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_1573413
_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         'C36 H54 F2 Si3 Y, 2(Al C12 F27.5 O3)'
_chemical_formula_sum            'C60 H54 Al2 F57 O6 Si3 Y'
_chemical_formula_weight         2181.17
_chemical_name_systematic        '[Y(Cp''')(Cp*)(FPh)2][{Al[OC(CF3)3]3}2(F)]'
_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             2024-04-15
_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                105.461(2)
_cell_angle_beta                 104.692(2)
_cell_angle_gamma                113.530(3)
_cell_formula_units_Z            2
_cell_length_a                   16.6426(5)
_cell_length_b                   16.7663(4)
_cell_length_c                   18.4889(3)
_cell_measurement_reflns_used    16189
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      74.9860
_cell_measurement_theta_min      2.6770
_cell_volume                     4163.3(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.69a (Rigaku OD, 2020)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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     -1.00  32.00   0.50    1.00    --   46.08  30.00 150.00   66
  2  \w    -43.00 134.00   0.50    1.00    --   46.08  30.00  60.00  354
  3  \w     76.00 103.00   0.50    1.00    --   46.08  50.00-180.00   54
  4  \w     57.00 133.00   0.50    1.00    --   46.08  30.00 150.00  152
  5  \w    -40.00 -13.00   0.50    1.00    --   46.08  30.00 150.00   54
  6  \w     99.00 135.00   0.50    1.00    --   46.08  60.00-150.00   72
  7  \w     33.00 134.00   0.50    1.00    --   46.08  60.00  60.00  202
  8  \w    -42.00  18.00   0.50    1.00    --   46.08  60.00  60.00  120
  9  \w    -42.00  29.00   0.50    1.00    --   46.08  50.00-180.00  142
 10  \w    143.00 196.00   0.50    2.00    --  108.20  59.00   2.66  106
 11  \w     28.00  73.00   0.50    2.00    --  108.20  59.00 -37.08   90
 12  \w     51.00 108.00   0.50    2.00    --  108.20  59.00   2.66  114
 13  \w     79.00 198.00   0.50    2.00    --  108.20  59.00 -37.08  238
 14  \w     56.00 142.00   0.50    2.00    --  108.20  59.00 121.68  172
 15  \w     19.00 189.00   0.50    2.00    --  108.20  60.00-131.37  340
 16  \w     20.00 173.00   0.50    2.00    --  108.20  60.00 165.10  306
 17  \w     35.00 143.00   0.50    2.00    --  108.20   0.00 120.00  216
 18  \w    147.00 172.00   0.50    2.00    --  108.20  60.00-113.38   50
 19  \w     80.00 131.00   0.50    2.00    --  108.20  50.00-180.00  102
 20  \w     24.00 196.00   0.50    2.00    --  108.20  59.00 -90.32  344
 21  \w     26.00 123.00   0.50    2.00    --  108.20  60.00-113.38  194
 22  \w    142.00 198.00   0.50    2.00    --  108.20  60.00  65.75  112
 23  \w    104.00 137.00   0.50    2.00    --  108.20  60.00  65.75   66
;
_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      -0.0675025000
_diffrn_orient_matrix_UB_12      -0.0259776000
_diffrn_orient_matrix_UB_13      -0.0873349000
_diffrn_orient_matrix_UB_21      0.0207128000
_diffrn_orient_matrix_UB_22      0.1038820000
_diffrn_orient_matrix_UB_23      0.0261203000
_diffrn_orient_matrix_UB_31      0.0850697000
_diffrn_orient_matrix_UB_32      0.0257665000
_diffrn_orient_matrix_UB_33      -0.0255336000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0691
_diffrn_reflns_av_unetI/netI     0.0709
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            46838
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.251
_diffrn_reflns_theta_min         2.715
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    3.232
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.916
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.69a (Rigaku Oxford Diffraction, 2020)
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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.740
_exptl_crystal_description       block
_exptl_crystal_F_000             2164
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: From fluorobenzene and hexane.'
_exptl_crystal_size_max          0.096
_exptl_crystal_size_mid          0.069
_exptl_crystal_size_min          0.053
_refine_diff_density_max         1.513
_refine_diff_density_min         -1.467
_refine_diff_density_rms         0.110
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1889
_refine_ls_number_reflns         15169
_refine_ls_number_restraints     7027
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.1057
_refine_ls_R_factor_gt           0.0906
_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^)+(0.1816P)^2^+5.0446P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2566
_refine_ls_wR_factor_ref         0.2741
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11860
_reflns_number_total             15169
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06661h2.cif
_cod_data_source_block           ldpm361
_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_original_cell_volume        4163.3(2)
_cod_database_code               1573413
_manchester_internal_diff_code   ldpm361
_manchester_internal_coll_client SCC
_manchester_internal_coll_date   04/03/24
_manchester_internal_process_date 04/03/24
_manchester_internal_process_user SCC
_manchester_internal_solution_date 04/03/24
_manchester_internal_solution_user SCC
_manchester_internal_refinement_date 04/03/24
_manchester_internal_refinement_user SCC
_manchester_internal_validation_date 06/06/24
_manchester_internal_validation_user SCC
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_reflns_odcompleteness_completeness 99.53
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F3_4-F6_6
 -2.8 with sigma of 0.02
 Y1-F2A \\sim Y1-F2
 with sigma of 0.02
 Y1-F1A \\sim Y1-F1
 with sigma of 0.02
 Al2-O1_7 \\sim Al2-O1_6 \\sim Al2-O1_4 \\sim Al2-O1_8 \\sim Al2-O1_4 \\sim
Al2-O1_8 \\sim Al1-O1_1 ~
 Al1-O1_10 \\sim Al1-O1_3 \\sim Al1-O1_11
 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
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. Same fragment restrains
{F1, C25, C26, C27, C28, C29, C30} sigma for 1-2: 0.02, 1-3: 0.04
as
{F1A, C25A, C26A, C27A, C28A, C29A, C30A}
{F2, C31, C32, C33, C34, C35, C36} sigma for 1-2: 0.02, 1-3: 0.04
as
{F2A, C31A, C32A, C33A, C34A, C35A, C36A}
{F3_6, F4_6, F5_6, F6_6, F7_6, F8_6, F9_6, F10_6, F11_6, O1_6, C37_6, C38_6,
C39_6, C40_6}
{F3_8, F4_8, F5_8, F6_8, F7_8, F8_8, F9_8, F10_8, F11_8, O1_8, C37_8, C38_8,
C39_8, C40_8}
{F3_4, F4_4, F5_4, F6_4, F7_4, F8_4, F9_4, F10_4, F11_4, O1_4, C37_4, C38_4,
C39_4, C40_4}
{F3_9, F4_9, F5_9, F6_9, F7_9, F8_9, F9_9, F10_9, F11_9, O1_9, C37_9, C38_9,
C39_9, C40_9}
{F3_5, F4_5, F5_5, F6_5, F7_5, F8_5, F9_5, F10_5, F11_5, O1_5, C37_5, C38_5,
C39_5, C40_5}
{F3_7, F4_7, F5_7, F6_7, F7_7, F8_7, F9_7, F10_7, F11_7, O1_7, C37_7, C38_7,
C39_7, C40_7}
{F3_10, F4_10, F5_10, F6_10, F7_10, F8_10, F9_10, F10_10, F11_10, O1_10,
C37_10, C38_10, C39_10, C40_10}
{F3_1, F4_1, F5_1, F6_1, F7_1, F8_1, F9_1, F10_1, F11_1, O1_1, C37_1, C38_1,
C39_1, C40_1}
{F3_11, F4_11, F5_11, F6_11, F7_11, F8_11, F9_11, F10_11, F11_11, O1_11,
C37_11, C38_11, C39_11, C40_11}
{F3_3, F4_3, F5_3, F6_3, F7_3, F8_3, F9_3, F10_3, F11_3, O1_3, C37_3, C38_3,
C39_3, C40_3}
as
{F3_2, F4_2, F5_2, F6_2, F7_2, F8_2, F9_2, F10_2, F11_2, O1_2, C37_2, C38_2,
C39_2, C40_2} sigma for 1-2: 0.02 1-3: 0.04
6. Others
 Sof(F1A)=Sof(C25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(H27A)=Sof(C28A)=
 Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=Sof(F2A)=Sof(C31A)=Sof(C32A)=
 Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(H34A)=Sof(C35A)=Sof(H35A)=
 Sof(C36A)=Sof(H36A)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=
 Sof(F10)=Sof(F11)=Sof(O1)=Sof(C37)=Sof(C38)=Sof(C39)=Sof(C40)=Sof(F3)=Sof(F4)=
 Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(O1)=Sof(C37)=
 Sof(C38)=Sof(C39)=Sof(C40)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=
 Sof(F9)=Sof(F10)=Sof(F11)=Sof(O1)=Sof(C37)=Sof(C38)=Sof(C39)=Sof(C40)=Sof(F3)=
 Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(O1)=
 Sof(C37)=Sof(C38)=Sof(C39)=Sof(C40)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=
 Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(O1)=Sof(C37)=Sof(C38)=Sof(C39)=Sof(C40)=
 1-FVAR(1)
 Sof(F1)=Sof(C25)=Sof(C26)=Sof(H26)=Sof(C27)=Sof(H27)=Sof(C28)=Sof(H28)=
 Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=Sof(F2)=Sof(C31)=Sof(C32)=Sof(H32)=
 Sof(C33)=Sof(H33)=Sof(C34)=Sof(H34)=Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36)=
 Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=
 Sof(O1)=Sof(C37)=Sof(C38)=Sof(C39)=Sof(C40)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(O1)=Sof(C37)=Sof(C38)=Sof(C39)=
 Sof(C40)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=
 Sof(F11)=Sof(O1)=Sof(C37)=Sof(C38)=Sof(C39)=Sof(C40)=Sof(F3)=Sof(F4)=Sof(F5)=
 Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(O1)=Sof(C37)=Sof(C38)=
 Sof(C39)=Sof(C40)=Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=Sof(F7)=Sof(F8)=Sof(F9)=
 Sof(F10)=Sof(F11)=Sof(O1)=Sof(C37)=Sof(C38)=Sof(C39)=Sof(C40)=FVAR(1)
7.a :
 C15(C16,C17,C18,C19,C20,C21,C22,C23,C24)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C32(H32),
 C33(H33), C34(H34), C35(H35), C36(H36), C26A(H26A), C27A(H27A), C28A(H28A),
 C29A(H29A), C30A(H30A), C32A(H32A), C33A(H33A), C34A(H34A), C35A(H35A),
 C36A(H36A)
7.c Fitted hexagon refined as free rotating group:
 C25(C26,C27,C28,C29,C30), C31(C32,C33,C34,C35,C36)
7.d Idealised Me refined as rotating group:
 C6(H6a,H6b,H6c), C7(H7a,H7b,H7c), C8(H8a,H8b,H8c), C9(H9a,H9b,H9c), C10(H10a,
 H10b,H10c), C11(H11a,H11b,H11c), C12(H12a,H12b,H12c), C13(H13a,H13b,H13c),
 C14(H14a,H14b,H14c), C20(H20a,H20b,H20c), C21(H21a,H21b,H21c), C22(H22a,H22b,
 H22c), C23(H23a,H23b,H23c), C24(H24a,H24b,H24c)
;
_shelx_res_checksum              60690
_shelx_hkl_checksum              28616
_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 2.116
_oxdiff_exptl_absorpt_empirical_full_min 0.410