# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2021

####################################################################### 
# 
# 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_b
_database_code_depnum_ccdc_archive 'CCDC 2092587'
loop_
_audit_author_name
_audit_author_address
'Da-Ming Du'
;Beijing Institute of Technology
China
;
_audit_update_record             
;
2021-06-27 deposited with the CCDC.	2021-09-13 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
'(5S,10R)-8-(4-Bromophenyl)-6-imino-4-methyl-1-oxo-10-phenyl-2-oxa-3-azaspiro[4.5]de ca-3,7-diene-7-carbonitrile'
_chemical_name_common            ?
_chemical_melting_point          451-453
_chemical_formula_moiety         ?
_chemical_formula_sum            'C22 H16 Br N3 O2'
_chemical_formula_weight         434.29

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'

_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_H-M_alt        'P 1'
_space_group_name_Hall           'P 1'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

loop_
_space_group_symop_operation_xyz
'x, y, z'

_cell_length_a                   6.062(2)
_cell_length_b                   12.279(5)
_cell_length_c                   13.666(5)
_cell_angle_alpha                75.605(8)
_cell_angle_beta                 86.331(8)
_cell_angle_gamma                89.054(9)
_cell_volume                     983.3(6)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    5332
_cell_measurement_theta_min      2.57
_cell_measurement_theta_max      20.34

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.467
_exptl_crystal_F_000             440
_exptl_transmission_factor_min   0.864
_exptl_transmission_factor_max   0.864
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.200
_exptl_absorpt_coefficient_mu    2.113
_shelx_estimated_absorpt_T_min   0.677
_shelx_estimated_absorpt_T_max   0.677
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   sadabs
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  CCD
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            20517
_diffrn_reflns_av_unetI/netI     0.1337
_diffrn_reflns_av_R_equivalents  0.0788
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.084
_diffrn_reflns_theta_max         25.279
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measured_fraction_theta_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.937
_diffrn_reflns_point_group_measured_fraction_full 0.942
_reflns_number_total             6734
_reflns_number_gt                3537
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.897
_reflns_Friedel_fraction_max     0.886
_reflns_Friedel_fraction_full    0.891

_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.0232P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Flack x determined using 1299 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.023(9)
_chemical_absolute_configuration AD
_refine_ls_number_reflns         6734
_refine_ls_number_parameters     507
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.1278
_refine_ls_R_factor_gt           0.0433
_refine_ls_wR_factor_ref         0.0977
_refine_ls_wR_factor_gt          0.0777
_refine_ls_goodness_of_fit_ref   0.901
_refine_ls_restrained_S_all      0.901
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br -0.08018(15) 0.03289(8) 0.89326(7) 0.0891(4) Uani 1 1 d . . . . .
Br2 Br 1.08449(12) 0.74783(7) 0.09944(6) 0.0710(4) Uani 1 1 d . . . . .
C1 C -0.0346(13) 0.2285(7) 0.6006(6) 0.053(2) Uani 1 1 d . . . . .
H1 H -0.1215 0.2822 0.5600 0.063 Uiso 1 1 calc R U . . .
C2 C -0.1087(14) 0.1777(8) 0.6989(6) 0.059(2) Uani 1 1 d . . . . .
H2 H -0.2460 0.1976 0.7236 0.070 Uiso 1 1 calc R U . . .
C3 C 0.0153(18) 0.0994(9) 0.7601(7) 0.055(3) Uani 1 1 d . . . . .
C4 C 0.2198(19) 0.0678(9) 0.7219(8) 0.065(3) Uani 1 1 d . . . . .
H4 H 0.3056 0.0137 0.7628 0.078 Uiso 1 1 calc R U . . .
C5 C 0.2941(18) 0.1175(9) 0.6230(8) 0.061(3) Uani 1 1 d . . . . .
H5 H 0.4286 0.0955 0.5972 0.074 Uiso 1 1 calc R U . . .
C6 C 0.1699(13) 0.1992(7) 0.5625(6) 0.046(2) Uani 1 1 d . . . . .
C7 C 0.2502(11) 0.2502(7) 0.4576(5) 0.042(2) Uani 1 1 d . . . . .
C8 C 0.2616(12) 0.3619(7) 0.4179(6) 0.041(2) Uani 1 1 d . . . . .
C9 C 0.3440(12) 0.4167(8) 0.3166(6) 0.043(2) Uani 1 1 d . . . . .
C10 C 0.4585(12) 0.3410(7) 0.2561(6) 0.039(2) Uani 1 1 d . . . . .
C11 C 0.3362(13) 0.2251(7) 0.2805(6) 0.041(2) Uani 1 1 d . . . . .
H11 H 0.1828 0.2412 0.2629 0.050 Uiso 1 1 calc R U . . .
C12 C 0.3293(16) 0.1731(8) 0.3939(7) 0.049(3) Uani 1 1 d . . . . .
H12A H 0.2335 0.1077 0.4094 0.059 Uiso 1 1 calc R U . . .
H12B H 0.4766 0.1472 0.4122 0.059 Uiso 1 1 calc R U . . .
C13 C 0.4242(13) 0.1445(7) 0.2212(6) 0.043(2) Uani 1 1 d . . . . .
C14 C 0.6290(16) 0.0933(8) 0.2380(7) 0.059(3) Uani 1 1 d . . . . .
H14 H 0.7211 0.1113 0.2835 0.071 Uiso 1 1 calc R U . . .
C15 C 0.6932(18) 0.0120(9) 0.1829(9) 0.074(3) Uani 1 1 d . . . . .
H15 H 0.8305 -0.0227 0.1922 0.089 Uiso 1 1 calc R U . . .
C16 C 0.561(2) -0.0151(8) 0.1186(8) 0.073(3) Uani 1 1 d . . . . .
H16 H 0.6051 -0.0698 0.0850 0.087 Uiso 1 1 calc R U . . .
C17 C 0.359(2) 0.0369(10) 0.1015(8) 0.073(3) Uani 1 1 d . . . . .
H17 H 0.2688 0.0187 0.0555 0.087 Uiso 1 1 calc R U . . .
C18 C 0.2922(15) 0.1171(7) 0.1533(7) 0.057(2) Uani 1 1 d . . . . .
H18 H 0.1561 0.1524 0.1418 0.068 Uiso 1 1 calc R U . . .
C19 C 0.1966(13) 0.4395(8) 0.4793(6) 0.053(2) Uani 1 1 d . . . . .
C20 C 0.6988(15) 0.3300(8) 0.2831(8) 0.053(2) Uani 1 1 d . . . . .
C21 C 0.4893(15) 0.3945(7) 0.1456(6) 0.047(2) Uani 1 1 d . . . . .
C22 C 0.3092(15) 0.4307(9) 0.0760(7) 0.062(3) Uani 1 1 d . . . . .
H22A H 0.3719 0.4625 0.0088 0.094 Uiso 1 1 calc R U . . .
H22B H 0.2195 0.4862 0.0983 0.094 Uiso 1 1 calc R U . . .
H22C H 0.2196 0.3670 0.0759 0.094 Uiso 1 1 calc R U . . .
C23 C 0.7166(16) 0.6867(8) 0.3692(8) 0.059(3) Uani 1 1 d . . . . .
H23 H 0.5838 0.6508 0.3949 0.071 Uiso 1 1 calc R U . . .
C24 C 0.7880(18) 0.6910(8) 0.2717(8) 0.058(3) Uani 1 1 d . . . . .
H24 H 0.7031 0.6602 0.2309 0.069 Uiso 1 1 calc R U . . .
C25 C 0.9843(17) 0.7407(8) 0.2349(7) 0.054(3) Uani 1 1 d . . . . .
C26 C 1.1124(14) 0.7874(7) 0.2937(6) 0.052(2) Uani 1 1 d . . . . .
H26 H 1.2469 0.8212 0.2677 0.062 Uiso 1 1 calc R U . . .
C27 C 1.0363(13) 0.7830(7) 0.3925(6) 0.049(2) Uani 1 1 d . . . . .
H27 H 1.1216 0.8134 0.4332 0.059 Uiso 1 1 calc R U . . .
C28 C 0.8363(13) 0.7342(6) 0.4310(6) 0.043(2) Uani 1 1 d . . . . .
C29 C 0.7560(11) 0.7285(7) 0.5360(5) 0.042(2) Uani 1 1 d . . . . .
C30 C 0.7462(11) 0.8177(7) 0.5768(6) 0.0392(19) Uani 1 1 d . . . . .
C31 C 0.6613(12) 0.8153(7) 0.6795(6) 0.045(2) Uani 1 1 d . . . . .
C32 C 0.5388(13) 0.7087(7) 0.7362(6) 0.037(2) Uani 1 1 d . . . . .
C33 C 0.6674(13) 0.6074(7) 0.7133(6) 0.045(2) Uani 1 1 d . . . . .
H33 H 0.8189 0.6133 0.7327 0.054 Uiso 1 1 calc R U . . .
C34 C 0.6823(15) 0.6149(7) 0.5997(7) 0.046(2) Uani 1 1 d . . . . .
H34A H 0.7854 0.5584 0.5862 0.055 Uiso 1 1 calc R U . . .
H34B H 0.5385 0.5979 0.5798 0.055 Uiso 1 1 calc R U . . .
C35 C 0.5807(14) 0.4929(7) 0.7730(6) 0.048(2) Uani 1 1 d . . . . .
C36 C 0.3803(16) 0.4532(8) 0.7525(7) 0.060(3) Uani 1 1 d . . . . .
H36 H 0.2940 0.4978 0.7042 0.073 Uiso 1 1 calc R U . . .
C37 C 0.3088(19) 0.3460(9) 0.8048(8) 0.075(3) Uani 1 1 d . . . . .
H37 H 0.1729 0.3195 0.7927 0.090 Uiso 1 1 calc R U . . .
C38 C 0.438(2) 0.2807(10) 0.8732(8) 0.086(3) Uani 1 1 d . . . . .
H38 H 0.3931 0.2081 0.9063 0.103 Uiso 1 1 calc R U . . .
C39 C 0.638(2) 0.3210(11) 0.8946(8) 0.084(4) Uani 1 1 d . . . . .
H39 H 0.7227 0.2764 0.9435 0.101 Uiso 1 1 calc R U . . .
C40 C 0.7096(17) 0.4260(8) 0.8438(6) 0.059(2) Uani 1 1 d . . . . .
H40 H 0.8448 0.4522 0.8570 0.070 Uiso 1 1 calc R U . . .
C41 C 0.3062(16) 0.7180(7) 0.7058(8) 0.053(3) Uani 1 1 d . . . . .
C42 C 0.5016(15) 0.7014(7) 0.8474(6) 0.050(2) Uani 1 1 d . . . . .
C43 C 0.6721(16) 0.6945(8) 0.9212(7) 0.069(3) Uani 1 1 d . . . . .
H43A H 0.6021 0.6918 0.9868 0.103 Uiso 1 1 calc R U . . .
H43B H 0.7661 0.7593 0.9005 0.103 Uiso 1 1 calc R U . . .
H43C H 0.7590 0.6278 0.9243 0.103 Uiso 1 1 calc R U . . .
C44 C 0.8102(13) 0.9274(9) 0.5170(6) 0.052(2) Uani 1 1 d . . . . .
N1 N 0.6882(13) 0.4096(7) 0.1139(6) 0.071(2) Uani 1 1 d . . . . .
N2 N 0.3449(12) 0.5207(6) 0.2737(5) 0.063(2) Uani 1 1 d . . . . .
H2A H 0.2894 0.5667 0.3070 0.076 Uiso 1 1 d R U . . .
N3 N 0.1527(13) 0.5056(7) 0.5237(6) 0.076(2) Uani 1 1 d . . . . .
N4 N 0.2982(14) 0.7014(7) 0.8768(6) 0.070(2) Uani 1 1 d . . . . .
N5 N 0.6672(11) 0.8956(6) 0.7230(5) 0.0597(19) Uani 1 1 d . . . . .
H5A H 0.7250 0.9586 0.6901 0.072 Uiso 1 1 d R U . . .
N6 N 0.8532(13) 1.0165(7) 0.4724(6) 0.075(3) Uani 1 1 d . . . . .
O1 O 0.7737(9) 0.2962(5) 0.3639(5) 0.0681(18) Uani 1 1 d . . . . .
O2 O 0.8256(9) 0.3677(6) 0.1989(5) 0.080(2) Uani 1 1 d . . . . .
O3 O 0.2368(9) 0.7313(5) 0.6245(5) 0.0678(17) Uani 1 1 d . . . . .
O4 O 0.1706(10) 0.7120(6) 0.7891(5) 0.0738(19) 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 C3 1.859(9) . ?
Br2 C25 1.893(9) . ?
C1 C2 1.381(10) . ?
C1 C6 1.390(10) . ?
C1 H1 0.9300 . ?
C2 C3 1.359(12) . ?
C2 H2 0.9300 . ?
C3 C4 1.401(14) . ?
C4 C5 1.387(13) . ?
C4 H4 0.9300 . ?
C5 C6 1.378(12) . ?
C5 H5 0.9300 . ?
C6 C7 1.470(10) . ?
C7 C8 1.345(10) . ?
C7 C12 1.491(11) . ?
C8 C9 1.442(11) . ?
C8 C19 1.452(13) . ?
C9 N2 1.266(9) . ?
C9 C10 1.522(11) . ?
C10 C21 1.490(10) . ?
C10 C20 1.521(12) . ?
C10 C11 1.567(11) . ?
C11 C13 1.499(11) . ?
C11 C12 1.521(11) . ?
C11 H11 0.9800 . ?
C12 H12A 0.9700 . ?
C12 H12B 0.9700 . ?
C13 C18 1.368(11) . ?
C13 C14 1.389(11) . ?
C14 C15 1.426(13) . ?
C14 H14 0.9300 . ?
C15 C16 1.331(14) . ?
C15 H15 0.9300 . ?
C16 C17 1.376(15) . ?
C16 H16 0.9300 . ?
C17 C18 1.390(13) . ?
C17 H17 0.9300 . ?
C18 H18 0.9300 . ?
C19 N3 1.148(10) . ?
C20 O1 1.194(10) . ?
C20 O2 1.328(10) . ?
C21 N1 1.256(10) . ?
C21 C22 1.484(12) . ?
C22 H22A 0.9600 . ?
C22 H22B 0.9600 . ?
C22 H22C 0.9600 . ?
C23 C24 1.363(12) . ?
C23 C28 1.385(12) . ?
C23 H23 0.9300 . ?
C24 C25 1.355(13) . ?
C24 H24 0.9300 . ?
C25 C26 1.378(12) . ?
C26 C27 1.386(10) . ?
C26 H26 0.9300 . ?
C27 C28 1.375(10) . ?
C27 H27 0.9300 . ?
C28 C29 1.471(10) . ?
C29 C30 1.345(10) . ?
C29 C34 1.507(11) . ?
C30 C44 1.436(12) . ?
C30 C31 1.458(10) . ?
C31 N5 1.274(9) . ?
C31 C32 1.524(11) . ?
C32 C41 1.490(12) . ?
C32 C42 1.502(11) . ?
C32 C33 1.543(11) . ?
C33 C35 1.523(11) . ?
C33 C34 1.530(10) . ?
C33 H33 0.9800 . ?
C34 H34A 0.9700 . ?
C34 H34B 0.9700 . ?
C35 C40 1.380(11) . ?
C35 C36 1.387(12) . ?
C36 C37 1.393(12) . ?
C36 H36 0.9300 . ?
C37 C38 1.354(15) . ?
C37 H37 0.9300 . ?
C38 C39 1.389(16) . ?
C38 H38 0.9300 . ?
C39 C40 1.367(14) . ?
C39 H39 0.9300 . ?
C40 H40 0.9300 . ?
C41 O3 1.185(10) . ?
C41 O4 1.348(10) . ?
C42 N4 1.272(10) . ?
C42 C43 1.477(12) . ?
C43 H43A 0.9600 . ?
C43 H43B 0.9600 . ?
C43 H43C 0.9600 . ?
C44 N6 1.137(10) . ?
N1 O2 1.456(9) . ?
N2 H2A 0.8600 . ?
N4 O4 1.446(10) . ?
N5 H5A 0.8600 . ?

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 C1 C6 120.0(8) . . ?
C2 C1 H1 120.0 . . ?
C6 C1 H1 120.0 . . ?
C3 C2 C1 121.3(8) . . ?
C3 C2 H2 119.4 . . ?
C1 C2 H2 119.4 . . ?
C2 C3 C4 119.2(9) . . ?
C2 C3 Br1 121.6(8) . . ?
C4 C3 Br1 119.2(8) . . ?
C5 C4 C3 119.8(10) . . ?
C5 C4 H4 120.1 . . ?
C3 C4 H4 120.1 . . ?
C6 C5 C4 120.4(10) . . ?
C6 C5 H5 119.8 . . ?
C4 C5 H5 119.8 . . ?
C5 C6 C1 119.2(8) . . ?
C5 C6 C7 119.7(8) . . ?
C1 C6 C7 121.0(7) . . ?
C8 C7 C6 123.3(7) . . ?
C8 C7 C12 119.0(7) . . ?
C6 C7 C12 117.7(7) . . ?
C7 C8 C9 125.8(7) . . ?
C7 C8 C19 120.5(7) . . ?
C9 C8 C19 113.6(7) . . ?
N2 C9 C8 128.1(8) . . ?
N2 C9 C10 115.8(7) . . ?
C8 C9 C10 115.9(7) . . ?
C21 C10 C20 99.8(7) . . ?
C21 C10 C9 113.6(6) . . ?
C20 C10 C9 107.3(7) . . ?
C21 C10 C11 113.3(7) . . ?
C20 C10 C11 112.8(6) . . ?
C9 C10 C11 109.6(6) . . ?
C13 C11 C12 111.8(7) . . ?
C13 C11 C10 115.1(6) . . ?
C12 C11 C10 109.3(7) . . ?
C13 C11 H11 106.7 . . ?
C12 C11 H11 106.7 . . ?
C10 C11 H11 106.7 . . ?
C7 C12 C11 114.6(7) . . ?
C7 C12 H12A 108.6 . . ?
C11 C12 H12A 108.6 . . ?
C7 C12 H12B 108.6 . . ?
C11 C12 H12B 108.6 . . ?
H12A C12 H12B 107.6 . . ?
C18 C13 C14 120.1(8) . . ?
C18 C13 C11 118.3(7) . . ?
C14 C13 C11 121.5(8) . . ?
C13 C14 C15 117.7(9) . . ?
C13 C14 H14 121.1 . . ?
C15 C14 H14 121.1 . . ?
C16 C15 C14 121.4(10) . . ?
C16 C15 H15 119.3 . . ?
C14 C15 H15 119.3 . . ?
C15 C16 C17 120.6(10) . . ?
C15 C16 H16 119.7 . . ?
C17 C16 H16 119.7 . . ?
C16 C17 C18 119.5(10) . . ?
C16 C17 H17 120.2 . . ?
C18 C17 H17 120.2 . . ?
C13 C18 C17 120.7(9) . . ?
C13 C18 H18 119.6 . . ?
C17 C18 H18 119.6 . . ?
N3 C19 C8 175.9(9) . . ?
O1 C20 O2 122.4(9) . . ?
O1 C20 C10 129.4(9) . . ?
O2 C20 C10 108.3(8) . . ?
N1 C21 C10 113.7(7) . . ?
N1 C21 C22 120.7(8) . . ?
C10 C21 C22 125.6(8) . . ?
C21 C22 H22A 109.5 . . ?
C21 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C21 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
C24 C23 C28 121.9(9) . . ?
C24 C23 H23 119.1 . . ?
C28 C23 H23 119.1 . . ?
C25 C24 C23 119.1(10) . . ?
C25 C24 H24 120.5 . . ?
C23 C24 H24 120.5 . . ?
C24 C25 C26 121.5(8) . . ?
C24 C25 Br2 119.5(8) . . ?
C26 C25 Br2 119.0(7) . . ?
C25 C26 C27 118.6(8) . . ?
C25 C26 H26 120.7 . . ?
C27 C26 H26 120.7 . . ?
C28 C27 C26 120.9(8) . . ?
C28 C27 H27 119.5 . . ?
C26 C27 H27 119.5 . . ?
C27 C28 C23 118.0(8) . . ?
C27 C28 C29 121.1(7) . . ?
C23 C28 C29 120.9(7) . . ?
C30 C29 C28 123.8(7) . . ?
C30 C29 C34 119.5(7) . . ?
C28 C29 C34 116.7(7) . . ?
C29 C30 C44 120.6(7) . . ?
C29 C30 C31 125.1(7) . . ?
C44 C30 C31 114.3(7) . . ?
N5 C31 C30 126.5(8) . . ?
N5 C31 C32 117.6(7) . . ?
C30 C31 C32 115.7(7) . . ?
C41 C32 C42 100.3(7) . . ?
C41 C32 C31 108.3(6) . . ?
C42 C32 C31 112.4(6) . . ?
C41 C32 C33 114.5(7) . . ?
C42 C32 C33 113.4(7) . . ?
C31 C32 C33 107.9(6) . . ?
C35 C33 C34 110.8(7) . . ?
C35 C33 C32 114.8(7) . . ?
C34 C33 C32 110.7(6) . . ?
C35 C33 H33 106.7 . . ?
C34 C33 H33 106.7 . . ?
C32 C33 H33 106.7 . . ?
C29 C34 C33 113.4(7) . . ?
C29 C34 H34A 108.9 . . ?
C33 C34 H34A 108.9 . . ?
C29 C34 H34B 108.9 . . ?
C33 C34 H34B 108.9 . . ?
H34A C34 H34B 107.7 . . ?
C40 C35 C36 120.0(9) . . ?
C40 C35 C33 119.3(8) . . ?
C36 C35 C33 120.6(8) . . ?
C37 C36 C35 119.6(10) . . ?
C37 C36 H36 120.2 . . ?
C35 C36 H36 120.2 . . ?
C38 C37 C36 119.7(11) . . ?
C38 C37 H37 120.2 . . ?
C36 C37 H37 120.2 . . ?
C37 C38 C39 120.7(11) . . ?
C37 C38 H38 119.7 . . ?
C39 C38 H38 119.7 . . ?
C40 C39 C38 120.2(11) . . ?
C40 C39 H39 119.9 . . ?
C38 C39 H39 119.9 . . ?
C39 C40 C35 119.8(11) . . ?
C39 C40 H40 120.1 . . ?
C35 C40 H40 120.1 . . ?
O3 C41 O4 121.7(9) . . ?
O3 C41 C32 129.9(8) . . ?
O4 C41 C32 108.4(9) . . ?
N4 C42 C43 119.6(8) . . ?
N4 C42 C32 113.3(8) . . ?
C43 C42 C32 127.1(8) . . ?
C42 C43 H43A 109.5 . . ?
C42 C43 H43B 109.5 . . ?
H43A C43 H43B 109.5 . . ?
C42 C43 H43C 109.5 . . ?
H43A C43 H43C 109.5 . . ?
H43B C43 H43C 109.5 . . ?
N6 C44 C30 176.6(9) . . ?
C21 N1 O2 108.3(7) . . ?
C9 N2 H2A 118.5 . . ?
C42 N4 O4 107.6(7) . . ?
C31 N5 H5A 118.9 . . ?
C20 O2 N1 109.9(7) . . ?
C41 O4 N4 110.2(7) . . ?

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
C6 C1 C2 C3 0.4(13) . . . . ?
C1 C2 C3 C4 -1.5(14) . . . . ?
C1 C2 C3 Br1 178.7(6) . . . . ?
C2 C3 C4 C5 0.7(14) . . . . ?
Br1 C3 C4 C5 -179.4(8) . . . . ?
C3 C4 C5 C6 1.2(15) . . . . ?
C4 C5 C6 C1 -2.3(14) . . . . ?
C4 C5 C6 C7 -179.4(8) . . . . ?
C2 C1 C6 C5 1.6(13) . . . . ?
C2 C1 C6 C7 178.6(7) . . . . ?
C5 C6 C7 C8 -129.6(9) . . . . ?
C1 C6 C7 C8 53.4(11) . . . . ?
C5 C6 C7 C12 48.3(11) . . . . ?
C1 C6 C7 C12 -128.7(9) . . . . ?
C6 C7 C8 C9 178.3(7) . . . . ?
C12 C7 C8 C9 0.4(11) . . . . ?
C6 C7 C8 C19 1.0(11) . . . . ?
C12 C7 C8 C19 -176.8(7) . . . . ?
C7 C8 C9 N2 174.9(8) . . . . ?
C19 C8 C9 N2 -7.7(12) . . . . ?
C7 C8 C9 C10 -9.7(11) . . . . ?
C19 C8 C9 C10 167.7(7) . . . . ?
N2 C9 C10 C21 -18.6(10) . . . . ?
C8 C9 C10 C21 165.4(7) . . . . ?
N2 C9 C10 C20 90.7(8) . . . . ?
C8 C9 C10 C20 -85.3(8) . . . . ?
N2 C9 C10 C11 -146.5(7) . . . . ?
C8 C9 C10 C11 37.5(9) . . . . ?
C21 C10 C11 C13 48.6(9) . . . . ?
C20 C10 C11 C13 -63.9(9) . . . . ?
C9 C10 C11 C13 176.6(7) . . . . ?
C21 C10 C11 C12 175.5(7) . . . . ?
C20 C10 C11 C12 63.0(9) . . . . ?
C9 C10 C11 C12 -56.5(8) . . . . ?
C8 C7 C12 C11 -21.6(11) . . . . ?
C6 C7 C12 C11 160.4(7) . . . . ?
C13 C11 C12 C7 178.1(7) . . . . ?
C10 C11 C12 C7 49.3(9) . . . . ?
C12 C11 C13 C18 120.9(9) . . . . ?
C10 C11 C13 C18 -113.5(8) . . . . ?
C12 C11 C13 C14 -55.5(10) . . . . ?
C10 C11 C13 C14 70.1(10) . . . . ?
C18 C13 C14 C15 -0.4(13) . . . . ?
C11 C13 C14 C15 175.9(8) . . . . ?
C13 C14 C15 C16 -0.9(14) . . . . ?
C14 C15 C16 C17 1.7(16) . . . . ?
C15 C16 C17 C18 -1.2(15) . . . . ?
C14 C13 C18 C17 0.9(13) . . . . ?
C11 C13 C18 C17 -175.5(8) . . . . ?
C16 C17 C18 C13 -0.1(14) . . . . ?
C21 C10 C20 O1 176.6(9) . . . . ?
C9 C10 C20 O1 57.9(12) . . . . ?
C11 C10 C20 O1 -62.9(12) . . . . ?
C21 C10 C20 O2 -2.1(9) . . . . ?
C9 C10 C20 O2 -120.8(8) . . . . ?
C11 C10 C20 O2 118.4(8) . . . . ?
C20 C10 C21 N1 1.1(9) . . . . ?
C9 C10 C21 N1 115.0(8) . . . . ?
C11 C10 C21 N1 -119.1(8) . . . . ?
C20 C10 C21 C22 -177.6(9) . . . . ?
C9 C10 C21 C22 -63.7(11) . . . . ?
C11 C10 C21 C22 62.2(11) . . . . ?
C28 C23 C24 C25 1.7(15) . . . . ?
C23 C24 C25 C26 -0.4(15) . . . . ?
C23 C24 C25 Br2 -179.7(7) . . . . ?
C24 C25 C26 C27 -0.1(13) . . . . ?
Br2 C25 C26 C27 179.2(6) . . . . ?
C25 C26 C27 C28 -0.7(12) . . . . ?
C26 C27 C28 C23 1.9(12) . . . . ?
C26 C27 C28 C29 179.5(7) . . . . ?
C24 C23 C28 C27 -2.5(14) . . . . ?
C24 C23 C28 C29 -180.0(8) . . . . ?
C27 C28 C29 C30 51.1(10) . . . . ?
C23 C28 C29 C30 -131.5(9) . . . . ?
C27 C28 C29 C34 -128.7(8) . . . . ?
C23 C28 C29 C34 48.7(10) . . . . ?
C28 C29 C30 C44 1.8(11) . . . . ?
C34 C29 C30 C44 -178.4(7) . . . . ?
C28 C29 C30 C31 178.0(7) . . . . ?
C34 C29 C30 C31 -2.2(11) . . . . ?
C29 C30 C31 N5 173.6(7) . . . . ?
C44 C30 C31 N5 -10.0(11) . . . . ?
C29 C30 C31 C32 -11.4(10) . . . . ?
C44 C30 C31 C32 165.1(6) . . . . ?
N5 C31 C32 C41 92.6(8) . . . . ?
C30 C31 C32 C41 -82.9(8) . . . . ?
N5 C31 C32 C42 -17.3(10) . . . . ?
C30 C31 C32 C42 167.2(7) . . . . ?
N5 C31 C32 C33 -143.0(7) . . . . ?
C30 C31 C32 C33 41.5(8) . . . . ?
C41 C32 C33 C35 -65.5(9) . . . . ?
C42 C32 C33 C35 48.8(10) . . . . ?
C31 C32 C33 C35 173.9(7) . . . . ?
C41 C32 C33 C34 60.8(9) . . . . ?
C42 C32 C33 C34 175.1(7) . . . . ?
C31 C32 C33 C34 -59.8(8) . . . . ?
C30 C29 C34 C33 -17.0(10) . . . . ?
C28 C29 C34 C33 162.8(7) . . . . ?
C35 C33 C34 C29 177.0(7) . . . . ?
C32 C33 C34 C29 48.5(9) . . . . ?
C34 C33 C35 C40 120.5(8) . . . . ?
C32 C33 C35 C40 -113.1(8) . . . . ?
C34 C33 C35 C36 -55.7(10) . . . . ?
C32 C33 C35 C36 70.6(10) . . . . ?
C40 C35 C36 C37 0.8(13) . . . . ?
C33 C35 C36 C37 177.1(8) . . . . ?
C35 C36 C37 C38 -1.6(15) . . . . ?
C36 C37 C38 C39 2.4(16) . . . . ?
C37 C38 C39 C40 -2.4(17) . . . . ?
C38 C39 C40 C35 1.5(15) . . . . ?
C36 C35 C40 C39 -0.8(13) . . . . ?
C33 C35 C40 C39 -177.1(8) . . . . ?
C42 C32 C41 O3 176.1(9) . . . . ?
C31 C32 C41 O3 58.2(12) . . . . ?
C33 C32 C41 O3 -62.1(12) . . . . ?
C42 C32 C41 O4 -2.0(8) . . . . ?
C31 C32 C41 O4 -119.9(7) . . . . ?
C33 C32 C41 O4 119.7(8) . . . . ?
C41 C32 C42 N4 2.3(9) . . . . ?
C31 C32 C42 N4 117.1(8) . . . . ?
C33 C32 C42 N4 -120.2(8) . . . . ?
C41 C32 C42 C43 -177.8(8) . . . . ?
C31 C32 C42 C43 -63.0(11) . . . . ?
C33 C32 C42 C43 59.6(11) . . . . ?
C10 C21 N1 O2 0.2(10) . . . . ?
C22 C21 N1 O2 179.0(8) . . . . ?
C43 C42 N4 O4 178.4(8) . . . . ?
C32 C42 N4 O4 -1.7(10) . . . . ?
O1 C20 O2 N1 -176.4(8) . . . . ?
C10 C20 O2 N1 2.4(10) . . . . ?
C21 N1 O2 C20 -1.7(10) . . . . ?
O3 C41 O4 N4 -177.1(8) . . . . ?
C32 C41 O4 N4 1.3(9) . . . . ?
C42 N4 O4 C41 0.2(10) . . . . ?

_refine_diff_density_max         0.263
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.057


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Petroleum ether/ethyl acetate 5:1'
