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_7132330
_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         '2(C52 H74 Mg N2 O3)'
_chemical_formula_sum            'C104 H148 Mg2 N4 O6'
_chemical_formula_weight         1598.88
_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
_audit_creation_date             2023-03-05
_audit_creation_method
;
Olex2 1.5
(compiled 2023.02.24 svn.rf166f9f3 for OlexSys, GUI svn.r6725)
;
_audit_update_record
;
2023-10-17 deposited with the CCDC.	2023-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.4550(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.18110(10)
_cell_length_b                   11.81750(10)
_cell_length_c                   27.6540(2)
_cell_measurement_reflns_used    36957
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      77.7350
_cell_measurement_theta_min      3.7310
_cell_volume                     4825.03(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.74a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.74a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.74a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.00
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_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   -114.00 -67.00   0.50    0.28    --  -46.57-135.00  49.00   94
  2  \w    -93.00 -55.00   0.50    0.28    --  -46.57 135.00 114.00   76
  3  \w    -74.00 -20.00   0.50    0.28    --  -46.57 134.00 -64.00  108
  4  \w   -117.00 -92.00   0.50    0.28    --  -46.57-134.00-131.00   50
  5  \w     61.00  86.00   0.50    0.28    --   46.57-135.00  49.00   50
  6  \w     40.00  97.00   0.50    0.28    --   46.57-134.00-131.00  114
  7  \w    109.00 134.00   0.50    1.11    --  107.75 134.00 -64.00   50
  8  \w     60.00 119.00   0.50    1.11    --  107.75-134.00-131.00  118
  9  \w     59.00  85.00   0.50    1.11    --  107.75-135.00  49.00   52
 10  \w     91.00 130.00   0.50    1.11    --  107.75 135.00 114.00   78
 11  \w   -118.00 -24.00   0.50    0.28    --  -46.57 -77.00  60.00  188
 12  \w   -119.00 -32.00   0.50    0.28    --  -46.57 -57.00 -60.00  174
 13  \w     43.00 119.00   0.50    0.28    --   46.57  77.00-120.00  152
 14  \w     35.00  81.00   0.50    0.28    --   46.57-125.00-180.00   92
 15  \w    -12.00  60.00   0.50    0.28    --   46.57 -38.00  90.00  144
 16  \w     95.00 175.00   0.50    1.11    --  107.75  45.00  30.00  160
 17  \w    119.00 178.00   0.50    1.11    --  107.75  45.00 150.00  118
 18  \w     39.00  68.00   0.50    1.11    --  107.75 -45.00   0.00   58
 19  \w     69.00 107.00   0.50    1.11    --  107.75-102.00 -33.50   76
 20  \w     53.00  81.00   0.50    1.11    --  107.75 -95.00-150.00   56
 21  \w     92.00 126.00   0.50    1.11    --  107.75-144.00  98.33   68
 22  \w     35.00 105.00   0.50    1.11    --  107.75 -95.00  60.00  140
 23  \w     95.00 161.00   0.50    1.11    --  107.75  15.00 -60.00  132
 24  \w    115.00 161.00   0.50    1.11    --  107.75  45.00 -60.00   92
 25  \w     41.00  79.00   0.50    1.11    --  107.75-125.00   0.00   76
 26  \w     59.00 119.00   0.50    1.11    --  107.75 -61.00 -90.00  120
 27  \w     36.00  96.00   0.50    1.11    --  107.75 -45.00  90.00  120
 28  \w     35.00 116.00   0.50    1.11    --  107.75 -77.00  60.00  162
 29  \w     95.00 177.00   0.50    1.11    --  107.75  15.00-150.00  164
 30  \w     70.00 100.00   0.50    1.11    --  107.75 -95.00 -90.00   60
 31  \w     56.00  95.00   0.50    1.11    --  107.75-125.00 150.00   78
 32  \w     53.00 121.00   0.50    1.11    --  107.75 -30.00  30.00  136
 33  \w     92.00 118.00   0.50    1.11    --  107.75 -45.00   0.00   52
 34  \w     35.00 114.00   0.50    1.11    --  107.75 -61.00-180.00  158
 35  \w     80.00 105.00   0.50    1.11    --  107.75 -95.00 120.00   50
 36  \w     36.00  74.00   0.50    1.11    --  107.75 -95.00 -60.00   76
 37  \w     62.00 107.00   0.50    1.11    --  107.75-102.00-111.47   90
 38  \w     70.00 107.00   0.50    1.11    --  107.75-104.00   4.21   74
 39  \w    105.00 178.00   0.50    1.11    --  107.75  30.00-120.00  146
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0171356000
_diffrn_orient_matrix_UB_12      -0.1278374000
_diffrn_orient_matrix_UB_13      -0.0082830000
_diffrn_orient_matrix_UB_21      -0.0225843000
_diffrn_orient_matrix_UB_22      0.0187485000
_diffrn_orient_matrix_UB_23      -0.0566741000
_diffrn_orient_matrix_UB_31      0.1003984000
_diffrn_orient_matrix_UB_32      -0.0175505000
_diffrn_orient_matrix_UB_33      -0.0003192000
_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  0.0405
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            65697
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.077
_diffrn_reflns_theta_min         3.735
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.629
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65465
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.74a (Rigaku Oxford Diffraction, 2022)
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    1.101
_exptl_crystal_description       block
_exptl_crystal_F_000             1744
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.220
_refine_diff_density_min         -0.255
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     568
_refine_ls_number_reflns         10166
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0437
_refine_ls_R_factor_gt           0.0390
_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^)+(0.0522P)^2^+1.1537P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1039
_refine_ls_wR_factor_ref         0.1078
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8994
_reflns_number_total             10166
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc05182j2.cif
_cod_data_source_block           2-THF
_cod_database_code               7132330
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C70H70O3N2Mg
_shelx_estimated_absorpt_t_max   0.940
_shelx_estimated_absorpt_t_min   0.810
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C7-C9A = C9-C7 = C7-C10A = C7-C10 = C7-C8A = C8-C7
 1.53 with sigma of 0.008
 C8-C9 = C9-C10 = C10-C8 = C8A-C9A = C9A-C10A = C10A-C8A
 2.5 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C7 \\sim C10 \\sim C10A \\sim C9 \\sim C9A \\sim C8 \\sim C8A: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
4. Others
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=
 Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=1-FVAR(1)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C27(H27), C42(H42), C39(H39), C30(H30)
5.b Secondary CH2 refined with riding coordinates:
 C48(H48A,H48B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C49(H49A,
 H49B), C52(H52A,H52B), C51(H51A,H51B), C50(H50A,H50B)
5.c Aromatic/amide H refined with riding coordinates:
 C16(H16), C15(H15), C13(H13), C6(H6), C5(H5), C3(H3), C23(H23), C25(H25),
 C24(H24), C35(H35), C37(H37), C36(H36)
5.d Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C19(H19A,H19B,H19C), C28(H28A,H28B,H28C), C44(H44A,H44B,
 H44C), C41(H41A,H41B,H41C), C20(H20A,H20B,H20C), C40(H40A,H40B,H40C), C18(H18A,
 H18B,H18C), C43(H43A,H43B,H43C), C31(H31A,H31B,H31C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C32(H32A,H32B,H32C), C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F),
 C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC)
;
_shelx_res_checksum              87379
_shelx_hkl_checksum              193
_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 1.426
_oxdiff_exptl_absorpt_empirical_full_min 0.601