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_1575928
_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 Cs2 O5 Pr Si5, 2(C7 H8)'
_chemical_formula_sum            'C104 H91 Cs2 O5 Pr Si5'
_chemical_formula_weight         1967.94
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-14
_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                 112.803(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.7994(3)
_cell_length_b                   24.8092(4)
_cell_length_c                   14.2323(3)
_cell_measurement_reflns_used    21071
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      72.6410
_cell_measurement_theta_min      3.4130
_cell_volume                     4491.64(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.66a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.66a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.66a (Rigaku OD, 2022)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.986
_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 -87.00   1.00    5.00    --  -40.91-149.00 -56.00   25
  2  \w    -69.00 -44.00   1.00    5.00    --  -40.91 123.00-172.00   25
  3  \w    -85.00 -60.00   1.00    5.00    --  -40.91 149.00  -9.00   25
  4  \w     53.00  93.00   1.00    5.00    --   40.91-123.00 107.00   40
  5  \w     43.00  92.00   1.00    5.00    --   40.91-149.00 -56.00   49
  6  \w     70.00 126.00   1.00   20.00    --  105.15-149.00 -56.00   56
  7  \w    106.00 138.00   1.00   20.00    --  105.15 123.00-172.00   32
  8  \w    101.00 126.00   1.00   20.00    --  105.15 149.00  -9.00   25
  9  \w     38.00 109.00   1.00   20.00    --  105.15-123.00 107.00   71
 10  \w    -65.00  30.00   1.00    5.00    --  -40.91  38.00  90.00   95
 11  \w   -112.00 -16.00   1.00    5.00    --  -40.91 -57.00 -90.00   96
 12  \w   -113.00 -17.00   1.00    5.00    --  -40.91 -38.00 150.00   96
 13  \w     10.00  56.00   1.00    5.00    --   40.91 -38.00  60.00   46
 14  \w     36.00 109.00   1.00   20.00    --  105.15-111.00-180.00   73
 15  \w     64.00 146.00   1.00   20.00    --  105.15 178.00  30.00   82
 16  \w    115.00 178.00   1.00   20.00    --  105.15 111.00-120.00   63
 17  \w    107.00 157.00   1.00   20.00    --  105.15  77.00-120.00   50
 18  \w    104.00 151.00   1.00   20.00    --  105.15 111.00  90.00   47
 19  \w    107.00 145.00   1.00   20.00    --  105.15  77.00 -60.00   38
 20  \w    105.00 157.00   1.00   20.00    --  105.15 111.00 -60.00   52
 21  \w     63.00 145.00   1.00   20.00    --  105.15 178.00 120.00   82
 22  \w    105.00 140.00   1.00   20.00    --  105.15  77.00-180.00   35
 23  \w     68.00 108.00   1.00   20.00    --  105.15-111.00   0.00   40
 24  \w     39.00 132.00   1.00   20.00    --  105.15 -30.00 120.00   93
 25  \w     54.00 113.00   1.00   20.00    --  105.15 -45.00-150.00   59
 26  \w     29.00  86.00   1.00   20.00    --  105.15 -30.00   0.00   57
 27  \w    100.00 133.00   1.00   20.00    --  105.15 -30.00   0.00   33
 28  \w    106.00 133.00   1.00   20.00    --  105.15 111.00 -30.00   27
 29  \w    143.00 168.00   1.00   20.00    --  105.15 111.00 -30.00   25
 30  \w     85.00 131.00   1.00   20.00    --  105.15 -45.00-120.00   46
;
_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      -0.0652739000
_diffrn_orient_matrix_UB_12      0.0519869000
_diffrn_orient_matrix_UB_13      -0.0347657000
_diffrn_orient_matrix_UB_21      -0.1019263000
_diffrn_orient_matrix_UB_22      -0.0335032000
_diffrn_orient_matrix_UB_23      -0.0363055000
_diffrn_orient_matrix_UB_31      -0.0043099000
_diffrn_orient_matrix_UB_32      0.0055847000
_diffrn_orient_matrix_UB_33      0.1061098000
_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  0.0843
_diffrn_reflns_av_unetI/netI     0.0935
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            40619
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.878
_diffrn_reflns_theta_min         3.369
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.443
_exptl_absorpt_correction_T_max  0.425
_exptl_absorpt_correction_T_min  0.192
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.66a (Rigaku Oxford Diffraction, 2022)
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 colourless'
_exptl_crystal_density_diffrn    1.455
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1988
_exptl_crystal_size_max          0.273
_exptl_crystal_size_mid          0.212
_exptl_crystal_size_min          0.132
_refine_diff_density_max         1.737
_refine_diff_density_min         -2.402
_refine_diff_density_rms         0.163
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   -0.034(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1057
_refine_ls_number_reflns         17329
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.0938
_refine_ls_R_factor_gt           0.0865
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1406P)^2^+20.8936P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2199
_refine_ls_wR_factor_ref         0.2294
_reflns_Friedel_coverage         0.917
_reflns_Friedel_fraction_full    0.985
_reflns_Friedel_fraction_max     0.949
_reflns_number_gt                15826
_reflns_number_total             17329
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05500h2.cif
_cod_data_source_block           mk-775
_cod_depositor_comments
'Adding full bibliography for 1575928--1575935.cif.'
_cod_database_code               1575928
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C104 H91 O5 Si5 Cs2 Pr1'
_shelx_estimated_absorpt_t_max   0.313
_shelx_estimated_absorpt_t_min   0.146
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 1.034(7)
 -0.034(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
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)
;
_shelx_res_checksum              65230
_olex2_date_sample_data_collection 2022-08-19
_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 6.081
_oxdiff_exptl_absorpt_empirical_full_min 0.308