The title compound possesses crystallographically imposed twofold symmetry with the two C atoms of the central benzene ring and the C atom of its methyl substituent lying on the twofold rotation axis. The two dansyl groups are twisted away from the plane of methylphenyl bridging unit in opposite directions. The crystal packing features weak C—H⋯O hydrogen bonds. 31H30N2S2O6, possesses crystallographically imposed twofold symmetry with the two C atoms of the central benzene ring and the C atom of its methyl substituent lying on the twofold rotation axis. The two dansyl groups are twisted away from the plane of methylphenyl bridging unit in opposite directions. The three-dimensional arrangement in the crystal is mainly stabilized by weak hydrogen bonds between the sulfonyl oxygen atoms and the hydrogen atoms from the N-methyl groups. Stacking of the dansyl group is not observed. From the DFT calculations, the HOMO–LUMO energy gap was found to be 2.99 eV and indicates n→π* and π→π* transitions within the molecule.The title compound, C Such modified oligonucleotides can be used to prepare and detect the sequence of fluorogenic probes in DNA  rings, Fig. 1O-dansyl groups on either side of a bridging methylphenyl ring that is essentially planar. The S1—O1—C4—C3 torsion angle is 72.98 (16)° with the methylphenyl ring plane. The S1 sulfur atoms have distorted tetrahedral geometries, with an O2—S1—C6 bond angle of 109.18 (8)°. The two naphthalene units in each dansyl group are inclined to one another at an angle of 52.29 (6)°; however, no stacking of the naphthalene units is observed.The title compound crystallizes in the space group le Fig. 1. The hydc-axis direction, Fig. 2B—O3 and C16—H16C—O2 contacts further link the molecules into sheets in the ab plane, Fig. 3a-axis direction, Fig. 4In the crystal structure, the supramolecular packing is dominated by weak C—H⋯O hydrogen bonds, Table 1GAUSSIAN09 program package  calculations were performed at the CAM-B3LYP/6-311G  level as implemented in the et al., 2016et al., 2015N-cyclododecyl-5-(dimethylamino)naphthalene-1-sulfonamide -5-(dimethylamino)naphthalene-1-sulfonamide di naphthalene-1-sulfonamido]phenyl 5-(dimethylamino)naphthalene-1-sulfonate arene  complexes [5-(dimethylamino)naphthalene-1-sulfonamido]bis(triphenylphosphine)digold (UZEJAL) and [5-(dimethylamino)naphthalene-1-sulfonamido]tris(triphenylphosphine)trigold perchlorate (UZEJEP) (Cho 2 atmosphere for 24 h. The solvent was removed with a rotary evaporator. The residue was added to water (15 ml) and extracted with dichloromethane (3 × 25ml). The organic layer was dried with anhydrous Na2SO4 and the product was purified by column chromatography using CH2Cl2 as the eluent. The dichloromethane was slowly evaporated to afford a green solid in 65% yield. Light-green block-like crystals were grown in chloroform at room temperature.The title compound was synthesized by mixing 3,5-dihydroxytoluene  and dansyl chloride  using potassium carbonate as a base in acetonitrile solvent (40 ml). The reaction mixture was heated at 363 K and stirred under an Nd(C—H) = 0.95 Å and Uiso(H) = 1.2Ueq(C) for aromatic and d(C—H) = 0.98 Å, Uiso(H) = 1.5Ueq(C) for methyl H atoms. As atom Cl lies on a twofold rotation axis, the H atoms of the Cl methyl group are disordered with occupancies fixed at 0.5.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989019009058/sj5573sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019009058/sj5573Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019009058/sj5573Isup3.cmlSupporting information file. DOI: 1535824CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the crystal, C—H⋯O and C—H⋯S hydrogen bonds and π–π interactions lead to the formation of a two-dimensional network structure parallel to (110). Hirshfeld surface analysis confirmed the intermolecular interactions.The title compound was synthesized from naphthalene diimide and methylthiopropiamine. The asymmetric unit consists of half of the total molecule as the molecule lies on an inversion center. Intramolecular C—H⋯O and C—H⋯S hydrogen bonds cause the molecule to have an  22H22N2O4S2, was synthesized by the reaction of 1,4,5,8-naphthalenetetracarboxylic dianhydride with 3-(methylsulfanyl)propylamine. The whole molecule is generated by an inversion operation of the asymmetric unit. This molecule has an anti form with the terminal methylthiopropyl groups above and below the aromatic diimide plane, where four intramolecular C—H⋯O and C—H⋯S hydrogen bonds are present and the O⋯H⋯S angle is 100.8°. DFT calculations revealed slight differences between the solid state and gas phase structures. In the crystal, C—H⋯O and C—H⋯S hydrogen bonds link the molecules into chains along the [2ABAB sequence along the c-axis direction. Hirshfeld surface analysis shows that van der Waals interactions make important contributions to the intermolecular contacts. The most important contacts found in the Hirshfeld surface analysis are H⋯H (44.2%), H⋯O/O⋯H (18.2%), H⋯C/C⋯H (14.4%), and H⋯S/S⋯H (10.2%).The title compound, C The mols Table 1. The terGAUSSIAN09 software package  Å; Cg1 and Cg2 are the centroids of the C6/C7/C7iii/C8iii/C10/C11iii and C6iv/C7iv/C7v/C8v/C10iv/C11v rings, respectively; symmetry codes: (iii) −x + 2, −y + 1, −z; (iv) −x + 2, −y, −z; (v) x, y − 1, z]. These π–π interactions lead to a two-dimensional network structure parallel to the (001) plane  indicate the Hirshfeld surface analysis was performed using a–e), which show the H⋯H, H⋯C/C⋯H, H⋯O/ O⋯H, H⋯N/N⋯H, and H⋯S/S⋯H contacts. The relative contributions of the atomic contacts to the Hirshfeld surface are summarized in Table 3The C—H⋯O and C—H⋯S hydrogen bonds and π–π stacking interactions are identified in the two-dimensional fingerprint plots Fig. 7a–e, whiA mixture of 1,4,5,8-naphthalenetetracarboxylic dianhydride  and 3-(methylsulfanyl)propylamine  in toluene (5 mL) and quinoline (15 mL) was heated at 453 K with stirring for 1h. Upon cooling to room temperature, a golden yellow crude solid was filtered off and washed with diethyl ether. A golden yellow powder was obtained. Crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of a dichloromethane solution of the title compound.1H NMR : δ 8.77 , 4.33 , 2.64 , 2.14 , 2.07 . 13C NMR : δ 162.81, 130.99, 126.69, 126.57, 40.01, 31.61, 27.16 and 15.31. IR : 3344 (m); 3071 (m); 2916 (s); 2848 (s); 1999 (s); 1693 (s).et al., 2016et al., 2013n-alkyl groups are known with 2,7-dibutylbenzo[lmn]phenanthroline-1,3,6,8-tetraone naphthalene-4,5,8,9-tetracarboxylic acid diimide  = 0.95 Å, Uiso = 1.2Ueq(C) for aromatic, d(C—H) = 0.99 Å, Uiso = 1.2Ueq(C) for methylene, and d(C—H) = 0.98 Å, Uiso = 1.5Ueq(C) for the methyl H atoms.Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989019007771/sj5571sup1.cifCrystal structure: contains datablock(s) I, New_Global_Publ_Block. DOI: 10.1107/S2056989019007771/sj5571Isup2.hklStructure factors: contains datablock(s) I. DOI: 1919395CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


III compounds is the octahedral coordination of the IrIII atom by a PCP pincer complex, a C atom of a (ethoxyoxoethanylidene)methane group and two variable ligands X  and Y .The common structural feature of the four title Ir 4P,C,C′,P′)chloridohydridoiridium(III) chloride methylene chloride 2.75-solvate (4), (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4P,C,C′,P′)chlorido(ethoxyoxoethanido)iridium(III) chloride–methanol–water (1/1/0.5) (5), (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4P,C,C′,P′)dichloridoiridium(III) chloride–methanol–water (1/1/2) (6) and (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ4P,C,C′,P′)carbonyl(ethoxyoxoethanide)iridium(III) dichloride–methylene chloride–water (1/2/1.5) (7) or in terms of their formulae [Ir(C55H50O2P4)ClH]Cl·2.75CH2Cl2 (4), [Ir(C4H7O2)(C55H50O2P4)Cl]Cl·CH3OH·0.5H2O (5), [Ir(C55H50O2P4)Cl2]Cl·CH3OH·2H2O (6) and [Ir(C4H7O2)(C55H50O2P4)(CO)]Cl2·2CH2Cl2·1.5H2O (7) is a central IrIII atom coordinated in a distorted octahedral fashion by a PCCP ligand system and two additional residues, such as chlorides, a hydride, a carbonyl or an alkyl unit. Thereby, the PCP pincer ligand system and the residue trans to the carbodiphosphorane (CDP) C atom surround the iridium(III) transition metal in the equatorial plane under the formation of two five-membered dissimilar chelate rings . A cyclopropane-like heterocycle is positioned approximately orthogonal (84.21–88.85°) to the equatorial plane, including an alkylidene bridge connecting the IrIII atom and the coordinating CDP atom of the PCP subunit. In general, the neutral PCCP ligand system coordinates the metal in a tetradentate way via three Lewis acid/base bonds and by an alkylidene unit presenting strengthened interactions. In all the crystal structures, (disordered) solvent molecules are present in the voids of the packed molecules that interact with the positively charged complex and its chloride counter-ion(s) through weak hydrogen bonding.The common feature of the four iridium(III) salt complexes, (bis{[(diphenylphosphanyl)methyl]diphenylphosphanylidene}(ethoxyoxoethanylidene)methane-κ Nomura et al., 2011et al., 1998et al., 1991et al., 2005Carbodiphosphoranes (CDP) in combination with transition metals initialize a huge variety of functionalities. As a result of the presence of two 2]Cl  atom, followed by deprotonation of the carbodiphosphorane carbon atom, the generation of a hydrido ligand caused by an oxidation of the iridium(I) atom and the formation of the Cl complex 1  an Cl2 precursor system (2) is generated in high yields (86%). Moreover, the preparation of complex 2 in a less polar solvent environment like chloroform/acetonitrile or in a solvent mixture of methylene chloride/acetonitrile (v/v 5:1) is not possible and quantitatively results in the substitution of one phosphine moiety of the carbodiphosphorane functionality against the carbene CHCO2Et subunit. An Cl complex 3 is generated, offering a phosphorus ylide carbon backbone  to 333 K for 2 h benefits the ring-opening reaction of the PCCP pincer ligand system. Therefore, a reorganization of the ligand system is supported, resulting in the quantitative formation of complex 3. Furthermore, evaporation of the reaction mixture of complex 2 causes an exchange of the acetonitrile solvent ligand with a chloride counter-ion and the creation of the desired Cl complex 4. If the starting materials Cl alkyl derivative 5. This reaction procedure is well known, and the mechanism of the intermolecular insertion reaction has been clarified via an intermediate carbene complex (dppm)2-κ4P,C,C′,P′}Cl2]Cl complex 6. Besides, a replacement of the chlorido ligand of compound 5 by a carbonyl group is possible and results in the Cl2 complex 7.The stucture of this iridium(III) PCCP complex was completely determined by NMR spectroscopy and X-ray crystallography, but up to now crystallization attempts of the intermediates, 4–7.Here we report details of the syntheses and crystal structures of complexes 4, Cl, comprises of one formula unit of 4 and additionally of 2.75 molecules of methylene chloride solvent molecules. The central iridium(III) transition metal is surrounded in a distorted octahedral fashion by a PCCP pincer-like ligand system, and anionic chlorido and hydrido ligands (dppm)2-κ4P,C,C′,P′] ligand coordinates the IrIII metal in a tetradentate fashion via two P and two C atoms under formation of two five-membered, dissimilar chelate rings  and one three membered heterocycle. The PCP ligand exhibits a meridional arrangement with the hydrido ligand completing the equatorial plane trans to the C1 carbodiphosphorane atom. A cyclopropane-like chelate ring is positioned nearly normal (84.21°) to the equatorial plane, and a chlorido ligand is positioned trans to the alkylidene carbon atom C4. The Ir—C1 [2.273 (4) Å] and Ir—C4 [2.072 (5) Å] distances differ significantly and consequently these values substantiate a strengthened interaction between the iridium(III) metal and the alkylidene carbon atom. The C1—C4 separation [1.515 (6) Å] is slightly shorter in comparison to a typical C—C single bond but, in general, very close to that of cyclopropanes. However, in comparison with a cyclopropane molecule the C4—Ir1—C1 [40.5 (2)°], C4—C1—Ir1 [62.6 (2)°] and C1—C4—Ir1 [76.9 (3)°] angles emphasise a significant distortion of the synthesized three-membered heterocycle. All mentioned geometric features of this strained Ir—C1—C4 metallacycle can be associated with the structural results of the Ru—C—C triangle reported by Zhang et al. (dppm)2-κ4P,C,C′,P′}(CH2CO2Et)Cl]Cl, is defined by one complex 5, one half-occupied water molecule and one disordered methanol solvent molecule. In comparison with the structural features discussed in detail for compound 4, significant differences pertain only to the equatorial position trans to C1. Here the hydrido ligand in 4 is exchanged by an ethyl acetate unit (dppm)2-κ4P,C,C′,P′}Cl2]Cl. In its crystalline form, besides one formula unit of 6, one solvent molecule of MeOH and two water molecules in total are present in the asymmetric unit. Overall, this PCCP derivative shows very similar structural characteristics (dppm)2-κ4P,C,C′,P′}(CH2CO2Et)(CO)]Cl2  = 2.83 Å] exhibiting distances shorter than the sum of the van der Waals radii ], 2.91 Å (H3A⋯Cl2) and 2.40 Å (H3B⋯O1)  Fig. 7.6, the methylene groups of the PCP unit and the chloride counter-ion and the solvent molecules form C—H⋯O and C—H⋯Cl interactions ], 2.66 Å (H3B⋯Cl3) and 2.40 Å [H6A⋯O3 ] ] Fig. 8.7, the chloride counter-ions interact with both the PCP pincer ligand system and the solvent molecules. The solvent molecules also show interactions with the iridium complex III{C(CHCO2Et)(dppm)2-Synthesis of Cl·2.75CH2Cl2 (4)κ: A mixture of [CH(dppm)2]Cl  and [IrCl(cod)]2  was solved in 0.1 ml of MeCN. After a reaction time of one minute, a solution of ethyl diazoacetate  in MeOH (0.5 ml) was added. 10 min later, a deep yellow liquid was obtained. The volatiles were removed and the remaining solid was dissolved in methylene chloride (0.6 ml), leading to complex 4 in high yield . Single crystals of complex 4 were grown from a solvent mixture of n-hexane (1.2 ml) and CH2Cl2 (0.2 ml). 31P {1H} NMR (CHCl3): δ = 18.8 , 38.1 , 34.7 , 10.7  ppm; 1H NMR : δ = −15.2  ppm; 13C {1H} NMR (CDCl3): δ = 3.6  ppm.III{C(CHCO2Et)(dppm)2-Synthesis of Cl·CH3OH·0.5 H2O (5):} was added to a solution of complex 4  in CH2Cl2 (0.6 ml), and the reaction mixture was stirred for 30 min. Complex 5  was formed quantitatively. Single crystals were obtained via slow evaporation of a 1:1methylene chloride/methanol mixture. 31P {1H} NMR (CHCl3): δ = 0.3 , 40.6 , 36.4 , −4.4  ppm; 13C {1H} NMR (CDCl3): δ = 3.1  ppm.III{C(CHCO2Et)(dppm)2-Synthesis of Cl·CH3OH·2H2O (6):}Cl A solution of complex 4  in CH2Cl2 (0.6 ml) was treated with hydrochloric acid  and stirred vigorously for approximately 10 min. The organic phase was separated and washed with water (0.5 ml) three times in total. Complex 6  was formed almost quantitatively. Yellow single crystals were generated by slow evaporation of a 1:1 solvent mixture of MeCN and MeOH. 31P {1H} NMR (CHCl3): δ = −6.1 , 46.9 , 45.8 , −10.3  ppm; 13C {1H} NMR (CDCl3): δ = 3.8  ppm.III{C(CHCO2Et)(dppm)2-Synthesis of Cl2·2CH2Cl2·1.5H2O (7):} in CH2Cl2 was placed under an atmosphere of CO. After a reaction time of 1 h, complex 7 had formed quantitatively . Single crystals were grown from a solution of methylene chloride, covered with a small amount of ethyl acetate. 31P {1H} NMR (CH2Cl2): δ = −6.5 , 41.2 , 39.7 , −16.4  ppm; 13C {1H} NMR (CD2Cl2): δ = 16.1 , 172.8  ppm.Crystal data, data collection and structure refinement details are summarized in Table 6Uiso(H) = 1.2Ueq(C) for phenyl and methylene H atoms and 1.5Ueq(C) for methyl H atoms.Unless noted otherwise, H atoms in the four structures were placed geometrically and refined in the riding-model approximation with 4, the two hydrogen atoms bound to the central Ir1 atom and the C4 atom of the ethoxyoxoethanylidene moiety were discernible from a difference-Fourier map. They were refined with bond-length restraints of 0.96 Å (C4) and 1.60 Å (Ir1) and with individual Uiso values. Three of the four methylene chloride solvent molecules are disordered. One solvent molecule  shows half-occupation, one  is disordered around an inversion centre (occupancy 0.25) and for one  the Cl atoms show a positional disorder over two sites (ratio 0.7:0.3). All H atoms of the solvent molecules were omitted from the final model.For compound 5 was poor. Hence, it was possible to collect reflections only up to 45°/2θ. The H atom attached to the C4 position was treated as described above. The methanol  and water (O7) solvent molecules are disordered around an inversion centre and were refined with half-occupation. H atoms of the disordered solvent molecules were omitted from the model. Furthermore, one phenyl group shows a 1:1 positional disorder and was refined over two sets of sites . All atoms of the disordered phenyl ring were refined isotropically.The scattering power of the crystal of compound 6 and 7, the H atom attached to the C4 position was treated as described above. For 6, localization of the H atoms of the methanol and water solvent molecules was not possible and hence they were omitted from the model. For 7, H atoms of water molecule O6 were located from a difference-Fourier map and refined with bond-length restraints of 0.84 Å. The O7 atom of the other water molecule was treated as being half-occupied, and its H atoms were omitted from the model. One methylene chloride solvent molecule  was refined over two sets of sites (ratio 0.65:0.35).In compounds 10.1107/S2056989018017024/wm5471sup1.cifCrystal structure: contains datablock(s) global, 4, 5, 6, 7. DOI: 10.1107/S2056989018017024/wm54714sup6.hklStructure factors: contains datablock(s) 4. DOI: 10.1107/S2056989018017024/wm54715sup7.hklStructure factors: contains datablock(s) 5. DOI: 10.1107/S2056989018017024/wm54716sup8.hklStructure factors: contains datablock(s) 6. DOI: 10.1107/S2056989018017024/wm54717sup9.hklStructure factors: contains datablock(s) 7. DOI: 1873392, 1873391, 1873390, 1873389CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


This is comparable to very weak CH hydrogen bonding interactions and is in line with the weak interaction energies calculated  of typical charge neutral adducts such as [Me3N-CH3···OH2] (2a). The interaction energy is enhanced to ≤–5 kcal·mol−1 when X is more electron withdrawing such as in [O2N-CH3··O=Cdme] (20b) and to ≤18 kcal·mol−1 in cationic species like [Me3O+-CH3···OH2]+ (8a).A systematic evaluation of the CSD and the PDB in conjunction with DFT calculations reveal that non-covalent Carbon-bonding interactions with X–CH The manner in which molecules interact with one another is largely determined by non-covalent interactions.c  So-calle3-hybridized C-atoms. Such interactions have been studied since about 2013  [3···OH2]   and [HO-3···OH2]  of −0.7 6–11a were computed as well and the most stable of these involved the Me3C+ carbocation in 6 (adducts with pentamethylated Carbon are unstable). The bonding interaction in 6b is largely covalent, as evidenced by the interaction energy of −82.4 kcal·mol−1, the large orbital contribution (55%), a dense bond critical point (18.4 · 102 a.u.) and a clear pyramidalization of the central C-atom (see 6a (Me3C+···O interaction) and 9 (with the least electronegative P) converged into an X–CH3···O Carbon bonding geometry. This is illustrated for 8a and 11a in methylC and Owater with a bond density of 1.15 · 102 and 0.98 · 102 a.u. for 8a and 11a respectively. The bonding energies in 7–11a are mainly electrostatic in origin (~70%) and about −8 kcal·mol−1 for water and −15 kcal·mol−1 for dma. The most stable adducts in both series involved the most electronegative O (3.44) in Me3O+ (8). Two alternative configurations with N-methylpyridinium were also computed (12 and 13). In 12, the O points in between two CH hydrogens as is illustrated for 12a in 13 the O atom is located directly above the cationic N+. Both 12 and 13 are more stable than the Carbon bonding geometry found in 11, suggesting that hydrogen bonding interactions are most preferred. The interaction energies of Carbon bonding interaction with cationic species is similar to previous data of the adducts: [H3N+-CH3···OCH2] ; [3N+-CH3···OC(H)NH2] ; [2S+-CH3···OH2/NH3/OCH2] ; [2S+-CH3···various lone-pairs]   ; [3···C2H2] ; [3···C2H4/NH3/PH3] ; [3···C2H4/dma] ; [2N-CH3···dma]  [As the calculations with cationic species imply that electron withdrawing substituents amplify the Carbon bonding interaction, it was decided to compute adducts with small molecules that have an electron withdrawing group: Iodomethane (·mol−1); ,51,52,53·mol−1);  [Hlg-CH3·mol−1);  [NC-CH3··mol−1); ,56 and [2-O in dma (adducts ‘b’) is consistently about twice as strong as the interaction with sp3-O in water (adducts ‘a’). This is in line with the larger amount of van der Waals overlap observed in the N(d’) plots , to moderately weak  to fairly strong in the cationic adducts . ΔE becomes smaller (more stable) in the order 2 < 14 < 16 < 18 < 20 < 7 < 8. Within this series, the orbital contribution remains constant at about 15–20%, while the electrostatic component increases from 30–35% in 2 to about 65% in 8. This implies that stronger Carbon bonding interactions are mainly driven by electrostatic interactions and that weaker such adducts are driven by dispersion. These computational results are consistent with recent literature reports [3 is strongly polarized  within a hemisphere of 5 Å basal radius (centered on C). It was found that X–CH3···ElR interactions can be as directional as very weak hydrogen bonding interaction involving C–H (Pmax ≤ 1.50) but not directional at all when X = C. Grouping of data with significant amounts of van der Waals overlap (up to ~30%) was observed in various sub-datasets in the region where the X–CH3···ElR angle α is 160°–180°. These distributions were significantly shifted to shorter distances  in the case of cationic R3N+–CH3···Owater/amide compared to charge-neutral R2N–CH3···Owater/amide interactions.The CSD and the PDB were systematically evaluated for potential directional behavior of intermolecular non-covalent Carbon bonding interactions involving X–CH3···O adducts with water and dimethylacetamide are very weak  and are often not the energy minima of the adducts . The interaction energies can be increased by deploying a more electron withdrawing X . Rendering X cationic leads to even more stable adducts  in 7, 8, 10 and 11). Carbon-bonding adducts with dimethylacetamide are consistently twice as stable as those with water. Energy decomposition analyses showed that increased stability is driven by electrostatics and atom-in-molecule analyses regularly gave a clear bond critical point involving the methyl C-atom.Model DFT calculations revealed that charge neutral X–CH3 is electrostatically driven and can be significant. The interaction can even by mildly directional in the solid state (comparable to weak CH hydrogen bonding interactions), provided X is sufficiently electron withdrawing.It is thus concluded that this combined database / DFT study reaffirms that intermolecular non-covalent Carbon interactions with X–CH


I) and 1,2‐disila[9]crown‐3 (II) with MgI2 yielded exclusively [MgI2] (1). The larger Ca2+ ion was then employed for cross‐coupling of I and II and yielded the complex [CaI2] (2). Cross‐coupling of I and 1,2,4,5‐tetrasila[9]crown‐3 (III) with SrI2 enables the synthesis of the silicon‐dominant 1,2,4,5,10,11‐hexasila[15]crown‐5 ether complex of SrI2 (3). Further, the compounds [SrI2] (4), [SrI2] (5), and [SrI2] (6) were obtained by coupling I, 1,2‐disila[12]crown‐4 (IV) or 1,2‐disila‐benzo[12]crown‐4 (V), respectively. Using various anions, the (cross‐)coupled ligands were also observed in an X‐ray structure within the mentioned complexes. These template‐assisted (cross‐)couplings of various ligands are the first of their kind and a novel method to obtain macrocycles and/or their metal complexes to be established. Further, the Si−O bond activations presented herein might be of importance for silane or even organic functionalization.Alkaline earth metal iodides were used as templates for the synthesis of novel silicon‐based ligands. Siloxane moieties were (cross‐)coupled and ion‐specific, silicon‐rich crown ether analogues were obtained. The reaction of 1,2,7,8‐tetrasila[12]crown‐4 coupled and ion specific, silicon‐rich crown ether analogues were obtained. The coupling of various ligands gives an outlook on Group 2 ion‐catalyzed macrocycle and/or silane syntheses. It is well known for crown ethers to form coordination compounds with metal centers across a wide range of the periodic table. These complexes are generally very stable and these polyethers as well as related systems such as cryptands, or in general, multidentate ligands, gained many fields of applications since their discovery in the mid‐sixties. The synthesis of such polyethers, however, is often not trivial because the molecules of the starting materials need to be brought into a suitable conformation for the formation of a specific (most often cyclic) product. The synthesis of these cyclic ethers is therefore mostly metal‐template assisted.Templates are known to provide a suitable coordination sphere for the starting materials, which favors the linkage to ring closure and allows obtaining cyclic ligand systems in much higher yields.δ+ and metaln+ disturbs silyl ether bonding.n type .+ and Cs+ so far relucted silyl ether coordination.Most recently, both concepts—covalency and ionicity—were considered as harmonious models to understand the basicity of siloxanes. Regarding a covalent model, negative hyperconjugation interactions are described in the case p(O)→σ*(Si−C).Apart from siloxane coordination chemistry, the metal⋅⋅⋅O−Si interaction should also be put in context to Si−O bond activation. From the perspective of Si−O bond activation, weakening of Si−O bonds is of considerable significance regarding the conversion of silicates to silanes. Especially dicatecholato‐silicate(IV) complexes are frequently used as precursors for either silane synthesis or functionalization of various organic molecules.2+ ion, we aimed at synthesizing a [15]crown‐5 ether by cross‐coupling the ligands 1,2,7,8‐tetrasila[12]crown‐4 (I) and 1,2‐disila[9]crown‐3 (II). However, the reaction in α,α,α‐trifluorotoluene heated at reflux failed (Scheme 2] (1) was obtained and, as can be seen from the molecular structure determined by single‐crystal X‐ray diffraction analysis (SC‐XRD), the moiety of crown ether I is large enough to bind Mg2+ I2] and the octahedral coordination towards Mg2+ is preferred.I with Mg2+ is present because the 29Si{1H} NMR chemical shift is observed at 22.8 ppm and thus, a strong lowfield shift in comparison with I (δ=10.8 ppm)Starting with the Mgsizing a 5crown‐5 2+ ion was described earlier and, as can be seen from various examples, seems to match perfectly.I and II with CaI2. After workup procedures two new signals in the 29Si{1H} NMR are observed at 19.6 and 19.9 ppm. Crystallization of the reaction product 2 however, was unsuccessful from different solvents and temperatures also due to poor solubility. We therefore expanded the anion I− to I3− upon iodine addition. The compound [Ca(I3)2] (2 a) then was crystallized and the molecular structure was determined by means of SC‐XRD  and 245.2(9) pm and compare well to the complex [CaOTf2] (OTf=CF3SO3−).The fivefold, coplanar coordination by sila‐crown ligands towards the larger Ca2] (3) is another example of a cross‐coupling reaction in which an alkaline earth metal cation is used. 3 represents the first hybrid disila‐crown ether bearing more disilane than ethylene units. The even larger Sr2+ cation can be used as a convex template to cross‐couple I and 1,2,4,5‐tetrasila[9]crown‐3 (III), which is accessible applying reaction conditions reported before.I and one equivalent of III. Due to three disilane units within the ligand framework, the Sr2+ cation fits well in the cavity of the obtained ligand. With 19.44, 19.27, and 13.32 ppm, three resonances are observed in the 29Si{1H} NMR spectrum, all of which compare well to those of OSi⋅⋅⋅Sr2+ coordination compounds characterized before.3 could not be obtained, even after iodine addition. Hence, the Lewis acidic salt GaI3 was added as an acceptor for the iodide anion. It is notable, that also in 3 a, the SiSi−O−SiSi fragment of the siloxane framework provides a small Si‐O‐Si angle, which measures 121.1(6)°. The OSi−O−Si⋅⋅⋅Sr2+ distance might be the longest O⋅⋅⋅Sr2+ distance observed in 3 a, but the high basicity of siloxanes towards Group 2 ions is clearly emphasized.The synthesis of [SrI4)2] (3 a) were obtained, which were analyzed through SC‐XRD  compare well to various complexes of Sr2+ and sila ligands, which were reported before.2+ cation as a template, we were able to observe reactions of other disila‐crown ethers as well. The small cavity of II does not allow for 1:1 complexation of Sr2+ and thus, a total of two equivalents of II react to form the 1,2,10,11‐tetrasila[18]crown‐6 ether. [SrI2] (4) is obtained as a colorless powder and in solution, a resonance at 17.5 ppm in the 29Si{1H} NMR spectrum was observed. Given that we were also experiencing problems with the crystallization of this compound, the X‐Ray structure could only be determined upon iodine addition. According to a reduced niggli formula, compound 1∞+ fragments to build infinite chains along [001] which is most likely the driving force for crystallization. The OSi⋅⋅⋅Sr2+ distances in 4 a compare well to those in compound 3 a and [SrI2].After several months, a few single crystals of [Sr(GaI4)2]  a were o4 as an example. As drawn here, the sila‐ligand is polarized by the Lewis acid first, which makes it electrophilic and thus accessible for nucleophilic attack of I−. Afterwards, the Si−O bond is cleaved. Subsequently, the intermediate then has to cleave the second sila‐crown. At this point of the reaction, the alkaline earth metal ion acts as a convex template, in which the open‐chained ligand species is brought into a suitable conformation for ring closure, which is the final step of the presented reactions. We want to emphasize, that such a mechanism was also postulated by Harder in a past work.At this point, it is clear that (cross‐)coupling reactions are possible with different alkaline earth metal iodides. We tried to understand how the reaction works and the mechanism behind the formation of these unprecedented macrocycles, but unfortunately, we were unable to characterize any intermediate products by means of NMR spectroscopy or SC‐XRD. We can assure that heating at reflux is needed to cleave the smaller rings. Further, we can assure that the reaction does only occur if an iodide salt is employed. Other alkaline earth metal halides do not form these ligands. This lets us conclude that one key step in the formation of the (cross‐)coupling product has to be a nucleophilic substitution reaction. Furthermore, as evident from different works, we could convincingly show that the Si−O bond is significantly weakened due to coordinating an alkaline earth metal ion. Thus, the Si−O bond instead of the C−O bond is cleaved, which is also represented by the herein obtained macrocycles. A proposed mechanism for the formation of the cross coupling products is depicted in Scheme 2 with the ligands 1,2‐disila[12]crown‐4 (IV) and 1,2‐disila‐benzo[12]crown‐4 (V) were performed. Both ligands are too small for Sr2+ and thus, template‐assisted ring opening yielded novel species by intermolecular coupling of the respective crown ether. The reaction of IV with SrI2 results in the formation of the first disilanyl‐bearing [24]crown‐8 ether. [SrI2] (5) was obtained by coupling two equivalents of IV I2].29Si{1H} NMR resonance signal for 5 is observed at 15.2 ppm. A split of this resonance at low temperature of 190 K was not observed.Further reactions of SrIwn‐8)I2]  was obta5 decomposes readily with only traces of moisture forming [SrI]I (EO7=heptaethylene glycol).Thus, the exchange between the coordinating disilane units is too fast on the NMR time scale and results in the described equivalency. At this point, it should be noted that the spectroscopic investigation of the compound is challenging. Compound 6) is more stable and was characterized by state‐of‐the‐art methods including SC‐XRD I]I  is more 6 was reacted with [222]cryptand and indeed we were able to obtain free ligand 1,2,13,14‐tetrasila‐dibenzo[24]crown‐8 (7) after workup. The metal‐free ligand species was characterized by means of HR‐ESI MS as well as NMR spectroscopy. In HR‐ESI+ MS, m/z relations of 625.2502 [7+H]+ (100) as well as 647.2320 [7+Na]+ (100) were found. In addition, 29Si{1H} NMR spectroscopy revealed highfield chemical shift and a single resonance at 11.5 ppm is found. This value compares well to the free ligand V and also to related metal‐free disila‐ligand systems.One of the remaining questions is of course whether it is possible to remove the metal center for possible use of such new ligand in coordination chemistry. We are currently investigating this subject, but are still at an early stage. To give an outlook, we performed exchange reactions. As an example, an excess of ted with 2cryptanda‐dibenzocrown‐8 ‐coupling reactions with BaI2+ ion is too small to cross‐couple small silicon‐based ligands, a cross‐coupling reaction was established with the larger Ca2+ and Sr2+ ions. Furthermore, the Sr2+ ion was used for coupling reactions of three different disila‐crown ethers. Barium as a template for coupling reaction, however, turned out to be unsuccessful. Although the organic [12]crown‐4 is too small for the Mg2+ ion, the cavity of the disilane‐bearing analogue 1,2,7,8‐tetrasila[12]crown‐4 (I) ether matches fine with the Mg2+ ion and the complex [MgI2] (1) was obtained. [CaI2] (2) and [SrI2] (3) were synthesized by cross‐coupling reaction of the small rings I and II for 2, and I and III for 3. The ligand in 3 represents the first crown ether with more disilane than ethylene units between the donor atoms. Finally, [SrI2] (4), [SrI2] (5) and [SrI]I (6) were characterized and obtained by template‐driven dimerization of II, IV, or V with SrI2. The ligand moieties observed in 2–6 cannot yet be synthesized by conventional silane chemistry and for this reason, the template‐assisted (cross‐)coupling of various ligands is an elegant way to obtain novel macrocycles and/or their metal complexes. Overall, this work gives an outlook on Group 2 ion‐catalyzed silane syntheses, especially due to the fact that first attempts showed that the metal ion can, in principle, be removed from a novel sila‐ether. We also hope that there will be a broader application of the presented Si−O bond activations as a mean of molecule functionalization.In this study alkaline earth metal iodides were successfully used for the coupling reaction of different silicon‐based crown ether analogues to form novel ligand environments. The work presents Si−O bond‐cleavage reactions driven by a macrocyclic effect due to metal‐template reaction of the respective silicon‐based ligands. Given that the Mg2 , CaI2 and SrI2 , BaI2  and GaI3  were finely ground and stored in a Mbraun glovebox under Ar. NMR spectra were recorded on a Bruker AV III HD 300 MHz or AV III 500 MHz spectrometer, respectively. Infrared (IR) spectra of the respective samples were measured using attenuated total reflectance (ATR) mode on the Bruker‐type spectrometer Alpha FT‐IR. ESI mass spectra were acquired with a LTQ‐FT Ultra mass spectrometer (Thermo Fischer Scientific) and LIFDI mass spectra were acquired on a JEOL AccuTOF‐GCv device. The resolution was set to 100.000. Elemental analysis was carried out on a Vario MicroCube. In case of complex 2 and 3, we were not able to obtain an accurate elemental analysis. This is probably due to the wax‐like, greasy characteristics of the compounds and/or formation of SiC during the measurement. The crown‐ethers I, II, IV, and V were synthesized according to literature‐known procedures.7 can only be obtained with major impurities of [222]crypt.All manipulations were carried out with rigorous exclusion of oxygen and moisture using basic Schlenk techniques establishing an inert‐gas atmosphere with a vacuum line. All solvents were dried and freshly distilled before use. The alkaline earth metal salts MgI3  were dissolved in THF (50 mL). Subsequently, O(Si2Me4Cl)2n‐pentane (50 mL) followed by filtration. Removing the solvent under reduced pressure yielded the crown ether as a colorless oil .Ethylene glycol  and NEt1H NMR : δ=0.18 2), 0.20 2), 3.69 ppm ; 13C{1H} NMR : δ=0.1 2), 2.8 2), 66.0 ppm ; 29Si{1H} NMR : δ=1.5 2), 11.4 ppm 2). HR‐MS: ESI(+) m/z (%): 309.1196 [M+H]+ (100), 639.2143 [2 m+Na]+ (100); IR: 2951 (m), 2896 (w), 2867 (w), 1457 (vw), 1388 (vw), 1247 (s), 1140 (m), 1089 (s), 1027 (s), 927 (m), 854 (m), 795 (s), 761 (vs.), 721 (m), 681 (m), 660 (m), 633 (m), 553 (m), 506 (vw), 487 cm−1 (m).I  was dissolved in α,α,α‐trifluorotoluene (10 mL). Subsequently, MgI2  was added. Stirring the mixture at 60 °C for 90 min gave a white suspension. Removing the solvent under reduced pressure yielded a white precipitate which was extracted with DCM (10 mL) followed by filtration. After washing with n‐pentane (4 mL), and drying in vacuo, 1 was obtained as a colorless powder . For single‐crystal growth, the powder was dissolved in DCM (4 mL) and layered with n‐pentane (20 mL). Single crystals were obtained overnight as colorless needles.Compound 1H NMR : δ=0.59 2), 4.23 ppm ; 13C{1H} NMR : δ=−0.46 2), 62.8 ppm ; 29Si{1H} NMR : δ=22.8 ppm 2). MS: ESI(+) m/z (%): 503.0270 [M−I]+ (15); IR: 2949 (vw), 2888 (vw), 1450 (w), 1398 (vw), 1369 (vw), 1247 (m), 1103 (m), 1056 (s), 1022 (s), 934 (vs.), 915 (s), 868 (m), 840 (m), 818 (s), 802 (s), 780 (vs.), 715 (s), 645 (m), 464 cm−1 (m). CHN calcd for C12H32I2MgO4Si4⋅ CH2Cl2 C, 21.81; H, 4.79. Found C, 21.66; H, 4.90.I  together with II  were dissolved in α,α,α‐trifluorotoluene (10 mL). Subsequently, CaI2  was added. Heating the mixture at reflux for 90 min resulted in a white suspension. Removing the solvent under reduced pressure yielded a white precipitate which was extracted with of DCM (10 mL) followed by filtration. After washing with two portions of n‐pentane (4 mL each), and drying in vacuo, 1 was obtained as a colorless powder . For single‐crystal growth, 2  and I2  were dissolved in DCM (4 mL) and filtered. The filtrate was then layered with n‐pentane (20 mL). A few brown platelets of 2 a were obtained after more than two weeks at ambient temperature.Compound 1H NMR : δ=0.47 , 0.48 , 3.95–4.03 ppm ; 13C{1H} NMR : δ=−0.7 , −0.7 , 63.2 , 64.8 , 71.2 ppm ; 29Si{1H} NMR : δ=19.6 , 19.9 ppm . MS: ESI(+) m/z (%): 419.1521 [M−CaI2+Na]+ (100), 397.1705 [M−CaI2+H]+ (5). IR: 2947 (m), 2881 (w), 1455 (vw), 1400 (vw), 1248 (s), 1057 (s), 1029 (s), 943 (s), 795 (s), 768 (vs.), 723 (s), 635 (m), 505 cm−1 (vw).I  and III  were dissolved in α,α,α‐trifluorotoluene (10 mL). Subsequently, SrI2  was added. Heating the mixture at reflux for 90 min resulted in a white suspension. Removing the solvent under reduced pressure yielded a white precipitate which was extracted with DCM (10 mL), followed by filtration. After washing with two portions of n‐pentane (4 mL each) and drying in vacuo, 3 was obtained as a colorless, greasy solid . For single‐crystal growth, product 3  and GaI3  were dissolved in α,α,α‐trifluorotoluene (5 mL). The suspension was stirred 30 min and gently warmed to 60 °C for 5 min. The mixture was then freed of the solvent, extracted with DCM (3 mL) and filtered. The filtrate was then concentrated until the saturation point was reached and stored at −32 °C. A few colorless platelets of 3 a were obtained after more than four weeks.Compounds 1H NMR : δ=0.44 2), 0.47 2), 0.56 2), 3.96 ppm ; 13C{1H} NMR δ=−0.5 2), −0.5 2), 4.1 2), 65.3 , 65.4 ppm ; 29Si{1H} NMR : δ=13.3 2), 19.3 2), 19.4 ppm 2). MS: ESI(+) m/z (%): 698.9902 [M−I]+ (100), 507.1697 [M−SrI2+Na]+ (30). IR: 2960 (w), 2879 (vw), 1456 (vw), 1400 (vw), 1369 (vw), 1258 (s), 1074 (s), 1024 (s), 951 (s), 894 (m), 851 (m), 794 (vs.), 769 (vs.), 712 (s), 634 (m), 557 (m), 497 (w), 448 cm−1 (w).II  was dissolved in α,α,α‐trifluorotoluene (10 mL). Subsequently SrI2  was added. Heating the mixture at reflux for 60 min. resulted in a white suspension. Removing the solvent under reduced pressure gave a white precipitate which was extracted with DCM (20 mL) followed by filtration. Upon washing with n‐pentane (5 mL) and removal of the solvent, 4 was obtained as a pale white powder . For single crystal growth, product 4 (30 mg 0.04 mmol) and I2  were dissolved in DCM (4 mL). Layering the solution with n‐pentane (20 mL) yielded single crystals of 4 a as brown blocks after three days.Compound 1H NMR : δ=0.45 , 3.88 , 4.08 ppm ; 13C{1H} NMR : δ=0.1 , 63.0 , 72.8 ppm ; 29Si{1H} NMR : δ=17.5 ppm . MS: ESI(+) m/z (%): 264.0475 [M−2I]2+ (93), 447.2058 [M−SrI2+Li]+ (3), 463.1797 [M−SrI2+Na]+ (55), 479.1537 [M−SrI2+K]+ (15), 655.0003 [M−I]+ (16). IR: 2943 (w), 2880 (w), 1459 (w), 1398 (vw), 1353 (w), 1247 (m), 1069 (s), 1039 (s), 944 (s), 927 (s), 861 (s), 840 (s), 819 (s), 795 (s), 768 (vs.), 718 (s), 629 (m), 546 (w), 523 cm−1 (w). CHN calcd for C16H40I2O6Si4Sr: C, 24.57; H, 5.15. Found: C, 25.42; H, 5.35.IV  was dissolved in α,α,α‐trifluorotoluene (15 mL). Subsequently SrI2  was added. Heating the mixture at reflux for three hours resulted in a white suspension. Removing the solvent under reduced pressure yielded a white precipitate which was extracted with DCM (20 mL), followed by filtration. The product 5 was then obtained as a colorless powder after removal of the solvent . For single‐crystal growth, the powder was dissolved in DCM (4 mL) and layered with n‐pentane (20 mL). Single crystals were obtained overnight as colorless needles.Compound 1H NMR : δ=0.37 2), 3.94 , 3.95 ppm ; 13C{1H} NMR : δ=−0.09 , 62.8 , 70.5 , 73.5 ppm ; 29Si{1H} NMR : δ=15.2 ppm . MS: ESI(+) m/z (%): 551.2311 [M−SrI2+Na]+ (82); IR: 2961 (m), 2943 (m), 2882 (w), 1454 (w), 1396 (w), 1366 (w), 1349 (w), 1302 (w), 1259 (s), 1091 (s), 1073 (s), 1039 (s), 1017 (s), 951 (s), 931 (s), 861 (m), 840 (m), 791 (vs.), 764 (s), 732 (s), 661 (s), 636 (m), 563 (w), 492 (w), 424 cm−1 (w). CHN calcd for C20H48I2O8Si4Sr: C, 27.86; H, 5.67. Found: C, 27.60; H, 5.67.V  was dissolved in α,α,α‐trifluorotoluene (15 mL). Subsequently, SrI2  was added. Heating the mixture at reflux for three hours resulted in a white suspension. Removing the solvent under reduced pressure yielded a white precipitate which was extracted with DCM (20 mL) followed by filtration. The product 6 was then obtained as a colorless powder after removal of the solvent . For single‐crystal growth, the powder was dissolved in DCM (3 mL) and layered with n‐pentane (20 mL). Single crystals were obtained overnight as colorless platelets.Compound 1H NMR : δ=0.45 , 4.15 , 4.42 , 7.02–7.16 ppm ; 13C{1H} NMR : δ=0.0 , 62.4 , 72.6 , 116.1 , 124.9 , 147.4 ppm ; 29Si{1H} NMR : δ=19.8 ppm . MS: ESI(+) m/z (%): 647.2311 [M−SrI2+Na]+ (78), 839.0525 [M−I]+ (35); IR: 2946 (w), 2885 (w), 1595 (w), 1500 (s), 1456 (m), 1400 (w), 1366 (w), 1250 (vs.), 1191 (m), 1161 (m), 1115 (m), 1063 (s), 934 (vs.), 916 (vs.), 862 (m), 837 (m), 817 (s), 774 (s), 750 (vs.), 734 (s), 711 (s), 630 (w), 605 (w), 533 (w), 516 (w), 484 (w), 456 (w), 422 cm−1 (w). CHN calcd for C28H48I2O8Si4Sr⋅0.5 CH2Cl2: C, 33.93; H, 4.90. Found: C, 33.92; H, 4.68.6  was dissolved in DCM (10 mL) and [222]cryptand  was added. The resulting suspension was stirred overnight to give a clear solution. The solvent was removed under reduced pressure to give an oily, greasy residue. Extracting with n‐pentane (10 mL) and subsequent filtering of the suspension yielded a clear solution. Removing the solvent under reduced pressure gave a greasy crown ether‐[222]cryptand mixture (0.13 g). [222]crypt contamination was more than 30 %.Compound 1H NMR : δ= 0.24 , 3.96–4.01 , 4.02–4.08 , 6.91 ppm ; 13C{1H} NMR : δ= 0.8 , 63.5 , 72.5 , 116.7 , 122.5 , 150.5 ppm ; 29Si{1H} NMR : δ= 11.5 ppm . MS: HR‐ESI(+) m/z (%): 625.2502 [M+H]+ (100), 647.2320 [M+Na]+ (100). IR: 2945 (w), 2869 (w), 1593 (w), 1501 (s), 1452 (m), 1396 (w), 1370 (w), 1328 (w), 1247 (s), 1221 (m), 1124 (s), 1098 (s), 1053 (s), 948 (m), 923 (m), 823 (m), 790 (s), 763 (vs.), 740 (s), 631 (m), 450 cm−1 (w).3 a, 5), STOE IPDS2 , STOE IPDS2T (2 a) or a STOE STADIVARI (4 a) diffractometer, respectively. Measurements were performed at 100 K with MoKα (λ=0.71073 Å) or CuKα (λ=1.54184 Å) radiation, graphite monochromatization or respective X‐ray optics. The structures were solved by direct methods and refinement with full‐matrix‐least‐squares against F2 using SHELXT and SHELXL on OLEX2 platform.3 a and 6, we applied the SQUEEZE operation. A selection of respective crystal data is given below.Single‐crystal X‐ray diffraction experiments were carried out on a Bruker D8 Quest  K, a=8.173(3), b=12.204(4), c=14.204(8) Å; β=93.02(4)°, V=1414.8(11) Å3, ρ=1.680 g cm−3, numerical absorption correction using STOE X‐AREA and X‐RED32.μ=2.618 mm−1, Tmin, Tmax=0.5303, 0.8053, 2Θ range 4.402–58.996°, reflections measured 21 645, independent reflections 7891  0.0244, wR2  0.0590, GoF 1.047, Δρmax, Δρmin 1.27/−0.52 e Å3.Crystal data of 2 a: C14H36CaI6O5Si4, monoclinic, C2/c, Z=4, 100(2) K, a=11.408(3), b=12.970(2), c=25.570 Å; β=92.38(2)°, V=3484.7(16) Å3, ρ=2.284 g cm−3, spherical absorption correction using STOE X‐AREA and LANA.μ=5.654 mm−1, Tmin, Tmax=0.1989, 0.4381, 2Θ range 3.458–50.994°, reflections measured 13 999, independent reflections 3250 [R(int)=0.0924], 154 parameters, R‐index [I≥2σ(I)] 0.0548, wR2  0.1400, GoF 1.072, Δρmax, Δρmin 1.56/−0.91 e Å3.Crystal data of 3 a: C16H44Ga2I8O5Si6Sr, monoclinic, P21/c, Z=4, 100(2) K, a=23.3580(16), b=11.3585(7), c=20.6920(14) Å; β=111.998(4)°, V=5090.2(6) Å3, ρ=2.254 g cm−3, spherical absorption correction using STOE X‐AREA and LANA,μ=7.110 mm−1, Tmin, Tmax=0.4793, 0.7452, 2Θ range 4.232–50.738°, reflections measured 171 072, independent reflections 9287 [R(int)=0.1514], 355 parameters, R‐index [I≥2σ(I)] 0.0675, wR2  0.1863, GoF 1.076, Δρmax, Δρmin 4.17/−1.57 e Å3.Crystal data of 4 a: C16H40I4O6Si4Sr, monoclinic, P21/c, Z=4, 100(2) K, a=12.0422(5), b=22.2125(6), c=12.8413(4) Å; β=95.734(3)°, V=3417.7(2) Å3, ρ=2.014 g cm−3, spherical absorption correction using STOE X‐AREA and LANA,μ=32.123 mm−1, Tmin, Tmax=0.212, 0.360, 2Θ range 7.378–50.994°, reflections measured 26 969, independent reflections 6337 [R(int)=0.0854], 288 parameters, R‐index [I≥2σ(I)] 0.0391, wR2  0.0894, GoF 0.804, Δρmax, Δρmin 1.23/−1.51 e Å3.Crystal data of 5: C20H48I2O8Si4Sr, triclinic, P‐1, Z=2, 110(2) K, a=8.4870(4), b=14.9819(7), c=15.4929(7) Å, α=105.457(2)°, β=102.187(2)°, γ=99.376(2)°, V=1804.98(15) Å3, ρ=1.601 g cm−3, multiscan absorption correction using SADABS2016[50],μ=3.371 mm−1, Tmin, Tmax=0.5094, 0.8894, 2Θ range 4.642–57.786°, reflections measured 54 208, independent reflections 9456 [R(int)=0.0442], 365 parameters, R‐index [I≥2σ(I)] 0.0323, wR2  0.0540, GoF 1.034, Δρmax, Δρmin 1.21/−0.80 e Å3.Crystal data of 6⋅1.5DCM: C29.5H51Cl3I2O8Si4Sr, triclinic, P‐1, Z=4, 100(2) K, a=11.9953(8) Å, b=16.0514(12) Å, c=24.936(2) Å, α=76.567(6)°, β=85.494(6)°, γ=86.477(6)°, V=4650.7(6) Å3, ρ=1.562 g cm−3, numerical absorption correction using STOE X‐AREA and X‐RED32,μ=2.801 mm−1, Tmin, Tmax=0.5094, 0.8894, 2Θ range 4.642–57.786°, reflections measured 52 818, refined as a two component twin, 901 parameters, R‐index [I≥2σ(I)] 0.0780, wR2  0.2325, GoF 0.871, Δρmax, Δρmin 2.32/−1.74 e Å3.The authors declare no conflict of interest.


The molecule has an E configuration about the C=C bond and the carbonyl group is syn with respect to the C=C bond. In the crystal, the molecules are linked along the a-axis direction through van der Waals forces and by face-to-face π-stacking between the thiophene rings and between the benzene rings of neighbouring molecules along the b axis into zigzag sheets lying parallel to the bc plane.The molecular structure of the title compound consists of a 2,5-dichlorothiophene ring and a 2-chlorophenyl ring linked  13H7Cl3OS, consists of a 2,5- dichlorothiophene ring and a 2-chlorophenyl ring linked via a prop-2-en-1-one spacer. The dihedral angle between the 2,5-dichlorothiophene and 2-chlorophenyl rings is 9.69 (12)°. The molecule has an E configuration about the C=C bond and the carbonyl group is syn with respect to the C=C bond. The molecular conformation is stabilized by two intramolecular C—H⋯Cl contacts and one intramolecular C—H⋯O contact, forming S(5)S(5)S(6) ring motifs. In the crystal, the molecules are linked along the a-axis direction through van der Waals forces and along the b axis by face-to-face π-stacking between the thiophene rings and between the benzene rings of neighbouring molecules, forming corrugated sheets lying parallel to the bc plane. The intermolecular interactions in the crystal packing were further analysed using Hirshfield surface analysis, which indicates that the most significant contacts are Cl⋯H/ H⋯Cl (28.6%), followed by C⋯H/H⋯C (11.9%), C⋯C (11.1%), H⋯H (11.0%), Cl⋯Cl (8.1%), O⋯H/H⋯O (8.0%) and S⋯H/H⋯S (6.6%).The molecular structure of the title compound, C The molecules are packed into corrugated sheets lying parallel to (011)  Figs. 2 and 3 ▸.CrystalExplorer ] with de + di ≃ 2.85 Å . The C⋯H/H⋯C interactions are shown in Fig. 4c). The scattered points show the van der Waals contacts and π–π stacking interactions. The interatomic C⋯C contacts appear as an arrow-shaped distribution of points in Fig. 4d), with the vertex at de = di = 1.75 Å. The C⋯C contacts reflect π–π interactions between the aromatic rings. The H⋯H interactions are reflected in Fig. 4e) as widely scattered points of high density due to the large hydrogen content of the molecule. The split spike with the tip at de = di ≃ 1.3 Å is due to the short interatomic H⋯H contacts. Cl⋯Cl contacts [Fig. 4f)] are disfavoured when the number of H atoms on the molecular surface is large because of competition with the more attractive H⋯Cl contacts. Cl⋯Cl contacts from a parallel alignment of C—Cl bonds  may be indicated. They are known in the literature as type-I halogen–halogen interactions ] also have a symmetrical distribution of points, with two pairs of thin and thick edges at de + di ≃ 2.75 Å. The S⋯H contacts shown in Fig. 4h) are contracted to a much lesser degree.The C—H⋯Cl interactions appear as two distinct spikes in the fingerprint plot -3-(thiophen-2-yl)prop-2-en-1- one [(X); Yesilyurt et al., 2018E)-1-(2-aminophenyl)-3- (thiophen-2-yl)prop-2-en-1-one [(XI); Chantrapromma et al., 2013et al., 2018P1, while (III) and (IV) are isostructural in space group P21/c. There are no hydrogen bonds of any kind in the structures of compounds (I)C(7) chains by means of C—H⋯O hydrogen bonds. In (V), there are again no hydrogen bonds nor any π–π stacking interactions but in (VI), the molecules are linked into C(5) chains by C—H⋯O hydrogen bonds. In each of compounds (I)–(VI), the molecular skeletons are close to planarity, and there are short halogen–halogen contacts in the structures of compounds (II) and (V) and a short Br⋯O contact in the structure of compound (VI). In (VII), the molecule is non-planar, with a dihedral angle of 22.6 (2)° between the aromatic rings. The molecules are linked by pairs of C—H⋯π interactions, forming inversion dimers. There are no other significant intermolecular interactions present. In (VIII), the molecule is nearly planar, the dihedral angle between the thiophene and phenyl rings being 9.07 (8)°. The molecules are linked via weak C—H⋯O and C—H⋯S hydrogen bonds, forming chains propagating along the c-axis direction. In (IX), the thienyl ring is not coplanar with the benzene ring, their planes forming a dihedral angle of 13.2 (4)°. In the crystal, molecules stack along the a-axis direction, with the interplanar separation between the thienyl rings and between the benzene rings being 3.925 (6) Å. In (X), the thiophene ring forms a dihedral angle of 26.04 (9)° with the benzene ring. The molecular conformation is stabilized by an O—H⋯N hydrogen bond. The molecules are connected through C—H⋯O hydrogen bonds, forming wave-like layers parallel to the ab plane, which are further linked into a three-dimensional network by C—H⋯π interactions. In (XI), the molecule is almost planar with a dihedral angle of 3.73 (8)° between the phenyl and thiophene rings. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. Adjacent molecules are linked into dimers in an anti-parallel face-to-face manner by pairs of C—H⋯O interactions. Neighbouring dimers are further linked into chains along the c-axis direction by N—H⋯N hydrogen bonds. In (XII), the dihedral angle between the thiophene and benzene rings increases to12.24 (15)°. The molecular conformation is stabilized by intramolecular C—H⋯Cl contacts, forming S(6) and S(5) ring motifs. In the crystal, the molecules are linked through face-to-face π-stacking between the thiophene rings and the benzene rings of the molecules into zigzag sheets lying parallel to the bc plane.The closest related compounds with the same skeleton and containing a similar bis-chalcone moiety to the title compound but with different substituents on the aromatic rings are:  = 1.2Ueq(C) or 1.5Ueq(C-methyl).Crystal data, data collection and structure refinement details are summarized in Table 410.1107/S2056989018018066/qm2131sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989018018066/qm2131Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018018066/qm2131Isup3.cmlSupporting information file. DOI: 1036796CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The asymmetric unit of the adduct contains a neodymium(III) cation, three coordinated nitrate anions, four coordinated water molecules and three uncoordinated neutraltriazine molecules. The crystal structure consists of a three-dimensional supramolecular framework held together by a network of O—H⋯O and O—H⋯N hydrogen bonds between the coordinated water molecules, nitrate ions and triazine molecules. The uncoordinated neutral triazine moieties form N—H⋯N hydrogen bonds. Hirshfeld surface and fingerprint plots identify the major contributors to the intermolecular interactions. 3)3(H2O)4]·3C3H4N4, neodymium is ten-coordinate with a distorted bicapped square-antiprismatic geometry formed from six O atoms from three nitrate ions and four O atoms from four coordinated water molecules. The structure also contains neutral 3-amino-1,2,4-triazine molecules which are not coordinated to the central metal atom. The coordinated water molecules and nitrate ions of adjacent complexes are linked by O—H⋯O hydrogen bonds to form cyclic R22(8) ring motifs, which in turn are further connected via hydrogen bonds to generate a sheet-like structure. The triazine molecules are involved in a number of hydrogen-bonding interactions: N—H⋯N and O—H⋯N interactions to form R33(9) motifs and N—H⋯N interactions to link the organic molecules into chains. Weak C—H⋯O hydrogen bonds also occur between triazine molecules and coordinated nitrate atoms. All these intermolecular contacts contribute to the stabilization of the three-dimensional supramolecular framework. Hirshfeld surface analysis shows that N⋯H/H⋯N and H⋯H interactions account for 42.9 and 20.6% of the surface, respectively.In the title compound, [Nd(NO All these intermolecular interactions appear to play a significant role in stabilizing the crystal structure and result in the formation of a three-dimensional supramolecular framework  is based on the distances from the nearest atom inside (di) and outside (de) the surface. The three-dimensional dnorm surface of the title compound is shown in Fig. 5dnorm values on the surface correspond to the N—H⋯N, N—H⋯O and O—H⋯O interactions. Analysis of the two-dimensional fingerprint plots reveal that the H⋯H (20.6%) and N⋯H/H⋯N (42.9%) interactions are the highest contributors to the Hirshfeld surface. Smaller contributions come from O⋯H/H⋯O (13.3%) C⋯H/H⋯C (6.3%), N⋯N (6.2%), C⋯N/N⋯C (4.6%), N⋯O/O⋯N (2.8%) and C⋯O/O⋯C (1.8%) interactions -biscopper(II)] and KUCNEC [with bishexakistricopper(II)] biscobalt]; Palion-Gazda et al., 2015catena-[bis(μ2-dicyanamido)biscobalt]; Şwitlicka-Olszewska et al., 2016A search of the Cambridge Structural Database 3·6H2O (0.219g) (Alfa Aesar). Dichloromethane (5 ml) was then added and the mixture refluxed for 7 h at 353 K. The resulting solution was then allowed to cool slowly to room temperature. After two weeks, brown-coloured crystals were obtained, m.p. = 378 K.The title compound was prepared by adding a hot methanolic solution (20 ml) of 3-amino-1,2,4-triazine (0.043g) (Aldrich) to a hot methanolic solution (20 ml) of Nd(NOUiso(H) set to 1.2–1.5Ueq(C). The water and N-bound H atoms were located in difference-Fourier maps and refined with Uiso(H) = 1.2Ueq(O) or 1.2Ueq(N).Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989018011714/cq2026sup1.cifCrystal structure: contains datablock(s) global, I. DOI: 10.1107/S2056989018011714/cq2026Isup2.hklStructure factors: contains datablock(s) I. DOI: 1583097CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


The conformations of the title compounds, (I) and (II), are very similar. The pyran rings adopt envelope conformations, the piperidine rings have chair conformations and the pyrrolidine rings adopt twist conformations. Intra- and intermolecular C—H⋯O hydrogen bonds occur. Compound (II) crystallizes with two independent molecules in the asymmetric unit which are linked by C—H⋯O hydrogen bonds. 32H25ClN2O4 (I) and C33H28N2O5 (II), the six-membered pyran and piperidine rings adopt envelope and chair conformations, respectively. The five-membered pyrrolidine rings adopt twist conformations. Compound (II) crystallizes with two independent molecules (A and B) in the asymmetric unit. In all three molecules there is a C—H⋯O intramolecular hydrogen bond present enclosing an S(7) ring motif. In (I), both oxygen atoms of the nitro group are disordered, while in (II) the methoxybenzene group is disordered in molecule B. The geometries were regularized by soft restraints. In the crystal of (I), molecules are linked by C—H⋯O hydrogen bonds, forming chains along [010]. The chains are linked by C—H⋯Cl hydrogen bonds, forming layers parallel to (10A and B molecules are linked via C—H⋯O hydrogen bonds, forming a square four-membered A–B–A–B unit. These units are linked by a number of C—H⋯π interactions, forming a three-dimensional supramolecular structure.In the title compounds, C The structural overlap of compound (I)B of compound (II)B of compound II (major component) on molecule A is shown in Fig. 5A and IIB) the pyran rings have envelope conformations with the methylene C atom C21 as the flap. The piperidine rings adopt chair conformations, while the pyrrolidine rings adopt twist conformations on the N1—C12 bond (N1A—C12A in IIA and N1B—C12B in IIB).The molecular structure of compound (I)A and B of compound (II)A and 66.7 (2) and 59.3 (5)° for molecule B. The benzene rings (C27–C32 and C14—C19) are inclined to each other by 50.0 (1)° in (I)A and 71.6 (2)° in molecule B of (II)A and 36.1 (2)° for molecule B in (II)A and 13.1 (2)° in molecule B of compound (II)A and 36.2 (2)° in molecule B of compound (II)supporting information. The keto atom O1 deviates from the mean plane of the plane of the acenaphthylene ring system (C1—C12) by 0.070 (2) Å in (I)et al., 2013abThe mean plane of the five-membered pyrrolidine ring (N1/C12/C13/C21/C22) is inclined to the mean plane of the cyclopen3–en-1-one ring (C1/C2/C10–C12) by 85.7 (1)° in compound (I)b-axis direction. The chains are linked by C—H⋯Cl hydrogen bonds, forming layers parallel to the s Table 2. These as Table 2.et al., 2016H,6′H,6b′H-spiroindolizin]-2-one skeleton yielded two hits: namely 6-(4-methoxyphenyl)-6a-nitro-6,6a,6b,7,8,9,10,12a-octahydrospiroindolizine-12,3-indolin]-2-one  for (I)H-chromene (1 mmol) for (II)To a solution of acenaphthoquinone (1.0 mmol) and piperidine-2-carboxylic acid (1.5 mmol) in dry toluene, was added 2-(4-chlorophenyl)-3-nitro-2Uiso(H) = 1.5Ueq(C-methyl) and 1.2Ueq(C) for other H atoms. In compound (I)B is disordered, as detectable from the large displacement parameters for the C and O atoms and short C—C and C—O bond lengths. This disorder over two positions was modelled and the site occupancies refined to 0.739 (5) and 0.261 (5). The geometry was regularized by soft restraints.Crystal data, data collection and structure refinement details are summarized in Table 310.1107/S2056989019000422/su5472sup1.cifCrystal structure: contains datablock(s) global, I, II. DOI: Click here for additional data file.10.1107/S2056989019000422/su5472Isup2.cmlSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019000422/su5472IIsup3.cmlSupporting information file. DOI: 10.1107/S2056989019000422/su5472sup4.pdfPuckering and asymmety parameters. DOI: 1024915, 1024235CCDC references:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Correction to: Infect Agents Cancer (2019) 14:46https://doi.org/10.1186/s13027-019-0262-5The original publication of this article  containeErrors in original publication:“Fish notch1b/Human NOTCH2” should be “Fish reck/Human RECK“Fish notch1b/Human NOTCH3” should be “Fish srd5a1/Human SRD5A1“Fish notch1b/Human NOTCH4” should be “Fish wnt7bb/ HumanWNT7B”“Fish notch1b/Human NOTCH5” should be “Fish pparg/Human PPARG”


Nature Communications 10.1038/s41467-019-12167-9, published online 19 September 2019.Correction to: Sλ(P) = 1.45, WP = 1.08 and Wω = 32.3’. The correct version reads ‘Sλ(P) = 0.90, WP = 0.71 and Wω = 25.3’. Similarly in Fig. 1b, the label at the top of the left panel incorrectly read ‘Sλ(P) = 0.90, WP = 0.71 and Wω = 25.3’. The correct version reads ‘Sλ(P) = 1.45, WP = 1.08 and Wω = 32.3’. This has been corrected in both the PDF and HTML versions of the Article.The original version of this Article contained errors in Fig. 1. In Fig. 1a, the label at the top of the left panel incorrectly read ‘


Correction to: Microbiomehttps://doi.org/10.1186/s40168-019-0643-4Following publication of the original article , the autPage 3, right column: Additional file 1: Table S1 → Table 1.Page 4, right column: detail in Additional file 1: Table S1 → detail in Additional file 2: Supplementary results.Page 5, right column: Table 2  → Table 2 .Page 12, left column: Additional file 1: Table S10 → Additional file 1: Table S11.Page 12, left column: Additional file 1: Table S12 → Additional file 5: Table S12.Description of additional files on Page 12 and 13:Table S10 and Table S12→ Table S12 and Table S10. Respectively.Additional file 5 Table S5 → Additional file 5: Table S12.Kim et al. [19] → Kim et al. [21]


In the crystal, the molecules form zigzag stacks along the  15H12ClNO3, consists of a 1,2-dihydroquinoline-4-carboxylate unit with 2-chloroethyl and propynyl substituents, where the quinoline moiety is almost planar and the propynyl substituent is nearly perpendicular to its mean plane. In the crystal, the molecules form zigzag stacks along the a-axis direction through slightly offset π-stacking interactions between inversion-related quinoline moieties which are tied together by intermolecular C—HPrpnyl⋯OCarbx and C—HChlethy⋯OCarbx  hydrogen bonds. The Hirshfeld surface analysis of the crystal structure indicates that the most important contributions for the crystal packing are from H⋯H (29.9%), H⋯O/O⋯H (21.4%), H⋯C/C⋯ H (19.4%), H⋯Cl/Cl⋯H (16.3%) and C⋯C (8.6%) interactions. Hydrogen bonding and van der Waals interactions are the dominant interactions in the crystal packing. Computational chemistry indicates that in the crystal, the C—HPrpnyl⋯OCarbx and C—HChlethy⋯OCarbx hydrogen bond energies are 67.1 and 61.7 kJ mol−1, respectively. Density functional theory (DFT) optimized structures at the B3LYP/ 6–311 G level are compared with the experimentally determined molecular structure in the solid state. The HOMO–LUMO behaviour was elucidated to determine the energy gap.The title compound, C We report herein on the synthesis and the molecular and crystal structures of the title compound along with the Hirshfeld surface analysis and the intermolecular interaction energies and the density functional theory (DFT) computational calculation carried out at the B3LYP/6–311 G level.The quinoline ring system is an important structural unit in naturally occurring quinoline alkaloids, therapeutics and synthetic analogues with interesting biological activities. Quinolone derivatives possess a variety of pharmacological properties such as anti-bacterial (Hu A (C1–C6) and B (N1/C1/C6–C9), of the dihydroquinoline unit are oriented at a dihedral angle of 2.69 (17)°. The mean plane through the dihydroquinoline unit is almost planar with a maximum deviation of 0.040 (3) Å for atom N1, and the propynyl substituent is nearly perpendicular to that plane, the C6—N1—C10—C11 torsion angle being −79.6 (4)°. The carboxyl group is twisted out of coplanarity with the dihydroquinoline unit by a dihedral angle of 47.13 (23)°; this is also indicated by the C1—C9—C13—O2 torsion angle of −44.2 (6)°.The title molecule consists of a 1,2-dihydroquinoline-4-carboxylate unit with 2-chloroethyl and propynyl substituents Fig. 1. The cona-axis direction through slightly offset π-stacking interactions between inversion-related quinoline moieties  hydrogen bonds, enclosing A (C1–C6) and B (N1/C1/C6–C9), of the dihydroquinoline unit, Cg2⋯Cg1i, Cg2⋯Cg1ii and Cg1⋯Cg1i , may further stabilize the structure.In the crystal, the molecules form zigzag stacks along the es Fig. 2. The stas Table 1. The π–πCrystalExplorer17.5  analysis  are viewed as a pair of spikes with the tips at de + di = 2.28 Å. In the absence of C—H⋯π interactions, the pairs of characteristic wings in Fig. 7d arise from H⋯C/C⋯H contacts (19.4%) and are viewed as pairs of spikes with the tips at de + di = 2.65 Å and 2.70 Å for the thin and thick spikes, respectively. The scattered points in the pair of wings in the fingerprint plot delineated into H⋯Cl/Cl⋯H  have a symmetrical distribution with the edges at de + di = 2.60 Å. The C⋯C contacts, Fig. 7f, have an arrow-shaped distribution of points with the tip at de = di = 1.72 Å. Finally, the characteristic tip and wings in the fingerprint plots delineated into C⋯N/N⋯C and O⋯Cl/Cl⋯O contacts  have the tips at de = di = 1.73 and 3.70 Å, respectively.The overall two-dimensional fingerprint plot, Fig. 7H Table 2, contribdnorm plotted onto the surface are shown for the H⋯H, H⋯O/O⋯H, H⋯C/C⋯H and H ⋯ Cl/Cl⋯H interactions in Fig. 8a–d, respectively.The Hirshfeld surface representations with the function et al., 2015The Hirshfeld surface analysis confirms the importance of H-atom contacts in establishing the packing. The large number of H⋯H, H⋯O/O⋯H, H ⋯ C/C⋯H and H⋯Cl/Cl⋯H interactions suggest that van der Waals interactions and hydrogen bonding play the major roles in the crystal packing  is the sum of electrostatic (Eele), polarization (Epol), dispersion (Edis) and exchange-repulsion (Erep) energies  were calculated to be −25.2 (Eele), −2.1 (Epol), −85.4 (Edis), 57.5 (Erep) and −67.1 (Etot) for the C—HPrpnyl⋯OCarbx hydrogen bond and −26.5 (Eele), −4.7 (Epol), −73.2 (Edis), 54.3 (Erep) and −61.7 (Etot) for the C—HChlethy⋯OCarbx hydrogen bond.The intermolecular interaction energies were calculated using the CE–B3LYP/6–31G energy model available in via density functional theory (DFT) using the standard B3LYP functional and 6–311 G basis-set calculations . The significance of η and σ is to evaluate both the reactivity and stability. The electron transition from the HOMO to the LUMO energy level is shown in Fig. 9E = ELUMO − EHOMO] of the molecule is 3.6984 eV, and the frontier molecular orbital energies, EHOMO and ELUMO are −6.3024 and −2.6040 eV, respectively.The optimized structure of the title compound in the gas phase was generated theoretically et al., 2016et al., 2018abet al., 2019A non-alkylated analogue, namely quinoline and its derivatives, has been reported  and TBAB . The reaction mixture was stirred at room temperature for 6 h. After removal of the salts by filtration, the solvent was evaporated under reduced pressure and the resulting residue was dissolved in dichloromethane. The organic phase was dried with Na2SO4, and then concentrated under reduced pressure. The pure compound was obtained by column chromatography using hexane/ethyl acetate (3/1) as eluent. The isolated solid was recrystallized from hexane/ethyl acetate (3:1) to afford colourless crystals .To a solution of 2-chloroethyl 2-oxo-1,2-dihydroquinoline-4-carboxylate  in DMF (10.00 ml) were added propargyl bromide , K2 H atoms, respectively) and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C). The largest peak and hole in the final difference map are +0.73 e Å−3 (1.00 Å away from Cl1) and −0.35 e Å−3 (0.64 Å away from C14), and are associated with the 2-chloroethylcarboxy group and may indicate a slight degree of disorder here but it was not considered serious enough to model.Crystal data, data collection and structure refinement details are summarized in Table 510.1107/S2056989019012283/lh5918sup1.cifCrystal structure: contains datablock(s) I, global. DOI: 10.1107/S2056989019012283/lh5918Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019012283/lh5918Isup3.cdxSupporting information file. DOI: Click here for additional data file.10.1107/S2056989019012283/lh5918Isup4.cmlSupporting information file. DOI: 1951439CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


Quantum chemical calculations revealed details on the strength and geometrical requirements of these N+-C-H···O hydrogen bonds, and a subsequent survey of the Protein Data Bank (PDB) based on these criteria suggested that numerous protein-ligand complexes contain such N+-C-H···O hydrogen bonds. An ensuing experimental investigation into the G9a-like protein (GLP)-inhibitor complex demonstrated that N+-C-H···O hydrogen bonds affect the activity of the inhibitors against the target enzyme. These results should provide the basis for the use of N+-C-H···O hydrogen bonds in drug discovery.In the context of drug design, C-H···O hydrogen bonds have received little attention so far, mostly because they are considered weak relative to other noncovalent interactions such as O-H···O hydrogen bonds, π/π interactions, and van der Waals interactions. Herein, we demonstrate the significance of hydrogen bonds between C-H groups adjacent to an ammonium cation and an oxygen atom (N Such interactions manifest between proteins and their ligands in many protein complexes registered on the Protein Data Bank (PDB). Accordingly, these interactions should always be considered when designing ligands for target proteins7.Noncovalent interactions, such as heteroatom-hydrogen bonds X-H···Y  and π/π interactions play a critical role in the formation of protein-ligand complexes11. However, when the C-H group is activated by electron-withdrawing groups, e.g. C-H groups that are covalently bound to a cationic nitrogen atom (N+-C-H), C-H···O hydrogen bonds may become as strong as heteroatom-hydrogen bonds, which could be important for molecular recognition19. For example, N+-C-H···Y hydrogen bonds are likely to be involved in the substrate recognition of tetraalkylammonium-based catalysts21, and the ligand/substrate recognition in receptors/enzymes may be controlled by N+-C-H···O hydrogen bonds , the latter are almost exhaustively protonated under physiological conditions (pH = 7–8). Accordingly, ligands bearing tetraalkylammonium or aliphatic amino groups could be recognized by the oxygen atoms of the proteins via N+-C-H···O hydrogen bonds  theoretical research and criteria setting for N+-C-H···O hydrogen bonds by quantum chemical calculations , propanoate (2), ethanol (3), and phenol (4) as hydrogen acceptor models for the protein peptide bond/Asn/Gln, Asp/Glu, Ser/Thr, and Tyr, respectively, and monomethylammonium (5), trimethylammonium (6) or N-methylpiperidium (7) as hydrogen donor models in protonated aliphatic amine-containing ligands. Geometry optimizations and single-point calculations were carried out at the M06-2X/6-311++G** level of theory26. The results of this computational study allowed us to establish selection criteria for N+-C-H···O hydrogen bonds  analysis28 of 5 indicated that the positive charge is distributed over the H atoms , including those of the CH3 group, rather than being localized on the N atom (−0.688)  is more positive than that of monomethylamine  or ethane . These results suggest high potential for the N+-C-H group to act as a hydrogen donor in hydrogen bonds.Initially, we analyzed the electrical charges on the hydrogen donors of the NA1, B1 and C1, i.e., complexes of 1, 2, and 3 with 6, as well as that of complex D1, which consists of 4 and 7 in the gas phase , which suggests the formation of intermolecular hydrogen bonds between these atoms  or 2,2-dimethylpropane (11), and 7 in D1 is replaced with N-methylpiperidine (12) or methyl cyclohexane (13) , the C-H···O angle (ψ), the H···O=C/H···O-C angle (ξ), and the H-elevation angle (θ)30  were calculated  30 Figs  and 5A. ant Fig. . For H··ted Fig. , which ited Fig. . The est7 Å Fig. . The dis Å) Figs  and 5B. A4 on the C-H···O angle (ψ). For 90° < ψ < 180°, the interaction energy is relatively low   Figs  and 5C. ses Fig. , a simil80° Figs  and 5C. ξ). Calculating the interaction energies, we discovered that these energies depend on the type of hydrogen acceptors. In the case of amide acceptors, i.e., for 105° < ξ < 180°, the interaction energies are low and the preferred angles are ξ > 135°  was permissible, and B4 exhibited a preference for ξ > 240°   Figs . For carθ). For θ < 70° (A4), θ < 60° (C4), and θ < 75° (D4), low interaction energies were calculated  and propanoate (2) are widely distributed  and phenol (4) is centered on the area where the plane bisecting the C-O-H angle intersects with the C-O-H plane  and H···O (dHO) bond distances  in the ξ dataset, we observed 13 interactions with 105° < ξ < 135°. According to our calculations  and C-elevation (ϕ) angles are subject to a certain degree of correlation , whereas contacts of carboxylate acceptors exhibited a wide distribution of these angles -inhibitor complex 14a . Relative to 14a, 14b significantly reduced the GLP-inhibitory activity (IC50 = 0.664 μM) in the 0.1–1 μM concentration range. In the same concentration range, 14c showed a decreased GLP-inhibitory activity (IC50 = 1.45 μM) compared to 14a and 14b, while 14d did not show any GLP inhibition up to 3 μM. The latter result should most likely be rationalized in terms of a lack in both electrostatic interactions and C-H···O hydrogen bonds between the ligand and GLP. Moreover, we determined the dissociation constant and thermodynamic parameters of 14a–c by means of isothermal titration calorimetry (ITC). As shown in Supplementary Fig. 14a–c was distinctly dependent on the number of methyl group , which is consistent with the IC50 values of 14a–c. The thermodynamic parameters were also dependent on the number of methyl group: the ΔH values for dimethyl 14a, monomethyl 14b, and non-methyl 14c were −10.7 kcal/mol, −8.58 kcal/mol, and −7.04 kcal/mol, respectively; the −TΔS values for 14a, 14b, and 14c were 1.42 kcal/mol, 0.10 kcal/mol, and −1.19 kcal/mol, respectively . It is well known that enthalpic forces such as hydrogen bond formation can decrease entropic forces by restricting the degrees of freedom of water molecules and protein conformation33. Based on this, there is a possibility that the methyl group of 14a and 14b reduced the ΔH value by the conformational fixation of GLP through the formation of N+-C-H···O hydrogen bonds, which resulted in reduction of the TΔS value by decreasing the degrees of freedom of water molecules and protein conformation, and the effect of enthalpy was larger than that of entropy. Taken together, the observed GLP-inhibitory activity, disassociation constant and thermodynamic parameters for 14a–d strongly suggests that the N+-C-H···O hydrogen bonds in the GLP-ligand complex are responsible for their GLP-inhibitory activity, although the effect might not be attributed exclusively to the N+-C-H···O hydrogen bonds.To experimentally validate the importance of the N14a Fig. , one of GLP Fig. . In ordetom Fig. . Compounely Fig. . If the ity Fig. . The par+-CH3 groups do not engage in N+-C-H···O hydrogen bonds with any protein-based oxygen atom. The X-ray crystal structure of tyrosine kinase with Ig and EGF homology domains-2 (tie-2) complexed to its inhibitor 15a indicates that the methylene group that is in conjugation with the aliphatic amino group forms an N+-C-H···O hydrogen bond, but the methyl groups do not 36, which is often used for long distance interactions, with the 6-311++G** basis set in the gas phase or in the water phase37. Structures were considered as minima in case of all harmonic frequencies being positive. All interaction energies were corrected for basis set superposition errors (BSSE) by the counterpoise procedure38. To gauge the accuracy of the M06-2X/6-311++G** level of theory, the thus obtained binding energies were compared to those obtained from MP2/aug-cc-pVTZ  C···O distance (dCO): <3.7 Å27; (ii) H···O distance (dHO): <2.7 Å; (iii) C-H···O angle (ψ): >90° for the peptide bond/Asn/Gln and Asp/Glu acceptors, or >105° for the Ser/Thr/Tyr acceptors; (iv) H···O=C angle (ξ): >105° for the peptide bond/Asn/Gln acceptors, >90° for the Asp/Glu acceptors, or 105°–150° for the Ser/Thr/Tyr acceptors; (v) H···elevation angle (θ): <70° for the peptide bond/Asn/Gln acceptors, <80° for the Asp/Glu acceptors; (vi) N+-C···O angle (α): 60°–160°; (vii) C···O-C angle (β): >95° for the peptide bond/Asn/Gln, >90° for the Asp/Glu acceptors, or 95°–160° for the Ser/Thr/Tyr acceptors; (viii) C-elevation (ϕ): <80° for the peptide bond/Asn/Gln and <90° for Asp/Glu. The H-elevation angle (θ) was calculated according to sinθ = sinξ · sinχ, whereby χ refers to the average of the two corresponding dihedral angles H···O=C-O(N) and H···O=C-C. Similarly, the C-elevation angle (ϕ) was calculated by sinϕ = sinβ · sinδ, whereby δ refers to the average of the two corresponding dihedral angles C···O=C-O(N) and C···O=C-C.All X-ray structures of proteins bound to amine-containing ligands were downloaded from the Protein Data Bank (PDB). To gain a better understanding of NThe GLP activity assay was carried out using a GLP Chemiluminescent Assay Kit . Microwells were rehydrated by adding 200 μL of tris buffered saline with Tween 20  to every well, followed by incubation at room temperature for 45 minutes. After removing TBS-T, the inhibitors were incubated in the presence of 2 μM SAM and 40 ng of GLP in the supplied buffer on the microwells of . After the enzymatic reaction, every well was washed three times with TBS-T (100 μL) and blocked for 10 min with blocking buffer. Then, 100 μL of primary anti-body solution (1:400 dilution) were added to the microwells, followed by incubation (2 h). The wells were probed with the primary antibody, washed three times with TBS-T (100 μL), incubated  with sheep secondary anti-body (1:1000 diluted), and again washed three times with TBS-T (100 μL). The chemiluminescence of the wells, to which detection reagents were added, was measured on a chemiluminescence reader (ARVO X3 Multilabel Plate Reader), and the values of % inhibition were calculated from the chemiluminescence readings of inhibited wells relative to those of control wells.−1. The heat of dilution of the ligand into the buffer measured independently was essentially similar to the heat signal obtained at the end of the titration; so the signal of the last injection was used as the background heat signal. The experimental data were analyzed using the MicroCal PEAQ-ITC Analysis software , and fitted using the one-site binding model. Values of ΔG, KD, and −TΔS were calculated using the thermodynamic relationships, ΔG = −RT lnKa, KD = 1/Ka, and ΔG = ΔH − TΔS.A GLP recombinant protein solution  was concentrated by ultrafiltration and the buffer was replaced with test buffer . ITC measurements of GLP inhibitors binding to the GLP were recorded at 25 °C using a MicroCal PEAQ-ITC microcalorimeter  in the test buffer. The titrations were performed using 10 μM GLP solution in the sample cell and 100 μM inhibitor solution in the syringe. A typical experiment consisted of 19 injections under the following parameters: one injection of 0.4 μL followed by 18 injections of 2.0 μL; 150 s spacing between injections; 750 rpm stirring speed; and reference power set to 5 μcal s2SO4 (1N). The absorbance at 450 nm of the wells, to which detection reagents were added, was measured in a chemiluminescence reader (ARVO X3 Multilabel Plate Reader), and the values of % inhibition were calculated from the absorbance readings of inhibited wells relative to those of control wells.The tie-2 activity assay was carried out using human recombinant active enzyme  and Universal Tyrosine Kinase Assay Kit . The inhibitors  were incubated in the presence of 40 mM ATP and 20 ng of tie-2 in the supplied buffer including 5 mM DTT on the microwells of the supplier . After the enzymatic reaction, the mixtures were removed from the wells and all wells were washed four times with phosphate buffered saline with Tween 20 . Then, the wells were blocked (30 min) with blocking buffer, before 50 μL of anti-phosphated Tyrosine-POD were added to the wells, and incubation was continued . The wells were probed, washed four times with PBS-T (100 μL), and subsequently incubated with HRP substrate solution . Finally, the reaction was stopped by addition of aqueous HSupplementary Information


Correction to: Biol Direct (2019) 14:14https://doi.org/10.1186/s13062-019-0247-8After publication of this article , the aut0 – f τR0 - fδτ2 ] + f τ [S(t) + τδ] (t < 80 years), rather than C = exp (τ −t/ [C0 – f τR0 -fδτ2] + f τ [S(t) + τδ] (t < 80 years) in the previous publication.The first error is in the equation of the footnote 1. The correct equation should be: C = exp(-t/ τ) [CThe second error is in the beginning of the third line from the bottom of the footnote currently reads dC/dt = S(t) - C/ τ whereas it should read dC/dt = f S(t) - C/ τ.The last error is the year in the last sentence of the response to Reviewer’s report 2: it should be 2018 rather than 1918.


NO2⋯π(N)NO2 interaction.The title tetranuclear cluster contains a tetrahedral arrangement of copper(II) ions bonded to a central oxygen atom. The extended structure shows short O⋯N interactions between the nitro groups of adjacent clusters, which are oriented perpendicular to each other in a manner that has previously been described as an O 4Cl6O(C6H9N3O3)4] or [Cu4Cl6O(MET)4] [MET is 1-(2-hydroxyethyl)-2-methyl-5-nitro-1H-imidazole or metronidazole], contains a tetrahedral arrangement of copper(II) ions. Each copper atom is also linked to the other three copper atoms in the tetrahedron via bridging chloride ions. A fifth coordination position on each metal atom is occupied by a nitrogen atom of the monodentate MET ligand. The result is a distorted CuCl3NO trigonal–bipyramidal coordination polyhedron with the axial positions occupied by oxygen and nitrogen atoms. The extended structure displays O—H⋯O hydrogen bonding, as well as unusual short O⋯N interactions [2.775 (4) Å] between the nitro groups of adjacent clusters that are oriented perpendicular to each other. The scattering contribution of disordered water and methanol solvent molecules was removed using the SQUEEZE procedure  in PLATON .The title tetranuclear copper complex, [CuSpek 2015. Acta CrSpek 2009. Acta Cr In the title complex, α = 110.80 (9)° and β = 109.55 (9)°, such that τ4 is 0.990, which indicates negligible deviation from a tetrahedral geometry for oxygen  to 2.4435 (9) Å . Each copper atom is also bound to a nitrogen atom of a MET ligand. The Cu—N lengths range from 1.949 (2) to 1.972 (3) Å . Thus, each copper atom sits within a trigonal–bipyramidal arrangement, with the oxygen and nitrogen atoms forming the axial coordination points, and the bridging chloride ligands occupying the equatorial plane. The trigonal–bipyramidal structure is somewhat distorted, as indicated by the fact that the O—Cu—N angles are less than 180°, ranging from 173.12 (10) to 176.91 (10)° , and the Cl—Cu—Cl angles differ significantly from 120°, ranging from 109.97 (3) to 134.02 (3)° . Furthermore, the O—Cu—Cl angles are all less than 90°, ranging from 83.33 (6) to 86.13 (6)° , indicating that the equatorial chloride ligands are displaced slightly more towards the axial oxygen atom in the center of the molecule, than towards the nitrogen-containing ligand in the opposite axial position.Each of the four copper atoms is linked to the other three copper atoms 5 geometry index is a general descriptor of five-coordinate molecules and provides a way to determine the extent of distortion of a molecule from trigonal bipyramidal to square pyramidal /60, where β − α is the difference between the two largest angles , 0.74 (Cu2), 0.84 (Cu3) and 0.73 (Cu4) for the five-coordinate copper centers, giving an average τ5 value of 0.74. The τ5 values obtained indicate that the copper-centered structures are closer to an idealized trigonal–bipyramidal (1.00) than a square-pyramidal geometry (0.00).The τA and O21—H21A probably form links to the disordered solvent molecules removed with SQUEEZE . The most interesting observation is the existence of short O⋯N interactions between the N13/O12/O13 and N33/O32/O33 nitro groups of adjacent clusters that are oriented perpendicular to each other, as illustrated in Fig. 3NO2⋯π(N)NO2 interaction 4] contains Cu—X distances that are similar to those in [Cu4Cl6O(imidazole)4] 4] are 1.8960 (18)–1.913 (2) Å, compared to 1.903 (4)–1.924 (4) Å for [Cu4Cl6O(imidazole)4]. Likewise, the Cu—Cl distances in [Cu4Cl6O(MET)4] are 2.3579 (10)–2.4435 (9) Å, compared to 2.374 (2)–2.564 (2) Å for [Cu4Cl6O(imidazole)4]. Moreover, the Cu—N distances in [Cu4Cl6O(MET)4] are 1.949 (2)–1.972 (3) Å, compared to 1.934 (6)–1.961 (6) Å.The title compound [CuAnhydrous copper(I) chloride  was mixed with MET  in methanol (2 ml) in a glass vial, forming a dark olive-colored solution. After allowing the solution to evaporate for eight days, gold-colored plates, suitable for X-ray diffraction, were obtained.Uiso(H) = 1.2Ueq(Csp2) or 1.5Ueq(Csp3). Atoms C34, C35 and O31 and their attached H atoms were modeled as disordered over two sets of sites in a 0.515 (19):0.485 (19) ratio. The structure contains two methanol molecules and one water molecule, but they are disordered and were removed by the SQUEEZE procedure in PLATON  only refer to the main molecule.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019008570/hb7801sup1.cifCrystal structure: contains datablock(s) I. DOI: 10.1107/S2056989019008570/hb7801Isup2.hklStructure factors: contains datablock(s) I. DOI: 1923275CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


In the title compound, 1,3-dioxolane and 1,3-dioxole rings adopt envelope forms, while amide moiety and benzene ring are essentially planar. An intramolecular O—H⋯O hydrogen bond supports the molecular conformation, and intermolecular weak C—H⋯O and C—H⋯π interactions connect the molecules into sheet structure. 20H27NO6, the amide moiety is essentially planar, with a maximum deviation of 0.073 (3) Å, and one of the N-methyl groups shows rotational disorder. The five-membered 1,3-dioxolane ring adopts an envelope form, with the C atom bonded to the olefin side chain as the flap, which deviates from the mean plane through the other four atoms by 0.564 (7) Å. The 1,3-dioxole ring fused to the benzene ring adopts a flattened envelope form, with the C atom between the two O atoms as the flap, which deviates from the mean plane through the other four atoms by 0.215 (7) Å. The C—C=C—C olefin moiety is essentially planar and makes a dihedral angle of 87.1 (3)° with the benzene ring. An intramolecular O—H⋯O hydrogen bond supports the molecular conformation, enclosing an S(11) graph-set motif. In the crystal, intermolecular C—H⋯O hydrogen bonding links the molecules into a tape running along the b axis. Furthermore, other weak C—H⋯O hydrogen bonds and a C—H⋯π interaction connect the tapes into a sheet structure parallel to (100).In the title compound, C These conversions are often carried out with protection of the contiguous diol  shows rotational disorder over two orientations, with refined occupancies of 0.54 (8) and 0.46 (8). The 1,3-dioxolane ring (C10/O11/C12/O13/C14) adopts an envelope form, with puckering parameters of Q(2) = 0.362 (5) Å and φ(2) = 40.6 (7)°. The flap atom C10 deviates from the mean plane through the other four atoms by 0.564 (7) Å. The 1,3-dioxole ring (C23/C24/O25/C26/O27) in benzodioxole adopts a flattened envelope form, with puckering parameter of Q(2) = 0.135 (5) Å and φ(2) = 326 (2)°. The flap atom C26 deviates from the mean plane through the other four atoms by 0.215 (7) Å. The olefin moiety (C7—C8=C9—C10) is essentially planar and makes a dihedral angle of 87.1 (3)° with the benzene ring (C19–C24). An intramolecular O—H⋯O hydrogen bond  graph-set motif.The molecular structure of the title compound is shown in Fig. 1i; symmetry code as in Table 1b axis, with a C(3) graph-set motif. Furthermore, other weak C—H⋯O hydrogen bonds and a C—H⋯π interaction , similar to the title compound , gives two entries with refcodes YERGUX , has yet been reported.On the other hand, searching the CSD for a structure with a combination of benzodioxole and oxymethyldioxolane components, . HRMS (ESI) m/z calculated for C20H27NO6Na+ [M + Na]+: 400.1736; found: 400.1731.The title compound was synthesized in two steps from 3,4-d-arabinose. The H atoms on one of the N-methyl groups (C4) are disordered; they were split into two sets of positions H4A–C and H4D–F, the refined occupancies being 0.54 (8) and 0.46 (8), respectively. C-bound H atoms were positioned geometrically, with C—H = 0.95–1.00 Å, and constrained to ride on their parent atoms, with Uiso(H) = 1.5Ueq(C) for methyl groups or 1.2Ueq(C) otherwise. The hydroxy H atom was placed in a difference map and treated as riding, with O—H = 0.84 Å and Uiso(H) = 1.5Ueq(O). One problematic reflection  global, I. DOI: 10.1107/S2056989018007132/is5496Isup2.hklStructure factors: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989018007132/is5496Isup3.cmlSupporting information file. DOI: 1842600CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


These are packed via C—H ⋯N and C—H⋯π interactions, resulting in a three-dimensional architecture with a tilted herringbone packing mode.The two independent molecules in the asymmetric unit of the title compound are connected  14H12N4S, was synthesized by the condensation reaction of hydralazine and 2-acetylthiophene and during the reaction, a proton transfer from the imino nitrogen atom to one of the endocylic nitrogen atoms occurred. The compound crystallizes in the monoclinic crystal system with two independent molecules (molecules 1 and 2) in the asymmetric unit. In each molecule, there is a slight difference in the orientation of the thiophene ring with respect to phthalazine ring system, molecule 1 showing a dihedral angle of 42.51 (1)° compared to 8.48 (1)° in molecule 2. This implies an r.m.s deviation of 0.428 (1) Å between the two molecules for the 19 non-H atoms. The two independent molecules are connected via two N—H⋯N hydrogen bonds, forming dimers which interact by two bifurcated π–π stacking interactions to build tetrameric motifs. The latter are packed in the ac plane via weak C—H⋯π interactions and along the b axis via C—H ⋯N and C—H⋯π interactions. This results a three-dimensional architecture with a tilted herringbone packing mode.The title compound, C The lengths of the N4—C9 and N4B—C9B bonds of 1.294 (2) and 1.296 (2) Å, respectively, are in agreement with that of an N=Csp2 bond (1.282 ±0.060) Å found in the CSD  Å] and N3B—C8B [1.309 (2) Å] and the single-bond character of N3—N4 [1.398 (2) Å] and N3B—N4B [1.400 (2) Å]. Indeed, these values are in agreement with the bond lengths for C=N and N-N bonds  in the C=N—N fragment with a cyclic carbon atom and acyclic nitrogen atoms for organic compounds in the CSD. Such a proton transfer has been reported in other hydrazinophthalazine derivatives  are in a planar conformation with a maximum deviation of 0.006 (1) Å for S1 in molecule 1 and of 0.003 (1) Å for S1via two N—H⋯N hydrogen bonds .Molecules 1 and 2 are linked on Fig. 4 and in tns Fig. 5. The reset al., 2016et al., 2007et al., 2014aA search of the Cambridge Structural Database  and hydralazine hydrochloride  in 20 ml of methanol and 10 ml of aqueous solution of sodium acetate  as buffering agent. The mixture was refluxed at 338 K under stirring for four h. The product was left overnight to cool. The yellow precipitate was filtered off and washed several times with water and methanol, and finally crystallized from a mixture of DMF/methanol (2:1) as yellow crystals (in a yield of around 80%) suitable for single-crystal X-ray diffraction studies.Uiso(H)= 1.2Ueq.Crystal data, data collection and structure refinement details are summarized in Table 210.1107/S2056989019000732/lh5889sup1.cifCrystal structure: contains datablock(s) I. DOI: Click here for additional data file.10.1107/S2056989019000732/lh5889Isup2.cmlSupporting information file. DOI: 1891271CCDC reference:  crystallographic information; 3D view; checkCIF reportAdditional supporting information:


R2∗ values for 1.5 T and 3 T are reversed. The corrected equation is as follows:In the article titled “Hepatic Iron Quantification on 3 Tesla (3 T) Magnetic Resonance (MR): Technical Challenges and Solutions” , there w