# 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_shelx
_database_code_depnum_ccdc_archive 'CCDC 1457778'
_audit_update_record             
;
2016-03-04 deposited with the CCDC.
2017-05-05 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
(2Z)-2-(aminomethylidene)-3-oxo-N-[4-(trifluoromethyl)phenyl]butanamide
_chemical_name_common            
(Z)-2-(aminomethylene)-3-oxo-N-(4-(trifluoromethyl)phenyl)butanamide
_chemical_melting_point          493.65-494.25
_chemical_formula_moiety         ?
_chemical_formula_sum            'C12 H11 F3 N2 O2'
_chemical_formula_weight         272.23

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'

_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                   7.1752(11)
_cell_length_b                   13.714(2)
_cell_length_c                   12.346(2)
_cell_angle_alpha                90
_cell_angle_beta                 91.918(5)
_cell_angle_gamma                90
_cell_volume                     1214.1(3)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    2641
_cell_measurement_theta_min      3.2
_cell_measurement_theta_max      21.58

_exptl_crystal_description       block
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.489
_exptl_crystal_F_000             560
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.250
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.200
_exptl_absorpt_coefficient_mu    0.133
_shelx_estimated_absorpt_T_min   0.968
_shelx_estimated_absorpt_T_max   0.974
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.9021
_exptl_absorpt_correction_T_max  0.962
_exptl_absorpt_process_details   'SADABS (Bruker, 2012)'
_exptl_absorpt_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            13410
_diffrn_reflns_av_unetI/netI     0.0457
_diffrn_reflns_av_R_equivalents  0.0492
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         2.220
_diffrn_reflns_theta_max         25.997
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             2383
_reflns_number_gt                1396
_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       'APEXII (Bruker, 2012)'
_computing_cell_refinement       'APEXII/SAINT (Bruker, 2012)'
_computing_data_reduction        'SAINT/XPREP (Bruker, 2012)'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'ORTEP3 (Farrugia, 1997) '
_computing_publication_material  'SHELXL-2014/7 (Sheldrick, 2014)'

_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)+(0.0585P)²+2.0296P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_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         2383
_refine_ls_number_parameters     176
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.1254
_refine_ls_R_factor_gt           0.0693
_refine_ls_wR_factor_ref         0.1866
_refine_ls_wR_factor_gt          0.1557
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_restrained_S_all      1.031
_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
C1 C 0.6419(6) 0.6750(3) -0.0444(4) 0.0526(11) Uani 1 1 d . . . . .
C2 C 0.4900(5) 0.7319(2) 0.0030(3) 0.0368(9) Uani 1 1 d . . . . .
C3 C 0.3453(5) 0.6862(3) 0.0531(3) 0.0462(10) Uani 1 1 d . . . . .
H3 H 0.3414 0.6185 0.0566 0.055 Uiso 1 1 calc R U . . .
C4 C 0.2074(5) 0.7401(3) 0.0977(3) 0.0442(10) Uani 1 1 d . . . . .
H4 H 0.1106 0.7085 0.1317 0.053 Uiso 1 1 calc R U . . .
C5 C 0.2092(5) 0.8415(2) 0.0934(3) 0.0357(8) Uani 1 1 d . . . . .
C6 C 0.3555(5) 0.8866(3) 0.0435(3) 0.0464(10) Uani 1 1 d . . . . .
H6 H 0.3601 0.9543 0.0399 0.056 Uiso 1 1 calc R U . . .
C7 C 0.4947(5) 0.8318(3) -0.0008(3) 0.0466(10) Uani 1 1 d . . . . .
H7 H 0.5930 0.8630 -0.0337 0.056 Uiso 1 1 calc R U . . .
C8 C 0.0328(5) 0.9870(2) 0.1534(3) 0.0400(9) Uani 1 1 d . . . . .
C9 C -0.1379(5) 1.0153(2) 0.2080(3) 0.0376(9) Uani 1 1 d . . . . .
C10 C -0.1737(5) 1.1144(2) 0.2190(3) 0.0405(9) Uani 1 1 d . . . . .
H10 H -0.2834 1.1307 0.2527 0.049 Uiso 1 1 calc R U . . .
C11 C -0.2677(5) 0.9465(3) 0.2501(3) 0.0434(10) Uani 1 1 d . . . . .
C12 C -0.4417(6) 0.9803(3) 0.3046(4) 0.0683(14) Uani 1 1 d . . . . .
H12A H -0.4466 1.0502 0.3040 0.102 Uiso 1 1 calc R U . . .
H12B H -0.5495 0.9546 0.2663 0.102 Uiso 1 1 calc R U . . .
H12C H -0.4395 0.9574 0.3781 0.102 Uiso 1 1 calc R U . . .
N1 N 0.0619(4) 0.8899(2) 0.1405(3) 0.0413(8) Uani 1 1 d D . . . .
N2 N -0.0732(4) 1.1865(2) 0.1882(3) 0.0523(9) Uani 1 1 d . . . . .
H2A H 0.0297 1.1757 0.1566 0.063 Uiso 1 1 calc R U . . .
H2B H -0.1092 1.2454 0.1993 0.063 Uiso 1 1 calc R U . . .
O1 O 0.1459(4) 1.04755(18) 0.1222(3) 0.0646(9) Uani 1 1 d . . . . .
O2 O -0.2437(4) 0.85662(18) 0.2453(3) 0.0594(9) Uani 1 1 d . . . . .
F1 F 0.6035(4) 0.58299(18) -0.0608(3) 0.1072(13) Uani 1 1 d . . . . .
F2 F 0.7984(4) 0.6778(3) 0.0157(3) 0.1140(13) Uani 1 1 d . . . . .
F3 F 0.6942(4) 0.7085(2) -0.1387(2) 0.0859(10) Uani 1 1 d . . . . .
H1 H -0.030(4) 0.855(2) 0.169(3) 0.053(12) Uiso 1 1 d 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 F1 1.306(4) . ?
C1 F3 1.318(5) . ?
C1 F2 1.326(5) . ?
C1 C2 1.477(5) . ?
C2 C7 1.372(5) . ?
C2 C3 1.377(5) . ?
C3 C4 1.366(5) . ?
C3 H3 0.9300 . ?
C4 C5 1.392(5) . ?
C4 H4 0.9300 . ?
C5 C6 1.380(5) . ?
C5 N1 1.392(4) . ?
C6 C7 1.377(5) . ?
C6 H6 0.9300 . ?
C7 H7 0.9300 . ?
C8 O1 1.232(4) . ?
C8 N1 1.357(4) . ?
C8 C9 1.470(5) . ?
C9 C10 1.392(5) . ?
C9 C11 1.435(5) . ?
C10 N2 1.288(4) . ?
C10 H10 0.9300 . ?
C11 O2 1.247(4) . ?
C11 C12 1.510(5) . ?
C12 H12A 0.9600 . ?
C12 H12B 0.9600 . ?
C12 H12C 0.9600 . ?
N1 H1 0.898(10) . ?
N2 H2A 0.8600 . ?
N2 H2B 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
F1 C1 F3 105.3(4) . . ?
F1 C1 F2 106.5(4) . . ?
F3 C1 F2 102.9(3) . . ?
F1 C1 C2 114.6(3) . . ?
F3 C1 C2 113.7(3) . . ?
F2 C1 C2 112.7(4) . . ?
C7 C2 C3 119.3(3) . . ?
C7 C2 C1 119.6(3) . . ?
C3 C2 C1 121.1(3) . . ?
C4 C3 C2 120.2(3) . . ?
C4 C3 H3 119.9 . . ?
C2 C3 H3 119.9 . . ?
C3 C4 C5 121.2(3) . . ?
C3 C4 H4 119.4 . . ?
C5 C4 H4 119.4 . . ?
C6 C5 C4 118.2(3) . . ?
C6 C5 N1 124.9(3) . . ?
C4 C5 N1 116.9(3) . . ?
C7 C6 C5 120.3(3) . . ?
C7 C6 H6 119.8 . . ?
C5 C6 H6 119.8 . . ?
C2 C7 C6 120.9(3) . . ?
C2 C7 H7 119.6 . . ?
C6 C7 H7 119.6 . . ?
O1 C8 N1 121.3(3) . . ?
O1 C8 C9 122.2(3) . . ?
N1 C8 C9 116.5(3) . . ?
C10 C9 C11 118.9(3) . . ?
C10 C9 C8 117.5(3) . . ?
C11 C9 C8 123.6(3) . . ?
N2 C10 C9 127.9(3) . . ?
N2 C10 H10 116.0 . . ?
C9 C10 H10 116.0 . . ?
O2 C11 C9 122.7(3) . . ?
O2 C11 C12 116.2(3) . . ?
C9 C11 C12 121.1(3) . . ?
C11 C12 H12A 109.5 . . ?
C11 C12 H12B 109.5 . . ?
H12A C12 H12B 109.5 . . ?
C11 C12 H12C 109.5 . . ?
H12A C12 H12C 109.5 . . ?
H12B C12 H12C 109.5 . . ?
C8 N1 C5 129.7(3) . . ?
C8 N1 H1 111(2) . . ?
C5 N1 H1 119(2) . . ?
C10 N2 H2A 120.0 . . ?
C10 N2 H2B 120.0 . . ?
H2A N2 H2B 120.0 . . ?

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
F1 C1 C2 C7 -164.0(4) . . . . ?
F3 C1 C2 C7 -42.7(6) . . . . ?
F2 C1 C2 C7 74.0(5) . . . . ?
F1 C1 C2 C3 17.5(6) . . . . ?
F3 C1 C2 C3 138.7(4) . . . . ?
F2 C1 C2 C3 -104.6(5) . . . . ?
C7 C2 C3 C4 0.5(6) . . . . ?
C1 C2 C3 C4 179.1(4) . . . . ?
C2 C3 C4 C5 0.3(7) . . . . ?
C3 C4 C5 C6 -0.7(6) . . . . ?
C3 C4 C5 N1 179.6(4) . . . . ?
C4 C5 C6 C7 0.3(6) . . . . ?
N1 C5 C6 C7 -180.0(4) . . . . ?
C3 C2 C7 C6 -0.9(6) . . . . ?
C1 C2 C7 C6 -179.5(4) . . . . ?
C5 C6 C7 C2 0.5(7) . . . . ?
O1 C8 C9 C10 3.1(6) . . . . ?
N1 C8 C9 C10 -178.0(4) . . . . ?
O1 C8 C9 C11 -176.7(4) . . . . ?
N1 C8 C9 C11 2.2(6) . . . . ?
C11 C9 C10 N2 178.8(4) . . . . ?
C8 C9 C10 N2 -1.0(6) . . . . ?
C10 C9 C11 O2 -178.6(4) . . . . ?
C8 C9 C11 O2 1.2(6) . . . . ?
C10 C9 C11 C12 0.7(6) . . . . ?
C8 C9 C11 C12 -179.5(4) . . . . ?
O1 C8 N1 C5 -0.6(7) . . . . ?
C9 C8 N1 C5 -179.5(4) . . . . ?
C6 C5 N1 C8 -3.7(7) . . . . ?
C4 C5 N1 C8 176.0(4) . . . . ?

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
N2 H2A F3 0.86 2.55 3.155(4) 127.8 3_675
N2 H2B O2 0.86 1.99 2.813(4) 160.0 2_455

_refine_diff_density_max         0.430
_refine_diff_density_min         -0.276
_refine_diff_density_rms         0.053


_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent'
_solvent_exptl_crystal_recrystallization_method Ethanol
