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_4517184
_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         'C30 H32 Mo N P S'
_chemical_formula_sum            'C30 H32 Mo N P S'
_chemical_formula_weight         565.57
_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'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2019-06-10
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90.632(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.1248(2)
_cell_length_b                   18.1970(3)
_cell_length_c                   12.9432(2)
_cell_measurement_reflns_used    7117
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      76.6800
_cell_measurement_theta_min      4.1550
_cell_volume                     2620.04(8)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.9889
_diffrn_measured_fraction_theta_max 0.9889
_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 -41.00   1.00    0.13    --  -48.45 -27.00  72.00   25
  2  \w   -123.00 -93.00   1.00    0.13    --  -48.45 -27.00  72.00   30
  3  \w    -61.00  25.00   1.00    0.13    --  -48.45  27.00-124.00   86
  4  \w   -115.00 -78.00   1.00    0.52    --  -86.25 -27.00  72.00   37
  5  \w    -52.00 -26.00   1.00    0.52    --  -86.25  27.00-124.00   26
  6  \w    -99.00 -59.00   1.00    0.52    --  -86.25  27.00-124.00   40
  7  \w    135.00 176.00   1.00    0.52    --  107.75  27.00-124.00   41
  8  \w     36.00  64.00   1.00    0.52    --  107.75 -27.00  72.00   28
  9  \w     56.00  81.00   1.00    0.13    --   48.45  27.00-124.00   25
 10  \w    -23.00  17.00   1.00    0.13    --   48.45 -37.00   0.00   40
 11  \w    -23.00   2.00   1.00    0.13    --   48.45 -27.00  72.00   25
 12  \w     20.00  61.00   1.00    0.13    --   48.45 -37.00   0.00   41
 13  \w    -90.00 -22.00   1.00    0.52    --  -86.25 125.00 -60.00   68
 14  \w     33.00 118.00   1.00    0.52    --  107.75 -19.00 150.00   85
 15  \w     41.00 109.00   1.00    0.52    --  107.75 -99.00  90.00   68
 16  \w     33.00 120.00   1.00    0.52    --  107.75 -19.00-120.00   87
 17  \w     37.00 106.00   1.00    0.52    --  107.75 -99.00  30.00   69
 18  \w     67.00 114.00   1.00    0.52    --  107.75 -27.00  72.00   47
;
_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      0.1299588000
_diffrn_orient_matrix_UB_12      0.0262463000
_diffrn_orient_matrix_UB_13      0.0189664000
_diffrn_orient_matrix_UB_21      0.0283519000
_diffrn_orient_matrix_UB_22      -0.0130685000
_diffrn_orient_matrix_UB_23      -0.1148378000
_diffrn_orient_matrix_UB_31      -0.0385516000
_diffrn_orient_matrix_UB_32      0.0793572000
_diffrn_orient_matrix_UB_33      -0.0253235000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0579
_diffrn_reflns_av_unetI/netI     0.0594
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            15568
_diffrn_reflns_theta_full        67.0759
_diffrn_reflns_theta_max         67.08
_diffrn_reflns_theta_min         4.19
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    5.548
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58480
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.4337
_exptl_crystal_description       block
_exptl_crystal_F_000             1172.6844
_refine_diff_density_max         1.8521
_refine_diff_density_min         -0.9901
_refine_diff_density_rms         0.1826
_refine_ls_d_res_high            0.8370
_refine_ls_d_res_low             10.5469
_refine_ls_goodness_of_fit_ref   1.0278
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    52
_refine_ls_number_parameters     313
_refine_ls_number_reflns         4632
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.0278
_refine_ls_R_factor_all          0.0585
_refine_ls_R_factor_gt           0.0433
_refine_ls_shift/su_max          0.0127
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0400P)^2^+7.4193P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1017
_refine_ls_wR_factor_ref         0.1163
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              10
_reflns_limit_h_min              -13
_reflns_limit_k_max              21
_reflns_limit_k_min              0
_reflns_limit_l_max              15
_reflns_limit_l_min              -9
_reflns_number_gt                3907
_reflns_number_total             4632
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            cs9b04455_si_002.cif
_cod_data_source_block           180524HSF-1
_cod_original_sg_symbol_Hall     '-P 2ybc (x-z,y,z)'
_cod_database_code               4517184
_chemical_oxdiff_formula         MoPNCHS
_reflns_odcompleteness_completeness 98.95
_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:
 C15(H15), C20(H20), C30(H30), C26(H26), C29(H29), C24(H24), C27(H27),
 C18(H18), C16(H16), C21(H21), C23(H23), C28(H28), C22(H22), C17(H17)
2.b Idealised Me refined as rotating group:
 C10(H10a,H10b,H10c), C9(H9a,H9b,H9c), C12(H12a,H12b,H12c), C6(H6a,H6b,H6c),
 C8(H8a,H8b,H8c), C7(H7a,H7b,H7c)
;
_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 1.778
_oxdiff_exptl_absorpt_empirical_full_min 0.426