Mixed sandwich thorium complexes incorporating bis(tri-isopropylsilyl)cyclooctatetraenyl and pentamethylcyclopentadienyl ligands: synthesis, structure and reactivity.
Button, Zoë E; Higgins, Jessica A.; Suvova, Markéta; Cloke, F Geoffrey N; Roe, S. Mark; Dalton transactions (Cambridge, England : 2003) 44 (2015) 2588–2596; doi:10.1039/c4dt02362e

data_7032841
_publ_section_title
;
 Mixed sandwich thorium complexes incorporating
 bis(tri-isopropylsilyl)cyclooctatetraenyl and pentamethylcyclopentadienyl
 ligands: synthesis, structure and reactivity.
;
_journal_issue                   6
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              2588
_journal_page_last               2596
_journal_paper_doi               10.1039/c4dt02362e
_journal_volume                  44
_journal_year                    2015
_chemical_formula_moiety         'C36.5 H63 O1.5 Si2 Th, C7 H8'
_chemical_formula_sum            'C43.5 H71 O1.5 Si2 Th'
_chemical_formula_weight         906.22
_chemical_name_common            complex_3_carbonate
_chemical_name_systematic
;
(mu-carbonato)bis{(eta-5-pentamethylcyclopentadienyl)
(eta-8-(bis{triisopropylsilyl}cyclooctatetraene))thorium(IV)}
;
_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             2014-10-07
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.09.19 svn.r3010 for OlexSys, GUI svn.r4874)
;
_cell_angle_alpha                65.93(3)
_cell_angle_beta                 67.92(3)
_cell_angle_gamma                72.30(3)
_cell_formula_units_Z            2
_cell_length_a                   12.283(3)
_cell_length_b                   13.356(3)
_cell_length_c                   15.689(3)
_cell_measurement_reflns_used    47322
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      27.878
_cell_measurement_theta_min      3.395
_cell_volume                     2142.8(10)
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_collection       'Collect (Bruker AXS BV, 1997-2004)'
_computing_data_reduction
'HKL Denzo and Scalepack (Otwinowski & Minor)'
_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    'SHELXL-97 (Sheldrick, 1997)'
_diffrn_ambient_temperature      173.15
_diffrn_detector_area_resol_mean 9
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.957
_diffrn_measurement_device_type  KappaCCD
_diffrn_measurement_method       'CCD rotation images, thick slices'
_diffrn_radiation_monochromator  'horizonally mounted graphite crystal'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0581
_diffrn_reflns_av_unetI/netI     0.0418
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            31495
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.880
_diffrn_reflns_theta_min         3.396
_diffrn_source                   'Enraf Nonius FR590'
_exptl_absorpt_coefficient_mu    3.567
_exptl_absorpt_correction_T_max  0.8817
_exptl_absorpt_correction_T_min  0.7964
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2007/2 (Sheldrick, G.M., 2007)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.405
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             924
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.879
_refine_diff_density_min         -0.859
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     442
_refine_ls_number_reflns         9765
_refine_ls_number_restraints     75
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.0329
_refine_ls_R_factor_gt           0.0277
_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^)+(0.0185P)^2^+3.5977P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0605
_refine_ls_wR_factor_ref         0.0624
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8954
_reflns_number_total             9765
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c4dt02362e2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 7032839--7032844.cif.'
_cod_original_cell_volume        2142.8(11)
_cod_original_formula_sum        'C43.50 H71 O1.50 Si2 Th'
_cod_database_code               7032841
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.814
_shelx_estimated_absorpt_t_min   0.599
_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
 C1-O2
 1.28 with sigma of 0.02
 C1-O1
 1.28 with sigma of 0.02
 C1-O3
 1.28 with sigma of 0.02
 O2-O1
 2.22 with sigma of 0.02
 O1-O3
 2.22 with sigma of 0.02
 O2-O3
 2.22 with sigma of 0.02
3. Rigid bond restraints
 C33A, C33B, C35A, C35B, C36A, C36B, C37A, C37B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C33A \\sim C33B \\sim C35A \\sim C35B \\sim C36A \\sim C36B \\sim C37A \\sim
C37B: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C33A) = Uanis(C33B) = Uanis(C35A) = Uanis(C35B) = Uanis(C36A) =
Uanis(C36B) = Uanis(C37A) = Uanis(C37B)
5. Rigid body (RIGU) restrains
 C43, C38, C39, C44, H43, C42, H39, C40, H44A, H44B, H44C, H42, C41, H40, H41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C33B)=Sof(H33D)=Sof(H33E)=Sof(H33F)=Sof(C35B)=Sof(H35D)=Sof(H35E)=
 Sof(H35F)=Sof(C36B)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C37B)=Sof(H37D)=
 Sof(H37E)=Sof(H37F)=1-FVAR(1)
 Sof(C33A)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C35A)=Sof(H35A)=Sof(H35B)=
 Sof(H35C)=Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37A)=Sof(H37A)=
 Sof(H37B)=Sof(H37C)=FVAR(1)
 Fixed Sof: O2(0.5) O1(0.5) C1(0.5) O3(0.5)
7.a Ternary CH refined with riding coordinates:
 C22(H22), C25(H25), C19(H19), C13(H13), C10(H10), C16(H16)
7.b Me refined with riding coordinates:
 C26(H26A,H26B,H26C), C12(H12A,H12B,H12C), C23(H23A,H23B,H23C), C11(H11A,H11B,
 H11C), C27(H27A,H27B,H27C), C15(H15A,H15B,H15C), C21(H21A,H21B,H21C), C17(H17A,
 H17B,H17C), C18(H18A,H18B,H18C), C33A(H33A,H33B,H33C), C35A(H35A,H35B,H35C),
 C36A(H36A,H36B,H36C), C37A(H37A,H37B,H37C), C33B(H33D,H33E,H33F), C36B(H36D,
 H36E,H36F), C37B(H37D,H37E,H37F), C34(H34A,H34B,H34C), C14(H14A,H14B,H14C),
 C24(H24A,H24B,H24C), C20(H20A,H20B,H20C), C44(H44A,H44B,H44C)
7.c Aromatic/amide H refined with riding coordinates:
 C8(H8), C5(H5), C9(H9), C3(H3), C4(H4), C6(H6), C43(H43), C39(H39), C40(H40),
 C42(H42), C41(H41)
7.d Idealised Me refined as rotating group:
 C35B(H35D,H35E,H35F)
;