A Copper-Catalyzed Double Coupling Enables a 3-Step Synthesis of the Quassinoid Core Architecture
Condakes, Matthew; Rosen, Rachel; Harwood, Stephen; Maimone, Thomas; Chemical Science  (2019) –; doi:10.1039/C8SC03835J

data_1550134
_publ_section_title
;
 A Copper-Catalyzed Double Coupling Enables a 3-Step Synthesis of the
 Quassinoid Core Architecture
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC03835J
_journal_year                    2019
_chemical_formula_moiety         'C19 H18 F2 O'
_chemical_formula_sum            'C19 H18 F2 O'
_chemical_formula_weight         300.33
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3'
_symmetry_space_group_name_Hall  '-R 3'
_symmetry_space_group_name_H-M   'R -3 :H'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-03-29
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-07-19 deposited with the CCDC.
2018-10-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   26.8452(2)
_cell_length_b                   26.8452(2)
_cell_length_c                   11.23090(10)
_cell_measurement_reflns_used    27203
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      78.8010
_cell_measurement_theta_min      4.3310
_cell_volume                     7009.36(10)
_computing_cell_refinement       'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.45f (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.45f (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_temperature      100(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.979
_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    -15.00  31.00   0.50    0.50    --    0.00 -99.00 120.00   92
  2  \w    -20.00  45.00   0.50    0.50    --    0.00  77.00-180.00  130
  3  \w    -45.00  20.00   0.50    0.50    --    0.00 -77.00-120.00  130
  4  \w    -20.00  45.00   0.50    0.50    --    0.00  77.00   0.00  130
  5  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00 -30.00   92
  6  \w    -20.00  45.00   0.50    0.50    --    0.00  77.00  60.00  130
  7  \w    -15.00  31.00   0.50    0.50    --    0.00 -99.00 -60.00   92
  8  \w    -20.00  45.00   0.50    0.50    --    0.00  77.00 -90.00  130
  9  \w   -170.00 -86.00   0.50    0.50    -- -100.00 -61.00-106.04  168
 10  \w   -172.00 -81.00   0.50    0.50    -- -100.00 -74.00  29.15  182
 11  \w   -112.00 -24.00   0.50    0.50    -- -100.00 111.00  30.00  176
 12  \w   -169.00 -84.00   0.50    0.50    -- -100.00 -66.00-118.39  170
 13  \w   -120.00 -28.00   0.50    0.50    -- -100.00  77.00 -90.00  184
 14  \w   -133.00 -31.00   0.50    0.50    -- -100.00 146.00  33.35  204
 15  \w   -120.00 -28.00   0.50    0.50    -- -100.00  77.00 150.00  184
 16  \w   -175.00 -91.00   0.50    0.50    -- -100.00 -45.00 -30.00  168
 17  \w   -133.00 -31.00   0.50    0.50    -- -100.00 146.00-132.72  204
 18  \w   -114.00 -30.00   0.50    0.50    -- -100.00  61.00  60.00  168
 19  \w   -158.00 -43.00   0.50    0.50    -- -100.00 179.00 -60.00  230
 20  \w   -131.00 -30.00   0.50    0.50    -- -100.00 143.00  95.78  202
 21  \w   -114.00 -30.00   0.50    0.50    -- -100.00  61.00 150.00  168
 22  \w   -170.00 -85.00   0.50    0.50    -- -100.00 -63.00 115.56  170
 23  \w   -112.00 -24.00   0.50    0.50    -- -100.00 111.00-180.00  176
 24  \w    -72.00 -23.00   0.50    0.50    -- -100.00  30.00  30.00   98
 25  \w   -158.00 -43.00   0.50    0.50    -- -100.00 179.00-150.00  230
 26  \w     29.00  66.00   0.50    0.50    --  106.00 -30.00 120.00   74
 27  \w     30.00 109.00   0.50    0.50    --  106.00 -94.00 -30.00  158
 28  \w     29.00  66.00   0.50    0.50    --  106.00 -30.00  90.00   74
 29  \w     31.00  74.00   0.50    0.50    --  106.00 -45.00  60.00   86
 30  \w     30.00 112.00   0.50    0.50    --  106.00-111.00  30.00  164
 31  \w     30.00 112.00   0.50    0.50    --  106.00-111.00-120.00  164
 32  \w     30.00  74.00   0.50    0.50    --  106.00-111.00  90.00   88
;
_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      0.0165362000
_diffrn_orient_matrix_UB_12      -0.0183259000
_diffrn_orient_matrix_UB_13      -0.1166402000
_diffrn_orient_matrix_UB_21      0.0489271000
_diffrn_orient_matrix_UB_22      0.0622838000
_diffrn_orient_matrix_UB_23      -0.0195535000
_diffrn_orient_matrix_UB_31      0.0414932000
_diffrn_orient_matrix_UB_32      -0.0132611000
_diffrn_orient_matrix_UB_33      0.0695166000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0417
_diffrn_reflns_av_unetI/netI     0.0142
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            41015
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.094
_diffrn_reflns_theta_min         3.293
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.776
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66456
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.45f (Rigaku Oxford Diffraction, 2018)
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    1.281
_exptl_crystal_description       block
_exptl_crystal_F_000             2844
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.07
_refine_diff_density_max         1.070
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     204
_refine_ls_number_reflns         3304
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0447
_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^)+(0.0560P)^2^+11.4901P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1205
_refine_ls_wR_factor_ref         0.1217
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3128
_reflns_number_total             3304
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc03835j2.cif
_cod_data_source_block           mc002
_cod_original_cell_volume        7009.36(12)
_cod_database_code               1550134
_shelx_shelxl_version_number     2017/1
_chemical_oxdiff_formula         'C19 H18 F2 O1'
_shelx_estimated_absorpt_t_max   0.948
_shelx_estimated_absorpt_t_min   0.860
_reflns_odcompleteness_completeness 99.94
_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:
 C6(H6), C3(H3)
2.b Secondary CH2 refined with riding coordinates:
 C5(H5A,H5B), C4(H4A,H4B)
2.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C19(H19), C16(H16), C18(H18), C9(H9), C10(H10), C13(H13), C12(H12)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C)
;
_shelx_res_checksum              62336
_shelx_hkl_checksum              29038
_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 1.578
_oxdiff_exptl_absorpt_empirical_full_min 0.583