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_7709993
_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 Ho N7 O14), C84 H66 Cu F48 Ho2 N14 O24'
_chemical_formula_sum            'C178 H134 Cu3 F108 Ho4 N28 O52'
_chemical_formula_weight         6399.46
_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
_atom_sites_solution_primary     direct
_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                85.124(3)
_cell_angle_beta                 71.356(4)
_cell_angle_gamma                85.871(3)
_cell_formula_units_Z            1
_cell_length_a                   14.6422(6)
_cell_length_b                   21.1036(9)
_cell_length_c                   21.4102(8)
_cell_measurement_reflns_used    11506
_cell_measurement_temperature    113
_cell_measurement_theta_max      29.2663
_cell_measurement_theta_min      2.9755
_cell_volume                     6238.9(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.35.11 (release 16-05-2011 CrysAlis171 .NET)
(compiled May 16 2011,17:55:39)
;
_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
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0790
_diffrn_reflns_av_unetI/netI     0.1272
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            52184
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.010
_diffrn_reflns_theta_max         25.010
_diffrn_reflns_theta_min         2.982
_exptl_absorpt_coefficient_mu    1.658
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.81442
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'metallic bluish violet'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.703
_exptl_crystal_description       plank
_exptl_crystal_F_000             3141
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.921
_refine_diff_density_min         -1.345
_refine_diff_density_rms         0.176
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1673
_refine_ls_number_reflns         21988
_refine_ls_number_restraints     1613
_refine_ls_restrained_S_all      1.022
_refine_ls_R_factor_all          0.1340
_refine_ls_R_factor_gt           0.0958
_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^)+(0.1177P)^2^+49.9122P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2410
_refine_ls_wR_factor_ref         0.2679
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14542
_reflns_number_total             21988
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt00220e2.cif
_cod_data_source_block           Ho-Cu
_cod_database_code               7709993
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.852
_shelx_estimated_absorpt_t_min   0.733
_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
 C21-C20
 1.5 with sigma of 0.01
 C26-C27
 1.46 with sigma of 0.01
 C68-C67
 1.46 with sigma of 0.01
 C22-C21
 1.47 with sigma of 0.01
3. Rigid bond restraints
 C23, F10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C22, O6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 O8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C73, C74
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C20, O5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C25, C26
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C71, F44
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C72, O21
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C71, C72
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C72, C73
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C28, F17
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C28, F18
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C68, C69
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 O19, C67
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C71, F43
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C19, F8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C19, F9
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C19, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C67, O19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C27, O8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C27, C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C11 \\sim C9 \\sim C57 \\sim C36 \\sim C13 \\sim C12 \\sim C10 \\sim C59 \\sim
C55 \\sim C37 \\sim C77 \\sim C58 \\sim C60 \\sim C63 \\sim C54 \\sim C84 \\sim
C56 \\sim C8 \\sim C49 \\sim C30 \\sim C7 \\sim C83 \\sim C44 \\sim C33 \\sim
C86 \\sim C52 \\sim C82 \\sim C2 \\sim C35 \\sim C17 \\sim C15 \\sim C18 \\sim
C45 \\sim C65 \\sim C5 \\sim C48 \\sim C16 \\sim C62 \\sim C87 \\sim C46 \\sim
C64 \\sim C6 \\sim C29 \\sim C80 \\sim C41 \\sim C31 \\sim C85 \\sim C14 \\sim
C53 \\sim C51 \\sim C78 \\sim C47 \\sim C43 \\sim C1 \\sim C81 \\sim C3 \\sim
C61 \\sim C39 \\sim C4 \\sim C32 \\sim C79 \\sim C42 \\sim C74 \\sim C50 \\sim
C40 \\sim C38 \\sim C34 \\sim C76 \\sim C67 \\sim C69 \\sim C72 \\sim C75 \\sim
C70 \\sim C71 \\sim C66 \\sim C73 \\sim C88 \\sim C89 \\sim C24 \\sim C19 \\sim
C28 \\sim C68 \\sim C25 \\sim C22 \\sim C21 \\sim C26 \\sim C23 \\sim C20:
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
C27 \\sim O8 \\sim C28 \\sim C26: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(C69) \\sim Ueq, Uanis(F46) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(F47) \\sim Ueq, Uanis(C67) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C22)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(F9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
5.a Aromatic/amide H refined with riding coordinates:
 C36(H36), C11(H11), C9(H9), C13(H13), C60(H60), C56(H56), C58(H58), C37(H37),
 C63(H63), C84(H84), C83(H83), C45(H45), C16(H16), C87(H87), C40(H40), C73(H73),
  C68(H68), C21(H21), C26(H26)
5.b Fitted hexagon refined as free rotating group:
 C12(C11,C10,C9,C8,C13), C60(C55,C56,C57,C58,C59)
5.c Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C6(H6A,H6B,H6C), C29(H29A,H29B,H29C), C31(H31A,H31B,
 H31C), C53(H53A,H53B,H53C), C51(H51A,H51B,H51C), C78(H78A,H78B,H78C), C1(H1A,
 H1B,H1C), C81(H81A,H81B,H81C), C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C32(H32A,H32B,
 H32C), C79(H79A,H79B,H79C), C50(H50A,H50B,H50C), C34(H34A,H34B,H34C), C76(H76A,
 H76B,H76C)
;
_shelx_res_checksum              3388
_shelx_hkl_checksum              40453
_shelx_fab_checksum              49748
_olex2_submission_special_instructions 'No special instructions were received'