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_1567302
_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 O26 Rb2 Si6 U2, 2(C7 H8)'
_chemical_formula_sum            'C86 H178 O26 Rb2 Si6 U2'
_chemical_formula_weight         2443.81
_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             2022-02-14
_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                79.6962(13)
_cell_angle_beta                 89.4157(13)
_cell_angle_gamma                67.0260(16)
_cell_formula_units_Z            2
_cell_length_a                   14.4840(2)
_cell_length_b                   17.5730(3)
_cell_length_c                   25.4883(4)
_cell_measurement_reflns_used    42188
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      75.9620
_cell_measurement_theta_min      3.4940
_cell_volume                     5863.83(18)
_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 0.989
_diffrn_measured_fraction_theta_max 0.973
_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    -72.00  18.00   1.00    3.00    --  -40.41  96.00  50.00   90
  2  \w     40.00  79.00   1.00    3.00    --   40.41 -96.00 -58.00   39
  3  \w    114.00 141.00   1.00   12.00    --  112.00  96.00  50.00   27
  4  \w     79.00 106.00   1.00   12.00    --  112.00 -96.00 -58.00   27
  5  \w   -113.00 -22.00   1.00    3.00    --  -40.41 -38.00 -30.00   91
  6  \w    -63.00  26.00   1.00    3.00    --  -40.41  38.00 -30.00   89
  7  \w     17.00 112.00   1.00    3.00    --   40.41  57.00-180.00   95
  8  \w     17.00  42.00   1.00    3.00    --   40.41  38.00 -60.00   25
  9  \w     29.00  75.00   1.00    3.00    --   40.41-125.00-120.00   46
 10  \w     29.00  72.00   1.00   12.00    --  112.00 -94.00 -30.00   43
 11  \w    134.00 177.00   1.00   12.00    --  112.00  30.00 120.00   43
 12  \w     82.00 128.00   1.00   12.00    --  112.00 -45.00 -60.00   46
 13  \w     58.00 108.00   1.00   12.00    --  112.00-111.00-180.00   50
 14  \w    128.00 178.00   1.00   12.00    --  112.00  30.00   0.00   50
 15  \w     51.00 109.00   1.00   12.00    --  112.00-111.00  60.00   58
 16  \w     59.00 104.00   1.00   12.00    --  112.00 -94.00-150.00   45
 17  \w     63.00 111.00   1.00   12.00    --  112.00 -45.00  30.00   48
 18  \w     38.00  70.00   1.00   12.00    --  112.00-111.00 -60.00   32
 19  \w    101.00 128.00   1.00   12.00    --  112.00  30.00 120.00   27
 20  \w    109.00 169.00   1.00   12.00    --  112.00 111.00-120.00   60
 21  \w     80.00 109.00   1.00   12.00    --  112.00-111.00-150.00   29
 22  \w     99.00 126.00   1.00   12.00    --  112.00  30.00   0.00   27
 23  \w    105.00 166.00   1.00   12.00    --  112.00 111.00-180.00   61
 24  \w    105.00 150.00   1.00   12.00    --  112.00 111.00 120.00   45
 25  \w     41.00  66.00   1.00   12.00    --  112.00 -61.00-180.00   25
 26  \w     87.00 137.00   1.00   12.00    --  112.00 -61.00-180.00   50
 27  \w     47.00  77.00   1.00   12.00    --  112.00 -94.00-180.00   30
 28  \w     63.00 133.00   1.00   12.00    --  112.00 178.00-120.00   70
 29  \w     84.00 171.00   1.00   12.00    --  112.00  30.00  60.00   87
 30  \w    103.00 137.00   1.00   12.00    --  112.00  77.00 -90.00   34
 31  \w     29.00  79.00   1.00   12.00    --  112.00 -94.00-120.00   50
 32  \w     76.00 109.00   1.00   12.00    --  112.00-111.00  90.00   33
 33  \w     46.00 107.00   1.00   12.00    --  112.00-111.00  30.00   61
 34  \w     83.00 109.00   1.00   12.00    --  112.00-111.00 -60.00   26
 35  \w    132.00 174.00   1.00   12.00    --  112.00  77.00  30.00   42
 36  \w     65.00  90.00   1.00   12.00    --  112.00 178.00 -30.00   25
 37  \w    128.00 166.00   1.00   12.00    --  112.00  45.00-180.00   38
 38  \w     68.00 107.00   1.00   12.00    --  112.00-111.00   0.00   39
 39  \w     45.00  70.00   1.00   12.00    --  112.00 -45.00 -60.00   25
 40  \w     37.00  64.00   1.00   12.00    --  112.00-111.00 -90.00   27
 41  \w     66.00 109.00   1.00   12.00    --  112.00-111.00 -90.00   43
 42  \w     53.00  78.00   1.00   12.00    --  112.00-111.00 150.00   25
 43  \w     31.00 107.00   1.00   12.00    --  112.00 -94.00  90.00   76
 44  \w     61.00  88.00   1.00   12.00    --  112.00 -94.00 120.00   27
 45  \w     43.00 139.00   1.00   12.00    --  112.00 -30.00  60.00   96
;
_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      -0.0011001000
_diffrn_orient_matrix_UB_12      -0.0452503000
_diffrn_orient_matrix_UB_13      0.0575050000
_diffrn_orient_matrix_UB_21      -0.1157263000
_diffrn_orient_matrix_UB_22      0.0408613000
_diffrn_orient_matrix_UB_23      -0.0039933000
_diffrn_orient_matrix_UB_31      -0.0032484000
_diffrn_orient_matrix_UB_32      -0.0754245000
_diffrn_orient_matrix_UB_33      -0.0216245000
_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  0.0269
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            68433
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.112
_diffrn_reflns_theta_min         2.999
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.795
_exptl_absorpt_correction_T_max  0.280
_exptl_absorpt_correction_T_min  0.104
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.121a (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 pale green'
_exptl_crystal_density_diffrn    1.384
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2488
_exptl_crystal_size_max          0.412
_exptl_crystal_size_mid          0.282
_exptl_crystal_size_min          0.267
_refine_diff_density_max         3.019
_refine_diff_density_min         -2.322
_refine_diff_density_rms         0.123
_refine_ls_extinction_coef       0.000048(7)
_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   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1228
_refine_ls_number_reflns         23858
_refine_ls_number_restraints     1603
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0391
_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^)+(0.0566P)^2^+17.4889P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1058
_refine_ls_wR_factor_ref         0.1093
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21871
_reflns_number_total             23858
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02530b2.cif
_cod_data_source_block           nj844
_cod_depositor_comments
'Adding full bibliography for 1567298--1567305.cif.'
_cod_original_cell_volume        5863.85(18)
_cod_database_code               1567302
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C86 H172 O26 Si6 Rb2 U2'
_shelx_estimated_absorpt_t_max   0.180
_shelx_estimated_absorpt_t_min   0.107
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 U1-O7 \\sim U1-O5 \\sim U1-O6 \\sim U2-O6 \\sim U2-O5 \\sim U2-O7 \\sim U2-O8
\\sim U1-O8
 with sigma of 0.02
 C50-C51 \\sim C51-C52 \\sim C50-C52
 with sigma of 0.02
 O44-C16 \\sim O44-C49
 with sigma of 0.02
 C19-C16 \\sim C17-C16 \\sim C37-C16 \\sim C50-C49 \\sim C51-C49 \\sim C52-C49
 with sigma of 0.02
 C17-C19 \\sim C19-C37 \\sim C17-C37
 with sigma of 0.02
 C13-C15 \\sim C15-C14 \\sim C13-C14
 with sigma of 0.02
 C110-C111 \\sim C111-C112 \\sim C110-C112
 with sigma of 0.02
 C110-C109 \\sim C13-C109 \\sim C111-C109 \\sim C14-C109 \\sim C112-C109 \\sim
C15-C109
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O5 \\sim O6 \\sim O7 \\sim O8: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132 \\sim C133 \\sim C134: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C16 \\sim C17 \\sim C19 \\sim C37 \\sim C49 \\sim C50 \\sim C51 \\sim C52:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C13 \\sim C14 \\sim C15 \\sim C109 \\sim C110 \\sim C111 \\sim C112: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
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(O6)=Sof(O8)=1-FVAR(1)
 Sof(O5)=Sof(O7)=FVAR(1)
 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(2)
 Sof(C110)=Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C111)=Sof(H11G)=Sof(H11H)=
 Sof(H11I)=Sof(C112)=Sof(H11J)=Sof(H11K)=Sof(H11L)=FVAR(2)
 Sof(C16)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 Sof(H19C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=1-FVAR(3)
 Sof(C49)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C51)=Sof(H51A)=Sof(H51B)=
 Sof(H51C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=FVAR(3)
 Fixed X: U1(0.737889) U2(0.69263)
 Fixed Y: U1(0.3807) U2(0.58012)
 Fixed Z: U1(0.28168) U2(0.21527)
6.a Aromatic/amide H refined with riding coordinates:
 C122(H122), C123(H123), C124(H124), C125(H125), C126(H126), C129(H129),
 C130(H130), C131(H131), C132(H132), C133(H133)
6.b Fitted hexagon refined as free rotating group:
 C121(C122,C123,C124,C125,C126)
6.c 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), 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),
 C37(H37A,H37B,H37C), 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), C127(H12D,H12E,H12F), C134(H13D,H13E,H13F)
;
_shelx_res_checksum              40929
_shelx_hkl_checksum              12865
_olex2_date_sample_data_collection 2021-11-30
_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 1.691
_oxdiff_exptl_absorpt_empirical_full_min 0.662