The effect of ancillary ligands on hydrocarbon C-H bond functionalization by uranyl photocatalysts.
Rutkauskaite, Ryte; Zhang, Xiaobin; Woodward, Adam W.; Liu, Yanlin; Herrera, Gabriel; Purkis, Jamie; Woodall, Sean D.; Sarsfield, Mark; Schreckenbach, Georg; Natrajan, Louise S.; Arnold, Polly L.; Chemical science 15 (2024) 6965–6978; doi:10.1039/d4sc01310g

data_1571456
_publ_section_title
;
 The effect of ancillary ligands on hydrocarbon C-H bond functionalization
 by uranyl photocatalysts.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              6965
_journal_page_last               6978
_journal_paper_doi               10.1039/d4sc01310g
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C48 H32 Cl4 N4 O4 U2, 2(C6 H5 Cl)'
_chemical_formula_sum            'C60 H42 Cl6 N4 O4 U2'
_chemical_formula_weight         1571.73
_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
_audit_creation_date             2023-02-03
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-02-03 deposited with the CCDC.	2024-03-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 89.3990(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.4589(2)
_cell_length_b                   26.3459(4)
_cell_length_c                   14.4152(2)
_cell_measurement_reflns_used    51984
_cell_measurement_temperature    99.98(12)
_cell_measurement_theta_max      31.0260
_cell_measurement_theta_min      2.0840
_cell_volume                     5490.92(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.104a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.104a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(12)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -42.00  30.00   0.50    4.57    --    4.95 -83.00 -10.00  144
  2  \w    -31.00  21.00   0.50    4.57    --   -5.34  83.00 110.00  104
  3  \w    -42.00  20.00   0.50    4.57    --   -5.34 -83.00 -10.00  124
  4  \w     -7.00  38.00   0.50    4.57    --    4.95 -99.00 -60.00   90
  5  \w    -59.00  20.00   0.50    4.57    --    4.95 -57.00 120.00  158
  6  \w    -10.00  59.00   0.50    4.57    --    4.95  57.00-180.00  138
  7  \w    -68.00  17.00   0.50    4.57    --    4.95 -37.00-150.00  170
  8  \w     -7.00  38.00   0.50    4.57    --    4.95 -99.00  60.00   90
  9  \w    -18.00  68.00   0.50    4.57    --   -5.34  35.00 154.72  172
 10  \w    -18.00  68.00   0.50    4.57    --   -5.34  37.00  30.00  172
 11  \w     -7.00  28.00   0.50    4.57    --   -5.34 -99.00-180.00   70
 12  \w    -18.00  70.00   0.50    4.57    --   -5.34  19.00 -60.00  176
 13  \w    -18.00  70.00   0.50    4.57    --   -5.34  30.00 105.80  176
 14  \w     -7.00  28.00   0.50    4.57    --   -5.34 -99.00-150.00   70
 15  \w     -7.00  28.00   0.50    4.57    --   -5.34 -99.00  30.00   70
 16  \w    -18.00  68.00   0.50    4.57    --   -5.34  37.00-120.00  172
 17  \w    -18.00  70.00   0.50    4.57    --   -5.34  27.00 -38.33  176
 18  \w    -58.00  10.00   0.50    4.57    --   -5.34 -57.00 -60.00  136
 19  \w    -18.00  69.00   0.50    4.57    --   -5.34  34.00  10.10  174
;
_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      -0.0390143000
_diffrn_orient_matrix_UB_12      0.0151910000
_diffrn_orient_matrix_UB_13      -0.0105924000
_diffrn_orient_matrix_UB_21      0.0293607000
_diffrn_orient_matrix_UB_22      0.0179326000
_diffrn_orient_matrix_UB_23      -0.0221908000
_diffrn_orient_matrix_UB_31      -0.0049946000
_diffrn_orient_matrix_UB_32      -0.0131266000
_diffrn_orient_matrix_UB_33      -0.0426068000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0639
_diffrn_reflns_av_unetI/netI     0.0230
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            115436
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.877
_diffrn_reflns_theta_min         2.094
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    6.235
_exptl_absorpt_correction_T_max  0.763
_exptl_absorpt_correction_T_min  0.221
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.104a (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            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.901
_exptl_crystal_description       block
_exptl_crystal_F_000             2992
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Crystallized by vapor diffusion of hexanes to a chlorobenzene solution'
_exptl_crystal_size_max          0.372
_exptl_crystal_size_mid          0.087
_exptl_crystal_size_min          0.042
_refine_diff_density_max         2.215
_refine_diff_density_min         -0.946
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     407
_refine_ls_number_reflns         6560
_refine_ls_number_restraints     355
_refine_ls_restrained_S_all      1.078
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0261
_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^)+(0.0185P)^2^+37.6201P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0547
_refine_ls_wR_factor_ref         0.0623
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5250
_reflns_number_total             6560
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01310g2.cif
_cod_data_source_block           pla21026refinalised
_cod_depositor_comments
'Adding full bibliography for 1571453--1571456.cif.'
_cod_database_code               1571456
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'U O2 Cl2 C20 H20 N2'
_shelx_estimated_absorpt_t_max   0.780
_shelx_estimated_absorpt_t_min   0.205
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 Cl3-C25
 1.74 with sigma of 0.02
 C25-C26 = C25-C30 = C29-C30
 1.39 with sigma of 0.02
 C26-C27 = C28-C29
 1.4 with sigma of 0.02
 C27-C28
 1.36 with sigma of 0.02
 C27-C29
 2.39 with sigma of 0.04
 C25-C27 = C26-C28
 2.4 with sigma of 0.04
 Cl3-C30
 2.71 with sigma of 0.04
 C25-C29
 2.38 with sigma of 0.04
 C28-C30
 2.43 with sigma of 0.04
 Cl3-C26
 2.7 with sigma of 0.04
 C25-C26 \\sim C26-C27 \\sim C27-C28 \\sim C28-C29 \\sim C29-C30 \\sim C30-C25
 with sigma of 0.02
 C25-C27 \\sim C27-C29 \\sim C26-C30 \\sim C26-C28 \\sim C28-C30 \\sim C25-C29
 with sigma of 0.02
 Cl3-C26 \\sim Cl3-C30
 with sigma of 0.02
 C26-C27 \\sim C26A-C27A
 with sigma of 0.02
 Cl3-C25 \\sim Cl3A-C25A
 with sigma of 0.02
 C28-C30 \\sim C28A-C30A
 with sigma of 0.04
 C26-C28 \\sim C26A-C28A
 with sigma of 0.04
 C25-C30 \\sim C25A-C30A
 with sigma of 0.02
 C25-C26 \\sim C25A-C26A
 with sigma of 0.02
 C25-C29 \\sim C25A-C29A
 with sigma of 0.04
 C27-C28 \\sim C27A-C28A
 with sigma of 0.02
 C26-C30 \\sim C26A-C30A
 with sigma of 0.04
 C28-C29 \\sim C28A-C29A
 with sigma of 0.02
 C27-C29 \\sim C27A-C29A
 with sigma of 0.04
 C29-C30 \\sim C29A-C30A
 with sigma of 0.02
 Cl3-C26 \\sim Cl3A-C26A
 with sigma of 0.04
 Cl3-C30 \\sim Cl3A-C30A
 with sigma of 0.04
 C25-C27 \\sim C25A-C27A
 with sigma of 0.04
3. Restrained planarity
 Cl3, C25, C26, C27, C28, C29, C30
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Cl3 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Cl3 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim Cl3A
\\sim C25A \\sim C30A \\sim C29A \\sim C28A \\sim C27A \\sim C26A: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
5. Rigid body (RIGU) restrains
 Cl3, C25, C26, C27, C28, C29, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Cl3A)=Sof(C25A)=Sof(C30A)=Sof(H30A)=Sof(C29A)=Sof(H29A)=Sof(C28A)=
 Sof(H28A)=Sof(C27A)=Sof(H27A)=Sof(C26A)=Sof(H26A)=1-FVAR(1)
 Sof(Cl3)=Sof(C25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=
 Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=FVAR(1)
7.a Aromatic/amide H refined with riding coordinates:
 C5(H5), C10(H10), C6(H6), C2(H2), C14(H14), C1(H1), C20(H20), C9(H9),
 C21(H21), C15(H15), C16(H16), C18(H18), C24(H24), C17(H17), C23(H23), C22(H22),
  C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C30A(H30A), C29A(H29A),
 C28A(H28A), C27A(H27A), C26A(H26A)
;
_shelx_res_checksum              60066
_olex2_exptl_crystal_mounting_method 'Mounted on a goniometer loop with fomblin'
_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 1.417
_oxdiff_exptl_absorpt_empirical_full_min 0.539