Toward N,P-Doped π-Extended PAHs: A One-Pot Synthesis to Diannulated 1,4,2-Diazaphospholium Triflate Salts.
Schoemaker, Robin; Schwedtmann, Kai; Hennersdorf, Felix; Bauzá, Antonio; Frontera, Antonio; Weigand, Jan J.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c00577

data_4038371
_publ_section_title
;
 Toward N,P-Doped \p-Extended PAHs: A One-Pot Synthesis to Diannulated
 1,4,2-Diazaphospholium Triflate Salts.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c00577
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C10 H8 Cl4 N2 P, C F3 O3 S'
_chemical_formula_sum            'C11 H8 Cl4 F3 N2 O3 P S'
_chemical_formula_weight         478.02
_space_group_crystal_system      monoclinic
_space_group_IT_number           7
_space_group_name_Hall           'P -2yac'
_space_group_name_H-M_alt        'P 1 n 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-02-26
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 109.4015(14)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   9.33396(12)
_cell_length_b                   8.28139(10)
_cell_length_c                   11.25557(14)
_cell_measurement_reflns_used    11804
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.0980
_cell_measurement_theta_min      4.1600
_cell_volume                     820.629(19)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2850
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.998
_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    -47.00 -17.00   0.50    1.00    --  -38.50 -57.00 -30.00   60
  2  \w    -65.00 -16.00   0.50    1.00    --  -38.50 -38.00-180.00   98
  3  \w      2.00  74.00   0.50    1.00    --   42.50 -99.00-180.00  144
  4  \w     58.00  98.00   0.50    4.00    --  111.00 -61.00-180.00   80
  5  \w    105.00 137.00   0.50    4.00    --  111.00 -61.00-180.00   64
  6  \w    111.00 136.00   0.50    4.00    --  111.00 -61.00-120.00   50
  7  \w     86.00 116.00   0.50    4.00    --  111.00-125.00 -30.00   60
  8  \w     80.00 109.00   0.50    4.00    --  111.00 -94.00-150.00   58
  9  \w     46.00  91.00   0.50    4.00    --  111.00 -94.00-180.00   90
 10  \w     40.00 120.00   0.50    4.00    --  111.00-125.00-180.00  160
 11  \w     41.00  70.00   0.50    4.00    --  111.00 -61.00-120.00   58
 12  \w     37.00  65.00   0.50    4.00    --  111.00 -94.00-150.00   56
 13  \w     32.00 100.00   0.50    4.00    --  111.00 -94.00 -30.00  136
 14  \w     52.00  77.00   0.50    4.00    --  111.00 -94.00  90.00   50
 15  \w     93.00 121.00   0.50    4.00    --  111.00-125.00 150.00   56
 16  \w     41.00  85.00   0.50    4.00    --  111.00-125.00 150.00   88
 17  \w     32.00 106.00   0.50    4.00    --  111.00 -94.00  30.00  148
 18  \w     24.00  84.00   0.50    1.00    --   42.50-125.00   0.00  120
 19  \w    -27.00  65.00   0.50    1.00    --   42.50 -57.00  30.00  184
 20  \w     86.00 163.00   0.50    4.00    --  111.00  61.00 -90.00  154
 21  \w    127.00 156.00   0.50    4.00    --  111.00  61.00-120.00   58
 22  \w    142.00 178.00   0.50    4.00    --  111.00  77.00-180.00   72
 23  \w     88.00 136.00   0.50    1.00    --   62.00  77.00 -94.72   96
 24  \w     84.00 109.00   0.50    4.00    --  111.00  61.00-120.00   50
 25  \w     81.00 108.00   0.50    4.00    --  111.00  77.00-120.00   54
 26  \w     80.00 175.00   0.50    4.00    --  111.00  77.00-150.00  190
 27  \w    128.00 175.00   0.50    4.00    --  111.00  61.00   0.00   94
 28  \w    122.00 169.00   0.50    4.00    --  111.00  77.00  30.00   94
 29  \w    127.00 161.00   0.50    4.00    --  111.00  61.00  60.00   68
 30  \w    103.00 130.00   0.50    1.00    --   62.00  76.00 106.13   54
 31  \w     81.00 147.00   0.50    1.00    --   74.00  77.00  18.64  132
 32  \w     87.00 120.00   0.50    4.00    --  111.00  61.00 -60.00   66
 33  \w     82.00 166.00   0.50    4.00    --  111.00  77.00 -60.00  168
 34  \w     83.00 112.00   0.50    4.00    --  111.00  61.00  90.00   58
 35  \w     84.00 122.00   0.50    4.00    --  111.00  61.00  60.00   76
 36  \w     84.00 136.00   0.50    4.00    --  111.00  61.00  30.00  104
 37  \w     83.00 116.00   0.50    4.00    --  111.00  61.00   0.00   66
 38  \w     81.00 108.00   0.50    4.00    --  111.00  77.00  60.00   54
 39  \w     80.00 151.00   0.50    4.00    --  111.00  77.00  90.00  142
 40  \w     84.00 128.00   0.50    4.00    --  111.00  61.00 150.00   88
 41  \w     82.00 174.00   0.50    4.00    --  111.00  77.00 150.00  184
 42  \w     83.00 178.00   0.50    4.00    --  111.00  61.00 120.00  190
 43  \w     80.00 106.00   0.50    4.00    --  111.00  77.00  30.00   52
 44  \w     80.00 178.00   0.50    4.00    --  111.00  77.00 -30.00  196
 45  \w     85.00 110.00   0.50    4.00    --  111.00  61.00-180.00   50
 46  \w     81.00 141.00   0.50    4.00    --  111.00  77.00-180.00  120
 47  \w     80.00 108.00   0.50    4.00    --  111.00  77.00 -90.00   56
 48  \w     43.00  76.00   0.50    1.00    --   74.00  77.00  18.64   66
 49  \w     38.00  65.00   0.50    1.00    --   66.00  74.00  62.90   54
 50  \w     32.00  61.00   0.50    1.00    --   62.00  76.00 106.13   58
 51  \w     29.00  57.00   0.50    1.00    --   58.00  77.00 135.48   56
 52  \w     31.00  63.00   0.50    1.00    --   62.00  77.00 174.78   64
 53  \w     80.00 106.00   0.50    4.00    --  111.00  77.00 120.00   52
 54  \w     33.00  74.00   0.50    1.00    --   62.00  76.00  -6.53   82
 55  \w     36.00  75.00   0.50    1.00    --   66.00  76.00 -63.26   78
 56  \w     31.00  57.00   0.50    1.00    --   62.00  77.00 -94.72   52
 57  \w     23.00  48.00   0.50    1.00    --   54.00  78.00 -70.19   50
 58  \w     17.00  42.00   0.50    1.00    --   50.00  82.00 -32.96   50
 59  \w     22.00  47.00   0.50    1.00    --   54.00  78.00  19.44   50
 60  \w      6.00  31.00   0.50    1.00    --   42.00  90.00 -19.65   50
 61  \w     18.00  44.00   0.50    1.00    --   50.00  80.00-123.98   52
 62  \w     44.00  86.00   0.50    1.00    --   74.00  76.00-154.72   84
 63  \w      6.00  32.00   0.50    1.00    --   42.00  90.00-172.74   52
 64  \w   -104.00 -60.00   0.50    1.00    --  -38.50 -57.00 -30.00   88
 65  \w   -108.00 -18.00   0.50    1.00    --  -38.50 -38.00  90.00  180
 66  \w      7.00  32.00   0.50    1.00    --   42.00  87.00 104.13   50
 67  \w   -109.00 -82.00   0.50    1.00    --  -38.50 -38.00-180.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1413772000
_diffrn_orient_matrix_UB_12      -0.0067946000
_diffrn_orient_matrix_UB_13      0.0415879000
_diffrn_orient_matrix_UB_21      0.0978145000
_diffrn_orient_matrix_UB_22      0.0500469000
_diffrn_orient_matrix_UB_23      0.1343116000
_diffrn_orient_matrix_UB_31      -0.0328502000
_diffrn_orient_matrix_UB_32      0.1789979000
_diffrn_orient_matrix_UB_33      -0.0358805000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0229
_diffrn_reflns_av_unetI/netI     0.0142
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            14816
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.573
_diffrn_reflns_theta_min         5.341
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.153
_exptl_absorpt_correction_T_max  0.633
_exptl_absorpt_correction_T_min  0.306
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
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            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.935
_exptl_crystal_description       block
_exptl_crystal_F_000             476
_exptl_crystal_size_max          0.188
_exptl_crystal_size_mid          0.115
_exptl_crystal_size_min          0.059
_refine_diff_density_max         0.236
_refine_diff_density_min         -0.397
_refine_diff_density_rms         0.062
_refine_ls_abs_structure_details
;
 Flack x determined using 1671 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.023(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         3415
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.092
_refine_ls_R_factor_all          0.0246
_refine_ls_R_factor_gt           0.0246
_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^)+(0.0115P)^2^+1.5744P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0587
_refine_ls_wR_factor_ref         0.0587
_reflns_Friedel_coverage         0.981
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                3415
_reflns_number_total             3415
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00577_si_003.cif
_cod_data_source_block           jjw0439
_cod_database_code               4038371
_chemical_oxdiff_formula         'C22 H16 Cl8 F6 N4 O6 P2 S2 '
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Shared sites
{N2A, C1B}
{C6A, N1B}
{N1A, C6B}
{C1A, N2B}
3. Uiso/Uaniso restraints and constraints
Uanis(N2A) = Uanis(C1B)
Uanis(C6A) = Uanis(N1B)
Uanis(C1A) = Uanis(N2B)
Uanis(N2A) = Uanis(C1B)
Uanis(C6A) = Uanis(N1B)
Uanis(C1A) = Uanis(N2B)
Uanis(N1A) = Uanis(C6B)
Uanis(N1A) = Uanis(C6B)
4. Others
 Sof(H10A)=Sof(H7B)=Sof(H5B)=Sof(H2B)=Sof(C1B)=Sof(C6B)=Sof(N2B)=Sof(N1B)=1-
 FVAR(1)
 Sof(N2A)=Sof(N1A)=Sof(C1A)=Sof(C6A)=Sof(H10)=Sof(H7)=Sof(H5)=Sof(H2)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C10(H10), C10(H10A), C7(H7), C7(H7B), C9(H9), C5(H5), C5(H5B), C4(H4),
  C2(H2), C2(H2B), C3(H3)
;
_shelx_res_checksum              21007
_shelx_hkl_checksum              71375
_shelx_shelxl_version_number     2014/7
_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 1.193
_oxdiff_exptl_absorpt_empirical_full_min 0.840