Controlled and sequential single-electron reduction of the uranyl dication.
Obey, Tom J. N.; Nichol, Gary S.; Love, Jason B.; Dalton transactions (Cambridge, England : 2003) 53 (2024) 16229–16240; doi:10.1039/d4dt02367f

data_7717387
_publ_section_title
;
 Controlled and sequential single-electron reduction of the uranyl
 dication.
;
_journal_issue                   39
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              16229
_journal_page_last               16240
_journal_paper_doi               10.1039/d4dt02367f
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C87 H109 N15 O4 U2 Y2, C6 H14, [+ solvents]'
_chemical_formula_sum            'C93 H123 N15 O4 U2 Y2'
_chemical_formula_weight         2168.94
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-29
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-12-11 deposited with the CCDC.	2024-09-20 downloaded from the CCDC.
;
_cell_angle_alpha                79.382(2)
_cell_angle_beta                 82.241(2)
_cell_angle_gamma                85.201(2)
_cell_formula_units_Z            2
_cell_length_a                   12.1503(3)
_cell_length_b                   16.1749(4)
_cell_length_c                   24.3853(7)
_cell_measurement_reflns_used    30892
_cell_measurement_temperature    120.1(4)
_cell_measurement_theta_max      29.2200
_cell_measurement_theta_min      3.5450
_cell_volume                     4658.7(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.1(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -71.00  -3.00   1.00   30.00    --  -15.82 129.00-153.00   68
  2  \w    -78.00 -11.00   1.00   30.00    --  -15.82 141.00  18.00   67
  3  \w     11.00  80.00   1.00   30.00    --   17.54-141.00 -39.00   69
  4  \w      3.00  72.00   1.00   30.00    --   17.54-129.00 133.00   69
  5  \w    -43.00  39.00   1.00   30.00    --  -15.82  77.00-120.00   82
  6  \w    -83.00   1.00   1.00   30.00    --  -15.82 -57.00 -60.00   84
  7  \w    -88.00 -39.00   1.00   30.00    --  -15.82-178.00 120.00   49
  8  \w     -9.00  39.00   1.00   30.00    --   17.54  77.00-150.00   48
  9  \w     39.00  90.00   1.00   30.00    --   17.54 178.00-120.00   51
 10  \w     -9.00  39.00   1.00   30.00    --   17.54  77.00 -60.00   48
 11  \w      1.00  85.00   1.00   30.00    --   17.54  57.00 120.00   84
 12  \w     -9.00  39.00   1.00   30.00    --   17.54  77.00  30.00   48
 13  \w    -52.00  36.00   1.00   30.00    --   17.54 -38.00 -30.00   88
 14  \w    -85.00   3.00   1.00   30.00    --  -15.82 -38.00-150.00   88
 15  \w     -9.00  39.00   1.00   30.00    --   17.54  77.00  90.00   48
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0043671000
_diffrn_orient_matrix_UB_12      0.0156942000
_diffrn_orient_matrix_UB_13      -0.0293055000
_diffrn_orient_matrix_UB_21      -0.0044812000
_diffrn_orient_matrix_UB_22      0.0418459000
_diffrn_orient_matrix_UB_23      0.0053944000
_diffrn_orient_matrix_UB_31      0.0586915000
_diffrn_orient_matrix_UB_32      -0.0006863000
_diffrn_orient_matrix_UB_33      -0.0010690000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0695
_diffrn_reflns_av_unetI/netI     0.0610
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            93776
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         3.388
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.755
_exptl_absorpt_correction_T_max  0.650
_exptl_absorpt_correction_T_min  0.311
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_density_diffrn    1.546
_exptl_crystal_description       prism
_exptl_crystal_F_000             2160
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Pyridene, hexane'
_exptl_crystal_size_max          0.504
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.124
_refine_diff_density_max         4.139
_refine_diff_density_min         -2.022
_refine_diff_density_rms         0.197
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1049
_refine_ls_number_reflns         19017
_refine_ls_number_restraints     1233
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0783
_refine_ls_R_factor_gt           0.0625
_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^)+(0.0349P)^2^+76.4691P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1383
_refine_ls_wR_factor_ref         0.1459
_reflns_Friedel_coverage         0.000
_reflns_number_gt                15700
_reflns_number_total             19017
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02367f2.cif
_cod_data_source_block           to517-pyr_twin1_hklf4_refinalised
_cod_database_code               7717387
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C93H123N15U2O4Y2
_chemical_oxdiff_usercomment     pyr/hex
_shelx_estimated_absorpt_t_max   0.590
_shelx_estimated_absorpt_t_min   0.198
_reflns_odcompleteness_completeness 99.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. 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
2. Restrained distances
 C88-C89 = C89-C90 = C90-C91 = C91-C92 = C92-C93
 1.52 with sigma of 0.02
 C89-C91 = C90-C92
 2.54 with sigma of 0.04
 C88-C90 = C91-C93
 2.53 with sigma of 0.04
 C88-C89 \\sim C89-C90 \\sim C90-C91 \\sim C91-C92 \\sim C92-C93
 with sigma of 0.02
 C88-C90 \\sim C90-C92 \\sim C89-C91 \\sim C91-C93
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Ternary CH refined with riding coordinates:
 C17(H17), C9(H9), C45(H45), C31(H31), C67(H67), C56(H56), C20(H20)
5.b Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C13(H13A,H13B), C50(H50A,H50B), C38(H38A,H38B), C46(H46A,
 H46B), C47(H47A,H47B), C61(H61A,H61B), C10(H10A,H10B), C2(H2A,H2B), C94(H94A,
 H94B), C36(H36A,H36B), C34(H34A,H34B), C22(H22A,H22B), C24(H24A,H24B),
 C23(H23A,H23B), C21(H21A,H21B), C72(H72A,H72B), C25(H25A,H25B), C32(H32A,H32B),
  C35(H35A,H35B), C12(H12A,H12B), C70(H70A,H70B), C48(H48A,H48B), C58(H58A,
 H58B), C49(H49A,H49B), C57(H57A,H57B), C59(H59A,H59B), C68(H68A,H68B),
 C69(H69A,H69B), C33(H33A,H33B), C71(H71A,H71B), C60(H60A,H60B), C89(H89A,H89B),
  C90(H90A,H90B), C91(H91A,H91B), C92(H92A,H92B)
5.c Aromatic/amide H refined with riding coordinates:
 C53(H53), C73(H73), C55(H55), C8(H8), C44(H44), C52(H52), C66(H66), C16(H16),
 C76(H76), C81(H81), C77(H77), C42(H42), C84(H84), C75(H75), C64(H64), C41(H41),
  C85(H85), C74(H74), C83(H83), C5(H5), C19(H19), C87(H87), C6(H6), C30(H30),
 C80(H80), C82(H82), C78(H78), C86(H86), C63(H63), C79(H79), C28(H28), C27(H27)
5.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C37(H37A,H37B,H37C), C88(H88A,H88B,H88C), C93(H93A,H93B,H93C)
;
_shelx_res_checksum              52584
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.232
_oxdiff_exptl_absorpt_empirical_full_min 0.760