Structural distortion by alkali metal cations modulates the redox and electronic properties of Ce<sup>3+</sup> imidophosphorane complexes.
Boggiano, Andrew C.; Studvick, Chad M.; Steiner, Alexander; Bacsa, John; Popov, Ivan A.; La Pierre, Henry S.; Chemical science 14 (2023) 11708–11717; doi:10.1039/d3sc04262f

data_1569945
_publ_section_title
;
 Structural distortion by alkali metal cations modulates the redox and
 electronic properties of Ce<sup>3+</sup> imidophosphorane complexes.
;
_journal_issue                   42
_journal_name_full               'Chemical science'
_journal_page_first              11708
_journal_page_last               11717
_journal_paper_doi               10.1039/d3sc04262f
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         '2(C60 H138 Ce Cs N16 O P4), 2(C4 H10 O)'
_chemical_formula_sum            'C128 H296 Ce2 Cs2 N32 O4 P8'
_chemical_formula_weight         3141.77
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2023-04-12
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-05-01 deposited with the CCDC.	2023-09-18 downloaded from the CCDC.
;
_cell_angle_alpha                105.027(7)
_cell_angle_beta                 96.887(7)
_cell_angle_gamma                109.734(6)
_cell_formula_units_Z            2
_cell_length_a                   13.915(3)
_cell_length_b                   13.928(2)
_cell_length_c                   24.247(5)
_cell_measurement_reflns_used    9323
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      38.02
_cell_measurement_theta_min      2.65
_cell_volume                     4159.3(14)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2016)'
_computing_data_collection       'APEX2  v2016.5-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2016)'
_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_temperature      100.00
_diffrn_detector_area_resol_mean 7.495
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker D8 VENTURE diffractometer'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0558
_diffrn_reflns_av_unetI/netI     0.0741
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            112618
_diffrn_reflns_point_group_measured_fraction_full 0.912
_diffrn_reflns_point_group_measured_fraction_max 0.837
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         35.631
_diffrn_reflns_theta_min         2.000
_exptl_absorpt_coefficient_mu    1.102
_exptl_absorpt_correction_T_max  0.7476
_exptl_absorpt_correction_T_min  0.6427
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS v.2016/2. (Krause, L. et al, 2015)'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.254
_exptl_crystal_description       plate
_exptl_crystal_F_000             1666
_exptl_crystal_size_max          0.308
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.18
_refine_diff_density_max         3.583
_refine_diff_density_min         -3.642
_refine_diff_density_rms         0.131
_refine_ls_abs_structure_details
;
 Flack x determined using 23102 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.006(5)
_refine_ls_extinction_coef       0.00096(17)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1659
_refine_ls_number_reflns         64250
_refine_ls_number_restraints     448
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0538
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0349P)^2^+8.9580P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1284
_refine_ls_wR_factor_ref         0.1363
_reflns_Friedel_coverage         0.682
_reflns_Friedel_fraction_full    0.831
_reflns_Friedel_fraction_max     0.679
_reflns_number_gt                61353
_reflns_number_total             64250
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04262f2.cif
_cod_data_source_block           ab-b168_p1
_cod_depositor_comments
'Adding full bibliography for 1569945--1569949.cif.'
_cod_database_code               1569945
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.7720(7)
 0.2280(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 Cs2-C5
 -3.92 with sigma of 0.01
 O2-C7 = O2-C5
 1.4204 with sigma of 0.002
 O2-C6
 2.3917 with sigma of 0.004
 O2-C8
 2.3917 with sigma of 0.004
 C5-C7
 2.3753 with sigma of 0.004
 C8-C7 = C6-C5
 1.52 with sigma of 0.002
 C1_18-C2_18
 1.525 with sigma of 0.002
 C2_18-C3_18
 2.375 with sigma of 0.002
 C4_18-C3_18
 1.525 with sigma of 0.002
 C3_19-C4_19 = C2_19-C1_19
 1.525 with sigma of 0.002
 C3_19-C2_19
 2.375 with sigma of 0.002
 O2-C6 \\sim O2-C8
 with sigma of 0.04
 O2-C5 \\sim O2-C7
 with sigma of 0.01
 C5-C6 \\sim C7-C8
 with sigma of 0.02
 O1_19-C3_19 \\sim O1_19-C2_19
 with sigma of 0.002
 N1_26-C13_26 \\sim N1_26-C11_26
 with sigma of 0.0002
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1A
Uanis(C6) \\sim Ueq, Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 O2, C5, C6
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 O2, C5, C6, C7, C8
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O2, C7, C8
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 O1_18, C1_18, C2_18, C3_18, C4_18
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 O1_18, C1_18, C2_18, C3_18, C4_18
 O1_19, C1_19, C2_19, C3_19, C4_19
 O1_27, C1_27, C2_27, C3_27, C4_27
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.002
 O1_19, C1_19, C2_19, C3_19, C4_19
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 O1_19, C1_19
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 N1_20, C11_20, C12_20, C13_20, C14_20
 N1_21, C11_21, C12_21, C13_21, C14_21
 N1_22, C11_22, C12_22, C13_22, C14_22
 N1_23, C11_23, C12_23, C13_23, C14_23
 N1_24, C11_24, C12_24, C13_24, C14_24
 N1_25, C11_25, C12_25, C13_25, C14_25
 N1_26, C11_26, C12_26, C13_26, C14_26
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
6. Same fragment restrains
{N1_21, C11_21, C12_21, C13_21, C14_21}
{N1_22, C11_22, C12_22, C13_22, C14_22}
{N1_23, C11_23, C12_23, C13_23, C14_23}
{N1_24, C11_24, C12_24, C13_24, C14_24}
{N1_25, C11_25, C12_25, C13_25, C14_25}
{N1_26, C11_26, C12_26, C13_26, C14_26}
as
{N1_20, C11_20, C12_20, C13_20, C14_20} sigma for 1-2: 0.02 1-3: 0.04
{O1_19, C1_19, C2_19, C3_19, C4_19}
{O1_27, C1_27, C2_27, C3_27, C4_27}
as
{O1_18, C1_18, C2_18, C3_18, C4_18} sigma for 1-2: 0.02 1-3: 0
7.a Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C7(H7A,H7B), C2(H2A,H2B), C3(H3A,H3B), C2(H2A,H2B), C3(H3A,H3B),
 C2(H2A,H2B), C3(H3A,H3B), C11(H11A,H11B), C13(H13A,H13B), C11(H11A,H11B),
 C13(H13A,H13B), C11(H11A,H11B), C13(H13A,H13B), C11(H11A,H11B), C13(H13A,H13B),
  C11(H11A,H11B), C13(H13A,H13B), C11(H11A,H11B), C13(H13A,H13B), C11(H11A,
 H11B), C13(H13A,H13B), C1(H1A,H1B), C2(H2A,H2B), C1(H1A,H1B), C2(H2A,H2B),
 C1(H1A,H1B), C2(H2A,H2B), C1(H1A,H1B), C2(H2A,H2B), C1(H1A,H1B), C2(H2A,H2B),
 C1(H1A,H1B), C2(H2A,H2B), C1(H1A,H1B), C2(H2A,H2B), C11(H11A,H11B), C13(H13A,
 H13B), C1(H1A,H1B), C2(H2A,H2B)
7.b Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C1(H1A,H1B,H1C), C4(H4A,H4B,H4C), C1(H1A,
 H1B,H1C), C4(H4A,H4B,H4C), C1(H1A,H1B,H1C), C4(H4A,H4B,H4C), C12(H12A,H12B,
 H12C), C14(H14A,H14B,H14C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C12(H12A,
 H12B,H12C), C14(H14A,H14B,H14C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C),
 C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C12(H12A,H12B,H12C), C14(H14A,H14B,
 H14C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C), C5(H5A,H5B,
 H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,
 H9C), C10(H10A,H10B,H10C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C),
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C4(H4A,H4B,H4C), C5(H5A,
 H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,
 H10C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C),
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,
 H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C4(H4A,H4B,
 H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C),
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C),
  C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,
 H10B,H10C)
;
_shelx_res_checksum              92482
_olex2_submission_special_instructions 'No special instructions were received'