Proc. R. Soc. A472, 20160062 (Published online May 4 2016) (doi:10.1098/rspa.2016.0062)K is symmetrical with respect to η. More generally they should be replaced by periodic boundary conditions on — The Neumann boundary conditions (3.6), (3.9), (3.26), (A 11), (A 15), (A 22), (A 27) and (A 31) are applicable only when — Equation (4.25) should read— Equations (4.26) and (4.27) should read— The two lines following equation (4.30) should read:Ω+ with Γ, and Ω+ with Γ, with both where — The line following equation (4.33) should read:Ω− with Γ, andwhere — Equation (A 18) should read:


III ions (each with site symmetry 2..) in the title compound have a distorted octahedral coordination environment with four N atoms of a cyclam ligands and two chloride ions or one oxalate bidentate ligand in a cis position whereby the cyclam ligands adopt a cis-V conformation. The crystal packing is stabilized by extensive hydrogen-bonding interactions among the cyclam N–H groups, the Cl ligands, and O atoms of the oxalate and ClO4− anions.Two Cr 2(C10H24N4)][Cr(C2O4)(C10H24N4)](ClO4)2 , there are two independent halves of the [CrCl2(cyclam)]+ and [Cr(ox)(cyclam)]+ cations, and one perchlorate anion. In the complex cations, which are completed by application of twofold rotation symmetry, the CrIII ions are coordinated by the four N atoms of a cyclam ligand, and by two chloride ions or one oxalate bidentate ligand in a cis arrangement, displaying an overall distorted octahedral coordination environment. The Cr—N(cyclam) bond lengths are in the range of 2.075 (5) to 2.096 (4) Å while the Cr—Cl and Cr—O(ox) bond lengths are 2.3358 (14) and 1.956 (4) Å, respectively. Both cyclam moieties adopt the cis-V conformation. The slightly distorted tetrahedral ClO4− anion remains outside the coordination sphere. The supramolecular architecture includes N—H⋯O and N—H⋯Cl hydrogen bonding between cyclam NH donor groups, O atoms of the oxalate ligand or ClO4− anions and one Cl ligand as acceptors, leading to a three-dimensional network structure.In the asymmetric unit of the title compound, [CrCl Each cyclam moiety exhibits point group symmetry ..2 and can be described as being in the cis-V (anti–anti) conformation 2(cyclam)]ClO4 [2.069 (3)–2.103 (3) Å] 2(cyclam)]NO2 [2.0874 (16)–2.0916 (15) Å] 2·0.5H2O [2.070 (5)–2.089 (5) Å] 2(cyclam)]NCS [2.0851 (14)–2.0897 (14) Å] 2(cyclam)]ClO4 [2.046 (2)–2.060 (2) Å] 2(cyclam)]BF4 [2.064 (4)–2.073 (4) Å] 2(cyclam)][ZnCl4]Cl·H2O [2.0501 (15)–2.0615 (15) Å] 2(cyclam)]ClO4 [2.058 (4)–2.064 (4) Å] 2]2ZnCl4 2(Me2tn)2]ClO4·2H2O 2(Me2tn)2]SCN·0.5H2O F2]ClO4  Å for the oxalate ligand is close to the mean of 1.959 (4) Å found in [Cr(ox)(cyclam)]ClO4  Å is comparable to those found in cis-[CrCl2(cyclam)]ClO4 [2.331 (2) Å] ]ClO4 [2.3157 (7) Å] 2]2ZnCl4 [2.3112 (6) Å] 2]Cl [2.3253 (7) Å] °, while the Cl1B—Cr1B—ClBi angle is 89.11 (9)° [symmetry code: (i) –x + y + z]. The folded angles of the cyclam in [CrCl2(cyclam)]+ and [Cr(ox)(cyclam)]+ cations are 93.7 (2) and 97.5 (2)°, respectively. The significant distortion of the octahedral coordination sphere and the larger folded angle in the [Cr(ox)(cyclam)] + cation seem to arise from the small bite angle of the oxalato ligand. The tetrahedral ClO4− anion remains outside the coordination sphere of two CrIII ions. It is distorted due to its involvement in hydrogen-bonding interactions. Cl—O bond lengths range from 1.426 (5) to 1.443 (5) Å and the O—Cl—O angles from 107.8 (4)–111.0 (3)°.The asymmetric unit contains two halves of the [CrClon Fig. 1. In eachon Fig. 1. The Cr—+ cation while N—H⋯O and N—H⋯Cl contacts interconnect two [Cr(ox)(cyclam)]+ and one cis-[CrCl2(cyclam)]+ cation (cyclam)]n Table 1 and 3 ▸.et al., 2016cis-[CrL2(C10H24N4)]+ unit. The crystal structure of cis-[CrCl2(cyclam)]ClO4 2(cyclam)]ClO4 2(cyclam)](ClO4)Cl2 2)(cyclam)]NO2 2·0.5H2O 2(cyclam)]NCS ][Cr(ox)(cyclam)]2+ with any anion has been deposited.A search of the Cambridge Structural Database ]ClO4 and [Cr(ox)(cyclam)]ClO4, were prepared according to literature methods ][Cr(ox)(cyclam)](ClO4)2, was prepared by mixing concentrated equimolar aqueous solutions of the two starting compounds. A saturated solution of NaClO4 was added to the resulting solution for crystallization, and allowed to stand at room temperature for two days to give needle-like orange crystals of (I)The free ligand cyclam was purchased from Fluka and used as provided. All chemicals were reagent grade materials and were used without further purification. The starting materials, Uiso(H) values of 1.2Ueq of the parent atoms.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016014134/wm5323sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016014134/wm5323Isup2.hklStructure factors: contains datablock(s) I. DOI: 1502530CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Secondary Sn⋯S interactions lead to centrosymmetric dimeric aggregates in the crystal.In (CH 3)2(C5H8NOS2)2], has the SnIV atom bound by two methyl groups which lie over the weaker Sn—S bonds formed by two asymmetrically chelating dithiocarbamate ligands so that the coordination geometry is skew-trapezoidal bipyramidal. The most prominent feature of the molecular packing are secondary Sn⋯S interactions [Sn⋯S = 3.5654 (7) Å] that lead to centrosymmetric dimers. These are connected into a three-dimensional architecture via methylene-C—H⋯S and methyl-C—H⋯O(morpholino) interactions. The Sn⋯S interactions are clearly evident in the Hirshfeld surface analysis of the title compound along with a number of other intermolecular contacts.The title compound, [Sn(CH Fewer examples are known for five-coordinate, trigonal–bipyramidal species, e.g. (t-Bu)2Sn(S2CNMe2)2 in which one dithiocarbamate ligand is monodentate CH2CH2]2Sn(S2CNMe)2 where the carbonyl-O atom of one Sn-bound organic substituent is also coordinating the tin atom 2 structures as the strong chelating ability of the dithiocarbamate ligand reduces the Lewis acidity of the tin atom. However, in (I)Both binary tin and organotin dithiocarbamates, IV atom in the title compound (I)R2Sn(S2CNRR’)2 molecules, i.e. skew-trapezoidal bipyramidal rather than octahedral  − d° at the tin atom. The angle subtended at the tin atom by the strongly bound sulfur atoms of 85.878 (19)° is significantly less than that formed by the weakly bound sulfur atoms, i.e. 143.066 (18)°, and is largely responsible for the formation of the skew-trapezoidal plane about the tin atom.The Sna, where two long edges of the translationally displaced trapezoidal planes approach each other to form the interactions. Here, Sn⋯S4i is 3.5654 (7) Å, which is approximately 0.4 Å shorter than the sum of the van der Waals radii of Sn and S of 3.97 Å , Table 2b.An interesting feature of the molecular packing in (I)et al., 2017dnorm in Fig. 3a indicate the formation of the supramolecular dimer through secondary Sn⋯S contacts. On the Hirshfeld surface mapped over electrostatic potential in Fig. 4a. The pair of bright-red spots appearing near the methyl-H12C and morpholine-O1 atoms in Fig. 3b represent the respective donor and acceptor atoms of the C12—H⋯O1 interaction. The comparatively weaker methylene-C10—H⋯S1 interaction is viewed as a pair of faint-red spots near these atoms in Fig. 3b. It is important to note from the immediate environments about a reference molecule within dnorm-mapped Hirshfeld surfaces highlighting intermolecular interactions in Fig. 5The Hirshfeld surfaces calculated on the structure of (I)a, and those delineated into H⋯H, S⋯H/H⋯S, O⋯H/H⋯O, C⋯H/H⋯C, N⋯H/H⋯N, Sn⋯S/S⋯Sn and S⋯S contacts 2. Of these, 12 feature secondary Sn⋯S interactions which, with (I)R2Sn(S2CNRR’)2 structures have Sn⋯S secondary interactions. Selected geometric details for the 13 structures are collated in Table 5A, is a dimeric aggregate disposed about a centre of inversion, as is in (I)i.e. nine. This motif is illustrated in Fig. 7a for (PhCH2)2Sn(S2CNEt2)2 CH2C6H4N-4)2  ligands and self-assemble into supramolecular chains. In {Me2SnS2CN(CH2Ph)CH2CH2(PhCH2)NCS2SnMe2}2 CH2CH2(PhCH2)NCS2SnMe2}2, where there are two independent, centrosymmetric molecules in the asymmetric unit. Here, the resulting supramolecular chain is twisted −1): 1465(s), 1423(s) ν(C—N), 1222(s) ν(C—O), 1110(m), 994(s) ν(C—S), 541(m) ν(Sn—C) cm−1. 1H NMR (CDCl3): 4.18 , 3.77 , 1.54 .Sodium morpholinedithiocarbamate (prepared from the reaction between carbon disulfide and morpholine (Merck) in the presence of sodium hydroxide; 1.0 mmol, 0.185 g) in methanol (20 ml) was added to dimethyltin dichloride  in methanol (10 ml). The resulting mixture was stirred and refluxed for 2 h. The filtrate was evaporated until an off-white precipitate was obtained. The precipitate was recrystallized from methanol solution by slow evaporation to yield colourless prisms. Yield: 0.305 g, 64.4%; m.p.: 448 K. IR (cmUiso(H) set to 1.2–1.5Ueq(C). Owing to poor agreement, one reflection, i.e.  I, global. DOI: 10.1107/S2056989017006855/hb7675Isup2.hklStructure factors: contains datablock(s) I. DOI: 1548414CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Diabetic neuropathy is the most common complication of diabetes. The idea of alterations in energy metabolism in diabetes is emerging. The biogenic antioxidant R(+)-thioctic acid has been successfully used in the treatment of diabetic polyneuropathic (DPN) patients.  The effects of R(+)-thioctic acid  administration were evaluated in 12 DPN patients at baseline and at 15, 30, 60, and 120 administration days throughout the assessment of oxidative stress (OxS); ROS production rate by electron paramagnetic resonance (EPR) technique; and oxidative damage biomarkers (thiobarbituric acid reactive substances (TBARS) and protein carbonyls (PC)), electroneurography (ENG) and visual analogue scale. p < 0.05) at 30 and 60 days. ROS production rate up to −16%; TBARS (−31%), PC (−38%), and TAC up to +48%. Motor nerve conduction velocity in SPE and ulnar nerves (+22% and +16%) and sensor conduction velocity in sural and median nerves (+22% and +5%). Patients reported a general wellness sensation improvement (+35%) at 30 days: lower limb pain sensation (−40%) and upper limbs (−23%).  Supplementation induced significant changes ( The results strongly indicate that an increased antioxidant capacity plays an important role in OxS, nerve conduction velocity, pain, and general wellness improvement. Nevertheless, the effects of the antioxidant compound were found positive up to 60 days. Then, a hormesis effect was observed. Novelty of the research would be a challenge for investigators to carefully address issues, including dose range factors, appropriate administration time, and targeting population to counteract possible “boomerang effects.” The great number of monitored parameters would firmly stress these conclusions. Type 2 diabetes mellitus (type 2 DM) is the most common form of diabetes, accounting for 90–95% of patients in developed countries: in 2030, up to 438 million people affected by type 2 DM have been estimated by recent studies .Type 2 DM is a metabolic disorder, formerly known as non-insulin-dependent diabetes mellitus or adult-onset diabetes, resulting from a combination of insulin resistance and inadequate insulin secretion .Long-term and serious complications of diabetes develop gradually; they can eventually be disabling or even life-threatening . One of 2•−), hydroxyl (HO•), peroxyl (RO2−•), and hydroperoxyl (HRO2−•−) and nonradical species, such as hydrogen peroxide (H2O2) and hydrochloric acid (HOCl)  is also reported in the text. Sample size calculation to determine the minimum number of subjects for adequate study power was made by using the Freeware G∗Power software (http://www.psycho.uni-duesseldorf.de/abteilungen/aap/gpower3/). At 80% power, the calculated sample size was of 11 subjects, slightly lower than the subject's population recruited in the present study.All data were presented as mean ± SD and were analysed using repeated Shapiro-Wilks 2, blood pressure, heart rate, and pharmacological therapy did not show any significant difference. At T0, the biochemical parameters and the haematological indices resulted in the reference ranges as follows: erythrocyte indices: RBCs: 4.63 ± 0.48 106/mm3, HGB: 14.04 ± 1.16 g/dL, HCT: 41.46 ± 3.52%, MCV: 89.83 ± 2.60 μm3, MCH: 30.44 ± 1.04 pg, MCHC: 33.89 ± 0.47 g/dL, and RDW: 13.78 ± 0.95%; leukocyte indices: WBCs: 6.58 ± 1.60 103/mm3, %LYM 27.65 ± 6.87, %MON 8.95 ± 2.62, %GRA 58.94 ± 8.88, #LYM: 1.89 ± 0.83 103/mm3, #MON: 0.56 ± 0.10 103/mm3, and #GRA 3.81 ± 0.80 103/mm3; platelet indices: PLT: 219.75 ± 51.01 103/mm3 and MPV: 9.50 ± 0.92 μm3; S-lactate dehydrogenase ((LDH): 327.63 ± 77.55 U/L); S-creatinine (0.86 ± 0.32 μmol/L); C-reactive protein ((CRP): 0.23 ± 0.33 mg/L). By contrast, haemoglobin A1c ((HbA1c): 6.93 ± 0.69%) and glycaemic index ((GI): 165.77 ± 32.34 mg/dL) resulted strong increases with respect to the normal range.During the supplementation period of R(+)-thioctic acid and for the whole duration of the study, subjects' weight, BMI, SaOAll biochemical and haematological parameters, monitored at T3, T4, T6, and T8, did not show any statistically significant differences with respect to the basal T0 level.However, the glycaemic index followed a trend parallel to OxS, showing an 8% decrease at T4 and a 26% increase at T6, slowly returning to the basal level after the wash out time period.μmol·min−1) measured at the different times (T0–T8) in type II DN patients' capillary blood and plasma. The ROS production rate data calculated at any time and the statistically significant differences between times of measurements are shown in Figures Capillary blood (A):T0 (2.14 ± 0.21) versus T1 (1.97 ± 0.25), T2 (1.77 ± 0.31), T3 (1.79 ± 0.21), and T6 (2.33 ± 0.28); T1 (1.97 ± 0.25) versus T6 (2.33 ± 0.28), T7 (2.19 ± 0.20), and T8 (2.16 ± 0.20); T2 (1.77 ± 0.31) versus T5 (2.24 ± 0.12) and T6 (2.33 ± 0.28); T3 (1.79 ± 0.21) versus T5 (2.24 ± 0.12), T6 (2.33 ± 0.28), T7 (2.19 ± 0.20), and T8 (2.16 ± 0.20).in Plasma (B):T0 (0.20 ± 0.03) versus T6 (0.27 ± 0.04); T2 (0.19 ± 0.03) versus T6 (0.27 ± 0.04); T3 (0.18 ± 0.03) versus T5 (0.22 ± 0.02), T6 (0.27 ± 0.04), and T7 (0.22 ± 0.02); T4 (0.22 ± 0.02) versus T6 (0.27 ± 0.04); T5 (0.22 ± 0.02) versus T6 (0.27 ± 0.04); T6 (0.27 ± 0.04) versus T7 (0.22 ± 0.02) and T8 (0.21 ± 0.02).The antioxidant supplementation of R(+)-thioctic acid induced EPR detectable changes in the ROS production levels (μM) and PC (nmol·mg−1 protein) concentration data measured at any time and the statistically significant differences between times of measurements are shown in Figures At the same time, the antioxidant supplementation induced changes in the investigated oxidative markers. TBARS (TBARS (A):T2 (14.37 ± 4.68) versus T6 (19.02 ± 5.60) and T7 (17.82 ± 4.93); T3 (12.38 ± 4.51) versus T6 (19.02 ± 5.60) and T7 (17.82 ± 4.93); T4 (11.57 ± 3.49) versus T6 (19.02 ± 5.60) and T7 (17.82 ± 4.93).PC (B):T0 (1.75 ± 0.62) versus T2 (1.39 ± 0.60), T3 (1.63 ± 0.46), T4 (1.08 ± 0.46), and T5 (1.56 ± 0.59); T2 (1.39 ± 0.60) versus T6 (1.99 ± 0.65), T7 (1.90 ± 0.60), and T8 (1.77 ± 0.59); T3 (1.63 ± 0.46) versus T6 (1.99 ± 0.65), T7 (1.90 ± 0.60), and T8 (1.77 ± 0.59); T4 (1.08 ± 0.46) versus T5 (1.56 ± 0.59), T6 (1.99 ± 0.65), T7 (1.90 ± 0.60), and T8 (1.77 ± 0.59); T5 (1.56 ± 0.59) versus T6 (1.99 ± 0.65).More specifically, the differences between brackets in the Figure are as follows:Finally, the antioxidant capacity in plasma, TAC (mM) concentration data measured at any time, and the statistically significant differences between times of measurements are reported in More specifically, the differences between brackets in the Figure are as follows:T0 (1.42 ± 0.38) versus T5 (2.21 ± 0.19) and T6 (2.36 ± 0.15); T2 (1.72 ± 0.17) versus T5 (2.21 ± 0.19) and T6 (2.36 ± 0.15); T3 (1.85 ± 0.18) versus T5 (2.21 ± 0.19) and T6 (2.36 ± 0.15); T4 (2.10 ± 0.19) versus T6 (2.36 ± 0.15) and T8 (1.59 ± 0.18); T5 (2.21 ± 0.19) versus T8 (1.59 ± 0.18); T6 (2.36 ± 0.15) versus T7 (1.80 ± 0.21) and T8 (1.59 ± 0.18).In the patient group examined in the present study, the four item symptom DNS score resulted as follows: neuropathic pain: 100% (12 patients); paraesthesia: 58% (7 patients); unsteadiness in walking: 8% (1 pz); numbness in the legs or feet: 0%. Therefore, a score (±SD) of 1.6 ± 0.65, positive for PNP, was calculated. ENG abnormalities were monitored in all patients. Changes in signal amplitude (mV) and distal latency (m/s) in sensory and motor nerves at T0, T3, T4, T6, and T8 were observed (data not shown).R(+)-thioctic acid supplementation induced changes in motor (MNCV m/s) and sensitive (SNCV m/s) conduction velocities see  calculatMNCV (m/s) in ulnar nerve increased significantly at :T3 (53.62 ± 6.48) versus T0 (48.06 ± 5.58); T3 versus T6 (49.52 ± 4.98) and T8 (48.28 ± 5.36);superficial peroneal nerve (SPE) MNCV (m/s) increased significantly at :T3 (46.68 ± 6.42) and T4 (46.70 ± 6.43) versus T0 (38.30 ± 5.53).SNCV (m/s) in median wrist-elbow changed significantly at :T0 (52.38 ± 4.89) versus T3 (58.76 ± 3.24); T3 (58.76 ± 3.24) versus T6 (59.16 ± 3.90) and T8 (53.60 ± 5.96); T6 (59.16 ± 3.90) versus T8 (53.60 ± 5.96).SNCV (m/s) in sural nerve changed significantly  at T0  (a), TBARS  (b), and PC concentration data  (c) and ROS production in plasma versus TBARS  (d), PC  (e), and glycaemic values  (f) are also displayed.In particular, ROS production in capillary blood versus ROS in plasma . In particular, multiple sources of OxS in diabetes can be found, including nonenzymatic , enzymatic , and mitochondrial pathways , 38. Hypα-lipoic acid, evening primrose oil (EPO), or sunflower oil was found to decrease plasma lipid levels and risk factors [α-lipoic acid on oxidative stress parameters are reported in the literature: increased super oxide dismutase (SOD) and subsequent reduction of H2O2 by catalase [Dietary supplementation with  factors . The poscatalase , 42.2−) levels [Direct evidence of OxS in diabetes was previously provided by the measurement of oxidative stress markers, such as plasma and urinary F2-isoprostane, as well as plasma and tissue nitrotyrosine and superoxide anion radicals (O•) levels , 44.Starting from these considerations, the present study aimed at investigating the effects produced by antioxidant supplementation -thioctic acid, 1.6 g/die) and after the wash out period (two months) on diabetic neuropathic patients throughout ROS production measurement by adopting an innovative EPR method.The study protocol was sketched in As observed in As a matter of fact, in all patients at T0 that is just before the antioxidant supply , a high degree of oxidative damage, as confirmed by the high ROS production rate concentration values, was measured in both capillary blood and plasma.Indeed, the acute effects, “one shot” of R(+)-thioctic acid supplementation in differently aged healthy subjects, were previously reported . A decreIndeed, the results of the present study conducted on diabetic patients, homogeneous for age and physical characteristics see  and concp < 0.01) and kept decreasing at T3  and T4  of daily supplementation. According to the ROS decrease, also, TBARS and PC levels significantly (p < 0.01) decreased at T3 (−26 and −39%) and T4 (−31% and 38%), respectively  increased as shown by the increase of ROS production in capillary blood  and plasma , when compared to the basal level  increased : the OxS values significantly , then returning slowly towards the baseline during the wash out and the periods without administration even if at a slightly higher level . This figure was found also for the ROS production and oxidative damage markers -thioctic acid on ROS production and oxidative damage markers, as well as on motor and sensory nerve conduction velocities see  and 3. TThe role played by OxS in nerve damage has been extensively studied in experiments carried out in an animal model  and moreDiabetic neuropathies are diabetes mellitus-associated disorders probably ascribable to different causes; some of them are not yet well elucidated and in particular how prolonged exposure to high blood glucose levels can produce nerve damage.α-lipoic acid on nerve functions. In fact, α-lipoic acid has been shown to improve motor nerve conduction velocity in experimental diabetic neuropathy and to protect peripheral nerves from ischemia in rats [Motor nerve (MNCV) and sensory nerve (SNCV) conduction velocities resulted in the primary endpoints for studying the therapeutic effectiveness of  in rats .Evidence related to changes in nerve conduction velocity after thioctic acid administration was observed primarily in experimental models –60.The conduction velocities (m/s) of the sensory component of ulnar and sural nerves in diabetic subjects affected with neuropathy were previously found significantly lower than those measured in diabetics without neuropathy as well as nondiabetic subjects . In wellα-lipoic acid (600 mg/die). This molecule is known to interact with many glucose-converting enzymes, fatty acids, and other energy sources in ATP. In the present study, nerve conduction significantly increased at T3 and T4 (30–60 supplementation days): MNCV: +16-17% in ulnar and external sciatic-popliteal (SPE) nerves; SNCV: +12-13% in median and about +16% in sural nerves.Again, the literature data  reportedIndeed, in human studies to date, a great number of studies targeting “thioctic acid” and “diabetes mellitus” have been published, from which only a few randomized control trials in humans are distinguished in terms of DPN treatment with thioctic acid. We are well aware that nerve conduction velocity cannot be used to monitor changes in oxidative stress; nonetheless, the data of the present study suggested us that the hormesis effect described above could be hypothesized for MNCV and SNCV too: the beneficial effects on nerve conduction were lost after long antioxidant administration time period (T6 and over), almost returning to the pretreatment (T0) conduction velocity values see .VAS is a suitable method to measure pain/pain relief and general wellness. In the present study, in all patients, a regression of the subjective pain sensation as well as a general wellness improvement was reported under R(+)-thioctic acid treatment mainly at T3 and T4 , followed by an improvement of about the 50% after 30–60 days of treatment , then returning to the basal level after the wash out period. At the same time, at T3-T4, the general wellness sensation was found to improve at about +35% as well.Side effects, like stomachache and nausea, were reported, but mild or moderate, since no patients interrupted the supplementation for this reason.Side effects as a consequence of alpha-lipoic acid oral administration were previously reported by Ziegler et al. . DespiteA significantly higher dose protocol was followed in the present study (1.6 g/die): patients referred stomachache and nausea mainly at T2-T3 and T5-T6, the symptoms returning to normal after the wash out period see .Nevertheless, during the supplementation time course, patients reported an improvement of the general wellness sensation mainly at T3-T4: in particular, pain at the lower limbs and feet  duration of the treatment, no significant differences were found in the haematological parameters all over the supplementation duration.p < 0.01) linear correlation was found at every time between the ROS production mean values in capillary blood and ROS production in plasma (R2 = 0.76), TBARS (R2 = 0.60), and PC (R2 = 0.79)  relationships were found at every time between ROS production mean values in plasma and TBARS (R2 = 0.58), PC (R2 = 0.66), and glycaemic levels (R2 = 0.54)  was large enough to ensure an adequate study power, as determined by the Freeware G∗Power software (see paragraph 2.7). In fact, as already pointed out, at 80% power, the calculated sample size was 11 subjects. However, the population recruited for the study is certainly well below the number of participants standardly recruited for a clinical trial. As a matter of fact, the present study has to be considered as a pilot test. The research concerns the use of an antioxidant substance, the R(+)-thioctic acid, whose acute effects were previously tested on healthy subjects by some of us. In type II diabetic patients, the pilot test study consisted in a very long administration time and the wash out period. Despite the long administration time, none of the patients interrupted the trail so that the results could be obtained at each time from the whole subject sample. It is worth noting the great number of monitored parameters joining oxidative stress by using innovative instruments (EPR) applied by a mini-invasive technique and electroneurography investigations, together with the homogeneity of the assessed results, supported and strengthened by the significance of the correlations -thioctic acid 1.6 mg administration was shown to produce EPR detectable changes in ROS formation as measured in capillary blood and plasma and related oxidative damage parameters with consequent positive effects on nerve conduction velocity too. The findings of the present study strongly indicated that an increased antioxidant capacity plays an important role in the improvement of OxS, nerve conduction velocity, pain, and general wellness. Nevertheless, at the same time, the results of the study showed that the safety effects of an exogenous antioxidant compound were positive up to 60 administration days. After this period, a hormesis effect was observed. Therefore, the novelty of the conducted research would be a challenge for investigators to carefully address issues, including dose range factors, as well as appropriate administration time and targeting population to counteract possible “boomerang effects” of the treatment. The great number of parameters monitored in this study would firmly stress these conclusions.


Scientific Reports6: Article number: 3157410.1038/srep31574; published online: 08172016; updated: 02172017–4 μ W cm−2, at 4.5 cm) illuminated the surface of the polymer samples”.This Article contains an error in the Methods section. “Two 30 W UVC lamps  illuminated the surface of the polymer samples”.“Two 30 W UVC lamps (253.7 nm, irradiance of 0.01 W cm


I atom in the molecular structure of the title compound exhibits a distorted tetrahedral coordination sphere, defined by two N atoms of the chelating ligand, one N atom of the acetonitrile ligand and one iodide ligand.The Cu 2H3N)(C26H24N2)], the CuI ion has a distorted tetrahedral coordination environment, defined by two N atoms of the chelating 2--6-[imino]pyridine ligand, one N atom of an acetonitrile ligand and one iodide ligand. Within the complex, there are weak intramolecular C—H⋯N hydrogen bonds, while weak intermolecular C—H⋯I interactions between complex molecules, help to facilitate a three-dimensional network.In the mononuclear title complex, [CuI(C The two N atoms of the bidentate ligand chelate to CuI with similar Cu—N bond lengths . A comparable N,N′-binding has been observed in related structures with bis[2-(2-pyridyl)ethyl]amine ligands  Å. The N2—Cu1—N1 bite angle of the chelating ligand is 78.86 (18)°, while the N3—Cu—I angle between the monodentate acetonitrile and iodide ligands is closer to tetrahedral, 112.74 (15)°. The naphthyl ring system is inclined by 58.20 (17)° to the central N=C(CH3)—pyridine moiety, whereas the trimethylphenyl ring is almost perpendicular to the latter, at 84.8 (3)°. Within the complex, an intramolecular C—H⋯N hydrogen-bonding interaction is present, stabilizing the molecular conformation  Å, 152°; symmetry code: (i) x, y − 1, z] and a H atom of the acetonitrile methyl group  link the complex molecules, forming a three-dimensional network  was synthesized according to a modified literature procedure  in 5 ml of acetonitrile. The mixture was stirred at room temperature for 24 h before evaporating the volatiles. The residue was extracted with n-hexane (5 × 3 ml). The extracts were combined and the solvent removed under reduced pressure to give a red solid which was recrystallized from acetonitrile solution. Yield: 54%. M.p. >253 K (decomp). 1H NMR : δ 1.88 , 1.97 , 2.16 , 2.20 , 6.84 , 7.39 , 7.45 , 7.51 , 7.73 , 7.81 , 7.87 , 8.04 . IR νmax (solid)/cm−1 1620 (C=Nimine), 1555 (C=Npy). ESI MS: m/z 428 [M–I–MeCN]+.A solution of 0.0262 g of CuI (0.137 mmol) in 5 ml of acetonitrile was mixed with a solution of 0.05 g of Uiso(H) = 1.2Ueq(C) for H atoms on Csp2 and 0.98 Å with Uiso(H) = 1.5Ueq(C) for H atoms on Csp3.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016018685/wm5341sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989016018685/wm5341Isup2.hklStructure factors: contains datablock(s) I. DOI: 1518571CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


II ion is completed by the ligation of two N atoms of two piperazinium ions. In the crystal, a network of N—H⋯O and O—H⋯O hydrogen bonds leads to the formation of a three-dimensional supramolecular structure.In the title compound, two thiosulfate ions coordinate to the zinc(II) ion through the terminal S atoms. The tetrahedral coordination around the Zn 4H11N2)2(S2O3)2]·2H2O, two thiosulfate ions coordinate to the zinc(II) atom through the terminal S atoms. The tetrahedral coordination around the ZnII ion is completed by ligating to two N atoms of two piperazinium ions. The remaining two N atoms of the piperazinium ions are diprotonated and do not coordinate to the metal centre. In the crystal, however, they are involved in N—H⋯Owater and N—H⋯Osulfato hydrogen bonds. Together, a series of N—H⋯O and O—H⋯O hydrogen bonds, involving the O atoms of the thiosulfate ions and the water molecules as acceptors and the hydrogen atoms of the piperazinium ions and the water molecules as donors, form a three-dimensional supramolecuar structure. Within this framework there are a number of intra- and intermolecular C—H⋯O and C—H⋯S contacts present.In the title compound, [Zn(C Recently, Natarajan and co-workers  and two nitrogen atoms from the piperazinium ions (N1 and N3), in an approximately tetrahedral geometry . The Zn—S bond lengths are 2.2927 (4) Å for Zn1—S1 and 2.3324 (4) Å for Zn1—S3. The Zn—N bond lengths are 2.0879 (13) Å for Zn1—N1 and 2.0727 (12) Å for Zn1—N3. The N/S—Zn1—S/N bond angles lie in the range 101.24 (4) to 116.79 (2)°, confirming the tetrahedral nature of the zinc ions. Within the two thiosulfate ligands, the S—S bond lengths are 2.0511 (5) Å for S1—S2 and 2.0332 (5) Å for S3—S4. The S—O bond lengths vary from 1.4437 (14) to 1.4623 (13) Å, while the O—S—O angles vary from 104.53 (5) to 112.85 (10)°, which is indicative of a fairly regular tetrahedral arrangement. In the molecular unit, the two thiosulfate units are bonded to the zinc(II) ion only through the terminal S atoms, and the oxygen atoms are uncoordinated. In addition, only one nitrogen atom of each piperazinium ion is bonded to the zinc(II) ion, the second being diprotonated in each case.The molecular structure of the title compound is illustrated in Fig. 1The supramolecular architecture Fig. 2 arises fet al., 2016et al. zinc(II) hemihydrate (CSD refcode: WEHTOT). The thiosulfate ligand is coordinated to the zinc ions through S and O atoms, forming octahedral zinc centres. In addition, a zinc–thiosulfate complex containing both one-dimensional cationic and anionic chains has been reported by the same authors, viz. catena-[tetraaquazinc(II) bisbis(thiosulfato-κS)dizinc(II) dihydrate]  (IJUWER), catena-[(μ-thiosulfato)zinc] (IJUWIV), and catena-[bisbis(μ-thiosulfato)dizinc dihydrate] (IJUWOB) and catena-[bisbis(μ-thiosulfato)dizinc (μ-thiosulfato)zinc trihydrate] (IJUWUH).Karthik & Natarajan 2016 have recet al., 1996et al., 2001et al., 2004A number of molecular cadmium–thiosulfate and manganese–thiosulfate structures have been reported by Baggio and co-workers (thiosulfato)cadmium (CSD refcode: ORUJOC), which was reported recently, was isolated in the presence of the aliphatic amine 1,3-diaminopropane 2·6H2O  was dissolved in 5 ml distilled water. Then (NH4)2S2O3  was added to the solution, which was stirred for 15 min. Piperazine  was dissolved separately in distilled water (5 ml) and the solution poured into the initial reaction mixture until the pH was 8. The resulting solution was left undisturbed and after 1 week, colourless block-shaped crystals were obtained. The product was filtered and washed with cold water. The yield was approximately 85% based on Zn metal. Elemental analysis calculated for C8H26N4O8S4Zn: C 19.20, H 5.24, N 11.20%; found: C 19.27, H 5.29, N 11.16%.Zn = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018000555/cq2022sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989018000555/cq2022Isup2.hklStructure factors: contains datablock(s) I. DOI: 1571150CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports 10.1038/s41598-017-03589-w, published online 12 June 2017Correction to: The original version of this Article contained a typographical error in the Abstract.9/L) × AST(U/L).”“The formula of the mFIB-4 index is 10 × Age(years) × AST(U/L)/Platelet count(10now reads:9/L) × ALT(U/L).”“The formula of the mFIB-4 index is 10 × Age(years) × AST(U/L)/Platelet count(10This has now been corrected in the PDF and HTML versions of the Article.


Crystal structures of hydrogen-bonded 1:2 dihydrate compounds of chloranilic acid with 2-carboxypyridine (I) and 2-carboxyquinoline (II) have been determined at 180 and 200 K, respectively. The base molecule in (I) is disordered over cationic and twitterionic states, while that in (II) is in a twitterionic form. In each crystal, the three components are linked by O—H⋯O and N—H⋯O hydrogen bonds, forming a layer structure. 6H5.5NO20.5+·C6HCl2O4−·2H2O, (I), has been determined at 180 K, and the structure of the 1:2 dihydrate compound of chloranilic acid with 2-carboxyquinoline , namely, 2C10H7NO2·C6H2Cl2O4·2H2O, (II), has been redetermined at 200 K. This determination presents a higher precision crystal structure than the previously published structure [Marfo-Owusu & Thompson  was analysed as a disordered structure over two states, viz. salt and co-crystal. The salt is bis(2-carboxypyridinium) chloranilate dihydrate, 2C6H6NO2+·C6Cl2O42−·2H2O, and the co-crystal is bis(pyridinium-2-carboxylate) chloranilic acid dihydrate, 2C6H5NO2·C6H2Cl2O4·2H2O, including zwitterionic 2-carboxypyridine. In both salt and co-crystal, the water molecule links the chloranilic acid and 2-carboxypyridine molecules through O—H⋯O and N—H⋯O hydrogen bonds. The 2-carboxypyridine molecules are connected into a head-to-head inversion dimer by a short O—H⋯O hydrogen bond, in which the H atom is disordered over two positions. Compound (II) is a 1:2 dihydrate co-crystal of chloranilic acid and zwitterionic 2-carboxyquinoline. The water molecule links the chloranilic acid and 2-carboxyquinoline molecules through O—H⋯O hydrogen bonds. The 2-carboxyquinoline molecules are connected into a head-to-tail inversion dimer by a pair of N—H⋯O hydrogen bonds.The crystal structure of the 1:2 dihydrate compound of chloranilic acid  with 2-carboxypyridine , namely, 2Cpson 2014. X-ray S The pyridine rings are also stacked along the b axis through a π–π interaction [centroid–centroid distance = 3.6851 (7) Å and interplanar spacing = 3.4787 (5) Å]. Between the layers, a short Cl⋯Cl contact is observed [Cl1⋯Cl1v = 3.3717 (5) Å; symmetry code: (v) −x + 1, y − z + In the crystal of compound (I)ne Fig. 4. In the via a pair of N—H⋯O hydrogen bonds  Å. The water molecule links the stacked base molecules related by translation along a via O—H⋯O hydrogen bonds [O5—H3⋯O4 and O5—H4⋯O4ii; Table 2via O—H⋯O hydrogen bonds, forming a layer structure parallel to et al., 2016A search of the Cambridge Structural Database Uiso(H) = 1.5Ueq(O). For the water H atoms, distant restraints of H⋯H = 1.37 (4) Å were also applied. C-bound H atoms were positioned geometrically (C—H = 0.95 Å) and were treated as riding with Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 3Uiso(H) = 1.2Ueq(C).All H atoms in compound (II)10.1107/S2056989017015997/lh5860sup1.cifCrystal structure: contains datablock(s) General, I, II. DOI: 10.1107/S2056989017015997/lh5860Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989017015997/lh5860IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989017015997/lh5860IIsup4.cmlSupporting information file. DOI: 1583721, 1583720CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


DNGR‐1 is receptor expressed by certain dendritic cell (DC) subsets and by DC precursors in mouse. It possesses a C‐type lectin‐like domain (CTLD) followed by a poorly characterized neck region coupled to a transmembrane region and short intracellular tail. The CTLD of DNGR‐1 binds F‐actin exposed by dead cell corpses and causes the receptor to signal and potentiate cross‐presentation of dead cell‐associated antigens by DCs. Here, we describe a conformational change that occurs in the neck region of DNGR‐1 in a pH‐ and ionic strength‐dependent manner and that controls cross‐presentation of dead cell‐associated antigens. We identify residues in the neck region that, when mutated, lock DNGR‐1 in one of the two conformational states to potentiate cross‐presentation. In contrast, we show that chimeric proteins in which the neck region of DNGR‐1 is replaced by that of unrelated C‐type lectin receptors fail to promote cross‐presentation. Our results suggest that the neck region of DNGR‐1 is an integral receptor component that senses receptor progression through the endocytic pathway and has evolved to maximize extraction of antigens from cell corpses, coupling DNGR‐1 function to its cellular localization. Bufferlong mouse DNGR‐1 ECD to mildly denaturing (Laemmli buffer) or strongly denaturing (8 M urea) conditions in the presence of DTT and analyzed the samples by SDS–PAGE and Western blot. As predicted, strongly denaturing conditions almost completely abolished the ability of DNGR‐1 to resist reduction, while under weakly denaturing conditions the reduction‐insensitive dimers could be observed. In the absence of reducing agents, the protein maintained its dimeric status regardless of the denaturing conditions  to induce the reduction‐resistant state, dialyzed the protein back into PBS, and tested its reduction sensitivity. As expected, we observed reduction‐resistant dimers under mildly acidic conditions , all the proteins were readily reducible while, when subjected to weakly acidic conditions (pH 6.1), they showed increased resistance to reduction Fig B. These We expressed a chimeric ECD, in which the neck region of DNGR‐1 was fused to the CTLD of another C‐type lectin receptor, dectin‐1 Fig A. Dectinlong mouse and human DNGR‐1 isoforms under neutral (PBS) or mildly acidic (MES pH 6.1) conditions, and observed almost perfect overlap between the two . Far‐UV CD spectra reflect the secondary structure content of the protein while near‐UV CD signals derive from the three aromatic residues  and, in some cases, from disulfide bonds, and reflect protein tertiary structure  conditions , suggesting that the part of the neck region involved in the process is conserved between the two. In order to pinpoint its location, we genetically removed overlapping blocks of 10–11 amino acids from the conserved part of the neck [K57–L66 (Δ1), L64–I73 (Δ2), L72–L82 (Δ3), N81–T90 (Δ4), R87–A96 (Δ5), and Q95–S104 (Δ6)  resulted in an ECD protein that behaved like the Δ4 mutant in that it formed type‐2 dimers in neutral conditions   overnight and measured the extent of T‐cell reactivation by assessing the amount of IFN‐γ that accumulated in the culture medium. Consistent with previous data . pH‐induced conformational changes have been reported for other proteins and are often mediated by protonation of one or more histidines stabilizing forces in the same range as electrostatic repulsion, they can contribute to, and perhaps even be sufficient for, pH‐sensitive conformational rearrangements . Thus, other parts of DNGR‐1 are also involved in determining the ability of the receptor to promote cross‐presentation of dead cell‐associated antigens.long mouse, K57–I238 for short mouse, and K57–V241 for the human isoform) or mouse dectin‐1 (R71–L244) was inserted into the p3xFLAG‐CMV‐9 expression vector (Sigma‐Aldrich) and all the constructs were verified by sequencing. The proteins were expressed by transient transfection in 239F cells, as described previously  and following primers: C94S: 5′‐CCATGCATGATCCAATTAGGAAGGCATGTTTCCTTGCTGTCCAGGGTCTG‐3′, Δ1: 5′‐CAAGGATGACGATGACAAGCTTGCGGCCGCGGAGCAGCAGGAAAGACTCATCCAACAGGAC‐3′, Δ2: 5′‐CGGCCGCGAAGTTCTTCCAGGTATCCTCTCAACAGGACACAGCATTGGTGAACCTTACAC‐3′, Δ3: 5′‐CCTCTCTTGTCTTGGAGCAGCAGGAAAGAACACAGTGGCAGAGGAAATACACACTGGAATACTGCC‐3′, Δ3A: 5′‐GGTATCCTCTCTTGTCTTGGAGCAGCAGGAAAGAGCCGCCGCCGCCGCCGCCGCCGCCGCCGCCGCCACACAGTGGCAGAGGAAATACACACTGGAATACTGCCAAGCC‐3′, Δ4: 5′‐GGAAAGACTCATCCAACAGGACACAGCATTGGTGCTGGAATACTGCCAAGCCTTACTGCAGAGATCTCTCC‐3′, Δ4A: 5′‐GCAGGAAAGACTCATCCAACAGGACACAGCATTGGTGGCCGCCGCCGCCGCCGCCGCCGCCGCCGCCCTGGAATACTGCCAAGCCTTACTGCAGAG‐3′, Δ5: 5′‐GACACAGCATTGGTGAACCTTACACAGTGGCAGTTACTGCAGAGATCTCTCCATTCAGGCAC‐3′, Δ6: 5′‐CAGTGGCAGAGGAAATACACACTGGAATACTGCGGCACAGATGCTTCTACTGGACCAG‐3′, Δ6A: 5′‐GTGAACCTTACACAGTGGCAGAGGAAATACACACTGGAATACTGCGCCGCCGCCGCCGCCGCCGCCGCCGCCGCCGGCACAGATGCTTCTACTGGACCAGTTCTTCTGAC‐3′.long mouse DNGR‐1 (K57–T130) with 5′ and 3′ sequences complementary to regions of the p3xFLAG‐CMV‐9 plasmid and dectin‐1, respectively, was amplified in a PCR with Phusion Hot Start II polymerase (Thermo Scientific), using the following primers: 5′‐GCTGGGTGCCCTAGCATTTTGGAAGTTCTTCCAGGTATCCTCTCTTG‐3′ and 5′‐CCATGCATGATCCAATTAGGAAGGCATGTTTCCTTGCTGTCCAGGGTCTG‐3′ and a DNGR‐1‐coding plasmid as a template, and then used in a modified reaction with QuikChange Lightning kit (Agilent Technologies) as per manufacturer's instructions with p3xFLAG‐CMV‐9 plasmid containing dectin‐1 ECD sequence as a template. For generation of chimeric DNGR‐1 proteins with the neck region of CD69 or Ly49, “megaprimers” covering the entire neck region of appropriate proteins were generated using the following primers: 5′‐GTTAGCAACGTCCATTTTCTTGGGCATCGGCAAGTACAATTGCCCAGGCTTG‐3′ and 5′‐GTGGACAAGGGCTGCAGTCACTACCAGCAACATGGTGGTCAGATG‐3′ for CD69 and 5′‐GTTAGCAACGTCCATTTTCTTGGGCATCAACATTTTTCAGAATAGTCAACAAAATCATGAACTGCAGG‐3′ and 5′‐GTGGACAAGGGCTGCAGTCACTACCTTCAAAACCTCTGCCTGTGTGCTGTGAGG‐3′ for Ly49. cDNA generated from total splenic mRNA of a C57BL/6 and a CBA/J mouse, respectively, was used as templates. “Megaprimers” were then used in a modified reaction with QuikChange Lightning kit (Agilent Technologies) as per manufacturer's instructions with pFB‐IRES GFP plasmid containing the entire sequence of DNGR‐1 as a template.For the chimeric DNGR‐1:dectin‐1 protein, a “megaprimer” covering the whole neck region of Samples for SDS–PAGE were prepared in 6× Laemmli buffer (60% (v/v) glycerol, 150 mg/ml SDS, 0.75 mg/ml bromophenol blue in 75 mM Tris–HCl pH 6.8) under reducing (+100 mM DTT) or non‐reducing conditions unless otherwise stated. Separation was carried out using 4–20% Mini‐PROTEAN TGX precast gels (Bio‐Rad). Proteins were transferred onto Immobilon P membrane (Merck Millipore) using wet transfer, the membrane was blocked in 5% milk in PBS + 0.05% Tween‐20, and ECD proteins were detected using HRP‐conjugated M2 anti‐FLAG antibody (Sigma‐Aldrich). Full‐length DNGR‐1 was detected using anti‐DNGR‐1 antibody (clone 397) followed by HRP‐conjugated polyclonal anti‐rat antibody (IgG (H+L); Stratatech).long DNGR‐1 ECD was concentrated to 7 mg/ml and, immediately before analysis, diluted into PBS or 10 mM MES pH 6.1 to final concentration 170 μg/ml. Human DNGR‐1 ECD was concentrated to 1.4 mg/ml and immediately before analysis diluted into PBS or 10 mM MES pH 6.1 to final concentration 140 μg/ml. Far‐UV CD spectra (260–195 nm) were recorded at 20°C in 1 mm fused silica cuvettes using a Jasco J‐815 spectropolarimeter fitted with a cell holder temperature controlled by a CDF‐426S Peltier unit. The spectra were typically recorded with 0.1‐nm resolution and baseline corrected by subtraction of the appropriate buffer spectrum. CD intensities are presented as the CD absorption coefficient calculated on a mean residue weight basis (ΔεMRW). Secondary structure content was estimated using methods originally described by Sreerama and Woody  were recorded at 20°C in 10 mm fused silica cuvettes. Near‐UV CD intensities are presented on a molecular weight basis (ΔεM).For far‐UV CD, mouse et al, et al, 2) and polymerized in F‐buffer . Polymerized actin was stabilized with 5 μM phalloidin (Life Technologies) and spotted onto nitrocellulose membrane (Whatman) in twofold dilution series. The membrane was blocked in 5% milk in PBS + 0.05% Tween‐20 overnight and incubated with protein supernatants diluted into appropriate buffers at equal concentrations. Binding of all proteins was detected using HRP‐conjugated M2 anti‐FLAG antibody (Sigma‐Aldrich) and revealed using SuperSignal West Pico Chemiluminescent Substrate (Thermo Scientific) or Luminata Forte Western HRP Substrate (Merck Millipore).Dot blot assay was performed as described previously  supplemented with β‐ME and 10% heat‐inactivated fetal calf serum (FCS) at 37°C and 5% CO2. 293F cells were grown in FreeStyle 293 Expression Medium (Gibco) at 37°C, 8% CO2, and with constant shaking on an orbital shaker at 120 rpm. 293FT cells were grown in DMEM medium (Gibco) supplemented with 10% heat‐inactivated fetal calf serum (FCS) at 37°C and 10% CO2.Phoenix, B3Z‐Syk , VSV‐G envelope protein‐coding plasmid, and a pFB plasmid coding for the desired protein. On days 1, 2, and 3 post‐transfection, the pseudotyped virus‐containing culture medium was recovered, filtered, supplemented with 8 μg/ml polybrene (Sigma‐Aldrich), and immediately applied to target cells. The plate was centrifuged for 90 min at 2,500 × g at room temperature and left in the incubator for a further 90 min. After the incubation, the medium was exchanged for fresh complete IMDM medium. On day 5, selection medium containing 0.5 μg/ml puromycin was applied. Surviving cells after 1 week of selection were expanded and transduced in an identical manner as described above with lentivirus generated in 293FT cells transfected with a mixture of Lipofectamine 2000, psPax2, pMD2.G, and pLX‐sgRNA plasmids. Successfully transduced cells were selected in medium containing 5 μg/ml blasticidin. Surviving cells after 1 week of selection were expanded and Cas‐9 expression was induced by addition of 1 μg/ml doxycycline to the culture medium for 3 weeks. Cells that lost DNGR‐1 expression were then purified by FACS sorting. The sequence of sgRNA used was as follows: CTGAACATTTGCTAGGGGAT. pCW‐Cas9 and pLX‐sgRNA plasmids were a gift from Eric Lander & David Sabatini (Addgene plasmids #50661 and #50662), pMD2.G and psPAX2 plasmids were a gift from Didier Trono (Addgene plasmids #12259 and #12260).293FT cells were transfected by a mixture of Lipofectamine 2000 (Thermo Fisher Scientific), psPax2, pMD2.G, and pCW‐Cas9 plasmids. Lentivirus‐containing culture medium was recovered on days 1, 2, and 3 post‐transfection, filtered, diluted 1:9, supplemented with 8 μg/ml polybrene (Sigma‐Aldrich), and immediately applied to MuTu cells. The plate was centrifuged for 90 min at 2,500 × et al, 2 for 45 min. After the incubation, the cells were harvested, washed in ice‐cold PBS + 5 mM EDTA, and fixed in 4% PFA. After fixation, the cells were washed in FACS buffer  and surface‐stained with PE‐conjugated anti‐DNGR‐1 antibody (clone 1F6). Staining was analyzed using LSR Fortessa Flow cytometer (BD Biosciences). Data analysis was performed in FlowJo 9.8.5 software (TreeStar).Internalization assay was described previously  293T cells at the indicated ratios, or in wells coated with anti‐DNGR‐1 antibody (clone 7H11) or in medium alone in a 96‐well plate. LacZ activity after incubation overnight at 37°C and 5% CO2 was determined by lysing the cells in CPRG (Roche) containing buffer and measuring OD595 with OD655 as a reference at multiple time points.B3Z‐Syk reporter assay was described previously  and left overnight to undergo secondary necrosis. Cell corpses were harvested, washed once in full RPMI1640 medium, and plated at indicated ratios with 6 × 104 MuTu cells per well in a U‐bottom 96‐well plate. After a 4‐h incubation at 37°C and 5% CO2, 3 × 104 pre‐activated OT‐I T cells (see below) were added to each well and incubated at 37°C and 5% CO2 overnight. Next morning, the plate was freeze–thawed once, and total amount of IFN‐γ in the supernatants was determined by ELISA.Ovalbumin‐expressing mouse embryonic fibroblasts (bm1 T OVA MEFs; Sancho −/− mice were bred at The Francis Crick Institute under specific pathogen‐free conditions in accordance with the national and institutional guidelines for animal care and approval by The Francis Crick Institute Animal Ethics Committee and by the Home Office, UK. Spleen and lymph nodes from one OT‐I Rag1−/− mouse were homogenized into a single cell suspension. Cells were plated at 1 × 105 per ml in complete RPMI1640 medium supplemented with 0.1 nM SIINFEKL peptide. On day 3 of culture, IL‐2 was added to a final concentration of 25 U/ml. CD8+ T cells were MACS‐enriched on day 5 and used immediately.OT‐I Rag1PH designed the study, performed and analyzed experiments, and wrote the manuscript. OS provided technical assistance, contributed to the design of experiments, and performed some of the experiments shown in Fig The authors declare that they have no conflict of interest.Review Process FileClick here for additional data file.Source Data for Figure 1Click here for additional data file.Source Data for Figure 2Click here for additional data file.Source Data for Figure 3Click here for additional data file.Source Data for Figure 4Click here for additional data file.Source Data for Figure 6Click here for additional data file.


The title structure consists of 3-aminopyridinium cations and 1′-carboxyferrocene-1-carboxylate monoanions held together by N—H⋯O and O—H⋯O hydrogen bonds. 5H7N2)[Fe(C6H4O2)(C6H5O2)], consists of 3-aminopyridinium cations and 1′-carboxyferrocene-1-carboxylate monoanions. The ferrocenyl moiety of the anion adopts a typical sandwich structure, with Fe—C distances in the range 2.0270 (15)–2.0568 (17) Å. The anion possesses an eclipsed conformation, with the torsion angle φ (Csubst—Cpcent—Cpcent— Csubst) equal to 66.0°. The conformations of other 1′-carboxyferrocene-1-carboxylate monoanions are compared and analyzed on the basis of literature data.The structure of the title salt, (C The C16—O bond lengths within the carboxylate anion are almost equal [1.2604 (19) and 1.2636 (19) Å], whereas, in contrast, they differ greatly within the carboxylic acid group, with C26=O22 = 1.2128 (19) Å and C26—O21 = 1.326 (2) Å, the latter involving the OH group. The planes of the cyclopentadienyl (Cp) rings are almost parallel to the planes of the corresponding carboxy/carboxylate groups, with O—C—C—C torsion angles less than 13°. The conformation of 1,1′-disubstituted ferrocenes is described by the torsion angle Csubst—Cpcent—Cpcent—Csubst, where Csubst stands for a ferrocene C atom with an additional bonding partner and Cpcent for the centre of gravity of the C atoms of the ring; this angle is hereafter referred to as φ. In (1), the anion possesses an eclipsed conformation with φ = 66.0°   consists of one 3-aminopyridinium cation and one 1′-carboxyferrocene-1-carboxylate monoanion Fig. 1. In the °) Fig. 2.−O2C hydrogen bonds of medium–strong-to-weak nature and of CO2H⋯−O2C hydrogen bonds of strong nature  by charge-supported NH⋯e Table 2.et al., 20162C-η5-C5H4)Fe(η5-C5H4-CO2−) units from 14 crystallographically independent monoanions. Among these 14 fragments, three adopt a trans-staggered conformation, with m = 5  was added dropwise to 1,1′-diacetylferrocene  under stirring at a temperature of 317–320 K. The solution was stirred at this temperature for 2 h. Three more 25 ml portions of NaOCl solution were added every 2 h. The reaction mixture was filtered and acidified to a pH of 1.1 with 10% hydrochloric acid and cooled to 277 K overnight. The yellow precipitate which formed was filtered off and recrystallized from ethanol to give an orange microcrystalline powder .Ferrocene-1,1′-dicarboxylic acid  was dissolved in methanol and mixed with a methanolic solution of 3-aminopyridine . The reaction mixture was filtered and subjected to slow evaporation at room temperature to give orange crystals of the title salt.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017007058/wm5388sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989017007058/wm5388Isup2.hklStructure factors: contains datablock(s) I. DOI: 1444115CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


E configuration with respect to the azomethine bond, and one nitrate anion.The title aroyl hydrazone Schiff base salt, consists of one molecular cation in the keto tautomeric form, adopting an  13H12N3O2+·N O3−, consists of one molecular cation in the keto tautomeric form, adopting an E configuration with respect to the azomethine bond, and one nitrate anion. The two units are linked via an N—H⋯O hydrogen bond. The molecule overall is non-planar, with the pyridinium and benzene rings being inclined to each other by 4.21 (4)°. In the crystal, cations and anions are linked via intermolecular O—H⋯O and bifurcated N—H⋯O hydrogen bonds, forming a two-dimensional network parallel to (101). These networks are further linked by C—H⋯O hydrogen bonds, forming slabs parallel to (101). The slabs are linked by offset π–π interactions, involving the benzene and pyridinium rings of adjacent slabs [intercentroid distance = 3.610 (2) Å], forming a three-dimensional structure. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯O/O⋯H (45.1%), H⋯H (19.3%), H⋯C/C⋯H (14.5%), H⋯N/N⋯H (7.9%) and C⋯C (6.0%) interactions.The asymmetric unit of the title aroyl hydrazone Schiff base salt, C The orgE, where torsion angle N1—N2—C8—C9 is −177.58 (14)°. On the other hand, torsion angles N2—N1—C7—C5 and C8—N2—N1—C7 are −179.66 (13) and −178.09 (15)°, respectively, and the benzene (C1–C6) and pyridinium (N3/C9–C13) rings are oriented at a dihedral angle of 4.21 (4)°, probably due to the steric interactions between the hydrogen atoms (Table 2The configuration at the N2=C8 [1.276 (2) Å] bond is s Table 2. Thus, tHydr⋯OHydrz, N—HPym⋯ON and bifurcated N—HHydrz⋯ON  hydrogen bonds ] link adjacent layers, forming slabs parallel to (101); see Fig. 3Cg1 is the centroid of atoms C1–C6) and pyridinium (Cg2 is the centroid of atoms N3/C9–C13) rings of adjacent slabs has an intercentroid Cg1⋯Cg2 distance of 3.610 (2) Å, while α is 4.2 (1)°, and the interplanar distances are 3.263 (7) and 3.366 (7) Å, with an offset distance of 1.303 Å.Hydrogen bonding and van der Waals contacts are the dominant interactions in the crystal packing. In the crystal, O—Hs Table 1 link theCrystal Explorer 17.5 , the 19.3% contribution to the overall crystal packing is reflected as widely scattered points of high density due to the large hydrogen content of the molecule. The single spike in the centre at de = di = 1.2 Å in Fig. 5c is due to the short interatomic H ⋯ H contacts  and C⋯O/O⋯C  contacts in the structure with 3.4% and 1.9% contributions to the HS have nearly symmetrical distributions of points, with the scattered points of low densities.In order to visualize the intermolecular interactions in the crystal of the title aroyl hydrazone Schiff base salt, a Hirshfeld surface (HS) analysis 2·4H2O  and 4-[(4-hydroxybenzoyl)hydrazonemethyl]pyridin  in ethanol by using a branched-tube method : 3526 m, ν(OH); 1375 m, ν(N—O); 1644 s, ν(C=N); 1501 s, ν(N=O); 1105 s, ν(NN).The title compound was prepared by the reaction of Cd(NOUiso(H) = 1.2Ueq(C). The highest residual electron density was found 2.48 Å from atom H1.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989018002141/su5422sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989018002141/su5422Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018002141/su5422Isup3.cmlSupporting information file. DOI: 1822116CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Two new salts – 2,6-diamino-4-chloropyrimidin-1-ium 5-chlorosalicylate and bis naphthalene-1,5-disulfonate – have been synthesized and characterized by single-crystal X-ray diffraction. The supramolecular interactions such as hydrogen bonding, halogen bonding, C—Cl⋯π and π–π interactions are investigated for these crystal structures. 4H6ClN4+·C7H4ClO3−, (I), and bis naphthalene-1,5-di-sulfonate, 2C4H6ClN4+·C10H6O6S22−, (II), have been synthesized and characterized by single-crystal X-ray diffraction. In both compounds, the N atom of the pyrimidine group in between the amino substituents is protonated and the pyrimidinium cation forms a pair of N—H⋯O hydrogen bonds with the carboxylate/sulfonate ion, leading to a robust R22(8) motif (supramolecular heterosynthon). In compound (I), a self-complementary base pairing involving the other pyrimidinium ring nitrogen atom and one of the amino groups via a pair of N—H⋯N hydrogen bonds [R22(8) homosynthon] is also present. In compound (II), the crystallographic inversion centre coincides with the inversion centre of the naphthalene-1,5-disulfonate ion and all the sulfonate O atoms are hydrogen-bond acceptors, generating fused-ring motifs and a quadruple DDAA array. A halogen-bond (Cl⋯Cl) interaction is present in (I) with a distance and angle of 3.3505 (12) Å and 151.37 (10)°, respectively. In addition, a C—Cl⋯π interaction and a π–π interaction in (I) and a π–π interaction in (II) further stabilize these crystal structures.The crystals of two new salts, 2,6-diamino-4-chloropyrimidin-1-ium 5-chlorosalicylate, C The pyrimidine group offers two protonation sites (the two ring nitrogens) and the site of protonation depends on the nature of the substituents. Tautomerism of the pyrimidinium cation has also been reported recently via two N—H⋯O bonds (Table 1S(6) motif (involving the carboxyl group and the phenolic –OH) observed in salicylates/salicylic acid is also present  hydrogen bonds forming an et al., 2014et al., 2012aet al., 2012bvia a Cl⋯Cl interaction  Å; symmetry code: x, −1 + y, z; Cg1 and Cg2 are the centroids of the N1/C2/N3/C4/C5/C6 and C8–C13 rings, respectively] and C—Cl⋯π interactions  s Table 1 forming et al., 1995et al., 2007et al., 2001et al., 2002et al., 2003et al., 2007et al., 2007via N—H⋯O bonds. Weak π–π stacking interactions  is also present 8) Fig. 5. This tynt Fig. 6.et al., 2014et al., 2017H-benzimidazole-3-ium) naphthalene-1,5-disulfonate Uiso(H) = kUeq, where k = 1.5 for hydroxy and 1.2 for all other H atoms.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989018001196/zl2723sup1.cifCrystal structure: contains datablock(s) I, II. DOI: 10.1107/S2056989018001196/zl2723Isup2.hklStructure factors: contains datablock(s) I. DOI: 10.1107/S2056989018001196/zl2723IIsup3.hklStructure factors: contains datablock(s) II. DOI: Click here for additional data file.10.1107/S2056989018001196/zl2723Isup4.cmlSupporting information file. DOI: 1817972, 1817971CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title Schiff base compound is considerably non-planar, with the outer phenol and pyridine rings being inclined to each other by 70.21 (3)°. 19H17N3O, the configuration about the C=N bond is E. The molecule is non-planar, with the phenolic and pyridine rings being inclined to the central benzene ring by 56.59 (4) and 15.13 (14)°, respectively. In the crystal, molecules are linked by pairs of O—H⋯N hydrogen bonds, forming inversion dimers. The dimers are connected to neighbouring dimers by N—H⋯O hydrogen bonds and C—H⋯π interactions, forming layers parallel to the bc plane. The layers are linked by offset π–π interactions [intercentroid distance = 3.779 (2) Å], forming a three-dimensional supramolecular structure. Quantum chemical calculations of the molecule are in good agreement with the solid-state structure.In the title Schiff base compound, C The configuration about the C14=N2 bond is E, with a C11—N2—C14—C15 torsion angle of 176.40 (2)°. The C7—N1—C8 angle is 123.43 (1)° and the C7—N1—H1A—C8 fragment is approximately planar; the amine N1 atom exhibits a geometry what is typical for an sp2 rather than an sp3 atom. Bond angles C11—N2—C14 and C15—N3—C19 are also near 120° , and the imine group has a torsion angle C11—N2—C14—C15 of 176.40 (2)°.The molecular structure of the title compound is illustrated in Fig. 1bc plane  Å; Cg is the centroid of the N3/C15–C19 ring; interplanar distance = 3.462 (1) Å and slippage = 1.516 Å; symmetry code (iii) −x + 1, −y + 2, −z + 1].In the crystal, pairs of O—H⋯N hydrogen bonds link the molecules to form inversion dimers, with an f Table 1. The dimf Table 1 and C—H⋯f Table 1, formingne Fig. 3. The slaet al., 2016i.e. N-(2-pyridylmethylene)benzene-1,4-diamine ° and the N atoms are also trans to each another. This is in contrast to the situation in the metal complexes of EXOQAK, e.g. dichloro{N-[(pyridin-2-yl)methylene]benzene-1,4-diamine}zinc(II)  level  and lowest unoccupied orbitals (LUMO) are named frontier orbitals (FMOs). The LUMO and HOMO orbital energy parameters are considerably answerable for the charge transfer, chemical reactivity and kinetic/thermodynamic stability of a molecule 1. The DFT study of the title compound revealed that the HOMO and LUMO are localized in the plane extending from the whole phenol ring to the pyridine ring and electron distribution of the HOMO-1, HOMO, LUMO and the LUMO+1 energy levels are shown in Fig. 4The title compound was prepared from an equimolar mixture of 4-aminophenylaminomethylphenol  and pyridine-2-carbaldehyde  in (50 ml) methanol. The yellow reaction mixture was stirred for 3 h at room temperature and solvent was evaporated to 5 ml. The resulting yellow solid was isolated by filtration, washed successively with a cold water and methanol mixture (10 ml) and hexane (20 ml). The compound was recrystallized from hot methanol, giving yellow plate-like crystals. Finally, the yellow solid was dried in a vacuum desiccator .max nm : 258 , 383 . IR : ν(C=N) 1625, ν(N—H) 3265.Spectroscopic data: UV–Vis (MeOH): λ1H NMR : δ 8.6 , 7.4 , 7.8 , 8.0 , 8.5 , 6.7 , 6.6 , 4.1 , 7.1 , 7.2 , 9.3 (–OH), 6.5 (NH).m/z [M + H]+ calculated for C19H17N3O: 304.1444; found: 304.1455.HRMS (ESI) ca 40% of the data can be considered to be observed; hence the large value for Rint of 0.122. The N—H and O—H H atoms were located in difference Fourier maps. The OH H atom was freely refined, while during refinement, the N- and C-bound H atoms were included in calculated positions and treated as riding, with N—H = 0.86 Å and C—H = 0.93 Å, and Uiso(H) = 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989018003043/su5421sup1.cifCrystal structure: contains datablock(s) I, Global. DOI: 10.1107/S2056989018003043/su5421Isup2.hklStructure factors: contains datablock(s) I. DOI: 1542988CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Two independent copper(II) cations with coordination numbers of 4 and 6 are bridged by dianionic salicylate anions into chains extending parallel [001]. O—H⋯O hydrogen-bonding interactions involving both the coordinating and the lattice water molecules result in the formation of a three-dimensional network. 2(C7H4O3)2(H2O)2]·2H2O}n, contains two copper(II) cations in special positions (one on a twofold rotation axis and one on an inversion centre) and the the salicylate ligand in its dianionic form. By four- and six-coordinate metal coordination, chains are formed parallel to [001], which are extended by O—H⋯O hydrogen bonding into sheets extending parallel to (100). These sheets are weakly connected by O—H⋯O hydrogen bonding via the non-coordinating lattice water molecules into a three-dimensional network.The title compound, {[Cu Cu2 is four-coordinated in a square-planar configuration with donor atoms O2 of the carboxylate and O3 of the deprotonated hydroxy group. The two pairs of Cu—O distances are 1.905 (2) Å and are the shortest in the present structure (Table 1i and the O4—Cu1—O4i angles . This allows the five atoms Cu1, O1, O4, O1i and O4i to deviate significantly from planarity. The sum of the cis angles is 382.8 (3)° and the dihedral angle between the O1—Cu1—O1i/O4—Cu1—O4i planes is 49.86 (14)°. If one decides to consider Cu1 as four-coordinated, the coordination environment is consequently best described as halfway between square-planar and tetrahedral with approximate Dd2 symmetry ·2H2O  Å from the least-squares plane. This small deviation involves the carboxylate group with torsion angles of −3.4 (5) ° for C7—C2—C1—O1 and −2.5 (6) ° for C3—C2—C1—O2. The C—OH bond length of 1.359 (2) Å in CuO Table 1. One of x = 0.25 and z = 0.25, which is the intersection of two glide planes. By symmetry, there are four channels per unit cell with a volume of 59 Å3 each, as calculated with the PLATON software TOPOS 0.55 g (4 mmol) salicylic acid were suspended in 8 ml water. With a concentrated NaOH solution the pH value was adjusted to approximately 5. A solution of 0.5 g (2 mmol) copper(II) sulfate pentahydrate in 10 ml water was added. Crystals appeared after a few days of standing. From the unit-cell determinations it became clear that the mixture of crystals contained at least three species: colourless salicylic acid, green CuCrystal data, data collection and structure refinement details are summarized in Table 3ca 2° rotation about hkl =  I, global. DOI: 10.1107/S2056989017000883/wm5360Isup2.hklStructure factors: contains datablock(s) I. DOI: 1528159CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the 1,3-dioxane ring has an envelope conformation. In the crystal, classical O—H⋯O and N—H⋯O hydrogen bonds link molecules into a sheet structure, and a weak intermolecular C—H⋯Cl interaction extends the sheet structure into a three-dimensional network. 10H14Cl3NO5, the five-membered dioxolane ring adopts an envelope conformation with the C atom bonded to the butenoate side chain as the flap. It deviates from the mean plane of the other atoms in the ring by 0.446 (6) Å. In the crystal, molecules are connected by O—H⋯O hydrogen bonds into helical chains running along the b-axis direction. The chains are linked into a sheet structure parallel to (001) by an N—H⋯O hydrogen bond. These classical hydrogen bonds enclose an R44(24) graph-set motif in the sheet structure. Furthermore, a weak intermolecular C—H⋯Cl interaction expands the sheet structures into a three-dimensional network.In the title compound, C On the basis of this concept, we have explored the utilization of cyclic orthoamides, prepared from allylic diol and triol with known conditions  = 0.285 (4) Å and φ(2) = 296.7 (8)°]. The C=C and C=O double bonds of the unsaturated ester are slightly skewed with torsion angle C13=C14—C16=O18 being of 8.4 (6)°. There is a weak intramolecular N6—H6A⋯Cl1 interaction present  graph-set motif  graph-set motif  short contact of 3.076 (3) Å is also observed.In the crystal, a classical O—H⋯O hydrogen bond , related to the title compound  has not yet been reported.In the Cambridge Structural Database , one derivative , and one derivative . The amino H atoms were refined as adopting an sp2 configuration for WEKWOY and WAXBEE, while they were refined assuming an sp3 configuration of the N atom for LIBHIO and LAGMAK, as in the present study. Each N—H bond of the amino group in LIBHIO is mostly eclipsed by the neighbouring C—Cl bonds of the trichloromethyl group, whereas those in the title compound are slightly tilted  Å; N6—H6A⋯Cl1 = 115 (3)°] in the title compound . HRMS (ESI) m/z calculated for C10H15Cl3NO5+ [M + H]+: 334.0016; found: 334.0016.The title compound was afforded from Uiso(H) = 1.5Ueq(methyl C) and 1.2Ueq(C) for other C-bound H atoms. The hydroxy H atom was placed, guided by difference-Fourier maps, with O—H = 0.84 Å and refined with Uiso(H) = 1.5Ueq(O). The amino H atoms were placed, guided by difference-Fourier maps, and were refined with distance restraints of N—H = 0.86 (2) Å and H⋯H = 1.40 (2) Å, with Uiso(H) = 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017008283/su5377sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989017008283/su5377Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017008283/su5377Isup3.cmlSupporting information file. DOI: 1554119CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports6: Article number: 3745510.1038/srep37455; published online: 11222016; updated: 05042017This Article contains errors. The position of the mutation p.(R91W); (V172D) was incorrectly calculated, taking as a starting point the beginning of cDNA rather than the start codon. The correct position of the mutation is c.[271C > T]; [515T > A]. As a result of this the following changes in the Article are made:The legend of Figure 3 is incorrect,“(C) c.[325C > T]; [569T > A] (RPE65)”should read:“(C) c.[271C > T]; [515T > A] (RPE65)”.In Table 3 for the family ID F7, the DNA mutation should read ‘c.[271C > T]; [515T > A]’.In Figure 5 for family F7 ‘RPE65, c.325C > T; 569T > A; p.R91W; V172D’ should read ‘RPE65, c.271C > T; 515T > A; p.R91W; V172D’. The correct Figure 5 appears below as In the Results section under the subheading ‘Mutation analysis’,“The second mutation was identified in family F7 and was a new compound heterozygous mutations c.[325C > T]; [569T > A] resulting in p.(R91W); (V172D) ”.should read:“The second mutation was identified in family F7 and was a new compound heterozygous mutations c.[271C > T]; [515T > A] resulting in p.(R91W); (V172D) ”.


In the crystal, molecules are linked by O—H⋯O and O—H⋯N hydrogen bonds, forming chains propagating along [101].In the title boronic acid derivative, the mean plane of the –B(OH) 7H6BNO2, the mean plane of the –B(OH)2 group is twisted by 21.28 (6)° relative to the cyanophenyl ring mean plane. In the crystal, molecules are linked by O—H⋯O and O—H⋯N hydrogen bonds, forming chains propagating along the [101] direction. Offset π–π and B⋯π stacking interactions link the chains, forming a three-dimensional network. Hirshfeld surface analysis shows that van der Waals interactions constitute a further major contribution to the intermolecular interactions, with H⋯H contacts accounting for 25.8% of the surface.In the title compound, C However, the –B(OH)2 moiety contains two O—H hydrogen-bond donors and can, thus, form two O—H⋯X hydrogen bonds and adopt different conformations . This enables the generation of hydrogen-bonding networks with increased dimensionality (one to three dimensions) in the solid state , alcohols (–OH) and pyridines, which are based on molecular recognition processes 2 mean plane is twisted by 21.28 (6)° relative to the cyanophenyl ring mean plane. This torsion disables intramolecular C—H⋯O hydrogen bonding between the oxygen atom of the exo-oriented B—OH function and weakens the B—C π–π bonding interactions A; graph set B; graph set C; graph set a, Table 1et al., 2017i, C2⋯N1ii and O2⋯N1ii separations in motifs A, B and C are 2.796 (1), 3.452 (2) and 2.909 (2) Å, respectively  Å, see Table 1Cg⋯Cgiv = 3.8064 (8) Å; slippage 1.38 Å; symmetry code (iv) = −1 + x, y, z] and η2-type B⋯π contacts with B⋯C distances of 3.595 (2) and 3.673 (2) Å . Similar interactions are also depicted in molecular crystals formed between 1,4-benzenediboronic acid and aromatic amine N-oxides y Table 1, and are Å Fig. 3c. SimilCrystalExplorer  and the shape-index (−1.0 to 1.0 Å). In the dnorm map, the vivid red spots in the Hirshfeld surface are due to short normalized O⋯H and N⋯H distances corresponding to O—H⋯O and O—H⋯N interactions. The white spots represent the contacts resulting from C—H⋯N hydrogen bonding . On the shape-index surface for compound (I)2 group behaves simultaneously as a donor and an acceptor, meanwhile the –C≡N group is an acceptor only. The occurrence of offset π–π interactions is indicated by adjacent red and blue triangles .Hirshfeld surfaces and fingerprint plots were generated for (I)ng Fig. 4a. On thes Fig. 4b.et al., 2007The two-dimensional fingerprint plots quantify the contributions of each type of non-covalent interaction to the Hirshfeld surface  in 5 ml of ethanol was heated to reflux for 15 min. The solution was left to evaporate slowly at room temperature, giving after one week colorless crystals suitable for single-crystal X-ray diffraction analysis.Uiso(H) = 1.2Ueq(C) and 1.5Ueq(O).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989018003146/su5425sup1.cifCrystal structure: contains datablock(s) Global, I. DOI: 10.1107/S2056989018003146/su5425Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018003146/su5425Isup3.cmlSupporting information file. DOI: 1825335CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, the indazole ring system is oriented at dihedral angles of 25.04 (4) and 5.10 (4)° o the furan and benzene rings, respectively 20H16Cl2N2O2, the indazole ring system is approximately planar [maximum deviation = 0.033 (1) Å], its mean plane is oriented at dihedral angles of 25.04 (4) and 5.10 (4)° to the furan and benzene rings, respectively. In the crystal, pairs of C—Hind⋯Obo (ind = indazole and bo = benzyloxy) hydrogen bonds link the molecules into centrosymmetric dimers with graph-set motif R22(12). Weak C—H⋯π interactions is also observed. Aromatic π–π stacking between the benzene and the pyrazole rings from neighbouring molecules [centroid–centroid distance = 3.8894 (7) Å] further consolidates the crystal packing.In the title compound, C Its mean plane is oriented with respect to the furan  and benzene  rings at dihedral angles of A/B = 25.04 (4) and B/C = 5.10 (4)°. The dihedral angle between the furan and benzene rings is 20.21 (5)°. Atom C6 is −0.054 (1) Å from the indazole ring plane, while atom C1 is 0.038 (1) Å from the furan ring plane. Atoms Cl1, Cl2 and C14 are displaced by −0.0430 (3), 0.0233 (4) and −0.016 (1) Å, respectively, to the benzene ring plane.In the molecule of the title compound, Fig. 1, the bonind⋯ Obo (ind = indazole and bo = benzyloxy) hydrogen bonds  Å; symmetry code: (i) 2 − x, 2 − y, − z; Cg3 and Cg4 are the centroids of rings C (C15–C20) and D (N1/N2/C7/C8/C13)].In the crystal, pairs of C—Hs Table 1, enclosirs Fig. 2, which aon Fig. 3. Weak C—on Fig. 3 occur. πH-indazol-2-yl)ethanol with NaH and 2,5-dichlorobenzyl bromide. NaH  was added in small fractions to a solution of alcohol  in DMF (3–4 ml). Then, 2,5-dichlorobenzyl bromide  was added portionwise. The mixture was stirred at room temperature for 3 h, and the excess hydride was decomposed with a small amount of methyl alcohol. After evaporation to dryness under reduced pressure, a small amount of water was added and extracted with methylene chloride. The organic layer was separated, dried over anhydrous sodium sulfate, and then evaporated to dryness. The crude residue was purified by chromatography on a silica-gel column using a hexane–ethyl acetate mixture (10:1) as eluent. The ether was recrystallized from 2-propanol solution to obtain colourless crystals suitable for X-ray analysis .The title compound was synthesized by the reaction of 1-(furan-2-yl)-2-(2Uiso(H) = 1.2Ueq(C).The experimental details including the crystal data, data collection and refinement are summarized in Table 210.1107/S2056989016013827/xu5891sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989016013827/xu5891Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016013827/xu5891Isup3.cmlSupporting information file. DOI: 1501341CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


S(6) ring motif in the title compound. In the crystal, molecules are linked by C—H⋯O hydrogen bonds with a C(4) chain motif, and also by C—H⋯π interactions. The chains are linked by π–π interactions, forming a sheet parallel to the bc plane.There is an intramolecular O—H⋯N hydrogen bond forming an  15H18N2O3, the coumarin ring is essentially planar, with an r.m.s. deviation of 0.012 Å. An intramolecular O—H⋯N hydrogen bond forms an S(6) ring motif. The piperazine ring adopts a chair conformation. In the crystal, a C—H⋯O hydrogen bond generates a C(4) chain motif running along the c axis. The chain structure is stabilized by a C—H⋯π interaction. The chains are linked by π–π interactions [centroid–centroid distance of 3.5745 (11) Å], forming a sheet structure parallel to the bc plane.In the title compound, C H-chromen-2-one) derivatives have wide applications in diverse areas such as pharmaceuticals  ring motif  Å, θ = 1.9 (2)° and φ = 22 (7)°. The C16—N4—C15—C14 and C19—N4—C15—C14 torsion angles are −78.8 (2) and 158.52 (16)°, respectively. The bond lengths and angles of the title compound are normal and agree with those values in other Mannich bases of 7-hydroxycoumarin  chain motif running parallel to the c axis. A C—H⋯π interaction  Å, inter-planar distance = 3.404 Å and slippage = 1.090 Å; symmetry code: (iii) −x, −y, −z + 1], forming a supramolecular sheet parallel to the bc plane.In the crystal, molecules are linked by a C—H⋯O hydrogen bond -l-alanine : [M + H]+, 275.1. Analysis calculated for C15H18N2O3: C 65.68, H 6.61, N 10.21%; found: C 65.40, H 6.45, N 10.06%.The title compound was prepared by modification of the reported procedure (Mazzei Uiso(H) = 1.2Ueq(C).Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989016017217/is5461sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989016017217/is5461Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989016017217/is5461Isup3.cmlSupporting information file. DOI: 1511659CCDC reference: crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The title compound comprises a central pyromellitic diimide moiety with terminal decyl groups, with potential applications as an acaricide, insecticide and mematicide. 30H44N2O4 isoindole-1,3,5,7-tetraone], consists of a central pyromellitic diimide moiety with terminal decyl groups at the N-atom positions. The centre of the molecule lies on a crystallographic inversion centre so the asymmetric unit contains one half-molecule. The molecule exhibits a rod-shaped conformation, like other similar compounds of this type, the distance between the ends of terminal decyl groups being 32.45 Å. The packing is dominated by a lamellar arrangement of the molecules, which is reinforced by C—H⋯O hydrogen bonds and C—O⋯π interactions, forming a classic herringbone structure. The molecular structure is consistent with the theoretical calculations performed by density functional theory (DFT).The title compound, C In addition, a reversible anti to syn transition was achieved by agitating in mixed organic solvents  x, −y + z − ii⋯Cg1 (Cg1 is the centroid of the N1/C1–C4 ring) interactions [O⋯π = 3.272 (1) Å; symmetry code: (ii) x, −y + z + bc plane : d = 8.27 , 3.74 , 1.70 , 1.32 , 0.88 A mixture of pyromellitic dianhydride  and decyl amine  in toluene (10 ml) and dimethyl sulfoxide (6 ml) was heated at 453 K with stirring for 5 h. Upon cooling to room temperature, an off-white crude solid was filtered and washed with water, methanol and ether. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a dichloromethane solution of the title compound. d(C—H) = 0.95 Å, Uiso(H) = 1.2Ueq(C) for aromatic C—H, d(C—H) = 0.99 Å, Uiso(H) = 1.2Ueq(C) for Csp3—H, d(C—H) = 0.98 Å, Uiso = 1.5Ueq(C) for methyl group.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989017006867/hb7674sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017006867/hb7674Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989017006867/hb7674Isup3.cmlSupporting information file. DOI: 1548456CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Scientific Reports6: Article number: 3762710.1038/srep37627; published online: 11222016; updated: 04052017This Article contains an error in the labelling of Figure 4D, where the panel labels ‘αCD3’ and ‘αCD3 + OFS’ are inverted. The correct


Both complexes display a bent metallocene unit, the metal centre is coordinated in a distorted tetrahedral geometry.The crystal structures of two  ansa-titanocene trifluoromethanesulfonate complexes bearing the Me2Si(C5Me4)2 ligand are reported, namely [dimethylbis(η5-tetramethylcyclopentadienyl)silane]titanium(III) toluene monosolvate, [Ti(CF3O3S)(C20H30Si)]·C7H8, 1, and chlorido[dimethylbis(η5-tetramethylcyclopentadienyl)silane](trifluoromethanesulfonato-κO)titanium(IV), [Ti(CF3O3S)(C20H30Si)Cl], 2. Both complexes display a bent metallocene unit, the metal atom being coordinated in a distorted tetrahedral geometry, with the trifluoromethanesulfonate anion acting as a bidentate or monodentate ligand in 1 and 2, respectively. In 1, weak π–π stacking interactions involving the toluene solvent molecules [centroid-to-centroid distance = 3.9491 (11) Å] are observed.The crystal structures of two  Photolysis of the latter results in a photoreduction and elimination of the OH ligand to give a TiIII trifluoromethanesulfonate complex. Several cycles of this synthetic model scheme for water splitting can be passed Ti].Variation of the 2Si(C5Me4)2Ti(OTf)]·C7H8 (1) and [Me2Si(C5Me4)2Ti(OTf)Cl] (2), respectively. Both metal complexes exhibit distorted tetrahedral coordination geometries and show the typical bent metallocene moiety.Figs. 11 crystallizes with one molecule of toluene in the asymmetric unit. The crystal structure of 1 confirms the bidentate binding mode of the trifluoromethanesulfonate ligand, which is in contrast to other complexes bearing different metallocene units 2]2Nd(κO-OTf) 3]2Ce , B: 2.058 (2) Å].However, this binding mode is known for group 4 complexes  Å, which is slightly shorter compared to the bis(pentamethylcyclopentadienyl) compound Cp*2Ti(Cl)(OTf) .Titanocene(IV) complexes with a trifluoromethanesulfonate ligand in a κ al. 1994; Taw et  al. 2003; Deacon  al. 2006; Kessler al. 2011 and Gode al. 2015. The cry1, weak π–π stacking interactions were observed between two neighbouring toluene solvent molecules along the a axis [distance between ring centroids 3.9491 (11) Å and ring slippage of 1.985 Å].For 2Si(C5Me4)2Ti(η2-Me3SiC2SiMe3) was prepared according to a published procedure 2Ti(η2-Me3SiC2SiMe3)  and Yb(OTf)3  were dissolved in 30 ml of toluene and heated at 333 K overnight, resulting in a colour change from dark yellow to green. All volatiles were removed in vacuo and the residue was again dissolved in toluene. The solution was filtered and the solvent was evaporated in vacuum to yield complex 1 as a dark-green powder. Single crystals suitable for an X-ray analysis were obtained from a saturated toluene solution at 195 K.Synthesis of 2: In an experiment which aimed at the synthesis of the above TiIII trifluoromethanesulfonate complex 1, a batch of the alkyne complex Me2Si(C5Me4)2Ti(η2-Me3SiC2SiMe3) was used that contained significant amounts of the monochloride complex Me2Si(C5Me4)2TiCl, which was formed by incomplete reduction of the dichloride complex Me2Si(C5Me4)2TiCl2 during synthesis of the alkyne complex. Reaction of the monochloride complex with Yb(OTf)3 yields the ansa-titanocene(IV) chloride trifluoromethanesulfonate complex 2. Single crystals suitable for an X-ray analysis were obtained from a saturated toluene solution by slow cooling from 353 K to room temperature.Uiso(H) = 1.2Ueq(C) or 1.5Ueq(C) for methyl H atoms. A rotating model was used for the methyl groups.Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2056989016018363/rz5199sup1.cifCrystal structure: contains datablock(s) 1, 2, New_Global_Publ_Block. DOI: 10.1107/S2056989016018363/rz51991sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989016018363/rz51992sup3.hklStructure factors: contains datablock(s) 2. DOI: 1517524, 1517523CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the original publication  one authIncorrect author name:Céline ChaleurCorrect author name:Céline Chauleur


II complex is centrosymmetric and the molecules are linked by O—H⋯O and C—H⋯O hydrogen bonds into the three-dimensional supramolecular network.The Mn 10H11O2)2(C10H14N2O)2(H2O)2], the MnII cation is located on an inversion centre. The four O atoms form a slightly distorted square-planar arrangement around the MnII cation, and the distorted octahedral coordination is completed by two pyridine N atoms at distances of 2.3289 (15) Å. The dihedral angle between the planar carboxylate group and the adjacent benzene ring is 87.73 (16)°, while the benzene and pyridine rings are oriented at a dihedral angle of 43.03 (8)°. In the crystal, the water molecules are involved in both intramolecular (to the non-coordinating carboxylate O atom) and intermolecular (to the amide carbonyl O atom) O—H⋯O hydrogen bonds. The latter lead to the formation of layers parallel to (100). These layers are further linked via weak C—H⋯O hydrogen bonds, resulting in a three-dimensional supramolecular network. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (70.0%), H⋯O/O⋯H (15.5%) and H⋯C/C⋯H (14.0%) interactions. One of the ethyl groups of the diethylnicotinamide ligand is disordered over two sets of sites, with an occupancy ratio of 0.282 (10):0.718 (10).In the title centrosymmetric complex, [Mn(C N,N-Diethylnicotinamide (DENA) is an important respiratory stimulant 2(DENA)2(H2O)2]  and some benzoic acid derivatives as ligands, e.g. [Zn(NA)2(C7H5O3)2] ·H2O      , was synthesized and its crystal structure is reported on herein.The structure–function–coordination relationships of the arylcarboxylate ion in MnII cation located on an inversion centre, one 2,4,6-trimethylbenzoate (TMB) anion and one N,N-diethylnicotinamide (DENA) molecule together with the one water molecule, with all ligands coordinating to the MnII cation in a monodentate manner  of the two symmetry-related TMB anions and the two symmetry-related water O atoms (O4 and O4i) at distances of 2.0999 (14) and 2.2230 (15) Å, respectively, to form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination sphere is completed by the two pyridine N atoms (N1 and N1i) at distances of 2.3289 (15) Å of the two symmetry-related DENA ligands in the axial positions   Å]. The Mn—N bond length [2.3289 (15) Å] is the longest one in the MnO4N2 octahedron. The Mn1 atom lies 0.0697 (1) Å above the planar (O1/O2/C1) carboxylate group. The O2—C1—O1 bond angle [125.5 (2)°] seems to be significantly increased than that present in a free acid [122.2°], in which the O2—C1—O1 bond angle may be compared with the corresponding values of 123.5 (2) and 120.4 (2)° in (II), 119.2 (3) and 123.8 (2)° in (III), 123.86 (13) and 118.49 (14)° in (IV), 125.11 (13) and 124.80 (14)° in (V) and 126.65 (14)° in (VI), where the benzoate ions are coordinated to the metal atoms only bidentately in (V), only monodentately in (VI) and both monodentately and bidentately in (II), (III) and (IV). The O—Mn—O and O–Mn—N bond angles  deviate slightly from ideal values, with same average values of 90.00 (6)°.The near equalities of the C1—O1 [1.254 (3) Å] and C1—O2 [1.243 (3) Å] bonds in the carboxylate groups indicate delocalized bonding arrangements, rather than localized single and double bonds. The Mn—O bond lengths [2.2230 (15) Å] for water oxygen atoms are by A (C2–C7) ring is 87.73 (16)°, while the benzene A and pyridine B (N1/C11–C15) rings are oriented at a dihedral angle of A/B = 43.03 (8)°.The dihedral angle between the planar carboxylate group (O1/O2/C1) and the adjacent benzene w⋯Oc  hydrogen bonds (Table 1S(6) ring motif  hydrogen bonds  and C—HDENA⋯ODENA hdyrogen bonds  analysis  in H2O (100 ml) and N,N-diethylnicotinamide  in H2O (10 ml) with sodium 2,4,6-trimethylbenzoate  in H2O (150 ml). The mixture was filtered and set aside to crystallize at ambient temperature for three weeks, giving colourless single crystals.The title compound was prepared by the reaction of MnSOUiso(H) = k × Ueq(C), where k = 1.5 for methyl H atoms and k = 1.2 for other H atoms. The disordered ethyl group  was refined over two sets of sites with distance restraints and SIMU and DELU restraints  I, global. DOI: 10.1107/S2056989018003377/xu5920Isup2.hklStructure factors: contains datablock(s) I. DOI: 1826038CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The current redetermination confirms the previous structure report, but with considerably higher precision and accuracy. 3)2(C5H7O2)2] or SnMe2(acac)2, from CCD data recorded at 100 K basically confirms the previous study based on integrated film data recorded at room temperature [Miller & Schlemper  > 6.7694 (4) Å]. The molecule belongs to point group iC with the SnIV atom on a centre of inversion. The SnIV atom shows a slightly distorted octahedral coordination sphere with the methyl groups in trans positions and a Sn—C bond length of 2.115 (2) Å which may serve as a standard value for an Sn—CH3 bond of an octahedrally coordinated SnIV atom. The Sn—O bonds involving the two carbonyl groups of the acetylacetonate ligand are of equal length [2.180 (1) and 2.183 (1) Å], as are the C=O [1.273 (1) and 1.274 (1) Å] and C—C bond lengths [1.393 (2) and 1.400 (2) Å]. The acetylacetonate ligand deviates considerably from planarity, with a dihedral angle of 5.57 (9)° between the least-squares planes of the two acetone moieties. The four O atoms of the two symmetry-related acetylacetonate ligands are arranged in a nearly quadratic rectangle. Weak C—H⋯O interactions consolidate the crystal packing.The redetermination of the title compound, [Sn(CHmper 1972. Inorg.  Moreover, the title compound is an excellent candidate for the determination of the Sn—CMe bond length as another reference in case the SnIV atom is in a well-defined octahedral coordination. The precise measurement of this Sn—C distance therefore should supplement the observations of Britton  and the constitution of the asymmetric unit comprising half a formula unit with the Sn atom at a crystallographic centre of inversion [Wyckhoff symbol: b]. As we performed the X-ray measurement at 100 K, the unit-cell volume is somewhat smaller in comparison with the original room-temperature data which is mainly caused by a considerable change of the a axis from 7.12 (1) to 6.7694 (4) Å while changes of all other lattice parameters  show a normal temperature-dependent shrinkage.The redetermination of the crystal structure of the title compound confirms the former results obtained by Miller & Schlemper 1973 with restrans position °. The four O atoms of the two symmetry-related acetylacetonate ligands around the Sn atom form a planar rectangle with similar edge lengths [O1⋯O2 = 2.975 (1)/O1⋯O1 = 3.191 (1) Å], and almost right angles [89.9 (1)° at O1 and 90.1 (1)° at O2]. This plane is nearly perpendicular to the axis through the two methyl groups [deviation: 0.44 (2)°] but constitutes a dihedral angle of 10.2 (1)° with the least-squares plane through the two carbonyl groups of the acetylacetonate ligand   x, y, 1 + z; (ii) 1 − x, 1 − y,1 − z; (iii) x, y, z; (iv) x, −y, z]  2 − x, 1 − y, 1 − z] for each oxygen atom. In summary, the intermolecular contacts result in a columnar arrangement of the molecules parallel to the a axis . The crystals are stable in air.The synthesis of the title compound by refluxing a suspension of dimethyltin oxide, Mebias 1965. Single 1H NMR , nJ [Hz]): δ(CH3—Sn) = 0.58, 2J(1H—119/117Sn) = 100.6/97.1; δ(CH3)acac = 1.96; δ(CH)acac = 5.31 ], nJ [Hz]): δ(CH3—Sn) = 7.75, 1J(13C—119/117Sn = 973.7/930.4), δ(CH3)acac = 27.94, δ(CH)acac = 100.09, δ(C=O)acac = 190.75 ]: 3010 w, 2920 w,1562 s, 1512 s, 1436 m, 1361 s,bd, 1256 m, 1203 m, 1015 m, 925 m, 803 m, 781 m, 655 m, 572 m, 552 m ]: 3092 w, 2999 w, 2920 s, 2708 w, 1574 w, 1427 w, 1366 m, 1263 m, 1206 m, 1194 m, 1021 w, 927 m, 668 m, 567 m, 512 s, 415 m, 220 m, 130 m 94 m, 68 m , and 0.95 Å (–CH–) and with Uiso(H) = 1.2 and 1.5Ueq(C), respectively.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989017003206/wm5370sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989017003206/wm5370Isup2.hklStructure factors: contains datablock(s) I. DOI: 1534819CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Ti and Al(Ga), and in a μ2 manner.The molecular structures of two isotypic titanium(III) complexes bearing an trimethylaluminium or -gallium motif are reported. In both compounds, two methyl groups coordinate to the metal atoms,  EMe3 unit  with two μ2-coordinating methyl groups, namely [μ-1(η5)-(adamantan-1-yl-2κC1)cycylopentadienyl]di-μ2-methyl-methyl-2κC-[1(η5)-pentamethylcyclopentadienyl]aluminiumtitanium(III), [AlTi(CH3)3(C10H15)(C15H18)], and [μ-1(η5)-(adamantan-1-yl-2κC1)cycylopentadienyl]di-μ2-methyl-methyl-2κC-[1(η5)-pentamethylcyclopentadienyl]galliumtitanium(III), [GaTi(CH3)3(C10H15)(C15H18)], are reported. Reacting a dinuclear nitrogen-bridged low-valent titanium(III) complex with the Lewis acids AlMe3 or GaMe3 results in the loss of molecular dinitrogen and the formation of two monomeric titanocene(III) fragments bearing two μ2-bridging methyl groups. Single crystal X-ray diffraction reveals the formation of a new E—C bond involving the pentafulvene ligand while the bridging and terminal methyl groups remain intact.The isotypic crystal structures of two titanocene complexes containing an  The crystal packing Fig. 3 appears et al., 20053 and GaMe3 solutions were purchased from Sigma Aldrich and used as received. Solvents were dried according to standard procedures over Na/K alloy with benzophenone as indicator and distilled under a nitrogen atmosphere.All reactions were carried out under a dry nitrogen atmosphere using Schlenk techniques or in a glove box. The starting titanium complex was prepared according to a published procedure (Scherer Synthesis of 1:η5-pentamethylcyclopentadienyl)(η5:η1-adamantylidenepentafulvene)titanium]-μ2,η1,η1-dinitrogen  was dissolved in toluene and AlMe3  was added. The colour of the solution changed from blue to green, after 48 h the volume had reduced to 5 ml and another 5 ml of n-hexane were added. Crystals suitable for X-ray diffraction separated after 48 h directly from the mother liquor.Bis[(Synthesis of 2:η5-pentamethylcyclopentadienyl)(η5:η1-adamantylidenepentafulvene)titanium]-μ2,η1,η1-dinitrogen  was dissolved in toluene and GaMe3  was added. The former blue solution turned brown and was stored at 233 K. After 10 days, brown–green crystals suitable for X-ray diffraction separated from the mother liquor.Bis[(Uiso(H) = 1.2Ueq(C); H atoms of all methyl groups were refined freely.Crystal data, data collection and structure refinement details are summarized in Table 110.1107/S2056989017004856/wm5378sup1.cifCrystal structure: contains datablock(s) global, 1, 2. DOI: 10.1107/S2056989017004856/wm53781sup2.hklStructure factors: contains datablock(s) 1. DOI: 10.1107/S2056989017004856/wm53782sup3.hklStructure factors: contains datablock(s) 2. DOI: 1540662, 1540661CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information: