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_1548000
_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 Ce N4 P4 Si4, C5 H12'
_chemical_formula_sum            'C67 H88 Ce N4 P4 Si4'
_chemical_formula_weight         1325.77
_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
_cell_angle_alpha                95.8269(16)
_cell_angle_beta                 101.8739(14)
_cell_angle_gamma                109.0531(17)
_cell_formula_units_Z            2
_cell_length_a                   12.5621(2)
_cell_length_b                   13.9370(3)
_cell_length_c                   21.4408(4)
_cell_measurement_reflns_used    15180
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.0260
_cell_measurement_theta_min      3.6770
_cell_volume                     3414.01(12)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_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      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 0.999
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details
;
  1 omega  -30.00   33.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   38.0000 -150.0000 63

  2 omega  -50.00   -5.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  125.0000 -120.0000 45

  3 omega  -89.00  -18.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  125.0000  -30.0000 71

  4 omega  -83.00  -35.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  125.0000  150.0000 48

  5 omega -110.00  -18.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -38.0000   30.0000 92

  6 omega -110.00  -61.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -38.0000  120.0000 49

  7 omega   47.00   92.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295  -94.0000 -150.0000 45

  8 omega   46.00  109.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295  -94.0000  -90.0000 63

  9 omega   69.00   96.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295  -45.0000   30.0000 27

 10 omega  137.00  178.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295   30.0000  120.0000 41

 11 omega  130.00  170.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295   77.0000   30.0000 40

 12 omega  131.00  175.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295   45.0000  -30.0000 44

 13 omega   75.00  102.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295   77.0000   30.0000 27

 14 omega   32.00  145.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295  -15.0000  -30.0000 113

 15 omega   43.00  109.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295  -94.0000    0.0000 66

 16 omega   37.00   99.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295  -45.0000 -120.0000 62

 17 omega   39.00  121.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295 -125.0000 -150.0000 82

 18 omega   32.00   85.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295  -30.0000  -60.0000 53

 19 omega   39.00   67.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295  -45.0000   90.0000 28

 20 omega   36.00   82.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295  -30.0000  150.0000 46

 21 omega   33.00   97.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      105.3295  -94.0000   90.0000 64
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'GV1000, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0529970000
_diffrn_orient_matrix_UB_12      -0.0228168000
_diffrn_orient_matrix_UB_13      -0.0559587000
_diffrn_orient_matrix_UB_21      0.0610004000
_diffrn_orient_matrix_UB_22      0.1167122000
_diffrn_orient_matrix_UB_23      0.0037985000
_diffrn_orient_matrix_UB_31      0.1070760000
_diffrn_orient_matrix_UB_32      -0.0020355000
_diffrn_orient_matrix_UB_33      0.0493008000
_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  0.0308
_diffrn_reflns_av_unetI/netI     0.0413
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.971
_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       26
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            25253
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.442
_diffrn_reflns_theta_min         3.412
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    7.022
_exptl_absorpt_correction_T_max  0.550
_exptl_absorpt_correction_T_min  0.345
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
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            'dark green'
_exptl_crystal_colour_lustre     .
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.290
_exptl_crystal_description       block
_exptl_crystal_F_000             1384
_exptl_crystal_size_max          0.2448
_exptl_crystal_size_mid          0.1911
_exptl_crystal_size_min          0.1244
_refine_diff_density_max         0.810
_refine_diff_density_min         -0.576
_refine_diff_density_rms         0.067
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     753
_refine_ls_number_reflns         13558
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0306
_refine_ls_R_factor_gt           0.0293
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0465P)^2^+0.1193P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0749
_refine_ls_wR_factor_ref         0.0761
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                13060
_reflns_number_total             13558
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ncomms14137-s6.cif
_cod_data_source_block           3Ce
_cod_original_cell_volume        3414.00(12)
_cod_database_code               1548000
_chemical_oxdiff_formula         'C62 H76 Ce1 N4 P4 Si4'
_reflns_odcompleteness_completeness 99.99
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C66-C65 \\sim C66A-C65A
 with sigma of 0.02
 C67-C66A \\sim C67-C66
 with sigma of 0.02
 C65-C64 \\sim C65A-C64
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 C65, C63, C64, C65A, C66, C66A, C67
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(H64C)=Sof(H64D)=Sof(H67D)=Sof(H67E)=Sof(H67F)=Sof(C66A)=Sof(H66C)=
 Sof(H66D)=Sof(C65A)=Sof(H65C)=Sof(H65D)=1-FVAR(1)
 Sof(H64A)=Sof(H64B)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(C66)=Sof(H66A)=Sof(H66B)=
 Sof(H67A)=Sof(H67B)=Sof(H67C)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C64(H64A,H64B), C64(H64C,H64D), C65(H65A,H65B), C66(H66A,H66B), C66A(H66C,
 H66D), C65A(H65C,H65D)
5.b Me refined with riding coordinates:
 C67(H67A,H67B,H67C), C67(H67D,H67E,H67F)
5.c 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)
5.d 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), C63(H63A,H63B,H63C)
;
_shelx_res_checksum              84751
_shelx_hkl_checksum              69543
_olex2_submission_special_instructions 'No special instructions were received'