Cation assisted binding and cleavage of dinitrogen by uranium complexes
Jori, Nadir; Rajeshkumar, Thayalan; Scopelliti, Rosario; Z̆ivković, Ivica; Sienkiewicz, Andrzej; Maron, Laurent; Mazzanti, Marinella; Chemical Science 13 (2022) 9232–9242; doi:10.1039/D2SC02530B

data_1567303
_publ_section_title
;
 Cation assisted binding and cleavage of dinitrogen by uranium complexes
;
_journal_issue                   32
_journal_name_full               'Chemical Science'
_journal_page_first              9232
_journal_page_last               9242
_journal_paper_doi               10.1039/D2SC02530B
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C60 H135 N2 O21 Si5 U2, 4(Cs), C12 H27 O4 Si'
_chemical_formula_sum            'C72 H162 Cs4 N2 O25 Si6 U2'
_chemical_formula_weight         2632.26
_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             2021-10-15
_audit_creation_method
;
Olex2 1.5
(compiled 2021.08.20 svn.r13c46975 for OlexSys, GUI svn.r6405)
;
_audit_update_record
;
2022-02-24 deposited with the CCDC.	2022-07-14 downloaded from the CCDC.
;
_cell_angle_alpha                115.8481(18)
_cell_angle_beta                 95.2709(16)
_cell_angle_gamma                98.8528(18)
_cell_formula_units_Z            4
_cell_length_a                   14.2492(3)
_cell_length_b                   30.7972(6)
_cell_length_c                   30.9557(5)
_cell_measurement_reflns_used    22725
_cell_measurement_temperature    219.99(10)
_cell_measurement_theta_max      72.6640
_cell_measurement_theta_min      3.3230
_cell_volume                     11885.2(5)
_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 1.5 (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      219.99(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 0.972
_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      5.00  32.00   1.00    3.00    --  -40.91   8.00  72.00   27
  2  \w    -45.00   3.00   1.00    3.00    --  -40.91   8.00  72.00   48
  3  \w   -120.00 -38.00   1.00    3.00    --  -40.91  -8.00-101.00   82
  4  \w    -40.00 124.00   1.00    3.00    --   40.91   8.00  72.00  164
  5  \w     23.00  98.00   1.00   12.00    --  105.15  -8.00-101.00   75
  6  \w    100.00 178.00   1.00   12.00    --  105.15   8.00  72.00   78
  7  \w     28.00  68.00   1.00    3.00    --   40.91-125.00-180.00   40
  8  \w     28.00  86.00   1.00    3.00    --   40.91-125.00 -90.00   58
  9  \w     16.00  41.00   1.00    3.00    --   40.91  -8.00-101.00   25
 10  \w     16.00  82.00   1.00    3.00    --   40.91 -99.00   0.00   66
 11  \w     38.00  66.00   1.00    3.00    --   40.91 -99.00-180.00   28
 12  \w     28.00  55.00   1.00    3.00    --   40.91-125.00  90.00   27
 13  \w     33.00 130.00   1.00   12.00    --  105.15 -45.00-120.00   97
 14  \w    105.00 165.00   1.00   12.00    --  105.15  77.00 -90.00   60
 15  \w     75.00 109.00   1.00   12.00    --  105.15-111.00-150.00   34
 16  \w    103.00 176.00   1.00   12.00    --  105.15  77.00-180.00   73
 17  \w     36.00  63.00   1.00   12.00    --  105.15-111.00  60.00   27
 18  \w     80.00 109.00   1.00   12.00    --  105.15-111.00  60.00   29
 19  \w     24.00  99.00   1.00   12.00    --  105.15 -94.00 -90.00   75
 20  \w     69.00  95.00   1.00   12.00    --  105.15 -61.00-180.00   26
 21  \w     79.00 108.00   1.00   12.00    --  105.15-111.00 120.00   29
 22  \w     32.00 114.00   1.00   12.00    --  105.15 -45.00 120.00   82
 23  \w     30.00  64.00   1.00   12.00    --  105.15-111.00 120.00   34
 24  \w     84.00 109.00   1.00   12.00    --  105.15-111.00 -60.00   25
 25  \w    113.00 173.00   1.00   12.00    --  105.15 111.00-120.00   60
 26  \w     55.00 134.00   1.00   12.00    --  105.15 -77.00 -30.00   79
 27  \w     61.00 109.00   1.00   12.00    --  105.15-111.00-180.00   48
 28  \w     35.00  62.00   1.00   12.00    --  105.15-111.00-150.00   27
;
_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      0.0512310000
_diffrn_orient_matrix_UB_12      0.0445109000
_diffrn_orient_matrix_UB_13      -0.0057691000
_diffrn_orient_matrix_UB_21      -0.0945027000
_diffrn_orient_matrix_UB_22      0.0187256000
_diffrn_orient_matrix_UB_23      0.0019013000
_diffrn_orient_matrix_UB_31      0.0285027000
_diffrn_orient_matrix_UB_32      0.0301581000
_diffrn_orient_matrix_UB_33      0.0558752000
_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  0.0838
_diffrn_reflns_av_unetI/netI     0.1121
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            105668
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.818
_diffrn_reflns_theta_min         2.871
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.051
_exptl_absorpt_correction_T_max  0.787
_exptl_absorpt_correction_T_min  0.191
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.118a (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 intense yellow'
_exptl_crystal_density_diffrn    1.471
_exptl_crystal_description       prism
_exptl_crystal_F_000             5184
_exptl_crystal_size_max          0.596
_exptl_crystal_size_mid          0.081
_exptl_crystal_size_min          0.063
_refine_diff_density_max         2.984
_refine_diff_density_min         -2.052
_refine_diff_density_rms         0.209
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.963
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1999
_refine_ls_number_reflns         46105
_refine_ls_number_restraints     2858
_refine_ls_restrained_S_all      0.957
_refine_ls_R_factor_all          0.1044
_refine_ls_R_factor_gt           0.0645
_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^)+(0.0853P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1541
_refine_ls_wR_factor_ref         0.1807
_reflns_Friedel_coverage         0.000
_reflns_number_gt                29497
_reflns_number_total             46105
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02530b2.cif
_cod_data_source_block           nj775_2
_cod_depositor_comments
;
Adding full bibliography for 1567298--1567305.cif.

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C144 H324 Cs8 N4 O50 Si12 U4'
_cod_original_formula_weight         5264.53
_cod_original_formula_moiety         'C144 H324 Cs8 N4 O50 Si12 U4'
_cod_original_formula_units_Z            2
_cod_original_cell_volume        11885.2(4)
_cod_database_code               1567303
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C72 H162 O25 N2 Cs4 U2 Si6'
_shelx_estimated_absorpt_t_max   0.396
_shelx_estimated_absorpt_t_min   0.033
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C206-C205 = C207-C205 = C208-C205
 1.54 with sigma of 0.02
 C206-C207 \\sim C207-C208
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O104) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C66)
\\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C106) \\sim Ueq,
Uanis(C109) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(O204) \\sim Ueq,
Uanis(C143) \\sim Ueq, Uanis(C182) \\sim Ueq, Uanis(C183) \\sim Ueq,
Uanis(C202) \\sim Ueq, Uanis(C222) \\sim Ueq, Uanis(C207) \\sim Ueq,
Uanis(C210) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. 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
5.a Me refined with riding coordinates:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,
 H12B,H12C), 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), 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), 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), C81(H81A,H81B,H81C), 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),
 C102(H10D,H10E,H10F), C103(H10G,H10H,H10I), C104(H10J,H10K,H10L), C106(H10M,
 H10N,H10O), C107(H10P,H10Q,H10R), C108(H10S,H10T,H10U), C110(H11D,H11E,H11F),
 C111(H11G,H11H,H11I), C112(H11J,H11K,H11L), C122(H12D,H12E,H12F), C123(H12G,
 H12H,H12I), C124(H12J,H12K,H12L), C126(H12M,H12N,H12O), C127(H12P,H12Q,H12R),
 C128(H12S,H12T,H12U), C130(H13A,H13B,H13C), C131(H13D,H13E,H13F), C132(H13G,
 H13H,H13I), C142(H14A,H14B,H14C), C143(H14D,H14E,H14F), C144(H14G,H14H,H14I),
 C146(H14J,H14K,H14L), C147(H14M,H14N,H14O), C148(H14P,H14Q,H14R), C150(H15A,
 H15B,H15C), C151(H15D,H15E,H15F), C152(H15G,H15H,H15I), C162(H16A,H16B,H16C),
 C163(H16D,H16E,H16F), C164(H16G,H16H,H16I), C166(H16J,H16K,H16L), C167(H16M,
 H16N,H16O), C168(H16P,H16Q,H16R), C170(H17A,H17B,H17C), C171(H17D,H17E,H17F),
 C182(H18A,H18B,H18C), C183(H18D,H18E,H18F), C184(H18G,H18H,H18I), C186(H18J,
 H18K,H18L), C187(H18M,H18N,H18O), C188(H18P,H18Q,H18R), C190(H19A,H19B,H19C),
 C191(H19D,H19E,H19F), C192(H19G,H19H,H19I), C202(H20A,H20B,H20C), C203(H20D,
 H20E,H20F), C204(H20G,H20H,H20I), C206(H20J,H20K,H20L), C207(H20M,H20N,H20O),
 C208(H20P,H20Q,H20R), C210(H21A,H21B,H21C), C211(H21D,H21E,H21F), C212(H21G,
 H21H,H21I), C222(H22D,H22E,H22F), C223(H22G,H22H,H22I), C224(H22J,H22K,H22L),
 C226(H22M,H22N,H22O), C227(H22P,H22Q,H22R), C228(H22S,H22T,H22U), C230(H23D,
 H23E,H23F), C231(H23G,H23H,H23I), C232(H23J,H23K,H23L), C172(H17G,H17H,H17I)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 200 electrons were 
found in a volume of 1836\%A^3^ in 6 voids per unit cell. 
This is consistent with the presence of 
1[C7H8] per Asymmetric Unit 
which account for 200 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              81583
_shelx_hkl_checksum              45901
_shelx_fab_checksum              79215
_olex2_date_sample_data_collection 2021-10-01
_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 3.888
_oxdiff_exptl_absorpt_empirical_full_min 0.451