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_7718897
_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         'C31 H42 Cl Ho3 N3 O13, 3(Cl), 0.167[C6H18O3]'
_chemical_formula_sum            'C32 H45 Cl4 Ho3 N3 O13.5'
_chemical_formula_weight         1324.30
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2024-11-26
_audit_creation_method
;
Olex2 1.5
(compiled 2024.01.12 svn.r2f8d729c for OlexSys, GUI svn.r6928)
;
_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
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   31.88400(10)
_cell_length_b                   31.88400(10)
_cell_length_c                   26.85650(10)
_cell_measurement_reflns_used    108699
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      75.5460
_cell_measurement_theta_min      2.2820
_cell_volume                     23644.26(14)
_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 (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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    -86.00  -1.00   0.50    0.25    --  -46.20 110.00-147.00  170
  2  \w     34.00 119.00   0.50    0.25    --   46.20  38.00-120.00  170
  3  \w     89.00 178.00   0.50    1.00    --  102.41  25.00-136.00  178
  4  \w     89.00 178.00   0.50    1.00    --  102.41  15.00-180.00  178
  5  \w     79.00 175.00   0.50    1.00    --  102.41  84.00  51.00  192
  6  \w     90.00 174.00   0.50    1.00    --  102.41  45.00 120.00  168
  7  \w     86.00 175.00   0.50    1.00    --  102.41  61.00  90.00  178
  8  \w     80.00 175.00   0.50    1.00    --  102.41  77.00 150.00  190
  9  \w     30.00 117.00   0.50    1.00    --  102.41 -57.00 -75.00  174
 10  \w     31.00 118.00   0.50    0.25    --   46.20  57.00  90.00  174
 11  \w     24.00 118.00   0.50    0.25    --   46.20  77.00 150.00  188
 12  \w     31.00 115.00   0.50    1.00    --  102.41 -45.00 150.00  168
 13  \w     30.00 111.00   0.50    1.00    --  102.41-125.00 150.00  162
 14  \w     30.00 125.00   0.50    1.00    --  102.41 -77.00 120.00  190
 15  \w     30.00 105.00   0.50    1.00    --  102.41 -94.00   0.00  150
 16  \w     13.00  94.00   0.50    0.25    --   46.20-125.00  90.00  162
 17  \w     31.00 118.00   0.50    0.25    --   46.20  57.00 -90.00  174
 18  \w     24.00 118.00   0.50    0.25    --   46.20  77.00 -60.00  188
 19  \w     24.00  57.00   0.50    0.25    --   46.20  77.00-150.00   66
 20  \w    -27.00  58.00   0.50    0.25    --   46.20 -38.00-180.00  170
 21  \w     31.00 118.00   0.50    0.25    --   46.20  57.00  30.00  174
 22  \w   -108.00 -30.00   0.50    1.00    -- -102.41 110.00-147.00  156
 23  \w   -175.00 -86.00   0.50    1.00    -- -102.41 -61.00   0.00  178
 24  \w   -118.00 -73.00   0.50    0.25    --  -46.20-125.00 -30.00   90
 25  \w   -118.00 -73.00   0.50    0.25    --  -46.20-125.00-120.00   90
 26  \w   -118.00 -73.00   0.50    0.25    --  -46.20-125.00-180.00   90
 27  \w   -177.00 -89.00   0.50    1.00    -- -102.41 -15.00 -30.00  176
 28  \w   -118.00 -23.00   0.50    0.25    --  -46.20 -77.00  30.00  190
 29  \w   -118.00 -23.00   0.50    0.25    --  -46.20 -77.00 120.00  190
 30  \w   -174.00 -90.00   0.50    1.00    -- -102.41 -45.00  60.00  168
 31  \w   -175.00 -79.00   0.50    1.00    -- -102.41 -84.00 -68.00  192
 32  \w   -174.00 -90.00   0.50    1.00    -- -102.41 -45.00 -60.00  168
 33  \w   -175.00 -80.00   0.50    1.00    -- -102.41 -77.00  60.00  190
 34  \w   -175.00 -80.00   0.50    1.00    -- -102.41 -77.00 -90.00  190
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0490
_diffrn_reflns_av_unetI/netI     0.0141
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -34
_diffrn_reflns_limit_k_max       39
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            160133
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.757
_diffrn_reflns_theta_min         2.295
_exptl_absorpt_coefficient_mu    10.398
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.555
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
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            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.674
_exptl_crystal_description       hexagons
_exptl_crystal_F_000             11430
_exptl_crystal_size_max          0.247
_exptl_crystal_size_mid          0.148
_exptl_crystal_size_min          0.144
_refine_diff_density_max         0.724
_refine_diff_density_min         -0.777
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     500
_refine_ls_number_reflns         10844
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0248
_refine_ls_R_factor_gt           0.0242
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0314P)^2^+79.6813P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0645
_refine_ls_wR_factor_ref         0.0649
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10519
_reflns_number_total             10844
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01067e2.cif
_cod_data_source_block           complex_3
_cod_depositor_comments
'Adding full bibliography for 7718894--7718899.cif.'
_cod_original_cell_volume        23644.24(17)
_cod_original_sg_symbol_H-M      'R -3'
_cod_original_formula_sum        'C32 H45 Cl4 Ho3 N3 O13.50'
_cod_database_code               7718897
_shelx_shelxl_version_number     2018/3
_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
 O11-H11
 0.85 with sigma of 0.01
 O12-H12
 0.85 with sigma of 0.01
 C28-H11
 1.921331 with sigma of 0.02
 Ho2-H11
 2.891975 with sigma of 0.02
 C31-H12
 1.908031 with sigma of 0.02
 Ho3-H12
 2.886313 with sigma of 0.02
 C30-C28 \\sim C29-C28
 with sigma of 0.02
 C29-C28 \\sim C30-C28 \\sim C31-C32
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C29) = Uanis(C28) = Uanis(C30)
4. Rigid body (RIGU) restrains
 C29, C28, C30
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C30, C29, C28, O11
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C30, C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Others
 Sof(H28C)=Sof(H28D)=Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(1)
 Sof(H28A)=Sof(H28B)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=FVAR(1)
6.a Rotating group:
 O10(H10A,H10B), O13(H13A,H13B), O9(H9A,H9B)
6.b Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C28(H28C,H28D), C28(H28A,H28B)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C20(H20), C27(H27), C7(H7), C5(H5), C15(H15), C9(H9), C8(H8),
 C26(H26), C11(H11A), C16(H16), C18(H18), C24(H24), C17(H17), C25(H25)
6.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C22(H22A,H22B,H22C), C4(H4A,H4B,H4C), C13(H13C,H13D,
 H13E), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              80115
_shelx_hkl_checksum              76982
_shelx_fab_checksum              56682
_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
;