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_1571677
_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         'C46 H60 Cr N2 O2'
_chemical_formula_sum            'C46 H60 Cr N2 O2'
_chemical_formula_weight         724.96
_chemical_name_systematic        Cr(O(tBu)2C6H3)2(XyNC)2
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-07-07
_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                90
_cell_angle_beta                 110.037(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.9280(4)
_cell_length_b                   28.6868(10)
_cell_length_c                   14.0779(6)
_cell_measurement_reflns_used    24728
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      78.5410
_cell_measurement_theta_min      2.9850
_cell_volume                     4146.1(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.61a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.61a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.61a (Rigaku OD, 2022)'
_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    'olex2.solve (Bourhis et al., 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 0.999
_diffrn_measured_fraction_theta_max 0.985
_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    -82.00  -8.00   0.50   10.70    --  -49.62 113.00 114.00  148
  2  \w     38.00  72.00   0.50   10.70    --   49.62-113.00  23.00   68
  3  \w   -144.00-119.00   0.50   14.40    --  -90.00-113.00  23.00   50
  4  \w    -76.00 -51.00   0.50   14.40    --  -90.00 113.00 114.00   50
  5  \w     79.00 108.00   0.50   14.40    --  111.50-113.00  23.00   58
  6  \w    103.00 155.00   0.50   14.40    --  111.50 113.00 114.00  104
  7  \w   -115.00 -73.00   0.50   10.70    --  -49.62-125.00 120.00   84
  8  \w   -115.00 -75.00   0.50   10.70    --  -49.62-125.00  60.00   80
  9  \w   -117.00 -73.00   0.50   10.70    --  -49.62-125.00-150.00   88
 10  \w   -116.00 -76.00   0.50   10.70    --  -49.62-125.00-120.00   80
 11  \w    -43.00  22.00   0.50   10.70    --  -49.62  38.00 150.00  130
 12  \w    -19.00  62.00   0.50   10.70    --   49.62 -57.00 -60.00  162
 13  \w     52.00  78.00   0.50   10.70    --   49.62 -99.00-150.00   52
 14  \w      5.00  32.00   0.50   10.70    --   49.62 -99.00-150.00   54
 15  \w    -47.00 -19.00   0.50   14.40    --  -90.00  45.00 -60.00   56
 16  \w    -46.00 -20.00   0.50   14.40    --  -90.00  45.00  60.00   52
 17  \w   -158.00-104.00   0.50   14.40    --  -90.00 -30.00 -90.00  108
 18  \w    106.00 159.00   0.50   14.40    --  111.50 125.00-180.00  106
 19  \w     44.00  74.00   0.50   14.40    --  111.50-125.00-180.00   60
 20  \w    105.00 173.00   0.50   14.40    --  111.50  30.00 120.00  136
 21  \w     45.00  71.00   0.50   14.40    --  111.50 -61.00   0.00   52
 22  \w     73.00 108.00   0.50   14.40    --  111.50-111.00 104.83   70
 23  \w     74.00 104.00   0.50   14.40    --  111.50 -95.00-180.00   60
 24  \w    118.00 166.00   0.50   14.40    --  111.50  30.00  90.00   96
 25  \w    148.00 173.00   0.50   14.40    --  111.50  30.00 -30.00   50
 26  \w    119.00 177.00   0.50   14.40    --  111.50  45.00  60.00  116
 27  \w    111.00 137.00   0.50   14.40    --  111.50  30.00 -30.00   52
 28  \w     71.00 104.00   0.50   14.40    --  111.50 -95.00-150.00   66
 29  \w     42.00  74.00   0.50   14.40    --  111.50 -77.00   0.00   64
 30  \w    126.00 176.00   0.50   14.40    --  111.50  30.00  30.00  100
 31  \w     43.00  83.00   0.50   14.40    --  111.50-125.00 150.00   80
 32  \w    105.00 177.00   0.50   14.40    --  111.50  45.00 -60.00  144
 33  \w     77.00 102.00   0.50   14.40    --  111.50 -95.00 150.00   50
 34  \w     67.00  94.00   0.50   14.40    --  111.50 -95.00 -30.00   54
 35  \w     43.00  68.00   0.50   14.40    --  111.50 -95.00-180.00   50
 36  \w     75.00 103.00   0.50   14.40    --  111.50 -95.00-120.00   56
 37  \w     47.00 110.00   0.50   14.40    --  111.50-125.00 -30.00  126
 38  \w     43.00  68.00   0.50   14.40    --  111.50 -61.00 150.00   50
 39  \w    139.00 167.00   0.50   14.40    --  111.50  30.00 -90.00   56
 40  \w     56.00  95.00   0.50   14.40    --  111.50-125.00   0.00   78
 41  \w     71.00 103.00   0.50   14.40    --  111.50 -95.00   0.00   64
 42  \w     97.00 148.00   0.50   14.40    --  111.50  61.00-150.00  102
 43  \w    153.00 178.00   0.50   14.40    --  111.50  61.00-150.00   50
 44  \w    111.00 177.00   0.50   14.40    --  111.50  15.00   0.00  132
 45  \w     41.00  67.00   0.50   14.40    --  111.50 -95.00   0.00   52
 46  \w    104.00 130.00   0.50   14.40    --  111.50  30.00 -90.00   52
 47  \w     41.00  94.00   0.50   14.40    --  111.50 -95.00  60.00  106
 48  \w     42.00  68.00   0.50   14.40    --  111.50-105.00 142.56   52
 49  \w     71.00 107.00   0.50   14.40    --  111.50-105.00 142.56   72
 50  \w     78.00 103.00   0.50   14.40    --  111.50 -95.00  30.00   50
 51  \w     49.00  75.00   0.50   14.40    --  111.50 -95.00  90.00   52
 52  \w     78.00 103.00   0.50   14.40    --  111.50 -95.00  90.00   50
 53  \w    113.00 148.00   0.50   14.40    --  111.50  30.00 150.00   70
 54  \w     69.00 103.00   0.50   14.40    --  111.50 -95.00 -90.00   68
 55  \w     45.00  70.00   0.50   14.40    --  111.50 -61.00 120.00   50
 56  \w    110.00 135.00   0.50   14.40    --  111.50  45.00 -30.00   50
 57  \w    104.00 131.00   0.50   14.40    --  111.50  30.00-150.00   54
;
_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      -0.0629829000
_diffrn_orient_matrix_UB_12      -0.0189204000
_diffrn_orient_matrix_UB_13      -0.1083533000
_diffrn_orient_matrix_UB_21      -0.0032511000
_diffrn_orient_matrix_UB_22      -0.0492557000
_diffrn_orient_matrix_UB_23      0.0426604000
_diffrn_orient_matrix_UB_31      -0.1360539000
_diffrn_orient_matrix_UB_32      0.0099383000
_diffrn_orient_matrix_UB_33      0.0051658000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0565
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            61380
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.840
_diffrn_reflns_theta_min         3.081
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.550
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.62029
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.61a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.161
_exptl_crystal_description       plate
_exptl_crystal_F_000             1560
_exptl_crystal_preparation       'recrystallization from DCM'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.758
_refine_diff_density_min         -0.528
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.108
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     700
_refine_ls_number_reflns         8955
_refine_ls_number_restraints     15
_refine_ls_restrained_S_all      1.107
_refine_ls_R_factor_all          0.0680
_refine_ls_R_factor_gt           0.0612
_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^)+(0.0416P)^2^+8.7780P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1456
_refine_ls_wR_factor_ref         0.1488
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8043
_reflns_number_total             8955
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cy01692g4.cif
_cod_data_source_block           yyk190_croar2_xync2_auto
_cod_depositor_comments
'Adding full bibliography for 1571676--1571678.cif.'
_cod_database_code               1571677
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CrNCHO
_chemical_oxdiff_usercomment
'yellow needle-like plate, acetonitrile at -30 deg'
_shelx_estimated_absorpt_t_max   0.883
_shelx_estimated_absorpt_t_min   0.515
_diffrn_oxdiff_digest_frames
;
01c8e9bc48dae11a120cfb99860a1ff71900025d207
;
_diffrn_oxdiff_digest_hkl
;
01afc570dd15094cefe99d6c2cb905afc2ac0c
;
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Restrained distances
 C00X-H00X \\sim C00D-H00D \\sim C013-H013 \\sim C00V-H00V \\sim C00Y-H00Y
\\sim C010-H010
 with sigma of 0.02
;
_shelx_res_checksum              85398
_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 1.426
_oxdiff_exptl_absorpt_empirical_full_min 0.631