Variation in pnictogen-oxygen bonding unlocks greatly enhanced Brønsted basicity for the monomeric stibine oxide.
Wenger, John S.; Getahun, Addis; Johnstone, Timothy C.; Dalton transactions (Cambridge, England : 2003)  (2023) –; doi:10.1039/d3dt02113k

data_7713643
_publ_section_title
;
 Variation in pnictogen-oxygen bonding unlocks greatly enhanced
 Br&#xf8;nsted basicity for the monomeric stibine oxide.
;
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_paper_doi               10.1039/d3dt02113k
_journal_year                    2023
_chemical_formula_moiety         'C36 H50 O P, C F3 O3 S'
_chemical_formula_sum            'C37 H50 F3 O4 P S'
_chemical_formula_weight         678.80
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-29
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-03-21 deposited with the CCDC.	2023-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.4440(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.49870(10)
_cell_length_b                   25.1021(3)
_cell_length_c                   14.9869(2)
_cell_measurement_reflns_used    26332
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.9280
_cell_measurement_theta_min      3.4640
_cell_volume                     3502.39(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.64a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.64a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.64a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -73.00  17.00   0.50    0.58    --  -49.66  88.00 -80.00  180
  2  \w     13.00  59.00   0.50    0.58    --   49.66 -88.00 163.00   92
  3  \w    -18.00   7.00   0.50    0.58    --   49.66 -88.00 163.00   50
  4  \w    -64.00 -38.00   0.50    2.32    --  -84.25  88.00 -80.00   52
  5  \w     37.00  84.00   0.50    2.32    --  105.75 -88.00 163.00   94
  6  \w    101.00 137.00   0.50    2.32    --  105.75  88.00 -80.00   72
  7  \w   -117.00 -91.00   0.50    0.58    --  -49.66-125.00-120.00   52
  8  \w   -111.00 -82.00   0.50    0.58    --  -49.66 -57.00 -30.00   58
  9  \w   -120.00 -82.00   0.50    0.58    --  -49.66 -57.00-150.00   76
 10  \w   -120.00 -95.00   0.50    0.58    --  -49.66 -57.00 -90.00   50
 11  \w   -112.00 -83.00   0.50    0.58    --  -49.66 -57.00 -60.00   58
 12  \w    -25.00  15.00   0.50    0.58    --  -49.66  19.00-150.00   80
 13  \w     84.00 121.00   0.50    0.58    --   49.66  57.00   0.00   74
 14  \w    -23.00  27.00   0.50    0.58    --   49.66 -19.00-150.00  100
 15  \w     90.00 116.00   0.50    0.58    --   49.66  57.00 -30.00   52
 16  \w   -129.00 -82.00   0.50    2.32    --  -84.25 -57.00 120.00   94
 17  \w   -145.00-115.00   0.50    2.32    --  -84.25 -52.00-174.91   60
 18  \w    -98.00 -73.00   0.50    2.32    --  -84.25 -52.00-174.91   50
 19  \w    -42.00 -13.00   0.50    2.32    --  -84.25  38.00 -60.00   58
 20  \w   -148.00-120.00   0.50    2.32    --  -84.25 -57.00-150.00   56
 21  \w    -42.00 -17.00   0.50    2.32    --  -84.25  38.00 120.00   50
 22  \w   -141.00-115.00   0.50    2.32    --  -84.25 -88.00 163.00   52
 23  \w   -151.00-107.00   0.50    2.32    --  -84.25-125.00 120.00   88
 24  \w    -38.00 -13.00   0.50    2.32    --  -84.25  38.00 150.00   50
 25  \w     47.00  73.00   0.50    2.32    --  105.75-125.00 -30.00   52
 26  \w     98.00 167.00   0.50    2.32    --  105.75  19.00  60.00  138
 27  \w     35.00  66.00   0.50    2.32    --  105.75 -57.00 150.00   62
 28  \w     37.00  63.00   0.50    2.32    --  105.75 -99.00  30.00   52
 29  \w     97.00 164.00   0.50    2.32    --  105.75 125.00  90.00  134
 30  \w     38.00  64.00   0.50    2.32    --  105.75 -57.00-150.00   52
 31  \w    102.00 172.00   0.50    2.32    --  105.75  19.00  30.00  140
 32  \w     78.00 105.00   0.50    2.32    --  105.75 -99.00  30.00   54
 33  \w     38.00  63.00   0.50    2.32    --  105.75 -99.00-180.00   50
 34  \w     71.00 106.00   0.50    2.32    --  105.75 -99.00-180.00   70
 35  \w     65.00 102.00   0.50    2.32    --  105.75 -99.00-120.00   74
 36  \w     95.00 124.00   0.50    2.32    --  105.75 125.00  30.00   58
 37  \w     36.00  61.00   0.50    2.32    --  105.75 -99.00-120.00   50
 38  \w     81.00 106.00   0.50    2.32    --  105.75 -99.00 -60.00   50
 39  \w     36.00  66.00   0.50    2.32    --  105.75 -57.00-120.00   60
 40  \w     35.00  67.00   0.50    2.32    --  105.75 -57.00-180.00   64
 41  \w     36.00  64.00   0.50    2.32    --  105.75 -57.00 -30.00   56
 42  \w     35.00 104.00   0.50    2.32    --  105.75 -77.00  30.00  138
 43  \w    101.00 155.00   0.50    2.32    --  105.75  19.00   0.00  108
 44  \w    105.00 158.00   0.50    2.32    --  105.75  77.00 -30.00  106
 45  \w     36.00  99.00   0.50    2.32    --  105.75 -99.00 120.00  126
 46  \w     80.00 110.00   0.50    2.32    --  105.75-125.00-180.00   60
 47  \w     37.00  64.00   0.50    2.32    --  105.75-125.00-180.00   54
 48  \w    137.00 163.00   0.50    2.32    --  105.75 125.00  30.00   52
 49  \w     79.00 104.00   0.50    2.32    --  105.75-125.00 -30.00   50
 50  \w     37.00 107.00   0.50    2.32    --  105.75-125.00   0.00  140
 51  \w     38.00  99.00   0.50    2.32    --  105.75 -77.00   0.00  122
;
_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      -0.0472786000
_diffrn_orient_matrix_UB_12      0.0412419000
_diffrn_orient_matrix_UB_13      0.0643620000
_diffrn_orient_matrix_UB_21      0.1249322000
_diffrn_orient_matrix_UB_22      0.0366122000
_diffrn_orient_matrix_UB_23      -0.0121393000
_diffrn_orient_matrix_UB_31      -0.0977129000
_diffrn_orient_matrix_UB_32      0.0269077000
_diffrn_orient_matrix_UB_33      -0.0819131000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0372
_diffrn_reflns_av_unetI/netI     0.0234
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            48293
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.077
_diffrn_reflns_theta_max         67.077
_diffrn_reflns_theta_min         3.486
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.704
_exptl_absorpt_correction_T_max  0.97156
_exptl_absorpt_correction_T_min  0.97156
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.64a (Rigaku Oxford Diffraction, 2022)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.287
_exptl_crystal_description       sphere
_exptl_crystal_F_000             1448
_exptl_crystal_size_max          0.11
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_exptl_crystal_size_rad          0.043
_refine_diff_density_max         1.098
_refine_diff_density_min         -0.351
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     455
_refine_ls_number_reflns         6253
_refine_ls_number_restraints     88
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0524
_refine_ls_R_factor_gt           0.0491
_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^+3.6853P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1282
_refine_ls_wR_factor_ref         0.1307
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5766
_reflns_number_total             6253
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02113k2.cif
_cod_data_source_block           3
_cod_database_code               7713643
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C37 H52 S1 O4 F3 P1 '
_chemical_oxdiff_usercomment     'Dipp3POH CF3SO3'
_shelx_estimated_absorpt_t_max   0.905
_shelx_estimated_absorpt_t_min   0.835
_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. Restrained distances
 C36-C38A \\sim C36-C38B
 with sigma of 0.02
 C38A-C81A \\sim C38B-C81B
 with sigma of 0.02
 C38A-C82A \\sim C38B-C82B
 with sigma of 0.02
 O1-C82A \\sim O1-C82B
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C38A \\sim C38B \\sim C81A \\sim C81B \\sim C82A \\sim C82B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C82A \\sim C82B: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
4. Rigid body (RIGU) restrains
 C38A, C38B, C81A, C81B, C82A, C82B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C38B)=Sof(H38B)=Sof(C81B)=Sof(H81D)=Sof(H81E)=Sof(H81F)=Sof(C82B)=
 Sof(H82C)=Sof(H82D)=1-FVAR(1)
 Sof(C38A)=Sof(H38A)=Sof(C81A)=Sof(H81A)=Sof(H81B)=Sof(H81C)=Sof(C82A)=
 Sof(H82A)=Sof(H82B)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C37(H37), C28(H28), C18(H18), C17(H17), C27(H27), C38A(H38A), C38B(H38B)
6.b Secondary CH2 refined with riding coordinates:
 C82A(H82A,H82B), C82B(H82C,H82D)
6.c Aromatic/amide H refined with riding coordinates:
 C13(H13), C15(H15), C33(H33), C14(H14), C34(H34), C35(H35), C25(H25),
 C24(H24), C23(H23)
6.d Idealised Me refined as rotating group:
 C282(H28A,H28B,H28C), C181(H18A,H18B,H18C), C371(H37A,H37B,H37C), C281(H28D,
 H28E,H28F), C171(H17A,H17B,H17C), C172(H17D,H17E,H17F), C372(H37D,H37E,H37F),
 C182(H18D,H18E,H18F), C271(H27A,H27B,H27C), C272(H27D,H27E,H27F), C81A(H81A,
 H81B,H81C), C81B(H81D,H81E,H81F)
;
_shelx_res_checksum              76280
_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 1.721
_oxdiff_exptl_absorpt_empirical_full_min 0.773