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_7718896
_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         'C90 H62 Dy2 N5 O11, 6[Cl-]'
_chemical_formula_sum            'C90 H62 Cl6 Dy2 N5 O11'
_chemical_formula_weight         1927.14
_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             2025-03-12
_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                 100.700(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.9809(2)
_cell_length_b                   33.1510(5)
_cell_length_c                   26.2513(6)
_cell_measurement_reflns_used    12963
_cell_measurement_temperature    149.8(3)
_cell_measurement_theta_max      70.8120
_cell_measurement_theta_min      3.6800
_cell_volume                     8534.9(3)
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.8(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.951
_diffrn_measured_fraction_theta_max 0.925
_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    -69.00 -35.00   0.50   26.55    --  -38.50 -42.00 -82.00   68
  2  \w    -40.00 -12.00   0.50   26.55    --  -38.50  42.00  70.00   56
  3  \w    -66.00 -41.00   0.50   26.55    --  -38.50 118.00 139.00   50
  4  \w   -102.00 -27.00   0.50   26.55    --  -38.50 158.00 -66.00  150
  5  \w    -41.00 -14.00   0.50   26.55    --  -38.50  80.00-107.00   54
  6  \w     58.00  83.00   0.50   26.55    --   42.60-158.00-100.00   50
  7  \w     61.00  86.00   0.50   26.55    --   42.60  42.00  70.00   50
  8  \w     31.00  56.00   0.50   26.55    --   42.60-118.00  53.00   50
  9  \w     67.00  92.00   0.50  106.20    --  100.00 -42.00 -82.00   50
 10  \w     87.00 145.00   0.50  106.20    --  100.00  42.00  70.00  116
 11  \w     38.00  86.00   0.50  106.20    --  100.00 -80.00 129.00   96
 12  \w     77.00 132.00   0.50  106.20    --  100.00 158.00 -66.00  110
 13  \w    109.00 134.00   0.50  106.20    --  100.00 118.00 139.00   50
 14  \w     50.00  80.00   0.50  106.20    --  100.00-118.00  53.00   60
 15  \w    107.00 162.00   0.50  106.20    --  100.00  80.00-107.00  110
 16  \w     34.00  94.00   0.50   26.55    --   42.60  54.00  90.00  120
 17  \w     57.00  90.00   0.50   26.55    --   42.60  32.00 120.00   66
 18  \w     43.00  81.00   0.50   26.55    --   42.60-138.00-180.00   76
 19  \w     35.00  94.00   0.50  106.20    --  100.00 -33.00  90.00  118
 20  \w    118.00 159.00   0.50  106.20    --  100.00 117.00 -30.00   82
 21  \w     84.00 109.00   0.50  106.20    --  100.00-117.00-180.00   50
 22  \w     82.00 155.00   0.50  106.20    --  100.00  59.00 -60.00  146
 23  \w     83.00 121.00   0.50  106.20    --  100.00 -77.00  30.00   76
 24  \w    112.00 137.00   0.50  106.20    --  100.00  96.00 -90.00   50
 25  \w    116.00 141.00   0.50  106.20    --  100.00  77.00 120.00   50
 26  \w    106.00 149.00   0.50  106.20    --  100.00  77.00-180.00   86
 27  \w    116.00 141.00   0.50  106.20    --  100.00 117.00 120.00   50
 28  \w    115.00 141.00   0.50  106.20    --  100.00  77.00  30.00   52
 29  \w    116.00 149.00   0.50  106.20    --  100.00  77.00   0.00   66
;
_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      0.1335790000
_diffrn_orient_matrix_UB_12      -0.0243571000
_diffrn_orient_matrix_UB_13      0.0070506000
_diffrn_orient_matrix_UB_21      -0.0023242000
_diffrn_orient_matrix_UB_22      0.0024999000
_diffrn_orient_matrix_UB_23      -0.0587640000
_diffrn_orient_matrix_UB_31      0.0826203000
_diffrn_orient_matrix_UB_32      0.0394969000
_diffrn_orient_matrix_UB_33      0.0080461000
_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  0.0390
_diffrn_reflns_av_unetI/netI     0.0468
_diffrn_reflns_Laue_measured_fraction_full 0.951
_diffrn_reflns_Laue_measured_fraction_max 0.925
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            37130
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.925
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.727
_diffrn_reflns_theta_min         3.169
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    11.491
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.33934
_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 yellowish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.500
_exptl_crystal_description       irregular
_exptl_crystal_F_000             3836
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.107
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1002
_refine_ls_number_reflns         15465
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0804
_refine_ls_R_factor_gt           0.0586
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1062P)^2^+6.1007P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1677
_refine_ls_wR_factor_ref         0.1861
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11116
_reflns_number_total             15465
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt01067e2.cif
_cod_data_source_block           complex_6
_cod_depositor_comments
'Adding full bibliography for 7718894--7718899.cif.'
_cod_database_code               7718896
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         Dy2C90N5O11H62Cl6
_chemical_oxdiff_usercomment     'yellow block'
_shelx_estimated_absorpt_t_max   0.597
_shelx_estimated_absorpt_t_min   0.245
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Shared sites
{C49, N5A}
{C95, N6}
3. Restrained distances
 C78-C46
 2.43 with sigma of 0.01
 C73-C47
 2.43 with sigma of 0.01
 C46-C48
 2.43 with sigma of 0.01
 C47-C50
 2.43 with sigma of 0.01
 C48-C78
 2.43 with sigma of 0.01
 C50-C73
 2.43 with sigma of 0.01
 C53B-C48A \\sim C46B-C48A
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
Uanis(C49) = Uanis(N5A)
Uiso(C95) = Uiso(N6)
5. Others
 Sof(H73B)=Sof(C75A)=Sof(H75A)=Sof(C76A)=Sof(H76A)=Sof(C78A)=Sof(H78A)=
 Sof(C77A)=Sof(H77A)=Sof(N5A)=Sof(H5A)=Sof(C95)=Sof(H95)=1-FVAR(1)
 Sof(H74A)=Sof(H79A)=0.5*(1-FVAR(2))
 Sof(H73)=Sof(H78)=0.5*FVAR(2)
 Sof(H73A)=Sof(C48)=Sof(H48)=Sof(C46)=Sof(H46)=Sof(C47)=Sof(H47)=Sof(C50)=
 Sof(H50)=Sof(C49)=Sof(H49)=Sof(N6)=Sof(H6)=FVAR(1)
 Fixed Sof: C54B(0.5) H54B(0.5) C46A(0.5) H46A(0.5) C53B(0.5) H53B(0.5)
 C48A(0.5) H48A(0.5) C49B(0.5) H49B(0.5) C50B(0.5) H50B(0.5) C51B(0.5)
 H51B(0.5) C50A(0.5) H50A(0.5) C51A(0.5) H51A(0.5) C49A(0.5) H49A(0.5)
 C48B(0.5) H48B(0.5) C53A(0.5) H53A(0.5) C54A(0.5) H54A(0.5) C46B(0.5)
 H46B(0.5) C47A(0.5) C52B(0.5) C52A(0.5) C1A(0.5)
6.a Rotating group:
 O11(H11A,H11B)
6.b Aromatic/amide H refined with riding coordinates:
 C10(H10), C64(H64), C12(H12), C28(H28), C7(H7), C83(H83), C4(H4), C25(H25),
 C15(H15), C72(H72), C13(H13), C55(H55), C43(H43), C22(H22), C58(H58), C61(H61),
  C29(H29), C56(H56), C14(H14), C1(H1), C69(H69), C66(H66), C38(H38), C18(H18),
 C3(H3), C57(H57), C71(H71), C2(H2), C19(H19), C36(H36), C73A(H73A), C73A(H73B),
  C68(H68), C20(H20), C40(H40), C39(H39), C37(H37), C31(H31), C33(H33),
 C73(H73), C21(H21), C67(H67), C32(H32), C80A(H80A), C74A(H74A), C34(H34),
 C80(H80), C17(H17), C78(H78), C54B(H54B), C79(H79), C79A(H79A), C46A(H46A),
 C53B(H53B), C48A(H48A), C49B(H49B), C50B(H50B), C51B(H51B), C50A(H50A),
 C51A(H51A), C49A(H49A), C48B(H48B), C53A(H53A), C54A(H54A), C46B(H46B),
 C48(H48), C46(H46), C47(H47), C50(H50), C75A(H75A), C76A(H76A), C78A(H78A),
 C77A(H77A), C49(H49), N5A(H5A), C95(H95), N6(H6)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 426 electrons were 
found in a volume of 1616\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
6[Cl-] per Formula Unit 
which account for 432 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              93558
_shelx_hkl_checksum              75274
_shelx_fab_checksum              66735
_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 2.669
_oxdiff_exptl_absorpt_empirical_full_min 0.577