Direct characterisation of <i>m</i><sub><i>J</i></sub> = ±15/2 ground state in octahedral Dy(III) single-molecule magnets.
Parmar, Vijay S.; Gransbury, Gemma K.; Corner, Sophie C.; Chou, Wei-Hao; Hill, Stephen; Winpenny, Richard E. P.; Chilton, Nicholas F.; Mills, David P.; Dalton transactions (Cambridge, England : 2003) 54 (2025) 7616–7620; doi:10.1039/d5dt00862j

data_7718533
_publ_section_title
;
 Direct characterisation of <i>m</i><sub><i>J</i></sub> = &#xb1;15/2
 ground state in octahedral Dy(III) single-molecule magnets.
;
_journal_issue                   19
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7616
_journal_page_last               7620
_journal_paper_doi               10.1039/d5dt00862j
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'C84 H90 Cl Dy O5, 2(C4 H10 O)'
_chemical_formula_sum            'C92 H110 Cl Dy O7'
_chemical_formula_weight         1525.74
_chemical_name_systematic        '[Dy(PH*O)2(THF)3Cl]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-06-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-01-30 deposited with the CCDC.	2025-04-17 downloaded from the CCDC.
;
_cell_angle_alpha                112.183(3)
_cell_angle_beta                 92.607(3)
_cell_angle_gamma                107.522(3)
_cell_formula_units_Z            2
_cell_length_a                   13.0454(5)
_cell_length_b                   16.6596(6)
_cell_length_c                   21.3210(6)
_cell_measurement_reflns_used    6533
_cell_measurement_temperature    149.9(4)
_cell_measurement_theta_max      24.9880
_cell_measurement_theta_min      1.8820
_cell_volume                     4024.6(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.9(4)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0714
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -17.00  22.00   1.00   30.00    --  -18.93 -99.00  90.00   39
  2  \w    -97.00 -35.00   1.00   30.00    --  -18.93-178.00   0.00   62
  3  \w    -40.00   0.00   1.00   30.00    --  -18.93 -77.00-150.00   40
  4  \w     -7.00  93.00   1.00   30.00    --   20.18  38.00   0.00  100
  5  \w      1.00  89.00   1.00   30.00    --   20.18  57.00-150.00   88
  6  \w    -19.00   8.00   1.00   30.00    --   20.18 -99.00 -30.00   27
  7  \w     -1.00  28.00   1.00   30.00    --   20.18  57.00  90.00   29
  8  \w      7.00  70.00   1.00   30.00    --   20.18 -19.00 -30.00   63
  9  \w     34.00  61.00   1.00   30.00    --   20.18 -99.00 -30.00   27
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Single source at offset/far, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0533565000
_diffrn_orient_matrix_UB_12      0.0316844000
_diffrn_orient_matrix_UB_13      0.0164908000
_diffrn_orient_matrix_UB_21      -0.0089529000
_diffrn_orient_matrix_UB_22      -0.0059259000
_diffrn_orient_matrix_UB_23      0.0307831000
_diffrn_orient_matrix_UB_31      0.0208091000
_diffrn_orient_matrix_UB_32      -0.0368631000
_diffrn_orient_matrix_UB_33      -0.0107019000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1191
_diffrn_reflns_av_unetI/netI     0.1700
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            33817
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_min         1.988
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.015
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.642
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_description       block
_exptl_crystal_F_000             1598
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.227
_exptl_crystal_size_mid          0.066
_exptl_crystal_size_min          0.043
_refine_diff_density_max         1.642
_refine_diff_density_min         -2.103
_refine_diff_density_rms         0.125
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.973
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     976
_refine_ls_number_reflns         16438
_refine_ls_number_restraints     1096
_refine_ls_restrained_S_all      0.963
_refine_ls_R_factor_all          0.1093
_refine_ls_R_factor_gt           0.0684
_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^)+(0.0377P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1319
_refine_ls_wR_factor_ref         0.1555
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10823
_reflns_number_total             16438
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00862j2.cif
_cod_data_source_block           adpm612
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_atom_sites_solution_secondary' value 'diffmap' was
changed to 'difmap'.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 7718533--7718536.cif.
;
_cod_original_cell_volume        4024.7(3)
_cod_database_code               7718533
_manchester_internal_diff_code   ADPM612
_manchester_internal_coll_client VP/DPM
_manchester_internal_coll_user   VP/DPM
_manchester_internal_coll_date   17/07/2019
_manchester_internal_process_date 17/07/2019
_manchester_internal_process_user VP/DPM
_manchester_internal_solution_date 17/07/2019
_manchester_internal_solution_user VP
_manchester_internal_refinement_date 25/06/24
_manchester_internal_refinement_user VP/SCC
_manchester_internal_validation_date 25/06/24
_manchester_internal_validation_user SCC
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C84H90ClDyO65
_chemical_oxdiff_usercomment     VJ/DPM
_shelx_estimated_absorpt_t_max   0.958
_shelx_estimated_absorpt_t_min   0.802
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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
2. Restrained distances
 O7A-C91 = O7-C91 = O7A-C90A = O7-C90
 1.45 with sigma of 0.02
 C90A-C89A = C90-C89 = C92-C91 = C92-C91
 1.55 with sigma of 0.02
 C80-C79 \\sim C80-C79A \\sim C79A-C78A \\sim C79-C78 \\sim C78A-C77 \\sim
C78-C77 \\sim C74A-C73 ~
 C75-C74 \\sim C74-C73 \\sim C75-C74A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
O4 \\sim C77 \\sim C78 \\sim C78A \\sim C79 \\sim C79A \\sim C80: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
O3 \\sim C73 \\sim C74 \\sim C74A \\sim C75 \\sim C76: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08
O7 \\sim O7A \\sim C89 \\sim C89A \\sim C90 \\sim C90A \\sim C91 \\sim C92:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H73C)=Sof(H73D)=Sof(C74A)=Sof(H74C)=Sof(H74D)=Sof(H75C)=Sof(H75D)=
 Sof(H77C)=Sof(H77D)=Sof(C78A)=Sof(H78C)=Sof(H78D)=Sof(C79A)=Sof(H79C)=
 Sof(H79D)=Sof(H80C)=Sof(H80D)=Sof(O7A)=Sof(C89A)=Sof(H89D)=Sof(H89E)=Sof(H89F)=
 Sof(C90A)=Sof(H90C)=Sof(H90D)=Sof(H91A)=1-FVAR(1)
 Sof(H73A)=Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H75A)=Sof(H75B)=
 Sof(H77A)=Sof(H77B)=Sof(C78)=Sof(H78A)=Sof(H78B)=Sof(C79)=Sof(H79A)=Sof(H79B)=
 Sof(H80A)=Sof(H80B)=Sof(O7)=Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(H89C)=Sof(C90)=
 Sof(H90A)=Sof(H90B)=Sof(H91A)=Sof(H91B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C24(H24), C43(H43), C60(H60)
6.b Secondary CH2 refined with riding coordinates:
 C73(H73A,H73B), C73(H73C,H73D), C74(H74A,H74B), C74A(H74C,H74D), C75(H75A,
 H75B), C75(H75C,H75D), C76(H76A,H76B), C77(H77A,H77B), C77(H77C,H77D),
 C78(H78A,H78B), C78A(H78C,H78D), C79(H79A,H79B), C79A(H79C,H79D), C80(H80A,
 H80B), C80(H80C,H80D), C81(H81A,H81B), C82(H82A,H82B), C83(H83A,H83B),
 C84(H84A,H84B), C87(H87A,H87B), C90(H90A,H90B), C90A(H90C,H90D)
6.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C15(H15),
 C16(H16), C17(H17), C18(H18), C19(H19), C26(H26), C27(H27), C28(H28), C29(H29),
  C30(H30), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36), C39(H39),
 C41(H41), C45(H45), C46(H46), C47(H47), C48(H48), C49(H49), C51(H51), C52(H52),
  C53(H53), C54(H54), C55(H55), C62(H62), C63(H63), C64(H64), C65(H65),
 C66(H66), C68(H68), C69(H69), C70(H70), C71(H71), C72(H72), C85(H85), C91(H91),
  C91(H91A)
6.d Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,H23C), C57(H57A,H57B,
 H57C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C86(H86A,H86B,H86C), C88(H88A,
 H88B,H88C), C89(H89A,H89B,H89C), C89A(H89D,H89E,H89F), C92(H92A,H92B,H92C)
;
_shelx_res_checksum              74250
_shelx_hkl_checksum              36063
_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 6.079
_oxdiff_exptl_absorpt_empirical_full_min 0.308