Electronic structure comparisons of isostructural early d- and f-block metal(iii) bis(cyclopentadienyl) silanide complexes.
Gransbury, Gemma K.; Réant, Benjamin L L; Wooles, Ashley J.; Emerson-King, Jack; Chilton, Nicholas F.; Liddle, Stephen T.; Mills, David P.; Chemical science 14 (2023) 621–634; doi:10.1039/d2sc04526e

data_1568053
_publ_section_title
;
 Electronic structure comparisons of isostructural early d- and f-block
 metal(iii) bis(cyclopentadienyl) silanide complexes.
;
_journal_issue                   3
_journal_name_full               'Chemical science'
_journal_page_first              621
_journal_page_last               634
_journal_paper_doi               10.1039/d2sc04526e
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C31 H69 Si8 Zr'
_chemical_formula_sum            'C31 H69 Si8 Zr'
_chemical_formula_weight         757.80
_chemical_name_systematic        '[Zr(Cp'')2{Si(SiMe3)3}]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-12-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-08-08 deposited with the CCDC.	2022-12-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   37.0378(4)
_cell_length_b                   11.77080(10)
_cell_length_c                   20.1996(3)
_cell_measurement_reflns_used    22918
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.3430
_cell_measurement_theta_min      3.9210
_cell_volume                     8806.31(18)
_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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.961
_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     54.00  81.00   1.00    1.00    --   44.70  60.00-120.00   27
  2  \w     89.00 134.00   1.00    1.00    --   44.70  60.00  90.00   45
  3  \w    -44.00  65.00   1.00    1.00    --   44.70  60.00 -60.00  109
  4  \w     63.00 125.00   1.00    1.00    --   44.70  30.00 -60.00   62
  5  \w    -45.00  53.00   1.00    1.00    --   44.70  60.00-120.00   98
  6  \w    -11.00  16.00   1.00    1.00    --   44.70  60.00  90.00   27
  7  \w     82.00 131.00   1.00    1.00    --  108.20  50.00  30.00   49
  8  \w     83.00 197.00   1.00    1.00    --  108.20  50.00 -90.00  114
  9  \w     26.00  52.00   1.00    1.00    --  108.20  50.00  60.00   26
 10  \w     62.00 197.00   1.00    1.00    --  108.20  50.00 -30.00  135
 11  \w     19.00 198.00   1.00    1.00    --  108.20   0.00-150.00  179
 12  \w    133.00 198.00   1.00    1.00    --  108.20  50.00  30.00   65
 13  \w    112.00 156.00   1.00    1.00    --  108.20  50.00 -60.00   44
 14  \w    103.00 162.00   1.00    1.00    --  108.20  50.00  60.00   59
;
_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      -0.0414330000
_diffrn_orient_matrix_UB_12      -0.0109002000
_diffrn_orient_matrix_UB_13      -0.0011861000
_diffrn_orient_matrix_UB_21      0.0034517000
_diffrn_orient_matrix_UB_22      -0.1304616000
_diffrn_orient_matrix_UB_23      -0.0011430000
_diffrn_orient_matrix_UB_31      -0.0005339000
_diffrn_orient_matrix_UB_32      -0.0020679000
_diffrn_orient_matrix_UB_33      0.0762453000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0393
_diffrn_reflns_av_unetI/netI     0.0367
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       45
_diffrn_reflns_limit_h_min       -46
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            57189
_diffrn_reflns_point_group_measured_fraction_full 0.826
_diffrn_reflns_point_group_measured_fraction_max 0.788
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.347
_diffrn_reflns_theta_min         2.386
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.260
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.420
_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 dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.143
_exptl_crystal_description       needle
_exptl_crystal_F_000             3256
_exptl_crystal_preparation       -
_exptl_crystal_recrystallization_method
'Crystallised from concentrated pentane solution at -25 oC'
_exptl_crystal_size_max          0.249
_exptl_crystal_size_mid          0.106
_exptl_crystal_size_min          0.065
_refine_diff_density_max         1.684
_refine_diff_density_min         -0.716
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.480(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     764
_refine_ls_number_reflns         14550
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0398
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0560P)^2^+11.3200P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1029
_refine_ls_wR_factor_ref         0.1045
_reflns_Friedel_coverage         0.593
_reflns_Friedel_fraction_full    0.659
_reflns_Friedel_fraction_max     0.604
_reflns_number_gt                13759
_reflns_number_total             14550
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04526e2.cif
_cod_data_source_block           3-Zr
_cod_depositor_comments
'Adding full bibliography for 1568047--1568055.cif.'
_cod_database_code               1568053
_manchester_internal_diff_code   ldpm172
_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 09/12/2020
_manchester_internal_solution_user BR
_manchester_internal_refinement_date 09/12/2020
_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
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Zr1 Si8 C31'
_shelx_estimated_absorpt_t_max   0.769
_shelx_estimated_absorpt_t_min   0.417
_reflns_odcompleteness_completeness 97.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.52
 0.48
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C20(H20), C21(H21), C26(H26), C27(H27), C45(H45),
 C46(H46), C51(H51), C52(H52), C57(H57), C58(H58)
3.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), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C23(H23A,H23B,H23C), C24(H24A,
 H24B,H24C), C25(H25A,H25B,H25C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,
 H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C),
 C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C48(H48A,H48B,H48C), C49(H49A,H49B,
 H49C), C50(H50A,H50B,H50C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,
 H56B,H56C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C)
;
_shelx_res_checksum              49954
_shelx_hkl_checksum              31774
_olex2_exptl_crystal_mounting_method 'Mounted from fomblin oil'
_olex2_submission_original_sample_id BR4.352
_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 1.492
_oxdiff_exptl_absorpt_empirical_full_min 0.696