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_7713646
_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 H52 O P, C F3 O3 S'
_chemical_formula_sum            'C37 H52 F3 O4 P S'
_chemical_formula_weight         680.81
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-18
_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                106.2340(10)
_cell_angle_beta                 99.4490(10)
_cell_angle_gamma                97.5890(10)
_cell_formula_units_Z            4
_cell_length_a                   14.3959(2)
_cell_length_b                   16.0784(2)
_cell_length_c                   16.8119(2)
_cell_measurement_reflns_used    28873
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      76.7690
_cell_measurement_theta_min      2.9270
_cell_volume                     3619.84(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_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(11)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -69.00  15.00   0.50    0.34    --  -49.41  78.00 -14.00  168
  2  \w     16.00  65.00   0.50    0.34    --   49.41 -78.00-140.00   98
  3  \w    -83.00 -58.00   0.50    1.35    --  -84.25  78.00 -14.00   50
  4  \w   -143.00-117.00   0.50    1.35    --  -84.25 -78.00-140.00   52
  5  \w    105.00 178.00   0.50    1.35    --  105.75  78.00 -14.00  146
  6  \w     52.00  98.00   0.50    1.35    --  105.75 -78.00-140.00   92
  7  \w   -120.00 -87.00   0.50    0.34    --  -49.41 -57.00 -90.00   66
  8  \w   -121.00 -87.00   0.50    0.34    --  -49.41-125.00  60.00   68
  9  \w    -19.00  21.00   0.50    0.34    --  -49.41  19.00   0.00   80
 10  \w   -117.00 -87.00   0.50    0.34    --  -49.41 -57.00 -60.00   60
 11  \w   -118.00 -87.00   0.50    0.34    --  -49.41-125.00 -90.00   62
 12  \w    -41.00  22.00   0.50    0.34    --  -49.41  38.00-120.00  126
 13  \w     -3.00  22.00   0.50    0.34    --  -49.41  19.00-150.00   50
 14  \w     82.00 120.00   0.50    0.34    --   49.41  57.00  30.00   76
 15  \w     84.00 110.00   0.50    0.34    --   49.41  57.00   0.00   52
 16  \w     89.00 118.00   0.50    0.34    --   49.41  57.00 -30.00   58
 17  \w    -40.00 -14.00   0.50    1.35    --  -84.25  38.00  90.00   52
 18  \w    -42.00 -13.00   0.50    1.35    --  -84.25  38.00 150.00   58
 19  \w    -42.00 -13.00   0.50    1.35    --  -84.25  38.00   0.00   58
 20  \w   -153.00-110.00   0.50    1.35    --  -84.25 -77.00-120.00   86
 21  \w    -40.00 -12.00   0.50    1.35    --  -84.25  57.00 -90.00   56
 22  \w    -42.00 -13.00   0.50    1.35    --  -84.25  38.00-180.00   58
 23  \w    114.00 158.00   0.50    1.35    --  105.75  77.00 -60.00   88
 24  \w     71.00 106.00   0.50    1.35    --  105.75 -99.00   0.00   70
 25  \w     34.00  68.00   0.50    1.35    --  105.75 -99.00   0.00   68
 26  \w    107.00 173.00   0.50    1.35    --  105.75  38.00  60.00  132
 27  \w     34.00  59.00   0.50    1.35    --  105.75 -57.00 -30.00   50
 28  \w     76.00 106.00   0.50    1.35    --  105.75 -99.00  30.00   60
 29  \w     40.00  66.00   0.50    1.35    --  105.75 -57.00 120.00   52
 30  \w     34.00 104.00   0.50    1.35    --  105.75 -77.00  30.00  140
 31  \w     35.00 104.00   0.50    1.35    --  105.75 -99.00-150.00  138
 32  \w     35.00  60.00   0.50    1.35    --  105.75 -77.00   0.00   50
 33  \w     35.00  66.00   0.50    1.35    --  105.75 -57.00  30.00   62
 34  \w     81.00 106.00   0.50    1.35    --  105.75 -99.00 120.00   50
 35  \w     98.00 137.00   0.50    1.35    --  105.75  19.00 120.00   78
 36  \w    141.00 167.00   0.50    1.35    --  105.75  19.00 120.00   52
 37  \w    107.00 135.00   0.50    1.35    --  105.75  38.00 -30.00   56
 38  \w     41.00  76.00   0.50    1.35    --  105.75 -99.00 120.00   70
 39  \w    140.00 178.00   0.50    1.35    --  105.75  19.00 -90.00   76
 40  \w     59.00 108.00   0.50    1.35    --  105.75-125.00 150.00   98
 41  \w     66.00 103.00   0.50    1.35    --  105.75 -77.00 -90.00   74
 42  \w     35.00  60.00   0.50    1.35    --  105.75 -77.00 -90.00   50
 43  \w     67.00 105.00   0.50    1.35    --  105.75 -99.00 -60.00   76
 44  \w     48.00 102.00   0.50    1.35    --  105.75 -77.00 120.00  108
 45  \w     77.00 111.00   0.50    1.35    --  105.75-125.00-120.00   68
 46  \w    149.00 174.00   0.50    1.35    --  105.75  38.00 -30.00   50
 47  \w     38.00  74.00   0.50    1.35    --  105.75-125.00-120.00   72
 48  \w     39.00  65.00   0.50    1.35    --  105.75 -99.00 -60.00   52
 49  \w     41.00  66.00   0.50    1.35    --  105.75 -57.00 -90.00   50
 50  \w     70.00  95.00   0.50    1.35    --  105.75 -77.00   0.00   50
 51  \w     36.00  61.00   0.50    1.35    --  105.75 -99.00  60.00   50
 52  \w     99.00 130.00   0.50    1.35    --  105.75  19.00 -90.00   62
;
_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      0.0691308000
_diffrn_orient_matrix_UB_12      -0.0610633000
_diffrn_orient_matrix_UB_13      0.0181494000
_diffrn_orient_matrix_UB_21      -0.0559057000
_diffrn_orient_matrix_UB_22      -0.0739893000
_diffrn_orient_matrix_UB_23      -0.0801477000
_diffrn_orient_matrix_UB_31      0.0655392000
_diffrn_orient_matrix_UB_32      0.0334708000
_diffrn_orient_matrix_UB_33      -0.0527403000
_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  0.0339
_diffrn_reflns_av_unetI/netI     0.0319
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            49143
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         2.801
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.649
_exptl_absorpt_correction_T_max  0.86543
_exptl_absorpt_correction_T_min  0.86543
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.121a (Rigaku Oxford Diffraction, 2021)
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    1.249
_exptl_crystal_description       sphere
_exptl_crystal_F_000             1456
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.07
_exptl_crystal_size_rad          0.059
_refine_diff_density_max         1.028
_refine_diff_density_min         -0.453
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     928
_refine_ls_number_reflns         12911
_refine_ls_number_restraints     329
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0486
_refine_ls_R_factor_gt           0.0435
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0691P)^2^+2.0564P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1207
_refine_ls_wR_factor_ref         0.1247
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11427
_reflns_number_total             12911
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02113k2.cif
_cod_data_source_block           2c
_cod_original_cell_volume        3619.84(8)
_cod_database_code               7713646
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C37 H52 P1 S1 O4 F3'
_chemical_oxdiff_usercomment     'Dipp3POH CF3SO3'
_shelx_estimated_absorpt_t_max   0.893
_shelx_estimated_absorpt_t_min   0.723
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 O6-C8 \\sim O6A-C8A
 with sigma of 0.04
 S2-O8 \\sim S2A-O7A
 with sigma of 0.02
 S2-O6 \\sim S2A-O6A
 with sigma of 0.02
 S2-O7 \\sim S2A-O9
 with sigma of 0.02
 S2-C8 \\sim S2A-C8A
 with sigma of 0.02
 F6-F5 \\sim F4A-F5A
 with sigma of 0.04
 O7-C8 \\sim O9-C8A
 with sigma of 0.04
 F5-F4 \\sim F5A-F6A
 with sigma of 0.04
 F6-C8 \\sim F4A-C8A
 with sigma of 0.02
 F5-C8 \\sim F5A-C8A
 with sigma of 0.02
 F4-C8 \\sim F6A-C8A
 with sigma of 0.02
 F6-F4 \\sim F4A-F6A
 with sigma of 0.04
 O6-O7 \\sim O6A-O9
 with sigma of 0.04
 S2-F6 \\sim S2A-F4A
 with sigma of 0.04
 S2-F5 \\sim S2A-F5A
 with sigma of 0.04
 S2-F4 \\sim S2A-F6A
 with sigma of 0.04
 O8-O6 \\sim O7A-O6A
 with sigma of 0.04
 O8-O7 \\sim O7A-O9
 with sigma of 0.04
 O8-C8 \\sim O7A-C8A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
S2A \\sim O7A \\sim O6A \\sim O9 \\sim C8A \\sim F6A \\sim F4A \\sim F5A \\sim
O8 \\sim O7 \\sim O6 \\sim C8 \\sim F6 \\sim F5 \\sim F4 \\sim S2: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Rigid body (RIGU) restrains
 O8, O7, O6, C8, F6, F5, F4, O7A, O6A, O9, C8A, F6A, F4A, F5A, S2A, S2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(S2A)=Sof(O6A)=Sof(O7A)=Sof(O9)=Sof(C8A)=Sof(F6A)=Sof(F4A)=Sof(F5A)=1-
 FVAR(1)
 Sof(S2)=Sof(O8)=Sof(F6)=Sof(F5)=Sof(O6)=Sof(O7)=Sof(F4)=Sof(C8)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C18(H18), C17(H17), C37(H37), C57(H57), C28(H28), C68(H68), C67(H67),
 C58(H58), C47(H47), C27(H27), C38(H38), C48(H48)
6.b Aromatic/amide H refined with riding coordinates:
 C64(H64), C53(H53), C55(H55), C54(H54), C65(H65), C15(H15), C13(H13),
 C63(H63), C23(H23), C14(H14), C24(H24), C25(H25), C35(H35), C43(H43), C34(H34),
  C33(H33), C45(H45), C44(H44)
6.c Tetrahedral OH refined as rotating group:
 O1(H1), O2(H2)
6.d Idealised Me refined as rotating group:
 C182(H18A,H18B,H18C), C282(H28A,H28B,H28C), C682(H68A,H68B,H68C), C181(H18D,
 H18E,H18F), C571(H57A,H57B,H57C), C371(H37A,H37B,H37C), C572(H57D,H57E,H57F),
 C382(H38A,H38B,H38C), C172(H17A,H17B,H17C), C671(H67A,H67B,H67C), C381(H38D,
 H38E,H38F), C672(H67D,H67E,H67F), C281(H28D,H28E,H28F), C472(H47A,H47B,H47C),
 C481(H48A,H48B,H48C), C171(H17D,H17E,H17F), C271(H27A,H27B,H27C), C582(H58A,
 H58B,H58C), C681(H68D,H68E,H68F), C372(H37D,H37E,H37F), C581(H58D,H58E,H58F),
 C471(H47D,H47E,H47F), C272(H27D,H27E,H27F), C482(H48D,H48E,H48F)
;
_shelx_res_checksum              37317
_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 1.366
_oxdiff_exptl_absorpt_empirical_full_min 0.833