Cyclooctatetraenide-based single-ion magnets featuring bulky cyclopentadienyl ligand
Korzyński, Maciej Damian; Bernhardt, Moritz; Romankov, Vladyslav; Dreiser, Jan; Matmon, Guy; Pointillart, Fabrice; Le Guennic, Boris; Cador, Olivier; Copéret, Christophe; Chemical Science  (2022) –; doi:10.1039/D2SC02560D

data_1567546
_publ_section_title
;
 Cyclooctatetraenide-based single-ion magnets featuring bulky
 cyclopentadienyl ligand
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC02560D
_journal_year                    2022
_chemical_formula_moiety
'2(C F3 Nd2 O3 S), 2(K), 4(C10 H15), 4(C8 H8), 4(C7 H8)'
_chemical_formula_sum            'C102 H124 F6 K2 Nd4 O6 S2'
_chemical_formula_weight         2279.28
_chemical_properties_physical    Air-sensitive,Moisture-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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2022-04-08
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-05-04 deposited with the CCDC.	2022-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 100.7174(13)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.4669(14)
_cell_length_b                   18.3458(12)
_cell_length_c                   25.0418(16)
_cell_measurement_reflns_used    9723
_cell_measurement_temperature    100.0
_cell_measurement_theta_max      28.48
_cell_measurement_theta_min      2.23
_cell_volume                     9690.1(11)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device       'fixed chi three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_xray_symbol    K-L~3~
_diffrn_reflns_av_R_equivalents  0.0570
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            178690
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.485
_diffrn_reflns_theta_min         1.149
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.300
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6146
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0753 before and 0.0525 after correction. The Ratio of minimum to maximum transmission is 0.8245. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'clear bluish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.562
_exptl_crystal_description       block
_exptl_crystal_F_000             4592
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.775
_refine_diff_density_min         -1.363
_refine_diff_density_rms         0.149
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.121
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1164
_refine_ls_number_reflns         22184
_refine_ls_number_restraints     238
_refine_ls_restrained_S_all      1.116
_refine_ls_R_factor_all          0.0718
_refine_ls_R_factor_gt           0.0413
_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^)+(0.0305P)^2^+48.4660P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0887
_refine_ls_wR_factor_ref         0.1046
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16012
_reflns_number_total             22184
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc02560d2.cif
_cod_data_source_block           cotndcpst_0m
_cod_database_code               1567546
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.803
_shelx_estimated_absorpt_t_min   0.803
_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
 C35-C34 = C35-C36 = C36-C37 = C37-C38 = C38-C9AA = C9AA-C32 = C8-C9 = C9-C10 =
  C11-C10 = C11-C12 = C12-C13 = C13-C6 = C6-C7 = C7-C8
 1.41 with sigma of 0.002
3. Rigid bond restraints
 C0BA, C8AA, C0AA, C7AA, C3BA, C1BA, C4BA, C2BA, C5CA, C6CA, C4CA, C2CA, C3CA,
 C8BA, C5BA, C6BA
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
Uanis(C0BA) \\sim Ueq, Uanis(C8AA) \\sim Ueq, Uanis(C0AA) \\sim Ueq,
Uanis(C7AA) \\sim Ueq, Uanis(C3BA) \\sim Ueq, Uanis(C1BA) \\sim Ueq,
Uanis(C4BA) \\sim Ueq, Uanis(C2BA) \\sim Ueq, Uanis(C5CA) \\sim Ueq,
Uanis(C6CA) \\sim Ueq, Uanis(C4CA) \\sim Ueq, Uanis(C2CA) \\sim Ueq,
Uanis(C3CA) \\sim Ueq, Uanis(C8BA) \\sim Ueq, Uanis(C5BA) \\sim Ueq,
Uanis(C6BA) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C5AA) = Uanis(C7BA) = Uanis(C2AA) = Uanis(C1AA) = Uanis(C3AA) =
Uanis(C4AA) = Uanis(C9BA) = Uanis(C0CA) = Uanis(C50) = Uanis(C1CA) = Uanis(C45)
= Uanis(C49) = Uanis(C47) = Uanis(C46) = Uanis(C48) = Uanis(C44)
5. Rigid body (RIGU) restrains
 C0BA, C8AA, C0AA, C7AA, C3BA, C1BA, C4BA, C2BA, C5CA, C6CA, C4CA, C2CA, C3CA,
 C8BA, C5BA, C6BA
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
6. Others
 Sof(C103)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C102)=Sof(C1J)=Sof(H1J)=Sof(C100)=
 Sof(H100)=Sof(C106)=Sof(H106)=Sof(C105)=Sof(H105)=Sof(C104)=Sof(H104)=1-FVAR(1)
 Sof(C6AA)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=Sof(C1B)=Sof(C1C)=Sof(H1C)=Sof(C1D)=
 Sof(H1D)=Sof(C1E)=Sof(H1E)=Sof(C1F)=Sof(H1F)=Sof(C101)=Sof(H101)=FVAR(1)
 Sof(C50)=Sof(H50)=Sof(C1CA)=Sof(H1CA)=Sof(C45)=Sof(H45)=Sof(C49)=Sof(H49)=
 Sof(C47)=Sof(H47)=Sof(C46)=Sof(H46)=Sof(C48)=Sof(H48)=Sof(C44)=Sof(H44)=1-
 FVAR(2)
 Sof(C5AA)=Sof(H5AD)=Sof(C7BA)=Sof(H7BA)=Sof(C2AA)=Sof(H2AD)=Sof(C1AA)=
 Sof(H1AD)=Sof(C3AA)=Sof(H3AD)=Sof(C4AA)=Sof(H4AD)=Sof(C9BA)=Sof(H9BA)=
 Sof(C0CA)=Sof(H0CA)=FVAR(2)
 Sof(C5CA)=Sof(H5CA)=Sof(C6CA)=Sof(H6CA)=Sof(C4CA)=Sof(H4CA)=Sof(C2CA)=
 Sof(H2CA)=Sof(C3CA)=Sof(H3CA)=Sof(C8BA)=Sof(H8BA)=Sof(C5BA)=Sof(H5BA)=
 Sof(C6BA)=Sof(H6BA)=1-FVAR(3)
 Sof(C0BA)=Sof(H0BA)=Sof(C8AA)=Sof(H8AA)=Sof(C0AA)=Sof(H0AA)=Sof(C7AA)=
 Sof(H7AA)=Sof(C3BA)=Sof(H3BA)=Sof(C1BA)=Sof(H1BA)=Sof(C4BA)=Sof(H4BA)=
 Sof(C2BA)=Sof(H2BA)=FVAR(3)
7.a Free rotating group:
 C103(C102,C1J,C100,C106,C105,C104), C6AA(C1B,C1C,C1D,C1E,C1F,C101)
7.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C10(H10), C8(H8), C6(H6), C13(H13), C127(H127), C124(H124),
 C126(H126), C125(H125), C109(H109), C110(H110), C120(H120), C119(H119),
 C118(H118), C117(H117), C112(H112), C111(H111), C113(H113), C116(H116),
 C123(H123), C9AA(H9AA), C37(H37), C35(H35), C36(H36), C32(H32), C33(H33),
 C1J(H1J), C100(H100), C106(H106), C105(H105), C104(H104), C1C(H1C), C1D(H1D),
 C1E(H1E), C1F(H1F), C101(H101), C5AA(H5AD), C7BA(H7BA), C2AA(H2AD), C1AA(H1AD),
  C3AA(H3AD), C4AA(H4AD), C9BA(H9BA), C0CA(H0CA), C50(H50), C1CA(H1CA),
 C45(H45), C49(H49), C47(H47), C46(H46), C48(H48), C44(H44), C0BA(H0BA),
 C8AA(H8AA), C0AA(H0AA), C7AA(H7AA), C3BA(H3BA), C1BA(H1BA), C4BA(H4BA),
 C2BA(H2BA), C5CA(H5CA), C6CA(H6CA), C4CA(H4CA), C2CA(H2CA), C3CA(H3CA),
 C8BA(H8BA), C5BA(H5BA), C6BA(H6BA)
7.c Idealised Me refined as rotating group:
 C30A(H30A,H30B,H30C), C29A(H29A,H29B,H29C), C31A(H31A,H31B,H31C), C28A(H28A,
 H28B,H28C), C27A(H27A,H27B,H27C), C2A(H2AA,H2AB,H2AC), C3A(H3AA,H3AB,H3AC),
 C5A(H5AA,H5AB,H5AC), C4A(H4AA,H4AB,H4AC), C1A(H1AA,H1AB,H1AC), C39A(H39A,H39B,
 H39C), C43A(H43A,H43B,H43C), C16A(H16A,H16B,H16C), C14A(H14A,H14B,H14C),
 C15A(H15A,H15B,H15C), C17A(H17A,H17B,H17C), C40A(H40A,H40B,H40C), C42A(H42A,
 H42B,H42C), C18A(H18A,H18B,H18C), C41A(H41A,H41B,H41C), C107(H10A,H10B,H10C),
 C114(H11A,H11B,H11C), C121(H12A,H12B,H12C), C103(H10D,H10E,H10F), C6AA(H6AA,
 H6AB,H6AC)
;
_shelx_res_checksum              7115
_olex2_submission_special_instructions 'No special instructions were received'