Dual role of polyphosphoric acid-activated nitroalkanes in oxidative peri-annulations: efficient synthesis of 1,3,6,8-tetraazapyrenes
Aksenov, Alexander V.; Ovcharov, Dmitrii S.; Aksenov, Nicolai A.; Aksenov, Dmitrii A.; Nadein, Oleg N.; Rubin, Michael; RSC Adv. 7 (2017) 29927–; doi:10.1039/C7RA04751G

data_7228451
_publ_section_title
;
 Dual role of polyphosphoric acid-activated nitroalkanes in oxidative
 peri-annulations: efficient synthesis of 1,3,6,8-tetraazapyrenes
;
_journal_issue                   48
_journal_name_full               'RSC Adv.'
_journal_page_first              29927
_journal_paper_doi               10.1039/C7RA04751G
_journal_volume                  7
_journal_year                    2017
_chemical_formula_moiety         'C14 H10 N4'
_chemical_formula_sum            'C14 H10 N4'
_chemical_formula_weight         234.26
_chemical_name_systematic        2,7-dimethyl-1,3,6,8-Tetraazapyrene
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-04-15
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_audit_update_record
;
2017-04-15 deposited with the CCDC.
2017-06-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.335(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   3.8706(2)
_cell_length_b                   7.4727(4)
_cell_length_c                   18.9360(12)
_cell_measurement_reflns_used    2767
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      73.3260
_cell_measurement_theta_min      5.9400
_cell_volume                     547.69(5)
_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_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2529
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_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   -116.00 -17.00   1.00    3.17    --  -41.60 -38.00   0.00   99
  2  \w    -33.00  66.00   1.00    3.17    --   41.60 -38.00 150.00   99
  3  \w     26.00  99.00   1.00    3.17    --   41.60-128.00 116.00   73
  4  \w     94.00 178.00   1.00   12.67    --  106.96 125.00-180.00   84
  5  \w     25.00 109.00   1.00   12.67    --  106.96 -95.00   0.00   84
  6  \w     25.00 160.00   1.00   12.67    --  106.96 -15.00   0.00  135
  7  \w   -118.00  -9.00   1.00    3.17    --  -41.60 -77.00-120.00  109
  8  \w    -70.00  32.00   1.00    3.17    --  -41.60  57.00 -30.00  102
  9  \w   -114.00 -13.00   1.00    3.17    --  -41.60 -57.00 120.00  101
 10  \w     54.00 117.00   1.00   12.67    --  106.96  15.00 150.00   63
 11  \w     94.00 178.00   1.00   12.67    --  106.96 125.00   0.00   84
 12  \w     87.00 126.00   1.00   12.67    --  106.96  45.00-150.00   39
 13  \w     87.00 119.00   1.00   12.67    --  106.96 -77.00-150.00   32
 14  \w   -118.00  -9.00   1.00    3.17    --  -41.85 -77.00 -30.00  109
 15  \w   -114.00 -62.00   1.00    3.17    --  -41.85-143.00 -52.00   52
 16  \w      9.00 118.00   1.00    3.17    --   41.85  77.00 150.00  109
 17  \w      9.00 118.00   1.00    3.17    --   41.85  77.00-120.00  109
 18  \w     23.00  98.00   1.00    3.17    --   41.85-125.00 150.00   75
 19  \w     94.00 178.00   1.00   12.67    --  106.96 125.00 -60.00   84
 20  \w     78.00 178.00   1.00   12.67    --  106.96  61.00 150.00  100
;
_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      -0.0264376000
_diffrn_orient_matrix_UB_12      0.1870967000
_diffrn_orient_matrix_UB_13      0.0337144000
_diffrn_orient_matrix_UB_21      -0.0067232000
_diffrn_orient_matrix_UB_22      -0.0859924000
_diffrn_orient_matrix_UB_23      0.0739296000
_diffrn_orient_matrix_UB_31      0.3970391000
_diffrn_orient_matrix_UB_32      0.0108655000
_diffrn_orient_matrix_UB_33      0.0039740000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0281
_diffrn_reflns_av_unetI/netI     0.0171
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_h_min       -3
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            5093
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.631
_diffrn_reflns_theta_min         4.670
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.715
_exptl_absorpt_correction_T_max  0.979
_exptl_absorpt_correction_T_min  0.869
_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 yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.420
_exptl_crystal_description       needle
_exptl_crystal_F_000             244
_exptl_crystal_recrystallization_method
'Crystallized by slow evaporation method with CDCl3 as slovent'
_exptl_crystal_size_max          0.511
_exptl_crystal_size_mid          0.078
_exptl_crystal_size_min          0.041
_refine_diff_density_max         0.207
_refine_diff_density_min         -0.227
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.139
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     83
_refine_ls_number_reflns         1087
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.139
_refine_ls_R_factor_all          0.0518
_refine_ls_R_factor_gt           0.0455
_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^)+(0.0786P)^2^+0.0866P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1312
_refine_ls_wR_factor_ref         0.1457
_reflns_Friedel_coverage         0.000
_reflns_number_gt                942
_reflns_number_total             1087
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7ra04751g2.cif
_cod_data_source_block           anna_me_14042017_2
_cod_database_code               7228451
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C11 H10 N O'
_reflns_odcompleteness_completeness 99.91
_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.a Aromatic/amide H refined with riding coordinates:
 C9(H9), C8(H8)
2.b Idealised Me refined as rotating group:
 C12(H12C,H12A,H12B)
;
_olex2_date_sample_data_collection 2017-04-14
_olex2_exptl_crystal_mounting_method
'Mounted by acrylic glue on the glass stick'
_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 1.843
_oxdiff_exptl_absorpt_empirical_full_min 0.574