Tuning the structure, reactivity and magnetic communication of nitride-bridged uranium complexes with the ancillary ligands
Palumbo, Chad T.; Barluzzi, Luciano; Scopelliti, Rosario; Zivkovic, Ivica; Fabrizio, Alberto; Corminboeuf, Clémence; Mazzanti, Marinella; Chemical Science  (2019) –; doi:10.1039/C9SC02149C

data_1552189
_publ_section_title
;
 Tuning the structure, reactivity and magnetic communication of
 nitride-bridged uranium complexes with the ancillary ligands
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C9SC02149C
_journal_year                    2019
_chemical_formula_moiety         'C36 H108 N7 Si12 U2, C16 H36 N'
_chemical_formula_sum            'C52 H144 N8 Si12 U2'
_chemical_formula_weight         1694.88
_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'
_symmetry_space_group_name_Hall  '-I 2ya'
_symmetry_space_group_name_H-M   'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2019-02-14
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-04-30 deposited with the CCDC.    2019-08-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.785(3)
_cell_angle_gamma                90
_cell_formula_units_Z            12
_cell_length_a                   27.5312(6)
_cell_length_b                   21.7757(6)
_cell_length_c                   43.5129(11)
_cell_measurement_reflns_used    17795
_cell_measurement_temperature    140.00(10)
_cell_measurement_theta_max      74.5380
_cell_measurement_theta_min      3.0370
_cell_volume                     24839.8(12)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (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 5.2817
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.972
_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    -63.00  30.00   1.00   10.00    --  -40.79  57.00 -30.00   93
  2  \w    -57.00  17.00   1.00   10.00    --  -40.79  38.00  90.00   74
  3  \w   -107.00 -13.00   1.00   10.00    --  -40.79 -57.00  90.00   94
  4  \w   -110.00 -13.00   1.00   10.00    --  -40.79 -57.00-180.00   97
  5  \w     63.00  90.00   1.00   10.00    --   40.79-125.00-180.00   27
  6  \w     76.00 101.00   1.00   10.00    --   40.79 167.00-179.00   25
  7  \w     44.00  89.00   1.00   10.00    --   40.79-125.00  30.00   45
  8  \w     77.00 104.00   1.00   40.00    --  111.85 -94.00-150.00   27
  9  \w     90.00 162.00   1.00   40.00    --  111.85  45.00 120.00   72
 10  \w     56.00 137.00   1.00   40.00    --  111.85 -77.00 -90.00   81
 11  \w     93.00 127.00   1.00   40.00    --  111.85  77.00 -90.00   34
 12  \w     52.00 138.00   1.00   40.00    --  111.85 -30.00 -90.00   86
 13  \w    129.00 157.00   1.00   40.00    --  111.85 167.00-179.00   28
 14  \w     67.00 104.00   1.00   40.00    --  111.85 167.00-179.00   37
 15  \w     96.00 122.00   1.00   40.00    --  111.85-125.00   0.00   26
 16  \w     87.00 113.00   1.00   40.00    --  111.85-125.00 120.00   26
 17  \w     43.00  70.00   1.00   40.00    --  111.85-125.00   0.00   27
 18  \w     41.00 134.00   1.00   40.00    --  111.85 -61.00  30.00   93
 19  \w     40.00 139.00   1.00   40.00    --  111.85 -61.00 150.00   99
 20  \w     39.00 161.00   1.00   40.00    --  111.85 -15.00  90.00  122
 21  \w     75.00 108.00   1.00   40.00    --  111.85 -94.00 120.00   33
;
_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      0.0067861000
_diffrn_orient_matrix_UB_12      0.0099362000
_diffrn_orient_matrix_UB_13      0.0361231000
_diffrn_orient_matrix_UB_21      -0.0124280000
_diffrn_orient_matrix_UB_22      0.0687177000
_diffrn_orient_matrix_UB_23      -0.0064906000
_diffrn_orient_matrix_UB_31      -0.0570057000
_diffrn_orient_matrix_UB_32      -0.0137164000
_diffrn_orient_matrix_UB_33      -0.0060036000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0531
_diffrn_reflns_av_unetI/netI     0.0546
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            87079
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.047
_diffrn_reflns_theta_min         2.638
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.840
_exptl_absorpt_correction_T_max  0.905
_exptl_absorpt_correction_T_min  0.282
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018).
 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            'clear light brown'
_exptl_crystal_density_diffrn    1.360
_exptl_crystal_description       plate
_exptl_crystal_F_000             10368
_exptl_crystal_size_max          0.148
_exptl_crystal_size_mid          0.061
_exptl_crystal_size_min          0.022
_refine_diff_density_max         1.463
_refine_diff_density_min         -2.401
_refine_diff_density_rms         0.137
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.986
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1298
_refine_ls_number_reflns         25540
_refine_ls_number_restraints     666
_refine_ls_restrained_S_all      0.979
_refine_ls_R_factor_all          0.0661
_refine_ls_R_factor_gt           0.0377
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0450P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0829
_refine_ls_wR_factor_ref         0.0945
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18125
_reflns_number_total             25540
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9sc02149c2.cif
_cod_data_source_block           ctp088
_cod_depositor_comments
;
The following automatic conversions were performed:

'_exptl_absorpt_correction_type' value 'Gaussian' changed to
'gaussian' according to
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_original_cell_volume        24839.8(11)
_cod_database_code               1552189
_shelx_shelxl_version_number     2018/3
_audit_contact_author            'Farzaneh Fadaei Tirani'
_chemical_oxdiff_formula         'C52 H144 N8 Si12 U2'
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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
 N12A-C113 = N12A-C101 = C105-C106 = C109-C110
 1.519 with sigma of 0.02
 N12A-C114 = N12A-C102
 2.562 with sigma of 0.04
 N12A-C105 = N12A-C109 = C113-C114 = C101-C102
 1.517 with sigma of 0.02
 N12A-C106 = N12A-C110
 2.591 with sigma of 0.04
 C113-C115 = C101-C103
 2.483 with sigma of 0.04
 C105-C107 = C109-C111
 2.479 with sigma of 0.04
 C114-C115 = C102-C103
 1.525 with sigma of 0.02
 C114-C116 = C102-C104
 2.527 with sigma of 0.04
 C106-C107 = C110-C111
 1.526 with sigma of 0.02
 C106-C108 = C110-C112
 2.531 with sigma of 0.04
 C115-C116 = C103-C104
 1.49 with sigma of 0.02
 C107-C108 = C111-C112
 1.493 with sigma of 0.02
 N13-C133 = N13-C121 = C125-C126 = C129-C130
 1.519 with sigma of 0.02
 N13-C134 = N13-C122
 2.562 with sigma of 0.04
 N13-C125 = N13-C129 = C133-C134 = C121-C122
 1.517 with sigma of 0.02
 N13-C126 = N13-C130
 2.591 with sigma of 0.04
 C133-C135 = C121-C123
 2.483 with sigma of 0.04
 C125-C127 = C129-C131
 2.479 with sigma of 0.04
 C134-C135 = C122-C123
 1.525 with sigma of 0.02
 C134-C136 = C122-C124
 2.527 with sigma of 0.04
 C126-C127 = C130-C131
 1.526 with sigma of 0.02
 C126-C128 = C130-C132
 2.531 with sigma of 0.04
 C135-C136 = C123-C124
 1.49 with sigma of 0.02
 C127-C128 = C131-C132
 1.493 with sigma of 0.02
 C7-C15 = C9-C17
 2.483 with sigma of 0.04
 C8-C16 = C10-C18
 2.479 with sigma of 0.04
 C11-C15 = C13-C17
 1.525 with sigma of 0.02
 C11-C19 = C13-C1B
 2.527 with sigma of 0.04
 C12-C16 = C14-C18
 1.526 with sigma of 0.02
 C12-C1A = C14-C1C
 2.531 with sigma of 0.04
 C15-C19 = C17-C1B
 1.49 with sigma of 0.02
 C16-C1A = C18-C1C
 1.493 with sigma of 0.02
 N12B-C7 = N12B-C9 = C8-C12 = C10-C14
 1.519 with sigma of 0.02
 N12B-C11 = N12B-C13
 2.562 with sigma of 0.04
 N12B-C8 = N12B-C10 = C7-C11 = C9-C13
 1.517 with sigma of 0.02
 N12B-C12 = N12B-C14
 2.591 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
N13 \\sim C121 \\sim C122 \\sim C123 \\sim C124 \\sim C125 \\sim C126 \\sim
C127 \\sim C128 \\sim C129 \\sim C130 \\sim C131 \\sim C132 \\sim C133 \\sim
C134 \\sim C135 \\sim C136: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01
N12A \\sim C101 \\sim C102 \\sim C103 \\sim C104 \\sim C105 \\sim C106 \\sim
C107 \\sim C108 \\sim C109 \\sim C110 \\sim C111 \\sim C112 \\sim C113 \\sim
C114 \\sim C115 \\sim C116 \\sim N12B \\sim C1A \\sim C1B \\sim C1C \\sim C7
\\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15
\\sim C16 \\sim C17 \\sim C18 \\sim C19: within 2A with sigma of 0.005 and
sigma for terminal atoms of 0.01
4. Others
 Sof(N12B)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=
 Sof(H1BC)=Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(H1CC)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10U)=
 Sof(H10V)=Sof(C11)=Sof(H11Q)=Sof(H11R)=Sof(C12)=Sof(H12A)=Sof(H12B)=Sof(C13)=
 Sof(H13A)=Sof(H13B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(C18)=Sof(H18A)=
 Sof(H18B)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=1-FVAR(1)
 Sof(N12A)=Sof(C101)=Sof(H10A)=Sof(H10B)=Sof(C102)=Sof(H10C)=Sof(H10D)=
 Sof(C103)=Sof(H10E)=Sof(H10F)=Sof(C104)=Sof(H10G)=Sof(H10H)=Sof(H10I)=
 Sof(C105)=Sof(H10J)=Sof(H10K)=Sof(C106)=Sof(H10L)=Sof(H10M)=Sof(C107)=
 Sof(H10N)=Sof(H10O)=Sof(C108)=Sof(H10P)=Sof(H10Q)=Sof(H10R)=Sof(C109)=
 Sof(H10S)=Sof(H10T)=Sof(C110)=Sof(H11A)=Sof(H11B)=Sof(C111)=Sof(H11C)=
 Sof(H11D)=Sof(C112)=Sof(H11E)=Sof(H11F)=Sof(H11G)=Sof(C113)=Sof(H11H)=
 Sof(H11I)=Sof(C114)=Sof(H11J)=Sof(H11K)=Sof(C115)=Sof(H11L)=Sof(H11M)=
 Sof(C116)=Sof(H11N)=Sof(H11O)=Sof(H11P)=FVAR(1)
 Fixed Sof: N13(0.5) C121(0.5) H12C(0.5) H12D(0.5) C122(0.5) H12E(0.5)
 H12F(0.5) C123(0.5) H12G(0.5) H12H(0.5) C124(0.5) H12I(0.5) H12J(0.5)
 H12K(0.5) C125(0.5) H12L(0.5) H12M(0.5) C126(0.5) H12N(0.5) H12O(0.5)
 C127(0.5) H12P(0.5) H12Q(0.5) C128(0.5) H12R(0.5) H12S(0.5) H12T(0.5)
 C129(0.5) H12U(0.5) H12V(0.5) C130(0.5) H13C(0.5) H13D(0.5) C131(0.5)
 H13E(0.5) H13F(0.5) C132(0.5) H13G(0.5) H13H(0.5) H13I(0.5) C133(0.5)
 H13J(0.5) H13K(0.5) C134(0.5) H13L(0.5) H13M(0.5) C135(0.5) H13N(0.5)
 H13O(0.5) C136(0.5) H13P(0.5) H13Q(0.5) H13R(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C101(H10A,H10B), C102(H10C,H10D), C103(H10E,H10F), C105(H10J,H10K), C106(H10L,
 H10M), C107(H10N,H10O), C109(H10S,H10T), C110(H11A,H11B), C111(H11C,H11D),
 C113(H11H,H11I), C114(H11J,H11K), C115(H11L,H11M), C7(H7A,H7B), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10U,H10V), C11(H11Q,H11R), C12(H12A,H12B), C13(H13A,H13B),
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B),
  C121(H12C,H12D), C122(H12E,H12F), C123(H12G,H12H), C125(H12L,H12M), C126(H12N,
 H12O), C127(H12P,H12Q), C129(H12U,H12V), C130(H13C,H13D), C131(H13E,H13F),
 C133(H13J,H13K), C134(H13L,H13M), C135(H13N,H13O)
5.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,
 H5B,H5C), C6(H6A,H6B,H6C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,
 H34C), C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C),
 C46(H46A,H46B,H46C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C53(H53A,H53B,
 H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C61(H61A,
 H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C),
 C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C71(H71A,H71B,H71C), C72(H72A,H72B,
 H72C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C76(H76A,
 H76B,H76C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C),
 C84(H84A,H84B,H84C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C91(H91A,H91B,
 H91C), C92(H92A,H92B,H92C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C95(H95A,
 H95B,H95C), C96(H96A,H96B,H96C), C104(H10G,H10H,H10I), C108(H10P,H10Q,H10R),
 C112(H11E,H11F,H11G), C116(H11N,H11O,H11P), C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,
 H1BC), C1C(H1CA,H1CB,H1CC), C19(H19A,H19B,H19C), C124(H12I,H12J,H12K),
 C128(H12R,H12S,H12T), C132(H13G,H13H,H13I), C136(H13P,H13Q,H13R)
;
_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 3.868
_oxdiff_exptl_absorpt_empirical_full_min 0.314