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_1576274
_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         'C68 H63 N7 O'
_chemical_formula_sum            'C68 H63 N7 O'
_chemical_formula_weight         994.25
_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
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2lzv6n
_audit_creation_date             2025-09-15
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-11-06 deposited with the CCDC.	2025-11-11 downloaded from the CCDC.
;
_cell_angle_alpha                94.975(2)
_cell_angle_beta                 91.129(2)
_cell_angle_gamma                111.187(2)
_cell_formula_units_Z            2
_cell_length_a                   10.7047(2)
_cell_length_b                   13.5587(2)
_cell_length_c                   20.6357(4)
_cell_measurement_reflns_used    18469
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      76.1250
_cell_measurement_theta_min      2.1020
_cell_volume                     2777.93(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.55a (Rigaku OD, 2022)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.953
_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    -78.00 -53.00   0.50    0.07    --  -47.40 125.00-158.00   50
  2  \w   -107.00 -33.00   0.50    0.29    -- -104.00 125.00-158.00  148
  3  \w    -74.00 -33.00   0.50    0.29    -- -104.00 125.00 -60.00   82
  4  \w   -127.00 -33.00   0.50    0.29    -- -104.00 147.00   7.00  188
  5  \w    -82.00 -56.00   0.50    0.07    --  -47.40 147.00   7.00   52
  6  \w   -103.00 -53.00   0.50    0.29    -- -104.00  77.00 -30.00  100
  7  \w    -64.00 -33.00   0.50    0.29    -- -104.00  57.00   0.00   62
  8  \w    -62.00 -32.00   0.50    0.29    -- -104.00  57.00  30.00   60
  9  \w    -19.00  18.00   0.50    0.07    --  -47.40  19.00  30.00   74
 10  \w    -25.00  25.00   0.50    0.07    --  -47.40  19.00-120.00  100
 11  \w   -115.00 -74.00   0.50    0.07    --  -47.40-125.00-150.00   82
 12  \w   -118.00 -74.00   0.50    0.07    --  -47.40-125.00-180.00   88
 13  \w    -88.00 -63.00   0.50    0.07    --  -47.40-147.00 -41.00   50
 14  \w   -112.00 -87.00   0.50    0.07    --  -47.40-125.00  90.00   50
 15  \w   -117.00 -77.00   0.50    0.07    --  -47.40-125.00 -30.00   80
 16  \w   -117.00 -27.00   0.50    0.07    --  -47.40 -77.00 -90.00  180
 17  \w   -139.00 -93.00   0.50    0.29    -- -104.00 -19.00-180.00   92
 18  \w   -173.00-148.00   0.50    0.29    -- -104.00 -19.00-180.00   50
 19  \w   -122.00 -94.00   0.50    0.29    -- -104.00 -38.00  30.00   56
 20  \w   -174.00-148.00   0.50    0.29    -- -104.00 -38.00  30.00   52
 21  \w   -175.00 -95.00   0.50    0.29    -- -104.00 -38.00 120.00  160
 22  \w   -143.00-117.00   0.50    0.29    -- -104.00-147.00 -41.00   52
 23  \w   -154.00 -79.00   0.50    0.29    -- -104.00-125.00 -90.00  150
 24  \w   -129.00-103.00   0.50    0.29    -- -104.00-125.00 124.00   52
 25  \w     38.00  64.00   0.50    0.29    --  104.75 -57.00-180.00   52
 26  \w    -23.00  29.00   0.50    0.07    --   47.40 -19.00   0.00  104
 27  \w     38.00  66.00   0.50    0.29    --  104.75 -57.00 120.00   56
 28  \w     33.00  65.00   0.50    0.29    --  104.75 -57.00 150.00   64
 29  \w     44.00  88.00   0.50    0.29    --  104.75 -99.00 150.00   88
 30  \w     33.00 104.00   0.50    0.29    --  104.75-125.00 124.00  142
 31  \w     22.00  93.00   0.50    0.07    --   47.40-125.00 124.00  142
 32  \w     68.00  97.00   0.50    0.29    --  104.75-125.00  60.00   58
 33  \w     68.00 107.00   0.50    0.07    --   47.40-147.00 -41.00   78
 34  \w     87.00 128.00   0.50    0.29    --  104.75-147.00 -41.00   82
 35  \w     34.00 127.00   0.50    0.29    --  104.75-146.00-121.34  186
 36  \w     34.00 102.00   0.50    0.29    --  104.75 -99.00 -60.00  136
 37  \w     64.00 103.00   0.50    0.29    --  104.75 -99.00 -30.00   78
 38  \w     34.00  98.00   0.50    0.29    --  104.75 -99.00 120.00  128
 39  \w     94.00 163.00   0.50    0.29    --  104.75  38.00 -60.00  138
 40  \w    105.00 131.00   0.50    0.29    --  104.75 125.00-158.00   52
 41  \w    130.00 161.00   0.50    0.29    --  104.75 125.00 -30.00   62
 42  \w     75.00 133.00   0.50    0.29    --  104.75 147.00   7.00  116
 43  \w     83.00 117.00   0.50    0.29    --  104.75 125.00 -30.00   68
 44  \w     70.00 120.00   0.50    0.07    --   47.40 147.00   7.00  100
;
_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      -0.0520836000
_diffrn_orient_matrix_UB_12      -0.0355653000
_diffrn_orient_matrix_UB_13      -0.0715538000
_diffrn_orient_matrix_UB_21      -0.1446415000
_diffrn_orient_matrix_UB_22      -0.0469201000
_diffrn_orient_matrix_UB_23      0.0219701000
_diffrn_orient_matrix_UB_31      -0.0161682000
_diffrn_orient_matrix_UB_32      0.1074019000
_diffrn_orient_matrix_UB_33      -0.0054804000
_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  0.0432
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            37390
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.616
_diffrn_reflns_theta_min         2.152
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.552
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85851
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.55a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.189
_exptl_crystal_description       block
_exptl_crystal_F_000             1056
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.226
_refine_diff_density_min         -0.203
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     693
_refine_ls_number_reflns         11154
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0677
_refine_ls_R_factor_gt           0.0545
_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^)+(0.0440P)^2^+1.5204P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1322
_refine_ls_wR_factor_ref         0.1382
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9109
_reflns_number_total             11154
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05923b2.cif
_cod_data_source_block           exp_4636_auto
_cod_database_code               1576274
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N Cl'
_chemical_oxdiff_usercomment     'C H O N Cl'
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.874
_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. Rigid bond restraints
 C01A, N004
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
3.a Secondary CH2 refined with riding coordinates:
 C014(H01A,H01B), C018(H01C,H01D)
3.b Aromatic/amide H refined with riding coordinates:
 C00H(H00H), C00Q(H00Q), C00T(H00T), C00U(H00U), C00V(H00V), C00W(H00W),
 C00X(H00X), C00Y(H00Y), C00Z(H00Z), C011(H011), C012(H012), C013(H013),
 C015(H015), C016(H016), C017(H017), C019(H019), C01B(H01E), C01D(H01F),
 C01G(H01J), C01H(H01K), C01J(H01L), C01L(H01P), C01M(H01Q), C01N(H01R),
 C01O(H01S), C01P(H01T), C01Q(H01U), C01S(H01Y), C01T(H01Z), C01U(H01),
 C01V(H1), C01Y(H4), C022(H022), C023(H023), C024(H024)
3.c Idealised Me refined as rotating group:
 C01E(H01G,H01H,H01I), C01K(H01M,H01N,H01O), C01R(H01V,H01W,H01X), C01W(H2,H,
 HA), C01X(H3,HB,HC), C01Z(H5,HD,HE), C020(H02A,H02B,H02C), C021(H02D,H02E,H02F)
;
_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 1.684
_oxdiff_exptl_absorpt_empirical_full_min 0.437