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_1548001
_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 U'
_chemical_formula_sum            'C39 H60 N2 P2 Si4 U'
_chemical_formula_weight         969.22
_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                   19.1815(18)
_cell_length_b                   19.1250(19)
_cell_length_c                   12.1896(12)
_cell_measurement_reflns_used    12244
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      75.8980
_cell_measurement_theta_min      3.6234
_cell_volume                     4471.7(8)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
;
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      90(2)
_diffrn_detector_area_resol_mean 10.3613
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.971
_diffrn_measurement_details
;
  1 omega   37.00   64.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       43.6002  -38.0000  -90.0000 27

  2 omega   23.00  112.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       43.6002   57.0000   60.0000 89

  3 omega   25.00  115.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       43.6002   38.0000 -180.0000 90

  4 omega  -23.00   39.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       43.6002  -57.0000 -120.0000 62

  5 omega   36.00   69.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000 -180.0000 33

  6 omega   34.00  101.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -95.0000  -30.0000 67

  7 omega   46.00   73.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -45.0000  -60.0000 27

  8 omega   89.00  158.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   30.0000   60.0000 69

  9 omega   33.00   62.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000   60.0000 29

 10 omega   41.00  116.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -61.0000  120.0000 75

 11 omega   88.00  158.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   30.0000    0.0000 70

 12 omega   39.00   69.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000 -150.0000 30

 13 omega   76.00  106.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   77.0000    0.0000 30

 14 omega  121.00  148.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   77.0000    0.0000 27

 15 omega   33.00   69.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -30.0000 -120.0000 36

 16 omega   40.00   67.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472  -46.0000   83.0000 27

 17 omega  -97.00   -2.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.6002  125.0000   30.0000 95

 18 omega  -77.00   33.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -      -43.6002   19.0000   60.0000 110

 19 omega   18.00  112.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       43.6002   57.0000    0.0000 94

 20 omega   18.00  112.00   1.0000   20.0000
omega____ theta____ kappa____ phi______ frames
    -       43.6002   57.0000  -90.0000 94

 21 omega   66.00  138.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   15.0000 -180.0000 72

 22 omega   66.00  142.00   1.0000   80.0000
omega____ theta____ kappa____ phi______ frames
    -      105.8472   15.0000  -90.0000 76
;
_diffrn_measurement_device_type  'SuperNova, Single source at offset), Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0425196000
_diffrn_orient_matrix_UB_12      0.0512360000
_diffrn_orient_matrix_UB_13      0.0720446000
_diffrn_orient_matrix_UB_21      0.0165501000
_diffrn_orient_matrix_UB_22      -0.0596006000
_diffrn_orient_matrix_UB_23      0.0798394000
_diffrn_orient_matrix_UB_31      0.0659847000
_diffrn_orient_matrix_UB_32      -0.0180823000
_diffrn_orient_matrix_UB_33      -0.0664088000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1033
_diffrn_reflns_av_unetI/netI     0.0526
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            31480
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.500
_diffrn_reflns_theta_max         76.209
_diffrn_reflns_theta_min         4.297
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    12.123
_exptl_absorpt_correction_T_max  0.619
_exptl_absorpt_correction_T_min  0.264
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.19 (release 27-10-2011 CrysAlis171 .NET)
(compiled Oct 27 2011,15:02:11)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.440
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       rod
_exptl_crystal_F_000             1944
_exptl_crystal_size_max          0.2072
_exptl_crystal_size_mid          0.0983
_exptl_crystal_size_min          0.0726
_refine_diff_density_max         12.246
_refine_diff_density_min         -3.245
_refine_diff_density_rms         0.343
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     314
_refine_ls_number_reflns         4684
_refine_ls_number_restraints     348
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0948
_refine_ls_R_factor_gt           0.0857
_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^)+(0.1447P)^2^+85.0511P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2269
_refine_ls_wR_factor_ref         0.2364
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3975
_reflns_number_total             4684
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ncomms14137-s10.cif
_cod_data_source_block           5U
_cod_original_cell_volume        4471.7(7)
_cod_database_code               1548001
_chemical_oxdiff_formula         'C39 H60 N2 P2 Si4 U'
_chemical_oxdiff_usercomment
'UOJCNS #11022 IN FOMBLIN FILM ON MICROMOUNT FOR OJC/STL'
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     67.13
_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
 Si1A-N1 \\sim Si1-N1
 with sigma of 0.02
 Si3-C21 \\sim Si2-C17
 with sigma of 0.02
 Si1-C14 \\sim Si1A-C14A \\sim Si1A-C16A \\sim Si1-C16 \\sim Si1A-C15A \\sim
Si1-C15 \\sim Si2-C19 ~
 Si2-C20 \\sim Si2-C18 \\sim Si3-C24 \\sim Si3-C23 \\sim Si3-C22
 with sigma of 0.02
 C20-C19 \\sim C19-C18 \\sim C18-C20 \\sim C14-C15 \\sim C15-C16 \\sim C16-C14
\\sim C15A-C14A \\sim C14A-
 C16A \\sim C16A-C15A \\sim C23-C24 \\sim C24-C22 \\sim C22-C23
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.7A with sigma of 0.01 and sigma
for terminal atoms of 0.01
5. Others
 Sof(Si1A)=Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15D)=
 Sof(H15E)=Sof(H15F)=Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(1)
 Sof(Si1)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=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)
6.a Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C21(H21A,H21B)
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)
6.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              564
_shelx_hkl_checksum              91934
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'