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_1564375
_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         'C32 H68 N3 O8 U2, 3(C24 H20 B)'
_chemical_formula_sum            'C104 H128 B3 N3 O8 U2'
_chemical_formula_weight         2056.58
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-04-26
_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                90
_cell_angle_beta                 106.7065(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   29.5736(3)
_cell_length_b                   13.29349(9)
_cell_length_c                   24.4177(2)
_cell_measurement_reflns_used    63894
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      75.8200
_cell_measurement_theta_min      3.6290
_cell_volume                     9194.29(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.107a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.107a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.107a (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 0.994
_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   -113.00 -61.00   1.00    5.00    --  -41.04-150.00 158.00   52
  2  \w    -68.00 -43.00   1.00    5.00    --  -41.04 122.00  41.00   25
  3  \w    -85.00 -60.00   1.00    5.00    --  -41.04 150.00-156.00   25
  4  \w     36.00  61.00   1.00    5.00    --   41.04-122.00 -39.00   25
  5  \w     76.00 101.00   1.00    5.00    --   41.04-150.00 158.00   25
  6  \w     60.00  85.00   1.00   20.00    --  112.00-150.00 158.00   25
  7  \w     50.00  75.00   1.00   20.00    --  112.00-122.00 -39.00   25
  8  \w     92.00 125.00   1.00   20.00    --  112.00 150.00-156.00   33
  9  \w    109.00 153.00   1.00   20.00    --  112.00 122.00  41.00   44
 10  \w   -109.00 -14.00   1.00    5.00    --  -41.04 -57.00  60.00   95
 11  \w   -109.00 -17.00   1.00    5.00    --  -41.04 -38.00 150.00   92
 12  \w    -87.00  -8.00   1.00    5.00    --  -41.04 125.00 -60.00   79
 13  \w    -28.00  62.00   1.00    5.00    --   41.04 -38.00  90.00   90
 14  \w     11.00  74.00   1.00    5.00    --   41.04 -99.00-120.00   63
 15  \w    109.00 135.00   1.00   20.00    --  112.00  30.00  90.00   26
 16  \w     37.00  98.00   1.00   20.00    --  112.00-111.00-120.00   61
 17  \w     86.00 175.00   1.00   20.00    --  112.00  45.00  30.00   89
 18  \w    106.00 136.00   1.00   20.00    --  112.00 -45.00 120.00   30
 19  \w    116.00 176.00   1.00   20.00    --  112.00 111.00  30.00   60
 20  \w     66.00 109.00   1.00   20.00    --  112.00-111.00  60.00   43
 21  \w     37.00 105.00   1.00   20.00    --  112.00-111.00-150.00   68
 22  \w     56.00  81.00   1.00   20.00    --  112.00 -77.00 150.00   25
 23  \w     87.00 112.00   1.00   20.00    --  112.00 -77.00 150.00   25
 24  \w     54.00  90.00   1.00   20.00    --  112.00 -45.00 120.00   36
 25  \w     87.00 151.00   1.00   20.00    --  112.00  30.00-180.00   64
 26  \w     40.00 108.00   1.00   20.00    --  112.00-111.00 150.00   68
 27  \w    133.00 174.00   1.00   20.00    --  112.00 111.00-180.00   41
 28  \w     36.00  85.00   1.00   20.00    --  112.00 -94.00  60.00   49
 29  \w    106.00 178.00   1.00   20.00    --  112.00  77.00-150.00   72
 30  \w     80.00 122.00   1.00   20.00    --  112.00 178.00-150.00   42
 31  \w     86.00 114.00   1.00   20.00    --  112.00  45.00   0.00   28
 32  \w    123.00 178.00   1.00   20.00    --  112.00  45.00   0.00   55
 33  \w     36.00 109.00   1.00   20.00    --  112.00-111.00 -30.00   73
 34  \w     81.00 107.00   1.00   20.00    --  112.00 -94.00 -30.00   26
 35  \w     68.00 109.00   1.00   20.00    --  112.00-111.00 -90.00   41
 36  \w    105.00 146.00   1.00   20.00    --  112.00  77.00 -60.00   41
 37  \w     62.00 109.00   1.00   20.00    --  112.00-111.00 120.00   47
 38  \w     52.00  81.00   1.00   20.00    --  112.00 -94.00  30.00   29
 39  \w     79.00 137.00   1.00   20.00    --  112.00 -61.00 -90.00   58
 40  \w    110.00 173.00   1.00   20.00    --  112.00 111.00 -90.00   63
 41  \w     90.00 174.00   1.00   20.00    --  112.00  61.00  90.00   84
 42  \w     47.00  72.00   1.00   20.00    --  112.00 -61.00-150.00   25
 43  \w    106.00 140.00   1.00   20.00    --  112.00 -61.00-150.00   34
 44  \w     61.00  86.00   1.00   20.00    --  112.00-111.00-180.00   25
 45  \w    124.00 153.00   1.00   20.00    --  112.00  61.00 -30.00   29
;
_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      0.0541305000
_diffrn_orient_matrix_UB_12      0.0046252000
_diffrn_orient_matrix_UB_13      0.0244882000
_diffrn_orient_matrix_UB_21      0.0005895000
_diffrn_orient_matrix_UB_22      0.0999581000
_diffrn_orient_matrix_UB_23      -0.0317010000
_diffrn_orient_matrix_UB_31      -0.0053277000
_diffrn_orient_matrix_UB_32      0.0584105000
_diffrn_orient_matrix_UB_33      0.0522870000
_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  0.0337
_diffrn_reflns_av_unetI/netI     0.0210
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            115292
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.142
_diffrn_reflns_theta_min         3.120
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.289
_exptl_absorpt_correction_T_max  0.597
_exptl_absorpt_correction_T_min  0.233
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.107a (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 intense orange'
_exptl_crystal_density_diffrn    1.486
_exptl_crystal_description       plate
_exptl_crystal_F_000             4144
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.133
_exptl_crystal_size_min          0.058
_refine_diff_density_max         1.967
_refine_diff_density_min         -2.698
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1243
_refine_ls_number_reflns         19118
_refine_ls_number_restraints     1969
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0302
_refine_ls_R_factor_gt           0.0281
_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^)+(0.0328P)^2^+17.0380P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0693
_refine_ls_wR_factor_ref         0.0709
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18009
_reflns_number_total             19118
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc03957a2.cif
_cod_data_source_block           mk-218
_cod_original_cell_volume        9194.26(14)
_cod_database_code               1564375
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C104 H128 B3 N3 O8 U2'
_shelx_estimated_absorpt_t_max   0.587
_shelx_estimated_absorpt_t_min   0.183
_reflns_odcompleteness_completeness 99.96
_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 C(H,H) groups, All C(H,H,H,H) groups, All N(H,H) groups
2. Restrained distances
 C30-C29 \\sim C33-C29 \\sim C31-C30 \\sim C34-C33 \\sim C32-C31 \\sim C35-C34
\\sim C45-C44 \\sim C49-C48
 \\sim C46-C45 \\sim C50-C49 \\sim C47-C46 \\sim C50-C47 \\sim C16-C12 \\sim
C13-C12 \\sim C14-C13 \\sim C17-
 C16 \\sim C15-C14 \\sim C18-C17 \\sim C8-C7 \\sim C8-C11 \\sim C9-C10 \\sim
C6-C5 \\sim C11-C10 \\sim C7-C6 ~
 C22-C21 \\sim C24-C23 \\sim C21-C20 \\sim C23-C20 \\sim C20-C19 \\sim C37-C36
\\sim C41-C40 \\sim C38-C37
 \\sim C42-C41 \\sim C43-C42 \\sim C39-C38
 with sigma of 0.02
 O6-C29 \\sim O6-C32 \\sim O6-C35 \\sim O8-C47 \\sim O8-C48 \\sim O8-C44 \\sim
O3-C15 \\sim O3-C18 \\sim O3-
 C12 \\sim O2-C9 \\sim O2-C5 \\sim O2-C8 \\sim O4-C22 \\sim O4-C24 \\sim O4-C19
\\sim O7-C40 \\sim O7-C36 \\sim O7-
 C39 \\sim O7-C43
 with sigma of 0.02
3. 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
4. Others
 Sof(H12C)=Sof(H12D)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=1-FVAR(1)
 Sof(H12A)=Sof(H12B)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(C15)=Sof(H15A)=Sof(H15B)=FVAR(1)
 Sof(H47C)=Sof(H47D)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(C49)=Sof(H49A)=Sof(H49B)=
 Sof(C50)=Sof(H50A)=Sof(H50B)=1-FVAR(2)
 Sof(C44)=Sof(H44A)=Sof(H44B)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(C46)=Sof(H46A)=
 Sof(H46B)=Sof(H47A)=Sof(H47B)=FVAR(2)
 Sof(H29C)=Sof(H29D)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(C34)=Sof(H34A)=Sof(H34B)=
 Sof(C35)=Sof(H35A)=Sof(H35B)=1-FVAR(3)
 Sof(H29A)=Sof(H29B)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(C31)=Sof(H31A)=Sof(H31B)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=FVAR(3)
 Sof(H20C)=Sof(H20D)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=
 1-FVAR(4)
 Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C22)=Sof(H22A)=Sof(H22B)=
 FVAR(4)
 Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(C42)=Sof(H42A)=
 Sof(H42B)=Sof(C43)=Sof(H43A)=Sof(H43B)=1-FVAR(5)
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(C38)=Sof(H38A)=
 Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=FVAR(5)
 Sof(H8BC)=Sof(H8BD)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10A)=Sof(H10B)=
 Sof(C11)=Sof(H11A)=Sof(H11B)=1-FVAR(6)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(H8AA)=Sof(H8AB)=FVAR(6)
 Fixed X: U1(0.20508) U2(0.32015)
 Fixed Y: U1(0.53156) U2(0.54191)
 Fixed Z: U1(0.735129) U2(0.758301)
5.a Secondary CH2 refined with riding coordinates:
 N2(H2A,H2B), N3(H3A,H3B), C1(H1A,H1B), C2(H2C,H2D), C3(H3C,H3D), C4(H4A,H4B),
 C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8AA,H8AB), C8(H8BC,H8BD), C9(H9A,
 H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C12(H12C,H12D), C13(H13A,
 H13B), C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B),
 C18(H18A,H18B), C19(H19A,H19B), C20(H20A,H20B), C20(H20C,H20D), C21(H21A,H21B),
  C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C25(H25A,H25B), C26(H26A,
 H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C29(H29C,H29D),
 C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B),
  C35(H35A,H35B), C36(H36A,H36B), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,
 H39B), C40(H40A,H40B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B),
 C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B), C47(H47A,H47B), C47(H47C,H47D),
  C48(H48A,H48B), C49(H49A,H49B), C50(H50A,H50B)
5.b Aromatic/amide H refined with riding coordinates:
 C52(H52), C53(H53), C54(H54), C55(H55), C56(H56), C58(H58), C59(H59),
 C60(H60), C61(H61), C62(H62), C64(H64), C65(H65), C66(H66), C67(H67), C68(H68),
  C70(H70), C71(H71), C72(H72), C73(H73), C74(H74), C76(H76), C77(H77),
 C78(H78), C79(H79), C80(H80), C82(H82), C83(H83), C84(H84), C85(H85), C86(H86),
  C88(H88), C89(H89), C90(H90), C91(H91), C92(H92), C94(H94), C95(H95),
 C96(H96), C97(H97), C98(H98), C100(H100), C101(H101), C102(H102), C103(H103),
 C104(H104), C106(H106), C107(H107), C108(H108), C109(H109), C110(H110),
 C112(H112), C113(H113), C114(H114), C115(H115), C116(H116), C118(H118),
 C119(H119), C120(H120), C121(H121), C122(H122)
;
_shelx_res_checksum              14230
_shelx_hkl_checksum              89030
_olex2_date_sample_data_collection 2021-04-23
_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 1.769
_oxdiff_exptl_absorpt_empirical_full_min 0.634