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_7132327
_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         'C52 H74 B Li N2 O3, C3 H7'
_chemical_formula_sum            'C55 H81 B Li N2 O3'
_chemical_formula_weight         835.96
_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             2023-10-17
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2023-10-17 deposited with the CCDC.	2023-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.504(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.7476(2)
_cell_length_b                   17.0185(3)
_cell_length_c                   26.4191(7)
_cell_measurement_reflns_used    5535
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      71.8400
_cell_measurement_theta_min      4.2500
_cell_volume                     5236.64(19)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_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_area_resol_mean 8.1297
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.969
_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  99.00   1.00   20.00    --   36.95  57.00 150.00   79
  2  \w     43.00 106.00   1.00   20.00    --   36.95  19.00  90.00   63
  3  \w    -27.00  63.00   1.00   20.00    --   36.95 -19.00-120.00   90
  4  \w      8.00  37.00   1.00   20.00    --   36.95  19.00  90.00   29
  5  \w     35.00  88.00   1.00   20.00    --   36.95-125.00  90.00   53
  6  \w     92.00 169.00   1.00  120.00    --  111.00  38.00  60.00   77
  7  \w     43.00 100.00   1.00  120.00    --  111.00 -92.00-120.00   57
  8  \w     87.00 178.00   1.00  120.00    --  111.00  25.00 120.00   91
  9  \w     43.00 100.00   1.00  120.00    --  111.00 -92.00  60.00   57
 10  \w    104.00 177.00   1.00  120.00    --  111.00 111.00 -60.00   73
 11  \w    104.00 172.00   1.00  120.00    --  111.00 111.00 150.00   68
 12  \w     45.00  90.00   1.00  120.00    --  111.00 -92.00 120.00   45
 13  \w    119.00 149.00   1.00  120.00    --  111.00 111.00  60.00   30
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0255
_diffrn_reflns_av_unetI/netI     0.0474
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            19495
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.778
_diffrn_reflns_theta_min         3.947
_exptl_absorpt_coefficient_mu    0.481
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81345
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (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    1.060
_exptl_crystal_description       plate
_exptl_crystal_F_000             1828
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.481
_refine_diff_density_min         -0.410
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     677
_refine_ls_number_reflns         10266
_refine_ls_number_restraints     294
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0865
_refine_ls_R_factor_gt           0.0644
_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^)+(0.0960P)^2^+1.0606P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1666
_refine_ls_wR_factor_ref         0.1838
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7575
_reflns_number_total             10266
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc05182j2.cif
_cod_data_source_block           4
_cod_database_code               7132327
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.897
_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
 C46-C45 = C47-C46 = C48-C47 = C50-C49 = C51-C50 = C52-C51
 1.5 with sigma of 0.008
 O3-C52 = O3-C49 = O2-C48 = O2-C45
 1.4 with sigma of 0.008
 C49A-C50A = C50A-C51A = C51A-C52A
 1.5 with sigma of 0.008
 O3-C52A = O3-C49A
 1.4 with sigma of 0.02
 O2-C45A = O2-C48A
 1.4 with sigma of 0.008
 C48A-C47A = C46A-C45A = C47A-C46A
 1.5 with sigma of 0.008
 C54-C53 = C55-C54 = C54A-C53A = C55A-C54A = C55_$1-C55 = C55A_$1-C55A
 1.53 with sigma of 0.008
 C53-C55 = C53A-C55A = C54-C55_$1 = C54A-C55A_$1
 2.5 with sigma of 0.008
3. Uiso/Uaniso restraints and constraints
O2 \\sim C45A \\sim C45 \\sim C46A \\sim C46 \\sim C47A \\sim C47 \\sim C48A
\\sim C48: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
within 2A
C52 \\sim O3 \\sim C52A \\sim C51 \\sim C51A \\sim C50 \\sim C50A \\sim C49
\\sim C49A: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
within 2A
C53A \\sim C54A \\sim C55A: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C53 \\sim C54 \\sim C55: within 2A with sigma of 0.005 and sigma for terminal
atoms of 0.01 within 2A
4. Others
 Sof(C46A)=Sof(H46C)=Sof(H46D)=Sof(C47A)=Sof(H47C)=Sof(H47D)=Sof(C45A)=
 Sof(H45C)=Sof(H45D)=Sof(C48A)=Sof(H48C)=Sof(H48D)=1-FVAR(1)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C47)=Sof(H47A)=
 Sof(H47B)=Sof(C46)=Sof(H46A)=Sof(H46B)=FVAR(1)
 Sof(C50A)=Sof(H50C)=Sof(H50D)=Sof(C49A)=Sof(H49C)=Sof(H49D)=Sof(C52A)=
 Sof(H52C)=Sof(H52D)=Sof(C51A)=Sof(H51C)=Sof(H51D)=1-FVAR(2)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(C51)=Sof(H51A)=
 Sof(H51B)=Sof(C50)=Sof(H50A)=Sof(H50B)=FVAR(2)
 Sof(C54A)=Sof(H54C)=Sof(H54D)=Sof(C55A)=Sof(H55C)=Sof(H55D)=Sof(C53A)=
 Sof(H53D)=Sof(H53E)=Sof(H53F)=1-FVAR(3)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C54)=
 Sof(H54A)=Sof(H54B)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C30(H30), C27(H27), C39(H39), C42(H42)
5.b Secondary CH2 refined with riding coordinates:
 C45(H45A,H45B), C48(H48A,H48B), C52(H52A,H52B), C49(H49A,H49B), C51(H51A,
 H51B), C50(H50A,H50B), C47(H47A,H47B), C46(H46A,H46B), C50A(H50C,H50D),
 C49A(H49C,H49D), C52A(H52C,H52D), C51A(H51C,H51D), C46A(H46C,H46D), C47A(H47C,
 H47D), C45A(H45C,H45D), C48A(H48C,H48D), C55(H55A,H55B), C54(H54A,H54B),
 C54A(H54C,H54D), C55A(H55C,H55D)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C2(H2), C5(H5), C23(H23), C11(H11), C4(H4), C25(H25), C24(H24),
 C10(H10), C37(H37), C35(H35), C36(H36)
5.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C28(H28A,H28B,H28C), C31(H31A,H31B,H31C), C41(H41A,H41B,
 H41C), C32(H32A,H32B,H32C), C29(H29A,H29B,H29C), C14(H14A,H14B,H14C), C18(H18A,
 H18B,H18C), C44(H44A,H44B,H44C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C),
 C15(H15A,H15B,H15C), C43(H43A,H43B,H43C), C16(H16A,H16B,H16C), C53(H53A,H53B,
 H53C), C53A(H53D,H53E,H53F)
;
_shelx_res_checksum              31594
_shelx_hkl_checksum              28563
_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
;