# 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_rkspyran
_database_code_depnum_ccdc_archive 'CCDC 1046365'
_audit_update_record             
;
2015-01-30 deposited with the CCDC.
2016-07-05 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C25 H17 N O S'
_chemical_formula_weight         379.46

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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   P21/n

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

_cell_length_a                   5.4373(6)
_cell_length_b                   22.5643(19)
_cell_length_c                   15.678(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 91.295(10)
_cell_angle_gamma                90.00
_cell_volume                     1923.0(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       needle
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.16
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.311
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             792
_exptl_absorpt_coefficient_mu    0.184
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.89619
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   'CrysAlisPro, Agilent Technologies'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6845
_diffrn_reflns_av_R_equivalents  0.0554
_diffrn_reflns_av_sigmaI/netI    0.1132
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         3.00
_diffrn_reflns_theta_max         25.00
_reflns_number_total             3390
_reflns_number_gt                1681
_reflns_threshold_expression     >2σ(I)

_computing_data_collection       'CrysAlisPro, Agilent Technologies'
_computing_cell_refinement       'CrysAlisPro, Agilent Technologies'
_computing_data_reduction        'CrysAlisPro, Agilent Technologies'
_computing_structure_solution    'SHELXL-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 Refinement of F² against ALL reflections.  The weighted R-factor wR and
 goodness of fit S are based on F², conventional R-factors R are based
 on F, with F set to zero for negative F². The threshold expression of
 F² > 2σ(F²) is used only for calculating R-factors(gt) etc. and is
 not relevant to the choice of reflections for refinement.  R-factors based
 on F² are statistically about twice as large as those based on F, and R-
 factors based on ALL data will be even larger.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0436P)²+1.7354P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3390
_refine_ls_number_parameters     241
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.1745
_refine_ls_R_factor_gt           0.0803
_refine_ls_wR_factor_ref         0.1715
_refine_ls_wR_factor_gt          0.1360
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_restrained_S_all      1.018
_refine_ls_shift/su_max          0.000
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
S1 S 0.4880(2) 0.26806(5) 0.62541(10) 0.0588(5) Uani 1 1 d . . .
O1 O 0.3548(6) 0.04136(14) 0.6311(2) 0.0655(11) Uani 1 1 d . . .
N1 N 0.8284(7) 0.19681(16) 0.5155(3) 0.0444(10) Uani 1 1 d . . .
C12 C 0.4915(8) 0.19157(18) 0.6198(3) 0.0389(11) Uani 1 1 d . . .
C5 C 0.9391(8) 0.1015(2) 0.4499(3) 0.0414(12) Uani 1 1 d . . .
C1 C 0.3654(8) 0.14687(19) 0.6587(3) 0.0396(12) Uani 1 1 d . . .
C10 C 0.9718(8) 0.1632(2) 0.4617(3) 0.0430(12) Uani 1 1 d . . .
C11 C 0.6653(8) 0.16702(19) 0.5572(3) 0.0391(12) Uani 1 1 d . . .
C4 C 0.7565(8) 0.0722(2) 0.4978(3) 0.0464(13) Uani 1 1 d . . .
H009 H 0.7287 0.0317 0.4916 0.056 Uiso 1 1 calc R . .
C2 C 0.4348(8) 0.0905(2) 0.6161(3) 0.0442(12) Uani 1 1 d . . .
C3 C 0.6248(8) 0.1049(2) 0.5524(3) 0.0415(12) Uani 1 1 d . . .
C6 C 1.0936(9) 0.0713(2) 0.3940(3) 0.0559(14) Uani 1 1 d . . .
H012 H 1.0730 0.0307 0.3856 0.067 Uiso 1 1 calc R . .
C20 C 0.1512(10) 0.3516(3) 0.6482(4) 0.0687(10) Uani 1 1 d D . .
C13 C 0.2114(8) 0.14780(19) 0.7336(3) 0.0393(12) Uani 1 1 d . . .
C18 C 0.0072(8) 0.1109(2) 0.7393(3) 0.0515(14) Uani 1 1 d . . .
H015 H -0.0381 0.0871 0.6931 0.062 Uiso 1 1 calc R . .
C9 C 1.1574(8) 0.1922(2) 0.4166(3) 0.0532(14) Uani 1 1 d . . .
H016 H 1.1795 0.2328 0.4232 0.064 Uiso 1 1 calc R . .
C15 C 0.1369(10) 0.1814(2) 0.8768(3) 0.0647(16) Uani 1 1 d . . .
H017 H 0.1807 0.2053 0.9230 0.078 Uiso 1 1 calc R . .
C17 C -0.1285(10) 0.1093(3) 0.8123(4) 0.0671(17) Uani 1 1 d . . .
H018 H -0.2639 0.0843 0.8154 0.080 Uiso 1 1 calc R . .
C7 C 1.2731(10) 0.1006(3) 0.3521(4) 0.0655(16) Uani 1 1 d . . .
H019 H 1.3752 0.0799 0.3157 0.079 Uiso 1 1 calc R . .
C8 C 1.3048(9) 0.1615(3) 0.3635(4) 0.0650(17) Uani 1 1 d . . .
H020 H 1.4277 0.1813 0.3345 0.078 Uiso 1 1 calc R . .
C19 C 0.1910(9) 0.2875(2) 0.6653(4) 0.0623(16) Uani 1 1 d . . .
H02A H 0.0637 0.2642 0.6369 0.075 Uiso 1 1 calc R . .
H02B H 0.1856 0.2798 0.7261 0.075 Uiso 1 1 calc R . .
C14 C 0.2730(9) 0.1825(2) 0.8034(3) 0.0494(13) Uani 1 1 d . . .
H022 H 0.4096 0.2071 0.8011 0.059 Uiso 1 1 calc R . .
C23 C 0.077(2) 0.4709(4) 0.6200(8) 0.148(6) Uani 1 1 d . . .
H023 H 0.0533 0.5110 0.6091 0.177 Uiso 1 1 calc R . .
C16 C -0.0642(12) 0.1446(3) 0.8807(4) 0.0740(18) Uani 1 1 d . . .
H024 H -0.1570 0.1436 0.9298 0.089 Uiso 1 1 calc R . .
C25 C -0.0104(10) 0.3703(3) 0.5881(4) 0.0687(10) Uani 1 1 d . . .
H025 H -0.0933 0.3427 0.5541 0.082 Uiso 1 1 calc R . .
C21 C 0.2801(10) 0.3937(2) 0.6938(4) 0.0687(10) Uani 1 1 d D . .
H026 H 0.3951 0.3821 0.7353 0.082 Uiso 1 1 calc R . .
C22 C 0.2397(19) 0.4533(3) 0.6783(6) 0.125(4) Uani 1 1 d . . .
H027 H 0.3286 0.4815 0.7095 0.150 Uiso 1 1 calc R . .
C24 C -0.0547(15) 0.4295(5) 0.5764(7) 0.142(4) Uani 1 1 d . . .
H028 H -0.1772 0.4415 0.5378 0.170 Uiso 1 1 calc R . .


_geom_special_details            
;
 All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell s.u.'s are taken
 into account individually in the estimation of s.u.'s in distances, angles
 and torsion angles; correlations between s.u.'s in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell s.u.'s is used for estimating s.u.'s 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
S1 C12 1.728(4) . ?
S1 C19 1.799(4) . ?
O1 C2 1.216(5) . ?
N1 C11 1.301(5) . ?
N1 C10 1.388(5) . ?
C12 C1 1.371(6) . ?
C12 C11 1.485(6) . ?
C5 C6 1.405(6) . ?
C5 C10 1.415(6) . ?
C5 C4 1.421(6) . ?
C1 C13 1.458(6) . ?
C1 C2 1.489(6) . ?
C10 C9 1.406(6) . ?
C11 C3 1.420(6) . ?
C4 C3 1.349(6) . ?
C4 H009 0.9300 . ?
C2 C3 1.488(6) . ?
C6 C7 1.361(6) . ?
C6 H012 0.9300 . ?
C20 C25 1.341(7) . ?
C20 C21 1.371(6) . ?
C20 C19 1.486(7) . ?
C13 C14 1.380(6) . ?
C13 C18 1.392(6) . ?
C18 C17 1.377(7) . ?
C18 H015 0.9300 . ?
C9 C8 1.357(6) . ?
C9 H016 0.9300 . ?
C15 C16 1.375(7) . ?
C15 C14 1.382(6) . ?
C15 H017 0.9300 . ?
C17 C16 1.374(8) . ?
C17 H018 0.9300 . ?
C7 C8 1.397(7) . ?
C7 H019 0.9300 . ?
C8 H020 0.9300 . ?
C19 H02A 0.9700 . ?
C19 H02B 0.9700 . ?
C14 H022 0.9300 . ?
C23 C22 1.317(13) . ?
C23 C24 1.353(13) . ?
C23 H023 0.9300 . ?
C16 H024 0.9300 . ?
C25 C24 1.370(10) . ?
C25 H025 0.9300 . ?
C21 C22 1.385(9) . ?
C21 H026 0.9300 . ?
C22 H027 0.9300 . ?
C24 H028 0.9300 . ?

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
C12 S1 C19 105.8(2) . . ?
C11 N1 C10 115.0(4) . . ?
C1 C12 C11 110.6(4) . . ?
C1 C12 S1 134.9(3) . . ?
C11 C12 S1 114.5(3) . . ?
C6 C5 C10 118.9(4) . . ?
C6 C5 C4 122.5(4) . . ?
C10 C5 C4 118.5(4) . . ?
C12 C1 C13 130.6(4) . . ?
C12 C1 C2 107.1(4) . . ?
C13 C1 C2 122.0(4) . . ?
N1 C10 C9 118.1(4) . . ?
N1 C10 C5 123.1(4) . . ?
C9 C10 C5 118.8(4) . . ?
N1 C11 C3 126.1(4) . . ?
N1 C11 C12 126.2(4) . . ?
C3 C11 C12 107.6(4) . . ?
C3 C4 C5 117.9(4) . . ?
C3 C4 H009 121.1 . . ?
C5 C4 H009 121.1 . . ?
O1 C2 C3 125.8(4) . . ?
O1 C2 C1 126.6(4) . . ?
C3 C2 C1 107.5(4) . . ?
C4 C3 C11 119.3(4) . . ?
C4 C3 C2 133.9(4) . . ?
C11 C3 C2 106.8(4) . . ?
C7 C6 C5 120.7(5) . . ?
C7 C6 H012 119.6 . . ?
C5 C6 H012 119.6 . . ?
C25 C20 C21 117.8(6) . . ?
C25 C20 C19 121.6(6) . . ?
C21 C20 C19 120.6(6) . . ?
C14 C13 C18 117.9(4) . . ?
C14 C13 C1 120.9(4) . . ?
C18 C13 C1 121.1(4) . . ?
C17 C18 C13 120.8(5) . . ?
C17 C18 H015 119.6 . . ?
C13 C18 H015 119.6 . . ?
C8 C9 C10 120.8(5) . . ?
C8 C9 H016 119.6 . . ?
C10 C9 H016 119.6 . . ?
C16 C15 C14 119.2(5) . . ?
C16 C15 H017 120.4 . . ?
C14 C15 H017 120.4 . . ?
C16 C17 C18 120.2(5) . . ?
C16 C17 H018 119.9 . . ?
C18 C17 H018 119.9 . . ?
C6 C7 C8 120.3(5) . . ?
C6 C7 H019 119.9 . . ?
C8 C7 H019 119.9 . . ?
C9 C8 C7 120.5(5) . . ?
C9 C8 H020 119.8 . . ?
C7 C8 H020 119.8 . . ?
C20 C19 S1 107.6(3) . . ?
C20 C19 H02A 110.2 . . ?
S1 C19 H02A 110.2 . . ?
C20 C19 H02B 110.2 . . ?
S1 C19 H02B 110.2 . . ?
H02A C19 H02B 108.5 . . ?
C13 C14 C15 121.7(5) . . ?
C13 C14 H022 119.2 . . ?
C15 C14 H022 119.2 . . ?
C22 C23 C24 118.9(9) . . ?
C22 C23 H023 120.5 . . ?
C24 C23 H023 120.5 . . ?
C17 C16 C15 120.2(5) . . ?
C17 C16 H024 119.9 . . ?
C15 C16 H024 119.9 . . ?
C20 C25 C24 120.8(7) . . ?
C20 C25 H025 119.6 . . ?
C24 C25 H025 119.6 . . ?
C20 C21 C22 120.3(7) . . ?
C20 C21 H026 119.9 . . ?
C22 C21 H026 119.9 . . ?
C23 C22 C21 121.0(9) . . ?
C23 C22 H027 119.5 . . ?
C21 C22 H027 119.5 . . ?
C23 C24 C25 121.0(9) . . ?
C23 C24 H028 119.5 . . ?
C25 C24 H028 119.5 . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.676
_refine_diff_density_min         -0.363
_refine_diff_density_rms         0.051
