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_1570266
_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
'C72 H162 K1.7 N2 O25 Si6 U2, C18 H36 K N2 O6, C7 H8'
_chemical_formula_sum            'C97 H206 K2.7 N4 O31 Si6 U2'
_chemical_formula_weight         2674.82
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-06-16
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-06-27 deposited with the CCDC.	2023-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.6381(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.1801(2)
_cell_length_b                   29.9313(6)
_cell_length_c                   33.7708(6)
_cell_measurement_reflns_used    12828
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      73.9210
_cell_measurement_theta_min      3.2140
_cell_volume                     14304.4(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.90a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.90a (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 2019/3 (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 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.975
_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   -113.00 -88.00   1.00   10.00    --  -40.91-142.00  71.00   25
  2  \w    -81.00 -56.00   1.00   10.00    --  -40.91 142.00 127.00   25
  3  \w    -73.00 -48.00   1.00   10.00    --  -40.91 128.00 -42.00   25
  4  \w     54.00  79.00   1.00   10.00    --   40.91-128.00-117.00   25
  5  \w     45.00  87.00   1.00   10.00    --   40.91-142.00  71.00   42
  6  \w     53.00  78.00   1.00   40.00    --  112.00-128.00-117.00   25
  7  \w     88.00 131.00   1.00   40.00    --  112.00 142.00 127.00   43
  8  \w    113.00 138.00   1.00   40.00    --  112.00 128.00 -42.00   25
  9  \w     73.00 100.00   1.00   40.00    --  112.00-142.00  71.00   27
 10  \w   -115.00 -16.00   1.00   10.00    --  -40.91 -38.00  30.00   99
 11  \w    -46.00 -19.00   1.00   10.00    --  -40.91  38.00-150.00   27
 12  \w    -16.00  29.00   1.00   10.00    --  -40.91  38.00-150.00   45
 13  \w     -8.00  72.00   1.00   10.00    --   40.91 -77.00-120.00   80
 14  \w     56.00 109.00   1.00   40.00    --  112.00-111.00 -30.00   53
 15  \w    103.00 178.00   1.00   40.00    --  112.00  77.00  60.00   75
 16  \w     82.00 107.00   1.00   40.00    --  112.00 -77.00  30.00   25
 17  \w     75.00 103.00   1.00   40.00    --  112.00-111.00 -90.00   28
 18  \w     38.00  64.00   1.00   40.00    --  112.00 -77.00  30.00   26
 19  \w    104.00 171.00   1.00   40.00    --  112.00  77.00 -30.00   67
 20  \w    105.00 171.00   1.00   40.00    --  112.00 111.00 -90.00   66
 21  \w     41.00 109.00   1.00   40.00    --  112.00-111.00-120.00   68
 22  \w     39.00 109.00   1.00   40.00    --  112.00-111.00   0.00   70
 23  \w    108.00 163.00   1.00   40.00    --  112.00  77.00-180.00   55
 24  \w    133.00 173.00   1.00   40.00    --  112.00 111.00  30.00   40
 25  \w    104.00 157.00   1.00   40.00    --  112.00  77.00-150.00   53
;
_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      0.0448342000
_diffrn_orient_matrix_UB_12      0.0087902000
_diffrn_orient_matrix_UB_13      0.0420149000
_diffrn_orient_matrix_UB_21      0.0022250000
_diffrn_orient_matrix_UB_22      -0.0506664000
_diffrn_orient_matrix_UB_23      0.0082120000
_diffrn_orient_matrix_UB_31      0.0991157000
_diffrn_orient_matrix_UB_32      -0.0027824000
_diffrn_orient_matrix_UB_33      -0.0160153000
_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  0.1140
_diffrn_reflns_av_unetI/netI     0.1353
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       42
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            91537
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.599
_diffrn_reflns_theta_min         3.009
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.002
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.36933
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.90a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale yellow'
_exptl_crystal_density_diffrn    1.242
_exptl_crystal_description       plate
_exptl_crystal_F_000             5533
_exptl_crystal_size_max          0.411
_exptl_crystal_size_mid          0.068
_exptl_crystal_size_min          0.059
_refine_diff_density_max         2.497
_refine_diff_density_min         -1.730
_refine_diff_density_rms         0.149
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.011
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1390
_refine_ls_number_reflns         29338
_refine_ls_number_restraints     1818
_refine_ls_restrained_S_all      1.005
_refine_ls_R_factor_all          0.1299
_refine_ls_R_factor_gt           0.0714
_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^)+(0.0779P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1696
_refine_ls_wR_factor_ref         0.2065
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16609
_reflns_number_total             29338
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05253b2.cif
_cod_data_source_block           nj1129
_cod_depositor_comments
'Adding full bibliography for 1570263--1570267.cif.'
_cod_original_cell_volume        14304.5(4)
_cod_original_formula_sum        'C97 H206 K2.70 N4 O31 Si6 U2'
_cod_database_code               1570266
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C100 H150 N4 O30 Si6 K3 U2'
_shelx_estimated_absorpt_t_max   0.650
_shelx_estimated_absorpt_t_min   0.138
_olex2_refinement_description
;
1. Restrained distances
 C100-C94
 1.5 with sigma of 0.02
 C95-C100
 2.5 with sigma of 0.02
 C99-C100
 2.5 with sigma of 0.02
 N5-C82 \\sim N5-C76 \\sim N5-C88 \\sim N6-C87 \\sim C81-N6 \\sim C93-N6
 with sigma of 0.02
 C82-C76 \\sim C76-C88
 with sigma of 0.02
 O31-C89 \\sim O31-C90 \\sim O32-C92 \\sim O32-C91 \\sim O30-C86 \\sim O30-C85
\\sim O28-C80 \\sim O28-C79
 \\sim O27-C78 \\sim O27-C77 \\sim O29-C83 \\sim O29-C84
 with sigma of 0.02
 C93-C92 \\sim C91-C90 \\sim C88-C89 \\sim C82-C83 \\sim C76-C77 \\sim C78-C79
\\sim C81-C80 \\sim C84-C85
 \\sim C86-C87
 with sigma of 0.02
 C87-C93 \\sim C93-C81
 with sigma of 0.02
 N4-N3 \\sim N2-N1
 with sigma of 0.02
 C9-C5 \\sim C7-C5 \\sim C10-C5 \\sim C8-C5 \\sim C6-C5 \\sim C11-C5
 with sigma of 0.02
 C9-C10 \\sim C10-C11 \\sim C9-C11
 with sigma of 0.02
 C6-C7 \\sim C7-C8 \\sim C6-C8
 with sigma of 0.02
 C69-C68 \\sim C71-C68 \\sim C70-C68
 with sigma of 0.02
 C71-C69 \\sim C69-C70 \\sim C70-C71
 with sigma of 0.02
2. Uiso/Uaniso restraints and constraints
Uanis(C55) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C79) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C85)
\\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C96) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
3. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(O2)=Sof(N3)=Sof(N4)=1-FVAR(1)
 Sof(O1)=Sof(N1)=Sof(N2)=FVAR(1)
 Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H9C)=Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=1-FVAR(2)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=FVAR(2)
 Fixed Sof: K2(0.7)
5.a Secondary CH2 refined with riding coordinates:
 C76(H76A,H76B), C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B), C80(H80A,
 H80B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C84(H84A,H84B),
 C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,H88B), C89(H89A,H89B),
  C90(H90A,H90B), C91(H91A,H91B), C92(H92A,H92B), C93(H93A,H93B)
5.b Aromatic/amide H refined with riding coordinates:
 C99(H99), C98(H98), C97(H97), C96(H96), C95(H95)
5.c Fitted hexagon refined as free rotating group:
 C94(C99,C98,C97,C96,C95)
5.d 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), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,
 H11C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C17(H17A,
 H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,H21C),
 C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C27(H27A,H27B,H27C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C31(H31A,
 H31B,H31C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C),
 C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C),
 C51(H51A,H51B,H51C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,
 H55C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C61(H61A,
 H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C65(H65A,H65B,H65C),
 C66(H66A,H66B,H66C), C67(H67A,H67B,H67C), C69(H69A,H69B,H69C), C70(H70A,H70B,
 H70C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,
 H75B,H75C), C100(H10D,H10E,H10F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 314 electrons were 
found in a volume of 2172\%A^3^ in 5 voids per unit cell. 
This is consistent with the presence of 
1[C7H8], 0.5[C7H8] per Asymmetric Unit 
which account for 300 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              79750
_shelx_fab_checksum              66443
_olex2_date_sample_data_collection 2023-04-20
_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 3.208
_oxdiff_exptl_absorpt_empirical_full_min 0.376