Comparison of group 4 and thorium M(IV) substituted cyclopentadienyl silanide complexes
Réant, Benjamin Luke Leonard; De Alwis Jayasinghe, Dukula Prathapa Bilesha; Wooles, Ashley; Liddle, Stephen; Mills, David P.; Dalton Transactions  (2023) –; doi:10.1039/D3DT00987D

data_7713014
_publ_section_title
;
 Comparison of group 4 and thorium M(IV) substituted cyclopentadienyl
 silanide complexes
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT00987D
_journal_year                    2023
_chemical_formula_moiety         'C28 H61 Cl Hf Si7, 0.5(C5H12)'
_chemical_formula_sum            'C30.5 H67 Cl Hf Si7'
_chemical_formula_weight         844.41
_chemical_name_systematic        '[Hf(Cp'')(Cp')(Cl){Si(SiMe3)3}]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-12-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-03-28 deposited with the CCDC.	2023-05-12 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.0313(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.53762(7)
_cell_length_b                   16.04434(7)
_cell_length_c                   19.91805(9)
_cell_measurement_reflns_used    45346
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      76.0130
_cell_measurement_theta_min      2.2190
_cell_volume                     4260.11(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.27b (Rigaku OD, 2015)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.972
_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    -36.00 -10.00   1.00    1.00    --   44.70  60.00  60.00   26
  2  \w     33.00 106.00   1.00    1.00    --   44.70  20.00  60.00   73
  3  \w    -14.00  25.00   1.00    1.00    --   44.70  20.00  60.00   39
  4  \w      7.00 134.00   1.00    1.00    --   44.70  40.00 150.00  127
  5  \w     90.00 130.00   1.00    1.00    --   44.70  60.00  60.00   40
  6  \w    -44.00   2.00   1.00    1.00    --   44.70  40.00 150.00   46
  7  \w     19.00 141.00   1.00    1.00    --  108.20  30.00-150.00  122
  8  \w    119.00 189.00   1.00    1.00    --  108.20  50.00  90.00   70
  9  \w    116.00 156.00   1.00    1.00    --  108.20  30.00 120.00   40
 10  \w     77.00 109.00   1.00    1.00    --  108.20  50.00  90.00   32
 11  \w     47.00  74.00   1.00    1.00    --  108.20  50.00  90.00   27
 12  \w     29.00  55.00   1.00    1.00    --  108.20  30.00 120.00   26
 13  \w    128.00 194.00   1.00    1.00    --  108.20  50.00 150.00   66
 14  \w     24.00 161.00   1.00    1.00    --  108.20  40.00-180.00  137
 15  \w     23.00 168.00   1.00    1.00    --  108.20  50.00 120.00  145
 16  \w     13.00  47.00   1.00    1.00    --   44.70  60.00  90.00   34
 17  \w    -43.00  24.00   1.00    1.00    --   44.70   0.00 -90.00   67
 18  \w    104.00 134.00   1.00    1.00    --   44.70  30.00-120.00   30
 19  \w    -31.00  11.00   1.00    1.00    --   44.70  60.00  90.00   42
 20  \w     89.00 131.00   1.00    1.00    --   44.70   0.00 -90.00   42
 21  \w     40.00  84.00   1.00    1.00    --   44.70  30.00-120.00   44
 22  \w     88.00 131.00   1.00    1.00    --   44.70  60.00  90.00   43
 23  \w     19.00  54.00   1.00    1.00    --  108.20  50.00  30.00   35
 24  \w     19.00  44.00   1.00    1.00    --  108.20  50.00  60.00   25
 25  \w    124.00 160.00   1.00    1.00    --  108.20  50.00 -90.00   36
 26  \w     20.00 118.00   1.00    1.00    --  108.20  30.00  60.00   98
 27  \w    108.00 134.00   1.00    1.00    --  108.20  50.00  60.00   26
 28  \w    147.00 174.00   1.00    1.00    --  108.20  50.00  60.00   27
 29  \w     78.00 104.00   1.00    1.00    --  108.20  20.00  90.00   26
 30  \w    137.00 173.00   1.00    1.00    --  108.20  50.00-150.00   36
 31  \w     19.00  47.00   1.00    1.00    --  108.20  40.00  60.00   28
 32  \w     94.00 120.00   1.00    1.00    --  108.20  50.00 -90.00   26
 33  \w    144.00 170.00   1.00    1.00    --  108.20  50.00-180.00   26
 34  \w    140.00 167.00   1.00    1.00    --  108.20  50.00-120.00   27
 35  \w     19.00  46.00   1.00    1.00    --  108.20  50.00-180.00   27
 36  \w    113.00 138.00   1.00    1.00    --  108.20  20.00  90.00   25
 37  \w    148.00 174.00   1.00    1.00    --  108.20  50.00 -60.00   26
 38  \w    101.00 175.00   1.00    1.00    --  108.20  50.00  30.00   74
 39  \w    125.00 150.00   1.00    1.00    --  108.20  30.00  60.00   25
 40  \w     19.00  53.00   1.00    1.00    --  108.20  40.00  90.00   34
 41  \w     56.00 197.00   1.00    1.00    --  108.20  50.00   0.00  141
 42  \w     27.00  53.00   1.00    1.00    --  108.20  50.00 -90.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0590922000
_diffrn_orient_matrix_UB_12      0.0792836000
_diffrn_orient_matrix_UB_13      -0.0252756000
_diffrn_orient_matrix_UB_21      0.0992993000
_diffrn_orient_matrix_UB_22      0.0475214000
_diffrn_orient_matrix_UB_23      0.0015163000
_diffrn_orient_matrix_UB_31      0.0008562000
_diffrn_orient_matrix_UB_32      -0.0260753000
_diffrn_orient_matrix_UB_33      -0.0743394000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0421
_diffrn_reflns_av_unetI/netI     0.0178
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            54010
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.277
_diffrn_reflns_theta_min         4.591
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.119
_exptl_absorpt_correction_T_max  0.788
_exptl_absorpt_correction_T_min  0.111
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.27b (Rigaku Oxford Diffraction, 2015)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.317
_exptl_crystal_description       block
_exptl_crystal_F_000             1748
_exptl_crystal_preparation       -
_exptl_crystal_recrystallization_method
'Crystallised from concentrated pentane at -25 oC'
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.171
_exptl_crystal_size_min          0.164
_refine_diff_density_max         1.658
_refine_diff_density_min         -1.964
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.161
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     352
_refine_ls_number_reflns         8678
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.161
_refine_ls_R_factor_all          0.0329
_refine_ls_R_factor_gt           0.0329
_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^)+(0.0455P)^2^+6.6588P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0876
_refine_ls_wR_factor_ref         0.0876
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8669
_reflns_number_total             8678
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt00987d2.cif
_cod_data_source_block           3
_cod_original_cell_volume        4260.11(3)
_cod_original_formula_sum        'C30.50 H67 Cl Hf Si7'
_cod_database_code               7713014
_manchester_internal_diff_code   ldpm178
_manchester_internal_coll_client IV
_manchester_internal_coll_user   IV
_manchester_internal_coll_date   27/11/2020
_manchester_internal_process_date 27/11/2020
_manchester_internal_process_user BR
_manchester_internal_solution_date 11/12/2020
_manchester_internal_solution_user BR
_manchester_internal_refinement_date 11/12/2020
_manchester_internal_refinement_user BR
_manchester_internal_validation_date 15/12/2020
_manchester_internal_validation_user AW
_manchester_internal_archive_date 15/12/2020
_manchester_internal_archive_user AW
_platon_squeeze_void_probe_radius 1.20
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Hf1 Cl1 Si7 C28 '
_shelx_estimated_absorpt_t_max   0.388
_shelx_estimated_absorpt_t_min   0.190
_reflns_odcompleteness_completeness 98.51
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C23(H23), C24(H24)
2.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,
 H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C),
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C20(H20A,H20B,
 H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C)
;
_shelx_res_checksum              14281
_shelx_fab_checksum              8957
_manchester_internal_coll_frame_method '\w scans'
_manchester_internal_coll_frame_time 1s
_manchester_internal_coll_frame_width 1
_manchester_internal_coll_type   custom
_olex2_exptl_crystal_mounting_method 'Mounted from fomblin oil'
_olex2_submission_original_sample_id BR4.340
_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 2.343
_oxdiff_exptl_absorpt_empirical_full_min 0.480