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_1573414
_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
'2(C46 H45 Dy F6), 4(Al2 C24 F55 O6), C6 H5 F, 2(C6 H14)'
_chemical_formula_sum            'C206 H123 Al8 Dy2 F233 O24'
_chemical_formula_weight         7949.88
_chemical_name_systematic        '[Dy(Cp*)(FPh)6][{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 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-06-06
_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                 94.8490(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   18.2139(3)
_cell_length_b                   19.3140(4)
_cell_length_c                   40.1803(6)
_cell_measurement_reflns_used    41993
_cell_measurement_temperature    99.9(2)
_cell_measurement_theta_max      75.7940
_cell_measurement_theta_min      2.1870
_cell_volume                     14084.2(4)
_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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.972
_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     27.00 126.00   0.50    1.00    --   43.87  50.00-150.00  198
  2  \w    -46.00 -18.00   0.50    1.00    --   43.87  50.00-150.00   56
  3  \w    -25.00   2.00   0.50    1.00    --   46.33  60.00 -90.00   54
  4  \w    -38.00  -8.00   0.50    1.00    --   46.33  40.00  30.00   60
  5  \w      3.00  39.00   0.50    1.00    --   46.33  40.00  30.00   72
  6  \w     51.00 112.00   0.50    1.00    --   46.33  60.00 -90.00  122
  7  \w    -43.00 136.00   0.50    1.00    --   46.33  60.00 -30.00  358
  8  \w     79.00 136.00   0.50    1.00    --   46.33  40.00  30.00  114
  9  \w     67.00 109.00   0.50    2.00    --  108.20  60.00  90.47   84
 10  \w     20.00  52.00   0.50    2.00    --  108.20  60.00-154.72   64
 11  \w    136.00 197.00   0.50    2.00    --  108.20  60.00-118.46  122
 12  \w     19.00  66.00   0.50    2.00    --  108.20  20.00-150.00   94
 13  \w     96.00 198.00   0.50    2.00    --  108.20  20.00-150.00  204
 14  \w     19.00 198.00   0.50    2.00    --  108.20  50.00  60.00  358
 15  \w    139.00 189.00   0.50    2.00    --  108.20  60.00  -5.79  100
 16  \w     39.00  69.00   0.50    2.00    --  108.20  60.00 -51.49   60
 17  \w     19.00 183.00   0.50    2.00    --  108.20  59.00  43.20  328
 18  \w     73.00 125.00   0.50    2.00    --  108.20  60.00-118.46  104
 19  \w     81.00 129.00   0.50    2.00    --  108.20  58.00 -57.84   96
 20  \w    158.00 184.00   0.50    2.00    --  108.20  60.00  90.47   52
 21  \w     20.00  46.00   0.50    2.00    --  108.20  60.00-118.46   52
 22  \w    140.00 165.00   0.50    2.00    --  108.20  60.00 -51.49   50
 23  \w     19.00 130.00   0.50    2.00    --  108.20  60.00  -5.79  222
 24  \w    155.00 197.00   0.50    2.00    --  108.20  60.00-154.72   84
 25  \w     65.00  95.00   0.50    2.00    --  108.20  50.00-180.00   60
 26  \w    126.00 193.00   0.50    2.00    --  108.20  50.00-180.00  134
;
_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      -0.0842480000
_diffrn_orient_matrix_UB_12      -0.0087136000
_diffrn_orient_matrix_UB_13      -0.0054844000
_diffrn_orient_matrix_UB_21      0.0105148000
_diffrn_orient_matrix_UB_22      -0.0669993000
_diffrn_orient_matrix_UB_23      -0.0198744000
_diffrn_orient_matrix_UB_31      0.0006975000
_diffrn_orient_matrix_UB_32      -0.0424019000
_diffrn_orient_matrix_UB_33      0.0324770000
_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  0.1105
_diffrn_reflns_av_unetI/netI     0.0807
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       50
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            148391
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.357
_diffrn_reflns_theta_min         2.207
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    5.042
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.715
_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    1.875
_exptl_crystal_description       block
_exptl_crystal_F_000             7768
_exptl_crystal_preparation       'Magnetic properties'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Fluorobenzene layered with n-hexane'
_exptl_crystal_size_max          0.164
_exptl_crystal_size_mid          0.144
_exptl_crystal_size_min          0.098
_refine_diff_density_max         1.305
_refine_diff_density_min         -1.211
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3277
_refine_ls_number_reflns         29078
_refine_ls_number_restraints     16088
_refine_ls_restrained_S_all      1.195
_refine_ls_R_factor_all          0.1074
_refine_ls_R_factor_gt           0.0910
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2580
_refine_ls_wR_factor_ref         0.2804
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21765
_reflns_number_total             29078
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06661h2.cif
_cod_data_source_block           ldpm347
_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               1573414
_manchester_internal_diff_code   ldpm347
_manchester_internal_coll_client SCC
_manchester_internal_coll_date   09/02/24
_manchester_internal_process_date 20/03/24
_manchester_internal_process_user SCC
_manchester_internal_solution_date 20/03/24
_manchester_internal_solution_user SCC
_manchester_internal_refinement_date 20/03/24
_manchester_internal_refinement_user SCC
_manchester_internal_validation_date 06/06/24
_manchester_internal_validation_user SCC
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         DyAlOCF
_shelx_estimated_absorpt_t_max   0.638
_shelx_estimated_absorpt_t_min   0.492
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F9-C50
 1.35 with sigma of 0.02
 F12_2-F10_5
 -2.8 with sigma of 0.02
 C58-C57 = C57-C56 = C55-C56 = C55-C54 = C53-C54
 1.5 with sigma of 0.02
 F12_5-F12_2
 -2.8 with sigma of 0.02
 F9_1-F14_18
 -2.8 with sigma of 0.02
 F9_1-F15_18
 -2.8 with sigma of 0.02
 F13_6-F10_6
 -2.8 with sigma of 0.02
 F8_16-F10_16
 -2.8 with sigma of 0.02
 F9_18-F13_21
 -2.8 with sigma of 0.02
 F14_18-F11_18
 -2.8 with sigma of 0.02
 F12_2-F11_5
 -2.8 with sigma of 0.02
 C53-C55 \\sim C54-C56 \\sim C57-C55 \\sim C58-C56
 with sigma of 0.02
 Al3-O1_12 \\sim Al3-O1_13 \\sim Al3-O1_9 \\sim Al3-O1_14 \\sim Al4-O1_15 \\sim
Al4-O1_10 \\sim Al4-
 O1_11 \\sim Al4-O1_16 \\sim Al3-O1_7 \\sim Al3-O1_17
 with sigma of 0.02
 F9-C49 \\sim F9-C51
 with sigma of 0.02
3. Restrained planarity
 F9, C47, C48, C49, C50, C51, C52
 with sigma of 0.1
4. 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
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
{F7_3, F8_3, F9_3, F10_3, F11_3, F12_3, F13_3, F14_3, F15_3, O1_3, C47_3,
C48_3, C49_3, C50_3}
{F7_4, F8_4, F9_4, F10_4, F11_4, F12_4, F13_4, F14_4, F15_4, O1_4, C47_4,
C48_4, C49_4, C50_4}
{F7_5, F8_5, F9_5, F10_5, F11_5, F12_5, F13_5, F14_5, F15_5, O1_5, C47_5,
C48_5, C49_5, C50_5}
{F7_6, F8_6, F9_6, F10_6, F11_6, F12_6, F13_6, F14_6, F15_6, O1_6, C47_6,
C48_6, C49_6, C50_6}
{F7_7, F8_7, F9_7, F10_7, F11_7, F12_7, F13_7, F14_7, F15_7, O1_7, C47_7,
C48_7, C49_7, C50_7}
{F7_8, F8_8, F9_8, F10_8, F11_8, F12_8, F13_8, F14_8, F15_8, O1_8, C47_8,
C48_8, C49_8, C50_8}
{F7_9, F8_9, F9_9, F10_9, F11_9, F12_9, F13_9, F14_9, F15_9, O1_9, C47_9,
C48_9, C49_9, C50_9}
{F7_10, F8_10, F9_10, F10_10, F11_10, F12_10, F13_10, F14_10, F15_10, O1_10,
C47_10, C48_10, C49_10, C50_10}
{F7_11, F8_11, F9_11, F10_11, F11_11, F12_11, F13_11, F14_11, F15_11, O1_11,
C47_11, C48_11, C49_11, C50_11}
{F7_12, F8_12, F9_12, F10_12, F11_12, F12_12, F13_12, F14_12, F15_12, O1_12,
C47_12, C48_12, C49_12, C50_12}
{F7_13, F8_13, F9_13, F10_13, F11_13, F12_13, F13_13, F14_13, F15_13, O1_13,
C47_13, C48_13, C49_13, C50_13}
{F7_14, F8_14, F9_14, F10_14, F11_14, F12_14, F13_14, F14_14, F15_14, O1_14,
C47_14, C48_14, C49_14, C50_14}
{F7_15, F8_15, F9_15, F10_15, F11_15, F12_15, F13_15, F14_15, F15_15, O1_15,
C47_15, C48_15, C49_15, C50_15}
{F7_16, F8_16, F9_16, F10_16, F11_16, F12_16, F13_16, F14_16, F15_16, O1_16,
C47_16, C48_16, C49_16, C50_16}
{F7_17, F8_17, F9_17, F10_17, F11_17, F12_17, F13_17, F14_17, F15_17, O1_17,
C47_17, C48_17, C49_17, C50_17}
{F7_18, F8_18, F9_18, F10_18, F11_18, F12_18, F13_18, F14_18, F15_18, O1_18,
C47_18, C48_18, C49_18, C50_18}
{F7_19, F8_19, F9_19, F10_19, F11_19, F12_19, F13_19, F14_19, F15_19, O1_19,
C47_19, C48_19, C49_19, C50_19}
{F7_20, F8_20, F9_20, F10_20, F11_20, F12_20, F13_20, F14_20, F15_20, O1_20,
C47_20, C48_20, C49_20, C50_20}
{F7_21, F8_21, F9_21, F10_21, F11_21, F12_21, F13_21, F14_21, F15_21, O1_21,
C47_21, C48_21, C49_21, C50_21}
{F7_2, F8_2, F9_2, F10_2, F11_2, F12_2, F13_2, F14_2, F15_2, O1_2, C47_2,
C48_2, C49_2, C50_2}
as
{F7_1, F8_1, F9_1, F10_1, F11_1, F12_1, F13_1, F14_1, F15_1, O1_1, C47_1,
C48_1, C49_1, C50_1} sigma for 1-2: 0.02 1-3: 0.04
7. Others
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=
 Sof(O1)=Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=
 Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=Sof(C48)=
 Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=
 Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=
 Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=
 Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=
 Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=
 Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=
 Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=Sof(C48)=Sof(C49)=
 Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=
 Sof(F15)=Sof(O1)=Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=
 Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=
 Sof(C48)=Sof(C49)=Sof(C50)=1-FVAR(1)
 Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=
 Sof(O1)=Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=
 Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=Sof(C48)=
 Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=
 Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=
 Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=
 Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=
 Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=
 Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=
 Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=
 Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=Sof(C48)=Sof(C49)=
 Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=
 Sof(F15)=Sof(O1)=Sof(C47)=Sof(C48)=Sof(C49)=Sof(C50)=Sof(F7)=Sof(F8)=Sof(F9)=
 Sof(F10)=Sof(F11)=Sof(F12)=Sof(F13)=Sof(F14)=Sof(F15)=Sof(O1)=Sof(C47)=
 Sof(C48)=Sof(C49)=Sof(C50)=FVAR(1)
 Fixed Sof: F9(0.5) C47(0.5) H47(0.5) C48(0.5) H48(0.5) C49(0.5) H49(0.5)
 C50(0.5) C51(0.5) H51(0.5) C52(0.5) H52(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C54(H54a,H54b), C55(H55a,H55b), C56(H56a,H56b), C57(H57a,H57b)
8.b Me refined with riding coordinates:
 C53(H53a,H53b,H53c), C58(H58a,H58b,H58c)
8.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C18(H18), C19(H19),
 C20(H20), C21(H21), C22(H22), C24(H24), C25(H25), C26(H26), C27(H27), C28(H28),
  C30(H30), C31(H31), C32(H32), C33(H33), C34(H34), C36(H36), C37(H37),
 C38(H38), C39(H39), C40(H40), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46),
  C47(H47), C48(H48), C49(H49), C51(H51), C52(H52)
8.d Fitted hexagon refined as free rotating group:
 C29(C30,C31,C32,C33,C34), C47(C48,C49,C50,C51,C52)
8.e 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)
;
_shelx_res_checksum              4928
_shelx_hkl_checksum              19450
_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 4.281
_oxdiff_exptl_absorpt_empirical_full_min 0.428