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_4085418
_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 Si6 Th2'
_chemical_formula_sum            'C48 H112 N8 Si6 Th2'
_chemical_formula_weight         1434.07
_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   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2014-09-30
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                90
_cell_angle_beta                 91.306(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.9997(3)
_cell_length_b                   21.9902(5)
_cell_length_c                   20.9322(5)
_cell_measurement_reflns_used    29213
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.3500
_cell_measurement_theta_min      3.7950
_cell_volume                     6442.4(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24a (release 19-12-2012 CrysAlis171 .NET)
(compiled Dec 19 2012,11:08:27)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24a (release 19-12-2012 CrysAlis171 .NET)
(compiled Dec 19 2012,11:08:27)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24a (release 19-12-2012 CrysAlis171 .NET)
(compiled Dec 19 2012,11:08:27)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (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 0.999
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_details
;
  1 omega  -20.00   16.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.6627   57.0000  120.0000 36

  2 omega   24.00  114.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       43.6627   38.0000    0.0000 90

  3 omega   46.00  111.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       43.6627   38.0000   60.0000 65

  4 omega -136.00 -106.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -60.0000  -95.0000   30.0000 30

  5 omega   41.00   68.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -45.0000   60.0000 27

  6 omega   40.00   77.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -45.0000  -60.0000 37

  7 omega   40.00   77.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -45.0000   90.0000 37

  8 omega   41.00   92.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -56.0000 -102.0000 51

  9 omega   33.00   69.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000 -120.0000 36

 10 omega  129.00  158.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   30.0000    0.0000 29

 11 omega   33.00   64.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000  -90.0000 31

 12 omega   41.00   69.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000 -150.0000 28

 13 omega   36.00   67.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -45.0000  150.0000 31

 14 omega   87.00  158.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   45.0000 -120.0000 71

 15 omega   45.00   72.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -45.0000  120.0000 27

 16 omega   33.00   60.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000  -30.0000 27

 17 omega   94.00  158.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   45.0000  150.0000 64

 18 omega   68.00  144.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   15.0000  150.0000 76

 19 omega -115.00  -14.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.6627  -77.0000 -150.0000 101

 20 omega -112.00  -19.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.6627  -57.0000   90.0000 93

 21 omega    2.00   98.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       43.6627 -125.0000  120.0000 96

 22 omega  -28.00   74.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       43.6627  -77.0000  -90.0000 102

 23 omega   36.00  122.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472 -125.0000  120.0000 86

 24 omega   85.00  110.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   30.0000  -30.0000 25

 25 omega   33.00   69.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000 -180.0000 36
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova-Duo, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0043852000
_diffrn_orient_matrix_UB_12      -0.0403465000
_diffrn_orient_matrix_UB_13      -0.0600144000
_diffrn_orient_matrix_UB_21      0.1014954000
_diffrn_orient_matrix_UB_22      0.0234828000
_diffrn_orient_matrix_UB_23      -0.0125448000
_diffrn_orient_matrix_UB_31      0.0422512000
_diffrn_orient_matrix_UB_32      -0.0522484000
_diffrn_orient_matrix_UB_33      0.0407861000
_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  0.0484
_diffrn_reflns_av_unetI/netI     0.0259
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            48245
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         74.606
_diffrn_reflns_theta_min         3.744
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    16.118
_exptl_absorpt_correction_T_max  0.270
_exptl_absorpt_correction_T_min  0.041
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24a (release 19-12-2012 CrysAlis171 .NET)
(compiled Dec 19 2012,11:08:27)
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    1.479
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2880
_exptl_crystal_size_max          0.3776
_exptl_crystal_size_mid          0.2201
_exptl_crystal_size_min          0.2145
_refine_diff_density_max         2.078
_refine_diff_density_min         -1.699
_refine_diff_density_rms         0.170
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.191
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     807
_refine_ls_number_reflns         12869
_refine_ls_number_restraints     1609
_refine_ls_restrained_S_all      1.137
_refine_ls_R_factor_all          0.0528
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0240P)^2^+94.6891P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1215
_refine_ls_wR_factor_ref         0.1221
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12453
_reflns_number_total             12869
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om501177s_si_001.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 4085415--4085420.cif.'
_cod_database_code               4085418
_nottingham_internal_coll_name   THBGLS
_nottingham_internal_coll_number 12096
_nottingham_internal_coll_client BMG/STL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_time '15s, 60s'
_nottingham_internal_coll_frame_width '1 degree'
_nottingham_internal_coll_frame_method '\w scans'
_nottingham_internal_coll_user   pczbg
_nottingham_internal_coll_date   07/01/2013
_nottingham_internal_coll_location NOTTS
_nottingham_internal_process_user pczbg
_nottingham_internal_process_date 10/01/2013
_nottingham_internal_solution_user BMG
_nottingham_internal_solution_date 10/01/2013
_nottingham_internal_refinement_user BMG
_nottingham_internal_refinement_date 30/09/2014
_nottingham_internal_self_validation_user BMG
_nottingham_internal_self_validation_date 30/09/2014
_nottingham_internal_self_archive_date 02/10/2014
_chemical_oxdiff_formula         'C48 H112 N8 Si6 Th2'
_chemical_oxdiff_usercomment
'THBGLS #12096 IN FOMBLIN FILM ON MICROMOUNT FOR BG/STL'
_reflns_odcompleteness_completeness 99.92
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H1B-H1A
 1.6 with sigma of 0.02
 H25C-H25D
 1.6 with sigma of 0.02
 H1AB-H1AA
 1.6 with sigma of 0.02
 H25A-H25B
 1.6 with sigma of 0.02
 C25A-H25D = C25-H25B = C25-H25A = C25A-H25C = C1-H1A = C1A-H1AA = C1-H1B =
 C1A-H1AB
 0.96 with sigma of 0.001
 Th1-H1AB = Th1-H1AA
 -3.45 with sigma of 0.02
 C4A-C5A \\sim C5A-C6A \\sim C6A-C4A
 with sigma of 0.02
 C6-C3 \\sim C5-C3 \\sim C4-C3 \\sim C6A-C3A \\sim C5A-C3A \\sim C4A-C3A
 with sigma of 0.02
 C30A-C27A \\sim C29A-C27A \\sim C28A-C27A \\sim C30-C27 \\sim C29-C27 \\sim
C28-C27
 with sigma of 0.02
 Si2-N2 \\sim Si2A-N2
 with sigma of 0.02
 Si2A-C11A \\sim Si2-C11
 with sigma of 0.02
 C13-C11 \\sim C12-C11 \\sim C14-C11 \\sim C13A-C11A \\sim C14A-C11A \\sim
C12A-C11A
 with sigma of 0.02
 Si2A-C9 \\sim Si2-C9A \\sim Si2A-C10A \\sim Si2-C10
 with sigma of 0.02
 Si1-C3 \\sim Si1A-C3A
 with sigma of 0.02
 Si4-C26 \\sim Si4A-C26A
 with sigma of 0.02
 Si4-C27 \\sim Si4A-C27A
 with sigma of 0.02
 Si1A-C1 \\sim Si1-C1
 with sigma of 0.02
 Si1A-C1A \\sim Si1-C1
 with sigma of 0.02
 H1AA-H1AB \\sim H1B-H1A
 with sigma of 0.02
 Si4-C25 \\sim Si4A-C25
 with sigma of 0.02
 Si4-C25 \\sim Si4A-C25A
 with sigma of 0.02
 H25A-H25B \\sim H25C-H25D
 with sigma of 0.02
 Th1-H1AB \\sim Th1-H1AA
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
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(Si4A)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=Sof(C27A)=Sof(C28A)=
 Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=
 Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C25A)=Sof(H25D)=Sof(H25C)=1-FVAR(1)
 Sof(Si4)=Sof(C25)=Sof(H25B)=Sof(H25A)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C27)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
 Sof(C1A)=Sof(H1AB)=Sof(H1AA)=Sof(Si1A)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=
 Sof(C3A)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=
 Sof(H5AC)=Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=1-FVAR(2)
 Sof(Si1)=Sof(C1)=Sof(H1B)=Sof(H1A)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C3)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=
 Sof(H6A)=Sof(H6B)=Sof(H6C)=FVAR(2)
 Sof(Si2A)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C14A)=Sof(H14A)=
 Sof(H14B)=Sof(H14C)=Sof(C11A)=Sof(C12A)=Sof(H12D)=Sof(H12E)=Sof(H12F)=
 Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C10A)=Sof(H10A)=Sof(H10B)=
 Sof(H10C)=1-FVAR(3)
 Sof(Si2)=Sof(C14)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C11)=Sof(C13)=Sof(H13A)=
 Sof(H13B)=Sof(H13C)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C9)=Sof(H9A)=
 Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10D)=Sof(H10E)=Sof(H10F)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C15(H15A,H15B), C16(H16A,H16B), C23(H23A,H23B),
 C24(H24A,H24B), C31(H31A,H31B), C32(H32A,H32B), C39(H39A,H39B), C40(H40A,H40B),
  C47(H47A,H47B), C48(H48A,H48B)
6.b Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C2A(H2AA,H2AB,H2AC),
 C4A(H4AA,H4AB,H4AC), C5A(H5AA,H5AB,H5AC), C6A(H6AA,H6AB,H6AC), 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), C26A(H26D,H26E,H26F), C28A(H28D,H28E,H28F), C29A(H29D,
 H29E,H29F), C30A(H30D,H30E,H30F), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C),
 C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C9A(H9AA,H9AB,H9AC), C14A(H14A,H14B,H14C), C14(H14D,H14E,H14F),
 C13(H13A,H13B,H13C), C12(H12A,H12B,H12C), C12A(H12D,H12E,H12F), C13A(H13D,H13E,
 H13F), C9(H9A,H9B,H9C), C10A(H10A,H10B,H10C), C10(H10D,H10E,H10F)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id THBGLS
_olex2_submission_special_instructions 'No special instructions were received'