Photoredox Mediated Nickel Catalyzed C(sp3)‒H Thiocarbonylation of Ethers
Kang, Byungjoon; Hong, Soon Hyeok; Chem. Sci.  (2017) –; doi:10.1039/C7SC02516E

data_1546619
_publ_section_title
;
 Photoredox Mediated Nickel Catalyzed C(sp3)--H Thiocarbonylation of
 Ethers
;
_journal_name_full               'Chem. Sci.'
_journal_paper_doi               10.1039/C7SC02516E
_journal_year                    2017
_chemical_formula_moiety         'C54 H76 Cl4 N4 Ni2'
_chemical_formula_sum            'C54 H76 Cl4 N4 Ni2'
_chemical_formula_weight         1040.40
_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             2016-11-11
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.07 svn.r3352 for OlexSys, GUI svn.r5261)
;
_audit_update_record
;
2016-11-11 deposited with the CCDC.
2017-07-21 downloaded from the CCDC.
;
_cell_angle_alpha                110.000(4)
_cell_angle_beta                 107.743(3)
_cell_angle_gamma                96.007(3)
_cell_formula_units_Z            1
_cell_length_a                   9.8953(4)
_cell_length_b                   12.1959(5)
_cell_length_c                   12.3731(5)
_cell_measurement_reflns_used    8816
_cell_measurement_temperature    99.9(5)
_cell_measurement_theta_max      76.0690
_cell_measurement_theta_min      3.9560
_cell_volume                     1299.51(11)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(5)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2262
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -66.00  33.00   1.00    2.63    --  -41.24  38.00  30.00   99
  2  \w   -116.00 -17.00   1.00    2.63    --  -41.24 -38.00-150.00   99
  3  \w     23.00  97.00   1.00    2.63    --   41.24-125.00  60.00   74
  4  \w      1.00  82.00   1.00    2.63    --   41.24 -99.00-180.00   81
  5  \w     17.00  47.00   1.00    2.63    --   50.00  79.00 110.21   30
  6  \w     30.00 137.00   1.00    2.63    --   62.00  75.00 119.97  107
  7  \w     29.00 109.00   1.00   10.52    --  112.00 -94.00   0.00   80
  8  \w     57.00 151.00   1.00   10.52    --  112.00 178.00 -60.00   94
  9  \w     86.00 178.00   1.00   10.52    --  112.00  45.00 150.00   92
 10  \w     36.00 116.00   1.00   10.52    --  112.00-111.00 -60.00   80
 11  \w     36.00 145.00   1.00   10.52    --  112.00 -77.00 -60.00  109
 12  \w     36.00 116.00   1.00   10.52    --  112.00-111.00  90.00   80
 13  \w     36.00 140.00   1.00   10.52    --  112.00 -30.00 120.00  104
 14  \w     83.00 178.00   1.00   10.52    --  112.00  61.00  90.00   95
 15  \w     83.00 178.00   1.00   10.52    --  112.00  61.00  30.00   95
 16  \w     29.00 109.00   1.00   10.52    --  112.00 -94.00  90.00   80
 17  \w     83.00 178.00   1.00   10.52    --  112.00  61.00  60.00   95
 18  \w     36.00 116.00   1.00   10.52    --  112.00-111.00 -90.00   80
 19  \w     86.00 178.00   1.00   10.52    --  112.00  45.00 120.00   92
 20  \w    100.00 178.00   1.00   10.52    --  112.00 111.00 150.00   78
 21  \w     36.00 116.00   1.00   10.52    --  112.00-111.00-180.00   80
 22  \w     40.00 141.00   1.00   10.52    --  112.00 -61.00  90.00  101
 23  \w     36.00 145.00   1.00   10.52    --  112.00 -77.00-180.00  109
 24  \w     57.00 151.00   1.00   10.52    --  112.00 178.00-180.00   94
 25  \w     16.00  45.00   1.00    2.63    --   50.00  82.00-147.94   29
 26  \w     21.00  47.00   1.00    2.63    --   54.00  79.00  -6.95   26
 27  \w     21.00  47.00   1.00    2.63    --   54.00  79.00  67.97   26
 28  \w     20.00  46.00   1.00    2.63    --   54.00  81.00 -66.16   26
 29  \w     30.00 137.00   1.00    2.63    --   62.00  75.00 -41.84  107
 30  \w     79.00 178.00   1.00   10.52    --  112.00  77.00-180.00   99
 31  \w     59.00 178.00   1.00   10.52    --  112.00  15.00 -60.00  119
 32  \w     86.00 153.00   1.00   10.52    --  112.00  45.00   0.00   67
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0924650000
_diffrn_orient_matrix_UB_12      0.1144759000
_diffrn_orient_matrix_UB_13      0.0083534000
_diffrn_orient_matrix_UB_21      0.0078208000
_diffrn_orient_matrix_UB_22      -0.0701678000
_diffrn_orient_matrix_UB_23      -0.1269275000
_diffrn_orient_matrix_UB_31      -0.1401714000
_diffrn_orient_matrix_UB_32      0.0329066000
_diffrn_orient_matrix_UB_33      -0.0637496000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0336
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            21503
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.547
_diffrn_reflns_theta_min         3.967
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.084
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.96464
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear reddish blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.329
_exptl_crystal_description       prism
_exptl_crystal_F_000             552
_exptl_crystal_size_max          0.083
_exptl_crystal_size_mid          0.053
_exptl_crystal_size_min          0.028
_refine_diff_density_max         0.514
_refine_diff_density_min         -1.362
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         5427
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.0604
_refine_ls_R_factor_gt           0.0535
_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^)+(0.0830P)^2^+1.7590P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1521
_refine_ls_wR_factor_ref         0.1583
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4718
_reflns_number_total             5427
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7sc02516e2.cif
_cod_data_source_block           exp_565
_cod_original_cell_volume        1299.50(10)
_cod_database_code               1546619
_shelxl_version_number           2013-4
_chemical_oxdiff_formula         C54H76Cl4N4Ni2
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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: Cl1(0.7) Cl0A(0.3)
3.a Ternary CH refined with riding coordinates:
 C010(H010), C016(H016), C018(H018), C021(H021)
3.b Secondary CH2 refined with riding coordinates:
 C014(H01A,H01B), C023(H02A,H02B)
3.c Aromatic/amide H refined with riding coordinates:
 C012(H012), C013(H013), C015(H015), C022(H022), C024(H024), C027(H027)
3.d Idealised Me refined as rotating group:
 C019(H01C,H01D,H01E), C025(H02C,H02D,H02E), C026(H02F,H02G,H02H), C028(H02I,
 H02J,H02K), C029(H02L,H02M,H02N), C030(H03A,H03B,H03C), C031(H03D,H03E,H03F),
 C032(H03G,H03H,H03I)
;
_shelx_res_checksum              89928
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.313
_oxdiff_exptl_absorpt_empirical_full_min 0.785