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_1568691
_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         'Cl6 Gd1, 3(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      hexagonal
_space_group_IT_number           176
_space_group_name_Hall           '-P 6c'
_space_group_name_H-M_alt        'P 63/m'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-23
_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                 90
_cell_angle_gamma                120
_cell_formula_units_Z            2
_cell_length_a                   12.8073(11)
_cell_length_b                   12.8073(11)
_cell_length_c                   11.5663(14)
_cell_measurement_reflns_used    9974
_cell_measurement_temperature    300.0
_cell_measurement_theta_max      28.227
_cell_measurement_theta_min      2.544
_cell_volume                     1643.0(3)
_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 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      300.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.997
_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  0.0530
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11333
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         28.267
_diffrn_reflns_theta_min         2.544
_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    3.203
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.4145
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1472 before and 0.0874 after correction.
The Ratio of minimum to maximum transmission is 0.5559.
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    1.828
_exptl_crystal_description       needle
_exptl_crystal_F_000             884
_exptl_crystal_preparation       'N.A.,Magnetic properties'
_exptl_crystal_recrystallization_method N.A.
_exptl_crystal_size_max          0.364
_exptl_crystal_size_mid          0.125
_exptl_crystal_size_min          0.028
_refine_diff_density_max         0.809
_refine_diff_density_min         -1.051
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.140
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     84
_refine_ls_number_reflns         1421
_refine_ls_number_restraints     42
_refine_ls_restrained_S_all      1.184
_refine_ls_R_factor_all          0.0425
_refine_ls_R_factor_gt           0.0356
_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^)+(0.0292P)^2^+4.6429P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0827
_refine_ls_wR_factor_ref         0.0889
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1287
_reflns_number_total             1421
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc06263a2.cif
_cod_data_source_block           mo_a951_0m
_cod_depositor_comments
'Adding full bibliography for 1568691--1568696.cif.'
_cod_database_code               1568691
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.916
_shelx_estimated_absorpt_t_min   0.389
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(C1A) \\sim Ueq, Uanis(C2A) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C4A)
\\sim Ueq, Uanis(C5A) \\sim Ueq, Uanis(C6A) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
Uanis(C1A) = Uanis(C1B)
Uanis(C2A) = Uanis(C2B)
Uanis(C3A) = Uanis(C3B)
Uanis(C4A) = Uanis(C4B)
Uanis(C5A) = Uanis(C5B)
Uanis(C6A) = Uanis(C6B)
2. Same fragment restrains
{C1B, C2B, C3B} sigma for 1-2: 0.005, 1-3: 0.01
as in
{C1A, C2A, C3A}
{C4B, C5B, C6B} sigma for 1-2: 0.005, 1-3: 0.01
as in
{C4A, C5A, C6A}
3. Others
 Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=1-FVAR(1)
 Sof(C1B)=Sof(H1B)=0.5*(1-FVAR(2))
 Sof(C1A)=Sof(H1A)=0.5*FVAR(2)
 Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=FVAR(1)
 Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=1-FVAR(2)
 Sof(C6B)=Sof(H6B)=0.5*(1-FVAR(3))
 Sof(C6A)=Sof(H6A)=0.5*FVAR(3)
 Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=FVAR(2)
4.a Ternary CH refined with riding coordinates:
 C1A(H1A), C2A(H2A), C5A(H5A), C6A(H6A), C3B(H3B), C5B(H5B), C6B(H6B)
4.b Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C1B(H1B), C2B(H2B), C4B(H4B)
;
_shelx_res_checksum              42632
_shelx_hkl_checksum              40829
_olex2_exptl_crystal_mounting_method N.A.
_olex2_submission_original_sample_id C30H30Cl6GdTI3
_olex2_submission_special_instructions 'No special instructions were received'