Isolation and redox reactivity of cerium complexes in four redox states.
Hsueh, Fang-Che; Rajeshkumar, Thayalan; Maron, Laurent; Scopelliti, Rosario; Sienkiewicz, Andrzej; Mazzanti, Marinella; Chemical science 14 (2023) 6011–6021; doi:10.1039/d3sc01478a

data_1569060
_publ_section_title
;
 Isolation and redox reactivity of cerium complexes in four redox states.
;
_journal_issue                   22
_journal_name_full               'Chemical science'
_journal_page_first              6011
_journal_page_last               6021
_journal_paper_doi               10.1039/d3sc01478a
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C48 H72 O9 Si3'
_chemical_formula_sum            'C48 H72 O9 Si3'
_chemical_formula_weight         877.32
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-09-09
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-01 deposited with the CCDC.	2023-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                67.818(6)
_cell_angle_beta                 89.464(5)
_cell_angle_gamma                89.905(6)
_cell_formula_units_Z            4
_cell_length_a                   13.5317(9)
_cell_length_b                   19.7750(16)
_cell_length_c                   20.4919(12)
_cell_measurement_reflns_used    2978
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.3140
_cell_measurement_theta_min      3.9290
_cell_volume                     5077.4(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_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      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -67.00 -23.00   1.00   10.00    --  -40.91  77.00 120.00   44
  2  \w    -65.00  31.00   1.00   10.00    --  -40.91  38.00 -60.00   96
  3  \w   -103.00 -16.00   1.00   10.00    --  -40.91 -57.00   0.00   87
  4  \w    -86.00 -51.00   1.00   10.00    --  -40.91 125.00-150.00   35
  5  \w   -108.00 -17.00   1.00   10.00    --  -40.91 -38.00 120.00   91
  6  \w    -33.00  -5.00   1.00   10.00    --   40.91 -38.00-150.00   28
  7  \w     30.00 109.00   1.00   40.00    --  105.15-111.00  60.00   79
  8  \w     76.00 100.00   1.00   40.00    --  105.15-111.00-120.00   24
  9  \w     78.00 171.00   1.00   40.00    --  105.15  30.00-150.00   93
 10  \w    108.00 173.00   1.00   40.00    --  105.15 111.00-150.00   65
 11  \w     31.00 130.00   1.00   40.00    --  105.15 -30.00-120.00   99
 12  \w    149.00 177.00   1.00   40.00    --  105.15  30.00 -60.00   28
 13  \w     49.00  74.00   1.00   40.00    --  105.15 -45.00   0.00   25
 14  \w     33.00 128.00   1.00   40.00    --  105.15 -61.00 120.00   95
 15  \w     84.00 109.00   1.00   40.00    --  105.15-111.00 -30.00   25
 16  \w     79.00 178.00   1.00   40.00    --  105.15  45.00 -90.00   99
 17  \w     34.00 103.00   1.00   40.00    --  105.15 -94.00 120.00   69
 18  \w     51.00 134.00   1.00   40.00    --  105.15 -77.00-120.00   83
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1131049000
_diffrn_orient_matrix_UB_12      -0.0086565000
_diffrn_orient_matrix_UB_13      -0.0009901000
_diffrn_orient_matrix_UB_21      0.0126251000
_diffrn_orient_matrix_UB_22      0.0658468000
_diffrn_orient_matrix_UB_23      0.0219984000
_diffrn_orient_matrix_UB_31      -0.0032364000
_diffrn_orient_matrix_UB_32      -0.0516470000
_diffrn_orient_matrix_UB_33      0.0781485000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1103
_diffrn_reflns_av_unetI/netI     0.1909
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            33428
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        66.593
_diffrn_reflns_theta_max         66.593
_diffrn_reflns_theta_min         3.266
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.261
_exptl_absorpt_correction_T_max  0.969
_exptl_absorpt_correction_T_min  0.904
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.51a (Rigaku Oxford Diffraction, 2022)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.148
_exptl_crystal_description       prism
_exptl_crystal_F_000             1896
_exptl_crystal_size_max          0.112
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.028
_refine_diff_density_max         0.254
_refine_diff_density_min         -0.364
_refine_diff_density_rms         0.057
_refine_ls_extinction_coef       0.000119(8)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   0.854
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1155
_refine_ls_number_reflns         17891
_refine_ls_number_restraints     75
_refine_ls_restrained_S_all      0.854
_refine_ls_R_factor_all          0.1621
_refine_ls_R_factor_gt           0.0634
_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^)] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0994
_refine_ls_wR_factor_ref         0.1382
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7956
_reflns_number_total             17891
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01478a2.cif
_cod_data_source_block           ah354
_cod_depositor_comments
'Adding full bibliography for 1569056--1569065.cif.'
_cod_original_cell_volume        5077.3(6)
_cod_database_code               1569060
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C48 H72 O9 Si3'
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.872
_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, All O(H) groups
2. Restrained distances
 C77-C75 \\sim C80-C75 \\sim C76-C75 \\sim C79-C75 \\sim C78-C75 \\sim C81-C75
 with sigma of 0.02
 C80-C79 \\sim C79-C81 \\sim C80-C81
 with sigma of 0.02
 C77-C76 \\sim C76-C78 \\sim C77-C78
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=1-FVAR(1)
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4A), C6(H6), C8(H8), C9(H9), C10(H10A), C11(H11), C22(H22),
 C23(H23), C24(H24), C25(H25), C36(H36), C37(H37), C38(H38), C39(H39), C50(H50),
  C52(H52), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59), C70(H70),
 C71(H71), C72(H72), C73(H73), C87(H87), C88(H88), C89(H89), C90(H90)
5.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C28(H28A,H28B,H28C), C29(H29A,
 H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C62(H62A,
 H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C66(H66A,H66B,H66C),
 C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C76(H76A,H76B,H76C), C77(H77A,H77B,
 H77C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C81(H81A,
 H81B,H81C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C),
 C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C95(H95A,H95B,H95C), C97(H97A,H97B,
 H97C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C)
5.c Idealised tetrahedral OH refined as rotating group:
 O1(H1), O4(H4), O7(H7), O10(H10), O13(H13), O16(H16)
;
_shelx_res_checksum              39418
_shelx_hkl_checksum              69728
_olex2_date_sample_data_collection 2022-04-12
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.937
_oxdiff_exptl_absorpt_empirical_full_min 0.389