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_7132331
_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 H60 N2 O'
_chemical_formula_sum            'C44 H60 N2 O'
_chemical_formula_weight         632.94
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-04-24
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2023-10-17 deposited with the CCDC.	2023-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.4574(14)
_cell_angle_gamma                90
_cell_formula_units_Z            32
_cell_length_a                   70.8297(10)
_cell_length_b                   10.40514(14)
_cell_length_c                   44.9198(6)
_cell_measurement_reflns_used    25907
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      73.6590
_cell_measurement_theta_min      3.7760
_cell_volume                     31908.1(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.67a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.67a (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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.958
_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     20.00 102.50   0.75    2.50    --   36.95  57.00-120.00  110
  2  \w     33.00  84.00   0.75    2.50    --   36.95-125.00 150.00   68
  3  \w     20.00 102.50   0.75    2.50    --   36.95  57.00 -30.00  110
  4  \w     36.00  85.50   0.75    2.50    --   36.95-125.00 -60.00   66
  5  \w     13.00 106.00   0.75    2.50    --   36.95  19.00  90.00  124
  6  \w    -32.00  55.00   0.75    2.50    --   36.95 -38.00  90.00  116
  7  \w     20.00  74.00   0.75    2.50    --   36.95 -99.00  30.00   72
  8  \w    116.00 161.00   0.75   10.00    --  111.00  77.00  60.00   60
  9  \w     42.00 108.00   0.75   10.00    --  111.00-111.00 150.00   88
 10  \w     42.00 105.00   0.75   10.00    --  111.00 -92.00 -90.00   84
 11  \w     97.00 178.00   0.75   10.00    --  111.00  50.00-180.00  108
 12  \w     43.00 108.25   0.75   10.00    --  111.00-111.00  90.00   87
 13  \w     92.00 171.50   0.75   10.00    --  111.00  38.00 -90.00  106
 14  \w     63.50 131.00   0.75   10.00    --  111.00 -64.00 120.00   90
 15  \w     50.00 108.50   0.75   10.00    --  111.00-111.00-120.00   78
 16  \w     41.00  74.00   0.75   10.00    --  111.00-111.00  60.00   44
 17  \w     42.00 128.25   0.75   10.00    --  111.00 -38.00-120.00  115
 18  \w     42.00 108.00   0.75   10.00    --  111.00-111.00  30.00   88
 19  \w    103.00 178.00   0.75   10.00    --  111.00  77.00 -60.00  100
 20  \w     53.00  87.50   0.75   10.00    --  111.00 -50.00  30.00   46
 21  \w    102.00 127.50   0.75   10.00    --  111.00 -50.00  30.00   34
 22  \w     95.00 167.75   0.75   10.00    --  111.00  50.00-150.00   97
;
_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      0.0148090000
_diffrn_orient_matrix_UB_12      0.0655145000
_diffrn_orient_matrix_UB_13      0.0271970000
_diffrn_orient_matrix_UB_21      -0.0010551000
_diffrn_orient_matrix_UB_22      -0.1162713000
_diffrn_orient_matrix_UB_23      0.0207433000
_diffrn_orient_matrix_UB_31      0.0169973000
_diffrn_orient_matrix_UB_32      -0.0643155000
_diffrn_orient_matrix_UB_33      -0.0098161000
_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  0.1069
_diffrn_reflns_av_unetI/netI     0.0846
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       86
_diffrn_reflns_limit_h_min       -77
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -55
_diffrn_reflns_number            107772
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.975
_diffrn_reflns_theta_min         5.039
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.466
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88531
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.67a (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    1.054
_exptl_crystal_description       block
_exptl_crystal_F_000             11072
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.583
_refine_diff_density_min         -0.427
_refine_diff_density_rms         0.051
_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     1910
_refine_ls_number_reflns         31872
_refine_ls_number_restraints     437
_refine_ls_restrained_S_all      1.243
_refine_ls_R_factor_all          0.0983
_refine_ls_R_factor_gt           0.0686
_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^)+(0.0900P)^2^+12.3772P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1782
_refine_ls_wR_factor_ref         0.2086
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23219
_reflns_number_total             31872
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc05182j2.cif
_cod_data_source_block           H2FNON
_cod_database_code               7132331
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C44H44N2O1
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.892
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C17-C18 = C17-C19 = C17-C20
 1.53 with sigma of 0.008
 C38-C39 = C39-C40 = C39-C41 = C39-C40A
 1.53 with sigma of 0.005
 C166-C274 = C274-C275 = C274-C276
 1.53 with sigma of 0.008
 C17-C18A = C17-C19A = C17-C20A
 1.53 with sigma of 0.008
 C70-C71 = C71-C72 = C71-C73
 1.53 with sigma of 0.008
 C70-C71A = C71A-C72A = C71A-C73A
 1.53 with sigma of 0.008
 C122-C130 = C130-C131 = C130-C132
 1.53 with sigma of 0.008
 C122-C230 = C230-C231 = C230-C232
 1.53 with sigma of 0.008
 C170-C171 = C171-C172 = C171-C173
 1.53 with sigma of 0.008
 C170-C271 = C271-C272 = C271-C273
 1.53 with sigma of 0.008
 C166-C174 = C174-C175 = C174-C176
 1.53 with sigma of 0.008
 C39-C40
 2.5 with sigma of 0.008
 C18-C19 = C19-C20 = C20-C18
 2.5 with sigma of 0.008
 C175-C176 = C275-C276
 2.5 with sigma of 0.008
 C18A-C19A = C19A-C20A = C20A-C18A
 2.5 with sigma of 0.008
 C72-C73 = C72A-C73A
 2.5 with sigma of 0.008
 C131-C132 = C231-C232
 2.5 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
C39 \\sim C40 \\sim C41 \\sim C40A: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C18A \\sim C19A \\sim C20A: within 2A
with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C174 \\sim C175 \\sim C176 \\sim C274 \\sim C275 \\sim C276: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.006 within 2A
C71 \\sim C72 \\sim C73 \\sim C71A \\sim C72A \\sim C73A: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.01 within 2A
C130 \\sim C131 \\sim C132 \\sim C230 \\sim C231 \\sim C232: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C171 \\sim C172 \\sim C173 \\sim C271 \\sim C272 \\sim C273: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(C75) \\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(C275) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=Sof(H19E)=
 Sof(H19F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
 Sof(H39A)=Sof(C71A)=Sof(H71A)=Sof(C72A)=Sof(H72D)=Sof(H72E)=Sof(H72F)=
 Sof(C73A)=Sof(H73D)=Sof(H73E)=Sof(H73F)=Sof(C40A)=Sof(H40D)=Sof(H40E)=
 Sof(H40F)=1-FVAR(2)
 Sof(H39)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C71)=Sof(H71)=Sof(C72)=
 Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=FVAR(2)
 Sof(C230)=Sof(H230)=Sof(C231)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C232)=
 Sof(H23D)=Sof(H23E)=Sof(H23F)=1-FVAR(3)
 Sof(C130)=Sof(H130)=Sof(C131)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C132)=
 Sof(H13D)=Sof(H13E)=Sof(H13F)=FVAR(3)
 Sof(C271)=Sof(H271)=Sof(C272)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C273)=
 Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(4)
 Sof(C171)=Sof(H171)=Sof(C172)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C173)=
 Sof(H17D)=Sof(H17E)=Sof(H17F)=FVAR(4)
 Sof(C274)=Sof(H274)=Sof(C275)=Sof(H27G)=Sof(H27H)=Sof(H27I)=Sof(C276)=
 Sof(H27J)=Sof(H27K)=Sof(H27L)=1-FVAR(5)
 Sof(C174)=Sof(H174)=Sof(C175)=Sof(H17G)=Sof(H17H)=Sof(H17I)=Sof(C176)=
 Sof(H17J)=Sof(H17K)=Sof(H17L)=FVAR(5)
5.a Ternary CH refined with riding coordinates:
 C27(H27), C30(H30), C39(H39), C39(H39A), C42(H42), C71(H71), C74(H74),
 C83(H83), C86(H86), C115(H115), C118(H118), C127(H127), C130(H130), C159(H159),
  C162(H162), C171(H171), C174(H174), C230(H230), C271(H271), C274(H274),
 C71A(H71A)
5.b Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), N3(H3A), C3(H3), N4(H4), N5(H5A), C5(H5), N6(H6A), C6(H6),
 N7(H7), N8(H8), C13(H13), C15(H15), C16(H16), C23(H23), C24(H24), C25(H25),
 C35(H35), C36(H36), C37(H37), C47(H47), C49(H49), C50(H50), C57(H57), C59(H59),
  C60(H60), C67(H67), C68(H68), C69(H69), C79(H79), C80(H80), C81(H81),
 C91(H91), C93(H93), C94(H94), C101(H101), C103(H103), C104(H104), C111(H111),
 C112(H112), C113(H113), C123(H123), C124(H124), C125(H125), C135(H135),
 C137(H137), C138(H138), C145(H145), C147(H147), C148(H148), C155(H155),
 C156(H156), C157(H157), C167(H167), C168(H168), C169(H169)
5.c Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C28(H28A,H28B,H28C), C29(H29A,H29B,
 H29C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C52(H52A,H52B,H52C),
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C62(H62A,H62B,H62C), C63(H63A,H63B,
 H63C), C64(H64A,H64B,H64C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C75(H75A,
 H75B,H75C), C76(H76A,H76B,H76C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C),
 C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C96(H96A,H96B,H96C), C97(H97A,H97B,
 H97C), C98(H98A,H98B,H98C), C106(H10D,H10E,H10F), C107(H10G,H10H,H10I),
 C108(H10J,H10K,H10L), C116(H11A,H11B,H11C), C117(H11D,H11E,H11F), C119(H11G,
 H11H,H11I), C120(H12A,H12B,H12C), C128(H12D,H12E,H12F), C129(H12G,H12H,H12I),
 C131(H13A,H13B,H13C), C132(H13D,H13E,H13F), C140(H14A,H14B,H14C), C141(H14D,
 H14E,H14F), C142(H14G,H14H,H14I), C150(H15A,H15B,H15C), C151(H15D,H15E,H15F),
 C152(H15G,H15H,H15I), C160(H16A,H16B,H16C), C161(H16D,H16E,H16F), C163(H16G,
 H16H,H16I), C164(H16J,H16K,H16L), C172(H17A,H17B,H17C), C173(H17D,H17E,H17F),
 C175(H17G,H17H,H17I), C176(H17J,H17K,H17L), C231(H23A,H23B,H23C), C232(H23D,
 H23E,H23F), C272(H27A,H27B,H27C), C273(H27D,H27E,H27F), C275(H27G,H27H,H27I),
 C276(H27J,H27K,H27L), C18A(H18D,H18E,H18F), C19A(H19D,H19E,H19F), C20A(H20D,
 H20E,H20F), C72A(H72D,H72E,H72F), C73A(H73D,H73E,H73F), C40A(H40D,H40E,H40F)
;
_shelx_res_checksum              9676
_shelx_hkl_checksum              727
_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 1.453
_oxdiff_exptl_absorpt_empirical_full_min 0.802