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_7718898
_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
'2(C27 H34 Cl Ho3 N3 O13), 6(Cl), 2(C2 H6 O), 1[C6H24O6Cl2]'
_chemical_formula_sum            'C64 H104 Cl10 Ho6 N6 O34'
_chemical_formula_weight         2845.61
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-20
_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                 94.5210(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.2181(2)
_cell_length_b                   15.50480(10)
_cell_length_c                   35.3931(4)
_cell_measurement_reflns_used    26902
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      70.9270
_cell_measurement_theta_min      3.7240
_cell_volume                     9966.31(17)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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      150.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_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    -81.00 -46.00   0.50    3.00    --  -38.50 118.00-163.00   70
  2  \w    -82.00 -55.00   0.50    3.00    --  -38.50-160.00 -42.00   54
  3  \w    -61.00 -28.00   0.50    3.00    --  -38.50 160.00 -11.00   66
  4  \w    -36.00  -6.00   0.50    3.00    --  -38.50 118.00-163.00   60
  5  \w     24.00  80.00   0.50    3.00    --   42.60-118.00 110.00  112
  6  \w     52.00 108.00   0.50    3.00    --   42.60-160.00 -42.00  112
  7  \w    120.00 146.00   0.50   12.00    --  100.00 118.00-163.00   52
  8  \w     98.00 124.00   0.50   12.00    --  100.00 160.00 -11.00   52
  9  \w     72.00  97.00   0.50   12.00    --  100.00-118.00 110.00   50
 10  \w    -33.00  28.00   0.50    3.00    --  -38.50  21.00 -30.00  122
 11  \w   -100.00 -42.00   0.50    3.00    --  -38.50 -43.00  30.00  116
 12  \w    -63.00 -37.00   0.50    3.00    --  -38.50  77.00   0.00   52
 13  \w    -49.00  -7.00   0.50    3.00    --  -38.50  21.00 -90.00   84
 14  \w    -30.00  22.00   0.50    3.00    --  -38.50  77.00   0.00  104
 15  \w     -2.00  31.00   0.50    3.00    --  -38.50  21.00 -90.00   66
 16  \w    -32.00  -6.00   0.50    3.00    --  -38.50 104.00 120.00   52
 17  \w    -96.00 -59.00   0.50    3.00    --  -38.50 -21.00 150.00   74
 18  \w    -99.00 -36.00   0.50    3.00    --  -38.50 -65.00 -30.00  126
 19  \w    -61.00 -36.00   0.50    3.00    --  -38.50 104.00 120.00   50
 20  \w   -101.00 -41.00   0.50    3.00    --  -38.50 -32.00  30.00  120
 21  \w      4.00  29.00   0.50    3.00    --  -38.50   0.00 -60.00   50
 22  \w    -47.00  -5.00   0.50    3.00    --  -38.50  43.00 -90.00   84
 23  \w    -51.00  15.00   0.50    3.00    --  -38.50  43.00-180.00  132
 24  \w     37.00 105.00   0.50    3.00    --   42.60  54.00 -60.00  136
 25  \w    -19.00   6.00   0.50    3.00    --   42.60 -54.00 -60.00   50
 26  \w     11.00  58.00   0.50    3.00    --   42.60 -54.00 -60.00   94
 27  \w    -18.00  65.00   0.50    3.00    --   42.60 -77.00 150.00  166
 28  \w     64.00 104.00   0.50    3.00    --   42.60  65.00  90.00   80
 29  \w      9.00  71.00   0.50    3.00    --   42.60 -89.00 -30.00  124
 30  \w     69.00  95.00   0.50   12.00    --  100.00-117.00  30.00   52
 31  \w     38.00  72.00   0.50   12.00    --  100.00-145.00 120.00   68
 32  \w     92.00 154.00   0.50   12.00    --  100.00  25.00  30.00  124
 33  \w     88.00 132.00   0.50   12.00    --  100.00 145.00-120.00   88
 34  \w     81.00 123.00   0.50   12.00    --  100.00 -77.00 -60.00   84
 35  \w     40.00  66.00   0.50   12.00    --  100.00 -77.00 -60.00   52
 36  \w     80.00 107.00   0.50   12.00    --  100.00  -8.00-150.00   54
 37  \w    125.00 161.00   0.50   12.00    --  100.00  77.00-180.00   72
 38  \w     38.00  79.00   0.50   12.00    --  100.00 -42.00   0.00   82
 39  \w     36.00  84.00   0.50   12.00    --  100.00 -96.00 -60.00   96
 40  \w     71.00 108.00   0.50   12.00    --  100.00 -42.00 150.00   74
 41  \w     78.00 104.00   0.50   12.00    --  100.00 -68.00 -60.00   52
 42  \w     40.00  81.00   0.50   12.00    --  100.00 -42.00 -60.00   82
 43  \w    105.00 136.00   0.50   12.00    --  100.00  96.00  60.00   62
 44  \w     85.00 127.00   0.50   12.00    --  100.00 -87.00  90.00   84
 45  \w     38.00 109.00   0.50   12.00    --  100.00-117.00   0.00  142
 46  \w    101.00 126.00   0.50   12.00    --  100.00-145.00-120.00   50
 47  \w     39.00 126.00   0.50   12.00    --  100.00-145.00   0.00  174
 48  \w    103.00 151.00   0.50   12.00    --  100.00 117.00 120.00   96
 49  \w     84.00 109.00   0.50   12.00    --  100.00-117.00  60.00   50
 50  \w     56.00  95.00   0.50   12.00    --  100.00-145.00-120.00   78
 51  \w     77.00 103.00   0.50   12.00    --  100.00 -59.00  60.00   52
 52  \w    109.00 156.00   0.50   12.00    --  100.00  50.00-120.00   94
 53  \w     83.00 109.00   0.50   12.00    --  100.00 -77.00-150.00   52
 54  \w    112.00 162.00   0.50   12.00    --  100.00  50.00-150.00  100
 55  \w     94.00 119.00   0.50   12.00    --  100.00 -59.00 -60.00   50
 56  \w     36.00  61.00   0.50   12.00    --  100.00-117.00 120.00   50
 57  \w     76.00 106.00   0.50   12.00    --  100.00-117.00 120.00   60
 58  \w     83.00 108.00   0.50   12.00    --  100.00-117.00  90.00   50
 59  \w    122.00 155.00   0.50   12.00    --  100.00  42.00 -90.00   66
 60  \w     39.00  64.00   0.50   12.00    --  100.00-117.00  60.00   50
 61  \w     30.00  92.00   0.50   12.00    --  100.00 -96.00-150.00  124
 62  \w    105.00 158.00   0.50   12.00    --  100.00  96.00 -30.00  106
 63  \w     84.00 109.00   0.50   12.00    --  100.00-117.00 -60.00   50
 64  \w     60.00 109.00   0.50   12.00    --  100.00 -33.00  30.00   98
 65  \w    130.00 158.00   0.50   12.00    --  100.00 145.00-180.00   56
 66  \w     77.00 102.00   0.50   12.00    --  100.00   8.00 150.00   50
 67  \w    140.00 165.00   0.50   12.00    --  100.00   8.00 150.00   50
 68  \w     96.00 163.00   0.50   12.00    --  100.00 145.00 -90.00  134
 69  \w     53.00  79.00   0.50   12.00    --  100.00-117.00 -60.00   52
 70  \w     85.00 110.00   0.50   12.00    --  100.00 -42.00   0.00   50
 71  \w     96.00 134.00   0.50   12.00    --  100.00  25.00-150.00   76
 72  \w     44.00  69.00   0.50   12.00    --  100.00 -77.00  60.00   50
 73  \w     37.00 121.00   0.50   12.00    --  100.00 -68.00  60.00  168
 74  \w    102.00 151.00   0.50   12.00    --  100.00 117.00  90.00   98
 75  \w     76.00 116.00   0.50   12.00    --  100.00 -68.00-180.00   80
 76  \w     96.00 121.00   0.50   12.00    --  100.00 -77.00  60.00   50
 77  \w    105.00 153.00   0.50   12.00    --  100.00  77.00-120.00   96
 78  \w    103.00 132.00   0.50   12.00    --  100.00 117.00-120.00   58
 79  \w    102.00 148.00   0.50   12.00    --  100.00 117.00   0.00   92
 80  \w     64.00 116.00   0.50   12.00    --  100.00 -55.00 156.63  104
 81  \w     87.00 134.00   0.50   12.00    --  100.00  42.00-180.00   94
 82  \w     60.00  86.00   0.50   12.00    --  100.00 -33.00-120.00   52
 83  \w     65.00 100.00   0.50   12.00    --  100.00 -33.00 120.00   70
 84  \w     83.00 159.00   0.50   12.00    --  100.00  68.00 120.00  152
 85  \w     81.00 106.00   0.50   12.00    --  100.00 -93.00 -87.42   50
 86  \w     81.00 106.00   0.50   12.00    --  100.00 -96.00 -30.00   50
 87  \w     53.00  79.00   0.50   12.00    --  100.00 -96.00  60.00   52
 88  \w     35.00 109.00   0.50   12.00    --  100.00 -25.00-180.00  148
 89  \w     81.00 115.00   0.50   12.00    --  100.00 -59.00 -90.00   68
 90  \w     83.00 108.00   0.50   12.00    --  100.00-160.00 -42.00   50
;
_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      0.0390945000
_diffrn_orient_matrix_UB_12      -0.0252875000
_diffrn_orient_matrix_UB_13      0.0385924000
_diffrn_orient_matrix_UB_21      0.0707485000
_diffrn_orient_matrix_UB_22      -0.0202577000
_diffrn_orient_matrix_UB_23      -0.0194476000
_diffrn_orient_matrix_UB_31      0.0258068000
_diffrn_orient_matrix_UB_32      0.0939150000
_diffrn_orient_matrix_UB_33      0.0061883000
_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  0.0783
_diffrn_reflns_av_unetI/netI     0.0433
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -42
_diffrn_reflns_number            144140
_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         71.341
_diffrn_reflns_theta_min         3.748
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.551
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.59979
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.896
_exptl_crystal_description       irregular
_exptl_crystal_F_000             5496
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.898
_refine_diff_density_min         -1.348
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     975
_refine_ls_number_reflns         19312
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0591
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0485P)^2^+36.5691P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1163
_refine_ls_wR_factor_ref         0.1211
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16156
_reflns_number_total             19312
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01067e2.cif
_cod_data_source_block           complex_1
_cod_depositor_comments
'Adding full bibliography for 7718894--7718899.cif.'
_cod_database_code               7718898
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N4 Ag'
_shelx_estimated_absorpt_t_max   0.723
_shelx_estimated_absorpt_t_min   0.230
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,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
 Ho1-H9a \\sim Ho1-H9b
 with sigma of 0.02
 Ho1-H12a \\sim Ho1-H12b
 with sigma of 0.02
 Ho6-H24a \\sim Ho6-H24b
 with sigma of 0.02
 Ho5-H23a \\sim Ho5-H23b
 with sigma of 0.02
 Ho2-H10a \\sim Ho2-H10b
 with sigma of 0.02
3. Others
 Fixed Sof: H55c(0.5) H55d(0.5) H55a(0.5) H55b(0.5) C56A(0.5) H56a(0.5)
 H56b(0.5) H56c(0.5) C56B(0.5) H56d(0.5) H56e(0.5) H56f(0.5)
4.a Free rotating group:
 O9(H9a,H9b), O12(H12a,H12b), O24(H24a,H24b), O23(H23a,H23b), O10(H10a,H10b)
4.b Rotating group:
 O22(H22a,H22b), O25(H25a,H25b), O11(H11a,H11b), O13(H13a,H13b), O26(H26a,H26b)
4.c Secondary CH2 refined with riding coordinates:
 C55(H55c,H55d), C55(H55a,H55b), C57(H57a,H57b)
4.d Aromatic/amide H refined with riding coordinates:
 C13(H13), C7(H7), C25(H25), C1(H1), C16(H16), C22(H22), C28(H28), C34(H34),
 C20(H20), C40(H40), C43(H43), C4(H4), C21(H21), C19(H19), C29(H29), C31(H31),
 C52(H52), C10(H10), C30(H30), C12(H12), C2(H2), C11(H11), C3(H3), C46(H46),
 C49(H49), C47(H47), C37(H37), C39(H39), C38(H38), C48(H48)
4.e Idealised Me refined as rotating group:
 C9(H9c,H9d,H9e), C18(H18a,H18b,H18c), C45(H45a,H45b,H45c), C27(H27a,H27b,
 H27c), C36(H36a,H36b,H36c), C54(H54a,H54b,H54c), C56A(H56a,H56b,H56c),
 C58(H58a,H58b,H58c), C56B(H56d,H56e,H56f)
4.f Idealised tetrahedral OH refined as rotating group:
 O27(H27), O28(H28a)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 594 electrons were 
found in a volume of 2236\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
2Cl-, 3[H2O] and 3[C2H6O1] per Formula Unit 
which account for 576 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              93111
_shelx_hkl_checksum              55165
_shelx_fab_checksum              73791
_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 3.118
_oxdiff_exptl_absorpt_empirical_full_min 0.477