# Electronic Supplementary Material (ESI) for Dalton Transactions
# This journal is © The Royal Society of Chemistry 2013

#######################################################################
#
#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
#######################################################################
# 
#  This CIF contains data from an original supplementary publication
#  deposited with the CCDC, and may include chemical, crystal,
#  experimental, refinement, atomic coordinates,
#  anisotropic displacement parameters and molecular geometry data,
#  as required by the journal to which it was submitted.
#
#  This CIF is provided on the understanding that it is used for bona
#  fide research purposes only. It may contain copyright material
#  of the CCDC or of third parties, and may not be copied or further
#  disseminated in any form, whether machine-readable or not,
#  except for the purpose of generating routine backup copies
#  on your local computer system.
# 
#  For further information on the CCDC, data deposition and
#  data retrieval see:
#                         www.ccdc.cam.ac.uk
#
#  Bona fide researchers may freely download Mercury and enCIFer
#  from this site to visualise CIF-encoded structures and 
#  to carry out CIF format checking respectively.
#
data_tt

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C14 H12 Br2 Co N2 O0'
_chemical_formula_weight         427.01

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 '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'

_symmetry_cell_setting           Monoclinic
_symmetry_space_group_name_H-M   'P2(1)/c  '

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

_cell_length_a                   9.422(5)
_cell_length_b                   18.361(9)
_cell_length_c                   9.331(4)
_cell_angle_alpha                90.00
_cell_angle_beta                 112.62(3)
_cell_angle_gamma                90.00
_cell_volume                     1490.1(13)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    971
_cell_measurement_theta_min      2.84
_cell_measurement_theta_max      20.54

_exptl_crystal_description       prism
_exptl_crystal_colour            green
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.08
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.903
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             828
_exptl_absorpt_coefficient_mu    6.501
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.354
_exptl_absorpt_correction_T_max  0.875
_exptl_absorpt_process_details   
;
The insufficient R value in the absence of disorder and solvent may be associated with the relative high Rint value although the absorption correction (multi-scan) was undertaken.
Rint value is 0.2274 and 0.1555 before and after absorption correction, respectively. 
;

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            6841
_diffrn_reflns_av_R_equivalents  0.10
_diffrn_reflns_av_unetI//netI    0.2427
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.59
_diffrn_reflns_theta_max         24.99
_reflns_number_total             2549
_reflns_number_gt                1068
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'Bruker SHELXTL'
_computing_structure_refinement  'Bruker SHELXTL'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F^2^ against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F^2^, conventional R-factors R are based 
 on F, with F set to zero for negative F^2^. The threshold expression of 
 F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F^2^ are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.0005P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.0149(12)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_number_reflns         2549
_refine_ls_number_parameters     173
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1852
_refine_ls_R_factor_gt           0.0868
_refine_ls_wR_factor_ref         0.1504
_refine_ls_wR_factor_gt          0.1309
_refine_ls_goodness_of_fit_ref   0.985
_refine_ls_restrained_S_all      0.985
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.66536(15) 0.13143(10) 0.75246(19) 0.0436(6) Uani 1 1 d . . .
Br1 Br 0.79653(15) 0.24103(9) 0.76696(19) 0.0754(7) Uani 1 1 d . . .
Br2 Br 0.74254(14) 0.03276(9) 0.63612(16) 0.0594(6) Uani 1 1 d . . .
C1 C 0.5541(14) 0.0646(8) 1.1958(14) 0.044(4) Uani 1 1 d . . .
H1A H 0.5263 0.0494 1.2765 0.053 Uiso 1 1 calc R . .
C2 C 0.6982(15) 0.0655(8) 1.2128(14) 0.050(4) Uani 1 1 d . . .
H2A H 0.7721 0.0538 1.3097 0.060 Uiso 1 1 calc R . .
C3 C 0.7488(13) 0.0831(7) 1.0921(15) 0.044(4) Uani 1 1 d . . .
C4 C 0.9108(12) 0.0879(9) 1.1058(13) 0.059(4) Uani 1 1 d . . .
H4A H 0.9131 0.1030 1.0082 0.088 Uiso 1 1 calc R . .
H4B H 0.9588 0.0410 1.1333 0.088 Uiso 1 1 calc R . .
H4C H 0.9651 0.1227 1.1846 0.088 Uiso 1 1 calc R . .
C5 C 0.4905(11) 0.1063(8) 0.9332(14) 0.041(4) Uani 1 1 d . . .
C6 C 0.4425(14) 0.0870(8) 1.0546(16) 0.056(4) Uani 1 1 d . . .
C7 C 0.2779(14) 0.0925(8) 1.0224(16) 0.048(4) Uani 1 1 d . . .
H7A H 0.2456 0.0800 1.1016 0.058 Uiso 1 1 calc R . .
C8 C 0.1687(15) 0.1147(8) 0.8847(17) 0.054(4) Uani 1 1 d . . .
H8A H 0.0653 0.1179 0.8692 0.065 Uiso 1 1 calc R . .
C9 C 0.2240(12) 0.1329(8) 0.7641(16) 0.052(4) Uani 1 1 d . . .
C10 C 0.3780(12) 0.1268(7) 0.7816(14) 0.038(3) Uani 1 1 d . . .
C11 C 0.1250(13) 0.1604(9) 0.6161(19) 0.061(5) Uani 1 1 d . . .
H11A H 0.0205 0.1658 0.5936 0.073 Uiso 1 1 calc R . .
C12 C 0.1802(14) 0.1779(10) 0.5130(18) 0.065(5) Uani 1 1 d . . .
H12A H 0.1142 0.1958 0.4172 0.078 Uiso 1 1 calc R . .
C13 C 0.3359(14) 0.1705(9) 0.5426(17) 0.052(4) Uani 1 1 d . . .
C14 C 0.4002(13) 0.1880(9) 0.4224(18) 0.075(6) Uani 1 1 d . . .
H14A H 0.5091 0.1796 0.4647 0.112 Uiso 1 1 calc R . .
H14B H 0.3801 0.2382 0.3925 0.112 Uiso 1 1 calc R . .
H14C H 0.3523 0.1575 0.3332 0.112 Uiso 1 1 calc R . .
N1 N 0.6394(8) 0.1039(5) 0.9468(10) 0.035(3) Uani 1 1 d . . .
N2 N 0.4318(10) 0.1461(6) 0.6710(11) 0.044(3) Uani 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
Co1 0.0406(10) 0.0345(13) 0.0526(11) 0.0043(10) 0.0144(8) -0.0005(9)
Br1 0.0665(10) 0.0450(12) 0.0997(13) 0.0115(10) 0.0154(8) -0.0104(9)
Br2 0.0660(10) 0.0476(12) 0.0591(10) 0.0034(8) 0.0179(7) 0.0123(8)
C1 0.055(8) 0.043(10) 0.053(9) -0.001(8) 0.040(7) 0.002(7)
C2 0.070(9) 0.039(10) 0.032(8) 0.001(7) 0.011(7) 0.027(8)
C3 0.051(8) 0.008(7) 0.053(9) 0.000(7) -0.003(6) 0.001(6)
C4 0.058(8) 0.066(12) 0.046(8) -0.007(9) 0.011(6) 0.018(8)
C5 0.033(6) 0.053(10) 0.043(8) -0.002(8) 0.020(6) -0.011(7)
C6 0.051(8) 0.018(8) 0.076(11) 0.016(8) -0.002(7) 0.000(7)
C7 0.075(9) 0.028(9) 0.074(10) -0.007(8) 0.066(8) -0.002(8)
C8 0.056(8) 0.053(12) 0.058(9) -0.015(9) 0.026(8) 0.002(8)
C9 0.022(6) 0.042(10) 0.072(10) -0.023(9) -0.004(6) 0.001(7)
C10 0.036(6) 0.021(8) 0.056(8) 0.017(7) 0.017(6) 0.004(6)
C11 0.029(7) 0.046(11) 0.095(12) -0.013(10) 0.011(8) 0.001(7)
C12 0.049(9) 0.071(13) 0.062(11) -0.019(10) 0.008(7) 0.014(9)
C13 0.054(8) 0.042(10) 0.055(10) 0.000(8) 0.015(8) 0.004(8)
C14 0.047(7) 0.039(10) 0.096(13) 0.001(9) -0.019(8) 0.020(8)
N1 0.015(4) 0.018(6) 0.051(6) 0.008(5) -0.009(4) 0.004(4)
N2 0.055(6) 0.028(7) 0.035(6) 0.016(6) 0.003(5) -0.001(6)

_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
Co1 N1 1.986(9) . ?
Co1 N2 2.051(9) . ?
Co1 Br1 2.338(3) . ?
Co1 Br2 2.366(3) . ?
C1 C2 1.305(14) . ?
C1 C6 1.395(16) . ?
C1 H1A 0.9300 . ?
C2 C3 1.419(17) . ?
C2 H2A 0.9300 . ?
C3 N1 1.404(13) . ?
C3 C4 1.485(15) . ?
C4 H4A 0.9600 . ?
C4 H4B 0.9600 . ?
C4 H4C 0.9600 . ?
C5 N1 1.360(12) . ?
C5 C6 1.417(16) . ?
C5 C10 1.453(15) . ?
C6 C7 1.466(16) . ?
C7 C8 1.363(17) . ?
C7 H7A 0.9300 . ?
C8 C9 1.450(18) . ?
C8 H8A 0.9300 . ?
C9 C10 1.401(15) . ?
C9 C11 1.429(19) . ?
C10 N2 1.361(14) . ?
C11 C12 1.298(19) . ?
C11 H11A 0.9300 . ?
C12 C13 1.392(18) . ?
C12 H12A 0.9300 . ?
C13 N2 1.272(14) . ?
C13 C14 1.500(18) . ?
C14 H14A 0.9600 . ?
C14 H14B 0.9600 . ?
C14 H14C 0.9600 . ?

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 Co1 N2 83.1(4) . . ?
N1 Co1 Br1 114.5(3) . . ?
N2 Co1 Br1 112.1(3) . . ?
N1 Co1 Br2 113.0(3) . . ?
N2 Co1 Br2 114.0(3) . . ?
Br1 Co1 Br2 115.90(9) . . ?
C2 C1 C6 118.8(13) . . ?
C2 C1 H1A 120.6 . . ?
C6 C1 H1A 120.6 . . ?
C1 C2 C3 123.9(11) . . ?
C1 C2 H2A 118.1 . . ?
C3 C2 H2A 118.1 . . ?
N1 C3 C2 118.9(11) . . ?
N1 C3 C4 114.6(12) . . ?
C2 C3 C4 126.4(10) . . ?
C3 C4 H4A 109.5 . . ?
C3 C4 H4B 109.5 . . ?
H4A C4 H4B 109.5 . . ?
C3 C4 H4C 109.5 . . ?
H4A C4 H4C 109.5 . . ?
H4B C4 H4C 109.5 . . ?
N1 C5 C6 123.5(11) . . ?
N1 C5 C10 116.1(11) . . ?
C6 C5 C10 120.4(10) . . ?
C1 C6 C5 118.2(12) . . ?
C1 C6 C7 124.6(15) . . ?
C5 C6 C7 117.2(11) . . ?
C8 C7 C6 124.7(13) . . ?
C8 C7 H7A 117.6 . . ?
C6 C7 H7A 117.6 . . ?
C7 C8 C9 115.7(12) . . ?
C7 C8 H8A 122.1 . . ?
C9 C8 H8A 122.1 . . ?
C10 C9 C11 113.7(14) . . ?
C10 C9 C8 123.8(12) . . ?
C11 C9 C8 122.4(12) . . ?
N2 C10 C9 124.2(11) . . ?
N2 C10 C5 117.4(9) . . ?
C9 C10 C5 118.0(12) . . ?
C12 C11 C9 120.4(13) . . ?
C12 C11 H11A 119.8 . . ?
C9 C11 H11A 119.8 . . ?
C11 C12 C13 121.4(15) . . ?
C11 C12 H12A 119.3 . . ?
C13 C12 H12A 119.3 . . ?
N2 C13 C12 122.3(16) . . ?
N2 C13 C14 115.8(12) . . ?
C12 C13 C14 121.9(13) . . ?
C13 C14 H14A 109.5 . . ?
C13 C14 H14B 109.5 . . ?
H14A C14 H14B 109.5 . . ?
C13 C14 H14C 109.5 . . ?
H14A C14 H14C 109.5 . . ?
H14B C14 H14C 109.5 . . ?
C5 N1 C3 116.5(11) . . ?
C5 N1 Co1 113.0(7) . . ?
C3 N1 Co1 130.4(8) . . ?
C13 N2 C10 118.0(11) . . ?
C13 N2 Co1 131.9(11) . . ?
C10 N2 Co1 110.1(7) . . ?

_diffrn_measured_fraction_theta_max 0.974
_diffrn_reflns_theta_full        24.99
_diffrn_measured_fraction_theta_full 0.974
_refine_diff_density_max         1.504
_refine_diff_density_min         -1.168
_refine_diff_density_rms         0.239
_database_code_depnum_ccdc_archive 'CCDC 948720'