Antinociceptive Grayanane Diterpenoids from the Leaves of <i>Pieris japonica</i>.
Zheng, Guijuan; Zhou, Junfei; Huang, Lang; Zhang, Hao; Sun, Na; Zhang, Hanqi; Jin, Pengfei; Yue, Mingbo; Meng, Lingkui; Yao, Guangmin; Journal of natural products 82 (2019) 3330–3339; doi:10.1021/acs.jnatprod.9b00569

data_1556569
_publ_section_title
;
 Antinociceptive Grayanane Diterpenoids from the Leaves of <i>Pieris
 japonica</i>.
;
_journal_issue                   12
_journal_name_full               'Journal of natural products'
_journal_page_first              3330
_journal_page_last               3339
_journal_paper_doi               10.1021/acs.jnatprod.9b00569
_journal_volume                  82
_journal_year                    2019
_chemical_absolute_configuration unk
_chemical_formula_moiety         '1.5(H4 O2), 2(C20 H32 O5)'
_chemical_formula_sum            'C40 H70 O13'
_chemical_formula_weight         758.96
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-06-11
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   22.86913(11)
_cell_length_b                   10.48269(4)
_cell_length_c                   8.06194(3)
_cell_measurement_reflns_used    42356
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.6760
_cell_measurement_theta_min      3.8600
_cell_volume                     1932.689(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.991
_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    -89.00 -54.00   0.50    0.50    --    0.00 -17.00-142.00   70
  2  \w    -47.00  20.00   0.50    0.50    --    0.00 -17.00-142.00  134
  3  \w      7.00  33.00   0.50    0.50    --   94.60 -17.00-142.00   52
  4  \w     39.00  65.00   0.50    0.50    --   94.60 -17.00-142.00   52
  5  \w    -17.00  36.00   0.50    0.50    --    0.00  38.00 120.00  106
  6  \w    -89.00 -21.00   0.50    0.50    --    0.00 -57.00 150.00  136
  7  \w    -22.00  56.00   0.50    0.50    --    0.00  57.00   0.00  156
  8  \w     43.00  89.00   0.50    0.50    --    0.00  38.00 120.00   92
  9  \w     10.00  35.00   0.50    0.50    --    0.00  17.00  26.00   50
 10  \w    -20.00  17.00   0.50    0.50    --    0.00 -82.00-150.00   74
 11  \w     63.00  88.00   0.50    0.50    --    0.00  57.00   0.00   50
 12  \w    -17.00   9.00   0.50    0.50    --    0.00 -57.00 150.00   52
 13  \w    -55.00 -30.00   0.50    0.50    --    0.00 -57.00 -30.00   50
 14  \w    -18.00  19.00   0.50    0.50    --    0.00 -57.00 -30.00   74
 15  \w    -17.00  68.00   0.50    0.50    --    0.00  38.00 -60.00  170
 16  \w      5.00  85.00   0.50    0.50    --   94.60 -82.00-120.00  160
 17  \w    158.00 183.00   0.50    0.50    --   94.60  61.00  90.00   50
 18  \w     90.00 125.00   0.50    0.50    --   94.60 -82.00-120.00   70
 19  \w     69.00  95.00   0.50    0.50    --   94.60  66.00 -25.11   52
 20  \w     71.00  97.00   0.50    0.50    --   94.60  61.00  60.00   52
 21  \w     76.00 175.00   0.50    0.50    --   94.60  45.00 -90.00  198
 22  \w     71.00  96.00   0.50    0.50    --   94.60  61.00  90.00   50
 23  \w     66.00  93.00   0.50    0.50    --   94.60  74.00 -55.99   54
 24  \w    142.00 173.00   0.50    0.50    --   94.60  71.00  32.94   62
 25  \w     70.00 181.00   0.50    0.50    --   94.60  63.00 -52.15  222
 26  \w     71.00  97.00   0.50    0.50    --   94.60  61.00 150.00   52
 27  \w     65.00 125.00   0.50    0.50    --   94.60 -82.00-150.00  120
 28  \w     27.00 105.00   0.50    0.50    --   94.60 -82.00  90.00  156
 29  \w    109.00 184.00   0.50    0.50    --   94.60  61.00 120.00  150
 30  \w     71.00 128.00   0.50    0.50    --   94.60  59.00  46.01  114
 31  \w     68.00  98.00   0.50    0.50    --   94.60  69.00 -73.67   60
 32  \w    104.00 143.00   0.50    0.50    --   94.60  69.00 -73.67   78
 33  \w     71.00  99.00   0.50    0.50    --   94.60  61.00-120.00   56
 34  \w    121.00 147.00   0.50    0.50    --   94.60  61.00-120.00   52
 35  \w     74.00 100.00   0.50    0.50    --   94.60  51.00  87.77   52
 36  \w     67.00  92.00   0.50    0.50    --   94.60  71.00  32.94   50
 37  \w     60.00 125.00   0.50    0.50    --   94.60 -82.00 150.00  130
 38  \w    159.00 184.00   0.50    0.50    --   94.60  66.00  24.57   50
 39  \w    134.00 177.00   0.50    0.50    --   94.60  67.00 116.05   86
 40  \w     69.00  94.00   0.50    0.50    --   94.60  66.00  24.57   50
 41  \w     67.00  92.00   0.50    0.50    --   94.60  72.00-171.04   50
 42  \w     70.00  96.00   0.50    0.50    --   94.60  67.00 116.05   52
 43  \w     45.00 104.00   0.50    0.50    --   94.60 -82.00   0.00  118
 44  \w     75.00 134.00   0.50    0.50    --   94.60  45.00 120.00  118
 45  \w     71.00 100.00   0.50    0.50    --   94.60  60.00 -94.02   58
 46  \w     66.00  91.00   0.50    0.50    --   94.60  75.00 -96.20   50
 47  \w     68.00 147.00   0.50    0.50    --   94.60  70.00-148.40  158
 48  \w      8.00 126.00   0.50    0.50    --   94.60 -82.00 -60.00  236
 49  \w     70.00 168.00   0.50    0.50    --   94.60  63.00  12.87  196
 50  \w     70.00  96.00   0.50    0.50    --   94.60  64.00 155.59   52
 51  \w    120.00 156.00   0.50    0.50    --   94.60  64.00 166.15   72
 52  \w     71.00 184.00   0.50    0.50    --   94.60  61.00 -30.00  226
 53  \w     76.00 102.00   0.50    0.50    --   94.60  42.00 157.68   52
 54  \w     71.00  97.00   0.50    0.50    --   94.60  61.00 120.00   52
 55  \w     71.00  99.00   0.50    0.50    --   94.60  64.00 166.15   56
 56  \w     71.00  96.00   0.50    0.50    --   94.60  61.00-180.00   50
 57  \w     77.00 184.00   0.50    0.50    --   94.60  51.00-158.41  214
 58  \w     75.00 182.00   0.50    0.50    --   94.60  45.00  90.00  214
 59  \w     74.00 128.00   0.50    0.50    --   94.60  49.00 159.59  108
 60  \w     71.00  96.00   0.50    0.50    --   94.60  62.00  -4.13   50
 61  \w    143.00 169.00   0.50    0.50    --   94.60  62.00  -4.13   52
 62  \w     25.00 103.00   0.50    0.50    --   94.60 -82.00  30.00  156
 63  \w     10.00  36.00   0.50    0.50    --   94.60 -82.00   0.00   52
 64  \w      7.00  32.00   0.50    0.50    --   94.60 -82.00 150.00   50
 65  \w    105.00 130.00   0.50    0.50    --   94.60  17.00  26.00   50
 66  \w     74.00 100.00   0.50    0.50    --   94.60  54.00  -0.08   52
 67  \w     75.00 101.00   0.50    0.50    --   94.60  61.00-150.00   52
 68  \w      8.00 104.00   0.50    0.50    --   94.60 -61.00  90.00  192
 69  \w     90.00 115.00   0.50    0.50    --   94.60 -17.00-142.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0084325000
_diffrn_orient_matrix_UB_12      -0.0586698000
_diffrn_orient_matrix_UB_13      0.1735055000
_diffrn_orient_matrix_UB_21      0.0128028000
_diffrn_orient_matrix_UB_22      -0.1334550000
_diffrn_orient_matrix_UB_23      -0.0714056000
_diffrn_orient_matrix_UB_31      0.0656056000
_diffrn_orient_matrix_UB_32      0.0184004000
_diffrn_orient_matrix_UB_33      0.0362669000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0279
_diffrn_reflns_av_unetI/netI     0.0090
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            48884
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.046
_diffrn_reflns_theta_min         4.640
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.786
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.81706
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             828
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.192
_refine_diff_density_min         -0.168
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 1633 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         3879
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0259
_refine_ls_R_factor_gt           0.0258
_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^)+(0.0439P)^2^+0.4158P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0688
_refine_ls_wR_factor_ref         0.0688
_reflns_Friedel_coverage         0.733
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                3876
_reflns_number_total             3879
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            np9b00569_si_005.cif
_cod_data_source_block           20180611_zgj4_49_2
_cod_depositor_comments
'Adding full bibliography for 1556567--1556572.cif.'
_cod_database_code               1556569
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.891
_shelx_estimated_absorpt_t_min   0.771
_reflns_odcompleteness_completeness 99.95
_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, All O(H) groups, All O(H,H) groups
2. Others
 Fixed Sof: H00(0.5) H(0.5)
3.a Free rotating group:
 O001(H00,H), O002(H0AA,HA)
3.b Ternary CH refined with riding coordinates:
 C00A(H00A), C00C(H00E), C00D(H00F), C00E(H00G), C00F(H00H), C00G(H00I)
3.c Secondary CH2 refined with riding coordinates:
 C00I(H00M,H00N), C00J(H00O,H00P), C00L(H00T,H00U), C00N(H00X,H00Y), C00O(H00Z,
 HB)
3.d X=CH2 refined with riding coordinates:
 C00M(H00V,H00W)
3.e Idealised Me refined as rotating group:
 C00B(H00B,H00C,H00D), C00H(H00J,H00K,H00L), C00K(H00Q,H00R,H00S)
3.f Idealised tetrahedral OH refined as rotating group:
 O007(H007)
;
_shelx_res_checksum              25428
_shelx_hkl_checksum              49520
_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 1.806
_oxdiff_exptl_absorpt_empirical_full_min 0.622