A two-coordinate Ni(I) silyl complex: CO2 insertion and oxidatively-induced silyl migrations
Witzke, Ryan J.; Tilley, T. Don; Chemical Communications  (2019) –; doi:10.1039/C9CC03128F

data_7123416
_publ_section_title
;
 A two-coordinate Ni(I) silyl complex: CO2 insertion and
 oxidatively-induced silyl migrations
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/C9CC03128F
_journal_year                    2019
_chemical_formula_moiety         'C27 H67 Ni P2 Si4, B C24 F20'
_chemical_formula_sum            'C51 H67 B F20 Ni P2 Si4'
_chemical_formula_weight         1303.86
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2019-01-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-02-11 deposited with the CCDC.    2019-05-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.410(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.5880(5)
_cell_length_b                   27.7435(9)
_cell_length_c                   17.8008(6)
_cell_measurement_reflns_used    13075
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.7500
_cell_measurement_theta_min      2.9630
_cell_volume                     5993.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -40.00 -15.00   0.50    3.50    --  -13.60 -19.00  77.00   50
  2  \w    -15.00  37.00   0.50    3.50    --  -13.60 -99.00   0.00  104
  3  \w    -15.00  30.00   0.50    3.50    --  -13.60 -99.00 120.00   90
  4  \w    -48.00  72.00   0.50    3.50    --  -13.60  38.00 -60.00  240
  5  \w     40.00  66.00   0.50    3.50    --   13.83 179.00 -30.00   52
  6  \w     42.00 103.00   0.50    3.50    --   13.83 179.00 -90.00  122
  7  \w     38.00  86.00   0.50    3.50    --   13.83 179.00 -60.00   96
  8  \w    -50.00 -24.00   0.50    3.50    --   13.83  19.00-114.00   52
  9  \w   -100.00 -50.00   0.50    3.50    --  -13.60  19.00-114.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0493217000
_diffrn_orient_matrix_UB_12      0.0060066000
_diffrn_orient_matrix_UB_13      -0.0099516000
_diffrn_orient_matrix_UB_21      -0.0279083000
_diffrn_orient_matrix_UB_22      -0.0020601000
_diffrn_orient_matrix_UB_23      -0.0400954000
_diffrn_orient_matrix_UB_31      -0.0142823000
_diffrn_orient_matrix_UB_32      0.0247730000
_diffrn_orient_matrix_UB_33      -0.0009105000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0844
_diffrn_reflns_av_unetI/netI     0.0879
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            50009
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         2.832
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.554
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79251
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.445
_exptl_crystal_description       block
_exptl_crystal_F_000             2688
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: ortho-difluorobenzene and pentane'
_exptl_crystal_size_max          0.198
_exptl_crystal_size_mid          0.167
_exptl_crystal_size_min          0.136
_refine_diff_density_max         1.033
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     744
_refine_ls_number_reflns         10967
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.1011
_refine_ls_R_factor_gt           0.0562
_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^)+(0.0631P)^2^+2.2169P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1202
_refine_ls_wR_factor_ref         0.1352
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7188
_reflns_number_total             10967
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9cc03128f2.cif
_cod_data_source_block           rjw6042_orange
_cod_database_code               7123416
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Ni Si P C B F H'
_reflns_odcompleteness_completeness 99.78
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B), C26(H26A,H26B)
2.b Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C12(H12A,H12B,H12C), C24(H24A,H24B,H24C), C23(H23A,H23B,
 H23C), C13(H13A,H13B,H13C), C9(H9A,H9B,H9C), C25(H25A,H25B,H25C), C3(H3A,H3B,
 H3C), C16(H16A,H16B,H16C), C20(H20A,H20B,H20C), C19(H19A,H19B,H19C), C11(H11A,
 H11B,H11C), C15(H15A,H15B,H15C), C4(H4A,H4B,H4C), C21(H21A,H21B,H21C),
 C17(H17A,H17B,H17C), C7(H7A,H7B,H7C), C2(H2A,H2B,H2C), C6(H6A,H6B,H6C), C5(H5A,
 H5B,H5C)
;
_shelx_res_checksum              8062
_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 2.568
_oxdiff_exptl_absorpt_empirical_full_min 0.415