Selective electrochemical capture and release of uranyl from aqueous alkali, lanthanide, and actinide mixtures using redox-switchable carboranes
Keener, Megan; Mattejat, Maxwell; Zheng, Shao-Liang; Wu, Guang; Hayton, Trevor W.; Ménard, Gabriel; Chemical Science  (2022) –; doi:10.1039/D1SC07070C

data_1566416
_publ_section_title
;
 Selective electrochemical capture and release of uranyl from aqueous
 alkali, lanthanide, and actinide mixtures using redox-switchable
 carboranes
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC07070C
_journal_year                    2022
_chemical_formula_moiety
'0.5(C8 H20 O2), 0.5(C40 H44 Co2 O2), C156 H180 B60 O12 P12 Th2, 3(C20 H30 Co), 3(C4 H6 N2), 0.5(C4 N2)'
_chemical_formula_sum            'C254 H332 B60 Co4 N7 O14 P12 Th2'
_chemical_formula_weight         5427.29
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2021-10-11
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2021-11-24 deposited with the CCDC.	2022-02-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.146(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   70.509(6)
_cell_length_b                   17.5517(16)
_cell_length_c                   23.4008(19)
_cell_measurement_reflns_used    9971
_cell_measurement_temperature    110(2)
_cell_measurement_theta_max      26.27
_cell_measurement_theta_min      2.32
_cell_volume                     27519(4)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL n/a (Sheldrick, 2008)'
_diffrn_ambient_temperature      109.97
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0598
_diffrn_reflns_av_unetI/netI     0.0745
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       88
_diffrn_reflns_limit_h_min       -88
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            77701
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.658
_diffrn_reflns_theta_min         0.608
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.440
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6419
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0631 before and 0.0530 after correction.
The Ratio of minimum to maximum transmission is 0.8611.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_density_diffrn    1.310
_exptl_crystal_description       block
_exptl_crystal_F_000             11140
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         3.010
_refine_diff_density_min         -3.375
_refine_diff_density_rms         0.141
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1550
_refine_ls_number_reflns         28546
_refine_ls_number_restraints     134
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0493
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0646P)^2^+107.2398P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1232
_refine_ls_wR_factor_ref         0.1360
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21388
_reflns_number_total             28546
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc07070c2.cif
_cod_data_source_block           mk1192_0m_a
_cod_database_code               1566416
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.813
_shelx_estimated_absorpt_t_min   0.715
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N1-C107 \\sim N2-C105 \\sim N4-C162 \\sim N5-C142
 with sigma of 0.01
 C107-C108 \\sim C161-C162 \\sim C105-C106 \\sim C142-C143
 with sigma of 0.01
 C111-Co3 \\sim C112-Co3 \\sim C113-Co3 \\sim C114-Co3 \\sim C115-Co3
 with sigma of 0.01
 C111-C112 \\sim C112-C113 \\sim C113-C114 \\sim C114-C115 \\sim C115-C111
 with sigma of 0.01
 C111-C113 \\sim C112-C114 \\sim C113-C115 \\sim C114-C111 \\sim C115-C112
\\sim C131-C133
 with sigma of 0.01
 C111-C116 \\sim C131-C134 \\sim C132-C135 \\sim C133-C136
 with sigma of 0.01
 C111-C116 \\sim C112-C117 \\sim C113-C118 \\sim C114-C119 \\sim C115-C120
 with sigma of 0.01
 C116-C117 \\sim C134-C135 \\sim C135-C136
 with sigma of 0.01
 C116-C117 \\sim C117-C118 \\sim C118-C119 \\sim C119-C120 \\sim C120-C116
 with sigma of 0.01
 C181-C182 \\sim C183-C184 \\sim C191-C192 \\sim C193-C194 \\sim C131-C132
\\sim C132-C133
 with sigma of 0.01
 C182-O8 \\sim C183-O8 \\sim C192-O9 \\sim C193-O9
 with sigma of 0.01
 C181-O8 \\sim C184-O8 \\sim C191-O9 \\sim C194-O9
 with sigma of 0.01
 C182-C183 \\sim C192-C193
 with sigma of 0.01
3. Restrained planarity
 C111, C112, C113, C114, C115, C116, C117, C118, C119, C120
 with sigma of 0.1
 C131, C132, C134, C135, C133, C136
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uiso(C131) = Uiso(C132) = Uiso(C133) = Uiso(C134) = Uiso(C135) = Uiso(C136)
5. Others
 Fixed Sof: O8(0.5) C181(0.5) H18B(0.5) H18C(0.5) H18D(0.5) C182(0.5)
 H18E(0.5) H18F(0.5) C183(0.5) H18G(0.5) H18H(0.5) C184(0.5) H18I(0.5)
 H18J(0.5) H18K(0.5) C111(0.5) C112(0.5) C113(0.5) C114(0.5) C115(0.5)
 C116(0.5) H11B(0.5) H11C(0.5) H11D(0.5) C117(0.5) H11E(0.5) H11F(0.5)
 H11G(0.5) C118(0.5) C119(0.5) H11H(0.5) H11I(0.5) H11J(0.5) C120(0.5)
 H12B(0.5) H12C(0.5) H12D(0.5) C161(0.5) C162(0.5) C193(0.5) H19A(0.5)
 H19B(0.5) C194(0.5) H19C(0.5) H19D(0.5) H19E(0.5) O9(0.5) C192(0.5) H19F(0.5)
 H19G(0.5) C191(0.5) H19H(0.5) H19I(0.5) H19J(0.5) Co3(0.5) C131(0.5) C132(0.5)
 C134(0.5) C135(0.5)
 Fixed Uiso: C131(0.1) C132(0.1) C133(0.1) C134(0.1) C135(0.1) C136(0.1)
6.a Secondary CH2 refined with riding coordinates:
 C182(H18E,H18F), C183(H18G,H18H), C193(H19A,H19B), C192(H19F,H19G)
6.b Aromatic/amide H refined with riding coordinates:
 C7(H7A), C9(H9A), C10(H10A), C11(H11A), C12(H12A), C14(H14A), C15(H15A),
 C16(H16A), C17(H17A), C18(H18A), C20(H20A), C21(H21A), C22(H22A), C23(H23A),
 C24(H24A), C26(H26A), C27(H27A), C28(H28A), C29(H29A), C30(H30A), C030(H030),
 C32(H32), C33(H33), C34(H34), C034(H034), C35(H35), C36(H36), C38(H38),
 C39(H39), C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47),
  C48(H48), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54), C56(H56),
 C57(H57), C58(H58), C59(H59), C60(H60), C62(H62), C63(H63), C64(H64), C65(H65),
  C66(H66), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C02D(H02D),
 C01N(H01N), C02X(H02X)
6.c Idealised Me refined as rotating group:
 C181(H18B,H18C,H18D), C184(H18I,H18J,H18K), C116(H11B,H11C,H11D), C117(H11E,
 H11F,H11G), C119(H11H,H11I,H11J), C120(H12B,H12C,H12D), C78(H78A,H78B,H78C),
 C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C), C82(H82A,H82B,
 H82C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C98(H98A,H98B,H98C), C99(H99A,
 H99B,H99C), C100(H10B,H10C,H10D), C101(H10E,H10F,H10G), C102(H10H,H10I,H10J),
 C106(H10K,H10L,H10M), C143(H14K,H14L,H14M), C146(H14B,H14C,H14D), C148(H14E,
 H14F,H14G), C149(H14H,H14I,H14J), C194(H19C,H19D,H19E), C191(H19H,H19I,H19J),
 C108(H10N,H10O,H10P)
6.d Boron cage BH refined with riding coordinates:
 B1(H1), B2(H2), B3(H3), B4(H4), B5(H5), B6(H6), B7(H7), B8(H8), B9(H9),
 B10(H10), B11(H11), B12(H12), B13(H13), B14(H14), B15(H15), B16(H16), B17(H17),
  B18(H18), B19(H19), B20(H20), B21(H21), B22(H22), B23(H23), B24(H24),
 B25(H25), B26(H26), B27(H27), B28(H28), B29(H29), B30(H30)
;
_shelx_res_checksum              89207
_shelx_hkl_checksum              51271
_olex2_submission_special_instructions 'No special instructions were received'