II dithiocarbazate complex features a square-planar trans-N2S2 donor set for the metal atom 2], features a trans-N2S2 donor set as a result of the CuII atom being located on a crystallographic centre of inversion and being coordinated by thiolate-S and imine-N atoms derived from two dithiocarbazate anions. The resulting geometry is distorted square-planar. In the crystal, π(chelate ring)–π(furyl) [inter-centroid separation = 3.6950 (14) Å and angle of inclination = 5.33 (13)°] and phenyl-C—H⋯π(phenyl) interactions sustain supramolecular layers lying parallel to (Cg(furyl) contacts (Cu⋯Cg = 3.74 Å) were also found. Interaction energy calculations suggest the contacts between molecules are largely dispersive in nature.The title Cu The conformation about the endocylic imine bond is Z, as a result of chelation, whereas the exocyclic imine bond has an E conformation.The molecular structure of (I)s Table 1. The res2CS chelate rings. While the r.m.s. deviation for the five atoms is relatively small at 0.0453 Å, suggesting a near planar ring, a better description for the conformation is that of an envelope with the copper atom being the flap atom. In this description, the r.m.s. deviation of the S1, N1, N2 and N3 atoms of the ring is 0.0002 Å, with the Cu atom lying 0.199 (3) Å out of the plane. The dihedral angle between the best plane through the chelate ring and the 2-furyl ring is 5.33 (18)° indicating an essentially co-planar relationship. By contrast, the dihedral between the chelate and phenyl rings is 86.75 (7)°, indicative of an orthogonal relationship. Finally, the dihedral angle between the peripheral organic rings is 81.42 (9)°.The bidentate mode of the coordination of the dithiocarbazate ligand leads to the formation of five-membered CuNet al., 2008II in (I)ca 10° in (I)ca 5°, changes consistent with the reorganization of π-electron density from the C1—S1 to C1—N1 bonds in (I)The structure of the acid form of the anion in (I)a). The association between molecules is of the type π(chelate ring)–π(furyl) whereby the inter-centroid Cg–Cgi separation is 3.6950 (14) Å with angle of inclination = 5.33 (13)°; symmetry operation (i) x, −1 + y, z. Such π–π interactions between chelate rings and aromatic rings are well documented in the literature, especially for sterically unencumbered square-planar complexes and can impart significant energies of stabilization to the molecular packing , Table 2b). Details of the weak intermolecular contacts connecting layers are given in the analysis of the calculated Hirshfeld surfaces below.The most prominent feature of the molecular packing is the formation of supramolecular layers lying parallel to a), and those delineated into H⋯H, C⋯H/H⋯C, S⋯H/H⋯S and C⋯C contacts are illustrated in Fig. 6b)–(e), respectively; the percentage contribution from all the identified interatomic contacts to the Hirshfeld surface are summarized quantitatively in Table 4The overall two-dimensional fingerprint plot, Fig. 6de + di ∼2.1 Å in the fingerprint plot delineated into H⋯H contacts in Fig. 6b), represents the short inter-layer H⋯H contact involving phenyl-H8 atoms, Table 3de + di ∼2.7 Å in the respective delineated fingerprint plot of Fig. 6c) and Table 3d), the short interatomic contact involving the S-benzyl atoms, Table 3de + di < 3.0 Å, i.e. at the sum of van der Waals radii. The distribution of points in the fingerprint plot delineated into C⋯C contacts, Fig. 6e), forming triangular tip at de + di ∼3.3 Å is due to the presence of such short interatomic contacts summarized in Table 3The conical tip appearing at Crystal Explorer , polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep). The energies were obtained using the wave function calculated at the HF/STO-3G level theory. The strength and nature of the intermolecular interactions are summarized quantitatively in Table 5x, −1 + y, z in Table 5Cg(furyl) = 3.74 Å], π(chelate)–π(furyl), C⋯C and S⋯H/H⋯S interactions. Among these interactions, the short interatomic S⋯H/H⋯S contact contributes to the electrostatic component while the others to the dispersion component of the energies. Even though the inter-centroid distance between symmetry-related phenyl (C3–C8) rings are greater than 4.0 Å  and the interatomic S⋯H distance is greater than sum of their van der Waal radii , they possess greater interaction energies compared to intermolecular phenyl-C—H⋯π(phenyl) and short interatomic H⋯H contacts, as summarized in Table 5b-axis direction in Fig. 7Eele, Edisp and Etot, respectively; the radius of the cylinder is proportional to the magnitude of interaction energy. It is clearly evident from the energy frameworks shown in Fig. 7Utilizing et al., 2016e.g. substituents carrying pyridyl or phenoxide, neutral molecules only and non-solvated structures yielded 24 analogues to (I)trans-N2S2 square-planar geometry as in (I)2)5Me]=NN=CC6H4OMe-4}2]2 arising from intermolecular Cu⋯S interactions between centrosymmetrically related trans-N2S2 square-planar geometries  was synthesized following a procedure adapted from a previous report : 3089 (w) ν(N—H), 1609 (m) ν(C=N), 1016 (s) ν(N—N), 763 (s), ν(C=S).26H22CuN4O2S4: C, 50.84; H, 3.61; N, 9.12; Cu, 10.34. Found; C, 50.49; H, 3.45; N, 8.77; Cu, 10.81. FTIR : 1593 (m), ν(C=N), 964 (s), ν(N—N), 760 (s), ν(C—S).Synthesis of (I)Uiso(H) set to 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 610.1107/S2056989019006145/hb7822sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019006145/hb7822Isup2.hklStructure factors: contains datablock(s) I. DOI: 1913482CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


We recently reported homologous [Ln(Cpttt)2][B(C6F5)4] (1‐Ln) for all the heavier Ln from Gd–Lu; herein, we extend this motif to the early Ln. We find, for the largest LnIII cations, that contact ion pairs [Ln(Cpttt)2{(C6F5‐κ1‐F)B(C6F5)3}]  are isolated from reactions of parent [Ln(Cpttt)2(Cl)] (2‐Ln) with [H(SiEt3)2][B(C6F5)4], where the anion binds weakly to the equatorial sites of [Ln(Cpttt)2]+ through a single fluorine atom in the solid state. For smaller SmIII, [Sm(Cpttt)2][B(C6F5)4] (1‐Sm) is isolated, which like heavier 1‐Ln does not exhibit equatorial anion interactions, but the EuIII analogue 1‐Eu could not be synthesised due to the facile reduction of EuIII precursors to EuII products. Thus with the exception of Eu and radioactive Pm this work constitutes a structurally similar family of Ln metallocenium complexes, over 50 years after the [M(Cp)2]+ series was isolated for the 3d metals.As the dysprosocenium complex [Dy(Cp Herein, we extend these studies to the lighter, larger Ln to define the characteristic features of analogous [Ln(Cpttt)2]+ cations across the Ln series. We find that for the largest members of the 1‐Ln series one meta‐F of the [B(C6F5)4]− anion coordinates to the exposed equatorial site in the solid state, giving [Ln(Cpttt)2{(C6F5‐κ1‐F)B(C6F5)3}] . However, smaller SmIII yields an isolated cation, [Sm(Cpttt)2][B(C6F5)4] (1‐Sm), which is structurally analogous to the heavier members of the series. We were unable to complete the series with the Eu analogue 1‐Eu as the stability associated with the +2 oxidation statettt)2(X)]  precursors.We previously reported that the bulky ion [BC6F4]− provi1‐Ln ,ttt)2{(C6F5‐κ1‐F)B(C6F5)3}]  and [Sm(Cpttt)2][B(C6F5)4] (1‐Sm) were all synthesised by the reactions of [Ln(Cpttt)2(Cl)]  with [H(SiEt3)2][B(C6F5)4]3)2][B(C6F5)4] was selected as a reagent for Ln metallocenium cation formation as: (i) it is soluble in benzene, hence strongly coordinating O‐donor solvents can be avoided; (ii) there is a significant enthalpic effect due to formation of a strong Si−Cl bond, and (iii) there is an additional entropic effect arising from two reactant species giving three product species. Complexes 1‐Ln  were crystallised from dichloromethane (DCM) layered with hexane and became more temperature‐sensitive as soon as DCM was added; thus, these complexes were stored at −25 °C and measurements were performed below −25 °C. Despite repeated efforts we were unable to recrystallise 1‐Ln  from DCM/hexane; we later found that these complexes dissolved in hot toluene and could be recrystallised and stored at room temperature.According to previously published synthetic methods for the synthesis of 2‐Ln were synthesized from LnCl3 and two equivalents of KCpttt by modification of the synthesis of 2‐Pr and 2‐Nd from the parent LnCl3 and NaCpttt (Scheme 3 with NaCpttt gives [Eu(Cpttt)2], with elimination of half an equivalent of (Cpttt)2 via reductive coupling.ttt)2(F)] by the oxidation of [Eu(Cpttt)2]2][PF6]5 and [Fe(Cp)2]. However, this did not occur and instead we obtained [{Eu(Cpttt)(μ‐PF6‐κ4‐F)(THF)}2] (3) in 60 % yield, along with several crystals of (Cpttt)2 (4), presumably due to the contamination of the EuII starting material with THF solvates, such as [Eu(Cpttt)2(THF)] or [Eu(Cpttt)(I)(THF)x]n, and subsequent ligand scrambling. Therefore, Eu is the only Ln apart from radioactive Pm that we were unable to access via these anion abstraction procedures. Crystalline yields for 2‐Ln are similar (46–52 %) except for 2‐La, which was isolated in 31 % yield. For 1‐Ln, the crystalline yields were dependent upon the solvent system; yields were significantly higher when crystallised from toluene (67 % for 1‐La and 69 % for 1‐Sm) compared to those crystallised from DCM layered with hexane (21–59 %).The precursors t Scheme .19 This 1‐Ln and 2‐Ln were generally in excellent agreement with expected values, although low carbon values, likely due to carbide formation from incomplete combustion, were consistently obtained in some cases. In spite of this, the bulk purity of 1‐Ln was indicated by the consistency of other analytical data with their formulations (see below). Complex 1‐Sm contains the largest LnIII ion in a Ln metallocenium cation with no equatorial interactions to be isolated to date. The most appropriate explanation for the structural change for the largest LnIII cations is a simple argument based on ionic radii, with the two Cpttt rings offering a sufficient amount of steric protection around the smaller SmIII ion III ions are large enough to accommodate a further interaction .R ligands and the weakly coordinating anion.Elemental analysis results obtained for 1H NMR spectra were recorded from −350 to +350 ppm for 1‐Ln and 2‐Ln 4]− anions in 1‐Ln were observed by 11B{1H} and 19F{1H} NMR spectroscopy (see Supporting Information). In the case of 1‐La, we could also employ 13C{19F} NMR spectroscopy to characterise the [B(C6F5)4]− anion: the expected four aromatic resonances were located at 124.26 (ipso‐), 136.91 (m‐), 138.79 (p‐) and 148.71 ppm (o‐); the signal for the ipso‐carbon is a quartet from coupling with 11B (1JBC=51.8 Hz). Signals in the 11B{1H} NMR spectra of 1‐Ln were observed between −20 and −16 ppm, and three peaks were observed in the 19F{1H} NMR spectra, corresponding to meta‐, para‐ and ortho‐F. In the 19F{1H} NMR spectrum of 1‐Sm, the para‐F signal is a triplet from coupling to two adjacent meta‐F atoms (JFF=20.4 Hz), but this is a singlet for 1‐La, presumably due to broadening by quadrupolar 139La (I=7/2). The 11B and 19F NMR spectra of [Sc(Cp*)2{(C6F5‐κ2‐F)B(C6F5)3}]2{(μ‐C6F5‐κ1‐F)2B(C6F5)2}]2 1‐Ln (Ln=Gd–Lu).6F5)4]− anions in light 1‐Ln are only weakly bound in solution, and dissociate to give isolated [Ln(Cpttt)2]+ cations, as evidenced by the symmetry of 19F NMR spectra.19F NMR studies of 1‐La in C7D8, but the spectra were unchanged down to 218 K. Finally, the paramagnetism of 3 precluded assignment of its 1H, 13C, 19F and 31P NMR spectra.1‐Ln, 2‐Ln, 3 and 4 were determined by single crystal XRD 2]+ cation of 1‐Sm exhibits identical structural features with 1‐Dy,meta‐fluorine of one of the C6F5 rings of the [B(C6F5)4]− anion. In all cases, the [Ln(Cpttt)2]+ fragments exhibit bent geometries and the Cpcentroid⋅⋅⋅Ln⋅⋅⋅Cpcentroid angles for 1‐Ln are closer to linearity than the corresponding precursors 2‐Ln. In the cases of 1‐Sm and the late Ln metallocenium cations in 1‐Ln ,centroid⋅⋅⋅Ln⋅⋅⋅Cpcentroid angles are significantly more linear than the [Ln(Cpttt)2]+ fragments in early 1‐Ln  which have Ln⋅⋅⋅F interactions . Two nearly eclipsed η5‐Cpttt rings coordinate to the LnIII centres in all 1‐Ln.centroid distances decrease regularly across the Ln series .1‐Sm, two equatorial electrostatic Ln⋅⋅⋅C interactions with carbon atoms from a tBu group were observed , with a C⋅⋅⋅Ln⋅⋅⋅C angle of 147.56(11)°; this feature has been noted for the heavier Lns previously.1‐Ln , Ln⋅⋅⋅F distances were observed between 2.679(9) Å (1‐La) to 2.632(4) Å (1‐Nd); similar contacts between LnCpR2 fragments and [B(C6F5)4]− anions have previously been seen for [Sc(Cp*)2{(C6F5‐κ2‐F)B(C6F5)3}]2{(μ‐C6F5‐κ1‐F)2B(C6F5)2}]2 .2]+ fragments are bridged by two [B(C6F5)4]− anions to give a total of four meta‐F⋅⋅⋅Ln interactions, but in the Sc example a single C6F5 ring binds to one ScIII centre via both a meta‐ and a para‐F atom. The shortest Ln⋅⋅⋅F distance in 1‐Sm is 5.693(2) Å, which indicates that Ln⋅⋅⋅F interactions are only observed for the 1‐Ln series when the LnIII ionic radius is larger than a critical value, when the bis‐Cpttt framework no longer provides sufficient coverage to prevent equatorial interactions with [B(C6F5)4]− anions.The solid‐state structures of to 149.48°; late L1‐Ln and 2‐Ln were obtained as microcrystalline powders , owing to the 4I9/2→4G5/2 transitions;1‐Sm shows absorptions at ν˜max=11 400 cm−1 (ϵ=20 mol−1 dm3 cm−1) and 8400 cm−1 (ϵ=50 mol−1 dm−3 cm−1), which likely arise from 6H5/2→6F11/2, 6F7/2 transitions, respectively.2‐Nd and 2‐Sm.The electronic spectra of 1‐Ln and 2‐Ln using MOLCAS 8.0Complete active space self‐consistent field spin‐orbit (CASSCF‐SO) calculations were performed on unoptimized XRD structures of Jm projections of the total angular momentum J, but can also be defined as an effective S=1/2 state. With this definition, the S=1/2 states have an effective g‐matrix describing the magnetic anisotropy owing to the varying Jm composition of each doublet. The 3×3 g‐matrix can always be diagonalised to yield three principal g‐values and their corresponding orientations in the molecular frame; here we define the principal g‐values such that g1<g2<g3. While the choice of quantisation axis for the CF is irrelevant for any physical observable, it defines how each state is decomposed into linear combinations of Jm projections . In the case of pure Jm states (Jm>1/2), g1=g2=0 and g3=2JmJg where Jg is the Landé g‐factor of the J multiplet of the LnIII ion. In the general case of mixed Jm states it is useful to define <Jz>, the expectation value of the Jz operator which measures the projection of J on the quantisation axis, to understand the magnetic nature of the states; in the limiting case of a pure Jm state, <Jz>=Jm.In the case of Kramers ions with an odd number of unpaired electrons, there will always be two‐fold electronic degeneracy in zero magnetic field, irrespective of a low‐symmetry CF. Each of these Kramers doublets is a linear combination of 1‐Ce , and is thus well‐described as Jm=±5/2 when the CF is quantised along the g3 direction 4]− anion (Table S18), showing only a marginal increase in axiality. For 2‐Ce however, while the ground doublet is also Jm=±5/2 with the CF defined along the Cpttt–Cpttt direction , the first excited state is almost isotropic and the most excited state also resembles the Jm=±5/2 state when the CF is quantised along the “pseudo‐C3” direction perpendicular to both the Cpttt–Cpttt direction and the Ce–Cl vector ; this demonstrates that the Cl− anion is competing with the Cpttt ligands and has a significant influence on the CF.For Ce Table  we obser1‐Sm , this makes 1‐Sm the antithesis of an SMM with the Jm=±1/2, ±3/2 and ±5/2 doublets in ascending energy , yet when the CF is quantised along this direction there is strong mixing between Jm=±1/2 and ±3/2 owing to the competition between the Cpttt and Cl− ligands (Table S29). For both 1‐Sm and 2‐Sm the g‐values are much reduced from those expected for an isolated 6H5/2 multiplet; this is due to considerable J‐mixing with the low‐lying 6H7/2 and 6H9/2 multiplets, rendering a CF model in the basis of a pure J=5/2 state an inaccurate representation of the wavefunction.The electronic structure of Sm Table , like 1‐y Figure  and S28.III the situation is less clear than for CeIII and SmIII because the magnitude of the quadrupolar terms in the expansion of the Jm electron densities are smaller than for the other LnIII ions,Jm states by the low symmetry CF is more severe. For 1‐Nd the two lowest lying doublets are 86 % Jm=±9/2 and 86 % Jm=±7/2, respectively, when the CF is quantised along the Cpttt‐Cpttt direction (Table S25), however the subsequent excited states are quite mixed and the highest‐energy doublet is 86 % Jm=±9/2 when the CF is quantised along the “pseudo‐C3” direction . Removal of the counterion reduces the axiality of the most excited state (Table S26), however this does not change the overall picture of the electronic structure. This suggests that it is the bent arrangement of the Cpttt rings, and not the influence of the [B(C6F5)4]− counterion, that forces the magnetic anisotropy of the most excited state to be perpendicular to that of the ground state, further highlighting the minimal electronic influence of the bulky anion. The electronic structure of 2‐Nd is generally similar to that of 1‐Nd, however the mixing is more severe (Table S27) and is not discussed further.For Ndpseudo‐doublets that are well described as pure Jm functions and a singlet state corresponding to Jm=0; the departure from axiality determines the degree to which the pseudo‐doublets are split into singlets. For pseudo‐doublets only a single principal g‐value can be defined and the other two are zero (note that this does not necessarily indicate a pure Jm state); thus, <Jz> is a useful indicator for non‐Kramers ions.In the case of non‐Kramers ions, the action of a low‐symmetry CF can completely remove the degeneracy of the electronic states, although it does not have to do so (e.g. in high symmetry environments). In the case of a near‐axial CF, there will be a number of 1‐Pr . Removal of the counterion in the CASSCF‐SO calculations for 1‐Pr results in larger energy gaps between the CF states and reduces the splitting within the pseudo‐doublets at higher energies, but generally does not have a large effect on the electronic structure (Table S22). For 2‐Pr, with an extra competitive element in the CF (the Cl− ion), the resulting electronic structure is nearly all singlets (Table S23), and application of a small magnetic field is inconsequential (Table S24).The situation for Pr Table  is similn Tables  and S20,III, NdIII and SmIII) of 1‐Ln and 2‐Ln. We note generally that the intensities of the signals are very weak, however that there is excellent agreement between experiment and theory , however the latter is apparently too weak or is broadened beyond detection.To experimentally probe the nature of the ground states, we have performed cryogenic electron paramagnetic resonance (EPR) spectroscopy on the Kramers ion analogues , however the data for 2‐Pr decrease rapidly at lower temperatures, and those for 1‐Pr decrease slowly below 20 K. For 2‐Pr this is due to a singlet ground state, which is confirmed by magnetisation measurements  and CASSCF‐SO calculations (Table S23), but for 1‐Pr the experimental decrease is much more substantial than predicted by CASSCF‐SO, suggesting that the calculations have underestimated the splitting within the ground pseudo‐doublet on the order of a few cm−1 (Table S20). Generally, these magnetic data are in good agreement with CASSCF‐SO‐calculated electronic structures, however we note that due to the small magnetic moments of the light LnIII ions (where the SO coupling gives J=|L−S| ground multiplets) the experimental data are sensitive to small errors in sample masses and diamagnetic corrections. The data for 1‐Sm and 2‐Sm are the most susceptible to this, as they feature not only the lowest magnetic moments, but also because they are highly sensitive to J mixing (see above) such that the calculations only reveal an approximate electronic structure.The χttt)2]+ seriesIII analogues. Therefore, we investigated the Kramers ions with AC susceptibility studies to examine their magnetisation dynamics , giving an effective barrier of Ueff=51.2 cm−1 with τ0=9.64×10−8 s; CASSCF‐SO predicts a first excited state at around 72 cm−1, so this is not unreasonable. In all other cases a Raman mechanism is the best model for the data, and indeed is also a possible explanation for 2‐Nd. For both pairs of 1‐Ce vs. 2‐Ce and 1‐Nd vs. 2‐Nd, the Raman exponent is smaller for 1‐Ln than for 2‐Ln where the Cl− is bound, similar to the trend we have observed previously for the heavy Ln metallocenium cations (Table ttt)2]+ is responsible for lowered Raman exponents. However, the exponents for 1‐Ce and 1‐Nd are considerably larger than for 1‐Tb, 1‐Dy and 1‐Ho, which suggests that there could be an influence of the proximate [B(C6F5)4]− anion on the relaxation dynamics of these species.We were curious if the anomalous Raman exponents we observed previously for the heavy [Ln(Cpttt)2]+, with the exception of Eu and Pm. In the case of the early Ln (Ln=La‐Nd) the [B(C6F5)4]− counter‐ions weakly coordinate to the metal centre through a meta‐fluorine atom in the solid state, as the metals are large enough to incorporate this additional interaction; these equatorial interactions are absent in the solid state for the later Ln  analogues which contain smaller Ln centres. However, in the solution phase these interactions could not be detected by VT 19F NMR spectroscopy, indicating that isolated Ln metallocenium cations are present in fluid solution.ttt)2]+ for the early Ln suggests that the weak equatorial meta‐fluorine interaction has little effect on the axiality of these systems. Measurement of the relaxation dynamics shows a consistent picture across the [Ln(Cpttt)2]+ series, where the absence of monodentate ligands leads to lower Raman exponents than when they are present, indicating that this effect is a hallmark of all Ln metallocenium cations. We cannot rule out the influence of [B(C6F5)4]− on the relaxation dynamics of 1‐Ce and 1‐Nd, and suggest that the effect of weak equatorial donors on magnetic relaxation mechanisms may be explored in the future by using different CpR ligands and a range of weakly coordinating anions.We have completed a series of analogous Ln metallocenium cations benzene and [D8]toluene were dried by refluxing over K, and [D2]DCM was dried by refluxing over CaH2. NMR solvents were degassed by three freeze‐pump‐thaw cycles, and vacuum‐transferred before use. Anhydrous LnCl3 were purchased from Alfa Aesar and were used as received. KCpttt,3)2][B(C6F5)4]ttt)2]2‐Ln  were made by a modification of published procedures.1H (400 and 500 MHz), 13C{1H} (100 and 125 MHz), 13C{19F} (125 MHz),11B{1H} (128 and 160 MHz), and 19F{1H} (376 MHz) NMR spectra were obtained on Avance III 400 or 500 MHz spectrometers at 298 K. UV/Vis/NIR spectroscopy was performed on samples in Youngs tap‐appended 10 mm path length quartz cuvettes on an Agilent Technologies Cary Series UV/Vis/NIR spectrophotometer at 175–3300 nm. ATR‐Fourier transform infrared (ATR‐FTIR) spectra were recorded as microcrystalline powders using a Bruker Tensor 27 spectrometer. Elemental analyses were performed by Mrs Anne Davies and Mr Martin Jennings at The University of Manchester School of Chemistry Microanalysis Service, Manchester, UK. General synthetic procedures for 1‐Ln and 2‐Ln are given below; full details are in the Supporting Information.ttt)2{(C6F5‐κ1‐F)B(C6F5)3}] (La=La‐Nd), [Sm(Cpttt)2] [B(C6F5)4] (1‐Ln)[Ln(Cp: Benzene (15 mL) was added to a mixture of [H(SiEt3)2][B(C6F5)4] (0.5–0.8 mmol) and 2‐Ln (0.5–0.8 mmol) at room temperature. The mixture was stirred for 16 hours and a precipitate formed. The volatiles were removed in vacuo to give a powder, which was washed with hexane (10–15 mL) and benzene (10–15 mL). In some cases, the crude material was dissolved in DCM  at −78 °C, and layered with 1–1.5 equiv of hexane. Storage at −25 °C overnight gave crystals of 1‐Ln . In other cases, the crude material was dissolved in hot toluene (5 mL). Storage at room temperature gave 1‐Ln .1‐La: Colourless crystals . Anal. Calcd (%) for C58H58BF20La: C, 54.22; H, 4.55; Found: C, 52.22; H, 4.15. 1H NMR : δ=1.38 3), 1.46 3), 6.26 ppm . 11B{1H} NMR : δ=−16.63 ppm (s). 13C{1H} NMR : δ=29.86 and 30.00 (C(CH3)3), 30.53 (C(CH3)3), 31.03 and 31.18 (C(CH3)3), 32.82 (C(CH3)3), 135.96 (Cp‐CH), 147.78 (Cp‐C), 149.70 ppm (Cp‐C). 13C{19F} NMR : δ=124.26 , 136.91 , 138.79 , 148.71 ppm . 19F{1H} NMR : δ=−166.98 , −162.89 , −132.67 ppm . The low solubility of 1‐La in [D6]benzene precluded assignment of 1H and 13C{1H} NMR spectra in this solvent. 11B{1H} NMR : δ=−16.00 ppm (s). 19F{1H} NMR : δ=−165.32 , −160.90 , −131.66 ppm . FTIR : ν˜=2967 , 2874 (w), 2819 (w), 1643 (m), 1513 (s), 1459 (s), 1365 (m), 1273 (m), 1240 (m), 1087 (s), 977 (s), 924 (w), 828 (s), 773 (s), 756 (s), 683 (s), 660 (s), 609 (m), 574 (m), 470 (w), 440 cm−1 (w).1‐Ce: Yellow crystals . Anal. Calcd (%) for C58H58BF20Ce⋅1.5CH2Cl2: C, 50.56; H, 4.35; Found: C, 50.90; H, 4.18. μeff : 2.12 μB. 1H NMR : δ=−13.26 3), −7.93 ppm 3); no other signals observed. 11B{1H} NMR : δ=−18.02 ppm (s). The paramagnetism of 1‐Ce precluded assignment of its 13C{1H} NMR spectrum. 19F{1H} NMR : δ=−170.26 , −164.33 , −134.61 ppm . FTIR : ν˜=2963 , 2871 (w), 2821 (w), 1643 (m), 1512 (s), 1459 (s), 1365 (m), 1273 (w), 1241 (w), 1087 (s), 976 (s), 924 (w), 867 (w), 830 (m), 773 (s), 756 (s), 683 (s), 660 (s), 609 (m), 574 (m), 441 cm−1 (w).1‐Pr: Yellow crystals . Anal. Calcd (%) for C58H58BF20Pr⋅2 CH2Cl2: C, 49.47; H, 4.29; Found: C, 47.68; H, 4.27. μeff : 2.70 μB. The paramagnetism of 1‐Pr precluded assignment of its 1H and 13C{1H} NMR spectra. 11B{1H} NMR : δ=−19.42 ppm (s). 19F{1H} NMR : δ=−172.86 , −166.16 , −136.51 ppm . FTIR : ν˜=2963 (m), 2909 (w), 2871 (w), 1643 (m), 1460 (s), 1365 (m), 1261 (s), 1242 (w), 1086 (s), 1021 (m), 977 (s), 798 (s), 774 (m), 755 (m), 683 (s), 660 (s), 609 (w), 573 (m), 473 (w), 441 cm−1 (w).1‐Nd: Green crystals . Anal. Calcd (%) for C58H58BF20Nd⋅2 CH2Cl2: C, 49.36; H, 4.28; Found: C, 49.51; H, 4.17. μeff : 3.42 μB. 1H NMR : δ=−17.88 3), −11.94 ppm 3); no other signals observed. 11B{1H} NMR : δ=−18.55 ppm (s). The paramagnetism of 1‐Nd precluded assignment of its 13C{1H} NMR spectrum. 19F{1H} NMR : δ=−170.31 , −164.92 , −135.17 ppm . FTIR : ν˜=2967 , 2875 (w), 2820 (w), 1643 (m), 1512 (s), 1460 (s), 1394 (w), 1365 (m), 1254 (w), 1241 (w), 1087 (s), 977 (s), 955 (w), 924 (w), 829 (m), 773 (s), 756 (s), 683 (s), 660 (s), 609 (w), 574 (m), 477 (w), 440 cm−1 (w).1‐Sm: Red crystals . Anal. Calcd (%) for C58H58BF20Sm: C, 53.74; H, 4.51; Found: C, 53.88; H, 4.49. μeff : 1.90 μB. The paramagnetism of 1‐Sm precluded assignment of its 13C{1H} NMR spectrum. 1H NMR : δ=−1.37 3), 19.69 ppm ; no other signals observed. 11B{1H} NMR : δ=−16.76 ppm (s). 19F{1H} NMR : δ=−167.89 , −163.76 , −133.13 ppm . 1H NMR : δ=−2.58 3), −0.90 3), 18.80 ppm . 11B{1H} NMR : δ=−16.32 ppm (s). 19F{1H} NMR : δ=−168.96 , −162.02 , −131.93 ppm . FTIR : ν˜=2964 , 2872 (w), 2796 (w), 1642 (m), 1512 (s), 1459 (s), 1367 (m), 1276 (m), 1239 (m), 1083 (s), 977 (s), 843 (w), 806 (w), 774 (m), 756 (m), 735 (m), 683 (m), 661 (s), 611 (w), 574 (w), 466 (w), 449 cm−1 (w).ttt)2(Cl)]  (2‐Ln)[Ln(Cp: THF (30 mL) was added to a Teflon tap‐appended ampoule containing a pre‐cooled (−78 °C) mixture of LnCl3 (2 mmol) and KCpttt (4 mmol). The reaction mixture was allowed to warm to room temperature and heated in an oil bath at 80 °C for 16 hours. The solvent was removed in vacuo and toluene (30 mL) was added. The reaction mixture was heated in an oil bath at 120 °C for 16 hours. The resultant suspension was allowed to settle for 3 hours and filtered. The solution was concentrated to 2 mL and stored at 8 °C to afford crystals of 2‐Ln.2‐La: Colourless crystals . Anal. Calcd (%) for C34H58LaCl: C, 63.69; H, 9.12; Found: C, 63.57; H, 9.30. 1H NMR : δ=1.25 3), 1.52 3), 6.51 ppm . 13C{1H} NMR : δ=31.19 (C(CH3)3), 32.86 (C(CH3)3), 34.50 (C(CH3)3), 34.68 (C(CH3)3), 114.78 (Cp‐CH), 138.17 (Cp‐C), 139.58 ppm (Cp‐C). FTIR : ν˜=2956 (s), 2904 (w), 2869 (w), 1461 (m), 1389 (m), 1361 (s), 1260 (s), 1241 (m), 1091 , 1016 (s), 866 (w), 797 (s), 678 (s), 590 (w), 566 (w), 551 (w), 436 cm−1 (w).2‐Ce: Orange crystals . Anal. Calcd (%) for C34H58CeCl: C, 63.57; H, 9.10. Found: C, 63.60; H, 9.22. μeff : 2.34 μB. The paramagnetism of 2‐Ce precluded assignment of its 13C{1H} NMR spectrum. 1H NMR : δ=−13.06 3), −2.53 ppm 3); no other signals observed. FTIR : ν˜=2954 (s), 2904 (m), 2868 (w), 1460 (s), 1389 (s), 1358 (s), 1241 (s), 1165 (m), 1001 (s), 958 (m), 816 (s), 774 (s), 678 (s), 566 (w), 436 cm−1 (s).2‐Pr: Pale green crystals . Anal. Calcd (%) for C34H58PrCl: C, 63.49; H, 9.09; Found: C, 63.37; H, 9.22. μeff : 3.35 μB. The paramagnetism of 2‐Pr precluded assignment of its 13C{1H} NMR spectrum. 1H NMR : δ=−36.08 3), −7.74 ppm 3); no other signals observed. FTIR : ν˜=2955 (s), 2905 (m), 2869 (w), 1460 (s), 1389 (s), 1359 (s), 1241 (s), 1166 (m), 1001 (s), 959 (m), 832 (m), 818 (s), 775 (s), 679 (s), 567 (m), 437 cm−1 (s).2‐Nd: Blue crystals . Anal. Calcd (%) for C34H58NdCl: C, 63.16; H, 9.04; Found: C, 61.22; H, 9.02. The paramagnetism of 2‐Nd precluded assignment of its 13C{1H} NMR spectrum. μeff : 3.55 μB. 1H NMR : δ=−18.95 3), −5.58 ppm 3); no other signals observed FTIR : ν˜=2955 (s), 2907 (m), 2870 (w), 1460 (s), 1389 (s), 1358 (s), 1241 (s), 1166 (m), 1001 (s), 833 (s), 820 (s), 775 (s), 679 (s), 439 cm−1 (s).2‐Sm: Yellow crystals . Anal. Calcd (%) for C34H58SmCl: C, 62.57; H, 8.96; Found: C, 60.93; H, 9.19. μeff : 1.69 μB. The paramagnetism of 2‐Sm precluded assignment of its 13C{1H} NMR spectrum. 1H NMR : δ=−6.01 3), 0.55 3), 19.80 ppm . FTIR : ν˜=2956 (s), 2905 (m), 2870 (w), 1460 (s), 1389 (s), 1356 (s), 1241 (s), 1221 (w), 1166 (s), 1000 (s), 959 (m), 836 (w), 824 (s), 776 (s), 679 (s), 591 (w), 438 cm−1 (s).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.


Scientific Reports 10.1038/s41598-017-01160-1, published online 21 April 2017Correction to: This Article contains errors in the first column of Table In addition, Table “oral 200 mg preoperative”should read:“oral 200 μg preoperative”


In salt(II), the anion consists of a 4-methoxybenzenesulfonate ion, and it crystallizes as a monohydrate.The title molecular salts are stilbazole, or 4-styrylpyridine, derivatives in which the cation has a methyl group attached to the pyridine ring N atom and a diethyl amine group attached to the benzene ring. In salt (I), the cadmium atom of the [CdI 18H23N2)2[CdI4], (I), and C18H23N2+·C7H7O4S−·H2O, (II), are stilbazole, or 4-styrylpyridine, derivatives. The cation, (E)-4-[4-(diethylamino)styryl]-1-methylpyridin-1-ium, has a methyl group attached to pyridine ring and a diethyl amine group attached to the benzene ring. The asymmetric unit of salt (I), comprises one cationic molecule and half a CdI4 dianion. The Cd atom is situated on a twofold rotation axis and has a slightly distorted tetrahedral coordination sphere. In (II), the anion consists of a 4-methoxybenzenesulfonate and it crystallizes as a monohydrate. In both salts, the cations adopt an E configuration with respect to the C=C bond and the pyridine and benzene rings are inclined to each other by 10.7 (4)° in (I) and 4.6 (2)° in (II). In the crystals of both salts, the packing is consolidated by offset π–π stacking interactions involving the pyridinium and benzene rings, with centroid–centroid distances of 3.627 (4) Å in (I) and 3.614 (3) Å in (II). In the crystal of (II), a pair of 4-methoxybenzenesulfonate anions are bridged by Owater—H⋯Osulfonate hydrogen bonds, forming loops with an R24(8) motif. These four-membered units are then linked to the cations by a number of C—H⋯O hydrogen bonds, forming slabs lying parallel to the ab plane.The title molecular salts, (C This shows that both compounds exhibit very good anticancer activity, which implies that they may be suitable for biomedical applications.Stilbene-based compounds have been reported to possess a wide range of biological applications including antibacterial (Chanawanno E)-4-[4-(diethylamino)styryl]-1-methylpyridin-1-ium. Their molecular structures are illustrated in Fig. 14]2− anion in the asymmetric unit, the cadmium atom being located on a twofold rotation axis. The cadmium atom is surrounded by four iodine atoms with a slightly distorted tetrahedral coordination sphere. In salt (II)E, with the C4—C7=C8—C9 torsion angle being 179.6 (6) ° in (I)The title molecular salts consist of the same cationic stilbazole derivative,  and benzene (C9–C14) rings are 10.7 (4) and 4.6 (2)° in (I)Cg2) and pyridine  rings .In the crystal of (I)water—H⋯Osulfonate hydrogen bonds, forming loops with an ab plane (Table 1Cg2⋯Cg1ii = 3.614 (3) Å, α = 4.6 (2)°, β = 15.5°, interplanar distances are 3.425 (2) and 3.484 (2) Å, offset = 0.963 Å, symmetry code: (ii) x − 1, y, z].In the crystal of (II)f Table 1. These fe Table 1. Within et al., 2016et al., 2004ca 4.08°, while in the tetraphenylborate salt A search of the Cambridge Structural Database ° in salt (II)p-toluenesulfonate anions via O—H⋯O hydrogen bonds, forming an There is only one salt reported with the title cation and a sulfonate anion, namely the Compound (I)E)-4-[4-(diethylamino)styryl]-1-methyl-pyridinium-iodide  and cadmium iodide  were dissolved in a composite solvent, 2:1 ratio of acetonitrile and double-distilled water. The mixture was stirred well at 343 K and then allowed to cool naturally to room temperature. The solution was filtered and the filtrate left for the solvent to slowly evaporate at room temperature. After 3–4 weeks, dark-brown block-like crystals of compound (I)(Compound (II)E)-4-[4-(diethylamino)styryl]-1-methylpyridinium iodide  was mixed with sodium 4-methoxybenzenesulfonate  in distilled water and heated at 373 K for 30 min. The mixture immediately yielded a grey precipitate of sodium iodide. After stirring the mixture for 30 min, the sodium iodide precipitate was removed. The filtrate was left to slowly evaporate and gave a deep-red solid. Red block-like crystals of compound (II)(Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq for other H atoms. The rotation angles for the methyl groups were optimized by least-squares. In compound (II)d(O—H) = 0.85 Å and Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details for salts (I)10.1107/S2056989018016808/su5462sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989018016808/su5462Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018016808/su5462IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989018016808/su5462IIsup4.cmlSupporting information file. DOI: 1589674, 1589675CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-(pyridin-2-ylmethyl)benzamide derivative, crystallizes with two independent molecules (A and B) in the asymmetric unit, which differ essentially in the orientation of the pyridine ring with respect to the benzene ring, with the two rings being inclined to each other by 53.3 (2) and 72.9 (2)° in molecules A and B, respectively.The title  18H18F2N2O3, crystallizes with two independent molecules (A and B) in the asymmetric unit. They differ essentially in the orientation of the pyridine ring with respect to the benzene ring; these two rings are inclined to each other by 53.3 (2)° in molecule A and by 72.9 (2)° in molecule B. The 3-(cyclopropylmethoxy) side chain has an extended conformation in both molecules. The two molecules are linked by a pair of C—H⋯O hydrogen bonds and two C—H⋯π interactions, forming an A–B unit. In the crystal, this unit is linked by N—H⋯O hydrogen bonds, forming a zigzag –A–B–A–B– chain along [001]. The chains are linked by C—H⋯N and C—H⋯F hydrogen bonds to form layers parallel to the ac plane. Finally, the layers are linked by a third C—H⋯π interaction, forming a three-dimensional structure. The major contributions to the Hirshfeld surface are those due to H⋯H contacts (39.7%), followed by F⋯H/H⋯F contacts (19.2%).The title compound, C The dihedral angle between the benzamide ring and the pyridine ring is 53.3 (2)° in molecule A and 72.9 (2)° in molecule B. The cyclopropane ring makes a dihedral angle of 57.7 (5)° with the benzene ring in molecule A and 58.7 (4)° in molecule B. The sum of the bond angles around atom N1 (359.9°) is in accordance with sp2 hybridization in both molecules. The bond lengths and bond angles in both molecules are comparable with those reported for a similar compound, 3-(cyclopropylmethoxy)-N--4-(difluoromethoxy) benzamide -4-(difluoromethoxy) benzamide  are very similar. Considering the low-temperature phase PEDWOM only, in each molecule the benzene and pyridine rings are positioned almost perpendicular to each other, with dihedral angles of 88.38 (14), 89.34 (14) and 84.72 (14)°, compared to 53.3 (2) and 72.9 (2)° for molecules A and B, respectively, in the title compound. In PEDWOM the cyclopropane ring makes dihedral angles of 55.43 (3), 49.6 (3) and 50.9 (3)° with the corresponding benzene ring. These dihedral angles are very similar to those observed in the title structure [57.7 (5)° in molecule A and 58.7 (4)° in molecule B]. In the second compound, methyl 3-(cyclopropylmethoxy)-4-hydroxybenzoate , followed by F⋯H/ H⋯F at 19.2% , C⋯H/H⋯C at 16.6% , O⋯H/ H⋯O at 14.0% , N⋯H/H⋯N at 6.8% . Hence, the H⋯H and F⋯H/H⋯F intermolecular contacts are the most abundant in the crystal packing, and make the most significant contributions to the total Hirshfeld surfaces.The Hirshfeld surface analysis  in methanol were heated first to 393 K for 2 h in the presence of the inexpensive ionic liquid tetrabutylammonium bromide (TBAB). The reaction was monitored by TLC, and on completion the reaction mixture was allowed to cool to room temperature, then filtered to remove the insoluble solids. The filtered solid was then washed with dichloromethane. Excess solvents were removed under reduced pressure and the obtained crude product was purified by crystallization using 1:1 ratio of chloroform and methanol. Colourless block-like crystals were obtained after two days.A mixture of 4-(difluoromethyl)-3-hydroxybenzoic acid (2 mmol), (chloromethyl)cyclopropane (2 mmol) and 2-picolylamine (3 mmol) with PPhUiso(H) =1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The absolute structure of the molecules in the crystal are unknown; the Flack parameter refined to 0.6 (3).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019012866/su5514sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989019012866/su5514Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019012866/su5514Isup3.cmlSupporting information file. DOI: 1954107CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Though such interactions are commonly attributed to “sigma-hole”-type electrostatic effects, we show that they exhibit profound similarities and analogies to the resonance-type 3-center, 4-electron (3c/4e) donor-acceptor interactions of hydrogen bonding, where classical-type “electrostatics” are known to play only a secondary modulating role. The general 3c/4e resonance perspective corresponds to a continuous range of interatomic A···B bond orders (bAB), spanning both the stronger “covalent” interactions of the molecular domain  and the weaker interactions  that underlie supramolecular complexation phenomena. We show how a unified NBO/NRT-based description of hydrogen, halogen, pnicogen, and related bonding yields an improved predictive utility and intuitive understanding of empirical trends in binding energies, structural geometry, and other measurable properties that are expected to be manifested in all such supramolecular interaction phenomena.We employ a variety of natural bond orbital (NBO) and natural resonance theory (NRT) tools to comprehensively investigate the nature of halogen and pnicogen bonding interactions in RPH Recent computational ,2,3,4 annB→σ*AH donor–acceptor interaction between the lone pair (nB) of the Lewis base B and the valence antibond (σ*AH) of the Lewis acid A—H. In natural resonance theory (NRT) [nB→σ*AH interaction represents resonance mixing between the parent natural Lewis structure (NLS) I and the secondary “charge–transfer” resonance structure II (with respective NRT weightings wI and wII):bAH, bBH bond orders are necessarily related by the characteristic “bond conservation” relationship [wI + wII = 1) for the composite resonance hybrid. Even in the absence of NRT bond order descriptors, the importance of NBO nB→σ*AH delocalization can be assessed by 2nd-order perturbative energy (ΔE(2)nσ*), intermolecular charge-transfer (Qnσ*), or the deletion of this NBO interaction (ΔE$DELnσ*), as well as the variational recalculation of structure, energetics, and vibrational frequencies [In the case of hydrogen bonding, the primacy of short-range covalency forces is now widely recognized ,36,37,38ry (NRT) ,41,42,43rchanged . As recorchanged , the resrchanged ,47. In ttionship ,bAH + bquencies . In contquencies  that mos2···IF/FI  that exhibit a wide range of binding strengths. A smaller subset of such species was previously examined [In the present work, we take up the analogous covalency versus electrostatics questions for title complexes RPHexamined  with an examined .n-σ* interaction) is strictly absent in uncorrelated Hartree–Fock theory. Though an empirical dispersion correction [3PH2···IF (see Ebind). Such “corrections” are not considered further in the present work. Note that we ignore the weaker effects of the London dispersion interaction , a pure rrection  is oftenE(2)nσ*, charge–transfer Qnσ*, and $DEL-deletion ΔE$DELnσ* measures of donor–acceptor attraction [E(pw)nσ) of filled orbitals [In the following, we first describe the species, computational levels, and NBO/NRT methods to be employed. The latter include NBO Δtraction , the cororbitals  that comorbitals . We then2···XY that included all possible  dihalogen species of the first four periodic rows. However, from a qualitative conceptual perspective, it soon became apparent that the properties of such complexes vary in a smooth and chemically reasonable fashion with dihalogen polarity, as maximized in the iodine–fluorine (IF) species. Accordingly, we focus here on the “polar extremes” of RPH2···IF versus RPH2···FI complexation, corresponding to opposed signs of any envisioned “dipole–dipole” contributions to intermolecular binding. A direct comparison of these two extremes thereby allows one to recognize the important modulating influence of classical dipole–dipole forces , while also verifying that resonance-type covalency forces yield robust supramolecular bonding even when the presumed classical electrostatic prerequisites for such complexation are profoundly violated. While the computational results presented here focus only on the extremal RPH2···IF versus RPH2···FI limits of this broader picture, the Our studies began with a larger data set of dihalogen complexes RPH2 monomers and LANL2DZ for dihalogen monomers of each complex. We employ simple B3LYP density functional methodology throughout this work, but alternative MP2 evaluations at different basis levels were also performed for comparison (see SI). All structures were optimized, and frequencies were computed to confirm equilibrium geometries corresponding to minimum energy points. The binding energy, ΔEbind = E(AB) − E(A) − E(B), was calculated as the direct energy difference between optimized dimer and relaxed monomers. All electronic structure calculations were performed with the Gaussian 16 program package [NBO 7.0 software [NBOPro@Jmol program [Though the conceptual picture we describe is insensitive to many details of the chosen computational method and basis set , the inc package . NBO/NRTsoftware , and bot program .2···IF and RPH2···FI species as obtained at the adopted “B3LYP/mixed-PP” level, showing the wide range of tuning by various R-substituents. Despite the fact that all complexes are appreciably bound , interesting structural contrasts are immediately evident between these two classes of species. Focusing first on the orientation angles (Θ) in 2···IF species all maintain nearly linear P···IF alignment (ΘPIF ≈ 180°) and a circa 120° bend angle between RP and IF axes (ΘRPI ≈ 120°). In contrast, the RPH2···FI species are noticeably tilted away from P···FI linearity (ΘPFI ≈ 160°), instead adopting increasingly near-linear alignment with respect to RP and FI axes (ΘRPF ≈ 170°). Such structural tendencies suggest that the principal underlying “linearizing” (H-bond-like) interaction differs in the two cases and that other RPH2···XY dihalogen species of intermediate polarity will likewise exhibit intermediate orientational preferences between these two competing tendencies. Indeed, this is the broader picture obtained from the full set  of optimized dihalogen structures, with the homopolar RPH2···X2 species forming the approximate “dividing line” between RPH2···IF-like versus RPH2···FI-like structural propensity. These structural features of RPH2···IF-like (“P···IF”) versus RPH2···FI-like (“RP···F”) complexes are also consistently exhibited at other theory levels, as shown in SI 2···IF versus RPH2···FI species for describing the full range of RPH2···XY complexation , including general consistency with previous MP2/aug-cc-pVTZ-level calculations.RP···F or RP···I  with increasing binding energy ΔEbind is also discernable in the details of the figure panels. From both Ebind with various R-substituents for the strongly bound complexes of the RPH2···IF type. The graph includes comparison values for the alternative theory levels given in IF with respect to the R-substituent . As shown in the figure, ΔνIF is strongly red-shifted for the most strongly bound complexes, similar to the well-known spectroscopic signature of H-bonding. IF  between these experimentally observable quantities that confirms the similarity to H-bonding.ding. IF  versus ΔF  to achieve the net binding energies displayed in Ebind binding affinity and RP···I separation in the deep sub-vdW region.Returning to the structural data of 2···IF and weak RPH2···FI complexes, the structural features hint at striking resemblances to familiar H-bonding phenomena, including deep sub-vdW penetration  and pronounced “linearization” tendency . We take up NBO/NRT investigation of these apparent similarities and bonding relationships in the following sections.The computed structural and binding characteristics noted above identify the propensities and patterns to be explained and provide helpful clues to the nature of the underlying attractive forces. Even the more weakly bound complexes of the P···FI type exhibit optimized P···F distances (2.1–2.6Å) that lie significantly (>0.5Å) inside vdW contact  donor–acceptor interactions of the present species.As suggested in  above, an NBO/NRT analysis of B:···HA hydrogen-bonding phenomena reveals a host of characteristic correlations ,23,60 thanalysis ,62,63. Tanalysis ,66,67,682···IF complexes, the key feature of envisioned P···I—F “halogen bonding” is the donor–acceptor delocalization of electronic charge from an occupied donor NBO of P (lone pair nP) to the favorably polarized acceptor NBO (antibond σ*IF) of the P···I—F triad. For RPH2···FI complexes, where the nP-σ*IF overlap is unfavorable, the analogous feature of envisioned F···P—R “pnicogen bonding” is the donation from a fluorine lone pair (nF) to the proximal antibond (σ*PR) of the phosphine monomer. Each such n→σ* delocalization can be alternatively quantified in terms of energetic (perturbative ΔE(2)nσ* or variational deletion ΔE($DEL)nσ*), charge transfer (Qnσ*), or fractional NRT bond order (bP···I or bP···F) descriptors.The analogies of the preceding section suggest appropriate NBO/NRT descriptors for the corresponding ···X— (“X-ogen”) species that can be similarly visualized in simple orbital overlap terms. For RPHEnσ* stabilization energy associated with each type of delocalization in the strongly bound RPH2···IF species. The first two columns display 2nd-order perturbative ΔE(2)nσ* estimates for nP→σ*IF  and nI→σ*PR (“pnicogen bond”) contributions. The final two columns of E($DEL)nσ* variational deletion estimates, obtained as the variational energy raising when the specific n→σ* NBO interaction is deleted from the total energy evaluation. The two estimates are seen to be in reasonable qualitative agreement for each interaction type. The ΔE(2)n(P)→σ*(IF) values range from 19 to 37 kcal/mol (in the same order as ΔEbind), whereas ΔE(2)n(I)→σ*(FI) is relatively negligible in each case, and a similar pattern is seen in the ΔE($DEL)nσ* values. We therefore expect that the stabilization energy of the nP→σ*IF interaction is the dominant attractive contribution to the structure and binding of RPH2···IF complexes, similar to the dominance of the nB→σ*AH interaction in H-bonding.2···FI species, the situation is more complex. Due to the unfavorable polarization of σ*FI away from the nP lone pair, the single nP→σ*IF interaction that dominates bonding in RPH2···IF species becomes only one of several such competing contributions to net binding. Specifically, for the opposed F···P—R (pnicogen bonding) motif, three possible nF lone pairs (one of sigma type and two of pi type) and three σ*PY acceptors (one σ*RP and two σ*PH) are within proximal interaction range as potential contributors to a complex resonance mixture. A particular interaction such as nF(σ)→σ*RP therefore represents only one of the nine related n→σ* interactions that may exert leverage on angular structure and binding energy. In such a case, only a more nuanced resonance-type description (see the discussion of NRT bond orders below) can describe the complete bonding picture that provides useful correlations with experimentally measurable properties. We therefore defer further discussion of RPH2···FI complexes to a later subsection.For the weakly bound RPHn→σ* interactions of halogen  or pnicogen (nI(π)→σ*RP, nI(σ)→σ*RP; final two columns) types, with corresponding numerical ΔE(2)nσ* values  is much stronger than the “edge-on” (pi-type) overlap of σ*RP with the in-plane iodine nI(π) (middle panel) or nI(σ) (right panel) lone pairs, in accordance with the ΔE(2)nσ* values shown in each panel. Even a casual glance at the overall patterns of the orbital overlap in nP→σ*IF) rather than pnicogen-type (nI(π)→σ*RP, nI(σ)→σ*RP) bonding throughout the RPH2···IF series, as numerically displayed in For example, in the three panels for CHEnσ* stabilization energies of Ebind binding energies of Enσ donor–donor interaction. E(pw)n-σ for repulsive “steric exchange energy” [2···IF series. As shown in the panels, the two leading intermolecular repulsions refer to the nP-nI steric clash between lone pairs of proximal P and I atoms (left) and nP-σIF clash between a lone pair and bond of the halogen bond P···I—F triad. However, weaker nI-σPR, nI-σPH clashes of the alternative pnicogen bond triads  also contribute to sub-vdW steric opposition, thereby further offsetting the apparently “excessive” NBO estimate of donor–acceptor attraction needed to achieve the final equilibrium geometry and net binding energy.Though the donor–acceptor Δ energy”  between nP, nI, and σIF NBOs (not shown) similarly serve to rationalize the trends in repulsive donor–donor interactions n(P)→σ*(IF) evaluations of n→σ* donor–acceptor strength in the equilibrium species (E($DEL)n(P)→σ*(IF) potential energy surface in which n→σ* delocalization is absent, as though nature (in accordance with common textbook presentations) failed to include such interactions.Still another widget from the NBO toolbox can be used to exhibit the profound effects of  species , one can2···IF dissociation, with the nP→σ*IF interaction deleted. Starting from the equilibrium values of the actual RPH2···IF species, the distance variables RP···I, RIF  were optimized to find the new binding energy (ΔEbind) and shifts  that describe the hypothetical “resonance-free” RPH2···IF that lacks nP→σ*IF donor–acceptor attraction. From the resulting values, one sees that characteristic structural and energetic signatures of RPH2···IF bonding are lost when the nP→σ*IF interaction is “turned off;” the RPH2 and IF monomers retreat (by circa 1.3Å) to beyond-vdW separation, the characteristic RIF elongation  from isolated monomer geometry essentially disappears, and the net binding energy drops precipitously (by >80%) to a remnant value that might plausibly be associated with residual “dipole–dipole” forces. Note that the monomer dipole moments or other aspects of electron density distribution are scarcely altered in the $DEL-reoptimized geometry, and the “lost” energy of nP→σ*IF stabilization is negligibly small  at the reoptimized separation distance. From the results of such $DEL-deletion calculations, one recognizes nP→σ*IF stabilization to be the unique “smoking gun” that is both necessary and sufficient to bring the supramolecular complex to the actual short-range geometry and other signatures of halogen bonding, which is in direct correspondence to the analogous nB→σ*HA role in H-bonding.n→σ* interactions lead to net binding against the essentially repulsive potential curve for hypothetical monomers that interact without benefit of resonance-type stabilization. 3PH2···IF dissociation, showing the potential curve for the fully interacting monomers . The “missing” resonance-type (purely attractive) interactions are shown as the difference curve . The blue curve exhibits a feeble attractive well beyond vdW contact at RP···I ≈ 4.0Å (presumably due to “dipole–dipole” attraction) but rises steeply as a repulsive steric wall in the sub-vdW region. Already in the region of the initial sub-vdW penetration, the red curve (n→σ* resonance attraction) has achieved sufficient stabilization to oppose thermal fluctuations  and yield significant sub-vdW binding in the black  curve down to RP···I ≈ 2.9 equilibrium separation. Inside this equilibrium distance, the intermolecular n-σ steric repulsion overcomes n-σ* attraction to give the steeply repulsive inner wall of the full potential, resonance-shifted inside circa 2.5Å. Where such nP-σIF versus nP-σ*IF “cross-over” occurs will evidently depend on the polarization of the dihalogen bond and is therefore expected to shift to a progressively larger RP···I separation (and weakened ΔEbind) for other members of the dihalogen series, thereby appearing as a secondary “electrostatic” modulating effect on the overall halogen bonding phenomenon.Still another use of $DEL-deletion techniques is to prepare relaxed-scan potential curves that illustrate how intermolecular 2···IF species  tends to increase steadily with strength of RPH2···IF binding or net QCT. This trend reflects the expected dominance of the nP→σ*IF interaction, which is evidently enhanced . The combined effect of repolarization (iIF) and net charge transfer (QCT) is to give a somewhat irregular pattern to individual atomic charges qI, qF, but all such IF charge descriptors are seen to properly “add up,” as they must according to the strict logic of a natural population analysis.city iIF ), compar2 monomer, the phosphorus charge qP reflects the still more complex effects of sigma-type induction versus intra- and intermolecular lone pair delocalizations. One can see in the table the evident effect of bonding the phosphorus to more electronegative oxygen (qP ≈ 0.73) or nitrogen (qP ≈ 0.45) rather than carbon (qP ≈ 0.3–0.4). However, also important in the present context is the intra- versus intermolecular competition for charge donation from the “busy” phosphorus lone pair nP to various pi-type acceptor orbitals of the R-substituent  versus the intermolecular nP→σ*IF interaction of principal interest.In the RPHbAB}, which balance the nuances of multiple resonance structure contributions to give a single composite measure of A···B “connectivity.” As described elsewhere [NBO 7.0 program [Perhaps the most useful and general descriptors of supramolecular bonding are NRT bond orders {lsewhere ,41,42,43lsewhere   versus the “noncovalent interaction” (dots). Most surprising in these species are the non-vanishing bond orders for the “long-bond” [2···IF species, certain P^I long bonds achieve bond orders that rival or exceed those of familiar bP···F or bIF linkages .The first three columns of ng-bond” ,77,78 inThe final two columns of E(2)nσ*, ΔE($DEL)nσ*, Qnσ*,...) intrinsically focus on orbitals of a specific n→σ* “delocalization” from a specific Lewis structural bonding pattern. Such orbital-specific descriptors are valuable when a single “parent” Lewis structure and “child” n→σ* delocalization clearly dominate quantum mechanical descriptions of the structural, energetic, and spectroscopic properties of the chosen system. However, for many chemical systems of interest (including the RPH2···FI species considered here), multiple n→σ* interactions come into play, corresponding to contributions of alternative resonance–structural bonding patterns that may no longer be “child-like” compared to a reference parent pattern. Such cases demand the more nuanced NRT descriptors such as interatomic bond orders {bAB} that balance the many possible orbital interactions contributing to the overall resonance hybrid.The principal NBO descriptors of donor–acceptor interactions  makes them better adapted to describe empirical correlations with measurable properties. Well-known examples include bond order–bond length (bAB-RAB) [n→σ* limit  as well as the more general correlations of NRT bond orders with experimentally measurable properties, spanning the full set of RPH2···IF/FI species considered in this work.As could be anticipated from the empirical origins of bond order descriptors in the pre-quantum mechanical conceptions of “mesomerism” theory , the “avbAB-RAB) , bond orbAB-RAB) , and bonbAB-RAB)  relation2···IF series, in which the nP→σ*IF interaction plays a clearly dominant role, we first consider the mutual correlations of ΔE(2)nσ*, ΔE($DEL)nσ*, Qnσ*, bP···I descriptors for this interaction. Taking perturbative ΔE(2)nσ* as the base descriptor for the group, we display (a) ΔE(2)nσ*-ΔE($DEL)nσ*, (b) ΔE(2)nσ*-Qnσ*, and (c) ΔE(2)nσ*-bP···I correlation diagrams in successive panels (a)–(c) of 2 correlation coefficients demonstrate the high quality of these mutual correlations: In the range 0.94–0.99 for NBO-specific descriptors, but slightly lower (0.94) for correlation with the NRT bond order bP···I (presumably due to the proper inclusion of secondary donor–acceptor interactions with R-substituents that are present only in the latter). The results show that descriptors of this group could be chosen rather interchangeably for correlations with measurable experimental properties when a single donor–acceptor interaction such as nP→σ*IF is clearly dominant.Starting with the RPHRP···I or RP···F, (b) intramolecular RIF, (c) binding energy ΔEbind, or (d) infrared stretching frequency νIF, we employed the NRT bond order bAB  as base descriptor in the correlation diagrams of 2···IF  and RPH2···FI (red: Multi-resonance) series. As examples of bond orderbond length correlations, bP···X-RP···X correlations  for each series, with reasonably high correlations (|χ|2 = 0.92) in each case. bIF-RIF correlation for the dihalogen monomer, with still higher correlation coefficients . As examples of bond order–bond energy correlation, bP···X-ΔEbind correlations , with similar correlation coefficients (|χ|2 = 0.94) in each series. Finally, as bond order–bond frequency examples, bIF-ΔνIF correlations, again with high correlation coefficients . All these correlations suggest the high predictive utility of NRT bond orders for both the tuning effects of R-substituents and the polarity variations of the various dihalogen monomers that govern the broad range of binding energies in these supramolecular species.For more general correlations with measurable experimental properties such as (a) intermolecular 2···IF/FI, R = CH3, OH, CF3, CN, NO2), focusing on the electronic origin of what might be identified as a “halogen bond,” “pnicogen bond,” or some combination of both. For this purpose, we employed a broad variety of natural bond orbital (NBO) and natural resonance theory (NRT) descriptors, searching for relationships to hydrogen bonding or other known forms of intermolecular attraction .We have computationally investigated the nature of supramolecular bonding in a series of R-substituted phosphine···dihalogen complexes  is the dominant feature of halogen-type  or pnicogen-type  bonding motifs, just as for the dominant nB→σ*HA interaction of B:···H—A hydrogen bonding. We obtained evidence both for resonance-type “bond conservation” rules and the complete set of mutually consistent correlations of NBO/NRT descriptors with experimentally measurable properties of RPH2···IF/FI complexes that closely parallel those previously demonstrated for H-bonded complexes. We also demonstrate that the removal of n→σ* interactions obliterates the signature features of halogen/pnicogen bonding, whereas such features persist  even if envisioned “dipole–dipole” contributions are reversed . Thus, our results establish that resonance-type n→σ* stabilization is both necessary and sufficient for the characteristic structural, energetic, and spectroscopic features of halogen or pnicogen bonding, as was previously demonstrated for H-bonding [Our results show that resonance-type “-bonding ,23. The -bonding ,83. Conn-bonding .n→σ* “fractional bonding” will be found for chalcogen bonds, tetrel bonds, and all other such supramolecular bonding phenomena. Our conclusions thereby extend “resonance covalency” concepts to the entire supramolecular domain of sub-integer bond orders, challenging the common “electrostatic” assumptions that underlie current empirical force field modeling and textbook expositions of supramolecular chemistry. Based on these results, we anticipate that similar unique associations with resonance-type


The title compound crystallizes with two independent molecules in the asymmetric unit. They differ essentially in the orientation of the 4-methoxyphenyl ring with respect to the pyridine ring of the quinoline moiety. 34H28ClN3O3S, contains two independent molecules (A and B). They differ essentially in the orientation of the 4-methoxyphenyl ring with respect to the pyridine ring of the quinoline moiety; this dihedral angle is 37.01 (18)° in molecule A but only 7.06 (17)° in molecule B. In both molecules, the cyclohexanone ring of the isoquinoline unit has a half-chair conformation. In the pyrrolothiazole ring system, the pyrrolo ring in molecule A has a twisted conformation on the N—C fused bond and an envelope conformation in molecule B with the N atom as the flap. The thiazole rings of both molecules have twisted conformations on the N—C fused bond. In the crystal, the A molecules are linked by pairs of N—H⋯O hydrogen bonds, forming inversion dimers with an R22(8) ring motif. These dimers are linked to the B molecules by an N—H⋯N hydrogen bond and a series of C—H⋯O hydrogen bonds, forming layers lying parallel to the (101) plane. The layers are linked by C—H⋯π interactions and offset π–π interactions [intercentroid distance = 3.427 (1) Å], forming a supramolecular framework. The contribution to the scattering from a region of highly disordered solvent molecules was removed with the SQUEEZE routine in PLATON [Spek (2015The asymmetric unit of the title compound, CSpek 2015. Acta Cr In molecule A, the dihedral angle between the two rings is 37.01 (18)° compared to 7.06 (17)° in B. There is also a slight difference in the orientation of the 4-chlorophenyl ring with respect to the mean plane of the pyrrolo ring, viz. in molecule A benzene ring C11A–C16A is inclined to the mean plane of the pyrrol ring (N1A/C1A–C4A) by 86.12 (17)°, while in molecule B the corresponding dihedral angle is 76.92 (17)°.The molecular structure of the two independent molecules, A/C21A/C22A/C26A–C28A) in molecule A and (C2B/C21B/C22B/C26B–C28B) in B] of the isoquinoline unit adopts a half-chair conformation in molecule A  and a distorted half-chair conformation in molecule B , the benzene and pyrrolidine rings make dihedral angles of 3.65 (3) and 3.67 (3)° in molecules A and B, respectively, while the keto atoms, O2A in molecule A and O2B in molecule B, deviate from the attached pyrrolidine rings by 0.1116 (1) and 0.0176 (1) Å, respectively.In the indolin-2-one ring systems -1,2′′(1′′H)-dione methanol solvate -dione chloroform solvate -6-(4-chlorobenzylidene)-2-(4-methoxyphenyl)-7,8-dihydroquinolin-5(6H)-one (1 mmol) was added and the reaction mixture was allowed to reflux for a further 14 h. After completion of the reaction, as evident from TLC, the solvent was removed under reduced pressure and the residue washed with ice-cold water (50 ml). The crude product was purified by column chromatography using 90:10 (v/v) petroleum ether–ethyl acetate mixtures to obtain the pure product. The product was dissolved in ethyl acetate and poured into a beaker, covered with perforated film and kept undisturbed. The solvent was allowed to evaporate slowly, yielding colourless block-like crystals after a period of seven days .A mixture of isatin (1.1 mmol) and thiazolidine-4-carboxylic acid (1.1 mmol) was taken in 10 ml of acetonitrile in a 50 ml round bottom flask and heated to reflux for 2 h. Then (Uiso = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. The residual electron density was difficult to model and therefore, the SQUEEZE routine in PLATON  contains approximately 100 electrons  global, I. DOI: 10.1107/S2056989019000112/su5469Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019000112/su5469sup3.pdfCSD search. DOI: 1888600CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


H-chromen-4-yl)oxy]acetamide derivatives are described and the intermolecular contacts in the crystals analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots.The crystal structures of two 2-[(2-oxo-2 H-chromen-4-yl)oxy]acetyl}piperazin-1-yl)acetamide, C17H19N3O5, (I), and N--2-[(2-oxo-2H-chromen-4-yl)oxy]acetamide, C20H19NO6, (II), are new coumarin derivatives. In compound (I), the six-membered piperazine adopts a chair conformation. The dihedral angles between the mean planes of the chromene ring and amide plane is 82.65 (7)° in (I) and 26.2 (4)° in (II). The dihedral angles between the mean planes of the chromene ring and the four planar C atoms of the piperazine ring in (I) and the benzene ring in (II) are 87.66 (6) and 65.0 (4)°, respectively. There are short intramolecular contacts in both molecules forming S(5) ring motifs, viz. N—H⋯N and C—H⋯O in (I), and N—H⋯O and C—H⋯N in (II). In the crystals of both compounds, molecules are linked by N—H⋯O hydrogen bonds, forming chains along  present within the layers. In the crystal of (II), there are only weak offset π–π interactions [intercentroid distance = 3.981 (6) Å] present within the layers. The intermolecular contacts in the crystals of both compounds have been analysed using Hirshfeld surface analysis and two-dimensional fingerprint plots.The title compounds, 2-(4-{2-[(2-oxo-2 The synthesis, and pharmacological and other properties of coumarin derivatives have been studied and reviewed (Kumar Q = 0.561 (2) Å, θ = 0.67 (2)° and φ = 149 (2)°], and is positioned anti with respect to the C—N rotamer of the amide. Nevertheless, because the asymmetry of the chromene residue, the anti conformation can assume a cis or trans geometry with respect to the relative position of the carbonyl O atom of the carboxamide and the C10—C11 and C16—C17 bonds. Both compounds exhibit a cis relation between these bonds, as can be seen in Figs. 1S(5) ring motifs. In addition, the carbonyl oxygen atom O4 acts as the acceptor for a weak interaction with a hydrogen bond of the exocyclic piperazine ring, forming a second S(5) ring motif in (I)S(5) ring motif in (II)The molecular structures of compounds (I)The values of the dihedral angles between the mean planes of the planar chromene ring system  and the amide plane (C10/C11/O4/N1) are 82.65 (7) and 26.2 (4)° in compounds (I)N-(substituted phenyl)-4H-chromene-2-carboxamides  and C(7) chains formed via the C10—H10A⋯O5iii and N3—H3A⋯O4i hydrogen bonds, respectively. A C—H⋯π interaction is also present within the layer (Table 1Cg2⋯Cg2iv = 3.691 (1) Å, interplanar distance = 3.490 (1) Å, offset = 1.20 Å; Cg2 is the centroid of the O1/C1–C9 ring; symmetry code: (iv) −x + 1, −y + 1, −z + 1].In the crystal of (I)ne Fig. 3. The C14r Table 1. An offsi hydrogen bonds, forming chains along the [010] direction, see Fig. 4ii, C5—H5⋯O4i and C15—H15⋯O4iii hydrogen bonds, forming layers parallel to the ab plane  Å, interplanar distances = 3.638 (4) and 3.508 (4) Å, offset 0 1.88 Å; Cg2 and Cg3 are the centroids of rings C1–C6 and C13–C18, respectively; symmetry code: (iv) −x + 1, y + z + 1].In the crystal of (II)ne Fig. 4. Within et al., 2019et al., 2007CrystalExplorer17  through white to blue . The dnorm surface was mapped over a fixed colour scale of −0.544 (red) to 1.418 (blue) for compound (I)The Hirshfeld surfaces of compounds (I)b) and O⋯H/H⋯O at 35.3% , followed by the C⋯H/H⋯C contacts at 11.8% . For compound (II)b) and O⋯H/H⋯O at 32.4% , followed by the C⋯H/H⋯C contacts at 16.7% . In both compounds, the H⋯H intermolecular contacts predominate, followed by the O⋯H/H⋯O contacts. However the C⋯H/H⋯C contacts are significantly different 11.8% cf. 16.7% for (I)The fingerprint plots are given in Figs. 83% Fig. 8c, follo8% Fig. 8d. For c4% Fig. 9c, follo7% Fig. 9d. In boet al., 2016H-chromen-4-yl)oxy]acetamide derivatives gave two hits. They include 2-[(2-oxo-2H-chromen-4-yl)oxy]-N-(1-phenylethyl)acetamide -2-[(2-oxo-2H-chromen-4-yl)oxy]propanamide  structures gave 35 hits. They include four reports, CSD refcodes AMYROL [Kato, 1970et al., 1982et al., 1985et al., 2011et al., 2014et al., 2017meta-substituted coumarin esters cyclopropyl sulfamate (Morin Compound (I) To a solution of 1 equiv. of 4-(2-(piperazine-1-yl)ethoxy)-2H-chromen-2-one (1.0 g) in dichloromethane (10 ml) at 273–278 K were added triethylamine  followed by iodoacetamide , and the reaction mixture was stirred at the same temperature for 1 h. On completion of the reaction (monitored by TLC), the reaction mixture was diluted with dichloromethane and water (10 ml). The organic layer was separated and washed with brine solution. It was then dried over anhydrous sodium sulfate, filtered and then evaporated under reduced pressure giving compound (I)Compound (II)N,N-Diisopropylethylamine  was added to a mixture of 2-(2-oxo-2H-chromen-4-yloxy)acetic acid , 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide , 1-hydroxybenzotriazole hydrate , 2,4-dimethoxybenzylamine  in N,N-dimethylformamide (5 ml) at 273–278 K. The temperature of the mixture was raised to ambient temperature and stirred for 8 h. Progress of the reaction was monitored by TLC (mobile phase: ethyl acetate/hexane). After completion of the reaction, the mixture was poured into ice–water and compound (II)Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989019003736/su5482sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: 10.1107/S2056989019003736/su5482Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989019003736/su5482IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989019003736/su5482Isup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019003736/su5482IIsup5.cmlSupporting information file. DOI: 1891497, 1891496CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structures of three salicyaldoxime compounds are discussed together with Hirshfeld surface and fingerprint analyses. 8H9NO2, 1, 2,4-dihydroxybenzaldehyde oxime, C7H7NO3, 2, and 2-hydroxy-4-methoxybenzaldehyde oxime, C8H9NO3, 3, are discussed. In each compound, the hydroxyl groups are essentially coplanar with their attached phenyl group. The interplanar angles between the C=N—O moieties of the oxime unit and their attached phenyl rings are 0.08 (9), 1.08 (15) and 6.65 (15)° in 1, 2 and 3, respectively. In all three molecules, the 2-hydroxy group forms an intramolecular O—H⋯N(oxime) hydrogen bond. In compound (1), intermolecular O—H(oxime)⋯O(hydroxyl) hydrogen bonds generate R22(14) dimers, related by inversion centres. In compound 2, intermolecular O—H(oxime)⋯O(4-hydroxy) hydrogen bonds generate C9 chains along the b-axis direction, while O—H(4-hydroxyl)⋯O(2-hydroxyl) interactions form zigzag C6 spiral chains along the c-axis direction, generated by a screw axis at 1, y, 1/4: the combination of the two chains provides a bimolecular sheet running parallel to the b axis, which lies between 0–1/2 c and 1/2–1 c. In compound 3, similar C9 chains, along the b-axis direction are generated by O—H(oxime)⋯O(4-methoxy) hydrogen bonds. Further weaker, C—H⋯π (in 1), π–π (in 2) and both C—H⋯π and π–π interactions (in 3) further cement the three-dimensional structures. Hirshfeld surface and fingerprint analyses are discussed.The crystal structures of three salicyaldoxime compounds, namely 2-hydroxy-4-methylbenzaldehyde oxime, C RCH=NOH, are found in many biologically active compounds  with different substituents in the 4-position, namely a methyl group, a hydroxy group and a methoxy group, respectively, in compounds, 1, 2 and 3. A frequent finding for salicylaldoxime derivatives is the formation of inversion-related et al., 2016The compounds described herein are all salicylaldoxime derivatives  geometry. Bond angles and bond lengths in the phenyl and oxime fragments are all in the expected ranges.There are no unusual features in the molecular structures. Compound 1 Fig. 1 crystallt Figs. 2 and 3 ▸,1, the hydroxyl group is essentially coplanar with its attached phenyl group [displaced by 0.020 (1) Å], while the interplanar angle between the C=NO moiety of the oxime unit and the attached phenyl rings is 0.08 (9)°. In compound 2, the hydroxyl groups lie essentially within the phenyl ring plane [O atoms deviate by −0.003 (1) and 0.006 (1) Å], while the interplanar angle between the C=NO moiety of the oxime unit and the attached phenyl rings is 1.08 (15)°. In compound 3, the interplanar angle between the C=NO moiety of the oxime unit and the attached phenyl rings is 6.65 (15)°.In compound In all three molecules, an intramolecular O2—H2⋯N12 hydrogen bond Tables 1–3 ▸ ▸ f1, molecules are linked by O13—H13 ⋯O2 hydrogen bonds into inversion-related via the intramolecular hydrogen bond) dimers are linked into two-molecule-wide chains, propagating in the a-axis direction by pairs of O13—H13⋯O13 hydrogen bonds, thereby creating ii hydrogen bond are rather long [2.611 (16) Å] with a small angle of 100.8 (12)°. However, such data fits well with published findings for H2O2 rings: a recent CSD ⋯O4(4-hydroxy)ii hydrogen bonds, propagating in the direction of the b axis, see Fig. 5C6 spiral chain formed from O4—H4⋯O2i hydrogen bonds, see Fig. 6b axis which lies between 0–½ c and ½–1 c. These sheets are further linked by moderately strong π–π stacking interactions, involving all the phenyl rings in the sheet: the Cg⋯Cg separation is 3.7242 (13) Å with a phenyl ring slippage of 1.586 Å. The lack of an 2 is apparent and results from the preferential interaction of the oxime group with the 4-hydroxyl group rather than with the 2-hydroxy group.Compound 3, C9 chains are generated from O13—H13⋯O41(methoxy)i hydrogen bonds, which propagate in the direction of the b axis, see Fig. 72, but involving the methoxy oxygen atom O41 involved instead of the hydroxy oxygen O4. Interestingly, the parameters of the two hydrogen bonds in the chains of compound 2 and 3 are very similar. The chains in compound 3 are linked into a two-dimensional array by C11—H11⋯Cg . The former hydrogen bond forms C9 chains, forming a corrugated ribbon which runs parallel to the a axis.In compound g Table 3 and π–π CrystalExplorer3.1  of the formation of intramolecular O—H⋯NO(oxime) hydrogen bonds involving the ortho hydroxyl group. In addition, this hydroxyl group is also most frequently involved in intermolecular interactions producing inversion-related et al., 2003et al., 2006bR = 2-HO-5-MeOC6H3, producing a C5 chain from O—H(oxime)⋯O(2-hydroxyl) hydrogen bonds; Pfluger et al., 1978R = 2-HO-5-tBu-C6H3, producing a C5 chain from O—H(oxime)⋯O(2-hydroxyl) hydrogen bonds; White et al., 2015aR = 2-HO-3-Me-5-(piperin-1-yl-CH2)-C6H2, producing a C9 chain from O—H(oxime)⋯N(piperinyl) hydrogen bonds; White et al., 2015bR = 2-HO-3-(piperin-1-ylmethyl)-5-tBu-C6H2, producing a C9 chain from O—H(oxime)⋯N(piperinyl) hydrogen bonds; Forgan et al., 2010A survey of the Cambridge Structural Database  and 2-HO-5-MeOC6H3CH=N—OH  = 1.2–1.5Uiso(C).Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989018013361/qm2128sup1.cifCrystal structure: contains datablock(s) 1, 2, 3, global. DOI: 10.1107/S2056989018013361/qm21281sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989018013361/qm21282sup3.hklStructure factors: contains datablock(s) 2. DOI: 10.1107/S2056989018013361/qm21283sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989018013361/qm21281sup5.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018013361/qm21282sup6.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989018013361/qm21283sup7.cmlSupporting information file. DOI: 1868656, 1868655, 1868654CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The correct citation is: Mækelæ MJ, Pfuhl G (2019) Deliberate reasoning is not affected by language. PLoS ONE 14(1): e0211428.


ER) stress shifts the unfolded protein response signaling from cell survival to cell death, although the switching mechanism remains unclear. Here, we report that mitochondrial ubiquitin ligase (MITOL/MARCH5) inhibits ER stress‐induced apoptosis through ubiquitylation of IRE1α at the mitochondria‐associated ER membrane (MAM). MITOL promotes K63‐linked chain ubiquitination of IRE1α at lysine 481 (K481), thereby preventing hyper‐oligomerization of IRE1α and regulated IRE1α‐dependent decay (RIDD). Therefore, under ER stress, MITOL depletion or the IRE1α mutant (K481R) allows for IRE1α hyper‐oligomerization and enhances RIDD activity, resulting in apoptosis. Similarly, in the spinal cord of MITOL‐deficient mice, ER stress enhances RIDD activity and subsequent apoptosis. Notably, unresolved ER stress attenuates IRE1α ubiquitylation, suggesting that this directs the apoptotic switch of IRE1α signaling. Our findings suggest that mitochondria regulate cell fate under ER stress through IRE1α ubiquitylation by MITOL at the MAM.Unresolved endoplasmic reticulum ( Various physiological and pathological changes require enhanced ER functions, such as protein folding, removal of unfolded proteins, and reduction of oxidative stress. An imbalance in ER homeostasis causes ER stress and triggers the unfolded protein response (UPR), which is initiated by three ER proteins, PERK, ATF6, and IRE1α. The UPR is involved in the recovery of ER homeostasis through ERAD and ER chaperones  and plays a central role in the lipid metabolism and Caet al, et al, et al, et al, We have previously identified mitochondrial ubiquitin ligase (MITOL/MARCH5) and demonstrated that MITOL ubiquitylates mitofusin 2 (Mfn2) and enhances its GTPase activity, resulting in the tethering between the ER and mitochondria rather than mitochondrial fusion  481 of IRE1α by adding a K63‐linked polyubiquitin chain, which in turn suppresses the activity and oligomerization of IRE1α. Here, we provide evidence that MITOL can directly regulate IRE1α through the MAM and thus play an important role in determining cell fate under ER stress.mitol/march5 gene ‐inducible MITOL‐knockout MEFs by flanking two loxP sequences with exon 2 of the ells Fig E–G, sugg2+ in the ER was increased in MITOL‐KO MEFs  showed abnormal morphology of the ER but not of the mitochondria Fig H and I. MEFs Fig J. We firMEFs Fig A. MITOL‐MEFs Fig B. To furMEFs Fig C. In conMEFs Fig C. These et al, ER stress has been shown to trigger apoptosis via mitochondrial permeability transition pore  was used to select the genomic sequence target in human MITOL (5ʹ‐CCAAGCCCTACAGCAGATGC‐3ʹ). Oligo pairs encoding 20‐nt guide sequences were annealed and ligated into the plasmid pX330 (purchased from Addgene). HEK293 cells were transfected and MITOL‐KO clones selected by serial dilution.MEFs, HEK293, and COS‐7 cells and HeLa cells were grown in Dulbecco's modified Eagle's medium (DMEM) supplemented with 10% fetal bovine serum (FBS) and penicillin/streptomycin. Cells were transfected with either Lipofectamine 3000 (Invitrogen) or RNAiMax (Invitrogen) according to the manufacturer's protocol. The following siRNAs were used: siIRE1α #1: sense, 5ʹ‐CGGGCUCCAUCAAGUGGACUUUAAATT‐3ʹ, antisense, 5ʹ‐UUUAAAGUCCACUUGAUGGAGCCCGTT‐3ʹ; siIRE1α #2: sense, 5ʹ‐AAGAUGGACUGGCGGGAGATT‐3ʹ, antisense, 5ʹ‐UCUCCCGCCAGUCCAUCUUTT‐3ʹ; siJNK1 #1: sense, 5ʹ‐AAAGAAUGUCCUACCUUCUTT‐3ʹ, antisense, 5ʹ‐AGAAGGUAGGACAUUCUUUTT‐3ʹ; and siJNK1 #2: sense, 5ʹ‐GCAGAAGCAAACGUGACAACATT‐3ʹ, antisense, 5ʹ‐UGUUGUCACGUUUGCUUCUGCTT‐3ʹ. siPACS2 and siMfn2 were described previously  was subjected to further separation by 30% Percoll gradient centrifugation at 95,000 × g for 30 min at 4°C. A low‐density band (denoted as the MAM fraction) was purified. The pure mitochondrial fraction in the high‐density band was resuspended in HB and pelleted by centrifugation . Microsomes were pelleted from the mitochondrial supernatant by centrifugation at 100,000 × g for 1 h. Cytosol was recovered as the supernatant from this centrifugation.Isolation of crude mitochondria or pure MAM was performed as described previously  and subjected to reverse transcription to cDNA using ReverTra Ace qPCR RT Kit (TOYOBO), following the manufacturer's protocol. PCR was performed using a THUNDERBIRD SYBR qPCR Mix (TOYOBO). The PCR conditions were as follows: 95°C for 1 min followed by 40 cycles at 95°C for 15 s, 60°C for 30 s, and 72°C for 60 s. RT–PCR was performed using miScript SYBR Green PCR Kit and miScript Primer Assays (Qiagen).atf4: forward, 5ʹ‐GGA CAGATTGGATGTTGGAGAAAATG‐3ʹ, reverse, 5ʹ‐GGAGATGGCCAATTGGGTTCAC‐3ʹ; caspase‐2: forward, 5ʹ‐ CCACAGATGCTACGGAACA‐3ʹ, reverse, 5ʹ‐ GCTGGTAGTGTGCCTGGTAA‐3ʹ; chop: forward, 5ʹ‐CATACACCACCACACCTGAAAG‐3ʹ, reverse, 5ʹ‐CCGTTTCCTAGTTCTTCCTTGC‐3ʹ; dr5: forward, 5ʹ‐CTGTGCTACAGGCTGTCTTTG‐3ʹ, reverse, 5ʹ‐GTACTGGCCTGCTAGACAG‐3ʹ; xbp1s: forward, 5ʹ‐GTGTCAGAGTCCATGGGA‐3ʹ, reverse, 5ʹ‐GAGTCCGCAGCAGGTG‐3ʹ; edem: forward, 5ʹ‐AAGCCCTCTGGAACTTGCG‐3ʹ, reverse, 5ʹ‐AACCCAATGGCCTGTCTGG‐3ʹ; Sec61: forward, 5ʹ‐CTATTTCCAGGGCTTCCGAGT‐3ʹ, reverse, 5ʹ‐AGGTGTTGTACTGGCCTCGGT‐3ʹ; herp: forward, 5ʹ‐CATGTACCTGCACCACGTCG‐3ʹ, reverse, 5ʹ‐GAGGACCACCATCATCCGG‐3ʹ; col6a1: forward, 5ʹ‐TGCTCAACATGAAGCAGACC‐3ʹ, reverse, 5ʹ‐TTGAGGGAGAAAGCTCTGGA‐3ʹ; blos1: forward, 5ʹ‐CAAGGAGCTGCAGGAGAAGA‐3ʹ, reverse, 5ʹ‐GCCTGGTTGAAGTTCTCCAC‐3ʹ; hgsnat: forward, 5ʹ‐TCTCCGCTTTCTCCATTTTG‐3ʹ, reverse, 5ʹ‐CGCATACACGTGGAAAGTCA‐3ʹ; pdgfrp: forward, 5ʹ‐AACCCCCTTACAGCTGTCCT‐3ʹ, reverse, 5ʹ‐TAATCCCGTCAGCATCTTCC‐3ʹ; txnip: forward, 5ʹ‐TCAAGGGCCCCTGGGAACATC‐3ʹ, reverse, 5ʹ‐GACACTGGTGCCATTAAGTCAG‐3ʹ; and gapdh: forward, 5ʹ‐AACTTTGGCATTGTGGAAGG‐3ʹ, reverse, 5ʹ‐GGATGCAGGGATGATGTTCT‐3ʹ. Primers for xbp1s were designed to amplify the region containing sequences removed by IRE1α.The following primers were used: g, the precipitate and supernatant were analyzed by immunoblotting.To extract cholesterol‐enriched lipid raft from MAM, 100 μg of crude mitochondria was incubated for 10 min with indicated final concentrations of digitonin on ice. After centrifugation at 8,000 × g for 20 min at 4°C. The supernatant was subjected to immunoprecipitation using indicated antibodies. To evaluate the ubiquitylation level of proteins, cells were solubilized with RIPA lysis buffer  and centrifuged at 20,000 g for 20 min at 4°C. The supernatant was sonicated 10 s and subjected to immunoprecipitation using indicated antibodies.To examine the protein interaction, cells were solubilized with NP‐40 lysis buffer  and centrifuged at 20,000 2 following the manufacturer's protocol.Whole lysates were separated by SDS–PAGE and transferred to the PVDF membranes (Millipore). The blots were probed with indicated antibodies, and protein bands on the blot were visualized by the enhanced chemiluminescence reagent (Millipore). Phos‐tag‐PAGE was performed using 7% SDS–PAGE minigels containing 10 μM Phos‐tag (Wako) in the presence of 100 μM MnCl2, 4 mM ATP, 200 ng of E1 , 600 ng of UbcH5b (Biomol), and 5 μg of His‐Ub (Biomol) for 2 h at 30°C and then terminated with 3 × SDS sample buffer.IRE1α‐FLAG and MITOL‐HA were purified from HEK293 cells by immunoprecipitation. The purified proteins were incubated with reaction buffer containing 50 mM Tris–HCl, pH 7.4, 2 mM MgClet al, To determine the specific domains required for the interaction between MITOL and IRE1α, GST‐fusion deletion mutants were prepared using glutathione high‐capacity magnetic agarose beads (Sigma) as described previously , and analyzed using an Olympus IX81 confocal fluorescence microscope. For classification of the morphology of mitochondrial network, four stacks of 0.2 μm were acquired for cells stained with anti‐Tom20 antibody using 60× objective. Images were compiled and classified in a blinded manner as normal in which the majority of mitochondria were connected in the cell or abnormal in which many mitochondria exhibited the spherical structure or showed the disconnected network overall. For quantification of the morphology of the ER network, four stacks of 0.2 μm were acquired for cells transfected with mC‐Sec61β using 60× objective and classified in a blinded manner as normal morphology with reticular‐like ER network or abnormal morphology either with a more sheet‐like ER network overall or with at least three aggregated parts in the ER network. Percentages of cells with abnormal ER network in each condition were calculated from 50 cells in each independent experiment.In Situ Cell Death Detection Kit (Roche). For Nissl, staining was performed using 0.5% cresyl violet. The sections were observed using an All‐in‐One Fluorescence Microscope BZ‐9000.Spinal cord was fixed with 10% formalin neutral buffer solution (Wako), and 5‐μm‐thick paraffin sections were prepared. TUNEL staining was performed using 2+ imaging was performed as described previously  and re‐fed with HBSS. G‐CEPIA1er signals of transfected cells were monitored per 500‐ms interval during 60 s. At 20 s after Ca2+ imaging started, these cells were co‐incubated with 5 μM ionomycin. The level of Ca2+ in the ER was obtained as ΔF values, calculated from F0 minus Fmax. F0 values were obtained by the average intensity of G‐CEPIA1er in each cell before ionomycin treatment. Fmax was calculated from the average intensity of G‐CEPIA1er in each cell treated with ionomycin. The intensities of G‐CEPIA1er were measured using ImageJ.ER Caet al, g for 20 min at 4°C. The supernatant was centrifuged at 250,000 g for 12 h at 4°C through 20–40% sucrose gradient , prepared freshly by progressively layering higher to lower density sucrose fractions in 5% increments. Each 4 ml gradient was divided evenly into 16 fractions (250 μl each), and then, aliquots of fractions 2–13 were analyzed by immunoblotting.Sucrose gradient assay was performed as described previously  in saline.MITOLAnnexin V‐FITC staining was performed with Annexin V‐FITC apoptosis detection kit (BioVision) according to the manufacturer's protocol. For the detection of mitochondrial depolarization, cells were incubated with 10 nM tetramethylrhodamine methyl ester (TMRM) for 30 min at 37°C and then washed with PBS. The fluorescence of TMRM was analyzed by flow cytometer (Becton Dickinson).Luciferase assay was performed with dual‐luciferase reporter assay system (Promega) according to the manufacturer's protocol.Cell viability and cell toxicity were monitored using the Cell Counting Kit‐8 (Dojindo) and Cytotoxicity LDH Assay Kit‐WST (Dojindo), respectively, according to the manufacturer's protocol.t‐test. The number of independent experiments is shown as n.All results are expressed as mean ± SD. Obtained data were compared between independent experiments using either two‐tailed Student's Flox/Flox mice and MITOL‐related MEFs. TI and TU generated IRE1α‐KO MEFs. TT, TF, and NM contributed to the understanding of MITOLnestin mice phenotype. KT and SY wrote the manuscript with contribution from RI.KT and SY designed and carried out the experiments. SN analyzed the data. AU carried out qRT–PCR and cultured cell analysis with contribution from IS and NI. SI generated MITOLThe authors declare that they have no conflict of interest.Expanded View Figures PDFClick here for additional data file.Review Process FileClick here for additional data file.


The conformation of the title compound is discussed and compared to those of related structures. In the crystal, molecules of the title compound are assembled into layers parallel to the  28H22N4O9, exhibits crystallographically imposed twofold rotational symmetry, with a dihedral angle of 66.0 (2)° between the planes of the two central benzene rings bounded to the central oxygen atom. The dihedral angle between the planes of the central benzene ring and the terminal phenol ring is 4.9 (2)°. Each half of the molecule exhibits an imine E configuration. An intramolecular O—H⋯N hydrogen bond is present. In the crystal, the molecules are linked into layers parallel to the ab plane via C—H⋯O hydrogen bonds. The crystal studied was refined as a two-component pseudomerohedral twin.The molecule of the title compound, C The dihedral angle between the benzene and 4-methoxy-2-nitrophenol rings in the same half of the molecules is 4.9 (2)°, indicating an almost coplanar arrangement of the benzene and phenol rings. The sp2-hybridized character of atoms N1 and C7 is confirmed by the N1—C7 [1.287 (6) Å] bond length and C7—N1—C8 [121.9 (4)°] and N1—C7—C6 [121.7 (4)°] bond angles °. In the molecule, atom N1 of the imine moiety acts as a hydrogen-bond acceptor for the adjacent phenol group, forming an intramolecular O—H⋯N hydrogen bond with an S(6) ring motif -N,N′-[oxybis]bis(1-phenylmethanimine) moiety with different substituents were found. The reference moiety is illustrated in Fig. 31R) together with the dihedral and torsion angles for oxybisbenzenyl moiety in these structures are tabulated in Table 2viz. non-coplanar [dihedral 2 = 18.0–73.5°] and nearly coplanar [dihedral 2 = 4.8–9.9°]. In all of these structures, the imine C=N double bond adopts an E configuration with torsion angles corresponding to C6—C7—N1—C8 in the range 172.9–180.0°.In a search of the Cambridge Structure Database  C, 60.16; H, 3.93; N, 10; found: C, 59.04; H, 3.85; N, 9.90%. 1H NMR : δ 10.23 , δ 9.12 , δ 7.69–7.21 , δ 3.83 . 13C NMR : δ 161.69 (C=N), δ 156.21–114.96 (C-aromatic), δ 56.25 (OCH3). IR (KBr pellets υmax/cm−1): 3441 υ(OH), 3109 υ, 2956 υ(CH3), 1598 υ(C=N), 1529 υ, 1497 υ, 1326 υ, 1257 υ, 1194 υ, 1056 υ(C—N), 979 υ.To a sample of 2-hydroxy-5-methoxy-3-nitrobenzaldehyde  dissolved in 25.0 mL of methanol, 0.20 mL of glacial acetic acid were added, and the mixture was refluxed for 30 min. A solution of 4,4′-oxydianiline  in 20.0 mL of methanol was added dropwise under stirring to the aldehyde solution. The resulting deep-red solution was refluxed for 4 h with stirring. The reaction scheme is shown in Fig. 4Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl group. The crystal investigated was refined as a two-component pseudomerohedral twin resulting from a 180° rotation about the [001] reciprocal lattice direction, with a twin ratio of 0.977 (3):0.023 (3).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989019016852/rz5267sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019016852/rz5267Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019016852/rz5267Isup3.cmlSupporting information file. DOI: 1445336CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure and supramolecular interactions between a hydroxy-functionalized pillarene and 1-octanamine guest molecule, which forms an interesting host–guest system, are reported. 44H48O10·C8H19N·H2O. The guest compound is stabilized inside the cavity by hydrogen-bonding and C—H⋯π interactions. The water molecule in the asymmetric unit mediates the formation of a supramolecular dimer by hydrogen-bonding interactions. These functionalized-pillararene hosts expand the possibility of exploring more supramolecular interactions with various guest species.Co-crystallization of a monofunctionalized hydroxy pillar[5]arene with 1-octanamine resulted in the formation of an inclusion complex where the alkyl chain is threaded in the macrocycle cavity, namely 1,2,3,4--5-(1-hydroxy-4-methoxy)-pillar[5]arene–1-octanamine–water (1/1/1), C Unlike cone-shaped calixarene or resorcinarene-type structures, the pillararenes have a tabular cavity, which makes them interesting molecular hosts. It is well known that pillar[5]arenes exhibit an outstanding ability to selectively bind different kinds of guest molecules and thus are valuable chemical entities in the areas of host–guest systems and molecular recognition . Furthermore, the OH– group in pillararenes could involve hydrogen bonding with guest molecules and/or with neighboring pillararenes, which makes them valuable compounds in molecular recognition and supramolecular chemistry. We have recently reported details of the host–guest complexation between mono-hydroxy-pillar[5]arenes with long-chain alkyl alcohol guests . It was observed that the encapsulation characteristics of the pillar[5]arene was affected by the presence of the hydroxy group, resulting in the formation of a 1:2 complex with long-chain alkyl alcohols.The pillar[5]rene system having one hydroxy group is interesting because this OH– function is susceptible for further chemical transformation (Al-Azemi et Pil-OH) and 1-octanamine (2OctNH). The structural features and supramolecular host–guest interactions of this co-crystalline system (2Pil-OH·OctNH) has been addressed and discussed.In this work we report the crystal structure of the inclusion complex consisting of 1-(1-hydroxy-4-methoxy)-2,3,4,5--pillar[5]arene  has a rigid three-dimensional macrocyclic architecture with a wide cavity having a pentagonal shape. The 1-octanamine molecule is threaded inside the pillararene cavity and one water is included in asymmetric unit, displaying strong hydrogen-bonding interactions with the amino group of the guest molecule inside the cavity and the hydroxy group on the pillararene system via O11—H11A⋯N1 and O11—H11B⋯O1 bonds respectively  −x + 2, −y + 1, −z + 1] and O11—H11⋯O1 hydrogen-bonding interactions  x − 1, y, z]. A weak C—H⋯O type pillararene–pillararene interaction is also observed .In the title inclusion complex, the water molecule mediates the formation of supramolecular dimers through O1s Table 1, as illuet al., 2018The synthesis of 1-(1-hydroxy-4-methoxy)-2,3,4,5-pillar[5]arene has been reported previously  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989018010034/dx2005sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018010034/dx2005Isup4.hklStructure factors: contains datablock(s) I. DOI: 1855261CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: