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_7713645
_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, C6 H2 N3 O7, 0.75(C6 H12)'
_chemical_formula_sum            'C46.5 H63 As N3 O8'
_chemical_formula_weight         866.92
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-13
_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                87.8670(10)
_cell_angle_beta                 80.2660(10)
_cell_angle_gamma                88.6100(10)
_cell_formula_units_Z            4
_cell_length_a                   11.82030(10)
_cell_length_b                   15.2864(2)
_cell_length_c                   24.9112(2)
_cell_measurement_reflns_used    42522
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      77.0650
_cell_measurement_theta_min      2.8610
_cell_volume                     4432.59(8)
_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     74.00 106.00   0.50    0.35    --  105.75 -99.00 -90.00   64
  2  \w     53.00  79.00   0.50    0.09    --   49.66-125.00 -30.00   52
  3  \w     65.00 100.00   0.50    0.35    --  105.75-125.00   0.00   70
  4  \w     38.00  64.00   0.50    0.35    --  105.75 -99.00 -90.00   52
  5  \w     35.00 104.00   0.50    0.35    --  105.75 -99.00   0.00  138
  6  \w     68.00  94.00   0.50    0.35    --  105.75 -99.00  30.00   52
  7  \w     35.00  63.00   0.50    0.35    --  105.75 -99.00  30.00   56
  8  \w     50.00 106.00   0.50    0.35    --  105.75 -99.00  60.00  112
  9  \w     72.00 104.00   0.50    0.35    --  105.75 -99.00  90.00   64
 10  \w     34.00 106.00   0.50    0.35    --  105.75 -99.00 150.00  144
 11  \w     54.00  97.00   0.50    0.35    --  105.75 -99.00 -60.00   86
 12  \w     35.00  61.00   0.50    0.35    --  105.75 -99.00-150.00   52
 13  \w     51.00  93.00   0.50    0.35    --  105.75 -99.00-180.00   84
 14  \w     68.00 104.00   0.50    0.35    --  105.75 -99.00-150.00   72
 15  \w    -20.00  26.00   0.50    0.09    --   49.66 -16.00 -76.00   92
 16  \w     34.00  67.00   0.50    0.35    --  105.75 -57.00-180.00   66
 17  \w     81.00 106.00   0.50    0.35    --  105.75 -77.00-180.00   50
 18  \w     42.00  67.00   0.50    0.35    --  105.75 -57.00-120.00   50
 19  \w     77.00 103.00   0.50    0.35    --  105.75 -77.00  60.00   52
 20  \w     35.00  69.00   0.50    0.35    --  105.75 -77.00  60.00   68
 21  \w     35.00  63.00   0.50    0.35    --  105.75 -57.00  90.00   56
 22  \w     39.00  67.00   0.50    0.35    --  105.75 -57.00 120.00   56
 23  \w     35.00  66.00   0.50    0.35    --  105.75 -57.00  60.00   62
 24  \w     34.00  63.00   0.50    0.35    --  105.75 -57.00 -90.00   58
 25  \w     98.00 175.00   0.50    0.35    --  105.75  16.00  93.00  154
 26  \w    109.00 166.00   0.50    0.35    --  105.75  77.00 150.00  114
 27  \w     93.00 161.00   0.50    0.35    --  105.75  57.00  30.00  136
 28  \w    123.00 170.00   0.50    0.35    --  105.75  19.00 -30.00   94
 29  \w     98.00 132.00   0.50    0.35    --  105.75  38.00 -90.00   68
 30  \w    148.00 176.00   0.50    0.35    --  105.75  38.00 -90.00   56
 31  \w    100.00 175.00   0.50    0.35    --  105.75  19.00-180.00  150
 32  \w     90.00 122.00   0.50    0.09    --   49.66  57.00 -90.00   64
 33  \w     71.00 122.00   0.50    0.09    --   49.66  16.00  93.00  102
 34  \w    -62.00  21.00   0.50    0.09    --  -49.66  57.00  90.00  166
 35  \w    -39.00 -13.00   0.50    0.35    --  -84.25  38.00  60.00   52
 36  \w    -23.00  24.00   0.50    0.09    --  -49.66  16.00  93.00   94
 37  \w    -40.00 -13.00   0.50    0.35    --  -84.25  38.00 -90.00   54
 38  \w    -65.00 -12.00   0.50    0.35    --  -84.25  57.00-120.00  106
 39  \w    -30.00  22.00   0.50    0.09    --  -49.66  38.00-150.00  104
 40  \w   -107.00 -41.00   0.50    0.09    --  -49.66 -16.00 -76.00  132
 41  \w   -116.00 -84.00   0.50    0.09    --  -49.66 -57.00 -60.00   64
 42  \w   -111.00 -85.00   0.50    0.09    --  -49.66 -57.00 -30.00   52
 43  \w   -136.00-110.00   0.50    0.35    --  -84.25 -99.00  90.00   52
 44  \w   -156.00 -76.00   0.50    0.35    --  -84.25 -16.00 -76.00  160
 45  \w    -70.00 -44.00   0.50    0.09    --  -49.66 125.00-180.00   52
 46  \w    -75.00 -42.00   0.50    0.35    --  -84.25 125.00 -90.00   66
;
_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      -0.0781647000
_diffrn_orient_matrix_UB_12      0.0773560000
_diffrn_orient_matrix_UB_13      -0.0128555000
_diffrn_orient_matrix_UB_21      -0.0979582000
_diffrn_orient_matrix_UB_22      -0.0638455000
_diffrn_orient_matrix_UB_23      -0.0019747000
_diffrn_orient_matrix_UB_31      -0.0422666000
_diffrn_orient_matrix_UB_32      0.0106723000
_diffrn_orient_matrix_UB_33      0.0614189000
_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  0.0359
_diffrn_reflns_av_unetI/netI     0.0327
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            60318
_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         2.893
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.486
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.509
_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    1.299
_exptl_crystal_description       block
_exptl_crystal_F_000             1840
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.664
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1086
_refine_ls_number_reflns         15821
_refine_ls_number_restraints     25
_refine_ls_restrained_S_all      1.072
_refine_ls_R_factor_all          0.0345
_refine_ls_R_factor_gt           0.0311
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0347P)^2^+2.5076P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0779
_refine_ls_wR_factor_ref         0.0799
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14390
_reflns_number_total             15821
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3dt02113k2.cif
_cod_data_source_block           4b
_cod_original_formula_sum        'C46.50 H63 As N3 O8'
_cod_database_code               7713645
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C42 H54 O8 As1 N3'
_chemical_oxdiff_usercomment     'Dipp3SbOH CF3SO3 JSW0564'
_shelx_estimated_absorpt_t_max   0.890
_shelx_estimated_absorpt_t_min   0.766
_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
 O11-H11
 0.84 with sigma of 0.02
 O21-H21
 0.84 with sigma of 0.02
 C102-C103
 1.51 with sigma of 0.001
 C102-C101
 1.51 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
C101 \\sim C102 \\sim C103: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.01 within 2A
4. Rigid body (RIGU) restrains
 C101, C102, C103
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
5.a Ternary CH refined with riding coordinates:
 C27(H27), C78(H78), C67(H67), C17(H17), C18(H18), C57(H57), C58(H58),
 C38(H38), C77(H77), C37(H37), C68(H68), C28(H28)
5.b Secondary CH2 refined with riding coordinates:
 C96(H96A,H96B), C91(H91A,H91B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,
 H94B), C95(H95A,H95B), C102(H10A,H10B), C101(H10C,H10D), C103(H10E,H10F)
5.c Aromatic/amide H refined with riding coordinates:
 C45(H45), C83(H83), C13(H13), C14(H14), C43(H43), C15(H15), C24(H24),
 C23(H23), C55(H55), C74(H74), C35(H35), C25(H25), C73(H73), C54(H54), C53(H53),
  C65(H65), C75(H75), C63(H63), C64(H64), C33(H33), C85(H85), C34(H34)
5.d Idealised Me refined as rotating group:
 C172(H17A,H17B,H17C), C781(H78A,H78B,H78C), C181(H18A,H18B,H18C), C782(H78D,
 H78E,H78F), C271(H27A,H27B,H27C), C572(H57A,H57B,H57C), C171(H17D,H17E,H17F),
 C272(H27D,H27E,H27F), C182(H18D,H18E,H18F), C571(H57D,H57E,H57F), C671(H67A,
 H67B,H67C), C771(H77A,H77B,H77C), C372(H37A,H37B,H37C), C581(H58A,H58B,H58C),
 C682(H68A,H68B,H68C), C582(H58D,H58E,H58F), C672(H67D,H67E,H67F), C381(H38A,
 H38B,H38C), C281(H28A,H28B,H28C), C772(H77D,H77E,H77F), C371(H37D,H37E,H37F),
 C382(H38D,H38E,H38F), C681(H68D,H68E,H68F), C282(H28D,H28E,H28F)
;
_shelx_res_checksum              46571
_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 1.426
_oxdiff_exptl_absorpt_empirical_full_min 0.811