<i>Ab initio</i>-based determination of lanthanoid-radical exchange as visualised by inelastic neutron scattering.
Dunstan, Maja A.; Giansiracusa, Marcus J.; Calvello, Simone; Sorace, Lorenzo; Krause-Heuer, Anwen M; Soncini, Alessandro; Mole, Richard A.; Boskovic, Colette; Chemical science 15 (2024) 4466–4477; doi:10.1039/d3sc04229d

data_1570987
_publ_section_title
;
 <i>Ab initio</i>-based determination of lanthanoid-radical exchange as
 visualised by inelastic neutron scattering.
;
_journal_issue                   12
_journal_name_full               'Chemical science'
_journal_page_first              4466
_journal_page_last               4477
_journal_paper_doi               10.1039/d3sc04229d
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C32 H40 B2 Er N12 O2'
_chemical_formula_sum            'C32 H40 B2 Er N12 O2'
_chemical_formula_weight         813.64
_chemical_name_systematic
erbium(III)bis(tris-pyrazolylborato)(3,5-di-tert-butylsemiquinonato)
_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
_audit_creation_date             2022-01-10
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-08-10 deposited with the CCDC.	2024-02-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.3210(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.59650(10)
_cell_length_b                   14.87660(10)
_cell_length_c                   19.51760(10)
_cell_measurement_reflns_used    32510
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      77.8430
_cell_measurement_theta_min      3.5550
_cell_volume                     3618.96(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14a (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.990
_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    -30.00  25.00   0.50    0.41    --  -48.30  19.00-120.00  110
  2  \w    -69.00  19.00   0.50    0.41    --  -48.30  77.00 -60.00  176
  3  \w      2.00  61.00   0.50    0.41    --   48.30 -57.00 150.00  118
  4  \w     43.00  91.00   0.50    0.41    --   48.30-125.00  30.00   96
  5  \w     44.00  71.00   0.50    1.64    --  107.75 -61.00  90.00   54
  6  \w     52.00  78.00   0.50    1.64    --  107.75 -94.00  90.00   52
  7  \w     81.00 106.00   0.50    1.64    --  107.75 -94.00  90.00   50
  8  \w     83.00 110.00   0.50    1.64    --  107.75-125.00  60.00   54
  9  \w     74.00 106.00   0.50    1.64    --  107.75 -94.00  60.00   64
 10  \w     78.00 106.00   0.50    1.64    --  107.75 -94.00   0.00   56
 11  \w     81.00 107.00   0.50    1.64    --  107.75-125.00 -60.00   52
 12  \w     74.00 101.00   0.50    1.64    --  107.75 -77.00 -60.00   54
 13  \w     72.00 106.00   0.50    1.64    --  107.75 -94.00 -60.00   68
 14  \w     55.00 107.00   0.50    1.64    --  107.75-108.00 -49.52  104
 15  \w     64.00 106.00   0.50    1.64    --  107.75 -97.00  39.47   84
 16  \w     59.00  95.00   0.50    1.64    --  107.75 -77.00 -30.00   72
 17  \w     38.00  64.00   0.50    1.64    --  107.75 -77.00  30.00   52
 18  \w     36.00  63.00   0.50    1.64    --  107.75 -94.00  60.00   54
 19  \w     42.00 105.00   0.50    1.64    --  107.75 -94.00 120.00  126
 20  \w     67.00 106.00   0.50    1.64    --  107.75 -98.00 170.00   78
 21  \w     37.00  65.00   0.50    1.64    --  107.75-125.00  60.00   56
 22  \w     43.00  69.00   0.50    1.64    --  107.75 -94.00   0.00   52
 23  \w     42.00  69.00   0.50    1.64    --  107.75 -61.00 -60.00   54
 24  \w     40.00  67.00   0.50    1.64    --  107.75 -94.00 -60.00   54
 25  \w     37.00  70.00   0.50    1.64    --  107.75 -77.00 -60.00   66
 26  \w     56.00  88.00   0.50    1.64    --  107.75 -77.00-120.00   64
 27  \w     81.00 106.00   0.50    1.64    --  107.75 -94.00-150.00   50
 28  \w     78.00 105.00   0.50    1.64    --  107.75 -94.00-180.00   54
 29  \w     55.00  91.00   0.50    1.64    --  107.75 -77.00-150.00   72
 30  \w     41.00  69.00   0.50    1.64    --  107.75 -61.00-150.00   56
 31  \w     53.00  91.00   0.50    1.64    --  107.75 -77.00-180.00   76
 32  \w     39.00  74.00   0.50    1.64    --  107.75 -94.00-180.00   70
 33  \w     39.00  64.00   0.50    1.64    --  107.75 -94.00-150.00   50
 34  \w     98.00 155.00   0.50    1.64    --  107.75  15.00   0.00  114
 35  \w     98.00 153.00   0.50    1.64    --  107.75  30.00 -60.00  110
 36  \w    103.00 174.00   0.50    1.64    --  107.75  30.00-150.00  142
 37  \w    104.00 174.00   0.50    1.64    --  107.75  30.00 -90.00  140
 38  \w     97.00 163.00   0.50    1.64    --  107.75  15.00-180.00  132
 39  \w     99.00 166.00   0.50    1.64    --  107.75  30.00-120.00  134
 40  \w     97.00 164.00   0.50    1.64    --  107.75  15.00  30.00  134
 41  \w     97.00 155.00   0.50    1.64    --  107.75  15.00 150.00  116
 42  \w    100.00 150.00   0.50    1.64    --  107.75  30.00  90.00  100
 43  \w     36.00  61.00   0.50    1.64    --  107.75 -61.00  30.00   50
 44  \w     39.00  65.00   0.50    1.64    --  107.75 -61.00  60.00   52
 45  \w     36.00  69.00   0.50    1.64    --  107.75 -61.00 120.00   66
 46  \w     40.00  66.00   0.50    1.64    --  107.75 -77.00 150.00   52
 47  \w     37.00  62.00   0.50    1.64    --  107.75 -77.00  60.00   50
 48  \w     36.00  61.00   0.50    1.64    --  107.75 -61.00   0.00   50
 49  \w   -114.00 -40.00   0.50    0.41    --  -48.30 -77.00 120.00  148
 50  \w   -114.00  10.00   0.50    0.41    --  -48.30   0.00  90.00  248
 51  \w   -136.00-111.00   0.50    1.64    --  -86.25 -45.00  90.00   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      0.1057828000
_diffrn_orient_matrix_UB_12      0.0520785000
_diffrn_orient_matrix_UB_13      0.0195141000
_diffrn_orient_matrix_UB_21      -0.0636144000
_diffrn_orient_matrix_UB_22      0.0881895000
_diffrn_orient_matrix_UB_23      0.0020162000
_diffrn_orient_matrix_UB_31      -0.0065223000
_diffrn_orient_matrix_UB_32      -0.0155073000
_diffrn_orient_matrix_UB_33      0.0772991000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0342
_diffrn_reflns_av_unetI/netI     0.0205
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            54321
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.074
_diffrn_reflns_theta_min         3.546
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.683
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.817
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14a (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            'dark blue'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.493
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             1640
_exptl_crystal_preparation
'Reactino of KTp, dbsq-, and Er(III) nitrate hexahydrate in methanol.'
_exptl_crystal_recrystallization_method 'Crystallisation from n-hexane at -18C.'
_exptl_crystal_size_max          0.133
_exptl_crystal_size_mid          0.079
_exptl_crystal_size_min          0.038
_refine_diff_density_max         0.824
_refine_diff_density_min         -0.950
_refine_diff_density_rms         0.071
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     448
_refine_ls_number_reflns         7666
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0270
_refine_ls_R_factor_gt           0.0262
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0326P)^2^+3.9293P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0683
_refine_ls_wR_factor_ref         0.0689
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7387
_reflns_number_total             7666
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc04229d3.cif
_cod_data_source_block           er-dbsq
_cod_depositor_comments
'Adding full bibliography for 1570987--1570990.cif.'
_cod_database_code               1570987
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Er C32 H40 O2 N12 B2'
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 B1(H1A), B2(H2A)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C9(H9),
 C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17),
  C18(H18), C22(H22), C23(H23)
2.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C27(H27A,H27B,H27C), C28(H28A,H28B,H28C), C30(H30A,H30B,
 H30C), C31(H31A,H31B,H31C), C32(H32A,H32B,H32C)
;
_shelx_res_checksum              27317
_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 1.816
_oxdiff_exptl_absorpt_empirical_full_min 0.763