S(6) ring motif.The title compound is a Schiff base that exists in the phenol–imine tautomeric form. The molecular structure is stabilized by an O—H⋯N hydrogen bond, forming an  24H24N2O4, was synthesized by the interaction of 2-hydroxy-3-methoxy benzaldehyde and 1,4-benzene dimethanamine in ethanol, and crystallizes in the monoclinic space group P21/n with Z′ = 0.5. The molecule is not planar, the 1,4-diethylbenzene and the phenol rings are twisted with respect to each other, making a dihedral angle of 74.27 (5)°. The molecular structure is stabilized by an O—H⋯N hydrogen bond, forming an S(6) ring motif. In the crystal, molecules are linked by C—H⋯O hydrogen bonds, resulting in the formation of sheets parallel to the bc plane. A Hirshfeld surface analysis was undertaken to investigate the various intermolecular contacts controlling the supramolecular topology, suggesting the H⋯O (18%) contacts to be the most significant interactions, whereas the H⋯H (50.5%) and C⋯H (24.3%) interactions are less significant.The Schiff base compound, C There is an intramolecular O2—H2⋯N1 hydrogen bond (Table 1S(6) ring motif and also induces the phenol ring and the Schiff base to be nearly coplanar, as indicated by the C6—C8—N1—C9 torsion angle of 178.54 (13)°. The molecule is non-planar, the 1,4-diethylbenzene ring being inclined to the phenol ring by 74.27 (5)°. The C7—C6—C8—N1 torsion angle [3.8 (2)°] further supports the co-planarity of the phenol ring and the Schiff base. The C7—O2 distance is 1.3438 (17) Å, which is close to normal values reported for single C—O bonds in phenols and salicylideneamines  moiety revealed some related structures. The most similar structures are 1,4-bis(2-pyridylmethyleneaminomethyl)benzene benzene  ring motif as in the title compound. The length of intramolecular O—H⋯N hydrogen bond in OCAPAK is especially short [1.65 (2) Å] compared to that in the title compound [1.789 (15) Å].A search of the Cambridge Structural Database  using CrystalExplorer17  to 1.404 a.u. (blue). The packing of molecules is mainly dependent on H⋯H (50.5%) and C⋯H (24.3%) interactions and the significant C—H⋯O interactions (18%). Blue regions in the dnorm map indicate intermolecular interactions with distances longer than van der Waals radius sum of the interacting elements  of 2-hydroxy-3-methoxy benzaldehyde was dissolved in 20 mL of ethanol and mixed with 0.0100 g (0.074 mmol) of 1,4-benzene dimethanamine dissolved in 20 mL of ethanol Fig. 4. The reaUiso(H) = 1.5Ueq(O) and a distance restraint. The C-bound H atoms were positioned geometrically  and refined using a riding model, with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989021013347/jq2011sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021013347/jq2011Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021013347/jq2011Isup3.cmlSupporting information file. DOI: 2128953CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the organic dication and perchlorate anions are linked through N—H⋯O, C—H⋯O and N—H⋯N hydrogen bonds, forming a three-dimensional network.In the title salt, C 20H42N42+·2ClO4−, has been determined using synchrotron radiation at 220 (2) K. The structure determination reveals that protonation has occurred at diagonally opposite amine N atoms. The asymmetric unit comprises one half of the organic dication, which lies about a center of inversion, and one perchlorate anion. The macrocyclic dication adopts the most stable endodentate trans-III conformation. The crystal structure is stabilized by intramolecular N—H⋯N, and intermolecular N—H⋯O and C–H⋯O hydrogen bonds involving the macrocycle N—H and C—H groups as donors and the O atoms of perchlorate anions as acceptors, giving rise to a three-dimensional network.The crystal structure of the title salt, C The macrocycle is basic and readily captures two or four protons to form the [C20H42N4]2+ dication or the [C20H44N4]4+ tetracation in which all of the N—H bonds are generally available for hydrogen-bond formation ](NO3)2·3H2O, [Cu(C20H40N4)](NO3)2, [Cu(C20H40N4)](ClO4)2 and [Cu(C20H40N4)(H2O)2](BF4)2·2H2O were reported together with [Zn(C20H40N4)(OCOCH3)2]. In these structures, the copper(II) or zinc(II) cations have tetragonally distorted octahedral environments with the four N atoms of the macrocyclic ligand in equatorial positions and the O atoms of the counter-anions, water molecules or acetato ligands in axial positions ·2(C11H10O) ·2(NO2OH) ·2MeOH 2, (I)We report here the preparation of a new dicationic compound, [Canti with respect to the macrocyclic plane as a result of the molecular inversion symmetry. The [C20H42N4]2+ dication adopts an endodentate conformation and trans-III configuration along the center of the macrocyclic cavity. The endo conformation of the dication may be due to the intramolecular N—H⋯N hydrogen-bonding interaction. Within the centrosymmetric diprotonated amine unit, the C—C and N—C bond lengths range from 1.5173 (18) to 1.5368 (18) Å and from 1.4795 (16) to 1.5044 (16) Å, respectively. The range of N—C—C and C—N—C angles is 108.89 (11) to 113.50 (11)° and 113.46 (11) to 114.61 (11)°, respectively. The bond lengths and angles within the dication are comparable to those found in the free ligand or other cations in (C20H40N4)·2C11H10O ·2MeOH 3}(CN)3]2·2H2O·2MeOH  Å] and N1—C3 [1.4795 (16) Å] are slightly shorter than N2—C8 [1.5044 (16) Å] and N2—C9 [1.4952 (18) Å]. Each of the two hydrogen atoms of N2 and N2′  is involved in hydrogen bonding with both of the two remaining nitrogen atoms (Table 14− anion vary from 1.4218 (19) to 1.4529 (16) Å, and the O—Cl—O angles vary from 106.45 (10) to 110.51 (12)°. The distorted geometry of the ClO4− anion undoubtedly results from its involvement in hydrogen-bonding interactions with the organic cation.An ellipsoid plot of the molecular components in (I)s Table 1. The int4− anions are connected to the [C20H42N4]2+ dication by N—H⋯O hydrogen bonds. The macrocyclic dication is linked to a neighboring ClO4− anion through a very weak C—H⋯O hydrogen bond. The extensive array of these contacts generates a three-dimensional network structure , [C20H42N4]2+ or [C20H44N4]4+. The crystal structures of (C20H40N4)·2C11H10O ·2MeOH  were used as provided. All chemicals were reagent grade and used without further purification. As a starting material, macrocycle 3,14-dimethyl-2,6,13,17-tetraazatricyclodocosane, L, was prepared according to a published procedure  was suspended in methanol (20 mL) and the pH was adjusted to 3.0 with 0.5 M HClO4. The mixture was stirred magnetically for 30 min and the resulting solution was filtered. The neat filtrate was allowed to stand for one week to give block-like colorless crystals of (I)Commercially available A and H2B) were placed in geometrically idealized positions and constrained to ride on their parent atoms, with C—H distances of 0.97–0.98 Å and an N—H distance of 0.99 Å, and with Uiso(H) values of 1.5 and 1.2 times, respectively, that of the parent atoms. The one N-bound H atom (H1N1) of the amine was assigned based on a difference-Fourier map, and a Uiso(H) value of 1.5Ueq(N1).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989021004278/vm2247sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021004278/vm2247Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021004278/vm2247Isup3.cmlSupporting information file. DOI: 2079010CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the molecules are linked by C—H⋯N and C—H⋯O hydrogen bonds into strips, which are connected by F⋯F contacts into layers. a]pyridine core in the molecule of the title compound, C10H7F3N2O, is planar within 0.004 (1) Å. In the crystal, the molecules are linked by pairs of C—H⋯N and C—H⋯O hydrogen bonds, forming strips. These strips are connected by the F⋯F contacts into layers, which are further joined by π–π stacking interactions. The Hirshfeld surface analysis and fingerprint plots reveal that molecular packing is governed by F⋯H/H⋯F (31.6%), H⋯H (16.8%), C⋯H/H⋯C (13.8%) and O⋯H/H⋯O (8.5%) contacts.The bicyclic imidazo[1,2- The C2—C1—C8—C9 and N2—C1—C8—O1 torsion angles of 1.04 (18) and 1.14 (19)°, respectively, show that the ethanone group lies near the plane of the bicycle. The bond lengths N1—C2, C2—C1 and C1—C8 of 1.3367 (16), 1.3987 (16) and 1.4247 (16) Å, respectively, indicate strong π-conjugation in the N1–O1 chain.In the molecule of the title compound Fig. 1, the fusCg1⋯Cg1; Cg1 is the centroid of the imidazole ring].In the crystal, the molecules are linked by pairs of C—H⋯N and C—H⋯O hydrogen bonds into strips elongated along the [210] direction Figs. 2. These ss Figs. 3. The lays Figs. 3 and π–π Crystal Explorer 17 imidazopyridin-3-amine imidazopyridin-3-amine  ring motif. In the crystal, a short H⋯H contact links adjacent molecules into centrosymmetric dimers. The dimers are joined by weak C—H⋯π and slipped π–π stacking interactions, forming layers parallel to (110), which are connected into a three-dimensional network by short Br⋯H contacts. In the crystal of PILGAV01, N—H⋯N hydrogen bonds link the molecules into [010] chains. The cohesion of the crystal structure of DABTEI is ensured by C—H⋯N and C—H⋯O hydrogen bonds, forming layers parallel to the ac plane. In ZAPJAD, the supramolecular structure is defined by two kinds of intermolecular hydrogen bonds. Pairs of N—H⋯N hydrogen bonds link the molecules into centrosymmetric dimers and N—H⋯O hydrogen bonds link the dimers into tubular chains running along the a-axis direction. In the crystal of ULEGOI, molecules are linked into chains through pairs of C—H⋯N interactions, forming a axis.The most closely related compounds containing a similar imidazo+.A mixture of (Uiso(H) = 1.2Ueq(C) for CH hydrogen atoms and Uiso(H) = 1.5Ueq(C) for CH3 hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989021012676/yk2161sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021012676/yk2161Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021012676/yk2161Isup3.cmlSupporting information file. DOI: 2124974CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


E)-2-benzyl-1,3-diphenylisothiouronium iodide, was prepared by the reaction of 1,3-diphenylthiourea and benzyl iodide. In the crystal, N—H⋯I hydrogen bonds link the components into [100] chains.The title compound, a salt form of ° and electrons are delocalized over the N+= C—N skeleton. The dihedral angle between the aromatic rings attached to the N atoms is 40.60 (9)°. In the crystal, N—H⋯I hydrogen bonds link the components into [100] chains.In the title molecular salt, C R–S–C–(NHR)2+ moiety have been investigated as their hydrogen–bonding motifs for molecular recognition of anions methylene]benzenaminium and toluyl units are linked to the sulfur atom as a thioether. The C7—S1 and C8—S1 bond lengths are 1.823 (2) and 1.751 (2) Å, respectively, and the C—S—C bond angle is 101.66 (9)°. The conformation of C1 and C8 about the C7—S1 bond is gauche [C1—C7—S1—C8 = 49.53 (16)°]. The C—S—C bond angle in the title compound is somewhat smaller than that for di-p-tolyl sulfide methylene]benzenaminium moiety of the title cation, the π-electrons of the iminium double bond are delocalized over the N1—C6—N2 skeleton .The title compound, CI− Fig. 1, is a moIn the crystal, the cations and anions are linked by almost linear N—H⋯I hydrogen bonds Fig. 2, generatvia CCDC Access Structures, November 2021; Groom et al., 2016N-[(phenylamino)methylene]benzenaminium but the compound most similar to the title compound is S-benzylisothiouronium chloride , to give a the title compound as a yellow solid . A solution of isothiouronium iodide in methanol was slowly evaporated at room temperature to give crystals of the title compound: m.p. 442–443 K; 1H NMR : δ 7.21–7.39 , δ 4.45 ; HR TOF–MS for C20H18N2S: calculated 318.1186 (M+), found 318.1185 (M+).1,3-Diphenylthiourea (4.4 mmol) was added to a solution of benzyl iodide (13.2 mmol) in dry dichloromethane at room temperature. The reaction mixture was then stirred for 24 h and concentrated Uiso(H) = 1.2Ueq(carrier).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989021013086/hb7997sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021013086/hb7997Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021013086/hb7997Isup3.cmlSupporting information file. DOI: 2127354CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


The parallel-aligned adtp4− ligands with an alternately reversed arrangement further link adjacent CoII ribbons into (010) layers, which are assembled into a three-dimensional supramolecular architecture via intermolecular hydrogen bonds.The title compound, {[Co 2(C12H7NO8)(H2O)2]·1.6H2O}n comprises two CoII ions, which are coordinated by fully deprotonated 2-aminodiacetic terephthalic acid (adtp4–) and terminal water molecules in distorted octahedral N1O5 and O6 coordination environments. The title compound features tetranuclear CoII units bridged by κ3O:O:O′- and κ3O:O,O′-carboxylate groups, which are joined into ribbons via syn–anti carboxylate bridges. The parallel adtp4– ligands with an alternately reversed arrangement further link adjacent CoII ribbons into (010) layers, which are assembled into a three-dimensional supramolecular network via intermolecular hydrogen bonds. The disordered water solvent molecules are situated in channels parallel to [100]. Magnetic measurements and analyses reveal that the title compound displays antiferromagnetic behaviour. The purity of the title compound was characterized by X-ray powder diffraction.The asymmetric unit of the polymeric title compound {[Co The crystal structure, power X-ray diffraction pattern and magnetism of (I) were also studied in detail.Our previous studies have focused on the construction of CPs based on semi-rigid multicarboxylic acids with the aminodiacetate moiety such as 2-aminodiacetic terephthalic acid (HI) comprises two CoII ions, one adtp4– ligand, two terminal water ligands and 1.6 disordered solvent water molecules. Regarding the adtp4– ligand, one carboxylate group  of the aminodiacetate moiety adopts a κ3-O:O:O′ coordination mode and the other one  employs a syn–anti bidentate bridging fashion, whereas the carboxylate group in the ortho-position  coordinates in a κ3-O:O,O′ mode and that in the meta-position  binds to one CoII ion in monodentate fashion (see Scheme). As shown in Fig. 11O5 coordination set for Co1 and an O6 set for Co2. The adip4– ligand chelates Co1 with the amino nitrogen atom (N1) and carboxylate oxygen atoms  from the aminodiacetate moiety and its ortho-positioned carboxylate group. The residual cis-related sites are occupied by one meta-positioned carboxylate oxygen atom (O4ii) and one aminodiacetate oxygen atom (O7i) from two other adip4– ligands (for symmetry codes refer to Table 1ortho-positioned carboxylate group (O1iii and O2iii) from another adip4– ligand chelates Co2, two cis-related positions of which are occupied by two aminodiacetate oxygen atoms (O8iv and O6) from two different adip4– ligands. The remaining two cis-related sites of Co2 are occupied by two terminal water ligands (O9 and O10). The length of the Co—N bond is 2.241 (3) Å and the Co—O distances are between 1.992 (3) and 2.362 (3) Å, which are all in the expected ranges. As shown in Fig. 24– ligands bridge two pairs of CoII ions  into a tetranuclear unit with their κ3O:O:O′-carboxylate groups from the aminodiacetate moieties and ortho-positioned κ3O:O,O′-carboxylate groups  from κ3O:O:O′-carboxylate groups doubly bridge Co1 and Co1ii into a dinuclear unit. The dinuclear unit is further joined with two equivalent Co2i and Co2iii atoms via κ3O:O:O′-carboxylate groups and μ2-oxygen bridges (O1 and O1i) from κ3O:O,O′-carboxylate groups. Adjacent tetranuclear units are linked into a ribbon via double syn–anti bridging carboxylate groups from the aminodiacetate moieties. The closest Co1⋯Co2 and Co1⋯Co1 distances in the ribbon are 3.7074 (8) and 3.5762 (8) Å, respectively. Parallel-aligned adtp4– ligands with an alternately reversed arrangement bind adjacent CoII ribbons into a layer extending parallel to (010)  Fig. 3.I) are assembled into a three-dimensional supramolecular network via intermolecular hydrogen bonds O9—H9A⋯O3v and O9—H9B⋯O2vi (Table 2The (010) layers of (i Table 2. The posχM) of (I) were measured in the range 2–300 K under 1000 Oe. The χM, χM−1 and χMT versus T plots are shown in Fig. 5χMT at 300 K is 5.43 cm3 K mol−1, which is much larger than the expected spin-only value (3.75 cm3 K mol−1) of two isolated CoII ions with g = 2.0, S = 3/2, which may be due to the contribution of the incompletely quenched orbital magnetic moment. As the temperature decreases, the χMT value decreases slowly between 300 and 50 K and then it descends more steeply to the minimum value of 0.51 cm3 K mol−1 at 2 K. The curve clearly indicates that the dominant antiferromagnetic coupling is operating. The temperature dependence of χM−1 follows the Curie–Weiss law, and the linear fit by the equation 1/χM = (T − θ)/C gives C = 5.76 cm−3 K mol−1 and θ = −21.99 K, which is consistent with an antiferromagnetic behaviour.The variable-temperature magnetic susceptibilities . The other two CoII complexes are discrete coordination molecules (H2O)6]·5H2O}n, has been synthesized, which consists of parallel stacked zigzag chains in which CoII cations are linked together through μ3-adtp4− anions.A search of the Cambridge Structural Database  of Co(NO3)2·6H2O and 5.0 ml of CH3CN, then transferred into a 25.0 ml Teflon-lined stainless steel autoclave. The autoclave was sealed, heated to 393 K and held at that temperature for 72 h. The autoclave was allowed to cool to 303 K within 24 h. Plate-like pink crystals of (I) were collected in 66% yield based on H4adtp. Analysis calculated (%) for C12Co2N1O11.6H14.2 (Mr = 475.90): C 30.29, H 3.01, N, 2.94; found: C 30.18, H 3.15, N 3.06. Selected IR data : 3389 (s), 1631 (s), 1570 (m), 1405 (s), 1373 (s), 1319 (b), 1111 (b), 780 (b), 712 (b).HI) was confirmed by powder X-ray diffraction analysis . The peak positions of the experimental PXRD patterns are in good agreement with those simulated on basis of the present single-crystal X-ray data, indicating that a pure phase was obtained.The phase purity of compound (Uiso(H) = 1.5 Ueq(O). Other hydrogen atoms were placed at geometrically calculated positions and treated as riding, with Csp2—H = 0.93 Å, Csp3—H = 0.97 Å and Uiso(H) = 1.2 Ueq(C). H atoms of O11, O12, O13 and O14 are not included in the model but were taken into account in the overall formula.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989021008355/wm5615sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021008355/wm5615Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989021008355/wm5615sup4.tifFigure S1 The simulated and experimental PXRD patterns for compound (I). DOI: 2063394CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure of a ciprofloxacin salt with 2,6-dihydroxybenzoic acid and a ciprofloxacin hydrochloride salt co-crystal with 3,5-dihydroxybenzoic acid are reported. 17H19FN3O3+·C7H5O4−, (I), and ciprofloxacin hydrochloride–3,5-dihydroxybenzoic–water (1/1/1), C17H19FN3O3+·Cl−·C7H6O4·H2O, (II), were determined. In (I) and (II), the ciprofloxacin cations are connected via head-to-tail N—H⋯O hydrogen bonding. Both structures show an alternating layered arrangement between ciprofloxacin and dihydroxybenzoic acid.The crystal structure of two multi-component crystals of ciprofloxacin [systematic name: 1-cyclopropyl-6-fluoro-4-oxo-7-(piperazin-1-yl)quinoline-3-carboxylic acid], a fluoroquinolone antibiotic, namely, ciprofloxacin 2,6-dihydroxybenzoate salt, C The formation of multi-component crystals, Ka of 1.30  and 1.325 (3) Å indicate that it exists as the neutral carboxylic form. However, in 2,6HBA, the C–O distances are very similar i.e., 1.263 (4) and 1.267 (3) Å due to resonance stabilization in the carboxylate anion on Fig. 1. The C—OP1 space group despite the lack of a chiral centre. The asymmetric unit comprises one ciprofloxacin cation, one chloride anion and one 3,5HBA molecule, as shown in Fig. 2Ka of 4.04  and 1.314 (4) Å, respectively, also confirm the neutral state of this moiety. On the other hand, the piperazinyl group is protonated. Hence, compound (II)Compound (II)A⋯F1 hydrogen bonding (Tables 1Compounds (I) Tables 1 and 2 ▸.i.e. N3—H3B⋯O4, N3—H3B⋯O5, and N3—H3A⋯O6, form an infinite chain structure along the a-axis direction a-axis, centrosymmetric pairs of ciprofloxacin molecules are stacked by π–π interactions. The distance between the centroids of symmetry-related C4–C9 rings is 3.4986 (11) Å. This arrangement leads to the formation of a columnar packing arrangement. Interestingly, a similar packing feature was observed in the 1.75 hydrate of ciprofloxacin salicylate n Table 1. The chaA⋯O1 hydrogen bonds (Table 2a). Interestingly, compound (II)b).The supramolecular features of compound (II)s Table 2, formings Table 2a. Interet al., 2019et al., 2020et al., 2020et al., 2020et al., 2014et al., 2016Several crystal structures of ciprofloxacin salts with benzoic acid derivatives have been reported, including salts with salicylic acid Uiso) were fixed to 1.2Ueq of the parent carbon or nitrogen atom and 1.5Ueq for hydroxyl groups.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989022001177/dx2042sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989022001177/dx2042Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989022001177/dx2042IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989022001177/dx2042Isup4.cmlSupporting information file. DOI: 2098049, 2098403CCDC references:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


N,N-dimethylformamide monosolvate was found to crystallize in the monoclinic space group P21/c. The crystal structure of this compound is stabilized by N—H⋯O and N—H⋯Cl hydrogen bonds, as well as π–π stacking.9-Aminoacridinium chloride  N,N-dimethylformamide monosolvate, C13H11N2+Cl−·C3H7NO, crystallizes in the monoclinic space group P21/c. The salt was crystallized from N,N-dimethylformamide. The asymmetric unit consists of two C13H11N2+Cl− formula units. The 9-aminoacridinium (9-AA) molecules are protonated with the proton on the N atom of the central ring. This N atom is connected to an N,N-dimethylformamide molecule by a hydrogen bond. The H atoms of the amino groups create short contacts with two chloride ions. The 9-AA cations in adjacent layers are oriented in an antiparallel manner. The molecules are linked via a network of multidirectional π–π interactions between the 9-AA rings, and the whole lattice is additionally stabilized by electrostatic interactions between ions.9-Aminoacridinium chloride  These bond lengths are characteristic for a C=N double bond that can originate from tautomerism of the cation, as shown on the scheme.The amino groups for two 9-aminoacridine molecules do not readily add a proton. The state of ionization is confirmed by both the H-atom positions (located from the difference map) and by the hydrogen bonding as shown in Table 1et al., 1960The acridine moieties are nearly planar in the crystalline phase with atoms N2, C1, N1 and N5, C17 and N4 arranged almost linearly (N2⋯C1—N1 = 176° and N5⋯C17—N4 = 180°). The dihedral angle between the two outer fused rings is 3.39 (14)° for the molecule containing N2, while the corresponding angle in the molecule containing N5 is 1.18 (15)°. The second value is comparable with that found for acridine , which stack perpendicularly to the c axis. There are two types of 9-AA fused rings in the crystal structure, which results in the propagation of layers in a zigzag manner along b-axis direction .The packing of the molecules in the crystal is illustrated in Fig. 2on Fig. 2.A, attached to N2 and N5, form hydrogen bonds to N,N-dimethylformamide atoms, O1 and O2, with d(N⋯O) = 2.723 (5)–2.740 (5) Å, N—H⋯O = 175-176°. The chloride ions are linked via N—H⋯Cl hydrogen bonds , forming dimers  = 3.608 (5)–3.688 (4) Å and C—H⋯Cl = 163-172°]  to 4.2236 (3) Å. On the other hand, only the two aromatic rings of the acridine B molecules participate in π–π interactions, with adjacent acridine skeletons rotated in-plane with respect to one another. The centroid–centroid distances vary from 3.6514 (3) to 4.7445 (5) Å.Adjacent acridine skeletons are linked nt Fig. 3. All of et al., 2016et al., 1974bP21/c space group with an 9-AA cation and a 3-chlorobenzoate anion in the asymmetric unit and the crystal structure features N—H⋯O and C—H⋯O hydrogen bonds and π–π stacking interactions. Inversely oriented cations and anions form a tetramer; these ions are linked via N(amino)—H⋯O (carboxy) hydrogen bonds, forming a ring motif. 9-Aminoacridinium 3-chlorobenzoate  was dissolved in N,N-dimethylformamide (4 ml) under heating at 418 K until the 9-AA·HCl had fully dissolved. The solution was left to cool to 280 K. Single crystals were obtained after 2 days.9-Aminoacridinium hydrochloride  = 1.2Ueq(C) for aromatic hydrogens and the C—H group and C—H = 0.96 Å and Uiso(H) = 1.5Ueq(C) for the CH3 group. A rotating model was used for the methyl group.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989021011816/dx2038sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021011816/dx2038Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021011816/dx2038Isup3.cmlSupporting information file. DOI: 2120699CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


This tiara-shaped hexamer crystallizing in the triclinic space group P4 centers, which are interconnected through twelve μ2-bridging benzyl thiolate groups. The Pd⋯Pd contacts range from 3.0892 (2) to 3.1609 (2) Å and can be considered as weakly bonding. The unit cell of Pd6 contains also a co-crystallized anthracene-9,10-dione molecule.The first title compound, C R)(H)–S  unit can either be synthesized by nucleophilic substitution of geminal dihalides X–C(R)(H)–X by thiolates RS− methyl]anthracenes with AgI salts 2], ] compounds is dominated by chelate complexes in which open-chain dithioether or macrocyclic polythioether ligands form five- or six-membered rings such as  ] ], in which the thiamacrocycle forms a strained four-membered chelate ring 4][ClO4]2, the strained chelate complexes [M(PhSCH2SPh)4](ClO4)2  are formed bis(benzylsulfane)-S,S′)] was not formed according to the NMR data. Instead, a crystallographic study of a yellow–orange crystal revealed the formation of a cyclic hexanuclear thiolate-bridged cluster [Pd6(μ2-SCH2Ph)12], Pd6. It is well known that thioacetals can be cleaved by soft HgII ions yielding aldehydes or other oxygenated products. One example is the HgIII-promoted deprotection of 3,5-bisBODIPYs, in which cleavage of a dithioacetal function to aldehyde groups occurs (benzyl)sulfane with ceric ammonium nitrate 2] with 2.1 equivalents of benzyl mercaptan in CH2Cl2 solution. However, the isolation of Pd6 was hampered by the co-crystallization of important amounts of the eight-membered cluster Pd8 [Pd8(μ2-SCH2Ph)16], having a structure similar to that of [Pd8(μ2-SPr)16] SBz] (SUNMAQ)  and 2-[bis(benzylsulfanyl)methyl]-6-methoxyphenol [107.76 (10)°], but considerably less than in [BzSCH2SBz] [117.33 (7)°]. The phenyl rings of the benzyl groups and that of the anthracene unit form dihedral angles of 49.21 (4) and 58.79 (5)°.Compound L1 with [PdCl2(PhCN)2] shown in Fig. 36(μ2-SPr)12] 12] 12] 12] 12] 12] has been reported 12] is that of the phenylethanethiolate-decorated nanocluster [Pd6(μ2-SCH2CH2Ph)12]  to 3.1609 (2) Å. The mean Pd⋯Pd separation of 3.1213 (2) Å is quite similar to that of the other derivatives and may be considered as weakly bonding  Å is close to those of the other [Pd6(μ2-SR)12] analogues. The S—Pd—S bridge angles vary within the range 81.033 (16)–99.246 (16)°. The twelve sulfur atoms form two S6 hexagons parallel to the central Pd6 ring from both sides, conferring finally a tiara-like shape to the Pd6S12 scaffold.The core of Note that the crystal structure of anthracene-9,10-dione  has already been the object of several crystallographic studies and is therefore not commented herein  distance of 2.519 (18) Å, the C14—H14⋯C24 distance of 2.741 (18) Å and the C1—H1B⋯C9 distance of 2.847 (16) Å are short enough to be considered as weak intermolecular interactions . The red spots on the surface indicate the close contacts to adjacent molecules. There are three areas of red spots which can be classified as C—H⋯π interactions. The first and most important interaction is the C—H⋯π contact of one of the phenylmethanethiolate substituents to the anthracene scaffold of a neighboring molecule (C14—H14⋯C24). Furthermore, there are significant interactions of the anthracene unit to an adjacent anthracene unit (C21—H21⋯C16/17/29). Then, there is also a weak C—H⋯π contact of two phenylmethanethiolate substituents (C1—H1B⋯C9). The contributions of the different types of intermolecular interactions are shown in the two-dimensional fingerprint plots in Fig. 8b and 6c illustrate the Hirshfeld surface mapped over the shape-index and the curvedness. The shape-index shows large red regions of concave curvature for the anthracene motif, whereas the C—H-donors shows opposite curvature.A Hirshfeld surface analysis methyl-3,5-dinitrothiobenzoate 2 revealed only three similar structures, namely 2,6,10,14,19,24-hexa-p-benz-4,8,12,16,17,21,22,26-octathiatricyclohexacosaphane benzene clathrate 2(PMe3)2] 2ethane)] 2propane)] 2(bis(diphenylphosphino)methane)Cl2] 12] clusters have found applications as precursors for the preparation of monodisperse PdS nanoparticles 12] molecules are interconnected in the solid state by hydrogen bonds through the hydroxy groups of the thiolate ligands, thus generating an infinite three-dimensional supramolecular network 12] has been prepared and probed as a macrocyclic host to include an AgI ion as guest . Crystals suitable for single-crystal X-ray crystallography were grown by slow diffusion of hexane into a dichloromethane solution of L1, m.p. 438–440 K. 1H NMR : 9.03 , 8.39 , 8.00 , 7.95 , 7.55–7.47 , ddd , 7.28–7.22 , 7.14–7.09 , 6.91 , 5.94 , 3.79 , 3.55 . 13C{1H} NMR  138.34 (C16), 132.50 (C17), 131.46 (Cq), 131.36 (Cq), 130.28 (Cq), 129.58 (CHAr), 129.56 (C21), 129.47 (C25), 129.13 (Cq), 128.96 (CHAr), 128.84 (C23), 127.75 (C18), 127.53 (CHAr), 126.63 (C26), 125.61 (C19), 125.12 (C20), 124.91 (C27), 122.99 (C28), 45.02 (S2CH), 37.89 (SCH2). IR (ATR) cm −1: 3050 and 3025 (C—H Ar), 2998, 2948 and 2906 , 1589, 1519 (C=C), 696 (C—S).9-Anthracenecarboxaldehyde  and benzyl mercaptan  were suspended in conc. HCl (2 ml) and allowed to stir at room temperature. After 2 h, the reaction mixture was neutralized with aqueous NaHCO2(PhCN)2Reaction of L1 with PdCl: L1  and PdCl2(PhCN)2  were dissolved in 5 ml of dichloromethane and allowed to stir at room temperature for 30 minutes. During the reaction, a red solution was obtained, which was kept in refrigerator overnight yielding yellow crystals of 9-anthraldehyde along with yellow–orange co-crystals of the  cluster, Pd6. 1H NMR ): 8.92–6.86 , 3.61 , 3.58 .Uiso(H) = 1.2Ueq(C). Hydrogen atoms H1B, H14 and H21 for L1 were located in the difference-Fourier map and refined freely.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989021006113/hb7976sup1.cifCrystal structure: contains datablock(s) mo_b0159_0m, mo_b0283_0m, New_Global_Publ_Block. DOI: 10.1107/S2056989021006113/hb7976mo_b0159_0msup2.hklStructure factors: contains datablock(s) mo_b0159_0m. DOI: 10.1107/S2056989021006113/hb7976mo_b0283_0msup3.hklStructure factors: contains datablock(s) mo_b0283_0m. DOI: 2089413, 2089412CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Preoperative pulmonary function testing is mandatory for non-small cell lung cancer (NSCLC) surgery. The predicted postoperative FEV1 (ppoFEV1) is used for further risk stratification. We compared the ppoFEV1 with the postoperative FEV1 (postFEV1) in order to improve the calculation of the ppoFEV1.87 patients voluntarily received an FEV1 assessment 1 year after surgery. ppoFEV1 was calculated according to the Brunelli calculation. Baseline characteristics and surgical procedure were compared in a uni- and multivariate analysis between different accuracy levels of the ppoFEV1. Parameters which remained significant in the multinominal regression analysis were evaluated for a modification of the ppoFEV1 calculation.p = 0.01), packyears , younger age , and patients undergoing pneumectomy . For the customized ppoFEV1 we excluded pneumonectomies. For patients < 60 years, an additional lung segment was added to the calculation. ppoFEV1 = preFEV1 × Independent factors for a more inaccurate ppoFEV1 were preoperative active smoking (odds ratio (OR) 4.1, confidence interval (CI) 3.6–6.41; We were able to enhance the predictability of the ppoFEV1 with modifications. The modified ppoFEV1 (1.828 l ± 0.479 l) closely approximates the postFEV1 of 1.823 l ± 0.476 l, (0.27%) while the original ppoFEV1 calculation is at 1.78 l ± 0.53 (2.19%). However, if patients require pneumectomy, more complex techniques to determine the ppoFEV1 should be included to stratify risk.The online version contains supplementary material available at 10.1007/s00408-021-00464-4. Anatomical lung resection is the gold standard for the treatment of early-stage non-small cell lung cancer (NSCLC) . PulmonaAll relevant patient data were taken from the electronic hospital information system of our institute. 87 patients voluntarily presented to our out-patient department 1 year after surgery for a routine surgical check-up which included a pulmonary function test. We included all patients who received a postFEV1 in our analysis.The ppoFEV1 is calculated based on the preoperative FEV1 (preFEV1), the number of functional lung segments resected (y), and the total number of functional segments available at time of resection (z). PpoFEV1 = preFEV1 × 1 − entclass1pt{minimamentclasspt{minimaAfter calculating the ppoFEV1, we compared our results with the postFEV1 1 year after surgery.We determined accuracy levels and classified the deviation of the ppoFEV1 in relation to the postFEV1. In order to reflect the greatest differences, we defined the accuracy level of ± 2% as most accurate, the accuracy level of ± 10% as moderately accurate, and the accuracy level of ±  > 10% as inaccurate. We performed a subgroup analysis excluding the ppoFEV1 ± 2% from the ppoFEV1 ± 10%, in order to prevent counting ppoFEV1 ± 2% patients twice. These patients were defined as ppoFEV1 ± 10% >  ± 2%. We analyzed baseline characteristics and surgical procedures which eventually resulted in the most accurate- or inaccurate ppoFEV1 with univariate and multivariate analyses.χ2 or Fisher’s exact test. Continuous parameters were expressed as mean ± standard deviation (SD) and were analyzed by an unpaired Student t test. p-value <0.05 was considered statistically significant. Statistical analysis was performed using the SPSS statistical software package .In cases where univariate analysis showed significant differences, we performed a multinominal regression analysis for further evaluation. Multinomial differences are described by odds ratio (OR) and 95% confidence interval (CI). Categorical variables were analyzed using Pearson’s Significant multinominal parameters were included in our customizing process. The primary objective of this customization was to determine baseline characteristics or surgical procedures which could be included in the calculation in order to improve the ppoFEV1.The customizing process is explained in the results part. The formulas calculated by us are the following.For patients < 60 years, an additional lung segment is added to the calculation ppoFEV1 = preFEV1 × A total of 464 patients underwent anatomical pulmonary resections since 2012 at our institution. 87 (18.8%) patients presented voluntarily for a postoperative check-up and a redo assessment of their pulmonary function 1 year after surgery. We classified patients into categories according to how accurately the ppoFEV1 predicted the postFEV1. The ppoFEV1 of 79% patients showed moderate accuracy of ± 10%. 24% of patients were most accurately predicted with a ± 2% deviation. Calculated values exceeded >  ± 10% in 21% of patients. 51 (45%) patients showed a ppoFEV1 ± 10% >  ± 2% accuracy level. The mean preFEV1 of the cohort was 2.34 l (l) ± 0.61 l and the mean postFEV1 was 1.82 l ± 0.47 l, respectively. Calculation of the ppoFEV1 yielded 1.78 l ± 0.53 l (2.19%).p = 0.01).The baseline characteristics according to the predictive accuracy level are presented in Tables p = 0.05). The preoperative DLCO% (preDLCO%) of patients with ppoFEV1 ± 2% showed a significantly higher value (87.4 ± 17.7) than in ppoFEV1 ± 10 >  ± 2% patients (77.3 ± 19.9) (p = 0.05). The postDLCO however did not differ between ± 2% and ± 10 >  ± 2%. 74.7% of patients were active smokers at the time of surgery (active smoking: smoking in 3 months prior to surgery). Active smoking did not differ between ppoFEV1 ± 2% and ppoFEV1 ± 10% >  ± 2%. 100% of ppoFEV1 >  ± 10% patients were active smokers compared to 71.0% of ppoFEV1 ± 10% . Patients with ppoFEV1 >  ± 10% smoked significantly more than ppoFEV1 ± 10% patients (61.4 ± 19.1 vs. 41.2 ± 24.5 p = 0.002). Heavy smoking is defined as > 30 packyears [p = 0.001).The distribution of age in relation of the ppoFEV1 is shown in Fig.  77.3 ± 1.9 . However, younger age , active smoking , packyears , and heavy smoking (> 30 packyears)  were independent factors for a more inaccurate ppoFEV1.We carried out a multinominal regression analysis for further evaluation of significant results from the univariate analysis (included in Tables p = 0.05). The right lower lobe was resected less often in patients with ppoFEV1 ± 2% . Patients with ppoFEV1 ± 2% never underwent pneumectomy (0 vs. 3.0%) or bilobectomy (0% vs. 6.0%). The most inaccurate FEV1 >  ± 10% was significantly more frequent in patients undergoing pneumectomy   . Pneumectomy on the other was an independent factor for ppoFEV1 >  ± 15% in the multivariate analysis   < 60 years and (3) active heavy smokers we used the original calculation as the modifications canceled each other.To improve the accuracy of the ppoFEV1, we tried to keep the method as simple as possible.In the following section we give two computational examples with the preFEV1 of two patients explaining our customized ppoFEV1.ppoFEV1 = preFEV1 x preFEV1 = 2.67 l; postFEV1 = 2.04 l; ppoFEV1 2.25 lCalculation method: 2.67 l × 1 − Customized method: 2.67 l × 1 − Patient undergoing an upper right lobe resection < 60 years:ppoFEV1 = PreFEV1 × Calculation method: 1.77 × Customized method: 1.77 × Patient undergoing a lower left lobe resection heavy smoker:The mean postFEV1 was 1.823 l ± 0.476 l. By customizing the ppoFEV1 the calculation was more accurate (1.828 l ± 0.479 l) (0.27%) compared to the original ppoFEV1 (1.78 l ± 0.53 l) (2.19%). In addition, customization also led to a redistribution of the accuracy levels we classified Below is the link to the electronic supplementary material.


The manganese(II) centers of each structure are six-coordinate with a distorted octahedral geometry. Although the bis(quinolin-2-ylmethyl)ethanamine ligands differ only by a methyl group, the structure of one complex is dimeric with bridging acetate ligands and exhibits a  4O:O′-bis{manganese(II)} bis(tetraphenylborate) dichloromethane 1.45-solvate, [Mn2(C23O2)2(C23H23N3O)2](C24H20B)·1.45CH2Cl2 or [Mn(DQMEA)(μ-OAc)2Mn(DQMEA)](BPh4)2·1.45CH2Cl2 or [1](BPh4)2·1.45CH2Cl2, and (acetato-κO)(methanol-κO)manganese(II) tetraphenylborate methanol monosolvate, [Mn(CH3COO)(C22H21N3O)(CH3OH)](C24H20B)·CH3OH or [Mn(DQEA)(OAc)(CH3OH)]BPh4·CH3OH or [2]BPh4·CH3OH, by single-crystal X-ray diffraction reveal distinct differences in the geometry of coordination of the tripodal DQEA and DQMEA ligands to MnII ions. In the asymmetric unit, compound [1](BPh4)2·(CH2Cl2)1.45 crystallizes as a dimer in which each manganese(II) center is coordinated by the central amine nitrogen, the nitrogen atom of each quinoline group, and the methoxy-oxygen of the tetradentate DQMEA ligand, and two bridging-acetate oxygen atoms. The symmetric MnII centers have a distorted, octahedral geometry in which the quinoline nitrogen atoms are trans to each other resulting in co-planarity of the quinoline rings. For each MnII center, a coordinated acetate oxygen participates in C—H⋯O hydrogen-bonding interactions with the two quinolyl moieties, further stabilizing the trans structure. Within the crystal, weak π–π stacking interactions and intermolecular cation–anion interactions stabilize the crystal packing. In the asymmetric unit, compound [2]BPh4·CH3OH crystallizes as a monomer in which the manganese(II) ion is coordinated to the central nitrogen, the nitrogen atom of each quinoline group, and the alcohol oxygen of the tetradentate DQEA ligand, an oxygen atom of OAc, and the oxygen atom of a methanol ligand. The geometry of the MnII center in [2]BPh4·CH3OH is also a distorted octahedron, but the quinoline nitrogen atoms are cis to each other in this structure. Hydrogen bonding between the acetate oxygen atoms and hydroxyl (O—H⋯O) and quinolyl (C—H⋯O and N—H⋯O) moieties of the DQEA ligand stabilize the complex in this cis configuration. Within the crystal, dimerization of complexes occurs by the formation of a pair of intermolecular O3—H3⋯O2 hydrogen bonds between the coordinated hydroxyl oxygen of the DQEA ligand of one complex and an acetate oxygen of another. Additional hydrogen-bonding and intermolecular cation–anion interactions contribute to the crystal packing.Structural analyses of the compounds di-μ-acetato-κ These compounds are prepared in a two-step reaction (see reaction scheme) in which manganese(II) acetate is reacted with either DQMEA or DQEA in methanol, followed by anion exchange with sodium tetraphenylborate. The resulting complexes demonstrate how minor alterations in ligand structure can result in significant differences in the complex structure.We have recently begun to study Mn[1](BPh4)2·(CH2Cl2)1.45 crystallizes in the triclinic space group P2Mn(DQMEA)]2+ cation, [1]  in the same octahedral plane and the methoxy oxygen (O1) located perpendicular to this nitrogen plane. This configuration of the DQMEA ligand results in the quinoline groups binding MnIItrans to each other, and in coplanarity of their rings. Hydrogen-bonding interactions between quinolyl hydrogens and an acetate oxygen, C—H⋯O, further stabilize this trans configuration  and 75.56 (5)°, respectively, which are significantly reduced from 90° (Table 1trans N1—Mn1—N3 angle of 148.35 (5)°. Likewise, the bond angle formed by cis coordination of the methoxy oxygen of DQMEA and central nitrogen, N2—Mn1—O1 is 75.32 (5)°. The remaining trans bond angles, O2—Mn1—N2 and O31—Mn1—O1 are 157.89 (5) and 163.58 (5)°, respectively. The Mn—O and Mn—N bond lengths for the neutral DQMEA ligand fall in the range 2.27–2.36 Å, which is typical of manganese(II) complexes  and 2.0908 (14) Å, are significantly shorter.Compound P Fig. 1. The str1] Fig. 2 balancedn Table 3. Oxygens° Table 1. This re[2]BPh4·CH3OH crystallizes in the monoclinic space group P21/c. The structure of this compound consists of the [Mn(DQEA)(OAc)(CH3OH)]+ monocation, [2], tetraphenyl borate counter-ion, and a methanol solvent molecule  and 73.81 (5)°, respectively °. The remaining trans bond angles, O1—Mn1—N1 and N2—Mn1—O4 are 175.54 (6) and 161.38 (6)°, respectively.The compound le Fig. 3. The MnIy Table 2. The alccis coordination of DQEA to Mn(II) in [2] may result from a hydrogen-bonding network involving the alcohol and quinolyl groups of DQEA and the acetate ligand, O—H⋯O and C—H⋯O 2·(CH2Cl2)1.45, no classical intermolecular hydrogen bonding interactions were found. The crystal packing  of a quinoline group . In addition, a network of weak C—H⋯π  intermolecular cation–anion interactions  intermolecular cation–anion interactions  compounds described herein have not been reported previously. We have previously reported the structure of a mononuclear copper(II) complex with DQMEA ethanamine (DQMEA). In a 250 ml round-bottom flask, 5 g (23 mmol) of 2-chlormethylquinoline hydrochloride was dissolved in 10 ml of H2O and cooled to 273 K in an ice bath. A solution of 1.9 g (47 mmol) of NaOH in 10 ml of H2O was added dropwise with stirring. Following this, a solution of 0.9 g (12 mmol) of 2-methoxyethylamine in 10 ml of CH2Cl2 was added. The reaction mixture was then removed from the ice bath, and brought to reflux for 7 days. The mixture was then cooled to room temperature, and the CH2Cl2 layer was separated, washed twice with brine, and dried over anhydrous sodium sulfate. The solution was then filtered, and the filtrate was chromatographed on alumina  eluting with 20:1 CH2Cl2/methanol. Fractions were collected that produced a single spot by TLC on alumina plates  with an RF value of 0.33. Rotary evaporation of these fractions gave 2.4 g (58%) of a light-yellow solid. 1H NMR  δ 2.87 , 3.30 , 3.54 , 4.06 , 7.48 , 7.65 , 7.75 , 8.01 , 8.10 .2-Hydroxy-N,N-bis(quinolin-2-ylmethyl)ethanamine (DQEA). In a 100 ml round-bottom flask, 2.5 g (12 mmol) of 2-chlormethylquinoline hydrochloride was dissolved in 10 ml of H2O and cooled to 273 K in an ice bath. A solution of 0.95 g (24 mmol) of NaOH in 10 ml of H2O was added dropwise with stirring. Following this, a solution of 0.36 g (6.0 mmol) of ethanolamine in 10 ml of CH2Cl2 was added. The reaction mixture was then removed from the ice bath, and brought to reflux for 7 days. The mixture was then cooled to room temperature, and the CH2Cl2 layer was separated, washed twice with brine, and dried over anhydrous sodium sulfate. The solution was then filtered, and the filtrate was chromatographed on alumina  eluting with 100:1 CH2Cl2/methanol. Fractions were collected that produced a single spot by TLC on alumina plates  with an RF value of 0.33. Rotary evaporation of these fractions gave 0.70 g (20%) of a light-yellow solid. 1H NMR  δ 3.02 , 3.54 , 4.17 , 7.51 , 7.74 , 8.07 .2Mn(DQMEA)](BPh4)2BPh4·CH3OH(BPh4)2·(CH2Cl2)1.45 and [2]BPh4·CH3OH are summarized in Table 5[1](BPh4)2·(CH2Cl2)1.45, all H atoms were positioned geometrically and refined using a riding model: C—H = 0.93–0.99 Å, with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-methyl). Idealized methyl groups were refined as rotating groups. A solvate methylene chloride molecule was refined as threefold disordered. All C—Cl bond distances were restrained to be the same within a standard deviation of 0.02 Å. Uij components of ADPs were restrained to be similar to each other . Occupancies were not constrained to unity and refined to 0.401 (3), 0.234 (4) and 0.090 (4). In [2]BPh4·CH3OH, the ethanol group of C21, C22 and O3 was found to be disordered. Bond distances and angles of major and minor moiety were restrained to be similar to each other . Uij components of ADPs were restrained to be similar to each other . The hydroxy H atoms  were located in a difference-Fourier map and refined with the distance restraint O—H = 0.8 (2) Å and with Uiso(H) = 1.5Ueq(O). C-bound H atoms were positioned geometrically and refined as riding: C—H = 0.95–0.99 Å with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C-methyl). Idealized methyl groups were refined as rotating groups. An idealized tetrahedral OH group was also refined as a rotating group: O1S(H1S).Crystal data, data collection and structure refinement details for 10.1107/S2056989021009786/zl5024sup1.cifCrystal structure: contains datablock(s) 1, 2. DOI: 10.1107/S2056989021009786/zl50241sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989021009786/zl50242sup3.hklStructure factors: contains datablock(s) 2. DOI: 2110882, 2110881CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Nature Communications 10.1038/s41467-021-21863-4, published online 12 March 2021.Correction to: 2π−1−σm2τ−1 . The correct form of the equation is: D = (M2π−1−σm2)τ−1.The original version of this Article contained an error in the Methods, section ‘Single-particle tracking photoactivated localization microscopy (sptPALM)’, where an equation incorrectly read: D = MThis has been corrected in both the PDF and HTML versions of the Article.


Embryo implantation into the uterus is a crucial step for human reproduction. A hypothesis has been proposed that the molecular circuit invented by trophoblasts for invasive embryo implantation during evolution might be misused by cancer cells to promote malignancy. Unfortunately, our current understanding of the molecular mechanism underlying embryo implantation is far from complete.Here we used the mouse as an animal model and generated a single-cell transcriptomic atlas of the embryo implantation site of mouse uterus at the invasion phase of embryo implantation on gestational day 6. We revealed 23 distinct cell clusters, including 5 stromal cell clusters, 2 epithelial cell clusters, 1 smooth muscle cell cluster, 2 pericyte clusters, 4 endothelial cell clusters, and 9 immune cell clusters. Through data analysis, we identified differentially expression changes in all uterine cell types upon embryo implantation. By integrated with single-cell RNA-seq data from E5.5 embryos, we predicted cell–cell crosstalk between trophoblasts and uterine cell types.Our study provides a valuable resource for understanding of the molecular mechanism of embryo implantation.The online version contains supplementary material available at 10.1186/s13578-022-00749-y. Embryo implantation in humans is interstitial. It consists of the following three phases: embryo apposition, attachment, and invasion. Immediately after apposition and attachment to endometrial epithelium, the blastocyst penetrates through the epithelium, followed by the basal lamina, and invades into the stroma . It has Due to ethical restrictions and experimental difficulties, in vivo analysis of embryo implantation heavily relies on mice . SlightlIn the present study, by using the-state-of-the-art single-cell RNA-seq approach , we resoAdult CD-1 mice of the SPF grade were used in this study. All mice were caged under light-controlled conditions (14 h/10 h light/dark cycles) with free access to regular food and water. Female mice were mated with fertile males and success of mating was confirmed the next morning by the presence of a vaginal plug. The day of the vaginal plug was denoted as gestation day 1 (GD1). On GD6, the implantation sites and inter-implantation sites (served as a control) were collected separately. All animal procedures were approved by the Institutional Animal Care and Use Committee of South China Agricultural University .The total RNAs from uterine tissues were extracted with the TRIzol reagent (Invitrogen). RNA-seq libraries were generated by using the TruSeq RNA sample preparation kit (Illumina) and sequenced on an Illumina HiSeq 2500 system. Using UCSC mm10 mouse genome as reference, raw data were analyzed using TopHat v2.0.4  and CuffSingle-cell suspension was prepared as described previously , 17. BriThe final concentration of single-cell suspension was adjusted to 1000 cells/μl and a volume of 15 µl was loaded into one channel of the ChromiumTM Single Cell B Chip , aiming at recovering 8000–10,000 cells. The Chromium Single Cell 3' Library & Gel Bead Kit v3  was used for single-cell bar-coding, cDNA synthesis and library preparation, following the manufacturer's instructions provided as the Single Cell 3' Reagent Kits User Guide Version 3. Library sequencing was performed on an Illumina novaseq 6000 system configured with the paired-end 150-bp protocol at a sequencing depth of approximately 400 million reads.Raw data bcl files from the Illumina NovaSeq 6000 platform were converted to fastq files using the bcl2fastq tool (v2.19.0.316). These fastq files were aligned to the mm10 mouse reference genome by using the CellRanger software . The resulting gene counts matrix was analyzed with the R package Seurat (v3.1.3) . Cell wiMonocle2 package v2.18.0  was usedGene ontology (GO) analysis was performed as described previously . GO termPathway enrichment analysis was conducted by using the Metascape v7.4 online tools . The sigThe CellChat v1.1.0 software  was usedTo create a cell-type resolved map of mouse uterus at the invasion phase of embryo implantation, we performed single-cell RNA-seq analysis Fig. A. The imUnsupervised clustering analysis revealed 23 distinct cell clusters for all cells from IIS and IS combined  [+Nkg7−Cd3e+Mki67+), T cells  [+Cd79a+Ms4a1+) [+Adgre1+) [+Adgre1+Mki67+), dendritic cells  [+Itgax+Mki67+) and plasmacytoid dendritic cells  [Hormone-responsive cells included epithelial cells expressing Epcam and Krt19  Fig. 2CC2C, stro7+Cd3e−) , prolife7−Cd3e+) , B cells+Ms4a1+) , macrophAdgre1+) , prolife+Itgax+) , prolifeiglech+) .Finally, we aimed to discover novel markers for each cell type. We selected genes that were expressed significantly higher in the cell type of interest than the other cell types by Wilcoxon rank sum test. A complete list of these marker genes was presented in Additional file –11), developmental processes (P = 1.10 × 10–4), cell organization and biogenesis (P = 3.27 × 10–4), stress response (P = 4.88 × 10–4) and protein metabolism (P = 3.87 × 10–2). Gene set 2 with 352 genes were decreased in S3 compared to its intermediate S2p. These genes were enriched in DNA metabolism (P = 1.00 × 10–11), cell cycle and proliferation (P = 1.00 × 10–11), cell organization and biogenesis (P = 2.59 × 10–11) and protein metabolism (P = 3.97 × 10–3). Gene set 3 of 300 genes were S2-specific. Based on GO, enriched terms were protein metabolism (P = 3.39 × 10–11), developmental processes (P = 6.05 × 10–8) and cell cycle & proliferation (P = 8.09 × 10–3). Gene set 4 of 729 genes were unchanged or increased in S3 compared to its intermediate S2p. Enriched GO terms were protein metabolism (P = 2.49 × 10–8), RNA metabolism (P = 3.23 × 10–7), DNA metabolism (P = 4.42 × 10–5), transport (P = 1.96 × 10–3) cell organization and biogenesis (P = 2.90 × 10–5), and cell cycle and proliferation (P = 4.91 × 10–3).In our single-cell RNA-seq data, we identified 5 clusters of stromal cells: S1 , S1p , S2 , S2p  and S3 . We selected signature genes for each cell cluster by using Wilcoxon rank sum test. After the removal of redundancy, we identified a total of 1784 signature genes  were examined. We found that PDZ expressed pan-stromal cell markers Pgr, Esr1 and Hoxa11, as well as the superficial stromal cell marker Hand2. Additionally, PDZ expressed decidualization marker Wnt4, but not Prl8a2 . PDZ cea were exaTo further reveal the relationship between these 5 stromal cell clusters, pseudotime trajectory analysis was conducted. Cells were arranged in a pseudotime manner with a pedigree reconstruction algorithm for biological processes based on transcriptional similarity. We found 2 paths of interest: (1) primary decidual zone formation, i.e. S2- > S2p/S3; and (2) secondary decidual zone formation, i.e. S1- > S1p , PI3K-Akt signaling pathway (FDR = 1.00 × 10–18), Regulation of actin cytoskeleton (FDR = 1.26 × 10–9), Rap1 signaling pathway (FDR = 1.58 × 10–6), Ras signaling pathway (FDR = 7.94 × 10–5), MAPK signaling pathway (FDR = 1.26 × 10–4), Phospholipase D signaling pathway (FDR = 7.94 × 10–3) and Cytokine-cytokine receptor interaction (FDR = 3.98 × 10–2)  and TGC. We found a total of 20 ligand-receptor interaction pairs Fig. F. Based FDR = 7.9 × 10–5, 2 test was employed to assess the significance of difference between two groups. By using the criteria of P < 0.05 and fold change > 2, we found that the proportion of S1 was unchanged, whereas the proportion of S2 significantly decreased in IS compared to IIS. Meanwhile, S1p and S2p were almost exclusively detected in IS , PI3K-Akt signaling pathway (FDR = 2.00 × 10–9), Regulation of actin cytoskeleton (FDR = 3.16 × 10–9), Hippo signaling pathway (FDR = 3.98 × 10–9), ECM-receptor interaction (FDR = 3.98 × 10–8), Rap1 signaling pathway (FDR = 1.00 × 10–6), MAPK (FDR = 3.16 × 10–6), Wnt signaling pathway (FDR = 2.00 × 10–5), Ras signaling pathway (FDR = 2.00 × 10–5), mTOR signaling pathway (FDR = 2.51 × 10–5), TGF-beta signaling pathway (FDR = 2.51 × 10–5), Endocytosis (FDR = 6.31 × 10–5) and Phagosome (FDR = 7.94 × 10–3)  on S1 and S2, we used the CellChat software to predict the ligand-receptor interactions. Only secreted factors from PDZ were considered. We found a total of 35 ligand-receptor interaction pairs Fig. A. PathwaFDR = 3.1 × 10–9, By using the criteria of P < 0.05 and fold change > 2, we found that the proportion of NKp, Mp and DCp were significantly increased at IS compared IIS Fig. A. Using –7), PI3K-Akt signaling pathway (FDR = 1.26 × 10–6), MAPK signaling pathway (FDR = 3.16 × 10–4), Endocytosis (FDR = 3.98 × 10–4), ECM-receptor interaction (FDR = 3.98 × 10–4), TGF-beta signaling pathway (FDR = 3.98 × 10–4), Rap1 signaling pathway (FDR = 7.94 × 10–4), Hippo signaling pathway (FDR = 2.51 × 10–3), Regulation of actin cytoskeleton (FDR = 7.94 × 10–3), Toll-like receptor signaling pathway (FDR = 1.00 × 10–2), Ras signaling pathway (FDR = 1.26 × 10–2), Natural killer cell mediated cytotoxicity (FDR = 1.58 × 10–2), Jak-STAT signaling pathway (FDR = 3.16 × 10–2) and NOD-like receptor signaling pathway (FDR = 3.98 × 10–2)  and immune cells  using the CellChat software. We found a total of 26 ligand-receptor interaction pairs Fig. A. PathwaFDR = 3.9 × 10–4, By using the criteria of P < 0.05 and fold change > 2, we found that the proportions of both VEC and LEC were significantly decreased in IS compared to IIS, which is in line with the fact that PDZ is avascular –44. Inte–23), Rap1 signaling pathway (FDR = 1.00 × 10–16), Ras signaling pathway (FDR = 1.00 × 10–14), Cytokine-cytokine receptor interaction (FDR = 1.00 × 10–14), HIF-1 signaling pathway (FDR = 1.26 × 10–7), Hippo signaling pathway (FDR = 1.00 × 10–6), Endocytosis (FDR = 3.16 × 10–6), Regulation of actin cytoskeleton (FDR = 6.31 × 10–6), mTOR signaling pathway (FDR = 1.58 × 10–5), MAPK signaling pathway (FDR = 1.58 × 10–5), ECM-receptor interaction (FDR = 3.98 × 10–4), TGF-beta signaling pathway (FDR = 3.98 × 10–4), NOD-like receptor signaling pathway (FDR = 5.01 × 10–3), Toll-like receptor signaling pathway (FDR = 1.26 × 10–2), AMPK signaling pathway (FDR = 2.00 × 10–2), Wnt signaling pathway (FDR = 3.16 × 10–2) and Jak-STAT signaling pathway (FDR = 3.98 × 10–2)  and VEC/LEC. We found a total of 34 ligand-receptor interaction pairs Fig. A. PathwaEmbryo implantation is a crucial step for human embryo implantation. Previously, we performed single-cell RNA analysis of the mouse uterus during the apposition phase and attachment phase of embryo implantation on gestational days (GD) 4–5 , 17. HerIn order to accommodate embryo implantation, an important change in mouse uterus is the formation of primary decidual zone (PDZ). The first sign of PDZ formation occurs on the afternoon of GD5. PDZ is fully established by GD6 –47. In tThe trophectoderm (TE) of mouse embryo is created by the end of the pre-implantation period. After implantation, TE develops into two different types, polar TE and mural TE. Polar TE differentiates into extraembryonic ectoderm (ExE) and ectoplacental cone (EPC), while mural TE differentiates into trophoblast giant cells (TGC). TGC cells are in closest contact to the uterus during embryo implantation . Thus, tBesides the emergence of PDZ, by comparing IS with IIS, we found apparent cell type abundance changes upon embryo implantation. In particular, the proliferating subsets of S1, S2, NK, M, DC and VEC were significantly increased. There were also massive gene expression changes in these cell types. Considering spatial relationships between cell types, uterine cell types other than PDZ are unable to directly communicate with embryonic cells during embryo implantation. Therefore, these changes were likely caused by PDZ indirectly via secreted signaling. Indeed, we found that many soluble factors from PDZ, such as Wnt4, Wnt5a and Wnt6, might have an influence on S1 and S2 cells. Wnt4 is most abundant in the decidual cells. In uterus-specific Wnt4 knockout mice, the embryos were able to attach to the uterine luminal epithelium, but they failed to successfully invade into the uterine stroma . During In conclusion, this study provided a comprehensive single-cell transcriptome atlas for mouse uterus at the invasion phase of embryo implantation. Our data present a valuable resource for deciphering the molecular mechanism underlying embryo implantation.Additional file 1: Table S1. The complete list of novel and known marker genes for each cell type.Additional file 2: Table S2. The complete list of signature genes for stromal cell clusters.Additional file 3: Table S3. The complete list of differentially expressed genes in IS compared to IIS for all cell types (logFC > 0.25 and P < 0.05).


Cadia purpurea roots were investigated herein for the first time. The phytochemical study led to the isolation of two compounds, di-(2-methylheptyl) phthalate (1) and 13-O-pyrrolecarboxyl lupanine (2), from methanol roots extract of C. purpurea. The antibacterial activity results revealed that the n-hexane extract presented a better inhibitory value (13.8 ± 0.0 mm) followed by chloroform (11.1 ± 0.4 mm) and chloroform : methanol (1 : 1) (10.7 ± 0.1 mm) extracts against E. coli at the maximum dose of 100 mg/mL. While, methanolic and ethanolic extracts displayed a mild activity against same bacterium at same dose. The methicillin resistant S. aureus was found with almost total resistance to all extracts up to the 100 mg/mL. The chloroform : methanol (1 : 1), chloroform, and n-hexane extracts recorded inhibition zone values  better than chloramphenicol (7.2 ± 0.6 mm at 30 μg dose) against P. aeruginosa. The alcoholic extracts also exhibited an activity better than chloramphenicol up to 25 mg/mL against same bacterium. Compound 2 produced a comparable inhibition value (9.6 ± 0.0 mm to 18.5 ± 0.0 mm) to that of chloramphenicol (21.5 ± 0.3 mm) against E. coli at doses up to 1.0 mg/mL; whereas, compound 1 showed a slight activity (7.1 ± 0.1 mm–10.3 ± 0.0 mm). Both compounds were found generally inactive against S. aureus, while they provided an activity better than chloramphenicol (7.2 ± 0.6 mm) against P. aeruginosa with inhibition zones ranging from 7.1 ± 0.0 mm to 9.0 ± 0.1 mm for compound 1 and 7.2 ± 0.0 mm to 10.6 ± 0.0 mm for compound 2. Ethanolic and methanolic extracts exhibited a better DPPH radical scavenging activity  and strong ferric ion reducing power  at a concentration of 500 μg/mL compared to the other extracts. Compound 1 also possessed a better anti-DPPH trapping activity  than compound 2 . The compounds, however, indicated a weak ferric ion reduction power even at higher amount. In general, the observed antibacterial and antioxidant activities of isolated compounds and extracts were found to be dose-dependent. Conducting further biochemical investigations on all parts of this plant could provide opportunities of finding extra alkaloidal compounds and other phthalate derivatives with better biological activity.Phytochemicals and antibacterial and antioxidant activities of  Cadia purpurea (Fabaceae) is a shrub which inhabits rift valley escarpment and bush land, commonly in altitudes about 1300–2700 m. In Ethiopia. it is found in Tigray, Welo, Shewa, Hararge, and Bale regions. C. purpurea is also distributed in Eritrea, Yemen, Oman, North Somalia, and North Kenya + at m/z of 390 was showed which is compatible with the molecular composition of C24H38O4, 149.0 (100%), 167 (30.31%), 57.1 (16.65%), 71.1 (11.57%), and 279.1 (10.71%).Compound 1H NMR spectrum, a methylene proton signal at δH 4.22–4.24 , integrated to four protons, was observed. Besides, proton signals at δH 0.96–0.98  and 0.91–0.94  integrated each to six protons were shown implying that there were four methyl groups, in which the first two (C-8′/8″-CH3) were attached to sp3 methine carbons (C-2′/2″), while the latter two (C-7′/7″-CH3) were found to be terminals affixed to sp3 methylene carbons (C-6′/6″). The presence of two symmetric sp3 methine groups was also confirmed by the proton signal at δH 1.58–1.71  in the 1H NMR spectrum. Other eight symmetric methylene protons were appeared at δH 1.30–1.36 as multiplet integrated to a total of sixteen protons. Furthermore, two proton signals (integrated to two protons each) in the low field region at δH 7.72–7.74  and 7.62–7.64  were indicative of four symmetric aryl protons having the same coupling pattern. From 13C and DEPT-135 NMR spectra, twelve intense carbon peaks were clearly shown, which ascribed to twenty-four carbon numbers indicating that there is a symmetry in compound 1. For instance, the presence of a quaternary carbon signal at δ 167.9 (C-7/8) and methylene carbon signal at δ 67.7 (C-1′/1″) confirmed the occurrence of two symmetric aryl ester carbonyl groups. The 13C and DEPT-135 spectra also further supported this by showing eight symmetric carbons, i.e., six aromatic carbons at δ 132.2 , 128.5 (C-2/5), and 131.0 (C-3/4). In addition, the occurrence of two carbon signals in the far right side of the 13C spectrum at δ 10.1 and 13.1 indicated that there were four equivalence methyl groups, C-8′/8″-CH3 (attached to C-2/'2″ at δ 38.8), and terminal C-7′/7″-CH3 (affixed to C-6′/6″ at δ 22.7). Moreover, other four symmetric methylene carbon peaks were observed at δ 23.6 (C-3′/3″), 28.7 (C-4′/4″), 30.2 (C-5′/5″), and 22.7 (C-6′/6″). In the resulted IR spectrum, the absence of a sharp intense hydroxyl peak at its absorption region and the presence of a peak at the carbonyl functional group region (1727 cm−1) along with the absorption bands of 1282 and 745 cm−1, which were due to the ester C=O, C-O and -CH stretches of aromatic protons, respectively, directed that compound 1 exhibits a diester of phthalic acid. Based on the above discussed spectral data (1 was deduced as di-(2-methylheptyl) phthalate (1. Eventhough di-(2-methylheptyl) phthalate is a member of the phthalate groups, unlike to other phthalate esters, it is not a petrochemical and plasticizer. Most of the phthalates and their derivatives are petrochemicals which have been used as plasticizers in chemical industry to improve the plasticity and flexibility of the industrial products +  was observed, 246.2 (100%), 134.05 (29.86%), 112.0 (weak), and 94.0 (weak).Compound 51–154o  along with a methylene carbon signal at the aliphatic region  in the 13C spectrum. Besides, the relatively deshielded multiplet  and triplet  proton signals indicate the presence of methine groups attached to heteroatoms , as also reported elsewhere [δH 1–3 ppm). From the 13C and DEPT-135 spectra, fifteen clear carbon signals were shown which represent a quaternary carbonyl carbon of the amide group at δ 172.8 (C-2), nine sp3 methylene carbons at δ 32.3 (C-3), 18.9 (C-4), 25.6 (C-5), 26.7 (C-8), 46.6 (C-10), 35.4 (C-12), 49.4 (C-15), 27.7 (C-14), and 51.2 (C-17), and five sp3 methine carbons appeared at δ 60.7 (C-6), 33.9 (C-7), 32.2 (C-9), 57.9 (C-11), and 67.7 (C-13). Generally, the abovementioned proton and carbon signals were complementary and characteristics of lupanine skeleton. Besides, the absorption bands shown at 1616 and 2918–2855 cm−1 in the IR spectrum, which belong to the amide carbonyl group (lactam C=O) and -CH stretch of the trans-quinolizidine, respectively, highlighted that compound 2 exhibits a lupanine skeleton. As also reported elsewhere [2 which was assured by three doublets of doublet proton signals occurred at δH 7.01 , 6.21–6.23 , and 6.90–6.92  assigned to the three olefinic methine protons of the pyrrolecarboxyl unit. Their corresponding carbon peaks appeared at δ 123.5 (C-4′), 109.4 (C-5′) and 115.6 (C-6′). In the DEPT-135 spectrum, the two quaternary carbon signals shown at δ 122.2 and 161.7 belong to C-2′ and the carbonyl carbon (C-1′), respectively, of the substituent. Also, the carbonyl (C=O) and secondary -NH groups of the esterified pyrrolecarboxyl moiety showed absorption bands in the wavenumbers (cm−1) of 1692 and 3342 (broad), respectively, in the IR spectrum. This esterified pyrrolecarboxyl unit was incorporated to the lupanine skeleton of compound 2 at C-13 which was identified by the relatively deshielded carbon signal at δ 67.7 (C-13) and triplet proton signal of H-13 at δH 5.19–5.21 . The detailed spectral information obtained of compound 2 is given in 2 was characterized as 13-O-pyrrolecarboxyl lupanine  extracts were found effective against E. coli (>7 mm inhibition zone) at all tested concentrations with the maximum inhibition diameters of 13.8 ± 0.0 mm, 11.1 ± 0.0 mm, and 10.7 ± 0.1 mm, respectively, recorded at the maximal concentration of 100 mg/mL, which were slightly comparable to chloramphenicol (24.5 ± 0.3 mm at 30 μg dose). The remaining lower concentrations, 50 mg/mL, 25 mg/mL, and 12.5 mg/mL, of these extracts also produced an activity with corresponding inhibition zone values of 10.2 ± 0.4 mm, 9.3 ± 0.0 mm, and 8.7 ± 0.0 mm recorded by n-hexane extract, 9.6 ± 0.3 mm, 8.3 ± 0.0 mm, and 7.2 ± 0.0 mm recorded by chloroform extract, and 9.0 ± 0.3 mm, 7.2 ± 0.0 mm, and 7.0 ± 0.0 mm recorded by chloroform/methanol (1 : 1) extract. Interestingly, both the alcoholic extracts experienced a lesser activity against E. coli at concentrations of 100 mg/mL and 50 mg/mL with respective inhibitory values of 9.6 ± 0.1 mm and 8.3 ± 0.1 mm for the methanol extract and 8.0 ± 0.0 mm and 7.6 ± 0.0 mm for the ethanol extract, while no inhibited area was visible at the remaining concentrations of the extracts. The Gram-positive S. aureus strain was found to be susceptible only to the n-hexane and methanol extracts up to the 25 mg/mL dose with measured inhibited area ranging from 7.6 ± 0.0 mm to 10.2 ± 0.5 mm and 7.3 ± 0.0 mm to 8.7 ± 0.0 mm, respectively. Whereas, completely no cleared zone was observed at the minimal concentration (12.5 mg/mL) of these extracts. Also, all tested concentrations of chloroform, chloroform/methanol (1 : 1), and ethanol extracts showed a totally zero zone of inhibition against S. aureus. On the other hand, the chloroform/methanol (1 : 1) extract exerted a positive action on the growth of P. aeruginosa bacterium at all tested dilutions with measured cleared area of 10.0 ± 0.1 mm at 100 mg/mL, 9.7 ± 0.1 mm at 50 mg/mL, 8.4 ± 0.2 mm at 25 mg/mL, and 8.0 ± 0.0 mm at 12.5 mg/mL. The chloroform and n-hexane extracts also made an attempt to inhibit some area of P. aeruginosa growth at all concentrations by providing measured values of 7.7 ± 0.0 mm–9.8 ± 0.1 mm and 7.3 ± 0.0 mm–8.9 ± 0.2 mm, respectively. However, the methanolic and ethanolic extracts scored a slightly lower inhibitory values  against P. aeruginosa at the doses up to 25 mg/mL, but a nil inhibition zone at the least concentration (12.5 mg/mL). To summarize, a better activity against E. coli, especially at the higher concentrations (100 mg/mL and 50 mg/mL), was noted in the nonalcoholic extracts though it looked like less as compared to chloramphenicol (24.5 ± 0.3 mm at dose of 30 μg). Whereas, the inhibitory action indicated by almost all extracts against S. aureus at all concentrations was noted weak in reference to chloramphenicol (18.8 ± 0.4 mm). To the contrary, the inhibition zone values, scored by the extracts against P. aeruginosa, were found even better than that of chloramphenicol (7.2 ± 0.6 mm).2 presented better inhibitory activity than compound 1 against E. coli with greater zone of inhibition of 18.5 ± 0.0 mm recorded at the higher concentration of 1.0 mg/mL, which was comparable to chloramphenicol (21.5 ± 0.3 mm at dose of 30 μg). The remaining concentrations, 0.5 mg/mL, 0.3 mg/mL, 0.1 mg/mL, and 0.05 mg/mL, of compound 2 also produced an activity against same bacterium with respective mean inhibition values of 16.2 ± 0.0 mm, 13.8 ± 0.0 mm, 10.0 ± 0.0 mm, and 9.6 ± 0.0 mm. Compound 1 displayed a moderate activity against E. coli at all concentrations (>7 mm) with inhibition zones laid in the range of 7.2 ± 0.1 mm–10.3 ± 0.0 mm. Whereas, against S. aureus, compound 1 showed a minor inhibitory effect only at concentrations of 1.0 mg/mL (9.1 ± 0.1 mm) and 0.5 mg/mL (8.4 ± 0.0 mm), but a zero effect at the remaining concentrations. Compound 2 was found totally inactive against S. aureus at all concentrations with nil inhibition zone values. However, the two compounds possessed an activity stronger than the chloramphenicol (7.2 ± 0.6 mm) against P. aeruginosa bacterium almost at all dilutions, that is, compound 2 produced mean inhibition zone values ranging from 7.2 ± 0.6 mm to 10.6 ± 0.0 mm and that of compound 1 was found between 7.1 ± 0.0 mm and 9.0 ± 0.1 mm. 2 provided a notable activity against E. coli, especially at the higher concentration, which resulted in an inhibition value close to that of chloramphenicol; whereas, compound 1 was found with lesser activity as compared with compound 2 and chloramphenicol. However, against the methicillin resistant S. aureus strain, both compounds exhibited a negligible activity up to 1.0 mg/mL in comparison to the chloramphenicol antibiotic (18.8 ± 0.4 mm at the dose of 30 μg). But, surprisingly, chloramphenicol had faced strong and unprecedented resistant from P. aeruginosa bacterium which led to even a smaller inhibition zone value (7.2 ± 0.6 mm) than that of the compounds. Overall, the resulted inhibitory potential of the extracts and isolated compounds examined herein was found slightly comparable against E. coli, very weak against S. aureus, and stronger against P. aeruginosa in reference to the standard antibiotic drug, chloramphenicol (at 30 μg dose). In fact, it is difficult to exactly compare the antimicrobial potency of extracts and/or isolates directly with synthesized standard antibiotics like chloramphenicol for similar doses, since there are huge differences between them in terms of chemical polarity, structural patterns, and others.As given in 1 and 2 of Cadia purpurea roots was evaluated against DPPH free radical and ferric ion oxidation. Six various dilutions  of each extract and compound, including ascorbic acid, were prepared from their respective stock solutions (1 mg/mL). Each solution was subjected to the UV-Vis spectrophotometer to measure their absorbance against DPPH radical and ferric reducing power at 517 and 700 nm, respectively. Resulted values of duplicates were expressed as mean ± standard deviation.In vitro antioxidant potential of four extracts  and two isolated compounds DPPH free radical scavenging activity: the DPPH free radical scavenging potential of extracts and isolated compounds was determined compared to ascorbic acid (AA). The obtained result showed that activity of the extracts and compounds against DPPH radical was dose-dependent, in which the DPPH scavenging activity percentage was directly correlated with concentrations .50 values of 12.9 and 16.03 μg/mL at 500 μg/mL concentration. The chloroform and chloroform/methanol (1 : 1) extracts provided the comparatively lesser anti-DPPH activity percentage of 77.07 ± 0.00  and of 79.38 ± 0.16 (26.14 μg/mL of IC50) at same concentration. In reference to the observed anti-DPPH potency of ascorbic acid  at 500 μg/mL, however, the inhibitory activity against the free radical of the tested extracts was found to be weak.As given in 1 presented a greater anti-DPPH activity percentage of 82.69 ± 0.11 at concentration of 500 μg/mL with an IC50 value of 7.99 μg/mL. The quinolizidine alkaloid compound 2 exhibited the smaller scavenging percentage value   for same concentration.Of the compounds evaluated, compound 4 μg/mL) . Here, t3+) ion into its ferrous (Fe2+) of extracts and isolates was known by first observing a change in color of the reaction solutions from yellow to green and then measuring the absorbance at 700 nm [Ferric reducing antioxidant power examination: the potential of reducing ferric  at same amount  toward DNA gyraseB protein of E. coli selected from the Protein Data Bank (PDB ID: 6F86). The docking analysis result  is observed in compound 2 which is comparable with that of ciprofloxacin . As shown in 2 makes three H-bond interactions with Thr-165 via water, Gly-77, and Ile-78 residual amino acids. Besides, this compound coordinates to Pro-79 including a Van der Walls interaction with Asp-73. The hydrophobic and π-anion binding ability of compound 1 with Ile-78 and Glu-50 binding pockets, respectively, is the only drug-likeness indicator of the compound in comparison to ciprofloxacin. Whereas, the ciprofloxacin-like property of compound 2 is recognized only via the formation of a H-bond with Thr-165 active binding site of 6F86.Isolated compounds s result  revealed1) and 13-O-pyrrolecarboxyl lupanine (2), were isolated from methanolic extract of Cadia purpurea roots for the first time. In vitro antibacterial and antioxidant activities of isolated compounds and crude extracts were also evaluated, and the results showed that n-hexane, chloroform, and chloroform/methanol (1 : 1) extracts were found effective against E. coli at all tested concentrations with the maximum inhibition diameters of 13.8 ± 0.0 mm, 11.1 ± 0.0 mm, and 10.7 ± 0.1 mm, respectively, recorded at the maximal concentration of 100 mg/mL, which were slightly comparable to chloramphenicol (24.5 ± 0.3 mm at 30 μg dose). The methanolic and ethanolic extracts, however, experienced a smaller activity against E. coli merely at concentrations of 100 mg/mL and 50 mg/mL with respective inhibitory values of 9.6 ± 0.1 mm and 8.3 ± 0.1 mm, and 8.0 ± 0.0 mm and 7.6 ± 0.0 mm. The methicillin resistant S. aureus strain was found to be sensitive only to the n-hexane and methanol extracts up to the 25 mg/mL dose with measured inhibited area ranging from 7.6 ± 0.0 mm to 10.2 ± 0.5 mm, and 7.3 ± 0.0 mm to 8.7 ± 0.0 mm, respectively. Whereas the chloroform, chloroform/methanol (1 : 1), and ethanol extracts did not indicate any sign of activity against S. aureus even at the higher concentration of 100 mg/mL. On the other hand, the chloroform/methanol (1 : 1) extract exerted an inhibitory action on the growth of P. aeruginosa bacterium at all tested dilutions with measured clear area of 8.0 ± 0.0 mm–10.0 ± 0.1 mm. The chloroform and n-hexane extracts also attempted to inhibit some growth of P. aeruginosa at all concentrations with corresponding measured values of 7.7 ± 0.0 mm–9.8 ± 0.1 mm and 7.3 ± 0.0 mm–8.9 ± 0.2 mm. However, the methanolic and ethanolic extracts scored a slightly lower inhibitory values  against P. aeruginosa up to 25 mg/mL concentration. Compound 2 presented a better inhibitory effect against E. coli than compound 1 with a comparable inhibition value (18.5 ± 0.0 mm) to chloramphenicol (21.5 ± 0.3 mm at dose of 30 μg) recorded at the higher concentration of 1.0 mg/mL. This compound 2 also produced an activity on same bacterium at the concentrations of 0.5 mg/mL, 0.3 mg/mL, 0.1 mg/mL, and 0.05 mg/mL with zone of inhibition values ranging between 9.6 ± 0.0 mm and 16.2 ± 0.0 mm. Compound 1 displayed a moderate activity (>7 mm) against E. coli at all concentrations with inhibition zones laid in the range of 7.2 ± 0.1 mm–10.3 ± 0.0 mm. Whereas, against S. aureus, compound 1 showed a minor inhibitory effect only at concentrations of 1.0 mg/mL (9.1 ± 0.1 mm) and 0.5 mg/mL (8.4 ± 0.0 mm) and compound 2 was found totally inactive at all concentrations. The two compounds, however, possessed an activity stronger than the chloramphenicol (7.2 ± 0.6 mm) against P. aeruginosa bacterium almost at all dilutions with mean inhibition zone values ranging from 7.2 ± 0.6 mm to 10.6 ± 0.0 mm of compound 2 and 7.1 ± 0.0 mm to 9.0 ± 0.1 mm of compound 1. The obtained antibacterial result generally revealed that nonalcoholic extracts were noted with a better activity against E. coli, especially at the higher concentrations (100 mg/mL and 50 mg/mL), though they seemed like weak compared to the chloramphenicol (24.5 ± 0.3 mm at dose of 30 μg). Compound 2 also provided a notable activity against E. coli, especially at the higher concentration, which resulted in an inhibition value close to that of chloramphenicol (21.5 ± 0.3 mm); whereas, compound 1 was found with weaker activity as compared with compound 2 and chloramphenicol. On the other hand, against the methicillin resistant S. aureus strain, both compounds and all the extracts exhibited a negligible activity up to the higher dosage in reference to the chloramphenicol antibiotic (18.8 ± 0.4 mm). On the contrary, the inhibition zone values, scored by the extracts and compounds against P. aeruginosa, were found even better than that of chloramphenicol (7.2 ± 0.6 mm). Regarding the antioxidant potency, ethanolic and methanolic extracts exhibited a better DPPH radical scavenging activity  at concentration of 500 μg/mL, whereas the chloroform and chloroform/methanol (1 : 1) extracts were observed weak with IC50 values of 27.52 and 26.14 μg/mL. Comparatively strong ferric ion reducing power was also shown in the alcoholic extracts with 0.810 ± 0.001 absorbance of methanol and 0.788 ± 0.000 of ethanol at the maximum amount (500 μg/mL). Compound 1 indicated a promising trapping potential against DPPH radical , while compound 2 recorded a higher IC50 value (58.34 μg/mL) at concentration of 500 μg/mL. However, at same dosage, the isolated compounds indicated a weak power of ferric ion reduction with recorded absorbance of 0.761 ± 0.002 by compound 1 and 0.458 ± 0.001 of compound 2. The molecular docking result revealed that compound 1 shows two hydrophobic (with Ile-78 and Ile-94), a π-anion (with Glu-50) and Van der Walls interactions with some amino residues of E. coli gyraseB; whereas, compound 2 makes three H-bond interactions with Thr-165, Gly-77, and Ile-78 in addition to the Van der Walls interaction with Asp-73. In conclusion, the present findings indicated that the resulted antibacterial inhibitory potential of the extracts and isolated compounds was found slightly active against E. coli, very weak against S. aureus, and stronger against P. aeruginosa as compared to chloramphenicol (at 30 μg dose); and the entire antibacterial and antioxidant activities of tested analytes were noted as dose-dependent. Besides, since other quinolizidine alkaloids (similar to compound 2) were also reported from the leaves of Ethiopian Cadia purpurea, conducting further biochemical investigations on all parts of the plant could provide opportunities of finding additional alkaloidal compounds and other phthalates with powerful biological activities.In this study, two compounds, di-(2-methylheptyl) phthalate (


Paratylenchus spp., are relatively small nematodes that can feed on a wide range of host plants. The morphological identification of this nematode is greatly hampered by their small size and variable characters. This study provides the first report of Paratylenchus lepidus from Vietnam with a combination of morphological and molecular characterizations. The 28S rDNA phylogenetic tree of the genus and the first COI mtDNA barcode of this species are also provided.The pin nematodes,  Paratylenchus  is commonly known as pin nematodes that are ectoparasites and can be frequently found at high density in perennial plants, hop gardens, orchards, or forest trees  Kuntze) in Vietnam. Nematodes were extracted using the modified Baermann tray method (COI mtDNA gene were amplified using D2A/D3B (5′–ACAAGTACCGTGGGGAAAGTTG–3′/5′–TCGGAAGGAACCAGCTACTA–3′) (www.geneious.com). The best fit model was chosen using Mega 7 and phylogenetic analysis was done following Nguyen et al. (2019c).Soil and root samples were collected from the rhizosphere of green tea (y method . After tACTA–3′)  and JB3/n = 20 (♀♀): L = 340 ± 20 (307-371) µm, a = 25 ± 1 (22-27), b = 4.1 ± 0.3 (3.7-4.6), c = 11.5 ± 1.4 (9.8-13.8), c′ = 3.5 ± 0.4 (3.0-4.1), V% = 82 ± 1 (81-84), Lip height = 2.7 ± 0.5 (1.9-3.6) µm, Lip width = 4.9 ± 0.5 (4.2-5.9) µm, Stylet = 25 ± 1 (24-27) µm, Median bulb length = 15.2 ± 2 (12.8-18.0) µm, Median bulb width = 6.9 ± 0.6 (5.9-7.7) µm, SE pore = 75 ± 4 (67-81) µm, Pharynx = 84 ± 3 (79-91) µm, Body width = 13.8 ± 0.4 (13.3-14.5) µm, Vulval body diam. = 12.2 ± 0.4 (11.3-12.6) µm, Anal body diam. = 8.5 ± 0.4 (7.9-9.5) µm, Tail length = 30 ± 3 (26-35) µm.Paratylenchus lepidus is characterized by having a slender body, curved ventrally; lateral field with four incisures; lip region weakly sclerotized, continuous to body contour; median bulb elongate with a distinct valve; isthmus slender, surrounded by nerve ring; basal bulb pyriform; secretory-excretory pore located at level of basal bulb to pharyngo-intestinal junction; hemizonid located just anterior to secretory-excretory pore; gonad monodelphic, post uterine sac absent; vulval lips not protruding but having prominent advulval ﬂap; tail curved ventrally with a finely rounded to bluntly pointed terminus  was 99.7% similar (2 bp difference) to the sequence of P. lepidus from GenBank (accession number: MK886692). The phylogenetic tree based on 28S rDNA sequences showed that the sequence of P. lepidus from Vietnam was placed together with the sequence of P. lepidus from GenBank (100% PP) (COI mtDNA sequence of P. lepidus from Vietnam (418 bp long) was also obtained and submitted to GenBank under the accession number MT828831.The 28S rDNA sequence of 100% PP) . A COI mP. lepidus from green tea in Vietnam is in agreement with the description of the type population (P. lepidus in Vietnam. The first COI mtDNA sequence of P. lepidus is also provided to serve as a molecular barcode for molecular identification of Paratylenchus species in the future.Morphology of pulation  with smapulation . In this


Two copper(II) cations are situated in distorted square-pyramidal environment, while two copper(II) cations are located in a slightly square-planar geometry. One bridging acetate group acting in an η1:η1-μ2-mode connects two copper(II) ions, while another bridging acetate group connects three copper(II) ions in an η1:-η2–μ3-mode.In the title Schiff base tetranuclear copper(II) complex, two discrete environments are present in the structure: CuNO 3-acetato)(μ2-acetato)bisethylidene]amino}propan-2-olato)tetracopper(II) monohydrate, [Cu4(C19H19N2O3)2(CH3CO2)2]·H2O, corresponds to a non-symmetric tetranuclear copper complex. The complex exhibits one ligand molecule that connects two copper CuII metal centres via its ethanolato oxygen anion acting in a μ2-mode and one ligand molecule that connects three copper CuII metal centres via its ethanolato oxygen anion acting in a μ3-mode. One bridging acetate group acting in an η1:η1-μ2-mode connects two copper(II) ions while another bridging acetate group connects three copper(II) ions in an η1:-η2-μ3-mode. A chair-like Cu3O3 structure is generated in which the two CuO4N units are connected by one μ2-O ethanolate oxygen atom. These two units are connected respectively to the CuO3N unit via one μ3-O ethanolate oxygen atom and one μ2-O atom from an acetate group. The μ3-O atom also connects one of the CuO4N units and the CuO3N unit to another CuO3N unit, which is out of the chair-like structure. Each of the two pentacoordinated CuII cations has a distorted NO4 square-pyramidal environment. The geometry of each of the two CuNO3 units is best described as a slightly square-planar environment. A series of intramolecular O—H⋯O hydrogen bonds is observed. In the crystal, the units are connected by intermolecular C—H⋯O and O—H⋯O hydrogen bonds, thus forming sheets parallel to the ac planeThe title molecular structure, namely, (μ Mixing H3L and hydrated copper acetate yielded a tetranuclear complex formulated as [Cu4L2(CH3CO2)2]·H2O in which the ligand acts in its tri-deprotonated −3L form. In the tetranuclear complex, one of the −3L anions acts in μ2-mode, connecting the two pentacoordinated CuII cations. The second −3L anion acts in μ3 mode, connecting the two tetracoordinated CuII cations and one of the pentacoordinated CuII cations. The second pentacoordinated CuII cation is connected to the two tetracoordinated CuII cations via an acetate group acting in η1:η2-μ3 mode. Additionally, the two pentacoordinated CuII cations are connected by an acetate group acting in η1:η1-μ2 mode. For each ligand, the azomethine nitrogen atom and the phenolate oxygen atom of one arm are both linked to one CuII cation while the corresponding atoms of the other arm are bonded to another CuII cation. No phenolate oxygen atom acts in bridging mode. In one ligand the ethanolate oxygen atom bridges the two pentacoordinated CuII cations, and in the second ligand the ethanolate oxygen atom bridges the two tetracoordinated CuII cations and one pentacoordinated CuII cation. The two −3L ligands are coordinated differently in hexadentate  and heptadentate  fashions. Four five-membered CuOCCN rings and four six-membered CuOCCCN rings are formed upon the coordination of the ligand molecules. In the tetranuclear complex, two discrete CuO4N and CuO3N units are observed.τ parameter  around the metal ion are τ = 0.1103 for Cu1 and τ = 0.1887 for Cu2. For Cu1 and Cu2, the basal planes are occupied by one phenolate oxygen anion, one azomethine nitrogen atom, one ethanolate oxygen atom and one oxygen atom from the η1:η1-μ2 acetate group, the apical position being occupied by an ethanolate oxygen atom from a second ligand molecule for Cu1 and an oxygen atom from the η1:η2-μ3 acetate group for Cu2. The atoms forming the basal plane for Cu1  are almost coplanar (r.m.s. deviation = 0.1088 Å) and the Cu1 atom is displaced toward the O5 atom, which occupies the apical position, by 0.0545 (2) Å. The Cu1—O5 distance of 2.749 (3) Å is longer than the distances between Cu1 and the atoms in the basal plane , as expected for a Jahn–Teller distortion –95.10 (14)° and 169.71 (16)–176.33 (14)°, respectively. The atoms forming the basal plane for Cu2  are less coplanar than those around Cu1 (r.m.s. deviation = 0.2086 Å) and the Cu2 atom is displaced toward the O8 atom, which occupies the apical position, by 0.0808 (1) Å. The from Cu2—O8 distance of 2.703 (4) Å is longer than those to atoms in the equatorial plane . As observed for Cu1, Jahn–Teller distortion –96.89 (14)° and 161.66 (15)–173.00 (15)°, respectively. The bond lengths involving the μ2-bridging ethanolato oxygen atom and the copper cations are asymmetrical: Cu1—O2 = 1.916 (3) Å and Cu2—O2 = 1.920 (3) Å. The distances between the μ3-bridging ethanolato oxygen atom and the copper cations are very different: Cu1—O5 = 2.749 (3) Å, Cu3—O5 = 1.907 (3) Å and Cu4—O5 = 1.921 (3) Å. The copper cations Cu3 and Cu4 are coordinated by one ethanolato oxygen anion, one phenoxo oxygen anion, one azomethine nitrogen atom of the ligand and one oxygen atom of a η1:η2-μ3 acetate group (O8 for Cu3 and O7 for Cu4). The Cu3—O4 [1.873 (3) Å], Cu3—O5 [1.907 (3) Å], Cu3—N3 [1.947 (4) Å], Cu3—O8 [1.957 (3) Å], Cu4—O6 [1.869 (3) Å], Cu4—O5 [1.921 (3) Å], Cu4—N4 [1.962 (4) Å] and Cu4—O7 [1.955 (3) Å] distances are in close proximity to values reported for copper(II) complexes with analogous Schiff base ligands  and 0.1801 (Cu4) suggested distorted square-planar geometries. For the two copper cations the cisoid angles are in the ranges 86.17 (14)–93.29 (15)° for Cu3 and 84.04 (14)–96.93 (14)° for Cu4 and the transoid angles are O4—Cu3—O5 = 177.07 (15)°, O8—Cu3—N3 = 173.28 (15)°, O6—Cu4—O5 = 170.48 (14)° and O7—Cu3—N4 = 164.11 (15)°. The C—N bonds are in the range 1.291 (6)–1.300 (6) Å, indicative of double-bond character and the presence of the imino groups in the two ligands.Atoms Cu1 and Cu2 are pentacoordinated and their environments can be best described as slightly distorted square-pyramidal. The Addison phenoxo are observed ethylidene)]-2-hydroxypropane-1,3-diamine is widely used in coordination chemistry. The current release of the CSD ethylidene)]-2-hydroxypropane-1,3-diamine (HL3) was prepared from 1-(2-hydroxyphenyl)ethanone and 2-hydroxypropane-1,3-diamine in a 2:1 ratio in ethanol according to a slight modification of a literature method : 3538 (OH), 3268 (OH), 1605 (C=N), 1538 (C=C), 1528 (C=C), 1455 (C=C), 1247 (C—O), 1043, 760. Analysis calculated for C19H22N2O3: C, 69.92; H, 6.79; N, 8.58. Found: C, 69.90; H, 6.76; N, 8.56%.The ligand 3CO2)2·(H2O)  in 5 mL of ethanol was added to a solution of H3L  in 10 mL of ethanol at room temperature. The initial yellow solution immediately turned deep green and was stirred for 30 min before being filtered. The filtrate was kept at 298 K. After one week, light-green crystals suitable for X-ray diffraction were collected and formulated as [Cu4L2(CH3CO2)2]·H2O. FT–IR : 3404, 1601, 1532, 1332, 1299, 895, 760. Analysis calculated for C42H46Cu4N4O11: C, 48.64; H, 4.47; N, 5.40. Found: C, 48.60; H, 4.49; N, 5.44%.A solution of Cu were geometrically optimized  and refined using a riding model (AFIX instructions) with Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for CH3 and OH groups.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989022002225/ex2053sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022002225/ex2053Isup3.hklStructure factors: contains datablock(s) I. DOI: 2154581CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information: