# Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.
# This journal is © the Partner Organisations 2016

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_ay66m
_database_code_depnum_ccdc_archive 'CCDC 1053806'
_audit_update_record             
;
2016-02-02 deposited with the CCDC.
2016-03-30 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C16 H16 O3 S'
_chemical_formula_sum            'C16 H16 O3 S'
_chemical_formula_weight         288.35

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'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_H-M_alt        'P 21 21 21'
_space_group_name_Hall           'P 2ac 2ab'

_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.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'

_cell_length_a                   5.9262(4)
_cell_length_b                   8.0475(5)
_cell_length_c                   31.957(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     1524.08(17)
_cell_formula_units_Z            4
_cell_measurement_temperature    294(2)
_cell_measurement_reflns_used    3190
_cell_measurement_theta_min      2.55
_cell_measurement_theta_max      19.61

_exptl_crystal_description       needle
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.257
_exptl_crystal_F_000             608
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.070
_exptl_absorpt_coefficient_mu    0.216
_shelx_estimated_absorpt_T_min   0.966
_shelx_estimated_absorpt_T_max   0.985
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.89
_exptl_absorpt_correction_T_max  0.95
_exptl_absorpt_process_details   'SABABS; Bruker,2001'

_diffrn_ambient_temperature      294(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area-detector'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16245
_diffrn_reflns_av_unetI/netI     0.0220
_diffrn_reflns_av_R_equivalents  0.0316
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_theta_min         2.549
_diffrn_reflns_theta_max         26.241
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3077
_reflns_number_gt                2225
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.687
_reflns_Friedel_fraction_max     1.000
_reflns_Friedel_fraction_full    1.000

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'SMART (Bruker, 2001)'
_computing_cell_refinement       'SAINT (Bruker, 2001)'
_computing_data_reduction        'SAINT (Bruker, 2001)'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2015)'
_computing_molecular_graphics    'SHELXL2014 (Sheldrick, 2015)'
_computing_publication_material  'SHELXL2014 (Sheldrick, 2015)'

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0923P)²+0.1152P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 658 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         3077
_refine_ls_number_parameters     201
_refine_ls_number_restraints     36
_refine_ls_R_factor_all          0.0890
_refine_ls_R_factor_gt           0.0663
_refine_ls_wR_factor_ref         0.1804
_refine_ls_wR_factor_gt          0.1648
_refine_ls_goodness_of_fit_ref   1.117
_refine_ls_restrained_S_all      1.112
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

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
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.3349(10) 0.9987(7) 0.77730(19) 0.0992(16) Uani 1 1 d . . . . .
C2 C 0.4139(10) 0.9153(7) 0.7425(3) 0.1107(19) Uani 1 1 d . . . . .
H2 H 0.5483 0.8561 0.7445 0.133 Uiso 1 1 calc R U . . .
C3 C 0.3010(11) 0.9171(7) 0.7055(2) 0.0996(15) Uani 1 1 d . . . . .
H3 H 0.3586 0.8603 0.6825 0.120 Uiso 1 1 calc R U . . .
C4 C 0.1031(8) 1.0024(7) 0.70223(15) 0.0831(12) Uani 1 1 d . . . . .
C5 C 0.0192(9) 1.0850(7) 0.73592(17) 0.0909(15) Uani 1 1 d . . . . .
H5 H -0.1161 1.1428 0.7337 0.109 Uiso 1 1 calc R U . . .
C6 C 0.1334(10) 1.0832(7) 0.77310(16) 0.0951(15) Uani 1 1 d . . . . .
H6 H 0.0743 1.1400 0.7960 0.114 Uiso 1 1 calc R U . . .
C9 C 0.5614(7) 0.8250(6) 0.91821(14) 0.0741(11) Uani 1 1 d . . . . .
C10 C 0.3632(8) 0.8408(6) 0.94035(14) 0.0811(13) Uani 1 1 d . . . . .
H10 H 0.2876 0.9420 0.9412 0.097 Uiso 1 1 calc R U . . .
C11 C 0.2791(8) 0.7054(7) 0.96106(15) 0.0842(13) Uani 1 1 d . . . . .
H11 H 0.1446 0.7157 0.9758 0.101 Uiso 1 1 calc R U . . .
C12 C 0.3886(9) 0.5544(6) 0.96061(14) 0.0846(13) Uani 1 1 d . . . . .
C13 C 0.5869(9) 0.5426(6) 0.93852(16) 0.0933(14) Uani 1 1 d . . . . .
H13 H 0.6639 0.4419 0.9377 0.112 Uiso 1 1 calc R U . . .
C14 C 0.6729(8) 0.6782(7) 0.91754(16) 0.0873(13) Uani 1 1 d . . . . .
H14 H 0.8079 0.6689 0.9029 0.105 Uiso 1 1 calc R U . . .
C15 C 0.2898(14) 0.4054(9) 0.9825(2) 0.133(2) Uani 1 1 d . . . . .
H15A H 0.1282 0.4133 0.9823 0.199 Uiso 1 1 calc R U . . .
H15B H 0.3429 0.4021 1.0108 0.199 Uiso 1 1 calc R U . . .
H15C H 0.3354 0.3060 0.9682 0.199 Uiso 1 1 calc R U . . .
C16 C -0.1820(13) 1.0945(16) 0.6566(3) 0.179(4) Uani 1 1 d . . . . .
H16A H -0.2901 1.0807 0.6787 0.268 Uiso 1 1 calc R U . . .
H16B H -0.2498 1.0641 0.6304 0.268 Uiso 1 1 calc R U . . .
H16C H -0.1346 1.2084 0.6555 0.268 Uiso 1 1 calc R U . . .
C7 C 0.5045(19) 0.9748(12) 0.8102(4) 0.075(2) Uani 0.5 1 d . U P A 1
H7 H 0.6453 0.9308 0.8036 0.090 Uiso 0.5 1 calc R U P A 1
C8 C 0.458(2) 1.0150(16) 0.8480(4) 0.082(3) Uani 0.5 1 d . U P A 1
H8 H 0.3143 1.0548 0.8544 0.098 Uiso 0.5 1 calc R U P A 1
C71 C 0.5835(18) 0.9540(13) 0.8391(4) 0.079(2) Uani 0.5 1 d . U P A 2
H71 H 0.6660 0.8810 0.8225 0.095 Uiso 0.5 1 calc R U P A 2
C81 C 0.404(2) 1.0260(15) 0.8245(4) 0.077(3) Uani 0.5 1 d . U P A 2
H81 H 0.3165 1.0933 0.8418 0.092 Uiso 0.5 1 calc R U P A 2
O1 O 0.0037(9) 0.9934(6) 0.66413(13) 0.1244(14) Uani 1 1 d . . . . .
O2 O 0.8965(8) 0.9680(7) 0.8801(2) 0.1573(19) Uani 1 1 d . . . . .
O3 O 0.5955(9) 1.1431(5) 0.90915(14) 0.1325(17) Uani 1 1 d . . . . .
S1 S 0.6654(2) 0.99537(18) 0.88916(4) 0.0941(5) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
C1 C2 1.380(9) . ?
C1 C6 1.381(8) . ?
C1 C7 1.467(13) . ?
C1 C81 1.578(15) . ?
C2 C3 1.359(10) . ?
C2 H2 0.9300 . ?
C3 C4 1.363(8) . ?
C3 H3 0.9300 . ?
C4 O1 1.355(6) . ?
C4 C5 1.360(7) . ?
C5 C6 1.367(7) . ?
C5 H5 0.9300 . ?
C6 H6 0.9300 . ?
C9 C14 1.354(7) . ?
C9 C10 1.377(6) . ?
C9 S1 1.767(5) . ?
C10 C11 1.369(7) . ?
C10 H10 0.9300 . ?
C11 C12 1.378(7) . ?
C11 H11 0.9300 . ?
C12 C13 1.374(7) . ?
C12 C15 1.506(8) . ?
C13 C14 1.379(7) . ?
C13 H13 0.9300 . ?
C14 H14 0.9300 . ?
C15 H15A 0.9600 . ?
C15 H15B 0.9600 . ?
C15 H15C 0.9600 . ?
C16 O1 1.389(10) . ?
C16 H16A 0.9600 . ?
C16 H16B 0.9600 . ?
C16 H16C 0.9600 . ?
C7 C8 1.282(19) . ?
C7 H7 0.9300 . ?
C8 S1 1.809(14) . ?
C8 H8 0.9300 . ?
C71 C81 1.299(18) . ?
C71 S1 1.705(13) . ?
C71 H71 0.9300 . ?
C81 H81 0.9300 . ?
O2 S1 1.417(5) . ?
O3 S1 1.412(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
_geom_angle_publ_flag
C2 C1 C6 117.1(5) . . ?
C2 C1 C7 106.3(7) . . ?
C6 C1 C7 136.6(7) . . ?
C2 C1 C81 138.5(8) . . ?
C6 C1 C81 104.4(7) . . ?
C3 C2 C1 121.9(6) . . ?
C3 C2 H2 119.0 . . ?
C1 C2 H2 119.0 . . ?
C2 C3 C4 119.8(6) . . ?
C2 C3 H3 120.1 . . ?
C4 C3 H3 120.1 . . ?
O1 C4 C5 125.4(5) . . ?
O1 C4 C3 114.6(5) . . ?
C5 C4 C3 120.0(5) . . ?
C4 C5 C6 120.2(5) . . ?
C4 C5 H5 119.9 . . ?
C6 C5 H5 119.9 . . ?
C5 C6 C1 121.2(5) . . ?
C5 C6 H6 119.4 . . ?
C1 C6 H6 119.4 . . ?
C14 C9 C10 120.3(5) . . ?
C14 C9 S1 119.9(4) . . ?
C10 C9 S1 119.7(4) . . ?
C11 C10 C9 119.0(4) . . ?
C11 C10 H10 120.5 . . ?
C9 C10 H10 120.5 . . ?
C10 C11 C12 121.7(4) . . ?
C10 C11 H11 119.1 . . ?
C12 C11 H11 119.1 . . ?
C13 C12 C11 118.0(5) . . ?
C13 C12 C15 121.0(5) . . ?
C11 C12 C15 121.0(5) . . ?
C12 C13 C14 120.7(5) . . ?
C12 C13 H13 119.6 . . ?
C14 C13 H13 119.6 . . ?
C9 C14 C13 120.2(5) . . ?
C9 C14 H14 119.9 . . ?
C13 C14 H14 119.9 . . ?
C12 C15 H15A 109.5 . . ?
C12 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C12 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
O1 C16 H16A 109.5 . . ?
O1 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
O1 C16 H16C 109.5 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
C8 C7 C1 119.6(12) . . ?
C8 C7 H7 120.2 . . ?
C1 C7 H7 120.2 . . ?
C7 C8 S1 121.1(12) . . ?
C7 C8 H8 119.5 . . ?
S1 C8 H8 119.5 . . ?
C81 C71 S1 118.9(12) . . ?
C81 C71 H71 120.6 . . ?
S1 C71 H71 120.6 . . ?
C71 C81 C1 119.5(13) . . ?
C71 C81 H81 120.2 . . ?
C1 C81 H81 120.2 . . ?
C4 O1 C16 118.0(6) . . ?
O3 S1 O2 120.4(4) . . ?
O3 S1 C71 120.4(4) . . ?
O2 S1 C71 93.1(5) . . ?
O3 S1 C9 108.2(2) . . ?
O2 S1 C9 108.9(3) . . ?
C71 S1 C9 104.0(4) . . ?
O3 S1 C8 93.2(5) . . ?
O2 S1 C8 121.5(5) . . ?
C9 S1 C8 102.2(4) . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C6 C1 C2 C3 0.8(8) . . . . ?
C7 C1 C2 C3 -177.4(6) . . . . ?
C81 C1 C2 C3 178.3(8) . . . . ?
C1 C2 C3 C4 -0.4(9) . . . . ?
C2 C3 C4 O1 -179.0(5) . . . . ?
C2 C3 C4 C5 -0.1(8) . . . . ?
O1 C4 C5 C6 179.0(5) . . . . ?
C3 C4 C5 C6 0.2(8) . . . . ?
C4 C5 C6 C1 0.1(8) . . . . ?
C2 C1 C6 C5 -0.6(8) . . . . ?
C7 C1 C6 C5 176.9(7) . . . . ?
C81 C1 C6 C5 -178.9(6) . . . . ?
C14 C9 C10 C11 -1.0(7) . . . . ?
S1 C9 C10 C11 176.9(4) . . . . ?
C9 C10 C11 C12 0.5(7) . . . . ?
C10 C11 C12 C13 -0.1(8) . . . . ?
C10 C11 C12 C15 -178.1(5) . . . . ?
C11 C12 C13 C14 0.1(8) . . . . ?
C15 C12 C13 C14 178.1(6) . . . . ?
C10 C9 C14 C13 1.0(7) . . . . ?
S1 C9 C14 C13 -176.9(4) . . . . ?
C12 C13 C14 C9 -0.5(8) . . . . ?
C2 C1 C7 C8 -168.2(9) . . . . ?
C6 C1 C7 C8 14.1(14) . . . . ?
C1 C7 C8 S1 -177.5(6) . . . . ?
S1 C71 C81 C1 175.9(6) . . . . ?
C2 C1 C81 C71 -1.1(15) . . . . ?
C6 C1 C81 C71 176.6(9) . . . . ?
C5 C4 O1 C16 9.5(9) . . . . ?
C3 C4 O1 C16 -171.6(6) . . . . ?
C81 C71 S1 O3 -22.4(11) . . . . ?
C81 C71 S1 O2 -150.7(9) . . . . ?
C81 C71 S1 C9 98.9(9) . . . . ?
C14 C9 S1 O3 -152.3(4) . . . . ?
C10 C9 S1 O3 29.8(4) . . . . ?
C14 C9 S1 O2 -19.7(5) . . . . ?
C10 C9 S1 O2 162.4(4) . . . . ?
C14 C9 S1 C71 78.6(6) . . . . ?
C10 C9 S1 C71 -99.4(5) . . . . ?
C14 C9 S1 C8 110.1(6) . . . . ?
C10 C9 S1 C8 -67.8(6) . . . . ?
C7 C8 S1 O3 142.0(10) . . . . ?
C7 C8 S1 O2 12.9(13) . . . . ?
C7 C8 S1 C9 -108.6(10) . . . . ?

_refine_diff_density_max         0.265
_refine_diff_density_min         -0.152
_refine_diff_density_rms         0.043



