Late-stage Modification of Electronic Properties of Antiaromatic and Diradicaloid Indeno[1,2-b]fluorene Analogues via Sulfur Oxidation.
Dressler, Justin; Barker, Joshua E.; Karas, Lucas J.; Hashimoto, Hannah; Kishi, Ryohei; Zakharov, Lev N.; MacMillan, Samantha N.; Gómez-García, Carlos J; Nakano, Masayoshi; Wu, Judy I.; Haley, Michael M.; The Journal of organic chemistry  (2020) –; doi:10.1021/acs.joc.0c01387

data_4038654
_publ_section_title
;
 Late-stage Modification of Electronic Properties of Antiaromatic and
 Diradicaloid Indeno[1,2-b]fluorene Analogues via Sulfur Oxidation.
;
_journal_name_full               'The Journal of organic chemistry'
_journal_paper_doi               10.1021/acs.joc.0c01387
_journal_year                    2020
_chemical_formula_moiety         'C52 H46 O4 S2, 2(C2 H3 N)'
_chemical_formula_sum            'C56 H52 N2 O4 S2'
_chemical_formula_weight         881.11
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-10-03
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_cell_angle_alpha                92.525(2)
_cell_angle_beta                 97.786(2)
_cell_angle_gamma                98.462(2)
_cell_formula_units_Z            1
_cell_length_a                   7.62440(10)
_cell_length_b                   10.3907(2)
_cell_length_c                   15.0797(3)
_cell_measurement_reflns_used    11179
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      76.9070
_cell_measurement_theta_min      5.9390
_cell_volume                     1168.26(4)
_computing_cell_refinement       'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.58a (Rigaku OD, 2019)'
_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      100.0(2)
_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 0.995
_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    -69.00  22.00   0.50    1.92    --  -49.81  77.00  60.00  182
  2  \w    -27.00  22.00   0.50    1.92    --  -49.81  19.00 150.00   98
  3  \w    -81.00   7.00   0.50    1.92    --  -49.81 103.00 -10.00  176
  4  \w    -51.00 -11.00   0.50    7.69    --  -82.50  45.00 -60.00   80
  5  \w    -81.00 -11.00   0.50    7.69    --  -82.50 103.00 -10.00  140
  6  \w    -22.00  27.00   0.50    1.92    --   49.81 -19.00 -30.00   98
  7  \w    -21.00  42.00   0.50    1.92    --   49.81 -37.00 -90.00  126
  8  \w     15.00  82.00   0.50    1.92    --   49.81-103.00-112.00  134
  9  \w     32.00 107.00   0.50    7.69    --  104.00-103.00-112.00  150
 10  \w     77.00 103.00   0.50    7.69    --  104.00 -94.00-120.00   52
 11  \w     73.00 112.00   0.50    7.69    --  104.00-125.00-180.00   78
 12  \w     70.00 105.00   0.50    7.69    --  104.00 -94.00 -90.00   70
 13  \w     94.00 119.00   0.50    7.69    --  104.00 -85.00 -51.16   50
 14  \w     80.00 107.00   0.50    7.69    --  104.00-105.00  29.90   54
 15  \w     73.00 102.00   0.50    7.69    --  104.00 -94.00  30.00   58
 16  \w     71.00 105.00   0.50    7.69    --  104.00 -77.00  60.00   68
 17  \w     64.00 110.00   0.50    7.69    --  104.00-125.00  30.00   92
 18  \w     55.00 105.00   0.50    7.69    --  104.00 -94.00  60.00  100
 19  \w     81.00 107.00   0.50    7.69    --  104.00 -81.00 133.74   52
 20  \w     79.00 106.00   0.50    7.69    --  104.00 -94.00 150.00   54
 21  \w     79.00 112.00   0.50    7.69    --  104.00-125.00 150.00   66
 22  \w     43.00  68.00   0.50    7.69    --  104.00 -61.00  90.00   50
 23  \w     38.00  74.00   0.50    7.69    --  104.00-105.00  29.90   72
 24  \w     51.00 110.00   0.50    7.69    --  104.00-125.00  60.00  118
 25  \w     41.00  67.00   0.50    7.69    --  104.00 -94.00 -30.00   52
 26  \w     37.00  63.00   0.50    7.69    --  104.00-125.00   0.00   52
 27  \w     32.00 106.00   0.50    7.69    --  104.00 -94.00 -60.00  148
 28  \w     82.00 107.00   0.50    7.69    --  104.00 -78.00 -90.17   50
 29  \w     59.00  98.00   0.50    7.69    --  104.00   0.00-150.00   78
 30  \w    126.00 152.00   0.50    7.69    --  104.00  15.00-180.00   52
 31  \w    131.00 171.00   0.50    7.69    --  104.00  77.00-180.00   80
 32  \w    144.00 170.00   0.50    7.69    --  104.00 125.00-180.00   52
 33  \w    104.00 130.00   0.50    7.69    --  104.00  45.00 -60.00   52
 34  \w    135.00 168.00   0.50    7.69    --  104.00  45.00 -60.00   66
 35  \w    119.00 147.00   0.50    7.69    --  104.00  15.00   0.00   56
 36  \w    140.00 166.00   0.50    7.69    --  104.00  45.00  90.00   52
 37  \w    112.00 138.00   0.50    7.69    --  104.00  15.00  90.00   52
 38  \w    106.00 176.00   0.50    7.69    --  104.00 103.00 -10.00  140
 39  \w     95.00 176.00   0.50    7.69    --  104.00 125.00 -60.00  162
 40  \w    105.00 141.00   0.50    7.69    --  104.00 125.00  90.00   72
 41  \w     60.00  93.00   0.50    7.69    --  104.00   0.00 150.00   66
 42  \w     40.00  70.00   0.50    7.69    --  104.00 -77.00 150.00   60
 43  \w     33.00  64.00   0.50    7.69    --  104.00 -61.00 150.00   62
 44  \w     36.00  65.00   0.50    7.69    --  104.00 -94.00  90.00   58
 45  \w     41.00  67.00   0.50    7.69    --  104.00-125.00 150.00   52
 46  \w     33.00  59.00   0.50    7.69    --  104.00 -94.00 120.00   52
 47  \w     32.00  71.00   0.50    7.69    --  104.00 -61.00  60.00   78
 48  \w     33.00  63.00   0.50    7.69    --  104.00  -3.00 131.92   60
 49  \w     36.00  63.00   0.50    7.69    --  104.00 -61.00 120.00   54
 50  \w     32.00 106.00   0.50    7.69    --  104.00 -77.00  30.00  148
 51  \w     34.00 112.00   0.50    7.69    --  104.00-125.00 -60.00  156
 52  \w     34.00 112.00   0.50    7.69    --  104.00-125.00-120.00  156
 53  \w     32.00  71.00   0.50    7.69    --  104.00 -61.00  30.00   78
 54  \w     32.00  73.00   0.50    7.69    --  104.00 -68.00  -6.21   82
 55  \w     33.00  70.00   0.50    7.69    --  104.00 -61.00 -60.00   74
 56  \w     32.00  60.00   0.50    7.69    --  104.00 -77.00-120.00   56
 57  \w     35.00  61.00   0.50    7.69    --  104.00 -78.00 -90.17   52
 58  \w     35.00  80.00   0.50    7.69    --  104.00-125.00-150.00   90
 59  \w     87.00 167.00   0.50    7.69    --  104.00  77.00-150.00  160
 60  \w     94.00 126.00   0.50    7.69    --  104.00  77.00-180.00   64
 61  \w     88.00 170.00   0.50    7.69    --  104.00  77.00-120.00  164
 62  \w   -120.00 -73.00   0.50    1.92    --  -49.81-125.00 -60.00   94
 63  \w   -120.00 -73.00   0.50    1.92    --  -49.81-125.00   0.00   94
 64  \w   -120.00 -73.00   0.50    1.92    --  -49.81-125.00  60.00   94
 65  \w   -154.00 -84.00   0.50    7.69    --  -82.50-103.00-112.00  140
;
_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      -0.0845278000
_diffrn_orient_matrix_UB_12      -0.1170229000
_diffrn_orient_matrix_UB_13      0.0473135000
_diffrn_orient_matrix_UB_21      -0.1262515000
_diffrn_orient_matrix_UB_22      -0.0488003000
_diffrn_orient_matrix_UB_23      -0.0873679000
_diffrn_orient_matrix_UB_31      0.1397328000
_diffrn_orient_matrix_UB_32      -0.0805537000
_diffrn_orient_matrix_UB_33      -0.0283888000
_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  0.0318
_diffrn_reflns_av_unetI/netI     0.0261
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            24859
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.503
_diffrn_reflns_theta_min         4.311
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.418
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.775
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.58a (Rigaku Oxford Diffraction, 2019)
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 red'
_exptl_crystal_density_diffrn    1.252
_exptl_crystal_description       plate
_exptl_crystal_F_000             466
_exptl_crystal_size_max          0.136
_exptl_crystal_size_mid          0.058
_exptl_crystal_size_min          0.047
_refine_diff_density_max         0.397
_refine_diff_density_min         -0.464
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.020
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     295
_refine_ls_number_reflns         4765
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.0470
_refine_ls_R_factor_gt           0.0427
_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^)+(0.0444P)^2^+0.9080P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1036
_refine_ls_wR_factor_ref         0.1063
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4367
_reflns_number_total             4765
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo0c01387_si_004.cif
_cod_data_source_block           rjd1_abs
_cod_database_code               4038654
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C56H52N2O4S2
_chemical_oxdiff_usercomment     'Crystallized from CHCl3/MeCN.'
_reflns_odcompleteness_completeness 99.46
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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:
 C2(H2), C4(H4), C8(H8), C9(H9), C10(H10), C11(H11), C17(H17), C19(H19)
2.b Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C27(H27A,H27B,H27C)
;
_shelx_res_checksum              32794
_shelx_hkl_checksum              10617
_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 1.421
_oxdiff_exptl_absorpt_empirical_full_min 0.803