Assigning 1H chemical shifts in paramagnetic mono- and bimetallic surface sites using DFT: a case study on the Union Carbide polymerization catalyst
Nobile, Anna Giorgia; Trummer, David; Berkson, Zachariah J.; Wörle, Michael; Copéret, Christophe; Payard, Pierre-Adrien; Chemical Science 14 (2023) 2361–2368; doi:10.1039/D2SC06827C

data_1568384
_publ_section_title
;
 Assigning 1H chemical shifts in paramagnetic mono- and bimetallic surface
 sites using DFT: a case study on the Union Carbide polymerization
 catalyst
;
_journal_issue                   9
_journal_name_full               'Chemical Science'
_journal_page_first              2361
_journal_page_last               2368
_journal_paper_doi               10.1039/D2SC06827C
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety
'C46 H91 Cr2 O12 Si3, C63 H123 Cr2 O16 Si4, C5 H12'
_chemical_formula_sum            'C114 H226 Cr4 O28 Si7'
_chemical_formula_weight         2449.56
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-11-24
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-12-09 deposited with the CCDC.	2023-01-30 downloaded from the CCDC.
;
_cell_angle_alpha                81.335(4)
_cell_angle_beta                 80.527(4)
_cell_angle_gamma                62.020(5)
_cell_formula_units_Z            2
_cell_length_a                   18.0228(8)
_cell_length_b                   18.6557(11)
_cell_length_c                   24.1397(10)
_cell_measurement_reflns_used    8356
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      27.5440
_cell_measurement_theta_min      2.0210
_cell_volume                     7044.8(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    OLEX2
_computing_publication_material  OLEX2
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Oxford Diffraction Sapphire 3'
_diffrn_detector_area_resol_mean 16.0839
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -91.00   0.00   1.00   60.00    --  -20.71 -44.00  51.00   91
  2  \w    -25.00  20.00   1.00   60.00    --  -20.71 -99.00 -30.00   45
  3  \w    -25.00  20.00   1.00   60.00    --  -20.71 -99.00-180.00   45
  4  \w    -95.00 -34.00   1.00   60.00    --  -20.71-179.00-180.00   61
  5  \w    -93.00  17.00   1.00   60.00    --  -20.71 -19.00 120.00  110
  6  \w    -43.00  50.00   1.00   60.00    --  -20.71  38.00 150.00   93
  7  \w    -89.00  -2.00   1.00   60.00    --  -20.71 -57.00   0.00   87
  8  \w    -89.00  -2.00   1.00   60.00    --  -20.71 -57.00 -90.00   87
  9  \w    -39.00  48.00   1.00   60.00    --  -20.71  57.00-150.00   87
 10  \w    -25.00  62.00   1.00   60.00    --   21.18 -99.00  30.00   87
 11  \w    -25.00  62.00   1.00   60.00    --   21.18 -99.00 120.00   87
;
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Sapphire3'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0394054000
_diffrn_orient_matrix_UB_12      0.0001899000
_diffrn_orient_matrix_UB_13      0.0098396000
_diffrn_orient_matrix_UB_21      0.0134360000
_diffrn_orient_matrix_UB_22      -0.0364656000
_diffrn_orient_matrix_UB_23      -0.0129203000
_diffrn_orient_matrix_UB_31      0.0166183000
_diffrn_orient_matrix_UB_32      -0.0231823000
_diffrn_orient_matrix_UB_33      0.0251036000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.1827
_diffrn_reflns_av_unetI/netI     0.1927
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            114334
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.350
_diffrn_reflns_theta_min         1.717
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.422
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93880
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (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    1.155
_exptl_crystal_description       plate
_exptl_crystal_F_000             2656
_exptl_crystal_size_max          0.307
_exptl_crystal_size_mid          0.112
_exptl_crystal_size_min          0.079
_refine_diff_density_max         0.742
_refine_diff_density_min         -0.468
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1445
_refine_ls_number_reflns         25795
_refine_ls_number_restraints     1396
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.1753
_refine_ls_R_factor_gt           0.0875
_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^)+(0.0450P)^2^+1.0681P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1533
_refine_ls_wR_factor_ref         0.1928
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13290
_reflns_number_total             25795
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06827c1.cif
_cod_data_source_block           dt195
_cod_depositor_comments          'Adding full bibliography for 1568384.cif.'
_cod_database_code               1568384
_shelx_shelxl_version_number     2019/1
_chemical_oxdiff_formula         C108Cr4O24Si7
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.881
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C53-C27 \\sim C55-C111 \\sim C109-C111 \\sim C107-C27 \\sim C107-C53 \\sim
C109-C55
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uiso(C117) = Uiso(C59) = Uiso(C119) = Uiso(C15) = Uiso(C121)
Uiso(C7) = Uiso(C113) = Uiso(C57) = Uiso(C115) = Uiso(C29)
4. Rigid body (RIGU) restrains
 Cr1, Cr2, Si1, Si2, Si5, O1, O4, O6, O13, O15, O17, O20, O22, O24, O25, O26,
 O27, C3, C5, C6, C8, C11, C22, C25, C28, C31, C32, C36, C38, C42, C43, C45,
 C49, C51, C58, C60, C62, C63, C64, C65, C66, C69, C73, C75, C76, C77, C80, C83,
  C84, C87, C88, C91, C97, C99, C103, C106, C110, C114, C116, C122, C27, C53,
 C107, C55, C109, C111, Cr3, Cr4, Si3, Si4, Si6, Si7, O2, O3, O5, O7, O8, O9,
 O10, O11, O12, O14, O16, O18, O19, O21, O23, O28, C1, C2, C4, C9, C10, C12,
 C13, C14, C16, C17, C18, C19, C20, C21, C23, C24, C26, C30, C33, C34, C35, C37,
  C39, C40, C41, C44, C46, C47, C48, C50, C52, C54, C56, C61, C67, C68, C70,
 C71, C72, C74, C78, C79, C81, C82, C85, C86, C89, C90, C92, C93, C94, C95, C96,
  C98, C100, C101, C102, C104, C105, C108, C112, C118, C120
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C109)=Sof(H10V)=Sof(H10W)=
 Sof(H10X)=Sof(C111)=Sof(H11P)=Sof(H11Q)=Sof(H11R)=1-FVAR(1)
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=
 Sof(C107)=Sof(H10S)=Sof(H10T)=Sof(H10U)=FVAR(1)
 Fixed Sof: C7(0.5) H7C(0.5) H7A(0.5) H7B(0.5) C29(0.5) H29B(0.5) H29C(0.5)
 H29A(0.5) C57(0.5) H57A(0.5) H57B(0.5) C113(0.5) H11S(0.5) H11T(0.5) C115(0.5)
 H11U(0.5) H11V(0.5) C117(0.5) H11W(0.5) H11X(0.5) H11Y(0.5) C15(0.5) H15A(0.5)
 H15B(0.5) C59(0.5) H59A(0.5) H59B(0.5) C119(0.5) H(0.5) H11Z(0.5) C121(0.5)
 H12D(0.5) H12E(0.5) H12F(0.5)
6.a Free rotating group:
 C7(C29,C57,C113,C115), C117(C15,C59,C119,C121)
6.b Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C113(H11S,H11T), C115(H11U,H11V), C15(H15A,H15B), C59(H59A,
 H59B), C119(H,H11Z)
6.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C8(H8), C22(H22), C36(H36), C38(H38), C42(H42), C62(H62), C69(H69),
 C80(H80), C88(H88), C1(H1), C4(H4), C10(H10), C12(H12), C14(H14), C16(H16),
 C18(H18), C20(H20), C24(H24), C30(H30), C44(H44), C72(H72), C78(H78), C92(H92),
  C100(H100)
6.d Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C11(H11M,H11N,H11O), C25(H25A,H25B,H25C),
 C31(H31A,H31B,H31C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C49(H49A,H49B,
 H49C), C51(H51A,H51B,H51C), C63(H63A,H63B,H63C), C65(H65A,H65B,H65C), C73(H73A,
 H73B,H73C), C75(H75A,H75B,H75C), C77(H77A,H77B,H77C), C83(H83A,H83B,H83C),
 C84(H84A,H84B,H84C), C87(H87A,H87B,H87C), C91(H91A,H91B,H91C), C97(H97A,H97B,
 H97C), C99(H99A,H99B,H99C), C103(H10P,H10Q,H10R), C106(H10M,H10N,H10O),
 C110(H11G,H11H,H11I), C114(H11J,H11K,H11L), C27(H27A,H27B,H27C), C53(H53A,H53B,
 H53C), C107(H10S,H10T,H10U), C55(H55A,H55B,H55C), C109(H10V,H10W,H10X),
 C111(H11P,H11Q,H11R), C2(H2A,H2B,H2C), C9(H9A,H9B,H9C), C13(H13A,H13B,H13C),
 C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C23(H23A,H23B,
 H23C), C33(H33A,H33B,H33C), C35(H35A,H35B,H35C), C37(H37A,H37B,H37C), C39(H39A,
 H39B,H39C), C41(H41A,H41B,H41C), C47(H47A,H47B,H47C), C61(H61A,H61B,H61C),
 C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C71(H71A,H71B,H71C), C79(H79A,H79B,
 H79C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C85(H85A,H85B,H85C), C86(H86A,
 H86B,H86C), C89(H89A,H89B,H89C), C90(H90A,H90B,H90C), C93(H93A,H93B,H93C),
 C94(H94A,H94B,H94C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C98(H98A,H98B,
 H98C), C101(H10G,H10H,H10I), C104(H10A,H10B,H10C), C105(H10J,H10K,H10L),
 C108(H10D,H10E,H10F), C112(H11A,H11B,H11C), C118(H11D,H11E,H11F), C120(H12A,
 H12B,H12C), C7(H7C,H7A,H7B), C29(H29B,H29C,H29A), C117(H11W,H11X,H11Y),
 C121(H12D,H12E,H12F)
;
_shelx_res_checksum              90430
_olex2_exptl_crystal_mounting_method tip-mounted
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.153
_oxdiff_exptl_absorpt_empirical_full_min 0.851