lengths of 1.9571 (15) and 1.9529 (15) Å, P—C bond lengths that range from 1.804 (4) to 1.824 (4) Å and a C=C bond length of 1.338 (5) Å. The P=S bonds are oriented in opposite directions with a S1—P1—P2—S2 torsion angle of 166.24 (7)°. The τ4 descriptor for fourfold coordination around both phosphorus atoms P1 and P2 is 0.94, indicating a near tetrahedral geometry of the phosphine sulfide groups  and 3.360 (4) Å with D—H⋯A dihedral angles of 113 and 116°, respectively (Table 1D⋯A distances of 3.367 (4) and 3.394 (4) Å with D—H⋯A dihedral angles of 113 and 115°, respectively. The Flack parameter for this structure is −0.10 (5)  and 97.19 (10)°, respectively . The τ4 descriptor for fourfold coordination around the PtII center is 0.05, indicating a nearly perfect square-planar orientation of the sulfur and chlorine atoms around the metal  to 1.816 (9) Å, with a C=C bond length of 1.312 (18) Å. The τ4 descriptor for fourfold coordination of the phosphorus atom P1 is 0.91, indicating a slightly distorted tetrahedral geometry of the groups bonded to this atom, and that this tetrahedron is more distorted than what was observed for compound I.For the Pt3.I are held together in the crystal by intermolecular π–π and C—H⋯π interactions  Å and a D—H⋯Cg angle of 171° (Cg is the centroid of the C15–C20 ring). Together, these intermolecular π–π and C—H⋯π interactions link the molecules into chains that propagate parallel to the z-axis  and 3.561 (5) Å with D—H⋯A angles of 155 and 135°, respectively. These hydrogen-bonding interactions occur between the supramolecular chains of compound I.Molecules of compound s Table 1. Ring C9is Fig. 5. Two potII are held together by C—H⋯Cl  Å with a D—H⋯A angle of 141° . Sulfur atom S1 hosts the other intermolecular hydrogen bond with atom C3(H3) (symmetry code: x + y + z + D⋯A distance of 3.538 (9) with a D—H⋯A angle of 133°. The intermolecular C—H⋯Cl interactions form chains of compound II that run parallel to the z-axis. These chains are then linked into a three-dimensional network through the intermolecular C—H⋯S hydrogen bonds.Molecules of compound 4.et al., 2016I resulted in 17 hits. The majority of these hits were metal–ligand complexes, where the ligand was a triazole ring bearing two diphenylphosphine sulfide groups. Crystal structures of this ligand bonded to copper(II), zinc(II), palladium(II), and cadmium(II) were reported  and elemental sulfur  were combined in a round-bottom flask and dissolved in tetrahydrofuran (5 mL). The reaction mixture was stirred for three h at room temperature. The solvent was removed under reduced pressure to give a white, gelatinous solid. The crude product was recrystallized from benzene (5 mL) at 333 K and isolated by vacuum filtration with a Hirsch funnel to give a white solid. Analysis of the solid by 31P NMR (CDCl3) showed that the target compound I was present along with trans-dppeS2 and unreacted starting material. Single crystals of compound I grew serendipitously upon slow evaporation of this solution. 31P NMR : Compound I: 32.3 ppm; trans-dppeS2: 36.6 ppm; cis-dppe: −22 ppm.Compound II: Equimolar amounts of compound I  and Pt(PhCN)2Cl2  were combined in a small vial and dissolved in 1 mL CDCl3. Crystals of compound II formed serendipitously via slow evaporation of the solvent.Compound 6.I and II, all hydrogen atoms bonded to carbon atoms were placed in calculated positions and refined as riding: C—H = 0.95–1.00 Å with Uiso(H) = 1.2Ueq(C) for vinylic and aromatic hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989022011847/pk2674sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989022011847/pk2674Isup4.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022011847/pk2674IIsup5.hklStructure factors: contains datablock(s) II. DOI: 1481532, 2226172CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Heterodimers between nearly identical molecules are connected via three hydrogen bonds from benzylic and ester methylene groups to phosphonate. The dimers form chains along the a-axis direction, stabilized by C—H⋯O bridges.The title compound was prepared in three steps from  12H17I2O3P, was prepared in three steps from p-xylene. Heterodimers between nearly identical molecules are connected via three hydrogen bonds from benzylic and ester methylene groups to phosphonate. The dimers form chains along the a-axis direction, stabilized by C—H⋯O bridges.The title compound, C The A,B dimers are connected via three slightly bent C—H⋯O hydrogen bridges: C7A—H7A⋯O9B , C14A—H14B⋯O9B , and C11B—H11D⋯O9A . Three further C—H⋯O bridges connect neighbouring dimers to form chains along the a-axis direction  Å 157.9°, B shifted −1 along a], C7B—H7C⋯O9A  and C14B—H14D⋯O9A .In a project focusing on phenylenevinylene emissive materials  I, global. DOI: 10.1107/S2414314621006544/bt4116Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621006544/bt4116Isup3.cmlSupporting information file. DOI: 2091488CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the original publication , referenFigure 1. Frequency of use of A. rhizogenes strains in the world: 1—ATCC15834; 2—A4+ATCC43057; 3—LBA9402; 4—R1000; 5—K599+NCPPB2659; 6—NCIB8196; 7—R1601; 8—C58C1; 9—NCPPB1855; 10—MAFF301724; 11—A4T; 12—TR7; 13—A4RS; 14—ARqual; 15—TR101; 16—ATCC11325; 17—1334; 18—TR105; 19—MSU440; 20—MTCC532; 21—HRI; 22—LMG150; 23—A13; 24—R1600 (this is a modified figure from ref. [68]).Biomics2015, 7, 70–120.Newly added reference [68] should read: Kuluev, B.R.; Vershinina, Z.R.; Knyazev, A.V.; Chemeris, D.A.; Baymiev, A.K.; Chumakov, M.I.; Baymiev, A.K.; Chemeris, A.V. Plant hairy roots are important instrumentation for researchers and powerful phytochembiofactory for manufacturers. With this correction, newly added reference [68] and the order of some references has been adjusted accordingly.The authors would like to apologize for any inconvenience caused to the readers by these changes. The original article has been updated.


The morpholine ring in the cation adopts a chair conformation. The structure is stabilized by C–H⋯O, O—H⋯O, O—H⋯N and N—H⋯O hydrogen-bonding interactions and π–π stacking. The intermolecular interactions of the synthesized compound were quantified by Hirshfeld surface analysis.The title compound was synthesized  6H15N2O+·C6H2N3O7−·H2O, was synthesized via slow evaporation of an aqueous solution of picric acid with the substituted morpholine base and crystallized with one cation (C6H15N2O)+, one anion (C6H2N3O7)− and a water molecule in the asymmetric unit. The morpholine ring in the cation adopts a chair conformation. The structure is stabilized by C—H⋯O, O—H⋯O, O—H⋯N and N—H⋯O hydrogen-bonding interactions and π–π stacking. The intermolecular interactions of the synthesized compound were quantified by Hirshfeld surface analysis.The title compound, C All three protons of the NH3+ group are involved in hydrogen bonding. The cation forms a strong charge-assisted hydrogen bond N5—H5A⋯O1  with the picrate anion, while H5C interacts with O9 from the solvating water molecule [D⋯A = 2.741 (2) Å] and H5B is involved in a bifurcated hydrogen bond with O5 from a neighbouring picrate anion  and O9 from other water molecule , respectively. Additionally, the two protons of the water molecule interact with a picrate anion or the nitrogen atom of the morpholinyl moiety . Further geometric details of these hydrogen bonds can be found in Table 1The title compound crystallizes in the triclinic up Fig. 1 with twoup Fig. 1. The asypara-bound nitro group is nearly coplanar with the plane of the benzene ring [dihedral angle of −1.0 (2)°] and two ortho-oriented nitro groups are, probably as a result of repulsion with the phenolic oxygen atom, twisted from the ring plane by −51.9 (2) and 43.8 (2)°. It has been mentioned previously that the nitro groups of the picrate anion play an important role in stabilizing the crystal packing via weak coulombic interactions , C10—H10B⋯O6 and C12—H12A⋯O2 non-classical hydrogen bonds  and 4.0303 (19) Å, respectively, for the rings related by symmetry operations 1 − x, 1 − y, 2 − z and 2 − x, 1 − y, 2 − z. Finally, a centrosymmetric twelve-membered ring [(picrate)O−⋯H—N—H⋯O—H]2 with a third order graph set Fig. 3s Table 1. Severalup Fig. 5. Furtheral Fig. 6.CrystalExplorer 21.5  Hirshfeld surface of the title compound mapped over the limits −0.6471 to 1.3714 a.u. with close contacts to neighboring molecules is shown in Fig. 7et al., 2016Analysis of the Hirshfeld surface and the associated two-dimensional fingerprint plot for 2-(morpholinyl)ethylammonium picrate monohydrate was performed with de and di represent the distances from a point on the Hirshfeld surface to the nearest atoms outside and inside the surface, respectively morpholinium] tetrakis[(μ3-phosphito)trizinc(II)] hemihydrate morpholinium] tetrakis(μ-iodo)tetrakis(iodo)dilead(II)] and : 3384 (O—H), 2905 (NH3), 3110 (C—H), 1382 (CH2), 993 (C—O); 1H NMR : 8.831 , 3.63 , 3.03 , 2.58 , 2.46 . A suitable single crystal of 2-(morpholinyl)ethylammonium picrate monohydrate was selected for X-ray diffraction studies.2-(Morpholinyl)ethylammonium picrate monohydrate was synthesized by mixing one mole of 4-(2-ammonioethyl)morpholine and one mole of picric acid in double-distilled water at about 303 K. The solution was then allowed to evaporate at room temperature, which yielded yellow plate-like crystals of 2-(morpholinyl)ethylammonium picrate monohydrate. The reaction scheme is shown in Fig. 96.Uiso(H) = 1.2 Ueq(C). The acidic protons were localized from the residual electron-density map and refined with distance restraints (0.82 Å for O—H and 0.86 Å for N—H) and Uiso(H) = 1.2Ueq(N) and 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989022011409/jq2022sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022011409/jq2022Isup3.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022011409/jq2022Isup3.cmlSupporting information file. DOI: 2222322CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


S-(Pyridn-2-yl) benzothioesters are presented with varying para-phenyl motifs . These structures presented are the first in their class. Distinct changes are observed in the interaction types present in the crystal lattice as a direct result of the electronic influence of the para-phenyl motif.The structures of three  S-(pyridin-2-yl) benzothioesters with varying para-phenyl substituents are presented, namely, S-(pyridin-2-yl) 4-nitrobenzothioate , S-(pyridin-2-yl) 4-methylbenzothioate  and S-(pyridin-2-yl) 4-methoxybenzothioate . This class of compounds are used in the mono-acylation of pyrrolic species to yield multifunctional tetrapyrroles. The structures presented herein are the first of their compound class. The dominant interactions present in this series are π–π stacking and C—H⋯O interactions, and as the para-phenyl motif changes from electron withdrawing  to electron donating , changes are observed in the interactions present in the crystal packing, from predominant π–π stacking in 1 to exclusively C—H⋯O/N interactions  in 3.The crystal structures of three  Each molecular structure shows an S-(pyridin-2-yl) benzothioate where the para-phenyl motif is modified, from NO2 in 1, CH3 in 2, and OCH3 in 3. All of the groups utilized herein are found extensively in the field of tetrapyrroles.The single-crystal XRD structures of title compounds 3 Figs. 2–4 ▸ ▸, 1–3, the substituted phenyl moieties are all essentially planar with the pyridine ring twisted relative to this plane. This is seen in the plane normal to plane normal angle and the torsion angle described by C8—S1—C6—N1. The twist of the methanethioate moiety to the phenyl ring also describes the change in the angle of the rings to each other. These values are shown in Table 1In all structures 1 . Furthermore, considering the respective previously determined Hammett constants, it is observed that the most electron donating is the OCH3 group in 3 (σp = −0.27), with 2 (CH3) lying somewhere in between (σp = −0.17)  and 3.371 (5) Å]. The pyridine N1 is also an acceptor to the phenyl C12-H [D⋯A = 3.315 (5) Å]. The nitro group is a dual acceptor with interactions between O18 and one pyridyl C3-H [D⋯A = 3.396 (5) Å] and also a bifurcated interaction between O17 and phenyl C14-H and C15-H .Compound s Table 2 to the c2 presents C—H⋯N-paired dimers between the H6-pyridyl protons C2-H2 and N1  and a C16-H⋯O9 interaction [D⋯A = 3.460 (2) Å].Compound 3 presents a multitude of non-classical hydrogen-bonding interactions, of the C—H⋯Ocarbonyl and the C—H⋯Npyridyl type (Table 4D⋯A = 3.2566 (15) and 3.4270 (16) Å, respectively]. There is another bifurcated hydrogen-bond interaction between the pyridine N1 and C11 and C12 , linking the molecules head to tail. The methoxy groups form C17-H⋯O16 interactions [D⋯A = 3.4475 (17) Å], comprising a supramolecular synthon linking two molecules together. The methoxy oxygen O16 is further linked by a phenyl C14-H⋯O16 interaction [D⋯A = 3.3340 (15) Å].Compound e Table 4. The car1 and 2. Weak dimeric offset π–π stacking is observed in 1 with columns of anti-parallel non-interacting molecules when viewed normal to (001)  x, y, −1 + z; x, y, 1 + z] is 3.850 (3) Å with a slippages of 1.823 and 1.856 Å, respectively, and angles between planes of 0.0 (2)°. In 2, π-stacking occurs only through phenyl ring pairs with the closest centroid–centroid distance being 3.8783 (11) Å, a slippage of 1.575 Å, and an angle between planes of 0.03 (9)°, as seen normal to the (011) plane. In 3 there is no relevant π–π stacking, with the closest centroid–centroid distance being 4.0847 (7) Å, with a slippage of 2.042 Å and an angle between the planes of 5.14 (6)°.π–π stacking is evident in both 1) Fig. 6. The clo4.et al., 2016S-phenyl benzothioate . The distinct C—H⋯N interactions seen particularly in 3 do not exist in the phenyl homologue.A search in the Cambridge Structural Database benzothioate benzothioate  benzene-1,4-dicarbothioate -5.1, 2, and 3 were synthesized following the reported procedure  in a solution of CH2Cl2 was added dropwise over 0.5 h to a stirring solution of 2-mercaptopyridine  in CH2Cl2. The solution was left to stir for a further 2 h at room temperature. Throughout the addition processes, minor exotherms were noted, particularly for 1. The solution was diluted with the same volume again of CH2Cl2, and the solution was washed with NaOH (2 M), water, brine, and the organic layer then dried (MgSO4). Excess solvent was removed under reduced pressure and the title compounds were purified in the following ways: for 1, crystals were generated via hot recrystallization from ethyl acetate, and for 2 and 3, crystals were generated via precipitation from diethyl ether and hexanes. Compound 1 was yielded in 69%, with yields for 2 and 3 comparable to those previously reported .1:Analytical data for 1H NMR  δ = 8.66–8.68 , 8.31 , 8.14 , 7.77–7.81 , 7.68–7.70 , 7.33–7.37 ; 13C{1H} NMR : δ = 188.3, 150.9, 150.3, 141.3, 137.7, 130.9, 128.7, 124.3, 124.2 ppm; RF = 0.58 ; m.p. = 427–429 K. Multiple attempts have been made to obtain a molecular ion peak via ESI–MS and all have been unsuccessful.6.Uiso(H) = 1.2–1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989023001056/yz2028sup1.cifCrystal structure: contains datablock(s) 1, 2, 3, global. DOI: 10.1107/S2056989023001056/yz20281sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989023001056/yz20282sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S2056989023001056/yz20283sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989023001056/yz20281sup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023001056/yz20282sup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989023001056/yz20283sup7.cmlSupporting information file. DOI: 10.1107/S2056989023001056/yz2028sup8.pdf1H, 13C, and 1H-13C-HSQC NMR spectra of compound 1, along with overlayed aromatic regions of the 1H NMR spectra of compounds 1, 2, and 3. DOI: 2239845, 2239844, 2239843CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the packing of the title compound, π–π, C—H⋯O, C—H⋯Br, and N—H⋯N interactions are present. 12H14BrN3O2, the pyrazole and benzene rings are nearly co-planar with a dihedral angle between the rings of 2.36 (5)°. In the crystal, inversion dimers linked by pairwise N—H⋯N hydrogen bonds generate R22(8) loops. The dimers are linked into a three-dimensional network by weak aromatic π–π stacking interactions [centroid–centroid separation = 3.7394 (6) Å] and C—H⋯O and C—H⋯Br hydrogen bonds.In the title compound, C Very weak C2—H2⋯O2, C11—H11C⋯O2 and C12—H12B⋯O2 intramolecular interactions are present  = 3.7394 (6) Å, where Cg1 is the centroid of the pyrazole ring.In the extended structure, pairwise N3—H3if Fig. 2. The dimon Fig. 3 also occ5-Bromo-1H-indazol-3-amine (1): To a solution of 5-bromo-2-fluoro benzonitrile (1.0 mmol) in ethanol (20 ml) was added hydrazine hydrate (99%) (10.0 mmol). The reaction mixture was heated in sealed tube at 343 K for 4 h and progress of the reaction was monitored by TLC. The reaction mixture was concentrated to dryness. The brown-coloured solid was purified by recrystallization from ethanol solution to afford pale-yellow needles (90%), m.p. 407 K : To a solution of compound (1) (5.0 mmol) in dichloromethane (40 ml) was added DMAP (5.0 mmol). The reaction mixture cooled to 273 K and boc anhydride (5.0 mmol) was added. The reaction mixture was slowly warmed to room temperature and stirred for 15 h. Progress of the reaction was monitored by TLC. The reaction mixture was diluted with dichloromethane (50 ml) and washed with water and brine (25 ml), dried over anhydrous sodium sulfate and concentrated. The crude compound was purified by column chromatography  to afford a gummy solid, which solidifies as transparent crystals after 2 d (62%), m.p. 389 K.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314621006945/hb4388sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2414314621006945/hb4388Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314621006945/hb4388Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2414314621006945/hb4388Isup4.cmlSupporting information file. DOI: 2094667CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Water molecules donate O—H⋯O and accept N—H⋯O hydrogen bonds, forming helical arrangements.In the crystal, molecules of the title compound, C 24H20N2O4·H2O, crystallizes with half a molecule of 2--N′-[2-acetyl]acetohydrazide and half a water molecule in the asymmetric unit. In the crystal, molecules form planes parallel to (011). Two molecules are connected by water molecules via O—H⋯O and N—H⋯O hydrogen bonds.The title compound, C An ORTEP representation is shown in Fig. 1et al., 2020The asymmetric unit comprises half a molecule of 2--N′-[2-acetyl]acetohydrazide molecules are connected by a water molecule via O—H⋯O and N—H⋯O bonds  Fig. 2. Two 2- and 2-acetohydrazide  in dry ethanol (10 mL) was heated with stirring under reflux for 2 h. The solid formed on cooling to room temperature. It was collected by filtration, washed with ethanol, dried and recrystallized from dimethylformamide to give colourless crystals, m.p. > 300°C  I. DOI: 10.1107/S241431462100314X/bt4110Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S241431462100314X/bt4110Isup3.cmlSupporting information file. DOI: 2072979CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Thereby, the titanium atom is stabilized by the Lewis bases triphenylphosphine oxide ( 6H11)2N]3Ti—CH3 with the Lewis acid B(C6F5)3, followed by addition of the Lewis bases (C6H5)3PO and p-F—C6H4CN led to the complex salts tris(dicyclohexylamido)(triphenylphosphine oxide)titanium methyltris(pentafluorophenyl)borate toluene sesquisolvate, [Ti(C12H22N)3(C18H15OP)](C19H3F15B)·1.5C7H8, (1), and tris(dicyclohexylamido)(4-fluorobenzonitrile)titanium methyltris(pentafluorophenyl)borate toluene sesquisolvate, [Ti(C12H22N)3(C7H4FN)](C19H3F15B)·1.5C7H8, (2), both crystallizing with 1.5 equivalents of toluene solvent molecules. The Lewis acid–base adducts (1) and (2) can be described by dative donor bonds. The packing of the complex cations, anions and solvent molecules in the crystal structure is consolidated by an intricate three-dimensional network of non-classical C—H⋯F interactions. Disorder of some of the cyclohexyl groups and the toluene solvent molecules is observed.The reaction of [(C An intricate three-dimensional network of non-classical C—H⋯F interactions is formed in the crystals of (1) and (2), involving the C—H groups of both cations and solvent molecules as donors, and some F atoms of the [H3CB(C6F5)3]− anions as acceptors  and (2) were obtained from a saturated solution of toluene at 243 K.All reactions were carried out under a dry nitrogen atmosphere using Schlenk techniques or in a glove box. Solvents were dried according to standard procedures over Na/K alloy with benzophenone as an indicator and distilled under a nitrogen atmosphere. The cationic titanium complex was synthesized by reacting tris-(dicyclohexylamido)methyltitanium and tris-pentafluorphenylborane (Adler 5.1) shows disorder of one cyclohexyl residue (C25 to C30), located at N3, over two sets of sites, with refined site occupancy factors 0.87:0.13. Compound (2) shows disorder of two of the six cyclohexyl residues , located at the N1 and N3 atoms, respectively, with refined site occupation factors of 0.76:0.24 and 0.85:0.15. No restraints or constraints were applied during the refinement of this kind of disorder. All non-H atoms were refined anisotropically with the exception of the minor components of the disordered parts, which have been refined isotropically. In addition, the toluene solvent molecule in compounds (1) and (2) are disordered. In (1), one toluene molecule (C81–C87) is equally disordered over an inversion centre, and one (C74–C80) over two sets of sites, with refined site occupation factors of 0.764 (4):0.236 (4). In (2), one toluene molecule (C63–C69) is disordered over two sets of sites, the site occupancy was constrained to 0.5 for each component. The other toluene molecule (C70–C76) is disordered over two sets of sites with refined occupation factors of 0.29 (3):0.210 (3), both of which are additionally disordered over an inversion centre, resulting in a disorder over four sites.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989022007952/wm5649sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989022007952/wm56491sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989022007952/wm56492sup3.hklStructure factors: contains datablock(s) 2. DOI: 2195527, 2195526CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


HLA‐DRB5*01:01:01‐DRB1*15:01:01‐DQA1*01:02:01‐DQB1*06:02:01 haplotype.Multiple sclerosis (MS) is a chronic neurological disease believed to be caused by autoimmune pathogenesis. The aetiology is likely explained by a complex interplay between inherited and environmental factors. Genetic investigations into MS have been conducted for over 50 years, yielding >100 associations to date. Globally, the strongest linkage is with the human leukocyte antigen (HLA) DRB3, DRB4, DRB5, DRB1, DQA1, DQB1, DPA1 and DPB1 as well as their extended haplotypes and genotypes in 100 Swedish MS patients. Results were compared to 636 population controls.Here, high‐resolution sequencing of HLA was used to determine the alleles of HLA‐DR‐DQ genotypes were found. Three extended HLA‐DR‐DQ genotypes were found to be correlated to MS; HLA‐DRB5*01:01:01‐DRB1*15:01:01‐DQA1*01:02:01‐DQB1*06:02:01 haplotype together withThe heterogeneity in HLA associations with MS was demonstrated; among 100 patients, 69 extended HLA‐DRB4*01:01:01//DRB4*01:01:01:01‐DRB1*07:01:01‐DQA1*02:01//02:01:01‐DQB1*02:02:01,(A) HLA‐DRBX*null‐DRB1*08:01:01‐DQA1*04:01:01‐DQB1*04:02:01, and(B) HLA‐DRB3*01:01:02‐DRB1*03:01:01‐DQA1*05:01:01‐DQB1*02:01:01.(C) HLA‐DRB3*01:01:02 was considered protective against MS. However, when combined with HLA‐DRB3*01:01:02‐DRB1*03:01:01‐DQA1*05:01:01‐DQB1*02:01:01, this extended haplotype was considered a predisposing risk factor. This highlights the limitations as included with investigations of single alleles relative to those of extended haplotypes/genotypes.At the allelic level, HLA‐DRB5*01:01:01‐DRB1*15:01:01‐DQA1*01:02:01‐DQB1*06:02:01.In conclusion, with 69 genotypes presented among 100 patients, high‐resolution sequencing was conducted to underscore the wide polymorphisms present among MS patients. Additional studies in larger cohorts will be of importance to define MS among the patient group not associated with  Studies in African‐Americans, among whom the HLA‐DQB1*06:02 allele is not found on HLA‐DRB1*15:01 haplotypes, has attributed the risk of MS to HLA‐DRB1*15:01. Additional HLA‐DRB1‐DQB1 alleles and haplotypes associated with MS includeHLA‐DRB1*03:01‐DQA1*05:01‐DQB1*02:01  is the most common inflammatory disease affecting the central nervous system. Epidemiological findings suggest a gene–environment interaction, and the pathogenesis of MS is widely assumed to be of autoimmune origin  included blood samples collected from the Neurology Department of the Skåne University Hospital in Malmö. The MS diagnosis of the patients was validated by treating physician (Table n = 636) included in the HLA Next Generation Sequencing (NGS) analysis were obtained as previously described  and (B) LifeGene controls  .2.2DNA was extracted using Qiagen Blood Maxi Kit according to manufacturer's protocol and as previously described , and second occasion: LifeGene controls (n = 188)]; in the meantime the resolution of typing was improved; therefore, that some alleles are written as follows in the manuscript DRB4*01:01:01//DRB4*01:01:01:01.HLA NGS was performed by Scisco Genetics . Samples  were sent blindly to the investigators. HLA NGS makes use of PCR‐based HLA amplification and sequencing with Illumina MiSeq technology, as described in previous studies , as previously described .A reference haplotype with a similar frequency between the study groups was selected in HLA 6 haplotypes with positive (A) and 1 haplotypes with negative (B) association for MS patients in comparison to population controls were identified :HLA‐DRB3*02:02:01‐DRB1*03:01:01‐DQA1*05:01:01‐DQB1*02:01:01, (2) HLA‐DRB4*01:03:01‐DRB1*04:02:01‐DQA1*03:01:01‐DQB1*03:02:01, (3) HLA‐DRB4*01:03:01‐DRB1*04:03:01‐DQA1*03:01:01‐DQB1*03:02:01, (4) HLA‐DRB5*01:01:01‐DRB1*15:01:01‐DQA1*01:02:01‐DQB1*06:02:01, (5) HLA‐DRB5*02:02//DRB5*02:02:01‐DRB1*16:01:01‐DQA1*01:02:02‐DQB1*05:02:01 and (6) HLA‐DRBX*null‐DRB1*01:02:01‐DQA1*01:01:02‐DQB1*05:01:01.Identified haplotypes with higher frequency among MS patients compared to GP were (1) HLA‐DRB4*01:03:01‐DRB1*07:01:01‐DQA1*02:01//*02:01:01‐DQB1*03:03:02 (Table Identified haplotypes with lower frequency among MS patients compared to GP were (1) Based on the Haplo‐Score, 3.3HLA‐DRB3, DRB4, and DRB5 alleles, 47 different HLA‐DRB1 alleles, 23 different HLA‐DQA1 alleles, 24 different HLA‐DQB1 alleles, 14 HLA‐DPA1 and 30 HLA‐DPB1 alleles were found. The complete results and associations for all the different alleles found in the study are reported in Supplementary Table HLA‐DRB3*03:01:01 , HLA‐DRB1*03:01:01 , HLA‐DQA1*03:01:01 , HLA DQB1*02:01:01 , HLA‐DPA1*01:03:01  and HLA‐DPB1*02:01:02 . Based on the Haplo‐Score, 9 alleles with positive and 7 alleles with negative association for MS patients in comparison to population controls were identified , HLA‐DRB3*01‐DR3‐DQ2, while the association with HLA‐DR7‐DQ2 appear novel.From the present study, we first report that previously found HLA‐associations to MS, most prominently to HLA‐DPB1*104:01 (predisposing), HLA‐DQB1*03:01 and HLA‐DQB1*03:03 (protective), and HLA‐DRB1*14:04:01 (protective) . Due to high degree of polymorphism presented, we suggest that mechanistic studies would be necessary to fully determine the role of HLA‐DQB1*03:01 to risk and progression of MS.Here, we could not confirm recent allelic MS associations using high‐resolution sequencing to HLA‐DRB3*01:01:02 was considered protective against MS at the allelic level, the extended genotype, abbreviated HLA‐DR15‐DQ6‐DRB3*01‐DR3‐DQ2, was considered a predisposing risk factor. This highlights the limitations of studies of single alleles relative to studies of extended haplotypes and genotypes. We speculate that the shifting association for HLA‐DRB3*01:01:02 from protective to predisposing, could be related to mechanisms of epistasis. Previously, HLA‐DQA1*01:02 was demonstrated to increase risk of MS if found in trans position to the haplotype of HLA‐DR15‐DQ6  and two‐thirds of all patients (68 of 100) encompassed haplotypes of either HLA‐DR15‐DQ6, HLA‐DRB3*01‐DR3‐DQ2 or HLA‐DRB3*02‐DR3‐DQ2.Lastly, we report heterogeneity in HLA associations to MS given that, among 100 patients, 69 different extended HLA‐DR15‐DQ6 haplotype is consistently reported, both here and elsewhere, as the major genetic contributor to MS. Some suggestions of the presence of this extended haplotype at the age at onset  as compared to 6%  is of interest, complementary triggers and pathways of autoimmunity could be present. It cannot be excluded that environmental factors are different between MS patients negative for HLA‐DR15‐DQ6 but positive for HLA‐DR7‐DQ2. Studies in larger and diversified cohorts would be needed to define MS in this group of patients.The group of non‐HLA‐DRB1*03:01 allele has been associated with MS. An increased risk was reported when the HLA‐DRB1*03:01 allele is homozygous  among both patients and controls, which precluded computation of the other rare allele variants among the families that were used as templates (Lind et al., HLA‐DR15‐DQ6 patients.A weakness of our study was the fact that the It appears overly simplistic to characterize MS as having a single aetiology and pathogenesis. The heterogeneous clinical presentation, variable clinical course, inconsistency in genetic markers, unpredictable therapeutic response and diverse histopathological findings may be indicative of divergence in the demyelination pathways (Lucchinetti et al., HLA‐DR15‐DQ6.2.In summary, we have confirmed previous HLA associations to MS, while also offering plausible explanations to help guide future research. Using high‐resolution sequencing, we have highlighted the widespread polymorphisms as 69 distinct genotypes present among 100 Swedish MS patients and further studies in a larger number of patients will be needed to further delineate MS not associated with There are no conflicts of interest.Supplement MaterialClick here for additional data file.Supplement MaterialClick here for additional data file.