In the crystal, hydrogen bonds connect the molecules into double layers, which are connected to each other by halogen bonds.The title compound was synthesized by a new type of reaction using Mg2 as a new catalyst and a possible mechanism for this reaction is proposed. The six-membered ring adopts a half-chair conformation. In the crystal, hydrogen bonds connect the molecules into double layers, which are connected to each other by halogen bonds. The Hirshfeld surface analysis revealed that the most important contributions for the crystal packing are from O⋯H/H⋯O (35.8%), Cl⋯Cl (19.6%), Cl⋯H/H⋯Cl (17.0%), H⋯H (8.3%), C⋯O/O⋯C (4.3%), Cl⋯O/O⋯Cl (4.2%) and O⋯O (4.1%) contacts.The molecular and crystal structures of the title compound, C The reaction scheme is shown in Fig. 15,5-Dichloro-6-hydroxydihydropyrimidine-2,4 Å  x, y + 1, z; (ii) x, −y + 2, z + A⋯O1i hydrogen bond also involves O1i with a H4A⋯O1i distance of 3.058 (2) Å  −x, −y + 2, −z + 1; (v) x, −y + 2, z − A⋯O2iii  with an N1⋯O2iii distance of 2.793 (2) Å. The hydrogen bonds connect the molecules into double layers parallel to the (100) plane, as shown in Fig. 4vi [3.3670 (9) Å] and Cl2⋯Cl2vii  connect the layers, forming a three-dimensional framework.The hydrogen-bond system is shown in Fig. 3Å Table 2. In the Crystal Explorer 17.5  to 0.986 (blue) a.u., as illustrated in Fig. 5dnorm plot indicate intermolecular contacts involving the hydrogen and halogen bonds. The brightest red spots correspond to the strongest hydrogen bonds, N1—H1A⋯O2 and O3—H3⋯O2  until the components were completely dissolved. Crystallization occurred with isothermal evaporation of the resulting solution at room temperature for several weeks, giving colourless needle-shaped crystals, composition according to chemical analysis : C, 24.12/24.14; H, 2.04/2.03; Cl, 35.64/35.63; N, 14.07/14.08; O, 24.13/24.12. Crystals suitable for a X-ray structural analysis were extracted manually from this batch.The title compound was synthesized by adding 5 mg of uracil (Sigma Aldrich) to 1 ml of 1 mol l4− does not react with HCl while TcO4− is actively reduced  and possibly through radical substitution.We suggest a possible mechanism of the observed reaction. Typically, ReOUiso(H) = 1.2Ueq(C)]. O- and N-bound H atoms were refined isotropically [Uiso(H) = 1.2Ueq].Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989020011809/zq2257sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020011809/zq2257Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020011809/zq2257Isup3.cmlSupporting information file. DOI: 2025758CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


A linear gold-atom geometry defined by phosphane-P and thiolate-S atoms is found in the title compound. The packing is stabilized by a combination of fluorobenzene-C—H⋯O(methoxy), phenyl-C—H⋯F, phenyl-C—H⋯S(thiolate) and phenyl-C—H⋯π interactions to generate a three-dimensional network. 26H22AuFNOPS or [Au(C8H7FNOS)(C18H15P)], has the AuI centre coordinated by phosphane-P [2.2494 (8) Å] and thiolate-S [2.3007 (8) Å] atoms to define a close to linear geometry [P—Au—S = 176.10 (3)°]. The thiolate ligand is orientated so that the methoxy-O atom is directed towards the Au atom, forming an Au⋯O close contact of 2.986 (2) Å. In the crystal, a variety of intermolecular contacts are discerned with fluorobenzene-C—H⋯O(methoxy) and phenyl-C—H⋯F interactions leading to dimeric aggregates. These are assembled into a three-dimensional architecture by phenyl-C—H⋯S(thiolate) and phenyl-C—H⋯π interactions. Accordingly, the analysis of the calculated Hirshfeld surface shows 30.8% of all contacts are of the type C⋯H/H⋯C but this is less than the H⋯H contacts, at 44.9%. Other significant contributions to the surface come from H⋯F/F⋯H [8.1%], H⋯S/S⋯H [6.9%] and H⋯O/O⋯H [3.2%] contacts. Two major stabilization energies have contributions from the phenyl-C—H⋯π(fluorobenzene) and fluorobenzene-C—H⋯C(imine) interactions , and from the fluorobenzene-C—H⋯F and phenyl-C—H⋯O interactions , the latter leading to the dimeric aggregate.The title phosphanegold(I) thiolate, C The deviation of the P1—Au—S1 angle of 176.10 (3)° from the ideal 180° is related to the close approach of the O1 atom, i.e. Au⋯O1 = 2.986 (2) Å, as the O1 atom is directed towards the gold atom. The elongation of the C1—S1 bond to 1.762 (3) Å and the shortening of the C1—N1 bond to 1.262 (4) Å with respect to the comparable bonds in the neutral thiocarbamide molecules, i.e. S=C(OMe)N(H)Ar R3PAu[SC(OR′)=NAr]. However, a less common form is known whereby the N-bound aryl ring is orientated towards the gold atom rather than the alkoxy-oxygen atom =NPh], i.e. with Au⋯O via pairwise fluorobenzene-C—H⋯O1 and phenyl-C—H⋯F1 contacts Fig. 2a). The dimeric aggregates are connected into a three-dimensional architecture by phenyl-C—H⋯S1 interactions, with the phenyl-H atom involved in the latter interaction, i.e. H13, also participating in a C—H⋯π(fluorobenzene) interaction and so may be considered bifurcated. The two remaining contacts are of the type phenyl-C—H⋯π so the fluorobenzene ring accepts two contacts, one to either side of the ring. A view of the unit-cell contents is shown in Fig. 2b).Several directional intermolecular points of contact between molecules are noted in the extended structure of (I)dnorm , where the cooperative phenyl-C13—H13⋯π(C2–C7) interaction is shown as a distinctive orange ‘pothole’ on the shape-index-mapped Hirshfeld surface in Fig. 4b). Although the phenyl-C22—H22⋯π(C2–C7) interaction was not manifested on the Hirshfeld surface mapped over dnorm, this interaction shows up as blue ‘bump’ and orange ‘pothole’ near the H22 atom and Cg1(C2–C7) centroid, respectively, in Fig. 5a). Simultaneously, a fluorobenzene-C7—H7⋯C1(imine) contact, Table 2dnorm surface in Fig. 5b). The presence of the phenyl-C24—H24⋯π(C11–C16) contact is evidenced through faint red spots in Fig. 6a) and the orange ‘pothole’ in Fig. 6b) on the dnorm and shape-index mapped Hirshfeld surface, respectively. In addition to the C—H⋯π contacts listed in Table 1In order to understand further the interactions operating in the molecular packing of (I)a), and those delineated into H⋯H, H⋯C/C⋯H, H⋯F/F⋯H, H⋯S/S⋯H and H⋯O/O⋯H contacts are shown in Fig. 8b)–(f), respectively. The percentage contributions for the different interatomic contacts to the Hirshfeld surface are summarized in Table 3b) features a beak-shaped peak tipped at de + di ∼2.3 Å. This tip corresponds to a methyl-H8C⋯H33(phenyl) contact and has a distance 0.1 Å shorter than the sum of their van de Waals radii, Table 2c) with two symmetric spikes at de + di ∼2.4 Å. The tips of pseudo-mirrored sharp spikes at de + di ∼2.4 Å represent the shortest H⋯F/F⋯H contacts (8.1%), Fig. 8d), and correspond to the phenyl-C36—H36⋯F1 contact in Table 1de + di ∼2.7 and ∼2.5 Å, respectively, Fig. 8e) and (f), these types of contacts only contribute 6.9 and 3.2%, respectively, to the total interatomic contacts. The accumulated contribution of the remaining six different interatomic contacts is around 6.0% and these do not have a significant influence on the molecular packing.The overall two-dimensional fingerprint plot of (I)et al., 2017via the long-range corrected ωB97XD functional combining the D2 version of Grimme’s dispersion model  are listed in Table 4The interaction energies in the crystal of (I)−1). This is followed by the phenyl-C36—H36⋯F1 and phenyl-C3—H3⋯O1 interactions , which lead to the dimeric aggregate in Fig. 2a). The other directional contacts outlined in Supramolecular features contribute minor stabilization energies to the molecular packing  while the pairwise weak phenyl-C15—H15⋯π(C21–C26) and phenyl-C32—H32⋯π(C11–C16) interactions, which were identified through the Hirshfeld surface analysis, have a greater stabilization energy .The greatest stabilization energy arises from the phenyl-C22—H22⋯π(C2–C7) and fluorobenzene-C7—H7⋯C1(imine) interactions =NC6H4Y-3]. Selected geometric parameters for these are given in Table 56 residues, which vary by up to nearly 15°. Finally, there is an isostructural relationship between (I)Y = Cl compound 1H and 13C{1H} NMR spectra were recorded in CDCl3 solution on a Bruker Ascend 400 MHz NMR spectrometer  with chemical shifts relative to tetramethylsilane; the 31P{1H} NMR spectrum was recorded in CDCl3 solution on the same instrument but with the chemical shift recorded relative to 85% aqueous H3PO4 as the external reference. IR spectra were measured on a Bruker Vertex 70v FTIR spectrophotometer  from 4000 to 400 cm−1. Elemental analyses were performed on a Leco TruSpec MicroCHN Elemental Analyser .All chemicals and solvents were used as sourced without further purification. Melting points were determined on a Biobase automatic melting point apparatus MP450 . M HCl. The resulting mixture was extracted using chloroform, yielding colourless crystals after 3 weeks standing. Yield: 0.421 g (91%), m.p. 334.0–334.5 K. Analysis calculated for C8H8FNOS: C, 51.88; H, 4.35; N, 7.56%. Found: C, 51.49; H, 4.46; N, 7.42%. IR (cm−1): 3241 (br) ν(N—H), 1438 (s) ν(C—N), 1150 (s) ν(C—O), 1048 (s) ν (C=S). 1H NMR : δ 8.88 , 7.29–6.87 , 4.15  ppm. 13C{1H} NMR : δ 189.4 (Cq), 162.8 , 138.5 (aryl-C1), 130.2 , 116.8 (aryl-C6), 112.2 , 109.1 (aryl-C2), 58.9 (OCH3) ppm.The thiol precursor, LH, was prepared from the reaction of 3-fluorophenyl isothiocyanate  and MeOH  in the presence of NaOH  followed by the addition of excess 1 3PAuCl precursor was prepared from the reduction of KAuCl4 using sodium sulfite, followed by the addition of a stoichiometric amount of triphenylphosphane. The precipitate was used as isolated.The Ph3PAuCl  in acetonitrile (20 ml), LH  in acetonitrile (20 ml) was added and the solution was stirred for 3 h. The solution was left for slow evaporation at room temperature, yielding colourless crystals after 2 weeks. Yield: 0.273 g (85%), m.p. 408.0–408.5 K. Analysis calculated for C26H22AuFNOPS: C, 48.53; H, 3.45; N, 2.18%. Found: C, 48.73; H, 3.56; N, 1.97%. IR (cm−1): 1575 (s) ν(C=N), 1122 (s) ν(C—O), 1100 (s) ν(C—S). 1H NMR : δ 7.55–7.43 , 6.95–6.89 , 6.63–6.61 , 6.39–6.36 , 3.90  ppm. 13C{1H} NMR : δ 165.4 (Cq), 163.2 , 152.8 , 134.3 , 131.7 , 129.7 , 129.3 , 129.1 , 117.8 , 109.3 , 109.1 , 55.5 (OCH3) ppm. 31P{1H} NMR : δ 38.8 ppm.NaOH  in water (5 ml) was added to a suspension of PhUiso(H) set to 1.2–1.5Ueq(C). The maximum and minimum electron density peaks of 1.17 and 1.22 e Å−3, respectively, are located 0.97 and 0.69 Å, respectively, from the Au atom.Crystal data, data collection and structure refinement details are summarized in Table 610.1107/S2056989020009469/hb7932sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020009469/hb7932Isup2.hklStructure factors: contains datablock(s) I. DOI: 2015568CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


PThe crystal structure of 4-allyl-2-methoxy-6-nitrophenol, which crystallizes in the centrosymmetric space group  10H11NO4, which was synthesized via nitration reaction of eugenol  with a mixture of nitric acid and sulfuric acid, consists of three independent molecules of similar geometry. Each molecule displays an intramolecular hydrogen bond involving the hydroxide and the nitro group forming an S(6) motif. The crystal cohesion is ensured by intermolecular C—H⋯O hydrogen bonds in addition to π–π stacking interactions between the aromatic rings [centroid–centroid distances = 3.6583 (17)–4.0624 (16) Å]. The Hirshfeld surface analysis and the two-dimensional fingerprint plots show that H⋯H (39.6%), O⋯H/H⋯O (37.7%), C⋯H/H⋯C (12.5%) and C⋯C (4%) are the most important contributors towards the crystal packing.The asymmetric unit of the title compound, C The benzene rings of molecules Mol-N2 and Mol-N3 are approximately parallel to each other [dihedral angle 10.60 (7)°], and roughly perpendicular to that of Mol-N1 . A strong intramolecular O—H⋯O hydrogen bond involving a nitro O atom and the H atom of the hydroxide group forming an S(6) motif is observed in each molecule  Å; Cg2⋯Cg3ii = 3.6613 (18) Å; Cg3⋯Cg3iii = 4.0624 (16) Å; symmetry codes: (i) 2 − x, 1 − y, 1 − z; (ii) 1 + x, y, z; (iii) −x, −y, 1 − z].In the crystal, the molecules are connected by intermolecular C12s Table 1 and 3 ▸.et al., 2007Crystal Explorer 17.5 . The shape-index of the Hirshfeld surface is a tool to visualize the π–π stacking interactions . The red spots in Fig. 4a correspond to the strong C—H⋯O hydrogen-bond interactions in the crystal structure; in Mol-N1 two of them involve the O atoms of the methoxy (O1) and nitro (O3) groups as acceptors with allyl H atoms (C22B– H22B⋯O1 and C12B—H12B⋯O3), while the other is due to the interatomic interaction between the aromatic H9 donor atom and the nitro O7 oxygen atom (C9—H9⋯O7). The longer O—H⋯O hydrogen bonds and O⋯O interactions are characterized by smaller red spots close to each other on the surface, where the faint red spot indicating the O—H⋯O interactions is associated with the longest O⋯O contact of 2.96 (3) Å in Mol-N1 and Mol-N3. In Mol-N2, the red spots correspond to C—H⋯O (C9—H9⋯O7 and C12A—H12A⋯O12) and C—H⋯C (C20—H20B⋯C11A) hydrogen-bond interactions. The corresponding fingerprint plots for each of the independent molecules and for the entire asymmetric unit, showing characteristic pseudo-symmetric wings in the de and di diagonal axes, and those delineated into H⋯H, O⋯H/H⋯O, C⋯H/H⋯C and C⋯C contacts are illustrated in Fig. 6b), which is reflected in the widely scattered points of high density due to the large hydrogen-atom content of the molecule. The contribution from the O⋯H/H⋯O contacts (31.7%), corresponding to C—H⋯O and O—H⋯O interactions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond interaction with de + di ≃ 2.5Å . In the absence of weak C—H⋯π interactions in the crystal, the pair of characteristic wings in the fingerprint plot delineated into H⋯C/C⋯H contacts (7.7% contribution) have a symmetrical distribution of points , with the tips at de + di ≃ 2.65 Å. The distribution of points in the de = di ≃ 1.6 Å range in the fingerprint plot delineated into C⋯C contacts  indicates the existence of weak π–π stacking interactions between the phenyl rings, which are indicated by adjacent red and blue triangles in the shape-index map . The small contribution of the other weak intermolecular O⋯O, N⋯H/H⋯N, C⋯O/O⋯C, C⋯N/N⋯C and N⋯O/O⋯N contacts has a negligible effect on the packing.In order to explore the nature of the intermolecular contacts and their role in the crystal packing, Hirshfeld surfaces  as eluent. The reaction mixture was diluted with dichloromethane, washed with brine (3 × 10 mL), dried over anhydrous Na2SO4 and concentrated under vacuum. The crude product was subjected to chromatography on a silica-gel column with n-hexane/AcOEt (9:1 v/v) as eluent to afford the title compound as a reddish-orange liquid. Reddish-orange crystals formed spontaneously with a yield of 56%. Good quality crystals suitable for single crystal X-ray diffraction analysis were obtained by slow evaporation of an n-hexane:AcOEt solution, m.p. = 317–319 K.In a 250 mL flat-bottom flask containing a stirred solution of eugenol  and dichloromethane (60 mL), a mixture of concentrated sulfuric acid (0.78 mL) and concentrated nitric acid (0.80 mL) was added dropwise for 30 min at 273 K. The complete disappearance of the starting product was confirmed by means of thin layer chromatography using −1): 3235, 3080, 3016, 2971, 2910, 1638, 1537, 1392, 1331, 1262, 1128, 1059, 909, 763. The FT–IR spectrum  δ 10.7 , 7.53 , 6.99 , 6.01–5.88 , 5.19–5.13 , 3.96 , 3.39–3.37 . 13C NMR  δ 149.87, 144.90, 135.95, 133.66, 131.24, 118.63, 117.16, 115.11, 114.29, 56.72, 39.41. FTMS–ESI, m/z: 208.04616 (100%) [C10H11NO4].Uiso(H) = 1.2 Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl groups. The hydroxyl H atoms were located in a difference-Fourier map and refined freely. The two allyl groups of Mol-N2 and Mol-N3 are disordered over two sets of sites with refined occupancy ratios of 0.648 (8):0.352 (8) and 0.668 (9):0.332 (9) respectively. One outlier (100) was omitted in the cycles of refinement.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020002601/rz5270sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020002601/rz5270Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020002601/rz5270Isup3.cmlSupporting information file. DOI: 1986157CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Its crystal structure was determined at 100 K. Both weak intramolecular O—H⋯O and intermolecular O—H⋯S hydrogen bonding can be observed.The title compound is an example of an  22H22O2S2, 1, represents an example of an ortho-vanillin-based functionalized dithioether, which could be useful as a potential chelating ligand or bridging ligand for coordination chemistry. This dithioacetal 1 crystallizes in the orthorhombic space group Pbca. The phenyl rings of the benzyl groups and that of the vanillin unit form dihedral angles of 35.38 (6) and 79.77 (6)°, respectively. The crystal structure, recorded at 100 K, displays both weak intramolecular O—H⋯O and intermolecular O—H⋯S hydrogen bonding.The title compound, C R)(H)–S–  motif are synthesized by nucleophilic substitution of geminal dihalides X–C(R)(H)–X in the presence of thiolate RS− nSH , yielding geminal dithio ethers, also called acyclic and cyclic thioacetals  Fe(CO)2(κ1-BzSCH2SBz)]+, the 1:1 adduct [Hg2(NO3)2·BzSCH2SBz)], the dinuclear PdI complex [ClPd(μ2-BzSCH2SBz)2PdCl], and the monodimensional coordination polymer [Ag2(BzSCH2SBz)2](ClO4)2 built upon dinuclear [Ag(μ2-BzSCH2SBz)2Ag]2+ units  as the starting material. This hydroxylated aldehyde is present in the extracts and essential oils of many plants. Several papers describe also its use (in its deprotonated vanillinato form or as a Schiff base-derived ligand) in coordination chemistry  and 1.8189 (12) Å are comparable with those of [BzSC(H)(C6H4NO2-p)SBz] [1.823 (3) and 1.8262 (19) Å], but are elongated compared with those of bis(benzylsulfanyl)methane (CSD TUQPAX) , but considerably more acute than in [BzSCH2SBz] [117.33 (7)°]. There is a weak intramolecular O1⋯H2 contact of 2.17 (2) Å between the H atom of the phenolic hydroxyl group and the O-atom of the methoxy group SBz] , O2⋯S1 = 3.1315 (13) Å] similar to those reported for 4--1,2-benzenediol , while the O—H⋯S angle is more acute [139.0 (17) °] Fig. 3. This O2The benzylic methylene group on sulfur atom S2 interacts with the π-cloud of the phenyl part of the vanillin unit through a C—H⋯π interaction Table 1. The secet al., 2016et al., 2003et al., 2005et al., 2013et al., 2013et al., 2018et al., 20131.There are several other examples of structurally characterized related dithioethers bearing hydroxy substituents that give rise to the formation of supramolecular networks. Selected examples found in the Cambridge Structural Database -1,3-dithiane (WADROY) and 2-(3-hydroxyphenyl)-1,3-dithiane (KALJUD) exhibit, like 1, only intermolecular O—H⋯S hydrogen bonding, the para-derivative 2-(4-hydroxyphenyl)-1,3-dithiane (KALKAK) features solely intermolecular phenolic O—H⋯H bonding .Note that in dithioether compounds with phenolic aryl groups as encountered in The reaction scheme for the synthesis of the title compound is illustrated in Fig. 43 (10 mL) and extracted with dichloromethane (3 × 10 mL). The combined extracts were washed with H2O (3 × 20 mL) and dried over Na2SO4. Evaporation of the solvent in vacuo gave a solid product, which was further purified by column chromatography. The product was obtained as a white solid, Yield: 83% (430 mg). X-ray quality crystals were obtained by keeping a dichloromethane:hexane (1:1) mixture of 1 at 278 K for 3–4 d. 1H NMR  δ 7.26–7.19 , 6.86 , 6.78 , 5.83 , 5.13 , 3.88 , 3.79 , 3.64 .13C{1H} NMR  δ 146.5 (CqOH), 142.8 (CqOCH3), 137.8 (SCH2Cq), 129.1 (SCH2CCH), 128.4 (SCH2CCHCH), 126.9 (SCH2CCHCHCH), 125.3 (S2CHCq), 120.9 (S2CHCqCH), 119.9 (S2CHCqCHCH), 110.0 (CHCqOCH3), 56.1 (OCH3), 44.8 (S2CH), 36.7 (S2CH2). IR (ATR) cm−1: 3419 (O—H), 1430-1612 (C=C). 1054 and 1264 (C—O), 766 (C—S). HRMS: (ESI) m/z calculated for C22H22O2S2Na [M + Na]+ 405.0953, found 405.0965.3-Methoxysalicylaldehyde , benzyl mercaptan , and conc. HCl (2 mL) were added to a flask at 273 K. The mixture was stirred for 60 min at room temperature. After the reaction was complete, the resulting mixture was neutralized with 10% aq NaHCOUiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso(H) = 1.5Ueq(C-methyl). The phenolic proton H2 was refined independently.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020002091/vm2228sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020002091/vm2228Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020002091/vm2228Isup3.cmlSupporting information file. DOI: 1983985CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecular and crystal structure as well as the Hirshfeld surface were analysed for this benzothiazine derivative with potential analgesic activity. 10H8ClNO5S, which has potential analgesic activity, crystallizes in space group P21/n. The benzothiazine ring system adopts an intermediate form between sofa and twist-boat conformations. The coplanarity of the ester substituent to the bicyclic fragment is stabilized by an O—H⋯O intramolecular hydrogen bond. In the crystal, hydrogen bonds of type N—H⋯O(SO2) link the molecules into zigzag chains extending along the b-axis direction. Neighbouring chains are linked by both O—H⋯Cl and C—H⋯Cl interactions. A Hirshfeld surface analysis was used to compare different types of intermolecular interactions, giving contributions of O⋯H/H⋯O = 42.0%, C⋯H/H⋯C = 17.3%, Cl⋯H/H⋯Cl = 14.2%, H⋯H = 11.1%.The title compound, C H-2λ6,1-benzothiazine-3-carboxylates are known to be highly active analgesics  Å, Θ = 111.6 (5)°, Ψ = 192.1 (6)°. The ester substituent is essentially coplanar to the C7—C8 endocyclic double bond [the C7—C8—C9—O2 torsion angle is 3.0 (7)°] as a result of the stabilizing influence of the O1—H1O⋯O2 intramolecular hydrogen bond (Table 1S(6) in terms of graph-set theory since the six atoms comprise a intramolecular hydrogen-bonded motif. The formation of the O—H⋯O hydrogen bond causes some elongation of the C9—O2 and C7—C8 bonds as compared with typical values of 1.210 Å (Csp2=O bond) and 1.326 Å (Csp2—Csp2 bond), respectively  for the same reason. The methyl group is located in an anti-periplanar position to the C8—C9 bond [the C10—O3—C9—C8 torsion angle is −178.4 (4)°]. The noticeable steric repulsion between chlorine and the hydroxyl group . The crs Table 1 in the  was added, the mixture was boiled and stored for 15 h at room temperature. The reaction mixture was diluted with cold water and acidified with 1 N HCl to pH = 4. The solid methyl 5-chloro-4-hydroxy-2,2-dioxo-1H-2λ6,1-benzothiazine-3-carboxylate was filtered, washed with water, and dried in air. Yield 2.43g (84%); colourless crystals; m.p. 464–466 K.Methyl (chlorosulfonyl)acetate  was added dropwise under stirring to a solution of methyl 6-chloroanthranilate  and triethylamine  in CHK) Fig. 5. After 1Uiso(H) = 1.5Ueq for methyl and hydroxyl groups and with C—H = 0.93 Å, N—H = 0.88 Å, Uiso(H) = 1.2Ueq for all other hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020012566/pk2647sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020012566/pk2647Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020012566/pk2647Isup3.cmlSupporting information file. DOI: 2032151CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Bnz⋯OThz (Bnz = benzene and Thz = thiazine) hydrogen bonds form chains of molecules extending along the a-axis direction which are connected to their inversion-related counterparts by C—HBnz⋯ClDchlphy  hydrogen bonds and C—HDchlphy⋯π (ring) interactions. These double chains are further linked by C—HDchlphy⋯OThz hydrogen bonds to form stepped layers approximately parallel to (012).The title compound contains 1,4-benzothiazine and 2,4-dichlorophenylmethylidene units in which the dihydrothiazine ring adopts a screw-boat conformation. In the crystal, intermolecular C—H 24H27Cl2NOS, contains 1,4-benzothiazine and 2,4-dichlorophenylmethylidene units in which the dihydrothiazine ring adopts a screw-boat conformation. In the crystal, intermolecular C—HBnz⋯OThz (Bnz = benzene and Thz = thiazine) hydrogen bonds form chains of molecules extending along the a-axis direction, which are connected to their inversion-related counterparts by C—HBnz⋯ClDchlphy  hydrogen bonds and C—HDchlphy⋯π (ring) interactions. These double chains are further linked by C—HDchlphy⋯OThz hydrogen bonds, forming stepped layers approximately parallel to (012). The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (44.7%), C⋯H/H⋯C (23.7%), Cl⋯H/H⋯Cl (18.9%), O⋯H/H⋯O (5.0%) and S⋯H/H⋯S (4.8%) interactions. Hydrogen-bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, C—HDchlphy⋯OThz, C—HBnz⋯OThz and C—HBnz⋯ClDchlphy hydrogen-bond energies are 134.3, 71.2 and 34.4 kJ mol−1, respectively. Density functional theory (DFT) optimized structures at the B3LYP/6–311 G level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap. The two carbon atoms at the end of the nonyl chain are disordered in a 0.562 (4)/0.438 (4) ratio.The title compound, C These molecules exhibit a wide range of biological applications, indicating that the 1,4-benzothiazine moiety is a potentially useful template in medicinal chemistry research with therapeutic applications in the antimicrobial (Armenise B (S1/N1/C1/C6–C8), adopts a screw-boat conformation with puckering parameters QT = 0.5581 (16) Å, θ = 69.76 (18)° and φ = 334.3 (2)°. The planar rings, A (C1–C6) and C (C10–C15) are oriented at a dihedral angle of 88.45 (7)°. Atoms Cl1, Cl2 and C9 are almost co-planar with ring C being displaced by 0.0247 (6), −0.0732 (9) and −0.0274 (2) Å, respectively.The title compound contains 1,4-benzothiazine and 2,4-dichlorophenylmethylidene units Fig. 1, in whicBnz⋯OThz (Bnz = benzene and Thz = thiazine) hydrogen bonds link the molecules, forming chains extending along the a-axis direction, which are connected to their inversion-related counterparts by C—HBnz⋯ClDchlphy  hydrogen bonds and C—HDchlphy⋯π (ring) interactions   Table 1 and 3 ▸.Crystal Explorer 17.5 . The two pairs of wings in the fingerprint plot delineated into Cl⋯Hl/H⋯Cl contacts  have an unsymmetrical distribution of points due to a third wing, with the edges at de + di = 2.74 Å (for the long wing), de + di = 2.92 Å (for the short wing) and de + di = 3.53 Å . The pair of wings in the fingerprint plot delineated into O⋯H/H⋯O contacts  has a pair of spikes with the tips at de + di = 2.22 Å. Finally, the wings in the fingerprint plot delineated into S⋯H/H⋯S contacts  have the tips at de + di = 2.99 Å.In order to visualize the intermolecular interactions in the crystal of the title compound, a Hirshfeld surface (HS) analysis  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated to be −53.7 (Eele), −13.6 (Epol), −161.9 (Edis), 119.0 (Erep) and −134.3 (Etot) for C—HDchlphy⋯OThz, 25.6 (Eele), −5.7 (Epol), −62.1 (Edis), 23.1 (Erep) and −71.2 (Etot) -4-nonyl-3,4-dihydro-2H-1,4-benzothiazin-3-one ring.The optimized structure of the title compound, (I)et al., 2016II gave 14 hits.A search in the Cambridge Structural Database , 29° (APAJUY), 28° (SAVTUH), 26° (WOCFUS) and 25° (COGRUN). By contrast, in both EVIYIT and OMEGEU, the benzothiazine unit is nearly planar with the corresponding dihedral angle being about 4°.The largest set contains Z)-2--2H-1,4-benzothiazin-3(4H)-one (1.5 mmol), potassium carbonate (2.7 mmol) and tetra-n-butyl ammonium bromide (0.14 mmol) in DMF (20 mL) was added 1-bromononane (2.6 mmol). Stirring was continued at room temperature for 24 h. The mixture was filtered and the solvent removed. The residue obtained was washed with water. The organic compound was chromatographed on a column of silica gel with ethyl acetate–hexane (9/1) as eluent. Colourless crystals were isolated when the solvent was allowed to evaporate (yield = 79%).To a solution of (Uiso(H) = 1.5Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989020001036/lh5943sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020001036/lh5943Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020001036/lh5943Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020001036/lh5943Isup4.cmlSupporting information file. DOI: 1980073CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The dihedral angle between the mean planes of the benzene ring and that of the twisted piperidine ring is 39.89 (7)°. In the crystal, weak C—H⋯O interactions link the molecules into infinite chains along the  13H16ClNO, contains a methylpiperidine ring in the stable chair conformation. The mean plane of the twisted piperidine ring subtends a dihedral angle of 39.89 (7)° with that of the benzene ring. In the crystal, weak C—H⋯O interactions link the molecules along the a-axis direction to form infinite molecular chains. H⋯H interatomic interactions, C—H⋯O intermolecular interactions and weak dispersive forces stabilize molecular packing and form a supramolecular network, as established by Hirshfeld surface analysis.The title compound, C The C1—N1—C6—O1 and O1—C6—C7—C8 torsion angles are −167.4 (2) and 50.7 (3)°, respectively. The C1—C2—C3—C13 torsion angle [177.7 (2)°] reveals the anti-periplanar (+ap) orientation of the methyl group with respect to the piperidine ring.The molecular structure of the title compound, which features a chlorobenzene ring and a methylpiperidine ring, is shown in Fig. 1x − 1, y, z), forming chains parallel to the a axis (Table 1a). Weak C—H⋯π close contacts between H5A and the benzene ring of an adjacent  molecule provide linkage between inversion-related  chains (Table 1b). Analysis of the Hirshfeld surface  = 1.5Ueq(C-methyl) or 1.2Ueq(C) for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020001930/jj2221sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020001930/jj2221Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020001930/jj2221Isup3.cmlSupporting information file. DOI: 1973841CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The packing of the title molecular salt, in which the tin atom lies on a crystallographic inversion centre, is dominated by N—H⋯Cl hydrogen bonds. 5H7N2)2[SnCl6], the cation is protonated at the pyridine N atom and the complete dianion is generated by a crystallographic centre of symmetry. In the crystal, N—H⋯Cl hydrogen bonds link the components into a three-dimensional network built up from the stacking of alternate cationic and anionic layers. The nature of the intermolecular interactions has been analysed in terms of the Hirshfeld surfaces of the cations and the anions. The thermal behaviour and the Raman spectrum of the title compound are reported.In the title molecular salt, (C For example, in these hybrid materials, the organic part can have non-linear optical properties  and an organic cation +2·[SnCl6]2−, crystallizes in the triclinic space group PCompound (I)P Fig. 1.et al., 2018i.e. none of the chloride ions are bridging although they do accept N—H⋯Cl hydrogen bonds from the organic cations, which ensures charge balance.In the synthesis, the oxidation number of tin changes from +2 to +4 such that the resultant tin(IV) atom is hexacoordinated by chlorine atoms, generating a weakly distorted octahedron in which the metal ion lies on a crystallographic inversion centre: the length of the Sn—Cl bonds varies from 2.4216 (4) to 2.4474 (5) Å. As for the Cl—Sn—Cl angles, the discrepancy of about ± 1° [89.109 (18)–90.805 (16)°] compared to the 90° value angle of a regular octahedron shows that the angular distortion is very small. These values are comparable to those of the same anion associated with other types of cations  to 1.405 (3) Å and the C—N bond lengths are 1.341 (3) Å and 1.344 (2) Å. The values of the C—C—C angles in the pyridinium ring vary from 118.9 (2) to 120.9 (2)° whereas the C—N—C angle is 124.30 (18)°: the larger angle can be attributed to the protonation of the N atom. These values are comparable with those of the same cation associated with other types of anions (Rao a). The intermolecular interactions in (I)PLATON  in the crystal of (I)A⋯Cl1 and N2—H2B⋯Cl2 hydrogen bonds generates a chain of rings propagating along the [001] direction with a graph-set pattern of et al., 1990b). The cohesion between chains is ensured by π-stacking interactions between centrosymmetrically related aromatic rings of the cations: Cg1⋯Cg1 = 3.552 (13) Å; inter-planar angle α = 0.0 (11)°; slippage = 1.246 Å. We also note the presence of a Y—X⋯Cg1 type interaction between Sn1—Cl2 and Cg1 at an X⋯Cg distance of 3.6581 (11) Å [Fig. 2a)].The combination of N2—H2Crystal Explorer 17 a)] shows red spots corresponding to H⋯Cl/Cl⋯H close contacts, which are due to the N—H⋯Cl hydrogen bonds. The presence of the adjacent red and blue triangles in Fig. 3b) demonstrates the presence of the Cg1⋯Cg1 and Sn—Cl2⋯Cg1 interactions. The contribution of different kinds of interatomic contacts to the Hirshfeld surfaces of the individual cations and anions is shown in the fingerprint plots in Fig. 4Y—X⋯ type (N⋯Cl and C⋯Cl), 6.6% of π–π stacking type (C⋯C and C⋯N/N⋯C), 15.6% of C—H⋯π type (C⋯H/H⋯C), 6.2% of N—H⋯π type (N⋯H/H⋯N) and 21.1% of H⋯H van der Waals interactions. The two-dimensional fingerprint analysis for the anionic moieties reveals that hydrogen bonds (Cl⋯H) represent 93.8%, Y—X⋯π type interactions represent 4.4% (Cl⋯N and Cl⋯C) and van der Waals interactions of the Cl⋯Cl type represent 1.8% of the surface contacts.The Hirshfeld surface 2− anions are associated with special positions and an organic–inorganic layered structure lying parallel to the (001) plane results.A search of the Cambridge Structural Database .Crystalline cohesion in RIGDER and (I)2 atmosphere at a heating rate of 10°C min−1 in the temperature range from 25 to 500°C. The thermogram of (I)supporting information) shows that the compound loses 64.4% of its mass in the temperature range of 270–304°C. The mass loss can be attributed to the degradation of the organic entity and two chlorine atoms 1H NMR (δ ppm), 400 MHz, CDCl3): 8.16 , 7.95–7.89 , 7.03 , 6.84 . 13C NMR (δ ppm), 125 MHz, CDCl3): 154.6 (quat C Py), 144.4 (CH Py), 136.1 (CH Py), 113.8 (CH Py), 112.5 (CH Py).Tin(II) chloride dihydrate (2.25 mmol) was mixed with 2-aminopyridine (0.94 mmol) and a few drops of hydrochloric acid in an aliquot of distilled water in 1:1 molar ratio was added. After stirring, the mixture was poured into a vial  that was put in an oven for three days at 393 K. Upon cooling, prism-shaped crystals of (I)−1. The Py, ν, δ, γ and τ are: pyridine ring, stretching, in-plane bending, out-of-plane bending and torsion, respectively. RS (cm−1): 3334 ν(N—H), 3215 ν (N—H), 3106 ν(C—H), 1657 ν(py)+δ(N—H)+δ(NH2), 1620 ν(py), 1542 ν(py), 1472 ν(py)+δ(C—H), 1412 ν(py)+δ(C—H), 1378 ν(py)+δ(C—H), 1324 ν(py)+δ(C—H), 1239 ν(py)+δ(C—H), 1164 δ(py)+δ(C—H), 1120 δ(py)+δ(C—H), 996 δ(py), 846 Pyridine ring breathing+γ(C—H), 623 γ(py), 551 γ(py), 406 γ(py), 384 γ(py), 305 ν1 (Sn—Cl), 216 ν2 (Sn—Cl), 106 τ(py)+ ν(N—H⋯Cl) Uiso(H) = 1.2Ueq(C)]; the pyridine N—H atom was located in a difference map and its position was freely refined.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698902000941X/hb7922sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902000941X/hb7922Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902000941X/hb7922sup3.jpgSupporting information file. DOI: Click here for additional data file.10.1107/S205698902000941X/hb7922sup4.docxSupporting information file. DOI: 1904730CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Theoretical calculations suggested that the new bis(hydroxyimine) will exhibit histone deacetylase SIRT2, histone deacetylase class III and histone deacetylase SIRT1 activities, and will act as inhibitor to aspulvinone dimethylallyltransferase, dehydro- 47H32N2O2·C6H4Cl2, contains two anil fragments in the enol–enol form, exhibiting intramolecular O—H⋯N hydrogen bonds. The two hydroxynaphthalene ring systems are approximately parallel to each other with a dihedral angle of 4.67 (8)° between them, and each ring system makes a large dihedral angle [55.11 (11) and 48.50 (10)°] with the adjacent benzene ring. In the crystal, the bis(anil) molecules form an inversion dimer by a pair of weak C—H⋯O interactions. The dimers arrange in a one-dimensional column along the b axis via another C—H⋯O interaction and a π–π stacking interaction between the hydroxynaphthalene ring system with a centroid–centroid distance of 3.6562 (16) Å. The solvent 1,2-dichlorobenzene molecules are located between the dimers and bind neighbouring columns by weak C—H⋯Cl interactions. Theoretical prediction of potential biological activities was performed, which suggested that the title anil compound can exhibit histone deacetylase SIRT2, histone deacetylase class III and histone deacetylase SIRT1 activities, and will act as inhibitor to aspulvinone dimethylallyltransferase, dehydro-l-gulonate decarboxylase and glutathione thiolesterase.The bis(anil) molecule of the title compound, C According to the PASS program – computer prediction of biological activities  and glutathione thiolesterase (71%).Schiff bases formed by the condensation of salicylaldehydes with amines are also known as anils. They often exhibit potent antibacterial, antiproliferative and antitoxic properties  forms large dihedral angles of 78.80 (10) and 61.41 (9)°, respectively, with the benzene C14–C19 and C31–C36 rings. Each hydroxynaphthalene ring system also forms a large dihedral angle with the adjacent benzene ring . Both fragments of the hydroxynaphthalene Schiff bases are in the enol form, forming intramolecular O—H⋯N hydrogen bonds (Table 1In the title bis(anil) molecule, two hydroxynaphthalene ring systems are approximately parallel to each other with a dihedral angle of 4.67 (8)° between them Fig. 1. The 9H-s Table 1.via a pair of weak C—H⋯O interactions . Dichlorobenzene molecules are located between the dimers and bind the neighboring columns by weak C—H⋯Cl interactions  molecules form an inversion dimer s Table 1.et al., 2016via the condensation of the corresponding diamine and an appropriate hydroxyaldehyde dianiline according to the literature  = 1.2Ueq(C)], while the H atoms of the OH groups were localized in a difference-Fourier map and refined with Uiso(H) = 1.5Ueq(O).Crystal data, details of data collection, and results of structure refinement are summarized in Table 210.1107/S2056989020012104/is5554sup1.cifCrystal structure: contains datablock(s) general, I. DOI: 10.1107/S2056989020012104/is5554Isup2.hklStructure factors: contains datablock(s) I. DOI: 2019265CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Compounds 1 and 2 crystallize, respectively, in space group P21/c with Z′ = 2 and in space group Pbca with Z′ = 1. The crystals of compound 1 contain neutral and anionic Bmphfp molecules, and form a one-dimensional hydrogen-bonded chain motif. The crystals of compound 2 contain anionic Bmphfp molecules, which form a complex three-dimensional hydrogen-bonded network with the ethylenediamine and water molecules.The crystal structures of two salt crystals of 2,2-bis(4-methylphenyl)hexafluoropropane (Bmphfp) with amines, namely, dipyridinium 4,4′-dibenzoate 4,4′-dibenzoic acid, 2C Interestingly, one of the two Bmphfp molecules is neutral and the other is anionic. The C—O bond lengths of the carboxy groups are summarized in Table 1A and B are in the neutral and divalent anionic forms, respectively. The two benzene rings are twisted with respect to each other, forming dihedral angles of 72.19 (6) and 69.98 (6)°. On the other hand, compound 2 crystallizes in the orthorhombic space group Pbcn. The asymmetric unit comprises one Bmphfp anion, one ethylenediammonium cation and one water molecule . The C—O bond lengths shown in Table 1Compound it Fig. 1a. Interle Fig. 1b. The C1, the pyridine molecules form strong N—H⋯O hydrogen bonds with the carboxyl groups of Bmphfp molecule B (Table 2a). The neutral (A) and anionic (B) Bmphfp molecules form a one-dimensional hydrogen-bonded chain motif along the a-axis direction . The lengths of the negative charge-assisted O—H⋯O hydrogen bonds, 2.5732 (13) and 2.5125 (13) Å, are shorter than in the common carboxyl dimer [2.643 Å; the mean value calculated from 505 research hits in the Cambridge Structural Database  Å (C⋯F) and 2.696 (1) Å (F⋯F), respectively.In the crystal of compound B Table 2a. The non Fig. 2b. The l2, one carboxylic group of the Bmphfp molecule is linked to an ethylenediammonium cation by two N—H⋯O hydrogen bonds. The N⋯O interatomic distances are 2.7749 (14) and 2.8015 (14) Å, respectively (Table 3a). Therefore, five of the six hydrogen-atom donors of the ethylenediammonium cations are connected to Bmphfp molecules, resulting in a complex three-dimensional hydrogen-bonding network. The water molecule is linked to both Bmphfp and ethylenediamine molecules via two O—H⋯O and one N—H⋯O hydrogen bonds. Thus, the water molecules are highly stabilized by these intermolecular interactions in the crystal structure . Weak C—H⋯F and F⋯F interactions are observed between Bmphfp molecules, resulting interatomic distances of 3.493 (1) Å (C⋯F) and 2.890 (1) Å (F⋯F), respectively. In compound 2, the Bmphfp molecules do not form a discrete 1-D hydrogen bond chain motif as observed in compound 1 because the one carboxyl group is terminated by an ethylenediamine molecule.In the crystal of compound y Table 3. The othy Table 3a. Therere Fig. 3b. Weak et al., 2007CrystalExplorer17  compared to molecule A. Thus, molecule B is more closely packed with the surrounding molecules in the crystal than molecule A. This may be due to the difference in the ionic state between neutral molecule A and anionic molecule B. Compound 1 (molecule A and B) has strong hydrogen-bonding interactions, with similar but slightly weaker interactions for compound 2. The contributions to the Hirshfeld surface for 2 are listed in Table 6Hirshfeld surfaces benzene hexafluoropropane, pyridine and ethylenediamine were purchased from TCI Co., Ltd. (Japan). 2,2-Bis(4-methylphenyl)hexafluoropropane  was dissolved in methanol 10 mL. The Bmphfp solution was mixed into 5 mL of a 1.0 sp2—H = 0.86, Nsp3—H = 0.89 Å with Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table 710.1107/S2056989020005575/lh5959sup1.cifCrystal structure: contains datablock(s) 1, 2, global. DOI: 10.1107/S2056989020005575/lh59591sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989020005575/lh59592sup3.hklStructure factors: contains datablock(s) 2. DOI: 1998170, 1998169CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The PtII atoms in both molecules adopt distorted square-planar geometries, coordinated by one C and two N atoms from the tridentate 2′,6′-difluoro-6-[3-(pyridin-2-yloxy)phenyl]-2,3′-bipyridine ligand and a chloride anion: the C and Cl atoms are trans. In the crystal, C—H⋯Cl/F hydrogen bonds, F⋯π and weak π–π stacking interactions between adjacent A and B molecules and between pairs of inversion-related B molecules lead to the formation of a two-dimensional supramolecular network lying parallel to the ab plane. The sheets are stacked along the c-axis direction and linked by F⋯π and weak π–π stacking interactions between pairs of inversion-related A molecules, forming a three-dimensional supramolecular network. The photoluminescence quantum efficiency of the title compound in the blue–green region of the visible region (λmax = 517 and 544 nm) is estimated to be ∼0.2–0.3, indicating that the title compound could be a suitable candidate as the emitting material in organic light-emitting diode (OLED) applications.The title compound, [Pt(C The average length [1.949 (4) Å] of the Pt—C bonds is slightly shorter than that [2.042 (3) Å] of the Pt—N bonds because of back bonding between the metal and the anionic C atom of the ligand. The Cl1 and Cl2 atoms deviate from the mean plane consisting of the Pt and coordinated N/C atoms [r.m.s. deviations = 0.013 (1) (A) and 0.017 (1) Å (B)] with deviations of 0.700 (6) Å for A and 0.720 (6) Å for B.The asymmetric unit of the title compound, Pt Å, Cl2⋯Cg8 = 3.455 (2) Å; green dashed lines in Fig. 1Cg4 and Cg8 are the centroids of the N3/C17–C21 and N6/C38–C42 rings, respectively] between the coordinated chloride ion and the pyridine ring with fluorine substituents are also observed. Molecules A and B are interlinked by a C—H⋯Cl interaction (Table 2A and 9.64 (11)° for B. However, the terminal difluoro-pyridine ring is tilted by 46.08 (9) for A and 46.96 (8)° for B with respect to phenylpyridine ring plane. This distortion may be caused by the intramolecular Cl⋯π interaction described above. The pyridine ring of the pyridine-2-yloxy group is slightly tilted by 22.09 (13) for A and 19.70 (13)° for B relative to the phenylpyridine ring plane.In each molecule, there are intramolecular C—H⋯Cl/F interactions, contributing to the stabilization of the molecular structure Table 2. Moreoven Table 2. In the A and B molecules and between pairs of inversion-related B molecules lead to the formation of a two-dimensional supramolecular network lying parallel to the ab plane. In addition, this network is consolidated by halogen⋯π and weak π–π stacking interactions  between pairs of inversion-related B molecules. These sheets are stacked along the c-axis direction and connected by F⋯π and weak π–π stacking interactions  between pairs of inversion-related A molecules, resulting in the formation of a three-dimensional supramolecular network.In the crystal structure, intermolecular C–H⋯Cl/F hydrogen bonds Table 2 and 2 ▸ The bright blueish-green emission of the title compound in solution is dominated by phosphorescence as supported by an excited-state lifetime of more than 1 ms. Emission maxima appear at 517 and 544 nm at room temperature, as shown in Fig. 4SciFinder , gave two hits. These are the reports of the crystal structures and photophysical properties of the free ligands for 2′,6′-difluoro-6-[3-(pyridin-2-yloxy)phenyl]-2,3′-bipyridine and 2′,6′-dimethoxy-6-[3-(pyridin-2-yloxy)phenyl]-2,3′-bipyridine phenyl]-2,3′-bipyridine 2, 2  and xylene (10 ml) was refluxed (433 K) for 48 h under an N2 flow. The xylene was removed by distillation and the crude product was purified by silica gel column chromatography  to give the title compound as a yellow solid in 40% yield. Orange–red crystals suitable for X-ray crystallography analysis were obtained from a CH2Cl2/hexane solution by slow evaporation. 1H NMR  δ 9.91 , 8.20, 7.97 , 7.90–7.84 , 7.50–7.42 , 7.30–7.22 , 7.06 , 6.97-6.91 . 13C NMR  δ 206.5, 167.3, 156.4, 155.9, 151.0, 148.1, 146.6, 146.5, 140.1, 139.0, 125.7, 125.0, 121.0, 118.4, 118.3, 117.6, 115.9, 106.0, 105.9, 105.7, 105.6. Analysis calculated for C21H12ClF2N3OPt: C 42.69; H 2.05; N 7.11%; found: C 42.70, H 2.06, N 7.09%.The title compound was synthesized as follows: A mixture of the ligand , PtClUiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989021000128/hb7960sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989021000128/hb7960Isup2.hklStructure factors: contains datablock(s) I. DOI: 2053861CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-019-47062-2, published online 22 July 2019Correction to: This Article contains errors in the Results section where,“It was noted that the vessel diameter of the untreated veins was (on average?) 132% higher than that of the treated veins , indicating that the treated veins were thinner.”should read:“It was noted that the vessel diameter of the untreated veins was 132% higher than that of the treated veins , indicating that the treated veins were thinner.”“Additionally, the (average?) RNV vessel diameter was estimated to be 29.83 ± 4.17 µm, which was 97.77% thinner than choroidal vessels (59.00 ± 11.47 µm), p < 0.05.”should read:“Additionally, the RNV vessel diameter was estimated to be 29.83 ± 4.17 µm, which was 97.77% thinner than choroidal vessels (59.00 ± 11.47 µm), p < 0.05.”


II ion is coordinated in a distorted octahedral [FeN4O2] environment by two dicyanoaurate anions, two water molecules and two partially protonated 1,2-di(4-pyridyl)ethylene molecules. Dicyanoaurate anions bridge the FeII cations, forming infinite chains, which propagate along the a-axis direction. The chains are connected via aurophillic interactions with two non-coordinated dicyanoaurate anions for each FeII ion.In the title compound, the Fe 2][Au(CN)2]2·bpe·2H2O}n , the FeII ion is coordinated in a distorted octahedral [FeN4O2] environment by two dicyanoaurate anions, two water molecules and two partially protonated 1,2-di(4-pyridyl)ethylene molecules. Dicyanoaurate anions bridge the FeII cations, forming infinite chains, which propagate along the a-axis direction. The chains are connected via aurophilic interactions with two non-coordinated dicyanoaurate anions for each FeII ion. The polymeric chains interact with each other via π–π stacking between the guest bpe molecules and multiple hydrogen bonds.In the title compound [Fe(bpe)(Hbpe)Au(CN) These layers are supported by N-donor aromatic ligands . Di-, tetra- and octacyanometallic  anions have been introduced to develop coordination compounds of this kind. It has been shown that the inclusion of guest molecules can significantly influence the temperature, completeness and step character of spin transition in complexes belonging to this class (Hbpe)Au(CN)2](Au(CN)2)2·bpe·2H2O in which the FeII ions are stabilized in the high-spin (HS) state.Here we describe the crystal structure of a new cyanometallic FeP4O2] octahedral environment  Å, N5—H5A⋯N5i = 176°; Table 1The title compound crystallizes in the triclinic nt Fig. 1 formed bII coordination environment is Σ|90 −  θ| = 6.8°, where θ are cis-N—Fe—N or cis-N—Fe—O angles. Two CN− anions bridge the Fe2+ and Au+ cations [Fe1⋯Au1 = 5.280 (3) Å], creating a one-dimensional polymer, Fe1—N1—C1 = 172.8 (7)°, N1—C1—Au1 = 179.1 (8)° and C1—Au1—C1 = 180.0°, leading to a very slight deviation from linearity of the chains. This chain binds one guest bpe and two guest water molecules per FeII centre.The deviation from the ideal octahedral geometry of the Fe2]− counter-ions are connected with the polymeric chains by aurophilic interactions and C7⋯N2B hydrogen bonds . These free counter-ions are disordered over two positions with Au1—Au2A = 3.324 (1) Å and Au1—Au2B = 3.101 (5) Å. The polymeric chains are connected to each other via π–π interactions  Å, α = 10.3°, offset = 1.043 Å, where Cg1 and Cg2 are the centroids of the N4/C4–C8 and N6/C16–C20 rings, respectively, and Cg3⋯Cg4 = 3.794 (6) Å, α = 6.8°, offset = 1.835 Å, where Cg3 and Cg4 are the centroids of N5/C11–C15 and N6ii/ Cii16–C20 rings, respectively]. Guest bpe molecules are additionally linked to the polymeric chains by hydrogen bonds with coordinated water molecules . One of the guest water molecules forms hydrogen bonds with the coordinated water [Fig. 3A⋯O2 = 156°] and weak hydrogen bonds with free dicyanoaurate counter-ions  and free dicyanoaurate counter-ions . Hydrogen-bonding parameters are summarized in Table 1The structure is characterized by the presence of several different kinds of weak interactions that create a three-dimensional supramolecular framework. Two free  bis(2-phenylpyrazine)bis(aqua)iron(II)gold(I) bis(cyano)gold(I)]  in water (0.5 ml), the second was a mixture of water/ethanol  and the third layer was a solution of 1,2-di(4-pyridyl)ethylene (0.05 mmol) and [Fe(OTs)2]·6H2O  in ethanol (0.5 ml) with 0.2 ml of water. After two weeks, red crystals grew in the second layer; the crystals were collected and kept in the mother solution prior to measurement.Crystals of the title compound were prepared by the slow diffusion method between three layers in a 3 ml tube. The first layer was a solution of K[Au(CN)iUso(H) = 1.2Uiso(C), Uiso(H) = 1.2Uiso(N), Uiso(H) = 1.5Uiso(O). Uaniso values for all C and N atoms in the guest dicyanoaurate anions and the O2 and O3 water molecules were constrained to be equal using the EADP command. Distances N3A—C3A and N2A—C2A were restrained to a target of 1.15 Å and distances Au2A—C3A and Au2A—C2A were restrained to a target of 1.99 Å using the DFIX command. The following distances were restrained to be equal using the SADI command: C2A—N2A and C2B—N2B; Au1—C2A and Au1—C2B; C3A—N3A and C3B—N3B; Au1—C3A and Au1—C3B; C2A—C3A and C2B—C3B.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020006738/tx2022sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020006738/tx2022Isup2.hklStructure factors: contains datablock(s) I. DOI: 2004716CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The dihedral angle between the mean plane of the anthraquinone ring system and the dioxepine ring in the title compound is 16.29 (8)°. The packing is consolidated by C—H⋯O, π–π and C=O⋯π interactions. 17H12O4, was synthesized from the dye alizarin. The dihedral angle between the mean plane of the anthraquinone ring system (r.m.s. deviation = 0.039 Å) and the dioxepine ring is 16.29 (8)°. In the crystal, the molecules are linked by C—H⋯O hydrogen bonds, forming sheets lying parallel to the ab plane. The sheets are connected through π–π and C=O⋯π interactions to generate a three-dimensional supramolecular network. Hirshfeld surface analysis was used to investigate intermolecular interactions in the solid-state: the most important contributions are from H⋯H (43.0%), H⋯O/O⋯H (27%), H⋯C/C⋯H (13.8%) and C⋯C (12.4%) contacts.The title compound, C The colour of anthraquinone-based compounds can be modified by the type and position of the substituents attached to the anthraquinone nucleus P21/n with one molecule in the asymmetric unit: it consists of three fused six-membered rings and one seven-membered ring as shown in Fig. 1Compound (I)q2 = 0.896 (2) Å, φ2 = 113.50 (12)°, q3 = 0.358 (2) Å, and φ3 = 217.8 (3)°. These metrics indicate that the ring adopts a screw boat conformation. The C—O and C=O bond lengths lie within the ranges 1.355 (2)–1.457 (2) Å and 1.216 (2)–1.226 (2) Å, respectively, confirming their single and double-bond character.A puckering analysis of the seven-membered ring yielded the parameters B⋯O1 hydrogen bonds form inversion dimers with an A⋯O3 contacts, thereby generating corrugated chains of molecules . A C17—H17B⋯O2 hydrogen bond links the chains together (Table 1b and 2c), forming sheets propagating in the ab plane. These sheets are supported by extensive π–π contacts between adjacent rings, with centroid-to-centroid distances Cg1⋯Cg2 = 3.599 (2) and Cg2⋯Cg3 = 3.683 (2) Å  and weak C12=O1⋯π [oxygen–centroid distance = 3.734 (2) Å] interactions es Fig. 2a. A C17r Table 1b and 2cns Fig. 3, linkinget al., 2016viz. 1-hydroxy-2-methoxy-6-methyl  and two-dimensional fingerprint plots  shows the molecular electrostatic potential surface generated using TONTO with a STO-3G basis set in the range −0.050 to 0.050 a.u. within the Hartree–Fock level of theory. Molecular sites evidenced in red correspond to positive potential energy and in blue to negative potential energy de and di diagonal axes. The most important interaction is H⋯H, contributing 43% to the overall crystal packing, which is reflected in Fig. 5b as widely scattered points of high density due to the large hydrogen content of the molecule, with small split tips at de ≃ di ≃ 1.2 Å. The contribution from the O⋯H/H⋯O contacts (27%) [note that the O⋯H interactions make a larger contribution (14.6%) than the H⋯O interactions (12.4%)], corresponding to C—H⋯O interactions, is represented by a pair of sharp spikes characteristic of a strong hydrogen-bond interaction, de + di ≃ 2.35 Å . The significant contribution from C⋯H/H⋯C contacts (13.8%) to the Hirshfeld surface of (I)d, with de + di ≃2.55 Å. The distribution of points in the de = di ≃ 1.75 Å range in the fingerprint plot delineated into C⋯C contacts indicates the existence of weak π–π stacking interactions between the central anthracene ring and the C6–C11 and C1–C4/C13–C14 rings . Aromatic π–π interactions are indicated by adjacent red and blue triangles in the shape-index map and also by the flat region around these rings in the Hirshfeld surfaces mapped over curvedness in Fig. S1c.As illustrated in Fig. 5 Å Fig. 5c. The sgs Fig. 4b and 5ede + di ≃ 3.2 Å in Fig. 5f.The contribution of 3.2% from C⋯O/O⋯C contacts is due to the presence of short interatomic C=O⋯π contacts, and is apparent as the pair of parabolic tips at N hydrochloric acid, extracted with chloroform (3 × 30 ml) and then chromatographed on a silica gel column with dichloromethane/petroleum ether (1/1) as eluent, which yielded 200 mg (35%) of 1,2-propylenedioxyanthraquinone as a yellow compound  was treated with 1,3-dibromo-propane  in dimethylformamide (30 ml) in the presence of anhydrous potassium carbonate  with stirring and heated to 393 K for 24 h. The reaction mixture was evaporated to dryness under vacuum and the resulting crude product was acidified with 12 nd Fig. 6. Colourl1H NMR : δ (ppm): 8.21 , 7.95 , 7.72 , 7.26 , 4.48 , 4.43 , 2.34 ; 13C NMR : δ (ppm): 182.9, 182.5, 157.3, 151.3, 135.2, 133.9, 133.4, 132.6, 129.6, 127.1, 126.5, 126.0, 125.9, 123.3, 70.5, 70.2, 30.0. Analysis calculated for C17H12O4: C, 72.85%; H, 4.32%; found: C, 72.82%; H, 4.29%.Uiso(H) = 1.2Ueq(C). The reflection (011), affected by the beam-stop, was removed during refinement.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020003965/hb7899sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020003965/hb7899Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020003965/hb7899Isup3.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020003965/hb7899sup4.docxSupplementary figures: Hirshfeld surface analysis. DOI: 1991271CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal of the title compound, the packing is driven by O—H⋯O, O—H⋯N and N—H⋯N hydrogen-bond interactions along with π–π stacking interactions. 10H8N8·2H2O or H2bmtz·2H2O , the asymmetric unit consists of one-half molecule of H2bmtz and one water molecule, the whole H2bmtz molecule being generated by a crystallographic twofold rotation axis passing through the middle point of the 1,4-dihydro-1,2,4,5-tetrazine moiety. In the crystal, N—H⋯O, N—H⋯N, O—H⋯O hydrogen bonds and aromatic π–π stacking interactions link the components into a three-dimensional supramolecular network. Hirshfeld surface analysis was used to further investigate the intermolecular interactions in the crystal structure.In the title compound, C Many compounds of this class are bioactive (Jubeen I) is shown in Fig. 12bmtz and one water molecule, in which the whole molecule of the H2bmtz is generated by a crystallographic twofold rotation axis passing through the middle point of the 1,4-dihydro-1,2,4,5-tetrazine moiety. The H2bmtz molecule is therefore not planar (r.m.s. deviation from planarity = 0.598 Å) with a C4—C5—N3—N4i torsion angle of 178.46 (14)° . The pyrimidine rings are twisted with respect to each other, making a dihedral angle of 43.67 (9)°. The 1,4-dihydro-1,2,4,5-tetrazine moiety adopts a twist-boat conformation with a C5—N3—N4i—C5i torsion angle of −41.17 (17)°. The N3—N4i and C5—N4 bond lengths of 1.423 (2) and 1.395 (2) Å, confirm their single-bond character, while the C3—N5 bond length of 1.278 (2) Å, is consistent with a double bond  Å]. At the same time, the water molecules are connected by O—H⋯O hydrogen bonds  make a less significant contribution. The contribution of the H⋯O/O⋯H (9.0%) contacts (i.e. C—H⋯O and O—H⋯O) and other contacts such as C⋯C (7.1%) (i.e. π–π stacking), H⋯C/C⋯H (6.1%) and N⋯N (4.7%) make a small contribution to the entire Hirshfeld surface.To further quantify the nature of the intermolecular interactions present in the crystal structure, Hirshfeld surfaces -1,2,4,5-tetrazine]bis[bis(triphenylphosphine)copper(I)] bis(tetrafluoridoborate) dichloromethane solvate -1,4-dihydro-1,2,4,5-tetrazine][μ2-(dicyanoethenylidene)amido][(dicyanoethenylidene)amido]acetonitriledisilver(I)] .All commercially available chemicals and solvents were of reagent grade and were used as received without further purification. HUiso(H) = 1.2Ueq(C). The 1,4-dihydro-1,2,4,5-tetrazine and water H atoms were located in difference-Fourier maps and were constrained to N—H = 0.86 ± 0.01 Å with Uiso(H) = 1.2Ueq(N) and O—H = 0.84 ± 0.01 Å with Uiso(H) = 1.5Ueq(O), respectively.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020002765/hb7895sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020002765/hb7895Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020002765/hb7895Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020002765/hb7895Isup4.cmlSupporting information file. DOI: 1986751CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The asymmetric unit of the title compound contains two independent molecules, consisting of perimidine and phenol units, which are linked through an N—H⋯O hydrogen bond. Intramolecular O—H⋯N hydrogen bonds are observed in both independent molecules. 17H14N2O, contains two independent molecules each consisting of perimidine and phenol units. The tricyclic perimidine units contain naphthalene ring systems and non-planar C4N2 rings adopting envelope conformations with the C atoms of the NCN groups hinged by 44.11 (7) and 48.50 (6)° with respect to the best planes of the other five atoms. Intramolecular O—H⋯N hydrogen bonds may help to consolidate the molecular conformations. The two independent molecules are linked through an N—H⋯O hydrogen bond. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (52.9%) and H⋯C/C⋯H (39.5%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Density functional theory (DFT) optimized structures at the B3LYP/ 6–311 G level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.The asymmetric unit of the title compound, C H Perimidines are defined as peri-naphtho-fused pyrimidines , carried out at the B3LYP/6-311G  level, are compared with the experimentally determined molecular structure in the solid state.I, contains two crystallographically independent molecules each consisting of perimidine and phenol units, where the tricyclic perimidine units contain naphthalene ring systems and non-planar C4N2 rings  and B′ (N1A/N2A/C1A/C9B–C11B) rings gave the parameters q2 = 0.9280 (12) Å, q3 = 0.1829 (12) Å, QT = 0.9459 (13) Å, θ2 = 75.85 (15)° and φ 2= 134.47 (18)° for B and q2 = 0.5320 (11) Å, q3 = 0.3791 (11) Å, QT = 0.6533 (14) Å, θ2 = 54.33 (12)° and φ 2= −5.47 (13)° for B′; both rings adopt envelope conformations, where atoms C1A and C1B are at the flap positions and at distances of 0.6044 (12) and −0.6590 (13) Å, respectively, from the best planes through the other five atoms. The C4N2 rings may alternatively be described as being hinged about the N⋯N vectors with the N1A/C1A/N2A and N1B/C1B/N2B planes being inclined by 44.11 (7) and 48.50 (6)°, respectively, to the best planes through the other five atoms (N1A/N2A/C9A–C11A) and (N1B/N2B/C9B–C11B). Rings A (C2A–C7A), C (C10A–C15A), D (C9A/C10A/C15A–C18A) and A′ (C2B–C7B), C′ (C10B–C15B), D′ (C9B/C10B/C15B–C18B) are oriented at dihedral angles of A/C = 76.78 (4), A/D = 78.49 (4), C/D = 2.09 (3)° and A′/C′ = 88.43 (3), A′/D′ = 88.31 (3), C′/D′ = 3.26 (4)°. Intramolecular O—H⋯N hydrogen bonds  analysis  have the tips at de + di = 2.50 Å. The scattered points in the pair of spikes in the fingerprint plot delineated into H⋯O/O⋯H  have a symmetrical distribution with the tips at de + di = 2.49 Å. The H⋯N/N⋯H contacts  have a distribution of points with the tips at de + di = 2.72 Å. Finally, the C⋯C interactions  are reflected in Fig. 4f as low density wings with the tips at de + di = 3.60 Å.The shape-index of the HS is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles; if there are no adjacent red and/or blue triangles, then there are no π–π interactions. Fig. 3dnorm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions in Fig. 5a–c, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H and H⋯C/C⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing  using standard B3LYP functional and 6–311 G basis-set calculations , hardness (η), potential (μ), electrophilicity (ω) and softness (σ) are recorded in Table 3σ is for the evaluation of both the reactivity and stability. The electron transition from the HOMO to the LUMO energy level is shown in Fig. 6H-perimidin-2-yl)phenol ring. The energy band gap [ΔE = ELUMO - EHOMO] of the molecule is 1.4933 eV, the frontier molecular orbital energies EHOMO and ELUMO being −3.2606 and −1.7673 eV, respectively.The optimized structure of the title compound, I, are II phenol product (Rf = 0.70 in hexane/ethyl acetate (1:0.5), yield: 97% A significant quantity of the colourless monocrystalline product was obtained by the slow evaporation of the solvent after 15 days.0.35 mol (1.48 g) of 1,8-diaminonaphthalene and 18.8 mmol (2 ml) of salicylaldehyde were introduced into a 250 ml flask and 30 ml of ether were added thereto. The mixture was stirred magnetically for 3 days. The grey precipitate that formed was recovered by filtration, washed with ether, rinsed with ethanol and dried under Büchner. The resulting brownish powder was recrystallized several times from ethanol to obtain colourless 2- = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in are summarized in Table 410.1107/S2056989020005939/lh5957sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020005939/lh5957Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020005939/lh5957Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020005939/lh5957Isup4.cmlSupporting information file. DOI: 1976884CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The metalated species were characterized in situ by NMR spectroscopy and in two cases isolated as crystalline solids. Single‐crystal XRD studies revealed the presence of salt‐like structures with strongly interacting ions. Synthetic applications of K[(R2N)2P(BH3)] were studied in reactions with a 1,2‐dichlorodisilane and CS2, which afforded either mono‐ or difunctional phosphine boranes with a rare combination of electronegative amino and electropositive functional disilanyl groups on phosphorus, or a phosphinodithioformate. Spectroscopic studies gave a first hint that removal of the borane fragment may be feasible.Metalation of secondary diaminophosphine boranes by alkali metal amides provides a robust and selective access route to a range of metal diaminophosphide boranes M[(R It′s just so plain borane: Alkali metal diaminophosphide boranes, which can be selectively prepared by metalation of PH‐substituted precursors with non‐nucleophilic amides, were for the first time isolated and characterized crystallographically. Their synthetic application as highly functional nucleophilic building blocks is illustrated in metatheses with a dichlorodisilane and the formation of a stable carbon disulfide adduct. I or diorganophosphide boranes II ,Ib,c/IIb,c)3Si, IdIb/IIb) parent (Ic/IIc) and silylated phosphides (Id) are special because their ability to undergo electrophilic post‐functionalization of reactive P−H and P−Si bonds after the initial metathesis step makes them essentially polyfunctional building blocks.Typical phosphide reagents carry usually chemically inert alkyls or aryls 2P(Fe(CO)4]KIII, R=Et, Ph) and [(Me2N)(Ph3C)P(W(CO)5]KIV) containing metal‐stabilized mono‐ or diamino‐phosphido ligands were generated as spectroscopically detectable entities by deprotonation of PH‐substituted precursor complexes and shown to react as P‐centered nucleophiles. The significance of diaminophosphide boranes as synthetic intermediates was first recognized by the group of Knochel,1 a] that had been generated in situ by lithium reduction of a chlorophosphine borane precursor but was neither positively identified nor further characterized (Scheme 1 a]) and lithium diethylaminophosphide borane (Li[1 a]) can be alternatively accessed through metalation of a secondary diaminophosphine borane precursor 2PCl and LiBH42N)2PCl with Me2S⋅BH3  furnished only inseparable mixtures of 2 b with Me2NH⋅BH3 (10–20 mol %). As the by‐product did not interfere with the subsequent metalation reactions, the mixtures were used without further purification. Reactions aiming at the generation of phosphides were carried out in THF, diethyl ether, or mixtures thereof, and reaction monitoring and product identification was generally achieved in situ by multinuclear  NMR spectroscopy. We found that reliable and highly selective generation  of phosphide boranes M[1 b–f] was feasible by treating the PH‐substituted precursors 2 b–e with a slight excess of a non‐nucleophilic alkali amide such as lithium di(isopropyl)amide (LDA) or a metal hexamethyldisilazide (MHMDS=MN(SiMe3)2, M=Li, Na, K, Scheme 2 b with NaHDMS in a THF/ether mixture and with KHMDS in the presence of a crown ether permitted also the isolation of first crystalline diaminophosphide boranes of composition Na[1 b]⋅THF and K[1 b] , respectively. Both products were characterized by single‐crystal X‐ray diffraction studies (see further below).To deepen our insight into the formation of diaminophosphide boranes, we tested the routes reported for accessing Li[1 c] and heterocyclic derivatives like K[1 d], K[1 e], while selective lithiation of heterocyclic secondary diaminophosphine borane 2 e was best accomplished with LDA. Metalation of the secondary diazaphospholene borane 2 f turned out a borderline case. Treatment with KHMDS produced detectable amounts of the expected, highly moisture and air sensitive phosphide K[1 f], which was identified by spectroscopic data and chemical trapping with a proton source. However, both deprotonation and recovery of the secondary phosphine borane were in this case unselective and produced side‐products that could neither be successfully identified nor separated. We relate the difficulties encountered in the generation of K[1 f] to the unusual electronic structure of unprotected secondary diazaphospholenes, which display a hydride reactivity that contrasts the behavior of alkyl and arylphosphines and is associated with an “Umpolung” of the P−H bond.Moreover, using KHMDS for deprotonation enabled both the generation of a sterically congested diaminophosphide reagent like K,1 c] but proceeded unselectively and irreproducibly with heterocyclic substrates. The use of Grignard reagents was tested with sterically uncongested diaminophosphine boranes 2 a,b. While MeMgCl converted both substrates cleanly into the corresponding phosphides, EtMgBr was found to be unreactive.Application of other deprotonating reagents than amides gave erratic results. Metalation with 3 a,b3 b, which afforded a low yield of the metalation product K[1 b] along with a main product later identified4 b  4 b and substantial amounts of unidentified by‐products. We have currently no concise explanation for the varying selectivity, even if it is tempting to relate the observed changes to different sterics of the substrates.Exploring the reduction of chlorophosphine boranes 1 b–f] comes from 31P and 11B NMR spectra. The signals display the expected multiplet structures arising from spin‐coupling between 11B (I=3/2) and 31P (I=1/2) nuclei and lack a characteristic splitting due to 1JPH coupling across a P−H bond. As previously noted1 a] and K[1 a], the 31P NMR chemical shifts of specimens with identical diaminophosphide units show metal‐dependent changes, and the presence of a cation sequestering reagent like dibenzo‐18‐crown‐6 induces increases in δ31P of potassium phosphide boranes K by 10 to 15 ppm. Both effects suggest the presence of tight contact ion pairs in solution. The non‐uniform trends observed  discredit a simplistic assumption that declining covalency in the phosphorus‐metal bonding with growing size of the metal ion induces a deshielding of the 31P nucleus. The 11B NMR signals of M[1 a–f] display positive “metalation shifts” (Δδ11B +5 to +11 ppm) and numerically reduced 1JP11B coupling constants relative to the corresponding secondary phosphine borane precursors 2 a–f. The same trends hold for dialkyl and diarylphosphide boranes  and an unusually low shift for sterically congested M[1 c] . A concise explanation for these effects is yet lacking.The diagnostically most valuable information for the identification of metalated diaminophosphide boranes M[ 11B I=3/ and 31P  11B I=3/ and 31P 1 b] (space group P1‾) and monoclinic K[1 b] (space group P21/c) and important metrical parameters are displayed in Figures Graphical representations of the results of single‐crystal X‐ray diffraction studies on triclinic Na(THF) b (space1 b] contain dimeric units assembled from two anionic diaminophosphide borane and two cationic Na(THF) fragments  to 2.39(2) Å) and a weaker contact to a B−H bond of the adjacent borane in the same unit (Na‐H 2.69(2) Å). Interactions of this type have precedence in the structures of alkyl/arylphosphide boranes[1 b] the dimeric units to form one‐dimensionally infinite strands aligned parallel to the crystallographic a‐axis. If we count the η2‐bound borane as one ligand, the metal ions exhibit an irregular pseudo‐[4+1] coordination geometry in which the weak “intramolecular” B−H interaction is aligned roughly opposite to the oxygen atom of the THF ligand. The phosphorus atom displays a distorted tetrahedral coordination with bond angles from 103.1(1)° (N1−P1−B1) to 118.8(1)° (Na1−P1−B1). The P−B and P−N distances are in the range of single bonds, with the deviation of 0.053(2) Å between the P−N distances reflecting the different coordination numbers of the nitrogen atoms. While the Na1−O1 distance of 2.311(1) Å is a close match to the sum of covalent radii (2.32(11) ÅCrystals of Na(THF) b contaie boranes15, 171 b] contains two independent anionic units and two cations which aggregate, as in the sodium analogue, via K⋅⋅⋅N and K⋅⋅⋅P interactions to form strongly puckered six‐membered cyclic arrays . The coordination sphere of the linking metal ion is completed by additional contacts to a η3‐bound borane unit (H⋅⋅⋅K2 2.645(27) to 2.762(31) Å) from the second next dimeric unit in the row, which reinforce the supramolecular assembly and give rise to the formation of a double stranded array of heterocyclic units extending along the crystallographic b‐axis. Completion of the coordination sphere of the N2‐coordinated potassium ion is accomplished by weaker BH⋅⋅⋅K interactions (H⋅⋅⋅K1 2.69(3) to 3.04(3) Å) with borane units from adjacent, parallel strands. These secondary interactions result ultimately in the formation of two‐dimensional layers, which extend in the crystallographic a,b‐plane and are held together by van‐der‐Waals interactions. The P−N (1.697(2) to 1.741(2) Å) and P−B distances (1.935(4), 1.947(3) Å are similar as in Na(THF)[1 b] and correspond to single bonds. The P⋅⋅⋅K (3.301(1), 3.352(1) Å) and N⋅⋅⋅K distances (2.849(2) to 2.961(2) Å) exceed the reported sum of covalent radii (P−K 3.10(15), N−K 2.74(13) ÅCrystalline K and K[1 e] afforded exclusively monosubstitution products , even when the nucleophile was employed in excess  or crystalline solids  and characterized by analytical and spectroscopic data. The 1H, 11B, 13C and 31P NMR spectra are unremarkable and confirm the proposed constitution. The 29Si NMR spectrum of 7 is peculiar as the expected multiplet (representing the X‐part of an ABX spin system) degenerates accidentally to a simple doublet. One of the two expected 29Si NMR signals of 6 e stayed undetected for unknown reasons.To explore the feasibility of this approach, we studied reactions of diaminophosphide boranes with commercially available 1,2‐dichloro‐1,1,2,2‐tetramethyldisilane s Scheme . In cont6 e and 7 were further confirmed by single‐crystal X‐ray diffraction studies. Crystals of 7 ° and 180°, Figures 6 e holds likewise two independent molecules, both of which exhibit, however, a nearly eclipsed conformation around the Si−Si bond. The chlorine and phosphorus atoms in one molecule adopt a gauche‐orientation . The N‐heterocyclic rings exhibit similar twist conformations as in borane‐free diazaphospholidines7 are unremarkable and suggest the presence of normal single bonds. The P−N distances in both complexes are shorter than in free acyclic or N‐heterocyclic phosphines,octane (DABCO).11B NMR spectroscopy as the expected bis‐borane adduct of DABCO  which lacks the characteristic broadening arising from spin‐coupling to a quadrupolar 11B nucleus and is tentatively assigned to the targeted borane‐free diphosphino‐disilane. In addition, signals attributable to unknown borane‐free phosphorus‐containing species  and bis(diethylamino)phosphine  were detected, and the 11B NMR spectrum revealed further the presence of residual 7 . The product distribution observed can be explained by assuming that de‐protection is in principle feasible but remains incomplete and is accompanied by P−Si bond cleavage arising from adventitious hydrolysis. Attempts to isolate any of the de‐protected phosphorus‐containing products remained unsuccessful.The 1,2‐diphosphino‐disilane representing the backbone of 1 a] with carbon dioxide and carbon disulfide. While the former gave rise to an intractable colorless solid that could as yet not be unambiguously characterized, the reaction with CS2 proceeded cleanly to afford a soluble species which was isolated as a red, air and moisture stable crystalline solid after work‐up and recrystallization from ether/pentane. Analytical and MS data are in accordance with the formation of phosphinodithioformate borane 8  to 3.435(2) Å, K⋅⋅⋅O (2.820(2) Å), and weaker contacts to a remote sulfur and two hydrogen atoms of a η2‐coordinated borane unit (K⋅⋅⋅S 3.806(2) Å, K⋅⋅⋅H 2.62(6), 2.85(6) Å). The anion is built around a phosphorus atom with distorted tetrahedral and a carbon atom with planar coordination. The P−N (1.653(4), 1.663(3) Å) and P−B (1.915(6) Å) distances are still shorter than in 6 e, 7 but remain in the range of single bonds. The P−C (1.849(4) Å) and C−S (1.680(54), 1.687(4) Å) distances match those reported for zwitterionic triaminophosphonio dithioformates (R2N)3P+–CS2− (P−C 1.848(4), 1.849(2) Å; C−S 1.651(4) to 1.675(3) Å2N)3P+–CS2Me (P−C 1.852(5) Å2N)2P–CS2–P(NR2)2 containing a tri‐coordinate P atom (P−C 1.895(4) Å2 fragment are rather insensitive to the nature of the P substituents.Considering all interactions together, the potassium ions can be assigned a [5+3] coordination sphere arising from close contacts to the sulfur atoms of two μIn this work, we established the metalation of secondary diaminophosphine boranes with alkali metal amides as broadly applicable and robust access route to nucleophilic diaminophosphide building blocks based on both acyclic and N‐heterocyclic molecular frameworks. Hexamethyldisilazides emerged as reagents of choice because of their ability to react as universally applicable bases which allow free selection of alkali metals. Alternative approaches to the target molecules, such as metalation of the diaminophosphine boranes with organometallic reagents or reductive metalation of P‐chloro‐substituted precursors, worked well in selected cases but gave generally erratic results. Moreover, borane complexes of diazaphospholenes materialized as critical substrates, which reacted unselectively to afford low yields of spectroscopically detectable metalation products beside unidentified by‐products. We presume that this behavior reflects the pertinent hydride character of the P−H bonds in the free phosphines.Beyond previous findings, sodium and potassium dimethylaminosphosphide boranes were for the first time isolated as room‐temperature‐stable solids. Their crystallographic characterization reveals the presence of salt‐like structures that are distinguished by intimate interactions between ions of opposite charge via a combination of dative M⋅⋅⋅N and M⋅⋅⋅P and agostic M⋅⋅⋅H−B contacts. While both types of interactions are not unprecedented for aryl and alkyl phosphide boranes, the availability of additional nitrogen donor centers increases the density of the interaction network.Last, but not least, the potential of diaminophosphide boranes to act as synthetic building blocks is illustrated by their conversion into phosphine boranes that are distinguished by a combination of electronegative amino and electropositive functional silyl groups. Initial studies indicate that removal of the borane units is in principle feasible, and we are currently striving to develop reliable synthetic protocols to accomplish this task.2O, toluene) or by using a solvent purification system . NMR spectra were recorded on Bruker Avance 250 or Avance 400 instruments. Chemical shifts in 1H NMR spectra were referenced to TMS using the residual signals of the deuterated solvent =1.73 ppm; δ(C6D6)=7.15 ppm) as secondary reference. NMR Spectra of heteronuclei were referenced using the Ξ‐scaleΞ=25.145020 MHz, 13C; Ξ=19.867187 MHz, 29Si), BF3Et2O  and 85 % H3PO4  as secondary references. Coupling constants involving boron refer to 11B isotopomers, with 1:1:1:1 multiplets being denoted as q. The product composition in metalation experiments was derived from analysis of the 1H NMR signals of the N‐substituents of 1 b–f. Elemental analyses were carried out with an Elementar Micro Cube elemental analyzer. Mass spectra were obtained with a Bruker Daltonics Mikrotof‐Q‐Mass spectrometer. Phosphine boranes 2 a,2 e3 aAll reactions were carried out under an atmosphere of inert Argon and in flame‐dried glassware if not mentioned otherwise. Solvents were dried by distillation from alkali metals  at T=130(2) K. The structures were solved by direct methods [1 b], K[1 b], 6 e, 7, 8) contain the supplementary crystallographic data for this paper. These data are provided free of charge by the joint Cambridge Crystallographic Data Centre and Fachinformationszentrum Karlsruhe Access Structures service.Deposition numbers Bis(dimethylamino)phosphine borane (2 b): Method A: PCl3 (0.1 mL 1.14 mmol) was added under stirring to a cooled (−78 °C) solution of P(NMe2)3 (0.42 mL 2.29 mmol) in Et2O (50 mL). Stirring was continued while the solution was allowed to warm to ambient temperature. The solution was cooled again to −78 °C and BH3⋅SMe2  was added. The mixture was stirred for 1 h at −78 °C and allowed to warm to RT. After cooling once more to −78 °C, LiAlH4  was added. The mixture was stirred for 1 h at −78 °C, allowed to warm to RT, and stirred for further 24 h. Water (0.5 mL) was added and volatiles were evaporated under reduced pressure. The solid residue was extracted with hexane (20 mL). The extract was dried (Na2SO4) and solids were removed by filtration. Evaporation of the solvent under reduced pressure afforded 2 b as colorless solid which melted around RT . Method B: PCl3 (0.49 mL 5.6 mmol), P(NMe2)3 (2.00 mL 11.2 mmol) and BH3⋅SMe2  were reacted in Et2O (30 mL) as described under A. Li[BEt3H]  was added. The mixture was allowed to warm to RT and stirred for further 18 h. Volatiles were evaporated under reduced pressure and the residue was taken up in pentane (150 mL). The resulting mixture was filtered over Celite. Evaporation of the solvent under reduced pressure gave 2 b as colorless oil , which contained according to NMR measurements 10 to 20 % dimethylamine borane. 31P{1H} NMR (C6D6): δ=89.2 ppm ; 11B{1H} NMR (C6D6): δ=−40.2 ppm ; 1H NMR (C6D6): δ=5.96 , 2.27 , 1.42 ppm ; 13C{1H} NMR (C6D6): δ=38.5 ppm ; MS(ESI): m/z=119.08 .Bis(diisopropylamino)phosphine borane (2 c): LiBH4  was added to a stirred solution of (iPr2N)2PCl  in Et2O (25 mL). The mixture was stirred for 1 h. Volatiles were evaporated under reduced pressure and the residue extracted with hexane (4×20 mL). The combined extracts were filtered, the filtrate concentrated under reduced pressure, and the product isolated by crystallization at −24 °C . 31P{1H} NMR (C6D6): δ=46.3 ppm ; 11B{1H} NMR (C6D6): δ=−35.6 ppm ; 1H NMR (C6D6): δ=6.70 , 3.43 , 1.61 , 1.10 , 0.98 ppm ; 13C{1H} NMR (C6D6): δ=46.4 ppm , 22.6 ; MS(ESI): m/z=246.2 [M+]; C12H32BN2P (246.19 g mol−1): calcd C 58.55 H 13.10 N 11.38, found C 58.28 H 12.84 N 11.13.1,3‐Bis‐1,3,2‐diazaphospholidine borane (2 d): NaBH4  was added under stirring to a cooled (0 °C) solution of 2‐chloro‐1,3‐bis1,3,2‐diazaphospholidine  in MeCN (10 mL). The mixture was stirred for 24 h and during this time allowed to warm slowly to RT. Water (0.5 mL) was added, volatiles evaporated under reduced pressure and the residue extracted with toluene (75 mL). The extract was dried (Na2SO4) and filtered. Evaporation of the filtrated gave 2 d as yellow solid . 31P{1H} NMR (C6D6): δ=75.3 ppm ; 11B{1H} NMR (C6D6): δ=−39.8 ppm ; 1H NMR (C6D6): δ=7.35 , 6.98 , 6.91 , 3.21–2.88 , 2.48 , 2.10 , 1.2 ppm ; 13C{1H} NMR (C6D6): δ=139.3 , 138.0 , 129.1 , 128.6 , 49.1 , 18.7 , 18.5 ppm ; MS ((+)‐ESI): m/z=337.14 [MK+–BH3]; C18H26BN2P (312.19 g mol−1): calcd C 69.25 H 8.39 N 8.97, found C 69.00 H 8.51 N 8.68.1,3‐Bis‐1,3,2‐diazaphospholene borane (2 f): NaBH4  was added to a suspension of 2‐bromo‐1,3‐bis‐1,3,2‐diazaphospholene  in MeCN (50 mL). The mixture was stirred for 18 h, filtered, and evaporated to dryness. The residue was washed with pentane and dried in vacuum to afford 477 mg (77 %) of crude 2 f. Further purification was feasible by extracting the crude product with benzene, filtration, and evaporation of the filtrate to dryness. 31P{1H} NMR (C6D6): δ=79.8 ppm ; 11B{1H} NMR (C6D6): δ=−40.2 ppm ; 1H NMR (C6D6): δ=8.10 , 7.01–6.82 , 5.37 , 2.43 , 2.10 , 1.6 ppm ; 13C{1H} (C6D6): δ=138.7 , 137.4 , 136.4 , 129.0 , 128.4 , 127.8 , 118.8 , 19.3 , 18.5 ppm ; MS ((+)‐ESI): m/z=310.19 [M+], 311.19 [M+H+]; C18H24BN2P (310.19 g mol−1): calcd C 69.70 H 7.80 N 9.03, found C 68.45 H 7.88 N 9.06. The reason for the low carbon content is not known.Chloro‐bis(dimethylamino)phosphine borane (3 b): BH3⋅SMe2  was added under stirring to a cooled (0 °C) solution of (Et2N)2PCl  in Et2O (10 mL). After 30 min, the solution was allowed to warm to RT and stirred for further 18 h. The solvent was then removed under reduced pressure and the residue dissolved in hexane (10 mL). After reaction control by 31P NMR, enough BH3⋅SMe2  to convert unreacted starting material and more hexane (10 mL) were added. Filtering the mixture over Celite and removal of the solvent under reduced pressure gave 3 b as yellow oil . The product is thermally unstable and decomposes even below room temperature; it must be used immediately and cannot be stored.31P{1H} NMR (C6D6): δ=139.7 ppm ; 11B{1H} NMR (C6D6): δ=−36.0 ppm ; 1H NMR (C6D6): δ=2.27 , 1.59 ppm ; 13C{1H} (C6D6): δ=36.7 ppm . The thermal instability precluded obtaining a meaningful elemental analysis.General procedure for the metalation of secondary diaminophosphine boranes 2 b,d,f with alkali metal bis(trimethylsilyl)amides: MHMDS  was added to a 0.06–0.2 m solution of the secondary diaminophosphine borane in THF or [D8]THF (1 to 2 mL). The solution was stirred for 10 min at RT. An aliquot of the reaction mixture was then transferred to an NMR tube and characterized by multinuclear NMR spectroscopy. Conversion to the metalation product was derived from evaluation of the integrals in 1H NMR spectra. Deprotonation at phosphorus was in all cases confirmed by the disappearance of the characteristic signal splitting due to 1JPH.1 b]: Conversion 86 %. 31P{1H} NMR (C6D6): δ=145.9 ppm ; 11B{1H} NMR (C6D6): δ=−34.6 ppm ; 1H NMR ([D8]THF): δ=2.73 , 0.64 ppm ; 13C{1H} NMR ([D8]THF): δ=43.8 ppm .Li[1 b]: Conversion 90 %. 31P{1H} NMR (C6D6): δ=145.0 ppm ; 11B{1H} NMR (C6D6): δ=−34.3 ppm ; 1H NMR ([D8]THF): δ=2.76 , 0.66 ppm ; 13C{1H} NMR ([D8]THF): δ=44.9 ppm .Na[1 b]: Conversion 84 %. 31P{1H} NMR (C6D6): δ=142.9 ppm ; 11B{1H} NMR (C6D6): δ=−32.9 ppm ; 1H NMR ([D8]THF): δ=2.7 , 0.70 ppm ; 13C{1H} NMR ([D8]THF): δ=44.3 ppm .K[1 f]: conversion 70 %. 31P{1H} NMR (C6D6): δ=201.6 ppm ; 11B{1H} NMR (C6D6): δ=−29.5 ppm ; 1H NMR ([D8]THF): δ=7.00–6.63 , 5.54 , 2.46 ppm ; 13C{1H} NMR ([D8]THF): δ=127.6 , 121.9 , 127.8 , 117.6 , 19.5 ppm .K[Isolation of sodium bis(dimethylamino)phosphide borane Na[1 b]: A solution of Na[1 b] was prepared as described above from NaHMDS  and 2 b  in THF (2 mL). Storage at −24 °C produced colorless, highly air and moisture sensitive crystals, which were separated by decantation (no yield determined) and characterized by NMR spectroscopy (see Table Isolation of potassium bis(dimethylamino)phosphine borane K[1 b]: KHMDS  and dibenzo‐18‐crown‐6  were added to a solution of 2 b  in a mixture of Et2O (3 mL) and THF (7 mL) was carried out as described above. The mixture was stirred for 5 min. Storage at −24 °C produced colorless, highly air and moisture sensitive crystals, which were separated by decantation (no yield determined) and characterized by NMR spectroscopy  was evaporated to dryness. A solution of 2 b  in [D8]THF (1 mL) was added. The solution was stirred for 5 min and then analyzed by multinuclear NMR spectroscopy : δ=142.4 ppm ; 11B{1H} NMR (C6D6): δ=−33.0 ppm ; 1H NMR ([D8]THF): δ=2.58 , 0.45 ppm ; 13C{1H} NMR ([D8]THF): δ=43.4 ppm .General procedure for the metalation of secondary diaminophosphine boranes 2 c,e: The metalation agent ][1 c]: 1.2 equiv. KHMDS and 1.0 equiv. dibenzo‐18‐crown‐6; for Li[1 e]: 1.33 equiv. LDA; for [K(dibenzo‐18‐crown‐6)][1 e]: 2.0 equiv. KHMDS and 1.0 equiv. dibenzo‐18‐crown‐6) was added to a 3–6 mm solution of the secondary diaminophosphine borane in Et2O (20 to 25 mL). After stirring for 1 h, volatiles were removed under reduced pressure. The residue was dissolved in [D8]THF or C6D6 and characterized by multinuclear NMR spectroscopy. 31P and 11B NMR data are included in Table 31P{1H} NMR spectra. Deprotonation at phosphorus was in all cases confirmed by the disappearance of the characteristic signal splitting due to 1JPH.1 c]: Conversion >98 %. 31P{1H} NMR (C6D6): δ=61.8 ppm ; 11B{1H} NMR (C6D6): δ=−32.9 ppm ; 1H NMR ([D8]THF): δ=3.56 , 1.12 , 1.02 , 0.33 ppm ; 13C{1H} NMR ([D8]THF): δ=47.3 , 23.9 ppm : δ=−0.39 ppm (s).Li[1 c]: 31P{1H} NMR (C6D6): δ=53.4 ppm ; 11B{1H} NMR (C6D6): δ=−29.5 ppm ; 1H NMR (C6D6): δ=3.75 , 1.43 , 1.23 , 0.47 ppm ; 13C{1H} NMR (C6D6): δ=47.9 , 24.7 , 24.2 ppm .K[1 c]: Conversion 94 %. 31P{1H} NMR (C6D6): δ=68.5 ppm ; 11B{1H} NMR (C6D6): δ=−30.4 ppm ; 1H NMR ([D8]THF): δ=6.97–6.84 , 4.22–4.14 , 3.61 , 1.13 , 1.04 , 0.76 ppm ; 13C{1H} NMR ([D8]THF): δ=120.7 , 110.7 , 68.6 , 67.3 , 47.3 , 24.1 ppm .[K(dibenzo‐18‐crown‐6)][1 e]: 31P{1H} NMR (C6D6): δ=185.7 ppm ; 11B{1H} NMR (C6D6): δ=−32.2 ppm ; 1H NMR ([D8]THF): δ=6.97 , 4.1 , 3.99 , 3.26 , 1.22 , 1.18 ppm ; 13C{1H} NMR ([D8]THF): δ=150.6 , 149.1 , 143.1 , 124.1 , 122.9 , 54.2 , 27.4 , 25.0–24.5 ppm .Li[1 e]: 31P{1H} NMR (C6D6): δ=187.7 ppm ; 11B{1H} NMR (C6D6): δ=−29.9 ppm ; 1H NMR ([D8]THF): δ=6.94 , 4.22–3.80 , 3.16 , 1.25–1.12 ppm ; 13C{1H} NMR ([D8]THF): δ=150.5 , 149.4 , 143.3 , 124.3 , 123.1 , 122.7 , 54.4 , 27.3 , 25.5 , 25.2 , 24.1 , 23.1 ppm .K[1 e]: 31P{1H} NMR (C6D6): δ=197.3 ppm ; 11B{1H} NMR (C6D6): δ=−29.8 ppm ; 1H NMR ([D8]THF): δ=6.95 , 6.82 , 4.27–4.04 ,3.98 , 3.84 , 3.22 , 1.20 , 1.15 , 0.67 ppm ; 13C{1H} NMR ([D8]THF): δ=142.2 , 122.1 , 118.8 , 108.8 , 66.6 , 65.3 , 52.6 , 25.6 , 22.9 , 22.7 ppm .[K(dibenzo‐18‐crown‐6)] was prepared as described above from 2 a , KHMDS  and Et2O (15 mL). CS2  was added through a microliter syringe. The solution was stirred for 18 h. The solvent was evaporated under reduced pressure. The remaining work‐up was carried out in air. The residue extracted with Et2O (10 mL). The extract was filtered in air over Celite, and pentane (10 mL) was added. Storing the solution at −24 °C afforded 8 as red crystalline solid . 31P{1H} NMR (C6D6): δ=93.4 ppm (broad); 11B{1H} NMR δ=−34.0 ppm (broad); 1H NMR (C6D6): δ=3.35 , 3.20 , 1.19 , 1.07 ppm ; 13C{1H} NMR (C6D6): δ=42.0 (broad), 14.4 , detection of the CS2‐carbon atom was precluded by low S/N; C9H22BKN2PS2⋅0.5 H2O (313.3 g mol−1): calcd C 34.50 H 7.72 N 8.94 S 20.47; found C 33.85 H 7.49 N 8.67 S 19.93. The deviation between calculated and found analytical data is presumably due to a higher water content of the hygroscopic sample ; MS ((−)‐ESI): m/z=264.11 [(M−K)−].The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file.


The title compound exists in the crystal as a dimer of ion pairs. Hydrogen bonding and weak π–π interactions along with N—H⋯π interactions are involved in consolidating this cluster. The three-dimensional crystal structure consists of stepped stacks of dimers of ion pairs associated by C—H⋯π(ring) and slipped π-stacking interactions. 21H15N2+·C7H5O2−, 2-phenyl-1H-phenanthroimidazole and benzoic acid form an ion pair complex. The system is consolidated by hydrogen bonds along with π–π interactions and N—H⋯π interactions between the constituent units. For a better understanding of the crystal structure and intermolecular interactions, a Hirshfeld surface analysis was performed.In the title compound, C The space group is monoclinic, P21/n and two asymmetric units, two M1+ ions and two benzoate ions, are combined in an inversion dimer of ion pairs °] to one another and the torsional angle C1—O1—N1—C22 is 78.24 (su?)°. Unit A is stabilized by hydrogen bonds  Å].The structure of the title compound is shown in Fig. 1A units are associated through weak, slipped, π-stacking interactions between the C9–C14 benzene rings and N1/C22/N2/C21/C8 imidazole rings across inversion centers .Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020005344/mw2157sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020005344/mw2157Isup2.hklStructure factors: contains datablock(s) I. DOI: 1997348CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: