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_4133359
_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         'C120 H182 N4 P2 Th2, 3(C6 H6)'
_chemical_formula_sum            'C138 H200 N4 P2 Th2'
_chemical_formula_weight         2441.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-04-08
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_cell_angle_alpha                90
_cell_angle_beta                 100.882(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   11.1972(2)
_cell_length_b                   20.3586(4)
_cell_length_c                   28.0100(5)
_cell_measurement_reflns_used    26240
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.0490
_cell_measurement_theta_min      3.8620
_cell_volume                     6270.3(2)
_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 0.999
_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    -64.00  -2.00   1.00    1.00    --  -41.49 125.00  90.00   62
  2  \w    -66.00  29.00   1.00    1.00    --  -41.49  37.00  30.00   95
  3  \w   -115.00 -18.00   1.00    1.00    --  -41.49 -37.00-150.00   97
  4  \w     13.00  61.00   1.00    1.00    --   41.49 -99.00  60.00   48
  5  \w     47.00  96.00   1.00    1.00    --   41.49-125.00-120.00   49
  6  \w     84.00 109.00   1.00    1.00    --   41.49  57.00 -90.00   25
  7  \w     44.00  70.00   1.00    1.00    --  107.19-125.00 -90.00   26
  8  \w     55.00 175.00   1.00    1.00    --  107.19  15.00 -30.00  120
  9  \w     59.00 119.00   1.00    1.00    --  107.19-125.00 150.00   60
 10  \w    110.00 176.00   1.00    1.00    --  107.19 125.00 150.00   66
 11  \w     71.00 121.00   1.00    1.00    --  107.19-125.00   0.00   50
 12  \w     62.00  97.00   1.00    1.00    --  107.19-125.00 -60.00   35
 13  \w     90.00 116.00   1.00    1.00    --  107.19-125.00 -90.00   26
 14  \w     33.00  98.00   1.00    1.00    --  107.19 -30.00  30.00   65
 15  \w     93.00 178.00   1.00    1.00    --  107.19  30.00-150.00   85
 16  \w     34.00 128.00   1.00    1.00    --  107.19 -45.00-120.00   94
 17  \w     37.00 136.00   1.00    1.00    --  107.19 -61.00 120.00   99
 18  \w     62.00 115.00   1.00    1.00    --  107.19 -61.00 -30.00   53
;
_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      -0.0225545000
_diffrn_orient_matrix_UB_12      0.0603585000
_diffrn_orient_matrix_UB_13      0.0303520000
_diffrn_orient_matrix_UB_21      -0.1320824000
_diffrn_orient_matrix_UB_22      -0.0226473000
_diffrn_orient_matrix_UB_23      -0.0017912000
_diffrn_orient_matrix_UB_31      0.0410120000
_diffrn_orient_matrix_UB_32      -0.0396176000
_diffrn_orient_matrix_UB_33      0.0470566000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0487
_diffrn_reflns_av_unetI/netI     0.0453
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            42539
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.436
_diffrn_reflns_theta_min         4.038
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.197
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.74637
_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            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.293
_exptl_crystal_description       prism
_exptl_crystal_F_000             2532
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.759
_refine_diff_density_min         -1.053
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     685
_refine_ls_number_reflns         12438
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0372
_refine_ls_R_factor_gt           0.0292
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0248P)^2^+7.1215P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0655
_refine_ls_wR_factor_ref         0.0696
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10722
_reflns_number_total             12438
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b09746_si_002.cif
_cod_data_source_block           compound11
_cod_database_code               4133359
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1N1Th1P1
_reflns_odcompleteness_completeness 99.95
_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(C61) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C64)
\\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C67) \\sim Ueq,
Uanis(C68) \\sim Ueq, Uanis(C69) \\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), C38(H38), C40(H40), C41(H41),
 C45(H45), C47(H47), C61(H61), C62(H62), C63(H63), C64(H64), C65(H65), C66(H66),
  C67(H67), C68(H68), C69(H69)
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), C50(H50A,H50B,
 H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C55(H55A,
 H55B,H55C), C56(H56A,H56B,H56C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C),
 C60(H60A,H60B,H60C)
;
_shelx_res_checksum              50411
_shelx_hkl_checksum              70513
_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 2.237
_oxdiff_exptl_absorpt_empirical_full_min 0.543