Interplay between molecular recognition and acid-base reactivity in tailored metal-based calix[6]arene receptors.
Lepeintre, Martin; Višnjevac, Aleksandar; Jabin, Ivan; Colasson, Benoit; Organic & biomolecular chemistry 23 (2025) 8012–8022; doi:10.1039/d5ob01099c

data_7160658
_publ_section_title
;
 Interplay between molecular recognition and acid-base reactivity in
 tailored metal-based calix[6]arene receptors.
;
_journal_issue                   35
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              8012
_journal_page_last               8022
_journal_paper_doi               10.1039/d5ob01099c
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         '2(C83 H105 N6 O8 Zn), C16 H36 N, 3(Cl O4)'
_chemical_formula_sum            'C142 H158 Cl0.5 N27 O21 Zn2'
_chemical_formula_weight         2727.41
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2025-04-10
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2025-05-20 deposited with the CCDC.	2025-07-29 downloaded from the CCDC.
;
_cell_angle_alpha                98.772(2)
_cell_angle_beta                 93.648(3)
_cell_angle_gamma                97.939(3)
_cell_formula_units_Z            2
_cell_length_a                   16.4168(7)
_cell_length_b                   24.6211(9)
_cell_length_c                   25.3326(6)
_cell_measurement_reflns_used    6949
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      51.2500
_cell_measurement_theta_min      3.3780
_cell_volume                     9985.1(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.705
_diffrn_measured_fraction_theta_max 0.705
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -22.00  22.00   0.50   20.00    --   -0.16  98.00  27.00   88
  2  \w     11.00  88.00   0.50   70.00    --   58.34 -98.00 -79.00  154
  3  \w    -71.00   4.00   0.50   70.00    --  -58.65  98.00  27.00  150
  4  \w    -67.00 -41.00   0.50   20.00    --   -0.16 -19.00-180.00   52
  5  \w      2.00  28.00   0.50   20.00    --   -0.16  57.00 -30.00   52
  6  \w     47.00  72.00   0.50   20.00    --   -0.16  57.00 -30.00   50
  7  \w     37.00  63.00   0.50   20.00    --   -0.16  19.00 120.00   52
  8  \w     -6.00  21.00   0.50   20.00    --   -0.16  57.00 -60.00   54
  9  \w     51.00 128.00   0.50   70.00    --   58.34  77.00 -30.00  154
 10  \w     38.00 131.00   0.50   70.00    --   58.34  77.00   0.00  186
 11  \w     35.00  60.00   0.50   70.00    --   58.34-125.00 -30.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0289821000
_diffrn_orient_matrix_UB_12      0.0182616000
_diffrn_orient_matrix_UB_13      -0.0527166000
_diffrn_orient_matrix_UB_21      -0.0774237000
_diffrn_orient_matrix_UB_22      0.0171605000
_diffrn_orient_matrix_UB_23      0.0252717000
_diffrn_orient_matrix_UB_31      0.0470177000
_diffrn_orient_matrix_UB_32      0.0589276000
_diffrn_orient_matrix_UB_33      0.0199297000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0609
_diffrn_reflns_av_unetI/netI     0.1120
_diffrn_reflns_Laue_measured_fraction_full 0.705
_diffrn_reflns_Laue_measured_fraction_max 0.705
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            30391
_diffrn_reflns_point_group_measured_fraction_full 0.705
_diffrn_reflns_point_group_measured_fraction_max 0.705
_diffrn_reflns_theta_full        53.741
_diffrn_reflns_theta_max         53.740
_diffrn_reflns_theta_min         3.052
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.794
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52793
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    0.907
_exptl_crystal_description       needle
_exptl_crystal_F_000             2871
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.754
_refine_diff_density_min         -0.474
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.987
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2137
_refine_ls_number_reflns         16875
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      0.998
_refine_ls_R_factor_all          0.1360
_refine_ls_R_factor_gt           0.0779
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1326P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1971
_refine_ls_wR_factor_ref         0.2321
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9161
_reflns_number_total             16875
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01099c2.cif
_cod_data_source_block           exp_307_auto
_cod_depositor_comments
'Adding full bibliography for 7160658--7160660.cif.'
_cod_original_formula_sum        'C142 H158 Cl0.50 N27 O21 Zn2'
_cod_database_code               7160658
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C83H105N6O8Zn
_shelx_estimated_absorpt_t_max   0.984
_shelx_estimated_absorpt_t_min   0.939
_reflns_odcompleteness_completeness 73.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     51.81
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O187-C186 = O185-C186
 1.28 with sigma of 0.02
 O187-O185
 2.3 with sigma of 0.02
3. Others
 Fixed Sof: C131(0.5) H13A(0.5) H13B(0.5) H13C(0.5) C94(0.5) H94A(0.5)
 H94B(0.5) H94C(0.5) C157(0.5) H15A(0.5) H15B(0.5) H15C(0.5) C152(0.5)
 H15D(0.5) H15E(0.5) H15F(0.5) C141(0.5) H14A(0.5) H14B(0.5) H14C(0.5)
 C129(0.5) H12A(0.5) H12B(0.5) H12C(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C50(H50A,H50B), C32(H32A,H32B), C28(H28A,H28B), C24(H24A,H24B), C89(H89A,
 H89B), C36(H36A,H36B), C130(H13D,H13E), C63(H63A,H63B), C40(H40A,H40B),
 C113(H11A,H11B), C18(H18A,H18B), C117(H11C,H11D), C109(H10A,H10B), C162(H16J,
 H16K), C125(H12D,H12E), C103(H10C,H10D), C121(H12F,H12G), C142(H14D,H14E),
 C178(H17H,H17I), C180(H18C,H18D), C179(H17J,H17K), C181(H18E,H18F), C182(H18J,
 H18K), C187(H18L,H18M), C144(H14I,H14J), C175(H17L,H17M), C146(H14K,H14L),
 C189(H18N,H18O), C184(H18P,H18Q), C183(H18R,H18S)
4.b Aromatic/amide H refined with riding coordinates:
 C126(H126), C22(H22), C43(H43), C14(H14), C76(H76), C61(H61), C160(H160),
 C59(H59), C41(H41), C138(H138), C20(H20), C81(H81), C46(H46), C107(H107),
 C158(H158), C105(H105), C79(H79), C74(H74), C140(H140), C128(H128), C149(H149),
  C154(H154), C151(H151), C156(H156), C92(H92), C67(H67), C93(H93), C53(H53),
 C135(H135), C134(H134), C54(H54), C166(H166), C165(H165), C66(H66), C145(H145),
  C170(H17D)
4.c Idealised Me refined as rotating group:
 C85(H85A,H85B,H85C), C84(H84A,H84B,H84C), C69(H69A,H69B,H69C), C176(H17A,H17B,
 H17C), C83(H83A,H83B,H83C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C58(H58A,
 H58B,H58C), C98(H98A,H98B,H98C), C56(H56A,H56B,H56C), C136(H13F,H13G,H13H),
 C73(H73A,H73B,H73C), C148(H14F,H14G,H14H), C99(H99A,H99B,H99C), C95(H95A,H95B,
 H95C), C188(H18G,H18H,H18I), C97(H97A,H97B,H97C), C168(H16L,H16M,H16N),
 C191(H19A,H19B,H19C), C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C49(H49A,H49B,H49C),
 C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C13(H13I,H13J,H13K), C68(H68A,H68B,H68C),
 C65(H65A,H65B,H65C), C173(H17E,H17F,H17G), C177(H17N,H17O,H17P), C12(H12H,H12I,
 H12J), C161(H16A,H16B,H16C), C91(H91A,H91B,H91C), C88(H88A,H88B,H88C), C7(H7A,
 H7B,H7C), C44(H44A,H44B,H44C), C48(H48A,H48B,H48C), C86(H86A,H86B,H86C),
 C9(H9A,H9B,H9C), C167(H16D,H16E,H16F), C131(H13A,H13B,H13C), C164(H16G,H16H,
 H16I), C94(H94A,H94B,H94C), C185(H18T,H18U,H18V), C157(H15A,H15B,H15C),
 C152(H15D,H15E,H15F), C141(H14A,H14B,H14C), C129(H12A,H12B,H12C), C77(H77A,
 H77B,H77C), C8(H8A,H8B,H8C), C11(H11E,H11F,H11G), C3(H3A,H3B,H3C)
4.d Idealised tetrahedral OH refined as rotating group:
 O77(H77), O44(H44), O86(H86), O157(H157), O152(H152), O170(H170)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              43091
_shelx_fab_checksum              88257
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.630
_oxdiff_exptl_absorpt_empirical_full_min 0.690