Reactivity of a Lewis base supported uranium terminal imido metallocene towards small molecules
Li, Tongyu; Wang, Dongwei; Heng, Yi; Hou, Guohua; Zi, Guofu; Walter, Marc D.; Dalton Transactions  (2023) –; doi:10.1039/D3DT02165C

data_7713812
_publ_section_title
;
 Reactivity of a Lewis base supported uranium terminal imido metallocene
 towards small molecules
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D3DT02165C
_journal_year                    2023
_chemical_formula_moiety         'C50 H80 N2 Si6 U'
_chemical_formula_sum            'C50 H80 N2 Si6 U'
_chemical_formula_weight         1115.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2022-01-21
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-06-29 deposited with the CCDC.	2023-08-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 94.7000(17)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   50.4898(9)
_cell_length_b                   11.7748(3)
_cell_length_c                   38.7911(8)
_cell_measurement_reflns_used    14931
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      75.7180
_cell_measurement_theta_min      3.6290
_cell_volume                     22984.0(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.110a (Rigaku OD, 2021)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.952
_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     93.00 176.00   0.50    0.05    --  104.75  45.00   0.00  166
  2  \w    138.00 163.00   0.50    0.05    --  104.75  51.00 -53.00   50
  3  \w    136.00 162.00   0.50    0.05    --  104.75  45.00  30.00   52
  4  \w    105.00 172.00   0.50    0.05    --  104.75  45.00  60.00  134
  5  \w     45.00 115.00   0.50    0.05    --   46.91  51.00 -53.00  140
  6  \w    -24.00  26.00   0.50    0.05    --  -46.91  19.00  60.00  100
  7  \w    -56.00 -29.00   0.50    0.05    -- -102.00  51.00 -53.00   54
  8  \w    -56.00  26.00   0.50    0.05    --  -46.91  51.00 -53.00  164
  9  \w    -67.00 -32.00   0.50    0.05    -- -102.00  61.00  90.00   70
 10  \w    -69.00 -31.00   0.50    0.05    -- -102.00  61.00 120.00   76
 11  \w    -65.00 -40.00   0.50    0.05    -- -102.00  61.00 150.00   50
 12  \w   -173.00 -88.00   0.50    0.05    -- -102.00 -51.00 160.00  170
 13  \w   -116.00 -72.00   0.50    0.05    --  -46.91-125.00 -60.00   88
 14  \w   -175.00 -83.00   0.50    0.05    -- -102.00 -94.00 -90.00  184
 15  \w    -90.00 -64.00   0.50    0.05    --  -46.91 -51.00 160.00   52
 16  \w     35.00  71.00   0.50    0.05    --  104.75 -94.00   0.00   72
 17  \w     84.00 109.00   0.50    0.05    --  104.75 -94.00   0.00   50
 18  \w     56.00  95.00   0.50    0.05    --  104.75 -94.00-150.00   78
 19  \w     56.00  82.00   0.50    0.05    --  104.75 -94.00 -90.00   52
 20  \w     37.00  62.00   0.50    0.05    --  104.75 -61.00 -60.00   50
 21  \w     32.00  73.00   0.50    0.05    --  104.75 -61.00-150.00   82
 22  \w    -24.00   1.00   0.50    0.05    --   46.91 -51.00 160.00   50
 23  \w     19.00  45.00   0.50    0.10    --   46.91 -51.00 160.00   52
 24  \w     32.00  65.00   0.50    0.10    --  104.75 -61.00 150.00   66
 25  \w     35.00  60.00   0.50    0.10    --  104.75 -51.00 160.00   50
 26  \w      3.00  29.00   0.50    0.10    --   46.91 -51.00 160.00   52
 27  \w   -103.00 -77.00   0.50    0.10    --  -46.91-125.00-150.00   52
 28  \w   -170.00-144.00   0.50    0.10    -- -102.00 -94.00 150.00   52
 29  \w   -127.00 -92.00   0.50    0.10    -- -102.00 -94.00 150.00   70
 30  \w    -69.00 -44.00   0.50    0.10    -- -102.00  61.00 -30.00   50
 31  \w     63.00  89.00   0.50    0.10    --  104.75 -94.00 -90.00   52
 32  \w     45.00  72.00   0.50    0.10    --  104.75 -61.00  60.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0212935000
_diffrn_orient_matrix_UB_12      0.0485923000
_diffrn_orient_matrix_UB_13      0.0222042000
_diffrn_orient_matrix_UB_21      0.0216737000
_diffrn_orient_matrix_UB_22      0.0654714000
_diffrn_orient_matrix_UB_23      0.0221087000
_diffrn_orient_matrix_UB_31      -0.0037799000
_diffrn_orient_matrix_UB_32      0.1023132000
_diffrn_orient_matrix_UB_33      -0.0246191000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1615
_diffrn_reflns_av_unetI/netI     0.1325
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.952
_diffrn_reflns_limit_h_max       63
_diffrn_reflns_limit_h_min       -62
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       46
_diffrn_reflns_limit_l_min       -48
_diffrn_reflns_number            93378
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.952
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.715
_diffrn_reflns_theta_min         3.513
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.378
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66107
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.110a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       block
_exptl_crystal_F_000             9120
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.05
_refine_diff_density_max         4.290
_refine_diff_density_min         -3.555
_refine_diff_density_rms         0.234
_refine_ls_extinction_coef       0.000015(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1114
_refine_ls_number_reflns         23043
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1162
_refine_ls_R_factor_gt           0.0809
_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^)+(0.1295P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2021
_refine_ls_wR_factor_ref         0.2373
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15340
_reflns_number_total             23043
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02165c2.cif
_cod_data_source_block           compound12
_cod_original_cell_volume        22984.1(9)
_cod_database_code               7713812
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1N1Si1U1
_shelx_estimated_absorpt_t_max   0.651
_shelx_estimated_absorpt_t_min   0.256
_diffrn_oxdiff_digest_frames
;
01070b205cb65d1ebd3f4af9fdde51aca002534221b
;
_diffrn_oxdiff_digest_hkl
;
01243725c8d1d4389d585cc064946a5d45f525
;
_reflns_odcompleteness_completeness 99.31
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-H1
 0.85 with sigma of 0.02
 N3-H3A
 0.85 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C62) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C56)
\\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C22) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Aromatic/amide H refined with riding coordinates:
 C53(H53), C55(H55), C67(H67), C69(H69), C80(H80), C81(H81), C83(H83),
 C84(H84), C88(H88), C89(H89), C91(H91), C92(H92), C95(H95), C96(H96), C98(H98),
  C99(H99), C3(H3), C5(H5), C17(H17), C19(H19), C30(H30), C31(H31), C33(H33),
 C34(H34), C38(H38), C39(H39), C41(H41), C42(H42), C45(H45), C46(H46), C48(H48),
  C49(H49)
4.b Idealised Me refined as rotating group:
 C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,
 H59C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,
 H63B,H63C), C64(H64A,H64B,H64C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C),
 C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,H75B,
 H75C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C85(H85A,
 H85B,H85C), C93(H93A,H93B,H93C), C100(H10D,H10E,H10F), C6(H6A,H6B,H6C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,
 H11C), C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C20(H20A,
 H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C),
 C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,
 H27C), C28(H28A,H28B,H28C), C35(H35A,H35B,H35C), C43(H43A,H43B,H43C), C50(H50A,
 H50B,H50C)
;
_shelx_res_checksum              62488
_shelx_fab_checksum              60560
_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 1.464
_oxdiff_exptl_absorpt_empirical_full_min 0.694