Nitrogen activation and cleavage by a multimetallic uranium complex.
Keener, Megan; Fadaei-Tirani, Farzaneh; Scopelliti, Rosario; Zivkovic, Ivica; Mazzanti, Marinella; Chemical science 13 (2022) 8025–8035; doi:10.1039/d2sc02997a

data_1567208
_publ_section_title
;
 Nitrogen activation and cleavage by a multimetallic uranium complex.
;
_journal_issue                   27
_journal_name_full               'Chemical science'
_journal_page_first              8025
_journal_page_last               8035
_journal_paper_doi               10.1039/d2sc02997a
_journal_volume                  13
_journal_year                    2022
_chemical_formula_moiety         'C48 H126 N5 O8 Si10 U2, 2(C18 H36 K N2 O6)'
_chemical_formula_sum            'C84 H198 K2 N9 O20 Si10 U2'
_chemical_formula_weight         2489.66
_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             2022-03-28
_audit_creation_method
;
Olex2 1.5
(compiled 2021.12.09 svn.r5202d8cf for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2022-05-24 deposited with the CCDC.	2022-06-22 downloaded from the CCDC.
;
_cell_angle_alpha                106.635(2)
_cell_angle_beta                 103.811(2)
_cell_angle_gamma                95.243(2)
_cell_formula_units_Z            1
_cell_length_a                   13.8976(4)
_cell_length_b                   14.7410(4)
_cell_length_c                   18.5692(4)
_cell_measurement_reflns_used    22776
_cell_measurement_temperature    139.99(10)
_cell_measurement_theta_max      75.6210
_cell_measurement_theta_min      4.1460
_cell_volume                     3487.04(17)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_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      139.99(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 0.986
_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   -114.00 -11.00   1.00    2.00    --  -40.91 -67.00 -61.00  103
  2  \w    -60.00  24.00   1.00    2.00    --  -40.91  67.00  72.00   84
  3  \w     38.00  63.00   1.00    2.00    --   40.91  67.00  72.00   25
  4  \w     98.00 125.00   1.00    8.00    --  112.00  67.00  72.00   27
  5  \w    103.00 140.00   1.00    8.00    --  112.00 -67.00 -61.00   37
  6  \w     50.00  91.00   1.00    8.00    --  112.00 -67.00 -61.00   41
  7  \w   -115.00 -18.00   1.00    2.00    --  -40.91 -38.00-180.00   97
  8  \w    -29.00   6.00   1.00    2.00    --   40.91 -57.00 150.00   35
  9  \w     -5.00  20.00   1.00    2.00    --   40.91 -67.00 -61.00   25
 10  \w     63.00  94.00   1.00    2.00    --   40.91-125.00-120.00   31
 11  \w     34.00  87.00   1.00    2.00    --   40.91-125.00-180.00   53
 12  \w     82.00 123.00   1.00    8.00    --  112.00 178.00-150.00   41
 13  \w     96.00 128.00   1.00    8.00    --  112.00  30.00-150.00   32
 14  \w    102.00 151.00   1.00    8.00    --  112.00  45.00   0.00   49
 15  \w     30.00  63.00   1.00    8.00    --  112.00 -94.00 -60.00   33
 16  \w     30.00 104.00   1.00    8.00    --  112.00 -94.00-150.00   74
 17  \w    129.00 178.00   1.00    8.00    --  112.00  30.00-150.00   49
 18  \w     84.00 111.00   1.00    8.00    --  112.00  61.00 150.00   27
 19  \w    113.00 178.00   1.00    8.00    --  112.00  61.00 150.00   65
 20  \w     50.00 109.00   1.00    8.00    --  112.00-111.00 120.00   59
 21  \w    104.00 177.00   1.00    8.00    --  112.00  77.00 -60.00   73
 22  \w     83.00 178.00   1.00    8.00    --  112.00  61.00  90.00   95
 23  \w     52.00  79.00   1.00    8.00    --  112.00 -94.00-180.00   27
 24  \w     76.00 109.00   1.00    8.00    --  112.00-111.00  60.00   33
 25  \w     29.00  71.00   1.00    8.00    --  112.00 -94.00-120.00   42
 26  \w     52.00 103.00   1.00    8.00    --  112.00-111.00  30.00   51
 27  \w     74.00 107.00   1.00    8.00    --  112.00-111.00  90.00   33
 28  \w     38.00 109.00   1.00    8.00    --  112.00-111.00 -30.00   71
 29  \w    105.00 175.00   1.00    8.00    --  112.00 111.00  30.00   70
 30  \w     63.00 109.00   1.00    8.00    --  112.00-111.00-150.00   46
 31  \w     47.00 107.00   1.00    8.00    --  112.00 -94.00 120.00   60
 32  \w     82.00 131.00   1.00    8.00    --  112.00 -45.00 -90.00   49
 33  \w    104.00 178.00   1.00    8.00    --  112.00  77.00-180.00   74
 34  \w    134.00 165.00   1.00    8.00    --  112.00  77.00  30.00   31
 35  \w     46.00 109.00   1.00    8.00    --  112.00-111.00   0.00   63
 36  \w    112.00 149.00   1.00    8.00    --  112.00  77.00  60.00   37
 37  \w     36.00 109.00   1.00    8.00    --  112.00-111.00 -90.00   73
 38  \w     78.00 109.00   1.00    8.00    --  112.00-111.00 -60.00   31
 39  \w    110.00 171.00   1.00    8.00    --  112.00 111.00 -90.00   61
 40  \w     46.00  71.00   1.00    8.00    --  112.00 -94.00 -90.00   25
 41  \w     61.00  86.00   1.00    8.00    --  112.00 -94.00 150.00   25
;
_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      -0.0778982000
_diffrn_orient_matrix_UB_12      -0.0773405000
_diffrn_orient_matrix_UB_13      -0.0683794000
_diffrn_orient_matrix_UB_21      0.0791006000
_diffrn_orient_matrix_UB_22      -0.0664324000
_diffrn_orient_matrix_UB_23      -0.0061939000
_diffrn_orient_matrix_UB_31      -0.0331819000
_diffrn_orient_matrix_UB_32      -0.0431692000
_diffrn_orient_matrix_UB_33      0.0583897000
_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  0.0513
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            41330
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.131
_diffrn_reflns_theta_min         3.176
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.254
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44245
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_density_diffrn    1.186
_exptl_crystal_description       irregular
_exptl_crystal_F_000             1287
_exptl_crystal_size_max          0.448
_exptl_crystal_size_mid          0.367
_exptl_crystal_size_min          0.22
_refine_diff_density_max         2.296
_refine_diff_density_min         -1.675
_refine_diff_density_rms         0.149
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     667
_refine_ls_number_reflns         14411
_refine_ls_number_restraints     922
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0634
_refine_ls_R_factor_gt           0.0592
_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^)+(0.1043P)^2^+7.6578P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1574
_refine_ls_wR_factor_ref         0.1614
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13148
_reflns_number_total             14411
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02997a2.cif
_cod_data_source_block           mk-539
_cod_depositor_comments
'Adding full bibliography for 1567201--1567212.cif.'
_cod_original_cell_volume        3487.02(17)
_cod_database_code               1567208
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C50 H60 N4 O20 Si8 K2 U2'
_shelx_estimated_absorpt_t_max   0.264
_shelx_estimated_absorpt_t_min   0.119
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 K1-C47
 3.6 with sigma of 0.02
 K1-C45
 3.6 with sigma of 0.02
 C44-C43 \\sim C32-C31 \\sim C33-C34 \\sim C36-C35 \\sim C46-C45 \\sim C48-C47
\\sim C38-C37 \\sim C39-C40
 \\sim C41-C42
 with sigma of 0.02
 N4-C43 \\sim N4-C31 \\sim N4-C42 \\sim N5-C48 \\sim N5-C36 \\sim N5-C37
 with sigma of 0.02
 C43-C31 \\sim C31-C42
 with sigma of 0.02
 C48-C37 \\sim C37-C36
 with sigma of 0.02
 O6-C34 \\sim O6-C35 \\sim O5-C33 \\sim O5-C32 \\sim O7-C41 \\sim O7-C40 \\sim
O8-C39 \\sim O8-C38 \\sim O10-
 C47 \\sim O10-C46 \\sim O9-C45 \\sim O9-C44
 with sigma of 0.02
 C40-C41 \\sim C39-C38 \\sim C47-C46 \\sim C45-C44 \\sim C35-C34 \\sim C33-C32
 with sigma of 0.02
 C29-C28 \\sim C28-C30 \\sim C29-C30
 with sigma of 0.02
 Si5-C25 \\sim Si5-C26 \\sim Si5-C27 \\sim Si6-C29 \\sim Si6-C28 \\sim Si6-C30
 with sigma of 0.02
 C25-C27 \\sim C27-C26 \\sim C25-C26
 with sigma of 0.02
 C13-C14 \\sim C14-C15 \\sim C13-C15
 with sigma of 0.02
 C10-C12 \\sim C12-C11 \\sim C10-C11
 with sigma of 0.02
 C9-C10 \\sim C9-C13 \\sim C9-C12 \\sim C9-C15 \\sim C9-C11 \\sim C9-C14
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C21) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(C31)
\\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C44) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
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(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=
 Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(1)
 Fixed Sof: Si5(0.5) Si6(0.5) N1(0.5) H1(0.5) C25(0.5) H25A(0.5) H25B(0.5)
 H25C(0.5) C26(0.5) H26A(0.5) H26B(0.5) H26C(0.5) C27(0.5) H27A(0.5) H27B(0.5)
 H27C(0.5) C28(0.5) H28A(0.5) H28B(0.5) H28C(0.5) C29(0.5) H29A(0.5) H29B(0.5)
 H29C(0.5) C30(0.5) H30A(0.5) H30B(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,
 H34B), C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B),
 C39(H39A,H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B),
  C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C48(H48A,H48B)
6.b Aromatic/amide H refined with riding coordinates:
 N1(H1)
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),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C),
 C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 109 electrons were 
found in a volume of 800\%A^3^ in 2 voids per unit cell. 
This is consistent with the presence of 
1.35[C4H8O] per Asymmetric Unit 
which account for 108 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              16974
_shelx_hkl_checksum              60989
_shelx_fab_checksum              99484
_olex2_date_sample_data_collection 2022-01-14
_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 2.587
_oxdiff_exptl_absorpt_empirical_full_min 0.484