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_1575960
_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 H100 N12 O28, 8[C2H6SO]'
_chemical_formula_sum            'C108 H146 N12 O36 S8'
_chemical_formula_weight         2444.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-12
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-17 deposited with the CCDC.	2025-09-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.767(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   34.8720(18)
_cell_length_b                   10.7892(6)
_cell_length_c                   35.963(2)
_cell_measurement_reflns_used    54855
_cell_measurement_temperature    250(2)
_cell_measurement_theta_max      45.39
_cell_measurement_theta_min      3.59
_cell_volume                     13524.3(13)
_computing_cell_refinement
;
X-Area Recipe 2.0.1 (STOE, 2023)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.192.0 (STOE, 2023)
;
_computing_data_reduction
;
X-Area Integrate 2.5.15.0 (STOE, 2023)
X-Area LANA 2.7.12 (STOE, 2023)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material
;
STOE & Cie GmbH, X-Area, software package for collecting single-crystal or
multi-domain crystal data on STOE area-detector diffractometers, for image 
processing, for the correction and scaling of reflection intensities and 
for outlier rejection, version 2.3, Darmstadt 2023
;
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      250(2)
_diffrn_detector                 Pilatus300K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 300K'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details
;
 2254 frames, detector distance = 50 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 mm, 0.6 diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  180
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0762
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            36018
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        37.500
_diffrn_reflns_theta_max         37.500
_diffrn_reflns_theta_min         4.278
_diffrn_source                   'Primux 100 micro'
_diffrn_source_current           1.00
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    1.851
_exptl_absorpt_correction_T_max  0.8841
_exptl_absorpt_correction_T_min  0.6248
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.201
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       'flat prism'
_exptl_crystal_F_000             5176
_exptl_crystal_recrystallization_method 'crystallized from DMSO'
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.443
_refine_diff_density_min         -0.368
_refine_diff_density_rms         0.083
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.358
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     498
_refine_ls_number_reflns         3481
_refine_ls_number_restraints     239
_refine_ls_restrained_S_all      1.323
_refine_ls_R_factor_all          0.2111
_refine_ls_R_factor_gt           0.1912
_refine_ls_shift/su_max          0.014
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1200P)^2^+142.4200P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4374
_refine_ls_wR_factor_ref         0.4484
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2853
_reflns_number_total             3481
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04138d2.cif
_cod_data_source_block           sl-905_pl
_cod_depositor_comments
'Adding full bibliography for 1575958--1575961.cif.'
_cod_database_code               1575960
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.822
_shelx_estimated_absorpt_t_min   0.510
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C35-C34
 1.44 with sigma of 0.03
 C25-C28
 1.44 with sigma of 0.03
 C7-C5
 1.44 with sigma of 0.03
 C21-C19
 1.44 with sigma of 0.03
3. Rigid bond restraints
 O3, C34, C35
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O10, C43, C44
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O13, C46
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C39) = Uanis(C41) = Uanis(C40) = Uanis(C42) = Uanis(C30) = Uanis(C32) =
Uanis(C33) = Uanis(C31)
Uanis(C37) = Uanis(C36) = Uanis(C46) = Uanis(C45)
5. Rigid body (RIGU) restrains
 C1, C2, C3, C4, C5, C6, C7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C8, C9, C10, C11, C12, C13
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C15, C16, C17, C18, C19, C20, C21
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C22, C23, C24, C25, C26, C27
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O13, C46
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O4, N2, C7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O7, N3, C14
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O11, N5, C21
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O10, C43, C44
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O8, O9, N4, C38
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 O14, N6, C28
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6.a Everything fixed:
 H35A, H35B, H35C
6.b Riding coordinates:
 N4(H4)
6.c Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C43(H43A,H43B)
6.d Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C4(H4A), C9(H9), C10(H10), C16(H16), C18(H18), C23(H23),
 C24(H24)
6.e Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,C6), C8(C9,C10,C11,C12,C13), C15(C16,C17,C18,C19,C20), C22(C23,
 C24,C25,C26,C27)
6.f Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C36(H36A,H36B,
 H36C), C37(H37A,H37B,H37C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 1312 electrons were 
found in a volume of 5407\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
8 DMSO molecules per formula unit 
which account for 1344 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              97914
_shelx_fab_checksum              14510
_olex2_exptl_crystal_mounting_method 'mounted on loop with oil'
_olex2_submission_original_sample_id SL-905
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '50.0 mm'
_stoe_detector_pixelsize_x       '0.172 mm'
_stoe_detector_pixelsize_y       '0.172 mm'
_stoe_detector_size_x            '8.4 cm'
_stoe_detector_size_y            '10.6 cm'
_stoe_evaluation_integration_a   7.0
_stoe_evaluation_integration_b   0.5
_stoe_evaluation_integration_ems 0.020
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 4
_stoe_evaluation_lana_bos_l_odd_max 1
_stoe_evaluation_lana_completeness 99.9
_stoe_evaluation_lana_dxs_max_order 1
_stoe_evaluation_lana_dys_max_order 1
_stoe_evaluation_lana_fs_max_order 3
_stoe_evaluation_lana_max_2theta_available 91.5
_stoe_evaluation_lana_max_2theta_desired 75.0
_stoe_evaluation_lana_mean_redundancy 5.4
_stoe_evaluation_lana_number_refls_after_or 37604
_stoe_evaluation_lana_number_refls_outliers 14943
_stoe_evaluation_lana_number_refls_total 52547
_stoe_evaluation_lana_number_refls_unique 6971
_stoe_evaluation_lana_number_refls_written 37604
_stoe_evaluation_lana_or_c1      0.035
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      0.7
_stoe_evaluation_lana_point_group -1
_stoe_evaluation_lana_table
;
2Theta           7.9   15.9   23.9   31.9   39.9   47.9   55.9   63.9   71.9
<Resolution>    9.05   5.25   3.67   2.77   2.25   1.89   1.64   1.46   1.32
N(total)         114   1069   1726   4033   6435   8221   9772  10918  10259
<Redundancy>     2.5    5.6    4.2    5.9    6.2    6.0    5.5    5.2    4.9
Complet. [%%]    93.8  100.0   99.6  100.0   99.7   99.8  100.0  100.0  100.0
<I/sigma>      547.0  596.5  393.5  121.8   69.2   37.7   11.4    4.5    2.5
R(int)         0.054  0.034  0.034  0.053  0.069  0.083  0.109  0.184  0.235
;
_stoe_measurement_identifier     SL-905
_stoe_measurement_max_exposure_per_frame '120.0 s'
_stoe_measurement_mean_exposure_per_frame '120.0 s'
_stoe_measurement_min_exposure_per_frame '120.0 s'
_stoe_measurement_total_exposure_time '75.1 h'
_stoe_measurement_total_frame_number 2254
_stoe_measurement_total_run_number 41
_stoe_measurement_tube_power     '50.0 W'