Accessing homoleptic neutral and anionic five-coordinate Pr(iv) siloxide complexes.
Pandey, Pragati; Keener, Megan; Rajeshkumar, Thayalan; Scopelliti, Rosario; Sienkiewicz, Andrzej; Zivkovic, Ivica; Maron, Laurent; Mazzanti, Marinella; Chemical science 16 (2025) 21056–21067; doi:10.1039/d5sc05500h

data_1575932
_publ_section_title
;
 Accessing homoleptic neutral and anionic five-coordinate Pr(iv) siloxide
 complexes.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              21056
_journal_page_last               21067
_journal_paper_doi               10.1039/d5sc05500h
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C90 H75 K O5 Pr Si5, 2(C7 H8)'
_chemical_formula_sum            'C104 H91 K O5 Pr Si5'
_chemical_formula_weight         1741.22
_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             2025-03-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-07-04 deposited with the CCDC.	2025-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 113.9745(11)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.73996(12)
_cell_length_b                   24.71494(17)
_cell_length_c                   14.12364(13)
_cell_measurement_reflns_used    25703
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      72.7110
_cell_measurement_theta_min      3.3910
_cell_volume                     4382.36(7)
_computing_cell_refinement       'CrysAlisPro 1.171.44.97a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.98a 64-bit (release 07-03-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.97a (Rigaku OD, 2025)'
_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      139.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.988
_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      1.00  27.00   1.00    5.00    --  -40.66  75.00 122.00   26
  2  \w    -66.00 -13.00   1.00    5.00    --  -40.66  75.00 122.00   53
  3  \w     56.00  91.00   1.00   20.00    --  105.15 -75.00  -5.00   35
  4  \w    101.00 155.00   1.00   20.00    --  105.15  75.00 122.00   54
  5  \w   -103.00 -29.00   1.00    5.00    --  -40.66 -38.00-150.00   74
  6  \w   -113.00 -48.00   1.00    5.00    --  -40.66 -57.00-180.00   65
  7  \w    -86.00  -7.00   1.00    5.00    --  -40.66 125.00 -90.00   79
  8  \w    -19.00  65.00   1.00    5.00    --   40.66 -77.00 150.00   84
  9  \w     12.00  56.00   1.00    5.00    --   40.66 -75.00  -5.00   44
 10  \w      6.00  36.00   1.00    5.00    --   40.66 -99.00 -90.00   30
 11  \w     65.00 150.00   1.00   20.00    --  105.15-178.00  90.00   85
 12  \w     39.00  65.00   1.00   20.00    --  105.15-111.00-180.00   26
 13  \w    123.00 178.00   1.00   20.00    --  105.15  30.00-120.00   55
 14  \w     77.00 145.00   1.00   20.00    --  105.15  30.00 -90.00   68
 15  \w     37.00 109.00   1.00   20.00    --  105.15-111.00  90.00   72
 16  \w     76.00 176.00   1.00   20.00    --  105.15  61.00-180.00  100
 17  \w    145.00 171.00   1.00   20.00    --  105.15  77.00   0.00   26
 18  \w     24.00  90.00   1.00   20.00    --  105.15 -94.00 120.00   66
 19  \w     36.00 107.00   1.00   20.00    --  105.15 -30.00  60.00   71
 20  \w     78.00 177.00   1.00   20.00    --  105.15  15.00  90.00   99
 21  \w     36.00 120.00   1.00   20.00    --  105.15 -45.00-150.00   84
 22  \w    105.00 131.00   1.00   20.00    --  105.15  77.00-120.00   26
 23  \w     84.00 109.00   1.00   20.00    --  105.15  30.00-120.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1033938000
_diffrn_orient_matrix_UB_12      0.0268939000
_diffrn_orient_matrix_UB_13      -0.0761145000
_diffrn_orient_matrix_UB_21      0.0661176000
_diffrn_orient_matrix_UB_22      0.0438186000
_diffrn_orient_matrix_UB_23      -0.0245422000
_diffrn_orient_matrix_UB_31      0.0031449000
_diffrn_orient_matrix_UB_32      -0.0353198000
_diffrn_orient_matrix_UB_33      -0.0885332000
_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  0.0406
_diffrn_reflns_av_unetI/netI     0.0510
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            35525
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.813
_diffrn_reflns_theta_min         3.425
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.768
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.533
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.97a (Rigaku Oxford Diffraction, 2025)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear intense red'
_exptl_crystal_density_diffrn    1.320
_exptl_crystal_description       plate
_exptl_crystal_F_000             1806
_exptl_crystal_size_max          0.222
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.103
_refine_diff_density_max         1.838
_refine_diff_density_min         -1.295
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Flack x determined using 7568 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.0095(16)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.163
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1047
_refine_ls_number_reflns         16970
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.163
_refine_ls_R_factor_all          0.0460
_refine_ls_R_factor_gt           0.0456
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0170P)^2^+12.6685P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1153
_refine_ls_wR_factor_ref         0.1155
_reflns_Friedel_coverage         0.922
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.956
_reflns_number_gt                16786
_reflns_number_total             16970
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05500h2.cif
_cod_data_source_block           pp367
_cod_depositor_comments
'Adding full bibliography for 1575928--1575935.cif.'
_cod_database_code               1575932
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C104 H91 O5 Si5 K1 Pr1'
_chemical_oxdiff_usercomment     'CSD: WUJLUJ'
_shelx_estimated_absorpt_t_max   0.588
_shelx_estimated_absorpt_t_min   0.361
_diffrn_oxdiff_digest_od_ed
;

;
_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.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24), C26(H26), C27(H27), C28(H28), C29(H29),
 C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C38(H38), C39(H39),
  C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47),
 C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57),
  C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65),
 C66(H66), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C74(H74), C75(H75),
  C76(H76), C77(H77), C78(H78), C80(H80), C81(H81), C82(H82), C83(H83),
 C84(H84), C86(H86), C87(H87), C88(H88), C89(H89), C90(H90), C92(H92), C93(H93),
  C94(H94), C95(H95), C96(H96), C99(H99), C100(H100), C101(H101), C102(H102),
 C103(H103)
2.b Idealised Me refined as rotating group:
 C97(H97A,H97B,H97C), C104(H10A,H10B,H10C)
;
_shelx_res_checksum              692
_olex2_date_sample_data_collection 2025-03-12
_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 1.954
_oxdiff_exptl_absorpt_empirical_full_min 0.444