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_1575930
_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         'C72 H162 O24 Pr2 Si6'
_chemical_formula_sum            'C72 H162 O24 Pr2 Si6'
_chemical_formula_weight         1862.37
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-14
_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                 98.0362(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.9527(5)
_cell_length_b                   14.2269(3)
_cell_length_c                   27.4839(5)
_cell_measurement_reflns_used    10308
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      72.6600
_cell_measurement_theta_min      4.3590
_cell_volume                     10048.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.143a 64-bit (release 25-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.143a (Rigaku OD, 2024)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.972
_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    -67.00 -21.00   1.00    7.50    --  -40.66  77.00 -61.00   46
  2  \w    -17.00  59.00   1.00    7.50    --   40.66 -77.00 172.00   76
  3  \w    117.00 156.00   1.00   30.00    --  105.15  77.00 -61.00   39
  4  \w     29.00 138.00   1.00   30.00    --  105.15 -77.00 172.00  109
  5  \w    -65.00  31.00   1.00    7.50    --  -40.66  38.00  60.00   96
  6  \w    -20.00   7.00   1.00    7.50    --   40.66 -77.00 -30.00   27
  7  \w     46.00  72.00   1.00    7.50    --   40.66 -77.00 -30.00   26
  8  \w     31.00 133.00   1.00   30.00    --  105.15 -30.00 150.00  102
  9  \w    134.00 177.00   1.00   30.00    --  105.15  77.00  90.00   43
 10  \w    114.00 165.00   1.00   30.00    --  105.15  77.00-180.00   51
 11  \w    105.00 178.00   1.00   30.00    --  105.15  77.00 -90.00   73
 12  \w    125.00 152.00   1.00   30.00    --  105.15 111.00-150.00   27
 13  \w     26.00 101.00   1.00   30.00    --  105.15 -94.00  30.00   75
;
_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      -0.0520443000
_diffrn_orient_matrix_UB_12      -0.0507511000
_diffrn_orient_matrix_UB_13      -0.0159632000
_diffrn_orient_matrix_UB_21      0.0285210000
_diffrn_orient_matrix_UB_22      -0.0750469000
_diffrn_orient_matrix_UB_23      -0.0266471000
_diffrn_orient_matrix_UB_31      0.0085568000
_diffrn_orient_matrix_UB_32      -0.0592847000
_diffrn_orient_matrix_UB_33      0.0473273000
_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  0.0373
_diffrn_reflns_av_unetI/netI     0.0405
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            22885
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.852
_diffrn_reflns_theta_min         3.248
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.523
_exptl_absorpt_correction_T_max  0.696
_exptl_absorpt_correction_T_min  0.430
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
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 pale colourless'
_exptl_crystal_density_diffrn    1.231
_exptl_crystal_description       prism
_exptl_crystal_F_000             3952
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.085
_exptl_crystal_size_min          0.073
_refine_diff_density_max         0.753
_refine_diff_density_min         -1.174
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     734
_refine_ls_number_reflns         9752
_refine_ls_number_restraints     822
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0466
_refine_ls_R_factor_gt           0.0399
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0477P)^2^+21.4880P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0966
_refine_ls_wR_factor_ref         0.1012
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8442
_reflns_number_total             9752
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05500h2.cif
_cod_data_source_block           pp310b
_cod_depositor_comments
'Adding full bibliography for 1575928--1575935.cif.'
_cod_database_code               1575930
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C72 H162 O24 Si6 Pr2'
_shelx_estimated_absorpt_t_max   0.575
_shelx_estimated_absorpt_t_min   0.335
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si03-O10 \\sim Si03-O13 \\sim Si03-O12 \\sim Si03-O15 \\sim Si03-O11 \\sim
Si03-O14
 with sigma of 0.02
 O13-O15 \\sim O15-O14 \\sim O13-O14
 with sigma of 0.02
 O10-O12 \\sim O12-O11 \\sim O10-O11
 with sigma of 0.02
 O13-C46 \\sim O10-C34 \\sim O12-C42 \\sim O15-C54 \\sim O14-C50 \\sim O11-C38
 with sigma of 0.02
 C36-C34 \\sim C35-C34 \\sim C37-C34 \\sim C46-C47 \\sim C46-C49 \\sim C46-C48
 with sigma of 0.02
 C47-C48 \\sim C48-C49 \\sim C47-C49
 with sigma of 0.02
 C36-C35 \\sim C35-C37 \\sim C36-C37
 with sigma of 0.02
 C44-C42 \\sim C45-C42 \\sim C43-C42 \\sim C54-C55 \\sim C54-C56 \\sim C57-C54
 with sigma of 0.02
 C44-C45 \\sim C45-C43 \\sim C44-C43
 with sigma of 0.02
 C55-C56 \\sim C56-C57 \\sim C55-C57
 with sigma of 0.02
 C50-C51 \\sim C50-C52 \\sim C50-C53 \\sim C41-C38 \\sim C39-C38 \\sim C40-C38
 with sigma of 0.02
 C52-C53 \\sim C53-C51 \\sim C51-C52
 with sigma of 0.02
 C39-C41 \\sim C41-C40 \\sim C39-C40
 with sigma of 0.02
 C23-C20 \\sim C26-C20 \\sim C24-C20 \\sim C21-C20 \\sim C25-C20 \\sim C22-C20
 with sigma of 0.02
 C21-C23 \\sim C23-C22 \\sim C21-C22
 with sigma of 0.02
 C24-C26 \\sim C26-C25 \\sim C24-C25
 with sigma of 0.02
 C11-C9 \\sim C14-C9 \\sim C13-C9 \\sim C10-C9 \\sim C15-C9 \\sim C12-C9
 with sigma of 0.02
 C10-C11 \\sim C11-C12 \\sim C10-C12
 with sigma of 0.02
 C13-C14 \\sim C14-C15 \\sim C13-C15
 with sigma of 0.02
 C31-C27 \\sim C28-C27 \\sim C32-C27 \\sim C29-C27 \\sim C30-C27 \\sim C33-C27
 with sigma of 0.02
 C30-C29 \\sim C29-C28 \\sim C28-C30
 with sigma of 0.02
 C33-C32 \\sim C32-C31 \\sim C31-C33
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si03 \\sim O10 \\sim O11 \\sim O12 \\sim O13 \\sim O14 \\sim O15 \\sim C34
\\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42
\\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49 \\sim C50
\\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56 \\sim C57: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(O13)=Sof(O14)=Sof(O15)=Sof(C46)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=
 Sof(C50)=Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=Sof(C52)=Sof(H52A)=Sof(H52B)=
 Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C54)=Sof(C55)=Sof(H55A)=
 Sof(H55B)=Sof(H55C)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C57)=Sof(H57A)=
 Sof(H57B)=Sof(H57C)=1-FVAR(1)
 Sof(O10)=Sof(O11)=Sof(O12)=Sof(C34)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=
 Sof(C38)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=
 Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(C43)=Sof(H43A)=
 Sof(H43B)=Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C45)=Sof(H45A)=
 Sof(H45B)=Sof(H45C)=FVAR(1)
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=Sof(H25B)=Sof(H25C)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=1-FVAR(2)
 Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=
 Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=FVAR(2)
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=1-FVAR(3)
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(3)
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=1-FVAR(4)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(4)
5.a Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,
 H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,
 H25B,H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C),
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,
 H33C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C39(H39A,
 H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C43(H43A,H43B,H43C),
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C47(H47A,H47B,H47C), C48(H48A,H48B,
 H48C), C49(H49A,H49B,H49C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,
 H53B,H53C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C)
;
_shelx_res_checksum              89660
_olex2_date_sample_data_collection 2024-12-06
_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 3.328
_oxdiff_exptl_absorpt_empirical_full_min 0.428