Nitride Protonation and NH3 Binding versus N‒H Bond Cleavage in Uranium Nitrides
Keener, Megan; Scopelliti, Rosario; Mazzanti, Marinella; Chemical Science  (2021) –; doi:10.1039/D1SC03957A

data_1564374
_publ_section_title
;
 Nitride Protonation and NH3 Binding versus N--H Bond Cleavage in Uranium
 Nitrides
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC03957A
_journal_year                    2021
_chemical_formula_moiety         'C36 H86 N4 O6 Si4 U2, 2(C24 H20 B)'
_chemical_formula_sum            'C84 H126 B2 N4 O6 Si4 U2'
_chemical_formula_weight         1897.92
_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             2021-02-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-07-16 deposited with the CCDC.	2021-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                70.121(4)
_cell_angle_beta                 69.828(4)
_cell_angle_gamma                89.220(3)
_cell_formula_units_Z            1
_cell_length_a                   11.3861(4)
_cell_length_b                   14.4053(6)
_cell_length_c                   15.2365(6)
_cell_measurement_reflns_used    7801
_cell_measurement_temperature    140.01(10)
_cell_measurement_theta_max      72.2210
_cell_measurement_theta_min      3.2230
_cell_volume                     2190.76(17)
_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      140.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.972
_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    -79.00  20.00   1.00    7.50    --  -43.13  92.00-126.00   99
  2  \w     32.00  59.00   1.00    7.50    --   43.13 -92.00 120.00   27
  3  \w    109.00 136.00   1.00   30.00    --  103.80  92.00-126.00   27
  4  \w     20.00 104.00   1.00   30.00    --  103.80 -92.00 120.00   84
  5  \w    -66.00  22.00   1.00    7.50    --  -43.13  37.00  60.00   88
  6  \w    -60.00  31.00   1.00    7.50    --  -43.13  37.00 150.00   91
  7  \w     68.00 116.00   1.00    7.50    --   43.13  57.00   0.00   48
  8  \w     29.00  59.00   1.00    7.50    --   43.13  57.00   0.00   30
  9  \w    111.00 178.00   1.00   30.00    --  103.80  77.00 -90.00   67
 10  \w    109.00 136.00   1.00   30.00    --  103.80 111.00-180.00   27
 11  \w     29.00  94.00   1.00   30.00    --  103.80 -77.00 -90.00   65
 12  \w     21.00  74.00   1.00   30.00    --  103.80 -94.00  30.00   53
 13  \w     79.00 175.00   1.00   30.00    --  103.80  61.00  60.00   96
 14  \w     91.00 178.00   1.00   30.00    --  103.80  30.00 -30.00   87
 15  \w     40.00  68.00   1.00   30.00    --  103.80-111.00 -90.00   28
 16  \w     43.00  74.00   1.00   30.00    --  103.80-111.00   0.00   31
 17  \w     56.00 108.00   1.00   30.00    --  103.80-111.00  90.00   52
 18  \w     35.00  70.00   1.00   30.00    --  103.80 -61.00 150.00   35
 19  \w     29.00 107.00   1.00   30.00    --  103.80-111.00-120.00   78
 20  \w    152.00 178.00   1.00   30.00    --  103.80  77.00 -60.00   26
 21  \w    103.00 171.00   1.00   30.00    --  103.80  77.00   0.00   68
 22  \w     83.00 108.00   1.00   30.00    --  103.80-111.00 -90.00   25
 23  \w     31.00  57.00   1.00   30.00    --  103.80-111.00  30.00   26
 24  \w     66.00 108.00   1.00   30.00    --  103.80-111.00  30.00   42
 25  \w    140.00 167.00   1.00   30.00    --  103.80  77.00 120.00   27
;
_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      0.0036122000
_diffrn_orient_matrix_UB_12      -0.1049972000
_diffrn_orient_matrix_UB_13      0.0708532000
_diffrn_orient_matrix_UB_21      -0.1279144000
_diffrn_orient_matrix_UB_22      0.0060375000
_diffrn_orient_matrix_UB_23      0.0760840000
_diffrn_orient_matrix_UB_31      -0.0685027000
_diffrn_orient_matrix_UB_32      -0.0453010000
_diffrn_orient_matrix_UB_33      -0.0499206000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0377
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            9042
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.738
_diffrn_reflns_theta_min         3.309
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.234
_exptl_absorpt_correction_T_max  0.521
_exptl_absorpt_correction_T_min  0.309
_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            yellow
_exptl_crystal_density_diffrn    1.439
_exptl_crystal_description       prism
_exptl_crystal_F_000             956
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.108
_exptl_crystal_size_min          0.084
_refine_diff_density_max         4.215
_refine_diff_density_min         -1.864
_refine_diff_density_rms         0.182
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     486
_refine_ls_number_reflns         9042
_refine_ls_number_restraints     75
_refine_ls_restrained_S_all      0.995
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0403
_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^)+(0.0793P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1004
_refine_ls_wR_factor_ref         0.1022
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7960
_reflns_number_total             9042
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9400\% 
around [0.89 0.01 0.45] (reciprocal) or [1.00 -0.01 0.03] (direct)
;
_cod_data_source_file            d1sc03957a2.cif
_cod_data_source_block           mk-27_sq
_cod_original_cell_volume        2190.76(16)
_cod_database_code               1564374
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C86 H128 B2 N4 O6.5 Si4 U2'
_shelx_estimated_absorpt_t_max   0.452
_shelx_estimated_absorpt_t_min   0.237
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6250(14)
 0.3750(14)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C16-C15 \\sim C44-C15 \\sim C44-C43 \\sim C17-C16 \\sim C43-C18 \\sim C18-C17
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C15 \\sim C16 \\sim C17 \\sim C18 \\sim C43 \\sim C44: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
5. Others
 Sof(H15C)=Sof(H15D)=Sof(H18C)=Sof(H18D)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(C44)=
 Sof(H44A)=Sof(H44B)=1-FVAR(1)
 Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(H18A)=Sof(H18B)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B), C13(H13A,H13B), C14(H14A,H14B), C15(H15A,H15B), C15(H15C,H15D),
  C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C18(H18C,H18D), C43(H43A,
 H43B), C44(H44A,H44B)
6.b Aromatic/amide H refined with riding coordinates:
 N2(H2), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24), C26(H26), C27(H27),
 C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36),
  C38(H38), C39(H39), C40(H40), C41(H41), C42(H42)
6.c Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,
 H5B,H5C), C6(H6A,H6B,H6C)
;
_shelx_res_checksum              75738
_shelx_hkl_checksum              91874
_shelx_fab_checksum              88265
_platon_squeeze_void_probe_radius 1.20
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.649
_oxdiff_exptl_absorpt_empirical_full_min 0.673
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2