Synthesis and Characterization of an f-Block Terminal Parent Imido [U═NH] Complex: A Masked Uranium(IV) Nitride.
King, David M.; McMaster, Jonathan; Tuna, Floriana; McInnes, Eric J. L.; Lewis, William; Blake, Alexander J.; Liddle, Stephen T.; Journal of the American Chemical Society 136 (2014) 5619–; doi:10.1021/ja502405e

data_4121636
_publ_section_title
;
 Synthesis and Characterization of an f-Block Terminal Parent Imido
 [U&#x2550;NH] Complex: A Masked Uranium(IV) Nitride.
;
_journal_issue                   15
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              5619
_journal_paper_doi               10.1021/ja502405e
_journal_volume                  136
_journal_year                    2014
_chemical_formula_moiety         'C66 H152 Cs2 N10 Si6 U2'
_chemical_formula_sum            'C66 H152 Cs2 N10 Si6 U2'
_chemical_formula_weight         1996.39
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_symmetry_space_group_name_Hall  '-P 2ac 2ab'
_symmetry_space_group_name_H-M   'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   direct
_audit_creation_date             2014-02-16
_audit_creation_method
;
Olex2 1.2
(compiled 2014.02.11 svn.r2872 for OlexSys, GUI svn.r4767)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.8289(5)
_cell_length_b                   22.9287(9)
_cell_length_c                   27.1901(13)
_cell_measurement_reflns_used    9253
_cell_measurement_temperature    120()
_cell_measurement_theta_max      28.6310
_cell_measurement_theta_min      3.4250
_cell_volume                     8621.4(6)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_diffrn_ambient_temperature      120(2)
_diffrn_detector_area_resol_mean 8.0750
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.891
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0196596000
_diffrn_orient_matrix_UB_12      0.0106826000
_diffrn_orient_matrix_UB_13      0.0192950000
_diffrn_orient_matrix_UB_21      -0.0133933000
_diffrn_orient_matrix_UB_22      0.0207821000
_diffrn_orient_matrix_UB_23      -0.0234037000
_diffrn_orient_matrix_UB_31      -0.0106927000
_diffrn_orient_matrix_UB_32      -0.0456646000
_diffrn_orient_matrix_UB_33      -0.0061141000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0384
_diffrn_reflns_av_unetI/netI     0.0458
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.891
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            32577
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.891
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.915
_diffrn_reflns_theta_min         3.167
_diffrn_source                   'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.708
_exptl_absorpt_correction_T_max  0.883
_exptl_absorpt_correction_T_min  0.232
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Numerical absorption correction based on gaussian integration over
            a multifaceted crystal model
;
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.538
_exptl_crystal_description       block
_exptl_crystal_F_000             3984
_exptl_crystal_size_max          0.4316
_exptl_crystal_size_mid          0.2261
_exptl_crystal_size_min          0.1751
_refine_diff_density_max         6.097
_refine_diff_density_min         -4.519
_refine_diff_density_rms         0.261
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.224
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     498
_refine_ls_number_reflns         10130
_refine_ls_number_restraints     1397
_refine_ls_restrained_S_all      1.174
_refine_ls_R_factor_all          0.1330
_refine_ls_R_factor_gt           0.1154
_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^)+433.3302P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2195
_refine_ls_wR_factor_ref         0.2274
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8303
_reflns_number_total             10130
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja502405e_si_002.cif
_cod_data_source_block           2e
_cod_depositor_comments
'Adding full bibliography for 4121632--4121637.cif.'
_cod_database_code               4121636
_nottingham_internal_coll_name   UDKIOZ
_nottingham_internal_coll_number 12751
_nottingham_internal_coll_client DK/STL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_time 28
_nottingham_internal_coll_frame_width 1
_nottingham_internal_coll_frame_method \w
_nottingham_internal_coll_user   DMK
_nottingham_internal_coll_date   27/08/2013
_nottingham_internal_coll_location NOTTS
_nottingham_internal_process_user DMK
_nottingham_internal_process_date 28/08/2013
_nottingham_internal_solution_user DMK
_nottingham_internal_solution_date 28/08/2013
_nottingham_internal_refinement_user DMK
_nottingham_internal_refinement_date 28/08/2013
_nottingham_internal_self_validation_user DMK
_nottingham_internal_self_validation_date 14/02/2014
_shelxl_version_number           2014-1
_chemical_oxdiff_formula         'C66 H152 N10 Cs2 Si6 U2'
_chemical_oxdiff_usercomment
'UDKIOZ #12751 IN FOMBLIN FILM ON MICROMOUNT FOR DMK/STL'
_reflns_odcompleteness_completeness 99.62
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 N5-H5
 0.98 with sigma of 0.01
 U1-H5
 2.5 with sigma of 0.02
 U1-N1 \\sim U1-N2 \\sim U1-N3
 with sigma of 0.02
 N2-C21 \\sim N3-C32 \\sim N1-C10
 with sigma of 0.02
 C21-C22 \\sim C32-C33 \\sim C10-C11
 with sigma of 0.02
 N4-C33 \\sim N4-C11 \\sim N4-C22
 with sigma of 0.02
 Si2-N2 \\sim Si3-N3 \\sim Si1-N1
 with sigma of 0.02
 Si3-C26A \\sim Si3-C23A \\sim Si3-C29A \\sim Si2-C18 \\sim Si2-C12 \\sim
Si2-C15 \\sim Si1-C1 \\sim Si1-
 C7 \\sim Si1-C4
 with sigma of 0.02
 C29A-C31A \\sim C30A-C29A \\sim C23A-C24A \\sim C23A-C25A \\sim C26A-C28A
\\sim C26A-C27A \\sim C20-
 C18 \\sim C19-C18 \\sim C14-C12 \\sim C13-C12 \\sim C17-C15 \\sim C15-C16
\\sim C8-C7 \\sim C9-C7 \\sim C2-C1
 \\sim C3-C1 \\sim C6-C4 \\sim C5-C4
 with sigma of 0.02
 C3-C2 \\sim C5-C6 \\sim C9-C8 \\sim C24A-C25A \\sim C28A-C27A \\sim C31A-C30A
\\sim C19-C20 \\sim C17-C16
 \\sim C14-C13
 with sigma of 0.02
 C16-Si2 \\sim Si2-C17 \\sim C13-Si2 \\sim Si2-C14 \\sim C19-Si2 \\sim Si2-C20
\\sim C8-Si1 \\sim Si1-C9 ~
 C2-Si1 \\sim Si1-C3 \\sim C6-Si1 \\sim Si1-C5 \\sim C25A-Si3 \\sim Si3-C24A
\\sim C28A-Si3 \\sim Si3-C27A
 \\sim C31A-Si3 \\sim Si3-C30A
 with sigma of 0.02
 Si3-C29 \\sim Si3-C29A \\sim Si3-C23A \\sim Si3-C23 \\sim Si3-C26 \\sim
Si3-C26A
 with sigma of 0.02
 C26A-C27A \\sim C28-C26 \\sim C26A-C28A \\sim C26-C27 \\sim C23-C24 \\sim
C23-C25 \\sim C23A-C25A ~
 C23A-C24A \\sim C29-C30 \\sim C29-C31 \\sim C29A-C30A \\sim C29A-C31A
 with sigma of 0.02
 C27A-C28A \\sim C28-C27 \\sim C25-C24 \\sim C25A-C24A \\sim C30A-C31A \\sim
C31-C30
 with sigma of 0.02
 C30-Si3 \\sim Si3-C31 \\sim C30A-Si3 \\sim Si3-C31A \\sim C27-Si3 \\sim
Si3-C28 \\sim C27A-Si3 \\sim Si3-
 C28A \\sim C24A-Si3 \\sim Si3-C25A \\sim C24-Si3 \\sim Si3-C25
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Si3 \\sim C27A \\sim C26A \\sim C23A \\sim C30A \\sim C24A \\sim C25A \\sim C30
\\sim C29 \\sim C23 \\sim C24 \\sim C25 \\sim C27 \\sim C26 \\sim C31 \\sim
C31A \\sim C28A \\sim C28 \\sim C29A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
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
 Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25A)=
 Sof(H25B)=Sof(H25C)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30A)=
 Sof(H30B)=Sof(H30C)=Sof(C31)=Sof(H31A)=Sof(H31B)=Sof(H31C)=1-FVAR(1)
 Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=
 Sof(H25D)=Sof(H25E)=Sof(H25F)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27D)=
 Sof(H27E)=Sof(H27F)=Sof(C28A)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29A)=
 Sof(H29A)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31A)=Sof(H31D)=
 Sof(H31E)=Sof(H31F)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4), C7(H7), C12(H12), C15(H15), C18(H18), C23(H23), C23A(H23A),
 C26(H26), C26A(H26A), C29(H29), C29A(H29A)
6.b Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C11(H11A,H11B), C21(H21A,H21B), C22(H22A,H22B), C32(H32A,
 H32B), C33(H33A,H33B)
6.c Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C6(H6A,H6B,H6C), C8(H8A,
 H8B,H8C), C9(H9A,H9B,H9C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C16(H16A,
 H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C),
 C24(H24A,H24B,H24C), C24A(H24D,H24E,H24F), C25(H25A,H25B,H25C), C25A(H25D,H25E,
 H25F), C27(H27A,H27B,H27C), C27A(H27D,H27E,H27F), C28(H28A,H28B,H28C),
 C28A(H28D,H28E,H28F), C30(H30A,H30B,H30C), C30A(H30D,H30E,H30F), C31(H31A,H31B,
 H31C), C31A(H31D,H31E,H31F)
;