Rhodium-Catalyzed Regiodivergent Hydrothiolation of Allyl Amines and Imines.
Kennemur, Jennifer L.; Kortman, Gregory D.; Hull, Kami L.; Journal of the American Chemical Society 138 (2016) 11914–11919; doi:10.1021/jacs.6b07142

data_4130818
_publ_section_title
;
 Rhodium-Catalyzed Regiodivergent Hydrothiolation of Allyl Amines and
 Imines.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11914
_journal_page_last               11919
_journal_paper_doi               10.1021/jacs.6b07142
_journal_volume                  138
_journal_year                    2016
_chemical_formula_moiety         'C22 H23 Cl N O2 S2'
_chemical_formula_sum            'C22 H23 Cl N O2 S2'
_chemical_formula_weight         432.98
_chemical_name_systematic        C22H23ClNO2S2
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P -2bc 2a'
_space_group_name_H-M_alt        'P 21 n b'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2015-12-15
_audit_creation_method
;
Olex2 1.2
(compiled 2015.09.30 svn.r3233 for OlexSys, GUI svn.r5103)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.4658(4)
_cell_length_b                   11.3757(4)
_cell_length_c                   19.3517(7)
_cell_measurement_reflns_used    5669
_cell_measurement_temperature    100.15
_cell_measurement_theta_max      27.914
_cell_measurement_theta_min      2.761
_cell_volume                     2083.79(14)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection
;
CrystalClear-SM Expert 2.0 r7 (Rigaku, 2011)
;
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 CCD
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'AFC12 (Right): Kappa 3 circle'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'profile data from \w-scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_radiation_collimation    0.3
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0696
_diffrn_reflns_av_unetI/netI     0.0530
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            26612
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         27.914
_diffrn_reflns_theta_min         2.077
_diffrn_source                   'Rotating Anode'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rotating Anode'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.402
_exptl_absorpt_correction_T_max  0.974
_exptl_absorpt_correction_T_min  0.872
_exptl_absorpt_correction_type   integration
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.0646 before and 0.0602 after correction.
The Ratio of minimum to maximum transmission is 0.8712.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_description       needle
_exptl_crystal_F_000             908
_exptl_crystal_recrystallization_method
;
A 40 mg sample was dissolved in 600 uL of DCM 
and layered with 2 mL hexane. The mixture was 
allowed to sit overnight resulting in the 
formation of colorless needles.
;
_exptl_crystal_size_max          0.342
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.066
_refine_diff_density_max         1.210
_refine_diff_density_min         -0.499
_refine_diff_density_rms         0.071
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.12(11)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     256
_refine_ls_number_reflns         4948
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0463
_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^)+(0.0733P)^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         0.1210
_reflns_Friedel_coverage         0.888
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                4113
_reflns_number_total             4948
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b07142_si_001.cif
_cod_data_source_block           cm76x_0m
_cod_database_code               4130818
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.974
_shelx_estimated_absorpt_t_min   0.875
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.88(11) 0.12(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Ternary CH refined with riding coordinates:
 C14(H14), C15(H15)
3.b Secondary CH2 refined with riding coordinates:
 N11(H11A,H11B)
3.c Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13),
 C18(H18), C19(H19), C20(H20), C21(H21), C22(H22)
3.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C16(H16A,H16B,H16C)
;
_olex2_exptl_crystal_mounting_method
;
The data crystal was mounted using oil (Parantone
-N, Exxon) to a 0.3 mm cryo-loop (Hampton 
Research) with the (1 1 2) scattering planes roughly
 normal to the spindle axis.
;
_olex2_submission_special_instructions 'No special instructions were received'