Intermolecular N—H⋯O and C —H⋯O hydrogen bonds connect centrosymmetrically related molecules into dimers, forming rings of a axis into a columnar arrangement.The title Schiff base molecule displays a  16H16N4O5S·C3H7NO, displays a trans conformation with respect to the C=N double bond. The C—N and N—N bonds are relatively short compared to their normal bond lengths, indicating some degree of delocalization in the molecule. The molecule is bent at the S atom, with an S—N—C—C torsion angle of 164.48 (11)°. The dihedral angle between the two aromatic rings is 84.594 (7)°. Intermolecular N—H⋯O and C —H⋯O hydrogen bonds connect centrosymmetrically related molecules into dimers forming rings of R33(11) and R22(10) graph-set motif stacked along the a axis into a columnar arrangement. The molecular columns are further linked into a three-dimensional network by C—H⋯π interactions.The molecule of the title Schiff base compound, C N-(p-toluenesulfonyl)amino acids have been studied extensively for their biological and medicinal activities -4-methyl-N-{2-[2-(4-nitrobenzylidene)hydrazin-1-yl]-2-oxoethyl}benzenesulfonamide N,N-dimethylformamide monosolvate.Hydrazones possess a wide variety of biological activities which include anti-inflammatory, analgesic, anticonvulsant, antituberculous, antitumor, anti-HIV and antimicrobial activity. Hydrazones and their derivatives which can be prepared easily are stable and crystalline in nature. These characteristics have made them suitable compounds in recent times for drug design, ligands for metal complexes and for heterocyclic synthesis. Thus, hydrazones derived from syn to each other. The C8—O3 and C9—N3 bond lengths of 1.219 (2) and 1.274 (2) Å, respectively, confirm their significant double-bond characters. Further, the C8—N2 and N2—N3 bond lengths of 1.354 (2) and 1.3723 (18) Å, respectively, also indicate a significant delocalization of π-electron density over the hydrazone portion of the molecule. The molecule is bent at the S atom, with an S1—N1—C7—C8 torsion angle of 164.48 (11)°. The sulfonamide bond exists in a synclinal conformation, with a C—S—N—C torsion angle of −78.2 (1)°, which is the most preferred conformation for aromatic sulfonamides ° and C6—C1—S1—N1 = 98.87 (16)°, while that of the hydrazone group with the attached 4-nitrobenzene ring is given by the torsion angles C11—C10—C9—N3 = 1.6 (2)° and C15—C10—C9—N3 = −177.27 (15)°, respectively. The dihedral angle between the C1–C6 sulfonyl benzene ring and the mean plane through the SO2—NH—CH2—CO segment is 81.452 (6)°, while that between the C10–C15 benzene ring and the plane through the C9—N3—N2—CO group is 4.296 (10)°. The dihedral angle between the two aromatic rings is 84.594 (7)°. The central part of the title compound, between atoms N1 and C9, is nearly planar with an extended chain conformation. The two benzene rings, i.e. C1–C6 and C10–C15, are inclined to the mean plane of the central spacer unit  by 85.59 (8) and 4.35 (8)°, respectively.The title compound crystallizes as a dimethylformamide (DMF) monosolvate with one molecule each of the Schiff base and solvent in the asymmetric unit Fig. 1, and twoa axis by C—H⋯O hydrogen bonds involving aromatic C3 and sulfonyl O3 atoms -N-{2-[2-(4-methylbenzylidene)hydrazin-1-yl]-2-oxoethyl}-p-toluenesulfonamide, (II) E)-N-{2-[2-(4-Nitrobenzylidene)hydrazine-1-yl]-2-oxoethyl}-4-methylbenzenesulfonamide N,N-dimethylformamide monosolvate was prepared as follows: p-toluenesulfonyl chloride (0.01 mol) was added to glycine (0.02 mol) dissolved in an aqueous solution of potassium carbonate . The reaction mixture was stirred at 373 K for 6 h, left overnight at room temperature, then filtered and treated with dilute hydrochloric acid. The solid N-(4-methylbenzenesulfonyl)glycine (L1) obtained was crystallized from aqueous ethanol. Sulfuric acid (0.5 ml) was added to L1 (0.02 mol) dissolved in ethanol (30 ml) and the mixture was refluxed. The reaction mixture was monitored by thin-layer chromatography (TLC) at regular intervals. After completion of the reaction, the reaction mixture was concentrated to remove excess ethanol. The product, N-(4-methylbenzenesulfonyl)glycine ethyl ester (L2), was poured into water, neutralized with sodium bicarbonate and recrystallized from acetone. Pure L2 (0.01 mol) was then added in small portions to a stirred solution of 99% hydrazine hydrate (10 ml) in 30 ml ethanol and the mixture was refluxed for 6 h. After cooling to room temperature, the resulting precipitate was filtered, washed with cold water and dried to obtain N-(4-methylbenzenesulfonyl)glycinyl hydrazide (L3). A mixture of L3 (0.01 mol) and p-nitrobenzaldehyde (0.01 mol) in anhydrous methanol (30 ml) and two drops of glacial acetic acid was refluxed for 8 h. After cooling, the precipitated (E)-N-{2-[2-(4-nitrobenzylidene)hydrazine-1-yl]-2-oxoethyl}-4-methylbenzenesulfonamide was collected by vacuum filtration, washed with cold methanol, dried and recrystallized to constant melting point from methanol (522–523 K). The purity of the compound was checked by TLC and characterized by its IR spectrum. The characteristic absorptions observed are 3236.6, 1687.7, 1587.4, 1338.6 and 1163.1 cm−1 for the stretching bands of N—H, C=O, C=N, S=O asymmetric and S=O symmetric, respectively. The characteristic 1H and 13C NMR specta of the title compound are as follows. 1H NMR , 3.61, 4.10 , 7.36–7.39 , 7.72–7.74 , 7.86 , 8.23–8.27 , 7.93 , 8.02 , 11.74 . 13C NMR : δ 20.91, 43.20, 44.55, 123.94, 126.60, 127.81, 129.48, 137.48, 140.24, 141.40, 142.64, 144.62, 147.73, 164.64, 169.44. Prism-like colourless single crystals of the title compound employed in the X-ray diffraction study were grown from a DMF solution by slow evaporation of the solvent. or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017014669/rz5222sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017014669/rz5222Isup2.hklStructure factors: contains datablock(s) I. DOI: 1433602CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III(CO)(C(dppm)2-κ3P,C,P′)ClH]Cl and Cl2 have been determined. Both complexes show a slightly distorted octahedral coordinated IrIII centre. The PCP pincer ligand system is arranged in a meridional manner.The crystal structures of [Ir et al. methyl]diphenylphosphanylidene}methane-κ3P,C,P′)carbonylchloridohydridoiridium(III) chloride dichloromethane trisolvate, Cl·3CH2Cl2 (1) and the closely related (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}methanide(1+)-κ3P,C,P′)carbonylchloridohydridoiridium(III) dichloride–hydrochloric acid–water (1/2/5.5), Cl}2 (2), have been designed and both complexes show a slightly distorted octahedral coordinated IrIII centre. The PCP pincer ligand system is arranged in a meridional manner, the CO ligand is located trans to the central PCP carbon and a hydride and chloride are located perpendicular above and below the P2C2 plane. With an Ir—CCDP distance of 2.157 (5) Å, an Ir—CO distance of 1.891 (6) Å and a quite short C—O distance of 1.117 (7) Å, complex 1 presents a strong carbonyl bond. Complex 2, the corresponding CH acid of 1, shows an additionally attached proton at the carbodiphosphorane carbon atom located antiperiplanar to the hydride of the metal centre. In comparison with complex 1, the Ir—CCDP distance of 2.207 (3) Å is lengthened and the Ir—C—O values indicate a weaker trans influence of the central carbodiphosphorane carbon atom.After the successful creation of the newly designed PCP carbodiphosphorane (CDP) ligand [Reitsamer  al. 2012. Dalton  al. 2007. Chem. C Consequently, this central atom disposes of two lone-electron pairs and is able to interact with one or two Lewis acids  functionality and can be described as a naked carbon atom or as a divalent carbon(0) atom in an excited singlet (12]Cl enters an oxidative addition reaction with Vaska’s compound [IrI(CO)Cl(PPh3)2], forming the iridium PCP pincer CDP complex Cl (1) (see reaction scheme). During this reaction sequence, the central carbon atom is deprotonated, becomes neutral and coordinates the iridium transition metal. Treatment of complex 1 with hydrochloric acid leads to the protonation of the central carbon atom and consequently to the formation of the conjugate CH acid of 1, the Cl2 complex 2 1 (C(dppm)2-κ3P,C,P′)ClH]+ monocation and the chloride counter-ion. The iridium transition metal centre exhibits an octahedral ligand system, formed by a meridional arranged C(dppm)2, relative to the C1 atom, a trans-coordinated carbonyl unit, and a chlorido and hydrido ligand located perpendicular to the meridional plane or more precisely trans to each other. The P1—Ir1—P4 angle of 170.69 (5)° indicates a small deviation from the octahedral geometry and this value is larger compared to many related Iridium PCP pincer complexes. The environment of the CDP carbon atom C1 is strictly planar  < Csp3]. Consequently, the Ir1—C1 separation of 2.157 (5) Å indicates an sp3 hybridization of the carbodiphosphorane carbon atom, which is substantiated by the data collected in Table 1B] and 2.62 Å [Cl2⋯H3B] illustrate the location within the van der Waals radii. These C—H⋯X interactions are a common feature of complexes containing dppm or related ligands ] and 2.47 Å [Cl2⋯H6B].Complex 1 Fig. 1 crystall2 comprises two Cl2 complex molecules (CH(dppm)2-κ3P,C,P′)ClH]2+ dication stabilized by two chloride counter-ions. Overall, complex 2 represents the conjugate CH acid of the Cl complex (1). The carbodiphosphorane carbon atom additionally coordinates a second Lewis acid, the proton H1, which adopts an anti-periplanar conformation relative to the hydrido ligand H11. As a consequence, atom C1 forms a distorted tetrahedron with the directly coordinated atoms (sum of angles = 344.3°). In comparison with complex 1, the values of the angles P2—C1–Ir1 and P3—C1—Ir1 are significantly reduced, whereas the P2—C1—P3 angles differs to a lesser extent (Table 21 [2.157 (5) Å], as has also been observed in other carbodiphosphorane complexes ], 2.89 Å [H2B⋯Cl7] and 2.57 Å [H3B⋯Cl5].The asymmetric unit of es Fig. 2, four mot Table 2. The coos Table 4 between 1, there are interactions  = 2.62 Å] with distances shorter than the sum of the van der Waals radii. Such C—H⋯X interactions are a common feature of complexes containing dppm or related ligands  = 2.59 Å and H5B⋯Cl2 = 2.47 Å].In s Table 3 between 2, C—H⋯O and C—H⋯Cl interactions ], 2.89 Å [H2B⋯Cl7] and 2.57 Å [H3B⋯Cl5]. A network of different interactions occurs between the two independent complex molecules. The water and hydrochloric acid solvent molecules form hydrogen bonds with the chloride ligands or counter-ions and the hydrogen atoms of the complex molecules, respectively.In s Table 4 occur be2) using standard Schlenk techniques. The 1H, 13C and 31P NMR spectra were recorded on a Bruker DPX 300 NMR spectrometer and were referenced against the 13C/1H solvent peaks of the solvents chloroform, methanol or the external 85% H3PO4 standard, respectively. The phosphorus atoms in the NMR data are labelled as in Figs. 1All preparations were carried out under an inert atmosphere (N2-Synthesis of Cl (1): A mixture of 19.5 mg of Vaska’s complex (0.025 mmol), 20.4 mg of [CH(dppm)2]Cl (0.025 mmol)  was stirred at ambient temperature for 15 min. The solvent was evaporated in vacuo and the residue was digested with a mixture of CH2Cl2 (0.1 ml) and ethyl acetate (0.7 ml). The solid was separated and washed twice with ethyl acetate (0.6 ml). Single crystals were grown by slow evaporation of a solution in CH2Cl2. 31P {1H} NMR (CHCl3): δ 31.9 , δ 8.2 (P1/P4); 13C {1H} NMR (CDCl3): δ −4.4  = 4); 1H NMR (CDCl3): δ −16.7 .2-Synthesis of Cl2 (2): 19.5 mg of Vaska’s complex (0.025 mmol) and 20.4 mg of [CH(dppm)2]Cl (0.025 mmol) . The mixture was stirred at ambient temperature for 15 min. After addition of 0.1 ml of hydrochloric acid (10 mol L−1), the product crystallized upon standing for a day. 31P {1H} NMR (CHCl3/MeOH): δ 45.3 , δ 1.7 (P1/P4); 13C {1H} NMR (CDCl3): δ 9.1  = 38, 1JC1H1 = 122); 1H NMR (CDCl3/MeOH): δ −18.9 .1 resulted in the location of the hydride hydrogen atom. The bond length was restrained to a distance of 1.6 Å and a fixed isotropic displacement parameter of 1.5Ueq of iridium was applied. The hydrido ligand of complex 2 was also detected and refined isotropically without the use of bond restraints. Furthermore, the proton of the CDP carbon atom was spotted and refined with bond restraints of 0.98 Å. The hydrogen atoms of the water and solvent molecules could only be partially detected and were omitted. A determination of a 1:1 positional disorder of one water molecule (O4 and O4A) and one HCl or chloride (Cl10 and Cl1A) was possible. Eight chloride positions can be detected, which are occupied by a total of four chlorides and four hydrochloric acid units. The hydrogen-atom positions of the phenyl subunits and methylene groups were refined with calculated positions (C—H = 0.94 and 0.98 Å) using a riding model with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 52 are related to each other by the presence of a pseudo-symmetry centre. A halving of the c axis and consequently the changing of the monoclinic setting from P21/n to P21/c allows the consideration of one formula unit of 2. A closer observation of the sections of the reciprocal lattice along c* (l = 2n + 1) at different values of l results in the presence of frequent weak reflections. Consequently, an interpretation of this system as three-dimensional network between two complex molecules, four hydrochloric acid units and eleven water molecules allows the involvement of these weak, but clearly existing reflections, and establishes the possibility of the distinction of the chloride and oxygen positions.The two complex molecules of 10.1107/S2056989018004905/eb2007sup1.cifCrystal structure: contains datablock(s) global, complex1, complex2. DOI: 10.1107/S2056989018004905/eb2007complex1sup2.hklStructure factors: contains datablock(s) complex1. DOI: 10.1107/S2056989018004905/eb2007complex2sup3.hklStructure factors: contains datablock(s) complex2. DOI: 1577807, 1577808CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure is stabilized by N/C—H⋯O hydrogen bond, C—H⋯F and C—H⋯π interactions with weak π–π interactions contacts to form a three-dimensional architecture.The title compound, C 18H22FN5O8S, is used as a herbicide (pyrimidinylsulfonylurea herbicide). The dihedral angle between the mean planes of the pyridine and pyrimidine rings is 86.90 (7)°. In the crystal, N/C—H⋯O hydrogen bonds, C—H⋯F and C—H⋯π interactions link adjacent molecules, forming a chain along [020]. A further two C—H⋯O hydrogen bonds together with weak π–π interactions [ring centroid separation = 3.7584 (12) Å] further aggregate the structure into a three-dimensional architecture.The title compound, {systematic name: 1-[3-carbamoyl]amino}sulfonyl)pyridin-2-yl]-2-fluoropropyl 2-methoxyacetate}, C DOI: 10.1107/S2056989017012737/hg5495Isup2.hklStructure factors: contains datablock(s) I. DOI: 1572854CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound, a bromo derivative of pyranocoumarin, possesses photobiological activity. It was formed by bromination of seselin by using NBS in MeOH at room temperature. In the crystal, molecules are linked by π–π stacking interactions and weak C—H⋯O interactions, forming layers parallel to (001). 15H14Br2O4 chromen-2(8H)-one], is a pyranocoumarin derivative formed by the bromination of seselin, which is a naturally occurring angular pyranocoumarin isolated from the Indian herb Trachyspermum stictocarpum. In the molecule, the benzopyran ring system is essentially planar, with a maximum deviation of 0.044 (2) Å for the O atom. The dihydropyran ring is in a half-chair conformation and the four essentially planar atoms of this ring form a dihedral angle of 4.6 (2)° with the benzopyran ring system. In the crystal, molecules are linked by weak C—H⋯O hydrogen bonds, forming chains propagating along [010]. In addition, π–π stacking interactions, with centroid–centroid distances of 3.902 (2) and 3.908 (2) Å, link the hydrogen-bonded chains into layers parallel to (001).The title compound, C The dihydropyran ring C1–C5/O1 is in a half-chair conformation and atoms C2 and C3 deviate by −0.385 (4) and 0.280 (4) Å from the plane through the other four essentially planar atoms (mean deviation 0.003 Å), which makes a dihedral angle of 4.6 (2)° with the benzopyran ring system. The relative stereochemistry at atoms C3 and C4 is R/S and S/R.The title molecule Fig. 1 is compoCg1⋯Cg1 of 3.902 (2) Å and Cg1⋯Cg2 of 3.908 (2) Å where Cg1 and Cg2 are the centroids of the C1/C5/C6/C10–C12 and O2/C6–C10 rings, respectively, link the hydrogen-bonded chains, forming layers parallel (001)  Fig. 3.et al., 2016et al., 2006A search of the Cambridge Structural Database  from ethyl acetate:hexane (1:4) at room temperature by slow evaporation of the solvents. NMR analysis: 1H NMR data : δH 8.02 , 7.32 , 6.82 , 5.36 , 4.26 , 3.56 , 1.50 , 1.54 .The title compound is a colourless solid substance formed on bromination of the naturally occurring seseline isolated from the methanol extract of iso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017006132/lh5842sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017006132/lh5842Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017006132/lh5842Isup3.cmlSupporting information file. DOI: 1545541CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecular and crystal structure of zwitterionic 2-{[methyl]carbamoyl}benzoate hemihydrate is reported. The crystal structure is stabilized by a variety of hydrogen bonds and offset π–π stacking interactions. 15H15N3O3·0.5H2O, comprises two 2-{[methyl]carbamoyl}benzoate zwitterions (A and B) and a water molecule. The dihedral angles between the pyridine and phenyl rings in the zwitterions are 53.69 (10) and 73.56 (11)° in A and B, respectively. In the crystal, molecules are linked by N—H⋯O, O—H⋯O, C—H⋯O and C—H⋯π(ring) hydrogen bonds into a three-dimensional network. The crystal structure also features π–π interactions involving the centroids of the pyridine and phenyl rings [centroid–centroid distances = 3.5618 (12) Å in A and 3.8182 (14) Å in B].The asymmetric unit of the title compound, C The study and synthesis of new zwitterions is therefore important in the search for new biomedical applications  and a cocrystallized water molecule, as shown in Fig. 12—Car single bond [1.38 (3) Å], but are similar to those found in related compounds with an N+=C double bond  Å and C15A—O2A = 1.257 (3) Å] in molecule A, with comparable values in molecule B, are similar to values found in other deprotonated carboxylate groups methyl]carbamoyl}benzoate zwitterions   Å, where Cg3 and Cg4 are the centroids of the N1A/C1A–C5A and C9A–C14A rings]  Fig. 4. The crys] Fig. 5. An overet al., 2016N-[2-ethyl]phthalamic acid tetrahydrate phthalamic acid -2-[(1-phenylethyl)carbamoyl]benzoate  -1-phenylethanaminium 2-{carbamoyl}benzoate -4H-1λ2-pyridine as the skeleton gave 15 hits, although none of these were zwitterionic derivatives comparable to the title compound. Of these, only three had aromatic rings in the cation in addition to the iminopoyridine unit phthalimide and 0.01 mol of 4-amino-3-methylpyridine in 10 ml of dimethylformamide with a catalytic amount of potassium carbonate. The mixture was stirred in a 50 ml round-bottomed flask at room temperature for about 3 h. The progress of the reaction was monitored by thin-layer chromatography and the mixture was poured into cold water once the reaction was complete. The resulting precipitate was filtered off, washed successively with distilled water, and recrystallized from acetone solution by slow evaporation to obtain colourless block-shaped single crystals.The title compound was obtained unexpectedly from the reaction of 0.01 mol of W were fixed at 0.86 Å, the H⋯H distance was fixed at 1.34 Å and the H atoms were refined with a riding model . The C-bound H atoms were positioned geometrically using a riding model, with Uiso(H) = 1.2 or 1.5Ueq(C) . A rotating-group model was applied to the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017007836/sj5531sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017007836/sj5531Isup2.hklStructure factors: contains datablock(s) I. DOI: 1552520CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


High resolution mass spectrometry (HRMS) was used to monitor library composition and establish conditions under which equilibria were established.Dynamic combinatorial chemistry (DCC) represents an approach, whereby traditional supramolecular scaffolds used for protein surface recognition might be exploited to achieve selective high affinity target recognition. Synthesis, in situ screening and amplification under selection pressure allows the generation of ligands, which bear different moieties capable of making multivalent non‐covalent interactions with target proteins. Generic tetracarboxyphenyl porphyrin scaffolds bearing four hydrazide moieties have been used to form dynamic combinatorial libraries (DCLs) using aniline‐catalyzed reversible hydrazone exchange reactions, in 10 % DMSO, 5 m The use of different amino acids was intended to allow improved scaffold solubility and to investigate the role of functionality proximal to the hydrazone linker in terms of influencing exchange rate.A tetraphenylporphyrin scaffold was chosen as a multivalent hydrazone scaffold. This choice was motivated by the ready accessibility of commercial porphyrins with a sufficient number of points at which a hydrazide linker could be introduced, and the established utility of porphyrins in protein surface recognition.1–3aaaa were achieved by direct coupling of protected amino acid hydrazides with tetracarboxyphenylporphyrin, using PyBOP, to generate protected hydrazide porphyrins 4–6. Hydrazone scaffolds 1–3aaaa ready for DCC studies bearing a simple phenyl hydrazone at each exchangeable bond were obtained from the corresponding protected hydrazides 4–6 by TFA deprotection followed by reaction with benzaldehyde 7.Attempts to synthesise tetracarboxyhydrzidophenylporphyrin resulted in analytically intractable products (see Supporting information). Subsequent efforts centred on the introduction of an amino acid spacer between the porphyrin scaffold and the labile hydrazone linker. Initial synthesis using a glycine spacer resulted in formation of an insoluble product (see Supporting information). Therefore amino acid spacers containing groups to aid scaffold solubility, serine, aspartic acid and glutamic acid, were used. The introduction of the acid functionalities was also envisioned to aid the hydrazone exchange chemistry necessary during the DCL generation, through intramolecular proton transfer effects as has been observed in recent work from the Kool group.1–3aaaa, with three different aldehydes: 4‐carboxybenzaldehyde 8, 4‐methyl ester benzaldehyde 9 and 2,4‐dimethoxybenzaldehyde 10  was used to follow hydrazone exchange. Preliminary efforts to employ HPLC to monitor library distribution indicated that identification of gradients to separate closely related products would be challenging, and in the context of a screening workflow, HRMS represents a method to establish compound identity and qualitative changes in library composition in response to template. Hydrazone exchanges were performed with the three different porphyrin scaffolds 2aaaa with 8), hydrazone exchange was observed within 24 h, and could be visualised by HRMS  to 8, at first increasing then decreasing. The products of successive hydrazone exchanges  then followed in succession.Considering one of these systems,  , with a shift to a greater number of hydrazone exchanges observed (see Supporting information).Having established effective exchange of the benzaldehyde moiety for another aldehyde it was necessary to assess the extent to which a thermodynamic rather than kinetic distribution of products was obtained. The speciation of porphyrins reacted with 25 equivalents of aldehyde for 24 h followed by addition of a further 25 equivalents of the same aldehyde and reaction for 24 h was monitored. Using 1–3aaaa were carried out using two aldehydes simultaneously to generate a DCL . Flash column chromatography was performed using silica gel 60 (0.043–0.063 mm VWR or Sigma Aldrich) or alumina (Brockman I from Sigma Aldrich), unless otherwise stated silica gel was used and pressure was applied by means of head bellows.Thin layer (silica) chromatography was performed using Merck Kiesegel 60 F1H NMR spectra were obtained on Bruker DPX 300 (300 MHz) Avance 500 (500 MHz) or DRX500 (500 MHz) spectrometers and referenced to either residual non‐deuterated solvent peaks or tetramethylsilane. 13C spectra were recorded on a Bruker DPX 300 (75 MHz) Bruker or an Avance 500 (126 MHz) and referenced to the solvent peak. 1H spectra are reported as follows: 1H NMR : δ = ppm to 2 d.p. . Chemical shifts are quoted in ppm with signal splitting recorded as singlet (s), doublet (d), triplet (t), quartet (q), multiplet (m), broad (br). Coupling constants, J, are measured to the nearest 0.1 Hz. Similarly, 13C spectra are reported as follows: δ : δ ppm to one decimal place. Infrared spectra were recorded on a Perkin–Elmer Fourier‐Transfer spectrometer. Spectra were analysed neat and structurally important absorptions are quoted. Absorption maxima (ν̃max=) are quoted in wavenumbers (cm –1). HPLC LC‐MS were recorded on a Bruker HCT ultra under electrospray ionisation (ESI) conditions. High resolution mass spectra were recorded on a Bruker Daltonics micrOTOF Premier Mass Spectrometer, under positive ESI conditions unless otherwise stated.tert‐butoxy)‐1‐{N′‐[(tert‐butoxy)carbonyl]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}‐17‐{4‐[((1S)‐2‐(tert‐butoxy)‐1‐{N′‐[(tert‐butoxy)carbonyl]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}‐21,22,23,24‐tetraazapentacyclotetracosa‐1,3(24),4,6,8,10,12,14,16(22),17,19‐undecaen‐2‐yl)‐N‐((1S)‐2‐(tert‐butoxy)‐1‐{N′‐[(tert‐butoxy)carbonyl]hydrazinecarbonyl}ethyl)benzamide (4):4‐‐2‐, PyBOP , tert‐butyl 2‐(2‐amino‐3‐tert‐butoxypropanoyl)hydrazinecarboxylate,  and diisopropylethylamine  in anhydrous dimethylformamide (5 mL) were stirred under a nitrogen atmosphere for 18 h. The reaction mixture was then diluted with ethyl acetate (50 mL) and washed with saturated sodium hydrogen carbonate solution (50 mL), 1 m hydrochloric acid (50 mL) and brine (3 × 50 mL). The organic phase was dried (sodium sulphate) and concentrated to yield the crude product as a purple solid. This was purified by flash column chromatography (1:1 ethyl acetate/dichloromethane then ethyl acetate) to yield the product as a purple solid . 1H NMR : δ = 1.29 , 1.45 , 3.51–3.63 , 4.07 , 4.83 , 6.40–6.57 , 8.15 , 8.21 , 8.40 , 8.73  ppm. 13C NMR : δ = 26.8, 27.5, 38.4, 53.3, 61.6, 74.0, 80.8, 106.6, 119.3, 125.8, 133.4, 134.4, 145.2, 156.2, 168.4, 170.8 ppm. IR (solid state): ν̃ = 3251 (N–H), 1696 (C=O carbamate), 1645 (C=O amide) cm–1. ESI‐MS m/z found 1820.9402 [M + 2H]+, [C96H124N16O20]+ calcd. 1820.9178.N′‐[(1E)‐phenylmethylidene]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}‐17‐{4‐[((1S)‐2‐hydroxy‐1‐{N′‐[(1E)‐phenylmethylidene]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}‐21,22,23,24‐tetraazapentacyclotetracosa‐1,3(24),4,6,8,10,12,14,16(22),17,19‐undecaen‐2‐yl)‐N‐((1S)‐2‐hydroxy‐1‐{N′‐[(1E)‐phenylmethylidene]hydrazinecarbonyl}ethyl)benzamide (1aaaa):4‐‐2‐hydroxy‐1‐{4  in trifluoroacetic acid (4.5 mL), water (0.25 mL) and triisopropylsilane (0.25 mL) was stirred for 6 h. The solution was then concentrated to yield the deprotected hydrazide as a green solid (complete deprotection was confirmed by HRMS). The green solid was then redissolved in water (2 mL) and acetonitrile (2 mL) and benzaldehyde (2 drops) was added, the mixture was then stirred for 30 min. The precipitate was isolated and washed with water and acetonitrile to yield the product as a dark purple solid . 1H NMR : δ = 1.67 , 3.94 , 4.76 , 5.63 , 7.51 , 7.63 , 7.75 , 7.95 , 8.12 , 8.39 , 8.84 , 8.91 , 11.56 , 11.73  (cis and trans hydrazone isomers observed in 1:1 ratio). IR (solid state): ν̃ = 3212 (N–H), 1633 (C=O amide), 1608 (C=N) cm–1. ESI‐MS m/z found 1547.5750 [M + H]+, [C88H75N16O12]+: calcd. 1547.5340.tert‐Butyl (3S)‐3‐{[4‐‐3‐(tert‐butoxy)‐1‐{N′‐[(tert‐butoxy)carbonyl]hydrazinecarbonyl}‐3‐oxopropyl)carbamoyl]phenyl}‐17‐{4‐[((1S)‐3‐(tert‐butoxy)‐1‐{N′‐[(tert‐butoxy)carbonyl]hydrazinecarbonyl}‐3‐oxopropyl)carbamoyl]phenyl}‐21,22,23,24‐tetraazapentacyclotetracosa‐1,3(24),4,6,8,10,12,14,16(22),17,19‐undecaen‐2‐yl)phenyl]formamido}‐3‐{N′‐[(tert‐butoxy)carbonyl]hydrazinecarbonyl}propanoate (5): Tetracarboxyphenylporphyrin , PyBOP , (S)‐tert‐butyl 2‐(2‐amino‐4‐tert‐butoxy‐4‐oxobutanoyl)hydrazinecarboxylate,  and anhydrous diisopropylethylamine  in anhydrous dimethylformamide (5 mL) were stirred under a nitrogen atmosphere for 18 h. The reaction mixture was then diluted with ethyl acetate (50 mL) and washed with saturated sodium hydrogen carbonate solution (50 mL), 1 m hydrochloric acid (50 mL) and brine (3 × 50 mL). The organic phase was dried (sodium sulphate) and concentrated to yield the crude product as a purple solid. This was purified by flash column chromatography (1:1 ethyl acetate/dichloromethane then ethyl acetate) to yield the product as a purple solid . 1H NMR : δ = 1.53 , 1.55 , 2.95 , 3.10 , 5.30 , 5.45 , 8.21 , 8.27 , 8.73 , 9.02 . 13C NMR : δ = 27.4, 27.6, 37.2, 49.3, 80.9, 81.5, 119.3, 125.9, 133.2, 134.4, 145.4, 149.5, 156.3, 168.4, 170.2, 171.3, 185.1 ppm. IR (solid state): ν̃ = 3275 (N–H), 1723 (C=O ester), 1711 (C=O carbamate), 1647 (C=O amide) cm–1. ESI‐MS m/z found 1931.9891 [M + H]+, [C100H123N16O24]+: calcd. 1931.8896.N′‐[(1E)‐phenylmethylidene]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}‐17‐{4‐[((1S)‐2‐carboxy‐1‐{N′‐[(1E)‐phenylmethylidene]hydrazinecarbonyl}ethyl)carbamoyl]phenyl}‐21,22,23,24‐tetraazapentacyclotetracosa‐1,3(24),4,6,8,10,12,14,16(22),17,19‐undecaen‐2‐yl)phenyl]formamido}–3‐{N′‐[(1E)‐phenylmethylidene]hydrazinecarbonyl}propanoic Acid (2aaaa):3(S)‐3‐{+, [C92H75N16O16]+: calcd. 1659.5547.tert‐Butyl (4S)‐4‐{[4‐‐1‐{N′‐[(tert‐butoxy)carbonyl]hydrazinecarbonyl}‐4‐oxobutyl)carbamoyl]phenyl}‐17‐{4‐[((1S)‐4‐(tert‐butoxy)‐1‐{N′‐[(tert‐butoxy)carbonyl]hydrazinecarbonyl}‐4‐oxobutyl)carbamoyl]phenyl}‐21,22,23,24‐tetraazapentacyclotetracosa‐1,3(24),4,6,8,10,12,14,16(22),17,19‐undecaen‐2‐yl)phenyl]formamido}‐4‐{N′‐[(tert‐butoxy)carbonyl]hydrazinecarbonyl}butanoate (6): {4‐+, [C104H131N16O24]+: calcd. 1987.9522.N′‐[(1E)‐phenylmethylidenehydrazinecarbonyl]propyl}carbamoyl)phenyl]‐17‐{4‐[((1S)‐3‐carboxy‐1‐{N′‐[(1E)‐phenylmethylidene]hydrazinecarbonyl}propyl)carbamoyl]phenyl}‐21,22,23,24‐tetraazapentacyclotetracosa‐1,3(24),4,6,8,10,12,14,16(22),17,19‐undecaen‐2‐yl)phenyl]formamido}‐4‐{N′‐[(1E)‐phenylmethylidene]hydrazinecarbonyl}butanoic Acid (3aaaa):(4S)‐4‐{4‐+, [C96H83N16O16]+: calcd. 1715.6173.Hydrazone Exchange Studies: Hydrazone exchange reactions were carried out in HPLC vials and were followed using high resolution mass spectrometry on a Bruker Daltonics micrOTOF Premier Mass Spectrometer, using 10 µL injections and summing the masses over a range of 1.0 to 3.0 min. The intensity of the maximum peak for each of the successive hydrazone exchanges was taken and the percentage associated with each of the porphyrin peaks calculated.1–3aaaa were made up to 5 mm concentration in DMSO and were stored in plastic Eppendorf tubes. 1 m stocks of catalyst (11 and 12) and aldehydes  were made up in DMSO.Hydrazone functionalised porphyrins 1–3aaaa in DMSO was added to a solution of the aldehyde and catalyst to give a total concentration of 10 % DMSO in 5 mm ammonium acetate buffer, pH 6.75, to a final porphyrin concentration of 100 µm and stated concentrations of other components. For time courses, mass spectra were obtained at appropriates time points . For measurements at single time points, mass spectra were obtained after 24 h incubation. For pre‐incubated samples, the pre‐incubated mixture was left for 24 h, and a mass spectrum obtained, prior to addition of further components.In all exchange reactions the hydrazone functionalised porphyrin Supporting InformationClick here for additional data file.


The asymmetric unit of the title compound consists of one and a half bischalcone molecules. In the crystal, molecules are linked into a three-dimensional network by C—H⋯F and C—H⋯O hydrogen bonds, some of the C—H⋯F links being unusually short (< 2.20 Å). Hirshfeld surface analyses are presented and discussed. 24H14F4O2, comprises of one and a half molecules; the half-molecule is completed by crystallographic inversion symmetry. In the crystal, molecules are linked into a three-dimensional network by C—H⋯F and C—H⋯O hydrogen bonds. Some of the C—H⋯F links are unusually short (< 2.20 Å). Hirshfeld surface analyses  for the title compound are presented and discussed.The asymmetric unit of the title compound, C They consist of two aromatic rings joined by a three-carbon-atom unsaturated carbonyl system (–CH=CH—CO–). Bischalcones with the general formula Ar—CH=CH—CO—CH=CH—Ar  A, the carbonyl groups form similar torsion angles with the 2,4-difluorophenyl ring  and the olefinic double bond . Conversely, the torsion angles between the olefinic double bond and the central benzene ring are slightly different . This leads to slight differences in the dihedral angles between the terminal 2,4-difluorophenyl and the central benzene rings [7.91 (2)° for C1A–C6A and 6.28 (2)° for C19A–C24A]. In molecule B, both torsion angles τ1 and τ3 are comparable to those in molecule A . However, molecule B is slightly closer to planar than molecule A, as its central and terminal rings subtend a dihedral angle of 5.49 (2)°. This might arise from the lower torsion angle between the olefinic double bond and the central benzene ring [O1B—C7B—C8B—C9B = 0.9 (6)°]. Selected torsion and dihedral angles are listed in Table 1et al., 2005The asymmetric unit of (I)B) Fig. 1. The molA—H8A⋯F1A, C17A—H17A⋯F3A and C8B—H8B⋯F1B hydrogen bonds generates an S(6) ring motif s Table 1 generates Table 2. As the er Fig. 2. Atom F2et al., 2004CrystalExplorer 3.1  and outside (de) of the Hirshfeld surface analyze the intermolecular interaction via the mapping of dnorm. In a dnorm surface, any intermolecular interactions will appear as a red spot.The Hirshfeld surface analyses . Similarly, the C—H⋯F interactions are identified by red spots near the F2A atom in molecule A . As illustrated in Fig. 5de and di diagonal axes represent the overall two-dimensional FP and those delineated into F⋯H/H⋯F, H⋯H and O⋯H/H⋯O contacts, respectively. The most significant intermolecular interactions are the reciprocal F⋯H/H⋯F interactions (30.1%), which appear as two sharp symmetric spikes in FP maps with a prominent long spike at de + di ≃ 2.3 Å . The H⋯H interactions appear in the central region of the FP with ed = id ≃ 2.4 Å and contribute 29.0% to the Hirshfeld surface  whereas two symmetrical narrow pointed wings corresponding to the O⋯H/H⋯O interactions with 12.7% contribution appear at diagonal axes of de + di ≃ 2.4 Å . The percentage contributions for other intermolecular contacts are less than 10% in the Hirshfeld surface mapping .Dark-red spots that are close to atoms O1ds Fig. 4a. Simil A Fig. 4b. As il Å Fig. 5b. The Hce Fig. 5c wherea Å Fig. 5d. The pet al., 2016E)-1-(4-fluorophenyl)-3-phenylprop-2-en-1-one as the main skeleton revealed the presence of seven structures containing the chalcone moiety with different substituent similar to the title compounds in this study. These structures are 4′-fluorochalcone -3-[4-(dimethylamino)phenyl]-1-(4fluorophenyl)prop-2-en-1-one -3-(4-chlorophenyl)-1-(4-fluorophenyl)prop-2-en-1-one  phenyl]prop-2-en-1-ones -1-(4-fluorophenyl)-3-(4-methylphenyl)prop-2-en-1-one  in methanol (20 ml) was mixed with 2,4-difluoroacetophenone (0.02 mol) in methanol (20 ml) in the presence of NaOH. The reaction mixtures were stirred for about 5–6 h at room temperature. The resultant crude products were filtered, washed successively with distilled water and recrystallized from ethanol solution to get the title compound. Yellow blocks of (I)-3,3′-bisprop-2-en-1-one), C Solvent for growing crystals: mixture of chloroform and acetonitrile (1:1 v/v); yield 85%, m.p. 447–449 K; FT–IR (ATR (solid) cm−1): 3101 , 1600 , 1593, 1420 , 1229 ; 1H NMR : δ 7.969–7.922 , 7.818–7.787 , 7.697 , 7.059–7.022 , 6.969–6.935 ; 13C NMR : 187.00 (C7), 143.62 (C9), 136.83 (C2), 133.11 (C10), 133.03 (C5), 129.14 , 126.18 (C6), 126.12 (C8) 112.47, 112.27 (C3), 105.01, 104.81 (C1), 104.59 (C4).Uiso(H) = 1.2Ueq(C) for H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S205698901701564X/hb7696sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901701564X/hb7696Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901701564X/hb7696Isup3.cmlSupporting information file. DOI: 1449628CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound, tetrahydroseselin (THS), a hydrogenated product of the angular pyranocoumarin seselin, possesses photo-biological activity against different kinds of inflammatory skin diseases such as atopic dermatitis and pigment disorders like vitiligo and psoriasis. 14H16O3, a pyranocoumarin chromen-2-one] obtained from the hydrogenation of seselin in the presence of Pd/C in MeOH at room temperature, the dihedral angle between the central benzene ring and the best planes of the outer fused ring systems are 6.20 (7) and 10.02 (8)°. In the crystal, molecules show only very weak intermolecular C—H⋯O interactions.In the title compound, tetrahydroseselin, C HL60 and A431, has been observed  cycloaddition] and diadducts [(4 + 2) cycloaddition]  and 178.73 (14)°, respectively, indicating that these rings are coplanar. The destruction of photo-biological activity and change of conformation of the pyran rings of the title molecule is considered to be due to the loss of the double bonds in seselin.In the title compound, the three different fused rings comprising the molecule Fig. 1, are thei (ring) [3.221 (2) Å] and methylene C9—H⋯O3i (carbonyl) [3.412 (2) Å] interactions  and methylene C8—H⋯O3ii (carbonyl) [3.593 (3) Å] interactions -[1]-benzopyran-7-one; bromohydroxy-seselin  = 1.2Ueq(C). Those on methyl groups were allowed to ride with C—H = 0.96 Å and with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S205698901700932X/zs2379sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698901700932X/zs2379Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901700932X/zs2379Isup3.cmlSupporting information file. DOI: 1557474CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds play an important role in the crystal packing, resulting in the formation of molecular sheets parallel to the bc plane.The molecules of C 15H14N2O3, crystallizes with two independent molecules (A and B) in the asymmetric unit that differ in the orientation of the 3-methoxyphenyl group with respect to the methylidenebenzohydrazide unit. The dihedral angles between the two benzene rings are 24.02 (10) and 29.30 (9)° in molecules A and B, respectively. In molecule A, the methoxy group is twisted slightly relative to its bound benzene ring, with a Cmethyl—O—C—C torsion angle of 14.2 (3)°, whereas it is almost co-planar in molecule B, where the corresponding angle is −2.4 (3)°. In the crystal, the molecules are linked by N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds, as well as by weak C—H⋯O interactions, forming sheets parallel to the bc plane. The N—H⋯O hydrogen bond and weak C—H⋯O interaction link different molecules (A⋯B) whereas both O—H⋯N and O—H⋯O hydrogen bonds link like molecules (A⋯A) and (B⋯B). Pairs of inversion-related B molecules are stacked approximately along the a axis by π–π interactions in which the distance between the centroids of the 3-methoxyphenyl rings is 3.5388 (12) Å. The B molecules also participate in weak C—H⋯π interactions between the 4-hydroxyphenyl and the 3-methoxyphenyl rings.The title compound, C Various derivatives of benzohydrazide have been reported to possess a range of biological properties, including antibacterial -4-hydroxy-N′-(3-hydroxy-4-methoxybenzylidene)benzohydrazide -4-hydroxy-N′-benzohydrazide A and B, of the title benzohydrazide derivative, C15H14N2O3, in the asymmetric unit of (I)A and B, respectively. The molecules exist in the trans-conformation with respect to the C8=N2 bond [1.275 (2) Å in molecule A and 1.271 (2) Å in molecule B] and the torsion angle N1—N2—C8—C9 = −178.14 (16)° in molecule A and −177.69 (16)° in molecule B. Five atoms  of the central fragment are approximately coplanar, having r.m.s. deviations of 0.0179 (2) Å in molecule A and 0.0327 (2) Å in molecule B. The mean plane through this central fragment makes dihedral angles of 23.87 (11) and 0.20 (12)° with the planes of the 4-hydroxyphenyl and 3-methoxyphenyl rings, respectively, in molecule A. The corresponding values are 22.58 (11) and 11.04 (11) ° in molecule B. In molecule A, the methoxy group is slightly twisted from the attached benzene ring [C15—O3—C11—C10 = 14.2 (3)°] whereas it is essentially coplanar in molecule B [where the corresponding torsion angle is −2.4 (3)°]. The bond distances agree with literature values and are comparable with those in related structures  whereas the O2A—H2A⋯N2Aiii and O2A—H2A⋯O1Aiii hydrogen bonds link equivalent A molecules, and O2B—H2B⋯N2Bii and O2B—H2B⋯O1Bii hydrogen bonds link equivalent B molecules. Stacking of planes of molecules in the a-axis direction involves π–π interactions between B molecules with Cg⋯Cgvi distance of 3.5388 (12) Å. A weak C—H⋯π interaction (C3B—H3B⋯Cgv) between the 4-hydroxyphenyl ring and the 3-methoxyphenyl ring of symmetry-related B molecules is also present  x, y, −z; (iii) x, y, −z; (iv) x, 1 + y, z; (v) −x, −y, z; (vi) 1 − x, 2 − y, 2 − z; Cg is the centroid of the C9B–C14B ring].In the crystal Fig. 2, the molnt Fig. 3 [symmetret al., 2011et al., 2011et al., 2012Chemical context section.A search of SciFinder  in ethanol (10 ml) and 3-methoxybenzaldehyde  in ethanol (10 ml) were mixed, stirred and refluxed for 5 h. The resulting mixture was then cooled to room temperature. The white precipitate that formed was filtered. Colorless block-shaped single crystals of (I)3OH) λmax (log∊): 212 (5.51), 302 (5.61) nm; FT–IR (KBr) ν: 3158, 2834, 1648, 1607, 1509 cm−1; 1H NMR  δ: 11.65 , 10.15 , 8.39 , 7.80 , 7.27 , 7.25 , 7.37 , 7.00 , 6.86 , 3.81  p.p.m.UV–Vis N′-benzylidenebenzohydrazide skeleton by showing the characteristic signals of an amine (N=CH) at 8.39  and an amide (N—H) at 11.65  p.p.m.The UV–Vis spectrum of (I)et al.  = 0.85 or 0.87 Å; d(O—H) = 0.82 Å; d(C—H) = 0.93 Å for aromatic and CH; and 0.96 Å for CH3 atoms. The Uiso values were constrained to be 1.5Ueq of the carrier atom for methyl and hydroxyl H atoms, and 1.2Ueq for the remaining H atoms. A rotating group model was used for the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016013268/pk2585sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016013268/pk2585Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016013268/pk2585Isup3.cmlSupporting information file. DOI: 1499671CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


E conformation about the C=C bond, and the quinoline ring system and the benzene ring are inclined to one another by 29.22 (7)°.The title 8-hydroxyquinoline derivative has an  19H15NO3, was synthesized by a Perkin reaction of 2-methyl-8-hydroxyquinoline and 4-formyl-2-methylbenzoate in acetic anhydride under a nitrogen atmosphere. The molecule has an E conformation about the C=C bond, and the quinoline ring system and the benzene ring are inclined to one another by 29.22 (7)°. There is an intramolecular O—H⋯N hydrogen bond in the 8-hydroxyquinoline moiety. In the crystal, molecules are linked by pairs of O—H⋯O hydrogen bonds, forming inversion dimers with an R22(28) ring motif. The dimers are linked by C—H⋯O hydrogen bonds and C—H⋯π interactions, forming sheets parallel to plane (10-1).The title compound, C The C11—C10 and C6—C9 bond lengths are 1.463 (2) and 1.466 (2) Å, respectively. These distances are shorter than the standard length of a C—C single bond (ca 1.5 Å) because of the conjugate system formed by the C9=C10 bond and the aromatic systems. The quinoline ring system and the benzene ring are inclined to one another by 29.22 (7)°.The molecular structure of the title compound is shown in Fig. 1In the crystal, molecules are linked by pairs of O—H⋯O hydrogen bonds, forming inversion dimers with an f Table 1. The dimet al., 2016E conformation about the C=C bond, and in the crystal they also form inversion dimers. They include 2-{2-[4-(trifluoromethyl)phenyl]vinyl}quinolin-8-ol  = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698901601210X/su5312sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S205698901601210X/su5312Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698901601210X/su5312Isup3.molSupporting information file. DOI: Click here for additional data file.10.1107/S205698901601210X/su5312Isup4.cmlSupporting information file. DOI: 859030CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


I atom in the title methanol solvate is coordinated octahedrally by two N atoms of the chelating organic ligand, one Br atom and three facially configured carbonyl ligands. Hydrogen bonds between the complex and methanol solvent molecules lead to a layered arrangement in the structure.The Re 16H16N4O3)(CO)3]·CH3OH, the ReI atom adopts a distorted octahedral coordination sphere with a facial arrangement of the three carbonyl ligands. Two N atoms of the chelating 5--3-(pyridin-2-yl)-1H-1,2,4-triazole ligand and two carbonyl ligands define the equatorial plane of the complex, with the third carbonyl ligand and the bromide ligand in axial positions. Conventional hydrogen bonds including the methanol solvent molecules assemble the complex molecules through mutual N—H⋯O—H⋯Br links [N⋯O = 2.703 (3) Å and O⋯Br = 3.255 (2) Å] into centrosymmetric dimers, whereas weaker C—H⋯O and C—H⋯Br hydrogen bonds [C⋯O = 3.215 (3)–3.390 (4) Å and C⋯Br = 3.927 (3) Å] connect the dimers into double layers parallel to the (111) plane.In the title compound, [ReBr(C The two N atoms and two carbonyl C atoms define the equatorial plane, while the octahedral coordination sphere is completed by the third carbonyl C atom and the Br atom [Re—Br = 2.6222 (3) Å] in axial positions. The CO ligands are almost linearly coordinated, with O—C—Re bond angles of 178.2 (3), 177.8 (3) and 177.8 (3)°. The C—Re—C bond angles between carbonyl C atoms are 90.6 (1), 90.2 (1) and 88.7 (1)°, close to ideal values, whereas the cis equatorial bite angle of the chelating ligand (N1—Re1—N4) is 73.42 (8)°.The three carbonyl ligands bonded to the ReL)(CO)3] . However, this situation is unlikely to be a consequence of slipped π–π interactions, since the corresponding slippage angle exceeds 56° and the intercentroid distance is as long as Cg(C6–C10/N4)⋯Cg(C4/C5/N1–N3)v = 4.090 (3) Å . Although such weak interactions are characteristic of related metal–carbonyl structures  in benzene (30 ml). The mixture was refluxed for 4 h under a stream of argon and then allowed to cool to room temperature. The yellow product was collected by suction filtration, washed with hexane and dried . Crystals suitable for X-ray diffraction were obtained by slow diffusion of hexane into a methanol–dichloromethane solution of the complex. IR : νas(CO) 2028 (s), νs(CO) 1894 (s). 1H NMR : δ 9.02 , 8.39 , 8.35 , 7.75 , 7.44 , 3.93 .Pentacarbonylrhenium(I) bromide  was mixed with 5--3-(pyridin-2-yl)-1Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq otherwise. The O-bound H atom of the methanol solvent molecule was found from a difference map and was refined with O—H = 0.95 Å and Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017003371/wm5372sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017003371/wm5372Isup2.hklStructure factors: contains datablock(s) I. DOI: 1535292CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Graphene plasmonics has become a highlighted research area due to the outstanding properties of deep-subwavelength plasmon excitation, long relaxation time, and electro-optical tunability. Although the giant conductivity of a graphene layer enables the low-dimensional confinement of light, the atomic scale of the layer thickness is severely mismatched with optical mode sizes, which impedes the efficient tuning of graphene plasmon modes from the degraded light-graphene overlap. Inspired by gap plasmon modes in noble metals, here we propose low-dimensional hybrid graphene gap plasmon waves for large light-graphene overlap factor. We show that gap plasmon waves exhibit improved in-plane and out-of-plane field concentrations on graphene compared to those of edge or wire-like graphene plasmons. By adjusting the chemical property of the graphene layer, efficient and linear modulation of hybrid graphene gap plasmon modes is also achieved. Our results provide potential opportunities to low-dimensional graphene plasmonic devices with strong tunability. In the context of light-matter interactions, the concentration of electromagnetic fields on materials is a critical issue for the performance of tunable optical devices, such as photodetectors3678Due to its two-dimensional (2D) structure with extremely large conductivity from the massless Dirac point111314161719212223242126272931Here, we focus on low-dimensional waveguide systems for the improved light-graphene overlap factor. We firstly reveal the existence of hybrid graphene gap plasmon (H-GGP) modes the field profile of which is strongly confined inside the graphene gap between metallic and dielectric graphene layers. We demonstrate that the H-GGP mode has larger field concentration on graphene layers than those of edge33w (the sheet conductivity σ(G) where Im{σ(G)} < 0) is inserted in-between semi-infinite metallic domain M (Im{σ(M)} > 0) and dielectric domain D (Im{σ(D)} < 0). The gap region G satisfies the condition of Im{σ(D)} < Im{σ(G)} < 0, as the analogy of plasmonic gap modes in noble metals8212627μ(x). μ-dependency of the graphene conductivity calculated by Kubo formula1121f = ω/2π = 20 THz, charged particle scattering rate8Ω(M))−1 > 0.6 and 0.5 < (Ω(D))−1 < (Ω(G))−1 < 0.6, where Ω−1 = μ/(ℏω) is the normalized chemical potential.We consider the 2D metal-gap-dielectric waveguide system composed of three distinct graphene domains ; a dielew = 5 nm, (Ω(M))−1 = 4, (Ω(G))−1 = 0.54, and (Ω(D))−1 = 0.5002). In the numerical analysis, the graphene is considered as the filmδ = 0.2 nm and the relative bulk permittivity of εg(ω) = 1 + jσg(ω)/(ωε0δ), where σg is sheet conductivity of graphene obtained from Kubo formula33σ~ − σ for all z) have improved confinement compared to that of the GEP mode with much stronger structural asymmetry | ≪ |σ| and |σ| = |σ| for z ≠ 0), H-GGP exhibits more confined transverse (Ex) field on the gap region than that of the 1D-SPP mode, as similar to the difference between gap plasmons and surface plasmons in noble metals8Im{σ(G)}·Ex(G)~Im{σ(D)}·Ex(D), deriving the enhancement of Ex(G) from the condition of Im{σ(D)} < Im{σ(G)} < 0. For the practical realization, we also note that H-GGP modes can be obtained at any finite temperatures when the conductivity of each domain satisfies the condition of Im{σ(D)} < Im{σ(G)} < 0 < Im{σ(M)}, as shown in f = 100 THz.w = 0) corresponds to the σ(M) − σ(D) 1D-SPP system with the effective mode indexneff = Re{q}/k0 ≈ 2·(3/2)1/2·εε0·c/(Im{σ(M)} + Im{σ(D)}), while the H-GGP system with infinite w is converged to the σ(M) − σ(G) 1D-SPP system. The effective mode index (de index  and the de index  of the Hw case is converged to that of the σ(M) − σ(G) 1D-SPP system, smaller w cases exhibit the intensity profiles focused of the graphene gap. Such a distinct in-plane intensity distribution imposes the unique property on out-of-plane confinement, in terms of the light-graphene overlap factor ρ = ∫∫graphene|E|2·dS/∫∫|E|2·dS: the concentration of electromagnetic fields on graphene. ρ as a function of the gap width w, which demonstrates the improved light-graphene overlap for the structures with apparent field concentration on the gap (0 < w < 40 nm). We note that the H-GGP mode acquires much higher field concentration on the graphene layer (ρ = 2.07 × 10−3 at w = 5 nm), when compared to those of 1D-SPP modes (σ(M) − σ(D) system of ρ = 1.81 × 10−3 and σ(M) − σ(G) system of ρ = 1.70 × 10−3) and the GEP mode (ρ = 0.728 × 10−3).Most importantly, there exist differentiated features of the H-GGP mode when compared to 1D-SPP modes, as shown in Ω(M))−1 = 4 + ΔΩ−1, (Ω(G))−1 = 0.54 + ΔΩ−1, and (Ω(D))−1 = 0.5002 + ΔΩ−1, with the spatially global (wmax modulation width) modulation range. As seen, the effective mode index of the H-GGP mode can be controlled with an order of smaller modulation of ΔΩ−1 when compared to the GEP mode. The H-GGP mode also provides more efficient regime of ΔΩ−1 for controlling effective index compared to 1D-SPP modes (ΔΩ−1 ≤ 0.015). Such improved efficiency is more apparent for the case of the finite modulation region for ΔΩ−1 (dotted lines in wmax modulation width around the graphene gap), due to the improved transverse localization of the H-GGP mode  will be required for increasing excitation efficiency, for example, by applying adiabatic procedure or matched layers.We demonstrated the existence of low-dimensional gap plasmon modes on graphene, which supports large light-graphene overlap factor. The system with spatially-varying chemical potential (or doping level) for H-GGP modes can be realized by several existing schemes such as electric field bias332137How to cite this article: Kim, Y. et al. Low-dimensional gap plasmons for enhanced light-graphene interactions. Sci. Rep.7, 43333; doi: 10.1038/srep43333 (2017).Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.


In the crystal, supramolecular layers sustained by C—H⋯O, π–π, C—H⋯π(arene) and C—H⋯π(chelate ring) interactions are formed.A highly distorted pentacoordinated C 3)2(C28H32N2O4)], features a distorted SnC2NO2 coordination geometry almost intermediate between ideal trigonal–bipyramidal and square-pyramidal. The dianionic Schiff base ligand coordinates in a tridentate fashion via two alkoxide O and hydrazinyl N atoms; an intramolecular hydroxy-O—H⋯N(hydrazinyl) hydrogen bond is noted. The alkoxy chain has an all-trans conformation, and to the first approximation, the molecule has local mirror symmetry relating the two Sn-bound methyl groups. Supramolecular layers sustained by imine-C—H⋯O(hydroxy), π–π [between decyloxy-substituted benzene rings with an inter-centroid separation of 3.7724 (13) Å], C—H⋯π(arene) and C—H⋯π(chelate ring) interactions are formed in the crystal; layers stack along the c axis with no directional interactions between them. The presence of C—H⋯π(chelate ring) interactions in the crystal is clearly evident from an analysis of the calculated Hirshfeld surface.The title diorganotin compound, [Sn(CH The bond lengths involving the nitrogen atoms comprising the backbone of the chelate rings suggest some conjugation, i.e. N1—C1, N1—N2 and N2—C12 are 1.317 (3), 1.397 (2) and 1.303 (3) Å, respectively. The 10 atoms of the fused-ring system appended to the five-membered chelate ring make a dihedral angle of 2.01 (3)° with the chelate ring, a conformation allowing the formation of an intramolecular hydroxy-O—H⋯N(hydrazinyl) hydrogen bond to close an S(6) loop, Table 2trans conformation with the range of torsion angles being −174.96 (18)°, for C21—C22—C23—C24, to 179.79 (19)°, for C25—C26—C27—C28. Indeed, the r.m.s. deviation for the least-squares plane through all non-hydrogen atoms except the Sn-bound methyl groups is relatively small at 0.1179 Å, with maximum deviations being for the terminal methyl group of the alkoxy chain, i.e. 0.296 (2) Å, and a central methylene-C22 atom, i.e. 0.194 (2) Å. Hence, to a first approximation, the molecule has mirror symmetry, relating the two Sn-bound methyl groups.The five-membered, SnON3N2CH}2 synthon is formed, which encapsulates two six-membered {⋯HOC3N} synthons formed by the intramolecular hydroxy-O—H⋯N(hydrazinyl) hydrogen bonding mentioned above, Fig. 2a. Centrosymmetrically related dimeric aggregates are linked via π–π interactions between decyloxy-substituted benzene rings . The remaining interactions are of the type C—H⋯π and involve methylene-C—H exclusively. While two of the interactions have benzene rings as acceptors, the other two have chelate rings as acceptors, i.e. are of the type C—H⋯π(chelate), a phenomenon gaining increasing attention  hydrogen bond, the hydroxy-O atom accepts an interaction from a centrosymmetrically-related imine-H atom, Table 2et al., 2017dnorm, in the range −0.053 to + 1.621 au, Fig. 33N2CH}2 synthon as discussed in the previous section; these are also viewed as blue and red regions near the H and O atoms on the Hirshfeld surface mapped over electrostatic potential (over the range ± 0.075 au), Fig. 4de mapped Hirshfeld surface, Fig. 5A⋯π(C13–C18) contacts at 1 − x, −y, 1 − z and their reciprocal contacts, i.e. π⋯H—C, are represented with blue and white dotted lines, respectively, in Fig. 6a. The other C—H⋯π contacts involving benzene rings and π–π stacking interactions at 1 − x, 1 − y, 1 − z are illustrated in Fig. 6b.The Hirshfeld surface analysis for (I)et al., 2007a–f; their relative contributions are summarized quantitatively in Table 3i.e. 97.0%.The overall two-dimensional fingerprint plot and those delineated into H⋯H, C⋯H/H⋯C, O⋯H/H⋯O, N⋯H/H⋯N and C⋯C contacts  interactions, Table 2c and e, as their ring centroids  benzene rings, and appears as an arrow-like distribution of points around de = di ∼ 1.9 Å in Fig. 7f. The other contacts, having low percentage contribution to the surface, are likely to have a negligible effect on the molecular packing.A pair of very short peaks at et al., 2016Chemical context). Two dimethyltin structures are available with identical ligands apart from having a substituent in the 5-position, i.e. chloride According to a search of the crystallographic literature -3-hydroxy-2-napthohydrazide  and triethylamine  in ethyl acetate (25 ml) were added to dimethyltin dichloride  in ethyl acetate (10 ml). The resulting mixture was stirred and refluxed for 3 h. The filtrate was evaporated until a precipitate was obtained. The precipitate was recrystallized from dichloromethane:dimethylformamide (1:1), and yellow prismatic crystals suitable for X-ray crystallographic studies were obtained from the slow evaporation of the filtrate. Yield: 0.366 g, 60%; M.p.: 507–508 K. IR (cm−1): 3162(br), 1633(s), 1597(s), 1169(s) cm−1. 1H NMR (in DMSO-d6): δ 11.34 , 8.57 , 6.25–6.40, 7.07–7.20 , 8.47 , 3.96 , 1.28-1.82 , 0.91, , 0.89 .Uiso(H) set to 1.2–1.5Ueq(C). The oxygen-bound H atom was located in a difference Fourier map but was refined with a distance restraint of O—H = 0.84±0.01 Å, and with Uiso(H) set to 1.5Ueq(O). The maximum and minimum residual electron density peaks of 0.80 and 1.32 e Å−3 were located 0.42 and 0.83 Å, respectively, from the H23B and Sn atoms.Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989017002365/hb7655sup1.cifCrystal structure: contains datablock(s) . DOI: 10.1107/S2056989017002365/hb7655Isup2.hklStructure factors: contains datablock(s) I. DOI: 1532445CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The reaction of manganese dichloride and iron dichloride with the ligand 5,6-bis(pyridin-2-yl)pyrazine-2,3-dicarboxylic acid leads to the formation of isotypic binuclear complexes which have a cage-like structure. 4N1,O2,N6:O3;κ4O3:N1,O2,N6-bis[diaquamanganese(II)] tetrahydrate, [Mn2(C16H8N4O4)2(H2O)4]·4H2O, (I), and bis-κ4N1,O2,N6:O3;κ4O3:N1,O2,N6-bis[diaquairon(II)] tetrahydrate, [Fe2(C16H8N4O4)2(H2O)4]·4H2O, (II), are, respectively, the manganese(II) and iron(II) complexes of the ligand 5,6-bis(pyridin-2-yl)-pyrazine-2,3-dicarboxylic acid. The complete molecule of each complex is generated by inversion symmetry. Each metal ion is coordinated by a pyrazine N atom, a pyridine N atom, two carboxylate O atoms, one of which is bridging, and two water O atoms. The metal atoms have MN2O4 coordination geometries and the complexes have a cage-like structure. In the crystals of both compounds, the complexes are linked by O—H⋯O and O—H⋯N hydrogen bonds involving the coordinating water molecules, forming chains along [100]. These chains are linked by O—H⋯O hydrogen bonds involving the non-coordinating water molecules, forming layers parallel to (011). The layers are linked by pairs of C—H⋯O hydrogen bonds and offset π–π interactions, so forming a hydrogen-bonded three-dimensional framework.The title isotypic complexes, bis-κ On exposure to air, this compound loses the solvent of crystallization and four water molecules, transforming into a polymeric two-dimensional network structure pyrazine-2,3-dicarboxylic acid , and by two carboxylate O atoms, O1 and O3i . Hence, the ligand coordinates to the metal atoms in a tridentate  and a monodentate (O) manner. Atom O3 is bridging, so leading to the formation of a cage-like complex situated about a centre of inversion; illustrated in Fig. 3II complex, (II)ica 6.58 Å, while the Fe1⋯Fe1i distance is ca 6.50 Å. Selected bond lengths and angles for compounds (I)The complete molecules of complexes (I)pyrazine, Mn1—N1, bond length is 2.242 (3) Å, which is shorter than the Mn—Npyridine, Mn1—N3, bond length of 2.311 (3) Å. The Mn1—Owater bond lengths [2.141 (3) and 2.148 (3) Å] are similar to the Mn—Ocarboxylate, Mn1—O3i, bond length of 2.139 (2) Å, while distance Mn1—O1 is longer at 2.228 (2) Å.In complex (I)II two-dimensional coordination polymer involving ligand 2LH, mentioned above. The Fe—Npyrazine bond length, Fe1—N1, is 2.126 (2) Å, which is slightly shorter than the Fe—Npyridine, Fe1—N3, bond length of 2.205 (3) Å. The Fe1—Owater bond lengths [2.115 (2) and 2.066 (2) Å] are similar to the Fe1—Ocarboxylate bond lengths [2.131 (2) and 2.139 (2) Å].In complex (II)W,O3i in the equatorial plane and atoms O2W and N1 in the apical positions with an O2W—Mn1—N1 bond angle of 163.62 (11) ° (Table 1W—Fe1—N1 bond angle of 165.15 (10)° (Table 2viz. 57.28 (17)°.The geometry of the sixfold coordinated metal atoms can best be described as a distorted octahedron, with atoms O1,N3,O1° Table 1, and an ° Table 2. The cooW and O2W), forming chains along [100]; illustrated in Fig. 4W and O4W), forming layers parallel to the bc plane, as illustrated in Fig. 5Cg⋯Cgii = 3.671 (4) Å in (I)Cg is the centroid of the ring N3/C5–C9; symmetry code: (ii) −x + 2, −y + 2, −z + 1], link the layers, forming a three-dimensional framework; illustrated in Fig. 6Details of the hydrogen-bonding interactions in the crystals of both compounds, are given in Table 3fs Fig. 5. Pairs oet al., 20162LH, and its dimethyl ester, gave eight hits. Some of these structures have been mentioned in the Chemical context above. In the case of (I)N,N,O) and monodentate (O) manner. This coordination mode of 2LH is the same as that observed in the CdII two-dimensional coordination polymer  has been reported previously pyrazine-2,3-dicarboxylic acid (Synthesis of compound (I): 2LH  was added in solid form to an aqueous solution (15 ml) of MnCl2·4H2O . The yellow solution immediately obtained was stirred for 10 min at room temperature, filtered and the filtrate allowed to slowly evaporate. After two weeks orange–yellow rod-like crystals were obtained. They were separated by filtration and dried in air . Selected IR bands : ν 3226, 3080(w), 1636(s), 1598(vs), 1545(w), 1475(m), 1440(m), 1410(w), 1366(s), 1348(s), 1301(w), 1275(w), 1170(m), 1126(m), 1007(w), 954(w), 850(w), 790(m), 562(m).Synthesis of compound (II): A degassed aqueous solution (20 ml) of 2LH  was treated with FeCl2·4H2O . The violet solution immediately obtained was stirred under N2 at 343 K for 1 h, filtered and the filtrate allowed to slowly evaporate. After two months deep-violet block-like crystals were obtained. They were separated by filtration and air dried . Precipitation of small amounts of iron(III) hydroxide accompanied the formation of the crystals. Selected IR bands : ν 3477, 3291, 3078(w), 1640(s), 1593(vs), 1545(w), 1475(m), 1440(m), 1405(w), 1359(m), 1300(w), 1286(w), 1269(w), 1172(m), 1124(m), 1008(w), 954(w), 847(w), 789(m), 772(w), 677(w), 565(m), 549(w), 494(m) %.Uiso(H) = 1.2Ueq(C). Intensity data for (I)Rint = 0, and as no suitable ψ-scans could be measured no absorption correction was applied. For compound (II)Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989016014055/pj2034sup1.cifCrystal structure: contains datablock(s) I, II, Global. DOI: 10.1107/S2056989016014055/pj2034Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989016014055/pj2034IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1502352, 1502351CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Single-molecule magnet (SMM) properties of these four complexes were observed to be dependent on the ROH lattice solvent molecule. There is an interesting magneto-structural correlation: the larger the R group, the higher the energy barrier. For the first time, the solvatomagnetic effect is used for the continuous fine adjustment of the energy barrier of 0D molecular nanomagnets. Additionally, [Cu3Dy2(H3L)2(OAc)2(hfac)4]∙2MeOH (5), an analogue of [Cu3Tb2(H3L)2(OAc)2(hfac)4]∙2MeOH (1), is also reported for comparison.Solvents play important roles in our lives, they are also of interest in molecular materials, especially for molecular magnets. The solvatomagnetic effect is generally used for trigger and/or regulation of magnetic properties in molecule-based systems, however, molecular nanomagnets showing solvatomagnetic effects are very difficult to obtain. Here we report four 3d-4f heterometallic cluster complexes containing ROH lattice solvent molecules, [Cu The solvatomagnetic effect is very interesting because solvent molecules can be used for trigger and/or regulation of magnetic properties while the molecular magnetic structure is always maintained. Therefore, molecular magnets showing solvatomagnetic effects can be used as molecule devices, molecular switches and/or molecular sensors. Naturally, solvatomagnetic effects are often found in porous metal-organic frameworks (MOFs) in which solvent molecules are guest molecules9, while low-dimensional systems with solvatomagnetic effects are more difficult to obtain due to the lack of pores. Recently, we found a chain-like azido-bridged manganese(III) coordination polymer showing both solvatomagnetic effect and spin-glass behaviour10. In studies of single molecule magnets (SMMs)11, we also hope to explore SMM systems with solvatomagnetic effects. However, it is a great challenging task because most SMMs reported are concentrated on zero-dimensional (0 D) cluster or mononuclear systems.Solvents, especially water, are critical to the origins of life, and they have penetrated into all aspects of human life. Besides as reaction mediums and extracting agents, chemical solvents are also of interest in molecular materials. For example, in the field of molecular magnets they can be utilized as the terminal ligand to complete the coordination configuration17; and the energy barrier leading to magnetic bistability and slow magnetic relaxation is a pivotal parameter. Therefore, except enhancing the relaxation energy barrier and increasing the blocking temperature21, tuning the relaxation energy barrier is another important target in the molecular nanomagnet field26. Surprisingly, systematic studies of SMMs with the same magnetic structure are still rare, however, some factors such as the electron-withdrawing effect27, the electrostatic potential of the key coordination atom28 have been observed to be able to modulate SMMs’ energy barriers recently. Regarding structures and magnetic properties may be affected by a small change of circumstance, solvent molecules may also be used to adjust SMMs’ properties. To the best of our knowledge, a direct correlation between energy barriers and different lattice solvent molecules of 0D molecular nanomagnets has never been documented, though a 3D Dy(III) MOF-type SMM was found to show an obvious solvatomagnetic effect in 201529, and guest-dependent single-ion magnet behaviours were observed in a 2D cobalt(II) coordination polymer in 201630. Herein we describe the lattice-solvent effect of ROH molecules  on the energy barrier of 0D SMMs with the same magnetic structure [Cu3Tb2(H3L)2(OAc)2(hfac)4] {H6L = 1,3-Bis[tris(hydroxymethyl)methylamino]propane, Fig. − = hexafluoroacetylacetonate}. Fine adjustment of the energy barrier  in this [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMM system was achieved by changing the ROH lattice solvent molecule. A similar [Cu3Dy2(H3L)2(OAc)2(hfac)4] SMM system was also studied, but only the crystal structure of [Cu3Dy2(H3L)2(OAc)2(hfac)4]∙2MeOH (5) was successfully solved; complex 5 also exhibits slow magnetic relaxation under zero dc field, with the energy barrier of 30.0 K, a relatively high value for reported relaxation barriers of the Cu-Dy heterometallic SMMs.It is well known that SMMs are of great potential for technological applications in high-density information storage, quantum computing and spintronics6L), an universal ligand due to flexible polydentate coordination sites, has been used to bind not only 3d transition metal ions32 but also 4 f lanthanide metal ions33. Furthermore, it can also be utilized to construct 3d-4f heterometallic complexes34. Recently, Murrie et al. reported a series of 3d-4f complexes formulated as {Ln2Cu3(H3L)2Xn} 35; they found that changing the auxiliary ligand OAc− through NO3− may lead to a remarkable improvement of the energy barrier of {Tb2Cu3(H3L)2Xn} (X = OAc− and NO3−) complexes, which suggests that the anion co-ligand has a great impact on the energy barrier of {Tb2Cu3(H3L)2Xn} SMMs. In the recent process of pursuing new SMMs, we observed that using Ln(OAc)(hfac)2(H2O)2 as the lanthanide (III) salt source may lead mixed co-ligands OAc− and hfac− into 3d-4f heterometallic clusters effectively36. Therefore, we adopted this synthesis strategy to obtain the [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMM with different ROH lattice solvent molecules , in which not only the OAc− anion but also the hfac− anion are co-ligands. Notably, our synthetic procedures were completed at room temperature rather than at 60 °C used by Murrie group35. Products using methanol, ethanol and isopropyl alcohol as reaction solvents were [Cu3Tb2(H3L)2(OAc)2(hfac)4]∙2MeOH (1), [Cu3Tb2(H3L)2(OAc)2(hfac)4]∙2EtOH (2) and [Cu3Tb2(H3L)2(OAc)2(hfac)4]∙2iso-C3H7OH (3), respectively; while [Cu3Tb2(H3L)2(OAc)2(hfac)4]∙2H2O (4) was quantitatively transformed from complex 1 by taking place of methanol molecules with water molecules. In order to yield [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMMs with larger ROH lattice solvent molecules, other ROH solvents such as isobutyl alcohol, n-butyl alcohol and isoamyl alcohol were also used instead of methanol for 1, but no any crystalline products could be obtained. Furthermore, the [Cu3Dy2(H3L)2(OAc)2(hfac)4] SMM system was also explored, but only the crystal structure of [Cu3Dy2(H3L)2(OAc)2(hfac)4]∙2MeOH (5) was successfully solved, the crystal structure of [Cu3Dy2(H3L)2(OAc)2(hfac)4] SMMs with other lattice solvent molecules  could not be obtained due to the severe twinning phenomenon.Bis-tris propane (H3Tb2(H3L)2(OAc)2(hfac)4]∙2ROH SMMs have the main structure [Cu3Tb2(H3L)2(OAc)2(hfac)4] 2(OAc)2(hfac)4]∙2MeOH (1) is chose to be described in detail. In the main structure [Cu3Tb2(H3L)2(OAc)2(hfac)4], a {Cu3(H3L)2} linear unit is formed through bridging two terminal {Cu(H3L)}− fragments using a central Cu2+ ion, then two Tb3+ ions link to this {Cu3(H3L)2} linear unit in the opposite direction, in which each Tb3+ ion connects with the central Cu2+ ion and one external Cu2+ ion through sharing one μ3-O atom and one μ-O atom from one H3L3− ligand, and one μ3-O atom from the other H3L3− ligand 2Xn}35. The eight-coordinate sphere of each Tb3+ ion is finally completed by two hfac− anions and one OAc− anion. Shape software37 was adopted to calculate the Tb(III) coordination polyhedron, giving a triangular dodecahedron as the most likely configuration for complex 1, and the deviation value from the ideal D2d symmetry is 1.015  coordination polyhedra of complexes 2–4 using Shape software37 are listed in Tables All  SMM system.The direct current (dc) variable-temperature magnetic susceptibility of complexes eld Fig. . The roo 24.91 cm K mol−1,χ′, Fig. χ′′, Fig. 1–4 are frequency-dependent in zero dc field, indicating slow magnetic relaxation typical for SMMs. Such thermally induced relaxation was fitted with the Arrhenius law, τ = τ0exp(Ueff/kT), extracting Ueff/k values of 30.0(0.4) K for 1, 32.4(0.2) K for 2, 33.1(0.7) K for 3 and 25.7(0.2) K for 4 as well as τ0 values of 3.7(0.2) × 10−8 s for 1, 6.2(0.1) × 10−9 s for 2, 2.6(0.3) × 10−8 s for 3 and 2.3(0.1) × 10−8 s for 4 13. A comparison of the effective barrier value for complexes 1–4 with the R group of the ROH lattice solvent molecules  reveals an important magneto-structural correlation for this [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMM system: The larger the R group in ROH, the higher the energy barrier of the [Cu3Tb2(H3L)2(OAc)2(hfac)4]∙2ROH SMM 2[Tb2Cu3(H3L)2(NO3)7(CH3OH)2](NO3) (36 K)35; the Ueff/k value of 1 is also remarkable, which is comparable with that of [Cu22Tb2(N3)6]·2CH3OH  38. In many cases44, a dc field is necessary for 3d-4f heterometallic complexes to display magnetic relaxation because of the obvious quantum-tunnelling effects.The solvatomagnetic effect could also be detected by alternating current (ac) magnetic susceptibility investigations. Both the in-phase χ′, Fig. , SI and r 4 Fig. . All fouSMM Fig. . It is n3Tb2(H3L)2Xn] system is not because of single-ion behaviours, and both the Cu···Cu and Cu···Tb ferromagnetic interactions maybe quench the tunnel splitting, which are similar to acting as an internal applied field, inducing to zero-field SMM behaviours35. Nevertheless, the difference of the Tb3+ coordination configurations has influence on the SMM characteristics35. Owing to great difficulty for theoretical calculation and comparison of the Cu···Cu and Cu···Tb ferromagnetic couplings35, we tried to make a magneto-structural correlation for complexes 1–4 using the deviation value from the ideal D2d symmetry of the biaugmented trigonal prism for the Tb3+ ion and the intermolecular distance as two main structural parameters. As shown in Table 3+ ions is closer to the biaugmented trigonal prism from 1 to 3, the corresponding energy barrier value becomes larger from 1 to 3, indicating the biaugmented trigonal prism configuration in the [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMM system is the dominant configuration; but 4 is a bit unusual, its deviation value (1.735) is comparable with that of 1 (1.756), which suggests that other structural factors such as intermolecular distances need to be considered; as shown in Table central…Cucentral separation), the higher the energy barrier; which is in line with the magneto-structural correlation using the R group itself, because larger ROH lattice solvent molecules may enhance intermolecular distances correspondingly.Simplified theoretical investigations by Murrie group suggested that the magnetic bistability in the (NO3)35, and the ferromagnetic coupling obviously exists between the Cu2+ ion and the Dy3+ ion as well as among the Cu2+ ions, similar to that observed in [Gd2Cu3(H3L)2(CH3COO)6]·THF·3H2O by Murrie group35.The l−1 Fig. , which i5 are similar to those of complexes 1–4. Under zero dc field, the appearance of frequency-dependent χ′  K and τ0 = 9.7(0.1) × 10−9 s 2{Dy2Cu3(H3L)2(NO3)7(CH3OH)2](NO3) [23.9(0.1) K], whose χ″ signals even do not appear peaks in zero dc field35. Notably, this Ueff/k value is the third high value for the Cu-Dy heterometallic SMMs, after 47 K of [{Dy(hfac)3}2{Cu(dpk)2}] (dpk− = di-2-pyridyl ketoximate)48 and 41.6 K of [Cu4Dy4(vanox)6(Hvanox)2(NO3)4(μ-HOMe)2]·6MeOH 49. Furthermore, this Ueff/k value is remarkable larger than those of the Cu-Dy heterometallic SMMs with higher nucleus (<20 K)51. Additionally, the parameter Φ value of 0.16 for 5 supports the SMM nature too.The magnetization dynamics of compound  χ′ Fig. , SI and als Fig.  indicate9 s Fig. . The ene5 revealed that the χ″ signals of 5 are temperature-dependent methylamino]propane ligand (H6L). The ROH lattice solvent molecules  in the [Cu3Tb2(H3L)2(OAc)2(hfac)4] SMM system have great influences on the energy barrier; the larger the R group, the higher the energy barrier. We predict that the larger ROH molecule may enlarge the intermolecular distance and can help to change the coordination configuration of the Ln(III) ions through the hydrogen bonding interaction between the ROH lattice solvent molecule and the [Cu3Tb2(H3L)2(OAc)2(hfac)4] main-structural molecule. Our work demonstrates that solvatomagnetic effects can be used to continuously fine-tune energy barriers in SMMs. The discovery is bound to have significances in enhancing and turning energy barriers of molecular nanomagnets via chemical methods such as using lattice-solvent effects.In summary, a mixed OAcThe elemental analyses were measured on a Vario ELIII elemental analyser. The magnetic susceptibility measurements were carried out on a Quantum Design MPMS-XL5 SQUID magnetometer, and diamagnetic corrections were calculated from Pascal’s constants of all components.6L (0.25 mmol) and Cu(ClO4)2·6H2O (0.375 mmol) in 20 mL of MeOH, was added Tb(OAc)(hfac)2(H2O)2 (0.15 mmol), a blue solution was formed after being stirred for 10 min; Et3N (0.75 mmol) was then added dropwise, the resultant solution was stirred for 3 h at room temperature and turned violet. Violet plate-like X-ray quality crystals were obtained through slow evaporation of the filtrate at room temperature over 1 week. Yield (25%). Anal. Calcd (%) for C48H64Cu3F24N4O26Tb2 (1) C 27.75; H 3.11; N 2.70. Found: C 27.80; H 3.14; N 2.67.To a mixture of H1 was followed, but using ethanol instead of methanol. Violet plate-like X-ray quality crystals were obtained through slow evaporation of the filtrate at room temperature over 10 days. Yield (27%). Anal. Calcd (%) for C50H68Cu3F24N4O26Tb2 (2): C 28.52; H 3.26; N 2.66. Found: C 28.55; H 3.29; N 2.63.The same synthetic procedure for complex 1 was followed, but using isopropyl alcohol instead of methanol. Violet plate-like X-ray quality crystals were obtained through slow evaporation of the filtrate at room temperature over 15 days. Yield (22%). Anal. Calcd (%) for C52H72Cu3F24N4O26Tb2 (3): C 29.27; H 3.40; N 2.63. Found: C 29.23; H 3.43; N 2.60.The same synthetic procedure for complex 1 was kept at 60 °C for 6 h, and then exposed on air for 24 h. Violet plate-like X-ray quality crystals of 4 were obtained quantitatively. Anal. Calcd (%) for C46H60Cu3F24N4O26Tb2 (4): C 26.96; H 2.95; N 2.73. Found: C 27.02; H 2.99; N 2.69.Complex 1 was followed, but using Dy(OAc)(hfac)2(H2O)2 instead of Tb(OAc)(hfac)2(H2O)2. Violet plate-like X-ray quality crystals were obtained through slow evaporation of the filtrate at room temperature over 1 week. Yield (28%). Anal. Calcd (%) for C48H64Cu3Dy2F24N4O26 (5): C 27.66; H 3.09; N 2.69. Found: C 27.69; H 3.11; N 2.67.The same synthetic procedure for complex 3 of 1, 0.178 × 0.063 × 0.024 mm3 of 2, 0.183 × 0.125 × 0.031 mm3 of 3, 0.108 × 0.067 × 0.025 mm3 of 4, and 0.134 × 0.125 × 0.027 mm3 of 5 was picked out to mount on a Bruker SMART APEX-CCD diffractometer with Mo-Kα radiation (λ = 0.71073 Å) for data collection at 173(2) K. Empirical absorption corrections from φ and ω scan were applied. Cell parameters were calculated by the global refinement of the positions of all collected reflections for five complexes. The structures were solved by direct methods and refined by a full matrix least-squares technique based on F2 using with the SHELX-2014 program package. All hydrogen atoms were set in calculated positions and refined as riding atoms, and all non-hydrogen atoms were refined anisotropically. CCDC 1574978–1574982 contain the supplementary crystallographic data, which can be obtained free of charge from the Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.A single crystal with dimensions 0.261 × 0.093 × 0.025 mm1: P−1, a = 10.086(2) Å, b = 12.463(3) Å, c = 15.594(3) Å, α = 104.67(3)°, β = 94.07(3)°, γ = 108.97(3)°, V = 1767.9(7) Å3, Mr = 2077.49, Dc = 1.951 g cm−3, Z = 1, R1 = 0.0366 (I > 2σ(I)), wR2 = 0.0878 (I > 2σ(I)), S = 1.080.Crystal data for 2: P−1, a = 10.243(2) Å, b = 12.469(3) Å, c = 15.602(3) Å, α = 101.71(3)°, β = 96.50(3)°, γ = 110.00(3)°, V = 1797.2(6) Å3, Mr = 2105.54, Dc = 1.945 g cm−3, Z = 1, R1 = 0.0498 (I > 2σ(I)), wR2 = 0.1085 (I > 2σ(I)), S = 1.122.Crystal data for 3: P−1, a = 10.309(2) Å, b = 12.473(3) Å, c = 15.677(3) Å, α = 101.80(3)°, β = 96.96(3)°, γ = 110.19(3)°, V = 1811.4(7) Å3, Mr = 2133.58, Dc = 1.956 g cm−3, Z = 1, R1 = 0.0345 (I > 2σ(I)), wR2 = 0.0797 (I > 2σ(I)), S = 1.084.Crystal data for 4: P−1, a = 10.042(2) Å, b = 12.480(3) Å, c = 15.819(3) Å, α = 107.08(3)°, β = 99.23(3)°, γ = 109.83(3)°, V = 1706.2(7) Å3, Mr = 2049.44, Dc = 1.995 g cm−3, Z = 1, R1 = 0.0488 (I > 2σ(I)), wR2 = 0.0945 (I > 2σ(I)), S = 1.153.Crystal data for 5: P−1, a = 10.085(2) Å, b = 12.427(3) Å, c = 15.581(3) Å, α = 104.59(3)°, β = 94.21(3)°, γ = 108.86(3)°, V = 1762.5(7) Å3, Mr = 2084.65, Dc = 1.964 g cm−3, Z = 1, R1 = 0.0321 (I > 2σ(I)), wR2 = 0.0762 (I > 2σ(I)), S = 1.074.Crystal data for Supplementary Information


Only a weak directional interaction of the C—H⋯O type combines molecules in infinite chains running along the  23H26O5 or CH2=C(CH3)—C(O)O—C6H4—O(O)C—C6H4—OC6H13, has been determined. The molecule is non-planar and the dihedral angle between the phenyl rings is 50.72 (4)°. The crystal packing differs from those typical for mesogenic compounds. Only a weak directional interaction of the C—H⋯O type combines molecules in endless chains running along the a axis.The structure of the title compound, C The structural studies of these compounds are of great interest as these investigations make it possible to clarify the structure of the mesophase and propose a mechanism of phase transitions in a crystal-mesophase-isotropic system.Phenylbenzoates bearing a rather long aliphatic substituent at the benzene ring are potentially mesogenic compounds. On melting, these compounds often form smectic or nematic phases. Cases where these compounds exhibit a monotropic mesomorphism, IIICr 367.7 K Iso 350.6 K IICr 349.9 K ICr.In this work we performed an X-ray structural determination and DSC study of the title compound. According to DSC the compound is non–mesomorphic, exhibiting three solid-state modifications: viz. benzene rings C8–C13 (plane I) and C2–C7 (plane II), ester groups C2/C1/O1/O2 (plane III) and O4/O5/C20/C21 (plane IV) and the hexyloxy group O3/C14–C19 (plane V). The dihedral angles between the planes I/II, II/III, II/V, I/III and I/IV are 50.72 (4), 4.84 (5), 7.05 (3), 52.82 (4) and 55.50 (5)°, respectively. According to the CSD Groom et al., 2016nHn+12 (n > 4), this substituent has an extended structure and its plane is nearly coplanar with the plane of the corresponding benzene ring.The unit cell contains one independent molecule whose structure is shown in Fig. 1et al., 2009et al., 2012et al., 2009n--n′-tolyidines  related molecules may be considered to be weak hydrogen bonds  I. DOI: 10.1107/S2056989017008568/rk2436Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017008568/rk2436Isup3.cmlSupporting information file. DOI: 1554948CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecule is V-shaped and possesses mirror symmetry; the mirror bisects the central benzene ring. There are two intramolecular O—H⋯N hydrogen bonds present forming S(6) ring motifs.The title Schiff base compound was synthesized  34H28N2O4, is generated by mirror symmetry, with the mirror bisecting the central benzene ring. It was synthesized via the condensation reaction of 1,2-diaminebenzene with 4-benzyloxy-2-hydroxybenzaldehyde. The molecule is V-shaped and there are two intramolecular O—H⋯N hydrogen bonds present forming S(6) ring motifs. The configuration about the C=N imine bonds is E. The central benzene ring makes dihedral angles of 41.9 (2) and 43.6 (2)° with the phenol ring and the outer benzyloxy ring, respectively. The latter two rings are inclined to each other by 84.4 (2)°. In the crystal, molecules are linked by C—H⋯π interactions, forming layers lying parallel to the ab plane. The Hirshfeld surface analysis and the two-dimensional fingerprint plots confirm the predominance of these interactions in the crystal structure. The antioxidant capacity of the compound was determined by the cupric reducing antioxidant capacity (CUPRAC) process.The whole molecule of the title Schiff base compound, C In view of this interest we have synthesized the title compound, (I)1H NMR NMR spectrum reveals the presence of an imino group (N=CH) in the range δ = 8.5–8.7 p.p.m. The antioxidant capacity of the compound was determined by the cupric reducing antioxidant capacity (CUPRAC) process.Schiff base derivatives are a biologically versatile class of compounds possessing diverse activities, such as anti-oxidant (Haribabu viz. bonds C1—C1i and C3—C3i . In the molecule there are two intramolecular O—H⋯N hydrogen bonds present (Table 1S(6) ring motifs as shown in Fig. 1E and the C4=N1 bond length is 1.278 (6) Å. The C3—N1=C4 bond angles are less than 120° [118.9 (4)°], and the imine group has a C3—N1—C4—C5 torsion angle of −176.8 (4)°. The molecule is V-shaped and the two arms are non-planar; the central benzene ring forms dihedral angles of 41.9 (2) and 43.6 (2)° with the phenol ring (C5-C10) and the outer benzyloxy ring (C12–C17), respectively. The latter two rings are almost normal to each other, with a dihedral angle of 84.4 (2)°.The molecular structure of compound (I)t Table 1, which fIn the crystal of (I)et al., 2007CrystalExplorer17  and H⋯C/C⋯H at 34.6% , followed by the H⋯O/O⋯H interactions at 13.6% .The Hirshfeld surface analysis ]diphenol ethanol solvate (II) ]diphenol (III)  ring motifs.A search of the Cambridge Structural Database  the phenol rings are inclined to the central benzene ring by 53.9 (3) and 4.0 (2)° and to each other by 49.9 (2)°. In (III) the corresponding dihedral angles are 48.12 (8), 21.44 (8) and 47.70 (8)°, while in (V) the corresponding dihedral angles are 58.29 (12), 2.20 (12) and 57.60 (12)°. In compound (IV), that possesses twofold rotational symmetry with the twofold axis bisecting the central benzene ring, the phenol rings are inclined to the central benzene ring by 82.30 (5)° and to each other by 63.76 (5)°. In the title compound, which possesses mirror symmetry, the corresponding dihedral angles are 41.9 (2) and 68.9 (2)°.o-phenylenebis(nitrilomethylidyne)]diphenolato)nickel(II) dihydrate methylylidene]}dibenzene-1,3-diolato-κO3)copper(II) methanol solvate II-Nc] (CUPRAC) method Nc2–Cu+2 complex. Indeed, in the presence of an antioxidant agent, the copper–neocuproene complex is reduced and this reaction is quantified spectrophotometrically at a wavelength of 450 nm.The antioxidant activity profile of the synthesized compound (I)0.50 = 15.03 ± 1.50 for a 4 mg dosage, compared to the results for buthylated toluene (BHT) [A0.50 = 8.97 ± 3.94], used as a positive control (see Table 2p < 0.05).According to the cupric ion reducing antioxidant capacity assay, the title compound displayed activity with variable potency in all tested concentrations, because the percentage (%) inhibition in the CUPRAC assay is good [Ain vacuo. The residue was recrystallized from ethanol, yielding yellow block-like crystals of the title compound on slow evaporation of the solvent. The purity of the compound was characterized by its NMR spectrum . The azomethine proton appears in the 8.5–8.7 p.p.m. range, while the imine bond is characterized in the 13C RMN spectrum with the imine C and OH signals in the range 162.23–163.34 p.p.m. 1H NMR: δ = 6.5–7.6 , δ = 13.7 , δ = 5.1 . 13C NMR: 70.15, 120.33, 127.30, 127.64, 128.26, 128.75, 142.32, 162.23, 163.33, 163.34.1,2-Diaminebenzene (0.027 g) and 4-benzyloxy-2-hydroxybenzaldehyde (0.1141 g) in ethanol (15 ml) were refluxed for 1 h, then the solvent was evaporated Uiso(H) = 1.5Ueq(O). The C-bound H atoms were positioned geometrically (C–H = 0.93–0.97 Å) and refined as riding with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989018005832/su5438sup1.cifCrystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989018005832/su5438Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018005832/su5438Isup3.cmlSupporting information file. DOI: 1837095CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecular and crystal structure of the title Schiff base derivative is reported. The crystal packing depends on O—H⋯N hydrogen-bonds, augmented by C—H⋯π interactions. 17H18N2O, the central carbon atom with the OH substituent and one of the (E)-benzylideneamino substituents are disordered over two sets of sites with occupancies of 0.851 (4) and 0.149 (4). The relative positions of the two disorder components is equivalent to a rotation of approximately 60° about the C—N single bond. In the crystal, the molecules are held together by O—H⋯N hydrogen bonds, forming simple C(5) chains along the b-axis direction. In addition, pairs of the chains are further aggregated by weak C—H⋯π interactions.In the title compound, C To gain more insight into the structural and spectroscopic properties of this potentially polydentate ligand, we report herein the molecular structure of the title compound.During the last decades, interest in Schiff bases and their complexes has been constant due to their extensive use for industrial purposes and also for their broad range of biological activities :0.149 (4). The difference between the two conformers is reflected in the relative arrangement of the central spacer units. In the major disorder component, the torsion angle C3—C4—N2—C5 is −158.7 (2)° whereas the corresponding angle C3′—C4′—N2′—C5′ in the minor component is −93.3 (14)°. This translates to a rotation of approximately 60° about the C4—N2 bond. In the second, fully ordered, (E)-benzylideneamino substituent, the equivalent torsion angles C1—N1—C2—C3 and C1—N1—C2—C3′ are −102.03 (18)° and −79.8 (8)°, respectively.The molecular structure of the title compound is shown in Fig. 1synclinal (-sc) alignment of the hydroxyl and imine nitrogen atoms around the N(imine)—C—C—O(hydroxyl) bond  indicate a slight loss of the sp2 character. The N1=C1 azomethine group is essentially co-planar with the attached benzene ring with an N1—C1—C11—C12 torsion angle being 2.0 (5)°. In contrast, in the disordered (E)-benzylideneamino substituent, the corresponding torsion angles N2—C5—C21—C22 and N2′—C5′—C21′—C22′ are −17.6 (6) and 21 (4)° for the major and minor disorder components, respectively. All these data suggest that the difference between these (E)-benzylideneamino substituents may result from some loss of conjugation between the phenyl ring and its azomethine substituent in the disordered branch of the molecule.The N1=C1 and N2=C5 distances in the molecule are 1.270 (2) and 1.259 (3) Å, respectively, consistent with C=N double bonding. The C1—N1—C2 bond angle of 118.61 (15)° confirms the C(5) chains along the b-axis direction. In addition, pairs of the chains are linked by weak C24—H24⋯Cg1 interactions bis] bis(4-methylbenzenesulfonamide) -(2-chlorobenzylidene)amino]propan-2-ol -(4-methoxybenzylidene)amino]propan-2-ol  = 0.95 Å for aromatic and azomethine atoms, d(C—H) = 0.99 Å for methylene and d(C—H) = 1.00 Å for C3—H3. The Uiso(H) values were constrained to 1.2Ueq(C). The C3/C4/N2/C5/C21–C26 segment of the molecule is disordered over two sets of sites with a refined occupancy ratio of 0.851 (4):0.149 (4).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017004741/sj5523sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017004741/sj5523Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017004741/sj5523Isup3.cmlSupporting information file. DOI: 1540296CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Mecp2ZFNΔ/y rats display respiratory abnormalities early in development.Post-publication, the authors discovered a scale factor error of 5 affecting volumetric readings from the whole-body plethysmography chamber used for juvenile male rats (PND 21-28) in this study (Buxco PLY3211). As such, reported tidal volume (TV) and minute ventilation (MV) data are erroneously high for this group. This change does not affect the interpretation of this data as the scale factor change is applicable to both groups being compared. The below figure shows the corrected graphical representation of juvenile male rats' TV and MV readings . All numerical values have been reduced by a factor of 5 to correct for the recognized instrument error. The text of the results section has been updated online to reflect this numerical correction and should be as follows:Mecp2ZFNΔ/y rats exhibited abnormal breathing compared to WTs . Juvenile WTs breathed at a rate of 126.6 ± 5.3 BPM, which is comparable to respiratory rates of similarly aged Sprague-Dawley rats (46); however, age-matched Mecp2ZFNΔ/y rats breathed at a rate of only 100.1 ± 4.7 BPM . The reduction in frequency was due to both an increase in inspiratory time (Ti) (0.20 ± 0.01 s WT vs. 0.25 ± 0.01 s Mecp2ZFNΔ/y)  and expiratory time (Te) (0.28 ± 0.01 s WT vs. 0.37 ± 0.03 s Mecp2ZFNΔ/y) . Despite these changes in respiratory frequency, juvenile Mecp2ZFNΔ/y males exhibit an otherwise normal tidal volume (9.1 ± .6 ml/kg WT vs. 10.6 ± .6 ml/kg Mecp2ZFNΔ/y) , minute ventilation (1151.6 ± 85.0 ml/min/kg WT vs. 1073.7 ± 101.1 ml/min/kg Mecp2ZFNΔ/y) , a relatively stable respiratory cycle (irregularity score = 5.0 ± 0.6 WT vs. 5.1 ± 0.6 Mecp2ZFNΔ/y) , and a similar number of spontaneous apneas , but of a shorter duration compared to controls  .Respiratory activity was measured in juvenile male (PND 21-28), adult male (PND 40+), and aged (18 month) female rats by whole-body plethysmography. We found that under control conditions (awake and breathing room air) juvenile