Annulation cascade of arylnitriles with alkynes to stable delocalized PAH carbocations via intramolecular rhodium migration
Yin, Jiangliang; Zhou, Fulin; Zhu, Lei; Yang, Mufan; Lan, Yu; You, Jingsong; Chemical Science  (2018) –; doi:10.1039/C8SC01963K

data_1549480
_publ_section_title
;
 Annulation cascade of arylnitriles with alkynes to stable delocalized PAH
 carbocations via intramolecular rhodium migration
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC01963K
_journal_year                    2018
_chemical_formula_moiety         'F6 Sb, C51 H34 N O3, 0.5(C H2 Cl2)'
_chemical_formula_sum            'C51.5 H35 Cl F6 N O3 Sb'
_chemical_formula_weight         987.00
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2017-12-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_audit_update_record
;
2017-12-27 deposited with the CCDC.
2018-05-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 109.9481(17)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.14367(15)
_cell_length_b                   44.3544(8)
_cell_length_c                   12.23171(19)
_cell_measurement_reflns_used    8320
_cell_measurement_temperature    296.7(8)
_cell_measurement_theta_max      72.4300
_cell_measurement_theta_min      4.9580
_cell_volume                     4663.08(14)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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      296.7(8)
_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
;
  1 omega    1.00   75.00   1.0000    2.8700
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -99.0000   90.0000 74

  2 omega  -31.00   63.00   1.0000    2.8700
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -77.0000  150.0000 94

  3 omega  -35.00   66.00   1.0000    2.8700
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -19.0000  -90.0000 101

  4 omega    7.00  108.00   1.0000    2.8700
omega____ theta____ kappa____ phi______ frames
    -       36.4171   19.0000  120.0000 101

  5 omega  -31.00   53.00   1.0000    2.8700
omega____ theta____ kappa____ phi______ frames
    -       36.4171  -57.0000 -120.0000 84

  6 omega   10.00  104.00   1.0000    2.8700
omega____ theta____ kappa____ phi______ frames
    -       36.4171   77.0000 -120.0000 94

  7 omega   39.00  109.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000 -180.0000 70

  8 omega   91.00  175.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000   57.0000 -108.8521 84

  9 omega   38.00   91.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000    0.0000 53

 10 omega   40.00   98.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -45.0000  120.0000 58

 11 omega   39.00  109.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000  120.0000 70

 12 omega   38.00   91.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000 -150.0000 53

 13 omega   40.00  135.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -77.0000  -90.0000 95

 14 omega   40.00   67.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -30.0000 27

 15 omega   38.00   74.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -30.0000  -60.0000 36

 16 omega   40.00   88.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000  -94.0000    0.0000 48

 17 omega  101.00  165.00   1.0000   11.4800
omega____ theta____ kappa____ phi______ frames
    -      108.0000   61.0000   30.0000 64
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'New Gemini, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      0.0204466000
_diffrn_orient_matrix_UB_12      -0.0331799000
_diffrn_orient_matrix_UB_13      0.0396879000
_diffrn_orient_matrix_UB_21      -0.1097455000
_diffrn_orient_matrix_UB_22      -0.0098762000
_diffrn_orient_matrix_UB_23      -0.1209044000
_diffrn_orient_matrix_UB_31      0.1401553000
_diffrn_orient_matrix_UB_32      -0.0028919000
_diffrn_orient_matrix_UB_33      -0.0420108000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0435
_diffrn_reflns_av_unetI/netI     0.0397
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       53
_diffrn_reflns_limit_k_min       -54
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            25902
_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         72.643
_diffrn_reflns_theta_min         4.872
_diffrn_source                   'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.787
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.32705
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.406
_exptl_crystal_description       needle
_exptl_crystal_F_000             1988
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.45
_exptl_crystal_size_min          0.35
_refine_diff_density_max         2.188
_refine_diff_density_min         -1.400
_refine_diff_density_rms         0.115
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.069
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     587
_refine_ls_number_reflns         9073
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0896
_refine_ls_R_factor_gt           0.0801
_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^)+(0.1320P)^2^+8.9324P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2260
_refine_ls_wR_factor_ref         0.2355
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7654
_reflns_number_total             9073
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc01963k2.cif
_cod_data_source_block           yjl-1
_cod_original_formula_sum        'C51.50 H35 Cl F6 N O3 Sb'
_cod_database_code               1549480
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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. Others
 Fixed Sof: Cl01(0.5) Cl1(0.5) C2(0.5) H2a(0.5) H2b(0.5)
3.a Secondary CH2 refined with riding coordinates:
 C2(H2a,H2b)
3.b Aromatic/amide H refined with riding coordinates:
 C00O(H00O), C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z),
 C010(H010), C011(H011), C013(H013), C014(H014), C015(H015), C017(H017),
 C018(H018), C019(H019), C01B(H01B), C01C(H01C), C01D(H01D), C01E(H01E),
 C01F(H01F), C01G(H01G), C01I(H01j), C01J(H01k), C01K(H01l), C01L(H01m),
 C01M(H01n), C01N(H01o), C01O(H01p), C01P(H01q), C01Q(H01r), C01R(H01s),
 C01S(H01t)
3.c Idealised Me refined as rotating group:
 C01H(H01a,H01h,H01i)
;
_olex2_date_sample_data_collection 2017-06-01
_olex2_submission_special_instructions 'No special instructions were received'