Thorium-phosphorus triamidoamine complexes containing Th-P single- and multiple-bond interactions
Elizabeth P. Wildman; Gabor Balazs; Ashley J. Wooles; Manfred Scheer; Stephen T. Liddle; Nature Communications 7 (2016) 12884–; doi:10.1038/ncomms12884

data_1548026
_publ_section_title
;
 Thorium-phosphorus triamidoamine complexes containing Th-P single- and
 multiple-bond interactions
;
_journal_name_full               'Nature Communications'
_journal_page_first              12884
_journal_paper_doi               10.1038/ncomms12884
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety         'C37 H85 N4 O2 Si3 Th, C24 H20 B, C6 H6'
_chemical_formula_sum            'C67 H111 B N4 O2 Si3 Th'
_chemical_formula_weight         1331.71
_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
_cell_angle_alpha                89.696(4)
_cell_angle_beta                 88.052(4)
_cell_angle_gamma                86.937(4)
_cell_formula_units_Z            4
_cell_length_a                   14.3496(6)
_cell_length_b                   17.9265(8)
_cell_length_c                   26.5741(12)
_cell_measurement_reflns_used    15399
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      25.8830
_cell_measurement_theta_min      3.4760
_cell_volume                     6822.1(5)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -26.00  31.00   1.00   18.00    --  -17.77  57.00  60.00   57
  2  \w    -54.00  10.00   1.00   18.00    --   18.86 -19.00-120.00   64
  3  \w    -40.00   5.00   1.00   18.00    --   18.86 -57.00-150.00   45
  4  \w     -7.00  59.00   1.00   18.00    --   18.86 -99.00 150.00   66
  5  \w    -87.00  -4.00   1.00   18.00    --  -17.77 -57.00-120.00   83
  6  \w    -85.00   8.00   1.00   18.00    --  -17.77 -77.00   0.00   93
  7  \w    -72.00  12.00   1.00   18.00    --  -17.77 -77.00 120.00   84
  8  \w    -49.00  40.00   1.00   18.00    --   18.86 -57.00 120.00   89
  9  \w    -20.00  61.00   1.00   18.00    --   18.86 -99.00   0.00   81
 10  \w      9.00  61.00   1.00   18.00    --   18.86 -99.00 -90.00   52
 11  \w     15.00  91.00   1.00   18.00    --   18.86  37.00-150.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0136380000
_diffrn_orient_matrix_UB_12      0.0333045000
_diffrn_orient_matrix_UB_13      0.0112881000
_diffrn_orient_matrix_UB_21      -0.0030606000
_diffrn_orient_matrix_UB_22      0.0186931000
_diffrn_orient_matrix_UB_23      -0.0235248000
_diffrn_orient_matrix_UB_31      -0.0475159000
_diffrn_orient_matrix_UB_32      0.0105559000
_diffrn_orient_matrix_UB_33      0.0056948000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_unetI/netI     0.1125
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            24033
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         3.235
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.282
_exptl_absorpt_correction_T_max  0.820
_exptl_absorpt_correction_T_min  0.715
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.297
_exptl_crystal_description       block
_exptl_crystal_F_000             2776
_exptl_crystal_size_max          0.207
_exptl_crystal_size_mid          0.161
_exptl_crystal_size_min          0.108
_refine_diff_density_max         12.923
_refine_diff_density_min         -11.451
_refine_diff_density_rms         0.441
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.248
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1335
_refine_ls_number_reflns         24033
_refine_ls_number_restraints     3906
_refine_ls_restrained_S_all      1.156
_refine_ls_R_factor_all          0.2352
_refine_ls_R_factor_gt           0.2147
_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^)+(0.0001P)^2^+1052.7897P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4880
_refine_ls_wR_factor_ref         0.4980
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                19730
_reflns_number_total             24033
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ncomms12884-s2.cif
_cod_data_source_block           1.DME
_cod_database_code               1548026
_chemical_oxdiff_formula         'Th C67 H111 N4 Si3 B O2'
_chemical_oxdiff_usercomment     EW/STL
_reflns_odcompleteness_completeness 99.79
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.683 0.239 0.078
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. Restrained distances
 N2-C21
 1.5 with sigma of 0.01
 C133-C132 = C134-C133 = C134-C129 = C130-C129 = C131-C130 = C132-C131
 1.39 with sigma of 0.02
 C127-C126 = C126-C125 = C125-C124 = C128-C123 = C124-C123 = C128-C127
 1.39 with sigma of 0.02
 C36-C35 = C97-C96
 1.55 with sigma of 0.02
 O1-C36 = O1-C37 = O2-C35 = O2-C34 = O4-C95 = O4-C96 = O3-C97 = O3-C98
 1.45 with sigma of 0.02
 C57-C56 \\sim C61-C56 \\sim C61-C60 \\sim C60-C59 \\sim C58-C57 \\sim C59-C58
\\sim C39-C38 \\sim C40-C39
 \\sim C41-C40 \\sim C42-C41 \\sim C43-C42 \\sim C43-C38 \\sim C55-C54 \\sim
C54-C53 \\sim C53-C52 \\sim C52-
 C51 \\sim C55-C50 \\sim C51-C50 \\sim C46-C45 \\sim C49-C48 \\sim C45-C44
\\sim C49-C44 \\sim C48-C47 ~
 C47-C46 \\sim C101-C100 \\sim C102-C101 \\sim C103-C102 \\sim C104-C103 \\sim
C99-C104 \\sim C99-C100
 \\sim C116-C115 \\sim C116-C111 \\sim C112-C111 \\sim C113-C112 \\sim
C114-C113 \\sim C115-C114 \\sim C110-
 C105 \\sim C107-C106 \\sim C106-C105 \\sim C110-C109 \\sim C108-C107 \\sim
C109-C108 \\sim C118-C117 ~
 C122-C117 \\sim C122-C121 \\sim C121-C120 \\sim C120-C119 \\sim C119-C118
 with sigma of 0.02
 C20-C18 \\sim C19-C18 \\sim C13-C12 \\sim C14-C12 \\sim C17-C15 \\sim C16-C15
\\sim C3-C1 \\sim C2-C1 ~
 C5-C4 \\sim C6-C4 \\sim C9-C7 \\sim C8-C7 \\sim C25-C23 \\sim C24-C23 \\sim
C27-C26 \\sim C28-C26 \\sim C30-
 C29 \\sim C31-C29 \\sim C78-C76 \\sim C77-C76 \\sim C80-C79 \\sim C81-C79
\\sim C74-C73 \\sim C75-C73 ~
 C91-C90 \\sim C92-C90 \\sim C86-C84 \\sim C85-C84 \\sim C89-C87 \\sim C88-C87
\\sim C63-C62 \\sim C64-C62
 \\sim C66-C65 \\sim C67-C65 \\sim C70-C68 \\sim C69-C68
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.001 and sigma
for terminal atoms of 0.002
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.a Ternary CH refined with riding coordinates:
 C62(H62), C65(H65), C68(H68), C73(H73), C76(H76), C79(H79), C84(H84),
 C87(H87), C90(H90), C1(H1), C4(H4), C7(H7), C12(H12), C15(H15), C18(H18),
 C23(H23), C26(H26), C29(H29)
6.b Secondary CH2 refined with riding coordinates:
 C71(H71A,H71B), C72(H72A,H72B), C82(H82A,H82B), C83(H83A,H83B), C93(H93A,
 H93B), C94(H94A,H94B), C96(H96A,H96B), C97(H97A,H97B), C10(H10A,H10B),
 C11(H11A,H11B), C21(H21A,H21B), C22(H22A,H22B), C32(H32A,H32B), C33(H33A,H33B),
  C35(H35A,H35B), C36(H36A,H36B)
6.c Me refined with riding coordinates:
 C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C66(H66A,H66B,H66C), C67(H67A,H67B,
 H67C), C69(H69A,H69B,H69C), C70(H70A,H70B,H70C), C74(H74A,H74B,H74C), C75(H75A,
 H75B,H75C), C77(H77A,H77B,H77C), C78(H78A,H78B,H78C), C80(H80A,H80B,H80C),
 C81(H81A,H81B,H81C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C88(H88A,H88B,
 H88C), C89(H89A,H89B,H89C), C91(H91A,H91B,H91C), C92(H92A,H92B,H92C), C95(H95A,
 H95B,H95C), C98(H98A,H98B,H98C), 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),
 C14(H14A,H14B,H14C), C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C19(H19A,H19B,
 H19C), C20(H20A,H20B,H20C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,H30C), C31(H31A,H31B,H31C),
 C34(H34A,H34B,H34C), C37(H37A,H37B,H37C)
6.d Aromatic/amide H refined with riding coordinates:
 C39(H39), C40(H40), C41(H41), C42(H42), C43(H43), C45(H45), C46(H46),
 C47(H47), C48(H48), C49(H49), C51(H51), C52(H52), C53(H53), C54(H54), C55(H55),
  C57(H57), C58(H58), C59(H59), C60(H60), C61(H61), C118(H118), C119(H119),
 C120(H120), C121(H121), C122(H122), C100(H100), C101(H101), C102(H102),
 C103(H103), C104(H104), C106(H106), C107(H107), C108(H108), C109(H109),
 C110(H110), C112(H112), C113(H113), C114(H114), C115(H115), C116(H116),
 C133(H133), C132(H132), C131(H131), C130(H130), C129(H129), C134(H134),
 C126(H126), C125(H125), C124(H124), C123(H123), C128(H128), C127(H127)
6.e Fitted hexagon refined as free rotating group:
 C126(C125,C124,C123,C128,C127)
;
_shelx_res_checksum              75281
_shelx_hkl_checksum              65788
_olex2_exptl_crystal_mounting_method 'in fomblin on micromount'
_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 1.582
_oxdiff_exptl_absorpt_empirical_full_min 0.708