Molecular Acrobatics in Polycyclic Frames: Synthesis of Functionalized D<sub>3</sub>-Trishomocubanes via the Rearrangement Approach.
Kotha, Sambasivarao; Cheekatla, Subba Rao; The Journal of organic chemistry 83 (2018) 6315–6324; doi:10.1021/acs.joc.8b00449

data_4035869
_publ_section_title
;
 Molecular Acrobatics in Polycyclic Frames: Synthesis of Functionalized
 D<sub>3</sub>-Trishomocubanes via the Rearrangement Approach.
;
_journal_issue                   12
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              6315
_journal_page_last               6324
_journal_paper_doi               10.1021/acs.joc.8b00449
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C28 H26 O'
_chemical_formula_sum            'C28 H26 O'
_chemical_formula_weight         378.49
_chemical_melting_point          468.15
_chemical_name_common            D3-trishomocubane
_chemical_name_systematic        'rearranged cage ketone'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2017-12-08
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 110.448(6)
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   21.4018(11)
_cell_length_b                   9.5715(4)
_cell_length_c                   19.6398(10)
_cell_measurement_reflns_used    12955
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      31.1580
_cell_measurement_theta_min      2.2160
_cell_volume                     3769.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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    -59.00  70.00   0.50    8.00    --  -20.00  72.00-180.00  258
  2  \w    -52.00  54.00   0.50    8.00    --  -20.00  72.00 108.00  212
  3  \w    -35.00  -5.00   0.50    8.00    --  -20.00 -72.00-180.00   60
  4  \w   -110.00  19.00   0.50    8.00    --  -20.00 -72.00 108.00  258
  5  \w    -83.50  19.00   0.50    8.00    --  -20.00 -72.00-108.00  205
  6  \w    -85.50 -50.50   0.50    8.00    --  -20.00 -72.00 -36.00   70
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0169049000
_diffrn_orient_matrix_UB_12      0.0641442000
_diffrn_orient_matrix_UB_13      0.0118112000
_diffrn_orient_matrix_UB_21      0.0308010000
_diffrn_orient_matrix_UB_22      -0.0362404000
_diffrn_orient_matrix_UB_23      0.0135499000
_diffrn_orient_matrix_UB_31      0.0041474000
_diffrn_orient_matrix_UB_32      0.0078355000
_diffrn_orient_matrix_UB_33      -0.0340935000
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0398
_diffrn_reflns_av_unetI/netI     0.0223
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -25
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            17971
_diffrn_reflns_theta_full        24.99
_diffrn_reflns_theta_max         24.99
_diffrn_reflns_theta_min         2.21
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.079
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68503
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
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    1.334
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             1616
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: EtOAc and petroleum ether'
_exptl_crystal_size_max          0.458
_exptl_crystal_size_mid          0.239
_exptl_crystal_size_min          0.135
_refine_diff_density_max         0.288
_refine_diff_density_min         -0.209
_refine_diff_density_rms         0.045
_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     262
_refine_ls_number_reflns         3296
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0430
_refine_ls_R_factor_gt           0.0390
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'calc w=1/[\s^2^(Fo^2^)+(0.0456P)^2^+3.4863P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0931
_refine_ls_wR_factor_ref         0.0966
_reflns_number_gt                3007
_reflns_number_total             3296
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo8b00449_si_002.cif
_cod_data_source_block           srk-sr-416_mo
_cod_database_code               4035869
_reflns_odcompleteness_completeness 93.50
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     31.12
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Ternary CH refined with riding coordinates:
 C6(H6), C16(H16), C5(H5), C2(H2), C7(H7), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C14(H14A,H14B), C13(H13A,H13B), C11(H11A,H11B), C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C22(H22), C26(H26), C28(H28), C27(H27), C18(H18), C21(H21), C24(H24),
 C19(H19), C25(H25), C20(H20)
;
_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 1.961
_oxdiff_exptl_absorpt_empirical_full_min 0.606