Solvent-free anhydrous Li+, Na+ and K+ salts of [B(3,5-(CF3)2C6H3)4]−, [BArF4]−. Improved synthesis and solid-state structures
Martínez-Martínez, Antonio J.; Weller, Andrew S.; Dalton Transactions  (2019) –; doi:10.1039/C9DT00235A

data_7049017
_publ_section_title
;
 Solvent-free anhydrous Li+, Na+ and K+ salts of
 [B(3,5-(CF3)2C6H3)4]&#x2212;, [BArF4]&#x2212;. Improved synthesis and
 solid-state structures
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/C9DT00235A
_journal_year                    2019
_chemical_formula_moiety         '0.5(C64 H28 B2 F48 Li2 O2)'
_chemical_formula_sum            'C32 H14 B F24 Li O'
_chemical_formula_weight         888.18
_chemical_properties_physical    Hygroscopic
_space_group_crystal_system      tetragonal
_space_group_IT_number           85
_space_group_name_Hall           '-P 4a'
_space_group_name_H-M_alt        'P 4/n'
_symmetry_space_group_name_Hall  '-P 4a'
_symmetry_space_group_name_H-M   'P 4/n :2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-12-20 deposited with the CCDC.
2019-01-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.45985(14)
_cell_length_b                   13.45985(14)
_cell_length_c                   9.66072(16)
_cell_measurement_reflns_used    11247
_cell_measurement_temperature    150.0(3)
_cell_measurement_theta_max      75.8330
_cell_measurement_theta_min      4.5410
_cell_volume                     1750.21(4)
_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      150.0(3)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4102
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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     59.00 125.00   1.00    1.00    --   42.66 178.00-120.00   66
  2  \w     63.00  98.00   1.00    1.00    --   42.66 178.00-180.00   35
  3  \w     60.00  97.00   1.00    1.00    --   42.66 178.00 -30.00   37
  4  \w     42.00  79.00   1.00    3.00    --  111.00 -45.00  30.00   37
  5  \w     47.00  75.00   1.00    3.00    --  111.00 -30.00-120.00   28
  6  \w     60.00 139.00   1.00    3.00    --  111.00 -61.00 -60.00   79
  7  \w     57.00  89.00   1.00    3.00    --  111.00 -30.00  30.00   32
  8  \w     52.00 103.00   1.00    3.00    --  111.00 -99.00 -85.00   51
  9  \w     42.00  67.00   1.00    3.00    --  111.00 -30.00 -30.00   25
 10  \w     44.00  98.00   1.00    3.00    --  111.00 -45.00 150.00   54
 11  \w    -99.00 -18.00   1.00    1.00    --  -42.66 -57.00 -30.00   81
 12  \w    -55.00 -28.00   1.00    1.00    --  -42.66 -57.00-120.00   27
 13  \w     42.00  68.00   1.00    3.00    --  111.00 -45.00 -30.00   26
 14  \w    143.00 169.00   1.00    3.00    --  111.00  45.00 -30.00   26
 15  \w     81.00 128.00   1.00    3.00    --  111.00  77.00 -90.00   47
 16  \w    121.00 174.00   1.00    3.00    --  111.00 125.00-180.00   53
 17  \w    135.00 172.00   1.00    3.00    --  111.00  45.00 -90.00   37
 18  \w     88.00 130.00   1.00    3.00    --  111.00  45.00 -90.00   42
 19  \w     84.00 110.00   1.00    3.00    --  111.00  61.00-120.00   26
 20  \w    141.00 167.00   1.00    3.00    --  111.00  61.00-120.00   26
 21  \w     96.00 131.00   1.00    3.00    --  111.00  45.00 -30.00   35
 22  \w    136.00 161.00   1.00    3.00    --  111.00  77.00 -90.00   25
 23  \w     84.00 111.00   1.00    3.00    --  111.00  77.00-120.00   27
 24  \w     62.00  90.00   1.00    3.00    --  111.00 -30.00 -90.00   28
 25  \w    -74.00 -48.00   1.00    1.00    --  -42.66  77.00 120.00   26
 26  \w      4.00  31.00   1.00    1.00    --  -42.66  77.00 120.00   27
 27  \w     91.00 116.00   1.00    1.00    --   42.66 178.00  30.00   25
 28  \w     32.00  96.00   1.00    3.00    --  111.00 -95.00-150.00   64
 29  \w     39.00  85.00   1.00    3.00    --  111.00 -30.00-180.00   46
 30  \w    145.00 177.00   1.00    3.00    --  111.00  45.00  30.00   32
 31  \w     97.00 123.00   1.00    3.00    --  111.00  61.00 -60.00   26
 32  \w    126.00 152.00   1.00    3.00    --  111.00  61.00-180.00   26
 33  \w     85.00 111.00   1.00    3.00    --  111.00  61.00-180.00   26
 34  \w    134.00 175.00   1.00    3.00    --  111.00  61.00 -60.00   41
 35  \w    116.00 155.00   1.00    3.00    --  111.00  30.00-150.00   39
 36  \w     -2.00  25.00   1.00    1.00    --  -42.66  38.00  30.00   27
 37  \w   -115.00 -16.00   1.00    1.00    --  -42.66 -19.00-150.00   99
 38  \w     56.00  83.00   1.00    1.00    --   42.66 -99.00 -30.00   27
 39  \w     90.00 121.00   1.00    3.00    --  111.00-131.00 119.02   31
 40  \w    125.00 152.00   1.00    3.00    --  111.00 125.00 150.00   27
 41  \w     43.00  89.00   1.00    3.00    --  111.00 -45.00-120.00   46
 42  \w     42.00  68.00   1.00    3.00    --  111.00-131.00 119.02   26
 43  \w     36.00  62.00   1.00    3.00    --  111.00 -30.00 -60.00   26
 44  \w     56.00  82.00   1.00    3.00    --  111.00-125.00 -90.00   26
 45  \w     43.00  81.00   1.00    3.00    --  111.00 -45.00  90.00   38
 46  \w     78.00 104.00   1.00    3.00    --  111.00-125.00-150.00   26
 47  \w     65.00  92.00   1.00    3.00    --  111.00-125.00   0.00   27
 48  \w     36.00  61.00   1.00    3.00    --  111.00 -30.00   0.00   25
 49  \w    106.00 133.00   1.00    3.00    --  111.00 125.00-150.00   27
 50  \w     75.00 118.00   1.00    3.00    --  111.00-125.00-180.00   43
 51  \w     81.00 142.00   1.00    3.00    --  111.00 -77.00   0.00   61
 52  \w     97.00 130.00   1.00    3.00    --  111.00-141.00  40.39   33
 53  \w     92.00 118.00   1.00    3.00    --  111.00-125.00-120.00   26
 54  \w     91.00 117.00   1.00    3.00    --  111.00-125.00 -60.00   26
 55  \w     46.00  91.00   1.00    3.00    --  111.00-141.00  40.39   45
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0914619000
_diffrn_orient_matrix_UB_12      0.0677943000
_diffrn_orient_matrix_UB_13      -0.0167063000
_diffrn_orient_matrix_UB_21      -0.0583373000
_diffrn_orient_matrix_UB_22      0.0658260000
_diffrn_orient_matrix_UB_23      -0.1020234000
_diffrn_orient_matrix_UB_31      -0.0365667000
_diffrn_orient_matrix_UB_32      0.0645689000
_diffrn_orient_matrix_UB_33      0.1213873000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0207
_diffrn_reflns_av_unetI/netI     0.0079
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            22082
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.216
_diffrn_reflns_theta_min         4.577
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.736
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.92535
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.685
_exptl_crystal_description       prism
_exptl_crystal_F_000             876
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.430
_refine_diff_density_min         -0.333
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     192
_refine_ls_number_reflns         1826
_refine_ls_number_restraints     231
_refine_ls_restrained_S_all      1.488
_refine_ls_R_factor_all          0.0537
_refine_ls_R_factor_gt           0.0523
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0640P)^2^+1.3632P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1380
_refine_ls_wR_factor_ref         0.1390
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1744
_reflns_number_total             1826
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt00235a2.cif
_cod_data_source_block           libarf4h2o
_cod_original_cell_volume        1750.21(5)
_cod_database_code               7049017
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C32 H12 B1 F24 Li1'
_shelx_estimated_absorpt_t_max   0.819
_shelx_estimated_absorpt_t_min   0.769
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 F5-F6 \\sim F5-F4 \\sim F5A-F6A \\sim F5A-F4A
 with sigma of 0.04
 C8-F5 \\sim C8-F5A \\sim C8-F6 \\sim C8-F6A \\sim C8-F4A \\sim C8-F4
 with sigma of 0.02
 F2-F3 \\sim F2-F1 \\sim F2A-F3A \\sim F2A-F1A \\sim F3A-F1A \\sim F3-F1
 with sigma of 0.04
 C7-F2 \\sim C7-F2A \\sim C7-F3A \\sim C7-F3 \\sim C7-F1 \\sim C7-F1A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
F5 \\sim F4 \\sim C8 \\sim F6 \\sim F5A \\sim F4A \\sim F6A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
F2 \\sim F3 \\sim F1 \\sim C7 \\sim F2A \\sim F3A \\sim F1A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 F5, F4, C8, F6, F5A, F4A, F6A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F2, F3, F1, F2A, F3A, F1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F5A)=Sof(F4A)=Sof(F6A)=1-FVAR(1)
 Sof(F5)=Sof(F4)=Sof(F6)=FVAR(1)
 Sof(F2A)=Sof(F3A)=Sof(F1A)=1-FVAR(2)
 Sof(F2)=Sof(F3)=Sof(F1)=FVAR(2)
 Fixed Sof: H1A(0.25) H1B(0.25)
6.a Rotating group:
 O1(H1A,H1B)
6.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C4(H4)
;
_shelx_res_checksum              39434
_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 1.111
_oxdiff_exptl_absorpt_empirical_full_min 0.939