Hidden Silylium-Type Reactivity of a Siloxane-Based Phosphonium–Hydroborate Ion Pair
Fontana, Nicolò; Espinosa-Jalapa, Noel Angel; Seidl, Michael; Bauer, Jonathan O.; Chemical Communications  (2022) –; doi:10.1039/D1CC07016A

data_7129585
_publ_section_title
;
 Hidden Silylium-Type Reactivity of a Siloxane-Based
 Phosphonium--Hydroborate Ion Pair
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC07016A
_journal_year                    2022
_chemical_formula_moiety         'C18 H2.5 B F14.5 O, 2(C4 H8 O)'
_chemical_formula_sum            'C26 H18.5 B F14.5 O3'
_chemical_formula_weight         665.236
_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'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2021-07-14
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.06.29 svn.r12e2184c for OlexSys, GUI svn.r6374)
;
_audit_update_record
;
2021-09-02 deposited with the CCDC.	2022-01-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.288(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.2436(3)
_cell_length_b                   29.8297(7)
_cell_length_c                   9.9706(3)
_cell_measurement_reflns_used    12818
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      32.5840
_cell_measurement_theta_min      2.2240
_cell_volume                     2651.94(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.90a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement
'olex2.refine 1.5-alpha (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      123.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.9996
_diffrn_measured_fraction_theta_max 0.9948
_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     11.00  48.00   0.50    4.00    --    0.14  41.00 -22.78   74
  2  \w     -8.00  38.00   0.50    4.00    --    0.14  92.00-108.20   92
  3  \w    -15.00  13.00   0.50    4.00    --    0.14 102.00 116.06   56
  4  \w     -9.00  47.00   0.50    4.00    --    0.14  19.00 120.00  112
  5  \w    -16.00  22.00   0.50    4.00    --   32.00 -42.00 -56.94   76
  6  \w    -14.00  20.00   0.50    4.00    --   32.00 -46.00 -82.40   68
  7  \w    -46.00  -9.00   0.50    4.00    --    0.14 -49.00-163.07   74
  8  \w    -22.00  15.00   0.50    4.00    --   24.00 -49.00-139.21   74
  9  \w    -13.00  15.00   0.50    4.00    --    0.14-101.00 147.51   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0760829000
_diffrn_orient_matrix_UB_12      0.0069489000
_diffrn_orient_matrix_UB_13      0.0173024000
_diffrn_orient_matrix_UB_21      -0.0224780000
_diffrn_orient_matrix_UB_22      0.0215429000
_diffrn_orient_matrix_UB_23      -0.0278623000
_diffrn_orient_matrix_UB_31      -0.0060145000
_diffrn_orient_matrix_UB_32      0.0072755000
_diffrn_orient_matrix_UB_33      0.0660437000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0289
_diffrn_reflns_av_unetI/netI     0.0269
_diffrn_reflns_Laue_measured_fraction_full 0.9996
_diffrn_reflns_Laue_measured_fraction_max 0.9948
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       45
_diffrn_reflns_limit_k_min       -44
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            44425
_diffrn_reflns_point_group_measured_fraction_full 0.9996
_diffrn_reflns_point_group_measured_fraction_max 0.9948
_diffrn_reflns_theta_full        25.2417
_diffrn_reflns_theta_max         32.62
_diffrn_reflns_theta_min         2.22
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.175
_exptl_absorpt_correction_T_max  0.989
_exptl_absorpt_correction_T_min  0.956
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.90a (Rigaku Oxford Diffraction, 2020)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
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    1.666
_exptl_crystal_description       plate
_exptl_crystal_F_000             1337.404
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: pentane/tetrahydrofuran'
_exptl_crystal_size_max          0.443
_exptl_crystal_size_mid          0.118
_exptl_crystal_size_min          0.078
_refine_diff_density_max         0.6516
_refine_diff_density_min         -0.5345
_refine_diff_density_rms         0.0749
_refine_ls_d_res_high            0.6593
_refine_ls_d_res_low             9.1537
_refine_ls_goodness_of_fit_ref   1.0261
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    54
_refine_ls_number_parameters     436
_refine_ls_number_reflns         9629
_refine_ls_number_restraints     59
_refine_ls_restrained_S_all      1.0228
_refine_ls_R_factor_all          0.0690
_refine_ls_R_factor_gt           0.0463
_refine_ls_shift/su_max          -0.0008
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0582P)^2^+0.7346P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1156
_refine_ls_wR_factor_ref         0.1263
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              13
_reflns_limit_h_min              -14
_reflns_limit_k_max              45
_reflns_limit_k_min              0
_reflns_limit_l_max              15
_reflns_limit_l_min              0
_reflns_number_gt                7025
_reflns_number_total             9629
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d1cc07016a2.cif
_cod_data_source_block           nf_771_subl_thf_2_mp_abs_ana
_cod_database_code               7129585
_chemical_oxdiff_formula         C26H18.5BF14.5O3
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 C24a-C23 \\sim C24b-C23 \\sim C25-C24a \\sim C25-C24b \\sim C26-C25
 with sigma of 0.005
3. Uiso/Uaniso restraints and constraints
C21b \\sim C21a \\sim C20b \\sim C20a: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
C24b \\sim C24a \\sim C25: within 1.7A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 1.7A
4. Others
 Fixed Sof: F3(0.9) F8(0.8) F13(0.8) H10(0.2) H16(0.2) H19a(0.75) H19b(0.75)
 H19c(0.25) H19d(0.25) H4(0.1) H22a(0.75) H22b(0.75) H22c(0.25) H22d(0.25)
 C20a(0.75) H20a(0.75) H20b(0.75) C21a(0.75) H21a(0.75) H21b(0.75) C21b(0.25)
 H21c(0.25) H21d(0.25) C20b(0.25) H20c(0.25) H20d(0.25) H23a(0.75) H23b(0.75)
 H23c(0.25) H23d(0.25) H25a(0.75) H25b(0.75) H25c(0.25) H25d(0.25) H24c(0.25)
 H24d(0.25) C24a(0.78) C24b(0.22) H23a(0.78) H23b(0.78) H23c(0.22) H23d(0.22)
 H25a(0.78) H25b(0.78) H25c(0.22) H25d(0.22) H24a(0.78) H24b(0.78) H24c(0.22)
 H24d(0.22)
5.a Free rotating group:
 O1(H1a,H1b)
5.b Secondary CH2 refined with riding coordinates:
 C19(H19a,H19b), C19(H19c,H19d), C22(H22a,H22b), C22(H22c,H22d), C20a(H20a,
 H20b), C21a(H21a,H21b), C21b(H21c,H21d), C20b(H20c,H20d), C26(H26a,H26b),
 C23(H23a,H23b), C23(H23c,H23d), C25(H25a,H25b), C25(H25c,H25d), C24a(H24a,
 H24b), C24b(H24c,H24d)
5.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C16(H16), C4(H4)
;
_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 1.668
_oxdiff_exptl_absorpt_empirical_full_min 0.573