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

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#                 Cambridge Crystallographic Data Centre
#                                CCDC 
# 
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# 
#  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.
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#  fide research purposes only. It may contain copyright material
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data_Fe_TMC_NCS

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            'iron(II) TMC thiocyanate triflate'
_chemical_formula_moiety         'C19 F3 Fe N7 O3 S2'
_chemical_formula_sum            'C19 F3 Fe N7 O3 S2'
_chemical_formula_weight         551.23

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'
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'

_symmetry_cell_setting           Orthorhombic
_symmetry_space_group_name_H-M   Pnma

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

_cell_length_a                   24.2856(5)
_cell_length_b                   12.7122(3)
_cell_length_c                   9.1833(2)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     2835.10(11)
_cell_formula_units_Z            4
_cell_measurement_temperature    170(2)
_cell_measurement_reflns_used    9895
_cell_measurement_theta_min      2.32
_cell_measurement_theta_max      27.62

_exptl_crystal_description       Needle
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    1.291
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1088
_exptl_absorpt_coefficient_mu    0.728
_exptl_absorpt_correction_type   none
_exptl_absorpt_correction_T_min  0.9785
_exptl_absorpt_correction_T_max  0.9928
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      170(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       '\f and \w scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            46265
_diffrn_reflns_av_R_equivalents  0.0323
_diffrn_reflns_av_sigmaI/netI    0.0148
_diffrn_reflns_limit_h_min       -31
_diffrn_reflns_limit_h_max       31
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         2.32
_diffrn_reflns_theta_max         27.50
_reflns_number_total             3348
_reflns_number_gt                2805
_reflns_threshold_expression     >2sigma(I)

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

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[\s^2^(Fo^2^)+(0.2000P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   none
_refine_ls_hydrogen_treatment    none
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       ?
_refine_ls_number_reflns         3348
_refine_ls_number_parameters     244
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0769
_refine_ls_R_factor_gt           0.0680
_refine_ls_wR_factor_ref         0.2413
_refine_ls_wR_factor_gt          0.2209
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_restrained_S_all      1.093
_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
Fe1 Fe 0.185668(19) 0.2500 0.08031(5) 0.0291(3) Uani 1 2 d S . 1
S1 S 0.33758(6) 0.2500 0.40481(15) 0.0576(4) Uani 1 2 d S . 1
C8 C 0.1224(2) 0.2500 0.3612(5) 0.0544(11) Uani 1 2 d S . 1
N4 N 0.24923(16) 0.2500 0.2158(4) 0.0470(9) Uani 1 2 d S . 1
C1 C 0.26921(16) 0.2500 -0.1587(5) 0.0404(9) Uani 1 2 d S . 1
C4 C 0.19878(16) 0.0124(3) 0.1350(4) 0.0502(8) Uani 1 1 d . . 1
C5 C 0.11125(13) 0.0627(3) 0.0315(5) 0.0528(8) Uani 1 1 d . . 1
C9 C 0.28572(17) 0.2500 0.2946(4) 0.0377(8) Uani 1 2 d S . 1
N2 N 0.17102(10) 0.08278(18) 0.0302(3) 0.0340(5) Uani 1 1 d . . 1
N1 N 0.20804(12) 0.2500 -0.1487(3) 0.0296(6) Uani 1 2 d S . 1
N5 N 0.15496(14) 0.9751(3) 0.5081(4) 0.0638(9) Uani 1 1 d . A 1
C3 C 0.19422(13) 0.0606(2) -0.1169(3) 0.0368(6) Uani 1 1 d . . 1
C2 C 0.18509(11) 0.1548(2) -0.2166(3) 0.0350(6) Uani 1 1 d . . 1
C7 C 0.0628(3) 0.2078(5) 0.1539(8) 0.0506(15) Uani 0.50 1 d P . 1
N3 N 0.11044(17) 0.2500 0.2066(5) 0.0800(19) Uani 1 2 d S . 1
F2 F 0.9136(2) 0.3192(6) 0.7480(8) 0.208(3) Uani 1 1 d . . 1
C10 C 0.9467(2) 0.2500 0.7930(7) 0.078(2) Uani 1 2 d S . 1
C11 C 0.11597(17) 0.9508(3) 0.5674(4) 0.0542(9) Uani 1 1 d . A 1
S2 S 1.0094(4) 0.274(4) 0.7043(11) 0.059(9) Uani 0.25 1 d P . 1
F1 F 0.9517(5) 0.283(3) 0.9338(11) 0.083(11) Uani 0.25 1 d P . 1
O2 O 1.0036(7) 0.258(6) 0.5647(19) 0.115(12) Uani 0.35 1 d P . 1
C6 C 0.0938(3) 0.1132(6) 0.1906(8) 0.0425(14) Uani 0.50 1 d P . 1
C12 C 0.0633(14) 0.916(4) 0.625(3) 0.152(14) Uani 0.50 1 d P A 1
O1 O 1.0496(3) 0.2154(10) 0.7754(9) 0.114(6) Uani 0.50 1 d P . 1
S2* S 1.0111(3) 0.226(2) 0.7059(9) 0.038(4) Uani 0.25 1 d P . 2
F1* F 0.9501(10) 0.196(2) 0.917(2) 0.144(13) Uani 0.25 1 d P . 2
O2* O 0.9919(14) 0.213(3) 0.560(4) 0.059(9) Uani 0.15 1 d P . 2
C6* C 0.0740(3) 0.0908(6) 0.1447(9) 0.0452(16) Uani 0.50 1 d P B 2
C12* C 0.0694(10) 0.918(2) 0.657(2) 0.087(5) Uani 0.50 1 d P C 2
O1* O 1.0233(6) 0.1258(13) 0.721(2) 0.192(8) Uani 0.50 1 d P . 2

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Fe1 0.0291(4) 0.0352(4) 0.0230(4) 0.000 -0.00217(16) 0.000
S1 0.0596(8) 0.0492(7) 0.0640(8) 0.000 -0.0348(6) 0.000
C8 0.058(3) 0.076(3) 0.029(2) 0.000 0.0119(18) 0.000
N4 0.0422(18) 0.061(2) 0.0384(19) 0.000 -0.0111(15) 0.000
C1 0.0339(18) 0.049(2) 0.038(2) 0.000 0.0043(15) 0.000
C4 0.0658(19) 0.0469(18) 0.0380(17) 0.0123(13) -0.0061(14) 0.0073(15)
C5 0.0434(16) 0.0443(18) 0.071(2) 0.0148(16) 0.0108(15) -0.0029(12)
C9 0.044(2) 0.0341(18) 0.035(2) 0.000 -0.0093(15) 0.000
N2 0.0407(11) 0.0315(12) 0.0299(11) 0.0035(9) 0.0006(9) -0.0004(9)
N1 0.0316(14) 0.0305(14) 0.0267(15) 0.000 -0.0004(11) 0.000
N5 0.0666(19) 0.080(2) 0.0452(17) -0.0063(15) 0.0011(14) -0.0034(16)
C3 0.0494(15) 0.0285(13) 0.0326(13) 0.0003(11) 0.0015(11) 0.0044(10)
C2 0.0492(15) 0.0285(13) 0.0272(12) -0.0026(10) -0.0006(9) -0.0023(9)
C7 0.033(3) 0.058(3) 0.061(4) -0.003(3) 0.013(3) -0.004(2)
N3 0.035(2) 0.172(6) 0.033(2) 0.000 0.0101(16) 0.000
F2 0.161(4) 0.280(8) 0.184(4) 0.033(5) 0.033(4) 0.149(5)
C10 0.025(2) 0.135(6) 0.074(4) 0.000 0.006(2) 0.000
C11 0.060(2) 0.060(2) 0.0427(17) -0.0090(14) -0.0057(15) -0.0086(16)
S2 0.037(4) 0.09(2) 0.055(5) -0.019(8) 0.001(3) 0.018(6)
F1 0.032(5) 0.19(3) 0.030(4) 0.029(10) 0.010(3) 0.026(8)
O2 0.041(9) 0.25(3) 0.050(5) 0.037(16) -0.009(4) 0.063(18)
C6 0.042(4) 0.047(4) 0.038(4) 0.000(3) 0.007(3) -0.001(3)
C12 0.062(10) 0.35(4) 0.044(10) 0.011(13) -0.019(7) -0.037(13)
O1 0.060(3) 0.201(18) 0.080(4) 0.014(5) -0.005(3) 0.061(7)
S2* 0.020(3) 0.054(9) 0.041(4) -0.021(5) -0.003(2) 0.019(5)
F1* 0.101(15) 0.19(3) 0.137(17) 0.111(18) 0.036(12) -0.040(13)
O2* 0.017(11) 0.098(18) 0.063(13) -0.059(13) -0.009(8) -0.028(14)
C6* 0.045(4) 0.046(4) 0.044(4) 0.003(3) 0.003(3) -0.013(3)
C12* 0.046(6) 0.168(14) 0.045(10) 0.007(7) -0.017(6) -0.048(7)
O1* 0.170(14) 0.149(14) 0.256(19) -0.035(13) -0.051(13) 0.096(11)

_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 N4 1.983(4) . ?
Fe1 N3 2.164(4) . ?
Fe1 N1 2.172(3) . ?
Fe1 N2 2.204(2) 7_565 ?
Fe1 N2 2.204(2) . ?
S1 C9 1.616(4) . ?
C8 N3 1.450(6) . ?
N4 C9 1.144(6) . ?
C1 N1 1.488(5) . ?
C4 N2 1.477(4) . ?
C5 N2 1.474(4) . ?
C5 C6 1.650(8) . ?
N2 C3 1.491(4) . ?
N1 C2 1.471(3) . ?
N1 C2 1.471(3) 7_565 ?
N5 C11 1.135(5) . ?
C3 C2 1.524(4) . ?
C7 C7 1.073(14) 7_565 ?
C7 N3 1.365(8) . ?
C7 C6 1.459(10) . ?
N3 C7 1.365(8) 7_565 ?
N3 C6 1.792(8) 7_565 ?
N3 C6 1.792(8) . ?
F2 C10 1.261(6) . ?
F2 F2 1.759(16) 7_565 ?
C10 F2 1.261(6) 7_565 ?
C10 F1 1.363(17) . ?
C10 F1 1.363(17) 7_565 ?
C10 S2 1.752(11) 7_565 ?
C10 S2 1.752(11) . ?
C11 C12 1.45(3) . ?
S2 S2 0.60(10) 7_565 ?
S2 O1 1.183(13) 7_565 ?
S2 O2 1.31(3) . ?
S2 O2 1.35(3) 7_565 ?
S2 O1 1.39(3) . ?
F1 F1 0.83(7) 7_565 ?
O2 O2 0.20(15) 7_565 ?
O2 S2 1.35(3) 7_565 ?
O1 O1 0.88(2) 7_565 ?
O1 S2 1.183(13) 7_565 ?
S2* S2* 0.62(6) 7_565 ?
S2* O1* 1.31(3) . ?
S2* O2* 1.43(4) . ?
S2* O2* 1.62(3) 7_565 ?
S2* O1* 1.92(3) 7_565 ?
F1* F1* 1.36(6) 7_565 ?
O2* O2* 0.95(9) 7_565 ?
O2* S2* 1.62(3) 7_565 ?
O1* S2* 1.92(3) 7_565 ?

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
N4 Fe1 N3 108.72(17) . . ?
N4 Fe1 N1 114.39(15) . . ?
N3 Fe1 N1 136.89(14) . . ?
N4 Fe1 N2 104.88(6) . 7_565 ?
N3 Fe1 N2 88.61(7) . 7_565 ?
N1 Fe1 N2 80.68(6) . 7_565 ?
N4 Fe1 N2 104.88(6) . . ?
N3 Fe1 N2 88.61(7) . . ?
N1 Fe1 N2 80.68(6) . . ?
N2 Fe1 N2 149.39(12) 7_565 . ?
C9 N4 Fe1 179.6(4) . . ?
N2 C5 C6 101.1(4) . . ?
N4 C9 S1 179.6(4) . . ?
C5 N2 C4 109.8(3) . . ?
C5 N2 C3 110.3(3) . . ?
C4 N2 C3 107.7(2) . . ?
C5 N2 Fe1 108.90(19) . . ?
C4 N2 Fe1 112.0(2) . . ?
C3 N2 Fe1 108.12(16) . . ?
C2 N1 C2 110.7(3) . 7_565 ?
C2 N1 C1 110.60(19) . . ?
C2 N1 C1 110.60(19) 7_565 . ?
C2 N1 Fe1 108.41(16) . . ?
C2 N1 Fe1 108.41(16) 7_565 . ?
C1 N1 Fe1 108.0(2) . . ?
N2 C3 C2 109.9(2) . . ?
N1 C2 C3 109.7(2) . . ?
C7 C7 N3 66.9(3) 7_565 . ?
C7 C7 C6 145.5(4) 7_565 . ?
N3 C7 C6 78.7(5) . . ?
C7 N3 C7 46.3(6) . 7_565 ?
C7 N3 C8 121.2(4) . . ?
C7 N3 C8 121.2(4) 7_565 . ?
C7 N3 C6 99.3(4) . 7_565 ?
C7 N3 C6 53.0(4) 7_565 7_565 ?
C8 N3 C6 97.2(3) . 7_565 ?
C7 N3 C6 53.0(4) . . ?
C7 N3 C6 99.3(4) 7_565 . ?
C8 N3 C6 97.2(3) . . ?
C6 N3 C6 152.2(6) 7_565 . ?
C7 N3 Fe1 121.8(4) . . ?
C7 N3 Fe1 121.8(4) 7_565 . ?
C8 N3 Fe1 110.8(3) . . ?
C6 N3 Fe1 98.4(2) 7_565 . ?
C6 N3 Fe1 98.4(2) . . ?
C10 F2 F2 45.8(4) . 7_565 ?
F2 C10 F2 88.4(9) 7_565 . ?
F2 C10 F1 125.4(11) 7_565 . ?
F2 C10 F1 98.9(11) . . ?
F2 C10 F1 98.9(11) 7_565 7_565 ?
F2 C10 F1 125.4(11) . 7_565 ?
F1 C10 F1 35(3) . 7_565 ?
F2 C10 S2 106.3(14) 7_565 7_565 ?
F2 C10 S2 121.4(13) . 7_565 ?
F1 C10 S2 114.6(8) . 7_565 ?
F1 C10 S2 108.2(10) 7_565 7_565 ?
F2 C10 S2 121.4(13) 7_565 . ?
F2 C10 S2 106.3(14) . . ?
F1 C10 S2 108.2(10) . . ?
F1 C10 S2 114.6(8) 7_565 . ?
S2 C10 S2 20(3) 7_565 . ?
N5 C11 C12 172.7(11) . . ?
S2 S2 O1 97(2) 7_565 7_565 ?
S2 S2 O2 81(4) 7_565 . ?
O1 S2 O2 130.4(11) 7_565 . ?
S2 S2 O2 73(4) 7_565 7_565 ?
O1 S2 O2 130.1(15) 7_565 7_565 ?
O2 S2 O2 8(6) . 7_565 ?
S2 S2 O1 57.8(18) 7_565 . ?
O1 S2 O1 39.0(13) 7_565 . ?
O2 S2 O1 117(3) . . ?
O2 S2 O1 111(3) 7_565 . ?
S2 S2 C10 80.1(16) 7_565 . ?
O1 S2 C10 118.7(8) 7_565 . ?
O2 S2 C10 109.8(18) . . ?
O2 S2 C10 107.5(14) 7_565 . ?
O1 S2 C10 107.5(18) . . ?
F1 F1 C10 72.3(13) 7_565 . ?
O2 O2 S2 99(4) 7_565 . ?
O2 O2 S2 73(4) 7_565 7_565 ?
S2 O2 S2 26(4) . 7_565 ?
C7 C6 C5 104.4(5) . . ?
C7 C6 N3 48.3(4) . . ?
C5 C6 N3 113.1(4) . . ?
O1 O1 S2 83(2) 7_565 7_565 ?
O1 O1 S2 57.8(18) 7_565 . ?
S2 O1 S2 25(4) 7_565 . ?
S2* S2* O1* 165.5(9) 7_565 . ?
S2* S2* O2* 97(2) 7_565 . ?
O1* S2* O2* 94(3) . . ?
S2* S2* O2* 61(2) 7_565 7_565 ?
O1* S2* O2* 129(2) . 7_565 ?
O2* S2* O2* 36(4) . 7_565 ?
S2* S2* O1* 9.8(5) 7_565 7_565 ?
O1* S2* O1* 155.7(14) . 7_565 ?
O2* S2* O1* 103(2) . 7_565 ?
O2* S2* O1* 68(2) 7_565 7_565 ?
O2* O2* S2* 83(2) 7_565 . ?
O2* O2* S2* 61(2) 7_565 7_565 ?
S2* O2* S2* 22(2) . 7_565 ?
S2* O1* S2* 4.6(5) . 7_565 ?

_diffrn_measured_fraction_theta_max 0.985
_diffrn_reflns_theta_full        27.50
_diffrn_measured_fraction_theta_full 0.985
_refine_diff_density_max         0.865
_refine_diff_density_min         -1.051
_refine_diff_density_rms         0.121
_database_code_depnum_ccdc_archive 'CCDC 959085'