Influence of strong π-acceptor ligands on Cr-K-edge X-ray absorption spectral signatures and consequences for the interpretation of surface sites in the Phillips catalyst.
Kakiuchi, Yuya; Shapovalova, Svetlana; Protsenko, Bogdan; Guda, Sergey; Safonova, Olga V.; Guda, Alexander; Copéret, Christophe; Catalysis science & technology 14 (2024) 3682–3690; doi:10.1039/d3cy01692g

data_1571676
_publ_section_title
;
 Influence of strong &#x3c0;-acceptor ligands on Cr-K-edge X-ray
 absorption spectral signatures and consequences for the interpretation of
 surface sites in the Phillips catalyst.
;
_journal_issue                   13
_journal_name_full               'Catalysis science &amp; technology'
_journal_page_first              3682
_journal_page_last               3690
_journal_paper_doi               10.1039/d3cy01692g
_journal_volume                  14
_journal_year                    2024
_chemical_formula_moiety         'C60 H90 Cr N4 O8 Si2'
_chemical_formula_sum            'C60 H90 Cr N4 O8 Si2'
_chemical_formula_weight         1103.53
_chemical_name_systematic        Cr(OSi(tBu)3)2(XyNC)4
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_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   difmap
_atom_sites_solution_primary     dual
_audit_creation_date             2023-07-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-08-02 deposited with the CCDC.	2024-05-20 downloaded from the CCDC.
;
_cell_angle_alpha                109.944(2)
_cell_angle_beta                 101.7450(10)
_cell_angle_gamma                105.8320(10)
_cell_formula_units_Z            1
_cell_length_a                   11.3465(2)
_cell_length_b                   12.5357(2)
_cell_length_c                   13.0549(2)
_cell_measurement_reflns_used    15182
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.5210
_cell_measurement_theta_min      3.8010
_cell_volume                     1586.41(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.975
_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    -69.00 -40.00   0.50    0.58    --  -49.60  89.00  27.00   58
  2  \w    -37.00  20.00   0.50    0.58    --  -49.60  89.00  27.00  114
  3  \w    -18.00  65.00   0.50    0.58    --   49.60 -89.00 -88.00  166
  4  \w    -73.00 -48.00   0.50    2.32    --  -90.00  89.00  27.00   50
  5  \w   -144.00-119.00   0.50    2.32    --  -90.00 -89.00 -88.00   50
  6  \w     60.00  87.00   0.50    2.32    --  111.50 -89.00 -88.00   54
  7  \w    -11.00  24.00   0.50    0.58    --  -49.60  19.00 120.00   70
  8  \w   -114.00 -74.00   0.50    0.58    --  -49.60-125.00  30.00   80
  9  \w    -26.00   3.00   0.50    0.58    --  -49.60  19.00-180.00   58
 10  \w   -108.00 -76.00   0.50    0.58    --  -49.60-125.00 -30.00   64
 11  \w    -26.00  -1.00   0.50    0.58    --  -49.60  19.00  60.00   50
 12  \w     49.00  76.00   0.50    0.58    --   49.60  38.00  60.00   54
 13  \w    -22.00  26.00   0.50    0.58    --   49.60 -19.00   0.00   96
 14  \w    -20.00  60.00   0.50    0.58    --   49.60 -57.00 -60.00  160
 15  \w     92.00 117.00   0.50    0.58    --   49.60  38.00  60.00   50
 16  \w    -50.00 -22.00   0.50    2.32    --  -90.00  45.00-120.00   56
 17  \w    -48.00 -18.00   0.50    2.32    --  -90.00  45.00 -30.00   60
 18  \w   -145.00-119.00   0.50    2.32    --  -90.00 -45.00 120.00   52
 19  \w    -50.00 -18.00   0.50    2.32    --  -90.00  45.00-150.00   64
 20  \w    104.00 166.00   0.50    2.32    --  111.50  15.00   0.00  124
 21  \w     54.00 105.00   0.50    2.32    --  111.50 -95.00-120.00  102
 22  \w     77.00 111.00   0.50    2.32    --  111.50-125.00-180.00   68
 23  \w     44.00  70.00   0.50    2.32    --  111.50 -61.00  90.00   52
 24  \w    136.00 162.00   0.50    2.32    --  111.50 125.00 150.00   52
 25  \w     43.00  68.00   0.50    2.32    --  111.50-125.00-180.00   50
 26  \w     41.00  71.00   0.50    2.32    --  111.50 -61.00  60.00   60
 27  \w    109.00 176.00   0.50    2.32    --  111.50  45.00 -90.00  134
 28  \w     43.00  69.00   0.50    2.32    --  111.50 -61.00 120.00   52
 29  \w    108.00 134.00   0.50    2.32    --  111.50  30.00-120.00   52
 30  \w     45.00  70.00   0.50    2.32    --  111.50-125.00-150.00   50
 31  \w     44.00  71.00   0.50    2.32    --  111.50 -61.00 -60.00   54
 32  \w    112.00 167.00   0.50    2.32    --  111.50  30.00  30.00  110
 33  \w     42.00 104.00   0.50    2.32    --  111.50 -95.00 -60.00  124
 34  \w     43.00  95.00   0.50    2.32    --  111.50 -95.00  60.00  104
 35  \w     44.00  71.00   0.50    2.32    --  111.50 -61.00-150.00   54
 36  \w     49.00 105.00   0.50    2.32    --  111.50 -95.00  30.00  112
 37  \w     48.00  77.00   0.50    2.32    --  111.50-125.00 150.00   58
 38  \w    109.00 149.00   0.50    2.32    --  111.50 125.00-150.00   80
 39  \w     53.00 108.00   0.50    2.32    --  111.50-109.00-130.90  110
 40  \w     77.00 103.00   0.50    2.32    --  111.50 -95.00 150.00   52
 41  \w     51.00 105.00   0.50    2.32    --  111.50 -96.00 -25.36  108
 42  \w     41.00  67.00   0.50    2.32    --  111.50 -95.00 150.00   52
 43  \w     41.00  89.00   0.50    2.32    --  111.50 -95.00-180.00   96
 44  \w     41.00  71.00   0.50    2.32    --  111.50 -61.00 -30.00   60
 45  \w    106.00 175.00   0.50    2.32    --  111.50  30.00-150.00  138
 46  \w     86.00 111.00   0.50    2.32    --  111.50-125.00 150.00   50
 47  \w    114.00 140.00   0.50    2.32    --  111.50  15.00 120.00   52
 48  \w     75.00 100.00   0.50    2.32    --  111.50 -95.00 -90.00   50
 49  \w     80.00 105.00   0.50    2.32    --  111.50 -95.00   0.00   50
 50  \w     52.00  78.00   0.50    2.32    --  111.50 -95.00   0.00   52
 51  \w     54.00 100.00   0.50    2.32    --  111.50 -95.00-150.00   92
 52  \w     77.00 105.00   0.50    2.32    --  111.50 -95.00  90.00   56
 53  \w    113.00 175.00   0.50    2.32    --  111.50  15.00 -30.00  124
 54  \w    138.00 172.00   0.50    2.32    --  111.50  30.00-120.00   68
 55  \w    105.00 175.00   0.50    2.32    --  111.50  89.00  27.00  140
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0497757000
_diffrn_orient_matrix_UB_12      -0.0208463000
_diffrn_orient_matrix_UB_13      -0.1037793000
_diffrn_orient_matrix_UB_21      0.0988201000
_diffrn_orient_matrix_UB_22      0.1326897000
_diffrn_orient_matrix_UB_23      0.0610375000
_diffrn_orient_matrix_UB_31      0.1003737000
_diffrn_orient_matrix_UB_32      -0.0423489000
_diffrn_orient_matrix_UB_33      0.0562395000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0263
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            24416
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.269
_diffrn_reflns_theta_min         3.813
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.258
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76272
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.155
_exptl_crystal_description       block
_exptl_crystal_F_000             594
_exptl_crystal_preparation       'recrystallization from pentane'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-pentane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.328
_refine_diff_density_min         -0.519
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.996
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     520
_refine_ls_number_reflns         6771
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.996
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0322
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1089
_refine_ls_wR_factor_ref         0.1118
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6592
_reflns_number_total             6771
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cy01692g4.cif
_cod_data_source_block           yyk_crii_20230721_auto
_cod_depositor_comments
'Adding full bibliography for 1571676--1571678.cif.'
_cod_original_cell_volume        1586.41(5)
_cod_database_code               1571676
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CrNCHOSi
_chemical_oxdiff_usercomment     'recry pentane'
_shelx_estimated_absorpt_t_max   0.895
_shelx_estimated_absorpt_t_min   0.661
_diffrn_oxdiff_digest_frames
;
01f83ef9ae2eb155e55d108397d7d6912f000311194
;
_diffrn_oxdiff_digest_hkl
;
015c58ec8883bba03244b94f5b8a078ed4111a
;
_reflns_odcompleteness_completeness 99.60
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
;
_shelx_res_checksum              9293
_olex2_exptl_crystal_mounting_method loop
_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 1.319
_oxdiff_exptl_absorpt_empirical_full_min 0.835