# Supplementary Information (SI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2026

####################################################################### 
# 
# 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_imtcbr_lt_0m
_database_code_depnum_ccdc_archive 'CCDC 2512687'
loop_
_audit_author_name
_audit_author_address
'Mikhail Grigoriev'
;IPCE RAS
Russia
;
_audit_update_record             
;
2025-12-02 deposited with the CCDC.	2026-02-11 downloaded from the CCDC.
;
_audit_creation_date             2025-07-07
_audit_creation_method           
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'Br6 Tc, 2(C3 H5 N2)'
_chemical_formula_sum            'C6 H10 Br6 N4 Tc'
_chemical_formula_weight         715.64
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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'
Tc Tc -1.4390 0.7593 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/c 1'
_space_group_name_Hall           '-P 2ybc'
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                   7.7038(5)
_cell_length_b                   8.3595(5)
_cell_length_c                   12.6218(8)
_cell_angle_alpha                90
_cell_angle_beta                 98.133(3)
_cell_angle_gamma                90
_cell_volume                     804.67(9)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    2870
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      29.767
_cell_measurement_theta_min      2.932
_shelx_estimated_absorpt_T_max   0.276
_shelx_estimated_absorpt_T_min   0.032
_exptl_absorpt_coefficient_mu    15.776
_exptl_absorpt_correction_T_max  1.0000
_exptl_absorpt_correction_T_min  0.6748
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0924 before and 0.0425 after correction.
The Ratio of minimum to maximum transmission is 0.6748.
The λ/2 correction factor is 0.0015.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.954
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       fragment
_exptl_crystal_F_000             654
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.41
_exptl_crystal_size_min          0.11
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0341
_diffrn_reflns_av_unetI/netI     0.0340
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            8718
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.988
_diffrn_reflns_theta_min         4.120
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measurement_device_type  
'Bruker KAPPA APEX II area-detector diffractometer'
_diffrn_measurement_method       ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_diffrn_source_current           30.0
_diffrn_source_power             1.5
_diffrn_source_voltage           50.0
_diffrn_special_details          ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1968
_reflns_number_total             2318
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_refine_diff_density_max         1.727
_refine_diff_density_min         -1.197
_refine_diff_density_rms         0.182
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     79
_refine_ls_number_reflns         2318
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0369
_refine_ls_R_factor_gt           0.0267
_refine_ls_restrained_S_all      1.042
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0215P)²+1.8578P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0554
_refine_ls_wR_factor_ref         0.0585
_refine_special_details          ?
_olex2_refinement_description    
;
1.a Aromatic/amide H refined with riding coordinates:
 N1(H1), N3(H3), C5(H5), C4(H4), C2(H2)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Tc1 Tc 0.500000 0.500000 0.500000 0.00657(9) Uani 1 2 d S . P . .
Br1 Br 0.81811(5) 0.47353(5) 0.58119(3) 0.01356(9) Uani 1 1 d . . . . .
Br2 Br 0.47577(5) 0.20018(5) 0.48218(3) 0.01486(9) Uani 1 1 d . . . . .
Br3 Br 0.40234(5) 0.47889(5) 0.68485(3) 0.01417(9) Uani 1 1 d . . . . .
N1 N 1.0531(4) 0.3749(4) 0.8701(3) 0.0178(7) Uani 1 1 d . . . . .
H1 H 1.138466 0.304102 0.875496 0.021 Uiso 1 1 calc R U . . .
N3 N 0.7965(5) 0.4774(4) 0.8525(3) 0.0207(7) Uani 1 1 d . . . . .
H3 H 0.681561 0.486039 0.844786 0.025 Uiso 1 1 calc R U . . .
C5 C 1.0753(5) 0.5385(5) 0.8747(3) 0.0163(8) Uani 1 1 d . . . . .
H5 H 1.183642 0.594577 0.884492 0.020 Uiso 1 1 calc R U . . .
C4 C 0.9125(5) 0.6042(5) 0.8627(3) 0.0181(8) Uani 1 1 d . . . . .
H4 H 0.884193 0.714803 0.861567 0.022 Uiso 1 1 calc R U . . .
C2 C 0.8843(6) 0.3407(5) 0.8562(3) 0.0207(8) Uani 1 1 d . . . . .
H2 H 0.834426 0.236638 0.849914 0.025 Uiso 1 1 calc R U . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Tc1 0.00550(17) 0.00644(19) 0.00781(17) 0.00039(14) 0.00100(13) 0.00027(14)
Br1 0.01057(17) 0.01512(19) 0.01473(17) 0.00044(13) 0.00088(13) 0.00078(13)
Br2 0.01256(17) 0.01150(18) 0.02047(18) -0.00077(14) 0.00216(13) 0.00047(13)
Br3 0.01191(17) 0.0190(2) 0.01164(16) 0.00114(13) 0.00198(13) 0.00090(14)
N1 0.0187(17) 0.0192(18) 0.0153(15) 0.0003(13) 0.0013(13) 0.0068(14)
N3 0.0106(15) 0.035(2) 0.0157(16) 0.0014(14) -0.0005(12) -0.0007(14)
C5 0.0147(18) 0.019(2) 0.0154(17) -0.0035(14) 0.0023(14) -0.0065(15)
C4 0.020(2) 0.020(2) 0.0151(17) 0.0022(15) 0.0026(15) 0.0007(16)
C2 0.023(2) 0.022(2) 0.0163(18) -0.0019(16) 0.0022(16) -0.0080(18)

_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 Br1 2.5287(4) 3_666 ?
Tc1 Br1 2.5287(4) . ?
Tc1 Br2 2.5210(4) . ?
Tc1 Br2 2.5210(4) 3_666 ?
Tc1 Br3 2.5568(4) 3_666 ?
Tc1 Br3 2.5568(4) . ?
N1 H1 0.8800 . ?
N1 C5 1.379(5) . ?
N1 C2 1.319(5) . ?
N3 H3 0.8800 . ?
N3 C4 1.380(5) . ?
N3 C2 1.325(6) . ?
C5 H5 0.9500 . ?
C5 C4 1.357(6) . ?
C4 H4 0.9500 . ?
C2 H2 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
Br1 Tc1 Br1 180.0 3_666 . ?
Br1 Tc1 Br3 91.005(12) . . ?
Br1 Tc1 Br3 88.995(12) . 3_666 ?
Br1 Tc1 Br3 88.995(13) 3_666 . ?
Br1 Tc1 Br3 91.005(12) 3_666 3_666 ?
Br2 Tc1 Br1 89.746(12) . 3_666 ?
Br2 Tc1 Br1 90.254(12) 3_666 3_666 ?
Br2 Tc1 Br1 89.745(12) 3_666 . ?
Br2 Tc1 Br1 90.255(12) . . ?
Br2 Tc1 Br2 180.0 . 3_666 ?
Br2 Tc1 Br3 89.150(12) . . ?
Br2 Tc1 Br3 90.850(12) . 3_666 ?
Br2 Tc1 Br3 89.151(12) 3_666 3_666 ?
Br2 Tc1 Br3 90.849(12) 3_666 . ?
Br3 Tc1 Br3 180.0 . 3_666 ?
C5 N1 H1 125.2 . . ?
C2 N1 H1 125.2 . . ?
C2 N1 C5 109.5(3) . . ?
C4 N3 H3 125.1 . . ?
C2 N3 H3 125.1 . . ?
C2 N3 C4 109.8(4) . . ?
N1 C5 H5 126.6 . . ?
C4 C5 N1 106.8(3) . . ?
C4 C5 H5 126.6 . . ?
N3 C4 H4 127.0 . . ?
C5 C4 N3 106.0(4) . . ?
C5 C4 H4 127.0 . . ?
N1 C2 N3 107.9(4) . . ?
N1 C2 H2 126.1 . . ?
N3 C2 H2 126.1 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N1 H1 Br2 0.88 2.75 3.420(3) 133.6 4_666 yes
N3 H3 Br2 0.88 2.95 3.483(4) 120.4 4_566 yes
N3 H3 Br3 0.88 2.73 3.447(3) 139.0 . yes

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 C5 C4 N3 0.8(4) . . . . ?
C5 N1 C2 N3 -0.5(4) . . . . ?
C4 N3 C2 N1 1.0(4) . . . . ?
C2 N1 C5 C4 -0.2(4) . . . . ?
C2 N3 C4 C5 -1.1(4) . . . . ?

_shelx_res_file                  
;
TITL imtcbr_lt_0m_a.res in P2(1)/c
    imtcbr_lt_0m.res
    created by SHELXL-2018/3 at 13:58:00 on 07-Jun-2021
REM Old TITL ImTcBr_LT_0m in P21/c #14
REM SHELXT solution in P2(1)/c: R1 0.066, Rweak 0.003, Alpha 0.017
REM <I/s> 0.358 for 124 systematic absences, Orientation as input
REM Formula found by SHELXT: C10 Br7
CELL 0.71073 7.7038 8.3595 12.6218 90 98.133 90
ZERR 2 0.0005 0.0005 0.0008 0 0.003 0
LATT 1
SYMM -X,0.5+Y,0.5-Z
SFAC C H Br N Tc
UNIT 12 20 12 8 2
EQIV $1 1+X,0.5-Y,0.5+Z
EQIV $2 +X,0.5-Y,0.5+Z

L.S. 4 0 0
PLAN  4
SIZE 0.7 0.11 0.41
TEMP -173.15
CONF
HTAB N1 Br2_$1
HTAB N3 Br2_$2
HTAB N3 Br3
BOND
list 4
MORE -1
BOND $H
fmap 2 53
acta
SHEL 5 0.5
OMIT -2 60
REM <olex2.extras>
REM <HklSrc "%.\\ImTcBr_LT_0m.hkl">
REM </olex2.extras>

WGHT    0.021500    1.857800
FVAR       0.23536
TC1   5    0.500000    0.500000    0.500000    10.50000    0.00550    0.00644 =
         0.00781    0.00039    0.00100    0.00027
BR1   3    0.818112    0.473530    0.581195    11.00000    0.01057    0.01512 =
         0.01473    0.00044    0.00088    0.00078
BR2   3    0.475769    0.200178    0.482177    11.00000    0.01256    0.01150 =
         0.02047   -0.00077    0.00216    0.00047
BR3   3    0.402344    0.478887    0.684846    11.00000    0.01191    0.01905 =
         0.01164    0.00114    0.00198    0.00090
N1    4    1.053105    0.374874    0.870060    11.00000    0.01872    0.01920 =
         0.01528    0.00035    0.00128    0.00680
AFIX  43
H1    2    1.138466    0.304102    0.875496    11.00000   -1.20000
AFIX   0
N3    4    0.796504    0.477389    0.852537    11.00000    0.01057    0.03500 =
         0.01569    0.00143   -0.00050   -0.00066
AFIX  43
H3    2    0.681561    0.486039    0.844786    11.00000   -1.20000
AFIX   0
C5    1    1.075278    0.538531    0.874738    11.00000    0.01474    0.01888 =
         0.01540   -0.00349    0.00226   -0.00651
AFIX  43
H5    2    1.183642    0.594577    0.884492    11.00000   -1.20000
AFIX   0
C4    1    0.912514    0.604153    0.862726    11.00000    0.01954    0.01967 =
         0.01506    0.00215    0.00261    0.00073
AFIX  43
H4    2    0.884193    0.714803    0.861567    11.00000   -1.20000
AFIX   0
C2    1    0.884271    0.340745    0.856184    11.00000    0.02328    0.02221 =
         0.01631   -0.00186    0.00220   -0.00796
AFIX  43
H2    2    0.834426    0.236638    0.849914    11.00000   -1.20000
AFIX   0
HKLF 4




REM  imtcbr_lt_0m_a.res in P2(1)/c
REM wR2 = 0.0585, GooF = S = 1.042, Restrained GooF = 1.042 for all data
REM R1 = 0.0267 for 1968 Fo > 4sig(Fo) and 0.0369 for all 2318 data
REM 79 parameters refined using 0 restraints

END

WGHT      0.0215      1.8579

REM Highest difference peak  1.727,  deepest hole -1.197,  1-sigma level  0.182
Q1    1   0.5023  0.5572  0.4954  11.00000  0.05    1.73
Q2    1   0.4392  0.4993  0.4687  11.00000  0.05    1.57
Q3    1   0.3804  0.1978  0.4395  11.00000  0.05    0.76
Q4    1   0.3230  0.3551  0.6632  11.00000  0.05    0.68
;
_shelx_res_checksum              51161
# end Validation Reply Form
_olex2_submission_special_instructions 'No special instructions were received'
# start Validation Reply Form
_vrf_PLAT110_imtcbr_lt_0m        
;
PROBLEM: ADDSYM Detects Potential Lattice Translation ... ? Check
RESPONSE: In the space group C2 / m, the imidazolium cation is disordered;
refinement gives worse results.
;
_vrf_PLAT112_imtcbr_lt_0m        
;
PROBLEM: ADDSYM Detects New (Pseudo) Symm. Elem A 100 %Fit
RESPONSE: In the space group C2 / m, the imidazolium cation is disordered;
refinement gives worse results.
;
_vrf_PLAT113_imtcbr_lt_0m        
;
PROBLEM: ADDSYM Suggests Possible Pseudo/New Space Group C2/m Check
RESPONSE: In the space group C2 / m, the imidazolium cation is disordered;
refinement gives worse results.
;
####################################################################### 
# 
# 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_tcb
_database_code_depnum_ccdc_archive 'CCDC 2512688'
loop_
_audit_author_name
_audit_author_address
'Mikhail Grigoriev'
;IPCE RAS
Russia
;
_audit_update_record             
;
2025-12-02 deposited with the CCDC.	2026-02-11 downloaded from the CCDC.
;
_audit_creation_date             2025-07-07
_audit_creation_method           
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_shelxl_version_number           2014-3
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         'Br6 Tc, 2(C4 H7 N2)'
_chemical_formula_sum            'C8 H14 Br6 N4 Tc'
_chemical_formula_weight         743.69
_chemical_absolute_configuration ?
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 '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'
Tc Tc -1.4390 0.7593 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_H-M_alt        'P 21 21 2'
_space_group_name_Hall           'P 2 2ab'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x+1/2, y+1/2, -z'
'x+1/2, -y+1/2, -z'

_cell_length_a                   7.8599(6)
_cell_length_b                   16.0412(13)
_cell_length_c                   7.2519(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     914.34(13)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    2456
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      30.057
_cell_measurement_theta_min      3.082
_shelx_estimated_absorpt_T_max   0.874
_shelx_estimated_absorpt_T_min   0.215
_exptl_absorpt_coefficient_mu    13.890
_exptl_absorpt_correction_T_max  0.874
_exptl_absorpt_correction_T_min  0.603
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1256 before and 0.0507 after correction.
The Ratio of minimum to maximum transmission is 0.5153.
The λ/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.701
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       fragment
_exptl_crystal_F_000             686
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.01
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   1.0000
_exptl_transmission_factor_min   0.6491
_diffrn_reflns_av_R_equivalents  0.0418
_diffrn_reflns_av_unetI/netI     0.0461
_diffrn_reflns_Laue_measured_fraction_full 0.988
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       10
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            8987
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.992
_diffrn_reflns_theta_min         4.592
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.988
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measurement_device_type  
'Bruker KAPPA APEX II area-detector diffractometer'
_diffrn_measurement_method       ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.715
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                2259
_reflns_number_total             2645
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       ?
_computing_data_collection       ?
_computing_data_reduction        ?
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    ?
_refine_diff_density_max         2.647
_refine_diff_density_min         -0.894
_refine_diff_density_rms         0.198
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.48(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     89
_refine_ls_number_reflns         2645
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0471
_refine_ls_R_factor_gt           0.0359
_refine_ls_restrained_S_all      1.050
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0291P)²+3.2821P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0773
_refine_ls_wR_factor_ref         0.0809
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.5205
 0.4795
2.a Aromatic/amide H refined with riding coordinates:
 N1(H1A), N2(H2A), C3(H3A), C4(H4A)
2.b Idealised Me refined as rotating group:
 C2(H2B,H2C,H2D)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Tc1 Tc 0.5000 0.5000 0.76631(14) 0.01403(19) Uani 1 2 d S T P . .
Br1 Br 0.70889(13) 0.54117(6) 0.52163(12) 0.0190(2) Uani 1 1 d . . . . .
Br2 Br 0.37316(9) 0.64421(4) 0.76837(14) 0.01930(19) Uani 1 1 d . . . . .
Br3 Br 0.29049(13) 0.45732(7) 1.00747(11) 0.0195(2) Uani 1 1 d . . . . .
N1 N 0.8965(8) 0.8492(4) 0.7240(13) 0.0242(17) Uani 1 1 d . . . . .
H1A H 0.9190 0.9022 0.7051 0.029 Uiso 1 1 calc R U . . .
N2 N 0.7633(8) 0.7357(4) 0.7635(14) 0.0244(15) Uani 1 1 d . . . . .
H2A H 0.6803 0.6995 0.7783 0.029 Uiso 1 1 calc R U . . .
C1 C 0.7416(9) 0.8171(4) 0.7441(14) 0.0173(14) Uani 1 1 d . . . . .
C2 C 0.5787(9) 0.8632(5) 0.7421(17) 0.0246(17) Uani 1 1 d . . . . .
H2B H 0.4844 0.8241 0.7610 0.037 Uiso 1 1 calc R U . . .
H2C H 0.5649 0.8912 0.6230 0.037 Uiso 1 1 calc R U . . .
H2D H 0.5787 0.9048 0.8411 0.037 Uiso 1 1 calc R U . . .
C3 C 1.0162(10) 0.7872(5) 0.7374(15) 0.0249(17) Uani 1 1 d . . . . .
H3A H 1.1362 0.7941 0.7330 0.030 Uiso 1 1 calc R U . . .
C4 C 0.9331(10) 0.7157(5) 0.7574(17) 0.0258(18) Uani 1 1 d . . . . .
H4A H 0.9815 0.6615 0.7659 0.031 Uiso 1 1 calc R U . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Tc1 0.0093(3) 0.0095(3) 0.0232(5) 0.000 0.000 0.0001(3)
Br1 0.0155(5) 0.0154(5) 0.0260(4) 0.0004(3) 0.0049(3) -0.0010(4)
Br2 0.0122(3) 0.0105(3) 0.0352(5) -0.0001(4) 0.0000(4) 0.0020(2)
Br3 0.0150(5) 0.0165(5) 0.0270(5) 0.0003(3) 0.0047(3) -0.0008(4)
N1 0.019(3) 0.010(3) 0.044(5) 0.002(4) 0.003(4) -0.002(2)
N2 0.015(3) 0.012(3) 0.046(5) 0.003(4) 0.001(4) -0.002(2)
C1 0.013(3) 0.014(3) 0.024(4) 0.000(4) 0.000(4) 0.000(2)
C2 0.016(3) 0.017(3) 0.041(5) 0.000(5) 0.005(4) 0.001(3)
C3 0.013(3) 0.020(3) 0.042(5) -0.003(5) -0.002(5) 0.002(3)
C4 0.021(4) 0.015(3) 0.041(5) -0.003(5) -0.010(5) 0.003(3)

_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 Br1 2.5060(12) 2_665 ?
Tc1 Br1 2.5060(12) . ?
Tc1 Br2 2.5190(7) 2_665 ?
Tc1 Br2 2.5190(7) . ?
Tc1 Br3 2.4978(12) 2_665 ?
Tc1 Br3 2.4978(12) . ?
N1 H1A 0.8800 . ?
N1 C1 1.330(9) . ?
N1 C3 1.372(9) . ?
N2 H2A 0.8800 . ?
N2 C1 1.324(8) . ?
N2 C4 1.374(10) . ?
C1 C2 1.479(10) . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?
C2 H2D 0.9800 . ?
C3 H3A 0.9500 . ?
C3 C4 1.328(11) . ?
C4 H4A 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
Br1 Tc1 Br1 89.85(6) 2_665 . ?
Br1 Tc1 Br2 91.23(4) 2_665 2_665 ?
Br1 Tc1 Br2 89.25(4) . 2_665 ?
Br1 Tc1 Br2 91.23(4) . . ?
Br1 Tc1 Br2 89.25(4) 2_665 . ?
Br2 Tc1 Br2 179.32(7) . 2_665 ?
Br3 Tc1 Br1 89.52(3) 2_665 . ?
Br3 Tc1 Br1 179.21(5) 2_665 2_665 ?
Br3 Tc1 Br1 89.52(3) . 2_665 ?
Br3 Tc1 Br1 179.21(5) . . ?
Br3 Tc1 Br2 90.29(4) 2_665 . ?
Br3 Tc1 Br2 90.29(4) . 2_665 ?
Br3 Tc1 Br2 89.23(4) . . ?
Br3 Tc1 Br2 89.23(4) 2_665 2_665 ?
Br3 Tc1 Br3 91.12(6) 2_665 . ?
C1 N1 H1A 125.1 . . ?
C1 N1 C3 109.9(6) . . ?
C3 N1 H1A 125.1 . . ?
C1 N2 H2A 124.7 . . ?
C1 N2 C4 110.6(6) . . ?
C4 N2 H2A 124.7 . . ?
N1 C1 C2 126.8(6) . . ?
N2 C1 N1 106.0(6) . . ?
N2 C1 C2 127.3(7) . . ?
C1 C2 H2B 109.5 . . ?
C1 C2 H2C 109.5 . . ?
C1 C2 H2D 109.5 . . ?
H2B C2 H2C 109.5 . . ?
H2B C2 H2D 109.5 . . ?
H2C C2 H2D 109.5 . . ?
N1 C3 H3A 126.4 . . ?
C4 C3 N1 107.3(7) . . ?
C4 C3 H3A 126.4 . . ?
N2 C4 H4A 126.9 . . ?
C3 C4 N2 106.2(7) . . ?
C3 C4 H4A 126.9 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N1 H1A Br1 0.88 2.95 3.653(7) 138.6 3_656
N1 H1A Br1 0.88 2.95 3.506(7) 122.6 4_566
N2 H2A Br2 0.88 2.57 3.400(6) 156.8 .
N2 H2A Br3 0.88 3.02 3.591(7) 124.1 2_665

_shelx_res_file                  
;
TITL Tcb in P2(1)2(1)2
CELL 0.71073   7.8599  16.0412   7.2519  90.000  90.000  90.000
ZERR    2.00   0.0006   0.0013   0.0006   0.000   0.000   0.000
LATT -1
SYMM -X, -Y, Z
SYMM 0.5-X, 0.5+Y, -Z
SYMM 0.5+X, 0.5-Y, -Z
SFAC C H N BR TC
UNIT 16 28 8 12 2
TEMP -173
SIZE 0.16 0.10 0.01
L.S. 8
BOND $H
FMAP 2
PLAN 20
HTAB
EQIV $1 -x+3/2, y+1/2, -z+1
HTAB N1 Br1_$1
EQIV $2 x+1/2, -y+3/2, -z+1
HTAB N1 Br1_$2
HTAB N2 Br2
EQIV $3 -x+1, -y+1, z
HTAB N2 Br3_$3
ACTA
SHEL 5 0.5
OMIT -2 60
OMIT     0   3   2
OMIT     0   1   4
OMIT     1   0   2
OMIT     0   0   3
OMIT     3   2   2
TWIN
WGHT    0.029100    3.282100
BASF   0.47950
FVAR       0.09612
TC1   5    0.500000    0.500000    0.766306    10.50000    0.00934    0.00954 =
         0.02322    0.00000    0.00000    0.00012
BR1   4    0.708887    0.541166    0.521629    11.00000    0.01546    0.01539 =
         0.02601    0.00037    0.00488   -0.00096
BR2   4    0.373164    0.644210    0.768374    11.00000    0.01218    0.01054 =
         0.03516   -0.00008    0.00004    0.00197
BR3   4    0.290493    0.457323    1.007466    11.00000    0.01504    0.01647 =
         0.02697    0.00034    0.00471   -0.00079
N1    3    0.896548    0.849176    0.724028    11.00000    0.01856    0.01044 =
         0.04353    0.00153    0.00262   -0.00159
AFIX  43
H1A   2    0.918993    0.902232    0.705055    11.00000   -1.20000
AFIX   0
N2    3    0.763253    0.735723    0.763526    11.00000    0.01533    0.01212 =
         0.04583    0.00313    0.00146   -0.00220
AFIX  43
H2A   2    0.680330    0.699475    0.778318    11.00000   -1.20000
AFIX   0
C1    1    0.741553    0.817121    0.744064    11.00000    0.01350    0.01431 =
         0.02410    0.00040    0.00049    0.00018
C2    1    0.578657    0.863212    0.742116    11.00000    0.01595    0.01681 =
         0.04102   -0.00016    0.00458    0.00075
AFIX 137
H2B   2    0.484416    0.824136    0.761027    11.00000   -1.50000
H2C   2    0.564897    0.891232    0.622960    11.00000   -1.50000
H2D   2    0.578690    0.904819    0.841070    11.00000   -1.50000
AFIX   0
C3    1    1.016212    0.787183    0.737355    11.00000    0.01304    0.01997 =
         0.04173   -0.00254   -0.00184    0.00192
AFIX  43
H3A   2    1.136179    0.794126    0.733024    11.00000   -1.20000
AFIX   0
C4    1    0.933133    0.715685    0.757431    11.00000    0.02076    0.01549 =
         0.04127   -0.00268   -0.01005    0.00316
AFIX  43
H4A   2    0.981450    0.661536    0.765885    11.00000   -1.20000

AFIX   0
HKLF 4

REM  Tcb in P2(1)2(1)2
REM R1 =  0.0359 for    2259 Fo > 4sig(Fo)  and  0.0471 for all    2645 data
REM     89 parameters refined using      0 restraints

END

WGHT      0.0290      3.2819

REM Instructions for potential hydrogen bonds
HTAB N1 Br1_$1
HTAB N1 Br1_$2
HTAB N2 Br2
HTAB N2 Br3_$3
HTAB C2 Br2
EQIV $4 x+1/2, -y+3/2, -z+2
HTAB C2 Br3_$4
EQIV $5 x+1, y, z
HTAB C3 Br2_$5
HTAB C4 Br2_$5

REM Highest difference peak  2.647,  deepest hole -0.894,  1-sigma level  0.198
Q1    1   0.5000  0.5000  0.6584  10.50000  0.05    2.65
Q2    1   0.3764  0.6478  0.6593  11.00000  0.05    2.09
Q3    1   0.2980  0.4554  0.9039  11.00000  0.05    1.95
Q4    1   0.7013  0.5434  0.4156  11.00000  0.05    1.70
Q5    1   0.7038  0.5461  0.6516  11.00000  0.05    0.81
Q6    1   0.8051  0.8363  0.7610  11.00000  0.05    0.76
Q7    1   0.3749  0.6623  0.9137  11.00000  0.05    0.75
Q8    1   0.2819  0.4668  1.1458  11.00000  0.05    0.74
Q9    1   0.6389  0.5011  0.4700  11.00000  0.05    0.72
Q10   1   0.5073  0.5263  0.9052  11.00000  0.05    0.68
Q11   1   0.7993  0.6756  0.5519  11.00000  0.05    0.59
Q12   1   0.7154  0.8688  0.8253  11.00000  0.05    0.59
Q13   1   0.6743  0.8469  0.7451  11.00000  0.05    0.59
Q14   1   0.2528  0.4196  1.1123  11.00000  0.05    0.59
Q15   1   0.2246  0.5003  1.1053  11.00000  0.05    0.55
Q16   1   0.9803  0.7383  0.6731  11.00000  0.05    0.54
Q17   1   0.2314  0.4069  0.9428  11.00000  0.05    0.54
Q18   1   0.4803  0.6054  0.6744  11.00000  0.05    0.53
Q19   1   0.3055  0.5505  0.9062  11.00000  0.05    0.53
Q20   1   0.3009  0.4155  1.2193  11.00000  0.05    0.53
;
_shelx_res_checksum              25733
_olex2_submission_special_instructions 'No special instructions were received'
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.5205
2 0.4795

# start Validation Reply Form
_vrf_PLAT971_tcb                 
;
PROBLEM: Check Calcd Resid. Dens. 0.80A From Tc1 2.86 eA-3
RESPONSE: The peak is near the heavy atom.
;
####################################################################### 
# 
# 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_tcem
_database_code_depnum_ccdc_archive 'CCDC 2512689'
loop_
_audit_author_name
_audit_author_address
'Mikhail Grigoriev'
;IPCE RAS
Russia
;
_audit_update_record             
;
2025-12-02 deposited with the CCDC.	2026-02-11 downloaded from the CCDC.
;
_audit_creation_date             2025-07-07
_audit_creation_method           
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         'Br6 Tc, 2(C5 H9 N2)'
_chemical_formula_sum            'C10 H18 Br6 N4 Tc'
_chemical_formula_weight         771.74
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 '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'
Tc Tc -1.4390 0.7593 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 1 21/n 1'
_space_group_name_Hall           '-P 2yn'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x-1/2, -y-1/2, z-1/2'

_cell_length_a                   7.9083(19)
_cell_length_b                   13.088(4)
_cell_length_c                   10.176(2)
_cell_angle_alpha                90
_cell_angle_beta                 107.329(8)
_cell_angle_gamma                90
_cell_volume                     1005.4(4)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    1791
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.156
_cell_measurement_theta_min      2.880
_shelx_estimated_absorpt_T_max   0.271
_shelx_estimated_absorpt_T_min   0.187
_exptl_absorpt_coefficient_mu    12.636
_exptl_absorpt_correction_T_max  0.271
_exptl_absorpt_correction_T_min  0.199
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.1256 before and 0.0507 after correction.
The Ratio of minimum to maximum transmission is 0.5153.
The λ/2 correction factor is 0.0015.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.549
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       fragment
_exptl_crystal_F_000             718
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.14
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0527
_diffrn_reflns_av_unetI/netI     0.0544
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            10940
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.985
_diffrn_reflns_theta_min         4.121
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device_type  
'Bruker KAPPA APEX II area-detector diffractometer'
_diffrn_measurement_method       ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                1913
_reflns_number_total             2906
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    ?
_refine_diff_density_max         0.797
_refine_diff_density_min         -0.932
_refine_diff_density_rms         0.139
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.012
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     97
_refine_ls_number_reflns         2906
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0726
_refine_ls_R_factor_gt           0.0347
_refine_ls_restrained_S_all      1.012
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0211P)²+0.2622P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0577
_refine_ls_wR_factor_ref         0.0668
_refine_special_details          ?
_olex2_refinement_description    
;
1.a Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B)
1.b Me refined with riding coordinates:
 C3(H3A,H3B,H3C)
1.c Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C4(H4), C5(H5)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Tc1 Tc 0.500000 0.500000 0.500000 0.02761(12) Uani 1 2 d S . P . .
Br1 Br 0.69261(6) 0.36397(3) 0.64261(4) 0.03902(13) Uani 1 1 d . . . . .
Br2 Br 0.51210(7) 0.59808(4) 0.71411(4) 0.05031(15) Uani 1 1 d . . . . .
Br3 Br 0.77037(6) 0.59227(4) 0.48294(5) 0.04867(15) Uani 1 1 d . . . . .
N1 N 0.2235(5) 0.5220(3) 1.0001(4) 0.0401(9) Uani 1 1 d . . . . .
H1 H 0.292037 0.500124 1.080058 0.048 Uiso 1 1 calc R U . . .
N2 N 0.0612(5) 0.5255(3) 0.7940(4) 0.0417(9) Uani 1 1 d . . . . .
H2 H 0.001494 0.506346 0.710085 0.050 Uiso 1 1 calc R U . . .
C1 C 0.1589(5) 0.4639(3) 0.8901(4) 0.0358(10) Uani 1 1 d . . . . .
C2 C 0.1846(6) 0.3527(4) 0.8783(6) 0.0507(13) Uani 1 1 d . . . . .
H2A H 0.117374 0.330476 0.784245 0.061 Uiso 1 1 calc R U . . .
H2B H 0.134288 0.316773 0.943706 0.061 Uiso 1 1 calc R U . . .
C3 C 0.3751(6) 0.3210(4) 0.9064(5) 0.0520(13) Uani 1 1 d . . . . .
H3A H 0.381532 0.246749 0.896659 0.078 Uiso 1 1 calc R U . . .
H3B H 0.425392 0.354709 0.840530 0.078 Uiso 1 1 calc R U . . .
H3C H 0.442330 0.340987 1.000217 0.078 Uiso 1 1 calc R U . . .
C4 C 0.1684(6) 0.6208(4) 0.9718(5) 0.0429(11) Uani 1 1 d . . . . .
H4 H 0.198163 0.677238 1.033114 0.051 Uiso 1 1 calc R U . . .
C5 C 0.0658(6) 0.6227(4) 0.8428(5) 0.0435(11) Uani 1 1 d . . . . .
H5 H 0.006691 0.680547 0.793745 0.052 Uiso 1 1 calc R U . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Tc1 0.0328(3) 0.0247(2) 0.0211(2) 0.00019(19) 0.00161(18) 0.0019(2)
Br1 0.0444(3) 0.0308(2) 0.0342(2) 0.00438(19) 0.00017(19) 0.0064(2)
Br2 0.0723(4) 0.0434(3) 0.0269(2) -0.0059(2) 0.0020(2) 0.0187(3)
Br3 0.0417(3) 0.0535(3) 0.0453(3) 0.0131(2) 0.0046(2) -0.0080(2)
N1 0.039(2) 0.041(2) 0.0336(19) 0.0076(17) 0.0005(16) -0.0027(18)
N2 0.044(2) 0.041(2) 0.0332(19) 0.0018(17) 0.0019(16) 0.0036(19)
C1 0.029(2) 0.035(2) 0.044(2) 0.006(2) 0.011(2) -0.003(2)
C2 0.048(3) 0.034(3) 0.071(3) 0.008(3) 0.019(3) 0.001(2)
C3 0.054(3) 0.054(3) 0.049(3) -0.005(3) 0.017(2) 0.021(3)
C4 0.050(3) 0.037(3) 0.043(3) -0.005(2) 0.016(2) -0.004(2)
C5 0.048(3) 0.037(3) 0.044(3) 0.009(2) 0.012(2) 0.011(2)

_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Tc1 Br1 2.5058(6) . ?
Tc1 Br1 2.5058(6) 3_666 ?
Tc1 Br2 2.5059(6) . ?
Tc1 Br2 2.5060(6) 3_666 ?
Tc1 Br3 2.5063(7) 3_666 ?
Tc1 Br3 2.5063(7) . ?
N1 H1 0.8800 . ?
N1 C1 1.324(5) . ?
N1 C4 1.368(6) . ?
N2 H2 0.8800 . ?
N2 C1 1.325(5) . ?
N2 C5 1.362(6) . ?
C1 C2 1.478(6) . ?
C2 H2A 0.9900 . ?
C2 H2B 0.9900 . ?
C2 C3 1.506(6) . ?
C3 H3A 0.9800 . ?
C3 H3B 0.9800 . ?
C3 H3C 0.9800 . ?
C4 H4 0.9500 . ?
C4 C5 1.322(6) . ?
C5 H5 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
Br1 Tc1 Br1 179.999(19) . 3_666 ?
Br1 Tc1 Br2 90.07(2) 3_666 3_666 ?
Br1 Tc1 Br2 90.07(2) . . ?
Br1 Tc1 Br2 89.93(2) 3_666 . ?
Br1 Tc1 Br2 89.93(2) . 3_666 ?
Br1 Tc1 Br3 90.09(2) 3_666 . ?
Br1 Tc1 Br3 90.09(2) . 3_666 ?
Br1 Tc1 Br3 89.91(2) . . ?
Br1 Tc1 Br3 89.91(2) 3_666 3_666 ?
Br2 Tc1 Br2 180.0 . 3_666 ?
Br2 Tc1 Br3 90.06(2) . . ?
Br2 Tc1 Br3 89.94(2) . 3_666 ?
Br2 Tc1 Br3 89.94(2) 3_666 . ?
Br2 Tc1 Br3 90.06(2) 3_666 3_666 ?
Br3 Tc1 Br3 180.00(2) . 3_666 ?
C1 N1 H1 124.9 . . ?
C1 N1 C4 110.3(4) . . ?
C4 N1 H1 124.9 . . ?
C1 N2 H2 124.7 . . ?
C1 N2 C5 110.7(4) . . ?
C5 N2 H2 124.7 . . ?
N1 C1 N2 105.5(4) . . ?
N1 C1 C2 127.3(4) . . ?
N2 C1 C2 127.1(4) . . ?
C1 C2 H2A 108.7 . . ?
C1 C2 H2B 108.7 . . ?
C1 C2 C3 114.2(4) . . ?
H2A C2 H2B 107.6 . . ?
C3 C2 H2A 108.7 . . ?
C3 C2 H2B 108.7 . . ?
C2 C3 H3A 109.5 . . ?
C2 C3 H3B 109.5 . . ?
C2 C3 H3C 109.5 . . ?
H3A C3 H3B 109.5 . . ?
H3A C3 H3C 109.5 . . ?
H3B C3 H3C 109.5 . . ?
N1 C4 H4 126.6 . . ?
C5 C4 N1 106.8(4) . . ?
C5 C4 H4 126.6 . . ?
N2 C5 H5 126.7 . . ?
C4 C5 N2 106.7(4) . . ?
C4 C5 H5 126.7 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N1 H1 Br2 0.88 2.55 3.417(4) 168.2 3_667 yes
N2 H2 Br1 0.88 2.99 3.559(4) 124.5 1_455 yes
N2 H2 Br3 0.88 2.73 3.425(4) 137.3 1_455 yes

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 -60.0(6) . . . . ?
N1 C4 C5 N2 -0.6(5) . . . . ?
N2 C1 C2 C3 122.6(5) . . . . ?
C1 N1 C4 C5 1.1(5) . . . . ?
C1 N2 C5 C4 -0.1(5) . . . . ?
C4 N1 C1 N2 -1.1(5) . . . . ?
C4 N1 C1 C2 -178.9(4) . . . . ?
C5 N2 C1 N1 0.7(5) . . . . ?
C5 N2 C1 C2 178.5(4) . . . . ?

_shelx_res_file                  
;
TITL TcHEtIm_LT_0m in P2(1)/n
    tcem.res
    created by SHELXL-2018/3 at 15:10:11 on 04-Jun-2021
CELL 0.71073 7.9083 13.088 10.176 90 107.329 90
ZERR 2 0.0019 0.004 0.002 0 0.008 0
LATT 1
SYMM 0.5-X,0.5+Y,0.5-Z
SFAC C H N Br Tc
UNIT 20 36 8 12 2
EQIV $1 1-X,1-Y,2-Z
EQIV $2 -1+X,+Y,+Z

L.S. 8
PLAN  5
SIZE 0.2 0.18 0.14
TEMP -173(2)
CONF
HTAB N1 Br2_$1
HTAB N2 Br1_$2
HTAB N2 Br3_$2
BOND $H
HTAB
MORE -1
fmap 2
acta
SHEL 5 0.5
OMIT -2 60
OMIT -3 4 3
OMIT 9 8 1
OMIT -5 10 5
OMIT -3 6 4
OMIT 1 12 0
OMIT 4 11 1
OMIT -2 16 6
REM <olex2.extras>
REM <HklSrc "%.\\tcem.hkl">
REM </olex2.extras>

WGHT    0.021100    0.262200
FVAR       0.36009
TC1   5    0.500000    0.500000    0.500000    10.50000    0.03285    0.02469 =
         0.02110    0.00019    0.00161    0.00187
BR1   4    0.692613    0.363970    0.642609    11.00000    0.04444    0.03081 =
         0.03425    0.00438    0.00017    0.00643
BR2   4    0.512095    0.598075    0.714108    11.00000    0.07227    0.04343 =
         0.02689   -0.00595    0.00202    0.01868
BR3   4    0.770373    0.592270    0.482941    11.00000    0.04174    0.05353 =
         0.04528    0.01314    0.00463   -0.00803
N1    3    0.223487    0.521958    1.000131    11.00000    0.03888    0.04111 =
         0.03356    0.00762    0.00055   -0.00270
AFIX  43
H1    2    0.292037    0.500124    1.080058    11.00000   -1.20000
AFIX   0
N2    3    0.061178    0.525528    0.793966    11.00000    0.04421    0.04138 =
         0.03321    0.00185    0.00193    0.00359
AFIX  43
H2    2    0.001494    0.506346    0.710085    11.00000   -1.20000
AFIX   0
C1    1    0.158942    0.463862    0.890095    11.00000    0.02907    0.03470 =
         0.04392    0.00596    0.01120   -0.00262
C2    1    0.184550    0.352726    0.878294    11.00000    0.04760    0.03420 =
         0.07087    0.00838    0.01852    0.00123
AFIX  23
H2A   2    0.117374    0.330476    0.784245    11.00000   -1.20000
H2B   2    0.134288    0.316773    0.943706    11.00000   -1.20000
AFIX   0
C3    1    0.375087    0.321025    0.906377    11.00000    0.05394    0.05386 =
         0.04944   -0.00450    0.01728    0.02121
AFIX  33
H3A   2    0.381532    0.246749    0.896659    11.00000   -1.50000
H3B   2    0.425392    0.354709    0.840530    11.00000   -1.50000
H3C   2    0.442330    0.340987    1.000217    11.00000   -1.50000
AFIX   0
C4    1    0.168398    0.620793    0.971839    11.00000    0.04994    0.03658 =
         0.04347   -0.00534    0.01605   -0.00416
AFIX  43
H4    2    0.198163    0.677238    1.033114    11.00000   -1.20000
AFIX   0
C5    1    0.065762    0.622669    0.842824    11.00000    0.04843    0.03710 =
         0.04385    0.00870    0.01188    0.01102
AFIX  43
H5    2    0.006691    0.680547    0.793745    11.00000   -1.20000
AFIX   0
HKLF 4




REM  TcHEtIm_LT_0m in P2(1)/n
REM wR2 = 0.0668, GooF = S = 1.012, Restrained GooF = 1.012 for all data
REM R1 = 0.0347 for 1913 Fo > 4sig(Fo) and 0.0726 for all 2906 data
REM 97 parameters refined using 0 restraints

END

WGHT      0.0213      0.2887

REM Instructions for potential hydrogen bonds
HTAB N1 Br2_$1
HTAB N2 Br1_$2
HTAB N2 Br3_$2
EQIV $4 x-1/2, -y+1/2, z+1/2
HTAB C2 Br1_$4
EQIV $5 -x+1/2, y+1/2, -z+3/2
HTAB C5 Br1_$5

REM Highest difference peak  0.797,  deepest hole -0.932,  1-sigma level  0.139
Q1    1   0.4642  0.5000  0.5369  11.00000  0.05    0.80
Q2    1   0.7345  0.6125  0.5404  11.00000  0.05    0.63
Q3    1   0.7548  0.5350  0.4676  11.00000  0.05    0.57
Q4    1   0.6377  0.5557  0.4954  11.00000  0.05    0.57
Q5    1   0.8045  0.6032  0.4721  11.00000  0.05    0.51
;
_shelx_res_checksum              67724
_olex2_submission_special_instructions 'No special instructions were received'
####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_tcm
_database_code_depnum_ccdc_archive 'CCDC 2512690'
loop_
_audit_author_name
_audit_author_address
'Mikhail Grigoriev'
;IPCE RAS
Russia
;
_audit_update_record             
;
2025-12-02 deposited with the CCDC.	2026-02-11 downloaded from the CCDC.
;
_audit_creation_date             2025-07-07
_audit_creation_method           
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_shelx_SHELXL_version_number     2018/3
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         'Br3 Tc0.5, C4 H7 N2'
_chemical_formula_sum            'C4 H7 Br3 N2 Tc0.50'
_chemical_formula_weight         371.85
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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'
Tc Tc -1.4390 0.7593 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_shelx_space_group_comment       
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_H-M_alt        'P -1'
_space_group_name_Hall           '-P 1'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   7.7095(8)
_cell_length_b                   7.9065(8)
_cell_length_c                   8.0783(8)
_cell_angle_alpha                79.107(5)
_cell_angle_beta                 86.065(5)
_cell_angle_gamma                66.969(5)
_cell_volume                     444.99(8)
_cell_formula_units_Z            2
_cell_measurement_reflns_used    8224
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      39.976
_cell_measurement_theta_min      2.844
_shelx_estimated_absorpt_T_max   0.183
_shelx_estimated_absorpt_T_min   0.079
_exptl_absorpt_coefficient_mu    14.270
_exptl_absorpt_correction_T_max  0.7479
_exptl_absorpt_correction_T_min  0.5018
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2008/1 (Bruker,2008) was used for absorption correction.
wR2(int) was 0.0949 before and 0.0470 after correction.
The Ratio of minimum to maximum transmission is 0.6709.
The λ/2 correction factor is 0.0015.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.775
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       fragment
_exptl_crystal_F_000             343
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.18
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.989
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            18576
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         39.996
_diffrn_reflns_theta_min         4.157
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.989
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  
'Bruker KAPPA APEX II area-detector diffractometer'
_diffrn_measurement_method       ?
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                4696
_reflns_number_total             5509
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT v7.68A (Bruker, 2009)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v7.68A (Bruker, 2009)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    ?
_refine_diff_density_max         1.264
_refine_diff_density_min         -1.307
_refine_diff_density_rms         0.204
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     89
_refine_ls_number_reflns         5509
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0368
_refine_ls_R_factor_gt           0.0282
_refine_ls_restrained_S_all      1.041
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0312P)²+0.3930P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0679
_refine_ls_wR_factor_ref         0.0705
_refine_special_details          ?
_olex2_refinement_description    
;
1.a Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), C3(H3), C4(H4)
1.b Idealised Me refined as rotating group:
 C2(H2A,H2B,H2C)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Tc1 Tc 0.000000 0.000000 0.500000 0.00821(4) Uani 1 2 d S . P . .
Br1 Br -0.28613(3) 0.29672(3) 0.48546(2) 0.01317(4) Uani 1 1 d . . . . .
Br2 Br 0.05881(3) 0.09183(3) 0.19248(2) 0.01238(4) Uani 1 1 d . . . . .
Br3 Br 0.19757(3) 0.16005(3) 0.58385(2) 0.01290(4) Uani 1 1 d . . . . .
N1 N 0.4401(3) 0.2464(3) 0.1884(3) 0.0220(4) Uani 1 1 d . . . . .
H1 H 0.446566 0.206337 0.298031 0.026 Uiso 1 1 calc R U . . .
N2 N 0.3443(3) 0.4143(3) -0.0635(2) 0.0196(3) Uani 1 1 d . . . . .
H2 H 0.276598 0.503129 -0.143848 0.023 Uiso 1 1 calc R U . . .
C1 C 0.3049(2) 0.3973(2) 0.1069(2) 0.0086(2) Uani 1 1 d . . . . .
C2 C 0.1415(3) 0.5249(3) 0.1852(3) 0.0172(3) Uani 1 1 d . . . . .
H2A H 0.118508 0.653987 0.132085 0.026 Uiso 1 1 calc R U . . .
H2B H 0.166192 0.508258 0.305839 0.026 Uiso 1 1 calc R U . . .
H2C H 0.030434 0.497950 0.170176 0.026 Uiso 1 1 calc R U . . .
C3 C 0.5638(3) 0.1666(3) 0.0757(3) 0.0150(3) Uani 1 1 d . . . . .
H3 H 0.674337 0.056340 0.100667 0.018 Uiso 1 1 calc R U . . .
C4 C 0.5065(3) 0.2690(3) -0.0836(3) 0.0179(4) Uani 1 1 d . . . . .
H4 H 0.568859 0.242555 -0.186799 0.021 Uiso 1 1 calc R U . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Tc1 0.00836(8) 0.00815(8) 0.00675(7) -0.00078(6) 0.00040(6) -0.00204(6)
Br1 0.01219(8) 0.01112(8) 0.01137(8) -0.00226(6) -0.00092(6) 0.00093(6)
Br2 0.01416(8) 0.01349(8) 0.00758(7) -0.00011(5) 0.00158(6) -0.00431(6)
Br3 0.01394(8) 0.01337(8) 0.01262(8) -0.00117(6) -0.00079(6) -0.00694(6)
N1 0.0198(8) 0.0246(9) 0.0198(8) 0.0029(7) -0.0031(7) -0.0093(7)
N2 0.0202(8) 0.0219(8) 0.0145(7) 0.0002(6) -0.0006(6) -0.0073(7)
C1 0.0078(6) 0.0098(6) 0.0087(6) -0.0002(5) -0.0007(5) -0.0046(5)
C2 0.0163(8) 0.0187(9) 0.0173(8) -0.0051(7) 0.0031(7) -0.0070(7)
C3 0.0094(7) 0.0134(7) 0.0192(8) 0.0006(6) -0.0011(6) -0.0027(6)
C4 0.0171(8) 0.0206(9) 0.0162(8) -0.0040(7) 0.0033(7) -0.0078(7)

_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 Br1 2.5032(3) . ?
Tc1 Br1 2.5032(3) 2_556 ?
Tc1 Br2 2.5150(3) 2_556 ?
Tc1 Br2 2.5150(3) . ?
Tc1 Br3 2.5207(3) 2_556 ?
Tc1 Br3 2.5207(3) . ?
N1 H1 0.8800 . ?
N1 C1 1.330(3) . ?
N1 C3 1.328(3) . ?
N2 H2 0.8800 . ?
N2 C1 1.382(3) . ?
N2 C4 1.352(3) . ?
C1 C2 1.464(3) . ?
C2 H2A 0.9800 . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?
C3 H3 0.9500 . ?
C3 C4 1.382(3) . ?
C4 H4 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
Br1 Tc1 Br1 180.0 . 2_556 ?
Br1 Tc1 Br2 90.361(10) 2_556 . ?
Br1 Tc1 Br2 89.640(9) . . ?
Br1 Tc1 Br2 89.639(9) 2_556 2_556 ?
Br1 Tc1 Br2 90.360(9) . 2_556 ?
Br1 Tc1 Br3 90.069(11) . . ?
Br1 Tc1 Br3 89.931(11) . 2_556 ?
Br1 Tc1 Br3 90.069(11) 2_556 2_556 ?
Br1 Tc1 Br3 89.931(11) 2_556 . ?
Br2 Tc1 Br2 180.0 2_556 . ?
Br2 Tc1 Br3 91.409(9) . . ?
Br2 Tc1 Br3 88.590(9) 2_556 . ?
Br2 Tc1 Br3 91.410(9) 2_556 2_556 ?
Br2 Tc1 Br3 88.591(8) . 2_556 ?
Br3 Tc1 Br3 180.0 . 2_556 ?
C1 N1 H1 125.9 . . ?
C3 N1 H1 125.9 . . ?
C3 N1 C1 108.12(19) . . ?
C1 N2 H2 126.4 . . ?
C4 N2 H2 126.4 . . ?
C4 N2 C1 107.15(18) . . ?
N1 C1 N2 108.91(18) . . ?
N1 C1 C2 125.46(19) . . ?
N2 C1 C2 125.63(18) . . ?
C1 C2 H2A 109.5 . . ?
C1 C2 H2B 109.5 . . ?
C1 C2 H2C 109.5 . . ?
H2A C2 H2B 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
N1 C3 H3 125.3 . . ?
N1 C3 C4 109.35(19) . . ?
C4 C3 H3 125.3 . . ?
N2 C4 C3 106.48(19) . . ?
N2 C4 H4 126.8 . . ?
C3 C4 H4 126.8 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
_geom_hbond_publ_flag
N1 H1 Br1 0.88 3.01 3.476(2) 115.4 1_655 yes
N1 H1 Br3 0.88 2.96 3.677(2) 139.7 . yes
N2 H2 Br1 0.88 2.92 3.675(2) 144.6 2_565 yes
C3 H3 Br3 0.95 2.79 3.451(2) 127.6 2_656 yes

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 C3 C4 N2 0.3(3) . . . . ?
C1 N1 C3 C4 -0.1(3) . . . . ?
C1 N2 C4 C3 -0.4(2) . . . . ?
C3 N1 C1 N2 -0.2(2) . . . . ?
C3 N1 C1 C2 -179.91(19) . . . . ?
C4 N2 C1 N1 0.4(2) . . . . ?
C4 N2 C1 C2 -179.9(2) . . . . ?

_shelx_res_file                  
;
TITL TcNaMeIm_LT_0m in P-1
    tcm.res
    created by SHELXL-2018/3 at 13:00:50 on 23-Aug-2021
CELL 0.71073 7.7095 7.9065 8.0783 79.107 86.065 66.969
ZERR 2 0.0008 0.0008 0.0008 0.005 0.005 0.005
LATT 1
SFAC C H Br N Tc
UNIT 8 14 6 4 1
EQIV $1 1+X,+Y,+Z
EQIV $2 -X,1-Y,-Z
EQIV $3 1-X,-Y,1-Z

L.S. 8
PLAN  5
SIZE 0.36 0.2 0.18
TEMP -173(2)
HTAB N1 Br1_$1
HTAB N1 Br3
HTAB N2 Br1_$2
CONF
HTAB C3 Br3_$3
BOND $H
HTAB
MORE -1
fmap 2
acta
SHEL 5 0.5
OMIT -2 80
OMIT -1 -2 2
OMIT 2 0 3
OMIT -3 1 1
OMIT 0 3 2
OMIT -1 1 1
OMIT 2 -1 2
OMIT 3 2 3
OMIT 5 6 4
REM <olex2.extras>
REM <HklSrc "%.\\tcm.hkl">
REM </olex2.extras>

WGHT    0.031200    0.393000
FVAR       0.15476
TC1   5    0.000000    0.000000    0.500000    10.50000    0.00836    0.00815 =
         0.00675   -0.00078    0.00040   -0.00204
BR1   3   -0.286131    0.296720    0.485456    11.00000    0.01219    0.01112 =
         0.01137   -0.00226   -0.00092    0.00093
BR2   3    0.058806    0.091832    0.192483    11.00000    0.01416    0.01349 =
         0.00758   -0.00011    0.00158   -0.00431
BR3   3    0.197570    0.160048    0.583845    11.00000    0.01394    0.01337 =
         0.01262   -0.00117   -0.00079   -0.00694
N1    4    0.440149    0.246359    0.188427    11.00000    0.01979    0.02462 =
         0.01984    0.00294   -0.00312   -0.00928
AFIX  43
H1    2    0.446566    0.206337    0.298031    11.00000   -1.20000
AFIX   0
N2    4    0.344337    0.414342   -0.063486    11.00000    0.02021    0.02187 =
         0.01452    0.00018   -0.00062   -0.00732
AFIX  43
H2    2    0.276598    0.503129   -0.143848    11.00000   -1.20000
AFIX   0
C1    1    0.304911    0.397267    0.106864    11.00000    0.00785    0.00977 =
         0.00871   -0.00017   -0.00074   -0.00457
C2    1    0.141504    0.524917    0.185217    11.00000    0.01635    0.01874 =
         0.01727   -0.00509    0.00308   -0.00705
AFIX 137
H2A   2    0.118508    0.653987    0.132085    11.00000   -1.50000
H2B   2    0.166192    0.508258    0.305839    11.00000   -1.50000
H2C   2    0.030434    0.497950    0.170176    11.00000   -1.50000
AFIX   0
C3    1    0.563801    0.166580    0.075735    11.00000    0.00936    0.01341 =
         0.01917    0.00058   -0.00110   -0.00265
AFIX  43
H3    2    0.674337    0.056340    0.100667    11.00000   -1.20000
AFIX   0
C4    1    0.506533    0.269030   -0.083562    11.00000    0.01712    0.02060 =
         0.01623   -0.00404    0.00329   -0.00777
AFIX  43
H4    2    0.568859    0.242555   -0.186799    11.00000   -1.20000
AFIX   0
HKLF 4




REM  TcNaMeIm_LT_0m in P-1
REM wR2 = 0.0705, GooF = S = 1.041, Restrained GooF = 1.041 for all data
REM R1 = 0.0282 for 4696 Fo > 4sig(Fo) and 0.0368 for all 5509 data
REM 89 parameters refined using 0 restraints

END

WGHT      0.0312      0.3928

REM Instructions for potential hydrogen bonds
HTAB N1 Br1_$1
HTAB N1 Br3
HTAB N2 Br1_$2
HTAB C2 Br2_$2
EQIV $5 -x, -y+1, -z+1
HTAB C2 Br1_$5
HTAB C2 Br2
EQIV $6 -x+1, -y, -z
HTAB C3 Br2_$6
HTAB C3 Br3_$3
EQIV $7 x+1, y, z-1
HTAB C4 Br1_$7
HTAB C4 Br2_$6

REM Highest difference peak  1.264,  deepest hole -1.307,  1-sigma level  0.204
Q1    1   0.3047  0.4013  0.0598  11.00000  0.05    1.26
Q2    1   0.2675  0.4264  0.1201  11.00000  0.05    1.23
Q3    1   0.3044  0.4390  0.1113  11.00000  0.05    1.19
Q4    1   0.3603  0.3598  0.1280  11.00000  0.05    1.18
Q5    1   0.5624  0.1236  0.0758  11.00000  0.05    1.07
;
_shelx_res_checksum              58945
_olex2_submission_special_instructions 'No special instructions were received'
