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_1569059
_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         'C52 H77 Ce O10 Si3, C7 H8'
_chemical_formula_sum            'C59 H85 Ce O10 Si3'
_chemical_formula_weight         1178.66
_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             2022-09-08
_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                109.329(2)
_cell_angle_beta                 108.864(2)
_cell_angle_gamma                101.873(2)
_cell_formula_units_Z            2
_cell_length_a                   14.0331(3)
_cell_length_b                   15.4209(4)
_cell_length_c                   16.9380(4)
_cell_measurement_reflns_used    20225
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      32.3930
_cell_measurement_theta_min      2.5480
_cell_volume                     3065.72(16)
_computing_cell_refinement       'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.57a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.57a (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      139.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -50.00  40.00   1.00   12.50    --   19.03 -70.00-138.00   90
  2  \w    -12.00  86.00   1.00   12.50    --   19.03  70.00  -6.00   98
  3  \w    -31.00  14.00   1.00   12.50    --  -17.94 -77.00  90.00   45
  4  \w    -13.00  12.00   1.00   12.50    --  -17.94 -77.00 -30.00   25
  5  \w    -40.00  12.00   1.00   12.50    --  -17.94  77.00 150.00   52
  6  \w    -24.00   2.00   1.00   12.50    --  -17.94  37.00-120.00   26
  7  \w     32.00  57.00   1.00   12.50    --  -17.94  37.00-120.00   25
  8  \w     -4.00  89.00   1.00   12.50    --   19.03  37.00 150.00   93
;
_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      0.0254379000
_diffrn_orient_matrix_UB_12      -0.0320775000
_diffrn_orient_matrix_UB_13      0.0116886000
_diffrn_orient_matrix_UB_21      -0.0446129000
_diffrn_orient_matrix_UB_22      -0.0409623000
_diffrn_orient_matrix_UB_23      -0.0367056000
_diffrn_orient_matrix_UB_31      0.0247895000
_diffrn_orient_matrix_UB_32      0.0011263000
_diffrn_orient_matrix_UB_33      -0.0302780000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0330
_diffrn_reflns_av_unetI/netI     0.0513
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            41898
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.508
_diffrn_reflns_theta_min         2.558
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.854
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.684
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.57a (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 light green'
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       prism
_exptl_crystal_F_000             1238
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.155
_exptl_crystal_size_min          0.137
_refine_diff_density_max         1.845
_refine_diff_density_min         -1.099
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.080
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     776
_refine_ls_number_reflns         18696
_refine_ls_number_restraints     1059
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0564
_refine_ls_R_factor_gt           0.0421
_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^)+(0.0428P)^2^+2.9725P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0994
_refine_ls_wR_factor_ref         0.1078
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15702
_reflns_number_total             18696
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01478a2.cif
_cod_data_source_block           ah404
_cod_depositor_comments
'Adding full bibliography for 1569056--1569065.cif.'
_cod_original_cell_volume        3065.73(15)
_cod_database_code               1569059
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C59 H85 O10 Si3 Ce1'
_shelx_estimated_absorpt_t_max   0.892
_shelx_estimated_absorpt_t_min   0.828
_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
 C57-C58
 1.54 with sigma of 0.02
 C49-C48 \\sim C52-C48 \\sim C53-C48 \\sim C50-C48 \\sim C54-C48 \\sim C51-C48
 with sigma of 0.02
 C29-C27 \\sim C32-C27 \\sim C30-C27 \\sim C28-C27 \\sim C31-C27 \\sim C33-C27
 with sigma of 0.02
 C49-C50 \\sim C50-C51 \\sim C49-C51 \\sim C52-C53 \\sim C53-C54 \\sim C52-C54
 with sigma of 0.02
 C28-C29 \\sim C29-C30 \\sim C28-C30 \\sim C31-C32 \\sim C32-C33 \\sim C31-C33
 with sigma of 0.02
 C62-C61 \\sim C61-C60 \\sim C60-C59 \\sim C56-C55 \\sim C57-C56
 with sigma of 0.02
 O10-C62 \\sim O10-C59 \\sim O10-C55 \\sim O10-C58
 with sigma of 0.02
 C58-C56 \\sim C57-C55 \\sim C62-C60 \\sim C61-C59
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
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
C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
O10 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim
C62: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 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(1)
 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(1)
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(C61)=Sof(H61A)=
 Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=1-FVAR(2)
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C57)=Sof(H57A)=
 Sof(H57B)=Sof(C58)=Sof(H58A)=Sof(H58B)=FVAR(2)
 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(3)
 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(3)
6.a Secondary CH2 refined with riding coordinates:
 C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,
 H59B), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B)
6.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), C39(H39), C40(H40), C41(H41), C42(H42), C64(H64),
  C65(H65), C66(H66), C67(H67), C68(H68)
6.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), C52(H52A,H52B,H52C),
 C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C69(H69A,H69B,H69C)
;
_shelx_res_checksum              27718
_shelx_hkl_checksum              31032
_olex2_date_sample_data_collection 2022-05-24
_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 1.304
_oxdiff_exptl_absorpt_empirical_full_min 0.814