Room temperature dinitrogen cleavage and hydrogenation with organometallic complexes of uranium.
Shephard, Angus C. G.; Pedussaut, Lucie; De Marchi, Linda; Demonti, Luca; Rajeshkumar, Thayalan; Casaretto, Nicolas; Maron, Laurent; Danoun, Grégory; Simler, Thomas; Nocton, Grégory; Chemical science 16 (2025) 21334–21345; doi:10.1039/d5sc07194a

data_1575977
_publ_section_title
;
 Room temperature dinitrogen cleavage and hydrogenation with
 organometallic complexes of uranium.
;
_journal_issue                   45
_journal_name_full               'Chemical science'
_journal_page_first              21334
_journal_page_last               21345
_journal_paper_doi               10.1039/d5sc07194a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C68 H117 I N2 U3, 3(C7 H8)'
_chemical_formula_sum            'C89 H141 I N2 U3'
_chemical_formula_weight         2080.02
_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
_audit_creation_date             2025-06-02
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7224)
;
_audit_update_record
;
2025-06-13 deposited with the CCDC.	2025-10-14 downloaded from the CCDC.
;
_cell_angle_alpha                78.484(2)
_cell_angle_beta                 83.187(2)
_cell_angle_gamma                65.206(2)
_cell_formula_units_Z            2
_cell_length_a                   14.2226(4)
_cell_length_b                   14.7263(3)
_cell_length_c                   22.8579(6)
_cell_measurement_reflns_used    56235
_cell_measurement_temperature    150
_cell_measurement_theta_max      29.06
_cell_measurement_theta_min      2.18
_cell_volume                     4255.4(2)
_computing_cell_refinement
;
X-Area Recipe 2.0.2 (STOE, 2024)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.194.0 (STOE, 2023)
;
_computing_data_reduction
;
X-Area Integrate 2.5.18.0 (STOE, 2024)
X-Area X-Red 2.3.1.0 (STOE, 2023)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150.15
_diffrn_detector_area_resol_mean 13.33
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
 1036 frames, detector distance = 60 mm
;
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'STOE STADIVARI'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0425
_diffrn_reflns_av_unetI/netI     0.0593
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            69853
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         2.183
_exptl_absorpt_coefficient_mu    6.100
_exptl_absorpt_correction_T_max  0.6563
_exptl_absorpt_correction_T_min  0.5674
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE LANA, absorption correction by scaling of reflection intensities.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_colour            'dark brown'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.623
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2036
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.163
_exptl_crystal_size_min          0.139
_refine_diff_density_max         1.133
_refine_diff_density_min         -0.834
_refine_diff_density_rms         0.148
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.981
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     929
_refine_ls_number_reflns         19358
_refine_ls_number_restraints     382
_refine_ls_restrained_S_all      0.973
_refine_ls_R_factor_all          0.0567
_refine_ls_R_factor_gt           0.0324
_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^)+(0.0366P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0667
_refine_ls_wR_factor_ref         0.0716
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14355
_reflns_number_total             19358
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07194a3.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 1575976--1575980.cif.'
_cod_database_code               1575977
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.484
_shelx_estimated_absorpt_t_min   0.395
_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. Restrained distances
 C88-C87 \\sim C87-C86 \\sim C86-C85 \\sim C85-C84 \\sim C84-C81 \\sim C81-C88
 with sigma of 0.02
 C88-C84 \\sim C88-C86 \\sim C81-C85 \\sim C87-C81 \\sim C86-C84 \\sim C87-C85
 with sigma of 0.04
 C76-C77 \\sim C77-C78 \\sim C78-C89 \\sim C89-C80 \\sim C80-C83 \\sim C83-C76
 with sigma of 0.02
 C90-C81 \\sim C90-C87
 with sigma of 0.04
 C76-C80 \\sim C76-C78 \\sim C83-C89 \\sim C77-C83 \\sim C78-C80 \\sim C77-C89
 with sigma of 0.04
 C82-C83 \\sim C82-C77
 with sigma of 0.04
3. Restrained planarity
 C90, C81, C84, C85, C86, C87, C88
 with sigma of 0.1
 C82, C76, C77, C78, C80, C83, C89
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C90 \\sim C81 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88: within 2A with
sigma of 0.004 and sigma for terminal atoms of 0.008 within 2A
C82 \\sim C76 \\sim C77 \\sim C78 \\sim C80 \\sim C83 \\sim C89: within 2A with
sigma of 0.004 and sigma for terminal atoms of 0.008 within 2A
C82 \\sim C76 \\sim C77 \\sim C78 \\sim C80 \\sim C83 \\sim C89 \\sim C90 \\sim
C81 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C88: within 2A with sigma of
0.004 and sigma for terminal atoms of 0.008 within 2A
5. Rigid body (RIGU) restrains
 C90, C81, C84, C85, C86, C87, C88
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C82, C76, C77, C78, C80, C83, C89
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=Sof(C81)=Sof(H81)=Sof(C84)=Sof(H84)=
 Sof(C85)=Sof(H85)=Sof(C86)=Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=1-FVAR(1)
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=Sof(C76)=Sof(C77)=Sof(H77)=Sof(C78)=
 Sof(H78)=Sof(C80)=Sof(H80)=Sof(C83)=Sof(H83)=Sof(C89)=Sof(H89)=FVAR(1)
7.a Free rotating group:
 C82(C76,C77,C78,C80,C83,C89), C90(C81,C84,C85,C86,C87,C88)
7.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C2(H2), C5(H5), C19(H19), C22(H22), C36(H36), C39(H39), C53(H53),
 C56(H56), C02B(H02B), C02C(H02C), C02D(H02D), C02H(H02H), C028(H028), C70(H70),
  C71(H71), C72(H72), C73(H73), C74(H74), C77(H77), C78(H78), C80(H80),
 C83(H83), C89(H89), C81(H81), C84(H84), C85(H85), C86(H86), C87(H87)
7.c Idealised Me refined with riding coordinates:
 C43(H43A,H43B,H43C)
7.d Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C16(H16A,H16B,
 H16C), C17(H17A,H17B,H17C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,
 H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,
 H47B,H47C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C),
 C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C62(H62A,H62B,
 H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C66(H66A,H66B,H66C), C67(H67A,
 H67B,H67C), C68(H68A,H68B,H68C), C02J(H02A,H02E,H02F), C75(H75A,H75B,H75C),
 C82(H82A,H82B,H82C), C90(H90A,H90B,H90C)
;
_shelx_res_checksum              89225
_olex2_submission_special_instructions 'No special instructions were received'