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_4135319
_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 N3 O16 Si4 U, C16 H36 N, C7 H8'
_chemical_formula_sum            'C71 H152 N4 O16 Si4 U'
_chemical_formula_weight         1668.35
_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             2020-06-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_cell_angle_alpha                91.909(3)
_cell_angle_beta                 91.064(3)
_cell_angle_gamma                101.560(3)
_cell_formula_units_Z            2
_cell_length_a                   13.7935(5)
_cell_length_b                   18.2700(6)
_cell_length_c                   18.3454(7)
_cell_measurement_reflns_used    12525
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      29.1680
_cell_measurement_theta_min      3.1820
_cell_volume                     4525.4(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.81a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.81a (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 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_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    -31.00  13.00   1.00   80.00    --  -18.09 -77.00-120.00   44
  2  \w   -103.00 -67.00   1.00   80.00    --  -18.09 178.00 -30.00   36
  3  \w   -107.00 -69.00   1.00   80.00    --  -18.09-178.00 -90.00   38
  4  \w    -35.00  14.00   1.00   80.00    --  -18.09 -77.00  90.00   49
  5  \w   -103.00 -64.00   1.00   80.00    --  -18.09-178.00 120.00   39
  6  \w    -31.00  -2.00   1.00   80.00    --   18.87 -37.00 -90.00   29
  7  \w    -67.00 107.00   1.00   80.00    --   18.87   0.00 -60.00  174
;
_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      -0.0276948000
_diffrn_orient_matrix_UB_12      -0.0044189000
_diffrn_orient_matrix_UB_13      0.0323137000
_diffrn_orient_matrix_UB_21      0.0089884000
_diffrn_orient_matrix_UB_22      0.0393863000
_diffrn_orient_matrix_UB_23      0.0057844000
_diffrn_orient_matrix_UB_31      -0.0436916000
_diffrn_orient_matrix_UB_32      0.0013180000
_diffrn_orient_matrix_UB_33      -0.0204916000
_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  0.0491
_diffrn_reflns_av_unetI/netI     0.0967
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            54845
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.508
_diffrn_reflns_theta_min         2.974
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.903
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.708
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.81a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.224
_exptl_crystal_description       prism
_exptl_crystal_F_000             1764
_exptl_crystal_size_max          0.282
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.095
_refine_diff_density_max         2.374
_refine_diff_density_min         -1.652
_refine_diff_density_rms         0.141
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     998
_refine_ls_number_reflns         27594
_refine_ls_number_restraints     1190
_refine_ls_restrained_S_all      1.082
_refine_ls_R_factor_all          0.0923
_refine_ls_R_factor_gt           0.0561
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0482P)^2^+3.8723P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1184
_refine_ls_wR_factor_ref         0.1363
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20403
_reflns_number_total             27594
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09814_si_004.cif
_cod_data_source_block           lb1011
_cod_database_code               4135319
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C71 H152 N4 O16 Si4 U1'
_shelx_estimated_absorpt_t_max   0.840
_shelx_estimated_absorpt_t_min   0.616
_reflns_odcompleteness_completeness 99.84
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C97-C94 \\sim C95-C94 \\sim C98-C97 \\sim C95-C96
 with sigma of 0.02
 C74-C69 \\sim C71-C69 \\sim C72-C69 \\sim C75-C69 \\sim C73-C69 \\sim C70-C69
 with sigma of 0.02
 C70-C71 \\sim C70-C72 \\sim C71-C72 \\sim C73-C75 \\sim C73-C74 \\sim C75-C74
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C94 \\sim C95 \\sim C96 \\sim C97 \\sim C98: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73 \\sim C74 \\sim C75: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C99 \\sim C104 \\sim C103 \\sim C102 \\sim C101 \\sim C100 \\sim C105 \\sim
C106 \\sim C111 \\sim C110 \\sim C109 \\sim C108 \\sim C107 \\sim C112: within
2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C61 \\sim C62 \\sim C63 \\sim C64: 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 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H94C)=Sof(H94D)=Sof(C97)=Sof(H97A)=Sof(H97B)=Sof(C98)=Sof(H98A)=Sof(H98B)=
 Sof(H98C)=1-FVAR(1)
 Sof(H94A)=Sof(H94B)=Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(C96)=Sof(H96A)=Sof(H96B)=
 Sof(H96C)=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)
 Sof(C106)=Sof(C111)=Sof(H111)=Sof(C110)=Sof(H110)=Sof(C109)=Sof(H109)=
 Sof(C108)=Sof(H108)=Sof(C107)=Sof(H107)=Sof(C112)=Sof(H11D)=Sof(H11E)=
 Sof(H11F)=1-FVAR(3)
 Sof(C99)=Sof(C104)=Sof(H104)=Sof(C103)=Sof(H103)=Sof(C102)=Sof(H102)=
 Sof(C101)=Sof(H101)=Sof(C100)=Sof(H100)=Sof(C105)=Sof(H10D)=Sof(H10E)=
 Sof(H10F)=FVAR(3)
6.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), C94(H94C,H94D), C95(H95A,H95B), C97(H97A,H97B)
6.b Aromatic/amide H refined with riding coordinates:
 C104(H104), C103(H103), C102(H102), C101(H101), C100(H100), C111(H111),
 C110(H110), C109(H109), C108(H108), C107(H107)
6.c Fitted hexagon refined as free rotating group:
 C99(C104,C103,C102,C101,C100), C106(C111,C110,C109,C108,C107)
6.d 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), 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), 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), C98(H98A,H98B,H98C), C105(H10D,H10E,H10F),
 C112(H11D,H11E,H11F)
;
_shelx_res_checksum              95687
_shelx_hkl_checksum              97710
_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 1.284
_oxdiff_exptl_absorpt_empirical_full_min 0.742