# Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.
# This journal is © the Partner Organisations 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_mo_d8v17755_0m
_database_code_depnum_ccdc_archive 'CCDC 1812836'
loop_
_audit_author_name
_audit_author_address
'Min Shi' 'Shanghai Institute of Organic Chemistry'
_audit_update_record             
;
2017-12-21 deposited with the CCDC.	2019-06-25 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C17 H15 N O3 S'
_chemical_formula_weight         313.36

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      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_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+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   5.9669(2)
_cell_length_b                   11.4767(3)
_cell_length_c                   21.9463(7)
_cell_angle_alpha                90
_cell_angle_beta                 96.7800(10)
_cell_angle_gamma                90
_cell_volume                     1492.38(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    9897
_cell_measurement_theta_min      5.155
_cell_measurement_theta_max      54.983

_exptl_crystal_description       prismatic
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.395
_exptl_crystal_F_000             656
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.190
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.130
_exptl_absorpt_coefficient_mu    0.229
_shelx_estimated_absorpt_T_min   0.958
_shelx_estimated_absorpt_T_max   0.971
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7000
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            23572
_diffrn_reflns_av_unetI/netI     0.0189
_diffrn_reflns_av_R_equivalents  0.0361
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_theta_min         2.578
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measured_fraction_theta_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_point_group_measured_fraction_full 0.992
_reflns_number_total             2921
_reflns_number_gt                2664
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.0422P)²+0.6167P] 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     SHELXL
_refine_ls_extinction_coef       0.015(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2921
_refine_ls_number_parameters     202
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0367
_refine_ls_R_factor_gt           0.0331
_refine_ls_wR_factor_ref         0.0891
_refine_ls_wR_factor_gt          0.0860
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_restrained_S_all      1.062
_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
S1 S 0.71262(6) 0.74041(3) 0.50093(2) 0.02765(14) Uani 1 1 d . . . . .
N1 N 0.57581(19) 0.65790(10) 0.44579(5) 0.0276(3) Uani 1 1 d . . . . .
O1 O 0.5210(2) 0.31526(9) 0.33391(5) 0.0388(3) Uani 1 1 d . . . . .
O2 O 0.88363(18) 0.67420(10) 0.53761(5) 0.0368(3) Uani 1 1 d . . . . .
O3 O 0.54151(18) 0.79709(10) 0.53063(5) 0.0369(3) Uani 1 1 d . . . . .
C1 C 0.6606(2) 0.55662(12) 0.43745(6) 0.0272(3) Uani 1 1 d . . . . .
H1 H 0.7939 0.5333 0.4625 0.033 Uiso 1 1 calc R U . . .
C2 C 0.5592(2) 0.47840(12) 0.39145(6) 0.0275(3) Uani 1 1 d . . . . .
C3 C 0.6475(3) 0.37294(13) 0.37946(7) 0.0338(3) Uani 1 1 d . . . . .
H3 H 0.7832 0.3430 0.4007 0.041 Uiso 1 1 calc R U . . .
C4 C 0.3388(3) 0.38708(13) 0.31551(7) 0.0338(3) Uani 1 1 d . . . . .
C5 C 0.3537(2) 0.48965(13) 0.34933(6) 0.0278(3) Uani 1 1 d . . . . .
C6 C 0.1855(2) 0.57355(14) 0.33745(7) 0.0317(3) Uani 1 1 d . . . . .
H6 H 0.1941 0.6449 0.3596 0.038 Uiso 1 1 calc R U . . .
C7 C 0.0051(3) 0.55173(16) 0.29285(7) 0.0395(4) Uani 1 1 d . . . . .
C8 C -0.0027(3) 0.44633(17) 0.26034(7) 0.0458(5) Uani 1 1 d . . . . .
H8 H -0.1271 0.4321 0.2301 0.055 Uiso 1 1 calc R U . . .
C9 C 0.1632(3) 0.36233(16) 0.27060(7) 0.0443(4) Uani 1 1 d . . . . .
H9 H 0.1568 0.2915 0.2480 0.053 Uiso 1 1 calc R U . . .
C10 C -0.1789(3) 0.64117(19) 0.27969(9) 0.0536(5) Uani 1 1 d . . . . .
H10A H -0.1492 0.7073 0.3077 0.080 Uiso 1 1 calc R U . . .
H10B H -0.3247 0.6061 0.2855 0.080 Uiso 1 1 calc R U . . .
H10C H -0.1827 0.6683 0.2372 0.080 Uiso 1 1 calc R U . . .
C11 C 0.8441(2) 0.84329(12) 0.45771(6) 0.0257(3) Uani 1 1 d . . . . .
C12 C 0.7406(2) 0.94944(13) 0.44323(7) 0.0296(3) Uani 1 1 d . . . . .
H12 H 0.6010 0.9681 0.4577 0.035 Uiso 1 1 calc R U . . .
C13 C 0.8435(2) 1.02792(13) 0.40746(7) 0.0319(3) Uani 1 1 d . . . . .
H13 H 0.7741 1.1012 0.3978 0.038 Uiso 1 1 calc R U . . .
C14 C 1.0468(2) 1.00134(13) 0.38545(6) 0.0292(3) Uani 1 1 d . . . . .
C15 C 1.1475(2) 0.89423(13) 0.40119(7) 0.0322(3) Uani 1 1 d . . . . .
H15 H 1.2863 0.8748 0.3865 0.039 Uiso 1 1 calc R U . . .
C16 C 1.0494(2) 0.81574(13) 0.43770(7) 0.0302(3) Uani 1 1 d . . . . .
H16 H 1.1216 0.7438 0.4489 0.036 Uiso 1 1 calc R U . . .
C17 C 1.1571(3) 1.08623(15) 0.34614(7) 0.0392(4) Uani 1 1 d . . . . .
H17A H 1.3179 1.0927 0.3612 0.059 Uiso 1 1 calc R U . . .
H17B H 1.0852 1.1627 0.3480 0.059 Uiso 1 1 calc R U . . .
H17C H 1.1399 1.0586 0.3036 0.059 Uiso 1 1 calc R U . . .


_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
S1 O3 1.4310(11) . ?
S1 O2 1.4397(11) . ?
S1 N1 1.6716(12) . ?
S1 C11 1.7564(14) . ?
N1 C1 1.2894(19) . ?
O1 C3 1.3524(19) . ?
O1 C4 1.386(2) . ?
C1 C2 1.431(2) . ?
C1 H1 0.9500 . ?
C2 C3 1.358(2) . ?
C2 C5 1.451(2) . ?
C3 H3 0.9500 . ?
C4 C9 1.381(2) . ?
C4 C5 1.389(2) . ?
C5 C6 1.393(2) . ?
C6 C7 1.390(2) . ?
C6 H6 0.9500 . ?
C7 C8 1.402(3) . ?
C7 C10 1.506(3) . ?
C8 C9 1.381(3) . ?
C8 H8 0.9500 . ?
C9 H9 0.9500 . ?
C10 H10A 0.9800 . ?
C10 H10B 0.9800 . ?
C10 H10C 0.9800 . ?
C11 C12 1.386(2) . ?
C11 C16 1.386(2) . ?
C12 C13 1.385(2) . ?
C12 H12 0.9500 . ?
C13 C14 1.392(2) . ?
C13 H13 0.9500 . ?
C14 C15 1.394(2) . ?
C14 C17 1.503(2) . ?
C15 C16 1.381(2) . ?
C15 H15 0.9500 . ?
C16 H16 0.9500 . ?
C17 H17A 0.9800 . ?
C17 H17B 0.9800 . ?
C17 H17C 0.9800 . ?

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
O3 S1 O2 118.81(7) . . ?
O3 S1 N1 105.88(6) . . ?
O2 S1 N1 111.05(6) . . ?
O3 S1 C11 109.18(7) . . ?
O2 S1 C11 108.94(7) . . ?
N1 S1 C11 101.59(6) . . ?
C1 N1 S1 116.56(10) . . ?
C3 O1 C4 105.92(12) . . ?
N1 C1 C2 121.69(13) . . ?
N1 C1 H1 119.2 . . ?
C2 C1 H1 119.2 . . ?
C3 C2 C1 123.67(14) . . ?
C3 C2 C5 105.88(13) . . ?
C1 C2 C5 130.44(13) . . ?
O1 C3 C2 112.59(14) . . ?
O1 C3 H3 123.7 . . ?
C2 C3 H3 123.7 . . ?
C9 C4 O1 126.07(15) . . ?
C9 C4 C5 123.44(16) . . ?
O1 C4 C5 110.48(13) . . ?
C4 C5 C6 119.12(14) . . ?
C4 C5 C2 105.12(13) . . ?
C6 C5 C2 135.76(14) . . ?
C7 C6 C5 119.24(15) . . ?
C7 C6 H6 120.4 . . ?
C5 C6 H6 120.4 . . ?
C6 C7 C8 119.37(16) . . ?
C6 C7 C10 119.94(17) . . ?
C8 C7 C10 120.69(16) . . ?
C9 C8 C7 122.60(15) . . ?
C9 C8 H8 118.7 . . ?
C7 C8 H8 118.7 . . ?
C4 C9 C8 116.23(16) . . ?
C4 C9 H9 121.9 . . ?
C8 C9 H9 121.9 . . ?
C7 C10 H10A 109.5 . . ?
C7 C10 H10B 109.5 . . ?
H10A C10 H10B 109.5 . . ?
C7 C10 H10C 109.5 . . ?
H10A C10 H10C 109.5 . . ?
H10B C10 H10C 109.5 . . ?
C12 C11 C16 120.97(14) . . ?
C12 C11 S1 119.98(11) . . ?
C16 C11 S1 119.05(11) . . ?
C13 C12 C11 119.11(13) . . ?
C13 C12 H12 120.4 . . ?
C11 C12 H12 120.4 . . ?
C12 C13 C14 121.14(14) . . ?
C12 C13 H13 119.4 . . ?
C14 C13 H13 119.4 . . ?
C13 C14 C15 118.37(14) . . ?
C13 C14 C17 121.03(14) . . ?
C15 C14 C17 120.59(14) . . ?
C16 C15 C14 121.29(13) . . ?
C16 C15 H15 119.4 . . ?
C14 C15 H15 119.4 . . ?
C15 C16 C11 119.09(14) . . ?
C15 C16 H16 120.5 . . ?
C11 C16 H16 120.5 . . ?
C14 C17 H17A 109.5 . . ?
C14 C17 H17B 109.5 . . ?
H17A C17 H17B 109.5 . . ?
C14 C17 H17C 109.5 . . ?
H17A C17 H17C 109.5 . . ?
H17B C17 H17C 109.5 . . ?

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
O3 S1 N1 C1 -140.65(11) . . . . ?
O2 S1 N1 C1 -10.38(13) . . . . ?
C11 S1 N1 C1 105.34(11) . . . . ?
S1 N1 C1 C2 -179.72(10) . . . . ?
N1 C1 C2 C3 177.31(14) . . . . ?
N1 C1 C2 C5 -2.9(2) . . . . ?
C4 O1 C3 C2 -0.47(16) . . . . ?
C1 C2 C3 O1 -179.90(13) . . . . ?
C5 C2 C3 O1 0.23(16) . . . . ?
C3 O1 C4 C9 -178.76(15) . . . . ?
C3 O1 C4 C5 0.52(16) . . . . ?
C9 C4 C5 C6 -0.8(2) . . . . ?
O1 C4 C5 C6 179.90(12) . . . . ?
C9 C4 C5 C2 178.92(14) . . . . ?
O1 C4 C5 C2 -0.38(15) . . . . ?
C3 C2 C5 C4 0.09(15) . . . . ?
C1 C2 C5 C4 -179.76(14) . . . . ?
C3 C2 C5 C6 179.74(16) . . . . ?
C1 C2 C5 C6 -0.1(3) . . . . ?
C4 C5 C6 C7 1.1(2) . . . . ?
C2 C5 C6 C7 -178.49(15) . . . . ?
C5 C6 C7 C8 -0.6(2) . . . . ?
C5 C6 C7 C10 179.62(14) . . . . ?
C6 C7 C8 C9 -0.2(2) . . . . ?
C10 C7 C8 C9 179.50(15) . . . . ?
O1 C4 C9 C8 179.14(14) . . . . ?
C5 C4 C9 C8 -0.1(2) . . . . ?
C7 C8 C9 C4 0.6(2) . . . . ?
O3 S1 C11 C12 -17.11(13) . . . . ?
O2 S1 C11 C12 -148.32(11) . . . . ?
N1 S1 C11 C12 94.42(12) . . . . ?
O3 S1 C11 C16 163.95(11) . . . . ?
O2 S1 C11 C16 32.74(13) . . . . ?
N1 S1 C11 C16 -84.52(12) . . . . ?
C16 C11 C12 C13 1.0(2) . . . . ?
S1 C11 C12 C13 -177.96(11) . . . . ?
C11 C12 C13 C14 0.7(2) . . . . ?
C12 C13 C14 C15 -1.1(2) . . . . ?
C12 C13 C14 C17 179.43(13) . . . . ?
C13 C14 C15 C16 0.0(2) . . . . ?
C17 C14 C15 C16 179.42(14) . . . . ?
C14 C15 C16 C11 1.6(2) . . . . ?
C12 C11 C16 C15 -2.1(2) . . . . ?
S1 C11 C16 C15 176.85(11) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C3 H3 O2 0.95 2.28 3.1986(19) 163.1 3_766

_refine_diff_density_max         0.304
_refine_diff_density_min         -0.348
_refine_diff_density_rms         0.039

_shelxl_version_number           2013-4



####################################################################### 
# 
# 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_mo_d8v18343_0m
_database_code_depnum_ccdc_archive 'CCDC 1839382'
loop_
_audit_author_name
_audit_author_address
'Min Shi'
;Shanghai Institute of Organic Chemistry
China
;
_audit_update_record             
;
2018-04-25 deposited with the CCDC.	2019-06-25 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C21 H16 Br N O4 S'
_chemical_formula_weight         458.32

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'
Br Br -0.2901 2.4595 '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      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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, -y, -z'

_cell_length_a                   7.1629(2)
_cell_length_b                   10.9804(4)
_cell_length_c                   12.5285(4)
_cell_angle_alpha                102.4310(10)
_cell_angle_beta                 97.6580(10)
_cell_angle_gamma                98.7680(10)
_cell_volume                     936.85(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    9489
_cell_measurement_theta_min      5.716
_cell_measurement_theta_max      54.984

_exptl_crystal_description       prismatic
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.625
_exptl_crystal_F_000             464
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.120
_exptl_absorpt_coefficient_mu    2.334
_shelx_estimated_absorpt_T_min   0.679
_shelx_estimated_absorpt_T_max   0.767
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.4536
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16426
_diffrn_reflns_av_unetI/netI     0.0384
_diffrn_reflns_av_R_equivalents  0.0713
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         2.858
_diffrn_reflns_theta_max         25.999
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.989
_diffrn_measured_fraction_theta_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.989
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.989
_diffrn_reflns_point_group_measured_fraction_full 0.988
_reflns_number_total             3647
_reflns_number_gt                3264
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_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    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.0488P)²+0.5742P] 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     SHELXL
_refine_ls_extinction_coef       0.028(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3647
_refine_ls_number_parameters     254
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0411
_refine_ls_R_factor_gt           0.0368
_refine_ls_wR_factor_ref         0.1042
_refine_ls_wR_factor_gt          0.1009
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_restrained_S_all      1.055
_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
Br1 Br 0.29855(5) 0.95445(3) 0.32203(3) 0.06430(18) Uani 1 1 d . . . . .
S1 S 0.80506(8) 0.53040(6) 0.19776(4) 0.03289(17) Uani 1 1 d . . . . .
O1 O 1.0460(4) 0.1586(3) 0.42813(18) 0.0769(8) Uani 1 1 d . . . . .
O2 O 0.6755(3) 0.5196(2) 0.59619(15) 0.0588(6) Uani 1 1 d . . . . .
O3 O 1.0033(2) 0.58107(19) 0.24004(15) 0.0461(4) Uani 1 1 d . . . . .
O4 O 0.7462(3) 0.45989(18) 0.08524(13) 0.0434(4) Uani 1 1 d . . . . .
N1 N 0.7192(3) 0.44031(18) 0.27687(14) 0.0304(4) Uani 1 1 d . . . . .
C1 C 0.9243(4) 0.1943(3) 0.3716(2) 0.0480(6) Uani 1 1 d . . . . .
C2 C 0.9348(4) 0.1986(3) 0.2575(2) 0.0458(6) Uani 1 1 d . . . . .
H2 H 1.0366 0.1711 0.2266 0.055 Uiso 1 1 calc R U . . .
C3 C 0.8050(3) 0.2402(2) 0.19530(19) 0.0367(5) Uani 1 1 d . . . . .
H3 H 0.8147 0.2324 0.1209 0.044 Uiso 1 1 calc R U . . .
C4 C 0.6421(3) 0.2995(2) 0.23693(17) 0.0311(5) Uani 1 1 d . . . . .
C5 C 0.5967(3) 0.2666(2) 0.34482(19) 0.0363(5) Uani 1 1 d . . . . .
H5 H 0.4631 0.2363 0.3501 0.044 Uiso 1 1 calc R U . . .
C6 C 0.7534(4) 0.2306(3) 0.4162(2) 0.0425(6) Uani 1 1 d . . . . .
H6 H 0.7090 0.1824 0.4683 0.051 Uiso 1 1 calc R U . . .
C7 C 0.7204(3) 0.3686(2) 0.43998(18) 0.0348(5) Uani 1 1 d . . . . .
C8 C 0.8275(3) 0.4659(2) 0.39125(17) 0.0348(5) Uani 1 1 d . . . . .
H8A H 0.8267 0.5513 0.4326 0.042 Uiso 1 1 calc R U . . .
H8B H 0.9592 0.4550 0.3906 0.042 Uiso 1 1 calc R U . . .
C9 C 0.6454(4) 0.4119(3) 0.5435(2) 0.0466(6) Uani 1 1 d . . . . .
H9 H 0.5700 0.3514 0.5691 0.056 Uiso 1 1 calc R U . . .
C10 C 0.4621(3) 0.2657(2) 0.14882(18) 0.0344(5) Uani 1 1 d . . . . .
C11 C 0.4208(4) 0.1479(3) 0.0753(3) 0.0623(9) Uani 1 1 d . . . . .
H11 H 0.5028 0.0905 0.0800 0.075 Uiso 1 1 calc R U . . .
C12 C 0.2574(5) 0.1148(4) -0.0057(3) 0.0759(11) Uani 1 1 d . . . . .
H12 H 0.2299 0.0348 -0.0542 0.091 Uiso 1 1 calc R U . . .
C13 C 0.1367(4) 0.1982(3) -0.0149(2) 0.0563(8) Uani 1 1 d . . . . .
H13 H 0.0298 0.1765 -0.0710 0.068 Uiso 1 1 calc R U . . .
C14 C 0.1746(3) 0.3144(3) 0.0592(2) 0.0441(6) Uani 1 1 d . . . . .
H14 H 0.0925 0.3716 0.0535 0.053 Uiso 1 1 calc R U . . .
C15 C 0.3344(3) 0.3473(2) 0.14256(19) 0.0372(5) Uani 1 1 d . . . . .
H15 H 0.3556 0.4247 0.1945 0.045 Uiso 1 1 calc R U . . .
C16 C 0.6787(3) 0.6569(2) 0.22327(18) 0.0345(5) Uani 1 1 d . . . . .
C17 C 0.5074(4) 0.6506(2) 0.1551(2) 0.0414(6) Uani 1 1 d . . . . .
H17 H 0.4666 0.5854 0.0912 0.050 Uiso 1 1 calc R U . . .
C18 C 0.3976(4) 0.7416(3) 0.1825(2) 0.0474(6) Uani 1 1 d . . . . .
H18 H 0.2817 0.7381 0.1375 0.057 Uiso 1 1 calc R U . . .
C19 C 0.4612(4) 0.8381(2) 0.2773(2) 0.0447(6) Uani 1 1 d . . . . .
C20 C 0.6367(4) 0.8488(3) 0.3431(2) 0.0471(6) Uani 1 1 d . . . . .
H20 H 0.6798 0.9163 0.4049 0.057 Uiso 1 1 calc R U . . .
C21 C 0.7475(4) 0.7577(2) 0.3157(2) 0.0427(6) Uani 1 1 d . . . . .
H21 H 0.8664 0.7636 0.3586 0.051 Uiso 1 1 calc R U . . .


_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
Br1 C19 1.903(3) . ?
S1 O4 1.4271(17) . ?
S1 O3 1.4280(18) . ?
S1 N1 1.6547(19) . ?
S1 C16 1.767(3) . ?
O1 C1 1.214(3) . ?
O2 C9 1.195(4) . ?
N1 C8 1.482(3) . ?
N1 C4 1.510(3) . ?
C1 C2 1.452(4) . ?
C1 C6 1.485(4) . ?
C2 C3 1.331(3) . ?
C2 H2 0.9300 . ?
C3 C4 1.518(3) . ?
C3 H3 0.9300 . ?
C4 C10 1.522(3) . ?
C4 C5 1.534(3) . ?
C5 C6 1.495(3) . ?
C5 C7 1.517(3) . ?
C5 H5 0.9800 . ?
C6 C7 1.541(4) . ?
C6 H6 0.9800 . ?
C7 C9 1.481(3) . ?
C7 C8 1.503(3) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C9 H9 0.9300 . ?
C10 C11 1.382(4) . ?
C10 C15 1.381(3) . ?
C11 C12 1.388(4) . ?
C11 H11 0.9300 . ?
C12 C13 1.364(5) . ?
C12 H12 0.9300 . ?
C13 C14 1.372(4) . ?
C13 H13 0.9300 . ?
C14 C15 1.388(3) . ?
C14 H14 0.9300 . ?
C15 H15 0.9300 . ?
C16 C17 1.381(3) . ?
C16 C21 1.392(3) . ?
C17 C18 1.378(4) . ?
C17 H17 0.9300 . ?
C18 C19 1.381(4) . ?
C18 H18 0.9300 . ?
C19 C20 1.382(4) . ?
C20 C21 1.384(4) . ?
C20 H20 0.9300 . ?
C21 H21 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
O4 S1 O3 120.00(11) . . ?
O4 S1 N1 107.33(10) . . ?
O3 S1 N1 109.33(10) . . ?
O4 S1 C16 109.45(11) . . ?
O3 S1 C16 107.55(11) . . ?
N1 S1 C16 101.64(10) . . ?
C8 N1 C4 108.48(17) . . ?
C8 N1 S1 115.83(14) . . ?
C4 N1 S1 124.09(14) . . ?
O1 C1 C2 122.1(3) . . ?
O1 C1 C6 120.6(3) . . ?
C2 C1 C6 117.3(2) . . ?
C3 C2 C1 122.8(2) . . ?
C3 C2 H2 118.6 . . ?
C1 C2 H2 118.6 . . ?
C2 C3 C4 124.7(2) . . ?
C2 C3 H3 117.6 . . ?
C4 C3 H3 117.6 . . ?
N1 C4 C3 106.18(17) . . ?
N1 C4 C10 113.82(18) . . ?
C3 C4 C10 111.94(18) . . ?
N1 C4 C5 101.03(17) . . ?
C3 C4 C5 112.78(19) . . ?
C10 C4 C5 110.60(18) . . ?
C6 C5 C7 61.51(16) . . ?
C6 C5 C4 117.2(2) . . ?
C7 C5 C4 107.05(18) . . ?
C6 C5 H5 119.0 . . ?
C7 C5 H5 119.0 . . ?
C4 C5 H5 119.0 . . ?
C1 C6 C5 120.9(2) . . ?
C1 C6 C7 122.1(2) . . ?
C5 C6 C7 59.93(16) . . ?
C1 C6 H6 114.4 . . ?
C5 C6 H6 114.4 . . ?
C7 C6 H6 114.4 . . ?
C9 C7 C8 118.8(2) . . ?
C9 C7 C5 120.1(2) . . ?
C8 C7 C5 107.78(18) . . ?
C9 C7 C6 115.5(2) . . ?
C8 C7 C6 121.2(2) . . ?
C5 C7 C6 58.56(16) . . ?
N1 C8 C7 103.36(17) . . ?
N1 C8 H8A 111.1 . . ?
C7 C8 H8A 111.1 . . ?
N1 C8 H8B 111.1 . . ?
C7 C8 H8B 111.1 . . ?
H8A C8 H8B 109.1 . . ?
O2 C9 C7 124.3(3) . . ?
O2 C9 H9 117.9 . . ?
C7 C9 H9 117.9 . . ?
C11 C10 C15 118.7(2) . . ?
C11 C10 C4 119.2(2) . . ?
C15 C10 C4 122.1(2) . . ?
C10 C11 C12 120.2(3) . . ?
C10 C11 H11 119.9 . . ?
C12 C11 H11 119.9 . . ?
C13 C12 C11 120.8(3) . . ?
C13 C12 H12 119.6 . . ?
C11 C12 H12 119.6 . . ?
C12 C13 C14 119.4(2) . . ?
C12 C13 H13 120.3 . . ?
C14 C13 H13 120.3 . . ?
C13 C14 C15 120.5(3) . . ?
C13 C14 H14 119.8 . . ?
C15 C14 H14 119.8 . . ?
C10 C15 C14 120.3(2) . . ?
C10 C15 H15 119.8 . . ?
C14 C15 H15 119.8 . . ?
C17 C16 C21 121.1(2) . . ?
C17 C16 S1 119.45(19) . . ?
C21 C16 S1 119.34(18) . . ?
C18 C17 C16 119.4(2) . . ?
C18 C17 H17 120.3 . . ?
C16 C17 H17 120.3 . . ?
C17 C18 C19 119.4(2) . . ?
C17 C18 H18 120.3 . . ?
C19 C18 H18 120.3 . . ?
C18 C19 C20 121.5(3) . . ?
C18 C19 Br1 119.2(2) . . ?
C20 C19 Br1 119.2(2) . . ?
C19 C20 C21 119.2(2) . . ?
C19 C20 H20 120.4 . . ?
C21 C20 H20 120.4 . . ?
C20 C21 C16 119.2(2) . . ?
C20 C21 H21 120.4 . . ?
C16 C21 H21 120.4 . . ?

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
O4 S1 N1 C8 153.74(17) . . . . ?
O3 S1 N1 C8 22.1(2) . . . . ?
C16 S1 N1 C8 -91.39(18) . . . . ?
O4 S1 N1 C4 14.9(2) . . . . ?
O3 S1 N1 C4 -116.76(18) . . . . ?
C16 S1 N1 C4 129.75(17) . . . . ?
O1 C1 C2 C3 -178.4(3) . . . . ?
C6 C1 C2 C3 4.0(4) . . . . ?
C1 C2 C3 C4 6.1(4) . . . . ?
C8 N1 C4 C3 -82.6(2) . . . . ?
S1 N1 C4 C3 58.7(2) . . . . ?
C8 N1 C4 C10 153.78(19) . . . . ?
S1 N1 C4 C10 -64.9(2) . . . . ?
C8 N1 C4 C5 35.2(2) . . . . ?
S1 N1 C4 C5 176.59(15) . . . . ?
C2 C3 C4 N1 89.8(3) . . . . ?
C2 C3 C4 C10 -145.4(3) . . . . ?
C2 C3 C4 C5 -19.9(3) . . . . ?
N1 C4 C5 C6 -89.2(2) . . . . ?
C3 C4 C5 C6 23.7(3) . . . . ?
C10 C4 C5 C6 149.9(2) . . . . ?
N1 C4 C5 C7 -23.0(2) . . . . ?
C3 C4 C5 C7 89.9(2) . . . . ?
C10 C4 C5 C7 -143.87(19) . . . . ?
O1 C1 C6 C5 -176.1(3) . . . . ?
C2 C1 C6 C5 1.6(4) . . . . ?
O1 C1 C6 C7 112.2(3) . . . . ?
C2 C1 C6 C7 -70.1(3) . . . . ?
C7 C5 C6 C1 -111.6(3) . . . . ?
C4 C5 C6 C1 -16.1(3) . . . . ?
C4 C5 C6 C7 95.5(2) . . . . ?
C6 C5 C7 C9 -103.3(3) . . . . ?
C4 C5 C7 C9 144.5(2) . . . . ?
C6 C5 C7 C8 116.2(2) . . . . ?
C4 C5 C7 C8 4.0(3) . . . . ?
C4 C5 C7 C6 -112.2(2) . . . . ?
C1 C6 C7 C9 -139.2(2) . . . . ?
C5 C6 C7 C9 111.1(2) . . . . ?
C1 C6 C7 C8 17.0(3) . . . . ?
C5 C6 C7 C8 -92.8(2) . . . . ?
C1 C6 C7 C5 109.7(3) . . . . ?
C4 N1 C8 C7 -33.4(2) . . . . ?
S1 N1 C8 C7 -178.32(15) . . . . ?
C9 C7 C8 N1 -123.8(2) . . . . ?
C5 C7 C8 N1 17.3(2) . . . . ?
C6 C7 C8 N1 80.8(2) . . . . ?
C8 C7 C9 O2 -5.5(4) . . . . ?
C5 C7 C9 O2 -141.8(3) . . . . ?
C6 C7 C9 O2 151.3(3) . . . . ?
N1 C4 C10 C11 154.4(3) . . . . ?
C3 C4 C10 C11 34.0(3) . . . . ?
C5 C4 C10 C11 -92.7(3) . . . . ?
N1 C4 C10 C15 -28.2(3) . . . . ?
C3 C4 C10 C15 -148.6(2) . . . . ?
C5 C4 C10 C15 84.8(3) . . . . ?
C15 C10 C11 C12 2.3(5) . . . . ?
C4 C10 C11 C12 179.9(3) . . . . ?
C10 C11 C12 C13 0.9(6) . . . . ?
C11 C12 C13 C14 -2.2(6) . . . . ?
C12 C13 C14 C15 0.3(5) . . . . ?
C11 C10 C15 C14 -4.3(4) . . . . ?
C4 C10 C15 C14 178.3(2) . . . . ?
C13 C14 C15 C10 3.0(4) . . . . ?
O4 S1 C16 C17 21.4(2) . . . . ?
O3 S1 C16 C17 153.3(2) . . . . ?
N1 S1 C16 C17 -91.9(2) . . . . ?
O4 S1 C16 C21 -162.49(19) . . . . ?
O3 S1 C16 C21 -30.6(2) . . . . ?
N1 S1 C16 C21 84.2(2) . . . . ?
C21 C16 C17 C18 -3.7(4) . . . . ?
S1 C16 C17 C18 172.3(2) . . . . ?
C16 C17 C18 C19 0.4(4) . . . . ?
C17 C18 C19 C20 2.8(4) . . . . ?
C17 C18 C19 Br1 -174.3(2) . . . . ?
C18 C19 C20 C21 -2.7(4) . . . . ?
Br1 C19 C20 C21 174.4(2) . . . . ?
C19 C20 C21 C16 -0.6(4) . . . . ?
C17 C16 C21 C20 3.8(4) . . . . ?
S1 C16 C21 C20 -172.3(2) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
C21 H21 O1 0.93 2.58 3.222(3) 126.4 2_766
C17 H17 O4 0.93 2.42 3.184(3) 139.3 2_665
C8 H8B O2 0.97 2.57 3.520(3) 167.2 2_766
C5 H5 Br1 0.98 3.07 3.685(2) 122.4 1_545

_refine_diff_density_max         0.780
_refine_diff_density_min         -0.786
_refine_diff_density_rms         0.056

_shelxl_version_number           2013-4



