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_1575968
_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         'C46 H64 Dy2 N4'
_chemical_formula_sum            'C46 H64 Dy2 N4'
_chemical_formula_weight         998.01
_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             2025-05-16
_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                90
_cell_angle_beta                 107.6150(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   12.46040(10)
_cell_length_b                   11.55780(10)
_cell_length_c                   15.47030(10)
_cell_measurement_reflns_used    21441
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      79.1710
_cell_measurement_theta_min      4.8460
_cell_volume                     2123.49(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.142a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.136a 64-bit (release 23-08-2024))'
_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 1.000
_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    -62.00  25.00   0.50    0.35    --  -47.63  57.00  30.00  174
  2  \w   -119.00   6.00   0.50    0.35    --  -47.63   0.00 120.00  250
  3  \w   -105.00 -35.00   0.50    0.35    --  -47.63 -19.00  60.00  140
  4  \w    -30.00  20.00   0.50    0.35    --  -47.63  19.00 -30.00  100
  5  \w     38.00  84.00   0.50    0.35    --   47.63-125.00-150.00   92
  6  \w    -24.00  41.00   0.50    0.35    --   47.63 -37.00-180.00  130
  7  \w     35.00  80.00   0.50    0.35    --   47.63 -99.00 -30.00   90
  8  \w    -50.00 -21.00   0.50    1.41    --  -91.75  45.00-150.00   58
  9  \w    106.00 133.00   0.50    1.41    --  113.25 -82.00 151.44   54
 10  \w     86.00 112.00   0.50    1.41    --  113.25 -84.00 -21.92   52
 11  \w     44.00  76.00   0.50    1.41    --  113.25 -82.00 151.44   64
 12  \w     75.00 104.00   0.50    1.41    --  113.25 -94.00 -90.00   58
 13  \w    102.00 133.00   0.50    1.41    --  113.25  45.00  60.00   62
 14  \w    106.00 147.00   0.50    1.41    --  113.25  30.00 -30.00   82
 15  \w     50.00  79.00   0.50    1.41    --  113.25 -86.00 119.90   58
 16  \w     89.00 115.00   0.50    1.41    --  113.25 -86.00 -21.75   52
 17  \w     76.00 102.00   0.50    1.41    --  113.25 -94.00-120.00   52
 18  \w     61.00  87.00   0.50    1.41    --  113.25 -86.00 -21.75   52
 19  \w     46.00 114.00   0.50    1.41    --  113.25 -86.00 -61.64  136
 20  \w     46.00 104.00   0.50    1.41    --  113.25 -94.00 -30.00  116
 21  \w    110.00 177.00   0.50    1.41    --  113.25  77.00 -30.00  134
 22  \w     42.00  67.00   0.50    1.41    --  113.25 -61.00 120.00   50
 23  \w    112.00 138.00   0.50    1.41    --  113.25  45.00-180.00   52
 24  \w     42.00  67.00   0.50    1.41    --  113.25 -94.00 -90.00   50
 25  \w    101.00 141.00   0.50    1.41    --  113.25  30.00 150.00   80
 26  \w    106.00 177.00   0.50    1.41    --  113.25  61.00-150.00  142
 27  \w     42.00  67.00   0.50    1.41    --  113.25 -61.00   0.00   50
 28  \w     42.00  67.00   0.50    1.41    --  113.25 -61.00  30.00   50
 29  \w     61.00 103.00   0.50    1.41    --  113.25 -94.00  30.00   84
 30  \w     42.00 104.00   0.50    1.41    --  113.25 -94.00 -60.00  124
 31  \w    137.00 175.00   0.50    1.41    --  113.25  45.00 -90.00   76
 32  \w    110.00 143.00   0.50    1.41    --  113.25  61.00  30.00   66
 33  \w     43.00  68.00   0.50    1.41    --  113.25 -61.00-150.00   50
 34  \w    113.00 138.00   0.50    1.41    --  113.25 -82.00  83.65   50
 35  \w     44.00  76.00   0.50    1.41    --  113.25 -94.00-150.00   64
 36  \w    153.00 178.00   0.50    1.41    --  113.25  61.00  30.00   50
 37  \w     43.00  68.00   0.50    1.41    --  113.25 -94.00  90.00   50
 38  \w     77.00 103.00   0.50    1.41    --  113.25 -94.00  90.00   52
 39  \w     63.00 100.00   0.50    1.41    --  113.25 -77.00-150.00   74
 40  \w    112.00 158.00   0.50    1.41    --  113.25  15.00 120.00   92
 41  \w    153.00 178.00   0.50    1.41    --  113.25  30.00 -60.00   50
 42  \w    101.00 147.00   0.50    1.41    --  113.25  30.00 -60.00   92
 43  \w    123.00 177.00   0.50    1.41    --  113.25  77.00 120.00  108
 44  \w     42.00  69.00   0.50    1.41    --  113.25 -94.00 120.00   54
 45  \w     78.00 103.00   0.50    1.41    --  113.25 -94.00 120.00   50
 46  \w     50.00  91.00   0.50    1.41    --  113.25 -77.00  60.00   82
 47  \w     46.00  89.00   0.50    1.41    --  113.25-125.00-150.00   86
 48  \w    103.00 129.00   0.50    1.41    --  113.25  45.00-120.00   52
 49  \w     47.00  73.00   0.50    1.41    --  113.25 -77.00   0.00   52
 50  \w    124.00 169.00   0.50    1.41    --  113.25  45.00   0.00   90
 51  \w     42.00  67.00   0.50    1.41    --  113.25 -61.00 -60.00   50
 52  \w    152.00 177.00   0.50    1.41    --  113.25  30.00 -30.00   50
 53  \w     47.00  72.00   0.50    1.41    --  113.25 -77.00  90.00   50
 54  \w    116.00 167.00   0.50    1.41    --  113.25  15.00 -90.00  102
 55  \w     42.00  74.00   0.50    1.41    --  113.25 -94.00-180.00   64
 56  \w     78.00 104.00   0.50    1.41    --  113.25 -94.00-180.00   52
 57  \w     70.00 101.00   0.50    1.41    --  113.25 -94.00   0.00   62
 58  \w    112.00 160.00   0.50    1.41    --  113.25 125.00   0.00   96
 59  \w     51.00  77.00   0.50    1.41    --  113.25 -82.00  83.65   52
 60  \w     60.00  86.00   0.50    1.41    --  113.25 -94.00  60.00   52
 61  \w     46.00  96.00   0.50    1.41    --  113.25-125.00  60.00  100
 62  \w    128.00 161.00   0.50    1.41    --  113.25  77.00-120.00   66
 63  \w    111.00 137.00   0.50    1.41    --  113.25 -86.00 119.90   52
 64  \w    121.00 165.00   0.50    1.41    --  113.25  45.00  90.00   88
 65  \w    139.00 164.00   0.50    1.41    --  113.25 125.00 -90.00   50
 66  \w    134.00 160.00   0.50    1.41    --  113.25 125.00  90.00   52
 67  \w    101.00 127.00   0.50    1.41    --  113.25 -85.00  14.67   52
 68  \w     65.00  91.00   0.50    1.41    --  113.25 -77.00 -60.00   52
 69  \w     72.00 104.00   0.50    1.41    --  113.25 -94.00 150.00   64
 70  \w     67.00 105.00   0.50    1.41    --  113.25-125.00  30.00   76
 71  \w    148.00 173.00   0.50    1.41    --  113.25  77.00  30.00   50
 72  \w    140.00 166.00   0.50    1.41    --  113.25  61.00-180.00   52
 73  \w    104.00 129.00   0.50    1.41    --  113.25  45.00  30.00   50
 74  \w    141.00 168.00   0.50    1.41    --  113.25  15.00-150.00   54
 75  \w    136.00 161.00   0.50    1.41    --  113.25 125.00 120.00   50
 76  \w    112.00 140.00   0.50    1.41    --  113.25 -86.00  93.75   56
;
_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      -0.0348632000
_diffrn_orient_matrix_UB_12      -0.0469877000
_diffrn_orient_matrix_UB_13      -0.0977488000
_diffrn_orient_matrix_UB_21      0.1059531000
_diffrn_orient_matrix_UB_22      -0.0769390000
_diffrn_orient_matrix_UB_23      0.0240713000
_diffrn_orient_matrix_UB_31      -0.0662835000
_diffrn_orient_matrix_UB_32      -0.0981602000
_diffrn_orient_matrix_UB_33      0.0279497000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0391
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            40102
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.259
_diffrn_reflns_theta_min         3.722
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.862
_exptl_absorpt_correction_T_max  0.750
_exptl_absorpt_correction_T_min  0.610
_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            'clear red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.561
_exptl_crystal_description       block
_exptl_crystal_F_000             1000
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.044
_refine_diff_density_max         0.445
_refine_diff_density_min         -1.433
_refine_diff_density_rms         0.076
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.097
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     437
_refine_ls_number_reflns         4631
_refine_ls_number_restraints     489
_refine_ls_restrained_S_all      1.075
_refine_ls_R_factor_all          0.0288
_refine_ls_R_factor_gt           0.0270
_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^)+(0.0130P)^2^+4.3686P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0635
_refine_ls_wR_factor_ref         0.0643
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4363
_reflns_number_total             4631
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05358g2.cif
_cod_data_source_block           ((CpStar)2Dy)2(tan)
_cod_depositor_comments
'Adding full bibliography for 1575968--1575969.cif.'
_cod_database_code               1575968
_shelxl_version_number           2013-3
_chemical_oxdiff_formula         C46H64N4Dy2
_shelx_estimated_absorpt_t_max   0.491
_shelx_estimated_absorpt_t_min   0.314
_reflns_odcompleteness_completeness 98.98
_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
 C6-C5 \\sim C7-C6 \\sim C8-C7 \\sim C8-C4 \\sim C5-C4 \\sim C9-C10 \\sim
C9-C13 \\sim C13-C12 \\sim C12-C11 ~
 C11-C10
 with sigma of 0.02
 Dy1-C5 \\sim Dy1-C4 \\sim Dy1-C9 \\sim Dy1-C11 \\sim Dy1-C6 \\sim Dy1-C13
\\sim Dy1-C8 \\sim Dy1-C12 ~
 Dy1-C10
 with sigma of 0.02
 C5-C15 \\sim C20-C10 \\sim C9-C19 \\sim C4-C14 \\sim C23-C13 \\sim C8-C18
\\sim C22-C12 \\sim C7-C17 ~
 C21-C11 \\sim C6-C16
 with sigma of 0.02
 C30-C29 \\sim C31-C30 \\sim C25-C24 \\sim C28-C24 \\sim C33-C29 \\sim C28-C27
\\sim C33-C32 \\sim C27-C26
 \\sim C32-C31 \\sim C26-C25
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C7 \\sim C12 \\sim C8 \\sim C13 \\sim C4 \\sim C9 \\sim C5 \\sim C10 \\sim C6
\\sim C11: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C25 \\sim C30 \\sim C31 \\sim C26 \\sim C32 \\sim C27 \\sim C33 \\sim C28 \\sim
C29 \\sim C24: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C15 \\sim C20: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(C29)=Sof(C30)=Sof(C31)=Sof(C32)=Sof(C33)=Sof(C39)=Sof(H39A)=Sof(H39B)=
 Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C41)=Sof(H41A)=Sof(H41B)=
 Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C43)=Sof(H43A)=Sof(H43B)=
 Sof(H43C)=1-FVAR(1)
 Sof(C24)=Sof(C25)=Sof(C26)=Sof(C27)=Sof(C28)=Sof(C34)=Sof(H34A)=Sof(H34B)=
 Sof(H34C)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(H35C)=Sof(C36)=Sof(H36A)=Sof(H36B)=
 Sof(H36C)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=Sof(C38)=Sof(H38A)=Sof(H38B)=
 Sof(H38C)=FVAR(1)
 Sof(C9)=Sof(C10)=Sof(C11)=Sof(C12)=Sof(C13)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C21)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C23)=Sof(H23A)=Sof(H23B)=
 Sof(H23C)=1-FVAR(2)
 Sof(C4)=Sof(C5)=Sof(C6)=Sof(C7)=Sof(C8)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(H14C)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C16)=Sof(H16A)=Sof(H16B)=
 Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=Sof(C18)=Sof(H18A)=Sof(H18B)=
 Sof(H18C)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3)
5.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C21(H21A,
 H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C34(H34A,H34B,H34C),
 C35(H35A,H35B,H35C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,
 H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C41(H41A,H41B,H41C), C42(H42A,
 H42B,H42C), C43(H43A,H43B,H43C)
;
_shelx_res_checksum              43734
_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 1.316
_oxdiff_exptl_absorpt_empirical_full_min 0.852