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_7132238
_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 H45 K N4 Ni O7, 2(C6 D6)'
_chemical_formula_sum            'C48 H45 D12 K N4 Ni O7'
_chemical_formula_weight         911.86
_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             2022-10-18
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-06-01 deposited with the CCDC.	2023-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.5160(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.32140(10)
_cell_length_b                   11.93520(10)
_cell_length_c                   25.59080(10)
_cell_measurement_reflns_used    47505
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      79.0430
_cell_measurement_theta_min      3.2530
_cell_volume                     4665.11(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_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 0.988
_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 -34.00   0.50    0.37    --  -47.28 -50.00 103.00  170
  2  \w    -54.00  25.00   0.50    0.37    --  -47.28  50.00-110.00  158
  3  \w    -24.00  58.00   0.50    0.37    --   47.28 -50.00 103.00  164
  4  \w     34.00 120.00   0.50    0.37    --   47.28  50.00-110.00  172
  5  \w    -54.00 -19.00   0.50    1.48    --  -91.75  50.00-110.00   70
  6  \w   -163.00 -78.00   0.50    1.48    --  -91.75 -50.00 103.00  170
  7  \w    100.00 178.00   0.50    1.48    --  113.25  50.00-110.00  156
  8  \w    -14.00  28.00   0.50    0.37    --  -47.28  19.00  30.00   84
  9  \w    -14.00  28.00   0.50    0.37    --  -47.28  19.00  60.00   84
 10  \w    -14.00  28.00   0.50    0.37    --  -47.28  19.00   0.00   84
 11  \w    -27.00  18.00   0.50    0.37    --   47.28 -19.00 120.00   90
 12  \w    -47.00 -20.00   0.50    1.48    --  -91.75  45.00  30.00   54
 13  \w    -47.00 -20.00   0.50    1.48    --  -91.75  45.00  90.00   54
 14  \w     42.00  76.00   0.50    1.48    --  113.25 -61.00  60.00   68
 15  \w     42.00  76.00   0.50    1.48    --  113.25 -61.00 -60.00   68
 16  \w     44.00 108.00   0.50    1.48    --  113.25-108.00 149.95  128
 17  \w     42.00  76.00   0.50    1.48    --  113.25 -61.00-120.00   68
 18  \w    101.00 178.00   0.50    1.48    --  113.25  30.00   0.00  154
 19  \w     42.00  76.00   0.50    1.48    --  113.25 -61.00 -30.00   68
 20  \w     42.00  76.00   0.50    1.48    --  113.25 -61.00-150.00   68
 21  \w     44.00 111.00   0.50    1.48    --  113.25-125.00 120.00  134
 22  \w     42.00 106.00   0.50    1.48    --  113.25 -94.00-150.00  128
 23  \w     42.00 106.00   0.50    1.48    --  113.25 -94.00 -30.00  128
 24  \w     42.00  76.00   0.50    1.48    --  113.25 -61.00  30.00   68
 25  \w     42.00  76.00   0.50    1.48    --  113.25 -61.00  90.00   68
 26  \w    100.00 178.00   0.50    1.48    --  113.25  15.00  90.00  156
 27  \w     42.00  76.00   0.50    1.48    --  113.25 -61.00-180.00   68
 28  \w    101.00 178.00   0.50    1.48    --  113.25  30.00  30.00  154
 29  \w    101.00 178.00   0.50    1.48    --  113.25  30.00 150.00  154
 30  \w     42.00 106.00   0.50    1.48    --  113.25 -94.00-180.00  128
 31  \w     42.00 106.00   0.50    1.48    --  113.25 -94.00 150.00  128
 32  \w     42.00  76.00   0.50    1.48    --  113.25 -61.00   0.00   68
 33  \w   -119.00 -25.00   0.50    0.37    --  -47.28 -77.00-150.00  188
 34  \w   -119.00 -25.00   0.50    0.37    --  -47.28 -77.00   0.00  188
 35  \w   -119.00 -25.00   0.50    0.37    --  -47.28 -77.00 -60.00  188
 36  \w   -119.00 -25.00   0.50    0.37    --  -47.28 -77.00  60.00  188
 37  \w     34.00  93.00   0.50    0.37    --   47.28-125.00 -30.00  118
 38  \w     32.00 120.00   0.50    0.37    --   47.28  57.00 -30.00  176
 39  \w   -163.00-119.00   0.50    1.48    --  -91.75 -76.00 -87.15   88
 40  \w   -163.00 -73.00   0.50    1.48    --  -91.75 -66.00 169.62  180
 41  \w    101.00 178.00   0.50    1.48    --  113.25  30.00-150.00  154
 42  \w     42.00  76.00   0.50    1.48    --  113.25 -61.00 -90.00   68
 43  \w    100.00 178.00   0.50    1.48    --  113.25  15.00 -30.00  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      0.0761580000
_diffrn_orient_matrix_UB_12      0.0790962000
_diffrn_orient_matrix_UB_13      -0.0104106000
_diffrn_orient_matrix_UB_21      -0.0268188000
_diffrn_orient_matrix_UB_22      -0.0048723000
_diffrn_orient_matrix_UB_23      -0.0592468000
_diffrn_orient_matrix_UB_31      -0.0604660000
_diffrn_orient_matrix_UB_32      0.1018876000
_diffrn_orient_matrix_UB_33      0.0052287000
_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  0.0379
_diffrn_reflns_av_unetI/netI     0.0206
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            81132
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.270
_diffrn_reflns_theta_min         3.253
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.829
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89067
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.298
_exptl_crystal_description       block
_exptl_crystal_F_000             1904
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.076
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.334
_refine_diff_density_min         -0.269
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     771
_refine_ls_number_reflns         10094
_refine_ls_number_restraints     316
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0347
_refine_ls_R_factor_gt           0.0317
_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^)+(0.0335P)^2^+2.0962P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0795
_refine_ls_wR_factor_ref         0.0812
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9202
_reflns_number_total             10094
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc04229d2.cif
_cod_data_source_block           kenaak15
_cod_database_code               7132238
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.898
_shelx_estimated_absorpt_t_min   0.797
_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
 O2-C36 \\sim O2'-C36'
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 0.8A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 0.8A
C43 \\sim C43': within 2A with sigma of 0.003 and sigma for terminal atoms of
0.006 within 2A
C44 \\sim C44': within 2A with sigma of 0.003 and sigma for terminal atoms of
0.006 within 2A
C48 \\sim C48': within 2A with sigma of 0.003 and sigma for terminal atoms of
0.006 within 2A
4. Same fragment restrains
{O2, C25, C26, O3, C27, C28, O4, C29, C30, O5, C31, C32, O6, C33, C34, O7, C35,
C36} sigma for 1-2: 0.02, 1-3: 0.04
as in
{O2', C25', C26', O3', C27', C28', O4', C29', C30', O5', C31', C32', O6', C33',
C34', O7', C35', C36'}
{C44, C45, C46, C47, C48, C43} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C43, C44, C45, C46, C47, C48}
{C43, C44, C45, C46, C47, C48} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C43', C44', C45', C46', C47', C48'}
5. Others
 Sof(O2')=Sof(C25')=Sof(H25C)=Sof(H25D)=Sof(C26')=Sof(H26C)=Sof(H26D)=Sof(O3')=
 Sof(C27')=Sof(H27C)=Sof(H27D)=Sof(C28')=Sof(H28C)=Sof(H28D)=Sof(O4')=Sof(C29')=
 Sof(H29C)=Sof(H29D)=Sof(C30')=Sof(H30C)=Sof(H30D)=Sof(O5')=Sof(C31')=Sof(H31C)=
 Sof(H31D)=Sof(C32')=Sof(H32C)=Sof(H32D)=Sof(O6')=Sof(C33')=Sof(H33C)=Sof(H33D)=
 Sof(C34')=Sof(H34C)=Sof(H34D)=Sof(O7')=Sof(C35')=Sof(H35C)=Sof(H35D)=Sof(C36')=
 Sof(H36C)=Sof(H36D)=1-FVAR(1)
 Sof(O2)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(O3)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(O4)=Sof(C29)=
 Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(O5)=Sof(C31)=Sof(H31A)=
 Sof(H31B)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(O6)=Sof(C33)=Sof(H33A)=Sof(H33B)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(O7)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(C36)=
 Sof(H36A)=Sof(H36B)=FVAR(1)
 Sof(C43')=Sof(D43')=Sof(C44')=Sof(D44')=Sof(C45')=Sof(D45')=Sof(C46')=
 Sof(D46')=Sof(C47')=Sof(D47')=Sof(C48')=Sof(D48')=1-FVAR(2)
 Sof(C43)=Sof(D43)=Sof(C44)=Sof(D44)=Sof(C45)=Sof(D45)=Sof(C46)=Sof(D46)=
 Sof(C47)=Sof(D47)=Sof(C48)=Sof(D48)=FVAR(2)
6.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), C25'(H25C,H25D), C26'(H26C,
 H26D), C27'(H27C,H27D), C28'(H28C,H28D), C29'(H29C,H29D), C30'(H30C,H30D),
 C31'(H31C,H31D), C32'(H32C,H32D), C33'(H33C,H33D), C34'(H34C,H34D), C35'(H35C,
 H35D), C36'(H36C,H36D)
6.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), C22(H22), C23(H23), C24(H24), C43(D43), C44(D44), C45(D45), C46(D46),
  C47(D47), C48(D48), C43'(D43'), C44'(D44'), C45'(D45'), C46'(D46'),
 C47'(D47'), C48'(D48'), C37(D37), C38(D38), C39(D39), C40(D40), C41(D41),
 C42(D42)
6.c Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
;
_shelx_res_checksum              92215
_shelx_hkl_checksum              59011
_olex2_submission_original_sample_id kenaak15
_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 1.164
_oxdiff_exptl_absorpt_empirical_full_min 0.843