Terbocenium: completing a heavy lanthanide metallocenium cation family with an alternative anion abstraction strategy.
Goodwin, Conrad A. P.; Reta, Daniel; Ortu, Fabrizio; Liu, Jingjing; Chilton, Nicholas F.; Mills, David P.; Chemical communications (Cambridge, England) 54 (2018) 9182–9185; doi:10.1039/c8cc05261a

data_7122028
_publ_section_title
;
 Terbocenium: completing a heavy lanthanide metallocenium cation family
 with an alternative anion abstraction strategy.
;
_journal_issue                   66
_journal_name_full
'Chemical communications (Cambridge, England)'
_journal_page_first              9182
_journal_page_last               9185
_journal_paper_doi               10.1039/c8cc05261a
_journal_volume                  54
_journal_year                    2018
_chemical_formula_moiety         '1(C34 H62 B1 Tb1)'
_chemical_formula_sum            'C34 H62 B Tb'
_chemical_formula_weight         640.56
_chemical_name_systematic        '[Tb(Cpttt)29BH4)]'
_chemical_properties_physical
Air-sensitive,Moisture-sensitive,Oxygen-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-05-19
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_audit_update_record
;
2018-05-21 deposited with the CCDC.
2018-07-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 99.173(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.3320(2)
_cell_length_b                   15.6294(3)
_cell_length_c                   20.5234(4)
_cell_measurement_reflns_used    11602
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      30.0820
_cell_measurement_theta_min      2.4510
_cell_volume                     3271.80(11)
_computing_cell_refinement       'CrysAlisPro 1.171.39.30c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.30c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.30c (Rigaku OD, 2017)'
_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      149.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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    -55.00 -28.00   0.50    2.00    --   -7.70 -33.00  52.00   54
  2  \w     -3.00  23.00   0.50    2.00    --   -7.70  33.00-148.00   52
  3  \w     38.00  65.00   0.50    2.00    --   -7.70  38.00  90.00   54
  4  \w    -97.00 -50.00   0.50    2.00    --   -7.70 -38.00-120.00   94
  5  \w    -42.00  32.00   0.50    2.00    --   -7.70 -38.00-120.00  148
  6  \w    -47.00  29.00   0.50    2.00    --   -7.70  38.00  90.00  152
;
_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      0.0600611000
_diffrn_orient_matrix_UB_12      0.0126407000
_diffrn_orient_matrix_UB_13      0.0193441000
_diffrn_orient_matrix_UB_21      0.0344672000
_diffrn_orient_matrix_UB_22      -0.0141535000
_diffrn_orient_matrix_UB_23      -0.0252503000
_diffrn_orient_matrix_UB_31      -0.0065299000
_diffrn_orient_matrix_UB_32      0.0412241000
_diffrn_orient_matrix_UB_33      -0.0145976000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0277
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            24081
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.348
_diffrn_reflns_theta_min         2.384
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    2.181
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.541
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.30c (Rigaku Oxford Diffraction, 2017)
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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.300
_exptl_crystal_description       block
_exptl_crystal_F_000             1344
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: toluene'
_exptl_crystal_size_max          0.363
_exptl_crystal_size_mid          0.181
_exptl_crystal_size_min          0.142
_refine_diff_density_max         2.036
_refine_diff_density_min         -1.536
_refine_diff_density_rms         0.146
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     662
_refine_ls_number_reflns         5942
_refine_ls_number_restraints     1880
_refine_ls_restrained_S_all      0.949
_refine_ls_R_factor_all          0.0404
_refine_ls_R_factor_gt           0.0357
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0724P)^2^+2.8169P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0989
_refine_ls_wR_factor_ref         0.1022
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5231
_reflns_number_total             5942
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8cc05261a2.cif
_cod_data_source_block           2-Tb
_cod_depositor_comments
'Adding full bibliography for 7122025--7122029.cif.'
_cod_original_cell_volume        3271.78(12)
_cod_database_code               7122028
_manchester_internal_coll_name   rdpm82
_manchester_internal_coll_client CAPG/FO
_manchester_internal_coll_type   custom
_manchester_internal_coll_frame_time 2s
_manchester_internal_coll_frame_width 0.5
_manchester_internal_coll_frame_method '\w scans'
_manchester_internal_coll_user   CAPG/FO
_manchester_internal_coll_date   20/11/17
_manchester_internal_process_user CAPG
_manchester_internal_process_date 20/11/17
_manchester_internal_solution_user CAPG
_manchester_internal_solution_date 20/11/17
_manchester_internal_refinement_user CAPG/FO
_manchester_internal_refinement_date 20/11/17
_manchester_internal_validation_user FO
_manchester_internal_validation_date 19/5/18
_manchester_internal_archive_date 19/5/18
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C11 H10 N O'
_chemical_oxdiff_usercomment     CAPG/FO
_reflns_odcompleteness_completeness 98.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All B(H,H,H,H,H,H,H,H) groups, All C(H,H,H) groups
2. Restrained distances
 B1A-H1AA = B1A-H1AB = B1A-H1AC = B1A-H1AD
 1.1 with sigma of 0.02
 B1B-H1BB = B1B-H1BD = B1B-H1BA = B1B-H1BC
 1.1 with sigma of 0.02
 Tb1B-H1BD
 1.66 with sigma of 0.02
 Tb1A-H1AA \\sim Tb1A-H1AB
 with sigma of 0.02
 H1BA-H1BB \\sim H1BA-H1BC \\sim H1BA-H1BD \\sim H1BB-H1BC \\sim H1BB-H1BD
\\sim H1BC-H1BD
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(Tb1B) = Uanis(Tb1A)
Uanis(B1B) = Uanis(B1A)
4. 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
5. Same fragment restrains
{Tb1A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A, C12A, C13A,
C14A, C15A, C16A, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C24A, C25A, C26A,
C27A, C28A, C29A, C30A, C31A, C32A, C33A, C34A, B1A} sigma for 1-2: 0.02, 1-3:
0.04
as
{Tb1B, C0AA, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B, C12B, C13B,
C14B, C15B, C16B, C17B, C18B, C19B, C20B, C21B, C22B, C23B, C24B, C25B, C26B,
C27B, C28B, C29B, C30B, C31B, C32B, C33B, C34B, B1B}
6. Others
 Sof(Tb1B)=Sof(C0AA)=Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(C4B)=Sof(C5B)=Sof(H5B)=
 Sof(C6B)=Sof(C7B)=Sof(H7BC)=Sof(H7BA)=Sof(H7BB)=Sof(C8B)=Sof(H8BB)=Sof(H8BC)=
 Sof(H8BA)=Sof(C9B)=Sof(H9BB)=Sof(H9BA)=Sof(H9BC)=Sof(C10B)=Sof(C11B)=Sof(H11D)=
 Sof(H11F)=Sof(H11E)=Sof(C12B)=Sof(H12D)=Sof(H12E)=Sof(H12F)=Sof(C13B)=
 Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14B)=Sof(C15B)=Sof(H15D)=Sof(H15E)=
 Sof(H15F)=Sof(C16B)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17B)=Sof(H17D)=
 Sof(H17E)=Sof(H17F)=Sof(C18B)=Sof(C19B)=Sof(H19B)=Sof(C20B)=Sof(C21B)=
 Sof(C22B)=Sof(H22B)=Sof(C23B)=Sof(C24B)=Sof(H24E)=Sof(H24D)=Sof(H24F)=
 Sof(C25B)=Sof(H25E)=Sof(H25F)=Sof(H25D)=Sof(C26B)=Sof(H26E)=Sof(H26F)=
 Sof(H26D)=Sof(C27B)=Sof(C28B)=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29B)=
 Sof(H29D)=Sof(H29E)=Sof(H29F)=Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=
 Sof(C31B)=Sof(C32B)=Sof(H32F)=Sof(H32D)=Sof(H32E)=Sof(C33B)=Sof(H33D)=
 Sof(H33E)=Sof(H33F)=Sof(C34B)=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(B1B)=Sof(H1BD)=
 Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=1-FVAR(1)
 Sof(Tb1A)=Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(C4A)=Sof(C5A)=Sof(H5A)=
 Sof(C6A)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AC)=Sof(H8AA)=
 Sof(H8AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H9AC)=Sof(C10A)=Sof(C11A)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=Sof(C12A)=Sof(H12A)=Sof(H12B)=Sof(H12C)=Sof(C13A)=
 Sof(H13B)=Sof(H13A)=Sof(H13C)=Sof(C14A)=Sof(C15A)=Sof(H15C)=Sof(H15A)=
 Sof(H15B)=Sof(C16A)=Sof(H16B)=Sof(H16A)=Sof(H16C)=Sof(C17A)=Sof(H17C)=
 Sof(H17A)=Sof(H17B)=Sof(C18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(C21A)=
 Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(C24A)=Sof(H24A)=Sof(H24B)=Sof(H24C)=
 Sof(C25A)=Sof(H25B)=Sof(H25A)=Sof(H25C)=Sof(C26A)=Sof(H26A)=Sof(H26B)=
 Sof(H26C)=Sof(C27A)=Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29A)=
 Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30A)=Sof(H30C)=Sof(H30A)=Sof(H30B)=
 Sof(C31A)=Sof(C32A)=Sof(H32C)=Sof(H32A)=Sof(H32B)=Sof(C33A)=Sof(H33A)=
 Sof(H33B)=Sof(H33C)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(B1A)=Sof(H1AA)=
 Sof(H1AB)=Sof(H1AC)=Sof(H1AD)=FVAR(1)
7.a Me refined with riding coordinates:
 C7A(H7AA,H7AB,H7AC), C8A(H8AC,H8AA,H8AB), C9A(H9AA,H9AB,H9AC), C11A(H11A,H11B,
 H11C), C12A(H12A,H12B,H12C), C13A(H13B,H13A,H13C), C15A(H15C,H15A,H15B),
 C16A(H16B,H16A,H16C), C17A(H17C,H17A,H17B), C24A(H24A,H24B,H24C), C25A(H25B,
 H25A,H25C), C26A(H26A,H26B,H26C), C28A(H28A,H28B,H28C), C29A(H29A,H29B,H29C),
 C30A(H30C,H30A,H30B), C32A(H32C,H32A,H32B), C33A(H33A,H33B,H33C), C34A(H34A,
 H34B,H34C), C7B(H7BC,H7BA,H7BB), C8B(H8BB,H8BC,H8BA), C9B(H9BB,H9BA,H9BC),
 C11B(H11D,H11F,H11E), C12B(H12D,H12E,H12F), C13B(H13D,H13E,H13F), C15B(H15D,
 H15E,H15F), C16B(H16D,H16E,H16F), C17B(H17D,H17E,H17F), C24B(H24E,H24D,H24F),
 C25B(H25E,H25F,H25D), C26B(H26E,H26F,H26D), C28B(H28D,H28E,H28F), C29B(H29D,
 H29E,H29F), C30B(H30D,H30E,H30F), C32B(H32F,H32D,H32E), C33B(H33D,H33E,H33F),
 C34B(H34D,H34E,H34F)
7.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C5A(H5A), C19A(H19A), C22A(H22A), C2B(H2B), C5B(H5B), C19B(H19B),
 C22B(H22B)
;
_shelx_res_checksum              664
_olex2_exptl_crystal_mounting_method 'From fomblin on a microscope slide.'
_olex2_submission_original_sample_id rdpm82
_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 1.413
_oxdiff_exptl_absorpt_empirical_full_min 0.636