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_1569057
_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         'C60 H99 Ce K2 O12 Si3'
_chemical_formula_sum            'C60 H99 Ce K2 O12 Si3'
_chemical_formula_weight         1314.98
_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             2022-11-19
_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                90
_cell_angle_beta                 105.250(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.2554(11)
_cell_length_b                   11.0935(6)
_cell_length_c                   25.7721(14)
_cell_measurement_reflns_used    3760
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.1220
_cell_measurement_theta_min      3.5930
_cell_volume                     6966.3(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.73a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.73a (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 0.997
_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     -9.00  29.00   1.00   10.00    --  -40.91  82.00  34.00   38
  2  \w     96.00 127.00   1.00   40.00    --  105.15 -82.00 -87.00   31
  3  \w     49.00  76.00   1.00   40.00    --  105.15 -82.00 -87.00   27
  4  \w    116.00 141.00   1.00   40.00    --  105.15  82.00  34.00   25
  5  \w     46.00  73.00   1.00   10.00    --   40.91 -77.00  30.00   27
  6  \w     36.00 112.00   1.00   10.00    --   40.91  38.00 120.00   76
  7  \w      7.00  58.00   1.00   10.00    --   40.91 -99.00-180.00   51
  8  \w    -21.00  33.00   1.00   10.00    --   40.91 -77.00  30.00   54
  9  \w    -17.00  73.00   1.00   10.00    --   40.91 -82.00 -87.00   90
 10  \w    104.00 177.00   1.00   40.00    --  105.15 111.00   0.00   73
 11  \w     35.00 122.00   1.00   40.00    --  105.15 -45.00 -30.00   87
 12  \w     54.00  96.00   1.00   40.00    --  105.15-111.00-150.00   42
 13  \w    111.00 177.00   1.00   40.00    --  105.15 111.00 -90.00   66
 14  \w     70.00 112.00   1.00   40.00    --  105.15 -30.00 -60.00   42
 15  \w    129.00 177.00   1.00   40.00    --  105.15 111.00  90.00   48
 16  \w     29.00  57.00   1.00   40.00    --  105.15 -30.00 -60.00   28
 17  \w    119.00 176.00   1.00   40.00    --  105.15 111.00  30.00   57
 18  \w    104.00 178.00   1.00   40.00    --  105.15 111.00-120.00   74
;
_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      -0.0400461000
_diffrn_orient_matrix_UB_12      0.1073929000
_diffrn_orient_matrix_UB_13      -0.0101258000
_diffrn_orient_matrix_UB_21      -0.0303053000
_diffrn_orient_matrix_UB_22      -0.0540449000
_diffrn_orient_matrix_UB_23      -0.0548332000
_diffrn_orient_matrix_UB_31      -0.0385008000
_diffrn_orient_matrix_UB_32      -0.0694327000
_diffrn_orient_matrix_UB_33      0.0269229000
_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  0.1266
_diffrn_reflns_av_unetI/netI     0.1546
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            35961
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.786
_diffrn_reflns_theta_min         3.555
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.035
_exptl_absorpt_correction_T_max  0.790
_exptl_absorpt_correction_T_min  0.285
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.73a (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            'translucent dark purple'
_exptl_crystal_density_diffrn    1.254
_exptl_crystal_description       plate
_exptl_crystal_F_000             2772
_exptl_crystal_size_max          0.287
_exptl_crystal_size_mid          0.052
_exptl_crystal_size_min          0.046
_refine_diff_density_max         1.351
_refine_diff_density_min         -0.655
_refine_diff_density_rms         0.117
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     809
_refine_ls_number_reflns         13487
_refine_ls_number_restraints     240
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.1349
_refine_ls_R_factor_gt           0.0762
_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^)+(0.0719P)^2^+4.0848P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1703
_refine_ls_wR_factor_ref         0.2000
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8102
_reflns_number_total             13487
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01478a2.cif
_cod_data_source_block           ah499-4
_cod_depositor_comments
'Adding full bibliography for 1569056--1569065.cif.'
_cod_database_code               1569057
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C63.5 H103 O12 Si3 K2 Ce1'
_shelx_estimated_absorpt_t_max   0.738
_shelx_estimated_absorpt_t_min   0.237
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C36-C34 \\sim C40-C34 \\sim C37-C34 \\sim C38-C34 \\sim C35-C34 \\sim C39-C34
 with sigma of 0.02
 C36-C37 \\sim C37-C35 \\sim C35-C36
 with sigma of 0.02
 C39-C40 \\sim C40-C38 \\sim C38-C39
 with sigma of 0.02
 C63-C64 \\sim C67-C68 \\sim C66-C65
 with sigma of 0.02
 O12-C67 \\sim O12-C65 \\sim O12-C63
 with sigma of 0.02
 C21-C22 \\sim C22-C23 \\sim C21-C23
 with sigma of 0.02
 C20-C19 \\sim C19-C18 \\sim C18-C20
 with sigma of 0.02
 C20-C17 \\sim C21-C17 \\sim C18-C17 \\sim C22-C17 \\sim C19-C17 \\sim C23-C17
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O12 \\sim C65 \\sim C66 \\sim C67 \\sim C68: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=1-FVAR(1)
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(1)
 Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=1-FVAR(2)
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=FVAR(2)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=1-FVAR(3)
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C2(H2), C4(H4), C6(H6)
5.b Secondary CH2 refined with riding coordinates:
 C55(H55A,H55B), C57(H57A,H57B), C59(H59A,H59B), C61(H61A,H61B), C63(H63A,
 H63B), C65(H65A,H65B), C67(H67A,H67B)
5.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C25(H25), C26(H26), C27(H27), C28(H28),
 C42(H42), C43(H43), C44(H44), C45(H45)
5.d 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), C21(H21A,H21B,H21C), C22(H22A,
 H22B,H22C), C23(H23A,H23B,H23C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C),
 C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C48(H48A,
 H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C52(H52A,H52B,H52C),
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C56(H56A,H56B,H56C), C58(H58A,H58B,
 H58C), C60(H60A,H60B,H60C), C62(H62A,H62B,H62C), C64(H64A,H64B,H64C), C66(H66A,
 H66B,H66C), C68(H68A,H68B,H68C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 80 electrons were 
found in a volume of 410\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.4[C7H8] per Asymmetric Unit 
which account for 80 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              77743
_shelx_hkl_checksum              53512
_shelx_fab_checksum              8644
_olex2_date_sample_data_collection 2022-11-16
_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 2.059
_oxdiff_exptl_absorpt_empirical_full_min 0.511