Dinitrogen cleavage by a dinuclear uranium(iii) complex.
Jori, Nadir; Keener, Megan; Rajeshkumar, Thayalan; Scopelliti, Rosario; Maron, Laurent; Mazzanti, Marinella; Chemical science 14 (2023) 13485–13494; doi:10.1039/d3sc05253b

data_1570264
_publ_section_title
;
 Dinitrogen cleavage by a dinuclear uranium(iii) complex.
;
_journal_issue                   46
_journal_name_full               'Chemical science'
_journal_page_first              13485
_journal_page_last               13494
_journal_paper_doi               10.1039/d3sc05253b
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety
;     
C72 H162 O25 Si6 U2,(C18 H36 K N2 O6),(C22 H44 K N2 O7),0.2(O25 Si6 U2),0.8(K)  
;
_chemical_formula_sum            'C112 H242 K2.8 N4 O42.8 Si7.2 U2.54'
_chemical_formula_weight         3246.21
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-05-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.02.04 svn.rd84adfe8 for OlexSys, GUI svn.r6032)
;
_audit_update_record
;
2023-06-27 deposited with the CCDC.	2023-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.4373(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.1765(3)
_cell_length_b                   24.9651(5)
_cell_length_c                   32.6981(6)
_cell_measurement_reflns_used    16363
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      31.4240
_cell_measurement_theta_min      2.8310
_cell_volume                     14837.3(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.56a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.56a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.56a (Rigaku OD, 2019)'
_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 2018/2 (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      140.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5633
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.892
_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     12.00  92.00   0.50   16.98    --   19.99  38.00  30.00  160
  2  \w    -41.00  35.00   0.50   16.98    --   19.99 -77.00-120.00  152
  3  \w    -39.00   9.00   0.50   16.98    --  -20.06 -77.00  30.00   96
  4  \w    -24.00   3.00   0.50   16.98    --  -20.06 -77.00-150.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0112603000
_diffrn_orient_matrix_UB_12      -0.0259630000
_diffrn_orient_matrix_UB_13      -0.0062266000
_diffrn_orient_matrix_UB_21      -0.0326526000
_diffrn_orient_matrix_UB_22      0.0109353000
_diffrn_orient_matrix_UB_23      -0.0085846000
_diffrn_orient_matrix_UB_31      0.0181732000
_diffrn_orient_matrix_UB_32      0.0035707000
_diffrn_orient_matrix_UB_33      -0.0189335000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0317
_diffrn_reflns_av_unetI/netI     0.0599
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.892
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       47
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            51655
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         32.991
_diffrn_reflns_theta_min         2.469
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.977
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.522
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
 CrysAlisPro 1.171.40.56a (Rigaku Oxford Diffraction, 2019)
 Numerical absorption correction based on Gaussian integration over
 a multifaceted crystal model.
 Empirical absorption correction using spherical harmonics
 as implemented in SCALE3 ABSPACK scaling algorithm
;
_exptl_crystal_colour            'translucent dark black'
_exptl_crystal_density_diffrn    1.453
_exptl_crystal_description       irregular
_exptl_crystal_F_000             6688
_exptl_crystal_size_max          0.414
_exptl_crystal_size_mid          0.256
_exptl_crystal_size_min          0.22
_refine_diff_density_max         2.632
_refine_diff_density_min         -4.469
_refine_diff_density_rms         0.246
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     897
_refine_ls_number_reflns         24947
_refine_ls_number_restraints     1487
_refine_ls_restrained_S_all      1.027
_refine_ls_R_factor_all          0.1323
_refine_ls_R_factor_gt           0.0939
_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^)+(0.1296P)^2^+314.6060P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2434
_refine_ls_wR_factor_ref         0.2752
_reflns_Friedel_coverage         0.000
_reflns_number_gt                17371
_reflns_number_total             24947
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc05253b2.cif
_cod_data_source_block           nj215
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_exptl_absorpt_correction_type' value 'Gaussian' was
changed to 'gaussian' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1570263--1570267.cif.
;
_cod_original_formula_sum        'C112 H242 K2.80 N4 O42.80 Si7.20 U2.54'
_cod_database_code               1570264
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C112 H242 K2 N4 O38 Si6 U2'
_shelx_estimated_absorpt_t_max   0.560
_shelx_estimated_absorpt_t_min   0.372
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.44
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Si1B-O2B = Si1B-O5B = Si1B-O4B = Si1B-O3B
 1.68 with sigma of 0.01
 C30-C29 = C31-C29 = C32-C29
 1.54 with sigma of 0.02
 O64-C70_$1
 1.42 with sigma of 0.01
 C71-C71_$1
 1.54 with sigma of 0.01
 C71_$1-C70_$1
 1.4 with sigma of 0.01
 C89_$2-C89
 1.5 with sigma of 0.01
 C83-C82 = C85-C84
 1.54 with sigma of 0.02
 N2-C83 = N2-C84 = N2-C87
 1.5 with sigma of 0.02
 O81-C82 = O82-C86
 1.4 with sigma of 0.02
 Si2B-O23B \\sim Si2B-O22B \\sim Si2B-O24B \\sim Si2B-O21B
 with sigma of 0.01
 O5B-O4B \\sim O4B-O3B \\sim O3B-O5B
 with sigma of 0.02
 O5B-O2B \\sim O2B-O3B
 with sigma of 0.02
 O43B-O44B \\sim O44B-O42B \\sim O42B-O43B
 with sigma of 0.02
 Si4B-O41B \\sim Si4B-O44B \\sim Si4B-O42B \\sim Si4B-O43B
 with sigma of 0.01
 C31-C32 \\sim C32-C30 \\sim C30-C31
 with sigma of 0.02
 O22B-O23B \\sim O23B-O24B \\sim O24B-O22B
 with sigma of 0.02
 N2-C83 \\sim N2-C84 \\sim N2-C87
 with sigma of 0.02
 C87-C84 \\sim C84-C83 \\sim C83-C87
 with sigma of 0.02
 C83-C84 \\sim C84-C87
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O1 \\sim O2 \\sim O2B \\sim O3 \\sim O3B \\sim O4 \\sim O4B \\sim O5 \\sim O5B
\\sim O21 \\sim O21B \\sim O22 \\sim O22B \\sim O23 \\sim O23B \\sim O24 \\sim
O24B \\sim O41 \\sim O41B \\sim O42 \\sim O42B \\sim O43 \\sim O43B \\sim O44
\\sim O44B \\sim O61 \\sim O62 \\sim O63 \\sim O64 \\sim O81 \\sim O82 \\sim
O83 \\sim N1 \\sim N2 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6
\\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C21 \\sim C22
\\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30
\\sim C31 \\sim C32 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46
\\sim C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C61 \\sim C62
\\sim C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70
\\sim C71 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87
\\sim C88 \\sim C89: within 2A with sigma of 0.005 and sigma for terminal atoms
of 0.01 within 2A
Uanis(O64) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(O1) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(Si4B) = Uanis(Si1B)
Uanis(K1) = Uanis(K1B)
Uanis(U1) = Uanis(U2)
Uanis(Si4B) = Uanis(Si2B)
Uanis(K2) = Uanis(K2B)
Uanis(K1) = Uanis(K2)
Uanis(Si2) = Uanis(Si1)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: U2(0.2) U3(0.07) Si1B(0.2) Si2B(0.2) Si4B(0.2) O2B(0.2) O3B(0.2)
 O4B(0.2) O5B(0.2) O21B(0.2) O22B(0.2) O23B(0.2) O24B(0.2) O41B(0.2) O42B(0.2)
 O43B(0.2) O44B(0.2) K1B(0.2) K2B(0.2)
 Fixed X: O21B(0.67091)
 Fixed Z: Si1B(0.3165) K1B(0.492849)
6.a Secondary CH2 refined with riding coordinates:
 C61(H61A,H61B), C62(H62A,H62B), C63(H63A,H63B), C64(H64A,H64B), C65(H65A,
 H65B), C66(H66A,H66B), C67(H67A,H67B), C68(H68A,H68B), C69(H69A,H69B),
 C70(H70A,H70B), C71(H71A,H71B), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B),
  C84(H84A,H84B), C85(H85A,H85B), C86(H86A,H86B), C87(H87A,H87B), C88(H88A,
 H88B), C89(H89A,H89B)
6.b 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), 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)
;
_shelx_res_checksum              53684
_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
- B-factor correction
;
_oxdiff_exptl_absorpt_empirical_full_max 1.279
_oxdiff_exptl_absorpt_empirical_full_min 0.867