Synthesis and reactivity of a terminal uranium(iv) sulfide supported by siloxide ligands
Andrez, Julie; Pécaut, Jacques; Scopelliti, Rosario; Kefalidis, Christos E.; Maron, Laurent; Rosenzweig, Michael W.; Meyer, Karsten; Mazzanti, Marinella; Chem. Sci. 7 (2016) 5846–; doi:10.1039/C6SC00675B

data_1543290
_publ_section_title
;
 Synthesis and reactivity of a terminal uranium(iv) sulfide supported by
 siloxide ligands
;
_journal_issue                   9
_journal_name_full               'Chem. Sci.'
_journal_page_first              5846
_journal_paper_doi               10.1039/C6SC00675B
_journal_volume                  7
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C72 H162 K2 O24 S3 Si6 U2, C7 H8'
_chemical_formula_sum            'C79 H170 K2 O24 S3 Si6 U2'
_chemical_formula_weight         2323.13
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2015-11-19
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_audit_update_record
;
2016-01-18 deposited with the CCDC.
2016-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90.00
_cell_angle_beta                 94.534(12)
_cell_angle_gamma                90.00
_cell_formula_units_Z            2
_cell_length_a                   13.9735(17)
_cell_length_b                   18.2720(11)
_cell_length_c                   22.168(3)
_cell_measurement_reflns_used    394
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      22
_cell_measurement_theta_min      3
_cell_volume                     5642.3(11)
_computing_cell_refinement       'Dirax/lsq (Duisenberg & Schreurs, 1989-2000)'
_computing_data_collection       'Collect (Bruker AXS BV, 1997-2004)'
_computing_data_reduction        'EvalCCD (Duisenberg & Schreurs, 1990-2000)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0680
_diffrn_reflns_av_unetI/netI     0.0779
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            72530
_diffrn_reflns_theta_full        26.37
_diffrn_reflns_theta_max         26.37
_diffrn_reflns_theta_min         1.45
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    3.117
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.4419
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS 2008, Bruker AXS, 2008'
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       prism
_exptl_crystal_F_000             2380
_exptl_crystal_size_max          0.147
_exptl_crystal_size_mid          0.143
_exptl_crystal_size_min          0.096
_refine_diff_density_max         2.307
_refine_diff_density_min         -1.485
_refine_diff_density_rms         0.325
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.000(5)
_refine_ls_extinction_coef       0.00476(14)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.156
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1204
_refine_ls_number_reflns         22269
_refine_ls_number_restraints     195
_refine_ls_restrained_S_all      1.155
_refine_ls_R_factor_all          0.0642
_refine_ls_R_factor_gt           0.0463
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0640P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1053
_refine_ls_wR_factor_ref         0.1327
_reflns_number_gt                19157
_reflns_number_total             22269
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            c6sc00675b2.cif
_cod_data_source_block           ja468
_cod_depositor_comments
'Adding full bibliography for 1543284--1543292.cif.'
_cod_original_cell_volume        5642.4(11)
_cod_database_code               1543290
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.937(5) 0.063(5)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C69-C71
 1.52 with sigma of 0.02
 C69-C72
 1.52 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C2B \\sim C3 \\sim C3B \\sim C4 \\sim C4B \\sim C2: within 1.7A with sigma of
0.01 and sigma for terminal atoms of 0.02
C48B \\sim C48 \\sim C47B \\sim C47 \\sim C46B \\sim C46: within 1.7A with
sigma of 0.01 and sigma for terminal atoms of 0.02
C69 \\sim C69B \\sim C71 \\sim C71B \\sim C72B \\sim C72 \\sim C70B \\sim C70:
within 1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
C124 \\sim C123 \\sim C122 \\sim C121 \\sim C126 \\sim C125 \\sim C127: within
1.7A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Others
 Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=
 Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=1-FVAR(1)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(H3C)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=Sof(H4C)=FVAR(1)
 Sof(C48B)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C46B)=Sof(H46D)=Sof(H46E)=
 Sof(H46F)=Sof(C47B)=Sof(H47D)=Sof(H47E)=Sof(H47F)=1-FVAR(2)
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=
 Sof(C48)=Sof(H48D)=Sof(H48E)=Sof(H48F)=FVAR(2)
 Sof(C69B)=Sof(C70B)=Sof(H70D)=Sof(H70E)=Sof(H70F)=Sof(C71B)=Sof(H71A)=
 Sof(H71B)=Sof(H71C)=Sof(C72B)=Sof(H72A)=Sof(H72B)=Sof(H72C)=1-FVAR(3)
 Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C72)=Sof(H72D)=Sof(H72E)=Sof(H72F)=
 Sof(C71)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C69)=FVAR(3)
6.a Aromatic/amide H refined with riding coordinates:
 C122(H122), C123(H123), C124(H124), C125(H125), C126(H126)
6.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,
 H12B,H12C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C),
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C42(H42A,H42B,H42C), C43(H43A,
 H43B,H43C), C44(H44A,H44B,H44C), C48B(H48A,H48B,H48C), C46(H46A,H46B,H46C),
 C47(H47A,H47B,H47C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,
 H52C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C66(H66A,
 H66B,H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C70(H70A,H70B,H70C),
 C70B(H70D,H70E,H70F), C71B(H71A,H71B,H71C), C82(H82A,H82B,H82C), C83(H83A,H83B,
 H83C), C84(H84A,H84B,H84C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,
 H88B,H88C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C),
 C102(H10D,H10E,H10F), C103(H10G,H10H,H10I), C104(H10J,H10K,H10L), C106(H10M,
 H10N,H10O), C107(H10P,H10Q,H10R), C108(H10S,H10T,H10U), C110(H11D,H11E,H11F),
 C111(H11G,H11H,H11I), C112(H11J,H11K,H11L), C127(H12D,H12E,H12F), C2B(H2BA,
 H2BB,H2BC), C4B(H4BA,H4BB,H4BC), C3B(H3BA,H3BB,H3BC), C48(H48D,H48E,H48F),
 C46B(H46D,H46E,H46F), C47B(H47D,H47E,H47F), C72B(H72A,H72B,H72C), C72(H72D,
 H72E,H72F), C71(H71D,H71E,H71F)
;
_olex2_submission_special_instructions 'No special instructions were received'