The role of uranium-arene bonding in H2O reduction catalysis
Dominik P. Halter; Frank W. Heinemann; Laurent Maron; Karsten Meyer; Nature Chemistry 10 (2018) 259–267; doi:10.1038/nchem.2899

data_1552025
_publ_section_title
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 The role of uranium-arene bonding in H2O reduction catalysis
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_journal_name_full               'Nature Chemistry'
_journal_page_first              259
_journal_page_last               267
_journal_paper_doi               10.1038/nchem.2899
_journal_volume                  10
_journal_year                    2018
_chemical_formula_moiety         'C63 H75 O4 U1, C18 H36 K1 N2 O6, C5 H12'
_chemical_formula_sum            'C86 H123 K N2 O10 U'
_chemical_formula_weight         1621.99
_space_group_crystal_system      cubic
_space_group_IT_number           198
_space_group_name_Hall           'P 2ac 2ab 3'
_space_group_name_H-M_alt        'P 21 3'
_atom_sites_solution_hydrogens   mixed
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.8738(16)
_cell_length_b                   19.8738(16)
_cell_length_c                   19.8738(16)
_cell_measurement_reflns_used    9982
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.67
_cell_measurement_theta_min      2.29
_cell_volume                     7849.5(11)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'SHELXTL 6.12 (Bruker AXS, 2002)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2008)'
_computing_structure_solution    'SHELXTL 6.12 (Bruker AXS, 2002)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 83.33
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker Kappa APEX II CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  'Quazar focussing montel optics'
_diffrn_radiation_source         'ImuS micro-focus tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0588
_diffrn_reflns_av_unetI/netI     0.0447
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            50661
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.838
_diffrn_reflns_theta_min         1.449
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.180
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6869
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0876 before and 0.0787 after correction.
The Ratio of minimum to maximum transmission is 0.9213.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.373
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             3376
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.972
_refine_diff_density_min         -0.805
_refine_diff_density_rms         0.077
_refine_ls_abs_structure_details
;
 Flack x determined using 2471 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(4)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     325
_refine_ls_number_reflns         6221
_refine_ls_number_restraints     33
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0389
_refine_ls_R_factor_gt           0.0336
_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^)+(0.0241P)^2^+9.0306P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0721
_refine_ls_wR_factor_ref         0.0737
_reflns_Friedel_coverage         0.841
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                5765
_reflns_number_total             6221
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2899-s2.cif
_cod_data_source_block           dh1601
_cod_original_cell_volume        7849.5(19)
_cod_database_code               1552025
_shelx_estimated_absorpt_t_max   0.862
_shelx_estimated_absorpt_t_min   0.795
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H10D,H10E} of C102, {H23A,H23B} of C23, {H24A,H24B} of
  C24, {H25A,H25B} of C25, {H26A,H26B} of C26, {H27A,H27B} of C27, {H22A,H22B}
  of C22, {H4A,H4B} of C4, {H15A,H15B} of C15, {H16A,H16B} of C16, {H17A,H17B}
  of C17, {H18A,H18B} of C18, {H19A,H19B} of C19, {H20A,H20B} of C20
 At 1.5 times of:
  All C(H,H,H) groups, {H10F,H10G} of C103
2. Restrained distances
 C101-C102 = C102-C103
 1.54 with sigma of 0.02
 C101-C103
 2.6 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C101 \\sim C102 \\sim C103: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C101) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C103) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(O1A)=1-FVAR(1)
 Sof(O1)=FVAR(1)
 Fixed Sof: C101(0.66667) H10A(0.66667) H10B(0.66667) H10C(0.66667)
 C102(0.66667) H10D(0.66667) H10E(0.66667) C103(0.33333) H10F(0.33333)
 H10G(0.33333)
5.a Riding coordinates:
 C102(H10D,H10E), C103(H10F,H10G)
5.b Ternary CH refined with riding coordinates:
 C12(H12), C13(H13), C14(H14)
5.c Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B),
 C19(H19A,H19B), C20(H20A,H20B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B),
  C25(H25A,H25B), C26(H26A,H26B), C27(H27A,H27B)
5.d Me refined with riding coordinates:
 C101(H10A,H10B,H10C)
5.e Aromatic/amide H refined with riding coordinates:
 C8(H8), C10(H10)
5.f Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C21(H21A,H21B,H21C)
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_shelx_res_checksum              43170
_shelx_hkl_checksum              24500