The inverse-trans-influence in tetravalent lanthanide and actinide bis(carbene) complexes
Matthew Gregson; Erli Lu; David P. Mills; Floriana Tuna; Eric J. L. McInnes; Christoph Hennig; Andreas C. Scheinost; Jonathan McMaster; William Lewis; Alexander J. Blake; Andrew Kerridge; Stephen T. Liddle; Nature Communications 8 (2017) 14137–; doi:10.1038/ncomms14137

data_1548005
_publ_section_title
;
 The inverse-trans-influence in tetravalent lanthanide and actinide
 bis(carbene) complexes
;
_journal_name_full               'Nature Communications'
_journal_page_first              14137
_journal_paper_doi               10.1038/ncomms14137
_journal_volume                  8
_journal_year                    2017
_chemical_formula_moiety         'C39 H60 N2 P2 Si4 Th'
_chemical_formula_sum            'C39 H60 N2 P2 Si4 Th'
_chemical_formula_weight         963.23
_space_group_crystal_system      orthorhombic
_space_group_IT_number           62
_space_group_name_Hall           '-P 2ac 2n'
_space_group_name_H-M_alt        'P n m a'
_symmetry_space_group_name_Hall  '-P 2ac 2n'
_symmetry_space_group_name_H-M   'P n m a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.2611(16)
_cell_length_b                   19.2083(18)
_cell_length_c                   12.2300(11)
_cell_measurement_reflns_used    14707
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      27.53
_cell_measurement_theta_min      2.24
_cell_volume                     4524.8(7)
_computing_cell_refinement       'Bruker SAINT version 6.36A (Bruker, 2002)'
_computing_data_collection       'Bruker SMART version 5.625 (Bruker, 2001)'
_computing_data_reduction        'Bruker SAINT; SHELXTL (Sheldrick, 2008)'
_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_temperature      90.15
_diffrn_detector_area_resol_mean 8.366
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0848
_diffrn_reflns_av_unetI/netI     0.0436
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            53724
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.662
_diffrn_reflns_theta_min         1.972
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.499
_exptl_absorpt_correction_T_max  0.0684
_exptl_absorpt_correction_T_min  0.0219
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2007/2 (Bruker,2007) was used for absorption correction.
wR2(int) was 0.1370 before and 0.0775 after correction.
The Ratio of minimum to maximum transmission is 0.3202.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.414
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1936
_exptl_crystal_size_max          1.49
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.26
_refine_diff_density_max         7.910
_refine_diff_density_min         -4.112
_refine_diff_density_rms         0.311
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.167
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     368
_refine_ls_number_reflns         5417
_refine_ls_number_restraints     204
_refine_ls_restrained_S_all      1.147
_refine_ls_R_factor_all          0.1123
_refine_ls_R_factor_gt           0.0828
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1081P)^2^+74.5288P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2095
_refine_ls_wR_factor_ref         0.2391
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3996
_reflns_number_total             5417
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ncomms14137-s9.cif
_cod_data_source_block           5Th
_cod_database_code               1548005
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si2-C23 \\sim Si2-C22 \\sim Si2-C24 \\sim Si3-C19 \\sim Si3-C18 \\sim Si3-C20
 with sigma of 0.02
 Si1A-N1 \\sim Si1-N1
 with sigma of 0.02
 Si1A-C15A \\sim Si1-C15 \\sim Si1A-C14A \\sim Si1-C16 \\sim Si1A-C16A \\sim
Si1-C14
 with sigma of 0.02
 C13-C12 \\sim C13A-C12A \\sim C10-C9 \\sim C10A-C9A
 with sigma of 0.02
 C12-C11 \\sim C12A-C11A \\sim C11A-C10A \\sim C11-C10
 with sigma of 0.02
 C9-C8 \\sim C9A-C8A \\sim C13-C8 \\sim C13A-C8A
 with sigma of 0.02
 P1-C8 \\sim P1-C8A
 with sigma of 0.02
3. Restrained planarity
 C8, C9, C10, C11, C12, C13
 with sigma of 0.1
 C8A, C9A, C10A, C11A, C12A, C13A
 with sigma of 0.1
4. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
C8A \\sim C9A \\sim C10A \\sim C11A \\sim C12A \\sim C13A: within 2A with sigma
of 0.04 and sigma for terminal atoms of 0.08
6. Others
 Sof(Si1)=Sof(C8A)=Sof(C9A)=Sof(H9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=
 Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13A)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15A)=Sof(H15D)=Sof(H15E)=Sof(H15F)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 1-FVAR(1)
 Sof(Si1A)=Sof(C8)=Sof(C9)=Sof(H9)=Sof(C10)=Sof(H10)=Sof(C11)=Sof(H11)=
 Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=
 FVAR(1)
 Fixed Sof: Si2(0.5) Si3(0.5) C17(0.5) H17A(0.5) H17B(0.5) C18(0.5) H18A(0.5)
 H18B(0.5) H18C(0.5) C19(0.5) H19A(0.5) H19B(0.5) H19C(0.5) C20(0.5) H20A(0.5)
 H20B(0.5) H20C(0.5) C21(0.5) H21A(0.5) H21B(0.5) C22(0.5) H22A(0.5) H22B(0.5)
 H22C(0.5) C23(0.5) H23A(0.5) H23B(0.5) H23C(0.5) C24(0.5) H24A(0.5) H24B(0.5)
 H24C(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C21(H21A,H21B)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C9A(H9A), C10(H10),
 C10A(H10A), C11(H11), C11A(H11A), C12(H12), C12A(H12A), C13(H13), C13A(H13A)
7.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C14A(H14D,H14E,H14F), C15(H15A,H15B,H15C), C15A(H15D,
 H15E,H15F), C16(H16A,H16B,H16C), C16A(H16D,H16E,H16F), C18(H18A,H18B,H18C),
 C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C)
;
_shelx_res_checksum              82524
_shelx_hkl_checksum              51614
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'