Heteroleptic Actinocenes: A Thorium(IV)-Cyclobutadienyl-Cyclooctatetraenyl-Di-Potassium-Cyclooctatetraenyl Complex
Boronski, Josef; Wooles, Ashley; Liddle, Stephen; Chemical Science  (2020) –; doi:10.1039/D0SC02479A

data_1558284
_publ_section_title
;
 Heteroleptic Actinocenes: A
 Thorium(IV)-Cyclobutadienyl-Cyclooctatetraenyl-Di-Potassium-Cyclooctatetraenyl
 Complex
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D0SC02479A
_journal_year                    2020
_chemical_formula_moiety         'C92 H136 K4 Si8 Th2, C7 H8'
_chemical_formula_sum            'C99 H144 K4 Si8 Th2'
_chemical_formula_weight         2179.33
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2020-03-04
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-03-24 deposited with the CCDC.	2020-06-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.3990(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   24.42520(10)
_cell_length_b                   10.92770(10)
_cell_length_c                   40.2845(2)
_cell_measurement_reflns_used    77806
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      75.6980
_cell_measurement_theta_min      2.4810
_cell_volume                     10260.42(13)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.983
_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    -56.00  20.00   1.00    1.00    --  -45.90  76.00 -90.00   76
  2  \w    -52.00 -25.00   1.00    1.00    --  -45.90  38.00-180.00   27
  3  \w     -3.00  41.00   1.00    1.00    --  -45.90  38.00-180.00   44
  4  \w    -86.00   5.00   1.00    1.00    --  -45.90  76.00-150.00   91
  5  \w    -36.00  23.00   1.00    1.00    --  -45.90  57.00 -30.00   59
  6  \w    -86.00   7.00   1.00    1.00    --  -45.90  76.00 120.00   93
  7  \w    -45.00  30.00   1.00    1.00    --  -45.90  57.00  60.00   75
  8  \w    -77.00 -18.00   1.00    1.00    -- -107.20  38.00  60.00   59
  9  \w   -196.00-105.00   1.00    1.00    -- -107.20 -76.00-150.00   91
 10  \w   -106.00 -62.00   1.00    1.00    -- -107.20  76.00   0.00   44
 11  \w   -108.00 -57.00   1.00    1.00    -- -107.20  76.00 120.00   51
 12  \w   -147.00 -18.00   1.00    1.00    -- -107.20  76.00  30.00  129
 13  \w   -132.00 -93.00   1.00    1.00    -- -107.20  76.00 -90.00   39
 14  \w   -124.00 -97.00   1.00    1.00    -- -107.20  76.00-120.00   27
 15  \w   -136.00 -91.00   1.00    1.00    -- -107.20  76.00 150.00   45
 16  \w   -196.00 -88.00   1.00    1.00    -- -107.20 -57.00 150.00  108
 17  \w    -57.00 -25.00   1.00    1.00    -- -107.20  76.00  90.00   32
 18  \w   -196.00 -68.00   1.00    1.00    -- -107.20 -38.00  60.00  128
 19  \w   -108.00 -63.00   1.00    1.00    -- -107.20  76.00  90.00   45
 20  \w   -139.00-114.00   1.00    1.00    -- -107.20  76.00  90.00   25
 21  \w   -128.00 -61.00   1.00    1.00    -- -107.20  76.00 -60.00   67
 22  \w    -89.00 -50.00   1.00    1.00    -- -107.20  76.00 -90.00   39
 23  \w   -197.00 -68.00   1.00    1.00    -- -107.20 -38.00  90.00  129
 24  \w   -148.00 -40.00   1.00    1.00    -- -107.20  76.00-150.00  108
 25  \w   -122.00 -96.00   1.00    1.00    -- -107.20  76.00 -30.00   26
 26  \w   -126.00-101.00   1.00    1.00    -- -107.20  76.00  60.00   25
 27  \w   -196.00 -87.00   1.00    1.00    -- -107.20 -57.00-180.00  109
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0277493000
_diffrn_orient_matrix_UB_12      0.0937465000
_diffrn_orient_matrix_UB_13      0.0185983000
_diffrn_orient_matrix_UB_21      -0.0398368000
_diffrn_orient_matrix_UB_22      -0.1005506000
_diffrn_orient_matrix_UB_23      0.0064622000
_diffrn_orient_matrix_UB_31      0.0448525000
_diffrn_orient_matrix_UB_32      -0.0313388000
_diffrn_orient_matrix_UB_33      0.0348992000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0303
_diffrn_reflns_av_unetI/netI     0.0196
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            121311
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.073
_diffrn_reflns_theta_min         2.494
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    11.943
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.459
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            'clear yellowish orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.411
_exptl_crystal_description       block
_exptl_crystal_F_000             4424
_exptl_crystal_size_max          0.247
_exptl_crystal_size_mid          0.227
_exptl_crystal_size_min          0.183
_refine_diff_density_max         1.237
_refine_diff_density_min         -1.548
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1119
_refine_ls_number_reflns         21092
_refine_ls_number_restraints     216
_refine_ls_restrained_S_all      1.064
_refine_ls_R_factor_all          0.0259
_refine_ls_R_factor_gt           0.0251
_refine_ls_shift/su_max          0.013
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0299P)^2^+19.3334P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0633
_refine_ls_wR_factor_ref         0.0637
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20548
_reflns_number_total             21092
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0sc02479a2.cif
_cod_data_source_block           1
_cod_original_cell_volume        10260.41(13)
_cod_database_code               1558284
_manchester_internal_diff_code   RSTL337
_manchester_internal_stl_name    THJB2
_manchester_internal_coll_client JB
_manchester_internal_coll_date   04/03/20
_manchester_internal_process_date 04/03/20
_manchester_internal_process_user AW/JB
_manchester_internal_solution_date 04/03/20
_manchester_internal_solution_user AW/JB
_manchester_internal_refinement_date 04/03/2020
_manchester_internal_refinement_user AW/JB
_manchester_internal_validation_date 04/03/2020
_manchester_internal_validation_user AW/JB
_manchester_internal_archive_date 05/03/2020
_manchester_internal_archive_user AW
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C120H100Th2Si8K4
_chemical_oxdiff_usercomment     jb
_shelx_estimated_absorpt_t_max   0.219
_shelx_estimated_absorpt_t_min   0.156
_reflns_odcompleteness_completeness 99.71
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C37A-C38A \\sim C39A-C38A \\sim C40A-C39A \\sim C33A-C40A \\sim C34A-C33A
\\sim C35A-C34A \\sim C36A-
 C35A \\sim C37A-C36A \\sim C39B-C38B \\sim C37B-C38B \\sim C37B-C36B \\sim
C35B-C36B \\sim C40B-C39B ~
 C35B-C34B \\sim C40B-C33B \\sim C34B-C33B
 with sigma of 0.01
3. Rigid body (RIGU) restrains
 C33A, C33B, C34A, C34B, C35A, C35B, C36A, C36B, C37A, C37B, C38A, C38B, C39A,
 C39B, C40A, C40B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
4. Others
 Sof(C33B)=Sof(H33B)=Sof(C34B)=Sof(H34B)=Sof(C35B)=Sof(H35B)=Sof(C36B)=
 Sof(H36B)=Sof(C37B)=Sof(H37B)=Sof(C38B)=Sof(H38B)=Sof(C39B)=Sof(H39B)=
 Sof(C40B)=Sof(H40B)=1-FVAR(1)
 Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35A)=Sof(C36A)=
 Sof(H36A)=Sof(C37A)=Sof(H37A)=Sof(C38A)=Sof(H38A)=Sof(C39A)=Sof(H39A)=
 Sof(C40A)=Sof(H40A)=FVAR(1)
5.a Me refined with riding coordinates:
 C79(H79A,H79B,H79C)
5.b Aromatic/amide H refined with riding coordinates:
 C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
  C25(H25), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31),
 C32(H32), C33A(H33A), C33B(H33B), C34A(H34A), C34B(H34B), C35A(H35A),
 C35B(H35B), C36A(H36A), C36B(H36B), C37A(H37A), C37B(H37B), C38A(H38A),
 C38B(H38B), C39A(H39A), C39B(H39B), C40A(H40A), C40B(H40B), C67(H67), C68(H68),
  C69(H69), C70(H70), C71(H71), C74(H74), C75(H75), C76(H76), C77(H77),
 C78(H78), C81(H81), C82(H82), C83(H83), C84(H84), C85(H85), C95(H95), C96(H96),
  C97(H97), C98(H98), C99(H99), C88(H88), C89(H89), C90(H90), C91(H91), C92(H92)
5.c Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,
 H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C48(H48A,
 H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C),
 C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,H54B,H54C), C55(H55A,H55B,
 H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C58(H58A,H58B,H58C), C59(H59A,
 H59B,H59C), C60(H60A,H60B,H60C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C),
 C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C72(H72A,H72B,
 H72C), C93(H93A,H93B,H93C), C86(H86A,H86B,H86C)
;
_shelx_res_checksum              64665
_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 2.076
_oxdiff_exptl_absorpt_empirical_full_min 0.655