# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_a31021a
_database_code_depnum_ccdc_archive 'CCDC 1410300'
_audit_update_record             
;
2015-07-02 deposited with the CCDC.
2015-08-06 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C14 H18 N2 O3 S'
_chemical_formula_weight         294.36

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           4
_space_group_name_H-M_alt        'P 21'
_space_group_name_Hall           'P 2yb'

_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+1/2, -z'

_cell_length_a                   6.306(4)
_cell_length_b                   8.935(6)
_cell_length_c                   13.518(9)
_cell_angle_alpha                90
_cell_angle_beta                 96.662(8)
_cell_angle_gamma                90
_cell_volume                     756.5(8)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    774
_cell_measurement_theta_min      2.738
_cell_measurement_theta_max      24.448

_exptl_crystal_description       rod
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.292
_exptl_crystal_F_000             312
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.380
_exptl_crystal_size_mid          0.120
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    0.222
_shelx_estimated_absorpt_T_min   0.920
_shelx_estimated_absorpt_T_max   0.978
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.587
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            3621
_diffrn_reflns_av_unetI/netI     0.0505
_diffrn_reflns_av_R_equivalents  0.0271
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         1.517
_diffrn_reflns_theta_max         27.000
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.908
_diffrn_reflns_point_group_measured_fraction_full 0.950
_reflns_number_total             2992
_reflns_number_gt                2002
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.735
_reflns_Friedel_fraction_max     0.823
_reflns_Friedel_fraction_full    0.896

_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 SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SHELXTL'
_computing_structure_solution    'Bruker SHELXTL'
_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)+(0.0583P)²] 
 where P=(Fo²+2Fc²)/3 
;
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
; 
 Flack x determined using 720 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.13(9)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         2992
_refine_ls_number_parameters     188
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0672
_refine_ls_R_factor_gt           0.0442
_refine_ls_wR_factor_ref         0.1040
_refine_ls_wR_factor_gt          0.0982
_refine_ls_goodness_of_fit_ref   0.912
_refine_ls_restrained_S_all      0.912
_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
S1 S 0.59061(18) 0.41856(9) 0.39831(7) 0.0622(3) Uani 1 1 d . . . . .
N1 N 0.7010(5) 0.2973(3) 0.4834(2) 0.0564(9) Uani 1 1 d . . . . .
N2 N 0.8189(5) 0.2768(4) 0.7073(2) 0.0587(8) Uani 1 1 d . . . . .
O1 O 0.4328(6) 0.5075(4) 0.4444(2) 0.0939(11) Uani 1 1 d . . . . .
O2 O 0.9686(5) 0.4582(3) 0.5265(2) 0.0755(9) Uani 1 1 d . . . . .
O3 O 1.1490(4) 0.3562(4) 0.7637(2) 0.0727(8) Uani 1 1 d . . . . .
C1 C 0.4405(7) 0.2883(5) 0.3141(3) 0.0612(11) Uani 1 1 d . . . . .
C2 C 0.2741(8) 0.2066(6) 0.3638(4) 0.0941(17) Uani 1 1 d . . . . .
H2A H 0.1811 0.1535 0.3146 0.141 Uiso 1 1 calc R U . . .
H2B H 0.1924 0.2772 0.3973 0.141 Uiso 1 1 calc R U . . .
H2C H 0.3423 0.1369 0.4113 0.141 Uiso 1 1 calc R U . . .
C3 C 0.3339(10) 0.3879(6) 0.2323(3) 0.1030(19) Uani 1 1 d . . . . .
H3A H 0.4412 0.4382 0.1998 0.155 Uiso 1 1 calc R U . . .
H3B H 0.2465 0.4607 0.2606 0.155 Uiso 1 1 calc R U . . .
H3C H 0.2466 0.3281 0.1847 0.155 Uiso 1 1 calc R U . . .
C4 C 0.5985(10) 0.1831(9) 0.2745(5) 0.133(3) Uani 1 1 d . . . . .
H4A H 0.5247 0.1183 0.2254 0.200 Uiso 1 1 calc R U . . .
H4B H 0.6677 0.1242 0.3282 0.200 Uiso 1 1 calc R U . . .
H4C H 0.7035 0.2402 0.2447 0.200 Uiso 1 1 calc R U . . .
C5 C 0.8806(7) 0.3422(5) 0.5415(3) 0.0540(9) Uani 1 1 d . . . . .
C6 C 0.9535(6) 0.2413(4) 0.6277(3) 0.0611(11) Uani 1 1 d . . . . .
H6 H 0.9405 0.1357 0.6084 0.073 Uiso 1 1 calc R U . . .
C7 C 1.1806(7) 0.2784(6) 0.6736(4) 0.0773(13) Uani 1 1 d . . . . .
H7A H 1.2638 0.1880 0.6879 0.093 Uiso 1 1 calc R U . . .
H7B H 1.2526 0.3415 0.6296 0.093 Uiso 1 1 calc R U . . .
C8 C 0.9396(6) 0.3428(4) 0.7740(3) 0.0528(9) Uani 1 1 d . . . . .
C9 C 0.8735(6) 0.4077(5) 0.8646(3) 0.0565(9) Uani 1 1 d . . . . .
C10 C 1.0068(8) 0.5038(6) 0.9228(4) 0.0833(14) Uani 1 1 d . . . . .
H10 H 1.1387 0.5299 0.9036 0.100 Uiso 1 1 calc R U . . .
C11 C 0.9440(13) 0.5608(7) 1.0092(5) 0.117(2) Uani 1 1 d . . . . .
H11 H 1.0358 0.6223 1.0498 0.140 Uiso 1 1 calc R U . . .
C12 C 0.7487(11) 0.5274(8) 1.0352(4) 0.114(2) Uani 1 1 d . . . . .
H12 H 0.7055 0.5699 1.0924 0.137 Uiso 1 1 calc R U . . .
C13 C 0.6136(9) 0.4326(9) 0.9793(4) 0.1055(18) Uani 1 1 d . . . . .
H13 H 0.4814 0.4081 0.9989 0.127 Uiso 1 1 calc R U . . .
C14 C 0.6769(7) 0.3742(6) 0.8935(3) 0.0737(14) Uani 1 1 d . . . . .
H14 H 0.5852 0.3109 0.8542 0.088 Uiso 1 1 calc R U . . .
H1 H 0.617(6) 0.228(5) 0.502(3) 0.060(12) Uiso 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
S1 O1 1.467(3) . ?
S1 N1 1.672(3) . ?
S1 C1 1.816(4) . ?
N1 C5 1.362(5) . ?
N1 H1 0.87(4) . ?
N2 C8 1.257(5) . ?
N2 C6 1.480(5) . ?
O2 C5 1.204(5) . ?
O3 C8 1.349(4) . ?
O3 C7 1.436(5) . ?
C1 C2 1.499(6) . ?
C1 C4 1.512(7) . ?
C1 C3 1.515(6) . ?
C2 H2A 0.9600 . ?
C2 H2B 0.9600 . ?
C2 H2C 0.9600 . ?
C3 H3A 0.9600 . ?
C3 H3B 0.9600 . ?
C3 H3C 0.9600 . ?
C4 H4A 0.9600 . ?
C4 H4B 0.9600 . ?
C4 H4C 0.9600 . ?
C5 C6 1.502(6) . ?
C6 C7 1.530(6) . ?
C6 H6 0.9800 . ?
C7 H7A 0.9700 . ?
C7 H7B 0.9700 . ?
C8 C9 1.458(5) . ?
C9 C14 1.375(6) . ?
C9 C10 1.382(6) . ?
C10 C11 1.374(7) . ?
C10 H10 0.9300 . ?
C11 C12 1.353(9) . ?
C11 H11 0.9300 . ?
C12 C13 1.366(9) . ?
C12 H12 0.9300 . ?
C13 C14 1.373(7) . ?
C13 H13 0.9300 . ?
C14 H14 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
O1 S1 N1 107.90(19) . . ?
O1 S1 C1 106.5(2) . . ?
N1 S1 C1 99.24(17) . . ?
C5 N1 S1 117.2(3) . . ?
C5 N1 H1 123(3) . . ?
S1 N1 H1 116(3) . . ?
C8 N2 C6 105.8(3) . . ?
C8 O3 C7 106.2(3) . . ?
C2 C1 C4 112.4(5) . . ?
C2 C1 C3 109.8(4) . . ?
C4 C1 C3 111.2(5) . . ?
C2 C1 S1 111.9(3) . . ?
C4 C1 S1 107.6(3) . . ?
C3 C1 S1 103.6(3) . . ?
C1 C2 H2A 109.5 . . ?
C1 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
C1 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
C1 C3 H3A 109.5 . . ?
C1 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
C1 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
C1 C4 H4A 109.5 . . ?
C1 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
C1 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
O2 C5 N1 121.7(4) . . ?
O2 C5 C6 122.8(4) . . ?
N1 C5 C6 115.5(4) . . ?
N2 C6 C5 106.6(3) . . ?
N2 C6 C7 104.3(3) . . ?
C5 C6 C7 111.9(4) . . ?
N2 C6 H6 111.2 . . ?
C5 C6 H6 111.2 . . ?
C7 C6 H6 111.2 . . ?
O3 C7 C6 103.5(3) . . ?
O3 C7 H7A 111.1 . . ?
C6 C7 H7A 111.1 . . ?
O3 C7 H7B 111.1 . . ?
C6 C7 H7B 111.1 . . ?
H7A C7 H7B 109.0 . . ?
N2 C8 O3 119.0(4) . . ?
N2 C8 C9 125.5(4) . . ?
O3 C8 C9 115.4(3) . . ?
C14 C9 C10 118.8(4) . . ?
C14 C9 C8 120.5(4) . . ?
C10 C9 C8 120.8(4) . . ?
C11 C10 C9 119.9(5) . . ?
C11 C10 H10 120.0 . . ?
C9 C10 H10 120.0 . . ?
C12 C11 C10 120.0(6) . . ?
C12 C11 H11 120.0 . . ?
C10 C11 H11 120.0 . . ?
C11 C12 C13 121.4(6) . . ?
C11 C12 H12 119.3 . . ?
C13 C12 H12 119.3 . . ?
C12 C13 C14 118.7(6) . . ?
C12 C13 H13 120.7 . . ?
C14 C13 H13 120.7 . . ?
C13 C14 C9 121.2(5) . . ?
C13 C14 H14 119.4 . . ?
C9 C14 H14 119.4 . . ?

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
O1 S1 N1 C5 -91.0(3) . . . . ?
C1 S1 N1 C5 158.3(3) . . . . ?
O1 S1 C1 C2 -49.6(4) . . . . ?
N1 S1 C1 C2 62.3(4) . . . . ?
O1 S1 C1 C4 -173.6(4) . . . . ?
N1 S1 C1 C4 -61.7(4) . . . . ?
O1 S1 C1 C3 68.6(4) . . . . ?
N1 S1 C1 C3 -179.5(3) . . . . ?
S1 N1 C5 O2 -6.9(5) . . . . ?
S1 N1 C5 C6 170.2(3) . . . . ?
C8 N2 C6 C5 -109.2(4) . . . . ?
C8 N2 C6 C7 9.4(4) . . . . ?
O2 C5 C6 N2 97.0(4) . . . . ?
N1 C5 C6 N2 -80.1(4) . . . . ?
O2 C5 C6 C7 -16.5(5) . . . . ?
N1 C5 C6 C7 166.5(3) . . . . ?
C8 O3 C7 C6 8.5(4) . . . . ?
N2 C6 C7 O3 -10.8(4) . . . . ?
C5 C6 C7 O3 104.1(4) . . . . ?
C6 N2 C8 O3 -4.5(5) . . . . ?
C6 N2 C8 C9 175.8(4) . . . . ?
C7 O3 C8 N2 -2.9(5) . . . . ?
C7 O3 C8 C9 176.8(4) . . . . ?
N2 C8 C9 C14 13.4(6) . . . . ?
O3 C8 C9 C14 -166.3(4) . . . . ?
N2 C8 C9 C10 -166.6(4) . . . . ?
O3 C8 C9 C10 13.7(6) . . . . ?
C14 C9 C10 C11 1.7(7) . . . . ?
C8 C9 C10 C11 -178.3(5) . . . . ?
C9 C10 C11 C12 -2.5(10) . . . . ?
C10 C11 C12 C13 2.7(11) . . . . ?
C11 C12 C13 C14 -1.9(10) . . . . ?
C12 C13 C14 C9 1.1(8) . . . . ?
C10 C9 C14 C13 -1.0(7) . . . . ?
C8 C9 C14 C13 179.0(5) . . . . ?

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
N1 H1 O1 0.87(4) 2.14(5) 2.926(5) 151(4) 2_646

_refine_diff_density_max         0.196
_refine_diff_density_min         -0.210
_refine_diff_density_rms         0.051

_shelxl_version_number           2013-2

####################################################################### 
# 
# 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_a40304a
_database_code_depnum_ccdc_archive 'CCDC 1410301'
_audit_update_record             
;
2015-07-02 deposited with the CCDC.
2015-08-06 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H17 Br2 F O4'
_chemical_formula_weight         500.15

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0171 0.0103 '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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_H-M_alt        'P 21'
_space_group_name_Hall           'P 2yb'

_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+1/2, -z'

_cell_length_a                   11.651(4)
_cell_length_b                   5.9117(18)
_cell_length_c                   14.797(5)
_cell_angle_alpha                90
_cell_angle_beta                 96.518(4)
_cell_angle_gamma                90
_cell_volume                     1012.6(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1776
_cell_measurement_theta_min      2.36
_cell_measurement_theta_max      25.30

_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.640
_exptl_crystal_F_000             496
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.260
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.080
_exptl_absorpt_coefficient_mu    4.033
_shelx_estimated_absorpt_T_min   0.420
_shelx_estimated_absorpt_T_max   0.739
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.542
_exptl_absorpt_correction_T_max  0.746
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(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            5347
_diffrn_reflns_av_unetI/netI     0.0713
_diffrn_reflns_av_R_equivalents  0.0219
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         1.385
_diffrn_reflns_theta_max         25.995
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measured_fraction_theta_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.926
_diffrn_reflns_point_group_measured_fraction_full 0.935
_reflns_number_total             3693
_reflns_number_gt                2973
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.699
_reflns_Friedel_fraction_max     0.849
_reflns_Friedel_fraction_full    0.867

_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)+(0.0250P)²] 
 where P=(Fo²+2Fc²)/3 
;
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
; 
 Flack x determined using 1087 quotients [(I+)-(I-)]/[(I+)+(I-)] 
 (Parsons and Flack (2004), Acta Cryst. A60, s61). 
;
_refine_ls_abs_structure_Flack   0.031(9)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         3693
_refine_ls_number_parameters     246
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0514
_refine_ls_R_factor_gt           0.0379
_refine_ls_wR_factor_ref         0.0979
_refine_ls_wR_factor_gt          0.0932
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_restrained_S_all      1.051
_refine_ls_shift/su_max          0.004
_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 -0.29631(6) 0.35823(17) 0.37166(6) 0.0791(3) Uani 1 1 d . . . . .
Br2 Br 0.20313(7) 0.52163(14) -0.17509(4) 0.0669(3) Uani 1 1 d . . . . .
F1 F 0.3030(3) 0.0762(6) 0.2499(2) 0.0551(10) Uani 1 1 d . . . . .
O1 O 0.3810(6) 0.2911(10) 0.3979(4) 0.0817(18) Uani 1 1 d . . . . .
O2 O 0.4018(4) 0.6088(8) 0.3221(3) 0.0555(13) Uani 1 1 d . . . . .
O3 O 0.4800(6) 0.1101(11) 0.1576(5) 0.100(2) Uani 1 1 d . . . . .
O4 O 0.4655(4) 0.4801(9) 0.1508(3) 0.0588(13) Uani 1 1 d . . . . .
C1 C 0.2354(5) 0.4280(9) 0.1857(4) 0.0350(13) Uani 1 1 d . . . . .
H1 H 0.2627 0.5819 0.1759 0.042 Uiso 1 1 calc R U . . .
C2 C 0.1366(5) 0.4466(10) 0.2424(4) 0.0382(14) Uani 1 1 d . . . . .
H2 H 0.0908 0.3196 0.2479 0.046 Uiso 1 1 calc R U . . .
C3 C 0.1116(5) 0.6326(11) 0.2844(4) 0.0415(14) Uani 1 1 d . . . . .
H3 H 0.1613 0.7545 0.2805 0.050 Uiso 1 1 calc R U . . .
C4 C 0.0134(6) 0.6687(11) 0.3369(4) 0.0429(14) Uani 1 1 d . . . . .
C5 C -0.0782(5) 0.5191(13) 0.3345(3) 0.0438(13) Uani 1 1 d . . . . .
H5 H -0.0772 0.3876 0.3001 0.053 Uiso 1 1 calc R U . . .
C6 C -0.1706(5) 0.5612(12) 0.3819(4) 0.0492(16) Uani 1 1 d . . . . .
C7 C -0.1739(7) 0.7552(14) 0.4341(5) 0.064(2) Uani 1 1 d . . . . .
H7 H -0.2366 0.7844 0.4660 0.077 Uiso 1 1 calc R U . . .
C8 C -0.0825(7) 0.9041(14) 0.4379(5) 0.069(2) Uani 1 1 d . . . . .
H8 H -0.0831 1.0335 0.4736 0.083 Uiso 1 1 calc R U . . .
C9 C 0.0098(6) 0.8643(14) 0.3896(4) 0.0536(16) Uani 1 1 d . . . . .
H9 H 0.0700 0.9681 0.3920 0.064 Uiso 1 1 calc R U . . .
C10 C 0.1959(4) 0.3285(10) 0.0929(4) 0.0348(12) Uani 1 1 d . . . . .
C11 C 0.2154(5) 0.4464(10) 0.0156(4) 0.0377(14) Uani 1 1 d . . . . .
H11 H 0.2539 0.5845 0.0205 0.045 Uiso 1 1 calc R U . . .
C12 C 0.1776(4) 0.3583(12) -0.0695(4) 0.0395(13) Uani 1 1 d . . . . .
C13 C 0.1256(5) 0.1495(12) -0.0785(4) 0.0487(16) Uani 1 1 d . . . . .
H13 H 0.1051 0.0877 -0.1359 0.058 Uiso 1 1 calc R U . . .
C14 C 0.1046(5) 0.0334(12) -0.0021(4) 0.0448(14) Uani 1 1 d . . . . .
H14 H 0.0666 -0.1051 -0.0076 0.054 Uiso 1 1 calc R U . . .
C15 C 0.1395(5) 0.1209(11) 0.0831(4) 0.0423(14) Uani 1 1 d . . . . .
H15 H 0.1251 0.0402 0.1346 0.051 Uiso 1 1 calc R U . . .
C16 C 0.3370(5) 0.2966(9) 0.2356(4) 0.0402(14) Uani 1 1 d . . . . .
C17 C 0.3766(5) 0.3967(12) 0.3284(4) 0.0450(16) Uani 1 1 d . . . . .
C18 C 0.4393(8) 0.7270(15) 0.4053(6) 0.079(3) Uani 1 1 d . . . . .
H18A H 0.3785 0.7258 0.4440 0.119 Uiso 1 1 calc R U . . .
H18B H 0.4580 0.8805 0.3917 0.119 Uiso 1 1 calc R U . . .
H18C H 0.5063 0.6536 0.4357 0.119 Uiso 1 1 calc R U . . .
C19 C 0.4387(6) 0.2809(12) 0.1773(4) 0.0476(16) Uani 1 1 d . . . . .
C20 C 0.5626(6) 0.498(2) 0.0980(5) 0.089(3) Uani 1 1 d . . . . .
H20A H 0.5982 0.3525 0.0943 0.133 Uiso 1 1 calc R U . . .
H20B H 0.6178 0.6034 0.1268 0.133 Uiso 1 1 calc R U . . .
H20C H 0.5359 0.5504 0.0378 0.133 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 C6 1.886(7) . ?
Br2 C12 1.889(6) . ?
F1 C16 1.385(6) . ?
O1 C17 1.200(8) . ?
O2 C17 1.293(8) . ?
O2 C18 1.439(9) . ?
O3 C19 1.170(9) . ?
O4 C19 1.291(8) . ?
O4 C20 1.449(8) . ?
C1 C2 1.503(8) . ?
C1 C10 1.517(7) . ?
C1 C16 1.532(8) . ?
C2 C3 1.312(8) . ?
C3 C4 1.471(9) . ?
C4 C5 1.383(9) . ?
C4 C9 1.398(10) . ?
C5 C6 1.373(8) . ?
C6 C7 1.386(10) . ?
C7 C8 1.378(11) . ?
C8 C9 1.377(10) . ?
C10 C11 1.381(7) . ?
C10 C15 1.392(9) . ?
C11 C12 1.388(8) . ?
C12 C13 1.374(10) . ?
C13 C14 1.369(9) . ?
C14 C15 1.381(9) . ?
C16 C17 1.518(9) . ?
C16 C19 1.546(8) . ?

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
C17 O2 C18 117.3(6) . . ?
C19 O4 C20 117.5(7) . . ?
C2 C1 C10 111.1(4) . . ?
C2 C1 C16 111.5(4) . . ?
C10 C1 C16 112.2(5) . . ?
C3 C2 C1 123.4(5) . . ?
C2 C3 C4 126.9(6) . . ?
C5 C4 C9 118.1(6) . . ?
C5 C4 C3 122.6(6) . . ?
C9 C4 C3 119.3(6) . . ?
C6 C5 C4 121.2(7) . . ?
C5 C6 C7 120.5(7) . . ?
C5 C6 Br1 119.4(5) . . ?
C7 C6 Br1 120.1(5) . . ?
C8 C7 C6 118.8(6) . . ?
C9 C8 C7 121.0(7) . . ?
C8 C9 C4 120.4(7) . . ?
C11 C10 C15 118.6(5) . . ?
C11 C10 C1 119.5(5) . . ?
C15 C10 C1 121.8(5) . . ?
C10 C11 C12 119.8(5) . . ?
C13 C12 C11 121.1(6) . . ?
C13 C12 Br2 119.2(5) . . ?
C11 C12 Br2 119.6(5) . . ?
C14 C13 C12 119.2(6) . . ?
C13 C14 C15 120.3(6) . . ?
C14 C15 C10 120.8(6) . . ?
F1 C16 C17 106.9(5) . . ?
F1 C16 C1 109.4(4) . . ?
C17 C16 C1 112.1(5) . . ?
F1 C16 C19 106.2(5) . . ?
C17 C16 C19 110.7(5) . . ?
C1 C16 C19 111.2(4) . . ?
O1 C17 O2 125.3(7) . . ?
O1 C17 C16 123.5(6) . . ?
O2 C17 C16 111.2(6) . . ?
O3 C19 O4 126.3(7) . . ?
O3 C19 C16 123.6(7) . . ?
O4 C19 C16 110.0(5) . . ?

_refine_diff_density_max         0.522
_refine_diff_density_min         -0.516
_refine_diff_density_rms         0.062

_shelxl_version_number           2013-2

