# 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_mvs663dmf
_database_code_depnum_ccdc_archive 'CCDC 2093521'
loop_
_audit_author_name
_audit_author_address
'Valentina Karnoukhova'
;A N Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences
Russia
;
_audit_update_record             
;
2021-06-30 deposited with the CCDC.	2021-09-23 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C15 H14 N4 S'
_chemical_formula_sum            'C15 H14 N4 S'
_chemical_formula_weight         282.36

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

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

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

_cell_length_a                   8.3093(4)
_cell_length_b                   7.7536(3)
_cell_length_c                   21.1019(9)
_cell_angle_alpha                90
_cell_angle_beta                 94.235(2)
_cell_angle_gamma                90
_cell_volume                     1355.82(10)
_cell_formula_units_Z            4
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    246
_cell_measurement_theta_min      3
_cell_measurement_theta_max      25

_exptl_crystal_description       prism
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.383
_exptl_crystal_F_000             592
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.210
_exptl_crystal_size_min          0.170
_exptl_absorpt_coefficient_mu    0.234
_shelx_estimated_absorpt_T_min   0.933
_shelx_estimated_absorpt_T_max   0.961
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.7028
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      120(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker SMART APEX II diffractometer'
_diffrn_detector_type            'Bruker PHOTON II CPAD detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            17592
_diffrn_reflns_av_unetI/netI     0.0250
_diffrn_reflns_av_R_equivalents  0.0257
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_theta_min         1.935
_diffrn_reflns_theta_max         30.523
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             4117
_reflns_number_gt                3525
_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 APEX3'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT (Sheldrick, 2015a)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2015b)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008)'
_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)+(0.0565P)²+0.4125P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4117
_refine_ls_number_parameters     188
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0402
_refine_ls_R_factor_gt           0.0341
_refine_ls_wR_factor_ref         0.1001
_refine_ls_wR_factor_gt          0.0976
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_restrained_S_all      1.030
_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
S1 S 0.30464(3) 0.57028(4) 0.31952(2) 0.01901(9) Uani 1 1 d . . . . .
N1 N 0.57228(11) 0.57778(12) 0.39250(4) 0.01641(18) Uani 1 1 d . . . . .
N2 N 0.03711(13) 0.74469(18) 0.42895(6) 0.0340(3) Uani 1 1 d . . . . .
N3 N 0.40245(10) 0.83634(12) 0.55092(4) 0.01542(18) Uani 1 1 d . . . . .
N4 N 0.60230(11) 0.72411(12) 0.50518(4) 0.01595(18) Uani 1 1 d . . . . .
H4N H 0.6456(19) 0.668(2) 0.4769(8) 0.030(4) Uiso 1 1 d . . . . .
C1 C 0.41799(13) 0.61920(14) 0.39168(5) 0.0160(2) Uani 1 1 d . . . . .
C2 C 0.47857(14) 0.48759(14) 0.28963(5) 0.0177(2) Uani 1 1 d . . . . .
C3 C 0.49860(15) 0.41541(14) 0.23011(5) 0.0212(2) Uani 1 1 d . . . . .
H3A H 0.410593 0.407726 0.198838 0.025 Uiso 1 1 calc R U . . .
C4 C 0.65050(16) 0.35519(15) 0.21785(6) 0.0233(2) Uani 1 1 d . . . . .
H4A H 0.666642 0.305044 0.177732 0.028 Uiso 1 1 calc R U . . .
C5 C 0.78008(15) 0.36745(15) 0.26384(6) 0.0229(2) Uani 1 1 d . . . . .
H5A H 0.882810 0.324278 0.254677 0.027 Uiso 1 1 calc R U . . .
C6 C 0.76099(14) 0.44165(14) 0.32265(5) 0.0197(2) Uani 1 1 d . . . . .
H6A H 0.849981 0.450991 0.353413 0.024 Uiso 1 1 calc R U . . .
C7 C 0.60868(13) 0.50244(14) 0.33589(5) 0.0168(2) Uani 1 1 d . . . . .
C8 C 0.34418(12) 0.70086(14) 0.44262(5) 0.0165(2) Uani 1 1 d . . . . .
C9 C 0.17504(14) 0.72716(16) 0.43627(5) 0.0213(2) Uani 1 1 d . . . . .
C10 C 0.44204(12) 0.75267(14) 0.49794(5) 0.0151(2) Uani 1 1 d . . . . .
C11 C 0.54145(12) 0.85720(14) 0.59228(5) 0.0159(2) Uani 1 1 d . . . . .
C12 C 0.66527(13) 0.78766(14) 0.56320(5) 0.0166(2) Uani 1 1 d . . . . .
C13 C 0.24278(14) 0.89662(18) 0.56493(6) 0.0244(2) Uani 1 1 d . . . . .
H13A H 0.165792 0.800929 0.560139 0.037 Uiso 1 1 calc R U . . .
H13B H 0.208445 0.989451 0.535444 0.037 Uiso 1 1 calc R U . . .
H13C H 0.246731 0.940017 0.608638 0.037 Uiso 1 1 calc R U . . .
C14 C 0.53632(14) 0.94212(15) 0.65524(5) 0.0206(2) Uani 1 1 d . . . . .
H14A H 0.643785 0.938222 0.677699 0.031 Uiso 1 1 calc R U . . .
H14B H 0.459176 0.881626 0.680296 0.031 Uiso 1 1 calc R U . . .
H14C H 0.502604 1.062494 0.649248 0.031 Uiso 1 1 calc R U . . .
C15 C 0.84126(13) 0.77492(16) 0.58242(6) 0.0226(2) Uani 1 1 d . . . . .
H15A H 0.859598 0.797912 0.628053 0.034 Uiso 1 1 calc R U . . .
H15B H 0.900206 0.859773 0.558661 0.034 Uiso 1 1 calc R U . . .
H15C H 0.879605 0.658724 0.573189 0.034 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
S1 C2 1.7413(12) . ?
S1 C1 1.7714(11) . ?
N1 C1 1.3205(14) . ?
N1 C7 1.3831(14) . ?
N2 C9 1.1532(15) . ?
N3 C10 1.3539(13) . ?
N3 C11 1.4047(13) . ?
N3 C13 1.4574(14) . ?
N4 C10 1.3474(13) . ?
N4 C12 1.3858(14) . ?
N4 H4N 0.839(17) . ?
C1 C8 1.4249(15) . ?
C2 C3 1.3961(15) . ?
C2 C7 1.4069(15) . ?
C3 C4 1.3880(17) . ?
C3 H3A 0.9500 . ?
C4 C5 1.3986(18) . ?
C4 H4A 0.9500 . ?
C5 C6 1.3875(16) . ?
C5 H5A 0.9500 . ?
C6 C7 1.3979(16) . ?
C6 H6A 0.9500 . ?
C8 C9 1.4167(15) . ?
C8 C10 1.4301(14) . ?
C11 C12 1.3487(15) . ?
C11 C14 1.4863(15) . ?
C12 C15 1.4918(15) . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?
C14 H14A 0.9800 . ?
C14 H14B 0.9800 . ?
C14 H14C 0.9800 . ?
C15 H15A 0.9800 . ?
C15 H15B 0.9800 . ?
C15 H15C 0.9800 . ?

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 S1 C1 89.28(5) . . ?
C1 N1 C7 111.43(9) . . ?
C10 N3 C11 109.23(8) . . ?
C10 N3 C13 126.98(9) . . ?
C11 N3 C13 123.78(9) . . ?
C10 N4 C12 110.32(9) . . ?
C10 N4 H4N 118.4(11) . . ?
C12 N4 H4N 131.1(11) . . ?
N1 C1 C8 124.73(10) . . ?
N1 C1 S1 114.41(8) . . ?
C8 C1 S1 120.84(8) . . ?
C3 C2 C7 121.36(11) . . ?
C3 C2 S1 129.10(9) . . ?
C7 C2 S1 109.53(8) . . ?
C4 C3 C2 118.23(11) . . ?
C4 C3 H3A 120.9 . . ?
C2 C3 H3A 120.9 . . ?
C3 C4 C5 120.79(11) . . ?
C3 C4 H4A 119.6 . . ?
C5 C4 H4A 119.6 . . ?
C6 C5 C4 121.06(11) . . ?
C6 C5 H5A 119.5 . . ?
C4 C5 H5A 119.5 . . ?
C5 C6 C7 118.92(11) . . ?
C5 C6 H6A 120.5 . . ?
C7 C6 H6A 120.5 . . ?
N1 C7 C6 125.03(10) . . ?
N1 C7 C2 115.34(10) . . ?
C6 C7 C2 119.63(10) . . ?
C9 C8 C1 118.15(10) . . ?
C9 C8 C10 122.49(10) . . ?
C1 C8 C10 119.35(9) . . ?
N2 C9 C8 177.30(13) . . ?
N4 C10 N3 106.47(9) . . ?
N4 C10 C8 122.96(10) . . ?
N3 C10 C8 130.57(9) . . ?
C12 C11 N3 106.92(9) . . ?
C12 C11 C14 131.08(10) . . ?
N3 C11 C14 122.00(9) . . ?
C11 C12 N4 107.05(9) . . ?
C11 C12 C15 131.92(10) . . ?
N4 C12 C15 121.02(10) . . ?
N3 C13 H13A 109.5 . . ?
N3 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
N3 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
C11 C14 H14A 109.5 . . ?
C11 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C11 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C12 C15 H15A 109.5 . . ?
C12 C15 H15B 109.5 . . ?
H15A C15 H15B 109.5 . . ?
C12 C15 H15C 109.5 . . ?
H15A C15 H15C 109.5 . . ?
H15B C15 H15C 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
C7 N1 C1 C8 -179.11(10) . . . . ?
C7 N1 C1 S1 -0.81(12) . . . . ?
C2 S1 C1 N1 0.42(9) . . . . ?
C2 S1 C1 C8 178.80(9) . . . . ?
C1 S1 C2 C3 -179.91(11) . . . . ?
C1 S1 C2 C7 0.08(8) . . . . ?
C7 C2 C3 C4 1.15(17) . . . . ?
S1 C2 C3 C4 -178.86(9) . . . . ?
C2 C3 C4 C5 -0.33(17) . . . . ?
C3 C4 C5 C6 -0.70(18) . . . . ?
C4 C5 C6 C7 0.91(17) . . . . ?
C1 N1 C7 C6 -178.71(10) . . . . ?
C1 N1 C7 C2 0.89(13) . . . . ?
C5 C6 C7 N1 179.49(10) . . . . ?
C5 C6 C7 C2 -0.10(16) . . . . ?
C3 C2 C7 N1 179.43(10) . . . . ?
S1 C2 C7 N1 -0.56(12) . . . . ?
C3 C2 C7 C6 -0.95(16) . . . . ?
S1 C2 C7 C6 179.06(8) . . . . ?
N1 C1 C8 C9 -176.00(11) . . . . ?
S1 C1 C8 C9 5.79(14) . . . . ?
N1 C1 C8 C10 3.85(17) . . . . ?
S1 C1 C8 C10 -174.35(8) . . . . ?
C12 N4 C10 N3 0.72(12) . . . . ?
C12 N4 C10 C8 -179.91(10) . . . . ?
C11 N3 C10 N4 -1.02(12) . . . . ?
C13 N3 C10 N4 179.29(10) . . . . ?
C11 N3 C10 C8 179.69(11) . . . . ?
C13 N3 C10 C8 0.00(19) . . . . ?
C9 C8 C10 N4 178.16(11) . . . . ?
C1 C8 C10 N4 -1.68(16) . . . . ?
C9 C8 C10 N3 -2.64(18) . . . . ?
C1 C8 C10 N3 177.51(11) . . . . ?
C10 N3 C11 C12 0.94(12) . . . . ?
C13 N3 C11 C12 -179.35(10) . . . . ?
C10 N3 C11 C14 -178.90(10) . . . . ?
C13 N3 C11 C14 0.80(16) . . . . ?
N3 C11 C12 N4 -0.48(12) . . . . ?
C14 C11 C12 N4 179.35(11) . . . . ?
N3 C11 C12 C15 178.17(11) . . . . ?
C14 C11 C12 C15 -2.0(2) . . . . ?
C10 N4 C12 C11 -0.14(12) . . . . ?
C10 N4 C12 C15 -178.97(10) . . . . ?

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
N4 H4N N1 0.839(17) 1.969(17) 2.6298(13) 135.0(15) .

_refine_diff_density_max         0.381
_refine_diff_density_min         -0.369
_refine_diff_density_rms         0.053

####################################################################### 
# 
# 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_mvs693
_database_code_depnum_ccdc_archive 'CCDC 2093522'
loop_
_audit_author_name
_audit_author_address
'Valentina Karnoukhova'
;A N Nesmeyanov Institute of Organoelement Compounds of Russian Academy of Sciences
Russia
;
_audit_update_record             
;
2021-06-30 deposited with the CCDC.	2021-09-23 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2016/6
_shelx_SHELXL_version_number     2016/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C21 H18 N4 O S'
_chemical_formula_sum            'C21 H18 N4 O S'
_chemical_formula_weight         374.45

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

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

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

_cell_length_a                   12.1703(4)
_cell_length_b                   8.7069(3)
_cell_length_c                   17.7917(6)
_cell_angle_alpha                90
_cell_angle_beta                 104.923(2)
_cell_angle_gamma                90
_cell_volume                     1821.72(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    120(2)
_cell_measurement_reflns_used    451
_cell_measurement_theta_min      3
_cell_measurement_theta_max      25

_exptl_crystal_description       prism
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_F_000             784
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.260
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.180
_exptl_absorpt_coefficient_mu    0.197
_shelx_estimated_absorpt_T_min   0.951
_shelx_estimated_absorpt_T_max   0.965
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6737
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_process_details   SADABS
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      120(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker SMART APEX II diffractometer'
_diffrn_detector_type            'Bruker PHOTON II CPAD detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            24031
_diffrn_reflns_av_unetI/netI     0.0479
_diffrn_reflns_av_R_equivalents  0.0385
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         1.829
_diffrn_reflns_theta_max         30.523
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             5572
_reflns_number_gt                4240
_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 APEX3'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT (Sheldrick, 2015a)'
_computing_structure_refinement  'SHELXL (Sheldrick, 2015b)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  'SHELXTL (Sheldrick, 2008)'
_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)+(0.0535P)²+0.3530P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         5572
_refine_ls_number_parameters     250
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0558
_refine_ls_R_factor_gt           0.0386
_refine_ls_wR_factor_ref         0.1076
_refine_ls_wR_factor_gt          0.1009
_refine_ls_goodness_of_fit_ref   1.038
_refine_ls_restrained_S_all      1.038
_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
S1 S 0.23416(3) 1.03331(4) 0.28645(2) 0.02073(9) Uani 1 1 d . . . . .
O1 O 0.12688(8) 0.49776(10) 0.42004(5) 0.01942(19) Uani 1 1 d . . . . .
N1 N 0.42654(9) 0.94241(12) 0.37370(6) 0.0170(2) Uani 1 1 d . . . . .
N2 N 0.04780(9) 0.87982(14) 0.39362(7) 0.0246(3) Uani 1 1 d . . . . .
N3 N 0.30863(8) 0.67075(12) 0.53533(6) 0.0149(2) Uani 1 1 d . . . . .
N4 N 0.44887(8) 0.75936(12) 0.49420(6) 0.0160(2) Uani 1 1 d . . . . .
H4N H 0.4821(15) 0.816(2) 0.4634(10) 0.041(5) Uiso 1 1 d . . . . .
C1 C 0.31588(10) 0.93472(14) 0.36771(7) 0.0164(2) Uani 1 1 d . . . . .
C2 C 0.35696(11) 1.08457(16) 0.26142(7) 0.0205(3) Uani 1 1 d . . . . .
H2A H 0.359273 1.144343 0.217184 0.025 Uiso 1 1 calc R U . . .
C3 C 0.45034(11) 1.02755(14) 0.31382(7) 0.0171(2) Uani 1 1 d . . . . .
C4 C 0.57054(10) 1.04866(14) 0.31325(7) 0.0166(2) Uani 1 1 d . . . . .
C5 C 0.60013(12) 1.13572(16) 0.25508(8) 0.0229(3) Uani 1 1 d . . . . .
H5A H 0.542094 1.180138 0.214737 0.027 Uiso 1 1 calc R U . . .
C6 C 0.71337(12) 1.15760(16) 0.25589(8) 0.0242(3) Uani 1 1 d . . . . .
H6A H 0.732198 1.218159 0.216573 0.029 Uiso 1 1 calc R U . . .
C7 C 0.79954(11) 1.09162(15) 0.31379(8) 0.0211(3) Uani 1 1 d . . . . .
H7A H 0.876929 1.105385 0.313666 0.025 Uiso 1 1 calc R U . . .
C8 C 0.77132(11) 1.00547(14) 0.37175(8) 0.0192(3) Uani 1 1 d . . . . .
H8A H 0.829692 0.960804 0.411783 0.023 Uiso 1 1 calc R U . . .
C9 C 0.65796(11) 0.98425(14) 0.37148(7) 0.0188(2) Uani 1 1 d . . . . .
H9A H 0.639700 0.925103 0.411482 0.023 Uiso 1 1 calc R U . . .
C10 C 0.26459(10) 0.85282(14) 0.41999(7) 0.0167(2) Uani 1 1 d . . . . .
C11 C 0.14558(11) 0.86467(14) 0.40738(7) 0.0181(2) Uani 1 1 d . . . . .
C12 C 0.33480(10) 0.76441(13) 0.48139(7) 0.0150(2) Uani 1 1 d . . . . .
C13 C 0.40960(10) 0.60512(14) 0.58169(7) 0.0166(2) Uani 1 1 d . . . . .
C14 C 0.49631(10) 0.66183(14) 0.55576(7) 0.0162(2) Uani 1 1 d . . . . .
C15 C 0.19421(10) 0.63295(14) 0.54291(7) 0.0170(2) Uani 1 1 d . . . . .
H15A H 0.142518 0.720058 0.523218 0.020 Uiso 1 1 calc R U . . .
H15B H 0.197314 0.618888 0.598631 0.020 Uiso 1 1 calc R U . . .
C16 C 0.14718(10) 0.49149(14) 0.49962(7) 0.0159(2) Uani 1 1 d . . . . .
C17 C 0.11824(10) 0.35227(15) 0.52185(8) 0.0198(3) Uani 1 1 d . . . . .
H17A H 0.124081 0.319064 0.573598 0.024 Uiso 1 1 calc R U . . .
C18 C 0.07700(11) 0.26432(15) 0.45223(8) 0.0222(3) Uani 1 1 d . . . . .
H18A H 0.050006 0.161506 0.448623 0.027 Uiso 1 1 calc R U . . .
C19 C 0.08418(11) 0.35666(15) 0.39289(8) 0.0223(3) Uani 1 1 d . . . . .
H19A H 0.062630 0.328005 0.339576 0.027 Uiso 1 1 calc R U . . .
C20 C 0.40985(12) 0.49561(16) 0.64590(8) 0.0242(3) Uani 1 1 d . . . . .
H20A H 0.487912 0.461994 0.669698 0.036 Uiso 1 1 calc R U . . .
H20B H 0.362798 0.406292 0.625101 0.036 Uiso 1 1 calc R U . . .
H20C H 0.378997 0.546383 0.685190 0.036 Uiso 1 1 calc R U . . .
C21 C 0.62155(10) 0.63667(16) 0.58132(7) 0.0199(3) Uani 1 1 d . . . . .
H21A H 0.637414 0.541288 0.611411 0.030 Uiso 1 1 calc R U . . .
H21B H 0.657507 0.723058 0.613762 0.030 Uiso 1 1 calc R U . . .
H21C H 0.652095 0.629115 0.535580 0.030 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
S1 C2 1.7246(14) . ?
S1 C1 1.7538(12) . ?
O1 C19 1.3724(16) . ?
O1 C16 1.3743(15) . ?
N1 C1 1.3250(16) . ?
N1 C3 1.3882(16) . ?
N2 C11 1.1589(16) . ?
N3 C12 1.3584(15) . ?
N3 C13 1.4124(15) . ?
N3 C15 1.4704(14) . ?
N4 C12 1.3483(15) . ?
N4 C14 1.3887(16) . ?
N4 H4N 0.908(18) . ?
C1 C10 1.4361(17) . ?
C2 C3 1.3644(17) . ?
C2 H2A 0.9500 . ?
C3 C4 1.4770(17) . ?
C4 C9 1.3973(17) . ?
C4 C5 1.4026(17) . ?
C5 C6 1.3876(19) . ?
C5 H5A 0.9500 . ?
C6 C7 1.3909(19) . ?
C6 H6A 0.9500 . ?
C7 C8 1.3880(18) . ?
C7 H7A 0.9500 . ?
C8 C9 1.3907(18) . ?
C8 H8A 0.9500 . ?
C9 H9A 0.9500 . ?
C10 C11 1.4112(17) . ?
C10 C12 1.4266(17) . ?
C13 C14 1.3494(17) . ?
C13 C20 1.4874(18) . ?
C14 C21 1.4903(17) . ?
C15 C16 1.4868(17) . ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?
C16 C17 1.3497(17) . ?
C17 C18 1.4326(19) . ?
C17 H17A 0.9500 . ?
C18 C19 1.3477(19) . ?
C18 H18A 0.9500 . ?
C19 H19A 0.9500 . ?
C20 H20A 0.9800 . ?
C20 H20B 0.9800 . ?
C20 H20C 0.9800 . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?

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 S1 C1 89.68(6) . . ?
C19 O1 C16 106.16(10) . . ?
C1 N1 C3 111.96(10) . . ?
C12 N3 C13 109.17(10) . . ?
C12 N3 C15 126.80(10) . . ?
C13 N3 C15 123.92(10) . . ?
C12 N4 C14 110.74(10) . . ?
C12 N4 H4N 118.7(11) . . ?
C14 N4 H4N 130.6(11) . . ?
N1 C1 C10 125.12(11) . . ?
N1 C1 S1 112.98(9) . . ?
C10 C1 S1 121.88(9) . . ?
C3 C2 S1 110.74(10) . . ?
C3 C2 H2A 124.6 . . ?
S1 C2 H2A 124.6 . . ?
C2 C3 N1 114.64(11) . . ?
C2 C3 C4 127.03(11) . . ?
N1 C3 C4 118.33(11) . . ?
C9 C4 C5 118.22(12) . . ?
C9 C4 C3 120.75(11) . . ?
C5 C4 C3 121.02(11) . . ?
C6 C5 C4 120.63(12) . . ?
C6 C5 H5A 119.7 . . ?
C4 C5 H5A 119.7 . . ?
C5 C6 C7 120.56(12) . . ?
C5 C6 H6A 119.7 . . ?
C7 C6 H6A 119.7 . . ?
C8 C7 C6 119.33(12) . . ?
C8 C7 H7A 120.3 . . ?
C6 C7 H7A 120.3 . . ?
C7 C8 C9 120.28(12) . . ?
C7 C8 H8A 119.9 . . ?
C9 C8 H8A 119.9 . . ?
C8 C9 C4 120.96(12) . . ?
C8 C9 H9A 119.5 . . ?
C4 C9 H9A 119.5 . . ?
C11 C10 C12 123.30(11) . . ?
C11 C10 C1 117.40(11) . . ?
C12 C10 C1 119.30(11) . . ?
N2 C11 C10 176.21(14) . . ?
N4 C12 N3 106.23(10) . . ?
N4 C12 C10 122.32(11) . . ?
N3 C12 C10 131.43(11) . . ?
C14 C13 N3 106.96(11) . . ?
C14 C13 C20 130.54(12) . . ?
N3 C13 C20 122.49(11) . . ?
C13 C14 N4 106.89(11) . . ?
C13 C14 C21 132.09(12) . . ?
N4 C14 C21 121.02(11) . . ?
N3 C15 C16 112.66(10) . . ?
N3 C15 H15A 109.1 . . ?
C16 C15 H15A 109.1 . . ?
N3 C15 H15B 109.1 . . ?
C16 C15 H15B 109.1 . . ?
H15A C15 H15B 107.8 . . ?
C17 C16 O1 110.27(11) . . ?
C17 C16 C15 133.38(12) . . ?
O1 C16 C15 116.35(10) . . ?
C16 C17 C18 106.65(12) . . ?
C16 C17 H17A 126.7 . . ?
C18 C17 H17A 126.7 . . ?
C19 C18 C17 106.23(12) . . ?
C19 C18 H18A 126.9 . . ?
C17 C18 H18A 126.9 . . ?
C18 C19 O1 110.69(12) . . ?
C18 C19 H19A 124.7 . . ?
O1 C19 H19A 124.7 . . ?
C13 C20 H20A 109.5 . . ?
C13 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C13 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C14 C21 H21A 109.5 . . ?
C14 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C14 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 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
C3 N1 C1 C10 178.88(11) . . . . ?
C3 N1 C1 S1 0.15(13) . . . . ?
C2 S1 C1 N1 0.07(10) . . . . ?
C2 S1 C1 C10 -178.71(11) . . . . ?
C1 S1 C2 C3 -0.27(10) . . . . ?
S1 C2 C3 N1 0.42(15) . . . . ?
S1 C2 C3 C4 -178.91(10) . . . . ?
C1 N1 C3 C2 -0.37(16) . . . . ?
C1 N1 C3 C4 179.02(10) . . . . ?
C2 C3 C4 C9 179.41(12) . . . . ?
N1 C3 C4 C9 0.10(17) . . . . ?
C2 C3 C4 C5 0.4(2) . . . . ?
N1 C3 C4 C5 -178.87(12) . . . . ?
C9 C4 C5 C6 -0.3(2) . . . . ?
C3 C4 C5 C6 178.66(12) . . . . ?
C4 C5 C6 C7 1.0(2) . . . . ?
C5 C6 C7 C8 -1.1(2) . . . . ?
C6 C7 C8 C9 0.58(19) . . . . ?
C7 C8 C9 C4 0.04(19) . . . . ?
C5 C4 C9 C8 -0.16(19) . . . . ?
C3 C4 C9 C8 -179.16(12) . . . . ?
N1 C1 C10 C11 176.30(12) . . . . ?
S1 C1 C10 C11 -5.08(16) . . . . ?
N1 C1 C10 C12 -3.73(19) . . . . ?
S1 C1 C10 C12 174.89(9) . . . . ?
C14 N4 C12 N3 0.50(13) . . . . ?
C14 N4 C12 C10 -178.26(11) . . . . ?
C13 N3 C12 N4 -0.81(13) . . . . ?
C15 N3 C12 N4 -177.11(10) . . . . ?
C13 N3 C12 C10 177.79(12) . . . . ?
C15 N3 C12 C10 1.5(2) . . . . ?
C11 C10 C12 N4 -177.41(11) . . . . ?
C1 C10 C12 N4 2.62(18) . . . . ?
C11 C10 C12 N3 4.2(2) . . . . ?
C1 C10 C12 N3 -175.79(12) . . . . ?
C12 N3 C13 C14 0.83(13) . . . . ?
C15 N3 C13 C14 177.26(11) . . . . ?
C12 N3 C13 C20 -179.44(12) . . . . ?
C15 N3 C13 C20 -3.01(18) . . . . ?
N3 C13 C14 N4 -0.50(13) . . . . ?
C20 C13 C14 N4 179.80(13) . . . . ?
N3 C13 C14 C21 179.55(12) . . . . ?
C20 C13 C14 C21 -0.1(2) . . . . ?
C12 N4 C14 C13 0.01(14) . . . . ?
C12 N4 C14 C21 179.97(11) . . . . ?
C12 N3 C15 C16 92.29(14) . . . . ?
C13 N3 C15 C16 -83.50(14) . . . . ?
C19 O1 C16 C17 -0.14(13) . . . . ?
C19 O1 C16 C15 -179.90(10) . . . . ?
N3 C15 C16 C17 115.43(15) . . . . ?
N3 C15 C16 O1 -64.88(14) . . . . ?
O1 C16 C17 C18 0.02(14) . . . . ?
C15 C16 C17 C18 179.72(13) . . . . ?
C16 C17 C18 C19 0.11(15) . . . . ?
C17 C18 C19 O1 -0.20(15) . . . . ?
C16 O1 C19 C18 0.22(14) . . . . ?

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
N4 H4N N1 0.908(18) 1.912(18) 2.6288(15) 134.5(15) .

_refine_diff_density_max         0.312
_refine_diff_density_min         -0.336
_refine_diff_density_rms         0.058

