# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_TcN(Cl)2bpa
_database_code_depnum_ccdc_archive 'CCDC 1851198'
_audit_update_record             
;
2018-09-07 deposited with the CCDC.
2018-09-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT934_TcN(Cl)2bpa         
;
PROBLEM: Number of (Iobs-Icalc)/SigmaW &gt; 10 Outliers ....          5 Check
RESPONSE: The crystal was not good quality.
;
# Added during the CSD deposition process: Friday 07 September 2018 08:32 AM
# end Validation Reply Form


#==============================================================================
# CHEMICAL DATA

_chemical_formula_sum            'C14 H16 Cl2 N5 Tc'
_chemical_formula_moiety         'C12 H13 Cl2 N4 Tc, C2 H3 N'
_chemical_formula_weight         424.13
_chemical_melting_point          ?

#==============================================================================
# CRYSTAL DATA
_space_group_crystal_system      monoclinic
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
_space_group_IT_number           14
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 +X,+Y,+Z
2 -X,1/2+Y,1/2-Z
3 -X,-Y,-Z
4 +X,-1/2-Y,-1/2+Z
#------------------------------------------------------------------------------
_cell_length_a                   10.2820(3)
_cell_length_b                   11.9687(3)
_cell_length_c                   14.2478(5)
_cell_angle_alpha                90.0000
_cell_angle_beta                 103.6947(8)
_cell_angle_gamma                90.0000
_cell_volume                     1703.52(9)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    12472
_cell_measurement_theta_min      3.16
_cell_measurement_theta_max      27.45
_cell_measurement_temperature    170
#------------------------------------------------------------------------------
_exptl_crystal_description       platelet
_exptl_crystal_colour            brown
_exptl_crystal_size_max          0.310
_exptl_crystal_size_mid          0.170
_exptl_crystal_size_min          0.100
_exptl_crystal_density_diffrn    1.646
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             848.00
_exptl_absorpt_coefficient_mu    1.153
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSCOR (Rigaku, 1995)'
_exptl_absorpt_correction_T_min  0.609
_exptl_absorpt_correction_T_max  0.891

#==============================================================================
# EXPERIMENTAL DATA

_diffrn_ambient_temperature      170
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean 10.000
_diffrn_reflns_number            16440
_diffrn_reflns_av_unetI/netI     0.0324
_diffrn_reflns_av_R_equivalents  0.0427
_diffrn_reflns_theta_max         27.451
_diffrn_reflns_theta_min         3.159
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_limit_l_max       18
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_decay_%        ?
_reflns_number_total             3888
_reflns_number_gt                3245
_reflns_threshold_expression     F²>2.0σ(F²)
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

#==============================================================================
# REFINEMENT DATA

_refine_special_details          
;
    Refinement was performed using all reflections. The weighted 
    R-factor (wR) and goodness of fit (S) are based on F².
    R-factor (gt) are based on F. The threshold expression of
    F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_R_factor_all          0.0469
_refine_ls_R_factor_gt           0.0333
_refine_ls_wR_factor_ref         0.0958
_refine_ls_wR_factor_gt          0.0736
_refine_ls_number_restraints     0
_refine_ls_hydrogen_treatment    constr
_refine_ls_number_reflns         3888
_refine_ls_number_parameters     200
_refine_ls_goodness_of_fit_ref   1.164
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w = 1/[σ²(Fo²)+(0.0317P)²+3.6824P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_shift/su_max          0.000
_refine_diff_density_max         1.58
_refine_diff_density_min         -0.65
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?

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 for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;
H H 0.0000 0.0000
;
International Tables for Crystallography
(Vol. C, Table 6.1.1.4)
;
N N 0.0061 0.0033
;
International Tables for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;
Tc Tc -1.4390 0.7593
;
International Tables for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;
Cl Cl 0.1484 0.1585
;
International Tables for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;

#==============================================================================
# ATOMIC COORDINATES AND THERMAL 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
Tc1 Tc 0.17401(3) 0.80830(2) 0.58676(2) 0.02275(10) Uani 1 1 d . . . . .
Cl1 Cl 0.19871(9) 0.99979(7) 0.63867(6) 0.03066(19) Uani 1 1 d . . . . .
Cl2 Cl -0.05737(8) 0.81687(7) 0.59173(6) 0.02897(19) Uani 1 1 d . . . . .
N1 N 0.2450(3) 0.7407(2) 0.6863(2) 0.0289(6) Uani 1 1 d . . . . .
N2 N 0.1362(3) 0.6620(2) 0.49838(19) 0.0236(6) Uani 1 1 d . . . . .
N3 N 0.3533(3) 0.8233(2) 0.5369(2) 0.0257(6) Uani 1 1 d . . . . .
N4 N 0.1044(3) 0.8755(2) 0.42526(19) 0.0250(6) Uani 1 1 d . . . . .
H4A H 0.040303 0.938490 0.424733 0.030 Uiso 1 1 calc R U . . .
N5 N 0.6441(8) 0.6138(7) 0.2969(4) 0.122(3) Uani 1 1 d . . . . .
C1 C 0.1756(4) 0.5597(3) 0.5343(3) 0.0287(7) Uani 1 1 d . . . . .
H1 H 0.214681 0.552519 0.601429 0.034 Uiso 1 1 calc R U . . .
C2 C 0.1613(4) 0.4653(3) 0.4774(3) 0.0338(8) Uani 1 1 d . . . . .
H2 H 0.188824 0.394423 0.505063 0.041 Uiso 1 1 calc R U . . .
C3 C 0.1062(4) 0.4753(3) 0.3793(3) 0.0394(9) Uani 1 1 d . . . . .
H3 H 0.096414 0.411655 0.338413 0.047 Uiso 1 1 calc R U . . .
C4 C 0.0656(4) 0.5793(3) 0.3420(3) 0.0348(8) Uani 1 1 d . . . . .
H4 H 0.027324 0.587894 0.274882 0.042 Uiso 1 1 calc R U . . .
C5 C 0.0809(4) 0.6709(3) 0.4026(2) 0.0259(7) Uani 1 1 d . . . . .
C6 C 0.0317(4) 0.7849(3) 0.3658(2) 0.0316(8) Uani 1 1 d . . . . .
H6A H 0.041696 0.793405 0.298703 0.038 Uiso 1 1 calc R U . . .
H6B H -0.064715 0.791037 0.364431 0.038 Uiso 1 1 calc R U . . .
C7 C 0.4711(4) 0.7829(3) 0.5894(3) 0.0323(8) Uani 1 1 d . . . . .
H7 H 0.473036 0.749086 0.650096 0.039 Uiso 1 1 calc R U . . .
C8 C 0.5885(4) 0.7886(4) 0.5587(3) 0.0408(10) Uani 1 1 d . . . . .
H8 H 0.669582 0.759899 0.597764 0.049 Uiso 1 1 calc R U . . .
C9 C 0.5861(4) 0.8369(4) 0.4699(3) 0.0430(10) Uani 1 1 d . . . . .
H9 H 0.665594 0.842231 0.447167 0.052 Uiso 1 1 calc R U . . .
C10 C 0.4670(4) 0.8770(3) 0.4155(3) 0.0373(9) Uani 1 1 d . . . . .
H10 H 0.463253 0.909344 0.354048 0.045 Uiso 1 1 calc R U . . .
C11 C 0.3512(4) 0.8703(3) 0.4502(3) 0.0284(7) Uani 1 1 d . . . . .
C12 C 0.2214(4) 0.9199(3) 0.3945(3) 0.0325(8) Uani 1 1 d . . . . .
H12A H 0.224671 1.002007 0.403137 0.039 Uiso 1 1 calc R U . . .
H12B H 0.210946 0.904172 0.324869 0.039 Uiso 1 1 calc R U . . .
C13 C 0.4336(7) 0.5693(5) 0.3609(5) 0.0806(18) Uani 1 1 d . . . . .
H13A H 0.410996 0.489755 0.352872 0.097 Uiso 1 1 calc R U . . .
H13B H 0.358329 0.613996 0.324903 0.097 Uiso 1 1 calc R U . . .
H13C H 0.451985 0.588887 0.429556 0.097 Uiso 1 1 calc R U . . .
C14 C 0.5499(8) 0.5915(6) 0.3248(4) 0.080(2) Uani 1 1 d . . . . .


#==============================================================================
_computing_data_collection       'RAPID AUTO (Rigaku, ????)'
_computing_cell_refinement       'RAPID AUTO'
_computing_data_reduction        'RAPID AUTO'
_computing_structure_solution    'SHELXT Version 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL Version 2017/1 (Sheldrick, 2008)'
_computing_publication_material  'CrystalStructure 4.3 (Rigaku, 2018)'
_computing_molecular_graphics    'CrystalStructure 4.3'

#==============================================================================
# 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
Tc1 N1 1.646(3) . ?
Tc1 N3 2.135(3) . ?
Tc1 N2 2.138(3) . ?
Tc1 N4 2.382(3) . ?
Tc1 Cl2 2.3991(9) . ?
Tc1 Cl1 2.4032(9) . ?
N2 C1 1.352(4) . ?
N2 C5 1.353(4) . ?
N3 C11 1.352(5) . ?
N3 C7 1.353(5) . ?
N4 C6 1.467(5) . ?
N4 C12 1.474(5) . ?
N4 H4A 1.0000 . ?
N5 C14 1.162(10) . ?
C1 C2 1.378(5) . ?
C1 H1 0.9500 . ?
C2 C3 1.383(5) . ?
C2 H2 0.9500 . ?
C3 C4 1.378(5) . ?
C3 H3 0.9500 . ?
C4 C5 1.381(5) . ?
C4 H4 0.9500 . ?
C5 C6 1.506(5) . ?
C6 H6A 0.9900 . ?
C6 H6B 0.9900 . ?
C7 C8 1.380(5) . ?
C7 H7 0.9500 . ?
C8 C9 1.386(6) . ?
C8 H8 0.9500 . ?
C9 C10 1.372(6) . ?
C9 H9 0.9500 . ?
C10 C11 1.395(5) . ?
C10 H10 0.9500 . ?
C11 C12 1.504(5) . ?
C12 H12A 0.9900 . ?
C12 H12B 0.9900 . ?
C13 C14 1.434(10) . ?
C13 H13A 0.9800 . ?
C13 H13B 0.9800 . ?
C13 H13C 0.9800 . ?

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 Tc1 N3 94.96(13) . . ?
N1 Tc1 N2 94.96(13) . . ?
N3 Tc1 N2 85.62(11) . . ?
N1 Tc1 N4 165.70(12) . . ?
N3 Tc1 N4 74.69(11) . . ?
N2 Tc1 N4 74.72(10) . . ?
N1 Tc1 Cl2 103.65(11) . . ?
N3 Tc1 Cl2 161.26(8) . . ?
N2 Tc1 Cl2 90.52(8) . . ?
N4 Tc1 Cl2 86.60(7) . . ?
N1 Tc1 Cl1 102.16(11) . . ?
N3 Tc1 Cl1 89.18(8) . . ?
N2 Tc1 Cl1 162.48(8) . . ?
N4 Tc1 Cl1 87.77(7) . . ?
Cl2 Tc1 Cl1 89.05(3) . . ?
C1 N2 C5 118.0(3) . . ?
C1 N2 Tc1 121.5(2) . . ?
C5 N2 Tc1 120.3(2) . . ?
C11 N3 C7 118.2(3) . . ?
C11 N3 Tc1 120.7(2) . . ?
C7 N3 Tc1 121.1(2) . . ?
C6 N4 C12 115.7(3) . . ?
C6 N4 Tc1 107.7(2) . . ?
C12 N4 Tc1 109.2(2) . . ?
C6 N4 H4A 108.0 . . ?
C12 N4 H4A 108.0 . . ?
Tc1 N4 H4A 108.0 . . ?
N2 C1 C2 122.6(3) . . ?
N2 C1 H1 118.7 . . ?
C2 C1 H1 118.7 . . ?
C1 C2 C3 119.0(3) . . ?
C1 C2 H2 120.5 . . ?
C3 C2 H2 120.5 . . ?
C4 C3 C2 118.8(4) . . ?
C4 C3 H3 120.6 . . ?
C2 C3 H3 120.6 . . ?
C3 C4 C5 119.8(3) . . ?
C3 C4 H4 120.1 . . ?
C5 C4 H4 120.1 . . ?
N2 C5 C4 121.8(3) . . ?
N2 C5 C6 116.7(3) . . ?
C4 C5 C6 121.5(3) . . ?
N4 C6 C5 112.7(3) . . ?
N4 C6 H6A 109.1 . . ?
C5 C6 H6A 109.1 . . ?
N4 C6 H6B 109.1 . . ?
C5 C6 H6B 109.1 . . ?
H6A C6 H6B 107.8 . . ?
N3 C7 C8 122.8(4) . . ?
N3 C7 H7 118.6 . . ?
C8 C7 H7 118.6 . . ?
C7 C8 C9 118.8(4) . . ?
C7 C8 H8 120.6 . . ?
C9 C8 H8 120.6 . . ?
C10 C9 C8 118.8(4) . . ?
C10 C9 H9 120.6 . . ?
C8 C9 H9 120.6 . . ?
C9 C10 C11 120.1(4) . . ?
C9 C10 H10 119.9 . . ?
C11 C10 H10 119.9 . . ?
N3 C11 C10 121.1(4) . . ?
N3 C11 C12 117.8(3) . . ?
C10 C11 C12 121.0(3) . . ?
N4 C12 C11 112.7(3) . . ?
N4 C12 H12A 109.1 . . ?
C11 C12 H12A 109.1 . . ?
N4 C12 H12B 109.1 . . ?
C11 C12 H12B 109.1 . . ?
H12A C12 H12B 107.8 . . ?
C14 C13 H13A 109.5 . . ?
C14 C13 H13B 109.5 . . ?
H13A C13 H13B 109.5 . . ?
C14 C13 H13C 109.5 . . ?
H13A C13 H13C 109.5 . . ?
H13B C13 H13C 109.5 . . ?
N5 C14 C13 177.3(9) . . ?

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 N2 C1 C2 -0.1(5) . . . . ?
Tc1 N2 C1 C2 -175.1(3) . . . . ?
N2 C1 C2 C3 0.9(6) . . . . ?
C1 C2 C3 C4 -0.9(6) . . . . ?
C2 C3 C4 C5 0.2(6) . . . . ?
C1 N2 C5 C4 -0.6(5) . . . . ?
Tc1 N2 C5 C4 174.4(3) . . . . ?
C1 N2 C5 C6 177.0(3) . . . . ?
Tc1 N2 C5 C6 -8.0(4) . . . . ?
C3 C4 C5 N2 0.6(6) . . . . ?
C3 C4 C5 C6 -176.9(4) . . . . ?
C12 N4 C6 C5 92.2(4) . . . . ?
Tc1 N4 C6 C5 -30.3(3) . . . . ?
N2 C5 C6 N4 27.3(4) . . . . ?
C4 C5 C6 N4 -155.1(3) . . . . ?
C11 N3 C7 C8 0.6(5) . . . . ?
Tc1 N3 C7 C8 178.5(3) . . . . ?
N3 C7 C8 C9 -0.5(6) . . . . ?
C7 C8 C9 C10 -0.3(6) . . . . ?
C8 C9 C10 C11 1.0(6) . . . . ?
C7 N3 C11 C10 0.1(5) . . . . ?
Tc1 N3 C11 C10 -177.8(3) . . . . ?
C7 N3 C11 C12 -177.1(3) . . . . ?
Tc1 N3 C11 C12 5.0(4) . . . . ?
C9 C10 C11 N3 -0.9(6) . . . . ?
C9 C10 C11 C12 176.3(4) . . . . ?
C6 N4 C12 C11 -97.8(4) . . . . ?
Tc1 N4 C12 C11 23.9(3) . . . . ?
N3 C11 C12 N4 -20.6(5) . . . . ?
C10 C11 C12 N4 162.1(3) . . . . ?


#==============================================================================
# Additional structures and associated data_? identifiers
# should be added at this point if there is more than one 
# structure analysis in the CIF.



#==============================================================================
#     End of CIF
#==============================================================================
_chemical_name_systematic        TcN(Cl)2bpa
####################################################################### 
# 
# 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_TcN(CN)2bpa
_database_code_depnum_ccdc_archive 'CCDC 1851199'
_audit_update_record             
;
2018-07-19 deposited with the CCDC.
2018-09-21 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT094_TcN(CN)2bpa         
;
PROBLEM: Ratio of Maximum / Minimum Residual Density ....       4.62 Report
RESPONSE: The crystal was not good quality.
;
_vrf_PLAT097_TcN(CN)2bpa         
;
PROBLEM: Large Reported Max.  (Positive) Residual Density       6.42 eA-3
RESPONSE: The crystal was not good quality.
;
# Added during the CSD deposition process: Thursday 19 July 2018 02:18 AM
# end Validation Reply Form


#==============================================================================
# CHEMICAL DATA

_chemical_formula_sum            'C17.5 H17 N6 Tc'
_chemical_formula_moiety         '2(C14 H13 N6 Tc), C7 H8'
_chemical_formula_weight         410.28
_chemical_melting_point          ?

#==============================================================================
# CRYSTAL DATA
_space_group_crystal_system      triclinic
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
_space_group_IT_number           2
loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 +X,+Y,+Z
2 -X,-Y,-Z
#------------------------------------------------------------------------------
_cell_length_a                   7.3182(3)
_cell_length_b                   10.7602(4)
_cell_length_c                   12.5043(5)
_cell_angle_alpha                66.5421(17)
_cell_angle_beta                 87.0938(14)
_cell_angle_gamma                72.793(2)
_cell_volume                     860.32(6)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    7821
_cell_measurement_theta_min      3.07
_cell_measurement_theta_max      27.48
_cell_measurement_temperature    170
#------------------------------------------------------------------------------
_exptl_crystal_description       block
_exptl_crystal_colour            yellow
_exptl_crystal_size_max          0.220
_exptl_crystal_size_mid          0.140
_exptl_crystal_size_min          0.140
_exptl_crystal_density_diffrn    1.576
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             414.00
_exptl_absorpt_coefficient_mu    0.840
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'ABSCOR (Rigaku, 1995)'
_exptl_absorpt_correction_T_min  0.466
_exptl_absorpt_correction_T_max  0.889

#==============================================================================
# EXPERIMENTAL DATA

_diffrn_ambient_temperature      170
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71075
_diffrn_measurement_device_type  'Rigaku R-AXIS RAPID'
_diffrn_measurement_method       ω
_diffrn_detector_area_resol_mean 10.000
_diffrn_reflns_number            8568
_diffrn_reflns_av_unetI/netI     0.0538
_diffrn_reflns_av_R_equivalents  0.0450
_diffrn_reflns_theta_max         27.475
_diffrn_reflns_theta_min         3.069
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       15
_diffrn_standards_number         0
_diffrn_standards_interval_count .
_diffrn_standards_decay_%        ?
_reflns_number_total             3919
_reflns_number_gt                3407
_reflns_threshold_expression     F²>2.0σ(F²)
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

#==============================================================================
# REFINEMENT DATA

_refine_special_details          
;
    Refinement was performed using all reflections. The weighted 
    R-factor (wR) and goodness of fit (S) are based on F².
    R-factor (gt) are based on F. The threshold expression of
    F² > 2.0 sigma(F²) is used only for calculating R-factor (gt).
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_R_factor_all          0.0901
_refine_ls_R_factor_gt           0.0795
_refine_ls_wR_factor_ref         0.2022
_refine_ls_wR_factor_gt          0.1953
_refine_ls_number_restraints     122
_refine_ls_hydrogen_treatment    constr
_refine_ls_number_reflns         3919
_refine_ls_number_parameters     254
_refine_ls_goodness_of_fit_ref   1.209
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w = 1/[σ²(Fo²)+(0.0714P)²+6.4311P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_refine_ls_shift/su_max          0.000
_refine_diff_density_max         6.42
_refine_diff_density_min         -1.39
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?

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 for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;
H H 0.0000 0.0000
;
International Tables for Crystallography
(Vol. C, Table 6.1.1.4)
;
N N 0.0061 0.0033
;
International Tables for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;
Tc Tc -1.4390 0.7593
;
International Tables for Crystallography
(Vol. C, Tables 4.2.6.8 and 6.1.1.4)
;

#==============================================================================
# ATOMIC COORDINATES AND THERMAL 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
Tc1 Tc 0.42640(8) 0.30752(6) 0.31381(5) 0.0304(2) Uani 1 1 d . . . . .
N5 N 0.1746(7) 0.4653(5) 0.3294(4) 0.0230(10) Uani 1 1 d . . . . .
N6 N 0.1936(8) 0.1877(6) 0.3929(5) 0.0277(11) Uani 1 1 d . . . . .
H6 H 0.236647 0.119653 0.475631 0.033 Uiso 1 1 calc R U . . .
N4 N 0.2768(8) 0.2987(6) 0.1703(5) 0.0307(12) Uani 1 1 d . . . . .
N3 N 0.7464(9) 0.0092(7) 0.3500(5) 0.0353(13) Uani 1 1 d . . . . .
N1 N 0.5424(9) 0.4160(7) 0.2298(6) 0.0403(14) Uani 1 1 d . . . . .
C1 C 0.5298(9) 0.2770(7) 0.4763(6) 0.0306(14) Uani 1 1 d . . . . .
C13 C 0.0100(8) 0.4361(7) 0.3622(5) 0.0228(12) Uani 1 1 d . . . . .
C2 C 0.6309(9) 0.1144(7) 0.3359(5) 0.0277(13) Uani 1 1 d . . . . .
N2 N 0.5885(10) 0.2638(8) 0.5639(6) 0.0453(16) Uani 1 1 d . . . . .
C9 C 0.1845(10) 0.5966(7) 0.3090(6) 0.0298(14) Uani 1 1 d . . . . .
H9 H 0.302308 0.616998 0.288505 0.036 Uiso 1 1 calc R U . . .
C12 C -0.1527(10) 0.5394(8) 0.3713(6) 0.0329(15) Uani 1 1 d . . . . .
H12 H -0.268848 0.517121 0.394054 0.039 Uiso 1 1 calc R U . . .
C10 C 0.0287(10) 0.7015(7) 0.3172(6) 0.0338(15) Uani 1 1 d . . . . .
H10 H 0.039360 0.792758 0.302274 0.041 Uiso 1 1 calc R U . . .
C8 C 0.1878(10) 0.1080(7) 0.3219(7) 0.0341(15) Uani 1 1 d . . . . .
H8A H 0.072744 0.074727 0.336745 0.041 Uiso 1 1 calc R U . . .
H8B H 0.302910 0.023849 0.342903 0.041 Uiso 1 1 calc R U . . .
C7 C 0.1816(10) 0.2040(8) 0.1945(7) 0.0364(16) Uani 1 1 d . . . . .
C11 C -0.1419(10) 0.6726(7) 0.3471(6) 0.0330(15) Uani 1 1 d . . . . .
H11 H -0.251469 0.744532 0.350942 0.040 Uiso 1 1 calc R U . . .
C3 C 0.2840(11) 0.3838(9) 0.0559(6) 0.0415(18) Uani 1 1 d . . . . .
H3 H 0.352339 0.451263 0.038630 0.050 Uiso 1 1 calc R U . . .
C14 C 0.0032(9) 0.2886(7) 0.3894(6) 0.0300(14) Uani 1 1 d . . . . .
H14A H -0.050761 0.252703 0.465986 0.036 Uiso 1 1 calc R U . . .
H14B H -0.084149 0.292370 0.329440 0.036 Uiso 1 1 calc R U . . .
C6 C 0.0866(13) 0.1924(11) 0.1061(9) 0.053(2) Uani 1 1 d . . . . .
H6A H 0.016304 0.126058 0.124263 0.064 Uiso 1 1 calc R U . . .
C5 C 0.0983(15) 0.2818(13) -0.0099(8) 0.063(3) Uani 1 1 d . . . . .
H5 H 0.035857 0.275695 -0.071575 0.076 Uiso 1 1 calc R U . . .
C4 C 0.1973(14) 0.3765(12) -0.0350(7) 0.057(2) Uani 1 1 d . . . . .
H4 H 0.206618 0.436451 -0.113667 0.069 Uiso 1 1 calc R U . . .
C21 C 0.322(4) -0.148(3) 0.037(2) 0.095(10) Uani 0.5 1 d D U P A -1
H21A H 0.381258 -0.234901 0.106344 0.142 Uiso 0.5 1 calc R U P A -1
H21B H 0.311389 -0.172371 -0.029141 0.142 Uiso 0.5 1 calc R U P A -1
H21C H 0.193851 -0.100776 0.053753 0.142 Uiso 0.5 1 calc R U P A -1
C18 C 0.441(2) -0.0521(18) 0.0096(13) 0.052(4) Uani 0.5 1 d D U P A -1
C17 C 0.533(4) -0.043(3) 0.0981(18) 0.063(7) Uani 0.5 1 d D U P A -1
H17 H 0.518547 -0.097468 0.177382 0.075 Uiso 0.5 1 calc R U P A -1
C16 C 0.645(3) 0.047(2) 0.0712(14) 0.070(5) Uani 0.5 1 d D U P A -1
H16 H 0.712381 0.051554 0.131765 0.084 Uiso 0.5 1 calc R U P A -1
C15 C 0.660(4) 0.129(3) -0.0443(15) 0.071(7) Uani 0.5 1 d D U P A -1
H15 H 0.730945 0.195091 -0.062698 0.085 Uiso 0.5 1 calc R U P A -1
C20 C 0.572(3) 0.1175(19) -0.1333(14) 0.053(4) Uani 0.5 1 d D U P A -1
H20 H 0.588115 0.170800 -0.212619 0.064 Uiso 0.5 1 calc R U P A -1
C19 C 0.461(4) 0.027(2) -0.1053(15) 0.044(5) Uani 0.5 1 d D U P A -1
H19 H 0.396890 0.019546 -0.165772 0.053 Uiso 0.5 1 calc R U P A -1


#==============================================================================
_computing_data_collection       'RAPID AUTO (Rigaku, ????)'
_computing_cell_refinement       'RAPID AUTO'
_computing_data_reduction        'RAPID AUTO'
_computing_structure_solution    'SHELXT Version 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL Version 2017/1 (Sheldrick, 2008)'
_computing_publication_material  'CrystalStructure 4.3 (Rigaku, 2018)'
_computing_molecular_graphics    'CrystalStructure 4.3'

#==============================================================================
# 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
Tc1 N1 1.645(7) . ?
Tc1 C1 2.070(7) . ?
Tc1 C2 2.093(7) . ?
Tc1 N5 2.166(5) . ?
Tc1 N4 2.196(5) . ?
Tc1 N6 2.378(5) . ?
N5 C13 1.338(8) . ?
N5 C9 1.355(8) . ?
N6 C8 1.469(9) . ?
N6 C14 1.482(8) . ?
N6 H6 1.0000 . ?
N4 C7 1.330(10) . ?
N4 C3 1.365(9) . ?
N3 C2 1.148(9) . ?
C1 N2 1.137(10) . ?
C13 C12 1.404(9) . ?
C13 C14 1.501(9) . ?
C9 C10 1.379(9) . ?
C9 H9 0.9500 . ?
C12 C11 1.368(10) . ?
C12 H12 0.9500 . ?
C10 C11 1.373(10) . ?
C10 H10 0.9500 . ?
C8 C7 1.508(11) . ?
C8 H8A 0.9900 . ?
C8 H8B 0.9900 . ?
C7 C6 1.400(11) . ?
C11 H11 0.9500 . ?
C3 C4 1.370(11) . ?
C3 H3 0.9500 . ?
C14 H14A 0.9900 . ?
C14 H14B 0.9900 . ?
C6 C5 1.401(14) . ?
C6 H6A 0.9500 . ?
C5 C4 1.349(15) . ?
C5 H5 0.9500 . ?
C4 H4 0.9500 . ?
C21 C18 1.47(3) . ?
C21 H21A 0.9800 . ?
C21 H21B 0.9800 . ?
C21 H21C 0.9800 . ?
C18 C17 1.373(14) . ?
C18 C19 1.373(14) . ?
C17 C16 1.378(15) . ?
C17 H17 0.9500 . ?
C16 C15 1.380(15) . ?
C16 H16 0.9500 . ?
C15 C20 1.377(15) . ?
C15 H15 0.9500 . ?
C20 C19 1.380(14) . ?
C20 H20 0.9500 . ?
C19 H19 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
N1 Tc1 C1 99.6(3) . . ?
N1 Tc1 C2 98.7(3) . . ?
C1 Tc1 C2 87.2(2) . . ?
N1 Tc1 N5 98.2(3) . . ?
C1 Tc1 N5 87.8(2) . . ?
C2 Tc1 N5 162.9(2) . . ?
N1 Tc1 N4 95.9(3) . . ?
C1 Tc1 N4 164.5(3) . . ?
C2 Tc1 N4 89.8(2) . . ?
N5 Tc1 N4 90.67(19) . . ?
N1 Tc1 N6 164.5(3) . . ?
C1 Tc1 N6 93.4(2) . . ?
C2 Tc1 N6 90.3(2) . . ?
N5 Tc1 N6 73.67(19) . . ?
N4 Tc1 N6 71.4(2) . . ?
C13 N5 C9 118.5(6) . . ?
C13 N5 Tc1 122.0(4) . . ?
C9 N5 Tc1 119.5(4) . . ?
C8 N6 C14 111.5(5) . . ?
C8 N6 Tc1 105.7(4) . . ?
C14 N6 Tc1 111.6(4) . . ?
C8 N6 H6 109.3 . . ?
C14 N6 H6 109.3 . . ?
Tc1 N6 H6 109.3 . . ?
C7 N4 C3 118.4(6) . . ?
C7 N4 Tc1 119.3(5) . . ?
C3 N4 Tc1 122.2(5) . . ?
N2 C1 Tc1 177.9(7) . . ?
N5 C13 C12 121.5(6) . . ?
N5 C13 C14 118.1(5) . . ?
C12 C13 C14 120.4(6) . . ?
N3 C2 Tc1 178.0(6) . . ?
N5 C9 C10 122.1(6) . . ?
N5 C9 H9 119.0 . . ?
C10 C9 H9 119.0 . . ?
C11 C12 C13 119.2(6) . . ?
C11 C12 H12 120.4 . . ?
C13 C12 H12 120.4 . . ?
C11 C10 C9 119.3(7) . . ?
C11 C10 H10 120.4 . . ?
C9 C10 H10 120.4 . . ?
N6 C8 C7 108.7(6) . . ?
N6 C8 H8A 109.9 . . ?
C7 C8 H8A 109.9 . . ?
N6 C8 H8B 109.9 . . ?
C7 C8 H8B 109.9 . . ?
H8A C8 H8B 108.3 . . ?
N4 C7 C6 121.5(8) . . ?
N4 C7 C8 115.9(6) . . ?
C6 C7 C8 122.5(8) . . ?
C12 C11 C10 119.4(6) . . ?
C12 C11 H11 120.3 . . ?
C10 C11 H11 120.3 . . ?
N4 C3 C4 123.1(8) . . ?
N4 C3 H3 118.4 . . ?
C4 C3 H3 118.4 . . ?
N6 C14 C13 113.3(5) . . ?
N6 C14 H14A 108.9 . . ?
C13 C14 H14A 108.9 . . ?
N6 C14 H14B 108.9 . . ?
C13 C14 H14B 108.9 . . ?
H14A C14 H14B 107.7 . . ?
C7 C6 C5 117.9(9) . . ?
C7 C6 H6A 121.0 . . ?
C5 C6 H6A 121.0 . . ?
C4 C5 C6 120.8(8) . . ?
C4 C5 H5 119.6 . . ?
C6 C5 H5 119.6 . . ?
C5 C4 C3 118.2(8) . . ?
C5 C4 H4 120.9 . . ?
C3 C4 H4 120.9 . . ?
C18 C21 H21A 109.5 . . ?
C18 C21 H21B 109.5 . . ?
H21A C21 H21B 109.5 . . ?
C18 C21 H21C 109.5 . . ?
H21A C21 H21C 109.5 . . ?
H21B C21 H21C 109.5 . . ?
C17 C18 C19 120.6(13) . . ?
C17 C18 C21 120.0(15) . . ?
C19 C18 C21 119.3(14) . . ?
C18 C17 C16 119.6(14) . . ?
C18 C17 H17 120.2 . . ?
C16 C17 H17 120.2 . . ?
C17 C16 C15 119.6(14) . . ?
C17 C16 H16 120.2 . . ?
C15 C16 H16 120.2 . . ?
C20 C15 C16 120.8(14) . . ?
C20 C15 H15 119.6 . . ?
C16 C15 H15 119.6 . . ?
C15 C20 C19 119.0(14) . . ?
C15 C20 H20 120.5 . . ?
C19 C20 H20 120.5 . . ?
C18 C19 C20 120.2(13) . . ?
C18 C19 H19 119.9 . . ?
C20 C19 H19 119.9 . . ?

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 N5 C13 C12 2.5(9) . . . . ?
Tc1 N5 C13 C12 -179.6(5) . . . . ?
C9 N5 C13 C14 -177.5(6) . . . . ?
Tc1 N5 C13 C14 0.4(7) . . . . ?
C13 N5 C9 C10 -2.3(9) . . . . ?
Tc1 N5 C9 C10 179.7(5) . . . . ?
N5 C13 C12 C11 -0.6(10) . . . . ?
C14 C13 C12 C11 179.4(6) . . . . ?
N5 C9 C10 C11 0.1(10) . . . . ?
C14 N6 C8 C7 75.8(7) . . . . ?
Tc1 N6 C8 C7 -45.7(6) . . . . ?
C3 N4 C7 C6 -1.4(10) . . . . ?
Tc1 N4 C7 C6 -178.9(6) . . . . ?
C3 N4 C7 C8 176.8(6) . . . . ?
Tc1 N4 C7 C8 -0.7(8) . . . . ?
N6 C8 C7 N4 33.6(8) . . . . ?
N6 C8 C7 C6 -148.2(7) . . . . ?
C13 C12 C11 C10 -1.6(10) . . . . ?
C9 C10 C11 C12 1.8(10) . . . . ?
C7 N4 C3 C4 0.2(11) . . . . ?
Tc1 N4 C3 C4 177.6(7) . . . . ?
C8 N6 C14 C13 -130.4(6) . . . . ?
Tc1 N6 C14 C13 -12.5(7) . . . . ?
N5 C13 C14 N6 8.7(8) . . . . ?
C12 C13 C14 N6 -171.2(6) . . . . ?
N4 C7 C6 C5 1.5(12) . . . . ?
C8 C7 C6 C5 -176.6(8) . . . . ?
C7 C6 C5 C4 -0.4(15) . . . . ?
C6 C5 C4 C3 -0.7(15) . . . . ?
N4 C3 C4 C5 0.9(14) . . . . ?
C19 C18 C17 C16 0(3) . . . . ?
C21 C18 C17 C16 179.6(18) . . . . ?
C18 C17 C16 C15 2(3) . . . . ?
C17 C16 C15 C20 -4(4) . . . . ?
C16 C15 C20 C19 3(4) . . . . ?
C17 C18 C19 C20 0(4) . . . . ?
C21 C18 C19 C20 -179.9(19) . . . . ?
C15 C20 C19 C18 -1(4) . . . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_D
_geom_hbond_site_symmetry_H
_geom_hbond_site_symmetry_A
_geom_hbond_distance_DA
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_angle_DHA
_geom_hbond_publ_flag
N6 H6 N3 . . 2_656 3.032(7) 1.000 2.053 165.8 no

#==============================================================================
# Additional structures and associated data_? identifiers
# should be added at this point if there is more than one 
# structure analysis in the CIF.



#==============================================================================
#     End of CIF
#==============================================================================




_chemical_name_systematic        TcNCN2bpa
