Actinide-transition metal bonding in heterobimetallic uranium- and thorium-molybdenum paddlewheel complexes.
Ayres, Alexander J.; Zegke, Markus; Ostrowski, Joseph P. A.; Tuna, Floriana; McInnes, Eric J. L.; Wooles, Ashley J.; Liddle, Stephen T.; Chemical communications (Cambridge, England) 54 (2018) 13515–13518; doi:10.1039/c8cc05268a

data_7122571
_publ_section_title
;
 Actinide-transition metal bonding in heterobimetallic uranium- and
 thorium-molybdenum paddlewheel complexes.
;
_journal_issue                   96
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              13515
_journal_page_last               13518
_journal_paper_doi               10.1039/c8cc05268a
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         'C66 H63 Cl Mo N3 O3 P3 Th, 2(C7 H8)'
_chemical_formula_sum            'C80 H79 Cl Mo N3 O3 P3 Th'
_chemical_formula_weight         1586.80
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2016-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2018-11-07 deposited with the CCDC.
2018-11-09 downloaded from the CCDC.
;
_cell_angle_alpha                88.897(3)
_cell_angle_beta                 74.385(4)
_cell_angle_gamma                89.611(3)
_cell_formula_units_Z            2
_cell_length_a                   12.3260(6)
_cell_length_b                   13.3087(4)
_cell_length_c                   21.9496(10)
_cell_measurement_reflns_used    6574
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      73.4440
_cell_measurement_theta_min      3.7250
_cell_volume                     3467.1(3)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
;
_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      120(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6296
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_details
;
  1 omega   -6.00   27.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   57.0000   30.0000 33

  2 omega -108.00  -12.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000  -77.0000  120.0000 96

  3 omega  -67.00   25.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.5000   77.0000 -120.0000 92

  4 omega  -20.00   73.00   1.0000   60.0000
omega____ theta____ kappa____ phi______ frames
    -       41.6804  -99.0000    0.0000 93

  5 omega   40.00   75.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -30.0000  -30.0000 35

  6 omega   79.00  106.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -94.0000  -30.0000 27

  7 omega   53.00   81.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -30.0000   90.0000 28

  8 omega   47.00  102.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -94.0000  -90.0000 55

  9 omega   40.00  121.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000 -125.0000 -120.0000 81

 10 omega   36.00  101.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000 -125.0000 -180.0000 65

 11 omega   85.00  178.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   30.0000    0.0000 93

 12 omega   89.00  157.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   30.0000   90.0000 68

 13 omega   51.00   97.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -45.0000   30.0000 46

 14 omega   78.00  127.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -77.0000  120.0000 49

 15 omega   47.00  104.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -94.0000   60.0000 57

 16 omega   31.00   80.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -30.0000 -180.0000 49

 17 omega   87.00  162.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000   45.0000  -60.0000 75

 18 omega   44.00  126.00   1.0000  240.0000
omega____ theta____ kappa____ phi______ frames
    -      104.5000  -61.0000  -90.0000 82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'GV1000, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1125060000
_diffrn_orient_matrix_UB_12      0.0495169000
_diffrn_orient_matrix_UB_13      -0.0017039000
_diffrn_orient_matrix_UB_21      0.0445653000
_diffrn_orient_matrix_UB_22      0.0155821000
_diffrn_orient_matrix_UB_23      -0.0721502000
_diffrn_orient_matrix_UB_31      -0.0468798000
_diffrn_orient_matrix_UB_32      -0.1034882000
_diffrn_orient_matrix_UB_33      -0.0102035000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1140
_diffrn_reflns_av_unetI/netI     0.1696
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            24004
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.249
_diffrn_reflns_theta_min         3.723
_diffrn_source                   'rotating-anode X-ray tube'
_diffrn_source_type              'GV1000 (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.758
_exptl_absorpt_correction_T_max  0.727
_exptl_absorpt_correction_T_min  0.644
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.31 (release 14-01-2014 CrysAlis171 .NET)
(compiled Jan 14 2014,18:38:05)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.520
_exptl_crystal_description       block
_exptl_crystal_F_000             1596
_exptl_crystal_size_max          0.0572
_exptl_crystal_size_mid          0.0475
_exptl_crystal_size_min          0.045
_refine_diff_density_max         3.074
_refine_diff_density_min         -1.503
_refine_diff_density_rms         0.209
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     980
_refine_ls_number_reflns         12669
_refine_ls_number_restraints     1835
_refine_ls_restrained_S_all      1.006
_refine_ls_R_factor_all          0.1147
_refine_ls_R_factor_gt           0.0806
_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^)+(0.0240P)^2^+16.0033P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1664
_refine_ls_wR_factor_ref         0.1849
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9296
_reflns_number_total             12669
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc05268a2.cif
_cod_data_source_block           ThClMo
_cod_depositor_comments
'Adding full bibliography for 7122562--7122573.cif.'
_cod_database_code               7122571
_nottingham_internal_coll_name   THAALG
_nottingham_internal_coll_number 14044
_nottingham_internal_coll_client AA/STL
_nottingham_internal_coll_type   custom
_nottingham_internal_coll_frame_method 'omega scans'
_nottingham_internal_coll_frame_time '60.0000, 240.0000'
_nottingham_internal_coll_frame_width 1.0000
_nottingham_internal_coll_user   pcxaa19
_nottingham_internal_coll_date   08/10/2014
_nottingham_internal_coll_location NOTTS
_nottingham_internal_coll_instrument 'GVB, PL13110001'
_nottingham_internal_process_date 13/10/2014
_nottingham_internal_process_user pcxaa19
_nottingham_internal_solution_date 13/10/2014
_nottingham_internal_solution_user AA
_nottingham_internal_refinement_date 29/09/2016
_nottingham_internal_refinement_user AW
_nottingham_internal_self_archive_date 29/09/2016
_nottingham_internal_self_validation_date 29/09/2016
_nottingham_internal_self_validation_user AW
_nottingham_internal_validation_date 29/09/2016
_nottingham_internal_validation_user AW
_nottingham_internal_archive_date 29/09/2016
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C80 H79 N3 P3 O3 Th Cl Mo'
_chemical_oxdiff_usercomment
'THAALG2 #14044 IN FOMBLIN FILM ON MICRMOUNT FOR AA/STL '
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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
 C75-C74 \\sim C82-C81 \\sim C68-C67
 with sigma of 0.02
 N2-C22 \\sim N2-C22A \\sim N1-C1 \\sim N3-C43
 with sigma of 0.01
 C80-C75 \\sim C76-C75 \\sim C77-C76 \\sim C80-C79 \\sim C79-C78 \\sim C78-C77
\\sim C86-C85 \\sim C85-C84
 \\sim C84-C83 \\sim C83-C82 \\sim C87-C82 \\sim C87-C86 \\sim C71-C70 \\sim
C72-C71 \\sim C73-C72 \\sim C73-
 C68 \\sim C69-C68 \\sim C70-C69
 with sigma of 0.02
 C69-C67 \\sim C67-C73 \\sim C87-C81 \\sim C81-C83 \\sim C80-C74 \\sim C74-C76
 with sigma of 0.02
3. Restrained planarity
 C74, C75, C76, C77, C78, C79, C80
 with sigma of 0.1
 C81, C82, C83, C84, C85, C86, C87
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim
C30 \\sim C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim
C28A \\sim C29A \\sim C30A \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47
\\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C1 \\sim C2 \\sim C3 \\sim C4
\\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim
C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87 \\sim C67 \\sim C68 \\sim
C69 \\sim C70 \\sim C71 \\sim C72 \\sim C73: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02
5. 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
6. Same fragment restrains
{C43, C44, C45, C46, C47, C48, C49, C50, C51} sigma for 1-2: 0.02, 1-3: 0.04
as
{C22, C23, C24, C25, C26, C27, C28, C29, C30}
{C43, C44, C45, C46, C47, C48, C49, C50, C51} sigma for 1-2: 0.02, 1-3: 0.04
as
{C22A, C23A, C24A, C25A, C26A, C27A, C28A, C29A, C30A}
7. Others
 Sof(C22A)=Sof(C23A)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=Sof(C25A)=
 Sof(H25A)=Sof(C26A)=Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28A)=
 Sof(H28A)=Sof(C29A)=Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(1)
 Sof(C22)=Sof(C23)=Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=Sof(C25)=Sof(H25)=
 Sof(C26)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C28)=Sof(H28)=Sof(C29)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
 Fixed Sof: C74(0.5) H74A(0.5) H74B(0.5) H74C(0.5) C75(0.5) C76(0.5) H76(0.5)
 C77(0.5) H77(0.5) C78(0.5) H78(0.5) C79(0.5) H79(0.5) C80(0.5) H80(0.5)
 C81(0.5) H81A(0.5) H81B(0.5) H81C(0.5) C82(0.5) C83(0.5) H83(0.5) C84(0.5)
 H84(0.5) C85(0.5) H85(0.5) C86(0.5) H86(0.5) C87(0.5) H87(0.5)
8.a Me refined with riding coordinates:
 C24(H24A,H24B,H24C), C27(H27A,H27B,H27C), C74(H74A,H74B,H74C), C81(H81A,H81B,
 H81C)
8.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C7(H7), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C17(H17),
 C18(H18), C19(H19), C20(H20), C21(H21), C25(H25), C28(H28), C32(H32), C33(H33),
  C34(H34), C35(H35), C36(H36), C38(H38), C39(H39), C40(H40), C41(H41),
 C42(H42), C46(H46), C49(H49), C53(H53), C54(H54), C55(H55), C56(H56), C57(H57),
  C59(H59), C60(H60), C61(H61), C62(H62), C63(H63), C76(H76), C77(H77),
 C78(H78), C79(H79), C80(H80), C83(H83), C84(H84), C85(H85), C86(H86), C87(H87),
  C69(H69), C70(H70), C71(H71), C72(H72), C73(H73), C25A(H25A), C28A(H28A)
8.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C6(H6A,H6B,H6C), C9(H9A,H9B,H9C), C30(H30A,H30B,H30C),
 C45(H45A,H45B,H45C), C48(H48A,H48B,H48C), C51(H51A,H51B,H51C), C67(H67A,H67B,
 H67C), C24A(H24D,H24E,H24F), C27A(H27D,H27E,H27F), C30A(H30D,H30E,H30F)
;
_shelx_res_checksum              33042
_olex2_submission_special_instructions 'No special instructions were received'