Smart apex

The data were collected with a Bruker AXS Smart Apex2 CCD (Bruker, Ettlingen, Germany) diffractometer, operating at 179(2) K and using graphite monochromated Mo-Kα radiation (λ = 0.71073 Å). Cell refinement, indexing, and scaling of the datasets were performed, using the program Bruker Smart Apex and Saint packages [55 ]. The structure was solved by direct methods and refined by full-matrix least-squares on F² with anisotropic displacement parameters for all non-hydrogen atoms, using the program SHELXL [56 (link)]. The H atoms were included as riding contributions with fixed isotropic displacement parameters in idealized positions. All the calculations were carried out by using the WinGX System, V2013.3 [57 (link)]. Crystal structure determination and refinement data are given in Table 5. CCDC-2014301 contains the supplementary crystallographic data for this paper (Supplementary Materials). These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html (or from the CCDC, 12 Union Road, Cambridge CB2 1EZ, UK; Fax: +44 1223 336033; E-mail: deposit@ccdc.cam.ac.uk).

Single crystals of D were obtained by the slow recrystallization from the DCM/heptane solution; crystals of D1 and FHPMOCl were obtained by the slow recrystallization from their DCM/octane solutions, and crystals of D2 and FHPMO₂ were obtained by the slow evaporation of their acetonitrile/water solutions. Single crystal X-ray analyses were performed on a SMART APEX equipped with CCD detector (Bruker) using MoKα (graphite, monochromated, λ = 0.71073 Å) radiation or CuKα (graphite, monochromated, λ = 1.54178 Å) radiation. The structures were solved by the direct method of SHELXS-97/2014/2018 and refined using the SHELXL-97/2014 or Olex2 1.2 program^{49 ,67 (link),68} . The positional parameters and thermal parameters of non-hydrogen atoms were refined anisotropically on F² by the full-matrix least-squares method. Hydrogen atoms were placed at calculated positions and refined riding on their corresponding carbon atoms. Detailed crystallographic data are provided in Supplementary Tables 2 and 3.

Appropriate crystal was selected for ionophore I, dipped in paratone oil, and mounted on cryo loop. Crystal data were collected at 100 K using graphite monochromatic MoKα (λ = 0.71073 Å) radiation on a Bruker SMART APEX diffractometer equipped CCD area detector. The SAINT software³⁷ was used for data integration and reduction. Empirical absorption correction was applied to the collected reflections with SADABS.³⁸ SHELXTL³⁹ was used to solve the structures by direct methods using and refined on F₂ by the full-matrix least-squares technique using the SHELXL-97 (ref. 40 ) package. Non-hydrogen atoms were refined anisotropically till convergence is reached. The MERCURY 3.8 (ref. 41 ) is used to generate graphics. The X-ray structure of ionophore I is shown in Fig. S17,† wherein chloroform and water molecules have been omitted for clarity. The phenolic OH of the alternate phenyl rings of the calix moiety are substituted by amide-linked chains. The presence of hydrogen bonding between amide NHs and phenolic oxygen atoms is also observed. Crystallographic parameters for the ionophore I are given in Table S1.†

Crystals suitable for single-crystal X-ray diffraction were selected, coated in perfluoropolyether oil, and mounted on MiTeGen sample holders. Diffraction data were collected on a Bruker Smart-Apex (compounds 5, 6, 7) or a Bruker X8 Apex II (compounds 1, 2, 4) 4-circle diffractometer with a CCD area detector using graphite-monochromated Mo-K_α radiation. The crystals were cooled using a home-made nitrogen gas jet or Bruker Kryoflex low-temperature device. Data were collected at 168 K (5, 6, 7) or 100 K (1, 2, 4). The images were processed and corrected for Lorentz-polarization effects and absorption as implemented in the Bruker software packages. The structures were solved using the intrinsic phasing method (SHELXT)³⁰ and Fourier expansion technique. All non-hydrogen atoms were refined in anisotropic approximation, with hydrogen atoms ‘riding’ in idealized positions, by full-matrix least squares against F² of all data, using SHELXL software.³⁰ Diamond³¹ software was used for graphical representation. Crystal data and experimental details are listed in Table S9 in the ESI;† full structural information has been deposited with Cambridge Crystallographic Data Centre. CCDC-2056492 (1), 2056493 (2), 2056494 (4), 2056495 (5), 2056496 (6), and 2056497 (7).