Synthesis, bonding properties and ether activation reactivity of cyclobutadienyl-ligated hybrid uranocenes
Tsoureas, Nikolaos; Mansikkamäki, Akseli; Layfield, Richard A.; Chemical Science 12 (2021) 2948–2954; doi:10.1039/D0SC05199C

data_1560033
_publ_section_title
;
 Synthesis, bonding properties and ether activation reactivity of
 cyclobutadienyl-ligated hybrid uranocenes
;
_journal_issue                   8
_journal_name_full               'Chemical Science'
_journal_page_first              2948
_journal_page_last               2954
_journal_paper_doi               10.1039/D0SC05199C
_journal_volume                  12
_journal_year                    2021
_chemical_formula_moiety
'C24 H44 Si4 U, C28.84 H52.97 O Si4 U, C3 H9 Si0.5, C2.5 H7.5 Si0.5'
_chemical_formula_sum            'C58.34 H113.47 O Si9 U2'
_chemical_formula_weight         1559.93
_chemical_name_common            '2 and 3'
_chemical_name_systematic        '2 and 3'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      tetragonal
_space_group_IT_number           81
_space_group_name_Hall           'P -4'
_space_group_name_H-M_alt        'P -4'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2020-06-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-08-31 deposited with the CCDC.	2021-01-08 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.3708(2)
_cell_length_b                   20.3708(2)
_cell_length_c                   16.6734(3)
_cell_measurement_reflns_used    17566
_cell_measurement_temperature    99.9(5)
_cell_measurement_theta_max      70.8080
_cell_measurement_theta_min      4.3280
_cell_volume                     6918.95(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.71a (Rigaku OD, 2020)'
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.1033
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_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    -22.00  69.00   1.00    2.50    --    0.00  57.00 120.00   91
  2  \w     34.00  78.00   1.00    2.50    --    0.00-178.00 -30.00   44
  3  \w    -12.00  16.00   1.00   10.00    --  -54.75  77.00   0.00   28
  4  \w    -76.00  13.00   1.00   10.00    --  -54.75  57.00 120.00   89
  5  \w    -86.00 -55.00   1.00   10.00    --  -54.75  77.00   0.00   31
  6  \w   -124.00 -33.00   1.00   10.00    --  -54.75 -57.00 -30.00   91
  7  \w   -124.00 -33.00   1.00   10.00    --  -54.75 -57.00 120.00   91
  8  \w    -16.00  73.00   1.00   10.00    --   54.75 -77.00 -30.00   89
  9  \w     86.00 126.00   1.00   10.00    --   54.75 125.00 -90.00   40
 10  \w     73.00 127.00   1.00   10.00    --   54.75 125.00  30.00   54
 11  \w     86.00 166.00   1.00   27.50    --  109.50  38.00-180.00   80
 12  \w     85.00 177.00   1.00   27.50    --  109.50  64.00-120.00   92
 13  \w     40.00 137.00   1.00   27.50    --  109.50 -38.00 -60.00   97
 14  \w     37.00 133.00   1.00   27.50    --  109.50 -91.00 -20.79   96
 15  \w     78.00 108.00   1.00   27.50    --  109.50 -91.00  62.80   30
 16  \w     84.00 178.00   1.00   27.50    --  109.50  38.00 120.00   94
 17  \w     40.00  65.00   1.00   27.50    --  109.50 -91.00  62.80   25
 18  \w     43.00 134.00   1.00   27.50    --  109.50 -64.00  60.00   91
 19  \w    130.00 169.00   1.00   27.50    --  109.50  77.00 -30.00   39
 20  \w     39.00 133.00   1.00   27.50    --  109.50 -50.00-180.00   94
 21  \w     78.00 109.00   1.00   27.50    --  109.50  77.00 -30.00   31
 22  \w     52.00 147.00   1.00   27.50    --  109.50 -91.00-172.40   95
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini ultra'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0675639000
_diffrn_orient_matrix_UB_12      0.0330221000
_diffrn_orient_matrix_UB_13      0.0098100000
_diffrn_orient_matrix_UB_21      0.0192163000
_diffrn_orient_matrix_UB_22      0.0224638000
_diffrn_orient_matrix_UB_23      0.0850607000
_diffrn_orient_matrix_UB_31      0.0280063000
_diffrn_orient_matrix_UB_32      0.0642010000
_diffrn_orient_matrix_UB_33      -0.0347865000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0510
_diffrn_reflns_av_unetI/netI     0.0505
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            42555
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.964
_diffrn_reflns_theta_min         3.425
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance Ultra (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    14.820
_exptl_absorpt_correction_T_max  0.11375
_exptl_absorpt_correction_T_min  0.02846
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.71a (Rigaku Oxford Diffraction, 2020)
Spherical absorption correction
 using equivalent radius and absorption coefficient.
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    1.498
_exptl_crystal_description       block
_exptl_crystal_F_000             3126
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Tetramethylsilane'
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_exptl_crystal_size_rad          0.400
_refine_diff_density_max         5.557
_refine_diff_density_min         -1.795
_refine_diff_density_rms         0.265
_refine_ls_abs_structure_details
;
 Flack x determined using 5502 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.000(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     672
_refine_ls_number_reflns         13128
_refine_ls_number_restraints     100
_refine_ls_restrained_S_all      1.074
_refine_ls_R_factor_all          0.0681
_refine_ls_R_factor_gt           0.0658
_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^)+(0.1233P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1594
_refine_ls_wR_factor_ref         0.1616
_reflns_Friedel_coverage         0.920
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                12661
_reflns_number_total             13128
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc05199c2.cif
_cod_data_source_block           2and3
_cod_depositor_comments
'Adding full bibliography for 1560031--1560036.cif.'
_cod_original_cell_volume        6919.0(2)
_cod_database_code               1560033
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C55 H86 Si8 U2'
_chemical_oxdiff_usercomment     'crystals from SiMe4'
_shelx_estimated_absorpt_t_max   0.319
_shelx_estimated_absorpt_t_min   0.066
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.6512(19)
 0.3488(19)
2. 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
3. Shared sites
{C57A, C57B}
{C59A, C59B}
4. Restrained distances
 Si5-C30B
 1.88 with sigma of 0.02
 C58A-C57A
 1.55 with sigma of 0.02
 Si3-C44
 1.88 with sigma of 0.02
 Si3-C46A
 1.88 with sigma of 0.02
 Si3-C46B
 1.88 with sigma of 0.02
 Si2-C48B
 1.88 with sigma of 0.02
 Si10-C53
 1.84 with sigma of 0.02
 Si10-C54
 1.84 with sigma of 0.02
 Si10-C55
 1.84 with sigma of 0.02
 C53-C55
 2.95 with sigma of 0.04
 C50-C51
 2.95 with sigma of 0.04
 Si7-C35A \\sim Si7-C35B
 with sigma of 0.02
 C58B-C56 \\sim C58A-C56
 with sigma of 0.04
 C58B-O1 \\sim C58A-O1
 with sigma of 0.04
 Si3-C45A \\sim Si3-C45B
 with sigma of 0.02
 Si2-C48B \\sim Si2-C48A
 with sigma of 0.02
5. Uiso/Uaniso restraints and constraints
Uanis(C35A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C30A) \\sim Ueq, Uanis(C30B) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.02
Uanis(C58A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C45A) \\sim Ueq, Uanis(C45B) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(C46B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C44) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C18) = Uanis(C19)
Uanis(C46B) = Uanis(C46A)
Uanis(C58A) = Uanis(C58B)
Uanis(C35A) = Uanis(C35B)
Uanis(C57A) = Uanis(C57B)
Uanis(C59A) = Uanis(C59B)
Uanis(C48A) = Uanis(C48B)
Uanis(C30A) = Uanis(C30B)
6. Rigid body (RIGU) restrains
 C53, C55, Si10, C54
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C50, C52, C51, Si9
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
7. Others
 Sof(C35B)=Sof(H35D)=Sof(H35E)=Sof(H35F)=1-FVAR(1)
 Sof(C35A)=Sof(H35A)=Sof(H35B)=Sof(H35C)=FVAR(1)
 Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(2)
 Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(2)
 Sof(H56A)=Sof(H56B)=Sof(C57A)=Sof(H57A)=Sof(H57B)=Sof(C59A)=Sof(H59A)=
 Sof(H59B)=Sof(C58A)=Sof(H58A)=Sof(H58B)=Sof(C57B)=Sof(H57C)=Sof(H57D)=
 Sof(C59B)=Sof(H59C)=Sof(H59D)=Sof(C58B)=Sof(H58C)=Sof(H58D)=FVAR(3)
 Sof(C46B)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C45B)=Sof(H45D)=Sof(H45E)=
 Sof(H45F)=1-FVAR(4)
 Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C45A)=Sof(H45A)=Sof(H45B)=
 Sof(H45C)=FVAR(4)
 Sof(C48B)=Sof(H48D)=Sof(H48E)=Sof(H48F)=1-FVAR(5)
 Sof(C48A)=Sof(H48A)=Sof(H48B)=Sof(H48C)=FVAR(5)
 Fixed Sof: H52A(0.5) H52B(0.5) H52C(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C56(H56A,H56B), C57A(H57A,H57B), C59A(H59A,H59B), C58A(H58A,H58B), C57B(H57C,
 H57D), C59B(H59C,H59D), C58B(H58C,H58D)
8.b Me refined with riding coordinates:
 C35A(H35A,H35B,H35C), C35B(H35D,H35E,H35F), C48A(H48A,H48B,H48C), C48B(H48D,
 H48E,H48F), C38(H38A,H38B,H38C), C30A(H30A,H30B,H30C), C30B(H30D,H30E,H30F),
 C52(H52A,H52B,H52C), C50(H50A,H50B,H50C), C44(H44A,H44B,H44C), C46A(H46A,H46B,
 H46C), C45A(H45A,H45B,H45C), C46B(H46D,H46E,H46F), C45B(H45D,H45E,H45F),
 C51(H51A,H51B,H51C)
8.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C19(H19), C21(H21), C25(H25), C24(H24), C23(H23), C22(H22),
 C12(H12), C10(H10), C17(H17), C11(H11), C18(H18), C14(H14), C15(H15), C16(H16),
  C13(H13)
8.d Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C29(H29A,H29B,
 H29C), C32(H32A,H32B,H32C), C34(H34A,H34B,H34C), C33(H33A,H33B,H33C), C28(H28A,
 H28B,H28C), C49(H49A,H49B,H49C), C41(H41A,H41B,H41C), C43(H43A,H43B,H43C),
 C26(H26A,H26B,H26C), C40(H40A,H40B,H40C), C42(H42A,H42B,H42C), C39(H39A,H39B,
 H39C), C47(H47A,H47B,H47C), C27(H27A,H27B,H27C), C54(H54A,H54B,H54C), C55(H55A,
 H55B,H55C), C53(H53A,H53B,H53C)
;
_shelx_res_checksum              16834
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.454
_oxdiff_exptl_absorpt_empirical_full_min 0.610