# Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.
# This journal is © the Partner Organisations 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_cd16158m_a
_database_code_depnum_ccdc_archive 'CCDC 1526502'
_audit_update_record             
;
2017-01-10 deposited with the CCDC.
2017-06-12 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C21 H21 Br N2 O2'
_chemical_formula_weight         413.31

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           2
_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'
'-x, -y, -z'

_cell_length_a                   5.095(8)
_cell_length_b                   12.261(19)
_cell_length_c                   17.00(3)
_cell_angle_alpha                73.395(18)
_cell_angle_beta                 81.56(2)
_cell_angle_gamma                78.69(2)
_cell_volume                     993(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    326
_cell_measurement_theta_min      4.823
_cell_measurement_theta_max      32.816

_exptl_crystal_description       prismatic
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.382
_exptl_crystal_F_000             424
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.080
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    2.085
_shelx_estimated_absorpt_T_min   0.731
_shelx_estimated_absorpt_T_max   0.921
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3425
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      273(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            4250
_diffrn_reflns_av_unetI/netI     0.3460
_diffrn_reflns_av_R_equivalents  0.1751
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         1.757
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.946
_diffrn_measured_fraction_theta_full 0.916
_diffrn_reflns_Laue_measured_fraction_max 0.946
_diffrn_reflns_Laue_measured_fraction_full 0.916
_diffrn_reflns_point_group_measured_fraction_max 0.946
_diffrn_reflns_point_group_measured_fraction_full 0.916
_reflns_number_total             3288
_reflns_number_gt                971
_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 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=exp[3.(sinθ/λ)²)]/[σ²(Fo²)+(0.1051P)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     SHELXL
_refine_ls_extinction_coef       ?
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         3288
_refine_ls_number_parameters     249
_refine_ls_number_restraints     78
_refine_ls_R_factor_all          0.2545
_refine_ls_R_factor_gt           0.0911
_refine_ls_wR_factor_ref         0.2887
_refine_ls_wR_factor_gt          0.2098
_refine_ls_goodness_of_fit_ref   0.963
_refine_ls_restrained_S_all      1.009
_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 0.1244(4) 0.93065(15) 0.89777(10) 0.1117(10) Uani 1 1 d . . . . .
N1 N 0.8515(18) 0.8351(7) 0.5479(5) 0.047(2) Uani 1 1 d . . . . .
N2 N 0.4572(19) 0.5347(8) 0.6998(6) 0.060(3) Uani 1 1 d . U . . .
H2A H 0.6183 0.5206 0.7139 0.072 Uiso 1 1 calc R U . . .
O2 O 0.361(2) 0.4148(10) 0.8162(6) 0.118(4) Uani 1 1 d . U . . .
O1 O 0.0357(18) 0.4970(7) 0.7334(5) 0.072(3) Uani 1 1 d . U . . .
C1 C 0.986(2) 0.8070(10) 0.4790(7) 0.054(3) Uani 1 1 d . . . . .
C2 C 1.177(3) 0.8744(10) 0.4313(7) 0.073(4) Uani 1 1 d . . . . .
H2 H 1.2049 0.9388 0.4455 0.088 Uiso 1 1 calc R U . . .
C3 C 1.319(3) 0.8445(12) 0.3646(8) 0.086(5) Uani 1 1 d . . . . .
H3 H 1.4461 0.8887 0.3340 0.104 Uiso 1 1 calc R U . . .
C4 C 1.281(3) 0.7516(13) 0.3407(8) 0.080(4) Uani 1 1 d . . . . .
H4 H 1.3786 0.7341 0.2939 0.096 Uiso 1 1 calc R U . . .
C5 C 1.099(3) 0.6848(12) 0.3870(8) 0.083(4) Uani 1 1 d . . . . .
H5 H 1.0749 0.6211 0.3710 0.100 Uiso 1 1 calc R U . . .
C6 C 0.947(2) 0.7085(10) 0.4573(7) 0.055(3) Uani 1 1 d . . . . .
C7 C 0.753(3) 0.6474(10) 0.5056(7) 0.059(3) Uani 1 1 d . . . . .
H7 H 0.7196 0.5840 0.4913 0.071 Uiso 1 1 calc R U . . .
C8 C 0.610(2) 0.6755(8) 0.5729(7) 0.048(3) Uani 1 1 d . . . . .
C9 C 0.668(2) 0.7731(10) 0.5917(7) 0.049(3) Uani 1 1 d . . . . .
C10 C 0.535(2) 0.8096(9) 0.6649(6) 0.051(3) Uani 1 1 d . . . . .
C11 C 0.641(4) 0.7741(14) 0.7388(10) 0.125(6) Uani 1 1 d . U . . .
H11 H 0.8102 0.7287 0.7421 0.150 Uiso 1 1 calc R U . . .
C12 C 0.508(4) 0.8025(16) 0.8096(10) 0.128(6) Uani 1 1 d . U . . .
H12 H 0.5727 0.7661 0.8606 0.154 Uiso 1 1 calc R U . . .
C13 C 0.291(3) 0.8812(11) 0.8034(8) 0.077(4) Uani 1 1 d . . . . .
C14 C 0.194(4) 0.9209(16) 0.7330(11) 0.127(6) Uani 1 1 d . U . . .
H14 H 0.0325 0.9718 0.7293 0.152 Uiso 1 1 calc R U . . .
C15 C 0.323(3) 0.8906(15) 0.6616(9) 0.114(5) Uani 1 1 d . U . . .
H15 H 0.2573 0.9286 0.6110 0.136 Uiso 1 1 calc R U . . .
C16 C 0.386(2) 0.6133(10) 0.6210(7) 0.062(3) Uani 1 1 d . . . . .
H16A H 0.2316 0.6699 0.6310 0.074 Uiso 1 1 calc R U . . .
H16B H 0.3328 0.5700 0.5880 0.074 Uiso 1 1 calc R U . . .
C17 C 0.263(3) 0.4866(10) 0.7478(8) 0.057(3) Uani 1 1 d . U . . .
C18 C 0.181(4) 0.3404(18) 0.8817(11) 0.115(6) Uani 1 1 d . U . . .
C19 C 0.411(7) 0.225(3) 0.929(2) 0.124(12) Uani 0.5 1 d . U P A 1
H19A H 0.3387 0.1904 0.9836 0.186 Uiso 0.5 1 calc R U P A 1
H19B H 0.5752 0.2508 0.9308 0.186 Uiso 0.5 1 calc R U P A 1
H19C H 0.4480 0.1682 0.8974 0.186 Uiso 0.5 1 calc R U P A 1
C19' C 0.301(6) 0.348(3) 0.9618(16) 0.095(9) Uani 0.5 1 d . U P A 2
C20 C 0.077(4) 0.2661(14) 0.8509(11) 0.132(7) Uani 1 1 d . U . . .
H20A H 0.2188 0.2251 0.8216 0.198 Uiso 1 1 calc R U . . .
H20B H -0.0556 0.3098 0.8142 0.198 Uiso 1 1 calc R U . . .
H20C H -0.0055 0.2121 0.8958 0.198 Uiso 1 1 calc R U . . .
C21 C -0.019(4) 0.4296(16) 0.9124(10) 0.134(7) Uani 1 1 d . U . . .
H21A H -0.1469 0.4661 0.8728 0.200 Uiso 1 1 calc R U . . .
H21B H 0.0728 0.4865 0.9203 0.200 Uiso 1 1 calc R U . . .
H21C H -0.1107 0.3935 0.9639 0.200 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 C13 1.901(11) . ?
N1 C9 1.326(12) . ?
N1 C1 1.365(12) . ?
N2 C17 1.307(14) . ?
N2 C16 1.456(14) . ?
N2 H2A 0.8600 . ?
O2 C17 1.338(15) . ?
O2 C18 1.535(18) . ?
O1 C17 1.194(14) . ?
C1 C2 1.408(15) . ?
C1 C6 1.417(15) . ?
C2 C3 1.356(15) . ?
C2 H2 0.9300 . ?
C3 C4 1.368(17) . ?
C3 H3 0.9300 . ?
C4 C5 1.368(17) . ?
C4 H4 0.9300 . ?
C5 C6 1.398(15) . ?
C5 H5 0.9300 . ?
C6 C7 1.381(15) . ?
C7 C8 1.357(14) . ?
C7 H7 0.9300 . ?
C8 C9 1.417(14) . ?
C8 C16 1.505(15) . ?
C9 C10 1.470(14) . ?
C10 C15 1.312(18) . ?
C10 C11 1.359(19) . ?
C11 C12 1.391(19) . ?
C11 H11 0.9300 . ?
C12 C13 1.32(2) . ?
C12 H12 0.9300 . ?
C13 C14 1.29(2) . ?
C14 C15 1.404(19) . ?
C14 H14 0.9300 . ?
C15 H15 0.9300 . ?
C16 H16A 0.9700 . ?
C16 H16B 0.9700 . ?
C18 C20 1.39(2) . ?
C18 C21 1.50(2) . ?
C18 C19' 1.60(3) . ?
C18 C19 1.73(4) . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?
C19' H19D 0.9600 . ?
C19' H19E 0.9600 . ?
C19' H19F 0.9600 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C9 N1 C1 118.9(9) . . ?
C17 N2 C16 116.4(11) . . ?
C17 N2 H2A 121.8 . . ?
C16 N2 H2A 121.8 . . ?
C17 O2 C18 120.8(13) . . ?
N1 C1 C2 119.0(11) . . ?
N1 C1 C6 121.2(10) . . ?
C2 C1 C6 119.8(10) . . ?
C3 C2 C1 119.4(12) . . ?
C3 C2 H2 120.3 . . ?
C1 C2 H2 120.3 . . ?
C2 C3 C4 122.4(13) . . ?
C2 C3 H3 118.8 . . ?
C4 C3 H3 118.8 . . ?
C3 C4 C5 118.8(11) . . ?
C3 C4 H4 120.6 . . ?
C5 C4 H4 120.6 . . ?
C4 C5 C6 122.5(12) . . ?
C4 C5 H5 118.8 . . ?
C6 C5 H5 118.8 . . ?
C7 C6 C5 125.9(12) . . ?
C7 C6 C1 116.9(9) . . ?
C5 C6 C1 117.1(12) . . ?
C8 C7 C6 123.2(11) . . ?
C8 C7 H7 118.4 . . ?
C6 C7 H7 118.4 . . ?
C7 C8 C9 116.2(11) . . ?
C7 C8 C16 122.4(11) . . ?
C9 C8 C16 121.3(10) . . ?
N1 C9 C8 123.6(9) . . ?
N1 C9 C10 114.8(10) . . ?
C8 C9 C10 121.6(10) . . ?
C15 C10 C11 114.1(12) . . ?
C15 C10 C9 122.4(11) . . ?
C11 C10 C9 123.0(12) . . ?
C10 C11 C12 123.2(16) . . ?
C10 C11 H11 118.4 . . ?
C12 C11 H11 118.4 . . ?
C13 C12 C11 119.2(17) . . ?
C13 C12 H12 120.4 . . ?
C11 C12 H12 120.4 . . ?
C14 C13 C12 118.1(14) . . ?
C14 C13 Br1 122.1(12) . . ?
C12 C13 Br1 119.8(13) . . ?
C13 C14 C15 122.8(16) . . ?
C13 C14 H14 118.6 . . ?
C15 C14 H14 118.6 . . ?
C10 C15 C14 121.2(15) . . ?
C10 C15 H15 119.4 . . ?
C14 C15 H15 119.4 . . ?
N2 C16 C8 113.7(10) . . ?
N2 C16 H16A 108.8 . . ?
C8 C16 H16A 108.8 . . ?
N2 C16 H16B 108.8 . . ?
C8 C16 H16B 108.8 . . ?
H16A C16 H16B 107.7 . . ?
O1 C17 N2 127.4(13) . . ?
O1 C17 O2 123.1(12) . . ?
N2 C17 O2 109.3(13) . . ?
C20 C18 C21 116.2(18) . . ?
C20 C18 O2 112.7(16) . . ?
C21 C18 O2 102.0(15) . . ?
C20 C18 C19' 142.2(19) . . ?
C21 C18 C19' 75.8(18) . . ?
O2 C18 C19' 97.9(16) . . ?
C20 C18 C19 89.0(19) . . ?
C21 C18 C19 134(2) . . ?
O2 C18 C19 102.6(15) . . ?
C18 C19 H19A 109.5 . . ?
C18 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
C18 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 109.5 . . ?
C18 C19' H19D 109.5 . . ?
C18 C19' H19E 109.5 . . ?
H19D C19' H19E 109.5 . . ?
C18 C19' H19F 109.5 . . ?
H19D C19' H19F 109.5 . . ?
H19E C19' H19F 109.5 . . ?
C18 C20 H20A 109.5 . . ?
C18 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C18 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C18 C21 H21A 109.5 . . ?
C18 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C18 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?

_refine_diff_density_max         0.494
_refine_diff_density_min         -0.436
_refine_diff_density_rms         0.110

_shelxl_version_number           2013-4



####################################################################### 
# 
# 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_cd16586
_database_code_depnum_ccdc_archive 'CCDC 1526503'
_audit_update_record             
;
2017-01-10 deposited with the CCDC.
2017-06-12 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C22 H26 N2 O4'
_chemical_formula_weight         382.45

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'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_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'
'-x, -y, -z'

_cell_length_a                   6.1408(17)
_cell_length_b                   10.540(3)
_cell_length_c                   16.567(5)
_cell_angle_alpha                87.399(7)
_cell_angle_beta                 81.181(6)
_cell_angle_gamma                79.922(6)
_cell_volume                     1043.1(5)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1115
_cell_measurement_theta_min      4.608
_cell_measurement_theta_max      42.345

_exptl_crystal_description       prismatic
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.218
_exptl_crystal_F_000             408
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.080
_exptl_absorpt_coefficient_mu    0.084
_shelx_estimated_absorpt_T_min   0.983
_shelx_estimated_absorpt_T_max   0.993
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5750
_exptl_absorpt_correction_T_max  0.7456
_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            5786
_diffrn_reflns_av_unetI/netI     0.0674
_diffrn_reflns_av_R_equivalents  0.0343
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         1.963
_diffrn_reflns_theta_max         24.994
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measured_fraction_theta_full 0.971
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_Laue_measured_fraction_full 0.971
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 0.971
_reflns_number_total             3671
_reflns_number_gt                2479
_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'
_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)+(0.0787P)²+0.1519P] 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_number_reflns         3671
_refine_ls_number_parameters     257
_refine_ls_number_restraints     12
_refine_ls_R_factor_all          0.1062
_refine_ls_R_factor_gt           0.0721
_refine_ls_wR_factor_ref         0.1818
_refine_ls_wR_factor_gt          0.1651
_refine_ls_goodness_of_fit_ref   1.081
_refine_ls_restrained_S_all      1.095
_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
N1 N 0.7209(4) 0.3352(2) 0.70316(15) 0.0503(6) Uani 1 1 d . . . . .
N2 N 0.6944(4) 0.6204(2) 0.68807(14) 0.0462(6) Uani 1 1 d . . . . .
O1 O 0.8640(3) 0.52615(18) 0.64463(12) 0.0532(6) Uani 1 1 d . . . . .
O2 O 0.2892(4) 0.95389(19) 0.39818(13) 0.0610(6) Uani 1 1 d . . . . .
O3 O 1.0597(4) 0.2199(2) 0.71325(14) 0.0681(7) Uani 1 1 d . . . . .
O4 O 0.7463(3) 0.17918(19) 0.79520(12) 0.0548(6) Uani 1 1 d . . . . .
C1 C 0.4805(5) 0.3725(3) 0.71420(19) 0.0519(8) Uani 1 1 d . . . . .
H1A H 0.4181 0.4147 0.7654 0.062 Uiso 1 1 calc R U . . .
H1B H 0.4014 0.3036 0.7050 0.062 Uiso 1 1 calc R U . . .
C2 C 0.5112(5) 0.4661(3) 0.64060(18) 0.0496(8) Uani 1 1 d . . . . .
H2 H 0.4431 0.4475 0.5936 0.060 Uiso 1 1 calc R U . . .
C3 C 0.7627(5) 0.4185(3) 0.63295(18) 0.0527(8) Uani 1 1 d . . . . .
H3 H 0.8264 0.3722 0.5825 0.063 Uiso 1 1 calc R U . . .
C4 C 0.4829(5) 0.6081(3) 0.65918(17) 0.0435(7) Uani 1 1 d . . . . .
H4 H 0.3590 0.6291 0.7039 0.052 Uiso 1 1 calc R U . . .
C5 C 0.4410(4) 0.6978(2) 0.58771(15) 0.0393(7) Uani 1 1 d . . . . .
C6 C 0.2231(5) 0.7530(3) 0.57861(17) 0.0476(7) Uani 1 1 d . . . . .
H6 H 0.1051 0.7326 0.6163 0.057 Uiso 1 1 calc R U . . .
C7 C 0.1787(5) 0.8367(3) 0.51531(19) 0.0515(8) Uani 1 1 d . . . . .
H7 H 0.0316 0.8728 0.5107 0.062 Uiso 1 1 calc R U . . .
C8 C 0.3502(5) 0.8679(3) 0.45840(16) 0.0439(7) Uani 1 1 d . . . . .
C9 C 0.5676(5) 0.8128(3) 0.46518(17) 0.0465(7) Uani 1 1 d . . . . .
H9 H 0.6845 0.8319 0.4265 0.056 Uiso 1 1 calc R U . . .
C10 C 0.6113(5) 0.7292(3) 0.52944(17) 0.0465(7) Uani 1 1 d . . . . .
H10 H 0.7586 0.6932 0.5338 0.056 Uiso 1 1 calc R U . . .
C11 C 0.4607(6) 1.0014(3) 0.34418(19) 0.0609(9) Uani 1 1 d . . . . .
H11A H 0.5663 1.0260 0.3751 0.091 Uiso 1 1 calc R U . . .
H11B H 0.3962 1.0750 0.3143 0.091 Uiso 1 1 calc R U . . .
H11C H 0.5356 0.9354 0.3067 0.091 Uiso 1 1 calc R U . . .
C12 C 0.7025(6) 0.6168(3) 0.77301(19) 0.0541(8) Uani 1 1 d . . . . .
C13 C 0.5325(8) 0.6875(4) 0.8248(2) 0.0889(13) Uani 1 1 d . . . . .
H13 H 0.4085 0.7334 0.8043 0.107 Uiso 1 1 calc R U . . .
C14 C 0.5456(10) 0.6905(5) 0.9071(3) 0.1319(16) Uani 1 1 d . U . . .
H14 H 0.4268 0.7349 0.9422 0.158 Uiso 1 1 calc R U . . .
C15 C 0.7304(11) 0.6292(5) 0.9371(3) 0.1309(15) Uani 1 1 d . U . . .
H15 H 0.7398 0.6331 0.9925 0.157 Uiso 1 1 calc R U . . .
C16 C 0.8995(10) 0.5629(5) 0.8867(3) 0.1272(16) Uani 1 1 d . U . . .
H16 H 1.0262 0.5217 0.9076 0.153 Uiso 1 1 calc R U . . .
C17 C 0.8901(7) 0.5544(4) 0.8046(2) 0.0820(12) Uani 1 1 d . . . . .
H17 H 1.0085 0.5073 0.7706 0.098 Uiso 1 1 calc R U . . .
C18 C 0.8609(5) 0.2415(3) 0.73532(18) 0.0474(7) Uani 1 1 d . . . . .
C19 C 0.8621(6) 0.0853(4) 0.8482(2) 0.0718(10) Uani 1 1 d . . . . .
C20 C 1.0036(9) 0.1530(6) 0.8932(3) 0.133(2) Uani 1 1 d . . . . .
H20A H 1.1153 0.1853 0.8546 0.199 Uiso 1 1 calc R U . . .
H20B H 1.0752 0.0933 0.9305 0.199 Uiso 1 1 calc R U . . .
H20C H 0.9103 0.2234 0.9231 0.199 Uiso 1 1 calc R U . . .
C21 C 0.9913(7) -0.0290(4) 0.7998(3) 0.1107(16) Uani 1 1 d . . . . .
H21A H 0.8920 -0.0649 0.7713 0.166 Uiso 1 1 calc R U . . .
H21B H 1.0560 -0.0931 0.8363 0.166 Uiso 1 1 calc R U . . .
H21C H 1.1079 -0.0017 0.7611 0.166 Uiso 1 1 calc R U . . .
C22 C 0.6667(7) 0.0449(4) 0.9057(2) 0.0933(13) Uani 1 1 d . . . . .
H22A H 0.5739 0.1199 0.9308 0.140 Uiso 1 1 calc R U . . .
H22B H 0.7226 -0.0128 0.9471 0.140 Uiso 1 1 calc R U . . .
H22C H 0.5803 0.0024 0.8753 0.140 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
N1 C18 1.340(4) . ?
N1 C3 1.444(4) . ?
N1 C1 1.445(4) . ?
N2 C12 1.414(4) . ?
N2 O1 1.436(3) . ?
N2 C4 1.479(3) . ?
O1 C3 1.419(3) . ?
O2 C8 1.368(3) . ?
O2 C11 1.420(4) . ?
O3 C18 1.204(3) . ?
O4 C18 1.341(3) . ?
O4 C19 1.456(4) . ?
C1 C2 1.543(4) . ?
C1 H1A 0.9700 . ?
C1 H1B 0.9700 . ?
C2 C4 1.517(4) . ?
C2 C3 1.525(4) . ?
C2 H2 0.9800 . ?
C3 H3 0.9800 . ?
C4 C5 1.506(4) . ?
C4 H4 0.9800 . ?
C5 C10 1.385(4) . ?
C5 C6 1.390(4) . ?
C6 C7 1.368(4) . ?
C6 H6 0.9300 . ?
C7 C8 1.377(4) . ?
C7 H7 0.9300 . ?
C8 C9 1.379(4) . ?
C9 C10 1.378(4) . ?
C9 H9 0.9300 . ?
C10 H10 0.9300 . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C12 C13 1.376(5) . ?
C12 C17 1.386(5) . ?
C13 C14 1.379(5) . ?
C13 H13 0.9300 . ?
C14 C15 1.357(7) . ?
C14 H14 0.9300 . ?
C15 C16 1.341(7) . ?
C15 H15 0.9300 . ?
C16 C17 1.378(5) . ?
C16 H16 0.9300 . ?
C17 H17 0.9300 . ?
C19 C21 1.511(5) . ?
C19 C20 1.512(6) . ?
C19 C22 1.523(5) . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
C22 H22A 0.9600 . ?
C22 H22B 0.9600 . ?
C22 H22C 0.9600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C18 N1 C3 129.8(2) . . ?
C18 N1 C1 133.8(2) . . ?
C3 N1 C1 95.5(2) . . ?
C12 N2 O1 112.6(2) . . ?
C12 N2 C4 119.1(2) . . ?
O1 N2 C4 105.96(19) . . ?
C3 O1 N2 107.2(2) . . ?
C8 O2 C11 118.2(2) . . ?
C18 O4 C19 120.9(2) . . ?
N1 C1 C2 87.7(2) . . ?
N1 C1 H1A 114.0 . . ?
C2 C1 H1A 114.0 . . ?
N1 C1 H1B 114.0 . . ?
C2 C1 H1B 114.0 . . ?
H1A C1 H1B 111.2 . . ?
C4 C2 C3 104.4(2) . . ?
C4 C2 C1 116.9(2) . . ?
C3 C2 C1 88.3(2) . . ?
C4 C2 H2 114.6 . . ?
C3 C2 H2 114.6 . . ?
C1 C2 H2 114.6 . . ?
O1 C3 N1 116.7(2) . . ?
O1 C3 C2 107.3(2) . . ?
N1 C3 C2 88.4(2) . . ?
O1 C3 H3 113.9 . . ?
N1 C3 H3 113.9 . . ?
C2 C3 H3 113.9 . . ?
N2 C4 C5 111.4(2) . . ?
N2 C4 C2 103.8(2) . . ?
C5 C4 C2 114.6(2) . . ?
N2 C4 H4 109.0 . . ?
C5 C4 H4 109.0 . . ?
C2 C4 H4 109.0 . . ?
C10 C5 C6 117.4(3) . . ?
C10 C5 C4 122.9(2) . . ?
C6 C5 C4 119.7(2) . . ?
C7 C6 C5 121.3(3) . . ?
C7 C6 H6 119.3 . . ?
C5 C6 H6 119.3 . . ?
C6 C7 C8 120.5(3) . . ?
C6 C7 H7 119.8 . . ?
C8 C7 H7 119.8 . . ?
O2 C8 C7 116.1(3) . . ?
O2 C8 C9 124.5(3) . . ?
C7 C8 C9 119.4(3) . . ?
C8 C9 C10 119.9(3) . . ?
C8 C9 H9 120.1 . . ?
C10 C9 H9 120.1 . . ?
C9 C10 C5 121.6(3) . . ?
C9 C10 H10 119.2 . . ?
C5 C10 H10 119.2 . . ?
O2 C11 H11A 109.5 . . ?
O2 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
O2 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
C13 C12 C17 118.6(3) . . ?
C13 C12 N2 119.8(3) . . ?
C17 C12 N2 121.2(3) . . ?
C12 C13 C14 120.2(4) . . ?
C12 C13 H13 119.9 . . ?
C14 C13 H13 119.9 . . ?
C15 C14 C13 120.5(5) . . ?
C15 C14 H14 119.7 . . ?
C13 C14 H14 119.7 . . ?
C16 C15 C14 119.6(4) . . ?
C16 C15 H15 120.2 . . ?
C14 C15 H15 120.2 . . ?
C15 C16 C17 121.6(5) . . ?
C15 C16 H16 119.2 . . ?
C17 C16 H16 119.2 . . ?
C16 C17 C12 119.4(4) . . ?
C16 C17 H17 120.3 . . ?
C12 C17 H17 120.3 . . ?
O3 C18 N1 123.8(3) . . ?
O3 C18 O4 126.5(3) . . ?
N1 C18 O4 109.8(3) . . ?
O4 C19 C21 110.6(3) . . ?
O4 C19 C20 108.5(3) . . ?
C21 C19 C20 114.2(4) . . ?
O4 C19 C22 101.5(3) . . ?
C21 C19 C22 109.9(3) . . ?
C20 C19 C22 111.5(3) . . ?
C19 C20 H20A 109.5 . . ?
C19 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C19 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C19 C21 H21A 109.5 . . ?
C19 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C19 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C19 C22 H22A 109.5 . . ?
C19 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C19 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 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
C12 N2 O1 C3 97.9(3) . . . . ?
C4 N2 O1 C3 -33.9(3) . . . . ?
C18 N1 C1 C2 -170.6(3) . . . . ?
C3 N1 C1 C2 -1.1(2) . . . . ?
N1 C1 C2 C4 -104.4(3) . . . . ?
N1 C1 C2 C3 1.0(2) . . . . ?
N2 O1 C3 N1 -75.8(3) . . . . ?
N2 O1 C3 C2 21.3(3) . . . . ?
C18 N1 C3 O1 -80.2(4) . . . . ?
C1 N1 C3 O1 109.7(3) . . . . ?
C18 N1 C3 C2 171.2(3) . . . . ?
C1 N1 C3 C2 1.1(2) . . . . ?
C4 C2 C3 O1 -1.1(3) . . . . ?
C1 C2 C3 O1 -118.6(2) . . . . ?
C4 C2 C3 N1 116.4(2) . . . . ?
C1 C2 C3 N1 -1.0(2) . . . . ?
C12 N2 C4 C5 140.1(2) . . . . ?
O1 N2 C4 C5 -91.8(2) . . . . ?
C12 N2 C4 C2 -96.1(3) . . . . ?
O1 N2 C4 C2 32.0(3) . . . . ?
C3 C2 C4 N2 -18.5(3) . . . . ?
C1 C2 C4 N2 77.0(3) . . . . ?
C3 C2 C4 C5 103.1(3) . . . . ?
C1 C2 C4 C5 -161.3(2) . . . . ?
N2 C4 C5 C10 33.9(3) . . . . ?
C2 C4 C5 C10 -83.6(3) . . . . ?
N2 C4 C5 C6 -145.9(2) . . . . ?
C2 C4 C5 C6 96.6(3) . . . . ?
C10 C5 C6 C7 -1.0(4) . . . . ?
C4 C5 C6 C7 178.8(2) . . . . ?
C5 C6 C7 C8 0.4(4) . . . . ?
C11 O2 C8 C7 172.2(2) . . . . ?
C11 O2 C8 C9 -7.5(4) . . . . ?
C6 C7 C8 O2 -179.0(2) . . . . ?
C6 C7 C8 C9 0.7(4) . . . . ?
O2 C8 C9 C10 178.5(2) . . . . ?
C7 C8 C9 C10 -1.2(4) . . . . ?
C8 C9 C10 C5 0.6(4) . . . . ?
C6 C5 C10 C9 0.5(4) . . . . ?
C4 C5 C10 C9 -179.3(2) . . . . ?
O1 N2 C12 C13 -170.6(3) . . . . ?
C4 N2 C12 C13 -45.6(4) . . . . ?
O1 N2 C12 C17 16.6(4) . . . . ?
C4 N2 C12 C17 141.5(3) . . . . ?
C17 C12 C13 C14 -3.1(6) . . . . ?
N2 C12 C13 C14 -176.2(4) . . . . ?
C12 C13 C14 C15 3.3(8) . . . . ?
C13 C14 C15 C16 -1.4(10) . . . . ?
C14 C15 C16 C17 -0.5(10) . . . . ?
C15 C16 C17 C12 0.6(8) . . . . ?
C13 C12 C17 C16 1.2(6) . . . . ?
N2 C12 C17 C16 174.2(4) . . . . ?
C3 N1 C18 O3 7.7(5) . . . . ?
C1 N1 C18 O3 174.1(3) . . . . ?
C3 N1 C18 O4 -173.3(3) . . . . ?
C1 N1 C18 O4 -6.9(4) . . . . ?
C19 O4 C18 O3 8.0(4) . . . . ?
C19 O4 C18 N1 -171.0(3) . . . . ?
C18 O4 C19 C21 -64.8(4) . . . . ?
C18 O4 C19 C20 61.1(4) . . . . ?
C18 O4 C19 C22 178.7(3) . . . . ?

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
C21 H21C O3 0.96 2.42 2.996(5) 118.6 .
C20 H20A O3 0.96 2.42 3.014(5) 119.7 .
C9 H9 O3 0.93 2.61 3.440(4) 148.6 2_766
C1 H1B O3 0.97 2.40 3.276(4) 150.3 1_455
C21 H21C O3 0.96 2.42 2.996(5) 118.6 .
C20 H20A O3 0.96 2.42 3.014(5) 119.7 .
C9 H9 O3 0.93 2.61 3.440(4) 148.6 2_766
C1 H1B O3 0.97 2.40 3.276(4) 150.3 1_455
C1 H1B O3 0.97 2.40 3.276(4) 150.3 1_455
C9 H9 O3 0.93 2.61 3.440(4) 148.6 2_766
C20 H20A O3 0.96 2.42 3.014(5) 119.7 .
C21 H21C O3 0.96 2.42 2.996(5) 118.6 .
C1 H1B O3 0.97 2.40 3.276(4) 150.3 1_455
C9 H9 O3 0.93 2.61 3.440(4) 148.6 2_766
C20 H20A O3 0.96 2.42 3.014(5) 119.7 .
C21 H21C O3 0.96 2.42 2.996(5) 118.6 .

_refine_diff_density_max         0.199
_refine_diff_density_min         -0.223
_refine_diff_density_rms         0.046

_shelxl_version_number           2013-4



