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_1569062
_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         'C98 H138 Ce2 O22 Si6, 2(C18 H36 K N2 O6)'
_chemical_formula_sum            'C134 H210 Ce2 K2 N4 O34 Si6'
_chemical_formula_weight         2948.03
_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             2022-10-22
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-07 deposited with the CCDC.	2023-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.1616(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.54182(9)
_cell_length_b                   33.4467(2)
_cell_length_c                   20.39623(15)
_cell_measurement_reflns_used    40559
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.4860
_cell_measurement_theta_min      3.3800
_cell_volume                     9236.15(11)
_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 0.985
_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   -115.00 -13.00   1.00    1.00    --  -43.01 -67.00-127.00  102
  2  \w    -61.00  25.00   1.00    1.00    --  -43.01  67.00   5.00   86
  3  \w     40.00  65.00   1.00    1.00    --   43.01  67.00   5.00   25
  4  \w     -3.00  22.00   1.00    1.00    --   43.01 -67.00-127.00   25
  5  \w     39.00 123.00   1.00    4.00    --  103.49 -67.00-127.00   84
  6  \w     76.00 176.00   1.00    4.00    --  103.49  67.00   5.00  100
  7  \w    -26.00  18.00   1.00    1.00    --  -43.01  37.00-180.00   44
  8  \w    -16.00  75.00   1.00    1.00    --   43.01 -77.00  90.00   91
  9  \w     42.00  79.00   1.00    4.00    --  103.49-111.00-150.00   37
 10  \w     30.00  58.00   1.00    4.00    --  103.49-111.00-180.00   28
 11  \w     55.00 126.00   1.00    4.00    --  103.49  15.00 -30.00   71
 12  \w    121.00 161.00   1.00    4.00    --  103.49  61.00-150.00   40
 13  \w     83.00 109.00   1.00    4.00    --  103.49-111.00 -30.00   26
 14  \w     40.00  65.00   1.00    4.00    --  103.49-111.00 -30.00   25
 15  \w     35.00 109.00   1.00    4.00    --  103.49-111.00  60.00   74
 16  \w     81.00 169.00   1.00    4.00    --  103.49  30.00 120.00   88
 17  \w     36.00 108.00   1.00    4.00    --  103.49-111.00-120.00   72
 18  \w     44.00  70.00   1.00    4.00    --  103.49-111.00 150.00   26
 19  \w     77.00 109.00   1.00    4.00    --  103.49-111.00 150.00   32
 20  \w    104.00 176.00   1.00    4.00    --  103.49  45.00 -30.00   72
 21  \w     32.00 128.00   1.00    4.00    --  103.49 -61.00  30.00   96
;
_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      -0.0580037000
_diffrn_orient_matrix_UB_12      0.0171280000
_diffrn_orient_matrix_UB_13      -0.0593540000
_diffrn_orient_matrix_UB_21      0.0488679000
_diffrn_orient_matrix_UB_22      -0.0308970000
_diffrn_orient_matrix_UB_23      -0.0450220000
_diffrn_orient_matrix_UB_31      -0.0848598000
_diffrn_orient_matrix_UB_32      -0.0295256000
_diffrn_orient_matrix_UB_33      0.0126293000
_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  0.0312
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            73474
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.555
_diffrn_reflns_theta_min         3.522
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.007
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.123
_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 pale colourless'
_exptl_crystal_density_diffrn    1.060
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3104
_exptl_crystal_size_max          0.443
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.218
_refine_diff_density_max         0.761
_refine_diff_density_min         -0.312
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     838
_refine_ls_number_reflns         18064
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0348
_refine_ls_R_factor_gt           0.0315
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0478P)^2^+2.5237P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0817
_refine_ls_wR_factor_ref         0.0839
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16533
_reflns_number_total             18064
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01478a2.cif
_cod_data_source_block           ah491
_cod_depositor_comments
'Adding full bibliography for 1569056--1569065.cif.'
_cod_database_code               1569062
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C166 H274 N4 O42 Si6 K2 Ce2'
_shelx_estimated_absorpt_t_max   0.408
_shelx_estimated_absorpt_t_min   0.215
_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.a Secondary CH2 refined with riding coordinates:
 C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,
 H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B),
 C59(H59A,H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B),
  C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), C67(H67A,H67B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C10(H10), C11(H11), C12(H12), C13(H13), C23(H23),
 C24(H24), C25(H25), C26(H26), C37(H37), C38(H38), C39(H39), C40(H40)
2.c Idealised Me refined as rotating group:
 C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C31(H31A,H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,
 H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 574 electrons were 
found in a volume of 2476\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
7.2[C4H8O] per Asymmetric Unit 
which account for 576 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              92072
_shelx_hkl_checksum              65727
_shelx_fab_checksum              11284
_olex2_date_sample_data_collection 2022-10-17
_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 1.466
_oxdiff_exptl_absorpt_empirical_full_min 0.728