Secondary-Sphere Preorganization Enables Nickel-Catalyzed Nitrile Hydroboration
Afandiyeva, Medina; Wu, Xijue; Brennessel, William W.; Kadam, Abhishek A.; Kennedy, C. Rose; Chemical Communications  (2023) –; doi:10.1039/D3CC04229D

data_7132235
_publ_section_title
;
 Secondary-Sphere Preorganization Enables Nickel-Catalyzed Nitrile
 Hydroboration
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC04229D
_journal_year                    2023
_chemical_formula_moiety         'C36 H52 B2 N4 Ni O5, 0.5(C6 D6)'
_chemical_formula_sum            'C39 H52 B2 D3 N4 Ni O5'
_chemical_formula_weight         743.22
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-03-27
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-01 deposited with the CCDC.	2023-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.5400(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.69320(10)
_cell_length_b                   15.81900(10)
_cell_length_c                   21.87530(10)
_cell_measurement_reflns_used    45389
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      79.5730
_cell_measurement_theta_min      3.4030
_cell_volume                     7936.33(8)
_computing_cell_refinement       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.85a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.85a (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 2019/2 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_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 0.982
_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   -120.00 -35.00   0.50    0.41    --  -47.28 -41.00-155.00  170
  2  \w    -42.00  25.00   0.50    0.41    --  -47.28  41.00  -2.00  134
  3  \w     35.00 120.00   0.50    0.41    --   47.28  41.00  -2.00  170
  4  \w    -25.00  46.00   0.50    0.41    --   47.28 -41.00-155.00  142
  5  \w   -164.00 -79.00   0.50    1.63    --  -91.75 -41.00-155.00  170
  6  \w    101.00 178.00   0.50    1.63    --  113.25  41.00  -2.00  154
  7  \w    -14.00  28.00   0.50    0.41    --  -47.28  19.00 150.00   84
  8  \w     34.00  93.00   0.50    0.41    --   47.28-125.00-180.00  118
  9  \w    -47.00 -20.00   0.50    1.63    --  -91.75  45.00-180.00   54
 10  \w     42.00  76.00   0.50    1.63    --  113.25 -61.00 -90.00   68
 11  \w     42.00  76.00   0.50    1.63    --  113.25 -61.00  60.00   68
 12  \w     42.00  76.00   0.50    1.63    --  113.25 -61.00-120.00   68
 13  \w     42.00  76.00   0.50    1.63    --  113.25 -61.00 -60.00   68
 14  \w     42.00  76.00   0.50    1.63    --  113.25 -61.00 -30.00   68
 15  \w     42.00 106.00   0.50    1.63    --  113.25 -94.00-120.00  128
 16  \w    101.00 178.00   0.50    1.63    --  113.25  45.00-120.00  154
 17  \w     44.00 111.00   0.50    1.63    --  113.25-125.00-180.00  134
 18  \w    100.00 178.00   0.50    1.63    --  113.25  15.00 120.00  156
 19  \w    100.00 178.00   0.50    1.63    --  113.25  15.00  60.00  156
 20  \w     42.00 136.00   0.50    1.63    --  113.25 -77.00-120.00  188
 21  \w     42.00  76.00   0.50    1.63    --  113.25 -61.00 150.00   68
 22  \w     42.00 106.00   0.50    1.63    --  113.25 -94.00 120.00  128
 23  \w     42.00  76.00   0.50    1.63    --  113.25 -61.00   0.00   68
 24  \w     42.00  76.00   0.50    1.63    --  113.25 -61.00  30.00   68
 25  \w     42.00  76.00   0.50    1.63    --  113.25 -61.00  90.00   68
 26  \w     42.00 106.00   0.50    1.63    --  113.25 -94.00   0.00  128
 27  \w     42.00 136.00   0.50    1.63    --  113.25 -77.00 150.00  188
 28  \w     34.00  93.00   0.50    0.41    --   47.28-125.00  30.00  118
 29  \w     32.00 120.00   0.50    0.41    --   47.28  57.00 150.00  176
 30  \w     25.00 120.00   0.50    0.41    --   47.28  77.00-180.00  190
 31  \w     32.00 120.00   0.50    0.41    --   47.28  57.00 -90.00  176
 32  \w     25.00 120.00   0.50    0.41    --   47.28  77.00  60.00  190
 33  \w     25.00 120.00   0.50    0.41    --   47.28  77.00 -60.00  190
 34  \w     35.00 120.00   0.50    0.41    --   47.28  38.00  90.00  170
 35  \w     25.00 120.00   0.50    0.41    --   47.28  77.00   0.00  190
 36  \w   -163.00-138.00   0.50    1.63    --  -91.75 -77.00 -90.00   50
 37  \w   -163.00 -69.00   0.50    1.63    --  -91.75 -77.00 120.00  188
 38  \w    101.00 178.00   0.50    1.63    --  113.25  30.00 -30.00  154
 39  \w    100.00 178.00   0.50    1.63    --  113.25  15.00-180.00  156
 40  \w    101.00 178.00   0.50    1.63    --  113.25  30.00 -60.00  154
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0659540000
_diffrn_orient_matrix_UB_12      0.0094934000
_diffrn_orient_matrix_UB_13      -0.0064592000
_diffrn_orient_matrix_UB_21      -0.0127598000
_diffrn_orient_matrix_UB_22      -0.0492436000
_diffrn_orient_matrix_UB_23      -0.0627151000
_diffrn_orient_matrix_UB_31      0.0000166000
_diffrn_orient_matrix_UB_32      -0.0834848000
_diffrn_orient_matrix_UB_33      0.0362944000
_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  0.0318
_diffrn_reflns_av_unetI/netI     0.0169
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            69642
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.698
_diffrn_reflns_theta_min         3.394
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.068
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88707
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.85a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       block
_exptl_crystal_F_000             3160
_exptl_crystal_size_max          0.168
_exptl_crystal_size_mid          0.136
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.359
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     502
_refine_ls_number_reflns         8562
_refine_ls_number_restraints     30
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0340
_refine_ls_R_factor_gt           0.0318
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0313P)^2^+8.4259P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0789
_refine_ls_wR_factor_ref         0.0801
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7959
_reflns_number_total             8562
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04229d2.cif
_cod_data_source_block           kenxw05
_cod_database_code               7132235
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.841
_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. Same fragment restrains
{C38, C39, C40, C41, C42, C37} sigma for 1-2: 0.02, 1-3: 0.04
{C42, C41, C40, C39, C38, C37} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C37, C38, C39, C40, C41, C42}
3. Others
 Fixed Sof: C37(0.5) D37(0.5) C38(0.5) D38(0.5) C39(0.5) D39(0.5) C40(0.5)
 D40(0.5) C41(0.5) D41(0.5) C42(0.5) D42(0.5)
4.a Ternary CH refined with riding coordinates:
 C19(H19)
4.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B)
4.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C14(H14), C15(H15), C16(H16), C37(D37),
 C38(D38), C39(D39), C40(D40), C41(D41), C42(D42)
4.d Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C33(H33A,
 H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C)
;
_shelx_res_checksum              44751
_shelx_hkl_checksum              15705
_olex2_submission_original_sample_id kenxw05
_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 1.238
_oxdiff_exptl_absorpt_empirical_full_min 0.822