Insights at the molecular level into the formation of oxo-bridged trinuclear uranyl complexes
Schaper, Gerrit; Wenzel, Marco; Schwarzenbolz, Uwe; Steup, Johannes; Hennersdorf, Felix; Henle, Thomas; Lindoy, Leonard F.; Weigand, Jan J.; Chemical Communications  (2022) –; doi:10.1039/D1CC06310C

data_7129572
_publ_section_title
;
 Insights at the molecular level into the formation of oxo-bridged
 trinuclear uranyl complexes
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC06310C
_journal_year                    2022
_chemical_formula_moiety
'C69 H70 N3 O34 U3, C53 H55 N3 O24 U2, H3 O, C4 H10 O, 2(C7 H5 N)'
_chemical_formula_sum            'C140 H148 N8 O60 U5'
_chemical_formula_weight         4092.81
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-12-07
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2021-12-07 deposited with the CCDC.	2022-01-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.89580(10)
_cell_length_b                   23.13860(10)
_cell_length_c                   40.88710(10)
_cell_measurement_reflns_used    139108
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.3040
_cell_measurement_theta_min      2.8480
_cell_volume                     19768.89(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.118a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_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    -65.00  29.00   0.50    3.00    --  -40.50  57.00  60.00  188
  2  \w   -111.00 -17.00   0.50    3.00    --  -40.50 -57.00 -90.00  188
  3  \w    -53.00  29.00   0.50    3.00    --  -40.50  38.00-150.00  164
  4  \w     24.00  79.00   0.50    3.00    --   42.27 -99.00-150.00  110
  5  \w      6.00  74.00   0.50    3.00    --   42.27 -99.00 120.00  136
  6  \w     37.00  95.00   0.50   12.00    --  111.00 -77.00 -90.00  116
  7  \w     54.00  88.00   0.50   12.00    --  111.00 -94.00  60.00   68
  8  \w     37.00  76.00   0.50   12.00    --  111.00 -30.00   0.00   78
  9  \w    108.00 176.00   0.50   12.00    --  111.00  30.00-150.00  136
 10  \w     51.00 109.00   0.50   12.00    --  111.00-111.00   0.00  116
 11  \w     87.00 173.00   0.50   12.00    --  111.00  30.00 -90.00  172
 12  \w     58.00 109.00   0.50   12.00    --  111.00-111.00 150.00  102
 13  \w     63.00  89.00   0.50   12.00    --  111.00 -61.00  30.00   52
 14  \w    138.00 164.00   0.50   12.00    --  111.00 111.00   0.00   52
 15  \w    125.00 178.00   0.50   12.00    --  111.00 111.00 120.00  106
 16  \w     36.00 109.00   0.50   12.00    --  111.00-111.00  60.00  146
 17  \w     83.00 109.00   0.50   12.00    --  111.00-111.00 -90.00   52
 18  \w    131.00 173.00   0.50   12.00    --  111.00  45.00 -60.00   84
 19  \w     71.00 109.00   0.50   12.00    --  111.00-111.00-150.00   76
 20  \w    107.00 132.00   0.50   12.00    --  111.00 111.00-150.00   50
 21  \w     36.00 102.00   0.50   12.00    --  111.00-111.00-180.00  132
 22  \w     75.00 135.00   0.50   12.00    --  111.00 -45.00  90.00  120
 23  \w     87.00 145.00   0.50   12.00    --  111.00  45.00 -30.00  116
 24  \w     36.00 108.00   0.50   12.00    --  111.00-111.00 120.00  144
 25  \w     83.00 109.00   0.50   12.00    --  111.00-111.00 -60.00   52
 26  \w    124.00 176.00   0.50   12.00    --  111.00  45.00   0.00  104
 27  \w    103.00 174.00   0.50   12.00    --  111.00  77.00 150.00  142
 28  \w    114.00 139.00   0.50   12.00    --  111.00 -61.00  30.00   50
 29  \w     89.00 119.00   0.50   12.00    --  111.00  45.00 -60.00   60
 30  \w     94.00 129.00   0.50   12.00    --  111.00 -30.00   0.00   70
 31  \w     84.00 140.00   0.50   12.00    --  111.00 -77.00 150.00  112
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0235547000
_diffrn_orient_matrix_UB_12      0.0413276000
_diffrn_orient_matrix_UB_13      -0.0269758000
_diffrn_orient_matrix_UB_21      0.0697911000
_diffrn_orient_matrix_UB_22      0.0164562000
_diffrn_orient_matrix_UB_23      -0.0078277000
_diffrn_orient_matrix_UB_31      0.0035183000
_diffrn_orient_matrix_UB_32      -0.0495564000
_diffrn_orient_matrix_UB_33      -0.0250928000
_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  0.0342
_diffrn_reflns_av_unetI/netI     0.0249
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -51
_diffrn_reflns_number            210322
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.697
_diffrn_reflns_theta_min         2.375
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.985
_exptl_absorpt_correction_T_max  0.490
_exptl_absorpt_correction_T_min  0.226
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.118a (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            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.375
_exptl_crystal_description       block
_exptl_crystal_F_000             7936
_exptl_crystal_size_max          0.196
_exptl_crystal_size_mid          0.152
_exptl_crystal_size_min          0.134
_refine_diff_density_max         1.338
_refine_diff_density_min         -2.194
_refine_diff_density_rms         0.129
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.036(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1745
_refine_ls_number_reflns         41376
_refine_ls_number_restraints     107
_refine_ls_restrained_S_all      NaN
_refine_ls_R_factor_all          0.0353
_refine_ls_R_factor_gt           0.0352
_refine_ls_shift/su_max          0.018
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0384P)^2^+105.7950P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0916
_refine_ls_wR_factor_ref         0.0916
_reflns_Friedel_coverage         0.869
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                41246
_reflns_number_total             41376
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc06310c2.cif
_cod_data_source_block           1
_cod_database_code               7129572
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C151H163N9O61U5
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.964(4)
 0.036(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups, All O(H,H) groups, All O(H,H,H) groups
3. Restrained distances
 O1-H1
 0.9 with sigma of 0
 H42E-O48
 2 with sigma of 0.2
 O55-H1
 1.8 with sigma of 0.1
 O2-H2A = O2-H2B = O2-H2C
 0.9 with sigma of 0
 O11-H2C = O7-H2A = O3-H2B
 2 with sigma of 0.1
 O42-H42E = O42-H42D
 0.9 with sigma of 0
 H1-U2 \\sim H1-U1 \\sim H1-U3
 with sigma of 0.01
 H2C-H2A \\sim H2A-H2B \\sim H2C-H2B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
N8 \\sim C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132 \\sim
C133: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within
2A
O60 \\sim C125 \\sim C126: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C16 \\sim C74 \\sim C75 \\sim C76 \\sim C77: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O60 \\sim C123 \\sim C124 \\sim C125 \\sim C126: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Uanis(O9) = Uanis(C25)
Uanis(N7) = Uanis(C134)
Uanis(C52) = Uanis(C51)
Uanis(C31) = Uanis(C30) = Uanis(C29) = Uanis(C28) = Uanis(C27) = Uanis(C32) =
Uanis(C25)
Uanis(C1) = Uanis(C2)
Uanis(C67) = Uanis(C66)
Uanis(C16) = Uanis(O59)
Uanis(C67) = Uanis(C16)
Uanis(C16) = Uanis(O60)
Uanis(O20) = Uanis(C16)
Uanis(C38) = Uanis(C34) = Uanis(C41) = Uanis(C2)
Uanis(C93) = Uanis(C95) = Uanis(C97) = Uanis(C98) = Uanis(C99)
5.a Rotating group:
 O42(H42D,H42E)
5.b Ternary CH refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C35(H35), C36(H36),
 C37(H37), C38(H38), C39(H39), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62),
  C81(H81), C82(H82), C83(H83), C84(H84), C85(H85), C104(H104), C105(H105),
 C106(H106), C107(H107), C108(H108)
5.c Secondary CH2 refined with riding coordinates:
 C17(H17A,H17B), C40(H40A,H40B), C63(H63A,H63B), C86(H86A,H86B), C109(H10A,
 H10B), C124(H12D,H12E), C125(H12F,H12G)
5.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C7(H7), C8(H8), C11(H11), C25(H25), C26(H26),
 C28(H28), C29(H29), C30(H30), C31(H31), C34(H34), C48(H48), C49(H49), C51(H51),
  C52(H52), C53(H53), C54(H54), C57(H57), C74(H74), C75(H75), C76(H76),
 C77(H77), C72(H72), C71(H71), C80(H80), C95(H95), C94(H94), C97(H97), C98(H98),
  C99(H99), C100(H100), C103(H103), C118(H118), C119(H119), C120(H120),
 C121(H121), C122(H122), C139(H139), C140(H140), C136(H136), C137(H137),
 C138(H138), C129(H129), C130(H130), C131(H131), C132(H132), C133(H133)
5.e Fitted hexagon refined as free rotating group:
 C27(C28,C29,C30,C31,C32), C48(C47,C56,C55,C50,C49), C79(C78,C73,C72,C71,C70),
 C96(C95,C94,C93,C102,C101), C139(C140,C135,C136,C137,C138), C129(C130,C131,
 C132,C133,C128)
5.f X=CH2 refined with riding coordinates:
 N6(H6A,H6B)
5.g Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C42(H42A,H42B,
 H42C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C), C65(H65A,H65B,H65C), C67(H67A,
 H67B,H67C), C69(H69A,H69B,H69C), C88(H88A,H88B,H88C), C90(H90A,H90B,H90C),
 C92(H92A,H92B,H92C), C111(H11A,H11B,H11C), C113(H11D,H11E,H11F), C115(H11G,
 H11H,H11I), C123(H12A,H12B,H12C), C126(H12H,H12I,H12J)
;
_shelx_res_checksum              56968
_shelx_fab_checksum              50606
_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 1.870
_oxdiff_exptl_absorpt_empirical_full_min 0.784