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_1569058
_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         'C48 H69 Ce Cl O9 Si3'
_chemical_formula_sum            'C48 H69 Ce Cl O9 Si3'
_chemical_formula_weight         1049.87
_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
_audit_creation_date             2022-10-09
_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                86.910(3)
_cell_angle_beta                 69.976(3)
_cell_angle_gamma                85.916(3)
_cell_formula_units_Z            2
_cell_length_a                   13.2982(5)
_cell_length_b                   13.6413(4)
_cell_length_c                   17.7827(6)
_cell_measurement_reflns_used    9270
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.1950
_cell_measurement_theta_min      3.4920
_cell_volume                     3021.66(19)
_computing_cell_refinement       'CrysAlisPro 1.171.42.71a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.71a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.71a (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 0.965
_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    -85.00 -14.00   1.00   10.00    --  -43.01 125.00-180.00   71
  2  \w   -117.00 -29.00   1.00   10.00    --  -43.01 -37.00 -60.00   88
  3  \w    -83.00 -49.00   1.00   10.00    --  -43.01 125.00   0.00   34
  4  \w   -115.00 -79.00   1.00   10.00    --  -43.01-142.00  23.00   36
  5  \w   -117.00 -19.00   1.00   10.00    --  -43.01 -37.00  30.00   98
  6  \w     68.00 109.00   1.00   40.00    --  103.49-111.00 -60.00   41
  7  \w    102.00 132.00   1.00   40.00    --  103.49 -30.00  60.00   30
  8  \w     30.00  99.00   1.00   40.00    --  103.49 -94.00-180.00   69
  9  \w    104.00 158.00   1.00   40.00    --  103.49 111.00 150.00   54
 10  \w     29.00  85.00   1.00   40.00    --  103.49 -30.00  60.00   56
 11  \w     30.00 113.00   1.00   40.00    --  103.49 -45.00-180.00   83
 12  \w     59.00  94.00   1.00   40.00    --  103.49 -94.00   0.00   35
 13  \w     34.00 107.00   1.00   40.00    --  103.49-111.00 120.00   73
 14  \w     79.00 166.00   1.00   40.00    --  103.49  30.00 -30.00   87
 15  \w    152.00 177.00   1.00   40.00    --  103.49 111.00-120.00   25
 16  \w    105.00 175.00   1.00   40.00    --  103.49 111.00-180.00   70
 17  \w     78.00 165.00   1.00   40.00    --  103.49  45.00-120.00   87
 18  \w     77.00 109.00   1.00   40.00    --  103.49-111.00-120.00   32
 19  \w     82.00 109.00   1.00   40.00    --  103.49-111.00  60.00   27
 20  \w     61.00 123.00   1.00   40.00    --  103.49 -45.00-120.00   62
;
_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      -0.0862919000
_diffrn_orient_matrix_UB_12      0.0674411000
_diffrn_orient_matrix_UB_13      0.0582021000
_diffrn_orient_matrix_UB_21      0.0101906000
_diffrn_orient_matrix_UB_22      -0.0639346000
_diffrn_orient_matrix_UB_23      0.0714135000
_diffrn_orient_matrix_UB_31      0.0877563000
_diffrn_orient_matrix_UB_32      0.0647750000
_diffrn_orient_matrix_UB_33      0.0048073000
_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  0.0448
_diffrn_reflns_av_unetI/netI     0.0588
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            22630
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.832
_diffrn_reflns_theta_min         3.250
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.145
_exptl_absorpt_correction_T_max  0.622
_exptl_absorpt_correction_T_min  0.343
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.71a (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            'clear dark yellow'
_exptl_crystal_density_diffrn    1.154
_exptl_crystal_description       plate
_exptl_crystal_F_000             1092
_exptl_crystal_size_max          0.247
_exptl_crystal_size_mid          0.145
_exptl_crystal_size_min          0.107
_refine_diff_density_max         2.585
_refine_diff_density_min         -0.807
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     701
_refine_ls_number_reflns         11626
_refine_ls_number_restraints     915
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0730
_refine_ls_R_factor_gt           0.0584
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1068P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1513
_refine_ls_wR_factor_ref         0.1636
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9353
_reflns_number_total             11626
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc01478a2.cif
_cod_data_source_block           ah478
_cod_depositor_comments
'Adding full bibliography for 1569056--1569065.cif.'
_cod_original_cell_volume        3021.68(19)
_cod_database_code               1569058
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C58.5 H80.5 O9 Si3 Cl1 Ce1'
_shelx_estimated_absorpt_t_max   0.515
_shelx_estimated_absorpt_t_min   0.271
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C59-C54 \\sim C58-C54 \\sim C60-C54 \\sim C55-C54 \\sim C56-C54 \\sim C57-C54
 with sigma of 0.02
 C59-C55 \\sim C57-C58 \\sim C60-C56
 with sigma of 0.02
 C22-C19 \\sim C19-C23
 with sigma of 0.02
 C19-C21 \\sim C17-C18 \\sim C17-C20 \\sim C21-C22 \\sim C23-C21
 with sigma of 0.02
 C19-C18 \\sim C20-C22 \\sim C23-C24
 with sigma of 0.02
 C17-C18 \\sim C21-C22 \\sim C23-C21 \\sim C24-C21 \\sim C17-C20 \\sim C19-C17
 with sigma of 0.02
 O3-C17 \\sim O3-C21
 with sigma of 0.02
 C37-C31 \\sim C36-C31 \\sim C35-C31 \\sim C34-C31 \\sim C33-C31 \\sim C32-C31
 with sigma of 0.02
 C49-C48 \\sim C50-C48 \\sim C52-C48 \\sim C51-C48 \\sim C53-C48
 with sigma of 0.02
 C50-C52 \\sim C51-C53
 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 C24 \\sim
C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C50) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C52) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
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(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C57)=Sof(H57A)=Sof(H57B)=Sof(H57C)=
 Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=1-FVAR(1)
 Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(1)
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=1-FVAR(2)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(2)
 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(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=
 FVAR(3)
 Sof(C21)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=1-FVAR(4)
 Sof(C17)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=FVAR(4)
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=
 1-FVAR(5)
 Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=
 FVAR(5)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12), C27(H27),
 C28(H28), C29(H29), C30(H30), C44(H44), C45(H45), C46(H46), C47(H47)
6.b 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), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C24(H24A,H24B,H24C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C),
 C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,
 H37C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C49(H49A,
 H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C),
 C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 120 electrons were 
found in a volume of 655\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1.2[C7H8] per Asymmetric Unit 
which account for 120 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              12318
_shelx_hkl_checksum              44893
_shelx_fab_checksum              88711
_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 2.370
_oxdiff_exptl_absorpt_empirical_full_min 0.635