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#$Date: 2025-08-20 11:41:31 +0200 (Wed 20 de Aug de 2025) $
#$Revision: 301828 $
#$URL: svn://www.crystallography.net/cod/cif/4/03/34/4033465.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4033465
loop_
_publ_author_name
'Saavedra, Diana I.'
'Rencher, Benjamin D.'
'Kwon, Doo-Hyun'
'Smith, Stacey J.'
'Ess, Daniel H.'
'Andrus, Merritt B.'
_publ_section_title
;
 Synthesis and Computational Studies Demonstrate the Utility of an
 Intramolecular Styryl Diels-Alder Reaction and Di-t-butylhydroxytoluene
 Assisted [1,3]-Shift to Construct Anticancer dl-Deoxypodophyllotoxin.
;
_journal_issue                   4
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              2018
_journal_page_last               2026
_journal_paper_doi               10.1021/acs.joc.7b02957
_journal_volume                  83
_journal_year                    2018
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C22 H20 O7, C H Cl3'
_chemical_formula_sum            'C23 H21 Cl3 O7'
_chemical_formula_weight         515.75
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.0365(7)
_cell_length_b                   15.2618(16)
_cell_length_c                   20.961(2)
_cell_measurement_reflns_used    5612
_cell_measurement_temperature    119(2)
_cell_measurement_theta_max      68.11
_cell_measurement_theta_min      3.58
_cell_volume                     2251.0(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_diffrn_ambient_temperature      119(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0783
_diffrn_reflns_av_unetI/netI     0.0570
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            21020
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.874
_diffrn_reflns_theta_min         3.582
_diffrn_source                   'Bruker-Nonius FR591 Cu rotating anode'
_exptl_absorpt_coefficient_mu    4.075
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5580
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, 2009)'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.522
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1064
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.060
_refine_diff_density_max         0.208
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.046
_refine_ls_abs_structure_details
; 
 Flack x determined using 1493 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   -0.005(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.008
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     314
_refine_ls_number_reflns         4145
_refine_ls_number_restraints     312
_refine_ls_restrained_S_all      0.985
_refine_ls_R_factor_all          0.0358
_refine_ls_R_factor_gt           0.0316
_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/[σ²(Fo²)+(0.0248P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0704
_refine_ls_wR_factor_ref         0.0720
_reflns_Friedel_coverage         0.733
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                3791
_reflns_number_total             4145
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            jo7b02957_si_002.cif
_cod_data_source_block           17003
_cod_depositor_comments
'Adding full bibliography for 4033464--4033465.cif.'
_cod_database_code               4033465
_shelx_shelxl_version_number     2014/7
_shelx_space_group_comment
; 
The symmetry employed for this shelxl refinement is uniquely defined 
by the following loop, which should always be used as a source of 
symmetry information in preference to the above space-group names. 
They are only intended as comments. 
;
_shelx_estimated_absorpt_t_min   0.496
_shelx_estimated_absorpt_t_max   0.792
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
O1 O -0.0697(3) 0.58356(14) 0.09475(10) 0.0319(5) Uani 1 1 d . U . . .
C1 C 0.0700(5) 0.5450(2) 0.05237(14) 0.0335(7) Uani 1 1 d . U . . .
H1A H 0.1457 0.5914 0.0313 0.040 Uiso 1 1 calc R U . . .
H1B H 0.0067 0.5095 0.0191 0.040 Uiso 1 1 calc R U . . .
C2 C 0.1974(4) 0.4874(2) 0.09374(13) 0.0239(6) Uani 1 1 d . U . . .
H2 H 0.1554 0.4250 0.0903 0.029 Uiso 1 1 calc R U . . .
C3 C 0.4072(5) 0.49345(19) 0.07991(13) 0.0244(6) Uani 1 1 d . U . . .
H3A H 0.4355 0.4647 0.0386 0.029 Uiso 1 1 calc R U . . .
H3B H 0.4456 0.5557 0.0768 0.029 Uiso 1 1 calc R U . . .
C4 C 0.5166(4) 0.44915(18) 0.13259(13) 0.0193(6) Uani 1 1 d . U . . .
C5 C 0.6837(4) 0.40341(19) 0.11876(13) 0.0225(6) Uani 1 1 d . U . . .
H5 H 0.7296 0.3987 0.0763 0.027 Uiso 1 1 calc R U . . .
C6 C 0.7790(4) 0.36559(18) 0.16860(13) 0.0209(6) Uani 1 1 d . U . . .
O2 O 0.9455(3) 0.31858(13) 0.16711(9) 0.0275(5) Uani 1 1 d . U . . .
C7 C 0.9740(5) 0.2874(2) 0.23043(14) 0.0317(7) Uani 1 1 d . U . . .
H7A H 1.1048 0.3010 0.2448 0.038 Uiso 1 1 calc R U . . .
H7B H 0.9561 0.2231 0.2320 0.038 Uiso 1 1 calc R U . . .
O3 O 0.8387(3) 0.32970(14) 0.27101(9) 0.0248(4) Uani 1 1 d . U . . .
C8 C 0.7146(4) 0.37199(18) 0.23069(12) 0.0189(6) Uani 1 1 d . U . . .
C9 C 0.5517(4) 0.41682(17) 0.24590(13) 0.0189(6) Uani 1 1 d . U . . .
H9 H 0.5084 0.4207 0.2887 0.023 Uiso 1 1 calc R U . . .
C10 C 0.4511(4) 0.45693(17) 0.19564(12) 0.0168(5) Uani 1 1 d . U . . .
C11 C 0.2765(4) 0.50795(17) 0.20884(12) 0.0174(5) Uani 1 1 d . U . . .
C12 C 0.1560(4) 0.52111(18) 0.15978(13) 0.0197(6) Uani 1 1 d . U . . .
C13 C -0.0163(4) 0.57545(19) 0.15691(14) 0.0247(6) Uani 1 1 d . U . . .
O4 O -0.1089(3) 0.61083(14) 0.19804(10) 0.0312(5) Uani 1 1 d . U . . .
C14 C 0.2520(4) 0.54395(16) 0.27436(12) 0.0164(5) Uani 1 1 d . U . . .
C15 C 0.3946(4) 0.59837(17) 0.29796(12) 0.0176(5) Uani 1 1 d . U . . .
H15 H 0.4997 0.6139 0.2718 0.021 Uiso 1 1 calc R U . . .
C16 C 0.3818(4) 0.62979(17) 0.36006(12) 0.0181(5) Uani 1 1 d . U . . .
C17 C 0.2295(4) 0.60596(17) 0.39869(12) 0.0178(5) Uani 1 1 d . U . . .
C18 C 0.0881(4) 0.55147(17) 0.37461(12) 0.0180(5) Uani 1 1 d . U . . .
C19 C 0.0975(4) 0.52141(17) 0.31212(12) 0.0184(5) Uani 1 1 d . U . . .
H19 H -0.0011 0.4857 0.2954 0.022 Uiso 1 1 calc R U . . .
O5 O 0.5133(3) 0.68329(13) 0.38777(9) 0.0244(5) Uani 1 1 d . U . . .
C20 C 0.6601(4) 0.7161(2) 0.34747(14) 0.0260(6) Uani 1 1 d . U . . .
H20A H 0.7389 0.6673 0.3325 0.039 Uiso 1 1 calc R U . . .
H20B H 0.7391 0.7575 0.3715 0.039 Uiso 1 1 calc R U . . .
H20C H 0.6033 0.7461 0.3108 0.039 Uiso 1 1 calc R U . . .
O6 O 0.2272(3) 0.63258(13) 0.46151(8) 0.0242(4) Uani 1 1 d . U . . .
C21 C 0.0948(5) 0.7008(2) 0.47471(14) 0.0324(7) Uani 1 1 d . U . . .
H21A H 0.1239 0.7518 0.4481 0.049 Uiso 1 1 calc R U . . .
H21B H 0.1035 0.7172 0.5198 0.049 Uiso 1 1 calc R U . . .
H21C H -0.0342 0.6803 0.4653 0.049 Uiso 1 1 calc R U . . .
O7 O -0.0532(3) 0.53098(14) 0.41702(9) 0.0256(5) Uani 1 1 d . U . . .
C22 C -0.2009(4) 0.4749(2) 0.39528(15) 0.0298(7) Uani 1 1 d . U . . .
H22A H -0.2648 0.5018 0.3587 0.045 Uiso 1 1 calc R U . . .
H22B H -0.2930 0.4657 0.4297 0.045 Uiso 1 1 calc R U . . .
H22C H -0.1468 0.4184 0.3825 0.045 Uiso 1 1 calc R U . . .
C1SA C 0.3664(8) 0.2405(4) 0.4037(2) 0.0277(11) Uani 0.85(2) 1 d D U P A 1
H1SA H 0.2860 0.1938 0.3838 0.033 Uiso 0.85(2) 1 calc R U P A 1
Cl1A Cl 0.5878(7) 0.2416(2) 0.36441(16) 0.0367(6) Uani 0.85(2) 1 d D U P A 1
Cl2A Cl 0.3947(7) 0.2153(3) 0.48503(18) 0.0329(6) Uani 0.85(2) 1 d D U P A 1
Cl3A Cl 0.2512(5) 0.3421(4) 0.39303(13) 0.0456(8) Uani 0.85(2) 1 d D U P A 1
C1SB C 0.349(4) 0.224(2) 0.4065(12) 0.0277(11) Uani 0.15(2) 1 d D U P A 2
H1SB H 0.2711 0.1706 0.3980 0.033 Uiso 0.15(2) 1 calc R U P A 2
Cl1B Cl 0.544(3) 0.2278(10) 0.3552(7) 0.0367(6) Uani 0.15(2) 1 d D U P A 2
Cl2B Cl 0.416(4) 0.2281(17) 0.4869(11) 0.0329(6) Uani 0.15(2) 1 d D U P A 2
Cl3B Cl 0.221(2) 0.3179(14) 0.3877(8) 0.0456(8) Uani 0.15(2) 1 d D U P A 2
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
C13 O1 C1 111.2(2)
O1 C1 C2 106.5(2)
O1 C1 H1A 110.4
C2 C1 H1A 110.4
O1 C1 H1B 110.4
C2 C1 H1B 110.4
H1A C1 H1B 108.6
C12 C2 C3 110.2(2)
C12 C2 C1 102.3(2)
C3 C2 C1 115.5(3)
C12 C2 H2 109.5
C3 C2 H2 109.5
C1 C2 H2 109.5
C4 C3 C2 109.4(2)
C4 C3 H3A 109.8
C2 C3 H3A 109.8
C4 C3 H3B 109.8
C2 C3 H3B 109.8
H3A C3 H3B 108.2
C5 C4 C10 120.9(3)
C5 C4 C3 120.2(2)
C10 C4 C3 118.9(3)
C6 C5 C4 117.7(3)
C6 C5 H5 121.2
C4 C5 H5 121.2
C5 C6 O2 128.3(2)
C5 C6 C8 121.9(3)
O2 C6 C8 109.8(2)
C6 O2 C7 105.9(2)
O2 C7 O3 108.0(2)
O2 C7 H7A 110.1
O3 C7 H7A 110.1
O2 C7 H7B 110.1
O3 C7 H7B 110.1
H7A C7 H7B 108.4
C8 O3 C7 105.6(2)
C9 C8 O3 128.4(2)
C9 C8 C6 121.9(3)
O3 C8 C6 109.7(2)
C8 C9 C10 117.5(2)
C8 C9 H9 121.2
C10 C9 H9 121.2
C4 C10 C9 120.1(3)
C4 C10 C11 119.5(2)
C9 C10 C11 120.4(2)
C12 C11 C10 117.2(2)
C12 C11 C14 125.2(2)
C10 C11 C14 117.5(2)
C11 C12 C13 129.3(3)
C11 C12 C2 122.0(3)
C13 C12 C2 108.3(2)
O4 C13 O1 119.6(3)
O4 C13 C12 131.9(3)
O1 C13 C12 108.6(2)
C19 C14 C15 120.6(2)
C19 C14 C11 121.7(2)
C15 C14 C11 117.6(2)
C16 C15 C14 119.4(3)
C16 C15 H15 120.3
C14 C15 H15 120.3
O5 C16 C15 124.1(2)
O5 C16 C17 115.5(2)
C15 C16 C17 120.3(3)
O6 C17 C16 119.2(2)
O6 C17 C18 120.9(2)
C16 C17 C18 119.7(2)
O7 C18 C19 124.8(3)
O7 C18 C17 114.8(2)
C19 C18 C17 120.3(2)
C14 C19 C18 119.6(3)
C14 C19 H19 120.2
C18 C19 H19 120.2
C16 O5 C20 116.7(2)
O5 C20 H20A 109.5
O5 C20 H20B 109.5
H20A C20 H20B 109.5
O5 C20 H20C 109.5
H20A C20 H20C 109.5
H20B C20 H20C 109.5
C17 O6 C21 114.1(2)
O6 C21 H21A 109.5
O6 C21 H21B 109.5
H21A C21 H21B 109.5
O6 C21 H21C 109.5
H21A C21 H21C 109.5
H21B C21 H21C 109.5
C18 O7 C22 117.4(2)
O7 C22 H22A 109.5
O7 C22 H22B 109.5
H22A C22 H22B 109.5
O7 C22 H22C 109.5
H22A C22 H22C 109.5
H22B C22 H22C 109.5
Cl2A C1SA Cl1A 110.8(3)
Cl2A C1SA Cl3A 111.5(3)
Cl1A C1SA Cl3A 109.8(2)
Cl2A C1SA H1SA 108.2
Cl1A C1SA H1SA 108.2
Cl3A C1SA H1SA 108.2
Cl3B C1SB Cl1B 104.0(15)
Cl3B C1SB Cl2B 109.3(19)
Cl1B C1SB Cl2B 112.3(19)
Cl3B C1SB H1SB 110.4
Cl1B C1SB H1SB 110.4
Cl2B C1SB H1SB 110.4
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
O1 C13 1.362(4)
O1 C1 1.449(4)
C1 C2 1.526(4)
C1 H1A 0.9900
C1 H1B 0.9900
C2 C12 1.505(4)
C2 C3 1.507(5)
C2 H2 1.0000
C3 C4 1.507(4)
C3 H3A 0.9900
C3 H3B 0.9900
C4 C5 1.398(4)
C4 C10 1.405(4)
C5 C6 1.369(4)
C5 H5 0.9500
C6 O2 1.374(4)
C6 C8 1.382(4)
O2 C7 1.424(4)
C7 O3 1.431(4)
C7 H7A 0.9900
C7 H7B 0.9900
O3 C8 1.376(3)
C8 C9 1.372(4)
C9 C10 1.409(4)
C9 H9 0.9500
C10 C11 1.481(4)
C11 C12 1.348(4)
C11 C14 1.489(4)
C12 C13 1.470(4)
C13 O4 1.208(4)
C14 C19 1.388(4)
C14 C15 1.394(4)
C15 C16 1.390(4)
C15 H15 0.9500
C16 O5 1.364(3)
C16 C17 1.392(4)
C17 O6 1.378(3)
C17 C18 1.392(4)
C18 O7 1.370(3)
C18 C19 1.389(4)
C19 H19 0.9500
O5 C20 1.425(3)
C20 H20A 0.9800
C20 H20B 0.9800
C20 H20C 0.9800
O6 C21 1.424(4)
C21 H21A 0.9800
C21 H21B 0.9800
C21 H21C 0.9800
O7 C22 1.422(4)
C22 H22A 0.9800
C22 H22B 0.9800
C22 H22C 0.9800
C1SA Cl2A 1.758(5)
C1SA Cl1A 1.762(4)
C1SA Cl3A 1.764(4)
C1SA H1SA 1.0000
C1SB Cl3B 1.74(2)
C1SB Cl1B 1.74(2)
C1SB Cl2B 1.75(2)
C1SB H1SB 1.0000
loop_
_cod_related_entry_id
_cod_related_entry_database
_cod_related_entry_code
1 PubChem 139095995
