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_1575935
_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_absolute_configuration rmad
_chemical_formula_moiety         'C90 H75 Cs O5 Pr Si5, 2(C7 H8)'
_chemical_formula_sum            'C104 H91 Cs O5 Pr Si5'
_chemical_formula_weight         1835.119
_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'
_symmetry_Int_Tables_number      4
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-30
_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                 113.942(16)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.7546(18)
_cell_length_b                   24.859(3)
_cell_length_c                   14.1649(18)
_cell_measurement_reflns_used    2458
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      71.4760
_cell_measurement_theta_min      3.4020
_cell_volume                     4426.6(11)
_computing_cell_refinement       'CrysAlisPro 1.171.44.106a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.105a 64-bit (release 14-04-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.106a (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  'olex2.refine 1.5 (Bourhis et al., 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 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.0000
_diffrn_measured_fraction_theta_max 1.0000
_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    -83.00   0.00   1.00   10.00    --  -40.91 112.00 122.00   83
  2  \w     36.00  77.00   1.00   10.00    --   40.91-112.00  29.00   41
  3  \w     83.00 109.00   1.00   40.00    --  105.15-112.00  29.00   26
  4  \w    105.00 178.00   1.00   40.00    --  105.15 112.00 122.00   73
  5  \w   -112.00 -17.00   1.00   10.00    --  -40.91 -38.00-150.00   95
  6  \w   -108.00 -17.00   1.00   10.00    --  -40.91 -38.00 -30.00   91
  7  \w    -62.00  29.00   1.00   10.00    --  -40.91  38.00 -60.00   91
  8  \w    103.00 177.00   1.00   40.00    --  105.15  77.00   0.00   74
  9  \w     35.00 108.00   1.00   40.00    --  105.15-111.00 -60.00   73
 10  \w    106.00 153.00   1.00   40.00    --  105.15 111.00 -30.00   47
 11  \w     87.00 133.00   1.00   40.00    --  105.15 -61.00  60.00   46
 12  \w     33.00 105.00   1.00   40.00    --  105.15-111.00-150.00   72
 13  \w     77.00 112.00   1.00   40.00    --  105.15 -61.00 150.00   35
 14  \w     32.00  89.00   1.00   40.00    --  105.15 -45.00-150.00   57
 15  \w     77.00 178.00   1.00   40.00    --  105.15  30.00 -60.00  101
 16  \w     82.00 109.00   1.00   40.00    --  105.15-111.00  90.00   27
 17  \w    105.00 175.00   1.00   40.00    --  105.15 111.00-120.00   70
 18  \w    106.00 164.00   1.00   40.00    --  105.15  77.00 150.00   58
 19  \w     34.00  59.00   1.00   40.00    --  105.15 -61.00  60.00   25
 20  \w     95.00 131.00   1.00   40.00    --  105.15 -61.00-150.00   36
 21  \w     32.00  90.00   1.00   40.00    --  105.15 -77.00  30.00   58
 22  \w     95.00 120.00   1.00   40.00    --  105.15 -77.00  30.00   25
 23  \w    132.00 177.00   1.00   40.00    --  105.15  45.00-150.00   45
 24  \w    116.00 142.00   1.00   40.00    --  105.15  77.00-150.00   26
 25  \w     81.00 106.00   1.00   40.00    --  105.15  45.00-150.00   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      -0.1072673000
_diffrn_orient_matrix_UB_12      0.0147988000
_diffrn_orient_matrix_UB_13      -0.0880052000
_diffrn_orient_matrix_UB_21      0.0364771000
_diffrn_orient_matrix_UB_22      0.0590210000
_diffrn_orient_matrix_UB_23      0.0059121000
_diffrn_orient_matrix_UB_31      0.0466396000
_diffrn_orient_matrix_UB_32      -0.0120900000
_diffrn_orient_matrix_UB_33      -0.0798539000
_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  0.1516
_diffrn_reflns_av_unetI/netI     0.2159
_diffrn_reflns_Laue_measured_fraction_full 1.0000
_diffrn_reflns_Laue_measured_fraction_max 1.0000
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            37886
_diffrn_reflns_point_group_measured_fraction_full 0.9995
_diffrn_reflns_point_group_measured_fraction_max 0.9995
_diffrn_reflns_theta_full        66.5900
_diffrn_reflns_theta_max         66.59
_diffrn_reflns_theta_min         3.41
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.448
_exptl_absorpt_correction_T_max  0.807
_exptl_absorpt_correction_T_min  0.546
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.106a (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 orange'
_exptl_crystal_density_diffrn    1.377
_exptl_crystal_description       prism
_exptl_crystal_F_000             1881.985
_exptl_crystal_size_max          0.085
_exptl_crystal_size_mid          0.062
_exptl_crystal_size_min          0.045
_refine_diff_density_max         1.4275
_refine_diff_density_min         -1.1123
_refine_diff_density_rms         0.1921
_refine_ls_abs_structure_details
'Hooft, R.W.W., Straver, L.H., Spek, A.L. (2010). J. Appl. Cryst., 43, 665-668.'
_refine_ls_abs_structure_Flack   -0.040(6)
_refine_ls_d_res_high            0.8401
_refine_ls_d_res_low             12.9461
_refine_ls_goodness_of_fit_ref   0.9344
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    178
_refine_ls_number_parameters     1097
_refine_ls_number_reflns         15611
_refine_ls_number_restraints     1363
_refine_ls_restrained_S_all      0.8934
_refine_ls_R_factor_all          0.1165
_refine_ls_R_factor_gt           0.0714
_refine_ls_shift/su_max          0.0010
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1436
_refine_ls_wR_factor_ref         0.1784
_reflns_Friedel_coverage         0.999
_reflns_limit_h_max              16
_reflns_limit_h_min              -16
_reflns_limit_k_max              29
_reflns_limit_k_min              -29
_reflns_limit_l_max              16
_reflns_limit_l_min              -16
_reflns_number_gt                9915
_reflns_number_total             15611
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5sc05500h2.cif
_cod_data_source_block           PP366
_cod_depositor_comments
'Adding full bibliography for 1575928--1575935.cif.'
_cod_original_sg_symbol_Hall     ' P 2yb'
_cod_database_code               1575935
_chemical_oxdiff_formula         'C104 H91 O5 Si5 Cs1 Pr1'
_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. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
3.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)
3.b Idealised Me refined as rotating group:
 C97(H97a,H97b,H97c), C104(H10a,H10b,H10c)
;
_olex2_date_sample_data_collection 2025-04-16
_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 2.432
_oxdiff_exptl_absorpt_empirical_full_min 0.536