Investigating the diastereoselective synthesis of a macrocycle under Curtin-Hammett control.
Yeung, Angus; Zwijnenburg, Martijn A.; Orton, Georgia R. F.; Robertson, Jennifer H.; Barendt, Timothy A.; Chemical science 15 (2024) 5516–5524; doi:10.1039/d3sc05715a

data_1571151
_publ_section_title
;
 Investigating the diastereoselective synthesis of a macrocycle under
 Curtin-Hammett control.
;
_journal_issue                   15
_journal_name_full               'Chemical science'
_journal_page_first              5516
_journal_page_last               5524
_journal_paper_doi               10.1039/d3sc05715a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         '0.83(C H Cl3), C66 H61.85 N8 O6'
_chemical_formula_sum            'C66.83 H62.68 Cl2.49 N8 O6'
_chemical_formula_weight         1162.16
_chemical_name_systematic        hydroquinone_PDI_macrocycle
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-03-03
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-03-16 deposited with the CCDC.	2024-03-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.1850(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.39140(10)
_cell_length_b                   14.94010(10)
_cell_length_c                   33.6959(2)
_cell_measurement_reflns_used    60928
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.7870
_cell_measurement_theta_min      2.9310
_cell_volume                     7243.37(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.955
_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   -120.00 -71.00   0.50    0.51    --  -49.15-129.00  50.00   98
  2  \w   -120.00 -63.00   0.50    0.51    --  -49.15-141.00-121.00  114
  3  \w    -98.00 -21.00   0.50    0.51    --  -49.15 141.00 -64.00  154
  4  \w    -89.00 -15.00   0.50    0.51    --  -49.15 129.00 123.00  148
  5  \w     37.00  98.00   0.50    0.51    --   49.15-129.00  50.00  122
  6  \w     43.00 105.00   0.50    0.51    --   49.15-141.00-121.00  124
  7  \w   -161.00 -71.00   0.50    2.04    --  -90.00-129.00  50.00  180
  8  \w    -89.00 -18.00   0.50    2.04    --  -90.00 129.00 123.00  142
  9  \w   -156.00 -63.00   0.50    2.04    --  -90.00-141.00-121.00  186
 10  \w     38.00 115.00   0.50    2.04    --  110.16-129.00  50.00  154
 11  \w     84.00 173.00   0.50    2.04    --  110.16 141.00 -64.00  178
 12  \w     43.00 123.00   0.50    2.04    --  110.16-141.00-121.00  160
 13  \w     93.00 178.00   0.50    2.04    --  110.16 129.00 123.00  170
 14  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00 -30.00   52
 15  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00  60.00   52
 16  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00 150.00   52
 17  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00  90.00   52
 18  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00 -90.00   52
 19  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00 -60.00   52
 20  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00-150.00   52
 21  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00-180.00   52
 22  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00  30.00   52
 23  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00   0.00   52
 24  \w   -120.00 -94.00   0.50    0.51    --  -49.15 -57.00 120.00   52
 25  \w     94.00 121.00   0.50    0.51    --   49.15  57.00-150.00   54
 26  \w    -24.00  26.00   0.50    0.51    --   49.15 -19.00 120.00  100
 27  \w     63.00 121.00   0.50    0.51    --   49.15 178.00  30.00  116
 28  \w    -47.00 -19.00   0.50    2.04    --  -90.00  38.00 -90.00   56
 29  \w   -149.00-123.00   0.50    2.04    --  -90.00 -52.00 113.63   52
 30  \w   -160.00-114.00   0.50    2.04    --  -90.00 -77.00  90.00   92
 31  \w    -43.00 -18.00   0.50    2.04    --  -90.00  38.00  90.00   50
 32  \w   -152.00 -94.00   0.50    2.04    --  -90.00 -57.00 -94.29  116
 33  \w    -47.00 -18.00   0.50    2.04    --  -90.00  38.00 150.00   58
 34  \w   -161.00 -94.00   0.50    2.04    --  -90.00 -56.00-126.98  134
 35  \w    -47.00 -19.00   0.50    2.04    --  -90.00  38.00  60.00   56
 36  \w    -45.00 -18.00   0.50    2.04    --  -90.00  38.00   0.00   54
 37  \w    -48.00 -20.00   0.50    2.04    --  -90.00  38.00-120.00   56
 38  \w   -152.00-109.00   0.50    2.04    --  -90.00 -77.00 -90.00   86
 39  \w   -159.00-109.00   0.50    2.04    --  -90.00 -77.00 120.00  100
 40  \w    -47.00 -18.00   0.50    2.04    --  -90.00  38.00 -30.00   58
 41  \w   -161.00-106.00   0.50    2.04    --  -90.00 -77.00-180.00  110
 42  \w   -105.00 -80.00   0.50    2.04    --  -90.00 -52.00 113.63   50
 43  \w    -47.00 -19.00   0.50    2.04    --  -90.00  38.00 120.00   56
 44  \w    -84.00 -59.00   0.50    2.04    --  -90.00 141.00 -64.00   50
 45  \w     43.00 100.00   0.50    2.04    --  110.16 -99.00 150.00  114
 46  \w     39.00 101.00   0.50    2.04    --  110.16 -99.00  60.00  124
 47  \w     87.00 112.00   0.50    2.04    --  110.16-125.00   0.00   50
 48  \w     39.00  67.00   0.50    2.04    --  110.16-125.00   0.00   56
 49  \w     46.00  87.00   0.50    2.04    --  110.16 -77.00-150.00   82
 50  \w     48.00 104.00   0.50    2.04    --  110.16 -99.00 -30.00  112
 51  \w     63.00 105.00   0.50    2.04    --  110.16 -99.00-120.00   84
 52  \w     73.00 107.00   0.50    2.04    --  110.16-105.00 120.82   68
 53  \w    102.00 141.00   0.50    2.04    --  110.16  38.00-150.00   78
 54  \w     71.00 110.00   0.50    2.04    --  110.16-125.00 -30.00   78
 55  \w     47.00  73.00   0.50    2.04    --  110.16 -77.00  90.00   52
 56  \w     39.00  97.00   0.50    2.04    --  110.16 -77.00  60.00  116
 57  \w     65.00 104.00   0.50    2.04    --  110.16 -99.00  30.00   78
 58  \w     40.00  68.00   0.50    2.04    --  110.16 -77.00 -90.00   56
 59  \w     43.00  83.00   0.50    2.04    --  110.16 -77.00-120.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0227944000
_diffrn_orient_matrix_UB_12      -0.0050066000
_diffrn_orient_matrix_UB_13      -0.0448381000
_diffrn_orient_matrix_UB_21      -0.0035400000
_diffrn_orient_matrix_UB_22      -0.1028766000
_diffrn_orient_matrix_UB_23      0.0025653000
_diffrn_orient_matrix_UB_31      -0.1045430000
_diffrn_orient_matrix_UB_32      0.0043810000
_diffrn_orient_matrix_UB_33      0.0087020000
_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  0.0433
_diffrn_reflns_av_unetI/netI     0.0229
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            134698
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.431
_diffrn_reflns_theta_min         2.958
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.369
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72052
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.066
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             2440
_exptl_crystal_preparation       'see experimental'
_exptl_crystal_recrystallization_method 'see experimental'
_exptl_crystal_size_max          0.304
_exptl_crystal_size_mid          0.203
_exptl_crystal_size_min          0.082
_refine_diff_density_max         1.567
_refine_diff_density_min         -1.398
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     734
_refine_ls_number_reflns         14866
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0882
_refine_ls_R_factor_gt           0.0829
_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^)+(0.1283P)^2^+13.7931P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2357
_refine_ls_wR_factor_ref         0.2406
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13167
_reflns_number_total             14866
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05715a3.cif
_cod_data_source_block           hydroquinone_pdi_macrocycle
_cod_depositor_comments          'Adding full bibliography for 1571151.cif.'
_cod_database_code               1571151
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C66 H62 N7 O6'
_shelx_estimated_absorpt_t_max   0.896
_shelx_estimated_absorpt_t_min   0.681
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H53A,H53B,H53} of C53, All C(H,H) groups, All C(H,H,H,H)
  groups
 At 1.5 times of:
  {H33A,H33B,H33C} of C33, {H48A,H48B,H48C} of C48, {H35A,H35B,H35C} of C35,
  {H44A,H44B,H44C} of C44, {H45A,H45B,H45C} of C45, {H36A,H36B,H36C} of C36,
  {H32A,H32B,H32C} of C32, {H47A,H47B,H47C} of C47
2. Uiso/Uaniso restraints and constraints
Uanis(C57B) = Uanis(C55B) = Uanis(C59B) = Uanis(C60B) = Uanis(C58B) =
Uanis(C56B)
3. Others
 Fixed Sof: Cl1(0.83) Cl2(0.83) Cl3(0.83) C67(0.83) H67(0.83) H53A(0.85)
 H53B(0.85) H53(0.15) H51A(0.85) H51B(0.85) H51C(0.15) H51D(0.15) O5A(0.85)
 C54A(0.85) H54A(0.85) H54B(0.85) C56A(0.85) H56A(0.85) C55A(0.85) C60A(0.85)
 H60A(0.85) C59A(0.85) H59A(0.85) C58A(0.85) C57A(0.85) H57A(0.85) C52A(0.85)
 H52A(0.85) H52B(0.85) O5B(0.15) C54B(0.15) H54C(0.15) H54D(0.15) C55B(0.15)
 C60B(0.15) H60B(0.15) C59B(0.15) H59B(0.15) C58B(0.15) C57B(0.15) H57B(0.15)
 C56B(0.15) H56B(0.15) C52B(0.15) H52C(0.15) H52D(0.15)
4.a Ternary CH refined with riding coordinates:
 C67(H67), C46(H46), C34(H34), C31(H31), C43(H43)
4.b Secondary CH2 refined with riding coordinates:
 C53(H53A,H53B), C62(H62A,H62B), C51(H51A,H51B), C51(H51C,H51D), C61(H61A,
 H61B), C63(H63A,H63B), C64(H64A,H64B), C54A(H54A,H54B), C52A(H52A,H52B),
 C54B(H54C,H54D), C52B(H52C,H52D)
4.c Aromatic/amide H refined with riding coordinates:
 C53(H53), C65(H65), C50(H50), C41(H41), C40(H40), C39(H39), C3(H3), C27(H27),
 C28(H28), C29(H29), C4(H4), C8(H8), C13(H13), C14(H14), C18(H18), C56A(H56A),
 C60A(H60A), C59A(H59A), C57A(H57A), C60B(H60B), C59B(H59B), C57B(H57B),
 C56B(H56B)
4.d Fitted hexagon refined as free rotating group:
 C38(C37,C42,C41,C40,C39), C25(C26,C27,C28,C29,C30), C8(C7,C6,C23,C24,C9),
 C16(C22,C21,C19,C18,C17), C56A(C55A,C60A,C59A,C58A,C57A), C55B(C60B,C59B,C58B,
 C57B,C56B)
4.e Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C45(H45A,H45B,H45C), C32(H32A,H32B,H32C), C47(H47A,H47B,
 H47C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C48(H48A,H48B,H48C), C44(H44A,
 H44B,H44C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 580 electrons were 
found in a volume of 1784\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2.5[HCCl3] per Asymmetric Unit 
which account for 580 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_olex2_exptl_crystal_mounting_method 'in fomblin on micromount'
_olex2_submission_original_sample_id hydroquinone_PDI_macrocycle
_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 1.302
_oxdiff_exptl_absorpt_empirical_full_min 0.840