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_1562342
_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 H174 N2 O25 Si6 U2, C4 H10 O'
_chemical_formula_sum            'C80 H184 N2 O26 Si6 U2'
_chemical_formula_weight         2234.88
_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             2021-01-15
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-03-22 deposited with the CCDC.	2021-04-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 91.5214(8)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   14.34057(14)
_cell_length_b                   17.69858(18)
_cell_length_c                   22.05000(18)
_cell_measurement_reflns_used    50770
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      75.6900
_cell_measurement_theta_min      3.6180
_cell_volume                     5594.49(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.94a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.94a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.94a (Rigaku OD, 2021)'
_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 1.000
_diffrn_measured_fraction_theta_max 0.989
_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    -22.00  38.00   1.00    3.00    --  -40.91  19.00-124.00   60
  2  \w   -119.00  -2.00   1.00    3.00    --  -40.91 -19.00  67.00  117
  3  \w     -3.00  22.00   1.00    3.00    --   40.91 -19.00  67.00   25
  4  \w     36.00  61.00   1.00    3.00    --   40.91  19.00-124.00   25
  5  \w     34.00  93.00   1.00   12.00    --  112.00 -19.00  67.00   59
  6  \w     89.00 167.00   1.00   12.00    --  112.00  19.00-124.00   78
  7  \w    -68.00  31.00   1.00    3.00    --  -40.91  57.00-120.00   99
  8  \w      7.00  33.00   1.00    3.00    --   40.91 -99.00  60.00   26
  9  \w     30.00  97.00   1.00    3.00    --   40.91-125.00 120.00   67
 10  \w    -13.00  70.00   1.00    3.00    --   40.91 -77.00 -30.00   83
 11  \w     32.00  91.00   1.00    3.00    --   40.91-125.00   0.00   59
 12  \w     35.00  60.00   1.00    3.00    --   40.91-125.00 -90.00   25
 13  \w     41.00 136.00   1.00   12.00    --  112.00 -61.00-180.00   95
 14  \w    135.00 162.00   1.00   12.00    --  112.00  30.00 120.00   27
 15  \w     41.00  76.00   1.00   12.00    --  112.00 -61.00 150.00   35
 16  \w     47.00 109.00   1.00   12.00    --  112.00-111.00  30.00   62
 17  \w     37.00 107.00   1.00   12.00    --  112.00-111.00-150.00   70
 18  \w     85.00 119.00   1.00   12.00    --  112.00  30.00 -90.00   34
 19  \w     88.00 177.00   1.00   12.00    --  112.00  61.00 120.00   89
 20  \w     58.00 109.00   1.00   12.00    --  112.00-111.00-180.00   51
 21  \w     87.00 146.00   1.00   12.00    --  112.00  61.00 150.00   59
 22  \w     75.00 109.00   1.00   12.00    --  112.00-111.00  90.00   34
 23  \w    100.00 160.00   1.00   12.00    --  112.00 -15.00-120.00   60
 24  \w     34.00  81.00   1.00   12.00    --  112.00 -15.00-120.00   47
 25  \w     75.00 122.00   1.00   12.00    --  112.00 -61.00 -30.00   47
 26  \w     77.00 109.00   1.00   12.00    --  112.00-111.00   0.00   32
 27  \w     38.00 107.00   1.00   12.00    --  112.00-111.00 120.00   69
 28  \w     58.00 109.00   1.00   12.00    --  112.00-111.00 -90.00   51
 29  \w     74.00 103.00   1.00   12.00    --  112.00-111.00-120.00   29
 30  \w    103.00 177.00   1.00   12.00    --  112.00  77.00-120.00   74
 31  \w     81.00 145.00   1.00   12.00    --  112.00 178.00 150.00   64
 32  \w     81.00 109.00   1.00   12.00    --  112.00-111.00 -60.00   28
 33  \w    104.00 173.00   1.00   12.00    --  112.00  77.00  60.00   69
 34  \w     48.00  75.00   1.00   12.00    --  112.00-111.00 -60.00   27
 35  \w     38.00  77.00   1.00   12.00    --  112.00 -94.00 -30.00   39
 36  \w     53.00 109.00   1.00   12.00    --  112.00-111.00 150.00   56
 37  \w     37.00  62.00   1.00   12.00    --  112.00-111.00-120.00   25
 38  \w     69.00 138.00   1.00   12.00    --  112.00 -45.00 -90.00   69
 39  \w    118.00 143.00   1.00   12.00    --  112.00 111.00-180.00   25
 40  \w     44.00  69.00   1.00   12.00    --  112.00 -94.00-180.00   25
 41  \w     71.00  98.00   1.00   12.00    --  112.00 -94.00 -60.00   27
;
_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      0.1045208000
_diffrn_orient_matrix_UB_12      -0.0109549000
_diffrn_orient_matrix_UB_13      0.0154931000
_diffrn_orient_matrix_UB_21      0.0162215000
_diffrn_orient_matrix_UB_22      0.0853998000
_diffrn_orient_matrix_UB_23      -0.0082080000
_diffrn_orient_matrix_UB_31      -0.0187179000
_diffrn_orient_matrix_UB_32      0.0128513000
_diffrn_orient_matrix_UB_33      0.0676881000
_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  0.0346
_diffrn_reflns_av_unetI/netI     0.0325
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            69237
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.469
_diffrn_reflns_theta_min         3.083
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.201
_exptl_absorpt_correction_T_max  0.331
_exptl_absorpt_correction_T_min  0.170
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.94a (Rigaku Oxford Diffraction, 2021)
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 pale green'
_exptl_crystal_density_diffrn    1.327
_exptl_crystal_description       irregular
_exptl_crystal_F_000             2308
_exptl_crystal_size_max          0.348
_exptl_crystal_size_mid          0.254
_exptl_crystal_size_min          0.215
_refine_diff_density_max         2.016
_refine_diff_density_min         -2.307
_refine_diff_density_rms         0.088
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.038(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1358
_refine_ls_number_reflns         22639
_refine_ls_number_restraints     2275
_refine_ls_restrained_S_all      1.030
_refine_ls_R_factor_all          0.0393
_refine_ls_R_factor_gt           0.0382
_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^)+(0.0448P)^2^+14.8116P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0940
_refine_ls_wR_factor_ref         0.0949
_reflns_Friedel_coverage         0.884
_reflns_Friedel_fraction_full    0.957
_reflns_Friedel_fraction_max     0.935
_reflns_number_gt                22047
_reflns_number_total             22639
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01796a2.cif
_cod_data_source_block           ah34
_cod_database_code               1562342
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C80 H184 N2 O26 Si6 U2'
_shelx_estimated_absorpt_t_max   0.242
_shelx_estimated_absorpt_t_min   0.142
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.962(6)
 0.038(6)
2. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 Si1-O5 \\sim Si1-O4 \\sim Si4-O63 \\sim Si1-O3 \\sim Si1-O2 \\sim Si1-O6
 with sigma of 0.02
 C10-C11 \\sim C11-C12 \\sim C10-C12
 with sigma of 0.02
 C7-C5 \\sim C5-C8 \\sim C8-C7
 with sigma of 0.02
 O5-C13 \\sim O4-C9 \\sim O3-C6 \\sim O2-C1
 with sigma of 0.02
 C2-C3 \\sim C3-C4 \\sim C2-C4
 with sigma of 0.02
 C9-C10 \\sim C9-C12 \\sim C15-C13 \\sim C16-C13 \\sim C14-C13 \\sim C9-C11
\\sim C7-C6 \\sim C2-C1 \\sim C4-
 C1 \\sim C8-C6 \\sim C3-C1 \\sim C6-C5
 with sigma of 0.02
 C15-C14 \\sim C14-C16 \\sim C15-C16
 with sigma of 0.02
 C30-C31 \\sim C31-C33 \\sim C30-C33
 with sigma of 0.02
 C32-C29 \\sim C30-C29 \\sim C34-C29 \\sim C31-C29 \\sim C33-C29 \\sim C35-C29
 with sigma of 0.02
 C32-C34 \\sim C34-C35 \\sim C32-C35
 with sigma of 0.02
 C54-C53 \\sim C53-C52 \\sim C52-C54
 with sigma of 0.02
 C50-C36 \\sim C54-C36 \\sim C51-C36 \\sim C52-C36 \\sim C53-C36 \\sim C49-C36
 with sigma of 0.02
 C50-C51 \\sim C51-C49 \\sim C49-C50
 with sigma of 0.02
 C68-C65 \\sim C72-C69 \\sim C70-C69 \\sim C67-C65 \\sim C71-C69 \\sim C66-C65
\\sim C74-C73 \\sim C75-C73
 \\sim C78-C77 \\sim C76-C73 \\sim C79-C77 \\sim C80-C77
 with sigma of 0.02
 C70-C71 \\sim C71-C72
 with sigma of 0.02
 C67-C66 \\sim C66-C68
 with sigma of 0.02
 O65-C65 \\sim O64-C69 \\sim O63-C73 \\sim O62-C77
 with sigma of 0.02
 C74-C75 \\sim C75-C76
 with sigma of 0.02
 C71-C70 \\sim C70-C72
 with sigma of 0.02
 C78-C79 \\sim C79-C80
 with sigma of 0.02
 C66-C67 \\sim C67-C68
 with sigma of 0.02
 Si4-O66 \\sim Si4-O65 \\sim Si4-O64 \\sim Si4-O63 \\sim Si4-O62
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O3 \\sim O2 \\sim Si1 \\sim O4 \\sim O5 \\sim C17 \\sim C18 \\sim C20 \\sim C19
\\sim O6 \\sim C12 \\sim C9 \\sim C10 \\sim C15 \\sim C13 \\sim C16 \\sim C11
\\sim C14 \\sim C6 \\sim C7 \\sim C1 \\sim C3 \\sim C4 \\sim C2 \\sim C5 \\sim
C8: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C29 \\sim C32 \\sim C30 \\sim C34 \\sim C31 \\sim C33 \\sim C35: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C36 \\sim C53 \\sim C50 \\sim C54 \\sim C51 \\sim C52 \\sim C49: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
Si4 \\sim O64 \\sim O65 \\sim O63 \\sim O62 \\sim O66 \\sim C61 \\sim C64 \\sim
C62 \\sim C63 \\sim C65 \\sim C67 \\sim C70 \\sim C69 \\sim C72 \\sim C71 \\sim
C68 \\sim C66 \\sim C77 \\sim C79 \\sim C78 \\sim C80 \\sim C75 \\sim C73 \\sim
C74 \\sim C76: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
Uanis(C44) \\sim Ueq, Uanis(C64) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C26) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C83) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
5. 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
6. Others
 Sof(O3)=Sof(O5)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=Sof(C6)=Sof(C7)=Sof(H7A)=
 Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C13)=Sof(C14)=
 Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=
 Sof(H16A)=Sof(H16B)=Sof(H16C)=1-FVAR(1)
 Sof(O2)=Sof(O4)=Sof(C1)=Sof(C2)=Sof(H2C)=Sof(H2D)=Sof(H2E)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(H3C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(H4C)=Sof(C9)=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)
 Sof(O62)=Sof(O64)=Sof(C69)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C71)=
 Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C77)=
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=
 Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=1-FVAR(2)
 Sof(O63)=Sof(O65)=Sof(C65)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C67)=
 Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C73)=
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=FVAR(2)
 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(3)
 Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=
 Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=FVAR(3)
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=
 Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=1-FVAR(4)
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(4)
7.a Secondary CH2 refined with riding coordinates:
 N1(H1A,H1B), N2(H2A,H2B), C121(H12D,H12E), C122(H12F,H12G), C123(H12H,H12I),
 C124(H12J,H12K), C126(H12O,H12P), C127(H12Q,H12R)
7.b Idealised Me refined as rotating group:
 C2(H2C,H2D,H2E), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C7(H7A,
 H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,
 H12B,H12C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C),
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), 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), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), 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), C52(H52A,H52B,H52C), C53(H53A,H53B,
 H53C), C54(H54A,H54B,H54C), 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), C74(H74A,H74B,
 H74C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C78(H78A,H78B,H78C), C79(H79A,
 H79B,H79C), C80(H80A,H80B,H80C), 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), C125(H12L,H12M,H12N), C128(H12S,
 H12T,H12U)
;
_shelx_res_checksum              19177
_shelx_hkl_checksum              81667
_olex2_date_sample_data_collection 2021-01-14
_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 2.018
_oxdiff_exptl_absorpt_empirical_full_min 0.488