Tuning symmetry and magnetic blocking of an exchange-coupled lanthanide ion in isomeric, tetrametallic complexes: [LnCl<sub>6</sub>(TiCp<sub>2</sub>)<sub>3</sub>].
Jiang, Ningxin; Nakritskaia, Daria D.; Xie, Jiaze; Ramanathan, Arun; Varganov, Sergey A.; La Pierre, Henry S.; Chemical science 14 (2023) 4302–4307; doi:10.1039/d2sc06263a

data_1568693
_publ_section_title
;
 Tuning symmetry and magnetic blocking of an exchange-coupled lanthanide
 ion in isomeric, tetrametallic complexes:
 [LnCl<sub>6</sub>(TiCp<sub>2</sub>)<sub>3</sub>].
;
_journal_issue                   16
_journal_name_full               'Chemical science'
_journal_page_first              4302
_journal_page_last               4307
_journal_paper_doi               10.1039/d2sc06263a
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C20 H20 Cl6 Gd Ti2, C10 H10 Ti'
_chemical_formula_sum            'C30 H30 Cl6 Gd Ti3'
_chemical_formula_weight         904.19
_chemical_name_systematic        C30H30Cl6GdTi3
_chemical_properties_physical    Air-sensitive
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-06-10 deposited with the CCDC.	2023-03-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 114.4540(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.7944(3)
_cell_length_b                   21.4986(5)
_cell_length_c                   12.9783(3)
_cell_measurement_reflns_used    9741
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      30.504
_cell_measurement_theta_min      2.562
_cell_volume                     3249.60(13)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0367
_diffrn_reflns_av_unetI/netI     0.0236
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            39063
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.484
_diffrn_reflns_theta_min         1.967
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.239
_exptl_absorpt_correction_T_max  0.6333
_exptl_absorpt_correction_T_min  0.4797
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0883 before and 0.0720 after correction.
The Ratio of minimum to maximum transmission is 0.7575.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.848
_exptl_crystal_description       prism
_exptl_crystal_F_000             1768
_exptl_crystal_preparation       'N.A.,Magnetic properties'
_exptl_crystal_recrystallization_method N.A.
_exptl_crystal_size_max          0.302
_exptl_crystal_size_mid          0.264
_exptl_crystal_size_min          0.214
_refine_diff_density_max         0.552
_refine_diff_density_min         -0.814
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.117
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     377
_refine_ls_number_reflns         7401
_refine_ls_number_restraints     16
_refine_ls_restrained_S_all      1.120
_refine_ls_R_factor_all          0.0234
_refine_ls_R_factor_gt           0.0232
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0245P)^2^+4.1347P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0584
_refine_ls_wR_factor_ref         0.0586
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7305
_reflns_number_total             7401
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06263a2.cif
_cod_data_source_block           mo_a903_0m
_cod_depositor_comments
'Adding full bibliography for 1568691--1568696.cif.'
_cod_database_code               1568693
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.544
_shelx_estimated_absorpt_t_min   0.441
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C20B) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C16A) = Uanis(C16B)
Uanis(C20A) = Uanis(C20B)
Uanis(C19A) = Uanis(C19B)
Uanis(C17A) = Uanis(C17B)
Uanis(C18A) = Uanis(C18B)
3. Same fragment restrains
{C16B, C17B, C18B, C19B, C20B} sigma for 1-2: 0.002, 1-3: 0.004
as in
{C16A, C17A, C18A, C19A, C20A}
4. Others
 Sof(C16B)=Sof(H16B)=Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(H18B)=Sof(C19B)=
 Sof(H19B)=Sof(C20B)=Sof(H20B)=1-FVAR(1)
 Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=Sof(C19A)=
 Sof(H19A)=Sof(C20A)=Sof(H20A)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9),
 C10(H10), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C27(H27),
  C28(H28), C29(H29), C30(H30), C11(H11), C12(H12), C13(H13), C14(H14),
 C15(H15), C16A(H16A), C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A),
 C16B(H16B), C17B(H17B), C18B(H18B), C19B(H19B), C20B(H20B)
;
_shelx_res_checksum              57540
_shelx_hkl_checksum              47434
_olex2_submission_special_instructions 'No special instructions were received'