Structure, magnetic properties and fluorescence selectivity of 1D chain complexes based on the pyrazolyl nitronyl nitroxide radical
Chu, Jiamin; Liu, Yi; Li, Jing; Zhu, Mei; CrystEngComm 27 (2025) 1583–1590; doi:10.1039/D4CE01113A

data_7249844
_publ_section_title
;
 Structure, magnetic properties and fluorescence selectivity of 1D chain
 complexes based on the pyrazolyl nitronyl nitroxide radical
;
_journal_issue                   11
_journal_name_full               CrystEngComm
_journal_page_first              1583
_journal_page_last               1590
_journal_paper_doi               10.1039/D4CE01113A
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C59 H47 Cu F30 N8 O16 Tb'
_chemical_formula_sum            'C59 H47 Cu F30 N8 O16 Tb'
_chemical_formula_weight         1916.50
_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     iterative
_audit_creation_date             2024-11-25
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-26 deposited with the CCDC.	2025-01-27 downloaded from the CCDC.
;
_cell_angle_alpha                110.962(4)
_cell_angle_beta                 92.013(4)
_cell_angle_gamma                102.791(4)
_cell_formula_units_Z            2
_cell_length_a                   11.9960(6)
_cell_length_b                   16.6031(7)
_cell_length_c                   20.3772(10)
_cell_measurement_reflns_used    17809
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      30.9960
_cell_measurement_theta_min      1.9150
_cell_volume                     3666.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.101a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.43.101a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.43.101a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -70.00 -43.00   0.50    3.50    --   -5.60 -57.00 120.00   54
  2  \w     -5.00  79.00   0.50    3.50    --    6.38  77.00 120.00  168
  3  \w     -8.00  79.00   0.50    3.50    --    6.38  38.00  60.00  174
  4  \w     -9.00  16.00   0.50    3.50    --    6.38  57.00-180.00   50
  5  \w    -18.00   8.00   0.50    3.50    --   -5.60 -99.00 -30.00   52
  6  \w    -18.00  40.00   0.50    3.50    --    6.38 -99.00 -60.00  116
  7  \w    -11.00  37.00   0.50    3.50    --    6.38 -99.00 -30.00   96
  8  \w    -49.00  20.00   0.50    3.50    --    6.38 -38.00-150.00  138
  9  \w     -4.00  21.00   0.50    3.50    --    6.24 -38.00-120.00   50
 10  \w    -81.00  10.00   0.50    3.50    --   -5.54 -19.00 150.00  182
 11  \w    -67.00 -16.00   0.50    3.50    --    6.24 -38.00  90.00  102
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1181
_diffrn_reflns_av_unetI/netI     0.0821
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            57462
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.026
_diffrn_reflns_theta_max         25.026
_diffrn_reflns_theta_min         1.755
_exptl_absorpt_coefficient_mu    1.391
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76482
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.101a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.736
_exptl_crystal_description       block
_exptl_crystal_F_000             1898
_exptl_crystal_size_max          0.69
_exptl_crystal_size_mid          0.58
_exptl_crystal_size_min          0.25
_refine_diff_density_max         4.948
_refine_diff_density_min         -1.935
_refine_diff_density_rms         0.194
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.105
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1184
_refine_ls_number_reflns         12912
_refine_ls_number_restraints     233
_refine_ls_restrained_S_all      1.103
_refine_ls_R_factor_all          0.1262
_refine_ls_R_factor_gt           0.1082
_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^)+(0.1125P)^2^+53.7710P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2632
_refine_ls_wR_factor_ref         0.2758
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10458
_reflns_number_total             12912
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4ce01113a2.cif
_cod_data_source_block           cu-tb
_cod_depositor_comments
'Adding full bibliography for 7249842--7249844.cif.'
_cod_database_code               7249844
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.722
_shelx_estimated_absorpt_t_min   0.447
_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
 Cu1-O5 \\sim Cu1-O17
 with sigma of 0.02
 Cu1-O4 \\sim Cu1-O00S
 with sigma of 0.02
 O5-C21 \\sim O17-C02L
 with sigma of 0.02
 O4-C19 \\sim O00S-C61
 with sigma of 0.02
 C21-C20 \\sim C02L-C60
 with sigma of 0.02
 C21-C22 \\sim C02L-C0
 with sigma of 0.02
 F6-C22 \\sim F02M-C0
 with sigma of 0.02
 C19-C20 \\sim C61-C60
 with sigma of 0.02
 C19-C18 \\sim C61-C62
 with sigma of 0.02
 F5-C22 \\sim F0-C0
 with sigma of 0.02
 C18-F1 \\sim C62-F40A
 with sigma of 0.02
 C18-F2 \\sim C62-F41A
 with sigma of 0.02
 Cu1-C21 \\sim Cu1-C02L
 with sigma of 0.04
 Cu1-C19 \\sim Cu1-C61
 with sigma of 0.04
 O5-C20 \\sim O17-C60
 with sigma of 0.04
 O5-C22 \\sim O17-C0
 with sigma of 0.04
 O4-C20 \\sim O00S-C60
 with sigma of 0.04
 O4-C18 \\sim O00S-C62
 with sigma of 0.04
 F3-C19 \\sim F34-C61
 with sigma of 0.04
 F3-F1 \\sim F34-F40A
 with sigma of 0.04
 F3-F2 \\sim F34-F41A
 with sigma of 0.04
 C21-F6 \\sim C02L-F02M
 with sigma of 0.04
 C21-F4 \\sim C02L-F02Q
 with sigma of 0.04
 C21-C19 \\sim C02L-C61
 with sigma of 0.04
 C21-F5 \\sim C02L-F0
 with sigma of 0.04
 F6-F4 \\sim F02M-F02Q
 with sigma of 0.04
 F6-F5 \\sim F02M-F0
 with sigma of 0.04
 F4-F5 \\sim F02Q-F0
 with sigma of 0.04
 C19-F1 \\sim C61-F40A
 with sigma of 0.04
 C19-F2 \\sim C61-F41A
 with sigma of 0.04
 C20-C22 \\sim C60-C0
 with sigma of 0.04
 C20-C18 \\sim C60-C62
 with sigma of 0.04
 F1-F2 \\sim F40A-F41A
 with sigma of 0.04
 Cu1-O00S \\sim Cu1-O4
 with sigma of 0.02
 Cu1-O17 \\sim Cu1-O5
 with sigma of 0.02
 O17-C02L \\sim O5-C21
 with sigma of 0.02
 O00S-C61 \\sim O4-C19
 with sigma of 0.02
 C61-C60 \\sim C20-C19
 with sigma of 0.02
 C02L-C60 \\sim C20-C21
 with sigma of 0.02
 C02L-C0 \\sim C22-C21
 with sigma of 0.02
 F0-C0 \\sim F5-C22
 with sigma of 0.02
 F4-C22 \\sim F02Q-C0
 with sigma of 0.02
 F02M-C0 \\sim F6-C22
 with sigma of 0.02
 C18-C19 \\sim C61-C62
 with sigma of 0.02
 F3-C18 \\sim F34-C62
 with sigma of 0.02
 F41A-C62 \\sim F2-C18
 with sigma of 0.02
 F40A-C62 \\sim F1-C18
 with sigma of 0.02
 F20-C55 \\sim F35-C55
 with sigma of 0.02
 F21-C55 \\sim F37-C55
 with sigma of 0.02
 F35-C55 \\sim F20-C55
 with sigma of 0.02
 F19-C55 \\sim F36-C55
 with sigma of 0.02
 F37-C55 \\sim F21-C55
 with sigma of 0.02
 F35-F36 \\sim F35-F37 \\sim F36-F37
 with sigma of 0.02
 F21-F19 \\sim F21-F20 \\sim F19-F20
 with sigma of 0.02
 F12-C27 \\sim F33-C27
 with sigma of 0.02
 F11-C27 \\sim F32-C27
 with sigma of 0.02
 F10-C27 \\sim F31-C27
 with sigma of 0.02
 F33-C27 \\sim F12-C27
 with sigma of 0.02
 F11-F10 \\sim F11-F12 \\sim F10-F12
 with sigma of 0.02
 F31-F32 \\sim F32-F33 \\sim F31-F33
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O5 \\sim F3 \\sim C21 \\sim F6 \\sim F4 \\sim C19 \\sim C20 \\sim F5 \\sim C22
\\sim C18 \\sim F1 \\sim F2 \\sim O4: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
F0 \\sim F02Q \\sim C0 \\sim F02M \\sim C02L \\sim O17 \\sim C60 \\sim C61
\\sim F34 \\sim C62 \\sim F40A \\sim F41A \\sim O00S: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
F19 \\sim F20 \\sim F21: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
F35 \\sim F36 \\sim F37: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
F12 \\sim F10 \\sim F11: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
F33 \\sim F32 \\sim F31: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
F36 \\sim F20 \\sim F19 \\sim F37 \\sim F21 \\sim F35: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(F33) = Uanis(F12)
Uanis(F19) = Uanis(F36)
Uanis(F11) = Uanis(F32)
Uanis(F31) = Uanis(F10)
Uanis(O4) = Uanis(O00S)
Uanis(O17) = Uanis(O5)
4. Others
 Sof(F0)=Sof(F02Q)=Sof(C0)=Sof(F02M)=Sof(C02L)=Sof(O17)=Sof(C60)=Sof(H60)=
 Sof(C61)=Sof(O00S)=Sof(F34)=Sof(C62)=Sof(F40A)=Sof(F41A)=1-FVAR(1)
 Sof(O5)=Sof(O4)=Sof(F3)=Sof(C21)=Sof(F6)=Sof(F4)=Sof(C19)=Sof(C20)=Sof(H20)=
 Sof(F5)=Sof(C22)=Sof(C18)=Sof(F1)=Sof(F2)=FVAR(1)
 Sof(F37)=Sof(F36)=Sof(F35)=1-FVAR(2)
 Sof(F19)=Sof(F20)=Sof(F21)=FVAR(2)
 Sof(F32)=Sof(F31)=Sof(F33)=1-FVAR(3)
 Sof(F11)=Sof(F12)=Sof(F10)=FVAR(3)
5.a Aromatic/amide H refined with riding coordinates:
 C35(H35), C9(H9), C10(H10), C16(H16), C13(H13), C33(H33), C57(H57), C17(H17),
 C36(H36), C47(H47), C52(H52), C25(H25), C28(H28), C15(H15), C29(H29), C20(H20),
  C30(H30), C60(H60)
5.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C40(H40A,H40B,H40C), C6(H6A,H6B,H6C), C43(H43A,H43B,H43C),
 C37(H37A,H37B,H37C), C3(H3A,H3B,H3C), C5(H5A,H5B,H5C), C44(H44A,H44B,H44C),
 C14(H14A,H14B,H14C), C41(H41A,H41B,H41C)
;
_shelx_res_checksum              52746
_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
;