# Electronic Supplementary Material (ESI) for RSC Advances.
# 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_20170818_0m
_database_code_depnum_ccdc_archive 'CCDC 1578072'
_audit_update_record             
;
2017-10-04 deposited with the CCDC.
2017-12-26 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
'1,5-dimethyl-2-(thiophen-3-yl)-6-(4-(trifluoromethyl)phenyl)-1,5-dihyrodipyrrolo[3,2-b:3?,2?-e]pyrazine (7g)'
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C21 H15 F3 N4 S'
_chemical_formula_weight         412.43

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'
F F 0.0171 0.0103 '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   P2(1)/c

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                   15.0769(2)
_cell_length_b                   8.80100(10)
_cell_length_c                   15.4166(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 115.2030(10)
_cell_angle_gamma                90.00
_cell_volume                     1850.92(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(1)
_cell_measurement_reflns_used    8374
_cell_measurement_theta_min      2.74
_cell_measurement_theta_max      27.30

_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.38
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.04
_exptl_crystal_density_meas      none
_exptl_crystal_density_diffrn    1.480
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             848
_exptl_absorpt_coefficient_mu    0.220
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9212
_exptl_absorpt_correction_T_max  0.9913
_exptl_absorpt_process_details   'Bruker SADABS'

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(1)
_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 APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            4596
_diffrn_reflns_av_R_equivalents  0.0000
_diffrn_reflns_av_sigmaI/netI    0.0213
_diffrn_reflns_limit_h_min       -20
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       0
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       0
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_theta_min         1.49
_diffrn_reflns_theta_max         28.28
_reflns_number_total             4596
_reflns_number_gt                3283
_reflns_threshold_expression     >2sigma(I)

_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-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_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)+(0.2000P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    refxyz
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         4596
_refine_ls_number_parameters     262
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1359
_refine_ls_R_factor_gt           0.1120
_refine_ls_wR_factor_ref         0.3831
_refine_ls_wR_factor_gt          0.3494
_refine_ls_goodness_of_fit_ref   1.554
_refine_ls_restrained_S_all      1.554
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.001

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
S1 S 1.27969(9) 0.02418(16) 0.15509(8) 0.0689(5) Uani 1 1 d . . .
F1 F 0.5503(3) 0.3146(10) 0.7117(3) 0.200(3) Uani 1 1 d . . .
F2 F 0.4561(4) 0.2178(11) 0.5992(6) 0.245(5) Uani 1 1 d . . .
F3 F 0.4815(8) 0.4247(10) 0.5947(8) 0.321(7) Uani 1 1 d . . .
N1 N 1.1301(2) 0.2151(3) 0.36925(18) 0.0365(6) Uani 1 1 d . . .
N2 N 1.0332(2) 0.2756(3) 0.45417(19) 0.0386(7) Uani 1 1 d . . .
N3 N 0.9138(2) 0.0216(3) 0.3419(2) 0.0372(7) Uani 1 1 d . . .
N4 N 0.8150(2) 0.0819(3) 0.4255(2) 0.0400(7) Uani 1 1 d . . .
C1 C 1.1791(3) 0.0441(5) 0.1746(3) 0.0516(9) Uani 1 1 d . . .
H1 H 1.1160 0.0238 0.1286 0.062 Uiso 1 1 calc R . .
C2 C 1.1993(2) 0.0933(4) 0.2650(2) 0.0391(7) Uani 1 1 d . . .
C3 C 1.3013(3) 0.1165(5) 0.3193(3) 0.0569(10) Uani 1 1 d . . .
H3 H 1.3290 0.1494 0.3827 0.068 Uiso 1 1 calc R . .
C4 C 1.3583(3) 0.0832(5) 0.2652(3) 0.0493(9) Uani 1 1 d . . .
H4 H 1.4258 0.0928 0.2875 0.059 Uiso 1 1 calc R . .
C5 C 1.1249(2) 0.1087(4) 0.3017(2) 0.0379(7) Uani 1 1 d . . .
C6 C 1.0423(2) 0.0174(4) 0.2795(2) 0.0406(8) Uani 1 1 d . . .
H6A H 1.0219 -0.0619 0.2355 0.049 Uiso 1 1 calc R . .
C7 C 0.9959(2) 0.0683(4) 0.3363(2) 0.0369(7) Uani 1 1 d . . .
C8 C 1.0519(2) 0.1936(4) 0.3919(2) 0.0345(7) Uani 1 1 d . . .
C9 C 1.1930(3) 0.3491(4) 0.3984(3) 0.0480(9) Uani 1 1 d . . .
H9A H 1.2428 0.3409 0.3754 0.072 Uiso 1 1 calc R . .
H9B H 1.2233 0.3561 0.4671 0.072 Uiso 1 1 calc R . .
H9C H 1.1543 0.4384 0.3720 0.072 Uiso 1 1 calc R . .
C10 C 0.8952(2) 0.1023(4) 0.4053(2) 0.0348(7) Uani 1 1 d . . .
C11 C 0.9517(2) 0.2237(4) 0.4614(2) 0.0372(7) Uani 1 1 d . . .
C12 C 0.9050(3) 0.2763(4) 0.5188(2) 0.0425(8) Uani 1 1 d . . .
H12A H 0.9266 0.3541 0.5638 0.051 Uiso 1 1 calc R . .
C13 C 0.8221(2) 0.1902(4) 0.4950(2) 0.0391(7) Uani 1 1 d . . .
C14 C 0.7535(3) -0.0497(5) 0.3952(3) 0.0526(10) Uani 1 1 d . . .
H14A H 0.7648 -0.1015 0.3460 0.079 Uiso 1 1 calc R . .
H14B H 0.6860 -0.0192 0.3704 0.079 Uiso 1 1 calc R . .
H14C H 0.7683 -0.1165 0.4488 0.079 Uiso 1 1 calc R . .
C15 C 0.7449(2) 0.2114(4) 0.5281(2) 0.0392(8) Uani 1 1 d . . .
C16 C 0.7713(3) 0.2598(4) 0.6227(2) 0.0419(8) Uani 1 1 d . . .
H16A H 0.8371 0.2708 0.6646 0.050 Uiso 1 1 calc R . .
C17 C 0.6995(3) 0.2912(4) 0.6537(3) 0.0474(9) Uani 1 1 d . . .
H17A H 0.7177 0.3220 0.7167 0.057 Uiso 1 1 calc R . .
C18 C 0.6020(3) 0.2777(5) 0.5933(3) 0.0532(10) Uani 1 1 d . . .
C19 C 0.5745(3) 0.2284(6) 0.4995(3) 0.0638(12) Uani 1 1 d . . .
H19A H 0.5086 0.2159 0.4583 0.077 Uiso 1 1 calc R . .
C20 C 0.6466(3) 0.1977(5) 0.4680(3) 0.0568(10) Uani 1 1 d . . .
H20A H 0.6279 0.1673 0.4049 0.068 Uiso 1 1 calc R . .
C21 C 0.5262(3) 0.3110(7) 0.6261(4) 0.0722(14) 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
S1 C1 1.676(4) . ?
S1 C4 1.686(4) . ?
F1 C21 1.211(6) . ?
F2 C21 1.260(8) . ?
F3 C21 1.188(7) . ?
N1 C8 1.377(4) . ?
N1 C5 1.377(4) . ?
N1 C9 1.459(4) . ?
N2 C8 1.324(4) . ?
N2 C11 1.360(4) . ?
N3 C10 1.331(4) . ?
N3 C7 1.341(4) . ?
N4 C10 1.383(4) . ?
N4 C13 1.403(4) . ?
N4 C14 1.433(5) . ?
C1 C2 1.364(5) . ?
C1 H1 0.9300 . ?
C2 C3 1.418(5) . ?
C2 C5 1.463(4) . ?
C3 C4 1.459(5) . ?
C3 H3 0.9300 . ?
C4 H4 0.9300 . ?
C5 C6 1.397(5) . ?
C6 C7 1.407(4) . ?
C6 H6A 0.9300 . ?
C7 C8 1.430(4) . ?
C9 H9A 0.9600 . ?
C9 H9B 0.9600 . ?
C9 H9C 0.9600 . ?
C10 C11 1.409(5) . ?
C11 C12 1.423(4) . ?
C12 C13 1.371(5) . ?
C12 H12A 0.9300 . ?
C13 C15 1.469(4) . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?
C15 C20 1.378(5) . ?
C15 C16 1.405(5) . ?
C16 C17 1.386(5) . ?
C16 H16A 0.9300 . ?
C17 C18 1.370(6) . ?
C17 H17A 0.9300 . ?
C18 C19 1.392(6) . ?
C18 C21 1.463(5) . ?
C19 C20 1.392(5) . ?
C19 H19A 0.9300 . ?
C20 H20A 0.9300 . ?

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
C1 S1 C4 95.08(18) . . ?
C8 N1 C5 108.6(3) . . ?
C8 N1 C9 123.2(3) . . ?
C5 N1 C9 127.1(3) . . ?
C8 N2 C11 110.8(3) . . ?
C10 N3 C7 111.9(3) . . ?
C10 N4 C13 107.1(3) . . ?
C10 N4 C14 122.6(3) . . ?
C13 N4 C14 128.8(3) . . ?
C2 C1 S1 113.0(3) . . ?
C2 C1 H1 123.5 . . ?
S1 C1 H1 123.5 . . ?
C1 C2 C3 111.3(3) . . ?
C1 C2 C5 123.4(3) . . ?
C3 C2 C5 125.1(3) . . ?
C2 C3 C4 112.8(3) . . ?
C2 C3 H3 123.6 . . ?
C4 C3 H3 123.6 . . ?
C3 C4 S1 107.8(3) . . ?
C3 C4 H4 126.1 . . ?
S1 C4 H4 126.1 . . ?
N1 C5 C6 109.5(3) . . ?
N1 C5 C2 123.4(3) . . ?
C6 C5 C2 127.0(3) . . ?
C5 C6 C7 107.0(3) . . ?
C5 C6 H6A 126.5 . . ?
C7 C6 H6A 126.5 . . ?
N3 C7 C6 131.3(3) . . ?
N3 C7 C8 121.6(3) . . ?
C6 C7 C8 107.1(3) . . ?
N2 C8 N1 125.3(3) . . ?
N2 C8 C7 126.9(3) . . ?
N1 C8 C7 107.8(3) . . ?
N1 C9 H9A 109.5 . . ?
N1 C9 H9B 109.5 . . ?
H9A C9 H9B 109.5 . . ?
N1 C9 H9C 109.5 . . ?
H9A C9 H9C 109.5 . . ?
H9B C9 H9C 109.5 . . ?
N3 C10 N4 125.0(3) . . ?
N3 C10 C11 126.4(3) . . ?
N4 C10 C11 108.5(3) . . ?
N2 C11 C10 122.4(3) . . ?
N2 C11 C12 130.2(3) . . ?
C10 C11 C12 107.4(3) . . ?
C13 C12 C11 106.9(3) . . ?
C13 C12 H12A 126.6 . . ?
C11 C12 H12A 126.6 . . ?
C12 C13 N4 110.1(3) . . ?
C12 C13 C15 127.2(3) . . ?
N4 C13 C15 122.5(3) . . ?
N4 C14 H14A 109.5 . . ?
N4 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
N4 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C20 C15 C16 118.2(3) . . ?
C20 C15 C13 122.8(3) . . ?
C16 C15 C13 118.9(3) . . ?
C17 C16 C15 120.1(3) . . ?
C17 C16 H16A 120.0 . . ?
C15 C16 H16A 120.0 . . ?
C18 C17 C16 121.2(3) . . ?
C18 C17 H17A 119.4 . . ?
C16 C17 H17A 119.4 . . ?
C17 C18 C19 119.5(3) . . ?
C17 C18 C21 121.2(4) . . ?
C19 C18 C21 119.4(4) . . ?
C20 C19 C18 119.4(4) . . ?
C20 C19 H19A 120.3 . . ?
C18 C19 H19A 120.3 . . ?
C15 C20 C19 121.7(3) . . ?
C15 C20 H20A 119.2 . . ?
C19 C20 H20A 119.2 . . ?
F3 C21 F1 106.1(7) . . ?
F3 C21 F2 99.4(8) . . ?
F1 C21 F2 101.3(7) . . ?
F3 C21 C18 114.7(5) . . ?
F1 C21 C18 117.8(4) . . ?
F2 C21 C18 115.1(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
C4 S1 C1 C2 -1.1(3) . . . . ?
S1 C1 C2 C3 0.6(5) . . . . ?
S1 C1 C2 C5 -175.3(3) . . . . ?
C1 C2 C3 C4 0.4(5) . . . . ?
C5 C2 C3 C4 176.2(3) . . . . ?
C2 C3 C4 S1 -1.1(5) . . . . ?
C1 S1 C4 C3 1.2(3) . . . . ?
C8 N1 C5 C6 0.4(4) . . . . ?
C9 N1 C5 C6 -167.3(3) . . . . ?
C8 N1 C5 C2 -176.7(3) . . . . ?
C9 N1 C5 C2 15.6(5) . . . . ?
C1 C2 C5 N1 -149.6(3) . . . . ?
C3 C2 C5 N1 35.1(5) . . . . ?
C1 C2 C5 C6 33.9(5) . . . . ?
C3 C2 C5 C6 -141.4(4) . . . . ?
N1 C5 C6 C7 -0.8(4) . . . . ?
C2 C5 C6 C7 176.1(3) . . . . ?
C10 N3 C7 C6 -179.5(3) . . . . ?
C10 N3 C7 C8 -1.6(4) . . . . ?
C5 C6 C7 N3 179.0(3) . . . . ?
C5 C6 C7 C8 0.9(4) . . . . ?
C11 N2 C8 N1 -178.9(3) . . . . ?
C11 N2 C8 C7 1.1(5) . . . . ?
C5 N1 C8 N2 -179.8(3) . . . . ?
C9 N1 C8 N2 -11.5(5) . . . . ?
C5 N1 C8 C7 0.2(3) . . . . ?
C9 N1 C8 C7 168.5(3) . . . . ?
N3 C7 C8 N2 1.0(5) . . . . ?
C6 C7 C8 N2 179.3(3) . . . . ?
N3 C7 C8 N1 -179.0(3) . . . . ?
C6 C7 C8 N1 -0.6(4) . . . . ?
C7 N3 C10 N4 178.9(3) . . . . ?
C7 N3 C10 C11 0.3(5) . . . . ?
C13 N4 C10 N3 -179.3(3) . . . . ?
C14 N4 C10 N3 13.6(5) . . . . ?
C13 N4 C10 C11 -0.5(3) . . . . ?
C14 N4 C10 C11 -167.5(3) . . . . ?
C8 N2 C11 C10 -2.4(4) . . . . ?
C8 N2 C11 C12 180.0(3) . . . . ?
N3 C10 C11 N2 1.9(5) . . . . ?
N4 C10 C11 N2 -176.9(3) . . . . ?
N3 C10 C11 C12 -180.0(3) . . . . ?
N4 C10 C11 C12 1.2(4) . . . . ?
N2 C11 C12 C13 176.5(3) . . . . ?
C10 C11 C12 C13 -1.4(4) . . . . ?
C11 C12 C13 N4 1.2(4) . . . . ?
C11 C12 C13 C15 -173.6(3) . . . . ?
C10 N4 C13 C12 -0.4(4) . . . . ?
C14 N4 C13 C12 165.5(3) . . . . ?
C10 N4 C13 C15 174.6(3) . . . . ?
C14 N4 C13 C15 -19.4(5) . . . . ?
C12 C13 C15 C20 138.0(4) . . . . ?
N4 C13 C15 C20 -36.1(5) . . . . ?
C12 C13 C15 C16 -36.6(5) . . . . ?
N4 C13 C15 C16 149.3(3) . . . . ?
C20 C15 C16 C17 0.5(5) . . . . ?
C13 C15 C16 C17 175.3(3) . . . . ?
C15 C16 C17 C18 -0.8(6) . . . . ?
C16 C17 C18 C19 1.4(6) . . . . ?
C16 C17 C18 C21 -180.0(4) . . . . ?
C17 C18 C19 C20 -1.8(7) . . . . ?
C21 C18 C19 C20 179.5(5) . . . . ?
C16 C15 C20 C19 -1.0(6) . . . . ?
C13 C15 C20 C19 -175.6(4) . . . . ?
C18 C19 C20 C15 1.6(7) . . . . ?
C17 C18 C21 F3 108.4(9) . . . . ?
C19 C18 C21 F3 -73.0(10) . . . . ?
C17 C18 C21 F1 -17.5(9) . . . . ?
C19 C18 C21 F1 161.1(7) . . . . ?
C17 C18 C21 F2 -137.0(7) . . . . ?
C19 C18 C21 F2 41.6(9) . . . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        28.28
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         1.296
_refine_diff_density_min         -0.778
_refine_diff_density_rms         0.134
