Photoinduced metal-free borylation of aryl halides catalysed by an in situ formed donor–acceptor complex
Li, Manhong; Liu, Siqi; Bao, Haoshi; Li, Qini; Deng, Yi-Hui; Sun, Tian-Yu; Wang, Leifeng; Chemical Science  (2022) –; doi:10.1039/D2SC00552B

data_1566775
_publ_section_title
;
 Photoinduced metal-free borylation of aryl halides catalysed by an in
 situ formed donor--acceptor complex
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC00552B
_journal_year                    2022
_chemical_formula_moiety         'C30 H38 B2 N2 O4'
_chemical_formula_sum            'C30 H38 B2 N2 O4'
_chemical_formula_weight         512.24
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-11-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-01-27 deposited with the CCDC.	2022-04-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.775(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.0763(3)
_cell_length_b                   9.9694(2)
_cell_length_c                   19.4363(4)
_cell_measurement_reflns_used    9577
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.9470
_cell_measurement_theta_min      3.3720
_cell_volume                     2837.29(10)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_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 0.963
_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     90.00 117.00   0.50    0.50    --  105.51  61.00 -90.00   54
  2  \w    138.00 164.00   0.50    0.50    --  105.51  61.00 -90.00   52
  3  \w     89.00 172.00   0.50    0.50    --  105.51  30.00-120.00  166
  4  \w    109.00 134.00   0.50    0.50    --  105.51  26.00-170.00   50
  5  \w     29.00 118.00   0.50    0.05    --   45.81  26.00-170.00  178
  6  \w    -25.00   9.00   0.50    0.05    --   45.81 -19.00-120.00   68
  7  \w     38.00  68.00   0.50    0.50    --  105.51 -61.00-150.00   60
  8  \w     66.00 103.00   0.50    0.50    --  105.51 -77.00  60.00   74
  9  \w     36.00  71.00   0.50    0.50    --  105.51 -61.00 150.00   70
 10  \w    118.00 166.00   0.50    0.50    --  105.51 125.00  90.00   96
 11  \w     82.00 113.00   0.50    0.50    --  105.51 125.00  90.00   62
 12  \w      0.00  26.00   0.50    0.05    --   45.81 -26.00  26.00   52
 13  \w   -104.00 -42.00   0.50    0.05    --  -45.81 -26.00  26.00  124
 14  \w    -64.00 -27.00   0.50    0.50    -- -100.00  61.00-180.00   74
 15  \w    -69.00 -29.00   0.50    0.50    -- -100.00  61.00 -30.00   80
 16  \w    -67.00 -29.00   0.50    0.50    -- -100.00  61.00 -60.00   76
 17  \w    -69.00 -43.00   0.50    0.50    -- -100.00  61.00   0.00   52
 18  \w    -65.00 -28.00   0.50    0.50    -- -100.00  61.00 120.00   74
 19  \w    -62.00 -29.00   0.50    0.50    -- -100.00  61.00 150.00   66
 20  \w    -99.00 -71.00   0.50    0.50    -- -100.00  77.00   0.00   56
 21  \w   -175.00 -83.00   0.50    0.50    -- -100.00 -26.00  26.00  184
 22  \w    -17.00   9.00   0.50    0.05    --  -45.81  26.00-170.00   52
 23  \w    -39.00  28.00   0.50    0.05    --  -45.81  38.00 -30.00  134
 24  \w     44.00 100.00   0.50    0.50    --  105.51 -94.00-120.00  112
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0014967000
_diffrn_orient_matrix_UB_12      0.0157564000
_diffrn_orient_matrix_UB_13      0.0785250000
_diffrn_orient_matrix_UB_21      0.0992096000
_diffrn_orient_matrix_UB_22      -0.0510721000
_diffrn_orient_matrix_UB_23      0.0221404000
_diffrn_orient_matrix_UB_31      0.0350402000
_diffrn_orient_matrix_UB_32      0.1450297000
_diffrn_orient_matrix_UB_33      -0.0008341000
_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  0.0786
_diffrn_reflns_av_unetI/netI     0.0694
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            18990
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.464
_diffrn_reflns_theta_min         3.351
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.616
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40745
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (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    1.199
_exptl_crystal_description       block
_exptl_crystal_F_000             1096
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: ??????????????'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.517
_refine_diff_density_min         -0.308
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         5671
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0616
_refine_ls_R_factor_gt           0.0512
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0715P)^2^+0.6506P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1356
_refine_ls_wR_factor_ref         0.1438
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4674
_reflns_number_total             5671
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc00552b2.cif
_cod_data_source_block           limh_211103_auto
_cod_database_code               1566775
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.941
_shelx_estimated_absorpt_t_min   0.913
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C1(H1), C20(H20)
2.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C12(H12), C18(H18), C13(H13), C8(H8), C3(H3), C15(H15), C6(H6),
 C17(H17), C4(H4), C16(H16), C5(H5)
2.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C26(H26A,H26B,
 H26C), C38(H38A,H38B,H38C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C36(H36A,
 H36B,H36C)
;
_shelx_res_checksum              29713
_shelx_hkl_checksum              46851
_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 3.173
_oxdiff_exptl_absorpt_empirical_full_min 0.348