Synthesis of Benzobicycloheptanones via the Trap of Photogenerated Ketene Methide Intermediate with Olefins.
Liu, Qiang; Meng, Jiang; Liu, Yang; Yang, Chao; Xia, Wujiong; The Journal of organic chemistry 79 (2014) 8143–8155; doi:10.1021/jo5013465

data_4029895
_publ_section_title
;
 Synthesis of Benzobicycloheptanones via the Trap of Photogenerated Ketene
 Methide Intermediate with Olefins.
;
_journal_issue                   17
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              8143
_journal_page_last               8155
_journal_paper_doi               10.1021/jo5013465
_journal_volume                  79
_journal_year                    2014
_chemical_formula_moiety         'C17 H13 Cl O'
_chemical_formula_sum            'C17 H13 Cl O'
_chemical_formula_weight         268.72
_space_group_crystal_system      tetragonal
_space_group_IT_number           86
_space_group_name_Hall           '-P 4bc'
_space_group_name_H-M_alt        'P 42/n'
_symmetry_space_group_name_Hall  '-P 4bc'
_symmetry_space_group_name_H-M   'P 42/n :2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             2012-12-24
_audit_creation_method
;
  Olex2 1.2
  (compiled Dec  5 2012 16:17:34, GUI svn.r4385)
;
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_formula_units_Z            8
_cell_length_a                   19.2843(9)
_cell_length_b                   19.2843(9)
_cell_length_c                   7.3129(2)
_cell_measurement_reflns_used    6306
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      71.3930
_cell_measurement_theta_min      4.5750
_cell_volume                     2719.55(19)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
;
_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
;
SHELXL, G.M. Sheldrick, Acta Cryst.
(2008). A64, 112-122
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 15.9737
_diffrn_measured_fraction_theta_full 0.99
_diffrn_measured_fraction_theta_max 0.99
_diffrn_measurement_details
;
  1 omega  -21.00   28.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   60.0000 49

  2 omega   37.00   71.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000   57.0000   60.0000 34

  3 omega  -69.00  -36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  120.0000 33

  4 omega  -77.00  -51.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  150.0000 26

  5 omega -123.00  -79.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.9497  -99.0000 -150.0000 44

  6 omega  -94.00  -63.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.9497  142.0000    0.0000 31

  7 omega   25.00   51.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       55.9497   77.0000   90.0000 26

  8 omega   23.00   51.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       55.9497   77.0000  120.0000 28

  9 omega   23.00   52.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       55.9497   77.0000   60.0000 29

 10 omega  -87.00  -39.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -64.5000  -77.0000   90.0000 48

 11 omega  -61.00    6.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -64.5000   50.0000 -180.0000 67

 12 omega -136.00  -42.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      -64.5000  -77.0000   60.0000 94

 13 omega   75.00  113.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   25.0000  150.0000 38

 14 omega   80.00  106.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   37.0000  120.0000 26

 15 omega  133.00  166.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   63.0000   60.0000 33

 16 omega   52.00   86.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994 -113.0000 -163.0000 34

 17 omega   79.00  104.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   77.0000   60.0000 25

 18 omega   84.00  110.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   70.0000   81.3221 26

 19 omega   82.00  116.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   37.0000  150.0000 34

 20 omega   79.00  104.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   77.0000   90.0000 25

 21 omega  115.00  144.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994  -77.0000 -150.0000 29

 22 omega   80.00  106.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   77.0000  120.0000 26

 23 omega   38.00  114.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994 -111.0000  -30.0000 76

 24 omega   88.00  114.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   63.0000   60.0000 26

 25 omega   86.00  112.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   63.0000  120.0000 26

 26 omega   92.00  178.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   50.0000   90.0000 86

 27 omega   83.00  178.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   74.0000  127.7584 95

 28 omega  139.00  165.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   72.0000   98.4154 26

 29 omega   84.00  110.00   1.0000    8.0000
omega____ theta____ kappa____ phi______ frames
    -      111.8994   72.0000   98.4154 26

 30 omega  -72.00   33.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  -77.0000  -60.0000 105

 31 omega  -82.00  -34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000    0.0000 48

 32 omega  -82.00  -34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -        0.0000  178.0000  -90.0000 48

 33 omega -128.00  -83.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -55.9497 -125.0000  150.0000 45

 34 omega   23.00  128.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       55.9497   77.0000 -150.0000 105
;
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0710741000
_diffrn_orient_matrix_UB_12      0.0361307000
_diffrn_orient_matrix_UB_13      -0.0063460000
_diffrn_orient_matrix_UB_21      -0.0358398000
_diffrn_orient_matrix_UB_22      -0.0693955000
_diffrn_orient_matrix_UB_23      0.0430599000
_diffrn_orient_matrix_UB_31      0.0053159000
_diffrn_orient_matrix_UB_32      0.0155901000
_diffrn_orient_matrix_UB_33      0.2061185000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0203
_diffrn_reflns_av_unetI/netI     0.0119
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            13529
_diffrn_reflns_theta_full        67.05
_diffrn_reflns_theta_max         67.05
_diffrn_reflns_theta_min         3.24
_diffrn_source                   'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.377
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.71445
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET)
(compiled Dec  3 2012,18:21:49)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour
;
;
_exptl_crystal_density_diffrn    1.313
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description
;
;
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.109
_refine_diff_density_min         -0.218
_refine_diff_density_rms         0.033
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     172
_refine_ls_number_reflns         2434
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0446
_refine_ls_R_factor_gt           0.0397
_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^)+(0.0486P)^2^+0.6743P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1024
_refine_ls_wR_factor_ref         0.1063
_reflns_number_gt                2125
_reflns_number_total             2434
_reflns_threshold_expression     >2sigma(I)
_cod_data_source_file            jo5013465_si_002.cif
_cod_data_source_block           xia_mjiang
_cod_depositor_comments          'Adding full bibliography for 4029895.cif.'
_cod_original_cell_volume        2719.53(19)
_cod_database_code               4029895
_chemical_oxdiff_formula         'Cl1 C1 N1 H1 O1'
_reflns_odcompleteness_completeness 99.92
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  H16 of C16, H14 of C14, H13 of C13, H15 of C15, H17 of C17, {H9A,H9B} of C9,
   H11 of C11, H3 of C3, H10 of C10, H2 of C2, H6 of C6, H8 of C8
2.a Ternary CH refined with riding coordinates:
 C8(H8), C10(H10), C11(H11)
2.b Secondary CH2 refined with riding coordinates:
 C9(H9A,H9B)
2.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C13(H13), C14(H14), C15(H15), C16(H16), C17(H17)
;