Palladacycle-Phosphine Catalyzed Methylation of Amines and Ketones Using Methanol.
Mamidala, Ramesh; Biswal, Priyabrata; Subramani, M. Siva; Samser, Shaikh; Venkatasubbaiah, Krishnan; The Journal of organic chemistry 84 (2019) 10472–10480; doi:10.1021/acs.joc.9b00983

data_4034013
_publ_section_title
;
 Palladacycle-Phosphine Catalyzed Methylation of Amines and Ketones Using
 Methanol.
;
_journal_issue                   16
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              10472
_journal_page_last               10480
_journal_paper_doi               10.1021/acs.joc.9b00983
_journal_volume                  84
_journal_year                    2019
_chemical_formula_moiety         'C7 H10 N2 O2 S'
_chemical_formula_sum            'C7 H10 N2 O2 S'
_chemical_formula_weight         186.23
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-09-19
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   17.0270(4)
_cell_length_b                   7.43120(16)
_cell_length_c                   6.87490(14)
_cell_measurement_reflns_used    3082
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.1630
_cell_measurement_theta_min      5.2050
_cell_volume                     869.89(3)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_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      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 200K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_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    -74.00  21.00   0.50    0.50    --  -38.50  98.00 154.00  190
  2  \w     34.00 110.00   0.50    2.00    --  102.63 -98.00  47.00  152
  3  \w    109.00 171.00   0.50    2.00    --  102.63  98.00 154.00  124
  4  \w    -74.00 -28.00   0.50    0.50    --  -38.50 -57.00 -30.00   92
  5  \w     41.00 111.00   0.50    0.50    --   49.31  57.00-120.00  140
  6  \w      1.00  40.00   0.50    0.50    --   49.31 -37.00 120.00   78
  7  \w     19.00  44.00   0.50    0.50    --   49.31 -98.00  47.00   50
  8  \w     94.00 163.00   0.50    2.00    --  102.63  61.00 120.00  138
  9  \w     43.00  72.00   0.50    2.00    --  102.63-125.00 150.00   58
 10  \w     76.00 118.00   0.50    2.00    --  102.63-125.00   0.00   84
 11  \w     99.00 151.00   0.50    2.00    --  102.63  30.00-120.00  104
 12  \w     81.00 113.00   0.50    2.00    --  102.63-125.00 150.00   64
 13  \w    106.00 132.00   0.50    2.00    --  102.63  45.00 -90.00   52
 14  \w     39.00 105.00   0.50    2.00    --  102.63 -45.00-180.00  132
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'SuperNova, Dual, Cu at home/near, Pilatus 200K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0171675000
_diffrn_orient_matrix_UB_12      0.1984520000
_diffrn_orient_matrix_UB_13      0.0489778000
_diffrn_orient_matrix_UB_21      0.0835430000
_diffrn_orient_matrix_UB_22      0.0516626000
_diffrn_orient_matrix_UB_23      -0.0651117000
_diffrn_orient_matrix_UB_31      -0.0301846000
_diffrn_orient_matrix_UB_32      0.0304104000
_diffrn_orient_matrix_UB_33      -0.2087632000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0420
_diffrn_reflns_av_unetI/netI     0.0417
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            3649
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        66.592
_diffrn_reflns_theta_max         66.592
_diffrn_reflns_theta_min         5.195
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.016
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.42686
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.422
_exptl_crystal_description       block
_exptl_crystal_F_000             392
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.169
_refine_diff_density_min         -0.205
_refine_diff_density_rms         0.039
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.69(4)
_refine_ls_extinction_coef       0.0052(9)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/4 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     124
_refine_ls_number_reflns         1230
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.070
_refine_ls_R_factor_all          0.0348
_refine_ls_R_factor_gt           0.0318
_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^)+(0.0447P)^2^+0.0500P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0783
_refine_ls_wR_factor_ref         0.0799
_reflns_Friedel_coverage         0.832
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.997
_reflns_number_gt                1168
_reflns_number_total             1230
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo9b00983_si_002.cif
_cod_data_source_block           vc-pbb-sulfanilimide
_cod_database_code               4034013
_chemical_oxdiff_formula         'C H N S O'
_diffrn_oxdiff_ac3_digest_frames
;
013c45cbc4334299b2a32cfe5569e80aa301458017c
;
_diffrn_oxdiff_ac3_digest_hkl
;
019efd87f94e96b0c310da15df7419950e226f
;
_reflns_odcompleteness_completeness 99.89
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.31(4) 0.69(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C5(H5), C3(H3)
3.b Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              61322
_shelx_hkl_checksum              16111
_shelx_shelxl_version_number     2016/4
_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 2.688
_oxdiff_exptl_absorpt_empirical_full_min 0.433