# Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_1
_database_code_depnum_ccdc_archive 'CCDC 1969138'
loop_
_audit_author_name
_audit_author_address
'Yulia Nelyubina'
;AN Nesmeyanov Institute of Organoelement Compounds
Russia
;
_audit_update_record             
;
2019-11-30 deposited with the CCDC.	2020-01-24 downloaded from the CCDC.
;
_audit_creation_date             2019-11-30
_audit_creation_method           
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_chemical_formula_moiety         'C13 H8 Br F N2'
_chemical_formula_sum            'C13 H8 Br F N2'
_chemical_formula_weight         291.12
loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_Cromer_Mann_a1
_atom_type_scat_Cromer_Mann_a2
_atom_type_scat_Cromer_Mann_a3
_atom_type_scat_Cromer_Mann_a4
_atom_type_scat_Cromer_Mann_b1
_atom_type_scat_Cromer_Mann_b2
_atom_type_scat_Cromer_Mann_b3
_atom_type_scat_Cromer_Mann_b4
_atom_type_scat_Cromer_Mann_c
_atom_type_scat_source
_atom_type_scat_dispersion_source
H 0.00000 0.00000 0.49300 0.32291 0.14019 0.04081 10.51090 26.12570 3.14236
57.79970 0.0030380000826
'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
C 0.00347 0.00161 2.31000 1.02000 1.58860 0.86500 20.84390 10.20750 0.56870
51.65120 0.215599998832
'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
F 0.01794 0.01033 3.53920 2.64120 1.51700 1.02430 10.28250 4.29440 0.26150
26.14760 0.277599990368
'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
Br -0.28346 2.55990 17.17890 5.23580 5.63770 3.98510 2.17230 16.57960 0.26090
41.43280 2.95569992065
'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'
N 0.00653 0.00323 12.21260 3.13220 2.01250 1.16630 0.00570 9.89330 28.99750
0.58260 -11.5290002823
'International Tables Volume C Table 6.1.1.4 (pp. 500-502)'
'Henke, Gullikson and Davis, At. Data and Nucl. Data Tables, 1993, 54, 2'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -x,y+1/2,-z+1/2
3 -x,-y,-z
4 x,-y-1/2,z-1/2

_symmetry_Int_Tables_number      14
_cell_length_a                   18.5420(12)
_cell_length_b                   4.0333(3)
_cell_length_c                   22.2351(15)
_cell_angle_alpha                90
_cell_angle_beta                 138.9436(10)
_cell_angle_gamma                90
_cell_volume                     1092.17(13)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    8113
_cell_measurement_temperature    120
_cell_measurement_theta_max      30.29
_cell_measurement_theta_min      2.21
_exptl_absorpt_coefficient_mu    3.752
_exptl_absorpt_correction_T_max  0.7461
_exptl_absorpt_correction_T_min  0.5530
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1126 before and 0.0501 after correction.
The Ratio of minimum to maximum transmission is 0.7412.
The λ/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.7704
_exptl_crystal_density_meas      .
_exptl_crystal_description       needle
_exptl_crystal_F_000             576
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.01
_diffrn_reflns_av_R_equivalents  0.0411
_diffrn_reflns_av_unetI/netI     0.0248
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            23407
_diffrn_reflns_theta_full        28.9828
_diffrn_reflns_theta_max         28.98
_diffrn_reflns_theta_min         1.88
_diffrn_ambient_temperature      120
_diffrn_measured_fraction_theta_full 0.9997
_diffrn_measured_fraction_theta_max 0.9997
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_standards_number         0
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              16
_reflns_limit_h_min              -25
_reflns_limit_k_max              5
_reflns_limit_k_min              0
_reflns_limit_l_max              30
_reflns_limit_l_min              0
_reflns_number_gt                2551
_reflns_number_total             2911
_reflns_threshold_expression     I>=2u(I)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine (Bourhis et al., 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.5856
_refine_diff_density_min         -0.3679
_refine_diff_density_rms         0.0884
_refine_ls_d_res_high            0.7334
_refine_ls_d_res_low             10.8223
_refine_ls_goodness_of_fit_ref   1.0206
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    16
_refine_ls_number_parameters     154
_refine_ls_number_reflns         2911
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0287
_refine_ls_R_factor_gt           0.0228
_refine_ls_restrained_S_all      1.0206
_refine_ls_shift/su_max          0.0000
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0281P)²+0.7264P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0547
_refine_ls_wR_factor_ref         0.0573
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C12(H12), C13(H13)
;
_atom_sites_solution_primary     dual
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_refinement_flags_posn
Br1 Br 0.643310(12) -0.12609(4) 0.931269(11) 0.01964(6) Uani 1.000000 .
F1 F 0.25018(8) 0.7726(3) 0.85941(6) 0.0228(2) Uani 1.000000 .
N1 N 0.12687(11) 0.5841(3) 0.64028(9) 0.0154(3) Uani 1.000000 .
N2 N 0.04943(11) 0.7636(4) 0.62097(9) 0.0142(3) Uani 1.000000 .
C1 C 0.21280(13) 0.5655(4) 0.73342(10) 0.0142(3) Uani 1.000000 .
C2 C -0.05162(13) 0.8430(4) 0.53394(11) 0.0170(3) Uani 1.000000 .
H2 H -0.07211(13) 0.7705(4) 0.48198(11) 0.0204(4) Uiso 1.000000 R
C3 C -0.12178(13) 1.0280(4) 0.52381(11) 0.0182(3) Uani 1.000000 .
H3 H -0.19162(13) 1.0871(4) 0.46416(11) 0.0218(4) Uiso 1.000000 R
C4 C -0.09147(14) 1.1342(4) 0.60194(12) 0.0196(3) Uani 1.000000 .
H4 H -0.14159(14) 1.2604(4) 0.59383(12) 0.0235(4) Uiso 1.000000 R
C5 C 0.00921(14) 1.0549(4) 0.68816(12) 0.0175(3) Uani 1.000000 .
H5 H 0.03003(14) 1.1272(4) 0.74028(12) 0.0210(4) Uiso 1.000000 R
C6 C 0.08206(13) 0.8631(4) 0.69854(11) 0.0153(3) Uani 1.000000 .
C7 C 0.18651(13) 0.7324(4) 0.76997(11) 0.0153(3) Uani 1.000000 .
C8 C 0.31441(13) 0.3949(4) 0.78016(11) 0.0147(3) Uani 1.000000 .
C9 C 0.39550(13) 0.3229(4) 0.87417(11) 0.0171(3) Uani 1.000000 .
H9 H 0.38378(13) 0.3818(4) 0.90767(11) 0.0205(4) Uiso 1.000000 R
C10 C 0.49273(13) 0.1666(4) 0.91878(11) 0.0176(3) Uani 1.000000 .
H10 H 0.54755(13) 0.1206(4) 0.98247(11) 0.0212(4) Uiso 1.000000 R
C11 C 0.50869(13) 0.0786(4) 0.86907(11) 0.0158(3) Uani 1.000000 .
C12 C 0.42975(13) 0.1433(4) 0.77585(11) 0.0184(3) Uani 1.000000 .
H12 H 0.44153(13) 0.0803(4) 0.74260(11) 0.0221(4) Uiso 1.000000 R
C13 C 0.33313(13) 0.3019(4) 0.73207(11) 0.0173(3) Uani 1.000000 .
H13 H 0.27886(13) 0.3481(4) 0.66841(11) 0.0208(4) Uiso 1.000000 R


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 C11 1.9022(16) . ?
F1 C7 1.3544(18) . ?
N1 N2 1.3564(19) . ?
N1 C1 1.363(2) . ?
N2 C2 1.375(2) . ?
N2 C6 1.389(2) . ?
C1 C7 1.396(2) . ?
C1 C8 1.466(2) . ?
C2 H2 0.9500 . ?
C2 C3 1.363(2) . ?
C3 H3 0.9500 . ?
C3 C4 1.430(2) . ?
C4 H4 0.9500 . ?
C4 C5 1.366(2) . ?
C5 H5 0.9500 . ?
C5 C6 1.416(2) . ?
C6 C7 1.383(2) . ?
C8 C9 1.405(2) . ?
C8 C13 1.402(2) . ?
C9 H9 0.9500 . ?
C9 C10 1.391(2) . ?
C10 H10 0.9500 . ?
C10 C11 1.389(2) . ?
C11 C12 1.390(2) . ?
C12 H12 0.9500 . ?
C12 C13 1.392(2) . ?
C13 H13 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 N2 104.83(13) . . ?
C2 N2 N1 124.32(13) . . ?
C6 N2 N1 113.28(13) . . ?
C6 N2 C2 122.39(14) . . ?
C7 C1 N1 109.68(14) . . ?
C8 C1 N1 120.53(14) . . ?
C8 C1 C7 129.77(14) . . ?
H2 C2 N2 120.72(9) . . ?
C3 C2 N2 118.57(15) . . ?
C3 C2 H2 120.72(10) . . ?
H3 C3 C2 119.62(10) . . ?
C4 C3 C2 120.76(15) . . ?
C4 C3 H3 119.62(10) . . ?
H4 C4 C3 119.86(10) . . ?
C5 C4 C3 120.28(15) . . ?
C5 C4 H4 119.86(10) . . ?
H5 C5 C4 120.56(10) . . ?
C6 C5 C4 118.87(15) . . ?
C6 C5 H5 120.56(9) . . ?
C5 C6 N2 119.12(14) . . ?
C7 C6 N2 103.73(14) . . ?
C7 C6 C5 137.14(15) . . ?
C1 C7 F1 127.76(14) . . ?
C6 C7 F1 123.77(14) . . ?
C6 C7 C1 108.46(14) . . ?
C9 C8 C1 120.86(14) . . ?
C13 C8 C1 120.65(14) . . ?
C13 C8 C9 118.49(15) . . ?
H9 C9 C8 119.60(9) . . ?
C10 C9 C8 120.79(15) . . ?
C10 C9 H9 119.60(10) . . ?
H10 C10 C9 120.40(10) . . ?
C11 C10 C9 119.20(15) . . ?
C11 C10 H10 120.40(9) . . ?
C10 C11 Br1 118.85(12) . . ?
C12 C11 Br1 119.66(12) . . ?
C12 C11 C10 121.48(15) . . ?
H12 C12 C11 120.59(10) . . ?
C13 C12 C11 118.83(15) . . ?
C13 C12 H12 120.59(9) . . ?
C12 C13 C8 121.21(15) . . ?
H13 C13 C8 119.40(9) . . ?
H13 C13 C12 119.40(9) . . ?

_olex2_submission_special_instructions 'No special instructions were received'
####################################################################### 
# 
# 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_VM1183
_database_code_depnum_ccdc_archive 'CCDC 1969358'
loop_
_audit_author_name
_audit_author_address
'Mikhail Minyaev'
;N D Zelinsky Institute of Organic Chemistry RAS
Russia
;
_audit_update_record             
;
2019-12-02 deposited with the CCDC.	2020-01-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        
2-(4-Bromophenyl)-3-fluoro-pyrazolo[1,5-a]pyridazine
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H7 Br F N3'
_chemical_formula_sum            'C12 H7 Br F N3'
_chemical_formula_weight         292.12

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'
Br Br -0.2901 2.4595 '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                   3.89430(10)
_cell_length_b                   25.4059(6)
_cell_length_c                   10.7978(3)
_cell_angle_alpha                90
_cell_angle_beta                 98.1600(10)
_cell_angle_gamma                90
_cell_volume                     1057.50(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9978
_cell_measurement_theta_min      3.07
_cell_measurement_theta_max      34.92

_exptl_crystal_description       needle
_exptl_crystal_colour            colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    1.835
_exptl_crystal_F_000             576
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.58
_exptl_crystal_size_mid          0.19
_exptl_crystal_size_min          0.14
_exptl_absorpt_coefficient_mu    3.878
_shelx_estimated_absorpt_T_min   0.212
_shelx_estimated_absorpt_T_max   0.613
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.5085
_exptl_absorpt_correction_T_max  0.7469
_exptl_absorpt_process_details   'SADABS 2016/2 (Krause et al., 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'X-Ray tube'
_diffrn_measurement_device_type  'Bruker AXS D8 QUEST'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            34602
_diffrn_reflns_av_unetI/netI     0.0238
_diffrn_reflns_av_R_equivalents  0.0481
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_k_max       38
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         2.490
_diffrn_reflns_theta_max         32.998
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             3957
_reflns_number_gt                3475
_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       'APEX3 (Bruker, 2016)'
_computing_cell_refinement       'SAINT (Bruker, 2016)'
_computing_data_reduction        'SAINT (Bruker, 2016)'
_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-2018 (Sheldrick, 2015a)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2015b)'
_computing_publication_material  'SHELXTL (Sheldrick, 2015b)'
_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)+(0.0201P)²+0.6421P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3957
_refine_ls_number_parameters     182
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0301
_refine_ls_R_factor_gt           0.0235
_refine_ls_wR_factor_ref         0.0554
_refine_ls_wR_factor_gt          0.0523
_refine_ls_goodness_of_fit_ref   1.060
_refine_ls_restrained_S_all      1.060
_refine_ls_shift/su_max          0.004
_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 1.28490(3) 0.57447(2) 0.82312(2) 0.01676(4) Uani 1 1 d . . . . .
F1 F 0.3006(2) 0.37214(3) 0.47289(7) 0.01943(17) Uani 1 1 d . . . . .
N1 N 0.6714(3) 0.31909(4) 0.76626(10) 0.01240(19) Uani 1 1 d . . . . .
N2 N 0.4816(3) 0.27968(4) 0.71023(9) 0.01118(18) Uani 1 1 d . . . . .
N3 N 0.4664(3) 0.23315(4) 0.76938(10) 0.01382(19) Uani 1 1 d . . . . .
H3 H 0.889(5) 0.5276(8) 0.5998(18) 0.022(5) Uiso 1 1 d . . . . .
C4 C 0.2685(3) 0.19787(5) 0.70548(12) 0.0148(2) Uani 1 1 d . . . . .
H4 H 0.253(4) 0.1652(7) 0.7472(16) 0.014(4) Uiso 1 1 d . . . . .
C5 C 0.0810(3) 0.20581(5) 0.58394(12) 0.0146(2) Uani 1 1 d . . . . .
H5 H -0.057(5) 0.1784(7) 0.5437(17) 0.018(4) Uiso 1 1 d . . . . .
C8 C 0.4107(3) 0.34335(5) 0.57533(11) 0.0127(2) Uani 1 1 d . . . . .
C7 C 0.3123(3) 0.29194(5) 0.59221(11) 0.0115(2) Uani 1 1 d . . . . .
C6 C 0.1016(3) 0.25302(5) 0.52631(11) 0.0134(2) Uani 1 1 d . . . . .
H6 H -0.020(5) 0.2602(7) 0.4475(17) 0.015(4) Uiso 1 1 d . . . . .
C10 C 0.7930(3) 0.41022(5) 0.71368(11) 0.0120(2) Uani 1 1 d . . . . .
C11 C 0.9798(4) 0.41853(5) 0.83234(12) 0.0151(2) Uani 1 1 d . . . . .
H11 H 1.004(5) 0.3913(8) 0.8906(17) 0.021(5) Uiso 1 1 d . . . . .
C12 C 1.1273(4) 0.46713(5) 0.86558(12) 0.0155(2) Uani 1 1 d . . . . .
H12 H 1.251(5) 0.4726(8) 0.9471(19) 0.026(5) Uiso 1 1 d . . . . .
C13 C 1.0883(3) 0.50758(5) 0.77901(12) 0.0133(2) Uani 1 1 d . . . . .
C14 C 0.9101(4) 0.50040(5) 0.66005(12) 0.0163(2) Uani 1 1 d . . . . .
C15 C 0.7633(4) 0.45163(5) 0.62776(12) 0.0153(2) Uani 1 1 d . . . . .
H15 H 0.645(6) 0.4471(9) 0.549(2) 0.034(6) Uiso 1 1 d . . . . .
C9 C 0.6283(3) 0.35925(5) 0.68246(11) 0.0117(2) 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
Br1 C13 1.8965(13) . ?
F1 C8 1.3447(14) . ?
N1 N2 1.3371(14) . ?
N1 C9 1.3583(16) . ?
N2 N3 1.3488(15) . ?
N2 C7 1.3847(15) . ?
N3 C4 1.3124(17) . ?
C4 C5 1.4226(18) . ?
C4 H4 0.950(18) . ?
C5 C6 1.3589(18) . ?
C5 H5 0.947(19) . ?
C8 C7 1.3803(17) . ?
C8 C9 1.3931(17) . ?
C7 C6 1.4113(17) . ?
C6 H6 0.931(18) . ?
C10 C15 1.3967(18) . ?
C10 C11 1.3967(18) . ?
C10 C9 1.4631(17) . ?
C11 C12 1.3875(18) . ?
C11 H11 0.931(19) . ?
C12 C13 1.3830(18) . ?
C12 H12 0.95(2) . ?
C13 C14 1.3828(18) . ?
C14 C15 1.3880(19) . ?
C14 H3 0.94(2) . ?
C15 H15 0.91(2) . ?

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
N2 N1 C9 104.65(10) . . ?
N1 N2 N3 120.04(10) . . ?
N1 N2 C7 114.09(10) . . ?
N3 N2 C7 125.87(11) . . ?
C4 N3 N2 114.30(11) . . ?
N3 C4 C5 125.06(12) . . ?
N3 C4 H4 114.8(11) . . ?
C5 C4 H4 120.1(11) . . ?
C6 C5 C4 119.45(12) . . ?
C6 C5 H5 120.4(11) . . ?
C4 C5 H5 120.2(11) . . ?
F1 C8 C7 124.13(11) . . ?
F1 C8 C9 127.64(11) . . ?
C7 C8 C9 108.20(11) . . ?
C8 C7 N2 103.27(10) . . ?
C8 C7 C6 138.49(12) . . ?
N2 C7 C6 118.23(11) . . ?
C5 C6 C7 117.10(11) . . ?
C5 C6 H6 122.4(11) . . ?
C7 C6 H6 120.5(11) . . ?
C15 C10 C11 118.60(12) . . ?
C15 C10 C9 121.43(11) . . ?
C11 C10 C9 119.96(11) . . ?
C12 C11 C10 120.95(12) . . ?
C12 C11 H11 119.2(12) . . ?
C10 C11 H11 119.8(12) . . ?
C13 C12 C11 119.00(12) . . ?
C13 C12 H12 120.6(13) . . ?
C11 C12 H12 120.4(13) . . ?
C14 C13 C12 121.48(12) . . ?
C14 C13 Br1 118.89(10) . . ?
C12 C13 Br1 119.63(10) . . ?
C13 C14 C15 119.06(12) . . ?
C13 C14 H3 121.7(12) . . ?
C15 C14 H3 119.2(12) . . ?
C14 C15 C10 120.88(12) . . ?
C14 C15 H15 118.7(14) . . ?
C10 C15 H15 120.4(14) . . ?
N1 C9 C8 109.78(11) . . ?
N1 C9 C10 120.18(11) . . ?
C8 C9 C10 130.02(11) . . ?

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
C9 N1 N2 N3 -179.75(11) . . . . ?
C9 N1 N2 C7 -0.15(14) . . . . ?
N1 N2 N3 C4 179.19(11) . . . . ?
C7 N2 N3 C4 -0.36(18) . . . . ?
N2 N3 C4 C5 0.13(19) . . . . ?
N3 C4 C5 C6 0.0(2) . . . . ?
F1 C8 C7 N2 -178.62(11) . . . . ?
C9 C8 C7 N2 -0.42(13) . . . . ?
F1 C8 C7 C6 0.7(2) . . . . ?
C9 C8 C7 C6 178.93(15) . . . . ?
N1 N2 C7 C8 0.36(14) . . . . ?
N3 N2 C7 C8 179.94(11) . . . . ?
N1 N2 C7 C6 -179.15(11) . . . . ?
N3 N2 C7 C6 0.42(18) . . . . ?
C4 C5 C6 C7 0.03(19) . . . . ?
C8 C7 C6 C5 -179.52(15) . . . . ?
N2 C7 C6 C5 -0.23(18) . . . . ?
C15 C10 C11 C12 1.3(2) . . . . ?
C9 C10 C11 C12 -177.58(12) . . . . ?
C10 C11 C12 C13 -0.3(2) . . . . ?
C11 C12 C13 C14 -0.8(2) . . . . ?
C11 C12 C13 Br1 179.51(10) . . . . ?
C12 C13 C14 C15 0.9(2) . . . . ?
Br1 C13 C14 C15 -179.46(10) . . . . ?
C13 C14 C15 C10 0.2(2) . . . . ?
C11 C10 C15 C14 -1.3(2) . . . . ?
C9 C10 C15 C14 177.61(12) . . . . ?
N2 N1 C9 C8 -0.14(14) . . . . ?
N2 N1 C9 C10 178.27(11) . . . . ?
F1 C8 C9 N1 178.48(12) . . . . ?
C7 C8 C9 N1 0.36(15) . . . . ?
F1 C8 C9 C10 0.3(2) . . . . ?
C7 C8 C9 C10 -177.83(12) . . . . ?
C15 C10 C9 N1 177.71(12) . . . . ?
C11 C10 C9 N1 -3.43(18) . . . . ?
C15 C10 C9 C8 -4.2(2) . . . . ?
C11 C10 C9 C8 174.61(13) . . . . ?

_refine_diff_density_max         0.533
_refine_diff_density_min         -0.727
_refine_diff_density_rms         0.076

