A tetraazanaphthalene radical-bridged dysprosium single-molecule magnet with a large coercive field.
Benner, Florian; Deshapriya, Saroshan; Demir, Selvan; Chemical science 16 (2025) 20806–20822; doi:10.1039/d5sc05358g

data_1575969
_publ_section_title
;
 A tetraazanaphthalene radical-bridged dysprosium single-molecule magnet
 with a large coercive field.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              20806
_journal_page_last               20822
_journal_paper_doi               10.1039/d5sc05358g
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'B C24 F20, 2(C23 H32 Dy N2)'
_chemical_formula_sum            'C70 H64 B Dy2 F20 N4'
_chemical_formula_weight         1677.06
_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     dual
_audit_creation_date             2025-05-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-05-30 deposited with the CCDC.	2025-09-15 downloaded from the CCDC.
;
_cell_angle_alpha                77.5000(10)
_cell_angle_beta                 78.9540(10)
_cell_angle_gamma                83.5720(10)
_cell_formula_units_Z            2
_cell_length_a                   10.56700(10)
_cell_length_b                   12.64630(10)
_cell_length_c                   25.5268(2)
_cell_measurement_reflns_used    38205
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      79.8370
_cell_measurement_theta_min      3.5520
_cell_volume                     3259.82(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.142a 64-bit (release 17-10-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.984
_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    -61.00 -35.00   0.50    0.40    --  -47.52 -52.00 131.00   52
  2  \w   -111.00 -85.00   0.50    0.40    --  -47.52 -52.00 131.00   52
  3  \w     59.00 120.00   0.50    0.40    --   47.52  52.00 -82.00  122
  4  \w    -13.00  27.00   0.50    0.40    --   47.52 -52.00 131.00   80
  5  \w   -145.00-120.00   0.50    1.60    --  -91.75 -52.00 131.00   50
  6  \w    -61.00 -36.00   0.50    1.60    --  -91.75  52.00 -82.00   50
  7  \w    138.00 164.00   0.50    1.60    --  113.25  52.00 -82.00   52
  8  \w    -69.00  16.00   0.50    0.40    --  -47.52  77.00-180.00  170
  9  \w    -30.00  28.00   0.50    0.40    --  -47.52  19.00-150.00  116
 10  \w    -59.00  25.00   0.50    0.40    --  -47.52  52.00 -82.00  168
 11  \w    -31.00  16.00   0.50    0.40    --  -47.52  19.00 -90.00   94
 12  \w     36.00  81.00   0.50    0.40    --   47.52-125.00   0.00   90
 13  \w    -26.00  27.00   0.50    0.40    --   47.52 -19.00  30.00  106
 14  \w    -69.00 -27.00   0.50    1.60    --  -91.75  61.00  30.00   84
 15  \w    -67.00 -19.00   0.50    1.60    --  -91.75  61.00  90.00   96
 16  \w     60.00  91.00   0.50    1.60    --  113.25-125.00  30.00   62
 17  \w     42.00  67.00   0.50    1.60    --  113.25 -61.00   0.00   50
 18  \w     49.00 103.00   0.50    1.60    --  113.25 -94.00  60.00  108
 19  \w     55.00 104.00   0.50    1.60    --  113.25 -94.00 -30.00   98
 20  \w     44.00 103.00   0.50    1.60    --  113.25 -98.00 -48.19  118
 21  \w    107.00 170.00   0.50    1.60    --  113.25  61.00  90.00  126
 22  \w     42.00  67.00   0.50    1.60    --  113.25 -61.00 -60.00   50
 23  \w    134.00 160.00   0.50    1.60    --  113.25  61.00 150.00   52
 24  \w    106.00 132.00   0.50    1.60    --  113.25  45.00-120.00   52
 25  \w     67.00 104.00   0.50    1.60    --  113.25 -94.00 120.00   74
 26  \w    153.00 178.00   0.50    1.60    --  113.25  45.00-180.00   50
 27  \w    151.00 178.00   0.50    1.60    --  113.25  45.00-120.00   54
 28  \w     59.00 104.00   0.50    1.60    --  113.25 -94.00-180.00   90
 29  \w    106.00 146.00   0.50    1.60    --  113.25  15.00   0.00   80
 30  \w     76.00 102.00   0.50    1.60    --  113.25 -94.00  30.00   52
 31  \w     47.00 101.00   0.50    1.60    --  113.25 -94.00-150.00  108
 32  \w     44.00  81.00   0.50    1.60    --  113.25-125.00 -30.00   74
 33  \w    120.00 154.00   0.50    1.60    --  113.25  45.00  60.00   68
 34  \w     47.00  73.00   0.50    1.60    --  113.25 -94.00   0.00   52
 35  \w     77.00 103.00   0.50    1.60    --  113.25 -94.00   0.00   52
 36  \w     45.00  83.00   0.50    1.60    --  113.25 -77.00-120.00   76
 37  \w     45.00  71.00   0.50    1.60    --  113.25 -85.00  43.47   52
 38  \w     70.00 104.00   0.50    1.60    --  113.25 -94.00  90.00   68
 39  \w    114.00 140.00   0.50    1.60    --  113.25  77.00  90.00   52
 40  \w     43.00  72.00   0.50    1.60    --  113.25 -77.00  60.00   58
 41  \w     56.00 104.00   0.50    1.60    --  113.25 -94.00-120.00   96
 42  \w    137.00 177.00   0.50    1.60    --  113.25  45.00 -90.00   80
 43  \w     42.00  67.00   0.50    1.60    --  113.25 -61.00 150.00   50
 44  \w    109.00 135.00   0.50    1.60    --  113.25  30.00-120.00   52
 45  \w    102.00 154.00   0.50    1.60    --  113.25  30.00   0.00  104
 46  \w     54.00 103.00   0.50    1.60    --  113.25 -94.00 150.00   98
 47  \w     46.00  81.00   0.50    1.60    --  113.25 -77.00 -90.00   70
 48  \w     45.00  93.00   0.50    1.60    --  113.25 -77.00 -30.00   96
 49  \w     73.00  99.00   0.50    1.60    --  113.25-125.00 150.00   52
 50  \w    102.00 144.00   0.50    1.60    --  113.25  45.00 150.00   84
 51  \w    105.00 174.00   0.50    1.60    --  113.25  15.00-120.00  138
 52  \w     45.00  73.00   0.50    1.60    --  113.25-125.00 -60.00   56
 53  \w     56.00 107.00   0.50    1.60    --  113.25-125.00  90.00  102
 54  \w    110.00 148.00   0.50    1.60    --  113.25  61.00-180.00   76
 55  \w     69.00  99.00   0.50    1.60    --  113.25 -77.00 150.00   60
 56  \w    104.00 135.00   0.50    1.60    --  113.25  15.00 150.00   62
 57  \w    151.00 178.00   0.50    1.60    --  113.25  15.00 150.00   54
 58  \w    106.00 146.00   0.50    1.60    --  113.25  61.00   0.00   80
 59  \w    122.00 177.00   0.50    1.60    --  113.25 125.00-180.00  110
 60  \w     60.00 104.00   0.50    1.60    --  113.25-125.00  60.00   88
 61  \w     80.00 106.00   0.50    1.60    --  113.25-125.00   0.00   52
 62  \w     50.00 106.00   0.50    1.60    --  113.25-125.00 120.00  112
 63  \w     65.00  91.00   0.50    1.60    --  113.25 -84.00 156.20   52
 64  \w    114.00 139.00   0.50    1.60    --  113.25 -84.00 156.20   50
 65  \w     45.00  70.00   0.50    1.60    --  113.25 -85.00 107.12   50
 66  \w     97.00 122.00   0.50    1.60    --  113.25 -85.00 107.12   50
 67  \w     52.00  78.00   0.50    1.60    --  113.25 -86.00-135.44   52
 68  \w     91.00 122.00   0.50    1.60    --  113.25 -86.00-135.44   62
 69  \w    101.00 157.00   0.50    1.60    --  113.25  30.00  60.00  112
 70  \w    151.00 178.00   0.50    1.60    --  113.25 125.00 -90.00   54
 71  \w     98.00 131.00   0.50    1.60    --  113.25 125.00 -90.00   66
 72  \w    111.00 155.00   0.50    1.60    --  113.25  15.00 -90.00   88
 73  \w    105.00 132.00   0.50    1.60    --  113.25 -85.00  43.47   54
 74  \w     44.00  69.00   0.50    1.60    --  113.25 -77.00   0.00   50
 75  \w    139.00 178.00   0.50    1.60    --  113.25  77.00 -30.00   78
 76  \w    115.00 140.00   0.50    1.60    --  113.25  77.00   0.00   50
 77  \w    153.00 178.00   0.50    1.60    --  113.25  77.00   0.00   50
 78  \w     47.00  72.00   0.50    1.60    --  113.25 -77.00 120.00   50
 79  \w    115.00 140.00   0.50    1.60    --  113.25  61.00 -90.00   50
 80  \w    110.00 160.00   0.50    1.60    --  113.25  61.00 -60.00  100
 81  \w    106.00 131.00   0.50    1.60    --  113.25  45.00   0.00   50
 82  \w     43.00  68.00   0.50    1.60    --  113.25 -61.00 120.00   50
 83  \w    103.00 128.00   0.50    1.60    --  113.25  30.00 -60.00   50
 84  \w    146.00 171.00   0.50    1.60    --  113.25  30.00 -60.00   50
 85  \w    120.00 148.00   0.50    1.60    --  113.25  30.00  90.00   56
 86  \w    122.00 147.00   0.50    1.60    --  113.25  15.00  60.00   50
 87  \w    137.00 163.00   0.50    1.60    --  113.25 125.00-150.00   52
 88  \w     49.00  95.00   0.50    1.60    --  113.25 -84.00-103.54   92
 89  \w     44.00  83.00   0.50    1.60    --  113.25 -84.00 117.90   78
 90  \w    114.00 139.00   0.50    1.60    --  113.25 -84.00 117.90   50
 91  \w     98.00 123.00   0.50    1.60    --  113.25 -86.00 -99.14   50
 92  \w    106.00 138.00   0.50    1.60    --  113.25  45.00-180.00   64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1324795000
_diffrn_orient_matrix_UB_12      0.0164494000
_diffrn_orient_matrix_UB_13      0.0360348000
_diffrn_orient_matrix_UB_21      -0.0080197000
_diffrn_orient_matrix_UB_22      -0.1239992000
_diffrn_orient_matrix_UB_23      0.0163581000
_diffrn_orient_matrix_UB_31      0.0675985000
_diffrn_orient_matrix_UB_32      -0.0027536000
_diffrn_orient_matrix_UB_33      0.0487066000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0459
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            71904
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.426
_diffrn_reflns_theta_min         3.590
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.033
_exptl_absorpt_correction_T_max  0.720
_exptl_absorpt_correction_T_min  0.157
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.142a (Rigaku Oxford Diffraction, 2024)
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            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.709
_exptl_crystal_description       block
_exptl_crystal_F_000             1658
_exptl_crystal_size_max          0.217
_exptl_crystal_size_mid          0.125
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.483
_refine_diff_density_min         -2.017
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.058
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1086
_refine_ls_number_reflns         14063
_refine_ls_number_restraints     624
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0410
_refine_ls_R_factor_gt           0.0383
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0515P)^2^+5.6559P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0974
_refine_ls_wR_factor_ref         0.0991
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13227
_reflns_number_total             14063
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05358g2.cif
_cod_data_source_block           '[((CpStar)2Dy)2(tan)]BArF'
_cod_depositor_comments
'Adding full bibliography for 1575968--1575969.cif.'
_cod_database_code               1575969
_shelxl_version_number           2013-3
_chemical_oxdiff_formula         C70H64BDy2F20N4
_shelx_estimated_absorpt_t_max   0.624
_shelx_estimated_absorpt_t_min   0.164
_reflns_odcompleteness_completeness 97.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.95
_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
 C30-C31 \\sim C27-C31 \\sim C28-C27 \\sim C29-C28 \\sim C30-C29
 with sigma of 0.02
 C35-C30 \\sim C36-C31 \\sim C32-C27 \\sim C33-C28 \\sim C34-C29
 with sigma of 0.02
 C38-C39 \\sim C59-C60 \\sim C40-C39 \\sim C61-C60 \\sim C41-C40 \\sim C41-C37
\\sim C57-C61 \\sim C57-C58
 \\sim C37-C38 \\sim C58-C59
 with sigma of 0.02
 C31-C27 \\sim C50-C51
 with sigma of 0.02
 C31-C30 \\sim C50-C49
 with sigma of 0.02
 C31-C36 \\sim C50-C55
 with sigma of 0.02
 C27-C28 \\sim C51-C47
 with sigma of 0.02
 C27-C32 \\sim C51-C56
 with sigma of 0.02
 C28-C29 \\sim C47-C48
 with sigma of 0.02
 C28-C33 \\sim C47-C52
 with sigma of 0.02
 C29-C30 \\sim C48-C49
 with sigma of 0.02
 C29-C34 \\sim C48-C53
 with sigma of 0.02
 C30-C35 \\sim C49-C54
 with sigma of 0.02
 C31-C28 \\sim C50-C47
 with sigma of 0.04
 C31-C29 \\sim C50-C48
 with sigma of 0.04
 C31-C32 \\sim C50-C56
 with sigma of 0.04
 C31-C35 \\sim C50-C54
 with sigma of 0.04
 C27-C29 \\sim C51-C48
 with sigma of 0.04
 C27-C30 \\sim C51-C49
 with sigma of 0.04
 C27-C36 \\sim C51-C55
 with sigma of 0.04
 C27-C33 \\sim C51-C52
 with sigma of 0.04
 C28-C30 \\sim C47-C49
 with sigma of 0.04
 C28-C32 \\sim C47-C56
 with sigma of 0.04
 C28-C34 \\sim C47-C53
 with sigma of 0.04
 C29-C33 \\sim C48-C52
 with sigma of 0.04
 C29-C35 \\sim C48-C54
 with sigma of 0.04
 C30-C36 \\sim C49-C55
 with sigma of 0.04
 C30-C34 \\sim C49-C53
 with sigma of 0.04
 Dy2-C47 \\sim Dy2-C28 \\sim Dy2-C51 \\sim Dy2-C27 \\sim Dy2-C48 \\sim Dy2-C29
\\sim Dy2-C50 \\sim Dy2-C31
 \\sim Dy2-C49 \\sim Dy2-C30
 with sigma of 0.01
 Dy2-C39 \\sim Dy2-C60 \\sim Dy2-C40 \\sim Dy2-C61 \\sim Dy2-C41 \\sim Dy2-C57
\\sim Dy2-C37 \\sim Dy2-C58
 \\sim Dy2-C59 \\sim Dy2-C38
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C48 \\sim C28 \\sim C47 \\sim C27 \\sim C51 \\sim C31 \\sim C50 \\sim C30 \\sim
C49 \\sim C29: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C34 \\sim C53 \\sim C33 \\sim C52 \\sim C32 \\sim C56 \\sim C36 \\sim C55 \\sim
C35 \\sim C54: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C60 \\sim C40 \\sim C61 \\sim C41 \\sim C57 \\sim C37 \\sim C58 \\sim C38 \\sim
C59 \\sim C39: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C43 \\sim C64 \\sim C63 \\sim C42 \\sim C62 \\sim C46 \\sim C66 \\sim C45 \\sim
C65 \\sim C44: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C57)=Sof(C58)=Sof(C59)=Sof(C60)=Sof(C61)=Sof(C62)=Sof(H62A)=Sof(H62B)=
 Sof(H62C)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=Sof(C64)=Sof(H64A)=Sof(H64B)=
 Sof(H64C)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C66)=Sof(H66A)=Sof(H66B)=
 Sof(H66C)=1-FVAR(1)
 Sof(C37)=Sof(C38)=Sof(C39)=Sof(C40)=Sof(C41)=Sof(C42)=Sof(H42A)=Sof(H42B)=
 Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C44)=Sof(H44A)=Sof(H44B)=
 Sof(H44C)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=Sof(C46)=Sof(H46A)=Sof(H46B)=
 Sof(H46C)=FVAR(1)
 Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(C51)=Sof(C52)=Sof(H52A)=Sof(H52B)=
 Sof(H52C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C54)=Sof(H54A)=Sof(H54B)=
 Sof(H54C)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=Sof(C56)=Sof(H56A)=Sof(H56B)=
 Sof(H56C)=1-FVAR(2)
 Sof(C27)=Sof(C28)=Sof(C29)=Sof(C30)=Sof(C31)=Sof(C32)=Sof(H32A)=Sof(H32B)=
 Sof(H32C)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=Sof(C34)=Sof(H34A)=Sof(H34B)=
 Sof(H34C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=Sof(H36B)=
 Sof(H36C)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C24(H24), C26(H26), C2(H2), C3(H3)
5.b Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,
 H35C), C36(H36A,H36B,H36C), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C), C54(H54A,
 H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C62(H62A,H62B,H62C),
 C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,
 H66C), C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,
 H12B,H12C), C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C),
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C42(H42A,H42B,
 H42C), C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,
 H46B,H46C)
;
_shelx_res_checksum              34506
_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 1.354
_oxdiff_exptl_absorpt_empirical_full_min 0.668