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_1551964
_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 H76 As N4 Si3 U, C28 H40 K O10'
_chemical_formula_sum            'C61 H116 As K N4 O10 Si3 U'
_chemical_formula_weight         1501.89
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_cell_angle_alpha                90
_cell_angle_beta                 104.2109(18)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.2073(3)
_cell_length_b                   19.3582(3)
_cell_length_c                   24.0982(4)
_cell_measurement_reflns_used    21949
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.5070
_cell_measurement_theta_min      2.9470
_cell_volume                     7329.3(2)
_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 1.000
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_details
;

  1 omega  -97.00  -64.00   1.0000   25.0000

omega____ theta____ kappa____ phi______ frames

    -      -38.5000 -153.0000    9.0000 33

  2 omega   30.00  114.00   1.0000   25.0000

omega____ theta____ kappa____ phi______ frames

    -       42.2223   37.0000    0.0000 84

  3 omega  -33.00   29.00   1.0000   25.0000

omega____ theta____ kappa____ phi______ frames

    -       42.2223  -19.0000    0.0000 62

  4 omega    6.00   54.00   1.0000   25.0000

omega____ theta____ kappa____ phi______ frames

    -       42.2223  -37.0000 -150.0000 48

  5 omega   34.00  130.00   1.0000  100.0000

omega____ theta____ kappa____ phi______ frames

    -      104.5000  -61.0000   60.0000 96

  6 omega   41.00   96.00   1.0000  100.0000

omega____ theta____ kappa____ phi______ frames

    -      104.5000  -45.0000  -60.0000 55

  7 omega   80.00  176.00   1.0000  100.0000

omega____ theta____ kappa____ phi______ frames

    -      104.5000   45.0000 -150.0000 96

  8 omega  124.00  151.00   1.0000  100.0000

omega____ theta____ kappa____ phi______ frames

    -      104.5000  125.0000   60.0000 27

  9 omega   74.00  176.00   1.0000  100.0000

omega____ theta____ kappa____ phi______ frames

    -      104.5000  125.0000   30.0000 102

 10 omega   52.00   79.00   1.0000  100.0000

omega____ theta____ kappa____ phi______ frames

    -      104.5000  -45.0000  -90.0000 27

 11 omega   91.00  118.00   1.0000  100.0000

omega____ theta____ kappa____ phi______ frames

    -      104.5000  125.0000   60.0000 27

 12 omega   34.00   91.00   1.0000  100.0000

omega____ theta____ kappa____ phi______ frames

    -      104.5000  -30.0000 -120.0000 57

 13 omega   16.00  112.00   1.0000   25.0000

omega____ theta____ kappa____ phi______ frames

    -       42.2223   57.0000  150.0000 96

 14 omega   11.00  116.00   1.0000   25.0000

omega____ theta____ kappa____ phi______ frames

    -       42.2223   77.0000 -120.0000 105

 15 omega   11.00  116.00   1.0000   25.0000

omega____ theta____ kappa____ phi______ frames

    -       42.2223   77.0000   30.0000 105

 16 omega   77.00  116.00   1.0000  100.0000

omega____ theta____ kappa____ phi______ frames

    -      104.5000   61.0000  -90.0000 39

 17 omega   81.00  178.00   1.0000  100.0000

omega____ theta____ kappa____ phi______ frames

    -      104.5000   30.0000    0.0000 97

;
_diffrn_measurement_device       'k-geometry diffractometer'
_diffrn_measurement_device_type  'GV1000, Atlas'
_diffrn_measurement_method       'w scans'
_diffrn_orient_matrix_UB_11      -0.0666150000
_diffrn_orient_matrix_UB_12      -0.0147935000
_diffrn_orient_matrix_UB_13      -0.0563083000
_diffrn_orient_matrix_UB_21      0.0535919000
_diffrn_orient_matrix_UB_22      0.0410114000
_diffrn_orient_matrix_UB_23      -0.0333554000
_diffrn_orient_matrix_UB_31      0.0479833000
_diffrn_orient_matrix_UB_32      -0.0665875000
_diffrn_orient_matrix_UB_33      -0.0079808000
_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  0.0655
_diffrn_reflns_av_unetI/netI     0.0462
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            50270
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.158
_diffrn_reflns_theta_min         2.813
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_target            Cu
_diffrn_source_type              'Agilent Diffraction microfocus tube'
_exptl_absorpt_coefficient_mu    8.126
_exptl_absorpt_correction_T_max  0.732
_exptl_absorpt_correction_T_min  0.338
_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            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.361
_exptl_crystal_description       plate
_exptl_crystal_F_000             3104
_exptl_crystal_size_max          0.1811
_exptl_crystal_size_mid          0.1586
_exptl_crystal_size_min          0.0414
_refine_diff_density_max         3.573
_refine_diff_density_min         -2.509
_refine_diff_density_rms         0.146
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1115
_refine_ls_number_reflns         14571
_refine_ls_number_restraints     2971
_refine_ls_restrained_S_all      0.961
_refine_ls_R_factor_all          0.0756
_refine_ls_R_factor_gt           0.0652
_refine_ls_shift/su_max          0.023
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[s^2^(Fo^2^)+(0.1008P)^2^+36.1359P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1762
_refine_ls_wR_factor_ref         0.1859
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                12270
_reflns_number_total             14571
_reflns_threshold_expression     'I > 2s(I)'
_cod_data_source_file            nchem.2279-s4.cif
_cod_data_source_block           3
_cod_database_code               1551964
_chemical_oxdiff_formula         C61H116AsKN4O10Si3U
_chemical_oxdiff_usercomment
'UBMGOL #13871 for BMG/STL in fomblin oil on micromount'
_reflns_odcompleteness_completeness 99.99
_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) groups

2. Restrained distances

 As1-H1

 1.58 with sigma of 0.02

 H32A-H26A

 -2.2 with sigma of 0.01

 H20D-H54A_$1

 -2.2 with sigma of 0.01

 H20E-H54A_$1

 -2.2 with sigma of 0.01

 C30-C29 sim C30A-C29A sim C31A-C29A sim C31-C29 sim C28A-C26A sim

C28-C26 sim C27A-C26A 

 C27-C26 sim C24A-C23A sim C24-C23 sim C25-C23 sim C25A-C23A

 with sigma of 0.02

 C47-C42 sim C47A-C42A

 with sigma of 0.02

 C47-C46 sim C47A-C46A sim C43-C42 sim C43A-C42A

 with sigma of 0.02

 C46-C45 sim C46A-C45A sim C44-C43 sim C44A-C43A

 with sigma of 0.02

 C45A-C44A sim C45-C44

 with sigma of 0.02

 O1-C47 sim O1A-C47A sim O5-C42 sim O5A-C42A

 with sigma of 0.02

 O1A-C34A sim O1-C34 sim O5-C41 sim O5A-C41A

 with sigma of 0.02

 C35-C34 sim C35A-C34A sim C41A-C40A sim C41-C40

 with sigma of 0.02

 O2A-C35A sim O2-C35 sim O4-C40 sim O4A-C40A

 with sigma of 0.02

 O2A-C36A sim O2-C36 sim O4-C39 sim O4A-C39A

 with sigma of 0.02

 C37-C36 sim C37A-C36A sim C39-C38 sim C39A-C38A

 with sigma of 0.02

 O3A-C37A sim O3-C37 sim O3A-C38A sim O3-C38

 with sigma of 0.02

 Si2A-N2 sim Si2-N2

 with sigma of 0.02

 Si2A-C12A sim Si2-C12 sim Si2-C15 sim Si2A-C15A sim Si2-C18

 with sigma of 0.02

 Si3-N3 sim Si3A-N3

 with sigma of 0.02

 Si3A-C29A sim Si3-C29 sim Si3A-C26A sim Si3-C26 sim Si3-C23 sim

Si3A-C23A

 with sigma of 0.02

 C14A-C12A sim C14-C12 sim C13-C12 sim C13A-C12A sim C17-C15 sim

C17A-C15A sim C16-C15 

 C16A-C15A sim C20-C18 sim C20A-C18A sim C19A-C18A sim C19-C18

 with sigma of 0.02

3. Uiso/Uaniso restraints and constraints

All non-hydrogen atoms have similar U: 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(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(Si3A)=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)=1-FVAR(2)

 Sof(Si3)=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)=FVAR(2)

 Sof(O1A)=Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(C35A)=Sof(H35C)=Sof(H35D)=Sof(O2A)=

 Sof(C36A)=Sof(H36C)=Sof(H36D)=Sof(C37A)=Sof(H37C)=Sof(H37D)=Sof(O3A)=Sof(C38A)=

 Sof(H38C)=Sof(H38D)=Sof(C39A)=Sof(H39C)=Sof(H39D)=Sof(O4A)=Sof(C40A)=Sof(H40C)=

 Sof(H40D)=Sof(C41A)=Sof(H41C)=Sof(H41D)=Sof(O5A)=Sof(C42A)=Sof(C43A)=Sof(H43A)=

 Sof(C44A)=Sof(H44A)=Sof(C45A)=Sof(H45A)=Sof(C46A)=Sof(H46A)=Sof(C47A)=1-FVAR(3)

 Sof(O1)=Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(O2)=

 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(O3)=Sof(C38)=

 Sof(H38A)=Sof(H38B)=Sof(C39)=Sof(H39A)=Sof(H39B)=Sof(O4)=Sof(C40)=Sof(H40A)=

 Sof(H40B)=Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(O5)=Sof(C42)=Sof(C43)=Sof(H43)=

 Sof(C44)=Sof(H44)=Sof(C45)=Sof(H45)=Sof(C46)=Sof(H46)=Sof(C47)=FVAR(3)

6.a Ternary CH refined with riding coordinates:

 C1(H1A), C4(H4), C7(H7), C12(H12), C12A(H12A), C15(H15), C15A(H15A), C18(H18),

  C18A(H18A), 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), C34(H34A,H34B), C34A(H34C,H34D), C35(H35A,H35B),

 C35A(H35C,H35D), C36(H36A,H36B), C36A(H36C,H36D), C37(H37A,H37B), C37A(H37C,

 H37D), C38(H38A,H38B), C38A(H38C,H38D), C39(H39A,H39B), C39A(H39C,H39D),

 C40(H40A,H40B), C40A(H40C,H40D), C41(H41A,H41B), C41A(H41C,H41D), C48(H48A,

 H48B), C49(H49A,H49B), C50(H50A,H50B), C51(H51A,H51B), C52(H52A,H52B),

 C53(H53A,H53B), C54(H54A,H54B), C55(H55A,H55B)

6.c Me refined with riding coordinates:

 C20(H20A,H20B,H20C), C20A(H20D,H20E,H20F)

6.d Aromatic/amide H refined with riding coordinates:

 C43(H43), C43A(H43A), C44(H44), C44A(H44A), C45(H45), C45A(H45A), C46(H46),

 C46A(H46A), C57(H57), C58(H58), C59(H59), C60(H60)

6.e 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), 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)

;