A precise crystal-structure analysis using a neutron diffractometer with high-power neutron sources at the J-PARC facility has been performed on non-deuterated triglycine sulfate at 20 K and 298 K and a new double-potential-well disorder model for the O—H⋯O hydrogen bond in the 298 K structure is proposed. 2H6NO2+·SO42−·C2H5NO2 (or C6H17N3O10S), non-deuterated triglycine sulfate (HTGS) at 20 K and 298 K were undertaken using time-of-flight neutron diffraction data. At 20 K for the O—H⋯O hydrogen bond between the glycinium cation and the zwitterionic, unprotonated glycine molecule that is associated with the ferroelectric behaviour of HTGS, O—H = 1.070 (3), H⋯O = 1.408 (3) [δ = 0.338 (4)], O⋯O = 2.4777 (15) Å and O—H⋯O = 179.0 (4)°, which is in good agreement with previous studies. Two reasonable structures for the same three atoms were refined for the 298 K dataset. One is a single-minimum potential-energy model, with O—H = 1.090 (12), H⋯O = 1.361 (12) [δ = 0.271 (17)], O⋯O = 2.450 (7) Å and O—H⋯O = 179.2 (10)°, having the H atom with a large ellipticity along the bond path between the O atoms. The other is a double-minimum potential-energy model having two H atom sites with occupancies of 0.876 (8) and 0.124 (8): for the major occupancy component, O—H = 1.065 (12), H⋯O = 1.387 (12), O⋯O = 2.451 (7) Å and O—H⋯O = 178.2 (11)° and for the minor component, O—H = 1.06 (4), H⋯O = 1.41 (4), O⋯O = 2.451 (7) Å and O—H⋯O = 166 (2)°. These models did not show any significant differences in R factors. In addition, the unit-cell parameters and other structural parameters of HTGS did not show any major differences compared to those of partially deuterated TGS and fully deuterated TGS for both 20 K and 298 K.Precise single-crystal structure analyses of the title compound, bis(glycinium) sulfate–glycine (1/1), 2C The authors also proposed a hydrogen-bonding scheme and pointed out that the hydrogen atom that lies between the oxygen atom of the carboxyl group in the glycine III cation (GIII) and the O atom in the glycine II molecule (GII) plays a crucial role in the dipole reversal. Many structural studies on TGS have subsequently been conducted (see Database survey): most of them were X-ray diffraction studies, but some of them were neutron diffraction studies. The atomic coordinates of non-deuterated TGS , including those of the hydrogen atoms at room temperature, were first revealed using single-crystal neutron diffraction  group in each glycine molecule and those in sulfuric acid molecules at 40 K and 180 K , where deuterium replaced the H atoms except for the hydrogen atoms of the methylene , all the hydrogen atoms in the glycine molecules and sulfuric acid molecules are substituted by deuterium atoms: the crystal structures did not show major changes between 20 K and 295 K  exist as monoprotonated C2H6NO2+ glycinium ions. The most significant feature of these glycine/glycinium species are the N—C—C—O(H) torsion angles ° for N11—C17—C19—O7, −1.5 (1)° for N14—C15—C18—O10 and −1.4 (1)° for N21—C20—C16—O2. The sulfate ion shows its expected tetrahedral shape with bond distances of 1.480 (2) Å (S1—O4), 1.470 (2) Å (S1—O5), 1.477 (2) Å (S1—O6) and 1.472 (2) Å (S1—O8) and bond angles of 110.3 (1)° (O4—S1—O5), 107.9 (1)° (O4—S1—O6), 108.7 (1)° (O4—S1—O8), 109.7 (1)° (O5—S1—O6), 110.6 (1)° (O5—S1—O8) and 109.7 (1)° (O6—S1—O8). The slight differences among these distances and angles may arise because of the different hydrogen bonds accepted by these O atoms. Numerous N—H⋯O and O—H⋯O hydrogen bonds (see supporting information) are formed between the glycine or glycinium species and the sulfate ions; four N—H⋯O hydrogen bonds and one O—H⋯O hydrogen bond are formed by GI, five N—H⋯O hydrogen bonds are formed by GII and five N—H⋯O hydrogen bonds with the sulfate ion and one O—H⋯O hydrogen bond to the glycine molecule is formed by GIII.The refined structures at 20 K are shown in Figs. 1i  bond lengths for HTGS, DTGS and FDTGS at low temperature are listed in Table 1et al. 1997The lattice constants and the key O15—H15⋯O3B amino group [refined site occupancies = 0.874 (8):0.126 (8)] in the GI cation and the O—H⋯O association for GIII and GII. Two models were refined considering the H atom between O15 in GIII and O3 in GII. For one model (298 K model 1), the H15 atom was refined with a large ellipticity along the bond path between O15 and O3 as a single minimum potential energy structure [Fig. 5a)]. A double-minimum potential-energy structure could be deduced because the distance between O15 and O3i  did not increase with an increase in the temperature; thus for the other model (298 K model 2), a pair of hydrogen atoms were refined along the bond path between O15 and O3i, the double-minimum potential structure [Fig. 5b)].The refined structures at 298 K are shown in Figs. 3i hydrogen bond at 298 K are summarized in Table 2i in GII. On the other hand, the distance between O15 and H15 [1.090 (12) Å] is almost the same as that at 20 K despite there being no distance restraint for the H15⋯O3i separation. Therefore, the mixed structure (model 2) of the major ferroelectric phase and minor paraelectric phase is strongly suggested, because the occupancies of N11 and N11B and H15 and H3i are related by symmetry.The key parameters for the O15—H15⋯O3et al., 1997The unit-cell parameters and bond lengths for HTGS, DTGS, and FDTGS at 298 K are listed in Table 2TC for FDTGS increased by approximately 12 K compared to HTGS. Choudhury & Chitra (2008B (12%); this occupancy ratio is in excellent agreement with the results in this study. For the hydrogen atom between the oxygen atom of the carboxyl group in GIII and that in the GII, the O⋯O distance was 2.470 (9) Å, and the H atom was approximately 0.241 Å closer to the GIII O atom than that in GII. They concluded that the structure of HTGS at room temperature has a single minimum potential energy in the O—H⋯O hydrogen-bond path between GIII and GII. In this study, two reasonable structures were refined as a single-minimum potential-energy model and a double-minimum model without any significant differences. Therefore, we conclude that there is a significant possibility of a double-minimum potential-energy model for HTGS at 298 K.In the previous studies using single-crystal neutron diffraction, Kay & Kleinberg 1973 proposeditra 2008 proposedsupporting information) and no additional intermolecular interactions were found. Therefore, the 20 K and 298 K structures form essentially the structural motif of a three-dimensional network of N—H⋯O and O—H⋯O hydrogen bonds between glycinium cations, glycine molecules and sulfate ions.Hydrogen bonds in the refined structures were consistent with those reported previously ; TGLYSU15  and sulfuric acid  was added to 50 ml of water in a 100 ml beaker. They were dissolved by heating at ∼313 K with a 300 r.p.m. magnetic stirrer. After completely dissolving them, plastic films were double-wrapped around the beaker, and some holes were knocked in the films to evaporate the water slowly. The beaker was left to stand at ∼293 K. HTGS was crystallized after approximately a month, and then the solution was filtered. The collected crystals were dried in a desiccator at ∼293 K.et al., 2016x, y, λ) were measured in 16 different orientations for each dataset. The measurement time was 1.5 h for one orientation; the raw data were processed using STARGazer  slice maps and merged TOF profiles.Crystal data, data collection, and structural refinement details are summarized in Table 3SHELXL2018  between O15 and O3 to minimize the model dependence. A nuclear density distribution  global, 20K, 298KModel1, 298KModel2. DOI: 10.1107/S2056989022000858/hb800420Ksup2.hklStructure factors: contains datablock(s) 20K. DOI: Click here for additional data file.10.1107/S2056989022000858/hb800420Ksup5.cmlSupporting information file. DOI: 10.1107/S2056989022000858/hb8004298KModel1sup3.hklStructure factors: contains datablock(s) 298KModel1. DOI: Click here for additional data file.10.1107/S2056989022000858/hb8004298KModel1sup6.cmlSupporting information file. DOI: 10.1107/S2056989022000858/hb8004298KModel2sup4.hklStructure factors: contains datablock(s) 298KModel2. DOI: Click here for additional data file.10.1107/S2056989022000858/hb8004298KModel2sup7.cmlSupporting information file. DOI: 2144164, 2144163, 2144162CCDC references:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


The packing of the title compound features C—H⋯O hydrogen bonds, C—F⋯π interactions, aromatic π–π stacking and short Br⋯O contacts. 14H8Br2FN3O2, the nitro-substituted benzene ring and the 4-fluorophenyl ring form a dihedral angle of 65.73 (7)°. In the crystal, molecules are linked into chains by C—H⋯O hydrogen bonds running parallel to the c-axis direction. The crystal packing is consolidated by C—F⋯π interactions and π–π stacking interactions, and short Br⋯O [2.9828 (13) Å] contacts are observed. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (17.4%), O⋯H/H⋯O (16.3%), Br⋯H/H⋯Br (15.5%), Br⋯C/C⋯Br (10.1%) and F⋯H/H⋯F (8.1%) contacts.In the title compound, C R—N=N—R′, where R and R′ can be either aryl, hetrocycle or alkyl functional groups. They find many applications such as molecular switches, optical data storage, antimicrobial agent, colour-changing materials, non-linear optics, molecular recognition, dye-sensitized solar cells, liquid crystals, catalysis, etc. °. All of the other bond lengths and angles in the title compound are similar to those in the related azo compounds reported in the Database survey.As shown in Fig. 1Cg1 = 3.4095 (12) Å; C—F⋯Cg1 = 136.95 (9)°] interactions and weak aromatic π–π stacking [Cg2⋯Cg2 = 3.9694 (9) Å], where Cg1 and Cg2 are the centroids of the C3–C8 and C9–C14 rings, respectively  = 2.9828 (13) Å; van der Waals contact distance = 3.37 Å] are observed.In the crystal, molecules are linked by C—H⋯O hydrogen bonds into chains propagating parallel to the c axis Table 1. The cryly Fig. 2. In addiCrystalExplorer17  and those delineated into H⋯H, O⋯H/H⋯O, Br⋯H/H⋯Br, Br⋯C/C⋯Br and F⋯H/H⋯F contacts . In the Br⋯H/H⋯Br fingerprint plot, there are two symmetrical wings with de + di ≃ 2.85 Å and they contribute 15.5% to the Hirshfeld surface . The pair of characteristic wings in the fingerprint plot delineated into Br⋯C/C⋯Br contacts , have the tips at de + di ≃ 3.80 Å, while for F⋯H/H⋯F contacts , they have the tips at de + di ≃ 2.60 Å. The remaining contributions from the other different interatomic contacts to the Hirshfeld surfaces are listed in Table 3et al., 2015The overall two-dimensional fingerprint plot Fig. 4a and thce Fig. 4c. In thce Fig. 4d. The pet al., 2016E)-1--2-phenyldiazene unit gave 26 hits. Seven compounds are closely related to the title compound, viz. CSD refcode GUPHIL (I)       , molecules are linked into inversion dimers via short halogen–halogen contacts [Cl1⋯Cl1 = 3.3763 (9) Å C16—Cl1⋯Cl1 = 141.47 (7)°] compared to the van der Waals radius sum of 3.50 Å for two chlorine atoms. No other directional contacts could be identified and the shortest aromatic-ring-centroid separation is greater than 5.25 Å. In the crystals of (II) and (III), the aromatic rings form dihedral angles of 64.1 (2) and 60.9 (2)°, respectively. Molecules are linked through weak X⋯Cl contacts [X = Cl for (II) and Br for (III)], C—H⋯Cl and C—Cl⋯π interactions into sheets lying parallel to the ab plane. In the crystal of (IV), the planes of the benzene rings make a dihedral angle of 56.13 (13)°. Molecules are stacked in columns along the a-axis direction via weak C—H⋯Cl hydrogen bonds and face-to-face π–π stacking interactions. The crystal packing is further consolidated by short Cl⋯Cl contacts. In (V), the benzene rings form a dihedral angle of 63.29 (8)°. Molecules are linked by C—H⋯O hydrogen bonds into zigzag chains running along the c-axis direction. The crystal packing also features C—Cl⋯π, C—F⋯π and N—O⋯π interactions. In the crystals of (VI) and (VII), the dihedral angles between the aromatic rings are 60.31 (14) and 56.18 (12) °, respectively. In (VI) C—H⋯N and short Cl⋯Cl contacts are observed and in (VII), C—H⋯N and C—H⋯O hydrogen bonds and short Cl⋯O contacts occur.In the crystal of (E)-1-(4-fluorophenyl)-2-(2-nitrobenzylidene)hydrazine (1 mmol), tetramethylethylenediamine (TMEDA) , CuCl  and CBr4 (4.5 mmol). After 1–3h  the reaction mixture was poured into a ∼0.01 M solution of HCl , and extracted with dichloromethane (3 × 20 ml). The combined organic phase was washed with water (3 × 50 ml), brine (30 ml), dried over anhydrous Na2SO4 and concentrated in vacuo using a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and dichloromethane (3/1–1/1). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution. Light-orange solid (52%); m.p. 377 K. Analysis calculated for C14H8Br2FN3O2 (M = 429.04): C 39.19, H 1.88, N 9.79; found: C 39.14, H 1.87, N 9.73%. 1H NMR  δ 7.86–7.14 . 13C NMR  δ 165.02, 163.23, 163.01, 149.72, 133.01, 132.10, 129.70, 124.98, 124.87, 124.80, 124.29, 116.07, 115.91, 86.88. ESI–MS: m/z: 430.02 [M + H]+.A 20 ml screw-neck vial was charged with DMSO (10 ml), (Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S205698902200278X/hb8012sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902200278X/hb8012Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902200278X/hb8012Isup3.cmlSupporting information file. DOI: 2158375CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


Five new bis(arylamide)dichloridozinc(II) complexes have been prepared and characterized. All of the complexes contain hydrogen bonds between the amide N—H group and the amide carbonyl oxygen atoms or the chlorine atoms, forming extended networks. O)dichloridozinc(II), [ZnCl2(C7H7NO)2], dichloridobis(2-methylbenzamide-κO)zinc(II), [ZnCl2(C8H9NO)2], dichloridobis(3-methylbenzamide-κO)zinc(II), [ZnCl2(C8H9NO)2], dichloridobis(4-methylbenzamide-κO)zinc(II), [ZnCl2(C8H9NO)2], and dichloridobis(4-hydroxybenzamide-κO)zinc(II), [ZnCl2(C7H7NO2)2]. All of the complexes contain hydrogen bonds between the amide N—H group and the amide carbonyl oxygen atoms or the chlorine atoms, forming extended networks.Ionic co-crystals are co-crystals between organic molecules and inorganic salt coformers. Co-crystals of pharmaceuticals are of interest to help control polymorph formation and potentially improve stability and other physical properties. We describe the preparation, crystal structures, and hydrogen bonding of five different 2:1 benzamide or toluamide/zinc(II) chloride co-crystal salts, namely, bis(benzamide-κ All five complexes are 2:1 O-bonded aryl amide:ZnCl2 complexes with approximately tetrahedral zinc(II) centers. The complexes crystallize in five different space groups and form hydrogen-bonding interactions between the amide N—H groups and either an amide oxygen or a zinc-bound chlorido ligand.Five new zinc complexes, (1), bis(benzamide-κO)dichloridozinc(II), [ZnCl2(C7H7NO)2], crystallizes in the P21/n space group with two independent molecules in the asymmetric unit and displays one N—H⋯O and one N—H⋯Cl intramolecular hydrogen bond in each molecule , dichloridobis(2-methylbenzamide-κO)zinc(II), [ZnCl2(C8H9NO)2], displays two intramolecular N—H⋯Cl hydrogen bonds to one chlorine atom (see Table 2P21 space group. Compound (3), dichloridobis(3-methylbenzamide-κO)zinc(II), [ZnCl2(C8H9NO)2], crystallizes in the C2/c space group with the zinc atom lying on the twofold axis  does not form any intramolecular hydrogen bonds. Compound (4), dichloridobis(4-methylbenzamide-κO)zinc(II), [ZnCl2(C8H9NO)2], crystallizes in the P21/c space group and compound (5), dichloridobis(4-hydroxybenzamide-κO)zinc(II), [ZnCl2(C7H7NO2)2], crystallizes in the Cc space group and both compounds form two intramolecular hydrogen bonds, one N—H⋯O and one N—H⋯Cl, similar to the interactions found in compound (1)  found in a search of the CSD  forms four N—H⋯Cl intermolecular hydrogen bonds (two from each independent molecule), forming an extended network as shown in Fig. 62) also utilizes N—H bonds in hydrogen-bonding interactions, two intramolecular and two intermolecular, to form layers within the structure   forms two N—H⋯Cl intermolecular contacts in addition to the two intramolecular hydrogen bonds, resulting in a complex set of layers that run perpendicular to the b axis  results in the greatest number of hydrogen bonds among this set of complexes, as shown in Fig. 10Each compound displays a unique hydrogen-bonding network, consisting primarily of N—H⋯O and N—H⋯Cl interactions, summarized in Table 11), (3), and (5) form π–π interactions between the benzene rings of the benzamide or toluamide groups as summarized in Table 72) or (4).Compounds . The similar dichloridobis(dmf)zinc(II)  has also been reported. Edwards et al. , the latter of which undergoes a reversible phase transition at 228 K 2 where X = Cl, Br, I . As part of a larger study, Smirnov et al. , thioacetamide (VUCTOD), and benzamide (VUCVAR).A number of zinc(II) iodide complexes, ZnI al. 2009 have alset al. , one water molecule, and two chlorido ligands. In the second form (CCDC 2010264), the zinc bonds to one nefiracetam molecule through the γ-lactam and to a second via the amide carbonyl, forming a cyclic zinc dimer.Three structural studies have prepared zinc(II)chloride complexes with pharmaceutically relevant molecules. Sultana  al. 2016 prepared al. 2020 describe1) through (5) were prepared by dissolution of the respective components in various solvents  followed by slow evaporation. In a typical preparation, a 1:1 stoichiometric ratio of benzamide (0.1352 g) and zinc(II) chloride (0.1336 g) was dissolved in approximately 5 mL of a 50:50 v:v ratio of water and ethanol. Slow evaporation of the resulting solution produced single crystals of compound (1).All reagents were used as received from the manufacturer. Compounds  = 1.2Ueq(C) (aromatic) or Uiso(H) = 1.5Ueq(C) (methyl). All amide H-atom positions were refined with N—H distances restrained to 0.88 (2) Å and Uiso(H) = 1.5Ueq(N). The hydroxyl H-atom positions in compound (5) were refined with O—H distances restrained to 0.84 (2) Å and Uiso(H) = 1.5Ueq(N).All carbon-bonded H atoms were placed in idealized positions using a riding model with aromatic C—H = 0.95 Å, methyl C—H = 0.98 Å and 1) was refined as a pseudo-merohedral twin  with a twin law of (0 0 −1 0 −1 0 −1 0 0) , corresponding to a twofold rotation about the [10Compound (3) was modeled as a disordered methyl group with each set of hydrogen atoms rotated by 60° (AFIX 127). The disorder was identified from multiple peaks near C8 in the difference map. The refined occupancies of the two hydrogen atom sets were 0.54 (2):0.46 (2).The methyl group in compound  global, 1, 2, 3, 4, 5. DOI: 10.1107/S2056989021008264/zl50231sup2.hklStructure factors: contains datablock(s) 1. DOI: Click here for additional data file.10.1107/S2056989021008264/zl50231sup7.molSupporting information file. DOI: 10.1107/S2056989021008264/zl50232sup3.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989021008264/zl50232sup8.molSupporting information file. DOI: 10.1107/S2056989021008264/zl50233sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989021008264/zl50233sup9.molSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021008264/zl50234sup10.molSupporting information file. DOI: 10.1107/S2056989021008264/zl50234sup5.hklStructure factors: contains datablock(s) 4. DOI: Click here for additional data file.10.1107/S2056989021008264/zl50235sup11.molSupporting information file. DOI: 10.1107/S2056989021008264/zl50235sup6.hklStructure factors: contains datablock(s) 5. DOI: 2102513, 2102512, 2102511, 2102510, 2102509CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II featuring piano-stool geometries and supported by triarylphosphine ligands, showing the effects of para substitution on supramolecular structure and allowing comparison to the large class of previously reported acetyl complexes.Solid-state structures are presented for three propionyl complexes of Mo para substituents, namely, dicarbonyl(η5-cyclopentadienyl)propionyl(triphenylphosphane-κP)molybdenum(II), [Mo(C5H5)(C3H5O)(C18H15P)(CO)2], (1), dicarbonyl(η5-cyclopentadienyl)propionyl[tris(4-fluorophenyl)phosphane-κP]molybdenum(II), [Mo(C5H5)(C3H5O)(C18H12F3P)(CO)2], (2), and dicarbonyl(η5-cyclopentadienyl)propionyl[tris(4-methoxyphenyl)phosphane-κP]molybdenum(II) dichloromethane solvate, [Mo(C5H5)(C3H5O)(C21H21O3P)(CO)2]·CH2Cl2, (3), have been prepared from the corresponding ethyl complexes via phosphine-induced migratory insertion. These complexes exhibit four-legged piano-stool geometries with molecular structures quite similar to each other and to related acetyl complexes. The extended structures of the three complexes differ somewhat, with the para substituent of the triarylphosphine of (2) (fluoro) or (3) (methoxy) engaging in non-classical C—H⋯F or C—H⋯O hydrogen-bonding interactions. The structure of (3) exhibits modest disorder in the position of one Cl atom of the dichloromethane solvent, which was modeled with two sites showing approximately equivalent occupancies [0.532 (15) and 0.478 (15)].Three cyclopentadienylmolybdenum(II) propionyl complexes featuring triarylphosphine ligands with different  Although substitution of phosphine aryl groups with electron-withdrawing or -donating groups minimally affects local structure, the supramolecular organization is substantially affected by non-classical hydrogen-bonding to the fluoro and methoxy groups in (2) and (3), respectively.We were interested in extending earlier studies to higher-order alkyl groups at molybdenum, and in this report we describe the synthesis and solid-state structures of related Mo1), (2), and (3) are illustrated in Figs. 1trans-disposed carbonyl ligands. As previously observed for most related acetyl complexes, the acyl C=O points up toward the Cp ring. In the case of (1), this phenomenon could be rationalized by presence of short C4—H4A⋯O1 (2.672 Å) and C4—H4B⋯O2 (2.639 Å) contacts involving the carbonyl ligands that are enabled when the acyl points up. However, the variation of the Mo1—C3—C4—C5 torsion angle across the series  argues against the general importance of such an interaction.The molecular structures of (1), (2), and (3) are presented in Tables 12) crystallized with two nearly equivalent molecules in the asymmetric unit, so geometric parameters are presented for both. In general, the three complexes are nearly identical, as might be expected based on the dominant role of sterics in determining structure and the fact that the steric profiles of the three triarylphosphine ligands are identical. The Mo—P bond length in (2) [2.4692 (4) Å (avg)] is slightly shorter than in (1) or (3) , which may be related to stronger π-backbonding to the tris(4-fluorophenyl)phosphine ligand. Stronger backbonding is supported by the observation by infrared spectroscopy of slightly higher-energy carbonyl stretching vibrations for (2) [ν(CO)avg = 1897 cm−1] compared with (1) and (3) . Geometric parameters for all complexes are quite similar to those for the related triphenylphosphine-supported CpMo acetyl complex , (2), and (3) in their molecular structures, the para substituent of the triarylphosphine ligand  plays an important role in determining the extended structure. The extended structure of (1) is dominated by non-classical C—H⋯O interactions involving its carbonyl ligands. A short C—H⋯O interaction between O2 and H12 of a phenyl ring (2.36 Å) joins molecules of (1) into centrosymmetrical dimers that are organized into chains along [010] by intermolecular C15—H15⋯Cg4  and intramolecular O2⋯Cg4 (3.295 Å) interactions  features two nearly equivalent molecules in the asymmetric unit exhibiting a non-classical C—H⋯O interaction between O6 of a propionyl ligand and H15 from a phenyl ring (2.59 Å) and a C—H⋯F close contact between F3 and H53 (2.60 Å). These pairs of molecules are joined into chains along [001] by C34—H34⋯O1 hydrogen bonding .The tris(4-fluorophenyl)phosphine-supported derivative (1), complex (3) is joined into centrosymmetrical dimers by a C—H⋯O interaction involving a carbonyl ligand . This further set of interactions involving methoxy groups, as well as important close contacts involving the dichloromethane solvent, are depicted in Fig. 9Like complex (CO)2(PR3)(COR). The trans-dicarbonyl structure, as observed for (1)–(3), is preferred except in cases where the phosphine and acyl ligands are covalently linked, forcing them to be cis CpMo(CO). This compound was prepared by modification of the method used of Gladysz et al.  was dissolved in THF (10 ml). Sodium triethylborohydride  was added dropwise by syringe with vigorous stirring, leading to an immediate color change from purple to green–yellow with evolution of H2 gas. The reaction was allowed to proceed with stirring for 20 min, and an excess of iodoethane  was added dropwise with stirring and the reaction was allowed to proceed for 6 h. Volatiles were removed in vacuo to afford a yellow–brown film that was stored at 238 K for 1 week. The solid was extracted with pentane (4 × 10 ml) and filtered through a 1 cm pad of activated alumina to afford a yellow solution, and removal of solvent in vacuo afforded 3(CH2CH3)CpMo(CO) as a pure yellow powder . 1H NMR : δ 5.28 , 1.72 , 1.45 . 13C{1H} NMR : δ 239.9 (Mo—CO), 227.8 (Mo—CO), 93.0 (Cp ring), 20.4 (Mo—CH2CH3) −3.7 (Mo—CH2CH3). IR  ν(CO): 2015, 1921 (split). al. 1979, as prev al. 1979 and Anst al. 2020. In a 202(PPh3)(COCH2CH3) (1)CpMo(CO). In an inert-atmosphere glove box, CpMo(CO)3(CH2CH3)  and triphenylphosphine  were dissolved in acetonitrile (5 ml) in a 20 ml scintillation vial equipped with a flea-sized stir bar. The mixture was stirred for 1 week, during which time a bright-yellow precipitate formed. The yellow solid was isolated by filtration and washed with pentane (2 × 5 ml), then dried in vacuo to afford pure 1. Yellow crystals of 1 suitable for X-ray diffraction were obtained from a concentrated dichloromethane solution by vapor cross diffusion with pentane at 238 K. 1H NMR : δ 7.50–7.30 , 5.00 , 3.03 CH2CH3), 0.90 CH2CH3). 13C{1H} NMR : δ 267.7 , 238.8 , 135.7 , 133.2 , 130.5 , 128.6 , 96.7 (Cp ring), 58.1 (Mo—COCH2CH3), 10.1 (Mo—COCH2CH3). 31P{1H} NMR : δ 68.4 (s). IR  ν(CO): 1935, 1851, 1614 (acetyl).2(P(4-FPh)3)(COCH2CH3) (2)CpMo(CO). In an inert-atmosphere glove box, CpMo(CO)3(CH2CH3)  and tris(4-fluorophenyl)phosphine  were dissolved in acetonitrile (5 ml) in a 20 ml scintillation vial equipped with a flea-sized stir bar. The mixture was stirred for 1 week, causing a color change to orange, but without formation of any precipitate. Solvent was removed in vacuo, causing precipitation of a yellow solid that was isolated by filtration and washed with pentane (2 × 3 ml) to afford the desired product 2 . Yellow crystals of 2 suitable for X-ray diffraction were obtained from a concentrated dichloromethane solution by vapor cross diffusion with pentane at 238 K. 1H NMR : δ 7.41–7.30 , 7.14 , 4.90 , 2.99 CH2CH3), 0.90 CH2CH3). 13C{1H} NMR : δ 265.4 , 238.2 , 164.0 , 135.0 , 131.3 , 116.0 , 96.5 (Cp ring), 58.2 (Mo—COCH2CH3), 10.9 (Mo—COCH2CH3). 31P{1H} NMR : δ 68.5 (s). IR  ν(CO): 1938, 1856, 1620 (acetyl).2(P(4-MeOPh)3)(COCH2CH3) (3)CpMo(CO). In an inert-atmosphere glove box, CpMo(CO)3(CH2CH3)  and tris(4-methoxyphenyl)phosphine  were dissolved in acetonitrile (5 ml) in a 20 nml scintillation vial equipped with a flea-sized stir bar. The mixture was stirred for 1 week, causing precipitation of 3 as a pure yellow powder that was isolated by filtration. Crystals of 3 suitable for X-ray diffraction were obtained from a concentrated dichloromethane solution by vapor cross diffusion with pentane at 238 K. 1H NMR : δ 7.37–7.23 , 7.14 , 4.99 , 3.03 CH2CH3), 0.89 CH2CH3). 13C{1H} NMR : δ 268.6 , 239.2 , 161.1 (C—OCH3 of phosphine), 134.6 , 127.4 , 114.0 , 96.6 (Cp ring), 58.0 (Mo—COCH2CH3), 10.1 (Mo—COCH2CH3). 31P{1H} NMR : δ 62.3 (s). IR  ν(CO): 1933, 1847, 1605 (acetyl).Uiso(H) = k×Ueq(C), k = 1.2 for cyclopentadienyl, phenyl, and methylene groups and 1.5 for methyl groups. Methyl group H atoms were allowed to rotate in order to find the best rotameric conformation.Crystal data, data collection and structure refinement details are summarized in Table 71); seven for (2); five for (3)] are missing from these high-quality data sets due to the arrangement of the instrument with a conservatively sized beam stop. The large number of reflections in the data sets (and the Fourier-transform relationship of intensities to atoms) ensures that no particular bias has been introduced.A small number of intense low-angle reflections .The structure of  global, 1, 2, 3. DOI: 10.1107/S2056989021008008/jq20081sup2.hklStructure factors: contains datablock(s) 1. DOI: Click here for additional data file.10.1107/S2056989021008008/jq20081sup5.cdxSupporting information file. DOI: 10.1107/S2056989021008008/jq20082sup3.hklStructure factors: contains datablock(s) 2. DOI: Click here for additional data file.10.1107/S2056989021008008/jq20082sup6.cdxSupporting information file. DOI: 10.1107/S2056989021008008/jq20083sup4.hklStructure factors: contains datablock(s) 3. DOI: Click here for additional data file.10.1107/S2056989021008008/jq20083sup7.cdxSupporting information file. DOI: 2101246, 2101245, 2101244CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The β-tubulin blot in Figure 5B (middle panel) was inadvertently taken from Figure 5F (MEK1 blot in the third panel) while preparing the figures. The amended Figure 5B (middle panel) here shows the correct β-tubulin blot.


In the title compound,the two pyridine side arms are not coplanar, with the terminal pyridine rings subtending a dihedral angle of 26.45 (6)°. In the crystal, hydrogen bonds, intermolecular C—H⋯Cl contacts and a weak C—H⋯O interaction connect the molecule with neighbouring chloride counter-anions and lattice water molecules. The crystal packing also features by π–π interactions. 19H23N52+·2Cl−·2H2O, the two pyridine side arms are not coplanar, with the terminal pyridine rings subtending a dihedral angle of 26.45 (6)°. In the crystal, hydrogen bonds, intermolecular C—H⋯Cl contacts and a weak C—H⋯O interaction connect the molecule with neighbouring chloride counter-anions and lattice water molecules. The crystal packing also features by π–π interactions with centroid-centroid distances of 3.4864 (12) and 3.5129 (13) Å.In the title compound, C Bond leIn the crystal, there are intermolecular hydrogen bonds Table 1 and C—H⋯a-axis direction with a Cg1⋯Cg2  centroid–centroid distance of 3.4864 (12) Å, a perpendicular distance from the centroid Cg1 to the plane of the other ring of 3.2472 (8) Å and a slippage between the centroids of 1.100 Å. Similarly, the second π–π stacking interaction has a Cg3⋯Cg3 centroid-centroid distance of 3.5129 (13) Å, a perpendicular distance from the centroid Cg3 to the plane of the other ring of 3.2177 (8) Å and a slippage between the centroids of 1.410 Å. Cg1, Cg2 and Cg3 are the centroids of N1/C8–C12, N3/C1–C5 and N5/C15–C19 pyridine rings, respectively pyridine-2,6-dicarboxamide methyl]pyridine-2,6-dicarboxamide hemihydrate methanaminium] dichloride dihydrate compound was obtained following the procedure previously reported in the literature (tosyl)amino]methyl}pyridine, which could be isolated after chromatography bis[Slow diffusion between toluene and a wet dichloromethane solution of the brown oil set aside at room temperature gave colourless needles of the title compound suitable for X-ray diffraction within five days.Uiso(H) = 1.2Ueq(C). For two similar N—H distances, a restraint was applied to make them approximately equal with an effective standard deviation of 0.02 Å.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698902101183X/tx2045sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902101183X/tx2045Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S205698902101183X/tx2045Isup3.cmlSupporting information file. DOI: 2120892CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


Z configuration. In the crystal, the molecules are linked by weak C—H⋯π hydrogen bonds and very weak π–π stacking interactions.The title Schiff base exists in the enol–imine tautomeric form and adopts a  16H17NO, is a Schiff base that exists in the enol–imine tautomeric form and adopts a Z configuration. The molecule is non-planar, with the twisted rings making a dihedral angle of 39.92 (4)°. The intramolecular O—H⋯N hydrogen bond forms an S(6) ring motif. In the crystal, molecules are linked by C—H⋯π interactions and very weak π-π stacking interactions also help to consolidate the crystal packing. A Hirshfeld surface analysis was performed to investigate the contributions of different intermolecular contacts within the supramolecular structure. The major contributions are from H⋯H (65%), C⋯H (19.2%) and O⋯H (6.6%) interactions.The title compound, C These compounds can be easily synthesized by condensation of a primary aliphatic or aromatic amine with an aldehyde or ketone in different solvent media and they can easily be purified, since the amount of by-products is negligible  ring motif. The C1—O1 [1.353 (2) Å] and C7—N1 [1.282 (2) Å] bond distances indicate their single- and double-bond characters, respectively, being consistent with the phenol–imine tautomeric form.The title compound crystallizes in the phenol–imine tautomeric form with an le Fig. 1, which iA⋯π (C9–C14) interactions  = 4.0220 (9) Å] lead to additional stabilization of the crystal packing. A view of the crystal packing parallel to the bc plane is shown in Fig. 2In the crystal, molecules are linked by C16—H16s Table 1, and veret al., 2016Z)-2-{[imino]methyl}-4-methylphenol unit, revealed ten hits where this fragment adopts the enol–imine tautomeric form. The imine bond length (N1—C7) in the title compound is the same within standard uncertainties as the corresponding bond lengths in the structures of 2-(diphenylmethyl)-6-[(mesitylimino)methyl]-4-methylphenol -N,N′-bis-5,5′,6,6′,7,7′,8,8′-octahydro-1,1′-binaphthyl-2,2′-diamine methyl]phenolato}tetrahydrofuranmagnesium imino]methyl}phenol  to 1.1632 Å (blue) . In Figs. 2normd and ed surfaces represent the C—H⋯Cg interactions. The most important interaction is H⋯H, contributing 65% to the overall crystal packing, which is illustrated in the 2D fingerprint -2-{[imino]methyl}-4-methylphenol was synthesized by condensation of 2-hydroxy-5-methylbenzaldehyde and 2,4-dimethylaniline  = 1.5Ueq(O). The C-bound H atoms were positioned geometrically and refined using a riding model with C—H = 0.93 and Uiso(H) = 1.2Ueq(C) for sp2-hybridized C atoms and with C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989021010215/yk2157sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021010215/yk2157Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021010215/yk2157Isup3.cmlSupporting information file. DOI: 2113562CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


Their structures with absolute configurations were elucidated by extensive spectroscopic methods. Compounds 1–3 showed antibacterial activity against four strains with MIC values in a range of 16–128 μg/mL.Five previously undescribed guanacastane diterpenoids, namely psathyrellins A–E (The online version contains supplementary material available at 10.1007/s13659-021-00316-x. Psathyrella candolleana (Psathyrellaceae) is a small agaric usually found in the vicinity of recently dead hardwood trees. It has a wide distribution on lawns or pastures in Europe and North America. Previous pharmacological studies indicated that the extracts of P. candolleana showed a marked anticlastogenic effect against DNA damage + . The UV data at 282 nm suggested a conjugated system in 2. The 1D and 2D NMR spectra revealed similar patterns to those of 1 except that one more double bond in 2. In the HMBC spectrum, correlations from δH 1.11  to δC 142.8  and 158.6 , from δH 6.99  to C-1 and δC 158.6 , and from δH 1.74  to C-3 and δC 131.5  suggested that three double bonds were distributed at C-12/C-13, C-1/C-2, and C-3/C-4, respectively. Detailed analysis of 2D NMR data suggested that the other parts of 2 were the same to those of 1. A single crystal X-ray diffraction not only proved the planar structure, but also determined the absolute configuration of 1 as shown in Fig. Psathyrellin B (3) was isolated as a yellow oil. The molecular formula was determined as C20H28O5 on the basis of HRESIMS data at m/z 349.20093 [M + H]+ . All NMR data suggested that 3 was structurally similar to that of 2  was isolated as a yellow oil. The molecular formula was determined as C22H28O6 on the basis of HRESIMS data at m/z 411.17749 [M + Na]+ . All spectroscopic data of 4 were similar to those of 2 excepted two additional carbons at δC 20.8 (q) and 172.8 (s) in 4 that were easily assigned as an O-acetyl moiety. The HMBC correlations from δH 4.40 and 4.30 to δC 172.8 (s) and from δH 1.27  to δC 32.3 , 67.1  suggested that the O-acetyl moiety should be placed at C-19. Detailed analysis of 2D NMR data suggested that the other parts of 4 were the same to those of 2. The CD spectrum almost showed the same curve to that of 2, indicating the absolute configuration of the main backbone in 4 to be the same to that of 2  was isolated as a yellow oil. The molecular formula was determined as C22H28O5 on the basis of HRESIMS data at m/z 373.20084 [M + H]+ . According to analysis of 1D and 2D NMR data, compound 5 was easily identified as a 19-O-acetyl derivative of 2, which was also similar to 4. The only difference was that the hydroxymethine of C-6 in 4 was reduced into a methylene at δC 34.5  in 5, as supported by the HMBC correlation from H-6 to C-5 and the 1H–1H COSY data between H-6 and H-7. The CD spectrum almost indicated the same curve to that of 2, indicating the absolute configuration of the backbone in 5 to be the same to that of 2  and a Dionex UltiMate 3000 RSLC UPLC system. Silica gel (200–300 mesh and 500–800 mesh), RP-18 gel (40–75 µm) and Sephadex LH-20 were used for column chromatography (CC). Preparative HPLC was performed on an Agilent 1260 liquid chromatography system with a Zorbax SB-C18  column, a Daicel chiral column  and a DAD detector.Optical rotations were measured on a Rudolph Autopol IV polarimeter. UV spectra were obtained on a UH5300 UV–VIS Double Beam Spectrophotometer. IR spectra were obtained by using a Shimadzu Fourier Transform Infrared spectrometer with KBr pellets. NMR spectra were acquired with a Bruker Avance III 600 instrument. CD spectra were recorded with an Applied Photophysics Chirascan-Plus spectrometer. High resolution electrospray ionization mass spectra (HRESIMS) were recorded on a LC–MS system consisting of a Q Exactive™ Orbitrap mass spectrometer with an ESI ion source used in ultra-high resolution mode  was deposited at School of Pharmaceutical Sciences, South-Central University for Nationalities. The strains were cultured in PDA and stored at − 4 °C. Culture medium was composed of glucose (5%), pork pepton (0.15%), yeast (0.5%), KH2PO4 (0.05%) and MgSO4 (0.05%). Initial pH was adjusted to 6.0, the fermentation was first carried out on an erlenmeyer flask for 6 days till the mycelium biomass reached to the maximum. Then it was transferred to rice medium at 24 °C in dark culture for 40 days. The rice medium in each 250 mL-Erlenmeyer flask was composed of rice (50 g) and water (50 mL). A total of 180 bottles were used in this study.Fruiting bodies of 2CO (from 20:1 to 1:1) to afford eight fractions A–H. Fraction C (3.8 g) was isolated by CC over silica gel using PE/Me2CO (6/1) to give subfractions C1–C6. Compound 1 was deposited from fraction C4 as colorless crystals . Fraction E (4 g) was first isolated by silica gel CC (200–300 mesh) eluted with PE/Me2CO (5/1) to give five subfractions E1-E5. Fraction E2 (800 mg) was further isolated by CC using RP-C18 silica gel (MeOH/H2O from 6/4 to 9/1) to give subfractions E2a-E2e. HPLC preparation (MeCN/H2O from 7/3 to 8/2 in 20 min) on fraction E2d (82 mg) afforded compounds 3  = 12.1 min; purity 90%), 4 , and 2 . Fraction E2e (70 mg) was separated by CC over Sephadex LH-20 (MeOH) to give a mixture. The mixture was subjected to HPLC (MeCN/H2O from 7/3 to 8/2 in 20 min) to give compound 5 .The rice fermentation (9 kg) was extracted four times with EtOAc. The organic layer was evaporated to give a crude extract (90 g). The extract was subjected to silica gel CC (200–300 mesh) eluted with a gradient solvent system of petroleum ether (PE)/Meα]D15 – 208.1 ; UV (MeOH) λmax (log ε) 192 (3.36), 244 (3.18) nm; IR (KBr) νmax 3421, 3349, 2829, 1710, 1702, 1640, 1462, 1038 cm−1; 1H (600 MHz) and 13C NMR (150 MHz) data (methanol-d4), see Table m/z 333.20584 [M + H]+ .Colorless crystals (MeOH); [α]D15 – 239.2 ; UV (H2O) λmax (log ε) 190 (3.34), 252 (3.20), 282 (2.86) nm; ECD (MeOH) λmax (Δε) 223 (+49), 251 (+45), 287 (–39), 339 (–27) nm; IR (KBr) νmax 3432, 3346, 2910, 1711, 1706, 1642, 1446, 1036 cm−1; 1H (600 MHz) and 13C NMR (150 MHz) data (methanol-d4), see Table m/z 331.19031 [M + H]+ .Colorless crystals (MeOH); [α]D15 – 182.9 ; ECD (MeOH) λmax (Δε) 209 (–33), 224 (+26), 287 (–29), 341 (–8) nm; 1H (600 MHz) and 13C NMR (150 MHz) data (methanol-d4), see Table m/z 349.20093 [M + H]+ .Yellow oil; [α]D15 – 221.9 ; ECD (MeOH) λmax (Δε) 222 (+20), 243 (+22), 287 (–15), 338 (–12) nm; 1H (600 MHz) and 13C NMR (150 MHz) data (methanol-d4), see Table m/z 411.17749 [M + Na]+ .Yellow oil; [α]D15 – 292.4 ; ECD (MeOH) λmax (Δε) 221 (+27), 242 (+31), 290 (–24), 338 (–18) nm; 1H (600 MHz) and 13C NMR (150 MHz) data (methanol-d4), see Table m/z 373.20084 [M + H]+ .Yellow oil; . The final wR(F2) values were 0.0799 [I > 2σ(I)]. The final R1 values were 0.0307 . The final wR(F2) values were 0.0800 . The goodness of fit on F2 was 1.056. Flack parameter = 0.05(3). CCDC: 2068966 (www.ccdc.cam.ac.uk).C20H26O4, M = 330.41, a = 8.0026(8) Å, b = 8.3729(9) Å, c = 14.4078(15) Å, α = 90.00°, β = 105.783(3)°, γ = 90.00°, V = 929.00(17) Å3, T = 150.(2) K, space group P1211, Z = 2, μ(CuKα) = 1.54178 mm−1, 12059 reflections measured, 3552 independent reflections (Rint = 0.0456). The final R1 values were 0.0559 [I > 2σ(I)]. The final R1 values were 0.0415 . The final wR(F2) values were 0.1156 . The goodness of fit on F2 was 1.092. Flack parameter = − 0.12(14). CCDC: 2068967 (www.ccdc.cam.ac.uk).CEscherichia coli ATCC25922, Staphylococcus aureus subsp. aureus ATCC29213, Salmonella enterica subsp. enterica ATCC14028, Pseudomonas aeruginosa ATCC27853 were purchased from China General Microbiological Culture Collection Center, (CGMCC). All these strains were cultured in Mueller Hinton broth (MHB)  at 37 °C overnight with shaking (200 rpm). A sample of each culture was then diluted 40-fold in fresh MHB broth and incubated with shaking (200 rpm) at 37 °C for 2.5 h. The resultant mid-log phase cultures were diluted to a concentration of 5 × 105 CFU/mL, then 50 mL was added to each well of the compound-containing plates. The minimum inhibition concentration (MIC) was determined by measuring bacterial growth after 24 h on performing 1:2 serial dilutions of each compound ranging from 1 to 128 μg/mL. Chloramphenicol was used as a positive control.The tested bacteria strains Supplementary file1 (PDF 2820 KB)Supplementary file2 (CIF 1031 KB)Supplementary file3 (CIF 379 KB)Below is the link to the electronic supplementary material.


In the crystal, the molecules are assembled into two-dimensional layers  33H28N2O4, comprises an indole unit (A), an isoquinoline moiety (B) and a benzene ring (C). The dihedral angles between these groups are A/B = 57.47 (1), A/C = 18.48 (1) and B/C = 57.97 (1) °. The ethyl acrylate group at the 2-position is nearly co-planar with the indole unit [3.81 (2)°], while that at the 7-position is distinctly non-coplanar [52.64 (1)°]. Intramolecular π–π interactions between the indole unit and benzene ring help to establish the clip-shaped conformation of the molecule. In the crystal, the molecules are assembled into two-dimensional layers via C—H⋯O hydrogen bonds, π–π and C—H⋯π interactions. Hirshfeld surface analysis illustrates that the greatest contributions are from H⋯H (63.2%), C⋯H/H⋯C (15.4%) and O⋯H/H⋯O (14.8%) contacts. The terminal C2H5 group of one of the ethyl acrylate side chains is disordered over two positions of equal occupancy.The molecule of title compound, C The benzene ring is almost parallel to the indole unit and hence intramolecular π–π interactions  are observed within the layers  to 1.7889 (blue) a.u. -diacrylate -8-phenylisoquinoline (0.20 mmol), Pd(OPiv)2 , L quinoline; 11.3 mg, 20 mol%], CuO  and Cu(OTf)2  and the tube was purged with O2 three times, followed by addition of ethyl acrylate (1.0 mmol) and anhydrous DCE . The formed mixture was stirred at 353 K under Ar for 24 h as monitored by TLC. The solution was then cooled to room temperature, and the solvent was removed under vacuum. The crude product was purified by column chromatography on silica gel to afford the pure product (55% yield). The recrystallization of the title compound in methanol afforded yellow block-shaped crystals. The synthesis is shown in Fig. 6To a 10 mL Schlenk tube was added indole substrate 1-(1Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-methyl). Atoms C32 and C33 were refined as disordered over two partially occupied positions of equal occupancy.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989021007829/zn2008sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021007829/zn2008Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021007829/zn2008Isup3.cmlSupporting information file. DOI: 2100362CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-020-76496-2, published online 11 November 2020Correction to: Ca,L, SR Ca2+ content and Ca2+ transient measurements’.This Article contains errors in the Results section under subheading ‘The I2+ content and found that SR Ca2+ content was significantly increased in the trained group compared to controls (− 1.84 ± 0.4 (pA*s)/pF vs − 1.25 ± 0.5 (pA*s)/pF n = 8/5 and 8/4, respectively, p < 0.05; Fig. 6b).”“We analyzed the integral of caffeine-induced NCX currents as an indicator of the SR Cashould read:2+ content and found that SR Ca2+ content was significantly increased in the trained group compared to controls (− 1.84 ± 0.4 (pA*s)/pF vs − 1.25 ± 0.5 (pA*s)/pF n = 8/5 and 8/5, respectively, p < 0.05; Fig. 6b).”“We analyzed the integral of caffeine-induced NCX currents as an indicator of the SR CaSecondly, this Article contains an error in Figure 6 where the experimental numbers of the control columns are incorrect (8/4) in panel (b). The correct Figure 6 appears below as Figure


The asymmetric unit contains one-half of the formula unit of the title compound. The crystal structure is stabilized by intermolecular C—H⋯O, C—H⋯Cl and C—Cl⋯π interactions, and short intermolecular Cl⋯O and Cl⋯Cl contacts, forming a three-dimensional network. 24H16Cl12N2O4, is generated by a crystallographic inversion centre at the midpoint of the central C—C bond. A kink in the molecule is defined by a torsion angle of −169.86 (15)° about this central bond of the alkyl bridge. The pyrrolidine ring is essentially planar [max. deviation = 0.014 (1) Å]. The cyclohexane ring has a boat conformation, while both cyclopentane rings adopt an envelope conformation. In the crystal structure, molecules are linked by intermolecular C—H⋯O, C—H⋯Cl and C—Cl⋯π interactions, and short intermolecular Cl⋯O and Cl⋯Cl contacts, forming a three-dimensional network.The molecule of the title compound, C N-heterocyclic compounds are of interest in the fields of synthetic organic chemistry, coordination chemistry and medicinal chemistry because of their important biological properties -4,5,6,7,8,8-hexachloro-2-{6-hexyl}-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione, which provides multiple inermolecular non-covalent interactions.QT = 0.9300 (14) Å, θ = 89.99 (9)°, φ = 59.37 (9)°], while both the cyclopentane rings (C2–C6 and C3–C5/C8/C9) adopt an envelope conformation  with the C4 atom bearing the dichloromethane group as the flap.The molecule of the title compound is generated by a crystallographic inversion centre at the midpoint of the central C—C bond. A kink in the molecule is defined by the C10—C11–C12—C12_a torsion angle of −169.86 (15)° about this central bond of the alkyl bridge Fig. 1. The pyrIn the crystal structure, molecules are linked by intermolecular C—H⋯O, C—H⋯Cl and C—Cl⋯π interactions Table 1, and shoCrystal Explorer 17.5 , Cl⋯Cl , O⋯H/H⋯O , Cl⋯O/O⋯Cl  and H⋯H  interactions. The remaining other weak interactions (contribution percentages) are Cl⋯C/C⋯Cl (3.2%), Cl⋯N/N⋯Cl (1.4%) and C⋯H/H⋯C (0.2%).In order to visualize the intermolecular interactions Table 2 in the cet al., 2016H-4,7-methanoisoindole-1,3(2H)-dione -2-(perfluoropyridin-4-yl)-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione -2-[(perfluoropyridin-4-yl)oxy]-3a,4,7,7a-tetrahydro-1H-4,7-methanoisoindole-1,3(2H)-dione ° with the 3,4-dimethoxyphenyl ring, which are attached to each other by an extended N—CHIn the crystal of QOVCAH, the cyclohexene ring adopts a boat conformation, and the five-membered rings have envelope conformations with the bridging atom as the flap. Their mean planes are oriented at a dihedral angle of 86.51 (7)°. The molecular structure is stabilized by a short intramolecular C—H⋯O contact. In the crystal, molecules are linked by O—H⋯O hydrogen bonds, forming chains propagating along [100]. The chains are linked by C—H⋯π interactions, forming slabs parallel to (001).PA and B, in the asymmetric unit, and MOJGAW in the monoclinic space group P21/n with one molecule per asymmetric unit. The synthesis of both compounds is conducted using endo starting materials, and the same configuration is observed in the resulting crystal structures. In MOJFUP, steric interactions between the ortho-fluorine atoms and the carbonyl oxygen atoms prevents free rotation about the nitrogen–ipso-carbon bond, which is evidenced by separate 19F NMR peaks in solution for the ortho-F atoms. In molecule A, the 2,3,5,6-tetrafluoropyridine plane is rotated by 58.05 (5)° relative to the pyrrolidine plane and the corresponding dihedral angle for molecule B is 61.65 (7)°. The addition of an oxygen atom between N and C in the bridge between the ring systems in MOJGAW alleviates this steric restriction and only one 19F NMR peak in solution is observed for the ortho-F atoms; even so, the dihedral angle between the 2,3,5,6-tetrafluoropyridine and pyrrolidine planes in the crystal of MOJGAW of 84.01 (5)° is larger than that found in MOJFUP.The compound MOJFUP crystallizes in the triclinic space group The main directional interactions in the crystal structures of MOJFUP and MOJGAW are of the type C—H⋯O, C—H⋯F, C—O⋯π, and C—F⋯π. In both compounds, weak hydrogen-bonding interactions are observed for the hydrogen atom(s) α to the carbonyl groups  and the olefinic hydrogen atoms . A weak interaction is also observed for a bridge hydrogen atom in MOJGAW, C—H⋯F. The packing is further aided by π-interactions with the pyridine ring in MOJGAW.R,4R,7R,7aS)-4,5,6,7,8,8-hexachloro-3a,4,7,7a-tetrahydro-4,7-methanoisobenzofuran-1,3-dione were added 0.12 mL (1 mmol) of hexane-1,6-diamine and 25 mL of dimethylformamide, and the mixture was stirred for 6 h at 373 K. Then, the reaction mixture was cooled to room temperature and poured into cold water. The obtained precipitate was filtered off, washed with water, recrystallized from chloroform and dried under vacuum. Yellow powder, yield 92%, m.p 404–405 K (decomp.). Analysis calculated for C24H16Cl12N2O4 (Mr = 821.80): C 35.08, H 1.96, N 3.41%; found: C 35.03, H 2.00, N 3.35%. ESI–MS: m/z: 822.9 [Mr + H]+. 1H NMR (300.130 MHz) in acetone-d6, internal TMS, δ (ppm): 1.29–3.43 , 3.86 . 13C{1H} NMR . δ: 25.8 (2CH2), 27.2 (2CH2), 39.3 (4C–H), 52.0 (2CH2), 79.3 (4CCl), 104.4 (2CCl2), 130.9 (2ClC=CCl) and 170.2 (4C=O). Off-white prismatic crystals suitable for X-ray analysis were obtained by slow evaporation of a chloroform–hexane  mixture.To 741 mg (2 mmol) of (3aUiso(H) = 1.2Ueq(C). Two reflections (100 and 002), affected by the incident beam-stop, and owing to poor agreement between observed and calculated intensities, two outliers (136 and 118) were omitted in the final cycles of refinement. Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989021006952/vm2251sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021006952/vm2251Isup2.hklStructure factors: contains datablock(s) I. DOI: 2094787CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure of the free base of the ubiquitous neurotransmitter serotonin is reported for the first time. H-indol-5-ol], C10H12N2O, has one molecule in the asymmetric unit. The conformation of the ethylamino side chain is gauche–gauche . In the crystal, the molecules are linked into a three-dimensional network by N—H⋯O and O—H⋯N hydrogen bonds.The title compound, serotonin or 5-hydroxytryptamine (5-HT) [systematic name: 3-(2-aminoethyl)-1 The ethylamino arm itself turns back toward the indole ring with a C8—C9—C10—N2 torsion angle of −61.9 (2)°.Serotonin or 5-hydroxytryptamine (5-HT) is an indolamine with a 5-hydroxy substitution. In the solid state, serotonin crystallizes with one molecule in the asymmetric unit Fig. 1 in the cA⋯O1 hydrogen bonds. Half of the amine H atoms link to the hydroxy groups of nearby molecules through N2—H2B⋯O1 hydrogen bonds. There are no observed π–π stacking interactions. Fig. 2In the crystal, the serotonin molecules are linked by a series of hydrogen bonds that produce a three-dimensional network in the solid state. The hydroxy groups form hydrogen bonds to the amine N atoms on an adjacent serotonin molecules forming O1—H1⋯N2 hydrogen bonds. The indole N atoms form hydrogen bonds to the hydroxy groups of adjacent serotonin molecules through N1—H110H13N2O+ cationic form. These include the creatine sulfate monohydrate .A, H2A and H2B were found from a difference-Fourier map and were refined isotropically, using DFIX restraints with an N—H(indole) distance of 0.87 (1) Å, N—H(amine) distances of 0.90 (1) Å, and an O—H distance of 0.86 (1) Å. Isotropic displacement parameters were set to 1.2 Ueq of the parent nitrogen atoms and 1.5 Ueq of the parent oxygen atom. All other hydrogen atoms were placed in calculated positions with C—H = 0.93 Å (sp2) or 0.97 Å (sp3). Isotropic displacement parameters were set to 1.2 Ueq of the parent carbon atoms. The absolute structure of the crystal chosen for data collection was indeterminate in the present refinement.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989022002559/hb8014sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989022002559/hb8014Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022002559/hb8014Isup3.cmlSupporting information file. DOI: 2156646CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]benzamide and its 4-methoxy derivative highlights the significance of strong and weak hydrogen bonds. The difference in the contributions of atom–atom contacts obtained from Hirshfeld surface analysis and fingerprint plots helps in distinguishing the variations in the crystal packing of the two compounds.Crystal structure analysis of  N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]benzamide, C21H16FN3O3S, crystallizes in the monoclinic centrosymmetric space group P21/c and its molecular conformation is stabilized via an intramolecular N—H⋯O hydrogen bond. The corresponding para-methoxy derivative, namely, N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]-4-methoxybenzamide, C22H18FN3O4S, crystallizes in the monoclinic centrosymmetric space group C2/c. The supramolecular network mainly comprises N—H⋯O, N—H⋯S and C—H⋯O hydrogen bonds, which contribute towards the formation of the crystal structures for the two molecules. The different intermolecular interactions have been further analysed using Hirshfeld surface analysis and fingerprint plots.The compound  R–(C=O)–NH–NH–(C=S)–R′ and find application in the synthesis of five- and six-membered heterocyclic compounds hydrazinecarbothioyl]benzamide (A1) and N-[2-(4-fluoro-3-phenoxybenzoyl)hydrazinecarbothioyl]-4-methoxybenzamide (A2) in the current study. The molecular conformations have been studied with respect to the various flexible bonds and the occurrence of various intermolecular interactions that contribute towards the stability of the molecules in the crystalline lattice has been investigated in detail via an investigation of the crystal packing and quantitative insights from Hirshfeld surface analysis.Substituted thiosemicarbazides (TSCs) constitute an important class of organic compounds with the general formula P21/c space group and A2 crystallizes in the centrosymmetric monoclinic C2/c space group. The molecular structure comprises one fluoro-substituted phenoxybenzoyl ring, a rigid and planar (C=O)—NH—NH—(C=S) moiety and a benzamide ring. The bond lengths and bond angles are in accordance with the magnitudes in the literature. The molecular conformations of A1 , the N2⋯O3 distance being 2.555 (2) and 2.589 (4) Å in A1 and A2, respectively. The molecular structure possesses four conformational degrees of freedom due to the free rotation with respect to the N1—N2, C7—O1, O1—C1 and C15—C16 single bonds. The torsion angles C13—N1—N2—C14, C8—C7—O1—C1, C7—O1—C1—C2 and N3—C15—C16—C21 are 163.27 (16)/-143.5 (4)°, 97.3 (2)/149.6 (5)°, 167.18 (18)/148.1 (4)° and −160.26 (15)/-174.7 (3)° in A1/A2, respectively.Compound A1 crystallizes in the centrosymmetric monoclinic A1 Fig. 1 and A2 , [3.384 (4) Å, 174.9 (1)°, −x + 1, y + 1, −z + In the crystal structure of A1, the molecules are primarily assembled through the presence of N3—H3s Table 1, formingnt Fig. 3. AdjacenA2 Fig. 4 primarilA2 Fig. 4, formingng Fig. 4. Intermet al., 2016A search for the dibenzoylthiosemicarbazide skeleton, Ph–(C=O)–NH–NH–(C=S)–NH–(C=O)–Ph was carried out in the Cambridge Structural Database , and A2, Fig. 5b) and 5(c), show the important hydrogen bonds. The red and blue spots correspond to intermolecular interactions that are less or greater than the sum of the van der Waals radii. The fingerprint plots depict the individual contributions of the different interactions. The fingerprint plots for A1/A2  = 1.2Ueq or 1.5Ueq(C-methyl).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989021001900/dj2021sup1.cifCrystal structure: contains datablock(s) A1, A2. DOI: 10.1107/S2056989021001900/dj2021A1sup2.hklStructure factors: contains datablock(s) A1. DOI: 10.1107/S2056989021001900/dj2021A2sup3.hklStructure factors: contains datablock(s) A2. DOI: Click here for additional data file.10.1107/S2056989021001900/dj2021A1sup4.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021001900/dj2021A2sup5.cmlSupporting information file. DOI: 2063226, 2063225CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: