# Electronic Supplementary Material (ESI) for RSC Advances.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# 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_hdp5
_database_code_depnum_ccdc_archive 'CCDC 1475885'
_audit_update_record             
;
2016-04-22 deposited with the CCDC.
2016-06-07 downloaded from the CCDC.
;
#==================================================================


# start Validation Reply Form
_vrf_THETM01_hdp5                
;
PROBLEM: The value of sine(theta_max)/wavelength is less than 0.575
RESPONSE: Data was collected on a Bruker APEX2-Duo instrument with 
Cu-source and APEX2 detector. Under these experimental conditions 
the maximum angle that can be collected is 120 degrees two-theta. 
;
# end Validation Reply Form




_audit_creation_date             2015-11-24
_audit_creation_method           

#==========================================================================

# SUBMISSION DETAILS
;
Olex2 1.2-beta
(compiled 2015.11.10 svn.r3248 for OlexSys, GUI svn.r5133)
;
_shelxl_version_number           2014-3
#==========================================================================
# CHEMICAL DATA
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         'C13 H9 Cl N4'
_chemical_formula_sum            'C13 H9 Cl N4'
_chemical_formula_weight         256.69
_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 0.0181 0.0091 '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 0.3639 0.7018 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0311 0.0180 '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.
;
#==========================================================================

# CRYSTAL DATA
_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                   5.1789(3)
_cell_length_b                   9.8168(4)
_cell_length_c                   22.5328(10)
_cell_angle_alpha                90
_cell_angle_beta                 93.543(2)
_cell_angle_gamma                90
_cell_volume                     1143.38(10)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    9966
_cell_measurement_temperature    110.15
_cell_measurement_theta_max      61.253
_cell_measurement_theta_min      3.930
_shelx_estimated_absorpt_T_max   0.629
_shelx_estimated_absorpt_T_min   0.295
_exptl_absorpt_coefficient_mu    2.836
_exptl_absorpt_correction_T_max  0.7520
_exptl_absorpt_correction_T_min  0.3470
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
#==========================================================================

# Experimental data
;
SADABS-2014/3 (Bruker,2014/3) was used for absorption correction.
wR2(int) was 0.1552 before and 0.0601 after correction.
The Ratio of minimum to maximum transmission is 0.4614.
The λ/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.491
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       block
_exptl_crystal_F_000             528
_exptl_crystal_size_max          0.57
_exptl_crystal_size_mid          0.32
_exptl_crystal_size_min          0.18
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0399
_diffrn_reflns_av_unetI/netI     0.0245
_diffrn_reflns_Laue_measured_fraction_full 0.809
_diffrn_reflns_Laue_measured_fraction_max 0.955
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            17151
_diffrn_reflns_point_group_measured_fraction_full 0.809
_diffrn_reflns_point_group_measured_fraction_max 0.955
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         61.256
_diffrn_reflns_theta_min         3.931
_diffrn_ambient_temperature      110.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.809
_diffrn_measured_fraction_theta_max 0.955
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_source                   ?
_diffrn_special_details          ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1636
_reflns_number_total             1671
_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       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    ?
_refine_diff_density_max         0.237
_refine_diff_density_min         -0.265
_refine_diff_density_rms         0.047
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     163
_refine_ls_number_reflns         1671
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0356
_refine_ls_R_factor_gt           0.0349
_refine_ls_restrained_S_all      1.096
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0329P)²+1.0115P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0863
_refine_ls_wR_factor_ref         0.0867
#==========================================================================

# Refinement data 
_refine_special_details          
;
 ?
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C7(H7), C13(H13), C9(H9), C10(H10), C4(H4), C2(H2), C3(H3), C12(H12), C11(H11)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
#==========================================================================

# ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS
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
Cl1 Cl -0.29654(9) 0.52300(5) 0.58529(2) 0.02663(19) Uani 1 1 d . . . . .
N1 N 0.0817(3) 0.69760(16) 0.59026(7) 0.0213(4) Uani 1 1 d . . . . .
N2 N 0.4281(3) 0.84578(16) 0.60648(7) 0.0204(4) Uani 1 1 d . . . . .
N4 N 0.7525(4) 0.97295(16) 0.63224(8) 0.0258(4) Uani 1 1 d . . . . .
N3 N 0.5742(4) 0.95244(17) 0.58970(7) 0.0265(4) Uani 1 1 d . . . . .
C8 C 0.9010(4) 0.87712(19) 0.73008(9) 0.0215(4) Uani 1 1 d . . . . .
C6 C 0.7234(4) 0.88001(19) 0.67683(8) 0.0210(4) Uani 1 1 d . . . . .
C5 C 0.2227(4) 0.79550(19) 0.56746(9) 0.0210(4) Uani 1 1 d . . . . .
C7 C 0.5155(4) 0.79841(19) 0.66042(8) 0.0217(4) Uani 1 1 d . . . . .
H7 H 0.4480 0.7250 0.6821 0.026 Uiso 1 1 calc R . . . .
C13 C 0.8750(4) 0.7791(2) 0.77440(9) 0.0248(5) Uani 1 1 d . . . . .
H13 H 0.7391 0.7142 0.7703 0.030 Uiso 1 1 calc R . . . .
C1 C -0.1101(4) 0.65022(19) 0.55480(9) 0.0222(5) Uani 1 1 d . . . . .
C9 C 1.1015(4) 0.9718(2) 0.73724(9) 0.0236(5) Uani 1 1 d . . . . .
H9 H 1.1207 1.0394 0.7077 0.028 Uiso 1 1 calc R . . . .
C10 C 1.2726(4) 0.9685(2) 0.78690(9) 0.0254(5) Uani 1 1 d . . . . .
H10 H 1.4091 1.0331 0.7911 0.031 Uiso 1 1 calc R . . . .
C4 C 0.1826(4) 0.8490(2) 0.51075(9) 0.0256(5) Uani 1 1 d . . . . .
H4 H 0.2906 0.9186 0.4967 0.031 Uiso 1 1 calc R . . . .
C2 C -0.1740(4) 0.6945(2) 0.49750(9) 0.0253(5) Uani 1 1 d . . . . .
H2 H -0.3159 0.6568 0.4743 0.030 Uiso 1 1 calc R . . . .
C3 C -0.0212(4) 0.7965(2) 0.47553(9) 0.0280(5) Uani 1 1 d . . . . .
H3 H -0.0567 0.8301 0.4363 0.034 Uiso 1 1 calc R . . . .
C12 C 1.0457(4) 0.7758(2) 0.82416(9) 0.0272(5) Uani 1 1 d . . . . .
H12 H 1.0266 0.7088 0.8540 0.033 Uiso 1 1 calc R . . . .
C11 C 1.2450(4) 0.8707(2) 0.83056(9) 0.0265(5) Uani 1 1 d . . . . .
H11 H 1.3620 0.8686 0.8647 0.032 Uiso 1 1 calc R . . . .

#==========================================================================

# MOLECULAR GEOMETRY 
_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
Cl1 C1 1.745(2) . ?
N1 C5 1.329(3) . ?
N1 C1 1.320(3) . ?
N2 N3 1.359(2) . ?
N2 C5 1.426(3) . ?
N2 C7 1.353(3) . ?
N4 N3 1.305(2) . ?
N4 C6 1.372(3) . ?
C8 C6 1.466(3) . ?
C8 C13 1.399(3) . ?
C8 C9 1.396(3) . ?
C6 C7 1.374(3) . ?
C5 C4 1.385(3) . ?
C7 H7 0.9500 . ?
C13 H13 0.9500 . ?
C13 C12 1.384(3) . ?
C1 C2 1.383(3) . ?
C9 H9 0.9500 . ?
C9 C10 1.384(3) . ?
C10 H10 0.9500 . ?
C10 C11 1.388(3) . ?
C4 H4 0.9500 . ?
C4 C3 1.381(3) . ?
C2 H2 0.9500 . ?
C2 C3 1.386(3) . ?
C3 H3 0.9500 . ?
C12 H12 0.9500 . ?
C12 C11 1.391(3) . ?
C11 H11 0.9500 . ?

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 N1 C5 115.56(17) . . ?
N3 N2 C5 120.14(16) . . ?
C7 N2 N3 110.73(16) . . ?
C7 N2 C5 129.07(17) . . ?
N3 N4 C6 109.30(17) . . ?
N4 N3 N2 107.17(15) . . ?
C13 C8 C6 120.95(19) . . ?
C9 C8 C6 120.42(18) . . ?
C9 C8 C13 118.63(19) . . ?
N4 C6 C8 121.36(18) . . ?
N4 C6 C7 108.06(17) . . ?
C7 C6 C8 130.56(18) . . ?
N1 C5 N2 114.75(17) . . ?
N1 C5 C4 125.17(19) . . ?
C4 C5 N2 120.08(18) . . ?
N2 C7 C6 104.73(17) . . ?
N2 C7 H7 127.6 . . ?
C6 C7 H7 127.6 . . ?
C8 C13 H13 119.7 . . ?
C12 C13 C8 120.6(2) . . ?
C12 C13 H13 119.7 . . ?
N1 C1 Cl1 115.33(15) . . ?
N1 C1 C2 125.60(19) . . ?
C2 C1 Cl1 119.07(16) . . ?
C8 C9 H9 119.6 . . ?
C10 C9 C8 120.82(19) . . ?
C10 C9 H9 119.6 . . ?
C9 C10 H10 120.0 . . ?
C9 C10 C11 120.0(2) . . ?
C11 C10 H10 120.0 . . ?
C5 C4 H4 121.5 . . ?
C3 C4 C5 117.03(19) . . ?
C3 C4 H4 121.5 . . ?
C1 C2 H2 121.6 . . ?
C1 C2 C3 116.82(19) . . ?
C3 C2 H2 121.6 . . ?
C4 C3 C2 119.82(19) . . ?
C4 C3 H3 120.1 . . ?
C2 C3 H3 120.1 . . ?
C13 C12 H12 120.0 . . ?
C13 C12 C11 120.1(2) . . ?
C11 C12 H12 120.0 . . ?
C10 C11 C12 119.8(2) . . ?
C10 C11 H11 120.1 . . ?
C12 C11 H11 120.1 . . ?

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
Cl1 C1 C2 C3 179.48(16) . . . . ?
N1 C5 C4 C3 0.4(3) . . . . ?
N1 C1 C2 C3 0.6(3) . . . . ?
N2 C5 C4 C3 -179.40(18) . . . . ?
N4 C6 C7 N2 0.0(2) . . . . ?
N3 N2 C5 N1 -175.38(17) . . . . ?
N3 N2 C5 C4 4.5(3) . . . . ?
N3 N2 C7 C6 -0.1(2) . . . . ?
N3 N4 C6 C8 178.75(17) . . . . ?
N3 N4 C6 C7 0.0(2) . . . . ?
C8 C6 C7 N2 -178.57(19) . . . . ?
C8 C13 C12 C11 0.1(3) . . . . ?
C8 C9 C10 C11 -0.5(3) . . . . ?
C6 N4 N3 N2 0.0(2) . . . . ?
C6 C8 C13 C12 179.09(19) . . . . ?
C6 C8 C9 C10 -178.92(18) . . . . ?
C5 N1 C1 Cl1 -179.34(14) . . . . ?
C5 N1 C1 C2 -0.5(3) . . . . ?
C5 N2 N3 N4 -177.33(17) . . . . ?
C5 N2 C7 C6 177.03(18) . . . . ?
C5 C4 C3 C2 -0.2(3) . . . . ?
C7 N2 N3 N4 0.1(2) . . . . ?
C7 N2 C5 N1 7.8(3) . . . . ?
C7 N2 C5 C4 -172.38(19) . . . . ?
C13 C8 C6 N4 -177.85(18) . . . . ?
C13 C8 C6 C7 0.6(3) . . . . ?
C13 C8 C9 C10 0.5(3) . . . . ?
C13 C12 C11 C10 -0.1(3) . . . . ?
C1 N1 C5 N2 179.74(16) . . . . ?
C1 N1 C5 C4 -0.1(3) . . . . ?
C1 C2 C3 C4 -0.3(3) . . . . ?
C9 C8 C6 N4 1.5(3) . . . . ?
C9 C8 C6 C7 180.0(2) . . . . ?
C9 C8 C13 C12 -0.3(3) . . . . ?
C9 C10 C11 C12 0.3(3) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
# End of CIF  ============================================================
####################################################################### 
# 
# 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_hdp9
_database_code_depnum_ccdc_archive 'CCDC 1475932'
_audit_update_record             
;
2016-04-22 deposited with the CCDC.
2016-06-07 downloaded from the CCDC.
;
#==================================================================
_audit_creation_date             2015-11-24
_audit_creation_method           
#==========================================================================

# SUBMISSION DETAILS
;
Olex2 1.2-beta
(compiled 2015.11.10 svn.r3248 for OlexSys, GUI svn.r5133)
;
_shelxl_version_number           2014-3
#==========================================================================
# CHEMICAL DATA
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         'C13 H8 Cl F N4'
_chemical_formula_sum            'C13 H8 Cl F N4'
_chemical_formula_weight         274.68
_chemical_absolute_configuration ?
_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'

_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.
;
#==========================================================================

# CRYSTAL DATA
_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_H-M_alt        'P c a 21'
_space_group_name_Hall           'P 2c -2ac'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z+1/2'
'x+1/2, -y, z'
'-x+1/2, y, z+1/2'

_cell_length_a                   27.89(4)
_cell_length_b                   5.933(9)
_cell_length_c                   14.48(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2396(6)
_cell_formula_units_Z            8
_cell_measurement_reflns_used    9851
_cell_measurement_temperature    110.15
_cell_measurement_theta_max      27.729
_cell_measurement_theta_min      2.838
_shelx_estimated_absorpt_T_max   0.939
_shelx_estimated_absorpt_T_min   0.838
_exptl_absorpt_coefficient_mu    0.321
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.4089
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
#==========================================================================

# Experimental data
;
SADABS-2014/3 (Bruker,2014/3) was used for absorption correction.
wR2(int) was 0.1364 before and 0.0735 after correction.
The Ratio of minimum to maximum transmission is 0.5485.
The λ/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.523
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       plate
_exptl_crystal_F_000             1120
_exptl_crystal_size_max          0.57
_exptl_crystal_size_mid          0.54
_exptl_crystal_size_min          0.2
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0853
_diffrn_reflns_av_unetI/netI     0.0493
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       36
_diffrn_reflns_limit_h_min       -36
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            41117
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.681
_diffrn_reflns_theta_min         2.027
_diffrn_ambient_temperature      110.15
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_special_details          ?
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.923
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.994
_reflns_number_gt                5292
_reflns_number_total             5583
_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       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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    ?
_refine_diff_density_max         0.300
_refine_diff_density_min         -0.255
_refine_diff_density_rms         0.047
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.50(7)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     344
_refine_ls_number_reflns         5583
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0364
_refine_ls_R_factor_gt           0.0338
_refine_ls_restrained_S_all      1.049
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0243P)²+1.0097P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0790
_refine_ls_wR_factor_ref         0.0806
#==========================================================================

# Refinement data
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.50(7) 0.50(7)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C5(H5), C7(H7), C9(H9), C10(H10), C11(H11), C12(H12), C13(H13),
 C3B(H3B), C5B(H5B), C7B(H7B), C9B(H9B), C10B(H10B), C11B(H11B), C12B(H12B),
 C13B(H13B)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
#==========================================================================

# ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS
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
Cl1 Cl 0.33944(2) 0.36341(12) 0.67216(6) 0.02666(17) Uani 1 1 d . . . . .
F1 F 0.36679(6) 0.7791(3) 0.56941(13) 0.0261(4) Uani 1 1 d . . . . .
N1 N 0.48722(8) 0.5512(3) 0.56546(16) 0.0148(4) Uani 1 1 d . . . . .
N2 N 0.52075(8) 0.2222(3) 0.62661(16) 0.0144(4) Uani 1 1 d . . . . .
N3 N 0.56586(8) 0.2884(4) 0.60658(16) 0.0150(5) Uani 1 1 d . . . . .
N4 N 0.51630(8) 0.0141(4) 0.66432(18) 0.0175(5) Uani 1 1 d . . . . .
C1 C 0.39614(10) 0.4321(5) 0.6316(2) 0.0175(5) Uani 1 1 d . . . . .
C2 C 0.40393(10) 0.6341(4) 0.5840(2) 0.0172(6) Uani 1 1 d . . . . .
C3 C 0.44917(10) 0.6882(4) 0.55188(19) 0.0159(5) Uani 1 1 d . . . . .
H3 H 0.4536 0.8256 0.5193 0.019 Uiso 1 1 calc R . . . .
C4 C 0.47937(10) 0.3609(4) 0.61167(18) 0.0143(5) Uani 1 1 d . . . . .
C5 C 0.43493(10) 0.2900(4) 0.64651(18) 0.0167(5) Uani 1 1 d . . . . .
H5 H 0.4315 0.1514 0.6787 0.020 Uiso 1 1 calc R . . . .
C6 C 0.59292(10) 0.1107(4) 0.6319(2) 0.0151(5) Uani 1 1 d . . . . .
C7 C 0.56158(9) -0.0591(4) 0.6670(2) 0.0170(5) Uani 1 1 d . . . . .
H7 H 0.5714 -0.2027 0.6889 0.020 Uiso 1 1 calc R . . . .
C8 C 0.64552(10) 0.1100(4) 0.62398(19) 0.0161(5) Uani 1 1 d . . . . .
C9 C 0.67004(11) 0.2940(5) 0.5846(2) 0.0215(6) Uani 1 1 d . . . . .
H9 H 0.6524 0.4185 0.5611 0.026 Uiso 1 1 calc R . . . .
C10 C 0.71998(11) 0.2945(5) 0.5798(2) 0.0256(6) Uani 1 1 d . . . . .
H10 H 0.7362 0.4196 0.5532 0.031 Uiso 1 1 calc R . . . .
C11 C 0.74637(11) 0.1126(5) 0.6139(2) 0.0248(6) Uani 1 1 d . . . . .
H11 H 0.7804 0.1142 0.6109 0.030 Uiso 1 1 calc R . . . .
C12 C 0.72241(11) -0.0727(5) 0.6526(2) 0.0265(7) Uani 1 1 d . . . . .
H12 H 0.7402 -0.1976 0.6752 0.032 Uiso 1 1 calc R . . . .
C13 C 0.67250(11) -0.0738(5) 0.6580(2) 0.0225(7) Uani 1 1 d . . . . .
H13 H 0.6565 -0.1990 0.6849 0.027 Uiso 1 1 calc R . . . .
Cl1B Cl 0.68274(2) 0.12223(11) 0.32794(6) 0.02509(17) Uani 1 1 d . . . . .
F1B F 0.65488(6) -0.2914(3) 0.42939(12) 0.0247(4) Uani 1 1 d . . . . .
N1B N 0.53424(8) -0.0650(4) 0.43124(16) 0.0157(5) Uani 1 1 d . . . . .
N2B N 0.50128(8) 0.2649(3) 0.37012(16) 0.0148(5) Uani 1 1 d . . . . .
N3B N 0.45608(8) 0.2030(4) 0.39177(17) 0.0160(5) Uani 1 1 d . . . . .
N4B N 0.50609(8) 0.4733(4) 0.33310(17) 0.0173(5) Uani 1 1 d . . . . .
C1B C 0.62574(9) 0.0534(4) 0.36577(19) 0.0167(5) Uani 1 1 d . . . . .
C2B C 0.61788(10) -0.1485(4) 0.4134(2) 0.0167(5) Uani 1 1 d . . . . .
C3B C 0.57239(10) -0.2020(4) 0.44555(19) 0.0169(6) Uani 1 1 d . . . . .
H3B H 0.5679 -0.3387 0.4786 0.020 Uiso 1 1 calc R . . . .
C4B C 0.54226(9) 0.1242(4) 0.38423(19) 0.0145(5) Uani 1 1 d . . . . .
C5B C 0.58699(9) 0.1954(4) 0.35019(18) 0.0163(5) Uani 1 1 d . . . . .
H5B H 0.5905 0.3340 0.3181 0.020 Uiso 1 1 calc R . . . .
C6B C 0.42944(9) 0.3827(4) 0.36687(19) 0.0143(5) Uani 1 1 d . . . . .
C7B C 0.46116(10) 0.5500(4) 0.3310(2) 0.0177(5) Uani 1 1 d . . . . .
H7B H 0.4517 0.6941 0.3089 0.021 Uiso 1 1 calc R . . . .
C8B C 0.37665(10) 0.3875(4) 0.3736(2) 0.0158(6) Uani 1 1 d . . . . .
C9B C 0.35074(10) 0.2054(5) 0.4113(2) 0.0208(6) Uani 1 1 d . . . . .
H9B H 0.3674 0.0794 0.4359 0.025 Uiso 1 1 calc R . . . .
C10B C 0.30063(11) 0.2097(5) 0.4125(2) 0.0250(7) Uani 1 1 d . . . . .
H10B H 0.2834 0.0864 0.4381 0.030 Uiso 1 1 calc R . . . .
C11B C 0.27566(11) 0.3935(5) 0.3765(2) 0.0253(6) Uani 1 1 d . . . . .
H11B H 0.2416 0.3950 0.3773 0.030 Uiso 1 1 calc R . . . .
C12B C 0.30091(11) 0.5751(5) 0.3394(3) 0.0258(7) Uani 1 1 d . . . . .
H12B H 0.2840 0.7004 0.3147 0.031 Uiso 1 1 calc R . . . .
C13B C 0.35116(10) 0.5727(4) 0.3385(2) 0.0202(6) Uani 1 1 d . . . . .
H13B H 0.3682 0.6978 0.3139 0.024 Uiso 1 1 calc R . . . .

#==========================================================================

# MOLECULAR GEOMETRY
_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
Cl1 C1 1.736(4) . ?
F1 C2 1.363(3) . ?
N1 C3 1.351(4) . ?
N1 C4 1.330(4) . ?
N2 N3 1.350(3) . ?
N2 N4 1.356(3) . ?
N2 C4 1.434(4) . ?
N3 C6 1.348(4) . ?
N4 C7 1.336(4) . ?
C1 C2 1.399(4) . ?
C1 C5 1.389(4) . ?
C2 C3 1.383(4) . ?
C3 H3 0.9500 . ?
C4 C5 1.403(4) . ?
C5 H5 0.9500 . ?
C6 C7 1.427(4) . ?
C6 C8 1.472(4) . ?
C7 H7 0.9500 . ?
C8 C9 1.409(4) . ?
C8 C13 1.414(4) . ?
C9 H9 0.9500 . ?
C9 C10 1.395(5) . ?
C10 H10 0.9500 . ?
C10 C11 1.397(5) . ?
C11 H11 0.9500 . ?
C11 C12 1.403(5) . ?
C12 H12 0.9500 . ?
C12 C13 1.394(5) . ?
C13 H13 0.9500 . ?
Cl1B C1B 1.730(3) . ?
F1B C2B 1.355(3) . ?
N1B C3B 1.355(4) . ?
N1B C4B 1.332(4) . ?
N2B N3B 1.350(4) . ?
N2B N4B 1.355(3) . ?
N2B C4B 1.430(4) . ?
N3B C6B 1.349(4) . ?
N4B C7B 1.333(4) . ?
C1B C2B 1.399(4) . ?
C1B C5B 1.389(4) . ?
C2B C3B 1.388(4) . ?
C3B H3B 0.9500 . ?
C4B C5B 1.406(4) . ?
C5B H5B 0.9500 . ?
C6B C7B 1.428(4) . ?
C6B C8B 1.476(4) . ?
C7B H7B 0.9500 . ?
C8B C9B 1.410(4) . ?
C8B C13B 1.404(4) . ?
C9B H9B 0.9500 . ?
C9B C10B 1.398(4) . ?
C10B H10B 0.9500 . ?
C10B C11B 1.395(5) . ?
C11B H11B 0.9500 . ?
C11B C12B 1.395(5) . ?
C12B H12B 0.9500 . ?
C12B C13B 1.402(4) . ?
C13B H13B 0.9500 . ?

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
C4 N1 C3 117.0(2) . . ?
N3 N2 N4 115.9(2) . . ?
N3 N2 C4 123.4(2) . . ?
N4 N2 C4 120.6(2) . . ?
C6 N3 N2 103.6(2) . . ?
C7 N4 N2 102.8(2) . . ?
C2 C1 Cl1 120.6(2) . . ?
C5 C1 Cl1 121.0(2) . . ?
C5 C1 C2 118.4(3) . . ?
F1 C2 C1 119.9(3) . . ?
F1 C2 C3 119.6(3) . . ?
C3 C2 C1 120.4(2) . . ?
N1 C3 C2 121.9(3) . . ?
N1 C3 H3 119.1 . . ?
C2 C3 H3 119.1 . . ?
N1 C4 N2 115.5(2) . . ?
N1 C4 C5 125.5(3) . . ?
C5 C4 N2 119.0(2) . . ?
C1 C5 C4 116.8(3) . . ?
C1 C5 H5 121.6 . . ?
C4 C5 H5 121.6 . . ?
N3 C6 C7 107.8(3) . . ?
N3 C6 C8 122.6(2) . . ?
C7 C6 C8 129.5(2) . . ?
N4 C7 C6 109.8(2) . . ?
N4 C7 H7 125.1 . . ?
C6 C7 H7 125.1 . . ?
C9 C8 C6 120.9(2) . . ?
C9 C8 C13 118.7(3) . . ?
C13 C8 C6 120.4(2) . . ?
C8 C9 H9 119.8 . . ?
C10 C9 C8 120.4(3) . . ?
C10 C9 H9 119.8 . . ?
C9 C10 H10 119.8 . . ?
C9 C10 C11 120.5(3) . . ?
C11 C10 H10 119.8 . . ?
C10 C11 H11 120.1 . . ?
C10 C11 C12 119.7(3) . . ?
C12 C11 H11 120.1 . . ?
C11 C12 H12 119.9 . . ?
C13 C12 C11 120.1(3) . . ?
C13 C12 H12 119.9 . . ?
C8 C13 H13 119.7 . . ?
C12 C13 C8 120.5(3) . . ?
C12 C13 H13 119.7 . . ?
C4B N1B C3B 116.9(2) . . ?
N3B N2B N4B 115.6(2) . . ?
N3B N2B C4B 123.7(2) . . ?
N4B N2B C4B 120.7(2) . . ?
C6B N3B N2B 103.7(2) . . ?
C7B N4B N2B 103.1(2) . . ?
C2B C1B Cl1B 120.1(2) . . ?
C5B C1B Cl1B 121.4(2) . . ?
C5B C1B C2B 118.5(3) . . ?
F1B C2B C1B 120.0(2) . . ?
F1B C2B C3B 119.7(3) . . ?
C3B C2B C1B 120.3(2) . . ?
N1B C3B C2B 121.9(3) . . ?
N1B C3B H3B 119.0 . . ?
C2B C3B H3B 119.0 . . ?
N1B C4B N2B 115.5(2) . . ?
N1B C4B C5B 125.6(2) . . ?
C5B C4B N2B 118.9(2) . . ?
C1B C5B C4B 116.8(3) . . ?
C1B C5B H5B 121.6 . . ?
C4B C5B H5B 121.6 . . ?
N3B C6B C7B 107.8(2) . . ?
N3B C6B C8B 123.2(2) . . ?
C7B C6B C8B 129.0(2) . . ?
N4B C7B C6B 109.7(2) . . ?
N4B C7B H7B 125.2 . . ?
C6B C7B H7B 125.2 . . ?
C9B C8B C6B 121.5(2) . . ?
C13B C8B C6B 119.8(2) . . ?
C13B C8B C9B 118.7(3) . . ?
C8B C9B H9B 119.9 . . ?
C10B C9B C8B 120.2(3) . . ?
C10B C9B H9B 119.9 . . ?
C9B C10B H10B 119.7 . . ?
C11B C10B C9B 120.6(3) . . ?
C11B C10B H10B 119.7 . . ?
C10B C11B H11B 120.1 . . ?
C10B C11B C12B 119.7(3) . . ?
C12B C11B H11B 120.1 . . ?
C11B C12B H12B 120.0 . . ?
C11B C12B C13B 120.0(3) . . ?
C13B C12B H12B 120.0 . . ?
C8B C13B H13B 119.6 . . ?
C12B C13B C8B 120.7(3) . . ?
C12B C13B H13B 119.6 . . ?

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
Cl1 C1 C2 F1 0.1(4) . . . . ?
Cl1 C1 C2 C3 180.0(2) . . . . ?
Cl1 C1 C5 C4 -179.5(2) . . . . ?
F1 C2 C3 N1 179.3(2) . . . . ?
N1 C4 C5 C1 -0.4(4) . . . . ?
N2 N3 C6 C7 0.0(3) . . . . ?
N2 N3 C6 C8 -178.7(2) . . . . ?
N2 N4 C7 C6 1.1(3) . . . . ?
N2 C4 C5 C1 178.9(2) . . . . ?
N3 N2 N4 C7 -1.2(3) . . . . ?
N3 N2 C4 N1 8.2(4) . . . . ?
N3 N2 C4 C5 -171.1(2) . . . . ?
N3 C6 C7 N4 -0.7(3) . . . . ?
N3 C6 C8 C9 -3.4(4) . . . . ?
N3 C6 C8 C13 175.1(3) . . . . ?
N4 N2 N3 C6 0.7(3) . . . . ?
N4 N2 C4 N1 -173.1(2) . . . . ?
N4 N2 C4 C5 7.5(4) . . . . ?
C1 C2 C3 N1 -0.5(4) . . . . ?
C2 C1 C5 C4 -0.4(4) . . . . ?
C3 N1 C4 N2 -178.6(2) . . . . ?
C3 N1 C4 C5 0.7(4) . . . . ?
C4 N1 C3 C2 -0.2(4) . . . . ?
C4 N2 N3 C6 179.4(2) . . . . ?
C4 N2 N4 C7 -179.9(2) . . . . ?
C5 C1 C2 F1 -179.0(2) . . . . ?
C5 C1 C2 C3 0.8(4) . . . . ?
C6 C8 C9 C10 178.2(3) . . . . ?
C6 C8 C13 C12 -178.5(3) . . . . ?
C7 C6 C8 C9 178.2(3) . . . . ?
C7 C6 C8 C13 -3.3(4) . . . . ?
C8 C6 C7 N4 177.8(3) . . . . ?
C8 C9 C10 C11 0.1(5) . . . . ?
C9 C8 C13 C12 0.0(4) . . . . ?
C9 C10 C11 C12 0.5(5) . . . . ?
C10 C11 C12 C13 -0.8(5) . . . . ?
C11 C12 C13 C8 0.6(4) . . . . ?
C13 C8 C9 C10 -0.3(4) . . . . ?
Cl1B C1B C2B F1B -0.5(4) . . . . ?
Cl1B C1B C2B C3B 178.6(2) . . . . ?
Cl1B C1B C5B C4B -179.7(2) . . . . ?
F1B C2B C3B N1B -179.9(2) . . . . ?
N1B C4B C5B C1B 1.2(4) . . . . ?
N2B N3B C6B C7B -0.5(3) . . . . ?
N2B N3B C6B C8B 176.8(2) . . . . ?
N2B N4B C7B C6B -0.4(3) . . . . ?
N2B C4B C5B C1B 179.9(2) . . . . ?
N3B N2B N4B C7B 0.1(3) . . . . ?
N3B N2B C4B N1B -8.0(4) . . . . ?
N3B N2B C4B C5B 173.2(2) . . . . ?
N3B C6B C7B N4B 0.6(3) . . . . ?
N3B C6B C8B C9B 3.2(4) . . . . ?
N3B C6B C8B C13B -174.2(3) . . . . ?
N4B N2B N3B C6B 0.3(3) . . . . ?
N4B N2B C4B N1B 172.1(2) . . . . ?
N4B N2B C4B C5B -6.7(4) . . . . ?
C1B C2B C3B N1B 1.0(4) . . . . ?
C2B C1B C5B C4B 0.2(4) . . . . ?
C3B N1B C4B N2B 179.9(2) . . . . ?
C3B N1B C4B C5B -1.4(4) . . . . ?
C4B N1B C3B C2B 0.3(4) . . . . ?
C4B N2B N3B C6B -179.7(2) . . . . ?
C4B N2B N4B C7B -180.0(2) . . . . ?
C5B C1B C2B F1B 179.7(2) . . . . ?
C5B C1B C2B C3B -1.2(4) . . . . ?
C6B C8B C9B C10B -176.8(3) . . . . ?
C6B C8B C13B C12B 176.4(3) . . . . ?
C7B C6B C8B C9B 179.9(3) . . . . ?
C7B C6B C8B C13B 2.5(4) . . . . ?
C8B C6B C7B N4B -176.5(3) . . . . ?
C8B C9B C10B C11B 0.1(5) . . . . ?
C9B C8B C13B C12B -1.1(4) . . . . ?
C9B C10B C11B C12B -0.3(5) . . . . ?
C10B C11B C12B C13B -0.1(5) . . . . ?
C11B C12B C13B C8B 0.9(5) . . . . ?
C13B C8B C9B C10B 0.7(4) . . . . ?

_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.50(7)
2 0.50(7)
# End of CIF  ============================================================

