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_1567300
_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 Na O25 Si6 U2, 1.25[C4 H10 O]'
_chemical_formula_sum            'C72 H162 Na O25 Si6 U2'
_chemical_formula_weight         2095.60
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-06-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-02-24 deposited with the CCDC.	2022-07-14 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.148(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.8302(3)
_cell_length_b                   31.0949(4)
_cell_length_c                   14.0653(4)
_cell_measurement_reflns_used    47479
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.2510
_cell_measurement_theta_min      3.4310
_cell_volume                     5333.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.93a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.988
_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   -116.00 -82.00   1.00    2.50    --  -43.01 -39.00-130.00   34
  2  \w    -68.00  30.00   1.00    2.50    --  -43.01  39.00  24.00   98
  3  \w    -73.00 -23.00   1.00    2.50    --  -43.01 -39.00-130.00   50
  4  \w     18.00 117.00   1.00    2.50    --   43.01  39.00  24.00   99
  5  \w     58.00 129.00   1.00   10.00    --  103.80 -39.00-130.00   71
  6  \w    104.00 129.00   1.00   10.00    --  103.80  39.00  24.00   25
  7  \w     -1.00  24.00   1.00    2.50    --   34.00  86.00 133.17   25
  8  \w     -5.00  20.00   1.00    2.50    --   34.00  94.00  35.17   25
  9  \w     -1.00  24.00   1.00    2.50    --   34.00  86.00 -47.53   25
 10  \w      0.00  28.00   1.00    2.50    --   34.00  90.00   6.83   28
 11  \w      8.00  33.00   1.00    2.50    --   42.00  83.00  62.32   25
 12  \w     28.00  95.00   1.00    2.50    --   43.01-125.00  90.00   67
 13  \w    -29.00  31.00   1.00    2.50    --   43.01 -39.00-130.00   60
 14  \w      3.00  75.00   1.00    2.50    --   43.01  19.00 -60.00   72
 15  \w     93.00 122.00   1.00    2.50    --   43.01  19.00 -60.00   29
 16  \w     28.00  96.00   1.00    2.50    --   43.01-125.00-150.00   68
 17  \w     16.00  41.00   1.00    2.50    --   50.00  81.00  35.49   25
 18  \w     16.00  42.00   1.00    2.50    --   50.00  81.00 -48.66   26
 19  \w     16.00  41.00   1.00    2.50    --   50.00  81.00  77.30   25
 20  \w     16.00  41.00   1.00    2.50    --   50.00  82.00 122.17   25
 21  \w     16.00  41.00   1.00    2.50    --   50.00  82.00-141.62   25
 22  \w     16.00  41.00   1.00    2.50    --   50.00  82.00 173.55   25
 23  \w     16.00  41.00   1.00    2.50    --   50.00  82.00-105.65   25
 24  \w     27.00  97.00   1.00    2.50    --   58.00  71.00-154.09   70
 25  \w    104.00 129.00   1.00    2.50    --   62.00  71.00  -1.42   25
 26  \w     31.00  57.00   1.00    2.50    --   62.00  71.00  -1.42   26
 27  \w     31.00  69.00   1.00    2.50    --   62.00  69.00 -40.28   38
 28  \w     35.00  62.00   1.00    2.50    --   66.00  71.00 -84.66   27
 29  \w     39.00  67.00   1.00    2.50    --   70.00  71.00  93.76   28
 30  \w     40.00  66.00   1.00    2.50    --   70.00  69.00 120.36   26
 31  \w     39.00  70.00   1.00    2.50    --   70.00  71.00 153.93   31
 32  \w     39.00  65.00   1.00    2.50    --   70.00  69.00  15.25   26
 33  \w     39.00  66.00   1.00    2.50    --   70.00  71.00-115.87   27
 34  \w     40.00  65.00   1.00    2.50    --   70.00  69.00  57.32   25
 35  \w     43.00  76.00   1.00   10.00    --   74.00  69.00  76.76   33
 36  \w    112.00 141.00   1.00   10.00    --   78.00  68.00 -66.69   29
 37  \w     49.00  74.00   1.00   10.00    --   78.00  68.00 -66.69   25
 38  \w     47.00  89.00   1.00   10.00    --   78.00  70.00-150.82   42
 39  \w     47.00  74.00   1.00   10.00    --   78.00  69.00-176.49   27
 40  \w     51.00  77.00   1.00   10.00    --   82.00  70.00 -53.94   26
 41  \w     52.00  79.00   1.00   10.00    --   82.00  65.00  32.06   27
 42  \w     55.00  81.00   1.00   10.00    --   86.00  70.00 -46.58   26
 43  \w     57.00  82.00   1.00   10.00    --   86.00  66.00 124.05   25
 44  \w     56.00  90.00   1.00   10.00    --   86.00  66.00  58.49   34
 45  \w     57.00  84.00   1.00   10.00    --   86.00  61.00 103.27   27
 46  \w     59.00  86.00   1.00   10.00    --   90.00  70.00 144.23   27
 47  \w     62.00  88.00   1.00   10.00    --   90.00  58.00-141.91   26
 48  \w    117.00 144.00   1.00   10.00    --   90.00  66.00 177.68   27
 49  \w     59.00  85.00   1.00   10.00    --   90.00  70.00-128.15   26
 50  \w     61.00  86.00   1.00   10.00    --   90.00  66.00 177.68   25
 51  \w     65.00  92.00   1.00   10.00    --   94.00  63.00   9.47   27
 52  \w     63.00  89.00   1.00   10.00    --   94.00  70.00-103.45   26
 53  \w     66.00 167.00   1.00   10.00    --   94.00  67.00-117.60  101
 54  \w    112.00 168.00   1.00   10.00    --   94.00  71.00 -12.57   56
 55  \w     63.00 102.00   1.00   10.00    --   94.00  71.00 -12.57   39
 56  \w     63.00 152.00   1.00   10.00    --   94.00  69.00 -31.12   89
 57  \w    107.00 137.00   1.00   10.00    --   98.00  69.00  90.73   30
 58  \w     67.00  93.00   1.00   10.00    --   98.00  69.00  90.73   26
 59  \w     41.00  93.00   1.00   10.00    --  103.80 -94.00 -90.00   52
 60  \w     29.00 108.00   1.00   10.00    --  103.80-111.00  60.00   79
 61  \w     22.00 104.00   1.00   10.00    --  103.80 -94.00 150.00   82
 62  \w     22.00  70.00   1.00   10.00    --  103.80 -94.00-150.00   48
 63  \w     77.00 146.00   1.00   10.00    --  103.80  55.00 -74.03   69
 64  \w     60.00 108.00   1.00   10.00    --  103.80-111.00   0.00   48
 65  \w     75.00 152.00   1.00   10.00    --  103.80  61.00 150.00   77
 66  \w     76.00 152.00   1.00   10.00    --  103.80  61.00-150.00   76
 67  \w     75.00 176.00   1.00   10.00    --  103.80  61.00  60.00  101
 68  \w    118.00 156.00   1.00   10.00    --  103.80  66.00 110.51   38
 69  \w     74.00 102.00   1.00   10.00    --  103.80  66.00 110.51   28
 70  \w     75.00 144.00   1.00   10.00    --  103.80  61.00  30.00   69
 71  \w     28.00 108.00   1.00   10.00    --  103.80-111.00 -90.00   80
 72  \w     73.00 176.00   1.00   10.00    --  103.80  68.00 -65.30  103
 73  \w    127.00 172.00   1.00   10.00    --  103.80  61.00-180.00   45
 74  \w     76.00 120.00   1.00   10.00    --  103.80  61.00-180.00   44
 75  \w     22.00 107.00   1.00   10.00    --  103.80 -94.00  90.00   85
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1194851000
_diffrn_orient_matrix_UB_12      -0.0148629000
_diffrn_orient_matrix_UB_13      -0.0419295000
_diffrn_orient_matrix_UB_21      -0.0007840000
_diffrn_orient_matrix_UB_22      0.0195758000
_diffrn_orient_matrix_UB_23      0.1002652000
_diffrn_orient_matrix_UB_31      -0.0409037000
_diffrn_orient_matrix_UB_32      0.0429981000
_diffrn_orient_matrix_UB_33      -0.0602493000
_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     0.0338
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -37
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            29907
_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         72.888
_diffrn_reflns_theta_min         3.564
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.643
_exptl_absorpt_correction_T_max  0.797
_exptl_absorpt_correction_T_min  0.168
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.93a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on Gaussian integration over
a multifaceted crystal model.
Empirical absorption correction using spherical harmonics
as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            'clear intense red'
_exptl_crystal_density_diffrn    1.305
_exptl_crystal_description       prism
_exptl_crystal_F_000             2146
_exptl_crystal_size_max          0.231
_exptl_crystal_size_mid          0.094
_exptl_crystal_size_min          0.06
_refine_diff_density_max         2.665
_refine_diff_density_min         -1.980
_refine_diff_density_rms         0.205
_refine_ls_abs_structure_details
;
 Flack x determined using 7738 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.015(7)
_refine_ls_extinction_coef       0.00084(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1010
_refine_ls_number_reflns         29907
_refine_ls_number_restraints     1694
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0895
_refine_ls_R_factor_gt           0.0809
_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^)+(0.1501P)^2^+19.9122P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2189
_refine_ls_wR_factor_ref         0.2285
_reflns_Friedel_coverage         0.930
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.956
_reflns_number_gt                26324
_reflns_number_total             29907
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.7060\% 
around [0.01 1.00 -0.01] (reciprocal) or [0.01 1.00 -0.04] (direct)
;
_cod_data_source_file            d2sc02530b2.cif
_cod_data_source_block           nj599_2_twin1_hklf5_sq
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 7556 2019-12-06 15:28:31Z antanas 

 Adding full bibliography for 1567298--1567305.cif.
;
_cod_original_cell_volume        5333.4(2)
_cod_database_code               1567300
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C72 H162 Na O25 Si6 U2'
_shelx_estimated_absorpt_t_max   0.595
_shelx_estimated_absorpt_t_min   0.214
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.552(2)
 0.448(2)
2. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C68-C65 = C66-C65 = C67-C65 = C62-C61 = C64-C61 = C63-C61 = C71-C69 = C70-C69
 = C72-C69 = C101-C103 = C101-C104 = C101-C102 = C110-C109 = C111-C109 = C112-
 C109 = C107-C105 = C108-C105 = C106-C105 = C87-C85 = C86-C85 = C88-C85 = C89-
 C90 = C91-C89 = C92-C89 = C83-C81 = C81-C84 = C82-C81 = C1-C3 = C1-C2 = C1-C4 =
  C5-C6 = C7-C5 = C8-C5 = C10-C9 = C11-C9 = C12-C9 = C49-C51 = C49-C52 = C49-
 C50 = C42-C41 = C41-C44 = C41-C43 = C47-C45 = C46-C45 = C48-C45 = C28-C25 =
 C27-C25 = C26-C25 = C29-C32 = C30-C29 = C29-C31 = C23-C21 = C24-C21 = C22-C21
 1.54 with sigma of 0.02
 O42-C41
 1.45 with sigma of 0.01
 Si3-O44 = Si3-O43 = Si3-O42
 1.6 with sigma of 0.02
 O44-C49
 1.45 with sigma of 0.01
 C50-C52 = C52-C51 = C51-C50
 2.5 with sigma of 0.01
 C23-C24 \\sim C24-C22 \\sim C22-C23
 with sigma of 0.02
 C88-C87 \\sim C87-C86 \\sim C86-C88
 with sigma of 0.02
 C112-C110 \\sim C110-C111 \\sim C111-C112
 with sigma of 0.02
 C66-C68 \\sim C68-C67 \\sim C67-C66
 with sigma of 0.02
 C91-C92 \\sim C92-C90 \\sim C90-C91
 with sigma of 0.02
 C26-C27 \\sim C27-C28 \\sim C28-C26
 with sigma of 0.02
 C46-C48 \\sim C48-C47 \\sim C47-C46
 with sigma of 0.02
 C83-C84 \\sim C84-C82 \\sim C82-C83
 with sigma of 0.02
 C30-C31 \\sim C31-C32 \\sim C32-C30
 with sigma of 0.02
 C71-C72 \\sim C72-C70 \\sim C70-C71
 with sigma of 0.02
 C51-C50 \\sim C50-C52 \\sim C52-C51
 with sigma of 0.02
 C103-C102 \\sim C102-C104 \\sim C104-C103
 with sigma of 0.02
 C12-C10 \\sim C10-C11 \\sim C11-C12
 with sigma of 0.02
 C106-C108 \\sim C108-C107 \\sim C107-C106
 with sigma of 0.02
 C4-C2 \\sim C2-C3 \\sim C3-C4
 with sigma of 0.02
 C43-C44 \\sim C44-C42 \\sim C42-C43
 with sigma of 0.02
 C8-C7 \\sim C7-C6 \\sim C6-C8
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002 within 2A
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6.a Me refined with riding coordinates:
 C22(H22A,H22B,H22C)
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), 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)
;
_shelx_res_checksum              21692
_shelx_hkl_checksum              74308
_shelx_fab_checksum              82713
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 4.051
_oxdiff_exptl_absorpt_empirical_full_min 0.331
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2