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_1569063
_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         'C120 H186 K8 O24 Si6'
_chemical_formula_sum            'C120 H186 K8 O24 Si6'
_chemical_formula_weight         2494.02
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-01-23
_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                 98.1608(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.21058(19)
_cell_length_b                   18.42416(15)
_cell_length_c                   29.16367(18)
_cell_measurement_reflns_used    27208
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      75.9150
_cell_measurement_theta_min      3.9820
_cell_volume                     15536.38(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_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    'SHELXS  (Sheldrick, 2008)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.987
_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    -84.00 -59.00   1.00    1.50    --  -40.66 147.00  44.00   25
  2  \w   -112.00 -87.00   1.00    1.50    --  -40.66-147.00  -4.00   25
  3  \w    -86.00 -13.00   1.00    1.50    --  -40.66 124.00-120.00   73
  4  \w     60.00  85.00   1.00    1.50    --   40.66-124.00 160.00   25
  5  \w     52.00  77.00   1.00    6.00    --  112.00-124.00 160.00   25
  6  \w    102.00 127.00   1.00    6.00    --  112.00 147.00  44.00   25
  7  \w    114.00 139.00   1.00    6.00    --  112.00 124.00-120.00   25
  8  \w     74.00 128.00   1.00    6.00    --  112.00-147.00  -4.00   54
  9  \w   -112.00 -14.00   1.00    1.50    --  -40.66 -57.00 -30.00   98
 10  \w    -29.00  63.00   1.00    1.50    --   40.66 -38.00  90.00   92
 11  \w     45.00  84.00   1.00    6.00    --  112.00 -77.00 -30.00   39
 12  \w     97.00 124.00   1.00    6.00    --  112.00  61.00  60.00   27
 13  \w     47.00 100.00   1.00    6.00    --  112.00-111.00-120.00   53
 14  \w     42.00 118.00   1.00    6.00    --  112.00 -45.00   0.00   76
 15  \w     61.00 142.00   1.00    6.00    --  112.00 178.00   0.00   81
 16  \w    116.00 178.00   1.00    6.00    --  112.00  77.00   0.00   62
 17  \w     66.00 103.00   1.00    6.00    --  112.00-111.00-180.00   37
 18  \w     55.00  81.00   1.00    6.00    --  112.00 -94.00-180.00   26
 19  \w    111.00 177.00   1.00    6.00    --  112.00  45.00 -90.00   66
 20  \w     67.00 108.00   1.00    6.00    --  112.00-111.00 150.00   41
 21  \w    106.00 155.00   1.00    6.00    --  112.00  77.00 120.00   49
 22  \w     64.00 109.00   1.00    6.00    --  112.00-111.00-150.00   45
 23  \w    103.00 178.00   1.00    6.00    --  112.00  77.00 -30.00   75
;
_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      0.0186949000
_diffrn_orient_matrix_UB_12      0.0782879000
_diffrn_orient_matrix_UB_13      0.0019891000
_diffrn_orient_matrix_UB_21      -0.0489145000
_diffrn_orient_matrix_UB_22      0.0285033000
_diffrn_orient_matrix_UB_23      -0.0176940000
_diffrn_orient_matrix_UB_31      -0.0098745000
_diffrn_orient_matrix_UB_32      0.0069343000
_diffrn_orient_matrix_UB_33      0.0503119000
_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  0.0241
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       35
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            50880
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.035
_diffrn_reflns_theta_min         3.057
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.864
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.277
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.80a (Rigaku Oxford Diffraction, 2023)
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            'translucent dark black'
_exptl_crystal_density_diffrn    1.066
_exptl_crystal_description       prism
_exptl_crystal_F_000             5336
_exptl_crystal_size_max          0.448
_exptl_crystal_size_mid          0.236
_exptl_crystal_size_min          0.211
_refine_diff_density_max         0.260
_refine_diff_density_min         -0.293
_refine_diff_density_rms         0.036
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     827
_refine_ls_number_reflns         16032
_refine_ls_number_restraints     329
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0331
_refine_ls_R_factor_gt           0.0301
_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^)+(0.0469P)^2^+4.9095P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0817
_refine_ls_wR_factor_ref         0.0840
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14602
_reflns_number_total             16032
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01478a2.cif
_cod_data_source_block           ah539a
_cod_depositor_comments
'Adding full bibliography for 1569056--1569065.cif.'
_cod_original_cell_volume        15536.37(19)
_cod_database_code               1569063
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C136 H218 O28 Si6 K8'
_shelx_estimated_absorpt_t_max   0.583
_shelx_estimated_absorpt_t_min   0.360
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C56-C52 \\sim C53-C52 \\sim C54-C53 \\sim C57-C56 \\sim C55-C54 \\sim C57-C55
\\sim C64-C63 \\sim C61-C60
 \\sim C60-C59 \\sim C63-C62 \\sim C59-C58 \\sim C62-C58
 with sigma of 0.02
 O10-C52 \\sim O10-C55 \\sim O11-C58 \\sim O11-C64 \\sim O11-C61
 with sigma of 0.02
 C70-C67 \\sim C69-C68 \\sim C69-C66 \\sim C70-C66 \\sim C66-C65
 with sigma of 0.02
 O12-C67 \\sim O12-C68 \\sim O12-C65
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O10 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
O11 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim C62 \\sim C63 \\sim C64:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
O12 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=1-FVAR(1)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
 Sof(H58C)=Sof(H58D)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=
 Sof(C64)=Sof(H64A)=Sof(H64B)=1-FVAR(2)
 Sof(H58A)=Sof(H58B)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=
 Sof(C61)=Sof(H61A)=Sof(H61B)=FVAR(2)
 Sof(H52C)=Sof(H52D)=Sof(H55C)=Sof(H55D)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C57)=
 Sof(H57A)=Sof(H57B)=1-FVAR(3)
 Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=Sof(H54A)=Sof(H54B)=
 Sof(H55A)=Sof(H55B)=FVAR(3)
 Sof(H66C)=Sof(H66D)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(C70)=Sof(H70A)=Sof(H70B)=
 1-FVAR(4)
 Sof(H66A)=Sof(H66B)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(C69)=Sof(H69A)=Sof(H69B)=
 FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C52(H52A,H52B), C52(H52C,H52D), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,
 H55B), C55(H55C,H55D), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B),
 C58(H58C,H58D), C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B),
  C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C66(H66C,
 H66D), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B), C70(H70A,H70B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12), C23(H23),
 C24(H24), C25(H25), C26(H26), C40(H40), C41(H41), C42(H42), C43(H43)
5.c 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), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C),
 C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,
 H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 664 electrons were 
found in a volume of 3448\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
4[C4H8O] per Asymmetric Unit 
which account for 640 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              99586
_shelx_hkl_checksum              57565
_shelx_fab_checksum              35516
_olex2_date_sample_data_collection 2023-01-17
_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 2.113
_oxdiff_exptl_absorpt_empirical_full_min 0.611