# Supplementary Information (SI) for Inorganic Chemistry Frontiers.
# This journal is © the Partner Organisations 2025

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_npbrown
_database_code_depnum_ccdc_archive 'CCDC 2417020'
loop_
_audit_author_name
_audit_author_address
'Connor J. Parker'
;Oak Ridge National Laboratory
United States of America
;
_audit_update_record             
;
2025-01-14 deposited with the CCDC.	2025-05-21 downloaded from the CCDC.
;
_audit_creation_date             2024-12-30
_audit_creation_method           
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        'Neptunium(VI) Ammonium Trinitrate'
_chemical_formula_moiety         'N3 Np O11, N'
_chemical_formula_sum            'N4 Np O11'
_chemical_formula_weight         469.09
_chemical_absolute_configuration unk
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Np Np -11.4937 4.1493 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      trigonal
_space_group_IT_number           155
_space_group_name_H-M_alt        'R 3 2'
_space_group_name_Hall           'R 3 2"'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'y, x, -z'
'x-y, -y, -z'
'-x, -x+y, -z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'y+2/3, x+1/3, -z+1/3'
'x-y+2/3, -y+1/3, -z+1/3'
'-x+2/3, -x+y+1/3, -z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'y+1/3, x+2/3, -z+2/3'
'x-y+1/3, -y+2/3, -z+2/3'
'-x+1/3, -x+y+2/3, -z+2/3'

_cell_length_a                   9.1621(2)
_cell_length_b                   9.1621(2)
_cell_length_c                   9.4414(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     686.37(4)
_cell_formula_units_Z            3
_cell_measurement_reflns_used    1589
_cell_measurement_temperature    298
_cell_measurement_theta_max      29.334
_cell_measurement_theta_min      3.352
_shelx_estimated_absorpt_T_max   0.894
_shelx_estimated_absorpt_T_min   0.804
_exptl_absorpt_coefficient_mu    11.424
_exptl_absorpt_correction_T_max  0.89
_exptl_absorpt_correction_T_min  0.865
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
 TWINABS-2012/1 (Bruker,2012) was used for absorption correction.
 
For component 1:
 wR2(int) was 0.0492 before and 0.0386 after correction.
 
For component 2:
 wR2(int) was 0.0522 before and 0.0356 after correction.
 The Ratio of minimum to maximum transmission is 0.90.

Final HKLF 4 output contains 7157 reflections, Rint = 0.0529
 (7031 with I > 3sig(I), Rint = 0.0525)
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear dark brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    3.404
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             627
_exptl_crystal_preparation       'Dried from Np production feedstock solution.'
_exptl_crystal_recrystallization_method 
'Allowed to dry overnight to form crystals within brown and green precipitate.'
_exptl_crystal_size_max          0.02
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_exptl_transmission_factor_max   0.892
_exptl_transmission_factor_min   0.872
_diffrn_reflns_av_R_equivalents  0.0335
_diffrn_reflns_av_unetI/netI     0.0262
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            1725
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.934
_diffrn_reflns_theta_min         3.354
_diffrn_ambient_temperature      298
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.726
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                585
_reflns_number_total             585
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences. Completness statistics refer to single and
 composite reflections containing twin component 1 only.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_refine_diff_density_max         1.288
_refine_diff_density_min         -0.767
_refine_diff_density_rms         0.205
_refine_ls_abs_structure_details 
;
 Flack x determined using 246 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.50(3)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.106
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     28
_refine_ls_number_reflns         585
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0195
_refine_ls_R_factor_gt           0.0195
_refine_ls_restrained_S_all      1.106
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0306P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0464
_refine_ls_wR_factor_ref         0.0464
_refine_special_details          
;
 Refined as a 2-component twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.999(6)
 0.001(6)
;
_atom_sites_solution_hydrogens   .
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O 0.333333 0.666667 0.4816(5) 0.0182(9) Uani 1 3 d S T P . .
O2 O 0.499(2) 0.522(3) 0.6772(5) 0.0275(18) Uani 1 1 d . . . . .
O3 O 0.333333 0.2179(7) 0.666667 0.0207(11) Uani 1 2 d S T P . .
N1 N 0.333333 0.3498(8) 0.666667 0.0161(11) Uani 1 2 d S T P . .
Np1 Np 0.333333 0.666667 0.666667 0.01207(12) Uani 1 6 d S T P . .
N2 N 0.333333 0.666667 0.166667 0.0185(14) Uani 1 6 d S T P . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
O1 Np1 1.747(5) . ?
O2 N1 1.55(2) . ?
O2 Np1 2.465(4) . ?
O3 N1 1.209(10) . ?
N1 Np1 2.903(7) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 O2 Np1 89.6(6) . . ?
O2 N1 O2 116.3(6) 12_556 . ?
O2 N1 Np1 58.1(3) 12_556 . ?
O2 N1 Np1 58.1(3) . . ?
O3 N1 O2 121.9(3) . 12_556 ?
O3 N1 O2 121.9(3) . . ?
O3 N1 Np1 180.0 . . ?
O1 Np1 O1 180.0 10_456 . ?
O1 Np1 O2 92.32(10) 10_456 11_566 ?
O1 Np1 O2 92.32(10) 10_456 12_556 ?
O1 Np1 O2 92.32(10) . . ?
O1 Np1 O2 87.68(10) . 10_456 ?
O1 Np1 O2 87.68(10) . 12_556 ?
O1 Np1 O2 92.32(10) . 3_565 ?
O1 Np1 O2 92.32(10) . 2_665 ?
O1 Np1 O2 92.32(10) 10_456 10_456 ?
O1 Np1 O2 87.68(10) . 11_566 ?
O1 Np1 O2 87.68(10) 10_456 2_665 ?
O1 Np1 O2 87.68(10) 10_456 3_565 ?
O1 Np1 O2 87.68(10) 10_456 . ?
O1 Np1 N1 90.000(3) . 2_665 ?
O1 Np1 N1 90.000(4) 10_456 2_665 ?
O1 Np1 N1 90.000(1) 10_456 . ?
O1 Np1 N1 89.999(1) 10_456 3_565 ?
O1 Np1 N1 90.000(1) . 3_565 ?
O1 Np1 N1 90.000(1) . . ?
O2 Np1 O2 64.4(11) 3_565 10_456 ?
O2 Np1 O2 64.4(11) 12_556 . ?
O2 Np1 O2 119.838(17) 3_565 . ?
O2 Np1 O2 119.837(16) 10_456 12_556 ?
O2 Np1 O2 175.7(11) 10_456 . ?
O2 Np1 O2 55.9(11) 2_665 10_456 ?
O2 Np1 O2 175.7(11) 2_665 12_556 ?
O2 Np1 O2 119.837(16) 10_456 11_566 ?
O2 Np1 O2 119.837(19) 2_665 . ?
O2 Np1 O2 64.4(11) 2_665 11_566 ?
O2 Np1 O2 175.7(11) 3_565 11_566 ?
O2 Np1 O2 119.839(15) 12_556 11_566 ?
O2 Np1 O2 55.9(11) 11_566 . ?
O2 Np1 O2 119.838(15) 2_665 3_565 ?
O2 Np1 O2 55.9(11) 3_565 12_556 ?
O2 Np1 N1 152.1(5) 11_566 3_565 ?
O2 Np1 N1 152.1(5) 10_456 . ?
O2 Np1 N1 32.2(5) 11_566 2_665 ?
O2 Np1 N1 152.1(5) 2_665 . ?
O2 Np1 N1 87.9(5) 3_565 . ?
O2 Np1 N1 32.2(5) 12_556 . ?
O2 Np1 N1 152.1(5) . 3_565 ?
O2 Np1 N1 87.9(5) . 2_665 ?
O2 Np1 N1 87.9(5) 10_456 2_665 ?
O2 Np1 N1 87.9(5) 2_665 3_565 ?
O2 Np1 N1 87.9(5) 12_556 3_565 ?
O2 Np1 N1 152.1(5) 12_556 2_665 ?
O2 Np1 N1 32.2(5) 3_565 3_565 ?
O2 Np1 N1 32.2(5) 2_665 2_665 ?
O2 Np1 N1 152.1(5) 3_565 2_665 ?
O2 Np1 N1 32.2(5) . . ?
O2 Np1 N1 32.2(5) 10_456 3_565 ?
O2 Np1 N1 87.9(5) 11_566 . ?
N1 Np1 N1 120.000(1) 2_665 . ?
N1 Np1 N1 120.000(1) 3_565 2_665 ?
N1 Np1 N1 120.000(3) 3_565 . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
Np1 O2 N1 O2 -0.001(1) . . . 12_556 ?
Np1 O2 N1 O3 180.000(0) . . . . ?

_olex2_exptl_crystal_mounting_method 
'Mounted on Mitegen cryoloop in microscopy oil, coated in 1-minute bonding epoxy, bound to loop. Coated again in epoxy as a secondary form of containment against radioactive contamination. '
_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.999(6)
2 0.001(6)
# start Validation Reply Form
_vrf_PLAT987_npbrown             
;
PROBLEM: The Flack x is >> 0 -  Do a BASF/TWIN Refinement     Please Check 
RESPONSE: Continued BASF/TWIN Refinements identified a twin but were unable to
eliminate this  B-Level Alert, and the twin was not observed within Bruker's
APEX4 domain modules.
Due to challenges posed by radiologic safety, this crystal quality was
the highest quality the team could achieve.   
;
# end Validation Reply Form
