Supramolecular heptanuclear Ln-Cu complexes involving nitronyl nitroxide biradicals: structure and magnetic behavior
Xi, Lu; Jin, Chaoyi; Song, Hong-Wei; Wang, Xiao-Tong; Li, Licun; Sutter, Jean-Pascal; Dalton Transactions  (2022) –; doi:10.1039/D2DT00220E

data_7709994
_publ_section_title
;
 Supramolecular heptanuclear Ln-Cu complexes involving nitronyl nitroxide
 biradicals: structure and magnetic behavior
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT00220E
_journal_year                    2022
_chemical_formula_moiety
'2(C47 H34 Cu F30 N7 O14 Y), C84 H66 Cu F48 N14 O24 Y2'
_chemical_formula_sum            'C178 H134 Cu3 F108 N28 O52 Y4'
_chemical_formula_weight         6095.38
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2022-03-22
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-03-26 deposited with the CCDC.	2022-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                85.16(3)
_cell_angle_beta                 71.34(3)
_cell_angle_gamma                85.75(3)
_cell_formula_units_Z            1
_cell_length_a                   14.695(3)
_cell_length_b                   21.213(4)
_cell_length_c                   21.502(4)
_cell_measurement_reflns_used    7005
_cell_measurement_temperature    113.1500
_cell_measurement_theta_max      27.9103
_cell_measurement_theta_min      1.0016
_cell_volume                     6320(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2014)'
_diffrn_ambient_temperature      113.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1425
_diffrn_reflns_av_unetI/netI     0.1949
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            61433
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.491
_exptl_absorpt_coefficient_mu    1.308
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.7616
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2008)'
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.602
_exptl_crystal_description       block
_exptl_crystal_F_000             3029
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.213
_refine_diff_density_min         -0.773
_refine_diff_density_rms         0.139
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2143
_refine_ls_number_reflns         22233
_refine_ls_number_restraints     2277
_refine_ls_restrained_S_all      1.514
_refine_ls_R_factor_all          0.2169
_refine_ls_R_factor_gt           0.1204
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1884P)^2^+0.6241P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3026
_refine_ls_wR_factor_ref         0.3768
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10725
_reflns_number_total             22233
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00220e2.cif
_cod_data_source_block           Y-Cu
_cod_database_code               7709994
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.880
_shelx_estimated_absorpt_t_min   0.859
_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
 O7-C25 = O8-C27 = O6-C22 = O5-C20
 1.25 with sigma of 0.01
 F48-C75 = F47-C75 = F46-C75 = F41-C70 = F42-C70 = F40-C70 = F44-C71 = F43-C71
 = F45-C71 = F38-C66 = F37-C66 = F39-C66
 1.39 with sigma of 0.01
 F18-C28 = F17-C28 = F16-C28
 1.39 with sigma of 0.01
 F15-C24 = F14-C24 = F13-C24
 1.39 with sigma of 0.01
 F7-C19 = F9-C19 = F8-C19
 1.39 with sigma of 0.01
 F11-C23 = F10-C23 = F12-C23
 1.39 with sigma of 0.01
 O22-C74 = O21-C72 = O19-C67 = O20-C69
 1.25 with sigma of 0.01
 C25-C24 = C28-C27 = C23-C22 = C20-C19
 1.54 with sigma of 0.01
 C73-C72 = C74-C73 = C69-C68 = C68-C67
 1.39 with sigma of 0.01
 C75-C74 = C70-C69 = C67-C66 = C72-C71
 1.54 with sigma of 0.01
 C21-C20 = C22-C21 = C26-C25 = C27-C26
 1.39 with sigma of 0.01
 C23A-C22A = C28A-C27A = C25A-C24A = C20A-C19A
 1.54 with sigma of 0.01
 C75A-C74A = C72A-C71A = C67A-C66A = C70A-C69A
 1.5 with sigma of 0.01
 C27A-C26A = C26A-C25A = C21A-C20A = C22A-C21A
 1.39 with sigma of 0.01
 O8A-C27A = O7A-C25A = O6A-C22A = O5A-C20A
 1.25 with sigma of 0.01
 O22A-C74A = O21A-C72A = O19A-C67A = O20A-C69A
 1.25 with sigma of 0.01
 C69A-C68A = C68A-C67A = C74A-C73A = C73A-C72A
 1.39 with sigma of 0.01
 F41A-C70A = F42A-C70A = F40A-C70A = F39A-C66A = F38A-C66A = F37A-C66A = F46A-
 C75A = F48A-C75A = F47A-C75A = F44A-C71A = F45A-C71A = F43A-C71A
 1.39 with sigma of 0.01
 F14A-C24A = F13A-C24A = F15A-C24A = F7A-C19A = F9A-C19A = F8A-C19A = F12A-
 C23A = F10A-C23A = F11A-C23A = F17A-C28A = F16A-C28A = F18A-C28A
 1.39 with sigma of 0.01
 C52-C49 = C5-C2
 1.53 with sigma of 0.001
 C20-C19 = C25A-C24A = C28A-C27A = C25-C24 = C23-C22 = C20A-C19A = C23A-C22A =
 C28-C27 = C15-C14 = C18-C17 = C86-C85 = C89-C88 = C39-C38 = C42-C41 = C44-C43 =
  C47-C46 = C72A-C71A = C67-C66 = C70-C69 = C67A-C66A = C70A-C69A = C75-C74
 1.53 with sigma of 0.001
 C52-C49 = C52-C51 = C52-C53 = C52-N9
 1.39 with sigma of 0.001
 C52-C51 = C53-C52 = C50-C49 = C49-C48 = C77-C76 = C78-C77 = C81-C80 = C80-C79
 = C31-C30 = C30-C29 = C33-C32 = C34-C33 = C2-C1 = C3-C2 = C6-C5 = C5-C4
 1.52 with sigma of 0.001
 C69-F41
 2.4 with sigma of 0.02
 C74-F48
 2.4 with sigma of 0.02
 C69-F42
 2.4 with sigma of 0.02
 C72-F45
 2.4 with sigma of 0.02
 C67-F39
 2.4 with sigma of 0.02
 C67-F38
 2.4 with sigma of 0.02
 C67-F37
 2.4 with sigma of 0.02
 C72-F44
 2.4 with sigma of 0.02
 C72-F43
 2.4 with sigma of 0.02
 C25-F15 = C27-F18
 2.4 with sigma of 0.02
 C69-F40
 2.4 with sigma of 0.02
 O21-C73
 2.287 with sigma of 0.02
 O20-C68
 2.287 with sigma of 0.02
 O22-C73
 2.287 with sigma of 0.02
 O19-C68
 2.287 with sigma of 0.02
 O19-C66
 2.421 with sigma of 0.02
 O20-C70
 2.421 with sigma of 0.02
 O21-C71
 2.421 with sigma of 0.02
 C73-C71
 2.539 with sigma of 0.02
 C20A-F7A
 2.4 with sigma of 0.02
 C68-C66
 2.539 with sigma of 0.02
 C25A-F14A
 2.4 with sigma of 0.02
 C68-C70
 2.539 with sigma of 0.02
 C73-C75
 2.539 with sigma of 0.02
 C25A-F13A
 2.4 with sigma of 0.02
 C20A-F9A
 2.4 with sigma of 0.02
 C22A-F11A
 2.4 with sigma of 0.02
 C25A-F15A
 2.4 with sigma of 0.02
 C22A-F10A
 2.4 with sigma of 0.02
 C22A-F12A
 2.4 with sigma of 0.02
 O22A-C73A
 2.287 with sigma of 0.02
 C20A-F8A
 2.4 with sigma of 0.02
 O21A-C73A
 2.287 with sigma of 0.02
 C27A-F16A
 2.4 with sigma of 0.02
 O20A-C68A
 2.287 with sigma of 0.02
 O19A-C68A
 2.287 with sigma of 0.02
 O22A-C75A
 2.421 with sigma of 0.02
 C27A-F18A
 2.4 with sigma of 0.02
 C27A-F17A
 2.4 with sigma of 0.02
 O21A-C71A
 2.421 with sigma of 0.02
 O20A-C70A
 2.421 with sigma of 0.02
 O19A-C66A
 2.421 with sigma of 0.02
 C68A-C66A
 2.539 with sigma of 0.02
 C68A-C70A
 2.539 with sigma of 0.02
 O7A-C26A
 2.287 with sigma of 0.02
 C73A-C75A
 2.539 with sigma of 0.02
 O8A-C26A
 2.287 with sigma of 0.02
 O5A-C21A
 2.287 with sigma of 0.02
 C73A-C71A
 2.539 with sigma of 0.02
 O6A-C21A
 2.287 with sigma of 0.02
 O8A-C28A
 2.421 with sigma of 0.02
 O5A-C19A
 2.421 with sigma of 0.02
 O7A-C24A
 2.421 with sigma of 0.02
 O6A-C23A
 2.421 with sigma of 0.02
 C21A-C23A
 2.539 with sigma of 0.02
 C74-F47
 2.4 with sigma of 0.02
 C74-F46
 2.4 with sigma of 0.02
 O22-C75
 2.421 with sigma of 0.02
 F42-F41 \\sim F42-F40 \\sim F41-F40
 with sigma of 0.02
 F18-F17 \\sim F17-F16 \\sim F18-F16
 with sigma of 0.02
 F9-F8 \\sim F8-F7 \\sim F9-F7
 with sigma of 0.02
 F38-F37 \\sim F39-F38 \\sim F39-F37
 with sigma of 0.02
 F15-F13 \\sim F15-F14 \\sim F14-F13
 with sigma of 0.02
 F12-F11 \\sim F11-F10 \\sim F12-F10
 with sigma of 0.02
 F8-C20 \\sim F7-C20 \\sim F9-C20
 with sigma of 0.02
 F11-C22 \\sim F12-C22 \\sim F10-C22
 with sigma of 0.02
 F15-C25 \\sim F14-C25 \\sim F13-C25
 with sigma of 0.02
 F18-C27 \\sim F17-C27 \\sim F16-C27
 with sigma of 0.02
 F48-F47 \\sim F48-F46 \\sim F47-F46
 with sigma of 0.02
 F45-F43 \\sim F44-F43 \\sim F45-F44
 with sigma of 0.02
 F9A-F7A \\sim F8A-F7A \\sim F9A-F8A
 with sigma of 0.02
 F42A-F41A \\sim F41A-F40A \\sim F42A-F40A
 with sigma of 0.02
 F48A-F47A \\sim F47A-F46A \\sim F48A-F46A
 with sigma of 0.02
 F45A-F43A \\sim F45A-F44A \\sim F44A-F43A
 with sigma of 0.02
 F38A-F37A \\sim F39A-F37A \\sim F39A-F38A
 with sigma of 0.02
 F15A-F13A \\sim F14A-F13A \\sim F15A-F14A
 with sigma of 0.02
 F17A-F16A \\sim F18A-F16A \\sim F18A-F17A
 with sigma of 0.02
 F12A-F11A \\sim F12A-F10A \\sim F11A-F10A
 with sigma of 0.02
3. Restrained planarity
 O8, C27, C28, C26, C25, O7, C24
 with sigma of 0.1
 O22, C75, C74, C73, O21, C72, C71
 with sigma of 0.1
 O20, C69, C68, C70, O19, C67, C66
 with sigma of 0.1
 O6, C22, C23, C21, C20, O5, C19
 with sigma of 0.1
 O7A, C25A, C24A, C26A, C27A, O8A, C28A
 with sigma of 0.1
 O20A, C69A, C68A, O19A, C67A, C66A, C70A
 with sigma of 0.1
 O22A, C74A, C75A, C73A, C72A, O21A, C71A
 with sigma of 0.1
 O5A, C20A, C21A, C23A, C22A, O6A, C19A
 with sigma of 0.1
 O5A, C20A, C22A, O6A, C21A, C23A, C19A
 with sigma of 0.1
 C19, C20, O5, C21, C22, O6, C23
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O6 \\sim O5 \\sim O7 \\sim O8 \\sim F8 \\sim F10 \\sim F7 \\sim F9 \\sim C19
\\sim F13 \\sim F14 \\sim C24 \\sim C20 \\sim C23 \\sim F15 \\sim F18 \\sim F16
\\sim C28 \\sim C27 \\sim F17 \\sim F12 \\sim F11 \\sim C22 \\sim C21 \\sim C25
\\sim C26: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
O7A \\sim F13A \\sim F18A \\sim O5A \\sim C27A \\sim F9A \\sim C25A \\sim C20A
\\sim F15A \\sim C19A \\sim C28A \\sim F7A \\sim O6A \\sim F8A \\sim C24A \\sim
F10A \\sim F14A \\sim C21A \\sim C26A \\sim C23A \\sim O8A \\sim C22A \\sim
F17A \\sim F12A \\sim F16A \\sim F11A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
F47 \\sim O22 \\sim C75 \\sim F46 \\sim C74 \\sim F48 \\sim F45 \\sim C73 \\sim
C72 \\sim C71 \\sim F44 \\sim O20A \\sim F46A \\sim C70A \\sim F40A \\sim F41A
\\sim F42A \\sim C69A \\sim C68A \\sim O20 \\sim O21 \\sim O19 \\sim C67 \\sim
C70 \\sim C66 \\sim F40 \\sim F41 \\sim F42 \\sim F43 \\sim C69 \\sim F37 \\sim
F38 \\sim F39 \\sim C68 \\sim F47A \\sim O22A \\sim O21A \\sim O19A \\sim C75A
\\sim C67A \\sim C74A \\sim F48A \\sim C66A \\sim F45A \\sim C73A \\sim F43A
\\sim C72A \\sim C71A \\sim F44A \\sim F37A \\sim F38A \\sim F39A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C53 \\sim C52 \\sim C51: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
5. Rigid body (RIGU) restrains
 F47A, O22A, O20A, O21A, O19A, C75A, C67A, F46A, C74A, F48A, C70A, C66A, F40A,
 F45A, F41A, F42A, C73A, F43A, C72A, C71A, C69A, F44A, F37A, F38A, C68A, F39A,
 Y2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F47, O22, O20, O21, O19, C75, C67, F46, C74, F48, C70, C66, F40, F45, F41,
 F42, C73, F43, C72, C71, C69, F44, F37, F38, F39, C68, Y2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 Y1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O6, F16, C25, O5, F12, O7, F15, O8, C27, F8, C22, F10, C23, F7, F18, F9, C28,
 C19, F17, F13, F11, F14, C21, C24, C26, C20, Y1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 O7A, F13A, F18A, O5A, C27A, F9A, C25A, C20A, F15A, C19A, C28A, F7A, O6A, F8A,
 C24A, F10A, F14A, C21A, C26A, C23A, O8A, C22A, F17A, F12A, F16A, F11A, Y1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Sof(O7A)=Sof(O5A)=Sof(F9A)=Sof(C20A)=Sof(C19A)=Sof(F7A)=Sof(F8A)=Sof(F10A)=
 Sof(C21A)=Sof(H21A)=Sof(C23A)=Sof(C22A)=Sof(F12A)=Sof(F11A)=Sof(O6A)=Sof(C25A)=
 Sof(C24A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(O8A)=
 Sof(C28A)=Sof(F17A)=Sof(F18A)=Sof(F16A)=1-FVAR(1)
 Sof(O6)=Sof(O5)=Sof(O7)=Sof(O8)=Sof(F8)=Sof(F10)=Sof(F7)=Sof(F9)=Sof(C19)=
 Sof(F13)=Sof(F14)=Sof(C24)=Sof(C20)=Sof(C23)=Sof(F15)=Sof(F18)=Sof(F16)=
 Sof(C28)=Sof(C27)=Sof(F17)=Sof(F12)=Sof(F11)=Sof(C22)=Sof(C21)=Sof(H21)=
 Sof(C25)=Sof(C26)=Sof(H26)=FVAR(1)
 Sof(F47A)=Sof(O22A)=Sof(O20A)=Sof(O21A)=Sof(O19A)=Sof(C75A)=Sof(C67A)=
 Sof(F46A)=Sof(C74A)=Sof(F48A)=Sof(C70A)=Sof(C66A)=Sof(F40A)=Sof(F45A)=
 Sof(F41A)=Sof(F42A)=Sof(C73A)=Sof(H73A)=Sof(F43A)=Sof(C72A)=Sof(C71A)=
 Sof(C69A)=Sof(F44A)=Sof(F37A)=Sof(F38A)=Sof(F39A)=Sof(C68A)=Sof(H68A)=1-FVAR(2)
 Sof(F47)=Sof(O22)=Sof(O20)=Sof(O21)=Sof(O19)=Sof(C75)=Sof(C67)=Sof(F46)=
 Sof(C74)=Sof(F48)=Sof(C70)=Sof(C66)=Sof(F40)=Sof(F45)=Sof(F41)=Sof(F42)=
 Sof(C73)=Sof(H73)=Sof(F43)=Sof(C72)=Sof(C71)=Sof(C69)=Sof(F44)=Sof(F37)=
 Sof(F38)=Sof(F39)=Sof(C68)=Sof(H68)=FVAR(2)
7.a Aromatic/amide H refined with riding coordinates:
 C36(H36), C58(H58), C60(H60), C56(H56), C37(H37), C63(H63), C11(H11), C9(H9),
 C13(H13), C84(H84), C83(H83), C87(H87), C45(H45), C16(H16), C40(H40), C73(H73),
  C21(H21), C26(H26), C68(H68), C21A(H21A), C26A(H26A), C73A(H73A), C68A(H68A)
7.b Fitted hexagon refined as free rotating group:
 C58(C59,C60,C55,C56,C57), C12(C11,C10,C9,C8,C13)
7.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C78(H78A,H78B,H78C), C48(H48A,H48B,H48C), C31(H31A,H31B,
 H31C), C6(H6A,H6B,H6C), C4(H4A,H4B,H4C), C51(H51A,H51B,H51C), C32(H32A,H32B,
 H32C), C1(H1A,H1B,H1C), C81(H81A,H81B,H81C), C3(H3A,H3B,H3C), C79(H79A,H79B,
 H79C), C76(H76A,H76B,H76C), C34(H34A,H34B,H34C), C50(H50A,H50B,H50C), C53(H53A,
 H53B,H53C)
;
_shelx_res_checksum              84950
_shelx_hkl_checksum              60109
_shelx_fab_checksum              50020
_olex2_submission_special_instructions 'No special instructions were received'