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_1569065
_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
'C54 H84 Ce O10 P Si3, C18 H36 K N2 O6, C4 H10 O'
_chemical_formula_sum            'C76 H130 Ce K N2 O17 P Si3'
_chemical_formula_weight         1638.27
_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             2022-11-11
_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                 93.1526(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.77347(11)
_cell_length_b                   45.4297(4)
_cell_length_c                   15.21804(13)
_cell_measurement_reflns_used    31229
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      76.4220
_cell_measurement_theta_min      3.0100
_cell_volume                     9507.89(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (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 10.2665
_diffrn_detector_type            Atlas
_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    -81.00 -30.00   0.75    2.00    --  -43.01 111.00 -82.00   68
  2  \w     42.00  84.00   0.75    2.00    --   43.01-111.00-175.00   56
  3  \w     49.00  74.50   0.75    8.00    --  112.00-111.00-175.00   34
  4  \w    116.00 141.50   0.75    8.00    --  112.00 111.00 -82.00   34
  5  \w   -115.00 -19.00   0.75    2.00    --  -43.01 -57.00 -90.00  128
  6  \w    -83.00  22.00   0.75    2.00    --  -43.01  19.00-150.00  140
  7  \w     20.00  57.50   0.75    2.00    --   43.01  37.00 120.00   50
  8  \w    122.00 177.50   0.75    8.00    --  112.00  77.00  30.00   74
  9  \w     87.00 141.00   0.75    8.00    --  112.00  61.00 120.00   72
 10  \w     81.00 107.25   0.75    8.00    --  112.00-111.00 -90.00   35
 11  \w    104.50 178.00   0.75    8.00    --  112.00  77.00  90.00   98
 12  \w     33.00 105.00   0.75    8.00    --  112.00 -94.00-180.00   96
 13  \w     83.00 176.00   0.75    8.00    --  112.00  61.00  60.00  124
 14  \w     74.00 100.25   0.75    8.00    --  112.00 -94.00 -60.00   35
 15  \w     76.00 131.50   0.75    8.00    --  112.00 -61.00   0.00   74
 16  \w     56.00 140.00   0.75    8.00    --  112.00 -61.00 150.00  112
 17  \w     58.00 104.50   0.75    8.00    --  112.00-111.00   0.00   62
 18  \w     89.00 174.50   0.75    8.00    --  112.00  61.00   0.00  114
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0708599000
_diffrn_orient_matrix_UB_12      0.0209043000
_diffrn_orient_matrix_UB_13      0.0510615000
_diffrn_orient_matrix_UB_21      -0.0368407000
_diffrn_orient_matrix_UB_22      0.0258527000
_diffrn_orient_matrix_UB_23      -0.0582649000
_diffrn_orient_matrix_UB_31      -0.0785177000
_diffrn_orient_matrix_UB_32      0.0067166000
_diffrn_orient_matrix_UB_33      0.0654065000
_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  0.0356
_diffrn_reflns_av_unetI/netI     0.0346
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       53
_diffrn_reflns_limit_k_min       -57
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            62211
_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         76.692
_diffrn_reflns_theta_min         3.067
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.062
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.239
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
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 blue'
_exptl_crystal_density_diffrn    1.144
_exptl_crystal_description       plate
_exptl_crystal_F_000             3480
_exptl_crystal_size_max          0.449
_exptl_crystal_size_mid          0.153
_exptl_crystal_size_min          0.095
_refine_diff_density_max         1.375
_refine_diff_density_min         -1.458
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.148
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1053
_refine_ls_number_reflns         19779
_refine_ls_number_restraints     305
_refine_ls_restrained_S_all      1.152
_refine_ls_R_factor_all          0.0586
_refine_ls_R_factor_gt           0.0554
_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^)+31.9927P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1199
_refine_ls_wR_factor_ref         0.1213
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18447
_reflns_number_total             19779
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01478a2.cif
_cod_data_source_block           ah482-2
_cod_depositor_comments
'Adding full bibliography for 1569056--1569065.cif.'
_cod_original_cell_volume        9507.90(14)
_cod_database_code               1569065
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C84 H150 N2 O19 Si3 P1 K1 Ce1'
_shelx_estimated_absorpt_t_max   0.645
_shelx_estimated_absorpt_t_min   0.210
_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
 P1-C61 \\sim P1-C55 \\sim P1-C59 \\sim P1-C65 \\sim P1-C57 \\sim P1-C63
 with sigma of 0.02
 C57-C58 \\sim C64-C63 \\sim C66-C65 \\sim C59-C60 \\sim C55-C56 \\sim C61-C62
 with sigma of 0.02
 C51-C48 \\sim C54-C48 \\sim C53-C48 \\sim C50-C48 \\sim C49-C48 \\sim C52-C48
 with sigma of 0.02
 C51-C50 \\sim C49-C54 \\sim C53-C52
 with sigma of 0.02
 C46-C47 \\sim C45-C43 \\sim C44-C42
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
P1 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim
C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63)=
 Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=Sof(C65)=Sof(H65A)=
 Sof(H65B)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=1-FVAR(1)
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C57)=
 Sof(H57A)=Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59A)=
 Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(1)
 Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=1-FVAR(2)
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(2)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=1-FVAR(3)
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=FVAR(3)
5.a 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), C68(H68A,H68B), C69(H69A,H69B),
 C70(H70A,H70B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B),
  C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,
 H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B),
 C84(H84A,H84B), C86(H86A,H86B), C87(H87A,H87B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11), C22(H22),
 C23(H23), C24(H24), C25(H25), C36(H36), C37(H37), C38(H38), C39(H39)
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), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,
 H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), 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), C85(H85A,H85B,H85C), C88(H88A,H88B,H88C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 284 electrons were 
found in a volume of 1520\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1.7[C4H10O] per Asymmetric Unit 
which account for 286 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              17822
_shelx_hkl_checksum              63509
_shelx_fab_checksum              97947
_olex2_date_sample_data_collection 2022-10-25
_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 1.505
_oxdiff_exptl_absorpt_empirical_full_min 0.788