A fluorobenzene-bound dysprosium half-sandwich dication single-molecule magnet.
Corner, Sophie C.; Blackmore, William J. A.; Gransbury, Gemma K.; Mattioni, Andrea; Whitehead, George F. S.; Chilton, Nicholas F.; Mills, David P.; Chemical science 16 (2025) 610–620; doi:10.1039/d4sc06661h

data_1573410
_publ_section_title
;
 A fluorobenzene-bound dysprosium half-sandwich dication single-molecule
 magnet.
;
_journal_issue                   2
_journal_name_full               'Chemical science'
_journal_page_first              610
_journal_page_last               620
_journal_paper_doi               10.1039/d4sc06661h
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C38 H25 Dy F23 O2, 2(Al C12 F27.5 O3)'
_chemical_formula_sum            'C62 H25 Al2 Dy F78 O8'
_chemical_formula_weight         2596.28
_chemical_name_systematic        '[Dy{OC(CF3)3}2(FPh)5][{Al[OC(CF3)3]3}2(F)]'
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2023-10-27
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-06-26 deposited with the CCDC.	2024-11-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.564(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.7517(7)
_cell_length_b                   20.9203(7)
_cell_length_c                   18.7796(5)
_cell_measurement_reflns_used    8884
_cell_measurement_temperature    103(5)
_cell_measurement_theta_max      72.3780
_cell_measurement_theta_min      2.0100
_cell_volume                     8529.2(5)
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      103(5)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.971
_diffrn_measured_fraction_theta_max 0.927
_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    -45.00 133.00   1.00   15.00    --   43.52  60.00  60.00  178
  2  \w    -43.00  60.00   1.00   15.00    --   46.08  40.00-150.00  103
  3  \w     71.00 128.00   1.00   15.00    --   46.08  60.00-120.00   57
  4  \w    110.00 135.00   1.00   15.00    --   46.08  40.00-150.00   25
  5  \w     77.00 174.00   1.00   20.00    --  108.20  40.00-150.00   97
  6  \w     19.00 167.00   1.00   20.00    --  108.20  40.00 -30.00  148
  7  \w    117.00 190.00   1.00   20.00    --  108.20  50.00 -90.00   73
  8  \w     21.00 146.00   1.00   20.00    --  108.20  40.00 -60.00  125
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0248940000
_diffrn_orient_matrix_UB_12      0.0668900000
_diffrn_orient_matrix_UB_13      0.0170270000
_diffrn_orient_matrix_UB_21      -0.0204767000
_diffrn_orient_matrix_UB_22      -0.0248883000
_diffrn_orient_matrix_UB_23      0.0720348000
_diffrn_orient_matrix_UB_31      0.0631800000
_diffrn_orient_matrix_UB_32      0.0182748000
_diffrn_orient_matrix_UB_33      0.0357312000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0918
_diffrn_reflns_av_unetI/netI     0.1274
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.927
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            42310
_diffrn_reflns_point_group_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.265
_diffrn_reflns_theta_min         2.035
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    6.988
_exptl_absorpt_correction_T_max  0.099
_exptl_absorpt_correction_T_min  0.006
_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 light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.022
_exptl_crystal_description       block
_exptl_crystal_F_000             5020
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Fluorobenzene layered with n-hexane'
_exptl_crystal_size_max          0.161
_exptl_crystal_size_mid          0.084
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.049
_refine_diff_density_min         -1.904
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.010
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1883
_refine_ls_number_reflns         16771
_refine_ls_number_restraints     5946
_refine_ls_restrained_S_all      0.956
_refine_ls_R_factor_all          0.1512
_refine_ls_R_factor_gt           0.0807
_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^)+(0.1433P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2111
_refine_ls_wR_factor_ref         0.2544
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8763
_reflns_number_total             16771
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06661h2.cif
_cod_data_source_block           ldpm285
_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 1573408--1573414.cif.
;
_cod_database_code               1573410
_manchester_internal_diff_code   ldpm285
_manchester_internal_coll_client SCC
_manchester_internal_coll_date   26/05/23
_manchester_internal_process_date 02/10/23
_manchester_internal_process_user SCC
_manchester_internal_solution_date 02/10/23
_manchester_internal_solution_user SCC
_manchester_internal_refinement_date 02/10/23
_manchester_internal_refinement_user SCC
_manchester_internal_validation_date 02/10/23
_manchester_internal_validation_user SCC
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         DyAlOCF
_reflns_odcompleteness_completeness 96.75
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Shared sites
{C5, C5A}
3. Restrained distances
 Al2-O3_5 \\sim Al2-O3_9 \\sim Al2-O3_8 \\sim Al2-O3_4 \\sim Al2-O3_6 \\sim
Al2-O3_7
 with sigma of 0.02
 F21-C21A \\sim F21-C21
 with sigma of 0.02
 Dy1-F19A \\sim Dy1-F19
 with sigma of 0.02
 O2-C5A \\sim O2-C5
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
F24 \\sim Al1 \\sim O3_1 \\sim O3_2 \\sim O3_3 \\sim C39_1 \\sim C39_2 \\sim
C39_3 \\sim C40_1 \\sim C41_1 \\sim C42_1 \\sim C40_2 \\sim C41_2 \\sim C42_2
\\sim C40_3 \\sim C41_3 \\sim C42_3 \\sim F24_1 \\sim F25_1 \\sim F26_1 \\sim
F27_1 \\sim F28_1 \\sim F29_1 \\sim F30_1 \\sim F31_1 \\sim F32_1 \\sim F24_2
\\sim F25_2 \\sim F26_2 \\sim F27_2 \\sim F28_2 \\sim F29_2 \\sim F30_2 \\sim
F31_2 \\sim F32_2 \\sim F24_3 \\sim F25_3 \\sim F26_3 \\sim F27_3 \\sim F28_3
\\sim F29_3 \\sim F30_3 \\sim F31_3 \\sim F32_3: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08
Al2 \\sim F25 \\sim O3_9 \\sim C39_9 \\sim C40_9 \\sim F24_9 \\sim F25_9 \\sim
F26_9 \\sim C41_9 \\sim F27_9 \\sim F28_9 \\sim F29_9 \\sim C42_9 \\sim F30_9
\\sim F31_9 \\sim F32_9 \\sim O3_4 \\sim C39_4 \\sim C40_4 \\sim F24_4 \\sim
F25_4 \\sim F26_4 \\sim C41_4 \\sim F27_4 \\sim F28_4 \\sim F29_4 \\sim C42_4
\\sim F30_4 \\sim F31_4 \\sim F32_4 \\sim O3_5 \\sim C39_5 \\sim C40_5 \\sim
F24_5 \\sim F25_5 \\sim F26_5 \\sim C41_5 \\sim F27_5 \\sim F28_5 \\sim F29_5
\\sim C42_5 \\sim F30_5 \\sim F31_5 \\sim F32_5 \\sim O3_6 \\sim C39_6 \\sim
C40_6 \\sim F24_6 \\sim F25_6 \\sim F26_6 \\sim C41_6 \\sim F27_6 \\sim F28_6
\\sim F29_6 \\sim C42_6 \\sim F30_6 \\sim F31_6 \\sim F32_6 \\sim O3_7 \\sim
C39_7 \\sim C40_7 \\sim F24_7 \\sim F25_7 \\sim F26_7 \\sim C41_7 \\sim F27_7
\\sim F28_7 \\sim F29_7 \\sim C42_7 \\sim F30_7 \\sim F31_7 \\sim F32_7 \\sim
O3_8 \\sim C39_8 \\sim C40_8 \\sim F24_8 \\sim F25_8 \\sim F26_8 \\sim C41_8
\\sim F27_8 \\sim F28_8 \\sim F29_8 \\sim C42_8 \\sim F30_8 \\sim F31_8 \\sim
F32_8: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
Dy1 \\sim F1 \\sim F2 \\sim F3 \\sim F4 \\sim F5 \\sim F6 \\sim F7 \\sim F8
\\sim F9 \\sim O2 \\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim F10 \\sim F11 \\sim
F12 \\sim F13 \\sim F14 \\sim F15 \\sim F16 \\sim F17 \\sim F18 \\sim F20 \\sim
F21 \\sim F22 \\sim F23 \\sim O1 \\sim C1 \\sim C2 \\sim C3 \\sim C4 \\sim F19
\\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16
\\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24
\\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32
\\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim F19A \\sim
C9A \\sim C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C21A \\sim
C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C5A \\sim C6A \\sim C7A
\\sim C8A \\sim F10A \\sim F11A \\sim F12A \\sim F13A \\sim F14A \\sim F15A
\\sim F16A \\sim F17A \\sim F18A: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Uanis(C5) = Uanis(C5A)
5. 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
6. Same fragment restrains
{F19, C9, C10, C11, C12, C13, C14} sigma for 1-2: 0.02, 1-3: 0.04
as
{F19A, C9A, C10A, C11A, C12A, C13A, C14A}
{C5, C6, C7, C8, F10, F11, F12, F13, F14, F15, F16, F17, F18} sigma for 1-2:
0.02, 1-3: 0.04
as
{C5A, C6A, C7A, C8A, F10A, F11A, F12A, F13A, F14A, F15A, F16A, F17A, F18A}
{O3_2, C39_2, C40_2, F24_2, F25_2, F26_2, C41_2, F27_2, F28_2, F29_2, C42_2,
F30_2, F31_2, F32_2}
{O3_3, C39_3, C40_3, F24_3, F25_3, F26_3, C41_3, F27_3, F28_3, F29_3, C42_3,
F30_3, F31_3, F32_3}
{O3_4, C39_4, C40_4, F24_4, F25_4, F26_4, C41_4, F27_4, F28_4, F29_4, C42_4,
F30_4, F31_4, F32_4}
{O3_5, C39_5, C40_5, F24_5, F25_5, F26_5, C41_5, F27_5, F28_5, F29_5, C42_5,
F30_5, F31_5, F32_5}
{O3_6, C39_6, C40_6, F24_6, F25_6, F26_6, C41_6, F27_6, F28_6, F29_6, C42_6,
F30_6, F31_6, F32_6}
{O3_7, C39_7, C40_7, F24_7, F25_7, F26_7, C41_7, F27_7, F28_7, F29_7, C42_7,
F30_7, F31_7, F32_7}
{O3_8, C39_8, C40_8, F24_8, F25_8, F26_8, C41_8, F27_8, F28_8, F29_8, C42_8,
F30_8, F31_8, F32_8}
{O3_9, C39_9, C40_9, F24_9, F25_9, F26_9, C41_9, F27_9, F28_9, F29_9, C42_9,
F30_9, F31_9, F32_9}
as
{O3_1, C39_1, C40_1, F24_1, F25_1, F26_1, C41_1, F27_1, F28_1, F29_1, C42_1,
F30_1, F31_1, F32_1} sigma for 1-2: 0.02 1-3: 0.04
7. Others
 Sof(F19A)=Sof(C9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=
 Sof(H12A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=Sof(C21A)=Sof(C22A)=
 Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(C25A)=Sof(H25A)=
 Sof(C26A)=Sof(H26A)=Sof(C5A)=Sof(C6A)=Sof(C7A)=Sof(C8A)=Sof(F10A)=Sof(F11A)=
 Sof(F12A)=Sof(F13A)=Sof(F14A)=Sof(F15A)=Sof(F16A)=Sof(F17A)=Sof(F18A)=Sof(O3)=
 Sof(C39)=Sof(C40)=Sof(F24)=Sof(F25)=Sof(F26)=Sof(C41)=Sof(F27)=Sof(F28)=
 Sof(F29)=Sof(C42)=Sof(F30)=Sof(F31)=Sof(F32)=Sof(O3)=Sof(C39)=Sof(C40)=
 Sof(F24)=Sof(F25)=Sof(F26)=Sof(C41)=Sof(F27)=Sof(F28)=Sof(F29)=Sof(C42)=
 Sof(F30)=Sof(F31)=Sof(F32)=Sof(O3)=Sof(C39)=Sof(C40)=Sof(F24)=Sof(F25)=
 Sof(F26)=Sof(C41)=Sof(F27)=Sof(F28)=Sof(F29)=Sof(C42)=Sof(F30)=Sof(F31)=
 Sof(F32)=1-FVAR(1)
 Sof(C5)=Sof(C6)=Sof(C7)=Sof(C8)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=
 Sof(F15)=Sof(F16)=Sof(F17)=Sof(F18)=Sof(F19)=Sof(C9)=Sof(C10)=Sof(H10)=
 Sof(C11)=Sof(H11)=Sof(C12)=Sof(H12)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=
 Sof(C21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=Sof(C25)=
 Sof(H25)=Sof(C26)=Sof(H26)=Sof(O3)=Sof(C39)=Sof(C40)=Sof(F24)=Sof(F25)=
 Sof(F26)=Sof(C41)=Sof(F27)=Sof(F28)=Sof(F29)=Sof(C42)=Sof(F30)=Sof(F31)=
 Sof(F32)=Sof(O3)=Sof(C39)=Sof(C40)=Sof(F24)=Sof(F25)=Sof(F26)=Sof(C41)=
 Sof(F27)=Sof(F28)=Sof(F29)=Sof(C42)=Sof(F30)=Sof(F31)=Sof(F32)=Sof(O3)=
 Sof(C39)=Sof(C40)=Sof(F24)=Sof(F25)=Sof(F26)=Sof(C41)=Sof(F27)=Sof(F28)=
 Sof(F29)=Sof(C42)=Sof(F30)=Sof(F31)=Sof(F32)=FVAR(1)
8.a Aromatic/amide H refined with riding coordinates:
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C16(H16), C17(H17),
 C18(H18), C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26),
  C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C34(H34), C35(H35),
 C36(H36), C37(H37), C38(H38), C10A(H10A), C11A(H11A), C12A(H12A), C13A(H13A),
 C14A(H14A), C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A)
8.b Fitted hexagon refined as free rotating group:
 C9(C10,C11,C12,C13,C14), C15(C16,C17,C18,C19,C20), C21(C22,C23,C24,C25,C26),
 C27(C28,C29,C30,C31,C32), C33(C34,C35,C36,C37,C38), C9A(C10A,C11A,C12A,C13A,
 C14A), C21A(C22A,C23A,C24A,C25A,C26A)
;
_shelx_res_checksum              6437
_shelx_hkl_checksum              61191
_olex2_exptl_crystal_mounting_method 'Mounted in fomblin.'
_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 4.568
_oxdiff_exptl_absorpt_empirical_full_min 0.225