Formation of complex cyclic compounds <i>via</i> a dehydrogenative Diels-Alder reaction.
Xu, Zhongwei; Lei, Yu; Chang, Meng; Qiang, Ruihua; Hu, Qiong; Hu, Yimin; Organic & biomolecular chemistry 23 (2025) 9330–9335; doi:10.1039/d5ob01117e

data_7160738
_publ_section_title
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 Formation of complex cyclic compounds <i>via</i> a dehydrogenative
 Diels-Alder reaction.
;
_journal_issue                   41
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              9330
_journal_page_last               9335
_journal_paper_doi               10.1039/d5ob01117e
_journal_volume                  23
_journal_year                    2025
_chemical_formula_moiety         'C45 H36 O4'
_chemical_formula_sum            'C45 H36 O4'
_chemical_formula_weight         640.74
_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_Hall           '-P 2n 2ab'
_space_group_name_H-M_alt        'P b c n'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-07-18
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
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2024-10-15 deposited with the CCDC.	2025-09-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   34.0625(7)
_cell_length_b                   15.8412(3)
_cell_length_c                   29.0629(6)
_cell_measurement_reflns_used    9858
_cell_measurement_temperature    298(2)
_cell_measurement_theta_max      58.418
_cell_measurement_theta_min      3.041
_cell_volume                     15682.1(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker D8 Venture diffractometer'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      298(2)
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1687
_diffrn_reflns_av_unetI/netI     0.0388
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       41
_diffrn_reflns_limit_h_min       -41
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            228135
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.462
_diffrn_reflns_theta_min         3.041
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_target            Mo
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.539
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.3055
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1560 before and 0.1043 after correction.
The Ratio of minimum to maximum transmission is 0.4057.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.086
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             5408
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.224
_refine_diff_density_min         -0.232
_refine_diff_density_rms         0.048
_refine_ls_extinction_coef       0.00149(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1038
_refine_ls_number_reflns         14367
_refine_ls_number_restraints     471
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.1232
_refine_ls_R_factor_gt           0.0835
_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^)+(0.1381P)^2^+5.7387P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2283
_refine_ls_wR_factor_ref         0.2698
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8652
_reflns_number_total             14367
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ob01117e2.cif
_cod_data_source_block           20240717b
_cod_depositor_comments
'Adding full bibliography for 7160738--7160742.cif.'
_cod_database_code               7160738
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.877
_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. Restrained planarity
 O1A, C1, O2A, C5
 with sigma of 0.01
 C25, C23, C22, C20, C24, C21, C19
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C1 \\sim C2 \\sim O1 \\sim O2 \\sim O1A \\sim O2A \\sim C2A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C66A \\sim C67A
\\sim C68A \\sim C69A \\sim C70A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C21A \\sim C22A
\\sim C23A \\sim C24A \\sim C25A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C46 \\sim O5 \\sim O6 \\sim C47A \\sim O5A \\sim O6A \\sim C47: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Same fragment restrains
{C1, C2A, O1A, O2A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C1, C2, O1, O2}
{C20, C21A, C22A, C23A, C24A, C25A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C20, C21, C22, C23, C24, C25}
{C46, C47A, O5A, O6A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C46, C47, O5, O6}
{C65, C66A, C67A, C68A, C69A, C70A} sigma for 1-2: 0.01, 1-3: 0.02
as in
{C65, C66, C67, C68, C69, C70}
5. Others
 Sof(C66A)=Sof(H66A)=Sof(C67A)=Sof(H67A)=Sof(C68A)=Sof(H68A)=Sof(C69A)=
 Sof(H69A)=Sof(C70A)=Sof(H70A)=1-FVAR(1)
 Sof(C66)=Sof(H66)=Sof(C67)=Sof(H67)=Sof(C68)=Sof(H68)=Sof(C69)=Sof(H69)=
 Sof(C70)=Sof(H70)=FVAR(1)
 Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(H2AC)=Sof(O1A)=Sof(O2A)=1-FVAR(2)
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H2C)=Sof(O1)=Sof(O2)=FVAR(2)
 Sof(C47A)=Sof(H47D)=Sof(H47E)=Sof(H47F)=Sof(O5A)=Sof(O6A)=1-FVAR(3)
 Sof(C47)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(O5)=Sof(O6)=FVAR(3)
 Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=
 Sof(H24A)=Sof(C25A)=Sof(H25A)=1-FVAR(4)
 Sof(C21)=Sof(H21)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=
 Sof(C25)=Sof(H25)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C11(H11), C14(H14), C56(H56), C59(H59)
6.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C17(H17A,H17B), C51(H51A,H51B), C62(H62A,H62B)
6.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C21(H21), C22(H22), C23(H23), C24(H24), C25(H25),
 C27(H27), C28(H28), C29(H29), C30(H30), C31(H31), C32(H32), C33(H33), C35(H35),
  C36(H36), C37(H37), C38(H38), C39(H39), C41(H41), C42(H42), C43(H43),
 C44(H44), C45(H45), C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C25A(H25A),
  C57(H57), C58(H58), C66(H66), C67(H67), C68(H68), C69(H69), C70(H70),
 C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C77(H77), C78(H78), C80(H80),
  C81(H81), C82(H82), C83(H83), C84(H84), C86(H86), C87(H87), C88(H88),
 C89(H89), C90(H90), C66A(H66A), C67A(H67A), C68A(H68A), C69A(H69A), C70A(H70A)
6.d Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C), C4(H4A,H4B,H4C), C2A(H2AA,H2AB,H2AC), C47(H47A,H47B,H47C),
 C49(H49A,H49B,H49C), C47A(H47D,H47E,H47F)
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_smtbx_masks_special_details
;
A solvent mask was calculated and 490 electrons were 
found in a volume of 2482\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.65[C4H8O2] per Asymmetric Unit 
which account for 499 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              90449
_shelx_fab_checksum              73738
_olex2_submission_special_instructions 'No special instructions were received'