Triborane (B<sub>3</sub>H<sub>7</sub>)-mediated regioselective substitution reactions of pyridine derivatives.
Fan, Zi-Heng; Kang, Jia-Xin; Jia, Sihan; Pan, Qiao-Jing; Cao, Lei; Chen, Xi-Meng; Xu, Cong-Qiao; Ma, Yan-Na; Chen, Xuenian; Chemical science 15 (2024) 13923–13929; doi:10.1039/d4sc03109a

data_1572200
_publ_section_title
;
 Triborane (B<sub>3</sub>H<sub>7</sub>)-mediated regioselective
 substitution reactions of pyridine derivatives.
;
_journal_issue                   34
_journal_name_full               'Chemical science'
_journal_page_first              13923
_journal_page_last               13929
_journal_paper_doi               10.1039/d4sc03109a
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C9 H20 B3 N'
_chemical_formula_sum            'C9 H20 B3 N'
_chemical_formula_weight         174.69
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-09-21
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-11-15 deposited with the CCDC.	2024-07-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.554(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.9799(3)
_cell_length_b                   8.8926(3)
_cell_length_c                   15.2066(4)
_cell_measurement_reflns_used    2304
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      71.0960
_cell_measurement_theta_min      5.1070
_cell_volume                     1169.85(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.982
_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    -71.00 -26.00   1.00    1.00    --  -35.62  92.00   0.00   45
  2  \w     -9.00  21.00   1.00    1.00    --  -35.62  92.00   0.00   30
  3  \w     58.00  84.00   1.00    2.38    --  106.81 -92.00-111.00   26
  4  \w    104.00 175.00   1.00    2.38    --  106.81  92.00   0.00   71
  5  \w    -70.00 -41.00   1.00    1.00    --  -35.62-178.00  60.00   29
  6  \w    -97.00 -21.00   1.00    1.00    --  -35.62 -57.00-180.00   76
  7  \w     27.00  68.00   1.00    1.00    --   35.62 -92.00-111.00   41
  8  \w     66.00  97.00   1.00    1.00    --   35.62 178.00 150.00   31
  9  \w     63.00 108.00   1.00    1.00    --   35.62-178.00-150.00   45
 10  \w     13.00  74.00   1.00    1.00    --   35.62 -99.00-180.00   61
 11  \w     64.00  91.00   1.00    2.38    --  106.81-111.00  90.00   27
 12  \w     38.00 124.00   1.00    2.38    --  106.81 -45.00 -90.00   86
 13  \w    120.00 150.00   1.00    2.38    --  106.81 111.00-180.00   30
 14  \w    105.00 170.00   1.00    2.38    --  106.81  77.00-150.00   65
 15  \w     39.00 103.00   1.00    2.38    --  106.81 -95.00 -60.00   64
 16  \w     41.00 125.00   1.00    2.38    --  106.81 -61.00  90.00   84
 17  \w    117.00 158.00   1.00    2.38    --  106.81  77.00  60.00   41
 18  \w    104.00 171.00   1.00    2.38    --  106.81  45.00 -60.00   67
;
_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      -0.0626711000
_diffrn_orient_matrix_UB_12      -0.0913880000
_diffrn_orient_matrix_UB_13      0.0685473000
_diffrn_orient_matrix_UB_21      0.0406417000
_diffrn_orient_matrix_UB_22      0.1304591000
_diffrn_orient_matrix_UB_23      0.0689911000
_diffrn_orient_matrix_UB_31      -0.1614743000
_diffrn_orient_matrix_UB_32      0.0680946000
_diffrn_orient_matrix_UB_33      -0.0401658000
_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  0.0187
_diffrn_reflns_av_unetI/netI     0.0244
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            4882
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.332
_diffrn_reflns_theta_min         5.113
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.383
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80007
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light white'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    0.992
_exptl_crystal_description       plate
_exptl_crystal_F_000             384
_exptl_crystal_size_max          0.001
_exptl_crystal_size_mid          0.001
_exptl_crystal_size_min          0.001
_refine_diff_density_max         0.140
_refine_diff_density_min         -0.144
_refine_diff_density_rms         0.026
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     169
_refine_ls_number_reflns         2230
_refine_ls_number_restraints     66
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0534
_refine_ls_R_factor_gt           0.0475
_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^)+(0.0737P)^2^+0.0791P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1362
_refine_ls_wR_factor_ref         0.1423
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1877
_reflns_number_total             2230
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03109a2.cif
_cod_data_source_block           20230920-fzh_auto
_cod_depositor_comments
'Adding full bibliography for 1572200--1572201.cif.'
_cod_database_code               1572200
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C1 N1 B1 O1 F1'
_shelx_estimated_absorpt_t_max   1.000
_shelx_estimated_absorpt_t_min   1.000
_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. Uiso/Uaniso restraints and constraints
C4: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C4 \\sim C1A \\sim C1 \\sim C7A \\sim C7: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
3. Rigid body (RIGU) restrains
 C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C4, C1A, C7A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C7, C1, C4
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Others
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C7)=Sof(H7C)=Sof(H7D)=Sof(H7E)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C1A(H1AA,H1AB)
5.b Aromatic/amide H refined with riding coordinates:
 C5(H5), C3(H3)
5.c Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C7(H7C,H7D,H7E), C7A(H7AA,H7AB,H7AC)
;
_smtbx_masks_void_probe_radius   0.3
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              7401
_shelx_hkl_checksum              76311
_shelx_fab_checksum              30147
_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 1.474
_oxdiff_exptl_absorpt_empirical_full_min 0.636