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_4038369
_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         'C28 H38 N6 P, C F3 O3 S, 0.5(C4 H10 O)'
_chemical_formula_sum            'C31 H43 F3 N6 O3.5 P S'
_chemical_formula_weight         675.74
_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
_audit_creation_date             2017-01-24
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                73.762(2)
_cell_angle_beta                 72.1020(10)
_cell_angle_gamma                78.218(2)
_cell_formula_units_Z            4
_cell_length_a                   13.8270(2)
_cell_length_b                   13.9544(3)
_cell_length_c                   20.1132(3)
_cell_measurement_reflns_used    25741
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.5830
_cell_measurement_theta_min      3.3840
_cell_volume                     3515.84(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (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 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.977
_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     21.00 109.00   0.50    1.00    --   42.50  38.00 -60.00  176
  2  \w     80.00 129.00   0.50    4.00    --  111.00  77.00  30.00   98
  3  \w    120.00 163.00   0.50    4.00    --  111.00  61.00  30.00   86
  4  \w    149.00 176.00   0.50    4.00    --  111.00  77.00  30.00   54
  5  \w    138.00 165.00   0.50    4.00    --  111.00  61.00  90.00   54
  6  \w    126.00 178.00   0.50    4.00    --  111.00  77.00 150.00  104
  7  \w    124.00 151.00   0.50    4.00    --  111.00  45.00 120.00   54
  8  \w    116.00 173.00   0.50    4.00    --  111.00  77.00  90.00  114
  9  \w    123.00 150.00   0.50    4.00    --  111.00  77.00   0.00   54
 10  \w    142.00 176.00   0.50    4.00    --  111.00  77.00 -60.00   68
 11  \w    132.00 164.00   0.50    4.00    --  111.00  61.00 -90.00   64
 12  \w    128.00 155.00   0.50    4.00    --  111.00  61.00-120.00   54
 13  \w    122.00 177.00   0.50    4.00    --  111.00  77.00-150.00  110
 14  \w     87.00 165.00   0.50    4.00    --  111.00  45.00 -60.00  156
 15  \w     87.00 121.00   0.50    4.00    --  111.00  45.00 -30.00   68
 16  \w     83.00 109.00   0.50    4.00    --  111.00  61.00  30.00   52
 17  \w     83.00 162.00   0.50    4.00    --  111.00  61.00   0.00  158
 18  \w     83.00 120.00   0.50    4.00    --  111.00  61.00 120.00   74
 19  \w     87.00 116.00   0.50    4.00    --  111.00  45.00 120.00   58
 20  \w     83.00 150.00   0.50    4.00    --  111.00  61.00 150.00  134
 21  \w     83.00 114.00   0.50    4.00    --  111.00  61.00  90.00   62
 22  \w     80.00 175.00   0.50    4.00    --  111.00  77.00 120.00  190
 23  \w     83.00 109.00   0.50    4.00    --  111.00  61.00 -60.00   52
 24  \w     83.00 109.00   0.50    4.00    --  111.00  61.00 -90.00   52
 25  \w     83.00 111.00   0.50    4.00    --  111.00  61.00-120.00   56
 26  \w     83.00 150.00   0.50    4.00    --  111.00  61.00-150.00  134
 27  \w     83.00 159.00   0.50    4.00    --  111.00  61.00-180.00  152
 28  \w     80.00 107.00   0.50    4.00    --  111.00  77.00 -90.00   54
 29  \w     80.00 106.00   0.50    4.00    --  111.00  77.00 -60.00   52
 30  \w     80.00 132.00   0.50    4.00    --  111.00  77.00 -30.00  104
 31  \w     80.00 106.00   0.50    4.00    --  111.00  77.00  60.00   52
 32  \w     80.00 107.00   0.50    4.00    --  111.00  77.00  90.00   54
 33  \w     83.00 171.00   0.50    4.00    --  111.00  61.00  60.00  176
 34  \w     80.00 107.00   0.50    4.00    --  111.00  77.00   0.00   54
 35  \w     83.00 174.00   0.50    4.00    --  111.00  61.00 -30.00  182
 36  \w    103.00 142.00   0.50    4.00    --  111.00 -77.00   0.00   78
 37  \w    115.00 141.00   0.50    4.00    --  111.00 -77.00-120.00   52
 38  \w     84.00 109.00   0.50    4.00    --  111.00 -94.00 -30.00   50
 39  \w     74.00 107.00   0.50    4.00    --  111.00-125.00-120.00   66
 40  \w     76.00 121.00   0.50    4.00    --  111.00-125.00-180.00   90
 41  \w     50.00  92.00   0.50    4.00    --  111.00 -77.00-120.00   84
 42  \w     39.00  71.00   0.50    4.00    --  111.00 -94.00 -30.00   64
 43  \w     45.00  85.00   0.50    4.00    --  111.00 -77.00   0.00   80
 44  \w     41.00 120.00   0.50    4.00    --  111.00-125.00  90.00  158
 45  \w     66.00 104.00   0.50    1.00    --   42.50-137.00 -27.00   76
 46  \w     40.00  65.00   0.50    1.00    --   42.50 -99.00  60.00   50
 47  \w     33.00 109.00   0.50    4.00    --  111.00 -94.00 -60.00  152
 48  \w     42.00 121.00   0.50    4.00    --  111.00-125.00 -90.00  158
 49  \w     40.00 134.00   0.50    4.00    --  111.00 -45.00  90.00  188
 50  \w     80.00 106.00   0.50    4.00    --  111.00  77.00 150.00   52
 51  \w     20.00  80.00   0.50    1.00    --   42.50  38.00 150.00  120
 52  \w     13.00  65.00   0.50    1.00    --   42.50  77.00 120.00  104
 53  \w     11.00 109.00   0.50    1.00    --   42.50  77.00  60.00  196
 54  \w     80.00 173.00   0.50    4.00    --  111.00  77.00-120.00  186
 55  \w     80.00 106.00   0.50    4.00    --  111.00  77.00-150.00   52
 56  \w     80.00 106.00   0.50    4.00    --  111.00  77.00-180.00   52
 57  \w     11.00  16.50   0.50    1.00    --   42.50  77.00 -30.00   11
;
_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      -0.0369132000
_diffrn_orient_matrix_UB_12      -0.0309695000
_diffrn_orient_matrix_UB_13      0.0825755000
_diffrn_orient_matrix_UB_21      0.0926451000
_diffrn_orient_matrix_UB_22      0.0397871000
_diffrn_orient_matrix_UB_23      0.0054982000
_diffrn_orient_matrix_UB_31      -0.0632161000
_diffrn_orient_matrix_UB_32      0.1044279000
_diffrn_orient_matrix_UB_33      0.0009970000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0121
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            25162
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.693
_diffrn_reflns_theta_min         3.327
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.736
_exptl_absorpt_correction_T_max  -0.010
_exptl_absorpt_correction_T_min  10000000.000
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.277
_exptl_crystal_description       plate
_exptl_crystal_F_000             1428
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.235
_exptl_crystal_size_min          0.105
_refine_diff_density_max         1.619
_refine_diff_density_min         -0.584
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     858
_refine_ls_number_reflns         25162
_refine_ls_number_restraints     118
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0635
_refine_ls_R_factor_gt           0.0609
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1262P)^2^+0.9081P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1638
_refine_ls_wR_factor_ref         0.1668
_reflns_Friedel_coverage         0.000
_reflns_number_gt                23250
_reflns_number_total             25162
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9825\% 
 around [0.00 0.71 0.71] (reciprocal) or [-0.34 0.87 0.36] (direct)
;
_cod_data_source_file            jo0c00577_si_012.cif
_cod_data_source_block           jjw0603_twin1_hklf5
_cod_original_formula_sum        'C31 H43 F3 N6 O3.50 P S'
_cod_database_code               4038369
_chemical_oxdiff_formula         C31H43F3N6O3.5PS
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.5229(8) 0.4771(8)
2. 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
3. Uiso/Uaniso restraints and constraints
O4A \\sim C30A \\sim C31A \\sim C32A \\sim C33A \\sim O4B \\sim C30B \\sim C31B
\\sim C32B \\sim C33B: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
4. Same fragment restrains
{O4B, C30B, C31B, C32B, C33B} sigma for 1-2: 0.02, 1-3: 0.02
as
{O4A, C30A, C31A, C32A, C33A}
5. Others
 Sof(O4B)=Sof(C30B)=Sof(H30D)=Sof(H30E)=Sof(H30F)=Sof(C31B)=Sof(H31C)=
 Sof(H31D)=Sof(C32B)=Sof(H32C)=Sof(H32D)=Sof(C33B)=Sof(H33D)=Sof(H33E)=
 Sof(H33F)=1-FVAR(1)
 Sof(O4A)=Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=Sof(C31A)=Sof(H31A)=
 Sof(H31B)=Sof(C32A)=Sof(H32A)=Sof(H32B)=Sof(C33A)=Sof(H33A)=Sof(H33B)=
 Sof(H33C)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C14B(H14B), C17B(H17B), C23B(H23B), C26B(H26B), C14A(H14A), C17A(H17A),
 C23A(H23A), C26A(H26A)
6.b Secondary CH2 refined with riding coordinates:
 C31A(H31A,H31B), C32A(H32A,H32B), C31B(H31C,H31D), C32B(H32C,H32D)
6.c Me refined with riding coordinates:
 C30A(H30A,H30B,H30C), C33A(H33A,H33B,H33C), C30B(H30D,H30E,H30F), C33B(H33D,
 H33E,H33F)
6.d Aromatic/amide H refined with riding coordinates:
 C2B(H2B), C3B(H3B), C4B(H4B), C5B(H5B), C7B(H7B), C8B(H8B), C9B(H9B),
 C10B(H10B), C12B(H12B), C21B(H21B), C2A(H2A), C3A(H3A), C4A(H4A), C5A(H5A),
 C7A(H7A), C8A(H8A), C9A(H9A), C10A(H10A), C12A(H12A), C21A(H21A)
6.e Idealised Me refined as rotating group:
 C15B(H15A,H15B,H15C), C16B(H16A,H16B,H16C), C18B(H18A,H18B,H18C), C19B(H19A,
 H19B,H19C), C24B(H24A,H24B,H24C), C25B(H25A,H25B,H25C), C27B(H27A,H27B,H27C),
 C28B(H28A,H28B,H28C), C15A(H15D,H15E,H15F), C16A(H16D,H16E,H16F), C18A(H18D,
 H18E,H18F), C19A(H19D,H19E,H19F), C24A(H24D,H24E,H24F), C25A(H25D,H25E,H25F),
 C27A(H27D,H27E,H27F), C28A(H28D,H28E,H28F)
;
_shelx_res_checksum              42902
_shelx_hkl_checksum              69727
_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 1.310
_oxdiff_exptl_absorpt_empirical_full_min 0.690
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2