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_7713644
_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 As O, C F3 O3 S, C H Cl3'
_chemical_formula_sum            'C38 H53 As Cl3 F3 O4 S'
_chemical_formula_weight         844.13
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-15
_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                 98.6020(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.06410(10)
_cell_length_b                   17.7940(3)
_cell_length_c                   23.5660(3)
_cell_measurement_reflns_used    19117
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.6130
_cell_measurement_theta_min      3.1140
_cell_volume                     4172.74(10)
_computing_cell_refinement       'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.53a (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    -42.00 -13.00   0.50    1.39    --  -84.25  38.00-180.00   58
  2  \w    -42.00 -14.00   0.50    1.39    --  -84.25  38.00 -90.00   56
  3  \w    -59.00 -13.00   0.50    1.39    --  -84.25  57.00  60.00   92
  4  \w    -41.00 -14.00   0.50    1.39    --  -84.25  38.00 150.00   54
  5  \w     59.00  84.00   0.50    0.35    --   49.41-154.00  76.00   50
  6  \w     79.00 105.00   0.50    1.39    --  105.75-125.00 150.00   52
  7  \w     35.00  61.00   0.50    1.39    --  105.75-125.00 150.00   52
  8  \w     49.00  77.00   0.50    1.39    --  105.75-154.00  76.00   56
  9  \w     86.00 131.00   0.50    1.39    --  105.75-154.00  76.00   90
 10  \w     84.00 109.00   0.50    1.39    --  105.75-122.00-124.00   50
 11  \w     48.00 102.00   0.50    1.39    --  105.75 -99.00 -90.00  108
 12  \w     53.00  79.00   0.50    1.39    --  105.75-125.00 -90.00   52
 13  \w     38.00  63.00   0.50    0.35    --   49.41-122.00-124.00   50
 14  \w     35.00  64.00   0.50    1.39    --  105.75 -57.00-120.00   58
 15  \w     39.00  66.00   0.50    1.39    --  105.75 -57.00 -60.00   54
 16  \w     41.00  66.00   0.50    1.39    --  105.75 -57.00   0.00   50
 17  \w     34.00  59.00   0.50    1.39    --  105.75 -57.00  30.00   50
 18  \w     37.00  62.00   0.50    1.39    --  105.75 -57.00  60.00   50
 19  \w     34.00  66.00   0.50    1.39    --  105.75 -57.00 120.00   64
 20  \w   -119.00 -83.00   0.50    0.35    --  -49.41 -57.00 -90.00   72
 21  \w   -121.00 -84.00   0.50    0.35    --  -49.41 -57.00 -30.00   74
 22  \w   -119.00 -84.00   0.50    0.35    --  -49.41 -57.00  60.00   70
 23  \w    -87.00 -62.00   0.50    0.35    --  -49.41-154.00  76.00   50
 24  \w   -120.00 -88.00   0.50    0.35    --  -49.41-125.00 -90.00   64
 25  \w   -121.00 -91.00   0.50    0.35    --  -49.41-122.00-124.00   60
 26  \w   -116.00 -86.00   0.50    1.39    --  -84.25-122.00-124.00   60
 27  \w    -72.00 -47.00   0.50    1.39    --  -84.25 122.00 -42.00   50
 28  \w    -91.00 -66.00   0.50    1.39    --  -84.25 154.00 116.00   50
 29  \w   -105.00 -35.00   0.50    0.35    --  -49.41 154.00 116.00  140
 30  \w    108.00 133.00   0.50    1.39    --  105.75  38.00 120.00   50
 31  \w    150.00 176.00   0.50    1.39    --  105.75  38.00 120.00   52
 32  \w     86.00 121.00   0.50    0.35    --   49.41  57.00   0.00   70
 33  \w    109.00 134.00   0.50    1.39    --  105.75  19.00-120.00   50
 34  \w    144.00 177.00   0.50    1.39    --  105.75  19.00-120.00   66
 35  \w     97.00 175.00   0.50    1.39    --  105.75 122.00 -42.00  156
 36  \w    100.00 178.00   0.50    1.39    --  105.75 125.00  60.00  156
 37  \w     95.00 120.00   0.50    1.39    --  105.75 154.00 116.00   50
;
_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      -0.1498248000
_diffrn_orient_matrix_UB_12      0.0101060000
_diffrn_orient_matrix_UB_13      -0.0242513000
_diffrn_orient_matrix_UB_21      -0.0136746000
_diffrn_orient_matrix_UB_22      -0.0854334000
_diffrn_orient_matrix_UB_23      -0.0095000000
_diffrn_orient_matrix_UB_31      -0.0367179000
_diffrn_orient_matrix_UB_32      -0.0093413000
_diffrn_orient_matrix_UB_33      0.0607832000
_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  0.0394
_diffrn_reflns_av_unetI/netI     0.0308
_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       -12
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            35950
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.074
_diffrn_reflns_theta_max         67.074
_diffrn_reflns_theta_min         3.125
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.752
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.439
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.53a (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.344
_exptl_crystal_description       block
_exptl_crystal_F_000             1760
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.692
_refine_diff_density_min         -0.487
_refine_diff_density_rms         0.066
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.164
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     504
_refine_ls_number_reflns         7436
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.198
_refine_ls_R_factor_all          0.0573
_refine_ls_R_factor_gt           0.0535
_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^)+(0.0076P)^2^+11.2685P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1154
_refine_ls_wR_factor_ref         0.1170
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6837
_reflns_number_total             7436
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02113k2.cif
_cod_data_source_block           2b_monoclinic
_cod_database_code               7713644
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C37 H52 S1 O4 F3 As1'
_chemical_oxdiff_usercomment     'AG0006 Dipp3AsOH CF3SO3'
_shelx_estimated_absorpt_t_max   0.835
_shelx_estimated_absorpt_t_min   0.479
_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
2. Restrained distances
 O1-H1
 0.84 with sigma of 0.02
 C4A-Cl1A \\sim C4B-Cl1B
 with sigma of 0.01
 C4A-Cl2A \\sim C4B-Cl2B
 with sigma of 0.01
 C4A-Cl3A \\sim C4B-Cl3B
 with sigma of 0.01
 C4A-Cl1A \\sim C4A-Cl2A
 with sigma of 0.01
 C4A-Cl1A \\sim C4A-Cl3A
 with sigma of 0.01
 Cl1A-Cl2A \\sim Cl1B-Cl2B
 with sigma of 0.02
 Cl2A-Cl3A \\sim Cl2B-Cl3B
 with sigma of 0.02
 Cl3A-Cl1A \\sim Cl3B-Cl1B
 with sigma of 0.02
 Cl1A-Cl2A \\sim Cl1A-Cl3A
 with sigma of 0.02
 Cl2A-Cl3A \\sim Cl1A-Cl2A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C4A \\sim C4B: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Cl1A \\sim Cl2A \\sim Cl3A \\sim Cl1B \\sim Cl2B \\sim Cl3B: within 2A with
sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
4. Rigid body (RIGU) restrains
 C4A, Cl1A, Cl2A, Cl3A, C4B, Cl1B, Cl2B, Cl3B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5. Others
 Sof(C4B)=Sof(H4B)=Sof(Cl1B)=Sof(Cl2B)=Sof(Cl3B)=1-FVAR(1)
 Sof(C4A)=Sof(H4A)=Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C17(H17), C18(H18), C27(H27), C38(H38), C37(H37), C28(H28), C4A(H4A), C4B(H4B)
6.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C14(H14), C15(H15), C25(H25), C24(H24), C23(H23), C33(H33),
 C34(H34), C35(H35)
6.c Idealised Me refined as rotating group:
 C272(H27A,H27B,H27C), C171(H17A,H17B,H17C), C172(H17D,H17E,H17F), C182(H18A,
 H18B,H18C), C181(H18D,H18E,H18F), C271(H27D,H27E,H27F), C281(H28A,H28B,H28C),
 C371(H37A,H37B,H37C), C372(H37D,H37E,H37F), C282(H28D,H28E,H28F), C382(H38A,
 H38B,H38C), C381(H38D,H38E,H38F)
;
_shelx_res_checksum              51949
_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 1.475
_oxdiff_exptl_absorpt_empirical_full_min 0.711