#------------------------------------------------------------------------------
#$Date: 2019-11-10 18:57:08 +0200 (Sun, 10 Nov 2019) $
#$Revision: 225966 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/51/58/4515874.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_4515874
loop_
_publ_author_name
'Fu, Dong'
'Fabre, Bruno'
'Loget, Gabriel'
'Mériadec, Cristelle'
'Ababou-Girard, Soraya'
'Cadot, Emmanuel'
'Leclerc-Laronze, Nathalie'
'Marrot, Jérôme'
'de Ponfilly, Quentin'
_publ_section_title
;
 Polyoxothiometalate-Derivatized Silicon Photocathodes for Sunlight-Driven
 Hydrogen Evolution Reaction.
;
_journal_issue                   10
_journal_name_full               'ACS omega'
_journal_page_first              13837
_journal_page_last               13849
_journal_paper_doi               10.1021/acsomega.8b01734
_journal_volume                  3
_journal_year                    2018
_chemical_formula_sum            'C27 H45 Cl Mo3 O10 S4'
_chemical_formula_weight         981.14
_space_group_crystal_system      hexagonal
_space_group_IT_number           176
_space_group_name_Hall           '-P 6c'
_space_group_name_H-M_alt        'P 63/m'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2018/3
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   20.702(2)
_cell_length_b                   20.702(2)
_cell_length_c                   16.158(2)
_cell_measurement_reflns_used    9597
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      29.87
_cell_measurement_theta_min      2.27
_cell_volume                     5997.1(11)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_diffrn_ambient_temperature      200(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0119
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            234315
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.030
_diffrn_reflns_theta_min         1.697
_diffrn_source                   'fine-focus sealed tube'
_exptl_absorpt_coefficient_mu    1.248
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS (Sheldrick, V2008/1)'
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.630
_exptl_crystal_description       needle
_exptl_crystal_F_000             2964
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.180
_exptl_crystal_size_min          0.100
_exptl_transmission_factor_max   0.7460
_exptl_transmission_factor_min   0.6348
_refine_diff_density_max         1.885
_refine_diff_density_min         -0.741
_refine_diff_density_rms         0.158
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.147
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     227
_refine_ls_number_reflns         6008
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.148
_refine_ls_R_factor_all          0.0566
_refine_ls_R_factor_gt           0.0500
_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/[σ²(Fo²)+(0.0567P)²+18.3378P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1298
_refine_ls_wR_factor_ref         0.1353
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5391
_reflns_number_total             6008
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            ao8b01734_si_002.cif
_cod_data_source_block           am01
_cod_original_cell_volume        5997.1(16)
_cod_database_code               4515874
_shelx_shelxl_version_number     2018/3
_shelx_space_group_comment
; 
The symmetry employed for this shelxl refinement is uniquely defined 
by the following loop, which should always be used as a source of 
symmetry information in preference to the above space-group names. 
They are only intended as comments. 
;
_shelx_estimated_absorpt_t_min   0.706
_shelx_estimated_absorpt_t_max   0.885
_exptl_absorpt_special_details   'Blessing, Acta Cryst. (1995) A51, 33-38'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-x, -y, z+1/2'
'y, -x+y, z+1/2'
'x-y, x, z+1/2'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'x, y, -z-1/2'
'-y, x-y, -z-1/2'
'-x+y, -x, -z-1/2'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
Mo1 Mo 0.49634(2) 0.46046(2) 0.33488(2) 0.02842(5) Uani 1 1 d . . .
Mo2 Mo 0.42857(2) 0.52494(2) 0.250000 0.02878(6) Uani 1 2 d S T P
S1 S 0.39135(4) 0.39852(4) 0.250000 0.02976(17) Uani 1 2 d S T P
S2 S 0.59742(5) 0.49681(5) 0.250000 0.0366(2) Uani 1 2 d S T P
S3 S 0.51193(3) 0.57671(3) 0.35721(4) 0.03470(13) Uani 1 1 d . . .
O1 O 0.57535(10) 0.48661(10) 0.43911(12) 0.0408(4) Uani 1 1 d . . .
O2 O 0.42623(14) 0.63163(13) 0.250000 0.0377(6) Uani 1 2 d S T P
O3 O 0.48693(10) 0.35552(9) 0.34997(12) 0.0375(4) Uani 1 1 d . . .
O4 O 0.41946(10) 0.41604(9) 0.43519(11) 0.0347(4) Uani 1 1 d . . .
O5 O 0.34121(10) 0.49763(10) 0.33243(12) 0.0368(4) Uani 1 1 d . . .
C1 C 0.43526(16) 0.29390(14) 0.37763(17) 0.0416(6) Uani 1 1 d . . .
C2 C 0.37351(16) 0.28556(14) 0.42280(18) 0.0421(7) Uani 1 1 d . . .
C3 C 0.37147(15) 0.34797(14) 0.45321(17) 0.0387(6) Uani 1 1 d . . .
C4 C 0.3099(2) 0.20857(18) 0.4431(3) 0.0614(10) Uani 1 1 d . . .
H4A H 0.292773 0.208593 0.500347 0.074 Uiso 1 1 calc R U .
H4B H 0.328143 0.172609 0.440901 0.074 Uiso 1 1 calc R U .
C5 C 0.2438(3) 0.1828(3) 0.3841(4) 0.106(2) Uani 1 1 d . . .
H5A H 0.229336 0.221602 0.381334 0.128 Uiso 1 1 calc R U .
H5B H 0.259468 0.177078 0.327911 0.128 Uiso 1 1 calc R U .
C6 C 0.1768(4) 0.1097(4) 0.4099(7) 0.163(4) Uani 1 1 d . . .
H6A H 0.164705 0.113654 0.468314 0.195 Uiso 1 1 calc R U .
H6B H 0.189759 0.069769 0.406665 0.195 Uiso 1 1 calc R U .
C7 C 0.1084(6) 0.0880(7) 0.3569(11) 0.280(7) Uani 1 1 d . . .
H7A H 0.103746 0.132121 0.346369 0.420 Uiso 1 1 calc R U .
H7B H 0.063799 0.050308 0.385958 0.420 Uiso 1 1 calc R U .
H7C H 0.113388 0.067503 0.304182 0.420 Uiso 1 1 calc R U .
C8 C 0.4466(2) 0.22908(16) 0.3604(2) 0.0607(9) Uani 1 1 d . . .
H8A H 0.493424 0.246446 0.330062 0.091 Uiso 1 1 calc R U .
H8B H 0.404986 0.192030 0.326978 0.091 Uiso 1 1 calc R U .
H8C H 0.448760 0.206392 0.412755 0.091 Uiso 1 1 calc R U .
C9 C 0.31297(19) 0.33999(19) 0.5129(2) 0.0562(9) Uani 1 1 d . . .
H9A H 0.328964 0.337839 0.569403 0.084 Uiso 1 1 calc R U .
H9B H 0.266152 0.294023 0.500851 0.084 Uiso 1 1 calc R U .
H9C H 0.305337 0.382871 0.507614 0.084 Uiso 1 1 calc R U .
C10 C 0.27046(15) 0.45825(14) 0.3248(2) 0.0413(6) Uani 1 1 d . . .
C11 C 0.2324(2) 0.4320(2) 0.250000 0.0450(10) Uani 1 2 d S T P
C12 C 0.1484(2) 0.3813(3) 0.250000 0.0629(15) Uani 1 2 d S T P
H12A H 0.127350 0.392223 0.200495 0.076 Uiso 0.5 1 calc R U P
H12B H 0.127351 0.392223 0.299505 0.076 Uiso 0.5 1 calc R U P
C13 C 0.1250(3) 0.2989(3) 0.250000 0.077(2) Uani 1 2 d DS T P
H13A H 0.161429 0.292229 0.283185 0.093 Uiso 0.5 1 calc R U P
H13B H 0.127351 0.283671 0.192509 0.093 Uiso 0.5 1 calc R U P
C14 C 0.0461(4) 0.2464(5) 0.2845(6) 0.080(3) Uani 0.5 1 d D . P
H14A H 0.032747 0.194202 0.272978 0.096 Uiso 0.5 1 calc R U P
H14B H 0.047130 0.252565 0.345302 0.096 Uiso 0.5 1 calc R U P
C15 C -0.0115(6) 0.2594(8) 0.250000 0.280(7) Uani 1 2 d DS T P
H15A H 0.005366 0.312862 0.251830 0.420 Uiso 1 2 calc R U P
H15B H -0.057384 0.232007 0.282534 0.420 Uiso 0.5 1 calc R U P
H15C H -0.021349 0.242099 0.192490 0.420 Uiso 0.5 1 calc R U P
C16 C 0.22964(19) 0.4469(2) 0.4052(2) 0.0649(10) Uani 1 1 d . . .
H16A H 0.265752 0.470901 0.450046 0.097 Uiso 1 1 calc R U .
H16B H 0.199018 0.393386 0.416472 0.097 Uiso 1 1 calc R U .
H16C H 0.197507 0.469018 0.401370 0.097 Uiso 1 1 calc R U .
Cl1 Cl 0.666667 0.333333 0.62460(8) 0.0435(3) Uani 1 3 d S T P
Cl2 Cl 0.666667 0.333333 0.3408(2) 0.0759(11) Uani 0.5 3 d S T P
O1W O 0.6019(3) 0.3828(2) 0.4775(3) 0.0746(10) Uani 0.5 1 d . . P
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mo Mo -1.6832 0.6857 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
O3 Mo1 O4 78.58(7) . .
O3 Mo1 O1 80.77(7) . .
O4 Mo1 O1 80.11(7) . .
O3 Mo1 S3 164.07(6) . .
O4 Mo1 S3 90.92(5) . .
O1 Mo1 S3 85.68(6) . .
O3 Mo1 S2 90.36(6) . .
O4 Mo1 S2 163.56(6) . .
O1 Mo1 S2 86.18(5) . .
S3 Mo1 S2 97.09(3) . .
O3 Mo1 S1 85.45(6) . .
O4 Mo1 S1 85.45(5) . .
O1 Mo1 S1 161.72(5) . .
S3 Mo1 S1 105.82(3) . .
S2 Mo1 S1 105.96(2) . .
O3 Mo1 Mo2 139.33(5) . .
O4 Mo1 Mo2 97.88(6) . .
O1 Mo1 Mo2 139.12(5) . .
S3 Mo1 Mo2 53.449(18) . .
S2 Mo1 Mo2 98.42(2) . .
S1 Mo1 Mo2 53.93(2) . .
O3 Mo1 Mo1 96.68(5) . 10_556
O4 Mo1 Mo1 139.51(5) . 10_556
O1 Mo1 Mo1 139.40(5) . 10_556
S3 Mo1 Mo1 99.062(18) . 10_556
S2 Mo1 Mo1 53.239(15) . 10_556
S1 Mo1 Mo1 54.068(13) . 10_556
Mo2 Mo1 Mo1 59.957(7) . 10_556
O5 Mo2 O5 79.46(11) 10_556 .
O5 Mo2 O2 79.82(7) 10_556 .
O5 Mo2 O2 79.82(7) . .
O5 Mo2 S3 89.55(5) 10_556 10_556
O5 Mo2 S3 162.96(6) . 10_556
O2 Mo2 S3 85.48(5) . 10_556
O5 Mo2 S3 162.96(6) 10_556 .
O5 Mo2 S3 89.55(5) . .
O2 Mo2 S3 85.49(5) . .
S3 Mo2 S3 97.88(3) 10_556 .
O5 Mo2 S1 86.59(6) 10_556 .
O5 Mo2 S1 86.59(6) . .
O2 Mo2 S1 162.28(7) . .
S3 Mo2 S1 105.87(2) 10_556 .
S3 Mo2 S1 105.87(2) . .
O5 Mo2 Mo1 140.74(5) 10_556 .
O5 Mo2 Mo1 97.72(6) . .
O2 Mo2 Mo1 138.73(4) . .
S3 Mo2 Mo1 99.01(2) 10_556 .
S3 Mo2 Mo1 53.245(19) . .
S1 Mo2 Mo1 54.184(18) . .
O5 Mo2 Mo1 97.72(6) 10_556 10_556
O5 Mo2 Mo1 140.74(5) . 10_556
O2 Mo2 Mo1 138.73(4) . 10_556
S3 Mo2 Mo1 53.247(19) 10_556 10_556
S3 Mo2 Mo1 99.01(2) . 10_556
S1 Mo2 Mo1 54.184(18) . 10_556
Mo1 Mo2 Mo1 60.087(14) . 10_556
Mo2 S1 Mo1 71.89(2) . .
Mo2 S1 Mo1 71.89(2) . 10_556
Mo1 S1 Mo1 71.86(3) . 10_556
Mo1 S2 Mo1 73.52(3) 10_556 .
Mo1 S3 Mo2 73.31(2) . .
C1 O3 Mo1 132.7(2) . .
C3 O4 Mo1 130.19(18) . .
C10 O5 Mo2 132.41(19) . .
O3 C1 C2 124.4(3) . .
O3 C1 C8 113.8(3) . .
C2 C1 C8 121.8(2) . .
C3 C2 C1 120.9(2) . .
C3 C2 C4 118.9(3) . .
C1 C2 C4 120.1(3) . .
O4 C3 C2 124.5(3) . .
O4 C3 C9 114.0(3) . .
C2 C3 C9 121.4(2) . .
C2 C4 C5 112.9(4) . .
C2 C4 H4A 109.0 . .
C5 C4 H4A 109.0 . .
C2 C4 H4B 109.0 . .
C5 C4 H4B 109.0 . .
H4A C4 H4B 107.8 . .
C6 C5 C4 113.0(6) . .
C6 C5 H5A 109.0 . .
C4 C5 H5A 109.0 . .
C6 C5 H5B 109.0 . .
C4 C5 H5B 109.0 . .
H5A C5 H5B 107.8 . .
C5 C6 C7 113.2(9) . .
C5 C6 H6A 108.9 . .
C7 C6 H6A 108.9 . .
C5 C6 H6B 108.9 . .
C7 C6 H6B 108.9 . .
H6A C6 H6B 107.8 . .
C6 C7 H7A 109.5 . .
C6 C7 H7B 109.5 . .
H7A C7 H7B 109.5 . .
C6 C7 H7C 109.5 . .
H7A C7 H7C 109.5 . .
H7B C7 H7C 109.5 . .
C1 C8 H8A 109.5 . .
C1 C8 H8B 109.5 . .
H8A C8 H8B 109.5 . .
C1 C8 H8C 109.5 . .
H8A C8 H8C 109.5 . .
H8B C8 H8C 109.5 . .
C3 C9 H9A 109.5 . .
C3 C9 H9B 109.5 . .
H9A C9 H9B 109.5 . .
C3 C9 H9C 109.5 . .
H9A C9 H9C 109.5 . .
H9B C9 H9C 109.5 . .
O5 C10 C11 125.1(3) . .
O5 C10 C16 113.1(3) . .
C11 C10 C16 121.6(3) . .
C10 C11 C10 120.0(3) . 10_556
C10 C11 C12 119.84(17) . .
C10 C11 C12 119.84(17) 10_556 .
C11 C12 C13 112.9(5) . .
C11 C12 H12A 109.0 . .
C13 C12 H12A 109.0 . .
C11 C12 H12B 109.0 . .
C13 C12 H12B 109.0 . .
H12A C12 H12B 107.8 . .
C12 C13 C14 114.9(6) . .
C12 C13 H13A 108.5 . .
C14 C13 H13A 108.5 . .
C12 C13 H13B 108.5 . .
C14 C13 H13B 108.5 . .
H13A C13 H13B 107.5 . .
C12 C13 H13A 108.5(2) . 10_556
C14 C13 H13A 135.1(4) . 10_556
H13A C13 H13A 65.6 . 10_556
H13B C13 H13A 44.3 . 10_556
C12 C13 H13B 108.54(4) . 10_556
C14 C13 H13B 68.9(4) . 10_556
H13A C13 H13B 44.3 . 10_556
H13B C13 H13B 139.5 . 10_556
H13A C13 H13B 107.5 10_556 10_556
C15 C14 C13 114.0(7) . .
C15 C14 H14A 108.7 . .
C13 C14 H14A 108.7 . .
C15 C14 H14B 108.7 . .
C13 C14 H14B 108.7 . .
H14A C14 H14B 107.6 . .
C15 C14 H13B 143.9(8) . 10_556
C13 C14 H13B 37.9(2) . 10_556
H14A C14 H13B 103.7 . 10_556
H14B C14 H13B 75.1 . 10_556
C15 C14 H15C 40(10) . 10_556
C13 C14 H15C 144(10) . 10_556
H14A C14 H15C 104.7 . 10_556
H14B C14 H15C 72.6 . 10_556
H13B C14 H15C 142.0 10_556 10_556
C14 C15 H15A 109.5 . .
C14 C15 H15B 109.5 . .
H15A C15 H15B 109.5 . .
C14 C15 H15C 109.5 . .
H15A C15 H15C 109.5 . .
H15B C15 H15C 109.5 . .
C14 C15 H15B 138.0(12) . 10_556
H15A C15 H15B 111.4 . 10_556
H15B C15 H15B 64.9 . 10_556
H15C C15 H15B 46.9 . 10_556
C14 C15 H15C 67.0(4) . 10_556
H15A C15 H15C 106.0 . 10_556
H15B C15 H15C 46.9 . 10_556
H15C C15 H15C 143.0 . 10_556
H15B C15 H15C 109.5 10_556 10_556
C10 C16 H16A 109.5 . .
C10 C16 H16B 109.5 . .
H16A C16 H16B 109.5 . .
C10 C16 H16C 109.5 . .
H16A C16 H16C 109.5 . .
H16B C16 H16C 109.5 . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Mo1 O3 2.0961(19) .
Mo1 O4 2.1312(18) .
Mo1 O1 2.2180(19) .
Mo1 S3 2.2913(7) .
Mo1 S2 2.2916(8) .
Mo1 S1 2.3370(7) .
Mo1 Mo2 2.7392(4) .
Mo1 Mo1 2.7429(5) 10_556
Mo2 O5 2.0838(18) 10_556
Mo2 O5 2.0838(18) .
Mo2 O2 2.233(3) .
Mo2 S3 2.2973(7) 10_556
Mo2 S3 2.2973(7) .
Mo2 S1 2.3294(9) .
O3 C1 1.268(3) .
O4 C3 1.288(3) .
O5 C10 1.277(3) .
C1 C2 1.406(4) .
C1 C8 1.499(5) .
C2 C3 1.402(4) .
C2 C4 1.511(4) .
C3 C9 1.491(5) .
C4 C5 1.528(7) .
C4 H4A 0.9900 .
C4 H4B 0.9900 .
C5 C6 1.512(8) .
C5 H5A 0.9900 .
C5 H5B 0.9900 .
C6 C7 1.519(16) .
C6 H6A 0.9900 .
C6 H6B 0.9900 .
C7 H7A 0.9800 .
C7 H7B 0.9800 .
C7 H7C 0.9800 .
C8 H8A 0.9800 .
C8 H8B 0.9800 .
C8 H8C 0.9800 .
C9 H9A 0.9800 .
C9 H9B 0.9800 .
C9 H9C 0.9800 .
C10 C11 1.396(4) .
C10 C16 1.502(5) .
C11 C12 1.517(6) .
C12 C13 1.522(8) .
C12 H12A 0.9900 .
C12 H12B 0.9900 .
C13 C14 1.543(8) .
C13 H13A 0.9900 .
C13 H13B 0.9900 .
C13 H13A 0.9899 10_556
C13 H13B 0.9900 10_556
C14 C15 1.460(13) .
C14 H14A 0.9900 .
C14 H14B 0.9900 .
C14 H15C 1.40(7) 10_556
C15 H15A 0.9800 .
C15 H15B 0.9800 .
C15 H15C 0.9800 .
C15 H15B 1.0(4) 10_556
C15 H15C 1.0(2) 10_556
C16 H16A 0.9800 .
C16 H16B 0.9800 .
C16 H16C 0.9800 .
