Redox-Inactive Metal Cations Modulate the Reduction Potential of the Uranyl Ion in Macrocyclic Complexes.
Kumar, Amit; Lionetti, Davide; Day, Victor; Blakemore, James D.; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.9b11903

data_4134085
_publ_section_title
;
 Redox-Inactive Metal Cations Modulate the Reduction Potential of the
 Uranyl Ion in Macrocyclic Complexes.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b11903
_journal_year                    2020
_chemical_formula_moiety         'C26 H31 F3 K N3 O11 S U'
_chemical_formula_sum            'C26 H31 F3 K N3 O11 S U'
_chemical_formula_weight         927.73
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-08-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9299(6)
_cell_length_b                   13.2222(6)
_cell_length_c                   18.4887(9)
_cell_measurement_reflns_used    8448
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      68.244
_cell_measurement_theta_min      4.111
_cell_volume                     3160.9(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      199.99
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.983
_diffrn_measurement_device_type  'Bruker Platinum 135 CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Helios high-brilliance multilayer optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0385
_diffrn_reflns_av_unetI/netI     0.0456
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            12833
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        66.000
_diffrn_reflns_theta_max         68.426
_diffrn_reflns_theta_min         4.110
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    16.968
_exptl_absorpt_correction_T_max  0.7133
_exptl_absorpt_correction_T_min  0.0386
_exptl_absorpt_correction_type   numerical
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1271 before and 0.0560 after correction. The Ratio of minimum to maximum transmission is 0.0541. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.950
_exptl_crystal_description       'Rectangular parallelepiped'
_exptl_crystal_F_000             1800
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.085
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.362
_refine_diff_density_min         -1.456
_refine_diff_density_rms         0.153
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.526(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     496
_refine_ls_number_reflns         5277
_refine_ls_number_restraints     74
_refine_ls_restrained_S_all      1.086
_refine_ls_R_factor_all          0.0400
_refine_ls_R_factor_gt           0.0357
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0547P)^2^+3.5456P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0953
_refine_ls_wR_factor_ref         0.0990
_reflns_Friedel_coverage         0.780
_reflns_Friedel_fraction_full    0.998
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                4839
_reflns_number_total             5277
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11903_si_002.cif
_cod_data_source_block           L(salben)UO2K
_cod_database_code               4134085
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.550
_shelx_estimated_absorpt_t_min   0.161
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.474(13)
 0.526(13)
2. 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
3. Shared sites
{C9, C9'}
4. Restrained distances
 S1-O11 = S1-O12 = S1-O13 = S1'-O11' = S1'-O12' = S1'-O13'
 1.40954 with sigma of 0.01
 C26-F11 = C26-F12 = C26-F13 = C26'-F11' = C26'-F12' = C26'-F13'
 1.305234 with sigma of 0.01
 S1-C26 = S1'-C26'
 1.805621 with sigma of 0.01
 F11-F12 = F11-F13 = F12-F13 = F11'-F12' = F11'-F13' = F12'-F13'
 2.098805 with sigma of 0.02
 O11-O12 = O11-O13 = O12-O13 = O11'-O12' = O11'-O13' = O12'-O13'
 2.384942 with sigma of 0.02
 C26-O11 = C26-O12 = C26-O13 = C26'-O11' = C26'-O12' = C26'-O13'
 2.517438 with sigma of 0.02
 S1-F11 = S1-F12 = S1-F13 = S1'-F11' = S1'-F12' = S1'-F13'
 2.592144 with sigma of 0.02
5. Uiso/Uaniso restraints and constraints
Uanis(C26) \\sim Ueq, Uanis(O12') \\sim Ueq, Uanis(O13') \\sim Ueq, Uanis(F12')
\\sim Ueq, Uanis(C26') \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(F13') \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C9) = Uanis(C9')
6. Others
 Sof(S1')=Sof(O11')=Sof(O12')=Sof(O13')=Sof(F11')=Sof(F12')=Sof(F13')=
 Sof(C26')=1-FVAR(1)
 Sof(S1)=Sof(O11)=Sof(O12)=Sof(O13)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(C26)=FVAR(1)
 Sof(C8')=Sof(H8'A)=Sof(H8'B)=Sof(C9')=Sof(H9'A)=Sof(H9'B)=1-FVAR(2)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=FVAR(2)
 1(DFIX)=0.926*FVAR(4)
 1(DFIX)=FVAR(3)
 1(DFIX)=1.281*FVAR(4)
 1(DFIX)=1.489*FVAR(4)
 1(DFIX)=1.692*FVAR(4)
 1(DFIX)=1.786*FVAR(4)
 1(DFIX)=1.839*FVAR(4)
7.a Riding coordinates:
 C8'(H8'A,H8'B)
7.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C9'(H9'A,H9'B), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B), C13(H13A,H13B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B),
  C24(H24A,H24B)
7.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C15(H15), C16(H16), C17(H17), C20(H20)
7.d Idealised Me refined as rotating group:
 C25(H25A,H25B,H25C)
;
_olex2_submission_special_instructions 'No special instructions were received'