Synthesis of highly condensed phospholes by Lewis acid-assisted dehydrogenative Mallory reaction under visible light irradiation
Kamiyoshi, Ikki; Kojima, Yuki; Xu, Shibo; Yasui, Kosuke; Nishii, Yuji; Hirano, Koji; Chemical Science  (2024) –; doi:10.1039/D4SC05657D

data_1573169
_publ_section_title
;
 Synthesis of highly condensed phospholes by Lewis acid-assisted
 dehydrogenative Mallory reaction under visible light irradiation
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D4SC05657D
_journal_year                    2024
_chemical_formula_moiety         'C32 H19 O P S, 2(C H Cl3)'
_chemical_formula_sum            'C34 H21 Cl6 O P S'
_chemical_formula_weight         721.23
_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             2024-06-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-08-16 deposited with the CCDC.	2024-11-13 downloaded from the CCDC.
;
_cell_angle_alpha                82.549(2)
_cell_angle_beta                 69.415(3)
_cell_angle_gamma                81.710(3)
_cell_formula_units_Z            4
_cell_length_a                   14.4990(5)
_cell_length_b                   15.0425(5)
_cell_length_c                   15.7255(4)
_cell_measurement_reflns_used    15148
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.9450
_cell_measurement_theta_min      3.9990
_cell_volume                     3165.65(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2017/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.963
_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    -81.00 -20.00   0.50    1.83    --  -42.55  99.00-178.00  122
  2  \w    -10.00  23.00   0.50    1.83    --  -42.55  99.00-178.00   66
  3  \w     20.00  45.00   0.50    1.83    --   42.55 -99.00  75.00   50
  4  \w    -17.00   9.00   0.50    1.83    --   42.55 -99.00  75.00   52
  5  \w    100.00 135.00   0.50    7.33    --   96.50  99.00-178.00   70
  6  \w   -105.00 -63.00   0.50    7.33    -- -111.75  99.00-178.00   84
  7  \w   -112.00 -15.00   0.50    1.83    --  -42.55 -19.00-120.00  194
  8  \w    -93.00 -20.00   0.50    1.83    --  -42.55 125.00-180.00  146
  9  \w    -49.00  32.00   0.50    1.83    --  -42.55  77.00   0.00  162
 10  \w   -116.00 -20.00   0.50    1.83    --  -42.55 -57.00  60.00  192
 11  \w    -33.00   5.00   0.50    1.83    --   42.55 -19.00   0.00   76
 12  \w     24.00  49.00   0.50    7.33    --   96.50 -61.00  90.00   50
 13  \w     22.00  49.00   0.50    7.33    --   96.50 -61.00 -60.00   54
 14  \w    121.00 151.00   0.50    7.33    --   96.50  61.00 150.00   60
 15  \w    106.00 155.00   0.50    7.33    --   96.50  30.00  90.00   98
 16  \w     74.00 155.00   0.50    7.33    --   96.50  30.00 120.00  162
 17  \w     22.00  50.00   0.50    7.33    --   96.50 -61.00-180.00   56
 18  \w     88.00 114.00   0.50    7.33    --   96.50  61.00 150.00   52
 19  \w     43.00  70.00   0.50    7.33    --   96.50 -99.00  75.00   54
 20  \w    -87.00 -39.00   0.50    7.33    -- -111.75  61.00-150.00   96
 21  \w   -108.00 -49.00   0.50    7.33    -- -111.75 125.00-120.00  118
 22  \w   -176.00 -91.00   0.50    7.33    -- -111.75 -30.00 -90.00  170
 23  \w   -109.00 -42.00   0.50    7.33    -- -111.75 125.00 150.00  134
 24  \w    -75.00 -49.00   0.50    7.33    -- -111.75  77.00 120.00   52
 25  \w    -67.00 -41.00   0.50    7.33    -- -111.75  77.00   0.00   52
 26  \w   -167.00 -88.00   0.50    7.33    -- -111.75 -61.00 150.00  158
 27  \w   -102.00 -45.00   0.50    7.33    -- -111.75 125.00  60.00  114
 28  \w   -134.00 -89.00   0.50    7.33    -- -111.75 -30.00 -30.00   90
 29  \w   -176.00 -92.00   0.50    7.33    -- -111.75 -45.00  60.00  168
 30  \w   -108.00 -82.00   0.50    7.33    -- -111.75 111.00 -15.29   52
 31  \w   -125.00 -99.00   0.50    7.33    -- -111.75  77.00 120.00   52
 32  \w   -177.00-146.00   0.50    7.33    -- -111.75 -30.00 -30.00   62
 33  \w    -77.00 -38.00   0.50    7.33    -- -111.75  61.00  60.00   78
 34  \w    -70.00 -36.00   0.50    7.33    -- -111.75  45.00 -60.00   68
 35  \w   -175.00-126.00   0.50    7.33    -- -111.75 -30.00   0.00   98
 36  \w   -122.00 -93.00   0.50    7.33    -- -111.75  77.00 150.00   58
 37  \w   -103.00 -76.00   0.50    7.33    -- -111.75  77.00   0.00   54
 38  \w   -108.00 -41.00   0.50    7.33    -- -111.75 109.00-126.57  134
 39  \w   -128.00 -90.00   0.50    7.33    -- -111.75 147.00  44.88   76
 40  \w    -83.00 -57.00   0.50    7.33    -- -111.75  61.00 -90.00   52
 41  \w    -68.00 -38.00   0.50    7.33    -- -111.75  45.00 -90.00   60
 42  \w    -79.00 -54.00   0.50    7.33    -- -111.75  77.00 150.00   50
 43  \w   -111.00 -76.00   0.50    7.33    -- -111.75 125.00 -30.00   70
 44  \w    -67.00 -42.00   0.50    7.33    -- -111.75  45.00 -30.00   50
 45  \w   -108.00 -55.00   0.50    7.33    -- -111.75 145.00 -89.40  106
 46  \w    -71.00 -37.00   0.50    7.33    -- -111.75  45.00  60.00   68
 47  \w   -111.00 -40.00   0.50    7.33    -- -111.75 125.00   0.00  142
 48  \w   -146.00-101.00   0.50    7.33    -- -111.75 -99.00  75.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at offset/far, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0832177000
_diffrn_orient_matrix_UB_12      -0.0616495000
_diffrn_orient_matrix_UB_13      0.0233713000
_diffrn_orient_matrix_UB_21      -0.0634180000
_diffrn_orient_matrix_UB_22      0.0765090000
_diffrn_orient_matrix_UB_23      -0.0356069000
_diffrn_orient_matrix_UB_31      0.0456306000
_diffrn_orient_matrix_UB_32      -0.0336955000
_diffrn_orient_matrix_UB_33      -0.0960065000
_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  0.0466
_diffrn_reflns_av_unetI/netI     0.0444
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            38109
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.963
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.070
_diffrn_reflns_theta_min         3.275
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.275
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56687
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.513
_exptl_crystal_description       plate
_exptl_crystal_F_000             1464
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.529
_refine_diff_density_min         -0.740
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.110
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     775
_refine_ls_number_reflns         12887
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.110
_refine_ls_R_factor_all          0.1068
_refine_ls_R_factor_gt           0.0967
_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^)+(0.1297P)^2^+17.3529P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2769
_refine_ls_wR_factor_ref         0.2838
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10962
_reflns_number_total             12887
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc05657d2.cif
_cod_data_source_block           20240622_1_autored
_cod_depositor_comments
;

2025-06-02
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C68 H42 Cl12 O2 P2 S2'
_cod_original_formula_weight         1442.47
_cod_original_formula_moiety         '2(C32 H19 O P S), 4(C H Cl3)'
_cod_original_formula_units_Z            2
_cod_database_code               1573169
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C28 P O S Cl6 H16'
_shelx_estimated_absorpt_t_max   0.787
_shelx_estimated_absorpt_t_min   0.339
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Ternary CH refined with riding coordinates:
 C72(H72), C76(H76), C84(H84), C80(H80)
2.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C61(H61), C39(H39), C13(H13), C57(H57), C62(H62), C10(H10), C34(H34),
 C45(H45), C26(H26), C22(H22), C59(H59), C30(H30), C14(H14), C48(H48), C60(H60),
  C58(H58), C25(H25), C69(H69), C33(H33), C15(H15), C23(H23), C16(H16),
 C65(H65), C64(H64), C49(H49), C68(H68), C63(H63), C24(H24), C51(H51), C28(H28),
  C29(H29), C27(H27), C32(H32), C66(H66), C31(H31), C67(H67), C50(H50)
;
_shelx_res_checksum              10458
_shelx_hkl_checksum              99128
_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 1.511
_oxdiff_exptl_absorpt_empirical_full_min 0.712