# Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.
# This journal is © the Partner Organisations 2016

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_1
_database_code_depnum_ccdc_archive 'CCDC 1407324'
_audit_update_record             
;
2015-07-21 deposited with the CCDC.
2016-08-18 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        (S)-3o
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C21 H19 Br N2 O4'
_chemical_formula_sum            'C21 H19 Br N2 O4'
_chemical_formula_weight         443.29

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'
Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   'P2(1)2(1)2(1) '

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

_cell_length_a                   8.4058(3)
_cell_length_b                   10.8659(4)
_cell_length_c                   21.9188(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2001.99(13)
_cell_formula_units_Z            4
_cell_measurement_temperature    173(2)
_cell_measurement_reflns_used    1528
_cell_measurement_theta_min      3.5580
_cell_measurement_theta_max      22.6980

_exptl_crystal_description       Block
_exptl_crystal_colour            Yellow
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.20
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.471
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             904
_exptl_absorpt_coefficient_mu    2.082
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6808
_exptl_absorpt_correction_T_max  0.8188
_exptl_absorpt_process_details   
; 
CrysAlisPro, Agilent Technologies, 
Version 1.171.36.24 (release 03-12-2012 CrysAlis171 .NET) 
(compiled Dec  3 2012,18:21:49) 
Empirical absorption correction using spherical harmonics, 
 implemented in SCALE3 ABSPACK scaling algorithm. 
;

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      173(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Xcalibur, Sapphire3, Gemini ultra'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            5801
_diffrn_reflns_av_R_equivalents  0.0368
_diffrn_reflns_av_sigmaI/netI    0.0664
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_theta_min         3.05
_diffrn_reflns_theta_max         26.00
_reflns_number_total             3551
_reflns_number_gt                3121
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker FRAMBO'
_computing_cell_refinement       'Bruker FRAMBO'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

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

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0367P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_chemical_absolute_configuration unk
_refine_ls_abs_structure_Flack   0.018(10)
_refine_ls_number_reflns         3551
_refine_ls_number_parameters     253
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0545
_refine_ls_R_factor_gt           0.0449
_refine_ls_wR_factor_ref         0.0898
_refine_ls_wR_factor_gt          0.0864
_refine_ls_goodness_of_fit_ref   0.999
_refine_ls_restrained_S_all      0.999
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.97087(5) 0.08586(4) 0.01664(2) 0.04306(15) Uani 1 1 d . . .
O1 O 1.3332(3) 0.6155(3) -0.11898(14) 0.0364(8) Uani 1 1 d . . .
O2 O 1.1465(3) 0.6959(3) -0.05880(13) 0.0312(7) Uani 1 1 d . . .
O3 O 1.1691(4) 0.7310(3) -0.23341(17) 0.0544(10) Uani 1 1 d . . .
O4 O 0.9871(4) 0.6336(3) -0.28323(14) 0.0600(10) Uani 1 1 d . . .
C1 C 1.0589(4) 0.5616(3) -0.13768(15) 0.0177(8) Uani 1 1 d . . .
C2 C 1.1952(4) 0.6292(3) -0.10613(18) 0.0214(9) Uani 1 1 d . . .
C3 C 1.2703(5) 0.7536(4) -0.0220(2) 0.0469(13) Uani 1 1 d . . .
H3A H 1.2212 0.8001 0.0113 0.070 Uiso 1 1 calc R . .
H3B H 1.3328 0.8096 -0.0476 0.070 Uiso 1 1 calc R . .
H3C H 1.3402 0.6900 -0.0051 0.070 Uiso 1 1 calc R . .
C4 C 1.1106(5) 0.5297(4) -0.20377(17) 0.0241(9) Uani 1 1 d . . .
H4A H 1.2239 0.5047 -0.2042 0.029 Uiso 1 1 calc R . .
H4B H 1.0462 0.4601 -0.2193 0.029 Uiso 1 1 calc R . .
C5 C 1.0425(4) 0.4417(3) -0.10051(16) 0.0192(8) Uani 1 1 d . . .
C6 C 0.9658(4) 0.4461(3) -0.04408(17) 0.0266(9) Uani 1 1 d . . .
H6A H 0.9264 0.5225 -0.0294 0.032 Uiso 1 1 calc R . .
C7 C 0.9463(5) 0.3416(4) -0.00927(19) 0.0324(10) Uani 1 1 d . . .
H7A H 0.8930 0.3455 0.0289 0.039 Uiso 1 1 calc R . .
C8 C 1.0055(4) 0.2304(3) -0.03074(16) 0.0256(9) Uani 1 1 d . . .
C9 C 1.0822(5) 0.2242(4) -0.08501(18) 0.0273(10) Uani 1 1 d . . .
H9A H 1.1220 0.1477 -0.0993 0.033 Uiso 1 1 calc R . .
C10 C 1.1024(4) 0.3298(4) -0.11955(18) 0.0220(9) Uani 1 1 d . . .
H10A H 1.1586 0.3252 -0.1571 0.026 Uiso 1 1 calc R . .
C11 C 0.9048(4) 0.6339(3) -0.14003(16) 0.0180(8) Uani 1 1 d . . .
C12 C 0.8859(4) 0.7640(3) -0.13961(17) 0.0198(8) Uani 1 1 d . . .
H12A H 0.9687 0.8223 -0.1335 0.024 Uiso 1 1 calc R . .
C13 C 0.7278(4) 0.7919(4) -0.14945(17) 0.0189(8) Uani 1 1 d . . .
C14 C 0.7551(4) 0.5845(4) -0.15215(16) 0.0198(8) Uani 1 1 d . . .
C15 C 0.6990(4) 0.4549(3) -0.1608(2) 0.0270(10) Uani 1 1 d . . .
H15A H 0.5842 0.4548 -0.1687 0.041 Uiso 1 1 calc R . .
H15B H 0.7212 0.4072 -0.1238 0.041 Uiso 1 1 calc R . .
H15C H 0.7548 0.4179 -0.1955 0.041 Uiso 1 1 calc R . .
C17 C 0.7173(5) 1.0152(4) -0.1302(2) 0.0321(11) Uani 1 1 d . . .
H17A H 0.8189 1.0089 -0.1115 0.039 Uiso 1 1 calc R . .
C18 C 0.6446(6) 1.1285(4) -0.1339(2) 0.0396(12) Uani 1 1 d . . .
H18A H 0.6959 1.1993 -0.1178 0.047 Uiso 1 1 calc R . .
C19 C 0.4965(5) 1.1390(4) -0.1612(2) 0.0438(12) Uani 1 1 d . . .
H19A H 0.4470 1.2173 -0.1646 0.053 Uiso 1 1 calc R . .
C20 C 0.4221(5) 1.0369(5) -0.1829(2) 0.0457(13) Uani 1 1 d . . .
H20A H 0.3194 1.0442 -0.2006 0.055 Uiso 1 1 calc R . .
C21 C 0.4953(4) 0.9210(4) -0.17954(19) 0.0381(10) Uani 1 1 d . . .
H21A H 0.4427 0.8502 -0.1951 0.046 Uiso 1 1 calc R . .
C22 C 0.6460(4) 0.9105(4) -0.15312(17) 0.0222(8) Uani 1 1 d . . .
N1 N 1.0876(5) 0.6400(4) -0.24382(17) 0.0391(10) Uani 1 1 d . . .
N2 N 0.6521(4) 0.6806(3) -0.15742(14) 0.0200(7) Uani 1 1 d . . .
H2A H 0.5498 0.6727 -0.1650 0.024 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 C8 1.905(3) . ?
O1 C2 1.203(4) . ?
O2 C2 1.330(5) . ?
O2 C3 1.458(5) . ?
O3 N1 1.224(5) . ?
O4 N1 1.210(5) . ?
C1 C11 1.516(5) . ?
C1 C2 1.526(5) . ?
C1 C5 1.543(5) . ?
C1 C4 1.552(5) . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C4 N1 1.498(5) . ?
C4 H4A 0.9900 . ?
C4 H4B 0.9900 . ?
C5 C10 1.381(5) . ?
C5 C6 1.396(5) . ?
C6 C7 1.378(5) . ?
C6 H6A 0.9500 . ?
C7 C8 1.389(5) . ?
C7 H7A 0.9500 . ?
C8 C9 1.355(5) . ?
C9 C10 1.385(5) . ?
C9 H9A 0.9500 . ?
C10 H10A 0.9500 . ?
C11 C14 1.393(5) . ?
C11 C12 1.423(5) . ?
C12 C13 1.381(5) . ?
C12 H12A 0.9500 . ?
C13 N2 1.377(5) . ?
C13 C22 1.463(5) . ?
C14 N2 1.361(5) . ?
C14 C15 1.497(5) . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?
C17 C18 1.377(6) . ?
C17 C22 1.381(6) . ?
C17 H17A 0.9500 . ?
C18 C19 1.386(6) . ?
C18 H18A 0.9500 . ?
C19 C20 1.359(6) . ?
C19 H19A 0.9500 . ?
C20 C21 1.404(6) . ?
C20 H20A 0.9500 . ?
C21 C22 1.398(5) . ?
C21 H21A 0.9500 . ?
N2 H2A 0.8800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C2 O2 C3 116.5(3) . . ?
C11 C1 C2 114.0(3) . . ?
C11 C1 C5 112.3(3) . . ?
C2 C1 C5 103.5(3) . . ?
C11 C1 C4 108.9(3) . . ?
C2 C1 C4 108.7(3) . . ?
C5 C1 C4 109.2(3) . . ?
O1 C2 O2 123.2(4) . . ?
O1 C2 C1 123.9(3) . . ?
O2 C2 C1 112.6(3) . . ?
O2 C3 H3A 109.5 . . ?
O2 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
O2 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N1 C4 C1 109.4(3) . . ?
N1 C4 H4A 109.8 . . ?
C1 C4 H4A 109.8 . . ?
N1 C4 H4B 109.8 . . ?
C1 C4 H4B 109.8 . . ?
H4A C4 H4B 108.2 . . ?
C10 C5 C6 117.8(3) . . ?
C10 C5 C1 123.5(3) . . ?
C6 C5 C1 118.7(3) . . ?
C7 C6 C5 121.2(3) . . ?
C7 C6 H6A 119.4 . . ?
C5 C6 H6A 119.4 . . ?
C6 C7 C8 119.1(3) . . ?
C6 C7 H7A 120.5 . . ?
C8 C7 H7A 120.5 . . ?
C9 C8 C7 120.8(4) . . ?
C9 C8 Br1 120.7(3) . . ?
C7 C8 Br1 118.5(3) . . ?
C8 C9 C10 119.8(4) . . ?
C8 C9 H9A 120.1 . . ?
C10 C9 H9A 120.1 . . ?
C5 C10 C9 121.3(3) . . ?
C5 C10 H10A 119.4 . . ?
C9 C10 H10A 119.4 . . ?
C14 C11 C12 106.5(3) . . ?
C14 C11 C1 125.3(3) . . ?
C12 C11 C1 127.6(3) . . ?
C13 C12 C11 108.9(3) . . ?
C13 C12 H12A 125.5 . . ?
C11 C12 H12A 125.5 . . ?
N2 C13 C12 105.8(3) . . ?
N2 C13 C22 123.4(3) . . ?
C12 C13 C22 130.8(3) . . ?
N2 C14 C11 107.1(3) . . ?
N2 C14 C15 120.7(3) . . ?
C11 C14 C15 132.1(3) . . ?
C14 C15 H15A 109.5 . . ?
C14 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C14 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 109.5 . . ?
C18 C17 C22 121.5(4) . . ?
C18 C17 H17A 119.2 . . ?
C22 C17 H17A 119.2 . . ?
C17 C18 C19 119.9(4) . . ?
C17 C18 H18A 120.1 . . ?
C19 C18 H18A 120.1 . . ?
C20 C19 C18 119.8(4) . . ?
C20 C19 H19A 120.1 . . ?
C18 C19 H19A 120.1 . . ?
C19 C20 C21 120.8(4) . . ?
C19 C20 H20A 119.6 . . ?
C21 C20 H20A 119.6 . . ?
C22 C21 C20 119.5(4) . . ?
C22 C21 H21A 120.3 . . ?
C20 C21 H21A 120.3 . . ?
C17 C22 C21 118.5(4) . . ?
C17 C22 C13 120.2(3) . . ?
C21 C22 C13 121.4(4) . . ?
O4 N1 O3 124.8(4) . . ?
O4 N1 C4 117.5(4) . . ?
O3 N1 C4 117.7(4) . . ?
C14 N2 C13 111.7(3) . . ?
C14 N2 H2A 124.2 . . ?
C13 N2 H2A 124.2 . . ?

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
C3 O2 C2 O1 0.1(5) . . . . ?
C3 O2 C2 C1 173.9(3) . . . . ?
C11 C1 C2 O1 -149.5(4) . . . . ?
C5 C1 C2 O1 88.2(4) . . . . ?
C4 C1 C2 O1 -27.9(5) . . . . ?
C11 C1 C2 O2 36.7(4) . . . . ?
C5 C1 C2 O2 -85.6(3) . . . . ?
C4 C1 C2 O2 158.4(3) . . . . ?
C11 C1 C4 N1 43.0(4) . . . . ?
C2 C1 C4 N1 -81.7(4) . . . . ?
C5 C1 C4 N1 166.0(3) . . . . ?
C11 C1 C5 C10 135.3(4) . . . . ?
C2 C1 C5 C10 -101.2(4) . . . . ?
C4 C1 C5 C10 14.4(5) . . . . ?
C11 C1 C5 C6 -45.9(4) . . . . ?
C2 C1 C5 C6 77.5(4) . . . . ?
C4 C1 C5 C6 -166.8(3) . . . . ?
C10 C5 C6 C7 -1.9(6) . . . . ?
C1 C5 C6 C7 179.3(3) . . . . ?
C5 C6 C7 C8 0.6(6) . . . . ?
C6 C7 C8 C9 0.3(6) . . . . ?
C6 C7 C8 Br1 -177.8(3) . . . . ?
C7 C8 C9 C10 0.2(6) . . . . ?
Br1 C8 C9 C10 178.3(3) . . . . ?
C6 C5 C10 C9 2.4(5) . . . . ?
C1 C5 C10 C9 -178.9(3) . . . . ?
C8 C9 C10 C5 -1.6(6) . . . . ?
C2 C1 C11 C14 -163.3(3) . . . . ?
C5 C1 C11 C14 -46.0(5) . . . . ?
C4 C1 C11 C14 75.1(4) . . . . ?
C2 C1 C11 C12 26.8(5) . . . . ?
C5 C1 C11 C12 144.2(4) . . . . ?
C4 C1 C11 C12 -94.7(4) . . . . ?
C14 C11 C12 C13 1.7(4) . . . . ?
C1 C11 C12 C13 173.1(3) . . . . ?
C11 C12 C13 N2 -1.6(4) . . . . ?
C11 C12 C13 C22 179.9(4) . . . . ?
C12 C11 C14 N2 -1.1(4) . . . . ?
C1 C11 C14 N2 -172.8(3) . . . . ?
C12 C11 C14 C15 177.2(4) . . . . ?
C1 C11 C14 C15 5.6(6) . . . . ?
C22 C17 C18 C19 -0.1(7) . . . . ?
C17 C18 C19 C20 1.5(7) . . . . ?
C18 C19 C20 C21 -1.6(7) . . . . ?
C19 C20 C21 C22 0.4(7) . . . . ?
C18 C17 C22 C21 -1.2(6) . . . . ?
C18 C17 C22 C13 178.9(4) . . . . ?
C20 C21 C22 C17 1.0(6) . . . . ?
C20 C21 C22 C13 -179.1(4) . . . . ?
N2 C13 C22 C17 163.9(4) . . . . ?
C12 C13 C22 C17 -17.8(6) . . . . ?
N2 C13 C22 C21 -16.0(6) . . . . ?
C12 C13 C22 C21 162.3(4) . . . . ?
C1 C4 N1 O4 -113.3(4) . . . . ?
C1 C4 N1 O3 65.1(4) . . . . ?
C11 C14 N2 C13 0.2(4) . . . . ?
C15 C14 N2 C13 -178.4(3) . . . . ?
C12 C13 N2 C14 0.9(4) . . . . ?
C22 C13 N2 C14 179.6(3) . . . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        26.00
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.496
_refine_diff_density_min         -0.398
_refine_diff_density_rms         0.064
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: nHexane'
