Density Functional Theory Calculations in Stereochemical Determination of Terpecurcumins J-W, Cytotoxic Terpene-Conjugated Curcuminoids from Curcuma longa L.
Xionghao Lin; Shuai Ji; Xue Qiao; Hongbo Hu; Ni Chen; Yinhui Dong; Yun Huang; Dean Guo; Pengfei Tu; Min Ye; Journal of Organic Chemistry 78 (2013) 11835–11848; doi:10.1021/jo401859u

data_4028793
_publ_contact_author_name
;
;
_publ_section_title
;
 Density Functional Theory Calculations in Stereochemical Determination of
 Terpecurcumins J-W, Cytotoxic Terpene-Conjugated Curcuminoids from
 Curcuma longa L.
;
_journal_name_full               'Journal of Organic Chemistry'
_journal_page_first              11835
_journal_page_last               11848
_journal_paper_doi               10.1021/jo401859u
_journal_volume                  78
_journal_year                    2013
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C34 H40 O6'
_chemical_formula_sum            'C34 H40 O6'
_chemical_formula_weight         544.65
_chemical_name_systematic
;
 ? 
;
_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'
_symmetry_space_group_name_Hall  'P 2yb'
_symmetry_space_group_name_H-M   'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2013-03-26
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:20:19, GUI svn.r4385)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 92.382(2)
_cell_angle_gamma                90.00
_cell_formula_units_Z            4
_cell_length_a                   9.3544(2)
_cell_length_b                   28.8050(7)
_cell_length_c                   11.3634(3)
_cell_measurement_reflns_used    6013
_cell_measurement_temperature    180.00(10)
_cell_measurement_theta_max      73.6500
_cell_measurement_theta_min      4.1940
_cell_volume                     3059.26(13)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection
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CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_publication_material
;
O. V. Dolomanov, L. J. Bourhis, R. J. Gildea, J. A. K. Howard and H. Puschmann,
OLEX2: a complete structure solution, refinement and analysis program.
J. Appl. Cryst. (2009). 42, 339-341.
;
_computing_structure_refinement
;
XL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution
;
XS, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_diffrn_ambient_temperature      180.00(10)
_diffrn_detector_area_resol_mean 10.3914
_diffrn_measured_fraction_theta_full 0.9953
_diffrn_measured_fraction_theta_max 0.6934
_diffrn_measurement_details
;
  1 omega -114.00  -11.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6056  -57.0000   90.0000 103

  2 omega  -48.00   36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -40.6056   37.0000 -120.0000 84

  3 omega -119.00  -93.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -61.5000 -125.0000 -150.0000 26

  4 omega -108.00  -73.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -61.5000 -125.0000 -180.0000 35

  5 omega   33.00   76.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3775  -30.0000 -180.0000 43

  6 omega   96.00  137.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3775  -61.0000   90.0000 41

  7 omega   34.00  113.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3775  -61.0000  -60.0000 79

  8 omega   36.00   81.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3775  -30.0000    0.0000 45

  9 omega   53.00   78.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3775  -30.0000 -120.0000 25

 10 omega   69.00  108.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3775  -94.0000  120.0000 39

 11 omega   33.00   86.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3775  -61.0000   90.0000 53

 12 omega   77.00  155.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      107.3775   61.0000 -180.0000 78
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0658178000
_diffrn_orient_matrix_UB_12      -0.0462236000
_diffrn_orient_matrix_UB_13      0.0391595000
_diffrn_orient_matrix_UB_21      -0.1483225000
_diffrn_orient_matrix_UB_22      0.0164398000
_diffrn_orient_matrix_UB_23      -0.0470713000
_diffrn_orient_matrix_UB_31      0.0286623000
_diffrn_orient_matrix_UB_32      -0.0212846000
_diffrn_orient_matrix_UB_33      -0.1211457000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0295
_diffrn_reflns_av_unetI/netI     0.0387
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            11980
_diffrn_reflns_theta_full        72.10
_diffrn_reflns_theta_max         72.10
_diffrn_reflns_theta_min         3.07
_diffrn_source                   'SuperNova (Cu) x-ray Source'
_exptl_absorpt_coefficient_mu    0.642
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66499
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.181
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1166
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_platon_squeeze_details
;
 ?
;
_refine_diff_density_max         1.490
_refine_diff_density_min         -0.312
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.09(19)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.037
_refine_ls_hydrogen_treatment    none
_refine_ls_matrix_type           full
_refine_ls_number_parameters     734
_refine_ls_number_reflns         8519
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0605
_refine_ls_R_factor_gt           0.0581
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.1170P)^2^+0.8744P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1624
_refine_ls_wR_factor_ref         0.1663
_reflns_number_gt                8019
_reflns_number_total             8519
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo401859u_si_002.cif
_cod_data_source_block           exp_1368
_cod_original_cell_volume        3059.27(13)
_cod_database_code               4028793
_chemical_oxdiff_formula         C34H40O6
_reflns_odcompleteness_completeness 99.53
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.49
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  {H6A,H6B} of C6, H7 of C7, H8 of C8, {H9A,H9B} of C9, H10 of C10, H12 of
  C12, H13 of C13, {H28A,H28B} of C28, H56 of C56, H18 of C18, {H4A,H4B} of C4,
  H42 of C42, H47 of C47, H46 of C46, {H61A,H61B} of C61, H64 of C64, H67 of
  C67, H65 of C65, {H38A,H38B} of C38, H30 of C30, H44 of C44, H41 of C41,
  {H40A,H40B} of C40, H33 of C33, {H43A,H43B} of C43, H24 of C24, H21 of C21,
  H19 of C19, H53 of C53, {H27A,H27B} of C27, H34 of C34, H22 of C22, H59 of
  C59, {H62A,H62B} of C62, H58 of C58, H25 of C25, H68 of C68, H52 of C52, H31
  of C31, H55 of C55
 At 1.5 times of:
  {H14A,H14B,H14C} of C14, {H15A,H15B,H15C} of C15, H4 of O4, {H50A,H50B,
  H50C} of C50, {H49A,H49B,H49C} of C49, H10A of O10, H9 of O9, H3 of O3, {H48A,
  H48B,H48C} of C48, H6 of O6, {H16A,H16B,H16C} of C16, {H51A,H51B,H51C} of C51,
   {H17A,H17B,H17C} of C17
2.a Ternary CH refined with riding coordinates:
 C7(H7), C8(H8), C10(H10), C13(H13), C41(H41), C42(H42), C44(H44), C47(H47)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B), C9(H9A,H9B), C27(H27A,H27B), C28(H28A,H28B),
 C38(H38A,H38B), C40(H40A,H40B), C43(H43A,H43B), C61(H61A,H61B), C62(H62A,H62B)
2.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C18(H18), C19(H19), C21(H21), C22(H22), C24(H24), C25(H25),
 C30(H30), C31(H31), C33(H33), C34(H34), C46(H46), C52(H52), C53(H53), C55(H55),
  C56(H56), C58(H58), C59(H59), C64(H64), C65(H65), C67(H67), C68(H68)
2.d Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,H16B,H16C), C17(H17A,H17B,
 H17C), C48(H48A,H48B,H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C51(H51A,
 H51B,H51C)
2.e Idealised tetrahedral OH refined as rotating group:
 O3(H3), O4(H4), O6(H6), O9(H9), O10(H10A)
;