Programmable synthesis of organic cages with reduced symmetry.
Andrews, Keith G.; Horton, Peter N.; Coles, Simon J.; Chemical science 15 (2024) 6536–6543; doi:10.1039/d4sc00889h

data_1571315
_publ_section_title
;
 Programmable synthesis of organic cages with reduced symmetry.
;
_journal_issue                   17
_journal_name_full               'Chemical science'
_journal_page_first              6536
_journal_page_last               6543
_journal_paper_doi               10.1039/d4sc00889h
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration unk
_chemical_formula_moiety
'2(C88 H88 N3 O5), 7.5[C4H8O], 1.5[C4H8O], 2[C4H8O]'
_chemical_formula_sum            'C220 H264 N6 O21'
_chemical_formula_weight         3328.36
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-31
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-09-27 deposited with the CCDC.	2024-04-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.591(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.2490(10)
_cell_length_b                   42.9082(14)
_cell_length_c                   23.6046(4)
_cell_measurement_reflns_used    28901
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      74.6060
_cell_measurement_theta_min      2.1340
_cell_volume                     22511.4(13)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_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_temperature      100(2)
_diffrn_detector                 'hybrid pixel array detector'
_diffrn_detector_area_resol_mean 10
_diffrn_detector_dtime           0.000
_diffrn_detector_type            'Rigaku, HyPix 6000HE'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.990
_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   -116.00 -72.00   0.50    5.00    --  -44.51   0.00-180.00   88
  2  \w    -92.00 -17.00   0.50    5.00    --  -44.51 125.00-150.00  150
  3  \w    -29.00  43.00   0.50    5.00    --   44.51 -37.00  30.00  144
  4  \w    -30.00  22.00   0.50    5.00    --   44.51 -19.00-150.00  104
  5  \w     23.00  92.00   0.50    5.00    --   44.51-125.00-120.00  138
  6  \w    -30.00  22.00   0.50    5.00    --   44.51 -19.00  60.00  104
  7  \w    -30.00  22.00   0.50    5.00    --   44.51 -19.00   0.00  104
  8  \w    -30.00  22.00   0.50    5.00    --   44.51 -19.00 120.00  104
  9  \w     30.00 116.00   0.50    5.00    --   44.51  57.00   0.00  172
 10  \w     29.00  76.00   0.50   16.00    --  101.75 -61.00 -30.00   94
 11  \w     29.00 106.00   0.50   16.00    --  101.75 -94.00 -90.00  154
 12  \w     29.00  76.00   0.50   16.00    --  101.75 -61.00  30.00   94
 13  \w     29.00 112.00   0.50   16.00    --  101.75-125.00 120.00  166
 14  \w     89.00 174.00   0.50   16.00    --  101.75  45.00 -60.00  170
 15  \w     85.00 175.00   0.50   16.00    --  101.75  61.00  30.00  180
 16  \w     29.00 112.00   0.50   16.00    --  101.75-125.00-120.00  166
 17  \w     29.00 106.00   0.50   16.00    --  101.75 -94.00-150.00  154
 18  \w     29.00 106.00   0.50   16.00    --  101.75 -94.00 120.00  154
 19  \w     29.00 112.00   0.50   16.00    --  101.75-125.00 150.00  166
 20  \w     63.00 106.00   0.50   16.00    --  101.75 -94.00 150.00   86
 21  \w     83.00 147.00   0.50   16.00    --  101.75 125.00 -60.00  128
 22  \w     86.00 123.00   0.50   16.00    --  101.75 125.00  30.00   74
 23  \w     67.00 104.00   0.50   16.00    --  101.75 -94.00   0.00   74
 24  \w     31.00 116.00   0.50   16.00    --  101.75-132.00 145.91  170
 25  \w    140.00 166.00   0.50   16.00    --  101.75 125.00  30.00   52
 26  \w   -173.00 -90.00   0.50   16.00    -- -103.00 -45.00 120.00  166
 27  \w   -120.00 -30.00   0.50   16.00    -- -103.00  77.00 -30.00  180
 28  \w   -110.00 -30.00   0.50   16.00    -- -103.00 125.00 -60.00  160
 29  \w    -70.00 -45.00   0.50   16.00    -- -103.00  61.00 -30.00   50
 30  \w    -70.00 -33.00   0.50   16.00    -- -103.00  61.00  90.00   74
 31  \w   -121.00 -95.00   0.50   16.00    -- -103.00 -50.00 144.16   52
 32  \w   -173.00 -97.00   0.50   16.00    -- -103.00 -60.00-131.60  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_details 'Rigaku, UG2 \k goniometer'
_diffrn_measurement_device_type
'Rigaku 007HF diffractometer equipped with Arc)Sec VHF Varimax confocal mirrors and a UG2 goniometer and HyPix 6000HE detector'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'MiTeGen loops'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0565159000
_diffrn_orient_matrix_UB_12      -0.0206250000
_diffrn_orient_matrix_UB_13      0.0073033000
_diffrn_orient_matrix_UB_21      -0.0382633000
_diffrn_orient_matrix_UB_22      -0.0290842000
_diffrn_orient_matrix_UB_23      -0.0144789000
_diffrn_orient_matrix_UB_31      0.0120723000
_diffrn_orient_matrix_UB_32      0.0043384000
_diffrn_orient_matrix_UB_33      -0.0632781000
_diffrn_radiation_collimation    'Arc)Sec VHF Varimax focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0953
_diffrn_reflns_av_unetI/netI     0.0708
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       51
_diffrn_reflns_limit_k_min       -51
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            114810
_diffrn_reflns_point_group_measured_fraction_full 0.938
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.243
_diffrn_reflns_theta_min         2.239
_diffrn_source                   'Rotating anode'
_diffrn_source_current           30.0
_diffrn_source_power             1.2
_diffrn_source_target            Cu
_diffrn_source_type              'Rigaku 007 HF'
_diffrn_source_voltage           40.0
_exptl_absorpt_coefficient_mu    0.486
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77478
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.982
_exptl_crystal_description       block
_exptl_crystal_F_000             7176
_exptl_crystal_recrystallization_method
"'The material was crystallised by vapour diffusion of methanol into a solution of THF'"
_exptl_crystal_size_max          0.52
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.22
_refine_diff_density_max         0.301
_refine_diff_density_min         -0.298
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.6(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.002
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1543
_refine_ls_number_reflns         38612
_refine_ls_number_restraints     3776
_refine_ls_restrained_S_all      1.003
_refine_ls_R_factor_all          0.1168
_refine_ls_R_factor_gt           0.0879
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1867P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2385
_refine_ls_wR_factor_ref         0.2720
_reflns_Friedel_coverage         0.863
_reflns_Friedel_fraction_full    0.883
_reflns_Friedel_fraction_max     0.880
_reflns_number_gt                24747
_reflns_number_total             38612
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00889h3.cif
_cod_data_source_block           2021ncs0274_3e
_cod_depositor_comments
'Adding full bibliography for 1571314--1571316.cif.'
_cod_database_code               1571315
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C176 H176 N6 O10'
_chemical_oxdiff_usercomment     k51_303
_shelx_estimated_absorpt_t_max   0.901
_shelx_estimated_absorpt_t_min   0.786
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.4(2)
 0.6(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C101-C191
 1.5 with sigma of 0.02
 O192-C192
 1.5 with sigma of 0.01
 C30-C28 = C28-C31
 1.54 with sigma of 0.02
 C41-C39 = C39-C40
 1.54 with sigma of 0.02
 C39-C42 = C39-C35
 1.55 with sigma of 0.02
 C52-C50 = C50-C51
 1.54 with sigma of 0.02
 C28-C29 = C28-C26
 1.55 with sigma of 0.02
 C50-C46 = C50-C53
 1.55 with sigma of 0.02
 C130-C128 = C128-C124
 1.54 with sigma of 0.02
 C128-C129 = C128-C131
 1.55 with sigma of 0.02
 C132-C133
 1.52 with sigma of 0.015
 C133-C132
 1.52 with sigma of 0.02
 C41-C42 = C41-C35
 2.52 with sigma of 0.04
 C130-C129 = C130-C131
 2.52 with sigma of 0.04
 C30-C29 = C30-C26
 2.52 with sigma of 0.04
 C41-C40
 2.56 with sigma of 0.04
 C30-C31
 2.56 with sigma of 0.04
 C52-C46 = C52-C53
 2.52 with sigma of 0.04
 C52-C51
 2.56 with sigma of 0.04
 C130-C124
 2.56 with sigma of 0.04
 C41-C40 \\sim C41-C42 \\sim C41-C35
 with sigma of 0.04
 C40-C42 \\sim C40-C35 \\sim C42-C35
 with sigma of 0.04
 C57-C71 \\sim C57-C70 \\sim C57-C69 \\sim C71-C70 \\sim C70-C69
 with sigma of 0.04
 C39-C40 \\sim C39-C42 \\sim C39-C35 \\sim C39-C41
 with sigma of 0.02
 C68-C57 \\sim C68-C71 \\sim C68-C70 \\sim C68-C69
 with sigma of 0.02
 C41-C40 \\sim C41-C42 \\sim C41-C35 \\sim C40-C42 \\sim C40-C35 \\sim C42-C35
 with sigma of 0.04
 C39-C41 \\sim C39-C40 \\sim C39-C42 \\sim C39-C35
 with sigma of 0.02
 C28-C31 \\sim C28-C29 \\sim C28-C26 \\sim C28-C30
 with sigma of 0.02
 C31-C29 \\sim C31-C26 \\sim C29-C26
 with sigma of 0.04
 C30-C31 \\sim C30-C29 \\sim C30-C26
 with sigma of 0.04
 C28-C26 \\sim C28-C30 \\sim C28-C31 \\sim C28-C29
 with sigma of 0.02
 C26-C30 \\sim C26-C31 \\sim C26-C29 \\sim C30-C31 \\sim C30-C29 \\sim C31-C29
 with sigma of 0.04
 C50-C51 \\sim C50-C46 \\sim C50-C53 \\sim C50-C52
 with sigma of 0.02
 C51-C46 \\sim C51-C53 \\sim C46-C53
 with sigma of 0.04
 C52-C51 \\sim C52-C46 \\sim C52-C53
 with sigma of 0.04
 C128-C124 \\sim C128-C129 \\sim C128-C131 \\sim C128-C130
 with sigma of 0.02
 C124-C129 \\sim C124-C131 \\sim C129-C131
 with sigma of 0.04
 C130-C124 \\sim C130-C129 \\sim C130-C131
 with sigma of 0.04
 C141-C135 \\sim C141-C140 \\sim C141-C142 \\sim C135-C140 \\sim C135-C142
\\sim C140-C142
 with sigma of 0.04
 C139-C141 \\sim C139-C135 \\sim C139-C140 \\sim C139-C142
 with sigma of 0.02
 C180-C186 \\sim C180-C185 \\sim C180-C184 \\sim C186-C185 \\sim C186-C184
\\sim C185-C184
 with sigma of 0.04
 C173-C174 \\sim C173-C164 \\sim C173-C175 \\sim C174-C175 \\sim C164-C175
 with sigma of 0.04
 C130-C129 \\sim C130-C131 \\sim C130-C124 \\sim C129-C131 \\sim C129-C124
\\sim C131-C124
 with sigma of 0.04
 C83-C80 \\sim C83-C85 \\sim C83-C86 \\sim C83-C84
 with sigma of 0.02
 C168-C170 \\sim C168-C157 \\sim C168-C169 \\sim C168-C171
 with sigma of 0.02
 C128-C130 \\sim C128-C129 \\sim C128-C131 \\sim C128-C124
 with sigma of 0.02
 C170-C157 \\sim C170-C171 \\sim C157-C169 \\sim C157-C171
 with sigma of 0.04
 C46-C52 \\sim C46-C51 \\sim C46-C53 \\sim C52-C51 \\sim C52-C53 \\sim C51-C53
 with sigma of 0.04
 C150-C151 \\sim C150-C146 \\sim C150-C153 \\sim C150-C152
 with sigma of 0.02
 C72-C74 \\sim C72-C64 \\sim C72-C73 \\sim C72-C75
 with sigma of 0.02
 C183-C180 \\sim C183-C186 \\sim C183-C185 \\sim C183-C184
 with sigma of 0.02
 C80-C86 \\sim C80-C84 \\sim C85-C84 \\sim C86-C84
 with sigma of 0.04
 C172-C173 \\sim C172-C174 \\sim C172-C164 \\sim C172-C175
 with sigma of 0.02
 C50-C46 \\sim C50-C52 \\sim C50-C51 \\sim C50-C53
 with sigma of 0.02
 C146-C152 \\sim C153-C152
 with sigma of 0.04
 C152-C146 \\sim C146-C151
 with sigma of 0.04
 C152-C146 \\sim C146-C153
 with sigma of 0.04
 C153-C146 \\sim C146-C151
 with sigma of 0.04
 C150-C146 \\sim C152-C150 \\sim C153-C150 \\sim C151-C150
 with sigma of 0.02
 N101-C107 \\sim N103-C119 \\sim N1-C7 \\sim N102-C113 \\sim N2-C13 \\sim N3-C19
 with sigma of 0.02
4. Restrained planarity
 O101, N101, C121, C122
 with sigma of 0.01
 N101, C103, C104, C105, C106, C107, C108
 with sigma of 0.01
5. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
6. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
7. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
8.a Ternary CH refined with riding coordinates:
 C2(H2A), C102(H10A)
8.b Me refined with riding coordinates:
 C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C40(H40A,H40B,
 H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C69(H69A,H69B,H69C), C70(H70A,
 H70B,H70C), C71(H71A,H71B,H71C)
8.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), N3(H3), C6(H6), C5(H5), C8(H8), C14(H14), C11(H11), C12(H12),
 C18(H18), C17(H17), C20(H20), C25(H25), C27(H27), C23(H23), C38(H38), C36(H36),
  C34(H34), C49(H49), C47(H47), C45(H45), C56(H56), C58(H58), C59(H59),
 C63(H63), C65(H65), C66(H66), C78(H78), C79(H79), C81(H81), N101(H101),
 N102(H102), N103(H103), C108(H108), C106(H106), C105(H105), C112(H112),
 C111(H111), C114(H114), C120(H120), C118(H118), C117(H117), C125(H125),
 C123(H123), C127(H127), C134(H134), C136(H136), C138(H138), C149(H149),
 C147(H147), C145(H145), C156(H156), C158(H158), C159(H159), C163(H163),
 C165(H165), C166(H166), C178(H178), C179(H179), C181(H181)
8.d Fitted hexagon refined as free rotating group:
 C7(C6,C5,C4,C3,C8), C13(C14,C9,C10,C11,C12), C19(C18,C17,C16,C15,C20),
 C24(C25,C26,C27,C22,C23), C33(C38,C37,C36,C35,C34), C44(C49,C48,C47,C46,C45),
 C55(C56,C57,C58,C59,C60), C67(C62,C63,C64,C65,C66), C77(C78,C79,C80,C81,C82),
 C103(C108,C107,C106,C105,C104), C113(C112,C111,C110,C109,C114), C115(C120,C119,
 C118,C117,C116), C126(C125,C124,C123,C122,C127), C133(C134,C135,C136,C137,
 C138), C144(C149,C148,C147,C146,C145), C155(C156,C157,C158,C159,C160),
 C167(C162,C163,C164,C165,C166), C177(C178,C179,C180,C181,C182)
8.e Idealised Me refined as rotating group:
 C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C73(H73A,H73B,
 H73C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C84(H84A,H84B,H84C), C85(H85A,
 H85B,H85C), C86(H86A,H86B,H86C), C92(H92A,H92B,H92C), C129(H12A,H12B,H12C),
 C130(H13A,H13B,H13C), C131(H13D,H13E,H13F), C140(H14A,H14B,H14C), C141(H14D,
 H14E,H14F), C142(H14G,H14H,H14I), C151(H15A,H15B,H15C), C152(H15D,H15E,H15F),
 C153(H15G,H15H,H15I), C169(H16A,H16B,H16C), C170(H17A,H17B,H17C), C171(H17D,
 H17E,H17F), C173(H17G,H17H,H17I), C174(H17J,H17K,H17L), C175(H17M,H17N,H17O),
 C184(H18A,H18B,H18C), C185(H18D,H18E,H18F), C186(H18G,H18H,H18I), C192(H19A,
 H19B,H19C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              82730
_shelx_fab_checksum              63815
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in oil'
_olex2_submission_original_sample_id k51_303
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.973
_oxdiff_exptl_absorpt_empirical_full_min 0.431