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_7717389
_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         'C66 H77 Cl3 Dy Li2 N12 O2 U, 2(C5 H5 N)'
_chemical_formula_sum            'C76 H87 Cl3 Dy Li2 N14 O2 U'
_chemical_formula_weight         1749.35
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-24
_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                90
_cell_angle_beta                 106.566(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.0653(4)
_cell_length_b                   17.0891(3)
_cell_length_c                   24.4481(5)
_cell_measurement_reflns_used    21649
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      28.5940
_cell_measurement_theta_min      3.5370
_cell_volume                     7634.8(3)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0521
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.871
_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    -35.00  55.00   1.00   15.00    --  -14.44  34.00 -95.00   90
  2  \w    -53.00  36.00   1.00   15.00    --   16.16 -34.00 106.00   89
  3  \w    -87.00 -39.00   1.00   15.00    --  -14.44-178.00 -90.00   48
  4  \w    -11.00  39.00   1.00   15.00    --   16.16  77.00   0.00   50
  5  \w    -11.00  39.00   1.00   15.00    --   16.16  77.00 120.00   50
  6  \w    -51.00  33.00   1.00   15.00    --   16.16 -57.00  60.00   84
  7  \w     -1.00  83.00   1.00   15.00    --   16.16  57.00-150.00   84
;
_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      -0.0281516000
_diffrn_orient_matrix_UB_12      -0.0058810000
_diffrn_orient_matrix_UB_13      0.0132839000
_diffrn_orient_matrix_UB_21      0.0070274000
_diffrn_orient_matrix_UB_22      -0.0408235000
_diffrn_orient_matrix_UB_23      0.0012268000
_diffrn_orient_matrix_UB_31      0.0257625000
_diffrn_orient_matrix_UB_32      0.0047192000
_diffrn_orient_matrix_UB_33      0.0271736000
_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  0.0674
_diffrn_reflns_av_unetI/netI     0.0738
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.871
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            79648
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.871
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.901
_diffrn_reflns_theta_min         3.335
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.249
_exptl_absorpt_correction_T_max  0.752
_exptl_absorpt_correction_T_min  0.224
_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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.522
_exptl_crystal_description       plate
_exptl_crystal_F_000             3488
_exptl_crystal_preparation
'Vapour diffusion of hexane into pyridine solution'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Pyridene, hexane'
_exptl_crystal_size_max          0.457
_exptl_crystal_size_mid          0.242
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.362
_refine_diff_density_min         -1.258
_refine_diff_density_rms         0.159
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     893
_refine_ls_number_reflns         17518
_refine_ls_number_restraints     100
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0711
_refine_ls_R_factor_gt           0.0420
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0231P)^2^+10.4983P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0703
_refine_ls_wR_factor_ref         0.0790
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13292
_reflns_number_total             17518
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02367f2.cif
_cod_data_source_block           to509_refinalised
_cod_database_code               7717389
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C36 H47 N6 U O2 Dy Li2 Cl3'
_chemical_oxdiff_usercomment     Pyr/hex
_shelx_estimated_absorpt_t_max   0.829
_shelx_estimated_absorpt_t_min   0.318
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.63
_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
 N14-C72 = N14-C76
 1.33 with sigma of 0.02
 C72-C73 = C75-C76
 1.38 with sigma of 0.02
 C73-C74 = C74-C75
 1.37 with sigma of 0.02
 N14-C75
 2.39 with sigma of 0.04
 C73-C75
 2.35 with sigma of 0.04
 C72-C74
 2.36 with sigma of 0.04
 C74-C76
 2.37 with sigma of 0.04
 N14-C73
 2.4 with sigma of 0.04
 N14-C72 \\sim N14-C76
 with sigma of 0.02
 C72-C73 \\sim C73-C74 \\sim C74-C75 \\sim C75-C76
 with sigma of 0.02
 N14-C75 \\sim N14-C73
 with sigma of 0.04
 C74-C76 \\sim C74-C72 \\sim C75-C73 \\sim C76-C72
 with sigma of 0.04
3. Restrained planarity
 N14, C72, C73, C74, C75, C76
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N14 \\sim C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 N14, C72, C73, C74, C75, C76
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Ternary CH refined with riding coordinates:
 C31(H31), C20(H20), C9(H9)
6.b Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C2(H2A,H2B), C36(H36A,H36B), C24(H24A,H24B), C21(H21A,H21B),
 C14(H14A,H14B), C23(H23A,H23B), C32(H32A,H32B), C22(H22A,H22B), C10(H10A,H10B),
  C35(H35A,H35B), C33(H33A,H33B), C11(H11A,H11B), C13(H13A,H13B), C12(H12A,
 H12B), C34(H34A,H34B)
6.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C19(H19), C41(H41), C17(H17), C28(H28), C27(H27), C16(H16),
 C37(H37), C8(H8), C57(H57), C61(H61), C5(H5), C66(H66), C51(H51), C62(H62),
 C67(H67), C40(H40), C6(H6), C68(H68), C39(H39), C71(H71), C52(H52), C38(H38),
 C54(H54), C56(H56), C46(H46), C58(H58), C60(H60), C65(H65), C47(H47), C70(H70),
  C42(H42), C59(H59), C63(H63), C55(H55), C64(H64), C44(H44), C45(H45),
 C53(H53), C43(H43), C69(H69), C50(H50), C48(H48), C49(H49), C72(H72), C73(H73),
  C74(H74), C75(H75), C76(H76)
6.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              7326
_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 1.274
_oxdiff_exptl_absorpt_empirical_full_min 0.716