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_1547997
_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, 2(C10 H20 K0.5 O4), 1(C7 H8)'
_chemical_formula_sum            'C89 H124 Ce K N4 O8 P4 Si4'
_chemical_formula_weight         1793.37
_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                71.281(3)
_cell_angle_beta                 64.086(3)
_cell_angle_gamma                65.421(3)
_cell_formula_units_Z            2
_cell_length_a                   16.9671(6)
_cell_length_b                   17.9463(5)
_cell_length_c                   19.1550(6)
_cell_measurement_reflns_used    20166
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.3120
_cell_measurement_theta_min      3.1750
_cell_volume                     4701.3(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
;
_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_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.3613
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.972
_diffrn_measurement_details
;
  1 omega   72.00  178.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322   15.0000   60.0000 106

  2 omega  118.00  168.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  125.0000  150.0000 50

  3 omega   75.00  150.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322   77.0000  120.0000 75

  4 omega   60.00   86.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  -30.0000  -30.0000 26

  5 omega   42.00   98.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  -45.0000  -90.0000 56

  6 omega   70.00   98.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  -95.0000 -180.0000 28

  7 omega   48.00   90.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  -30.0000 -150.0000 42

  8 omega   27.00   95.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  -95.0000  -90.0000 68

  9 omega   39.00   67.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  -30.0000   30.0000 28

 10 omega   33.00  138.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  -77.0000   60.0000 105

 11 omega   86.00  121.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322 -125.0000  120.0000 35

 12 omega   31.00   84.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  -30.0000  120.0000 53

 13 omega   25.00  104.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  -95.0000  -30.0000 79

 14 omega   35.00  119.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322 -125.0000  -90.0000 84

 15 omega  -47.00   28.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   38.0000    0.0000 75

 16 omega  -64.00   32.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   54.0000 -151.0000 96

 17 omega   94.00  133.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      106.1322  125.0000 -120.0000 39

 18 omega  -93.00   -9.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  125.0000 -120.0000 84

 19 omega -108.00  -20.00   1.0000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -57.0000   60.0000 88
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'SuperNova-Duo, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0390674000
_diffrn_orient_matrix_UB_12      0.0727340000
_diffrn_orient_matrix_UB_13      -0.0428144000
_diffrn_orient_matrix_UB_21      0.0729465000
_diffrn_orient_matrix_UB_22      -0.0407269000
_diffrn_orient_matrix_UB_23      0.0400808000
_diffrn_orient_matrix_UB_31      0.0673444000
_diffrn_orient_matrix_UB_32      -0.0471949000
_diffrn_orient_matrix_UB_33      -0.0692398000
_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_radiation_wavelength_determination fundamental
_diffrn_reflns_av_R_equivalents  0.0410
_diffrn_reflns_av_unetI/netI     0.0469
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            37567
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.439
_diffrn_reflns_theta_min         3.060
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           0.8
_diffrn_source_power             0.04
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    5.688
_exptl_absorpt_correction_T_max  0.659
_exptl_absorpt_correction_T_min  0.433
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.34 (release 22-05-2014 CrysAlis171 .NET)
(compiled May 22 2014,16:03:01)
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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   .
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.267
_exptl_crystal_description       block
_exptl_crystal_F_000             1886
_exptl_crystal_size_max          0.2035
_exptl_crystal_size_mid          0.1491
_exptl_crystal_size_min          0.1107
_refine_diff_density_max         0.925
_refine_diff_density_min         -0.869
_refine_diff_density_rms         0.083
_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     1077
_refine_ls_number_reflns         18660
_refine_ls_number_restraints     177
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0432
_refine_ls_R_factor_gt           0.0415
_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^)+(0.0772P)^2^+0.4075P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1083
_refine_ls_wR_factor_ref         0.1109
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                17879
_reflns_number_total             18660
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ncomms14137-s3.cif
_cod_data_source_block           2Ce
_cod_original_cell_volume        4701.2(3)
_cod_database_code               1547997
_chemical_oxdiff_formula         'C82 H116 Ce1 K1 N4 O8 P4 Si4'
_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, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C80A-C79A \\sim C80-C79 \\sim C82-C81 \\sim C82A-C81A \\sim C72-C71 \\sim
C70-C69
 with sigma of 0.01
 C81-C80 \\sim C81A-C80A \\sim C71-C70
 with sigma of 0.01
 K2-O8 \\sim K1-O4 \\sim K2-O8A
 with sigma of 0.01
 O8A-C82A \\sim O8-C82 \\sim O8A-C79A \\sim O8-C79 \\sim O4-C72 \\sim O4-C69
 with sigma of 0.01
 C79A-C81A \\sim C80A-C82A \\sim C81-C79 \\sim C80-C82
 with sigma of 0.01
 C84A-C83A \\sim C84-C83
 with sigma of 0.01
 C85-C84 \\sim C85A-C84A \\sim C89-C84 \\sim C89A-C84A
 with sigma of 0.01
 C86A-C85A \\sim C86-C85 \\sim C89-C88 \\sim C89A-C88A
 with sigma of 0.01
 C87A-C86A \\sim C87-C86 \\sim C88A-C87A \\sim C88-C87
 with sigma of 0.01
 C83-C85 \\sim C83-C89
 with sigma of 0.02
 C83A-C89A \\sim C83A-C85A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C86 \\sim C85 \\sim C87 \\sim C89 \\sim C88 \\sim C84 \\sim C83: within 1.7A
with sigma of 0.02 and sigma for terminal atoms of 0.04
4. Rigid body (RIGU) restrains
 C86, C85, C87, C89, C88, C84, C83, C83A, C84A, C89A, C88A, C87A, C86A, C85
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(O8)=Sof(C82)=Sof(H82C)=Sof(H82D)=Sof(C79)=Sof(H79C)=Sof(H79D)=Sof(C80)=
 Sof(H80C)=Sof(H80D)=Sof(C81)=Sof(H81C)=Sof(H81D)=1-FVAR(1)
 Sof(C79A)=Sof(H79A)=Sof(H79B)=Sof(C80A)=Sof(H80A)=Sof(H80B)=Sof(C81A)=
 Sof(H81A)=Sof(H81B)=Sof(C82A)=Sof(H82A)=Sof(H82B)=Sof(O8A)=FVAR(1)
 Sof(C83A)=Sof(H83D)=Sof(H83E)=Sof(H83F)=Sof(C84A)=Sof(C85A)=Sof(H85A)=
 Sof(C86A)=Sof(H86A)=Sof(C87A)=Sof(H87A)=Sof(C88A)=Sof(H88A)=Sof(C89A)=
 Sof(H89A)=1-FVAR(2)
 Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=Sof(C84)=Sof(C85)=Sof(H85)=Sof(C86)=
 Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(H88)=Sof(C89)=Sof(H89)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C73(H73A,H73B), C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B), C77(H77A,
 H77B), C78(H78A,H78B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,H65B),
 C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C79A(H79A,H79B), C80A(H80A,
 H80B), C81A(H81A,H81B), C82A(H82A,H82B), C82(H82C,H82D), C79(H79C,H79D),
 C80(H80C,H80D), C81(H81C,H81D), C69(H69A,H69B), C72(H72A,H72B), C71(H71A,H71B),
  C70(H70A,H70B)
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), C85(H85), C86(H86), C87(H87), C88(H88), C89(H89), C85A(H85A),
 C86A(H86A), C87A(H87A), C88A(H88A), C89A(H89A)
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), C83(H83A,H83B,H83C), C83A(H83D,H83E,H83F)
;
_shelx_res_checksum              47075
_shelx_hkl_checksum              22092
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_special_instructions 'No special instructions were received'