Uranium(iv) terminal hydrosulfido and sulfido complexes: insights into the nature of the uranium‒sulfur bond
Rosenzweig, Michael W.; Scheurer, Andreas; Lamsfus, Carlos A.; Heinemann, Frank W.; Maron, Laurent; Andrez, Julie; Mazzanti, Marinella; Meyer, Karsten; Chem. Sci. 7 (2016) 5857–; doi:10.1039/C6SC00677A

data_1543282
_publ_section_title
;
 Uranium(iv) terminal hydrosulfido and sulfido complexes: insights into
 the nature of the uranium--sulfur bond
;
_journal_issue                   9
_journal_name_full               'Chem. Sci.'
_journal_page_first              5857
_journal_paper_doi               10.1039/C6SC00677A
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety
'C80 H102 K N3 O9 S U, 0.62(C6 H6), 0.38(C4 H10 O)'
_chemical_formula_sum            'C85.23 H109.53 K N3 O9.38 S U'
_chemical_formula_weight         1635.38
_chemical_name_systematic
;
 ? 
;
_chemical_properties_physical
'Air-sensitive, Moisture-sensitive, Oxygen-sensitive'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-10-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-02-11 deposited with the CCDC.
2016-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.271(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.017(2)
_cell_length_b                   12.8557(12)
_cell_length_c                   28.173(3)
_cell_measurement_reflns_used    9175
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      27.43
_cell_measurement_theta_min      2.26
_cell_volume                     7465.2(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 0.999
_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  0.0632
_diffrn_reflns_av_unetI/netI     0.0299
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            233649
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.942
_diffrn_reflns_theta_min         0.988
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.320
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6722
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0598 before and 0.0521 after correction.
The Ratio of minimum to maximum transmission is 0.9016.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            orange
_exptl_crystal_density_diffrn    1.455
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             3376
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: diethyl ether/benzene'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.302
_refine_diff_density_min         -0.973
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.286
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     949
_refine_ls_number_reflns         17883
_refine_ls_number_restraints     60
_refine_ls_restrained_S_all      1.287
_refine_ls_R_factor_all          0.0561
_refine_ls_R_factor_gt           0.0434
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0135P)^2^+19.9650P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0829
_refine_ls_wR_factor_ref         0.0867
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15242
_reflns_number_total             17883
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc00677a2.cif
_cod_data_source_block           mr1520
_cod_depositor_comments
'Adding full bibliography for 1543281--1543283.cif.'
_cod_original_cell_volume        7465.1(12)
_cod_database_code               1543282
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.836
_shelx_estimated_absorpt_t_min   0.629
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H11A,H11B,H11C} of C111, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H,H,H,H) groups, {H42A,H42B,H42C} of C42, {H24A,H24B,H24C} of C24,
   {H11H,H11I,H11J} of C115
2. Uiso/Uaniso restraints and constraints
C101 \\sim C102 \\sim C103 \\sim C104 \\sim C105 \\sim C106: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01
C111 \\sim C112 \\sim O113 \\sim C114 \\sim C115: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01
3. Others
 Sof(H60D)=Sof(H60E)=Sof(H60F)=Sof(C111)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C112)=Sof(H11D)=Sof(H11E)=Sof(O113)=Sof(C114)=Sof(H11F)=Sof(H11G)=
 Sof(C115)=Sof(H11H)=Sof(H11I)=Sof(H11J)=1-FVAR(1)
 Sof(H60A)=Sof(H60B)=Sof(H60C)=Sof(C101)=Sof(H101)=Sof(C102)=Sof(H102)=
 Sof(C103)=Sof(H103)=Sof(C104)=Sof(H104)=Sof(C105)=Sof(H105)=Sof(C106)=
 Sof(H106)=FVAR(1)
4.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)
4.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), C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B),
  C64(H64A,H64B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,
 H74B), C112(H11D,H11E), C114(H11F,H11G)
4.c Aromatic/amide H refined with riding coordinates:
 C11(H11), C13(H13), C29(H29), C31(H31), C47(H47), C49(H49), C66(H66),
 C67(H67), C68(H68), C69(H69), C76(H76), C77(H77), C78(H78), C79(H79),
 C101(H101), C102(H102), C103(H103), C104(H104), C105(H105), C106(H106)
4.d Fitted hexagon refined as free rotating group:
 C101(C102,C103,C104,C105,C106)
4.e Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C42(H42A,H42B,H42C), C60(H60A,H60B,H60C), C60(H60D,H60E,
 H60F), C111(H11A,H11B,H11C), C115(H11H,H11I,H11J)
;
_shelx_res_checksum              57487
_olex2_submission_special_instructions 'No special instructions were received'