A Base-Free Terminal Actinide Phosphinidene Metallocene: Synthesis, Structure, Reactivity, and Computational Studies.
Zhang, Congcong; Hou, Guohua; Zi, Guofu; Ding, Wanjian; Walter, Marc D.; Journal of the American Chemical Society 140 (2018) 14511–14525; doi:10.1021/jacs.8b09746

data_4133354
_publ_section_title
;
 A Base-Free Terminal Actinide Phosphinidene Metallocene: Synthesis,
 Structure, Reactivity, and Computational Studies.
;
_journal_issue                   43
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14511
_journal_page_last               14525
_journal_paper_doi               10.1021/jacs.8b09746
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C68 H116 S2 Th2'
_chemical_formula_sum            'C68 H116 S2 Th2'
_chemical_formula_weight         1461.80
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-11-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.8176(2)
_cell_length_b                   10.78270(10)
_cell_length_c                   27.5783(3)
_cell_measurement_reflns_used    12108
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.0500
_cell_measurement_theta_min      4.0910
_cell_volume                     6487.87(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.32a (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3127
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_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   -115.00 -54.00   1.00    1.00    --  -41.49 -37.00 120.00   61
  2  \w    -82.00 -24.00   1.00    1.00    --  -41.49 -37.00 150.00   58
  3  \w    -86.00 -11.00   1.00    1.00    --  -41.49 125.00 -90.00   75
  4  \w     28.00  77.00   1.00    1.00    --   41.49-125.00-180.00   49
  5  \w     53.00 108.00   1.00    1.50    --  107.19 -94.00  90.00   55
  6  \w     79.00 168.00   1.00    1.50    --  107.19  30.00-120.00   89
  7  \w     86.00 153.00   1.00    1.50    --  107.19  77.00   0.00   67
  8  \w     56.00 107.00   1.00    1.50    --  107.19 -94.00-180.00   51
  9  \w     88.00 159.00   1.00    1.50    --  107.19  45.00 120.00   71
 10  \w     68.00 139.00   1.00    1.50    --  107.19 -77.00-120.00   71
 11  \w     61.00 103.00   1.00    1.50    --  107.19-125.00  90.00   42
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0070998000
_diffrn_orient_matrix_UB_12      -0.1380411000
_diffrn_orient_matrix_UB_13      0.0133926000
_diffrn_orient_matrix_UB_21      0.0662749000
_diffrn_orient_matrix_UB_22      -0.0244361000
_diffrn_orient_matrix_UB_23      -0.0167486000
_diffrn_orient_matrix_UB_31      0.0233263000
_diffrn_orient_matrix_UB_32      0.0277261000
_diffrn_orient_matrix_UB_33      0.0515644000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0443
_diffrn_reflns_av_unetI/netI     0.0487
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            25626
_diffrn_reflns_point_group_measured_fraction_full 0.807
_diffrn_reflns_point_group_measured_fraction_max 0.783
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.394
_diffrn_reflns_theta_min         4.052
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    15.545
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85962
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.32a (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.497
_exptl_crystal_description       block
_exptl_crystal_F_000             2944
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.11
_refine_diff_density_max         0.794
_refine_diff_density_min         -0.602
_refine_diff_density_rms         0.106
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   -0.019(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     685
_refine_ls_number_reflns         10232
_refine_ls_number_restraints     13
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0300
_refine_ls_R_factor_gt           0.0261
_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^)+(0.0076P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0489
_refine_ls_wR_factor_ref         0.0509
_reflns_Friedel_coverage         0.553
_reflns_Friedel_fraction_full    0.604
_reflns_Friedel_fraction_max     0.571
_reflns_number_gt                9445
_reflns_number_total             10232
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09746_si_002.cif
_cod_data_source_block           compound6
_cod_database_code               4133354
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1N1S1P1Th1
_reflns_odcompleteness_completeness 99.94
_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. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C24) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C20(H20), C22(H22), C37(H37), C39(H39), C54(H54), C56(H56)
3.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C),
 C51(H51A,H51B,H51C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C66(H66A,
 H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C)
;
_shelx_res_checksum              18099
_shelx_hkl_checksum              22950
_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 1.334
_oxdiff_exptl_absorpt_empirical_full_min 0.839