Understanding homogeneous hydrogen evolution reactivity and deactivation pathways of molecular molybdenum sulfide catalysts
Dave, M.; Rajagopal, A.; Damm-Ruttensperger, M.; Schwarz, B.; Nägele, F.; Daccache, L.; Fantauzzi, D.; Jacob, T.; Streb, C.; Sustainable Energy & Fuels 2 (2018) 1020–; doi:10.1039/C7SE00599G

data_1553991
_publ_section_title
;
 Understanding homogeneous hydrogen evolution reactivity and deactivation
 pathways of molecular molybdenum sulfide catalysts
;
_journal_issue                   5
_journal_name_full               'Sustainable Energy &amp; Fuels'
_journal_page_first              1020
_journal_paper_doi               10.1039/C7SE00599G
_journal_volume                  2
_journal_year                    2018
_chemical_formula_moiety         'Cl6 Mo3 S7, 2(C16 H36 N)'
_chemical_formula_sum            'C32 H72 Cl6 Mo3 N2 S7'
_chemical_formula_weight         1209.85
_chemical_name_systematic        C32H72Cl6Mo3S7N2
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_audit_update_record
;
2017-08-17 deposited with the CCDC.
2018-03-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.3547(3)
_cell_length_b                   18.6200(3)
_cell_length_c                   29.2421(5)
_cell_measurement_reflns_used    19477
_cell_measurement_temperature    150.05(10)
_cell_measurement_theta_max      29.1020
_cell_measurement_theta_min      3.1840
_cell_volume                     9993.9(3)
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.05(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.3385
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.892
_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     36.00  66.00   1.00   60.00    --   11.14-178.00 -90.00   30
  2  \w    -62.00 -37.00   1.00   60.00    --   11.14 -57.00-180.00   25
  3  \w      4.00  39.00   1.00   60.00    --   11.14 -57.00-180.00   35
  4  \w    -19.00  51.00   1.00   60.00    --   11.14 -99.00 120.00   70
  5  \w     38.00  63.00   1.00   60.00    --   11.14  19.00-120.00   25
  6  \w     59.00  84.00   1.00   60.00    --   11.14  38.00  30.00   25
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0125347000
_diffrn_orient_matrix_UB_12      -0.0327337000
_diffrn_orient_matrix_UB_13      -0.0096043000
_diffrn_orient_matrix_UB_21      -0.0187429000
_diffrn_orient_matrix_UB_22      0.0194421000
_diffrn_orient_matrix_UB_23      -0.0172143000
_diffrn_orient_matrix_UB_31      0.0313956000
_diffrn_orient_matrix_UB_32      -0.0014590000
_diffrn_orient_matrix_UB_33      -0.0141169000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0382
_diffrn_reflns_av_unetI/netI     0.0371
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.892
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            54440
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.892
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.425
_diffrn_reflns_theta_min         2.999
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.380
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60278
_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 dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.608
_exptl_crystal_description       block
_exptl_crystal_F_000             4944
_exptl_crystal_recrystallization_method
;
Acetonitrile/diethyl ether
acetonitrile/diethylether
;
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         3.438
_refine_diff_density_min         -1.309
_refine_diff_density_rms         0.181
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     459
_refine_ls_number_reflns         12332
_refine_ls_number_restraints     827
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0881
_refine_ls_R_factor_gt           0.0641
_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^)+(0.0755P)^2^+86.1963P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1665
_refine_ls_wR_factor_ref         0.1858
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9512
_reflns_number_total             12332
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7se00599g2.cif
_cod_data_source_block           bs16061
_cod_database_code               1553991
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C32-C31
 1.5 with sigma of 0.02
3. Rigid bond restraints
 N1, C1, C3, C4, C5, C6, C2, C9, C10, C11, C13, C8, C7, C25, C30, C29, C12, N2,
  C14, C19, C15, C18, C20, C16, C17, C23, C22, C24, C21, C27, C26, C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N1, C1, H1A, H1B, C3, C4, C5, C6, C2, H3A, H3B, H4A, H4B, C9, H5A, H5B, C10,
 H6A, H6B, C11, H2A, H2B, C13, C8, H9A, H9B, C7, H10A, H10B, H11A, H11B, C30,
 H13A, H13B, H13C, H8A, H8B, C12, H7A, H7B, C25, C29, H30A, H30B, H12A, H12B,
 H12C, H25A, H25B, H25C, H29A, H29B, H29C, N2, C14, H14A, H14B, C19, C15, C18,
 C20, C16, H19A, H19B, H15A, H15B, C17, H18A, H18B, C23, H20A, H20B, C22, C24,
 H17A, H17B, C21, H23A, H23B, C27, H24A, H24B, H24C, H21A, H21B, C26, H27A,
 H27B, C28, H26A, H26B, H26C, H28A, H28B, H28C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 N1, C1, H1A, H1B, C3, C4, C5, C6, C2, H3A, H3B, H4A, H4B, C9, H5A, H5B, C10,
 H6A, H6B, C11, H9B, H11A, H11B, H2A, H2B, C13, C8, H9A, C7, H10A, H10B, C25,
 C30, C29, H13A, H13B, H13C, H8A, H8B, C12, H7A, H7B, H25A, H25B, H25C, H30A,
 H30B, H29A, H29B, H29C, H12A, H12B, H12C, N2, C14, H14A, H14B, C19, C15, C18,
 C20, C16, H19A, H19B, H15A, H15B, C17, H18A, H18B, C23, H20A, H20B, C22, C24,
 H17A, H17B, C21, H23A, H23B, C27, H24A, H24B, H24C, H21A, H21B, C26, H27A,
 H27B, C28, H26A, H26B, H26C, H28A, H28B, H28C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C14, H14A, H14B, N2, C19, C15, C18, C20, C16, H19A, H19B, H15A, H15B, C17,
 H18A, H18B, C23, H20A, H20B, C22, C24, H17A, H17B, C21, H23A, H23B, C27, C32,
 H24A, H24B, H24C, H21A, H21B, C26, H27A, H27B, C28, C31, H26A, H26B, H26C,
 H28A, H28B, H28C
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
N2 \\sim C14 \\sim C19 \\sim C15 \\sim C18 \\sim C20 \\sim C16 \\sim C17 \\sim
C23 \\sim C22 \\sim C24 \\sim C21 \\sim C27 \\sim C26 \\sim C28 \\sim N1 \\sim
C1 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C2 \\sim C9 \\sim C10 \\sim C11
\\sim C13 \\sim C8 \\sim C7 \\sim C25 \\sim C30 \\sim C29 \\sim C12: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08
N1 \\sim C1 \\sim H1A \\sim H1B \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C2
\\sim H3A \\sim H3B \\sim H4A \\sim H4B \\sim C9 \\sim H5A \\sim H5B \\sim C10
\\sim H6A \\sim H6B \\sim C11 \\sim H2A \\sim H2B \\sim C13 \\sim C8 \\sim H9A
\\sim H9B \\sim C7 \\sim H10A \\sim H10B \\sim H11A \\sim H11B \\sim C30 \\sim
H13A \\sim H13B \\sim H13C \\sim H8A \\sim H8B \\sim C12 \\sim H7A \\sim H7B
\\sim C25 \\sim C29 \\sim H30A \\sim H30B \\sim H12A \\sim H12B \\sim H12C
\\sim H25A \\sim H25B \\sim H25C \\sim H29A \\sim H29B \\sim H29C \\sim N2
\\sim C14 \\sim H14A \\sim H14B \\sim C19 \\sim C15 \\sim C18 \\sim C20 \\sim
C16 \\sim H19A \\sim H19B \\sim H15A \\sim H15B \\sim C17 \\sim H18A \\sim H18B
\\sim C23 \\sim H20A \\sim H20B \\sim C22 \\sim C24 \\sim H17A \\sim H17B \\sim
C21 \\sim H23A \\sim H23B \\sim C27 \\sim H24A \\sim H24B \\sim H24C \\sim H21A
\\sim H21B \\sim C26 \\sim H27A \\sim H27B \\sim C28 \\sim H26A \\sim H26B
\\sim H26C \\sim H28A \\sim H28B \\sim H28C: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
N2 \\sim C14 \\sim H14A \\sim H14B \\sim C19 \\sim C15 \\sim C18 \\sim C20
\\sim C16 \\sim H19A \\sim H19B \\sim H15A \\sim H15B \\sim C17 \\sim H18A
\\sim H18B \\sim C23 \\sim H20A \\sim H20B \\sim C22 \\sim C24 \\sim H17A \\sim
H17B \\sim C21 \\sim H23A \\sim H23B \\sim C27 \\sim H24A \\sim H24B \\sim H24C
\\sim H21A \\sim H21B \\sim C26 \\sim H27A \\sim H27B \\sim C28 \\sim H26A
\\sim H26B \\sim H26C \\sim H28A \\sim H28B \\sim H28C \\sim N1 \\sim C1 \\sim
H1A \\sim H1B \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C2 \\sim H3A \\sim H3B
\\sim H4A \\sim H4B \\sim C9 \\sim H5A \\sim H5B \\sim C10 \\sim H6A \\sim H6B
\\sim C11 \\sim H9B \\sim H11A \\sim H11B \\sim H2A \\sim H2B \\sim C13 \\sim
C8 \\sim H9A \\sim C7 \\sim H10A \\sim H10B \\sim C25 \\sim C30 \\sim C29 \\sim
H13A \\sim H13B \\sim H13C \\sim H8A \\sim H8B \\sim C12 \\sim H7A \\sim H7B
\\sim H25A \\sim H25B \\sim H25C \\sim H30A \\sim H30B \\sim H29A \\sim H29B
\\sim H29C \\sim H12A \\sim H12B \\sim H12C: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08
N2 \\sim C14 \\sim H14A \\sim H14B \\sim C19 \\sim C15 \\sim C18 \\sim C20
\\sim C16 \\sim H19A \\sim H19B \\sim H15A \\sim H15B \\sim C17 \\sim H18A
\\sim H18B \\sim C23 \\sim H20A \\sim H20B \\sim C22 \\sim C24 \\sim H17A \\sim
H17B \\sim C21 \\sim H23A \\sim H23B \\sim C27 \\sim C32 \\sim H24A \\sim H24B
\\sim H24C \\sim H21A \\sim H21B \\sim C26 \\sim H27A \\sim H27B \\sim C28
\\sim C31 \\sim H26A \\sim H26B \\sim H26C \\sim H28A \\sim H28B \\sim H28C:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B),
 C7(H7A,H7B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B),
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B),
  C19(H19A,H19B), C20(H20A,H20B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,
 H23B), C27(H27A,H27B), C30(H30A,H30B), C32(H32A,H32B)
5.b Idealised Me refined as rotating group:
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C24(H24A,H24B,H24C), C25(H25A,H25B,
 H25C), C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C31(H31A,
 H31B,H31C)
;
_shelx_res_checksum              64873
_shelx_hkl_checksum              44381
_shelx_shelxl_version_number     2014/7
_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 1.758
_oxdiff_exptl_absorpt_empirical_full_min 0.695