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_1575934
_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 Ce K2 O5 Si5, 0.5[C7H8]'
_chemical_formula_sum            'C93.5 H79 Ce K2 O5 Si5'
_chemical_formula_weight         1641.33
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-06-16
_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                109.761(6)
_cell_angle_beta                 95.331(6)
_cell_angle_gamma                90.676(5)
_cell_formula_units_Z            4
_cell_length_a                   13.6841(9)
_cell_length_b                   23.2083(15)
_cell_length_c                   27.761(2)
_cell_measurement_reflns_used    2806
_cell_measurement_temperature    200.00(11)
_cell_measurement_theta_max      49.2660
_cell_measurement_theta_min      3.0020
_cell_volume                     8252.6(10)
_computing_cell_refinement       'CrysAlisPro 1.171.44.113a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.113a 64-bit (release 02-06-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.113a (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      200.00(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_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   -112.00 -66.00   1.00   10.00    --  -43.01-142.00 -85.00   46
  2  \w    -87.00 -43.00   1.00   10.00    --  -43.01 128.00 160.00   44
  3  \w    -68.00 -43.00   1.00   10.00    --  -43.01 142.00 -29.00   25
  4  \w     41.00  66.00   1.00   10.00    --   43.01-128.00  85.00   25
  5  \w     49.00  74.00   1.00   10.00    --   43.01-142.00 -85.00   25
  6  \w     56.00  81.00   1.00   40.00    --  103.18-142.00 -85.00   25
  7  \w     32.00 115.00   1.00   40.00    --  103.18-128.00  85.00   83
  8  \w    125.00 153.00   1.00   40.00    --  103.18 142.00 -29.00   28
  9  \w    112.00 137.00   1.00   40.00    --  103.18 128.00 160.00   25
 10  \w   -115.00 -20.00   1.00   10.00    --  -43.01 -37.00 -90.00   95
 11  \w   -115.00 -15.00   1.00   10.00    --  -43.01 -57.00-180.00  100
 12  \w     11.00  83.00   1.00   10.00    --   43.01 -99.00  90.00   72
 13  \w    104.00 163.00   1.00   40.00    --  103.18 111.00  30.00   59
 14  \w     30.00  81.00   1.00   40.00    --  103.18-111.00 -30.00   51
 15  \w     43.00  70.00   1.00   40.00    --  103.18-111.00   0.00   27
 16  \w     93.00 128.00   1.00   40.00    --  103.18 -30.00 -60.00   35
 17  \w     75.00 109.00   1.00   40.00    --  103.18-111.00-180.00   34
 18  \w     61.00 136.00   1.00   40.00    --  103.18 178.00 -90.00   75
 19  \w    108.00 177.00   1.00   40.00    --  103.18  77.00   0.00   69
 20  \w     94.00 136.00   1.00   40.00    --  103.18 -77.00-120.00   42
 21  \w     59.00 147.00   1.00   40.00    --  103.18-178.00-150.00   88
 22  \w     32.00  57.00   1.00   40.00    --  103.18 -45.00  30.00   25
 23  \w     89.00 116.00   1.00   40.00    --  103.18 -45.00  30.00   27
 24  \w     83.00 109.00   1.00   40.00    --  103.18-111.00   0.00   26
 25  \w     28.00  64.00   1.00   40.00    --  103.18 -30.00 -60.00   36
 26  \w    103.00 158.00   1.00   40.00    --  103.18  77.00 -60.00   55
 27  \w     76.00 140.00   1.00   40.00    --  103.18  61.00  30.00   64
 28  \w    120.00 147.00   1.00   40.00    --  103.18  77.00 120.00   27
 29  \w     62.00 109.00   1.00   40.00    --  103.18-111.00 -90.00   47
 30  \w     74.00 175.00   1.00   40.00    --  103.18  61.00  90.00  101
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0385213000
_diffrn_orient_matrix_UB_12      -0.0619091000
_diffrn_orient_matrix_UB_13      -0.0320032000
_diffrn_orient_matrix_UB_21      0.0324376000
_diffrn_orient_matrix_UB_22      -0.0130593000
_diffrn_orient_matrix_UB_23      0.0498092000
_diffrn_orient_matrix_UB_31      -0.1013699000
_diffrn_orient_matrix_UB_32      -0.0313412000
_diffrn_orient_matrix_UB_33      -0.0030395000
_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  0.2397
_diffrn_reflns_av_unetI/netI     0.2965
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            78686
_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         72.471
_diffrn_reflns_theta_min         3.056
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.268
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76747
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.113a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.321
_exptl_crystal_description       needle
_exptl_crystal_F_000             3384
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.070
_refine_diff_density_min         -1.253
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.954
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1855
_refine_ls_number_reflns         31787
_refine_ls_number_restraints     3559
_refine_ls_restrained_S_all      0.915
_refine_ls_R_factor_all          0.2340
_refine_ls_R_factor_gt           0.0966
_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^)+(0.0230P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1855
_refine_ls_wR_factor_ref         0.2740
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11191
_reflns_number_total             31787
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05500h2.cif
_cod_data_source_block           pp418
_cod_depositor_comments
'Adding full bibliography for 1575928--1575935.cif.'
_cod_original_formula_sum        'C93.50 H79 Ce K2 O5 Si5'
_cod_database_code               1575934
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C93 H82 O5 Si5 K2 Ce1'
_shelx_estimated_absorpt_t_max   0.474
_shelx_estimated_absorpt_t_min   0.273
_diffrn_oxdiff_digest_creation
;
CAP 1.171.44.113a, AC 1.5-ac7-016
;
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17
\\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim 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 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73
\\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81
\\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89
\\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim C94 \\sim C95 \\sim C96 \\sim C97
\\sim C98 \\sim C99 \\sim C100 \\sim C101 \\sim C102 \\sim C103 \\sim C104
\\sim C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110 \\sim C111
\\sim C112 \\sim C113 \\sim C114 \\sim C115 \\sim C116 \\sim C117 \\sim C118
\\sim C119 \\sim C120 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125
\\sim C126 \\sim C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132
\\sim C133 \\sim C134 \\sim C135 \\sim C136 \\sim C137 \\sim C138 \\sim C139
\\sim C140 \\sim C141 \\sim C142 \\sim C143 \\sim C144 \\sim C145 \\sim C146
\\sim C147 \\sim C148 \\sim C149 \\sim C150 \\sim C151 \\sim C152 \\sim C153
\\sim C154 \\sim C155 \\sim C156 \\sim C157 \\sim C158 \\sim C159 \\sim C160
\\sim C161 \\sim C162 \\sim C163 \\sim C164 \\sim C165 \\sim C166 \\sim C167
\\sim C168 \\sim C169 \\sim C170 \\sim C171 \\sim C172 \\sim C173 \\sim C174
\\sim C175 \\sim C176 \\sim C177 \\sim C178 \\sim C179 \\sim C180: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
3. 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
4.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), C98(H98), C99(H99), C100(H100), C101(H101),
 C102(H102), C104(H104), C105(H105), C106(H106), C107(H107), C108(H108),
 C110(H110), C111(H111), C112(H112), C113(H113), C114(H114), C116(H116),
 C117(H117), C118(H118), C119(H119), C120(H120), C121(H121), C122(H122),
 C124(H124), C125(H125), C126(H126), C128(H128), C129(H129), C130(H130),
 C131(H131), C132(H132), C134(H134), C135(H135), C136(H136), C137(H137),
 C138(H138), C140(H140), C141(H141), C142(H142), C143(H143), C144(H144),
 C146(H146), C147(H147), C148(H148), C149(H149), C150(H150), C152(H152),
 C153(H153), C154(H154), C155(H155), C156(H156), C158(H158), C159(H159),
 C160(H160), C161(H161), C162(H162), C164(H164), C165(H165), C166(H166),
 C167(H167), C168(H168), C170(H170), C171(H171), C172(H172), C173(H173),
 C174(H174), C176(H176), C177(H177), C178(H178), C179(H179), C180(H180)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 107 electrons were 
found in a volume of 710\%A^3^ in 4 voids per unit cell. 
This is consistent with the presence of 
0.5[C7H8] per formula unit 
which account for 100 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              72232
_shelx_fab_checksum              98283
_olex2_date_sample_data_collection 2025-06-13
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.508
_oxdiff_exptl_absorpt_empirical_full_min 0.746