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_1564376
_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
'C42 H68 N10 Si4 U2, 4(C5 H5 N), 2(C24 H20 B)'
_chemical_formula_sum            'C110 H128 B2 N14 Si4 U2'
_chemical_formula_weight         2256.30
_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             2020-12-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_audit_update_record
;
2021-07-16 deposited with the CCDC.	2021-08-13 downloaded from the CCDC.
;
_cell_angle_alpha                103.7856(18)
_cell_angle_beta                 98.6207(18)
_cell_angle_gamma                115.188(2)
_cell_formula_units_Z            1
_cell_length_a                   13.3639(3)
_cell_length_b                   14.7692(3)
_cell_length_c                   17.1055(4)
_cell_measurement_reflns_used    19007
_cell_measurement_temperature    140.01(10)
_cell_measurement_theta_max      76.1660
_cell_measurement_theta_min      3.6160
_cell_volume                     2843.26(13)
_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 1.000
_diffrn_measured_fraction_theta_max 0.987
_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   -115.00 -13.00   1.00    2.50    --  -43.01 -66.00 -79.00  102
  2  \w    -60.00  22.00   1.00    2.50    --  -43.01  66.00  54.00   82
  3  \w    137.00 178.00   1.00   10.00    --  112.00  66.00  54.00   41
  4  \w    113.00 140.00   1.00   10.00    --  112.00 -66.00 -79.00   27
  5  \w     40.00  72.00   1.00   10.00    --  112.00 -66.00 -79.00   32
  6  \w     93.00 118.00   1.00   10.00    --  112.00  66.00  54.00   25
  7  \w   -114.00 -16.00   1.00    2.50    --  -43.01 -57.00-180.00   98
  8  \w    -21.00  15.00   1.00    2.50    --   43.01 -77.00 150.00   36
  9  \w     -7.00  20.00   1.00    2.50    --   43.01 -77.00 -60.00   27
 10  \w      4.00  29.00   1.00    2.50    --   43.01 -66.00 -79.00   25
 11  \w     40.00  65.00   1.00    2.50    --   43.01  66.00  54.00   25
 12  \w     36.00  98.00   1.00    2.50    --   43.01-125.00-180.00   62
 13  \w     36.00 109.00   1.00   10.00    --  112.00-111.00 120.00   73
 14  \w    128.00 174.00   1.00   10.00    --  112.00  30.00   0.00   46
 15  \w     53.00 134.00   1.00   10.00    --  112.00 -45.00  60.00   81
 16  \w    105.00 178.00   1.00   10.00    --  112.00  77.00 120.00   73
 17  \w     41.00 109.00   1.00   10.00    --  112.00-111.00  60.00   68
 18  \w     85.00 110.00   1.00   10.00    --  112.00 -77.00 120.00   25
 19  \w    105.00 147.00   1.00   10.00    --  112.00 111.00-180.00   42
 20  \w     59.00  86.00   1.00   10.00    --  112.00 -45.00 120.00   27
 21  \w     37.00 108.00   1.00   10.00    --  112.00-111.00 -60.00   71
 22  \w     85.00 110.00   1.00   10.00    --  112.00  30.00   0.00   25
 23  \w     57.00 109.00   1.00   10.00    --  112.00-111.00   0.00   52
 24  \w    107.00 136.00   1.00   10.00    --  112.00  77.00 150.00   29
 25  \w     84.00 178.00   1.00   10.00    --  112.00  30.00 -90.00   94
 26  \w     55.00  92.00   1.00   10.00    --  112.00-111.00 -90.00   37
 27  \w    113.00 155.00   1.00   10.00    --  112.00 111.00  90.00   42
 28  \w    106.00 144.00   1.00   10.00    --  112.00  77.00  30.00   38
 29  \w    153.00 178.00   1.00   10.00    --  112.00  77.00  30.00   25
 30  \w     64.00  89.00   1.00   10.00    --  112.00-111.00 -30.00   25
 31  \w     38.00  63.00   1.00   10.00    --  112.00-111.00 150.00   25
 32  \w     75.00 106.00   1.00   10.00    --  112.00-111.00 150.00   31
 33  \w     52.00  96.00   1.00   10.00    --  112.00-111.00  30.00   44
 34  \w    109.00 144.00   1.00   10.00    --  112.00 111.00 150.00   35
 35  \w    131.00 177.00   1.00   10.00    --  112.00  45.00  90.00   46
 36  \w     65.00 104.00   1.00   10.00    --  112.00-111.00  90.00   39
 37  \w     87.00 113.00   1.00   10.00    --  112.00 -45.00 120.00   26
 38  \w     86.00 121.00   1.00   10.00    --  112.00  45.00  90.00   35
 39  \w     66.00 108.00   1.00   10.00    --  112.00-102.00 164.26   42
 40  \w     38.00 109.00   1.00   10.00    --  112.00-111.00-120.00   71
;
_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      0.0597880000
_diffrn_orient_matrix_UB_12      0.1080646000
_diffrn_orient_matrix_UB_13      0.0715188000
_diffrn_orient_matrix_UB_21      0.1170948000
_diffrn_orient_matrix_UB_22      0.0206548000
_diffrn_orient_matrix_UB_23      -0.0157351000
_diffrn_orient_matrix_UB_31      -0.0196830000
_diffrn_orient_matrix_UB_32      0.0537771000
_diffrn_orient_matrix_UB_33      -0.0632672000
_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  0.0234
_diffrn_reflns_av_unetI/netI     0.0263
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            32842
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.529
_diffrn_reflns_theta_min         2.776
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    8.735
_exptl_absorpt_correction_T_max  0.600
_exptl_absorpt_correction_T_min  0.153
_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    1.318
_exptl_crystal_description       prism
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.357
_exptl_crystal_size_mid          0.103
_exptl_crystal_size_min          0.078
_refine_diff_density_max         1.402
_refine_diff_density_min         -1.062
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.032
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     601
_refine_ls_number_reflns         11800
_refine_ls_number_restraints     491
_refine_ls_restrained_S_all      1.014
_refine_ls_R_factor_all          0.0311
_refine_ls_R_factor_gt           0.0298
_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^)+(0.0540P)^2^+2.0899P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0802
_refine_ls_wR_factor_ref         0.0814
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11293
_reflns_number_total             11800
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc03957a2.cif
_cod_data_source_block           mk-65-py
_cod_original_cell_volume        2843.27(12)
_cod_database_code               1564376
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C120 H138 B2 N16 Si4 U2'
_shelx_estimated_absorpt_t_max   0.549
_shelx_estimated_absorpt_t_min   0.147
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. 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
3.a Aromatic/amide H refined with riding coordinates:
 N1(H1), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13),
 C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19), C20(H20), C21(H21),
  C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
 C29(H29), C30(H30), C31(H31), C33(H33), C34(H34), C35(H35), C36(H36), C37(H37),
  C39(H39), C40(H40), C41(H41), C42(H42), C43(H43), C45(H45), C46(H46),
 C47(H47), C48(H48), C49(H49), C51(H51), C52(H52), C53(H53), C54(H54), C55(H55)
3.b 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)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 83 electrons were 
found in a volume of 352\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
1[C5H5N] per Asymmetric Unit 
which account for 84 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              56674
_shelx_hkl_checksum              38944
_shelx_fab_checksum              66169
_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 1.571
_oxdiff_exptl_absorpt_empirical_full_min 0.753