Design of a new nitronyl-nitroxide biradical and its complexes: synthesis, crystal structures and magnetic properties
Spinu, Cristian Andrei; Novitchi, Ghenadie; Hillebrand, Mihaela; Mocanu, Teodora; Ionita, Gabriela; Hanganu, Anamaria; Tecuceanu, Victoriţa; Andruh, Marius; CrystEngComm 27 (2025) 6462–6472; doi:10.1039/D5CE00795J

data_7250847
_publ_section_title
;
 Design of a new nitronyl-nitroxide biradical and its complexes:
 synthesis, crystal structures and magnetic properties
;
_journal_issue                   39
_journal_name_full               CrystEngComm
_journal_page_first              6462
_journal_page_last               6472
_journal_paper_doi               10.1039/D5CE00795J
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety
'C49 H38 F24 N6 Ni2 O18, 2(C6 H16 N), C H Cl2.59, 0.411(Cl)'
_chemical_formula_sum            'C62 H71 Cl3 F24 N8 Ni2 O18'
_chemical_formula_weight         1896.03
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-08-04
_audit_creation_method
;
Olex2 1.5-ac6-016
(compiled 2024.01.13 svn.r2f8d729c for Rigaku Oxford Diffraction, GUI svn.r6897)
;
_audit_update_record
;
2025-08-04 deposited with the CCDC.	2025-09-09 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.976(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.6913(9)
_cell_length_b                   34.9180(19)
_cell_length_c                   18.9060(8)
_cell_measurement_reflns_used    7631
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      31.1050
_cell_measurement_theta_min      2.1360
_cell_volume                     8332.8(8)
_computing_molecular_graphics    'Olex2 1.5-ac6-016 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-016 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.991
_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    -76.00   6.00   0.50  200.00    --   -4.89 -37.00 120.00  164
  2  \w    -18.00  49.50   0.50  200.00    --   -4.89  57.00 -90.00  135
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0025446000
_diffrn_orient_matrix_UB_12      0.0202844000
_diffrn_orient_matrix_UB_13      -0.0002426000
_diffrn_orient_matrix_UB_21      -0.0526762000
_diffrn_orient_matrix_UB_22      0.0007777000
_diffrn_orient_matrix_UB_23      -0.0167140000
_diffrn_orient_matrix_UB_31      -0.0194849000
_diffrn_orient_matrix_UB_32      0.0005604000
_diffrn_orient_matrix_UB_33      0.0338089000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0630
_diffrn_reflns_av_unetI/netI     0.0801
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       41
_diffrn_reflns_limit_k_min       -39
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            37357
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.937
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.668
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.556
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.76a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.511
_exptl_crystal_description       plate
_exptl_crystal_F_000             3864
_exptl_crystal_size_max          0.384
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.096
_refine_diff_density_max         0.892
_refine_diff_density_min         -0.646
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1323
_refine_ls_number_reflns         14552
_refine_ls_number_restraints     330
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.1423
_refine_ls_R_factor_gt           0.0716
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1206P)^2^+0.6969P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1893
_refine_ls_wR_factor_ref         0.2311
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7359
_reflns_number_total             14552
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00795j2.cif
_cod_data_source_block           cs385
_cod_depositor_comments
'Adding full bibliography for 7250845--7250847.cif.'
_cod_database_code               7250847
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C20 N4 O5 H10 Ni2 F12'
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.784
_olex2_refinement_description
;
1. Restrained distances
 C56-C57
 1.456 with sigma of 0.002
 C33-C34
 1.456 with sigma of 0.002
 C58B-C59B
 1.456 with sigma of 0.002
 C59B-N8
 2.432 with sigma of 0.004
 C59A-N8
 2.432 with sigma of 0.004
 F10A-C39 \\sim F11A-C39 \\sim F12A-C39 \\sim F12B-C39 \\sim F11B-C39 \\sim
F10B-C39
 with sigma of 0.01
 N8-C58A \\sim N8-C58B \\sim N8-C60A \\sim N8-C60B
 with sigma of 0.01
 C58A-C59A \\sim C58B-C59B \\sim C60A-C61A \\sim C60B-C61B
 with sigma of 0.01
 F15A-C41 \\sim F14A-C41 \\sim F14B-C41 \\sim F15B-C41 \\sim F13A-C41
 with sigma of 0.01
 F7A-C36 \\sim F7B-C36 \\sim F8A-C36 \\sim F9B-C36 \\sim F8B-C36 \\sim F9A-C36
 with sigma of 0.01
 F1B-C31 \\sim F3B-C31 \\sim F2B-C31 \\sim F3A-C31 \\sim F2A-C31 \\sim F1A-C31
 with sigma of 0.01
 F17A-C44 \\sim F18A-C44 \\sim F16A-C44 \\sim F16B-C44 \\sim F18B-C44 \\sim
F17B-C44
 with sigma of 0.01
 F6B-C34 \\sim F4B-C34 \\sim F5B-C34 \\sim F5A-C34 \\sim F4A-C34 \\sim F6A-C34
 with sigma of 0.01
 F24B-C46 \\sim F22A-C46 \\sim F22B-C46 \\sim F23A-C46 \\sim F23B-C46 \\sim
F24A-C46
 with sigma of 0.01
2. Rigid bond restraints
 F10A, C39, F11A, C39, F11B, C39, F10B, C39, F12A, C39
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F14A, C41
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C58A, N8, C58A, N8, C58A, C59A, C60A, C61A, C58B, C59B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F7A, C36, F8B, C36, F9A, C36, F8A, C36, F9B, C36, F7B, C36
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F3A, C31, F1B, C31, F2B, C31
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C50, C51
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 F6A, C34, F5B, C34
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
F10A \\sim F10B \\sim F11A \\sim F11B \\sim F12A \\sim F12B \\sim C39: within
1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
F9B \\sim F8B \\sim F7A \\sim F7B \\sim F9A \\sim F8A \\sim C36: within 1.7A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
C35 \\sim C36 \\sim C37: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 1.7A
C50 \\sim C51: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
C56 \\sim C57: within 1.7A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 1.7A
Cl3A \\sim Cl2B \\sim Cl2A \\sim Cl1B \\sim Cl1A \\sim Cl3B: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 1.7A
4. Others
 Sof(F15A)=Sof(H8B)=Sof(H62A)=Sof(F24B)=Sof(F23B)=Sof(F22B)=Sof(F16B)=
 Sof(F18B)=Sof(F17B)=Sof(F4B)=Sof(F10A)=Sof(F12A)=Sof(F1A)=Sof(F3A)=Sof(F2A)=
 Sof(F5A)=Sof(F6A)=Sof(F15B)=Sof(F14B)=Sof(F11B)=Sof(F7A)=Sof(F8B)=Sof(F9A)=
 Sof(C58A)=Sof(H58A)=Sof(H58B)=Sof(C60A)=Sof(H60A)=Sof(H60B)=Sof(C59A)=
 Sof(H59A)=Sof(H59B)=Sof(H59C)=Sof(C61A)=Sof(H61D)=Sof(H61E)=Sof(H61F)=
 Sof(Cl2B)=Sof(Cl1B)=Sof(Cl3B)=1-FVAR(1)
 Sof(F18A)=Sof(F14A)=Sof(F17A)=Sof(F22A)=Sof(H8A)=Sof(F6B)=Sof(F1B)=Sof(F16A)=
 Sof(F24A)=Sof(F23A)=Sof(Cl1A)=Sof(Cl3A)=Sof(Cl2A)=Sof(H62)=Sof(F5B)=Sof(F3B)=
 Sof(F2B)=Sof(F11A)=Sof(F4A)=Sof(F13A)=Sof(F12B)=Sof(F10B)=Sof(F9B)=Sof(F8A)=
 Sof(F7B)=Sof(C61B)=Sof(H61A)=Sof(H61B)=Sof(H61C)=Sof(C58B)=Sof(H58C)=Sof(H58D)=
 Sof(C59B)=Sof(H59D)=Sof(H59E)=Sof(H59F)=Sof(C60B)=Sof(H60C)=Sof(H60D)=
 Sof(F13B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 N7(H7), N8(H8B), N8(H8A), C62(H62), C62(H62A)
5.b Secondary CH2 refined with riding coordinates:
 C54(H54A,H54B), C52(H52A,H52B), C56(H56A,H56B), C50(H50A,H50B), C58A(H58A,
 H58B), C60A(H60A,H60B), C58B(H58C,H58D), C60B(H60C,H60D)
5.c Me refined with riding coordinates:
 C59B(H59D,H59E,H59F), C61A(H61D,H61E,H61F)
5.d Aromatic/amide H refined with riding coordinates:
 C9(H9), C22(H22), C11(H11), C18(H18), C42(H42), C32(H32), C47(H47), C37(H37)
5.e Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C29(H29A,H29B,H29C), C25(H25A,H25B,H25C), C15(H15A,H15B,
 H15C), C28(H28A,H28B,H28C), C16(H16A,H16B,H16C), C2(H2A,H2B,H2C), C5(H5A,H5B,
 H5C), C55(H55A,H55B,H55C), C6(H6A,H6B,H6C), C3(H3A,H3B,H3C), C51(H51A,H51B,
 H51C), C57(H57A,H57B,H57C), C53(H53A,H53B,H53C), C61B(H61A,H61B,H61C),
 C59A(H59A,H59B,H59C)
;
_shelx_res_checksum              84340
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 1.546
_oxdiff_exptl_absorpt_empirical_full_min 0.555