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_1547998
_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 Pr Si4, 2(C10 H20 K0.5 O4), C7 H8'
_chemical_formula_sum            'C89 H124 K N4 O8 P4 Pr Si4'
_chemical_formula_weight         1794.16
_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     iterative
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                71.135(3)
_cell_angle_beta                 64.209(4)
_cell_angle_gamma                65.333(3)
_cell_formula_units_Z            2
_cell_length_a                   16.9776(6)
_cell_length_b                   17.8949(6)
_cell_length_c                   19.1874(7)
_cell_measurement_reflns_used    19042
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.2550
_cell_measurement_theta_min      2.5850
_cell_volume                     4697.6(3)
_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, 2008)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      'N2 gas'
_diffrn_ambient_temperature      120(2)
_diffrn_crystal_treatment        'flash frozen in gaseous N2'
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.6296
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.964
_diffrn_measurement_details
;
  1 omega   82.00  178.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641   30.0000  120.0000 96

  2 omega   68.00  101.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       42.5973  142.0000   90.0000 33

  3 omega   59.00  177.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641   15.0000   60.0000 118

  4 omega   86.00  117.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641 -125.0000  150.0000 31

  5 omega   42.00   90.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641  -30.0000   90.0000 48

  6 omega   43.00  124.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641  -61.0000   30.0000 81

  7 omega   64.00   96.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641  -94.0000  -60.0000 32

  8 omega   45.00   87.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641  -45.0000  -30.0000 42

  9 omega   33.00   87.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641  -45.0000 -120.0000 54

 10 omega   47.00   99.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641  -94.0000 -180.0000 52

 11 omega   42.00  120.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641 -125.0000  -60.0000 78

 12 omega   32.00  108.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641  -94.0000    0.0000 76

 13 omega   37.00   63.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641  -30.0000  150.0000 26

 14 omega   41.00   96.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641  -45.0000  150.0000 55

 15 omega   25.00   51.00   1.0000   12.0000
omega____ theta____ kappa____ phi______ frames
    -      104.4641  -94.0000  -60.0000 26

 16 omega  -27.00   68.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       42.5973  -57.0000   30.0000 95

 17 omega   16.00  111.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -       42.5973   57.0000 -180.0000 95

 18 omega  -38.00   23.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   37.0000  -60.0000 61

 19 omega  -85.00  -36.00   1.0000    3.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  125.0000 -120.0000 49
;
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'GV1000, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_UB_11      -0.0712766000
_diffrn_orient_matrix_UB_12      0.0448749000
_diffrn_orient_matrix_UB_13      -0.0418958000
_diffrn_orient_matrix_UB_21      0.0791813000
_diffrn_orient_matrix_UB_22      0.0004614000
_diffrn_orient_matrix_UB_23      -0.0801224000
_diffrn_orient_matrix_UB_31      0.0019536000
_diffrn_orient_matrix_UB_32      -0.0850787000
_diffrn_orient_matrix_UB_33      -0.0047982000
_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  0.0521
_diffrn_reflns_av_unetI/netI     0.0588
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.964
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            35419
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.964
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.581
_diffrn_reflns_theta_min         2.597
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    5.927
_exptl_absorpt_correction_T_max  0.610
_exptl_absorpt_correction_T_min  0.393
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   .
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       block
_exptl_crystal_F_000             1888
_exptl_crystal_size_max          0.2814
_exptl_crystal_size_mid          0.1938
_exptl_crystal_size_min          0.1139
_refine_diff_density_max         3.239
_refine_diff_density_min         -1.400
_refine_diff_density_rms         0.116
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1077
_refine_ls_number_reflns         18557
_refine_ls_number_restraints     177
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0580
_refine_ls_R_factor_gt           0.0558
_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^)+(0.1109P)^2^+0.1660P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1517
_refine_ls_wR_factor_ref         0.1554
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                17525
_reflns_number_total             18557
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ncomms14137-s4.cif
_cod_data_source_block           2Pr
_cod_database_code               1547998
_chemical_oxdiff_formula         'C82 H116 K1 N4 O8 P4 Pr1 Si4'
_reflns_odcompleteness_completeness 99.86
_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
 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_shelxl_version_number     2014/7
_olex2_exptl_crystal_mounting_method 'in fomblin film on a micromount'
_olex2_submission_special_instructions 'No special instructions were received'