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_7717381
_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         'C92 H114 Cl2 Dy2 N16 O4 U2, 3(C5 H5 N)'
_chemical_formula_sum            'C107 H129 Cl2 Dy2 N19 O4 U2'
_chemical_formula_weight         2617.24
_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                 104.739(4)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.5882(7)
_cell_length_b                   17.0832(4)
_cell_length_c                   17.6031(5)
_cell_measurement_reflns_used    12385
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      29.0180
_cell_measurement_theta_min      3.6800
_cell_volume                     5115.0(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_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 0.954
_diffrn_measured_fraction_theta_max 0.944
_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    -53.00  21.00   1.00   60.00    --  -15.82  98.00-155.00   74
  2  \w    -21.00  55.00   1.00   60.00    --   17.54 -98.00  97.00   76
  3  \w    -39.00  11.00   1.00   60.00    --  -15.82 -77.00 -60.00   50
  4  \w     -9.00  29.00   1.00   60.00    --   17.54  77.00  30.00   38
  5  \w     -8.00  38.00   1.00   60.00    --   17.54  77.00  60.00   46
;
_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      0.0097873000
_diffrn_orient_matrix_UB_12      -0.0188712000
_diffrn_orient_matrix_UB_13      -0.0321055000
_diffrn_orient_matrix_UB_21      -0.0403281000
_diffrn_orient_matrix_UB_22      -0.0083800000
_diffrn_orient_matrix_UB_23      -0.0166525000
_diffrn_orient_matrix_UB_31      -0.0042172000
_diffrn_orient_matrix_UB_32      0.0360141000
_diffrn_orient_matrix_UB_33      -0.0207068000
_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  0.0462
_diffrn_reflns_av_unetI/netI     0.0607
_diffrn_reflns_Laue_measured_fraction_full 0.954
_diffrn_reflns_Laue_measured_fraction_max 0.944
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            28997
_diffrn_reflns_point_group_measured_fraction_full 0.954
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         3.376
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.714
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75481
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.699
_exptl_crystal_description       block
_exptl_crystal_F_000             2572
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Pyridene, hexane'
_exptl_crystal_size_max          0.458
_exptl_crystal_size_mid          0.256
_exptl_crystal_size_min          0.241
_refine_diff_density_max         3.018
_refine_diff_density_min         -2.343
_refine_diff_density_rms         0.215
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     641
_refine_ls_number_reflns         9868
_refine_ls_number_restraints     200
_refine_ls_restrained_S_all      1.118
_refine_ls_R_factor_all          0.0796
_refine_ls_R_factor_gt           0.0514
_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^)+(0.0419P)^2^+66.7969P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1179
_refine_ls_wR_factor_ref         0.1359
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7702
_reflns_number_total             9868
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02367f2.cif
_cod_data_source_block           to499_mp_221123
_cod_database_code               7717381
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C80H110N12U2O4Dy2Cl2
_chemical_oxdiff_usercomment     Pyr/hex
_shelx_estimated_absorpt_t_max   0.396
_shelx_estimated_absorpt_t_min   0.221
_reflns_odcompleteness_completeness 94.17
_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
 N9-C47 = N9-C51
 1.33 with sigma of 0.02
 C47-C48 = C50-C51
 1.38 with sigma of 0.02
 C48-C49 = C49-C50
 1.37 with sigma of 0.02
 N10-C56 = N10-C52
 1.33 with sigma of 0.02
 C56-C55 = C53-C52
 1.38 with sigma of 0.02
 C55-C54 = C54-C53
 1.37 with sigma of 0.02
 N9-C50
 2.39 with sigma of 0.04
 C48-C50
 2.35 with sigma of 0.04
 C47-C49
 2.36 with sigma of 0.04
 C49-C51
 2.37 with sigma of 0.04
 N9-C48
 2.4 with sigma of 0.04
 C54-C52
 2.37 with sigma of 0.04
 N10-C53
 2.39 with sigma of 0.04
 C55-C53
 2.35 with sigma of 0.04
 N10-C55
 2.4 with sigma of 0.04
 C56-C54
 2.36 with sigma of 0.04
 N9-C47 \\sim N9-C51
 with sigma of 0.02
 C47-C48 \\sim C48-C49 \\sim C49-C50 \\sim C50-C51
 with sigma of 0.02
 N9-C50 \\sim N9-C48
 with sigma of 0.04
 C49-C51 \\sim C49-C47 \\sim C50-C48 \\sim C51-C47
 with sigma of 0.04
 C56-C55 \\sim C55-C54 \\sim C54-C53 \\sim C53-C52
 with sigma of 0.02
 N10-C53 \\sim N10-C55
 with sigma of 0.04
 N10-C56 \\sim N10-C52
 with sigma of 0.02
 C54-C52 \\sim C54-C56 \\sim C53-C55 \\sim C52-C56
 with sigma of 0.04
3. Restrained planarity
 N9, C47, C48, C49, C50, C51
 with sigma of 0.1
 N10, C56, C55, C54, C53, C52
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N9 \\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
N10 \\sim C56 \\sim C55 \\sim C54 \\sim C53 \\sim C52: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 N9, C47, C48, C49, C50, C51
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N10, C56, C55, C54, C53, C52
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: N10(0.5) C56(0.5) H56(0.5) C55(0.5) H55(0.5) C54(0.5) H54(0.5)
 C53(0.5) H53(0.5) C52(0.5) H52(0.5)
7.a Ternary CH refined with riding coordinates:
 C31(H31), C20(H20), C9(H9)
7.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C36(H36A,H36B), C21(H21A,H21B), C22(H22A,H22B), C35(H35A,H35B),
 C34(H34A,H34B), C25(H25A,H25B), C10(H10A,H10B), C32(H32A,H32B), C33(H33A,H33B),
  C23(H23A,H23B), C14(H14A,H14B), C11(H11A,H11B), C24(H24A,H24B), C12(H12A,
 H12B), C13(H13A,H13B)
7.c Aromatic/amide H refined with riding coordinates:
 C19(H19), C30(H30), C17(H17), C27(H27), C16(H16), C6(H6), C28(H28), C5(H5),
 C41(H41), C42(H42), C8(H8), C37(H37), C39(H39), C43(H43), C46(H46), C40(H40),
 C44(H44), C38(H38), C45(H45), C47(H47), C48(H48), C49(H49), C50(H50), C51(H51),
  C56(H56), C55(H55), C54(H54), C53(H53), C52(H52)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              64952
_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 1.338
_oxdiff_exptl_absorpt_empirical_full_min 0.837