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_4085415
_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         'C28 H65 Cl N4 O Si3 Th, C6 H14'
_chemical_formula_sum            'C34 H79 Cl N4 O Si3 Th'
_chemical_formula_weight         911.77
_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   geom
_audit_creation_date             2014-11-10
_audit_creation_method
;
Olex2 1.2
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                71.861(5)
_cell_angle_beta                 74.644(5)
_cell_angle_gamma                81.898(5)
_cell_formula_units_Z            6
_cell_length_a                   14.481(5)
_cell_length_b                   20.964(7)
_cell_length_c                   22.540(7)
_cell_measurement_reflns_used    10738
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      27.07
_cell_measurement_theta_min      2.25
_cell_volume                     6258(4)
_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      90(2)
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.917
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       \w
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0986
_diffrn_reflns_av_unetI/netI     0.2022
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.917
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            54396
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.917
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         28.086
_diffrn_reflns_theta_min         1.556
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    3.755
_exptl_absorpt_correction_T_max  0.4306
_exptl_absorpt_correction_T_min  0.2667
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2007/2 (Bruker,2007) was used for absorption correction.
wR2(int) was 0.0894 before and 0.0580 after correction.
The Ratio of minimum to maximum transmission is 0.6194.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.452
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             2808
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_refine_diff_density_max         2.216
_refine_diff_density_min         -3.082
_refine_diff_density_rms         0.248
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.016
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1092
_refine_ls_number_reflns         27954
_refine_ls_number_restraints     1107
_refine_ls_restrained_S_all      1.000
_refine_ls_R_factor_all          0.1808
_refine_ls_R_factor_gt           0.0838
_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^)+(0.0795P)^2^+100.6395P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1949
_refine_ls_wR_factor_ref         0.2306
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13920
_reflns_number_total             27954
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            om501177s_si_001.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 4085415--4085420.cif.'
_cod_original_cell_volume        6257(3)
_cod_database_code               4085415
_nottingham_internal_coll_name   THBGLE
_nottingham_internal_coll_number 11755
_nottingham_internal_coll_client BMG/STL
_nottingham_internal_coll_type   sphere
_nottingham_internal_coll_frame_method \w
_nottingham_internal_coll_frame_time 90
_nottingham_internal_coll_frame_width 0.3
_nottingham_internal_coll_user   BMG
_nottingham_internal_coll_date   10/08/2012
_nottingham_internal_coll_location NOTTS
_nottingham_internal_process_date 15/08/2012
_nottingham_internal_process_user BMG
_nottingham_internal_solution_date 15/08/2012
_nottingham_internal_solution_user BMG
_nottingham_internal_refinement_date 10/11/2012
_nottingham_internal_refinement_user BMG/WL
_nottingham_internal_validation_date 21/11/2014
_nottingham_internal_validation_user pczwl
_nottingham_internal_archive_date 21/11/2014
_platon_squeeze_void_probe_radius 1.20
_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
 O3-C81A \\sim O3-C81
 with sigma of 0.02
 C82A-C81A \\sim C82-C81
 with sigma of 0.02
 C83-C82A \\sim C83-C82
 with sigma of 0.02
3. 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
4. Others
 Sof(C81A)=Sof(H81C)=Sof(H81D)=1-FVAR(1)
 Sof(C81)=Sof(H81A)=Sof(H81B)=FVAR(1)
 Sof(H83C)=Sof(H83D)=Sof(C82A)=Sof(H82C)=Sof(H82D)=1-FVAR(2)
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H83A)=Sof(H83B)=FVAR(2)
5.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), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B),
  C35(H35A,H35B), C36(H36A,H36B), C43(H43A,H43B), C44(H44A,H44B), C51(H51A,
 H51B), C52(H52A,H52B), C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B),
 C56(H56A,H56B), C63(H63A,H63B), C64(H64A,H64B), C71(H71A,H71B), C72(H72A,H72B),
  C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,
 H83B), C83(H83C,H83D), C84(H84A,H84B), C81A(H81C,H81D), C82A(H82C,H82D)
5.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C6(H6A,
 H6B,H6C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C13(H13A,
 H13B,H13C), C14(H14A,H14B,H14C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C),
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,
 H34B,H34C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C40(H40A,H40B,H40C),
 C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C57(H57A,
 H57B,H57C), C58(H58A,H58B,H58C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C),
 C62(H62A,H62B,H62C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C68(H68A,H68B,
 H68C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C73(H73A,H73B,H73C), C74(H74A,
 H74B,H74C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'