Unprecedented pairs of uranium (iv/v) hydroxido and (iv/v/vi) oxido complexes supported by a seven-coordinate cyclen-anchored tris-aryloxide ligand
Löffler, Sascha T.; Hümmer, Julian; Scheurer, Andreas; Heinemann, Frank W.; Meyer, Karsten; Chemical Science  (2022) –; doi:10.1039/D2SC02736D

data_1567570
_publ_section_title
;
 Unprecedented pairs of uranium (iv/v) hydroxido and (iv/v/vi) oxido
 complexes supported by a seven-coordinate cyclen-anchored tris-aryloxide
 ligand
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC02736D
_journal_year                    2022
_chemical_formula_moiety         'C54 H85 N4 O4 U, 1.5(C4 H8 O)'
_chemical_formula_sum            'C60 H97 N4 O5.5 U'
_chemical_formula_weight         1200.44
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2021-09-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2022-02-08 deposited with the CCDC.	2022-08-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.97(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   30.404(6)
_cell_length_b                   10.566(2)
_cell_length_c                   37.842(8)
_cell_measurement_reflns_used    9304
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.71
_cell_measurement_theta_min      2.28
_cell_volume                     11627(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX3'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'SHELXTL 6.12 (Bruker AXS, 2002)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELX XT 2014/5 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker Kappa ImuS Duo Photon II CPAD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Quazar focussing montel optics'
_diffrn_radiation_source         'ImuS high brilliance micro-focus tube'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0637
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       40
_diffrn_reflns_limit_h_min       -40
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -49
_diffrn_reflns_number            211780
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.877
_diffrn_reflns_theta_min         2.037
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.842
_exptl_absorpt_correction_T_max  0.7458
_exptl_absorpt_correction_T_min  0.6490
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1097 before and 0.0565 after correction.
The Ratio of minimum to maximum transmission is 0.8702.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.372
_exptl_crystal_description       needle
_exptl_crystal_F_000             4968
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: tetrahydrofuran, n-hexane'
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.481
_refine_diff_density_min         -2.379
_refine_diff_density_rms         0.104
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.135
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     837
_refine_ls_number_reflns         13853
_refine_ls_number_restraints     552
_refine_ls_restrained_S_all      1.136
_refine_ls_R_factor_all          0.0640
_refine_ls_R_factor_gt           0.0482
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0180P)^2^+107.8216P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0896
_refine_ls_wR_factor_ref         0.0952
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11084
_reflns_number_total             13853
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02736d2.cif
_cod_data_source_block           jbh1805
_cod_original_formula_sum        'C60 H97 N4 O5.50 U'
_cod_database_code               1567570
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.895
_shelx_estimated_absorpt_t_min   0.614
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All C(H,H,H,H,H,H) groups
2. Uiso/Uaniso restraints and constraints
C40 \\sim C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C40A \\sim C41A
\\sim C42A \\sim C43A \\sim C44A \\sim C45A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C50 \\sim C51 \\sim C52 \\sim C53 \\sim C50A \\sim C51A \\sim C52A \\sim C53A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
O100 \\sim C101 \\sim C102 \\sim C103 \\sim C104 \\sim O110 \\sim C111 \\sim
C112 \\sim C113 \\sim C114: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
O200 \\sim C201 \\sim C202 \\sim C203 \\sim C204: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02
Uanis(C50) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53)
\\sim Ueq, Uanis(C50A) \\sim Ueq, Uanis(C51A) \\sim Ueq, Uanis(C52A) \\sim Ueq,
Uanis(C53A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
3. Same fragment restrains
{C20, C21, C22, C23} sigma for 1-2: 0.02, 1-3: 0.04
as
{C50, C51, C52, C53}
{C20, C21, C22, C23} sigma for 1-2: 0.02, 1-3: 0.04
as
{C50A, C51A, C52A, C53A}
{O100, C101, C102, C103, C104} sigma for 1-2: 0.02, 1-3: 0.04
as
{O110, C111, C112, C113, C114}
{O100, C101, C102, C103, C104} sigma for 1-2: 0.02, 1-3: 0.04
as
{O200, C201, C202, C203, C204}
4. Others
 Sof(C36A)=Sof(H36D)=Sof(H36E)=Sof(H36F)=Sof(C37A)=Sof(H37D)=Sof(H37E)=
 Sof(H37F)=Sof(C38A)=Sof(H38D)=Sof(H38E)=Sof(H38F)=1-FVAR(1)
 Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=
 Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=FVAR(1)
 Sof(H39C)=Sof(H39D)=Sof(C40A)=Sof(C41A)=Sof(C42A)=Sof(C43A)=Sof(H43A)=
 Sof(C44A)=Sof(C45A)=Sof(H45A)=Sof(H48D)=Sof(H48E)=Sof(H48F)=Sof(C50A)=
 Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=Sof(C52A)=Sof(H52D)=Sof(H52E)=
 Sof(H52F)=Sof(C53A)=Sof(H53D)=Sof(H53E)=Sof(H53F)=1-FVAR(2)
 Sof(H39A)=Sof(H39B)=Sof(C40)=Sof(C41)=Sof(C42)=Sof(C43)=Sof(H43)=Sof(C44)=
 Sof(C45)=Sof(H45)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C50)=Sof(C51)=Sof(H51A)=
 Sof(H51B)=Sof(H51C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=Sof(C53)=Sof(H53A)=
 Sof(H53B)=Sof(H53C)=FVAR(2)
 Sof(O110)=Sof(C111)=Sof(H11A)=Sof(H11B)=Sof(C112)=Sof(H11C)=Sof(H11D)=
 Sof(C113)=Sof(H11E)=Sof(H11F)=Sof(C114)=Sof(H11G)=Sof(H11H)=1-FVAR(3)
 Sof(O100)=Sof(C101)=Sof(H10A)=Sof(H10B)=Sof(C102)=Sof(H10C)=Sof(H10D)=
 Sof(C103)=Sof(H10E)=Sof(H10F)=Sof(C104)=Sof(H10G)=Sof(H10H)=FVAR(3)
 Fixed Sof: O200(0.5) C201(0.5) H20A(0.5) H20B(0.5) H20C(0.5) H20D(0.5)
 C203(0.5) H20E(0.5) H20F(0.5) C204(0.5) H20G(0.5) H20H(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C24(H24A,H24B), C39(H39A,H39B),
 C39(H39C,H39D), C101(H10A,H10B), C102(H10C,H10D), C103(H10E,H10F), C104(H10G,
 H10H), C111(H11A,H11B), C112(H11C,H11D), C113(H11E,H11F), C114(H11G,H11H),
 C201(H20A,H20B), C202(H20C,H20D), C203(H20E,H20F), C204(H20G,H20H)
5.b Me refined with riding coordinates:
 C48(H48A,H48B,H48C), C48(H48D,H48E,H48F), C51(H51A,H51B,H51C), C52(H52A,H52B,
 H52C), C53(H53A,H53B,H53C), C51A(H51D,H51E,H51F), C52A(H52D,H52E,H52F),
 C53A(H53D,H53E,H53F)
5.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C15(H15), C28(H28), C30(H30), C43(H43), C45(H45), C43A(H43A),
 C45A(H45A)
5.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C21(H21A,H21B,
 H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C32(H32A,H32B,H32C), C33(H33A,
 H33B,H33C), C34(H34A,H34B,H34C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C),
 C38(H38A,H38B,H38C), C36A(H36D,H36E,H36F), C37A(H37D,H37E,H37F), C38A(H38D,
 H38E,H38F), C47(H47A,H47B,H47C), C49(H49A,H49B,H49C), C54(H54A,H54B,H54C)
;
_shelx_res_checksum              21670
_shelx_hkl_checksum              89709
_olex2_submission_special_instructions 'No special instructions were received'