These aluminates have been characterised by X‐ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non‐covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li(tBuDHP)(TMP)Al(iBu)2] and [(TMEDA)Na(tBuDHP)(TMP)Al(iBu)2] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali‐metal‐aluminium hydride surrog[ATES].A series of group 1 hydrocarbon‐soluble donor free aluminates [AM( Saturated 2,2,6,6‐tetramethylpiperidide, TMP, has long played a key role in synthesis, here combined with an unsaturated dihydropyridine unit, 2‐tBuC5H5N, both contribute to the stability of a series of alkali metal aluminate structures by engaging in non‐covalent interactions with alkali metal cations, the extent of which depends on the alkali metal. Thermal Volatility Analysis (TVA) of the resultant samples showed that the propensity of hydride expulsion of the AM(tBuDHP) complexes increased down the group from lithium to potassium, following the trend of decomposition of saline hydrides.In 2015, our group reported another strategy, wherein a saturated C−H bond in an alkyldihydropyridyl anion bound to lithium in  has a track record in stabilizing a range of organolithium components to form heterobimetallic ‘ate’ complexes. These ates have had an important role to play in the development of bimetallic cooperativity.[iBu)2Al(TMP)] in tandem have ascertained that the sterically encumbered TMP ligands allow the lithium amide to display its basic function by deprotonation of an aryl/alkyl substrate, while the organoaluminium moiety traps the new, less hindered organolithium molecule in a method labelled as “trans‐metal‐trapping” (TMT).[tBuDHP)], an amide carrying a surrogate hydride, as an alternative to Li(TMP). From a structural perspective this would open up a new avenue to isolate rarer aluminates of heavier alkali metals. Hence, our target here was to synthesise and characterise a new class of ate compound combining the complete set of alkali metal dihydropyridines with the dialkylamidoaluminium reagent [(iBu)2Al(TMP)], in effect heteroleptic alkali metal aluminium hydride surrog[ATES].Di‐iso‐butylaluminium‐2,2,6,6‐tetramethylpiperidide [2Al(TMP)] was subjected to a suspensiontBuDHP)] in n‐pentane, the resultant mixture turned homogeneous at room temperature (Scheme 6D6 solution hinted at the formation of a new species as evident from a definite shift in the dihydropyridyl C−H resonances in comparison to those in free Li(tBuDHP) . Meanwhile, a concentrated solution of the above mixture in n‐pentane cooled to −20 °C overnight yielded colourless crystalline blocks. Single crystal X‐ray analysis of the crystals unveiled a solvent‐free monomer of a bimetallic ate complex, [Li(tBuDHP)(TMP)Al(iBu)2] (1)  analogues ether, PMDETA=N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine, and Me6TREN=tris[2‐(dimethylamino)ethyl]amine].4H4)]n allows the alkali metal to modify its bonding nature towards the anionic N‐heterocyclic ligand from σ‐bonding in [(PMDETA)Na(NC4H4)]2 to π‐bonding in the corresponding lower‐order and higher‐order zincate derivatives .1 fall in the range of 2.272(3) Å to 2.411(3) Å. The sp3 hybridized ring carbon is slightly elevated from the conjugated plane lying at a distance of 2.705(3) Å from lithium. The alternating arrangement of short and long bond lengths within C6−C7−C8−C9−N1  Å in contrast to those in the solvated structures of Li(tBuDHP) reported earlier by our group .1 is related to some of the diamido‐dialkyl lithium aluminate examples in the literature1 is unusual being a structurally well‐defined example of a donor‐free monomeric ate featuring π‐stabilization.Pleasingly, it was found that when an equivalent amount of  (1 a)  cannot be cast as a substitute to Li(TMP) since one decisive criterion for a TMT system states that the lithium and aluminium species should not co‐complex with each other to any significant extent to form an ate in order to display unique reactivity profiles. The lower steric profile of Li(tBuDHP) rules it out of consideration as a partner in trans‐metal‐trapping chemistry as it readily co‐complexes with the organoaluminium moiety. However, the formation of 1 and 1 a can be treated as among the first illustrations of a trapped amido anion with a surrogate hydride as opposed to the trapped carbanions in all previous examples.It may be assumed that Li(tBuDHP) and having recently reported rubidium and caesium aluminyl compounds,tBuDHP). Owing to the practical difficulties involved in the process of isolating a pure batch of heavy alkali metal tert‐butoxide, in benzene provided the corresponding alkali metal alkoxides [Rb−OtAm and Cs−OtAm], obtained as white powders upon evacuation of the solvent and other volatiles under reduced pressure (Scheme tBuDHP) in benzene at room temperature allowed the precipitation of unsolvated hydride surrogates of rubidium [Rb(tBuDHP)] and caesium [Cs(tBuDHP] in quantitative yields. Each compound can be stored under inert conditions as a solid powder after washing away any lithium impurities with benzene. The identities of the above compounds were confirmed by multinuclear NMR spectroscopy (See Supporting Information for NMR characterisation). The dihydropyridyl signals in the 1H NMR spectra were in the range of 3.2 ppm to 6.7 ppm and comparable to those of the lighter congeners.tBuDHP) and Cs(tBuDHP) respectively in deuterated THF. Following the solubility trend of alkali metal dihydropyridines, Rb(tBuDHP) and Cs(tBuDHP) were found to be insoluble in hydrocarbon solvents. A possible explanation for this observation is that with increase in atomic radii down the group, the tendency to form higher order oligomers/polymers also intensifies.On the back of the progress made with Li2Al(TMP)] to combine with the heavier members of the group one tBuDHPs and remain homogeneous in solution (Scheme tBuDHP) and [(iBu)2Al(TMP)] produced colourless blocks of crystals after leaving the mixture with slow evaporation of hexane at room temperature. The structure of the compound was determined by single crystal X‐ray diffraction studies and identified as [Na(tBuDHP)(TMP)Al(iBu)2]∞  contact of 2.977(2) Å from a neighbouring dihydropyridyl anion to construct a polymeric zig‐zag chain. The asymmetric unit of 2 bears a resemblance to 1 by virtue of having a similar bridging alignment [M−N1−Al−N2] with a distorted tetrahedral geometry at the aluminium centre.Benzene was found to be a suitable medium for [Na(tBuDHP)(TMP)Al(iBu)2] (2 a) were formed  aluminate [(TMEDA)Na(TMP)(iBu)Al(iBu)2]  protons were found to be split into three separate multiplets in the 1H NMR spectrum , of which two protons appear shielded at −0.02 (1H) and −0.30 ppm (1H) respectively  indicating the close interaction of the sodium centre to the axial H‐ atoms of the TMP moiety in the donor‐free aluminate. The structures of 2 and 2 a bear significance on the grounds of the paucity of structures of bisamido bridged sodium aluminates with only a few crystallographically characterised examples present in the literature from the Fedyushkin and Chivers groups.[When an equivalent amount of TMEDA was added to a benzene solution of d Figure ‐top. Inte Figure ‐bottom. s groups.21biBu)Al(iBu)2] .[iBu)2Al(TMP)] induced the deprotonation of one α‐CH3 of a TMP unit to give the monomer [(TMEDA)K(μ‐TMP*)(μ‐iBu)Al(iBu)], where TMP* represents a CH3‐ and NH‐deprotonated dianionic variant of TMP.tBuDHP) produced the first donor free bis‐amido potassium aluminate in [K(tBuDHP)(TMP)Al(iBu)2]∞ (3) in a 74 % yield. Similarly, crystals from a Rb−Al combination in benzene were obtained in a yield of 75 % after removing the solvent in vacuo followed by adding hexane to the resultant yellow oil at room temperature. Aluminates 3, and [Rb(tBuDHP)(TMP)Al(iBu)2]∞ (4) K(μ‐amide), which lies opposite to the sp3 carbon (C5) atom [3.926 Å in 2>3.319 Å in 3>3.294 Å in 4]. Contrary to the above observation, it is found that the distances between neighbouring methyl groups (C1) on the tBu substituent and the alkali metal follows a reverse order . While Li prefers to sit ‘trans’ to the tBu group of the tBuDHP, Na likes to rest itself on the site ‘cis’ to the tBu group of the tBuDHP ligand. This is evident from the contrasting CH3(TMP)⋅⋅⋅AM contacts Na(TMP)(iBu)Al(iBu)2}iBu)Al(iBu)2}].4 are distinctively shorter than the ones reported earlier by our group in the homoleptic TMEDA solvate [(TMEDA)Rb(TMP)]2.The π‐stabilization offered by the tBuDHP) and [(iBu)2Al(TMP)] in benzene solution could be proved from the comparable 1H NMR resonances  against those of its lighter siblings, attempts to crystallize the same from its oil were unsuccessful. Addition of hexane to the oily substance resulted in the formation of a sticky solid. The presence of a variety of nitrogen and oxygen donors such as PMDETA, TMEDA, THF or 18‐crown‐6‐ether in a hexane suspension of the bimetallic mixture failed to produce crystalline samples suitable for X‐ray crystallographic study. However, the solubility of the compound in benzene, points to the effectiveness of the aluminium agent in minimizing the oligomerization of the surrogate caesium hydride.While the formation of a co‐complexation product from a mixture of Cs. The electrostatic interaction energy was calculated according to Equation (1). We minimized basis set superposition error (BSSE) by calculating a counterpoise corrected interaction energy which increased electronic interaction energies of these four complexes by an average of 32 kJ mol−1.It has been well documented that attractive London Dispersion Forces (LDF) influence the stability, structure, and reactivity of organometallic compounds.28b Late−1 for lithium to −393 kJ mol−1 for rubidium. As evident from Figure E) (kJ mol−1) in order of increasing stability=−630.23 (Li)>−511.65 (Na)>−410.02 (K)>−370.45 (Rb)], which is antithetical to the calculated LDF values [Energy (E) (kJ mol−1) in order of increasing stability=−4.47 (Li)<−15.07 (Na)<−18.92 (K)<−22.67 (Rb)] . These results support the existence of the observed short contacts [AM⋅⋅⋅H−C(TMP)] in the donor‐free heavy alkali‐metal aluminates (3 and 4). Surprisingly, considering the high utility of TMP and the numerous structures it is found in,In order to better visualize and understand the myriad of non‐covalent interactions (NCI) we used the NCIPlot software with ultrafine integration to generate the representations in Figure 1–4 at 85 °C in deuterated benzene. This showed that lithium aluminate 1 is the most stable, with no evidence of MH elimination/rearomatized pyridine formation even after heating for 24 h. However, this study provided evidence of metal hydride elimination, as seen by the appearance of the characteristic 2‐t‐butylpyridine resonances in the 1H NMR spectra  over 2–3 days. In order to preliminarily test the surrogate hydride reactivity of these aluminates, experiments with the lightest and heaviest aluminates of the series (Li and Cs) were carried out at room temperature in hexane and benzene solution respectively with stoichiometric amounts of benzophenone. Quenching these mixtures with H2O resulted in the precipitation of insoluble hydroxide salts along with the formation of benzhydrol, which was characterised by NMR spectroscopy . However, these results do not explain the origin of the hydride source, since a previous report by our group indicated the availability of masked (β) hydride on the isobutyl groups bound to aluminium in the reduction of benzophenone, mimicking a Meerwein‐Pondorf‐Verley type mechanism.1 in C6D6 at room temperature . The appearance of characteristic isobutene resonances (δ=4.73 and 1.59 ppm) in the 1H NMR spectrum suggests the role of the masked hydride from the isobutyl groups. Addition of a further equivalent of benzophenone to this mixture revealed a complete loss of isobutyl resonances, confirming the aforementioned possibility. To our surprise, addition of a third equivalent of benzophenone at room temperature did not yield any 2‐t‐butylpyridine. The dihydropyridyl resonances appear shifted compared to both the starting material and also homometallic [Li(tBuDHP)], while the 7Li resonance shifts from −2.10 in 1 to 1.90 ppm , suggesting an unidentified bimetallic species is formed. This lack of reactivity of the dihydropyridyl moiety suggests that the presence of the aluminium component provides a stabilizing influence since [Li(tBuDHP)] itself readily reduces benzophenone with concomitant generation of 2‐t‐butylpyridine. When this experiment was replicated with isolated crystals of the rubidium aluminate (4), the appearance of both isobutene as well as the 2‐t‐butylpyridine resonances in the 1H NMR spectrum were seen, hinting towards increased surrogate hydride reactivity of the heavier group one aluminates . Resonances at 6.09 and 6.27 ppm in the 1H NMR spectrum allude to the fact that there are potentially two distinct −OC(H)Ph2 environments in the product which has been witnessed previously in homometallic [(TMP)(Ph2(H)CO)Al(μ‐OC(H)Ph2)]2 which shows distinct bridging and terminal resonances.We next attempted to study the stability of these complexes in light of the presence of these stabilizing interactions, by heating samples of the donor free ates tBuDHP)] into the chemistry of aluminates. The dialkyl amido aluminium compound [(iBu)2Al(TMP)] plays a fundamental role as a stabilizer by delivering the alkali metal surrogate hydride [AM(tBuDHP)] into a hydrocarbon solvent when added in stoichiometric quantities. The crystal structures of [Li(tBuDHP)(TMP)Al(iBu)2] (1), [Na(tBuDHP)(TMP)Al(iBu)2]∞ (2), [K(tBuDHP)(TMP)Al(iBu)2]∞ (3), and [Rb(tBuDHP)(TMP)Al(iBu)2]∞ (4) demonstrated that the dihydropyridyl anion can act as a N‐heterocyclic group with a surrogate hydride providing stability to the alkali metals through π‐donation. These structures are one of the first in a series of donor free ates with two distinct amido bridges. The difference in the aggregation states is reflected in their solubility. While the lithium congener is soluble in an aliphatic hydrocarbon solvent, it takes an aromatic (benzene) solvent to dissolve the other group one aluminates. The polymers can be broken down into monomeric units by the employment of neutral Lewis base donors as observed during the isolation of [(THF)Li(tBuDHP)(TMP)Al(iBu)2] (1 a) and [(TMEDA)Na(tBuDHP)(TMP)Al(iBu)2] (2 a). Energy calculations on the stable donor free complexes provided us with an insight into the nature of alkali‐metal‐ligand interactions where a definite trend in increased contribution of attractive London Dispersion Forces can be observed on moving down group one, which is in sharp contrast to the electrostatic forces of attraction. The NCI plots demonstrated that the methylene groups of a saturated TMP ligand can lend stability to the large cations of group one. Preliminary test reactions suggest that the stability imparted on the dihydropyridyl unit as a consequence of the presence of the organoaluminium fragment modifies its reactivity as a metal hydride source, with the degree of modification depending upon the identity of the alkali metal. Our ongoing work is to investigate further this facet of their behaviour as well as to probe other reactivity scenarios in both stoichiometric and catalytic applications.In summary, this study has exported alkali metal dihydropyridines : δ 0.98 ppm , δ 3.83 ppm , δ 4.94 ppm , δ 5.34 ppm , δ 6.27 ppm , δ 7.14 ppm , δ 1.72 ppm , δ 0.92 ppm , δ 0.80 ppm , δ 1.96 ppm , δ 1.47–1.54 ppm , δ 1.11–1.16 ppm , δ 2.13 ppm , δ 0.19–0.35 ppm , δ 0.49–0.57 ppm ; 13C {1 H} NMR : δ 147.62 ppm (−CH(6)[DHP]), δ 123.42 ppm (−CH(4)[DHP]), δ 107.16 ppm (−CH(3)[DHP]), δ 99.09 ppm (−CH(5)[DHP]), δ 59.70 ppm (−CH(2)[DHP]), δ 24.76 ppm (−tBu[DHP]), δ 40.68 ppm (quaternary[DHP]), δ 45.45+46.24 ppm (β‐CH2[TMP]), δ 17.81 ppm (γCH2[TMP]), δ 36.69+38.01 ppm (CH3[TMP]), δ 51.99+51.76 ppm (2×quaternary[TMP]), δ 26.73 ppm (−CH[iBu]), δ 27.97+28.10 ppm (−CH3[iBu]), The resonances of −CH2[iBu] could not be observed;7Li  δ=−1.71 ppm (s).tBuDHP)(TMP)Al(iBu)2)] (1 a)Synthesis of [(THF)Li(: Li(tBuDHP)iBu2AlTMPtBuDHP)(TMP)Al(iBu)]∞ (2)Synthesis of [Na(: Na(tBuDHP)iBu2AlTMP26H50AlNaN2] (440.66 g mol−1): C 70.87, H 11.44, N 6.36; Found: C 70.80, H 11.36, N 5.98. 1H NMR : δ 1.18 ppm , δ 3.76 ppm , δ 4.59 ppm , δ 4.74 ppm , δ 5.85 ppm , δ 7.11 ppm , δ 1.35 ppm , δ −0.30 ppm , δ −0.02 ppm , δ 1.73 ppm , δ 1.09+1.15+1.39+1.51 ppm , δ 1.09 ppm , δ 1.43–1.47 ppm , δ 2.46 ppm , δ 0.38–0.87 ppm ; 13C {1 H} NMR : δ 147.65 ppm (−CH(6)[DHP]), δ 125.41 ppm (−CH(4)[DHP]), δ 105.02 ppm (−CH(3)[DHP]), δ 94.96 ppm (−CH(5)[DHP]), δ 59.96 ppm (−CH(2)[DHP]), δ 25.66 ppm (−tBu[DHP]), δ 41.55 ppm (quaternary[DHP]), δ 45.27 ppm (β‐CH2[TMP]), δ 17.72 ppm (γCH2[TMP]), δ 37.56+38.80 ppm (CH3[TMP]), δ 27.34+27.51 ppm (−CH[iBu]), δ 28.24+28.59+29.27+29.94 ppm (−CH3[iBu]), The resonances of −CH2[iBu] and quatenary[TMP] could not be observed.tBuDHP)(TMP)Al(iBu)] (2 a)Synthesis of [(TMEDA)Na(: Na(tBuDHP)iBu2AlTMPtBuDHP)(TMP)Al(iBu)2] (2a) was not obtained, which may be attributed to decomposition during shipping and/or sample preparation. Best values are given, nevertheless. Elemental analysis: Calculated values for C32H66AlN4Na (556.86 g mol−1): C 69.02, H 11.95, N 10.06; Found: C 68.98, H 11.73, N 7.59. 1H NMR : δ 0.94 ppm , δ 3.74 ppm , δ 4.70 ppm , δ 4.76 ppm , δ 6.02 ppm , δ 7.04 ppm , δ 2.37 ppm , δ 2.27 ppm , δ 1.70 ppm , δ 1.31–1.41 ppm , δ 1.04 ppm , δ 2.06 ppm , δ 0.04–0.47 ppm ; 13C {1 H} NMR : δ 147.06 ppm (−CH(6)[DHP]), δ 123.98 ppm (−CH(4)[DHP]), δ 105.62 ppm (−CH(3)[DHP]), δ 93.75 ppm (−CH(5)[DHP]), δ 60.21 ppm (−CH(2)[DHP]), δ 25.19 ppm (−(CH3)3[DHP]), δ 41.32 ppm (quaternary[DHP]), δ 57.91 ppm (−CH2[TMEDA]), δ 46.73 ppm (−CH3[TMEDA]), δ 45.83 ppm (β‐CH2[TMP]), δ 18.16 ppm (γCH2[TMP]), δ 26.09 ppm (CH3[TMP]), δ 51.65 ppm (quaternary[TMP]), δ 26.92+27.03 ppm (−CH[iBu]), δ 27.97+28.60+29.06 ppm (−CH3[iBu]), The resonances of −CH2[iBu] could not be observed.tBuDHP)(TMP)Al(iBu)]∞ (3)Synthesis of  (3) was not obtained, which may be attributed to decomposition during shipping and/or sample preparation. Best values are given, nevertheless. Elemental analysis: Calculated values for [C26H50AlKN2] (456.77 g mol−1): C 68.37, H 11.03, N 6.13; Found: C 67.84, H 9.98, N 4.67. 1H NMR : δ 1.25 ppm 3[DHP]+6H, −CH3[TMP]+2H, β‐CH2[TMP]), δ 3.79 ppm , δ 4.54 ppm , δ 4.67 ppm , δ 5.74 ppm , δ 7.04 ppm , δ 1.38 ppm , δ 0.87 ppm , δ 1.47 ppm , δ 2.50 ppm , δ 0.41–0.83 ppm ; 13C {1 H} NMR : δ 147.92 ppm (−CH(6)[DHP]), δ 125.67 ppm (−CH(4)[DHP]), δ 104.02 ppm (−CH(3)[DHP]), δ 95.18 ppm (−CH(5)[DHP]), δ 66.28 ppm (−CH(2)[DHP]), δ 26.08 ppm (−tBu[DHP]), δ 41.78 ppm (quaternary[DHP]), δ 18.13 ppm (γCH2[TMP]), δ 51.50 ppm (quaternary[TMP]), δ 27.44+27.73 ppm (−CH[iBu]), δ 28.44+28.76+29.63+29.88 ppm (−CH3[iBu]). The resonances of −CH2[iBu] could not be observed. The resonances of β‐CH2[TMP] and −CH3[TMP] were not assigned due to overlap of the methyl signals (from TMP and iBu groups) in 1H13C‐HSQC NMR spectrum.iBu)]∞ (4)Synthesis of  (4) was not obtained, which may be attributed to decomposition during shipping and/or sample preparation. Best values are given, nevertheless. Elemental analysis: Calculated values for [C26H50AlRbN2] (503.14 g mol−1): C 62.07, H 10.02, N 5.57; Found: C 61.75, H 9.73, N 4.62. 1H NMR : δ 1.30 ppm , δ 3.85 ppm , δ 4.56 ppm , δ 4.61 ppm , δ 5.66 ppm , δ 7.03 ppm , δ 0.83 ppm , δ 1.63 ppm , δ 1.34 ppm , δ 1.48 ppm , δ 2.50 ppm , δ 0.43–0.75 ppm ; 13C {1 H} NMR : δ 148.13 ppm (−CH(6)[DHP]), δ 125.87 ppm (−CH(4)[DHP]), δ 103.95 ppm (−CH(3)[DHP]), δ 94.94 ppm (−CH(5)[DHP]), δ 60.59 ppm (−CH(2)[DHP]), δ 26.30 ppm (−tBu[DHP]), δ 41.88 ppm (quaternary[DHP]), δ 43.66 ppm (β‐CH2[TMP]), δ 18.33 ppm (γCH2[TMP]), δ 33.69+34.08 ppm (CH3[TMP]), δ 51.55 ppm (quaternary[TMP]), δ 27.41+27.75 ppm (−CH[iBu]), δ 28.58+29.09+29.68+29.76 ppm (−CH3[iBu]), The resonances of −CH2[iBu] and quaternary[TMP] could not be observed.The authors declare no conflict of interest.As a service to our authors and readers, this journal provides supporting information supplied by the authors. Such materials are peer reviewed and may be re‐organized for online delivery, but are not copy‐edited or typeset. Technical support issues arising from supporting information (other than missing files) should be addressed to the authors.Supporting InformationClick here for additional data file.


In the crystal structure, centrosymmetric molecules are linked through intermolecular N—H⋯O hydrogen bonds into sheets extending parallel to (0 2(en)2)] , has been synthesized. The complex molecules are located on inversion centers. Two DNBA anions monodentately coordinate the CdII atom through an oxygen atom of the carboxylate group while two en molecules coordinate in a chelate fashion, resulting in a distorted O2N4 coordination set. There is a weak intramolecular hydrogen bond of 3.099 (4) Å between the non-coordinating oxygen atom of the carboxylate group and one of the en amine groups. Three relatively weak intermolecular N—H⋯O hydrogen bonds associate complex molecules into sheets extending parallel to  and H⋯H (21.1%) interactions.During systematic investigations of bioavailability and biological action enhancement of well known compounds with low bioactivity, a new mixed-ligand metal complex, [Cd(DNBA) It is a well known bidentate chelating ligand for coordination complexes  to 102.66 (12)°, indicating a rather strong distortion from the ideal octahedral shape. The conformation of the complex molecule is stabilized through a weak intramolecular hydrogen bond [3.099 (4) Å and 143 (3)°] between the N4—H4A donor and the O2 acceptor (Table 1S(6). Most coplanar with the aromatic ring is the N1O2 nitro group [dihedral angle of 3.873 (3)°] while the carboxylate group is considerably twisted from the aromatic ring [dihedral angle = 19.332 (9)°]. The arrangement of the N2O2 nitro group is intermediate between the latter two, the corresponding dihedral angle being 13.529 (6)°.In the crystal of the title compound, the complex molecules are located on inversion centers. Two symmetry-related DNBA anions monodentately coordinate to Cdms Fig. 1. The bonr Table 1 definingA⋯O4i and N4—H4B⋯O4ii hydrogen bonds define rings with graph-set notation via N3—H3B⋯O5iii hydrogen bonds, forming sheets extending parallel to (0Cg1⋯Cg1 = 3.715 (3) Å, slippage = 1.608 Å, symmetry operation: 1 − x, −y, 1 − z; Cg1 is the centroid of the phenyl (C1–C6) ring].There are three relatively weak intermolecular hydrogen bonds in the crystal structure Table 1. N4—H4A⋯1) Fig. 2. The sheCrystal Explorer 17.5  analysis was carried out using rm Fig. 3 shows thet al., 20162(en)2)] complex. The silver complexes with refcodes EQOKEA 2  was slowly added an ethanol solution (4 ml) containing en (60 μl) and DNBA  under constant stirring. A colourless crystalline product was obtained at room temperature by slow solvent evaporation after 6 d. Single crystals for X-ray structure determination were selected from this product. Yield: 65%. Elemental analysis for C18H22CdN8O12 (654.83): calculated C 33.02; H 3.39; N 17.11%; found: C 32.96; H 3.32; N 17.08%.To an aqueous solution (2.5 ml) of Cd I. DOI: 10.1107/S2414314620008433/wm4132Isup2.hklStructure factors: contains datablock(s) I. DOI: 2011747CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-022-13747-4, published online 11 June 2022Correction to: The original version of this Article contained an error in the y-axis label of Figure 4(C), where “stereoacuity improvement (%)” should read “stereoacuity improvement”.The original Figure The original Article has been corrected.


In the crystal, corrugated layers parallel to the ab plane are formed by a combination of C—H⋯O, C—H⋯π(ring) and π-stacking interactions.The inner part of the ester substituent is nearly perpendicular to the dihydropyridazine ring while the  17H20N2O4, the inner part of the ester substituent is nearly perpendicular to the dihydropyridazine ring, forming a dihedral angle of 83.21 (7)°. In the crystal, inversion dimers are formed by pairwise C—H⋯O interactions with the dimers connected into chains extending along the b-axis direction by C—H⋯π(ring) interactions. The chains are connected by π-stacking interactions to give corrugated layers parallel to the ab plane. The terminal ethyl group is disordered over two two sets of sites with the major component having a site occupancy factor of 0.715 (10)In the title molecule, C This latter angle indicates that the inner end of the substituent on N2 is nearly perpendicular to the tetrahydropyridazine ring. The C2—C3—C5—C6 torsion angle of −9.4 (2)° indicates that the centroid of the 4-methoxyphenyl ring is only slightly below the plane of the pyridazine ring. This conformation appears to be the result of the intermolecular π-stacking interaction (see below).B⋯O1 interactions (Table 1b-axis direction by C16—H16B⋯Cg1 interactions (Table 1i–C11i rings [symmetry code: (i) −x + y + z + ab plane -one precursor. To this pyridazine derivative (0.05 mol) was added potassium carbonate (0.1 mmol), tetrabutylammonium bromide (0.01 mmol) and 2-ethyl bromoacetate (0.1 mol) in dimethylformamide (20 ml). The mixture was stirred for 24 h at room temperature. At the end of the reaction, the solution was filtered and the solvent evaporated under reduced pressure. The residue was washed with water and methylene chloride. The solvent was removed and colourless blocks of the title compound were obtained by recrystallization of the product from its acetone solution.A mixture of 3-(4-methoxybenzylidene)-4-oxopentanoic acid (0.05 mol) and hydrazine hydrate (0.1 mol) in ethanol (100 ml) was refluxed for 2 h. The precipitate that formed was filtered off and recrystallized from acetone solution to obtain the 5-(4-methoxybenzyl)-6-methylpyridazin-3(2−1): 1743 , 1660 (C=ON), 1599 (C=C), 1205 (C—N), 1011 and 1145 . 1H NMR (p.p.m.): 1.23 ; 2.22 ; 2.33 ; 3.85 ; 4.17 ; 4.87 ; 6.48 ; 6.93–6.96 ; 7.25–7.27 . 13C NMR (p.p.m.): 14.11 (CH3); 21.03 ; 25.21 ; 37.67 (CH2); 51.34 (CH2); 60.95 (CH2); 127.13–127.44 (CH aromatic); 129.13–130.35 (CH aromatic); 132.12 (C—Cα aromatic); 136.51 ; 138.49 ; 144.97 ; 147.17 (C=N); 161.19 ; 169.52 .Yield 79%; m.p. 406–408 K. IR  global, I. DOI: 10.1107/S241431462200582X/tk4077Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S241431462200582X/tk4077Isup3.cmlSupporting information file. DOI: 2175897CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II ion has an N4Cl2 octahedral coordination sphere defined by three N atoms of the tridentate 2,3,5,6-tetra-2-pyridylpyrazine ligand, one N atom of the pyridine ligand and two Cl− anions.The central Ni 2(C5H5N)(C24H16N6)], the NiII ion is six-coordinated in a distorted octahedral coordination environment defined by three N atoms of the tridentate 2,3,5,6-tetra-2-pyridylpyrazine ligand, one N atom of the pyridine ligand and two Cl− anions, with the latter being mutually trans. The complex is disposed about a twofold rotation axis along the a axis. The complex molecules are connected in the crystal via C—H⋯Cl, C—H⋯N and π–π [closest inter-centroid separation = 3.7446 (14) Å between pyridyl rings].In the title complex, [NiCl The Ni—N[pyrazine(N1) or pyridyl] bond lengths are roughly equivalent, with distances of 2.008 (3) – 2.1026 (19) Å. The pyrazine ring (N1—C1i) slightly deviates from planarity, with a maximum deviation of 0.057 (2) Å for the C2 atom from the least-squares plane of the ring. The dihedral angles between the nearly planar pyridyl rings and the least-squares plane of their carrier pyrazine ring are 14.90 (4)° for the coordinating pyridyl ring (N3—C7) and 54.42 (9)° for the non-coordinating pyridyl ring (N4—C12), respectively. The dihedral angle between the pyrazine ring and the pyridine ligand (N5—C13i) is 57.8 (1)°.In the title complex, the central Nins Fig. 1. The comCg1 (the centroid of the ring N3/C3–C7) and Cg1ii [symmetry code: (ii) x, x − y, −z + In the crystal, the complex displays numerous inter- and intramolecular π–π interactions between adjacent six-membered rings. The most significant interaction of this kind is that between s Table 1 that cons Table 1.2·6H2O  in ethanol (20 ml) was added 2,3,5,6-tetra-2-pyridylpyrazine , followed by stirring for 24 h at rooom temperature. The formed precipitate was separated by filtration, washed with ethanol and acetone, and dried at 323 K, to give a brown powder (0.5045 g). Brown crystals suitable for X-ray analysis were obtained by slow evaporation from its pyridine/N,N-dimethylformamide (DMF) solution at 333 K.To a solution of NiClCrystal data, data collection and structure refinement details are summarized in Table 210.1107/S2414314621000948/wm4144sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314621000948/wm4144Isup2.hklStructure factors: contains datablock(s) I. DOI: 2058988CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Yarrowia lipolytica as an alternative host for ergothioneine production. We expressed the biosynthetic enzymes EGT1 from Neurospora crassa and EGT2 from Claviceps purpurea to obtain 158 mg·L−1 of ergothioneine in small‐scale cultivation, with an additional copy of each gene improving the titer to 205 mg·L−1. The effect of phosphate limitation on ergothioneine production was studied, and finally, a phosphate‐limited fed‐batch fermentation in 1 L bioreactors yielded 1.63 ± 0.04 g·L−1 ergothioneine in 220 h, corresponding to an overall volumetric productivity of 7.41 mg·L−1·h−1, showing that Y. lipolytica is a promising host for ergothioneine production.Ergothioneine is a naturally occurring antioxidant that has shown potential in ameliorating neurodegenerative and cardiovascular diseases. In this study, we investigated the potential of the Crabtree‐negative, oleaginous yeast  Yarrowia lipolytica is a viable host to produce the antioxidant ergothioneine. Yarrowia lipolytica could reach ergothioneine production levels comparable to or exceeding those reported in other hosts, such as Escherichia coli and Saccharomyces cerevisiae, by genomic integration of the ergothioneine biosynthetic pathway and fed‐batch fermentation on mineral medium.Here, we report that the oleaginous yeast  CDW, cell dry weightERG, ergothioneineMES, 2‐(N‐morpholino)ethanesulfonic acidSAM, S‐adenosylmethionineThe amino acid‐derived nutraceutical ergothioneine (ERG) has recently gained much scientific interest for its potential application in preventing or treating neurodegenerative and cardiovascular diseases , 2. CurrS‐adenosylmethionine  was bought from Sigma‐Aldrich . Synthetic genes were ordered through the GeneArt Gene Synthesis service of Thermo Fisher Scientific  or the custom gene synthesis service of IDT . Sequencing results were obtained through Eurofins Genomics  using their Mix2Seq kit.The n ST6512  was used−1 of glucose, 7.5 g·L−1 of (NH4)2SO4, 14.4 g·L−1 of KH2PO4, 0.5 g·L−1 of MgSO4.7H2O, 2 mL·L−1 of trace metal solution, and 1 mL·L−1 of vitamin solution, adjusted to pH 6.0 using 2 m of NaOH. Mineral medium without phosphate was prepared using the same recipe, but KH2PO4 was substituted with the same concentration of 2‐(N‐morpholino)ethanesulfonic acid (MES) hydrate. High glucose mineral medium without phosphate consisted of 50 g·L−1 of glucose, 20 g·L−1 of (NH4)2SO4, 30 g·L−1 of MES hydrate, 1.25 g·L−1 of MgSO4.7H2O, 5 mL·L−1 of trace metal solution, and 2.5 mL·L−1 of vitamin solution, adjusted to pH 6.0 using 2 m of NaOH.Mineral medium consisted of 20 g·L−1 of CaCl2.2H2O, 4.5 g·L−1 of ZnSO4.7H2O, 3 g·L−1 of FeSO4.7H2O, 1 g·L−1 of H3BO3, 1 g·L−1 of MnCl2.4H2O, 0.4 g·L−1 of Na2MoO4.2H2O, 0.3 g·L−1 of CoCl2.6H2O, 0.1 g·L−1 of CuSO4.5H2O, 0.1 g·L−1 of KI, and 15 g·L−1 of EDTA. Vitamin solution consisted of 50 mg·L−1 of biotin, 200 mg·L−1 of p‐aminobenzoic acid, 1 g·L−1 of nicotinic acid, 1 g·L−1 of calcium pantothenate, 1 g·L−1 of pyridoxine HCl, 1 g·L−1 of thiamine HCl, and 25 g·L−1 of myo‐inositol.Trace metal solution consisted of 4.5 g·LY. lipolytica was performed using the EasyCloneYALI method . , 9. Y. lY. lipolytica. Phosphate limitation was a viable strategy to limit biomass accumulation in the bioreactors. ERG titer reached 1.63 ± 0.04 g·L−1 after 220 h of fermentation in mineral medium with glucose as the only carbon source.In conclusion, we integrated the ERG biosynthesis pathway into oleaginous yeast SH, DBK, and IB are named inventors on a European Patent application covering parts of the work described above.IB and DBK conceived the study; IB and JLM supervised the study; SAH, IHJ, and JLM designed the experiments; SAH, IHJ, and MR performed the experiments and data analysis; SAH and IB wrote the manuscript; SAH, IB, DBK, IHJ, and JLM reviewed and revised the manuscript; IB and JLM provided resources for the study; IB acquired funding for the study.Fig. S1. Bacterial ergothioneine biosynthesis pathway.Fig. S2. The effect of phosphate limitation on the growth of the ergothioneine‐producing Yarrowia lipolytica strain ST10264.Fig. S3. Ergothioneine production and biomass accumulation of ST10264 under phosphate‐limited fed‐batch conditions in a single 1 L bioreactor with an initial amount of 240 mg KH2PO4.Table S1. List with genes and their DNA sequences used in this paper.Table S2. List of primers used in this study for cloning purposes.Table S3. List of primers used in this study for sequencing.Table S4. List of biobricks used in this study.Table S5. List of plasmids used in this study, made by USER cloning.Table S6. List of strains used in this study.Click here for additional data file.


The crystal structure of the ‘magic’ mushroom natural product baeocystin is reported for the first time. N-methyltryptamine {systematic name: 3-[2-(methylazaniumyl)ethyl]-1H-indol-4-yl hydrogen phosphate}, C11H15N2O4P, has a single zwitterionic molecule in the asymmetric unit. The molecule has an intramolecular N—H⋯O hydrogen bond between the ammonium cation and the hydrophosphate anion. In the crystal, the molecules are linked by N—H⋯O and O—H⋯O hydrogen bonds into a three-dimensional network.The title compound, baeocystin or 4-phosphoryloxy- This minor tryptamine natural product was first isolated from the Psilocybe baeocystis mushroom in 1968 , the metabolite of baeocystin, as a Psilocybe natural product  in mice, which is strongly correlated with 5-HT2A receptor-mediated psychoactive effects °. The phosphoryloxy group is similarly turned away from the indole plane, with a C5—C6—O1—P1 torsion angle of 33.8 (3)°. Both groups are turned to the same side of the indole ring, which is likely supported by an intramolecular N2—H2A⋯O4 hydrogen bond  distance of 0.87 (1) Å, N—H(ammonium) distances of 0.90 (1) Å, and an O—H distance of 0.90 (1) Å. Isotropic displacement parameters were set to 1.2 Ueq of the parent nitrogen atoms and 1.5 Ueq of the parent oxygen atom. All other hydrogen atoms were placed in calculated positions . Isotropic displacement parameters were set to 1.2 Ueq of the parent carbon atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989022004467/hb8018sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022004467/hb8018Isup2.hklStructure factors: contains datablock(s) I. DOI: 2169087CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound crystallizes with two molecules in the asymmetric unit. In the crystal, asymmetric, bifurcated N—H⋯ hydrogen bonds link the molecules into [100] chains. The packing is consolidated by weak C—H⋯O interactions. 25H25N3O4, crystallizes with two molecules in the asymmetric unit. In both molecules, the central ethane hydrazide moiety is almost planar. In the crystal, asymmetric, bifurcated N—H⋯ hydrogen bonds link the molecules into [100] chains. The packing is consolidated by weak C—H⋯O interactions.The title compound, C This latter ring and the C1A toluyl ring are almost perpendicular, with a dihedral angle of 82.1 (1)°The title compound crystallizes with two molecules, B, the central ethane hydrazide moiety N2B/N3B/C17B/O3B is also close to planar, with an r.m.s. deviation of 0.01 Å for the fitted atoms. The equivalent dihedral angles to those in molecule A are 13.3 (2), 80.5 (2) and 86.1 (1)°, respectively.For molecule A and B molecules into a zigzag chain propagating in the a-axis direction, as shown in Fig. 2In the crystal, bifurcated, asymmetric N—H⋯ hydrogen bonds Table 1 link altet al., 2004o-tolyl groups at the other end of the molecule: in the current structure these are 82.1 (1) and 86.1 (1)° while in JUFCIY the equivalent angles are 46.98 (5) and 48.23 (4)°.A search for related structures resulted in two close matches. The first is the parent azide from which the current structure is derived (Chopra E)-2-(Methoxyimino)-2-{2-[(2-methylphenoxy)methyl]phenyl}ethanohydrazide  was refluxed for 8 h with p-methoxybenzaldehyde  in 20 ml of absolute ethanol with the addition of 5 drops of glacial acetic acid to obtain a white-colored product. This was dissolved in DMSO and, by the process of slow evaporation, colourless needles of the title compound grew. I. DOI: 10.1107/S2414314620010603/hb4356Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314620010603/hb4356Isup3.cmlSupporting information file. DOI: 2020760CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title hydrochloride salt, the cation shows an unusually long Si—C bond length. In the crystal, the cations and anions are linked by N—H⋯Cl hydrogen bonds to generate [001] chains. N-{[Diphenyl(vinyl)silyl]methyl}-2-methylpropan-2-amine, C19H25NSi, is a newly synthesized secondary aminomethylsilane that can be used, for example, to study carbolithiation reactions of vinylsilanes. Because the neutral compound did not crystallize well, the hydrochloride salt, C19H26NSi+·Cl−, was formed, in which the two chloride ions in the asymmetric unit have crystallographic + species. In the crystal, the cations and anions are linked by N—H⋯Cl hydrogen bonds to generate [001] chains. To further investigate the intermolecular interactions, a Hirshfeld surface analysis was performed, which showed that H⋯H, C⋯H/H⋯C and H⋯Cl/Cl⋯H contacts contribute 70.4, 20.0 and 8.3%, respectively. Because the (aminomethyl)silane 1 did not crystallize well, the hydrochloride salt 2 was formed to characterize the compound via X-ray diffraction. For example, the newly synthesized (aminomethyl)vinylsilane 1, C19H25NSi, can be used for investigations of a carbolithiation reaction of the silane’s vinyl group via lithiumalkyls. The received product can be used for the synthesis of functionalized alcohols by a Tamao oxidation silanes known to date because the synthesis is not feasible due to the high energy requirement and reaction time. With the assistance of a 2.2 crystallized in a few minutes from an aqueous 1 M HCl solution of 1 at room temperature as a hydrochloride salt, C19H26NSi+·Cl−, in the form of colorless needles in the centrosymmetric space group P21/n. The molecular structure is illustrated in Fig. 1Compound 3sp—SiX3 compounds °, which is caused by the steric repulsion of the aromatic hydrogen atoms. The Si1—C1 bond length is 1.8577 (11) Å and C1—C2 is 1.3293 (16) Å; the latter is positioned at the end of the default range of Csp2—Csp2 bonds, which lie between 1.299 and 1.328 Å.The Si1—C15 bond length in the cation is 1.9117 (10) Å, which is slightly longer than the average for an Si—C bond and the Si1—C15—N1 bond angle is 116.21 (7)°. The Si—C bond lengths are normally in the range of 1.857 to 1.905 Å for CA—N1—H1B), the angles between the C atoms and the H atoms are 107.8 (10)° (H1B—N1—C15) and 109.6 (9)° (H1A—N1—C15). Between the carbon atoms, the angle is 117.10 (7)° (C15—N1—C16). All angles vary slightly from the ideal tetrahedron angles of 109.5°: the large C—N—C angle results from the bigger space requirement of the carbon atoms in comparison to the H atoms. The sum of angles around the nitrogen atom is 441.7°, so the overall structure is distorted tetrahedral. The bond length between N1 and C15 is 1.4928 (12) Å and it is 1.5330 (13) Å between N1 and C16. In the literature, C3sp—N bond lengths are in the range of 1.4816 to 1.5034 Å, so the N1—C16 bond is slightly extended.The cationic nitrogen center features a slightly disordered tetrahedral geometry. The angle between the hydrogen atoms is 107.2 (13)°  Å. This may be due to the different surroundings of the Cl1 and Cl2 ions in the crystal. As shown in Fig. 3para-hydrogen atoms H6 with a C6⋯Cl1 distance of 4.0013 (11) Å while Cl2 accepts two weak, near linear hydrogen-bond contacts [C7—H7⋯Cl2: 165.74 (7)°] from the aromatic meta-hydrogen atoms H7 with a C7⋯Cl2 distance of 3.9419 (12) Å. Both contacts are formed by the same aromatic ring. The bond angle for N1—H1B⋯Cl2 is 164.0 (13)°, compared to 172.8 (13)° for N1—H1A⋯Cl1. They differ from the optimal angle of 180° because of the different surroundings in the crystal packing.In the extended structure of 2 Fig. 2, the cat2 Fig. 2 to generdnorm in the range from −0.54 to 1.49 arbitrary units, generated by CrystalExplorer2021  and D12(3), which means that the hydrogen bond extends from N1—H1A⋯Cl1 to another H1A—N1 grouping of a neighboring molecule. H2 can also be assigned D11(2) and D12(3) -2-methoxymethyl-1-[1-phenylethyl(dimethyl)silylmethyl]pyrrolidinium iodide, C17H30NOSi+·I−  Å] and the Si—C—N bond angle is comparable [115.86 (14)°]. The lengths between the carbon atoms and the cationic nitrogen center are similar to the corresponding bond lengths in 2 [1.498 (3) and 1.494 (3) Å].In LAGLUE, the N—H⋯Cl hydrogen bond has a slightly longer N⋯Cl separation (3.124 Å) than compound 2 but the Si—C—N bond angle is similar [114.9 (2)°] and the C—N bond is a bit extended [1.505 (6) Å]. This could be caused by the ring strain of the aziridine ring and the electron-withdrawing effect of the (nitrophenyl)sulfonyl group located at the nitrogen center. In addition, the Si—Csp2 bond length is 1.859 (7) Å, which is only slightly longer that the value for 2.In WOLSEY, the Si—C distance of 1.871 (4) Å is shorter than in Finally, in AGILIL, the Si—C bond length is slightly shorter [1.907 (7) Å] and the Si—C—N bond angle is slightly extended [120.8 (4)°], which is caused by the cyclic structure of the compound. The C—N distance is equal [1.498 (8) Å] and the cyclic N—C bond lengths marginally shorter [1.509 (8) and 1.516 (8) Å], again due to the cyclic structure.+) to 2. In WAVXAW and DAFKUT, the Si—C bond lengths are 1.9074 (11) and 1.907 (3) Å, respectively, comparable to the value in 2. These extended bond lengths are due to the same electronic effects already described.The structures of WAVXAW and DAFKUT contain a similar structure motive  was added to N-{[diphenyl(vinyl)silyl]methyl}-2-methylpropan-2-amine (1)  at room temperature. The product (2) was formed after five minutes as colorless needles.The reaction scheme for the synthesis of compound 6.A and H1B were positioned geometrically (C—H = 0.95–1.00 Å) and refined using a riding model, with Uiso(H) = 1.2Ueq(C) for CH2 and CH hydrogen atoms and Uiso(H) = 1.5Ueq(C) for CH3 hydrogen atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989022009112/hb8033sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022009112/hb8033Isup2.hklStructure factors: contains datablock(s) I. DOI: 2207007CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


IV—S bond lengths. The packing of the complexes enable intermolecular interactions between the qdt ligands  and an amine hydrogen atom (hydrogen bonding) or other qdt ligands (π–π stacking).The title compound exhibits typical Pt 8H4N2S2)2(C5H6N2)2]·C2H6OS or trans-[Pt(4-ap)2(qdt)2]·dmso  the centrosymmetric complex exhibits Pt—S distances in agreement with other PtIV—S bond lengths found in platinum(IV) dithiolene complexes. The qdt ligands have intermolecular interactions with an amine hydrogen atom on a 4-ap ligand (hydrogen bonding) and have sandwich π–π interactions with a neighboring qdt ligand.In the structure of the title solvated complex, [Pt(C These distances are similar to those in other platinum(IV) complexes containing bis(dithiolene) ligands and either trans-bis(NH3) co-ligands, with Pt—S distances of 2.3434 (8) and 2.3461 (7) Å  co-ligands, with a Pt—S distance of 2.3619 (8) Å 2(mnt)2] complex  and S2 . This tilt enables sandwich packing between intermolecular qdt ligands with a distance between centroids of the two qdt rings of 3.610 Å  atom on a neighboring qdt ligand, with a distance of 2.23 Å (Table 1The chelating qdt ligands of this platinum(IV) complex are slightly canted relative to the platinum-sulfur atoms, with a 15.59 (11)° angle between the plane of all the non-H atoms of the qdt ligand  Å Fig. 2, within Å Table 1. N—H⋯O ha3 with 25 ml of water and heating at 333 K for 5 h. Upon cooling to room temperature, the orange solution was added, via cannula, to a Schlenk flask containing 34.3 mg of [Pt(4-ap)4](BF4)2, prepared in a similar manner to [Pt(pyz)4](BF4)2 2(qdt)]). Oxidation of platinum(II) to platinum(IV) likely occurred upon prolonged air exposure of the compound in solution  I. DOI: 10.1107/S2414314622001018/wm4160Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2414314622001018/wm4160Isup3.molSupporting information file. DOI: 2145270CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title piperidine derivative, the molecules are linked by C—H⋯π interactions into dimers related by twofold symmetry. 20H21NO, the dihedral angle between the phenyl ring is 47.5 (1)° and the piperidine ring adopts a chair conformation. In the crystal, molecules are linked by C—H⋯π interactions into dimers with the molecules related by twofold symmetry.In the title compound, C This leads to dimers with the molecules related by twofold rotation symmetry  and the C6–C11 and C15–C20 benzene rings are 70.31 (11) and 79.00 (11)°, respectively. The dihedral angle between the C6–C11 and C15–C20 benzene rings is 47.51 (12)°. In the crystal, a C2—H2⋯ry Fig. 2. The N1—A mixture of hexene-2-one (0.05 mol), benzaldehyde (0.1 mol), ammonium acetate (0.05 mol) and ethanol (40 ml) was heated gently and poured into ether (50 ml) and treated with concentrated hydrochloric acid (25 ml). The precipitated hydrochloride was washed with an ethanol–ether mixture. The base was liberated by adding strong ammonia until the hydrochloride dissolved. Dilution with water afforded the free base. The pure compound was was further recrystallized with benzene–petroleum ether to yield the title compound.Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S241431462000526X/hb4345sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S241431462000526X/hb4345Isup2.hklStructure factors: contains datablock(s) I. DOI: 1996936CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II centre is coordinated by four pyrrole N atoms of the porphyrin ring and one S atom of the axial 4-methylbenzenethiolate ligand. Two tetrahydrofuran molecules and a potassium cation chelated inside a [2.2.2]cryptand  are also present.The Mn 18H36N2O6)][Mn(C44H24Cl4N4)(C7H7S)]·2C4H8O, were obtained by the solvent evaporation method. The MnII cation is coordinated by four pyrrole N atoms (Np) of the porphyrin ring and one S atom of the apical 4-methylbenzenethiolate ligand with the average Mn—Np and the apical Mn—S bond lengths being 2.160 (9) and 2.4642 (8) Å, respectively. Two tetrahydrofuran solvent molecules and a potassium cation chelated inside a [2.2.2]cryptand  are also present.Single crystals of the title compound, [K(C II porphyrin analogues are often used as substitutes and supplements for FeIII porphyrin model compounds when simulating the relevant reactions of heme-active sites, so as to provide a more comprehensive understanding of structure–function relationships in hemoproteins  [Mn(TPP)(1-MeIm)] has a large metal out-of-plane distance (Δ24 and Δ4 ≥ 0.51), and the authors suggested that when the dy2x2– orbital is populated, the metal atom is too far out of the porphyrin plane to permit effective interaction with a sixth ligand. Subsequently, some other crystal structures of five-coordinate manganese porphyrins were reported, e.g. [K(222)][Mn(TPP)(CN)] ] (p-CH3PhS−)].MnII porphyrinate, i.e. the [MnII(TpClPP)(p-CH3PhS−)]− anion, is a [K(222)]+ cation in which the potassium ion is chelated inside a [2.2.2]cryptand molecule. Six O and two N atoms of the [2.2.2]cryptand bind to the potassium cation, and the average K—O and K—N distances are 2.85 (4) and 2.989 (11) Å, respectively. There are also two tetrahydrofuran (THF) solvent molecules in the asymmetric unit, one of which is disordered.The molecular entities of the title compound are shown in Fig. 1II has a larger ionic radius than FeIII , longer M—Np (Np is a porphyrin N atom) bond lengths [2.160 (9) Å versus 2.057 (5)–2.06 (12) Å], and a longer Mn—S apical distance [2.4642 (8) Å versus 2.298 (5)–2.311 (3) Å] Cl], and [Mn(TpClPP)OH] were prepared according to a literature method ] was prepared by reduction of [MnIII(TpClPP)OH]  with ethanethiol (1.5 ml) in benzene (5 ml)  atmosphere using standard Schlenk techniques, and all solvents used were treated under anhydrous and anaerobic conditions. Benzene and tetrahydrofuran  were distilled over sodium/benzophenone. Hexane  was distilled from sodium/potassium alloy under argon. Pyrrole, Synthesis of ([2.2.2]cryptand)potassium (4-methylbenzenethiolato)manganese(II) tetrahydrofuran disolvateII(TpClPP)]  powder was dried under vacuum and then dissolved in 5 ml of tetrahydrofuran. 6.0 mg (0.050 mmol) of p-CH3PhSK and 17.0 mg (0.045 mmol) of Kryptofix 222 were added to the solution. The mixture was stirred for about 30 minutes and hexane was layered. After 2 weeks, X-ray quality dark-purple flake-shaped crystals of [K(222)][Mn(TpClPP)(p-CH3PhS−)] were obtained and a large well-formed specimen was selected for the diffraction experiment.The purple [MnA, C71A and C72A were restrained with the RIGU instruction to get a better disorder model. The refined occupancy ratio of the disordered atoms is 0.576 (7):0.524 (7).Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2414314622002413/bt4121sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2414314622002413/bt4121Isup3.hklStructure factors: contains datablock(s) I. DOI: 2142607CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-benzoylamidophosphate is reported and discussed.The crystal structure of the caesium salt of dimethyl- N-benzoylamidophosphate, namely, aqua[dimethyl (N-benzoylamido-κO)phosphonato-κO]caesium, [Cs(C9H11NO4P)(H2O)] or CsL·H2O, is reported. The compound crystallizes in the monoclinic crystal system in the P21/c space group and forms a mono-periodic polymeric structure due to the bridging function of the dimethyl-N-benzoylamidophosphate anions towards the caesium cations.The caesium salt of dimethyl- In addition, the phosphoryl or the carbonyl oxygen atom or both usually bridge the cations. Caesium salts of CAPhs have not been reported to date and are of interest as possible dopants in oxide film materials for the improvement of their electric and electron functional characteristics . The oxygen atoms of the carbonyl and phosphoryl groups of the dimethyl-N-benzoylamidophosphate anions act as μ2-bridges between Cs+ cations , and each Cs+ cation links four ligand anions. Additionally, a water molecule acts as a μ2-bridge between two Cs+ cations.The asymmetric unit contains the Csle Fig. 2a. The ons Fig. 1. Additions Fig. 2b, and e+ ion contacts nine oxygen atoms. It is involved in the six-membered Cs1–O1–C1–N1–P1–O2 ring with one ligand by bonding with the oxygen atoms of the carbonyl and phosphoryl groups, in the four-membered Cs1–O2–P1–O4 ring with another CAPh ligand by bonding with the oxygen atoms of the phosphoryl and methoxy groups and in the six-membered Cs1–O1–C1–N1–P1–O3 ring with the third ligand by bonding with the μ2-oxygen atoms of the carbonyl and methoxy groups. In addition, the Cs+ ion contacts with the μ2-O3 atom of the fourth neighboring CAPh as well as with two molecules of water , so the majority of the Cs—O contacts might be considered as a mainly ionic type of bond. The Cs1—O1 distance is the longest LH = 1.219 (6) Å, d(P—O)LH = 1.461 (4) Å] and the C—N and P—N bond lengths are decreased , 1591 [ν(CC)], 1535 [ν(CO)], 1378 [ν(CN)], 1205 [ν(PO)], 1076, 1038, 928 [ν(PN)], 838, 800, 734, 710, 540, 502,466, 452 cm−1. The low-frequency shift of ν(P=O) and ν(C=O) bands in the IR spectrum of CsL·H2O with respect to HL(ΔνLH(P=O) ∼37cm−1, ΔνLH(C=O) ∼147cm−1] is typical for bidentate coordination of dimethyl-N-benzoylamidophosphate. 1H NMR (DMSO-d6): δ = 3.24 , 3.54 , 7.27 , 8.04 . 31P NMR (acetone): δ = 15.2 (s).Cs7.Uiso(H) = 1.2–1.5Ueq(C). O-bound H atoms were refined with the restraints O5—H5A = O5—H5B = 0.84±0.01 Å and H5A⋯H5B = 1.62±0.02 Å with Uiso(H) = 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989022012166/mw2194sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989022012166/mw2194Isup2.hklStructure factors: contains datablock(s) I. DOI: 2232690CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Iclaprim and mesylate molecules are linked into a hydrogen-bonded molecular tape, the central section of which is composed of fused rings. 2H-1-benzopyran-5-yl)methyl]pyrimidin-1-ium methanesulfonate, C19H23N4O3+·CH3O3S−, is a salt made up from a protonated iclaprim molecule and a mesylate anion. The pyrimidine and chromene units of the iclaprim molecule form an orthogonal arrangement [interplanar angle of 89.67 (6)°], and the 3-nitrogen position of the pyrimidine ring is protonated. Four distinct N—H⋯O interactions and an additional N—H⋯N hydrogen bond connect iclaprim and mesylate molecules to one another, resulting in an infinite hydrogen-bonded molecular tape structure. The central section of the tape is formed by a sequence of fused hydrogen-bonded rings involving four distinct ring types.The title compound, 2,6-diamino-5-[(2-cyclopropyl-7,8-dimethoxy- Iclaprim was synthesized according to the original route described by Jaeger  al. 2005, using 32.3SO3− anion and an iclaprim cation in which the 3-nitrogen atom of the pyrimidine ring is protonated, i.e. N1  with the fused benzene ring of the chromene unit . With regard to the two bridging bonds, the torsion angles C3—C4—C5—C6 [–160.8 (2)°] and C4—C5—C6—C7 [–96.5 (3)°] indicate that the C5—C6 bond is twisted slightly out of the pyrimidine plane, whilst the C4—C5 bond is oriented approximately perpendicular to the benzene ring. Accordingly, the two six-membered rings linked via C5 form an orthogonal arrangement with an interplanar angle of 89.67 (6)°. In the chromene moiety, the 7-methoxy substituent is significantly twisted out of the ring plane [C10—C9—O3—C19 = −70.3 (3)°], whilst the 8-methoxy substituent is almost coplanar with the plane of the fused benzene ring [C9—C8—O2—C18 = 167.6 (2)°]. The 2H-pyran ring displays the expected bond lengths [C12—C13 = 1.323 (4) Å]. The program PLATON °, φ = 328.4 (7)° and q = 0.253 (3) Å, are consistent with the presence of a skew-boat conformation N1 Fig. 1. The mol3.2 groups attached to the pyrimidine ring  and the protonated N1 atom of the pyrimidine ring as potential hydrogen-bond donor groups. These hydrogen-bond donor functions are engaged in five distinct intermolecular N—H⋯A interactions .Iclaprim mesylate was prepared according to a modified procedure based on the original synthesis by Jaeger  al. 2005 shown in6.a axis. The refined value of the minor twin component fraction was 0.260 (1). All H atoms were identified in difference-Fourier maps and those of NH and NH2 groups were refined with a restrained N—H distance of 0.88 (2) Å and their Uiso parameters refined freely. The H atoms at the cyclopropyl ring  were refined with a restrained C—H distance of 0.96 (2) Å and with Uiso(H) = 1.2Ueq(C). Other H atoms bonded to secondary CH2 (C—H = 0.98 Å) or aromatic CH (C—H = 0.94 Å) carbon atoms were positioned geometrically. Their Uiso parameters were set to 1.2Ueq(C). Methyl H atoms were idealized and included as rigid groups allowed to rotate but not tip (C—H = 0.97 Å) and their Uiso parameters were set to 1.5 Ueq(C) of the parent carbon atom.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989022011689/wm5666sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022011689/wm5666Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022011689/wm5666Isup3.cmlSupporting information file. DOI: 2224639CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


N-butyl-2,3-bis(dicyclohexylamino)cyclopropenimine is reported.The structure of the acid chloride salt of the superbase  N-Butyl-2,3-bis(dicyclohexylamino)cyclopropenimine (1) crystallizes from benzene and hexanes in the presence of HCl as a monobenzene solvate of the hydrochloride salt, [1H]Cl·C6H6 or C31H54N3+·Cl−·C6H6, in the P21/n space group. The protonation of 1 results in the generation of an aromatic structure based upon the delocalization of the cyclopropene double bond around the cyclopropene ring, giving three intermediate C—C bond lengths of ∼1.41 Å, and the delocalization of the imine-type C—N double bond, giving three intermediate C—N bond lengths of ∼1.32 Å. Ion–ion and ion–benzene packing interactions are described and illustrated. Originally reported as four-electron Lewis donors cyclopropenimine (1) is a newer version of superbase with improved basicity, which has been explored as a catalyst for ring-opening polymerization. Cyclopropenimines have a conjugate acid apK of about 27, an improvement over that of the superbase 2-tert-butyl-1,1,3,3-tetramethylguanidine (BTMG), which has a apK of 23.56  Å on average. The C—N bond to the protonated butyl nitrogen is only slightly shorter at 1.319 (2) Å. The three cyclopropene C—C bonds exhibit lengths consistent with aromaticity; the unique C—C bond opposite the n-butyl group is 1.388 (2) Å, while the other two C—C bonds are similar or slightly shorter at 1.377 (2) and 1.383 (2) Å. Though these latter two bonds are equivalent under molecular point symmetry, their differences are attributed to the asymmetric crystal packing environment of the P21/n space group. The comparable nature of the bond metrics of the three C—N bonds and the three cyclopropenyl C—C bonds is consistent with aromatization, and an analogous aromatization of the C3N3 core of 1-mesityl-2,3-bis(diisopropylamino)cyclopropeniminium tetrafluoroborate was observed in the crystal structure of this salt , which ranges from about 6–25 kJ mol−1 per π electron , and 2.7169 (6) Å from an intramolecular axial cyclohexyl proton, H29A (+0.050). The crystal packing demonstrates that the C3N3 planes of all molecules pack parallel to each other (as required by the space-group symmetry), with a normal slightly oblique to the (101) plane  Å, Fig. 3n-butyl chain Cl·C6H6 were observed inside. The yield of crystalline [1H]Cl·C6H6 was significantly improved by the addition of HCl. To a glass shell vial containing 7.2 mg of N-butyl-2,3-bis(dicyclohexylamino)cyclopropenimine, 2 mL of benzene were added. A drop of dilute HCl (0.730 M) was added. This was diffused with 3 mL of hexanes in the outer vial for 2–3 days. Crystallization works best when the drop is not in contact with the walls of the vial where the crystals grow. Crystals were isolated by decanting the liquid from the inner vial using a disposable pipette, and taking care to remove the visible aqueous HCl droplet with the first pipette draw. After removing the mother liquor, the crystals were rinsed with hexanes. Yield 6.3 mg (70%). Yields in this small-scale preparation ranged from 22% to 70% across multiple attempts. 1H NMR (ppm) 400 MHz, CDCl3): δ(ppm): 0.97 , 1.62–1.82 , 1.62–1.76 , 1.80 , 1.96 , 3.34 , 3.56 , 7.4 . 13C NMR (ppm) : δ(ppm): 13.97, 19.94, 24.58, 25.84, 32.34, 33.79, 46.15, 59.55, 114.01, 128.35. FTIR (cm−1): 2926 (m), 2851 (m), 1503 (s), 1445 (m), 1383 (w), 1374 (w), 1345 (w), 1324 (w), 1253 (w), 1188 (w), 1180 (w), 1102 (w), 1092 (w), 1004 (w), 895 (w), 696 (m). Analysis calculated for C31H53N3·0.5 C6H6 (%): C, 76.31; H, 10.38; N, 7.22. Found: C, 75.873; H, 10.83; N, 7.24. M.p. 353–356 K (decomposes).Initially, crystals of Cl·C6H6 using ORCA  I. DOI: 10.1107/S2056989022008076/jq2013Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022008076/jq2013Isup3.cdxSupporting information file. DOI: 2200141CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Anopheles gambiae sensu lato (s.l.) mosquitoes to pyrethroids and their expression of metabolic enzymes.Malaria remains one of the most devastating diseases globally, and the control of mosquitoes as the vector is mainly dependent on chemical insecticides. Elevated temperatures associated with future warmer climates could affect mosquitoes' metabolic enzyme expression and increase insecticide resistance, making vector control difficult. Understanding how mosquito rearing temperatures influence their susceptibility to insecticide and expression of metabolic enzymes could aid in the development of novel tools and strategies to control mosquitoes in a future warmer climate. This study evaluated the effects of temperature on the susceptibility of Anopheles gambiae s.l. eggs obtained from laboratory-established colonies were reared under eight temperature regimes . Upon adult emergence, 3- to 5-day-old female non-blood-fed mosquitoes were used for susceptibility tests following the World Health Organization (WHO) bioassay protocol. Batches of 20–25 mosquitoes from each temperature regime (25–34 °C) were exposed to two pyrethroid insecticides (0.75% permethrin and 0.05% deltamethrin). In addition, the levels of four metabolic enzymes  were examined in mosquitoes that were not exposed and those that were exposed to pyrethroids.An. gambiae s.l. mosquitoes exposed to deltamethrin and permethrin decreased at temperatures above 28 °C. In addition, mosquitoes reared at higher temperatures were more resistant and had more elevated enzyme levels than those raised at low temperatures. Overall, mosquitoes that survived after being exposed to pyrethroids had higher levels of metabolic enzymes than those that were not exposed to pyrethroids.Mortality in An. gambiae s.l. mosquitoes' susceptibility to pyrethroids and increased the expression of metabolic enzymes. This evidence suggests that elevated temperatures projected in a future warmer climate could increase mosquitoes' resistance to insecticides and complicate malaria vector control measures. This study therefore provides vital information, and suggests useful areas of future research, on the effects of temperature variability on mosquitoes that could guide vector control measures in a future warmer climate.This study provides evidence that elevated temperatures decreased The online version contains supplementary material available at 10.1186/s13071-022-05273-z. Anopheles gambiae could affect malaria control measures. The An. gambiae complex consists of nine morphologically identical sibling species. They include An. gambiae sensu stricto (s.s.), An. arabiensis, An. merus, An. melas, An. quadriannulatus, An. amharicus, An. bwambae, An. coluzzii, and An. fontenillei ) were first used to identify species of the protocol . Subsequectively . The PCRAn. gambiae s.l. mosquitoes  raised at 25, 28, 30, 32, and 34 °C. Permethrin and deltamethrin insecticides were selected because they are the most common insecticides used in malaria control programs  compared to those reared at 34 °C [1.94 × 10–9 ], 30 °C [1.49 × 10–9 ], 28 °C [8.85 × 10–10 ], and 25 °C [7.21 × 10–10  mol cytochrome P450/min/mg protein]  with increasing temperature. Dunn's multiple range test showed that all but 30 vs 28 °C (P = 0.113) and 34 vs 30 °C (P = 0.010) showed a statistically significant difference in oxidase level  mol cytochrome P450/min/mg protein] levels compared to those reared at 32 °C [2.40 × 10–9 ], 25 °C [2.07 × 10–9 ], and 28 °C [1.34 × 10–9  mol cytochrome P450/min/mg protein]  in MFO levels among the different temperature regimes. Further tests using Dunn's multiple range test showed a significant difference (P < 0.008) in the various temperature regime comparisons , 28 °C , and 30 °C  and not exposed to pyrethroids were significantly lower than those that were exposed to pyrethroids. However, mosquitoes reared at 32 °C and not exposed to pyrethroids had significantly higher  MFO levels than those exposed to pyrethroids  in the GST levels in mosquitoes among the different temperature regimes. However, further analysis using Dunn's multiple range test showed statistically significant differences for 32 vs 25 °C (P < 0.001), 34 vs 25 °C (P = 0.002), 32 vs 28 °C (P < 0.001), 32 vs 30 °C (P < 0.001), and 34 vs 32 °C (P < 0.001)  similar to that of the MFO level ], followed by 25 °C [2.72 × 10–3 ], 30 °C [2.62 × 10–3 ] and the lowest recorded at 28 °C [1.35 × 10–3  mol cDNB/min/mg protein]  in the GST level in mosquitoes among the different temperature regimes. Further statistical tests using Dunn's multiple range test showed statistically significant differences for 28 vs 25 °C (P = 0.002), 32 vs 28 °C (P < 0.001), and 32 vs 30 °C (P = 0.005)  showed a statistically significant difference in GST levels ], followed by 34 °C [4.04 × 10–7 ], 28 °C [2.83 × 10–7 ], 25 °C [2.52 × 10–7 ] and 30 °C [2.12 × 10–7  mol α-naphthol/min/mg protein]  in α-esterase level in mosquitoes among the different temperature regimes. Further statistical tests using Dunn's multiple range test showed a statistically significant difference for 32 vs 25 °C (P < 0.001), 34 vs 25 °C (P < 0.001), 32 vs 28 °C (P < 0.001), 32 vs 30 °C (P < 0.001), 34 vs 30 °C (P < 0.001), and 34 vs 32 °C (P < 0.001) ] and lowest at 28 °C [1.44 × 10–7 (2.40 × 10–7) mol α-naphthol/min/mg protein]  in α-esterase levels in mosquitoes among the different temperature regimes. According to Dunn's multiple range tests, a statistical difference existed only for 30 vs 28 °C (P = 0.003) and 32 vs 28 °C (P = 0.001)  showed a statistically significant difference in α-esterase level ] > 32 °C [2.87 × 10–7 ] > 28 °C [1.38 × 10–7 ] > 25 °C [1.36 × 10–7 ] > 30 °C [1.30 × 10–7  mol β-naphthol/min/mg protein]  in β-esterase levels in mosquitoes with increasing temperature. However, post hoc analysis using Dunn's multiple range test showed a statistically significant difference for 32 vs 25 °C (P = 0.001), 34 vs 25 °C (P < 0.001), 34 vs 28 °C (P < 0.001), 34 vs 30 °C (P < 0.001), and 34 vs 32 °C (P = 0.003)  at 28 °C to 2.64 × 10–7 (1.63 × 10–7) mol β-naphthol/min/mg protein at 32 °C  in β-esterase levels in mosquitoes raised at different temperatures. Multiple comparisons using Dunn's test showed statistically significant differences for 28 vs 25 °C (P < 0.001), 30 vs 28 °C (P < 0.001), 32 vs 28 °C (P < 0.001), and 32 vs 30 °C (P = 0.007)  in β-esterase levels  to pyrethroids decreased with increasing temperature. Another important finding was that deltamethrin induced higher mortality in mosquitoes than permethrin, indicating that mosquitoes were resistant to permethrin based on WHO criteria [An. gambiae s.l. mosquitoes were more susceptible to deltamethrin than permethrin. With projections of warmer temperatures in coming years, especially in sub-Saharan Africa, high resistance to pyrethroids with increasing temperatures could affect the effectiveness of malaria control programs using pyrethroids [Mosquito susceptibility to pyrethroids decreased with increasing temperature. This may be attributed to the higher expression of enzymes at high temperatures . At highcriteria . These fcriteria . This cocriteria , which sethroids . In Ghanethroids , and anyDrosophila melanogaster adapted to high temperatures as compared with those acclimatized to low temperatures [With regard to metabolic enzymes, MFO and GST levels in mosquitoes that were not exposed to pyrethroids increased with increasing temperature from 25 to 32 °C. On the other hand, enzyme expression levels decreased at 34 °C, suggesting that enzyme expression may be impaired above a certain optimum temperature range . In addieratures . The eleeratures .An. gambiae s.s. mosquitoes exposed to permethrin insecticides were higher than in mosquitoes that were not exposed to insecticides.Comparing the enzyme levels in mosquitoes that were not exposed and those exposed to pyrethroids, levels of MFO, GST, α-esterase, and β-esterase were higher in those exposed to pyrethroids than in those that were not exposed, especially at 25 and 30 °C. The high resistance of mosquitoes to insecticides might have involved metabolic detoxification due to the elevated enzyme expression in mosquitoes exposed to pyrethroids . These fAn. arabiensis mosquitoes. However, the findings of the current study are contrary to those reported by Leong et al. [A. aegypti mosquitoes. These findings raise the possibility that the levels of metabolic enzymes may differ among mosquito species [The study further revealed that MFO was the least expressed enzyme in mosquitoes. The findings are in agreement with those of Alemayehu et al. , who obsg et al. , who fou species . TherefoAn. gambiae s.l. mosquitoes' susceptibility to insecticides and metabolic enzyme expression. The results suggest that An. gambiae s.l. mosquitoes reared at higher temperatures have increased insecticide resistance than those reared at lower temperatures. In addition, increased rearing temperatures of An. gambiae s.l. mosquitoes were associated with increased expression of metabolic enzymes. Increased metabolic enzyme levels are usually associated with insecticide resistance. This suggests that elevated temperatures projected in a future warmer climate could increase mosquitoes' resistance to insecticides and thus reduce the effectiveness of vector control measures for diseases such as malaria. Therefore, it is essential to research new tools for vector management rather than depending only on chemical insecticides.This study contributes to the knowledge of the effects of temperature variability on Additional file 1: Table S1. Ambient and rearing water conditions for each temperature regime. Table S2. Mortality in An. gambiae s.l. mosquitoes exposed to pyrethroids. Table S3. Median levels of metabolic enzymes in An. gambiae s.l. mosquitoes reared at different temperature regimes. Table S4. Pairwise comparisons of enzyme levels in An. gambiae s.l. mosquitoes reared at different temperature regimes. Table S5. Mann–Whitney U-test between mosquitoes that were not exposed and those exposed to pyrethroids.


H = DSz2 − γNV(Sx(BAx + Bx) + Sy(BAy + By) + Sz(BAz + Bz))”. It should read “H = DSz2 − γNV(Sx(BAx + Bx) + Sy(BAy + By) + Sz(BAz + Bz))”. On line 7 in the left column on page 180 of the original article, the text originally read “Bmin ≅ 4 Γ (33 γNV × C)−1 (I0 × t)−1”. It should read “Bmin ≅ 4 Γ (3√3 γNV × C)−1 (I0 × t)−1/2”. On line 23 in the left column on page 180 of the original article, the text originally read “S = Fl(f1) − Fl(f2))/(Fl(f1) + Fl(f2)”. It should read “S = (Fl(f1) − Fl(f2))/(Fl(f1) + Fl(f2))”.The authors regret that there were errors that appear in the Results and discussion section. On line 47 in the right column on page 179, the text originally read “The authors regret that there was an error in the text in the Author contributions section on line 24 in the right column on page 183 of the original article. The text originally read “ASQ”. It should read “SQAS”.The Royal Society of Chemistry apologises for these errors and any consequent inconvenience to authors and readers.


The hypoxanthinium and xanthinium cations in salts I and II are both in the oxo-N(9)–H tautomeric form. The crystal packing of the two salts is governed predominantly by N—H⋯O, N—H⋯Br, C—H⋯Br and O—H⋯Br interactions described by Two new crystalline salts, namely, hypoxanthinium bromide monohydrate, C 5H5N4O+·Br−·H2O (I) and xanthinium bromide monohydrate, C5H5N4O2+·Br−·H2O (II), were synthesized and characterized by single-crystal X-ray diffraction technique and Hirshfeld surface analysis. The hypoxanthinium and xanthinium cations in salts I and II are both in the oxo-N(9)–H tautomeric form. The crystal packing of the two salts is governed predominantly by N–H⋯O, N–H⋯Br, C–H⋯Br and O–H⋯Br interactions described by R23(9) and R22(8) synthons. The crystal packing is also consolidated by carbonyl⋯π interactions between symmetry-related hypoxanthinium (+HX) cations in salt I and xanthinium cations (+XA) in salt II. The combination of all these interactions leads to the formation of wave- and staircase-like architectures in salts I and II, respectively. The largest contributions to the overall Hirshfeld surface are from Br⋯H/H⋯Br contacts (22.3% in I and 25.4% in II) .Two new crystalline salts, namely, hypoxanthinium bromide monohydrate, C Similarly, xanthinium nitrate monohydrate, xanthinium hydrogensulfate monohydrate  crystallizes in the monoclinic space group P21/c with one hypoxanthinium cation (+HX), one bromide anion (−Br) and one water molecule in the asymmetric unit, as shown in Fig. 1+HX cation exists in the oxo-N(9)–H tautomeric form with the N7 atom of the purine ring protonated, as can be seen from the N—C bond distance [N7—C8 = 1.3219 (17) Å vs N9—C8 = 1.3419 (18) Å] and C—N—C bond angles [C5—N7—C8 = 107.98 (11)° and C4—N9—C8 = 108.32 (10)°]. Those values are similar to those in the crystal structure of hypoxanthinium chloride monohydrate  shorter than N9–C8 one [1.344 (5) Å]. The C—N—C bond angles are C5—N7—C8 = 108.2 (3)° and C4—N9—C8 = 107.7 (3)° and, therefore, the cation can also be described as the oxo-N(9)–H tautomer. These values are similar to those in xanthinium perchlorate dihydrate  . The dimer is flanked on both sides by a water molecule (O1W), forming a pair of O1W—H2W⋯O2iv and O1W—H1W⋯O6ii hydrogen bonds with an HDADA array  along the ac plane. Neighbouring tetrameric units are then connected through two sets of W and O1W—H1W⋯O6ii hydrogen bonds and an L) motif formed by a pair of O1W—H1W⋯O6ii interactions. The tetrameric units combine into a supramolecular ribbon extended along the ac plane  of the +XA unit) with C=O⋯Cg2vi and C=O⋯Cg2vii distances of 3.366 (3) and 3.477 (3) Å, respectively, and angles of 108.2 (2) and 118.7 (2)° [symmetry codes: (vi) 1 + x, y, z; (vii) 1 − x, 1 − y, 1 − z; Fig. 8In the crystal structure of salt s Table 2 with an ne Fig. 5. Neighbo4.et al., 2007Crystal Explorer 17.5  interactions  or shorter (red) than the sum of the van der Waals radii of the two interacting atoms. The Hirshfeld surfaces of salts I and II are shown in Fig. 9a and 10aI and II and the respective neighbouring moieties are shown in Fig. 9b and 10bI and II are shown in Figs. 11I 19.7%, II 23.4%), N⋯H/H⋯N  C⋯H/H⋯C , H⋯H/H⋯H  and C⋯C/C⋯C  (Table 5), indicating that the most abundant contact is Br⋯H/H⋯Br with 22.3% in I and 25.4% in II, respectively.Hirshfeld surface analyses and their associated two-dimensional fingerprint plots   and xanthinium bromide monohydrate (II) using the following quantities: 0.0340 mg (0.25mmol) of hypoxanthine for I and 0.0380 mg (0.25 mmol) of xanthine for II.A general method was used for the preparation and crystallization of the hypoxanthinium bromide monohydrate (The indicated amount of the base was dissolved in 20 mL of distilled water and 2 mL of hydrobromic acid (5% in water) were added. The reaction mixture was heated to 358 K for 30 min using a water bath. The resulting solution was allowed to slowly evaporate at room temperature. After a few days, colourless plate-like crystals were obtained.8.I and II are summarized in Table 4Uiso(H) = 1.2Ueq (C). The H atoms of the water molecule were located in a difference-Fourier map and refined with the O—H distance restrained to 0.85–0.86 Å and with Uiso(H) = 1.5 Ueq(O). The hydrogen atoms bound to the nitrogen atoms in salts I and II were located in difference-Fourier maps and either refined freely (in I) or with the distance restraint N—H = 0.82 Å and with Uiso(H) = 1.2Ueq(N) (in II).Crystal data, data collection and structure refinement details for salts 10.1107/S2056989022005278/jq2017sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989022005278/jq2017Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989022005278/jq2017Isup4.cmlSupporting information file. DOI: 10.1107/S2056989022005278/jq2017IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989022005278/jq2017IIsup5.cmlSupporting information file. DOI: 2170923, 2170922CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


C—H⋯O and C—H⋯F hydrogen bonds link molecules in the crystal into layers parallel to (011). The crystal packing is consolidated through C—Br⋯π and C—F⋯π interactions, as well as π–π stacking interactions. 14H8Br2FN3O2, the 4-fluorophenyl ring and the nitro-substituted phenyl ring form a dihedral angle of 64.37 (10)°. Molecules in the crystal are connected by C—H⋯O and C—H⋯F hydrogen bonds into layers parallel to (011). The crystal packing is consolidated by C—Br⋯π and C—F⋯π interactions, as well as by π–π stacking interactions. According to a Hirshfeld surface analysis of the crystal structure, the most significant contributions to the crystal packing are from O⋯H/H⋯O (15.0%), H⋯H (14.3%), Br⋯H/H⋯Br (14.2%), C⋯H/H⋯C (10.1%), F⋯H/H⋯F (7.9%), Br⋯Br (7.2%) and Br⋯C/C⋯Br (5.8%) contacts.In the title compound, C Depending on the attached substituents, azo compounds have attracted attention because of their high synthetic potential for organic and inorganic chemistry and numerous useful properties. For example, azo dyes find applications in the design of functional materials attributed to smart hydrogen bonding, as self-assembled layers, photo-triggered structural switching, liquid crystals, ionophors, indicators, semiconductors, spectrophotometric reagents for determination of metal ions, catalysts, photoluminescent materials, optical recording media, spin-coating films and antimicrobial agents -1--2-(4-fluorophenyl)diazene, the molecular and crystal structure of which along with a Hirshfeld surface analysis are reported here.In the above context, we have attached F, Br and NO2.trans-configured with regard to the N=N double bond and are practically coplanar as revealed by the C2—N2=N3—C9 torsion angle of −178.63 (16)°. All of the bond lengths and angles in the title compound are similar to those for the related azo compounds reported in the Database survey section.The molecular conformation of the title compound is not planar, as seen in Fig. 13.Cg1  = 3.6016 (9) Å, C1—Br1⋯Cg1 = 104.24 (7)°] and C—F⋯π  interactions, and weak π–π stacking , where Cg1 and Cg2 are the centroids of the C3–C8 and C9–C14 rings, respectively,  Table 1–4 ▸ ▸. 4.Crystal Explorer 17.5  to 1.1463 (blue) a.u. -1--2-phenyldiazene moiety resulted in 27 hits. Eight compounds are closely related to the title compound, viz. those with CSD refcodes GUPHIL (I)        , molecules are linked into inversion dimers via short halogen⋯halogen contacts  compared to the van der Waals radius sum of 3.50 Å for two chlorine atoms. No other directional contacts could be identified, and the shortest aromatic ring centroid separation is greater than 5.25 Å. In the crystals of (II) and (III), molecules are linked through weak X⋯Cl contacts [X = Cl for (II) and Br for (III)], C—H⋯Cl and C—Cl⋯π interactions into sheets lying parallel to (001). In the crystal of (IV), molecules are stacked in columns parallel to [100] via weak C—H⋯Cl hydrogen bonds and face-to-face π–π stacking interactions. The crystal packing is further consolidated by short Cl⋯Cl contacts. In (V), molecules are linked by C—H⋯O hydrogen bonds into zigzag chains running parallel to [001]. The crystal packing also features C—Cl⋯π, C—F⋯π and N—O⋯π interactions. In (VI), C—H⋯N and short Cl⋯Cl contacts are observed, and in (VII), C—H⋯N and C—H⋯O hydrogen bonds and short Cl⋯O contacts occur. In the crystal of (VIII), molecules are linked into chains running parallel to [001] by C—H⋯O hydrogen bonds. The crystal packing is consolidated by C—F⋯π interactions and π–π stacking interactions, and short Br⋯O [2.9828 (13) Å] contacts are also observed.In the crystal of (6.ababE)-1-(4-fluorophenyl)-2-(4-nitrobenzylidene)hydrazine (1 mmol), tetramethylethylenediamine , CuCl  and CBr4 (4.5 mmol). After 1–3 h , the reaction mixture was poured into a 0.01 M HCl solution , and extracted with dichloromethane (3 × 20 ml). The combined organic phase was washed with water (3 × 50 ml), brine (30 ml), dried over anhydrous Na2SO4 and concentrated in vacuo using a rotary evaporator. The residue was purified by column chromatography on silica gel using appropriate mixtures of hexane and dichloromethane (v/v 3/1–1/1). Light-orange solid (yield 52%); m.p. 377 K. Analysis calculated for C14H8Br2FN3O2 (M = 429.04): C 39.19, H 1.88, N 9.79; found: C 39.17, H 1.85, N 9.76%. 1H NMR  δ 7.36–7.14 . 13C NMR  δ 164.35, 153.13, 152.46, 133.69, 133.24, 131.74, 127.98, 127.89, 127.75, 127.42, 119.07, 89.02. ESI–MS: m/z: 430.06 [M + H]+. Crystals suitable for X-ray analysis were obtained by slow evaporation of an ethanol solution.The title compound was synthesized according to a reported method  = 1.2Ueq(C). The maximum electron density in the final difference map is located 0.75 Å from atom Br1, while the minimum electron density is located 0.72 Å from Br2.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989022004388/wm5642sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989022004388/wm5642Isup2.hklStructure factors: contains datablock(s) I. DOI: 2168678CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Colorless, block-shaped crystals were grown in a potassium hydroflux, i.e. under ultra-alkaline conditions, within 10 h. K2SeO3 crystallizes isostructural with Na2SO3 and K2TeO3 in the trigonal space group Pa = 6.1063 (4) Å and c = 6.9242 (4) Å at 100 (1) K. In the trigonal–pyramidal, C3v-symmetric [SeO3]2– anion, the bond length is 1.687 (1) Å, and the bond angle is 103.0 (1)°. Two of the three unique potassium cations exhibit a coordination number of six, and the third a coordination number of nine.Crystal structure data for potassium orthoselenate(IV), K K2Se2O5  are a long-known but poorly studied class of compounds. After the discovery of the first salts of selenic acid by Berzelius, comprehensive studies on these salts were not carried out until the beginning of the 1930s, when Janitzki reported the syntheses of sodium and potassium salts of selenic acid 2] , K2.2SeO3, one selenium atom , three potassium atoms  and one oxygen atom . The unit cell of K2SeO3 is depicted in Fig. 1C3v-symmetric [SeO3]2– anion can be attributed to the electron lone pair of the selenium(IV) atom. This oxidation state is supported by the bond-valence sum calculation  = ∑exp [(RSeO – dSeO)/b)] = 3 · exp [(1.811 Å – 1.687 (1) Å) / 0.37 Å)] = 4.2 valence units. The potassium cations K1 and K2 are octahedrally coordinated by oxygen atoms with K—O distances of 2.631 (1) and 2.771 (1) Å, respectively. K3 has nine oxygen neighbors at distances of 2.792 (1), 3.020 (1) Å, and 3.474 (1) Å  groups is responsible for the symmetry reduction to PK4.2SeO3, was synthesized in a potassium hydroxide hydroflux with a molar water-base ratio of 1.7. The reaction was carried out in a PTFE-lined 50 mL Berghof-type DAB-2 stainless steel autoclave to prevent evaporation of water. The starting material SeO2  was dissolved in 3 ml of water before adding 6.3 g of KOH . After closing the autoclave, the reaction mixture was heated to 473 K at a rate of 2 K min−1 and, after 8 h, cooled to room temperature at a rate of −1 K min−1. The solid reaction product was washed twice with 2 ml of methanol on a Schlenk frit under inert conditions to remove adherent hydroflux. The colorless, block-shaped crystals of K2SeO3 , KO3 Fig. 4 dissolveO3 Fig. 4. Due to JANA2006 was used . The composition of selected single crystals was determined by semi-quantitative energy dispersive X-ray analysis (Ua = 15 kV) using a Silicon Drift Detector X–MaxN (Oxford Instruments). The data were processed applying the AZtec software package  global, I. DOI: 10.1107/S2056989022005175/wm5645Isup2.hklStructure factors: contains datablock(s) I. DOI: 2172487CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Correction: BMC Neuroscience (2022) 23:68 10.1186/s12868-022-00754-4fMRI data acquisition section.Following the publication of the original article , an errobold typeface.The updated text is given below, and the changes have been highlighted in fMRI data acquisition8°, 256 × 256 matrix, voxel size 0.7 × 0.7 × 0.7 mm3. For the resting state scans before and after stress induction (RS1 and RS2), 355 volumes of T2*-weighted echo-planar images were acquired for each session with the following parameters: 34 axial slices covering the whole brain, repetition time = 2000 ms, echo time = 30 ms, flip angle = 90°, 9696 matrix, field of view = 240,240 mm2, voxel size = 2.5 × 2.5 × 3 mm3.A Philips 3T scanner was used for fMRI data acquisition. Structural T1-weighted images for spatial normalization were measured using a turbo field echo sequence with the following parameters: 274 sagittal slices covering the whole brain, flip angle = Moreover, the authors identified an error in Table 1. The correct Table Finally, the authors identified an error in Fig. 4. The correct Fig. The original article  has been