meso-Triaryl-Substituted Smaragdyrins: Facile Aromaticity Switching.
Xie, Daguan; Liu, Yang; Rao, Yutao; Kim, Gakhyun; Zhou, Mingbo; Yu, Donghai; Xu, Ling; Yin, Bangshao; Liu, Shubin; Tanaka, Takayuki; Aratani, Naoki; Osuka, Atsuhiro; Liu, Qingyun; Kim, Dongho; Song, Jianxin; Journal of the American Chemical Society 140 (2018) 16553–16559; doi:10.1021/jacs.8b07973

data_4133022
_publ_section_title
;
 meso-Triaryl-Substituted Smaragdyrins: Facile Aromaticity Switching.
;
_journal_issue                   48
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              16553
_journal_page_last               16559
_journal_paper_doi               10.1021/jacs.8b07973
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C50 H44 B F2 N5, C H Cl3'
_chemical_formula_sum            'C51 H45 B Cl3 F2 N5'
_chemical_formula_weight         883.08
_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     iterative
_audit_creation_date             2018-04-18
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 119.446(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.2483(3)
_cell_length_b                   15.01136(14)
_cell_length_c                   18.4890(4)
_cell_measurement_reflns_used    46288
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      74.2820
_cell_measurement_theta_min      4.0160
_cell_volume                     4410.46(18)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0697
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_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     20.00  47.00   1.00    2.00    --   36.54  38.00   0.00   27
  2  \w     67.00  98.00   1.00    2.00    --   36.54  38.00   0.00   31
  3  \w     77.00 104.00   1.00    2.00    --   36.54   0.00   0.00   27
  4  \w     72.00 103.00   1.00    2.00    --   36.54  57.00  60.00   31
  5  \w     59.00 104.00   1.00    2.00    --   36.54  77.00  90.00   45
  6  \w     44.00  97.00   1.00    2.00    --   36.54  77.00   0.00   53
  7  \w     67.00  93.00   1.00    2.00    --   36.54  38.00 -60.00   26
  8  \w     63.00 103.00   1.00    2.00    --   36.54  77.00-120.00   40
  9  \w     78.00 104.00   1.00    2.00    --   36.54  38.00-150.00   26
 10  \w     63.00 100.00   1.00    2.00    --   36.54  19.00-150.00   37
 11  \w     67.00  93.00   1.00    2.00    --   36.54  57.00-150.00   26
 12  \w     30.00  55.00   1.00    2.00    --   36.54 -38.00 -60.00   25
 13  \w     24.00  59.00   1.00    2.00    --   36.54   0.00   0.00   35
 14  \w     27.00  63.00   1.00    2.00    --   36.54  57.00  60.00   36
 15  \w     29.00  69.00   1.00    2.00    --   36.54  77.00 120.00   40
 16  \w     40.00  82.00   1.00    2.00    --   36.54  38.00 150.00   42
 17  \w     22.00  54.00   1.00    2.00    --   36.54 -38.00  90.00   32
 18  \w     14.00  40.00   1.00    2.00    --   36.54 -57.00  90.00   26
 19  \w     15.00  48.00   1.00    2.00    --   36.54 -38.00 120.00   33
 20  \w     13.00  73.00   1.00    2.00    --   36.54 -99.00  60.00   60
 21  \w     49.00  75.00   1.00    2.00    --   36.54 -99.00   0.00   26
 22  \w     25.00  69.00   1.00    2.00    --   36.54 -99.00  90.00   44
 23  \w      8.00  57.00   1.00    2.00    --   36.54 -99.00 -30.00   49
 24  \w     19.00  52.00   1.00    2.00    --   36.54 -57.00 -90.00   33
 25  \w     20.00  46.00   1.00    2.00    --   36.54 -57.00-150.00   26
 26  \w     28.00  55.00   1.00    2.00    --   36.54 -38.00-180.00   27
 27  \w     43.00  74.00   1.00    2.00    --   36.54 -99.00-120.00   31
 28  \w     31.00  85.00   1.00    2.00    --   36.54-125.00-120.00   54
 29  \w     14.00  45.00   1.00    2.00    --   36.54 -57.00 -60.00   31
 30  \w      4.00  29.00   1.00    2.00    --   36.54 -99.00   0.00   25
 31  \w    -18.00   8.00   1.00    2.00    --   36.54 -38.00  90.00   26
 32  \w    -21.00   4.00   1.00    2.00    --   36.54 -57.00  90.00   25
 33  \w      2.00  43.00   1.00    2.00    --   36.54 -57.00 150.00   41
 34  \w     20.00  72.00   1.00    2.00    --   36.54  38.00 120.00   52
 35  \w     15.00  71.00   1.00    2.00    --   36.54  77.00  30.00   56
 36  \w     21.00  75.00   1.00    2.00    --   36.54  57.00   0.00   54
 37  \w     19.00  75.00   1.00    2.00    --   36.54  38.00 -90.00   56
 38  \w     25.00  54.00   1.00    2.00    --   36.54  38.00-150.00   29
 39  \w     23.00  54.00   1.00    2.00    --   36.54  57.00-150.00   31
 40  \w     14.00  80.00   1.00    2.00    --   36.54  77.00-180.00   66
 41  \w     13.00  59.00   1.00    2.00    --   36.54  77.00 -90.00   46
 42  \w     11.00  36.00   1.00    2.00    --   36.54  77.00-120.00   25
 43  \w      1.00  28.00   1.00    2.00    --   36.54  92.00 -47.97   27
 44  \w    -32.00  13.00   1.00    2.00    --   36.54   0.00   0.00   45
 45  \w    -28.00   5.00   1.00    2.00    --   36.54 -57.00 -60.00   33
 46  \w    -22.00   6.00   1.00    2.00    --   36.54 -57.00 -90.00   28
 47  \w    -28.00   3.00   1.00    2.00    --   36.54 -38.00 -60.00   31
 48  \w    -28.00  -3.00   1.00    2.00    --   36.54 -57.00-150.00   25
 49  \w    -33.00   8.00   1.00    2.00    --   36.54 -38.00-180.00   41
 50  \w      1.00  34.00   1.00    2.00    --   36.54 -99.00-120.00   33
 51  \w     51.00  77.00   1.00    8.00    --  111.00 -91.00-180.00   26
 52  \w     49.00 127.00   1.00    8.00    --  111.00 -50.00-180.00   78
 53  \w    116.00 141.00   1.00    8.00    --  111.00 -91.00-180.00   25
 54  \w    101.00 145.00   1.00    8.00    --  111.00 -91.00 -60.00   44
 55  \w     92.00 145.00   1.00    8.00    --  111.00 -91.00  30.00   53
 56  \w    114.00 146.00   1.00    8.00    --  111.00 -91.00  90.00   32
 57  \w     90.00 115.00   1.00    8.00    --  111.00-111.00 150.00   25
 58  \w     48.00  73.00   1.00    8.00    --  111.00 -91.00  30.00   25
 59  \w     44.00  69.00   1.00    8.00    --  111.00-111.00 -30.00   25
 60  \w     71.00 116.00   1.00    8.00    --  111.00-111.00 -30.00   45
 61  \w     69.00 115.00   1.00    8.00    --  111.00-111.00 -90.00   46
 62  \w     45.00 117.00   1.00    8.00    --  111.00 -63.00 -60.00   72
 63  \w     89.00 115.00   1.00    8.00    --  111.00  25.00   0.00   26
 64  \w     98.00 124.00   1.00    8.00    --  111.00  50.00 -30.00   26
 65  \w    144.00 177.00   1.00    8.00    --  111.00  50.00 -30.00   33
 66  \w    153.00 178.00   1.00    8.00    --  111.00  38.00 -60.00   25
 67  \w    152.00 177.00   1.00    8.00    --  111.00  77.00 -30.00   25
 68  \w    145.00 172.00   1.00    8.00    --  111.00  77.00   0.00   27
 69  \w    142.00 168.00   1.00    8.00    --  111.00  77.00  60.00   26
 70  \w    143.00 178.00   1.00    8.00    --  111.00  38.00   0.00   35
 71  \w    149.00 174.00   1.00    8.00    --  111.00  25.00 -60.00   25
 72  \w    137.00 171.00   1.00    8.00    --  111.00  77.00 -60.00   34
 73  \w    138.00 172.00   1.00    8.00    --  111.00  63.00-150.00   34
 74  \w    122.00 178.00   1.00    8.00    --  111.00  77.00-180.00   56
 75  \w    115.00 177.00   1.00    8.00    --  111.00  77.00 -90.00   62
 76  \w    128.00 169.00   1.00    8.00    --  111.00  77.00  30.00   41
 77  \w    121.00 176.00   1.00    8.00    --  111.00  77.00 120.00   55
 78  \w    123.00 171.00   1.00    8.00    --  111.00  77.00 150.00   48
 79  \w    101.00 127.00   1.00    8.00    --  111.00  50.00 150.00   26
 80  \w     92.00 175.00   1.00    8.00    --  111.00  63.00  90.00   83
 81  \w     92.00 118.00   1.00    8.00    --  111.00  63.00   0.00   26
 82  \w     92.00 118.00   1.00    8.00    --  111.00  63.00  30.00   26
 83  \w     92.00 119.00   1.00    8.00    --  111.00  38.00  30.00   27
 84  \w     95.00 121.00   1.00    8.00    --  111.00  50.00  30.00   26
 85  \w     95.00 120.00   1.00    8.00    --  111.00  38.00   0.00   25
 86  \w     92.00 117.00   1.00    8.00    --  111.00  63.00 -30.00   25
 87  \w     92.00 118.00   1.00    8.00    --  111.00  38.00 -60.00   26
 88  \w     92.00 127.00   1.00    8.00    --  111.00  38.00 -90.00   35
 89  \w     95.00 121.00   1.00    8.00    --  111.00  50.00-150.00   26
 90  \w     94.00 122.00   1.00    8.00    --  111.00  38.00-150.00   28
 91  \w     94.00 178.00   1.00    8.00    --  111.00  50.00-120.00   84
 92  \w     92.00 117.00   1.00    8.00    --  111.00  63.00-120.00   25
 93  \w     93.00 133.00   1.00    8.00    --  111.00  63.00-150.00   40
 94  \w     94.00 120.00   1.00    8.00    --  111.00  50.00-180.00   26
 95  \w     92.00 120.00   1.00    8.00    --  111.00  38.00-180.00   28
 96  \w     92.00 117.00   1.00    8.00    --  111.00  63.00-180.00   25
 97  \w     84.00 109.00   1.00    8.00    --  111.00  77.00-180.00   25
 98  \w     84.00 110.00   1.00    8.00    --  111.00  77.00-150.00   26
 99  \w     85.00 110.00   1.00    8.00    --  111.00  77.00-120.00   25
100  \w     84.00 109.00   1.00    8.00    --  111.00  77.00 -90.00   25
101  \w     94.00 120.00   1.00    8.00    --  111.00  50.00 -60.00   26
102  \w     92.00 118.00   1.00    8.00    --  111.00  63.00 -60.00   26
103  \w     91.00 128.00   1.00    8.00    --  111.00  30.00-114.00   37
104  \w     88.00 114.00   1.00    8.00    --  111.00  25.00 -60.00   26
105  \w     89.00 114.00   1.00    8.00    --  111.00  26.00 -20.77   25
106  \w     87.00 119.00   1.00    8.00    --  111.00  25.00  30.00   32
107  \w     92.00 118.00   1.00    8.00    --  111.00  38.00  60.00   26
108  \w     93.00 147.00   1.00    8.00    --  111.00  38.00  90.00   54
109  \w     95.00 121.00   1.00    8.00    --  111.00  50.00  90.00   26
110  \w     94.00 119.00   1.00    8.00    --  111.00  50.00 120.00   25
111  \w     92.00 122.00   1.00    8.00    --  111.00  38.00 150.00   30
112  \w     92.00 117.00   1.00    8.00    --  111.00  63.00 120.00   25
113  \w     84.00 109.00   1.00    8.00    --  111.00  77.00  60.00   25
114  \w     92.00 118.00   1.00    8.00    --  111.00  63.00  60.00   26
115  \w     84.00 110.00   1.00    8.00    --  111.00  77.00  90.00   26
116  \w     84.00 109.00   1.00    8.00    --  111.00  77.00 120.00   25
117  \w     84.00 110.00   1.00    8.00    --  111.00  77.00 150.00   26
118  \w     86.00 140.00   1.00    8.00    --  111.00  25.00  90.00   54
119  \w     85.00 111.00   1.00    8.00    --  111.00  77.00  30.00   26
120  \w     84.00 110.00   1.00    8.00    --  111.00  77.00   0.00   26
121  \w     84.00 110.00   1.00    8.00    --  111.00  77.00 -30.00   26
122  \w     85.00 111.00   1.00    8.00    --  111.00  77.00 -60.00   26
123  \w     11.00  51.00   1.00    2.00    --   36.54  77.00  90.00   40
124  \w      0.00  25.00   1.00    2.00    --   36.54  94.00 125.69   25
125  \w    -46.00 -21.00   1.00    2.00    --  -36.54 -30.00  84.00   25
126  \w    -32.00  -5.00   1.00    2.00    --   36.54 -38.00 120.00   27
127  \w    -31.00   3.00   1.00    2.00    --   36.54 -57.00  60.00   34
128  \w     41.00  75.00   1.00    8.00    --  111.00-111.00 150.00   34
129  \w     42.00  78.00   1.00    8.00    --  111.00 -91.00  90.00   36
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0159765000
_diffrn_orient_matrix_UB_12      -0.0857025000
_diffrn_orient_matrix_UB_13      -0.0360236000
_diffrn_orient_matrix_UB_21      -0.0693430000
_diffrn_orient_matrix_UB_22      -0.0480169000
_diffrn_orient_matrix_UB_23      0.0096082000
_diffrn_orient_matrix_UB_31      -0.0658087000
_diffrn_orient_matrix_UB_32      0.0297318000
_diffrn_orient_matrix_UB_33      -0.0881216000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0692
_diffrn_reflns_av_unetI/netI     0.0272
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            78692
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.597
_diffrn_reflns_theta_max         66.597
_diffrn_reflns_theta_min         4.026
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.289
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29992
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            brown
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.330
_exptl_crystal_description       needle
_exptl_crystal_F_000             1840
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.556
_refine_diff_density_min         -0.514
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     572
_refine_ls_number_reflns         7774
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.0539
_refine_ls_R_factor_gt           0.0504
_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^)+(0.0578P)^2^+4.4565P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1290
_refine_ls_wR_factor_ref         0.1313
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7175
_reflns_number_total             7774
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07973_si_003.cif
_cod_data_source_block           4
_cod_original_cell_volume        4410.46(16)
_cod_database_code               4133022
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         'C100 H100 N5 B1 F2'
_shelx_estimated_absorpt_t_max   0.803
_shelx_estimated_absorpt_t_min   0.547
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     71.98
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Ternary CH refined with riding coordinates:
 C51(H51)
2.b Aromatic/amide H refined with riding coordinates:
 N4(H4), C21(H21), C22(H22), C3(H3), C4(H4A), C12(H12), C13(H13), C18(H18),
 C17(H17), C46(H46), C44(H44), C37(H37), C35(H35), C8(H8), C28(H28), C26(H26)
2.c Idealised Me refined as rotating group:
 C48(H48A,H48B,H48C), C50(H50A,H50B,H50C), C49(H49A,H49B,H49C), C39(H39A,H39B,
 H39C), C41(H41A,H41B,H41C), C40(H40A,H40B,H40C), C31(H31A,H31B,H31C), C32(H32A,
 H32B,H32C), C30(H30A,H30B,H30C)
;
_shelx_res_checksum              25716
_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 3.031
_oxdiff_exptl_absorpt_empirical_full_min 0.317