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_7717383
_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         'C112.003 H136.003 K4 N20.001 O4 U2'
_chemical_formula_sum            'C112 H136 K4 N20 O4 U2'
_chemical_formula_weight         2458.86
_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             2023-11-17
_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                76.777(2)
_cell_angle_beta                 79.539(2)
_cell_angle_gamma                68.993(2)
_cell_formula_units_Z            1
_cell_length_a                   12.5339(3)
_cell_length_b                   12.5763(2)
_cell_length_c                   19.5151(5)
_cell_measurement_reflns_used    24560
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      29.2040
_cell_measurement_theta_min      3.6730
_cell_volume                     2778.75(11)
_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 0.869
_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    -88.00 -25.00   1.00    5.70    --  -16.54 161.00   7.00   63
  2  \w    -62.00   6.00   1.00    5.70    --  -16.54 117.00-143.00   68
  3  \w     24.00  91.00   1.00    5.70    --   18.41-161.00 -22.00   67
  4  \w     -6.00  64.00   1.00    5.70    --   18.41-117.00 129.00   70
  5  \w    -35.00  53.00   1.00    5.70    --  -16.54  38.00 -30.00   88
  6  \w    -89.00 -39.00   1.00    5.70    --  -16.54-178.00 120.00   50
  7  \w    -43.00  39.00   1.00    5.70    --  -16.54  77.00-120.00   82
  8  \w     -8.00  39.00   1.00    5.70    --   18.41  77.00-150.00   47
  9  \w     -8.00  39.00   1.00    5.70    --   18.41  77.00   0.00   47
 10  \w      2.00  86.00   1.00    5.70    --   18.41  57.00 120.00   84
 11  \w    -51.00  37.00   1.00    5.70    --   18.41 -38.00 -30.00   88
 12  \w    -86.00 -20.00   1.00    5.70    --  -16.54 -38.00-150.00   66
;
_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      0.0033709000
_diffrn_orient_matrix_UB_12      -0.0200555000
_diffrn_orient_matrix_UB_13      0.0368558000
_diffrn_orient_matrix_UB_21      0.0588065000
_diffrn_orient_matrix_UB_22      -0.0043797000
_diffrn_orient_matrix_UB_23      -0.0049591000
_diffrn_orient_matrix_UB_31      -0.0158058000
_diffrn_orient_matrix_UB_32      0.0578649000
_diffrn_orient_matrix_UB_33      0.0052951000
_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  0.0505
_diffrn_reflns_av_unetI/netI     0.0501
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.869
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            51201
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.869
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.734
_diffrn_reflns_theta_min         3.360
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.120
_exptl_absorpt_correction_T_max  0.274
_exptl_absorpt_correction_T_min  0.069
_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            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.469
_exptl_crystal_description       hexagonal
_exptl_crystal_F_000             1240
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Pyridene, hexane'
_exptl_crystal_size_max          0.62
_exptl_crystal_size_mid          0.47
_exptl_crystal_size_min          0.24
_refine_diff_density_max         2.415
_refine_diff_density_min         -1.118
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     752
_refine_ls_number_reflns         13766
_refine_ls_number_restraints     301
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0420
_refine_ls_R_factor_gt           0.0328
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0333P)^2^+1.7319P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0699
_refine_ls_wR_factor_ref         0.0740
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12167
_reflns_number_total             13766
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt02367f2.cif
_cod_data_source_block           to506_2_refinalised
_cod_original_cell_volume        2778.75(12)
_cod_database_code               7717383
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C70H90N6U2O4K4
_chemical_oxdiff_usercomment     Pyr/hex
_shelx_estimated_absorpt_t_max   0.521
_shelx_estimated_absorpt_t_min   0.248
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.67
_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
 N8-C42 = N8-C46
 1.33 with sigma of 0.02
 C42-C43 = C45-C46
 1.38 with sigma of 0.02
 C43-C44 = C44-C45
 1.37 with sigma of 0.02
 N8A-C46A = N8A-C42A
 1.33 with sigma of 0.02
 C46A-C45A = C43A-C42A
 1.38 with sigma of 0.02
 C45A-C44A = C44A-C43A
 1.37 with sigma of 0.02
 N8B-C42B = N8B-C46B
 1.33 with sigma of 0.02
 C42B-C43B = C45B-C46B
 1.38 with sigma of 0.02
 C43B-C44B = C44B-C45B
 1.37 with sigma of 0.02
 N8-C43
 2.4 with sigma of 0.04
 N8-C45
 2.39 with sigma of 0.04
 C42-C44
 2.36 with sigma of 0.04
 C43-C45
 2.35 with sigma of 0.04
 C44-C46
 2.37 with sigma of 0.04
 N8A-C45A
 2.4 with sigma of 0.04
 N8A-C43A
 2.39 with sigma of 0.04
 C46A-C44A
 2.36 with sigma of 0.04
 C45A-C43A
 2.35 with sigma of 0.04
 C44A-C42A
 2.37 with sigma of 0.04
 N8B-C43B
 2.4 with sigma of 0.04
 N8B-C45B
 2.39 with sigma of 0.04
 C42B-C44B
 2.36 with sigma of 0.04
 C43B-C45B
 2.35 with sigma of 0.04
 C44B-C46B
 2.37 with sigma of 0.04
 N8-C42 \\sim N8-C46
 with sigma of 0.02
 C42-C43 \\sim C43-C44 \\sim C44-C45 \\sim C45-C46
 with sigma of 0.02
 N8-C45 \\sim N8-C43
 with sigma of 0.04
 C44-C46 \\sim C44-C42 \\sim C45-C43 \\sim C46-C42
 with sigma of 0.04
 N8A-C46A \\sim N8A-C42A
 with sigma of 0.02
 C46A-C45A \\sim C45A-C44A \\sim C44A-C43A \\sim C43A-C42A
 with sigma of 0.02
 N8A-C43A \\sim N8A-C45A
 with sigma of 0.04
 C44A-C42A \\sim C44A-C46A \\sim C43A-C45A \\sim C42A-C46A
 with sigma of 0.04
 N8B-C42B \\sim N8B-C46B
 with sigma of 0.02
 C42B-C43B \\sim C43B-C44B \\sim C44B-C45B \\sim C45B-C46B
 with sigma of 0.02
 N8B-C45B \\sim N8B-C43B
 with sigma of 0.04
 C44B-C46B \\sim C44B-C42B \\sim C45B-C43B \\sim C46B-C42B
 with sigma of 0.04
3. Restrained planarity
 N8, C42, C43, C44, C45, C46
 with sigma of 0.1
 N8A, C46A, C45A, C44A, C43A, C42A
 with sigma of 0.1
 N8B, C42B, C43B, C44B, C45B, C46B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N8 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
N8A \\sim C46A \\sim C45A \\sim C44A \\sim C43A \\sim C42A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
N8B \\sim C42B \\sim C43B \\sim C44B \\sim C45B \\sim C46B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 N8, C42, C43, C44, C45, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N8A, C46A, C45A, C44A, C43A, C42A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N8B, C42B, C43B, C44B, C45B, C46B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 1*[Sof(N8)+Sof(C42)+Sof(H42)+Sof(C43)+Sof(H43)+Sof(C44)+Sof(H44)+Sof(C45)+
 Sof(H45)+Sof(C46)+Sof(H46)]+1*[Sof(N8A)+Sof(C46A)+Sof(H46A)+Sof(C45A)+
 Sof(H45A)+Sof(C44A)+Sof(H44A)+Sof(C43A)+Sof(H43A)+Sof(C42A)+Sof(H42A)]+1*
 [Sof(N8B)+Sof(C42B)+Sof(H42B)+Sof(C43B)+Sof(H43B)+Sof(C44B)+Sof(H44B)+
 Sof(C45B)+Sof(H45B)+Sof(C46B)+Sof(H46B)]=1 with esd of 0.001
 Sof(N8)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(H44)=Sof(C45)=
 Sof(H45)=Sof(C46)=Sof(H46)=FVAR(1)
 Sof(N8A)=Sof(C46A)=Sof(H46A)=Sof(C45A)=Sof(H45A)=Sof(C44A)=Sof(H44A)=
 Sof(C43A)=Sof(H43A)=Sof(C42A)=Sof(H42A)=FVAR(2)
 Sof(N8B)=Sof(C42B)=Sof(H42B)=Sof(C43B)=Sof(H43B)=Sof(C44B)=Sof(H44B)=
 Sof(C45B)=Sof(H45B)=Sof(C46B)=Sof(H46B)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C4(H4), C7(H7), C18(H18), C29(H29)
7.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B), C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B),
  C23(H23A,H23B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,
 H33B), C34(H34A,H34B), C35(H35A,H35B)
7.c Aromatic/amide H refined with riding coordinates:
 C42(H42), C43(H43), C44(H44), C45(H45), C46(H46), C46A(H46A), C45A(H45A),
 C44A(H44A), C43A(H43A), C42A(H42A), C42B(H42B), C43B(H43B), C44B(H44B),
 C45B(H45B), C46B(H46B), C6(H6), C14(H14), C15(H15), C17(H17), C25(H25),
 C26(H26), C28(H28), C37(H37), C38(H38), C39(H39), C40(H40), C41(H41), C47(H47),
  C48(H48), C49(H49), C50(H50), C51(H51), C52(H52), C53(H53), C54(H54),
 C55(H55), C56(H56)
7.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C)
;
_shelx_res_checksum              10543
_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 1.282
_oxdiff_exptl_absorpt_empirical_full_min 0.713