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_1573411
_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         'C10 H23 B2 Dy'
_chemical_formula_sum            'C10 H23 B2 Dy'
_chemical_formula_weight         327.40
_chemical_name_systematic        '[Dy(Cp*)(BH4)2]'
_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   mixed
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-04-30
_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                 117.930(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.3735(3)
_cell_length_b                   20.8167(5)
_cell_length_c                   8.5037(3)
_cell_measurement_reflns_used    8066
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.2380
_cell_measurement_theta_min      4.2350
_cell_volume                     1309.61(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.106a 64-bit (release 01-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.106a (Rigaku OD, 2024)'
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.955
_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     83.00 114.00   0.50    0.20    --  113.25-135.00 107.00   62
  2  \w     55.00  95.00   0.50    0.10    --   46.94-135.00 107.00   80
  3  \w    -13.00  29.00   0.50    0.10    --  -46.94  19.00 -30.00   84
  4  \w    -21.00  29.00   0.50    0.10    --  -46.94  19.00 -90.00  100
  5  \w    -26.00  28.00   0.50    0.10    --  -46.94  19.00-150.00  108
  6  \w     42.00  98.00   0.50    0.10    --   46.94-134.00 -73.00  112
  7  \w     62.00  96.00   0.50    0.20    --  113.25-125.00  30.00   68
  8  \w     67.00 109.00   0.50    0.20    --  113.25-125.00  60.00   84
  9  \w     44.00  70.00   0.50    0.20    --  113.25-125.00 -30.00   52
 10  \w     86.00 111.00   0.50    0.20    --  113.25-125.00 -30.00   50
 11  \w     88.00 113.00   0.50    0.20    --  113.25-134.00 -73.00   50
 12  \w     57.00 106.00   0.50    0.20    --  113.25-125.00-120.00   98
 13  \w     45.00  90.00   0.50    0.20    --  113.25 -94.00 -90.00   90
 14  \w     71.00  98.00   0.50    0.20    --  113.25 -94.00 -60.00   54
 15  \w     43.00  99.00   0.50    0.20    --  113.25 -94.00  90.00  112
 16  \w     63.00 102.00   0.50    0.20    --  113.25 -94.00 120.00   78
 17  \w     52.00  93.00   0.50    0.20    --  113.25 -94.00 150.00   82
 18  \w     43.00  69.00   0.50    0.20    --  113.25 -61.00 150.00   52
 19  \w     43.00  70.00   0.50    0.20    --  113.25 -61.00  90.00   54
 20  \w     46.00  71.00   0.50    0.20    --  113.25 -61.00  60.00   50
 21  \w     43.00  71.00   0.50    0.20    --  113.25 -61.00 120.00   56
 22  \w     42.00  67.00   0.50    0.20    --  113.25 -61.00 -30.00   50
 23  \w     42.00  69.00   0.50    0.20    --  113.25 -61.00 -60.00   54
 24  \w    -17.00   8.00   0.50    0.10    --   46.94 -19.00-120.00   50
 25  \w    -18.00  26.00   0.50    0.10    --   46.94 -19.00   0.00   88
 26  \w     44.00  70.00   0.50    0.20    --  113.25 -61.00 -90.00   52
 27  \w    100.00 146.00   0.50    0.20    --  113.25  15.00-180.00   92
 28  \w    152.00 177.00   0.50    0.20    --  113.25  15.00-180.00   50
 29  \w    102.00 177.00   0.50    0.20    --  113.25  30.00 -90.00  150
 30  \w    109.00 138.00   0.50    0.20    --  113.25 134.00  -5.00   58
 31  \w    143.00 175.00   0.50    0.20    --  113.25 134.00  -5.00   64
 32  \w     93.00 148.00   0.50    0.20    --  113.25 135.00 173.00  110
 33  \w    -73.00 -46.00   0.50    0.20    --  -91.75 134.00  -5.00   54
 34  \w    -57.00 -20.00   0.50    0.20    --  -91.75  61.00-150.00   74
 35  \w    -46.00 -21.00   0.50    0.20    --  -91.75  45.00-120.00   50
 36  \w    -80.00 -55.00   0.50    0.10    --  -46.94 134.00  -5.00   50
 37  \w    -50.00 -21.00   0.50    0.20    --  -91.75  45.00  60.00   58
 38  \w    -82.00 -57.00   0.50    0.10    --  -46.94 135.00 173.00   50
 39  \w    -49.00 -21.00   0.50    0.20    --  -91.75  45.00 150.00   56
 40  \w    -51.00 -26.00   0.50    0.20    --  -91.75  45.00 120.00   50
 41  \w    -79.00 -23.00   0.50    0.20    --  -91.75   0.00-120.00  112
 42  \w   -127.00-102.00   0.50    0.20    --  -91.75   0.00-120.00   50
 43  \w   -164.00-133.00   0.50    0.20    --  -91.75   0.00-120.00   62
 44  \w   -113.00 -79.00   0.50    0.20    --  -91.75 -61.00 -60.00   68
 45  \w    -78.00 -48.00   0.50    0.10    --  -46.94 -37.00-150.00   60
 46  \w   -119.00 -94.00   0.50    0.10    --  -46.94 -37.00-150.00   50
 47  \w   -161.00-124.00   0.50    0.20    --  -91.75 -61.00 -60.00   74
 48  \w   -158.00 -84.00   0.50    0.20    --  -91.75 -30.00 -30.00  148
 49  \w   -127.00 -83.00   0.50    0.20    --  -91.75 -94.00  60.00   88
 50  \w    -98.00 -72.00   0.50    0.20    --  -91.75-135.00 107.00   52
 51  \w   -158.00-106.00   0.50    0.20    --  -91.75-135.00 107.00  104
 52  \w   -108.00 -76.00   0.50    0.10    --  -46.94-135.00 107.00   64
 53  \w   -115.00 -70.00   0.50    0.10    --  -46.94-134.00 -73.00   90
 54  \w   -139.00-114.00   0.50    0.20    --  -91.75-134.00 -73.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0789122000
_diffrn_orient_matrix_UB_12      0.0568621000
_diffrn_orient_matrix_UB_13      0.1299453000
_diffrn_orient_matrix_UB_21      0.0935330000
_diffrn_orient_matrix_UB_22      -0.0474197000
_diffrn_orient_matrix_UB_23      0.1559826000
_diffrn_orient_matrix_UB_31      0.1683933000
_diffrn_orient_matrix_UB_32      -0.0002537000
_diffrn_orient_matrix_UB_33      -0.0287688000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0685
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            15015
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.121
_diffrn_reflns_theta_min         4.248
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    30.145
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.477
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.106a (Rigaku Oxford Diffraction, 2024)
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    1.661
_exptl_crystal_description       block
_exptl_crystal_F_000             636
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Toluene'
_exptl_crystal_size_max          0.254
_exptl_crystal_size_mid          0.228
_exptl_crystal_size_min          0.206
_refine_diff_density_max         2.019
_refine_diff_density_min         -1.846
_refine_diff_density_rms         0.266
_refine_ls_extinction_coef       0.0025(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.065
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     148
_refine_ls_number_reflns         2738
_refine_ls_number_restraints     272
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0485
_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^)+(0.1010P)^2^+2.0665P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1319
_refine_ls_wR_factor_ref         0.1347
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2516
_reflns_number_total             2738
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06661h2.cif
_cod_data_source_block           cdpm82
_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               1573411
_manchester_internal_diff_code   cdpm82
_manchester_internal_coll_client SCC
_manchester_internal_coll_date   30/04/24
_manchester_internal_process_date 30/04/24
_manchester_internal_process_user SCC
_manchester_internal_solution_date 30/04/24
_manchester_internal_solution_user SCC
_manchester_internal_refinement_date 30/04/24
_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         DyCB
_chemical_oxdiff_usercomment     XHD
_shelx_estimated_absorpt_t_max   0.063
_shelx_estimated_absorpt_t_min   0.049
_reflns_odcompleteness_completeness 99.80
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All B(H,H,H,H) groups, All C(H,H,H) groups
2. Restrained distances
 B2-H2C = B2-H2B = B2-H2D = B2-H2A = B1-H1B = B1-H1D = B1-H1A = B1-H1C
 1.15 with sigma of 0.02
 H1B-H1A \\sim H1C-H1A \\sim H1C-H1B \\sim H1D-H1B \\sim H1D-H1C \\sim H1D-H1A
\\sim H2B-H2A \\sim H2C-H2A
 \\sim H2D-H2A \\sim H2D-H2C \\sim H2D-H2B \\sim H2C-H2B
 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(C5) \\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 0.001 and sigma for 1-3 distances of 0.001
5.a Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C8(H8A,H8B,H8C), C7(H7A,H7B,H7C),
 C9(H9A,H9B,H9C)
;
_shelx_res_checksum              23188
_shelx_hkl_checksum              56644
_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 2.403
_oxdiff_exptl_absorpt_empirical_full_min 0.482