Self-assembly of achiral building blocks into chiral cyclophanes using non-directional interactions.
Zhang, Yuan; Ourri, Benjamin; Skowron, Pierre-Thomas; Jeamet, Emeric; Chetot, Titouan; Duchamp, Christian; Belenguer, Ana M.; Vanthuyne, Nicolas; Cala, Olivier; Dumont, Elise; Mandal, Pradeep K.; Huc, Ivan; Perret, Florent; Vial, Laurent; Leclaire, Julien; Chemical science 14 (2023) 7126–7135; doi:10.1039/d3sc01235b

data_1569204
_publ_section_title
;
 Self-assembly of achiral building blocks into chiral cyclophanes using
 non-directional interactions.
;
_journal_issue                   26
_journal_name_full               'Chemical science'
_journal_page_first              7126
_journal_page_last               7135
_journal_paper_doi               10.1039/d3sc01235b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C192 H96 O64 S16'
_chemical_formula_sum            'C192 H96 O64 S16'
_chemical_formula_weight         3939.64
_chemical_properties_physical    Air-sensitive,Moisture-sensitive,Heat-sensitive
_space_group_crystal_system      hexagonal
_space_group_IT_number           177
_space_group_name_Hall           'P 6 2'
_space_group_name_H-M_alt        'P 6 2 2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2020-05-12
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2020-05-12 deposited with the CCDC.	2023-05-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   49.4947(7)
_cell_length_b                   49.4947(7)
_cell_length_c                   35.6973(5)
_cell_measurement_reflns_used    23079
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.1270
_cell_measurement_theta_min      1.5680
_cell_volume                     75732.7(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       MxCube
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Dectris Pilatus 6M'
_diffrn_measurement_method       \w-scans
_diffrn_radiation_type           Synchrotron
_diffrn_radiation_wavelength     0.97625
_diffrn_reflns_av_R_equivalents  0.1503
_diffrn_reflns_av_unetI/netI     0.0784
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       43
_diffrn_reflns_limit_h_min       -43
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            251908
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.343
_diffrn_reflns_theta_max         26.343
_diffrn_reflns_theta_min         1.567
_diffrn_source                   'PetraIII DESY'
_exptl_absorpt_coefficient_mu    0.262
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.08555
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            Clear
_exptl_crystal_density_diffrn    0.518
_exptl_crystal_description       'Hexagonal plates'
_exptl_crystal_F_000             12096
_exptl_crystal_recrystallization_method 'vapor diffusion'
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.261
_refine_diff_density_min         -0.254
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 2068 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.51(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.918
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     855
_refine_ls_number_reflns         19896
_refine_ls_number_restraints     1035
_refine_ls_restrained_S_all      0.966
_refine_ls_R_factor_all          0.1871
_refine_ls_R_factor_gt           0.1083
_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          0.2740
_refine_ls_wR_factor_ref         0.3616
_reflns_Friedel_coverage         0.817
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                6265
_reflns_number_total             19896
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01235b2.cif
_cod_data_source_block           Y8
_cod_depositor_comments
'Adding full bibliography for 1569201--1569204.cif.'
_cod_original_cell_volume        75733(2)
_cod_database_code               1569204
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 S2-C4 = S1-C1
 1.83 with sigma of 0.005
 C9-C8 = C18-C17
 1.57 with sigma of 0.005
 C14-C13 = C23-C22
 1.34 with sigma of 0.005
 C13-C12 = C15-C14 = C22-C21 = C24-C23
 1.34 with sigma of 0.005
 C56-C62 = C81-C85
 2.11 with sigma of 0.02
 C6-C7 \\sim C7-C8 \\sim C9-C10 \\sim C10-C5 \\sim C7-C11 \\sim C11-C10 \\sim
C2-C16 \\sim C16-C17 \\sim C18-
 C19 \\sim C19-C3 \\sim C16-C20 \\sim C20-C19
 with sigma of 0.01
 C8-C13 \\sim C9-C14 \\sim C17-C22 \\sim C18-C23
 with sigma of 0.02
 C8-C9 \\sim C17-C18
 with sigma of 0.02
 C12-C13 \\sim C14-C15 \\sim C21-C22 \\sim C23-C24
 with sigma of 0.01
 C12-O1 \\sim C12-O2 \\sim C15-O3 \\sim C15-O4 \\sim C21-O7 \\sim C21-O8 \\sim
C24-O5 \\sim C24-O6
 with sigma of 0.01
 O1-O2 \\sim O3-O4 \\sim O5-O6 \\sim O7-O8
 with sigma of 0.01
 S3-S2 \\sim S6-S7
 with sigma of 0.01
 C2-C17 \\sim C3-C18 \\sim C5-C9 \\sim C6-C8
 with sigma of 0.01
 C8-C14 \\sim C9-C13 \\sim C17-C23 \\sim C18-C22
 with sigma of 0.02
 C2-C20 \\sim C3-C20 \\sim C5-C11 \\sim C6-C11
 with sigma of 0.01
 C8-C11 \\sim C9-C11 \\sim C17-C20 \\sim C18-C20
 with sigma of 0.02
 C11-C20 \\sim C35-C44 \\sim C59-C68 \\sim C83-C92
 with sigma of 0.01
 C7-C10 \\sim C16-C19
 with sigma of 0.01
 C12-C15 \\sim C21-C24
 with sigma of 0.01
 O2-O3 \\sim O6-O7
 with sigma of 0.01
 C14-C13 \\sim C23-C22
 with sigma of 0.02
3. Restrained planarity
 S1, C1, C4, S2
 with sigma of 0.1
 C1, C2, C3, C4, C5, C6, C7, C10, C16, C19
 with sigma of 0.1
 C8, C9, C14, C13, C12, O2, O1, C15, O4, O3
 with sigma of 0.1
 C18, C17, C22, C23, C24, O5, O6, C21, O7, O8
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C76 \\sim C77 \\sim C78 \\sim C73 \\sim C74 \\sim C75: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
C33 \\sim C32: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C1: within 1.7A with sigma of 0.04
and sigma for terminal atoms of 0.08
C25 \\sim C30 \\sim C29 \\sim C28 \\sim C27 \\sim C26: within 1.7A with sigma
of 0.04 and sigma for terminal atoms of 0.08
Uanis(C31) = Uanis(C34)
Uanis(C64) = Uanis(C49) = Uanis(C50) = Uanis(C51) = Uanis(C52) = Uanis(C53) =
Uanis(C54)
Uanis(C58) = Uanis(C55)
Uanis(O22) = Uanis(O19)
Uanis(O18) = Uanis(O23)
Uanis(C18) = Uanis(C19) = Uanis(C17) = Uanis(C16)
Uanis(C8) = Uanis(C9) = Uanis(C10) = Uanis(C7)
Uanis(C82) = Uanis(C79)
Uanis(C90) = Uanis(C89)
Uanis(C16) = Uanis(C20)
Uanis(C68) = Uanis(C59)
5. Same fragment restrains
{S1, S2, O1, O2, O3, O4, O5, O6, O7, O8, C1, C2, C3, C4, C5, C6, C7, C8, C9,
C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24}
sigma for 1-2: 0.02, 1-3: 0.04
as
{S3, S4, O9, O10, O11, O12, O13, O14, O15, O16, C25, C26, C27, C28, C29, C30,
C31, C32, C33, C34, C35, C36, C37, C38, C39, C40, C41, C42, C43, C44, C45, C46,
C47, C48}
{S1, S2, O1, O2, O3, O4, O5, O6, O7, O8, C1, C2, C3, C4, C5, C6, C7, C8, C9,
C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24}
sigma for 1-2: 0.02, 1-3: 0.04
as
{S5, S6, O17, O18, O19, O20, O21, O22, O23, O24, C49, C50, C51, C52, C53, C54,
C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65, C66, C67, C68, C69, C70,
C71, C72}
{S1, S2, O1, O2, O3, O4, O5, O6, O7, O8, C1, C2, C3, C4, C5, C6, C7, C8, C9,
C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24}
sigma for 1-2: 0.02, 1-3: 0.04
as
{S7, S8, O25, O26, O27, O28, O29, O30, O31, O32, C73, C74, C75, C76, C77, C78,
C79, C80, C81, C82, C83, C84, C85, C86, C87, C88, C89, C90, C91, C92, C93, C94,
C95, C96}
6. Others
 Uiso(C12)=Uiso(C15)=Uiso(C21)=Uiso(C24)=Uiso(C36)=Uiso(C39)=Uiso(C45)=
 Uiso(C48)=Uiso(C60)=Uiso(C63)=Uiso(C69)=Uiso(C72)=Uiso(C84)=Uiso(C87)=
 Uiso(C93)=Uiso(C96)=FVAR(1)
 Fixed Uiso: C32(0.28) C37(0.32) C46(0.32) C56(0.28) C61(0.28) C71(0.32)
 C94(0.31)
7.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8), C9(H9), C10(H10), C16(H16), C17(H17), C18(H18), C19(H19),
 C31(H31), C32(H32), C33(H33), C34(H34), C40(H40), C41(H41), C42(H42), C43(H43),
  C55(H55), C56(H56), C57(H57), C58(H58), C64(H64), C65(H65), C66(H66),
 C67(H67), C79(H79), C80(H80), C81(H81), C82(H82), C88(H88), C89(H89), C90(H90),
  C91(H91)
7.b Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C20(H20A,H20B), C35(H35A,H35B), C44(H44A,H44B), C59(H59A,
 H59B), C68(H68A,H68B), C83(H83A,H83B), C92(H92A,H92B)
7.c Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,C6), C25(C26,C27,C28,C29,C30), C49(C50,C51,C52,C53,C54),
 C73(C74,C75,C76,C77,C78)
;
_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
;