Palladium-Catalyzed [3 + 2] Annulation of Alkynes with Concomitant Aromatic Ring Expansion: A Concise Approach to (Pseudo)azulenes
Zhou, Fulin; Shi, Weiming; Liao, Xingrong; Yang, Yudong; Yu, Zhi-Xiang; You, Jingsong; ACS Catalysis  (2021) 676–686; doi:10.1021/acscatal.1c04549

data_4519221
_publ_section_title
;
 Palladium-Catalyzed [3 + 2] Annulation of Alkynes with Concomitant
 Aromatic Ring Expansion: A Concise Approach to (Pseudo)azulenes
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              676
_journal_page_last               686
_journal_paper_doi               10.1021/acscatal.1c04549
_journal_year                    2021
_chemical_formula_moiety         'C28 H20'
_chemical_formula_sum            'C28 H20'
_chemical_formula_weight         356.44
_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     direct
_audit_creation_date             2019-12-06
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                110.376(5)
_cell_angle_beta                 95.240(5)
_cell_angle_gamma                92.506(5)
_cell_formula_units_Z            2
_cell_length_a                   8.4176(5)
_cell_length_b                   10.9015(6)
_cell_length_c                   11.3672(7)
_cell_measurement_reflns_used    2990
_cell_measurement_temperature    291.4(7)
_cell_measurement_theta_max      71.4950
_cell_measurement_theta_min      4.1530
_cell_volume                     970.56(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46e (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46e (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_environment      air
_diffrn_ambient_temperature      291.4(7)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 15.9595
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.978
_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    -63.00  32.00   1.00    1.03    --  -36.04  77.00  60.00   95
  2  \w    -55.00  33.00   1.00    1.03    --  -36.04  38.00-150.00   88
  3  \w   -105.00 -17.00   1.00    1.03    --  -36.04 -38.00-150.00   88
  4  \w   -103.00 -19.00   1.00    1.03    --  -36.04 -57.00 -60.00   84
  5  \w     19.00 103.00   1.00    1.03    --   36.04  57.00-150.00   84
  6  \w     23.00  89.00   1.00    1.03    --   36.04-125.00 -90.00   66
  7  \w      1.00  75.00   1.00    1.03    --   36.04 -99.00 120.00   74
  8  \w     38.00 124.00   1.00    4.12    --  106.21 -45.00 -90.00   86
  9  \w     89.00 175.00   1.00    4.12    --  106.21  45.00 150.00   86
 10  \w     39.00 133.00   1.00    4.12    --  106.21 -77.00  30.00   94
 11  \w     38.00 124.00   1.00    4.12    --  106.21 -45.00 150.00   86
 12  \w     79.00 174.00   1.00    4.12    --  106.21  77.00-120.00   95
 13  \w     36.00 113.00   1.00    4.12    --  106.21-111.00   0.00   77
 14  \w     37.00 109.00   1.00    4.12    --  106.21 -94.00  90.00   72
 15  \w     36.00 113.00   1.00    4.12    --  106.21-111.00-150.00   77
 16  \w     89.00 175.00   1.00    4.12    --  106.21  45.00 -60.00   86
 17  \w     36.00 128.00   1.00    4.12    --  106.21 -30.00 -30.00   92
 18  \w     39.00 133.00   1.00    4.12    --  106.21 -77.00-150.00   94
 19  \w     68.00 177.00   1.00    4.12    --  106.21  15.00-120.00  109
 20  \w   -103.00 -19.00   1.00    1.03    --  -36.04 -57.00  60.00   84
 21  \w      9.00  40.00   1.00    1.03    --   36.04  77.00  30.00   31
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at home/near, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1089478000
_diffrn_orient_matrix_UB_12      -0.0088467000
_diffrn_orient_matrix_UB_13      0.0990083000
_diffrn_orient_matrix_UB_21      0.0232154000
_diffrn_orient_matrix_UB_22      0.1502452000
_diffrn_orient_matrix_UB_23      0.0660127000
_diffrn_orient_matrix_UB_31      -0.1469397000
_diffrn_orient_matrix_UB_32      0.0149408000
_diffrn_orient_matrix_UB_33      -0.0837566000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0353
_diffrn_reflns_av_unetI/netI     0.0396
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            8096
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         71.659
_diffrn_reflns_theta_min         4.176
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.521
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.72179
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46e (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear bluish blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.220
_exptl_crystal_description       plate
_exptl_crystal_F_000             376
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.5
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.226
_refine_diff_density_min         -0.310
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.018
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     253
_refine_ls_number_reflns         3720
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.018
_refine_ls_R_factor_all          0.0706
_refine_ls_R_factor_gt           0.0627
_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^)+(0.1212P)^2^+0.0903P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1746
_refine_ls_wR_factor_ref         0.1885
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3098
_reflns_number_total             3720
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs1c04549_si_002.cif
_cod_data_source_block           zfl-00
_cod_original_cell_volume        970.55(10)
_cod_database_code               4519221
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C009(H009), C00A(H00A), C00B(H00B), C00C(H00C), C00D(H00D), C00E(H00E),
 C00F(H00F), C00G(H00G), C00H(H00H), C00I(H00I), C00J(H00J), C00K(H00K),
 C00L(H00L), C00M(H00M), C00N(H00N), C00O(H00O), C00P(H00P), C00Q(H00Q),
 C00R(H00R), C00S(H00S)
;
_shelx_res_checksum              27606
_shelx_hkl_checksum              65561
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2019-12-06
_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 1.859
_oxdiff_exptl_absorpt_empirical_full_min 0.720