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_1570041
_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_absolute_configuration unk
_chemical_formula_moiety         '1(C23 H20 O2)'
_chemical_formula_sum            'C23 H20 O2'
_chemical_formula_weight         328.39
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-10-27
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-03-02 deposited with the CCDC.	2023-09-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.837(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.9522(3)
_cell_length_b                   8.0449(2)
_cell_length_c                   16.5583(4)
_cell_measurement_reflns_used    21834
_cell_measurement_temperature    100
_cell_measurement_theta_max      78.1650
_cell_measurement_theta_min      3.4220
_cell_volume                     1704.88(7)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.00
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     39.00 106.00   0.50    0.50    --  107.75 -94.00-180.00  134
  2  \w     35.00 109.00   0.50    0.50    --  107.75-111.00 -30.00  148
  3  \w     31.00 106.00   0.50    0.50    --  107.75 -94.00   0.00  150
  4  \w     37.00  69.00   0.50    0.50    --  107.75-111.00  30.00   64
  5  \w     72.00  99.00   0.50    0.50    --  107.75-111.00  30.00   54
  6  \w    -29.00  24.00   0.50    0.50    --   50.46 -19.00  90.00  106
  7  \w    -20.00  68.00   0.50    0.50    --   50.46 -64.00 -99.00  176
  8  \w     38.00  73.00   0.50    0.50    --  107.75 -64.00 -99.00   70
  9  \w     36.00  68.00   0.50    0.50    --  107.75 -61.00-120.00   64
 10  \w     34.00 102.00   0.50    0.50    --  107.75 -77.00 -30.00  136
 11  \w     36.00  68.00   0.50    0.50    --  107.75 -61.00   0.00   64
 12  \w     36.00  68.00   0.50    0.50    --  107.75 -61.00  90.00   64
 13  \w     36.00  67.00   0.50    0.50    --  107.75 -61.00 -90.00   62
 14  \w     36.00  68.00   0.50    0.50    --  107.75 -61.00-150.00   64
 15  \w     83.00 175.00   0.50    0.50    --  107.75 111.00 -30.00  184
 16  \w     95.00 175.00   0.50    0.50    --  107.75  15.00   0.00  160
 17  \w     85.00 175.00   0.50    0.50    --  107.75  77.00 -60.00  180
 18  \w     81.00 124.00   0.50    0.50    --   50.46  77.00-180.00   86
 19  \w     81.00 124.00   0.50    0.50    --   50.46  77.00 -30.00   86
 20  \w     33.00 121.00   0.50    0.50    --   50.46  64.00  36.00  176
 21  \w     85.00 175.00   0.50    0.50    --  107.75  77.00 150.00  180
 22  \w     85.00 175.00   0.50    0.50    --  107.75  77.00  90.00  180
 23  \w     91.00 175.00   0.50    0.50    --  107.75  61.00 120.00  168
 24  \w     91.00 175.00   0.50    0.50    --  107.75  61.00 150.00  168
 25  \w     90.00 175.00   0.50    0.50    --  107.75  64.00  36.00  170
 26  \w     91.00 175.00   0.50    0.50    --  107.75  61.00 -90.00  168
 27  \w     92.00 122.00   0.50    0.50    --  107.75  61.00-180.00   60
 28  \w    125.00 163.00   0.50    0.50    --  107.75  61.00-180.00   76
 29  \w     94.00 175.00   0.50    0.50    --  107.75  45.00-180.00  162
 30  \w    120.00 171.00   0.50    0.50    --  107.75  45.00 -30.00  102
 31  \w     95.00 175.00   0.50    0.50    --  107.75  15.00  90.00  160
 32  \w    -30.00  30.00   0.50    0.50    --  -50.46  19.00  30.00  120
 33  \w    -68.00  20.00   0.50    0.50    --  -50.46  64.00  36.00  176
 34  \w   -108.00 -26.00   0.50    0.50    -- -100.00  77.00 120.00  164
 35  \w    -54.00 -24.00   0.50    0.50    -- -100.00  45.00  90.00   60
 36  \w    -79.00 -30.00   0.50    0.50    -- -100.00  64.00  36.00   98
 37  \w    -54.00 -24.00   0.50    0.50    -- -100.00  45.00  30.00   60
 38  \w    -54.00 -24.00   0.50    0.50    -- -100.00  45.00 -30.00   60
 39  \w    -54.00 -24.00   0.50    0.50    -- -100.00  45.00-120.00   60
 40  \w    -54.00 -24.00   0.50    0.50    -- -100.00  45.00-150.00   60
 41  \w   -174.00 -81.00   0.50    0.50    -- -100.00 -77.00-180.00  186
 42  \w   -170.00 -83.00   0.50    0.50    -- -100.00 -64.00 -99.00  174
 43  \w   -178.00 -86.00   0.50    0.50    -- -100.00 -30.00  60.00  184
 44  \w   -178.00 -86.00   0.50    0.50    -- -100.00 -30.00  90.00  184
 45  \w   -127.50 -88.00   0.50    0.50    -- -100.00 -15.00 150.00   79
;
_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      -0.0278002000
_diffrn_orient_matrix_UB_12      0.1214867000
_diffrn_orient_matrix_UB_13      -0.0720949000
_diffrn_orient_matrix_UB_21      0.0885676000
_diffrn_orient_matrix_UB_22      -0.0737339000
_diffrn_orient_matrix_UB_23      -0.0413560000
_diffrn_orient_matrix_UB_31      -0.0764920000
_diffrn_orient_matrix_UB_32      -0.1283098000
_diffrn_orient_matrix_UB_33      -0.0444134000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0434
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            31264
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.502
_diffrn_reflns_theta_min         3.453
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.631
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89267
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.279
_exptl_crystal_description       block
_exptl_crystal_F_000             696
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: THF'
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.287
_refine_diff_density_min         -0.258
_refine_diff_density_rms         0.066
_refine_ls_abs_structure_details
;
 Flack x determined using 2807 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.12(17)
_refine_ls_extinction_coef       0.0036(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     527
_refine_ls_number_reflns         6878
_refine_ls_number_restraints     79
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0533
_refine_ls_R_factor_gt           0.0513
_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^)+(0.0725P)^2^+0.7590P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1356
_refine_ls_wR_factor_ref         0.1372
_reflns_Friedel_coverage         0.842
_reflns_Friedel_fraction_full    0.979
_reflns_Friedel_fraction_max     0.978
_reflns_number_gt                6497
_reflns_number_total             6878
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03222a1.cif
_cod_data_source_block           KGoyal06_Sarpong
_cod_depositor_comments
'Adding full bibliography for 1570039--1570041.cif.'
_cod_original_sg_symbol_H-M      P21
_cod_database_code               1570041
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C O H'
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.819
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained planarity
 C5BA, C6BA, C7BA, C8BA, C9BA, C10B
 with sigma of 0.01
 C1, C5BB, C6BB, C7BB, C8BB, C9BB
 with sigma of 0.01
3. Rigid body (RIGU) restrains
 C1, C5BA, C5BB, C6BA, C6BB, C7BA, C7BB, C8BA, C8BB, C9BA, C9BB, C10B
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(C1)=Sof(H1)=Sof(C3BB)=Sof(H3BC)=Sof(H3BD)=Sof(C4BB)=Sof(H4BB)=Sof(C5BB)=
 Sof(C6BB)=Sof(H6BB)=Sof(C7BB)=Sof(H7BB)=Sof(C8BB)=Sof(H8BB)=Sof(C9BB)=
 Sof(H9BB)=Sof(H11C)=Sof(H11D)=1-FVAR(1)
 Sof(C3BA)=Sof(H3BA)=Sof(H3BB)=Sof(C4BA)=Sof(H4BA)=Sof(C5BA)=Sof(C6BA)=
 Sof(H6BA)=Sof(C7BA)=Sof(H7BA)=Sof(C8BA)=Sof(H8BA)=Sof(C9BA)=Sof(H9BA)=
 Sof(C10B)=Sof(H10B)=Sof(H11A)=Sof(H11B)=FVAR(1)
5.a Ternary CH refined with riding coordinates:
 C4A(H4A), C4BA(H4BA), C4BB(H4BB)
5.b Secondary CH2 refined with riding coordinates:
 C3A(H3AA,H3AB), C11A(H11E,H11F), C3BA(H3BA,H3BB), C3BB(H3BC,H3BD), C11B(H11A,
 H11B), C11B(H11C,H11D)
5.c Aromatic/amide H refined with riding coordinates:
 C6A(H6A), C7A(H7A), C8A(H8A), C9A(H9A), C10A(H10A), C12A(H12A), C14A(H14A),
 C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A), C21A(H21A), C1(H1), C6BA(H6BA),
  C6BB(H6BB), C7BA(H7BA), C7BB(H7BB), C8BA(H8BA), C8BB(H8BB), C9BA(H9BA),
 C9BB(H9BB), C10B(H10B), C12B(H12B), C14B(H14B), C17B(H17B), C18B(H18B),
 C19B(H19B), C20B(H20B), C21B(H21B)
5.d Idealised Me refined as rotating group:
 C23A(H23D,H23E,H23F), C23B(H23A,H23B,H23C)
;
_shelx_res_checksum              93702
_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 2.182
_oxdiff_exptl_absorpt_empirical_full_min 0.569