Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether Directing Group for Pd(II) Catalysis
Romine, Andrew M.; Yang, Kin S.; Karunananda, Malkanthi K.; Chen, Jason S.; Engle, Keary M.; ACS Catalysis 9 (2019) 7626–; doi:10.1021/acscatal.9b01471

data_4514847
_publ_section_title
;
 Synthetic and Mechanistic Studies of a Versatile Heteroaryl Thioether
 Directing Group for Pd(II) Catalysis
;
_journal_issue                   9
_journal_name_full               'ACS Catalysis'
_journal_page_first              7626
_journal_paper_doi               10.1021/acscatal.9b01471
_journal_volume                  9
_journal_year                    2019
_chemical_formula_moiety         'C22 H23 N O2 S2'
_chemical_formula_sum            'C22 H23 N O2 S2'
_chemical_formula_weight         397.53
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2018-02-09
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                70.251(5)
_cell_angle_beta                 85.755(5)
_cell_angle_gamma                83.165(5)
_cell_formula_units_Z            2
_cell_length_a                   8.6349(6)
_cell_length_b                   9.3163(4)
_cell_length_c                   13.5605(9)
_cell_measurement_reflns_used    3237
_cell_measurement_temperature    100
_cell_measurement_theta_max      68.398
_cell_measurement_theta_min      3.465
_cell_volume                     1018.75(11)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX3 v2016.9-0 (Bruker, 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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.0
_diffrn_detector                 'Bruker APEX-II CCD'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD Area Detector'
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device       'Kappa Four-Circle Diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  'Double Bounce Multilayer Mirrors'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0399
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            10983
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        65.996
_diffrn_reflns_theta_max         65.996
_diffrn_reflns_theta_min         3.465
_diffrn_source                   'Micro Focus Rotating Anode'
_diffrn_source_type              'Bruker MicroStar FR-592'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.496
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.5935
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0718 before and 0.0517 after correction. The Ratio of minimum to maximum transmission is 0.7881. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.296
_exptl_crystal_description       block
_exptl_crystal_F_000             420
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.22
_refine_diff_density_max         1.034
_refine_diff_density_min         -0.939
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     296
_refine_ls_number_reflns         3493
_refine_ls_number_restraints     3
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0943
_refine_ls_R_factor_gt           0.0757
_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^)+(0.0647P)^2^+2.6400P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1763
_refine_ls_wR_factor_ref         0.1909
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2743
_reflns_number_total             3493
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b01471_si_004.cif
_cod_data_source_block           engle82_0m_a
_cod_depositor_comments
;
The following automatic conversions were performed:

'_diffrn_radiation_probe' value 'X-ray' changed to 'x-ray' according
to
/home/data/users/saulius/crontab/automatic-downloads/current/ACS/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 from 2011-04-26.

Automatic conversion script
Id: cif_fix_values 4973 2017-02-22 13:04:09Z antanas 
;
_cod_database_code               4514847
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.610
_shelx_estimated_absorpt_t_min   0.542
_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. Restrained distances
 O2-C17
 1.5 with sigma of 0.001
 C17'-C18'
 1.5 with sigma of 0.001
 C17-C18
 1.5 with sigma of 0.001
3. Others
 Sof(O2)=1-FVAR(1)
 Sof(O2')=FVAR(1)
 Sof(H20A)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C22)=Sof(H22A)=Sof(H22B)=
 Sof(H22C)=1-FVAR(2)
 Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(H20)=Sof(C21)=Sof(H21A)=Sof(H21B)=
 Sof(H21C)=FVAR(2)
 Fixed Sof: C17(0.5) H17A(0.5) H17B(0.5) C17'(0.5) H17C(0.5) H17D(0.5)
 C18(0.5) H18A(0.5) H18B(0.5) H18C(0.5) C18'(0.5) H18D(0.5) H18E(0.5) H18F(0.5)
 Fixed Z: C20(0.18966)
4.a Ternary CH refined with riding coordinates:
 C20(H20), C20(H20A)
4.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C17(H17A,H17B), C17'(H17C,H17D)
4.c Aromatic/amide H refined with riding coordinates:
 C15(H15), C14(H14), C12(H12), C2(H2), C9(H9), C3(H3), C10(H10), C5(H5), C4(H4)
4.d Idealised Me refined as rotating group:
 C19(H19A,H19B,H19C), C21(H21A,H21B,H21C), C1A(H1AA,H1AB,H1AC), C22(H22A,H22B,
 H22C), C18(H18A,H18B,H18C), C18'(H18D,H18E,H18F)
;
_shelx_res_checksum              12291
_shelx_hkl_checksum              58241
_olex2_submission_special_instructions 'No special instructions were received'