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_1568054
_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 U'
_chemical_formula_sum            'C31 H69 Si8 U'
_chemical_formula_weight         904.61
_chemical_name_systematic        '[U(Cp'')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     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-11-06
_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                 111.407(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.9833(8)
_cell_length_b                   13.2292(5)
_cell_length_c                   20.4047(13)
_cell_measurement_reflns_used    12728
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      75.7010
_cell_measurement_theta_min      2.8130
_cell_volume                     4519.5(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 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -41.00   2.00   0.50    1.12    --  -45.90  74.00  16.00   86
  2  \w    -44.00  -8.00   0.50    1.12    --  -45.90 -74.00-111.00   72
  3  \w   -114.00 -89.00   0.50    1.12    --  -45.90 -74.00-111.00   50
  4  \w   -154.00 -83.00   0.50    5.30    -- -107.20 -74.00-111.00  142
  5  \w   -110.00 -76.00   0.50    5.30    -- -107.20  74.00  16.00   68
  6  \w    -15.00  11.00   0.50    1.12    --    5.00  74.00  16.00   52
  7  \w    -84.00  42.00   0.50    1.12    --  -45.90  38.00  90.00  252
  8  \w    -77.00  14.00   0.50    1.12    --  -45.90  57.00-180.00  182
  9  \w   -110.00 -70.00   0.50    5.30    -- -107.20 -76.00 -30.00   80
 10  \w   -147.00 -27.00   0.50    5.30    -- -107.20  76.00 150.00  240
 11  \w   -131.00-105.00   0.50    5.30    -- -107.20  76.00  60.00   52
 12  \w   -106.00 -80.00   0.50    5.30    -- -107.20 -76.00 -60.00   52
 13  \w   -143.00-103.00   0.50    5.30    -- -107.20  71.00 121.01   80
 14  \w    -97.00 -64.00   0.50    5.30    -- -107.20  71.00 121.01   66
 15  \w    -47.00 -21.00   0.50    5.30    -- -107.20  71.00 121.01   52
 16  \w   -194.00-169.00   0.50    5.30    -- -107.20 -57.00 -90.00   50
 17  \w   -142.00-116.00   0.50    5.30    -- -107.20 -57.00 -90.00   52
 18  \w   -196.00 -75.00   0.50    5.30    -- -107.20 -57.00-180.00  242
 19  \w    -75.00 -26.00   0.50    5.30    -- -107.20  76.00  60.00   98
 20  \w   -196.00-125.00   0.50    5.30    -- -107.20 -38.00 -90.00  142
 21  \w   -185.00-138.00   0.50    5.30    -- -107.20 -76.00 -60.00   94
 22  \w   -196.00-143.00   0.50    5.30    -- -107.20 -57.00 150.00  106
 23  \w   -113.00 -88.00   0.50    5.30    -- -107.20 -57.00 150.00   50
 24  \w   -144.00 -95.00   0.50    5.30    -- -107.20  76.00  90.00   98
 25  \w    -43.00 -18.00   0.50    5.30    -- -107.20  76.00  90.00   50
 26  \w   -194.00-169.00   0.50    5.30    -- -107.20 -38.00   0.00   50
 27  \w   -151.00 -80.00   0.50    5.30    -- -107.20 -38.00   0.00  142
 28  \w   -112.00 -87.00   0.50    5.30    -- -107.20  76.00-180.00   50
 29  \w   -130.00 -18.00   0.50    5.30    -- -107.20  57.00-120.00  224
 30  \w   -127.00-102.00   0.50    5.30    -- -107.20  76.00 120.00   50
 31  \w   -169.00-144.00   0.50    5.30    -- -107.20 -76.00 -30.00   50
;
_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      -0.0714817000
_diffrn_orient_matrix_UB_12      -0.0648853000
_diffrn_orient_matrix_UB_13      -0.0450629000
_diffrn_orient_matrix_UB_21      0.0338351000
_diffrn_orient_matrix_UB_22      -0.0907384000
_diffrn_orient_matrix_UB_23      0.0492930000
_diffrn_orient_matrix_UB_31      -0.0470323000
_diffrn_orient_matrix_UB_32      0.0334492000
_diffrn_orient_matrix_UB_33      0.0460063000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0961
_diffrn_reflns_av_unetI/netI     0.0823
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            43377
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.241
_diffrn_reflns_theta_min         2.810
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.266
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.662
_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 green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       plate
_exptl_crystal_F_000             1836
_exptl_crystal_preparation       -
_exptl_crystal_recrystallization_method 'Crystallised from pentane at -25 oC'
_exptl_crystal_size_max          0.151
_exptl_crystal_size_mid          0.046
_exptl_crystal_size_min          0.033
_refine_diff_density_max         1.059
_refine_diff_density_min         -2.289
_refine_diff_density_rms         0.133
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     500
_refine_ls_number_reflns         8268
_refine_ls_number_restraints     168
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0621
_refine_ls_R_factor_gt           0.0503
_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^)+(0.0385P)^2^+14.2312P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1228
_refine_ls_wR_factor_ref         0.1288
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6715
_reflns_number_total             8268
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04526e2.cif
_cod_data_source_block           3-U
_cod_depositor_comments
'Adding full bibliography for 1568047--1568055.cif.'
_cod_database_code               1568054
_manchester_internal_diff_code   rdpm197
_manchester_internal_coll_client BR/PC
_manchester_internal_coll_user   BR/PC
_manchester_internal_coll_date   31/10/2019
_manchester_internal_process_date 31/10/2019
_manchester_internal_process_user BR
_manchester_internal_solution_date 31/10/2019
_manchester_internal_solution_user BR
_manchester_internal_refinement_date 31/10/2019
_manchester_internal_refinement_user BR
_manchester_internal_validation_date 06/11/2019
_manchester_internal_validation_user AW
_manchester_internal_archive_date 06/11/2019
_manchester_internal_archive_user AW
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'U1 Si12 C27'
_chemical_oxdiff_usercomment     br
_shelx_estimated_absorpt_t_max   0.688
_shelx_estimated_absorpt_t_min   0.259
_reflns_odcompleteness_completeness 99.47
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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. Restrained distances
 Si2A-Si1 \\sim Si4-Si1 \\sim Si4A-Si1 \\sim Si3-Si1 \\sim Si3A-Si1 \\sim
Si2-Si1
 with sigma of 0.02
 Si4-C9 \\sim Si4-C8 \\sim Si4-C7 \\sim Si4A-C9A \\sim Si4A-C7A \\sim Si4A-C8A
\\sim Si2A-C2A \\sim Si2A-
 C3A \\sim Si2A-C1A \\sim Si2-C2 \\sim Si2-C1 \\sim Si2-C3 \\sim Si3A-C5A \\sim
Si3A-C4A \\sim Si3A-C6A ~
 Si3-C4 \\sim Si3-C6 \\sim Si3-C5
 with sigma of 0.01
3. 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)
4.a Aromatic/amide H refined with riding coordinates:
 C14(H14), C15(H15), C20(H20), C25(H25), C26(H26), C31(H31)
4.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              19627
_shelx_hkl_checksum              5729
_manchester_internal_coll_frame_method '\w scans'
_manchester_internal_coll_frame_time 5.30s
_manchester_internal_coll_frame_width 0.5
_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 2.906
_oxdiff_exptl_absorpt_empirical_full_min 0.422