A study of their luminescence properties indicates that co-crystals 1 and 2 exhibit distinctly different luminescence in the solid state at room temperature.Two new co-crystals of tetraiodoethylene with two azaphenanthrenes were successfully synthesized. In the crystals, C—I⋯ 2I4·C13H9N (1) and tetraiodoethylene–benzo[f]quinoline (1/2), 0.5C2I4·C13H9N (2), were obtained from tetraiodoethylene and azaphenanthrenes, and characterized by IR and fluorescence spectroscopy, elemental analysis and X-ray crystallography. In the crystal structures, C—I⋯π and C—I⋯N halogen bonds link the independent molecules into one-dimensional chains and two-dimensional networks with subloops. In addition, the planar azaphenanthrenes lend themselves to π–π stacking and C—H⋯π interactions, leading to a diversity of supramolecular three-dimensional structural motifs being formed by these interactions. Luminescence studies show that co-crystals 1 and 2 exhibit distinctly different luminescence properties in the solid state at room temperature.Two new co-crystals, tetraiodoethylene–phenanthridine (1/2), 0.5C Halogen bonding (XB) is a powerful tool to assemble supramolecular materials and to promote chemical or biological molecular recognition , which is expected to tune their luminescence behaviour via a change of the co-crystal structures. Single crystal X-ray diffraction (XRD) data reveal that the two co-crystals of TIE with PHN and BfQ reported here have interesting structural properties and exhibit different luminescence behaviour from previous reports. TIE as a quadridentate XB donor allows the formation of three-dimensional halogen-bonded networks with XB acceptors, PHN and BfQ. Using the conventional solution-based method, yellow co-crystals suitable for XRD measurement were obtained. The crystal structures of the co-crystals are mainly constructed by C—I⋯π and C—I⋯N halogen bonds. Other multiple intermolecular interactions, such as π–π stacking, C—H⋯π, C—H⋯I as well as C—H⋯H—C interactions, are also observed in the co-crystals.Nitrogen heteroaromatic rings are a common type of luminescence or luminescent precursor materials. However, in general, it is difficult to use them to generate phosphorescence or delayed fluorescence. Haloperfluorobenzenes, as XB donors, have been used in attempts to assemble luminescence co-crystals with azaphenanthrenes . The I1⋯N1i distance is 2.864 (7) Å and the corresponding C14–I1⋯N1i angle is 172.8 (2)° . The strong C14—I1⋯N1 halogen bond results in a I1⋯C13i distance [3.553 (8) Å] shorter than the sum of the van der Waals radii, which indicates a C1—I1⋯C13 halogen interaction. In addition, the C14—I2⋯C9ii/C10ii C—I⋯π separations  are 3.432 (9) and 3.612 (8) Å, and the corresponding bond angles are 165.6 (2) and 156.7 (2)°, respectively. Furthermore, π–π stacking  and C—H⋯H—C interactions between two adjacent PHN molecules contribute to the extension of the two-dimensional network into a three-dimensional supramolecular structure , I1⋯C1 = 3.641 (5), I2⋯C13 = 3.436 (5) and I2⋯C8 = 3.733 (4) Å, respectively] in co-crystal 2 are all a little longer (0.004–0.121 Å) than in 1 . In addition, the two-dimensional network  Å, Cg1⋯Cg2ii = 3.963 (2) Å, Cg1⋯Cg3ii = 3.746 (3) Å, Cg2⋯Cg2ii = 3.768 (2) Å; Cg1, Cg2 and Cg3 are the centroids of rings N1/C1–C5, C4–C9 and C8–C13, respectively; symmetry codes: (i) 1 − x, 1 − y, 1 − z; (ii) 1 − x, −y, 1 − z] and C—H⋯I hydrogen bonds  in the 2θ range of 5 to 50°. As shown in Fig. 61 and 2 match well with the spectra simulated from the XRD data, which confirms the purity of 1 and 2.The powder X-ray diffraction (PXRD) experiments were carried out for the title co-crystals using a Bruker D8-ADVANCE X-ray diffractometer  state to drop below that of the 3 state. It is supposed that for the singlet states the 0–0 transition of emitters in co-crystals is localized at 375 nm and 450 nm, respectively, and for triplet states the 0–0 transition is at about 600 nm. The energy gap between S1 and T1 is largely greater than 20 kJ mol−1, so the delayed fluorescence most likely originates from the triplet–triplet annihilation process, named P-type delayed fluorescence (P-DF). Both delayed fluorescence and phosphorescence are relative to triplet states, so they should be significant for improving the exciton emission efficiency of luminescence materials  are about 10 ns, while the delayed fluorescence lifetime (4.36 µs for 1 and 6.45 µs for 2) is less than the 10 µs level because of the strong heavy-atom effect leading to a faster decay of the triplet state. Additionally, the phosphorescence is too weak to measure its decay lifetime. However, the phosphorescence lifetime can be estimated to be about 20 µs based on the relationship between P-DF and the accompanying phosphorescence  measurements were obtained by slow evaporation of the solvent at room temperature after about two weeks. Elemental analysis  calculated for C14H9NI2 (445.02): C 37.78, H 2.04, N 3.15. Found: C 37.54, H 2.31, N 3.26. For co-crystal 1, and C 37.85, H 2.16, N 3.04 for co-crystal 2. IR  For 1: 3048(w), 1603(w), 1572(w), 1494(m), 1446(w), 1382(m), 1293(m), 1267(m), 1189(m), 1089(m), 948(m), 870(s), 832(s), 802(s), 749(s), 707(s), 615(m), 538(m), 487(m), 435(m). For 2: 3048(w), 1611(w), 1576(s), 1522(w), 1486(w), 1458(m), 1440(m), 1238(m), 1132(m), 1032(m), 953(m), 924(m), 889(s), 745(s), 714(s), 610(m), 552(m), 448(m), 423(m).0.1 mmol of PHN/BfQ and 0.05 mmol of TIE were dissolved in an acetone/chloroform (2:1) mixture in a glass vial. Well–formed co-crystals Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989020002182/vm2225sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989020002182/vm22251sup4.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989020002182/vm22252sup5.hklStructure factors: contains datablock(s) 2. DOI: 1899078, 1899077CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The three para-phenylene rings bonded to the N atom are in a propeller form. All of the naphthalene ring systems are slightly bent. In the crystal, molecules form an inversion dimer, through two pairs of C—H⋯π interactions, which further interacts with the adjacent dimer via another two pairs of C—H⋯π interactions, forming a column structure along the a axis. There are no significant interactions between these column structures.In the title molecule, C The torsion angles C3—C2—N1—C34, C19—C18—N1—C2 and C35—C34—N1—C18 are −35.0 (2), −60.6 (2) and −30.3 (2)°, respectively. The para-phenylene ring and the mean plane of the neighboring naphthalene ring system are inclined to each other by 54.66 (7)° for (C2–C7)/(C8–C17), 48.80 (7)° for (C18–C23)/(C24–C33) and 56.21 (7)° for (C34–C39)/(C40–C49).The molecular structure of the title compound is shown in Fig. 1via four intermolecular C—H⋯π interactions  −x + 1, −y, −z + 2], forming an inversion dimer  −x, −y, −z + 2] , which included eleven hits (nine compounds) with heteroaromatic rings and eight hits (seven compounds) with phenyl rings. The seven compounds with phenyl rings at the three para-position of the triphenylamine skeleton include tris(biphenyl-4-yl)amine [WEHLIE phenyl]amine , toluene (42 mL) and water (10.4 mL) were placed in a 100 mL round-bottom flask. After the solution was purged with nitrogen for 10 minutes, it was heated at 373 K under nitrogen for 24 h. The reaction mixture was extracted with ethyl acetate. After drying over anhydrous Na2SO4, the organic layer was evaporated. The residue was redissolved in a small amount of ethyl acetate. The addition of a large amount of methanol gave the pure product as a white precipitate . Colorless single crystals suitable for X-ray diffraction were obtained by means of the vapor diffusion method from chloroform as a rich solvent and n-hexane as a poor solvent after standing for one week.The title compound was prepared by a modification of the previously reported Suzuki–Miyaura coupling reaction (Kwon Uiso(H) = 1.2Ueq(C). One outlier (011) was omitted from the refinement.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020012529/is5556sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020012529/is5556Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020012529/is5556Isup3.cmlSupporting information file. DOI: 2031765CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Biological screening showed these compounds as good inhibitors for several glycosidases. Especially  Glycosidases are involved in many important biological processes, and inhibitors of glycosidases –3 are diAn extended search in literature as of 2020, October, revealed there are some 30,600 structures containing the substructure of a 6-amino-6-deoxy-hexopyranose (or -pyranoside). Monofluorinated analogs, however, have scarcely been prepared  –37—but t1 D = +39.9° ]; Rƒ  = 0.53; analysis calcd for C23H26O6 (398.45): C 69.33, H 6.58; found: C 69.09, H 6.63.Data for C ; Rƒ  = 0.63; analysis calcd for C23H26O6 (398.45): C 69.33, H 6.58; found: C 69.17, H 6.71.Data for C (lit.:  124 °C);1  in dry DCM (40.0 mL) while maintaining the temperature at −78 °C. The mixture was stirred for 2 h at −78 °C, then a solution of Et3N  in dry DCM (40.0 mL) was added dropwise. The mixture was stirred at −78 °C for another 30 min and at 25 °C for 12 h. Usual aqueous workup followed by chromatography  gave 2  as a white solid; MP 130–132 °C; [α]D = −47.95° ; Rƒ  = 0.40 (ketone); Rƒ  = 0.19 (hydrate); analysis calcd for C23H24O6 (396.43): C 69.68, H 6.10; found: C 69.43, H 6.27.To a solution of dry DMSO  in dry DCM (40.0 mL) at −78 °C, a solution of trifluoroacetic anhydride  in dry DCM (10.0 mL) was slowly added dropwise, and the mixture was stirred at this temperature for 45 min followed by adding a solution of 2  in dry DCM (6.0 mL), DAST (417 μL 3.03 mmol) was added dropwise under argon, and the mixture was stirred at 25 °C for 5 days. Methanol (1.0 mL) was carefully added, and the solvents were removed under diminished pressure. The oily residue was dissolved in DCM (90 mL) and washed with water (50 mL). The aqueous phase was re-extracted with DCM (3 × 100 L); the organic layers were combined, and the solvent was evaporated under reduced pressure. The remaining residue was subjected to chromatography  to afford 3  as a white solid; MP 79–81 °C; [α]D = −26.10°  Rƒ  = 0.75; analysis calcd for C23H24O5F2 (418.43): C 66.02, H 5.78; found: C 65.85, H 5.92.To a solution of 3  in dry ether (30 mL) and THF (30 mL), lithium aluminum hydride  was added in several portions, and the suspension was stirred for 15 min at 25 °C. Then, the suspension was heated to reflux, and a solution of dry aluminum chloride  in dry ether (30 mL) was added dropwise followed by stirring under reflux for another 48 h. The suspension was cooled to 25 °C, methanol (30 mL) was carefully added, and stirring was continued for another 30 min. After usual aqueous workup followed by chromatography  4  and 5  were obtained each as a colorless oil.To an ice-cold solution of 4: [α]D = −48.23° ; Rƒ  = 0.51; analysis calcd for C23H26O5F2 (420.45): C 65.70, H 6.23; found: C 65.55, H 6.40.Data for 5: [α]D = −18.27° ; Rƒ  = 0.41; analysis calcd for C23H26O5F2 (420.45): C 65.70, H 6.23; found: C 65.47, H 6.39.Data for 5  in toluene (30 mL) containing triphenylphosphane  and imidazole , iodine  was added in several portions. After stirring at 90 °C for 2 h, the reaction mixture was decanted, and the remaining oil was washed with ether (3 × 100 mL). The combined organic layers were evaporated, and the remaining residue was subjected to chromatography  to afford 6  as a colorless oil; [α]D = −25.32° ; Rƒ  = 0.56; analysis calcd for C23H25O4F2I (530.34): C 52.09, H 4.75; found: C 51.84, H 4.92.To a solution of 6  in dry DMF (19 mL) a solution of lithium azide  was added at 25 °C, and the solution was stirred at this temperature for 4 days. The solvents were removed under diminished pressure, and the remaining residue was dissolved in DCM (100 mL) and water (50 mL). The aq. phase was extracted with DCM (3 × 100 mL), and the combined organic layers were dried (Na2SO4). The solvent was removed under reduced pressure, and the remaining residue was subjected to chromatography  to afford 7  as a colorless oil; [α]D = −33.01° ; Rƒ  = 0.39; analysis calcd for C23H25O4F2N3 (445.44): C 62.01, H 5.66, N 9.43; found: C 61.80, H 5.81, N 9.25.To a solution of 7  in dry MeOH (20.0 mL) containing palladium on charcoal  was hydrogenated . The solution was filtered through a pad of Celite; the pad was rinsed with methanol (4 × 50 mL). The combined organic layers were dried (MgSO4), the solvent was removed under reduced pressure, and the residue was subjected to chromatography  to afford 8  as a white foam; [α]D = −20.26° ; Rƒ  = 0.14; analysis calcd for C9H17O4F2N (241.23): C 44.81, H 7.10, N 5.81; found: C 44.69, H 7.32, N 5.69.A solution of 9  in dry dichloromethane (40.0 mL) was added dropwise, maintaining the temperature at −78 °C during this addition. The mixture was stirred for 2 h at −78 °C, then a solution of Et3N  in dry DCM (40.0 ml) was added. The mixture was stirred at −78 °C for another 30 min and at 25 °C for 12 h. Usual aqueous workup followed by chromatography  gave 10  as a white solid; MP 125–127 °C; [α]D = −64.84° ; Rƒ  = 0.73; analysis calcd for C23H24O6 (396.43): C 69.68, H 6.10; found: C 69.50, H 6.37.To a mixture of dry DMSO  and dry DCM (72.0 ml) at −78 °C, a solution of trifluoroacetic anhydride  in dry DCM (18.0 mL) was slowly added, and the mixture was stirred at this temperature for 45 min. Then a solution of 10  in dry DCM (6.0 mL) DAST  was added dropwise, and the mixture was stirred at 25 °C for 5 days. Methanol (2.0 mL) was carefully added, and the solvents were removed under diminished pressure. Usual aqueous workup followed by chromatography  gave 11  as a white amorphous solid; [α]D = −27.89° ; Rƒ  = 0.67; analysis calcd for C23H24O5F2 (418.43): C 66.02, H 5.78; H 65.79, H 5.93.To a solution of 11  in dry ether (40 mL) and THF (40 mL) lithium aluminum hydride  was added in several portions, and the suspension was stirred for 15 min at 25 °C. Then, the suspension was heated under reflux, and a solution of dry aluminum chloride  in dry ether (30 mL) was added followed by stirring under reflux for 72 h. The suspension was cooled to 25 °C, methanol (30 mL) was carefully added, and stirring was continued for another 45 min. Usual aqueous workup followed by chromatography  gave 12  and 13  each as a viscous oil;To an ice-cold solution of 12: [α]D = +14.57° ; Rƒ  = 0.47; analysis calcd for C23H26O5F2 (420.45): C 65.70, H 6.23; found: C 65.59, H 6.46.Data for 13: [α]D = −17.26° ; Rƒ  = 0.61; analysis calcd for C23H26O5F2 (420.45): C 65.70, H 6.23; found: C 65.56, H 6.41.Data for 12  in toluene (40 mL) containing triphenylphosphane  and imidazole  iodine  was added in several portions. After stirring at 90 °C for 1 h, the reaction mixture was decanted and the remaining oil was washed with ether (4 × 100 mL). The combined organic layers were evaporated, and the remaining residue was subjected to chromatography  to afford 14  as a colorless oil; [α]D = +23.79° ; Rƒ  = 0.51; analysis calcd for C23H25O4F2I (530.34): C 52.09, H 4.75; found: C 51.84, H 4.93.To a solution of 14  in dry DMF (29 mL) a solution of lithium azide  was added at 25 °C, and the solution was stirred at this temperature for 4 days. The solvents were removed under diminished pressure, and the remaining residue was dissolved in DCM (100 mL) and water (50 mL). The aq. phase was extracted with DCM (3 × 100 ml), and the combined organic layers were dried (Na2SO4). The solvent was removed under reduced pressure, and the remaining residue was subjected to chromatography  to afford 15  as a colorless oil; [α]D = +33.95° ; Rƒ  = 0.48; analysis calcd for C23H25O4F2N3 (445.44): C 62.01, H 5.66, N 9.43; found: C 61.86, H 5.71, N 9.21.To a solution of 15  in dry methanol (20.0 mL) containing palladium on charcoal  was hydrogenated . Workup as described above followed by chromatography  gave 16  as a white foam; [α]D = −27.95° ; Rƒ  = 0.13; analysis calcd for C9H17O4F2N (241.23): C 44.81, H 7.10, N 5.81; found: C 44.65, H 7.34, N 5.68.A solution of Supplementary Materials


Scientific Reports 10.1038/srep45179, published online 23 March 2017Correction to: 3 NFs synthesized at 210 °C for 12 h shown in panels d-f were incorrectly given as SEM images of P(VDF-HFP) based nanocomposites with 5.0 vol%, 10.0 vol% and 20.0 vol% BaTiO3 NFs synthesized at 210 °C for 24 h. The correct Figure 5 appears below as Fig. This article contains errors in Figure 5. The SEM images of the nanocomposites with 2.5 vol%, 5.0 vol% and 7.5 vol% BaTiO


Corrections to the article, “Multilabel segmentation of cancer cell culture on vascular structures with deep neural networks,” by S. Rahkonen et al. J. Med. Imag.7(2), 024001 (2020) doi: 10.1117/1.JMI.7.2.024001] was originally published online on 7 April 2020 with errors in the panel labels for Fig. 6.This article [The following corrections were made to the originally published version:1.in Fig 6(h), “Prediction (O)” was corrected to read “Prediction (S)”;2.in Fig 6(i), “Prediction (I)” was corrected to read “Prediction (IP)”;3.in Fig 6(j), “Errors (R)” was corrected to read “Errors (P)”;4.in Fig 6(k), “Errors (O)” was corrected to read “Errors (S)”;5.in Fig 6(l), “Errors (I)” was corrected to read “Errors (IP)”;6.in Fig 6(m), “Abs. errors (R)” was corrected to read “Abs. errors (P)”;7.in Fig 6(n), “Abs. errors (O)” was corrected to read “Abs. errors (S)”; and8.in Fig 6(o), “Abs. errors (I)” was corrected to read “Abs. errors (IP).”This article was corrected on 13 April 2020.


MF6  compounds and a related coordination polymer are reported.The crystal structures of three copper(II)-bipyridine– 2N,N′)copper(II) hexafluoridosilicate tetrahydrate, [Cu(bpy)2(H2O)][SiF6]·4H2O , (I), bis-di-μ-fluorido-1:3κ2F:F;2:3κ2F:F-decafluorido-1κ5F,2κ5F-ditantalum(V)copper(II), [Cu(bpy)2(TaF6)2], (II), triscopper(II) bis[hexafluoridotantalate(V)], [Cu(bpy)3][TaF6]2, (III), and catena-poly[[diaquacopper(II)]-μ-fluorido-tetrafluoridotin-μ-fluorido], [Cu(bpy)(H2O)2SnF6]n, (IV). Compounds (I), (II) and (III) contain locally chiral copper coordination complexes with C2, D2, and D3 symmetry, respectively. The extended structures of (I) and (IV) are consolidated by O—H⋯F and O—H⋯O hydrogen bonds. The structure of (III) was found to be a merohedral (racemic) twin.We report the hydrothermal syntheses and crystal structures of aquabis(2,2′-bipyridine-κ The structure features isolated C2-symmetric Δ- and Λ-[Cu(bpy)2(H2O)]2+ cations and octahedral SiF62– anions , as described by the parameter τ = (β − α)/60, where β and α are the two largest angles of the complex  2(H2O)]2+ complexes ns Fig. 1. The fiv2(TaF6)2 and crystallizes in space group P2(TaF6)2 complexes with local D2 symmetry. Each CuII center is equatorially coordinated by two bpy ligands and axially coordinated by two TaF6− groups. Two independent Cu(bpy)2(TaF6)2 units with the same handedness are present within the arbitrarily chosen asymmetric unit it Fig. 2. These c3][TaF6]2 and crystallizes in the enantiomorphous space group P32. The structure of (III)D3-symmetric Λ-Cu(bpy)32+ cations with CuII in an octahedral CuN6 coordination environment. The Cu—N distances are in agreement with those of the Cu(bpy)32+ cations in [Cu(bpy)3][PF6]2 it Fig. 3.2O)2SnF6 and crystallizes in space group P2/n. The structure is composed of one-dimensional coordination chains propagating in the [101] direction that can be described as alternating Cu(bpy)(H2O)22+ cations (Cu site symmetry 2) and SnF62− anions catenated through bridging Cu—F—Sn linkages. The Sn4+ ion occupies a crystallographic inversion center. Intramolecular hydrogen bonding is present along the chains via O1—H1A⋯F2 and O1—H1B⋯F3 contacts ts Fig. 4. The Cu—2(H2O)2+ and SiF62− groups are linked via O—H⋯F hydrogen bonding between the apical water molecule and two SiF62− ions (Table 12(H2O)2+ units participate in displaced heterochiral π–π stacking interactions between the N1/C1–C5 and N2/C6–C10 rings with an interplanar angle of 1.11 (11)°, centroid–centroid distance of 3.8774 (12) Å, and a slippage distance of 1.490 Å to form Δup–Λdown–Δup–Λdown and Δdown–Λup–Δdown–Λup chains (up/down refers to the orientation of the Cu—O bond vector in the +a or –a direction). The water molecules of hydration are involved in O—H⋯F hydrogen bonding interactions with the SiF62− anion as well as O—H⋯O bonds with other water molecules s Table 1. The Δ/Λes Fig. 5.2(TaF6)2 complexes in (II)a + b or b – a directions, as shown in Fig. 6c-axis direction, each chain is neighbored by a chain with the opposite chirality and same orientation on one side and a chain with the same chirality and opposite orientation on the other.The neutral Cu(bpy)32+ complexes participate in displaced π–π stacking interactions propagating along the 32 screw axes with an interplanar angle of 13.9 (2)°, centroid–centroid distance of 3.933 (2) Å between adjacent N1/C1–C5 and N5/C21–C25 pyridine rings, and a horizontal shift distance of 1.970 Å. Each Λ-Cu(bpy)32+ cation is surrounded by six TaF6− anions ns Fig. 7.via parallel displaced π–π stacking interactions ns Fig. 8. One of et al., 20162(H2O)]2+ complexes and fluorinated inorganic anions: [Cu(bpy)2(H2O)][BF4]2 ][PF6]2 ][MF6] MF62− anions hydrogen bonded to the [Cu(bpy)2(H2O)]2+ complex are both hydrogen bonded to the same pair of [Cu(bpy)2)(H2O)]2+ complexes in the ETM case, whereas they are bound to two different complexes in the SiF62− case. Further, while the [Cu(bpy)2(H2O)][MF6]  compounds display both face-to-face and displaced π–π stacking interactions, (I)A survey of structures related to (I)et al., 2017a-axis direction. Additionally, these complexes participate in heterochiral π–π stacking interactions.A search of the CSD for structures related to (II)A(bpy)3][PF6] 32+ complexes.Compound (III)2O)HfF6 (H2O)2MOxFx6– compounds , which display polar zigzag chains et al., 1993−1 to 150°C and held at 150°C for 24 h. The autoclaves were allowed to cool to room temperature at a rate of 6°C h−1 and the solid products were recovered by vacuum filtration. Compound (I)3)2·H2O, 5 mmol of 2,2′-bipyridine, 1.5 mmol of (NH4)2SiF6 and 1ml of deionized H2O. Compound (II)2O5, 0.8 ml HF(aq), and 0.3 ml of deionized H2O. Compound (III)2O5, 1 ml of HF(aq) and 0.1 ml of deionized H2O. Compound (IV)3)2·H2O, 1.3 mmol of 2,2′-bipyridine, 1.7 mmol of (NH4)2SnF6 and 1 ml of deionized H2O.The compounds reported here were synthesized by the hydrothermal pouch method (Harrison Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 3m1. The twinning occurs with a BASF of 0.5, suggesting that both the P31 and P32 configurations are present in equal proportions within the sample.The measured crystal of (III)10.1107/S2056989021000633/hb7957sup1.cifCrystal structure: contains datablock(s) global, II, III, IV, I. DOI: 2048914, 2048918, 2048917, 2048915CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Completion of the overall layer structure occurs through weak C—H⋯O, C—H⋯π (ring) and head-to-tail slipped π-stacking interactions.The title molecule is only a few degrees out of planarity except for the 2-hydroxyethyl substituent. In the crystal, O—H⋯N hydrogen bonds form stepped chains along the  12H13N3O2S, the benzothiazine moiety is slightly non-planar, with the imidazolidine portion twisted only a few degrees out of the mean plane of the former. In the crystal, a layer structure parallel to the bc plane is formed by a combination of O—HHydethy⋯NThz hydrogen bonds and weak C—HImdz⋯OImdz and C—HBnz⋯OImdz  interactions, together with C—HImdz⋯π(ring) and head-to-tail slipped π-stacking [centroid-to-centroid distances = 3.6507 (7) and 3.6866 (7) Å] interactions between thiazole rings. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (47.0%), H⋯O/O⋯H (16.9%), H⋯C/C⋯H (8.0%) and H⋯S/S⋯H (7.6%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, C—H⋯N and C—H⋯O hydrogen-bond energies are 68.5 (for O—HHydethy⋯NThz), 60.1 (for C—HBnz⋯OImdz) and 41.8 kJ mol−1 (for C—HImdz⋯OImdz). Density functional theory (DFT) optimized structures at the B3LYP/6–311 G level are compared with the experimentally determined molecular structure in the solid state.In the title molecule, C A plausible mechanism for the formationof the product, 1--3-(2-hydroxyethyl)imidazolidin-2-one (I), is given in the reaction scheme.Compounds containing the benzothiazole backbone have been studied extensively in both academic and industrial laboratories , carried out at the B3LYP/6-311G  level, are compared with the experimentally determined molecular structure in the solid state.I)  and B (S1/N1/C1/C6/C7)]. A puckering analysis of the conformation of the imidazolidine ring C (N2/N3/C8-C10) gave the parameters Q(2) = 0.0767 (14) Å and φ(2) = 66.5 (10)°. The conformation is described as an ‘envelope on C9′. This ring is almost coplanar with the thiazole ring B with a dihedral angle of 3.61 (4)° between their mean planes.In the title molecule (I) Fig. 1, the benHydethy⋯NThz (Hydethy = hydroxyethyl and Thz = thiazole) hydrogen bonds  and C—HImdz⋯π(ring) interactions (Table 1Bnz⋯OImdz (Bnz = benzene) interactions. Both the layer formation and stacking are also assisted by head-to-tail slipped π-stacking interactions  and 3.6866 (7) Å, respectively; symmetry codes: (i) −x + 1, −y + 1, −z + 1; (ii) −x + 2, −y + z + Cg2 is the centroid of ring B].In the crystal, O—Hs Table 1 form steon Fig. 2. These as Table 1. The lays Figs. 3 and 4 ▸ I, a Hirshfeld surface (HS) analysis  has a symmetrical distribution of points with the edges at de + di = 2.40 Å. The presence of C—H⋯π interactions is indicated by the characteristic wings with a spikes with the tips at de + di = 2.63 Å in the fingerprint plot delineated into H⋯C/C⋯H contacts . The H⋯S/S⋯H contacts contribute 7.6% to the overall crystal packing and are seen in Fig. 8e as widely scattered points with the tips at de + di = 3.03 Å. The pair of spikes in the fingerprint plot delineated into H⋯N/N⋯H contacts  has a symmetrical distribution of points with the tips at de + di = 1.88 Å. The C⋯C contacts  have an arrow-shaped distribution of points with the tip at de = di = 1.70 Å. The N⋯C/C⋯N interactions  give rise to tiny wings with the tips at de + di = 3.41 Å. The O⋯C/C⋯O contacts  give widely scattered points with the tips at de + di = 3.56 Å. Finally, the S⋯C/C⋯S and S⋯N/N⋯S interactions, contributing 2.2% and 1.3% to the overall crystal packing  give rise to tiny wings with the tips at de + di = 3.63 Å and de + di = 3.63 Å, respectively.The overall two-dimensional fingerprint plot, Fig. 8n Table 2 is H⋯H, ts Fig. 8f, 5.3% ng Fig. 8j and k dnorm plotted onto the surface are shown for the H⋯H, H⋯O/O⋯H, H⋯C/C⋯H, H ⋯ S/S⋯H, H⋯N/N⋯H and C⋯C interactions in Fig. 9a--f, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯O/O⋯H and H⋯C/C⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated to be −67.2 (Eele), −18.0 (Epol), −35.4 (Edis), 75.7 (Erep) and −68.5 (Etot) for O2—H2A⋯N1, −21.5 (Eele), −6.1 (Epol), −82.0 (Edis), 62.3 (Erep) and −60.1 (Etot) for C5—H5⋯O1 and −1.2 (Eele), −6.3 (Epol), −73.7 (Edis), 45.7 (Erep) and −41.8 (Etot) for C8—H8B⋯O1.The intermolecular interaction energies were calculated by the CE–B3LYP/6–311G energy model available in I in the gas phase have been computed using the B3LYP functional level of theory and the 6-31G  basis set ° while the corresponding dihedral angle in the others vary from 13.64° in III to 0.61° in V.A search of the Cambridge Structural Database . The mixture was stirred at 353 K for 24 h. The solid material was removed by filtration and the solvent evaporated in vacuo. The solid product was purified by recrystallization from ethanol to give colourless crystals (yield: 70%).To a mixture of 2-aminobenzothiazole (2.22 mmol), bis(2-chloroethyl)amine (1.11 mmol) and potassium carbonate (3.21 mmol) in DMF (25 mL) was added a catalytic amount of tetra-Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989020001723/jj2219sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020001723/jj2219Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020001723/jj2219Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020001723/jj2219Isup4.cmlSupporting information file. DOI: 1982595CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Correction to: BMC Public Health (2019) 19:1599https://doi.org/10.1186/s12889-019-7985-5It was highlighted that in the original article  the dataIncorrect statementEven though the prevalence rate of hypertension in male (29.1%) was mildly lower than female (32.7%), our finding showed a significantly higher PRAL in the male (25.3 ± 20.2 mEq/d) comparing to the female (19.4 ± 16.7 mEq/d).Correct statementPrevalence rate of hypertension in male (32.7%) was mildly higher than female (29.1%) and a significantly higher PRAL in the male (25.3 ± 20.2 mEq/d) was also identified comparing to the female (19.4 ± 16.7 mEq/d).


Febuxostat and ethanol molecules are linked into an O—H⋯O and O—H⋯N bonded chain structure. 16H16N2O3S·C2H6O, (I), displays intermolecular O—H⋯O and O—H⋯N bonds in which the carboxyl group of the febuxostat molecule and the hydroxyl group of the ethanol molecule serve as hydrogen-bond donor sites. These interactions result in a helical hydrogen-bonded chain structure. The title structure is isostructural with a previously reported methanol analogue.The title compound, 2-(3-cyano-4-isobutoxyphenyl)-4-methyl-1,3-thiazole-5-carboxylic acid ethanol monosolvate, C The hydroxy group of the solvent additionally serves as a hydrogen-bond donor group for an O14—H14⋯O23 bond to a second febuxostat molecule  typically adopts a value close to 0°. However, an opposite geometry with τ values close to 180° has been reported for the polymorphs Q and H1, a co-crystal with 4-aminobenzoic acid and a 2-(pyridin-2-ylamino)pyridinium salt.Table 2The preparation of febuxostat was carried out according to the scheme in Fig. 32, 10.0 g) and hexamethylenetetramine (5.86 g) were added to trifluoroacetic acid (100 ml). The reaction mixture was heated to reflux under stirring for 40 h, and trifluoroacetic acid was distilled out. The obtained residue was cooled to 298 K, water (200 ml) was added slowly, and the slurry was stirred for 4 h. After filtration, the product was washed and dried under vacuum to give 9.60 g of 3.Ethyl 2-(4-hydroxyphenyl)-4-methyl-5-thiazole carboxylate , potassium carbonate (332 g) and isobutyl bromide (330 g) were added to DMF (1.75 1). The reaction mixture was heated to 383±3 K and stirred for 4 h. The reaction mixture was cooled to 298 K, and water (0.50 l) was added slowly. The slurry was stirred for 2 h. After filtration, the product was washed and dried under vacuum to give 389 g of 4. 1H NMR (CDCl3), 400 MHz): δ = 1.079–1.101 , 1.366–1.413 , 2.185–2.230 , 2.769 , 3.914–3.935 , 4.316–4.387 , 7.045–7.074 , 8.188–8.225 , 8.353–8.361 .Ethyl 2-(3-formyl-4-hydroxyphenyl)-4-methyl-5-thiazolecarboxylate , sodium formate (123 g) and hydroxylamine hydrochloride (84 g) were successively added to formic acid (1.4 l). The reaction mixture was heated to reflux and stirred for 5 h to complete the reaction. The reaction solution was cooled to 298 K, and water (2.8 l) was slowly added. After stirring for approximately 1 h, the slurry was filtered, the product was washed with water and dried under vacuum to give 321 g of 5. 1H NMR (CDCl3), 400 MHz): δ = 1.053–1.104 , 1.368–1.463 , 2.164–2.225 , 2.768 , 3.890–3.911 , 4.324–4.395 , 6.998–7.027 , 8 8.188–8.225 , 8.353–8.361 .Ethyl 2-(3-formyl-4-isobutoxyphenyl)-4-methyl-5-thiazolecarboxylate  and potassium carbonate (200 g) were successively added to a mixture of MeOH (7.5 l) and water (250 ml). To complete the reaction, the solution was heated to reflux for 3 h under stirring. The clear solution was cooled, and vacuum was applied to distil out the solvent below 313 K. Water (5 l) was added to the residue. After stirring, EtOAc (2.5 l) was added. The solution was stirred, and the layers were separated. The pH of the aqueous solution was adjusted to 2.5±0.2 by adding diluted hydrochloric acid solution at 313 K. After stirring for 1 h, the slurry was filtered, and the product was washed with water and dried under vacuum to give 215 g of 1.Ethyl 2-(3-cyano-4-isobutoxyphenyl)-4-methyl-5-thiazolecarboxylate (Febuxostat (1 g) was dissolved in ethanol (10 ml), which yielded a clear solution upon heating to 338 K. After filtration, the solution was allowed to cool to room temperature, and the subsequent crystallization resulted in febuxostat ethanol solvate.Uiso parameters were set to 1.5Ueq(C) of the parent carbon atom. H atoms bonded to secondary CH2 (C—H = 0.99 Å) or tertiary CH (C—H = 0.99 Å) carbon atoms and H atoms bonded to C atoms in aromatic rings (C—H = 0.95 Å) were positioned geometrically and refined with Uiso set to 1.2Ueq(C) of the parent carbon atom. H atoms in OH groups were identified in difference maps, refined with a distance restraint [O—H = 0.84 (2) Å] and a free Uiso parameter. Two outliers  I. DOI: 10.1107/S2056989020006076/fy2145Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020006076/fy2145Isup3.cmlSupporting information file. DOI: 2000973CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The structures of both compounds are dominated by hydrogen bonds involving water coordination ligands, with an underlying 3.6 −  8H4N4O2)(H2O)4]n, (I), and [Sr(C8H4N4O2)(H2O)3]n, (II), from the one-pot hydrolysis transformation of benzoyl chloride and the in situ self-assembled [2 + 3] cycloaddition of nitrile are presented. These coordination compounds are prepared by reacting 4-cyanobenzoyl chloride with divalent alkaline-earth salts (BaCl2 and SrCl2) in aqueous solution under hydrothermal conditions. The mononuclear coordination compounds (I) and (II) show the same mode of coordination of the organic ligands. The cohesion of the crystalline structures is provided by hydrogen bonds and π-stacking interactions, thus forming three-dimensional supramolecular networks. The two compounds have a three-dimensional -connected topology, and the structural differences between them is in the number of water molecules around the alkaline earth metals. Having the same emission frequencies, the compounds exhibit photoluminescence properties with a downward absorption value from (I) to (II).Two alkaline-earth coordination compounds, [Ba(C In these two coordination compounds, the asymmetric unit comprises half of a crystallographically independent alkaline-earth metal ion, half of a deprotonated 4-(tetrrazol-5-yl)benzoate anion (ttzbenz), and two halves of water molecules in compound (I)et al., 2009et al., 2007et al., 2009Compound (I)10 sphenocorona coordination geometry . In (I)2+ ion is eightfold coordinated, being surrounded by four bridging water molecules and by four oxygen atoms from three symmetry-related ttzbenz ligands .The crystal structures of compounds (I)ds Fig. 2, thus geAe2+ ion (Ae2+ = Ba2+ and Sr2+) range between 42.49 (6) and 142.50 (2)° in compound (I)et al., 2010Ae2+ one-dimensional coordination polymers: Ba—O = 2.647–3.179 Å, Sr—O = 2.486–2.843 Å in [C24H28N2O13Cl2CuSr]n and [C24H28N2O13Cl2CuBa]n 6(H2O)4]n, Ba—O = 2.801 (2)–3.6143 (2) Å for M = Ni, Ba—O = 2.797 (2)–2.999 (2) Å for M = Zn, and Ba—O = 2.801 (2)–3.004 (2) Å for M = Co  Å for compound (I)The ttzbenz ligand can adopt several coordination modes by involving the tetrazole ring ed Fig. 4 with a cCg1) and the phenyl rings (centroid Cg2) with centroid–centroid distances Cg1⋯Cg2 = 3.622 (3) Å and Cg2⋯Cg2 = 3.897 (3) Å  Å Fig. 4.et al., 2011c net with stoichiometry (3-C)2(6-C), which can be represented by the point symbol {43}2{46.66.83}. Thus the two structures consist of planar layers running parallel to (100)  to obtain the underlying network. In such models, only metal centers and the centroids of organic ligands are considered as structural units (Alexandrov 0) Fig. 5.et al., 2016et al., 2009et al., 2012et al., 2012et al., 2007et al., 2009et al., 2013et al., 2016et al., 2009et al., 2011et al., 2017et al., 2016et al., 2016et al., 2015et al., 2016N,N-dimethylacetamide  benzoate in the Cambridge Structural Database  for (I)2·6H2O  for (II)Colorless crystals suitable for X-ray diffraction were obtained by hydrothermal synthesis in an aqueous solution according to a literature procedure −1): 3300 ν(O—H)water, 3100 ν(C—H)Ph, 1435 νsym (C—C), 1523 ν(N—N)ring, 1603 ν(C—N)ring, 628–1050 γ,δ (tetrazole).FT–IR of (I)−1): 3600 ν(O—H)water, 3200 ν(C—H)Ph, 1408 νsym (C—C), 1530 ν(N—N)ring, 1585 ν(C—N)ring, 654–1009 γ, δ (tetrazole) .FT–IR of (II)The thermogravimetric analysis (TGA) was performed in the range 25–600°C under air atmosphere at a flow rate of 5°C/min Fig. 6. The pyr−1  was performed in the range 25–600°C under an air atmosphere at a flow rate of 5°C min−1 Fig. 6. The pyreX = 322 nm) on an Agilent Cary Eclipse Fluorescence Spectrophotometer at room temperature. Excitation of the two compounds after dissolution in DMSO leads to similar fluorescence emission spectra. The emission maximum of (I)supporting information), probably corresponding to π* → π or π*→n electronic transition of the aromatic ring ttzbenz ligands Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989020006386/tx2021sup1.cifCrystal structure: contains datablock(s) TTZBENZ_AE, I, II. DOI: 10.1107/S2056989020006386/tx2021Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020006386/tx2021IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989020006386/tx2021sup4.jpgInfrared spectra. DOI: Click here for additional data file.10.1107/S2056989020006386/tx2021sup5.jpgPhotoluminescent spectra. DOI: Click here for additional data file.10.1107/S2056989020006386/tx2021sup6.docTable S1. Comparative shape analysis of two polymers. DOI: 2003538, 2003537CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecule forms a centrosymmetric water-bridged hydrogen-bonding dimer with graph-set notation via two longer intermolecular hydrogen-bonding interactions between the second hydrogen atom on the bridging water molecule and both a pyridine nitrogen atom and carbonyl oxygen. The trifluoromethyl groups extend out the faces of the sheet providing for F⋯F and C—H⋯F contacts between the sheets, completing the three-dimensional packing.The title compound, [systematic name: 5-(trifluoromethyl)pyridine-2-carboxylic acid monohydrate], C 7H4F3NO2·H2O, is the acid hydrate of a pyridine with a carboxylic acid group and a trifluoromethyl substituent situated para to one another on the aromatic ring. The molecule forms a centrosymmetric water-bridged hydrogen-bonding dimer with graph-set notation R44 (12). Hydrogen-bonding distances of 2.5219 (11) and 2.8213 (11) Å are observed between the donor carboxylic acid and the bridging water acceptor, and the donor water and carbonyl oxygen acceptor, respectively. The dimers are further linked into a two-dimensional sheet via two longer intermolecular hydrogen-bonding interactions between the second hydrogen atom on the bridging water molecule and both a pyridine nitrogen atom and carbonyl oxygen with distances of 3.1769 (11) and 2.8455 (11) Å, respectively. The trifluoromethyl groups extend out the faces of the sheet providing for F⋯F and C—H⋯F contacts between the sheets, completing the three-dimensional packing.The title compound [systematic name: 5-(trifluoromethyl)pyridine-2-carboxylic acid monohydrate], C The twoThe structure of 5-(trifluoromethyl)picolinic acid (I)W distance of 2.5219 (11) Å characterizing the O1—H1⋯O1W hydrogen bond, while the water hydrogen atom H2W bonds to the carbonyl oxygen atom with an O1W⋯O2i distance of 2.8213 (11) Å charaterizing the O1W-–H2W⋯O2i hydrogen bond .The molecular packing in the solid state can be characterized by the 5-(trifluoromethyl)picolinic acid (I)2) Fig. 2. The carW, further bridge the dimer units together to form a pleated strip or tape motif that propagates along the crystallographic [010] direction  and 2.8455 (11) Å, respectively, characterize the O1W—H1W⋯Nii and O1W—H1W⋯O2ii hydrogen bonds NO3·H2O hydrogen bonds into thick two-dimensional sheets with the trifluoromethylaromatic groups extending to the faces of the sheets -2-pyridinecarboxylic acid has been used as a monoanionic ligand in several metal complexes, including with Co5-(Trifluoromethyl)-2-pyridinecarboxylic acid  was purchased from Aldrich Chemical Company, USA, and was used as received.Uiso(H) = 1.2Ueq(C) of the aryl C-atoms. The position of the carboxylic acid and water hydrogen atoms were found in the difference map and refined freely.Crystal data, data collection and structure refinement details are summarized in Table 21H NMR : δ 3.70 , 8.21 , 8.37 , 9.07 . 13C NMR : δ 123.23 , 124.73 , 127.30 , 135.12 , 146.24 , 151.98 , 165.13 . 19F NMR : δ −61.35 . IR : 3469 , 3050 , 2849 (w), 2571 (w), 1961 (m), 1707 , 1606 (s), 1582 (s), 1493 (s), 1440 (s), 1392 (s), 1328 (m), 1290 (m), 1251 (s), 1163 (m), 1126 (s), 1075 (s), 1023 (s), 948 (s), 878 (m), 864 (s), 806 (s), 760 (s), 704 (s), 643 (s), 524 (s). GC–MS (Agilent Technologies 7890A GC/5975C MS): +M = 191 amu, corresponding to the anhydrous form, 5-(trifluoromethyl)pyridine-2-carboxylic acid (I)10.1107/S2056989020013523/dj2015sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989020013523/dj2015Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020013523/dj2015Isup3.cmlSupporting information file. DOI: 2036131CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-018-22971-w, published online 16 March 2018Correction to: In Figure 4, the panels r and s were presented as s and r respectively. The correct Figure 4 appears below as Figure In addition, this Article contains an error in the Methods section under subheading ‘Collagen gel preparation’ where“Rat tail type 1 collagen gels (Merck 08–115) were prepared at 1 mg/ml in 10 × M199 (Life Technologies 11825–015) and the pH was adjusted to 7.5 with 2.2% (w/v) NaHCO3. 10 × M199 and NaHCO3 were both measured at 1/10 of the final volume.”should read:“Rat tail type 1 collagen gels (Merck 08–115) were prepared at 1 mg/ml in 10 × M199 (Life Technologies 11825–015) and the pH was adjusted with 2.2% (w/v) NaHCO3. 10 × M199 and NaHCO3 were both measured at 1/10 of the final volume.”


The asymmetric unit of the title compound comprises three independent molecules of similar geometry. The crystal structure is stabilized by intermolecular C—H⋯N and C—H⋯Cl hydrogen bonds in addition to C—Cl⋯π interactions. 16H14Cl3N3, comprises three molecules of similar shape in the asymmetric unit. The crystal cohesion is ensured by intermolecular C—H⋯N and C—H⋯Cl hydrogen bonds in addition to C—Cl⋯π interactions. Hirshfeld surface analysis and two-dimensional fingerprint plots reveal that Cl⋯H/H⋯Cl (33.6%), H⋯H (27.9%) and C⋯H/H⋯C (17.6%) are the most important contributors towards the crystal packing.The title compound, C Nevertheless, they can control the reactivity of molecules, the crystal packing, tautomerization and other properties -(4-chlorophenyl)diazenyl]ethenyl}-N,N-dimethylaniline, which features C—H⋯N, C—H⋯π and C—Cl⋯Cl types of weak intermolecular interactions.In a previous study we have attached resonance-assisted hydrogen-bonded synthons or chlorine atoms to dye molecules, which leads to intermolecular weak interactions for the resulting products with interesting analytical and solvatochromic properties (Maharramov A (C1A–C16A/N1A–N3A/Cl1A–Cl3A) and Mol-N1B (C1B–C16B/N1B–N3B/Cl1B–Cl3B). The conformational differences between molecules Mol-N1, Mol-N1A and Mol-N1B are highlighted in an overlay diagram shown in Fig. 2A–C6A and C8A–C13A (molecule Mol-N1A), and C1B–C6B and C8B–C13B (molecule Mol-N1B)] of the 4-chlorophenyl and N,N-dimethylaniline groups are 69.94 (10), 79.68 (12) and 88.08 (13)°, respectively. In molecule Mol-N1, the N1—N2—C7—C14, N2—C7—C14—Cl2, N2—C7—C14—Cl3 and C8—C7—C14—Cl3 torsion angles are −178.7 (2), 3.1 (3), −176.21 (16) and 4.1 (3)°, respectively. The corresponding angles are 178.4 (2), 3.8 (3), −175.1 (2) and 2.5 (3)° for molecule Mol-N1A, and −175.0 (2), 0.3 (3), 179.71 (18) and −0.1 (4) for molecule Mol-N1B.The asymmetric unit of the title compound Fig. 1 containsIn the crystal, the molecules are connected by intermolecular C—H⋯N and C—H⋯Cl hydrogen bonds and C—Cl⋯π interactions, which contribute to the overall packing, forming a three-dimensional network Table 1.et al., 2007Crystal Explorer 17.5 . The shape-index of the Hirshfeld surface is a tool to visualize π–π stacking interactions; Fig. 4b clearly suggest that there are no π–π interactions in the title compound. The red spots in Fig. 4a correspond to the relatively strong C—H⋯N hydrogen-bonding interactions in the crystal structure; in Mol-N1A it involves the N3A atoms of the N,N-dimethylaniline group as acceptors with the aromatic H2A donor atom of the chlorobenzene ring in Mol-N1 (C2—H2A⋯N3A).Hirshfeld surface analysis was used to investigate the presence of hydrogen bonds and intermolecular interactions in the crystal structure. The Hirshfeld surfaces . Another significant reciprocal interaction (H⋯H) with a contribution of 27.9% is present as broad symmetrical spikes at diagonal axes de + di ≃ 2.2 Å . The pair of characteristic wings in the fingerprint plot delineated into C⋯H/H⋯C contacts , have tips at de + di ≃ 2.80 Å. The Cl⋯Cl contacts, Fig. 5e (5.7% contribution), have an arrow-shaped distribution of points with the tip at de = di = 3.50 Å.Two-dimensional fingerprint plots are presented in Fig. 5ce Fig. 5b. Anoth Å Fig. 5c. The pviz. Cl⋯C/C⋯Cl (5.4%), N⋯H/H⋯N (4.7%), C⋯C (1.7%), Cl⋯N/N⋯Cl (1.6%), N⋯C/C⋯N (1.0%) and N⋯N (0.8%) contacts, show only small contributions and thus have a negligible effect on the packing.The other weak intermolecular interactions, et al., 2016E)-1--2-phenyldiazene skeleton gave 25 hits, of which six closely resemble the title compound, viz. 1-(4-bromophenyl)-2-diazene . Additional van der Waals interactions consolidate the three-dimensional packing. In the crystal of HODQAV, molecules are stacked in columns along [100] via weak C—H⋯Cl hydrogen bonds and face-to-face π–π stacking interactions. The crystal packing is further stabilized by short Cl⋯Cl contacts. In XIZREG, molecules are linked by C—H⋯O hydrogen bonds into zigzag chains running along [001]. The crystal packing is further stabilized by C—Cl⋯π, C—F⋯π and N—O⋯π interactions. In the crystal of LEQXIR, C—H⋯N and C—H⋯O hydrogen bonds and Cl⋯O contacts were found, and in LEQXOX, C—H⋯N and Cl⋯Cl contacts are observed.In the crystal structures of HONBOE and HONBUK, the aromatic rings form dihedral angles of 60.9 (2) and 64.1 (2)°, respectively. Molecules are linked through weak et al., 2018E)-4-[(2-(4-chlorophenyl)hydrazineylidene]methyl)-N,N-dimethylaniline , tetramethylethylenediamine (TMEDA) , CuCl  and CCl4 . After 1–3 h , 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 x 50 ml), brine (30 ml), dried over anhydrous Na2SO4 and concentrated in vacuo in a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and dichloromethane (3/1–1/1) to give an orange solid. Yield: 72%; mp 408 K. Analysis: calculated for C16H14Cl3N3: C 54.19, H 3.98, N 11.85; found: C 54.08, H 3.91, N 11.82%. 1H NMR  δ 3.05 , 6.79–7.79 . 13C NMR  δ 152.41, 151.45, 150.29, 137.26, 135.11, 131.08, 129.27, 124.50, 119.11, 111.48, 40.29. ESI–MS: m/z: 355.48 [M + H]+.The title compound was synthesized according to a reported literature protocol  = 0.93 Å, iUso(H) = 1.2Ueq(C) for aromatic H atoms, and 0.96 Å, Uiso(H) = 1.5Ueq(C) for methyl H atoms. Owing to poor agreement between observed and calculated intensities, five outliers  I. DOI: 10.1107/S2056989020007549/wm5554Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020007549/wm5554Isup3.cmlSupporting information file. DOI: 2007970CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The phenol ring makes a dihedral angle of 44.77 (3)° with the benzene ring of the trifluoromethyl group. In the crystal, molecules are linked by C—H⋯O interactions, forming polymeric chain along the b-axis direction.The title compound, C 15H12F3NO, crystallizes with one molecule in the asymmetric unit. The configuration of the C=N bond is E and there is an intramolecular O—H⋯N hydrogen bond present, forming an S(6) ring motif. The dihedral angle between the mean planes of the phenol and the 4-trifluoromethylphenyl rings is 44.77 (3)°. In the crystal, molecules are linked by C—H⋯O interactions, forming polymeric chains extending along the a-axis direction. The Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from C⋯H/H⋯C (29.2%), H⋯H (28.6%), F⋯H/H⋯F (25.6%), O⋯H/H⋯O (5.7%) and F⋯F (4.6%) interactions. The density functional theory (DFT) optimized structure at the B3LYP/6-311 G level is compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap. The crystal studied was refined as an inversion twin.The title compound, C These compounds show biological activities including antibacterial, antifungal, anticancer and herbicidal activities  carried out at the B3LYP/6-311 G level are compared with the experimentally determined molecular structure of (I)S(6) ring motif; this is a common feature in related imine–phenol compounds. The imine group displays a C9—C8—N1—C6 torsion angle of 170.1 (4)° while the mean plane of the phenol ring (C9–C14) is inclined to that of the 4-trifluoromethylphenyl group (C1–C6) by 44.77 (3)°. The configuration of the C8=N1 bond is E. The C10—O1 bond length [1.357 (8) Å  and 1.342 Å ] indicates single-bond character a-axis direction on Fig. 2. The cryet al., 2007CrystalExplorer17.5  and shape-index  surfaces of (I)b) interactions that involve C1—H1A and the oxygen atom O1 of the phenol group de and di diagonal axes. The presence of C—H⋯O interactions in the crystal is indicated by the pair of characteristic wings in the fingerprint plot delineated into C⋯H/H⋯C  contacts (29.2% contributions to the Hirshfeld surface). In Fig. 5c, the widely scattered points in the fingerprint plot are related to H⋯H contacts, which make a contribution of 28.6% to the Hirshfeld surface. There are also F⋯H/H⋯F , O⋯H/H⋯O  and F⋯F  contacts, with smaller contributions from N⋯H/H.·N (2.4%), O⋯C/C⋯O (2.2%), F⋯C/C⋯F (0.8%) and O⋯N/N⋯O (0.2%) contacts.In order to visualize the role of weak intermolecular interactions in the crystal, a Hirshfeld surface (HS) analysis  using the standard B3LYP functional and the 6-311G basis-set calculations A = −EHOMO), the ionization potential (I = −ELUMO), the HOMO–LUMO energy gap (ΔE), the chemical hardness (η) and softness (S)  and the lowest-unoccupied molecular orbital (LUMO) are very important aspects as many electronic, optical and chemical reactivity properties of compounds can be predicted from these frontier molecular orbitals -2-{[(3-chlorophenyl)imino]methyl}-6-methylphenol -2-[(2-hydroxy-5-methoxybenzylidene)amino]benzonitrile -1-phenyl-N-imino}methyl)phenolato]rhodium(III) chlorido[2-({[4-(trifluoromethyl) phenyl]imino}methyl)phenolato]iridium(III) salicylaldiminato)titanium(IV) toluene solvate methyl]aminato}copper(II) iminomethyl]phenolato}bis(tetrahydrofuran)vanadium(III) iminomethyl]phenolato}(tetrahydrofuran)vanadium(III) phenyl]-3-methoxysalicylaldimine -3-{[3-(trifluoromethyl)phenylimino]methyl}benzene-1,2-diol -5-(trifluoromethyl)aniline -2-methyl-6-[3-(trifluoromethyl)phenyliminomethyl]phenol -2-[(4-chlorophenyl)iminomethyl]-4-(trifluoromethoxy)phenol -4-methyl-2-[3-(trifluoromethyl)phenyliminomethyl]phenol  in ethanol (15 mL) and 4-trifluoromethylphenylamine  in ethanol (15 mL) and stirring the mixture for 8 h under reflux. Single crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution .Uiso(H) = 1.2–1.5Ueq(C). The hydrogen atom of the phenol group was located in a difference map and also included as a riding contributor with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O). During refinement, the twin transformation matrix , was used.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989020009615/mw2164sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020009615/mw2164Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020009615/mw2164Isup3.cmlSupporting information file. DOI: 2016363CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Pseudomonas putida and Bacillus subtilis. Notably, the more water‐soluble cIPTG derivative proved to be particularly suitable for light‐mediated gene expression in these alternative expression hosts.Photolabile protecting groups play a significant role in controlling biological functions and cellular processes in living cells and tissues, as light offers high spatiotemporal control, is non‐invasive as well as easily tuneable. In the recent past, photo‐responsive inducer molecules such as 6‐nitropiperonyl‐caged IPTG (NP‐cIPTG) have been used as optochemical tools for Lac repressor‐controlled microbial expression systems. To further expand the applicability of the versatile optochemical on‐switch, we have investigated whether the modulation of cIPTG water solubility can improve the light responsiveness of appropriate expression systems in bacteria. To this end, we developed two new cIPTG derivatives with different hydrophobicity and demonstrated both an easy applicability for the light‐mediated control of gene expression and a simple transferability of this optochemical toolbox to the biotechnologically relevant bacteria  Extended toolbox: New photocaged IPTG derivatives with various hydrophobicities for light‐induced gene expression were synthesised and tested with three different expression host strains. The most water‐soluble compound showed superior performance, especially in Bacillus subtilis. A dean‐stark trap filled with molecular sieve (3 Å) was utilised for the constant removal of water. After the reaction was completed as indicated by TLC, it was washed with saturated NaHCO3 solution. The aqueous phase was then extracted with CH2Cl2 and the combined organic phase was dried with anhydrous Na2SO4 and concentrated under reduced pressure. The residue was purified by flash column chromatography on SiO2 (petroleum ether/ethyl acetate 85 : 15) to yield a yellow solid . Rf=0.25 (petroleum ether/ethyl acetate 80 : 20) m.p. 62.1 °C; 1H NMR : δ=1.12 , 1.22 , 3.50 , 3.62 , 4.18 , 4.19 , 4.96 , 4.99 , 5.88 , 7.09 , 7.57 ppm ; 13C NMR : δ=14.0 (C‐11 and C‐11′), 14.9 (C‐2′), 60.8 (C‐10 or C‐10′), 60.9 (C‐10 or C‐10′), 65.5 (C‐8 or C‐8′), 65.6 (C‐8 or C‐8′), 97.7 (C‐7), 110.6 (C‐3), 111.5 (C‐6), 127.9 (C‐1), 141.4 (C‐2), 146.5 (C‐4), 150.2 (C‐5), 168.1 (C‐9 or C‐9′), 168.1 ppm (C‐9 or C‐9′); IR (ATR‐film): ṽ=2981, 1755, 1692, 1581, 1526, 1446, 1346, 1291, 1196, 1176, 1080, 878, 796 cm−1; HRMS (ESI): m/z calcd for C19H27NO10+: 447.1973 [M+NH4]+; found: 447.1972.Synthesis of BEC‐cIPTG (10 a): To a solution of 4,5‐bis(ethoxycarbonylmethoxy)‐2‐nitrobenzylaldehyde diethyl acetal (12)  in dry CH2Cl2 (6 mL) IPTG  was added. After 5 min p‐TSA  was added to the suspension and it was stirred at room temperature for 20 h. After the reaction was completed as indicated by TLC, a small amount of triethylamine was added and the reaction was concentrated under reduced pressure. The residue was purified by flash column chromatography on SiO2 (petroleum ether/ethyl acetate 50 : 50 to 20 : 80) to yield a white solid . Rf=0.35 (petroleum ether/ethyl acetate 20 : 80); m.p. 104.5 °C; [α]= −68 (c=1.0 in CHCl3); 1H NMR : δ=1.31 , 1.35 , 1.36 , 2.56 , 3.25 , 3.52 , 3.64–3.70 , 4.08 , 4.24–4.31 , 4.41 , 4.77 , 4.82 , 6.21 , 7.35 , 7.54 ppm ; 13C NMR : δ=14.3 (C‐11 or C‐11′), 14.3 (C‐11 or C‐11′), 24.1 (CH3‐a or CH3‐b), 24.3 (CH3‐a or CH3‐b), 35.5 (SCH), 61.8 (C‐10 or C‐10′), 61.9 (C‐10 or C‐10′), 66.4 (C‐8 or C‐8′), 66.6 (C‐8 or C‐8′), 69.8 (C‐6′′), 70.1 (C‐5′′), 70.3 (C‐3′′), 73.9 (C‐2′′), 76.2 (C‐4′′), 85.7 (C‐1′′), 96.6 (C‐7), 111.5 (C‐3), 112.8 (C‐6), 127.7 (C‐1), 141.3 (C‐2), 147.6 (C‐4), 151.7 (C‐5), 167.9 (C‐9 or C‐9′), 167.9 ppm (C‐9 or C‐9′); IR (ATR‐film): ṽ=3478, 2967, 2916, 2866, 1747, 1520, 1287, 1176, 1097, 1077, 1027, 989 cm−1; UV/Vis (MeOH): λmax (ϵ)=298 nm (8006 dm3 mol−1 cm−1); HRMS (ESI): m/z calcd for C24H37N2O13S: 593.2011 [M+NH4]+; found: 593.2011.Synthesis of BC‐cIPTG (10 b): A solution of BEC‐cIPTG (10a)  in MeOH (3.5 mL) was cooled to 0 °C and a 0.2 m solution of LiOH (3.5 mL) was added. The reaction mixture was stirred for 1 h at room temperature. After the reaction was completed as indicated by TLC, the MeOH was evaporated under reduced pressure and the remaining solution was lyophilised overnight. The residue was suspended in THF, sonicated for 15 min and filtrated. After washing with small amounts of cold THF a white solid  was obtained. m.p. 190 °C (decay); [α]=−92 (c=1.0 in H2O); 1H NMR : δ=1.29 , 1.31 , 3.26 , 3.66 , 3.71–3.82 , 4.18 , 4.37 , 4.60 , 4.62 , 4.67 , 6.20 , 7.32 , 7.55 ppm ; 13C NMR : δ=22.9 (CH3‐a), 23.3 (CH3‐b), 35.0 (SCH), 67.3(C‐8′), 67.4 (C‐8), 69.1 (C‐2′′), 69.3 (C‐6′′), 69.6 (C‐5′′), 72.8 (C‐3′′), 76.5 (C‐4′′), 84.8 (C‐1′′), 96.4 (C‐7), 109.2 (C‐3), 110.8 (C‐6), 126.3 (C‐1), 140.0 (C‐2), 147.2 (C‐4), 151.5 (C‐5), 175.1 (C‐9), 175.4 ppm (C‐9′); IR (ATR‐film): ṽ=3124, 3043, 1605, 1522, 1398, 1335, 1277, 1077, 1047, 1024, 824 cm−1; UV/Vis (H2O): λmax (ϵ)=245 (5008), 342 nm (3191 dm3 mol‐1 cm−1); HRMS (ESI): m/z calcd for C20H29N2O13S+: 537.1385 [M+NH4]+; found: 537.1382.Determination of purity by qNMR: The purity of the photocaged IPTG derivatives 10 a, 10 b and 1 was determined via quantitative NMR. 3,5‐bis(trifluoromethyl)bromobenzene was utilised as internal standard for 10 a as well as 1 and (methanesulfonyl)methane for 10 b. The spectra were measured at 20 °C on a Bruker Avance/DRX 600 spectrometer with 64 scans each and 30 μs relaxation time between each scan. The results in Table S3 are means of triplicate measurements.Solubility analysis: The solubility of 10 a, 10 b and 14 was determined photometrically at 25 °C using a spectrophotometer Shimadzu UV‐1800 (CPS‐240A). The absorbance of a serial dilution in degassed and deionised water was measured at the absorption maximum of the respective compound. A saturated solution was measured under the same conditions. The solubility was calculated using the Beer‐Lambert law.Hydrolytic stability: For the determination of the hydrolytic stability, a 1 mm solution of the respective compound in methanol or sodium phosphate buffer  was stored in the dark at room temperature. Samples were removed after 0 and 24 h and analysed by reversed‐phase HPLC.Quantification of uncaging half‐life times: A 1 mm solution of each photocaged compound in methanol or sodium phosphate buffer  was prepared. In a cuvette 1 mL of this solution was irradiated at room temperature using the LUMOS 43 (375 nm) for a certain time period. The sample was then analysed by reverse phase HPLC Jasco HPLC system [column: Hyperclone 5 μ ODS (C18) 120 (Phenomenex)]. For each photocaged compound, the procedure was repeated for different irradiation times. The decrease of concentration was measured by an UV detector.Determination of uncaging quantum yields: The quantum yields of 1, 10 a and 10 b were determined by a relative method in comparison to the quantum yield of 2‐nitropiperonylacetate (NPA‐Ac), as this substrate shows a sufficient similarity to 1, 10 a and 10 b. The procedure was followed as previously described in literature .[Bacterial strains and plasmids: The E. coli strain DH5αE. coli strain S17‐1E. coli strains, the P. putida strain KT2440B. subtilis strain DB430E. coli) or 30 °C . Media were supplemented either with kanamycin (50 μg mL−1), gentamicin (25 μg mL−1), irgasan (25 μg mL−1) or chloramphenicol (5 μg mL−1), when appropriate.All bacterial strains and plasmids used in this study are listed in Table S1, Supporting Information.Plasmid construction: All recombinant DNA techniques were carried out as described by Sambrook et al.B. subtilis expression vector pHT01‐sfGFP, the sfGFP‐encoding gene was synthesised with flanking NdeI and HindIII restriction sites  and subsequently cloned into pET‐22(b) . The resulting vector pET‐22(b)‐sfGFP was used as template for SLIC cloningsfgfp gene into the B. subtilis expression vector pHT01  using oligos 3–6 . The P. putida expression vector pVLT33‐GFPmut3 was constructed by restriction and ligation. To this end, the gfpmut3 gene was amplified with flanking EcoRI and XbaI restriction sites via PCR using oligos 1–2 (Table S1). Afterwards, the EcoRI/XbaI hydrolysed fragment was ligated into the likewise hydrolysed vector backbone pVLT33, resulting in the final expression vector pVLT33‐GFPmut3. Correct nucleotide sequences of all constructs were confirmed by Sanger sequencing (Eurofins Genomics).Cultivation conditions: All E. coli, P. putida and B. subtilis expression cultures were grown in 48‐well Flowerplates® in a BioLector microbioreactor system  , inoculated with an optical density at 580 nm of 0.05. During cultivation, the cell density was measured online through the scattered light intensity at 620 nm. In addition, fluorescence of eYFP and GFP variants (GFPmut3 and sfGFP) were continuously determined using a 508/532 nm and 488/520 nm filter, respectively. cIPTG variants 10 a, 10 b or NP‐cIPTG (1) were added prior inoculation  and expression of reporter genes was induced during the early logarithmic growth phase  via UV‐A light exposure  or by addition of equal amounts of conventional IPTG (14) after illumination.Determination of expression heterogeneity: For measurement of the expression heterogeneity, E. coli and B. subtilis cultures were analysed on the single‐cell level by flow cytometry regarding their fluorescence intensity and distribution. Expression cultures were grown as described above and were subsequently sampled as soon as they reached the late logarithmic growth phase (after 8 h for E. coli and after 10 h for B. subtilis). For this purpose, 40 μL was taken out of the Flowerplate® cultures and added to 600 μL PBS buffer (pH 7.4). Subsequently, the cells were harvested by centrifugation , adjusted to an optical density of 0.5 (OD580) in 100 μL PBS buffer and then transferred into a 96‐well microtiter plate . Finally, these samples were analysed with a flow cytometer . The individual cellular fluorescence brightness was measured using a 488‐nm laser (15 % intensity for E. coli and 5 % for B. subtilis) for excitation and a 528/46 nm bandpass filter for detection. To exclude cell debris and cell aggregates, the cells were also analysed regarding their size  and granularity . FSC was measured using an FSC laser (nm) with 80 % of the laser power for E. coli and 50 % for B. subtilis and a 456/51 nm bandpass filter for detection. For determination of SSC a nm‐light laser with 80 % of the laser power for E. coli and 50 % for B. subtilis (773/56 nm bandpass filter) was used. Based on the scatter plots, bacterial cells were gated from irrelevant counts for fluorescence analysis. Flow cytometric data were evaluated with the CellStreamTM Analysis Software .The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file.


The crystal structure features both intra- and intermolecular C—H⋯O hydrogen bonds, as well as intermolecular C—H⋯π and π–π interactions, leading to the formation of sheets parallel to the ac plane.The crystal structure of a pyrrolidine-substituted  11H15NO2S, features a sulfonamide group with S=O bond lengths of 1.4357 (16) and 1.4349 (16) Å, an S—N bond length of 1.625 (2) Å, and an S—C bond length of 1.770 (2) Å. When viewing the molecule down the S—N bond, both N—C bonds of the pyrrolidine ring are oriented gauche to the S—C bond with torsion angles of −65.6 (2)° and 76.2 (2)°. The crystal structure features both intra- and intermolecular C—H⋯O hydrogen bonds, as well as intermolecular C—H⋯π and π–π interactions, leading to the formation of sheets parallel to the ac plane.The molecular structure of the title compound, C Sulfonamides are of significant value in organic chemistry because of their therapeutic properties. These molecules are referred to in the pharmaceutical industry as sulfa drugs. This class of drugs has been widely used in various pharmaceutical applications owing to their antibacterial, antiviral, antimalarial, antifungal, anticancer, antidepressant, and other properties ° and C5—S1—N1—C4 = 76.16 (19)°. A conformational analysis of the five-membered pyrrolidine ring pucker gives a puckering amplitude (Q2) parameter of 0.352 (3) Å and a φ2 parameter of 262.2 (4)°. Consequently, this ring is in a half-chair conformation with a twist along the C2—C3 bond. Lastly, an intramolecular C—H⋯O contact  and a symmetry-derived ring . The π–π interaction has a centroid-to-centroid distance of 3.8162 (15) Å with a slippage of 1.307 Å. The result of these interactions is the formation of sheets that lie in the ac plane  to a stirring mixture of pyrrolidine  and 10 ml of tetrahydrofuran. This was followed by the dropwise addition of 0.59 M aqueous potassium carbonate  and the mixture was stirred at room temperate for 6 h. Upon acidification with 5 M HCl, a white precipitate was isolated by vacuum filtration to give the crude sulfonamide product. The crude product was dissolved in hot ethanol and filtered. The filtrate was transferred to a scintillation vial and crystallized upon standing for 24 h to afford colorless crystals, filtered from the mother liquor .The title compound was prepared by the dropwise addition of Uiso(H) = 1.2Ueq(C) for methylene groups and aromatic hydrogen atoms, and Uiso(H) = 1.5Ueq(C) for methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S205698902000208X/wm5540sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S205698902000208X/wm5540Isup2.hklStructure factors: contains datablock(s) I. DOI: 1983920CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Phnl⋯NPrmdn and N—HPrmdn⋯OPhnl (Phnl = phenol and Prmdn = perimidine) hydrogen bonds link the molecules into infinite chains along the b-axis direction. C—H⋯π interactions may further stabilize the crystal structure.The title compound consists of perimidin and methoxyphenol units. In the crystal, O—H 18H16N2O2, consists of perimidine and methoxyphenol units, where the tricyclic perimidine unit contains a naphthalene ring system and a non-planar C4N2 ring adopting an envelope conformation with the NCN group hinged by 47.44 (7)° with respect to the best plane of the other five atoms. In the crystal, O—HPhnl⋯NPrmdn and N—HPrmdn⋯OPhnl (Phnl = phenol and Prmdn = perimidine) hydrogen bonds link the molecules into infinite chains along the b-axis direction. Weak C—H⋯π interactions may further stabilize the crystal structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (49.0%), H⋯C/C⋯H (35.8%) and H⋯O/O⋯H (12.0%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, the O—HPhnl⋯NPrmdn and N—HPrmdn⋯OPhnl hydrogen-bond energies are 58.4 and 38.0 kJ mol−1, respectively. Density functional theory (DFT) optimized structures at the B3LYP/ 6–311 G level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.The title compound, C We report herein the synthesis, the molecular and crystal structures along with Hirshfeld surface analysis and computational calculations of the title compound, (I)Six-membered heterocyclic compounds carrying two nitrogen atoms have been widely studied , ring gave the parameters q2 = 0.3879 (12) Å, q3 = −0.2565 (12) Å, QT = 0.4650 (13) Å, θ2 = 123.47 (15)° and φ2 = 235.98 (18)°]. The ring adopts an envelope conformation, where atom C1 is at the flap position and at a distance of 0.6454 (12) Å from the best plane through the other five atoms. The C4N2 ring is hinged about the N⋯N vector with the N1—C1—N2 plane being inclined by 47.44 (7)° to the best plane of the other five atoms (N1/N2/C9–C11). In the methoxyphenol moiety, the C8—O2—C4—C5 and C8—O2—C4—C3 torsion angles are −2.9 (2)° and 176.72 (12)°, respectively. Rings A (C2–C7), C (C10–C15) and D (C9/C10/C15–C18) are oriented at dihedral angles of A/C = 65.39 (4)°, A/D = 69.63 (4)° and C/D = 4.31 (3)°.The title compound, (I)ng Fig. 1. A puckePhnl⋯NPrmdn and N—HPrmdn⋯OPhnl (Phnl = phenol and Prmdn = perimidine) hydrogen bonds  analysis  have a symmetrical distribution of points with the tips at de + di = 3.03 Å. The H⋯N/N⋯H contacts  have a distribution of points with the tips at de + di = 2.72 Å. The C⋯C contacts  have the tip at de = di = 3.37 Å. Finally, the O⋯C/C⋯O interactions make only a 0.5% contribution to the overall crystal packing.The overall two-dimensional fingerprint plot, Fig. 6dnorm plotted onto the surface are shown for the H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions in Fig. 7a–c, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated as −37.5 (Eele), −7.8 (Epol), −52.0 (Edis), 52.4 (Erep) and −58.4 (Etot)  of the molecule is about 2.6162 eV, and the frontier molecular orbital energies, EHOMO and ELUMO are −3.1985 and −0.5823 eV, respectively.The optimized structure of the title compound, (I)et al., 2011et al., 2013et al., 2013bet al., 2014et al., 2011et al., 2013bet al., 2013bet al., 2011et al., 2013et al., 2014Similar compounds of the perimidine derivative have also been reported  and 1,8- diaminonaphthalene (4 mmol) in ether (30 ml) under agitation at room temperature. Brown single crystals were obtained by the slow evaporation of the acetone solvent after 15 days (yield: 75%).The title compound, (I)C, H15A and H15B of the allyl moiety), 0.98 Å (for methine H atom) and 0.97 Å (for methylene H atoms), and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The hydroxyl H atom was placed in a calculated position with O—H = 0.82 Å and Uiso(H) = 1.5Ueq(O) while H atoms bonded to N atoms were refined independently with Uiso(H) = 1.2Ueq(N)Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989020004284/lh5952sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020004284/lh5952Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020004284/lh5952Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989020004284/lh5952Isup4.cmlSupporting information file. DOI: 1976883CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the PDF version of this Article, the abbreviations for corresponding authors have been reversed“Correspondence and requests for materials should be addressed to Y.Z. (email: jinrong@bjmu.edu.cn) or R.J. (email: zhangyu007@bjmu.edu.cn)”should read:“Correspondence and requests for materials should be addressed to R.J. (email: jinrong@bjmu.edu.cn) or Y.Z. (email: zhangyu007@bjmu.edu.cn)This is correct in the HTML version of the ArticleIn the Materials and Methods section under the subheading “Thymic stromal cell isolation” section,+), pDCs (CD11cint/hiCD45RA+), resident conventional DCs (CD11c+CD8α+CD172α−), and migratory DCs (CD11c+CD8α−CD172α−)”“To purify thymic DCs, cells were stained with fluorescence-labeled antibodies against CD11c, CD45RA, CD8α and CD172α and sorted on a BD FACS Aria II into the following fractions: total DCs (CD11cshould read:+), pDCs (CD11cint/hiCD45RA+), resident conventional DCs (CD11c+CD8α+CD172α−), and migratory DCs (CD11c+CD8α−CD172α+)”“To purify thymic DCs, cells were stained with fluorescence-labeled antibodies against CD11c, CD45RA, CD8α and CD172α and sorted on a BD FACS Aria II into the following fractions: total DCs ,+ and CD172+ cDC was analyzed by flow cytometry following intracellular staining with anti-IL-27”.“(B) IL-27 protein expression in pDC, CD8Should read+ and CD172α+ cDC was analyzed by flow cytometry following intracellular staining with anti-IL-27”.“(B) IL-27 protein expression in pDC, CD8αFigure 6B and 6C were inverted. The correct Figure 6 appears below as


After publication, an error was noticed in the "Cell spreading is altered by RGD mutations" section of the Results. The error occurred in the first paragraph, and the corrected text appears below.RGE and cFNΔRGD allows α5β1 and αv-class integrin–mediated adhesion maturation and spreading, we plated pKO-αv, pKO-β1, and pKO-αv/β1 fibroblasts in serum replacement medium (SRM) on purified cFN variants and determined cell spreading as well as morphology and distribution of FAs  and pKO-αv/β1 fibroblasts (79.6 ± 7.9%) spread on cFNRGE; and a neglectable percentage of pKO-β1 fibroblasts spread on cFNRGE. On cFNΔRGD, the numbers of spread pKO-αv and pKO-αv/β1 fibroblasts dropped to 22.2 ± 15% and 10.4 ± 7.0%, respectively, and of pKO-β1 fibroblasts to <1% , similar to pKO-αv (583 ± 42 µm2) and pKO-αv/β1 fibroblasts (514 ± 49 µm2) on cFNRGE. 2 (P < 0.05 compared to pKO-αv cells) on cFNRGE. In RGE cells from P < 0.001 to P < 0.05.The few adherent pKO-β1 fibroblasts covered a reduced area of 419 ± 36 µm On cFNΔRGD, the adherent pKO-αv, pKO-β1, and pKO-αv/β1 fibroblasts covered significantly smaller spreading areas  when compared with the same cell lines seeded on cFNRGD ("To test whether full-length cFNn of FAs . At 60 ms to <1% . Moreoven cFNRGD ."The P values in


II ion lies on a crystallographic twofold rotation axis and is coordinated by four P atoms from two -1,2-bis(binaphthylphosphonito)ethane (BPE) ligands and two Cl ligands in a distorted cis-FeCl2P4 octahedral coordination geometry. Weak C—H⋯O and C—H⋯π interactions occur in the crystal.In the title compound, the Fe 2,11.03,8.018,23]tricosa-1(15),2(11),3(8),4,6,9,16,18(23),19,21-decaen-13-yl]ethane}dichloridoiron(II) dichloromethane disolvate), [FeCl2(C42H28O4P2)2]·2CH2Cl2, the FeII ion lies on a crystallographic twofold rotation axis and is coordinated by four P atoms from two -1,2-bis(binaphthylphosphonito)ethane (BPE) ligands and two Cl ligands in a distorted cis-FeCl2P4 octahedral coordination geometry. In the crystal, weak C—H⋯O and C—H⋯π interactions link the molecules into layers lying parallel to (001). A weak intramolecular C—H⋯O hydrogen bond is also observed. The asymmetric unit contains one CH2Cl2 solvent molecule, which is disordered over two sets of site with refined occupancies in the ratio 0.700 (6):0.300 (6).In the title compound (systematic name: bis{1,2-bis[12,14-dioxa-13-phosphapentacyclo[13.8.0.0 R,R)- or -1,2-bis(binaphthylphosphonito)ethane  prepared from either (R)- or (S)-1,1′-bi(2-naphthol)  has been used extensively in asymmetric catalysis, as has the related ligand (R) or (S)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl . For example, the BINAP ligand has been coordinated to ruthenium and used for the asymmetric hydrogenation of ketones 2]. The BPE ligand and similar bidentate and monodentate phosphonite ligands have been coordinated to rhodium and iridium and used for asymmetric alkene and quinoline hydrogenation reactions, respectively 2, which crystallized as a dichloromethane solvate.As an extension of these studies, we now describe the synthesis and crystal structure of the iron(II) complex FeClII ion lies on a crystallographic twofold rotation axis and is coordinated by four P atoms from two BPE ligands and two Cl ligands in a distorted cis-FeCl2P4 octahedral coordination geometry. The largest distortion from ideal coordination geometry is the P2—Fe—P2i angle of 108.49 (7)°  are the same, with values of 54.5 (2)°. A weak intramolecular C—H⋯O hydrogen bond is observed :0.300 (6).The molecular structure of the title compound is shown in Fig. 1d Table 2. The asyCg2⋯Cg2 of 4.171 (5) Å (where Cg2 is the centroid of the C4–C9 benzene ring) may be a very weak π-stacking interaction.In the crystal, weak C—H⋯O hydrogen bonds link molecules into sheets parallel to (001) Table 2. Within et al., 20162(P2)2 (P2 = a diphosphine) with P—C bonds reported. The majority, 33 complexes, crystallize with the chloride ions trans to each other, while there are three examples where the chloride ions are cis, as in the title complex. The complex trans-FeCl2ethylene)2, for example, crystallizes with the chloride ions trans 2  and 2.3423 (11) Å in the title complex.A search of the Cambridge Structural Database -BINOL  was combined with -BPE  in 10 ml THF and stirred in a 20 ml dram vial for 24 h. The THF was vacuumed off to yield a brown powder: 31P{1H} NMR : 257.72 ppm, singlet.The ligand was synthesized according to a literature procedure using  = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 32Cl2 solvent molecule was refined without restraints while the minor component was restrained to have similar geometry and anisotropic displacement parameters to the major component using the SAME and SADI instructions in SHELXL  I. DOI: 10.1107/S2056989020011160/hb7939Isup2.hklStructure factors: contains datablock(s) I. DOI: 2023248CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


An intramolecular short S⋯O contact [3.215 (2) Å] is observed. The crystal packing features C—H⋯π interactions.In the title compound, the dihedral angle between the fused pyrazole and pyridine rings is 1.76 (7)°. The benzene and methoxy phenyl rings make dihedral angles of 44.8 (5) and 63.86 (5)°, respectively, with the pyrazolo pyridine moiety. An intramolecular short S⋯O contact [3.215 (2) Å] is observed. The crystal packing features C—H⋯π interactions.In the title compound, C The thiomethyl (–SCH3) group fused to the pyrazolopyridine unit exhibits a (+)anti-periplanar conformation [C8—S1—C7—C6 = 175.47 (15)°]. The torsion angles involving the –SCH3 group differ from those for NUDWOB  group. The –COOC2H5 group attached to the pyrazolopyridine moiety has a (+)anti-periplanar conformation [N3—C7—C6—C9 = 176.44 (16)°]. Further, the methyl group attached to the pyrazole subunit is (+)anti-periplanar [C1—N2—N1—C4 = 178.78 (17)°] and it is attached to the pyridine ring showing a (+)syn-periplanar conformation [C1—N2—C2—N3 = 1.3 (3)°]. The fused pyrazole and pyridine rings in the title compound are not exactly planar, as in NUDWOB ° and that between the methoxyphenyl and pyrazolopyridine rings is 63.86 (5)°.In the title compound Fig. 1, the pheCg and C23—H23⋯Cg) interactions  = 3.291 (2) Å] may also exist  noted by Thomas et al. methanone; Ravi et al., 2017a]pyridine; Wu et al., 2016H-pyrazolopyridine-5-carboxylate; Rao et al., 20202CH3 substituent in the title compound are comparable with those reported for FIZLEI and NUDWOB. The bond distances for the thiomethyl and aryl moieties in the title compound are comparable with those of NUDWOB. Moreover, the bond lengths in the pyrazolopyridine unit of the title compound are comparable with those in NUDWOB, FIZLEI, ALAFID, DAWKAQ and NADPIU. The pyrazolopyridine moiety (N1–N3/C2–C4/C5–C7) of the title compound is approximately planar, as is also observed for NUDWOB, FIZLEI, ALAFID, DAWKAQ and NADPIU. In the title compound, a short intramolecular S⋯O contact of 3.215 (2) Å occurs, but this is not observed in FIZLEI, ALAFID, DAWKAQ, NADPIU and NUDWOB. Moreover, the interaction distance [3.291 (2) Å] of the short intermolecular C⋯O contact in the title compound is comparable with the C⋯O interaction [3.424 (2) Å] in the structure of NUDWOB. Furthermore, as in the title compound, C—H⋯π interactions are observed in the crystal structures of ALAFID, DAWKAQ and NADPIU. The interaction distance of these related structures ranges from 2.89 to 3.23 Å, comparable with the C—H⋯π interactions observed in the title compound.A similarity search of the Cambridge Structural Database  and ethyl 2-(4-methoxybenzoyl)-3,3-bis(methylthio)acrylate  in toluene (3 mL), a catalytic amount of TFA (trifluoroacetic acid) 30 mol % in toluene (3 mL) was added under an N2 atmosphere. The reaction mixture was refluxed for 24 h in an oil bath, the progress of the reaction being monitored by TLC using a mixture of hexane and ethyl acetate (9.9:0.1). After completion of the reaction, the mixture was loaded on a silica gel column  and eluted with increasing amounts of ethyl acetate in hexanes (1% to 5%) to obtain 186 mg (yield = 75%) of ethyl 6-(4-methoxyphenyl)-1-methyl-4-(methylthio)-3-phenyl-1H-pyrazolopyridine-5-carboxylate as a colourless crystalline solid; m.p. 406 K; Rf = 0.3 cm (hexane: ethyl acetate 9.9:0.1). A sample suitable for single-crystal X-ray analysis was obtained by recrystallization from 2 mL of dry methanol.To a solution of 1-methyl-3-phenyl-1Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-methyl).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020008841/dx2029sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020008841/dx2029Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020008841/dx2029Isup3.cmlSupporting information file. DOI: 2005976CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Acetaminophen assists as a co-former in the crystallization of hexamethylenetetramine carboacetaminophenborane, which may otherwise be challenging to form a crystal itself. 15H22BN5O3·C8H9NO2. In the first of these molecules, both the borate-ester and acetylamino groups are considerably twisted away from the plane of the intervening benzene ring . The extended structure of this co-crystal features N—H⋯O and O—H⋯O hydrogen bonds, which link the components into (100) sheets and weak C—H⋯O hydrogen bonds help to consolidate the structure.Hexamethylenetetramine carboacetaminophenborane, a molecule with two pharmacophores attached to a central carboxyborate moiety, was synthesized and crystals were grown with an acetaminophen co-crystal former to result in the title 1:1 co-crystal [hexamethylenetetramine 4-acetamidophenyl 2-boranylacetate–4-acetamidophenol (1/1)], C This type of bond has been previously reported in the acetaminophen co-crystal with citric acid  of this hydrogen bond is similar to the N—H⋯O—H bond (2.09 Å) from the known acetaminophen crystal form II  is identical in length to that of acetaminophen crystal form II (1.85 Å). Several weak C—H⋯O hydrogen bonds may help to consolidate the structure.During crystallization, the new difunctionalized molecule, CORCB-1-APAP, forms a co-crystal with acetaminophen at a 1:1 ratio with hydrogen-bonding interactions Table 1 between et al., 1998A molecular packing projection of (I)et al., 1980et al., 2002et al., 2002et al., 2017et al., 2009et al., 2011et al., 2007et al., 2002The crystal structures of amine carboxyborane have been reported as dimers  involves several steps using trimethylamine carboxyborane (CORCB-3) as the starting material. Trimethylamine carboxyborane, synthesized by the previously reported method  = 1.2Ueq or 1.2Ueq(Cmethyl)].Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020015327/hb7947sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989020015327/hb7947Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020015327/hb7947sup4.pdfCheckCIF. DOI: 1828957CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, molecules of the title compound, a potential ligand containing two 8-quinolinol and one 2-pyridine units, are linked by intermolecular O—H⋯N and O—H⋯O quadruple hydrogen bonds, forming an inversion dimer with two  24H15Cl2N3O2, one quinoline ring system is essentially planar and the other is slightly bent. An intramolecular O—H⋯N hydrogen bond involving the hydroxy group and a pyridine N atom forms an S(5) ring motif. In the crystal, two molecules are associated into an inversion dimer with two R22(7) ring motifs through intermolecular O—H⋯N and O—H⋯O hydrogen bonds. The dimers are further linked by an intermolecular C—H⋯O hydrogen bond and four C—H⋯π interactions, forming a two-dimensional network parallel to (001).In the title compound, C The torsion angles C8—C16—C17—C18, C26—C18—C17—C27, and C28—C27—C17—C16 are −88.6 (2), −101.2 (2) and −87.8 (2)°, respectively.The molecular structure of the title compound is shown in Fig. 1fs Fig. 1. The arri and O4—H4⋯N5i; symmetry code: (i) –x + 1, –y + 2, –z + 2], forming an inversion dimer with two et al., 1999Cg1iii and C24—H24⋯Cg3v; Cg1 is the centroid of the C18–C21/C25/C26 ring and Cg3 is the centroid of the N7/C27–C31 ring; symmetry codes: (iii) x + 1, y + 1, z; (v) –x, –y + 1, –z + 2], forming a ribbon structure along [110]  x – 1, y, z] and a C—H⋯π interaction . The chains are linked by two C—H⋯π interactions , generating a two-dimensional network parallel to (001)  Fig. 4.et al., 2016et al., 19992 methane  and ethanol (6 mL) were placed in a 15 mL capped pressure tube. It was heated at 353 K for 96 h. The generated pale-white precipitate was filtered to give a pale-white solid . Single crystals of title compound suitable for X-ray diffraction were grown by slow evaporation of a solution in CHCl3/n-hexane  at ambient temperature. 1H NMR  δ = 6.63 , 7.21 , 7.33 , 7.52 , 7.52 , 7.67 , 8.48 , 8.64 , 8.81 , 8.84 .The title compound was prepared by a modification of the reported KUiso(H) = 1.2Ueq (C). One outlier  global, I. DOI: 10.1107/S2056989020009317/is5545Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020009317/is5545Isup3.cmlSupporting information file. DOI: 2014831CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


These are connected in three-dimensions by benzene-C—H⋯O(DTBA), DTBA-C=O⋯π(benzene) and benzene-C—H⋯π(benzene) interactions.In the title 1:1 solvate, 2,2′-dithiodibenzoic acid (DTBA):dimethylformamide (DMF), the DTBA molecule is twisted [C—S—S—C = −88.57 (6)°]. Four-molecule aggregates are formed in the crystal  14H10O4S2·C3H7NO, features a twisted molecule of 2,2′-dithiodibenzoic acid (DTBA), with the central C—S—S—C torsion angle being −88.57 (6)°, and a molecule of dimethylformamide (DMF). The carboxylic acid groups are, respectively, close to co-planar and twisted with respect to the benzene rings to which they are connected as seen in the CO2/C6 torsion angles of 1.03 (19) and 7.4 (2)°. Intramolecular, hypervalent S←O interactions are noted [S⋯O = 2.6140 (9) and 2.6827 (9) Å]. In the crystal, four-molecule aggregates are formed via DTBA-O—H⋯O(DMF) and DTBA-O—H⋯O(DTBA) hydrogen bonding, the latter via an eight-membered {⋯OHCO}2 homosynthon. These are linked into supramolecular layers parallel to (011) via benzene-C—H⋯O(DTBA) and DTBA-C=O⋯π(benzene) interactions, with the connections between these, giving rise to a three-dimensional architecture, being of the type benzene-C—H⋯π(benzene). An analysis of the calculated Hirshfeld surfaces indicates, in addition to the aforementioned intermolecular contacts, the presence of stabilizing interactions between a benzene ring and a quasi-π-system defined by O—H⋯O hydrogen bonds between a DTBA dimer, i.e. the eight-membered {⋯OCOH}2 ring system, and between a benzene ring and a quasi-π(OCOH⋯OCH) system arising from the DTBA-O—H⋯O(DMF) hydrogen bond. The inter-centroid separations are 3.65 and 3.49 Å, respectively.The title 1:1 solvate, C In a recent study, it was found the anticipated {⋯HOCO}2 synthon was not always formed but was usurped by a DTBA-O—H⋯O(DMF) hydrogen bond for one of the carboxylic acids, i.e. in the 1:1:1 co-crystal solvate DTBA:2-ClBA:DMF  solution also gave the DTBA:2DMF solvate  solution yielded the mono-solvate, i.e. the title compound DTBA:DMF, (I)Co-crystal formation with 2-mercaptobenzoic acid (2-MBA) is fraught as during crystallization, this is usually oxidized to 2,2′-dithiodibenzoic acid (DTBA)  solution indicating the acid oxidized to DTBA during crystallization. The observed disparity in the C—O bond lengths in the carboxylic acid residues  confirms the location of the acidic H atoms on the O1 and O3 atoms, respectively. A characteristic twisted conformation is evidenced in the C3—S1—S2—C8 torsion angle of −88.57 (6)°. The dihedral angle between the benzene rings is 87.71 (3)°, consistent with an orthogonal disposition. The C1-carboxylic acid group is almost co-planar with the (C2–C7) benzene ring to which it is connected with the dihedral angle between the least-squares planes being 1.03 (19)°. By contrast, a small twist is noted for the C14-carboxylic acid residue where the comparable dihedral angle is 7.4 (2)°. Intramolecular hypervalent S←O interactions via an eight-membered {⋯OHCO}2 homosynthon. The result is the four-molecule aggregate shown in Fig. 2a). For the DTBA⋯DMF interaction, further stabilization is realized through a DMF-C15—H⋯O2(carbonyl) contact, Table 1via benzene-C7—H⋯O(hydroxyl) interactions occurring between centrosymmetrically related molecules. The chains are connected by parallel C=O⋯π(benzene) interactions as detailed in Fig. 2b) and Table 1c), with connections between them leading to a three-dimensional architecture being benzene-C11—H⋯π(benzene), Fig. 2d).The key feature of the supramolecular aggregation in the crystal of (I)Mercury Crystal Explorer 17  and hydroxy-O3—H3O⋯O4(carbonyl) hydrogen bonds with the corresponding dnorm contact distances being 1.62 and 1.64 Å, respectively, i.e. significantly shorter by almost 1 Å compared to the sum of the van der Waals radii of 2.61 Å , Table 2To better comprehend the supramolecular features of (I)π–π interaction formed between the C8–C13 benzene ring and a quasi-π-system defined by O3—H3O⋯O4 hydrogen bonds between a DTBA dimer, i.e. the eight-membered {⋯O4–C14–O3–H3O}2 ring system. A similar observation is also noted for the C1⋯C15 contact which is encapsulated within an apparent π(C2–C7)⋯quasi-π(O2–C1–O1–H1O⋯O5–C15–H15) interaction. The separation between the ring centroids of the aforementioned π–π contacts are 3.65 and 3.49 Å, respectively. The stacking arrangement between the relevant aromatic and quasi-aromatic rings is supported by shape complementarity as revealed by the concave (red) and convex (blue) regions in the shape index, Fig. 5a)–(d), as well as curvedness mappings, Fig. 5e) and (f), obtained through the Hirshfeld surface analysis.Of particular interest among all close contacts present in (I)d,p) approach to verify the nature of the contacts present in (I)O⋯O5 followed by H3O⋯O4 interactions which is consistent with their corresponding short contact distances. By contrast, for the H⋯C and C⋯O interactions relatively smaller charge disparity is noted indicating weaker attractions between the participating atoms,. The exception is found for the C⋯C contacts which exhibit positive electrostatic charge for both donor and acceptor atoms signifying the dispersive nature of the contacts.The electrostatic potential property was mapped onto the Hirshfeld surface using the DFT-B3LYP/6-31G of 2.89 Å, Fig. 6e). Further delineation of H⋯O/O⋯H, H⋯C/C⋯H and H⋯S/S⋯H shows that those heterogeneous contacts are more inclined towards -X⋯H- in DTBA, while the opposite is true for DMF indicating the complementary H-bond accepting and donating nature of DTBA and DMF, respectively. The inclination is more towards -X⋯H- for (I)The quantification of the corresponding close contacts on the Hirshfeld surface through fingerprint plot analysis for overall (I)NCIPLOT 2 and π(C2–C7)–quasi-π(O2–C1–O1–H1O⋯O5–C15–H15) interactions as detected in the Hirshfeld surface analysis by calculating the electron density derivatives through wavefunction approach. The visualization of the resulting gradient isosurface supported the existence of the π–quasi-π contacts based on the corresponding large green domain sandwiched between the aromatic and quasi-aromatic rings. The overall density is in the range of −0.05 < sign(λ2)ρ < 0.03 a.u. indicating a weak but attractive interaction  hydrogen bond, leading to the eight-membered homosynthon as well as the seven-membered heterosynthon formed between hydroxy-O1—H1O⋯O5(carbonyl) and DMF-C15—H15⋯O2(carbonyl) exhibit the greatest interaction energies (Eint) of −69.8 and −58.9 kJ mol−1, respectively. These are relatively stronger than the other supplementary contacts in (I)viz. electrostatic (Eele), polarization (Epol), dispersion (Edis), exchange-repulsion (Erep) together with the total energy are collated in Table 4The strength of each close contact between all pairwise molecules in (I)Crystal Explorer 17, the Eint for the pairs of π⋯quasi-π interactions were modelled in Gaussian16 ⋯quasi-π(⋯O4–C14–O3–H3O)2 or π(C2–C7)⋯quasi-π(O2–C1–O1–H1O⋯O5–C15–H15) interactions, i.e. −59.3 and −59.2 kJ mol−1, respectively.Complementing the calculations with Eele topological framework as shown in Fig. 8a). On the other hand, the dispersion force sustained by the specified π–π interactions results in a boat-shape topology, Fig. 8b). The combination of the electrostatic and dispersion forces supersedes the strong interaction energy from O—H⋯O contacts and lead to a refined overall energy framework with razor-blade-like topology, Fig. 8c).The crystal of (I)et al., 2006et al., 2013i.e. occupied unit-cell volume = 220.8 Å3 = 25.4% for (I)3 and 47.5% for (II).The crystal structure of DTBA·2DMF (II) is also known, being reported four times In term of contact distribution on the Hirshfeld surface for the corresponding individual DTBA molecules and overall (I)Chemical Context, DTBA is usually generated during co-crystallization experiments with 2-mercaptobenzoic acid (2-MBA), implying oxidation of the latter. In addition to oxidation of 2-MBA, other crystallization outcomes have been observed during recent experiments suggesting chemical reactions are occurring. A less common outcome of crystallization experiments with 2-MBA was the sulfur extrusion product, 2,2′-thiodibenzoic acid methylene]cyclohexane-1,4-diamine, for n = 2, 3 and 4  was co-crystallized with 2-MBA, a salt of composition [DTBA_2H]·DMF·H2O was isolated  is 2-(4-ammoniocyclohexyl)-3-(pyridin-2-yl)imidazopyridin-2-ium di-cation, isolated from the co-crystallization of 2-MBA with the n = 2 isomer of (III) C6H10N(+)H3][4-DTBA_2H]·DMSO·H2O was the crystallization product : 3072 ν(C—H), 1680 ν(C=O), 1464 ν(C=C), 1410 δ(C—H), 722 ν(C—S).The DMF monosolvate of DTBA, (I)Uiso(H) set to 1.2Ueq(C). The oxygen-bound H atoms were located from a difference-Fourier map and refined with O—H = 0.84±0.01 Å, and with Uiso(H) set to 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989020008257/hb7925sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020008257/hb7925Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020008257/hb7925Isup3.cmlSupporting information file. DOI: 2011285CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: