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_1569061
_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         'C96 H138 K6 O18 Si6, 2(C18 H36 K N2 O6)'
_chemical_formula_sum            'C132 H210 K8 N4 O30 Si6'
_chemical_formula_weight         2814.37
_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             2022-09-13
_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                112.666(3)
_cell_angle_beta                 95.795(2)
_cell_angle_gamma                108.276(2)
_cell_formula_units_Z            1
_cell_length_a                   15.5349(4)
_cell_length_b                   16.9728(5)
_cell_length_c                   21.2514(6)
_cell_measurement_reflns_used    18920
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.3120
_cell_measurement_theta_min      3.3050
_cell_volume                     4749.9(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.65a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.65a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.65a (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 0.974
_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   8.00   1.00    6.00    --  -42.88  95.00 163.00   89
  2  \w     25.00  64.00   1.00    6.00    --   42.88 -95.00  53.00   39
  3  \w    114.00 166.00   1.00   24.00    --  103.49  95.00 163.00   52
  4  \w     48.00  73.00   1.00   24.00    --  103.49 -95.00  53.00   25
  5  \w   -117.00 -21.00   1.00    6.00    --  -42.88 -37.00 -60.00   96
  6  \w   -117.00 -19.00   1.00    6.00    --  -42.88 -37.00  30.00   98
  7  \w     71.00  98.00   1.00    6.00    --   42.88  57.00 -60.00   27
  8  \w     15.00  66.00   1.00    6.00    --   42.88  57.00 -60.00   51
  9  \w    148.00 175.00   1.00   24.00    --  103.49 111.00-120.00   27
 10  \w    112.00 139.00   1.00   24.00    --  103.49 111.00  30.00   27
 11  \w     28.00 132.00   1.00   24.00    --  103.49 -30.00  30.00  104
 12  \w    136.00 163.00   1.00   24.00    --  103.49 111.00-150.00   27
 13  \w     49.00 107.00   1.00   24.00    --  103.49-111.00-180.00   58
 14  \w    104.00 130.00   1.00   24.00    --  103.49 111.00-120.00   26
 15  \w     50.00  98.00   1.00   24.00    --  103.49-111.00 -30.00   48
 16  \w    105.00 163.00   1.00   24.00    --  103.49 111.00  90.00   58
 17  \w    145.00 175.00   1.00   24.00    --  103.49 111.00  30.00   30
 18  \w     78.00 177.00   1.00   24.00    --  103.49  45.00-150.00   99
 19  \w    104.00 176.00   1.00   24.00    --  103.49 111.00 120.00   72
 20  \w     44.00 109.00   1.00   24.00    --  103.49-111.00  90.00   65
 21  \w     84.00 109.00   1.00   24.00    --  103.49-111.00   0.00   25
 22  \w    133.00 160.00   1.00   24.00    --  103.49 111.00   0.00   27
 23  \w     37.00  64.00   1.00   24.00    --  103.49 -94.00-150.00   27
 24  \w     33.00 109.00   1.00   24.00    --  103.49-111.00-120.00   76
 25  \w     37.00 124.00   1.00   24.00    --  103.49 -30.00-180.00   87
;
_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      0.1028264000
_diffrn_orient_matrix_UB_12      0.0683387000
_diffrn_orient_matrix_UB_13      0.0243220000
_diffrn_orient_matrix_UB_21      -0.0088821000
_diffrn_orient_matrix_UB_22      0.0030166000
_diffrn_orient_matrix_UB_23      -0.0718203000
_diffrn_orient_matrix_UB_31      -0.0316470000
_diffrn_orient_matrix_UB_32      0.0816657000
_diffrn_orient_matrix_UB_33      0.0290603000
_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  0.0297
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            41088
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.465
_diffrn_reflns_theta_min         2.912
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.418
_exptl_absorpt_correction_T_max  0.717
_exptl_absorpt_correction_T_min  0.562
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.65a (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            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    0.984
_exptl_crystal_description       prism
_exptl_crystal_F_000             1506
_exptl_crystal_size_max          0.379
_exptl_crystal_size_mid          0.235
_exptl_crystal_size_min          0.198
_refine_diff_density_max         0.692
_refine_diff_density_min         -0.271
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     920
_refine_ls_number_reflns         18336
_refine_ls_number_restraints     898
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0521
_refine_ls_R_factor_gt           0.0410
_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^)+(0.0670P)^2^+0.1620P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1096
_refine_ls_wR_factor_ref         0.1167
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14570
_reflns_number_total             18336
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01478a2.cif
_cod_data_source_block           ah448
_cod_depositor_comments
'Adding full bibliography for 1569056--1569065.cif.'
_cod_original_cell_volume        4749.9(2)
_cod_database_code               1569061
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C168 H286 N4 O36 K8 Si6'
_shelx_estimated_absorpt_t_max   0.646
_shelx_estimated_absorpt_t_min   0.461
_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
 C60-C54 = C49-C72
 2.4 with sigma of 0.02
 C49-C61
 2.4 with sigma of 0.02
 N1-C55 \\sim N1-C61 \\sim N1-C49 \\sim N3-C55 \\sim N3-C49 \\sim N3-C72 \\sim
N12-C54 \\sim N2-C54 \\sim N2-
 C60 \\sim N12-C60 \\sim N12-C67 \\sim N2-C66
 with sigma of 0.02
 O16-C71 \\sim O16-C70 \\sim O14-C62 \\sim O14-C63 \\sim O17-C69 \\sim O17-C68
\\sim O15-C64 \\sim O15-C65
 with sigma of 0.02
 C72-C71 \\sim C62-C61 \\sim C70-C69 \\sim C64-C63 \\sim C68-C67 \\sim C66-C65
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O14 \\sim O15 \\sim O16 \\sim O17 \\sim N1 \\sim N2 \\sim N3 \\sim N12 \\sim
C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim
C69 \\sim C70 \\sim C71 \\sim C72: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C55) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 K4, O10, O11, O12, O13, O14, O15, O16, O17, N1, N2, N3, N12, C49, C50, C51,
 C52, C53, C54, C55, C56, C57, C58, C59, C60, C61, C62, C63, C64, C65, C66, C67,
  C68, C69, C70, C71, C72
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(O16)=Sof(O17)=Sof(N3)=Sof(N12)=Sof(H49C)=Sof(H49D)=Sof(H54C)=Sof(H54D)=
 Sof(H55C)=Sof(H55D)=Sof(H60C)=Sof(H60D)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(C68)=
 Sof(H68A)=Sof(H68B)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=1-FVAR(1)
 Sof(O14)=Sof(O15)=Sof(N1)=Sof(N2)=Sof(H49A)=Sof(H49B)=Sof(H54A)=Sof(H54B)=
 Sof(H55A)=Sof(H55B)=Sof(H60A)=Sof(H60B)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=
 Sof(H62A)=Sof(H62B)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(C64)=Sof(H64A)=Sof(H64B)=
 Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(C66)=Sof(H66A)=Sof(H66B)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C49(H49A,H49B), C49(H49C,H49D), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,
 H52B), C53(H53A,H53B), C54(H54A,H54B), C54(H54C,H54D), C55(H55A,H55B),
 C55(H55C,H55D), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B),
  C60(H60A,H60B), C60(H60C,H60D), 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)
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), C36(H36), C37(H37), C38(H38), C39(H39)
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), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 314 electrons were 
found in a volume of 1508\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
6[C4H8O], 2[C6H14] per Asymmetric Unit 
which account for 340 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              68225
_shelx_hkl_checksum              85314
_shelx_fab_checksum              34727
_olex2_date_sample_data_collection 2022-08-16
_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 1.473
_oxdiff_exptl_absorpt_empirical_full_min 0.759