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_1575931
_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 K2 O5 Pr Si5, 4(C7 H8)'
_chemical_formula_sum            'C118 H107 K2 O5 Pr Si5'
_chemical_formula_weight         1964.59
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-04-02
_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                 92.3363(16)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.0205(3)
_cell_length_b                   23.9582(7)
_cell_length_c                   22.3860(4)
_cell_measurement_reflns_used    6975
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.3240
_cell_measurement_theta_min      3.4890
_cell_volume                     10192.8(4)
_computing_cell_refinement       'CrysAlisPro 1.171.44.101a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.100a 64-bit (release 20-03-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.101a (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 2018/2 (Sheldrick, 2018)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.974
_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 -42.00   1.00   12.50    --  -40.91 118.00 115.00   25
  2  \w   -105.00 -79.00   1.00   12.50    --  -40.91-159.00-123.00   26
  3  \w     32.00  57.00   1.00   12.50    --   40.91-118.00  29.00   25
  4  \w     82.00 107.00   1.00   12.50    --   40.91-159.00-123.00   25
  5  \w     47.00  72.00   1.00   50.00    --  105.15-118.00  29.00   25
  6  \w     93.00 118.00   1.00   50.00    --  105.15 159.00 -91.00   25
  7  \w     89.00 123.00   1.00   50.00    --  105.15-159.00-123.00   34
  8  \w    128.00 167.00   1.00   50.00    --  105.15 118.00 115.00   39
  9  \w   -113.00 -16.00   1.00   12.50    --  -40.91 -38.00 -90.00   97
 10  \w    -64.00  -4.00   1.00   12.50    --  -40.91  38.00-120.00   60
 11  \w      7.00  78.00   1.00   12.50    --   40.91 -99.00 -60.00   71
 12  \w    141.00 167.00   1.00   50.00    --  105.15  77.00 -30.00   26
 13  \w     81.00 109.00   1.00   50.00    --  105.15-111.00  90.00   28
 14  \w    104.00 176.00   1.00   50.00    --  105.15  77.00  30.00   72
 15  \w    103.00 168.00   1.00   50.00    --  105.15  77.00 150.00   65
 16  \w     79.00 130.00   1.00   50.00    --  105.15 -45.00  30.00   51
 17  \w     40.00  96.00   1.00   50.00    --  105.15-111.00  60.00   56
 18  \w     32.00  70.00   1.00   50.00    --  105.15-111.00  90.00   38
 19  \w     91.00 144.00   1.00   50.00    --  105.15 178.00 -30.00   53
 20  \w    107.00 159.00   1.00   50.00    --  105.15  77.00   0.00   52
;
_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      0.0546772000
_diffrn_orient_matrix_UB_12      0.0192002000
_diffrn_orient_matrix_UB_13      0.0483762000
_diffrn_orient_matrix_UB_21      -0.0251131000
_diffrn_orient_matrix_UB_22      0.0607418000
_diffrn_orient_matrix_UB_23      -0.0083205000
_diffrn_orient_matrix_UB_31      -0.0544093000
_diffrn_orient_matrix_UB_32      -0.0087216000
_diffrn_orient_matrix_UB_33      0.0482502000
_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  0.0856
_diffrn_reflns_av_unetI/netI     0.1189
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            52870
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.976
_diffrn_reflns_theta_min         2.968
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.378
_exptl_absorpt_correction_T_max  0.924
_exptl_absorpt_correction_T_min  0.756
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.101a (Rigaku Oxford Diffraction, 2025)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale orange'
_exptl_crystal_density_diffrn    1.280
_exptl_crystal_description       prism
_exptl_crystal_F_000             4088
_exptl_crystal_size_max          0.138
_exptl_crystal_size_mid          0.082
_exptl_crystal_size_min          0.039
_refine_diff_density_max         0.679
_refine_diff_density_min         -0.850
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.006
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1405
_refine_ls_number_reflns         19833
_refine_ls_number_restraints     1094
_refine_ls_restrained_S_all      0.982
_refine_ls_R_factor_all          0.0997
_refine_ls_R_factor_gt           0.0588
_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^)+(0.0456P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1196
_refine_ls_wR_factor_ref         0.1401
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13355
_reflns_number_total             19833
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05500h2.cif
_cod_data_source_block           pp372b2
_cod_depositor_comments
'Adding full bibliography for 1575928--1575935.cif.'
_cod_database_code               1575931
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C118 H107 O5 Si5 K2 Pr1'
_shelx_estimated_absorpt_t_max   0.818
_shelx_estimated_absorpt_t_min   0.524
_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. Restrained distances
 C129-C125
 2.5 with sigma of 0.02
 C125-C126
 2.5 with sigma of 0.02
 C124-C118 \\sim C117-C111 \\sim C133-C125
 with sigma of 0.02
 Si1-C130 \\sim Si1-C12
 with sigma of 0.02
 Si2-C137 \\sim Si2-C18
 with sigma of 0.02
 Si4-C143 \\sim Si4-C66
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C115 \\sim C111 \\sim C112 \\sim C116 \\sim C117 \\sim C113 \\sim C114 \\sim
C125 \\sim C133 \\sim C129 \\sim C126 \\sim C128 \\sim C198 \\sim C127 \\sim
C119 \\sim C118 \\sim C123 \\sim C124 \\sim C120 \\sim C122 \\sim C121: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C143 \\sim C70 \\sim C66 \\sim C145 \\sim C68 \\sim C146 \\sim C71 \\sim C148
\\sim C69 \\sim C144 \\sim C67 \\sim C147: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C130 \\sim C131
\\sim C132 \\sim C134 \\sim C135 \\sim C136: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
C18 \\sim C139 \\sim C137 \\sim C20 \\sim C141 \\sim C21 \\sim C138 \\sim C23
\\sim C140 \\sim C19 \\sim C142 \\sim C22: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C130)=Sof(C131)=Sof(H131)=Sof(C132)=Sof(H132)=Sof(C134)=Sof(H134)=
 Sof(C135)=Sof(H135)=Sof(C136)=Sof(H136)=1-FVAR(1)
 Sof(C12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=
 Sof(H16)=Sof(C17)=Sof(H17)=FVAR(1)
 Sof(C137)=Sof(C142)=Sof(H142)=Sof(C141)=Sof(H141)=Sof(C140)=Sof(H140)=
 Sof(C139)=Sof(H139)=Sof(C138)=Sof(H138)=1-FVAR(2)
 Sof(C18)=Sof(C19)=Sof(H19)=Sof(C20)=Sof(H20)=Sof(C21)=Sof(H21)=Sof(C22)=
 Sof(H22)=Sof(C23)=Sof(H23)=FVAR(2)
 Sof(C143)=Sof(C144)=Sof(H144)=Sof(C145)=Sof(H145)=Sof(C146)=Sof(H146)=
 Sof(C147)=Sof(H147)=Sof(C148)=Sof(H148)=1-FVAR(3)
 Sof(C66)=Sof(C67)=Sof(H67)=Sof(C68)=Sof(H68)=Sof(C69)=Sof(H69)=Sof(C70)=
 Sof(H70)=Sof(C71)=Sof(H71)=FVAR(3)
 Fixed Sof: C111(0.5) C112(0.5) H112(0.5) C113(0.5) H113(0.5) C114(0.5)
 H114(0.5) C115(0.5) H115(0.5) C116(0.5) H116(0.5) C117(0.5) H11D(0.5)
 H11E(0.5) H11F(0.5) C118(0.3) C119(0.3) H119(0.3) C120(0.3) H120(0.3)
 C121(0.3) H121(0.3) C122(0.3) H122(0.3) C123(0.3) H123(0.3) C124(0.3)
 H12A(0.3) H12B(0.3) H12C(0.3) C125(0.2) H12D(0.2) H12E(0.2) H12F(0.2)
 C133(0.2) C129(0.2) H129(0.2) C128(0.2) H128(0.2) C127(0.2) H127(0.2)
 C198(0.2) H198(0.2) C126(0.2) H126(0.2)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10),
 C11(H11), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17), C19(H19), C20(H20),
  C21(H21), C22(H22), C23(H23), C25(H25), C26(H26), C27(H27), C28(H28),
 C29(H29), C31(H31), C32(H32), C33(H33), C34(H34), C35(H35), C37(H37), C38(H38),
  C39(H39), C40(H40), C41(H41), C43(H43), C44(H44), C45(H45), C46(H46),
 C47(H47), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53), C55(H55), C56(H56),
  C57(H57), C58(H58), C59(H59), C61(H61), C62(H62), C63(H63), C64(H64),
 C65(H65), C67(H67), C68(H68), C69(H69), C70(H70), C71(H71), C73(H73), C74(H74),
  C75(H75), C76(H76), C77(H77), C79(H79), C80(H80), C81(H81), C82(H82),
 C83(H83), C85(H85), C86(H86), C87(H87), C88(H88), C89(H89), C91(H91), C92(H92),
  C93(H93), C94(H94), C95(H95), C98(H98), C99(H99), C100(H100), C101(H101),
 C102(H102), C105(H105), C106(H106), C107(H107), C108(H108), C109(H109),
 C112(H112), C113(H113), C114(H114), C115(H115), C116(H116), C119(H119),
 C120(H120), C121(H121), C122(H122), C123(H123), C129(H129), C128(H128),
 C127(H127), C198(H198), C126(H126), C131(H131), C132(H132), C134(H134),
 C135(H135), C136(H136), C142(H142), C141(H141), C140(H140), C139(H139),
 C138(H138), C144(H144), C145(H145), C146(H146), C147(H147), C148(H148)
5.b Fitted hexagon refined as free rotating group:
 C111(C112,C113,C114,C115,C116), C118(C119,C120,C121,C122,C123), C133(C129,
 C128,C127,C198,C126), C130(C131,C132,C134,C135,C136), C137(C142,C141,C140,C139,
 C138), C143(C144,C145,C146,C147,C148)
5.c Idealised Me refined as rotating group:
 C96(H96A,H96B,H96C), C103(H10A,H10B,H10C), C110(H11A,H11B,H11C), C117(H11D,
 H11E,H11F), C124(H12A,H12B,H12C), C125(H12D,H12E,H12F)
;
_shelx_res_checksum              58687
_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 2.423
_oxdiff_exptl_absorpt_empirical_full_min 0.532