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_1553990
_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         'Br6 Mo3 S7, 2(C24 H20 P)'
_chemical_formula_sum            'C48 H40 Br6 Mo3 P2 S7'
_chemical_formula_weight         1670.44
_chemical_name_systematic        C48H40P2Mo3S7Br6
_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             2016-06-28
_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                   17.9676(3)
_cell_length_b                   25.7114(6)
_cell_length_c                   27.2220(5)
_cell_measurement_reflns_used    18089
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      28.7720
_cell_measurement_theta_min      3.4400
_cell_volume                     12575.8(4)
_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      150.00(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 0.881
_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    -64.00  39.00   1.00  103.26    --   11.14 -77.00-150.00  103
  2  \w     -1.00  24.00   1.00  103.26    --   11.14 -38.00  30.00   25
  3  \w    -21.00  19.00   1.00  103.26    --   11.14 -19.00-120.00   40
;
_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      -0.0171884000
_diffrn_orient_matrix_UB_12      -0.0024928000
_diffrn_orient_matrix_UB_13      -0.0233484000
_diffrn_orient_matrix_UB_21      0.0283911000
_diffrn_orient_matrix_UB_22      0.0155573000
_diffrn_orient_matrix_UB_23      -0.0105777000
_diffrn_orient_matrix_UB_31      0.0213932000
_diffrn_orient_matrix_UB_32      -0.0226324000
_diffrn_orient_matrix_UB_33      -0.0046971000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0312
_diffrn_reflns_av_unetI/netI     0.0354
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.881
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       37
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            58921
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.881
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         29.432
_diffrn_reflns_theta_min         2.972
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.715
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78588
_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 reddish brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.765
_exptl_crystal_description       block
_exptl_crystal_F_000             6448
_exptl_crystal_recrystallization_method Acetonitrile/acetone
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.155
_refine_diff_density_min         -1.461
_refine_diff_density_rms         0.122
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.135
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     595
_refine_ls_number_reflns         15343
_refine_ls_number_restraints     480
_refine_ls_restrained_S_all      1.141
_refine_ls_R_factor_all          0.0668
_refine_ls_R_factor_gt           0.0451
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0609P)^2^+12.5204P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1182
_refine_ls_wR_factor_ref         0.1266
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11215
_reflns_number_total             15343
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7se00599g2.cif
_cod_data_source_block           bs16040
_cod_database_code               1553990
_reflns_odcompleteness_completeness 99.68
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C40-C33 = C8-C2 = C2-C11 = C3-C10 = C3-C18 = C5-C12 = C5-C16 = C9-C7 = C7-C31
 = C8-C14 = C13-C11 = C21-C10 = C23-C18 = C17-C12 = C40-C16 = C9-C30 = C32-C31 =
  C15-C14 = C15-C13 = C22-C21 = C23-C22 = C33-C17 = C34-C30 = C34-C32 = C27-C1 =
  C28-C1 = C4-C36 = C44-C4 = C6-C20 = C6-C25 = C42-C19 = C43-C19 = C35-C27 =
 C41-C28 = C36-C24 = C45-C44 = C38-C20 = C37-C25 = C48-C42 = C46-C43 = C35-C29 =
  C41-C29 = C26-C24 = C45-C26 = C39-C38 = C39-C37 = C48-C47 = C47-C46
 1.35 with sigma of 0.02
 C17-C12 = C8-C2 = C2-C11 = C3-C10 = C3-C18 = C5-C12 = C5-C16 = C9-C7 = C7-C31
 = C8-C14 = C13-C11 = C21-C10 = C23-C18 = C40-C16 = C9-C30 = C32-C31 = C15-C14 =
  C15-C13 = C22-C21 = C23-C22 = C33-C17 = C40-C33 = C34-C30 = C34-C32 = C27-C1 =
  C28-C1 = C4-C36 = C44-C4 = C6-C20 = C6-C25 = C42-C19 = C43-C19 = C35-C27 =
 C41-C28 = C36-C24 = C45-C44 = C38-C20 = C37-C25 = C48-C42 = C46-C43 = C35-C29 =
  C41-C29 = C26-C24 = C45-C26 = C39-C38 = C39-C37 = C48-C47 = C47-C46
 1.4 with sigma of 0.02
3. Rigid bond restraints
 C2, C3, C5, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C21, C22,
  C23, C30, C31, C32, C33, C34, C40, C1, C4, C6, C19, C20, C24, C25, C26, C27,
 C28, C29, C35, C36, C37, C38, C39, C41, C42, C43, C44, C45, C46, C47, C48
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 H8, H9, H10, H11, H12, H13, H14, H15, H16, H17, H18, H21, H22, H23, H30, H31,
 H32, H33, H34, H40, H20, H24, H25, H26, H28, H29, H35, H36, H37, H38, H39, H41,
  H42, H43, H44, H45, H46, H47, H48
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S16, P1, P2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 H8, H9, H10, H11, H12, H13, H14, H15, H16, H17, H18, H21, H22, H23, H30, H31,
 H32, H33, H34, H40, H20, H24, H25, H26, H27, H28, H29, H35, H36, H37, H38, H39,
  H41, H42, H43, H44, H45, H46, H47, H48
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C2 \\sim C3 \\sim C5 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12
\\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C21 \\sim C22
\\sim C23 \\sim C30 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C40 \\sim C1
\\sim C4 \\sim C6 \\sim C19 \\sim C20 \\sim C24 \\sim C25 \\sim C26 \\sim C27
\\sim C28 \\sim C29 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C41
\\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46 \\sim C47 \\sim C48: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
H8 \\sim H9 \\sim H10 \\sim H11 \\sim H12 \\sim H13 \\sim H14 \\sim H15 \\sim
H16 \\sim H17 \\sim H18 \\sim H21 \\sim H22 \\sim H23 \\sim H30 \\sim H31 \\sim
H32 \\sim H33 \\sim H34 \\sim H40 \\sim H20 \\sim H24 \\sim H25 \\sim H26 \\sim
H28 \\sim H29 \\sim H35 \\sim H36 \\sim H37 \\sim H38 \\sim H39 \\sim H41 \\sim
H42 \\sim H43 \\sim H44 \\sim H45 \\sim H46 \\sim H47 \\sim H48: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
S16 \\sim P1 \\sim P2: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
H8 \\sim H9 \\sim H10 \\sim H11 \\sim H12 \\sim H13 \\sim H14 \\sim H15 \\sim
H16 \\sim H17 \\sim H18 \\sim H21 \\sim H22 \\sim H23 \\sim H30 \\sim H31 \\sim
H32 \\sim H33 \\sim H34 \\sim H40 \\sim H20 \\sim H24 \\sim H25 \\sim H26 \\sim
H27 \\sim H28 \\sim H29 \\sim H35 \\sim H36 \\sim H37 \\sim H38 \\sim H39 \\sim
H41 \\sim H42 \\sim H43 \\sim H44 \\sim H45 \\sim H46 \\sim H47 \\sim H48:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
5.a Aromatic/amide H refined with riding coordinates:
 C8(H8), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C21(H21), C22(H22), C23(H23), C30(H30), C31(H31),
  C32(H32), C33(H33), C34(H34), C40(H40), C20(H20), C24(H24), C25(H25),
 C26(H26), C27(H27), C28(H28), C29(H29), C35(H35), C36(H36), C37(H37), C38(H38),
  C39(H39), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C46(H46),
 C47(H47), C48(H48)
;
_shelx_res_checksum              12715
_shelx_hkl_checksum              59860
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id C48H40P2Mo3S7Br6
_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 1.193
_oxdiff_exptl_absorpt_empirical_full_min 0.815