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_1571678
_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         'C54 H99 Cr N2 O12 Si3'
_chemical_formula_sum            'C54 H99 Cr N2 O12 Si3'
_chemical_formula_weight         1104.62
_chemical_name_systematic        Cr(OSi(tBu)3)3(XyNC)2
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2023-07-25
_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                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.1907(3)
_cell_length_b                   20.8362(5)
_cell_length_c                   23.4449(6)
_cell_measurement_reflns_used    27244
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      80.0280
_cell_measurement_theta_min      2.7300
_cell_volume                     6443.7(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    'ShelXS (Sheldrick, 2008)'
_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 0.984
_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    -99.00 -41.00   0.50    0.69    --  -49.62 -48.00-100.00  116
  2  \w    -54.00 -29.00   0.50    2.77    --  -90.00  48.00  47.00   50
  3  \w   -151.00-124.00   0.50    2.77    --  -90.00 -97.00  39.00   54
  4  \w    105.00 138.00   0.50    2.77    --  111.50  83.00-104.00   66
  5  \w    111.00 146.00   0.50    2.77    --  111.50  48.00  47.00   70
  6  \w    144.00 178.00   0.50    2.77    --  111.50  83.00-104.00   68
  7  \w   -114.00 -87.00   0.50    0.69    --  -49.62-125.00-150.00   54
  8  \w    -43.00  20.00   0.50    0.69    --  -49.62  48.00  47.00  126
  9  \w   -118.00 -73.00   0.50    0.69    --  -49.62-125.00  60.00   90
 10  \w     45.00  70.00   0.50    2.77    --  111.50 -61.00  30.00   50
 11  \w     45.00  70.00   0.50    2.77    --  111.50 -61.00   0.00   50
 12  \w    117.00 156.00   0.50    2.77    --  111.50  30.00  90.00   78
 13  \w    123.00 175.00   0.50    2.77    --  111.50  15.00   0.00  104
 14  \w     60.00  87.00   0.50    2.77    --  111.50 -95.00  60.00   54
 15  \w     45.00  70.00   0.50    2.77    --  111.50 -61.00 -90.00   50
 16  \w     42.00  71.00   0.50    2.77    --  111.50 -77.00-150.00   58
 17  \w     60.00  85.00   0.50    2.77    --  111.50 -77.00   0.00   50
 18  \w     98.00 125.00   0.50    2.77    --  111.50  61.00-120.00   54
 19  \w    151.00 178.00   0.50    2.77    --  111.50  61.00-120.00   54
 20  \w     41.00  66.00   0.50    2.77    --  111.50 -61.00 -30.00   50
 21  \w    119.00 164.00   0.50    2.77    --  111.50  30.00 150.00   90
 22  \w    130.00 177.00   0.50    2.77    --  111.50 125.00 -60.00   94
 23  \w    105.00 136.00   0.50    2.77    --  111.50  30.00 -30.00   62
 24  \w    105.00 131.00   0.50    2.77    --  111.50  15.00  60.00   52
 25  \w    136.00 170.00   0.50    2.77    --  111.50  15.00  60.00   68
 26  \w     43.00  68.00   0.50    2.77    --  111.50 -61.00 120.00   50
 27  \w     80.00 105.00   0.50    2.77    --  111.50 -77.00  30.00   50
 28  \w     55.00  80.00   0.50    2.77    --  111.50-125.00   0.00   50
 29  \w     81.00 111.00   0.50    2.77    --  111.50-125.00 150.00   60
 30  \w    138.00 164.00   0.50    2.77    --  111.50  15.00 -30.00   52
 31  \w    143.00 177.00   0.50    2.77    --  111.50  77.00 -60.00   68
 32  \w    150.00 176.00   0.50    2.77    --  111.50  48.00  47.00   52
;
_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      -0.0622349000
_diffrn_orient_matrix_UB_12      -0.0046166000
_diffrn_orient_matrix_UB_13      -0.0554552000
_diffrn_orient_matrix_UB_21      0.0306297000
_diffrn_orient_matrix_UB_22      0.0691575000
_diffrn_orient_matrix_UB_23      -0.0154480000
_diffrn_orient_matrix_UB_31      0.0939671000
_diffrn_orient_matrix_UB_32      -0.0256475000
_diffrn_orient_matrix_UB_33      -0.0317369000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0546
_diffrn_reflns_av_unetI/netI     0.0430
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            47345
_diffrn_reflns_point_group_measured_fraction_full 0.986
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.871
_diffrn_reflns_theta_min         2.837
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.429
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76106
_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            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.139
_exptl_crystal_description       block
_exptl_crystal_F_000             2396
_exptl_crystal_preparation       'recrystallization from pentane'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: n-pentane'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.402
_refine_diff_density_min         -1.074
_refine_diff_density_rms         0.098
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.068(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.104
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     804
_refine_ls_number_reflns         13511
_refine_ls_number_restraints     773
_refine_ls_restrained_S_all      1.084
_refine_ls_R_factor_all          0.0854
_refine_ls_R_factor_gt           0.0835
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+31.7748P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1905
_refine_ls_wR_factor_ref         0.1915
_reflns_Friedel_coverage         0.769
_reflns_Friedel_fraction_full    0.969
_reflns_Friedel_fraction_max     0.915
_reflns_number_gt                13046
_reflns_number_total             13511
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cy01692g4.cif
_cod_data_source_block           yyk_criii_crtbos3xync2_auto
_cod_depositor_comments
'Adding full bibliography for 1571676--1571678.cif.'
_cod_database_code               1571678
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CrNCHOSi
_chemical_oxdiff_usercomment     'pentane, -30 deg, half year'
_diffrn_oxdiff_digest_frames
;
01f3be118ff862737a9b17d4c565a76fbf000319b15
;
_diffrn_oxdiff_digest_hkl
;
01d8c79c2a07a808d96d0eb674ed752f03327a
;
_reflns_odcompleteness_completeness 98.14
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.95
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.932(11)
 0.068(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Rigid body (RIGU) restrains
 C7, C8, C11, C4AA, O2, Si18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O8, C0AA, C1Q, C1P, C1O, Si32
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C16, C18, C1A, C19, O1, Si18
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1M, C1L, C1J, C1K, O6, Si7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1G, C1H, C1I, C1F, O5, Si7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O3, C1AA, C1D, C1B, C1C, Si7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O7, C3AA, C1N, C10, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2AA, C1E, C17, C5AA, O4, Si7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, C18, C19
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C18, C7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(O1)=Sof(C16)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=
 Sof(H19B)=Sof(H19C)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(O2)=Sof(C4AA)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=
 Sof(H8B)=Sof(H8C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=FVAR(1)
 Sof(O4)=Sof(C2AA)=Sof(C5AA)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=Sof(C17)=Sof(H17A)=
 Sof(H17B)=Sof(H17C)=Sof(C1E)=Sof(H1EA)=Sof(H1EB)=Sof(H1EC)=Sof(O6)=Sof(C1J)=
 Sof(C1K)=Sof(H1KA)=Sof(H1KB)=Sof(H1KC)=Sof(C1L)=Sof(H1LA)=Sof(H1LB)=Sof(H1LC)=
 Sof(C1M)=Sof(H1MA)=Sof(H1MB)=Sof(H1MC)=1-FVAR(2)
 Sof(O3)=Sof(C1AA)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C1C)=Sof(H1CA)=
 Sof(H1CB)=Sof(H1CC)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(H1DC)=Sof(O5)=Sof(C1F)=
 Sof(C1G)=Sof(H1GA)=Sof(H1GB)=Sof(H1GC)=Sof(C1H)=Sof(H1HA)=Sof(H1HB)=Sof(H1HC)=
 Sof(C1I)=Sof(H1IA)=Sof(H1IB)=Sof(H1IC)=FVAR(2)
 Sof(O8)=Sof(C0AA)=Sof(C1O)=Sof(H1OA)=Sof(H1OB)=Sof(H1OC)=Sof(C1P)=Sof(H1PA)=
 Sof(H1PB)=Sof(H1PC)=Sof(C1Q)=Sof(H1QA)=Sof(H1QB)=Sof(H1QC)=1-FVAR(3)
 Sof(O7)=Sof(C3AA)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=Sof(H10C)=Sof(C1N)=Sof(H1NA)=Sof(H1NB)=Sof(H1NC)=FVAR(3)
5.a Free rotating group:
 O2(C4AA,C7,C8,C11), O1(C16,C18,C19,C1A), O3(C1AA,C1B,C1C,C1D), O4(C2AA,C5AA,
 C17,C1E), O5(C1F,C1G,C1H,C1I), O6(C1J,C1K,C1L,C1M), O7(C3AA,C9,C10,C1N),
 O8(C0AA,C1O,C1P,C1Q)
5.b Aromatic/amide H refined with riding coordinates:
 C62(H62), C60(H60), C51(H51), C52(H52), C50(H50), C61(H61)
5.c Idealised Me refined as rotating group:
 C73(H73A,H73B,H73C), C40(H40A,H40B,H40C), C21(H21A,H21B,H21C), C67(H67A,H67B,
 H67C), C25(H25A,H25B,H25C), C27(H27A,H27B,H27C), C26(H26A,H26B,H26C), C15(H15A,
 H15B,H15C), C43(H43A,H43B,H43C), C66(H66A,H66B,H66C), C13(H13A,H13B,H13C),
 C14(H14A,H14B,H14C), C45(H45A,H45B,H45C), C24(H24A,H24B,H24C), C57(H57A,H57B,
 H57C), C28(H28A,H28B,H28C), C35(H35A,H35B,H35C), C46(H46A,H46B,H46C), C44(H44A,
 H44B,H44C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C11(H11A,H11B,H11C), C18(H18A,
 H18B,H18C), C19(H19A,H19B,H19C), C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,H1BC),
 C1C(H1CA,H1CB,H1CC), C1D(H1DA,H1DB,H1DC), C5AA(H5AA,H5AB,H5AC), C17(H17A,H17B,
 H17C), C1E(H1EA,H1EB,H1EC), C1G(H1GA,H1GB,H1GC), C1H(H1HA,H1HB,H1HC), C1I(H1IA,
 H1IB,H1IC), C1K(H1KA,H1KB,H1KC), C1L(H1LA,H1LB,H1LC), C1M(H1MA,H1MB,H1MC),
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C1N(H1NA,H1NB,H1NC), C1O(H1OA,H1OB,H1OC),
  C1P(H1PA,H1PB,H1PC), C1Q(H1QA,H1QB,H1QC)
;
_shelx_res_checksum              25226
_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 1.598
_oxdiff_exptl_absorpt_empirical_full_min 0.525