Nitrile formation via dichlorocarbene insertion into the Si-N bond of Ln(III) bis(trimethylsilyl)amide complexes
Li, Yangjuan; Gong, Yu; Chemical Communications  (2022) –; doi:10.1039/D2CC04538A

data_7130879
_publ_section_title
;
 Nitrile formation via dichlorocarbene insertion into the Si-N bond of
 Ln(III) bis(trimethylsilyl)amide complexes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC04538A
_journal_year                    2022
_chemical_formula_moiety         'C32 H90 Cl2 N6 Si10 Sm2'
_chemical_formula_sum            'C32 H90 Cl2 N6 Si10 Sm2'
_chemical_formula_weight         1211.59
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-13
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-07-13 deposited with the CCDC.	2022-10-18 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.368(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.8019(3)
_cell_length_b                   11.9155(2)
_cell_length_c                   25.0378(4)
_cell_measurement_reflns_used    26827
_cell_measurement_temperature    179.99(10)
_cell_measurement_theta_max      31.0580
_cell_measurement_theta_min      1.9620
_cell_volume                     6195.28(17)
_computing_cell_refinement       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.109a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179.99(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 0.804
_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    -68.00 -43.00   0.50    1.20    --    4.55 -38.00   0.00   50
  2  \w    -81.00   8.00   0.50    1.20    --   -6.43 -14.00  48.00  178
  3  \w    -68.00  27.00   0.50    1.20    --    4.55 -77.00 120.00  190
  4  \w    -18.00  27.00   0.50    1.20    --   -6.43 -99.00   0.00   90
  5  \w    -21.00  69.00   0.50    1.20    --   -6.43  14.00-140.00  180
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0146359000
_diffrn_orient_matrix_UB_12      0.0074281000
_diffrn_orient_matrix_UB_13      -0.0246357000
_diffrn_orient_matrix_UB_21      -0.0302783000
_diffrn_orient_matrix_UB_22      -0.0080125000
_diffrn_orient_matrix_UB_23      -0.0140265000
_diffrn_orient_matrix_UB_31      -0.0060200000
_diffrn_orient_matrix_UB_32      0.0585075000
_diffrn_orient_matrix_UB_33      0.0012095000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0237
_diffrn_reflns_av_unetI/netI     0.0185
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.804
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            37264
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.804
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.102
_diffrn_reflns_theta_min         1.961
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.182
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52390
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.109a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.299
_exptl_crystal_description       block
_exptl_crystal_F_000             2488
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.370
_refine_diff_density_min         -0.454
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     250
_refine_ls_number_reflns         8020
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0238
_refine_ls_R_factor_gt           0.0201
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0158P)^2^+6.4804P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0435
_refine_ls_wR_factor_ref         0.0445
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7259
_reflns_number_total             8020
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc04538a2.cif
_cod_data_source_block           yj-657_auto
_cod_database_code               7130879
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Sm1C1N1Si1Cl1H1
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2.a Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C),
 C14(H14A,H14B,H14C), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C15(H15A,H15B,H15C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C11(H11A,H11B,H11C), C16(H16A,H16B,
 H16C), C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C3(H3A,H3B,H3C)
;
_shelx_res_checksum              58282
_shelx_hkl_checksum              86099
_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 1.594
_oxdiff_exptl_absorpt_empirical_full_min 0.763