Thorium Triamidoamine Complexes: Synthesis of an Unusual Dinuclear Tuck-in–Tuck-over Thorium Metallacycle Featuring the Longest Known Thorium−σ-Alkyl Bond
Gardner, Benedict M.; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.; Organometallics 34 (2015) 2386–; doi:10.1021/om501177s

data_4085420
_publ_section_title
;
 Thorium Triamidoamine Complexes: Synthesis of an Unusual Dinuclear
 Tuck-in--Tuck-over Thorium Metallacycle Featuring the Longest Known
 Thorium&#x2212;\s-Alkyl Bond
;
_journal_issue                   11
_journal_name_full               Organometallics
_journal_page_first              2386
_journal_paper_doi               10.1021/om501177s
_journal_volume                  34
_journal_year                    2015
_chemical_formula_moiety         'C48 H112 N8 O2 Si6 Th2'
_chemical_formula_sum            'C48 H112 N8 O2 Si6 Th2'
_chemical_formula_weight         1466.07
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   'geom, Me from difmap'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-10-01
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.3624(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3210(3)
_cell_length_b                   22.3137(4)
_cell_length_c                   20.5302(4)
_cell_measurement_reflns_used    32027
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.5472
_cell_measurement_theta_min      3.6338
_cell_volume                     6541.5(2)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.3613
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega -100.00  -55.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127 -153.0000   67.0000 45

  2 omega  -70.00  -12.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127   77.0000  150.0000 58

  3 omega   26.00  111.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       43.9127   57.0000  -30.0000 85

  4 omega -101.00  -75.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -60.0000 -125.0000  -60.0000 26

  5 omega   29.00   88.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -95.0000  120.0000 59

  6 omega  115.00  158.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   45.0000  150.0000 43

  7 omega   34.00   67.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000  -90.0000 33

  8 omega   47.00   74.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -45.0000  120.0000 27

  9 omega   36.00  109.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472 -121.0000   51.0000 73

 10 omega   27.00   97.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -95.0000   60.0000 70

 11 omega   72.00  101.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472 -125.0000 -150.0000 29

 12 omega   79.00  158.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   77.0000 -150.0000 79

 13 omega   40.00   68.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000   30.0000 28

 14 omega   90.00  120.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472 -125.0000  -90.0000 30

 15 omega   41.00   70.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -45.0000  150.0000 29

 16 omega   45.00   71.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -45.0000 -120.0000 26

 17 omega  -24.00   69.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       43.9127  -57.0000 -120.0000 93

 18 omega   14.00  115.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       43.9127   77.0000 -150.0000 101

 19 omega   19.00  112.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       43.9127   57.0000  120.0000 93

 20 omega -131.00  -30.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      -60.0000  -77.0000   30.0000 101

 21 omega   76.00  158.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   77.0000 -120.0000 82

 22 omega   36.00   77.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -45.0000 -150.0000 41

 23 omega   85.00  158.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   30.0000  120.0000 73

 24 omega   27.00  110.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -95.0000 -120.0000 83

 25 omega   83.00  158.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   45.0000  -60.0000 75

 26 omega   33.00   69.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000   90.0000 36

 27 omega   76.00  158.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   77.0000 -180.0000 82

 28 omega   66.00  158.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   15.0000   60.0000 92

 29 omega -112.00  -19.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127  -57.0000   90.0000 93

 30 omega -113.00  -55.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.9127 -153.0000 -108.0000 58

 31 omega   14.00  115.00   1.0000   10.0000
omega____ theta____ kappa____ phi______ frames
    -       43.9127   77.0000  -60.0000 101

 32 omega   80.00  105.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   61.0000   60.0000 25

 33 omega   76.00  158.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   77.0000  120.0000 82

 34 omega   80.00  158.00   1.0000   40.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   61.0000  -30.0000 78
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova-Duo, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.1034965000
_diffrn_orient_matrix_UB_12      0.0029634000
_diffrn_orient_matrix_UB_13      0.0263995000
_diffrn_orient_matrix_UB_21      0.0009707000
_diffrn_orient_matrix_UB_22      -0.0685425000
_diffrn_orient_matrix_UB_23      0.0091809000
_diffrn_orient_matrix_UB_31      0.0304759000
_diffrn_orient_matrix_UB_32      -0.0079441000
_diffrn_orient_matrix_UB_33      -0.0698364000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0645
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            87133
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         74.720
_diffrn_reflns_theta_min         3.637
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    15.911
_exptl_absorpt_correction_T_max  0.458
_exptl_absorpt_correction_T_min  0.185
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.21 (release 14-08-2012 CrysAlis171 .NET)
(compiled Sep 14 2012,17:21:16)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.489
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2944
_exptl_crystal_size_max          0.1685
_exptl_crystal_size_mid          0.1117
_exptl_crystal_size_min          0.0796
_refine_diff_density_max         4.319
_refine_diff_density_min         -2.033
_refine_diff_density_rms         0.130
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     770
_refine_ls_number_reflns         13232
_refine_ls_number_restraints     1264
_refine_ls_restrained_S_all      1.012
_refine_ls_R_factor_all          0.0531
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0524P)^2^+31.9469P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1128
_refine_ls_wR_factor_ref         0.1184
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11326
_reflns_number_total             13232
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om501177s_si_001.cif
_cod_data_source_block           6
_cod_depositor_comments
'Adding full bibliography for 4085415--4085420.cif.'
_cod_database_code               4085420
_nottingham_internal_coll_name   THBGLP
_nottingham_internal_coll_number 12008
_nottingham_internal_coll_client BMG/STL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_time '10s, 40s'
_nottingham_internal_coll_frame_width '1 degree'
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_user   pczbg
_nottingham_internal_coll_date   19/11/2012
_nottingham_internal_coll_location NOTTS
_nottingham_internal_process_user pczbg
_nottingham_internal_process_date 20/11/2012
_nottingham_internal_solution_user BMG
_nottingham_internal_solution_date 20/11/2012
_nottingham_internal_refinement_user BMG
_nottingham_internal_refinement_date 01/10/2014
_nottingham_internal_self_validation_user BMG
_nottingham_internal_self_validation_date 01/10/2014
_nottingham_internal_self_archive_date 02/10/2014
_nottingham_internal_validation_user pczwl
_nottingham_internal_validation_date 10/11/2014
_nottingham_internal_archive_date 10/11/2014
_chemical_oxdiff_formula         'C48 H112 N8 Si6 Th2'
_chemical_oxdiff_usercomment
'THBGLP #12008 IN FOMBLIN FILM ON MICROMOUNT FOR BG/STL'
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C12A-C11A \\sim C13A-C11A \\sim C14A-C11A \\sim C12-C11 \\sim C13-C11 \\sim
C14-C11
 with sigma of 0.02
 C37-C35 \\sim C37A-C35A \\sim C38-C35 \\sim C38A-C35A \\sim C36A-C35A \\sim
C36-C35
 with sigma of 0.02
 Si5A-N6A \\sim Si5-N6
 with sigma of 0.02
 Si5-C35 \\sim Si5A-C35A
 with sigma of 0.02
 Si5-C33 \\sim Si5A-C33A \\sim Si5A-C34A \\sim Si5-C34
 with sigma of 0.02
 Si2A-N2 \\sim Si2-N2
 with sigma of 0.02
 Si2A-C11A \\sim Si2-C11
 with sigma of 0.02
 Si2-C10 \\sim Si2-C9 \\sim Si2A-C10A \\sim Si2A-C9A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.02 and sigma
for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Si2A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(H10D)=
 Sof(H10E)=Sof(H10F)=Sof(C11A)=Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=
 Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=Sof(H14D)=Sof(H14E)=
 Sof(H14F)=1-FVAR(1)
 Sof(Si2)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=
 Sof(H10C)=Sof(C11)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13)=Sof(H13A)=
 Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=FVAR(1)
 Sof(N6A)=Sof(Si5A)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C34A)=
 Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(C35A)=Sof(C36A)=Sof(H36D)=Sof(H36E)=
 Sof(H36F)=Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C38A)=Sof(H38D)=
 Sof(H38E)=Sof(H38F)=Sof(H39C)=Sof(H39D)=1-FVAR(2)
 Sof(N6)=Sof(Si5)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34)=Sof(H34A)=
 Sof(H34B)=Sof(H34C)=Sof(C35)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=
 Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(H39A)=
 Sof(H39B)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C7(H7A,H7B), C8(H8A,H8B), C15(H15A,H15B), C16(H16A,H16B),
 C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C31(H31A,H31B), C32(H32A,H32B),
  C39(H39C,H39D), C39(H39A,H39B), C40(H40A,H40B), C47(H47A,H47B), C48(H48A,H48B)
6.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C9(H9A,
 H9B,H9C), C9A(H9AA,H9AB,H9AC), C10(H10A,H10B,H10C), C10A(H10D,H10E,H10F),
 C12(H12A,H12B,H12C), C12A(H12D,H12E,H12F), C13(H13A,H13B,H13C), C13A(H13D,H13E,
 H13F), C14(H14A,H14B,H14C), C14A(H14D,H14E,H14F), C17(H17A,H17B,H17C),
 C18(H18A,H18B,H18C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,
 H22C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,
 H30B,H30C), C33(H33A,H33B,H33C), C33A(H33D,H33E,H33F), C34(H34A,H34B,H34C),
 C34A(H34D,H34E,H34F), C36(H36A,H36B,H36C), C36A(H36D,H36E,H36F), C37(H37A,H37B,
 H37C), C37A(H37D,H37E,H37F), C38(H38A,H38B,H38C), C38A(H38D,H38E,H38F),
 C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,
 H45C), C46(H46A,H46B,H46C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id THBGLP
_olex2_submission_special_instructions 'No special instructions were received'