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_4133021
_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 H45 N5, 0.5(C7 H8)'
_chemical_formula_sum            'C53.5 H49 N5'
_chemical_formula_weight         761.97
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-03-02
_audit_creation_method
;
Olex2 1.2
(compiled 2017.02.23 svn.r3390 for OlexSys, GUI svn.r5320)
;
_cell_angle_alpha                90
_cell_angle_beta                 95.3076(13)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   12.02532(19)
_cell_length_b                   16.4219(2)
_cell_length_c                   43.1429(5)
_cell_measurement_reflns_used    56436
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      72.5660
_cell_measurement_theta_min      4.5640
_cell_volume                     8483.3(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41k (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41k (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    'ShelXS (Sheldrick, 2008)'
_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 0.975
_diffrn_measured_fraction_theta_max 1.000
_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      6.00  87.00   1.00    1.00    --   34.73  19.00 -30.00   81
  2  \w     63.00 103.00   1.00    1.00    --   34.73  38.00   0.00   40
  3  \w     50.00 102.00   1.00    1.00    --   34.73  77.00  30.00   52
  4  \w     49.00  94.00   1.00    1.00    --   34.73  77.00  90.00   45
  5  \w    125.00 171.00   1.00    5.50    --  107.46  77.00 -30.00   46
  6  \w    131.00 157.00   1.00    5.50    --  107.46  77.00 -90.00   26
  7  \w    137.00 174.00   1.00    5.50    --  107.46  77.00-150.00   37
  8  \w    142.00 170.00   1.00    5.50    --  107.46  77.00-180.00   28
  9  \w    128.00 176.00   1.00    5.50    --  107.46  30.00-150.00   48
 10  \w    116.00 142.00   1.00    5.50    --  107.46  77.00-120.00   26
 11  \w    111.00 171.00   1.00    5.50    --  107.46  77.00 -60.00   60
 12  \w    124.00 174.00   1.00    5.50    --  107.46  77.00   0.00   50
 13  \w    122.00 174.00   1.00    5.50    --  107.46  77.00  90.00   52
 14  \w    120.00 169.00   1.00    5.50    --  107.46  77.00  60.00   49
 15  \w    122.00 175.00   1.00    5.50    --  107.46  77.00 150.00   53
 16  \w    116.00 174.00   1.00    5.50    --  107.46  77.00 120.00   58
 17  \w    113.00 175.00   1.00    5.50    --  107.46  77.00  30.00   62
 18  \w    104.00 175.00   1.00    5.50    --  107.46 111.00-120.00   71
 19  \w     89.00 115.00   1.00    5.50    --  107.46  61.00-180.00   26
 20  \w     89.00 115.00   1.00    5.50    --  107.46  61.00-150.00   26
 21  \w     89.00 115.00   1.00    5.50    --  107.46  61.00-120.00   26
 22  \w     89.00 115.00   1.00    5.50    --  107.46  61.00 -90.00   26
 23  \w     89.00 121.00   1.00    5.50    --  107.46  61.00 -60.00   32
 24  \w     86.00 112.00   1.00    5.50    --  107.46  30.00   0.00   26
 25  \w     89.00 115.00   1.00    5.50    --  107.46  61.00  30.00   26
 26  \w     89.00 117.00   1.00    5.50    --  107.46  61.00   0.00   28
 27  \w     89.00 115.00   1.00    5.50    --  107.46  61.00 -30.00   26
 28  \w     81.00 106.00   1.00    5.50    --  107.46  77.00 -60.00   25
 29  \w     81.00 108.00   1.00    5.50    --  107.46  77.00 -30.00   27
 30  \w     81.00 106.00   1.00    5.50    --  107.46  77.00   0.00   25
 31  \w     81.00 106.00   1.00    5.50    --  107.46  77.00  30.00   25
 32  \w     89.00 115.00   1.00    5.50    --  107.46  61.00  60.00   26
 33  \w     89.00 115.00   1.00    5.50    --  107.46  61.00  90.00   26
 34  \w     89.00 114.00   1.00    5.50    --  107.46  61.00 120.00   25
 35  \w     89.00 115.00   1.00    5.50    --  107.46  61.00 150.00   26
 36  \w     81.00 107.00   1.00    5.50    --  107.46  77.00  90.00   26
 37  \w     81.00 115.00   1.00    5.50    --  107.46  77.00  60.00   34
 38  \w     81.00 112.00   1.00    5.50    --  107.46  77.00 120.00   31
 39  \w     86.00 111.00   1.00    5.50    --  107.46  30.00  90.00   25
 40  \w     86.00 118.00   1.00    5.50    --  107.46  30.00  60.00   32
 41  \w     86.00 114.00   1.00    5.50    --  107.46  30.00 120.00   28
 42  \w     86.00 112.00   1.00    5.50    --  107.46  30.00 150.00   26
 43  \w     81.00 106.00   1.00    5.50    --  107.46  77.00 150.00   25
 44  \w     86.00 114.00   1.00    5.50    --  107.46  30.00  30.00   28
 45  \w     86.00 117.00   1.00    5.50    --  107.46  30.00 -30.00   31
 46  \w     86.00 117.00   1.00    5.50    --  107.46  30.00 -90.00   31
 47  \w     86.00 114.00   1.00    5.50    --  107.46  30.00 -60.00   28
 48  \w     81.00 107.00   1.00    5.50    --  107.46  77.00-120.00   26
 49  \w     81.00 106.00   1.00    5.50    --  107.46  77.00 -90.00   25
 50  \w     86.00 114.00   1.00    5.50    --  107.46  30.00-120.00   28
 51  \w     86.00 114.00   1.00    5.50    --  107.46  30.00-150.00   28
 52  \w     86.00 115.00   1.00    5.50    --  107.46  30.00-180.00   29
 53  \w     81.00 106.00   1.00    5.50    --  107.46  77.00-150.00   25
 54  \w     81.00 127.00   1.00    5.50    --  107.46  77.00-180.00   46
 55  \w     19.00  53.00   1.00    1.00    --   34.73  38.00   0.00   34
 56  \w      9.00 101.00   1.00    1.00    --   34.73  77.00 -60.00   92
 57  \w     18.00  84.00   1.00    1.00    --   34.73  57.00  90.00   66
 58  \w     18.00  98.00   1.00    1.00    --   34.73  57.00 150.00   80
 59  \w      8.00  43.00   1.00    1.00    --   34.73  77.00  30.00   35
 60  \w      9.00  36.00   1.00    1.00    --   34.73  77.00  90.00   27
 61  \w      1.00  28.00   1.00    1.00    --   34.73  92.00  55.55   27
 62  \w      5.00  89.00   1.00    1.00    --   34.73  19.00 120.00   84
 63  \w     26.00  72.00   1.00    1.00    --   34.73 -99.00  60.00   46
 64  \w     23.00  88.00   1.00    1.00    --   34.73-125.00 -60.00   65
 65  \w     40.00 120.00   1.00    5.50    --  107.46 -77.00 -60.00   80
 66  \w     64.00 114.00   1.00    5.50    --  107.46-111.00 -60.00   50
 67  \w     52.00 114.00   1.00    5.50    --  107.46-111.00  90.00   62
 68  \w     38.00 106.00   1.00    5.50    --  107.46 -94.00 150.00   68
 69  \w      1.00  74.00   1.00    1.00    --   34.73 -99.00 120.00   73
 70  \w    -23.00  61.00   1.00    1.00    --   34.73 -77.00 -60.00   84
 71  \w     40.00 125.00   1.00    5.50    --  107.46 -77.00-180.00   85
 72  \w      8.00 100.00   1.00    1.00    --   34.73  77.00-180.00   92
 73  \w      8.00 102.00   1.00    1.00    --   34.73  77.00-120.00   94
 74  \w     -3.00  23.00   1.00    1.00    --   34.73  96.00-104.37   26
 75  \w    -21.00  51.00   1.00    1.00    --   34.73 -57.00-180.00   72
 76  \w    -27.00  31.00   1.00    1.00    --   34.73 -57.00 -30.00   58
 77  \w    -27.00  48.00   1.00    1.00    --   34.73 -57.00  30.00   75
 78  \w    -31.00  19.00   1.00    1.00    --   34.73 -57.00 150.00   50
;
_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      0.0207930000
_diffrn_orient_matrix_UB_12      -0.0454295000
_diffrn_orient_matrix_UB_13      0.0312422000
_diffrn_orient_matrix_UB_21      -0.0479181000
_diffrn_orient_matrix_UB_22      0.0729293000
_diffrn_orient_matrix_UB_23      0.0168711000
_diffrn_orient_matrix_UB_31      -0.1175923000
_diffrn_orient_matrix_UB_32      -0.0377037000
_diffrn_orient_matrix_UB_33      -0.0049460000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0616
_diffrn_reflns_av_unetI/netI     0.0312
_diffrn_reflns_Laue_measured_fraction_full 0.975
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       51
_diffrn_reflns_limit_l_min       -51
_diffrn_reflns_number            120271
_diffrn_reflns_point_group_measured_fraction_full 0.975
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         3.923
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.538
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66530
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41k (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    1.193
_exptl_crystal_description       plate
_exptl_crystal_F_000             3240
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.409
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.048
_refine_ls_extinction_coef       0.00008(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     SHELXL
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1074
_refine_ls_number_reflns         14991
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.055
_refine_ls_R_factor_all          0.0559
_refine_ls_R_factor_gt           0.0509
_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^)+(0.0670P)^2^+4.9921P]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1296
_refine_ls_wR_factor_ref         0.1331
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13510
_reflns_number_total             14991
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b07973_si_004.cif
_cod_data_source_block           5
_cod_depositor_comments
;

2020-07-21
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C107 H98 N10'
_cod_original_formula_weight         1523.95
_cod_original_formula_moiety         '2(C50 H45 N5), C7 H8'
_cod_original_formula_units_Z            4
_cod_database_code               4133021
_shelxl_version_number           2013-2
_chemical_oxdiff_formula         'C60 H60 N5'
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Others
 Fixed Uiso: H10(0.021) H8(0.021) H68(0.022) H67(0.022) H71(0.026) H94(0.027)
 H96(0.026) H62(0.023) H54(0.029) H76(0.029) H78(0.027) H53(0.027) H63(0.024)
 H57(0.03) H87(0.027) H58(0.029) H98A(0.041) H98B(0.041) H98C(0.041)
 H91A(0.043) H91B(0.043) H91C(0.043) H85(0.027) H72(0.026) H10A(0.041)
 H10B(0.041) H10C(0.041) H82A(0.045) H82B(0.045) H82C(0.045) H80A(0.049)
 H80B(0.049) H80C(0.049) H99A(0.042) H99B(0.042) H99C(0.042) H89A(0.039)
 H89B(0.039) H89C(0.039) H90A(0.048) H90B(0.048) H90C(0.048) H81A(0.052)
 H81B(0.052) H81C(0.052) H1(0.024) H3(0.02) H22(0.027) H7(0.028) H4(0.028)
 H8A(0.027) H13(0.027) H12(0.026) H21(0.027) H35(0.029) H17(0.028) H3A(0.027)
 H18(0.029) H30A(0.043) H30B(0.043) H30C(0.043) H103(0.03) H28(0.032)
 H41A(0.05) H41B(0.05) H41C(0.05) H106(0.036) H10D(0.051) H10E(0.051)
 H10F(0.051) H105(0.035) H26(0.03) H39A(0.046) H39B(0.046) H39C(0.046)
 H104(0.03) H32A(0.045) H32B(0.045) H32C(0.045) H102(0.029) H40A(0.053)
 H40B(0.053) H40C(0.053) H46(0.044) H31A(0.056) H31B(0.056) H31C(0.056)
 H50A(0.056) H50B(0.056) H50C(0.056) H37(0.031) H44(0.05) H48A(0.074)
 H48B(0.074) H48C(0.074) H49A(0.098) H49B(0.098) H49C(0.098)
 Fixed X: H10(0.5546) H8(0.7705) H68(0.4101) H67(0.5629) H71(0.312)
 H94(0.7787) H96(0.9022) H62(1.0271) H54(0.7172) H76(0.3889) H78(0.1783)
 H53(0.5573) H63(0.9371) H57(0.8566) H87(1.2901) H58(0.9751) H98A(0.6555)
 H98B(0.6493) H98C(0.7536) H91A(1.1511) H91B(1.2538) H91C(1.141) H85(1.0478)
 H72(0.2902) H10A(0.8874) H10B(0.8788) H10C(0.7708) H82A(0.255) H82B(0.1947)
 H82C(0.3201) H80A(0.5976) H80B(0.5341) H80C(0.5295) H99A(0.9741) H99B(0.9036)
 H99C(0.8544) H89A(0.8375) H89B(0.8584) H89C(0.8265) H90A(1.3075) H90B(1.2321)
 H90C(1.3212) H81A(0.2546) H81B(0.1628) H81C(0.156) H1(0.9001) H3(1.0193)
 H22(0.541) H7(1.1982) H4(1.0382) H8A(1.3139) H13(1.1341) H12(1.2757)
 H21(0.5384) H35(1.4339) H17(0.727) H3A(0.8668) H18(0.6086) H30A(0.8532)
 H30B(0.7819) H30C(0.7666) H103(0.7922) H28(0.466) H41A(1.3747) H41B(1.5034)
 H41C(1.418) H106(0.843) H10D(0.6986) H10E(0.6195) H10F(0.6069) H105(0.9691)
 H26(0.6389) H39A(1.1833) H39B(1.1833) H39C(1.2441) H104(0.9446) H32A(0.5175)
 H32B(0.5382) H32C(0.6383) H102(0.6667) H40A(1.6363) H40B(1.7007) H40C(1.6455)
 H46(0.9649) H31A(0.4277) H31B(0.5125) H31C(0.414) H50A(0.9198) H50B(1.0083)
 H50C(1.0431) H37(1.5954) H44(0.8762) H48A(0.9339) H48B(0.8487) H48C(0.8095)
 H49A(0.9166) H49B(0.8549) H49C(0.9857)
 Fixed Y: H10(0.5145) H8(0.395) H68(0.5137) H67(0.4494) H71(0.5927)
 H94(0.2579) H96(0.4836) H62(0.2565) H54(0.53) H76(0.8658) H78(0.6901)
 H53(0.6225) H63(0.3016) H57(0.4091) H87(0.2243) H58(0.3136) H98A(0.212)
 H98B(0.2605) H98C(0.206) H91A(0.3657) H91B(0.3589) H91C(0.3955) H85(0.0658)
 H72(0.6574) H10A(0.5668) H10B(0.5231) H10C(0.5563) H82A(0.5446) H82B(0.5556)
 H82C(0.5283) H80A(0.764) H80B(0.8427) H80C(0.7639) H99A(0.3337) H99B(0.4072)
 H99C(0.3188) H89A(0.1796) H89B(0.096) H89C(0.1731) H90A(0.0545) H90B(0.0238)
 H90C(0.092) H81A(0.8874) H81B(0.8212) H81C(0.8769) H1(0.804) H3(0.806)
 H22(0.6825) H7(0.9611) H4(0.911) H8A(0.9685) H13(0.7802) H12(0.8545)
 H21(0.6583) H35(1.0815) H17(0.6628) H3A(0.8389) H18(0.6485) H30A(0.6458)
 H30B(0.5772) H30C(0.5961) H103(1.1628) H28(0.827) H41A(0.766) H41B(0.7755)
 H41C(0.81) H106(0.8887) H10D(0.9018) H10E(0.9779) H10F(0.9101) H105(0.9581)
 H26(0.6264) H39A(1.0278) H39B(1.0453) H39C(1.1052) H104(1.0948) H32A(0.8636)
 H32B(0.9207) H32C(0.895) H102(1.0938) H40A(1.0766) H40B(1.0008) H40C(0.9972)
 H46(0.569) H31A(0.6588) H31B(0.707) H31C(0.753) H50A(0.5593) H50B(0.5252)
 H50C(0.5912) H37(0.8841) H44(0.7973) H48A(0.8873) H48B(0.8949) H48C(0.8602)
 H49A(0.603) H49B(0.6855) H49C(0.6822)
 Fixed Z: H10(0.1465) H8(0.1244) H68(0.0427) H67(0.0176) H71(0.0869) H94(-
 0.0305) H96(-0.0247) H62(0.1095) H54(0.2621) H76(0.2204) H78(0.241)
 H53(0.2504) H63(0.0584) H57(0.2546) H87(0.1829) H58(0.2284) H98A(0.0078)
 H98B(0.0389) H98C(0.0343) H91A(0.1427) H91B(0.1677) H91C(0.1768) H85(0.1966)
 H72(0.1382) H10A(0.0184) H10B(0.0504) H10C(0.0314) H82A(0.1927) H82B(0.2231)
 H82C(0.2253) H80A(0.2009) H80B(0.1887) H80C(0.1681) H99A(-0.059) H99B(-0.0734)
 H99C(-0.0756) H89A(0.1992) H89B(0.1832) H89C(0.1628) H90A(0.1838) H90B(0.2092)
 H90C(0.2173) H81A(0.2609) H81B(0.2644) H81C(0.2348) H1(0.0191) H3(0.0949) H22(-
 0.0098) H7(-0.007) H4(-0.0492) H8A(0.0429) H13(0.1827) H12(0.1556) H21(0.0467)
 H35(0.1428) H17(0.1545) H3A(-0.0714) H18(0.1052) H30A(-0.0626) H30B(-0.0802)
 H30C(-0.0452) H103(0.0979) H28(-0.0992) H41A(0.0932) H41B(0.0907) H41C(0.0643)
 H106(0.0789) H10D(0.0327) H10E(0.031) H10F(0.056) H105(0.1129) H26(-0.1153)
 H39A(0.1357) H39B(0.1) H39C(0.1243) H104(0.1226) H32A(-0.0308) H32B(-0.0589)
 H32C(-0.035) H102(0.0636) H40A(0.1509) H40B(0.1396) H40C(0.1712) H46(0.2305)
 H31A(-0.1403) H31B(-0.1589) H31C(-0.1451) H50A(0.156) H50B(0.1817)
 H50C(0.1582) H37(0.1168) H44(0.247) H48A(0.1823) H48B(0.2076) H48C(0.1745)
 H49A(0.2812) H49B(0.286) H49C(0.2897)
;
_olex2_date_sample_data_collection 2017-02-27
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.902
_oxdiff_exptl_absorpt_empirical_full_min 0.392