# Electronic Supplementary Material (ESI) for Chemical Communications.
# 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_arup1m
_database_code_depnum_ccdc_archive 'CCDC 1043667'
_audit_update_record             
;
2015-01-15 deposited with the CCDC.
2015-03-18 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
"ethyl 12-formyl-2-(trifluoromethyl)-5,6-dihydropyrazolo (5',1':3,4) pyrazino [1,2-a] indole-1-carboxylate"
_chemical_name_common            ?
_chemical_melting_point          427.15
_chemical_formula_moiety         ?
_chemical_formula_sum            'C18 H14 F3 N3 O3'
_chemical_formula_weight         62.03

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'
F F 0.0171 0.0103 '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)/n

loop_
_symmetry_equiv_pos_as_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                   11.296(12)
_cell_length_b                   13.615(14)
_cell_length_c                   11.516(12)
_cell_angle_alpha                90.00
_cell_angle_beta                 105.89(2)
_cell_angle_gamma                90.00
_cell_volume                     1704(3)
_cell_formula_units_Z            28
_cell_measurement_temperature    273(2)
_cell_measurement_reflns_used    1379
_cell_measurement_theta_min      2.37
_cell_measurement_theta_max      20.41

_exptl_crystal_description       parallelepiped
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_crystal_density_meas      0
_exptl_crystal_density_diffrn    1.693
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             868
_exptl_absorpt_coefficient_mu    0.190
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      273(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         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8417
_diffrn_reflns_av_R_equivalents  0.0428
_diffrn_reflns_av_sigmaI/netI    0.0571
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         2.24
_diffrn_reflns_theta_max         25.00
_reflns_number_total             2989
_reflns_number_gt                2217
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_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)+(0.0435P)²+1.7712P] 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_number_reflns         2989
_refine_ls_number_parameters     245
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1032
_refine_ls_R_factor_gt           0.0760
_refine_ls_wR_factor_ref         0.1624
_refine_ls_wR_factor_gt          0.1505
_refine_ls_goodness_of_fit_ref   1.077
_refine_ls_restrained_S_all      1.077
_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
C1 C 0.4228(3) 0.0150(2) 0.7625(3) 0.0389(8) Uani 1 1 d . . .
C2 C 0.5170(3) 0.0186(2) 0.6985(3) 0.0396(8) Uani 1 1 d . . .
C3 C 0.3440(3) -0.0476(3) 0.9047(3) 0.0426(8) Uani 1 1 d . . .
C4 C 0.2745(3) 0.0365(2) 0.8576(3) 0.0441(8) Uani 1 1 d . . .
C5 C 0.6640(3) 0.0399(3) 0.6098(3) 0.0453(8) Uani 1 1 d . . .
C6 C 0.5258(3) -0.1375(2) 0.8616(3) 0.0440(8) Uani 1 1 d . . .
H6A H 0.4965 -0.1965 0.8917 0.053 Uiso 1 1 calc R . .
H6B H 0.6002 -0.1160 0.9206 0.053 Uiso 1 1 calc R . .
C7 C 0.3239(3) 0.0748(2) 0.7643(3) 0.0428(8) Uani 1 1 d . . .
C8 C 0.5723(3) 0.0907(2) 0.6460(3) 0.0411(8) Uani 1 1 d . . .
C9 C 0.2707(3) 0.1510(3) 0.6795(4) 0.0560(10) Uani 1 1 d . . .
H9 H 0.3063 0.1629 0.6170 0.067 Uiso 1 1 calc R . .
C10 C 0.5536(3) 0.1981(3) 0.6405(3) 0.0532(10) Uani 1 1 d . . .
C11 C 0.5043(4) 0.3370(3) 0.7429(4) 0.0611(11) Uani 1 1 d . . .
H11A H 0.4451 0.3585 0.6693 0.073 Uiso 1 1 calc R . .
H11B H 0.5803 0.3731 0.7516 0.073 Uiso 1 1 calc R . .
C12 C 0.1815(3) 0.0670(3) 0.9078(4) 0.0568(10) Uani 1 1 d . . .
H12 H 0.1333 0.1216 0.8777 0.068 Uiso 1 1 calc R . .
C13 C 0.3236(3) -0.1022(3) 0.9992(3) 0.0525(9) Uani 1 1 d . . .
H13 H 0.3693 -0.1581 1.0285 0.063 Uiso 1 1 calc R . .
C14 C 0.1629(3) 0.0144(3) 1.0027(4) 0.0643(11) Uani 1 1 d . . .
H14 H 0.1025 0.0348 1.0384 0.077 Uiso 1 1 calc R . .
C15 C 0.7610(4) 0.0785(3) 0.5577(4) 0.0589(10) Uani 1 1 d . . .
C16 C 0.5531(3) -0.1587(2) 0.7429(3) 0.0497(9) Uani 1 1 d . . .
H16A H 0.6245 -0.2012 0.7560 0.060 Uiso 1 1 calc R . .
H16B H 0.4836 -0.1918 0.6887 0.060 Uiso 1 1 calc R . .
C17 C 0.2321(4) -0.0690(3) 1.0472(4) 0.0630(11) Uani 1 1 d . . .
H17 H 0.2159 -0.1031 1.1111 0.076 Uiso 1 1 calc R . .
C18 C 0.4562(4) 0.3550(3) 0.8479(4) 0.0795(14) Uani 1 1 d . . .
H18A H 0.3830 0.3168 0.8400 0.119 Uiso 1 1 calc R . .
H18B H 0.4372 0.4235 0.8514 0.119 Uiso 1 1 calc R . .
H18C H 0.5171 0.3365 0.9205 0.119 Uiso 1 1 calc R . .
F1 F 0.8337(3) 0.1401(2) 0.6300(3) 0.1204(13) Uani 1 1 d . . .
F2 F 0.8309(2) 0.0094(2) 0.5327(3) 0.0965(9) Uani 1 1 d . . .
F3 F 0.7154(2) 0.1246(2) 0.4531(3) 0.0950(9) Uani 1 1 d . . .
N1 N 0.4318(2) -0.06031(19) 0.8432(2) 0.0404(7) Uani 1 1 d . . .
N2 N 0.5767(2) -0.06591(19) 0.6901(3) 0.0453(7) Uani 1 1 d . . .
N3 N 0.6677(3) -0.0550(2) 0.6374(3) 0.0512(8) Uani 1 1 d . . .
O1 O 0.5623(4) 0.2485(2) 0.5586(3) 0.1130(15) Uani 1 1 d . . .
O2 O 0.5265(2) 0.23176(16) 0.7374(2) 0.0512(7) Uani 1 1 d . . .
O3 O 0.1833(3) 0.2005(2) 0.6834(3) 0.0844(10) 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 N1 1.369(4) . ?
C1 C7 1.387(4) . ?
C1 C2 1.452(5) . ?
C2 N2 1.350(4) . ?
C2 C8 1.388(5) . ?
C3 N1 1.378(4) . ?
C3 C13 1.389(5) . ?
C3 C4 1.410(5) . ?
C4 C12 1.395(5) . ?
C4 C7 1.437(5) . ?
C5 N3 1.328(5) . ?
C5 C8 1.400(5) . ?
C5 C15 1.483(5) . ?
C6 N1 1.468(4) . ?
C6 C16 1.509(5) . ?
C6 H6A 0.9700 . ?
C6 H6B 0.9700 . ?
C7 C9 1.439(5) . ?
C8 C10 1.477(5) . ?
C9 O3 1.207(4) . ?
C9 H9 0.9300 . ?
C10 O1 1.191(4) . ?
C10 O2 1.317(4) . ?
C11 O2 1.458(4) . ?
C11 C18 1.476(5) . ?
C11 H11A 0.9700 . ?
C11 H11B 0.9700 . ?
C12 C14 1.370(6) . ?
C12 H12 0.9300 . ?
C13 C17 1.375(5) . ?
C13 H13 0.9300 . ?
C14 C17 1.394(6) . ?
C14 H14 0.9300 . ?
C15 F1 1.302(5) . ?
C15 F2 1.309(4) . ?
C15 F3 1.331(5) . ?
C16 N2 1.458(4) . ?
C16 H16A 0.9700 . ?
C16 H16B 0.9700 . ?
C17 H17 0.9300 . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
N2 N3 1.337(4) . ?

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
N1 C1 C7 109.9(3) . . ?
N1 C1 C2 116.2(3) . . ?
C7 C1 C2 133.9(3) . . ?
N2 C2 C8 106.1(3) . . ?
N2 C2 C1 117.3(3) . . ?
C8 C2 C1 136.4(3) . . ?
N1 C3 C13 129.3(3) . . ?
N1 C3 C4 107.9(3) . . ?
C13 C3 C4 122.8(3) . . ?
C12 C4 C3 119.1(3) . . ?
C12 C4 C7 133.8(3) . . ?
C3 C4 C7 107.0(3) . . ?
N3 C5 C8 112.7(3) . . ?
N3 C5 C15 117.6(3) . . ?
C8 C5 C15 129.4(3) . . ?
N1 C6 C16 109.0(3) . . ?
N1 C6 H6A 109.9 . . ?
C16 C6 H6A 109.9 . . ?
N1 C6 H6B 109.9 . . ?
C16 C6 H6B 109.9 . . ?
H6A C6 H6B 108.3 . . ?
C1 C7 C4 106.1(3) . . ?
C1 C7 C9 127.0(3) . . ?
C4 C7 C9 126.4(3) . . ?
C2 C8 C5 103.8(3) . . ?
C2 C8 C10 130.0(3) . . ?
C5 C8 C10 125.8(3) . . ?
O3 C9 C7 124.8(4) . . ?
O3 C9 H9 117.6 . . ?
C7 C9 H9 117.6 . . ?
O1 C10 O2 124.0(4) . . ?
O1 C10 C8 124.2(4) . . ?
O2 C10 C8 111.8(3) . . ?
O2 C11 C18 107.8(3) . . ?
O2 C11 H11A 110.1 . . ?
C18 C11 H11A 110.1 . . ?
O2 C11 H11B 110.1 . . ?
C18 C11 H11B 110.1 . . ?
H11A C11 H11B 108.5 . . ?
C14 C12 C4 118.2(4) . . ?
C14 C12 H12 120.9 . . ?
C4 C12 H12 120.9 . . ?
C17 C13 C3 116.3(4) . . ?
C17 C13 H13 121.8 . . ?
C3 C13 H13 121.8 . . ?
C12 C14 C17 121.8(4) . . ?
C12 C14 H14 119.1 . . ?
C17 C14 H14 119.1 . . ?
F1 C15 F2 106.9(4) . . ?
F1 C15 F3 107.1(4) . . ?
F2 C15 F3 104.4(3) . . ?
F1 C15 C5 112.1(3) . . ?
F2 C15 C5 113.0(3) . . ?
F3 C15 C5 112.8(3) . . ?
N2 C16 C6 108.5(3) . . ?
N2 C16 H16A 110.0 . . ?
C6 C16 H16A 110.0 . . ?
N2 C16 H16B 110.0 . . ?
C6 C16 H16B 110.0 . . ?
H16A C16 H16B 108.4 . . ?
C13 C17 C14 121.8(4) . . ?
C13 C17 H17 119.1 . . ?
C14 C17 H17 119.1 . . ?
C11 C18 H18A 109.5 . . ?
C11 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C11 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C1 N1 C3 108.9(3) . . ?
C1 N1 C6 123.4(3) . . ?
C3 N1 C6 127.6(3) . . ?
N3 N2 C2 113.5(3) . . ?
N3 N2 C16 122.4(3) . . ?
C2 N2 C16 123.8(3) . . ?
C5 N3 N2 103.8(3) . . ?
C10 O2 C11 117.5(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
N1 C1 C2 N2 22.4(4) . . . . ?
C7 C1 C2 N2 -160.4(3) . . . . ?
N1 C1 C2 C8 -152.3(4) . . . . ?
C7 C1 C2 C8 24.9(7) . . . . ?
N1 C3 C4 C12 -178.0(3) . . . . ?
C13 C3 C4 C12 0.4(5) . . . . ?
N1 C3 C4 C7 -0.1(3) . . . . ?
C13 C3 C4 C7 178.3(3) . . . . ?
N1 C1 C7 C4 3.7(4) . . . . ?
C2 C1 C7 C4 -173.5(3) . . . . ?
N1 C1 C7 C9 -168.5(3) . . . . ?
C2 C1 C7 C9 14.3(6) . . . . ?
C12 C4 C7 C1 175.3(4) . . . . ?
C3 C4 C7 C1 -2.2(3) . . . . ?
C12 C4 C7 C9 -12.4(6) . . . . ?
C3 C4 C7 C9 170.1(3) . . . . ?
N2 C2 C8 C5 -0.1(4) . . . . ?
C1 C2 C8 C5 175.0(4) . . . . ?
N2 C2 C8 C10 -173.1(4) . . . . ?
C1 C2 C8 C10 2.0(7) . . . . ?
N3 C5 C8 C2 -0.5(4) . . . . ?
C15 C5 C8 C2 -174.2(4) . . . . ?
N3 C5 C8 C10 172.9(3) . . . . ?
C15 C5 C8 C10 -0.7(6) . . . . ?
C1 C7 C9 O3 178.9(4) . . . . ?
C4 C7 C9 O3 8.3(6) . . . . ?
C2 C8 C10 O1 -147.5(4) . . . . ?
C5 C8 C10 O1 40.8(6) . . . . ?
C2 C8 C10 O2 32.6(5) . . . . ?
C5 C8 C10 O2 -139.0(3) . . . . ?
C3 C4 C12 C14 1.0(5) . . . . ?
C7 C4 C12 C14 -176.3(4) . . . . ?
N1 C3 C13 C17 176.9(3) . . . . ?
C4 C3 C13 C17 -1.1(5) . . . . ?
C4 C12 C14 C17 -1.6(5) . . . . ?
N3 C5 C15 F1 -113.4(4) . . . . ?
C8 C5 C15 F1 60.0(6) . . . . ?
N3 C5 C15 F2 7.4(5) . . . . ?
C8 C5 C15 F2 -179.2(4) . . . . ?
N3 C5 C15 F3 125.6(4) . . . . ?
C8 C5 C15 F3 -61.0(5) . . . . ?
N1 C6 C16 N2 50.0(4) . . . . ?
C3 C13 C17 C14 0.6(5) . . . . ?
C12 C14 C17 C13 0.8(6) . . . . ?
C7 C1 N1 C3 -3.9(4) . . . . ?
C2 C1 N1 C3 173.9(3) . . . . ?
C7 C1 N1 C6 178.9(3) . . . . ?
C2 C1 N1 C6 -3.2(4) . . . . ?
C13 C3 N1 C1 -175.9(3) . . . . ?
C4 C3 N1 C1 2.4(3) . . . . ?
C13 C3 N1 C6 1.1(5) . . . . ?
C4 C3 N1 C6 179.4(3) . . . . ?
C16 C6 N1 C1 -34.0(4) . . . . ?
C16 C6 N1 C3 149.4(3) . . . . ?
C8 C2 N2 N3 0.7(4) . . . . ?
C1 C2 N2 N3 -175.5(3) . . . . ?
C8 C2 N2 C16 175.2(3) . . . . ?
C1 C2 N2 C16 -1.0(5) . . . . ?
C6 C16 N2 N3 137.7(3) . . . . ?
C6 C16 N2 C2 -36.3(4) . . . . ?
C8 C5 N3 N2 0.9(4) . . . . ?
C15 C5 N3 N2 175.3(3) . . . . ?
C2 N2 N3 C5 -1.0(4) . . . . ?
C16 N2 N3 C5 -175.5(3) . . . . ?
O1 C10 O2 C11 0.9(6) . . . . ?
C8 C10 O2 C11 -179.3(3) . . . . ?
C18 C11 O2 C10 170.8(3) . . . . ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        25.00
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         0.440
_refine_diff_density_min         -0.367
_refine_diff_density_rms         0.044
_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: Ethyl acetate'
_chemical_properties_physical    Moisture-sensitive
