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_1562344
_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 I1 K2 N2 O24 Si6 U2, 1[C7H8]'
_chemical_formula_sum            'C72 H162 I K2 N2 O24 Si6 U2'
_chemical_formula_weight         2289.80
_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             2020-04-30
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2021-03-22 deposited with the CCDC.	2021-04-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.822(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.9014(3)
_cell_length_b                   18.1586(5)
_cell_length_c                   22.0984(5)
_cell_measurement_reflns_used    38679
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.4090
_cell_measurement_theta_min      3.9120
_cell_volume                     5571.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.71a (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 2018/2 (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 1.000
_diffrn_measured_fraction_theta_max 0.988
_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     -4.00  21.00   1.00    3.00    --   34.00  92.00-114.87   25
  2  \w     -3.00  22.00   1.00    3.00    --   34.00  90.00 112.47   25
  3  \w   -112.00 -18.00   1.00    3.00    --  -42.76 -37.00   0.00   94
  4  \w    -96.00 -18.00   1.00    3.00    --  -42.76 -37.00-120.00   78
  5  \w   -113.00 -18.00   1.00    3.00    --  -42.76 -37.00  90.00   95
  6  \w   -121.00  -7.00   1.00    3.00    --  -42.76 -19.00-180.00  114
  7  \w    -86.00 -10.00   1.00    3.00    --  -42.76 125.00-120.00   76
  8  \w      8.00  84.00   1.00    3.00    --   42.76 -99.00  90.00   76
  9  \w     16.00  41.00   1.00    3.00    --   50.00  82.00  28.41   25
 10  \w     16.00  41.00   1.00    3.00    --   50.00  81.00 178.59   25
 11  \w     16.00  41.00   1.00    3.00    --   50.00  81.00 121.96   25
 12  \w     16.00  41.00   1.00    3.00    --   50.00  81.00  79.33   25
 13  \w     16.00  41.00   1.00    3.00    --   50.00  82.00-113.58   25
 14  \w     16.00  42.00   1.00    3.00    --   50.00  81.00 -41.46   26
 15  \w     31.00  58.00   1.00    3.00    --   62.00  72.00 -88.66   27
 16  \w     32.00  59.00   1.00    3.00    --   62.00  73.00 -44.61   27
 17  \w     97.00 137.00   1.00    3.00    --   62.00  73.00 -44.61   40
 18  \w     96.00 136.00   1.00    3.00    --   62.00  72.00 -88.66   40
 19  \w     34.00  60.00   1.00    3.00    --   66.00  74.00  -2.93   26
 20  \w     34.00  60.00   1.00    3.00    --   66.00  74.00-176.96   26
 21  \w     34.00  61.00   1.00    3.00    --   66.00  74.00-137.37   27
 22  \w     34.00  61.00   1.00    3.00    --   66.00  73.00 101.32   27
 23  \w     99.00 126.00   1.00    3.00    --   70.00  72.00 153.04   27
 24  \w     39.00  66.00   1.00    3.00    --   70.00  72.00 153.04   27
 25  \w     38.00  64.00   1.00    3.00    --   70.00  73.00  43.95   26
 26  \w     43.00  70.00   1.00   12.00    --   74.00  69.00-158.38   27
 27  \w     43.00  69.00   1.00   12.00    --   74.00  72.00 119.04   26
 28  \w     47.00  74.00   1.00   12.00    --   78.00  71.00 -84.71   27
 29  \w     46.00  73.00   1.00   12.00    --   78.00  73.00-115.71   27
 30  \w     46.00  74.00   1.00   12.00    --   78.00  74.00 -58.53   28
 31  \w     47.00  74.00   1.00   12.00    --   78.00  69.00  12.48   27
 32  \w     47.00  74.00   1.00   12.00    --   78.00  69.00  -3.22   27
 33  \w     50.00  77.00   1.00   12.00    --   82.00  74.00  46.01   27
 34  \w    132.00 157.00   1.00   12.00    --   82.00  73.00 -41.58   25
 35  \w     50.00  76.00   1.00   12.00    --   82.00  73.00 -41.58   26
 36  \w     52.00  79.00   1.00   12.00    --   82.00  67.00 113.28   27
 37  \w     54.00  81.00   1.00   12.00    --   82.00  60.00-127.09   27
 38  \w     58.00  84.00   1.00   12.00    --   90.00  74.00 125.95   26
 39  \w     59.00  85.00   1.00   12.00    --   90.00  69.00 174.18   26
 40  \w     60.00  87.00   1.00   12.00    --   90.00  66.00  77.44   27
 41  \w     62.00  88.00   1.00   12.00    --   94.00  73.00 -19.06   26
 42  \w     63.00 102.00   1.00   12.00    --   94.00  71.00  18.06   39
 43  \w    136.00 163.00   1.00   12.00    --   94.00  73.00 -19.06   27
 44  \w     96.00 165.00   1.00   12.00    --   98.00  73.00 179.25   69
 45  \w     66.00  94.00   1.00   12.00    --   98.00  73.00 179.25   28
 46  \w     94.00 168.00   1.00   12.00    --   98.00  74.00 139.59   74
 47  \w     66.00  93.00   1.00   12.00    --   98.00  74.00 139.59   27
 48  \w     68.00 161.00   1.00   12.00    --   98.00  73.00  38.79   93
 49  \w     75.00 101.00   1.00   12.00    --  103.80  61.00-120.00   26
 50  \w     76.00 171.00   1.00   12.00    --  103.80  61.00   0.00   95
 51  \w     33.00 133.00   1.00   12.00    --  103.80 -61.00   0.00  100
 52  \w     74.00 141.00   1.00   12.00    --  103.80  66.00-102.26   67
 53  \w    115.00 176.00   1.00   12.00    --  103.80  61.00-150.00   61
 54  \w     75.00 102.00   1.00   12.00    --  103.80  61.00-150.00   27
 55  \w     38.00 108.00   1.00   12.00    --  103.80-111.00 -60.00   70
 56  \w     77.00 167.00   1.00   12.00    --  103.80  48.00 -30.97   90
 57  \w     78.00 105.00   1.00   12.00    --  103.80-111.00  60.00   27
 58  \w    147.00 174.00   1.00   12.00    --  103.80  61.00-120.00   27
 59  \w     28.00  55.00   1.00   12.00    --  103.80-111.00  60.00   27
 60  \w     41.00 106.00   1.00   12.00    --  103.80 -94.00 -30.00   65
 61  \w     67.00 100.00   1.00   12.00    --  103.80-111.00-120.00   33
 62  \w     75.00 176.00   1.00   12.00    --  103.80  62.00  82.15  101
 63  \w     74.00 177.00   1.00   12.00    --  103.80  69.00 118.85  103
 64  \w     75.00 108.00   1.00   12.00    --  103.80-111.00 150.00   33
 65  \w     31.00 124.00   1.00   12.00    --  103.80 -45.00 120.00   93
 66  \w    116.00 165.00   1.00   12.00    --  103.80  70.00 -76.52   49
 67  \w     46.00 108.00   1.00   12.00    --  103.80-111.00-180.00   62
 68  \w     73.00 101.00   1.00   12.00    --  103.80  70.00 -76.52   28
;
_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      -0.0443554000
_diffrn_orient_matrix_UB_12      -0.0068873000
_diffrn_orient_matrix_UB_13      -0.0650333000
_diffrn_orient_matrix_UB_21      0.0307310000
_diffrn_orient_matrix_UB_22      -0.0814879000
_diffrn_orient_matrix_UB_23      -0.0015739000
_diffrn_orient_matrix_UB_31      -0.0969205000
_diffrn_orient_matrix_UB_32      -0.0227423000
_diffrn_orient_matrix_UB_33      0.0252558000
_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  0.0698
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            107607
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.133
_diffrn_reflns_theta_min         3.151
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.045
_exptl_absorpt_correction_T_max  0.602
_exptl_absorpt_correction_T_min  0.169
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.71a (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
 as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            'clear light brown'
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_description       needle
_exptl_crystal_F_000             2318
_exptl_crystal_size_max          0.391
_exptl_crystal_size_mid          0.053
_exptl_crystal_size_min          0.051
_refine_diff_density_max         1.693
_refine_diff_density_min         -1.328
_refine_diff_density_rms         0.109
_refine_ls_abs_structure_details
;
 Flack x determined using 8037 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.026(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1054
_refine_ls_number_reflns         21762
_refine_ls_number_restraints     1851
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0481
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0707P)^2^+10.0363P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1200
_refine_ls_wR_factor_ref         0.1274
_reflns_Friedel_coverage         0.910
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.961
_reflns_number_gt                19157
_reflns_number_total             21762
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc01796a2.cif
_cod_data_source_block           lb944
_cod_database_code               1562344
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C79 H170 I K2 N2 O24 Si6 U2'
_shelx_estimated_absorpt_t_max   0.579
_shelx_estimated_absorpt_t_min   0.088
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C44A-C41 = C44B-C41 = C42-C41 = C43-C41
 1.54 with sigma of 0.02
 U1-N2B = U2-N2B = U2-N1B = U1-N1B = U1-N1C = U2-N1C = U1-N2C = U2-N2C
 2.2 with sigma of 0.01
 C47-C45 = C48-C45 = C46-C45
 1.54 with sigma of 0.02
 N1B-N2B
 2.37 with sigma of 0.02
 N1C-N2C
 2.37 with sigma of 0.02
 N2C-I1C = I1C-N1C
 3.3 with sigma of 0.02
 N1B-I1B = I1B-N2B
 3.3 with sigma of 0.02
 C47-C48 \\sim C48-C46 \\sim C46-C47
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1 \\sim O2 \\sim O3 \\sim O4 \\sim O21 \\sim O22 \\sim O23 \\sim O24 \\sim O41
\\sim O42A \\sim O42B \\sim O43A \\sim O43B \\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 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 C44A \\sim C44B \\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: within 2A with sigma of 0.005
and sigma for terminal atoms of 0.01 within 2A
Uanis(N1A) \\sim Ueq, Uanis(N1B) \\sim Ueq, Uanis(N1C) \\sim Ueq, Uanis(N2A)
\\sim Ueq, Uanis(N2B) \\sim Ueq, Uanis(N2C) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(I1A) = Uanis(I1C)
Uanis(I1A) = Uanis(I1B)
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
 1*[Sof(I1A)+Sof(N1A)+Sof(N2A)]+1*[Sof(I1B)+Sof(N1B)+Sof(N2B)]+1*[Sof(I1C)+
 Sof(N1C)+Sof(N2C)]=1 with esd of 0.001
 Sof(O42B)=Sof(O43B)=Sof(C44B)=Sof(H44D)=Sof(H44E)=Sof(H44F)=1-FVAR(1)
 Sof(O42A)=Sof(O43A)=Sof(C44A)=Sof(H44A)=Sof(H44B)=Sof(H44C)=FVAR(1)
 Sof(I1A)=Sof(N1A)=Sof(N2A)=FVAR(2)
 Sof(I1B)=Sof(N1B)=Sof(N2B)=FVAR(3)
 Sof(I1C)=Sof(N1C)=Sof(N2C)=FVAR(4)
 Fixed Y: U1(0.525921)
6.a 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), C44A(H44A,H44B,H44C), C44B(H44D,H44E,H44F), 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(H1C,H63A,H63B), 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              70329
_shelx_hkl_checksum              77277
_shelx_fab_checksum              41231
_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 3.138
_oxdiff_exptl_absorpt_empirical_full_min 0.446