Ring-fused dimethoxybenzimidazole-benzimidazolequinone (DMBBQ): tunable halogenation and quinone formation using NaX/Oxone.
Conboy, Darren; Kielty, Patrick; Bear, Joseph C.; Cockcroft, Jeremy K.; Farràs, Pau; McArdle, Patrick; Singer, Richard J.; Smith, Dennis A.; Aldabbagh, Fawaz; Organic & biomolecular chemistry 19 (2021) 2716–2724; doi:10.1039/d1ob00032b

data_7157910
_publ_section_title
;
 Ring-fused dimethoxybenzimidazole-benzimidazolequinone (DMBBQ): tunable
 halogenation and quinone formation using NaX/Oxone.
;
_journal_issue                   12
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              2716
_journal_page_last               2724
_journal_paper_doi               10.1039/d1ob00032b
_journal_volume                  19
_journal_year                    2021
_chemical_formula_moiety         'C22 H19 Br N4 O4'
_chemical_formula_sum            'C22 H19 Br N4 O4'
_chemical_formula_weight         483.32
_chemical_name_systematic
7''-bromo-5'',8''-dimethoxy-[6,6''-bipyrrolo[1,2-a]benzimidazole]-5,8-dione
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-07-15
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-08-07 deposited with the CCDC.	2021-02-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.3635(2)
_cell_length_b                   9.58790(10)
_cell_length_c                   17.6817(2)
_cell_measurement_reflns_used    48903
_cell_measurement_temperature    150
_cell_measurement_theta_max      72.4470
_cell_measurement_theta_min      4.4850
_cell_volume                     3960.82(7)
_computing_cell_refinement       'CrysAlisPro 1.171.40.76a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.76a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.76a (Rigaku OD, 2020)'
_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      150
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2031
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_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     -4.00  21.00   1.00    1.00    --   34.00  93.00  66.76   25
  2  \w     -5.00  20.00   1.00    1.00    --   34.00  94.00-159.89   25
  3  \w     -4.00  21.00   1.00    1.00    --   34.00  93.00 -52.81   25
  4  \w      8.00  33.00   1.00    1.00    --   42.00  83.00  40.12   25
  5  \w      8.00  34.00   1.00    1.00    --   42.00  83.00 160.87   26
  6  \w    -86.00 -15.00   1.00    1.00    --  -42.62 125.00 -90.00   71
  7  \w   -115.00 -18.00   1.00    1.00    --  -42.62 -38.00   0.00   97
  8  \w   -116.00 -18.00   1.00    1.00    --  -42.62 -38.00-180.00   98
  9  \w    -74.00  34.00   1.00    1.00    --  -42.62  83.00 128.00  108
 10  \w   -112.00 -28.00   1.00    1.00    --  -42.62 -38.00  90.00   84
 11  \w     14.00  41.00   1.00    1.00    --   46.00  79.00 -92.49   27
 12  \w     14.00  42.00   1.00    1.00    --   46.00  77.00-179.01   28
 13  \w     26.00  52.00   1.00    1.00    --   58.00  74.00 -46.52   26
 14  \w     30.00  56.00   1.00    1.00    --   62.00  74.00  98.81   26
 15  \w     30.00  56.00   1.00    1.00    --   62.00  74.00  69.01   26
 16  \w     31.00  57.00   1.00    1.00    --   62.00  72.00 -98.93   26
 17  \w     71.00  98.00   1.00    1.00    --   62.00  72.00 -98.93   27
 18  \w     30.00  59.00   1.00    1.00    --   62.00  73.00-143.88   29
 19  \w     34.00  66.00   1.00    1.00    --   66.00  73.00 -38.41   32
 20  \w     36.00  61.00   1.00    1.00    --   66.00  69.00 137.11   25
 21  \w    109.00 145.00   1.00    1.00    --   70.00  74.00  20.43   36
 22  \w     39.00  65.00   1.00    1.00    --   70.00  72.00 -19.60   26
 23  \w     39.00  65.00   1.00    1.00    --   70.00  72.00 147.97   26
 24  \w     38.00  75.00   1.00    1.00    --   70.00  74.00  20.43   37
 25  \w    111.00 146.00   1.00    1.00    --   74.00  67.00-179.52   35
 26  \w     45.00  76.00   1.00    1.00    --   74.00  67.00-179.52   31
 27  \w     46.00  76.00   1.00    1.00    --   78.00  74.00 147.29   30
 28  \w     48.00  74.00   1.00    1.00    --   78.00  67.00  91.25   26
 29  \w     49.00  76.00   1.00    1.00    --   78.00  63.00 -75.55   27
 30  \w     50.00  76.00   1.00    1.00    --   82.00  73.00 -53.40   26
 31  \w     54.00  80.00   1.00    1.00    --   86.00  73.00 -20.77   26
 32  \w     55.00  85.00   1.00    1.00    --   86.00  72.00   6.56   30
 33  \w    135.00 161.00   1.00    1.00    --   86.00  73.00 -20.77   26
 34  \w     58.00  84.00   1.00    1.00    --   90.00  73.00  45.78   26
 35  \w     59.00  85.00   1.00    1.00    --   90.00  71.00 -39.12   26
 36  \w     61.00  96.00   1.00    1.00    --   90.00  59.00 -91.15   35
 37  \w     59.00  89.00   1.00    1.00    --   90.00  70.00-139.52   30
 38  \w     97.00 162.00   1.00    1.00    --   94.00  72.00  95.16   65
 39  \w     63.00  89.00   1.00    1.00    --   94.00  72.00  95.16   26
 40  \w    109.00 166.00   1.00    1.00    --   94.00  68.00 129.10   57
 41  \w     64.00  90.00   1.00    1.00    --   94.00  68.00 129.10   26
 42  \w     71.00 172.00   1.00    1.00    --  102.00  71.00  67.06  101
 43  \w     74.00 164.00   1.00    1.00    --  104.49  72.00  -1.90   90
 44  \w     76.00 102.00   1.00    1.00    --  104.49  61.00 -90.00   26
 45  \w    141.00 172.00   1.00    1.00    --  104.49  63.00 -66.65   31
 46  \w     30.00 106.00   1.00    1.00    --  104.49 -94.00  90.00   76
 47  \w     76.00 131.00   1.00    1.00    --  104.49  63.00 -66.65   55
 48  \w     75.00 107.00   1.00    1.00    --  104.49  61.00-180.00   32
 49  \w     32.00 106.00   1.00    1.00    --  104.49 -97.00 -65.26   74
 50  \w    107.00 134.00   1.00    1.00    --  104.49 -61.00 120.00   27
 51  \w     32.00  98.00   1.00    1.00    --  104.49 -61.00 120.00   66
 52  \w     75.00 176.00   1.00    1.00    --  104.49  61.00-120.00  101
 53  \w    121.00 177.00   1.00    1.00    --  104.49  61.00 150.00   56
 54  \w     75.00 103.00   1.00    1.00    --  104.49  61.00 150.00   28
 55  \w     32.00 117.00   1.00    1.00    --  104.49 -61.00 -60.00   85
 56  \w     52.00 106.00   1.00    1.00    --  104.49 -94.00-150.00   54
 57  \w     76.00 176.00   1.00    1.00    --  104.49  61.00-170.16  100
 58  \w     75.00 172.00   1.00    1.00    --  104.49  61.00 -30.00   97
 59  \w     72.00 103.00   1.00    1.00    --  104.49 -94.00  30.00   31
 60  \w     81.00 106.00   1.00    1.00    --  104.49 -94.00 120.00   25
 61  \w    136.00 170.00   1.00    1.00    --  104.49  61.00 -90.00   34
 62  \w     28.00  53.00   1.00    1.00    --  104.49 -94.00 120.00   25
 63  \w     75.00 161.00   1.00    1.00    --  104.49  72.00  32.06   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0215741000
_diffrn_orient_matrix_UB_12      -0.1298782000
_diffrn_orient_matrix_UB_13      0.0425400000
_diffrn_orient_matrix_UB_21      0.0536055000
_diffrn_orient_matrix_UB_22      0.0811453000
_diffrn_orient_matrix_UB_23      0.0254689000
_diffrn_orient_matrix_UB_31      -0.0318061000
_diffrn_orient_matrix_UB_32      0.0485752000
_diffrn_orient_matrix_UB_33      0.0716213000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0494
_diffrn_reflns_av_unetI/netI     0.0130
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            68493
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.775
_diffrn_reflns_theta_min         3.784
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.171
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.245
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.76a (Rigaku Oxford Diffraction, 2020)
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 orangish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.621
_exptl_crystal_description       block
_exptl_crystal_F_000             1968
_exptl_crystal_size_max          0.415
_exptl_crystal_size_mid          0.271
_exptl_crystal_size_min          0.183
_refine_diff_density_max         0.795
_refine_diff_density_min         -0.834
_refine_diff_density_rms         0.080
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.153
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     351
_refine_ls_number_reflns         3921
_refine_ls_number_restraints     76
_refine_ls_restrained_S_all      1.149
_refine_ls_R_factor_all          0.0434
_refine_ls_R_factor_gt           0.0431
_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^)+(0.0488P)^2^+9.0343P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1161
_refine_ls_wR_factor_ref         0.1163
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3865
_reflns_number_total             3921
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1ob00032b2.cif
_cod_data_source_block           exp_2189
_cod_depositor_comments
'Adding full bibliography for 7157908--7157910.cif.'
_cod_database_code               7157910
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C22 H20 Br N4 O4'
_chemical_oxdiff_usercomment     'Darren Conboy 199D'
_shelx_estimated_absorpt_t_max   0.595
_shelx_estimated_absorpt_t_min   0.353
_reflns_odcompleteness_completeness 99.90
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C14-H14A \\sim C14-H14B \\sim C14-H14C
 with sigma of 0.001
 C16-H16A \\sim C16-H16B \\sim C17-H17A \\sim C17-H17B \\sim C18-H18A \\sim
C18-H18B \\sim C20-H20A ~
 C20-H20B \\sim C21-H21A \\sim C21-H21B \\sim C22-H22A \\sim C22-H22B
 with sigma of 0.001
3. Rigid bond restraints
 O3, O3, C13A, C13B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
C13A \\sim C13B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
5. Others
 Sof(C13B)=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(1)
 Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(H13C)=FVAR(1)
6.a Idealised Me refined as rotating group:
 C13A(H13A,H13B,H13C), C13B(H13D,H13E,H13F)
;
_shelx_res_checksum              11426
_olex2_date_sample_data_collection 2020-02-24
_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 1.513
_oxdiff_exptl_absorpt_empirical_full_min 0.808