Synthesis, Structure, and Reactivity of Uranium(VI) Nitrides
Barluzzi, Luciano; Hsueh, Fang-Che; Scopelliti, Rosario; Atkinson, Benjamin E.; Kaltsoyannis, Nikolas; Mazzanti, Marinella; Chemical Science  (2021) –; doi:10.1039/D1SC01796A

data_1562343
_publ_section_title
;
 Synthesis, Structure, and Reactivity of Uranium(VI) Nitrides
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC01796A
_journal_year                    2021
_chemical_formula_moiety         'C76 H170 N2 O25 Si6 U2'
_chemical_formula_sum            'C76 H170 N2 O25 Si6 U2'
_chemical_formula_weight         2156.73
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-10-20
_audit_creation_method
;
Olex2 1.3
(compiled 2020.07.31 svn.rc2a77460 for OlexSys, GUI svn.r6145)
;
_audit_update_record
;
2021-03-22 deposited with the CCDC.	2021-04-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.4964(17)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.1108(3)
_cell_length_b                   17.5538(3)
_cell_length_c                   22.2467(4)
_cell_measurement_reflns_used    29462
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      31.2060
_cell_measurement_theta_min      2.9950
_cell_volume                     5508.59(18)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (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 10.5633
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_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     11.00  36.00   1.00   17.37    --   19.75-117.00-129.00   25
  2  \w     38.00  63.00   1.00   17.37    --   19.75-161.00  79.00   25
  3  \w    -70.00 -45.00   1.00   17.37    --  -19.91 117.00 -42.00   25
  4  \w    -97.00 -72.00   1.00   17.37    --  -19.91 161.00 108.00   25
  5  \w    -54.00  36.00   1.00   17.37    --   19.75 -38.00-150.00   90
  6  \w    -12.00  60.00   1.00   17.37    --   19.75 -99.00 120.00   72
  7  \w     -4.00  94.00   1.00   17.37    --   19.75  38.00  90.00   98
  8  \w    -52.00  20.00   1.00   17.37    --  -19.91  77.00  60.00   72
  9  \w    -42.00  12.00   1.00   17.37    --  -19.91 -77.00-150.00   54
 10  \w    -91.00 -33.00   1.00   17.37    --  -19.91 -57.00-180.00   58
 11  \w    -43.00 -17.00   1.00   17.37    --  -19.91  38.00-180.00   26
 12  \w    -32.00   4.00   1.00   17.37    --  -19.91 -77.00  60.00   36
 13  \w      7.00  32.00   1.00   17.37    --  -19.91  38.00-180.00   25
 14  \w    -11.00  21.00   1.00   17.37    --  -19.91  77.00  90.00   32
;
_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      -0.0402834000
_diffrn_orient_matrix_UB_12      0.0026795000
_diffrn_orient_matrix_UB_13      -0.0196172000
_diffrn_orient_matrix_UB_21      0.0016203000
_diffrn_orient_matrix_UB_22      -0.0399104000
_diffrn_orient_matrix_UB_23      -0.0048896000
_diffrn_orient_matrix_UB_31      -0.0300688000
_diffrn_orient_matrix_UB_32      -0.0057794000
_diffrn_orient_matrix_UB_33      0.0246500000
_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  0.0467
_diffrn_reflns_av_unetI/netI     0.0473
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            78955
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.373
_diffrn_reflns_theta_min         2.733
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.060
_exptl_absorpt_correction_T_max  0.856
_exptl_absorpt_correction_T_min  0.090
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (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 dark red'
_exptl_crystal_density_diffrn    1.300
_exptl_crystal_description       prism
_exptl_crystal_F_000             2216
_exptl_crystal_size_max          0.833
_exptl_crystal_size_mid          0.67
_exptl_crystal_size_min          0.558
_refine_diff_density_max         5.384
_refine_diff_density_min         -1.371
_refine_diff_density_rms         0.195
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.440(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.014
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     995
_refine_ls_number_reflns         22528
_refine_ls_number_restraints     1624
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.0782
_refine_ls_R_factor_gt           0.0697
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1557P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1877
_refine_ls_wR_factor_ref         0.1974
_reflns_Friedel_coverage         0.934
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                19800
_reflns_number_total             22528
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01796a2.cif
_cod_data_source_block           lb1155b
_cod_original_cell_volume        5508.59(17)
_cod_database_code               1562343
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C76 H167 N2 O25 Si6 U2'
_shelx_estimated_absorpt_t_max   0.280
_shelx_estimated_absorpt_t_min   0.185
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.560(11)
 0.440(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C107-C105 = C108-C105 = C106-C105 = C104-C101 = C101-C103 = C102-C101 = C112-
 C109 = C110-C109 = C111-C109 = C67-C65 = C65-C66 = C68-C65 = C72-C69 = C70-C69
 = C71-C69 = C61-C62 = C64-C61 = C63-C61 = C43-C41 = C42-C41 = C44-C41 = C46-
 C45 = C47-C45 = C48-C45 = C50-C49 = C52-C49 = C51-C49 = C12-C9 = C10-C9 = C11-
 C9 = C2-C1 = C4-C1 = C3-C1 = C26-C25 = C27-C25 = C25-C28 = C24-C21 = C22-C21 =
 C23-C21 = C7-C5 = C6-C5 = C8-C5 = C32-C29 = C30-C29 = C31-C29 = C82-C81 = C83-
 C81 = C84-C81 = C89-C91 = C89-C92 = C89-C90 = C86-C85 = C88-C85 = C87-C85
 1.54 with sigma of 0.02
 O102-C101 = O63-C65 = O64-C69 = O62-C61 = O42-C41 = O43-C45 = O44-C49 = O4-C9
 = O2-C1 = O23-C25 = O24-C29 = O3-C5 = O22-C21 = O82-C81 = O83-C85 = O84-C89 =
 O103-C105 = O104-C109
 1.43 with sigma of 0.02
 C10-O4
 2.4 with sigma of 0.02
 O103-C108
 2.4 with sigma of 0.02
 C70-C71 \\sim C71-C72 \\sim C70-C72
 with sigma of 0.02
 C10-C11 \\sim C11-C12 \\sim C10-C12
 with sigma of 0.02
 C4-C3 \\sim C3-C2 \\sim C2-C4
 with sigma of 0.02
 C6-C7 \\sim C7-C8 \\sim C6-C8
 with sigma of 0.02
 C31-C30 \\sim C30-C32 \\sim C31-C32
 with sigma of 0.02
 C22-C24 \\sim C24-C23 \\sim C22-C23
 with sigma of 0.02
 C28-C27 \\sim C27-C26 \\sim C26-C28
 with sigma of 0.02
 C42-C43 \\sim C43-C44 \\sim C42-C44
 with sigma of 0.02
 C48-C46 \\sim C46-C47 \\sim C47-C48
 with sigma of 0.02
 C50-C52 \\sim C52-C51 \\sim C50-C51
 with sigma of 0.02
 C63-C62 \\sim C62-C64 \\sim C63-C64
 with sigma of 0.02
 C68-C66 \\sim C66-C67 \\sim C67-C68
 with sigma of 0.02
 C86-C87 \\sim C87-C88 \\sim C86-C88
 with sigma of 0.02
 C90-C92 \\sim C92-C91 \\sim C90-C91
 with sigma of 0.02
 C82-C83 \\sim C83-C84 \\sim C82-C84
 with sigma of 0.02
 C102-C103 \\sim C103-C104 \\sim C102-C104
 with sigma of 0.02
 C106-C108 \\sim C108-C107 \\sim C106-C107
 with sigma of 0.02
 C112-C110 \\sim C110-C111 \\sim C111-C112
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9
\\sim C10 \\sim C11 \\sim C12 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25
\\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48 \\sim C49
\\sim C50 \\sim C51 \\sim C52 \\sim C61 \\sim C62 \\sim C63 \\sim C64 \\sim C65
\\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C71 \\sim C72 \\sim C81
\\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88 \\sim C89
\\sim C90 \\sim C91 \\sim C92 \\sim C101 \\sim C102 \\sim C103 \\sim C104 \\sim
C105 \\sim C106 \\sim C107 \\sim C108 \\sim C109 \\sim C110 \\sim C111 \\sim
C112 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim O1 \\sim O2 \\sim O3
\\sim O4 \\sim O21 \\sim O22 \\sim O23 \\sim O24 \\sim O41 \\sim O42 \\sim O43
\\sim O44 \\sim O61 \\sim O62 \\sim O63 \\sim O64 \\sim O81 \\sim O82 \\sim O83
\\sim O84 \\sim O101 \\sim O102 \\sim O103 \\sim O104 \\sim O121: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(O2) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C4) \\sim
Ueq, Uanis(C2) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(O42) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C43)
\\sim Ueq, Uanis(C92) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C46) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C90) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. 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
6. Others
 Fixed X: U1(0.79161) U2(0.760409)
 Fixed Y: U1(0.363481) U2(0.482689)
 Fixed Z: U1(0.68844) U2(0.80173)
7.a Secondary CH2 refined with riding coordinates:
 C121(H12D,H12E), C122(H12F,H12G), C123(H12H,H12I), C124(H12J,H12K)
7.b Me refined with riding coordinates:
 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), 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(H10D,H10E,H10F), C103(H10G,H10H,H10I), C104(H10J,H10K,H10L), C106(H10M,
 H10N,H10O), C107(H10P,H10Q,H10R), C108(H10S,H10T,H10U), C110(H11D,H11E,H11F),
 C111(H11G,H11H,H11I), C112(H11J,H11K,H11L)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              6361
_shelx_hkl_checksum              46821
_shelx_fab_checksum              18511
_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 2.171
_oxdiff_exptl_absorpt_empirical_full_min 0.496