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_4038377
_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_formula_moiety
'C20 H16 N4 P, 3(C F3 O3 S), 1.71(C2 H3 N), 0.29(C2 N)'
_chemical_formula_sum            'C27 H21.13 F9 N6 O9 P S3'
_chemical_formula_weight         871.78
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-09-03
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 110.0904(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   30.8800(3)
_cell_length_b                   7.96591(7)
_cell_length_c                   29.4064(3)
_cell_measurement_reflns_used    12138
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.4360
_cell_measurement_theta_min      3.0500
_cell_volume                     6793.45(12)
_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      100.00(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 0.985
_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     27.00  53.00   0.50    1.00    --   42.75 -19.00   0.00   52
  2  \w     87.00 119.00   0.50    4.00    --  111.00  45.00 120.00   64
  3  \w    130.00 177.00   0.50    4.00    --  111.00  45.00 120.00   94
  4  \w    125.00 177.00   0.50    4.00    --  111.00  77.00  30.00  104
  5  \w    103.00 134.00   0.50    4.00    --  111.00 107.00-129.00   62
  6  \w     80.00 110.00   0.50    4.00    --  111.00  77.00  30.00   60
  7  \w     94.00 120.00   0.50    4.00    --  111.00 125.00  60.00   52
  8  \w     42.00  83.00   0.50    4.00    --  111.00 -61.00 -30.00   82
  9  \w     87.00 138.00   0.50    4.00    --  111.00 -61.00 -30.00  102
 10  \w     71.00 100.00   0.50    4.00    --  111.00-125.00 -30.00   58
 11  \w     69.00 106.00   0.50    4.00    --  111.00-125.00 -60.00   74
 12  \w     68.00 108.00   0.50    4.00    --  111.00 -94.00   0.00   80
 13  \w     56.00 116.00   0.50    4.00    --  111.00-125.00   0.00  120
 14  \w     54.00  99.00   0.50    4.00    --  111.00 -94.00 120.00   90
 15  \w     50.00  75.00   0.50    4.00    --  111.00 -94.00 150.00   50
 16  \w     30.00  56.00   0.50    4.00    --  111.00 -94.00   0.00   52
 17  \w     40.00  67.00   0.50    4.00    --  111.00-125.00 -30.00   54
 18  \w     73.00 115.00   0.50    4.00    --  111.00-125.00-150.00   84
 19  \w     84.00 109.00   0.50    4.00    --  111.00 -94.00-180.00   50
 20  \w    -35.00 -10.00   0.50    1.00    --   42.75 -19.00   0.00   50
 21  \w    -94.00 -12.00   0.50    1.00    --  -38.50 -57.00 120.00  164
 22  \w    -69.00  35.00   0.50    1.00    --  -38.50  77.00 -60.00  208
;
_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      -0.0130271000
_diffrn_orient_matrix_UB_12      -0.1875027000
_diffrn_orient_matrix_UB_13      -0.0038644000
_diffrn_orient_matrix_UB_21      0.0007550000
_diffrn_orient_matrix_UB_22      -0.0041502000
_diffrn_orient_matrix_UB_23      -0.0521168000
_diffrn_orient_matrix_UB_31      0.0514777000
_diffrn_orient_matrix_UB_32      -0.0471626000
_diffrn_orient_matrix_UB_33      0.0195827000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0186
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -37
_diffrn_reflns_number            18509
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.684
_diffrn_reflns_theta_min         3.582
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.472
_exptl_absorpt_correction_T_max  0.754
_exptl_absorpt_correction_T_min  0.464
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.705
_exptl_crystal_description       block
_exptl_crystal_F_000             3529
_exptl_crystal_size_max          0.327
_exptl_crystal_size_mid          0.176
_exptl_crystal_size_min          0.097
_refine_diff_density_max         1.092
_refine_diff_density_min         -0.739
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     713
_refine_ls_number_reflns         7053
_refine_ls_number_restraints     771
_refine_ls_restrained_S_all      1.197
_refine_ls_R_factor_all          0.0710
_refine_ls_R_factor_gt           0.0697
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0974P)^2^+32.9952P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1846
_refine_ls_wR_factor_ref         0.1857
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6831
_reflns_number_total             7053
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c00577_si_011.cif
_cod_data_source_block           jjw0935
_cod_original_cell_volume        6793.46(11)
_cod_database_code               4038377
_chemical_oxdiff_formula         'C208 H140 F72 N44 O72 P8 S24 '
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Uiso/Uaniso restraints and constraints
S1A \\sim F1A \\sim F2A \\sim F3A \\sim O1A \\sim O2A \\sim O3A \\sim C21A
\\sim S1B \\sim F1B \\sim F2B \\sim F3B \\sim O1B \\sim O2B \\sim O3B \\sim
C21B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.01
S3A \\sim F7A \\sim F8A \\sim F9A \\sim O7A \\sim O8A \\sim O9A \\sim C23A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
S3A \\sim F7A \\sim F8A \\sim F9A \\sim O7A \\sim O8A \\sim O9A \\sim C23A
\\sim S3B \\sim F7B \\sim F8B \\sim F9B \\sim O7B \\sim O8B \\sim O9B \\sim
C23B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
S2 \\sim F4A \\sim F4B \\sim F5A \\sim F5B \\sim F6A \\sim F6B \\sim O4A \\sim
O4B \\sim O5A \\sim O5B \\sim O6 \\sim C22A \\sim C22B: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02
N6B \\sim C26B \\sim C27B \\sim N6A \\sim C26A \\sim C27A \\sim N6C \\sim C26C
\\sim C27C: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
3. Same fragment restrains
{S3A, F8A, F7A, F9A, O7A, O8A, O9A, C23A} sigma for 1-2: 0.02, 1-3: 0.02
{S3B, F9B, F8B, F7B, O9B, O8B, O7B, C23B} sigma for 1-2: 0.02, 1-3: 0.02
as
{S1A, F1A, F2A, F3A, O1A, O2A, O3A, C21A}
{N6A, C26A, C27A} sigma for 1-2: 0.01, 1-3: 0.01
{N6C, C26C, C27C} sigma for 1-2: 0.01, 1-3: 0.01
{N6B, C26B, C27B} sigma for 1-2: 0.01, 1-3: 0.01
as
{N5, C24, C25}
4. Others
 0.5*[Sof(F4A)+Sof(F4B)+Sof(F5A)+Sof(F5B)+Sof(F6A)+Sof(F6B)+Sof(O4A)+Sof(O4B)+
 Sof(O5A)+Sof(O5B)+Sof(C22A)+Sof(C22B)+Sof(N6A)+Sof(C26A)+Sof(C27A)+Sof(H)+
 Sof(Ha)+Sof(Hb)]+1*[Sof(N6B)+Sof(C26B)+Sof(C27B)+Sof(H27a)+Sof(H27b)+
 Sof(H27c)]+1*[Sof(N6C)+Sof(C26C)+Sof(C27C)+Sof(H27d)+Sof(H27e)+Sof(H27f)]=1
 with esd of 0.0001
 Sof(S1B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(O1B)=Sof(O2B)=Sof(O3B)=Sof(C21B)=1-
 FVAR(1)
 Sof(S1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(C21A)=
 FVAR(1)
 Sof(F4B)=Sof(F5B)=Sof(F6B)=Sof(O4B)=Sof(O5B)=Sof(C22B)=1-FVAR(2)
 Sof(N6A)=Sof(C26A)=Sof(C27A)=Sof(H)=Sof(Ha)=Sof(Hb)=0.5*FVAR(3)
 Sof(F4A)=Sof(F5A)=Sof(F6A)=Sof(O4A)=Sof(O5A)=Sof(C22A)=FVAR(2)
 Sof(S3B)=Sof(F9B)=Sof(F8B)=Sof(F7B)=Sof(O9B)=Sof(O8B)=Sof(O7B)=Sof(C23B)=1-
 FVAR(3)
 Sof(S3A)=Sof(F8A)=Sof(F7A)=Sof(F9A)=Sof(O7A)=Sof(O8A)=Sof(O9A)=Sof(C23A)=
 FVAR(3)
 Sof(N6C)=Sof(C26C)=Sof(C27C)=Sof(H27d)=Sof(H27e)=Sof(H27f)=FVAR(4)
 Sof(N6B)=Sof(C26B)=Sof(C27B)=Sof(H27a)=Sof(H27b)=Sof(H27c)=FVAR(5)
5.a Me refined with riding coordinates:
 C27C(H27d,H27e,H27f)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C13(H13), C14(H14), C17(H17), C18(H18), C19(H19), C20(H20)
5.c Idealised Me refined as rotating group:
 C25(H25a,H25b,H25c), C27B(H27a,H27b,H27c)
;
_shelx_res_checksum              97068
_shelx_hkl_checksum              49480
_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 1.340
_oxdiff_exptl_absorpt_empirical_full_min 0.727