C(6) chains propgagating along [001].The title compound 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, weak N—H⋯O and C—H⋯F interactions, which form  21H23F2NO, 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 title compound, C Ramachandran et al., 2007et al., 2020Piperidin-4-one compounds have various biological properties and have applications as anti-viral, antitumor, and antihistaminic agents As part of our studies in this area, we now describe the synthesis and structure of the title compound, C1/cP2 with one molecule in the asymmetric unit  Å, θ = 6.56 (15)°, φ = 356.9 (14)°. The dihedral angles for the C1–C5/N1  piperidine (A), C6–C11 fluorophenyl (B) and C12–C17 fluorophenyl (C) rings are A/B = 65.50 (8), A/C = 73.87 (8) and B/C = 72.11 (8)°. The substituents on the piperidine ring adopt equatorial orientations with the keto oxygen atom being anti-clinal [O1—C3—C2—C1 = −124.44 (16)°]. The butyl group lies in a syn-periplanar orientation [O1—C3—C2—C18 = 0.7 (2)] while the fluorophenyl groups are both anti-clinal [N1—C5—C6—C7 = −148.28 (13) and N1—C1—C12—C17 = −75.42 (16)°]. The sum of the bond angles around N1 is 336.8°, which is consistent with sp3 hybridization for this atom it Fig. 1. In the C(6) chains (via the N—H⋯O bond) along [001]. Some longer C—H⋯O and C—H⋯F contacts are also present as well as a single weak C—H⋯π interaction n Table 1.CrystalExplorer17.5 . The curvedness of the HS can be used to divide the molecular surface into contact patches with each neighbouring molecule thereby using it to define a coordination number in the crystal .A Hirshfeld surface (HS) analysis  are the most important interactions , presumably because of the large hydrogen content of (I)de + di) < 1.19 Å. The pair of wings for the H⋯C/C⋯H contacts  is in the region 1.04 Å < (de + di) < 1.58 Å and includes the weak C—H⋯π interaction. The H⋯F/F⋯H contacts  are seen as a pair of wings in the region 1.04 Å < (de + di) < 1.38 Å. The wings for the H⋯O/O⋯H contacts  are in the region of 0.88 Å < (de + di) < 1.20 Å while the blunt wings in the plot for F⋯F contacts  are in the region 1.60 Å < (de + di) < 1.70 Å. The C⋯C contacts  make a negligible 0.1% contribution and are viewed as a dash pattern pointing diagonally left. The O⋯O contacts  make no contribution to the HS. The most significant of these contributions to the overall Hirshfeld surface are shown in Figure S3 in the supporting information.Two-dimensional fingerprint plots show the relative contributions of the various types of contacts to the Hirshfeld surface for (I)ns Fig. 4b, presuts Fig. 4f; 2.6% ts Fig. 4g make ats Fig. 4h make nWebMo Pro ° with respect to each other.A density functional theory (DFT) geometry-optimized calculation for (I)supplementary Table S2. Both the HOMO and HOMO−1 are localized largely on the piperidine ring. For the LUMO, LUMO+1 and LUMO+2, the orbitals are delocalized over the piperidine ring as well as both phenyl rings. The observed UV/vis absorption spectrum . The molar extinction coefficients, ∊, are 1.12 and 2.50 l mol−1 cm−1, respectively. We tentatively assign the first absorption band envelope at 256 nm to overlapping contributions from HOMO → LUMO (energy gap 5.71 eV), HOMO → LUMO+1 (5.83 eV) and HOMO−1 → LUMO (5.82 eV). The band at 216 nm is assigned to overlapping contributions from HOMO → LUMO+2 (5.89 eV), HOMO−1 → LUMO+1 (5.95 eV) and HOMO−1 → LUMO+2 (6.01 eV).The calculated energies (eV) for the frontier molecular orbitals are shown in Fig. 5um Fig. 6 shows twet al.. 2016et al., 2001t(3)-pentyl-r(2),c6)-diphenylpiperidin-4-one ,c(6)-diphenylpiperidin-4-one ,c(6)-bis(4-fluorophenyl)piperidin-4-one : found C 74.24, H 6.16, N 4.03; calculated C 73.45, H 6.75, N 4.08; melting point 381.5 K.A mixture of ammonium acetate , 4-fluorobenzaldehyde  and 2-heptanone  in distilled ethanol was heated first to boiling. After cooling, the viscous liquid obtained was dissolved in ether (200 ml) and shaken with 100 ml concentrated hydrochloric acid. The precipitated hydrochloride of 3-butyl-2,6-bis(4-fluorophenyl)piperidin-4-one was removed by filtration and washed first with a 50 ml mixture of ethanol and ether (1:1) and then with ether to remove most of the coloured impurities. The resulting yellowish base was liberated from an alcoholic solution by adding aqueous ammonia (15 ml) and then diluted with water (200 ml). Then, 1.0 g of the crude sample was dissolved in 100 ml of absolute alcohol, warmed until the sample dissolved, and 2.0 g of animal charcoal added in the resulting solution. The hot solution was filtered and the procedure repeated again. The filtered solution was left for 48 h and colourless prisms of (I)−1) (KBr): 3287 (νN—H), 3134, 2929, 2866 (νC—H), 1702 (νC=O), 1605, 1508 (νC=C), 793 (νC—Cl); 1H NMR : δ 7.01–7.45 , 4.04 , 3.68 , 2.67 , 2.56 , 2.0 (NH proton), 0.95–1.0 CH2(3), 1.09–1.15 CH2(2), 1.59–1.63 CH2(1), 0.74, ; 13C NMR : δ 129.16, 129.38, 128.18, 128.10, 115.64, 115.56, 115.43, 115.35 (aromatic carbon atoms), 138.52 and 137.64 (aromatic ipso carbon atoms), 66.33 (C2), 57.50 (C3), 208.7 (C4), 51.63 (C5), 61.08 (C6), 24.30 C18H2, 29.71 C19H2, 22.75 C20H2, 13.81 C21H3.FT–IR (cmUiso(H) = 1.2Ueq(carrier) or 1.5Ueq(methyl carrier) was applied in all cases.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020004636/hb7882sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020004636/hb7882Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020004636/hb7882sup3.docxTheoretical chemistry data and Hirshfeld figures. DOI: 1994539CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Hirshfeld surface and simultaneous TGA–DTA analyses are also describedThe molecular and crystal structure of bis, crystallizes with one half molecule in the asymmetric unit of the monoclinic unit cell. The complex adopts an octahedral coordination geometry with two mutually trans benzyl-2-(heptan-4-ylidene)hydrazine-1-carboxylate ligands in the equatorial plane with the axial positions occupied by N-bound thiocyanato ligands. The overall conformation of the molecule is also affected by two, inversion-related, intramolecular C—H⋯O hydrogen bonds. The crystal structure features N—H⋯S, C—H⋯S and C—H⋯N hydrogen bonds together with C—H⋯π contacts that stack the complexes along the b-axis direction. The packing was further explored by Hirshfeld surface analysis. The thermal properties of the complex were also investigated by simultaneous TGA–DTA analyses.The title centrosymmetric Ni The coordination chemistry of benzyl carbazate Schiff base complexes has gained importance not only from the inorganic point of view, but also because of their biological and thermal properties. In the course of our recent studies on such complexes, we reported the cobalt(II) complex of a Schiff base derived from benzyl carbazate and heptan-4-one with thiocyanates as the charge-compensating ligands °. Bond lengths and angles in the closely related Ni and Co complexes are generally similar, although the Ni1—N1 bond [2.1332 (12) Å] is significantly shorter here than the corresponding Co1—N11 and Co2—N21 vectors [2.206 (5) and 2.248 (6) Å respectively].The title compound, N⋯S1 and weaker C8—H8⋯S1 and C10—H10A⋯S1 hydrogen bonds, Table 1bc diagonal, Fig. 2B⋯S1 hydrogen bonds link adjacent molecules into rows along the b-axis direction, Fig. 3a, through C2—H2A⋯Cg3, C—H⋯π contacts, Fig. 4Cg3 is the centroid of the C3–C8 phenyl ring. These contacts combine to stack molecules of the complex in a regular fashion along the b-axis direction, Fig. 5In the crystal structure, atom S1 acts as a trifurcated acceptor forming N2—H21 were obtained using Hirshfeld surface analysis  and (b). Bold red circles on the Hirshfeld surfaces correspond to the N—H⋯S hydrogen bonds while the weaker C—H⋯S and C—H⋯π contacts appear as faint red circles. Fingerprint plots, Fig. 7Further details of the intermolecular interactions in 1. Simultaneous TGA–DTA analyses were recorded in air on a Perkin–Elmer SII Thermal Analyser over the temperature range 50–800°C. With the equipment used here, the TGA curve shows the temperature range but not the individual peak temperatures. However, peak temperatures can be seen in the DTA curve. In the first step of decomposition, the weight loss of 74% occurs over the temperature range 115–260°C (TGA). This corresponds to the loss of the Schiff base ligands to form NiII thiocyanate as an intermediate. This was marked by both endothermic (170°C) and exothermic peaks (190 and 210°C) in the DTA curve. As the thermal analysis was carried out under a dynamic flowing air atmosphere, the S and N atoms are oxidized to SO2 and NO2, while nickel ultimately forms nickel oxide. Similar decomposition processes have been observed in our recent wok on numerous similar complexes, see for example NHN=C(CH2)2 unit produced only two hits. One was our own report of the ligand benzyl 2-cyclopentylidenehydrazinecarboxylate -1-ethyl 8-methyl 7-(2-(benzyloxycarbonyl)hydrazono)oct-2-enedioate, 2·6H2O,  dissolved in 10 mL of doubly distilled water was added to this solution. The resulting blue solution was layered with heptan-4-one (dipropyl ketone) and the solution changed to a green colour. The final solution was left to evaporate at room temperature. After slow evaporation, bluish–green rhombus-shaped crystals suitable for X-ray diffraction analysis were collected, washed with doubly distilled water and air-dried.Equimolar amounts of ammonium thiocyanate  and benzyl carbazate  were dissolved in methanol (10 mL). Nickel nitrate, Ni and 3Ag2(F) →3Tg1(P) transitions, respectively, supporting the six-coordinate octahedral geometry around the NiII cation  spectrometer using tetramethylsilane as an internal reference. Chemical shifts are expressed in parts per million (ppm): 0.84–0.88 and 1.33–2.20 ppm: CH3 and CH2 groups, respectively; –OCH2 proton: 5.08 ppm; aromatic protons multiplets 7.29–7.34 ppm; NH: 9.882 ppm.The Simultaneous TGA–DTA analyses were recorded in air on a PerkinElmer SII Thermal Analyser over the temperature range 50-800°C.Uiso(H) = 1.2Ueq(N). All C-bound H atoms were refined using a riding model with d(C—H) = 0.95 Å, Uiso = 1.2Ueq(C) for aromatic 0.99 Å, Uiso = 1.2Ueq(C) for CH2 and 0.98 Å, Uiso = 1.5Ueq(C) for CH3 H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989020004260/vm2230sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020004260/vm2230Isup2.hklStructure factors: contains datablock(s) I. DOI: 1993291CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the complex molecule, the tetradentate ligand N1,N3-bis[methylene]-2,2-dimethylpropane-1,3-diamine coordinates to the FeII ion through the N atoms of the 1,2,3-triazole moieties and aldimine groups. Two thiocyanate anions, coordinating through their N atoms, complete the coordination sphere of the central ion. In the crystal, neighbouring molecules are linked through weak C—H⋯π, C—H⋯S and C—H⋯N interactions into a two-dimensional network extending parallel to (011). The intermolecular contacts were quantified using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing the relative contributions of the contacts to the crystal packing to be H⋯H (35.2%), H⋯C/C⋯H (26.4%), H⋯S/S⋯H (19.3%) and H⋯N/N⋯H (13.9%).The unit cell of the title compound, [Fe The average trigonal distortion parameters Σ = Σ112(|90 − φi|), where φi is the angle N—Fe—N′ , where θi is the angle generated by superposition of two opposite faces of an octahedron . The volume of the [FeN6] coordination polyhedron is 12.4 Å3.The Fens Fig. 1. The aveB⋯Cgi of 3.330 (3) Å  Å] with a thiocyanate anion. This, together with the C4—H4B⋯C27ii and C4—H4B⋯N10ii interactions [3.709 (3) and 3.617 (3) Å] involving the C≡N group of the anion, links the dimers into a supramolecular chain propagating parallel to [01iii = 3.603 (3) Å] and triazole groups [C19—H19A⋯N7iii = 3.311 (3) Å] of neighbouring complex molecules, forming a two-dimensional supramolecular array extending parallel to (011).Neighbouring complex molecules form dimers through double weak contacts C18—H181] Fig. 2. These cCrystal Explorer  to 1.8236 (blue) a.u. The pale-red spots symbolize short contacts and negative dnorm values on the surface correspond to the interactions described above. The overall two-dimensional fingerprint plot is illustrated in Fig. 3dnorm are shown for the H⋯H, H⋯C/C⋯H, H⋯S/S⋯H, and H⋯N/N⋯H contacts, and the two-dimensional fingerprint plots are presented in Fig. 4Hirshfeld surface analysis was performed and the associated two-dimensional fingerprint plots were generated using et al., 2016II thiocyanate complexes, derivatives of a 1,3-diaminopropanes and N-substituted 1,2,3-triazole aldehydes, viz. DURXEV, ADAQUU, ADAREF and solvatomorphs ADAROP and ADARUV 4(NCS)2] dissolved in a minimum amount of boiling methanol with a minimum amount of ascorbic acid. The formed yellow solution was slowly cooled to ambient temperature. The formed orange crystals were subsequently filtered off. Elemental analysis calculated (%) for C27H28FeN10S2: C, 52.94; H, 4.61; N, 22.87; S, 10.47; found: C, 52.88; H, 4.37; N, 22.40; S, 10.35. IR vKBr (cm−1): 1615 (C=N), 2071, 2115 (NCS).The ligand of the title compound was obtained Uiso(H) = 1.2–1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989020012608/wm5580sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020012608/wm5580Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020012608/wm5580Isup3.cdxSupporting information file. DOI: 2032292CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, centrosymmetric, eight-membered {⋯HNCS}2 synthons are formed by thioamide-N—H⋯S(thioamide) hydrogen bonds.The title hydrazine carbodithioate features an almost planar C 13H18N2OS2, is constructed about a central and almost planar C2N2S2 chromophore (r.m.s. deviation = 0.0263 Å); the terminal methoxybenzene group is close to coplanar with this plane [dihedral angle = 3.92 (11)°]. The n-butyl group has an extended all-trans conformation . The most prominent feature of the molecular packing is the formation of centrosymmetric eight-membered {⋯HNCS}2 synthons, as a result of thioamide-N—H⋯S(thioamide) hydrogen bonds; these are linked via methoxy-C–H⋯π(methoxybenzene) interactions to form a linear supramolecular chain propagating along the a-axis direction. An analysis of the calculated Hirshfeld surfaces and two-dimensional fingerprint plots point to the significance of H⋯H (58.4%), S⋯H/H⋯S (17.1%), C⋯H/H⋯C (8.2%) and O⋯H/H⋯O (4.9%) contacts in the packing. The energies of the most significant interactions, i.e. the N—H⋯S and C—H⋯π interactions have their most significant contributions from electrostatic and dispersive components, respectively. The energies of two other identified close contacts at close to van der Waals distances, i.e. a thione–sulfur and methoxybenzene–hydrogen contact  and between methylene-H atoms , are largely dispersive in nature.The title hydrazine carbodithioate, C The methoxybenzene ring forms a dihedral angle of 3.92 (11)° with the central residue indicating a close to co-planar relationship. The C9—O1—C6 —C7 dihedral angle of 176.9 (3)° indicates that the methoxy substituent lies almost in the plane of the benzene ring to which it is connected. The configuration about the C2=N2 imine bond [1.278 (3) Å] is E and this bond length is significantly shorter than the C1—N1 bond [1.330 (3) Å]; the N1—N2 bond length is 1.378 (3) Å. There is a large disparity in the C1—S1 [1.662 (3) Å] and C1—S2 [1.745 (3) Å] bond lengths, which correlate with significant double-bond character in the former; the C10—S2 bond length at 1.793 (3) Å is longer than each of these. The thione character of the C1—S1 bond is also reflected in the range of angles subtended at the C1 atom, which are systematically wider for those involving the thione-S1 atom, i.e. S1—C1—S2 [126.35 (16)°] and S1—C1—N1 [120.9 (2)°], cf. S2—C1—N1 [112.76 (19)°]. The thioamide-N—H and thioamide-S atoms have a syn disposition. Finally, the n-butyl group has an extended, all-trans conformation as seen in the S2—C10—C11—C12 [−173.2 (3)°] and C10—C11—C12—C13 [180.0 (4)°] torsion angles.The molecular structure of (I)via an eight-membered {⋯HNCS}2 synthon, the molecular packing is largely devoid of directional interactions  interactions, Fig. 2a), being the only other identified supramolecular association. Globally, chains pack without specific interactions between them, Fig. 2b). An analysis of the weak non-covalent contacts within and connecting chains is given in the Analysis of the Hirshfeld surfaces.With the exception of thioamide-N—H⋯S(thioamide) hydrogen bonding between centrosymmetrically related molecules, Table 1et al., 2019Crystal Explorer 17 a)–(e), respectively; the percentage contributions from the different interatomic contacts are summarized in Table 2b), a short interatomic H⋯H contact involving methylene-H10B with a symmetry-related mate  and occurring between supramolecular chains aligned along the a axis, is observed as a single peak at de + di ∼ 2.2 Å. In the fingerprint delineated into S⋯H/H⋯S contacts, shown in Fig. 6c), the pair of well-defined spikes at de + di ∼ 2.5 Å arise as a result of the prominent intermolecular N—H⋯S interaction. The points corresponding to S⋯H/H⋯S contacts involving the thione-S1 and methoxybenzene-H4 atoms, occurring within the supramolecular chain shown in Fig. 2a), albeit at nearly van der Waals separations , and reflected as an electrostatic interaction in the Hirshfeld surface plotted over the electrostatic potential of Fig. 4d) are at distances equal to or greater than the sum of van der Waals radii, the presence of characteristic wings is the result of the intermolecular methyoxy-C—H⋯π(methoxybenzene) contact. The points corresponding to interatomic O⋯H/H⋯O contacts illustrated in the corresponding fingerprint plot of Fig. 6e), also show a pair of forceps-like tips at de + di ∼ 2.8 Å, i.e. at van der Waals distances. The contribution from the other interatomic contacts summarized in Table 2The overall two-dimensional fingerprint plot for (I)Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep)  level of theory. The nature and strength of the intermolecular interactions in terms of their energies are quantitatively summarized in Table 3Eele, Edisp and Etot components, respectively; the radius of the cylinder is proportional to the magnitude of the interaction energies. This is reflected in the relatively thick red cylinders corresponding to the electrostatic interactions via the N—H⋯S hydrogen bonding in Fig. 7a) and the thick green cylinders corresponding to the strong dispersive interactions provided by the methyoxy-C—H⋯π(methoxybenzene) interactions in Fig. 7b).The pairwise interaction energies between molecules in the crystal of (I)6H4C(H)=NN(H)C(=S)SR. These are of the R = Me Reflecting the interest in the chemistry of hydrazine carbodithioates related to (I)S-butyldithiocarbazate (SBuDTC). An ethanolic solution (28 ml) of 4-methoxybenzaldehyde  was added directly to the SBuDTC in situ. This mixture was heated to 323 K with continuous stirring for 30 min. The yellow product (I)13H18N2OS2: C, 55.3; H, 6.4; N, 9.9; S, 22.7. Found: C, 55.9; H, 6.6; N, 9.8; S, 23.2. FT–IR (cm−1): 3120 ν(NH), 2927 ν(CH), 1600 ν(C=N), 1248 and 1107 ν(COC), 1017 ν(NN), 861 ν(CSS). MS: calculated m/z = 282; Found m/z = 282. 1H NMR : δ 13.11 , 8.15 , 6.97, 7.02, 7.61, 7.78 (ArH), 3.76 , 3.14 , 1.58 , 1.36 , 0.86 . 13C{1H} NMR : δ 196.96 (C=S), 146.87 (C=N), 161.90, 129.65, 126.36, 115.00 (ArC), 55.86 (OCH3), 33.19, 31.05, 22.10 (CH2), 14.07 (CH3). NMR data were measured on a JOEL ECX500 FT NMR spectrometer.In an ice-bath, carbon disulfide  was added dropwise to an absolute ethanol (35 ml) solution comprising KOH  and hydrazine hydrate . After 30 min, 1-bromobutane  was added. The solution was stirred at 278 K for 1 h to form Uiso(H) set to 1.2Ueq(C). The N-bound H atom was located in a difference-Fourier map but was refined with a N—H distance restraint of 0.86 (1) Å.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989020000328/hb7887sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020000328/hb7887Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020000328/hb7887Isup3.cmlSupporting information file. DOI: 1977066CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


V with the dihedral angle between the phthalazin-1-one and mesityl residues being 83.26 (4)°. Molecules assemble into a linear, supramolecular tape by phthalazinone-C6-C—H⋯O(sulfoxide) and π–π stacking interactions.The molecule in the title crystal has the shape of the letter  17H16N2O3S {systematic name: 2-[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–π 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 X-ray crystal structure of the title phthalazin-1-one derivative, C H)-one derivatives are a group of diazaheterobicycles that are noteworthy for their interesting medicinal applications. Thus, this class of compound has been reported to possess a wide variety of biological properties such as anti-diabetic , anti-inflammatory and analgesic -one-based drugs are in use -ones, have also been reported -one was described. In the present study, the title compound, 2-[sulfonyl]-1,2-dihydrophthalazin-1-one, (I)Phthalazin-1° for N1—S1—C1, involving the singly-bonded N1 and C1 atoms, to a wide 118.39 (6)°, for O1—S1—O2, involving the doubly-bonded sulfoxide-O1, O2 atoms. The organic residues lie to the opposite side of the molecule to the SO2 residue, forming dihedral angles of 67.35 (4)° [phthalazin-1-one with r.m.s. deviation = 0.0105 Å] and 49.79 (6)° [mesityl]. The dihedral angle between the organic residues of 83.26 (4)° indicates a close to orthogonal relationship. The N2—N1—C10—O3 torsion angle of −179.88 (12)° indicates a co-planar arrangement for these atoms, which allows for the close approach of the N2 and O3 atoms, i.e. 2.6631 (15) Å, suggestive of a stabilizing contact  Å and C10—N1 = 1.4003 (17) Å. In each of the C17=N2 [1.2911 (18) Å] and C10=O3 [1.2175 (15) Å] bonds, double-bond character is noted. The bond angles about the N1 atom are non-symmetric, with the endocyclic N2—N1—C10 angle of 126.97 (11) Å being significantly wider than the exocyclic N2—N1—S1 [113.93 (9) Å] and C10—N1—S1 [118.89 (8) Å] angles.The molecule of (I)6-C—H⋯O(sulfoxide) contacts, Table 1a). The π-stacking occurs between centrosymmetrically related phthalazinone rings, i.e. between the N2C4 and C6i rings with an inter-centroid distance = 3.5474 (9) Å, angle of inclination = 1.17 (7)° for symmetry operation (i) 1 − x, 1 − y, 2 − z. As shown in Fig. 2b), the tapes inter-digitate along the c-axis direction allowing for putative π-stacking between mesityl rings but, the inter-centroid separation is long at 4.1963 (8) Å. The assemblies shown in Fig. 2b) stack along the a-axis direction, again without directional interactions between them, Fig. 2c).The formation of a supramolecular tape sustained by phthalazinone-CCrystal Explorer 17 ,(b), the presence of diminutive red spots near methyl-C7 and benzene-H5 are indicative of intermolecular C—H⋯C contacts as C—H⋯π contacts are not preferred because of the V-shaped molecular geometry of (I)6 ring on the dnorm-mapped Hirshfeld surface in Fig. 3b) is indicative of short intra-chain C⋯C contacts [Table 2a)] and is consistent with the significant contribution from π–π stacking between centrosymmetrically related phthalazinone-N2C4 and C6 rings, encompassing connections between phthalazinone-C6 rings [3.6657 (9) Å with angle of inclination = 0.03 (7)°]. The involvement of the methyl-C8 atom in C—H⋯O [to provide links between the chains shown in Fig. 2b)] and C—H⋯C contacts, Table 2c). The blue and red regions corresponding to positive and negative electrostatic potentials, respectively, on the Hirshfeld surface mapped over electrostatic potential shown in Fig. 4In order to probe the interactions between molecules of (I) al. 2019. In addia)–(e), respectively; the percentage contributions from the different interatomic contacts to the Hirshfeld surfaces are summarized in Table 3A atoms, Table 2de + di ∼2.2 Å in the fingerprint plot delineated into H⋯H contacts, Fig. 5b). In the fingerprint plot delineated into O⋯H/H⋯O contacts illustrated in Fig. 5c), a pair of forceps-like tips at de + di ∼2.3 Å, indicate the intermolecular C—H⋯O interaction involving the phthalazinone-H12 and sulfoxide-O2 atoms, whereas the other interatomic O⋯H/H⋯O contacts are merged within the plot and appear as a pair of intense blue spikes at de + di ∼2.8 Å. Despite the observation that intermolecular C—H⋯π contacts are usually preferred by methyl groups, none are found involving those substituted at (C1–C6) benzene ring in the crystal due to the V-shaped geometry. Rather, the involvement of methyl-C7 and H5A atoms, and benzene-C5 and H7C atoms [to provide links between the chains shown in Fig. 2b)] in C—H⋯C interactions, Table 2de + di ∼2.8 Å in the fingerprint plot delineated into C⋯H/H⋯C contacts, Fig. 5d). The presence of π–π stacking interactions between symmetry-related phthalazinone-N2C4 and C6 rings is also evident as the arrow-shaped distribution of points around de, di ∼1.8 Å in the fingerprint plot delineated into C⋯C contacts, Fig. 5e). The contribution from other interatomic contacts, summarized in Table 2The overall two-dimensional fingerprint plots for (I)Eele), polarization (Epol), dispersion (Edis) and exchange–repulsion (Erep) following Turner et al.  level of theory. The nature and strength of the intermolecular interactions in terms of their energies are quantitatively summarized in Table 42C4 and C6 rings and the short interatomic O1⋯H14 contact have the greatest energy. The short interatomic C5⋯H7C, O3⋯H8A and C10⋯H8A contacts also have significant interaction energies due to their participation in inversion-related contacts. Lower energies, compared to above interactions, are calculated for the H12⋯H9A, C7⋯H5 and O1⋯H9C contacts.The pairwise interaction energies between the molecules within the crystal of (I) al. 2017. The eneEele, Edisp and Etot, respectively. The images emphasize the importance of dispersion interactions in the molecular packing.Fig. 6H)-one et al., 20182CCH3)3·4H2O  was added with constant stirring to an ethanol solution (20 ml) of (III) . The resulting mixture was refluxed for 3 h in an oil bath. The obtained colourless solution was concentrated to afford a colourless precipitate, which was filtered, dried under suction and further dried in vacuo over CaCl2. The precipitates were dissolved in ethanol, the resultant colourless solution was filtered and left at room temperature for 48 h to obtain colourless crystals of (I)2-{[2-hydrazinylidene]methyl}benzoic acid (III) was obtained by a method reported earlier (Asegbeloyin Uiso(H) set to 1.2–1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 610.1107/S2056989020005101/lh5956sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020005101/lh5956Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020005101/lh5956Isup3.cmlSupporting information file. DOI: 1996401CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound belongs to the class of neutral pyridine aroylhydrazone complexes. In the crystal, π–π stacking leads to dimerization of the complex molecules, which, in turn, are connected by weak C⋯O and C⋯C interactions, thus giving rise to a supramolecular layered architecture. 17H18N3O4)2]·CH4O·C2H6O, contains two complex molecules related by an inversion centre, plus one methanol and one ethanol solvent molecule per complex molecule. In each complex, two deprotonated pyridine aroylhydrazone ligands {3,4,5-trimethoxy-N′-[1-(pyridin-2-yl)ethylidene]benzohydrazide} coordinate to the ZnII ion through the N atoms of the pyridine group and the ketamine, and, additionally, through the O atom of the enolate group. In the crystal, dimers are formed by π–π interactions between the planar ligand moieties, which are further connected by C⋯O and C⋯C interactions. The intermolecular interactions were investigated using Hirshfeld surface analysis and two-dimensional fingerprint plots, revealing that the most important contributions for the crystal packing are from H⋯H (44.8%), H⋯C/C⋯H (22.2%), H⋯O/O⋯H (18.7%) and C⋯C (3.9%) interactions.The unit cell of the title compound, [Zn(C These dynamic reversible properties have led to the exploration of charged and neutral spin-crossover iron(II) and iron(III) complexes, some with multifunctional properties /24, where θi is the angle generated by superposition of two opposite faces of the octahedron /12, where φi is the deviation from 90° of the cis-N—Zn—N angles in the coordination sphere  Å. In the dimer, the Zn⋯Zni separation is 7.612 (2) Å   −x, −y, −z + 1] = 3.100 (5) Å (Table 1ii interdimer separation of 6.965 (5) Å. It is worth noting that a related FeII pyridine-based complex with butyl substituents consisting of uniform supramolecular chains with Fe⋯Fe separation of 7.676 Å has previously been described  Å and b = 13.8056 (8) Å. There are interchain contacts C33⋯C34iii/C34⋯C33iii , below the sum of the van der Waals radii, between the methoxy groups of neighbouring supramolecular chains at 3.385 (5) Å.The ligand molecules exhibit slipped parallel π–π stacking between coplanar ligands of neighbouring molecules, thus forming a dimeric structure; the closest C4⋯C61] Fig. 2. NeighboÅ Table 1, with thiv  between the ethanol methyl group and a methoxy methyl group is 3.300 (5)Å. Additionally, neighbouring molecules of ethanol are mutually bound forming dimers with C36⋯C37v and O10⋯C37v  contacts with distances of 3.227 (5) and 2.751 (2) Å, respectively. Furthermore, the co-crystallized molecules of methanol form O—H⋯O hydrogen bonds with the methoxy group of the ligand, with an O9⋯O2 separation between the O atoms of 2.776 (4) Å.The neutral nature of the complex molecule and therefore the absence of anions and, on the other hand, the relatively large size of the planar rigid substituents prevent the formation of a tightly packed lattice. Therefore, intermolecular voids are filled by the co-crystallized molecules of ethanol, which act as bridges connecting the closest complex molecules by O—H⋯N hydrogen bonding, with the distance between the donor and acceptor atoms O10⋯N6 equal to 2.825 (5) Å. The contact C15⋯C37CrystalExplorer17.5 software  to 2.2951 (blue) a.u. The pale-red spots symbolize short contacts and negative dnorm values on the surface correspond to the interactions described above. The overall two-dimensional fingerprint plot is illustrated in Fig. 3dnorm are shown for the H⋯H, H⋯C/C⋯H, H⋯O/O⋯H, and C⋯C contacts, and the two-dimensional fingerprint plots are presented in Fig. 4The Hirshfeld surface analysis and the associated two-dimensional fingerprint plots were undertaken using et al., 2016N′-[1-(pyridin-2-yl)ethylidene]benzohydrazide ethylidene]benzohydrazide ethylidene]benzohydrazide ethylidene]benzohydrazide  to 177.76° (MAKLES), while intermediate values of 168.09 and 170.56° are observed for PATXAK and HIGPOD, respectively.A search of the Cambridge Structural Database  to give a colourless complex. A pale-yellow solution was obtained after deprotonation with NEt3 (1 mmol). The neutral complex was isolated by slow cooling the solution to ambient temperature and subsequently by filtering off the yellowish crystals. Elemental analysis calculated (%) for C37H46N6O10Zn: C 55.54, H 5.79, N 10.50; found: C 55.86, H 5.31, N 10.84. IR νKBr (cm−1): 1617 (N=C—O), 1588, 1461 (C=Npy + C=CAr), 1252 (C—O). MS ESI m/z (relative intensity): theoretically calculated 721.19 [M + H+] (100.0%). Found 721.21 [M + H+] (100.0%). TGA (up to 400 K) expected weight loss for EtOH + MeOH: 9.8%; found: 9.5%.The complex was obtained by condensation of 3,4,5-trimethoxybenzohydrazide (1 mmol) and acetyl pyridine (1.1 mmol) in a mixture of absolute MeOH and EtOH (1:1) overnight in the presence of two drops of glacial acetic acid. The ligand obtained Uiso(H) = 1.2–1.5Ueq(C). None of the hydrogen atoms of the methanol or ethanol molecules could be located.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020000857/tx2017sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020000857/tx2017Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020000857/tx2017Isup3.cdxSupporting information file. DOI: 1979477CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


S(6) ring motif.The title molecule is planar with an r.m.s. deviation for all non-hydrogen atoms of 0.018 Å. An intramolecular O1—H1⋯O5 hydrogen bond involving the adjacent hydroxyl and nitro groups closes an  8H7NO5, is planar with an r.m.s. deviation for all non-hydrogen atoms of 0.018 Å. An intramolecular O—H⋯O hydrogen bond involving the adjacent hydroxy and nitro groups forms an S(6) ring motif. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming chains propagating along the b-axis direction. The chains are linked by C—H⋯O hydrogen bonds, forming layers parallel to the bc plane. The layers are linked by a further C—H⋯O hydrogen bond, forming slabs, which are linked by C=O⋯π interactions, forming a three-dimensional supramolecular structure. Hirshfeld surface analysis was used to investigate intermolecular interactions in the solid state. The molecule was also characterized spectroscopically and its thermal stability investigated by differential scanning calorimetry and by thermogravimetric analysis.The title compound, C Several synthetic routes for the synthesis of entacapone have been reported , was synthesized and its spectroscopic and structural features were studied. There are two reasons for this study, one is connected with the utilization of crystal structures in the identification of materials in the solid state, and the other is to build a library of structurally related compounds of entacapone that will be utilized in a future crystallization study.The title compound is a key starting material in the preparation of entacapone  ring motif. The molecule is planar  with the maximum deviation from the mean plane being 0.038 (1) Å for atom O5. The bonds lengths and bond angles are close to those found for similar structures (see §4. Database survey).The molecular structure of the title compound I, molecules are linked by intermolecular bifurcated hydrogen bonds involving the hydroxyl group. Details of the hydrogen bonding together with the symmetry codes are given in Table 1ialdehyde hydrogen bonds [2.6989 (12) Å] link the molecules into chains with a C(8) motif. Each oxygen atom is involved in one or more intermolecular hydrogen bonds, except for the O5nitro atom, which is involved only in the intramolecular hydrogen bond. Each molecule is connected by six adjacent molecules through strong O1—H1⋯O3aldehyde and weak C7—H7⋯O4iinitro and C8—H8A⋯O3iiialdehyde hydrogen bonds, forming undulating layers parallel to the bc plane, enclosing two type of ring motifs – B⋯O4ivnitro, forming slabs  Å] and C2—O1⋯π [3.353 (su?) Å] close contacts  Fig. 2. The laybs Fig. 3. Moreovets Fig. 4 are preset al., 2016viz. a tin complex of the 4-hydroxy-3-methoxy-5-nitrobenzaldehyde with a deprotonated hydroxyl group and benzyl anions -2-cyano-3--N,N-diethylprop-2-enamide 1,3-dimethyl-3,7-dihydro-1H-purine-2,6-dione monohydrate -2-cyano-3--N,N-diethylprop-2-enamide pyridine-4-carboxamide -2-cyano-3--N,N-diethylprop-2-enamide pyrazine-2-carboxamide -2-cyano-3--N,N-diethylprop-2-enamide acetamide , while the most negative region is around the carbonyl oxygen atom . Those two atoms are involved in the shortest intermolecular hydrogen bond in the crystal structure (O1—H1⋯O3i), where O1⋯O3i = 2.6989 (12) Å; see Table 1Electrostatic potentials were calculated using ce Fig. 7 in the ece Fig. 7a, whileom Fig. 7b. Those3 (10.5 ml) was added dropwise over 30 min. The reaction mixture was stirred for 30 min at 283–288 K and 30 min at 293–298 K. The suspension was then filtered and the crystals obtained were washed with water (3 × 20 ml). The crystals were dried in a vacuum dryer  to obtain pure yellow compound I . Yellow block-like crystals, suitable for X-ray diffraction analysis, were obtained by slow evaporation of a solution in acetone after 10 d at room temperature.4-Hydroxy-3-methoxybenzaldehyde  was dissolved in acetic acid (200 ml) and the solution was cooled to 283–288 K and 65% HNOSpectroscopic analysis:I  and 125.8 MHz (13C) in CD3OD ; see Tables 2The structure of compound I Fig. 8 was confI was investigated in the solid state by differential scanning calorimetry (DSC) and by thermogravimetric analysis (TGA). DSC analysis was performed on a TA Instruments Discovery DSC in a closed aluminium pan (40 µL) under nitrogen flow (50 ml min−1) and a heating rate of 10°C min−1 in the temperature range 25–300 °C  and a heating rate of 10°C min−1 in the temperature range 25–300°C  technique. It shows a broad band at about 3200 cm−1, which corresponds to the O—H stretching vibrations. Strong stretching vibrations of C=O  and C—O (aromatic ether) appear at 1683 and 1266 cm−1, respectively. Bands corresponding to N—O asymmetric and symmetric stretching modes can be found at 1547 and 1366 cm−1, respectively. Characteristic weak overtones of the aromatic ring can be seen at 1800–1700 cm−1.The IR spectrum Fig. 12 of compoUiso(H) = 1.5Ueq(O) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989020000225/su5534sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020000225/su5534Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020000225/su5534Isup3.cmlSupporting information file. DOI: 1957893CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


I tricarbonyl complexes bearing ester-substituted bipyridine or biquinoline ligands is reported.The structural comparison of two Mn fac-bromidotricarbonylmanganese(I), [MnBr(C16H16N2O4)(CO)3], I, and fac-bromidotricarbonylmanganese(I), [MnBr(C24H20N2O4)(CO)3], II. In both complexes, the manganese(I) atom adopts a distorted octahedral coordination sphere defined by three carbonyl C atoms, a Br− anion and two N atoms from the chelating α-diimine ligand. Both complexes show fac configurations of the carbonyl ligands. In I, the complex molecules are linked by C—H⋯Br hydrogen bonds and aromatic π–π contacts. In II, intramolecular C—H⋯O hydrogen bonds are present as well as intermolecular C—H⋯O and C—H⋯Br hydrogen bonds and π–π interactions.The crystal structures of two manganese(I) complexes with ester-substituted bipyridine or biquinoline supporting ligands are reported, namely,  We successfully compared their crystal structures and photophysical properties. As expected, a CT band shift in the visible region was confirmed, depending on the size of the π-conjugation system in α-diimine ligands. This finding will provide information in the future design of suitable complexes for a variety of photoreactions  and 2.047 (2) Å, while in II, the Mn—N bond lengths are 2.063 (2) and 2.068 (2) Å. In I and II, the fac configuration of three CO ligands around the central manganese(I) atom is in agreement with their IR data. On the basis of their bond parameters, all CO ligands have typical triple-bond characters.The molecular structures of compounds I (C3—Mn1—N1—C8 and C2—Mn1—N2—C9) are −169.17 (15) and 168.81 (14)°, respectively; the corresponding torsion angles in II (C3—Mn1—N1—C12 and C2—Mn1—N2—C13) are −147.52 (16) and 147.08 (17)°, respectively  in debqn, and the equatorial CO ligands (C3≡O3 and C2≡O2). On the basis of similar steric hindrance, comparable torsion angles [150.4 (15) and −150.7 (5)°] have been also observed in the related ReI complex  Å and C10—C11 = 1.392 (3) Å] are considerably longer than the corresponding one in II [C10—C11 = 1.364 (4) Å and C14—C15 = 1.368 (4) Å]. This difference in structural parameters may eventually affect the intramolecular hydrogen-bond formation.Despite similar molecular skeletons, only g Table 2. The C—CI, complex molecules are linked by pairs of weak C—H⋯Br hydrogen bonds (Table 1Cg1⋯Cg2iii = 3.683 (1) Å; Cg1 and Cg2 are the centroids of the N1/C4–C8 and N2/C9–C13 rings, respectively; symmetry code: (iii) 1 − x, −y, 1 − z], forming a three-dimensional supramolecular structure  Å and Cg5⋯Cg6iv = 4.002 (2) Å; Cg3, Cg4, Cg5 and Cg6 are the centroids of the C4–C9, C16–C21, N1/C8–C12 and N2/C13–C17 rings, respectively; symmetry code: (iv) 1 − x, 1 − y, −z]. These interactions lead to the formation of a three-dimensional network structure 3(N-N)], some structures have been reported  complexes with a bidentate bipyridine derivative ligand (N-N) of the form et al. .The ligands, debpy and debqn, were prepared as described by Chandrasekharam  al. 2011 and Hoer al. 2006. The ligSynthesis of I and II: Compounds I and II were handled and stored in the dark to minimize exposure to light. For the synthesis of I, [MnBr(CO)5]  and debpy  were dissolved in CHCl3 (10 ml). The reaction mixture was stirred at 313 K for 14 h under N2. After the solvent was evaporated under reduced pressure, an excess of Et2O (30 ml) was added to the solution; then, the solution was allowed to stand at 253 K overnight. The resultant precipitate was collected by filtration, washed with Et2O, and then dried under vacuum . Red crystals, suitable for the X-ray diffraction experiment, were grown by diffusion of n-hexane into an acetone solution of I for one week. FTIR (KBr pellet): νCO /cm−1 = 2028, 1918 (br) (C≡O), 1730 (C=O). UV–vis (CHCl3): λ /nm (∊ /M−1 cm−1) = 483 (3700), 367 (4100), 318 (21000), 247 (24000).5]  and debqn  for 20 h afforded II . Purple crystals, suitable for the X-ray diffraction experiment, were grown by diffusion of n-hexane into an acetone solution of II for one week. FTIR (KBr pellet): νCO /cm−1 = 2016, 1942, 1926 (C≡O), 1725 (C=O). UV–vis (CHCl3): λ /nm (∊ /M−1 cm−1) = 548 (3200), 383 (19000), 276 (37000).A similar reaction between [MnBr(CO)Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989020010750/dj2012sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989020010750/dj2012Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020010750/dj2012Isup4.molSupporting information file. DOI: 10.1107/S2056989020010750/dj2012IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989020010750/dj2012IIsup5.molSupporting information file. DOI: 2021226, 2021225CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II complex, a newly synthesized dye, the metal atom is coordinated by two N atoms and two O atoms from two bidentate (E)-1-[diazenyl]naphthalen-2-olate ligands.In the title Cu 16H8Br3N2O)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-[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.In the title compound, [Cu(C The N—Cu—N bond angle is 177.8 (2)°. The two Cu—O distances are 1.882 (4) and 1.892 (4) Å. All bond lengths are similar to those observed in similar crystal structures  shows a multiplet around 7 and 8 ppm attributed to the aromatic protons. The IR spectrum of the complex shows the vibration bands: ν(N=N); 1360 cm−1, ν(C—N): 1149 cm −1, ν(C—Br): 645 cm−1, ν(C—O): 1207 cm−1 (aromatic), ν(C=C): 1498 cm−1 (aromatic), ν(C—H): 2945 cm−1 (aromatic), ν(Cu—N): 417 cm−1, ν(Cu-O): 558 cm−1. The UV–Vis spectrum measured in CH2Cl2 (10 −5 M), shows three absorption bands: an intense band at 268 nm (∊ = 29.94 108 M−1 cm−1) attributed to intra-ligand charge-transfer transition, a band at 382 nm (∊ = 79.21 107 M−1 cm−1) associated with the azo form of the ligand and a band at 462 nm (∊ = 63.84 107 M−1 cm−1) attributed to metal–ligand charge transfer.The complex, bis-1--2-naphtholatecopper(II), was obtained by mixing 1 mmol of 1--2-naphthol dissolved in 20 ml of THF with 0.5 mmol of Cu(OAc)Uiso(H) = 1.2 Ueq(C). An absorption correction was not applied in view of the very small size of the crystal [0.1 × 0.09 × 0.08 mm]. The DMSO solvent molecule shows disorder over two positions with final occupancies of 0.70 and 0.30. The disordered atoms were modelled as anisotropic using EADP restraints. H atoms of the disordered DMSO were omitted.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020001863/tx2018sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020001863/tx2018Isup2.hklStructure factors: contains datablock(s) I. DOI: 1983017CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The cationic layers are made up from two types of [Na(H2O)6] octahedra that form linear 1∞[Na(H2O)4/2(H2O)2/1] chains linked by dimeric [Na(H2O)2/2(H2O)4/1]2 units on both sides of the chains. The isolated trigonal–pyramidal sulfite anions are connected to the cationic layers through an intricate network of O—H⋯O hydrogen bonds, together with a remarkable O—H⋯S hydrogen bond, with an O⋯S donor–acceptor distance of 3.2582 (6) Å, which is about 0.05 Å shorter than the average for O—H⋯S hydrogen bonds in thiosalt hydrates and organic sulfur compounds of the type Y—S—Z . Structural relationships between monoclinic Na2SO3(H2O)7 and orthorhombic Na2CO3(H2O)7 are discussed in detail.The monoclinic crystal structure of Na Indeed, the two heptahydrates show not only a close metrical relationship , as a corrosion inhibitor in aqueous media, as a bleaching agent, as a solubilizing agent for cellulose, straw and wood in the pulp and paper industry, or as an additive in dying processes. In the USA alone, the production of sodium sulfite reached 150 000 tons in 2002 7 were grown by recrystallization of a commercial anhydrous sample  from an aqueous solution at room temperature by slow evaporation over the course of several days. In order to remove adherent mother liquor, the crystals were placed on filter paper and subsequently immersed in Paratone oil. The crystal under investigation was cleaved from a larger specimen.Colourless prismatic crystals of Na2SO3(H2O)7 was originally solved and refined in the space group P121/n1 (No. 14), with lattice parameters a = 11.8576 (8), b = 7.2197 (5), c = 12.6965 (9) Å and β = 106.7938 (17)° at 100 K . The values for the lattice parameters at 100 K are in good agreement with the previous study, with values of a = 11.922, b = 7.260, c = 12.765 Å and β = 107.22° obtained at room temperature from Weissenberg film data 7 7, using the matrix 7 and β-Na2CO3(H2O)7. All H atoms present in the crystal structure of Na2SO3(H2O)7 were located in a difference Fourier map and were refined freely.Crystal data, data collection and structure refinement details are summarized in Table 22SO3(H2O)7, all atoms  are located on general sites. The two sodium cations are surrounded by six water molecules, defining a distorted octahedral coordination polyhedron in each case. The Na—O distances range from 2.3690 (6) to 2.4952 (6) Å (Table 3[6]—O of 2.44 (11) Å calculated for 5520 individual bonds –176.42 (2)° for Na1 and 165.81 (2)–174.23 (2)° for Na2, and for cis O atoms in the range 81.464 (19)–101.74 (2)° for Na1 and 81.51 (2)–103.23 (2)° for Na2. The two types of [Na(H2O)6] octahedra show a different linkage pattern. Octahedra centred by Na1 share common edges 4/2(H2O)2/1] chains running parallel to [001], whereas octahedra centred by Na2 make up dimeric [Na2(H2O)2/2(H2O)4/1]2 units by sharing an edge (O5 and O5iii). In both cases, the corresponding Na—O bonds to the shared O atoms at the edges are the shortest in the respective octahedron. The dimeric units connect adjacent chains by sharing the terminal water molecules (O9 and O7) on both sides of the chains (corner-sharing links). This way, the sodium–water octahedra are assembled by edge- and corner-sharing into an infinite layer extending parallel to (100) .In the crystal structure of NaÅ Table 3, with me0) Fig. 1a.IV atom occupying the pyramidal position. Atom S1 is 0.5912 (4) Å above the basal plane formed by atoms O1, O2 and O3. The S—O bond lengths are in a narrow range 1.5224 (5)–1.5338 (5) Å [mean 1.527 (6) Å], just like the O—S—O angles . Again, these values are in good agreement with the grand mean SIV—O bond length of 1.529 (15) Å calculated for 90 bonds and with the O—SIV—O angles in the range ∼99–107° with a mean value of ∼104° 4/2(H2O)2/1] chains .The sulfite anion has the characteristic trigonal–pyramidal configuration, with the Sns Fig. 2a.a). Based on the donor–acceptor distances between 2.7204 (7) and 2.9110 (8) Å (Table 4a). Thereby, atom O1 is the acceptor of three, O2 of four and O3 of three hydrogen bonds. It is worth noting that the S—O bond lengths reflect this situation nicely, with S1—O2 = 1.5338 (5) Å being about 0.01 Å longer than the remaining two. The O9 water molecule, bonded to Na1, Na2 and via H9A to O2, lacks a clearcut hydrogen bond for its second H atom (H9B), which points to H6B of the O6—H6B⋯O3 hydrogen bond ·H2O 2]·2.25H2O (S2O5) 7 7 and orthorhombic Na2CO3(H2O)7 (Table 12O)6] octahedra  is present in the carbonate, likewise situated at x ≃ 0, b). The carbonate groups do not show pyramidalization 2/2(H2O)4/1]2 dimers.The close structural relationship between monoclinic Na7 Table 1 becomes ll Fig. 2b. The c2O)2/2(H2O)4/1]2 dimers in the layers. Whereas in the sulfite structure, the dimers at y ≃ 0 and y ≃ c-glide plane 7, to NH4SO3(H2O) 6 6, which is built up from [Mg(H2O)6] octahedra and isolated SO3 pyramids within a lattice of the space group type R3, and with Mg and S atoms both located on threefold rotation axes, there are two independent water molecules that donate, apart from one water–water hydrogen bond, three water–Osulfite hydrogen bonds to each sulfite O atom, comparable to O1 and O3 in Na2SO3(H2O)7, but with shorter O⋯O distances  than in the latter. An electron deformation density study of MgSO3(H2O)6 6 nor NH4SO3(H2O) contain O—H⋯S or N—H⋯S hydrogen bonds.Crystal structures with sulfite groups anchored exclusively by hydrogen bonds are at present restricted to the title compound Na2SO4(H2O)7  has a completely different arrangement of the principal building units. Its crystal structure is comprised of [Na(H2O)]6 octahedra concatenated by edge- and corner-sharing into a three-dimensional network with isolated tetrahedral sulfate anions hydrogen bonded to the chains. Also, for sodium compounds with analogous trigonal–pyramidal oxoanions and the same charge, i.e.XO32−, with X = Se and Te, no phases related structurally or compositionally to Na2SO3(H2O)7 are known. For Na2SeO3, the anhydrous form  is made up from [NaO6] octahedra and trigonal–pyramidal SeO32− anions 5 5 . These structures are based on two- or three-dimensional assemblies of [NaO5] polyhedra (Se) and [NaO6] octahedra (Se and Te), to which SeO3/TeO3 groups are bonded via two (Se) or one (Te) O atom. The [NaO6] octahedra in these two salts share common faces and edges but no vertices. As pointed out by Philippot et al. (19792TeO3(H2O)5 and confirmed also for Na2SeO3(H2O)5 7 structure and vice versa. A further comparison with other hydrated sodium compounds comprised of related oxo anions shows no close structural relationship to the title heptahydrate. For example, Na al. 1979 for Na2T10.1107/S2053229620004404/ep3004sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2053229620004404/ep3004Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2053229620004404/ep3004sup3.txtCIF with full numerical data (setting P121/n1). DOI: Click here for additional data file.10.1107/S2053229620004404/ep3004Isup4.cmlSupporting information file. DOI: 1993827CCDC reference:


Within the sheets, very weak π–π stacking interactions occur. The Hirshfeld surface analysis and fingerprint plots reveal that the crystal structure is dominated by H⋯H (37.1%) and C⋯H (30.1%) contacts.In the crystal, molecules are linked by C—H⋯π interactions, resulting in the formation of sheets along the  14H12INO, was synthesized by condensation of 2-hydroxy-3-methylbenzaldehyde and 2-iodoaniline, and crystallizes in the orthorhombic space group P212121. The 2-iodophenyl and benzene rings are twisted with respect to each other, making a dihedral angle of 31.38 (2)°. The molecular structure is stabilized by an O—H⋯N hydrogen bond, forming an S(6) ring motif. In the crystal, molecules are linked by C—H⋯π interactions, resulting in the formation of sheets along the a-axis direction. Within the sheets, very weak π–π stacking interactions lead to additional stabilization. The Hirshfeld surface analysis and fingerprint plots reveal that the crystal structure is dominated by H⋯H (37.1%) and C⋯H (30.1%) contacts. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. The crystal studied was refined as a two-component inversion twin.The title compound, C We report here the synthesis and the crystal and molecular structures of the title compound, along with the results of a Hirshfeld surface analysis.In the present study, a new Schiff base, S(6) ring motif, which stabilizes the molecular structure and induces the Schiff base atoms  to be coplanar with the methylphenol moiety. Of this planar unit (r.m.s deviation = 0.0274 Å), atoms O1 and N1 show the largest deviations from planarity in positive and negative directions [O1 = 0.035 (4) Å and N1 = −0.060 (4) Å]. The C7—N1 and C13—O1 bonds of the title compound are the most important indicators of the tautomeric type. The C13—O1 bond is of double-bond character for the keto–amine tautomer, whereas this bond displays single-bond character in the enol–imine tautomer. In addition, the C7—N1 bond is also a double bond in the enol–imine tautomer and a single bond length in the keto–amine tautomer. In the title compound, the enol–imine form is favored over the keto-amine form, as indicated by the C13—O1 [1.352 (6) Å] and C7—N1 [1.286 (8) Å] bonds, whose lengths indicate a high degree of single-bond and double-bond character, respectively. The shortest C—C distance (C3—C4) is 1.344 (11) Å in the C1–C6 ring with the weighted average ring bond distance being 1.376 (11) Å for this ring.Depending on the tautomers, two types of intramolecular hydrogen bonds are observed in Schiff bases: O—H⋯N in enol–imine and N—H⋯O in keto–amine tautomers. Most of these compounds are non-planar. The title compound, (I)a-axis direction by C2—H2⋯Cg2i interactions (Table 1Cg1⋯Cg2ii of 4.093 (2) Å  of the title compound are illustrated in Fig. 4a and red areas on phenyl rings mapped with shape-index  correspond to the H⋯π contacts resulting from hydrogen bond C—H⋯π(ring)  Table 1 and π–π et al., 2016E)-2-[(2-iodophenylimino)methyl]phenol gave six hits: biscopper(II) bisimino]methyl}phenolato)bis(isothiocyanato)diiron(III) methanol solvate bis(m-methanolato)tetrakisimino]methyl}phenolato)bis(isothiocyanato)tetrairon(III) dichloromethane solvate  in ethanol (20 ml) and 2-iodoaniline  in ethanol (20 ml). The reaction mixture was stirred for 4 h under reflux. Single crystals of the title compound for X-ray analysis were obtained by slow evaporation of an ethanol solution .Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. Hydroxyl H atoms were placed according to a difference-Fourier map and were freely refined. The crystal studied was refined as a two-component inversion twin. This reflection file contains the non-overlapping reflections of the two twin components as well as the overlapping reflections. The BASF parameter for this two-component twin refined to −0.03242 (8).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020011974/zl2795sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020011974/zl2795Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020011974/zl2795Isup3.cmlSupporting information file. DOI: 2026445CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Alzheimer’s disease (AD)-related tauopathy can be measured with CSF phosphorylated tau (pTau) and tau PET. We aim to investigate the associations between these measurements and their relative ability to predict subsequent disease progression.18F-florbetapir or 18F-florbetaben), 18F-flortaucipir (FTP) PET, CSF measurements, structural MRI, and cognition, we examined inter-relationships between these biomarkers and their predictions of subsequent FTP and cognition changes.In 219 cognitively unimpaired and 122 impaired Alzheimer’s Disease Neuroimaging Initiative participants with concurrent amyloid-β (Aβ) PET  were 4 times more prevalent (p <  0.001) than abnormal FTP only individuals (6.8%). Furthermore, among individuals on the AD pathway, CSF pTau/Aβ40 mediates the association between Aβ PET and FTP PET accumulation, but FTP PET is more closely linked to subsequent cognitive decline than CSF pTau/Aβ40.The use of a CSF pTau/Aβ40 may be a superior measure of tauopathy compared to CSF pTau alone, and CSF pTau/Aβ40 enables detection of tau accumulation at an earlier stage than FTP among Aβ+ individuals.Together, these findings suggest that CSF pTau/Aβ Extracellular amyloid-β (Aβ) peptides in cortical Aβ plaques and intracellular phosphorylated tau protein as neurofibrillary tangles are key hallmarks of Alzheimer’s disease (AD) that can be measured in vivo with positron emission tomography (PET) imaging and biofluid markers including plasma and cerebrospinal fluid (CSF) assays. The relationship between CSF Aβ and Aβ PET in AD has been widely reported –8, but r42 in the Aβ− range ) associated with CSF Aβ42 in Aβ PET− participants, whereas no association was found in Aβ+ participants  sample of 384 Aβ− participants  and Aβ+  participants.CSF Aβtus Fig. a, b. Bef40 , CSF pTau/Aβ40 , and tau PET in Temporal-metaROI  and entorhinal  in Aβ+ participants. Notably, the association with Aβ PET increased from rho value 0.38 when using CSF pTau alone to 0.60 using the CSF pTau/Aβ40 .We found Aβ PET was significantly associated with CSF and PET tau measurements, which were driven by Aβ+ individuals. Baseline Aβ PET was positively associated with CSF pTau , Aβ− and Aβ+ participants were classified as tau normal (T−)/abnormal (T+) using CSF pTau or CSF pTau/Aβ40 or tau PET thresholds, dividing the whole cohort into A−/T−, A−/T+, A+/T−, and A+/T+ groups. Few Aβ− participants had abnormal CSF pTau/Aβ40 (7.6%) and temporal tau PET (5.3%), whereas Aβ+ participants showed a 3.0–4.5 times higher percentage of abnormal CSF pTau/Aβ40 (32.6%) and temporal tau PET (24.0%) than Aβ− participants /abnormal (+) on CSF pTau or CSF pTau/Aβ40 (PTAU+/−) and entorhinal or Temporal-metaROI FTP SUVR (FTP+/−). Abnormal CSF pTau only had higher prevalence  than abnormal CSF pTau/Aβ40 only in Aβ− participants, whereas abnormal CSF pTau/Aβ40 only had marginally higher prevalence  than abnormal CSF pTau only in Aβ+ participants. CSF pTau/Aβ40  were positively associated with temporal tau PET across all participants. Aβ+ participants were responsible for this relationship because no association was found in Aβ− participants  . The results were similar for entorhinal tau PET , CSF pTau/Aβ40 , and Temporal-metaROI tau PET  were all associated with subsequent tau PET increase (ΔFTP) in Aβ+ participants . CSF pTau/Aβ40-involved pathways  explained 70% of the association  between Aβ PET and ΔFTP increase in Aβ+ participants.The latent variable model demonstrated that the direct association between Aβ and ΔFTP increase in Aβ+ participants was not significant after including the CSF pTau/AβFTP Fig. d, reduciβstd = − 0.41 ), CSF pTau/Aβ40 , and Temporal-metaROI tau PET  were all associated with subsequent cognitive decline in Aβ+ participants  remained predictive when all variables were added into one multivariate model. The results were similar for entorhinal tau PET. In contrast, only CSF pTau/Aβ40  was associated with subsequent cognitive decline in Aβ− participants.Baseline Aβ PET  Tau PET associations with CSF pTau/Aβ40 were highest in medial and lateral temporal regions. (3) Associations between Aβ PET, CSF pTau/Aβ40, and tau PET  were substantially driven by Aβ PET-positive individuals. (4) Among these Aβ+ individuals, most participants (66%) were concordant on CSF pTau/Aβ40 and Temporal-metaROI tau PET, but among discordant individuals, those with abnormal CSF pTau/Aβ40 and normal tau PET were 4 times more prevalent (26.7%) than those with abnormal tau PET and normal CSF pTau/Aβ40 (6.8%). (5) Among these Aβ+ individuals, baseline Aβ PET, CSF pTau/Aβ40, and tau PET were all associated with subsequent tau PET increase, while CSF pTau/Aβ40 significantly mediates the association between Aβ PET and tau PET . (6) Only tau PET was predictive of longitudinal cognitive decline when baseline Aβ PET, CSF pTau/Aβ40, and tau PET were put in one multivariate model.This study had several primary findings: (1) use of a CSF pTau/Aβ42 , but it is possible that early and late changes in CSF Aβ40 may contribute to the tau-related effects we observed.Our motivation to adjust CSF pTau measurements was based on our observation that Aβ PET-negative individuals had abnormal (“positive”) CSF pTau that correlated positively with high  CSF Aβ42 Fig. c, suggesiversity , 16, and42 alone , 17–19, 42 alone . However studies –51 have al study  observed40 and tau PET were stronger in ROIs in the temporal lobe than other areas such as frontal and occipital lobes that accumulate tau in later stages of disease [40 and tau PET was primarily driven by Aβ PET positivity and less influenced by clinical diagnosis  in the Aβ− individuals, which was in line with previous reports [40 or tau PET) was rarely (5.3–7.9%) abnormal in the Aβ− range  and40 ratio improves the sensitivity to detect CSF tau by adjusting for individual differences in CSF production. Furthermore, although PET and CSF measures of tau are broadly concordant in the majority (76%) of individuals when measured dichotomously, our findings support recent work [In summary, we found that the use of a CSF pTau/Aβent work  indicatient work . Among aAdditional file 1:Figure S1. The ROC analysis using the Youden index classifying 280 Aβ- ADNI cognitively unimpaired (CU) participants and 183 Aβ + ADNI MCI and AD patients as the endpoint to define the cutoff ≥1.25 for Temporal-metaROI FTP SUVR. AUC: 0.876 . Among these 463 ADNI participants, 217 (47%) participants were included in the analyses of the manuscript. Figure S2. Histograms of Temporal-metaROI FTP SUVRs of (A) all 775 ADNI participants, (B) 280 Aβ- ADNI CU participants and (C) 183 Aβ + ADNI MCI and AD patients with tau PET scan. Red dotted line is the cutoff of Temporal-metaROI FTP SUVR 1.25. Figure S3. The ROC analysis using the Youden index classifying 280 Aβ- ADNI CU participants and 183 Aβ + ADNI MCI and AD patients as the endpoint to define the cutoff ≥1.21 for entorhinal FTP SUVR. AUC: 0.891 . Figure S4. Histograms of entorhinal FTP SUVRs of (A) all 775 ADNI participants, (B) 280 Aβ- ADNI CU participants and (C) 183 Aβ + ADNI MCI and AD patients with tau PET scan. Red dotted line is the cutoff of entorhinal FTP SUVR 1.21. Figure S5. The ROC analysis using the Youden index classifying 320 Aβ- ADNI CU participants and 429 Aβ + ADNI MCI and AD patients as the endpoint to define the cutoff ≥22 for CSF p-Tau. AUC: 0.865 . Among these 749 ADNI participants, 212 (28%) participants were included in the analyses of the manuscript. Figure S6. Histograms of CSF p-Tau of (A) all 1534 ADNI participants, (B) 320 Aβ- ADNI CU participants and (C) 429 Aβ + ADNI MCI and AD patients with CSF p-Tau measurement. Red dotted line is the cutoff of CSF p-Tau 22. Figure S7. The ROC analysis using the Youden index classifying 169 Aβ- ADNI CU participants and 160 Aβ + ADNI MCI and AD patients as the endpoint to define the cutoff ≥0.0012 for CSF p-Tau/Aβ40 ratio. AUC: 0.976 . Among these 329 ADNI participants, 201 (61%) participants were included in the analyses of the manuscript. Figure S8. Histograms of CSF p-Tau/Aβ40 for (A) all 447 ADNI participants, (B) 169 Aβ- ADNI CU participants and (C) 160 Aβ + ADNI MCI and AD patients with CSF p-Tau/Aβ40. Red dotted line is the 0.0012 cutoff for the CSF p-Tau/Aβ40 ratio. Figure S9. Cross-sectional associations between CSF MASS Aβ42 and CSF p-Tau. The vertical gray dashed line reflects the abnormal threshold of CSF p-Tau. Abbreviations: p-Tau = phosphorylated tau; Aβ = amyloid-β; CU = cognitively unimpaired; MCI = mild cognitive impairment; AD = Alzheimer’s disease. Figure S10. Regions with significant association between CSF P-tau and FTP tau in (A) Aβ+, (B) CU and (C) non-demented participants. Abbreviations: Spearman rho = Spearman’s correlation coefficient; p-Tau = phosphorylated tau; Aβ = amyloid-β; FTP = 18F-flortaucipir; SUVR = standardized uptake value ratio; CU = cognitively unimpaired; MCI = mild cognitive impairment; AD = Alzheimer’s disease. Figure S11. Cross-sectional associations between Aβ PET, CSF p-Tau/Aβ40 and entorhinal tau PET. (A). Associations between baseline entorhinal tau PET and Aβ PET. Associations between baseline CSF p-Tau/Aβ40 and entorhinal tau PET in the whole cohort (B), Aβ- (C) and Aβ + (D) participants. The vertical and horizontal gray dashed lines reflect the abnormal thresholds of corresponding biomarkers in x-axis and y-axis respectively. Abbreviations: Aβ = amyloid-β; A = Aβ PET; − = negative; + = positive; AD = Alzheimer’s disease; CU = cognitively unimpaired; FTP = 18F-flortaucipir; MCI = mild cognitive impairment. Figure S12. Cross-sectional associations between Aβ PET, CSF pTau/Aβ40 and tau PET using alternative cutoffs. Associations between baseline Aβ PET and (A) CSF pTau, (B) CSF pTau/Aβ40 and (C) temporal tau PET. Associations between baseline CSF pTau and CSF pTau/Aβ40 in the whole cohort (D), Aβ- (E) and Aβ + (F) participants. Associations between baseline CSF pTau/Aβ40 and Temporal-metaROI tau PET in the whole cohort (G), Aβ- (H) and Aβ + (I) participants. The vertical and horizontal gray dashed lines reflect the abnormal thresholds of corresponding biomarkers in x-axis and y-axis respectively. Abbreviations: Aβ = amyloid-β; A = Aβ PET; − = negative; + = positive; AD = Alzheimer’s disease; CU = cognitively unimpaired; FTP = 18F-flortaucipir; MCI = mild cognitive impairment; pTau = phosphorylated tau; PTAU = CSF pTau or CSF pTau/Aβ40 ratio; SUVR = standardized uptake value ratio; T = CSF pTau or CSF pTau/Aβ40 or tau PET. Figure S13. Cross-sectional associations between Aβ PET, CSF p-Tau/Aβ40 and entorhinal tau PET using alternative cutoffs. (A). Associations between baseline entorhinal tau PET and Aβ PET. Associations between baseline CSF p-Tau/Aβ40 and entorhinal tau PET in the whole cohort (B), Aβ- (C) and Aβ + (D) participants. The vertical and horizontal gray dashed lines reflect the abnormal thresholds of corresponding biomarkers in x-axis and y-axis respectively. Abbreviations: Aβ = amyloid-β; A = Aβ PET; − = negative; + = positive; AD = Alzheimer’s disease; CU = cognitively unimpaired; FTP = 18F-flortaucipir; MCI = mild cognitive impairment.


The three-molecule aggregates are connected into a supramolecular tape by amide-N—H⋯O(amide) hydrogen bonding.In the title 1:2 co-crystal,  14H14N4O2·2C7H5ClO2, comprises two half molecules of oxalamide (4LH2), as each is disposed about a centre of inversion, and two molecules of 4-chlorobenzoic acid (CBA), each in general positions. Each 4LH2 molecule has a (+)antiperiplanar conformation with the pyridin-4-yl residues lying to either side of the central, planar C2N2O2 chromophore with the dihedral angles between the respective central core and the pyridyl rings being 68.65 (3) and 86.25 (3)°, respectively, representing the major difference between the independent 4LH2 molecules. The anti conformation of the carbonyl groups enables the formation of intramolecular amide-N—H⋯O(amide) hydrogen bonds, each completing an S(5) loop. The two independent CBA molecules are similar and exhibit C6/CO2 dihedral angles of 8.06 (10) and 17.24 (8)°, indicating twisted conformations. In the crystal, two independent, three-molecule aggregates are formed via carboxylic acid-O—H⋯N(pyridyl) hydrogen bonding. These are connected into a supramolecular tape propagating parallel to [100] through amide-N—H⋯O(amide) hydrogen bonding between the independent aggregates and ten-membered {⋯HNC2O}2 synthons. The tapes assemble into a three-dimensional architecture through pyridyl- and methylene-C—H⋯O(carbonyl) and CBA-C—H⋯O(amide) interactions. As revealed by a more detailed analysis of the molecular packing by calculating the Hirshfeld surfaces and computational chemistry, are the presence of attractive and dispersive Cl⋯C=O interactions which provide interaction energies approximately one-quarter of those provided by the amide-N—H⋯O(amide) hydrogen bonding sustaining the supramolecular tape.The asymmetric unit of the title 1:2 co-crystal, C The formation of such O—H⋯N hydrogen bonding is consistent with literature precedent, which indicates a very high propensity for these hydrogen-bonding patterns between carboxylic acids and pyridyl entities, at least in the absence of competing supramolecular synthons  hydrogen bonds are formed instead , each in a general position. Pairs of 4LH2 and CBA molecules are connected via carboxylic acid-O—H⋯N(pyridyl) hydrogen bonding, Table 1i.e. 4LH2(CBA)2, as shown in Fig. 1The crystallographic asymmetric unit of (I)4LH2 molecule is centrosymmetric, the central C2N2O2 chromophore in each is strictly planar. As is usually found in these molecules  Å] and C14—C14ii [1.539 (2) Å] bond lengths are longer than usual owing to the electronegative substituents connected to both carbon atoms . The conformation of each 4LH2 molecule is (+)antiperiplanar whereby the pyridin-4-yl residues lie to either side of the planar region of the molecule. The dihedral angles between the respective central core and the N1- and N3-pyridyl rings are 68.65 (3) and 86.25 (3)°, respectively. This represents the greatest conformational difference between the 4LH2 molecules and is emphasized in the overlay diagram of Fig. 2anti, enabling the formation of intramolecular amide-N—H⋯O(amide) hydrogen bonds that complete S(5) loops, Table 1As each 2 group is 8.06 (10)° for the O3-molecule indicating a closer to co-planar molecule than for the O5-molecule for which the equivalent dihedral angle is 17.24 (8)°. Consistent with the carboxylic acid assignment, the C15—O3(carbonyl) bond length of 1.2172 (17) Å is considerably shorter than the C15—O4(hydroxy) bond of 1.3196 (16) Å; the bonds of the O5-benzoic acid follow the same trend with C22—O5 of 1.2173 (17) Å compared with C22—O6 of 1.3181 (16) Å. As seen from Fig. 2To a first approximation, the two independent CBA molecules in (I)a axis by amide-N—H⋯O(amide) hydrogen bonding and concatenated, centrosymmetric 10-membered {⋯HNC2O}2 synthons, Fig. 3a). The tapes are consolidated into a three-dimensional architecture by pyridyl- and methylene-C—H⋯O(carbonyl) and CBA-C—H⋯O(amide) interactions, Fig. 3b).The formation of two independent, three-molecule aggregates has already been noted above in the crystal of (I)Crystal Explorer 17  hydrogen bonds. Analogous calculations were also performed on the symmetry expanded N1- and N3-oxalamide molecules, hereafter 4LH2-I and 4LH2-II, respectively, and on the independent O3- and O5-chlorobenzoic acid molecules, hereafter CBA-I and CBA-II, respectively. The dnorm distances for short contacts identified through the Hirshfeld surface analysis are given in Table 2The calculation of the Hirshfeld surfaces and two-dimensional fingerprint plots were accomplished with the program dnorm maps showing red spots ranging from moderate to strong intensity are illustrated in Fig. 4O⋯N1(pyridyl) in 3M-I, carboxylic-O6–H6O⋯N3(pyridyl) in 3M-II as well as the interactions between amide-N2–H2N⋯O2(amide) and amide-N4—H4N⋯O1(amide) in 3M-I and 3M-II, respectively, while relatively weaker interactions with moderately to weakly intense red spots between amide-C7⋯Cl1, pyridyl-C1—H1⋯O3(carboxylic acid), pyridyl-C2—H2⋯O3(carboxylic acid), methylene-C—H6A⋯O3(carboxylic acid), amide-O1⋯Cl1 in 3M-I, and Cl2⋯C14(amide), methylene-C13—H13A⋯O5(carboxylic acid), pyridyl-C8—H8⋯O5(carboxylic acid), pyridyl-C9—H9⋯O5(carboxylic acid), Cl2⋯O2(amide) in 3M-II are observed. As well, spots due to benzene-C27—H27⋯O1(amide) are seen, i.e. providing connections between 3M-I and 3M-II.Several dnorm maps for 3M-I and 3M-II exhibit similarity for the corresponding 4LH2 and CBA molecules with the exception of CBA-II. Pairs of CBA-II are aligned around an inversion centre with Cl2 and H25 being directly opposite each other, ostensibly forming an eight-membered heterosynthon despite the distance being longer than the cut-off value of 2.84 Å  for the independent 4LH2 and CBA molecules in (I)A⋯O3, C7⋯Cl1, Cl2⋯C14, O1⋯Cl1 and Cl2⋯O2 contacts are indeed electrostatic in nature, as shown from the red (electronegative) and blue (electropositive) regions on the ESP maps despite being relatively less intense when compared to those arising from the classical hydrogen bonds.To establish the nature of the intermolecular interactions, particularly for the weaker contacts, a mapping of the electrostatic potential (ESP) was performed over the Hirshfeld surfaces through DFT-B3LYP/6-31G basis set  are comparable to the data obtained from Gaussian 16, in which Cl1, O1, Cl2 and O2 possess charges of +0.0054, −0.0147, +0.0054 and −0.0125 atomic units (a.u.), respectively; while the C7 and C14 atoms each exhibit a weak electrostatic potential charge of +0.0251 and +0.0263 a.u., respectively. Therefore, the C7⋯Cl1 and C14⋯Cl2 interactions are dispersive in nature. On the other hand, the apparent charge complementarity between the Cl2 and H25 atoms, which align around a centre of inversion as described above, indicate the existence of an electrostatic interaction between two CBA-II molecules, Fig. 5d).Of particular interest is the observation that the chlorine atom interacts with the amide-C=O residue through an electron-deficient σ-hole region. To complement the ESP findings on these O⋯Cl and C⋯Cl contacts, non-covalent interaction plots were generated for the relevant pairwise molecules using 4LH2-I, 4LH2-II, CBA-I, CBA-II, 3M-I and 3M-II. The overall fingerprint plots for the specified molecules/aggregates are shown in Fig. 8a) and those decomposed into H⋯O/O⋯H/ H⋯C/C⋯H, H⋯N/N⋯H and H⋯Cl/Cl⋯H plots are shown in Fig. 8b)-(e).The two-dimensional fingerprint plots were generated in order to quantify the close contacts for di + de distances shorter than the sum of the respective van der Waals radii of 2.61, 2.64 and 2.84 Å . For 3M-I, the di + de values for the H⋯O/O⋯H and H⋯N contacts are, respectively, tipped at ∼1.98, ∼1.95 and ∼1.68 Å, and are attributed to -N2—H2N⋯O2-, -O1⋯H4N- and -N1⋯H4O- contacts, respectively. The analogous contacts for 3M-II are tipped at 1.95 Å for -H4N⋯O1-, ∼1.98 Å for -O2⋯H2N- and ∼1.64 Å for -N3⋯H6O-. For H⋯Cl/Cl⋯H in 3M-II, the contacts are each tipped at ∼2.80 Å owing to the pair of -H25⋯Cl2- and -Cl2⋯H25- interactions. As for the H⋯H and H⋯C/ C⋯H contacts, their di + de distances are longer than the sum of their respective van der Waals radii of 2.18 and 2.79 Å, and hence contribute little to the overall packing of the crystal despite providing the predominant surface contacts.The overall fingerprint plot of the individual components and the corresponding three-molecule aggregates exhibit a paw-like profile with asymmetric spikes indicating the inter-dependency of the intermolecular interactions between molecules to sustain the packing. The 3M-I and 3M-II aggregates display almost identical fingerprint profiles which, upon decomposition, can be delineated into H⋯H , H⋯C/C⋯H , H⋯O/O⋯H [21.2 and 20.7%], H⋯Cl/Cl⋯H [7.5 and 10.8%], H⋯N/N⋯H [6.4 and 3.8%] and other minor contacts [10.0 and 10.7%]. A detailed analysis on the corresponding decomposed fingerprint plots shows that only the H⋯O/O⋯H and H⋯N/N⋯H contacts for both 3M-I and 3M-II as well as H⋯Cl/Cl⋯H for 3M-II have 4LH2-I and 4LH2-II molecules exhibit similar fingerprint profiles with only slight differences in the contact distributions. In order of dominance, these are H⋯H (36.3% for 4LH2-I and 33.8% for 4LH2-II), H⋯O/O⋯H , H⋯C/C⋯H (21.4 and 21.2%), H⋯N/N⋯H (11.0 and 8.3%), H⋯Cl (1.7 and 6.1%) and other minor contacts (6.0 and 7.8%). There is no major deviations in the di + de distances cf. 3M-1 and 3M-II, with only the H⋯O/O⋯H as well as N⋯H contacts being shorter than the sums of their respective van der Waals radii. Each of 4LH2-I and 4LH2-II have di + de of about 1.98 Å for H⋯O/O⋯H and ∼1.64 Å for N⋯H contacts.The individual X⋯H- rather than -H⋯X-, as evidenced most notably from the distribution for O⋯H  versus H⋯O  and Cl⋯H  vs H⋯Cl . The inclination arises due to the lack of hydrogen-bond donor atoms in the CBA-I and CBA-II molecules, other than the carboxylic acid groups, so they act primarily as hydrogen-bond acceptors. Among the contacts, O⋯H and H⋯N for CBA-I have di + de distances of ∼2.40 and ∼1.64 Å, respectively, each being shorter than the sum of the respective van der Waals radii, while the same is true for H⋯O/O⋯H, H⋯N and H⋯Cl/Cl⋯H contact for CBA-II with di + de distances of ∼2.38, ∼1.62 and ∼2.82 Å, respectively.As for the individual CBA-I and CBA-II molecules, major contacts comprise H⋯H (23.7% for CBA-I and 22.1% for CBA-II), H⋯C/C⋯H , H⋯O/O⋯H (17.7 and 17.9%), H⋯Cl/Cl⋯H (16.8 and 17.5%), H⋯N (5.3 and 4.4%) and other minor contacts (15.7 and 13.9%). A detailed analysis of the corresponding contacts shows all major interactions for CBA-I and CBA-II are more inclined toward -Crystal Explorer 17  and amide-N4—H4N⋯O1(amide) hydrogen bonds has the greatest energy among all close contacts present in the crystal with an interaction energy (Eint) of −61.9 kJ mol−1. This is followed by the seven-membered heterosynthon formed between 4LH2-II and CBA-II through the carboxylic acid-O4—H4O⋯N1(pyridyl) hydrogen bond with the supporting pyridyl-C—H8⋯O5(carbonyl) contact so that Eint = −52.0 kJ mol−1. For the analogous contact between 4LH2-I and CBA-I but lacking the supporting pyridyl-C—H⋯O5(carbonyl) contact, it is gratifying to note the interaction energy is correspondingly less, i.e. Eint = −49.4 kJ mol−1. The interactions between amide-C7⋯Cl1 and amide-O1⋯Cl1, summing to Eint of −16.6 kJ mol−1, are also significant, as are the interactions between methylene-C–H6A⋯O3(amide) and pyridyl-C2–H2⋯O3(amide) with Eint = −15.8 kJ mol−1. The equivalent interactions surrounding the 4LH2-II molecule follow the same trends and give similar energies, Table 3Eint of −8.7 kJ mol−1. Finally, the C27—H27⋯O1(amide) interaction exhibits an Eint of −20.4 kJ mol−1.The calculation of the interaction energies for all pairwise interacting molecules was performed through Eele) as highlighted by the rod-shaped energy framework with a zigzag topology due to the combination of several strong interactions, Fig. 9a). Specifically, the combination of interactions between 4LH2-I and CBA-I through the terminal O4—H4O⋯N1 hydrogen bonding as well as between 4LH2-II and CBA-II via O6—H6O⋯N3 and C8—H8⋯O5 interactions leads to the formation of the core framework parallel to (101). The overall Eele of these interactions is much greater than that associated with the ten-membered synthons formed by a combination of N2—H2N⋯O2 and N4—H4N⋯O1 hydrogen bonds as evidenced from the relatively small rod radius in the energy model of the latter interactions, which align in a parallel fashion along the b axis, Fig. 9a).The crystal of (I)2O}2 synthon along with the peripheral C7⋯Cl1/O1⋯Cl1 and C14⋯Cl2/O2⋯Cl2 interactions which lead to a ladder-like topology, Fig. 9b). The combination of the electrostatic and dispersion forces results in an enhancement of the influence of the ten-membered synthons which supersedes the energy force for the terminal carboxylic acid-O—H⋯N(pyridyl) hydrogen bonds as seen in the total energy framework, Fig. 9c).Apart from the electrostatic forces, the crystal is also sustained by substantial dispersion forces, which are mainly associated with the ten-membered {⋯HNC4LH2 and mono-functional carboxylic acids; one exception was noted in the Chemical context. A different situation pertains when bi-functional carboxylic acids are employed in co-crystal formation. In these circumstances, e.g. when the carboxylic acid is bis(carboxymethyl)urea and diglycineoxamide urea  hydrogen bonds, involving both pyridyl rings, leading to three-molecule aggregates, is an almost universal trait when co-crystals are formed between N,N′-bis(pyridin-4-ylmethyl)oxalamide (4LH2) was prepared according to a literature procedure: m.p.: 486.3–487.6 K; lit. 486–487 K  was mixed with 4-chlorobenzoic acid  and the mixture was then ground for 15 min in the presence of a few drops of methanol. The procedure was repeated twice. Colourless blocks were obtained through careful layering of toluene (1 ml) on an N,N-dimethylformamide (1 ml) solution of the ground mixture. M.p.: 456.9–458.6 K. IR (cm−1): 3211 ν(N—H), 3052—2935 ν(C—H), 1669–1604 ν(C=O), 1492 ν(C=C), 1419 ν(C—N), 794 ν(C—Cl).The precursor, Uiso(H) set to 1.2Ueq(C). The oxygen- and nitrogen-bound H atoms were located from a difference-Fourier map and refined with O—H = 0.84±0.01 Å and N—H = 0.88±0.01 Å, respectively, and with Uiso(H) set to 1.5Ueq(O) or 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989020000572/hb7889sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020000572/hb7889Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020000572/hb7889Isup3.cmlSupporting information file. DOI: 1978104CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The intermolecular interactions at play were characterized via Hirshfeld surface analysis and fingerprint plots, highlighting the evident role of C—H⋯O, C—H⋯F and C—H⋯π interactions in the formation of the observed crystal structure.The structural analysis of a phenylindolizine-based drug, namely methyl 3-(4-flurobenzoyl)-7-methyl-2-phenylindolizine-1-carboxylate (I) was carried out; this drug shows an inhibitory action towards  24H18FNO3, crystallizes in the monoclinic centrosymmetric space group 1/nP2 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.The title compound, C The heterocycle is substituted at the carbon atoms C6, C7 and C8 with a methoxy carbonyl group, a phenyl ring , and a fluorobenzoyl ring , respectively  Å]. The dihedral angle between the mean plane through ring Cg3  Å, 157°; C15⋯O3iii = 3.519 (4) Å, 137°; symmetry codes: (ii) x, y − 1, z; (iii) x, y + 1, z] and C1—H1⋯π(C15)ii , forming ribbons along the [010] direction, as shown by the green shading in Fig. 3via C11—H11B⋯F1v , C11—H11A⋯π(C5) , C11—H11C⋯π(C8)  (CN), etc.Structural details of compounds such as CAJTAI  , 4-methylpyridine (2) , 2-bromo-1-(4-fluorophenyl)ethan-1-one (3) , and triethylamine  in 4.5 mL of acetonitrile were added to a 10 mL microwave tube under a nitrogen atmosphere  of the title compound  =1.2Ueq(C) or 1.5Ueq(C-methyl).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020003837/xi2021sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020003837/xi2021Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020003837/xi2021Isup3.cmlSupporting information file. DOI: 1865697CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the molecular packing, molecules are assembled into supramolecular layers in the  32H30N4O2S4, is generated by a crystallographic twofold axis that bisects the disulfide bond. The molecule is twisted about this bond with the C—S—S—C torsion angle of 90.70 (8)° indicating an orthogonal relationship between the symmetry-related halves of the molecule. The conformation about the imine bond [1.282 (2) Å] is E and there is limited delocalization of π-electron density over the CN2C residue as there is a twist about the N—N bond [C—N—N—C torsion angle = −166.57 (15)°]. An intramolecular hydroxyl-O—H⋯N(imine) hydrogen bond closes an S(6) loop. In the crystal, methylene-C—H⋯π(tolyl) contacts assemble molecules into a supramolecular layer propagating in the ab plane: the layers stack without directional interactions between them. The analysis of the calculated Hirshfeld surfaces confirm the importance of H⋯H contacts, which contribute 46.7% of all contacts followed by H⋯C/C⋯H contacts [25.5%] reflecting, in part, the C—H⋯π(tolyl) contacts. The calculation of the interaction energies confirm the importance of the dispersion term and the influence of the stabilizing H⋯H contacts in the inter-layer region.The complete molecule of the title hydrazine carbodithioate derivative, C S-alkyl-dithiocarbazate derivatives with heterocyclic aldehydes and ketones to form molecules of the general formula RSC(=S)N(H)N=C(R′)R′′, where R′, R′′ = alkyl and aryl. These molecules are effective ligands for a variety of metals and the motivation for complexation largely stems from the promising biological activity exhibited by the derived metal complexes  Å to the other side; symmetry operation (i): 1 − x, y, z. The C1—S1 bond length of 1.7921 (17) Å is significantly longer than the C1—S2 bond of 1.7463 (17) Å, which is ascribed to the S1 atom participating in the S1—S1i bond of 2.0439 (8) Å; each C1—S bond is shorter than the C9—S2 bond length of 1.8308 (18) Å.The crystallographic asymmetric unit of (I)E-conformation), N1—N2 and C2=N2 bond lengths is 1.282 (2), 1.409 (2) and 1.286 (2) Å, respectively, and suggests limited delocalization of π-electron density over this residue which is consistent with a twist about the N1—N2 bond as seen in the C1—N1—N2—C2 torsion angle of −166.57 (15)°. The presence of an intramolecular hydroxyl-O—H⋯N(imine) hydrogen bond, Table 1i—C1i torsion angle being 90.70 (8)° and the dihedral angle between the two CNS2 planes being 88.22 (3)°.The sequence of C1=N1 . Layers stack along the c axis without directional interactions between them, Fig. 2b).In the crystal, the only directional contact identified in the geometric analysis of the molecular packing employing dnorm surface, electrostatic potential  and two-dimensional fingerprint plot calculations were performed for (I)Crystal Explorer 17 , i.e. near the imine-C2 and tolyl ring, centroid designated Cg1, correspond to the C2⋯O1, C2⋯C4 short contacts  interaction, Table 1A⋯π(tolyl) interaction shows up as a distinctive orange ‘pothole’ on the shape-index-mapped Hirshfeld surface, Fig. 3b).The Hirshfeld surface analysis comprising a), the faint red spots appearing near the tolyl-H12, methylene-H9B and phenol-H8 atoms correlate with the faint red spots near the sulfanyl-S1, hydrazine-N1 and tolyl-C11 atoms, and correspond to the intra-layer tolyl-C12—H12⋯S1(sulfanyl), methylene-C9—H9B⋯N1(hydrazine) and phenol-C8—H8⋯C11(tolyl) interactions, Table 2b), with the blue and red regions corresponding to positive and negative electrostatic potentials, respectively.In the views of Fig. 4de and di diagonal axes for the overall fingerprint plot, Fig. 5a); those delineated into H⋯H, H⋯C/C⋯H, H⋯S/S⋯H, H⋯O/O⋯H, N⋯C/C⋯N and H⋯N/N⋯H contacts are illustrated in Fig. 5b)–(g), respectively. The percentage contributions for the different interatomic contacts to the Hirshfeld surface are summarized in Table 3de = di ∼2.4 Å, Fig. 5b). The tip of this H⋯H contact corresponds to an inter-layer H6⋯H14 contact with a distance of 2.39 Å, Table 2de + di ∼2.7 Å in Fig. 5c). The H⋯S/S⋯H contacts contribute 13.6% and appear as two sharp-symmetric wings at de + di ∼2.8 Å, Fig. 5d). This feature reflects the intra-layer tolyl-C12—H12⋯S1(sulfanyl) interaction, Table 2de + di ∼2.8 Å, Fig. 5e); this separation is ∼0.08 Å longer than the sum of their van der Waals radii. Although both N⋯C/C⋯N and H⋯N/N⋯H contacts appear at de + di ∼2.6–2.8 Å in the respective fingerprint plots, Fig. 5f) and (g), their contributions to the overall Hirshfeld surface are only 3.6 and 3.4%, respectively. The contributions from the other interatomic contacts summarized in Table 3The corresponding two-dimensional fingerprint plots for the calculated Hirshfeld surface of (I)d,p) basis set with the B3LYP function. The total energy comprises four terms: i.e. the electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies and these were calculated in Crystal Explorer 17  occurs within the intra-layer region and arises from the combination of C—H⋯π, C⋯O and C⋯C short contacts as well as weak C—H⋯N/C interactions. The second most significant energy of stabilization within the intra-layer region involves a major contribution from the tolyl-C12—H12⋯S1(sulfanyl) interaction (dominated by Edis) with a total energy of −29.7 kJ mol−1. In addition, a long-range H6⋯H16B contact is observed within the intra-layer region with a H⋯H separation of 2.44 Å.In the present analysis, the pairwise interaction energies between the molecules in the crystal of (I)Edis energy term also makes the major contribution to the energies of stabilization in the inter-layer region, with the separation between molecules in the inter-layer region being H⋯H contacts. The maximum energy is not found for the shortest H6⋯H14 contact (–9.5 kJ mol−1), Table 2−1), each with a distance of 2.51 Å. Views of the energy framework diagrams down the b axis are shown in Fig. 6Edis in the stabilization of the crystal.The R group, i.e. R = Me S-4-methylbenzyldithiocarbazate (10 mmol) and salicylaldehyde (10 mmol) in ∼30 ml of acetonitrile for about 2 h Uiso(H) set to 1.2Ueq(C). The O-bound H atom was located in a difference-Fourier map, but was refined with an O—H = 0.84±0.01 Å distance restraint, and with Uiso(H) set to 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 610.1107/S2056989020008762/hb7929sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020008762/hb7929Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020008762/hb7929Isup3.cmlSupporting information file. DOI: 2013050CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: