Photoinduced Irreversible Intramolecular Proton Transfer of Arnebinones B, D, and E: The Case of Photoenolization at the <i>p</i>-Benzoquinone-CH<sub>2</sub>/CH-π System.
Yan, Hai-Wei; Zhao, Ling-Hao; Zhang, Xu; Yang, Ya-Nan; Yuan, Xiang; Zhang, Pei-Cheng; Journal of natural products 84 (2021) 2981–2989; doi:10.1021/acs.jnatprod.1c00830

data_1565505
_publ_section_title
;
 Photoinduced Irreversible Intramolecular Proton Transfer of Arnebinones
 B, D, and E: The Case of Photoenolization at the
 <i>p</i>-Benzoquinone-CH<sub>2</sub>/CH-\p System.
;
_journal_issue                   11
_journal_name_full               'Journal of natural products'
_journal_page_first              2981
_journal_page_last               2989
_journal_paper_doi               10.1021/acs.jnatprod.1c00830
_journal_volume                  84
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C17 H16 O5'
_chemical_formula_sum            'C17 H16 O5'
_chemical_formula_weight         300.30
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2021-02-05
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6226)
;
_cell_angle_alpha                90
_cell_angle_beta                 94.4777(12)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.55217(9)
_cell_length_b                   7.61602(11)
_cell_length_c                   14.54252(19)
_cell_measurement_reflns_used    10291
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      75.1260
_cell_measurement_theta_min      6.0660
_cell_volume                     723.478(17)
_computing_cell_refinement       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.95a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.95a (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  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(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 0.983
_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     25.00 120.00   0.50    0.05    --   47.70  77.00-120.00  190
  2  \w     25.00 120.00   0.50    0.05    --   47.70  77.00 -30.00  190
  3  \w     33.00 120.00   0.50    0.05    --   47.70  57.00  60.00  174
  4  \w    -68.00 -28.00   0.50    0.05    -- -101.00  61.00-180.00   80
  5  \w    -68.00 -28.00   0.50    0.05    -- -101.00  61.00-150.00   80
  6  \w    -68.00 -28.00   0.50    0.05    -- -101.00  61.00  60.00   80
  7  \w    -68.00 -28.00   0.50    0.05    -- -101.00  61.00 150.00   80
  8  \w    -68.00 -28.00   0.50    0.05    -- -101.00  61.00 -30.00   80
  9  \w    -68.00 -28.00   0.50    0.05    -- -101.00  61.00 -60.00   80
 10  \w    -23.00  28.00   0.50    0.05    --  -47.70  19.00  30.00  102
 11  \w     90.00 178.00   0.50    0.05    --  103.25  15.00  60.00  176
 12  \w     90.00 178.00   0.50    0.05    --  103.25  15.00  90.00  176
 13  \w     90.00 178.00   0.50    0.05    --  103.25  15.00 150.00  176
 14  \w     87.00 176.00   0.50    0.05    --  103.25  61.00  30.00  178
 15  \w     91.00 130.00   0.50    0.05    --  103.25  45.00-120.00   78
 16  \w     31.00 105.00   0.50    0.05    --  103.25 -90.00-139.00  148
 17  \w     31.00 106.00   0.50    0.05    --  103.25 -94.00-150.00  150
 18  \w     31.00 111.00   0.50    0.05    --  103.25-125.00-150.00  160
 19  \w    -24.00  76.00   0.50    0.05    --   47.70 -90.00-139.00  200
 20  \w     31.00 106.00   0.50    0.05    --  103.25 -94.00 120.00  150
 21  \w     31.00 111.00   0.50    0.05    --  103.25-125.00  60.00  160
 22  \w     31.00  75.00   0.50    0.05    --  103.25 -61.00  30.00   88
 23  \w     31.00  75.00   0.50    0.05    --  103.25 -61.00   0.00   88
 24  \w     31.00  75.00   0.50    0.05    --  103.25 -61.00 -90.00   88
 25  \w     31.00  75.00   0.50    0.05    --  103.25 -61.00-150.00   88
 26  \w     86.00 176.00   0.50    0.05    --  103.25  90.00 -24.00  180
 27  \w    -76.00  25.00   0.50    0.05    --  -47.70  90.00 -24.00  202
 28  \w   -106.00 -28.00   0.50    0.05    -- -101.00  90.00 -24.00  156
 29  \w   -119.00 -25.00   0.50    0.05    --  -47.70 -77.00-150.00  188
 30  \w   -119.00 -25.00   0.50    0.05    --  -47.70 -77.00-180.00  188
 31  \w   -119.00 -46.50   0.50    0.05    --  -47.70 -77.00 -60.00  145
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0664348000
_diffrn_orient_matrix_UB_12      -0.0252154000
_diffrn_orient_matrix_UB_13      0.0984642000
_diffrn_orient_matrix_UB_21      0.0871564000
_diffrn_orient_matrix_UB_22      0.1822706000
_diffrn_orient_matrix_UB_23      0.0271463000
_diffrn_orient_matrix_UB_31      -0.2088207000
_diffrn_orient_matrix_UB_32      0.0840028000
_diffrn_orient_matrix_UB_33      -0.0293266000
_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  0.0311
_diffrn_reflns_av_unetI/netI     0.0199
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            10189
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.219
_diffrn_reflns_theta_min         6.105
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.846
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.65418
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.95a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.378
_exptl_crystal_description       block
_exptl_crystal_F_000             316
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.163
_refine_diff_density_min         -0.196
_refine_diff_density_rms         0.053
_refine_ls_abs_structure_details
;
 Flack x determined using 1263 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.06(10)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         2867
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0319
_refine_ls_R_factor_gt           0.0317
_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^)+(0.0488P)^2^+0.1730P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0824
_refine_ls_wR_factor_ref         0.0825
_reflns_Friedel_coverage         0.807
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.928
_reflns_number_gt                2849
_reflns_number_total             2867
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np1c00830_si_002.cif
_cod_data_source_block           yhwa_43_p1
_cod_database_code               1565505
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.959
_shelx_estimated_absorpt_t_min   0.780
_reflns_odcompleteness_completeness 99.86
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. 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
2.a Ternary CH refined with riding coordinates:
 C1(H1)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C5(H5A,H5B), C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C11(H11)
2.d Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C), C19(H19A,H19B,H19C)
;
_shelx_res_checksum              23061
_shelx_hkl_checksum              40473
_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 3.970
_oxdiff_exptl_absorpt_empirical_full_min 0.644