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_4135321
_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         'C49 H108 N O17 Si4 U, C16 H36 N, C7 H8'
_chemical_formula_sum            'C72 H152 N2 O17 Si4 U'
_chemical_formula_weight         1668.34
_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             2020-07-13
_audit_creation_method
;
Olex2 1.3
(compiled 2020.06.28 svn.raecde09e for OlexSys, GUI svn.r6132)
;
_cell_angle_alpha                91.9047(17)
_cell_angle_beta                 91.0275(16)
_cell_angle_gamma                101.2611(16)
_cell_formula_units_Z            2
_cell_length_a                   13.8047(2)
_cell_length_b                   18.2614(4)
_cell_length_c                   18.3619(4)
_cell_measurement_reflns_used    19194
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      32.4300
_cell_measurement_theta_min      3.2630
_cell_volume                     4535.87(16)
_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 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.892
_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    -15.00  51.00   1.00   28.77    --  -18.09  57.00   0.00   66
  2  \w   -107.00 -82.00   1.00   28.77    --  -18.09-178.00  30.00   25
  3  \w    -18.00  19.00   1.00   28.77    --  -18.09 -90.00  -5.00   37
  4  \w    -32.00   0.00   1.00   28.77    --  -18.09 -77.00-180.00   32
  5  \w     -5.00  83.00   1.00   28.77    --   18.87  37.00 -90.00   88
  6  \w     -3.00  60.00   1.00   28.77    --   18.87 -99.00 -30.00   63
  7  \w    -56.00  43.00   1.00   28.77    --   18.87 -37.00  90.00   99
;
_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      -0.0077789000
_diffrn_orient_matrix_UB_12      -0.0320911000
_diffrn_orient_matrix_UB_13      0.0214982000
_diffrn_orient_matrix_UB_21      -0.0198980000
_diffrn_orient_matrix_UB_22      0.0201228000
_diffrn_orient_matrix_UB_23      0.0278036000
_diffrn_orient_matrix_UB_31      -0.0478532000
_diffrn_orient_matrix_UB_32      -0.0116582000
_diffrn_orient_matrix_UB_33      -0.0161108000
_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  0.0302
_diffrn_reflns_av_unetI/netI     0.0563
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.892
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            58441
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.846
_diffrn_reflns_theta_min         2.968
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.898
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.564
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.82a (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    1.222
_exptl_crystal_description       prism
_exptl_crystal_F_000             1764
_exptl_crystal_size_max          0.258
_exptl_crystal_size_mid          0.253
_exptl_crystal_size_min          0.178
_refine_diff_density_max         2.489
_refine_diff_density_min         -1.520
_refine_diff_density_rms         0.097
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1029
_refine_ls_number_reflns         30122
_refine_ls_number_restraints     480
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0575
_refine_ls_R_factor_gt           0.0379
_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^)+(0.0375P)^2^+1.0093P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0793
_refine_ls_wR_factor_ref         0.0890
_reflns_Friedel_coverage         0.000
_reflns_number_gt                24531
_reflns_number_total             30122
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c09814_si_005.cif
_cod_data_source_block           lb1035
_cod_original_cell_volume        4535.89(16)
_cod_database_code               4135321
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C72 H152 N2 O17 Si4 U1'
_shelx_estimated_absorpt_t_max   0.729
_shelx_estimated_absorpt_t_min   0.640
_reflns_odcompleteness_completeness 99.88
_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
 C69-C65 \\sim C66-C65 \\sim C68-C65 \\sim C71-C65 \\sim C70-C65 \\sim C67-C65
 with sigma of 0.02
 C66-C67 \\sim C66-C68 \\sim C67-C68 \\sim C69-C70 \\sim C69-C71 \\sim C70-C71
 with sigma of 0.02
 C77-C72 \\sim C73-C72 \\sim C76-C72 \\sim C75-C72 \\sim C74-C72 \\sim C78-C72
 with sigma of 0.02
 C73-C74 \\sim C73-C75 \\sim C74-C75 \\sim C76-C77 \\sim C76-C78 \\sim C77-C78
 with sigma of 0.02
 C94-C93 \\sim C96-C93 \\sim C95-C94 \\sim C97-C96
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C72 \\sim C73 \\sim C77 \\sim C76 \\sim C75 \\sim C78 \\sim C74: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C93 \\sim C96 \\sim C97 \\sim C95 \\sim C94: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110 \\sim C98 \\sim C99
\\sim C100 \\sim C101 \\sim C102 \\sim C103 \\sim C104 \\sim C111: within 2A
with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. Others
 Sof(H93C)=Sof(H93D)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(C97)=Sof(H97A)=Sof(H97B)=
 Sof(H97C)=1-FVAR(1)
 Sof(H93A)=Sof(H93B)=Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(C95)=Sof(H95A)=Sof(H95B)=
 Sof(H95C)=FVAR(1)
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=1-FVAR(2)
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=FVAR(2)
 Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=1-FVAR(3)
 Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=
 Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=FVAR(3)
 Sof(C105)=Sof(C110)=Sof(H110)=Sof(C109)=Sof(H109)=Sof(C108)=Sof(H108)=
 Sof(C107)=Sof(H107)=Sof(C106)=Sof(H106)=Sof(C111)=Sof(H11D)=Sof(H11E)=
 Sof(H11F)=1-FVAR(4)
 Sof(C98)=Sof(C103)=Sof(H103)=Sof(C102)=Sof(H102)=Sof(C101)=Sof(H101)=
 Sof(C100)=Sof(H100)=Sof(C99)=Sof(H99)=Sof(C104)=Sof(H10D)=Sof(H10E)=Sof(H10F)=
 FVAR(4)
5.a Secondary CH2 refined with riding coordinates:
 C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B), C84(H84A,H84B), C85(H85A,
 H85B), C86(H86A,H86B), C88(H88A,H88B), C89(H89A,H89B), C90(H90A,H90B),
 C92(H92A,H92B), C93(H93A,H93B), C93(H93C,H93D), C94(H94A,H94B), C96(H96A,H96B)
5.b Aromatic/amide H refined with riding coordinates:
 C103(H103), C102(H102), C101(H101), C100(H100), C99(H99), C110(H110),
 C109(H109), C108(H108), C107(H107), C106(H106)
5.c Fitted hexagon refined as free rotating group:
 C98(C103,C102,C101,C100,C99), C105(C110,C109,C108,C107,C106)
5.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), C69(H69A,H69B,H69C),
 C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C73(H73A,H73B,H73C), C74(H74A,H74B,
 H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C78(H78A,
 H78B,H78C), C83(H83A,H83B,H83C), C87(H87A,H87B,H87C), C91(H91A,H91B,H91C),
 C95(H95A,H95B,H95C), C97(H97A,H97B,H97C), C104(H10D,H10E,H10F), C111(H11D,H11E,
 H11F)
;
_shelx_res_checksum              88397
_shelx_hkl_checksum              94249
_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 1.314
_oxdiff_exptl_absorpt_empirical_full_min 0.789