II atom has a distorted square-pyramidal coordination environment. The molecular structure exhibits an intramolecular O—H⋯N hydrogen bond. In the crystal, the molecules are linked by intermolecular C—H⋯Br hydrogen bonds, generating ribbon structures. These ribbons are linked though intermolecular C—H⋯Br hydrogen bonds, forming a two-dimensional network sheet.In the title compound, the Zn 2(C22H19ClN4O)], the ZnII atom adopts a distorted square-pyramidal coordination geometry, formed by two bromido ligands and three N atoms of the bis(pyridin-2-ylmethyl)amine moiety in the pentadentate ligand containing quinolinol. The ZnII atom is located well above the mean basal plane of the square-based pyramid. The apical position is occupied by a Br atom. The O and N atoms of the quinolinol moiety in the ligand are not coordinated to the ZnII atom. An intramolecular O—H⋯N hydrogen bond, generating an S(5) ring motif, stabilizes the molecular structure. In the crystal, the molecules are linked by intermolecular C—H⋯Br hydrogen bonds, generating ribbon structures containing alternating R22(22) and R22(14) rings. These ribbons are linked through an intermolecular C—H⋯Br hydrogen bond, forming a two-dimensional network sheet.In the title compound, [ZnBr Its derivatives are utilized as chemosensors for detecting ZnII at low concentration in biological samples  bromide. Here, the crystal structure of the respective title compound is reported.8-Quinolinol (Hq) is a notable bidentate ligand and an excellent analytical reagent for the determination of the concentration and separation of metal ions  and three N atoms  of the dpa moiety in HClqdpa forming the ZnBr2(dpa) unit. The Hq moiety of the pentadentate ligand (HClqdpa) is not coordinated to the ZnII center. The five-coordinate geometry parameter, τ = (β − α)/60, derived from the two largest angles (α < β) in a structure has ideal values of 0 for square-pyramidal and of 1 for trigonal–bipyramidal geometry  Å above the mean basal plane (Br2/N8/N7/N9) of the square-based pyramid. The dpa moiety is meridionally bound to the ZnII atom. The apical position is occupied by the Br1 atom with the apical bond being slightly elongated to 2.4419 (4) Å compared to the equatorial Br2—Zn3 bond length of 2.4085 (4) Å. The Zn—N bond lengths in the title compound are 2.1455 (18) and 2.1497 (18) Å for the pyridyl atoms , and 2.2670 (18) Å for the tertiary atom N7. In comparison, the Zn—N bond lengths in the crystal structure of a related complex with a mesityl methylene-appended dpa derivative are 2.093 (3), 2.066 (3), and 2.521 (3) Å  ring motif  1 − x, −y, −z]  1 − x, 1 − y, 1 − z]  x + 1, y − 1, z] (Table 1C(6) chain motif running along  Table 1, forming] Table 1, which ffs Fig. 2. In the ] Table 1, forming0] Fig. 3. The rib] Fig. 3.et al., 2016ConQuest amino]methyl fragment as ligand gave 517 hits, and among those, eight hits with two bromido ligands. Of these eight analogues, three structures are complexes with dpa bearing a tertiary N donor atom directly bound to an aromatic moiety , the tertiary N atoms are bound to aliphatic carbon atoms as in the title complex. Four of these five closely related structures exhibit square-pyramidal geometries with dpa being meridionally coordinated methyl]propan-2-amine}dibromidozinc(II) . Of these, six structures (three compounds) are ion-pairs between tetrachloridozincate(II) and an 8-hydroxyquinolin-1-ium (H2q+) derivative, for example, (H2q)2[ZnCl4]  and quinolin-8-lato derivatives, e.g. 8-hydroxy-2-methylquinolinolinium diiodo(2-methyluinolin-8-lato)zinc(II)  tris(4-nitrophenol) biszinc(II) dihydrate zinc(II) trihydrate amino]methyl at the 2-position of Hq or respective derivatives, gave three hits  was dissolved in 15 mL of hot acetonitrile. Then a solution of zinc(II) bromide  in 15 mL of hot acetonitrile was added to the ligand solution. The mixture was stirred for 20 min at 333 K. After removal of the solvent at room temperature in air for one week, colorless crystals of the title compound were obtained . Analysis calculated for CUiso(H) = 1.2Ueq(C). One outlier reflex (002) was omitted from the refinement.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989022001530/yz2016sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989022001530/yz2016Isup2.hklStructure factors: contains datablock(s) I. DOI: 2150991CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


Heterodera microulae sp. n., was isolated from the roots and rhizosphere soil of Microula sikkimensis in China. Morphologically, the new species is characterized by lemon-shaped body with an extruded neck and obtuse vulval cone. The vulval cone of the new species appeared to be ambifenestrate without bullae and a weak underbridge. The second-stage juveniles have a longer body length with four lateral lines, strong stylets with rounded and flat stylet knobs, tail with a comparatively longer hyaline area, and a sharp terminus. The phylogenetic analyses based on ITS-rDNA, D2-D3 of 28S rDNA, and COI sequences revealed that the new species formed a separate clade from other Heterodera species in Goettingiana group, which further support the unique status of H. microulae sp. n. Therefore, it is described herein as a new species of genus Heterodera; additionally, the present study provided the first record of Goettingiana group in Gansu Province, China.A new cyst-forming nematode,  Heterodera was erected by Schmidt (1871) and currently contains about 80 species  units are good candidate genes for molecular taxonomic and phylogenetic studies  were recovered from hatched eggs and kept in water suspension until further use  and AB28 (5′-ATATGCTTAAGTTCAGCGGGT-3′) (COI gene was amplified using primers Het-coxiF (5′-TAGTTGATCGTAATTTTAATGG-3′) and Het-coxiR (5′-CCTAAAACATAATGAAAATGWGC-3′) . Three sets of primers  were used in the PCR analyses to amplify sequences of the ITS, D2-D3 expansion segments of 28S, and GGGT-3′) . The 28SGGGT-3′) . FinallyGWGC-3′) . PCR conCOI gene) were compared with known sequences of Heterodera using BLASTn homology search program. Outgroup taxa for phylogenetic analyses were selected based on the previously published studies (http://tree.bio.ed.ac.uk/software/figtree/)  . The speHeterodera microulae sp. n. It is lemon-shaped with an obtuse vulval cone, neck extruding, and cuticle thick with an irregular zig-zag pattern. The color was white to pale to medium brown; remnants of the subcrystalline layer were rarely present. The egg sac was usually absent , 3B, C. The female was lemon-shaped, pearl white, or pale yellow in color. It was rarely rounded with a protruding neck and vulva, the subcrystalline layer was present, and the egg sac absent . There wThe body was straight or slightly curved ventrally after heat treatment . The lipBody hyaline without any markings was presented; juveniles folded six times .The male was not found.Holotype and paratype material  were deposited in the nematode collection of the Department of Plant Protection, Biocontrol Engineering Laboratory of Crop Diseases and Pests of Gansu Province, Lanzhou, China.Heterodera microulae sp. n. was collected from the roots and rhizosphere soil of Microula sikkimensis Hemsl.  in Tianzhu county of Gansu Province, China. The geographical position is N 37°11′46″; E 102°47′6″. This site was located in continental highland with the vegetation type of meadow grassland and the soil is composed of chernozems. The climatic parameters of the site include 450 mm of average rainfall and an approximate −2 air temperature.The species is named after the host of its isolation.Heterodera microulae sp. n. is characterized by having lemon-shaped cysts that have protruding necks and obtuse vulval cones. The cysts are 414 to 543-µm long and 305 to 456-µm wide having ambifenestrate vulval cone and bullae are absent. Females are white in color with a subcrystalline layer. Second-stage juveniles are straight or slightly curved ventrally with four incisures in the lateral field. The juveniles are 506 to 628-µm long having strong stylets with well-developed rounded stylet knobs, genital primordium situated at 59 to 62% of body length, and tail 49 to 61-µm long with a hyaline portion of 24 to 33 µm. Eggs are hyaline without any markings; juveniles inside the eggs form sixfold.Goettingiana group of Heterodera; currently, the group contains seven valid species, viz, Heterodera goettingiana , absence of bullae (vs few), weak underbridge (vs 117 µm), longer J2s body length (568 µm vs 486 µm), stylet knobs rounded and flat or slightly concave anteriorly vs smoothly rounded to slightly hook-shaped with a recurved anterior surface, longer distance of median bulb from the anterior end (MB) (86 µm vs 70 µm), shorter excretory pore distance from the anterior end (114 µm vs 158 µm), and shorter length of hyaline tail portion (29 µm vs 37 µm).The new species differs from H. carotae by having a bigger size of cysts (495 × 384 µm vs 408 × 309 µm), shorter vulval slit length (39 µm vs 47 µm), longer J2s body length (568 µm vs 422 µm), stylet knobs rounded and flat or slightly concave anteriorly vs concave anterior face, higher MB value (86 µm vs 66 µm), longer excretory pore distance from the anterior end (114 µm vs 99 µm), and longer tail length (57 µm vs 52 µm).The new species is differentiated from H. cruciferae by having a bigger size of cysts (495 × 384 µm vs 429 × 333 µm), slightly shorter fenestral length (31 µm vs 34 µm), shorter vulval length (39 µm vs 45 µm), longer J2s body length (568 µm vs 431 µm), higher MB value (86 µm vs 68 µm), longer excretory pore distance from the anterior end (114 µm vs 101 µm), longer tail length (57 µm vs 50 µm), and longer length of hyaline tail portion (29 µm vs 25 µm).The new species differs from H. persica by a shorter fenestral length (31 µm vs 47 µm), absence of bullae (vs present), shorter vulval slit length (39 µm vs 49 µm), longer J2s body length (568 µm vs 440 µm), stylet knobs , longer stylet (26 µm vs 23 µm), higher MB value (86 µm vs 70 µm), longer excretory pore distance from the anterior end (114 µm vs 103 µm), longer tail length (57 µm vs 47 µm), and longer length of hyaline tail portion (29 µm vs 24 µm).The new species differs from H. urticae, the new species has a smaller size of cysts (495 × 384 µm vs 492 × 435 µm), vulval cone obtrusive (vs unobtrusive) and absence of egg sac (vs presence), shorter fenestral length (31 µm vs 38 µm), shorter vulval slit length (39 µm vs 46 µm), longer J2s body length (568 µm vs 541 µm), shorter DGO (8 µm vs 5 µm), and shorter excretory pore distance from the anterior end (114 µm vs 130 µm).Compared with H. circeae having a smaller size of cysts (495 × 384 µm vs 555 × 397 µm), a shorter fenestral length (31 µm vs 43 µm), vulval slit length (39 µm vs 48 µm), longer J2s body length (568 µm vs 434 µm), stylet knobs (rounded and slightly sloping posteriorly vs rounded and flat or slightly concave anteriorly), higher MB value (86 µm vs 70 µm), longer excretory pore distance from the anterior end (114 µm vs 101 µm), longer tail length (57 µm vs 52 µm), and longer length of hyaline tail portion (29 µm vs 26 µm).The new species differs from H. scutellariae, having smaller cysts (495 × 384 µm vs 560 × 424 µm), by a shorter fenestral length (31 µm vs 35 µm), vulval slit length (39 µm vs 43 µm), longer J2s body length (568 µm vs 408 µm), higher MB value (86 µm vs 62 µm), longer excretory pore distance from the anterior end (114 µm vs 89 µm), longer tail length (57 µm vs 47 µm), and longer length of hyaline tail portion (29 µm vs 25 µm).The new species differs from H. microulae sp. n. with other valid species of Goettingiana group are listed in Additionally, comparative morphological and morphometric characters of H. microulae sp. n. sequences of D2-D3 region of 28 S (734 bp), ITS (993 bp), and COI (415 bp) gene were obtained and submitted to the GenBank.The H. microulae sp. n. showed 97.09% (19-bp difference), 97.66 to 98.49% (11-17-bp difference), 98.38% (9-bp difference), 98.62% (9-bp difference), 98.45% (11-bp difference), and 99.86 to 100% (0-1-bp difference) sequence identities with H. goettingiana (DQ328697), H. carotae (KX463292 and KX463293), H. cruciferae (KP114546), H. urticae (DQ328696), Heterodera sp. RH-2010 (GU456692) from Iran, and Heterodera sp. DP-2010 (HM560856 and HM560855) from Qinghai, China, respectively. The Bayesian phylogenetic tree of the D2-D3 of 28S gene  from Qinghai, China and forms a 100% supported clade.The D2-D3 of 28S-rRNA sequence (accession no. MT573436) of 28S gene  represenH. microulae sp. n. with other Goettingiana group species is as follows: 0.20% (2-bp difference), 0.4 to 0.5% (4-bp difference), 3.02% (29-bp difference), 5.01% (48-bp difference), 5.11% (49-bp difference), 7.45% (72-bp difference), 6.77 to 6.95% (67-68-bp difference), 6.29 to 7.25% (66-70-bp difference), and 7.41 to 8% (74-77-bp difference) for Heterodera sp. DP-2010 (HM560761), H. goettingiana , H. persica (AF498377), H. scutellariae (AY368995), H. circeae (AY368994), H. urticae (AF274412), H. carotae , H. cruciferae , and H. goettingiana , respectively. The Bayesian phylogenetic tree of the ITS gene  clustered with H. persica (AF498377), H. scutellariae (AY368994), H. circeae (AY368995), Heterodera sp. DP-2010 (HM560791), and H. goettingiana  from Qinghai, China with high-probability support (pp = 91%). It is also noted that sequences of H. goettingiana  from Qinghai, China, clustered outside with other H. goettingiana  subclades and should be considered a misidentification. However, H. microulae sp. n. (MT573437) is clustered with H. sp. DP-2010 (HM560791) and H. goettingiana  from Qinghai, China, with 100% support. It is also noted that H. microulae sp. n. (MT573437) clustered with two Chinese populations of Heterodera species  with 100% support.The ITS-rDNA sequence (accession no. MT573437) divergence of ITS gene  represenCOI gene sequence of H. microulae sp. n. showed 87.21 to 89.53% (differing from 36 to 44 bp), 88.19% (differing from 43 bp), 88.67 to 88.92% (differing from 46 to 47 bp), and 88.67 to 89.40% (differing from 44 to 47 bp), sequence identities with H. goettingiana (KY129829-KY129831), H. urticae (MK093155 and MK093156), H. cruciferae (MG563230 and MG563234), and H. carotae , respectively. The Bayesian phylogenetic tree of the COI gene  and Subbotin et al. (2001) used J2’s lateral field characters and host preferences to separate Heterodera species into different groups . The key morphological characters of the Goettingiana group include lemon-shaped cysts having a protruding neck, ambifenestration, and absence of bullae ; some species may have an egg sac, vulval slit length > 35 µm, a thin vulval bridge, fenestral length (30-45 µm), and a weak underbridge. There were second-stage juveniles with body length > 400 µm, stylet length > 20 µm, tail length > 45 µm, hyaline tail portion > 20 µm, and lateral field with four lines  and H. goettingiana (HM370423 and HM370425) from Qinghai, China, formed a well-supported molecular clade with the H. microulae sp. n. Moreover, the nucleotide differences of these sequences with our new species sequences are also very low (2-4-bp difference for ITS and 0-1 bp for 28S). Previously, H. goettingiana (HM370423 and HM370425) from Qinghai, China, might be a case of misidentification. Based on our phylogenetic and sequence analysis results, we regard Heterodera sp. DP-2010  and H. goettingiana (HM370423 and HM370425) as H. microulae sp. n.Phylogenetically, it is evident that Heterodera microulae sp. n. is isolated from Microula sikkimensis, it is a biennial herbaceous plant that grows in forests, meadows, and forest edges at altitudes of 2,200 to 4,700 m, and it is widely distributed in South and East Asian countries  are growing in the same locality. Therefore, host-suitability tests of H. microulae sp. n. are an open research field to investigate the damage potential of this species.The present study described a new species found in the rhizosphere of


The structure of the racemic form of the diuretic drug trichlormethiazide was determined from laboratory X-ray powder diffraction data: the extended structure features an intricate combination of N—H⋯O hydrogen bonds and π–π and C—Cl⋯π interactions. RS)-trichlormethiazide , C8H8Cl3N3O4S2 (RS-TCMZ), a diuretic drug used in the treatment of oedema and hypertension, was determined from laboratory X-ray powder diffraction data using DASH [David et al. . Energy framework calculations confirm the major contribution of electrostatic interactions (Eelec) to the total energy (Etot). A comparison with the structure of S-TCMZ is also presented.The structure of racemic ( al. 2006. J. Applelho 2018. J. Appl H-1λ6,2,4-benzothiadiazine-7-sulfonamide (C8H8Cl3N3O4S2), is a diuretic drug derived from thiazide, the precursor of a classic family of diuretic compounds, discovered in the 1950s. The first approved drug of this class, chlorothiazide, was marketed under the trade name Diuril in 1958 , systematic name 6-chloro-3-(dichloromethyl)-1,1-dioxo-3,4-dihydro-2Mogul geometry check  exhibits a conformation that could be described as distorted half-chair to distorted envelope at N3  and equatorial  conformations. The almost planar benzosulfonamide ring (ring B) makes an angle of 8.2 (2)° with the best plane through the thiazide ring. The molecule is oriented almost parallel to the a-axis as indicated by a 3.11 (8)° angle °].The asymmetric unit contains one TCMZ molecule Fig. 1: the steS-configuration in racemic TCMZ with the molecule of the S-enantiomer in KIKCUD. When flexibility is allowed in the superposition , the r.m.s.d. deviation is 0.070 and the maximum deviation (max. D) is 0.146 Å. Without flexibility, the values for r.m.s.d. and max. D are 0.785 and 2.763 Å, respectively . The difference between the two conformations lies in the orientation of the sulfonamide group and leads to differences in the hydrogen-bonding patterns between the two compounds as discussed below.Fig. 2on Fig. 2a, the rly Fig. 2b. The dIntramolecular hydrogen bondsRS-TCMZ  Å and a D—H⋯A angle of 106.9 (5)°. A second intramolecular hydrogen bond occurs between C7—H7 and O4 . The third contact, N3—H3A⋯Cl3, has geometric parameters 2.767 (8) Å and 102.1 (5)°. The three hydrogen bonds can all be represented by the graph-set symbol S(5) .Three different intramolecular hydrogen bonds are present in MZ Fig. 3b.Intermolecular hydrogen bondsRS-TCMZ is very rich and relevant geometric parameters are summarized in Table 1a, an A as the donated H  alternate with a motif , occur between molecules related by the symmetry operation −x, 2 − y, −z . At the same time, the original molecule interacts via a C—Cl⋯π contact of 3.761 (5) Å with another molecule related by symmetry operation 1 − x, 2 − y, 1 − z . The molecules are arranged as head-to-tail dimers producing chains along [101] as depicted in Fig. 5c. In contrast, in the structure of S-TCMZ only C—Cl⋯π interactions are observed (Table 1d = 3.456 (2) Å] than in RS-TCMZ.In addition, π–π and C—Cl⋯π interactions , which form columns along the b-axis. These columns are further connected by N—H⋯O and N—H⋯N hydrogen bonds .The structure of ns Fig. 6c, whichds Fig. 6d.et al., 2016S-trichlormethiazide  shows that they correspond to the same phase. It is worth mentioning that a broader search of the CSD resulted in 100 structures related to TCMZ, among them chlorothiazide and hydrochlorothiazide, their polymorphs, derivatives, solvates, and co-crystals.A search in the Cambridge Structural Database -Trichlormethiazide was kindly provided by Tecnoquímicas . Based on the FT–IR spectra and the quality of the preliminary diffraction patterns, the present study was carried out on the sample as it was received. Crystallization experiments in different solvents, in search of possible polymorphs, are underway in our laboratories. Å, b = 8.8919 (9) Å, c = 9.720 (2) Å, α = 91.30 (1)°, β = 106.07 (2)°, γ = 97.19 (1)°, V = 693.4 (2) Å3. The de Wolf , respectively. A reduced-cell search in the CSD  using GRACE  analysis for this molecule. The HBP analysis was carried out with supporting information.The HBP tool provides an insight into the expected intra- and intermolecular hydrogen bonds in the structures. For the analysis, the donor atoms considered were N1 (sulfonamide), N2 (secondary amine) and N3 (next to the sulfonyl group). The acceptors were Cl1 (aryl chloride), Cl2/Cl3 , N2 (secondary amine), O1/O2 (sulfonamide), and O3/O4 (sulfonyl). The area under the receiver operating characteristics (ROC) curve was 0.863, indicating good statistical discrimination in the analysis. The results of the calculations are presented in the B⋯Cl1 (0.60). This hydrogen bond is observed only in the S-enantiomer. The intramolecular interaction involving N3—H3A⋯Cl3, observed in the two structures, has the second highest propensity value (0.48).The intramolecular hydrogen bond with the highest propensity is N1—H1B⋯O3 and N1—H1A⋯O4) have the highest propensities (0.69). They are present in the structure of RS-TCMZ (motifs II and III). However, only one of them (N1—H1A⋯O4) is present in the S-enantiomer. The next two interactions with highest propensities (0.68) are between the H and O atoms of the sulfonamide groups of two neighboring molecules. One of them (N1—H1B⋯O2) is observed only in the S-enantiomer.Regarding the intermolecular interactions, two hydrogen bonds involving the hydrogen atoms bonded to the nitrogen of the sulfonamide group and the two oxygen atoms of the sulfonyl group (N1—H1A) and for the secondary amine (N2—H2A) with the sulfonyl O atoms , which are not present in either structure. However, N3—H3A⋯O1 and N3—H3A⋯O2 contacts with 0.42 propensities are displayed in S-TCMZ and RS-TCMZ (motifs I and IV), respectively. In addition, the hydrogen bond N2—H2A⋯O1 is present in RS-TCMZ (motifs V and VI) but not in S-TCMZ. The hydrogen bond N2—H2A⋯N1 was not predicted because the N1 atom was not considered an acceptor. The hydrogen-bond patterns found in the two structures are consistent with the hydrogen-bond propensity analysis results. Every donor and acceptor in RS-TCMZ and in S-TCMZ has a hydrogen-bond coordination with a high likelihood. Figure S2 of the additional supporting information shows the putative landscape for trichlormethiazide. The two structures fall in the high propensity and hydrogen-bond coordination zone.The CSD statistics predicts hydrogen bonds for the sulfonyl nitrogen atom  with 36.0 and 16.9%, respectively. The next interaction, O⋯Cl, is slightly less important in RS-TCMZ than in S-TCMZ (8.7% versus 9.6%). The remaining interactions differ in order of importance. For example, the H⋯H interaction is more important (8.5%) in RS-TCMZ than in S-TCMZ (7.2%). It is worth noting that the fingerprint plot delineated into the H⋯H interaction for RS-TCMZ shows a tip at de + di = 2.20 Å, which is less than 2 times the van der Waals radii of hydrogen. In contrast, in S-TCMZ this interaction is dispersed over a range of de + di values. Weaker interactions such as π–π contacts are present only in racemic TCMZ and they represent 1.8% of the contribution to the Hirshfeld surface. The Cl⋯π interaction is more important in S-TCMZ, contributing 9.1% in contrast to RS-TCMZ where it represents 2.8%. This is the result of two interactions in the S-enantiomer that lead to layers parallel to the ab plane. In RS-TCMZ, the Cl⋯π interactions alternate with π–π contacts to produce chains nearly along [101]. Another interesting feature is displayed by the H⋯N contacts. There is a lower degree of directionality and strength of this interaction in RS-TCMZ (2.1%) than in S-TCMZ (3.3%) as a result of the additional N2—H2A⋯N1 interaction in the latter.Fig. 8ts Fig. 8m–8x witEele), dispersive (Edis), and total energies (Etot) for the intermolecular interactions in RS-TCMZ and S-TCMZ were calculated with CrystalExplorer21  and dispersive  components are similar although their contributions are quite different. They result in an offset tile arrangement for Etot when viewed down the b-axis direction . In the structure of S-TCMZ, Eele and Edis make similar contributions to Etot and their topology is similar . The pattern viewed down the b-axis direction resembles a herringbone arrangement .As depicted in Fig. 9on Fig. 9c. In thar Fig. 9d and 9ent Fig. 9f.supporting information). The stretches for the secondary N—H grouping of the sulfonamide group appear at 3387 and 3322 cm−1 followed by the stretching bands of the S—N—H and N—H groups of the amine on the dihydrothiadiazine at 3281 and 3232 cm−1, respectively. The stretches of the Csp2—H (3150–3100 cm−1) and Csp3—H (3000–2900 cm−1) bonds are observed as weak bands. The Csp2—Csp2 stretch of the aromatic ring appears at 1596 cm−1 while the C—N and S—N stretches overlap at 1351 and 1332 cm−1. The stretches of the two S=O groups appear as strong absorptions at 1176 and 1157 cm−1. Table S2 summarizes the assignment of the most important absorptions for RS-TCMZ.The FT–IR spectrum shows the absorption bands expected for TCMZ  recorded indicates the material is stable up to 240°C. A series of weight loss events occur from 240°C to 450°C. A 24.2% weight loss (2.270 mg) between 245 and 301°C coincides with the first two transitions in the DSC . The endotherm at 281.1°C (ΔH = 81.19 J g−1) is associated with melting of the material. This transition is followed by an exotherm with peak temperature 287.9°C (ΔH = 103.70 J g−1). The TGA curve shows two continuous weight loss processes at 302–384°C  and 384–448°C , associated with ill-defined transitions in the DSC. The total weight loss due to decomposition is 49.6%.The TGA curve  TCMZ, I. DOI: 10.1107/S2056989021013633/hb7999Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021013633/hb7999Isup3.molSupporting information file. DOI: 10.1107/S2056989021013633/hb7999sup4.pdfPowder pattern superposition, Hydrogen bond propensity analysis, Hirshfeld surface, energy frameworks calculations, FT-IR, and TGA/DSC. DOI: Click here for additional data file.10.1107/S2056989021013633/hb7999Isup5.cmlSupporting information file. DOI: 2034096, 2034096CCDC references:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


In the crystal, the molecules are connected by N—H⋯O hydrogen-bond pairs along the b-axis direction as dimers with R22(8) and R22(14) ring motifs and as ribbons formed by intermolecular C—H⋯N hydrogen bonds. There are weak van der Waals interactions between the ribbons. The most important contributions to the surface contacts are from H⋯H (34.9%), O⋯H/H⋯O (19.2%), C⋯H/H⋯C (11.9%), Cl⋯H/H⋯Cl (10.7%) and N⋯H/H⋯N (10.4%) interactions, as concluded from a Hirshfeld surface analysis.The molecular conformation of the title compound, C The planes of the 2,3-dihydro-1H-indole ring system and the 4H-pyran ring are approximately perpendicular to each other, subtending a dihedral angle of 84.52 (5)°. The C5—C6—C11—Cl1, C6—C5—C8—O2, C6—C5—C8—O3, C5—C8—O3—C9 and C8—O3—C9—C10 torsion angles are −103.28 (13), −29.78 (18), 150.69 (11), 178.03 (10) and −169.29 (12)°, respectively. An intramolecular C11—H11B⋯O2 contact stabilizes the molecular conformation of the title compound  ring motif  interactions are the major factor in the crystal packing with O⋯H/H⋯O , C⋯H/H⋯C , Cl⋯H/H⋯Cl  and N⋯H/H⋯N  interactions representing the next highest contributions. Other weak interactions (contribution percentages) are O⋯N/N⋯O (2.3%), O⋯C/C⋯O (2.1%), N⋯C/C⋯N (2.1%), Cl⋯N/N⋯Cl (1.7%), Cl⋯O/O⋯Cl (1.4%), C⋯C (1.0%), N⋯N (0.7%), O⋯O (0.6%), Cl⋯C/C⋯Cl (0.6%) and Cl⋯Cl (0.3%).Fig. 7et al., 2016H-pyran-3-carbonitrile as the main skeleton revealed the presence of three structures, ethyl 6-amino-2-(chloromethyl)-5-cyano-4-(o-tolyl)-4H-pyran-3-carboxylate  and C(8). Combination of these primary motifs leads to a secondary In the crystal of HIRNUS, the six-membered pyran ring adopts a near-boat conformation. The crystal structure features two intramolecular C—H⋯O interactions and the crystal packing is stabilized by intermolecular N—H⋯O hydrogen bonds. These lead to two primary motifs, In the crystal of JEGWEX, a potential precursor for fluoroquinoline synthesis, the pyran ring is nearly planar, with the most outlying atoms displaced from the best-plane fit through all non-H atoms by 0.163 (2) and 0.118 (2) Å. The molecules are arranged in layers oriented parallel to the (011) plane. In addition, the molecules are linked by a weak C—H⋯O hydrogen bond, which gives rise to chains with base vector [111].QT = 0.085 (7) Å, θ = 84 (5)° and φ = 154 (5)°. In the crystal, molecules are linked as dimers by pairs of N—H⋯O hydrogen bonds, forming ribbons along the b-axis direction. These ribbons are connected by weak van der Waals interactions, stabilizing the molecular packing.In WIMBEC, the pyran ring exhibits a near-boat conformation with puckering parameters et al., 2015et al., 2018The title compound was synthesized using previously reported procedures , N2—H2A = 0.843 (19) and N2—H2B = 0.889 (18) Å], but their isotropic displacement parameters were constrained to take a value of 1.2Ueq(N). All H atoms bound to C atoms were positioned geometrically and refined as riding with C—H = 0.95 (aromatic), 0.99 (methylene) and 0.98 Å (methyl), with Uiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for the others. Four reflections, 0 0 1, 0 1 0, 1 0 0 and 1 2 0, affected by the incident beam-stop and owing to poor agreement between observed and calculated intensities, and five outliers, Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989021006459/vm2250sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021006459/vm2250Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021006459/vm2250Isup3.cmlSupporting information file. DOI: 2091350CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The molecular complex is based on the heterobimetallic AgI—VV fragment {AgI2(VVO2F2)2(tr)4} supported by four 1,2,4-triazole ligands [4-benzyl-]. The triazole functional group demonstrates homo- and heterometallic connectivity (Ag—Ag and Ag—V) of the metal centers through the [–NN–] double and single bridges, respectively. The vanadium atom possesses a distorted trigonal–bipyramidal coordination environment [VO2F2N] with the Reedijk structural parameter τ = 0.59. In the crystal, C—H⋯O and C—H⋯F hydrogen bonds as well as C—H⋯π contacts are observed involving the organic ligands and the vanadium oxofluoride anions. A Hirshfeld surface analysis of the hydrogen-bonding interactions is also described.The crystal structure of the title compound, [Ag The 1,2,4-triazole heterocycle, as a functional group, demonstrates a favorable coordination affinity towards AgI cations, connecting them into polynuclear units 2(tr)4} SBUs with bi-1,2,4-triazole ligands with different geometries 2(2Phtr-CH)4] (I), which has the ligand 4-benzyl- (tr-CH2Ph).There is considerable interest in the chemistry of organic–inorganic hybrids, including the vanadium oxide–fluoride (VOF) matrix, which is motivated by the numerous potential applications in catalysis, magnetism, optics, I crystallizes in the monoclinic space group P21/c. Its asymmetric unit contains one AgI cation, one [VVO2F2]− anion and two organic ligands (tr-CH2Ph), which, after inversion across a center of symmetry, form the molecular tetranuclear cluster {AgI2(VVO2F2)2(tr-CH2Ph)4}  Å; symmetry code (i) −x, −y + 1, −z], while the other two link Ag and V centers [the Ag⋯V distance is 3.8044 (6) Å]. Thus, the coordination environment of the AgI cation can be described as [AgN3O] with typical Ag—N(triazole) bond lengths [in the range of 2.197 (2) – 2.390 (3) Å] and a slightly elongated Ag—O bond [2.562 (2) Å]  and 1.8330 (18) Å], two short V—O [1.632 (2) and 1.660 (2) Å] and elongated V—N [2.203 (2) Å] bonds  Å, symmetry code (v) −x + 1, −y + 1, −z] hydrogen-bond contacts. The other triazole group, which provides the heterometallic Ag–V linkage, forms bifurcated C—H⋯O and C—H⋯F contacts with vanadium oxofluoride anions of neighboring molecular complexes. Additionally, methylene –CH2– fragments show directed C—H⋯O and C—H⋯F contacts to the VOF fragments. The phenyl rings are here oriented towards each other in an edge-to-face C—H⋯π interaction mode.Since the organic ligand contains a hydrophobic benzyl tail, the crystal structure of s Figs. 2. The cenet al., 2004CrystalExplorer17  to 1.385 (blue) a.u. visualizes the set of shortest intermolecular contacts  contacts  suggests the dominant role of the hydrogen-bond interactions. The strongest ones  have a similar nature and they are reflected by pairs of spikes pointing to the lower left of the plot. However, the contribution from the contacts with F-atom acceptors is higher (15.6% for F⋯H/H⋯F and 11.6% for O⋯H/H⋯O) and they are also essentially shorter, as indicated by different lengths of the spikes (the shortest contacts are F⋯H = 2.0 and O⋯H = 2.2 Å). One may suppose that the preferable sites for hydrogen bonding of the vanadium oxofluoride groups are the F atoms. This is consistent with the results of Hirshfeld analysis for the [VOF5]2− anion 4,4′-bis salt  with the polarized methylene H atoms. There are no mutual π–π interactions involving phenyl rings, which are responsible for larger fractions of the C⋯C contacts in the case of polycyclic species  and C⋯H/H⋯C (22.2%) contacts, which appear as pairs of nearly identical, very diffuse and short features (N⋯H = 2.9 and C⋯H = 2.9 Å). Both of them correspond to edge-to-face stacking or C—H⋯et al., 2016H-1,2,4-triazol-4-yl) and it revealed five hits for coordination compounds based on this ligand. There are no examples of AgI compounds, only two FeII complexes [FAYQAA  ligand.A structure survey was carried out in the Cambridge Structural Database  (tr-CH2Ph) was synthesized by refluxing benzylamine  and dimethylformamide azine  in the presence of toluenesulfonic acid monohydrate  as a catalyst in DMF (30.0 ml).4-Benzyl-, tr-CH2Ph , V2O5  and 5 mL of water with aqueous HF  was added into a Teflon vessel. Then the components were heated at 423 K for 24 h and slowly cooled to room temperature over 50 h, yielding light-yellow prisms of I .Compound 2C6H5 linkage and similarity restraints applied to the closely separated contributions of C12 and C12A, C13 and C13A. H atoms were positioned geometrically and refined as riding, with C—H = 0.93 Å (CH) and 0.97 Å (CH2) and with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989022001712/dj2039sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022001712/dj2039Isup2.hklStructure factors: contains datablock(s) I. DOI: 2151864CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


The pyran ring is modestly non-planar while the tetrahydrodiazepine ring adopts a boat conformation. In the crystal, N—H⋯O hydrogen bonds and slipped π–π stacking interactions build a three-dimensional network structure. S,E)-3-diazepin-2-ylidene]-6-methyl-2H-pyran-2,4(3H)-dione}, C19H16N2O4, is constructed from a benzodiazepine ring system linked to furan and pendant dihydropyran rings, where the benzene and furan rings are oriented at a dihedral angle of 48.7 (2)°. The pyran ring is modestly non-planar [largest deviation of 0.029 (4) Å from the least-squares plane] while the tetrahydrodiazepine ring adopts a boat conformation. The rotational orientation of the pendant dihydropyran ring is partially determined by an intramolecular N—HDiazp⋯ODhydp (Diazp = diazepine and Dhydp = dihydropyran) hydrogen bond. In the crystal, layers of molecules parallel to the bc plane are formed by N—HDiazp⋯ODhydp hydrogen bonds and slipped π–π stacking interactions. The layers are connected by additional slipped π–π stacking interactions. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (46.8%), H⋯O/O⋯H (23.5%) and H⋯C/C⋯H (15.8%) interactions, indicating that van der Waals interactions are the dominant forces in the crystal packing. Computational chemistry indicates that in the crystal the N—H⋯O hydrogen-bond energy is 57.5 kJ mol−1.The title compound {systematic name: ( In the seven-membered ring, N1 and N2 are displaced from the C1–C6 plane by 0.159 (6) and 0.158 (6) Å, respectively, in the direction away from C8  = 0.915 (4) Å, Q(3) = 0.187 (4) Å, φ(2) = 38.9 (2)° and φ(3) = 156.3 (12)° [total puckering amplitude Q = 0.933 (4) Å]. This ring adopts a boat conformation. The mean plane of the O1/C10–C14 ring is inclined to that of the C1–C6 ring by 34.8 (1)°, while the C1–C6 and O4/C16–C19 rings make a dihedral angle of 48.7 (2)°. The orientation of the O1/C10–C14 ring is partially determined by an intramolecular N1—H1⋯O2 hydrogen bond  hydrogen bonds  distance = 3.690 (2) Å, slippage = 1.47 Å] , the white surface indicates contacts with distances equal to the sum of van der Waals radii, and the red and blue colours indicate distances shorter or longer than the van der Waals radii, respectively , while the red regions indicate the negative electrostatic potential (hydrogen-bond acceptors). The shape-index of the HS is a tool to visualize the π–π stacking by the presence of adjacent red and blue triangles. Fig. 4c clearly suggests that there are π–π interactions in (I)a, and those delineated into H⋯H, H⋯O/O⋯H, H⋯C/C⋯H, C⋯C, H⋯N/N⋯H, C⋯ O/O⋯C and O⋯O contacts  have tips at de + di = 2.95 Å. The C⋯C contacts  have an arrow-shaped distribution of points with its tip at de = di = 1.65 Å. The H⋯N/N⋯H contacts  have tips at de + di = 2.78 Å. Finally, the C⋯O/O⋯C  and O⋯O  contacts  appear with tips at de + di = 3.50 Å and de = di = 1.73 Å, respectively.In order to visualize the intermolecular interactions in the crystal of (I)rm Fig. 4a, the wH Table 2 contributs Fig. 5d, 15.8%ts Fig. 5e, 7.4% ts Fig. 5f, 2.8% ⋯C Fig. 5g and O⋯⋯O Fig. 5h contacdnorm plotted onto the surface are shown for the H⋯H, H⋯O/O⋯H, H⋯C/C⋯H and C⋯C interactions in Fig. 6a–d, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯O/O⋯H, and H⋯C/C⋯H interactions suggest that van der Waals interactions play the major role in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  as −32.6 (Eele), −7.4 (Epol), −60.8 (Edis), 57.3 (Erep) and −57.5 (Etot).The intermolecular interaction energies were calculated using the CE–B3LYP/6–31G energy model available in et al., 2016Hbenzo[b] diazepines substituted at the 2- and 4-positions gave a substantial number of hits with seven deemed closely similar to the title molecule C6H3 and R′ = 6- methyl-2H-pyran-2,4-(3H)-dione as well as R = 6-methyl-2H- pyran-2,4-(3H)-dione and R′ = 3-BrC6H4  to 0.957 (2) Å . The dihedral angles between the mean planes of the benzo rings and those of the ring-containing substituents on the seven-membered ring vary considerably, likely due to packing considerations as the steric bulk of these groups differ markedly.A search of the Cambridge Structural Database ethyl]-4-hydroxy-6-methylpyran-2-one (4 mmol) in ethanol (40 ml) were added 1.5 equivalents of furan-2-carboxaldehyde and four drops of trifluoroacetic acid (TFA). The mixture was refluxed for 3 h. Cooling to room temperature induced the precipitation of a yellow solid, which was filtered off, and then washed with 20 ml of cold ethanol. Crystals suitable for X-ray analysis were obtained by recrystallization of the bulk from ethanol solution to afford colourless crystals (yield: 75%).CELL_NOW  was used for the final refinement. Hydrogen atoms attached to carbon were included as riding contributions in idealized positions (C—H = 0.95–0.99 Å) with Uiso(H) = 1.2–1.5Ueq(C). Those attached to nitrogen were restrained to a target bond length of 0.91 Å using the DFIX instruction in SHELXL. The displacement ellipsoids of the O1/C10–C14 ring suggest a possible slight disorder in this group, but it does not appear large enough to model with alternate locations of the atoms.Crystal, data collection and refinement details are presented in Table 310.1107/S2056989021007441/wm5612sup1.cifCrystal structure: contains datablock(s) I, global. DOI: Click here for additional data file.10.1107/S2056989021007441/wm5612Isup3.cdxSupporting information file. DOI: 10.1107/S2056989021007441/wm5612Isup4.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021007441/wm5612Isup4.cmlSupporting information file. DOI: 2097593CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-020-68370-y, published online 21 August 2020Correction to: This Article contains a typographical error in the Results section under subheading ‘Mechanical properties’ where,“The compressive strength of the scaffolds calculated as the maximum compression force divided by the cross-sectional area of tested specimen, was 87.4 ± 22.1 and 6.5 ± 0.8 MPa for ATE-G3 and Repros (BCP) scaffolds, respectively.”should read:“The compressive strength of the scaffolds calculated as the maximum compression force divided by the cross-sectional area of tested specimen, was 8.7 ± 2.2 and 6.5 ± 0.8 MPa for ATE-G3 and Repros (BCP) scaffolds, respectively.”


The daily life of Chronic obstructive pulmonary disease (COPD) patients is characterised not only by chronic respiratory symptoms but also by exercise intolerance due to their breathlessness. Proper diagnosis and management of this disease consequently includes evaluation of exercise tolerance , frequenAn observational study was performed with inclusion of seventy one men with moderate COPD (FEV1 54.6 ± 7.1%); age 63.8 ± 3.1 yrs; weight, 71.2 ± 8.3 kg; height, 169.0 ± 8.1 cm constituted the COPD group (COPDG), and 150 healthy subjects, age 64.2 ± 5.8 yrs; weight, 76.2 ± 11.3 kg; height, 169.8 ± 7.5 cm, were included as the healthy group – HG. The physical parameters assessed were strength, aerobic endurance, flexibility and agility/balance, by the Fullerton’s functional fitness tests. The health status was evaluated through the Medical Outcomes 36-item Short Form Health Survey (SF-36) questionnaire. The study was approved by the Ethics Committee of the Garcia de Orta Hospital and all participants gave their informed consent.p < .05) between COPDG and HG groups for the following variables all expressed in mean ± SD: body mass index, 25.9 ± 3 vs 27.7 ± 4.1 kg.m2; 30-second chair stand 14.1 ± 1.7 vs. 18.2 ± 1.9 times; arm curl 15.7 ± 2.8 vs. 18.8 ± 4.9 times; 6-minute walk 498.8 ± 58.3 vs. 589.7 ± 88.6 m; 8-foot up-and-go 4.7 ± 0.8 vs. 5.1 ± 1 sec; chair sit-and-reach 0.81 ± 9.9 vs. −7.1 ± 10.6 cm respectively and no differences were observed for the back scratch test . In health status DPOCG presented a significant decrease (p < .05) on perception of all domains of SF-36, except on body pain.The values of the functional fitness test were significantly different (In this study COPD patients have lower levels of functional capacity compared to healthy subjects. However, they were able to perform short tasks with higher speed. This trend was also evident in other study where COPD patients performed short term activities faster than healthy persons . Limitat


In Xu et al.,p value < 0.05 vs. NC group; NC: negative control). F, Overexpression of lncRNA‐CASC7 increased the expression of IL‐11 in H9C2 cellsFIGURE 9: lncRNA‐CASC7 suppressed the expression of miR‐30c in H9C2 cells (*Supplementary MaterialClick here for additional data file.


A series of platinum(II) complexes with differently substituted iminomethyl groups were synthesized, and their photophysical properties were examined in solution, in the crystalline, and in the PMMA film‐dispersed state, respectively (PMMA=poly(methyl methacrylate)). These complexes showed structure‐dependent emission spectra, in which the color of the luminescence in the crystalline state varied over a range of about 40 nm depending on the specific bowl‐shaped molecular structure. The chiral complexes with ‐ and ‐configurations were found to have structure‐dependent chiroptical properties both in solution and the PMMA film‐dispersed state such that the intensity of circular dichroism (CD) and circularly polarized luminescence (CPL) were enhanced with bulky cyclic substituents at the nitrogen atoms. A theoretical study using density functional theory (DFT) and time‐dependent (TD)‐DFT calculations revealed that the enhancement of chiroptical responses is due to the amplification of the magnetic dipole moment caused by the distortion of the square planar geometry.The relationship between the coordination geometry and photophysical properties of  Chiral platium(II) complexes exhibit structure‐dependent chiroptical properties in dilute solution and in the poly(methyl methacrylate) film‐dispersed state. DFT and TD‐DFT calculations of the structures and electronic configurations revealed that the enhancement of the chiroptical responses is due to the distortion of the square planar geometry. Complexes ‐ and ‐1 a–e were successfully characterized by 1H and 13C nuclear magnetic resonance (NMR) spectroscopy , infrared (IR) spectroscopy, and high‐resolution mass spectrometry (HRMS). The same treatment with the racemic ligand yielded a mixture of rac‐/‐1 a and meso‐‐1 a (ca. 1 : 1). Recrystallization from CH2Cl2/n‐hexane gave enriched ‐1 a in 46 % diastereomeric excess. Repeated crystallization from CH2Cl2/n‐hexane yielded pure crystals of ‐1 a. From the mother liquor of the first recrystallization, enriched /‐1 a in 6 % diastereomeric excess was obtained. Crystallization of the enriched /‐1 a from CH2Cl2/n‐hexane several times afforded pure crystals of /‐1 a.A series of chiral 1 a–e were obtained by recrystallization from CH2Cl2/n‐hexane and employed in single‐crystal X‐ray diffraction (XRD) analysis. Details of the crystal data and the structure refinement are presented in Table S1 (Supporting Information), including analysis of the intermolecular interactions . ORTEPS,S)‐1 a, /‐1 a, ‐1 a, ‐1 b–d, and ‐1 e are shown in Figures ϕ) and bowl angles θ between the mean planes of the naphthalene rings are provided to express the degree of distortion of the coordination planes.Single crystals of platinum complexes S,S)‐1 a, /‐1 a, and ‐1 a are shown in Figures S,S)‐1 a has a bowl configuration (θ=49.6°), and the two methyl groups have a syn‐orientation ‐1 a in the spiro‐chelate rings has a positive value of 7.94°. Hence, ‐1 a has a  configuration in the crystal. These structural data correspond well with the previously reported palladium(II) complex.R,R)/‐1 a have an envelope form with a ϕ angle of −2.64° . Therefore, ‐1 a in /‐1 a has a  configuration in the crystal, whilst ‐1 a in the enantiopure crystal showed the opposite Λ configuration. ‐1 a adopts a step configuration with C2 symmetry, and the two methyl groups in ‐1 a take an anti‐orientation .The molecular structures of ‐1 b–d and ‐1 e are shown in Figures S,S)‐1 b adopts the bowl configuration (θ=19.2°) with anti‐orientation between the phenyl groups ‐1 c are in anti‐orientation, and the structure can be described as a distorted bowl‐configuration with a low bowl angle (θ=3.56°) ‐1 d has a bowl‐configuration with θ=48.2° as the bowl angle and a Λ configuration with a positive value of ϕ=1.30° ‐1 e adopts the step configuration (θ=5.14°) with an anti‐orientation between the methyl groups ‐ and ‐1 a–e were recorded in solution and in the PMMA (PMMA=poly(methyl methacrylate) film‐dispersed state at room temperature ‐1 a–d exhibited a strong negative Cotton effect at approximately 420 nm, which can be assigned to a mixture of intra‐ligand charge transfer (1ILCT) and metal‐to‐ligand charge transfer (1MLCT) from the UV/Vis spectra showing a mixture of 1ILCT and 1MLCT bands around 370–500 nm observed under the same measurement conditions ‐1 e showed a comparably weak negative Cotton effect in the same region, although it has almost the same UV/Vis spectrum as ‐1 a–d. The gabs (=Δϵ/ϵ) values around the absorption maxima in the low energy region are −0.0026 (422 nm) for ‐1 a, −0.0023 (422 nm) for ‐1 b, −0.0030 (417 nm) for ‐1 c, −0.0025 (418 nm) for ‐1 d, and −0.00088 (410 nm) for ‐1 e, respectively. These results indicate that the bulkiness of the substituents at the nitrogen atoms exert a strong influence on the chiral properties of 1 even in the diluted solution state.Circular dichroism (CD) spectra of ‐1 d (λmax=589 nm) with the bulkiest 1‐naphthyl substituent at the nitrogen atoms compared to those of ‐1 a–c ‐1 a, 601 nm for ‐1 b, and 602 nm for ‐1 c, respectively). In contrast, a bathochromic shift was observed for ‐1 e (λmax=608 nm) with the less bulky alkyl substituents at the nitrogen atoms. These results indicate that the bulkiness of the substituents at the nitrogen atoms affects the d‐π conjugation of the coordination platform in dilute solution.All the complexes exhibited orange to red luminescence under UV excitation at room temperature in solution, crystalline, and PMMA film‐dispersed state, respectively . The photophysical data of complexes S,S)‐1 a–e was more remarkable in the crystalline state. Figure S,S)‐1 a–e in the crystalline state, where the emission peak maxima clearly changes depending on the substituent at the nitrogen atoms ‐1 a, 623 nm for ‐1 b, 605, 628 nm for ‐1 c, 605 nm for ‐1 d, and 632 nm for ‐1 e).The change in the emission color of /‐1 a and ‐1 a showed bathochromic emission patterns that were different from that of enantiopure crystals ‐1 a . XRD analysis showed that the maximum emission wavelength (λmax) in the crystalline state of complexes 1 was negatively correlated with the bowl angle . Therefore, we assume that bowl‐shaped structures exert a strong influence on the d‐π conjugation of 1, resulting in a change in the emission color in the crystalline state.It is noteworthy that the crystals of (I) and total luminescence (I) spectra measured for ‐ and ‐1 a–e in the PMMA film‐dispersed state at 298 K are shown in Figures R,R)‐ and ‐1 a–d exhibit mirror‐image positive and negative signals around 570–590 nm, which are corresponding to the emission maxima (λmax) observed in their total emission spectra taken under the same measurement conditions  for ‐1 a, −0.0011 (575 nm) for ‐1 b, −0.0036 (590 nm) for ‐1 c, and −0.0018 (575 nm) for ‐1 d, respectively. It should be noted that ‐ and ‐1 e did not exhibit detectable CPL signals , which indicates that circularly polarized luminescence was induced by introduction of bulky substituents at the nitrogen atoms.The circularly polarized luminescence ‐1 a–e in an isolated system were estimated using DFT  calculations on the basis of the X‐ray structures. The optimized structures of ‐1 a–e are shown in Figure ϕ) are 0.90° for 1 a, 0.78° for 1 b, 0.29° for 1 c, 1.39° for 1 d, and 0.20° for 1 e, indicating that the substituents on the nitrogen atoms distort the coordination geometry which induces Λ chirality. In addition, ‐1 a–d have a bowl‐configuration with similar bowl angles θ, while ‐1 e has a step‐configuration with a small θ value. These structural differences are expected to affect the chiroptical properties in solution and in the PMMA film‐dispersed state.In order to clarify the structure‐dependence of the photophysical properties of the series of platinum complexes S,S)‐1 a–e and their eigenvalues were estimated by using DFT  calculations on the basis of the optimized structure in the ground state. The HOMOs of all complexes are principally Pt(dzx)–ligand (π) hybrids, whereas the LUMOs are in the ligand (π*)  states is the HOMO‐to‐LUMO transition, which implies that the present emission is principally attributable to a mixture of MLCT/ILCT. The S0–T1 transition energies were calculated to be 2.17 eV (570 nm) for 1 a, 2.18 eV (568 nm) for 1 b, 2.19 eV (567 nm) for 1 c, 2.21 eV (561 nm) for 1 d, and 2.14 eV (579 nm) for 1 e, which is consistent with the hypsochromic and bathochromic shift of the emission peak maxima for 1 d and 1 e in CH2Cl2  calculations  (Table S2). The major consequence of the electronic configuration of the S 2.17 eV 70 nm forS,S)‐1 a–e using TD‐DFT calculations . The validity of the calculation was confirmed by comparison between theoretical and experimental CD spectra of ‐1 a–e /(|μe|2+|μm|2), where |μe|, |μm|, and θe,m are the electric transition dipole moments, magnetic transition dipole moments, and the angles between two vectors μe and μm, respectively. , corresponding chiral ligands (0.58 mmol), and K2CO3 (1.5 mmol) in toluene/DMSO (20/5 mL) was warmed at 80 °C for 16 h. The red reaction mixture was added to water (30 mL) and extracted with EtOAc (20 mL×3). The organic layers were dried over Na2SO4 and evaporated in vacuo. The residue was washed with cold methanol to give the complexes. Suitable crystals for the X‐ray analysis were prepared by recrystallization from CH2Cl2/n‐hexane.transN‐Bis[1‐[(1‐phenylethyl)imino]methyl‐2‐naphthalenolato‐,OR]‐platinum(II) ‐ and ‐1 a): Orange crystals (38 %); m.p. 230 °C (decomp); IR (KBr): ν=1616 cm−1 (N=C); 1H NMR  δ=8.64 , 7.67 , 7.64 , 7.59 , 7.44 , 7.39–7.32 , 7.19 , 7.10 , 6.36 , 1.93 ppm ; 13C NMR  δ=163.03, 152.69, 142.30, 134.00, 133.82, 128.80, 128.73, 128.12, 127.71, 127.39, 127.33, 123.23, 122.48, 119.16, 111.65, 58.53, 21.76 ppm; HRMS (ESI+): m/z [M+H]+ calcd. for C38H33N2O2195Pt: 742.2092, found 742.2094; Anal. Calcd for C38H32N2O2Pt: C, 61.37; H, 4.34; N, 3.77. Found: C, 61.21; H, 4.33; N, 3.65. ‐1 a: [α]D25=−166 .transN‐Bis[1‐[(1‐phenylpropyl)imino]methyl‐2‐naphthalenolato‐,OR]‐platinum(II) ‐ and ‐1 b): Orange crystals (36 %); m.p. 254 °C (decomp); IR (KBr): ν=1614 cm−1 (N=C); 1H NMR  δ=8.66 , 7.69 , 7.66 , 7.57 , 7.45–7.32 , 7.20 , 7.14 , 6.10 , 2.53–2.23 , 1.18 ppm ; 13C NMR  δ=162.80, 152.47, 140.52, 133.94, 133.91, 128.88, 128.75, 127.79, 127.37, 127.33, 123.20, 122.44, 119.17, 111.62, 64.51, 28.64, 11,70 ppm; HRMS (APCI+): m/z [M+H]+ calcd. for C40H37N2O2195Pt: 772.2501, found 772.2513; Anal. calcd for C40H36N2O2Pt: C, 62.25; H, 4.70; N, 3.63. Found: C, 62.25; H, 4.67; N, 3.68. ‐1 b: [α]D25=−231 .transN‐Bis[1‐[(1‐cyclohexylethyl)imino]methyl‐2‐naphthalenolato‐,OR]platinum(II) ‐ and ‐1 c): Orange crystals (23 %); m.p. 278 °C (decomp); IR (KBr): ν=1616 cm−1 (N=C); 1H NMR  δ=8.63 , 7.81 , 7.70 , 7.51 , 7.25 , 7.10 , 4.72 , 2.08–1.65 , 1.50 , 1.35–1.15 ppm ; 13C NMR  δ=163.01, 150.76, 133.98, 133.61, 128.83, 127.39, 127.30, 123.20, 122.39, 119.30, 111.74, 61.77, 43.98, 30.43, 28.64, 26.51, 26.29, 26.23, 18.72 ppm; HRMS (APCI+): m/z [M+H]+ calcd. for C38H45N2O2195Pt: 756.3127, found 756.3149; Anal. calcd for C38H44N2O2Pt ⋅ 1/2CH2Cl2: C, 57.92; H, 5.68; N, 3.51. Found: C, 57.83; H, 5.19; N, 3.39. ‐1 c: [α]D25=−153 transN‐Bis[1‐[ethyl)imino]methyl‐2‐naphthalenolato‐,OR]platinum(II) ‐ and ‐1 d): Orange crystals (48 %); m.p. >300 °C; IR (KBr): ν=1615 cm−1 (N=C); 1H NMR  δ=8.75–8.72 , 8.65 , 7.96 , 7.92–7.87 , 7.67 , 7.60 , 7.57 , 7.52–7.46 , 7.22 , 7.13–7.09 , 6.99 , 2.14 ppm ; 13C NMR  δ=163.19, 151.27, 137.26, 134.27, 133.93, 133.76, 131.76, 129.23, 128.61, 128.53, 127.28, 127.22, 127.17, 126.08, 125.55, 125.12, 124.87, 123.09, 122.37, 119.01, 111.81, 55.67, 22.64 ppm; HRMS (APCI+): m/z [M+H]+ calcd. for C46H37N2O2195Pt: 844.2501, found 844.2479; Anal. calcd for C46H36N2O2Pt ⋅ CH2Cl2: C, 60.78; H, 4.12; N, 3.02. Found: C, 60.79; H, 4.33; N, 2.83. ‐1 d: [α]D25=−243 .transN‐Bis[1‐[(1‐methyllpropyl)imino]methyl‐2‐naphthalenolato‐,OR]platinum(II) ‐ and ‐1 e): Orange crystals (34 %); m.p. 264 °C (decomp); IR (KBr): ν=1608 cm−1 (N=C); 1H NMR  δ=8.72 , 7.83 , 7.70–7.68 , 7.50 , 7.26–7.23 , 7.10 , 4.88–4.81 , 2.15–2.06 , 1.85–1.76 , 1.54 , 1.09 ppm ; 13C NMR  δ=163.02, 150.11, 133.95, 133.67, 128.83, 127.41, 127.29, 123.18, 122.41, 119.24, 111.71, 58.46, 31.10, 21.46, 11.02 ppm; HRMS (APCI+): m/z [M+H]+ calcd. for C30H33N2O2195Pt: 648.2187, found 648.2185. ‐1 e: [α]D25=−27 .RPreparation of /(S)‐ and imino]‐methyl‐2‐naphthalenolato‐N),OR]platinum(II) /(S)‐1 a and ‐1 a: A solution of [PtCl2(CH3CN)2] , 2 a , and K2CO3  in toluene/DMSO (20/5 mL) was warmed at 80 °C for 16 h. The dark red reaction mixture was added to water (30 mL) and extracted with EtOAc (20 mL×3). After evaporation of the solvent, the residue was washed with cold methanol to give a mixture of ‐1 a and /‐1 a (51 : 49 ratio) in 50 % (213 mg) yield. From the first recrystallization of CH2Cl2/n‐hexane, the filtrate gave a ‐1 a enriched powder (46 % de). Pure ‐1 a  was obtained by recrystallization of CH2Cl2/n‐hexane after several times, crystals of which were suitable for X‐ray analysis. After evaporation of the first mother liquor, a /‐1 a enriched orange powder (6 % de) was obtained. Pure /‐1 a  was obtained by recrystallization of CH2Cl2/n‐hexane after several times, crystals of which were suitable for X‐ray analysis. Pure crystals of /‐1 a were prepared by crystallization of an 1 : 1 mixture of ‐1 a and ‐1 a in CH2Cl2/n‐hexane.R‐1 a: m.p. 265 °C (decomp); IR (KBr): 1606 cm−1 (N=C). 1H NMR : δ=8.64 , 7.67 , 7.64 , 7.61 , 7.45 , 7.39–7.34 , 7.19 , 7.10 , 6.36 , 1.90 ppm . 13C NMR : δ=163.03, 152.68, 142.26, 134.00, 133.83, 128.83, 128.74, 128.17, 127.73, 127.39, 127.33, 123.21, 122.48, 119.16, 111.65, 58.69, 21.76 ppm. HRMS (ESI+): m/z [M+H]+ calcd. for C38H33N2O2195Pt: 745.2184, found 745.2147.R,R)/‐1 a The NMR and IR spectra corresponded well with the data of ‐ and ‐1 a. HRMS (ESI+): m/z [M+H]+ calcd. for C38H33N2O2195Pt: 745.2184, found 745.2156.X‐Ray Crystallography: Crystals suitable for XRD studies were analyzed using a Rigaku RAXIS‐RAPID imaging plate diffractometer using Mo‐Kα radiation  and a Rigaku XtaLAB mini2 benchtop X‐ray crystallography system equipped with a Mo rotating‐anode X‐ray generator with monochromated Mo‐Kα radiation (λ=0.71073 Å). The molecular structures and packings in crystals ‐1 a–d, ‐1 e, /‐1 a, and ‐1 a were solved by direct methods and refined using the full‐matrix least‐squares method. In subsequent refinements, the function Σω(Fo2−Fc2)2 was minimized, where Fo and Fc are the observed and calculated structure factor amplitudes, respectively. The positions of non‐hydrogen atoms were found from difference Fourier electron density maps and refined anisotropically. All calculations were performed using the Crystal Structure crystallographic or CrysAlisPro program software package, and illustrations were drawn by using ORTEP.S,S)‐1a), 1918308 /‐1a), 1918309 ‐1a), 1918310 ‐1b), 1918311 ‐1c), 1918312 ‐1d), 2119929 ‐1e)1918306 ) and singlet–triplet (E(Tn)) transition energies were estimated by time‐dependent (TD) DFT calculation .The authors declare no conflict of interest.1As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file.


In the crystal, molecules are linked by weak C—H⋯S hydrogen bonds, forming a two-dimensional supramolecular architecture. 3H5OS2)2(C6H16N2)] or [Hg(C3H5OS2)2(tmeda)] , has a distorted tetrahedral geometry. The HgII ion is coordinated to two N atoms of the N,N,N′,N′-tetramethylethylenediamine ligand and two S atoms from two ethylxanthate xanthate ligands. In the crystal, molecules are linked by weak C—H⋯S hydrogen bonds, forming a two-dimensional supramolecular architecture in the ab plane. The most important contributions for the crystal packing are from H⋯H (59.3%), S⋯H (27.4%) and O⋯H (7.5%) interactions.The title four-coordinate mononuclear complex, [Hg(C The bond lengths and angles of the HgN2S2 coordination units correspond to those in the structures of mixed-ligand HgII coordination compounds (see Database survey). The C1—O1 and C2—O1 bond lengths are 1.355 (11) to 1.460 (12) Å, respectively, although all of the C—O bonds show single-bond character. In the {S2C} section of the xanthate ligands, the C1—S1 distance is 1.727 (9) Å, which is typical of a single bond, whereas the C1=S2 distance of 1.633 (10) Å is typical of a carbon-to-sulfur double bond. The C—N and C—C bond lengths in the N,N,N′,N′-tetramethylethylenediamine ligand are normal 2(tmeda)].In the crystal, there is a weak intermolecular hydrogen bonding Table 2 between et al., 201614H26O2S4)]n 2(C6H16N2)] (C9H13NS)2](PF6)2 (C6H16N2)] ] 2  in ethanol (10 mL) under stirring. The formed precipitate was filtered off, washed with water and air-dried. The precipitate was suspended in hot ethanol (10 mL) and tetramethylethylenediamine  was added under stirring. The colour changed to dark brown. The precipitate was filtered off and dried and then recrystallized from ethanol. Brown rods were formed.Potassium ethylxanthate  in hot ethanol (10 mL) was added to a hot solution of Hg(CHUiso(H) = 1.5Ueq(C) for methyl H atoms and 1.2Ueq(C) for all othersCrystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989021010549/ey2008sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021010549/ey2008Isup2.hklStructure factors: contains datablock(s) I. DOI: 2115100CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


The sheets are associated through additional C—H⋯π(ring) interactions.The conformation of the title compound is partially determined by a strong, intramolecular O—H⋯O hydrogen bond. In the crystal, C—H⋯O hydrogen bonds link the molecules, forming chains along the  13H11NO2, is partially determined by a strong, intramolecular O—H⋯O hydrogen bond. The crystal packing consists of strongly corrugated layers parallel to the ac plane and associated through C—H⋯π(ring) interactions. A Hirshfeld surface analysis of the crystal structure indicates that the most significant contributions to the crystal packing are from H⋯H (44.1%), C⋯H/H⋯C (29.4%) and O⋯H/H⋯O (17.3%) contacts.The conformation of the title compound, C They show antifungal  is 1.94 (12) °. The torsion angles C2—C1—C7—N1, C1—C7—N1—C8, C1—C7—N1—O2, C7—N1—C8—C9 and O2—N1—C8–C-9 are −30.2 (3), −179.7 (2), −0.4 (3), 27.3 (3) and −152.0 (2)°, respectively. The conformation of the title compound is partially determined by a strong, intramolecular O1—H1⋯O2 hydrogen bond -N-[methanimine]-N-oxido -1,2-bis(3-bromophenyl)diazene 1-oxide -N-benzylidene-1-phenylmethanamine oxide hydrogen peroxide solvate -N-(2-chlorobenzylidene)aniline N-oxide °] and the phenyl and benzene rings are trans-oriented around the C=N bond. The phenyl and benzene rings make a dihedral angle of 56.99 (2)°.In the crystal of DEPVOM, (101) layers are generated by C—H⋯O hydrogen bonds coupled with C—H⋯π(ring) and offset π–π stacking interactions. In the crystal of SIYHAK01, C—H⋯O and C—H⋯Br hydrogen bonds together with offset π–π interactions stack the molecules along the Z)-(2-Hydroxyphenyl)methylidene]benzenimine N-oxide (nitrone) was prepared according to the reported procedures  = 1.5Ueq(O). The C-bound H atoms were positioned geometrically, with C—H = 0.95 Å, and constrained to ride on their parent atoms, withUiso(H) = 1.2Ueq(C). Attempts to determine the absolute structure did not produce a definitive result, viz.: Flack x = 0.2 (3) by classical fit to all intensities 0.30 (14) from 611 selected quotients (Parsons’ method). A round of TWIN/BASF refinement gave BASF = 0.2 (4) with no improvement in the model.Crystal and refinement details are presented in Table 410.1107/S2056989021004813/ey2006sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989021004813/ey2006Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021004813/ey2006Isup3.cmlSupporting information file. DOI: 2082055CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In addition, the mononuclear Dy and Tb complexes [{(thf)2Li(NtBu)2S(tBuN)2LnCl2(thf)2]  show slow magnetic relaxation under applied dc fields.Lanthanide ions are particularly well‐suited for the design of single‐molecule magnets owing to their large unquenched orbital angular momentum and strong spin‐orbit coupling that gives rise to high magnetic anisotropy. Such nanoscopic bar magnets can potentially revolutionize high‐density information storage and processing technologies, if blocking temperatures can be increased substantially. Exploring non‐classical ligand scaffolds with the aim to boost the barriers to spin‐relaxation are prerequisite. Here, the synthesis, crystallographic and magnetic characterization of a series of each isomorphous mono‐ and dinuclear lanthanide  complexes comprising tetraimido sulfate ligands are presented. The dinuclear Dy complex [{(thf) The first series of isomorphous lanthanide Gd to Er complexes containing the tetraimido sulfate ligand renders these compounds compelling to be investigated for their single‐molecule magnet behaviour. The displayed Dy dimer shows slow magnetic relaxation at zero field. The monomeric Tb and Dy complexes show field‐induced single‐molecule magnet behaviour. The ligand holds great potential for higher blocking systems, that is, removal of chloride ions, lithium transmetalation and promotion of the magnetic communication between the metal ions. S‐alkyltriimidosulfonates [RS(NR)3]−  and in the triimidosulfonic acid MeS(NtBu)2NHtBu the sum of all three S−N bond lengths is constant at 4.70(2) Å.[3]2− it was later also found in the tetraimido sulfates [S(NR)4]2−.tBu)]− ligand in [Co{(NtBu)3SMe}2], ,tBu)4]2− anion.[Single‐molecule magnets (SMMs)4Li2(NtBu)4S] with the appropriate lanthanide(III) chloride in thf yields after extraction and crystallization from toluene the binuclear lanthanide(III) compounds [{(thf)2Li(NtBu)2S(tBuN)2LnCl2}2 ⋅ ClLi(thf)2] 1 a–e with a: Ln=Gd, b: Tb, c: Dy, d: Ho, e: Er 2Li(NtBu)2S(tBuN)2LnCl2(thf)2] 2 a–e  in good yields and purity. Instead, 2 c was also isolated upon layering the reaction mixture with n‐pentane. However, since the crystallization parameters for this reaction are very tedious to control and the final product is insoluble in thf the derivatives rather precipitate than crystallize. Therefore, we concentrated on the optimization of the synthetic route to give the μ‐LiCl‐bridged dimers 1 a–e. They crystallize in the monoclinic space group C2/c with half a molecule and half a toluene molecule in the asymmetric unit 42−, the S−N bond distances for all metal complexes are almost identical. Nevertheless, it should be stated that the av. S−N1/N2 distances from the lithium coordinating nitrogen atoms of 1.567 Å are significantly shorter than the S−N3/N4 distances of 1.626 Å to the lanthanide‐coordinated nitrogen atoms. That mirrors the two opposite coordination sites of the tetrahedral ligand which are unsymmetrically coordinated by a lithium ion at the site with shorter S−N bonds and the lanthanide(III) ion at the opposite site. The triply positive charged lanthanides obviously are in much stronger demand of the negatively charged nitrogen atoms, for their part taking advantage of the electropositive central sulfur atom. A stronger demand of the negatively charged nitrogen atoms causes a longer distance between the nitrogen and the positively charged sulfur. The reduced lanthanide radii are also displayed in the reduction of the Ln1⋅⋅⋅Ln1A distances that ranges from 3.835 Å in 1 a to 3.752 Å in 1 e. Interestingly, the reduced radii have the opposite effect on the N1−Ln1−N2 angles increasing from 60.91° in 1 a to 62.24° in 1 e. Even though all Cl−Ln−Cl angles for one specific metal are different, they remain almost identical when proceeding from one lanthanide cation to the next. The same is valid for the N−S1−N angles. A comparable coordination is found in a series of rare earth metal complexes with β‐diketiminato ligands. Substitution at the nitrogen position with 2,6‐dimethylphenyl,1 c with 2.726 Å. The same is valid for the Dy−N bond lengths of 2.313 Å and 2.270 Å, respectively.We found these dimeric complexes, dissolved in small amounts of thf to recrystallize within hours at room temperature, forming the mononuclear lanthanide(III) compounds  3 b could be isolated from toluene . All Tb−Cl distances are similar, although the terbium atoms in 3 b are fourfold chlorine coordinated and those in 1 b and 2 b only two‐fold. With the rising nuclearity in 3 b the TbΛTb distance increases to 4.307 Å compared to 3.831 Å in 1 b. The acute N1−Tb−N2 bite angles of 61.22° (1 b), 60.67° (2 b), and 61.10° (3 b) differ only marginally. The same is valid for the N1−S1−N2 ligand angles at the Tb side of 91.47° (1 b), 92.77° (2 b) and 92.60° (3 b).Tetranuclear 1 a–e and 2 b–c in the temperature range 2–300 K at 0.1, 0.5 and 1 T fields  are in good agreement with the expected values  for two non‐interacting triply positive lanthanide atoms. As the temperature is decreased to 15 K, χMT undergoes a gradual decline and decreases below that temperature rapidly to reach at 2 K a minimum value of 10.24, 8.99, 9.57, 9.14, and 6.46 cm3K/mol for 1 a–e, respectively. Such downturn in χMT can be generally assigned to the Zeeman effect and/or weak intermolecular interactions. Notably, the decline in χMT is much more pronounced for 1 e and can potentially be ascribed to quite anisotropic trivalent erbium atoms in this ligand environment compared to the lighter lanthanide analogs. By contrast, χMT only decreases more noticeably below 10 K for 1 a hinting at the presence of very weak antiferromagnetic coupling. Due to the half‐filled f‐electron valence shell (4f7), trivalent gadolinium ions offer the possibility to determine the magnetic exchange interaction precisely. Fitting the dc data of 1 a to a spin‐only Hamiltonian Ĥ=−2JŜGd(1)+−2JŜGd(2) where J is the intramolecular coupling constant and Ŝ the spin operator for each paramagnetic center yielded a coupling constant of J=−0.045(1) cm−1 which is indicative of weak antiferromagnetic interaction between the GdIII ions. The magnitude of the coupling between the lanthanide ions via superexchange is typically very weak as is the case for the parent compound 1 a and comparable to various chloride‐bridged complexes or other bridges leading to superexchange pathways in bimetallic gadolinium complexes. was synthesized according to literature known procedure.All experiments were performed under inert gas conditions in N2Li(NtBu)2S(tBuN)2LnCl2}2General synthesis for [{(thf) 2] 1 a⋅ ClLi(thf)–e: A mixture of [(thf)4Li2(NtBu)4S]  and LnCl3 (0.8080 mmol) is dissolved in thf (20 mL) at ambient temperature. After stirring for 1 d the reaction mixture is concentrated under reduced pressure (7 mL), filtered and subsequently, the solvent is removed under reduced pressure. The residue is dissolved in toluene (5 mL) and the solution is filtered. Crystal growth of 1 a–e starts within several minutes to hours at ambient temperature. For a complete crystallization, the mixture is stored at −34 °C yielding colorless crystals suitable for X‐ray analysis after several days. The solvent is removed, and the crystalline product is washed with n‐pentane (2×2 mL). 1 a: Yield: 266.9 mg (40 %); elemental analysis calcd (%) for C56H120Cl5Gd2Li3N8O6S2(C7H8): C 45.30, H 7.72, N 6.71, S 3.84; found: C 42.91, H 6.92, N 6.51, S 4.47. 1 b: Yield: 304.6 mg (45 %); elemental analysis calcd (%) for C56H120Cl5Tb2Li3N8O6 S2(C7H8): C 45.21, H 7.71, N 6.69, S 3.84; found: C 43.64, H 7.87, N 6.88, S 4.80. 1 c: Yield: 281.5 mg (41 %); elemental analysis calcd (%) for C56H120Cl5Dy2Li3N8O6S2(C7H8): C 45.02, H 7.68, N 6.67, S 3.91; found: C 42.63, H 7.62, N 6.61, S 4.14. 1 d: Yield: 137.1 mg (20 %); elemental analysis calcd (%) for C56H120Cl5Ho2Li3N8O6S2(C7H8): C 44.89, H 7.65, N 6.65, S 3.80; found: C 41.27, H 7.06, N 6.71, S 3.92. 1 e: Yield: 113.8 mg (17 %); elemental analysis calcd (%) for C56H120Cl5Er2Li3N8O6S2(C7H8): C 44.76, H 7.60, N 6.63, S 3.79; found: C 42.67, H 7.60, N 7.14, S 5.08.2Li(NtBu)2S(tBuN)2LnCl2(thf)2] 2 aGeneral synthesis for [{(thf)–e: [{(thf)2Li(NtBu)2S(tBuN)2LnCl2}2 ⋅ ClLi(thf)2] (1 a–e) (150.0 mg) is dissolved in thf (3 mL) and filtered. Crystallization of 2 a–e starts within hours at ambient temperature where upon the mixture is stored at −34 °C to improve the yield. The target compound is isolated and washed with n‐pentane (2×1 mL) yielding crystals suitable for X‐ray analysis. 2 a: color: colorless; Yield: 98.3 mg (65 %); elemental analysis calcd (%) for C32H68Cl2GdLiN4O4S: C 45.75, H 8.16, N 6.67, S 3.82; found: C 45.82, H 8.59, N 6.54, S 4.01. 2 b: color: colorless; Yield: 99.6 mg (66 %); elemental analysis calcd (%) for C32H68Cl2TbLiN4O4S: C 45.66, H 8.14, N 6.66, S 3.81; found: C 45.98, H 8.66, N 6.50, S 4.34. 2 c: color: colorless; Yield: 105.2 mg (70 %); elemental analysis calcd (%) for C32H68Cl2DyLiN4O4S: C 45.47, H 8.11, N 6.63, S 3.79; found: C 46.58, H 8.71, N 6.44, S 4.77. 2 d: color: pale orange; Yield: 115.5 mg (77 %); elemental analysis calcd (%) for C32H68Cl2HoLiN4O4S: C 45.34, H 8.09, N 6.61, S 3.78; found: C 45.89, H 8.50, N 6.38, S 3.90. 2 e: color: light pink; here, only 100.0 mg of 2 e were used (1 e); Yield: 74.6 mg (74 %); elemental analysis calcd (%) for C32H68Cl2ErLiN4O4S: C 45.21, H 8.06, N 6.59, S 3.77; found: C 45.55, H 8.61, N 6.35, S 4.13.Crystallographic data: Single crystals were selected under cooling using the X‐Temp2 device.2 using SHELXL1 a); 2069110 (1 b), 2069111 (1 c), 2069112 (1 d), 2069113 (1 e), 2069114 (2 a); 2069115 (2 b), 2069116 (2 c), 2069117 (2 d), 2069118 (2 e), 2069119 (3 b)2069109 2Li(NtBu)2S(tBuN)2LnCl2}2 ⋅ ClLi(thf)2] 1 a–e, with a: Ln=Gd, b: Tb, c: Dy, d: Ho, e: Er and species [{(thf)2Li(NtBu)2S (tBuN)2LnCl2(thf)2] 2 a–e  were prepared by loading crushed crystalline samples into tubes in an argon glove‐box. Sufficient liquid eicosane (at 60 °C) was added to saturate and cover the samples to prevent crystallite torquing and provide good thermal contact between the sample and the bath. Tubes were sealed air‐tight before transferred to the magnetometer. Magnetic susceptibility measurements were collected using a Quantum Design MPMSXL SQUID magnetometer and Quantum Design MPMS3 SQUID magnetometer, respectively. DC susceptibility data measurements were performed at temperatures ranging from 2 to 300 K for 1 a–e and 2 b–e, using applied fields of 0.1, 0.5 and 1 T. Ac magnetic susceptibility data measurements were performed using a 3.6 (MPMSXL) and 4 Oe (MPMS3) switching field, respectively. All data were corrected for diamagnetic contributions from the eicosane and core diamagnetism estimated using Pascal's constants.χ′ and χ′′ in terms of frequency, constant temperature susceptibility (χT), adiabatic susceptibility (χS), relaxation time (τ), and a variable representing the distribution of relaxation times (α).The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file.


Cell Discovery (2021) 7:103Correction to: 10.1038/s41421-021-00341-7, Published online 31 October 20211, we missed some errors while proofreading the manuscript for the publication. The statistical values in Abstract and Results sections were inconsistent with those in Table FMR1NB, Pmeta = 7.61 × 10−9, OR = 1.31; rs7259428, 19q12, ZNF536, Pmeta = 8.20 × 10−15, OR = 0.65) showing consistent association with male sexual orientation.” On page 2, the second column, the lines 28–35 should be “All four SNPs showed consistent association in the independent validation samples, and two SNPs reached a genome-wide significance level (P < 5 × 10−8) after meta-analysis, including SNP rs7259428 on chromosome 19q12 (located in ZNF536, P = 8.20 × 10−15, OR = 0.65; Fig. 1e and Table FMR1NB, P = 7.61 × 10−9, OR = 1.31; Fig. 1d and Table ZNF356’ should be ‘ZNF536’. The corrected version of the Table In the initial published version of this article


Four copper(II) cations are situated in a distorted square-pyramidal environment, while two copper(II) cations are located in a slightly square-planar geometry. Three of the copper(II) cations occupy three vertices of an open cubane Cu3O4.In the title Schiff base hexanuclear copper(II) complex, two discrete environments are present in the structure: CuNO 3-1,3-bis{[1-(2-oxidophenyl)ethylidene]amino}propan-2-olato)-μ3-hydroxido-dinitratohexacopper(II) ethanol trisolvate, [Cu6(C19H19N2O3)3(NO3)2(OH)(H2O)2]·3C2H5OH, corresponds to a non-symmetric hexanuclear copper complex. The complex exhibits one core in which three CuII metal centres are mutually interconnected, two by two, via three phenolato oxygen anions acting in a μ2-mode. These three copper cations are interconnected in a μ3-mode by one hydroxyl group. An open-cube structure is generated in which each of the CuII cations of the three CuO4N units is connected by two μ2-O anions from phenolate groups and one μ3-O atom from a hydroxy anion. Each of the three pentacoordinated CuII cations situated in the open-cube unit has a distorted NO4 square-pyramidal environment. Each of these three CuII centres is interconnected with another CuII cation via one enolate O atom in μ2-mode, yielding one CuNO4 unit and two CuNO3 units. The pentacoordinated CuII atom has a distorted square-pyramidal environment while the two tetracoordinated copper(II) cations are situated in a square-planar environment. A series of intramolecular O—H⋯O hydrogen bonds are observed. In the crystal, the units are connected two by two by intermolecular C—H⋯O and O—H⋯O hydrogen bonds, thus forming sheets parallel to the ac plane.The title molecular structure, namely, diaquatris(μ That their structures present symmetrical or asymmetrical pendant arms and bear donor atoms is an asset widely exploited in coordination chemistry. The presence of donor sites on aliphatic or aromatic arms has made it possible to prepare a wide variety of compounds with various structures and interesting physical and chemical properties. 1,3-Diaminopropan-2-ol, which has three donor sites, is a good precursor for the synthesis of ligands with several cavities that can act as chelating agents and/or as bridging ligands ethylidene]}-2-hydroxypropane-1,3-diamine (H3L). The reaction of ligand H3L with copper nitrate yielded a complex in which the ligand reacted in tri-deprotonated form as L3−. The coordination complex is formulated as [Cu6L3(NO3)2(OH)(H2O)2]·3(EtOH) (I)II cations. The two imino nitrogen atoms of the ligand are coordinated to two different Cu cations. One of the phenolato O atoms bridges two copper cations, while the second phenolato O atom is coordinated to a third copper cation. The third copper cation is bridged to the central copper cation via the enolato oxygen anion. The tri-deprotonated ligand coordinates in a heptadentate mode , thus forming four fused chelate rings (two five-membered and two six-membered). Two discrete environments are observed in the structure: CuNO4 and CuNO3. The coordination environments for Cu1, Cu3, Cu5 and Cu6 are best described as square-pyramidal, as shown by the Addison τ parameter calculated from the largest angles (Table 1W) of the basal coordination plane are almost coplanar and the Cu6 cation is displaced toward the apical atom (O201) by 0.0963 (9) Å. The cissoid angles are in the range 86.12 (9)–94.66 (9)° while the transoid angles are 171.23 (9) and 174.18 (9)°. In the basal plane, the Cu6—N6 [1.942 (2) Å] and the Cu6—Oligand distances [1.935 (2) and 1.863 (2) Å] are shorter than the distance of Cu6—O2W [2.028 (2) Å]. The distance between the copper and the nitrato oxygen anion [Cu6—O14B = 2.45 (2) Å] in the apical position is longer than the distances to the atoms in the equatorial plane because of Jahn–Teller distortion, which is typical for copper(II) d9 atoms ethanone and 1,3-diaminopropan-2-ol in a 2:1 ratio in ethanol yielded the ligand s Table 1 around C3O4 open cube, the basal planes are occupied by one imino nitrogen atom, one phenolate oxygen anion, one enolato oxygen anion from the same ligand molecule and the O atom of the hydroxy oxygen anion that connects the three copper cations. The copper cations situated on the corners of the open cube are connected by two μ2-Ophenolato and one μ3-Ohydroxy atoms. In each case, the apical position is occupied by one phenolate oxygen anion from another ligand. The donor atoms of the basal coordination planes of Cu1, Cu3 and Cu5 centres are situated almost in the same plane and the copper cations are displaced from the corresponding apical positions  and O—Cu—O [72.34 (7)–86.17 (8)°] angles, which deviate severely from the ideal value of 90° expected for a perfect cube. The atoms defining the three sides of the open cube are almost coplanar  and are irregular with edges of different lengths, i.e. for Cu1/O1/Cu5/O10 these are O1—Cu1 = 1.877 (2) Å, O10—Cu1 = 2.004 (2) Å, O1—Cu5 = 2.453 (2) Å and O10—Cu5 = 1.978 (2) Å. Additionally, the dihedral angles values of 78.11 (6), 75.77 (5) and 77.57 (5)° between the sides, two by two, confirm the distortion of the open cube. The bond lengths involving the bridging phenolate oxygen anions and the copper cations are asymmetrical: O1—Cu1 = 1.877 (2) Å and O1—Cu5 = 2. 453 (2) Å; O4—Cu1 = 2.389 (2) Å and O4—Cu3 = 1.896 (2); and O7—Cu5 = 1.889 (2) Å and O7—Cu3 = 2.365 (2) Å. The distances of the μ3-bridging O atom to the copper cations are slightly different: O10—Cu1 = 2.005 (2) Å, O10—Cu5 = 1.978 (2) Å and O10—Cu3 = 2.004 (2) Å. The axial bond lengths are longer than the equatorial bond lengths as a result of the Jahn–Teller distortion . The three copper cations are placed at the vertices of an almost isosceles triangle with distances values of 3.1801 (4) Å (Cu1—Cu5), 3.1823 (4) Å (Cu3—Cu5) and 3.2140 (5) Å (Cu1—Cu3) and angle values of 60.68 (1)° (Cu1—Cu5—Cu3), 59.69 (1)° (Cu5—Cu1—Cu3) and 59.62 (1)° (Cu1—Cu3—Cu5).For Cu1, Cu3 and Cu5, which are situated on the vertices of the CuW/O6. The τ4 –94.26 (10)°] and the transoid angles are 171.59 (9) and 174.77 (10)°. The Cu4 cation is coordinated by one enolato oxygen anion (O5), one phenoxo oxygen anion (O6), one azomethine nitrogen atom (N4) of the ligand, and one O atom from a coordinated water molecule. The distances of Cu4 to the coordinated atoms from the ligand  are comparable with those involving Cu2. The Cu4—O1W distance value of 1.961 (2) Å is similar to those reported for square-planar copper(II) complexes –95.34 (9)° and the transoid angles are 171.10 (9) and 173.69 (9)°. The double-bond character of the C—N bonds [overall values 1.286 (3)–1.295 (3) Å] is indicative of the presence of the imino groups in the three ligands.For the Cu2 and Cu4 centres, the coordination environments can be best described as slightly distorted square planar with r.m.s. deviations from planarity of 0.0601 Å for Cu2/O2/N2/O3/O11 and 0.0909 Å for Cu4/N4/O5/O1water—H⋯Oethanol and Owater—H⋯Onitrate) and C—H⋯O (Cphenolate—H⋯Onitrate)   Fig. 2. The comne Fig. 3. The cooN,N′-bis[(1-(2-hydroxyphenyl)ethylidene)]-2-hydroxypropane-1,3-diamine has been widely used in coordination chemistry. The current release of the CSD ethylidene]}-2-hydroxypropane-1,3-diamine (HL3), which was prepared according to 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%. A solution of Cu(NO3)2·3H2O  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 dark green and was stirred for 30 min. The mixture was filtered, and the filtrate was kept at 298 K. After one week, light-green crystals suitable for X-ray diffraction were collected and formulated as [Cu6L3(NO3)2(OH)(H2O)2]·3EtOH. FT–IR : 1625, 1600, 1540, 1446, 1382, 1304, 1258, 1180, 1120, 1007, 895, 760. Analysis calculated for C63H80Cu6N8O21: C, 45.40; H, 4.84; N, 6.72. Found: C, 45.38; H, 4.82; N, 6.74%.Reaction of 1-(2-hydroxyphenyl)ethanone and 2-hydroxypropane-1,3-diamine in a 2:1 ratio in ethanol yielded the ligand 2, CH3 groups, hydroxyl groups of ethanol molecules and water molecules) were geometrically optimized  and refined as riding with Uiso(H) = 1.2Ueq(C) (1.5 for CH3 and OH groups).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989021005570/ex2045sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989021005570/ex2045Isup2.hklStructure factors: contains datablock(s) I. DOI: 2086932CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The crystal structure of the title compound comprises two independent molecules that mainly differ in the orientation of the phenyl ring to the rest of the molecule. 16H13N3OS, comprises two molecules (A and B) with similar conformations that differ mainly in the orientation of the phenyl group relative to the rest of the molecule, as expressed by the Cthioamide—Nthioamide—Cphenyl—Cphenyl torsion angle of 49.3 (3)° for molecule A and of 5.4 (3)° for molecule B. In the crystal, two intermolecular N—H⋯N hydrogen bonds lead to the formation of a dimer with R22(10) graph-set notation. A Hirshfeld surface analysis revealed that H⋯H interactions are the most important intermolecular interactions, contributing 40.9% to the Hirshfeld surface.The asymmetric unit of the title compound, C The presence of bifunctional properties in thioamides, resulting from the presence of nitrogen and sulfur atoms, and their participation in reactions as electrophilic or nucleophilic reagents can lead to the formation of different heterocyclic compounds. Several review articles have been published on the syntheses, physico-chemical properties and applications of thioamides  and 49.3 (3)°, respectively, in molecule A and 83.78 (19) and 5.4 (3)° in molecule B. As a result, there are differences in the intramolecular distances between the sulfur and hydrogen atoms in molecules A and B. In molecule A, the contacts S1A⋯H9AB and S1A⋯H13A are 2.873 and 2.897 Å whereas the corresponding distances in molecule B are 3.054 and 2.578 Å. The phenyl and pyrimidine rings in both molecules are essentially coplanar, with r.m.s. deviations of 0.0225 and 0.0119 Å for molecule A and B, respectively. Fig. 2The title compound crystallizes with two molecules, it Fig. 1. In molA and B form a dimer with an A interacts with molecule B by a C—H⋯ π interaction . Other weak C7A—H7A⋯O1B, C7A—H7A ⋯O1B, C7B—H7B⋯O1A, C9A—H9AB⋯S1A and C13B—H13B⋯S1B hydrogen bonds link adjacent dimers, forming supramolecular layers expanding parallel to (010)  Fig. 4. The ovell Fig. 5.CrystalExplorer17.5  whereby H⋯H contacts are responsible for the largest contribution (40.9%) to the Hirshfeld surface. C⋯H/H⋯C contribute 23.7%, S⋯H/H⋯S contacts 10.7%, N⋯H/H⋯N contacts 8.1% and O⋯H/H⋯O contacts 7.0% to the total Hirshfeld surface. The contributions of further contacts are only minor and amount to C⋯C (4.0%), S⋯C/C⋯S (1.9%), N⋯C/C⋯N (1.2%), S⋯S (1.0%), S⋯C/C⋯S (0.6%), O⋯N/N⋯O (0.2%) and O⋯C/C⋯O (0.1%).A Hirshfeld surface (HS) analysis -one moiety with a similar planar conformation as that in the title structure: AFOCIJ  and 4 ml of dimethyl sulfoxide were injected into a round-bottomed flask with a volume of 100 ml. Then the reaction flask was heated to 403 K for 6 h. After the end of the reaction, the flask was cooled and 40 ml of an aqueous sodium hydroxide solution were added. The resulting mixture was filtered, then added to a dilute solution of sulfuric acid (pH 6). The formed precipitate was filtered off and recrystallized in methanol. In total, 0.5 g (64.0%) of the product were obtained, m.p. 481–483 K.0.435 g (0.0025 mol) of 2,3-dimethylquinazoline-4-one, 0.465 g (0.005 mol) of aniline, 0.24 g (0.0075 mol) of sulfur, 0.05 g of sodium sulfide (NaUiso(H) = 1.5Ueq(Cmethyl) and 1.2Ueq(C), respectively. H atoms bonded to nitrogen were located in a difference-Fourier map, and their positional and isotropic displacement parameters were freely refined.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989021013116/wm5629sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021013116/wm5629Isup3.cmlSupporting information file. DOI: 10.1107/S2056989021013116/wm5629Isup3.hklStructure factors: contains datablock(s) I. DOI: 2127513CCDC reference:  crystallographicinformation; 3D view; checkCIF reportAdditional supporting information:


Two similar molecules make up the asymmetric unit of the title compound. The crystal structure features short C—H⋯Cl and C—H⋯O contacts and C—H⋯π and van der Waals interactions. 16H14Cl2N2O, comprises two similar molecules, A and B, in which the dihedral angles between the two aromatic rings are 70.1 (3) and 73.2 (2)°, respectively. The crystal structure features short C—H⋯Cl and C—H⋯O contacts and C—H⋯π and van der Waals interactions. The title compound was refined as a two-component non-merohedral twin, BASF 0.1076 (5). The Hirshfeld surface analysis and two-dimensional fingerprint plots show that H⋯H , Cl⋯H/H⋯Cl  and C⋯H/H⋯C  interactions are the most important contributors to the crystal packing.The asymmetric unit of the title compound, C In molecule A, the N2/N1/C2/C1/Cl1/Cl2 moiety is approximately planar, with a maximum deviation of 0.110 (2) Å, and makes dihedral angles of 1.2 (2) and 71.3 (2)°, respectively, with the C3–C8 and C10–C15 rings. In molecule B, the N4/N3/C18/C17/Cl3/Cl4 moiety is approximately planar with a maximum deviation of 0.046 (6) Å, and makes dihedral angles of 9.57 (18) and 75.94 (19)°, respectively, with the C19–C24 and C26–C31 rings.There are two comparable molecules A (with Cl1) and B (with Cl3) in the asymmetric unit of the title compound Fig. 1. The dihvia C—H⋯Cl short contacts, yielding supramolecular chains along the b-axis direction. Adjacent chains are linked by C—H⋯O contacts, generating a two-dimensional array parallel to the bc plane . The Cl⋯H/H⋯Cl interactions appear as two symmetrical broad wings with de + di = 2.70 Å and contribute 24.6% to the Hirshfeld surface for molecule A, and with de + di = 2.70 Å and contribute 26.7% to the Hirshfeld surface for molecule B . The pair of characteristic wings in the fingerprint plot delineated into H⋯C/C⋯H contacts  have the tips at de + di = 2.80 Å for molecule A and at de + di = 2.85 Å for molecule B. The remaining contributions for both molecules A and B are from N⋯H/H⋯N, O⋯H/H⋯O, N⋯C/C⋯N, Cl⋯O/O⋯Cl, Cl⋯C/C⋯Cl, C⋯C, Cl⋯N/N⋯Cl, O⋯C/C⋯O and Cl⋯Cl contacts, which are less than 4.6% and have a negligible effect on the packing. The percentage contributions of all interactions are listed in Table 3A and B can be attributed to the different molecular environments of the A and B molecules in the crystal structure.The overall two-dimensional fingerprint plot and those delineated into H⋯H, Cl⋯H/H⋯Cl and C⋯H/H⋯C contacts in molecules ng Fig. 6b. The C B Fig. 6c. The pet al., 2016E)-1--2-phenyldiazene unit resulted in 27 hits. Eight compounds are closely related to the title compound, viz. 4-{2,2-dichloro-1-[diazenyl]ethenyl}-N,N-dimethylaniline  Å]. In DULTAI, the dihedral angle between the two aromatic rings is 64.12 (14)°. The crystal structure is stabilized by a short C—H⋯Cl contact, C—Cl⋯π and van der Waals interactions. In HONBOE and HONBUK, the aromatic rings form dihedral angles of 60.9 (2) and 64.1 (2)°, respectively. In the crystals, molecules are linked through weak X⋯Cl contacts (X = Br for HONBOE and Cl for HONBUK), C—H⋯Cl and C—Cl⋯π interactions into sheets parallel to the ab plane. Additional van der Waals interactions consolidate the three-dimensional packing. In HODQAV, the benzene rings make a dihedral angle of 56.13 (13)°. Molecules are stacked in columns along the a-axis direction via weak C—H⋯Cl hydrogen bonds and face-to-face π–π stacking interactions. The crystal packing is further consolidated by short Cl⋯Cl contacts. In XIZREG, the benzene rings form a dihedral angle of 63.29 (8)° and the molecules are linked by C—H⋯O hydrogen bonds into zigzag chains running along the c-axis direction. The crystal packing also features C—Cl⋯π, C—F⋯π and N—O⋯π interactions. In the crystals of LEQXIR and LEQXOX, the dihedral angles between the aromatic rings are 56.18 (12) and 60.31 (14)°, respectively. In LEQXIR, C—H⋯N and C—H⋯O hydrogen bonds and short C—Cl⋯O contacts occur and in LEQXOX, C—H⋯N and short Cl⋯Cl contacts are observed.In GUPHIL, the benzene rings subtend a dihedral angle of 77.07 (10)°. In the crystal, molecules are associated into inversion dimers et al., 2021et al., 2018Z)-1-(4-methoxyphenyl)-2-(4-methylbenzylidene)hydrazine , tetramethylethylenediamine , CuCl  and CCl4 . After 1–3 h , the reaction mixture was poured into a 0.01 M solution of HCl , and extracted with dichloromethane (3 × 20 mL). The combined organic phase was washed with water (3 × 50 mL) and brine (30 mL), dried over anhydrous Na2SO4 and concentrated in vacuo by a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and dichloromethane (3/1–1/1). Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution. Colorless solid (65%); m.p. 355 K. Analysis calculated for C16H14Cl2N2O: C 59.83, H 4.39, N 8.72; found: C 59.78, H 4.32, N 8.69%. 1H NMR  δ 7.79 , 7.26 , 7.10 , 6.95 , 3.88 , 2.42 . 13C NMR  δ 162.48, 148.12, 147.82, 138.47, 129.90, 129.76, 129.41, 128.85, 125.23, 114.14, 55.58 and 21.48. ESI–MS: m/z: 322.14 [M + H]+.The title compound was synthesized according to a reported method (Mukhtarova Uiso(H) = 1.2 or 1.5Ueq(C). Owing to poor agreement between observed and calculated intensities, eight outliers  I. DOI: 10.1107/S2056989021008756/zn2009Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989021008756/zn2009Isup3.cmlSupporting information file. DOI: 1984582CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: