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_1548004
_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         'C62 H76 N4 P4 Si4 Th, 0.5(C7 H8)'
_chemical_formula_sum            'C65.5 H80 N4 P4 Si4 Th'
_chemical_formula_weight         1391.61
_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
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                95.067(2)
_cell_angle_beta                 92.9824(18)
_cell_angle_gamma                110.180(3)
_cell_formula_units_Z            2
_cell_length_a                   12.9528(3)
_cell_length_b                   14.0462(5)
_cell_length_c                   19.2134(3)
_cell_measurement_reflns_used    14722
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.6120
_cell_measurement_theta_min      3.6400
_cell_volume                     3255.49(16)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.6296
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_details
;
  1 omega  -35.00   43.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       39.7650  -38.0000   60.0000 78

  2 omega   14.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       39.7650   50.0000    7.0000 95

  3 omega  100.00  178.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214   45.0000  -90.0000 78

  4 omega   88.00  120.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214 -125.0000    0.0000 32

  5 omega   69.00  115.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214 -125.0000  120.0000 46

  6 omega   38.00   91.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214  -30.0000  120.0000 53

  7 omega   38.00  109.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214  -94.0000  150.0000 71

  8 omega   32.00  158.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214  -15.0000   90.0000 126

  9 omega   54.00  136.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214  -77.0000  -60.0000 82

 10 omega   48.00  103.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214  -94.0000 -150.0000 55

 11 omega   38.00   91.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214  -30.0000 -120.0000 53

 12 omega   33.00  107.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214  -61.0000 -150.0000 74

 13 omega   30.00   89.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214  -30.0000  -60.0000 59

 14 omega   30.00   82.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214  -30.0000    0.0000 52

 15 omega   35.00   76.00   1.0000   16.0000
omega____ theta____ kappa____ phi______ frames
    -      105.4214 -125.0000  150.0000 41

 16 omega  -29.00   65.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -       39.7650  -57.0000 -150.0000 94

 17 omega  -80.00  -37.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.7650  -38.0000  120.0000 43

 18 omega  -96.00  -53.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      -39.7650  125.0000   60.0000 43
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'GV1000, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0496257000
_diffrn_orient_matrix_UB_12      -0.0825126000
_diffrn_orient_matrix_UB_13      -0.0206381000
_diffrn_orient_matrix_UB_21      0.1075050000
_diffrn_orient_matrix_UB_22      0.0631822000
_diffrn_orient_matrix_UB_23      0.0454425000
_diffrn_orient_matrix_UB_31      -0.0464996000
_diffrn_orient_matrix_UB_32      -0.0550836000
_diffrn_orient_matrix_UB_33      0.0635373000
_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  0.0226
_diffrn_reflns_av_unetI/netI     0.0271
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            23373
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.696
_diffrn_reflns_theta_min         4.007
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    9.340
_exptl_absorpt_correction_T_max  0.355
_exptl_absorpt_correction_T_min  0.135
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   .
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_description       plank
_exptl_crystal_F_000             1414
_exptl_crystal_size_max          0.2106
_exptl_crystal_size_mid          0.1311
_exptl_crystal_size_min          0.0869
_refine_diff_density_max         1.707
_refine_diff_density_min         -1.375
_refine_diff_density_rms         0.080
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     751
_refine_ls_number_reflns         12741
_refine_ls_number_restraints     103
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0236
_refine_ls_R_factor_gt           0.0233
_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^)+(0.0383P)^2^+1.9838P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0609
_refine_ls_wR_factor_ref         0.0611
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                12556
_reflns_number_total             12741
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ncomms14137-s8.cif
_cod_data_source_block           3Th
_cod_original_formula_sum        'C65.50 H80 N4 P4 Si4 Th'
_cod_database_code               1548004
_chemical_oxdiff_formula         'C62 H76 N4 P4 Si4 Th'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C65-C64 \\sim C69-C64 \\sim C69-C68 \\sim C68-C67 \\sim C67-C66 \\sim C66-C65
 with sigma of 0.02
 C65-C63 \\sim C63-C69
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C63, C64, C65, C66, C67, C68, C69
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C63(0.5) H63A(0.5) H63B(0.5) H63C(0.5) C64(0.5) C65(0.5) H65(0.5)
 C66(0.5) H66(0.5) C67(0.5) H67(0.5) C68(0.5) H68(0.5) C69(0.5) H69(0.5)
6.a Me refined with riding coordinates:
 C63(H63A,H63B,H63C)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24), C25(H25),
  C26(H26), C27(H27), C28(H28), C34(H34), C35(H35), C36(H36), C37(H37),
 C38(H38), C40(H40), C41(H41), C42(H42), C43(H43), C44(H44), C49(H49), C50(H50),
  C51(H51), C52(H52), C53(H53), C55(H55), C56(H56), C57(H57), C58(H58),
 C59(H59), C65(H65), C66(H66), C67(H67), C68(H68), C69(H69)
6.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C47(H47A,H47B,H47C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C),
 C62(H62A,H62B,H62C)
;
_shelx_res_checksum              32079
_shelx_hkl_checksum              34683
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_special_instructions 'No special instructions were received'