Rearrangement of a carboxy-substituted spiro[4.4]nonatriene to annulated fulvenes through a Pd(ii)-mediated 1,5-vinyl shift.
Goyal, Karan; Kukier, Garrett A.; Chen, Xiangyang; Turlik, Aneta; Houk, K. N.; Sarpong, Richmond; Chemical science 14 (2023) 11809–11817; doi:10.1039/d3sc03222a

data_1570039
_publ_section_title
;
 Rearrangement of a carboxy-substituted spiro[4.4]nonatriene to annulated
 fulvenes through a Pd(ii)-mediated 1,5-vinyl shift.
;
_journal_issue                   42
_journal_name_full               'Chemical science'
_journal_page_first              11809
_journal_page_last               11817
_journal_paper_doi               10.1039/d3sc03222a
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C18 H16 O4'
_chemical_formula_sum            'C18 H16 O4'
_chemical_formula_weight         296.31
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2021-09-07
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2023-03-02 deposited with the CCDC.	2023-09-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.4998(12)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   10.18735(13)
_cell_length_b                   13.9611(2)
_cell_length_c                   21.4180(3)
_cell_measurement_reflns_used    19242
_cell_measurement_temperature    100
_cell_measurement_theta_max      78.4650
_cell_measurement_theta_min      4.1240
_cell_volume                     3040.53(7)
_computing_cell_refinement       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.112a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.983
_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     83.00 123.00   0.50    0.50    --   50.71  77.00  60.00   80
  2  \w     95.00 151.00   0.50    0.50    --  107.75  61.00  90.00  112
  3  \w     86.00 124.00   0.50    0.50    --   50.71  77.00   0.00   76
  4  \w     91.00 116.00   0.50    0.50    --   50.71  77.00 -30.00   50
  5  \w     84.00 122.00   0.50    0.50    --   50.71  77.00-150.00   76
  6  \w     95.00 163.00   0.50    0.50    --  107.75  15.00-120.00  136
  7  \w    120.00 146.00   0.50    0.50    --  107.75  13.00-151.00   52
  8  \w     38.00 131.00   0.50    0.50    --   50.71  13.00-151.00  186
  9  \w     31.00 104.00   0.50    0.50    --  107.75 -94.00 -60.00  146
 10  \w     37.00  64.00   0.50    0.50    --  107.75-111.00-180.00   54
 11  \w     84.00 109.00   0.50    0.50    --  107.75-111.00-180.00   50
 12  \w     54.00 106.00   0.50    0.50    --  107.75 -94.00 -90.00  104
 13  \w     52.00 104.00   0.50    0.50    --  107.75 -94.00 -30.00  104
 14  \w     34.00 101.00   0.50    0.50    --  107.75 -77.00 -60.00  134
 15  \w     39.00 102.00   0.50    0.50    --  107.75 -77.00-150.00  126
 16  \w     39.00  67.00   0.50    0.50    --  107.75 -61.00-150.00   56
 17  \w     36.00  61.00   0.50    0.50    --  107.75 -61.00-120.00   50
 18  \w     40.00  66.00   0.50    0.50    --  107.75 -61.00 -30.00   52
 19  \w     37.00  65.00   0.50    0.50    --  107.75 -61.00  60.00   56
 20  \w     51.00 100.00   0.50    0.50    --  107.75 -77.00 150.00   98
 21  \w     38.00  64.00   0.50    0.50    --  107.75 -61.00 150.00   52
 22  \w    -28.00  21.00   0.50    0.50    --   50.71 -13.00  36.00   98
 23  \w    -26.00  40.00   0.50    0.50    --   50.71 -38.00 -60.00  132
 24  \w    -27.00  29.00   0.50    0.50    --  -50.71  13.00-151.00  112
 25  \w    -51.00 -24.00   0.50    0.50    -- -100.00  45.00-180.00   54
 26  \w    -54.00 -29.00   0.50    0.50    -- -100.00  45.00-150.00   50
 27  \w    -71.00 -10.00   0.50    0.50    --  -50.71  77.00  90.00  122
 28  \w     -6.00  20.00   0.50    0.50    --  -50.71  77.00  90.00   52
 29  \w    -54.00 -29.00   0.50    0.50    -- -100.00  45.00 150.00   50
 30  \w    -67.00 -40.00   0.50    0.50    -- -100.00  61.00 -60.00   54
 31  \w   -178.00-107.00   0.50    0.50    -- -100.00 -13.00  36.00  142
 32  \w   -175.00-133.00   0.50    0.50    -- -100.00 -45.00  90.00   84
 33  \w   -125.00-100.00   0.50    0.50    -- -100.00 -45.00  90.00   50
 34  \w   -117.00 -88.00   0.50    0.50    -- -100.00 -15.00 -30.00   58
 35  \w   -178.00-122.00   0.50    0.50    -- -100.00 -15.00 -30.00  112
 36  \w   -130.00 -38.00   0.50    0.50    --  -50.71 -13.00  36.00  184
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1372645000
_diffrn_orient_matrix_UB_12      -0.0067224000
_diffrn_orient_matrix_UB_13      0.0340645000
_diffrn_orient_matrix_UB_21      0.0640039000
_diffrn_orient_matrix_UB_22      0.0197521000
_diffrn_orient_matrix_UB_23      -0.0620816000
_diffrn_orient_matrix_UB_31      -0.0033090000
_diffrn_orient_matrix_UB_32      0.1083424000
_diffrn_orient_matrix_UB_33      0.0134312000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0295
_diffrn_reflns_av_unetI/netI     0.0208
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            33501
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.502
_diffrn_reflns_theta_min         3.781
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.748
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85005
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.112a (Rigaku Oxford Diffraction, 2021)
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    1.295
_exptl_crystal_description       block
_exptl_crystal_F_000             1248
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: dichloromethane'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.240
_refine_diff_density_min         -0.222
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     407
_refine_ls_number_reflns         6110
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.024
_refine_ls_R_factor_all          0.0405
_refine_ls_R_factor_gt           0.0351
_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^)+(0.0439P)^2^+1.1344P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0887
_refine_ls_wR_factor_ref         0.0939
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5463
_reflns_number_total             6110
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03222a1.cif
_cod_data_source_block           KGoyal03_Sarpong
_cod_depositor_comments
'Adding full bibliography for 1570039--1570041.cif.'
_cod_original_cell_volume        3040.55(7)
_cod_database_code               1570039
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C N O H'
_shelx_estimated_absorpt_t_max   0.943
_shelx_estimated_absorpt_t_min   0.865
_diffrn_oxdiff_digest_frames
;
01c00ba8899cc97f7dd74dedae370ee4b903204558b
;
_diffrn_oxdiff_digest_hkl
;
0196b3eb0e70612aaf65e36b516a0da5b84a7b
;
_reflns_odcompleteness_completeness 98.23
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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:
 C11A(H11A), C11B(H11B)
2.b Secondary CH2 refined with riding coordinates:
 C12A(H12A,H12B), C12B(H12C,H12D)
2.c Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C4A(H4A), C9A(H9A), C10A(H10A), C14A(H14A), C15A(H15A), C16A(H16A),
 C17A(H17A), C18A(H18A), C3B(H3B), C4B(H4B), C9B(H9B), C10B(H10B), C14B(H14B),
 C15B(H15B), C16B(H16B), C17B(H17B), C18B(H18B)
2.d Idealised Me refined as rotating group:
 C7A(H7AA,H7AB,H7AC), C7B(H7BA,H7BB,H7BC)
;
_shelx_res_checksum              42850
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.135
_oxdiff_exptl_absorpt_empirical_full_min 0.861