A new skeletal rearrangement of 1,7-dimethyl Cookson's cage dione catalyzed by a Lewis acid.
Kotha, Sambasivarao; Cheekatla, Subba Rao; Organic & biomolecular chemistry 18 (2020) 1377–1383; doi:10.1039/c9ob02298h

data_7157317
_publ_section_title
;
 A new skeletal rearrangement of 1,7-dimethyl Cookson's cage dione
 catalyzed by a Lewis acid.
;
_journal_issue                   7
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              1377
_journal_page_last               1383
_journal_paper_doi               10.1039/c9ob02298h
_journal_volume                  18
_journal_year                    2020
_chemical_formula_moiety         '4(C20 H22 O2)'
_chemical_formula_sum            'C80 H88 O8'
_chemical_formula_weight         1177.50
_chemical_melting_point          383
_chemical_name_common            'cage rearranged ketone'
_chemical_name_systematic
(1R,5S,6aS,8R)-8-methoxy-2a-methyl-4-phenyloctahydro-1,4,5-(epiethane[1,1,2]triyl)cyclopenta[cd]pentalen-2(1H)-one
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-12-19
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2019-04-04 deposited with the CCDC.	2020-01-22 downloaded from the CCDC.
;
_cell_angle_alpha                106.423(3)
_cell_angle_beta                 90.464(3)
_cell_angle_gamma                90.866(3)
_cell_formula_units_Z            2
_cell_length_a                   12.1732(5)
_cell_length_b                   12.4347(4)
_cell_length_c                   21.2275(7)
_cell_measurement_reflns_used    7469
_cell_measurement_temperature    150
_cell_measurement_theta_max      30.9070
_cell_measurement_theta_min      1.9820
_cell_volume                     3081.5(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_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_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.977
_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   -110.00  70.00   0.50    8.00    --  -20.00   0.00-180.00  360
  2  \w    -63.00  19.00   0.50    8.00    --  -20.00 -72.00 -36.00  164
  3  \w    -75.50 -14.50   0.50    8.00    --  -20.00 -72.00-180.00  122
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0066580000
_diffrn_orient_matrix_UB_12      -0.0521579000
_diffrn_orient_matrix_UB_13      0.0068532000
_diffrn_orient_matrix_UB_21      -0.0235139000
_diffrn_orient_matrix_UB_22      -0.0281880000
_diffrn_orient_matrix_UB_23      -0.0310760000
_diffrn_orient_matrix_UB_31      0.0529062000
_diffrn_orient_matrix_UB_32      -0.0047785000
_diffrn_orient_matrix_UB_33      -0.0141822000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0737
_diffrn_reflns_av_unetI/netI     0.1127
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            19146
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         1.708
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.080
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.82096
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
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    1.269
_exptl_crystal_description       block
_exptl_crystal_F_000             1264
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: DCM in Hexane'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.294
_refine_diff_density_min         -0.335
_refine_diff_density_rms         0.081
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     801
_refine_ls_number_reflns         10620
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.1132
_refine_ls_R_factor_gt           0.0689
_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^)+(0.0596P)^2^+1.0287P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1438
_refine_ls_wR_factor_ref         0.1835
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6578
_reflns_number_total             10620
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9ob02298h2.cif
_cod_data_source_block           srk-sr-617-s1_mo
_cod_depositor_comments
'Adding full bibliography for 7157317--7157318.cif.'
_cod_original_cell_volume        3081.50(19)
_cod_database_code               7157317
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.990
_shelx_estimated_absorpt_t_min   0.983
_reflns_odcompleteness_completeness 84.12
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     30.99
_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:
 C66(H66), C65(H65), C12(H12), C5(H5), C7(H7), C48(H48), C67(H67), C69(H69),
 C6(H6), C29(H29), C72(H72), C27(H27), C45(H45), C32(H32), C9(H9), C47(H47),
 C26(H26), C43(H43), C25(H25), C44(H44)
2.b Secondary CH2 refined with riding coordinates:
 C70(H70A,H70B), C50(H50A,H50B), C23(H23A,H23B), C63(H63A,H63B), C10(H10A,
 H10B), C3(H3A,H3B), C68(H68A,H68B), C30(H30A,H30B), C8(H8A,H8B), C53(H53A,
 H53B), C49(H49A,H49B), C28(H28A,H28B)
2.c Aromatic/amide H refined with riding coordinates:
 C20(H20), C16(H16), C18(H18), C17(H17), C77(H77), C79(H79), C58(H58),
 C39(H39), C38(H38), C75(H75), C59(H59), C40(H40), C56(H56), C76(H76), C78(H78),
  C57(H57), C60(H60), C36(H36), C19(H19), C37(H37)
2.d Idealised Me refined as rotating group:
 C41(H41A,H41B,H41C), C61(H61A,H61B,H61C), C73(H73A,H73B,H73C), C54(H54A,H54B,
 H54C), C14(H14A,H14B,H14C), C21(H21A,H21B,H21C), C1(H1A,H1B,H1C), C34(H34A,
 H34B,H34C)
;
_shelx_res_checksum              58147
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.700
_oxdiff_exptl_absorpt_empirical_full_min 0.486