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_7129583
_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         'C31 H45 O P S Si2'
_chemical_formula_sum            'C31 H45 O P S Si2'
_chemical_formula_weight         552.88
_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   mixed
_audit_creation_date             2021-08-10
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2018.07.26 svn.r3523 for OlexSys, GUI svn.r5532)
;
_audit_update_record
;
2021-09-02 deposited with the CCDC.	2022-01-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.304(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.3897(2)
_cell_length_b                   35.0632(6)
_cell_length_c                   11.2062(2)
_cell_measurement_reflns_used    18788
_cell_measurement_temperature    123.01(10)
_cell_measurement_theta_max      66.4990
_cell_measurement_theta_min      4.2740
_cell_volume                     3147.32(11)
_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 (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      123.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 4.2047
_diffrn_detector_type            TitanS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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   -121.00  -7.00   1.00    2.50    --  -43.23 -17.00  70.00  114
  2  \w    -80.00  35.00   1.00    2.50    --  -43.23  17.00-120.00  115
  3  \w    -35.00  80.00   1.00    2.50    --   43.23 -17.00  70.00  115
  4  \w      7.00 121.00   1.00    2.50    --   43.23  17.00-120.00  114
  5  \w     50.00 158.00   1.00   12.50    --   86.50  17.00-120.00  108
  6  \w   -155.00 -54.00   1.00   12.50    --  -90.00 -17.00  70.00  101
  7  \w    -96.00 -70.00   1.00   12.50    --  -90.00  17.00-120.00   26
  8  \w      7.00  87.00   1.00    2.50    --   43.23-125.00-180.00   80
  9  \w     41.00  66.00   1.00   12.50    --   86.50 -17.00  70.00   25
 10  \w    -78.00 -28.00   1.00   12.50    --  -90.00 125.00 -30.00   50
 11  \w   -167.00-105.00   1.00   12.50    --  -90.00 -94.00  60.00   62
 12  \w    -84.00 -35.00   1.00   12.50    --  -90.00  45.00  60.00   49
 13  \w    -86.00 -36.00   1.00   12.50    --  -90.00  45.00-180.00   50
 14  \w   -121.00 -84.00   1.00   12.50    --  -90.00  77.00  90.00   37
 15  \w    -72.00 -46.00   1.00   12.50    --  -90.00 139.00-111.93   26
 16  \w   -102.00 -34.00   1.00   12.50    --  -90.00  30.00  30.00   68
 17  \w   -155.00 -66.00   1.00   12.50    --  -90.00 -45.00-120.00   89
 18  \w   -152.00 -57.00   1.00   12.50    --  -90.00 -15.00 -90.00   95
 19  \w   -111.00 -27.00   1.00   12.50    --  -90.00 125.00  30.00   84
 20  \w   -117.00 -57.00   1.00   12.50    --  -90.00  61.00   0.00   60
 21  \w   -120.00 -94.00   1.00   12.50    --  -90.00 139.00-111.93   26
 22  \w   -151.00-125.00   1.00   12.50    --  -90.00-125.00 120.00   26
 23  \w   -145.00-103.00   1.00   12.50    --  -90.00 -15.00  30.00   42
 24  \w   -156.00-108.00   1.00   12.50    --  -90.00 -77.00  30.00   48
 25  \w   -141.00-113.00   1.00   12.50    --  -90.00-122.00 108.43   28
 26  \w   -100.00 -74.00   1.00   12.50    --  -90.00 110.00-169.88   26
 27  \w   -102.00 -76.00   1.00   12.50    --  -90.00  61.00 120.00   26
 28  \w   -164.00-127.00   1.00   12.50    --  -90.00-125.00-150.00   37
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dualflex, TitanS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1869137000
_diffrn_orient_matrix_UB_12      -0.0090457000
_diffrn_orient_matrix_UB_13      -0.0258102000
_diffrn_orient_matrix_UB_21      -0.0264083000
_diffrn_orient_matrix_UB_22      0.0043473000
_diffrn_orient_matrix_UB_23      -0.1413975000
_diffrn_orient_matrix_UB_31      0.0367795000
_diffrn_orient_matrix_UB_32      -0.0427729000
_diffrn_orient_matrix_UB_33      -0.0087994000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0563
_diffrn_reflns_av_unetI/netI     0.0280
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -41
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            35977
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         4.320
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.276
_exptl_absorpt_correction_T_max  0.880
_exptl_absorpt_correction_T_min  0.827
_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    1.167
_exptl_crystal_description       block
_exptl_crystal_F_000             1192
_exptl_crystal_recrystallization_method 'From the Melt'
_exptl_crystal_size_max          0.121
_exptl_crystal_size_mid          0.096
_exptl_crystal_size_min          0.079
_refine_diff_density_max         0.506
_refine_diff_density_min         -0.342
_refine_diff_density_rms         0.066
_refine_ls_extinction_coef       0.00036(6)
_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   1.208
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     359
_refine_ls_number_reflns         5524
_refine_ls_number_restraints     36
_refine_ls_restrained_S_all      1.206
_refine_ls_R_factor_all          0.0619
_refine_ls_R_factor_gt           0.0584
_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^)+(0.0204P)^2^+7.9113P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1336
_refine_ls_wR_factor_ref         0.1353
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5124
_reflns_number_total             5524
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc07016a2.cif
_cod_data_source_block           nf_719_2b_gv_2_mp_abs_ana
_cod_database_code               7129583
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C31H45OPSSi2
_reflns_odcompleteness_completeness 98.50
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
C22 \\sim C24A \\sim C24B \\sim C25A \\sim C25B: within 1.7A with sigma of 0.01
and sigma for terminal atoms of 0.02
3. Others
 Fixed Sof: C24A(0.6) H24A(0.6) H24B(0.6) H24C(0.6) C24B(0.4) H24D(0.4)
 H24E(0.4) H24F(0.4) C25A(0.6) H25A(0.6) H25B(0.6) H25C(0.6) C25B(0.4)
 H25D(0.4) H25E(0.4) H25F(0.4)
4.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B)
4.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C13(H13), C14(H14), C15(H15), C17(H17), C18(H18),
 C19(H19), C20(H20), C21(H21), C27(H27), C28(H28), C29(H29), C30(H30), C31(H31)
4.c Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C7(H7A,H7B,H7C), C8(H8A,
 H8B,H8C), C9(H9A,H9B,H9C), C23(H23A,H23B,H23C), C24A(H24A,H24B,H24C),
 C24B(H24D,H24E,H24F), C25A(H25A,H25B,H25C), C25B(H25D,H25E,H25F)
;
_shelx_res_checksum              428
_shelx_hkl_checksum              36100
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 2.459
_oxdiff_exptl_absorpt_empirical_full_min 0.747