Late-Stage Diversification by Selectivity Switch in meta-C–H Activation: Evidence for Singlet Stabilization
Korvorapun, Korkit; Kuniyil, Rositha; Ackermann, Lutz; ACS Catalysis  (2019) 435–; doi:10.1021/acscatal.9b04592

data_4517172
_publ_section_title
;
 Late-Stage Diversification by Selectivity Switch in meta-C--H Activation:
 Evidence for Singlet Stabilization
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              435
_journal_paper_doi               10.1021/acscatal.9b04592
_journal_year                    2019
_chemical_formula_moiety         'C18 H15 F N2'
_chemical_formula_sum            'C18 H15 F N2'
_chemical_formula_weight         278.32
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-08-24
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 106.294(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.3115(8)
_cell_length_b                   5.8472(3)
_cell_length_c                   12.7090(5)
_cell_measurement_reflns_used    9861
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      33.76
_cell_measurement_theta_min      3.21
_cell_volume                     1377.44(11)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.01
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0356
_diffrn_reflns_av_unetI/netI     0.0218
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            39008
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.998
_diffrn_reflns_theta_min         2.197
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.089
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.9641
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1373 before and 0.0539 after correction. The Ratio of minimum to maximum transmission is 0.9641. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_description       plate
_exptl_crystal_F_000             584
_exptl_crystal_size_max          0.29
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.065
_refine_diff_density_max         0.402
_refine_diff_density_min         -0.330
_refine_diff_density_rms         0.048
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.159
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     295
_refine_ls_number_reflns         4019
_refine_ls_number_restraints     54
_refine_ls_restrained_S_all      1.154
_refine_ls_R_factor_all          0.0600
_refine_ls_R_factor_gt           0.0546
_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^)+(0.0229P)^2^+1.2421P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1202
_refine_ls_wR_factor_ref         0.1234
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3617
_reflns_number_total             4019
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04592_si_005.cif
_cod_data_source_block           mo_0065_cg_0m
_cod_database_code               4517172
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.994
_shelx_estimated_absorpt_t_min   0.975
_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. Uiso/Uaniso restraints and constraints
C1A \\sim C1B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
C2A \\sim C2B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
C12B \\sim C12A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
C13A \\sim C13B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
C11A \\sim C11B: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.001
C4A \\sim C4B: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.01
C6B \\sim C6A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.01
C10B \\sim C10A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.01
C14B \\sim C14A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.01
3. Others
 Sof(C2B)=Sof(H2B)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=
 Sof(H6B)=Sof(C1B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(H8BC)=
 Sof(C12B)=Sof(H12B)=Sof(C11B)=Sof(H11B)=Sof(C10B)=Sof(H10B)=Sof(C9B)=Sof(C14B)=
 Sof(H14B)=Sof(C13B)=1-FVAR(1)
 Sof(C1A)=Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(C5A)=Sof(H5A)=
 Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=
 Sof(C9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=Sof(C13A)=
 Sof(C14A)=Sof(H14A)=FVAR(1)
4.a Ternary CH refined with riding coordinates:
 C7A(H7A), C7B(H7B)
4.b Aromatic/amide H refined with riding coordinates:
 C2A(H2A), C2B(H2B), C3B(H3B), C5B(H5B), C6B(H6B), C3A(H3A), C5A(H5A),
 C6A(H6A), C10A(H10A), C11A(H11A), C12A(H12A), C12B(H12B), C11B(H11B),
 C10B(H10B), C14B(H14B), C14A(H14A), C16(H16), C17(H17), C18(H18)
4.c Fitted hexagon refined as free rotating group:
 C2B(C3B,C4B,C5B,C6B,C1B), C12B(C11B,C10B,C9B,C14B,C13B)
4.d Idealised Me refined as rotating group:
 C8A(H8AA,H8AB,H8AC), C8B(H8BA,H8BB,H8BC)
;
_shelx_res_checksum              52279
_shelx_hkl_checksum              83389
_olex2_submission_special_instructions 'No special instructions were received'