The nickel(II) ion in 1 is octahedrally coordinated by the O atoms of two water molecules, two O atoms from O-monodentate 6-fluoronicotinate ligands and two N atoms from bridging 4,4′-bipyridine ligands.A one-dimensional nickel(II) coordination polymer with the mixed ligands 6-fluoronicotinate (6-Fnic) and 4,4′-bipyridine , namely, [Ni(H catena-poly[[diaquabis(6-fluoropyridine-3-carboxylato-κO)nickel(II)]-μ-4,4′-bipyridine-κ2N:N′] trihydrate], {[Ni(6-Fnic)2(H2O)2]·3H2O}n, (1), was prepared by the reaction of nickel(II) sulfate heptahydrate, 6-fluoronicotinic acid (C6H4FNO2) and 4,4′-bipyridine (C10H8N2) in a mixture of water and ethanol. The nickel(II) ion in 1 is octahedrally coordinated by the O atoms of two water molecules, two O atoms from O-monodentate 6-fluoronicotinate ligands and two N atoms from bridging 4,4′-bipyridine ligands, forming a trans isomer. The bridging 4,4′-bipyridine ligands connect symmetry-related nickel(II) ions into infinite one-dimensional polymeric chains running in the [11, the polymeric chains and lattice water molecules are connected into a three-dimensional hydrogen-bonded network via strong O—H⋯O and O—H⋯N hydrogen bonds, leading to the formation of distinct hydrogen-bond ring motifs: octameric R88(24) and hexameric R86(16) loops.A one-dimensional nickel(II) coordination polymer with the mixed ligands 6-fluoronicotinate (6-Fnic) and 4,4′-bipyridine , namely,  On the other hand, no metal complexes of other fluorinated analogues of nicotinate  have been reported so far.Although metal complexes with nicotinate have been well-studied and documented ·3H2O} (1). The synthesis was carried out in a mixture of water and ethanol in the hope that the coordinated water molecules would complete the coordination sphere around the nickel(II) ion and participate in the formation of various hydrogen-bond motifs within the hydrogen-bonded framework, along with the anticipated lattice water molecules. Furthermore, we wanted to explore the effect of the probable weak intermolecular interactions involving the aromatic F atoms (for example C—H⋯F interactions) on the assembly of the polymeric chains in the crystal packing.In this work, we report the synthesis and characterization of the first metal complex with 6-fluoronicotinate – the one-dimensional nickel(II) coordination polymer {. In this way, a trans isomer is formed (N2i—Ni1—N2 = 180°)  ions into an infinite one-dimensional polymeric chain extending in the [12(H2O)2]·3H2O}.As the nickel(II) ion and the lattice water molecule (atom O4) are situated on an inversion center and a twofold axis, respectively, the asymmetric unit of °) Fig. 1. The 6-fon Fig. 2. There acis pairs of the ligating atoms [89.65 (6)–90.87 (6)°]. The Ni1—O1 bond length [2.1067 (16) Å] is somewhat longer than the Ni1—O2 and Ni1—N2 bond lengths , which is in agreement with the fact that the water molecules are bound in the axial positions of the octahedron. The Ni—Oc (c = carboxylate) bond lengths in 1 are comparable to those seen in the related nickel(II) complexes with 6-chloronicotinate  ligands  ion is slightly distorted, as indicated by the angles for the The 4,4′-bypyridine ring is not coplanar with the coordinated water molecule atom O1, but it is rotated slightly (approximately 4°) about the Ni1—N2 bond, as is evident from the torsion angles Ni1—N2—C7—C8 [176.35 (19)°] and Ni1—N2—C11—C10 [−176.03 (18)°]. The values of these torsion angles ought to be 180° in the case of coplanarity of the 4,4′-bipyridine ring and the O1 atom of the coordinated water molecule.1 mainly features strong O—H⋯O and O—H⋯N hydrogen bonds (Table 1Cg1⋯Cg1(−x + y + z + 1) = 3.8148 (16) Å; dihedral angle between the planes = 0.00 (14)°; slippage = 1.792 Å and Cg1⋯Cg2 = 3.8798 (16) Å; dihedral angle between the planes = 11.68 (13)°; slippage = 1.917 Å; Cg1 and Cg2 are the centroids of the 6-fluoronicotinate pyridine (N1/C1–C5) and 4,4′-bipyridine (N2/C7–C11) rings, respectively]. The strong hydrogen bonds link the polymeric chains and the lattice water molecules into an infinite three-dimensional network. The structure can be better analysed if viewed down the [1Cg1⋯Cg1].The extended structure of s Table 1 and π–π rk Fig. 3. While b1  coordination polymers containing bridging 4,4′-bipyridine and pyridinedicarboxylate ligands, there are only two structurally similar one-dimensional nickel(II) polymers with 4,4′-bipyridine and pyridinecarboxylate . Both the coordinated (two) and lattice (three) water molecules were released in the same step . The two small endothermic peaks in the DSC curve (63 and 115°C) suggest that the process of the water evolution is not straightforward and that the water molecules are differently bound in 1 (coordinated vs lattice). Indeed, the polymeric chains and lattice water molecules are assembled into a hydrogen-bonded three-dimensional structure (see Supramolecular features). It is therefore not surprising that the release of some water molecules affects the whole hydrogen-bonded structure and leads to its complete collapse in a single, not well-resolved thermal step. The thermal decomposition of 1 continues in a broad step (observed mass loss 56.7%) in the wide temperature range of 150–570°C (without any well-defined peaks in the DSC curve), which probably corresponds to the complete degradation of 1. The remaining residue at 600°C is most probably NiO.The thermal stability of −1 on a Perkin–Elmer Spectrum TwoTM FTIR spectrometer in the ATR mode. The PXRD trace was recorded on a Philips PW 1850 diffractometer, Cu Kα radiation, voltage 40 kV, current 40 mA, in the angle range 5–50° (2θ) with a step size of 0.02°. Simultaneous TGA/DSC measurements were performed at a heating rate of 10°C min−1 in the temperature range 25–600°C, under a nitrogen flow of 50 mL min−1 on an Mettler-Toledo TGA/DSC 3+ instrument. Approximately 2 mg of the sample were placed in a standard alumina crucible (70 µl).All chemicals for the synthesis were purchased from commercial sources  and used as received without further purification. The IR spectrum was obtained in the range 4000–400 cm1, suitable for X-ray diffraction measurements, were obtained. These were collected by filtration, washed with their mother liquor and dried in vacuo. Yield: 0.0483 g (45%). Selected IR bands (ATR) : 3351 [ν(O—H)], 3088 [ν(C—H)], 1607 [ν(C=O)], 1558, 1475, 1415, 1392, 1368  .6-Fluoronicotinic acid  was dissolved in distilled water (5 ml), 4,4′-bipyridine  was dissolved in ethanol (2 mL) and nickel(II) sulfate heptahydrate  was dissolved in distilled water (2 mL). The solutions of the two ligands were first mixed together under stirring. The resulting solution was then slowly added to the nickel(II) sulfate solution under stirring. The pH of the final solution was adjusted to 7 by adding an ammonia solution dropwise. The obtained, clear solution was left to evaporate slowly at room temperature for approximately three weeks until light–blue crystals of Uiso(H) = 1.2Ueq(C) for aromatic H atoms]. Water H atoms were found in difference-Fourier maps, O—H distances were restrained to an average value of 0.82 Å using DFIX and DANG instructions and they were refined isotropically [Uiso(H) = 1.2Ueq(O)].Crystal data, data collection and structure refinement details are summarized in Table 2The highest difference peak is 0.92 Å away from the O3 atom and the deepest difference hole is 0.50 Å away from the Ni1 atom.10.1107/S2056989020003023/xi2024sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020003023/xi2024Isup4.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989020003023/xi2024sup3.docxTGA, DSC and IR data. DOI: 1988000CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Five-minute epoxy serves as a waterproof case enabling the operation of our supercapacitors while submerged underwater and a gel electrolyte extends cycling stability to 10,000 cycles with ~90% capacitance retention.Fired brick is a universal building material, produced by thousand-year-old technology, that throughout history has seldom served any other purpose. Here, we develop a scalable, cost-effective and versatile chemical synthesis using a fired brick to control oxidative radical polymerization and deposition of a nanofibrillar coating of the conducting polymer poly (PEDOT). A fired brick’s open microstructure, mechanical robustness and ~8 wt% α-Fe Fired brick is a universal building material, produced by thousand-year-old technology, which throughout history has seldom served any other purpose. Here, the authors show that bricks can store energy after chemical treatment to convert their iron oxide content into conducting polymer nanofibers. This masonry building block is commonly found in various red tones and mostly comprised of fused particles of silica (SiO2), alumina (Al2O3) and hematite (α-Fe2O3)2. The red color of a brick originates from hematite, a pigment first utilized by humans 73,000 years ago4 and serving today as a low-cost naturally abundant inorganic precursor for catalysts5, magnets6, and alloys7. State-of-the-art energy storage materials are also produced from hematite. For example, FeNx, FeP, and Li5FeO4 are synthesized via anionic or cationic exchange for potassium-ion batteries, Zn–air batteries, pseudocapacitors, and lithium-ion batteries11; electrochemical transformation of hematite leads to FeOOH supercapacitor anodes12.Fired brick, typically used for construction and architectural esthetics, is one of the most durable materials with a 5000-year history dating back to Neolithic China13. Chemistries enabled by hematite provide an opportunity for developing cutting-edge functionalities on a fired brick where 8 wt% α-Fe2O3 content and a 3D porous microstructure afford an ideal substrate for engineering a mechanically robust electrode. Here, we develop a supercapacitor using a brick’s hematite microstructure as reactant to vapor-deposit a nanofibrillar coating of the conducting polymer poly (PEDOT). Vapor-phase synthesis leads to PEDOT coatings exhibiting a high electronic conductivity14 and facile charge transfer, making it an ideal route for producing electrodes15. This synthesis utilizes a brick’s open microstructure and thermal stability to permeate acid and monomer vapor through its pores at 160 °C to control α-Fe2O3 dissolution and Fe3+ hydrolysis with concomitant oxidative radical polymerization.This work is inspired by our recently published rust-assisted vapor phase polymerization−2 and energy density of 222 µWh cm−2 at a current density of 0.5 mA cm−2. This two-electrode-based measurement is collected using 1 M H2SO4 aqueous electrolyte under 1 V operating voltage window. To mimic a “brick-mortar-brick” structure, a supercapacitor is modified using a quasi-solid-state electrolyte /1 M H2SO4) that also plays the role of binder and separator. Our devices are water-resistant because they are coated with an epoxy encapsulating layer that protects them enabling charge storage at temperatures between −20 and 60 °C. A supercapacitor is stable in ambient conditions undergoing 10,000 charge–discharge cycles with ~100% coulombic efficiency and ~90% capacitance retention. Moreover, a supercapacitor brick module is produced reaching a 3.6 V voltage window by connecting three devices in series.A symmetric brick-based supercapacitor shows an areal capacitance of 1.60 F cm2O3 at 160 °C with HCl vapor; this process liberates Fe3+ ions, promotes hydrolysis and initiates precipitation of colloidal 1D FeOOH nuclei  and acid (HCl) where the former leads to oxidative radical polymerization and the latter, to acid-catalyzed polymerization . Using a HCl vapor concentration less than 4.8 mM leads to an incomplete reaction because both oxidative radical polymerization and acid-catalyzed polymerization are impeded  exhibiting 2Ω two-point probe electrical resistance and nanofibers characterized by a ~30 µm length and ~190 nm diameter  evaporation, (2) dissolution, (3) hydrolysis, and (4) polymerization. A blue PEDOT coating is visible on a brick 4 h after initiating a reaction and its thickness increases inversely proportional with electrical resistance until the end of reaction at 14 h. An extended polymerization time increases the polymer coating’s two-point probe electrical resistance  sizes and porosities are investigated  with different gravel SiO sizes anted Fig.  that fac–3 with dses Fig. . These tses Fig. . Porositsly Fig. . Our polsly Fig.  and pattsly Fig.  as demonsly Fig. . Note th2O3 particles enables deposition of PEDOT coatings on customized substrates such as concrete road pavers  weighing 249 mg and carrying 6.97 mg PEDOT is fabricated into an electrode with one 1 cm × 0.5 cm face exposed . The electrode exhibits a quasi-rectangular shaped three-electrode cyclic voltammogram and a capacitance of 2.61 F cm−2 (187 F g−1 based on PEDOT’s mass) at 2 mV s−1 in 1 M H2SO4  arise due to iron species in brick and disappears as scan rate increases to 25 mV s−1 because Faradaic processes in PEDOT are faster than those occurring from solid Fe2O3  than sodium sulfate (0.878 F cm−2) at 25 mV s−1  vs. Na+ (5.19 × 10−8 m2 V−1 s−1) or a lower electrical resistance caused by doping at low pH14. We probed this behavior further using electrochemical impedance spectroscopy. Nyquist plots and an equivalent circuit diagram demonstrate a significantly lower ion diffusion resistance for H2SO4 (1.7Ω) vs. Na2SO4 (4.6Ω) and minimal change in electrode material electrical resistance at low pH . Diffraction patterns remain unchanged demonstrating that most inorganic species in a brick remain unaffected by synthesis and electrochemical cycling  and Al (1.97 µg mL−1) in the electrolyte after cycling, these concentrations are equivalent to mass losses (based on the entire brick) of 0.0127 and 0.0075 wt% for α-Fe2O3 and Al2O3, respectively. These results confirm that inorganic species in a brick are preserved after electrochemical cycling.To quantify dissolution of a brick’s α-Fe2SO4 aqueous electrolyte  encompassing two PEDOT-coated bricks and a separator and its total mass (499 mg) includes 13.94 mg of PEDOT. Nyquist plot shows an aggregated internal resistance of 3Ω and a line with a ~45° slope between semicircle and low-frequency domain (Warburg region)  leading to a device areal capacitance of 1.59 F cm−2 calculated using the electrode area directly in contact with separator (0.5 cm2)  serve as electrodes in a symmetric supercapacitor (1 cm × 0.5 cm × 0.5625 cm) using 1 M Hyte Fig. . A devicm2) Fig. . In our −2 current density in a 1 V window  as well as areal energy and power densities of 222 and 0.25 mW cm−2, respectively (394 µWh cm−3 and 0.44 mW cm−3 for volumetric). High power density (12.5 mW cm−2) is obtained at a current density of 25 mA cm−2 albeit with lowered capacitance (0.706 F cm−2) and energy density (98 µWh cm−2) because ion transport in our thick electrode is limited (shown by high IR drop of 0.4 V). Our device works in an extended voltage window (1.2 V) resulting in cyclic voltammograms and galvanostatic charge–discharge curves that retain shape  during galvanostatic charge-discharge experiments at 0.5 mA cmitance 0.06 F cm−2 V during2SO4 gel that binds PEDOT-coated bricks and serves as electrolyte and separator  containing 13.94 mg of PEDOT. In a tensile test, our electrode–gel–electrode structure withstands a shearing force equal to 1000 times the device’s weight20  and areal energy density (121 µWh cm−2) originating from PEDOT-coated brick electrodes are calculated from galvanostatic charge–discharge curves ; cyclic voltammograms also show capacitive behavior  using a poly/1 M Htor Fig. . The gelior Fig. . The absces Fig. .−2)  with ~87% capacitance retention , methanol (≥99.8%), and hydrochloric acid (37%) are purchased from Sigma-Aldrich; sulfuric acid (AR) is purchased from Macron. The PEDOT:PSS solution (Clevios PH 1000) is purchased from Heraeus company. All chemicals are used without further purification. Platinum foil  is purchased from Alfa Aesar and utilized for engineering electrode leads and Celgard 3501 membrane is used as a separator. Fired bricks are purchased from local hardware stores: The Home Depot Inc. , Lowe’s Inc.  and Menards Inc. . Road pavers are purchased from Menards Inc.  and all construction materials used for developing electrodes are cut using a diamond saw. Red cement color (α-Fe2O3 particles) produced by NewLook Inc. is purchased from The Home Depot Inc.  and serves as an oxidant source for developing chemical syntheses. Materials for making concrete  include commercial-grade Quikrete Portland cement (Type I/II) , Quikrete all-purpose sand (Internet #100318450Model # 115251Store SKU #137263) and Pavestone multi-purpose patio/paver base .Chlorobenzene (99%), 3,4-ethylenedioxythiophene (97%), poly (Rs), electrode material resistance (Rm), material capacitance (Cm), double-layer capacitance (Cdl), and constant phase element (CPE). Here, Rs reflects the electrolyte ionic mobility and Rm represents the electrical resistance of the electrode. Powder X-ray diffraction spectra of brick powders pulverized by mortar and pestle are obtained in a Bruker d8 Advance X-ray diffractometer at room temperature, with a Cu Kα radiation source (λ = 1.5406 Å) and LynxEyeXe detector. The sample holder is a background-free silicon disk rotating at 30 rpm when collecting data with a 0.02° scan step at 40 kV and 40 mA. Current–voltage tests are performed on a 3D printed two-point probe station with two gold probes separated by 2 mm23. Water absorption experiments are performed as described in ASTM C67/C67M-18 except brick samples are 1 cm × 0.5 cm × 0.28 cm in size. Inductively coupled plasma mass spectrometry is performed on a Perkin Elmer ELAN DRC II ICP–MS. Samples for testing are obtained from electrolytes (5 mL 1 M H2SO4) after three-electrode cyclic voltammetry experiments and are diluted to 1/100 with Mili-Q water before analyses. External calibration curves are obtained with IV-ICPMS-71A standard solution purchased from Inorganic Ventures, Inc.Scanning electron micrographs and energy-dispersive X-ray spectra are collected with a JEOL 7001LVF FE-SEM. Two-point probe resistance measurements are carried out using a Fluke 177 True RMS digital multimeter with 3 mm distance between two probes. Thermogravimetric analysis is conducted on a Discovery TGA (TA Instruments). Cyclic voltammetry, galvanostatic charge–discharge measurements and electrochemical impedance spectroscopy are performed in a BioLogic VMP3 multipotentiostat. For electrochemical impedance spectroscopy, the sinusoidal disturbance is 10 mV with frequencies scanned between 100 kHz and 0.1 Hz. A Nyquist plot shows real impedance Z′ vs. imaginary impedance −Z′′ under a sinusoidal disturbance at the open circuit potential. Fitting of Nyquist plot using an equivalent circuit diagram contains solution resistance (2SO4 (1 M) is then carried out by pipetting acid on the inner wall under vigorous stirring to prevent carbonization of poly. Stirring minimizes localized heating and is carried out for 1 h resulting in a homogeneous, translucent, and colorless solution.The gel electrolyte is formulated using 1 g of poly powder dissolved in 10 mL deionized water under vigorous stirring at 90 °C and cooled to around 50 °C. Dropwise addition of 1 g of concentrated HBrick is cut using a diamond saw (±0.03 cm error) into the following 4 different sizes: 1.00 cm ⨯ 0.50 cm ⨯ 0.28 cm (for studying synthesis and electrochemistry), 1.27 cm ⨯ 1.27 cm ⨯ 0.20 cm (for patterning), 2.00 cm ⨯ 1.00 cm ⨯ 1.00 cm  and 10.16 cm ⨯ 6.77 cm ⨯ 5.72 cm . A brick is thrice washed with deionized water to remove surface dust then dried at 160 °C for 1 h and cooled to room temperature.The syntheses of all types of 1 cm ⨯ 0.5 cm ⨯ 0.28 cm brick are performed in a 25 mL Teflon-lined stainless-steel autoclave as shown in Fig. A brick (1.27 cm ⨯ 1.27 cm ⨯ 0.20 cm) is patterned using a polyimide tape mask. Synthesis is carried out at 150 °C for 14 h in a 125 mL Teflon-lined stainless-steel autoclave containing 1 mL of a 0.85 M EDOT solution in chlorobenzene and 0.6 mL of 12 M HCl  with a large brick (10.16 cm ⨯ 6.77 cm ⨯ 5.72 cm). The reaction is carried out using 15 mL of 12 M HCl and 15 mL of a 0.85 M EDOT in chlorobenzene solution at 150 °C for 6 h Fig. .2O3 particles to a concrete surface  for 3 s, then dried in air. Synthesis is performed at 150 °C for 14 h in a 125 mL Teflon-lined stainless-steel autoclave loaded with 1 mL of a 0.45 M EDOT in chlorobenzene solution and 0.1 mL of 12 M HCl.We produce a PEDOT coating on concrete by applying α-Fe−1 poly/1 M H2SO4) is pipetted onto two 1 cm ⨯ 0.5 cm ⨯ 0.28 cm PEDOT-coated bricks (100 µL each brick on the 1 cm ⨯ 0.5 cm face). This electrolyte is allowed to impregnate for 12 h at ambient conditions  forming a semidry gel layer. An additional 25 µL of gel electrolyte is added serving as a binder between two bricks to assemble a sandwich-type supercapacitor. A device is dried in ambient conditions  for 1 h before sealing with epoxy . This electrolyte is allowed to stabilize for 12 h at ambient conditions ; this process is repeated for all brick electrodes resulting in a thick gel layer  in 1 mL of 1 M HSupplementary InformationPeer Review FileDescription of Additional Supplementary FilesSupplementary Movie 1


The complex has hexagonal layers of Cs3Yb3 with THF ligands and Me3Si groups in between the layers.Reduction of (C 5:η5-1-(trimethylsilyl)cyclopentadienyl]caesium(I)ytterbium(II)], [CsYb(C8H13Si)3(C4H8O)]n or [(THF)Cs(μ-η5:η5-Cp′)3YbII]n was synthesized by reduction of a red THF solution of (C5H4SiMe3)3YbIII with excess Cs metal and identified by X-ray diffraction. The compound crystallizes as a two-dimensional array of hexagons with alternating CsI and YbII ions at the vertices and cyclopentadienyl groups bridging each edge. This, based off the six-electron cyclopentadienyl rings occupying three coordination positions, gives a formally nine-coordinate tris(cyclopentadienyl) coordination environment to Yb and the Cs is ten-coordinate due to the three cyclopentadienyl rings and a coordinated molecule of THF. The complex comprises layers of Cs3Yb3 hexagons with THF ligands and Me3Si groups in between the layers. The Yb—C metrical parameters are consistent with a 4f14 YbII electron configuration.The green compound poly[(tetrahydrofuran)tris[μ-η However, the Cs reductions yielded polymeric complexes of general formula [Cp′′M(μ-Cp′′)2Cs(THF)2]n where the Cs cation has coordinated THF and cyclopentadienide ligands. Attempts to extend this chemistry to smaller rare-earth metals by reduction of Cp′3Ln  showed evidence of LnII in solution; however, the reduction products were highly unstable and decomposed even at 238 K.The new +2 oxidation states for the rare-earth metals Y, La, Ce, Pr, Gd, Tb, Ho, Er, and Lu were recently discovered by reduction of CpC8 Fig. 1 3Yb]n, 1 (Cp′ = C5H4SiMe3) was isolated by reduction of the Cp′3YbIII complex ][Cp′3YbII] (crypt = 2.2.2-cryptand), which was fully characterized as a 4f14 YbII complex, Table 23Ln reduction chemistry, the difference in Ln⋯Cp(centroid) distances between the LnIII and LnII complexes provides important information on the electronic configuration of the lanthanide ion  distances for reduction of 4fnLnIII ions to 4fn+1LnII ions range from 0.1 to 0.2 Å  distance is characteristic of a 4f13 YbIII reduction to a 4f14 YbII ion. In contrast, LnII ions with 4nf5d1 configurations where the additional electron populates a d-orbital instead of the an f-orbital have differences of only 0.02–0.05 Å ⋯Yb⋯Cp′(centroid) and 109.0–121.4° Cp′(centroid)⋯Cs⋯Cp′(centroid) angles generate the undulation of the hexagons shown in Fig. 6The side view of these layers in Fig. 61 are shorter than the 3.278 and 3.435 Å Cs⋯Cp′′(centroid) distances in [(THF)2Cs][(μ-η5:η5-Cp′′)2UII(η5-Cp′′)]n,  distances in {[(Me3Si)2NCs]2·[(C5H5)2Fe)] 0.5·(C6H5Me)}n,  distances in [(THF)2Cs(μ3-O)3{[Ti(C5Me5)]3-(μ3-CCH2)}] 2UII(η5-Cp′′)]n 3{[Ti(C5Me5)]3(μ3-CCH2)}] , 3.197 (1), and 3.268 (2) Å Cs⋯Cp′(centroid) distances in 1 differs from that of the [(THF)2Cs][(μ-η5:η5-Cp′′)2MII(η5-Cp′′)]n, complexes , which comprise zigzag chains of –M–(μ-Cp′′)–Cs–(μ-Cp′′)– repeat units with a terminal Cp′′ attached to M and two terminal THF ligands attached to Cs  coordination like Yb in 1, but the Cs is coordinated by only two cyclopentadienyl ligands to give a bent metallocene Cp′′2Cs(THF)2 sub-structure with these larger rings.The extended structure of et al., 2016x moieties with various types of cyclopentadienyl rings (Cpx): [Na(μ-η5:η5-C5H5)3YbII]n 2YbII2(μ-η5:η5-Cp′′)2]n Yb(μ-I)(μ-η5:η5-C5Me5)Yb(C5Me5)]n (Ph2Pz)(THF)]n  3YbII]n 3SmII] is similar 2UII(η5-Cp′′)]n 2NCs]2[(C5H5)2Fe)]·0.5(C6H5Me)}n 3{[Ti(C5Me5)]3(μ3-CCH2)}] Li]n  in THF (2 mL) to excess Cs as a smear produced a green solution. This was stirred for 15 min at room temperature and then layered at the bottom of a vial below an Et2O (10 mL) layer for crystallization at −35°C. After 1 d, X-ray quality dark-green crystals of [(THF)Cs(μ-η5:η5-Cp′)3YbII]n were isolated. A small number of crystals were obtained and used for crystallographic analysis. Too little sample was available for other characterization.In an argon-filled glovebox, addition of a red solution of Cp′5:η5-Cp′)3YbII]n, 1 are summarized in Table 3Uiso(H) values of 1.2Ueq(C) for CH2 and aromatic hydrogens and 1.5Ueq(C) for CH3 hydrogens with C—H distances of 0.99 (CH2), 0.95 (aromatic), and 0.98 Å (CH3).Crystal data and structure refinement for [(THF)Cs I. DOI: 10.1107/S2056989020008051/zl2785Isup2.hklStructure factors: contains datablock(s) I. DOI: 2010185CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Lolium multiflorum L.) including a cultivar , bred to accumulate larger concentrations of Mg.Magnesium (Mg) deficiency (known as grass tetany) is a serious metabolic disorder that affects grazing ruminants. We tested whether Mg-fertiliser can increase Mg concentration of Italian ryegrasses (2.6H2O). Under field conditions, the three cultivars in the CE condition and cv. Alamo were grown at two sites, and four rates of MgSO4 fertiliser application rates (0–200 kg ha−1 MgO). Multiple grass cuts were taken over two-years.Under controlled environment (CE) conditions, three cultivars  were grown in low-nutrient compost at six fertiliser rates (0–1500 μM MgClp < 0.05) smaller than cv. Alamo. The effect of Mg-fertiliser rate on DM yield was not significant (p ≥ 0.05).Grass Mg concentration increased with increasing Mg-fertiliser application rates in all cultivars and conditions. Under field conditions, cv. Bb2067 had 11–73% greater grass Mg concentration and smaller forage tetany index (FTI) than other cultivars across the Mg-fertiliser application rates, sites and cuts. Grass dry matter (DM) yield of cv. Bb2067 was significantly  contains supplementary material, which is available to authorized users. Grazing landscapes and ruminant livestock have a dominant role in the environmental, economic and food security of many countries, especially in temperate regions. For example, in 2017/18, 72% of the UK’s land area (17.5 M ha) was utilised for agriculture; of that area the proportion of grazing land was 35% permanent grass, 22% sole rights rough grazing, 6.9% common land rough grazing, and 6.5% temporary grass DEFRA . These g−1 DM for cattle, and 900 and 1200 mg kg−1 DM for sheep  and potassium (K+) ions, which is termed as the forage tetany index (FTI)  is divided by the atomic weight and multiplied by the valence of the respective elements).In livestock, ~70% of Mg is stored in the skeleton and this pool is not easily mobilised when dietary Mg intake is reduced (Martens and Stumpff FTI) Eq.  (Kemp anFTI) Eq. . The risFTI) Eq. . AnnuallFTI) Eq. .1\docume+ in the soil solution suppresses the absorption of Mg2+ by plant roots  digestibility which accelerates rumen passage and reducing the ruminal absorption of Mg Suttle . This iss Elliot .−1 DM ± SD) reported include: grass hay 1400 ± 520, grass silage 1700 ± 540, clover silage 2300 ± 750, lucerne hay 1700 ± 270, maize silage 2200 ± 690 (Suttle −1 DM) in New Zealand  synthetic variety called Magnet  with increased grass Mg concentration was bred by the Welsh Plant Breeding Station in the 1970s  containing low nutrient media . Plants were watered every other day with Hortimix standard. In total there were 18 trays, each containing 8 plants of each line, randomly assigned to the central part of the tray. These plants were surrounded by cv. RvP plants to act as guard rows.The CE experiment was conducted at the Sutton Bonington Campus of the University of Nottingham in 2016. Three cultivars, cv. Bb2067, cv. Bb2068 and cv. RvP were sown on 09 August 2016 in 576 cell trays  in compost  with a topping of fine horticultural grade silver sand (Dejex Supplies Ltd). The trays were transferred to a controlled environment room  and watered every other day with HortiMix standard (Dejex Supplies Ltd) at 10 ml L2.6H2O. These were applied as 1 L per tray of a liquid feed based on Hoagland’s media, containing 0.25 mM KH2P04, 0.5 mM KOH, 0.75 mM MgCl2.6H2O, 0.75 mM H2SO4, 0.1 mM FeNaEDTA, 2 mM Ca(NO3)2.4H2O, 2 mM NH4NO3, 30 μM H3BO3, 10 μM MnSO4.4H2O, 1 μM ZnSO4.7H2O, 3 μM CuSO4.5H2O, and 0.5 μM Na2MoO4.2H2O. The pH was maintained at 6.4.Thirty seven days after transplanting, the plants were cut leaving ~1 cm of aerial tissue. The cut plants were then watered every other day with 6 Mg treatments at 0, 75, 188, 375, 750 and 1500 μM MgCl3 and analysed by ICP-MS as described by Thomas et al.  and Edinburgh, Scotland  across two years (2017–2018). The soil type at Aberystwyth is well drained loam over gravel in the Eutric Endoskeleti-Eutric Cambisols  was added at a rate of 60 kg ha−1 prior to the first cut (March 2017), and then at 100, 100, and 60 kg ha−1 after cuts 1, 2, 3, respectively, and then 35 kg ha−1 after all subsequent cuts. No fertiliser was added after the final cut. The Mg fertiliser was applied in April 2017 and March 2018 as magnesium sulphate (MgSO4) at MgO equivalent rates of 0, 50, 100, and 200 kg ha−1. Reagent grade ≥ 97% anhydrous MgSO4  was dissolved in warm water and applied with a calibrated knap sack sprayer after the first sward management cutting. Magnesium fertiliser application rates were scaled in relation to a recommendation of 50–200 kg ha−1 of MgO application every 3–4 years when exchangeable soil Mg is < 26 mg L−1  HNO3 and analysed using ICP-MS  at the University of Nottingham  were collected with an auger, using a “W” transect across each site to determine baseline soil physico-chemical properties. Soil samples were also collected from the 16 treatments (samples from the centre of each of four replicate plots were composited) at the beginning of June 2018, after the second Mg-fertiliser application. The baseline soil pH (in water), and exchangeable Mg, Ca and K were analysed at Lancrop Laboratory  while the second-year soil pH, and exchangeable Mg, Ca and K concentrations were analysed at the University of Nottingham. At both laboratories, a similar procedure was followed. Thus, 5 mg of <2 mm sieved soil was dissolved in 25 mL of 1 Data were compiled in MS Excel and Access. For field experiments where repeated observations  were made, statistical analyses were conducted using R  was addressed by the use of a linear mixed model. Two models were considered. In the first (sphericity assumption) where the correlation between the residuals for any two measures on the same unit were treated as uniform. In the second an exponential autocorrelation for successive measurements was assumed. The two models were fitted using the nlme package  as shown in the Online Resource (Sup Table 2.6H2O), the grass Mg concentration  was 4966 ± 880 (cv. Bb2067), 3115 ± 1018 (cv. Bb2068), and 3889 ± 878 (cv. RvP). At the zero Mg application rate, the grass Mg concentration  was 2366 ± 381 (cv. Bb2067), 1382 ± 343 (cv. Bb2068), and 1629 ± 320 (cv. RvP). There was no significant interaction effect of cultivar × Mg application rate on grass Mg concentration (p ≥ 0.05) (Table Grass Mg concentration increased with increasing Mg application rate (p ≥ 0.05) decrease with increasing Mg application rate (Table p < 0.01) as shown in the Online Resource Sup Table p ≥ 0.05, Table The FTI did not significantly (te Table . Cultivate Table . At the −1 at Aberystwyth and 193 mg L−1 at Edinburgh (Table p < 0.05) due to the application of MgSO4 (Table −1) for control plots was 80 at Aberystwyth and 177 at Edinburgh. The increase in the exchangeable soil Mg concentration at Aberystwyth was 20%, 39%, and 74%, and at Edinburgh was 10%, 12% and 32%, at Mg-fertiliser application rates of 50, 100 and 200 kg MgO ha−1, respectively. Baseline exchangeable soil Ca and K concentration, and soil pH were below the recommended optimal for forage cultivation at both sites  except the one between cv. Alamo and cv. RvP as shown in the Online Resource (Sup Table −1), the grass Mg concentrations  were 2637 ± 506 , 1674 ± 314 , 2009 ± 454 , and 1907 ± 431 . At the zero Mg-fertiliser application rate, the grass Mg concentrations  were 2104 ± 495 , 1543 ± 423 , 1786 ± 457 , and 1787 ± 490 . In 2018, at the largest Mg-fertiliser application rate, the grass Mg concentrations  were 2990 ± 628 (cv. Bb2067), 2414 ± 671 (cv. Bb2068), 2691 ± 624 (cv. Alamo), and 2563 ± 643 (cv. RvP). At the zero Mg-fertiliser application rate, the grass Mg concentrations  were 2545 ± 589 (cv. Bb2067), 2201 ± 694 (cv. Bb2068), 2101 ± 572 (cv. Alamo) and 2050 ± 553 (cv. RVP)  cultivar × Mg-fertiliser application rate, cultivar × cutting date, and Mg-fertiliser rate × cutting date interaction effect on grass Mg concentration. In 2017, there was cultivar × cutting date, and Mg-fertiliser rate × cutting date interaction effect on grass Mg concentration. There was no significant (p ≥ 0.05) cultivar × Mg-fertiliser application rate × cutting date interaction effect on the grass Mg concentration in either year  except the one between cv. Alamo and cv. RvP as shown in the Online Resource (Sup Table p < 0.05) affected by cultivar, cutting date, and cultivar × cutting date interaction in 2017 and 2018, but the effect of Mg-fertiliser rate on FTI was only significant in 2018. There was no statistically significant (p ≥ 0.05) cultivar × Mg-fertiliser rate, Mg-fertiliser rate × cutting date, or cultivar × Mg-fertiliser rate × cutting date, interaction effect on the FTI  except the one between cv. Alamo and cv. RvP as shown in the Online Resource (Sup Table −1), the grass Mg concentrations  were 2801 ± 521 , 1698 ± 410 , 2122 ± 514  and 1945 ± 433 . At the zero Mg-fertiliser application rate the grass Mg concentrations  were 2337 ± 478 , 1354 ± 304 (cv. Bb2068), 1732 ± 438  and 1632 ± 386 . In 2018, at the largest Mg-fertiliser application rate, the grass Mg concentrations  were 4205 ± 746 (cv. Bb2067), 2578 ± 503 (cv. Bb2068), 3094 ± 726 (cv. Alamo) and 2965 ± 707 (cv. RvP). At the zero Mg-fertiliser application rate, the grass Mg concentrations  were 3239 ± 531 , 2103 ± 395 (cv. Bb2068), 2526 ± 498 (cv. Alamo) and 2437 ± 480 (cv. RVP)  affected by cultivar, Mg-fertiliser application rate and cutting date. The cultivar × cutting date, and Mg-fertiliser application rate × cutting date interaction effect on grass Mg concentration was significant (p < 0.05) in both years. There was significant (p < 0.05) cultivar × Mg-fertiliser rate × cutting date interaction effect on grass Mg concentration in 2018 but not in 2017  except the one between cv. Alamo and cv. RvP in 2017 as shown in the Online Resource (Sup Table p < 0.05) affected by cultivar, Mg-fertiliser application rate and cutting date. Cultivar × cutting date, and Mg-fertiliser rate × cutting date interaction effect was significant (p < 0.05) on FTI in 2017 and 2018. There was no significant (p ≥ 0.05) cultivar × Mg-fertiliser, and cultivar × Mg-fertiliser rate × cutting date interaction effect on FTI in both years  were 21.0 ± 0.7 (cv. Bb2067), 21.0 ± 0.7 (cv. Bb2068), 24.5 ± 2 (cv. Alamo), and 22.9 ± 1.0 (cv. RvP) in 2017. At the largest Mg-fertiliser application rate (200 kg ha−1), total dry matter yields  were 21.0 ± 0.9 (cv. Bb2067), 21.2 ± 0.9 (cv. Bb2068), 24.1 ± 0.5 (cv. Alamo), and 23.3 ± 0.9 (cv. RvP). In 2018, at the zero Mg-fertiliser application rate, total dry matter yields  were 6.6 ± 0.6 (cv. Bb2067), 6.4 ± 0.5 (cv. Bb2068), 8.7 ± 0.7 (cv. Alamo), and 8.2 ± 0.8 (cv. RvP). At the largest Mg-fertiliser application rate, total dry matter yields  were 6.9 ± 0.3 (cv. Bb2067), 6.7 ± 0.5 (cv. Bb2068), 9 ± 0.6 (cv. Alamo), and 9.1 ± 0.3 (cv. RvP)  were 19.8 ± 0.5 (cv. Bb2067), 19.6 ± 0.9 (cv. Bb2068), 21.8 ± 1.6 (cv. Alamo), and 19.9 ± 1.5 (cv. RvP). At the largest Mg-fertiliser application rate, total dry matter yields  were 19.6 ± 1.4 (cv. Bb2067), 19.7 ± 0.7 (cv. Bb2068), 20.4 ± 0.6 (cv. Alamo), and 20.2 ± 1.6 (cv. RvP). In 2018, at the zero Mg-fertiliser application rate, total dry matter yields  were 7.8 ± 0.2 (cv. Bb2067), 8 ± 0.1 (cv. Bb2068), 9.4 ± 0.8 (cv. Alamo), and 9.3 ± 0.3 (cv. RvP). At the largest Mg-fertiliser application rate, dry matter yields  were 7.5 ± 1 (cv. Bb2067), 8.3 ± 0.2 (cv. Bb2068), 9.1 ± 0.1 (cv. Alamo), and 8.4 ± 0.4 (cv. RvP)  interaction effects of cultivar × Mg-fertiliser application rate, cultivar × cutting date, cultivar × Mg-fertiliser or cultivar × Mg-fertiliser rate × cutting date on the grass biomass yield at both sites in both years. There was a highly significant (p < 0.01) negative correlation between grass biomass yield and Mg concentration. The correlation between grass DM yield and Mg concentration at Aberystwyth was , and at Edinburgh was .There were no significant (4) application rate for all the cultivars in 2017 and 2018  more S in its biomass than the other three Italian ryegrass cultivars. Planned contrasts among the cultivars mean S concentration were significant (p < 0.01) except the one between cv. Alamo and cv. RvP as shown in the Online Resource (Sup Table p < 0.05) affected by cultivar, Mg-fertiliser application rate, cutting date, and by the interaction effect of cultivar × cutting date and Mg-fertiliser rate × cutting date, in 2017 and 2018 (Table p < 0.05) affected by cultivar, Mg-fertiliser application rate and cutting date. The cultivar × Mg-fertiliser application rate, and cultivar × cutting date interaction effect on grass S concentration was significant (p < 0.05) in 2018 but not in 2017 (Table p < 0.05) in both years. There was no significant (p ≥ 0.05) cultivar × Mg-fertiliser application rate × cutting date interaction effect on grass S concentration , the grass S concentrations  were 3257 ± 703 (cv. Bb2067), 2738 ± 476 , 2790 ± 697 (cv. Alamo) and 2838 ± 595 (cv. RvP). At the zero Mg-fertiliser application rate the grass S concentrations  were 2814 ± 588 , 2540 ± 512 (cv. Bb2068), 2599 ± 561 (cv. Alamo) and 2662 ± 573 (cv. RvP). In 2018, at the largest Mg-fertiliser application rate, the grass S concentrations  were 3970 ± 845 (cv. Bb2067), 3266 ± 592 (cv. Bb2068), 3345 ± 429 (cv. Alamo) and 3382 ± 604 (cv. RvP). At the zero Mg-fertiliser application rate, the grass S concentrations  were 3309 ± 601 , 3155 ± 575 (cv. Bb2068), 2861 ± 637 (cv. Alamo) and 2830 ± 639 (cv. RVP) , the grass S concentrations  were 4063 ± 844 , 3153 ± 600 , 3510 ± 860  and 3372 ± 782 . At the zero Mg-fertiliser application rate the grass S concentrations  were 3393 ± 1033 , 2638 ± 819 (cv. Bb2068), 2973 ± 898  and 2931 ± 904 (cv. RVP). In 2018, at the largest Mg-fertiliser application rate, the grass S concentrations  were 4303 ± 908 (cv. Bb2067), 3292 ± 813 (cv. Bb2068), 3526 ± 909 (cv. Alamo) and 3502 ± 820 (cv. RVP). At the zero Mg-fertiliser application rate, the grass S concentrations  were 3154 ± 747 , 2885 ± 645 (cv. Bb2068), 2835 ± 627 (cv. Alamo) and 2742 ± 614 (cv. RVP)  for the field experiment. There are a range of potential Mg resources including dolomitic limestone  of cv. Bb2067 in these trials in 2017 was well above that perennial ryegrass under conservation sward management and comparable to cv. Alamo under farmer management. There is a need to transfer cv. Bb2067 Mg-accumulating trait into the cultivars that yield larger biomass  ratio in lush grasses with large N in spring during lambing season when animal requirement for S increases ESM 2(XLSX 149 kb)ESM 3(XLSX 14 kb)ESM 4(XLSX 12 kb)ESM 5(XLSX 9 kb)ESM 6(XLSX 12 kb)


The structure of the title compound is stabilized by the presence of N—H⋯O and C—H⋯O hydrogen bonds. Other interactions such as C—H⋯π are also important in the analysis of the Hirshfeld surface. Molecular docking studies show this compound to be a potential anticoagulant agent. 21H17N3O5, consists of three rings, A, B and C, linked by amide bonds with the benzene rings A and C being inclined to the mean plane of the central benzene ring B by 2.99 (18) and 4.57 (18)°, respectively. In the crystal, molecules are linked via N—H⋯O and C—H⋯O hydrogen bonds, forming fused R22(18), R34(30), R44(38) rings running along [R33(37) and R33(15) rings along [001]. Hirshfeld analysis was undertaken to study the intermolecular contacts in the crystal, showing that the most significant contacts are H⋯O/O⋯H (30.5%), H⋯C/C⋯H (28.2%) and H⋯H (29.0%). Two zones with positive  potentials and two zones with negative  potentials promote the N—H⋯O interactions in the crystal. An evaluation of the molecular coupling of the title compound and the protein with enzymatic properties known as human coagulation factor Xa (hfXa) showed the potential for coupling in three arrangements with a similar minimum binding energy, which differs by approximately 3 kcal mol−1 from the value for the molecule Apixaban, which was used as a positive control inhibitor. This suggests the title compound exhibits inhibitory activity.The title compound, C Some aminobenzamide derivatives present high efficiencies in their non-linear optical properties  and C  form dihedral angles of of 2.99 (18) and 4.57 (18)°, respectively, with the mean plane of the central ring B . In turn, the amide groups C8/N2/C7(O3)/C1 (r.m.s deviation = 0.0081 Å) and C15/N3/C14(O4)/C10 (r.m.s deviation = 0.0101 Å), which link the rings, are inclined by 37.72 (15) and 29.35 (16)°, respectively, to ring B. The nitro group forms an angle of 5.3 (2)° with ring A while the methoxy group is approximately coplanar with ring C, forming an angle of 1.1 (5)°. The molecule is formed by three main planes resulting from the planes that form the rings with the B ring resembling a fallen step between A and C. All bond lengths  −x + 1, y + z + 1; (ii) −x, y + z + 1] form fused a). In turn, playing the role of complementary interactions in crystal growth, other C—H⋯O-type interactions  link the molecules at their ends, ensuring their stability in the growth process. Together with the N—H⋯O interactions, they contribute to the formation of additional fused b). Weak C21—H21B⋯Cg1 interactions occur, where Cg1 is the centroid of the C1–C6 benzene ring, with a H21B⋯Cg1 distance of 2.83 Å.The crystalline packing in compound (I)CrystalExplorer program . The overall two-dimensional fingerprint plot , and those delineated into by H⋯O/O⋯H, H⋯H, H⋯C/C⋯H, C⋯C, N⋯C/C⋯N, H⋯N/N⋯H, O⋯O, O⋯C/C⋯O, and N⋯O/O⋯N contacts are illustrated in Fig. 4b–j, respectively, together with their relative contributions to the Hirshfeld surface. The most important interaction corresponds to H⋯O/O⋯H contributing 30.5% to the overall crystal packing, as shown in Fig. 4b. The pair of spikes in the fingerprint plot have a symmetrical distribution of high-density points with the tip at de + di = 1.98 Å. The H⋯H interactions, shown in Fig. 4c, contribute 29.0% to the total crystal packing and appear as widely dispersed points of high density due to the large hydrogen-atom content of the molecule with the rounded tip at de + di = 1.20 Å. The presence of C—H⋯π interactions is shown as a pair of characteristic wings on the fingerprint plot , delineated into H⋯C/C⋯H contacts (28.2% contribution to the HS) having the tip at de + di = 2.84 Å. These results reveal the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯C/C⋯H and H⋯O/O⋯H interactions suggest that van der Waals interactions and hydrogen bonding play major roles in the crystal packing  using the ot Fig. 4a, and tot Fig. 4d, delinGauss09W  level of theory, to obtain a qualitative analysis and the Multiwfn 3.6 program for a quantitative analysis  of (I)Autodock Vina 4.2.6 d Table 2. Compound Table 2, which det al., 20162-azanyl)phenyl](phenyl-λ2-azanyl)methanone as the main skeleton gave 76 hits. Seven structures containing the [3-(benzoyl-λ2-azanyl)phenyl](phenyl-λ2-azanyl)methanone framework with nitro and methoxy groups as substituents similar to the title compound were found, viz., N-{3-[N′-(2-methoxyphenyl)carbamoyl]-5-methyl-2-methoxyphenyl}-2-methoxy-5-methyl-3-nitrobenzamide carbamoyl]-5-methyl-2-methoxyphenyl}-2-hydroxy-5-methyl-3-nitrobenzamide amino]benzoyl}amino)-2-methoxybenzoate]aquasodium methanol solvate] benzamide (ii) , previously synthesized, was subjected to an acylation reaction in 3-nitrobenzoyl chloride (a)  under chloroform reflux conditions to obtain compound (I)3-Amino-−1) = 3338, 3285 (N—H), 3076, 2969, 1650, 1637 (C=O), 1585 (C=C), 1526, 1510, 1434, 1353 (NO2), 1316, 1301, 1241, 1137, 1026, 898, 829, 819, 721, 683 cm−1. The UV–Vis spectrum for (I)M) was obtained in DMF with a maximum of 273 nm (0.62 absorption). MS , m/z [M+] calculated for C21H17N3O5+: 391.12 (100%) and 392.12 (23.1%); found: 391.10 and 392.10 (25.1%).FT–IR (ATR): υ (cmUiso(H) = 1.2Ueq(parent atom) or 1.5Ueq(C). After refinement, ROTAX suggested twinning by a 180° about [100]. This law was used to generate an hklf5 format reflection file. Refinement against this file improved R factors and residual Q peaks·BASF refined to 0.090 (4)Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989020013730/dj2013sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020013730/dj2013Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020013730/dj2013sup3.pdfSynthesis and characterization of (I). DOI: Click here for additional data file.10.1107/S2056989020013730/dj2013Isup4.cmlSupporting information file. DOI: 2016019CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The phenyl rings in the [C24H38N4O2Te2]2+ cation are in a cis arrangement to enable this species to participate in Te⋯Cl cation–anion interactions. There are also C—H⋯O interactions involving the dimethyl sulfoxide ligands and numerous cation–anion and anion–anion C—H⋯Cl interactions, which link the ions into a complex three-dimensional array.In the title salt, di-μ-oxido-bis{2,6-bis[(dimethylamino)methyl]phenyl-κ This might be due to the formation of the highly stable tellurenium(II) cation where the Te is T-shaped and involved in a three-centered, four-electron bond. While checking the reproducibility of the reaction, in one instance, because of the adventitious uptake of oxygen, the reaction unexpectedly resulted in the isolation of the title compound, which contains the ditelluroxonium(IV) cation 2, 2 with the PdCl3(DMSO) anion. It is worth noting that Furukawa and coworkers have reported a similar diorganotelluroxonium(IV) cation namely, 2·PF6, by the reaction of the diorganotelluride 2Te with the oxidizing agent NOPF6 ]−2, 3, crystallizes in the triclinic space group P2 there is a cis arrangement of the aryl rings of the attached 2,6-[(dimethylamino)methyl)]phenyl substituents 2C6H3Te(μ-O)]2+·PF6−, wherein the cation lies on a center of inversion and thus the aryl groups are in a trans configuration –2.495 (2) Å for 2, are in good agreement with the values observed in 2+·PF6− [2.475 (5)–2.486 (5) Å] ° and those between the Te2O2 plane and the aryl rings are 88.77 (8) and 85.00 (8)°, indicating that the two aryl groups are not coplanar, and are too far apart to form π–π stacking interactions (the closest contact is between C1 and C1A at 3.672 Å). Thus, the driving force for the adoption of this sterically unfavorable cis conformation appears to be the formation of Te⋯Cl cation–anion interactions, which would not be possible if the trans conformation were adopted. In this case, there is a short Te2⋯Cl3 contact of 3.386 (1) Å and longer contacts of 3.833 (1) Å (Te2⋯Cl2) and 3.991 (1) Å (Te1⋯Cl5) 2C6H3Te(μ-O)]2+·PF6−, no such cation–anion interactions are present and hence the more sterically favorable trans conformation is adopted. In the other two related structures containing the Te2O22+ core dication, the same cis configuration is adopted to allow the formation of interionic Te⋯O interactions  cation and key geometrical data are listed in Table 1ts Fig. 1. This isIn addition to the Te⋯Cl cation–anion interactions mentioned above, there are also C—H⋯O interactions involving the DMSO ligands and numerous cation–anion and anion–anion C—H⋯Cl interactions Table 2, which l2O22+ core. The first report on the molecular structure of a diorganotelluroxonium(IV) cation was made by Furukawa and co-workers 2C6H3Te(μ-O)]2+ charge-balanced as the PF6− salt. Beckmann and coworkers reported the molecular structure of [(6-Ph2P(O)-Ace-5-) Te(μ-O)]2·2OTf +: 336.0545, found: 336.0541.Yield: 59%; m.p. 444–446 K; Ueq(C) [1.5Ueq(CH3)] and C—H distances ranging from 0.95 to 0.99 Å.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989020011482/hb7941sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989020011482/hb7941Isup2.hklStructure factors: contains datablock(s) I. DOI: 1563166CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Complexes 1 and 2 both contain the ‘diamond core’ motif found previously in a number of iron, copper, and manganese high-valent bis-oxo compounds. The flexibility in the propyl linker in the ligand scaffold of 2, as compared to that of the ethyl linker in 1, results in more elongated Mn—N bonds, as one would expect. The Mn—Mn distances and Mn—O bond lengths support an MnIV oxidation state assignment for the Mn ions in both 1 and 2. The angles around the Mn centers are consistent with the local pseudo-octahedral geometry.The addition of  The isolation and crystallographic characterization of the bis-oxo complexes 1 and 2 . The Mn ion of 1 is in a pseudo-octahedral environment, with small deviations in the O—Mn—N angles relative to an ideal octahedral geometry: O1—Mn1—N1 = 93.76 (12), O1—Mn1—N2 = 92.13 (12), O1—Mn1—N3 = 174.90 (12), and O1—Mn1—N4 = 95.77 (12)°. As is true for all diamond cores, the O1—Mn1—O1′ angle is slightly compressed at 85.53 (12)°. Metrical parameters, Mn1—O1 = 1.829 (3) Å and Mn1—O1′= 1.835 (3) Å  Å] is slightly longer than that involving the secondary amine [Mn1—N3 = 2.111 (4) Å]. The Mn1⋯Mn1′ separation of 2.6899 (15) Å, falls within the normal range (2.6 to 2.8 Å) for bis-oxo-bridged MnIVMnIV dimers containing a diamond core. Complex 1 crystallizes with two crystallographically equivalent tetraphenylborate counter-ions and two crystallographically equivalent water molecules. The water molecule is disordered over two sites with site occupancies refined to 0.870 (12) and 0.130 (12) for O2 and O2B respectively, with the applied constraint that both together give 100% occupancy.Complex Å Table 1 fall wit2 also sits on an inversion center , making the two Mn atoms crystallographically equivalent. There is disorder in the position of the propyl linker carbon atoms . The site occupancies of N3, C1–C3 and N3B, C1B–C3B refined to 0.804 (5) and 0.196 (5), respectively, with the constraint of both together giving 100% occupancy. The Mn ion of 2 is again in a pseudo-octahedral environment, with small deviations in O—Mn—N angles relative to ideal octahedral geometry: O1—Mn1—N1 = 106.39 (7), O1—Mn1—N2 = 174.90 (7), O1—Mn1—N3 = 89.11 (13), and O1—Mn1—N4 = 103.70 (6)°. Again, as is true for all diamond cores, the O1—Mn1—O1′ angle of 2 is slightly compressed at 85.98 (7)°, and is similar to that in 1. Metrical parameters, Mn—O1 = 1.8325 (15) and Mn—O1′ = 1.8349 (15) Å, are also similar to those found in 1, and fall within the reported range (1.8 to 1.9 Å) for oxo-bridged MnIV complexes. The pyridine nitrogen atoms are once again further from the Mn ions than expected for a formal Mn—N bond, but are oriented towards Mn at distances of Mn1—N1 = 2.3251 (18) Å and Mn1—N4 = 2.3522 (18) Å. This bond elongation is likely to be due to steric interference from the methyl groups at the 6-position of the pyridine rings. The nitrogens on the amine arms are much closer to the Mn center, and fall within the normal Mn—N range (1.9 to 2.1 Å) for MnIV. The Mn—N distance involving the tertiary amine [Mn1—N2 = 2.1828 (18) Å] is noticeably longer than that involving the secondary amine [Mn1—N3= 2.133 (6) Å]. The large difference between these bond lengths in 2, relative to those of 1, likely reflects the increased flexibility of the propyl linker in 2. The Mn1—Mn1′ distance [2.6825 (7) Å] in 2 is essentially the same as that found in 1, and falls within the normal range (2.6 to 2.8 Å) for bis-oxo-bridged MnIVMnIV dimers containing a diamond core. Complex 2 crystallizes with two tetraphenylborate counter-ions and two diethyl ether molecules per cation.Complex 1 and 2 are analogous to other reported MnIVMnIV(μ-O)2 dimers. The Mn1—Mn1′ distances of 2.6899 (15) Å in 1 and 2.6825 (7) Å in 2 are comparable to other literature examples  and 1.8325 (15) Å for 2 are also similar to literature reported values for MnIVMnIV(μ-O)2 dimers , MeCN (CaH2), and CH2Cl2 (CaH2) were dried and distilled prior to use. Et2O was rigorously degassed and purified using solvent purification columns housed in a custom stainless steel cabinet and dispensed by a stainless steel Schlenk-line (GlassContour). Complexes 3 and 4 were synthesized as described by Coggins et al.  or 1.5Ueq(C-methyl). For the disordered water molecule in complex 1, the water was set-up as a rigid group free to rotate and move during refinement, with DFIX restraints between O and H and between both H per water. The displacement parameters of O2 and O2B were made the same with the EADP constraint. Hydrogen-atom isotropic displacement parameters were fixed at 1.5 times that of the water oxygen atoms. For the disorder in complex 2, the geometry of both groups was set to be similar with the ‘SAME’ option. Displacement parameters of N3-N3B, C1-C1B, C2-C2B, and C3-C3B were restrained with the SIMU command at 0.005 strength.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989020004557/cq2034sup1.cifCrystal structure: contains datablock(s) global, Complex1, Complex2. DOI: 10.1107/S2056989020004557/cq2034Complex1sup4.hklStructure factors: contains datablock(s) Complex1. DOI: 10.1107/S2056989020004557/cq2034Complex2sup5.hklStructure factors: contains datablock(s) Complex2. DOI: 1994292, 1994291CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Enzyme promiscuity has important implications in the field of biocatalysis. In some cases, structural analogues of simple metabolic building blocks can be processed through entire pathways to give natural product derivatives that are not readily accessible by chemical means. In this study, we explored the plasticity of the aurachin biosynthesis pathway with regard to using fluoro‐ and chloroanthranilic acids, which are not abundant in the bacterial producers of these quinolone antibiotics. The incorporation rates of the tested precursor molecules disclosed a regiopreference for halogen substitution as well as steric limitations of enzymatic substrate tolerance. Three previously undescribed fluorinated aurachin derivatives were produced in preparative amounts by fermentation and structurally characterized. Furthermore, their antibacterial activities were evaluated in comparison to their natural congener aurachin D. Room for a halogen: The plasticity of the aurachin biosynthetic pathway in the myxobacterium S. erecta was explored for the use of fluoro‐ and chloroanthranilic acids. Incorporation of the unnatural precursors was quantified. Three fluorinated aurachin analogues were produced in sufficient quantity to enable their antibacterial activities to be assessed. Nature is a rich source of bioactive compounds, which have been optimized during evolution regarding their affinity to cellular targets.Stigmatella aurantiaca and later also found in other Stigmatella spp. as well as members of the actinomycete genera Rhodococcus and Streptomyces.[11] Their structural relatedness to the known respiratory chain inhibitor 2‐heptyl‐4‐hydroxyquinoline‐N‐oxide (HQNO) suggested early on that the aurachins might interfere with electron transport processes.6fb complex.1) and C (2).The aurachins are a large family of prenylated quinolone antibiotics, which were first discovered in cultures of the myxobacterium ptomyces. Their st19F NMR spectroscopy.To explore this yet underexplored chemical space, we considered precursor‐directed biosynthesis as a viable option to introduce functional groups at these positions. Isotopic labelling studiesStigmatella erecta strain, which had been confirmed as an authentic aurachin producer.S. erecta in the presence of halogenated anthranilic acids, irrespective of the fluorine or chlorine substitution pattern. This may hint at interferences with tryptophan metabolism, as recently reported for mycobacteria.S. erecta, like many other myxobacteria, does not grow homogeneously in liquid media, but is known to form cellular aggregates.S. erecta, the amounts of biosynthesized aurachins were normalized to the production of myxothiazol A. This known secondary metabolite from S. erectaThe feeding studies were conducted in shaken Erlenmeyer flasks with a In accordance with previous studies, the addition of anthranilic acid was found to have a positive effect on aurachin production.19F NMR guided fractionation . The recovery of 6‐chloroaurachin D remained unsuccessful despite repeated attempts.In order to enable full NMR‐based structural characterization, feeding studies were repeated on multilitre scale to produce sufficient quantities of some aurachin analogues. Owing to the very low production titres that were achieved  and a laborious chromatographic separation process Figure , only th1 a (0.5 mg) originated from a 10‐L culture of S. erecta grown in the presence of 3‐fluoroanthranilic acid. The [M+H]+ ion peak of 1 a possesses a m/z value of 382.2546, corresponding to a molecular formula of C25H32NOF and 10 double bond equivalents. UV maxima at 241, 321 and 333 nm as well as NMR data  of the purified compound are almost consistent with those of 1,1H NMR spectrum of 1 a features only three aromatic signals with a distinctive coupling pattern characteristic for a 3‐fluoroanthranilate‐derived moiety. COSY and HMBC experiments confirmed the presence of a farnesyl chain and a methyl group, which are connected to the assumed quinolone core of 1 a at C‐3 and C‐2, respectively. Thus, 1 a was identified as 8‐fluoroaurachin D.Compound 1 b after multi‐step HPLC. The high‐resolution ESI‐MS spectrum confirmed the same molecular formula as 1 a as well as similar UV maxima at 249, 321 and 331 nm . A comparison of 1H NMR spectra corroborated that 1 a and 1 b are indeed structurally similar, but not identical. The differences pertained to the aromatic region. Following an analysis of their multiplicities and coupling constants, the aromatic proton signals of 1 b could be assigned to a spin system for a 1,2,4‐trisubstituted benzene ring. Further interpretation of 1D and 2D NMR data  then led to the conclusion that 1 b represents 7‐fluoroaurachin D.The extract from the 4‐fluoroanthranilic acid culture yielded 0.3 mg of compound 1 c was purified from a culture that had been supplied with 5‐fluoroanthranilic acid, yielding 0.3 mg of material. Again, high‐resolution ESI‐MS and UV data pointed to an aurachin D derivative bearing a single fluorine substituent . The substitution pattern with the halogen at C‐6 position of the quinolone ring was deduced from the heteronuclear coupling observed in the 1H NMR spectrum .Compound 1 a–c are equipotent to 1  was grown in modified Zein medium . To facilitate the recovery of secreted aurachins, adsorber resin XAD7HP (2 % w/v) was added prior to sterilization. The medium was inoculated with seed culture (10 % v/v inoculum) and the fermentation was conducted in an incubator shaker at 30 °C and 130 rpm for 7 days. Anthranilic acid or its halogenated derivatives were supplemented as filter‐sterilized aqueous solutions (33 mg L−1) after inoculation of the medium. For extraction the adsorber resin was separated from the culture broth by filtration, washed with water and retained compounds eluted three times with acetone and methanol. The extract was dried and used for relative quantification or compound purification.Quantitative analysis: For relative quantification experiments, the dried extracts of 1.5 L cultures were resuspended in methanol, filtered and supplied to LC‐ESI‐MS  in positive mode. HPLC flow rate was 0.4 mL min−1 on a Nucleodur RP 18 ec column  and a gradient from 5 to 98 % acetonitrile in water supplemented with 0.1 % formic acid over 10 min, followed by 5 min at 98 % acetonitrile. All analyses were carried out at a capillary voltage of 4.5 kV, desolvation gas (N2) temperature of 220 °C, with a dry gas (N2) flow rate of 12 L min−1.Compound purification: Dried raw extracts were resuspended in 60 % aqueous methanol (100 mL) and extracted three times with dichloromethane (60 mL). Aurachins were exclusively present in the dichloromethane fraction. The purification continued on a Shimadzu HPLC system (LC‐20AD) equipped with a diode array detector (SPD‐M20A). The initial separation was carried out on a VarioPrep C18 Gravity column  by two consecutive isocratic elutions with pure methanol and 90 % aqueous methanol, respectively. The aqueous eluent was supplemented with 0.1 % (v/v) trifluoroacetic acid and the flow rates were set to 4 mL min−1. For 1 c, an additional purification on a Nucleodur gravity column  was performed (60 % to 100 % acetonitrile in water supplemented with 0.1 % (v/v) trifluoroacetic acid within 10 min, followed by 100 % acetonitrile for additional 10 min), at a flow rate of 2 mL min−1. NMR spectra were acquired at 300 K on a Bruker AV 700 Avance III HD (CryoProbe) or on a Bruker AV 600 Avance III HD (CryoProbe). Compounds were dissolved in methanol‐4d, which also served as internal standard to calibrate spectra to δH=3.31 ppm and δC=49.0 ppm. 19F NMR spectra were referenced to residual trifluoroacetic acid at δF=−76.5 ppm.8‐Fluoroaurachin D (1 a): 1H NMR : δ=8.02 , 7.43 , 7.30 , 5.09 , 5.04 , 4.98 , 3.40 , 2.51 , 2.10 , 2.03 , 1.92 , 1.87 , 1.81 , 1.60 , 1.55 , 1.49 ppm ; 13C NMR : δ=177.8 (C‐4), 153.3 , 150.4 (C‐2), 136.1 (C‐3′), 135.9 (C‐7′), 132.0 (C‐11′), 130.1 (C‐8a), 127.1 (C‐4a), 125.3 (C‐6′), 125.3 (C‐10′), 123.9 , 123.5 (C‐2′), 121.7 (C‐3), 122.0 , 116.7 , 40.8 (C‐8′), 40.7 (C‐4′), 27.8 (C‐9′), 27.2 (C‐5′), 25.8 (C‐12′), 24.8 (C‐1′), 18.0 (C‐9), 17.6 (C‐15′), 16.3 (C‐13′), 16.2 ppm (C‐14′); 19F NMR : δ=133.5 ppm ; HRMS (ESI): m/z calcd for C25H32FNO: 382.2541 &bk:[M+H]+; found: 382.2546.7‐Fluoroaurachin D (1 b): 1H NMR : δ=8.25 , 7.16 , 7.11 , 5.09 , 5.05 , 4.99 , 3.38 , 2.45 , 2.10 , 2.02 , 1.94 , 1.87 , 1.80 , 1.61 , 1.55 , 1.51 ppm ; 13C NMR : δ=177.9 (C‐4), 165.8 , 150.0 (C‐2), 141.4 (C‐8a), 135.9 (C‐7′), 135.7 (C‐3′), 132.0 (C‐11′), 129.5 (C‐5),125.4 (C‐10′), 125.2 (C‐6′), 123.9 (C‐2′), 121.9 (C‐4a), 120.8 (C‐3), 113.3 (C‐6), 103.4 (C‐8), 40.8 (C‐4′), 40.8 (C‐8′), 27.8 (C‐9′), 27.2 (C‐5′), 25.7 (C‐12′), 24.4 (C‐1′), 18.3 (C‐9), 17.7 (C‐15′), 16.1 (C‐13′), 16.0 ppm (C‐14′); 19F NMR : δ=109.3 ppm ; HRMS (ESI): m/z calcd for C25H32FNO: 382.2541 [M+H]+; found: 382.2549.6‐Fluoroaurachin D (1 c): 1H NMR : δ=7.84 , 7.56 , 7.45 , 5.09 , 5.05 , 4.99 , 3.40 , 2.47 , 2.09 , 2.02 , 1.94 , 1.88 , 1.81 , 1.61 , 1.55 , 1.51 ppm ; 13C NMR : δ=177.7 (C‐4), 160.5 , 150.0 (C‐2), 137.2 (C‐8a), 136.1 (C‐3′), 135.9 (C‐7′), 132.1 (C‐11′), 125.4 (C‐6′), 125.3 (C‐10′), 126.2 (C‐4a), 123.6 (C‐2′), 121.6 (C‐8), 121.3 (C‐7), 120.8 (C‐3), 110.1 (C‐5), 40.8 (C‐4′), 40.7 (C‐8′), 27.8 (C‐9′), 27.3 (C‐5′), 25.8 (C‐12′), 24.8 (C‐1′), 18.3 (C‐9), 17.6 (C‐15′), 16.3 (C‐13′), 16.1 ppm (C‐14′); 19F NMR : δ=119.2 ppm ; HRMS (ESI): m/z calcd for C25H32FNO: 382.2541 [M+H]+; found: 382.2541.Antibacterial activity screening: An agar diffusion assay was performed with the purified compounds 1 and 1 a–c to test their antimicrobial activities against Escherichia coli SG458, Pseudomonas aeruginosa SG137, Staphylococcus aureus (MRSA) 134/94 and Mycobacterium vaccae IMET 10670. For this purpose, 50 μL compound test solution (500 μg mL−1 in DMSO) was pipetted into agar plates with pre‐punched 9 mm holes. Ciprofloxacin (5 μg L−1) was used as positive control.The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.SupplementaryClick here for additional data file.


Scientific Reports 10.1038/srep40064, published online 06 January 2017Correction to: This Article contains errors in Figure A) A total of 40 mice were subcutaneously inoculated with H460 and H460/MX20 cells (≈5 × 106) in the right flank, respectively. (B) The changes in tumor volume and body weight over time following the implantation. Data points represented the mean ± SD of tumor volumes and body weight from each group. n = 20. (C) Solid tumor formation rate of H460 and H460/MX20 cells (100%). (D) The selected cell xenografts were cut into about 5 mm × 5 mm and fixed with 10% neutral formalin. (E) ABCG2 expression analysis by immunohistochemistry in tumor tissues collected from H460 and H460/MX20 cell xenografts.”“(should read:A) A total of 40 mice were subcutaneously inoculated with H460 and H460/MX20 cells (≈ 5 × 106) in the right flank, respectively.  The changes in tumor volume and body weight over time following the implantation. Data points represented the mean ± SD of tumor volumes and body weight from each group. n = 20. (D) Solid tumor formation rate of H460 and H460/MX20 cells (100%). (E) The selected cell xenografts were cut into about 5 mm × 5 mm and fixed with 10% neutral formalin. (F) ABCG2 expression analysis by immunohistochemistry in tumor tissues collected from H460 and H460/MX20 cell xenografts.”“(The correct Figure


Slc17a9, P2x7r, and P2y2r was increased concomitant with an increase in extracellular ATP levels. Furthermore, compressive force decreased the osteoblast differentiation capacity of MC3T3‐E1 cells. shRNA knockdown of Slc17a9 in MC3T3‐E1 cells reduced levels of extracellular ATP and also led to increased osteoblast differentiation after the application of compressive force as assessed by qPCR analysis of osteoblast markers such as Runx2, Osterix, and alkaline phosphatase (ALP) as well as ALP activity. Consistent with these observations, knockdown of P2x7r or P2y2r by siRNA partially rescued the downregulation of osteoblast differentiation markers, caused by mechanical loading. In conclusion, our results demonstrate that VNUT is expressed in osteoblasts and that VNUT inhibits osteoblast differentiation in response to compressive force by mechanisms related to ATP release and P2X7R and/or P2Y2R activity.Osteoblasts release adenosine triphosphate (ATP) out of the cell following mechanical stress. Although it is well established that extracellular ATP affects bone metabolism via P2 receptors [such as purinergic receptor P2X7 (P2X7R) and purinergic receptor P2Y2 (P2Y2R)], the mechanism of ATP release from osteoblasts remains unknown. Recently, a vesicular nucleotide transporter  that preserves ATP in vesicles has been identified. The purpose of this study was to elucidate the role of VNUT in osteoblast bone metabolism. mRNA and protein expression of VNUT were confirmed in mouse bone and in osteoblasts by quantitative real‐time PCR (qPCR) and immunohistochemistry. Next, when compressive force was applied to MC3T3‐E1 cells by centrifugation, the expression of  In this study, we show that VNUT (SLC17A9), a vesicular nucleotide transporter, regulates osteoblast differentiation in response to mechanical loading. Mechanical loading promotes adenosine triphosphate (ATP) exocytosis via VNUT. Extracellular ATP subsequently inhibits osteoblast differentiation via activation of P2X7 and/or P2Y2 receptors. Thus, VNUT modulation of purinergic signaling contributes to the regulation of bone metabolism by mechanical loading. ALPalkaline phosphataseATPadenosine triphosphate P2X1Rpurinergic receptor P2X1P2X7Rpurinergic receptor P2X7P2Y2Rpurinergic receptor P2Y2qPCRquantitative real‐time PCRSLC17A9solute carrier family 17 member 9VNUTvesicular nucleotide transporterBone homeostasis is maintained by the balanced activity of bone‐forming osteoblasts and bone‐resorbing osteoclasts. Mechanical stress and loading are key factors for the regulation of bone homeostasis . OsteoblMechanical loading induces multiple cellular events in osteoblasts. A major effect of mechanical loading on osteoblasts is the efflux of adenosine triphosphate (ATP) into the extracellular space , 13, 14.Solute carrier family 17 member 9 (SLC17A9) was recently identified as a vesicular nucleotide transporter (VNUT), essential for ATP secretion from adrenal PC12 cells . ATP canHere, we report that VNUT is expressed in osteoblasts where it plays a role in ATP secretion as well as osteoblast differentiation.−1 penicillin–streptomycin . Osteoblast differentiation was induced by culturing cells in an osteogenic medium containing 50 μg·mL−1 ascorbic acid  and 10 mm β‐glycerophosphate  for 7 days. Cells were treated with 1, or 10 μm clodronate (Sigma‐Aldrich). Ionomycin  treatments were performed at 1 μm. Brefeldin A  was used at 10 μm. HEK293T cells  were cultured in Dulbecco's modified Eagle's medium (DMEM)  supplemented with 10% FBS (Biosera Nuaillé) and 100 U·mL−1 penicillin–streptomycin .MC3T3‐E1 cells, a mouse calvarial osteoblast cell line, were obtained from Riken Bio Resource Center . MC3T3‐E1 cells were maintained in α‐minimal essential medium  supplemented with 10% FBS  and 100 U·mL5 cells per well in 12‐well plates. Medium was changed into 4‐(2‐hydroxyethyl)‐1‐piperazineethanesulfonic acid (HEPES)‐buffered DMEM without bicarbonate , supplemented with 18 µm of hydrochloric acid  to stabilize pH and then cells placed in an incubator  at 37 °C for 1 h. The plates were subsequently centrifuged at 4.4 × 10−2 N·cm−2 (5.0 g·cm−2) or 8.8 × 10−2 N·cm−2 (9.0 g·cm−2) using a PlateSpin II centrifuge  in the incubator at 37 °C for 12 h. Compressive force by weights was also previously described . Boxed areas in the  left panel are shown as magnified images in the right panel. Scale bars indicate 20 µm  and 100 µm  respectively.Click here for additional data file.Fig. S2. Immunocytochemistry with VNUT antibodies. (A) MC3T3‐E1 cells are immunostained with Rabbit VNUT antibody preabsorbed with VNUT blocking antigen peptide (Control) or VNUT antibody (Rabbit). (B) MC3T3‐E1 cells stably expressing control scrambled shRNA or shRNA against murine Slc17a9 were stained with VNUT antibody (Rabbit), rhodamine phalloidin, or DAPI. (C) MC3T3‐E1 cells were transfected with V5‐tagged VNUT and immunostained with VNUT antibody (Rabbit or Guinea pig), and anti‐V5 antibody and DAPI. Scale bars indicate 100 µm, scrambled shRNA, Scr; shRNA against murine Slc17a9, Sh.Click here for additional data file.Fig. S3. Knock down of VNUT does not alter extracellular ATP levels in the absence of mechanical force. Extracellular ATP levels from MC3T3‐E1 cells stably expressing control scrambled shRNA or shRNA against Slc17a9. Scrambled shRNA, Scr; shRNA against murine Slc17a9, sh. Data are expressed as the mean ± SD (n = 3). Statistical analysis was performed with unpaired t‐test. *P < 0.05 or **P < 0.01 versus control.Click here for additional data file.Fig. S4. Inhibition of Vnut function does not affect cell proliferation of MC3T3‐E1 cells. MC3T3‐E1 cells were plated into 96‐well plates and incubated with 0, 1.0, or 10 μM clodronate. Cell proliferation was assessed on day 1, 2, or 3 using a Cell Counting Kit‐8 (DOJINDO).Click here for additional data file.


IVX5}−  synthon to a pocket‐based ligand to provide supramolecular design using halogen⋅⋅⋅halogen interactions within an FeIII system that has the potential to undergo spin crossover (SCO). By removing the solvent from the crystal lattice, we “switch on” halogen⋅⋅⋅halogen interactions between neighboring molecules, providing a supramolecular cooperative pathway for SCO. Furthermore, changes to the halogen‐based interaction allow us to modify the temperature and nature of the SCO event.We have added the {Re Inorganic synthon controls SCO behavior: Incorporating an {ReIVX5}− synthon into an FeIII system provides a highly directional supramolecular design using halogen⋅⋅⋅halogen interactions. Removal of solvent from the crystal lattice “switches on” these interactions, providing a long‐range cooperative pathway ideal for an SCO event. In practice we found that the transition metal preferentially occupies pocket 2, giving a mer‐coordinated system with the general formula [ReIVX5(μ‐Rpch)Fe(R’‐Im)3] where H2Rpch has the formula (E)‐N’‐(2‐hydroxy‐3‐R‐benzylidene)pyrazine‐2‐carbohydrazide, and R’‐Im has the formula 1‐R’‐imidazole ‐(8) (see ESI), showed that the SCO properties of the FeIII center could be readily modified. Crystal structures are labelled with the general name “(Compound)w/d_TEMP”, where w or d denotes “wet” (solvated) or “dry” (desolvated) crystals, and TEMP is the temperature of the structural determination.Whilst the use of the {ReX1)w_100 shows that the complex crystallizes in the space group C2/c with Z=8. Complex (1) was chosen as a representative of the series with structural details of complexes (1)–(4) including halogen bond parameters in the ESI. The asymmetric unit contains a [ReBr5(μ‐MeOpch)Fe(Me‐Im)3] complex with the {ReIVBr5} synthon bound to a nitrogen atom of the pyrazine ring of the deprotonated MeOpch ligand. The central FeIII ion is coordinated to the ligand through an azine nitrogen (N1), a carbonyl oxygen (O3), and a hydroxy oxygen (O1), whilst three additional Me‐Im co‐ligands complete the coordination sphere through nitrogen atoms N5, N9, and N7. In addition to this there were two interstitial MeCN molecules within the lattice connected through nonclassical hydrogen bonds. The shortest intermolecular Br⋅⋅⋅Br distance was 4.663 Å and is therefore too long to be considered a halogen bond, and is unlikely to contribute to information exchange.4O2 coordination sphere of the FeIII ion is often observed in SCO active compounds,1)w_280. FeIII−N bond lengths are characteristic of the spin state (LS≈1.95 Å and HS≈2.15 Å)1) using a SQUID magnetometer revealed an SCO active system with an incomplete transition occurring between 220 K and 90 K, from fully HS to only 22 % of molecules in the HS electronic configuration with T1/2=155 K d_100 crystallized in the same space group, C2/c, with the same neutral metal complex in the asymmetric unit. However, the average Fe−N bond length (1.982 Å) indicated the complex was now at least partially in the LS state; it was also observed that the sample had desolvated (between measurements) with loss of the interstitial MeCN molecules  whilst retaining crystallinity. Crystallographic data were also collected at 140, 180, 230 and 280 K and by plotting the adjusted change in unit cell volume (see ESI for details) against the temperature the SCO event clearly correlates with the changes in the crystal structure , however the loss of the solvent leads to reorientation of molecules in the crystal resulting in a significant shortening of the Br⋅⋅⋅Br distances, “switching on” a type I halogen bond .A more detailed investigation revealed that, by removing the lattice solvent and therefore the hydrogen bonding, halogen⋅⋅⋅halogen interactions become the dominant supramolecular effect Figure . In the 2)–(4) were then synthesized to characterize the importance of these halogen⋅⋅⋅halogen interactions. The modifications are summarized in Table 2). Complex (2)w_100 also crystallized in the space group C2/c with the neutral metal complex now [ReCl5(μ‐MeOpch)Fe(Me‐Im)3] together with two MeCN molecules in the asymmetric unit. Analysis of the Fe−N bond lengths (average: 2.111 Å) shows the iron(III) center to be in the HS state at 100 K. In this solvated sample there is again no appreciable halogen⋅⋅⋅halogen interaction, with the shortest Cl⋅⋅⋅Cl distance at 4.539 Å. Despite the apparent HS structure, magnetic investigation revealed that at 100 K the FeIII is mostly LS (74 % LS)  with the halogen bond “switching on” upon loss of solvent. Since this sample lost crystal quality during desolvation, the exact nature of the halogen⋅⋅⋅halogen interaction could not be clearly defined. Previous work has ordered the strength of halogen bonds as F < Cl <Br < I.1). Both events start at 230 K from a χT value of ≈5.8 cm3 mol−1 K, however the T1/2 value is 33 K lower (T1/2=124 K) for (2) consistent with the gradual nature of the crossover which occurs over a wider temperature range (130 K and 170 K for (1) and (2), respectively).Complexes (2)– were the3) was produced by changing the non‐coordinated MeO group on the primary‐ligand for the sterically larger EtO group. (3)w_180 crystallized with a similar unit cell and packing, but in P21/n due to loss of C‐centering. The asymmetric unit thus contains two [ReBr5(μ‐EtOpch)Fe(Me‐Im)3] complexes and a single molecule of MeCN. Both crystallographically independent complexes appear to be HS at 180 K with the average Fe‐N lengths of 2.116 Å and 2.101 Å for Fe1 and Fe2, respectively. In the complex containing Fe2 there is evidence of a weak type II halogen bond , which is missing for the molecule containing Fe1, thus only half the molecules in the crystal lattice can utilize a halogen bond mediated process. Upon complete solvent loss, sample (3)d_180 undergoes a transformation to a structure with only one [ReBr5(μ‐EtOpch)Fe(Me‐Im)3] molecule in the asymmetric unit. In this case the halogen⋅⋅⋅halogen interaction is stronger than previously observed  involving all molecules in the crystal. SCO events are highly sensitive and this slight change in peripheral substituent from MeO to EtO is enough to modify the SCO properties.1/2=98 K  which replaces the methyl group on the imidazole‐based secondary ligand, R’, with a larger ethyl group crystallizes without interstitial solvent, (4)d_180. In the case of (3) only one additional CH2 unit was added to the molecule in a position placing it at a maximum distance from the {ReX5}− synthon. However, in complex (4) a total of three additional CH2 units were introduced pushing the molecules further apart. In addition, a methyl group on one imidazole points directly into the {ReX5}− synthon . This results in a desolvated complex lacking halogen⋅⋅⋅halogen interactions and therefore without the desired SCO behavior  rule out the possibility that removing solvent alone is enough to induce SCO properties and provide further evidence that in these systems a halogen⋅⋅⋅halogen interaction is required. This highlights the key role of halogen bond mediated information exchange and demonstrates the potential for halogen bonding within SCO research.The results for the desolvated complex  to (11) and compounds (1) to (4), with the CoIII analogues, compounds (5) to (8), presented in the ESI along with the full details of the analytical equipment.The experimental section below covers the ligands (4)2ReBr6  and H2MeOpch  were dissolved in a mixture of 2‐propanol/acetone  and heated to 75 °C for 2 hours. After cooling to room temperature, the solvent volume was reduced to ≈80 mL and the orange precipitate collected via filtration and dried in vacuo. Yield: 1.34 g (87 %). C29H48Br5N5O3Re (1098.44 g mol−1): Calculated C: 31.7 %, H: 4.4 %, N: 6.4 %, Found: C: 31.0 %, H: 4.3 %, N: 6.1 %. IR (ν˜cm−1): 2960 (m), 2932 (w), 2872 (w), 1683 (s), 1608 (w), 1528 (m), 1462 (s), 1406 (m), 1377 (m), 1353 (m), 1244 (vs), 1148 (s), 1077 (s), 968 (m), 952 (m), 905 (m), 881 (m), 781 (m), 629 (w), 482 (m). UV/Vis: (MeCN) (λ nm)=201, 220, 305, 339, 357 (sh), 590.(NBu4)2ReCl6  and H2MeOpch  were dissolved in a mixture of 2‐propanol/acetone  and heated to 75 °C for 6 hours. After cooling to room temperature, the solution was filtered and left to stand under an inert atmosphere. After six days orange needles were collected via filtration and dried in vacuo. Yield: 0.067 g (67 %). C29H48Cl5N5O3Re (997.35 g mol−1): Calculated C: 42.2 %, H: 6.4 %, N: 7.0 %, Found: C: 40.9 %, H: 6.4 %, N: 7.0 %. IR (ν˜cm−1): 3490 (vw), 2960 (s), 2932 (m), 2873 (m), 1682 (vs), 1608 (m), 1576 (w), 1533 (s), 1464 (vs), 1407 (m), 1377 (m), 1354 (s), 1282 (s), 1246 (vs), 1147 (vs), 1076 (s), 1024 (m), 952 (s), 906 (m), 881 (m), 835 (w), 817 (w), 783 (m), 739 (vs), 486 (m), 344 (s). UV/Vis: (MeCN) (λ nm)=200, 221, 292, 353 (sh).(NBu4)2ReBr6  and H2EtOpch  were dissolved in a mixture of 2‐propanol/acetone  and heated to 70 °C for 3 hours. After cooling to room temperature, the solvent volume was reduced to ≈10 mL and the orange precipitate collected via filtration and dried in vacuo. Yield: 0.064 g (82 %). C30H49Br5N5O3Re (1113.48 g mol−1): Calculated C: 32.4 %, H: 4.4 %, N: 6.3 %, Found: C: 32.6 %, H: 4.5 %, N: 6.3 %. IR (ν˜cm−1): 3298 (vw), 2953 (w), 2928 (w), 2868 (w), 1708 (s), 1607 (m), 1513 (s), 1461 (s), 1403 (s), 1377 (m), 1354 (m), 1255 (vs), 1153 (vs), 1111 (m), 1057 (s), 1023 (s), 948 (m), 922 (w), 882 (s), 778 (m), 732 (vs), 581 (s), 486 (s), 443 (w). UV/Vis: (MeCN) (λ nm)=221, 265, 305, 339, 357 (sh).(NBu4)2⋅6 H20  in MeCN (5 mL) was slowly added to a solution of (NBu4)[ReBr5(H2MeOpch)] (9)  and 1‐Me‐Im  in MeCN (5 mL). The reddish‐brown clear solution was sealed and left to stand for three weeks until dark brown needle crystals were formed. Yield: 5 mg (48 %). C25H28Br5FeN10O3Re (1158.2 g mol−1): Calculated C: 25.9 %, H: 2.4 %, N: 12.1 %, Found: C: 26.5 %, H: 2.7 %, N: 12.7 %. IR (ν˜cm−1): 3123 (w), 1589 (m), 1536 (m), 1515 (m), 1466 (w), 1431 (s), 1349 (s), 1287 (m), 1252 (s), 1231 (m),1213 (m), 1156 (m), 1087 (vs), 1020 (w), 969 (w), 948 (m), 923 (w), 825 (w), 785 (w), 750 (vs), 655 (s), 618 (m), 584 (s), 509 (w), 416 (s), 370 (m). UV/Vis: (MeCN) (λ nm)=216, 281, 337, 350, 360.A solution of Fe(ClO4)2⋅6 H20  in MeCN (5 mL) was slowly added to a solution of (NBu4)[ReCl5(H2MeOpch)] (10)  and 1‐Me‐Im  in MeCN (5 mL). The reddish‐brown clear solution was sealed and left to stand for eight days until dark brown needle crystals were formed. Yield: 6 mg (54 %). C25H28Cl5FeN10O3Re (1158.2 g mol−1): Calculated C: 32.1 %, H: 3.0 %, N: 15.0 %, Found: C: 31.2 %, H: 3.0 %, N: 14.7 %. IR (ν˜cm−1): 2959 (vw), 2932 (vw), 2834 (vw), 1599 (s), 1548(s), 1509 (m), 1436 (s), 1354 (s), 1298 (m), 1242 (s), 1219 (vs), 1157 (s), 1081 (m), 1020 (w), 971 (w), 921 (w), 856 (m), 741 (vs), 629 (w), 552 (m), 492 (w), 442 (m), 404 (m), 360 (w). UV/Vis: (MeCN) (λ nm)=205, 282, 326 (sh), 338, 381, 477.A solution of Fe(ClO4)2⋅6 H20  in MeCN (10 mL) was slowly added to a solution of (NBu4)[ReBr5(H2EtOpch)] (11)  and 1‐Me‐Im  in MeCN (10 mL). The reddish‐brown clear solution was sealed and left to stand for four days until dark brown block crystals were formed. Yield: 5 mg (48 %). C26H31Br5FeN10O3Re (1172.67 g mol−1): Calculated C: 26.6 %, H: 2.6 %, N: 11.9 %, Found: C: 26.1 %, H: 2.4 %, N: 12.1 %. IR (ν˜cm−1): 3117 (w), 1606 (w), 1588 (m), 1532 (w), 1433 (m), 1391 (m), 1350 (m), 1280 (w), 1254 (s), 1211 (m), 1157 (m), 1086 (vs), 1023 (m), 946 (m), 901 (w), 844 (m), 783 (w), 741 (vs), 655 (s), 616 (m), 569 (m), 510 (m), 463 (w), 432 (m), 365 (w). UV/Vis: (MeCN) (λ nm)=195, 208, 221, 307, 335, 355, 388 (sh).A solution of Fe(ClO4)2⋅6 H20  in MeCN (10 mL) was slowly added to a solution of (NBu4)[ReBr5(H2MeOpch)] (9)  and 1‐Et‐Im  in MeCN (15 mL). The reddish‐brown clear solution was sealed and left to stand for one day until dark brown block crystals were formed. Yield: 31 mg (43 %). C28H34Br5CoN10O3Re (1153.26 g mol−1): Calculated C: 26.9 %, H: 2.6 %, N: 11.3 %, Found: C: 26.6 %, H: 2.7 %, N: 11.3 %. IR (ν˜cm−1): 3118 (w), 2976 (vw), 934 (vw), 1589 (m), 1550 (m), 1531 (m), 1462 (m), 1426 (m), 1350 (s), 1278 (m), 1245 (m), 1230 (m), 1215 (m), 1182 (w), 1158 (m), 1087 (vs), 1020 (m), 958 (m), 945 (m), 838 (m), 798 (w), 744 (vs), 660 (s), 590 (m), 567 (m), 512 (m), 431 (m), 359 (s). UV/Vis: (MeCN) (λ nm)=191, 209, 274 (sh), 338, 363, 392.A solution of Fe should be addressed to the authors.SupplementaryClick here for additional data file.


Correction to: JA Clin Rep 6, 62 (2020)https://doi.org/10.1186/s40981-020-00368-xFollowing the publication of the original article , the autWe thought that the coefficient 0.0031 was the Bunsen coefficient of oxygen to water measured at 37 °C, but it turned out that the Bunsen coefficient was the coefficient obtained by converting the value measured at the relevant temperature to 0 °C under 1 atm conditions.As a result, we determined that the formula calculated below is appropriate when temperature correction is performed at 37 °C.From:In lieu of Eq. (1), we propose a new temperature correction formula: CaO2 (ml/dl) = 1.58 × Hb (g/dl) × SaO2 + 0.0031 × PaO2 (mmHg) at 37 °C and 1 atm.To:2 (ml/dl) = 1.58 × Hb (g/dl) × SaO2 + 0.0035 × PaO2 (mmHg) at 37 °C and 1 atm.In lieu of Eq. (1), we propose a new temperature correction formula: CaOThe authors apologise for this error.


N,N′,N′′,N′′′-tetrakis(N-methylaniline), the ligand coordinates in a mono-tridentate fashion, and both metal atoms have fivefold coordination spheres with distorted shapes.In the cadmium(II) and zinc(II) complexes of the tetrakis-substituted pyrazine ligand,  N,N′,N′′,N′′′-tetrakis(N-methylaniline)-κ3N2,N1,N6}cadmium(II), [CdI2(C36H40N6)], (I), of the ligand N,N′,N′′,N′′′-tetrakis(N-methylaniline) (L), is generated by a twofold rotation symmetry; the twofold axis bisects the cadmium atom and the nitrogen atoms of the pyrazine ring. The ligand coordinates in a mono-tridentate manner and the cadmium atom has a fivefold CdN3I2 coordination environment with a distorted shape. In the zinc(II) complex, dichlorido{N,N′,N′′,N′′′-tetrakis(N-methylaniline)-κ3N2,N1,N6}zinc(II) dichloromethane 0.6-solvate, [ZnCl2(C36H40N6)]·0.6CH2Cl2, (II), ligand L also coordinates in a mono-tridentate manner and the zinc atom has a fivefold ZnN3Cl2 coordination environment with a distorted shape. It crystallized as a partial dichloromethane solvate. In the crystal of I, the complex molecules are linked by weak C—H⋯I contacts, forming ribbons propagating along [100]. In the crystal of II, the complex molecules are linked by a series of C—H⋯π interactions, forming layers lying parallel to the (1The whole molecule of the cadmium(II) complex, diiodido{ N,N′,N′′,N′′′-tetrakis(N-methylaniline) (L), whose synthesis and crystal structure have been described in the preceding publication I2 (I), of the ligand N,N′,N′′,N′′′-tetrakis(N-methylaniline) (L), is illustrated in Fig. 13I2 coordination environment with a distorted shape . The τ5 parameter for the fivefold coordination of atom Cd1 is 0.14  complex, Cdpyrazine (TPPZ), viz. complex pyrazine)bis(iodo)cadmium(II)  Å in I, while the Cd—I bond lengths are ca 2.741 and 2.727 Å compared to 2.7038 (3) Å in I. The N-methylaniline groups on the non-coordinated side of the ligand are linked by intramolecular C—H⋯π interactions Cl2·0.6(CH2Cl2) (II), is illustrated in Fig. 3L coordinates in a mono-tridentate manner and the zinc atom, Zn1, has a fivefold ZnN3Cl2 coordination environment with a distorted shape . The τ5 parameter for atom Zn1 is 0.30.The molecular structure of the zinc(II) complex, Znpyrazine-N,N′,N′′]zinc(II): a monoclinic polymorph pyrazine]tetrachlorodizinc(II): one hydrated bisdodecachlorotetraaquadecazinc  Å in II, while the Zn—Cl bond lengths vary from ca 2.232 to 2.343 Å compared to 2.2251 (10) and 2.2425 (11) Å in II.A search of the CSD for a ZnNL differs in the two complexes  with respect to ring E (ring Ci in I).The conformation of the ligand es Fig. 4. The oriI is shown in Fig. 5a-axis direction  contact of 3.045 (5) Å and do not participate in any significant intermolecular interactions with the complex molecule. There are Zn—Cl⋯π(pyrazine) contacts present, which link inversion-related molecules, forming dimers  distance of ca 3.987 Å and a Zn—Cl⋯centroid angle of ca. 170.96°. In complex II, the corresponding Cl⋯centroid(pyrazine ring) distance and Zn—Cl⋯centroid angle are 3.683 (2) Å and 155.96 (6)°, respectively  through white to blue . A summary of the short intermolecular contacts in the crystal structures of I and II is given in Table 6The Hirshfeld surface analysis  mapped over dnorm, and the two-dimensional fingerprint plots are given in Fig. 8a) correspond to the I⋯H contacts, which give a pair of spikes in the fingerprint plot  at de + di ≃ 3.0 Å, contributing 14.2% to the HS. The H⋯H contacts contribute 63.4% and the C⋯H contacts 18.0%. Any other atom–atom contacts contributed less than 2% and have not been included here.For complex ot Fig. 8b at deII, the Hirshfeld surface mapped over dnorm, is shown in Fig. 9a, and that for the complex itself and the solvent molecule in Figs. 9b and 9c, respectively. The faint red spots correspond to the Cl⋯H contacts in the crystal. These give a pair of spikes in the fingerprint plots, at de + di ≃ 2.7 Å, contributing 22.7%, in the compound  and at de + di ≃ 2.7 Å, contributing 18.1%, in the complex . For the solvent molecule, a single sharp spike is observed (de + di ≃ 2.8 Å) with a contribution of 59.6% to the HS . The H⋯H contacts contribute 55.1, 59.4 and 25.2% to the Hirshfeld surfaces of the compound, the complex and the solvent molecule, respectively, while the C⋯H contributions are 17.7, 18.8 and 6.8%, respectively. Any other atom–atom contacts contributed less than 2% and have not been included here.For compound d Fig. 10a and atx Fig. 10b. For tS Fig. 10c. The HN,N′,N′′,N′′′-tetrakis(N-methylaniline) L, have been described in the preceding publication Synthesis of the complex ·0.6(CH2Cl2) (II)Synthesis of the complex ·0.6CH2Cl2 (743.99 g mol−1): calculated C 60.50, H 5.68, N 11.65%; found C 60.66, H 5.78, N 11.93%.To a solution of ZnClUiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 7II the _diffrn_reflns_Laue_measured_fraction_full of 0.939 is below the required minimum of 0.95. For II, a small number of low-angle reflections, either in the shadow of the beam-stop or with bad agreement, were omitted during the final cycles of refinement.With the STOE IPDS I, a one-circle diffractometer, for the triclinic system often only 93% of the Ewald sphere is accessible. Hence, for compound 10.1107/S2056989020001644/xi2022sup1.cifCrystal structure: contains datablock(s) I, II, global. DOI: 10.1107/S2056989020001644/xi2022Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989020001644/xi2022IIsup3.hklStructure factors: contains datablock(s) II. DOI: 1982100, 1982099CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: