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_1569064
_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, C18 H36 K N2 O6, 2(C4 H10 O)'
_chemical_formula_sum            'C78 H133 Ce K N2 O18 Si3'
_chemical_formula_weight         1650.35
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-09-09
_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                 105.036(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.1856(4)
_cell_length_b                   20.8622(4)
_cell_length_c                   21.3727(4)
_cell_measurement_reflns_used    17535
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      71.9670
_cell_measurement_theta_min      4.0400
_cell_volume                     8692.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.67a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.67a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.67a (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 0.998
_diffrn_measured_fraction_theta_max 0.976
_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    -56.00  21.00   1.00    6.00    --  -43.01  70.00-134.00   77
  2  \w   -112.00 -12.00   1.00    6.00    --  -43.01 -70.00  93.00  100
  3  \w     -3.00  22.00   1.00    6.00    --   43.01 -70.00  93.00   25
  4  \w     83.00 150.00   1.00   24.00    --  103.49  70.00-134.00   67
  5  \w     59.00 134.00   1.00   24.00    --  103.49 -70.00  93.00   75
  6  \w     28.00  66.00   1.00    6.00    --   43.01-125.00   0.00   38
  7  \w     27.00  97.00   1.00    6.00    --   43.01-125.00 120.00   70
  8  \w     46.00  72.00   1.00    6.00    --   43.01-125.00 -60.00   26
  9  \w     32.00 109.00   1.00   24.00    --  103.49-111.00 120.00   77
 10  \w    117.00 167.00   1.00   24.00    --  103.49  77.00 120.00   50
 11  \w    145.00 175.00   1.00   24.00    --  103.49  77.00 -60.00   30
 12  \w     65.00 146.00   1.00   24.00    --  103.49 178.00   0.00   81
 13  \w    111.00 176.00   1.00   24.00    --  103.49  77.00  90.00   65
 14  \w     51.00  77.00   1.00   24.00    --  103.49-111.00  60.00   26
 15  \w    103.00 177.00   1.00   24.00    --  103.49  77.00 150.00   74
;
_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      0.0492037000
_diffrn_orient_matrix_UB_12      -0.0544668000
_diffrn_orient_matrix_UB_13      -0.0068334000
_diffrn_orient_matrix_UB_21      0.0497827000
_diffrn_orient_matrix_UB_22      0.0201806000
_diffrn_orient_matrix_UB_23      0.0645686000
_diffrn_orient_matrix_UB_31      -0.0366327000
_diffrn_orient_matrix_UB_32      -0.0456425000
_diffrn_orient_matrix_UB_33      0.0367997000
_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  0.0641
_diffrn_reflns_av_unetI/netI     0.0629
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            46797
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.506
_diffrn_reflns_theta_min         3.012
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.381
_exptl_absorpt_correction_T_max  0.751
_exptl_absorpt_correction_T_min  0.197
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.67a (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            'lustrous dark blue'
_exptl_crystal_density_diffrn    1.261
_exptl_crystal_description       plate
_exptl_crystal_F_000             3512
_exptl_crystal_size_max          0.485
_exptl_crystal_size_mid          0.243
_exptl_crystal_size_min          0.065
_refine_diff_density_max         1.003
_refine_diff_density_min         -1.048
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1021
_refine_ls_number_reflns         16810
_refine_ls_number_restraints     262
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0805
_refine_ls_R_factor_gt           0.0560
_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^)+(0.0803P)^2^+6.0896P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1406
_refine_ls_wR_factor_ref         0.1613
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12656
_reflns_number_total             16810
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01478a2.cif
_cod_data_source_block           ah445-3
_cod_depositor_comments
'Adding full bibliography for 1569056--1569065.cif.'
_cod_database_code               1569064
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C78 H133 N2 O18 Si3 K1 Ce1'
_shelx_estimated_absorpt_t_max   0.721
_shelx_estimated_absorpt_t_min   0.180
_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
 O16-C79 = O16-C78
 1.43 with sigma of 0.02
 C78-C77 = C80-C79
 1.54 with sigma of 0.02
 C22-C17 \\sim C18-C17 \\sim C19-C17 \\sim C23-C17 \\sim C20-C17 \\sim C21-C17
\\sim C35-C34 \\sim C38-C34
 \\sim C37-C34 \\sim C39-C34 \\sim C36-C34 \\sim C40-C34
 with sigma of 0.02
 C39-C38 \\sim C38-C40 \\sim C39-C40 \\sim C35-C36 \\sim C36-C37 \\sim C35-C37
 with sigma of 0.02
 C18-C19 \\sim C19-C20 \\sim C18-C20 \\sim C22-C21 \\sim C21-C23 \\sim C22-C23
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C34 \\sim
C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
Uanis(C56) \\sim Ueq, Uanis(C57) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C58) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(Ce2)=1-FVAR(1)
 Sof(Ce1)=FVAR(1)
 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(2)
 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(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 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), C63(H63A,H63B),
 C64(H64A,H64B), C65(H65A,H65B), C66(H66A,H66B), 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), C78(H78A,H78B),
 C79(H79A,H79B), C82(H82A,H82B), C83(H83A,H83B)
5.b Me refined with riding coordinates:
 C77(H77A,H77B,H77C)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), 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), C80(H80A,H80B,H80C), C81(H81A,H81B,
 H81C), C84(H84A,H84B,H84C)
;
_shelx_res_checksum              37862
_shelx_hkl_checksum              21623
_olex2_date_sample_data_collection 2022-08-29
_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 1.622
_oxdiff_exptl_absorpt_empirical_full_min 0.602