Comparison of Ce(iv)/Th(iv)-alkynyl complexes and observation of a <i>trans</i>-influence ligand series for Ce(iv).
Yang, Qiaomu; Yu, Xiaojuan; Lapsheva, Ekaterina; Pandey, Pragati; Smith, Patrick W.; Gupta, Himanshu; Gau, Michael R.; Carroll, Patrick J.; Minasian, Stefan G.; Autschbach, Jochen; Schelter, Eric J.; Chemical science 16 (2025) 16597–16609; doi:10.1039/d5sc03222a

data_1575354
_publ_section_title
;
 Comparison of Ce(iv)/Th(iv)-alkynyl complexes and observation of a
 <i>trans</i>-influence ligand series for Ce(iv).
;
_journal_issue                   36
_journal_name_full               'Chemical science'
_journal_page_first              16597
_journal_page_last               16609
_journal_paper_doi               10.1039/d5sc03222a
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C38 H54 N4 O3 Si Th, 1.5(C H2 Cl2)'
_chemical_formula_sum            'C39.5 H57 Cl3 N4 O3 Si Th'
_chemical_formula_weight         1002.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-31
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-04-30 deposited with the CCDC.	2025-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.847(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.9331(3)
_cell_length_b                   17.7463(4)
_cell_length_c                   21.5867(9)
_cell_measurement_reflns_used    26539
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.25
_cell_measurement_theta_min      2.21
_cell_volume                     4565.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'HPC area detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Dectris Pilatus3 R 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_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    -25.00  30.00   0.50   60.00    --    6.66 -77.00  90.00  110
  2  \w     -9.00  59.00   0.50   60.00    --    6.66  57.00-150.00  136
  3  \w    -17.00  25.00   0.50   60.00    --    6.66  77.00 -30.00   84
  4  \w     -9.00  59.00   0.50   60.00    --    6.66  57.00  90.00  136
  5  \w    -25.00  30.00   0.50   60.00    --    6.66 -77.00   0.00  110
  6  \w    -31.00  25.00   0.50   60.00    --   -7.13  77.00  90.00  112
  7  \w    -85.00   8.00   0.50   60.00    --   -7.13 -37.00-150.00  186
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-S'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0553707000
_diffrn_orient_matrix_UB_12      0.0043579000
_diffrn_orient_matrix_UB_13      -0.0130936000
_diffrn_orient_matrix_UB_21      -0.0199937000
_diffrn_orient_matrix_UB_22      0.0051580000
_diffrn_orient_matrix_UB_23      0.0300936000
_diffrn_orient_matrix_UB_31      0.0087015000
_diffrn_orient_matrix_UB_32      0.0393793000
_diffrn_orient_matrix_UB_33      -0.0025313000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0612
_diffrn_reflns_av_unetI/netI     0.0701
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            66333
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.948
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.282
_diffrn_reflns_theta_min         2.058
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.505
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.4328
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SCALE3 ABSPACK'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.458
_exptl_crystal_description       plate
_exptl_crystal_F_000             2004
_exptl_crystal_size_max          0.42
_exptl_crystal_size_mid          0.26
_exptl_crystal_size_min          0.06
_refine_diff_density_max         4.772
_refine_diff_density_min         -2.035
_refine_diff_density_rms         0.175
_refine_ls_abs_structure_details
;
 Flack x determined using 6739 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.010(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     991
_refine_ls_number_reflns         21479
_refine_ls_number_restraints     123
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0757
_refine_ls_R_factor_gt           0.0601
_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^)+(0.0674P)^2^+30.6561P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1412
_refine_ls_wR_factor_ref         0.1475
_reflns_Friedel_coverage         0.848
_reflns_Friedel_fraction_full    0.948
_reflns_Friedel_fraction_max     0.898
_reflns_number_gt                17871
_reflns_number_total             21479
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03222a2.cif
_cod_data_source_block           40646_1-ThTMS
_cod_depositor_comments
'Adding full bibliography for 1575353--1575355.cif.'
_cod_original_formula_sum        'C39.50 H57 Cl3 N4 O3 Si Th'
_cod_database_code               1575354
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.817
_shelx_estimated_absorpt_t_min   0.321
_shelx_res_checksum              4983
_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 1.906
_oxdiff_exptl_absorpt_empirical_full_min 0.613