Design and synthesis of macrocycles with tuneable diameters and helical foldamers with customizable peripheral side chains.
Farooq, Saquib; Crochet, Aurelien; Kilbinger, Andreas F. M.; Chemical science 16 (2025) 20570–20579; doi:10.1039/d5sc04138d

data_1575959
_publ_section_title
;
 Design and synthesis of macrocycles with tuneable diameters and helical
 foldamers with customizable peripheral side chains.
;
_journal_issue                   43
_journal_name_full               'Chemical science'
_journal_page_first              20570
_journal_page_last               20579
_journal_paper_doi               10.1039/d5sc04138d
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C92 N8 O24, 10[CH4O]'
_chemical_formula_sum            'C102 H40 N8 O34'
_chemical_formula_weight         1921.42
_space_group_crystal_system      tetragonal
_space_group_IT_number           122
_space_group_name_Hall           'I -4 2bw'
_space_group_name_H-M_alt        'I -4 2 d'
_atom_sites_solution_primary     dual
_audit_creation_date             2024-02-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-02-17 deposited with the CCDC.	2025-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   28.9569(8)
_cell_length_b                   28.9569(8)
_cell_length_c                   13.4749(8)
_cell_measurement_reflns_used    7225
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      47.8890
_cell_measurement_theta_min      3.0330
_cell_volume                     11298.7(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_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    -47.00 -21.00   0.50   40.00    --  -10.00 141.00 168.96   52
  2  \w    -53.00 -22.00   0.50   40.00    --  -14.00 143.00 122.89   62
  3  \w    -56.00 -27.00   0.50   40.00    --  -14.00 153.00  91.13   58
  4  \w     -4.00  40.00   0.50   40.00    --   29.66 -99.00   0.00   88
  5  \w    -16.00   9.00   0.50   40.00    --   29.66 -19.00  30.00   50
  6  \w     49.00  75.00   0.50   40.00    --   30.17  48.00 -31.99   52
  7  \w     43.00  70.00   0.50   40.00    --   30.17  50.00   7.39   54
  8  \w     41.00  67.00   0.50   40.00    --   30.17  54.00 -44.12   52
  9  \w     40.00  73.00   0.50   40.00    --   30.67  19.00-180.00   66
 10  \w    -15.00  10.00   0.50   40.00    --   30.67 -19.00  60.00   50
 11  \w      9.00  35.00   0.50   40.00    --   30.67 -99.00 -90.00   52
 12  \w      4.00  34.00   0.50   40.00    --   30.67  19.00-180.00   60
 13  \w    -16.00   9.00   0.50   40.00    --  -31.42  19.00  60.00   50
 14  \w    -19.00   9.00   0.50   40.00    --  -31.42  51.00 121.38   56
 15  \w    -54.00 -13.00   0.50   40.00    --  -31.42 125.00-120.00   82
 16  \w    -10.00  15.00   0.50   40.00    --  -31.42  19.00 -30.00   50
 17  \w    -58.00 -33.00   0.50   40.00    --  -31.42 125.00-150.00   50
 18  \w    -16.00  11.00   0.50   40.00    --  -31.42  57.00 148.81   54
 19  \w    -50.00 -24.00   0.50   40.00    --  -31.42 125.00 -60.00   52
 20  \w    -36.00 -10.00   0.50   40.00    --  -31.42 -19.00 120.00   52
 21  \w    -77.00 -43.00   0.50   40.00    --  -31.42 -19.00 120.00   68
 22  \w    -13.00  12.00   0.50   40.00    --  -31.42  19.00 -90.00   50
 23  \w    -16.00  14.00   0.50   40.00    --  -31.42  19.00 120.00   60
 24  \w    -57.00 -22.00   0.50   40.00    --  -31.42 125.00 -30.00   70
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0320598000
_diffrn_orient_matrix_UB_12      -0.0118538000
_diffrn_orient_matrix_UB_13      -0.0875795000
_diffrn_orient_matrix_UB_21      -0.0207668000
_diffrn_orient_matrix_UB_22      0.0401881000
_diffrn_orient_matrix_UB_23      -0.0602926000
_diffrn_orient_matrix_UB_31      0.0370201000
_diffrn_orient_matrix_UB_32      0.0327769000
_diffrn_orient_matrix_UB_33      0.0421000000
_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  0.0494
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            26986
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        51.403
_diffrn_reflns_theta_max         51.403
_diffrn_reflns_theta_min         3.052
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.740
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53534
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.130
_exptl_crystal_description       prism
_exptl_crystal_F_000             3920
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.427
_refine_diff_density_min         -0.317
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.5(15)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.517
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     257
_refine_ls_number_reflns         3060
_refine_ls_number_restraints     362
_refine_ls_restrained_S_all      1.561
_refine_ls_R_factor_all          0.2433
_refine_ls_R_factor_gt           0.1626
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4253
_refine_ls_wR_factor_ref         0.4878
_reflns_Friedel_coverage         0.799
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                1236
_reflns_number_total             3060
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04138d2.cif
_cod_data_source_block           sl754-tetramer
_cod_depositor_comments
'Adding full bibliography for 1575958--1575961.cif.'
_cod_original_cell_volume        11298.7(9)
_cod_database_code               1575959
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C92 H112 N8 O24'
_shelx_estimated_absorpt_t_max   0.930
_shelx_estimated_absorpt_t_min   0.808
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5(15)
 0.5(15)
2. Restrained distances
 O1-C7
 1.2 with sigma of 0.02
 O2-C14 = O1-C7
 1.2 with sigma of 0.02
 C11-C14
 2.4 with sigma of 0.02
 C21-C22
 1.54 with sigma of 0.02
 N2-C11
 1.43 with sigma of 0.01
 N1-C6 = N2-C11
 1.43 with sigma of 0.01
 N1-C7 = N2-C14
 1.3 with sigma of 0.01
 O1-C7 = O2-C14
 1.2 with sigma of 0.01
 C23-C22
 1.54 with sigma of 0.02
 C7-C8
 1.43 with sigma of 0.02
 C2_$1-C14
 1.43 with sigma of 0.01
 C7_$1-C8_$1
 1.43 with sigma of 0.01
 N1_$1-C7_$1
 1.3 with sigma of 0.01
 N1_$1-C6_$1
 1.43 with sigma of 0.01
 C6_$1-C7_$1
 2.3 with sigma of 0.01
 O6_$2-C18_$2
 1.43 with sigma of 0.01
 O6_$2-C3_$2
 2.3 with sigma of 0.01
 O6-C5
 2.3 with sigma of 0.01
 O6-C3
 2.3 with sigma of 0.01
 C6-O3
 2.3 with sigma of 0.01
 C2-O3
 2.3 with sigma of 0.01
 O5-C17
 1.43 with sigma of 0.02
 C19-C18 = C20-C19 = C21-C20 = C22-C21 = C23-C22
 1.54 with sigma of 0.02
 C18-C20
 2.5 with sigma of 0.02
 C19-C21
 2.5 with sigma of 0.02
 C20-C22
 2.5 with sigma of 0.02
 C21-C23
 2.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C1 \\sim C6 \\sim C5 \\sim C4 \\sim C3 \\sim C2 \\sim C7 \\sim C8 \\sim C13
\\sim C12 \\sim C11 \\sim C10 \\sim C9 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5.a Fitted hexagon refined as free rotating group:
 C1(C6,C5,C4,C3,C2), C8(C13,C12,C11,C10,C9)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 743 electrons were 
found in a volume of 4049\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
10[CH4O] per Asymmetric Unit 
which account for 720 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              61220
_shelx_fab_checksum              65772
_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 1.915
_oxdiff_exptl_absorpt_empirical_full_min 0.661