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_1575976
_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_absolute_configuration rm
_chemical_formula_moiety         'C68 H116 N2 U2, C5 H12'
_chemical_formula_sum            'C73 H128 N2 U2'
_chemical_formula_weight         1509.83
_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_Hall           '-P 2yac'
_space_group_name_H-M_alt        'P 1 2/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-05-22
_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                90
_cell_angle_beta                 109.753(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   18.4067(9)
_cell_length_b                   10.3962(5)
_cell_length_c                   19.3564(9)
_cell_measurement_reflns_used    16465
_cell_measurement_temperature    150
_cell_measurement_theta_max      28.91
_cell_measurement_theta_min      2.15
_cell_volume                     3486.1(3)
_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 2.5.3.0 (STOE, 2021)
X-Area LANA 2.7.5.0 (STOE, 2022)
;
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'EIGER2 1M CDTE'
_diffrn_detector_area_resol_mean 13.33
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
 1067 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_collimation    '1.2 0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_polarisn_norm  270
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0773
_diffrn_reflns_av_unetI/netI     0.0925
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            17049
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        24.998
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.236
_diffrn_source                   Axo_Mo
_diffrn_source_current           1.00
_diffrn_source_power             0.050
_diffrn_source_voltage           50
_exptl_absorpt_coefficient_mu    4.679
_exptl_absorpt_correction_T_max  0.9117
_exptl_absorpt_correction_T_min  0.4905
_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 green'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.438
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       needle
_exptl_crystal_F_000             1528
_exptl_crystal_size_max          0.203
_exptl_crystal_size_mid          0.032
_exptl_crystal_size_min          0.024
_refine_diff_density_max         1.394
_refine_diff_density_min         -1.620
_refine_diff_density_rms         0.175
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     386
_refine_ls_number_reflns         6098
_refine_ls_number_restraints     45
_refine_ls_restrained_S_all      1.011
_refine_ls_R_factor_all          0.1211
_refine_ls_R_factor_gt           0.0629
_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/[\s^2^(Fo^2^)+(0.0994P)^2^+2.8407P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1438
_refine_ls_wR_factor_ref         0.1742
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3821
_reflns_number_total             6098
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc07194a3.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 1575976--1575980.cif.'
_cod_database_code               1575976
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.896
_shelx_estimated_absorpt_t_min   0.450
_diffrn_oxdiff_ac3_digest_hkl    01192eec34bfefe7478890271fd3814851b4a9
_olex2_refinement_description
;
1. Others
 Fixed Sof: C35(0.5) H35A(0.5) H35B(0.5) C36(0.5) H36A(0.5) H36B(0.5)
 H36C(0.5) C37(0.5) H37A(0.5) H37B(0.5) C38(0.5) H38A(0.5) H38B(0.5) C39(0.5)
 H39A(0.5) H39B(0.5) H39C(0.5)
 Fixed U12: N2(0) N3(0)
 Fixed U23: N2(0) N3(0)
 Fixed Uiso: H1(0.035) H4(0.052) H7A(0.063) H7B(0.063) H7C(0.063) H8A(0.066)
 H8B(0.066) H8C(0.066) H9A(0.061) H9B(0.061) H9C(0.061) H11A(0.065) H11B(0.065)
 H11C(0.065) H12A(0.062) H12B(0.062) H12C(0.062) H13A(0.061) H13B(0.061)
 H13C(0.061) H15A(0.062) H15B(0.062) H15C(0.062) H16A(0.076) H16B(0.076)
 H16C(0.076) H17A(0.061) H17B(0.061) H17C(0.061) H18(0.035) H21(0.046)
 H24A(0.059) H24B(0.059) H24C(0.059) H25A(0.066) H25B(0.066) H25C(0.066)
 H26A(0.053) H26B(0.053) H26C(0.053) H28A(0.08) H28B(0.08) H28C(0.08)
 H29A(0.083) H29B(0.083) H29C(0.083) H30A(0.072) H30B(0.072) H30C(0.072)
 H32A(0.066) H32B(0.066) H32C(0.066) H33A(0.068) H33B(0.068) H33C(0.068)
 H34A(0.063) H34B(0.063) H34C(0.063) H35A(0.17) H35B(0.17) H36A(0.213)
 H36B(0.213) H36C(0.213) H37A(0.17) H37B(0.17) H38A(0.17) H38B(0.17)
 H39A(0.213) H39B(0.213) H39C(0.213)
 Fixed X: H1(0.551797) H4(0.541336) H7A(0.446326) H7B(0.530823) H7C(0.473156)
 H8A(0.414404) H8B(0.454243) H8C(0.484105) H9A(0.588313) H9B(0.635459)
 H9C(0.616652) H11A(0.566778) H11B(0.636677) H11C(0.563948) H12A(0.558017)
 H12B(0.61738) H12C(0.530148) H13A(0.436055) H13B(0.43924) H13C(0.426375)
 H15A(0.447455) H15B(0.495592) H15C(0.49668) H16A(0.610287) H16B(0.557241)
 H16C(0.518298) H17A(0.645035) H17B(0.637088) H17C(0.684057) H18(0.878253)
 H21(0.721647) H24A(0.798804) H24B(0.79905) H24C(0.728319) H25A(0.741311)
 H25B(0.814468) H25C(0.819798) H26A(0.937784) H26B(0.921789) H26C(0.930192)
 H28A(0.831809) H28B(0.764803) H28C(0.798952) H29A(0.66687) H29B(0.632387)
 H29C(0.613791) H30A(0.660394) H30B(0.680033) H30C(0.745308) H32A(0.74729)
 H32B(0.81402) H32C(0.767356) H33A(0.924292) H33B(0.925124) H33C(0.854924)
 H34A(0.886018) H34B(0.926919) H34C(0.952094) N2(0.75) N3(0.75) H35A(0.804788)
 H35B(0.713132) H36A(0.755662) H36B(0.713391) H36C(0.805466) H37A(0.701817)
 H37B(0.793641) H38A(0.78965) H38B(0.698126) H39A(0.722711) H39B(0.807859)
 H39C(0.734685)
 Fixed Y: H1(0.626311) H4(0.59313) H7A(0.411803) H7B(0.360568) H7C(0.271825)
 H8A(0.438921) H8B(0.304047) H8C(0.43302) H9A(0.255114) H9B(0.365466)
 H9C(0.379819) H11A(1.033187) H11B(0.979299) H11C(1.045103) H12A(0.864729)
 H12B(0.77115) H12C(0.72619) H13A(0.912775) H13B(0.942145) H13C(0.798032)
 H15A(0.928043) H15B(1.047003) H15C(1.016957) H16A(0.800055) H16B(0.920513)
 H16C(0.788353) H17A(1.000804) H17B(1.046011) H17C(0.917966) H18(0.619805)
 H21(0.650754) H24A(0.85322) H24B(0.9853) H24C(0.887336) H25A(0.876876)
 H25B(0.970739) H25C(0.829743) H26A(0.811747) H26B(0.942425) H26C(0.809599)
 H28A(0.323729) H28B(0.304857) H28C(0.445262) H29A(0.5136) H29B(0.371177)
 H29C(0.457793) H30A(0.261816) H30B(0.197859) H30C(0.207881) H32A(0.24792)
 H32B(0.199132) H32C(0.327927) H33A(0.320106) H33B(0.205882) H33C(0.218522)
 H34A(0.464776) H34B(0.326866) H34C(0.437514) H35A(0.862639) H35B(0.859171)
 H36A(0.638635) H36B(0.562245) H36C(0.5747) H37A(0.741995) H37B(0.74421)
 H38A(0.988915) H38B(0.987018) H39A(1.094397) H39B(1.120557) H39C(1.180391)
 Fixed Z: H1(0.203215) H4(0.408801) H7A(0.346778) H7B(0.392892) H7C(0.330769)
 H8A(0.207394) H8B(0.202401) H8C(0.175628) H9A(0.289653) H9B(0.344077)
 H9C(0.257455) H11A(0.368375) H11B(0.436493) H11C(0.449855) H12A(0.51988)
 H12B(0.5004) H12C(0.484907) H13A(0.329859) H13B(0.411991) H13C(0.381176)
 H15A(0.201343) H15B(0.18686) H15C(0.268291) H16A(0.163094) H16B(0.126151)
 H16C(0.137766) H17A(0.314707) H17B(0.233442) H17C(0.266945) H18(0.429341)
 H21(0.533143) H24A(0.385622) H24B(0.428164) H24C(0.413173) H25A(0.542104)
 H25B(0.568285) H25C(0.60283) H26A(0.566797) H26B(0.520371) H26C(0.481967)
 H28A(0.604106) H28B(0.638575) H28C(0.634898) H29A(0.577186) H29B(0.571728)
 H29C(0.499461) H30A(0.449422) H30B(0.528854) H30C(0.491578) H32A(0.385322)
 H32B(0.355954) H32C(0.323459) H33A(0.534325) H33B(0.479173) H33C(0.509923)
 H34A(0.357967) H34B(0.374125) H34C(0.435095) N2(0.25) N3(0.25) H35A(0.728051)
 H35B(0.689261) H36A(0.69094) H36B(0.738354) H36C(0.767523) H37A(0.790308)
 H37B(0.82818) H38A(0.824477) H38B(0.784367) H39A(0.681321) H39B(0.737508)
 H39C(0.7529)
;
_shelx_res_checksum              30099
_olex2_submission_special_instructions 'No special instructions were received'
_stoe_detector_distance          '60.0 mm'
_stoe_detector_pixelsize_x       '0.075 mm'
_stoe_detector_pixelsize_y       '0.075 mm'
_stoe_detector_size_x            '8.0 cm'
_stoe_detector_size_y            '7.7 cm'
_stoe_evaluation_integration_a   10.1
_stoe_evaluation_integration_b   0.1
_stoe_evaluation_integration_ems 0.011
_stoe_evaluation_lana_bis_l_even_max -
_stoe_evaluation_lana_bis_l_odd_max -
_stoe_evaluation_lana_bos_l_even_max 4
_stoe_evaluation_lana_bos_l_odd_max 1
_stoe_evaluation_lana_completeness 91.9
_stoe_evaluation_lana_dxs_max_order 3
_stoe_evaluation_lana_dys_max_order 3
_stoe_evaluation_lana_fs_max_order 3
_stoe_evaluation_lana_max_2theta_available 58.5
_stoe_evaluation_lana_max_2theta_desired 58.5
_stoe_evaluation_lana_mean_redundancy 7.0
_stoe_evaluation_lana_number_refls_after_or 21453
_stoe_evaluation_lana_number_refls_outliers 535
_stoe_evaluation_lana_number_refls_total 21988
_stoe_evaluation_lana_number_refls_unique 3064
_stoe_evaluation_lana_number_refls_written 21453
_stoe_evaluation_lana_or_c1      0.050
_stoe_evaluation_lana_or_c2      0
_stoe_evaluation_lana_or_c3      0
_stoe_evaluation_lana_or_c4      1.0
_stoe_evaluation_lana_point_group 2/m
_stoe_evaluation_lana_table
;
2Theta           6.7   12.9   19.1   25.3   31.5   37.7   43.9   50.1   56.3
<Resolution>    4.99   3.08   2.15   1.60   1.30   1.10   0.95   0.84   0.77
N(total)         313   1008   1308   1982   3039   3810   4311   4620   1597
<Redundancy>    14.5   15.1    9.2    8.7    8.7    8.2    7.2    6.1    3.2
Complet. [%%]   100.0  100.0   99.3  100.0  100.0  100.0  100.0  100.0   64.7
<I/sigma>      200.5   83.1   55.5   27.5   19.6   11.1    6.1    3.7    2.2
R(int)         0.016  0.016  0.018  0.021  0.026  0.037  0.058  0.086  0.113
;
_stoe_measurement_identifier     LB262
_stoe_measurement_max_exposure_per_frame '8.0 s'
_stoe_measurement_mean_exposure_per_frame '8.0 s'
_stoe_measurement_min_exposure_per_frame '8.0 s'
_stoe_measurement_total_exposure_time '2.4 h'
_stoe_measurement_total_frame_number 1067
_stoe_measurement_total_run_number 18
_stoe_measurement_tube_power     '50.0 W'