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_1543281
_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_absolute_configuration ad
_chemical_formula_moiety         '2(C60 H79 N3 O3 S1 U1), 6.5(C H2 Cl2)'
_chemical_formula_sum            'C126.5 H171 Cl13 N6 O6 S2 U2'
_chemical_formula_weight         2872.71
_chemical_properties_physical
'Air-sensitive, Moisture-sensitive, Oxygen-sensitive'
_space_group_crystal_system      hexagonal
_space_group_IT_number           173
_space_group_name_Hall           'P 6c'
_space_group_name_H-M_alt        'P 63'
_symmetry_space_group_name_Hall  'P 6c'
_symmetry_space_group_name_H-M   'P 63'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2015-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2016-02-11 deposited with the CCDC.
2016-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            2
_cell_length_a                   20.258(5)
_cell_length_b                   20.258(5)
_cell_length_c                   18.302(4)
_cell_measurement_reflns_used    9633
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.16
_cell_measurement_theta_min      2.23
_cell_volume                     6505(3)
_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(2)
_diffrn_detector_area_resol_mean 83.33
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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  0.0613
_diffrn_reflns_av_unetI/netI     0.0364
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            165921
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.741
_diffrn_reflns_theta_min         1.161
_diffrn_source                   'fine-focus sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.839
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6466
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0916 before and 0.0796 after correction.
The Ratio of minimum to maximum transmission is 0.8670.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_description       prism
_exptl_crystal_F_000             2914
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane/n-pentane'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.148
_refine_diff_density_min         -0.803
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.015(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.133
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     532
_refine_ls_number_reflns         11217
_refine_ls_number_restraints     182
_refine_ls_restrained_S_all      1.160
_refine_ls_R_factor_all          0.0385
_refine_ls_R_factor_gt           0.0307
_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^)+(0.0266P)^2^+9.1836P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0696
_refine_ls_wR_factor_ref         0.0714
_reflns_Friedel_coverage         0.941
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.998
_reflns_number_gt                10199
_reflns_number_total             11217
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc00677a2.cif
_cod_data_source_block           mr1517
_cod_depositor_comments
'Adding full bibliography for 1543281--1543283.cif.'
_cod_original_formula_sum        'C126.50 H171 Cl13 N6 O6 S2 U2'
_cod_database_code               1543281
_shelxl_version_number           2014/6
_shelx_estimated_absorpt_t_max   0.764
_shelx_estimated_absorpt_t_min   0.574
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.985(7) 0.015(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H14A,H14B} of C14, {H3A,H3B} of C3, {H10A,H10B} of C100,
  {H11A,H11B} of C110, {H20D,H20E} of C200, {H21C,H21D} of C210, {H15A,H15B} of
  C15, {H16A,H16B} of C16, {H17A,H17B} of C17, {H18A,H18B} of C18, {H19A,H19B}
  of C19, {H21A,H21B} of C21, {H23A,H23B} of C23, {H34A,H34B} of C34, {H35A,
  H35B} of C35, {H36A,H36B} of C36, {H37A,H37B} of C37, {H38A,H38B} of C38,
  {H39A,H39B} of C39
 At 1.5 times of:
  All C(H,H,H) groups, {H2A,H2B} of C2, {H1A,H1B} of C1, {H22A,H22B} of C22,
  All S(H) groups
3. Restrained distances
 C100-Cl11 = C100-Cl12 = C110-Cl13 = C110-Cl14
 1.8 with sigma of 0.01
 Cl11-Cl12 = Cl13-Cl14 = Cl21-Cl22 = Cl23-Cl24
 2.9 with sigma of 0.01
 C200-Cl21 = C200-Cl22 = C210-Cl23 = C210-Cl24
 1.8 with sigma of 0.01
 C300-Cl31
 1.8 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
C100 \\sim Cl11 \\sim Cl12 \\sim C110 \\sim Cl13 \\sim Cl14: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C200 \\sim Cl21 \\sim Cl22 \\sim C210 \\sim Cl23 \\sim Cl24: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C300 \\sim Cl31: within 1.7A with sigma of 0.003 and sigma for terminal atoms
of 0.006
Uanis(C100) \\sim Ueq, Uanis(Cl11) \\sim Ueq, Uanis(Cl12) \\sim Ueq,
Uanis(C110) \\sim Ueq, Uanis(Cl13) \\sim Ueq, Uanis(Cl14) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C200) \\sim Ueq, Uanis(Cl21) \\sim Ueq, Uanis(Cl22) \\sim Ueq,
Uanis(C210) \\sim Ueq, Uanis(Cl23) \\sim Ueq, Uanis(Cl24) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C300) \\sim Ueq, Uanis(Cl31) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
5. Same fragment restrains
{C110, Cl13, Cl14} sigma for 1-2: 0.02, 1-3: 0.04
as
{C100, Cl11, Cl12}
{C110, Cl13, Cl14} sigma for 1-2: 0.02, 1-3: 0.04
as
{C200, Cl21, Cl22}
{C110, Cl13, Cl14} sigma for 1-2: 0.02, 1-3: 0.04
as
{C210, Cl23, Cl24}
6. Others
 Sof(C110)=Sof(H11A)=Sof(H11B)=Sof(Cl13)=Sof(Cl14)=1-FVAR(1)
 Sof(C100)=Sof(H10A)=Sof(H10B)=Sof(Cl11)=Sof(Cl12)=FVAR(1)
 Sof(C210)=Sof(H21C)=Sof(H21D)=Sof(Cl23)=Sof(Cl24)=1-FVAR(2)
 Sof(C200)=Sof(H20D)=Sof(H20E)=Sof(Cl21)=Sof(Cl22)=FVAR(2)
 Fixed Sof: H1(0.33333) H2(0.33333) C300(0.16667) Cl31(0.33333)
7.a Riding coordinates:
 S1(H1), S2(H2)
7.b Ternary CH refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C31(H31), C32(H32), C33(H33)
7.c Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C14(H14A,H14B), C15(H15A,H15B),
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B), C21(H21A,H21B),
  C22(H22A,H22B), C23(H23A,H23B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,
 H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C100(H10A,H10B),
 C110(H11A,H11B), C200(H20D,H20E), C210(H21C,H21D)
7.d Me refined with riding coordinates:
 C20(H20A,H20B,H20C), C40(H40A,H40B,H40C)
7.e Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C27(H27), C29(H29)
;
_shelx_res_checksum              95930
_olex2_submission_special_instructions 'No special instructions were received'