Photochemical Synthesis of a Stable Terminal Uranium(VI) Nitride
Barluzzi, Luciano; Scopelliti, Rosario; Mazzanti, Marinella; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c09814

data_4135322
_publ_section_title
;
 Photochemical Synthesis of a Stable Terminal Uranium(VI) Nitride
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c09814
_journal_year                    2020
_chemical_formula_moiety         'C48 H108 N O16 Si4 U, C16 H36 N, 2(C7 H8)'
_chemical_formula_sum            'C78 H160 N2 O16 Si4 U'
_chemical_formula_weight         1732.46
_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             2020-07-28
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.16 svn.r6f6c53a7 for OlexSys, GUI svn.r6139)
;
_cell_angle_alpha                88.6774(9)
_cell_angle_beta                 81.8561(10)
_cell_angle_gamma                86.4823(10)
_cell_formula_units_Z            2
_cell_length_a                   14.10407(17)
_cell_length_b                   16.7659(2)
_cell_length_c                   19.9097(2)
_cell_measurement_reflns_used    31322
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.5900
_cell_measurement_theta_min      3.5980
_cell_volume                     4651.24(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.82a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.82a (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  (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 0.998
_diffrn_measured_fraction_theta_max 0.974
_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   -113.00 -88.00   1.00    5.00    --  -40.91-146.00 -58.00   25
  2  \w    -87.00  -6.00   1.00    5.00    --  -40.91 125.00-173.00   81
  3  \w    -83.00 -58.00   1.00    5.00    --  -40.91 146.00  -7.00   25
  4  \w     50.00  86.00   1.00    5.00    --   40.91-125.00 108.00   36
  5  \w     49.00  74.00   1.00    5.00    --   40.91-146.00 -58.00   25
  6  \w    103.00 128.00   1.00   20.00    --  105.15 146.00  -7.00   25
  7  \w     48.00  73.00   1.00   20.00    --  105.15-125.00 108.00   25
  8  \w    111.00 169.00   1.00   20.00    --  105.15 125.00-173.00   58
  9  \w     41.00 128.00   1.00   20.00    --  105.15-146.00 -58.00   87
 10  \w   -114.00 -16.00   1.00    5.00    --  -40.91 -38.00 -60.00   98
 11  \w   -104.00 -17.00   1.00    5.00    --  -40.91 -38.00  30.00   87
 12  \w    -56.00  -9.00   1.00    5.00    --  -40.91 125.00  90.00   47
 13  \w     -2.00  24.00   1.00    5.00    --   40.91 -77.00-180.00   26
 14  \w     47.00  74.00   1.00    5.00    --   40.91-125.00 -60.00   27
 15  \w     36.00  70.00   1.00   20.00    --  105.15-111.00 -30.00   34
 16  \w     48.00 130.00   1.00   20.00    --  105.15 -45.00 -90.00   82
 17  \w    146.00 171.00   1.00   20.00    --  105.15 111.00 120.00   25
 18  \w    105.00 133.00   1.00   20.00    --  105.15 111.00-120.00   28
 19  \w     63.00 143.00   1.00   20.00    --  105.15 178.00 -60.00   80
 20  \w     87.00 172.00   1.00   20.00    --  105.15  30.00  60.00   85
 21  \w     64.00 109.00   1.00   20.00    --  105.15-111.00  60.00   45
 22  \w     23.00  84.00   1.00   20.00    --  105.15 -94.00 120.00   61
 23  \w     30.00  86.00   1.00   20.00    --  105.15 -77.00 -90.00   56
 24  \w    112.00 151.00   1.00   20.00    --  105.15  77.00 -30.00   39
 25  \w     78.00 109.00   1.00   20.00    --  105.15-111.00 -30.00   31
 26  \w     34.00 125.00   1.00   20.00    --  105.15 -45.00  60.00   91
 27  \w    105.00 132.00   1.00   20.00    --  105.15 111.00 120.00   27
 28  \w     70.00 109.00   1.00   20.00    --  105.15-111.00-180.00   39
 29  \w     94.00 174.00   1.00   20.00    --  105.15  45.00 -60.00   80
;
_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      -0.0477209000
_diffrn_orient_matrix_UB_12      0.0415110000
_diffrn_orient_matrix_UB_13      0.0654913000
_diffrn_orient_matrix_UB_21      -0.0562115000
_diffrn_orient_matrix_UB_22      0.0590740000
_diffrn_orient_matrix_UB_23      -0.0423070000
_diffrn_orient_matrix_UB_31      -0.0823419000
_diffrn_orient_matrix_UB_32      -0.0571308000
_diffrn_orient_matrix_UB_33      0.0056746000
_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  0.0194
_diffrn_reflns_av_unetI/netI     0.0243
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            41424
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.733
_diffrn_reflns_theta_min         3.171
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.857
_exptl_absorpt_correction_T_max  0.722
_exptl_absorpt_correction_T_min  0.549
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (Rigaku Oxford Diffraction, 2020)
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 intense orange'
_exptl_crystal_density_diffrn    1.237
_exptl_crystal_description       prism
_exptl_crystal_F_000             1836
_exptl_crystal_size_max          0.156
_exptl_crystal_size_mid          0.122
_exptl_crystal_size_min          0.075
_refine_diff_density_max         0.790
_refine_diff_density_min         -0.767
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1014
_refine_ls_number_reflns         18050
_refine_ls_number_restraints     159
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0203
_refine_ls_R_factor_gt           0.0188
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0182P)^2^+2.7049P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0440
_refine_ls_wR_factor_ref         0.0446
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17247
_reflns_number_total             18050
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09814_si_006.cif
_cod_data_source_block           lb1068
_cod_original_cell_volume        4651.24(10)
_cod_database_code               4135322
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C78 H160 N2 O16 Si4 U'
_shelx_estimated_absorpt_t_max   0.668
_shelx_estimated_absorpt_t_min   0.462
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C46-C45 \\sim C49-C45 \\sim C47-C45 \\sim C50-C45 \\sim C48-C45 \\sim C51-C45
 with sigma of 0.02
 C46-C47 \\sim C46-C48 \\sim C47-C48 \\sim C49-C50 \\sim C49-C51 \\sim C50-C51
 with sigma of 0.02
 C70-C71 \\sim C70-C72 \\sim C71-C72 \\sim C73-C74 \\sim C73-C75 \\sim C74-C75
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C45 \\sim C48 \\sim C51 \\sim C46 \\sim C49 \\sim C50 \\sim C47: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C69 \\sim C74 \\sim C71 \\sim C72 \\sim C70 \\sim C73: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=
 Sof(C51)=Sof(H51A)=Sof(H51B)=Sof(H51C)=1-FVAR(1)
 Sof(C46)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=FVAR(1)
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=1-FVAR(2)
 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)
5.a Secondary CH2 refined with riding coordinates:
 C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B), C85(H85A,H85B), C86(H86A,
 H86B), C87(H87A,H87B), C89(H89A,H89B), C90(H90A,H90B), C91(H91A,H91B),
 C93(H93A,H93B), C94(H94A,H94B), C95(H95A,H95B)
5.b Aromatic/amide H refined with riding coordinates:
 C98(H98), C99(H99), C100(H100), C101(H101), C102(H102), C105(H105),
 C106(H106), C107(H107), C108(H108), C109(H109)
5.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), 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), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,
 H51C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), 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), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,
 H75B,H75C), C84(H84A,H84B,H84C), C88(H88A,H88B,H88C), C92(H92A,H92B,H92C),
 C96(H96A,H96B,H96C), C103(H10D,H10E,H10F), C110(H11D,H11E,H11F)
;
_shelx_res_checksum              53639
_shelx_hkl_checksum              52615
_olex2_date_sample_data_collection 2020-07-24
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.307
_oxdiff_exptl_absorpt_empirical_full_min 0.740