Metal-catalyzed B–H acylmethylation of pyridylcarboranes: access to carborane-fused indoliziniums and quinoliziniums
Cao, Hou-Ji; Wei, Xing; Sun, Fangxiang; Zhang, Xiaolei; Lu, Changsheng; Yan, Hong; Chemical Science  (2021) –; doi:10.1039/D1SC05296A

data_1565423
_publ_section_title
;
 Metal-catalyzed B--H acylmethylation of pyridylcarboranes: access to
 carborane-fused indoliziniums and quinoliziniums
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC05296A
_journal_year                    2021
_chemical_formula_moiety         'C16 H22 B10 O'
_chemical_formula_sum            'C16 H22 B10 O'
_chemical_formula_weight         338.43
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-14
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.06.18 svn.r64d69d6c for OlexSys, GUI svn.r6354)
;
_audit_update_record
;
2021-09-17 deposited with the CCDC.	2021-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                70.744(18)
_cell_angle_beta                 72.905(18)
_cell_angle_gamma                70.884(19)
_cell_formula_units_Z            4
_cell_length_a                   12.097(8)
_cell_length_b                   13.280(10)
_cell_length_c                   13.603(9)
_cell_measurement_reflns_used    1799
_cell_measurement_temperature    296.15
_cell_measurement_theta_max      24.69
_cell_measurement_theta_min      2.17
_cell_volume                     1906(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2016/6 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.986
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0967
_diffrn_reflns_av_unetI/netI     0.1944
_diffrn_reflns_Laue_measured_fraction_full 0.986
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            13580
_diffrn_reflns_point_group_measured_fraction_full 0.626
_diffrn_reflns_point_group_measured_fraction_max 0.602
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.687
_diffrn_reflns_theta_min         2.011
_diffrn_source_current           40.0
_diffrn_source_power             2.0
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.062
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4264
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1223 before and 0.0804 after correction.
The Ratio of minimum to maximum transmission is 0.5719.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.179
_exptl_crystal_description       block
_exptl_crystal_F_000             704
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.476
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.084
_refine_ls_abs_structure_details
;
 Flack x determined using 671 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   1.9(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.987
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     973
_refine_ls_number_reflns         10731
_refine_ls_number_restraints     53
_refine_ls_restrained_S_all      0.989
_refine_ls_R_factor_all          0.2331
_refine_ls_R_factor_gt           0.1150
_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^)+(0.1449P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2620
_refine_ls_wR_factor_ref         0.3313
_reflns_Friedel_coverage         0.248
_reflns_Friedel_fraction_full    0.267
_reflns_Friedel_fraction_max     0.239
_reflns_number_gt                4293
_reflns_number_total             10731
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc05296a2.cif
_cod_data_source_block           7K
_cod_original_cell_volume        1907(2)
_cod_database_code               1565423
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.991
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
2. Rigid bond restraints
 O1B, C9B, C10B, C11B, C11B, C12B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.004
3. Uiso/Uaniso restraints and constraints
Uanis(C9A) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(C8B) \\sim Ueq, Uanis(C8C)
\\sim Ueq, Uanis(C10B) \\sim Ueq, Uanis(B4B) \\sim Ueq, Uanis(B12B) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Secondary CH2 refined with riding coordinates:
 C9(H9B,H9C), C9A(H9AA,H9AB), C9B(H9BB,H9BC), C9C(H9CA,H9CB)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7B), C8(H8), C12(H12), C13(H13), C14(H14),
 C15(H15), C16(H16), C4A(H4A), C5A(H5AA), C6A(H6AA), C7A(H7AA), C8A(H8AA),
 C12A(H12A), C13A(H13A), C14A(H14A), C15A(H15A), C16A(H16A), C4B(H4B),
 C5B(H5BA), C6B(H6BA), C7B(H7BA), C8B(H8BA), C12B(H12D), C13B(H13B), C14B(H14B),
  C15B(H15B), C16B(H16B), C4C(H4C), C5C(H5CA), C6C(H6C), C7C(H7C), C8C(H8CA),
 C12C(H12F), C13C(H13C), C14C(H14C), C15C(H15C), C16C(H16C)
4.c Boron cage BH refined with riding coordinates:
 C1(H1), B3(H3), B5(H5B), B6(H6B), B7(H7), B8(H8B), B9(H9), B10(H10), B11(H11),
  B12(H12C), C1A(H1A), B3A(H3A), B5A(H5A), B6A(H6A), B7A(H7A), B8A(H8A),
 B9A(H9A), B10A(H10A), B11A(H11A), B12A(H12B), C1B(H1B), B3B(H3B), B5B(H5BB),
 B6B(H6BB), B7B(H7BB), B8B(H8BB), B9B(H9BA), B10B(H10B), B11B(H11B), B12B(H12E),
  C1C(H1C), B3C(H3C), B5C(H5C), B6C(H6CA), B7C(H7CA), B8C(H8C), B9C(H9CC),
 B10C(H10C), B11C(H11C), B12C(H12G)
;
_shelx_res_checksum              36845
_olex2_submission_special_instructions 'No special instructions were received'