Trinuclear rare earth pyridyl-β-diketonate complexes: developing new methods towards finding lost toroidal spin states.
Mangundu, Patrick; Tanner, Kate E.; Bloomfield, Andrew; Barnard, Peter J.; White, Keith F.; Ho, Curtis C.; Yepuri, Nageshwar R.; Mole, Richard A.; Fuller, Rebecca O.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 10455–10466; doi:10.1039/d5dt01067e

data_7718895
_publ_section_title
;
 Trinuclear rare earth pyridyl-&#x3b2;-diketonate complexes: developing
 new methods towards finding lost toroidal spin states.
;
_journal_issue                   26
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              10455
_journal_page_last               10466
_journal_paper_doi               10.1039/d5dt01067e
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C27 H29 Dy3 N7 O22, H2 O, 2[[NO3]]'
_chemical_formula_sum            'C27 H31 Dy3 N9 O29'
_chemical_formula_weight         1433.11
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-12
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-05-05 deposited with the CCDC.	2025-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.417(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.4903(3)
_cell_length_b                   19.5628(5)
_cell_length_c                   20.6987(5)
_cell_measurement_reflns_used    16868
_cell_measurement_temperature    151(2)
_cell_measurement_theta_max      71.0110
_cell_measurement_theta_min      3.8180
_cell_volume                     4652.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 40.53 (release 29-04-2019))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      151(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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    -10.00  16.00   0.50   10.00    --  -38.50  77.00 -43.00   52
  2  \w    -61.00 -19.00   0.50   10.00    --  -38.50  77.00 -43.00   84
  3  \w    135.00 164.00   0.50   40.00    --  100.00  77.00 -43.00   58
  4  \w     37.00  93.00   0.50   40.00    --  100.00 -77.00-169.00  112
  5  \w    -45.00  24.00   0.50   10.00    --  -38.50  32.00  90.00  138
  6  \w     -5.00  22.00   0.50   10.00    --  -38.50  32.00 -30.00   54
  7  \w    -27.00  25.00   0.50   10.00    --  -38.50  77.00  90.00  104
  8  \w     -7.00  19.00   0.50   10.00    --  -38.50  43.00-150.00   52
  9  \w    -41.00 -15.00   0.50   10.00    --  -38.50  43.00-150.00   52
 10  \w   -101.00 -30.00   0.50   10.00    --  -38.50 -54.00  90.00  142
 11  \w   -106.00 -30.00   0.50   10.00    --  -38.50 -21.00-120.00  152
 12  \w    -59.00 -22.00   0.50   10.00    --  -38.50 -54.00 -30.00   74
 13  \w    -47.00   9.00   0.50   10.00    --  -38.50 104.00-180.00  112
 14  \w    -74.00 -35.00   0.50   10.00    --  -38.50 104.00 -30.00   78
 15  \w    -98.00 -73.00   0.50   10.00    --  -38.50 -54.00 -30.00   50
 16  \w   -100.00 -21.00   0.50   10.00    --  -38.50 -65.00  60.00  158
 17  \w   -108.00 -42.00   0.50   10.00    --  -38.50 -21.00 150.00  132
 18  \w    -94.00 -54.00   0.50   10.00    --  -38.50 138.00 120.00   80
 19  \w    -41.00 -16.00   0.50   10.00    --  -38.50 138.00 120.00   50
 20  \w    -31.00  12.00   0.50   10.00    --  -38.50 104.00 -30.00   86
 21  \w    -19.00  21.00   0.50   10.00    --   42.60 -77.00-169.00   80
 22  \w     22.00 105.00   0.50   10.00    --   42.60  65.00 -30.00  166
 23  \w    -19.00  55.00   0.50   10.00    --   42.60 -43.00-180.00  148
 24  \w      8.00  78.00   0.50   10.00    --   42.60-104.00  60.00  140
 25  \w     13.00  54.00   0.50   10.00    --   42.60 -43.00  60.00   82
 26  \w    -18.00   8.00   0.50   10.00    --   42.60 -43.00  60.00   52
 27  \w     28.00  56.00   0.50   10.00    --   42.60-104.00  30.00   56
 28  \w     25.00  84.00   0.50   40.00    --  100.00  -8.00 120.00  118
 29  \w     35.00  69.00   0.50   40.00    --  100.00 -33.00  60.00   68
 30  \w     41.00 108.00   0.50   40.00    --  100.00-117.00-180.00  134
 31  \w     38.00 119.00   0.50   40.00    --  100.00 -59.00  60.00  162
 32  \w     54.00 103.00   0.50   40.00    --  100.00 -50.00 -30.00   98
 33  \w     81.00 106.00   0.50   40.00    --  100.00 -25.00  90.00   50
 34  \w    125.00 152.00   0.50   40.00    --  100.00  33.00  90.00   54
 35  \w     52.00 109.00   0.50   40.00    --  100.00-117.00 -30.00  114
 36  \w     38.00  63.00   0.50   40.00    --  100.00-145.00 -60.00   50
 37  \w     94.00 120.00   0.50   40.00    --  100.00 -87.00-180.00   52
 38  \w    125.00 165.00   0.50   40.00    --  100.00  77.00 -60.00   80
 39  \w     56.00 112.00   0.50   40.00    --  100.00 -59.00 -60.00  112
 40  \w    106.00 150.00   0.50   40.00    --  100.00 145.00-150.00   88
 41  \w     39.00 108.00   0.50   40.00    --  100.00-117.00  90.00  138
 42  \w     63.00  99.00   0.50   40.00    --  100.00 -87.00  60.00   72
 43  \w     81.00 106.00   0.50   40.00    --  100.00 -96.00 -30.00   50
 44  \w     44.00 100.00   0.50   40.00    --  100.00 -50.00  90.00  112
 45  \w     37.00 116.00   0.50   40.00    --  100.00 -50.00-180.00  158
 46  \w     30.00  61.00   0.50   40.00    --  100.00 -96.00 -30.00   62
 47  \w    129.00 164.00   0.50   40.00    --  100.00  68.00 -90.00   70
 48  \w     87.00 152.00   0.50   40.00    --  100.00  50.00  60.00  130
 49  \w     53.00 107.00   0.50   40.00    --  100.00-117.00   0.00  108
 50  \w     66.00  92.00   0.50   40.00    --  100.00 -87.00-180.00   52
 51  \w     65.00 126.00   0.50   40.00    --  100.00-145.00  90.00  122
 52  \w    105.00 161.00   0.50   40.00    --  100.00  17.00  30.00  112
 53  \w     42.00  89.00   0.50   40.00    --  100.00 -96.00-180.00   94
 54  \w     89.00 126.00   0.50   40.00    --  100.00-145.00 -60.00   74
 55  \w     98.00 125.00   0.50   40.00    --  100.00 -77.00 -30.00   54
 56  \w     85.00 111.00   0.50   40.00    --  100.00 -42.00-180.00   52
 57  \w    119.00 144.00   0.50   40.00    --  100.00 117.00-120.00   50
 58  \w     79.00 157.00   0.50   40.00    --  100.00  68.00 -30.00  156
 59  \w     36.00 109.00   0.50   40.00    --  100.00 -25.00 -30.00  146
 60  \w     36.00  61.00   0.50   40.00    --  100.00-117.00 -90.00   50
 61  \w     72.00 104.00   0.50   40.00    --  100.00-117.00 -60.00   64
 62  \w     32.00  60.00   0.50   40.00    --  100.00 -25.00  90.00   56
 63  \w     84.00 119.00   0.50   40.00    --  100.00 -77.00  60.00   70
 64  \w     60.00  86.00   0.50   40.00    --  100.00 -87.00 -60.00   52
 65  \w    124.00 157.00   0.50   40.00    --  100.00 145.00 120.00   66
 66  \w     34.00  89.00   0.50   40.00    --  100.00 -17.00-150.00  110
 67  \w    132.00 162.00   0.50   40.00    --  100.00  50.00 120.00   60
 68  \w     84.00 109.00   0.50   40.00    --  100.00-117.00 150.00   50
 69  \w     85.00 111.00   0.50   40.00    --  100.00  50.00 120.00   52
 70  \w     64.00 108.00   0.50   40.00    --  100.00 -44.00-109.94   88
 71  \w     88.00 114.00   0.50   40.00    --  100.00  -8.00 120.00   52
 72  \w    117.00 142.00   0.50   40.00    --  100.00 117.00 -60.00   50
 73  \w    124.00 165.00   0.50   40.00    --  100.00 117.00  90.00   82
 74  \w     53.00  98.00   0.50   40.00    --  100.00-117.00 120.00   90
 75  \w     58.00 109.00   0.50   40.00    --  100.00 -33.00 150.00  102
 76  \w    131.00 157.00   0.50   40.00    --  100.00  50.00  30.00   52
 77  \w     81.00 106.00   0.50   40.00    --  100.00  68.00 -90.00   50
 78  \w    100.00 125.00   0.50   40.00    --  100.00 -77.00  90.00   50
 79  \w     59.00 120.00   0.50   40.00    --  100.00  -9.00 176.85  122
 80  \w     87.00 113.00   0.50   40.00    --  100.00  42.00  30.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1292925000
_diffrn_orient_matrix_UB_12      -0.0082156000
_diffrn_orient_matrix_UB_13      0.0186243000
_diffrn_orient_matrix_UB_21      -0.0183867000
_diffrn_orient_matrix_UB_22      0.0463093000
_diffrn_orient_matrix_UB_23      0.0592783000
_diffrn_orient_matrix_UB_31      -0.0303711000
_diffrn_orient_matrix_UB_32      -0.0631099000
_diffrn_orient_matrix_UB_33      0.0410447000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1147
_diffrn_reflns_av_unetI/netI     0.0618
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            62556
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.864
_diffrn_reflns_theta_min         3.847
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    26.301
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44780
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.046
_exptl_crystal_description       plate
_exptl_crystal_F_000             2744
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.02
_refine_diff_density_max         1.315
_refine_diff_density_min         -1.723
_refine_diff_density_rms         0.166
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.061
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     552
_refine_ls_number_reflns         8994
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.061
_refine_ls_R_factor_all          0.0799
_refine_ls_R_factor_gt           0.0598
_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^)+(0.1024P)^2^+0.0746P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1605
_refine_ls_wR_factor_ref         0.1726
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6549
_reflns_number_total             8994
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01067e2.cif
_cod_data_source_block           complex_5
_cod_depositor_comments
'Adding full bibliography for 7718894--7718899.cif.'
_cod_database_code               7718895
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N4 O4 Cl4 Dy'
_shelx_estimated_absorpt_t_max   0.621
_shelx_estimated_absorpt_t_min   0.260
_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, All O(H) groups, All O(H,H) groups
2. Restrained distances
 Dy1-H2Wa \\sim Dy1-H2Wb
 with sigma of 0.02
3.a Free rotating group:
 O2W(H2Wa,H2Wb), O20(H20a,H20b)
3.b Rotating group:
 O1W(H1Wa,H1Wb)
3.c Ternary CH refined with riding coordinates and stretchable bonds:
 O7(H7)
3.d Aromatic/amide H refined with riding coordinates:
 C16(H16), C19(H19), C1(H1), C22(H22), C7(H7a), C4(H4), C25(H25), C10(H10),
 C12(H12), C2(H2), C20(H20), C13(H13), C11(H11), C3(H3), C21(H21)
3.e Idealised Me refined as rotating group:
 C18(H18a,H18b,H18c), C9(H9a,H9b,H9c), C27(H27a,H27b,H27c)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 262 electrons were 
found in a volume of 1008\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2[[NO3]-] per Formula Unit 
which account for 256 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              48706
_shelx_hkl_checksum              81584
_shelx_fab_checksum              21714
_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 2.764
_oxdiff_exptl_absorpt_empirical_full_min 0.391