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_1575933
_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         'C111 H101 Cl2 K O11 Pr Si5, 1[CH2Cl2]'
_chemical_formula_sum            'C112 H103 Cl4 K O11 Pr Si5'
_chemical_formula_weight         2087.20
_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
_audit_creation_date             2025-07-09
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-07-09 deposited with the CCDC.	2025-10-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 103.8097(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.1726(2)
_cell_length_b                   28.1742(7)
_cell_length_c                   26.7761(4)
_cell_measurement_reflns_used    19106
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      69.1390
_cell_measurement_theta_min      2.3060
_cell_volume                     10382.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.44.116a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.116a 64-bit (release 30-06-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.116a (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      140.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.937
_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     42.00  67.00   0.50    2.73    --   66.04-142.00 120.00   50
  2  \w     36.00  61.00   0.50    2.73    --   66.04-129.00 -67.00   50
  3  \w    -72.00 -38.00   0.50    2.73    --  -67.39 129.00   5.00   68
  4  \w    -89.00 -64.00   0.50    2.73    --  -67.39-142.00 120.00   50
  5  \w   -107.00 -78.00   0.50    2.73    --  -69.31 142.00 177.00   58
  6  \w   -110.00 -85.00   0.50    2.73    --  -69.31-142.00 120.00   50
  7  \w     60.00  85.00   0.50    2.73    --   69.52-129.00 -67.00   50
  8  \w     52.00  77.00   0.50    2.73    --   69.52-142.00 120.00   50
  9  \w     80.00 113.00   0.50    2.73    --   77.97-142.00 120.00   66
 10  \w     77.00 108.00   0.50    2.73    --   77.97-129.00 -67.00   62
 11  \w     46.00  71.00   0.50    2.73    --   77.97-129.00 -67.00   50
 12  \w     75.00 101.00   0.50    2.73    --   77.97 142.00 177.00   52
 13  \w     28.00  53.00   0.50    2.73    --   66.04 -95.00 -60.00   50
 14  \w     30.00  74.00   0.50    2.73    --   66.04 -95.00-150.00   88
 15  \w     36.00  98.00   0.50    2.73    --   66.04  15.00-180.00  124
 16  \w     31.00  74.00   0.50    2.73    --   66.04 -95.00 120.00   86
 17  \w     33.00  60.00   0.50    2.73    --   66.04 -95.00 150.00   54
 18  \w   -104.00 -72.00   0.50    2.73    --  -67.39   0.00 150.00   64
 19  \w   -101.00 -73.00   0.50    2.73    --  -67.39   0.00 120.00   56
 20  \w   -105.00 -79.00   0.50    2.73    --  -67.39   0.00-150.00   52
 21  \w   -103.00 -73.00   0.50    2.73    --  -67.39   0.00-180.00   60
 22  \w    -87.00 -62.00   0.50    2.73    --  -69.31 129.00   5.00   50
 23  \w     38.00 112.00   0.50    2.73    --   69.52  15.00-120.00  148
 24  \w   -113.00 -35.00   0.50    2.73    --  -74.80 144.00 -60.34  156
 25  \w   -102.00 -54.00   0.50    2.73    --  -74.80 122.00 -66.35   96
 26  \w   -111.00 -35.00   0.50    2.73    --  -74.80 143.00-135.28  152
 27  \w     34.00 105.00   0.50    2.73    --   77.97-125.00   0.00  142
 28  \w     73.00 106.00   0.50    2.73    --   77.97-125.00  60.00   66
 29  \w     46.00  71.00   0.50    2.73    --   77.97 -95.00 -30.00   50
 30  \w     47.00 113.00   0.50    2.73    --   77.97  15.00 -90.00  132
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0172247000
_diffrn_orient_matrix_UB_12      0.0469080000
_diffrn_orient_matrix_UB_13      0.0303893000
_diffrn_orient_matrix_UB_21      0.0186094000
_diffrn_orient_matrix_UB_22      -0.0279888000
_diffrn_orient_matrix_UB_23      0.0508498000
_diffrn_orient_matrix_UB_31      0.1090025000
_diffrn_orient_matrix_UB_32      -0.0026292000
_diffrn_orient_matrix_UB_33      0.0010170000
_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  0.1005
_diffrn_reflns_av_unetI/netI     0.1021
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.937
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            99230
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.535
_diffrn_reflns_theta_min         2.312
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.929
_exptl_absorpt_correction_T_max  0.884
_exptl_absorpt_correction_T_min  0.424
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.116a (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 intense orange'
_exptl_crystal_density_diffrn    1.335
_exptl_crystal_description       needle
_exptl_crystal_F_000             4316
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.035
_exptl_crystal_size_min          0.025
_refine_diff_density_max         1.832
_refine_diff_density_min         -1.090
_refine_diff_density_rms         0.109
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1180
_refine_ls_number_reflns         20180
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.1329
_refine_ls_R_factor_gt           0.0711
_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^)+(0.1215P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1828
_refine_ls_wR_factor_ref         0.2107
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11772
_reflns_number_total             20180
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05500h2.cif
_cod_data_source_block           pp432b
_cod_depositor_comments
'Adding full bibliography for 1575928--1575935.cif.'
_cod_database_code               1575933
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C112 H103 Cl4 K1 O11 Pr1 Si5'
_shelx_estimated_absorpt_t_max   0.866
_shelx_estimated_absorpt_t_min   0.261
_diffrn_oxdiff_digest_od_ed
;

;
_diffrn_oxdiff_measurement_exp_name PP432b.par
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C91(H91A,H91B), C92(H92A,H92B), C99(H99A,H99B), C100(H10A,H10B), C101(H10C,
 H10D), C102(H10E,H10F), C109(H10G,H10H), C110(H11A,H11B), C111(H11C,H11D)
2.b 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), C94(H94), C95(H95),
  C96(H96), C97(H97), C104(H104), C105(H105), C106(H106), C107(H107)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 168 electrons were 
found in a volume of 888\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1[CH2Cl2] per formula unit 
which account for 168 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              6194
_shelx_fab_checksum              24435
_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 4.078
_oxdiff_exptl_absorpt_empirical_full_min 0.264