Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium Complex.
Rice, Natalie T.; Popov, Ivan A.; Russo, Dominic R.; Bacsa, John; Batista, Enrique R.; Yang, Ping; Telser, Joshua; La Pierre, Henry S.; Journal of the American Chemical Society 141 (2019) 13222–13233; doi:10.1021/jacs.9b06622

data_4127828
_publ_section_title
;
 Design, Isolation, and Spectroscopic Analysis of a Tetravalent Terbium
 Complex.
;
_journal_issue                   33
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13222
_journal_page_last               13233
_journal_paper_doi               10.1021/jacs.9b06622
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C60 H138 K N16 O P4 Tb, C4 H10 O'
_chemical_formula_sum            'C64 H148 K N16 O2 P4 Tb'
_chemical_formula_weight         1495.88
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-05-09
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_cell_angle_alpha                90
_cell_angle_beta                 114.727(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.587(3)
_cell_length_b                   15.454(2)
_cell_length_c                   25.702(4)
_cell_measurement_reflns_used    9438
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.595
_cell_measurement_theta_min      2.72
_cell_volume                     8149(2)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2016)'
_computing_data_collection       'APEX2 v2016.5-1 (Bruker, 2014)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2016)'
_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_temperature      100(2)
_diffrn_detector_area_resol_mean 7.495
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker D8 Venture'
_diffrn_measurement_method       '\f and \w scans with a narrow frame width'
_diffrn_radiation_monochromator  'multilayer mirror'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0539
_diffrn_reflns_av_unetI/netI     0.0406
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            131605
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.670
_diffrn_reflns_theta_min         2.234
_diffrn_source                   'microfocus sealed tube'
_diffrn_source_current           1
_diffrn_source_voltage           50
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.045
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5580
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1199 before and 0.0900 after correction. The Ratio of minimum to maximum transmission is 0.7479. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.219
_exptl_crystal_description       plate
_exptl_crystal_F_000             3216
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.383
_exptl_crystal_size_mid          0.374
_exptl_crystal_size_min          0.276
_refine_diff_density_max         4.297
_refine_diff_density_min         -3.646
_refine_diff_density_rms         0.187
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.219
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     855
_refine_ls_number_reflns         24826
_refine_ls_number_restraints     152
_refine_ls_restrained_S_all      1.217
_refine_ls_R_factor_all          0.1015
_refine_ls_R_factor_gt           0.0846
_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^)+107.8614P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1845
_refine_ls_wR_factor_ref         0.1944
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21189
_reflns_number_total             24826
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b06622_si_004.cif
_cod_data_source_block           ntr-03-018_l
_cod_database_code               4127828
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O1S_1-C2S_1 \\sim O1S_1-C4S_1
 with sigma of 0.002
 K1-O1S_1 \\sim K1-O1S_2
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(O1S_1) \\sim Ueq, Uanis(C3S_2) \\sim Ueq: with sigma of 0.002 and sigma
for terminal atoms of 0.004
Uanis(O1S_3) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of
0.004
Uanis(C5S_4) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of
0.004
Uanis(C2S_1) = Uanis(C2S_2)
Uanis(C3S_1) = Uanis(C3S_2)
Uanis(C5S_2) = Uanis(C4S_1)
Uanis(C5S_1) = Uanis(C4S_2)
Uanis(O1S_2) = Uanis(O1S_1)
Uanis(O1S_4) = Uanis(O1S_3)
Uanis(C2S_4) = Uanis(C2S_3)
Uanis(C4S_4) = Uanis(C4S_3)
Uanis(C3S_4) = Uanis(C3S_3)
Uanis(C5S_4) = Uanis(C5S_3)
4. Rigid body (RIGU) restrains
 O1S_3, C2S_3, C3S_3, C4S_3
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0002
 O1S_1, C2S_1, C3S_1, C4S_1, C5S_1
 O1S_2, C2S_2, C3S_2, C4S_2, C5S_2
 O1S_3, C2S_3, C3S_3, C4S_3, C5S_3
 O1S_4, C2S_4, C3S_4, C4S_4, C5S_4
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Same fragment restrains
{O1S_2, C2S_2, C3S_2, C4S_2, C5S_2}
{O1S_3, C2S_3, C3S_3, C4S_3, C5S_3}
{O1S_4, C2S_4, C3S_4, C4S_4, C5S_4}
as
{O1S_1, C2S_1, C3S_1, C4S_1, C5S_1} sigma for 1-2: 0.001 1-3: 0.001
6. Others
 Sof(O1S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(H3SC)=
 Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(C5S)=Sof(H5SA)=Sof(H5SB)=Sof(H5SC)=1-FVAR(1)
 Sof(O1S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(H3SC)=
 Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(C5S)=Sof(H5SA)=Sof(H5SB)=Sof(H5SC)=FVAR(1)
 Sof(O1S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(H3SC)=
 Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(C5S)=Sof(H5SA)=Sof(H5SB)=Sof(H5SC)=1-FVAR(2)
 Sof(O1S)=Sof(C2S)=Sof(H2SA)=Sof(H2SB)=Sof(C3S)=Sof(H3SA)=Sof(H3SB)=Sof(H3SC)=
 Sof(C4S)=Sof(H4SA)=Sof(H4SB)=Sof(C5S)=Sof(H5SA)=Sof(H5SB)=Sof(H5SC)=FVAR(2)
7.a Secondary CH2 refined with riding coordinates:
 C2S(H2SA,H2SB), C4S(H4SA,H4SB), C2S(H2SA,H2SB), C4S(H4SA,H4SB), C2S(H2SA,
 H2SB), C4S(H4SA,H4SB), C2S(H2SA,H2SB), C4S(H4SA,H4SB), C1(H1A,H1B), C2(H2A,
 H2B), C12(H12A,H12B), C13(H13A,H13B), C1(H1A,H1B), C2(H2A,H2B), C12(H12A,H12B),
  C13(H13A,H13B), C1(H1A,H1B), C2(H2A,H2B), C12(H12A,H12B), C13(H13A,H13B),
 C1(H1A,H1B), C2(H2A,H2B), C12(H12A,H12B), C13(H13A,H13B)
7.b Idealised Me refined with riding coordinates:
 C3S(H3SA,H3SB,H3SC), C5S(H5SA,H5SB,H5SC), C3S(H3SA,H3SB,H3SC), C5S(H5SA,H5SB,
 H5SC), C3S(H3SA,H3SB,H3SC), C5S(H5SA,H5SB,H5SC), C3S(H3SA,H3SB,H3SC), C5S(H5SA,
 H5SB,H5SC), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C)
7.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C),
 C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C),
 C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C11(H11A,H11B,H11C), C14(H14A,H14B,H14C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C),
 C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C),
 C11(H11A,H11B,H11C), C14(H14A,H14B,H14C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              7420
_shelx_hkl_checksum              31407
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'