Inherently Chiral Homo-Heteracalixarenes: Design and Synthesis via Enantioselective Intramolecular Sonogashira Cross-coupling Reaction
Jiang, Yi-Fan Shuo; Zhang, Yue; Tong, Shuo; Zhu, Jieping; Wang, Mei-Xiang; Chemical Science  (2025) –; doi:10.1039/D5SC05923B

data_1576276
_publ_section_title
;
 Inherently Chiral Homo-Heteracalixarenes: Design and Synthesis via
 Enantioselective Intramolecular Sonogashira Cross-coupling Reaction
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC05923B
_journal_year                    2025
_chemical_formula_moiety         'C52 H53 N7 O'
_chemical_formula_sum            'C52 H53 N7 O'
_chemical_formula_weight         792.01
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-09-12
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-10-26 deposited with the CCDC.	2025-11-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.1044(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.96977(5)
_cell_length_b                   21.66155(14)
_cell_length_c                   25.66659(15)
_cell_measurement_reflns_used    53382
_cell_measurement_temperature    100.0(5)
_cell_measurement_theta_max      76.6010
_cell_measurement_theta_min      2.6270
_cell_volume                     4431.01(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.134a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.134a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.134a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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     36.00 111.00   0.50    0.25    --  104.75-125.00 150.00  150
  2  \w     36.00 108.00   0.50    0.25    --  104.75-107.00  67.05  144
  3  \w     36.00 108.00   0.50    0.25    --  104.75-107.00  -2.32  144
  4  \w     35.00 106.00   0.50    0.25    --  104.75-103.00 132.63  142
  5  \w     35.00 106.00   0.50    0.25    --  104.75 -99.00   0.00  142
  6  \w    -21.00  79.00   0.50    0.10    --   47.76 -98.00 164.00  200
  7  \w     35.00 106.00   0.50    0.25    --  104.75 -98.00 164.00  142
  8  \w     36.00 111.00   0.50    0.25    --  104.75-125.00 -30.00  150
  9  \w     36.00 111.00   0.50    0.25    --  104.75-125.00 -90.00  150
 10  \w     35.00 106.00   0.50    0.25    --  104.75 -99.00-180.00  142
 11  \w     33.00 107.00   0.50    0.25    --  104.75 -77.00-180.00  148
 12  \w    -26.00  29.00   0.50    0.10    --   47.76 -19.00-120.00  110
 13  \w     35.00  66.00   0.50    0.25    --  104.75 -57.00   0.00   62
 14  \w     35.00  67.00   0.50    0.25    --  104.75 -57.00  30.00   64
 15  \w     33.00  68.00   0.50    0.25    --  104.75 -57.00  60.00   70
 16  \w     94.00 178.00   0.50    0.25    --  104.75  19.00   0.00  168
 17  \w     94.00 178.00   0.50    0.25    --  104.75  19.00   0.00  168
 18  \w     83.00 177.00   0.50    0.25    --  104.75  77.00-120.00  188
 19  \w     91.00 175.00   0.50    0.25    --  104.75  98.00 -88.00  168
 20  \w     38.00 120.00   0.50    0.10    --   47.76  38.00  60.00  164
 21  \w    -62.00  25.00   0.50    0.10    --  -47.76  57.00-150.00  174
 22  \w    -25.00  27.00   0.50    0.10    --  -47.76  19.00 -90.00  104
 23  \w    -25.00  27.00   0.50    0.10    --  -47.76  19.00-120.00  104
 24  \w    -25.00  27.00   0.50    0.10    --  -47.76  19.00-180.00  104
 25  \w    -78.00  23.00   0.50    0.10    --  -47.76  98.00 -88.00  202
 26  \w    -64.00 -32.00   0.50    0.25    -- -104.00  57.00-180.00   64
 27  \w   -127.00 -32.00   0.50    0.25    -- -104.00 146.00-134.31  190
 28  \w    -64.00 -32.00   0.50    0.25    -- -104.00  57.00-120.00   64
 29  \w   -106.00 -34.00   0.50    0.25    -- -104.00  98.00 -88.00  144
 30  \w    -64.00 -32.00   0.50    0.25    -- -104.00  57.00   0.00   64
 31  \w    -64.00 -32.00   0.50    0.25    -- -104.00  57.00  30.00   64
 32  \w    -64.00 -32.00   0.50    0.25    -- -104.00  57.00  60.00   64
 33  \w   -175.00 -83.00   0.50    0.25    -- -104.00 -74.00  83.03  184
 34  \w   -175.00 -90.00   0.50    0.25    -- -104.00 -57.00  90.00  170
 35  \w   -175.00 -88.00   0.50    0.25    -- -104.00 -63.00-102.85  174
 36  \w   -175.00 -88.00   0.50    0.25    -- -104.00 -63.00-102.85  174
 37  \w   -175.00 -91.00   0.50    0.25    -- -104.00 -52.00-168.90  168
 38  \w   -173.00 -73.00   0.50    0.25    -- -104.00-125.00-120.00  200
 39  \w   -174.00 -86.00   0.50    0.25    -- -104.00 -98.00 164.00  176
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0927365000
_diffrn_orient_matrix_UB_12      0.0329931000
_diffrn_orient_matrix_UB_13      -0.0446638000
_diffrn_orient_matrix_UB_21      -0.0227297000
_diffrn_orient_matrix_UB_22      -0.0574943000
_diffrn_orient_matrix_UB_23      -0.0346870000
_diffrn_orient_matrix_UB_31      -0.1680028000
_diffrn_orient_matrix_UB_32      0.0257888000
_diffrn_orient_matrix_UB_33      -0.0201520000
_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  0.0336
_diffrn_reflns_av_unetI/netI     0.0139
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            80435
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.618
_diffrn_reflns_theta_min         2.669
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.562
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92291
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.134a (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    1.187
_exptl_crystal_description       cube
_exptl_crystal_F_000             1688
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.266
_refine_diff_density_min         -0.198
_refine_diff_density_rms         0.038
_refine_ls_extinction_coef       0.00063(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     550
_refine_ls_number_reflns         9188
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0432
_refine_ls_R_factor_gt           0.0399
_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^)+(0.0282P)^2^+2.4968P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0889
_refine_ls_wR_factor_ref         0.0905
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8546
_reflns_number_total             9188
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05923b2.cif
_cod_data_source_block           exp_7818-jyf-7-01_auto
_cod_database_code               1576276
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N '
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.872
_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
2.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C34(H34A,H34B)
2.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C7(H7), C16(H16), C22(H22), C24(H24), C20(H20), C21(H21), C40(H40),
 C12(H12), C42(H42), C14(H14), C48(H48), C36(H36), C13(H13), C46(H46), C37(H37),
  C52(H52), C38(H38), C39(H39), C49(H49), C44(H44), C45(H45), C43(H43),
 C50(H50), C51(H51)
2.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C33(H33A,H33B,
 H33C), C26(H26A,H26B,H26C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C25(H25A,
 H25B,H25C)
;
_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 2.408
_oxdiff_exptl_absorpt_empirical_full_min 0.515