Zinc catalysed electrophilic C-H borylation of heteroarenes
Grundy, Matthew; Yuan, Kang; Nichol, Gary Stephen; Ingleson, Michael James; Chemical Science  (2021) –; doi:10.1039/D1SC01883C

data_1562552
_publ_section_title
;
 Zinc catalysed electrophilic C-H borylation of heteroarenes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01883C
_journal_year                    2021
_chemical_formula_moiety         'C33 H52 N2 Zn'
_chemical_formula_sum            'C33 H52 N2 Zn'
_chemical_formula_weight         542.13
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2021-03-12
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-03-30 deposited with the CCDC.	2021-05-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.0090(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.9444(3)
_cell_length_b                   19.6420(3)
_cell_length_c                   19.6889(3)
_cell_measurement_reflns_used    41884
_cell_measurement_temperature    120.0(5)
_cell_measurement_theta_max      26.8160
_cell_measurement_theta_min      3.5130
_cell_volume                     6166.17(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.0(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.947
_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    -33.00  51.00   1.00   40.00    --  -15.66  60.00 132.00   84
  2  \w      0.00  85.00   1.00   40.00    --   17.54  60.00 132.00   85
  3  \w    -49.00  35.00   1.00   40.00    --   17.54 -60.00  -6.00   84
  4  \w    -42.00  39.00   1.00   40.00    --  -15.66  77.00-120.00   81
  5  \w     -9.00  39.00   1.00   40.00    --   17.54  77.00 -60.00   48
  6  \w     -9.00  39.00   1.00   40.00    --   17.54  77.00   0.00   48
  7  \w     39.00  90.00   1.00   40.00    --   17.54 178.00 -30.00   51
  8  \w     -9.00  39.00   1.00   40.00    --   17.54  77.00  90.00   48
  9  \w      1.00  85.00   1.00   40.00    --   17.54  57.00-180.00   84
 10  \w     -9.00  39.00   1.00   40.00    --   17.54  77.00-150.00   48
 11  \w      1.00  85.00   1.00   40.00    --   17.54  57.00  30.00   84
 12  \w    -20.00  56.00   1.00   40.00    --   17.54 -99.00-180.00   76
 13  \w    -20.00  40.00   1.00   40.00    --   17.54 -99.00 -30.00   60
 14  \w    -52.00  37.00   1.00   40.00    --   17.54 -37.00  30.00   89
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0337711000
_diffrn_orient_matrix_UB_12      0.0204711000
_diffrn_orient_matrix_UB_13      -0.0115569000
_diffrn_orient_matrix_UB_21      -0.0122453000
_diffrn_orient_matrix_UB_22      -0.0262098000
_diffrn_orient_matrix_UB_23      -0.0227373000
_diffrn_orient_matrix_UB_31      -0.0262352000
_diffrn_orient_matrix_UB_32      -0.0140886000
_diffrn_orient_matrix_UB_33      0.0254363000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0479
_diffrn_reflns_av_unetI/netI     0.0566
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            135687
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.520
_diffrn_reflns_theta_min         3.291
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.819
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.98737
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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    1.168
_exptl_crystal_description       plank
_exptl_crystal_F_000             2352
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene'
_exptl_crystal_size_max          0.451
_exptl_crystal_size_mid          0.247
_exptl_crystal_size_min          0.143
_refine_diff_density_max         0.610
_refine_diff_density_min         -0.506
_refine_diff_density_rms         0.064
_refine_ls_abs_structure_details
;
 Twinning involves inversion, so Flack parameter cannot be determined
;
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1359
_refine_ls_number_reflns         30273
_refine_ls_number_restraints     34
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0474
_refine_ls_R_factor_gt           0.0389
_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^)+(0.0294P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0647
_refine_ls_wR_factor_ref         0.0675
_reflns_Friedel_coverage         0.947
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.948
_reflns_number_gt                27447
_reflns_number_total             30273
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01883c2.cif
_cod_data_source_block           mg211
_cod_database_code               1562552
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N Zn'
_chemical_oxdiff_usercomment     '@ 120 K  '
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.347(9)
 0.126(5) 0.239(6) 0.288(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Rigid body (RIGU) restrains
 C68, C69, C69A, C70, C70A, C71
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C79, C80
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C132, C131
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(H68c)=Sof(H68d)=Sof(C69A)=Sof(H69c)=Sof(H69d)=Sof(C70A)=Sof(H70c)=
 Sof(H70d)=Sof(H71c)=Sof(H71d)=1-FVAR(1)
 Sof(H68a)=Sof(H68b)=Sof(C69)=Sof(H69a)=Sof(H69b)=Sof(C70)=Sof(H70a)=Sof(H70b)=
 Sof(H71a)=Sof(H71b)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27), C45(H45), C48(H48), C57(H57),
 C60(H60), C78(H78), C81(H81), C90(H90), C93(H93), C111(H111), C114(H114),
 C123(H123), C126(H126)
5.b Secondary CH2 refined with riding coordinates:
 C2(H2a,H2b), C3(H3a,H3b), C4(H4a,H4b), C5(H5a,H5b), C30(H30a,H30b), C32(H32a,
 H32b), C35(H35a,H35b), C36(H36a,H36b), C37(H37a,H37b), C38(H38a,H38b),
 C63(H63a,H63b), C65(H65a,H65b), C68(H68a,H68b), C68(H68c,H68d), C69(H69a,H69b),
  C69A(H69c,H69d), C70(H70a,H70b), C70A(H70c,H70d), C71(H71a,H71b), C71(H71c,
 H71d), C96(H96a,H96b), C98(H98a,H98b), C101(H10a,H10b), C102(H10c,H10d),
 C103(H10e,H10f), C104(H10g,H10h), C129(H12m,H12n), C131(H13g,H13h)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C41(H41), C42(H42),
 C43(H43), C53(H53), C54(H54), C55(H55), C74(H74), C75(H75), C76(H76), C86(H86),
  C87(H87), C88(H88), C107(H107), C108(H108), C109(H109), C119(H119),
 C120(H120), C121(H121)
5.d Idealised Me refined as rotating group:
 C13(H13a,H13b,H13c), C14(H14a,H14b,H14c), C16(H16a,H16b,H16c), C17(H17a,H17b,
 H17c), C25(H25a,H25b,H25c), C26(H26a,H26b,H26c), C28(H28a,H28b,H28c), C29(H29a,
 H29b,H29c), C31(H31a,H31b,H31c), C33(H33a,H33b,H33c), C46(H46a,H46b,H46c),
 C47(H47a,H47b,H47c), C49(H49a,H49b,H49c), C50(H50a,H50b,H50c), C58(H58a,H58b,
 H58c), C59(H59a,H59b,H59c), C61(H61a,H61b,H61c), C62(H62a,H62b,H62c), C64(H64a,
 H64b,H64c), C66(H66a,H66b,H66c), C79(H79a,H79b,H79c), C80(H80a,H80b,H80c),
 C82(H82a,H82b,H82c), C83(H83a,H83b,H83c), C91(H91a,H91b,H91c), C92(H92a,H92b,
 H92c), C94(H94a,H94b,H94c), C95(H95a,H95b,H95c), C97(H97a,H97b,H97c), C99(H99a,
 H99b,H99c), C112(H11a,H11b,H11c), C113(H11d,H11e,H11f), C115(H11g,H11h,H11i),
 C116(H11j,H11k,H11l), C124(H12a,H12b,H12c), C125(H12d,H12e,H12f), C127(H12g,
 H12h,H12i), C128(H12j,H12k,H12l), C130(H13d,H13e,H13f), C132(H13i,H13j,H13k)
;
_shelx_res_checksum              2798
_shelx_hkl_checksum              47636
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in oil'
_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 1.072
_oxdiff_exptl_absorpt_empirical_full_min 0.917