# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2014

#######################################################################
#
#                 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_cmpnd_1a

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C24 H18 Cl2 Mn N6 S2'
_chemical_formula_sum            'C24 H18 Cl2 Mn N6 S2'
_chemical_formula_weight         580.40

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pbcn
_symmetry_space_group_name_Hall  '-P 2n 2ab'
loop_
_symmetry_equiv_pos_as_xyz
'x, y, z'
'-x+1/2, -y+1/2, z+1/2'
'-x, y, -z+1/2'
'x+1/2, -y+1/2, -z'
'-x, -y, -z'
'x-1/2, y-1/2, -z-1/2'
'x, -y, z-1/2'
'-x-1/2, y-1/2, z'

_cell_length_a                   13.468(6)
_cell_length_b                   9.758(4)
_cell_length_c                   18.440(8)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2423.3(17)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    4126
_cell_measurement_theta_min      2.58
_cell_measurement_theta_max      27.46

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.04
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.591
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1180
_exptl_absorpt_coefficient_mu    0.965
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.8768
_exptl_absorpt_correction_T_max  0.9624
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
Bruker APEX-II, Bruker AXS, Madison, WI, USA. 
;

_diffrn_ambient_temperature      150(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  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            26085
_diffrn_reflns_av_R_equivalents  0.0656
_diffrn_reflns_av_sigmaI/netI    0.0361
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.21
_diffrn_reflns_theta_max         27.61
_reflns_number_total             2803
_reflns_number_gt                2375
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
 Structure solved by direct methods to reveal all non-H atoms. H atoms added
 at calculated positions and refined with a riding model. All non-H atoms
 refined anisotropically.The S atom of the ligand was found to exhibit some
 disorder which was modelled over three positions with a common U(ij) in
 order to reduce the residualelectron density to < 1e/A3. The final site
 occupancy factors for the three positions were 0.85:0.10:0.05. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0368P)²+1.8870P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2803
_refine_ls_number_parameters     169
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0593
_refine_ls_R_factor_gt           0.0458
_refine_ls_wR_factor_ref         0.1005
_refine_ls_wR_factor_gt          0.0951
_refine_ls_goodness_of_fit_ref   1.156
_refine_ls_restrained_S_all      1.156
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Mn Mn 0.5000 0.16114(5) 0.2500 0.01889(15) Uani 1 2 d S . .
Cl1 Cl 0.46170(4) 0.33081(7) 0.15535(3) 0.02343(16) Uani 1 1 d . . .
S1 S 0.51827(7) -0.04992(13) 0.39858(7) 0.0327(3) Uani 0.850(3) 1 d P . .
S1A S 0.5023(6) -0.0967(13) 0.3703(8) 0.0327(3) Uani 0.104(3) 1 d P . .
S1B S 0.5025(11) -0.149(2) 0.3379(12) 0.0327(3) Uani 0.046(2) 1 d P . .
N1 N 0.57468(15) -0.0025(2) 0.31820(12) 0.0250(5) Uani 1 1 d . . .
N2 N 0.72383(16) -0.1174(2) 0.34647(12) 0.0296(5) Uani 1 1 d . . .
H2 H 0.7884 -0.1168 0.3392 0.036 Uiso 1 1 calc R . .
N3 N 0.65517(15) 0.1256(2) 0.20725(11) 0.0207(4) Uani 1 1 d . . .
C11 C 0.5884(2) -0.1956(3) 0.42357(15) 0.0278(6) Uani 1 1 d . . .
C12 C 0.5504(2) -0.2875(3) 0.47280(15) 0.0288(6) Uani 1 1 d . . .
H12 H 0.4833 -0.2802 0.4883 0.035 Uiso 1 1 calc R . .
C13 C 0.6106(2) -0.3911(3) 0.49958(14) 0.0307(6) Uani 1 1 d . . .
H13 H 0.5849 -0.4548 0.5337 0.037 Uiso 1 1 calc R . .
C14 C 0.7076(2) -0.4017(3) 0.47675(15) 0.0316(6) Uani 1 1 d . . .
H14 H 0.7488 -0.4720 0.4958 0.038 Uiso 1 1 calc R . .
C15 C 0.7459(2) -0.3107(3) 0.42619(14) 0.0265(6) Uani 1 1 d . . .
H15 H 0.8128 -0.3187 0.4106 0.032 Uiso 1 1 calc R . .
C16 C 0.68582(19) -0.2082(3) 0.39871(14) 0.0240(5) Uani 1 1 d . . .
C20 C 0.66710(18) -0.0307(3) 0.30665(14) 0.0221(5) Uani 1 1 d . . .
C21 C 0.71554(18) 0.0414(2) 0.24468(13) 0.0194(5) Uani 1 1 d . . .
C22 C 0.8151(2) 0.0281(3) 0.22759(15) 0.0291(6) Uani 1 1 d . . .
H22 H 0.8564 -0.0318 0.2548 0.035 Uiso 1 1 calc R . .
C23 C 0.8538(2) 0.1028(3) 0.17062(16) 0.0361(7) Uani 1 1 d . . .
H23 H 0.9222 0.0960 0.1584 0.043 Uiso 1 1 calc R . .
C24 C 0.7916(2) 0.1870(3) 0.13199(16) 0.0366(7) Uani 1 1 d . . .
H24 H 0.8161 0.2389 0.0922 0.044 Uiso 1 1 calc R . .
C25 C 0.6932(2) 0.1951(3) 0.15167(14) 0.0288(6) Uani 1 1 d . . .
H25 H 0.6506 0.2529 0.1244 0.035 Uiso 1 1 calc R . .


_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
Mn N3 2.260(2) . ?
Mn N3 2.260(2) 3_655 ?
Mn N1 2.268(2) . ?
Mn N1 2.268(2) 3_655 ?
Mn Cl1 2.4604(10) . ?
Mn Cl1 2.4604(10) 3_655 ?
S1 N1 1.729(2) . ?
S1 C11 1.768(3) . ?
S1A N1 1.649(8) . ?
S1A C11 1.801(9) . ?
S1B N1 1.765(18) . ?
S1B C11 2.010(19) . ?
N1 C20 1.293(3) . ?
N2 C20 1.356(3) . ?
N2 C16 1.405(3) . ?
N2 H2 0.8800 . ?
N3 C25 1.332(3) . ?
N3 C21 1.346(3) . ?
C11 C12 1.375(4) . ?
C11 C16 1.395(4) . ?
C12 C13 1.387(4) . ?
C12 H12 0.9500 . ?
C13 C14 1.377(4) . ?
C13 H13 0.9500 . ?
C14 C15 1.387(4) . ?
C14 H14 0.9500 . ?
C15 C16 1.382(4) . ?
C15 H15 0.9500 . ?
C20 C21 1.492(3) . ?
C21 C22 1.384(4) . ?
C22 C23 1.380(4) . ?
C22 H22 0.9500 . ?
C23 C24 1.373(4) . ?
C23 H23 0.9500 . ?
C24 C25 1.376(4) . ?
C24 H24 0.9500 . ?
C25 H25 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
N3 Mn N3 162.33(11) . 3_655 ?
N3 Mn N1 71.04(8) . . ?
N3 Mn N1 96.23(8) 3_655 . ?
N3 Mn N1 96.23(8) . 3_655 ?
N3 Mn N1 71.04(8) 3_655 3_655 ?
N1 Mn N1 90.50(12) . 3_655 ?
N3 Mn Cl1 92.85(6) . . ?
N3 Mn Cl1 99.03(6) 3_655 . ?
N1 Mn Cl1 163.77(5) . . ?
N1 Mn Cl1 89.27(7) 3_655 . ?
N3 Mn Cl1 99.03(6) . 3_655 ?
N3 Mn Cl1 92.85(6) 3_655 3_655 ?
N1 Mn Cl1 89.27(7) . 3_655 ?
N1 Mn Cl1 163.77(5) 3_655 3_655 ?
Cl1 Mn Cl1 95.42(5) . 3_655 ?
N1 S1 C11 101.76(13) . . ?
N1 S1A C11 103.6(5) . . ?
N1 S1B C11 91.7(9) . . ?
C20 N1 S1A 123.1(4) . . ?
C20 N1 S1 120.48(19) . . ?
C20 N1 S1B 113.1(6) . . ?
C20 N1 Mn 119.08(17) . . ?
S1A N1 Mn 117.0(3) . . ?
S1 N1 Mn 117.98(11) . . ?
S1B N1 Mn 116.1(5) . . ?
C20 N2 C16 124.0(2) . . ?
C20 N2 H2 118.0 . . ?
C16 N2 H2 118.0 . . ?
C25 N3 C21 118.2(2) . . ?
C25 N3 Mn 123.10(17) . . ?
C21 N3 Mn 118.25(16) . . ?
C12 C11 C16 120.7(3) . . ?
C12 C11 S1 119.8(2) . . ?
C16 C11 S1 119.2(2) . . ?
C12 C11 S1A 118.0(3) . . ?
C16 C11 S1A 118.3(3) . . ?
C12 C11 S1B 116.9(5) . . ?
C16 C11 S1B 107.6(5) . . ?
C11 C12 C13 119.5(3) . . ?
C11 C12 H12 120.3 . . ?
C13 C12 H12 120.3 . . ?
C14 C13 C12 120.1(3) . . ?
C14 C13 H13 120.0 . . ?
C12 C13 H13 120.0 . . ?
C13 C14 C15 120.7(3) . . ?
C13 C14 H14 119.7 . . ?
C15 C14 H14 119.7 . . ?
C16 C15 C14 119.5(3) . . ?
C16 C15 H15 120.2 . . ?
C14 C15 H15 120.2 . . ?
C15 C16 C11 119.6(2) . . ?
C15 C16 N2 119.6(2) . . ?
C11 C16 N2 120.8(2) . . ?
N1 C20 N2 125.9(2) . . ?
N1 C20 C21 116.5(2) . . ?
N2 C20 C21 117.6(2) . . ?
N3 C21 C22 121.7(2) . . ?
N3 C21 C20 114.6(2) . . ?
C22 C21 C20 123.6(2) . . ?
C23 C22 C21 119.3(2) . . ?
C23 C22 H22 120.3 . . ?
C21 C22 H22 120.3 . . ?
C24 C23 C22 118.7(3) . . ?
C24 C23 H23 120.7 . . ?
C22 C23 H23 120.7 . . ?
C23 C24 C25 119.0(3) . . ?
C23 C24 H24 120.5 . . ?
C25 C24 H24 120.5 . . ?
N3 C25 C24 123.0(2) . . ?
N3 C25 H25 118.5 . . ?
C24 C25 H25 118.5 . . ?

_diffrn_measured_fraction_theta_max 0.994
_diffrn_reflns_theta_full        27.61
_diffrn_measured_fraction_theta_full 0.994
_refine_diff_density_max         0.380
_refine_diff_density_min         -0.324
_refine_diff_density_rms         0.074
_database_code_depnum_ccdc_archive 'CCDC 1002532'
#######################################################################
#
#                 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_cmpnd_1b

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C24 H18 Cl2 Fe N6 S2'
_chemical_formula_sum            'C24 H18 Cl2 Fe N6 S2'
_chemical_formula_weight         581.31

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pbcn
_symmetry_space_group_name_Hall  '-P 2n 2ab'

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

_cell_length_a                   13.3122(16)
_cell_length_b                   9.8775(12)
_cell_length_c                   18.354(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2413.4(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    8395
_cell_measurement_theta_min      2.219
_cell_measurement_theta_max      28.171

_exptl_crystal_description       lathe
_exptl_crystal_colour            red
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.08
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.600
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1184
_exptl_absorpt_coefficient_mu    1.047
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.7374
_exptl_absorpt_correction_T_max  0.9209
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
; 
Saint Plus, Bruker AXS, Madison, WI, USA.  
;

_diffrn_ambient_temperature      150(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_reflns_number            25673
_diffrn_reflns_av_R_equivalents  0.0311
_diffrn_reflns_av_sigmaI/netI    0.0174
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.22
_diffrn_reflns_theta_max         27.50
_reflns_number_total             2764
_reflns_number_gt                2434
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SAINT, v6.45a'
_computing_data_reduction        'Bruker SHELXTL XPREP'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1997)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Mercury v3.0'
_computing_publication_material  'Bruker SHELXTL XCIF'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
 The structure was solved by direct methods to reveal all non-H atoms.
 The S atom of the chelate heterocycle was found to be disordered over two
 positions and the site occupancies were initially refined with a common 
 isotropic displacement parameter. The occupancies were then fixed (89:11)
 and the thermal parameters refined anisotropically with equivalent U(ij). 
 H atoms were added at calculated positions. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0599P)²+3.1561P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2764
_refine_ls_number_parameters     165
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.0473
_refine_ls_R_factor_gt           0.0413
_refine_ls_wR_factor_ref         0.1134
_refine_ls_wR_factor_gt          0.1079
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_restrained_S_all      1.046
_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
Fe Fe 0.0000 0.15842(5) 0.2500 0.02175(15) Uani 1 2 d S . .
S1 S 0.01390(6) -0.04290(9) 0.39965(5) 0.0391(2) Uani 0.8914(18) 1 d PD A 1
S1A S -0.0075(4) -0.1124(8) 0.3576(4) 0.0391(2) Uani 0.1086(18) 1 d PD A 2
N1 N 0.06952(14) 0.0018(2) 0.31811(12) 0.0284(4) Uani 1 1 d D . .
Cl1 Cl 0.04213(4) 0.32769(6) 0.34096(3) 0.02728(16) Uani 1 1 d . . .
N2 N 0.21927(16) -0.1151(2) 0.34529(13) 0.0357(5) Uani 1 1 d . . .
H2 H 0.2846 -0.1145 0.3382 0.043 Uiso 1 1 calc R A .
C11 C 0.08245(19) -0.1895(3) 0.42361(14) 0.0318(5) Uani 1 1 d D . .
C12 C 0.0435(2) -0.2809(3) 0.47274(14) 0.0328(6) Uani 1 1 d . A .
H12 H -0.0239 -0.2721 0.4891 0.039 Uiso 1 1 calc R . .
C13 C 0.1031(2) -0.3858(3) 0.49812(14) 0.0384(6) Uani 1 1 d . . .
H13 H 0.0765 -0.4484 0.5323 0.046 Uiso 1 1 calc R A .
C14 C 0.2006(2) -0.3998(3) 0.47402(15) 0.0400(6) Uani 1 1 d . A .
H14 H 0.2412 -0.4713 0.4921 0.048 Uiso 1 1 calc R . .
C15 C 0.2397(2) -0.3095(3) 0.42329(14) 0.0342(6) Uani 1 1 d . . .
H15 H 0.3068 -0.3193 0.4066 0.041 Uiso 1 1 calc R A .
C16 C 0.18048(18) -0.2057(3) 0.39723(13) 0.0285(5) Uani 1 1 d . A .
C20 C 0.16269(17) -0.0290(2) 0.30562(13) 0.0262(5) Uani 1 1 d . A .
C21 C 0.21089(17) 0.0413(2) 0.24293(12) 0.0235(5) Uani 1 1 d . . .
C22 C 0.31115(19) 0.0244(3) 0.22428(15) 0.0339(6) Uani 1 1 d . A .
H22 H 0.3525 -0.0372 0.2504 0.041 Uiso 1 1 calc R . .
C23 C 0.3497(2) 0.0990(3) 0.16679(16) 0.0435(7) Uani 1 1 d . . .
H23 H 0.4184 0.0902 0.1534 0.052 Uiso 1 1 calc R A .
C24 C 0.2882(2) 0.1856(3) 0.12943(16) 0.0430(7) Uani 1 1 d . A .
H24 H 0.3131 0.2373 0.0897 0.052 Uiso 1 1 calc R . .
C25 C 0.18849(19) 0.1962(3) 0.15091(14) 0.0326(6) Uani 1 1 d . . .
H25 H 0.1454 0.2552 0.1246 0.039 Uiso 1 1 calc R A .
N26 N 0.15075(14) 0.1274(2) 0.20675(11) 0.0237(4) Uani 1 1 d . A .


_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
Fe N26 2.1797(18) 3 ?
Fe N26 2.1797(18) . ?
Fe N1 2.194(2) 3 ?
Fe N1 2.194(2) . ?
Fe Cl1 2.4285(7) . ?
Fe Cl1 2.4285(7) 3 ?
S1 N1 1.727(2) . ?
S1 C11 1.767(3) . ?
S1A N1 1.689(7) . ?
S1A C11 1.865(7) . ?
N1 C20 1.298(3) . ?
N2 C20 1.349(3) . ?
N2 C16 1.406(3) . ?
N2 H2 0.8800 . ?
C11 C12 1.377(3) . ?
C11 C16 1.401(3) . ?
C12 C13 1.385(4) . ?
C12 H12 0.9500 . ?
C13 C14 1.379(4) . ?
C13 H13 0.9500 . ?
C14 C15 1.390(4) . ?
C14 H14 0.9500 . ?
C15 C16 1.379(4) . ?
C15 H15 0.9500 . ?
C20 C21 1.489(3) . ?
C21 N26 1.344(3) . ?
C21 C22 1.388(3) . ?
C22 C23 1.386(4) . ?
C22 H22 0.9500 . ?
C23 C24 1.369(4) . ?
C23 H23 0.9500 . ?
C24 C25 1.388(4) . ?
C24 H24 0.9500 . ?
C25 N26 1.328(3) . ?
C25 H25 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
N26 Fe N26 163.85(11) 3 . ?
N26 Fe N1 73.74(7) 3 3 ?
N26 Fe N1 94.69(7) . 3 ?
N26 Fe N1 94.69(7) 3 . ?
N26 Fe N1 73.74(7) . . ?
N1 Fe N1 90.32(12) 3 . ?
N26 Fe Cl1 93.38(5) 3 . ?
N26 Fe Cl1 97.73(5) . . ?
N1 Fe Cl1 167.09(5) 3 . ?
N1 Fe Cl1 89.79(6) . . ?
N26 Fe Cl1 97.73(5) 3 3 ?
N26 Fe Cl1 93.38(5) . 3 ?
N1 Fe Cl1 89.79(6) 3 3 ?
N1 Fe Cl1 167.09(5) . 3 ?
Cl1 Fe Cl1 92.98(3) . 3 ?
N1 S1 C11 101.76(11) . . ?
N1 S1A C11 99.3(3) . . ?
C20 N1 S1A 120.0(3) . . ?
C20 N1 S1 120.19(18) . . ?
C20 N1 Fe 117.91(16) . . ?
S1A N1 Fe 117.4(2) . . ?
S1 N1 Fe 119.56(10) . . ?
C20 N2 C16 124.2(2) . . ?
C20 N2 H2 117.9 . . ?
C16 N2 H2 117.9 . . ?
C12 C11 C16 120.1(2) . . ?
C12 C11 S1 120.4(2) . . ?
C16 C11 S1 119.23(19) . . ?
C12 C11 S1A 116.8(3) . . ?
C16 C11 S1A 114.8(3) . . ?
C11 C12 C13 119.7(2) . . ?
C11 C12 H12 120.2 . . ?
C13 C12 H12 120.2 . . ?
C14 C13 C12 120.4(2) . . ?
C14 C13 H13 119.8 . . ?
C12 C13 H13 119.8 . . ?
C13 C14 C15 120.2(3) . . ?
C13 C14 H14 119.9 . . ?
C15 C14 H14 119.9 . . ?
C16 C15 C14 119.7(3) . . ?
C16 C15 H15 120.1 . . ?
C14 C15 H15 120.1 . . ?
C15 C16 C11 119.8(2) . . ?
C15 C16 N2 119.9(2) . . ?
C11 C16 N2 120.3(2) . . ?
N1 C20 N2 125.9(2) . . ?
N1 C20 C21 116.0(2) . . ?
N2 C20 C21 118.1(2) . . ?
N26 C21 C22 121.8(2) . . ?
N26 C21 C20 114.86(19) . . ?
C22 C21 C20 123.3(2) . . ?
C23 C22 C21 118.7(2) . . ?
C23 C22 H22 120.7 . . ?
C21 C22 H22 120.7 . . ?
C24 C23 C22 119.5(2) . . ?
C24 C23 H23 120.3 . . ?
C22 C23 H23 120.3 . . ?
C23 C24 C25 118.5(2) . . ?
C23 C24 H24 120.8 . . ?
C25 C24 H24 120.8 . . ?
N26 C25 C24 122.8(2) . . ?
N26 C25 H25 118.6 . . ?
C24 C25 H25 118.6 . . ?
C25 N26 C21 118.7(2) . . ?
C25 N26 Fe 123.86(16) . . ?
C21 N26 Fe 117.23(15) . . ?

_diffrn_measured_fraction_theta_max 0.998
_diffrn_reflns_theta_full        27.50
_diffrn_measured_fraction_theta_full 0.998
_refine_diff_density_max         0.996
_refine_diff_density_min         -0.502
_refine_diff_density_rms         0.083
_database_code_depnum_ccdc_archive 'CCDC 1002533'
#######################################################################
#
#                 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_cmpnd_1c

# start Validation Reply Form
_vrf_PLAT019_cmpnd_1c            
;
PROBLEM: diffrn_measured_fraction_theta_full/_max < 1.0    0.974
RESPONSE: The crystal was poorly diffracting to high angle, so data beyond 
2theta = 50' were omitted.In addition three highly disagreeable low angle 
reflections were omitted because they were obscured by beamstop affording
zero or negative intensities.
;


# end Validation Reply Form

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C24 H18 Cl2 Co N6 S2'
_chemical_formula_sum            'C24 H18 Cl2 Co N6 S2'
_chemical_formula_weight         584.39

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           60
_space_group_name_H-M_alt        'P b c n'
_space_group_name_Hall           '-P 2n 2ab'

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

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

_cell_length_a                   13.294(3)
_cell_length_b                   9.846(2)
_cell_length_c                   18.407(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2409.2(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    180(2)
_cell_measurement_reflns_used    11246
_cell_measurement_theta_min      1.02
_cell_measurement_theta_max      27.48

_exptl_crystal_description       rod
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.611
_exptl_crystal_F_000             1188
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.120
_exptl_crystal_size_mid          0.050
_exptl_crystal_size_min          0.020
_exptl_absorpt_coefficient_mu    1.135
_shelx_estimated_absorpt_T_min   0.876
_shelx_estimated_absorpt_T_max   0.978
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.835
_exptl_absorpt_correction_T_max  0.965
_exptl_absorpt_process_details   sortav

_exptl_special_details           
;
multi-scan from symmetry related measurements
Sortav (Blessing 1995)
;

_diffrn_ambient_temperature      180(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine focus sealed tube'
_diffrn_measurement_device_type  'Nonius Kappa CCD'
_diffrn_measurement_method       'thin slice omega and phi scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            16726
_diffrn_reflns_av_unetI/netI     0.0655
_diffrn_reflns_av_R_equivalents  0.1112
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         2.692
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.973
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.973
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.973
_reflns_number_total             2118
_reflns_number_gt                1383
_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       'Collect (Nonius B.V. 1998)'
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_reduction        
;
 HKL Denzo and Scalepack (Otwinowski & Minor 1997)
;
_computing_structure_solution    'SIR-92 (Altomare et al. 1994)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'SHELXL-2013 (Sheldrick, 2013)'
_computing_publication_material  'SHELXL-2013 (Sheldrick, 2013)'

_refine_special_details          
;
All non-H atoms refined anisotropically. H atoms added at
calculated positions using a riding model except N-H which was
located in difmap and refined with U(iso) = 1.2 x U(N(1)).
The S atom was refined over two sites with common U(ij) to give
relative sofs of 87:13.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0611P)²+5.4286P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2118
_refine_ls_number_parameters     163
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1029
_refine_ls_R_factor_gt           0.0562
_refine_ls_wR_factor_ref         0.1536
_refine_ls_wR_factor_gt          0.1275
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_restrained_S_all      1.068
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Co1 Co 0.5000 1.15117(10) 0.2500 0.0361(3) Uani 1 2 d S T P A .
Cl2 Cl 0.54437(10) 1.32106(14) 0.16079(8) 0.0457(4) Uani 1 1 d . . . . .
S1 S 0.48965(14) 0.9551(2) 0.39918(12) 0.0587(7) Uani 0.871(3) 1 d . . P A 1
S1' S 0.5097(10) 0.8752(14) 0.3526(9) 0.0587(7) Uani 0.129(3) 1 d . . P A 2
C1 C 0.3979(5) 0.6135(6) 0.4990(4) 0.0609(18) Uani 1 1 d . . . . .
H1 H 0.4246 0.5496 0.5324 0.073 Uiso 1 1 calc R U . . .
C2 C 0.3005(5) 0.6008(7) 0.4762(4) 0.0626(18) Uani 1 1 d . . . . .
H2 H 0.2593 0.5305 0.4954 0.075 Uiso 1 1 calc R U . . .
C3 C 0.2618(5) 0.6896(6) 0.4255(3) 0.0539(16) Uani 1 1 d . . . . .
H3 H 0.1943 0.6800 0.4095 0.065 Uiso 1 1 calc R U . . .
C4 C 0.3218(4) 0.7935(6) 0.3978(3) 0.0466(15) Uani 1 1 d . . . . .
C5 C 0.4205(5) 0.8080(6) 0.4236(3) 0.0485(15) Uani 1 1 d . . . . .
C6 C 0.4592(5) 0.7201(6) 0.4735(3) 0.0539(16) Uani 1 1 d . . . . .
H6 H 0.5261 0.7305 0.4908 0.065 Uiso 1 1 calc R U . . .
C7 C 0.3390(4) 0.9704(5) 0.3055(3) 0.0402(14) Uani 1 1 d . . . . .
C8 C 0.2897(4) 1.0426(5) 0.2445(3) 0.0366(12) Uani 1 1 d . . . . .
C10 C 0.3120(4) 1.1998(6) 0.1536(3) 0.0470(15) Uani 1 1 d . . . . .
H10 H 0.3548 1.2603 0.1278 0.056 Uiso 1 1 calc R U . . .
C11 C 0.2128(4) 1.1891(7) 0.1324(4) 0.0603(19) Uani 1 1 d . . . . .
H11 H 0.1879 1.2408 0.0928 0.072 Uiso 1 1 calc R U . . .
C12 C 0.1504(5) 1.1018(7) 0.1700(4) 0.0623(19) Uani 1 1 d . . . . .
H12 H 0.0814 1.0937 0.1572 0.075 Uiso 1 1 calc R U . . .
C13 C 0.1891(4) 1.0276(6) 0.2256(3) 0.0487(16) Uani 1 1 d . . . . .
H13 H 0.1476 0.9658 0.2514 0.058 Uiso 1 1 calc R U . . .
N1 N 0.4318(3) 0.9998(5) 0.3175(3) 0.0450(12) Uani 1 1 d . . . . .
N2 N 0.2824(4) 0.8831(5) 0.3454(3) 0.0548(14) Uani 1 1 d . . . . .
H2A H 0.2170 0.8824 0.3380 0.066 Uiso 1 1 calc R U . . .
N3 N 0.3502(3) 1.1294(4) 0.2083(3) 0.0367(11) Uani 1 1 d . . . . .


_geom_special_details            
;
 All esds (except the esd in the dihedral angle between two l.s. planes)
 are estimated using the full covariance matrix.  The cell esds are taken
 into account individually in the estimation of esds in distances, angles
 and torsion angles; correlations between esds in cell parameters are only
 used when they are defined by crystal symmetry.  An approximate (isotropic)
 treatment of cell esds is used for estimating esds involving l.s. planes.
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Co1 N1 2.142(5) . ?
Co1 N1 2.142(5) 3_655 ?
Co1 N3 2.144(4) 3_655 ?
Co1 N3 2.144(4) . ?
Co1 Cl2 2.4171(16) . ?
Co1 Cl2 2.4171(16) 3_655 ?
S1 N1 1.745(5) . ?
S1 C5 1.773(6) . ?
S1' N1 1.730(13) . ?
S1' C5 1.885(15) . ?
C1 C2 1.367(9) . ?
C1 C6 1.408(9) . ?
C1 H1 0.9500 . ?
C2 C3 1.378(8) . ?
C2 H2 0.9500 . ?
C3 C4 1.394(8) . ?
C3 H3 0.9500 . ?
C4 N2 1.408(7) . ?
C4 C5 1.402(8) . ?
C5 C6 1.364(8) . ?
C6 H6 0.9500 . ?
C7 N1 1.287(6) . ?
C7 N2 1.358(7) . ?
C7 C8 1.483(8) . ?
C8 N3 1.349(6) . ?
C8 C13 1.389(7) . ?
C10 N3 1.325(7) . ?
C10 C11 1.380(8) . ?
C10 H10 0.9500 . ?
C11 C12 1.380(8) . ?
C11 H11 0.9500 . ?
C12 C13 1.358(8) . ?
C12 H12 0.9500 . ?
C13 H13 0.9500 . ?
N2 H2A 0.8800 . ?

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 N1 91.8(3) . 3_655 ?
N1 Co1 N3 96.66(17) . 3_655 ?
N1 Co1 N3 75.22(17) 3_655 3_655 ?
N1 Co1 N3 75.22(17) . . ?
N1 Co1 N3 96.66(17) 3_655 . ?
N3 Co1 N3 168.5(2) 3_655 . ?
N1 Co1 Cl2 168.24(12) . . ?
N1 Co1 Cl2 89.10(14) 3_655 . ?
N3 Co1 Cl2 94.90(12) 3_655 . ?
N3 Co1 Cl2 93.03(12) . . ?
N1 Co1 Cl2 89.10(14) . 3_655 ?
N1 Co1 Cl2 168.24(12) 3_655 3_655 ?
N3 Co1 Cl2 93.03(12) 3_655 3_655 ?
N3 Co1 Cl2 94.90(12) . 3_655 ?
Cl2 Co1 Cl2 92.42(8) . 3_655 ?
N1 S1 C5 101.3(3) . . ?
N1 S1' C5 97.5(7) . . ?
C2 C1 C6 121.0(6) . . ?
C2 C1 H1 119.5 . . ?
C6 C1 H1 119.5 . . ?
C3 C2 C1 120.2(6) . . ?
C3 C2 H2 119.9 . . ?
C1 C2 H2 119.9 . . ?
C2 C3 C4 120.0(6) . . ?
C2 C3 H3 120.0 . . ?
C4 C3 H3 120.0 . . ?
C3 C4 N2 119.9(5) . . ?
C3 C4 C5 119.1(5) . . ?
N2 C4 C5 121.1(5) . . ?
C6 C5 C4 121.1(6) . . ?
C6 C5 S1 119.6(5) . . ?
C4 C5 S1 118.9(4) . . ?
C6 C5 S1' 116.9(6) . . ?
C4 C5 S1' 113.0(6) . . ?
C5 C6 C1 118.6(6) . . ?
C5 C6 H6 120.7 . . ?
C1 C6 H6 120.7 . . ?
N1 C7 N2 125.6(5) . . ?
N1 C7 C8 116.5(5) . . ?
N2 C7 C8 117.9(5) . . ?
N3 C8 C13 121.2(5) . . ?
N3 C8 C7 114.5(4) . . ?
C13 C8 C7 124.3(5) . . ?
N3 C10 C11 122.8(5) . . ?
N3 C10 H10 118.6 . . ?
C11 C10 H10 118.6 . . ?
C12 C11 C10 118.8(6) . . ?
C12 C11 H11 120.6 . . ?
C10 C11 H11 120.6 . . ?
C13 C12 C11 118.9(6) . . ?
C13 C12 H12 120.5 . . ?
C11 C12 H12 120.5 . . ?
C12 C13 C8 119.8(6) . . ?
C12 C13 H13 120.1 . . ?
C8 C13 H13 120.1 . . ?
C7 N1 S1' 118.6(6) . . ?
C7 N1 S1 120.9(4) . . ?
C7 N1 Co1 117.6(4) . . ?
S1' N1 Co1 117.2(5) . . ?
S1 N1 Co1 119.3(2) . . ?
C7 N2 C4 124.1(5) . . ?
C7 N2 H2A 118.0 . . ?
C4 N2 H2A 118.0 . . ?
C10 N3 C8 118.6(5) . . ?
C10 N3 Co1 125.2(4) . . ?
C8 N3 Co1 116.2(3) . . ?

_refine_diff_density_max         0.429
_refine_diff_density_min         -0.428
_refine_diff_density_rms         0.098

_shelxl_version_number           2013-3

_database_code_depnum_ccdc_archive 'CCDC 1002534'
#######################################################################
#
#                 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_cmpnd_1d

# start Validation Reply Form
_vrf_PLAT113_cmpnd_1d            
;
PROBLEM: ADDSYM suggests possible pseudo/New Space-group Pbcn
RESPONSE: A test for higher symmetry using PLATON(ADDSYM) suggested the 
 presence of a pseudo center of symmetry, and suggested the centrosymmetric
 space group Pbcn isomorphous with 1a - 1c. In the current case the Cu-Cl and
 related bond lengths are inequivalent due to a Jahn-Teller distortion, so 
 this is a case of pseudo-symmetry and the Pca2(1) space group is correct.
;

# end Validation Reply Form


_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C24 H18 Cl2 Cu N6 S2'
_chemical_formula_sum            'C24 H18 Cl2 Cu N6 S2'
_chemical_formula_weight         589.00

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      orthorhombic
_space_group_IT_number           29
_space_group_name_H-M_alt        'P c a 21'
_space_group_name_Hall           'P 2c -2ac'

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

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

_cell_length_a                   9.890(2)
_cell_length_b                   13.180(3)
_cell_length_c                   18.563(4)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     2419.7(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    180(2)
_cell_measurement_reflns_used    8528
_cell_measurement_theta_min      1.02
_cell_measurement_theta_max      27.48

_exptl_crystal_description       Prism
_exptl_crystal_colour            red
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.617
_exptl_crystal_F_000             1196
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.180
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.140
_exptl_absorpt_coefficient_mu    1.323
_shelx_estimated_absorpt_T_min   0.797
_shelx_estimated_absorpt_T_max   0.836
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.747
_exptl_absorpt_correction_T_max  0.834
_exptl_absorpt_process_details   
;
multi-scan from symmetry-related measurements
sortav (Blessing 1995)
;
_exptl_special_details           
;
 A test for higher symmetry using PLATON(ADDSYM) suggested the presence of 
 a pseudo center of symmetry, and suggested the centrosymmetric space group
 Pbcn. However, attempts to solve the structure in Pbcn did not give any 
 meaningful results. In addition, the refined Flack parameter was ambiguous, 
 and so the absolute structure cannot be determined. The Friedel pairs were 
 merged in the final stages of refinement.

;

_diffrn_ambient_temperature      180(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine-focus sealed tube'
_diffrn_measurement_device_type  'Nonius Kappa CCD'
_diffrn_measurement_method       'thin slice phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            9660
_diffrn_reflns_av_unetI/netI     0.0612
_diffrn_reflns_av_R_equivalents  0.0548
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.684
_diffrn_reflns_theta_max         26.372
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measured_fraction_theta_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_point_group_measured_fraction_full 0.995
_reflns_number_total             4274
_reflns_number_gt                3722
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.936
_reflns_Friedel_fraction_max     0.997
_reflns_Friedel_fraction_full    0.996

_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       'Collect (Nonius B.V. 1998)'
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_reduction        
;
 HKL Denzo and Scalepack (Otwinowski & Minor 1997)
;
_computing_structure_solution    'SIR-92 (Altomare et al. 1994)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'SHELXTL, Bruker AXS, Madison, WI, USA'
_computing_publication_material  'SHELXTL, Bruker AXS, Madison, WI, USA'

_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0394P)²+1.9809P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
'Flack H D (1983), Acta Cryst. A39, 876-881, 1728 Friedel Pairs' 

;
_refine_ls_abs_structure_Flack   0.38(3)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         4274
_refine_ls_number_parameters     317
_refine_ls_number_restraints     1
_refine_ls_R_factor_all          0.0540
_refine_ls_R_factor_gt           0.0428
_refine_ls_wR_factor_ref         0.1064
_refine_ls_wR_factor_gt          0.0992
_refine_ls_goodness_of_fit_ref   1.092
_refine_ls_restrained_S_all      1.092
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.09932(7) 0.25420(6) 0.20318(5) 0.02542(19) Uani 1 1 d . . . . .
Cl1 Cl -0.07069(15) 0.21087(12) 0.12225(9) 0.0296(3) Uani 1 1 d . . . . .
Cl2 Cl -0.09641(16) 0.30038(12) 0.30388(9) 0.0333(4) Uani 1 1 d . . . . .
N11 N 0.1167(5) 0.3978(4) 0.1643(3) 0.0248(12) Uani 1 1 d . . . . .
C101 C 0.0554(8) 0.4340(5) 0.1058(4) 0.0351(17) Uani 1 1 d . . . . .
H101 H -0.0030 0.3907 0.0793 0.042 Uiso 1 1 calc R U . . .
C102 C 0.0741(8) 0.5329(5) 0.0824(4) 0.0385(18) Uani 1 1 d . . . . .
H102 H 0.0300 0.5566 0.0402 0.046 Uiso 1 1 calc R U . . .
C103 C 0.1573(7) 0.5960(5) 0.1211(4) 0.0398(17) Uani 1 1 d . . . . .
H103 H 0.1696 0.6646 0.1067 0.048 Uiso 1 1 calc R U . . .
C104 C 0.2229(7) 0.5586(5) 0.1812(4) 0.0338(17) Uani 1 1 d . . . . .
H104 H 0.2819 0.6007 0.2082 0.041 Uiso 1 1 calc R U . . .
C105 C 0.2016(6) 0.4590(4) 0.2014(4) 0.0244(12) Uani 1 1 d . . . . .
S11 S 0.2690(2) 0.25777(14) 0.35680(11) 0.0425(5) Uani 1 1 d . . . . .
N12 N 0.2312(5) 0.3153(4) 0.2755(3) 0.0291(12) Uani 1 1 d . . . . .
N13 N 0.3447(5) 0.4659(4) 0.3088(3) 0.0281(11) Uani 1 1 d . . . . .
H13 H 0.3402 0.5324 0.3058 0.034 Uiso 1 1 calc R U . . .
C106 C 0.2632(7) 0.4096(5) 0.2655(4) 0.0264(14) Uani 1 1 d . . . . .
C107 C 0.4364(6) 0.4226(5) 0.3583(4) 0.0277(14) Uani 1 1 d . . . . .
C108 C 0.4179(7) 0.3227(5) 0.3809(4) 0.0294(15) Uani 1 1 d . . . . .
C109 C 0.5115(7) 0.2789(6) 0.4275(4) 0.0353(16) Uani 1 1 d . . . . .
H109 H 0.5018 0.2101 0.4418 0.042 Uiso 1 1 calc R U . . .
C110 C 0.6186(7) 0.3359(6) 0.4529(4) 0.0371(17) Uani 1 1 d . . . . .
H110 H 0.6815 0.3061 0.4853 0.044 Uiso 1 1 calc R U . . .
C111 C 0.6353(7) 0.4346(7) 0.4321(4) 0.0421(19) Uani 1 1 d . . . . .
H111 H 0.7086 0.4733 0.4504 0.050 Uiso 1 1 calc R U . . .
C112 C 0.5437(7) 0.4788(6) 0.3833(4) 0.0336(16) Uani 1 1 d . . . . .
H112 H 0.5558 0.5469 0.3678 0.040 Uiso 1 1 calc R U . . .
N21 N 0.1206(5) 0.1090(4) 0.2394(3) 0.0246(11) Uani 1 1 d . . . . .
C201 C 0.0454(7) 0.0715(5) 0.2927(4) 0.0305(15) Uani 1 1 d . . . . .
H201 H -0.0161 0.1157 0.3163 0.037 Uiso 1 1 calc R U . . .
C202 C 0.0519(7) -0.0276(5) 0.3152(4) 0.0339(16) Uani 1 1 d . . . . .
H202 H -0.0039 -0.0510 0.3534 0.041 Uiso 1 1 calc R U . . .
C203 C 0.1413(8) -0.0929(5) 0.2812(4) 0.0358(17) Uani 1 1 d . . . . .
H203 H 0.1477 -0.1620 0.2952 0.043 Uiso 1 1 calc R U . . .
C204 C 0.2211(7) -0.0545(5) 0.2261(4) 0.0323(16) Uani 1 1 d . . . . .
H204 H 0.2841 -0.0975 0.2024 0.039 Uiso 1 1 calc R U . . .
C205 C 0.2095(6) 0.0461(4) 0.2054(4) 0.0240(13) Uani 1 1 d . . . . .
S21 S 0.3225(2) 0.24262(15) 0.05522(13) 0.0519(6) Uani 1 1 d . . . . .
N22 N 0.2636(5) 0.1859(4) 0.1313(3) 0.0287(12) Uani 1 1 d . . . . .
N23 N 0.3767(5) 0.0298(4) 0.1097(3) 0.0351(14) Uani 1 1 d . . . . .
H23 H 0.3777 -0.0351 0.1208 0.042 Uiso 1 1 calc R U . . .
C206 C 0.2875(6) 0.0921(5) 0.1455(4) 0.0265(15) Uani 1 1 d . . . . .
C207 C 0.4674(6) 0.0648(5) 0.0554(4) 0.0273(14) Uani 1 1 d . . . . .
C208 C 0.4563(6) 0.1628(5) 0.0277(4) 0.0305(14) Uani 1 1 d . . . . .
C209 C 0.5460(7) 0.1960(5) -0.0243(4) 0.0333(15) Uani 1 1 d . . . . .
H209 H 0.5392 0.2629 -0.0429 0.040 Uiso 1 1 calc R U . . .
C210 C 0.6465(7) 0.1306(6) -0.0492(4) 0.0351(16) Uani 1 1 d . . . . .
H210 H 0.7097 0.1534 -0.0842 0.042 Uiso 1 1 calc R U . . .
C211 C 0.6540(7) 0.0338(6) -0.0233(4) 0.0344(15) Uani 1 1 d . . . . .
H211 H 0.7207 -0.0112 -0.0417 0.041 Uiso 1 1 calc R U . . .
C212 C 0.5645(6) 0.0000(5) 0.0300(4) 0.0291(14) Uani 1 1 d . . . . .
H212 H 0.5711 -0.0671 0.0484 0.035 Uiso 1 1 calc R U . . .


_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
Cu1 N11 2.033(5) . ?
Cu1 N12 2.037(5) . ?
Cu1 N21 2.039(5) . ?
Cu1 N22 2.287(5) . ?
Cu1 Cl1 2.3260(18) . ?
Cu1 Cl2 2.7589(19) . ?
N11 C101 1.332(8) . ?
N11 C105 1.352(8) . ?
C101 C102 1.386(9) . ?
C101 H101 0.9500 . ?
C102 C103 1.373(10) . ?
C102 H102 0.9500 . ?
C103 C104 1.381(10) . ?
C103 H103 0.9500 . ?
C104 C105 1.381(9) . ?
C104 H104 0.9500 . ?
C105 C106 1.488(9) . ?
S11 N12 1.730(6) . ?
S11 C108 1.761(7) . ?
N12 C106 1.296(8) . ?
N13 C106 1.359(8) . ?
N13 C107 1.412(9) . ?
N13 H13 0.8800 . ?
C107 C112 1.375(9) . ?
C107 C108 1.395(9) . ?
C108 C109 1.392(9) . ?
C109 C110 1.381(10) . ?
C109 H109 0.9500 . ?
C110 C111 1.368(11) . ?
C110 H110 0.9500 . ?
C111 C112 1.406(10) . ?
C111 H111 0.9500 . ?
C112 H112 0.9500 . ?
N21 C201 1.333(9) . ?
N21 C205 1.363(8) . ?
C201 C202 1.372(9) . ?
C201 H201 0.9500 . ?
C202 C203 1.386(10) . ?
C202 H202 0.9500 . ?
C203 C204 1.387(10) . ?
C203 H203 0.9500 . ?
C204 C205 1.386(8) . ?
C204 H204 0.9500 . ?
C205 C206 1.483(9) . ?
S21 N22 1.701(6) . ?
S21 C208 1.765(7) . ?
N22 C206 1.286(8) . ?
N23 C206 1.375(8) . ?
N23 C207 1.425(8) . ?
N23 H23 0.8800 . ?
C207 C212 1.369(9) . ?
C207 C208 1.395(9) . ?
C208 C209 1.382(10) . ?
C209 C210 1.395(10) . ?
C209 H209 0.9500 . ?
C210 C211 1.366(10) . ?
C210 H210 0.9500 . ?
C211 C212 1.402(9) . ?
C211 H211 0.9500 . ?
C212 H212 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
N11 Cu1 N12 79.2(2) . . ?
N11 Cu1 N21 169.11(17) . . ?
N12 Cu1 N21 95.0(2) . . ?
N11 Cu1 N22 95.7(2) . . ?
N12 Cu1 N22 94.88(19) . . ?
N21 Cu1 N22 75.5(2) . . ?
N11 Cu1 Cl1 93.46(16) . . ?
N12 Cu1 Cl1 170.16(16) . . ?
N21 Cu1 Cl1 93.27(16) . . ?
N22 Cu1 Cl1 92.29(15) . . ?
N11 Cu1 Cl2 95.43(16) . . ?
N12 Cu1 Cl2 85.16(16) . . ?
N21 Cu1 Cl2 93.23(15) . . ?
N22 Cu1 Cl2 168.68(14) . . ?
Cl1 Cu1 Cl2 89.12(6) . . ?
C101 N11 C105 118.9(6) . . ?
C101 N11 Cu1 125.8(5) . . ?
C105 N11 Cu1 115.3(4) . . ?
N11 C101 C102 122.1(7) . . ?
N11 C101 H101 118.9 . . ?
C102 C101 H101 118.9 . . ?
C103 C102 C101 119.1(7) . . ?
C103 C102 H102 120.5 . . ?
C101 C102 H102 120.5 . . ?
C102 C103 C104 119.1(6) . . ?
C102 C103 H103 120.4 . . ?
C104 C103 H103 120.4 . . ?
C103 C104 C105 119.2(6) . . ?
C103 C104 H104 120.4 . . ?
C105 C104 H104 120.4 . . ?
N11 C105 C104 121.6(6) . . ?
N11 C105 C106 113.6(5) . . ?
C104 C105 C106 124.8(6) . . ?
N12 S11 C108 100.9(3) . . ?
C106 N12 S11 119.5(5) . . ?
C106 N12 Cu1 116.2(5) . . ?
S11 N12 Cu1 122.7(3) . . ?
C106 N13 C107 123.1(5) . . ?
C106 N13 H13 118.5 . . ?
C107 N13 H13 118.5 . . ?
N12 C106 N13 125.7(6) . . ?
N12 C106 C105 115.7(6) . . ?
N13 C106 C105 118.5(5) . . ?
C112 C107 C108 120.6(6) . . ?
C112 C107 N13 119.8(6) . . ?
C108 C107 N13 119.5(6) . . ?
C109 C108 C107 119.3(6) . . ?
C109 C108 S11 120.9(5) . . ?
C107 C108 S11 119.5(5) . . ?
C110 C109 C108 119.8(7) . . ?
C110 C109 H109 120.1 . . ?
C108 C109 H109 120.1 . . ?
C111 C110 C109 120.8(7) . . ?
C111 C110 H110 119.6 . . ?
C109 C110 H110 119.6 . . ?
C110 C111 C112 119.9(7) . . ?
C110 C111 H111 120.0 . . ?
C112 C111 H111 120.0 . . ?
C107 C112 C111 119.4(7) . . ?
C107 C112 H112 120.3 . . ?
C111 C112 H112 120.3 . . ?
C201 N21 C205 118.6(5) . . ?
C201 N21 Cu1 122.4(4) . . ?
C205 N21 Cu1 119.0(4) . . ?
N21 C201 C202 123.6(6) . . ?
N21 C201 H201 118.2 . . ?
C202 C201 H201 118.2 . . ?
C201 C202 C203 118.8(6) . . ?
C201 C202 H202 120.6 . . ?
C203 C202 H202 120.6 . . ?
C202 C203 C204 118.2(6) . . ?
C202 C203 H203 120.9 . . ?
C204 C203 H203 120.9 . . ?
C203 C204 C205 120.4(7) . . ?
C203 C204 H204 119.8 . . ?
C205 C204 H204 119.8 . . ?
N21 C205 C204 120.5(6) . . ?
N21 C205 C206 115.8(5) . . ?
C204 C205 C206 123.8(6) . . ?
N22 S21 C208 103.6(3) . . ?
C206 N22 S21 121.9(5) . . ?
C206 N22 Cu1 113.0(4) . . ?
S21 N22 Cu1 123.7(3) . . ?
C206 N23 C207 123.5(6) . . ?
C206 N23 H23 118.3 . . ?
C207 N23 H23 118.3 . . ?
N22 C206 N23 126.4(6) . . ?
N22 C206 C205 116.7(6) . . ?
N23 C206 C205 116.9(5) . . ?
C212 C207 C208 120.4(6) . . ?
C212 C207 N23 118.9(6) . . ?
C208 C207 N23 120.7(6) . . ?
C209 C208 C207 120.0(6) . . ?
C209 C208 S21 119.7(5) . . ?
C207 C208 S21 120.3(5) . . ?
C208 C209 C210 119.6(6) . . ?
C208 C209 H209 120.2 . . ?
C210 C209 H209 120.2 . . ?
C211 C210 C209 120.0(6) . . ?
C211 C210 H210 120.0 . . ?
C209 C210 H210 120.0 . . ?
C210 C211 C212 120.7(6) . . ?
C210 C211 H211 119.6 . . ?
C212 C211 H211 119.6 . . ?
C207 C212 C211 119.2(6) . . ?
C207 C212 H212 120.4 . . ?
C211 C212 H212 120.4 . . ?

_refine_diff_density_max         0.667
_refine_diff_density_min         -0.532
_refine_diff_density_rms         0.075

_shelxl_version_number           2013-3

_database_code_depnum_ccdc_archive 'CCDC 1002535'
#######################################################################
#
#                 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_cmpnd_1e

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C24 H18 Cl2 N6 S2 Zn'
_chemical_formula_sum            'C24 H18 Cl2 N6 S2 Zn'
_chemical_formula_weight         590.83

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pbcn
_symmetry_space_group_name_Hall  '-P 2n 2ab'

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

_cell_length_a                   13.282(7)
_cell_length_b                   9.799(5)
_cell_length_c                   18.426(10)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2398(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    4412
_cell_measurement_theta_min      2.58
_cell_measurement_theta_max      26.80

_exptl_crystal_description       block
_exptl_crystal_colour            orange
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.637
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1200
_exptl_absorpt_coefficient_mu    1.449
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8340
_exptl_absorpt_correction_T_max  0.9311
_exptl_absorpt_process_details   multi-scan

_exptl_special_details           
; 
Bruker APEX2, Bruker AXS, Wisconsin,USA  
;

_diffrn_ambient_temperature      150(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  'Bruker CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            24749
_diffrn_reflns_av_R_equivalents  0.0707
_diffrn_reflns_av_sigmaI/netI    0.0387
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.21
_diffrn_reflns_theta_max         27.53
_reflns_number_total             2735
_reflns_number_gt                2283
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
 Structure solved by direct methods to reveal all non-H atoms. H atoms added
 at calculated positions and refined with a riding model. All non-H atoms
 were refined anisotropically. Residual electron density peaks near S were
 indicative of some disorder. The S atom was refined over two sites with a
 common U(ij) to a ratio of 0.92:0.08 and implemented DFIX restraints to 
 the C-S and S-N bond lengths.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0322P)²+1.2745P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         2735
_refine_ls_number_parameters     165
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.0472
_refine_ls_R_factor_gt           0.0362
_refine_ls_wR_factor_ref         0.0823
_refine_ls_wR_factor_gt          0.0779
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_restrained_S_all      1.086
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Zn1 Zn 0.0000 0.15975(4) 0.7500 0.01596(11) Uani 1 2 d S . .
Cl1 Cl 0.04175(4) 0.32711(6) 0.84090(3) 0.01949(14) Uani 1 1 d . . .
S1 S -0.01120(6) -0.04652(12) 0.60145(7) 0.0290(3) Uani 0.923(4) 1 d PD A 1
S1A S 0.0041(8) -0.0933(15) 0.6286(8) 0.0290(3) Uani 0.077(4) 1 d PD A 2
N1 N -0.06860(14) 0.00089(19) 0.68106(10) 0.0187(4) Uani 1 1 d D . .
N2 N -0.21951(14) -0.1155(2) 0.65359(11) 0.0236(5) Uani 1 1 d . . .
H2 H -0.2850 -0.1152 0.6609 0.028 Uiso 1 1 calc R A .
N3 N -0.15005(13) 0.12884(18) 0.79186(10) 0.0165(4) Uani 1 1 d . . .
C11 C -0.08270(18) -0.1910(2) 0.57554(12) 0.0209(5) Uani 1 1 d D . .
C12 C -0.04436(19) -0.2821(2) 0.52567(13) 0.0233(5) Uani 1 1 d . A .
H12 H 0.0231 -0.2730 0.5091 0.028 Uiso 1 1 calc R . .
C13 C -0.10461(19) -0.3872(2) 0.49967(13) 0.0248(5) Uani 1 1 d . . .
H13 H -0.0784 -0.4499 0.4652 0.030 Uiso 1 1 calc R A .
C14 C -0.2018(2) -0.4006(2) 0.52377(13) 0.0265(6) Uani 1 1 d . A .
H14 H -0.2430 -0.4721 0.5056 0.032 Uiso 1 1 calc R . .
C15 C -0.24052(19) -0.3100(2) 0.57469(12) 0.0228(5) Uani 1 1 d . . .
H15 H -0.3080 -0.3195 0.5911 0.027 Uiso 1 1 calc R A .
C16 C -0.18038(17) -0.2060(2) 0.60140(12) 0.0192(5) Uani 1 1 d . A .
C20 C -0.16172(16) -0.0286(2) 0.69339(12) 0.0172(5) Uani 1 1 d . A .
C21 C -0.21055(17) 0.0426(2) 0.75553(12) 0.0158(5) Uani 1 1 d . A .
C22 C -0.31103(18) 0.0262(2) 0.77402(13) 0.0231(5) Uani 1 1 d . . .
H22 H -0.3526 -0.0353 0.7478 0.028 Uiso 1 1 calc R A .
C23 C -0.34970(19) 0.1012(3) 0.83129(13) 0.0276(6) Uani 1 1 d . A .
H23 H -0.4186 0.0927 0.8443 0.033 Uiso 1 1 calc R . .
C24 C -0.28776(19) 0.1877(3) 0.86910(14) 0.0279(6) Uani 1 1 d . . .
H24 H -0.3126 0.2392 0.9090 0.033 Uiso 1 1 calc R A .
C25 C -0.18786(18) 0.1982(2) 0.84762(13) 0.0224(5) Uani 1 1 d . A .
H25 H -0.1446 0.2575 0.8739 0.027 Uiso 1 1 calc R . .


_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
Zn1 N3 2.158(2) 3_556 ?
Zn1 N3 2.158(2) . ?
Zn1 N1 2.206(2) 3_556 ?
Zn1 N1 2.206(2) . ?
Zn1 Cl1 2.4087(11) . ?
Zn1 Cl1 2.4088(11) 3_556 ?
S1 N1 1.717(2) . ?
S1 C11 1.771(2) . ?
S1A N1 1.648(10) . ?
S1A C11 1.790(10) . ?
N1 C20 1.290(3) . ?
N2 C20 1.361(3) . ?
N2 C16 1.407(3) . ?
N2 H2 0.8800 . ?
N3 C25 1.330(3) . ?
N3 C21 1.345(3) . ?
C11 C12 1.378(3) . ?
C11 C16 1.390(3) . ?
C12 C13 1.389(3) . ?
C12 H12 0.9500 . ?
C13 C14 1.372(4) . ?
C13 H13 0.9500 . ?
C14 C15 1.390(3) . ?
C14 H14 0.9500 . ?
C15 C16 1.386(3) . ?
C15 H15 0.9500 . ?
C20 C21 1.489(3) . ?
C21 C22 1.387(3) . ?
C22 C23 1.384(3) . ?
C22 H22 0.9500 . ?
C23 C24 1.372(3) . ?
C23 H23 0.9500 . ?
C24 C25 1.388(3) . ?
C24 H24 0.9500 . ?
C25 H25 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
N3 Zn1 N3 163.86(10) 3_556 . ?
N3 Zn1 N1 74.06(7) 3_556 3_556 ?
N3 Zn1 N1 94.39(7) . 3_556 ?
N3 Zn1 N1 94.39(7) 3_556 . ?
N3 Zn1 N1 74.06(7) . . ?
N1 Zn1 N1 90.24(11) 3_556 . ?
N3 Zn1 Cl1 97.56(6) 3_556 . ?
N3 Zn1 Cl1 93.42(5) . . ?
N1 Zn1 Cl1 89.14(6) 3_556 . ?
N1 Zn1 Cl1 167.38(5) . . ?
N3 Zn1 Cl1 93.42(5) 3_556 3_556 ?
N3 Zn1 Cl1 97.56(5) . 3_556 ?
N1 Zn1 Cl1 167.38(5) 3_556 3_556 ?
N1 Zn1 Cl1 89.13(6) . 3_556 ?
Cl1 Zn1 Cl1 94.19(5) . 3_556 ?
N1 S1 C11 102.04(11) . . ?
N1 S1A C11 104.0(6) . . ?
C20 N1 S1A 122.7(4) . . ?
C20 N1 S1 121.03(16) . . ?
C20 N1 Zn1 116.89(15) . . ?
S1A N1 Zn1 119.4(4) . . ?
S1 N1 Zn1 119.96(10) . . ?
C20 N2 C16 123.65(19) . . ?
C20 N2 H2 118.2 . . ?
C16 N2 H2 118.2 . . ?
C25 N3 C21 118.68(19) . . ?
C25 N3 Zn1 123.57(15) . . ?
C21 N3 Zn1 117.53(14) . . ?
C12 C11 C16 120.4(2) . . ?
C12 C11 S1 119.95(19) . . ?
C16 C11 S1 119.50(17) . . ?
C12 C11 S1A 118.2(4) . . ?
C16 C11 S1A 118.1(4) . . ?
C11 C12 C13 119.8(2) . . ?
C11 C12 H12 120.1 . . ?
C13 C12 H12 120.1 . . ?
C14 C13 C12 120.1(2) . . ?
C14 C13 H13 120.0 . . ?
C12 C13 H13 120.0 . . ?
C13 C14 C15 120.4(2) . . ?
C13 C14 H14 119.8 . . ?
C15 C14 H14 119.8 . . ?
C16 C15 C14 119.8(2) . . ?
C16 C15 H15 120.1 . . ?
C14 C15 H15 120.1 . . ?
C15 C16 C11 119.6(2) . . ?
C15 C16 N2 119.5(2) . . ?
C11 C16 N2 120.9(2) . . ?
N1 C20 N2 125.8(2) . . ?
N1 C20 C21 116.6(2) . . ?
N2 C20 C21 117.51(19) . . ?
N3 C21 C22 121.7(2) . . ?
N3 C21 C20 114.63(19) . . ?
C22 C21 C20 123.6(2) . . ?
C23 C22 C21 118.9(2) . . ?
C23 C22 H22 120.6 . . ?
C21 C22 H22 120.6 . . ?
C24 C23 C22 119.5(2) . . ?
C24 C23 H23 120.2 . . ?
C22 C23 H23 120.2 . . ?
C23 C24 C25 118.3(2) . . ?
C23 C24 H24 120.9 . . ?
C25 C24 H24 120.9 . . ?
N3 C25 C24 122.9(2) . . ?
N3 C25 H25 118.5 . . ?
C24 C25 H25 118.5 . . ?

_diffrn_measured_fraction_theta_max 0.991
_diffrn_reflns_theta_full        27.53
_diffrn_measured_fraction_theta_full 0.991
_refine_diff_density_max         0.386
_refine_diff_density_min         -0.302
_refine_diff_density_rms         0.077
_database_code_depnum_ccdc_archive 'CCDC 1002536'
#######################################################################
#
#                 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_cmpnd2

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C12 H9 Cl2 Cu N3 S'
_chemical_formula_sum            'C12 H9 Cl2 Cu N3 S'
_chemical_formula_weight         361.72

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           monoclinic
_symmetry_space_group_name_H-M   'C c'
_symmetry_space_group_name_Hall  'C -2yc'

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

_cell_length_a                   9.0429(3)
_cell_length_b                   22.3081(5)
_cell_length_c                   7.1341(3)
_cell_angle_alpha                90.00
_cell_angle_beta                 116.720(3)
_cell_angle_gamma                90.00
_cell_volume                     1285.48(8)
_cell_formula_units_Z            4
_cell_measurement_temperature    180(2)
_cell_measurement_reflns_used    11719
_cell_measurement_theta_min      1.00
_cell_measurement_theta_max      27.48

_exptl_crystal_description       brick
_exptl_crystal_colour            'dark red'
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.05
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.869
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             724
_exptl_absorpt_coefficient_mu    2.262
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.805
_exptl_absorpt_correction_T_max  0.890
_exptl_absorpt_process_details   
;
multi-scan from symmetry-related measurements 
 Sortav (Blessing 1995)
;

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      180(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  'Nonius Kappa CCD'
_diffrn_measurement_method       'thin slice ω and φ scans'
_diffrn_reflns_number            7761
_diffrn_reflns_av_R_equivalents  0.0401
_diffrn_reflns_av_sigmaI/netI    0.0419
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_theta_min         3.19
_diffrn_reflns_theta_max         27.43
_reflns_number_total             2593
_reflns_number_gt                2448
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Collect (Nonius B.V. 1998)'
_computing_cell_refinement       'HKL Scalepack (Otwinowski & Minor 1997)'
_computing_data_reduction        
;
 HKL Denzo and Scalepack (Otwinowski & Minor 1997)
;
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'SHELXL-97 (Sheldrick 1997)'

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² 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/[σ²(Fo²)+(0.0140P)²+3.5139P] where P=(Fo²+2Fc²)/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     none
_refine_ls_extinction_coef       ?
_refine_ls_abs_structure_details 
'Flack H D (1983), Acta Cryst. A39, 876-881, 1122 Friedel pairs'
_refine_ls_abs_structure_Flack   -0.028(14)
_refine_ls_number_reflns         2593
_refine_ls_number_parameters     176
_refine_ls_number_restraints     3
_refine_ls_R_factor_all          0.0357
_refine_ls_R_factor_gt           0.0320
_refine_ls_wR_factor_ref         0.0685
_refine_ls_wR_factor_gt          0.0657
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_restrained_S_all      1.055
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu1 Cu 0.41217(6) 0.583216(18) 0.46302(7) 0.02337(12) Uani 1 1 d . . .
Cl1 Cl 0.53031(13) 0.66693(4) 0.63563(17) 0.0309(2) Uani 1 1 d . . .
Cl2 Cl 0.63396(11) 0.54970(4) 0.43176(15) 0.0292(2) Uani 1 1 d . . .
N1 N 0.1753(4) 0.61248(13) 0.3467(5) 0.0211(6) Uani 1 1 d . . .
N2 N 0.2919(4) 0.50583(13) 0.3594(5) 0.0226(7) Uani 1 1 d . . .
S1 S 0.39374(11) 0.44094(4) 0.35675(15) 0.0224(2) Uani 1 1 d . . .
C1 C 0.1250(5) 0.66857(17) 0.3462(6) 0.0271(9) Uani 1 1 d . . .
H1A H 0.2053 0.6997 0.3968 0.033 Uiso 1 1 calc R . .
C2 C -0.0406(5) 0.68313(18) 0.2743(7) 0.0302(9) Uani 1 1 d . . .
H2A H -0.0726 0.7235 0.2781 0.036 Uiso 1 1 calc R . .
C3 C -0.1582(5) 0.63873(19) 0.1974(7) 0.0295(10) Uani 1 1 d . . .
H3A H -0.2724 0.6480 0.1462 0.035 Uiso 1 1 calc R . .
C4 C -0.1068(5) 0.57990(18) 0.1960(7) 0.0279(9) Uani 1 1 d . . .
H4A H -0.1853 0.5483 0.1446 0.033 Uiso 1 1 calc R . .
C5 C 0.0594(5) 0.56842(17) 0.2704(6) 0.0215(8) Uani 1 1 d . . .
C6 C 0.1324(5) 0.50796(16) 0.2817(5) 0.0202(7) Uani 1 1 d . . .
N3 N 0.0301(4) 0.45983(14) 0.2147(5) 0.0237(7) Uani 1 1 d D . .
H3B H -0.081(3) 0.466(2) 0.161(7) 0.032(12) Uiso 1 1 d D . .
C7 C 0.0854(5) 0.40077(17) 0.2834(6) 0.0225(8) Uani 1 1 d . . .
C8 C -0.0270(5) 0.35723(19) 0.2760(6) 0.0271(9) Uani 1 1 d . . .
H8A H -0.1410 0.3668 0.2242 0.033 Uiso 1 1 calc R . .
C9 C 0.0284(5) 0.30001(17) 0.3444(6) 0.0262(8) Uani 1 1 d . . .
H9A H -0.0489 0.2697 0.3340 0.031 Uiso 1 1 calc R . .
C10 C 0.1946(5) 0.28607(18) 0.4278(6) 0.0283(9) Uani 1 1 d . . .
H10A H 0.2313 0.2465 0.4750 0.034 Uiso 1 1 calc R . .
C11 C 0.3083(5) 0.33002(18) 0.4426(6) 0.0278(9) Uani 1 1 d . . .
H11A H 0.4233 0.3211 0.5055 0.033 Uiso 1 1 calc R . .
C12 C 0.2532(5) 0.38704(16) 0.3652(6) 0.0219(8) Uani 1 1 d . . .


_geom_special_details            
; 
 All esds (except the esd in the dihedral angle between two l.s. planes) 
 are estimated using the full covariance matrix.  The cell esds are taken 
 into account individually in the estimation of esds in distances, angles 
 and torsion angles; correlations between esds in cell parameters are only 
 used when they are defined by crystal symmetry.  An approximate (isotropic) 
 treatment of cell esds is used for estimating esds involving l.s. planes. 
;

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Cu1 N2 1.997(3) . ?
Cu1 N1 2.026(3) . ?
Cu1 Cl1 2.2276(11) . ?
Cu1 Cl2 2.2435(11) . ?
N1 C1 1.331(5) . ?
N1 C5 1.360(5) . ?
N2 C6 1.293(5) . ?
N2 S1 1.720(3) . ?
S1 C12 1.770(4) . ?
C1 C2 1.386(6) . ?
C2 C3 1.374(6) . ?
C3 C4 1.394(6) . ?
C4 C5 1.374(6) . ?
C5 C6 1.488(5) . ?
C6 N3 1.356(5) . ?
N3 C7 1.416(5) . ?
C7 C8 1.389(6) . ?
C7 C12 1.393(5) . ?
C8 C9 1.378(6) . ?
C9 C10 1.381(6) . ?
C10 C11 1.390(6) . ?
C11 C12 1.387(5) . ?
N3 H3B 0.91(4) . ?
C1 H1A 0.95 . ?
C2 H2A 0.95 . ?
C3 H3A 0.95 . ?
C4 H4A 0.95 . ?
C8 H8A 0.95 . ?
C9 H9A 0.95 . ?
C10 H10A 0.95 . ?
C11 H11A 0.95 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N2 Cu1 N1 80.07(13) . . ?
N2 Cu1 Cl1 167.30(10) . . ?
N1 Cu1 Cl1 96.44(9) . . ?
N2 Cu1 Cl2 92.14(10) . . ?
N1 Cu1 Cl2 153.42(9) . . ?
Cl1 Cu1 Cl2 96.11(4) . . ?
C1 N1 C5 118.5(3) . . ?
C1 N1 Cu1 127.0(3) . . ?
C5 N1 Cu1 114.5(2) . . ?
C6 N2 S1 121.7(3) . . ?
C6 N2 Cu1 116.4(2) . . ?
S1 N2 Cu1 121.78(17) . . ?
N2 S1 C12 100.08(17) . . ?
N1 C1 C2 122.2(4) . . ?
C3 C2 C1 119.5(4) . . ?
C2 C3 C4 118.7(4) . . ?
C5 C4 C3 118.9(4) . . ?
N1 C5 C4 122.2(4) . . ?
N1 C5 C6 112.9(3) . . ?
C4 C5 C6 124.9(4) . . ?
N2 C6 N3 125.1(3) . . ?
N2 C6 C5 116.0(3) . . ?
N3 C6 C5 118.9(3) . . ?
C6 N3 C7 122.4(3) . . ?
C8 C7 C12 120.2(4) . . ?
C8 C7 N3 119.9(4) . . ?
C12 C7 N3 119.9(3) . . ?
C9 C8 C7 119.4(4) . . ?
C8 C9 C10 120.9(4) . . ?
C9 C10 C11 119.9(4) . . ?
C12 C11 C10 119.7(4) . . ?
C11 C12 C7 119.8(3) . . ?
C11 C12 S1 120.1(3) . . ?
C7 C12 S1 120.0(3) . . ?
C6 N3 H3B 119(3) . . ?
C7 N3 H3B 116(3) . . ?
N1 C1 H1A 119 . . ?
C2 C1 H1A 119 . . ?
C1 C2 H2A 120 . . ?
C3 C2 H2A 120 . . ?
C2 C3 H3A 121 . . ?
C4 C3 H3A 121 . . ?
C3 C4 H4A 121 . . ?
C5 C4 H4A 121 . . ?
C7 C8 H8A 120 . . ?
C9 C8 H8A 120 . . ?
C11 C10 H10A 120 . . ?
C10 C11 H11A 120 . . ?
C12 C11 H11A 120 . . ?

_diffrn_measured_fraction_theta_max 0.996
_diffrn_reflns_theta_full        27.43
_diffrn_measured_fraction_theta_full 0.996
_refine_diff_density_max         0.340
_refine_diff_density_min         -0.429
_refine_diff_density_rms         0.073
_database_code_depnum_ccdc_archive 'CCDC 1002537'
#######################################################################
#
#                 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_cmpnd_3

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C36 H27 Fe N9 S3, 2(C F3 O3 S)'
_chemical_formula_sum            'C38 H27 F6 Fe N9 O6 S5'
_chemical_formula_weight         1035.83

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'
F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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

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

loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, -z'

_cell_length_a                   12.236(4)
_cell_length_b                   14.022(4)
_cell_length_c                   15.179(5)
_cell_angle_alpha                88.805(3)
_cell_angle_beta                 79.225(3)
_cell_angle_gamma                73.710(3)
_cell_volume                     2454.4(13)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    9717
_cell_measurement_theta_min      2.236
_cell_measurement_theta_max      27.525

_exptl_crystal_description       block
_exptl_crystal_colour            red
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_diffrn    1.402
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             1052
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.120
_exptl_absorpt_coefficient_mu    0.594
_shelx_estimated_absorpt_T_min   0.891
_shelx_estimated_absorpt_T_max   0.932
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.671
_exptl_absorpt_correction_T_max  0.746
_exptl_absorpt_process_details   
;
sadabs-2012/1, Bruker AXS, Madison, wisconsin, USA
;

_exptl_special_details           
;
Intial structure solution revealed at least three MeCN part 
occupancy molecules which did not refine well and with significant
diffuse electron density elsewhere in the structure. In this case
SQUEEZE was applied to remove the diffuse solvent scattering.
This led to significant improvement in final wR2 from 0.30 to 0.17
as well as other final residuals.

The void volume of 502 A3 corresponds to 9.3 MeCN molecules
per unit cell or 4.6 per asymmetric unit assuming 18 A3 per
non-H atom. Similarly 181 e- corresponds to 8.2 MeCN molecules
per unit cell or 4.1 MeCN per asymmetric unit. Both parameters
indicate 4 MeCN molecules per asymmetric unit.
 
# SQUEEZE RESULTS
# Note: Data are Listed for all Voids in the P1 Unit Cell
# i.e. Centre of Gravity, Solvent Accessible Volume,
# Recovered number of Electrons in the Void and
# Details about the Squeezed Material

;
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 0.500 0.585 0.500 502 181 ' '
_platon_squeeze_details          
;
;


_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'fine focus sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            28322
_diffrn_reflns_av_unetI/netI     0.0475
_diffrn_reflns_av_R_equivalents  0.0395
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         1.976
_diffrn_reflns_theta_max         27.499
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measured_fraction_theta_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.974
_diffrn_reflns_point_group_measured_fraction_full 0.997
_reflns_number_total             10986
_reflns_number_gt                8880
_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.

 Structure factors included contributions from the .fab file.
 
 _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       'Bruker APEX-II'
_computing_cell_refinement       'Bruker APEX-II'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
structure solved by direct methods to reveal the cation and two
triflate counterions. Some evidence for disordered MeCN present but
solvent treated with SQUEEZE due to large amount of diffuse scattering.
One of the three heterocyclic rings showed slight evidence of disorder
which was modelled as disorder of the S atom over two positions.
Each triflate showed substantial disorder reflected in a rocking of
the anion about one O atom (which was hydrogen bonded to an N-H group
of the cation). Site occupancy factors for each position were refined
with common U(iso) for equivalent atoms, leading to a 44:56 and 51:49
disorder in the two independent triflates.
Both S and F atoms were refined anisotropically but attempted refinement
of the O atoms led to significant splitting indicative of further disorder. 
As a consequnce both lighter O and C atoms were refined isotropically.
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0979P)²+4.2867P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         10986
_refine_ls_number_parameters     576
_refine_ls_number_restraints     146
_refine_ls_R_factor_all          0.0794
_refine_ls_R_factor_gt           0.0667
_refine_ls_wR_factor_ref         0.1856
_refine_ls_wR_factor_gt          0.1754
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_restrained_S_all      1.104
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
Fe1 Fe 0.82379(4) 0.18622(3) 0.20697(3) 0.01989(13) Uani 1 1 d . . . . .
S11A S 0.8925(3) 0.19386(12) 0.39805(11) 0.0361(5) Uani 0.841(7) 1 d . . P A 1
S11B S 0.8378(14) 0.2086(7) 0.4133(6) 0.0361(5) Uani 0.159(7) 1 d . . P A 2
N11 N 0.8424(3) 0.1322(2) 0.32492(18) 0.0257(6) Uani 1 1 d . . . . .
C11 C 0.8651(4) 0.1300(3) 0.4984(2) 0.0327(8) Uani 1 1 d . . . . .
N12 N 0.8443(4) -0.0073(2) 0.4147(2) 0.0434(9) Uani 1 1 d . . . . .
H12 H 0.8491 -0.0711 0.4134 0.052 Uiso 1 1 calc R U . . .
C12 C 0.8491(3) 0.0363(3) 0.4953(2) 0.0312(8) Uani 1 1 d . . . . .
C13 C 0.8377(4) -0.0152(3) 0.5735(3) 0.0451(10) Uani 1 1 d . . . . .
H13 H 0.8276 -0.0799 0.5721 0.054 Uiso 1 1 calc R U . . .
C14 C 0.8408(7) 0.0275(4) 0.6527(3) 0.078(2) Uani 1 1 d . . . . .
H14 H 0.8327 -0.0079 0.7065 0.093 Uiso 1 1 calc R U . . .
C15 C 0.8557(7) 0.1210(4) 0.6557(3) 0.083(2) Uani 1 1 d . . . . .
H15 H 0.8574 0.1499 0.7113 0.100 Uiso 1 1 calc R U . . .
C16 C 0.8681(5) 0.1723(3) 0.5783(3) 0.0505(12) Uani 1 1 d . . . . .
H16 H 0.8787 0.2368 0.5800 0.061 Uiso 1 1 calc R U . . .
C20 C 0.8328(3) 0.0430(3) 0.3389(2) 0.0276(7) Uani 1 1 d . . . . .
C21 C 0.8062(3) -0.0032(2) 0.2624(2) 0.0249(7) Uani 1 1 d . . . . .
C22 C 0.7942(4) -0.0980(3) 0.2606(2) 0.0333(8) Uani 1 1 d . . . . .
H22 H 0.8022 -0.1383 0.3115 0.040 Uiso 1 1 calc R U . . .
C23 C 0.7708(4) -0.1336(3) 0.1847(3) 0.0346(8) Uani 1 1 d . . . . .
H23 H 0.7624 -0.1988 0.1823 0.042 Uiso 1 1 calc R U . . .
C24 C 0.7598(3) -0.0733(3) 0.1122(2) 0.0307(8) Uani 1 1 d . . . . .
H24 H 0.7435 -0.0961 0.0589 0.037 Uiso 1 1 calc R U . . .
C25 C 0.7727(3) 0.0207(3) 0.1183(2) 0.0251(7) Uani 1 1 d . . . . .
H25 H 0.7642 0.0621 0.0682 0.030 Uiso 1 1 calc R U . . .
N26 N 0.7966(2) 0.0565(2) 0.19126(18) 0.0225(6) Uani 1 1 d . . . . .
S31 S 1.05539(7) 0.02094(6) 0.11306(6) 0.02705(19) Uani 1 1 d . . . . .
N31 N 0.9915(2) 0.1372(2) 0.16322(18) 0.0221(5) Uani 1 1 d . . . . .
C31 C 1.2019(3) 0.0054(3) 0.1182(2) 0.0282(7) Uani 1 1 d . . . . .
C32 C 1.2420(3) 0.0882(3) 0.1205(2) 0.0328(8) Uani 1 1 d . . . . .
N33 N 1.1637(3) 0.1841(2) 0.1259(2) 0.0323(7) Uani 1 1 d . . . . .
H33A H 1.1903 0.2343 0.1062 0.039 Uiso 1 1 calc R U . . .
C33 C 1.3591(3) 0.0760(4) 0.1184(3) 0.0489(11) Uani 1 1 d . . . . .
H33 H 1.3877 0.1321 0.1202 0.059 Uiso 1 1 calc R U . . .
C34 C 1.4334(4) -0.0192(4) 0.1137(4) 0.0611(14) Uani 1 1 d . . . . .
H34 H 1.5137 -0.0277 0.1114 0.073 Uiso 1 1 calc R U . . .
C35 C 1.3944(4) -0.1012(4) 0.1123(3) 0.0539(12) Uani 1 1 d . . . . .
H35 H 1.4473 -0.1658 0.1085 0.065 Uiso 1 1 calc R U . . .
C36 C 1.2773(3) -0.0898(3) 0.1164(3) 0.0392(9) Uani 1 1 d . . . . .
H36 H 1.2488 -0.1464 0.1180 0.047 Uiso 1 1 calc R U . . .
C40 C 1.0500(3) 0.2019(2) 0.1602(2) 0.0246(7) Uani 1 1 d . . . . .
C41 C 0.9820(3) 0.2998(3) 0.2009(2) 0.0258(7) Uani 1 1 d . . . . .
C42 C 1.0270(4) 0.3770(3) 0.2144(3) 0.0383(9) Uani 1 1 d . . . . .
H42 H 1.1067 0.3711 0.1927 0.046 Uiso 1 1 calc R U . . .
C43 C 0.9555(4) 0.4625(3) 0.2594(3) 0.0470(11) Uani 1 1 d . . . . .
H43 H 0.9853 0.5159 0.2699 0.056 Uiso 1 1 calc R U . . .
C44 C 0.8396(4) 0.4695(3) 0.2891(3) 0.0423(10) Uani 1 1 d . . . . .
H44 H 0.7887 0.5276 0.3207 0.051 Uiso 1 1 calc R U . . .
C45 C 0.7990(4) 0.3905(3) 0.2720(2) 0.0315(8) Uani 1 1 d . . . . .
H45 H 0.7189 0.3961 0.2912 0.038 Uiso 1 1 calc R U . . .
N46 N 0.8681(3) 0.3063(2) 0.22927(18) 0.0238(6) Uani 1 1 d . . . . .
S51 S 0.90044(7) 0.21665(7) -0.00306(6) 0.0316(2) Uani 1 1 d . . . . .
N51 N 0.6448(2) 0.3265(2) 0.01294(19) 0.0298(7) Uani 1 1 d . . . . .
H51 H 0.5692 0.3481 0.0168 0.036 Uiso 1 1 calc R U . . .
C51 C 0.8346(3) 0.2933(2) -0.0829(2) 0.0247(7) Uani 1 1 d . . . . .
N52 N 0.7915(2) 0.2372(2) 0.08983(17) 0.0209(5) Uani 1 1 d . . . . .
C52 C 0.7162(3) 0.3370(2) -0.0691(2) 0.0247(7) Uani 1 1 d . . . . .
C53 C 0.6665(3) 0.3902(3) -0.1361(2) 0.0311(8) Uani 1 1 d . . . . .
H53 H 0.5850 0.4196 -0.1268 0.037 Uiso 1 1 calc R U . . .
C54 C 0.7357(4) 0.4005(3) -0.2171(3) 0.0378(9) Uani 1 1 d . . . . .
H54 H 0.7015 0.4372 -0.2633 0.045 Uiso 1 1 calc R U . . .
C55 C 0.8539(3) 0.3578(3) -0.2309(3) 0.0367(9) Uani 1 1 d . . . . .
H55 H 0.9010 0.3650 -0.2866 0.044 Uiso 1 1 calc R U . . .
C56 C 0.9042(3) 0.3045(3) -0.1637(2) 0.0312(8) Uani 1 1 d . . . . .
H56 H 0.9858 0.2759 -0.1729 0.037 Uiso 1 1 calc R U . . .
C60 C 0.6852(3) 0.2854(2) 0.0859(2) 0.0225(6) Uani 1 1 d . . . . .
C61 C 0.6039(3) 0.2919(2) 0.1720(2) 0.0242(7) Uani 1 1 d . . . . .
C62 C 0.4862(3) 0.3361(3) 0.1839(3) 0.0341(8) Uani 1 1 d . . . . .
H62 H 0.4520 0.3674 0.1356 0.041 Uiso 1 1 calc R U . . .
C63 C 0.4185(3) 0.3340(3) 0.2681(3) 0.0441(10) Uani 1 1 d . . . . .
H63 H 0.3370 0.3631 0.2781 0.053 Uiso 1 1 calc R U . . .
C64 C 0.4714(3) 0.2891(3) 0.3368(3) 0.0422(10) Uani 1 1 d . . . . .
H64 H 0.4267 0.2867 0.3947 0.051 Uiso 1 1 calc R U . . .
C65 C 0.5898(3) 0.2476(3) 0.3207(2) 0.0324(8) Uani 1 1 d . . . . .
H65 H 0.6257 0.2178 0.3687 0.039 Uiso 1 1 calc R U . . .
N66 N 0.6562(2) 0.2476(2) 0.23964(19) 0.0249(6) Uani 1 1 d . . . . .
O1A O 0.7085(3) -0.3249(3) 0.4595(2) 0.0643(9) Uiso 0.511(5) 1 d D . P B 1
S1A S 0.8181(7) -0.2997(6) 0.4523(6) 0.0435(9) Uani 0.511(5) 1 d D . P B 1
O1B O 0.9090(6) -0.3495(5) 0.3812(5) 0.0531(12) Uiso 0.511(5) 1 d D . P B 1
O1C O 0.8175(6) -0.1970(4) 0.4607(5) 0.0496(11) Uiso 0.511(5) 1 d D . P B 1
C1A C 0.8746(8) -0.3406(6) 0.5550(7) 0.0519(16) Uiso 0.511(5) 1 d D . P B 1
F1A F 0.8629(7) -0.4290(5) 0.5791(6) 0.0813(9) Uani 0.511(5) 1 d D . P B 1
F1B F 0.8145(6) -0.2764(6) 0.6212(5) 0.0813(9) Uani 0.511(5) 1 d D . P B 1
F1C F 0.9869(6) -0.3513(6) 0.5505(6) 0.0813(9) Uani 0.511(5) 1 d D . P B 1
O1D O 0.7085(3) -0.3249(3) 0.4595(2) 0.0643(9) Uiso 0.489(5) 1 d D . P B 2
S1B S 0.8071(8) -0.2885(7) 0.4416(6) 0.0435(9) Uani 0.489(5) 1 d D . P B 2
O1E O 0.8752(6) -0.3181(5) 0.3552(5) 0.0531(12) Uiso 0.489(5) 1 d D . P B 2
O1F O 0.7694(6) -0.1844(5) 0.4647(5) 0.0496(11) Uiso 0.489(5) 1 d D . P B 2
C1B C 0.8847(8) -0.3547(7) 0.5246(7) 0.0519(16) Uiso 0.489(5) 1 d D . P B 2
F1D F 0.8966(7) -0.4508(5) 0.5221(6) 0.0813(9) Uani 0.489(5) 1 d D . P B 2
F1E F 0.8263(7) -0.3241(6) 0.6111(5) 0.0813(9) Uani 0.489(5) 1 d D . P B 2
F1F F 0.9863(6) -0.3360(6) 0.5146(6) 0.0813(9) Uani 0.489(5) 1 d D . P B 2
O2A O 1.2819(3) 0.3297(3) 0.0843(2) 0.0622(9) Uiso 0.442(3) 1 d D . P C 1
S2A S 1.3257(6) 0.3494(5) -0.0067(4) 0.0328(19) Uani 0.442(3) 1 d D . P C 1
O2B O 1.3498(6) 0.2823(6) -0.0828(5) 0.0495(11) Uiso 0.442(3) 1 d D . P C 1
O2C O 1.4021(6) 0.4142(5) -0.0111(4) 0.0331(8) Uiso 0.442(3) 1 d D . P C 1
C2A C 1.2018(8) 0.4223(7) -0.0520(6) 0.0470(15) Uiso 0.442(3) 1 d D . P C 1
F2A F 1.1702(6) 0.5159(5) -0.0186(7) 0.0747(9) Uani 0.442(3) 1 d D . P C 1
F2B F 1.2304(6) 0.4212(5) -0.1368(5) 0.0747(9) Uani 0.442(3) 1 d D . P C 1
F2C F 1.1111(8) 0.3849(7) -0.0243(8) 0.0747(9) Uani 0.442(3) 1 d D . P C 1
O2D O 1.2819(3) 0.3297(3) 0.0843(2) 0.0622(9) Uiso 0.558(3) 1 d D . P C 2
S2B S 1.3196(5) 0.3444(4) -0.0094(4) 0.0361(16) Uani 0.558(3) 1 d D . P C 2
O2E O 1.3397(5) 0.2472(4) -0.0512(4) 0.0495(11) Uiso 0.558(3) 1 d D . P C 2
O2F O 1.4129(5) 0.3873(4) -0.0260(4) 0.0331(8) Uiso 0.558(3) 1 d D . P C 2
C2B C 1.1923(7) 0.4394(6) -0.0243(5) 0.0470(15) Uiso 0.558(3) 1 d D . P C 2
F2D F 1.1467(5) 0.4993(4) 0.0495(5) 0.0747(9) Uani 0.558(3) 1 d D . P C 2
F2E F 1.1114(7) 0.4018(5) -0.0436(6) 0.0747(9) Uani 0.558(3) 1 d D . P C 2
F2F F 1.2053(5) 0.5072(4) -0.0854(5) 0.0747(9) Uani 0.558(3) 1 d D . P C 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
Fe1 N11 1.957(3) . ?
Fe1 N66 1.959(3) . ?
Fe1 N31 1.961(3) . ?
Fe1 N46 1.962(3) . ?
Fe1 N26 1.965(3) . ?
Fe1 N52 1.970(3) . ?
S11A N11 1.717(3) . ?
S11A C11 1.777(4) . ?
S11B C11 1.701(9) . ?
S11B N11 1.718(9) . ?
N11 C20 1.298(4) . ?
C11 C16 1.373(5) . ?
C11 C12 1.384(5) . ?
N12 C20 1.346(4) . ?
N12 C12 1.398(5) . ?
N12 H12 0.8800 . ?
C12 C13 1.381(5) . ?
C13 C14 1.367(6) . ?
C13 H13 0.9500 . ?
C14 C15 1.376(7) . ?
C14 H14 0.9500 . ?
C15 C16 1.371(6) . ?
C15 H15 0.9500 . ?
C16 H16 0.9500 . ?
C20 C21 1.472(5) . ?
C21 N26 1.354(4) . ?
C21 C22 1.379(5) . ?
C22 C23 1.373(5) . ?
C22 H22 0.9500 . ?
C23 C24 1.378(5) . ?
C23 H23 0.9500 . ?
C24 C25 1.376(5) . ?
C24 H24 0.9500 . ?
C25 N26 1.339(4) . ?
C25 H25 0.9500 . ?
S31 N31 1.721(3) . ?
S31 C31 1.761(3) . ?
N31 C40 1.298(4) . ?
C31 C32 1.385(5) . ?
C31 C36 1.391(5) . ?
C32 C33 1.389(5) . ?
C32 N33 1.408(5) . ?
N33 C40 1.346(4) . ?
N33 H33A 0.8800 . ?
C33 C34 1.382(7) . ?
C33 H33 0.9500 . ?
C34 C35 1.365(8) . ?
C34 H34 0.9500 . ?
C35 C36 1.386(6) . ?
C35 H35 0.9500 . ?
C36 H36 0.9500 . ?
C40 C41 1.470(5) . ?
C41 N46 1.356(4) . ?
C41 C42 1.379(5) . ?
C42 C43 1.375(6) . ?
C42 H42 0.9500 . ?
C43 C44 1.381(6) . ?
C43 H43 0.9500 . ?
C44 C45 1.381(5) . ?
C44 H44 0.9500 . ?
C45 N46 1.341(4) . ?
C45 H45 0.9500 . ?
S51 N52 1.717(3) . ?
S51 C51 1.760(3) . ?
N51 C60 1.350(4) . ?
N51 C52 1.412(4) . ?
N51 H51 0.8800 . ?
C51 C52 1.383(5) . ?
C51 C56 1.390(5) . ?
N52 C60 1.298(4) . ?
C52 C53 1.381(5) . ?
C53 C54 1.386(5) . ?
C53 H53 0.9500 . ?
C54 C55 1.379(6) . ?
C54 H54 0.9500 . ?
C55 C56 1.387(5) . ?
C55 H55 0.9500 . ?
C56 H56 0.9500 . ?
C60 C61 1.475(4) . ?
C61 N66 1.359(4) . ?
C61 C62 1.376(5) . ?
C62 C63 1.393(5) . ?
C62 H62 0.9500 . ?
C63 C64 1.377(6) . ?
C63 H63 0.9500 . ?
C64 C65 1.378(5) . ?
C64 H64 0.9500 . ?
C65 N66 1.342(4) . ?
C65 H65 0.9500 . ?
O1A S1A 1.464(9) . ?
S1A O1B 1.427(9) . ?
S1A O1C 1.447(9) . ?
S1A C1A 1.838(11) . ?
C1A F1A 1.324(9) . ?
C1A F1B 1.324(10) . ?
C1A F1C 1.328(9) . ?
S1B O1E 1.417(9) . ?
S1B O1F 1.432(9) . ?
S1B C1B 1.804(11) . ?
C1B F1D 1.314(9) . ?
C1B F1F 1.322(9) . ?
C1B F1E 1.386(10) . ?
O2A S2A 1.436(7) . ?
S2A O2B 1.438(8) . ?
S2A O2C 1.467(8) . ?
S2A C2A 1.819(10) . ?
C2A F2B 1.268(10) . ?
C2A F2A 1.341(10) . ?
C2A F2C 1.351(10) . ?
S2B O2F 1.415(7) . ?
S2B O2E 1.453(7) . ?
S2B C2B 1.792(9) . ?
C2B F2E 1.323(9) . ?
C2B F2F 1.335(8) . ?
C2B F2D 1.347(9) . ?

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
N11 Fe1 N66 95.70(12) . . ?
N11 Fe1 N31 90.57(12) . . ?
N66 Fe1 N31 173.00(11) . . ?
N11 Fe1 N46 94.50(11) . . ?
N66 Fe1 N46 95.79(12) . . ?
N31 Fe1 N46 80.57(12) . . ?
N11 Fe1 N26 80.34(11) . . ?
N66 Fe1 N26 90.01(11) . . ?
N31 Fe1 N26 94.13(11) . . ?
N46 Fe1 N26 172.61(11) . . ?
N11 Fe1 N52 174.67(12) . . ?
N66 Fe1 N52 80.18(11) . . ?
N31 Fe1 N52 93.74(11) . . ?
N46 Fe1 N52 89.30(11) . . ?
N26 Fe1 N52 96.21(11) . . ?
N11 S11A C11 101.09(17) . . ?
C11 S11B N11 104.2(5) . . ?
C20 N11 S11A 122.1(2) . . ?
C20 N11 S11B 120.3(4) . . ?
C20 N11 Fe1 117.4(2) . . ?
S11A N11 Fe1 119.66(16) . . ?
S11B N11 Fe1 120.6(3) . . ?
C16 C11 C12 120.7(4) . . ?
C16 C11 S11B 116.5(4) . . ?
C12 C11 S11B 120.0(4) . . ?
C16 C11 S11A 118.6(3) . . ?
C12 C11 S11A 120.5(3) . . ?
C20 N12 C12 123.5(3) . . ?
C20 N12 H12 118.2 . . ?
C12 N12 H12 118.2 . . ?
C13 C12 C11 119.4(3) . . ?
C13 C12 N12 119.3(3) . . ?
C11 C12 N12 121.4(3) . . ?
C14 C13 C12 119.6(4) . . ?
C14 C13 H13 120.2 . . ?
C12 C13 H13 120.2 . . ?
C13 C14 C15 120.9(4) . . ?
C13 C14 H14 119.6 . . ?
C15 C14 H14 119.6 . . ?
C16 C15 C14 119.9(4) . . ?
C16 C15 H15 120.0 . . ?
C14 C15 H15 120.0 . . ?
C15 C16 C11 119.6(4) . . ?
C15 C16 H16 120.2 . . ?
C11 C16 H16 120.2 . . ?
N11 C20 N12 126.2(3) . . ?
N11 C20 C21 114.0(3) . . ?
N12 C20 C21 119.8(3) . . ?
N26 C21 C22 122.4(3) . . ?
N26 C21 C20 113.0(3) . . ?
C22 C21 C20 124.6(3) . . ?
C23 C22 C21 119.3(3) . . ?
C23 C22 H22 120.3 . . ?
C21 C22 H22 120.3 . . ?
C22 C23 C24 118.9(3) . . ?
C22 C23 H23 120.6 . . ?
C24 C23 H23 120.6 . . ?
C25 C24 C23 118.9(3) . . ?
C25 C24 H24 120.6 . . ?
C23 C24 H24 120.6 . . ?
N26 C25 C24 123.2(3) . . ?
N26 C25 H25 118.4 . . ?
C24 C25 H25 118.4 . . ?
C25 N26 C21 117.3(3) . . ?
C25 N26 Fe1 127.4(2) . . ?
C21 N26 Fe1 115.3(2) . . ?
N31 S31 C31 101.18(16) . . ?
C40 N31 S31 120.5(2) . . ?
C40 N31 Fe1 116.6(2) . . ?
S31 N31 Fe1 121.95(15) . . ?
C32 C31 C36 120.6(3) . . ?
C32 C31 S31 119.5(3) . . ?
C36 C31 S31 119.8(3) . . ?
C31 C32 C33 119.6(4) . . ?
C31 C32 N33 119.9(3) . . ?
C33 C32 N33 120.5(4) . . ?
C40 N33 C32 122.6(3) . . ?
C40 N33 H33A 118.7 . . ?
C32 N33 H33A 118.7 . . ?
C34 C33 C32 119.0(4) . . ?
C34 C33 H33 120.5 . . ?
C32 C33 H33 120.5 . . ?
C35 C34 C33 121.7(4) . . ?
C35 C34 H34 119.1 . . ?
C33 C34 H34 119.1 . . ?
C34 C35 C36 119.8(4) . . ?
C34 C35 H35 120.1 . . ?
C36 C35 H35 120.1 . . ?
C35 C36 C31 119.2(4) . . ?
C35 C36 H36 120.4 . . ?
C31 C36 H36 120.4 . . ?
N31 C40 N33 125.2(3) . . ?
N31 C40 C41 114.3(3) . . ?
N33 C40 C41 120.5(3) . . ?
N46 C41 C42 121.9(3) . . ?
N46 C41 C40 113.0(3) . . ?
C42 C41 C40 125.1(3) . . ?
C43 C42 C41 119.4(4) . . ?
C43 C42 H42 120.3 . . ?
C41 C42 H42 120.3 . . ?
C42 C43 C44 119.1(4) . . ?
C42 C43 H43 120.5 . . ?
C44 C43 H43 120.5 . . ?
C43 C44 C45 118.9(4) . . ?
C43 C44 H44 120.6 . . ?
C45 C44 H44 120.6 . . ?
N46 C45 C44 122.6(4) . . ?
N46 C45 H45 118.7 . . ?
C44 C45 H45 118.7 . . ?
C45 N46 C41 118.1(3) . . ?
C45 N46 Fe1 126.7(3) . . ?
C41 N46 Fe1 115.1(2) . . ?
N52 S51 C51 102.96(15) . . ?
C60 N51 C52 124.1(3) . . ?
C60 N51 H51 118.0 . . ?
C52 N51 H51 118.0 . . ?
C52 C51 C56 120.0(3) . . ?
C52 C51 S51 121.8(3) . . ?
C56 C51 S51 118.1(3) . . ?
C60 N52 S51 121.9(2) . . ?
C60 N52 Fe1 117.4(2) . . ?
S51 N52 Fe1 120.65(15) . . ?
C53 C52 C51 120.2(3) . . ?
C53 C52 N51 119.4(3) . . ?
C51 C52 N51 120.5(3) . . ?
C52 C53 C54 119.9(3) . . ?
C52 C53 H53 120.1 . . ?
C54 C53 H53 120.1 . . ?
C55 C54 C53 120.2(3) . . ?
C55 C54 H54 119.9 . . ?
C53 C54 H54 119.9 . . ?
C54 C55 C56 120.1(3) . . ?
C54 C55 H55 119.9 . . ?
C56 C55 H55 119.9 . . ?
C55 C56 C51 119.7(3) . . ?
C55 C56 H56 120.2 . . ?
C51 C56 H56 120.2 . . ?
N52 C60 N51 127.0(3) . . ?
N52 C60 C61 113.6(3) . . ?
N51 C60 C61 119.4(3) . . ?
N66 C61 C62 122.5(3) . . ?
N66 C61 C60 113.1(3) . . ?
C62 C61 C60 124.4(3) . . ?
C61 C62 C63 118.6(4) . . ?
C61 C62 H62 120.7 . . ?
C63 C62 H62 120.7 . . ?
C64 C63 C62 119.1(4) . . ?
C64 C63 H63 120.5 . . ?
C62 C63 H63 120.5 . . ?
C63 C64 C65 119.4(4) . . ?
C63 C64 H64 120.3 . . ?
C65 C64 H64 120.3 . . ?
N66 C65 C64 122.4(3) . . ?
N66 C65 H65 118.8 . . ?
C64 C65 H65 118.8 . . ?
C65 N66 C61 118.1(3) . . ?
C65 N66 Fe1 126.3(2) . . ?
C61 N66 Fe1 115.6(2) . . ?
O1B S1A O1C 110.1(6) . . ?
O1B S1A O1A 115.8(7) . . ?
O1C S1A O1A 119.9(7) . . ?
O1B S1A C1A 104.4(6) . . ?
O1C S1A C1A 96.3(6) . . ?
O1A S1A C1A 107.2(6) . . ?
F1A C1A F1B 107.3(8) . . ?
F1A C1A F1C 103.6(7) . . ?
F1B C1A F1C 109.0(8) . . ?
F1A C1A S1A 112.3(7) . . ?
F1B C1A S1A 108.4(7) . . ?
F1C C1A S1A 115.9(7) . . ?
O1E S1B O1F 117.3(7) . . ?
O1E S1B C1B 108.9(7) . . ?
O1F S1B C1B 109.4(7) . . ?
F1D C1B F1F 111.4(8) . . ?
F1D C1B F1E 104.0(7) . . ?
F1F C1B F1E 107.4(8) . . ?
F1D C1B S1B 113.3(7) . . ?
F1F C1B S1B 108.8(7) . . ?
F1E C1B S1B 111.8(7) . . ?
O2A S2A O2B 125.6(6) . . ?
O2A S2A O2C 111.7(5) . . ?
O2B S2A O2C 115.3(6) . . ?
O2A S2A C2A 106.6(5) . . ?
O2B S2A C2A 86.7(5) . . ?
O2C S2A C2A 104.7(5) . . ?
F2B C2A F2A 110.2(8) . . ?
F2B C2A F2C 112.7(9) . . ?
F2A C2A F2C 106.9(8) . . ?
F2B C2A S2A 108.7(7) . . ?
F2A C2A S2A 109.3(7) . . ?
F2C C2A S2A 109.1(7) . . ?
O2F S2B O2E 116.7(5) . . ?
O2F S2B C2B 107.0(5) . . ?
O2E S2B C2B 117.5(5) . . ?
F2E C2B F2F 106.7(6) . . ?
F2E C2B F2D 108.4(7) . . ?
F2F C2B F2D 99.8(6) . . ?
F2E C2B S2B 112.0(6) . . ?
F2F C2B S2B 117.6(6) . . ?
F2D C2B S2B 111.5(6) . . ?

_refine_diff_density_max         1.704
_refine_diff_density_min         -0.841
_refine_diff_density_rms         0.107

_shelxl_version_number           2013-3


_database_code_depnum_ccdc_archive 'CCDC 1002538'
#######################################################################
#
#                 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_cmpnd_4

# start Validation Reply Form
_vrf_PLAT097_cmpnd_4             
;
PROBLEM: Large reported max(positive) residual electron density 2.04 eA-3
RESPONSE: The two highest residual electron density peaks occur within 1A
of vanadium (Q1) and a chlorine atom (Q2). 
;

# end Validation Reply Form

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C24 H18 Cl N6 O S2 V, C H4 O, Cl'
_chemical_formula_sum            'C25 H22 Cl2 N6 O2 S2 V'
_chemical_formula_weight         624.44

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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

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

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

_cell_length_a                   12.606(6)
_cell_length_b                   12.609(6)
_cell_length_c                   17.194(8)
_cell_angle_alpha                90
_cell_angle_beta                 96.886(5)
_cell_angle_gamma                90
_cell_volume                     2713(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    5196
_cell_measurement_theta_min      2.29
_cell_measurement_theta_max      26.73

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.529
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1276
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.160
_exptl_crystal_size_min          0.060
_exptl_absorpt_coefficient_mu    0.752
_shelx_estimated_absorpt_T_min   0.864
_shelx_estimated_absorpt_T_max   0.956
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.608
_exptl_absorpt_correction_T_max  0.746
_exptl_absorpt_process_details   sadabs

_exptl_special_details           
;
 SAINT, Bruker AXS, Wisconsin, USA.
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'sealed tube'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            29057
_diffrn_reflns_av_unetI/netI     0.0528
_diffrn_reflns_av_R_equivalents  0.0587
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_theta_min         1.899
_diffrn_reflns_theta_max         27.498
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.992
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             6191
_reflns_number_gt                4172
_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       'Bruker APEX2'
_computing_cell_refinement       'Bruker SAINT'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

_refine_special_details          
;
Structure solved by direct methods to reveal all non-H atoms
which were refined anisotropically. H atoms added at calculated
positions and refined using a riding model. 
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0824P)²+10.8399P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     'direct methods'
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    constr
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         6191
_refine_ls_number_parameters     345
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1208
_refine_ls_R_factor_gt           0.0770
_refine_ls_wR_factor_ref         0.2139
_refine_ls_wR_factor_gt          0.1841
_refine_ls_goodness_of_fit_ref   1.071
_refine_ls_restrained_S_all      1.071
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
V1 V 0.21319(9) 0.40003(7) 0.13333(5) 0.0421(3) Uani 1 1 d . . . . .
S1 S 0.42677(13) 0.52899(12) 0.06892(8) 0.0433(4) Uani 1 1 d . . . . .
O1 O 0.0966(2) 0.3213(3) 0.14333(17) 0.0315(8) Uani 1 1 d . . . . .
S2 S 0.13292(11) 0.62949(10) 0.20608(7) 0.0351(3) Uani 1 1 d . . . . .
Cl2 Cl 0.32073(13) 0.25925(13) 0.12042(9) 0.0534(4) Uani 1 1 d . . . . .
N11 N 0.3590(3) 0.5025(3) 0.1464(2) 0.0288(9) Uani 1 1 d . . . . .
C11 C 0.4880(4) 0.6506(4) 0.0992(3) 0.0327(11) Uani 1 1 d . . . . .
N12 N 0.4822(3) 0.5958(3) 0.2338(2) 0.0322(9) Uani 1 1 d . . . . .
H12A H 0.5186 0.5923 0.2808 0.039 Uiso 1 1 calc R U . . .
C12 C 0.5139(5) 0.7235(5) 0.0446(3) 0.0408(13) Uani 1 1 d . . . . .
H12 H 0.4948 0.7110 -0.0097 0.049 Uiso 1 1 calc R U . . .
N13 N 0.2598(3) 0.4212(3) 0.2553(2) 0.0295(9) Uani 1 1 d . . . . .
C13 C 0.5682(5) 0.8151(4) 0.0702(3) 0.0425(13) Uani 1 1 d . . . . .
H13 H 0.5861 0.8661 0.0332 0.051 Uiso 1 1 calc R U . . .
C14 C 0.5962(5) 0.8321(4) 0.1491(3) 0.0410(13) Uani 1 1 d . . . . .
H14 H 0.6357 0.8938 0.1661 0.049 Uiso 1 1 calc R U . . .
C15 C 0.5677(4) 0.7609(4) 0.2037(3) 0.0354(12) Uani 1 1 d . . . . .
H15 H 0.5845 0.7749 0.2581 0.043 Uiso 1 1 calc R U . . .
C16 C 0.5144(4) 0.6690(4) 0.1789(3) 0.0293(10) Uani 1 1 d . . . . .
C20 C 0.3974(4) 0.5312(4) 0.2163(3) 0.0261(10) Uani 1 1 d . . . . .
N21 N 0.1400(3) 0.5524(3) 0.1246(2) 0.0294(9) Uani 1 1 d . . . . .
C21 C 0.3416(4) 0.4876(4) 0.2804(3) 0.0278(10) Uani 1 1 d . . . . .
N22 N 0.0820(4) 0.6918(3) 0.0393(3) 0.0355(10) Uani 1 1 d . . . . .
H22A H 0.0935 0.7225 -0.0048 0.043 Uiso 1 1 calc R U . . .
C22 C 0.3693(5) 0.5110(5) 0.3579(3) 0.0395(13) Uani 1 1 d . . . . .
H22 H 0.4254 0.5595 0.3739 0.047 Uiso 1 1 calc R U . . .
N23 N 0.1959(3) 0.4342(3) 0.0118(2) 0.0300(9) Uani 1 1 d . . . . .
C23 C 0.3127(5) 0.4614(5) 0.4132(3) 0.0490(15) Uani 1 1 d . . . . .
H23 H 0.3310 0.4744 0.4675 0.059 Uiso 1 1 calc R U . . .
C24 C 0.2306(5) 0.3939(5) 0.3879(3) 0.0439(14) Uani 1 1 d . . . . .
H24 H 0.1909 0.3601 0.4244 0.053 Uiso 1 1 calc R U . . .
C25 C 0.2064(4) 0.3754(4) 0.3086(3) 0.0362(12) Uani 1 1 d . . . . .
H25 H 0.1495 0.3283 0.2914 0.043 Uiso 1 1 calc R U . . .
C31 C 0.0355(4) 0.7229(4) 0.1697(3) 0.0324(11) Uani 1 1 d . . . . .
C32 C -0.0253(4) 0.7745(4) 0.2201(3) 0.0364(12) Uani 1 1 d . . . . .
H32 H -0.0169 0.7577 0.2744 0.044 Uiso 1 1 calc R U . . .
C33 C -0.0988(5) 0.8511(4) 0.1904(3) 0.0415(13) Uani 1 1 d . . . . .
H33 H -0.1393 0.8882 0.2248 0.050 Uiso 1 1 calc R U . . .
C34 C -0.1131(5) 0.8735(4) 0.1118(4) 0.0418(13) Uani 1 1 d . . . . .
H34 H -0.1639 0.9255 0.0921 0.050 Uiso 1 1 calc R U . . .
C35 C -0.0538(4) 0.8206(4) 0.0608(3) 0.0383(12) Uani 1 1 d . . . . .
H35 H -0.0650 0.8349 0.0061 0.046 Uiso 1 1 calc R U . . .
C36 C 0.0220(4) 0.7466(4) 0.0906(3) 0.0336(11) Uani 1 1 d . . . . .
C40 C 0.1225(4) 0.5938(4) 0.0554(3) 0.0285(10) Uani 1 1 d . . . . .
C41 C 0.1497(4) 0.5277(4) -0.0105(3) 0.0290(10) Uani 1 1 d . . . . .
C42 C 0.1315(4) 0.5579(4) -0.0877(3) 0.0373(12) Uani 1 1 d . . . . .
H42 H 0.0971 0.6233 -0.1020 0.045 Uiso 1 1 calc R U . . .
C43 C 0.1643(5) 0.4911(5) -0.1445(3) 0.0424(13) Uani 1 1 d . . . . .
H43 H 0.1537 0.5107 -0.1982 0.051 Uiso 1 1 calc R U . . .
C44 C 0.2119(4) 0.3970(4) -0.1223(3) 0.0352(12) Uani 1 1 d . . . . .
H44 H 0.2348 0.3501 -0.1603 0.042 Uiso 1 1 calc R U . . .
C45 C 0.2265(4) 0.3707(4) -0.0435(3) 0.0324(11) Uani 1 1 d . . . . .
H45 H 0.2595 0.3050 -0.0282 0.039 Uiso 1 1 calc R U . . .
Cl3 Cl 0.11670(12) 0.84395(10) -0.10105(7) 0.0407(3) Uani 1 1 d . . . . .
O1S O 0.3126(4) 0.9194(4) -0.1777(3) 0.0654(13) Uani 1 1 d . . . . .
H1S H 0.2537 0.8977 -0.1656 0.098 Uiso 1 1 calc R U . . .
C1S C 0.3951(7) 0.8880(7) -0.1197(5) 0.080(2) Uani 1 1 d . . . . .
H1S1 H 0.3921 0.8110 -0.1124 0.120 Uiso 1 1 calc R U . . .
H1S2 H 0.3863 0.9237 -0.0703 0.120 Uiso 1 1 calc R U . . .
H1S3 H 0.4644 0.9073 -0.1362 0.120 Uiso 1 1 calc R U . . .


_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
V1 O1 1.799(3) . ?
V1 N23 2.120(4) . ?
V1 N13 2.125(4) . ?
V1 N21 2.129(4) . ?
V1 N11 2.236(4) . ?
V1 Cl2 2.261(2) . ?
S1 N11 1.699(4) . ?
S1 C11 1.766(5) . ?
S2 N21 1.715(4) . ?
S2 C31 1.761(5) . ?
N11 C20 1.292(6) . ?
C11 C12 1.381(7) . ?
C11 C16 1.389(7) . ?
N12 C20 1.350(6) . ?
N12 C16 1.415(6) . ?
N12 H12A 0.8800 . ?
C12 C13 1.387(8) . ?
C12 H12 0.9500 . ?
N13 C25 1.333(6) . ?
N13 C21 1.359(6) . ?
C13 C14 1.378(8) . ?
C13 H13 0.9500 . ?
C14 C15 1.378(7) . ?
C14 H14 0.9500 . ?
C15 C16 1.381(7) . ?
C15 H15 0.9500 . ?
C20 C21 1.483(6) . ?
N21 C40 1.294(6) . ?
C21 C22 1.369(7) . ?
N22 C40 1.352(6) . ?
N22 C36 1.409(6) . ?
N22 H22A 0.8800 . ?
C22 C23 1.403(7) . ?
C22 H22 0.9500 . ?
N23 C45 1.335(6) . ?
N23 C41 1.349(6) . ?
C23 C24 1.369(8) . ?
C23 H23 0.9500 . ?
C24 C25 1.380(8) . ?
C24 H24 0.9500 . ?
C25 H25 0.9500 . ?
C31 C36 1.383(7) . ?
C31 C32 1.386(7) . ?
C32 C33 1.393(8) . ?
C32 H32 0.9500 . ?
C33 C34 1.372(8) . ?
C33 H33 0.9500 . ?
C34 C35 1.389(8) . ?
C34 H34 0.9500 . ?
C35 C36 1.389(7) . ?
C35 H35 0.9500 . ?
C40 C41 1.480(7) . ?
C41 C42 1.374(7) . ?
C42 C43 1.390(7) . ?
C42 H42 0.9500 . ?
C43 C44 1.364(8) . ?
C43 H43 0.9500 . ?
C44 C45 1.386(7) . ?
C44 H44 0.9500 . ?
C45 H45 0.9500 . ?
O1S C1S 1.409(9) . ?
O1S H1S 0.8400 . ?
C1S H1S1 0.9800 . ?
C1S H1S2 0.9800 . ?
C1S H1S3 0.9800 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 V1 N23 102.58(15) . . ?
O1 V1 N13 96.17(15) . . ?
N23 V1 N13 158.56(16) . . ?
O1 V1 N21 98.77(17) . . ?
N23 V1 N21 75.80(15) . . ?
N13 V1 N21 91.25(16) . . ?
O1 V1 N11 168.69(15) . . ?
N23 V1 N11 88.15(15) . . ?
N13 V1 N11 72.65(15) . . ?
N21 V1 N11 80.21(16) . . ?
O1 V1 Cl2 94.74(13) . . ?
N23 V1 Cl2 93.15(12) . . ?
N13 V1 Cl2 95.60(12) . . ?
N21 V1 Cl2 164.11(13) . . ?
N11 V1 Cl2 88.16(13) . . ?
N11 S1 C11 100.5(2) . . ?
N21 S2 C31 101.0(2) . . ?
C20 N11 S1 120.4(3) . . ?
C20 N11 V1 117.8(3) . . ?
S1 N11 V1 121.3(2) . . ?
C12 C11 C16 120.7(5) . . ?
C12 C11 S1 120.5(4) . . ?
C16 C11 S1 118.7(4) . . ?
C20 N12 C16 121.8(4) . . ?
C20 N12 H12A 119.1 . . ?
C16 N12 H12A 119.1 . . ?
C11 C12 C13 119.2(5) . . ?
C11 C12 H12 120.4 . . ?
C13 C12 H12 120.4 . . ?
C25 N13 C21 118.4(4) . . ?
C25 N13 V1 121.4(4) . . ?
C21 N13 V1 120.1(3) . . ?
C14 C13 C12 120.0(5) . . ?
C14 C13 H13 120.0 . . ?
C12 C13 H13 120.0 . . ?
C15 C14 C13 120.8(5) . . ?
C15 C14 H14 119.6 . . ?
C13 C14 H14 119.6 . . ?
C14 C15 C16 119.6(5) . . ?
C14 C15 H15 120.2 . . ?
C16 C15 H15 120.2 . . ?
C15 C16 C11 119.7(5) . . ?
C15 C16 N12 120.5(4) . . ?
C11 C16 N12 119.7(4) . . ?
N11 C20 N12 125.1(4) . . ?
N11 C20 C21 115.5(4) . . ?
N12 C20 C21 119.4(4) . . ?
C40 N21 S2 120.2(3) . . ?
C40 N21 V1 117.0(3) . . ?
S2 N21 V1 121.2(2) . . ?
N13 C21 C22 122.5(4) . . ?
N13 C21 C20 113.7(4) . . ?
C22 C21 C20 123.8(5) . . ?
C40 N22 C36 122.6(4) . . ?
C40 N22 H22A 118.7 . . ?
C36 N22 H22A 118.7 . . ?
C21 C22 C23 118.2(5) . . ?
C21 C22 H22 120.9 . . ?
C23 C22 H22 120.9 . . ?
C45 N23 C41 118.3(4) . . ?
C45 N23 V1 125.1(3) . . ?
C41 N23 V1 116.6(3) . . ?
C24 C23 C22 119.3(5) . . ?
C24 C23 H23 120.4 . . ?
C22 C23 H23 120.4 . . ?
C23 C24 C25 119.2(5) . . ?
C23 C24 H24 120.4 . . ?
C25 C24 H24 120.4 . . ?
N13 C25 C24 122.4(5) . . ?
N13 C25 H25 118.8 . . ?
C24 C25 H25 118.8 . . ?
C36 C31 C32 120.1(5) . . ?
C36 C31 S2 119.5(4) . . ?
C32 C31 S2 120.4(4) . . ?
C31 C32 C33 119.3(5) . . ?
C31 C32 H32 120.3 . . ?
C33 C32 H32 120.3 . . ?
C34 C33 C32 120.5(5) . . ?
C34 C33 H33 119.8 . . ?
C32 C33 H33 119.8 . . ?
C33 C34 C35 120.4(5) . . ?
C33 C34 H34 119.8 . . ?
C35 C34 H34 119.8 . . ?
C34 C35 C36 119.2(5) . . ?
C34 C35 H35 120.4 . . ?
C36 C35 H35 120.4 . . ?
C31 C36 C35 120.4(5) . . ?
C31 C36 N22 119.8(4) . . ?
C35 C36 N22 119.8(5) . . ?
N21 C40 N22 125.1(4) . . ?
N21 C40 C41 116.5(4) . . ?
N22 C40 C41 118.4(4) . . ?
N23 C41 C42 122.2(5) . . ?
N23 C41 C40 114.0(4) . . ?
C42 C41 C40 123.8(4) . . ?
C41 C42 C43 118.8(5) . . ?
C41 C42 H42 120.6 . . ?
C43 C42 H42 120.6 . . ?
C44 C43 C42 119.3(5) . . ?
C44 C43 H43 120.4 . . ?
C42 C43 H43 120.4 . . ?
C43 C44 C45 118.9(5) . . ?
C43 C44 H44 120.5 . . ?
C45 C44 H44 120.5 . . ?
N23 C45 C44 122.5(5) . . ?
N23 C45 H45 118.7 . . ?
C44 C45 H45 118.7 . . ?
C1S O1S H1S 109.5 . . ?
O1S C1S H1S1 109.5 . . ?
O1S C1S H1S2 109.5 . . ?
H1S1 C1S H1S2 109.5 . . ?
O1S C1S H1S3 109.5 . . ?
H1S1 C1S H1S3 109.5 . . ?
H1S2 C1S H1S3 109.5 . . ?

_refine_diff_density_max         2.039
_refine_diff_density_min         -1.470
_refine_diff_density_rms         0.118

_shelxl_version_number           2013-3

_database_code_depnum_ccdc_archive 'CCDC 1002539'
