# Electronic Supplementary Material (ESI) for ChemComm.
# 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_t_sq
_audit_block_doi                 10.5517/ccdc.csd.cc1q3c8g
_database_code_depnum_ccdc_archive 'CCDC 1582155'
_audit_update_record             
;
2017-10-26 deposited with the CCDC.
2017-10-27 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         'C19 H16 Br F N4 O'
_chemical_formula_sum            'C19 H16 Br F N4 O'
_chemical_formula_weight         415.27

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'
Br Br -0.2901 2.4595 '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'
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'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

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

_cell_length_a                   14.3713(15)
_cell_length_b                   13.0309(13)
_cell_length_c                   11.6849(11)
_cell_angle_alpha                90
_cell_angle_beta                 112.040(3)
_cell_angle_gamma                90
_cell_volume                     2028.3(4)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    9169
_cell_measurement_theta_min      2.45
_cell_measurement_theta_max      27.19

_exptl_crystal_description       block
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.360
_exptl_crystal_F_000             840
_exptl_transmission_factor_min   0.618
_exptl_transmission_factor_max   0.815
_exptl_crystal_size_max          0.300
_exptl_crystal_size_mid          0.200
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    2.049
_shelx_estimated_absorpt_T_min   0.578
_shelx_estimated_absorpt_T_max   0.821
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_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 APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            42413
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_av_R_equivalents  0.0400
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         2.186
_diffrn_reflns_theta_max         27.523
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measured_fraction_theta_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_point_group_measured_fraction_full 0.996
_reflns_number_total             4643
_reflns_number_gt                3698
_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.
 
 Structure factors included contributions from the .fab file.
 
 _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 APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick 2008)'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_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)+(0.1800P)²+2.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4643
_refine_ls_number_parameters     237
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0758
_refine_ls_R_factor_gt           0.0581
_refine_ls_wR_factor_ref         0.2302
_refine_ls_wR_factor_gt          0.2075
_refine_ls_goodness_of_fit_ref   0.922
_refine_ls_restrained_S_all      0.922
_refine_ls_shift/su_max          0.001
_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
Br1 Br 0.53568(3) 0.39190(4) 0.12725(5) 0.0700(3) Uani 1 1 d . . . . .
F1 F -0.0432(2) -0.0920(2) 0.1263(3) 0.0635(7) Uani 1 1 d . . . . .
O1 O -0.2925(2) 0.3185(2) -0.1439(2) 0.0514(6) Uani 1 1 d . . . . .
N1 N 0.2319(2) 0.0531(2) 0.2869(3) 0.0421(6) Uani 1 1 d . . . . .
N2 N 0.1496(2) 0.0184(2) 0.2972(3) 0.0439(7) Uani 1 1 d . . . . .
N3 N 0.0737(2) 0.0771(2) 0.2244(2) 0.0346(6) Uani 1 1 d . . . . .
N4 N -0.0033(4) 0.1305(4) 0.4539(4) 0.0710(11) Uani 1 1 d . . . . .
C1 C 0.2861(2) 0.1921(2) 0.1826(3) 0.0359(6) Uani 1 1 d . . . . .
C2 C 0.3860(3) 0.1840(4) 0.2636(4) 0.0571(10) Uani 1 1 d . . . . .
H2 H 0.403055 0.139220 0.330350 0.069 Uiso 1 1 calc R U . . .
C3 C 0.4592(3) 0.2416(4) 0.2453(4) 0.0635(12) Uani 1 1 d . . . . .
H3 H 0.525725 0.235376 0.299162 0.076 Uiso 1 1 calc R U . . .
C4 C 0.4339(3) 0.3088(3) 0.1468(4) 0.0476(8) Uani 1 1 d . . . . .
C5 C 0.3366(3) 0.3189(3) 0.0671(3) 0.0482(8) Uani 1 1 d . . . . .
H5 H 0.320070 0.364782 0.001492 0.058 Uiso 1 1 calc R U . . .
C6 C 0.2629(3) 0.2604(3) 0.0849(3) 0.0441(8) Uani 1 1 d . . . . .
H6 H 0.196655 0.266967 0.030394 0.053 Uiso 1 1 calc R U . . .
C7 C 0.2085(2) 0.1344(2) 0.2078(3) 0.0346(6) Uani 1 1 d . . . . .
C8 C 0.1072(2) 0.1504(2) 0.1667(3) 0.0356(6) Uani 1 1 d . . . . .
H8 H 0.069722 0.200215 0.111691 0.043 Uiso 1 1 calc R U . . .
C9 C -0.0280(3) 0.0640(3) 0.2297(3) 0.0405(7) Uani 1 1 d . . . . .
C10 C -0.0531(3) -0.0497(3) 0.2285(4) 0.0542(9) Uani 1 1 d . . . . .
H10 H -0.004250 -0.081969 0.302454 0.065 Uiso 1 1 calc R U . . .
C11 C -0.1568(4) -0.0709(4) 0.2248(5) 0.0718(13) Uani 1 1 d . . . . .
H11A H -0.163856 -0.042098 0.296733 0.108 Uiso 1 1 calc R U . . .
H11B H -0.167483 -0.143659 0.223263 0.108 Uiso 1 1 calc R U . . .
H11C H -0.205289 -0.040434 0.152052 0.108 Uiso 1 1 calc R U . . .
C12 C -0.0138(4) 0.1052(3) 0.3610(4) 0.0567(11) Uani 1 1 d . . . . .
C13 C -0.1039(2) 0.1303(2) 0.1306(3) 0.0344(6) Uani 1 1 d . . . . .
C14 C -0.1358(3) 0.2219(3) 0.1622(3) 0.0453(8) Uani 1 1 d . . . . .
H14 H -0.113746 0.240814 0.244853 0.054 Uiso 1 1 calc R U . . .
C15 C -0.2002(3) 0.2868(3) 0.0729(3) 0.0472(8) Uani 1 1 d . . . . .
H15 H -0.221182 0.348304 0.095758 0.057 Uiso 1 1 calc R U . . .
C16 C -0.2327(2) 0.2590(3) -0.0502(3) 0.0388(7) Uani 1 1 d . . . . .
C17 C -0.2031(3) 0.1658(3) -0.0833(3) 0.0407(7) Uani 1 1 d . . . . .
H17 H -0.226711 0.146074 -0.165755 0.049 Uiso 1 1 calc R U . . .
C18 C -0.1388(3) 0.1023(3) 0.0061(3) 0.0415(8) Uani 1 1 d . . . . .
H18 H -0.118437 0.040409 -0.016717 0.050 Uiso 1 1 calc R U . . .
C19 C -0.3148(5) 0.4189(4) -0.1125(5) 0.0705(13) Uani 1 1 d . . . . .
H19A H -0.349004 0.413692 -0.056184 0.106 Uiso 1 1 calc R U . . .
H19B H -0.356907 0.453976 -0.185927 0.106 Uiso 1 1 calc R U . . .
H19C H -0.253512 0.456632 -0.074202 0.106 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
Br1 C4 1.902(4) . ?
F1 C10 1.371(5) . ?
O1 C16 1.353(4) . ?
O1 C19 1.428(5) . ?
N1 N2 1.313(4) . ?
N1 C7 1.361(4) . ?
N2 N3 1.343(4) . ?
N3 C8 1.357(4) . ?
N3 C9 1.495(4) . ?
N4 C12 1.090(6) . ?
C1 C6 1.386(5) . ?
C1 C2 1.395(5) . ?
C1 C7 1.465(5) . ?
C2 C3 1.373(6) . ?
C2 H2 0.9300 . ?
C3 C4 1.382(5) . ?
C3 H3 0.9300 . ?
C4 C5 1.364(5) . ?
C5 C6 1.383(5) . ?
C5 H5 0.9300 . ?
C6 H6 0.9300 . ?
C7 C8 1.367(5) . ?
C8 H8 0.9300 . ?
C9 C13 1.526(5) . ?
C9 C10 1.523(5) . ?
C9 C12 1.565(6) . ?
C10 C11 1.500(6) . ?
C10 H10 0.9800 . ?
C11 H11A 0.9600 . ?
C11 H11B 0.9600 . ?
C11 H11C 0.9600 . ?
C13 C14 1.378(5) . ?
C13 C18 1.398(5) . ?
C14 C15 1.391(5) . ?
C14 H14 0.9300 . ?
C15 C16 1.384(5) . ?
C15 H15 0.9300 . ?
C16 C17 1.389(5) . ?
C17 C18 1.380(5) . ?
C17 H17 0.9300 . ?
C18 H18 0.9300 . ?
C19 H19A 0.9600 . ?
C19 H19B 0.9600 . ?
C19 H19C 0.9600 . ?

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
C16 O1 C19 116.9(3) . . ?
N2 N1 C7 109.2(3) . . ?
N1 N2 N3 106.9(3) . . ?
N2 N3 C8 111.1(3) . . ?
N2 N3 C9 118.9(3) . . ?
C8 N3 C9 129.4(3) . . ?
C6 C1 C2 118.4(3) . . ?
C6 C1 C7 122.0(3) . . ?
C2 C1 C7 119.5(3) . . ?
C3 C2 C1 120.4(3) . . ?
C3 C2 H2 119.8 . . ?
C1 C2 H2 119.8 . . ?
C4 C3 C2 119.9(4) . . ?
C4 C3 H3 120.1 . . ?
C2 C3 H3 120.1 . . ?
C5 C4 C3 120.8(3) . . ?
C5 C4 Br1 120.0(3) . . ?
C3 C4 Br1 119.1(3) . . ?
C4 C5 C6 119.3(3) . . ?
C4 C5 H5 120.3 . . ?
C6 C5 H5 120.3 . . ?
C1 C6 C5 121.1(3) . . ?
C1 C6 H6 119.4 . . ?
C5 C6 H6 119.4 . . ?
N1 C7 C8 108.5(3) . . ?
N1 C7 C1 121.5(3) . . ?
C8 C7 C1 130.0(3) . . ?
N3 C8 C7 104.3(3) . . ?
N3 C8 H8 127.8 . . ?
C7 C8 H8 127.8 . . ?
N3 C9 C13 109.6(3) . . ?
N3 C9 C10 110.0(3) . . ?
C13 C9 C10 116.3(3) . . ?
N3 C9 C12 103.4(3) . . ?
C13 C9 C12 110.0(3) . . ?
C10 C9 C12 106.6(3) . . ?
F1 C10 C11 109.1(4) . . ?
F1 C10 C9 107.3(3) . . ?
C11 C10 C9 114.1(4) . . ?
F1 C10 H10 108.7 . . ?
C11 C10 H10 108.7 . . ?
C9 C10 H10 108.7 . . ?
C10 C11 H11A 109.5 . . ?
C10 C11 H11B 109.5 . . ?
H11A C11 H11B 109.5 . . ?
C10 C11 H11C 109.5 . . ?
H11A C11 H11C 109.5 . . ?
H11B C11 H11C 109.5 . . ?
N4 C12 C9 177.6(5) . . ?
C14 C13 C18 118.7(3) . . ?
C14 C13 C9 120.2(3) . . ?
C18 C13 C9 121.1(3) . . ?
C13 C14 C15 121.4(3) . . ?
C13 C14 H14 119.3 . . ?
C15 C14 H14 119.3 . . ?
C16 C15 C14 119.4(3) . . ?
C16 C15 H15 120.3 . . ?
C14 C15 H15 120.3 . . ?
O1 C16 C15 123.7(3) . . ?
O1 C16 C17 116.3(3) . . ?
C15 C16 C17 119.9(3) . . ?
C18 C17 C16 120.2(3) . . ?
C18 C17 H17 119.9 . . ?
C16 C17 H17 119.9 . . ?
C17 C18 C13 120.5(3) . . ?
C17 C18 H18 119.8 . . ?
C13 C18 H18 119.8 . . ?
O1 C19 H19A 109.5 . . ?
O1 C19 H19B 109.5 . . ?
H19A C19 H19B 109.5 . . ?
O1 C19 H19C 109.5 . . ?
H19A C19 H19C 109.5 . . ?
H19B C19 H19C 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 N2 N3 0.2(4) . . . . ?
N1 N2 N3 C8 0.0(4) . . . . ?
N1 N2 N3 C9 -172.3(3) . . . . ?
C6 C1 C2 C3 -0.8(7) . . . . ?
C7 C1 C2 C3 -176.5(4) . . . . ?
C1 C2 C3 C4 0.6(8) . . . . ?
C2 C3 C4 C5 0.1(7) . . . . ?
C2 C3 C4 Br1 177.4(4) . . . . ?
C3 C4 C5 C6 -0.6(6) . . . . ?
Br1 C4 C5 C6 -177.9(3) . . . . ?
C2 C1 C6 C5 0.3(6) . . . . ?
C7 C1 C6 C5 175.9(3) . . . . ?
C4 C5 C6 C1 0.4(6) . . . . ?
N2 N1 C7 C8 -0.4(4) . . . . ?
N2 N1 C7 C1 177.1(3) . . . . ?
C6 C1 C7 N1 166.5(3) . . . . ?
C2 C1 C7 N1 -18.0(5) . . . . ?
C6 C1 C7 C8 -16.6(5) . . . . ?
C2 C1 C7 C8 158.9(4) . . . . ?
N2 N3 C8 C7 -0.2(4) . . . . ?
C9 N3 C8 C7 171.0(3) . . . . ?
N1 C7 C8 N3 0.3(4) . . . . ?
C1 C7 C8 N3 -176.9(3) . . . . ?
N2 N3 C9 C13 -174.3(3) . . . . ?
C8 N3 C9 C13 15.1(5) . . . . ?
N2 N3 C9 C10 -45.1(4) . . . . ?
C8 N3 C9 C10 144.3(3) . . . . ?
N2 N3 C9 C12 68.4(4) . . . . ?
C8 N3 C9 C12 -102.2(4) . . . . ?
N3 C9 C10 F1 -55.0(4) . . . . ?
C13 C9 C10 F1 70.4(4) . . . . ?
C12 C9 C10 F1 -166.5(3) . . . . ?
N3 C9 C10 C11 -176.0(3) . . . . ?
C13 C9 C10 C11 -50.6(5) . . . . ?
C12 C9 C10 C11 72.5(5) . . . . ?
N3 C9 C13 C14 -102.1(4) . . . . ?
C10 C9 C13 C14 132.3(4) . . . . ?
C12 C9 C13 C14 11.0(5) . . . . ?
N3 C9 C13 C18 74.7(4) . . . . ?
C10 C9 C13 C18 -51.0(5) . . . . ?
C12 C9 C13 C18 -172.3(3) . . . . ?
C18 C13 C14 C15 -0.9(6) . . . . ?
C9 C13 C14 C15 176.0(3) . . . . ?
C13 C14 C15 C16 -0.3(6) . . . . ?
C19 O1 C16 C15 5.8(6) . . . . ?
C19 O1 C16 C17 -173.6(4) . . . . ?
C14 C15 C16 O1 -177.6(3) . . . . ?
C14 C15 C16 C17 1.7(6) . . . . ?
O1 C16 C17 C18 177.3(3) . . . . ?
C15 C16 C17 C18 -2.1(5) . . . . ?
C16 C17 C18 C13 1.0(6) . . . . ?
C14 C13 C18 C17 0.5(5) . . . . ?
C9 C13 C18 C17 -176.3(3) . . . . ?

_refine_diff_density_max         1.017
_refine_diff_density_min         -0.970
_refine_diff_density_rms         0.153




####################################################################### 
# 
# 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_g170327c
_database_code_depnum_ccdc_archive 'CCDC 1556663'
_audit_update_record             
;
2017-06-17 deposited with the CCDC.
2017-10-27 downloaded from the CCDC.
;
_audit_creation_date             2017-03-28
_audit_creation_method           
;
Olex2 1.2
(compiled 2017.02.23 svn.r3390 for OlexSys, GUI svn.r5320)
;
_shelx_SHELXL_version_number     2014/7
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C20 H17 F N4 O, C H2 Cl2'
_chemical_formula_sum            'C21 H19 Cl2 F N4 O'
_chemical_formula_weight         433.30
_chemical_melting_point          ?
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'
Cl Cl 0.1484 0.1585 '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'
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'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/n 1'
_space_group_name_Hall           '-P 2yn'
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                   9.168(5)
_cell_length_b                   26.759(9)
_cell_length_c                   9.365(3)
_cell_angle_alpha                90
_cell_angle_beta                 108.96(5)
_cell_angle_gamma                90
_cell_volume                     2172.7(17)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    939
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      20.6630
_cell_measurement_theta_min      4.5290
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    0.326
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.00445
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    1.325
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             896
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.1026
_diffrn_reflns_av_unetI/netI     0.1323
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            12518
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.371
_diffrn_reflns_theta_min         3.101
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4471
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_details      
;
#__ type_ start__ end____ width___ exp.time_
  1 omega   38.00   63.80   0.3000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       10.8090  178.0000   60.0000 86

#__ type_ start__ end____ width___ exp.time_
  2 omega  -52.00   42.20   0.3000   15.0000
omega____ theta____ kappa____ phi______ frames
    -       10.8090  -77.0000   90.0000 314

#__ type_ start__ end____ width___ exp.time_
  3 omega  -11.00   14.20   0.3000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.7465  -99.0000   90.0000 84

#__ type_ start__ end____ width___ exp.time_
  4 omega  -69.00   13.50   0.3000   15.0000
omega____ theta____ kappa____ phi______ frames
    -      -11.7465  -57.0000 -180.0000 275
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Atlas, Gemini'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_UB_11      0.0530256000
_diffrn_orient_matrix_UB_12      0.0127759000
_diffrn_orient_matrix_UB_13      -0.0279086000
_diffrn_orient_matrix_UB_21      0.0207891000
_diffrn_orient_matrix_UB_22      -0.0230032000
_diffrn_orient_matrix_UB_23      -0.0256948000
_diffrn_orient_matrix_UB_31      -0.0585786000
_diffrn_orient_matrix_UB_32      0.0033147000
_diffrn_orient_matrix_UB_33      -0.0705643000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1535
_reflns_number_total             4444
_reflns_odcompleteness_completeness 99.65
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XS (Sheldrick, 2008)'
_refine_diff_density_max         0.248
_refine_diff_density_min         -0.235
_refine_diff_density_rms         0.048
_refine_ls_extinction_coef       0.007(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   0.970
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     283
_refine_ls_number_reflns         4444
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.2290
_refine_ls_R_factor_gt           0.0823
_refine_ls_restrained_S_all      0.970
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1930
_refine_ls_wR_factor_ref         0.2800
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Others
 Sof(H21D)=Sof(H21C)=Sof(Cl1A)=Sof(Cl2A)=1-FVAR(1)
 Sof(Cl1)=Sof(Cl2)=Sof(H21B)=Sof(H21A)=FVAR(1)
3.a Ternary CH refined with riding coordinates:
 C1(H1)
3.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3A,H3B), C21(H21B,H21A), C21(H21D,H21C)
3.c Aromatic/amide H refined with riding coordinates:
 C5(H5), C6(H6), C7(H7), C8(H8), C12(H12), C15(H15), C16(H16), C18(H18),
 C19(H19)
3.d Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   ?
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
F1 F 0.8771(4) 0.34730(11) 0.4677(3) 0.1076(11) Uani 1 1 d . . . . .
O1 O 1.2091(5) 0.01544(14) 0.4432(4) 0.1116(13) Uani 1 1 d . . . . .
N1 N 0.5077(6) 0.34489(17) 0.4893(4) 0.0974(15) Uani 1 1 d . . . . .
N2 N 0.7882(4) 0.25473(13) 0.5591(3) 0.0620(10) Uani 1 1 d . . . . .
N3 N 0.6957(4) 0.24402(15) 0.4183(3) 0.0692(11) Uani 1 1 d . . . . .
N4 N 0.7458(4) 0.20150(15) 0.3803(3) 0.0713(11) Uani 1 1 d . . . . .
C1 C 0.9006(6) 0.33809(17) 0.6221(4) 0.0757(14) Uani 1 1 d . . . . .
H1 H 1.0007 0.3217 0.6664 0.091 Uiso 1 1 calc R . . . .
C2 C 0.9003(7) 0.38620(17) 0.7056(6) 0.0942(17) Uani 1 1 d . . . . .
H2A H 0.7994 0.4017 0.6682 0.113 Uiso 1 1 calc R . . . .
H2B H 0.9753 0.4092 0.6894 0.113 Uiso 1 1 calc R . . . .
C3 C 0.9406(6) 0.37493(19) 0.8728(5) 0.0875(16) Uani 1 1 d . . . . .
H3A H 1.0510 0.3695 0.9151 0.105 Uiso 1 1 calc R . . . .
H3B H 0.9152 0.4038 0.9227 0.105 Uiso 1 1 calc R . . . .
C4 C 0.8581(5) 0.32986(17) 0.9062(4) 0.0693(13) Uani 1 1 d . . . . .
C5 C 0.8610(7) 0.3205(2) 1.0546(5) 0.0931(17) Uani 1 1 d . . . . .
H5 H 0.9110 0.3429 1.1304 0.112 Uiso 1 1 calc R . . . .
C6 C 0.7932(8) 0.2797(3) 1.0900(6) 0.0995(19) Uani 1 1 d . . . . .
H6 H 0.7987 0.2744 1.1898 0.119 Uiso 1 1 calc R . . . .
C7 C 0.7164(7) 0.2459(2) 0.9821(6) 0.0968(18) Uani 1 1 d . . . . .
H7 H 0.6684 0.2182 1.0070 0.116 Uiso 1 1 calc R . . . .
C8 C 0.7118(6) 0.25414(18) 0.8334(5) 0.0743(14) Uani 1 1 d . . . . .
H8 H 0.6599 0.2317 0.7584 0.089 Uiso 1 1 calc R . . . .
C9 C 0.7833(5) 0.29518(17) 0.7963(4) 0.0663(12) Uani 1 1 d . . . . .
C10 C 0.7736(5) 0.30246(16) 0.6310(4) 0.0580(11) Uani 1 1 d . . . . .
C11 C 0.6213(6) 0.32414(18) 0.5450(5) 0.0718(13) Uani 1 1 d . . . . .
C12 C 0.8966(5) 0.21924(16) 0.6111(4) 0.0637(12) Uani 1 1 d . . . . .
H12 H 0.9734 0.2182 0.7048 0.076 Uiso 1 1 calc R . . . .
C13 C 0.8698(5) 0.18500(16) 0.4968(4) 0.0625(12) Uani 1 1 d . . . . .
C14 C 0.9539(5) 0.13989(16) 0.4857(4) 0.0637(12) Uani 1 1 d . . . . .
C15 C 1.0384(6) 0.11346(18) 0.6139(5) 0.0786(14) Uani 1 1 d . . . . .
H15 H 1.0375 0.1241 0.7081 0.094 Uiso 1 1 calc R . . . .
C16 C 1.1242(6) 0.07151(19) 0.6044(6) 0.0877(16) Uani 1 1 d . . . . .
H16 H 1.1798 0.0544 0.6915 0.105 Uiso 1 1 calc R . . . .
C17 C 1.1264(6) 0.05554(18) 0.4667(6) 0.0800(14) Uani 1 1 d . . . . .
C18 C 1.0411(7) 0.08081(19) 0.3377(5) 0.0857(15) Uani 1 1 d . . . . .
H18 H 1.0408 0.0696 0.2436 0.103 Uiso 1 1 calc R . . . .
C19 C 0.9570(6) 0.12224(18) 0.3480(5) 0.0768(14) Uani 1 1 d . . . . .
H19 H 0.9007 0.1389 0.2601 0.092 Uiso 1 1 calc R . . . .
C20 C 1.2951(9) -0.0131(2) 0.5690(8) 0.137(2) Uani 1 1 d . . . . .
H20A H 1.3391 -0.0414 0.5352 0.205 Uiso 1 1 calc GR . . . .
H20B H 1.2287 -0.0243 0.6233 0.205 Uiso 1 1 calc GR . . . .
H20C H 1.3762 0.0071 0.6341 0.205 Uiso 1 1 calc GR . . . .
Cl1 Cl 0.6234(7) 0.0825(3) 0.8580(15) 0.278(5) Uani 0.697(12) 1 d . . P A 1
Cl2 Cl 0.8007(13) 0.0006(2) 0.9968(5) 0.235(5) Uani 0.697(12) 1 d . . P A 1
C21 C 0.7854(11) 0.0501(3) 0.8758(10) 0.181(4) Uani 1 1 d . . . . .
H21B H 0.8744 0.0717 0.9145 0.217 Uiso 0.697(12) 1 calc R . P A 1
H21A H 0.7834 0.0378 0.7777 0.217 Uiso 0.697(12) 1 calc R . P A 1
H21D H 0.8779 0.0669 0.9382 0.217 Uiso 0.303(12) 1 calc R . P A 2
H21C H 0.8146 0.0224 0.8238 0.217 Uiso 0.303(12) 1 calc R . P A 2
Cl1A Cl 0.6738(16) 0.0877(6) 0.7594(10) 0.197(6) Uani 0.303(12) 1 d . . P A 2
Cl2A Cl 0.657(2) 0.0266(6) 0.9995(14) 0.247(8) Uani 0.303(12) 1 d . . P A 2


_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
F1 C1 1.412(4) . ?
O1 C17 1.373(6) . ?
O1 C20 1.410(7) . ?
N1 C11 1.146(6) . ?
N2 N3 1.346(4) . ?
N2 C10 1.470(5) . ?
N2 C12 1.346(5) . ?
N3 N4 1.319(5) . ?
N4 C13 1.368(5) . ?
C1 C2 1.506(6) . ?
C1 C10 1.527(6) . ?
C2 C3 1.518(6) . ?
C3 C4 1.509(7) . ?
C4 C5 1.404(6) . ?
C4 C9 1.390(6) . ?
C5 C6 1.351(7) . ?
C6 C7 1.367(8) . ?
C7 C8 1.397(6) . ?
C8 C9 1.380(6) . ?
C9 C10 1.533(5) . ?
C10 C11 1.485(6) . ?
C12 C13 1.369(5) . ?
C13 C14 1.454(6) . ?
C14 C15 1.392(6) . ?
C14 C19 1.383(6) . ?
C15 C16 1.390(6) . ?
C16 C17 1.364(6) . ?
C17 C18 1.383(6) . ?
C18 C19 1.372(6) . ?
Cl1 C21 1.682(11) . ?
Cl2 C21 1.718(9) . ?
C21 Cl1A 1.590(14) . ?
C21 Cl2A 2.002(17) . ?

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
C17 O1 C20 118.5(5) . . ?
N3 N2 C10 120.8(3) . . ?
C12 N2 N3 111.1(3) . . ?
C12 N2 C10 127.8(3) . . ?
N4 N3 N2 106.5(3) . . ?
N3 N4 C13 109.6(3) . . ?
F1 C1 C2 110.9(4) . . ?
F1 C1 C10 107.4(3) . . ?
C2 C1 C10 112.1(4) . . ?
C1 C2 C3 109.0(4) . . ?
C4 C3 C2 113.7(4) . . ?
C5 C4 C3 119.9(4) . . ?
C9 C4 C3 122.7(4) . . ?
C9 C4 C5 117.4(5) . . ?
C6 C5 C4 121.7(5) . . ?
C5 C6 C7 121.3(5) . . ?
C6 C7 C8 118.3(5) . . ?
C9 C8 C7 120.9(5) . . ?
C4 C9 C10 121.0(4) . . ?
C8 C9 C4 120.3(4) . . ?
C8 C9 C10 118.6(4) . . ?
N2 C10 C1 109.5(4) . . ?
N2 C10 C9 111.6(3) . . ?
N2 C10 C11 107.5(3) . . ?
C1 C10 C9 109.8(3) . . ?
C11 C10 C1 109.0(4) . . ?
C11 C10 C9 109.4(4) . . ?
N1 C11 C10 172.8(5) . . ?
N2 C12 C13 105.4(3) . . ?
N4 C13 C12 107.4(4) . . ?
N4 C13 C14 122.2(4) . . ?
C12 C13 C14 130.3(4) . . ?
C15 C14 C13 121.3(4) . . ?
C19 C14 C13 121.5(4) . . ?
C19 C14 C15 117.2(4) . . ?
C16 C15 C14 121.5(4) . . ?
C17 C16 C15 119.7(5) . . ?
O1 C17 C18 115.2(5) . . ?
C16 C17 O1 125.1(5) . . ?
C16 C17 C18 119.6(5) . . ?
C19 C18 C17 120.3(4) . . ?
C18 C19 C14 121.6(4) . . ?
Cl1 C21 Cl2 110.1(7) . . ?
Cl1A C21 Cl2A 103.1(8) . . ?


_olex2_submission_special_instructions 'No special instructions were received'
