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_1567301
_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         '2(C36 H81 Cs O13 Si3 U), C7 H8'
_chemical_formula_sum            'C79 H170 Cs2 O26 Si6 U2'
_chemical_formula_weight         2446.56
_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             2022-02-11
_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                88.132(2)
_cell_angle_beta                 79.130(2)
_cell_angle_gamma                60.661(3)
_cell_formula_units_Z            2
_cell_length_a                   14.3992(5)
_cell_length_b                   14.5329(5)
_cell_length_c                   30.7352(7)
_cell_measurement_reflns_used    24336
_cell_measurement_temperature    140.0(3)
_cell_measurement_theta_max      30.1230
_cell_measurement_theta_min      2.8120
_cell_volume                     5492.7(3)
_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      140.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     -9.00  56.00   1.00   20.00    --  -17.94  38.00   2.00   65
  2  \w    -46.00  22.00   1.00   20.00    --   19.03 -38.00-151.00   68
  3  \w     -5.00  61.00   1.00   20.00    --   19.03  38.00   2.00   66
  4  \w    -37.00   8.00   1.00   20.00    --  -17.94 -77.00 -30.00   45
  5  \w    -48.00  20.00   1.00   20.00    --  -17.94  77.00 120.00   68
  6  \w    -46.00  19.00   1.00   20.00    --  -17.94  77.00  60.00   65
  7  \w    -39.00   8.00   1.00   20.00    --  -17.94 -77.00-150.00   47
  8  \w    -66.00 -39.00   1.00   20.00    --  -17.94 -37.00 -90.00   27
  9  \w    -39.00  -6.00   1.00   20.00    --  -17.94 -77.00 150.00   33
;
_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      0.0267253000
_diffrn_orient_matrix_UB_12      0.0304416000
_diffrn_orient_matrix_UB_13      -0.0030152000
_diffrn_orient_matrix_UB_21      -0.0483177000
_diffrn_orient_matrix_UB_22      0.0447423000
_diffrn_orient_matrix_UB_23      0.0109750000
_diffrn_orient_matrix_UB_31      0.0165732000
_diffrn_orient_matrix_UB_32      -0.0148801000
_diffrn_orient_matrix_UB_33      0.0206250000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0446
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            53255
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.028
_diffrn_reflns_theta_max         25.028
_diffrn_reflns_theta_min         2.678
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.724
_exptl_absorpt_correction_T_max  0.767
_exptl_absorpt_correction_T_min  0.478
_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 light yellow'
_exptl_crystal_density_diffrn    1.479
_exptl_crystal_description       prism
_exptl_crystal_F_000             2460
_exptl_crystal_size_max          0.284
_exptl_crystal_size_mid          0.137
_exptl_crystal_size_min          0.09
_refine_diff_density_max         1.276
_refine_diff_density_min         -1.325
_refine_diff_density_rms         0.131
_refine_ls_extinction_coef       0.00018(3)
_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   1.190
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1278
_refine_ls_number_reflns         19362
_refine_ls_number_restraints     1886
_refine_ls_restrained_S_all      1.169
_refine_ls_R_factor_all          0.0644
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0186P)^2^+43.3170P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1043
_refine_ls_wR_factor_ref         0.1074
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16944
_reflns_number_total             19362
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02530b2.cif
_cod_data_source_block           nj845
_cod_depositor_comments
'Adding full bibliography for 1567298--1567305.cif.'
_cod_database_code               1567301
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C158 H322 O52 Si12 Cs4 U4'
_shelx_estimated_absorpt_t_max   0.730
_shelx_estimated_absorpt_t_min   0.418
_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
 O9-C38
 2.45 with sigma of 0.02
 O9-C39 \\sim O103-C105 \\sim O8-C20 \\sim O102-C101 \\sim O35-C17 \\sim
O104-C109
 with sigma of 0.02
 C18-C17 \\sim C17-C16 \\sim C19-C17 \\sim C111-C109 \\sim C112-C109 \\sim
C110-C109 \\sim C103-C101 ~
 C33-C20 \\sim C35-C20 \\sim C102-C101 \\sim C104-C101 \\sim C34-C20 \\sim
C39-C36 \\sim C39-C37 \\sim C39-
 C38 \\sim C108-C105 \\sim C107-C105 \\sim C106-C105
 with sigma of 0.02
 C111-C110 \\sim C110-C112
 with sigma of 0.02
 C16-C18 \\sim C18-C19
 with sigma of 0.02
 C37-C36 \\sim C36-C38
 with sigma of 0.02
 C34-C35 \\sim C35-C33
 with sigma of 0.02
 C104-C102 \\sim C102-C103
 with sigma of 0.02
 Si6-O102 \\sim Si6-O8 \\sim Si6-O103 \\sim Si6-O9 \\sim Si6-O104 \\sim Si6-O35
 with sigma of 0.02
 C37-C38 \\sim C38-C36
 with sigma of 0.02
 C107-C106 \\sim C106-C108
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O8 \\sim O102 \\sim C20 \\sim C101 \\sim C104 \\sim C34 \\sim C33 \\sim C103
\\sim C102 \\sim C35 \\sim C105 \\sim C39 \\sim C107 \\sim C37 \\sim C106 \\sim
C36 \\sim C38 \\sim C17 \\sim C16 \\sim C111 \\sim C109 \\sim C110 \\sim C112
\\sim C19 \\sim C18 \\sim O103 \\sim O9 \\sim O104 \\sim O35: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C70) \\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C121) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C112) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
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(O7)=1-FVAR(1)
 Sof(O6)=FVAR(1)
 Sof(C10)=Sof(H10S)=Sof(H10T)=Sof(H10U)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=1-FVAR(2)
 Sof(C11)=Sof(H11J)=Sof(H11K)=Sof(H11L)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=FVAR(2)
 Sof(O8)=Sof(O9)=Sof(O35)=Sof(C17)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C20)=Sof(C36)=Sof(H36A)=Sof(H36B)=
 Sof(H36C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C37)=Sof(H37A)=Sof(H37B)=
 Sof(H37C)=Sof(C39)=1-FVAR(3)
 Sof(O102)=Sof(O103)=Sof(O104)=Sof(C101)=Sof(C102)=Sof(H10A)=Sof(H10B)=
 Sof(H10C)=Sof(C103)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C104)=Sof(H10G)=
 Sof(H10H)=Sof(H10I)=Sof(C105)=Sof(C106)=Sof(H10J)=Sof(H10K)=Sof(H10L)=
 Sof(C107)=Sof(H10M)=Sof(H10N)=Sof(H10O)=Sof(C108)=Sof(H10P)=Sof(H10Q)=
 Sof(H10R)=Sof(C109)=Sof(C110)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C111)=
 Sof(H11D)=Sof(H11E)=Sof(H11F)=Sof(C112)=Sof(H11G)=Sof(H11H)=Sof(H11I)=FVAR(3)
6.a Aromatic/amide H refined with riding coordinates:
 C122(H122), C123(H123), C124(H124), C125(H125), C126(H126)
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(H10S,H10T,H10U), C11(H11J,H11K,H11L), C12(H12A,
 H12B,H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C),
 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(H10A,H10B,
 H10C), C103(H10D,H10E,H10F), C104(H10G,H10H,H10I), C106(H10J,H10K,H10L),
 C107(H10M,H10N,H10O), C108(H10P,H10Q,H10R), C110(H11A,H11B,H11C), C111(H11D,
 H11E,H11F), C112(H11G,H11H,H11I), C127(H12D,H12E,H12F), C19(H19A,H19B,H19C),
 C18(H18A,H18B,H18C), C16(H16A,H16B,H16C), C35(H35A,H35B,H35C), C33(H33A,H33B,
 H33C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C37(H37A,
 H37B,H37C)
;
_shelx_res_checksum              10858
_shelx_hkl_checksum              95310
_olex2_date_sample_data_collection 2022-01-11
_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 1.455
_oxdiff_exptl_absorpt_empirical_full_min 0.656