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_1568052
_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 Ce Si8'
_chemical_formula_sum            'C31 H69 Ce Si8'
_chemical_formula_weight         806.70
_chemical_name_systematic        '[Ce(C5H3-1,3-SiMe3)2{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             2020-10-02
_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                 111.045(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.8079(6)
_cell_length_b                   13.2758(3)
_cell_length_c                   20.3529(6)
_cell_measurement_reflns_used    12561
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.3580
_cell_measurement_theta_min      2.8250
_cell_volume                     4490.8(2)
_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 0.980
_diffrn_measured_fraction_theta_max 0.955
_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   -134.00 -58.00   1.00    1.00    --  -45.40 -76.00 -30.00   76
  2  \w    -82.00  22.00   1.00    1.00    --  -45.40  76.00  30.00  104
  3  \w    -82.00   9.00   1.00    1.00    --  -45.40  38.00  30.00   91
  4  \w    -33.00  -8.00   1.00    1.00    --  -45.40 -76.00 -30.00   25
  5  \w   -143.00 -31.00   1.00    1.00    -- -107.20  76.00-150.00  112
  6  \w   -169.00 -76.00   1.00    1.00    -- -107.20 -38.00 -60.00   93
  7  \w    -77.00 -20.00   1.00    1.00    -- -107.20  76.00 -90.00   57
  8  \w   -108.00 -27.00   1.00    1.00    -- -107.20  76.00 -60.00   81
  9  \w   -115.00 -62.00   1.00    1.00    -- -107.20  76.00-180.00   53
 10  \w   -118.00 -82.00   1.00    1.00    -- -107.20  76.00 -90.00   36
 11  \w   -135.00 -76.00   1.00    1.00    -- -107.20  57.00 120.00   59
 12  \w    -50.00 -25.00   1.00    1.00    -- -107.20  57.00 120.00   25
 13  \w   -171.00 -19.00   1.00    1.00    -- -107.20 -19.00 -30.00  152
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0035820000
_diffrn_orient_matrix_UB_12      0.1158710000
_diffrn_orient_matrix_UB_13      0.0006656000
_diffrn_orient_matrix_UB_21      0.0922066000
_diffrn_orient_matrix_UB_22      0.0042009000
_diffrn_orient_matrix_UB_23      0.0366128000
_diffrn_orient_matrix_UB_31      0.0092275000
_diffrn_orient_matrix_UB_32      0.0031210000
_diffrn_orient_matrix_UB_33      -0.0723845000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1030
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 0.980
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            8916
_diffrn_reflns_point_group_measured_fraction_full 0.980
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.697
_diffrn_reflns_theta_min         2.835
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.002
_exptl_absorpt_correction_T_max  0.861
_exptl_absorpt_correction_T_min  0.069
_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 red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.193
_exptl_crystal_description       block
_exptl_crystal_F_000             1700
_exptl_crystal_preparation       -
_exptl_crystal_recrystallization_method -
_exptl_crystal_size_max          0.47
_exptl_crystal_size_mid          0.116
_exptl_crystal_size_min          0.105
_refine_diff_density_max         2.909
_refine_diff_density_min         -1.272
_refine_diff_density_rms         0.156
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.103
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     501
_refine_ls_number_reflns         8916
_refine_ls_number_restraints     666
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0679
_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^)+(0.0817P)^2^+22.5993P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1921
_refine_ls_wR_factor_ref         0.1936
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8056
_reflns_number_total             8916
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04526e2.cif
_cod_data_source_block           3-Ce
_cod_depositor_comments
'Adding full bibliography for 1568047--1568055.cif.'
_cod_database_code               1568052
_manchester_internal_diff_code   rdpm236
_manchester_internal_coll_client IV
_manchester_internal_coll_user   IV
_manchester_internal_coll_date   02/10/2020
_manchester_internal_process_date 02/10/2020
_manchester_internal_process_user BR
_manchester_internal_solution_date 02/10/2020
_manchester_internal_solution_user BR
_manchester_internal_refinement_date 02/10/2020
_manchester_internal_refinement_user BR
_manchester_internal_validation_date 02/10/2020
_manchester_internal_validation_user AW
_manchester_internal_archive_date 02/10/2020
_manchester_internal_archive_user AW
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Ce1 Si8 C31 H69'
_shelx_estimated_absorpt_t_max   0.420
_shelx_estimated_absorpt_t_min   0.089
_reflns_odcompleteness_completeness 97.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.648(3)
 0.352(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 Si2A-C2A \\sim Si2A-C1A \\sim Si2A-C3A \\sim Si2-C1 \\sim Si2-C2 \\sim Si2-C3
\\sim Si4-C7 \\sim Si4-C9 ~
 Si4-C8 \\sim Si4A-C7A \\sim Si4A-C9A \\sim Si4A-C8A \\sim Si3-C6 \\sim Si3-C4
\\sim Si3-C5 \\sim Si3A-C6A
 \\sim Si3A-C4A \\sim Si3A-C5A
 with sigma of 0.02
 C5-C4 \\sim C6-C5 \\sim C6-C4 \\sim C8A-C7A \\sim C9A-C8A \\sim C9A-C7A \\sim
C8-C7 \\sim C9-C7 \\sim C9-C8 ~
 C2A-C1A \\sim C3A-C1A \\sim C3A-C2A \\sim C3-C1 \\sim C2-C1 \\sim C3-C2 \\sim
C5A-C4A \\sim C6A-C5A \\sim C6A-
 C4A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Si1 \\sim Si2 \\sim Si3 \\sim Si4 \\sim Si2A \\sim Si3A \\sim Si4A \\sim C1
\\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim
C1A \\sim C2A \\sim C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim
C9A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 Si2, Si2A, Si3A, C1, C2, C3, C5, C7, C2A, C3A, C4A, C5A, C6A, Si1, Si3, Si4,
 Si4A, C4, C6, C8, C9, C1A, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Si2A)=Sof(Si3A)=Sof(Si4A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C2A)=
 Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=
 Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C6A)=
 Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=
 Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=1-FVAR(1)
 Sof(Si2)=Sof(Si3)=Sof(Si4)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=
 Sof(H4B)=Sof(H4C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(H6A)=Sof(H6B)=
 Sof(H6C)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=FVAR(1)
7.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C20(H20), C25(H25), C26(H26), C31(H31)
7.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), C23(H23A,H23B,H23C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C), 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), C1A(H1AA,H1AB,H1AC), C2A(H2AA,H2AB,H2AC), C3A(H3AA,H3AB,H3AC),
  C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,H5AC), C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,
 H7AC), C8A(H8AA,H8AB,H8AC), C9A(H9AA,H9AB,H9AC)
;
_shelx_res_checksum              48322
_shelx_hkl_checksum              9628
_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_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 1.598
_oxdiff_exptl_absorpt_empirical_full_min 0.520