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_1552027
_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         'C67 H83 O5 U, 3(C4 H8 O1)'
_chemical_formula_sum            'C79 H107 O8 U'
_chemical_formula_weight         1422.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_cell_angle_alpha                90
_cell_angle_beta                 124.439(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   41.761(2)
_cell_length_b                   15.8422(6)
_cell_length_c                   24.5005(15)
_cell_measurement_reflns_used    9936
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.53
_cell_measurement_theta_min      2.19
_cell_volume                     13368.2(13)
_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 0.995
_diffrn_measurement_device_type  'Bruker Smart APEX II CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  'Triumph curved graphite'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0406
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       56
_diffrn_reflns_limit_h_min       -56
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            270266
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.715
_diffrn_reflns_theta_min         1.182
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.486
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6525
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0658 before and 0.0463 after correction.
The Ratio of minimum to maximum transmission is 0.8749.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.414
_exptl_crystal_description       prism
_exptl_crystal_F_000             5896
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_refine_diff_density_max         1.789
_refine_diff_density_min         -1.085
_refine_diff_density_rms         0.094
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     901
_refine_ls_number_reflns         17231
_refine_ls_number_restraints     368
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0373
_refine_ls_R_factor_gt           0.0260
_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^)+(0.0299P)^2^+41.9018P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0608
_refine_ls_wR_factor_ref         0.0655
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                14593
_reflns_number_total             17231
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            nchem.2899-s3.cif
_cod_data_source_block           dh1605
_cod_original_cell_volume        13368.2(12)
_cod_database_code               1552027
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
O100 \\sim C101 \\sim C102 \\sim C103 \\sim C104 \\sim O110 \\sim C111 \\sim
C112 \\sim C113 \\sim C114: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
O200 \\sim C201 \\sim C202 \\sim C203 \\sim C204 \\sim C214: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01
O300 \\sim C301 \\sim C302 \\sim C303 \\sim C304 \\sim O310 \\sim C311 \\sim
C312 \\sim C313 \\sim C314: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
3. Same fragment restrains
{O100, C101, C102, C103, C104} sigma for 1-2: 0.02, 1-3: 0.04
as
{O110, C111, C112, C113, C114}
{O300, C301, C302, C303, C304} sigma for 1-2: 0.02, 1-3: 0.04
as
{O310, C311, C312, C313, C314}
4. Others
 Sof(O110)=Sof(C111)=Sof(H11A)=Sof(H11B)=Sof(C112)=Sof(H11C)=Sof(H11D)=
 Sof(C113)=Sof(H11E)=Sof(H11F)=Sof(C114)=Sof(H11G)=Sof(H11H)=1-FVAR(1)
 Sof(O100)=Sof(C101)=Sof(H10C)=Sof(H10D)=Sof(C102)=Sof(H10E)=Sof(H10F)=
 Sof(C103)=Sof(H10G)=Sof(H10H)=Sof(C104)=Sof(H10I)=Sof(H10J)=FVAR(1)
 Sof(H20G)=Sof(H20H)=Sof(C214)=Sof(H21C)=Sof(H21D)=1-FVAR(2)
 Sof(H20E)=Sof(H20F)=Sof(C204)=Sof(H20I)=Sof(H20J)=FVAR(2)
 Sof(O310)=Sof(C311)=Sof(H31A)=Sof(H31B)=Sof(C312)=Sof(H31C)=Sof(H31D)=
 Sof(C313)=Sof(H31E)=Sof(H31F)=Sof(C314)=Sof(H31G)=Sof(H31H)=1-FVAR(3)
 Sof(O300)=Sof(C301)=Sof(H30A)=Sof(H30B)=Sof(C302)=Sof(H30C)=Sof(H30D)=
 Sof(C303)=Sof(H30E)=Sof(H30F)=Sof(C304)=Sof(H30G)=Sof(H30H)=FVAR(3)
5.a Ternary CH refined with riding coordinates:
 C18(H18), C19(H19), C20(H20), C36(H36), C37(H37), C38(H38), C59(H59),
 C60(H60), C62(H62)
5.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,
 H24B), C25(H25A,H25B), C26(H26A,H26B), C28(H28A,H28B), C39(H39A,H39B),
 C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B),
  C46(H46A,H46B), C54(H54A,H54B), C55(H55A,H55B), C56(H56A,H56B), C57(H57A,
 H57B), C58(H58A,H58B), C61(H61A,H61B), C64(H64A,H64B), C65(H65A,H65B),
 C66(H66A,H66B), C67(H67A,H67B), C101(H10C,H10D), C102(H10E,H10F), C103(H10G,
 H10H), C104(H10I,H10J), C111(H11A,H11B), C112(H11C,H11D), C113(H11E,H11F),
 C114(H11G,H11H), C201(H20A,H20B), C202(H20C,H20D), C203(H20E,H20F), C203(H20G,
 H20H), C204(H20I,H20J), C214(H21C,H21D), C301(H30A,H30B), C302(H30C,H30D),
 C303(H30E,H30F), C304(H30G,H30H), C311(H31A,H31B), C312(H31C,H31D), C313(H31E,
 H31F), C314(H31G,H31H)
5.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C16(H16), C32(H32), C34(H34), C50(H50), C52(H52)
5.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C27(H27A,H27B,H27C),
 C45(H45A,H45B,H45C), C63(H63A,H63B,H63C)
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