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_1567557
_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         '2(C22 H57 N5 Si6 U), C24 H20 B, C3 H7'
_chemical_formula_sum            'C71 H141 B N10 Si12 U2'
_chemical_formula_weight         1958.88
_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             2021-11-25
_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                98.8987(12)
_cell_angle_beta                 91.1267(12)
_cell_angle_gamma                92.6498(13)
_cell_formula_units_Z            2
_cell_length_a                   15.1222(2)
_cell_length_b                   15.2178(2)
_cell_length_c                   23.8147(4)
_cell_measurement_reflns_used    32124
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      76.3760
_cell_measurement_theta_min      3.3670
_cell_volume                     5406.64(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.103a (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 0.994
_diffrn_measured_fraction_theta_max 0.976
_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  17.00   1.00    2.50    --  -42.76  75.00 -29.00   70
  2  \w     -8.00  17.00   1.00    2.50    --   42.76 -75.00-157.00   25
  3  \w     41.00  68.00   1.00   10.00    --  112.00 -75.00-157.00   27
  4  \w    112.00 143.00   1.00   10.00    --  112.00  75.00 -29.00   31
  5  \w    -62.00  32.00   1.00    2.50    --  -42.76  37.00-150.00   94
  6  \w   -116.00 -27.00   1.00    2.50    --  -42.76 -37.00-120.00   89
  7  \w   -115.00 -26.00   1.00    2.50    --  -42.76 -57.00  60.00   89
  8  \w     30.00  99.00   1.00    2.50    --   42.76-125.00  90.00   69
  9  \w     35.00  74.00   1.00    2.50    --   42.76 -77.00-180.00   39
 10  \w      1.00  28.00   1.00    2.50    --   42.76 -77.00-180.00   27
 11  \w     68.00 108.00   1.00   10.00    --  112.00-111.00   0.00   40
 12  \w     78.00 176.00   1.00   10.00    --  112.00  15.00  30.00   98
 13  \w     62.00 131.00   1.00   10.00    --  112.00 178.00 120.00   69
 14  \w     42.00  93.00   1.00   10.00    --  112.00 -45.00-120.00   51
 15  \w    106.00 133.00   1.00   10.00    --  112.00 -45.00-120.00   27
 16  \w     72.00 109.00   1.00   10.00    --  112.00-111.00 -90.00   37
 17  \w    109.00 141.00   1.00   10.00    --  112.00 111.00  60.00   32
 18  \w     36.00 109.00   1.00   10.00    --  112.00-111.00-150.00   73
 19  \w    104.00 174.00   1.00   10.00    --  112.00  77.00  90.00   70
 20  \w     57.00 111.00   1.00   10.00    --  112.00 -45.00  60.00   54
 21  \w    104.00 177.00   1.00   10.00    --  112.00  77.00-150.00   73
 22  \w     44.00 109.00   1.00   10.00    --  112.00-111.00 120.00   65
 23  \w     72.00 109.00   1.00   10.00    --  112.00-111.00 -30.00   37
 24  \w     45.00  75.00   1.00   10.00    --  112.00 -94.00  60.00   30
 25  \w     37.00  85.00   1.00   10.00    --  112.00 -77.00-120.00   48
 26  \w    116.00 144.00   1.00   10.00    --  112.00 -77.00-120.00   28
 27  \w    153.00 178.00   1.00   10.00    --  112.00  77.00 150.00   25
 28  \w     36.00  97.00   1.00   10.00    --  112.00-111.00-120.00   61
 29  \w     60.00 116.00   1.00   10.00    --  112.00  15.00-150.00   56
 30  \w    120.00 147.00   1.00   10.00    --  112.00  15.00-150.00   27
 31  \w     36.00  63.00   1.00   10.00    --  112.00 -94.00   0.00   27
 32  \w     45.00 109.00   1.00   10.00    --  112.00-111.00 150.00   64
 33  \w    143.00 170.00   1.00   10.00    --  112.00 111.00  60.00   27
 34  \w     82.00 108.00   1.00   10.00    --  112.00-111.00  30.00   26
 35  \w     81.00 108.00   1.00   10.00    --  112.00-111.00  60.00   27
 36  \w     39.00 109.00   1.00   10.00    --  112.00-111.00  90.00   70
 37  \w    109.00 155.00   1.00   10.00    --  112.00 111.00   0.00   46
 38  \w     37.00  85.00   1.00   10.00    --  112.00-111.00-180.00   48
 39  \w     89.00 171.00   1.00   10.00    --  112.00  45.00 -90.00   82
 40  \w    104.00 140.00   1.00   10.00    --  112.00 111.00-150.00   36
;
_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      -0.0880325000
_diffrn_orient_matrix_UB_12      -0.0559593000
_diffrn_orient_matrix_UB_13      -0.0034631000
_diffrn_orient_matrix_UB_21      -0.0278693000
_diffrn_orient_matrix_UB_22      0.0378159000
_diffrn_orient_matrix_UB_23      -0.0537028000
_diffrn_orient_matrix_UB_31      0.0433800000
_diffrn_orient_matrix_UB_32      -0.0772293000
_diffrn_orient_matrix_UB_33      -0.0373433000
_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  0.0426
_diffrn_reflns_av_unetI/netI     0.0463
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            66393
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.976
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.884
_diffrn_reflns_theta_min         2.926
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.910
_exptl_absorpt_correction_T_max  0.483
_exptl_absorpt_correction_T_min  0.154
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.103a (Rigaku Oxford Diffraction, 2021)
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            black
_exptl_crystal_density_diffrn    1.203
_exptl_crystal_description       prism
_exptl_crystal_F_000             1988
_exptl_crystal_size_max          0.406
_exptl_crystal_size_mid          0.154
_exptl_crystal_size_min          0.109
_refine_diff_density_max         1.842
_refine_diff_density_min         -1.573
_refine_diff_density_rms         0.120
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     990
_refine_ls_number_reflns         22270
_refine_ls_number_restraints     385
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.0551
_refine_ls_R_factor_gt           0.0411
_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^)+(0.0325P)^2^+25.8647P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0959
_refine_ls_wR_factor_ref         0.1041
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17947
_reflns_number_total             22270
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03592h2.cif
_cod_data_source_block           dkm478
_cod_original_cell_volume        5406.63(14)
_cod_database_code               1567557
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C83 H169 B1 N10 Si12 U2'
_shelx_estimated_absorpt_t_max   0.411
_shelx_estimated_absorpt_t_min   0.108
_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
 Si11-N10 \\sim Si12-N10 \\sim Si13-N11 \\sim Si14-N11
 with sigma of 0.02
 U2-N10 \\sim U2-N11
 with sigma of 0.02
 Si13-C45 \\sim Si11-C41 \\sim Si11-C39 \\sim Si11-C40 \\sim Si13-C46 \\sim
Si13-C47 \\sim Si12-C42 ~
 Si14-C48 \\sim Si12-C44 \\sim Si14-C50 \\sim Si14-C49 \\sim Si12-C43
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si11 \\sim Si12 \\sim Si13 \\sim Si14 \\sim N10 \\sim N11 \\sim C39 \\sim C40
\\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48
\\sim C49 \\sim C50: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
4. Rigid body (RIGU) restrains
 Si11, Si12, Si13, Si14, N10, N11, C39, C40, C41, C42, C43, C44, C45, C46, C47,
  C48, C49, C50
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(Si13)=Sof(Si14)=Sof(N11)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46)=
 Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C48)=
 Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=
 Sof(H50A)=Sof(H50B)=Sof(H50C)=1-FVAR(1)
 Sof(Si11)=Sof(Si12)=Sof(N10)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=
 Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=
 Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C44)=
 Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C76(H76A,H76B), C77(H77A,H77B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C24(H24), C25(H25), C26(H26), C52(H52), C53(H53),
 C54(H54), C55(H55), C56(H56), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62),
  C64(H64), C65(H65), C66(H66), C67(H67), C68(H68), C70(H70), C71(H71),
 C72(H72), C73(H73), C74(H74)
6.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), C27(H27A,H27B,H27C),
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,
 H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C),
 C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,H42B,
 H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C),
 C50(H50A,H50B,H50C), C75(H75A,H75B,H75C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 211 electrons were 
found in a volume of 1336\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[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              77568
_shelx_hkl_checksum              93274
_shelx_fab_checksum              72547
_olex2_date_sample_data_collection 2021-03-19
_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 1.700
_oxdiff_exptl_absorpt_empirical_full_min 0.642