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_4134084
_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_absolute_configuration ad
_chemical_formula_moiety         'C25 H31 N3 O8 U'
_chemical_formula_sum            'C25 H31 N3 O8 U'
_chemical_formula_weight         739.56
_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   geom
_audit_creation_date             2019-08-07
_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                   11.8509(3)
_cell_length_b                   12.0635(4)
_cell_length_c                   17.8749(5)
_cell_measurement_reflns_used    9945
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      68.272
_cell_measurement_theta_min      4.421
_cell_volume                     2555.46(13)
_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 0.998
_diffrn_measured_fraction_theta_max 0.991
_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  0.0523
_diffrn_reflns_av_unetI/netI     0.0442
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            21288
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        66.000
_diffrn_reflns_theta_max         68.357
_diffrn_reflns_theta_min         4.422
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    18.348
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4291
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2014/5 (Bruker,2014/5) was used for absorption correction. wR2(int) was 0.1291 before and 0.0813 after correction. The Ratio of minimum to maximum transmission is 0.5698. The \l/2 correction factor is 0.00150.'
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.922
_exptl_crystal_description       Chunk
_exptl_crystal_F_000             1432
_exptl_crystal_size_max          0.135
_exptl_crystal_size_mid          0.095
_exptl_crystal_size_min          0.065
_refine_diff_density_max         1.564
_refine_diff_density_min         -1.206
_refine_diff_density_rms         0.113
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.012(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     364
_refine_ls_number_reflns         4586
_refine_ls_number_restraints     38
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0322
_refine_ls_R_factor_gt           0.0298
_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^)+(0.0277P)^2^+4.9947P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0700
_refine_ls_wR_factor_ref         0.0711
_reflns_Friedel_coverage         0.765
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.992
_reflns_number_gt                4390
_reflns_number_total             4586
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b11903_si_002.cif
_cod_data_source_block           L(salben)UO2
_cod_database_code               4134084
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.382
_shelx_estimated_absorpt_t_min   0.191
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.988(13)
 0.012(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
{N3A, N3}
{C24A, C24}
{C21A, C21}
4. Restrained distances
 C23A-C24A = C21A-C22A = C23-C24 = C21-C22
 1.51765 with sigma of 0.01
 N3A-C23A = N3A-C22A = N3A-C25A = N3-C23 = N3-C22 = N3-C25
 1.409138 with sigma of 0.01
 N3A-C24A = N3A-C21A = C23A-C22A = C23A-C25A = C22A-C25A
 2.478778 with sigma of 0.02
 N3-C24 = N3-C21 = C23-C22 = C23-C25 = C22-C25
 2.478778 with sigma of 0.02
5. Uiso/Uaniso restraints and constraints
Uanis(C23) \\sim Ueq, Uanis(C22) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C25) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N3A) = Uanis(N3)
Uanis(C24A) = Uanis(C24)
Uanis(C21A) = Uanis(C21)
6. Others
 1(DFIX)=0.9285*FVAR(2)
 1(DFIX)=FVAR(1)
 1(DFIX)=1(DFIX)=1.6333*FVAR(2)
 Sof(N3)=Sof(C23)=Sof(H24C)=Sof(H24D)=Sof(C24)=Sof(H25C)=Sof(H25D)=Sof(C21)=
 Sof(H21C)=Sof(H21D)=Sof(C22)=Sof(H22C)=Sof(H22D)=Sof(C25)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=1-FVAR(2)
 Sof(N3A)=Sof(C23A)=Sof(H23A)=Sof(H23B)=Sof(C24A)=Sof(H24A)=Sof(H24B)=
 Sof(C21A)=Sof(H21A)=Sof(H21B)=Sof(C22A)=Sof(H22A)=Sof(H22B)=Sof(C25A)=
 Sof(H25A)=Sof(H25B)=Sof(H25E)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C23A(H23A,H23B), C24A(H24A,H24B), C21A(H21A,H21B), C22A(H22A,H22B), C23(H24C,
 H24D), C24(H25C,H25D), C21(H21C,H21D), C22(H22C,H22D), C8(H8A,H8B), C9(H9A,
 H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C13(H13A,H13B)
7.b Me refined with riding coordinates:
 C25A(H25A,H25B,H25E), C25(H23D,H23E,H23F)
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)
;
_olex2_submission_special_instructions 'No special instructions were received'