# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_28
_database_code_depnum_ccdc_archive 'CCDC 1900974'
loop_
_audit_author_name
_audit_author_address
'Antonio DiPasquale'
;Genentech Inc.
United States of America
;
_audit_update_record             
;
2019-03-04 deposited with the CCDC.	2019-10-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        28
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C25 H24 N2 O2 S'
_chemical_formula_weight         416.52

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'
N N 0.0061 0.0033 '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'

_diffrn_refln_scan_width         1.0
_diffrn_refln_scan_rate          20
_space_group.centring_type       primitive

_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                   9.0518(4)
_cell_length_b                   12.1315(5)
_cell_length_c                   18.9731(8)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2083.47(15)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    8729
_cell_measurement_theta_min      2.49
_cell_measurement_theta_max      25.38

_exptl_crystal_description       prism
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.328
_exptl_crystal_F_000             880
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.070
_exptl_crystal_size_mid          0.030
_exptl_crystal_size_min          0.030
_exptl_absorpt_coefficient_mu    0.180
_shelx_estimated_absorpt_T_min   0.987
_shelx_estimated_absorpt_T_max   0.995
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.851
_exptl_absorpt_correction_T_max  0.928
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-I CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.366
_diffrn_reflns_number            26438
_diffrn_reflns_av_unetI/netI     0.0430
_diffrn_reflns_av_R_equivalents  0.0602
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         1.993
_diffrn_reflns_theta_max         25.377
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3817
_reflns_number_gt                3452
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.744
_reflns_Friedel_fraction_max     0.998
_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    SHELXT-2014
_computing_structure_refinement  SHELXL-2014
_computing_molecular_graphics    ORTEP-32
_computing_publication_material  WinGX
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0396P)²+0.7032P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_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 1342 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   0.04(5)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         3817
_refine_ls_number_parameters     273
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0472
_refine_ls_R_factor_gt           0.0403
_refine_ls_wR_factor_ref         0.0922
_refine_ls_wR_factor_gt          0.0889
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_restrained_S_all      1.081
_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_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 0.6266(4) 0.4514(3) 0.30739(17) 0.0186(7) Uani 1 1 d . . . . .
H1 H 0.5558 0.4624 0.2675 0.022 Uiso 1 1 calc R U . . .
C2 C 0.6141(4) 0.5525(2) 0.35464(17) 0.0189(7) Uani 1 1 d . . . . .
H2A H 0.6627 0.6163 0.3318 0.023 Uiso 1 1 calc R U . . .
H2B H 0.5088 0.5710 0.3621 0.023 Uiso 1 1 calc R U . . .
C3 C 0.6867(4) 0.5289(3) 0.42410(17) 0.0178(7) Uani 1 1 d . . . . .
C4 C 0.7543(4) 0.6004(3) 0.47500(17) 0.0183(7) Uani 1 1 d . . . . .
C5 C 0.7737(4) 0.7154(3) 0.48045(17) 0.0212(8) Uani 1 1 d . . . . .
H5 H 0.7353 0.7635 0.4454 0.025 Uiso 1 1 calc R U . . .
C6 C 0.8497(4) 0.7568(3) 0.53764(19) 0.0245(8) Uani 1 1 d . . . . .
H6 H 0.8654 0.8341 0.5410 0.029 Uiso 1 1 calc R U . . .
C7 C 0.9041(4) 0.6881(3) 0.59081(17) 0.0222(7) Uani 1 1 d . . . . .
H7 H 0.9547 0.7196 0.6298 0.027 Uiso 1 1 calc R U . . .
C8 C 0.8855(4) 0.5748(3) 0.58762(17) 0.0207(8) Uani 1 1 d . . . . .
H8 H 0.9214 0.5277 0.6238 0.025 Uiso 1 1 calc R U . . .
C9 C 0.8117(4) 0.5329(3) 0.52884(17) 0.0171(7) Uani 1 1 d . . . . .
C10 C 0.7032(4) 0.4246(3) 0.44857(17) 0.0174(7) Uani 1 1 d . . . . .
C11 C 0.6411(4) 0.3214(2) 0.41674(16) 0.0165(7) Uani 1 1 d . . . . .
H11 H 0.5570 0.2974 0.4473 0.020 Uiso 1 1 calc R U . . .
C12 C 0.7792(4) 0.4369(3) 0.27486(18) 0.0231(8) Uani 1 1 d . . . . .
H12A H 0.8539 0.4362 0.3122 0.035 Uiso 1 1 calc R U . . .
H12B H 0.7991 0.4980 0.2425 0.035 Uiso 1 1 calc R U . . .
H12C H 0.7827 0.3671 0.2489 0.035 Uiso 1 1 calc R U . . .
C13 C 0.7496(4) 0.2259(3) 0.41323(16) 0.0170(7) Uani 1 1 d . . . . .
C14 C 0.8995(4) 0.2426(3) 0.39919(16) 0.0213(8) Uani 1 1 d . . . . .
H14 H 0.9355 0.3153 0.3919 0.026 Uiso 1 1 calc R U . . .
C15 C 0.9961(4) 0.1542(3) 0.39581(18) 0.0254(8) Uani 1 1 d . . . . .
H15 H 1.0972 0.1665 0.3850 0.030 Uiso 1 1 calc R U . . .
C16 C 0.9457(4) 0.0476(3) 0.40810(18) 0.0265(9) Uani 1 1 d . . . . .
H16 H 1.0123 -0.0129 0.4065 0.032 Uiso 1 1 calc R U . . .
C17 C 0.7977(4) 0.0304(3) 0.42263(18) 0.0248(8) Uani 1 1 d . . . . .
H17 H 0.7623 -0.0421 0.4311 0.030 Uiso 1 1 calc R U . . .
C18 C 0.7007(4) 0.1192(3) 0.42482(17) 0.0212(8) Uani 1 1 d . . . . .
H18 H 0.5991 0.1064 0.4344 0.025 Uiso 1 1 calc R U . . .
C19 C 0.2905(4) 0.4076(3) 0.32548(18) 0.0185(7) Uani 1 1 d . . . . .
C20 C 0.2634(4) 0.4696(3) 0.26555(18) 0.0237(8) Uani 1 1 d . . . . .
H20 H 0.3037 0.4480 0.2214 0.028 Uiso 1 1 calc R U . . .
C21 C 0.1768(4) 0.5637(3) 0.27056(19) 0.0257(8) Uani 1 1 d . . . . .
H21 H 0.1604 0.6074 0.2297 0.031 Uiso 1 1 calc R U . . .
C22 C 0.1137(4) 0.5951(3) 0.33413(18) 0.0248(8) Uani 1 1 d . . . . .
C23 C 0.1380(4) 0.5287(3) 0.39300(19) 0.0253(8) Uani 1 1 d . . . . .
H23 H 0.0918 0.5472 0.4364 0.030 Uiso 1 1 calc R U . . .
C24 C 0.2274(4) 0.4370(3) 0.38962(18) 0.0216(8) Uani 1 1 d . . . . .
H24 H 0.2458 0.3943 0.4307 0.026 Uiso 1 1 calc R U . . .
C25 C 0.0218(4) 0.6986(3) 0.3387(2) 0.0333(9) Uani 1 1 d . . . . .
H25A H -0.0772 0.6802 0.3560 0.050 Uiso 1 1 calc R U . . .
H25B H 0.0140 0.7322 0.2919 0.050 Uiso 1 1 calc R U . . .
H25C H 0.0688 0.7507 0.3712 0.050 Uiso 1 1 calc R U . . .
N1 N 0.5777(3) 0.3503(2) 0.34610(13) 0.0180(6) Uani 1 1 d . . . . .
N2 N 0.7804(3) 0.4249(2) 0.51124(14) 0.0176(6) Uani 1 1 d . . . . .
H2 H 0.8053 0.3663 0.5358 0.021 Uiso 1 1 calc R U . . .
O1 O 0.3801(3) 0.21661(18) 0.37308(12) 0.0236(6) Uani 1 1 d . . . . .
O2 O 0.4304(3) 0.26679(18) 0.24914(12) 0.0237(6) Uani 1 1 d . . . . .
S1 S 0.41966(9) 0.29870(6) 0.32168(4) 0.0186(2) 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 N1 1.497(4) . ?
C1 C12 1.523(5) . ?
C1 C2 1.524(4) . ?
C1 H1 1.0000 . ?
C2 C3 1.500(4) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C3 C10 1.356(4) . ?
C3 C4 1.435(5) . ?
C4 C9 1.409(5) . ?
C4 C5 1.410(4) . ?
C5 C6 1.379(5) . ?
C5 H5 0.9500 . ?
C6 C7 1.398(5) . ?
C6 H6 0.9500 . ?
C7 C8 1.387(4) . ?
C7 H7 0.9500 . ?
C8 C9 1.396(4) . ?
C8 H8 0.9500 . ?
C9 N2 1.382(4) . ?
C10 N2 1.379(4) . ?
C10 C11 1.499(4) . ?
C11 N1 1.499(4) . ?
C11 C13 1.521(4) . ?
C11 H11 1.0000 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 C18 1.387(4) . ?
C13 C14 1.397(5) . ?
C14 C15 1.385(5) . ?
C14 H14 0.9500 . ?
C15 C16 1.391(5) . ?
C15 H15 0.9500 . ?
C16 C17 1.383(5) . ?
C16 H16 0.9500 . ?
C17 C18 1.390(5) . ?
C17 H17 0.9500 . ?
C18 H18 0.9500 . ?
C19 C20 1.386(5) . ?
C19 C24 1.391(5) . ?
C19 S1 1.765(3) . ?
C20 C21 1.388(5) . ?
C20 H20 0.9500 . ?
C21 C22 1.388(5) . ?
C21 H21 0.9500 . ?
C22 C23 1.395(5) . ?
C22 C25 1.508(5) . ?
C23 C24 1.378(5) . ?
C23 H23 0.9500 . ?
C24 H24 0.9500 . ?
C25 H25A 0.9800 . ?
C25 H25B 0.9800 . ?
C25 H25C 0.9800 . ?
N1 S1 1.629(3) . ?
N2 H2 0.8800 . ?
O1 S1 1.439(2) . ?
O2 S1 1.433(2) . ?

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
N1 C1 C12 111.9(3) . . ?
N1 C1 C2 110.4(3) . . ?
C12 C1 C2 113.5(3) . . ?
N1 C1 H1 106.9 . . ?
C12 C1 H1 106.9 . . ?
C2 C1 H1 106.9 . . ?
C3 C2 C1 109.3(3) . . ?
C3 C2 H2A 109.8 . . ?
C1 C2 H2A 109.8 . . ?
C3 C2 H2B 109.8 . . ?
C1 C2 H2B 109.8 . . ?
H2A C2 H2B 108.3 . . ?
C10 C3 C4 106.7(3) . . ?
C10 C3 C2 121.8(3) . . ?
C4 C3 C2 131.5(3) . . ?
C9 C4 C5 118.4(3) . . ?
C9 C4 C3 107.1(3) . . ?
C5 C4 C3 134.5(3) . . ?
C6 C5 C4 118.7(3) . . ?
C6 C5 H5 120.7 . . ?
C4 C5 H5 120.7 . . ?
C5 C6 C7 121.8(3) . . ?
C5 C6 H6 119.1 . . ?
C7 C6 H6 119.1 . . ?
C8 C7 C6 121.1(3) . . ?
C8 C7 H7 119.4 . . ?
C6 C7 H7 119.4 . . ?
C7 C8 C9 117.0(3) . . ?
C7 C8 H8 121.5 . . ?
C9 C8 H8 121.5 . . ?
N2 C9 C8 129.5(3) . . ?
N2 C9 C4 107.5(3) . . ?
C8 C9 C4 123.0(3) . . ?
C3 C10 N2 110.4(3) . . ?
C3 C10 C11 126.8(3) . . ?
N2 C10 C11 122.6(3) . . ?
N1 C11 C10 108.0(2) . . ?
N1 C11 C13 112.7(2) . . ?
C10 C11 C13 114.3(3) . . ?
N1 C11 H11 107.2 . . ?
C10 C11 H11 107.2 . . ?
C13 C11 H11 107.2 . . ?
C1 C12 H12A 109.5 . . ?
C1 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C1 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C18 C13 C14 118.4(3) . . ?
C18 C13 C11 119.9(3) . . ?
C14 C13 C11 121.7(3) . . ?
C15 C14 C13 120.6(3) . . ?
C15 C14 H14 119.7 . . ?
C13 C14 H14 119.7 . . ?
C14 C15 C16 120.3(3) . . ?
C14 C15 H15 119.8 . . ?
C16 C15 H15 119.8 . . ?
C17 C16 C15 119.4(3) . . ?
C17 C16 H16 120.3 . . ?
C15 C16 H16 120.3 . . ?
C16 C17 C18 120.1(3) . . ?
C16 C17 H17 120.0 . . ?
C18 C17 H17 120.0 . . ?
C13 C18 C17 121.1(3) . . ?
C13 C18 H18 119.4 . . ?
C17 C18 H18 119.4 . . ?
C20 C19 C24 120.4(3) . . ?
C20 C19 S1 119.4(3) . . ?
C24 C19 S1 120.0(3) . . ?
C19 C20 C21 119.4(3) . . ?
C19 C20 H20 120.3 . . ?
C21 C20 H20 120.3 . . ?
C20 C21 C22 121.2(3) . . ?
C20 C21 H21 119.4 . . ?
C22 C21 H21 119.4 . . ?
C21 C22 C23 118.2(3) . . ?
C21 C22 C25 120.3(3) . . ?
C23 C22 C25 121.5(3) . . ?
C24 C23 C22 121.5(3) . . ?
C24 C23 H23 119.3 . . ?
C22 C23 H23 119.3 . . ?
C23 C24 C19 119.3(3) . . ?
C23 C24 H24 120.3 . . ?
C19 C24 H24 120.3 . . ?
C22 C25 H25A 109.5 . . ?
C22 C25 H25B 109.5 . . ?
H25A C25 H25B 109.5 . . ?
C22 C25 H25C 109.5 . . ?
H25A C25 H25C 109.5 . . ?
H25B C25 H25C 109.5 . . ?
C1 N1 C11 121.1(3) . . ?
C1 N1 S1 115.8(2) . . ?
C11 N1 S1 120.0(2) . . ?
C10 N2 C9 108.3(3) . . ?
C10 N2 H2 125.8 . . ?
C9 N2 H2 125.8 . . ?
O2 S1 O1 118.74(14) . . ?
O2 S1 N1 108.52(14) . . ?
O1 S1 N1 106.97(14) . . ?
O2 S1 C19 106.62(15) . . ?
O1 S1 C19 108.96(15) . . ?
N1 S1 C19 106.43(14) . . ?

_refine_diff_density_max         0.255
_refine_diff_density_min         -0.290
_refine_diff_density_rms         0.050

####################################################################### 
# 
# 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_14
_database_code_depnum_ccdc_archive 'CCDC 1900975'
loop_
_audit_author_name
_audit_author_address
'Antonio DiPasquale'
;Genentech Inc.
United States of America
;
_audit_update_record             
;
2019-03-04 deposited with the CCDC.	2019-10-09 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        14
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C23 H26 N2 O3 S'
_chemical_formula_weight         410.52

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'
N N 0.0061 0.0033 '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'

_diffrn_refln_scan_width         1.0
_diffrn_refln_scan_rate          10
_space_group.centring_type       primitive

_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                   9.2149(3)
_cell_length_b                   11.3488(4)
_cell_length_c                   19.7251(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2062.81(12)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9888
_cell_measurement_theta_min      2.74
_cell_measurement_theta_max      25.33

_exptl_crystal_description       plate
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.322
_exptl_crystal_F_000             872
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.080
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    0.184
_shelx_estimated_absorpt_T_min   0.985
_shelx_estimated_absorpt_T_max   0.993
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.842
_exptl_absorpt_correction_T_max  0.928
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-I CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.366
_diffrn_reflns_number            42376
_diffrn_reflns_av_unetI/netI     0.0227
_diffrn_reflns_av_R_equivalents  0.0450
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.065
_diffrn_reflns_theta_max         25.367
_diffrn_reflns_theta_full        25.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             3784
_reflns_number_gt                3597
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.743
_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    SHELXT-2014
_computing_structure_refinement  SHELXL-2014
_computing_molecular_graphics    ORTEP-32
_computing_publication_material  WinGX
_refine_special_details          ?
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0474P)²+0.6579P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     iterative
_atom_sites_solution_secondary   difmap
_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 1494 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259). 
;
_refine_ls_abs_structure_Flack   -0.03(3)
_chemical_absolute_configuration ad
_refine_ls_number_reflns         3784
_refine_ls_number_parameters     265
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0364
_refine_ls_R_factor_gt           0.0342
_refine_ls_wR_factor_ref         0.0843
_refine_ls_wR_factor_gt          0.0826
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_restrained_S_all      1.063
_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_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 0.3143(3) 0.3338(2) 0.75610(13) 0.0172(5) Uani 1 1 d . . . . .
H1 H 0.3812 0.2655 0.7630 0.021 Uiso 1 1 calc R U . . .
C2 C 0.2466(3) 0.3234(2) 0.68750(13) 0.0174(5) Uani 1 1 d . . . . .
C3 C 0.1188(3) 0.2453(2) 0.60199(12) 0.0196(6) Uani 1 1 d . . . . .
C4 C 0.0376(3) 0.1729(2) 0.55953(13) 0.0255(6) Uani 1 1 d . . . . .
H4 H 0.0221 0.0922 0.5700 0.031 Uiso 1 1 calc R U . . .
C5 C -0.0199(3) 0.2232(3) 0.50123(14) 0.0281(6) Uani 1 1 d . . . . .
H5 H -0.0769 0.1762 0.4716 0.034 Uiso 1 1 calc R U . . .
C6 C 0.0043(3) 0.3412(3) 0.48522(14) 0.0296(7) Uani 1 1 d . . . . .
H6 H -0.0342 0.3727 0.4444 0.036 Uiso 1 1 calc R U . . .
C7 C 0.0840(3) 0.4134(2) 0.52821(13) 0.0247(6) Uani 1 1 d . . . . .
H7 H 0.0993 0.4940 0.5173 0.030 Uiso 1 1 calc R U . . .
C8 C 0.1413(3) 0.3657(2) 0.58777(13) 0.0195(5) Uani 1 1 d . . . . .
C9 C 0.2227(3) 0.4139(2) 0.64375(12) 0.0189(5) Uani 1 1 d . . . . .
C10 C 0.2770(3) 0.5370(2) 0.65530(14) 0.0240(6) Uani 1 1 d . . . . .
H10A H 0.1977 0.5936 0.6462 0.029 Uiso 1 1 calc R U . . .
H10B H 0.3569 0.5538 0.6232 0.029 Uiso 1 1 calc R U . . .
C11 C 0.3321(3) 0.5541(2) 0.72849(13) 0.0209(6) Uani 1 1 d . . . . .
H11 H 0.4087 0.6164 0.7268 0.025 Uiso 1 1 calc R U . . .
C12 C 0.2137(3) 0.5988(2) 0.77591(15) 0.0281(6) Uani 1 1 d . . . . .
H12A H 0.1262 0.5508 0.7702 0.042 Uiso 1 1 calc R U . . .
H12B H 0.1916 0.6812 0.7651 0.042 Uiso 1 1 calc R U . . .
H12C H 0.2474 0.5932 0.8229 0.042 Uiso 1 1 calc R U . . .
C13 C 0.6144(3) 0.4016(2) 0.66065(13) 0.0240(6) Uani 1 1 d . . . . .
H13 H 0.5602 0.3340 0.6402 0.029 Uiso 1 1 calc R U . . .
C14 C 0.7686(3) 0.4177(3) 0.63697(14) 0.0317(7) Uani 1 1 d . . . . .
H14A H 0.8402 0.4479 0.6701 0.038 Uiso 1 1 calc R U . . .
H14B H 0.8075 0.3601 0.6040 0.038 Uiso 1 1 calc R U . . .
C15 C 0.6531(4) 0.5001(3) 0.61318(16) 0.0329(7) Uani 1 1 d . . . . .
H15A H 0.6209 0.4935 0.5655 0.040 Uiso 1 1 calc R U . . .
H15B H 0.6535 0.5813 0.6316 0.040 Uiso 1 1 calc R U . . .
C16 C 0.2024(3) 0.3341(2) 0.81287(12) 0.0184(6) Uani 1 1 d . . . . .
C17 C 0.0551(3) 0.3335(2) 0.79812(13) 0.0207(6) Uani 1 1 d . . . . .
H17 H 0.0261 0.3269 0.7521 0.025 Uiso 1 1 calc R U . . .
C18 C -0.0518(3) 0.3422(2) 0.84741(13) 0.0225(6) Uani 1 1 d . . . . .
H18 H -0.1517 0.3423 0.8355 0.027 Uiso 1 1 calc R U . . .
C19 C -0.0088(3) 0.3507(2) 0.91444(13) 0.0210(6) Uani 1 1 d . . . . .
C20 C 0.1374(3) 0.3475(2) 0.93143(13) 0.0218(6) Uani 1 1 d . . . . .
H20 H 0.1649 0.3518 0.9778 0.026 Uiso 1 1 calc R U . . .
C21 C 0.2443(3) 0.3381(2) 0.88219(13) 0.0199(6) Uani 1 1 d . . . . .
C22 C 0.4004(3) 0.3360(2) 0.90369(13) 0.0225(6) Uani 1 1 d . . . . .
H22A H 0.4435 0.4139 0.8965 0.034 Uiso 1 1 calc R U . . .
H22B H 0.4532 0.2774 0.8768 0.034 Uiso 1 1 calc R U . . .
H22C H 0.4066 0.3152 0.9518 0.034 Uiso 1 1 calc R U . . .
C23 C -0.2528(3) 0.3793(3) 0.95107(15) 0.0283(7) Uani 1 1 d . . . . .
H23A H -0.2641 0.4493 0.9224 0.042 Uiso 1 1 calc R U . . .
H23B H -0.3097 0.3892 0.9927 0.042 Uiso 1 1 calc R U . . .
H23C H -0.2873 0.3097 0.9265 0.042 Uiso 1 1 calc R U . . .
N1 N 0.4023(2) 0.44499(17) 0.75651(10) 0.0170(4) Uani 1 1 d . . . . .
N2 N 0.1848(2) 0.22074(18) 0.66306(10) 0.0193(5) Uani 1 1 d . . . . .
H2 H 0.1873 0.1515 0.6831 0.023 Uiso 1 1 calc R U . . .
O1 O 0.6215(2) 0.32993(16) 0.78399(9) 0.0224(4) Uani 1 1 d . . . . .
O2 O 0.6424(2) 0.54305(16) 0.76278(10) 0.0257(4) Uani 1 1 d . . . . .
O3 O -0.1033(2) 0.36434(18) 0.96804(9) 0.0272(5) Uani 1 1 d . . . . .
S1 S 0.57727(7) 0.43160(5) 0.74600(3) 0.01760(16) 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 1.495(3) . ?
C1 N1 1.499(3) . ?
C1 C16 1.522(4) . ?
C1 H1 1.0000 . ?
C2 C9 1.359(4) . ?
C2 N2 1.384(3) . ?
C3 N2 1.378(3) . ?
C3 C4 1.391(4) . ?
C3 C8 1.411(4) . ?
C4 C5 1.389(4) . ?
C4 H4 0.9500 . ?
C5 C6 1.394(4) . ?
C5 H5 0.9500 . ?
C6 C7 1.389(4) . ?
C6 H6 0.9500 . ?
C7 C8 1.397(4) . ?
C7 H7 0.9500 . ?
C8 C9 1.442(4) . ?
C9 C10 1.501(4) . ?
C10 C11 1.543(4) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 N1 1.503(3) . ?
C11 C12 1.523(4) . ?
C11 H11 1.0000 . ?
C12 H12A 0.9800 . ?
C12 H12B 0.9800 . ?
C12 H12C 0.9800 . ?
C13 C15 1.501(4) . ?
C13 C14 1.507(4) . ?
C13 S1 1.751(3) . ?
C13 H13 1.0000 . ?
C14 C15 1.492(4) . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?
C16 C17 1.388(4) . ?
C16 C21 1.421(4) . ?
C17 C18 1.388(4) . ?
C17 H17 0.9500 . ?
C18 C19 1.384(4) . ?
C18 H18 0.9500 . ?
C19 O3 1.378(3) . ?
C19 C20 1.389(4) . ?
C20 C21 1.388(4) . ?
C20 H20 0.9500 . ?
C21 C22 1.500(4) . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
C23 O3 1.428(3) . ?
C23 H23A 0.9800 . ?
C23 H23B 0.9800 . ?
C23 H23C 0.9800 . ?
N1 S1 1.633(2) . ?
N2 H2 0.8800 . ?
O1 S1 1.4349(19) . ?
O2 S1 1.4384(18) . ?

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 N1 107.3(2) . . ?
C2 C1 C16 112.5(2) . . ?
N1 C1 C16 111.1(2) . . ?
C2 C1 H1 108.6 . . ?
N1 C1 H1 108.6 . . ?
C16 C1 H1 108.6 . . ?
C9 C2 N2 110.4(2) . . ?
C9 C2 C1 125.7(2) . . ?
N2 C2 C1 123.6(2) . . ?
N2 C3 C4 130.1(2) . . ?
N2 C3 C8 107.8(2) . . ?
C4 C3 C8 122.1(2) . . ?
C5 C4 C3 117.5(3) . . ?
C5 C4 H4 121.3 . . ?
C3 C4 H4 121.3 . . ?
C4 C5 C6 121.4(3) . . ?
C4 C5 H5 119.3 . . ?
C6 C5 H5 119.3 . . ?
C7 C6 C5 120.9(3) . . ?
C7 C6 H6 119.6 . . ?
C5 C6 H6 119.6 . . ?
C6 C7 C8 119.0(3) . . ?
C6 C7 H7 120.5 . . ?
C8 C7 H7 120.5 . . ?
C7 C8 C3 119.2(3) . . ?
C7 C8 C9 133.9(3) . . ?
C3 C8 C9 106.9(2) . . ?
C2 C9 C8 106.5(2) . . ?
C2 C9 C10 123.5(2) . . ?
C8 C9 C10 129.9(2) . . ?
C9 C10 C11 111.7(2) . . ?
C9 C10 H10A 109.3 . . ?
C11 C10 H10A 109.3 . . ?
C9 C10 H10B 109.3 . . ?
C11 C10 H10B 109.3 . . ?
H10A C10 H10B 107.9 . . ?
N1 C11 C12 110.9(2) . . ?
N1 C11 C10 112.4(2) . . ?
C12 C11 C10 112.4(2) . . ?
N1 C11 H11 106.9 . . ?
C12 C11 H11 106.9 . . ?
C10 C11 H11 106.9 . . ?
C11 C12 H12A 109.5 . . ?
C11 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C11 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C15 C13 C14 59.49(19) . . ?
C15 C13 S1 120.1(2) . . ?
C14 C13 S1 117.3(2) . . ?
C15 C13 H13 116.0 . . ?
C14 C13 H13 116.0 . . ?
S1 C13 H13 116.0 . . ?
C15 C14 C13 60.07(19) . . ?
C15 C14 H14A 117.8 . . ?
C13 C14 H14A 117.8 . . ?
C15 C14 H14B 117.8 . . ?
C13 C14 H14B 117.8 . . ?
H14A C14 H14B 114.9 . . ?
C14 C15 C13 60.44(19) . . ?
C14 C15 H15A 117.7 . . ?
C13 C15 H15A 117.7 . . ?
C14 C15 H15B 117.7 . . ?
C13 C15 H15B 117.7 . . ?
H15A C15 H15B 114.8 . . ?
C17 C16 C21 117.9(2) . . ?
C17 C16 C1 120.5(2) . . ?
C21 C16 C1 121.6(2) . . ?
C18 C17 C16 123.2(2) . . ?
C18 C17 H17 118.4 . . ?
C16 C17 H17 118.4 . . ?
C19 C18 C17 118.1(3) . . ?
C19 C18 H18 120.9 . . ?
C17 C18 H18 120.9 . . ?
O3 C19 C18 124.1(2) . . ?
O3 C19 C20 115.5(2) . . ?
C18 C19 C20 120.4(2) . . ?
C21 C20 C19 121.5(2) . . ?
C21 C20 H20 119.3 . . ?
C19 C20 H20 119.3 . . ?
C20 C21 C16 118.9(2) . . ?
C20 C21 C22 119.0(2) . . ?
C16 C21 C22 122.1(2) . . ?
C21 C22 H22A 109.5 . . ?
C21 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C21 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
O3 C23 H23A 109.5 . . ?
O3 C23 H23B 109.5 . . ?
H23A C23 H23B 109.5 . . ?
O3 C23 H23C 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?
C1 N1 C11 117.32(19) . . ?
C1 N1 S1 117.04(15) . . ?
C11 N1 S1 117.07(16) . . ?
C3 N2 C2 108.4(2) . . ?
C3 N2 H2 125.8 . . ?
C2 N2 H2 125.8 . . ?
C19 O3 C23 116.3(2) . . ?
O1 S1 O2 117.94(11) . . ?
O1 S1 N1 106.79(11) . . ?
O2 S1 N1 107.51(11) . . ?
O1 S1 C13 106.88(12) . . ?
O2 S1 C13 108.08(13) . . ?
N1 S1 C13 109.46(12) . . ?

_refine_diff_density_max         0.377
_refine_diff_density_min         -0.230
_refine_diff_density_rms         0.048

