Lanthanide–radical complexes derived from a nitronyl nitroxide ligand with chelating and bridging functions: structure and magnetic properties
Zhou, Yan; Xie, Junfang; Huang, Xiaohui; Jin, Chaoyi; Ma, Yue; Li, Licun; CrystEngComm 27 (2025) 1120–1127; doi:10.1039/D4CE01184H

data_7249760
_publ_section_title
;
 Lanthanide--radical complexes derived from a nitronyl nitroxide ligand
 with chelating and bridging functions: structure and magnetic properties
;
_journal_issue                   8
_journal_name_full               CrystEngComm
_journal_page_first              1120
_journal_page_last               1127
_journal_paper_doi               10.1039/D4CE01184H
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C79 H47 Dy3 F54 N8 O22'
_chemical_formula_sum            'C79 H47 Dy3 F54 N8 O22'
_chemical_formula_weight         2973.74
_chemical_name_systematic        3-Dy
_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             2024-11-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-23 deposited with the CCDC.	2025-01-09 downloaded from the CCDC.
;
_cell_angle_alpha                93.091(3)
_cell_angle_beta                 93.967(3)
_cell_angle_gamma                111.555(3)
_cell_formula_units_Z            2
_cell_length_a                   12.6512(5)
_cell_length_b                   16.6417(6)
_cell_length_c                   27.8412(10)
_cell_measurement_reflns_used    19545
_cell_measurement_temperature    113.1500
_cell_measurement_theta_max      32.2620
_cell_measurement_theta_min      1.7850
_cell_volume                     5418.7(4)
_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 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      113.15
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -120.00  60.00   1.00    5.00    --  -30.00  45.00   0.00  180
  2  \w   -120.00  60.00   1.00    5.00    --  -30.00  45.00  90.00  180
  3  \w   -120.00  60.00   1.00    5.00    --  -30.00  45.00 180.00  180
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_unetI/netI     0.0551
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            45275
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         25.349
_diffrn_reflns_theta_min         1.876
_diffrn_source                   'fine-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    2.207
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58866
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.823
_exptl_crystal_description       block
_exptl_crystal_F_000             2874
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.101
_refine_diff_density_min         -1.617
_refine_diff_density_rms         0.212
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1530
_refine_ls_number_reflns         19739
_refine_ls_number_restraints     1841
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.1011
_refine_ls_R_factor_gt           0.0860
_refine_ls_shift/su_max          0.007
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0999P)^2^+104.2513P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2212
_refine_ls_wR_factor_ref         0.2318
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16063
_reflns_number_total             19739
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce01184h2.cif
_cod_data_source_block           3-Dy
_cod_depositor_comments
'Adding full bibliography for 7249760--7249762.cif.'
_cod_database_code               7249760
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.809
_shelx_estimated_absorpt_t_min   0.809
_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
 H14A-H16C
 2.35 with sigma of 0.01
 H32A-H34C
 2.35 with sigma of 0.01
 C22-C21 = C21-C20 = C20-C19 = C19-C18 = C5-C4 = C4-C3 = C3-C2 = C2-C1
 1.33 with sigma of 0.01
 C9-C10 = C9-C8 = C6-C10 = C7-C6 = C26-C25 = C25-C24 = C24-C23 = C27-C23
 1.33 with sigma of 0.01
 C17-C12 = C16-C12 = C15-C13 = C14-C13 = C33-C29 = C34-C29 = C32-C30 = C31-C30
 1.54 with sigma of 0.01
 C66-C65 = C69-C68 = C74-C73 = C71-C70 = C79-C78 = C56-C55 = C54-C53 = C36-C35
 = C44-C43 = C41-C40 = C49-C48
 1.51 with sigma of 0.001
 F33-C70 = F31-C70 = F32-C70 = F19-C75 = F21-C75 = F20-C75 = F25-C65 = F27-C65
 = F26-C65 = F23-C79 = F30B-C69 = F30A-C69 = F29B-C69 = F29A-C69 = F28B-C69 =
 F18-C39 = F16-C39 = F17-C39 = F12-C44 = F10-C44 = F11-C44 = F7-C40 = F9-C40 =
 F8-C40 = F3-C49 = F2-C49 = F1-C49 = F4-C45 = F5-C45 = F6-C45 = F13-C35 = F15-
 C35 = F14-C35 = F22-C79 = F24-C79 = F53-C60 = F54-C60 = F52-C60 = F42-C50 =
 F41-C50 = F40-C50 = F38-C54 = F49-C64 = F51-C64 = F50-C64 = F43-C59 = F45-C59 =
  F44-C59 = F34-C74 = F35-C74 = F36-C74 = F48-C55 = F46-C55 = F47-C55
 1.35 with sigma of 0.001
 N7-C28 = N5-C11 = N3-C5 = N2-C27 = N2-C26
 1.36 with sigma of 0.01
 C43-C42 = C37-C36 = C48-C47 = C78-C77 = C67-C66 = C68-C67 = C72-C71 = C52-C51
 = C53-C52 = C57-C56 = C58-C57 = C62-C61
 1.39 with sigma of 0.01
 C69-F28A \\sim C69-F29A \\sim C69-F30A
 with sigma of 0.01
 C69-F28B \\sim C69-F29B \\sim C69-F30B
 with sigma of 0.01
 F29A-F29B \\sim F28A-F28B \\sim F30A-F30B
 with sigma of 0.02
3. Rigid bond restraints
 O13
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C53
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 F17, C39
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 F40, C50
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 F48, C55
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 F10, C44
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C51
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 O13, C56
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 F14, C35
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 F18, C39
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 F16, C39
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C69
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C44, F11
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 C58, C57
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 C53, C54
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 F37, C54
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 O14, C58
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.005
 F24, C79
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
O7 \\sim C38 \\sim Dy1: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O12 \\sim Dy3 \\sim C53: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C53 \\sim C52 \\sim O12: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C22 \\sim C3 \\sim C28 \\sim C71 \\sim C68 \\sim C67 \\sim C26 \\sim C66 \\sim
C5 \\sim C7 \\sim C1 \\sim C21 \\sim C11 \\sim C25 \\sim C18 \\sim C24 \\sim C8
\\sim C65 \\sim C27 \\sim C2 \\sim C12 \\sim C23 \\sim C62 \\sim C61 \\sim C76
\\sim C4 \\sim C29 \\sim C73 \\sim C6 \\sim C63 \\sim C78 \\sim C72 \\sim C10
\\sim C70 \\sim C47 \\sim C9 \\sim C48 \\sim C30 \\sim C77 \\sim C20 \\sim C45
\\sim C75 \\sim C46 \\sim C49 \\sim C64 \\sim C74 \\sim C69 \\sim C19 \\sim C13
\\sim C60 \\sim C31 \\sim C39 \\sim C79 \\sim C34 \\sim C40 \\sim C14 \\sim C33
\\sim C15 \\sim C43 \\sim C36 \\sim C16 \\sim C42 \\sim C32 \\sim C44 \\sim C17
\\sim C51 \\sim C41 \\sim C55 \\sim C50 \\sim C52 \\sim C38 \\sim C58 \\sim C53
\\sim C35 \\sim C37: within 3.8A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 3.8A
F27 \\sim F33 \\sim F25 \\sim F26 \\sim F49 \\sim F2 \\sim F54 \\sim F50 \\sim
F5 \\sim F6 \\sim F1 \\sim F35 \\sim F36 \\sim F34 \\sim F32 \\sim F3 \\sim F51
\\sim F23 \\sim F31 \\sim F20 \\sim F7 \\sim F53 \\sim F9 \\sim F52 \\sim F21
\\sim F8 \\sim F19 \\sim F12 \\sim F22 \\sim F24 \\sim F16 \\sim F15 \\sim F18
\\sim F17 \\sim F10 \\sim F11 \\sim F4 \\sim F13 \\sim F47 \\sim F46 \\sim F48
\\sim F41 \\sim F42 \\sim F40: within 3.8A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 3.8A
C37 \\sim C36 \\sim C38: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
F27 \\sim F33 \\sim F25 \\sim F26 \\sim F49 \\sim F2 \\sim F54 \\sim F50 \\sim
F5 \\sim F6 \\sim F1 \\sim F35 \\sim F36 \\sim F34 \\sim F32 \\sim F3 \\sim F51
\\sim F23 \\sim F31 \\sim F20 \\sim F7 \\sim F53 \\sim F9 \\sim F52 \\sim F21
\\sim F8 \\sim F19 \\sim F12 \\sim F22 \\sim F24 \\sim F16 \\sim F15 \\sim F18
\\sim F17 \\sim F10 \\sim F11 \\sim F4 \\sim F13 \\sim F47 \\sim F46 \\sim F48
\\sim F41 \\sim F42 \\sim F40 \\sim F14 \\sim F44 \\sim F43 \\sim F45: within
3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
C22 \\sim C3 \\sim C28 \\sim C71 \\sim C68 \\sim C67 \\sim C26 \\sim C66 \\sim
C5 \\sim C7 \\sim C1 \\sim C21 \\sim C11 \\sim C25 \\sim C18 \\sim C24 \\sim C8
\\sim C65 \\sim C27 \\sim C2 \\sim C12 \\sim C23 \\sim C62 \\sim C61 \\sim C76
\\sim C4 \\sim C29 \\sim C73 \\sim C6 \\sim C63 \\sim C78 \\sim C72 \\sim C10
\\sim C70 \\sim C47 \\sim C9 \\sim C48 \\sim C30 \\sim C77 \\sim C20 \\sim C45
\\sim C75 \\sim C46 \\sim C49 \\sim C64 \\sim C74 \\sim C69 \\sim C19 \\sim C13
\\sim C60 \\sim C31 \\sim C39 \\sim C79 \\sim C34 \\sim C40 \\sim C14 \\sim C33
\\sim C15 \\sim C43 \\sim C36 \\sim C16 \\sim C42 \\sim C32 \\sim C44 \\sim C17
\\sim C51 \\sim C41 \\sim C55 \\sim C50 \\sim C52 \\sim C38 \\sim C58 \\sim C53
\\sim C35 \\sim C37 \\sim C56 \\sim C57 \\sim C59 \\sim C54: within 3.8A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 3.8A
F27 \\sim F33 \\sim F25 \\sim F26 \\sim F49 \\sim F2 \\sim F54 \\sim F50 \\sim
F5 \\sim F6 \\sim F1 \\sim F35 \\sim F36 \\sim F34 \\sim F32 \\sim F3 \\sim F51
\\sim F23 \\sim F31 \\sim F20 \\sim F7 \\sim F53 \\sim F9 \\sim F52 \\sim F21
\\sim F8 \\sim F19 \\sim F12 \\sim F22 \\sim F24 \\sim F16 \\sim F15 \\sim F18
\\sim F17 \\sim F10 \\sim F11 \\sim F4 \\sim F13 \\sim F47 \\sim F46 \\sim F48
\\sim F41 \\sim F42 \\sim F40 \\sim F14 \\sim F44 \\sim F43 \\sim F45 \\sim F38
\\sim F39 \\sim F37: within 3.8A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 3.8A
F27 \\sim F33 \\sim F25 \\sim F26 \\sim F49 \\sim F2 \\sim F54 \\sim F50 \\sim
F5 \\sim F6 \\sim F1 \\sim F35 \\sim F36 \\sim F34 \\sim F32 \\sim F3 \\sim F51
\\sim F23 \\sim F31 \\sim F20 \\sim F7 \\sim F53 \\sim F9 \\sim F52 \\sim F21
\\sim F8 \\sim F19 \\sim F12 \\sim F22 \\sim F24 \\sim F16 \\sim F15 \\sim F18
\\sim F17 \\sim F10 \\sim F11 \\sim F4 \\sim F13 \\sim F47 \\sim F46 \\sim F48
\\sim F41 \\sim F42 \\sim F40 \\sim F14 \\sim F44 \\sim F43 \\sim F45 \\sim F38
\\sim F39 \\sim F37 \\sim F30A \\sim F29A \\sim F28A \\sim F29B \\sim F28B
\\sim F30B: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 3.8A
Uanis(C58) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C55) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C59) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C54) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Others
 Fixed Sof: F30A(0.5) F29A(0.5) F28A(0.5) F29B(0.5) F28B(0.5) F30B(0.5)
6.a Aromatic/amide H refined with riding coordinates:
 C22(H22), C3(H3), C67(H67), C5(H5), C7(H7), C1(H1), C25(H25), C18(H18),
 C24(H24), C27(H27), C2(H2), C62(H62), C72(H72), C10(H10), C47(H47), C9(H9),
 C77(H77), C20(H20), C19(H19), C42(H42), C52(H52), C37(H37), C57(H57)
6.b Idealised Me refined as rotating group:
 C31(H31A,H31B,H31C), C34(H34A,H34B,H34C), C14(H14A,H14B,H14C), C33(H33A,H33B,
 H33C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C32(H32A,H32B,H32C), C17(H17A,
 H17B,H17C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              26756
_shelx_hkl_checksum              13898
_shelx_fab_checksum              17604
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
- Detector area scaling
;