# Electronic Supplementary Material (ESI) for Organic Chemistry Frontiers.
# This journal is © the Partner Organisations 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_xe1012
_database_code_depnum_ccdc_archive 'CCDC 1539496'
_audit_update_record             
;
2017-03-22 deposited with the CCDC.
2017-04-17 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C21 H17 Cl F3 N3'
_chemical_formula_sum            'C21 H17 Cl F3 N3'
_chemical_formula_weight         403.83
_chemical_absolute_configuration ad


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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'P 1 21 1'
_symmetry_space_group_name_Hall  'P 2yb'

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

_cell_length_a                   8.6045(6)
_cell_length_b                   11.4959(7)
_cell_length_c                   10.3691(6)
_cell_angle_alpha                90.00
_cell_angle_beta                 114.544(2)
_cell_angle_gamma                90.00
_cell_volume                     933.00(10)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    5992
_cell_measurement_theta_min      3.1
_cell_measurement_theta_max      27.5

_exptl_crystal_description       platelet
_exptl_crystal_colour            colorless
_exptl_crystal_size_max          0.52
_exptl_crystal_size_mid          0.36
_exptl_crystal_size_min          0.11
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.437
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             416
_exptl_absorpt_coefficient_mu    0.245
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8831
_exptl_absorpt_correction_T_max  0.9735
_exptl_absorpt_process_details   'Higashi, T. (1995)'

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'rotating anode'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'Rigaku RAXIS-RAPID/ZJUG'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean 10.00
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8130
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_sigmaI/netI    0.0436
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         3.15
_diffrn_reflns_theta_max         25.99
_reflns_number_total             3197
_reflns_number_gt                2112
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'PROCESS-AUTO  (Rigaku,2006)'
_computing_cell_refinement       'PROCESS-AUTO  (Rigaku,2006)'
_computing_data_reduction        'CrystalStructure (Rigaku,2007)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2014)'
_computing_molecular_graphics    'Ortep3 for windows (Farrugia,1997)'
_computing_publication_material  'WinGX (Farrugia, 1999)'

_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)+(0.0239P)²+0.4674P] 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     SHELXL
_refine_ls_extinction_coef       0.0268(18)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   -0.02(9)
_refine_ls_number_reflns         3197
_refine_ls_number_parameters     255
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0341
_refine_ls_wR_factor_ref         0.0903
_refine_ls_wR_factor_gt          0.0633
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_restrained_S_all      1.003
_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 0.2414(5) 0.7082(3) 0.8247(3) 0.0526(9) Uani 1 1 d . . .
C2 C 0.0939(4) 0.6832(4) 0.7041(3) 0.0538(9) Uani 1 1 d . . .
H2 H 0.0013 0.6485 0.7131 0.065 Uiso 1 1 calc R . .
C3 C 0.0844(4) 0.7098(3) 0.5712(4) 0.0563(10) Uani 1 1 d . . .
H3 H -0.0127 0.6927 0.4897 0.068 Uiso 1 1 calc R . .
C4 C 0.2253(4) 0.7630(3) 0.5639(3) 0.0450(9) Uani 1 1 d . . .
C5 C 0.4129(4) 0.8468(3) 0.4942(3) 0.0463(9) Uani 1 1 d . . .
C6 C 0.4930(4) 0.8928(3) 0.3999(3) 0.0463(8) Uani 1 1 d . . .
C7 C 0.7515(5) 0.9124(4) 0.6174(4) 0.0668(11) Uani 1 1 d . . .
H7A H 0.8508 0.9615 0.6646 0.080 Uiso 1 1 calc R . .
H7B H 0.7892 0.8408 0.5900 0.080 Uiso 1 1 calc R . .
C8 C 0.6702(4) 0.8846(4) 0.7203(4) 0.0586(10) Uani 1 1 d . . .
H8A H 0.7368 0.8255 0.7872 0.070 Uiso 1 1 calc R . .
H8B H 0.6686 0.9538 0.7732 0.070 Uiso 1 1 calc R . .
C9 C 0.4933(4) 0.8423(3) 0.6383(3) 0.0465(9) Uani 1 1 d . . .
C10 C 0.3756(4) 0.7884(3) 0.6861(3) 0.0450(8) Uani 1 1 d . . .
C11 C 0.3816(5) 0.7593(3) 0.8196(4) 0.0506(9) Uani 1 1 d . . .
H11 H 0.4784 0.7745 0.9022 0.061 Uiso 1 1 calc R . .
C12 C 0.3649(5) 0.9706(4) 0.2868(4) 0.0559(10) Uani 1 1 d . . .
C13 C 0.5536(4) 0.7937(3) 0.3359(3) 0.0430(8) Uani 1 1 d . . .
C14 C 0.5325(4) 0.6788(3) 0.3565(3) 0.0481(8) Uani 1 1 d . . .
H14 H 0.4706 0.6504 0.4049 0.058 Uiso 1 1 calc R . .
C15 C 0.6936(4) 0.6825(3) 0.2345(3) 0.0439(8) Uani 1 1 d . . .
C16 C 0.7917(4) 0.6496(3) 0.1622(3) 0.0509(9) Uani 1 1 d . . .
C17 C 0.8609(5) 0.7395(4) 0.1156(4) 0.0612(11) Uani 1 1 d . . .
H17 H 0.9291 0.7224 0.0682 0.073 Uiso 1 1 calc R . .
C18 C 0.8318(5) 0.8550(4) 0.1375(4) 0.0628(11) Uani 1 1 d . . .
H18 H 0.8818 0.9131 0.1051 0.075 Uiso 1 1 calc R . .
C19 C 0.7307(4) 0.8861(3) 0.2061(4) 0.0563(10) Uani 1 1 d . . .
H19 H 0.7110 0.9641 0.2182 0.068 Uiso 1 1 calc R . .
C20 C 0.6585(4) 0.7987(3) 0.2569(3) 0.0438(8) Uani 1 1 d . . .
C21 C 0.8128(5) 0.5231(4) 0.1356(4) 0.0692(12) Uani 1 1 d . . .
H21A H 0.7055 0.4923 0.0696 0.104 Uiso 1 1 calc R . .
H21B H 0.8502 0.4809 0.2232 0.104 Uiso 1 1 calc R . .
H21C H 0.8962 0.5154 0.0969 0.104 Uiso 1 1 calc R . .
N2 N 0.6302(4) 0.9718(3) 0.4905(3) 0.0539(8) Uani 1 1 d . . .
H2A H 0.6865 0.9985 0.4403 0.065 Uiso 1 1 d R . .
N1 N 0.2519(3) 0.7980(3) 0.4471(3) 0.0494(7) Uani 1 1 d . . .
H1A H 0.1804 0.7906 0.3600 0.059 Uiso 1 1 calc R . .
N3 N 0.6150(4) 0.6111(3) 0.2963(3) 0.0513(8) Uani 1 1 d . . .
H3A H 0.6175 0.5363 0.2968 0.062 Uiso 1 1 calc R . .
F1 F 0.2343(2) 0.90921(19) 0.19183(19) 0.0643(6) Uani 1 1 d . . .
F2 F 0.4337(3) 1.0283(2) 0.2104(2) 0.0715(7) Uani 1 1 d . . .
F3 F 0.2936(3) 1.0506(2) 0.3384(2) 0.0804(7) Uani 1 1 d . . .
Cl1 Cl 0.24330(15) 0.67338(11) 0.98982(10) 0.0768(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
C1 C11 1.363(5) . ?
C1 C2 1.392(5) . ?
C1 Cl1 1.752(3) . ?
C2 C3 1.380(4) . ?
C2 H2 0.9300 . ?
C3 C4 1.388(5) . ?
C3 H3 0.9300 . ?
C4 N1 1.382(4) . ?
C4 C10 1.415(4) . ?
C5 C9 1.362(4) . ?
C5 N1 1.383(4) . ?
C5 C6 1.506(4) . ?
C6 N2 1.477(4) . ?
C6 C13 1.515(5) . ?
C6 C12 1.523(5) . ?
C7 N2 1.464(5) . ?
C7 C8 1.532(5) . ?
C7 H7A 0.9700 . ?
C7 H7B 0.9700 . ?
C8 C9 1.484(4) . ?
C8 H8A 0.9700 . ?
C8 H8B 0.9700 . ?
C9 C10 1.439(5) . ?
C10 C11 1.404(4) . ?
C11 H11 0.9300 . ?
C12 F3 1.334(4) . ?
C12 F2 1.343(4) . ?
C12 F1 1.346(4) . ?
C13 C14 1.363(5) . ?
C13 C20 1.450(4) . ?
C14 N3 1.367(4) . ?
C14 H14 0.9300 . ?
C15 N3 1.379(4) . ?
C15 C16 1.394(4) . ?
C15 C20 1.410(5) . ?
C16 C17 1.377(5) . ?
C16 C21 1.506(5) . ?
C17 C18 1.387(6) . ?
C17 H17 0.9300 . ?
C18 C19 1.380(5) . ?
C18 H18 0.9300 . ?
C19 C20 1.395(5) . ?
C19 H19 0.9300 . ?
C21 H21A 0.9600 . ?
C21 H21B 0.9600 . ?
C21 H21C 0.9600 . ?
N2 H2A 0.9000 . ?
N1 H1A 0.8600 . ?
N3 H3A 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
C11 C1 C2 123.1(3) . . ?
C11 C1 Cl1 119.1(3) . . ?
C2 C1 Cl1 117.8(3) . . ?
C3 C2 C1 120.3(3) . . ?
C3 C2 H2 119.8 . . ?
C1 C2 H2 119.8 . . ?
C2 C3 C4 117.5(3) . . ?
C2 C3 H3 121.3 . . ?
C4 C3 H3 121.3 . . ?
N1 C4 C3 130.0(3) . . ?
N1 C4 C10 107.6(3) . . ?
C3 C4 C10 122.4(3) . . ?
C9 C5 N1 110.4(3) . . ?
C9 C5 C6 124.4(3) . . ?
N1 C5 C6 125.1(3) . . ?
N2 C6 C5 105.3(3) . . ?
N2 C6 C13 114.3(3) . . ?
C5 C6 C13 110.8(3) . . ?
N2 C6 C12 105.1(3) . . ?
C5 C6 C12 109.0(3) . . ?
C13 C6 C12 112.0(3) . . ?
N2 C7 C8 111.3(3) . . ?
N2 C7 H7A 109.4 . . ?
C8 C7 H7A 109.4 . . ?
N2 C7 H7B 109.4 . . ?
C8 C7 H7B 109.4 . . ?
H7A C7 H7B 108.0 . . ?
C9 C8 C7 109.0(3) . . ?
C9 C8 H8A 109.9 . . ?
C7 C8 H8A 109.9 . . ?
C9 C8 H8B 109.9 . . ?
C7 C8 H8B 109.9 . . ?
H8A C8 H8B 108.3 . . ?
C5 C9 C10 106.6(3) . . ?
C5 C9 C8 123.2(3) . . ?
C10 C9 C8 130.2(3) . . ?
C11 C10 C4 118.7(3) . . ?
C11 C10 C9 134.3(3) . . ?
C4 C10 C9 107.0(3) . . ?
C1 C11 C10 118.0(3) . . ?
C1 C11 H11 121.0 . . ?
C10 C11 H11 121.0 . . ?
F3 C12 F2 106.6(3) . . ?
F3 C12 F1 105.7(3) . . ?
F2 C12 F1 105.4(3) . . ?
F3 C12 C6 113.7(3) . . ?
F2 C12 C6 112.9(3) . . ?
F1 C12 C6 111.9(3) . . ?
C14 C13 C20 106.4(3) . . ?
C14 C13 C6 124.5(3) . . ?
C20 C13 C6 128.8(3) . . ?
C13 C14 N3 110.6(3) . . ?
C13 C14 H14 124.7 . . ?
N3 C14 H14 124.7 . . ?
N3 C15 C16 127.7(3) . . ?
N3 C15 C20 107.9(3) . . ?
C16 C15 C20 124.4(3) . . ?
C17 C16 C15 115.6(4) . . ?
C17 C16 C21 124.0(3) . . ?
C15 C16 C21 120.5(4) . . ?
C16 C17 C18 121.9(3) . . ?
C16 C17 H17 119.1 . . ?
C18 C17 H17 119.1 . . ?
C19 C18 C17 121.8(4) . . ?
C19 C18 H18 119.1 . . ?
C17 C18 H18 119.1 . . ?
C18 C19 C20 118.9(4) . . ?
C18 C19 H19 120.6 . . ?
C20 C19 H19 120.6 . . ?
C19 C20 C15 117.4(3) . . ?
C19 C20 C13 136.2(3) . . ?
C15 C20 C13 106.4(3) . . ?
C16 C21 H21A 109.5 . . ?
C16 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C16 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C7 N2 C6 111.6(3) . . ?
C7 N2 H2A 109.0 . . ?
C6 N2 H2A 108.8 . . ?
C4 N1 C5 108.4(3) . . ?
C4 N1 H1A 125.8 . . ?
C5 N1 H1A 125.8 . . ?
C14 N3 C15 108.7(3) . . ?
C14 N3 H3A 125.6 . . ?
C15 N3 H3A 125.6 . . ?

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
C11 C1 C2 C3 0.2(6) . . . . ?
Cl1 C1 C2 C3 179.3(3) . . . . ?
C1 C2 C3 C4 -0.8(6) . . . . ?
C2 C3 C4 N1 179.4(4) . . . . ?
C2 C3 C4 C10 0.9(5) . . . . ?
C9 C5 C6 N2 -23.5(5) . . . . ?
N1 C5 C6 N2 160.1(3) . . . . ?
C9 C5 C6 C13 100.6(4) . . . . ?
N1 C5 C6 C13 -75.8(4) . . . . ?
C9 C5 C6 C12 -135.8(3) . . . . ?
N1 C5 C6 C12 47.8(5) . . . . ?
N2 C7 C8 C9 41.6(5) . . . . ?
N1 C5 C9 C10 -0.7(4) . . . . ?
C6 C5 C9 C10 -177.5(3) . . . . ?
N1 C5 C9 C8 178.0(3) . . . . ?
C6 C5 C9 C8 1.2(6) . . . . ?
C7 C8 C9 C5 -9.5(5) . . . . ?
C7 C8 C9 C10 168.9(4) . . . . ?
N1 C4 C10 C11 -179.2(3) . . . . ?
C3 C4 C10 C11 -0.4(5) . . . . ?
N1 C4 C10 C9 1.0(4) . . . . ?
C3 C4 C10 C9 179.8(3) . . . . ?
C5 C9 C10 C11 180.0(4) . . . . ?
C8 C9 C10 C11 1.4(7) . . . . ?
C5 C9 C10 C4 -0.2(4) . . . . ?
C8 C9 C10 C4 -178.8(4) . . . . ?
C2 C1 C11 C10 0.3(5) . . . . ?
Cl1 C1 C11 C10 -178.8(3) . . . . ?
C4 C10 C11 C1 -0.2(5) . . . . ?
C9 C10 C11 C1 179.5(4) . . . . ?
N2 C6 C12 F3 -62.8(4) . . . . ?
C5 C6 C12 F3 49.6(4) . . . . ?
C13 C6 C12 F3 172.6(3) . . . . ?
N2 C6 C12 F2 58.8(4) . . . . ?
C5 C6 C12 F2 171.2(3) . . . . ?
C13 C6 C12 F2 -65.9(4) . . . . ?
N2 C6 C12 F1 177.5(3) . . . . ?
C5 C6 C12 F1 -70.1(4) . . . . ?
C13 C6 C12 F1 52.9(4) . . . . ?
N2 C6 C13 C14 121.0(4) . . . . ?
C5 C6 C13 C14 2.3(4) . . . . ?
C12 C6 C13 C14 -119.6(4) . . . . ?
N2 C6 C13 C20 -51.4(4) . . . . ?
C5 C6 C13 C20 -170.1(3) . . . . ?
C12 C6 C13 C20 67.9(4) . . . . ?
C20 C13 C14 N3 -0.3(4) . . . . ?
C6 C13 C14 N3 -174.2(3) . . . . ?
N3 C15 C16 C17 -177.6(3) . . . . ?
C20 C15 C16 C17 2.2(5) . . . . ?
N3 C15 C16 C21 4.1(5) . . . . ?
C20 C15 C16 C21 -176.1(3) . . . . ?
C15 C16 C17 C18 -1.1(5) . . . . ?
C21 C16 C17 C18 177.2(3) . . . . ?
C16 C17 C18 C19 -0.6(6) . . . . ?
C17 C18 C19 C20 1.2(6) . . . . ?
C18 C19 C20 C15 -0.1(5) . . . . ?
C18 C19 C20 C13 177.5(4) . . . . ?
N3 C15 C20 C19 178.2(3) . . . . ?
C16 C15 C20 C19 -1.6(5) . . . . ?
N3 C15 C20 C13 -0.1(3) . . . . ?
C16 C15 C20 C13 -179.9(3) . . . . ?
C14 C13 C20 C19 -177.6(4) . . . . ?
C6 C13 C20 C19 -4.1(6) . . . . ?
C14 C13 C20 C15 0.2(3) . . . . ?
C6 C13 C20 C15 173.7(3) . . . . ?
C8 C7 N2 C6 -70.1(4) . . . . ?
C5 C6 N2 C7 56.4(3) . . . . ?
C13 C6 N2 C7 -65.4(3) . . . . ?
C12 C6 N2 C7 171.5(3) . . . . ?
C3 C4 N1 C5 180.0(4) . . . . ?
C10 C4 N1 C5 -1.4(4) . . . . ?
C9 C5 N1 C4 1.3(4) . . . . ?
C6 C5 N1 C4 178.2(3) . . . . ?
C13 C14 N3 C15 0.3(4) . . . . ?
C16 C15 N3 C14 179.7(3) . . . . ?
C20 C15 N3 C14 -0.1(4) . . . . ?

_diffrn_measured_fraction_theta_max 0.997
_diffrn_reflns_theta_full        25.99
_diffrn_measured_fraction_theta_full 0.997
_refine_diff_density_max         0.208
_refine_diff_density_min         -0.264
_refine_diff_density_rms         0.051

