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_4134087
_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
'C27.5 H38 Ca F3 N3 O13 S U, C H4 O, C F3 O3 S'
_chemical_formula_sum            'C29.5 H42 Ca F6 N3 O17 S2 U'
_chemical_formula_weight         1166.89
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2019-09-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                79.402(3)
_cell_angle_beta                 64.575(3)
_cell_angle_gamma                81.805(3)
_cell_formula_units_Z            2
_cell_length_a                   12.7589(9)
_cell_length_b                   13.2831(9)
_cell_length_c                   13.7644(10)
_cell_measurement_reflns_used    9758
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      67.933
_cell_measurement_theta_min      3.590
_cell_volume                     2065.6(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_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker APEX-II 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  0.0591
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            32430
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        66.000
_diffrn_reflns_theta_max         68.453
_diffrn_reflns_theta_min         3.394
_diffrn_source                   'sealed tube'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    14.000
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.4621
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1112 before and 0.0749 after correction. The Ratio of minimum to maximum transmission is 0.6137. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.876
_exptl_crystal_description       'Near cube'
_exptl_crystal_F_000             1148
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.085
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.521
_refine_diff_density_min         -1.159
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     581
_refine_ls_number_reflns         7473
_refine_ls_number_restraints     19
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.0403
_refine_ls_R_factor_gt           0.0370
_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^)+(0.0255P)^2^+5.7162P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0850
_refine_ls_wR_factor_ref         0.0866
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6979
_reflns_number_total             7473
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11903_si_002.cif
_cod_data_source_block           L(salben)UO2Ca
_cod_original_formula_sum        'C29.50 H42 Ca F6 N3 O17 S2 U'
_cod_database_code               4134087
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.487
_shelx_estimated_absorpt_t_min   0.263
_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, All O(H) groups
2. Restrained distances
 C23-C24 = C21-C22
 1.52549 with sigma of 0.01
 N3-C23 = N3-C22 = N3-C25
 1.416417 with sigma of 0.01
 C23A-C22A = C23A-C25A = C22A-C25A
 2.491583 with sigma of 0.02
 N3-C24 = N3-C21 = C23-C22 = C23-C25 = C22-C25
 2.491583 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C25A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 1(DFIX)=0.9285*FVAR(2)
 1(DFIX)=FVAR(1)
 1(DFIX)=1(DFIX)=1.6333*FVAR(2)
 Sof(H21C)=Sof(H21D)=Sof(H24C)=Sof(H24D)=Sof(C22A)=Sof(H22A)=Sof(H22B)=
 Sof(C23A)=Sof(H23C)=Sof(H23D)=Sof(C25A)=Sof(H25D)=Sof(H25E)=Sof(H25F)=1-FVAR(2)
 Sof(H21A)=Sof(H21B)=Sof(H24A)=Sof(H24B)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C25)=
 Sof(H25A)=Sof(H25B)=Sof(H25C)=Sof(C22)=Sof(H22C)=Sof(H22D)=FVAR(2)
 Fixed Sof: H2SB(0.5) C2S(0.5) H2SC(0.5) H2SD(0.5) H2SE(0.5)
5.a Everything fixed:
 H2SB
5.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B),
 C13(H13A,H13B), C21(H21C,H21D), C21(H21A,H21B), C24(H24A,H24B), C24(H24C,H24D),
  C23(H23A,H23B), C22A(H22A,H22B), C23A(H23C,H23D), C22(H22C,H22D)
5.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C15(H15), C16(H16), C17(H17), C20(H20)
5.d Tetrahedral OH refined with riding coordinates:
 O1S(H1S)
5.e Idealised Me refined as rotating group:
 C1S(H1SA,H1SB,H1SC), C2S(H2SC,H2SD,H2SE), C25(H25A,H25B,H25C), C25A(H25D,H25E,
 H25F), C3S(H3SA,H3SB,H3SC)
5.f Idealised tetrahedral OH refined as rotating group:
 O3S(H3S)
;
_olex2_submission_special_instructions 'No special instructions were received'