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_7718894
_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 H36 Cl Ho3 N3 O13, 3(Cl), 3[Cl], 2[H2O]'
_chemical_formula_sum            'C27 H40 Cl7 Ho3 N3 O15'
_chemical_formula_weight         1389.56
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-04-04
_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                106.212(2)
_cell_angle_beta                 100.122(2)
_cell_angle_gamma                102.811(2)
_cell_formula_units_Z            2
_cell_length_a                   10.7890(2)
_cell_length_b                   13.8732(2)
_cell_length_c                   16.9814(4)
_cell_measurement_reflns_used    17734
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      71.0980
_cell_measurement_theta_min      3.4520
_cell_volume                     2301.98(9)
_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      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_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    -64.00 -35.00   0.50    1.50    --  -38.50  80.00  18.00   58
  2  \w     75.00 102.00   0.50    6.00    --  100.00 -80.00-104.00   54
  3  \w     40.00  66.00   0.50    6.00    --  100.00 -80.00-104.00   52
  4  \w    112.00 161.00   0.50    6.00    --  100.00  80.00  18.00   98
  5  \w    -50.00 -25.00   0.50    1.50    --  -38.50 -65.00  30.00   50
  6  \w    -74.00   7.00   0.50    1.50    --  -38.50 104.00-120.00  162
  7  \w    -47.00 -17.00   0.50    1.50    --  -38.50  32.00 120.00   60
  8  \w   -105.00 -32.00   0.50    1.50    --  -38.50 -21.00 -90.00  146
  9  \w    -32.00   2.00   0.50    1.50    --  -38.50  80.00  18.00   68
 10  \w    -46.00  26.00   0.50    1.50    --  -38.50  32.00 150.00  144
 11  \w    -95.00 -66.00   0.50    1.50    --  -38.50 -65.00  30.00   58
 12  \w    -14.00  11.00   0.50    1.50    --  -38.50  32.00 120.00   50
 13  \w    -55.00  20.00   0.50    1.50    --  -38.50  65.00-150.00  150
 14  \w     19.00 115.00   0.50    1.50    --   42.60  11.00  60.00  192
 15  \w    -21.00  29.00   0.50    1.50    --   42.60 -11.00 120.00  100
 16  \w     50.00  76.00   0.50    1.50    --   42.60-104.00  30.00   52
 17  \w     29.00  62.00   0.50    1.50    --   42.60 -65.00 150.00   66
 18  \w     38.00  64.00   0.50    1.50    --   42.60 -11.00 120.00   52
 19  \w    -18.00  17.00   0.50    1.50    --   42.60 -65.00 150.00   70
 20  \w     31.00  56.00   0.50    1.50    --   42.60  43.00 -60.00   50
 21  \w     11.00  45.00   0.50    1.50    --   42.60-104.00  30.00   68
 22  \w     27.00  53.00   0.50    1.50    --   42.60 -89.00 150.00   52
 23  \w     36.00  93.00   0.50    1.50    --   42.60-138.00-180.00  114
 24  \w     43.00  86.00   0.50    1.50    --   42.60  54.00 -30.00   86
 25  \w     44.00  82.00   0.50    1.50    --   42.60  32.00 -60.00   76
 26  \w     30.00  55.00   0.50    1.50    --   42.60 -80.00-104.00   50
 27  \w     70.00 105.00   0.50    1.50    --   42.60  43.00 -60.00   70
 28  \w     -8.00  17.00   0.50    1.50    --   42.60 -89.00 150.00   50
 29  \w     35.00 107.00   0.50    6.00    --  100.00-117.00 150.00  144
 30  \w     55.00 107.00   0.50    6.00    --  100.00 -33.00   0.00  104
 31  \w     71.00 126.00   0.50    6.00    --  100.00-145.00 120.00  110
 32  \w     74.00 109.00   0.50    6.00    --  100.00 -25.00 -90.00   70
 33  \w    119.00 158.00   0.50    6.00    --  100.00  96.00-150.00   78
 34  \w     46.00  72.00   0.50    6.00    --  100.00 -96.00 150.00   52
 35  \w     43.00  95.00   0.50    6.00    --  100.00 -25.00-150.00  104
 36  \w     38.00 107.00   0.50    6.00    --  100.00 -59.00 120.00  138
 37  \w    102.00 170.00   0.50    6.00    --  100.00  17.00 -60.00  136
 38  \w     77.00 103.00   0.50    6.00    --  100.00 -96.00 -30.00   52
 39  \w     32.00  69.00   0.50    6.00    --  100.00 -25.00 -90.00   74
 40  \w    108.00 138.00   0.50    6.00    --  100.00  50.00  90.00   60
 41  \w    134.00 160.00   0.50    6.00    --  100.00  77.00 -90.00   52
 42  \w     58.00  83.00   0.50    6.00    --  100.00-117.00-150.00   50
 43  \w     37.00  62.00   0.50    6.00    --  100.00 -96.00 -30.00   50
 44  \w    125.00 164.00   0.50    6.00    --  100.00  77.00  30.00   78
 45  \w     38.00  65.00   0.50    6.00    --  100.00 -96.00  30.00   54
 46  \w     36.00 107.00   0.50    6.00    --  100.00-117.00   0.00  142
 47  \w     45.00 100.00   0.50    6.00    --  100.00 -96.00-120.00  110
 48  \w    105.00 170.00   0.50    6.00    --  100.00  96.00   0.00  130
 49  \w     88.00 161.00   0.50    6.00    --  100.00  42.00-180.00  146
 50  \w    121.00 148.00   0.50    6.00    --  100.00  77.00 -60.00   54
 51  \w     55.00 109.00   0.50    6.00    --  100.00 -59.00   0.00  108
 52  \w    118.00 165.00   0.50    6.00    --  100.00 117.00  30.00   94
 53  \w    116.00 170.00   0.50    6.00    --  100.00  96.00 120.00  108
 54  \w     42.00 111.00   0.50    6.00    --  100.00 -42.00 -60.00  138
 55  \w     91.00 150.00   0.50    6.00    --  100.00  50.00  60.00  118
 56  \w     74.00 126.00   0.50    6.00    --  100.00-145.00 150.00  104
 57  \w     42.00  67.00   0.50    6.00    --  100.00-145.00 150.00   50
 58  \w     36.00 109.00   0.50    6.00    --  100.00-117.00 -30.00  146
 59  \w     61.00  87.00   0.50    6.00    --  100.00 -50.00-120.00   52
 60  \w    122.00 156.00   0.50    6.00    --  100.00  68.00-180.00   68
 61  \w     65.00 101.00   0.50    6.00    --  100.00 -96.00  60.00   72
 62  \w    137.00 162.00   0.50    6.00    --  100.00 145.00 150.00   50
 63  \w     40.00  65.00   0.50    6.00    --  100.00 -87.00 120.00   50
 64  \w     42.00  76.00   0.50    6.00    --  100.00-145.00 -90.00   68
 65  \w     94.00 119.00   0.50    6.00    --  100.00  68.00 120.00   50
 66  \w    138.00 163.00   0.50    6.00    --  100.00  68.00 120.00   50
 67  \w     80.00 110.00   0.50    6.00    --  100.00  68.00-180.00   60
 68  \w     83.00 109.00   0.50    6.00    --  100.00-117.00-120.00   52
 69  \w     89.00 126.00   0.50    6.00    --  100.00 -87.00 120.00   74
 70  \w     35.00 109.00   0.50    6.00    --  100.00-117.00-180.00  148
 71  \w     59.00  84.00   0.50    6.00    --  100.00 -35.00 -63.66   50
 72  \w     36.00  61.00   0.50    6.00    --  100.00 -96.00 -90.00   50
 73  \w     56.00  82.00   0.50    6.00    --  100.00 -96.00   0.00   52
 74  \w    114.00 139.00   0.50    6.00    --  100.00 145.00  30.00   50
 75  \w    107.00 160.00   0.50    6.00    --  100.00  77.00 -30.00  106
;
_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      -0.1178700000
_diffrn_orient_matrix_UB_12      0.0077156000
_diffrn_orient_matrix_UB_13      -0.0614307000
_diffrn_orient_matrix_UB_21      -0.0895350000
_diffrn_orient_matrix_UB_22      -0.0269523000
_diffrn_orient_matrix_UB_23      0.0568323000
_diffrn_orient_matrix_UB_31      0.0317819000
_diffrn_orient_matrix_UB_32      0.1174031000
_diffrn_orient_matrix_UB_33      0.0503686000
_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  0.0269
_diffrn_reflns_av_unetI/netI     0.0265
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            28930
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.274
_diffrn_reflns_theta_min         3.463
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    13.494
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45484
_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 pink'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    2.005
_exptl_crystal_description       plate
_exptl_crystal_F_000             1326
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.688
_refine_diff_density_min         -1.294
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     622
_refine_ls_number_reflns         8868
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0355
_refine_ls_R_factor_gt           0.0332
_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^)+(0.0387P)^2^+3.6973P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0842
_refine_ls_wR_factor_ref         0.0856
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8208
_reflns_number_total             8868
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01067e2.cif
_cod_data_source_block           complex_4
_cod_depositor_comments
'Adding full bibliography for 7718894--7718899.cif.'
_cod_original_cell_volume        2301.98(8)
_cod_database_code               7718894
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     'BOF79 pink crystal'
_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
 O8-H8
 0.85 with sigma of 0.01
 Ho01-H12A \\sim Ho01-H12B
 with sigma of 0.02
 Ho02-H13A \\sim Ho02-H13B
 with sigma of 0.02
3. Others
 Sof(O3B)=Sof(O4B)=Sof(N2B)=Sof(C14B)=Sof(C15B)=Sof(C17B)=Sof(C10B)=Sof(H10C)=
 Sof(C16B)=Sof(H16B)=Sof(C13B)=Sof(H13C)=Sof(C11B)=Sof(H11C)=Sof(C12B)=
 Sof(H12C)=Sof(C18B)=Sof(H18A)=Sof(H18B)=Sof(H18C)=1-FVAR(1)
 Sof(N2A)=Sof(C10A)=Sof(H10D)=Sof(C11A)=Sof(H11D)=Sof(C12A)=Sof(H12D)=
 Sof(C13A)=Sof(H13D)=Sof(C14A)=Sof(C15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=
 Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(O3A)=Sof(O4A)=FVAR(1)
 Sof(N3B)=Sof(C24B)=Sof(C26B)=Sof(C25B)=Sof(H25B)=Sof(C23B)=Sof(C27B)=
 Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C22B)=Sof(H22B)=Sof(C19B)=Sof(H19B)=
 Sof(C21B)=Sof(H21B)=Sof(C20B)=Sof(H20B)=1-FVAR(2)
 Sof(N3A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21A)=
 Sof(C22A)=Sof(H22A)=Sof(C24A)=Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(C27A)=
 Sof(H27D)=Sof(H27E)=Sof(H27F)=Sof(C23A)=FVAR(2)
4.a Free rotating group:
 O13(H13A,H13B), O12(H12A,H12B)
4.b Rotating group:
 O11(H11A,H11B), O9(H9A,H9B), O10(H10A,H10B)
4.c Ternary CH refined with riding coordinates and stretchable bonds:
 O8(H8), O7(H7)
4.d Aromatic/amide H refined with riding coordinates:
 C7(H7A), C4(H4), C3(H3), C1(H1), C25B(H25B), C2(H2), C10B(H10C), C16B(H16B),
 C22B(H22B), C13B(H13C), C11B(H11C), C19B(H19B), C12B(H12C), C21B(H21B),
 C20B(H20B), C10A(H10D), C11A(H11D), C12A(H12D), C13A(H13D), C16A(H16A),
 C19A(H19A), C20A(H20A), C21A(H21A), C22A(H22A), C25A(H25A)
4.e Idealised Me refined as rotating group:
 C9(H9C,H9D,H9E), C27B(H27A,H27B,H27C), C18B(H18A,H18B,H18C), C18A(H18D,H18E,
 H18F), C27A(H27D,H27E,H27F)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 145 electrons were 
found in a volume of 479\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3[Cl-], 2[H2O] per Asymmetric Unit 
which account for 148 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 2.306
_oxdiff_exptl_absorpt_empirical_full_min 0.480