# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2017

####################################################################### 
# 
# 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_No1
_database_code_depnum_ccdc_archive 'CCDC 1505485'
_audit_update_record             
;
2016-09-21 deposited with the CCDC.
2017-07-17 downloaded from the CCDC.
;

_audit_creation_method           SHELXTL
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C19 H20 N2 O3'
_chemical_formula_sum            'C19 H20 N2 O3'
_chemical_formula_weight         324.37

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'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   C2/c
_symmetry_space_group_name_Hall  '-C 2yc'

loop_
_symmetry_equiv_pos_as_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                   17.4957(4)
_cell_length_b                   13.0591(4)
_cell_length_c                   16.2596(5)
_cell_angle_alpha                90.00
_cell_angle_beta                 113.4471(11)
_cell_angle_gamma                90.00
_cell_volume                     3408.21(17)
_cell_formula_units_Z            8
_cell_measurement_temperature    223(2)
_cell_measurement_reflns_used    9374
_cell_measurement_theta_min      2.54
_cell_measurement_theta_max      27.85

_exptl_crystal_description       Block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.10
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.264
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1376
_exptl_absorpt_coefficient_mu    0.086
_exptl_absorpt_correction_type   Multi-scan
_exptl_absorpt_correction_T_min  0.9804
_exptl_absorpt_correction_T_max  0.9914
_exptl_absorpt_process_details   'Bruker SADABS'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      223(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  'PHOTON 100 CMOS'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            80577
_diffrn_reflns_av_R_equivalents  0.0572
_diffrn_reflns_av_sigmaI/netI    0.0172
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         2.13
_diffrn_reflns_theta_max         28.33
_reflns_number_total             4246
_reflns_number_gt                3262
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_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)+(0.0443P)²+3.0587P] 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_number_reflns         4246
_refine_ls_number_parameters     220
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0621
_refine_ls_R_factor_gt           0.0435
_refine_ls_wR_factor_ref         0.1180
_refine_ls_wR_factor_gt          0.1073
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_restrained_S_all      1.040
_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
C1 C 0.14678(9) 0.97202(11) 0.09701(9) 0.0318(3) Uani 1 1 d . . .
O1 O 0.15979(7) 1.06098(8) 0.12377(8) 0.0448(3) Uani 1 1 d . . .
C2 C 0.07843(9) 0.90993(11) 0.10498(9) 0.0315(3) Uani 1 1 d . . .
C3 C 0.01071(10) 0.95969(11) 0.11084(11) 0.0382(3) Uani 1 1 d . . .
H3 H 0.0089 1.0316 0.1096 0.046 Uiso 1 1 calc R . .
C4 C -0.05422(10) 0.90594(12) 0.11847(11) 0.0419(4) Uani 1 1 d . . .
H4 H -0.0997 0.9412 0.1219 0.050 Uiso 1 1 calc R . .
C5 C -0.05190(10) 0.80019(12) 0.12106(12) 0.0414(4) Uani 1 1 d . . .
C6 C 0.01605(11) 0.74915(13) 0.11658(14) 0.0507(4) Uani 1 1 d . . .
H6 H 0.0182 0.6772 0.1192 0.061 Uiso 1 1 calc R . .
C7 C 0.08012(10) 0.80325(12) 0.10839(12) 0.0425(4) Uani 1 1 d . . .
H7 H 0.1256 0.7679 0.1051 0.051 Uiso 1 1 calc R . .
O2 O -0.11287(8) 0.73928(10) 0.12712(11) 0.0607(4) Uani 1 1 d . . .
C8 C -0.18385(12) 0.78742(15) 0.13177(15) 0.0595(5) Uani 1 1 d . . .
H8A H -0.1665 0.8310 0.1844 0.089 Uiso 1 1 calc R . .
H8B H -0.2220 0.7356 0.1357 0.089 Uiso 1 1 calc R . .
H8C H -0.2115 0.8285 0.0784 0.089 Uiso 1 1 calc R . .
N1 N 0.19264(7) 0.92455(9) 0.05835(8) 0.0307(3) Uani 1 1 d . . .
H1A H 0.1774 0.8642 0.0349 0.037 Uiso 1 1 calc R . .
C9 C 0.26637(8) 0.97086(10) 0.05475(9) 0.0304(3) Uani 1 1 d . . .
H9A H 0.2654 1.0447 0.0653 0.036 Uiso 1 1 calc R . .
H9B H 0.2655 0.9612 -0.0054 0.036 Uiso 1 1 calc R . .
C10 C 0.34720(8) 0.92538(10) 0.12412(8) 0.0260(3) Uani 1 1 d . . .
C11 C 0.35065(8) 0.81024(10) 0.10801(9) 0.0282(3) Uani 1 1 d . . .
O3 O 0.34669(7) 0.77097(8) 0.03812(7) 0.0397(3) Uani 1 1 d . . .
N2 N 0.35968(8) 0.75947(9) 0.18431(8) 0.0321(3) Uani 1 1 d . . .
C12 C 0.36128(8) 0.82803(10) 0.25191(9) 0.0282(3) Uani 1 1 d . . .
C13 C 0.37135(10) 0.80627(12) 0.33879(10) 0.0369(3) Uani 1 1 d . . .
H13 H 0.3786 0.7388 0.3607 0.044 Uiso 1 1 calc R . .
C14 C 0.37026(10) 0.88898(13) 0.39227(10) 0.0399(4) Uani 1 1 d . . .
H14 H 0.3772 0.8770 0.4518 0.048 Uiso 1 1 calc R . .
C15 C 0.35931(10) 0.98804(12) 0.36020(10) 0.0376(3) Uani 1 1 d . . .
H15 H 0.3581 1.0422 0.3977 0.045 Uiso 1 1 calc R . .
C16 C 0.35004(9) 1.00832(11) 0.27252(9) 0.0328(3) Uani 1 1 d . . .
H16 H 0.3428 1.0758 0.2506 0.039 Uiso 1 1 calc R . .
C17 C 0.35168(8) 0.92759(10) 0.21873(8) 0.0260(3) Uani 1 1 d . . .
C18 C 0.42318(9) 0.97617(12) 0.11690(10) 0.0351(3) Uani 1 1 d . . .
H18A H 0.4223 1.0491 0.1278 0.053 Uiso 1 1 calc R . .
H18B H 0.4217 0.9651 0.0573 0.053 Uiso 1 1 calc R . .
H18C H 0.4737 0.9465 0.1610 0.053 Uiso 1 1 calc R . .
C19 C 0.36586(13) 0.64901(12) 0.19350(12) 0.0521(5) Uani 1 1 d . . .
H19A H 0.3547 0.6183 0.1355 0.078 Uiso 1 1 calc R . .
H19B H 0.3255 0.6244 0.2160 0.078 Uiso 1 1 calc R . .
H19C H 0.4215 0.6305 0.2352 0.078 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
C1 O1 1.2296(17) . ?
C1 N1 1.3508(17) . ?
C1 C2 1.493(2) . ?
C2 C3 1.3873(19) . ?
C2 C7 1.394(2) . ?
C3 C4 1.382(2) . ?
C3 H3 0.9400 . ?
C4 C5 1.382(2) . ?
C4 H4 0.9400 . ?
C5 O2 1.3653(19) . ?
C5 C6 1.390(2) . ?
C6 C7 1.376(2) . ?
C6 H6 0.9400 . ?
C7 H7 0.9400 . ?
O2 C8 1.420(2) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C8 H8C 0.9700 . ?
N1 C9 1.4468(17) . ?
N1 H1A 0.8700 . ?
C9 C10 1.5347(18) . ?
C9 H9A 0.9800 . ?
C9 H9B 0.9800 . ?
C10 C17 1.5091(17) . ?
C10 C18 1.5313(18) . ?
C10 C11 1.5317(18) . ?
C11 O3 1.2233(16) . ?
C11 N2 1.3592(18) . ?
N2 C12 1.4094(17) . ?
N2 C19 1.4499(18) . ?
C12 C13 1.3816(19) . ?
C12 C17 1.3919(18) . ?
C13 C14 1.392(2) . ?
C13 H13 0.9400 . ?
C14 C15 1.379(2) . ?
C14 H14 0.9400 . ?
C15 C16 1.394(2) . ?
C15 H15 0.9400 . ?
C16 C17 1.3775(19) . ?
C16 H16 0.9400 . ?
C18 H18A 0.9700 . ?
C18 H18B 0.9700 . ?
C18 H18C 0.9700 . ?
C19 H19A 0.9700 . ?
C19 H19B 0.9700 . ?
C19 H19C 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
O1 C1 N1 122.52(14) . . ?
O1 C1 C2 121.63(13) . . ?
N1 C1 C2 115.84(12) . . ?
C3 C2 C7 118.07(14) . . ?
C3 C2 C1 119.15(13) . . ?
C7 C2 C1 122.77(13) . . ?
C4 C3 C2 121.54(14) . . ?
C4 C3 H3 119.2 . . ?
C2 C3 H3 119.2 . . ?
C5 C4 C3 119.68(14) . . ?
C5 C4 H4 120.2 . . ?
C3 C4 H4 120.2 . . ?
O2 C5 C4 124.77(14) . . ?
O2 C5 C6 115.69(14) . . ?
C4 C5 C6 119.54(15) . . ?
C7 C6 C5 120.38(15) . . ?
C7 C6 H6 119.8 . . ?
C5 C6 H6 119.8 . . ?
C6 C7 C2 120.79(14) . . ?
C6 C7 H7 119.6 . . ?
C2 C7 H7 119.6 . . ?
C5 O2 C8 118.08(14) . . ?
O2 C8 H8A 109.5 . . ?
O2 C8 H8B 109.5 . . ?
H8A C8 H8B 109.5 . . ?
O2 C8 H8C 109.5 . . ?
H8A C8 H8C 109.5 . . ?
H8B C8 H8C 109.5 . . ?
C1 N1 C9 122.09(11) . . ?
C1 N1 H1A 119.0 . . ?
C9 N1 H1A 119.0 . . ?
N1 C9 C10 112.59(11) . . ?
N1 C9 H9A 109.1 . . ?
C10 C9 H9A 109.1 . . ?
N1 C9 H9B 109.1 . . ?
C10 C9 H9B 109.1 . . ?
H9A C9 H9B 107.8 . . ?
C17 C10 C18 112.04(11) . . ?
C17 C10 C11 101.74(10) . . ?
C18 C10 C11 108.52(11) . . ?
C17 C10 C9 113.62(11) . . ?
C18 C10 C9 110.50(11) . . ?
C11 C10 C9 109.98(11) . . ?
O3 C11 N2 125.91(13) . . ?
O3 C11 C10 125.37(12) . . ?
N2 C11 C10 108.72(11) . . ?
C11 N2 C12 111.17(11) . . ?
C11 N2 C19 123.80(12) . . ?
C12 N2 C19 125.04(12) . . ?
C13 C12 C17 122.35(13) . . ?
C13 C12 N2 128.43(13) . . ?
C17 C12 N2 109.22(11) . . ?
C12 C13 C14 116.83(14) . . ?
C12 C13 H13 121.6 . . ?
C14 C13 H13 121.6 . . ?
C15 C14 C13 121.74(13) . . ?
C15 C14 H14 119.1 . . ?
C13 C14 H14 119.1 . . ?
C14 C15 C16 120.45(14) . . ?
C14 C15 H15 119.8 . . ?
C16 C15 H15 119.8 . . ?
C17 C16 C15 118.71(13) . . ?
C17 C16 H16 120.6 . . ?
C15 C16 H16 120.6 . . ?
C16 C17 C12 119.90(12) . . ?
C16 C17 C10 131.01(12) . . ?
C12 C17 C10 109.07(11) . . ?
C10 C18 H18A 109.5 . . ?
C10 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C10 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
N2 C19 H19A 109.5 . . ?
N2 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
N2 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 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
O1 C1 C2 C3 24.0(2) . . . . ?
N1 C1 C2 C3 -155.67(13) . . . . ?
O1 C1 C2 C7 -154.87(16) . . . . ?
N1 C1 C2 C7 25.5(2) . . . . ?
C7 C2 C3 C4 -1.0(2) . . . . ?
C1 C2 C3 C4 -179.90(14) . . . . ?
C2 C3 C4 C5 0.5(3) . . . . ?
C3 C4 C5 O2 -178.99(16) . . . . ?
C3 C4 C5 C6 0.4(3) . . . . ?
O2 C5 C6 C7 178.60(18) . . . . ?
C4 C5 C6 C7 -0.9(3) . . . . ?
C5 C6 C7 C2 0.4(3) . . . . ?
C3 C2 C7 C6 0.5(3) . . . . ?
C1 C2 C7 C6 179.41(16) . . . . ?
C4 C5 O2 C8 -0.5(3) . . . . ?
C6 C5 O2 C8 -179.91(18) . . . . ?
O1 C1 N1 C9 7.2(2) . . . . ?
C2 C1 N1 C9 -173.17(12) . . . . ?
C1 N1 C9 C10 102.99(15) . . . . ?
N1 C9 C10 C17 -53.63(15) . . . . ?
N1 C9 C10 C18 179.44(11) . . . . ?
N1 C9 C10 C11 59.65(14) . . . . ?
C17 C10 C11 O3 178.09(13) . . . . ?
C18 C10 C11 O3 -63.62(17) . . . . ?
C9 C10 C11 O3 57.36(17) . . . . ?
C17 C10 C11 N2 -2.54(14) . . . . ?
C18 C10 C11 N2 115.74(12) . . . . ?
C9 C10 C11 N2 -123.27(12) . . . . ?
O3 C11 N2 C12 -179.50(13) . . . . ?
C10 C11 N2 C12 1.14(15) . . . . ?
O3 C11 N2 C19 -0.1(2) . . . . ?
C10 C11 N2 C19 -179.49(14) . . . . ?
C11 N2 C12 C13 -178.40(14) . . . . ?
C19 N2 C12 C13 2.2(2) . . . . ?
C11 N2 C12 C17 0.94(16) . . . . ?
C19 N2 C12 C17 -178.42(15) . . . . ?
C17 C12 C13 C14 1.0(2) . . . . ?
N2 C12 C13 C14 -179.79(14) . . . . ?
C12 C13 C14 C15 0.3(2) . . . . ?
C13 C14 C15 C16 -0.9(2) . . . . ?
C14 C15 C16 C17 0.3(2) . . . . ?
C15 C16 C17 C12 0.9(2) . . . . ?
C15 C16 C17 C10 -176.98(13) . . . . ?
C13 C12 C17 C16 -1.5(2) . . . . ?
N2 C12 C17 C16 179.07(12) . . . . ?
C13 C12 C17 C10 176.75(13) . . . . ?
N2 C12 C17 C10 -2.64(15) . . . . ?
C18 C10 C17 C16 65.41(19) . . . . ?
C11 C10 C17 C16 -178.86(14) . . . . ?
C9 C10 C17 C16 -60.71(19) . . . . ?
C18 C10 C17 C12 -112.63(13) . . . . ?
C11 C10 C17 C12 3.10(14) . . . . ?
C9 C10 C17 C12 121.25(12) . . . . ?

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        28.33
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.245
_refine_diff_density_min         -0.164
_refine_diff_density_rms         0.041
####################################################################### 
# 
# 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_p21c_a
_database_code_depnum_ccdc_archive 'CCDC 1505486'
_audit_update_record             
;
2016-09-21 deposited with the CCDC.
2017-07-17 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        'DB- 0276'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C20 H19 Br N2 O2'
_chemical_formula_weight         399.28

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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

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

_cell_length_a                   9.5310(5)
_cell_length_b                   9.5367(4)
_cell_length_c                   19.5389(9)
_cell_angle_alpha                90
_cell_angle_beta                 93.809(2)
_cell_angle_gamma                90
_cell_volume                     1772.05(14)
_cell_formula_units_Z            4
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    9801
_cell_measurement_theta_min      2.987
_cell_measurement_theta_max      39.445

_exptl_crystal_description       Block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.497
_exptl_crystal_F_000             816
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.310
_exptl_crystal_size_mid          0.240
_exptl_crystal_size_min          0.210
_exptl_absorpt_coefficient_mu    2.335
_shelx_estimated_absorpt_T_min   0.531
_shelx_estimated_absorpt_T_max   0.640
_exptl_absorpt_correction_type   MULTI-SCAN
_exptl_absorpt_correction_T_min  0.6249
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      120(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'omega phi scan'
_diffrn_reflns_number            42182
_diffrn_reflns_av_unetI/netI     0.0844
_diffrn_reflns_av_R_equivalents  0.0551
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_theta_min         2.891
_diffrn_reflns_theta_max         39.502
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.937
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.937
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             9950
_reflns_number_gt                6026
_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 SMART APEXll'
_computing_cell_refinement       'Bruker SMART APEXll'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    SHELXTL
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'SHELXL-2013 (Sheldrick, 2013)'
_computing_publication_material  'SHELXL-2013 (Sheldrick, 2013)'


_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)+(0.0680P)²+1.9333P] 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_number_reflns         9950
_refine_ls_number_parameters     227
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1562
_refine_ls_R_factor_gt           0.0818
_refine_ls_wR_factor_ref         0.1710
_refine_ls_wR_factor_gt          0.1503
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_restrained_S_all      1.049
_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
Br1 Br -0.03721(3) 0.77279(3) 0.77457(2) 0.03154(9) Uani 1 1 d . . . . .
C1 C 0.4295(2) 0.79344(19) 0.37278(10) 0.0159(3) Uani 1 1 d . . . . .
C2 C 0.5541(2) 0.8343(2) 0.42274(10) 0.0193(4) Uani 1 1 d . . . . .
C3 C 0.7527(2) 0.7103(3) 0.48611(13) 0.0316(5) Uani 1 1 d . . . . .
H3A H 0.7719 0.8030 0.5061 0.047 Uiso 1 1 calc R U . . .
H3B H 0.8292 0.6838 0.4576 0.047 Uiso 1 1 calc R U . . .
H3C H 0.7458 0.6412 0.5229 0.047 Uiso 1 1 calc R U . . .
C4 C 0.5526(2) 0.5956(2) 0.41626(10) 0.0202(4) Uani 1 1 d . . . . .
C5 C 0.5885(2) 0.4560(3) 0.42643(13) 0.0295(5) Uani 1 1 d . . . . .
H5 H 0.6683 0.4298 0.4553 0.035 Uiso 1 1 calc R U . . .
C6 C 0.5034(3) 0.3558(3) 0.39286(14) 0.0313(5) Uani 1 1 d . . . . .
H6 H 0.5262 0.2593 0.3983 0.038 Uiso 1 1 calc R U . . .
C7 C 0.3858(3) 0.3943(2) 0.35161(12) 0.0279(4) Uani 1 1 d . . . . .
H7 H 0.3283 0.3241 0.3296 0.033 Uiso 1 1 calc R U . . .
C8 C 0.3510(2) 0.5358(2) 0.34216(11) 0.0231(4) Uani 1 1 d . . . . .
H8 H 0.2702 0.5621 0.3139 0.028 Uiso 1 1 calc R U . . .
C9 C 0.4354(2) 0.6365(2) 0.37433(10) 0.0178(3) Uani 1 1 d . . . . .
C10 C 0.4504(3) 0.8578(2) 0.30132(11) 0.0258(4) Uani 1 1 d . . . . .
H10A H 0.5517 0.8616 0.2929 0.031 Uiso 1 1 calc R U . . .
H10B H 0.4013 0.8009 0.2648 0.031 Uiso 1 1 calc R U . . .
C11 C 0.3886(4) 1.0054(3) 0.30217(15) 0.0437(7) Uani 1 1 d . . . . .
H11A H 0.3276 1.0224 0.2600 0.052 Uiso 1 1 calc R U . . .
H11B H 0.4647 1.0763 0.3048 0.052 Uiso 1 1 calc R U . . .
C12 C 0.3027(2) 1.0144(2) 0.36569(12) 0.0271(4) Uani 1 1 d . . . . .
H12A H 0.3516 1.0730 0.4017 0.033 Uiso 1 1 calc R U . . .
H12B H 0.2087 1.0551 0.3537 0.033 Uiso 1 1 calc R U . . .
C13 C 0.2897(2) 0.8631(2) 0.39024(10) 0.0177(3) Uani 1 1 d . . . . .
H13 H 0.2126 0.8178 0.3609 0.021 Uiso 1 1 calc R U . . .
C14 C 0.1532(2) 0.7613(2) 0.47943(11) 0.0182(3) Uani 1 1 d . . . . .
C15 C 0.1123(2) 0.7682(2) 0.55200(10) 0.0172(3) Uani 1 1 d . . . . .
C16 C 0.1307(2) 0.8876(2) 0.59309(11) 0.0252(4) Uani 1 1 d . . . . .
H16 H 0.1730 0.9691 0.5755 0.030 Uiso 1 1 calc R U . . .
C17 C 0.0874(2) 0.8877(2) 0.65954(12) 0.0264(4) Uani 1 1 d . . . . .
H17 H 0.1001 0.9687 0.6876 0.032 Uiso 1 1 calc R U . . .
C18 C 0.0258(2) 0.7690(2) 0.68446(10) 0.0217(4) Uani 1 1 d . . . . .
C19 C 0.0063(2) 0.6489(2) 0.64493(11) 0.0218(4) Uani 1 1 d . . . . .
H19 H -0.0360 0.5678 0.6629 0.026 Uiso 1 1 calc R U . . .
C20 C 0.0499(2) 0.6498(2) 0.57879(10) 0.0205(4) Uani 1 1 d . . . . .
H20 H 0.0371 0.5683 0.5511 0.025 Uiso 1 1 calc R U . . .
N1 N 0.25371(17) 0.85072(18) 0.46097(9) 0.0183(3) Uani 1 1 d . . . . .
H1 H 0.2985 0.9027 0.4926 0.022 Uiso 1 1 calc R U . . .
N2 N 0.62121(19) 0.7142(2) 0.44427(10) 0.0224(3) Uani 1 1 d . . . . .
O1 O 0.09483(17) 0.67653(19) 0.43918(8) 0.0287(4) Uani 1 1 d . . . . .
O2 O 0.59108(17) 0.95339(18) 0.43938(9) 0.0278(3) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Br1 C18 1.898(2) . ?
C1 C9 1.498(3) . ?
C1 C2 1.537(3) . ?
C1 C13 1.546(3) . ?
C1 C10 1.550(3) . ?
C2 O2 1.227(3) . ?
C2 N2 1.364(3) . ?
C3 N2 1.450(3) . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C4 C5 1.385(3) . ?
C4 C9 1.396(3) . ?
C4 N2 1.400(3) . ?
C5 C6 1.390(4) . ?
C5 H5 0.9500 . ?
C6 C7 1.386(4) . ?
C6 H6 0.9500 . ?
C7 C8 1.399(3) . ?
C7 H7 0.9500 . ?
C8 C9 1.378(3) . ?
C8 H8 0.9500 . ?
C10 C11 1.526(4) . ?
C10 H10A 0.9900 . ?
C10 H10B 0.9900 . ?
C11 C12 1.534(4) . ?
C11 H11A 0.9900 . ?
C11 H11B 0.9900 . ?
C12 C13 1.528(3) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 N1 1.451(2) . ?
C13 H13 1.0000 . ?
C14 O1 1.234(2) . ?
C14 N1 1.349(3) . ?
C14 C15 1.497(3) . ?
C15 C20 1.394(3) . ?
C15 C16 1.398(3) . ?
C16 C17 1.388(3) . ?
C16 H16 0.9500 . ?
C17 C18 1.379(3) . ?
C17 H17 0.9500 . ?
C18 C19 1.387(3) . ?
C19 C20 1.383(3) . ?
C19 H19 0.9500 . ?
C20 H20 0.9500 . ?
N1 H1 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
C9 C1 C2 102.32(15) . . ?
C9 C1 C13 117.18(16) . . ?
C2 C1 C13 113.07(16) . . ?
C9 C1 C10 114.01(17) . . ?
C2 C1 C10 109.35(16) . . ?
C13 C1 C10 101.13(16) . . ?
O2 C2 N2 125.10(19) . . ?
O2 C2 C1 126.80(19) . . ?
N2 C2 C1 108.07(17) . . ?
N2 C3 H3A 109.5 . . ?
N2 C3 H3B 109.5 . . ?
H3A C3 H3B 109.5 . . ?
N2 C3 H3C 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
C5 C4 C9 122.2(2) . . ?
C5 C4 N2 128.0(2) . . ?
C9 C4 N2 109.80(18) . . ?
C4 C5 C6 117.6(2) . . ?
C4 C5 H5 121.2 . . ?
C6 C5 H5 121.2 . . ?
C7 C6 C5 121.1(2) . . ?
C7 C6 H6 119.5 . . ?
C5 C6 H6 119.5 . . ?
C6 C7 C8 120.5(2) . . ?
C6 C7 H7 119.7 . . ?
C8 C7 H7 119.7 . . ?
C9 C8 C7 119.1(2) . . ?
C9 C8 H8 120.5 . . ?
C7 C8 H8 120.5 . . ?
C8 C9 C4 119.60(19) . . ?
C8 C9 C1 131.81(18) . . ?
C4 C9 C1 108.58(17) . . ?
C11 C10 C1 106.40(18) . . ?
C11 C10 H10A 110.4 . . ?
C1 C10 H10A 110.4 . . ?
C11 C10 H10B 110.4 . . ?
C1 C10 H10B 110.4 . . ?
H10A C10 H10B 108.6 . . ?
C10 C11 C12 106.72(19) . . ?
C10 C11 H11A 110.4 . . ?
C12 C11 H11A 110.4 . . ?
C10 C11 H11B 110.4 . . ?
C12 C11 H11B 110.4 . . ?
H11A C11 H11B 108.6 . . ?
C13 C12 C11 105.05(19) . . ?
C13 C12 H12A 110.7 . . ?
C11 C12 H12A 110.7 . . ?
C13 C12 H12B 110.7 . . ?
C11 C12 H12B 110.7 . . ?
H12A C12 H12B 108.8 . . ?
N1 C13 C12 113.89(17) . . ?
N1 C13 C1 115.91(15) . . ?
C12 C13 C1 104.34(16) . . ?
N1 C13 H13 107.4 . . ?
C12 C13 H13 107.4 . . ?
C1 C13 H13 107.4 . . ?
O1 C14 N1 122.79(19) . . ?
O1 C14 C15 119.83(18) . . ?
N1 C14 C15 117.38(17) . . ?
C20 C15 C16 118.98(19) . . ?
C20 C15 C14 117.71(17) . . ?
C16 C15 C14 123.29(18) . . ?
C17 C16 C15 120.2(2) . . ?
C17 C16 H16 119.9 . . ?
C15 C16 H16 119.9 . . ?
C18 C17 C16 119.3(2) . . ?
C18 C17 H17 120.3 . . ?
C16 C17 H17 120.3 . . ?
C17 C18 C19 121.7(2) . . ?
C17 C18 Br1 118.72(16) . . ?
C19 C18 Br1 119.55(17) . . ?
C20 C19 C18 118.52(19) . . ?
C20 C19 H19 120.7 . . ?
C18 C19 H19 120.7 . . ?
C19 C20 C15 121.20(19) . . ?
C19 C20 H20 119.4 . . ?
C15 C20 H20 119.4 . . ?
C14 N1 C13 121.55(17) . . ?
C14 N1 H1 119.2 . . ?
C13 N1 H1 119.2 . . ?
C2 N2 C4 111.12(17) . . ?
C2 N2 C3 124.44(19) . . ?
C4 N2 C3 124.26(19) . . ?

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
C9 C1 C2 O2 -178.8(2) . . . . ?
C13 C1 C2 O2 -51.9(3) . . . . ?
C10 C1 C2 O2 59.9(3) . . . . ?
C9 C1 C2 N2 3.2(2) . . . . ?
C13 C1 C2 N2 130.13(17) . . . . ?
C10 C1 C2 N2 -118.04(19) . . . . ?
C9 C4 C5 C6 0.3(3) . . . . ?
N2 C4 C5 C6 179.9(2) . . . . ?
C4 C5 C6 C7 -1.0(4) . . . . ?
C5 C6 C7 C8 0.8(4) . . . . ?
C6 C7 C8 C9 0.1(3) . . . . ?
C7 C8 C9 C4 -0.8(3) . . . . ?
C7 C8 C9 C1 177.8(2) . . . . ?
C5 C4 C9 C8 0.6(3) . . . . ?
N2 C4 C9 C8 -179.06(19) . . . . ?
C5 C4 C9 C1 -178.3(2) . . . . ?
N2 C4 C9 C1 2.1(2) . . . . ?
C2 C1 C9 C8 178.2(2) . . . . ?
C13 C1 C9 C8 53.9(3) . . . . ?
C10 C1 C9 C8 -63.9(3) . . . . ?
C2 C1 C9 C4 -3.1(2) . . . . ?
C13 C1 C9 C4 -127.39(18) . . . . ?
C10 C1 C9 C4 114.82(19) . . . . ?
C9 C1 C10 C11 159.4(2) . . . . ?
C2 C1 C10 C11 -86.8(2) . . . . ?
C13 C1 C10 C11 32.7(2) . . . . ?
C1 C10 C11 C12 -13.0(3) . . . . ?
C10 C11 C12 C13 -12.6(3) . . . . ?
C11 C12 C13 N1 160.8(2) . . . . ?
C11 C12 C13 C1 33.4(2) . . . . ?
C9 C1 C13 N1 68.8(2) . . . . ?
C2 C1 C13 N1 -49.8(2) . . . . ?
C10 C1 C13 N1 -166.63(17) . . . . ?
C9 C1 C13 C12 -165.10(17) . . . . ?
C2 C1 C13 C12 76.3(2) . . . . ?
C10 C1 C13 C12 -40.54(19) . . . . ?
O1 C14 C15 C20 22.8(3) . . . . ?
N1 C14 C15 C20 -157.49(19) . . . . ?
O1 C14 C15 C16 -155.7(2) . . . . ?
N1 C14 C15 C16 24.1(3) . . . . ?
C20 C15 C16 C17 0.1(3) . . . . ?
C14 C15 C16 C17 178.5(2) . . . . ?
C15 C16 C17 C18 -0.2(4) . . . . ?
C16 C17 C18 C19 0.3(3) . . . . ?
C16 C17 C18 Br1 -178.36(18) . . . . ?
C17 C18 C19 C20 -0.3(3) . . . . ?
Br1 C18 C19 C20 178.41(15) . . . . ?
C18 C19 C20 C15 0.1(3) . . . . ?
C16 C15 C20 C19 0.0(3) . . . . ?
C14 C15 C20 C19 -178.54(18) . . . . ?
O1 C14 N1 C13 6.6(3) . . . . ?
C15 C14 N1 C13 -173.14(17) . . . . ?
C12 C13 N1 C14 134.1(2) . . . . ?
C1 C13 N1 C14 -104.8(2) . . . . ?
O2 C2 N2 C4 179.8(2) . . . . ?
C1 C2 N2 C4 -2.1(2) . . . . ?
O2 C2 N2 C3 -4.9(3) . . . . ?
C1 C2 N2 C3 173.1(2) . . . . ?
C5 C4 N2 C2 -179.5(2) . . . . ?
C9 C4 N2 C2 0.1(2) . . . . ?
C5 C4 N2 C3 5.2(4) . . . . ?
C9 C4 N2 C3 -175.2(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
C3 H3B O1 0.98 2.58 3.461(3) 149.3 1_655
C13 H13 Br1 1.00 2.95 3.9449(19) 171.0 4_575
C17 H17 Br1 0.95 3.06 3.931(2) 152.9 2_556
N1 H1 O2 0.88 2.14 3.014(2) 173.5 3_676

_refine_diff_density_max         1.691
_refine_diff_density_min         -0.730
_refine_diff_density_rms         0.121

_shelxl_version_number           2013-4



