Assembling Diuranium Complexes in Different States of Charge with a Bridging Redox-Active Ligand
Modder, dieuwertje; Batov, Mikhail; Rajeshkumar, Thayalan; Scopelliti, Rosario; Zivkovic, Ivica; Sienkiewicz, Andrzej; Maron, Laurent; Mazzanti, Marinella; Chemical Science  (2022) –; doi:10.1039/D2SC03592H

data_1567555
_publ_section_title
;
 Assembling Diuranium Complexes in Different States of Charge with a
 Bridging Redox-Active Ligand
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC03592H
_journal_year                    2022
_chemical_formula_moiety         'C44 H114 N10 Si12 U2, C18 H36 K N2 O6'
_chemical_formula_sum            'C62 H150 K N12 O6 Si12 U2'
_chemical_formula_weight         2012.17
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-11-30
_audit_creation_method
;
Olex2 1.5
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6429)
;
_audit_update_record
;
2022-06-23 deposited with the CCDC.	2022-08-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.332(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.9688(16)
_cell_length_b                   11.6805(5)
_cell_length_c                   32.306(3)
_cell_measurement_reflns_used    8607
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.1800
_cell_measurement_theta_min      3.0220
_cell_volume                     10221.3(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.971
_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   -117.00 -21.00   1.00   10.00    --  -42.38 -37.00   0.00   96
  2  \w    -39.00 -11.00   1.00   10.00    --  -42.38 125.00  60.00   28
  3  \w    -64.00  -6.00   1.00   10.00    --  -42.38 125.00-180.00   58
  4  \w   -117.00 -25.00   1.00   10.00    --  -42.38 -37.00 -90.00   92
  5  \w     15.00  64.00   1.00   10.00    --   42.38 -99.00 150.00   49
  6  \w     53.00  92.00   1.00   10.00    --   42.38-125.00 -30.00   39
  7  \w    105.00 152.00   1.00   40.00    --  103.80 111.00  30.00   47
  8  \w     76.00 108.00   1.00   40.00    --  103.80  61.00 120.00   32
  9  \w     78.00 172.00   1.00   40.00    --  103.80  45.00  90.00   94
 10  \w     35.00 108.00   1.00   40.00    --  103.80-111.00   0.00   73
 11  \w     69.00 105.00   1.00   40.00    --  103.80 -94.00  30.00   36
 12  \w    135.00 175.00   1.00   40.00    --  103.80  61.00 120.00   40
 13  \w     21.00  68.00   1.00   40.00    --  103.80 -94.00  30.00   47
 14  \w     31.00  64.00   1.00   40.00    --  103.80 -77.00  30.00   33
 15  \w     30.00 108.00   1.00   40.00    --  103.80-111.00 -90.00   78
 16  \w     32.00 106.00   1.00   40.00    --  103.80 -94.00-180.00   74
 17  \w    104.00 131.00   1.00   40.00    --  103.80 -77.00  30.00   27
 18  \w     37.00  77.00   1.00   40.00    --  103.80 -45.00 150.00   40
 19  \w     28.00  76.00   1.00   40.00    --  103.80 -94.00 -60.00   48
 20  \w     38.00 108.00   1.00   40.00    --  103.80-111.00 120.00   70
 21  \w     51.00 175.00   1.00   40.00    --  103.80  15.00-150.00  124
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0093896000
_diffrn_orient_matrix_UB_12      -0.0261679000
_diffrn_orient_matrix_UB_13      0.0423218000
_diffrn_orient_matrix_UB_21      -0.0241561000
_diffrn_orient_matrix_UB_22      0.1184439000
_diffrn_orient_matrix_UB_23      -0.0042705000
_diffrn_orient_matrix_UB_31      -0.0506287000
_diffrn_orient_matrix_UB_32      -0.0519344000
_diffrn_orient_matrix_UB_33      -0.0311773000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0827
_diffrn_reflns_av_unetI/netI     0.0629
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            37255
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.679
_diffrn_reflns_theta_min         3.027
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.903
_exptl_absorpt_correction_T_max  0.980
_exptl_absorpt_correction_T_min  0.143
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.308
_exptl_crystal_description       irregular
_exptl_crystal_F_000             4100
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.073
_exptl_crystal_size_min          0.054
_refine_diff_density_max         2.844
_refine_diff_density_min         -2.447
_refine_diff_density_rms         0.198
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.019
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     447
_refine_ls_number_reflns         10025
_refine_ls_number_restraints     446
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.1091
_refine_ls_R_factor_gt           0.0771
_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^)+(0.1510P)^2^+66.7292P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2026
_refine_ls_wR_factor_ref         0.2502
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6715
_reflns_number_total             10025
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03592h2.cif
_cod_data_source_block           mb8
_cod_database_code               1567555
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C68 H164 N12 O6 Si12 K1 U2'
_shelx_estimated_absorpt_t_max   0.591
_shelx_estimated_absorpt_t_min   0.133
_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
 C29_$1-C29
 1.54 with sigma of 0.02
 O3-C29
 1.43 with sigma of 0.02
 O3-C29_$1 = O3_$1-C29
 2.4 with sigma of 0.02
 C31-C30 = C24-C23 = C26-C25 = C28-C27
 1.54 with sigma of 0.02
 O2-C26 = O1-C25 = O1-C24 = O3-C28 = O3-C29
 1.43 with sigma of 0.02
 N6_$1-C27_$1 = N6_$1-C23_$1 = N6_$1-C30_$1
 1.47 with sigma of 0.02
 C28_$1-C27_$1 \\sim C28-C27 \\sim C29_$1-C29
 with sigma of 0.02
 O3-C28 \\sim O3-C29 \\sim O3_$1-C29_$1 \\sim O3_$1-C28_$1
 with sigma of 0.02
 N6-C27 \\sim N6_$1-C27_$1
 with sigma of 0.02
 C30-C23 \\sim C23-C27
 with sigma of 0.02
 N6-C30 \\sim N6-C27 \\sim N6-C23
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(Si2) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C9) \\sim
Ueq, Uanis(C13) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of 0.01 and sigma
for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5.a Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,H26B), C27(H27A,
 H27B), C28(H28A,H28B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4)
5.c Idealised Me refined as rotating group:
 C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,
 H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C),
 C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,
 H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 200 electrons were 
found in a volume of 1392\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[C6H14] per Asymmetric Unit 
which account for 200 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              15092
_shelx_hkl_checksum              8039
_shelx_fab_checksum              96326
_olex2_date_sample_data_collection 2021-07-05
_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
- Detector area scaling
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 3.298
_oxdiff_exptl_absorpt_empirical_full_min 0.543