Uranium(iv) alkyl cations: synthesis, structures, comparison with thorium(iv) analogues, and the influence of arene-coordination on thermal stability and ethylene polymerization activity
Andreychuk, Nicholas R.; Vidjayacoumar, Balamurugan; Price, Jeffrey S.; Kervazo, Sophie; Peeples, Craig A.; Emslie, David J. H.; Vallet, Valérie; Gomes, André S. P.; Réal, Florent; Schreckenbach, Georg; Ayers, Paul W.; Vargas-Baca, Ignacio; Jenkins, Hilary A.; Britten, James F.; Chemical Science  (2022) –; doi:10.1039/D2SC04302E

data_1567952
_publ_section_title
;
 Uranium(iv) alkyl cations: synthesis, structures, comparison with
 thorium(iv) analogues, and the influence of arene-coordination on thermal
 stability and ethylene polymerization activity
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC04302E
_journal_year                    2022
_chemical_formula_moiety         'C57 H78 F N2 O Si U, B C24 F20, C6 H5 F'
_chemical_formula_sum            'C87 H83 B F22 N2 O Si U'
_chemical_formula_weight         1867.48
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_Hall           'P 2c -2ac'
_space_group_name_H-M_alt        'P c a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2022-05-18
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-08-03 deposited with the CCDC.	2022-11-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   26.5251(18)
_cell_length_b                   15.7375(11)
_cell_length_c                   18.8824(13)
_cell_measurement_reflns_used    9994
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.25
_cell_measurement_theta_min      2.16
_cell_volume                     7882.2(9)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0490
_diffrn_reflns_av_unetI/netI     0.0641
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            120436
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.839
_diffrn_reflns_theta_min         1.505
_exptl_absorpt_coefficient_mu    2.176
_exptl_absorpt_correction_T_max  0.8492
_exptl_absorpt_correction_T_min  0.6622
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details   SADABS
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.574
_exptl_crystal_description       plate
_exptl_crystal_F_000             3744
_exptl_crystal_size_max          0.316
_exptl_crystal_size_mid          0.138
_exptl_crystal_size_min          0.098
_refine_diff_density_max         1.950
_refine_diff_density_min         -0.745
_refine_diff_density_rms         0.094
_refine_ls_abs_structure_details
;
 Flack x determined using 8341 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0008(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.000
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1055
_refine_ls_number_reflns         24641
_refine_ls_number_restraints     93
_refine_ls_restrained_S_all      1.000
_refine_ls_R_factor_all          0.0485
_refine_ls_R_factor_gt           0.0301
_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^)+(0.0103P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0620
_refine_ls_wR_factor_ref         0.0669
_reflns_Friedel_coverage         0.938
_reflns_Friedel_fraction_full    0.988
_reflns_Friedel_fraction_max     0.991
_reflns_number_gt                19593
_reflns_number_total             24641
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc04302e2.cif
_cod_data_source_block           XA2_U_R_PhF_cation
_cod_database_code               1567952
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.815
_shelx_estimated_absorpt_t_min   0.546
_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
 C58-F2 = C61A-F2A
 1.36 with sigma of 0.003
 C58-C59 \\sim C59-C60 \\sim C60-C61 \\sim C61-C62 \\sim C62-C63 \\sim C63-C58
\\sim C58A-C59A \\sim C59A-
 C60A \\sim C60A-C61A \\sim C61A-C62A \\sim C62A-C63A \\sim C63A-C58A
 with sigma of 0.003
 C63-C59 \\sim C62-C60 \\sim C63A-C59A \\sim C62A-C60A
 with sigma of 0.003
 F2-C63 \\sim F2-C59 \\sim F2A-C62A \\sim F2A-C60A
 with sigma of 0.003
3. Uiso/Uaniso restraints and constraints
Uiso(C63) = Uiso(C63A)
Uiso(C61) = Uiso(C61A)
Uiso(C60) = Uiso(C60A)
Uiso(C62) = Uiso(C62A)
Uiso(C58) = Uiso(C58A)
Uiso(C59) = Uiso(C59A)
Uanis(F2A) = Uanis(F2)
4. Same fragment restrains
{C58, C59, C60, C61, C62, C63} sigma for 1-2: 0.002, 1-3: 0.004
as in
{C58A, C59A, C60A, C61A, C62A, C63A}
5. Others
 Sof(F2A)=Sof(C58A)=Sof(H58A)=Sof(C59A)=Sof(H59A)=Sof(C60A)=Sof(H60A)=
 Sof(C61A)=Sof(C62A)=Sof(H62A)=Sof(C63A)=Sof(H63A)=1-FVAR(1)
 Sof(F2)=Sof(C58)=Sof(C59)=Sof(H59)=Sof(C60)=Sof(H60)=Sof(C61)=Sof(H61)=
 Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C30(H30), C33(H33), C42(H42), C45(H45)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C6(H6), C8(H8), C26(H26), C27(H27), C28(H28), C38(H38),
 C39(H39), C40(H40), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C59(H59),
  C60(H60), C61(H61), C62(H62), C63(H63), C58A(H58A), C59A(H59A), C60A(H60A),
 C62A(H62A), C63A(H63A)
6.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,H17B,H17C), C18(H18A,H18B,
 H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,
 H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,
 H51B,H51C)
;
_shelx_res_checksum              1748
_olex2_submission_special_instructions 'No special instructions were received'