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_7718535
_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 Br Dy O5, 3(C3 H7)'
_chemical_formula_sum            'C93 H111 Br Dy O5'
_chemical_formula_weight         1551.22
_chemical_name_systematic        '[Dy(OPh*)2(THF)3Br]'
_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
;
2024-06-28 deposited with the CCDC.	2025-04-17 downloaded from the CCDC.
;
_cell_angle_alpha                105.495(4)
_cell_angle_beta                 93.553(3)
_cell_angle_gamma                94.744(3)
_cell_formula_units_Z            2
_cell_length_a                   12.1093(4)
_cell_length_b                   15.3634(7)
_cell_length_c                   23.6294(9)
_cell_measurement_reflns_used    11252
_cell_measurement_temperature    150.03(10)
_cell_measurement_theta_max      27.5010
_cell_measurement_theta_min      1.9600
_cell_volume                     4205.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.7b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.7b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.7b (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.03(10)
_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    -72.00   0.00   1.00    6.58    --  -18.77 -19.00-150.00   72
  2  \w    -16.00  12.00   1.00    6.58    --  -18.77 -99.00 120.00   28
  3  \w    -12.00  16.00   1.00    6.58    --  -18.77 -99.00 -60.00   28
  4  \w    -76.00 -43.00   1.00    6.58    --  -18.77-178.00  60.00   33
  5  \w    -86.00   3.00   1.00    6.58    --  -18.77 -57.00-180.00   89
  6  \w      1.00  91.00   1.00    6.58    --   20.02  38.00   0.00   90
  7  \w      8.00  87.00   1.00    6.58    --   20.02  57.00  60.00   79
  8  \w     44.00  96.00   1.00    6.58    --   20.02 178.00-180.00   52
;
_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      -0.0020365000
_diffrn_orient_matrix_UB_12      -0.0477672000
_diffrn_orient_matrix_UB_13      -0.0050921000
_diffrn_orient_matrix_UB_21      0.0262110000
_diffrn_orient_matrix_UB_22      -0.0031998000
_diffrn_orient_matrix_UB_23      -0.0264022000
_diffrn_orient_matrix_UB_31      0.0528220000
_diffrn_orient_matrix_UB_32      0.0052990000
_diffrn_orient_matrix_UB_33      0.0159625000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0593
_diffrn_reflns_av_unetI/netI     0.0948
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            36781
_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         1.846
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.412
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.826
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.7b (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    1.225
_exptl_crystal_description       block
_exptl_crystal_F_000             1620
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_size_max          0.204
_exptl_crystal_size_mid          0.144
_exptl_crystal_size_min          0.118
_refine_diff_density_max         1.253
_refine_diff_density_min         -1.117
_refine_diff_density_rms         0.112
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1071
_refine_ls_number_reflns         17189
_refine_ls_number_restraints     2119
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0728
_refine_ls_R_factor_gt           0.0511
_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^)+(0.0475P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1133
_refine_ls_wR_factor_ref         0.1277
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13384
_reflns_number_total             17189
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00862j2.cif
_cod_data_source_block           adpm620
_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_database_code               7718535
_manchester_internal_diff_code   adpm620
_manchester_internal_coll_client VP
_manchester_internal_coll_date   19/02/20
_manchester_internal_process_date 19/02/20
_manchester_internal_process_user VP
_manchester_internal_solution_date 19/02/20
_manchester_internal_solution_user VP
_manchester_internal_refinement_date 26/06/24
_manchester_internal_refinement_user VP/SCC
_manchester_internal_validation_date 26/06/24
_manchester_internal_validation_user SCC
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H O Dy Br'
_shelx_estimated_absorpt_t_max   0.851
_shelx_estimated_absorpt_t_min   0.762
_reflns_odcompleteness_completeness 99.94
_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
 C34-C33 \\sim C34A-C33A \\sim C35-C33 \\sim C35A-C33A \\sim C36A-C33A \\sim
C36-C33 \\sim C70A-C69 ~
 C70-C69 \\sim C71A-C69 \\sim C71-C69 \\sim C72A-C69 \\sim C72-C69
 with sigma of 0.02
 C89-C88 \\sim C90-C89 \\sim C91-C90 \\sim C92-C91 \\sim C93-C92 \\sim
C89A-C88A \\sim C90A-C89A ~
 C91A-C90A \\sim C92A-C91A \\sim C93A-C92A
 with sigma of 0.02
 C93A-C91A \\sim C92A-C90A \\sim C91A-C89A \\sim C90A-C88A \\sim C93-C91 \\sim
C92-C90 \\sim C91-C89 ~
 C90-C88
 with sigma of 0.02
 C82-C81A \\sim C82-C81
 with sigma of 0.02
 C4-C33 \\sim C4-C33A \\sim C27-C20 \\sim C27A-C20
 with sigma of 0.02
 O5-C81A \\sim O5-C81
 with sigma of 0.02
 C35-C34 \\sim C36-C35 \\sim C36-C34 \\sim C36A-C34A \\sim C35A-C34A \\sim
C36A-C35A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C35) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(H20a)=Sof(C27A)=Sof(C32A)=Sof(H32A)=Sof(C31A)=Sof(H31A)=Sof(C30A)=
 Sof(H30A)=Sof(C29A)=Sof(H29A)=Sof(C28A)=Sof(H28A)=Sof(C33A)=Sof(C34A)=
 Sof(H34d)=Sof(H34e)=Sof(H34f)=Sof(C35)=Sof(H35a)=Sof(H35b)=Sof(H35c)=Sof(C36)=
 Sof(H36a)=Sof(H36b)=Sof(H36c)=Sof(C70A)=Sof(H70d)=Sof(H70e)=Sof(H70f)=
 Sof(C71A)=Sof(H71d)=Sof(H71e)=Sof(H71f)=Sof(C72A)=Sof(H72d)=Sof(H72e)=
 Sof(H72f)=Sof(C81A)=Sof(H81c)=Sof(H81d)=Sof(H82c)=Sof(H82d)=Sof(C88A)=
 Sof(H88d)=Sof(H88e)=Sof(H88f)=Sof(C89A)=Sof(H89c)=Sof(H89d)=Sof(C90A)=
 Sof(H90c)=Sof(H90d)=Sof(C91A)=Sof(H91c)=Sof(H91d)=Sof(C92A)=Sof(H92c)=
 Sof(H92d)=Sof(C93A)=Sof(H93d)=Sof(H93e)=Sof(H93f)=1-FVAR(1)
 Sof(H20)=Sof(C27)=Sof(C32)=Sof(H32)=Sof(C31)=Sof(H31)=Sof(C30)=Sof(H30)=
 Sof(C29)=Sof(H29)=Sof(C28)=Sof(H28)=Sof(C33)=Sof(C34)=Sof(H34a)=Sof(H34b)=
 Sof(H34c)=Sof(C35A)=Sof(H35d)=Sof(H35e)=Sof(H35f)=Sof(C36A)=Sof(H36d)=
 Sof(H36e)=Sof(H36f)=Sof(C70)=Sof(H70a)=Sof(H70b)=Sof(H70c)=Sof(C71)=Sof(H71a)=
 Sof(H71b)=Sof(H71c)=Sof(C72)=Sof(H72a)=Sof(H72b)=Sof(H72c)=Sof(C81)=Sof(H81a)=
 Sof(H81b)=Sof(H82a)=Sof(H82b)=Sof(C88)=Sof(H88b)=Sof(H88c)=Sof(H88a)=Sof(C89)=
 Sof(H89a)=Sof(H89b)=Sof(C90)=Sof(H90a)=Sof(H90b)=Sof(C91)=Sof(H91a)=Sof(H91b)=
 Sof(C92)=Sof(H92a)=Sof(H92b)=Sof(C93)=Sof(H93a)=Sof(H93b)=Sof(H93c)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C7(H7), C20(H20), C20(H20a), C43(H43), C56(H56)
6.b Secondary CH2 refined with riding coordinates:
 C73(H73a,H73b), C74(H74a,H74b), C75(H75a,H75b), C76(H76a,H76b), C77(H77a,
 H77b), C78(H78a,H78b), C79(H79a,H79b), C80(H80a,H80b), C81(H81a,H81b),
 C81A(H81c,H81d), C82(H82a,H82b), C82(H82c,H82d), C83(H83a,H83b), C84(H84a,
 H84b), C86(H86a,H86b), C87(H87a,H87b), C89(H89a,H89b), C90(H90a,H90b),
 C91(H91a,H91b), C92(H92a,H92b), C89A(H89c,H89d), C90A(H90c,H90d), C91A(H91c,
 H91d), C92A(H92c,H92d)
6.c Me refined with riding coordinates:
 C88(H88b,H88c,H88a), C93(H93a,H93b,H93c), C88A(H88d,H88e,H88f), C93A(H93d,
 H93e,H93f)
6.d 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), C22(H22), C23(H23), C24(H24), C25(H25),
  C26(H26), C32(H32), C31(H31), C30(H30), C29(H29), C28(H28), C32A(H32A),
 C31A(H31A), C30A(H30A), C29A(H29A), C28A(H28A), C39(H39), C41(H41), C45(H45),
 C46(H46), C47(H47), C48(H48), C49(H49), C51(H51), C52(H52), C53(H53), C54(H54),
  C55(H55), C58(H58), C59(H59), C60(H60), C61(H61), C62(H62), C64(H64),
 C65(H65), C66(H66), C67(H67), C68(H68)
6.e Fitted hexagon refined as free rotating group:
 C27(C32,C31,C30,C29,C28), C27A(C32A,C31A,C30A,C29A,C28A)
6.f Idealised Me refined as rotating group:
 C34(H34a,H34b,H34c), C34A(H34d,H34e,H34f), C35(H35a,H35b,H35c), C35A(H35d,
 H35e,H35f), C36(H36a,H36b,H36c), C36A(H36d,H36e,H36f), C70(H70a,H70b,H70c),
 C70A(H70d,H70e,H70f), C71(H71a,H71b,H71c), C71A(H71d,H71e,H71f), C72(H72a,H72b,
 H72c), C72A(H72d,H72e,H72f), C85(H85a,H85b,H85c)
;
_shelx_res_checksum              48330
_shelx_hkl_checksum              35240
_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 3.248
_oxdiff_exptl_absorpt_empirical_full_min 0.490