Facile N-functionalization and strong magnetic communication in a diuranium(v) bis-nitride complex
Barluzzi, Luciano; Chatelain, Lucile; Fadaei-Tirani, Farzaneh; Zivkovic, Ivica; Mazzanti, Marinella; Chemical Science  (2019) –; doi:10.1039/C8SC05721D

data_1550616
_publ_section_title
;
 Facile N-functionalization and strong magnetic communication in a
 diuranium(v) bis-nitride complex
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC05721D
_journal_year                    2019
_chemical_formula_moiety         'C73 H162 K2 N2 O26 Si6 U2, 1[C7H8]'
_chemical_formula_sum            'C73 H162 K2 N2 O26 Si6 U2'
_chemical_formula_weight         2206.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2018-08-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-12-06 deposited with the CCDC.
2019-02-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.306(3)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.9377(5)
_cell_length_b                   17.9175(5)
_cell_length_c                   22.0849(6)
_cell_measurement_reflns_used    13850
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.5020
_cell_measurement_theta_min      3.8170
_cell_volume                     5510.8(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (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      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.985
_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   -110.00 -16.00   1.00   10.00    --  -40.66 -57.00 -90.00   94
  2  \w    -55.00  34.00   1.00   10.00    --  -40.66  38.00-150.00   89
  3  \w    -65.00  32.00   1.00   10.00    --  -40.66  57.00  60.00   97
  4  \w     24.00  82.00   1.00   10.00    --   40.66 -99.00-150.00   58
  5  \w      2.00  65.00   1.00   10.00    --   40.66 -99.00 120.00   63
  6  \w    101.00 174.00   1.00   40.00    --  107.03 125.00 -90.00   73
  7  \w    100.00 172.00   1.00   40.00    --  107.03  30.00  30.00   72
  8  \w     34.00 140.00   1.00   40.00    --  107.03 -77.00-180.00  106
  9  \w     48.00 135.00   1.00   40.00    --  107.03 -30.00 150.00   87
 10  \w     94.00 172.00   1.00   40.00    --  107.03 125.00-150.00   78
 11  \w     89.00 117.00   1.00   40.00    --  107.03-125.00-180.00   28
 12  \w     94.00 155.00   1.00   40.00    --  107.03 125.00-120.00   61
 13  \w     30.00  55.00   1.00   40.00    --  107.03 -94.00-150.00   25
 14  \w     81.00 106.00   1.00   40.00    --  107.03 -94.00-150.00   25
 15  \w     34.00 127.00   1.00   40.00    --  107.03 -45.00 -60.00   93
 16  \w     38.00 119.00   1.00   40.00    --  107.03-125.00  30.00   81
 17  \w     71.00 105.00   1.00   40.00    --  107.03-125.00  90.00   34
 18  \w     81.00 174.00   1.00   40.00    --  107.03  45.00 -30.00   93
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1085115000
_diffrn_orient_matrix_UB_12      -0.0074012000
_diffrn_orient_matrix_UB_13      0.0147605000
_diffrn_orient_matrix_UB_21      0.0177472000
_diffrn_orient_matrix_UB_22      0.0736428000
_diffrn_orient_matrix_UB_23      -0.0337929000
_diffrn_orient_matrix_UB_31      -0.0116707000
_diffrn_orient_matrix_UB_32      0.0438275000
_diffrn_orient_matrix_UB_33      0.0592802000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0796
_diffrn_reflns_av_unetI/netI     0.0960
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            39631
_diffrn_reflns_point_group_measured_fraction_full 0.829
_diffrn_reflns_point_group_measured_fraction_max 0.805
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.911
_diffrn_reflns_theta_min         3.177
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    10.000
_exptl_absorpt_correction_T_max  0.742
_exptl_absorpt_correction_T_min  0.510
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
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            'clear intense yellow'
_exptl_crystal_density_diffrn    1.330
_exptl_crystal_description       plate
_exptl_crystal_F_000             2256
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.063
_exptl_crystal_size_min          0.045
_refine_diff_density_max         2.543
_refine_diff_density_min         -3.689
_refine_diff_density_rms         0.176
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.482(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1182
_refine_ls_number_reflns         17996
_refine_ls_number_restraints     2450
_refine_ls_restrained_S_all      0.968
_refine_ls_R_factor_all          0.0857
_refine_ls_R_factor_gt           0.0640
_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^)+(0.1106P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1592
_refine_ls_wR_factor_ref         0.1724
_reflns_Friedel_coverage         0.581
_reflns_Friedel_fraction_full    0.647
_reflns_Friedel_fraction_max     0.612
_reflns_number_gt                14700
_reflns_number_total             17996
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc05721d2.cif
_cod_data_source_block           lb188
_cod_database_code               1550616
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C73 H162 N2 O26 Si6 K2 U2'
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.518(11)
 0.482(11)
2. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C104-C101 = C102-C101 = C103-C101 = C110-C109 = C111-C109 = C112-C109 = C107-
 C105 = C108-C105 = C106-C105 = C69-C70 = C69-C71 = C69-C72 = C61A-C63A = C61A-
 C64A = C61A-C62A = C67A-C65A = C68A-C65A = C66-C65A = C88-C85 = C86-C85 = C87-
 C85 = C83-C81 = C84-C81 = C82-C81 = C8A-C5A = C5A-C7A = C5A-C6A = C92-C89 =
 C91-C89 = C90-C89 = C51-C49 = C50-C49 = C52-C49 = C42-C41 = C44-C41 = C43-C41 =
  C27-C25 = C28-C25 = C26-C25 = C21-C24 = C21-C23 = C21-C22 = C29-C30 = C31-C29
 = C29-C32 = C9-C11 = C12-C9 = C9-C10 = C4B-C1B = C3B-C1B = C2B-C1B = C46-C45 =
 C47-C45 = C48-C45 = C66B-C65B = C67B-C65B = C68B-C65B = C64B-C61B = C62B-C61B =
  C63B-C61B = C7B-C5B = C8B-C5B = C6B-C5B = C3A-C1A = C4A-C1A = C2A-C1A
 1.54 with sigma of 0.01
 C10-C11 \\sim C11-C12 \\sim C12-C10
 with sigma of 0.02
 C28-C26 \\sim C26-C27 \\sim C27-C28
 with sigma of 0.02
 C43-C42 \\sim C42-C44 \\sim C44-C43
 with sigma of 0.02
 C47-C48 \\sim C48-C46 \\sim C46-C47
 with sigma of 0.02
 C52-C51 \\sim C51-C50 \\sim C50-C52
 with sigma of 0.02
 C23-C22 \\sim C22-C24 \\sim C24-C23
 with sigma of 0.02
 C112-C110 \\sim C110-C111 \\sim C111-C112
 with sigma of 0.02
 C104-C103 \\sim C103-C102 \\sim C102-C104
 with sigma of 0.02
 C72-C71 \\sim C71-C70 \\sim C70-C72
 with sigma of 0.02
 C88-C87 \\sim C87-C86 \\sim C86-C88
 with sigma of 0.02
 C106-C107 \\sim C107-C108 \\sim C108-C106
 with sigma of 0.01
 C62A-C64A \\sim C64A-C63A \\sim C63A-C62A
 with sigma of 0.01
 Si1-O3A \\sim Si1-O3B \\sim Si1-O2A \\sim Si1-O2B
 with sigma of 0.02
 O3A-O2A \\sim O3B-O2B \\sim O62A-O63A \\sim O62B-O63B
 with sigma of 0.01
 O3A-C5A \\sim O3B-C5B \\sim O2B-C1B \\sim O2A-C1A \\sim O62A-C61A \\sim
O62B-C61B \\sim O63A-C65A ~
 O63B-C65B
 with sigma of 0.01
 C8B-C6B \\sim C6B-C7B \\sim C7B-C8B \\sim C7A-C8A \\sim C8A-C6A \\sim C6A-C7A
 with sigma of 0.02
 C3B-C4B \\sim C4B-C2B \\sim C2B-C3B \\sim C3A-C4A \\sim C4A-C2A \\sim C2A-C3A
 with sigma of 0.02
 Si4-O62A \\sim Si4-O62B \\sim Si4-O63A \\sim Si4-O63B
 with sigma of 0.01
 C64A-C62A \\sim C62A-C63A \\sim C63A-C64A \\sim C64B-C62B \\sim C62B-C63B
\\sim C63B-C64B
 with sigma of 0.01
 C66-C67A \\sim C67A-C68A \\sim C68A-C66 \\sim C66B-C67B \\sim C67B-C68B \\sim
C68B-C66B
 with sigma of 0.01
4. Uiso/Uaniso restraints and constraints
O1 \\sim O1A \\sim O2 \\sim O2A \\sim O2B \\sim O3A \\sim O3B \\sim O4 \\sim
O21 \\sim O22 \\sim O23 \\sim O24 \\sim O41 \\sim O42 \\sim O43 \\sim O44 \\sim
O61 \\sim O62A \\sim O62B \\sim O63A \\sim O63B \\sim O64 \\sim O81 \\sim O82
\\sim O83 \\sim O84 \\sim O101 \\sim O102 \\sim O103 \\sim O104 \\sim C1A \\sim
C1B \\sim C2 \\sim C2A \\sim C2B \\sim C3A \\sim C3B \\sim C4A \\sim C4B \\sim
C5A \\sim C5B \\sim C6A \\sim C6B \\sim C7A \\sim C7B \\sim C8A \\sim C8B \\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 C61A \\sim C61B \\sim C62A \\sim C62B
\\sim C63A \\sim C63B \\sim C64A \\sim C64B \\sim C65A \\sim C65B \\sim C66
\\sim C66B \\sim C67A \\sim C67B \\sim C68A \\sim C68B \\sim C69 \\sim C70
\\sim C71 \\sim C72 \\sim C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86
\\sim C87 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92 \\sim C101 \\sim
C102 \\sim C103 \\sim C104 \\sim C105 \\sim C106 \\sim C107 \\sim C108 \\sim
C109 \\sim C110 \\sim C111 \\sim C112: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
5. 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
6. Others
 Sof(O2B)=Sof(O3B)=Sof(C1B)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=Sof(C3B)=
 Sof(H3BA)=Sof(H3BB)=Sof(H3BC)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=Sof(C5B)=
 Sof(C6B)=Sof(H6BA)=Sof(H6BB)=Sof(H6BC)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(H7BC)=
 Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(H8BC)=1-FVAR(1)
 Sof(O2A)=Sof(O3A)=Sof(C1A)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(C3A)=
 Sof(H3AA)=Sof(H3AB)=Sof(H3AC)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(H4AC)=Sof(C5A)=
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=FVAR(1)
 Sof(O62B)=Sof(O63B)=Sof(C61B)=Sof(C62B)=Sof(H62D)=Sof(H62E)=Sof(H62F)=
 Sof(C63B)=Sof(H63D)=Sof(H63E)=Sof(H63F)=Sof(C64B)=Sof(H64D)=Sof(H64E)=
 Sof(H64F)=Sof(C65B)=Sof(C66B)=Sof(H66D)=Sof(H66E)=Sof(H66F)=Sof(C67B)=
 Sof(H67D)=Sof(H67E)=Sof(H67F)=Sof(C68B)=Sof(H68D)=Sof(H68E)=Sof(H68F)=1-FVAR(2)
 Sof(O62A)=Sof(O63A)=Sof(C61A)=Sof(C62A)=Sof(H62A)=Sof(H62B)=Sof(H62C)=
 Sof(C63A)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C64A)=Sof(H64A)=Sof(H64B)=
 Sof(H64C)=Sof(C65A)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C67A)=Sof(H67A)=
 Sof(H67B)=Sof(H67C)=Sof(C68A)=Sof(H68A)=Sof(H68B)=Sof(H68C)=FVAR(2)
 Fixed Y: U2(0.57739)
7.a Me refined with riding coordinates:
 C2A(H2AA,H2AB,H2AC), C2B(H2BA,H2BB,H2BC), C3A(H3AA,H3AB,H3AC), C3B(H3BA,H3BB,
 H3BC), C4A(H4AA,H4AB,H4AC), C4B(H4BA,H4BB,H4BC), C6A(H6AA,H6AB,H6AC), C6B(H6BA,
 H6BB,H6BC), C7A(H7AA,H7AB,H7AC), C7B(H7BA,H7BB,H7BC), C8A(H8AA,H8AB,H8AC),
 C8B(H8BA,H8BB,H8BC), 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),
 C62A(H62A,H62B,H62C), C62B(H62D,H62E,H62F), C63A(H63A,H63B,H63C), C63B(H63D,
 H63E,H63F), C64A(H64A,H64B,H64C), C64B(H64D,H64E,H64F), C66(H66A,H66B,H66C),
 C66B(H66D,H66E,H66F), C67A(H67A,H67B,H67C), C67B(H67D,H67E,H67F), C68A(H68A,
 H68B,H68C), C68B(H68D,H68E,H68F), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C),
 C72(H72A,H72B,H72C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,
 H84C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C90(H90A,
 H90B,H90C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C102(H10D,H10E,H10F),
 C103(H10G,H10H,H10I), C104(H10J,H10K,H10L), C106(H10M,H10N,H10O), C107(H10P,
 H10Q,H10R), C108(H10S,H10T,H10U), C110(H11D,H11E,H11F), C111(H11G,H11H,H11I),
 C112(H11J,H11K,H11L)
;
_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 6.511
_oxdiff_exptl_absorpt_empirical_full_min 0.227