Cooperative Molybdenum-Thiolate Reactivity for Transfer Hydrogenation of Nitriles
Hou, Shu-Fen; Chen, Jia-Yi; Xue, Minghui; Jia, Mengjing; Zhai, Xiaofang; Liao, Rong-Zhen; Tung, Chen-Ho; Wang, Wenguang; ACS Catalysis  (2019) 380–; doi:10.1021/acscatal.9b04455

data_4517185
_publ_section_title
;
 Cooperative Molybdenum-Thiolate Reactivity for Transfer Hydrogenation of
 Nitriles
;
_journal_name_full               'ACS Catalysis'
_journal_page_first              380
_journal_paper_doi               10.1021/acscatal.9b04455
_journal_year                    2019
_chemical_formula_moiety         'C28 H32 B Mo P S'
_chemical_formula_sum            'C28 H32 B Mo P S'
_chemical_formula_weight         538.31
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2019-09-09
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.260(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.8462(2)
_cell_length_b                   16.9076(3)
_cell_length_c                   14.8894(3)
_cell_measurement_reflns_used    10189
_cell_measurement_temperature    173.00(10)
_cell_measurement_theta_max      76.1000
_cell_measurement_theta_min      4.0030
_cell_volume                     2634.19(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.25a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.25a (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_environment      N~2~
_diffrn_ambient_temperature      173.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.978
_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   -120.00 -69.00   1.00    0.10    --  -48.45-130.00-104.00   51
  2  \w    -86.00 -61.00   1.00    0.10    --  -48.45 140.00 141.00   25
  3  \w   -114.00 -89.00   1.00    0.10    --  -48.45-140.00  81.00   25
  4  \w     53.00 105.00   1.00    0.10    --   48.45-140.00  81.00   52
  5  \w     42.00  67.00   1.00    0.10    --   48.45-130.00-104.00   25
  6  \w   -134.00 -76.00   1.00    0.10    --  -86.25-130.00-104.00   58
  7  \w    -84.00 -59.00   1.00    0.10    --  -86.25 140.00 141.00   25
  8  \w    106.00 131.00   1.00    0.10    --  106.49 140.00 141.00   25
  9  \w     82.00 126.00   1.00    0.10    --  106.49-140.00  81.00   44
 10  \w    109.00 134.00   1.00    0.10    --  106.49 130.00 -32.00   25
 11  \w     35.00 119.00   1.00    0.10    --  106.49-130.00-104.00   84
 12  \w   -112.00 -27.00   1.00    0.10    --  -48.45 -77.00-120.00   85
 13  \w   -148.00 -80.00   1.00    0.10    --  -86.25 -94.00   0.00   68
 14  \w    103.00 178.00   1.00    0.10    --  106.49  30.00 -30.00   75
 15  \w     36.00 107.00   1.00    0.10    --  106.49 -94.00  60.00   71
 16  \w     37.00 119.00   1.00    0.10    --  106.49 -30.00-180.00   82
 17  \w     39.00 119.00   1.00    0.10    --  106.49 -45.00-150.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1355458000
_diffrn_orient_matrix_UB_12      -0.0337423000
_diffrn_orient_matrix_UB_13      -0.0132070000
_diffrn_orient_matrix_UB_21      -0.0532728000
_diffrn_orient_matrix_UB_22      0.0845630000
_diffrn_orient_matrix_UB_23      -0.0010513000
_diffrn_orient_matrix_UB_31      -0.0214760000
_diffrn_orient_matrix_UB_32      0.0033150000
_diffrn_orient_matrix_UB_33      -0.1064048000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0475
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            16030
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.055
_diffrn_reflns_theta_min         4.038
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.471
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.35349
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.25a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.357
_exptl_crystal_description       block
_exptl_crystal_F_000             1112
_refine_diff_density_max         0.966
_refine_diff_density_min         -0.744
_refine_diff_density_rms         0.111
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     306
_refine_ls_number_reflns         4648
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0463
_refine_ls_R_factor_gt           0.0364
_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^)+(0.0466P)^2^+5.3849P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0933
_refine_ls_wR_factor_ref         0.1029
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4190
_reflns_number_total             4648
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04455_si_002.cif
_cod_data_source_block           20190327hsf-1
_cod_database_code               4517185
_shelxl_version_number           2013-4
_reflns_odcompleteness_completeness 99.30
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C18(H18), C19(H19), C22(H22), C20(H20), C28(H28), C16(H16), C13(H13),
 C21(H21), C24(H24), C27(H27), C26(H26), C14(H14), C15(H15), C25(H25)
2.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C6(H6A,H6B,H6C),
 C7(H7A,H7B,H7C)
;
_shelx_res_checksum              23289
_shelx_hkl_checksum              4388
_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 1.772
_oxdiff_exptl_absorpt_empirical_full_min 0.626