Triamidoamine uranium(IV)-arsenic complexes containing one-, two- and threefold U-As bonding interactions
Benedict M. Gardner; Gabor Balazs; Manfred Scheer; Floriana Tuna; Eric J. L. McInnes; Jonathan McMaster; William Lewis; Alexander J. Blake; Stephen T. Liddle; Nature Chemistry 7 (2015) 582–590; doi:10.1038/nchem.2279

data_1551963
_publ_section_title
;
 Triamidoamine uranium(IV)-arsenic complexes containing one-, two- and
 threefold U-As bonding interactions
;
_journal_name_full               'Nature Chemistry'
_journal_page_first              582
_journal_page_last               590
_journal_paper_doi               10.1038/nchem.2279
_journal_volume                  7
_journal_year                    2015
_chemical_formula_moiety         'C33 H77 As N4 Si3 U'
_chemical_formula_sum            'C33 H77 As N4 Si3 U'
_chemical_formula_weight         927.20
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   'Geom, Me and AsH from difmap'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.04632(14)
_cell_length_b                   12.55844(13)
_cell_length_c                   20.9096(2)
_cell_measurement_reflns_used    40007
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      74.2450
_cell_measurement_theta_min      2.7280
_cell_volume                     4213.63(7)
_computing_cell_refinement
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48)'
_computing_data_collection
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48)'
_computing_data_reduction
'CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 10.6296
_diffrn_detector_type            'Agilent Diffraction Atlas detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_details
;
  1 omega  -80.00  -36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  125.0000  -60.0000 44

  2 omega   12.00   98.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.4723   19.0000 -180.0000 86

  3 omega   31.00   58.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -30.0000  120.0000 27

  4 omega   33.00   83.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -45.0000  -30.0000 50

  5 omega   31.00   78.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -30.0000 -180.0000 47

  6 omega   81.00  107.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -94.0000    0.0000 26

  7 omega   39.00   89.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -30.0000   60.0000 50

  8 omega   61.00   88.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -30.0000  120.0000 27

  9 omega   38.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -94.0000  -60.0000 71

 10 omega   16.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.4723   57.0000  -90.0000 97

 11 omega   16.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.4723   57.0000   30.0000 97

 12 omega   81.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   30.0000  150.0000 97

 13 omega   80.00  176.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   45.0000   60.0000 96

 14 omega   23.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -94.0000  150.0000 86

 15 omega   80.00  176.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   45.0000 -120.0000 96

 16 omega  -94.00   -2.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  125.0000  120.0000 92

 17 omega   11.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.4723   77.0000  150.0000 105

 18 omega   81.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   30.0000  -30.0000 97

 19 omega   73.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   77.0000   90.0000 105

 20 omega   73.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   77.0000    0.0000 105

 21 omega   73.00  178.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   77.0000 -180.0000 105

 22 omega  -49.00   34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   37.0000   60.0000 83

 23 omega   11.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.4723   77.0000   60.0000 105

 24 omega   33.00  122.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000 -125.0000  120.0000 89

 25 omega   23.00  109.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -94.0000 -150.0000 86

 26 omega   77.00  175.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   61.0000  150.0000 98

 27 omega   77.00  175.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   61.0000  -90.0000 98

 28 omega  -49.00   34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   37.0000  -60.0000 83

 29 omega   11.00  116.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       42.4723   77.0000  -60.0000 105

 30 omega   77.00  104.00   1.0000    4.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   61.0000  -30.0000 27
;
_diffrn_measurement_device       'k-geometry diffractometer'
_diffrn_measurement_device_type  'GV1000, Atlas'
_diffrn_measurement_method       'w scans'
_diffrn_orient_matrix_UB_11      0.0931061000
_diffrn_orient_matrix_UB_12      -0.0023003000
_diffrn_orient_matrix_UB_13      -0.0179469000
_diffrn_orient_matrix_UB_21      -0.0122890000
_diffrn_orient_matrix_UB_22      -0.1090257000
_diffrn_orient_matrix_UB_23      -0.0324138000
_diffrn_orient_matrix_UB_31      -0.0199384000
_diffrn_orient_matrix_UB_32      0.0561325000
_diffrn_orient_matrix_UB_33      -0.0636993000
_diffrn_radiation_collimation    'focusing mirrors'
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuKa
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0774
_diffrn_reflns_av_unetI/netI     0.0335
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            61910
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.967
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.386
_diffrn_reflns_theta_min         4.106
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    12.712
_exptl_absorpt_correction_T_max  0.363
_exptl_absorpt_correction_T_min  0.075
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies, Version 1.171.37.33 (release 27-03-2014 
CrysAlis171 .NET) (compiled Mar 27 2014,17:12:48) Numerical absorption 
correction based on gaussian integration over a multifaceted crystal model.
Empirical absorption correction using spherical harmonics, implemented in 
SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.462
_exptl_crystal_description       block
_exptl_crystal_F_000             1880
_exptl_crystal_size_max          0.3199
_exptl_crystal_size_mid          0.1877
_exptl_crystal_size_min          0.1312
_refine_diff_density_max         9.462
_refine_diff_density_min         -12.356
_refine_diff_density_rms         0.352
_refine_ls_abs_structure_details
;
 Flack x determined using 3372 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.505(5)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.302
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     588
_refine_ls_number_reflns         8321
_refine_ls_number_restraints     1242
_refine_ls_restrained_S_all      1.217
_refine_ls_R_factor_all          0.1059
_refine_ls_R_factor_gt           0.1052
_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^)+325.2004P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2533
_refine_ls_wR_factor_ref         0.2537
_reflns_Friedel_coverage         0.894
_reflns_Friedel_fraction_full    0.957
_reflns_Friedel_fraction_max     0.940
_reflns_number_gt                8240
_reflns_number_total             8321
_reflns_threshold_expression     'I > 2s(I)'
_cod_data_source_file            nchem.2279-s3.cif
_cod_data_source_block           2
_cod_original_cell_volume        4213.64(7)
_cod_database_code               1551963
_chemical_oxdiff_formula         C33H77AsN4Si3U
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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, All As(H,H) groups
2. Restrained distances
 C17-C16
 -2.5 with sigma of 0.02
 C17A-C16A
 -2.5 with sigma of 0.01
 C31-C30
 -2.4 with sigma of 0.02
 C27-C28
 -2.4 with sigma of 0.02
 C9-C8 = C28A-C27A
 -2.5 with sigma of 0.02
 Si3-C24A
 -3 with sigma of 0.02
 C24A-C25A
 -2.4 with sigma of 0.02
 C27A-C28A
 -2.4 with sigma of 0.02
 C13A-C14A
 -2.4 with sigma of 0.02
 H1A-U1
 3.48 with sigma of 0.02
 H1B-U1
 3.48 with sigma of 0.02
 H1A-H1B
 2.2 with sigma of 0.01
 As1-H1A = As1-H1B
 1.54 with sigma of 0.01
 C25-C24
 -2.4 with sigma of 0.02
 Si3-C24
 -3 with sigma of 0.02
 H21A-H14F
 -2 with sigma of 0.02
 H32A-H24D
 -2 with sigma of 0.02
 H1B-H15
 -2 with sigma of 0.02
 H21A-H14D
 -2 with sigma of 0.02
 H32A-H24F
 -2 with sigma of 0.02
 H1A-H29
 -2 with sigma of 0.02
 H2A-H31B
 -2 with sigma of 0.02
 C31A-C30A
 -2.5 with sigma of 0.02
 Si2-N2 sim Si2A-N2
 with sigma of 0.02
 Si2-C12 sim Si2A-C12A sim Si2A-C18A sim Si2-C18 sim Si2-C15
 with sigma of 0.01
 Si3-C26A sim Si3-C26 sim Si3-C23A sim Si3-C23 sim Si3-C29A sim
Si3-C29
 with sigma of 0.01
 C15-C16 sim C15-C17 sim C13-C12 sim C12-C14 sim C12A-C13A sim
C12A-C14A sim C20-C18 sim C18-
 C19 sim C18A-C19A sim C20A-C18A
 with sigma of 0.01
 C30-C29 sim C30A-C29A sim C31-C29 sim C31A-C29A sim C25-C23 sim
C24A-C23A sim C25A-C23A
 C24-C23 sim C28-C26 sim C27A-C26A sim C28A-C26A sim C27-C26
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.002 and sigma
for terminal atoms of 0.004
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(Si2A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=
 Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=Sof(C15A)=Sof(H15A)=Sof(C16A)=
 Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=
 Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C20A)=
 Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(1)
 Sof(Si2)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=
 Sof(H14A)=Sof(H14B)=Sof(H14C)=Sof(C15)=Sof(H15)=Sof(C16)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18)=Sof(C19)=
 Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(1)
 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)=Sof(C23A)=
 Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25A)=Sof(H25D)=
 Sof(H25E)=Sof(H25F)=1-FVAR(2)
 Sof(C23)=Sof(H23)=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)=Sof(C24)=Sof(H24D)=Sof(H24E)=Sof(H24F)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C4(H4), C7(H7), C12(H12), C12A(H12A), C15(H15), C15A(H15A), C18(H18),
 C18A(H18A), C23(H23), C26(H26), C26A(H26A), C29(H29), C29A(H29A), C23A(H23A)
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), C13A(H13D,H13E,H13F), C14(H14A,
 H14B,H14C), C14A(H14D,H14E,H14F), C16(H16A,H16B,H16C), C16A(H16D,H16E,H16F),
 C17(H17A,H17B,H17C), C17A(H17D,H17E,H17F), C19(H19A,H19B,H19C), C19A(H19D,H19E,
 H19F), C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F), C25(H25A,H25B,H25C),
 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), C24A(H24A,H24B,H24C), C25A(H25D,H25E,H25F), C24(H24D,
 H24E,H24F)
;