Intramolecular C–N bond activation by a transient boryl anion
Nahon, Emily E.; Nelmes, Gareth Roland; Brothers, Penelope Jane; Hicks, Jamie; Chemical Communications  (2023) –; doi:10.1039/D3CC05182J

data_7132326
_publ_section_title
;
 Intramolecular C--N bond activation by a transient boryl anion
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC05182J
_journal_year                    2023
_chemical_formula_moiety         'C44 H58 B Br N2 O, C6 H6'
_chemical_formula_sum            'C50 H64 B Br N2 O'
_chemical_formula_weight         799.75
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-10-17
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2023-10-17 deposited with the CCDC.	2023-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                74.717(7)
_cell_angle_beta                 74.915(7)
_cell_angle_gamma                64.183(7)
_cell_formula_units_Z            2
_cell_length_a                   11.0832(8)
_cell_length_b                   12.2624(9)
_cell_length_c                   19.3619(17)
_cell_measurement_reflns_used    4529
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      72.8510
_cell_measurement_theta_min      4.7310
_cell_volume                     2252.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.971
_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    -98.00 -23.00   1.00    8.00    --  -36.13 -57.00-150.00   75
  2  \w   -103.00 -24.00   1.00    8.00    --  -36.13 -57.00 150.00   79
  3  \w     36.00  90.00   1.00    8.00    --   36.13-125.00   0.00   54
  4  \w    -21.00  55.00   1.00    8.00    --   36.13 -38.00-120.00   76
  5  \w    -31.00  52.00   1.00    8.00    --   36.13 -57.00   0.00   83
  6  \w     30.00 103.00   1.00    8.00    --   36.13  38.00 120.00   73
  7  \w     34.00  90.00   1.00    8.00    --   36.13-125.00-180.00   56
  8  \w    105.00 177.00   1.00   32.00    --  109.00  45.00  30.00   72
  9  \w    115.00 177.00   1.00   32.00    --  109.00  77.00 -60.00   62
 10  \w    112.00 162.00   1.00   32.00    --  109.00  77.00 -30.00   50
 11  \w     46.00 114.00   1.00   32.00    --  109.00 -45.00 -60.00   68
 12  \w     97.00 130.00   1.00   32.00    --  109.00  61.00   0.00   33
 13  \w    135.00 171.00   1.00   32.00    --  109.00  61.00   0.00   36
 14  \w    105.00 177.00   1.00   32.00    --  109.00  30.00  90.00   72
 15  \w     67.00 108.00   1.00   32.00    --  109.00-111.00  30.00   41
 16  \w     41.00  98.00   1.00   32.00    --  109.00 -95.00-150.00   57
 17  \w     39.00 126.00   1.00   32.00    --  109.00 -30.00-150.00   87
 18  \w    109.00 177.00   1.00   32.00    --  109.00 111.00 -90.00   68
 19  \w     42.00 128.00   1.00   32.00    --  109.00 -30.00   0.00   86
 20  \w     41.00 109.00   1.00   32.00    --  109.00-111.00 -90.00   68
 21  \w     53.00 104.00   1.00   32.00    --  109.00 -95.00 -60.00   51
 22  \w     48.00 106.00   1.00   32.00    --  109.00 -95.00  60.00   58
 23  \w     45.00 117.00   1.00   32.00    --  109.00 -61.00-120.00   72
 24  \w     42.00 106.00   1.00   32.00    --  109.00 -95.00 120.00   64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1355684000
_diffrn_orient_matrix_UB_12      0.1130099000
_diffrn_orient_matrix_UB_13      -0.0037284000
_diffrn_orient_matrix_UB_21      -0.0707177000
_diffrn_orient_matrix_UB_22      -0.0684544000
_diffrn_orient_matrix_UB_23      0.0639918000
_diffrn_orient_matrix_UB_31      0.0339356000
_diffrn_orient_matrix_UB_32      0.0511913000
_diffrn_orient_matrix_UB_33      0.0537697000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0561
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            9202
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.305
_diffrn_reflns_theta_min         4.066
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.512
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88136
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2020)
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    1.179
_exptl_crystal_description       plate
_exptl_crystal_F_000             852
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.712
_refine_diff_density_min         -0.678
_refine_diff_density_rms         0.082
_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     542
_refine_ls_number_reflns         9202
_refine_ls_number_restraints     96
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0785
_refine_ls_R_factor_gt           0.0614
_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^)+(0.0057P)^2^+8.7677P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1358
_refine_ls_wR_factor_ref         0.1437
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7573
_reflns_number_total             9202
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 179.9572\% 
around [0.00 0.00 1.00] (reciprocal) or [-0.29 -0.26 0.92] (direct)
;
_cod_data_source_file            d3cc05182j2.cif
_cod_data_source_block           3-Br
_cod_database_code               7132326
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C40H40B1Br1N2O1
_shelx_estimated_absorpt_t_max   0.985
_shelx_estimated_absorpt_t_min   0.889
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7010(13)
 0.2990(13)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
C50 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
C46A \\sim C47A \\sim C48A \\sim C49A \\sim C50A \\sim C45A: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C20 \\sim C17 \\sim C18 \\sim C19: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
Uanis(B1) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
4. Others
 Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(H47A)=Sof(C48A)=Sof(H48A)=Sof(C49A)=
 Sof(H49A)=Sof(C50A)=Sof(H50A)=Sof(C45A)=Sof(H45A)=1-FVAR(1)
 Sof(C50)=Sof(H50)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46)=Sof(C47)=Sof(H47)=
 Sof(C48)=Sof(H48)=Sof(C49)=Sof(H49)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C27(H27), C39(H39), C30(H30), C42(H42)
5.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C25(H25), C6(H6), C23(H23), C3(H3), C12(H12), C5(H5), C24(H24),
 C37(H37), C36(H36), C11(H11), C35(H35), C50(H50), C45(H45), C46(H46), C47(H47),
  C48(H48), C49(H49), C46A(H46A), C47A(H47A), C48A(H48A), C49A(H49A),
 C50A(H50A), C45A(H45A)
5.c Fitted hexagon refined as free rotating group:
 C50(C45,C46,C47,C48,C49), C46A(C47A,C48A,C49A,C50A,C45A)
5.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C29(H29A,H29B,H29C), C16(H16A,H16B,H16C), C28(H28A,H28B,
 H28C), C15(H15A,H15B,H15C), C40(H40A,H40B,H40C), C32(H32A,H32B,H32C), C44(H44A,
 H44B,H44C), C41(H41A,H41B,H41C), C43(H43A,H43B,H43C), C18(H18A,H18B,H18C),
 C14(H14A,H14B,H14C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C)
;
_shelx_res_checksum              77224
_shelx_hkl_checksum              78845
_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 1.513
_oxdiff_exptl_absorpt_empirical_full_min 0.680
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2