Quantitative U=O bond activation in uranyl complexes via silyl radical transfer
Valerio, Leyla R.; Hakey, Brett; Brennessel, William W.; Matson, Ellen; Chemical Communications  (2022) –; doi:10.1039/D2CC04424B

data_7130612
_publ_section_title
;
 Quantitative U=O bond activation in uranyl complexes via silyl radical
 transfer
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D2CC04424B
_journal_year                    2022
_chemical_formula_moiety         'C57 H57 N7 O2 U'
_chemical_formula_sum            'C57 H57 N7 O2 U'
_chemical_formula_weight         1110.12
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-05-10
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2022-07-26 deposited with the CCDC.	2022-08-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 97.3495(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   30.86731(15)
_cell_length_b                   18.79028(9)
_cell_length_c                   19.81812(9)
_cell_measurement_reflns_used    41060
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      78.7870
_cell_measurement_theta_min      3.4330
_cell_volume                     11400.18(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.120a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.120a (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, 2015b)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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  26.00   0.50    3.78    --  -47.17  38.00-149.00  122
  2  \w   -120.00 -35.00   0.50    3.78    --  -47.17 -38.00  54.00  170
  3  \w     35.00 120.00   0.50    3.78    --   47.17  38.00-149.00  170
  4  \w    -26.00  49.00   0.50    3.78    --   47.17 -38.00  54.00  150
  5  \w   -165.00 -78.00   0.50   15.13    --  -91.75 -38.00  54.00  174
  6  \w    101.00 178.00   0.50   15.13    --  113.25  38.00-149.00  154
  7  \w    -35.00  26.00   0.50    3.78    --  -47.17  38.00-180.00  122
  8  \w    -16.00  28.00   0.50    3.78    --  -47.17  19.00 -90.00   88
  9  \w    -16.00  28.00   0.50    3.78    --  -47.17  19.00   0.00   88
 10  \w    -16.00  28.00   0.50    3.78    --  -47.17  19.00-120.00   88
 11  \w    -65.00 -19.00   0.50   15.13    --  -91.75  61.00   0.00   92
 12  \w    -65.00 -19.00   0.50   15.13    --  -91.75  61.00 -30.00   92
 13  \w     42.00  79.00   0.50   15.13    --  113.25 -61.00 120.00   74
 14  \w     42.00  79.00   0.50   15.13    --  113.25 -61.00  60.00   74
 15  \w    100.00 178.00   0.50   15.13    --  113.25  15.00 150.00  156
 16  \w     91.00 178.00   0.50   15.13    --  113.25  77.00-150.00  174
 17  \w     42.00  79.00   0.50   15.13    --  113.25 -61.00 150.00   74
 18  \w     42.00  79.00   0.50   15.13    --  113.25 -61.00   0.00   74
 19  \w     42.00  79.00   0.50   15.13    --  113.25 -61.00  90.00   74
 20  \w     42.00 106.00   0.50   15.13    --  113.25 -94.00 120.00  128
 21  \w     42.00 111.00   0.50   15.13    --  113.25-125.00 -30.00  138
 22  \w     42.00  79.00   0.50   15.13    --  113.25 -61.00-180.00   74
 23  \w     42.00 111.00   0.50   15.13    --  113.25-125.00  30.00  138
 24  \w     42.00  79.00   0.50   15.13    --  113.25 -61.00  30.00   74
 25  \w    101.00 178.00   0.50   15.13    --  113.25  30.00 -30.00  154
 26  \w     42.00  79.00   0.50   15.13    --  113.25 -61.00 -90.00   74
 27  \w     42.00  79.00   0.50   15.13    --  113.25 -61.00-150.00   74
 28  \w     97.00 178.00   0.50   15.13    --  113.25  61.00 -30.00  162
 29  \w     42.00  79.00   0.50   15.13    --  113.25 -61.00 -60.00   74
 30  \w     42.00 106.00   0.50   15.13    --  113.25 -94.00  60.00  128
 31  \w     42.00 106.00   0.50   15.13    --  113.25 -94.00  30.00  128
 32  \w     25.00 108.00   0.50    3.78    --   47.17  77.00  90.00  166
 33  \w     25.00 119.00   0.50    3.78    --   47.17  77.00 -90.00  188
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0032049000
_diffrn_orient_matrix_UB_12      0.0266691000
_diffrn_orient_matrix_UB_13      0.0739900000
_diffrn_orient_matrix_UB_21      0.0470644000
_diffrn_orient_matrix_UB_22      -0.0286639000
_diffrn_orient_matrix_UB_23      0.0138363000
_diffrn_orient_matrix_UB_31      0.0175480000
_diffrn_orient_matrix_UB_32      0.0720244000
_diffrn_orient_matrix_UB_33      -0.0218350000
_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  0.0349
_diffrn_reflns_av_unetI/netI     0.0236
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            74323
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        74.504
_diffrn_reflns_theta_max         80.280
_diffrn_reflns_theta_min         3.441
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.349
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78437
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.120a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow-orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.294
_exptl_crystal_description       plate
_exptl_crystal_F_000             4448
_exptl_crystal_size_max          0.088
_exptl_crystal_size_mid          0.044
_exptl_crystal_size_min          0.017
_refine_diff_density_max         1.059
_refine_diff_density_min         -1.312
_refine_diff_density_rms         0.077
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     745
_refine_ls_number_reflns         12275
_refine_ls_number_restraints     272
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0295
_refine_ls_R_factor_gt           0.0250
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0289P)^2^+24.7823P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0632
_refine_ls_wR_factor_ref         0.0648
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10832
_reflns_number_total             12275
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2cc04424b2.cif
_cod_data_source_block           matlrv03
_cod_original_cell_volume        11400.18(10)
_cod_database_code               7130612
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.871
_shelx_estimated_absorpt_t_min   0.527
_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
 U1-N4 \\sim U1-N4'
 with sigma of 0.02
 C46-C49 \\sim C46'-C49'
 with sigma of 0.04
 C48-C44 \\sim C48-C44'
 with sigma of 0.04
 C47-C46 \\sim C47-C46'
 with sigma of 0.02
 C48-N4 \\sim C48-N4'
 with sigma of 0.02
 C44-C46 \\sim C44'-C46'
 with sigma of 0.04
 N4-C44 \\sim N4'-C44'
 with sigma of 0.02
 C49-C50 \\sim C49'-C50'
 with sigma of 0.04
 C44-C45 \\sim C44'-C45'
 with sigma of 0.02
 C47-N5 \\sim C47-N5'
 with sigma of 0.04
 C45-C46 \\sim C45'-C46'
 with sigma of 0.02
 N4-C45 \\sim N4'-C45'
 with sigma of 0.04
 C46-N5 \\sim C46'-N5'
 with sigma of 0.02
 C45-N5 \\sim C45'-N5'
 with sigma of 0.04
 N5-C49 \\sim N5'-C49'
 with sigma of 0.02
 C46-C50 \\sim C46'-C50'
 with sigma of 0.04
 N5-C50 \\sim N5'-C50'
 with sigma of 0.02
 U1-C44 \\sim U1-C44'
 with sigma of 0.04
 C47-C45 \\sim C47-C45'
 with sigma of 0.04
 N7-C53 \\sim N7'-C53'
 with sigma of 0.02
 N7-C52 \\sim N7'-C52'
 with sigma of 0.04
 C52-C54 \\sim C52'-C54
 with sigma of 0.04
 N7-C56 \\sim N7'-C56'
 with sigma of 0.02
 C51-C53 \\sim C51'-C53'
 with sigma of 0.04
 N7-C57 \\sim N7'-C57'
 with sigma of 0.02
 C53-C57 \\sim C53'-C57'
 with sigma of 0.04
 C51-C52 \\sim C51'-C52'
 with sigma of 0.02
 N7-C54 \\sim N7'-C54
 with sigma of 0.04
 C52-C53 \\sim C52'-C53'
 with sigma of 0.02
 C51-C55 \\sim C51'-C55
 with sigma of 0.04
 C53-C54 \\sim C53'-C54
 with sigma of 0.02
 C53-C56 \\sim C53'-C56'
 with sigma of 0.04
 C56-C57 \\sim C56'-C57'
 with sigma of 0.04
 N6-C52 \\sim N6'-C52'
 with sigma of 0.04
 U1-C51 \\sim U1-C51'
 with sigma of 0.04
 U1-N6 \\sim U1-N6'
 with sigma of 0.02
 N6-C51 \\sim N6'-C51'
 with sigma of 0.02
 N6-C55 \\sim N6'-C55
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 1.2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 1.2A
4. Rigid body (RIGU) restrains
 N4', N5', C44', C45', C46', C49', C50'
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N4, N5, C44, C45, C46, C49, C50
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N6', N7', C51', C52', C53', C56', C57'
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 N6, N7, C51, C52, C53, C56, C57
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H47A)=Sof(H48A)=Sof(H54A)=Sof(H55A)=Sof(N4')=Sof(N5')=Sof(C44')=Sof(H44')=
 Sof(C45')=Sof(H45')=Sof(C46')=Sof(C49')=Sof(H49D)=Sof(H49E)=Sof(H49F)=
 Sof(C50')=Sof(H50D)=Sof(H50E)=Sof(H50F)=Sof(N6')=Sof(N7')=Sof(C51')=Sof(H51')=
 Sof(C52')=Sof(H52')=Sof(C53')=Sof(C56')=Sof(H56D)=Sof(H56E)=Sof(H56F)=
 Sof(C57')=Sof(H57D)=Sof(H57E)=Sof(H57F)=1-FVAR(1)
 Sof(H47)=Sof(H48)=Sof(H54)=Sof(H55)=Sof(N4)=Sof(N5)=Sof(C44)=Sof(H44)=
 Sof(C45)=Sof(H45)=Sof(C46)=Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=
 Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(N6)=Sof(N7)=Sof(C51)=Sof(H51)=Sof(C52)=
 Sof(H52)=Sof(C53)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=Sof(C57)=Sof(H57A)=
 Sof(H57B)=Sof(H57C)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C7(H7), C8(H8), C12(H12), C15(H15), C16(H16), C17(H17),
 C18(H18), C19(H19), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C28(H28),
  C30(H30), C37(H37), C39(H39), C47(H47), C47(H47A), C48(H48), C48(H48A),
 C54(H54), C54(H54A), C55(H55), C55(H55A), C44(H44), C45(H45), C51(H51),
 C52(H52), C44'(H44'), C45'(H45'), C51'(H51'), C52'(H52')
6.b Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C49'(H49D,H49E,H49F),
 C50'(H50D,H50E,H50F), C56'(H56D,H56E,H56F), C57'(H57D,H57E,H57F)
;
_shelx_res_checksum              41175
_shelx_hkl_checksum              33325
_shelx_fab_checksum              14835
_olex2_submission_original_sample_id matlrv03
_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 1.399
_oxdiff_exptl_absorpt_empirical_full_min 0.818