# Electronic Supplementary Material (ESI) for Chemical Communications.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_KA161_0M
_database_code_depnum_ccdc_archive 'CCDC 1872728'
loop_
_audit_author_name
_audit_author_address
'Ramavath Babu'
;Indian Institute of Chemical Technology 
India
;
_audit_update_record             
;
2018-10-11 deposited with the CCDC.	2019-05-23 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        MA2CoBr4
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'Br4 Co 2-, 2(C H6 N +)'
_chemical_formula_sum            'C2 H12 Br4 Co N2'
_chemical_formula_weight         442.71

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'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_H-M_alt        'P 21/c'
_space_group_name_Hall           '-P 2ybc'

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

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

_cell_length_a                   7.946(4)
_cell_length_b                   13.016(6)
_cell_length_c                   11.246(4)
_cell_angle_alpha                90
_cell_angle_beta                 96.419(13)
_cell_angle_gamma                90
_cell_volume                     1155.8(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9819
_cell_measurement_theta_min      2.40
_cell_measurement_theta_max      28.78

_exptl_crystal_description       block
_exptl_crystal_colour            'dark blue'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.544
_exptl_crystal_F_000             820
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.320
_exptl_crystal_size_mid          0.280
_exptl_crystal_size_min          0.180
_exptl_absorpt_coefficient_mu    15.255
_shelx_estimated_absorpt_T_min   0.085
_shelx_estimated_absorpt_T_max   0.170
_exptl_absorpt_process_details   'SADABS, Bruker, 2016'
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.2475

_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker D8 QUEST PHOTON-100'
_diffrn_measurement_method       'ω and φ'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            31945
_diffrn_reflns_av_unetI/netI     0.0388
_diffrn_reflns_av_R_equivalents  0.0789
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.402
_diffrn_reflns_theta_max         28.302
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             2872
_reflns_number_gt                2680
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_max     .
_reflns_Friedel_fraction_full    .

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       'APEX3 (Bruker, 2016)'
_computing_cell_refinement       'SAINT (Bruker, 2016)'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXT (Sheldrick, 2015)'
_computing_structure_refinement  'SHELXL2014 (Sheldrick, 2015)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0533P)²+18.0754P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_extinction_coef       0.0108(7)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_number_reflns         2872
_refine_ls_number_parameters     106
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0467
_refine_ls_R_factor_gt           0.0437
_refine_ls_wR_factor_ref         0.1236
_refine_ls_wR_factor_gt          0.1223
_refine_ls_goodness_of_fit_ref   1.129
_refine_ls_restrained_S_all      1.128
_refine_ls_shift/su_max          0.035
_refine_ls_shift/su_mean         0.002

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Br1 Br 0.50577(8) 0.61089(5) 0.63114(6) 0.01183(19) Uani 1 1 d . . . . .
Br2 Br 0.23137(9) 0.38002(5) 0.73196(6) 0.01199(19) Uani 1 1 d . . . . .
Br3 Br 0.29572(8) 0.63511(5) 0.92935(5) 0.00914(18) Uani 1 1 d . . . . .
Br4 Br 0.00518(8) 0.62850(5) 0.62002(5) 0.00882(18) Uani 1 1 d . . . . .
C1 C 0.8182(10) 0.6355(6) 0.9359(6) 0.0179(15) Uani 1 1 d . . . . .
H1A H 0.7994 0.6356 0.8483 0.027 Uiso 1 1 calc R U . . .
H1B H 0.7963 0.5666 0.9658 0.027 Uiso 1 1 calc R U . . .
H1C H 0.9357 0.6549 0.9620 0.027 Uiso 1 1 calc R U . . .
C2 C 0.2471(11) 0.6199(6) 0.2458(6) 0.0199(16) Uani 1 1 d . . . . .
H2A H 0.2595 0.5538 0.2059 0.030 Uiso 1 1 calc R U . . .
H2B H 0.3500 0.6608 0.2427 0.030 Uiso 1 1 calc R U . . .
H2C H 0.1499 0.6570 0.2051 0.030 Uiso 1 1 calc R U . . .
Co1 Co 0.26191(10) 0.56468(6) 0.72873(7) 0.0045(2) Uani 1 1 d . . . . .
N1 N 0.7028(7) 0.7096(4) 0.9835(5) 0.0106(10) Uani 1 1 d . . . . .
H1N H 0.710(11) 0.712(7) 1.064(8) 0.016 Uiso 1 1 d . U . . .
H2N H 0.610(13) 0.688(7) 0.967(8) 0.016 Uiso 1 1 d . U . . .
H3N H 0.708(11) 0.774(7) 0.948(8) 0.016 Uiso 1 1 d . U . . .
N2 N 0.2198(8) 0.6020(5) 0.3715(5) 0.0138(11) Uani 1 1 d D . . . .
H4N H 0.296(17) 0.560(10) 0.403(12) 0.05(4) Uiso 1 1 d . . . . .
H5N H 0.118(10) 0.577(14) 0.381(17) 0.11(6) Uiso 1 1 d D . . . .
H6N H 0.214(13) 0.663(8) 0.400(9) 0.02(2) Uiso 1 1 d . . . . .

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
Br1 0.0069(3) 0.0151(3) 0.0142(3) 0.0043(2) 0.0043(2) -0.0015(2)
Br2 0.0224(4) 0.0046(3) 0.0085(3) 0.0001(2) -0.0007(2) -0.0008(2)
Br3 0.0100(3) 0.0126(3) 0.0045(3) -0.0032(2) -0.0006(2) -0.0028(2)
Br4 0.0054(3) 0.0120(3) 0.0082(3) 0.0013(2) -0.0027(2) 0.0028(2)
C1 0.025(4) 0.017(3) 0.013(3) 0.000(3) 0.008(3) 0.010(3)
C2 0.034(4) 0.019(4) 0.009(3) 0.004(3) 0.009(3) 0.004(3)
Co1 0.0037(4) 0.0059(4) 0.0036(4) 0.0000(3) -0.0007(3) -0.0006(3)
N1 0.008(3) 0.012(3) 0.012(3) 0.002(2) 0.003(2) -0.002(2)
N2 0.019(3) 0.015(3) 0.007(3) -0.003(2) 0.001(2) -0.005(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
Br1 Co1 2.4075(13) . ?
Br2 Co1 2.4165(15) . ?
Br3 Co1 2.4222(13) . ?
Br4 Co1 2.4060(13) . ?
C1 N1 1.472(9) . ?
C1 H1A 0.9800 . ?
C1 H1B 0.9800 . ?
C1 H1C 0.9800 . ?
C2 N2 1.472(9) . ?
C2 H2A 0.9800 . ?
C2 H2B 0.9800 . ?
C2 H2C 0.9800 . ?
N1 H1N 0.91(9) . ?
N1 H2N 0.79(10) . ?
N1 H3N 0.94(9) . ?
N2 H4N 0.86(14) . ?
N2 H5N 0.89(2) . ?
N2 H6N 0.86(11) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 C1 H1A 109.5 . . ?
N1 C1 H1B 109.5 . . ?
H1A C1 H1B 109.5 . . ?
N1 C1 H1C 109.5 . . ?
H1A C1 H1C 109.5 . . ?
H1B C1 H1C 109.5 . . ?
N2 C2 H2A 109.5 . . ?
N2 C2 H2B 109.5 . . ?
H2A C2 H2B 109.5 . . ?
N2 C2 H2C 109.5 . . ?
H2A C2 H2C 109.5 . . ?
H2B C2 H2C 109.5 . . ?
Br4 Co1 Br1 111.23(5) . . ?
Br4 Co1 Br2 105.68(4) . . ?
Br1 Co1 Br2 110.04(4) . . ?
Br4 Co1 Br3 110.00(4) . . ?
Br1 Co1 Br3 108.60(4) . . ?
Br2 Co1 Br3 111.30(4) . . ?
C1 N1 H1N 115(6) . . ?
C1 N1 H2N 107(7) . . ?
H1N N1 H2N 101(8) . . ?
C1 N1 H3N 112(5) . . ?
H1N N1 H3N 113(8) . . ?
H2N N1 H3N 108(9) . . ?
C2 N2 H4N 109(9) . . ?
C2 N2 H5N 114(10) . . ?
H4N N2 H5N 109(10) . . ?
C2 N2 H6N 104(7) . . ?
H4N N2 H6N 120(10) . . ?
H5N N2 H6N 102(10) . . ?

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 H2N Br3 0.79(10) 2.58(10) 3.367(6) 174(9) .
N1 H1N Br2 0.91(9) 2.58(9) 3.391(6) 149(8) 3_667
N1 H3N Br2 0.94(9) 2.53(9) 3.369(6) 148(7) 2_656
N2 H4N Br1 0.86(14) 2.98(13) 3.496(6) 121(11) .
N2 H4N Br1 0.86(14) 2.78(14) 3.528(7) 147(11) 3_666
N2 H5N Br2 0.89(2) 2.97(14) 3.651(7) 134(15) 3_566
N2 H5N Br4 0.89(2) 2.85(15) 3.499(6) 131(15) 3_566
N2 H6N Br3 0.86(11) 2.71(11) 3.523(7) 156(9) 4_575

_refine_diff_density_max         1.608
_refine_diff_density_min         -1.661
_refine_diff_density_rms         0.296

_shelx_res_file                  
;

    KA161_0M.res created by SHELXL-2014/7


TITL KA161_0m_a.res in P2(1)/c
CELL  0.71073   7.9460  13.0161  11.2456   90.000   96.419   90.000
ZERR   4.000   0.0038   0.0060   0.0043    0.000    0.013    0.000
LATT 1
SYMM -X, 1/2+Y, 1/2-Z
SFAC C  H  Br Co N
UNIT 8  48  16  4  8
L.S. 10
ACTA
BOND $H
FMAP 2
PLAN 5
EQIV $1 -x+1, -y+1, -z+2
EQIV $2 -x+1, y+1/2, -z+3/2
EQIV $3 -x+1, -y+1, -z+1
EQIV $4 -x, -y+1, -z+1
EQIV $5 x, -y+3/2, z-1/2
HTAB N1 Br3
HTAB N1 Br2_$1
HTAB N1 Br2_$2
HTAB N2 Br1
HTAB N2 Br1_$3
HTAB N2 Br2_$4
HTAB N2 Br4_$4
HTAB N2 Br3_$5
DFIX 0.89 N2 H5N
CONF
SIZE 0.32 0.28 0.18
TEMP -173
WGHT    0.053300   18.075394
EXTI    0.010804
FVAR       0.28805
BR1   3    0.505770    0.610886    0.631139    11.00000    0.00694    0.01507 =
         0.01419    0.00432    0.00432   -0.00148
BR2   3    0.231368    0.380015    0.731964    11.00000    0.02238    0.00456 =
         0.00849    0.00012   -0.00070   -0.00085
BR3   3    0.295720    0.635110    0.929345    11.00000    0.01003    0.01256 =
         0.00449   -0.00324   -0.00063   -0.00282
BR4   3    0.005176    0.628503    0.620016    11.00000    0.00538    0.01203 =
         0.00825    0.00127   -0.00272    0.00284
C1    1    0.818177    0.635489    0.935910    11.00000    0.02516    0.01658 =
         0.01344   -0.00006    0.00816    0.01039
AFIX 137
H1A   2    0.799390    0.635645    0.848285    11.00000   -1.50000
H1B   2    0.796267    0.566584    0.965755    11.00000   -1.50000
H1C   2    0.935676    0.654909    0.961992    11.00000   -1.50000
AFIX   0
C2    1    0.247070    0.619894    0.245827    11.00000    0.03351    0.01894 =
         0.00859    0.00443    0.00881    0.00441
AFIX 137
H2A   2    0.259462    0.553817    0.205948    11.00000   -1.50000
H2B   2    0.350050    0.660782    0.242732    11.00000   -1.50000
H2C   2    0.149861    0.657015    0.205143    11.00000   -1.50000
AFIX   0
CO1   4    0.261915    0.564681    0.728725    11.00000    0.00373    0.00588 =
         0.00357    0.00004   -0.00072   -0.00060
N1    5    0.702800    0.709591    0.983528    11.00000    0.00780    0.01216 =
         0.01222    0.00191    0.00274   -0.00199
H1N   2    0.709898    0.712093    1.064361    11.00000   -1.50000
H2N   2    0.609622    0.688305    0.967188    11.00000   -1.50000
H3N   2    0.708350    0.774478    0.947903    11.00000   -1.50000
N2    5    0.219795    0.601975    0.371450    11.00000    0.01858    0.01526 =
         0.00732   -0.00277    0.00070   -0.00474
H4N   2    0.296016    0.560114    0.402666    11.00000    0.05179
H5N   2    0.117616    0.576846    0.380503    11.00000    0.10651
H6N   2    0.214231    0.663189    0.400392    11.00000    0.02452
HKLF 4

REM  KA161_0m_a.res in P2(1)/c
REM R1 =  0.0437 for    2680 Fo > 4sig(Fo)  and  0.0467 for all    2872 data
REM    106 parameters refined using      1 restraints

END

WGHT      0.0533     17.5003

REM Highest difference peak  1.608,  deepest hole -1.661,  1-sigma level  0.296
Q1    1   0.0403  0.6603  0.6774  11.00000  0.05    1.61
Q2    1   0.0382  0.6007  0.6761  11.00000  0.05    1.52
Q3    1   0.3274  0.6708  0.9858  11.00000  0.05    1.39
Q4    1   0.2568  0.6045  0.8760  11.00000  0.05    1.35
Q5    1   0.3227  0.6012  0.9812  11.00000  0.05    1.32
;
_shelx_res_checksum              14558

_exptl_crystal_recrystallization_method Anti-solvent
_chemical_properties_physical    Air-sensitive
_exptl_crystal_preparation       Luminescent
