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_4517183
_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         'C34 H38 Mo N3 P S, 2(B F4)'
_chemical_formula_sum            'C34 H38 B2 F8 Mo N3 P S'
_chemical_formula_weight         821.26
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-06-11
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                75.533(3)
_cell_angle_beta                 73.017(4)
_cell_angle_gamma                67.252(4)
_cell_formula_units_Z            2
_cell_length_a                   11.1302(5)
_cell_length_b                   13.2104(5)
_cell_length_c                   13.9442(5)
_cell_measurement_reflns_used    6324
_cell_measurement_temperature    172.99(10)
_cell_measurement_theta_max      76.4880
_cell_measurement_theta_min      4.4370
_cell_volume                     1786.43(14)
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      173.0
_diffrn_measured_fraction_theta_full 0.972
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.710
_diffrn_reflns_av_R_equivalents  0.0399
_diffrn_reflns_av_unetI/netI     0.0488
_diffrn_reflns_Laue_measured_fraction_full 0.972
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            11933
_diffrn_reflns_point_group_measured_fraction_full 0.972
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.214
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.544
_exptl_absorpt_coefficient_mu    0.542
_exptl_crystal_density_diffrn    1.527
_exptl_crystal_description       block
_exptl_crystal_F_000             836
_refine_diff_density_max         1.375
_refine_diff_density_min         -1.122
_refine_diff_density_rms         0.087
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     459
_refine_ls_number_reflns         6298
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.081
_refine_ls_R_factor_all          0.0519
_refine_ls_R_factor_gt           0.0438
_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^)+(0.0489P)^2^+2.7534P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1065
_refine_ls_wR_factor_ref         0.1135
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5515
_reflns_number_total             6298
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cs9b04455_si_002.cif
_cod_data_source_block           p
_cod_database_code               4517183
_shelxl_version_number           2013-4
_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. Rigid bond restraints
 P1, Mo1
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.001
 Mo1, P1
 with sigma for 1-2 distances of 0.0002 and sigma for 1-3 distances of 0.0001
3. Uiso/Uaniso restraints and constraints
P1 \\sim Mo1: within 1.7A with sigma of 0.004 and sigma for terminal atoms of
0.008
4.a Aromatic/amide H refined with riding coordinates:
 C28(H28), C34(H34), C22(H22), C19(H19), C26(H26), C31(H31), C25(H25),
 C30(H30), C18(H18), C21(H21), C33(H33), C27(H27), C32(H32), C20(H20)
4.b Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C12(H12A,H12B,H12C), C16(H16A,H16B,H16C), C9(H9A,H9B,
 H9C), C6(H6A,H6B,H6C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C), C7(H7A,H7B,H7C)
;
_shelx_res_checksum              81700
_shelx_hkl_checksum              60086
_olex2_submission_special_instructions 'No special instructions were received'