Assembly of a trapped valent Ce<sup>III/IV</sup>-TCNQ complex through metal-ligand redox cooperativity.
Gupta, Himanshu; Vincenzini, Brett D.; Bacon, Alexandra M.; Schelter, Eric J.; Chemical communications (Cambridge, England) 60 (2024) 6909–6912; doi:10.1039/d4cc01478b

data_7133167
_publ_section_title
;
 Assembly of a trapped valent Ce<sup>III/IV</sup>-TCNQ complex through
 metal-ligand redox cooperativity.
;
_journal_issue                   54
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6909
_journal_page_last               6912
_journal_paper_doi               10.1039/d4cc01478b
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C72 H64 Ce4 N4, 3(C7 H8)'
_chemical_formula_sum            'C93 H88 Ce4 N4'
_chemical_formula_weight         1822.15
_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
_audit_creation_date             2024-03-25
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2024-03-27 deposited with the CCDC.	2024-06-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.1720(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   8.09830(10)
_cell_length_b                   17.55890(10)
_cell_length_c                   27.1102(2)
_cell_measurement_reflns_used    33616
_cell_measurement_temperature    100
_cell_measurement_theta_max      74.2760
_cell_measurement_theta_min      2.9780
_cell_volume                     3854.98(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.94a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.94a 64-bit (release 20-10-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.94a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100
_diffrn_detector                 'HPC area detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-6000HE
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.993
_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    -46.00  26.00   0.50    0.31    --  -47.54  38.00 -90.00  144
  2  \w    -30.00  29.00   0.50    0.31    --  -47.54  19.00-180.00  118
  3  \w   -121.00 -32.00   0.50    0.31    --  -47.54 -57.00 120.00  178
  4  \w    -71.00  26.00   0.50    0.31    --  -47.54  77.00  30.00  194
  5  \w    -26.00  40.00   0.50    0.31    --   47.54 -38.00 -90.00  132
  6  \w    -25.00 120.00   0.50    0.31    --   47.54   0.00 -90.00  290
  7  \w    -28.00  24.00   0.50    0.31    --   47.54 -19.00  60.00  104
  8  \w   -115.00 -16.00   0.50    1.23    --  -90.00  80.00 115.26  198
  9  \w   -115.00 -16.00   0.50    1.23    --  -90.00  80.00 115.26  198
 10  \w   -115.00 -16.00   0.50    1.23    --  -90.00  80.00 -37.72  198
 11  \w   -108.00 -64.00   0.50    1.23    --  -90.00  80.00 -37.72   88
 12  \w     42.00  68.00   0.50    1.23    --  113.25 -61.00  30.00   52
 13  \w     54.00 100.00   0.50    1.23    --  113.25 -80.00-114.18   92
 14  \w    100.00 177.00   0.50    1.23    --  113.25  30.00 150.00  154
 15  \w     56.00 138.00   0.50    1.23    --  113.25 -80.00 -88.11  164
 16  \w    100.00 178.00   0.50    1.23    --  113.25  61.00  30.00  156
 17  \w     65.00 137.00   0.50    1.23    --  113.25 -80.00 170.66  144
 18  \w     41.00 138.00   0.50    1.23    --  113.25 -80.00 -62.97  194
 19  \w    100.00 132.00   0.50    1.23    --  113.25  30.00 -60.00   64
 20  \w     41.00 117.00   0.50    1.23    --  113.25 -80.00-141.60  152
 21  \w     62.00  94.00   0.50    1.23    --  113.25 -77.00  30.00   64
 22  \w    153.00 178.00   0.50    1.23    --  113.25  30.00 -60.00   50
 23  \w    143.00 178.00   0.50    1.23    --  113.25  45.00 -30.00   70
 24  \w     41.00  68.00   0.50    1.23    --  113.25 -61.00 120.00   54
 25  \w     43.00  68.00   0.50    1.23    --  113.25 -61.00 -60.00   50
 26  \w     99.00 164.00   0.50    1.23    --  113.25  15.00-150.00  130
 27  \w    100.00 135.00   0.50    1.23    --  113.25  45.00 -30.00   70
 28  \w     95.00 128.00   0.50    1.23    --  113.25 -79.00 -27.25   66
 29  \w    110.00 144.00   0.50    1.23    --  113.25  61.00-120.00   68
 30  \w     42.00  70.00   0.50    1.23    --  113.25 -77.00 150.00   56
 31  \w    146.00 176.00   0.50    1.23    --  113.25  45.00   0.00   60
 32  \w     93.00 141.00   0.50    1.23    --  113.25  77.00   0.00   96
 33  \w    101.00 137.00   0.50    1.23    --  113.25  45.00   0.00   72
 34  \w     60.00  86.00   0.50    1.23    --  113.25 -79.00 -27.25   52
 35  \w     41.00  67.00   0.50    1.23    --  113.25 -61.00  60.00   52
 36  \w    150.00 177.00   0.50    1.23    --  113.25  77.00   0.00   54
 37  \w     48.00  79.00   0.50    1.23    --  113.25 -77.00-180.00   62
 38  \w     53.00  91.00   0.50    1.23    --  113.25 -77.00  90.00   76
 39  \w    100.00 178.00   0.50    1.23    --  113.25  45.00  90.00  156
 40  \w    103.00 157.00   0.50    1.23    --  113.25  30.00 120.00  108
 41  \w     84.00 125.00   0.50    1.23    --  113.25 -79.00 107.65   82
 42  \w     70.00  96.00   0.50    1.23    --  113.25 -77.00 120.00   52
 43  \w    123.00 150.00   0.50    1.23    --  113.25  45.00  60.00   54
 44  \w     66.00 130.00   0.50    1.23    --  113.25 -80.00  61.73  128
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1490728000
_diffrn_orient_matrix_UB_12      -0.0245825000
_diffrn_orient_matrix_UB_13      0.0316726000
_diffrn_orient_matrix_UB_21      0.0321287000
_diffrn_orient_matrix_UB_22      0.0837999000
_diffrn_orient_matrix_UB_23      0.0138738000
_diffrn_orient_matrix_UB_31      -0.1137372000
_diffrn_orient_matrix_UB_32      -0.0085069000
_diffrn_orient_matrix_UB_33      0.0450866000
_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  0.0615
_diffrn_reflns_av_unetI/netI     0.0290
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            61439
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.503
_diffrn_reflns_theta_min         2.998
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.257
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27259
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SCALE3 ABSPACK'
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.570
_exptl_crystal_description       plate
_exptl_crystal_F_000             1812
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.262
_refine_diff_density_min         -0.772
_refine_diff_density_rms         0.105
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     474
_refine_ls_number_reflns         7821
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0304
_refine_ls_R_factor_gt           0.0280
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0466P)^2^+4.6224P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0739
_refine_ls_wR_factor_ref         0.0769
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7312
_reflns_number_total             7821
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01478b2.cif
_cod_data_source_block           40763_Cmpd1
_cod_depositor_comments          'Adding full bibliography for 7133167.cif.'
_cod_database_code               7133167
_shelx_shelxl_version_number     2019/3
_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. Uiso/Uaniso restraints and constraints
C49 \\sim C50 \\sim C44 \\sim C45 \\sim C48 \\sim C46 \\sim C47: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
3. Others
 Fixed Sof: C50(0.5) H50A(0.5) H50B(0.5) H50C(0.5) C44(0.5) C49(0.5) H49(0.5)
 C48(0.5) H48(0.5) C47(0.5) H47(0.5) C46(0.5) H46(0.5) C45(0.5) H45(0.5)
4.a Free rotating group:
 C50(C44,C49,C48,C47,C46,C45)
4.b Ternary CH refined with riding coordinates:
 C8(H8), C11(H11), C12(H12), C16(H16)
4.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C13(H13), C14(H14), C15(H15),
 C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
  C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31),
 C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39), C40(H40),
  C41(H41), C42(H42), C49(H49), C48(H48), C47(H47), C46(H46), C45(H45)
4.d Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C), C50(H50A,H50B,H50C)
;
_shelx_res_checksum              55657
_shelx_hkl_checksum              3503
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 3.554
_oxdiff_exptl_absorpt_empirical_full_min 0.568