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_1552028
_publ_section_title
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 The role of uranium-arene bonding in H2O reduction catalysis
;
_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         'C60 H78 N3 O4 U, C4 H12 Si, 1.5(C4 H10 O2)'
_chemical_formula_sum            'C70 H105 N3 O7 Si U'
_chemical_formula_weight         1366.68
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_cell_angle_alpha                90
_cell_angle_beta                 97.314(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.360(2)
_cell_length_b                   25.522(5)
_cell_length_c                   22.856(4)
_cell_measurement_reflns_used    9909
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      2.40
_cell_measurement_theta_min      28.53
_cell_volume                     6573(2)
_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 0.997
_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 high brilliance micro-focus tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0482
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            264464
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.754
_diffrn_reflns_theta_min         1.201
_exptl_absorpt_coefficient_mu    2.542
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6889
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0534 before and 0.0502 after correction.
The Ratio of minimum to maximum transmission is 0.9237.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.381
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2832
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.101
_refine_diff_density_min         -1.311
_refine_diff_density_rms         0.088
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     783
_refine_ls_number_reflns         17034
_refine_ls_number_restraints     71
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0343
_refine_ls_R_factor_gt           0.0267
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0301P)^2^+10.6108P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0655
_refine_ls_wR_factor_ref         0.0689
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                14765
_reflns_number_total             17034
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2899-s5.cif
_cod_data_source_block           dh1604
_cod_database_code               1552028
_shelx_estimated_absorpt_t_max   0.717
_shelx_estimated_absorpt_t_min   0.630
_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
 C106-O105 \\sim C101-O102
 with sigma of 0.02
 C106-O105 \\sim C111-O102
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C201 \\sim O202 \\sim C203 \\sim C204 \\sim O205 \\sim C206: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C101 \\sim C111: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(C101) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(O205) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
4. Same fragment restrains
{C111, O102, C103, C104, O105, C106} sigma for 1-2: 0.02, 1-3: 0.04
as
{C201, O202, C203, C204, O205, C206}
5. Others
 Sof(C111)=Sof(H11A)=Sof(H11B)=Sof(H11C)=1-FVAR(1)
 Sof(C101)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(1)
 Fixed Sof: C201(0.5) H20C(0.5) H20D(0.5) H20E(0.5) O202(0.5) C203(0.5)
 H20F(0.5) H20G(0.5) C204(0.5) H20H(0.5) H20I(0.5) O205(0.5) C206(0.5)
 H20J(0.5) H20K(0.5) H20L(0.5)
6.a Ternary CH refined with riding coordinates:
 C15(H15), C16(H16), C17(H17), C33(H33), C34(H34), C35(H35), C51(H51),
 C52(H52), C53(H53)
6.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B),
 C22(H22A,H22B), C23(H23A,H23B), C25(H25A,H25B), C36(H36A,H36B), C37(H37A,H37B),
  C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C43(H43A,
 H43B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,H57B),
 C58(H58A,H58B), C59(H59A,H59B), C103(H10D,H10E), C104(H10F,H10G), C203(H20F,
 H20G), C204(H20H,H20I)
6.c Me refined with riding coordinates:
 C64(H64A,H64B,H64C), C101(H10A,H10B,H10C), C106(H10H,H10I,H10J), C201(H20C,
 H20D,H20E), C206(H20J,H20K,H20L)
6.d Aromatic/amide H refined with riding coordinates:
 C11(H11), C13(H13), C29(H29), C31(H31), C47(H47), C49(H49)
6.e Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C42(H42A,H42B,H42C), C60(H60A,H60B,H60C), C61(H61A,H61B,
 H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C111(H11A,H11B,H11C)
;
_shelx_res_checksum              62191
_shelx_hkl_checksum              36103