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_1564373
_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         'C80 H179 N O26 Si6 U2'
_chemical_formula_sum            'C80 H179 N O26 Si6 U2'
_chemical_formula_weight         2215.83
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-05-26
_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                 90.9900(19)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   25.5184(4)
_cell_length_b                   14.0899(4)
_cell_length_c                   61.6564(14)
_cell_measurement_reflns_used    11869
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      72.2510
_cell_measurement_theta_min      3.3920
_cell_volume                     22165.4(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.108a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.108a (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 10.2665
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.963
_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    -72.00   5.00   0.50    8.00    --  -43.13 109.00 -70.00  154
  2  \w     46.00  71.00   0.50    8.00    --   43.13-109.00-166.00   50
  3  \w     76.00 102.00   0.50   32.00    --  103.80-109.00-166.00   52
  4  \w    123.00 149.00   0.50   32.00    --  103.80 109.00 -70.00   52
  5  \w    -67.00  27.00   0.50    8.00    --  -43.13  37.00  90.00  188
  6  \w     20.00  67.00   0.50    8.00    --   43.13 -37.00  60.00   94
  7  \w     14.00  39.00   0.50    8.00    --   43.13  80.00   3.74   50
  8  \w     28.00  99.00   0.50   32.00    --  103.80 -94.00-120.00  142
  9  \w     34.00  80.00   0.50   32.00    --  103.80 -61.00 -60.00   92
 10  \w    136.00 162.00   0.50   32.00    --  103.80  77.00-180.00   52
 11  \w     61.00  95.00   0.50   32.00    --  103.80-111.00 -60.00   68
 12  \w     79.00 163.00   0.50   32.00    --  103.80  45.00 120.00  168
 13  \w    119.00 177.00   0.50   32.00    --  103.80 111.00 -90.00  116
 14  \w     51.00 130.00   0.50   32.00    --  103.80 -61.00 -30.00  158
;
_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      -0.0037038000
_diffrn_orient_matrix_UB_12      -0.0514729000
_diffrn_orient_matrix_UB_13      -0.0220421000
_diffrn_orient_matrix_UB_21      0.0166431000
_diffrn_orient_matrix_UB_22      -0.0936716000
_diffrn_orient_matrix_UB_23      0.0110359000
_diffrn_orient_matrix_UB_31      -0.0578640000
_diffrn_orient_matrix_UB_32      -0.0234850000
_diffrn_orient_matrix_UB_33      0.0041259000
_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  0.0755
_diffrn_reflns_av_unetI/netI     0.1146
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       76
_diffrn_reflns_limit_l_min       -74
_diffrn_reflns_number            49968
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.903
_diffrn_reflns_theta_min         3.464
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.283
_exptl_absorpt_correction_T_max  0.731
_exptl_absorpt_correction_T_min  0.490
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.108a (Rigaku Oxford Diffraction, 2021)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear pale colourless'
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_description       irregular
_exptl_crystal_F_000             9136
_exptl_crystal_size_max          0.123
_exptl_crystal_size_mid          0.069
_exptl_crystal_size_min          0.059
_refine_diff_density_max         2.450
_refine_diff_density_min         -1.176
_refine_diff_density_rms         0.177
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1272
_refine_ls_number_reflns         21305
_refine_ls_number_restraints     1474
_refine_ls_restrained_S_all      1.019
_refine_ls_R_factor_all          0.1012
_refine_ls_R_factor_gt           0.0565
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0614P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1209
_refine_ls_wR_factor_ref         0.1387
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14109
_reflns_number_total             21305
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc03957a2.cif
_cod_data_source_block           mk-303
_cod_original_cell_volume        22165.3(9)
_cod_database_code               1564373
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C80 H179 N1 O26 Si6 U2'
_reflns_odcompleteness_completeness 99.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  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
2. Restrained distances
 O103-C104 = O105-C106
 2.3 with sigma of 0.02
 O42-C43
 2.3 with sigma of 0.02
 O27-C33 \\sim O26-C33 \\sim O25-C29 \\sim O24-C25 \\sim O22-C21 \\sim O23-C21
 with sigma of 0.02
 O27-O25 \\sim O25-O23
 with sigma of 0.02
 O22-O26 \\sim O26-O24
 with sigma of 0.02
 Si2-O27 \\sim Si2-O26 \\sim Si2-O25 \\sim Si2-O24 \\sim Si2-O23 \\sim Si2-O22
 with sigma of 0.02
 C37-C33 \\sim C34-C33 \\sim C38-C33 \\sim C35-C33 \\sim C39-C33 \\sim C36-C33
\\sim C29-C32 \\sim C28-C25
 \\sim C27-C25 \\sim C29-C31 \\sim C26-C25 \\sim C30-C29
 with sigma of 0.02
 C37-C38 \\sim C38-C39
 with sigma of 0.02
 C32-C30 \\sim C30-C31
 with sigma of 0.02
 C28-C26 \\sim C26-C27
 with sigma of 0.02
 C34-C36 \\sim C36-C35
 with sigma of 0.02
 O105-C105 \\sim O104-C105 \\sim O107-C109 \\sim O106-C109 \\sim O102-C101
\\sim O103-C101
 with sigma of 0.02
 Si6-O106 \\sim Si6-O107 \\sim Si6-O102 \\sim Si6-O103 \\sim Si6-O104 \\sim
Si6-O105
 with sigma of 0.02
 O106-O102 \\sim O102-O104
 with sigma of 0.02
 O105-O103 \\sim O103-O107
 with sigma of 0.02
 O44-O42 \\sim O42-O46
 with sigma of 0.02
 O47-O43 \\sim O43-O45
 with sigma of 0.02
 O44-C45 \\sim O45-C45 \\sim O43-C41 \\sim O42-C41 \\sim O46-C49 \\sim O47-C49
 with sigma of 0.02
 Si3-O42 \\sim Si3-O43 \\sim Si3-O44 \\sim Si3-O45 \\sim Si3-O47 \\sim Si3-O46
 with sigma of 0.02
 C129-C128 \\sim C130-C128 \\sim C129-C131 \\sim C130-C131
 with sigma of 0.02
 C122-C121 \\sim C123-C121 \\sim C122-C125 \\sim C124-C123 \\sim C124-C126
\\sim C125-C126
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125 \\sim C126: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
4. 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
5. Others
 Sof(O23)=Sof(O25)=Sof(O27)=Sof(C29)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=
 Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=
 Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(H39C)=1-FVAR(1)
 Sof(O22)=Sof(O24)=Sof(O26)=Sof(C25)=Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=
 Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=FVAR(1)
 Sof(H12F)=Sof(H12G)=Sof(C122)=Sof(H12H)=Sof(H12I)=Sof(C125)=Sof(H12N)=
 Sof(H12O)=Sof(H12R)=Sof(H12S)=1-FVAR(2)
 Sof(H12D)=Sof(H12E)=Sof(C123)=Sof(H12J)=Sof(H12K)=Sof(C124)=Sof(H12L)=
 Sof(H12M)=Sof(H12P)=Sof(H12Q)=FVAR(2)
 Sof(H12X)=Sof(H12Y)=Sof(C130)=Sof(H13A)=Sof(H13B)=Sof(H13E)=Sof(H13F)=1-FVAR(3)
 Sof(H12V)=Sof(H12W)=Sof(C129)=Sof(H12Z)=Sof(H)=Sof(H13C)=Sof(H13D)=FVAR(3)
 Sof(O103)=Sof(O105)=Sof(O107)=1-FVAR(4)
 Sof(O102)=Sof(O104)=Sof(O106)=FVAR(4)
 Sof(O42)=Sof(O44)=Sof(O46)=1-FVAR(5)
 Sof(O43)=Sof(O45)=Sof(O47)=FVAR(5)
6.a Secondary CH2 refined with riding coordinates:
 C121(H12F,H12G), C121(H12D,H12E), C122(H12H,H12I), C123(H12J,H12K), C124(H12L,
 H12M), C125(H12N,H12O), C126(H12P,H12Q), C126(H12R,H12S), C127(H12T,H12U),
 C128(H12V,H12W), C128(H12X,H12Y), C129(H12Z,H), C130(H13A,H13B), C131(H13C,
 H13D), C131(H13E,H13F)
6.b Aromatic/amide H refined with riding coordinates:
 N1(H1)
6.c 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), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C35(H35A,
 H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C),
 C39(H39A,H39B,H39C), 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)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 308 electrons were 
found in a volume of 1588\%A^3^ in 3 voids per unit cell. 
This is consistent with the presence of 
0.45[C4H8O], 0.5[C4H8O] per Asymmetric Unit 
which account for 304 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              31769
_shelx_hkl_checksum              62160
_shelx_fab_checksum              14018
_olex2_date_sample_data_collection 2021-05-19
_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 3.547
_oxdiff_exptl_absorpt_empirical_full_min 0.299