Photochemical synthesis and ring-chain-ring tautomerism of benzo[4,5]imidazo[1,2-<i>a</i>]cyclopenta[<i>e</i>]pyridines.
Komogortsev, Andrey N.; Lichitskii, Boris V.; Milyutin, Constantine V.; Melekhina, Valeriya G.; Organic & biomolecular chemistry 21 (2023) 2720–2728; doi:10.1039/d3ob00273j

data_7159226
_publ_section_title
;
 Photochemical synthesis and ring-chain-ring tautomerism of
 benzo[4,5]imidazo[1,2-<i>a</i>]cyclopenta[<i>e</i>]pyridines.
;
_journal_issue                   13
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2720
_journal_page_last               2728
_journal_paper_doi               10.1039/d3ob00273j
_journal_volume                  21
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C20 H22 N2 O3'
_chemical_formula_sum            'C20 H22 N2 O3'
_chemical_formula_weight         338.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2022-01-26
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2022-12-29 deposited with the CCDC.	2023-03-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 110.8694(11)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.68226(12)
_cell_length_b                   9.54123(6)
_cell_length_c                   15.99352(16)
_cell_measurement_reflns_used    39700
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.4630
_cell_measurement_theta_min      2.9540
_cell_volume                     1665.73(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.996
_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     49.00  75.00   0.40    0.08    --   48.65  16.00-155.00   65
  2  \w     56.00  81.20   0.40    0.08    --   48.65  16.00-155.00   63
  3  \w     89.00 115.00   0.40    0.08    --   48.65  16.00-155.00   65
  4  \w     46.00  72.00   0.40    0.18    --  111.50 -77.00-180.00   65
  5  \w     50.00  76.00   0.40    0.18    --  111.50 -78.00-141.27   65
  6  \w     77.00 103.00   0.40    0.18    --  111.50 -77.00-180.00   65
  7  \w    104.00 130.00   0.40    0.18    --  111.50 -79.00-109.18   65
  8  \w     66.00 103.20   0.40    0.18    --  111.50 -77.00-157.28   93
  9  \w     44.00  71.20   0.40    0.18    --  111.50 -77.00-128.30   68
 10  \w     49.00  75.00   0.40    0.18    --  111.50 -79.00-109.18   65
 11  \w     59.00  85.00   0.40    0.18    --  111.50 -77.00 -30.00   65
 12  \w     61.00  99.00   0.40    0.18    --  111.50 -77.00 -60.00   95
 13  \w     54.00  79.20   0.40    0.18    --  111.50 -77.00   0.00   63
 14  \w     79.00 104.20   0.40    0.18    --  111.50 -77.00 -30.00   63
 15  \w     76.00 102.00   0.40    0.18    --  111.50 -77.00  30.00   65
 16  \w     58.00  92.00   0.40    0.18    --  111.50 -77.00  60.00   85
 17  \w     51.00  87.00   0.40    0.18    --  111.50 -77.00 120.00   90
 18  \w     40.00  66.00   0.40    0.18    --  111.50 -77.00  90.00   65
 19  \w     43.00  69.00   0.40    0.18    --  111.50 -77.00  30.00   65
 20  \w     44.00  70.00   0.40    0.18    --  111.50 -61.00  30.00   65
 21  \w     57.00  95.00   0.40    0.18    --  111.50 -77.00  60.00   95
 22  \w     40.00  65.20   0.40    0.18    --  111.50 -61.00  90.00   63
 23  \w     41.00  69.00   0.40    0.18    --  111.50 -61.00 150.00   70
 24  \w     42.00  69.20   0.40    0.18    --  111.50 -61.00 -60.00   68
 25  \w     40.00  65.20   0.40    0.18    --  111.50 -61.00 -90.00   63
 26  \w     43.00  69.00   0.40    0.18    --  111.50 -61.00 -30.00   65
 27  \w     43.00  69.00   0.40    0.18    --  111.50 -61.00-120.00   65
 28  \w     50.00  76.00   0.40    0.18    --  111.50 -77.00-180.00   65
 29  \w     40.00  67.20   0.40    0.18    --  111.50 -61.00-180.00   68
 30  \w     18.00  56.00   0.40    0.08    --   48.65 -57.00-150.00   95
 31  \w     -3.00  22.20   0.40    0.08    --   48.65 -16.00  34.00   63
 32  \w     47.00  73.00   0.40    0.18    --  111.50  -1.00 169.36   65
 33  \w     93.00 119.00   0.40    0.18    --  111.50  -1.00 169.36   65
 34  \w     93.00 119.00   0.40    0.18    --  111.50 -81.00  91.66   65
 35  \w     58.00 110.00   0.40    0.18    --  111.50-125.00  90.00  130
 36  \w     70.00 119.20   0.40    0.18    --  111.50-137.00 103.61  123
 37  \w     71.00 108.20   0.40    0.18    --  111.50-125.00  60.00   93
 38  \w     51.00  92.20   0.40    0.08    --   48.65-125.00-120.00  103
 39  \w     60.00  94.00   0.40    0.08    --   48.65-125.00-180.00   85
 40  \w     47.00  79.00   0.40    0.18    --  111.50-125.00-180.00   80
 41  \w     84.00 110.00   0.40    0.18    --  111.50-125.00-180.00   65
 42  \w     81.00 106.20   0.40    0.18    --  111.50-125.00-150.00   63
 43  \w     84.00 110.00   0.40    0.18    --  111.50-125.00 -90.00   65
 44  \w     57.00  83.00   0.40    0.18    --  111.50-125.00 -30.00   65
 45  \w     77.00 108.20   0.40    0.18    --  111.50-117.00 -87.17   78
 46  \w     45.00  71.00   0.40    0.18    --  111.50-117.00 -87.17   65
 47  \w     81.00 106.20   0.40    0.18    --  111.50-105.00 -28.94   63
 48  \w     48.00  74.00   0.40    0.18    --  111.50-118.00   9.99   65
 49  \w     48.00  80.00   0.40    0.18    --  111.50-125.00 120.00   80
 50  \w     63.00 110.20   0.40    0.18    --  111.50-125.00 150.00  118
 51  \w     82.80 108.00   0.40    0.18    --  111.50-115.00  87.02   63
 52  \w     80.80 106.00   0.40    0.18    --  111.50-100.00-104.69   63
 53  \w     69.00  94.20   0.40    0.18    --  111.50 -95.00-180.00   63
 54  \w     79.00 105.00   0.40    0.18    --  111.50 -97.00 -90.48   65
 55  \w     47.00  73.00   0.40    0.18    --  111.50 -95.00-150.00   65
 56  \w     51.00 100.20   0.40    0.18    --  111.50 -95.00 -90.00  123
 57  \w     59.00 101.00   0.40    0.18    --  111.50 -95.00 -60.00  105
 58  \w     45.00  71.00   0.40    0.18    --  111.50 -95.00   0.00   65
 59  \w     78.00 104.00   0.40    0.18    --  111.50 -95.00 -90.00   65
 60  \w     46.00  72.00   0.40    0.18    --  111.50 -95.00  60.00   65
 61  \w     74.00 100.00   0.40    0.18    --  111.50 -95.00  90.00   65
 62  \w     76.00 102.00   0.40    0.18    --  111.50 -95.00 120.00   65
 63  \w     40.00  71.20   0.40    0.18    --  111.50 -95.00 150.00   78
 64  \w    109.00 135.00   0.40    0.18    --  111.50 -88.00 -57.26   65
 65  \w     54.00  80.00   0.40    0.18    --  111.50 -88.00 -57.26   65
 66  \w     42.00  67.20   0.40    0.18    --  111.50 -95.00-120.00   63
 67  \w     57.00 104.20   0.40    0.18    --  111.50 -92.00 -77.71  118
 68  \w     87.00 113.00   0.40    0.18    --  111.50 -88.00 -22.40   65
 69  \w     64.00 122.00   0.40    0.18    --  111.50 -85.00 -67.99  145
 70  \w     54.00  80.00   0.40    0.18    --  111.50 -83.00  15.82   65
 71  \w    105.00 131.00   0.40    0.18    --  111.50 -83.00  18.70   65
 72  \w     61.00 112.20   0.40    0.18    --  111.50 -87.00 149.46  128
 73  \w     99.00 127.00   0.40    0.18    --  111.50 -87.00 174.70   70
 74  \w     84.00 110.00   0.40    0.18    --  111.50 -82.00 166.81   65
 75  \w     53.00  87.00   0.40    0.18    --  111.50 -87.00 174.70   85
 76  \w     49.00  75.00   0.40    0.18    --  111.50 -82.00 166.81   65
 77  \w    104.00 132.00   0.40    0.18    --  111.50 -81.00 104.91   70
 78  \w     74.00 100.00   0.40    0.18    --  111.50 -81.00 104.91   65
 79  \w     40.00  73.20   0.40    0.18    --  111.50 -81.00  91.66   83
 80  \w    142.00 168.00   0.40    0.18    --  111.50  15.00 -60.00   65
 81  \w     97.00 123.00   0.40    0.18    --  111.50  77.00  30.00   65
 82  \w    126.00 152.00   0.40    0.18    --  111.50  77.00 -60.00   65
 83  \w     97.00 123.00   0.40    0.18    --  111.50  77.00 -60.00   65
 84  \w     92.00 120.00   0.40    0.18    --  111.50  77.00-150.00   70
 85  \w    118.00 167.20   0.40    0.18    --  111.50  77.00-180.00  123
 86  \w    102.00 128.00   0.40    0.18    --  111.50  61.00-120.00   65
 87  \w    140.80 178.00   0.40    0.18    --  111.50  61.00  30.00   93
 88  \w    114.00 140.00   0.40    0.18    --  111.50  61.00  60.00   65
 89  \w    130.00 156.00   0.40    0.18    --  111.50  45.00  90.00   65
 90  \w    148.00 178.00   0.40    0.18    --  111.50  61.00 150.00   75
 91  \w    101.00 127.00   0.40    0.18    --  111.50  61.00 150.00   65
 92  \w    103.00 129.00   0.40    0.18    --  111.50  45.00   0.00   65
 93  \w    103.00 145.00   0.40    0.18    --  111.50  45.00 -30.00  105
 94  \w    103.00 171.00   0.40    0.18    --  111.50  45.00 -60.00  170
 95  \w    122.00 176.00   0.40    0.18    --  111.50  45.00-150.00  135
 96  \w    102.00 164.00   0.40    0.18    --  111.50  45.00 -90.00  155
 97  \w    152.00 177.20   0.40    0.18    --  111.50  45.00 -30.00   63
 98  \w    135.00 164.20   0.40    0.18    --  111.50  45.00  60.00   73
 99  \w    109.00 177.00   0.40    0.18    --  111.50  30.00  90.00  170
100  \w    102.00 128.00   0.40    0.18    --  111.50  43.00 177.98   65
101  \w    107.00 161.00   0.40    0.18    --  111.50  30.00 120.00  135
102  \w    102.00 131.20   0.40    0.18    --  111.50  15.00  90.00   73
103  \w    148.00 173.20   0.40    0.18    --  111.50  15.00 -30.00   63
104  \w    112.00 139.20   0.40    0.18    --  111.50  15.00 -60.00   68
105  \w    102.00 177.20   0.40    0.18    --  111.50  16.00-155.00  188
106  \w    138.00 163.20   0.40    0.18    --  111.50 125.00-180.00   63
107  \w    105.00 149.00   0.40    0.18    --  111.50 125.00  60.00  110
108  \w     99.00 130.20   0.40    0.18    --  111.50 125.00 120.00   78
109  \w    129.00 177.00   0.40    0.18    --  111.50 105.00 143.69  120
110  \w    -26.00  25.20   0.40    0.08    --  -48.65  19.00   0.00  128
111  \w    -24.00  15.20   0.40    0.08    --  -48.65  18.00-149.00   98
112  \w    -10.00  16.00   0.40    0.08    --  -48.65  16.00-155.00   65
113  \w    -26.00  16.00   0.40    0.08    --  -48.65  19.00-120.00  105
114  \w    -15.20  26.00   0.40    0.08    --  -48.65  19.00  90.00  103
115  \w    -51.00 -25.80   0.40    0.18    --  -90.00  45.00  30.00   63
116  \w    -51.00 -25.80   0.40    0.18    --  -90.00  45.00   0.00   63
117  \w    -51.00 -25.80   0.40    0.18    --  -90.00  45.00  90.00   63
118  \w   -121.00 -39.80   0.40    0.08    --  -48.65 -16.00  34.00  203
119  \w   -146.00-120.80   0.40    0.18    --  -90.00 -16.00  34.00   63
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1387313000
_diffrn_orient_matrix_UB_12      -0.0167027000
_diffrn_orient_matrix_UB_13      -0.0506700000
_diffrn_orient_matrix_UB_21      0.0184095000
_diffrn_orient_matrix_UB_22      0.0293818000
_diffrn_orient_matrix_UB_23      -0.0890925000
_diffrn_orient_matrix_UB_31      0.0181587000
_diffrn_orient_matrix_UB_32      -0.1578713000
_diffrn_orient_matrix_UB_33      -0.0111905000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0080
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            6684
_diffrn_reflns_point_group_measured_fraction_full 0.838
_diffrn_reflns_point_group_measured_fraction_max 0.828
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.481
_diffrn_reflns_theta_min         2.957
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.737
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41618
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.349
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.533
_refine_diff_density_min         -0.349
_refine_diff_density_rms         0.086
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.01(13)
_refine_ls_extinction_coef       0.0095(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     467
_refine_ls_number_reflns         6684
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0548
_refine_ls_R_factor_gt           0.0548
_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^)+(0.1239P)^2^+0.1421P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1411
_refine_ls_wR_factor_ref         0.1412
_reflns_Friedel_coverage         0.567
_reflns_Friedel_fraction_full    0.654
_reflns_Friedel_fraction_max     0.639
_reflns_number_gt                6666
_reflns_number_total             6684
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by -179.9937\% 
around [-0.25 0.00 0.97] (reciprocal) or [-0.00 0.00 1.00] (direct)
;
_cod_data_source_file            d3ob00273j2.cif
_cod_data_source_block           KOJBNIM-2
_cod_depositor_comments
'Adding full bibliography for 7159223--7159229.cif.'
_cod_database_code               7159226
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H23 N2 O3'
_chemical_oxdiff_usercomment     KOJBNIM-2
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.793
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.662(3)
 0.338(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All O(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 O1A-H1A \\sim O2A-H2A \\sim O1B-H1B \\sim O2B-H2B
 with sigma of 0.02
4.a Secondary CH2 refined with riding coordinates:
 C15A(H15A,H15B), C16A(H16A,H16B), C17A(H17A,H17B), C18A(H18A,H18B), C19A(H19A,
 H19B), C20A(H20A,H20B), C15B(H15C,H15D), C16B(H16C,H16D), C17B(H17C,H17D),
 C18B(H18C,H18D), C19B(H19C,H19D), C20B(H20C,H20D)
4.b Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C5A(H5A), C6A(H6A), C11A(H11A), C3B(H3B), C4B(H4B),
 C5B(H5B), C6B(H6B), C11B(H11B)
4.c Idealised Me refined as rotating group:
 C13A(H13A,H13B,H13C), C13B(H13D,H13E,H13F)
;
_shelx_res_checksum              95680
_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 2.336
_oxdiff_exptl_absorpt_empirical_full_min 0.202
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2