α-Phenylthioaldehydes for the effective generation of acyl azolium and azolium enolate intermediates.
Ewing, Paul M. D. A.; Majhi, Pankaj Kumar; Prentice, Callum; Young, Claire M.; van Rees, Karlotta; Arnold, Polly L.; Zysman-Colman, Eli; Smith, Andrew D.; Chemical science 15 (2024) 9369–9375; doi:10.1039/d3sc06879j

data_1571634
_publ_section_title
;
 &#x3b1;-Phenylthioaldehydes for the effective generation of acyl azolium
 and azolium enolate intermediates.
;
_journal_issue                   24
_journal_name_full               'Chemical science'
_journal_page_first              9369
_journal_page_last               9375
_journal_paper_doi               10.1039/d3sc06879j
_journal_volume                  15
_journal_year                    2024
_chemical_absolute_configuration syn
_chemical_formula_moiety         'C30 H24 F N O3 S'
_chemical_formula_sum            'C30 H24 F N O3 S'
_chemical_formula_weight         497.56
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-02-04
_audit_creation_method
;
Olex2 1.3-alpha
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-11-24 deposited with the CCDC.	2024-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.40710(10)
_cell_length_b                   15.89600(10)
_cell_length_c                   21.0437(2)
_cell_measurement_reflns_used    17149
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      75.8360
_cell_measurement_theta_min      5.0430
_cell_volume                     2477.75(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-alpha (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      120.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.1574
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_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   -119.00 -49.00   1.00    2.00    --  -41.67-165.00 119.00   70
  2  \w    -65.00  33.00   1.00    2.00    --  -41.67  30.00 144.00   98
  3  \w     36.00 135.00   1.00    8.00    --  111.00 -30.00 -16.00   99
  4  \w     31.00 106.00   1.00    8.00    --  111.00 -96.00 163.00   75
  5  \w    104.00 178.00   1.00    8.00    --  111.00  96.00 -87.00   74
  6  \w     50.00 139.00   1.00    8.00    --  111.00-165.00 119.00   89
  7  \w     10.00  42.00   1.00    2.00    --   41.67  79.00  -6.55   32
  8  \w     10.00  42.00   1.00    2.00    --   41.67  79.00 175.37   32
  9  \w      9.00  42.00   1.00    2.00    --   41.67  81.00  94.01   33
 10  \w      9.00  42.00   1.00    2.00    --   41.67  81.00  59.65   33
 11  \w     30.00 107.00   1.00    8.00    --  111.00 -94.00   0.00   77
 12  \w     30.00 107.00   1.00    8.00    --  111.00 -94.00 120.00   77
 13  \w     67.00  94.00   1.00    8.00    --  111.00  15.00 -90.00   27
 14  \w     70.00 106.00   1.00    8.00    --  111.00 -94.00-180.00   36
 15  \w    119.00 146.00   1.00    8.00    --  111.00  15.00 -90.00   27
 16  \w    129.00 156.00   1.00    8.00    --  111.00 125.00  30.00   27
 17  \w     75.00 137.00   1.00    8.00    --  111.00 -61.00  60.00   62
 18  \w     91.00 178.00   1.00    8.00    --  111.00  56.00 129.09   87
 19  \w     93.00 152.00   1.00    8.00    --  111.00  70.00   8.72   59
 20  \w     55.00  97.00   1.00    8.00    --  111.00-125.00 -90.00   42
 21  \w    128.00 155.00   1.00    8.00    --  111.00 125.00   0.00   27
 22  \w     61.00 100.00   1.00    8.00    --  111.00 -30.00 150.00   39
 23  \w     55.00 102.00   1.00    8.00    --  111.00 -94.00 -60.00   47
 24  \w    139.00 171.00   1.00    8.00    --  111.00  45.00   0.00   32
 25  \w    117.00 178.00   1.00    8.00    --  111.00  30.00-180.00   61
 26  \w     37.00  71.00   1.00    8.00    --  111.00 -30.00-150.00   34
 27  \w     91.00 118.00   1.00    8.00    --  111.00 -30.00-150.00   27
 28  \w     97.00 178.00   1.00    8.00    --  111.00  45.00-150.00   81
 29  \w    105.00 137.00   1.00    8.00    --  111.00  77.00 -60.00   32
 30  \w     71.00  98.00   1.00    8.00    --  111.00 -77.00-150.00   27
 31  \w     42.00 117.00   1.00    8.00    --  111.00 -45.00 150.00   75
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0352572000
_diffrn_orient_matrix_UB_12      -0.0715271000
_diffrn_orient_matrix_UB_13      -0.0478071000
_diffrn_orient_matrix_UB_21      0.0716831000
_diffrn_orient_matrix_UB_22      -0.0559120000
_diffrn_orient_matrix_UB_23      0.0542483000
_diffrn_orient_matrix_UB_31      -0.1919629000
_diffrn_orient_matrix_UB_32      -0.0339576000
_diffrn_orient_matrix_UB_33      0.0115137000
_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  0.0694
_diffrn_reflns_av_unetI/netI     0.0436
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            26615
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.972
_diffrn_reflns_theta_min         3.485
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.496
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67719
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.99a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.334
_exptl_crystal_description       block
_exptl_crystal_F_000             1040
_exptl_crystal_recrystallization_method
'Slow diffusion from a concentrated diethyl ether solution at room temperature.'
_exptl_crystal_size_max          0.171
_exptl_crystal_size_mid          0.121
_exptl_crystal_size_min          0.088
_refine_diff_density_max         0.302
_refine_diff_density_min         -0.504
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 2079 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.010(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     326
_refine_ls_number_reflns         5159
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0458
_refine_ls_R_factor_gt           0.0446
_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^)+(0.0908P)^2^+0.1472P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1167
_refine_ls_wR_factor_ref         0.1183
_reflns_Friedel_coverage         0.749
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.993
_reflns_number_gt                4987
_reflns_number_total             5159
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc06879j2.cif
_cod_data_source_block           jl22002_refinalized
_cod_depositor_comments          'Adding full bibliography for 1571634.cif.'
_cod_database_code               1571634
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C30 H24 F1 N1 O3 S1'
_chemical_oxdiff_usercomment     '@ 120 K KvR_PE_1'
_shelx_estimated_absorpt_t_max   0.880
_shelx_estimated_absorpt_t_min   0.784
_reflns_odcompleteness_completeness 98.64
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     76.55
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C3(H3), C2(H2)
2.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C30(H30), C25(H25), C13(H13), C16(H16), C29(H29), C17(H17), C11(H11),
 C26(H26), C8(H8), C7(H7), C14(H14), C15(H15), C19(H19), C10(H10), C23(H23),
 C22(H22), C20(H20), C21(H21)
2.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C)
;
_shelx_res_checksum              43589
_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 1.382
_oxdiff_exptl_absorpt_empirical_full_min 0.779