Electron-rich benzofulvenes as effective dipolarophiles in copper(i)-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine ylides.
Chang, Xin; Liu, Xue-Tao; Li, Fangfang; Yang, Yuhong; Chung, Lung Wa; Wang, Chun-Jiang; Chemical science 14 (2023) 5460–5469; doi:10.1039/d3sc00435j

data_1568956
_publ_section_title
;
 Electron-rich benzofulvenes as effective dipolarophiles in
 copper(i)-catalyzed asymmetric 1,3-dipolar cycloaddition of azomethine
 ylides.
;
_journal_issue                   20
_journal_name_full               'Chemical science'
_journal_page_first              5460
_journal_page_last               5469
_journal_paper_doi               10.1039/d3sc00435j
_journal_volume                  14
_journal_year                    2023
_chemical_absolute_configuration ad
_chemical_formula_moiety         '2(C31 H24 F3 N O2)'
_chemical_formula_sum            'C62 H48 F6 N2 O4'
_chemical_formula_weight         999.02
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-12
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2023-04-13 deposited with the CCDC.	2023-04-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.7640(4)
_cell_length_b                   15.5751(5)
_cell_length_c                   29.2364(8)
_cell_measurement_reflns_used    17725
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.1620
_cell_measurement_theta_min      2.9920
_cell_volume                     4901.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.961
_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   -118.00 -85.00   0.50    0.30    --  -76.64 -15.00 -30.00   66
  2  \w   -113.00 -66.00   0.50    0.30    --  -71.53 -15.00  60.00   94
  3  \w   -122.00 -78.00   0.50    0.30    --  -81.66 -15.00  60.00   88
  4  \w   -104.00 -73.00   0.50    0.30    --  -81.66 -15.00  90.00   62
  5  \w    -95.00 -54.00   0.50    0.30    --  -63.55 -15.00 150.00   82
  6  \w    -86.00 -50.00   0.50    0.30    --  -63.55 -11.00-178.00   72
  7  \w    -85.00 -41.00   0.50    0.30    --  -81.66 131.00-158.00   88
  8  \w    -64.00 -38.00   0.50    0.30    --  -63.55 125.00 -90.00   52
  9  \w   -100.00 -50.00   0.50    0.30    --  -81.66 125.00   0.00  100
 10  \w   -100.00 -73.00   0.50    0.30    --  -81.66 125.00  30.00   54
 11  \w   -100.00 -75.00   0.50    0.30    --  -81.66 125.00  60.00   50
 12  \w   -100.00 -44.00   0.50    0.30    --  -81.66 125.00  90.00  112
 13  \w    -93.00 -68.00   0.50    0.30    --  -81.66 117.00 118.00   50
 14  \w     37.00  99.00   0.50    0.30    --   76.53-131.00 130.00  124
 15  \w     68.00  96.00   0.50    0.30    --   76.53-125.00 150.00   56
 16  \w     44.00  86.00   0.50    0.30    --   76.53-117.00  31.00   84
 17  \w     28.00  54.00   0.50    0.30    --   62.66-117.00  31.00   52
 18  \w     22.00  75.00   0.50    0.30    --   62.66-125.00-120.00  106
 19  \w     37.00  84.00   0.50    0.30    --   76.53-125.00 -30.00   94
 20  \w     47.00  77.00   0.50    0.30    --   76.53  11.00  -6.00   60
 21  \w     62.00 116.00   0.50    0.30    --   72.93  15.00  30.00  108
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1385520000
_diffrn_orient_matrix_UB_12      0.0247836000
_diffrn_orient_matrix_UB_13      -0.0002168000
_diffrn_orient_matrix_UB_21      0.0355900000
_diffrn_orient_matrix_UB_22      0.0946666000
_diffrn_orient_matrix_UB_23      -0.0080018000
_diffrn_orient_matrix_UB_31      -0.0048618000
_diffrn_orient_matrix_UB_32      -0.0147921000
_diffrn_orient_matrix_UB_33      -0.0520480000
_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  0.0397
_diffrn_reflns_av_unetI/netI     0.0388
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.961
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            34555
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.944
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.062
_diffrn_reflns_theta_min         3.023
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.829
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75696
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.354
_exptl_crystal_description       block
_exptl_crystal_F_000             2080
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.305
_refine_diff_density_min         -0.234
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 3231 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.11(6)
_refine_ls_extinction_coef       0.00152(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.109
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     706
_refine_ls_number_reflns         9786
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.128
_refine_ls_R_factor_all          0.0520
_refine_ls_R_factor_gt           0.0438
_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^)+(0.0759P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1159
_refine_ls_wR_factor_ref         0.1239
_reflns_Friedel_coverage         0.770
_reflns_Friedel_fraction_full    0.995
_reflns_Friedel_fraction_max     0.922
_reflns_number_gt                8452
_reflns_number_total             9786
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc00435j2.cif
_cod_data_source_block           20230412-lxt_1_auto
_cod_depositor_comments
'Adding full bibliography for 1568955--1568956.cif.'
_cod_database_code               1568956
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHONF
_chemical_oxdiff_usercomment     CHO
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F61-C57 \\sim F61A-C57
 with sigma of 0.02
 C57-F1 \\sim C57-F1A
 with sigma of 0.02
 C57-F2 \\sim C57-F2A
 with sigma of 0.02
3. Others
 Sof(F61A)=Sof(F1A)=Sof(F2A)=1-FVAR(1)
 Sof(F61)=Sof(F1)=Sof(F2)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C11(H11), C3(H3), C12(H12), C2(H2), C48(H48), C38(H38), C47(H47), C39(H39)
4.b Aromatic/amide H refined with riding coordinates:
 C37(H37), C9(H9), C15(H15), C44(H44), C64(H64), C6(H6), C36(H36), C71(H71),
 C70(H70), C33(H33), C22(H22), C8(H8), C7(H7), C56(H56), C35(H35), C20(H20),
 C69(H69), C67(H67), C34(H34), C55(H55), C21(H21), C65(H65), C52(H52), C18(H18),
  C41(H41), C16(H16), C54(H54), C43(H43), C17(H17), C66(H66), C42(H42), C53(H53)
4.c Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C74(H74A,H74B,H74C)
;
_shelx_res_checksum              95461
_shelx_hkl_checksum              39623
_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 2.691
_oxdiff_exptl_absorpt_empirical_full_min 0.417