# 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_exp_316
_database_code_depnum_ccdc_archive 'CCDC 1578144'
_audit_update_record             
;
2018-04-12 deposited with the CCDC.
2019-01-03 downloaded from the CCDC.
;
_audit_creation_date             2017-03-18
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5324)
;
_shelx_SHELXL_version_number     2016/6
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C21 H21 N O2 S'
_chemical_formula_sum            'C21 H21 N O2 S'
_chemical_formula_weight         351.45
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 1 2/c 1'
_space_group_name_Hall           '-C 2yc'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   31.1655(5)
_cell_length_b                   8.49460(10)
_cell_length_c                   13.3472(2)
_cell_angle_alpha                90
_cell_angle_beta                 98.752(2)
_cell_angle_gamma                90
_cell_volume                     3492.37(9)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    5441
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      73.4240
_cell_measurement_theta_min      4.0800
_shelx_estimated_absorpt_T_max   0.767
_shelx_estimated_absorpt_T_min   0.668
_exptl_absorpt_coefficient_mu    1.753
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55160
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.43f (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.337
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             1488
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.16
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0194
_diffrn_reflns_av_unetI/netI     0.0222
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            6848
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.559
_diffrn_reflns_theta_min         5.402
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2684
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.977
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     13.00 116.00   1.00    1.00    --   40.98  77.00   0.00  103
  2  ω     92.00 138.00   1.00    1.00    --  106.95  45.00-150.00   46
  3  ω    106.00 161.00   1.00    1.00    --  106.95 125.00-180.00   55
  4  ω     36.00 135.00   1.00    1.00    --  106.95 -61.00  60.00   99
  5  ω     61.00 108.00   1.00    1.00    --  106.95 -94.00 -30.00   47
  6  ω     55.00  81.00   1.00    1.00    --  106.95 -94.00 -90.00   26
  7  ω     24.00 107.00   1.00    1.00    --  106.95 -94.00-120.00   83
  8  ω     85.00 171.00   1.00    1.00    --  106.95  45.00 150.00   86
  9  ω    -32.00  -5.00   1.00    1.00    --  -40.98 125.00-180.00   27
 10  ω    -64.00  28.00   1.00    1.00    --  -40.98  37.00 -30.00   92
 11  ω    -86.00 -60.00   1.00    1.00    --  -40.98 125.00-180.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, AtlasS2'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0078630000
_diffrn_orient_matrix_UB_12      0.1250332000
_diffrn_orient_matrix_UB_13      0.0845307000
_diffrn_orient_matrix_UB_21      -0.0004668000
_diffrn_orient_matrix_UB_22      -0.1297325000
_diffrn_orient_matrix_UB_23      0.0804545000
_diffrn_orient_matrix_UB_31      0.0493689000
_diffrn_orient_matrix_UB_32      -0.0207924000
_diffrn_orient_matrix_UB_33      0.0052709000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3310
_reflns_number_total             3443
_reflns_odcompleteness_completeness 99.88
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43f (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.747
_refine_diff_density_rms         0.121
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.082
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     228
_refine_ls_number_reflns         3443
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0434
_refine_ls_R_factor_gt           0.0423
_refine_ls_restrained_S_all      1.082
_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)+(0.0679P)²+3.0347P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1101
_refine_ls_wR_factor_ref         0.1111
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C2(H2A,H2B)
2.b Aromatic/amide H refined with riding coordinates:
 C13(H13), C20(H20), C9(H9), C16(H16), C10(H10), C19(H19), C12(H12), C17(H17),
 C11(H11)
2.c Idealised Me refined as rotating group:
 C14(H14A,H14B,H14C), C21(H21A,H21B,H21C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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 0.38031(2) 0.04264(4) 0.58506(3) 0.01411(13) Uani 1 1 d . . . . .
O2 O 0.36612(4) -0.10571(12) 0.53808(8) 0.0197(3) Uani 1 1 d . . . . .
O1 O 0.39121(4) 0.04768(13) 0.69390(8) 0.0200(3) Uani 1 1 d . . . . .
N1 N 0.30648(4) 0.40815(15) 0.51639(9) 0.0138(3) Uani 1 1 d . . . . .
C7 C 0.33540(4) 0.32986(17) 0.58605(10) 0.0132(3) Uani 1 1 d . . . . .
C4 C 0.29429(5) 0.31797(18) 0.43178(11) 0.0149(3) Uani 1 1 d . . . . .
C5 C 0.31535(5) 0.17677(17) 0.44282(11) 0.0147(3) Uani 1 1 d . . . . .
C13 C 0.37022(5) 0.55783(17) 0.68244(11) 0.0162(3) Uani 1 1 d . . . . .
H13 H 0.369636 0.611003 0.621344 0.019 Uiso 1 1 calc R . . . .
C8 C 0.35392(5) 0.40424(17) 0.68265(11) 0.0135(3) Uani 1 1 d . . . . .
C20 C 0.43366(5) 0.05013(17) 0.43971(12) 0.0172(3) Uani 1 1 d . . . . .
H20 H 0.415563 -0.026112 0.405784 0.021 Uiso 1 1 calc R . . . .
C15 C 0.42657(5) 0.10551(17) 0.53397(11) 0.0151(3) Uani 1 1 d . . . . .
C6 C 0.34127(4) 0.18238(17) 0.54192(10) 0.0134(3) Uani 1 1 d . . . . .
C9 C 0.35511(5) 0.32658(18) 0.77528(11) 0.0166(3) Uani 1 1 d . . . . .
H9 H 0.343841 0.225374 0.776769 0.020 Uiso 1 1 calc R . . . .
C16 C 0.45403(5) 0.21722(19) 0.58651(12) 0.0189(3) Uani 1 1 d . . . . .
H16 H 0.449372 0.252128 0.650018 0.023 Uiso 1 1 calc R . . . .
C10 C 0.37299(5) 0.3993(2) 0.86517(11) 0.0200(3) Uani 1 1 d . . . . .
H10 H 0.374255 0.345722 0.926296 0.024 Uiso 1 1 calc R . . . .
C19 C 0.46823(5) 0.11056(19) 0.39702(11) 0.0195(3) Uani 1 1 d . . . . .
H19 H 0.473137 0.073940 0.334089 0.023 Uiso 1 1 calc R . . . .
C12 C 0.38722(5) 0.63140(18) 0.77261(12) 0.0195(3) Uani 1 1 d . . . . .
H12 H 0.397464 0.734154 0.771763 0.023 Uiso 1 1 calc R . . . .
C18 C 0.49562(5) 0.22489(19) 0.44677(12) 0.0204(3) Uani 1 1 d . . . . .
C1 C 0.28416(5) 0.56001(19) 0.51423(12) 0.0212(3) Uani 1 1 d . . . . .
H1A H 0.304670 0.646559 0.518835 0.025 Uiso 1 1 calc R . . . .
H1B H 0.267226 0.568235 0.569266 0.025 Uiso 1 1 calc R . . . .
C17 C 0.48844(5) 0.27573(19) 0.54273(13) 0.0217(3) Uani 1 1 d . . . . .
H17 H 0.506997 0.349758 0.577632 0.026 Uiso 1 1 calc R . . . .
C14 C 0.31237(5) 0.05230(18) 0.36245(12) 0.0203(3) Uani 1 1 d . . . . .
H14A H 0.288773 0.076273 0.309612 0.030 Uiso 1 1 calc GR . . . .
H14B H 0.307398 -0.048148 0.391578 0.030 Uiso 1 1 calc GR . . . .
H14C H 0.339014 0.049078 0.334674 0.030 Uiso 1 1 calc GR . . . .
C11 C 0.38900(5) 0.55192(19) 0.86419(12) 0.0204(3) Uani 1 1 d . . . . .
H11 H 0.400839 0.600614 0.924500 0.025 Uiso 1 1 calc R . . . .
C3 C 0.26292(5) 0.4047(2) 0.35593(12) 0.0221(3) Uani 1 1 d . . . . .
H3A H 0.236262 0.345408 0.338099 0.027 Uiso 1 1 calc R . . . .
H3B H 0.275306 0.425886 0.294881 0.027 Uiso 1 1 calc R . . . .
C2 C 0.25462(5) 0.55880(19) 0.41072(13) 0.0218(3) Uani 1 1 d . . . . .
H2A H 0.261076 0.648641 0.370696 0.026 Uiso 1 1 calc R . . . .
H2B H 0.224412 0.564894 0.420115 0.026 Uiso 1 1 calc R . . . .
C21 C 0.53195(5) 0.2931(2) 0.39795(14) 0.0284(4) Uani 1 1 d . . . . .
H21A H 0.545733 0.210663 0.365335 0.043 Uiso 1 1 calc GR . . . .
H21B H 0.552831 0.341840 0.448834 0.043 Uiso 1 1 calc GR . . . .
H21C H 0.520442 0.370344 0.348563 0.043 Uiso 1 1 calc GR . . . .


_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 O2 1.4465(11) . ?
S1 O1 1.4413(11) . ?
S1 C15 1.7684(15) . ?
S1 C6 1.7344(14) . ?
N1 C7 1.3653(18) . ?
N1 C4 1.3697(18) . ?
N1 C1 1.4637(19) . ?
C7 C8 1.4725(19) . ?
C7 C6 1.4080(19) . ?
C4 C5 1.365(2) . ?
C4 C3 1.491(2) . ?
C5 C6 1.4419(19) . ?
C5 C14 1.499(2) . ?
C13 H13 0.9300 . ?
C13 C8 1.400(2) . ?
C13 C12 1.388(2) . ?
C8 C9 1.397(2) . ?
C20 H20 0.9300 . ?
C20 C15 1.392(2) . ?
C20 C19 1.391(2) . ?
C15 C16 1.394(2) . ?
C9 H9 0.9300 . ?
C9 C10 1.389(2) . ?
C16 H16 0.9300 . ?
C16 C17 1.389(2) . ?
C10 H10 0.9300 . ?
C10 C11 1.389(2) . ?
C19 H19 0.9300 . ?
C19 C18 1.393(2) . ?
C12 H12 0.9300 . ?
C12 C11 1.390(2) . ?
C18 C17 1.402(2) . ?
C18 C21 1.505(2) . ?
C1 H1A 0.9700 . ?
C1 H1B 0.9700 . ?
C1 C2 1.539(2) . ?
C17 H17 0.9300 . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C11 H11 0.9300 . ?
C3 H3A 0.9700 . ?
C3 H3B 0.9700 . ?
C3 C2 1.540(2) . ?
C2 H2A 0.9700 . ?
C2 H2B 0.9700 . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?

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
O2 S1 C15 108.02(7) . . ?
O2 S1 C6 107.43(7) . . ?
O1 S1 O2 118.19(6) . . ?
O1 S1 C15 107.38(7) . . ?
O1 S1 C6 111.10(7) . . ?
C6 S1 C15 103.72(7) . . ?
C7 N1 C4 111.13(12) . . ?
C7 N1 C1 134.85(13) . . ?
C4 N1 C1 113.91(12) . . ?
N1 C7 C8 121.16(13) . . ?
N1 C7 C6 105.24(12) . . ?
C6 C7 C8 133.59(13) . . ?
N1 C4 C3 110.75(13) . . ?
C5 C4 N1 109.52(13) . . ?
C5 C4 C3 139.72(14) . . ?
C4 C5 C6 105.26(12) . . ?
C4 C5 C14 124.49(13) . . ?
C6 C5 C14 130.16(13) . . ?
C8 C13 H13 119.7 . . ?
C12 C13 H13 119.7 . . ?
C12 C13 C8 120.58(14) . . ?
C13 C8 C7 119.47(13) . . ?
C9 C8 C7 121.77(13) . . ?
C9 C8 C13 118.75(13) . . ?
C15 C20 H20 120.5 . . ?
C19 C20 H20 120.5 . . ?
C19 C20 C15 119.00(14) . . ?
C20 C15 S1 119.82(12) . . ?
C20 C15 C16 121.00(14) . . ?
C16 C15 S1 119.07(11) . . ?
C7 C6 S1 126.82(11) . . ?
C7 C6 C5 108.83(12) . . ?
C5 C6 S1 123.28(11) . . ?
C8 C9 H9 119.7 . . ?
C10 C9 C8 120.50(14) . . ?
C10 C9 H9 119.7 . . ?
C15 C16 H16 120.4 . . ?
C17 C16 C15 119.10(14) . . ?
C17 C16 H16 120.4 . . ?
C9 C10 H10 119.9 . . ?
C9 C10 C11 120.30(14) . . ?
C11 C10 H10 119.9 . . ?
C20 C19 H19 119.4 . . ?
C20 C19 C18 121.25(14) . . ?
C18 C19 H19 119.4 . . ?
C13 C12 H12 119.9 . . ?
C13 C12 C11 120.17(14) . . ?
C11 C12 H12 119.9 . . ?
C19 C18 C17 118.61(14) . . ?
C19 C18 C21 120.59(15) . . ?
C17 C18 C21 120.80(16) . . ?
N1 C1 H1A 111.1 . . ?
N1 C1 H1B 111.1 . . ?
N1 C1 C2 103.25(12) . . ?
H1A C1 H1B 109.1 . . ?
C2 C1 H1A 111.1 . . ?
C2 C1 H1B 111.1 . . ?
C16 C17 C18 121.00(15) . . ?
C16 C17 H17 119.5 . . ?
C18 C17 H17 119.5 . . ?
C5 C14 H14A 109.5 . . ?
C5 C14 H14B 109.5 . . ?
C5 C14 H14C 109.5 . . ?
H14A C14 H14B 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C10 C11 C12 119.67(14) . . ?
C10 C11 H11 120.2 . . ?
C12 C11 H11 120.2 . . ?
C4 C3 H3A 111.0 . . ?
C4 C3 H3B 111.0 . . ?
C4 C3 C2 103.76(12) . . ?
H3A C3 H3B 109.0 . . ?
C2 C3 H3A 111.0 . . ?
C2 C3 H3B 111.0 . . ?
C1 C2 C3 108.13(12) . . ?
C1 C2 H2A 110.1 . . ?
C1 C2 H2B 110.1 . . ?
C3 C2 H2A 110.1 . . ?
C3 C2 H2B 110.1 . . ?
H2A C2 H2B 108.4 . . ?
C18 C21 H21A 109.5 . . ?
C18 C21 H21B 109.5 . . ?
C18 C21 H21C 109.5 . . ?
H21A C21 H21B 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?


_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.390
_oxdiff_exptl_absorpt_empirical_full_min 0.714
####################################################################### 
# 
# 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_20171013
_database_code_depnum_ccdc_archive 'CCDC 1836652'
_audit_update_record             
;
2018-04-12 deposited with the CCDC.
2019-01-03 downloaded from the CCDC.
;
_audit_creation_date             2017-10-14
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_shelx_SHELXL_version_number     2017/1
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C21 H18 Br N O3 S'
_chemical_formula_sum            'C21 H18 Br N O3 S'
_chemical_formula_weight         444.33
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/n 1'
_space_group_name_Hall           '-P 2yn'
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                   8.6549(5)
_cell_length_b                   18.2100(11)
_cell_length_c                   11.9124(6)
_cell_angle_alpha                90
_cell_angle_beta                 94.769(5)
_cell_angle_gamma                90
_cell_volume                     1870.96(18)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    5668
_cell_measurement_temperature    172.95(10)
_cell_measurement_theta_max      73.6420
_cell_measurement_theta_min      3.7400
_shelx_estimated_absorpt_T_max   0.631
_shelx_estimated_absorpt_T_min   0.551
_exptl_absorpt_coefficient_mu    4.223
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.18849
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.577
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             904
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.12
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0766
_diffrn_reflns_av_unetI/netI     0.0608
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            9309
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.477
_diffrn_reflns_theta_min         4.446
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      172.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.962
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -19.00  25.00   0.50    0.50    --    0.00 -77.00-150.00   88
  2  ω      6.00  88.00   0.50    0.50    --    0.00  19.00 -30.00  164
  3  ω    -86.00 -42.00   0.50    0.50    --    0.00 -77.00-150.00   88
  4  ω    -57.00 -32.00   0.50    0.50    --    0.00 -38.00-180.00   50
  5  ω     75.00 134.00   0.50    0.50    --   95.20  61.00 120.00  118
  6  ω     61.00  89.00   0.50    0.50    --   95.20 -30.00 -60.00   56
  7  ω      9.00  70.00   0.50    0.50    --   95.20 -61.00 -90.00  122
  8  ω    157.00 183.00   0.50    0.50    --   95.20  30.00   0.00   52
  9  ω     80.00 139.00   0.50    0.50    --   95.20  30.00   0.00  118
 10  ω     16.00 107.00   0.50    0.50    --   95.20 -77.00 -90.00  182
 11  ω     75.00 119.00   0.50    0.50    --   95.20 -61.00 -90.00   88
 12  ω     10.00  44.00   0.50    0.50    --   95.20 -30.00 -60.00   68
 13  ω     89.00 163.00   0.50    0.50    --   95.20  82.00  90.00  148
 14  ω     92.00 177.00   0.50    0.50    --   95.20  30.00  30.00  170
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa dual home/near'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0876242000
_diffrn_orient_matrix_UB_12      -0.0603833000
_diffrn_orient_matrix_UB_13      0.0701141000
_diffrn_orient_matrix_UB_21      0.1466177000
_diffrn_orient_matrix_UB_22      0.0481972000
_diffrn_orient_matrix_UB_23      0.0099537000
_diffrn_orient_matrix_UB_31      -0.0520303000
_diffrn_orient_matrix_UB_32      0.0346058000
_diffrn_orient_matrix_UB_33      0.1087102000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                3093
_reflns_number_total             3679
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         1.307
_refine_diff_density_min         -1.536
_refine_diff_density_rms         0.155
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     245
_refine_ls_number_reflns         3679
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0832
_refine_ls_R_factor_gt           0.0759
_refine_ls_restrained_S_all      1.017
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1740P)²+1.3174P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2101
_refine_ls_wR_factor_ref         0.2302
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C3(H3A,H3B), C2(H2A,H2B)
2.b Aromatic/amide H refined with riding coordinates:
 C12(H12), C13(H13), C19(H19), C9(H9), C15(H15), C10(H10), C18(H18), C21(H21),
 C16(H16)
2.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
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 0.22852(6) 0.22111(3) -0.06594(4) 0.0452(3) Uani 1 1 d . . . . .
S1 S 0.22105(11) 0.19206(7) 0.55615(8) 0.0317(3) Uani 1 1 d . . . . .
O3 O 0.1151(3) 0.19286(19) 0.4561(3) 0.0368(7) Uani 1 1 d . . . . .
O2 O 0.1707(4) 0.1604(2) 0.6579(3) 0.0423(8) Uani 1 1 d . . . . .
N1 N 0.5753(4) 0.0947(2) 0.4383(3) 0.0281(7) Uani 1 1 d . . . . .
O1 O 0.5955(5) 0.0737(2) 0.7907(3) 0.0558(10) Uani 1 1 d . . . . .
C5 C 0.4962(5) 0.1100(3) 0.6098(4) 0.0329(9) Uani 1 1 d . . . . .
C8 C 0.3866(4) 0.1578(2) 0.3061(3) 0.0269(8) Uani 1 1 d . . . . .
C4 C 0.6100(5) 0.0807(2) 0.5486(3) 0.0293(8) Uani 1 1 d . . . . .
C7 C 0.4415(4) 0.1351(3) 0.4205(3) 0.0301(9) Uani 1 1 d . . . . .
C12 C 0.3299(5) 0.1236(3) 0.1100(4) 0.0375(10) Uani 1 1 d . . . . .
H12 H 0.322083 0.087989 0.053846 0.045 Uiso 1 1 calc R . . . .
C14 C 0.2839(5) 0.2832(2) 0.5856(4) 0.0288(9) Uani 1 1 d . . . . .
C11 C 0.2961(5) 0.1965(3) 0.0845(4) 0.0339(9) Uani 1 1 d . . . . .
C13 C 0.3751(5) 0.1047(3) 0.2195(3) 0.0323(9) Uani 1 1 d . . . . .
H13 H 0.398640 0.055985 0.236949 0.039 Uiso 1 1 calc R . . . .
C19 C 0.3996(5) 0.2978(3) 0.6711(4) 0.0343(10) Uani 1 1 d . . . . .
H19 H 0.441810 0.259582 0.715463 0.041 Uiso 1 1 calc R . . . .
C6 C 0.3888(4) 0.1460(3) 0.5267(3) 0.0290(9) Uani 1 1 d . . . . .
C1 C 0.6928(5) 0.0709(3) 0.3652(4) 0.0355(10) Uani 1 1 d . . . . .
H1A H 0.721456 0.110357 0.316350 0.043 Uiso 1 1 calc R . . . .
H1B H 0.656981 0.029207 0.319347 0.043 Uiso 1 1 calc R . . . .
C9 C 0.3540(5) 0.2310(3) 0.2768(4) 0.0345(10) Uani 1 1 d . . . . .
H9 H 0.363057 0.266968 0.332274 0.041 Uiso 1 1 calc R . . . .
C15 C 0.2187(5) 0.3408(3) 0.5205(3) 0.0342(9) Uani 1 1 d . . . . .
H15 H 0.141524 0.331760 0.463099 0.041 Uiso 1 1 calc R . . . .
C10 C 0.3089(5) 0.2506(3) 0.1679(4) 0.0342(9) Uani 1 1 d . . . . .
H10 H 0.287079 0.299349 0.149672 0.041 Uiso 1 1 calc R . . . .
C17 C 0.3884(5) 0.4263(3) 0.6269(4) 0.0353(10) Uani 1 1 d . . . . .
C3 C 0.7623(5) 0.0412(3) 0.5656(4) 0.0386(11) Uani 1 1 d . . . . .
H3A H 0.747622 -0.010070 0.584157 0.046 Uiso 1 1 calc R . . . .
H3B H 0.829648 0.063956 0.624839 0.046 Uiso 1 1 calc R . . . .
C18 C 0.4514(5) 0.3681(3) 0.6902(4) 0.0355(10) Uani 1 1 d . . . . .
H18 H 0.530212 0.376948 0.746517 0.043 Uiso 1 1 calc R . . . .
C21 C 0.4956(6) 0.1065(3) 0.7312(4) 0.0410(11) Uani 1 1 d . . . . .
H21 H 0.416529 0.130011 0.765423 0.049 Uiso 1 1 calc R . . . .
C16 C 0.2702(5) 0.4109(3) 0.5425(4) 0.0419(11) Uani 1 1 d . . . . .
H16 H 0.225310 0.449447 0.500207 0.050 Uiso 1 1 calc R . . . .
C20 C 0.4430(7) 0.5047(3) 0.6491(4) 0.0496(13) Uani 1 1 d . . . . .
H20A H 0.395170 0.523993 0.712680 0.074 Uiso 1 1 calc GR . . . .
H20B H 0.414723 0.534321 0.583981 0.074 Uiso 1 1 calc GR . . . .
H20C H 0.553639 0.505160 0.664588 0.074 Uiso 1 1 calc GR . . . .
C2 C 0.8286(5) 0.0494(3) 0.4499(4) 0.0453(12) Uani 1 1 d . . . . .
H2A H 0.907990 0.087151 0.453192 0.054 Uiso 1 1 calc R . . . .
H2B H 0.874193 0.003516 0.427887 0.054 Uiso 1 1 calc R . . . .


_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 C11 1.892(4) . ?
S1 O3 1.442(3) . ?
S1 O2 1.442(3) . ?
S1 C14 1.772(5) . ?
S1 C6 1.738(4) . ?
N1 C4 1.348(5) . ?
N1 C7 1.373(5) . ?
N1 C1 1.459(5) . ?
O1 C21 1.226(6) . ?
C5 C4 1.381(6) . ?
C5 C6 1.457(6) . ?
C5 C21 1.448(6) . ?
C8 C7 1.465(5) . ?
C8 C13 1.411(6) . ?
C8 C9 1.400(6) . ?
C4 C3 1.500(6) . ?
C7 C6 1.394(6) . ?
C12 H12 0.9300 . ?
C12 C11 1.388(7) . ?
C12 C13 1.374(6) . ?
C14 C19 1.394(6) . ?
C14 C15 1.395(6) . ?
C11 C10 1.396(6) . ?
C13 H13 0.9300 . ?
C19 H19 0.9300 . ?
C19 C18 1.370(7) . ?
C1 H1A 0.9700 . ?
C1 H1B 0.9700 . ?
C1 C2 1.535(6) . ?
C9 H9 0.9300 . ?
C9 C10 1.371(6) . ?
C15 H15 0.9300 . ?
C15 C16 1.370(7) . ?
C10 H10 0.9300 . ?
C17 C18 1.386(7) . ?
C17 C16 1.402(6) . ?
C17 C20 1.519(7) . ?
C3 H3A 0.9700 . ?
C3 H3B 0.9700 . ?
C3 C2 1.544(7) . ?
C18 H18 0.9300 . ?
C21 H21 0.9300 . ?
C16 H16 0.9300 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C2 H2A 0.9700 . ?
C2 H2B 0.9700 . ?

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 C14 108.5(2) . . ?
O3 S1 C6 108.82(19) . . ?
O2 S1 O3 118.9(2) . . ?
O2 S1 C14 108.5(2) . . ?
O2 S1 C6 107.0(2) . . ?
C6 S1 C14 104.12(19) . . ?
C4 N1 C7 111.6(3) . . ?
C4 N1 C1 114.5(3) . . ?
C7 N1 C1 133.5(4) . . ?
C4 C5 C6 105.0(4) . . ?
C4 C5 C21 124.9(4) . . ?
C21 C5 C6 130.1(4) . . ?
C13 C8 C7 119.0(4) . . ?
C9 C8 C7 122.9(4) . . ?
C9 C8 C13 118.0(4) . . ?
N1 C4 C5 109.3(4) . . ?
N1 C4 C3 110.2(4) . . ?
C5 C4 C3 140.5(4) . . ?
N1 C7 C8 119.9(4) . . ?
N1 C7 C6 105.8(3) . . ?
C6 C7 C8 134.3(4) . . ?
C11 C12 H12 120.5 . . ?
C13 C12 H12 120.5 . . ?
C13 C12 C11 119.0(4) . . ?
C19 C14 S1 120.9(3) . . ?
C19 C14 C15 119.7(4) . . ?
C15 C14 S1 119.4(3) . . ?
C12 C11 Br1 118.5(4) . . ?
C12 C11 C10 121.1(4) . . ?
C10 C11 Br1 120.4(4) . . ?
C8 C13 H13 119.3 . . ?
C12 C13 C8 121.3(4) . . ?
C12 C13 H13 119.3 . . ?
C14 C19 H19 119.8 . . ?
C18 C19 C14 120.3(4) . . ?
C18 C19 H19 119.8 . . ?
C5 C6 S1 125.2(3) . . ?
C7 C6 S1 126.4(3) . . ?
C7 C6 C5 108.3(4) . . ?
N1 C1 H1A 111.3 . . ?
N1 C1 H1B 111.3 . . ?
N1 C1 C2 102.5(3) . . ?
H1A C1 H1B 109.2 . . ?
C2 C1 H1A 111.3 . . ?
C2 C1 H1B 111.3 . . ?
C8 C9 H9 119.3 . . ?
C10 C9 C8 121.3(4) . . ?
C10 C9 H9 119.3 . . ?
C14 C15 H15 120.5 . . ?
C16 C15 C14 119.0(4) . . ?
C16 C15 H15 120.5 . . ?
C11 C10 H10 120.4 . . ?
C9 C10 C11 119.3(5) . . ?
C9 C10 H10 120.4 . . ?
C18 C17 C16 117.9(5) . . ?
C18 C17 C20 121.4(4) . . ?
C16 C17 C20 120.7(5) . . ?
C4 C3 H3A 111.2 . . ?
C4 C3 H3B 111.2 . . ?
C4 C3 C2 102.7(3) . . ?
H3A C3 H3B 109.1 . . ?
C2 C3 H3A 111.2 . . ?
C2 C3 H3B 111.2 . . ?
C19 C18 C17 121.1(4) . . ?
C19 C18 H18 119.5 . . ?
C17 C18 H18 119.5 . . ?
O1 C21 C5 122.5(5) . . ?
O1 C21 H21 118.7 . . ?
C5 C21 H21 118.7 . . ?
C15 C16 C17 122.0(5) . . ?
C15 C16 H16 119.0 . . ?
C17 C16 H16 119.0 . . ?
C17 C20 H20A 109.5 . . ?
C17 C20 H20B 109.5 . . ?
C17 C20 H20C 109.5 . . ?
H20A C20 H20B 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C1 C2 C3 106.9(3) . . ?
C1 C2 H2A 110.3 . . ?
C1 C2 H2B 110.3 . . ?
C3 C2 H2A 110.3 . . ?
C3 C2 H2B 110.3 . . ?
H2A C2 H2B 108.6 . . ?


_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 4.706
_oxdiff_exptl_absorpt_empirical_full_min 0.332
