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_7159227
_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_formula_moiety         'C20 H22 N2 O3, 0.5(C3 H6 O)'
_chemical_formula_sum            'C21.5 H25 N2 O3.5'
_chemical_formula_weight         367.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2021-10-25
_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                 93.0248(6)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   22.38682(16)
_cell_length_b                   12.13681(9)
_cell_length_c                   13.54889(7)
_cell_measurement_reflns_used    65993
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      79.2710
_cell_measurement_theta_min      2.0300
_cell_volume                     3676.17(4)
_computing_cell_refinement       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.117a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.117a (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      100.00(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 0.997
_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   -115.00 -90.00   0.50    0.15    --  -48.76-140.00-149.00   50
  2  \w    -75.00 -50.00   0.50    0.15    --  -48.76 140.00 -90.00   50
  3  \w   -120.00 -73.00   0.50    0.15    --  -48.76-130.00  23.00   94
  4  \w    -76.00 -48.00   0.50    0.15    --  -48.76 130.00  95.00   56
  5  \w     37.00  97.00   0.50    0.15    --   48.76-130.00  23.00  120
  6  \w     65.00 102.00   0.50    0.15    --   48.76-140.00-149.00   74
  7  \w    -83.00 -58.00   0.50    0.60    --  -90.00 140.00 -90.00   50
  8  \w   -134.00-109.00   0.50    0.60    --  -90.00-140.00-149.00   50
  9  \w   -140.00-115.00   0.50    0.60    --  -90.00-130.00  23.00   50
 10  \w    111.00 136.00   0.50    0.60    --  111.50 130.00  95.00   50
 11  \w    129.00 154.00   0.50    0.60    --  111.50 140.00 -90.00   50
 12  \w     74.00 123.00   0.50    0.60    --  111.50-140.00-149.00   98
 13  \w     63.00  93.00   0.50    0.60    --  111.50-130.00  23.00   60
 14  \w    -26.00  23.00   0.50    0.15    --  -48.76  19.00 120.00   98
 15  \w   -120.00 -81.00   0.50    0.15    --  -48.76-125.00-150.00   78
 16  \w    -26.00  17.00   0.50    0.15    --  -48.76  19.00 -60.00   86
 17  \w   -116.00 -75.00   0.50    0.15    --  -48.76-125.00  60.00   82
 18  \w   -119.00 -93.00   0.50    0.15    --  -48.76-125.00-120.00   52
 19  \w    -25.00  25.00   0.50    0.15    --  -48.76  19.00-180.00  100
 20  \w     36.00 116.00   0.50    0.15    --   48.76  57.00-180.00  160
 21  \w    -20.00  42.00   0.50    0.15    --   48.76 -38.00-120.00  124
 22  \w    -46.00 -18.00   0.50    0.60    --  -90.00  45.00 -30.00   56
 23  \w    -51.00 -18.00   0.50    0.60    --  -90.00  45.00  90.00   66
 24  \w    -48.00 -23.00   0.50    0.60    --  -90.00  45.00 120.00   50
 25  \w    127.00 154.00   0.50    0.60    --  111.50  15.00  90.00   54
 26  \w     42.00  69.00   0.50    0.60    --  111.50 -61.00-120.00   54
 27  \w    124.00 171.00   0.50    0.60    --  111.50  30.00  90.00   94
 28  \w     42.00 108.00   0.50    0.60    --  111.50-111.00-138.60  132
 29  \w     49.00  77.00   0.50    0.60    --  111.50-106.00 160.55   56
 30  \w    122.00 178.00   0.50    0.60    --  111.50  15.00 150.00  112
 31  \w     41.00  83.00   0.50    0.60    --  111.50 -77.00   0.00   84
 32  \w     63.00 105.00   0.50    0.60    --  111.50-106.00  70.66   84
 33  \w     42.00 107.00   0.50    0.60    --  111.50-103.00  92.62  130
 34  \w    144.00 169.00   0.50    0.60    --  111.50  30.00  60.00   50
 35  \w     44.00 109.00   0.50    0.60    --  111.50-116.00 -12.58  130
 36  \w     82.00 107.00   0.50    0.60    --  111.50-106.00 160.55   50
 37  \w     95.00 169.00   0.50    0.60    --  111.50 125.00 -30.00  148
 38  \w     72.00 107.00   0.50    0.60    --  111.50-105.00-114.17   70
 39  \w    132.00 158.00   0.50    0.60    --  111.50  30.00-150.00   52
 40  \w     93.00 121.00   0.50    0.60    --  111.50 -87.00   0.33   56
 41  \w     45.00  77.00   0.50    0.60    --  111.50 -77.00 -90.00   64
 42  \w     40.00  88.00   0.50    0.60    --  111.50-102.00 166.61   96
 43  \w     49.00 107.00   0.50    0.60    --  111.50-103.00 110.77  116
 44  \w    129.00 174.00   0.50    0.60    --  111.50  30.00  30.00   90
 45  \w    123.00 178.00   0.50    0.60    --  111.50  45.00-120.00  110
 46  \w    102.00 159.00   0.50    0.60    --  111.50  45.00 -90.00  114
 47  \w     44.00  69.00   0.50    0.60    --  111.50 -95.00-150.00   50
 48  \w     50.00  80.00   0.50    0.60    --  111.50-125.00 150.00   60
 49  \w    102.00 177.00   0.50    0.60    --  111.50  66.00-153.09  150
 50  \w     59.00 106.00   0.50    0.60    --  111.50 -97.00  10.51   94
 51  \w     72.00 103.00   0.50    0.60    --  111.50 -95.00-150.00   62
 52  \w     48.00  77.00   0.50    0.60    --  111.50-125.00  90.00   58
 53  \w    102.00 135.00   0.50    0.60    --  111.50  30.00  60.00   66
 54  \w    108.00 138.00   0.50    0.60    --  111.50  15.00-180.00   60
 55  \w     41.00  67.00   0.50    0.60    --  111.50 -77.00-150.00   52
 56  \w     69.00 104.00   0.50    0.60    --  111.50 -96.00 -71.93   70
 57  \w     79.00 106.00   0.50    0.60    --  111.50 -97.00 -29.75   54
 58  \w     41.00  81.00   0.50    0.60    --  111.50-125.00-150.00   80
 59  \w     42.00  83.00   0.50    0.60    --  111.50 -95.00  90.00   82
 60  \w     77.00 110.00   0.50    0.60    --  111.50-125.00  60.00   66
 61  \w     52.00 103.00   0.50    0.60    --  111.50-112.00 -78.71  102
 62  \w     66.00 105.00   0.50    0.60    --  111.50 -95.00 -90.00   78
 63  \w    105.00 178.00   0.50    0.60    --  111.50 125.00-120.00  146
 64  \w     96.00 127.00   0.50    0.60    --  111.50 125.00  90.00   62
 65  \w    131.00 160.00   0.50    0.60    --  111.50 125.00  90.00   58
 66  \w     76.00 107.00   0.50    0.60    --  111.50-106.00-100.79   62
 67  \w    111.00 177.00   0.50    0.60    --  111.50  45.00 150.00  132
 68  \w     41.00  66.00   0.50    0.60    --  111.50-125.00  60.00   50
 69  \w     96.00 125.00   0.50    0.60    --  111.50 125.00  60.00   58
 70  \w     45.00  74.00   0.50    0.60    --  111.50-111.00  18.81   58
 71  \w     83.00 108.00   0.50    0.60    --  111.50-111.00  18.81   50
 72  \w    133.00 159.00   0.50    0.60    --  111.50  30.00 -90.00   52
 73  \w     67.00 103.00   0.50    0.60    --  111.50 -77.00 -30.00   72
 74  \w     72.00  98.00   0.50    0.60    --  111.50 -95.00 150.00   52
 75  \w     49.00 107.00   0.50    0.60    --  111.50-106.00  67.84  116
 76  \w    129.00 155.00   0.50    0.60    --  111.50  61.00 120.00   52
 77  \w     41.00  71.00   0.50    0.60    --  111.50 -61.00   0.00   60
 78  \w     99.00 178.00   0.50    0.60    --  111.50  61.00 -90.00  158
 79  \w     41.00 108.00   0.50    0.60    --  111.50-109.00-172.50  134
 80  \w    134.00 160.00   0.50    0.60    --  111.50 125.00  60.00   52
 81  \w    109.00 135.00   0.50    0.60    --  111.50  77.00-150.00   52
 82  \w     48.00  83.00   0.50    0.60    --  111.50 -95.00 -60.00   70
 83  \w    138.00 169.00   0.50    0.60    --  111.50   0.00  60.00   62
 84  \w     50.00  76.00   0.50    0.60    --  111.50 -77.00-180.00   52
 85  \w     42.00  69.00   0.50    0.60    --  111.50 -77.00-120.00   54
 86  \w     44.00  70.00   0.50    0.60    --  111.50 -77.00  30.00   52
 87  \w     60.00  85.00   0.50    0.60    --  111.50 -77.00 120.00   50
 88  \w     51.00  77.00   0.50    0.60    --  111.50 -95.00-180.00   52
 89  \w     50.00  76.00   0.50    0.60    --  111.50 -95.00-120.00   52
 90  \w     46.00  72.00   0.50    0.60    --  111.50-111.00 -14.89   52
 91  \w     79.00 108.00   0.50    0.60    --  111.50-111.00 -14.89   58
 92  \w     75.00 101.00   0.50    0.60    --  111.50-125.00-180.00   52
 93  \w     58.00 110.00   0.50    0.60    --  111.50-125.00  30.00  104
 94  \w     67.00  93.00   0.50    0.60    --  111.50-125.00 120.00   52
 95  \w    102.00 172.00   0.50    0.60    --  111.50  30.00 -30.00  140
 96  \w     40.00  68.00   0.50    0.60    --  111.50 -61.00-150.00   56
 97  \w    104.00 137.00   0.50    0.60    --  111.50  15.00-150.00   66
 98  \w    103.00 146.00   0.50    0.60    --  111.50  61.00 -30.00   86
 99  \w     97.00 169.00   0.50    0.60    --  111.50  61.00  90.00  144
100  \w    117.00 143.00   0.50    0.60    --  111.50 124.00 147.77   52
101  \w    142.00 167.00   0.50    0.60    --  111.50 125.00 150.00   50
102  \w     84.00 110.00   0.50    0.60    --  111.50-162.00 -17.59   52
103  \w     86.00 112.00   0.50    0.60    --  111.50 -85.00-140.77   52
104  \w     87.00 113.00   0.50    0.60    --  111.50 -86.00  69.67   52
105  \w     47.00  73.00   0.50    0.60    --  111.50 -88.00-167.96   52
106  \w     42.00  85.00   0.50    0.60    --  111.50 -88.00 105.10   86
107  \w    110.00 136.00   0.50    0.60    --  111.50 -88.00 105.10   52
108  \w     99.00 171.00   0.50    0.60    --  111.50  53.00   1.33  144
;
_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      0.0594560000
_diffrn_orient_matrix_UB_12      0.0637336000
_diffrn_orient_matrix_UB_13      0.0109876000
_diffrn_orient_matrix_UB_21      -0.0347072000
_diffrn_orient_matrix_UB_22      0.1096387000
_diffrn_orient_matrix_UB_23      -0.0016310000
_diffrn_orient_matrix_UB_31      -0.0026066000
_diffrn_orient_matrix_UB_32      -0.0047205000
_diffrn_orient_matrix_UB_33      0.1133756000
_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  0.0528
_diffrn_reflns_av_unetI/netI     0.0202
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            103526
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.500
_diffrn_reflns_theta_min         3.266
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.731
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.86655
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.117a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1568
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.470
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.187
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     504
_refine_ls_number_reflns         7887
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.187
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0718
_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^)+(0.0989P)^2^+8.7132P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2347
_refine_ls_wR_factor_ref         0.2380
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7522
_reflns_number_total             7887
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3ob00273j2.cif
_cod_data_source_block           C6BIMFT
_cod_depositor_comments
'Adding full bibliography for 7159223--7159229.cif.'
_cod_original_formula_sum        'C21.50 H25 N2 O3.50'
_cod_database_code               7159227
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C21.5 H25 N2 O3.5'
_chemical_oxdiff_usercomment     C6BIMFT
_shelx_estimated_absorpt_t_max   0.944
_shelx_estimated_absorpt_t_min   0.862
_reflns_odcompleteness_completeness 94.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     86.18
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9763(7)
 0.0237(7)
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, All O(H) groups
3.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)
3.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)
3.c Idealised Me refined as rotating group:
 C13A(H13A,H13B,H13C), C13B(H13D,H13E,H13F), C22(H22A,H22B,H22C), C23(H23A,
 H23B,H23C)
;
_shelx_res_checksum              49708
_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 1.347
_oxdiff_exptl_absorpt_empirical_full_min 0.559