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_1567298
_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         'C72 H162 O25 Rb2 Si6 U2, 2(C3 H7)'
_chemical_formula_sum            'C78 H176 O25 Rb2 Si6 U2'
_chemical_formula_weight         2329.72
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-02-21
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-02-24 deposited with the CCDC.	2022-07-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.0486(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.04416(15)
_cell_length_b                   29.0153(3)
_cell_length_c                   27.5170(3)
_cell_measurement_reflns_used    27315
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.5750
_cell_measurement_theta_min      3.4880
_cell_volume                     11211.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.121a (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      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.997
_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    -11.00  18.00   1.00    2.00    --  -40.91  71.00 -45.00   29
  2  \w   -115.00 -15.00   1.00    2.00    --  -40.91 -71.00-176.00  100
  3  \w    -47.00 -21.00   1.00    2.00    --  -40.91  71.00 -45.00   26
  4  \w     45.00 126.00   1.00    8.00    --  105.15 -71.00-176.00   81
  5  \w     74.00 178.00   1.00    8.00    --  105.15  71.00 -45.00  104
  6  \w     62.00  95.00   1.00    2.00    --   40.91  71.00 -45.00   33
  7  \w      7.00  77.00   1.00    2.00    --   40.91 -99.00  30.00   70
  8  \w      8.00  52.00   1.00    2.00    --   40.91 -99.00   0.00   44
  9  \w     27.00  96.00   1.00    2.00    --   40.91-125.00-150.00   69
 10  \w     30.00  57.00   1.00    8.00    --  105.15-111.00  30.00   27
 11  \w    115.00 177.00   1.00    8.00    --  105.15  77.00-150.00   62
 12  \w    103.00 171.00   1.00    8.00    --  105.15  77.00   0.00   68
 13  \w     76.00 166.00   1.00    8.00    --  105.15  61.00 -90.00   90
 14  \w    106.00 132.00   1.00    8.00    --  105.15 111.00 150.00   26
 15  \w    141.00 166.00   1.00    8.00    --  105.15 111.00 150.00   25
 16  \w     80.00 107.00   1.00    8.00    --  105.15-111.00  30.00   27
 17  \w     91.00 122.00   1.00    8.00    --  105.15 178.00-150.00   31
;
_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      0.0201352000
_diffrn_orient_matrix_UB_12      -0.0153380000
_diffrn_orient_matrix_UB_13      0.0528053000
_diffrn_orient_matrix_UB_21      -0.0722514000
_diffrn_orient_matrix_UB_22      -0.0395683000
_diffrn_orient_matrix_UB_23      -0.0062587000
_diffrn_orient_matrix_UB_31      0.0801842000
_diffrn_orient_matrix_UB_32      -0.0318765000
_diffrn_orient_matrix_UB_33      -0.0174823000
_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  0.0449
_diffrn_reflns_av_unetI/netI     0.0415
_diffrn_reflns_Laue_measured_fraction_full 0.997
_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       28
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            57578
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.781
_diffrn_reflns_theta_min         3.046
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.209
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.046
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.121a (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            'clear dark red'
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_description       plate
_exptl_crystal_F_000             4744
_exptl_crystal_size_max          0.518
_exptl_crystal_size_mid          0.437
_exptl_crystal_size_min          0.055
_refine_diff_density_max         3.154
_refine_diff_density_min         -1.551
_refine_diff_density_rms         0.188
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1145
_refine_ls_number_reflns         21687
_refine_ls_number_restraints     1446
_refine_ls_restrained_S_all      1.080
_refine_ls_R_factor_all          0.0609
_refine_ls_R_factor_gt           0.0555
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0872P)^2^+50.7878P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1551
_refine_ls_wR_factor_ref         0.1592
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19605
_reflns_number_total             21687
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02530b2.cif
_cod_data_source_block           nj871cu
_cod_depositor_comments
'Adding full bibliography for 1567298--1567305.cif.'
_cod_database_code               1567298
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C78 H176 O25 Si6 Rb2 U2'
_shelx_estimated_absorpt_t_max   0.604
_shelx_estimated_absorpt_t_min   0.077
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C123-C122 = C122-C121
 1.54 with sigma of 0.02
 C33-C20 = C34-C33
 1.54 with sigma of 0.02
 C7-C5 \\sim C5-C14 \\sim C8-C5 \\sim C5-C15 \\sim C6-C5 \\sim C5-C13
 with sigma of 0.02
 C7-C6 \\sim C6-C8 \\sim C7-C8
 with sigma of 0.02
 C14-C13 \\sim C13-C15 \\sim C14-C15
 with sigma of 0.02
 C18-C19 \\sim C19-C17 \\sim C17-C18
 with sigma of 0.02
 C71-C72 \\sim C72-C70 \\sim C70-C71
 with sigma of 0.02
 C71-C69 \\sim C72-C69 \\sim C70-C69 \\sim C18-C16 \\sim C17-C16 \\sim C19-C16
 with sigma of 0.02
 C106-C105 \\sim C107-C105 \\sim C108-C105
 with sigma of 0.02
 C106-C108 \\sim C108-C107 \\sim C106-C107
 with sigma of 0.02
 O64-C69 \\sim O64-C16
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C5 \\sim C6 \\sim C7 \\sim C8 \\sim C13 \\sim C14 \\sim C15: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C105 \\sim C106 \\sim C107 \\sim C108: within 2A with sigma of 0.01 and sigma
for terminal atoms of 2 within 2A
C16 \\sim C17 \\sim C18 \\sim C19 \\sim C69 \\sim C70 \\sim C71 \\sim C72:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C91) \\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C110) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C63) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
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. Others
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=1-FVAR(1)
 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(1)
 Sof(C16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=1-FVAR(2)
 Sof(C69)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C71)=Sof(H71A)=Sof(H71B)=
 Sof(H71C)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C34(H34A,H34B), C121(H12D,H12E), C122(H12F,H12G)
6.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), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), 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), 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), 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), C20(H20A,H20B,H20C), C123(H12H,H12I,H12J)
;
_shelx_res_checksum              3870
_shelx_hkl_checksum              38069
_olex2_date_sample_data_collection 2022-01-19
_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 6.904
_oxdiff_exptl_absorpt_empirical_full_min 0.631