Synthesis and Magnetism of Neutral, Linear Metallocene Complexes of Terbium(II) and Dysprosium(II).
Gould, Colin A.; McClain, K. Randall; Yu, Jason M.; Groshens, Thomas J.; Furche, Filipp; Harvey, Benjamin G.; Long, Jeffrey R.; Journal of the American Chemical Society 141 (2019) 12967–12973; doi:10.1021/jacs.9b05816

data_4127838
_publ_section_title
;
 Synthesis and Magnetism of Neutral, Linear Metallocene Complexes of
 Terbium(II) and Dysprosium(II).
;
_journal_issue                   33
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12967
_journal_page_last               12973
_journal_paper_doi               10.1021/jacs.9b05816
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C40 H70 Tb, B C24 F20'
_chemical_formula_sum            'C64 H70 B F20 Tb'
_chemical_formula_weight         1388.93
_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             2019-07-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.9430(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.2155(6)
_cell_length_b                   23.1873(9)
_cell_length_c                   16.8829(7)
_cell_measurement_reflns_used    9371
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.39
_cell_measurement_theta_min      2.41
_cell_volume                     5955.6(4)
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(1)
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0319
_diffrn_reflns_av_unetI/netI     0.0204
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            69665
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.688
_diffrn_reflns_theta_min         1.492
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.291
_exptl_absorpt_correction_T_max  0.7453
_exptl_absorpt_correction_T_min  0.6677
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0630 before and 0.0439 after correction.
The Ratio of minimum to maximum transmission is 0.8959.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.549
_exptl_crystal_description       block
_exptl_crystal_F_000             2816
_exptl_crystal_size_max          0.504
_exptl_crystal_size_mid          0.364
_exptl_crystal_size_min          0.316
_refine_diff_density_max         1.420
_refine_diff_density_min         -0.625
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1103
_refine_ls_number_reflns         11317
_refine_ls_number_restraints     1554
_refine_ls_restrained_S_all      1.168
_refine_ls_R_factor_all          0.0716
_refine_ls_R_factor_gt           0.0563
_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^)+(0.0816P)^2^+8.5417P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1506
_refine_ls_wR_factor_ref         0.1632
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8815
_reflns_number_total             11317
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b05816_si_002.cif
_cod_data_source_block           tg_rm_6_48_1_0m
_cod_database_code               4127838
_shelx_shelxl_version_number     2016/6
_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
 C26A-C21 \\sim C26-C21 \\sim C29-C22 \\sim C29A-C22 \\sim C32A-C23 \\sim
C35A-C24 \\sim C35-C24 \\sim C38-
 C25 \\sim C38A-C25 \\sim C18-C4 \\sim C18A-C4 \\sim C6A-C5 \\sim C6-C5 \\sim
C9-C1 \\sim C9A-C1 \\sim C12-C2 ~
 C12A-C2 \\sim C15A-C3 \\sim C32-C23 \\sim C15-C3
 with sigma of 0.02
 C18A-C20A \\sim C20-C18 \\sim C18A-C19A \\sim C18-C19 \\sim C15-C17 \\sim
C15A-C17A \\sim C15A-C16 ~
 C15-C16A \\sim C12A-C14A \\sim C13A-C12A \\sim C12-C14 \\sim C13-C12 \\sim
C11A-C9A \\sim C11-C9 ~
 C10A-C9A \\sim C10-C9 \\sim C7-C6 \\sim C7A-C6A \\sim C8A-C6A \\sim C8-C6
\\sim C33A-C32A \\sim C32-C33 ~
 C32-C34 \\sim C34A-C32A \\sim C35A-C37 \\sim C36-C35A \\sim C35-C37A \\sim
C35-C36A \\sim C39-C38 ~
 C38A-C40A \\sim C40-C38 \\sim C38A-C39A \\sim C27A-C26A \\sim C26-C27 \\sim
C26-C28 \\sim C28A-C26A ~
 C30A-C29A \\sim C31A-C29A \\sim C30-C29 \\sim C31-C29
 with sigma of 0.02
 C25-C35A \\sim C35A-C23 \\sim C23-C35 \\sim C35-C25
 with sigma of 0.02
 C21-C29A \\sim C29A-C23 \\sim C21-C29 \\sim C29-C23
 with sigma of 0.02
 C24-C32A \\sim C32A-C22 \\sim C24-C32 \\sim C32-C22
 with sigma of 0.02
 C25-C26 \\sim C26-C22 \\sim C25-C26A \\sim C26A-C22
 with sigma of 0.02
 C21-C38A \\sim C38A-C24 \\sim C21-C38 \\sim C38-C24
 with sigma of 0.02
 C36A-C24 \\sim C24-C37A
 with sigma of 0.02
 C1-C12A \\sim C12A-C3 \\sim C1-C12 \\sim C12-C3
 with sigma of 0.02
 C2-C15A \\sim C15A-C4 \\sim C2-C15 \\sim C15-C4
 with sigma of 0.02
 C3-C18A \\sim C18A-C5 \\sim C3-C18 \\sim C18-C5
 with sigma of 0.02
 C4-C6A \\sim C6A-C1 \\sim C4-C6 \\sim C6-C1
 with sigma of 0.02
 C5-C9 \\sim C9-C2 \\sim C5-C9A \\sim C9A-C2
 with sigma of 0.02
 C31-C22 \\sim C22-C30
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C39) = Uanis(C40A)
Uanis(C16A) = Uanis(C15)
4. Rigid body (RIGU) restrains
 C31, C29, C30, C30A, C29A, C31A, C22, C21, C25, C24, C23, C34, C34A, C32A,
 C32, C33A, C33, C36, C36A, C35, C35A, C37, C37A, C40, C40A, C38A, C38, C39A,
 C39, C27, C26A, C28A, C26, C27A
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
 C14, C12, C12A, C14A, C13A, C13, C2, C1, C5, C3, C4, C17, C17A, C15A, C16,
 C15, C18A, C20A, C19, C19A, C20, C18, C7A, C7, C6A, C6, C8A, C8, C10, C9A, C9,
 C11A, C11, C10A
 with sigma for 1-2 distances of 0.0005 and sigma for 1-3 distances of 0.0005
5. Others
 Sof(C29)=Sof(H29)=Sof(C31)=Sof(H31D)=Sof(H31E)=Sof(H31F)=Sof(C30)=Sof(H30D)=
 Sof(H30E)=Sof(H30F)=1-FVAR(1)
 Sof(C29A)=Sof(H29A)=Sof(C31A)=Sof(H31A)=Sof(H31B)=Sof(H31C)=Sof(C30A)=
 Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
 Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C28)=Sof(H28D)=
 Sof(H28E)=Sof(H28F)=1-FVAR(2)
 Sof(C26A)=Sof(H26A)=Sof(C28A)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C27A)=
 Sof(H27A)=Sof(H27B)=Sof(H27C)=FVAR(2)
 Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C38A)=Sof(H38A)=Sof(C40A)=
 Sof(H40D)=Sof(H40E)=Sof(H40F)=1-FVAR(3)
 Sof(C38)=Sof(H38)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C39)=Sof(H39A)=
 Sof(H39B)=Sof(H39C)=FVAR(3)
 Sof(C34)=Sof(H34D)=Sof(H34E)=Sof(H34F)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33D)=
 Sof(H33E)=Sof(H33F)=1-FVAR(4)
 Sof(C32A)=Sof(H32A)=Sof(C34A)=Sof(H34A)=Sof(H34B)=Sof(H34C)=Sof(C33A)=
 Sof(H33A)=Sof(H33B)=Sof(H33C)=FVAR(4)
 Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=Sof(C35)=Sof(H35)=Sof(C36A)=Sof(H36D)=
 Sof(H36E)=Sof(H36F)=1-FVAR(5)
 Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C35A)=Sof(H35A)=Sof(C36)=Sof(H36A)=
 Sof(H36B)=Sof(H36C)=FVAR(5)
 Sof(C15A)=Sof(H15A)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C16)=
 Sof(H16D)=Sof(H16E)=Sof(H16F)=1-FVAR(6)
 Sof(C16A)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=
 Sof(H17C)=Sof(C15)=Sof(H15)=FVAR(6)
 Sof(C10A)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C9A)=Sof(H9A)=Sof(C11A)=Sof(H11D)=
 Sof(H11E)=Sof(H11F)=1-FVAR(7)
 Sof(C9)=Sof(H9)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(H11C)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=Sof(H10C)=FVAR(7)
 Sof(C12A)=Sof(H12A)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14A)=
 Sof(H14A)=Sof(H14B)=Sof(H14C)=1-FVAR(8)
 Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14)=Sof(H14D)=
 Sof(H14E)=Sof(H14F)=FVAR(8)
 Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C20A)=
 Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(9)
 Sof(C18)=Sof(H18)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C19)=Sof(H19A)=
 Sof(H19B)=Sof(H19C)=FVAR(9)
 Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C6)=Sof(H6)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(H7C)=1-FVAR(10)
 Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=
 Sof(H8AB)=Sof(H8AC)=FVAR(10)
 Fixed Sof: Tb3(0.33) Tb2(0.36) Tb4(0.21) Tb1(0.1)
6.a Ternary CH refined with riding coordinates:
 C32A(H32A), C29A(H29A), C38(H38), C26A(H26A), C6A(H6A), C35A(H35A), C9(H9),
 C15(H15), C26(H26), C29(H29), C35(H35), C32(H32), C38A(H38A), C15A(H15A),
 C9A(H9A), C12(H12), C12A(H12A), C18(H18), C18A(H18A), C6(H6)
6.b Me refined with riding coordinates:
 C16A(H16A,H16B,H16C), C27(H27D,H27E,H27F), C28(H28D,H28E,H28F), C31(H31D,H31E,
 H31F), C30(H30D,H30E,H30F), C16(H16D,H16E,H16F), C36A(H36D,H36E,H36F)
6.c Idealised Me refined as rotating group:
 C34A(H34A,H34B,H34C), C31A(H31A,H31B,H31C), C30A(H30A,H30B,H30C), C33A(H33A,
 H33B,H33C), C37(H37A,H37B,H37C), C11(H11A,H11B,H11C), C40(H40A,H40B,H40C),
 C17(H17A,H17B,H17C), C28A(H28A,H28B,H28C), C27A(H27A,H27B,H27C), C7A(H7AA,H7AB,
 H7AC), C36(H36A,H36B,H36C), C8A(H8AA,H8AB,H8AC), C10(H10A,H10B,H10C), C39(H39A,
 H39B,H39C), C34(H34D,H34E,H34F), C37A(H37D,H37E,H37F), C39A(H39D,H39E,H39F),
 C33(H33D,H33E,H33F), C40A(H40D,H40E,H40F), C10A(H10D,H10E,H10F), C17A(H17D,
 H17E,H17F), C11A(H11D,H11E,H11F), C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F),
 C14A(H14A,H14B,H14C), C14(H14D,H14E,H14F), C20(H20A,H20B,H20C), C19(H19A,H19B,
 H19C), C19A(H19D,H19E,H19F), C20A(H20D,H20E,H20F), C8(H8A,H8B,H8C), C7(H7A,H7B,
 H7C)
;
_shelx_res_checksum              15657
_shelx_hkl_checksum              99121
_olex2_submission_special_instructions 'No special instructions were received'