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_1575929
_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         'C48 H108 O16 Pr Si4'
_chemical_formula_sum            'C48 H108 O16 Pr Si4'
_chemical_formula_weight         1194.61
_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             2025-01-21
_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                 96.2414(15)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   24.1029(3)
_cell_length_b                   13.5279(2)
_cell_length_c                   40.7549(6)
_cell_measurement_reflns_used    12991
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      72.6720
_cell_measurement_theta_min      3.2550
_cell_volume                     13209.8(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 0.994
_diffrn_measured_fraction_theta_max 0.967
_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   -100.00 -73.00   1.00    5.00    --  -40.66-146.00-124.00   27
  2  \w   -100.00 -72.00   1.00    5.00    --  -40.66 146.00 -73.00   28
  3  \w    -80.00  -8.00   1.00    5.00    --  -40.66 125.00 119.00   72
  4  \w    112.00 137.00   1.00   20.00    --  105.15 125.00 119.00   25
  5  \w     65.00 108.00   1.00   20.00    --  105.15-125.00  41.00   43
  6  \w     97.00 126.00   1.00   20.00    --  105.15-146.00-124.00   29
  7  \w     85.00 151.00   1.00   20.00    --  105.15 146.00 -73.00   66
  8  \w   -112.00 -13.00   1.00    5.00    --  -40.66 -57.00-150.00   99
  9  \w    -27.00  60.00   1.00    5.00    --   40.66 -38.00 -90.00   87
 10  \w    104.00 176.00   1.00   20.00    --  105.15  77.00  60.00   72
 11  \w    103.00 177.00   1.00   20.00    --  105.15  77.00 120.00   74
 12  \w     36.00 137.00   1.00   20.00    --  105.15 -77.00-150.00  101
 13  \w    104.00 175.00   1.00   20.00    --  105.15  77.00   0.00   71
 14  \w     39.00  66.00   1.00   20.00    --  105.15-111.00  90.00   27
 15  \w     81.00 106.00   1.00   20.00    --  105.15-111.00  90.00   25
 16  \w    130.00 157.00   1.00   20.00    --  105.15 111.00 -90.00   27
 17  \w    134.00 159.00   1.00   20.00    --  105.15  77.00-150.00   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      -0.0212013000
_diffrn_orient_matrix_UB_12      0.0181889000
_diffrn_orient_matrix_UB_13      -0.0365254000
_diffrn_orient_matrix_UB_21      0.0080029000
_diffrn_orient_matrix_UB_22      0.1121237000
_diffrn_orient_matrix_UB_23      0.0052349000
_diffrn_orient_matrix_UB_31      0.0601469000
_diffrn_orient_matrix_UB_32      -0.0085448000
_diffrn_orient_matrix_UB_33      -0.0091934000
_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  0.0431
_diffrn_reflns_av_unetI/netI     0.0458
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -50
_diffrn_reflns_number            33765
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.855
_diffrn_reflns_theta_min         3.690
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.803
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25020
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.143a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark orange'
_exptl_crystal_density_diffrn    1.201
_exptl_crystal_description       plate
_exptl_crystal_F_000             5112
_exptl_crystal_size_max          0.383
_exptl_crystal_size_mid          0.267
_exptl_crystal_size_min          0.071
_refine_diff_density_max         0.810
_refine_diff_density_min         -0.517
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.183
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     839
_refine_ls_number_reflns         12735
_refine_ls_number_restraints     1283
_refine_ls_restrained_S_all      1.161
_refine_ls_R_factor_all          0.0770
_refine_ls_R_factor_gt           0.0684
_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^)+(0.0325P)^2^+86.6402P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1410
_refine_ls_wR_factor_ref         0.1454
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11218
_reflns_number_total             12735
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05500h2.cif
_cod_data_source_block           pp306c
_cod_depositor_comments
'Adding full bibliography for 1575928--1575935.cif.'
_cod_database_code               1575929
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C48 H108 O16 Si4 Pr1'
_shelx_estimated_absorpt_t_max   0.644
_shelx_estimated_absorpt_t_min   0.180
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O18-C62
 2.5 with sigma of 0.02
 C31-C29 \\sim C34-C29 \\sim C32-C29 \\sim C35-C29 \\sim C30-C29 \\sim C33-C29
 with sigma of 0.02
 C31-C32 \\sim C32-C30 \\sim C31-C30
 with sigma of 0.02
 C33-C34 \\sim C34-C35 \\sim C33-C35
 with sigma of 0.02
 C59-C57 \\sim C58-C57 \\sim C60-C57
 with sigma of 0.02
 C59-C58 \\sim C58-C60 \\sim C59-C60
 with sigma of 0.02
 C41-C36 \\sim C38-C36 \\sim C40-C36 \\sim C37-C36 \\sim C39-C36 \\sim C42-C36
 with sigma of 0.02
 C41-C40 \\sim C40-C42 \\sim C42-C41
 with sigma of 0.02
 C38-C37 \\sim C37-C39 \\sim C38-C39
 with sigma of 0.02
 C45-C43 \\sim C47-C43 \\sim C44-C43 \\sim C49-C43 \\sim C46-C43 \\sim C48-C43
 with sigma of 0.02
 C44-C45 \\sim C45-C46 \\sim C46-C44
 with sigma of 0.02
 C47-C49 \\sim C49-C48 \\sim C47-C48
 with sigma of 0.02
 C56-C50 \\sim C53-C50 \\sim C52-C50 \\sim C55-C50 \\sim C51-C50 \\sim C54-C50
 with sigma of 0.02
 C55-C56 \\sim C56-C54 \\sim C55-C54
 with sigma of 0.02
 C53-C52 \\sim C52-C51 \\sim C53-C51
 with sigma of 0.02
 Si4-O17 \\sim Si4-O15 \\sim Si4-O18 \\sim Si4-O16 \\sim Si4-O14
 with sigma of 0.02
 O18-C57 \\sim O16-C57 \\sim O15-C50 \\sim O17-C50
 with sigma of 0.02
 C59-C57 \\sim C60-C57 \\sim C63-C57 \\sim C62-C57 \\sim C58-C57 \\sim C61-C57
 with sigma of 0.02
 C59-C60 \\sim C60-C58 \\sim C59-C58
 with sigma of 0.02
 C63-C61 \\sim C61-C62 \\sim C63-C62
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C29 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\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 \\sim C58 \\sim C59 \\sim C60:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
O15 \\sim O16 \\sim O17 \\sim O18 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim
C54 \\sim C55 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim
C62 \\sim C63: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(Pr2)=1-FVAR(1)
 Sof(Pr1)=FVAR(1)
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=1-FVAR(2)
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(2)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=1-FVAR(3)
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=FVAR(3)
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=1-FVAR(4)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(H44C)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=FVAR(4)
 Sof(O17)=Sof(O18)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55)=Sof(H55A)=
 Sof(H55B)=Sof(H55C)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C61)=Sof(H61A)=
 Sof(H61B)=Sof(H61C)=Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63)=Sof(H63A)=
 Sof(H63B)=Sof(H63C)=1-FVAR(5)
 Sof(O15)=Sof(O16)=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(C58)=Sof(H58A)=
 Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C60)=Sof(H60A)=
 Sof(H60B)=Sof(H60C)=FVAR(5)
6.a Me refined with riding coordinates:
 C62(H62A,H62B,H62C)
6.b 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), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,
 H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C),
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,
 H48C), C49(H49A,H49B,H49C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,
 H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C),
 C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,H61B,
 H61C), C63(H63A,H63B,H63C)
;
_shelx_res_checksum              13116
_olex2_date_sample_data_collection 2024-11-28
_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 4.778
_oxdiff_exptl_absorpt_empirical_full_min 0.528