# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_AR01
_database_code_depnum_ccdc_archive 'CCDC 1430146'
_audit_update_record             
;
2015-10-08 deposited with the CCDC.
2016-03-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
(E)-1,2-bis(5-chloro-4-(trifluoromethyl)pyridin-2-yl)diazene
_chemical_name_common            ?
_chemical_formula_moiety         'C12 H4 Cl2 F6 N4'
_chemical_formula_sum            'C12 H4 Cl2 F6 N4'
_chemical_melting_point          ?

_exptl_crystal_description       needle
_exptl_crystal_colour            orange
_diffrn_ambient_temperature      200(2)
_chemical_formula_weight         389.09

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'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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, -z'

_cell_length_a                   4.7813(5)
_cell_length_b                   6.6169(7)
_cell_length_c                   11.6910(12)
_cell_angle_alpha                75.795(8)
_cell_angle_beta                 86.893(8)
_cell_angle_gamma                88.052(8)
_cell_volume                     357.95(7)
_cell_formula_units_Z            1
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    5535
_cell_measurement_theta_min      1.80
_cell_measurement_theta_max      25.55
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.805
_exptl_crystal_F_000             192
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.670
_exptl_crystal_size_mid          0.050
_exptl_crystal_size_min          0.050
_exptl_absorpt_coefficient_mu    0.526
_shelx_estimated_absorpt_T_min   0.719
_shelx_estimated_absorpt_T_max   0.974
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            4600
_diffrn_reflns_av_unetI/netI     0.1008
_diffrn_reflns_av_R_equivalents  0.1694
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         1.799
_diffrn_reflns_theta_max         24.993
_diffrn_reflns_theta_full        24.993
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             1265
_reflns_number_gt                1106
_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       'X-Area (Stoe & Cie, 2009)'
_computing_cell_refinement       'X-Area (Stoe & Cie, 2009)'
_computing_data_reduction        'X-RED32(Stoe & Cie, 2009)'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+0.0052P] 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         1265
_refine_ls_number_parameters     109
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0397
_refine_ls_R_factor_gt           0.0348
_refine_ls_wR_factor_ref         0.0812
_refine_ls_wR_factor_gt          0.0784
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_restrained_S_all      1.042
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Cl1 Cl 0.05487(8) 0.19284(6) 0.84001(4) 0.04375(18) Uani 1 1 d . . . . .
F3 F 0.5150(2) -0.40794(15) 0.85211(11) 0.0526(3) Uani 1 1 d . . . . .
F2 F 0.4291(3) -0.19452(18) 0.96173(10) 0.0548(3) Uani 1 1 d . . . . .
F1 F 0.1017(2) -0.28154(17) 0.86635(12) 0.0554(3) Uani 1 1 d . . . . .
N2 N 0.9288(3) 0.0826(2) 0.49042(13) 0.0367(3) Uani 1 1 d . . . . .
N1 N 0.5914(3) 0.2745(2) 0.56600(14) 0.0405(4) Uani 1 1 d . . . . .
C5 C 0.7200(3) 0.0886(2) 0.58117(15) 0.0334(4) Uani 1 1 d . . . . .
C3 C 0.4454(3) -0.0555(2) 0.75663(15) 0.0322(4) Uani 1 1 d . . . . .
C4 C 0.6498(3) -0.0816(2) 0.67414(15) 0.0331(4) Uani 1 1 d . . . . .
H4 H 0.7419 -0.2131 0.6802 0.040 Uiso 1 1 calc R U . . .
C2 C 0.3127(3) 0.1403(2) 0.74278(16) 0.0350(4) Uani 1 1 d . . . . .
C1 C 0.3942(3) 0.2986(2) 0.64532(17) 0.0392(4) Uani 1 1 d . . . . .
H1 H 0.3028 0.4311 0.6354 0.047 Uiso 1 1 calc R U . . .
C6 C 0.3714(3) -0.2355(3) 0.85993(16) 0.0389(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
Cl1 C2 1.7163(18) . ?
F3 C6 1.331(2) . ?
F2 C6 1.329(2) . ?
F1 C6 1.329(2) . ?
N2 N2 1.246(3) 2_756 ?
N2 C5 1.424(2) . ?
N1 C1 1.320(2) . ?
N1 C5 1.332(2) . ?
C5 C4 1.396(2) . ?
C3 C4 1.372(2) . ?
C3 C2 1.400(2) . ?
C3 C6 1.510(2) . ?
C2 C1 1.393(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 N2 C5 113.33(16) 2_756 . ?
C1 N1 C5 117.80(13) . . ?
N1 C5 C4 123.19(15) . . ?
N1 C5 N2 112.47(13) . . ?
C4 C5 N2 124.31(14) . . ?
C4 C3 C2 118.49(14) . . ?
C4 C3 C6 119.78(14) . . ?
C2 C3 C6 121.73(15) . . ?
C3 C4 C5 118.75(13) . . ?
C1 C2 C3 118.17(16) . . ?
C1 C2 Cl1 118.90(12) . . ?
C3 C2 Cl1 122.93(12) . . ?
N1 C1 C2 123.56(14) . . ?
F2 C6 F1 107.45(15) . . ?
F2 C6 F3 107.43(14) . . ?
F1 C6 F3 106.65(14) . . ?
F2 C6 C3 111.33(15) . . ?
F1 C6 C3 112.50(13) . . ?
F3 C6 C3 111.20(15) . . ?

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
C1 N1 C5 C4 2.1(3) . . . . ?
C1 N1 C5 N2 -179.68(16) . . . . ?
N2 N2 C5 N1 172.90(18) 2_756 . . . ?
N2 N2 C5 C4 -8.9(3) 2_756 . . . ?
C2 C3 C4 C5 1.0(3) . . . . ?
C6 C3 C4 C5 -178.29(16) . . . . ?
N1 C5 C4 C3 -2.4(3) . . . . ?
N2 C5 C4 C3 179.62(15) . . . . ?
C4 C3 C2 C1 0.4(3) . . . . ?
C6 C3 C2 C1 179.68(17) . . . . ?
C4 C3 C2 Cl1 -179.84(13) . . . . ?
C6 C3 C2 Cl1 -0.5(2) . . . . ?
C5 N1 C1 C2 -0.5(3) . . . . ?
C3 C2 C1 N1 -0.7(3) . . . . ?
Cl1 C2 C1 N1 179.54(15) . . . . ?
C4 C3 C6 F2 116.36(18) . . . . ?
C2 C3 C6 F2 -62.9(2) . . . . ?
C4 C3 C6 F1 -122.96(18) . . . . ?
C2 C3 C6 F1 57.7(2) . . . . ?
C4 C3 C6 F3 -3.4(2) . . . . ?
C2 C3 C6 F3 177.29(15) . . . . ?

_refine_diff_density_max         0.271
_refine_diff_density_min         -0.402
_refine_diff_density_rms         0.057

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_h-m   'P -1'
_symmetry_int_tables_number      2
_chemical_absolute_configuration .

####################################################################### 
# 
# 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_AR-02
_database_code_depnum_ccdc_archive 'CCDC 1430147'
_audit_update_record             
;
2015-10-08 deposited with the CCDC.
2016-03-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        
(E)-1,2-bis(4-(trifluoromethyl)pyridin-2-yl)diazene
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H6 F6 N4'
_chemical_formula_sum            'C12 H6 F6 N4'
_chemical_formula_weight         320.21

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'

_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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, -z'

_cell_length_a                   4.6634(4)
_cell_length_b                   11.6504(12)
_cell_length_c                   13.1188(14)
_cell_angle_alpha                113.797(8)
_cell_angle_beta                 93.861(8)
_cell_angle_gamma                100.985(8)
_cell_volume                     631.90(12)
_cell_formula_units_Z            2
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    2161
_cell_measurement_theta_min      1.96
_cell_measurement_theta_max      22.90

_exptl_crystal_description       'rectangular plate'
_exptl_crystal_colour            orange
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.683
_exptl_crystal_F_000             320
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.100
_exptl_crystal_size_min          0.020
_exptl_absorpt_coefficient_mu    0.167
_shelx_estimated_absorpt_T_min   0.967
_shelx_estimated_absorpt_T_max   0.997
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      200(2)
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            8137
_diffrn_reflns_av_unetI/netI     0.1068
_diffrn_reflns_av_R_equivalents  0.0982
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_theta_min         1.719
_diffrn_reflns_theta_max         24.989
_diffrn_reflns_theta_full        24.989
_diffrn_measured_fraction_theta_max 0.941
_diffrn_measured_fraction_theta_full 0.941
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_Laue_measured_fraction_full 0.941
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_point_group_measured_fraction_full 0.941
_reflns_number_total             2095
_reflns_number_gt                868
_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       'X-Area (Stoe & Cie, 2009)'
_computing_cell_refinement       'X-Area (Stoe & Cie, 2009)'
_computing_data_reduction        'X-RED32(Stoe & Cie, 2009)'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.0408P)²] 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         2095
_refine_ls_number_parameters     199
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1351
_refine_ls_R_factor_gt           0.0463
_refine_ls_wR_factor_ref         0.1029
_refine_ls_wR_factor_gt          0.0864
_refine_ls_goodness_of_fit_ref   0.779
_refine_ls_restrained_S_all      0.779
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.7338(9) 0.2765(4) 0.0653(4) 0.0560(11) Uani 1 1 d . . . . .
H1 H 0.8524 0.3220 0.0311 0.067 Uiso 1 1 calc R U . . .
C2 C 0.8204(9) 0.3077(4) 0.1764(4) 0.0529(11) Uani 1 1 d . . . . .
H2 H 0.9942 0.3730 0.2177 0.063 Uiso 1 1 calc R U . . .
C3 C 0.6521(8) 0.2431(3) 0.2277(3) 0.0431(9) Uani 1 1 d . . . . .
C4 C 0.4032(8) 0.1471(3) 0.1644(3) 0.0441(9) Uani 1 1 d . . . . .
H4 H 0.2847 0.0989 0.1966 0.053 Uiso 1 1 calc R U . . .
C5 C 0.3336(8) 0.1241(3) 0.0528(3) 0.0429(9) Uani 1 1 d . . . . .
C6 C 0.7373(10) 0.2778(4) 0.3498(3) 0.0580(11) Uani 1 1 d . . . . .
C7 C -0.4644(10) 0.6231(4) 0.3323(3) 0.0650(13) Uani 1 1 d . . . . .
H7 H -0.5413 0.5976 0.3872 0.078 Uiso 1 1 calc R U . . .
C8 C -0.2471(9) 0.7376(4) 0.3700(3) 0.0580(12) Uani 1 1 d . . . . .
H8 H -0.1764 0.7891 0.4482 0.070 Uiso 1 1 calc R U . . .
C9 C -0.1387(9) 0.7732(3) 0.2891(3) 0.0455(10) Uani 1 1 d . . . . .
C10 C -0.2414(8) 0.6962(3) 0.1769(3) 0.0447(10) Uani 1 1 d . . . . .
H10 H -0.1681 0.7192 0.1202 0.054 Uiso 1 1 calc R U . . .
C11 C -0.4555(9) 0.5839(3) 0.1492(3) 0.0460(10) Uani 1 1 d . . . . .
C12 C 0.0868(10) 0.8973(4) 0.3231(3) 0.0591(12) Uani 1 1 d . . . . .
N1 N 0.4917(7) 0.1854(3) 0.0009(3) 0.0509(9) Uani 1 1 d . . . . .
N2 N 0.0780(7) 0.0281(3) -0.0234(2) 0.0489(8) Uani 1 1 d . . . . .
N4 N -0.5802(7) 0.4950(3) 0.0346(2) 0.0472(8) Uani 1 1 d . . . . .
N3 N -0.5714(8) 0.5468(3) 0.2237(3) 0.0576(10) Uani 1 1 d . . . . .
F1 F 1.0216(6) 0.2862(3) 0.3773(2) 0.0934(10) Uani 1 1 d . . . . .
F2 F 0.5886(6) 0.1963(2) 0.38587(18) 0.0749(8) Uani 1 1 d . . . . .
F3 F 0.6890(6) 0.3930(2) 0.41486(19) 0.0853(9) Uani 1 1 d . . . . .
F4 F 0.2701(6) 0.8922(2) 0.2496(2) 0.0821(8) Uani 1 1 d . . . . .
F5 F 0.2543(6) 0.9340(3) 0.4214(2) 0.1031(10) Uani 1 1 d . . . . .
F6 F -0.0354(6) 0.9946(2) 0.3340(2) 0.0917(10) 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 N1 1.344(5) . ?
C1 C2 1.362(5) . ?
C1 H1 0.9500 . ?
C2 C3 1.375(5) . ?
C2 H2 0.9500 . ?
C3 C4 1.383(5) . ?
C3 C6 1.489(5) . ?
C4 C5 1.381(5) . ?
C4 H4 0.9500 . ?
C5 N1 1.333(4) . ?
C5 N2 1.449(4) . ?
C6 F1 1.325(5) . ?
C6 F2 1.328(4) . ?
C6 F3 1.341(5) . ?
C7 N3 1.335(5) . ?
C7 C8 1.392(5) . ?
C7 H7 0.9500 . ?
C8 C9 1.379(5) . ?
C8 H8 0.9500 . ?
C9 C10 1.369(5) . ?
C9 C12 1.495(5) . ?
C10 C11 1.382(4) . ?
C10 H10 0.9500 . ?
C11 N3 1.325(4) . ?
C11 N4 1.438(4) . ?
C12 F5 1.322(5) . ?
C12 F4 1.322(5) . ?
C12 F6 1.325(5) . ?
N2 N2 1.239(5) 2 ?
N4 N4 1.240(5) 2_465 ?

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
N1 C1 C2 124.3(3) . . ?
N1 C1 H1 117.9 . . ?
C2 C1 H1 117.9 . . ?
C1 C2 C3 118.9(4) . . ?
C1 C2 H2 120.6 . . ?
C3 C2 H2 120.6 . . ?
C4 C3 C2 119.0(3) . . ?
C4 C3 C6 121.1(3) . . ?
C2 C3 C6 120.0(3) . . ?
C3 C4 C5 117.4(3) . . ?
C3 C4 H4 121.3 . . ?
C5 C4 H4 121.3 . . ?
N1 C5 C4 124.9(3) . . ?
N1 C5 N2 111.3(3) . . ?
C4 C5 N2 123.8(3) . . ?
F1 C6 F2 106.3(4) . . ?
F1 C6 F3 106.1(3) . . ?
F2 C6 F3 105.0(3) . . ?
F1 C6 C3 112.7(3) . . ?
F2 C6 C3 114.6(3) . . ?
F3 C6 C3 111.5(4) . . ?
N3 C7 C8 124.0(4) . . ?
N3 C7 H7 118.0 . . ?
C8 C7 H7 118.0 . . ?
C9 C8 C7 117.1(4) . . ?
C9 C8 H8 121.4 . . ?
C7 C8 H8 121.4 . . ?
C10 C9 C8 120.2(3) . . ?
C10 C9 C12 119.5(3) . . ?
C8 C9 C12 120.3(3) . . ?
C9 C10 C11 117.6(3) . . ?
C9 C10 H10 121.2 . . ?
C11 C10 H10 121.2 . . ?
N3 C11 C10 124.5(3) . . ?
N3 C11 N4 112.6(3) . . ?
C10 C11 N4 122.9(3) . . ?
F5 C12 F4 106.2(4) . . ?
F5 C12 F6 105.6(4) . . ?
F4 C12 F6 106.0(4) . . ?
F5 C12 C9 112.9(4) . . ?
F4 C12 C9 113.1(4) . . ?
F6 C12 C9 112.4(4) . . ?
C1 N1 C5 115.5(3) . . ?
N2 N2 C5 112.8(4) 2 . ?
N4 N4 C11 113.2(4) 2_465 . ?
C11 N3 C7 116.5(3) . . ?

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
N1 C1 C2 C3 -0.1(6) . . . . ?
C1 C2 C3 C4 1.1(6) . . . . ?
C1 C2 C3 C6 -178.4(4) . . . . ?
C2 C3 C4 C5 -1.7(5) . . . . ?
C6 C3 C4 C5 177.7(4) . . . . ?
C3 C4 C5 N1 1.5(6) . . . . ?
C3 C4 C5 N2 -179.1(3) . . . . ?
C4 C3 C6 F1 132.6(4) . . . . ?
C2 C3 C6 F1 -48.0(5) . . . . ?
C4 C3 C6 F2 10.9(6) . . . . ?
C2 C3 C6 F2 -169.7(4) . . . . ?
C4 C3 C6 F3 -108.1(4) . . . . ?
C2 C3 C6 F3 71.3(5) . . . . ?
N3 C7 C8 C9 0.2(7) . . . . ?
C7 C8 C9 C10 -0.9(6) . . . . ?
C7 C8 C9 C12 177.7(4) . . . . ?
C8 C9 C10 C11 0.3(6) . . . . ?
C12 C9 C10 C11 -178.3(4) . . . . ?
C9 C10 C11 N3 1.2(6) . . . . ?
C9 C10 C11 N4 -179.8(4) . . . . ?
C10 C9 C12 F5 -153.2(4) . . . . ?
C8 C9 C12 F5 28.1(6) . . . . ?
C10 C9 C12 F4 -32.6(6) . . . . ?
C8 C9 C12 F4 148.8(4) . . . . ?
C10 C9 C12 F6 87.5(5) . . . . ?
C8 C9 C12 F6 -91.2(5) . . . . ?
C2 C1 N1 C5 -0.2(6) . . . . ?
C4 C5 N1 C1 -0.6(5) . . . . ?
N2 C5 N1 C1 -180.0(3) . . . . ?
N1 C5 N2 N2 -178.1(4) . . . 2 ?
C4 C5 N2 N2 2.5(6) . . . 2 ?
N3 C11 N4 N4 -159.2(4) . . . 2_465 ?
C10 C11 N4 N4 21.7(6) . . . 2_465 ?
C10 C11 N3 C7 -1.9(6) . . . . ?
N4 C11 N3 C7 179.0(4) . . . . ?
C8 C7 N3 C11 1.2(6) . . . . ?

_refine_diff_density_max         0.186
_refine_diff_density_min         -0.170
_refine_diff_density_rms         0.045


# start Validation Reply Form

_vrf_PLAT029_AR-02               
;
PROBLEM: _diffrn_measured_fraction_theta_full Low .......      0.941 Note  
RESPONSE: Too low diffraction in high angles
;
_vrf_PLAT911_AR-02               
;
PROBLEM: Missing # FCF Refl Between THmin & STh/L=  0.594        132 Report
RESPONSE: Too low diffraction in high angles
;
# end Validation Reply Form
####################################################################### 
# 
# 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_ek173_twin
_database_code_depnum_ccdc_archive 'CCDC 1430148'
_audit_update_record             
;
2015-10-08 deposited with the CCDC.
2016-03-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        'dimanganese tetraazopyridine tetrabromide'
_chemical_name_common            ?
_chemical_formula_moiety         'C30 H24 Br4 Mn2 N12'
_chemical_formula_sum            'C30 H24 Br4 Mn2 N12'
_chemical_melting_point          ?
_exptl_crystal_description       needle
_exptl_crystal_colour            'dark brown'
_diffrn_ambient_temperature      200(2)
_chemical_formula_weight         982.13

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'
Mn Mn 0.3368 0.7283 '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                   12.0263(9)
_cell_length_b                   7.7630(4)
_cell_length_c                   19.2201(15)
_cell_angle_alpha                90
_cell_angle_beta                 105.517(6)
_cell_angle_gamma                90
_cell_volume                     1729.0(2)
_cell_formula_units_Z            2
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    5490
_cell_measurement_theta_min      1.76
_cell_measurement_theta_max      22.71
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.886
_exptl_crystal_F_000             956
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.060
_exptl_crystal_size_mid          0.050
_exptl_crystal_size_min          0.040
_exptl_absorpt_coefficient_mu    5.395
_shelx_estimated_absorpt_T_min   0.738
_shelx_estimated_absorpt_T_max   0.813
_exptl_absorpt_correction_type   integration
_exptl_absorpt_correction_T_min  0.3877
_exptl_absorpt_correction_T_max  0.5053
_exptl_absorpt_process_details   
;
Stoe & Cie (2002). X-SHAPE. Stoe & Cie, Darmstadt, Germany
;
_exptl_absorpt_special_details   ?
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            2987
_diffrn_reflns_av_unetI/netI     0.1017
_diffrn_reflns_av_R_equivalents  ?
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         1.757
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_full        24.999
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measured_fraction_theta_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_point_group_measured_fraction_full 0.991
_reflns_number_total             2987
_reflns_number_gt                1523
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 _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       'X-Area (Stoe & Cie, 2009)'
_computing_cell_refinement       'X-Area (Stoe & Cie, 2009)'
_computing_data_reduction        'X-RED32(Stoe & Cie, 2009)'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_refine_special_details          
;
 Refined as a 2-component perfect twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1172P)²] 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         2987
_refine_ls_number_parameters     217
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1380
_refine_ls_R_factor_gt           0.0743
_refine_ls_wR_factor_ref         0.1982
_refine_ls_wR_factor_gt          0.1732
_refine_ls_goodness_of_fit_ref   0.876
_refine_ls_restrained_S_all      0.876
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
C1 C 0.5520(10) 0.2124(17) 0.3211(7) 0.056(3) Uani 1 1 d . . . . .
H1 H 0.5893 0.2368 0.2844 0.068 Uiso 1 1 calc R U . . .
C2 C 0.4552(12) 0.1111(18) 0.3042(7) 0.063(3) Uani 1 1 d . . . . .
H2 H 0.4274 0.0652 0.2569 0.075 Uiso 1 1 calc R U . . .
C3 C 0.3974(11) 0.0755(17) 0.3567(8) 0.064(4) Uani 1 1 d . . . . .
H3 H 0.3297 0.0065 0.3458 0.076 Uiso 1 1 calc R U . . .
C4 C 0.4421(12) 0.1442(18) 0.4254(9) 0.066(4) Uani 1 1 d . . . . .
H4 H 0.4049 0.1231 0.4624 0.079 Uiso 1 1 calc R U . . .
C5 C 0.5403(11) 0.2428(16) 0.4392(7) 0.055(3) Uani 1 1 d . . . . .
C6 C 0.7156(11) 0.4674(16) 0.5889(6) 0.050(3) Uani 1 1 d . . . . .
C7 C 0.6581(12) 0.4527(17) 0.6433(8) 0.062(3) Uani 1 1 d . . . . .
H7 H 0.5870 0.3928 0.6356 0.074 Uiso 1 1 calc R U . . .
C8 C 0.7101(13) 0.5294(18) 0.7081(7) 0.062(3) Uani 1 1 d . . . . .
H8 H 0.6750 0.5227 0.7469 0.075 Uiso 1 1 calc R U . . .
C9 C 0.8129(11) 0.6161(18) 0.7173(7) 0.059(3) Uani 1 1 d . . . . .
H9 H 0.8503 0.6695 0.7619 0.071 Uiso 1 1 calc R U . . .
C10 C 0.8592(12) 0.6220(19) 0.6594(7) 0.067(4) Uani 1 1 d . . . . .
H10 H 0.9298 0.6826 0.6655 0.081 Uiso 1 1 calc R U . . .
C11 C 0.8302(11) 0.1002(16) 0.5007(7) 0.055(3) Uani 1 1 d . . . . .
H11 H 0.7580 0.0682 0.4692 0.066 Uiso 1 1 calc R U . . .
C12 C 0.8886(13) -0.0131(17) 0.5550(8) 0.066(4) Uani 1 1 d . . . . .
H12 H 0.8550 -0.1213 0.5604 0.079 Uiso 1 1 calc R U . . .
C13 C 0.9937(12) 0.0301(18) 0.6004(8) 0.063(3) Uani 1 1 d . . . . .
H13 H 1.0320 -0.0453 0.6382 0.076 Uiso 1 1 calc R U . . .
C14 C 1.0431(10) 0.1873(15) 0.5899(7) 0.049(3) Uani 1 1 d . . . . .
H14 H 1.1168 0.2209 0.6191 0.059 Uiso 1 1 calc R U . . .
C15 C 0.9798(10) 0.2935(16) 0.5346(6) 0.048(3) Uani 1 1 d . . . . .
N1 N 0.5967(8) 0.2792(12) 0.3877(6) 0.052(2) Uani 1 1 d . . . . .
N2 N 0.5806(9) 0.3105(13) 0.5090(6) 0.052(2) Uani 1 1 d . . . . .
N3 N 0.6690(9) 0.4050(14) 0.5176(5) 0.056(3) Uani 1 1 d . . . . .
N4 N 0.8156(10) 0.5534(16) 0.5987(6) 0.063(3) Uani 1 1 d . . . . .
N5 N 0.8756(8) 0.2507(12) 0.4935(5) 0.047(2) Uani 1 1 d . . . . .
N6 N 1.0333(8) 0.4494(12) 0.5218(5) 0.046(2) Uani 1 1 d . . . . .
Mn1 Mn 0.76063(15) 0.4528(2) 0.42351(10) 0.0498(5) Uani 1 1 d . . . . .
Br1 Br 0.65900(11) 0.74303(17) 0.39902(8) 0.0584(4) Uani 1 1 d . . . . .
Br2 Br 0.81997(11) 0.39063(19) 0.30704(7) 0.0613(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 N1 1.353(16) . ?
C1 C2 1.370(19) . ?
C1 H1 0.9500 . ?
C2 C3 1.40(2) . ?
C2 H2 0.9500 . ?
C3 C4 1.39(2) . ?
C3 H3 0.9500 . ?
C4 C5 1.372(18) . ?
C4 H4 0.9500 . ?
C5 N1 1.371(16) . ?
C5 N2 1.401(16) . ?
C6 N4 1.343(16) . ?
C6 C7 1.405(19) . ?
C6 N3 1.419(16) . ?
C7 C8 1.371(19) . ?
C7 H7 0.9500 . ?
C8 C9 1.377(18) . ?
C8 H8 0.9500 . ?
C9 C10 1.37(2) . ?
C9 H9 0.9500 . ?
C10 N4 1.262(17) . ?
C10 H10 0.9500 . ?
C11 N5 1.312(16) . ?
C11 C12 1.401(18) . ?
C11 H11 0.9500 . ?
C12 C13 1.372(19) . ?
C12 H12 0.9500 . ?
C13 C14 1.395(18) . ?
C13 H13 0.9500 . ?
C14 C15 1.398(17) . ?
C14 H14 0.9500 . ?
C15 N5 1.333(14) . ?
C15 N6 1.422(15) . ?
N1 Mn1 2.335(9) . ?
N2 N3 1.266(14) . ?
N3 Mn1 2.385(11) . ?
N5 Mn1 2.278(9) . ?
N6 N6 1.266(18) 3_766 ?
N6 Mn1 2.536(9) 3_766 ?
Mn1 N6 2.536(10) 3_766 ?
Mn1 Br1 2.546(2) . ?
Mn1 Br2 2.571(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
N1 C1 C2 122.8(13) . . ?
N1 C1 H1 118.6 . . ?
C2 C1 H1 118.6 . . ?
C1 C2 C3 119.8(13) . . ?
C1 C2 H2 120.1 . . ?
C3 C2 H2 120.1 . . ?
C4 C3 C2 118.0(13) . . ?
C4 C3 H3 121.0 . . ?
C2 C3 H3 121.0 . . ?
C5 C4 C3 119.4(14) . . ?
C5 C4 H4 120.3 . . ?
C3 C4 H4 120.3 . . ?
N1 C5 C4 122.8(13) . . ?
N1 C5 N2 120.2(11) . . ?
C4 C5 N2 117.0(12) . . ?
N4 C6 C7 122.4(12) . . ?
N4 C6 N3 114.4(11) . . ?
C7 C6 N3 123.0(12) . . ?
C8 C7 C6 116.5(12) . . ?
C8 C7 H7 121.8 . . ?
C6 C7 H7 121.8 . . ?
C9 C8 C7 120.2(13) . . ?
C9 C8 H8 119.9 . . ?
C7 C8 H8 119.9 . . ?
C8 C9 C10 117.3(12) . . ?
C8 C9 H9 121.4 . . ?
C10 C9 H9 121.4 . . ?
N4 C10 C9 125.2(13) . . ?
N4 C10 H10 117.4 . . ?
C9 C10 H10 117.4 . . ?
N5 C11 C12 119.9(12) . . ?
N5 C11 H11 120.1 . . ?
C12 C11 H11 120.1 . . ?
C13 C12 C11 120.9(13) . . ?
C13 C12 H12 119.5 . . ?
C11 C12 H12 119.5 . . ?
C12 C13 C14 118.4(13) . . ?
C12 C13 H13 120.8 . . ?
C14 C13 H13 120.8 . . ?
C13 C14 C15 117.4(11) . . ?
C13 C14 H14 121.3 . . ?
C15 C14 H14 121.3 . . ?
N5 C15 C14 122.5(11) . . ?
N5 C15 N6 120.5(10) . . ?
C14 C15 N6 117.0(10) . . ?
C1 N1 C5 117.2(10) . . ?
C1 N1 Mn1 126.2(9) . . ?
C5 N1 Mn1 116.6(8) . . ?
N3 N2 C5 114.0(11) . . ?
N2 N3 C6 115.2(10) . . ?
N2 N3 Mn1 122.2(8) . . ?
C6 N3 Mn1 122.4(8) . . ?
C10 N4 C6 118.4(12) . . ?
C11 N5 C15 120.7(10) . . ?
C11 N5 Mn1 118.2(8) . . ?
C15 N5 Mn1 120.3(8) . . ?
N6 N6 C15 114.1(12) 3_766 . ?
N6 N6 Mn1 117.6(10) 3_766 3_766 ?
C15 N6 Mn1 128.3(7) . 3_766 ?
N5 Mn1 N1 96.2(4) . . ?
N5 Mn1 N3 77.0(4) . . ?
N1 Mn1 N3 67.0(4) . . ?
N5 Mn1 N6 65.8(3) . 3_766 ?
N1 Mn1 N6 161.8(3) . 3_766 ?
N3 Mn1 N6 109.3(3) . 3_766 ?
N5 Mn1 Br1 154.7(3) . . ?
N1 Mn1 Br1 97.5(2) . . ?
N3 Mn1 Br1 88.9(3) . . ?
N6 Mn1 Br1 100.3(2) 3_766 . ?
N5 Mn1 Br2 96.8(3) . . ?
N1 Mn1 Br2 92.5(3) . . ?
N3 Mn1 Br2 157.4(3) . . ?
N6 Mn1 Br2 87.1(2) 3_766 . ?
Br1 Mn1 Br2 103.68(8) . . ?

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
N1 C1 C2 C3 1(2) . . . . ?
C1 C2 C3 C4 -1(2) . . . . ?
C2 C3 C4 C5 -0.2(19) . . . . ?
C3 C4 C5 N1 1(2) . . . . ?
C3 C4 C5 N2 179.2(12) . . . . ?
N4 C6 C7 C8 -0.8(19) . . . . ?
N3 C6 C7 C8 -175.7(12) . . . . ?
C6 C7 C8 C9 0(2) . . . . ?
C7 C8 C9 C10 0(2) . . . . ?
C8 C9 C10 N4 -1(2) . . . . ?
N5 C11 C12 C13 -1(2) . . . . ?
C11 C12 C13 C14 -2(2) . . . . ?
C12 C13 C14 C15 2.0(19) . . . . ?
C13 C14 C15 N5 1.0(19) . . . . ?
C13 C14 C15 N6 -176.9(11) . . . . ?
C2 C1 N1 C5 -0.5(18) . . . . ?
C2 C1 N1 Mn1 179.9(9) . . . . ?
C4 C5 N1 C1 -0.4(18) . . . . ?
N2 C5 N1 C1 -178.8(11) . . . . ?
C4 C5 N1 Mn1 179.2(10) . . . . ?
N2 C5 N1 Mn1 0.8(14) . . . . ?
N1 C5 N2 N3 0.8(16) . . . . ?
C4 C5 N2 N3 -177.7(11) . . . . ?
C5 N2 N3 C6 -176.5(10) . . . . ?
C5 N2 N3 Mn1 -2.1(14) . . . . ?
N4 C6 N3 N2 173.9(11) . . . . ?
C7 C6 N3 N2 -10.9(17) . . . . ?
N4 C6 N3 Mn1 -0.6(14) . . . . ?
C7 C6 N3 Mn1 174.6(9) . . . . ?
C9 C10 N4 C6 0(2) . . . . ?
C7 C6 N4 C10 0.5(19) . . . . ?
N3 C6 N4 C10 175.8(12) . . . . ?
C12 C11 N5 C15 3.8(18) . . . . ?
C12 C11 N5 Mn1 -165.9(10) . . . . ?
C14 C15 N5 C11 -4.0(18) . . . . ?
N6 C15 N5 C11 173.8(11) . . . . ?
C14 C15 N5 Mn1 165.5(9) . . . . ?
N6 C15 N5 Mn1 -16.7(14) . . . . ?
N5 C15 N6 N6 11.1(18) . . . 3_766 ?
C14 C15 N6 N6 -171.0(13) . . . 3_766 ?
N5 C15 N6 Mn1 -170.1(8) . . . 3_766 ?
C14 C15 N6 Mn1 7.9(15) . . . 3_766 ?

_refine_diff_density_max         0.728
_refine_diff_density_min         -1.189
_refine_diff_density_rms         0.191

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_h-m   'P 21/c'
_symmetry_int_tables_number      14
_chemical_absolute_configuration .

# start Validation Reply Form
_vrf_PLAT341_shelx               
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............     0.0193 Ang.  
RESPONSE: diffraction in high angle
	_cell_measurement_theta_max      22.71
;

# end Validation Reply Form
_chemical_properties_physical    Light-sensitive
####################################################################### 
# 
# 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_EK186
_database_code_depnum_ccdc_archive 'CCDC 1430149'
_audit_update_record             
;
2015-10-08 deposited with the CCDC.
2016-03-03 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        'Manganese triscarbonyl azopyridine bromide'
_chemical_name_common            ?
_chemical_formula_moiety         'C13 H8 Br Mn N4 O3'
_chemical_formula_sum            'C13 H8 Br Mn N4 O3'
_chemical_melting_point          ?

_exptl_crystal_description       rhombohedral
_exptl_crystal_colour            'dark blue'
_diffrn_ambient_temperature      200(2)
_chemical_formula_weight         403.08

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'
Mn Mn 0.3368 0.7283 '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      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'

_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, -z'

_cell_length_a                   7.0251(4)
_cell_length_b                   8.8782(5)
_cell_length_c                   12.4114(7)
_cell_angle_alpha                87.090(5)
_cell_angle_beta                 80.778(5)
_cell_angle_gamma                69.965(4)
_cell_volume                     717.85(7)
_cell_formula_units_Z            2
_cell_measurement_temperature    200(2)
_cell_measurement_reflns_used    9960
_cell_measurement_theta_min      1.66
_cell_measurement_theta_max      25.69
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.865
_exptl_crystal_F_000             396
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.220
_exptl_crystal_size_mid          0.170
_exptl_crystal_size_min          0.150
_exptl_absorpt_coefficient_mu    3.720
_shelx_estimated_absorpt_T_min   0.495
_shelx_estimated_absorpt_T_max   0.605
_exptl_absorpt_correction_type   integration
_exptl_absorpt_correction_T_min  0.5548
_exptl_absorpt_correction_T_max  0.8108

_exptl_absorpt_process_details   
;
Stoe & Cie (2002). X-SHAPE. Stoe & Cie, Darmstadt, Germany
;
_exptl_absorpt_special_details   ?
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            9293
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_av_R_equivalents  0.0491
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         1.662
_diffrn_reflns_theta_max         24.987
_diffrn_reflns_theta_full        24.987
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             2529
_reflns_number_gt                2304
_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       'X-Area (Stoe & Cie, 2009)'
_computing_cell_refinement       'X-Area (Stoe & Cie, 2009)'
_computing_data_reduction        'X-RED32(Stoe & Cie, 2009)'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.0391P)²+0.3917P] 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         2529
_refine_ls_number_parameters     199
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0307
_refine_ls_R_factor_gt           0.0275
_refine_ls_wR_factor_ref         0.0716
_refine_ls_wR_factor_gt          0.0701
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_restrained_S_all      1.046
_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
C1 C 0.4239(4) 0.5718(4) 0.3131(2) 0.0412(6) Uani 1 1 d . . . . .
C2 C 0.2435(4) 0.4514(3) 0.1996(2) 0.0362(6) Uani 1 1 d . . . . .
C3 C 0.6208(4) 0.4301(3) 0.1380(2) 0.0389(6) Uani 1 1 d . . . . .
C4 C 0.2501(4) 0.3674(3) 0.4892(2) 0.0369(6) Uani 1 1 d . . . . .
H4 H 0.2457 0.4743 0.4979 0.044 Uiso 1 1 calc R U . . .
C5 C 0.1629(4) 0.2954(4) 0.5754(2) 0.0412(6) Uani 1 1 d . . . . .
H5 H 0.1012 0.3521 0.6420 0.049 Uiso 1 1 calc R U . . .
C6 C 0.1660(4) 0.1409(4) 0.5640(2) 0.0416(6) Uani 1 1 d . . . . .
H6 H 0.1044 0.0905 0.6218 0.050 Uiso 1 1 calc R U . . .
C7 C 0.2602(4) 0.0609(3) 0.4669(2) 0.0381(6) Uani 1 1 d . . . . .
H7 H 0.2658 -0.0460 0.4566 0.046 Uiso 1 1 calc R U . . .
C8 C 0.3462(4) 0.1394(3) 0.3852(2) 0.0327(5) Uani 1 1 d . . . . .
C9 C 0.6349(4) 0.0620(3) 0.1214(2) 0.0334(5) Uani 1 1 d . . . . .
C10 C 0.7211(4) -0.1037(3) 0.1179(2) 0.0416(6) Uani 1 1 d . . . . .
H10 H 0.7082 -0.1668 0.1810 0.050 Uiso 1 1 calc R U . . .
C11 C 0.8265(5) -0.1737(4) 0.0191(3) 0.0472(7) Uani 1 1 d . . . . .
H11 H 0.8883 -0.2869 0.0129 0.057 Uiso 1 1 calc R U . . .
C12 C 0.8411(4) -0.0777(4) -0.0704(2) 0.0470(7) Uani 1 1 d . . . . .
H12 H 0.9119 -0.1231 -0.1393 0.056 Uiso 1 1 calc R U . . .
C13 C 0.7506(4) 0.0858(4) -0.0576(2) 0.0470(7) Uani 1 1 d . . . . .
H13 H 0.7612 0.1516 -0.1195 0.056 Uiso 1 1 calc R U . . .
Br1 Br 0.80331(4) 0.27436(3) 0.34094(2) 0.03812(11) Uani 1 1 d . . . . .
Mn1 Mn 0.47574(6) 0.37395(4) 0.25969(3) 0.03049(12) Uani 1 1 d . . . . .
N1 N 0.3404(3) 0.2920(3) 0.39411(17) 0.0319(5) Uani 1 1 d . . . . .
N2 N 0.4505(3) 0.0590(3) 0.28783(18) 0.0346(5) Uani 1 1 d . . . . .
N3 N 0.5217(3) 0.1463(3) 0.22045(17) 0.0323(5) Uani 1 1 d . . . . .
N4 N 0.6483(4) 0.1575(3) 0.03717(18) 0.0399(5) Uani 1 1 d . . . . .
O1 O 0.3876(4) 0.6998(3) 0.3429(2) 0.0628(6) Uani 1 1 d . . . . .
O2 O 0.0965(3) 0.5059(3) 0.16303(18) 0.0527(5) Uani 1 1 d . . . . .
O3 O 0.7073(4) 0.4793(3) 0.06718(17) 0.0526(5) 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 O1 1.144(4) . ?
C1 Mn1 1.805(3) . ?
C2 O2 1.137(3) . ?
C2 Mn1 1.806(3) . ?
C3 O3 1.142(3) . ?
C3 Mn1 1.829(3) . ?
C4 N1 1.339(3) . ?
C4 C5 1.385(4) . ?
C4 H4 0.9500 . ?
C5 C6 1.378(4) . ?
C5 H5 0.9500 . ?
C6 C7 1.380(4) . ?
C6 H6 0.9500 . ?
C7 C8 1.378(4) . ?
C7 H7 0.9500 . ?
C8 N1 1.351(3) . ?
C8 N2 1.397(3) . ?
C9 N4 1.324(4) . ?
C9 C10 1.386(4) . ?
C9 N3 1.441(3) . ?
C10 C11 1.382(4) . ?
C10 H10 0.9500 . ?
C11 C12 1.378(5) . ?
C11 H11 0.9500 . ?
C12 C13 1.377(5) . ?
C12 H12 0.9500 . ?
C13 N4 1.340(4) . ?
C13 H13 0.9500 . ?
Br1 Mn1 2.5206(5) . ?
Mn1 N3 2.007(2) . ?
Mn1 N1 2.014(2) . ?
N2 N3 1.271(3) . ?

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
O1 C1 Mn1 177.0(3) . . ?
O2 C2 Mn1 177.4(3) . . ?
O3 C3 Mn1 173.2(3) . . ?
N1 C4 C5 122.4(3) . . ?
N1 C4 H4 118.8 . . ?
C5 C4 H4 118.8 . . ?
C6 C5 C4 119.6(3) . . ?
C6 C5 H5 120.2 . . ?
C4 C5 H5 120.2 . . ?
C5 C6 C7 118.7(2) . . ?
C5 C6 H6 120.7 . . ?
C7 C6 H6 120.7 . . ?
C8 C7 C6 118.5(3) . . ?
C8 C7 H7 120.8 . . ?
C6 C7 H7 120.8 . . ?
N1 C8 C7 123.6(2) . . ?
N1 C8 N2 116.6(2) . . ?
C7 C8 N2 119.8(2) . . ?
N4 C9 C10 124.6(2) . . ?
N4 C9 N3 113.7(2) . . ?
C10 C9 N3 121.6(2) . . ?
C11 C10 C9 117.4(3) . . ?
C11 C10 H10 121.3 . . ?
C9 C10 H10 121.3 . . ?
C12 C11 C10 119.4(3) . . ?
C12 C11 H11 120.3 . . ?
C10 C11 H11 120.3 . . ?
C13 C12 C11 118.4(3) . . ?
C13 C12 H12 120.8 . . ?
C11 C12 H12 120.8 . . ?
N4 C13 C12 123.8(3) . . ?
N4 C13 H13 118.1 . . ?
C12 C13 H13 118.1 . . ?
C1 Mn1 C2 88.82(13) . . ?
C1 Mn1 C3 87.68(12) . . ?
C2 Mn1 C3 90.55(12) . . ?
C1 Mn1 N3 172.48(11) . . ?
C2 Mn1 N3 93.15(11) . . ?
C3 Mn1 N3 99.55(11) . . ?
C1 Mn1 N1 96.01(11) . . ?
C2 Mn1 N1 93.90(10) . . ?
C3 Mn1 N1 174.27(11) . . ?
N3 Mn1 N1 76.62(8) . . ?
C1 Mn1 Br1 89.78(10) . . ?
C2 Mn1 Br1 177.96(8) . . ?
C3 Mn1 Br1 87.92(9) . . ?
N3 Mn1 Br1 88.43(6) . . ?
N1 Mn1 Br1 87.72(6) . . ?
C4 N1 C8 117.2(2) . . ?
C4 N1 Mn1 128.76(18) . . ?
C8 N1 Mn1 114.08(17) . . ?
N3 N2 C8 112.7(2) . . ?
N2 N3 C9 112.7(2) . . ?
N2 N3 Mn1 119.95(17) . . ?
C9 N3 Mn1 127.31(16) . . ?
C9 N4 C13 116.5(3) . . ?

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
N1 C4 C5 C6 -0.6(4) . . . . ?
C4 C5 C6 C7 1.2(4) . . . . ?
C5 C6 C7 C8 -0.4(4) . . . . ?
C6 C7 C8 N1 -1.2(4) . . . . ?
C6 C7 C8 N2 177.2(2) . . . . ?
N4 C9 C10 C11 -0.7(4) . . . . ?
N3 C9 C10 C11 179.9(2) . . . . ?
C9 C10 C11 C12 -0.1(4) . . . . ?
C10 C11 C12 C13 0.5(4) . . . . ?
C11 C12 C13 N4 -0.1(5) . . . . ?
C5 C4 N1 C8 -0.8(4) . . . . ?
C5 C4 N1 Mn1 -179.9(2) . . . . ?
C7 C8 N1 C4 1.8(4) . . . . ?
N2 C8 N1 C4 -176.6(2) . . . . ?
C7 C8 N1 Mn1 -179.0(2) . . . . ?
N2 C8 N1 Mn1 2.6(3) . . . . ?
N1 C8 N2 N3 -1.4(3) . . . . ?
C7 C8 N2 N3 -179.8(2) . . . . ?
C8 N2 N3 C9 178.1(2) . . . . ?
C8 N2 N3 Mn1 -0.5(3) . . . . ?
N4 C9 N3 N2 157.5(2) . . . . ?
C10 C9 N3 N2 -22.9(3) . . . . ?
N4 C9 N3 Mn1 -24.0(3) . . . . ?
C10 C9 N3 Mn1 155.6(2) . . . . ?
C10 C9 N4 C13 1.0(4) . . . . ?
N3 C9 N4 C13 -179.5(2) . . . . ?
C12 C13 N4 C9 -0.6(4) . . . . ?

_refine_diff_density_max         0.763
_refine_diff_density_min         -0.522
_refine_diff_density_rms         0.065

_symmetry_cell_setting           triclinic
_symmetry_space_group_name_h-m   'P -1'
_symmetry_int_tables_number      2
_chemical_absolute_configuration .

_chemical_properties_physical    Light-sensitive
####################################################################### 
# 
# 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_EK210
_audit_block_doi                 10.5517/cc1kk9s6
_database_code_depnum_ccdc_archive 'CCDC 1446608'
_audit_update_record             
;
2016-01-11 deposited with the CCDC.
2016-03-03 downloaded from the CCDC.
;
_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        (E)-1,2-bis(4-bromopyridin-2-yl)diazene
_chemical_name_common            ?
_chemical_formula_moiety         'C10 H6 Br2 N4'
_chemical_formula_sum            'C10 H6 Br2 N4'
_chemical_melting_point          ?

_exptl_crystal_description       needle
_exptl_crystal_colour            brown
_diffrn_ambient_temperature      300(2)
_chemical_formula_weight         342.01

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'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/n'
_space_group_name_Hall           '-P 2yn'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;

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

_cell_length_a                   3.9747(3)
_cell_length_b                   9.2426(11)
_cell_length_c                   14.9310(14)
_cell_angle_alpha                90
_cell_angle_beta                 95.821(7)
_cell_angle_gamma                90
_cell_volume                     545.69(9)
_cell_formula_units_Z            2
_cell_measurement_temperature    300(2)
_cell_measurement_reflns_used    7399
_cell_measurement_theta_min      2.20
_cell_measurement_theta_max      25.43
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.081
_exptl_crystal_F_000             328
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.420
_exptl_crystal_size_mid          0.120
_exptl_crystal_size_min          0.080
_exptl_absorpt_coefficient_mu    7.402
_shelx_estimated_absorpt_T_min   0.147
_shelx_estimated_absorpt_T_max   0.589
_exptl_absorpt_correction_type   integration
_exptl_absorpt_correction_T_min  0.1446
_exptl_absorpt_correction_T_max  0.8404

_exptl_absorpt_process_details   
;
Stoe & Cie (2002). X-SHAPE. Stoe & Cie, Darmstadt, Germany
;
_exptl_absorpt_special_details   ?
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'STOE IPDS 2'
_diffrn_measurement_method       'rotation method'
_diffrn_detector_area_resol_mean 6.67
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6662
_diffrn_reflns_av_unetI/netI     0.0480
_diffrn_reflns_av_R_equivalents  0.1061
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_theta_min         2.595
_diffrn_reflns_theta_max         24.985
_diffrn_reflns_theta_full        24.985
_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             952
_reflns_number_gt                803
_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       'X-Area (Stoe & Cie, 2009)'
_computing_cell_refinement       'X-Area (Stoe & Cie, 2009)'
_computing_data_reduction        'X-RED32(Stoe & Cie, 2009)'
_computing_structure_solution    'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.0200P)²+0.1933P] 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         952
_refine_ls_number_parameters     73
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0401
_refine_ls_R_factor_gt           0.0322
_refine_ls_wR_factor_ref         0.0732
_refine_ls_wR_factor_gt          0.0708
_refine_ls_goodness_of_fit_ref   1.118
_refine_ls_restrained_S_all      1.118
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.38737(10) 0.24329(4) 0.31474(3) 0.04362(19) Uani 1 1 d . . . . .
N1 N 0.7149(9) 0.2092(3) 0.0236(2) 0.0423(8) Uani 1 1 d . . . . .
N2 N 0.5722(9) 0.4459(3) -0.0110(2) 0.0434(8) Uani 1 1 d . . . . .
C1 C 0.7346(10) 0.0974(4) 0.0810(3) 0.0446(9) Uani 1 1 d . . . . .
H1 H 0.8177 0.0102 0.0613 0.053 Uiso 1 1 calc R U . . .
C2 C 0.6411(9) 0.1025(4) 0.1666(3) 0.0402(9) Uani 1 1 d . . . . .
H2 H 0.6627 0.0215 0.2037 0.048 Uiso 1 1 calc R U . . .
C3 C 0.5142(10) 0.2304(3) 0.1966(3) 0.0361(8) Uani 1 1 d . . . . .
C4 C 0.4856(9) 0.3490(4) 0.1392(2) 0.0367(8) Uani 1 1 d . . . . .
H4 H 0.4016 0.4371 0.1572 0.044 Uiso 1 1 calc R U . . .
C5 C 0.5871(10) 0.3307(4) 0.0544(2) 0.0373(8) 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 C3 1.887(4) . ?
N1 C5 1.333(5) . ?
N1 C1 1.340(5) . ?
N2 N2 1.215(6) 3_665 ?
N2 C5 1.442(5) . ?
C1 C2 1.367(5) . ?
C1 H1 0.9300 . ?
C2 C3 1.378(5) . ?
C2 H2 0.9300 . ?
C3 C4 1.389(5) . ?
C4 C5 1.378(5) . ?
C4 H4 0.9300 . ?

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
C5 N1 C1 115.4(3) . . ?
N2 N2 C5 114.3(4) 3_665 . ?
N1 C1 C2 124.6(4) . . ?
N1 C1 H1 117.7 . . ?
C2 C1 H1 117.7 . . ?
C1 C2 C3 118.4(3) . . ?
C1 C2 H2 120.8 . . ?
C3 C2 H2 120.8 . . ?
C2 C3 C4 119.1(4) . . ?
C2 C3 Br1 119.9(3) . . ?
C4 C3 Br1 120.9(3) . . ?
C5 C4 C3 117.2(3) . . ?
C5 C4 H4 121.4 . . ?
C3 C4 H4 121.4 . . ?
N1 C5 C4 125.3(3) . . ?
N1 C5 N2 112.3(3) . . ?
C4 C5 N2 122.4(3) . . ?

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
C5 N1 C1 C2 -1.4(6) . . . . ?
N1 C1 C2 C3 0.7(6) . . . . ?
C1 C2 C3 C4 0.0(6) . . . . ?
C1 C2 C3 Br1 -179.2(3) . . . . ?
C2 C3 C4 C5 0.2(6) . . . . ?
Br1 C3 C4 C5 179.3(3) . . . . ?
C1 N1 C5 C4 1.7(6) . . . . ?
C1 N1 C5 N2 -179.7(4) . . . . ?
C3 C4 C5 N1 -1.1(6) . . . . ?
C3 C4 C5 N2 -179.5(3) . . . . ?
N2 N2 C5 N1 173.3(4) 3_665 . . . ?
N2 N2 C5 C4 -8.0(7) 3_665 . . . ?

_refine_diff_density_max         0.445
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.082

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_h-m   'P 21/n'
_symmetry_int_tables_number      14
_chemical_absolute_configuration .

