Experimental and computational studies on a three-membered diphosphido thorium metallaheterocycle [η<sup>5</sup>-1,3-(Me<sub>3</sub>C)<sub>2</sub>C<sub>5</sub>H<sub>3</sub>]<sub>2</sub>Th[η<sup>2</sup>-P<sub>2</sub>(2,4,6-<sup>i</sup>Pr<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)<sub>2</sub>].
Zhang, Congcong; Wang, Yongsong; Hou, Guohua; Ding, Wanjian; Zi, Guofu; Walter, Marc D.; Dalton transactions (Cambridge, England : 2003) 48 (2019) 6921–6930; doi:10.1039/c9dt01160a

data_7049927
_publ_section_title
;
 Experimental and computational studies on a three-membered diphosphido
 thorium metallaheterocycle
 [\h<sup>5</sup>-1,3-(Me<sub>3</sub>C)<sub>2</sub>C<sub>5</sub>H<sub>3</sub>]<sub>2</sub>Th[\h<sup>2</sup>-P<sub>2</sub>(2,4,6-<sup>i</sup>Pr<sub>3</sub>C<sub>6</sub>H<sub>2</sub>)<sub>2</sub>].
;
_journal_issue                   20
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6921
_journal_page_last               6930
_journal_paper_doi               10.1039/c9dt01160a
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         'C41 H66 Cl P Th, C3 H3'
_chemical_formula_sum            'C44 H69 Cl P Th'
_chemical_formula_weight         896.45
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2019-02-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-02-25 deposited with the CCDC.    2019-04-16 downloaded from the CCDC.
;
_cell_angle_alpha                70.744(4)
_cell_angle_beta                 80.695(4)
_cell_angle_gamma                70.864(4)
_cell_formula_units_Z            2
_cell_length_a                   10.3144(4)
_cell_length_b                   14.1787(5)
_cell_length_c                   16.4620(7)
_cell_measurement_reflns_used    7316
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.9180
_cell_measurement_theta_min      3.7280
_cell_volume                     2143.33(16)
_computing_cell_refinement       'CrysAlisPro 1.171.39.6a (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.6a (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.6a (Rigaku OD, 2015)'
_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      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.3127
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.973
_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    -60.00 -16.00   1.00    1.00    --  -41.49  37.00 -60.00   44
  2  \w    -89.00  -5.00   1.00    1.00    --  -41.49 125.00-120.00   84
  3  \w   -109.00 -18.00   1.00    1.00    --  -41.49 -37.00 -30.00   91
  4  \w     23.00  96.00   1.00    1.00    --   41.49-125.00-150.00   73
  5  \w     42.00 136.00   1.00    1.00    --  107.19 -61.00-180.00   94
  6  \w     81.00 118.00   1.00    1.00    --  107.19-125.00-120.00   37
  7  \w     84.00 114.00   1.00    1.00    --  107.19-125.00  30.00   30
  8  \w     74.00 140.00   1.00    1.00    --  107.19 -77.00  60.00   66
  9  \w     62.00 142.00   1.00    1.00    --  107.19  15.00 -30.00   80
 10  \w    135.00 162.00   1.00    1.00    --  107.19  15.00 -90.00   27
 11  \w    150.00 178.00   1.00    1.00    --  107.19  45.00-150.00   28
 12  \w    152.00 177.00   1.00    1.00    --  107.19 125.00  30.00   25
 13  \w    109.00 169.00   1.00    1.00    --  107.19 125.00  90.00   60
 14  \w     80.00 176.00   1.00    1.00    --  107.19  61.00 150.00   96
 15  \w     75.00 124.00   1.00    1.00    --  107.19  15.00 -90.00   49
 16  \w     84.00 119.00   1.00    1.00    --  107.19  45.00-150.00   35
 17  \w     34.00 126.00   1.00    1.00    --  107.19 -45.00   0.00   92
 18  \w     35.00 108.00   1.00    1.00    --  107.19 -94.00  30.00   73
 19  \w    -66.00  33.00   1.00    1.00    --  -41.49  37.00 150.00   99
;
_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      0.1031927000
_diffrn_orient_matrix_UB_12      -0.0558989000
_diffrn_orient_matrix_UB_13      -0.0603763000
_diffrn_orient_matrix_UB_21      -0.1197328000
_diffrn_orient_matrix_UB_22      0.0076640000
_diffrn_orient_matrix_UB_23      -0.0492927000
_diffrn_orient_matrix_UB_31      0.0100173000
_diffrn_orient_matrix_UB_32      0.1064046000
_diffrn_orient_matrix_UB_33      -0.0615389000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0878
_diffrn_reflns_av_unetI/netI     0.1107
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            15319
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.158
_diffrn_reflns_theta_min         3.455
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.329
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53174
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.6a (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.389
_exptl_crystal_description       block
_exptl_crystal_F_000             910
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         3.660
_refine_diff_density_min         -3.963
_refine_diff_density_rms         0.305
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     474
_refine_ls_number_reflns         8345
_refine_ls_number_restraints     295
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0730
_refine_ls_R_factor_gt           0.0614
_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^)+80.9561P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1788
_refine_ls_wR_factor_ref         0.1851
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7263
_reflns_number_total             8345
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt01160a2.cif
_cod_data_source_block           compound2
_cod_depositor_comments
'Adding full bibliography for 7049925--7049929.cif.'
_cod_original_cell_volume        2143.32(17)
_cod_database_code               7049927
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C1H1Cl1K1P1Th1
_reflns_odcompleteness_completeness 99.96
_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
 P1-H1
 1.3 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C11) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18) \\sim Ueq,
Uanis(C19) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22A)
\\sim Ueq, Uanis(C23B) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C24) \\sim Ueq,
Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C28)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C31) \\sim Ueq,
Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35)
\\sim Ueq, Uanis(C36A) \\sim Ueq, Uanis(C36B) \\sim Ueq, Uanis(C37A) \\sim Ueq,
Uanis(C37B) \\sim Ueq, Uanis(C38A) \\sim Ueq, Uanis(C38B) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(P1) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C28) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C40) = Uanis(C41)
Uanis(C36A) = Uanis(C36B)
4. Others
 Sof(C23B)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C36B)=Sof(H36B)=Sof(C37B)=
 Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C38B)=Sof(H38D)=Sof(H38E)=Sof(H38F)=1-FVAR(1)
 Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C36A)=Sof(H36A)=Sof(C37A)=
 Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38A)=Sof(H38A)=Sof(H38B)=Sof(H38C)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C33(H33), C36A(H36A), C36B(H36B), C39(H39)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C5(H5), C15(H15), C17(H17), C18(H18), C29(H29), C31(H31),
 C42(H42), C43(H43), C44(H44)
5.c 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), C20(H20A,H20B,H20C), C21(H21A,H21B,
 H21C), C22A(H22A,H22B,H22C), C23B(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), C37A(H37A,H37B,H37C), C37B(H37D,H37E,H37F), C38A(H38A,H38B,H38C),
 C38B(H38D,H38E,H38F), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              80844
_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 1.612
_oxdiff_exptl_absorpt_empirical_full_min 0.668