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_1562341
_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         'C72 H162 K N2 O24 Si6 U2'
_chemical_formula_sum            'C72 H162 K N2 O24 Si6 U2'
_chemical_formula_weight         2123.73
_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             2020-11-06
_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                80.0596(15)
_cell_angle_beta                 88.3887(15)
_cell_angle_gamma                71.6290(16)
_cell_formula_units_Z            2
_cell_length_a                   13.4396(3)
_cell_length_b                   17.7067(3)
_cell_length_c                   25.0094(5)
_cell_measurement_reflns_used    25359
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      29.2780
_cell_measurement_theta_min      3.1740
_cell_volume                     5561.2(2)
_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 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.844
_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     -8.00  58.00   1.00   12.50    --   11.66-108.00  -0.00   66
  2  \w     15.00  86.00   1.00   12.50    --   11.66  38.00-180.00   71
  3  \w    -29.00  89.00   1.00   12.50    --   11.66  19.00 120.00  118
  4  \w     75.00 100.00   1.00   12.50    --   11.66 178.00-180.00   25
  5  \w    -17.00  15.00   1.00   12.50    --  -11.81 -77.00   0.00   32
  6  \w    -34.00  -7.00   1.00   12.50    --  -11.81 -77.00-120.00   27
  7  \w    -23.00  17.00   1.00   12.50    --  -11.81 -77.00 150.00   40
  8  \w    -36.00  -8.00   1.00   12.50    --  -11.81 -77.00-150.00   28
  9  \w    -27.00  -2.00   1.00   12.50    --  -11.81  77.00 150.00   25
;
_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      0.0424604000
_diffrn_orient_matrix_UB_12      -0.0202867000
_diffrn_orient_matrix_UB_13      0.0187904000
_diffrn_orient_matrix_UB_21      -0.0359366000
_diffrn_orient_matrix_UB_22      -0.0039472000
_diffrn_orient_matrix_UB_23      0.0207903000
_diffrn_orient_matrix_UB_31      0.0008480000
_diffrn_orient_matrix_UB_32      -0.0375395000
_diffrn_orient_matrix_UB_33      -0.0066644000
_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  0.0319
_diffrn_reflns_av_unetI/netI     0.0554
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.844
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            62738
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.844
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.679
_diffrn_reflns_theta_min         2.682
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    3.066
_exptl_absorpt_correction_T_max  0.843
_exptl_absorpt_correction_T_min  0.548
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (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 dark brown'
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       prism
_exptl_crystal_F_000             2174
_exptl_crystal_size_max          0.497
_exptl_crystal_size_mid          0.289
_exptl_crystal_size_min          0.144
_refine_diff_density_max         4.644
_refine_diff_density_min         -1.598
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1125
_refine_ls_number_reflns         26553
_refine_ls_number_restraints     896
_refine_ls_restrained_S_all      1.068
_refine_ls_R_factor_all          0.0689
_refine_ls_R_factor_gt           0.0461
_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^)+(0.0558P)^2^+10.3587P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1071
_refine_ls_wR_factor_ref         0.1173
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19930
_reflns_number_total             26553
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01796a2.cif
_cod_data_source_block           km23-3
_cod_original_cell_volume        5561.21(18)
_cod_database_code               1562341
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C86 H178 N2 O24 Si6 K1 U1'
_shelx_estimated_absorpt_t_max   0.667
_shelx_estimated_absorpt_t_min   0.311
_reflns_odcompleteness_completeness 99.85
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O106-C106
 2.4 with sigma of 0.02
 O104-C109 \\sim O107-C109 \\sim O105-C101 \\sim O102-C101 \\sim O106-C105
\\sim O103-C105
 with sigma of 0.02
 Si6-O102 \\sim Si7-O105 \\sim Si6-O103 \\sim Si7-O106 \\sim Si6-O104 \\sim
Si7-O107
 with sigma of 0.02
 Si7-O101 \\sim Si6-O101
 with sigma of 0.02
 C113-C115 \\sim C113-C114 \\sim C113-C116 \\sim C102-C101 \\sim C103-C101
\\sim C104-C101
 with sigma of 0.02
 O102-C101 \\sim O105-C113 \\sim O103-C105 \\sim O106-C105 \\sim O107-C109
\\sim O104-C109
 with sigma of 0.02
 C26-C25 \\sim C29-C25 \\sim C30-C25 \\sim C27-C25 \\sim C31-C25 \\sim C28-C25
 with sigma of 0.02
 C116-C115 \\sim C115-C114 \\sim C114-C116
 with sigma of 0.02
 C103-C102 \\sim C102-C104 \\sim C103-C104
 with sigma of 0.02
 C27-C26 \\sim C26-C28 \\sim C28-C27
 with sigma of 0.02
 C31-C29 \\sim C29-C30 \\sim C30-C31
 with sigma of 0.02
 C106-C105 \\sim C107-C105 \\sim C108-C105
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C43) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C48)
\\sim Ueq, Uanis(C91) \\sim Ueq: with sigma of 0.005 and sigma for terminal
atoms of 0.01
Uanis(C84) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C114)
\\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Rigid body (RIGU) restrains
 C1, C2, C3, C4, C5, C6, C7, C8, C9, C10, C11, C12, C21, C22, C23, C24, C25,
 C26, C27, C28, C29, C30, C31, C32, C33, C34, C35, C41, C42, C43, C44, C45, C46,
  C47, C48, C49, C50, C51, C52, C61, C62, C63, C64, C65, C66, C67, C68, C69,
 C70, C71, C72, C81, C82, C83, C84, C85, C86, C87, C88, C89, C90, C91, C92,
 C101, C102, C103, C104, C105, C106, C107, C108, C109, C110, C111, C112, C113,
 C114, C115, C116, O1, O2, O3, O4, O21, O22, O23, O24, O41, O42, O43, O44, O61,
 O62, O63, O64, O81, O82, O83, O84, O101, O102, O103, O104, O105, O106, O107,
 Si6, Si7
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(Si7)=Sof(O105)=Sof(O106)=Sof(O107)=Sof(C113)=Sof(C114)=Sof(H11M)=
 Sof(H11N)=Sof(H11O)=Sof(C115)=Sof(H11P)=Sof(H11Q)=Sof(H11R)=Sof(C116)=
 Sof(H11S)=Sof(H11T)=Sof(H11U)=1-FVAR(1)
 Sof(Si6)=Sof(O102)=Sof(O103)=Sof(O104)=Sof(C101)=Sof(C102)=Sof(H10D)=
 Sof(H10E)=Sof(H10F)=Sof(C103)=Sof(H10G)=Sof(H10H)=Sof(H10I)=Sof(C104)=
 Sof(H10J)=Sof(H10K)=Sof(H10L)=FVAR(1)
 Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=1-FVAR(2)
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=FVAR(2)
6.a 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), C29(H29A,H29B,
 H29C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C), 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), 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), C114(H11M,H11N,H11O), C115(H11P,H11Q,H11R),
 C116(H11S,H11T,H11U)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              35082
_shelx_hkl_checksum              28140
_shelx_fab_checksum              51549
_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 1.460
_oxdiff_exptl_absorpt_empirical_full_min 0.564