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_7159223
_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         'C19 H20 N2 O4'
_chemical_formula_sum            'C19 H20 N2 O4'
_chemical_formula_weight         340.37
_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   difmap
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-12-15
_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                 110.6652(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.38512(6)
_cell_length_b                   9.48447(4)
_cell_length_c                   15.80604(8)
_cell_measurement_reflns_used    39851
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      79.3290
_cell_measurement_theta_min      2.9590
_cell_volume                     1596.949(15)
_computing_cell_refinement       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.121a (Rigaku OD, 2021)'
_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)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_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     27.00 121.00   0.40    0.05    --   48.63  77.00  90.00  235
  2  \w     27.00 121.00   0.40    0.05    --   48.63  77.00 150.00  235
  3  \w     39.00 121.00   0.40    0.05    --   48.63  38.00  90.00  205
  4  \w     39.00 123.00   0.40    0.05    --   48.63  25.00  30.00  210
  5  \w     27.00 121.00   0.40    0.05    --   48.63  77.00-180.00  235
  6  \w    -31.00  25.00   0.40    0.05    --  -48.63  25.00  30.00  140
  7  \w   -121.00 -39.00   0.40    0.05    --  -48.63 -38.00 150.00  205
  8  \w   -123.00 -37.00   0.40    0.05    --  -48.63 -25.00-133.00  215
  9  \w    100.00 126.00   0.40    0.20    --  111.50 -82.00 166.48   65
 10  \w     81.00 107.00   0.40    0.20    --  111.50-147.00  25.41   65
 11  \w     51.00 101.00   0.40    0.20    --  111.50-125.00 -60.00  125
 12  \w     63.00 104.20   0.40    0.20    --  111.50-125.00-120.00  103
 13  \w     92.00 118.00   0.40    0.20    --  111.50-133.00-166.62   65
 14  \w     42.00  81.20   0.40    0.20    --  111.50-133.00-166.62   98
 15  \w     45.00  71.00   0.40    0.20    --  111.50-125.00-180.00   65
 16  \w     40.00  77.20   0.40    0.20    --  111.50-111.00 -75.51   93
 17  \w     34.00  94.00   0.40    0.05    --   48.63-125.00-120.00  150
 18  \w     41.00  72.20   0.40    0.20    --  111.50-107.00-157.95   78
 19  \w     82.00 108.00   0.40    0.20    --  111.50-111.00 -75.51   65
 20  \w     56.00  82.00   0.40    0.20    --  111.50-103.00 -57.47   65
 21  \w     42.00  91.20   0.40    0.20    --  111.50-122.00  38.98  123
 22  \w     66.00  96.00   0.40    0.20    --  111.50 -95.00   0.00   75
 23  \w     42.00 102.00   0.40    0.20    --  111.50 -99.00 109.09  150
 24  \w     64.00  90.00   0.40    0.20    --  111.50 -95.00 120.00   65
 25  \w     80.00 106.00   0.40    0.20    --  111.50-119.00 175.83   65
 26  \w     43.00  93.00   0.40    0.20    --  111.50 -95.00 150.00  125
 27  \w     41.00  70.20   0.40    0.20    --  111.50-125.00  90.00   73
 28  \w     70.00  96.00   0.40    0.20    --  111.50 -95.00  30.00   65
 29  \w     40.00  65.20   0.40    0.20    --  111.50 -95.00  30.00   63
 30  \w     42.00  71.20   0.40    0.20    --  111.50 -77.00  60.00   73
 31  \w     57.00  88.20   0.40    0.20    --  111.50 -77.00 150.00   78
 32  \w     47.00 104.20   0.40    0.20    --  111.50 -77.00  30.00  143
 33  \w     56.00 104.00   0.40    0.20    --  111.50 -77.00 -30.00  120
 34  \w     46.00  85.20   0.40    0.20    --  111.50 -77.00 -90.00   98
 35  \w     42.00  69.20   0.40    0.20    --  111.50 -61.00 -60.00   68
 36  \w     53.00 103.00   0.40    0.20    --  111.50 -77.00 -60.00  125
 37  \w     46.00  71.20   0.40    0.20    --  111.50 -63.00  -0.18   63
 38  \w     42.00  76.00   0.40    0.20    --  111.50 -67.00  59.07   85
 39  \w    -22.00  25.20   0.40    0.05    --   48.63 -19.00  60.00  118
 40  \w    -25.00  31.00   0.40    0.05    --   48.63 -25.00-133.00  140
 41  \w    123.00 154.20   0.40    0.20    --  111.50  15.00 -60.00   78
 42  \w    146.00 175.20   0.40    0.20    --  111.50  77.00  60.00   73
 43  \w    141.00 168.20   0.40    0.20    --  111.50  77.00  90.00   68
 44  \w     90.00 118.00   0.40    0.20    --  111.50  77.00 150.00   70
 45  \w     90.00 138.00   0.40    0.20    --  111.50  77.00  90.00  120
 46  \w     94.00 121.20   0.40    0.20    --  111.50  77.00 120.00   68
 47  \w     90.00 139.20   0.40    0.20    --  111.50  77.00  60.00  123
 48  \w     93.00 157.00   0.40    0.20    --  111.50  71.00 -44.50  160
 49  \w     90.00 128.00   0.40    0.20    --  111.50  77.00-150.00   95
 50  \w    142.00 171.20   0.40    0.20    --  111.50  77.00-180.00   73
 51  \w    142.00 169.20   0.40    0.20    --  111.50  77.00-150.00   68
 52  \w     90.00 123.20   0.40    0.20    --  111.50  77.00-180.00   83
 53  \w    103.00 129.00   0.40    0.20    --  111.50  62.00  52.98   65
 54  \w     98.00 127.20   0.40    0.20    --  111.50  61.00  90.00   73
 55  \w    138.00 177.20   0.40    0.20    --  111.50  62.00  52.98   98
 56  \w    138.00 163.20   0.40    0.20    --  111.50  61.00  90.00   63
 57  \w     96.00 134.00   0.40    0.20    --  111.50  61.00 120.00   95
 58  \w     96.00 122.00   0.40    0.20    --  111.50  61.00 150.00   65
 59  \w     95.00 177.00   0.40    0.20    --  111.50  65.00 154.82  205
 60  \w    140.00 174.00   0.40    0.20    --  111.50  61.00 120.00   85
 61  \w    102.00 129.20   0.40    0.20    --  111.50  30.00 -30.00   68
 62  \w    120.00 146.00   0.40    0.20    --  111.50  45.00 -90.00   65
 63  \w     98.00 163.20   0.40    0.20    --  111.50  61.00-180.00  163
 64  \w    146.00 175.20   0.40    0.20    --  111.50  45.00-150.00   73
 65  \w    141.00 174.20   0.40    0.20    --  111.50  30.00-120.00   83
 66  \w    106.00 137.20   0.40    0.20    --  111.50  30.00-120.00   78
 67  \w    101.00 177.00   0.40    0.20    --  111.50  25.00  30.00  190
 68  \w    146.00 176.00   0.40    0.20    --  111.50  30.00  90.00   75
 69  \w    152.00 177.20   0.40    0.20    --  111.50  30.00 120.00   63
 70  \w    101.00 135.00   0.40    0.20    --  111.50  30.00 120.00   85
 71  \w    120.00 152.00   0.40    0.20    --  111.50  15.00  90.00   80
 72  \w    102.00 171.20   0.40    0.20    --  111.50  15.00-150.00  173
 73  \w    101.00 154.20   0.40    0.20    --  111.50  15.00-180.00  133
 74  \w    -94.00 -68.80   0.40    0.20    --  -90.00 -77.00-180.00   63
 75  \w    -96.00 -70.00   0.40    0.20    --  -90.00 -77.00-150.00   65
 76  \w    -97.00 -71.00   0.40    0.20    --  -90.00 -77.00  90.00   65
 77  \w    -94.00 -68.80   0.40    0.20    --  -90.00 -77.00 120.00   63
 78  \w    -96.00 -70.00   0.40    0.20    --  -90.00 -77.00 150.00   65
 79  \w    -96.00 -70.80   0.40    0.20    --  -90.00 -72.00 154.63   63
 80  \w    -99.00 -73.00   0.40    0.20    --  -90.00 -73.00 131.59   65
 81  \w   -157.00-129.80   0.40    0.20    --  -90.00 -72.00 154.63   68
 82  \w    -97.00 -71.00   0.40    0.20    --  -90.00 -75.00  72.28   65
 83  \w    -96.20 -71.00   0.40    0.20    --  -90.00 -71.00  89.23   63
 84  \w   -100.00 -74.00   0.40    0.20    --  -90.00 -68.00 160.52   65
 85  \w   -100.00 -72.80   0.40    0.20    --  -90.00 -67.00 153.26   68
 86  \w    -97.00 -71.00   0.40    0.20    --  -90.00 -72.00  72.86   65
 87  \w    -99.00 -73.00   0.40    0.20    --  -90.00 -65.00 164.06   65
 88  \w    -99.00 -73.00   0.40    0.20    --  -90.00 -65.00  93.36   65
 89  \w   -101.00 -75.00   0.40    0.20    --  -90.00 -61.00 120.00   65
 90  \w   -100.20 -75.00   0.40    0.20    --  -90.00 -61.00  86.64   63
 91  \w   -106.00 -76.80   0.40    0.20    --  -90.00 -57.00 163.34   73
 92  \w   -102.20 -77.00   0.40    0.20    --  -90.00 -52.00  97.83   63
 93  \w   -163.00 -79.00   0.40    0.20    --  -90.00 -25.00-133.00  210
 94  \w    -99.00 -73.00   0.40    0.20    --  -90.00 -67.00-172.37   65
 95  \w    -94.20 -69.00   0.40    0.20    --  -90.00 -74.00-167.18   63
 96  \w   -150.00-124.80   0.40    0.20    --  -90.00 -74.00-167.18   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      0.0791495000
_diffrn_orient_matrix_UB_12      -0.0333199000
_diffrn_orient_matrix_UB_13      -0.0589672000
_diffrn_orient_matrix_UB_21      -0.1111123000
_diffrn_orient_matrix_UB_22      0.0424261000
_diffrn_orient_matrix_UB_23      -0.0851980000
_diffrn_orient_matrix_UB_31      0.0479874000
_diffrn_orient_matrix_UB_32      0.1532076000
_diffrn_orient_matrix_UB_33      0.0107492000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0282
_diffrn_reflns_av_unetI/netI     0.0150
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            41676
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.491
_diffrn_reflns_theta_min         2.988
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.822
_exptl_absorpt_correction_T_max  0.83418
_exptl_absorpt_correction_T_min  0.83014
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.121a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.416
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             720
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.274
_refine_diff_density_min         -0.157
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 3048 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(4)
_refine_ls_extinction_coef       0.0048(4)
_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   1.040
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_matrix_type           full
_refine_ls_number_parameters     610
_refine_ls_number_reflns         6778
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.040
_refine_ls_R_factor_all          0.0276
_refine_ls_R_factor_gt           0.0275
_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^)+(0.0451P)^2^+0.3879P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0730
_refine_ls_wR_factor_ref         0.0731
_reflns_Friedel_coverage         0.838
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     0.947
_reflns_number_gt                6769
_reflns_number_total             6778
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00273j2.cif
_cod_data_source_block           BNIMOKETUV
_cod_depositor_comments
'Adding full bibliography for 7159223--7159229.cif.'
_cod_original_cell_volume        1596.950(14)
_cod_database_code               7159223
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C19 H20 N2 O4'
_chemical_oxdiff_usercomment     BNIMOKETUV
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.767
_reflns_odcompleteness_completeness 98.77
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     80.50
_olex2_refinement_description
;
1. Fixed Uiso
 At 1 times of:
  All C(H) groups
;
_shelx_res_checksum              4142
_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 1.622
_oxdiff_exptl_absorpt_empirical_full_min 0.662