Dinitrogen cleavage by a dinuclear uranium(iii) complex.
Jori, Nadir; Keener, Megan; Rajeshkumar, Thayalan; Scopelliti, Rosario; Maron, Laurent; Mazzanti, Marinella; Chemical science 14 (2023) 13485–13494; doi:10.1039/d3sc05253b

data_1570267
_publ_section_title
;
 Dinitrogen cleavage by a dinuclear uranium(iii) complex.
;
_journal_issue                   46
_journal_name_full               'Chemical science'
_journal_page_first              13485
_journal_page_last               13494
_journal_paper_doi               10.1039/d3sc05253b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C60 H135 N2 O21 Si5 U2, 2(C18 H36 K N2 O6)'
_chemical_formula_sum            'C96 H207 K2 N6 O33 Si5 U2'
_chemical_formula_weight         2668.37
_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
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-02-07
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-06-27 deposited with the CCDC.	2023-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                111.0011(18)
_cell_angle_beta                 94.4333(17)
_cell_angle_gamma                104.1127(18)
_cell_formula_units_Z            4
_cell_length_a                   16.3644(3)
_cell_length_b                   30.3735(6)
_cell_length_c                   32.8860(6)
_cell_measurement_reflns_used    28919
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      72.4400
_cell_measurement_theta_min      3.2050
_cell_volume                     14552.5(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_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      139.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.965
_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    -26.00   7.00   1.00    8.50    --  -40.91  26.00 154.00   33
  2  \w   -116.00  -9.00   1.00    8.50    --  -40.91 -26.00  -8.00  107
  3  \w    -30.00  18.00   1.00    8.50    --   40.91 -26.00  -8.00   48
  4  \w     19.00 118.00   1.00    8.50    --   40.91  26.00 154.00   99
  5  \w     28.00 137.00   1.00   34.00    --  105.15 -26.00  -8.00  109
  6  \w    119.00 145.00   1.00   34.00    --  105.15  26.00 154.00   26
  7  \w    -22.00  40.00   1.00    8.50    --   40.91 -38.00-120.00   62
  8  \w     35.00  81.00   1.00    8.50    --   40.91-125.00-180.00   46
  9  \w      6.00  42.00   1.00    8.50    --   40.91 -99.00-120.00   36
 10  \w     27.00  94.00   1.00    8.50    --   40.91-125.00   0.00   67
 11  \w    105.00 172.00   1.00   34.00    --  105.15 111.00 150.00   67
 12  \w     80.00 177.00   1.00   34.00    --  105.15  45.00   0.00   97
 13  \w    123.00 166.00   1.00   34.00    --  105.15  77.00  30.00   43
 14  \w    109.00 137.00   1.00   34.00    --  105.15 -77.00  60.00   28
 15  \w     94.00 121.00   1.00   34.00    --  105.15 -45.00 120.00   27
 16  \w     52.00 109.00   1.00   34.00    --  105.15-111.00  90.00   57
 17  \w     38.00 108.00   1.00   34.00    --  105.15-111.00 -60.00   70
 18  \w    120.00 177.00   1.00   34.00    --  105.15  45.00  90.00   57
 19  \w     39.00 108.00   1.00   34.00    --  105.15-111.00 150.00   69
 20  \w     32.00  57.00   1.00   34.00    --  105.15 -45.00 120.00   25
 21  \w     67.00  93.00   1.00   34.00    --  105.15 -77.00  60.00   26
 22  \w    147.00 173.00   1.00   34.00    --  105.15 111.00 120.00   26
 23  \w    133.00 178.00   1.00   34.00    --  105.15  77.00 -60.00   45
 24  \w     33.00 106.00   1.00   34.00    --  105.15 -94.00 -30.00   73
 25  \w     35.00 107.00   1.00   34.00    --  105.15-111.00-120.00   72
;
_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      -0.0934170000
_diffrn_orient_matrix_UB_12      -0.0301824000
_diffrn_orient_matrix_UB_13      -0.0050413000
_diffrn_orient_matrix_UB_21      0.0262094000
_diffrn_orient_matrix_UB_22      -0.0479503000
_diffrn_orient_matrix_UB_23      -0.0163935000
_diffrn_orient_matrix_UB_31      0.0182059000
_diffrn_orient_matrix_UB_32      0.0040073000
_diffrn_orient_matrix_UB_33      0.0480614000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.1147
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            63246
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.123
_diffrn_reflns_theta_min         2.825
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.627
_exptl_absorpt_correction_T_max  0.787
_exptl_absorpt_correction_T_min  0.213
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.80a (Rigaku Oxford Diffraction, 2023)
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            'clear intense yellow'
_exptl_crystal_density_diffrn    1.218
_exptl_crystal_description       irregular
_exptl_crystal_F_000             5524
_exptl_crystal_size_max          0.328
_exptl_crystal_size_mid          0.246
_exptl_crystal_size_min          0.116
_refine_diff_density_max         3.044
_refine_diff_density_min         -2.657
_refine_diff_density_rms         0.159
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.928
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2684
_refine_ls_number_reflns         63246
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      0.929
_refine_ls_R_factor_all          0.1068
_refine_ls_R_factor_gt           0.0588
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0877P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1401
_refine_ls_wR_factor_ref         0.1538
_reflns_Friedel_coverage         0.000
_reflns_number_gt                35657
_reflns_number_total             63246
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 2.6056\% 
around [0.46 -0.51 0.72] (reciprocal) or [0.93 -0.02 0.37] (direct)
;
_cod_data_source_file            d3sc05253b2.cif
_cod_data_source_block           nj1053-cryp_sq
_cod_depositor_comments
'Adding full bibliography for 1570263--1570267.cif.'
_cod_database_code               1570267
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C113.5 H227 N6 O33 Si5 K2 U2'
_shelx_estimated_absorpt_t_max   0.472
_shelx_estimated_absorpt_t_min   0.189
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6313(7)
 0.3687(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Uiso/Uaniso restraints and constraints
Uanis(C12) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C44)
\\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C172) \\sim Ueq,
Uanis(C179) \\sim Ueq, Uanis(C184) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C58) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C87)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4.a Secondary CH2 refined with riding coordinates:
 C121(H12G,H12H), C122(H12I,H12J), C123(H12K,H12L), C124(H12M,H12N), C125(H12O,
 H12P), C126(H12Q,H12R), C127(H12S,H12T), C128(H12U,H12V), C129(H12W,H12X),
 C130(H13A,H13B), C131(H13C,H13D), C132(H13E,H13F), C133(H13G,H13H), C134(H13I,
 H13J), C135(H13K,H13L), C136(H13M,H13N), C137(H13O,H13P), C138(H13Q,H13R),
 C139(H13S,H13T), C140(H14D,H14E), C141(H14F,H14G), C142(H14H,H14I), C143(H14J,
 H14K), C144(H14L,H14M), C145(H14N,H14O), C146(H14P,H14Q), C147(H14R,H14S),
 C148(H14T,H14U), C149(H14V,H14W), C150(H15D,H15E), C151(H15F,H15G), C152(H15H,
 H15I), C153(H15J,H15K), C154(H15L,H15M), C155(H15N,H15O), C156(H15P,H15Q),
 C157(H15R,H15S), C158(H15T,H15U), C159(H15V,H15W), C160(H16D,H16E), C161(H16F,
 H16G), C162(H16H,H16I), C163(H16J,H16K), C164(H16L,H16M), C165(H16N,H16O),
 C166(H16P,H16Q), C167(H16R,H16S), C168(H16T,H16U), C169(H16V,H16W), C170(H17A,
 H17B), C171(H17C,H17D), C172(H17E,H17F), C173(H17G,H17H), C174(H17I,H17J),
 C175(H17K,H17L), C176(H17M,H17N), C177(H17O,H17P), C178(H17Q,H17R), C179(H17S,
 H17T), C180(H18D,H18E), C181(H18F,H18G), C182(H18H,H18I), C183(H18J,H18K),
 C184(H18L,H18M), C185(H18N,H18O), C186(H18P,H18Q), C187(H18R,H18S), C188(H18T,
 H18U), C189(H18V,H18W), C190(H19D,H19E), C191(H19F,H19G), C192(H19H,H19I)
4.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C6(H6A,H6B,H6C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,
 H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,
 H22C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C),
 C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,
 H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C46(H46A,H46B,H46C),
 C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C50(H50A,H50B,H50C), C51(H51A,H51B,
 H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,
 H56B,H56C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C),
 C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C66(H66A,H66B,
 H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C70(H70A,H70B,H70C), C71(H71A,
 H71B,H71C), C72(H72A,H72B,H72C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C),
 C76(H76A,H76B,H76C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,H80B,
 H80C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C86(H86A,
 H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C90(H90A,H90B,H90C),
 C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C94(H94A,H94B,H94C), C95(H95A,H95B,
 H95C), C96(H96A,H96B,H96C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C),
 C100(H10D,H10E,H10F), C102(H10G,H10H,H10I), C103(H10J,H10K,H10L), C104(H10M,
 H10N,H10O), C106(H10P,H10Q,H10R), C107(H10S,H10T,H10U), C108(H10V,H10W,H10X),
 C110(H11D,H11E,H11F), C111(H11G,H11H,H11I), C112(H11J,H11K,H11L), C114(H11M,
 H11N,H11O), C115(H11P,H11Q,H11R), C116(H11S,H11T,H11U), C118(H11V,H11W,H11X),
 C119(H11Y,H,HA), C120(H12D,H12E,H12F)
;
_shelx_res_checksum              45396
_shelx_fab_checksum              19581
_platon_squeeze_special_details
;
A solvent mask was calculated and 451 electrons were 
found in a volume of 2425\%A^3^ in 11 voids per unit cell. 
This is consistent with the presence of 
0.25[], 0.2[C7H8], 0.25[], 0.2[C7H8], 1[C7H8], 0.5[C7H8], 0.25[], 0.25[], 0.5[C7H8], 0.25[], 0.25[] per Asymmetric Unit 
which account for 480 electrons 
per unit cell.
;
_platon_squeeze_void_probe_radius 1.20
_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 4.728
_oxdiff_exptl_absorpt_empirical_full_min 0.198
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2