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_4517180
_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         'C33 H35 N5 O2'
_chemical_formula_sum            'C33 H35 N5 O2'
_chemical_formula_weight         533.66
_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'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-23
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 101.977(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.1416(6)
_cell_length_b                   27.4937(13)
_cell_length_c                   10.2461(6)
_cell_measurement_reflns_used    4777
_cell_measurement_temperature    100
_cell_measurement_theta_max      28.89
_cell_measurement_theta_min      2.51
_cell_volume                     2794.7(3)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0219
_diffrn_reflns_av_unetI/netI     0.0176
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       40
_diffrn_reflns_limit_k_min       -40
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            44140
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.493
_diffrn_reflns_theta_min         2.515
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.081
_exptl_absorpt_correction_T_max  0.8880
_exptl_absorpt_correction_T_min  0.8243
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0663 before and 0.0453 after correction. The Ratio of minimum to maximum transmission is 0.9283. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.268
_exptl_crystal_description       block
_exptl_crystal_F_000             1136
_exptl_crystal_size_max          0.438
_exptl_crystal_size_mid          0.434
_exptl_crystal_size_min          0.37
_refine_diff_density_max         0.459
_refine_diff_density_min         -0.237
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     366
_refine_ls_number_reflns         9275
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.039
_refine_ls_R_factor_all          0.0455
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0548P)^2^+0.9417P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1081
_refine_ls_wR_factor_ref         0.1117
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8331
_reflns_number_total             9275
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04592_si_009.cif
_cod_data_source_block           mo_0241_cg_0m
_cod_database_code               4517180
_shelx_shelxl_version_number     2016/6
_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:
 C28(H28), C31(H31)
2.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C20(H20A,H20B)
2.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C10(H10), C12(H12), C13(H13), C14(H14),
 C16(H16), C19(H19), C22(H22), C23(H23), C25(H25), C26(H26)
2.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C32(H32A,H32B,
 H32C), C33(H33A,H33B,H33C)
;
_shelx_res_checksum              88321
_shelx_hkl_checksum              50912
_olex2_submission_special_instructions 'No special instructions were received'