Iron promoted end-on dinitrogen-bridging in heterobimetallic complexes of uranium and lanthanides.
Jori, Nadir; Moreno, Juan J.; Shivaraam, R. A. Keerthi; Rajeshkumar, Thayalan; Scopelliti, Rosario; Maron, Laurent; Campos, Jesús; Mazzanti, Marinella; Chemical science 15 (2024) 6842–6852; doi:10.1039/d4sc01050g

data_1571320
_publ_section_title
;
 Iron promoted end-on dinitrogen-bridging in heterobimetallic complexes of
 uranium and lanthanides.
;
_journal_issue                   18
_journal_name_full               'Chemical science'
_journal_page_first              6842
_journal_page_last               6852
_journal_paper_doi               10.1039/d4sc01050g
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C62 H111 Fe N2 O3 P4 U'
_chemical_formula_sum            'C62 H111 Fe N2 O3 P4 U'
_chemical_formula_weight         1350.28
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-10-20
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-02-01 deposited with the CCDC.	2024-04-02 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.81721(16)
_cell_length_b                   19.7326(2)
_cell_length_c                   20.13034(17)
_cell_measurement_reflns_used    26871
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      76.5280
_cell_measurement_theta_min      3.0870
_cell_volume                     6680.20(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 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_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 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   -112.00 -26.00   1.00    5.00    --  -43.01 -43.00-170.00   86
  2  \w    -19.00  10.00   1.00    5.00    --   43.01 -82.00  -2.00   29
  3  \w     40.00  71.00   1.00   20.00    --  112.00 -43.00-170.00   31
  4  \w    140.00 165.00   1.00   20.00    --  112.00  82.00 119.00   25
  5  \w     92.00 119.00   1.00   20.00    --  112.00 -43.00-170.00   27
  6  \w    104.00 153.00   1.00   20.00    --  112.00 110.00-156.00   49
  7  \w    -89.00 -16.00   1.00    5.00    --  -43.01 -57.00 120.00   73
  8  \w     34.00  93.00   1.00    5.00    --   43.01-125.00-150.00   59
  9  \w     39.00  81.00   1.00   20.00    --  112.00-111.00 -30.00   42
 10  \w    130.00 178.00   1.00   20.00    --  112.00  77.00-120.00   48
 11  \w    105.00 149.00   1.00   20.00    --  112.00 111.00-180.00   44
 12  \w    152.00 178.00   1.00   20.00    --  112.00 111.00-180.00   26
 13  \w     74.00 137.00   1.00   20.00    --  112.00 -45.00  90.00   63
 14  \w    146.00 172.00   1.00   20.00    --  112.00  45.00 120.00   26
 15  \w     42.00 101.00   1.00   20.00    --  112.00-111.00 120.00   59
 16  \w     97.00 138.00   1.00   20.00    --  112.00  45.00 -90.00   41
 17  \w    140.00 173.00   1.00   20.00    --  112.00  45.00 -90.00   33
 18  \w    104.00 171.00   1.00   20.00    --  112.00  77.00 150.00   67
 19  \w     86.00 148.00   1.00   20.00    --  112.00  45.00 150.00   62
 20  \w     86.00 117.00   1.00   20.00    --  112.00  45.00 120.00   31
 21  \w     61.00  88.00   1.00   20.00    --  112.00-111.00-150.00   27
 22  \w     66.00 107.00   1.00   20.00    --  112.00 -82.00  -2.00   41
;
_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      -0.0035879000
_diffrn_orient_matrix_UB_12      0.0356451000
_diffrn_orient_matrix_UB_13      0.0680587000
_diffrn_orient_matrix_UB_21      -0.0484435000
_diffrn_orient_matrix_UB_22      0.0582201000
_diffrn_orient_matrix_UB_23      -0.0310064000
_diffrn_orient_matrix_UB_31      -0.0775617000
_diffrn_orient_matrix_UB_32      -0.0380279000
_diffrn_orient_matrix_UB_33      0.0162527000
_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  0.0331
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            41209
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.745
_diffrn_reflns_theta_min         3.136
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.726
_exptl_absorpt_correction_T_max  0.554
_exptl_absorpt_correction_T_min  0.265
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
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            'translucent dark black'
_exptl_crystal_density_diffrn    1.343
_exptl_crystal_description       prism
_exptl_crystal_F_000             2796
_exptl_crystal_size_max          0.207
_exptl_crystal_size_mid          0.089
_exptl_crystal_size_min          0.084
_refine_diff_density_max         0.981
_refine_diff_density_min         -0.674
_refine_diff_density_rms         0.074
_refine_ls_abs_structure_details
;
 Flack x determined using 5821 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.015(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     859
_refine_ls_number_reflns         13920
_refine_ls_number_restraints     769
_refine_ls_restrained_S_all      1.130
_refine_ls_R_factor_all          0.0283
_refine_ls_R_factor_gt           0.0263
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0247P)^2^+4.8817P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0621
_refine_ls_wR_factor_ref         0.0630
_reflns_Friedel_coverage         0.822
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.983
_reflns_number_gt                13436
_reflns_number_total             13920
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01050g2.cif
_cod_data_source_block           jj-017
_cod_depositor_comments
'Adding full bibliography for 1571317--1571325.cif.'
_cod_original_cell_volume        6680.19(11)
_cod_database_code               1571320
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C62 H111 N2 O3 P4 Fe1 U1'
_shelx_estimated_absorpt_t_max   0.495
_shelx_estimated_absorpt_t_min   0.238
_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
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C74-C63 \\sim C74-C69
 with sigma of 0.02
 O3-C62 \\sim O3-C68
 with sigma of 0.02
 C62-C63 \\sim C68-C69
 with sigma of 0.02
 C62-C67 \\sim C68-C73
 with sigma of 0.02
 C67-C81 \\sim C73-C81
 with sigma of 0.02
 C67-C66 \\sim C73-C72
 with sigma of 0.02
 C67-C65 \\sim C73-C71
 with sigma of 0.04
 C66-C81 \\sim C72-C81
 with sigma of 0.04
 C65-C63 \\sim C71-C69
 with sigma of 0.04
 C65-C64 \\sim C71-C70
 with sigma of 0.02
 C66-C65 \\sim C72-C71
 with sigma of 0.02
 C67-C63 \\sim C73-C69
 with sigma of 0.04
 C66-C64 \\sim C72-C70
 with sigma of 0.04
 C64-C63 \\sim C70-C69
 with sigma of 0.02
 O3-C67 \\sim O3-C73
 with sigma of 0.04
 O3-C63 \\sim O3-C69
 with sigma of 0.04
 C74-C62 \\sim C74-C68
 with sigma of 0.04
 C74-C64 \\sim C74-C70
 with sigma of 0.04
 C62-C66 \\sim C68-C72
 with sigma of 0.04
 C62-C64 \\sim C68-C70
 with sigma of 0.04
 C62-C81 \\sim C68-C81
 with sigma of 0.04
 P2-C11 \\sim P2-C15 \\sim P2-C13 \\sim P2-C9 \\sim P2-C8 \\sim P2-C6 \\sim
P5-C25 \\sim P4-C29 \\sim P4-C27 ~
 P5-C23 \\sim P5-C21 \\sim P4-C22 \\sim P1-C7 \\sim P1-C5
 with sigma of 0.02
 C30-C29 \\sim C26-C25 \\sim C28-C27 \\sim C24-C23 \\sim C21-C20 \\sim C22-C20
\\sim C14-C13 \\sim C9-C10
 \\sim C8-C7 \\sim C6-C5 \\sim C12-C11 \\sim C85-C15
 with sigma of 0.02
 C44-C41 \\sim C43-C41 \\sim C42-C41
 with sigma of 0.02
 C43-C44 \\sim C44-C42 \\sim C42-C43
 with sigma of 0.02
 C79-C74 \\sim C75-C74 \\sim C78-C74 \\sim C76-C74 \\sim C80-C74 \\sim C77-C74
 with sigma of 0.02
 C78-C79 \\sim C79-C80 \\sim C78-C80
 with sigma of 0.02
 C75-C76 \\sim C76-C77 \\sim C75-C77
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
P4 \\sim P5 \\sim C29 \\sim C25 \\sim C30 \\sim C26 \\sim C28 \\sim C27 \\sim
C23 \\sim C24 \\sim C21 \\sim C22 \\sim C20 \\sim P3 \\sim P1 \\sim C7 \\sim C5
\\sim C6 \\sim C8 \\sim C9 \\sim C13 \\sim C14 \\sim C10 \\sim C11 \\sim C15
\\sim C12 \\sim C85: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
C41 \\sim C43 \\sim C44 \\sim C42: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
C64 \\sim C68 \\sim C70 \\sim C66 \\sim C72 \\sim C67 \\sim C69 \\sim C63 \\sim
C73 \\sim C65 \\sim C71 \\sim C62 \\sim C74 \\sim C79 \\sim C75 \\sim C78 \\sim
C76 \\sim C80 \\sim C77: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
Uanis(C51) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C83) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(P4)=Sof(H20C)=Sof(H20D)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(C27)=Sof(H27A)=
 Sof(H27B)=Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(1)
 Sof(P5)=Sof(H20A)=Sof(H20B)=Sof(C21)=Sof(H21A)=Sof(H21B)=Sof(C23)=Sof(H23A)=
 Sof(H23B)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=Sof(H25B)=
 Sof(C26)=Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C13)=Sof(H13A)=
 Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 Sof(C68)=Sof(C73)=Sof(C72)=Sof(H72)=Sof(C71)=Sof(H71)=Sof(C70)=Sof(H70)=
 Sof(C69)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(H85C)=1-FVAR(2)
 Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(C9)=Sof(H9A)=Sof(H9B)=
 Sof(C10)=Sof(H10A)=Sof(H10B)=Sof(H10C)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=
 Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C62)=Sof(C67)=Sof(C66)=Sof(H66)=Sof(C65)=
 Sof(H65)=Sof(C64)=Sof(H64)=Sof(C63)=FVAR(2)
 Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(H78C)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(H79C)=
 Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(H80C)=1-FVAR(3)
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=
 Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(H77C)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C7(H7A,H7B), C8(H8A,H8B),
 C9(H9A,H9B), C11(H11A,H11B), C13(H13A,H13B), C15(H15A,H15B), C16(H16A,H16B),
 C18(H18A,H18B), C20(H20A,H20B), C20(H20C,H20D), C21(H21A,H21B), C22(H22A,H22B),
  C23(H23A,H23B), C25(H25A,H25B), C27(H27A,H27B), C29(H29A,H29B)
5.b Aromatic/amide H refined with riding coordinates:
 C33(H33), C34(H34), C35(H35), C50(H50), C51(H51), C52(H52), C66(H66),
 C65(H65), C64(H64), C72(H72), C71(H71), C70(H70)
5.c Fitted hexagon refined as free rotating group:
 C62(C67,C66,C65,C64,C63), C68(C73,C72,C71,C70,C69)
5.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C10(H10A,H10B,H10C), C12(H12A,H12B,H12C),
 C14(H14A,H14B,H14C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C24(H24A,H24B,
 H24C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C38(H38A,
 H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C),
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C55(H55A,H55B,H55C), C56(H56A,H56B,
 H56C), C57(H57A,H57B,H57C), C59(H59A,H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,
 H61B,H61C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C),
 C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C82(H82A,H82B,
 H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C)
;
_shelx_res_checksum              29004
_olex2_date_sample_data_collection 2022-10-10
_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 1.366
_oxdiff_exptl_absorpt_empirical_full_min 0.762