Syntheses, characterizations, crystal structures and Hirshfeld surface analyses of methyl 4-[4-(di-fluorometh-oxy)phen-yl]-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexa-hydro-quinoline-3-carboxyl-ate, isopropyl 4-[4-(di-fluoro-meth-oxy)phen-yl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexa-hydro-quinoline-3-carboxyl-ate and tert-butyl 4-[4-(di-fluoro-meth-oxy)phen-yl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexa-hydro-quinoline-3-carboxyl-ate.

The crystal structures and Hirshfeld surface analyses of three similar compounds are reported. Methyl 4-[4-(di-fluoro-meth-oxy)phen-yl]-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexa-hydro-quinoline-3-carboxyl-ate, (C21H23F2NO4), (I), crystallizes in the monoclinic space group C2/c with Z = 8, while isopropyl 4-[4-(di-fluoro-meth-oxy)phen-yl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexa-hydro-quinoline-3-carb-oxyl-ate, (C23H27F2NO4), (II) and tert-butyl 4-[4-(di-fluoro-meth-oxy)phen-yl]-2,6,6-trimethyl-5-oxo-1,4,5,6,7,8-hexa-hydro-quinoline-3-carboxyl-ate, (C24H29F2NO4), (III) crystallize in the ortho-rhom-bic space group Pbca with Z = 8. In the crystal structure of (I), mol-ecules are linked by N-H⋯O and C-H⋯O inter-actions, forming a tri-periodic network, while mol-ecules of (II) and (III) are linked by N-H⋯O, C-H⋯F and C-H⋯π inter-actions, forming layers parallel to (002). The cohesion of the mol-ecular packing is ensured by van der Waals forces between these layers. In (I), the atoms of the 4-di-fluoro-meth-oxy-phenyl group are disordered over two sets of sites in a 0.647 (3): 0.353 (3) ratio. In (III), the atoms of the dimethyl group attached to the cyclo-hexane ring, and the two carbon atoms of the cyclo-hexane ring are disordered over two sets of sites in a 0.646 (3):0.354 (3) ratio.

Hydrogen-bonding interactions in 5-fluorocytosine-urea (2/1), 5-fluorocytosine-5-fluorocytosinium 3,5-dinitrosalicylate-water (2/1/1) and 2-amino-4-chloro-6-methylpyrimidine-6-chloronicotinic acid (1/1).

Three new compounds, namely, 5-fluorocytosine-urea (2/1), 2C4H4FN3O·CH4N2O, (I), 5-fluorocytosine-5-fluorocytosinium 3,5-dinitrosalicylate-water (2/1/1), 2C4H4FN3O·C4H5FN3O+·C7H2N2O7-·H2O, (II), and 2-amino-4-chloro-6-methylpyrimidine-6-chloronicotinic acid (1/1), C6H4ClNO2·C5H6ClN3, (III), have been synthesized and characterized by single-crystal X-ray diffraction. In compound (I), 5-fluorocytosine (5FC) molecules A and B form two different homosynthons [R22(8) ring motif], one formed via N-H...O hydrogen bonds and the second via N-H...N hydrogen bonds. In addition to this interaction, a sequence of fused-ring motifs [R21(6), R33(8), R22(8), R43(10) and R22(8)] are formed, generating a supramolecular ladder-like hydrogen-bonded pattern. In compound (II), 5FC and 5-fluorocytosinium are linked by triple hydrogen bonds, generating two fused-ring motifs [R22(8)]. The neutral 5FC and protonated 5-fluorocytosinum cation form a dimeric synthon [R22(8) ring motif] via N-H...O and N-H...N hydrogen bonds. On either side of the dimeric synthon, the neutral 5FC, 5-fluorocytosinium cation, 3,5-dinitrosalicylate anion and water molecule are hydrogen bonded through N-H...O, N-H...N, N-H...OW and OW-HW...O hydrogen bonds, forming a large ring motif [R1010(56)], leading to a three-dimensional supramolecular network. In compound (III), 2-amino-4-chloro-6-methylpyrimidine (ACP) interacts with the carboxylic acid group of 6-chloronicotinic acid via N-H...O and O-H...O hydrogen bonds, generating an R22(8) primary ring motif. Furthermore, the ACP molecules form a base pair via N-H...N hydrogen bonds. The primary motif and base pair combine to form tetrameric units, which are further connected by Cl...Cl interactions. In addition to this hydrogen-bonding interaction, compounds (I) and (III) are further enriched by π-π stacking interactions.

Synthesis, characterization, and cancer cell-selective cytotoxicity of mixed-ligand cobalt(III) complexes of 8-hydroxyquinolines and phenanthroline bases.

Transition metal complexes exhibiting selective toxicity towards a broad range of cancer types are highly desirable as potential anticancer agents. Herein, we report the synthesis, characterization, and cytotoxicity studies of six new mixed-ligand cobalt(III) complexes of general formula [Co(B)2(L)](ClO4)2 (1-6), where B is a N,N-donor phenanthroline base, namely, 1,10-phenanthroline (phen in 1, 2), dipyrido[3,2-d:2',3'-f]quinoxaline (dpq in 3, 4), and dipyrido[3,2-a:2',3'-c]phenazine (dppz in 5, 6), and L is the monoanion of 8-hydroxyquinoline (HQ in 1, 3, 5) and 5-chloro-7-iodo-8-hydroxyquinoline (CQ in 2, 4, 6). The X-ray single crystal structures of complexes 1 and 2 as PF6- salts revealed a distorted octahedral CoN5O coordination environment. Complexes demonstrated good stability in an aqueous buffer medium and in the presence of ascorbic acid as a reductant. Cytotoxicity studies using a panel of nine cancer cell lines showed that complex 6, with the dppz and CQ ligands, was significantly toxic against most cancer cell types, yielding IC50 values in the range of 2 to 14 µM. Complexes 1, 3, and 5, containing the HQ ligand, displayed lower toxicity compared to their CQ counterparts. The phenanthroline complexes demonstrated marginal toxicity towards the tested cell lines, while the dpq complexes exhibited moderate toxicity. Interestingly, all complexes demonstrated negligible toxicity towards normal HEK-293 kidney cells (IC50 > 100 µM). The observed cytotoxicity of the complexes correlated well with their lipophilicities (dppz > dpq > phen). The cytotoxicity of complex 6 was comparable to that of the clinical drug cisplatin under similar conditions. Notably, neither the HQ nor the CQ ligands alone demonstrated noticeable toxicity against any of the tested cell lines. The Annexin-V-FITC and DCFDA assays revealed that the cell death mechanism induced by the complexes involved apoptosis, which could be attributed to the metal-assisted generation of reactive oxygen species. Overall, the dppz complex 6, with its remarkable cytotoxicity against a broad range of cancer cells and negligible toxicity toward normal cells, holds significant potential for cancer chemotherapeutic applications.

Chemistry of a series of heterobimetallic complexes MnIII2(CaII/SrII)X2 (X = Cl-, Br-).

This manuscript describes the syntheses, structures and magnetism of MnIII-CaII/SrII complexes which are compositionally relevant in the context of the oxygen evolving complex (OEC) of photosystem II (PS II). A series of trimetallic tetraoxo complexes containing redox-inactive metal ions CaII or SrII were synthesized using a tetranucleating ligand framework. The structural characteristics of these complexes, with the oxido ligands bridging the redox-inactive metals and the manganese centres, make them particularly relevant to biological and heterogeneous metal-oxido clusters. Electrochemical studies of these compounds show that the reduction potentials are highly dependent upon the Lewis acidity of the redox-inactive metal, identifying the chemical basis for the observed differences in electrochemistry. This correlation provides insights into the role of the CaII/SrII ion in modulating the redox potential of the OEC and of other redox-inactive ions in tuning the redox potentials of other metal-oxide electrocatalysts. Temperature dependent magnetic measurements have also been performed for the complexes.

Neuromodulation for Craniofacial Pain and Headaches.

Headaches and facial pain are highly prevalent diseases but are often difficult to treat. Though there have been significant advances in medical management, many continue to suffer from refractory pain. Neuromodulation has been gaining interest for its therapeutic purposes in many chronic pain conditions, including headaches and facial pain. There are many potential targets of neuromodulation for headache and facial pain, and some have more robust evidence in favor of their use than others. Despite the need for more high-quality research, the available evidence for the use of neuromodulation in treating headaches and facial pain is promising. Considering the suffering that afflicts patients with intractable headache, neuromodulation may be an appropriate tool to improve not only pain but also disability and quality of life.

Disentangling the trajectories of maternal depressive symptoms and partnership problems in the transition to parenthood and their impact on child adjustment difficulties.

Maternal perinatal depression (PND) and partnership problems have been identified to influence the development of later child adjustment difficulties. However, PND and partnership problems are closely linked which makes it difficult to draw conclusions about the exact transmission pathways. The aim of the present study was to investigate to what extent PND symptoms and partnership problems influence each other longitudinally and to examine the influence of their trajectories on child adjustment difficulties at the age of three. Analyses were based on publicly available data from the German family panel "pairfam". N = 354 mothers were surveyed on depressive symptoms and partnership problems annually from pregnancy (T0) until child age three (T4). Child adjustment difficulties were assessed at age three. Results of latent change score modeling showed that partnership problems predicted change in PND symptoms at T0 and T3 while PND symptoms did not predict change in partnership problems. Child adjustment difficulties at age three were predicted by PND symptoms, but not by partnership problems. Partnership problems predicted externalizing, but not internalizing symptoms. Results underline the effects of family factors for the development of child adjustment difficulties and emphasize the importance of early interventions from pregnancy onwards.

Synthesis, crystal structure, Hirshfeld surface analysis, DFT and NBO study of ethyl 1-(4-fluoro-phen-yl)-4-[(4-fluoro-phen-yl)amino]-2,6-diphenyl-1,2,5,6-tetra-hydro-pyridine-3-carboxyl-ate.

The title com-pound, C32H28F2N2O2, a highly functionalized tetra-hydro-pyridine, was synthesized by a one-pot multi-com-ponent reaction of 4-fluoro-aniline, ethyl aceto-acetate and benzaldehyde at room temperature using sodium lauryl sulfate as a catalyst. The com-pound crystallizes with two mol-ecules in the asymmetric unit. The tetra-hydro-pyridine ring adopts a distorted boat conformation in both mol-ecules and the dihedral angles between the planes of the fluoro-substituted rings are 77.1 (6) and 77.3 (6)°. The amino group and carbonyl O atom are involved in an intra-molecular N-H⋯O hydrogen bond, thereby generating an S(6) ring motif. In the crystal, mol-ecules are linked by C-H⋯F hydrogen bonds forming a three-dimensional network and C-H⋯π inter-actions. A Hirshfeld surface analysis of the crystal structure indicates that the most important contributions to the crystal packing are from H⋯H (47.9%), C⋯H/H⋯C (30.7%) and F⋯H/H⋯F (12.4%) contacts. The optimized structure calculated using density functional theory (DFT) at the B3LYP/6-311+G(2d,p) level is compared with the experimentally determined molecular structure in the solid state. The HOMO-LUMO behaviour was used to determine the energy gap and the Natural Bond Orbital (NBO) analysis was done to study donor-acceptor interconnections.

Securing maize reproductive success under drought stress by harnessing CO2 fertilization for greater productivity.

Securing maize grain yield is crucial to meet food and energy needs for the future growing population, especially under frequent drought events and elevated CO2 (eCO2) due to climate change. To maximize the kernel setting rate under drought stress is a key strategy in battling against the negative impacts. Firstly, we summarize the major limitations to leaf source and kernel sink in maize under drought stress, and identified that loss in grain yield is mainly attributed to reduced kernel set. Reproductive drought tolerance can be realized by collective contribution with a greater assimilate import into ear, more available sugars for ovary and silk use, and higher capacity to remobilize assimilate reserve. As such, utilization of CO2 fertilization by improved photosynthesis and greater reserve remobilization is a key strategy for coping with drought stress under climate change condition. We propose that optimizing planting methods and mining natural genetic variation still need to be done continuously, meanwhile, by virtue of advanced genetic engineering and plant phenomics tools, the breeding program of higher photosynthetic efficiency maize varieties adapted to eCO2 can be accelerated. Consequently, stabilizing maize production under drought stress can be achieved by securing reproductive success by harnessing CO2 fertilization.

Supramolecular interactions in some organic hydrated 2,4,6-triaminopyrimidinium carboxylate and sulfate salts.

Four salts, namely, 2,4,6-triaminopyrimidinium 6-chloronicotinate dihydrate, C4H8N5+·C6H3ClNO2-·2H2O, (I), 2,4,6-triaminopyrimidinediium pyridine-2,6-dicarboxylate dihydrate, C4H9N52+·C7H3NO42-·2H2O, (II), 2,4,6-triaminopyrimidinediium sulfate monohydrate, C4H9N52+·SO42-·H2O, (III), and 2,4,6-triaminopyrimidinium 3,5-dinitrobenzoate dihydrate, C4H8N5+·C7H3N2O6-·2H2O, (IV), were synthesized and characterized by X-ray diffraction techniques. Proton transfer from the corresponding acid to the pyrimidine base has occurred in all four crystal structures. Of the four salts, two [(I) and (IV)] exist as monoprotonated bases and two [(II) and (III)] exist as diprotonated bases. In all four crystal structures, the acid interacts with the pyrimidine base through N-H...O hydrogen bonds, generating an R22(8) ring motif. The sulfate group mimics the role of the carboxylate anions. The water molecules present in compounds (I)-(IV) form water-mediated large ring motifs. The formation of water-mediated interactions in these crystal structures can be used as a model in the study of the hydration of nucleobases. Water molecules play an important role in building supramolecular structures. In addition to these strong hydrogen-bonding interactions, some of the crystal structures are further enriched by aromatic π-π stacking interactions [(I) and (II)].

Late-stage Ligand Modification After Coordination Strengthens Stereoselectively Self-Assembled Hemiaminal Ether Complexes.

Fragile hemiaminal ether linkages present in the backbone of koneramines (LR OR'), tridentate ligands, bound to copper(II) in stereoselectively self-assembled syn-[Cu(LR OR')X2 ] complexes were transformed into sturdy methylene linkages to make corresponding rac-[Cu(LR H)Cl2 ] complexes by late-stage ligand modification after coordination with the retention of coordination sphere. The generality of stereoselective self-assembly of koneramine complexes is shown by utilising a number of metal ions, anions, amines, alcohols and thiols with complete characterisations.

Synthesis, crystal structure and Hirshfeld surface analysis of tert-butyl 4-[4-(di-fluoro-meth-oxy)phen-yl]-2,7,7-trimethyl-5-oxo-1,4,5,6,7,8-hexa-hydro-quinoline-3-carboxyl-ate.

The 1,4-di-hydro-pyridine ring of the title compound, C24H29F2NO4, adopts a distorted boat conformation, while the cyclo-hexene ring is in an almost twist-boat conformation. In the crystal, N-H⋯O and C-H⋯O hydrogen bonds as well as C-H⋯π inter-actions connect mol-ecules, forming layers parallel to the (100) plane. These layers are linked by van der Waals forces and C-H⋯F inter-actions, which consolidate the crystal structure. Hirshfeld surface analysis shows the major contributions to the crystal packing are from H⋯H (54.1%), F⋯H/H⋯F (16.9%), O⋯H/H⋯O (15.4%) and C⋯H/H⋯C (12.6%) contacts.

Minimally invasive colectomies can be performed with similar outcomes to open counterparts for colorectal cancer emergencies: a propensity score matching analysis utilizing ACS-NSQIP.

PURPOSE: The safety and feasibility of minimally invasive surgery (MIS) in the setting of colorectal cancer emergencies have been debated. We sought to compare postoperative outcomes of MIS with open techniques in the setting of colorectal cancer emergencies from the American College of Surgeons National Surgical Quality Improvement Program (ACS-NSQIP) database. METHODS: We included patients undergoing colectomy for colorectal cancer emergency between 2012 and 2019 "2012-2019" from the ACS-NSQIP dataset. We compared short-term morbidity, mortality, short-term oncological outcomes, and secondary outcomes for MIS vs open colectomies using propensity score matching. We then evaluated the trends of MIS versus open colectomies using linear regression analysis. RESULTS: We examined a total of 5544 patients (open n = 4070; MIS n = 1474) and included 1352 patients for our postoperative outcome analyses after propensity score matching 1:1 (open n = 676; MIS n = 676). Within the matched cohort, mortality was significantly higher in the open group (open 6.95% vs MIS 3.99%, OR 1.8, p = 0.023). Anastomotic leak rates were comparable between the  two groups (open 4.46% vs MIS 4.02%, OR 1.12, p = 0.787). Pulmonary complications were significantly higher after open surgery (open 10.06% vs MIS 4.73%, OR 2.25, p < 0.001). Rates of ileus were significantly higher amongst open patients (open 29.08% vs MIS 19.94%, p < 0.001). Patients stayed on average 1 day longer in the hospital after open surgery (p < 0.001). Rates of MIS for early tumors (N0 and T1/T2, n = 289) did not significantly change over 7 years (p = 0.597, rate = - 0.065%/year); however, utilization of MIS for late tumors (N1 or T3/T4, n = 4359) increased by 2.06% per year (p < 0.001). CONCLUSIONS: This study demonstrates that MIS was associated with superior postoperative outcomes compared to open surgery without compromising oncological outcomes in patients undergoing emergency colectomy for colon cancer. Within the matched cohort, MIS was associated with lower rates of mortality, pulmonary complications, ileus, and shorter postoperative length of stay.

Catalytic Acceptorless Dehydrogenation (CAD) of Secondary Benzylic Alcohols into Value-Added Ketones Using Pd(II)-NHC Complexes.

For the creation of adaptable carbonyl compounds in organic synthesis, the oxidation of alcohols is a crucial step. As a sustainable alternative to the harmful traditional oxidation processes, transition-metal catalysts have recently attracted a lot of interest in acceptorless dehydrogenation reactions of alcohols. Here, using well-defined, air-stable palladium(II)-NHC catalysts (A-F), we demonstrate an effective method for the catalytic acceptorless dehydrogenation (CAD) reaction of secondary benzylic alcohols to produce the corresponding ketones and molecular hydrogen (H2). Catalytic acceptorless dehydrogenation (CAD) has been successfully used to convert a variety of alcohols, including electron-rich/electron-poor aromatic secondary alcohols, heteroaromatic secondary alcohols, and aliphatic cyclic alcohols, into their corresponding value-added ketones while only releasing molecular hydrogen as a byproduct.

Enhancing LED spectral output with perylene dye-based remote phosphor.

LEDs offer a wide range of spectral output with high efficiencies. However, the efficiencies of solid-state LEDs with green and yellow wavelengths are rather low due to the lack of suitable direct bandgap materials. Here, we introduce and develop perylene-enhanced green LEDs that produce a higher wall-plug efficiency of 48% compared to 38% for a solid-state green LED. While the wall-plug efficiency of the perylene-enhanced red LED is still lower than that of a solid-state red LED, we demonstrate that remote phosphor colour converters are effective solutions for targeted spectral tuning across the visible spectrum for horticultural lighting. In this work, we retrofit existing white LEDs and augment photosynthesis via spectral output tuning to achieve a higher red-to-blue ratio. Our results show a significant improvement in plant growth by up to 39%, after a 4-month growth cycle. We observe no visible degradation of the colour converter even under continuous illumination with a current of 400 mA. This opens up new opportunities for using perylene-based colour converters for tuneable illumination with high brightness.

Coordination Behavior of the Tellurium Incorporated Mercuraazametallamacrocycle and Investigation of d10 ⋠⋠⋠d10 Interactions between Closed Shell (Ag+ Hg2+ ) Metal Ions.

Herein, a new tellurium and mercury containing mercuraazametallamacrocycle has been prepared via (2+2) condensation of bis(o-aminophenyl)telluride and bis(o-formylphenyl)mercury(II). The isolated bright yellow solid of mercuraazametallamacrocycle has adopted unsymmetrical figure-of-eight conformation in the crystal structure. To study the metallophilic interactions between closed shell metal ions, the macrocyclic ligand has been treated with two equiv. of AgOTf (OTf=trifluoromethansulfonate) and AgBF4 , which afforded greenish-yellow bimetallic silver complexes. The isolated silver complexes displayed intramolecular Hg⋅⋅⋅Ag, Te⋅⋅⋅Ag interactions as well as intermolecular Hg⋅⋅⋅Hg interactions and formed an extended 1D molecular chain by directing six atoms to interact as TeII ⋅⋅⋅AgI ⋅⋅⋅HgII ⋅⋅⋅HgII ⋅⋅⋅AgI ⋅⋅⋅TeII in a non linear fashion. The Hg⋅⋅⋅Ag, Te⋅⋅⋅Ag interactions have also been studied in solution by 199 Hg, 125 Te NMR spectroscopy, absorption, and emission spectroscopy. In DFT calculations, the Atom in Molecule (AIM) analysis, non-covalent interactions (NCI), natural bonding orbital (NBO) analysis strongly supported for experimental evidences and revealed that the intermolecular Hg⋅⋅⋅Hg interaction is stronger than the intramolecular Hg⋅⋅⋅Ag interactions.

NFIC regulates ribosomal biology and ER stress in pancreatic acinar cells and restrains PDAC initiation.

Pancreatic acinar cells rely on PTF1 and other transcription factors to deploy their transcriptional program. We identify NFIC as a NR5A2 interactor and regulator of acinar differentiation. NFIC binding sites are enriched in NR5A2 ChIP-Sequencing peaks. Nfic knockout mice have a smaller, histologically normal, pancreas with reduced acinar gene expression. NFIC binds and regulates the promoters of acinar genes and those involved in RNA/protein metabolism, and Nfic knockout pancreata show defective ribosomal RNA maturation. NFIC dampens the endoplasmic reticulum stress program through binding to gene promoters and is required for resolution of Tunicamycin-mediated stress. NFIC is down-regulated during caerulein pancreatitis and is required for recovery after damage. Normal human pancreata with low levels of NFIC transcripts display reduced expression of genes down-regulated in Nfic knockout mice. NFIC expression is down-regulated in mouse and human pancreatic ductal adenocarcinoma. Consistently, Nfic knockout mice develop a higher number of mutant Kras-driven pre-neoplastic lesions.

Pushing the Boundary of Covalency in Lanthanoid-Tellurium Bonds: Insights from the Synthesis, Molecular and Electronic Structures of Low-Coordinate, Monomeric Europium(II) and Ytterbium(II) Tellurolates.

Owing to the strict hard/soft dichotomy between the lanthanoids and tellurium atoms, and the strong affinity of lanthanoid ions for high coordination numbers, low-coordinate, monomeric lanthanoid tellurolate complexes have remained elusive as compared to the lanthanoid complexes with lighter group 16 elements (O, S, and Se). This makes the development of suitable ligand systems for low-coordinate, monomeric lanthanoid tellurolate complexes an appealing endeavor. In a first report, a series of low-coordinate, monomeric lanthanoid (Yb, Eu) tellurolate complexes were synthesized by utilizing hybrid organotellurolate ligands containing N-donor pendant arms. The reaction of bis[2-((dimethylamino)methyl)phenyl] ditelluride, 1 and 8,8'diquinolinyl ditelluride, 2 with Ln0 metals (Ln=Eu, Yb) resulted in the formation of monomeric complexes [LnII (TeR)2 (Solv)2 ] [R=C6 H4 -2-CH2 NMe2 ] [3: Ln=Eu, Solv=tetrahydrofuran; 4: Ln=Eu, Solv=acetonitrile; 5: Ln=Yb, Solv=tetrahydrofuran; 6: Ln=Yb, Solv=pyridine] and [EuII (TeNC9 H6 )2 (Solv)n ] (7: Solv=tetrahydrofuran, n=3; 8: Solv=1,2-dimethoxyethane, n=2), respectively. Complexes 3-4 and 7-8 represent the first sets of examples of monomeric europium tellurolate complexes. The molecular structures of complexes 3-8 are validated by single-crystal X-ray diffraction studies. The electronic structures of these complexes were investigated using Density Functional Theory (DFT) calculations, which revealed appreciable covalency between the tellurolate ligands and lanthanoids.

Syntheses and crystal structures of three salts of 1-(4-nitro-phenyl)-piperazine.

The crystal structures and Hirshfeld surface analyses of three salts of 1-(4-nitro-phenyl)-piperazine with 2-chloro-benzoic acid, 2-bromo-benzoic acid and 2-iodo-benzoic acid are reported. The chloro-benzoate salt, C10H14N3O2 +·C7H4ClO2 -, contains whole-ion-disordered cations and anions, which were modeled with two equivalent conformations with occupancies of 0.745 (10)/0.255 (10) and 0.563 (13)/0.437 (13), respectively. The bromo-benzoate and iodo-benzoate derivatives are isomorphous and crystallize as hemihydrates, viz. C10H14N3O2 +·C7H4BrO2 -·0.5H2O and C10H14N3O2 +·C7H4IO2 -·0.5H2O, respectively [the water mol-ecule is disordered over two locations with occupancies of 0.276 (3)/0.223 (3) for the iodo-benzoate derivative]. In the extended structures, all three salts feature an R 4 4(12) loop of two anions and two cations linked by N-H⋯O hydrogen bonds.

5-([(Z)-Meth-oxy-imino]{2-[(2-methyl-phen-oxy)meth-yl]phen-yl}meth-yl)-1,3,4-oxa-diazole-2(3H)-thione dimethyl sulfoxide monosolvate.

The title compound, C18H17N3O3S·C2H6OS, crystallizes in the monoclinic space group P21 /c. In the crystal, C 1 1(9) chains of C-H⋯O inter-actions are formed, propogating in the c-axis direction. The N-H hydrogen atom forms a strong hydrogen bond with the oxygen atom of a DMSO solvate mol-ecule.

Syntheses, crystal structures and Hirshfeld surface analysis of three salts of 1-(4-nitro-phenyl)-piperazine.

The structures and Hirshfeld surface analysis of three salts of 1-(4-nitro-phenyl)-piperazine are discussed. In 4-(4-nitro-phen-yl)piperazin-1-ium salicylate (C10H14N3O2 +·C7H5O3 -), there are strong hydrogen bonds between cation and anion and the 4-nitro-phenyl substituent occupies an equatorial position in the piperazinium ring. The cation and anion are linked together by supra-molecular inter-actions [graph-set notation of hydrogen bonding (6) propagating in the a-axis direction]. Additionally, there is π-π stacking involving the salicylate anion and the piperazinium cation in adjacent asymmetric units as well as a C-H⋯π inter-action between a hydrogen atom on the piperazine ring and the phenyl ring within the salicyclate anion. In bis-[4-(4-nitro-phen-yl)piperazin-1-ium] bis-(4-fluoro-benzoate) trihydrate (2C10H14N3O2 +·2C7H4FO2 -·3H2O), there are two cations, two anions, and three water mol-ecules of solvation in the asymmetric unit, all linked by hydrogen bonds [graph-set notation of hydrogen bonding R 2 2(20) between adjacent cations and R 3 3(9) between a cation and its adjacent anion]. In the anion, the 4-nitro-phenyl ring occupies an axial substitution position in the piperazinium ring, which is relatively rare. Within the asymmetric unit, the phenyl groups in the cations show an offset π-π inter-action. Additionally, there is a C-H⋯π inter-action between a hydrogen atom on the phenyl ring within a cation and the phenyl ring within an anion. In 4-(4-nitro-phen-yl)piperazin-1-ium 3,5-di-nitro-benzoate (C10H14N3O2 +·C7H4N2O6 -), there is a strong N-H⋯O hydrogen bond linking the cation and anion and the 4-nitro-phenyl ring occupies an axial substitution position in the piperazinium ring, as seen in the previous structure. In the crystal, the cation and the anion form a complex three-dimensional hydrogen-bonded array involving R 2 2(8), R 4 4(12) and R 4 4(20) rings propogating in the a-axis direction. The nitro-phenyl group is disordered with occupancies of 0.806 (10) and 0.194 (10).