# Electronic Supplementary Material (ESI) for Green Chemistry.
# 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_I
_audit_block_doi                 10.5517/cc1jps44
_database_code_depnum_ccdc_archive 'CCDC 1421106'
loop_
_citation_id
_citation_doi
_citation_year
1 10.1107/S2056989015018241 2015
_audit_update_record             
;
2015-09-29 deposited with the CCDC.
2017-03-31 downloaded from the CCDC.
;
_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
1-methyl-2-(methylamino)-3-nitro-1H-chromeno[2,3-b]pyridin-5(10aH)-one
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C14 H13 N3 O4'
_chemical_formula_sum            'C14 H13 N3 O4'
_chemical_formula_weight         287.27

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   'F d d 2'
_symmetry_space_group_name_Hall  'F 2 -2d'

loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x, -y, z'
'-x+1/4, y+1/4, z+1/4'
'x+1/4, -y+1/4, z+1/4'
'x, y+1/2, z+1/2'
'-x, -y+1/2, z+1/2'
'-x+1/4, y+3/4, z+3/4'
'x+1/4, -y+3/4, z+3/4'
'x+1/2, y, z+1/2'
'-x+1/2, -y, z+1/2'
'-x+3/4, y+1/4, z+3/4'
'x+3/4, -y+1/4, z+3/4'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1/2, z'
'-x+3/4, y+3/4, z+1/4'
'x+3/4, -y+3/4, z+1/4'

_cell_length_a                   24.0182(13)
_cell_length_b                   26.8445(14)
_cell_length_c                   7.9140(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     5102.6(5)
_cell_formula_units_Z            16
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2096
_cell_measurement_theta_min      2.28
_cell_measurement_theta_max      25.00

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.30
_exptl_crystal_size_min          0.25
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.496
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             2400
_exptl_absorpt_coefficient_mu    0.112
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.962
_exptl_absorpt_correction_T_max  0.972
_exptl_absorpt_process_details   'SADABS (Bruker, 2008)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(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  'Bruker SMART APEXII CCD'
_diffrn_measurement_method       'ω and φ scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            12952
_diffrn_reflns_av_R_equivalents  0.0210
_diffrn_reflns_av_sigmaI/netI    0.0169
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         2.28
_diffrn_reflns_theta_max         25.00
_reflns_number_total             2261
_reflns_number_gt                2096
_reflns_threshold_expression     I>2σ(I)

_computing_data_collection       'APEX2 (Bruker, 2008)'
_computing_cell_refinement       'SAINT (Bruker, 2008)'
_computing_data_reduction        SAINT
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'ORTEP-3 (Farrugia, 2012)'
_computing_publication_material  
'SHELXL-97 and PLATON (Spek, 2009)'

_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)+(0.0468P)²+1.3678P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details none
_refine_ls_number_reflns         2261
_refine_ls_number_parameters     192
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0336
_refine_ls_R_factor_gt           0.0300
_refine_ls_wR_factor_ref         0.0759
_refine_ls_wR_factor_gt          0.0733
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_restrained_S_all      1.044
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

_diffrn_measured_fraction_theta_max 0.999
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.999
_refine_diff_density_max         0.110
_refine_diff_density_min         -0.138
_refine_diff_density_rms         0.030


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 0.03152(7) 0.07119(6) 0.5103(2) 0.0316(4) Uani 1 1 d . . .
C2 C 0.07422(7) 0.05817(6) 0.6093(2) 0.0348(4) Uani 1 1 d . . .
H2 H 0.0673 0.0483 0.7200 0.042 Uiso 1 1 calc R . .
C3 C 0.12950(7) 0.05908(6) 0.5492(2) 0.0348(4) Uani 1 1 d . . .
C4 C 0.14101(7) 0.07284(6) 0.3758(2) 0.0323(4) Uani 1 1 d . . .
C5 C 0.21801(8) 0.07230(9) 0.1521(3) 0.0562(6) Uani 1 1 d . . .
H5A H 0.1937 0.0565 0.0723 0.084 Uiso 1 1 calc R . .
H5B H 0.2531 0.0551 0.1543 0.084 Uiso 1 1 calc R . .
H5C H 0.2239 0.1063 0.1193 0.084 Uiso 1 1 calc R . .
C6 C 0.10471(8) 0.10996(8) 0.1107(2) 0.0514(5) Uani 1 1 d . . .
H6A H 0.1378 0.1300 0.1095 0.077 Uiso 1 1 calc R . .
H6B H 0.0731 0.1305 0.0853 0.077 Uiso 1 1 calc R . .
H6C H 0.1078 0.0841 0.0275 0.077 Uiso 1 1 calc R . .
C7 C 0.04068(6) 0.08867(6) 0.33547(19) 0.0305(4) Uani 1 1 d . . .
H7 H 0.0273 0.1231 0.3273 0.037 Uiso 1 1 calc R . .
C8 C -0.04681(7) 0.05675(6) 0.2547(2) 0.0315(4) Uani 1 1 d . . .
C9 C -0.08276(7) 0.04527(7) 0.1229(2) 0.0400(4) Uani 1 1 d . . .
H9 H -0.0692 0.0389 0.0149 0.048 Uiso 1 1 calc R . .
C10 C -0.13915(8) 0.04360(7) 0.1563(3) 0.0439(5) Uani 1 1 d . . .
H10 H -0.1637 0.0361 0.0691 0.053 Uiso 1 1 calc R . .
C11 C -0.16010(8) 0.05281(7) 0.3162(3) 0.0428(5) Uani 1 1 d . . .
H11 H -0.1983 0.0528 0.3352 0.051 Uiso 1 1 calc R . .
C12 C -0.12390(8) 0.06192(7) 0.4459(3) 0.0403(4) Uani 1 1 d . . .
H12 H -0.1377 0.0669 0.5543 0.048 Uiso 1 1 calc R . .
C13 C -0.06647(7) 0.06394(6) 0.4184(2) 0.0333(4) Uani 1 1 d . . .
C14 C -0.02720(8) 0.06748(6) 0.5610(2) 0.0353(4) Uani 1 1 d . . .
O1 O 0.22180(6) 0.04252(6) 0.6136(2) 0.0619(4) Uani 1 1 d . . .
O2 O 0.15774(6) 0.02632(7) 0.79971(18) 0.0710(5) Uani 1 1 d . . .
O3 O -0.04181(6) 0.06418(6) 0.70928(16) 0.0523(4) Uani 1 1 d . . .
O4 O 0.00911(5) 0.05848(4) 0.21703(15) 0.0356(3) Uani 1 1 d . . .
N1 N 0.17083(7) 0.04246(6) 0.6569(2) 0.0458(4) Uani 1 1 d . . .
N2 N 0.19283(6) 0.07078(5) 0.3198(2) 0.0409(4) Uani 1 1 d . . .
H2A H 0.2169 0.0679 0.3996 0.049 Uiso 1 1 calc R . .
N3 N 0.09766(5) 0.08753(5) 0.27888(17) 0.0339(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
C1 C2 1.337(2) . ?
C1 C14 1.470(2) . ?
C1 C7 1.478(2) . ?
C2 C3 1.410(2) . ?
C2 H2 0.9300 . ?
C3 N1 1.383(2) . ?
C3 C4 1.448(3) . ?
C4 N2 1.322(2) . ?
C4 N3 1.352(2) . ?
C5 N2 1.459(3) . ?
C5 H5A 0.9600 . ?
C5 H5B 0.9600 . ?
C5 H5C 0.9600 . ?
C6 N3 1.471(2) . ?
C6 H6A 0.9600 . ?
C6 H6B 0.9600 . ?
C6 H6C 0.9600 . ?
C7 N3 1.440(2) . ?
C7 O4 1.4527(19) . ?
C7 H7 0.9800 . ?
C8 O4 1.3767(19) . ?
C8 C9 1.389(2) . ?
C8 C13 1.392(2) . ?
C9 C10 1.381(3) . ?
C9 H9 0.9300 . ?
C10 C11 1.384(3) . ?
C10 H10 0.9300 . ?
C11 C12 1.367(3) . ?
C11 H11 0.9300 . ?
C12 C13 1.398(2) . ?
C12 H12 0.9300 . ?
C13 C14 1.474(2) . ?
C14 O3 1.228(2) . ?
O1 N1 1.271(2) . ?
O2 N1 1.250(2) . ?
N2 H2A 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 C14 123.98(15) . . ?
C2 C1 C7 121.15(15) . . ?
C14 C1 C7 114.82(14) . . ?
C1 C2 C3 121.34(16) . . ?
C1 C2 H2 119.3 . . ?
C3 C2 H2 119.3 . . ?
N1 C3 C2 117.53(16) . . ?
N1 C3 C4 121.99(16) . . ?
C2 C3 C4 120.25(15) . . ?
N2 C4 N3 123.19(16) . . ?
N2 C4 C3 119.11(15) . . ?
N3 C4 C3 117.71(15) . . ?
N2 C5 H5A 109.5 . . ?
N2 C5 H5B 109.5 . . ?
H5A C5 H5B 109.5 . . ?
N2 C5 H5C 109.5 . . ?
H5A C5 H5C 109.5 . . ?
H5B C5 H5C 109.5 . . ?
N3 C6 H6A 109.5 . . ?
N3 C6 H6B 109.5 . . ?
H6A C6 H6B 109.5 . . ?
N3 C6 H6C 109.5 . . ?
H6A C6 H6C 109.5 . . ?
H6B C6 H6C 109.5 . . ?
N3 C7 O4 106.47(12) . . ?
N3 C7 C1 115.21(13) . . ?
O4 C7 C1 110.46(13) . . ?
N3 C7 H7 108.2 . . ?
O4 C7 H7 108.2 . . ?
C1 C7 H7 108.2 . . ?
O4 C8 C9 116.82(15) . . ?
O4 C8 C13 121.86(15) . . ?
C9 C8 C13 121.26(16) . . ?
C10 C9 C8 118.23(18) . . ?
C10 C9 H9 120.9 . . ?
C8 C9 H9 120.9 . . ?
C9 C10 C11 121.74(18) . . ?
C9 C10 H10 119.1 . . ?
C11 C10 H10 119.1 . . ?
C12 C11 C10 119.15(17) . . ?
C12 C11 H11 120.4 . . ?
C10 C11 H11 120.4 . . ?
C11 C12 C13 121.18(18) . . ?
C11 C12 H12 119.4 . . ?
C13 C12 H12 119.4 . . ?
C8 C13 C12 118.32(16) . . ?
C8 C13 C14 120.29(15) . . ?
C12 C13 C14 120.99(16) . . ?
O3 C14 C1 122.65(16) . . ?
O3 C14 C13 122.98(17) . . ?
C1 C14 C13 114.19(15) . . ?
C8 O4 C7 112.85(13) . . ?
O2 N1 O1 119.09(16) . . ?
O2 N1 C3 119.25(16) . . ?
O1 N1 C3 121.65(16) . . ?
C4 N2 C5 133.91(16) . . ?
C4 N2 H2A 113.0 . . ?
C5 N2 H2A 113.0 . . ?
C4 N3 C7 124.17(14) . . ?
C4 N3 C6 122.96(15) . . ?
C7 N3 C6 112.47(13) . . ?

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
C14 C1 C2 C3 175.22(15) . . . . ?
C7 C1 C2 C3 -2.0(3) . . . . ?
C1 C2 C3 N1 -176.57(17) . . . . ?
C1 C2 C3 C4 -1.9(2) . . . . ?
N1 C3 C4 N2 -1.9(2) . . . . ?
C2 C3 C4 N2 -176.32(15) . . . . ?
N1 C3 C4 N3 178.45(15) . . . . ?
C2 C3 C4 N3 4.0(2) . . . . ?
C2 C1 C7 N3 3.6(2) . . . . ?
C14 C1 C7 N3 -173.86(14) . . . . ?
C2 C1 C7 O4 124.28(17) . . . . ?
C14 C1 C7 O4 -53.19(18) . . . . ?
O4 C8 C9 C10 -179.54(16) . . . . ?
C13 C8 C9 C10 3.2(2) . . . . ?
C8 C9 C10 C11 -0.2(3) . . . . ?
C9 C10 C11 C12 -2.6(3) . . . . ?
C10 C11 C12 C13 2.5(3) . . . . ?
O4 C8 C13 C12 179.59(16) . . . . ?
C9 C8 C13 C12 -3.3(2) . . . . ?
O4 C8 C13 C14 -7.7(2) . . . . ?
C9 C8 C13 C14 169.44(16) . . . . ?
C11 C12 C13 C8 0.4(3) . . . . ?
C11 C12 C13 C14 -172.27(16) . . . . ?
C2 C1 C14 O3 18.8(3) . . . . ?
C7 C1 C14 O3 -163.82(17) . . . . ?
C2 C1 C14 C13 -156.47(16) . . . . ?
C7 C1 C14 C13 20.9(2) . . . . ?
C8 C13 C14 O3 -165.56(17) . . . . ?
C12 C13 C14 O3 7.0(3) . . . . ?
C8 C13 C14 C1 9.7(2) . . . . ?
C12 C13 C14 C1 -177.78(15) . . . . ?
C9 C8 O4 C7 157.13(15) . . . . ?
C13 C8 O4 C7 -25.6(2) . . . . ?
N3 C7 O4 C8 -179.19(12) . . . . ?
C1 C7 O4 C8 55.05(17) . . . . ?
C2 C3 N1 O2 1.8(3) . . . . ?
C4 C3 N1 O2 -172.78(17) . . . . ?
C2 C3 N1 O1 -179.23(17) . . . . ?
C4 C3 N1 O1 6.2(3) . . . . ?
N3 C4 N2 C5 -14.2(3) . . . . ?
C3 C4 N2 C5 166.2(2) . . . . ?
N2 C4 N3 C7 178.08(15) . . . . ?
C3 C4 N3 C7 -2.3(2) . . . . ?
N2 C4 N3 C6 -9.7(2) . . . . ?
C3 C4 N3 C6 169.90(16) . . . . ?
O4 C7 N3 C4 -124.20(15) . . . . ?
C1 C7 N3 C4 -1.4(2) . . . . ?
O4 C7 N3 C6 62.89(17) . . . . ?
C1 C7 N3 C6 -174.29(15) . . . . ?

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

C5 H5A O2 0.96 2.46 3.376(3) 159 1_554
C5 H5C O3 0.96 2.51 3.416(3) 157 4_554
C6 H6A O3 0.96 2.55 3.429(2) 152 4_554
C9 H9 O3 0.93 2.60 3.455(2) 154 1_554

#=====================================================================
#                         END of CIF
# =====================================================================





####################################################################### 
# 
# 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_shelxl
_database_code_depnum_ccdc_archive 'CCDC 1063584'
_audit_update_record             
;
2015-05-06 deposited with the CCDC.
2017-03-31 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2012
_chemical_name_systematic        '3,3-disubstituted oxindole'
_chemical_name_common            ?
_chemical_melting_point          220
_chemical_formula_moiety         ?
_chemical_formula_sum            'C27 H22 Br N3 O4 S'
_chemical_formula_weight         564.44

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_H-M_alt        'P b c a'
_space_group_name_Hall           '-P 2ac 2ab'

_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+1/2, -y, z+1/2'
'-x, y+1/2, -z+1/2'
'x+1/2, -y+1/2, -z'
'-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                   14.158(3)
_cell_length_b                   14.747(3)
_cell_length_c                   23.048(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     4812(2)
_cell_formula_units_Z            8
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    2105
_cell_measurement_theta_min      2.24
_cell_measurement_theta_max      20.18

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.558
_exptl_crystal_F_000             2304
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    1.836
_shelx_estimated_absorpt_T_min   0.657
_shelx_estimated_absorpt_T_max   0.838
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.657
_exptl_absorpt_correction_T_max  0.838
_exptl_absorpt_process_details   'SADABS (Bruker, 2012)'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker kappa apex2 CCD Diffractometer'
_diffrn_measurement_method       'ω and φ scan'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            6282
_diffrn_reflns_av_unetI/netI     0.0896
_diffrn_reflns_av_R_equivalents  0.0561
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_theta_min         1.767
_diffrn_reflns_theta_max         20.902
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.987
_diffrn_measured_fraction_theta_full 0.579
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_Laue_measured_fraction_full 0.579
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_point_group_measured_fraction_full 0.579
_reflns_number_total             2518
_reflns_number_gt                1806
_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-2014/7 (Sheldrick, 2014)'
_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)+(0.1727P)²+25.3654P]
 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         2518
_refine_ls_number_parameters     327
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1138
_refine_ls_R_factor_gt           0.0904
_refine_ls_wR_factor_ref         0.3003
_refine_ls_wR_factor_gt          0.2816
_refine_ls_goodness_of_fit_ref   1.123
_refine_ls_restrained_S_all      1.123
_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
N1 N 1.0101(7) 0.1381(7) 0.1141(5) 0.041(3) Uani 1 1 d . . . . .
H1 H 1.0605 0.1212 0.0963 0.049 Uiso 1 1 calc R U . . .
N2 N 0.9926(7) 0.3497(7) 0.2824(5) 0.043(3) Uani 1 1 d . . . . .
H2 H 1.0055 0.4054 0.2900 0.052 Uiso 1 1 calc R U . . .
N3 N 0.7094(7) 0.0384(7) 0.2600(4) 0.044(3) Uani 1 1 d . . . . .
H3 H 0.6715 0.0265 0.2881 0.053 Uiso 1 1 calc R U . . .
O1 O 1.0229(5) 0.0463(5) 0.1950(4) 0.038(2) Uani 1 1 d . . . . .
O2 O 0.7285(6) -0.0189(5) 0.2132(4) 0.051(2) Uani 1 1 d . . . . .
O3 O 0.8340(6) -0.0189(6) 0.1412(4) 0.052(2) Uani 1 1 d . . . . .
Br1 Br 1.03014(13) -0.00014(11) 0.41139(7) 0.0729(8) Uani 1 1 d . . . . .
C1 C 0.9520(10) 0.2418(9) 0.0385(6) 0.052(4) Uani 1 1 d . . . . .
H1 H 1.0011 0.2305 0.0127 0.062 Uiso 1 1 calc R U . . .
C2 C 0.8775(11) 0.3021(9) 0.0248(6) 0.054(4) Uani 1 1 d . . . . .
H2 H 0.8775 0.3320 -0.0108 0.065 Uiso 1 1 calc R U . . .
C3 C 0.8061(10) 0.3167(8) 0.0628(6) 0.052(4) Uani 1 1 d . . . . .
H3 H 0.7561 0.3539 0.0522 0.063 Uiso 1 1 calc R U . . .
C4 C 0.8063(9) 0.2768(8) 0.1179(6) 0.041(3) Uani 1 1 d . . . . .
H4 H 0.7581 0.2889 0.1442 0.049 Uiso 1 1 calc R U . . .
C5 C 0.8782(8) 0.2201(7) 0.1322(5) 0.032(3) Uani 1 1 d . . . . .
C6 C 0.8998(7) 0.1665(6) 0.1868(5) 0.028(3) Uani 1 1 d . . . . .
C7 C 0.9843(8) 0.1050(8) 0.1672(6) 0.033(3) Uani 1 1 d . . . . .
C8 C 0.9481(9) 0.2007(8) 0.0920(5) 0.037(3) Uani 1 1 d . . . . .
C9 C 0.9388(8) 0.2275(8) 0.2345(5) 0.033(3) Uani 1 1 d . . . . .
C10 C 0.9517(8) 0.3199(7) 0.2331(6) 0.040(3) Uani 1 1 d . . . . .
H10 H 0.9346 0.3570 0.2022 0.048 Uiso 1 1 calc R U . . .
C11 C 1.0104(8) 0.2782(8) 0.3186(5) 0.035(3) Uani 1 1 d . . . . .
C12 C 1.0522(9) 0.2740(9) 0.3716(6) 0.045(3) Uani 1 1 d . . . . .
H12 H 1.0755 0.3260 0.3893 0.054 Uiso 1 1 calc R U . . .
C13 C 1.0591(9) 0.1916(10) 0.3980(6) 0.050(4) Uani 1 1 d . . . . .
H13 H 1.0879 0.1869 0.4341 0.060 Uiso 1 1 calc R U . . .
C14 C 1.0236(9) 0.1148(8) 0.3713(6) 0.041(3) Uani 1 1 d . . . . .
C15 C 0.9830(8) 0.1147(8) 0.3174(5) 0.036(3) Uani 1 1 d . . . . .
H15 H 0.9613 0.0616 0.3003 0.043 Uiso 1 1 calc R U . . .
C16 C 0.9757(8) 0.1985(8) 0.2895(5) 0.037(3) Uani 1 1 d . . . . .
C17 C 0.8198(8) 0.1083(7) 0.2088(5) 0.033(3) Uani 1 1 d . . . . .
C18 C 0.7601(8) 0.1156(7) 0.2539(5) 0.035(3) Uani 1 1 d . . . . .
C19 C 0.8008(8) 0.0202(8) 0.1817(6) 0.037(3) Uani 1 1 d . . . . .
C20 C 0.7400(8) 0.1878(8) 0.2960(5) 0.039(3) Uani 1 1 d . . . . .
C21 C 0.7101(9) 0.2753(8) 0.2780(6) 0.050(3) Uani 1 1 d . . . . .
H21 H 0.7101 0.2902 0.2388 0.060 Uiso 1 1 calc R U . . .
C22 C 0.6816(10) 0.3372(9) 0.3181(7) 0.057(4) Uani 1 1 d . . . . .
H22 H 0.6613 0.3941 0.3059 0.069 Uiso 1 1 calc R U . . .
C23 C 0.6821(10) 0.3173(10) 0.3761(6) 0.060(4) Uani 1 1 d . . . . .
H23 H 0.6603 0.3597 0.4028 0.072 Uiso 1 1 calc R U . . .
C24 C 0.7143(10) 0.2362(11) 0.3947(6) 0.059(4) Uani 1 1 d . . . . .
H24 H 0.7175 0.2247 0.4343 0.071 Uiso 1 1 calc R U . . .
C25 C 0.7425(10) 0.1697(10) 0.3561(6) 0.056(4) Uani 1 1 d . . . . .
H25 H 0.7630 0.1137 0.3697 0.067 Uiso 1 1 calc R U . . .
C26 C 0.2339(10) 0.9431(10) -0.0126(7) 0.065(4) Uani 1 1 d . . . . .
H26A H 0.2592 0.9795 -0.0434 0.098 Uiso 1 1 calc R U . . .
H26B H 0.2312 0.8809 -0.0247 0.098 Uiso 1 1 calc R U . . .
H26C H 0.2736 0.9483 0.0210 0.098 Uiso 1 1 calc R U . . .
C27 C 0.1065(12) 0.9248(11) 0.0727(7) 0.074(5) Uani 1 1 d . . . . .
H27A H 0.1571 0.9420 0.0981 0.112 Uiso 1 1 calc R U . . .
H27B H 0.1078 0.8603 0.0669 0.112 Uiso 1 1 calc R U . . .
H27C H 0.0472 0.9418 0.0898 0.112 Uiso 1 1 calc R U . . .
O4 O 0.1306(7) 1.0792(6) 0.0210(4) 0.067(3) Uani 1 1 d . . . . .
S2 S 0.1199(3) 0.9809(2) 0.00454(16) 0.0575(11) 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
N1 C7 1.366(16) . ?
N1 C8 1.373(16) . ?
N1 H1 0.8600 . ?
N2 C10 1.349(16) . ?
N2 C11 1.367(16) . ?
N2 H2 0.8600 . ?
N3 C18 1.353(15) . ?
N3 O2 1.396(13) . ?
N3 H3 0.8600 . ?
O1 C7 1.209(14) . ?
O2 C19 1.380(15) . ?
O3 C19 1.193(14) . ?
Br1 C14 1.933(12) . ?
C1 C8 1.374(17) . ?
C1 C2 1.416(19) . ?
C1 H1 0.9300 . ?
C2 C3 1.355(18) . ?
C2 H2 0.9300 . ?
C3 C4 1.398(18) . ?
C3 H3 0.9300 . ?
C4 C5 1.358(16) . ?
C4 H4 0.9300 . ?
C5 C8 1.386(16) . ?
C5 C6 1.517(15) . ?
C6 C17 1.509(16) . ?
C6 C9 1.523(15) . ?
C6 C7 1.568(16) . ?
C9 C10 1.376(16) . ?
C9 C16 1.436(17) . ?
C10 H10 0.9300 . ?
C11 C12 1.358(18) . ?
C11 C16 1.439(17) . ?
C12 C13 1.363(18) . ?
C12 H12 0.9300 . ?
C13 C14 1.383(18) . ?
C13 H13 0.9300 . ?
C14 C15 1.368(17) . ?
C15 C16 1.396(17) . ?
C15 H15 0.9300 . ?
C17 C18 1.344(16) . ?
C17 C19 1.468(17) . ?
C18 C20 1.468(16) . ?
C20 C25 1.411(17) . ?
C20 C21 1.419(17) . ?
C21 C22 1.362(18) . ?
C21 H21 0.9300 . ?
C22 C23 1.368(19) . ?
C22 H22 0.9300 . ?
C23 C24 1.35(2) . ?
C23 H23 0.9300 . ?
C24 C25 1.382(19) . ?
C24 H24 0.9300 . ?
C25 H25 0.9300 . ?
C26 S2 1.751(14) . ?
C26 H26A 0.9600 . ?
C26 H26B 0.9600 . ?
C26 H26C 0.9600 . ?
C27 S2 1.786(15) . ?
C27 H27A 0.9600 . ?
C27 H27B 0.9600 . ?
C27 H27C 0.9600 . ?
O4 S2 1.506(9) . ?

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
C7 N1 C8 113.7(10) . . ?
C7 N1 H1 123.1 . . ?
C8 N1 H1 123.1 . . ?
C10 N2 C11 110.0(9) . . ?
C10 N2 H2 125.0 . . ?
C11 N2 H2 125.0 . . ?
C18 N3 O2 109.1(9) . . ?
C18 N3 H3 125.5 . . ?
O2 N3 H3 125.5 . . ?
C19 O2 N3 107.3(8) . . ?
C8 C1 C2 116.6(13) . . ?
C8 C1 H1 121.7 . . ?
C2 C1 H1 121.7 . . ?
C3 C2 C1 120.7(12) . . ?
C3 C2 H2 119.7 . . ?
C1 C2 H2 119.7 . . ?
C2 C3 C4 121.3(12) . . ?
C2 C3 H3 119.3 . . ?
C4 C3 H3 119.3 . . ?
C5 C4 C3 118.8(12) . . ?
C5 C4 H4 120.6 . . ?
C3 C4 H4 120.6 . . ?
C4 C5 C8 119.9(11) . . ?
C4 C5 C6 132.4(11) . . ?
C8 C5 C6 107.7(9) . . ?
C17 C6 C5 115.1(9) . . ?
C17 C6 C9 111.4(9) . . ?
C5 C6 C9 111.4(8) . . ?
C17 C6 C7 109.9(8) . . ?
C5 C6 C7 102.4(9) . . ?
C9 C6 C7 105.9(8) . . ?
O1 C7 N1 127.6(11) . . ?
O1 C7 C6 127.3(11) . . ?
N1 C7 C6 104.8(10) . . ?
N1 C8 C1 127.2(12) . . ?
N1 C8 C5 110.2(10) . . ?
C1 C8 C5 122.6(12) . . ?
C10 C9 C16 105.5(10) . . ?
C10 C9 C6 128.0(10) . . ?
C16 C9 C6 126.4(10) . . ?
N2 C10 C9 111.0(11) . . ?
N2 C10 H10 124.5 . . ?
C9 C10 H10 124.5 . . ?
C12 C11 N2 131.5(11) . . ?
C12 C11 C16 122.0(11) . . ?
N2 C11 C16 106.4(10) . . ?
C11 C12 C13 118.2(11) . . ?
C11 C12 H12 120.9 . . ?
C13 C12 H12 120.9 . . ?
C12 C13 C14 120.4(12) . . ?
C12 C13 H13 119.8 . . ?
C14 C13 H13 119.8 . . ?
C15 C14 C13 123.8(11) . . ?
C15 C14 Br1 117.0(9) . . ?
C13 C14 Br1 119.2(10) . . ?
C14 C15 C16 116.6(11) . . ?
C14 C15 H15 121.7 . . ?
C16 C15 H15 121.7 . . ?
C15 C16 C9 134.1(11) . . ?
C15 C16 C11 118.9(11) . . ?
C9 C16 C11 107.0(10) . . ?
C18 C17 C19 106.5(10) . . ?
C18 C17 C6 133.4(10) . . ?
C19 C17 C6 119.9(10) . . ?
C17 C18 N3 110.2(10) . . ?
C17 C18 C20 133.7(11) . . ?
N3 C18 C20 116.1(10) . . ?
O3 C19 O2 120.2(11) . . ?
O3 C19 C17 133.5(11) . . ?
O2 C19 C17 106.4(11) . . ?
C25 C20 C21 117.8(12) . . ?
C25 C20 C18 120.5(11) . . ?
C21 C20 C18 121.5(11) . . ?
C22 C21 C20 120.0(12) . . ?
C22 C21 H21 120.0 . . ?
C20 C21 H21 120.0 . . ?
C21 C22 C23 121.2(13) . . ?
C21 C22 H22 119.4 . . ?
C23 C22 H22 119.4 . . ?
C24 C23 C22 120.1(14) . . ?
C24 C23 H23 119.9 . . ?
C22 C23 H23 119.9 . . ?
C23 C24 C25 121.5(14) . . ?
C23 C24 H24 119.2 . . ?
C25 C24 H24 119.2 . . ?
C24 C25 C20 119.3(14) . . ?
C24 C25 H25 120.3 . . ?
C20 C25 H25 120.3 . . ?
S2 C26 H26A 109.5 . . ?
S2 C26 H26B 109.5 . . ?
H26A C26 H26B 109.5 . . ?
S2 C26 H26C 109.5 . . ?
H26A C26 H26C 109.5 . . ?
H26B C26 H26C 109.5 . . ?
S2 C27 H27A 109.5 . . ?
S2 C27 H27B 109.5 . . ?
H27A C27 H27B 109.5 . . ?
S2 C27 H27C 109.5 . . ?
H27A C27 H27C 109.5 . . ?
H27B C27 H27C 109.5 . . ?
O4 S2 C26 105.7(6) . . ?
O4 S2 C27 103.6(7) . . ?
C26 S2 C27 98.6(8) . . ?

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
C18 N3 O2 C19 7.1(12) . . . . ?
C8 C1 C2 C3 -0.7(19) . . . . ?
C1 C2 C3 C4 4(2) . . . . ?
C2 C3 C4 C5 -2.2(19) . . . . ?
C3 C4 C5 C8 -1.8(17) . . . . ?
C3 C4 C5 C6 -179.9(11) . . . . ?
C4 C5 C6 C17 51.6(16) . . . . ?
C8 C5 C6 C17 -126.6(10) . . . . ?
C4 C5 C6 C9 -76.4(15) . . . . ?
C8 C5 C6 C9 105.4(10) . . . . ?
C4 C5 C6 C7 170.8(12) . . . . ?
C8 C5 C6 C7 -7.4(11) . . . . ?
C8 N1 C7 O1 175.9(11) . . . . ?
C8 N1 C7 C6 -9.7(12) . . . . ?
C17 C6 C7 O1 -52.8(14) . . . . ?
C5 C6 C7 O1 -175.5(10) . . . . ?
C9 C6 C7 O1 67.6(13) . . . . ?
C17 C6 C7 N1 132.8(9) . . . . ?
C5 C6 C7 N1 10.0(10) . . . . ?
C9 C6 C7 N1 -106.8(9) . . . . ?
C7 N1 C8 C1 -176.0(12) . . . . ?
C7 N1 C8 C5 5.1(13) . . . . ?
C2 C1 C8 N1 177.8(12) . . . . ?
C2 C1 C8 C5 -3.4(18) . . . . ?
C4 C5 C8 N1 -176.3(10) . . . . ?
C6 C5 C8 N1 2.2(13) . . . . ?
C4 C5 C8 C1 4.8(18) . . . . ?
C6 C5 C8 C1 -176.7(11) . . . . ?
C17 C6 C9 C10 -127.5(12) . . . . ?
C5 C6 C9 C10 2.4(16) . . . . ?
C7 C6 C9 C10 113.0(13) . . . . ?
C17 C6 C9 C16 56.9(14) . . . . ?
C5 C6 C9 C16 -173.2(10) . . . . ?
C7 C6 C9 C16 -62.5(13) . . . . ?
C11 N2 C10 C9 1.1(14) . . . . ?
C16 C9 C10 N2 -0.4(13) . . . . ?
C6 C9 C10 N2 -176.7(10) . . . . ?
C10 N2 C11 C12 178.1(12) . . . . ?
C10 N2 C11 C16 -1.4(12) . . . . ?
N2 C11 C12 C13 179.2(12) . . . . ?
C16 C11 C12 C13 -1.4(18) . . . . ?
C11 C12 C13 C14 -0.5(19) . . . . ?
C12 C13 C14 C15 2(2) . . . . ?
C12 C13 C14 Br1 -177.5(10) . . . . ?
C13 C14 C15 C16 -1.8(18) . . . . ?
Br1 C14 C15 C16 178.0(8) . . . . ?
C14 C15 C16 C9 -179.9(12) . . . . ?
C14 C15 C16 C11 -0.1(16) . . . . ?
C10 C9 C16 C15 179.3(12) . . . . ?
C6 C9 C16 C15 -4(2) . . . . ?
C10 C9 C16 C11 -0.5(13) . . . . ?
C6 C9 C16 C11 175.9(10) . . . . ?
C12 C11 C16 C15 1.8(17) . . . . ?
N2 C11 C16 C15 -178.7(10) . . . . ?
C12 C11 C16 C9 -178.4(11) . . . . ?
N2 C11 C16 C9 1.1(12) . . . . ?
C5 C6 C17 C18 -106.0(14) . . . . ?
C9 C6 C17 C18 22.0(16) . . . . ?
C7 C6 C17 C18 139.0(12) . . . . ?
C5 C6 C17 C19 79.7(12) . . . . ?
C9 C6 C17 C19 -152.3(10) . . . . ?
C7 C6 C17 C19 -35.3(13) . . . . ?
C19 C17 C18 N3 3.8(13) . . . . ?
C6 C17 C18 N3 -171.1(11) . . . . ?
C19 C17 C18 C20 -176.3(12) . . . . ?
C6 C17 C18 C20 9(2) . . . . ?
O2 N3 C18 C17 -6.9(13) . . . . ?
O2 N3 C18 C20 173.2(9) . . . . ?
N3 O2 C19 O3 175.4(10) . . . . ?
N3 O2 C19 C17 -4.7(12) . . . . ?
C18 C17 C19 O3 -179.4(14) . . . . ?
C6 C17 C19 O3 -4(2) . . . . ?
C18 C17 C19 O2 0.7(12) . . . . ?
C6 C17 C19 O2 176.3(9) . . . . ?
C17 C18 C20 C25 -127.2(14) . . . . ?
N3 C18 C20 C25 52.6(16) . . . . ?
C17 C18 C20 C21 57.9(18) . . . . ?
N3 C18 C20 C21 -122.2(12) . . . . ?
C25 C20 C21 C22 -2.6(19) . . . . ?
C18 C20 C21 C22 172.3(12) . . . . ?
C20 C21 C22 C23 1(2) . . . . ?
C21 C22 C23 C24 2(2) . . . . ?
C22 C23 C24 C25 -4(2) . . . . ?
C23 C24 C25 C20 2(2) . . . . ?
C21 C20 C25 C24 1.4(19) . . . . ?
C18 C20 C25 C24 -173.6(11) . . . . ?

_refine_diff_density_max         0.969
_refine_diff_density_min         -0.987
_refine_diff_density_rms         0.147

_shelxl_version_number           2012-9


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Ethanol, DMSO'
