# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2015

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

data_1
_database_code_depnum_ccdc_archive 'CCDC 957578'
_audit_update_record             
;
2013-08-27 deposited with the CCDC.
2015-08-07 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C21 H12 N4, C2 H6 O S'
_chemical_formula_sum            'C23 H18 N4 O S'
_chemical_formula_weight         398.48

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

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   P21/c
_symmetry_space_group_name_Hall  -P2ybc

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

_cell_length_a                   7.387(6)
_cell_length_b                   32.39(3)
_cell_length_c                   8.251(7)
_cell_angle_alpha                90.00
_cell_angle_beta                 92.434(10)
_cell_angle_gamma                90.00
_cell_volume                     1972(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    3082
_cell_measurement_theta_min      6.09
_cell_measurement_theta_max      31.59

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.224
_exptl_crystal_size_mid          0.190
_exptl_crystal_size_min          0.154
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             832
_exptl_absorpt_coefficient_mu    0.186
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.959
_exptl_absorpt_correction_T_max  0.972
_exptl_absorpt_process_details   '(SADABS; Bruker, 2000)'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(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  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         0
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8156
_diffrn_reflns_av_R_equivalents  0.0540
_diffrn_reflns_av_sigmaI/netI    0.0664
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         6.09
_diffrn_reflns_theta_max         25.00
_reflns_number_total             3473
_reflns_number_gt                2374
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_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)+(0.1321P)²+0.9376P] 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         3319
_refine_ls_number_parameters     264
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0951
_refine_ls_R_factor_gt           0.0745
_refine_ls_wR_factor_ref         0.2380
_refine_ls_wR_factor_gt          0.2232
_refine_ls_goodness_of_fit_ref   1.099
_refine_ls_restrained_S_all      1.099
_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
N1 N 0.2494(4) -0.13668(10) 1.1055(4) 0.0568(9) Uani 1 1 d . . .
H1A H 0.3055 -0.1153 1.0716 0.068 Uiso 1 1 calc R . .
H1B H 0.3079 -0.1554 1.1599 0.068 Uiso 1 1 calc R . .
N2 N -0.0747(5) -0.20648(11) 1.1795(5) 0.0653(10) Uani 1 1 d . . .
N3 N -0.3678(5) -0.12275(12) 0.9185(5) 0.0670(11) Uani 1 1 d . . .
N4 N 0.0553(4) -0.07721(8) 0.9392(3) 0.0390(7) Uani 1 1 d . . .
C1 C -0.0122(5) -0.17702(12) 1.1335(5) 0.0446(9) Uani 1 1 d . . .
C2 C 0.0719(5) -0.14077(11) 1.0739(4) 0.0402(8) Uani 1 1 d . . .
C3 C -0.0297(4) -0.11237(10) 0.9886(4) 0.0376(8) Uani 1 1 d . . .
C4 C -0.2183(5) -0.11970(11) 0.9525(4) 0.0433(9) Uani 1 1 d . . .
C5 C -0.0303(4) -0.05017(10) 0.8528(4) 0.0369(8) Uani 1 1 d . . .
H5 H -0.1512 -0.0548 0.8221 0.044 Uiso 1 1 calc R . .
C6 C 0.0554(4) -0.01290(10) 0.8022(4) 0.0343(8) Uani 1 1 d . . .
C7 C 0.2335(5) -0.00475(12) 0.8545(4) 0.0428(9) Uani 1 1 d . . .
H7 H 0.2948 -0.0238 0.9208 0.051 Uiso 1 1 calc R . .
C8 C 0.3204(5) 0.03033(11) 0.8112(5) 0.0435(9) Uani 1 1 d . . .
H8 H 0.4389 0.0349 0.8495 0.052 Uiso 1 1 calc R . .
C9 C 0.2345(4) 0.05945(11) 0.7105(4) 0.0396(8) Uani 1 1 d . . .
C10 C 0.3210(5) 0.09615(12) 0.6619(5) 0.0502(10) Uani 1 1 d . . .
H10 H 0.4397 0.1012 0.6987 0.060 Uiso 1 1 calc R . .
C11 C 0.2366(6) 0.12398(12) 0.5639(5) 0.0538(10) Uani 1 1 d . . .
H11 H 0.2980 0.1476 0.5335 0.065 Uiso 1 1 calc R . .
C12 C 0.0556(5) 0.11767(11) 0.5068(5) 0.0449(9) Uani 1 1 d . . .
C13 C -0.0371(6) 0.14645(12) 0.4057(5) 0.0572(11) Uani 1 1 d . . .
H13 H 0.0211 0.1705 0.3753 0.069 Uiso 1 1 calc R . .
C14 C -0.2116(6) 0.13925(13) 0.3522(5) 0.0586(11) Uani 1 1 d . . .
H14 H -0.2709 0.1585 0.2851 0.070 Uiso 1 1 calc R . .
C15 C -0.3003(5) 0.10426(12) 0.3957(5) 0.0504(10) Uani 1 1 d . . .
H15 H -0.4187 0.0998 0.3568 0.060 Uiso 1 1 calc R . .
C16 C -0.2164(5) 0.07529(10) 0.4971(4) 0.0381(8) Uani 1 1 d . . .
C17 C -0.3034(4) 0.03904(11) 0.5455(4) 0.0418(9) Uani 1 1 d . . .
H17 H -0.4223 0.0343 0.5087 0.050 Uiso 1 1 calc R . .
C18 C -0.2208(4) 0.01080(10) 0.6432(4) 0.0393(8) Uani 1 1 d . . .
H18 H -0.2842 -0.0126 0.6728 0.047 Uiso 1 1 calc R . .
C19 C -0.0378(4) 0.01618(10) 0.7021(4) 0.0328(7) Uani 1 1 d . . .
C20 C 0.0533(4) 0.05216(10) 0.6563(4) 0.0343(8) Uani 1 1 d . . .
C21 C -0.0360(4) 0.08183(10) 0.5533(4) 0.0361(8) Uani 1 1 d . . .
C22 C 0.7451(7) 0.25117(17) 0.5767(8) 0.0844(17) Uani 1 1 d . . .
H22A H 0.7647 0.2686 0.6698 0.127 Uiso 1 1 calc R . .
H22B H 0.7366 0.2678 0.4804 0.127 Uiso 1 1 calc R . .
H22C H 0.8445 0.2322 0.5698 0.127 Uiso 1 1 calc R . .
C23 C 0.4002(7) 0.26624(16) 0.6205(7) 0.0784(15) Uani 1 1 d . . .
H23A H 0.2803 0.2566 0.6401 0.118 Uiso 1 1 calc R . .
H23B H 0.3972 0.2829 0.5243 0.118 Uiso 1 1 calc R . .
H23C H 0.4445 0.2824 0.7113 0.118 Uiso 1 1 calc R . .
O1 O 0.5605(4) 0.20199(8) 0.7544(4) 0.0670(9) Uani 1 1 d . . .
S1 S 0.54477(16) 0.22366(3) 0.59476(13) 0.0589(4) 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 C2 1.333(5) . ?
N1 H1A 0.8600 . ?
N1 H1B 0.8600 . ?
N2 C1 1.133(5) . ?
N3 C4 1.132(5) . ?
N4 C5 1.279(4) . ?
N4 C3 1.371(4) . ?
C1 C2 1.425(5) . ?
C2 C3 1.364(5) . ?
C3 C4 1.432(5) . ?
C5 C6 1.433(5) . ?
C5 H5 0.9300 . ?
C6 C7 1.392(5) . ?
C6 C19 1.413(5) . ?
C7 C8 1.360(5) . ?
C7 H7 0.9300 . ?
C8 C9 1.392(5) . ?
C8 H8 0.9300 . ?
C9 C20 1.413(5) . ?
C9 C10 1.416(5) . ?
C10 C11 1.346(6) . ?
C10 H10 0.9300 . ?
C11 C12 1.413(6) . ?
C11 H11 0.9300 . ?
C12 C21 1.405(5) . ?
C12 C13 1.409(6) . ?
C13 C14 1.365(6) . ?
C13 H13 0.9300 . ?
C14 C15 1.365(6) . ?
C14 H14 0.9300 . ?
C15 C16 1.386(5) . ?
C15 H15 0.9300 . ?
C16 C17 1.404(5) . ?
C16 C21 1.408(5) . ?
C17 C18 1.348(5) . ?
C17 H17 0.9300 . ?
C18 C19 1.427(5) . ?
C18 H18 0.9300 . ?
C19 C20 1.405(5) . ?
C20 C21 1.426(5) . ?
C22 S1 1.739(6) . ?
C22 H22A 0.9600 . ?
C22 H22B 0.9600 . ?
C22 H22C 0.9600 . ?
C23 S1 1.762(5) . ?
C23 H23A 0.9600 . ?
C23 H23B 0.9600 . ?
C23 H23C 0.9600 . ?
O1 S1 1.493(3) . ?

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 N1 H1A 120.0 . . ?
C2 N1 H1B 120.0 . . ?
H1A N1 H1B 120.0 . . ?
C5 N4 C3 120.9(3) . . ?
N2 C1 C2 178.0(4) . . ?
N1 C2 C3 123.3(3) . . ?
N1 C2 C1 117.0(3) . . ?
C3 C2 C1 119.7(3) . . ?
C2 C3 N4 117.7(3) . . ?
C2 C3 C4 120.3(3) . . ?
N4 C3 C4 122.0(3) . . ?
N3 C4 C3 175.0(4) . . ?
N4 C5 C6 121.7(3) . . ?
N4 C5 H5 119.2 . . ?
C6 C5 H5 119.2 . . ?
C7 C6 C19 119.1(3) . . ?
C7 C6 C5 119.5(3) . . ?
C19 C6 C5 121.4(3) . . ?
C8 C7 C6 121.8(3) . . ?
C8 C7 H7 119.1 . . ?
C6 C7 H7 119.1 . . ?
C7 C8 C9 121.0(3) . . ?
C7 C8 H8 119.5 . . ?
C9 C8 H8 119.5 . . ?
C8 C9 C20 118.5(3) . . ?
C8 C9 C10 122.6(3) . . ?
C20 C9 C10 118.9(3) . . ?
C11 C10 C9 122.0(4) . . ?
C11 C10 H10 119.0 . . ?
C9 C10 H10 119.0 . . ?
C10 C11 C12 120.7(4) . . ?
C10 C11 H11 119.6 . . ?
C12 C11 H11 119.6 . . ?
C21 C12 C13 118.7(4) . . ?
C21 C12 C11 119.2(3) . . ?
C13 C12 C11 122.1(4) . . ?
C14 C13 C12 120.5(4) . . ?
C14 C13 H13 119.8 . . ?
C12 C13 H13 119.8 . . ?
C13 C14 C15 120.9(4) . . ?
C13 C14 H14 119.5 . . ?
C15 C14 H14 119.5 . . ?
C14 C15 C16 120.9(4) . . ?
C14 C15 H15 119.5 . . ?
C16 C15 H15 119.5 . . ?
C15 C16 C17 122.6(3) . . ?
C15 C16 C21 119.3(3) . . ?
C17 C16 C21 118.1(3) . . ?
C18 C17 C16 122.4(3) . . ?
C18 C17 H17 118.8 . . ?
C16 C17 H17 118.8 . . ?
C17 C18 C19 121.2(3) . . ?
C17 C18 H18 119.4 . . ?
C19 C18 H18 119.4 . . ?
C20 C19 C6 118.9(3) . . ?
C20 C19 C18 117.8(3) . . ?
C6 C19 C18 123.3(3) . . ?
C19 C20 C9 120.8(3) . . ?
C19 C20 C21 120.3(3) . . ?
C9 C20 C21 118.9(3) . . ?
C12 C21 C16 119.6(3) . . ?
C12 C21 C20 120.3(3) . . ?
C16 C21 C20 120.1(3) . . ?
S1 C22 H22A 109.5 . . ?
S1 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
S1 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
S1 C23 H23A 109.5 . . ?
S1 C23 H23B 109.5 . . ?
H23A C23 H23B 109.5 . . ?
S1 C23 H23C 109.5 . . ?
H23A C23 H23C 109.5 . . ?
H23B C23 H23C 109.5 . . ?
O1 S1 C22 106.4(2) . . ?
O1 S1 C23 106.6(2) . . ?
C22 S1 C23 97.6(3) . . ?

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
N2 C1 C2 N1 -41(12) . . . . ?
N2 C1 C2 C3 139(12) . . . . ?
N1 C2 C3 N4 -2.7(5) . . . . ?
C1 C2 C3 N4 177.5(3) . . . . ?
N1 C2 C3 C4 177.0(4) . . . . ?
C1 C2 C3 C4 -2.8(5) . . . . ?
C5 N4 C3 C2 177.0(3) . . . . ?
C5 N4 C3 C4 -2.7(5) . . . . ?
C2 C3 C4 N3 179(100) . . . . ?
N4 C3 C4 N3 -1(5) . . . . ?
C3 N4 C5 C6 179.0(3) . . . . ?
N4 C5 C6 C7 -3.3(5) . . . . ?
N4 C5 C6 C19 177.7(3) . . . . ?
C19 C6 C7 C8 -0.3(5) . . . . ?
C5 C6 C7 C8 -179.4(3) . . . . ?
C6 C7 C8 C9 -0.8(6) . . . . ?
C7 C8 C9 C20 1.2(5) . . . . ?
C7 C8 C9 C10 -179.5(3) . . . . ?
C8 C9 C10 C11 179.8(4) . . . . ?
C20 C9 C10 C11 -0.9(6) . . . . ?
C9 C10 C11 C12 0.7(6) . . . . ?
C10 C11 C12 C21 0.0(6) . . . . ?
C10 C11 C12 C13 179.2(4) . . . . ?
C21 C12 C13 C14 -1.0(6) . . . . ?
C11 C12 C13 C14 179.7(4) . . . . ?
C12 C13 C14 C15 0.3(6) . . . . ?
C13 C14 C15 C16 0.8(6) . . . . ?
C14 C15 C16 C17 179.6(4) . . . . ?
C14 C15 C16 C21 -1.2(6) . . . . ?
C15 C16 C17 C18 179.5(4) . . . . ?
C21 C16 C17 C18 0.3(5) . . . . ?
C16 C17 C18 C19 -0.6(6) . . . . ?
C7 C6 C19 C20 1.0(5) . . . . ?
C5 C6 C19 C20 -180.0(3) . . . . ?
C7 C6 C19 C18 -179.5(3) . . . . ?
C5 C6 C19 C18 -0.5(5) . . . . ?
C17 C18 C19 C20 0.7(5) . . . . ?
C17 C18 C19 C6 -178.8(3) . . . . ?
C6 C19 C20 C9 -0.6(5) . . . . ?
C18 C19 C20 C9 179.9(3) . . . . ?
C6 C19 C20 C21 179.0(3) . . . . ?
C18 C19 C20 C21 -0.5(5) . . . . ?
C8 C9 C20 C19 -0.5(5) . . . . ?
C10 C9 C20 C19 -179.8(3) . . . . ?
C8 C9 C20 C21 179.9(3) . . . . ?
C10 C9 C20 C21 0.5(5) . . . . ?
C13 C12 C21 C16 0.6(5) . . . . ?
C11 C12 C21 C16 179.9(3) . . . . ?
C13 C12 C21 C20 -179.6(3) . . . . ?
C11 C12 C21 C20 -0.3(5) . . . . ?
C15 C16 C21 C12 0.4(5) . . . . ?
C17 C16 C21 C12 179.7(3) . . . . ?
C15 C16 C21 C20 -179.3(3) . . . . ?
C17 C16 C21 C20 -0.1(5) . . . . ?
C19 C20 C21 C12 -179.6(3) . . . . ?
C9 C20 C21 C12 0.1(5) . . . . ?
C19 C20 C21 C16 0.2(5) . . . . ?
C9 C20 C21 C16 179.8(3) . . . . ?

_diffrn_measured_fraction_theta_max 0.956
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.956
_refine_diff_density_max         0.354
_refine_diff_density_min         -0.606
_refine_diff_density_rms         0.071
