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_7132236
_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 H44 F K N4 Ni O7, C2 D3 N'
_chemical_formula_sum            'C38 H44 D3 F K N5 Ni O7'
_chemical_formula_weight         805.63
_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
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-03-31
_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                 98.8823(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.20850(11)
_cell_length_b                   30.7037(3)
_cell_length_c                   11.62735(12)
_cell_measurement_reflns_used    30803
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.2650
_cell_measurement_theta_min      4.0990
_cell_volume                     3953.48(7)
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.984
_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   -119.00 -32.00   0.50    1.89    --  -47.16 -56.00 151.00  174
  2  \w    -62.00  25.00   0.50    1.89    --  -47.16  56.00 -66.00  174
  3  \w    -24.00  62.00   0.50    1.89    --   47.16 -56.00 151.00  172
  4  \w     33.00 120.00   0.50    1.89    --   47.16  56.00 -66.00  174
  5  \w    -14.00  28.00   0.50    1.89    --  -47.16  19.00  90.00   84
  6  \w    -86.00 -13.00   0.50    1.89    --  -47.16 125.00  60.00  146
  7  \w     25.00 120.00   0.50    1.89    --   47.16  77.00  90.00  190
  8  \w     25.00 120.00   0.50    1.89    --   47.16  77.00-150.00  190
  9  \w     25.00 120.00   0.50    1.89    --   47.16  77.00   0.00  190
 10  \w     32.00 120.00   0.50    1.89    --   47.16  57.00-180.00  176
 11  \w     34.00  93.00   0.50    1.89    --   47.16-125.00   0.00  118
 12  \w     25.00 120.00   0.50    1.89    --   47.16  77.00  30.00  190
 13  \w     25.00 120.00   0.50    1.89    --   47.16  77.00 -60.00  190
 14  \w    -63.00 -19.00   0.50    7.58    --  -91.75  56.00 -66.00   88
 15  \w   -163.00 -77.00   0.50    7.58    --  -91.75 -56.00 151.00  172
 16  \w    -47.00 -20.00   0.50    7.58    --  -91.75  45.00 150.00   54
 17  \w    -47.00 -20.00   0.50    7.58    --  -91.75  45.00 120.00   54
 18  \w    -47.00 -20.00   0.50    7.58    --  -91.75  45.00  90.00   54
 19  \w   -163.00-138.00   0.50    7.58    --  -91.75 -69.00-150.78   50
 20  \w     99.00 178.00   0.50    7.58    --  113.25  56.00 -66.00  158
 21  \w     42.00 106.00   0.50    7.58    --  113.25 -94.00 -90.00  128
 22  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00 150.00   68
 23  \w     97.00 178.00   0.50    7.58    --  113.25  61.00   0.00  162
 24  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00-180.00   68
 25  \w     95.00 178.00   0.50    7.58    --  113.25 125.00-180.00  166
 26  \w    100.00 178.00   0.50    7.58    --  113.25  15.00  60.00  156
 27  \w     42.00 106.00   0.50    7.58    --  113.25 -94.00 -30.00  128
 28  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00 120.00   68
 29  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00  60.00   68
 30  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00 -60.00   68
 31  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00-120.00   68
 32  \w    100.00 178.00   0.50    7.58    --  113.25  15.00-150.00  156
 33  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00   0.00   68
 34  \w     44.00 111.00   0.50    7.58    --  113.25-125.00   0.00  134
 35  \w    101.00 178.00   0.50    7.58    --  113.25  45.00 -30.00  154
 36  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00-150.00   68
 37  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00 -90.00   68
 38  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00  90.00   68
 39  \w     43.00 107.00   0.50    7.58    --  113.25-104.00-121.39  128
 40  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00  30.00   68
 41  \w     42.00  76.00   0.50    7.58    --  113.25 -61.00 -30.00   68
 42  \w    101.00 178.00   0.50    7.58    --  113.25  30.00 120.00  154
 43  \w    100.00 178.00   0.50    7.58    --  113.25  15.00 -90.00  156
;
_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      -0.0520032000
_diffrn_orient_matrix_UB_12      0.0250091000
_diffrn_orient_matrix_UB_13      0.0959077000
_diffrn_orient_matrix_UB_21      0.1225594000
_diffrn_orient_matrix_UB_22      0.0228148000
_diffrn_orient_matrix_UB_23      0.0357512000
_diffrn_orient_matrix_UB_31      -0.0402749000
_diffrn_orient_matrix_UB_32      0.0370354000
_diffrn_orient_matrix_UB_33      -0.0866893000
_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  0.0457
_diffrn_reflns_av_unetI/netI     0.0274
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            62996
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.220
_diffrn_reflns_theta_min         4.109
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.135
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65431
_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    1.354
_exptl_crystal_description       needle
_exptl_crystal_F_000             1688
_exptl_crystal_size_max          0.267
_exptl_crystal_size_mid          0.031
_exptl_crystal_size_min          0.026
_refine_diff_density_max         0.334
_refine_diff_density_min         -0.651
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     482
_refine_ls_number_reflns         8506
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.0442
_refine_ls_R_factor_gt           0.0365
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0460P)^2^+1.9199P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0946
_refine_ls_wR_factor_ref         0.0985
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7281
_reflns_number_total             8506
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04229d2.cif
_cod_data_source_block           kenma09
_cod_database_code               7132236
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.600
_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.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,
 H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B),
 C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C8(H8), C14(H14), C15(H15), C16(H16), C20(H20),
 C21(H21), C23(H23), C24(H24)
2.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C38(D38A,D38B,
 D38C)
;
_shelx_res_checksum              56104
_shelx_hkl_checksum              20181
_olex2_submission_original_sample_id kenma09
_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 1.591
_oxdiff_exptl_absorpt_empirical_full_min 0.523