# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2016

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx
_database_code_depnum_ccdc_archive 'CCDC 1452167'
_audit_update_record             
;
2016-02-08 deposited with the CCDC.
2016-04-22 downloaded from the CCDC.
;
_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C8 H24 F1.33 Mn2 N2.67 O12 S2.67'
_chemical_formula_weight         570.34

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Mn Mn -0.5299 2.8052 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           13
_space_group_name_H-M_alt        'P 2/c'
_space_group_name_Hall           '-P 2yc'

_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, -y, -z'
'x, -y, z-1/2'

_cell_length_a                   12.0101(5)
_cell_length_b                   5.6681(2)
_cell_length_c                   20.4103(8)
_cell_angle_alpha                90
_cell_angle_beta                 90.425(4)
_cell_angle_gamma                90
_cell_volume                     1389.38(9)
_cell_formula_units_Z            3
_cell_measurement_temperature    150.87(10)
_cell_measurement_reflns_used    3643
_cell_measurement_theta_min      4.2600
_cell_measurement_theta_max      71.6950

_exptl_crystal_description       Rod
_exptl_crystal_colour            'Pale pink'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.045
_exptl_crystal_F_000             874
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_exptl_absorpt_coefficient_mu    14.674
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.95027
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;


_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150.87(10)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'sealed X-ray tube'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_reflns_number            6311
_diffrn_reflns_av_unetI/netI     0.0382
_diffrn_reflns_av_R_equivalents  0.0294
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_theta_min         5.668
_diffrn_reflns_theta_max         71.939
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.933
_diffrn_measured_fraction_theta_full 'ACTA 50'
_diffrn_reflns_Laue_measured_fraction_max 0.933
_diffrn_reflns_Laue_measured_fraction_full 0.946
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_point_group_measured_fraction_full 0.946
_reflns_number_total             2539
_reflns_number_gt                2281
_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0311P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2539
_refine_ls_number_parameters     268
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0294
_refine_ls_R_factor_gt           0.0256
_refine_ls_wR_factor_ref         0.0604
_refine_ls_wR_factor_gt          0.0591
_refine_ls_goodness_of_fit_ref   1.003
_refine_ls_restrained_S_all      1.003
_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
C1 C -0.63268(18) 0.8907(4) 0.65494(11) 0.0120(4) Uani 1 1 d . . . . .
C2 C -0.61564(19) 1.0468(4) 0.59515(12) 0.0154(5) Uani 1 1 d . . . . .
C3 C -0.4937(2) 1.1230(4) 0.59297(12) 0.0154(5) Uani 1 1 d . . . . .
C4 C -0.41578(19) 0.9113(4) 0.59192(11) 0.0136(5) Uani 1 1 d . . . . .
C5 C -0.43721(19) 0.7418(4) 0.64848(12) 0.0150(5) Uani 1 1 d . . . . .
C6 C -0.56039(19) 0.6716(4) 0.65070(12) 0.0147(5) Uani 1 1 d . . . . .
N1 N -0.75254(16) 0.8255(4) 0.66056(10) 0.0132(4) Uani 1 1 d . . . . .
N2 N -0.29823(17) 1.0002(4) 0.59672(10) 0.0148(4) Uani 1 1 d . . . . .
O1 O 0.16124(14) 0.2762(3) 0.69695(8) 0.0148(3) Uani 1 1 d . . . . .
O2 O 0.20339(14) 0.5815(3) 0.77568(8) 0.0148(3) Uani 1 1 d . . . . .
O3 O 0.30022(14) 0.2063(3) 0.77991(8) 0.0169(4) Uani 1 1 d . . . . .
O4 O -0.00201(15) 0.6946(3) 0.67296(9) 0.0155(4) Uani 1 1 d . . . . .
O5 O 0.14608(13) 0.5147(3) 0.56470(8) 0.0129(3) Uani 1 1 d . . . . .
O6 O -0.10829(14) 0.2260(3) 0.68944(8) 0.0161(4) Uani 1 1 d . . . . .
O7 O -0.08798(13) 0.3201(3) 0.53933(8) 0.0131(3) Uani 1 1 d . . . . .
O8 O -0.27795(13) 0.4471(3) 0.52318(8) 0.0170(4) Uani 1 1 d . . . . .
O9 O -0.13030(13) 0.7361(3) 0.53141(8) 0.0142(3) Uani 1 1 d . . . . .
F1 F 0.05975(11) 0.0240(2) 0.59334(6) 0.0131(3) Uani 1 1 d . . . . .
S1 S 0.19369(4) 0.32398(10) 0.76622(3) 0.01076(12) Uani 1 1 d . . . . .
S2 S -0.16246(4) 0.49892(9) 0.50705(2) 0.00977(12) Uani 1 1 d . . . . .
Mn1 Mn 0.02398(3) 0.35782(6) 0.63160(2) 0.00965(10) Uani 1 1 d . . . . .
Mn2 Mn 0.0000 0.0000 0.5000 0.01102(12) Uani 1 2 d S . P . .
H1 H -0.060(3) 0.695(6) 0.6926(17) 0.030(9) Uiso 1 1 d . . . . .
H2 H -0.248(3) 0.892(7) 0.5864(18) 0.033(9) Uiso 1 1 d . . . . .
H3 H -0.285(2) 1.048(6) 0.6360(16) 0.014(7) Uiso 1 1 d . . . . .
H4 H -0.287(3) 1.132(6) 0.5699(17) 0.026(8) Uiso 1 1 d . . . . .
H5 H -0.417(2) 0.822(6) 0.6865(15) 0.014(7) Uiso 1 1 d . . . . .
H6 H -0.392(2) 0.604(6) 0.6479(14) 0.014(7) Uiso 1 1 d . . . . .
H7 H -0.425(2) 0.831(5) 0.5525(14) 0.010(6) Uiso 1 1 d . . . . .
H8 H -0.584(2) 0.581(5) 0.6140(14) 0.009(6) Uiso 1 1 d . . . . .
H10 H -0.479(3) 1.228(6) 0.5540(15) 0.019(8) Uiso 1 1 d . . . . .
H11 H -0.476(3) 1.216(6) 0.6301(16) 0.017(7) Uiso 1 1 d . . . . .
H12 H -0.616(2) 0.978(6) 0.6925(15) 0.014(7) Uiso 1 1 d . . . . .
H13 H -0.663(3) 1.183(6) 0.5983(16) 0.026(8) Uiso 1 1 d . . . . .
H14 H -0.634(3) 0.961(6) 0.5580(16) 0.021(8) Uiso 1 1 d . . . . .
H15 H -0.795(3) 0.960(6) 0.6584(14) 0.016(7) Uiso 1 1 d . . . . .
H16 H -0.780(3) 0.740(6) 0.6249(18) 0.027(9) Uiso 1 1 d . . . . .
H17 H -0.763(3) 0.738(6) 0.6960(19) 0.029(9) Uiso 1 1 d . . . . .
H18 H -0.572(2) 0.576(6) 0.6860(15) 0.014(7) Uiso 1 1 d . . . . .
H19 H 0.005(4) 0.799(8) 0.656(2) 0.043(13) Uiso 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
C1 N1 1.492(3) . ?
C1 C6 1.518(3) . ?
C1 C2 1.522(3) . ?
C2 C3 1.527(3) . ?
C3 C4 1.522(3) . ?
C4 N2 1.502(3) . ?
C4 C5 1.525(3) . ?
C5 C6 1.533(3) . ?
O1 S1 1.4887(17) . ?
O1 Mn1 2.1628(17) . ?
O2 S1 1.4770(17) . ?
O3 S1 1.4678(17) . ?
O4 Mn1 2.1113(18) . ?
O5 S2 1.4810(15) 3_566 ?
O5 Mn1 2.1990(15) . ?
O6 S1 1.4808(15) 2_556 ?
O6 Mn1 2.1221(15) . ?
O7 S2 1.5012(17) . ?
O7 Mn2 2.2505(16) . ?
O7 Mn1 2.3158(17) . ?
O8 S2 1.4579(16) . ?
O9 S2 1.4834(17) . ?
O9 Mn2 2.2611(16) 1_565 ?
F1 Mn2 2.0354(13) . ?
F1 Mn1 2.0927(13) . ?
S1 O6 1.4808(15) 2_556 ?
S2 O5 1.4809(15) 3_566 ?
Mn2 F1 2.0355(13) 3_556 ?
Mn2 O7 2.2505(16) 3_556 ?
Mn2 O9 2.2611(16) 1_545 ?
Mn2 O9 2.2611(16) 3_566 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
N1 C1 C6 110.75(19) . . ?
N1 C1 C2 109.9(2) . . ?
C6 C1 C2 110.45(18) . . ?
C1 C2 C3 108.8(2) . . ?
C4 C3 C2 111.6(2) . . ?
N2 C4 C3 108.23(19) . . ?
N2 C4 C5 109.0(2) . . ?
C3 C4 C5 112.26(18) . . ?
C4 C5 C6 110.7(2) . . ?
C1 C6 C5 109.99(19) . . ?
S1 O1 Mn1 137.71(10) . . ?
S2 O5 Mn1 133.40(10) 3_566 . ?
S1 O6 Mn1 137.11(11) 2_556 . ?
S2 O7 Mn2 131.89(10) . . ?
S2 O7 Mn1 129.42(10) . . ?
Mn2 O7 Mn1 95.35(6) . . ?
S2 O9 Mn2 133.12(9) . 1_565 ?
Mn2 F1 Mn1 109.74(6) . . ?
O3 S1 O2 110.88(11) . . ?
O3 S1 O6 108.66(10) . 2_556 ?
O2 S1 O6 110.19(9) . 2_556 ?
O3 S1 O1 108.65(10) . . ?
O2 S1 O1 108.89(10) . . ?
O6 S1 O1 109.54(10) 2_556 . ?
O8 S2 O5 110.27(10) . 3_566 ?
O8 S2 O9 110.66(10) . . ?
O5 S2 O9 110.02(9) 3_566 . ?
O8 S2 O7 109.24(10) . . ?
O5 S2 O7 108.41(9) 3_566 . ?
O9 S2 O7 108.18(10) . . ?
F1 Mn1 O4 176.38(6) . . ?
F1 Mn1 O6 92.63(6) . . ?
O4 Mn1 O6 88.99(7) . . ?
F1 Mn1 O1 83.05(6) . . ?
O4 Mn1 O1 93.51(7) . . ?
O6 Mn1 O1 98.74(7) . . ?
F1 Mn1 O5 89.66(6) . . ?
O4 Mn1 O5 89.08(7) . . ?
O6 Mn1 O5 173.34(7) . . ?
O1 Mn1 O5 87.75(6) . . ?
F1 Mn1 O7 74.49(6) . . ?
O4 Mn1 O7 108.78(7) . . ?
O6 Mn1 O7 89.27(6) . . ?
O1 Mn1 O7 156.49(6) . . ?
O5 Mn1 O7 85.31(6) . . ?
F1 Mn2 F1 180.0 . 3_556 ?
F1 Mn2 O7 102.97(6) . 3_556 ?
F1 Mn2 O7 77.03(6) 3_556 3_556 ?
F1 Mn2 O7 77.02(6) . . ?
F1 Mn2 O7 102.98(6) 3_556 . ?
O7 Mn2 O7 180.00(5) 3_556 . ?
F1 Mn2 O9 91.08(6) . 1_545 ?
F1 Mn2 O9 88.92(6) 3_556 1_545 ?
O7 Mn2 O9 84.01(6) 3_556 1_545 ?
O7 Mn2 O9 95.99(6) . 1_545 ?
F1 Mn2 O9 88.92(6) . 3_566 ?
F1 Mn2 O9 91.08(6) 3_556 3_566 ?
O7 Mn2 O9 95.99(6) 3_556 3_566 ?
O7 Mn2 O9 84.01(6) . 3_566 ?
O9 Mn2 O9 180.0 1_545 3_566 ?

_refine_diff_density_max         0.388
_refine_diff_density_min         -0.382
_refine_diff_density_rms         0.070

_shelxl_version_number           2013-4

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx
_database_code_depnum_ccdc_archive 'CCDC 1452168'
_audit_update_record             
;
2016-02-08 deposited with the CCDC.
2016-04-22 downloaded from the CCDC.
;
_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H16 F Fe N2 O8 S2'
_chemical_formula_weight         383.18

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0727 0.0534 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.3331 0.5567 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Fe Fe -1.1336 3.1974 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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

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

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

_cell_length_a                   10.2220(3)
_cell_length_b                   17.6599(4)
_cell_length_c                   7.0437(2)
_cell_angle_alpha                90
_cell_angle_beta                 93.894(2)
_cell_angle_gamma                90
_cell_volume                     1268.59(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    150.20(10)
_cell_measurement_reflns_used    6891
_cell_measurement_theta_min      4.3630
_cell_measurement_theta_max      71.6790

_exptl_crystal_description       Needle
_exptl_crystal_colour            'Dark brown'
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    2.006
_exptl_crystal_F_000             788
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.01
_exptl_absorpt_coefficient_mu    13.169
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.65543
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;


_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150.20(10)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'sealed X-ray tube'
_diffrn_measurement_device_type  'SuperNova, Dual Cu at zero, EosS2'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 8.1150
_diffrn_reflns_number            11754
_diffrn_reflns_av_unetI/netI     0.0247
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         4.335
_diffrn_reflns_theta_max         71.911
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             2493
_reflns_number_gt                2373
_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXL-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0665P)²+4.3394P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         2493
_refine_ls_number_parameters     245
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0423
_refine_ls_R_factor_gt           0.0406
_refine_ls_wR_factor_ref         0.1216
_refine_ls_wR_factor_gt          0.1195
_refine_ls_goodness_of_fit_ref   1.072
_refine_ls_restrained_S_all      1.072
_refine_ls_shift/su_max          0.003
_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
C1 C 0.7184(3) 0.3603(2) 0.8677(5) 0.0117(7) Uani 1 1 d . . . . .
C2 C 0.7800(4) 0.4288(2) 0.7770(5) 0.0150(7) Uani 1 1 d . . . . .
C3 C 0.8286(3) 0.4834(2) 0.9343(5) 0.0128(7) Uani 1 1 d . . . . .
C4 C 0.7202(3) 0.50516(19) 1.0636(5) 0.0105(6) Uani 1 1 d . . . . .
C5 C 0.6431(3) 0.4380(2) 1.1316(5) 0.0110(7) Uani 1 1 d . . . . .
C6 C 0.5986(3) 0.3848(2) 0.9683(5) 0.0130(7) Uani 1 1 d . . . . .
N1 N 0.7830(3) 0.54384(18) 1.2359(5) 0.0134(6) Uani 1 1 d . . . . .
N2 N 0.6830(3) 0.30111(19) 0.7214(5) 0.0147(6) Uani 1 1 d . . . . .
O1 O 0.0734(2) 0.17003(13) 0.0427(3) 0.0095(5) Uani 1 1 d . . . . .
O2 O 0.0288(2) 0.31435(14) 0.1997(3) 0.0115(5) Uani 1 1 d . . . . .
O3 O 0.2981(2) 0.33589(13) 0.2564(3) 0.0096(5) Uani 1 1 d . . . . .
O4 O 0.3414(2) 0.19681(14) 0.0926(3) 0.0112(5) Uani 1 1 d . . . . .
O5 O 0.5190(2) 0.31629(14) 0.3915(3) 0.0124(5) Uani 1 1 d . . . . .
O6 O 0.3951(2) 0.42603(14) 0.4782(4) 0.0137(5) Uani 1 1 d . . . . .
O7 O -0.1465(2) 0.30581(15) 0.4077(4) 0.0152(5) Uani 1 1 d . . . . .
O8 O -0.0393(2) 0.42590(14) 0.3609(4) 0.0138(5) Uani 1 1 d . . . . .
F1 F 0.18202(17) 0.30067(11) -0.1081(2) 0.0087(4) Uani 1 1 d . . . . .
S1 S 0.39061(7) 0.34640(4) 0.42814(11) 0.0068(2) Uani 1 1 d . . . . .
S2 S -0.02498(7) 0.34503(4) 0.37817(11) 0.0068(2) Uani 1 1 d . . . . .
Fe1 Fe 0.18301(5) 0.25434(3) 0.14597(7) 0.00910(18) Uani 1 1 d . . . . .
H1 H 0.542(5) 0.408(3) 0.884(7) 0.014(11) Uiso 1 1 d . . . . .
H2 H 0.554(5) 0.347(3) 1.005(7) 0.014(11) Uiso 1 1 d . . . . .
H3 H 0.693(5) 0.415(3) 1.209(7) 0.012(11) Uiso 1 1 d . . . . .
H4 H 0.578(5) 0.455(3) 1.193(8) 0.027(13) Uiso 1 1 d . . . . .
H5 H 0.668(4) 0.540(2) 1.008(6) 0.004(9) Uiso 1 1 d . . . . .
H6 H 0.861(5) 0.526(3) 0.880(7) 0.021(12) Uiso 1 1 d . . . . .
H7 H 0.710(5) 0.451(3) 0.688(7) 0.018(11) Uiso 1 1 d . . . . .
H8 H 0.777(5) 0.338(3) 0.954(7) 0.013(11) Uiso 1 1 d . . . . .
H9 H 0.897(5) 0.457(3) 1.004(7) 0.023(12) Uiso 1 1 d . . . . .
H10 H 0.843(5) 0.519(3) 1.285(7) 0.019(12) Uiso 1 1 d . . . . .
H11 H 0.653(5) 0.261(3) 0.761(8) 0.019(12) Uiso 1 1 d . . . . .
H12 H 0.644(5) 0.314(3) 0.639(8) 0.019(13) Uiso 1 1 d . . . . .
H13 H 0.750(6) 0.285(3) 0.670(9) 0.037(16) Uiso 1 1 d . . . . .
H14 H 0.853(5) 0.414(3) 0.713(7) 0.020(12) Uiso 1 1 d . . . . .
H15 H 0.729(6) 0.547(3) 1.315(9) 0.032(15) Uiso 1 1 d . . . . .
H16 H 0.821(5) 0.585(3) 1.213(7) 0.015(11) Uiso 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
C1 N2 1.495(4) . ?
C1 C6 1.518(5) . ?
C1 C2 1.523(5) . ?
C2 C3 1.526(5) . ?
C3 C4 1.530(4) . ?
C4 N1 1.499(4) . ?
C4 C5 1.520(5) . ?
C5 C6 1.530(5) . ?
O1 S2 1.506(2) 4_565 ?
O1 Fe1 1.973(2) . ?
O2 S2 1.507(2) . ?
O2 Fe1 1.958(2) . ?
O3 S1 1.495(2) . ?
O3 Fe1 1.985(2) . ?
O4 S1 1.502(2) 4_565 ?
O4 Fe1 1.970(2) . ?
O5 S1 1.456(2) . ?
O6 S1 1.450(2) . ?
O7 S2 1.449(2) . ?
O8 S2 1.440(3) . ?
F1 Fe1 1.9670(19) . ?
F1 Fe1 1.9868(19) 4_565 ?
S1 O4 1.502(2) 4_566 ?
S2 O1 1.506(2) 4_566 ?
Fe1 F1 1.9868(19) 4_566 ?

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 C1 C6 110.8(3) . . ?
N2 C1 C2 110.7(3) . . ?
C6 C1 C2 109.8(3) . . ?
C1 C2 C3 108.7(3) . . ?
C2 C3 C4 112.2(3) . . ?
N1 C4 C5 107.6(3) . . ?
N1 C4 C3 108.0(3) . . ?
C5 C4 C3 113.8(3) . . ?
C4 C5 C6 112.1(3) . . ?
C1 C6 C5 108.5(3) . . ?
S2 O1 Fe1 138.60(15) 4_565 . ?
S2 O2 Fe1 134.43(15) . . ?
S1 O3 Fe1 137.09(15) . . ?
S1 O4 Fe1 137.05(15) 4_565 . ?
Fe1 F1 Fe1 126.14(10) . 4_565 ?
O6 S1 O5 112.53(15) . . ?
O6 S1 O3 108.97(14) . . ?
O5 S1 O3 109.83(14) . . ?
O6 S1 O4 108.19(15) . 4_566 ?
O5 S1 O4 107.71(14) . 4_566 ?
O3 S1 O4 109.55(13) . 4_566 ?
O8 S2 O7 113.76(15) . . ?
O8 S2 O1 107.39(14) . 4_566 ?
O7 S2 O1 109.81(15) . 4_566 ?
O8 S2 O2 109.09(15) . . ?
O7 S2 O2 108.23(15) . . ?
O1 S2 O2 108.45(13) 4_566 . ?
O2 Fe1 F1 89.78(9) . . ?
O2 Fe1 O4 178.25(11) . . ?
F1 Fe1 O4 89.68(9) . . ?
O2 Fe1 O1 92.01(10) . . ?
F1 Fe1 O1 90.62(9) . . ?
O4 Fe1 O1 89.66(10) . . ?
O2 Fe1 O3 89.73(10) . . ?
F1 Fe1 O3 91.20(9) . . ?
O4 Fe1 O3 88.61(10) . . ?
O1 Fe1 O3 177.48(10) . . ?
O2 Fe1 F1 92.54(9) . 4_566 ?
F1 Fe1 F1 175.27(6) . 4_566 ?
O4 Fe1 F1 88.12(9) . 4_566 ?
O1 Fe1 F1 85.18(9) . 4_566 ?
O3 Fe1 F1 92.93(9) . 4_566 ?

_refine_diff_density_max         0.636
_refine_diff_density_min         -0.915
_refine_diff_density_rms         0.118

_shelxl_version_number           2013-4

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx
_database_code_depnum_ccdc_archive 'CCDC 1452169'
_audit_update_record             
;
2016-02-08 deposited with the CCDC.
2016-04-22 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_RINTA01_shelx               
;
PROBLEM: The value of Rint is greater than 0.18
RESPONSE: Poor quality crystals, isostructural with [N2C6H16]FeF(SO4)2  
which obtained much better Rint values, so it is accepted that a re-run 
was not necessary
;
_vrf_PLAT020_shelx               
;
PROBLEM: The value of Rint is greater than 0.12 .........      0.228 Report
RESPONSE: See response above
;
_vrf_PLAT353_shelx               
;
PROBLEM: Long    N-H (N0.87,N1.01A)  N1     -   H1C    ..       1.08 Ang.  
RESPONSE: Some long and short N-H bond distances, due to cationic nature
of protonated amines and distortion due to hydrogen bonding.
;
_vrf_PLAT352_shelx               
;
PROBLEM: Short   N-H (X0.87,N1.01A)  N2     -   H2C    ..       0.76 Ang.  
RESPONSE: See response above 
;
# end Validation Reply Form

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C6 H16 F N2 O8 S2 V'
_chemical_formula_weight         378.27

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'
V V 0.3005 0.5294 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

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

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

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

_cell_length_a                   10.262(2)
_cell_length_b                   17.761(4)
_cell_length_c                   7.0518(14)
_cell_angle_alpha                90
_cell_angle_beta                 93.93(3)
_cell_angle_gamma                90
_cell_volume                     1282.3(5)
_cell_formula_units_Z            4
_cell_measurement_temperature    150(5)
_cell_measurement_reflns_used    4446
_cell_measurement_theta_min      1.1
_cell_measurement_theta_max      35.0

_exptl_crystal_description       Needle
_exptl_crystal_colour            Green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.959
_exptl_crystal_F_000             776
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_exptl_absorpt_coefficient_mu    1.152
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6652
_exptl_absorpt_correction_T_max  0.8086
_exptl_absorpt_process_details   
;
CrysAlis PRO; Agilent, 2014
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(5)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Rotating Anode'
_diffrn_measurement_device_type  
;
Rigaku Saturn724+ (2x2 bin mode)
;

_diffrn_measurement_method       'profile data from ω scans'
_diffrn_detector_area_resol_mean 28.5714
_diffrn_reflns_number            17161
_diffrn_reflns_av_unetI/netI     0.1255
_diffrn_reflns_av_R_equivalents  0.2277
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         1.989
_diffrn_reflns_theta_max         34.777
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.920
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.920
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.920
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             5115
_reflns_number_gt                4403
_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1214P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         5115
_refine_ls_number_parameters     205
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0822
_refine_ls_R_factor_gt           0.0736
_refine_ls_wR_factor_ref         0.2120
_refine_ls_wR_factor_gt          0.1957
_refine_ls_goodness_of_fit_ref   1.059
_refine_ls_restrained_S_all      1.059
_refine_ls_shift/su_max          0.047
_refine_ls_shift/su_mean         0.002

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
N1 N 0.2163(2) 0.95629(13) 0.2612(3) 0.0272(4) Uani 1 1 d . . . . .
C1 C 0.2788(2) 0.99495(12) 0.4342(3) 0.0212(4) Uani 1 1 d . . . . .
H1 H 0.3391 0.9599 0.5022 0.025 Uiso 1 1 calc R U . . .
C6 C 0.3557(2) 1.06175(14) 0.3663(3) 0.0235(4) Uani 1 1 d . . . . .
H6A H 0.3018 1.0894 0.2719 0.028 Uiso 1 1 calc R U . . .
H6B H 0.4318 1.0435 0.3061 0.028 Uiso 1 1 calc R U . . .
N2 N 0.3160(3) 1.19846(14) 0.7759(3) 0.0300(5) Uani 1 1 d . . . . .
C4 C 0.2813(2) 1.13904(14) 0.6304(3) 0.0225(4) Uani 1 1 d . . . . .
H4 H 0.2173 1.1604 0.5357 0.027 Uiso 1 1 calc R U . . .
C2 C 0.1711(2) 1.01640(15) 0.5630(4) 0.0265(5) Uani 1 1 d . . . . .
H2A H 0.1381 0.9712 0.6202 0.032 Uiso 1 1 calc R U . . .
H2B H 0.0995 1.0395 0.4870 0.032 Uiso 1 1 calc R U . . .
C5 C 0.4001(2) 1.11505(14) 0.5294(4) 0.0265(5) Uani 1 1 d . . . . .
H5A H 0.4620 1.0896 0.6178 0.032 Uiso 1 1 calc R U . . .
H5B H 0.4427 1.1589 0.4796 0.032 Uiso 1 1 calc R U . . .
C3 C 0.2194(3) 1.07097(16) 0.7202(4) 0.0301(5) Uani 1 1 d . . . . .
H3A H 0.1468 1.0870 0.7917 0.036 Uiso 1 1 calc R U . . .
H3B H 0.2831 1.0462 0.8070 0.036 Uiso 1 1 calc R U . . .
V1 V 0.81676(3) 0.25425(2) 0.85228(4) 0.01218(12) Uani 1 1 d . . . . .
S2 S 1.02429(5) 0.15518(3) 1.12030(7) 0.01484(14) Uani 1 1 d . . . . .
S1 S 0.60951(5) 0.34577(3) 0.57074(7) 0.01493(14) Uani 1 1 d . . . . .
F1 F 0.81788(12) 0.19961(8) 0.60602(15) 0.0179(3) Uani 1 1 d . . . . .
O1 O 0.70096(16) 0.33501(10) 0.7425(2) 0.0197(3) Uani 1 1 d . . . . .
O2 O 0.92832(16) 0.17097(9) 0.9542(2) 0.0203(3) Uani 1 1 d . . . . .
O3 O 0.66035(17) 0.19603(11) 0.9054(2) 0.0237(4) Uani 1 1 d . . . . .
O4 O 0.96935(16) 0.31494(11) 0.7977(2) 0.0236(3) Uani 1 1 d . . . . .
O5 O 0.6037(2) 0.42491(11) 0.5227(3) 0.0300(4) Uani 1 1 d . . . . .
O7 O 1.14623(18) 0.19345(12) 1.0928(3) 0.0306(4) Uani 1 1 d . . . . .
O8 O 1.0379(2) 0.07427(10) 1.1362(3) 0.0277(4) Uani 1 1 d . . . . .
O6 O 0.48206(17) 0.31488(11) 0.6049(3) 0.0281(4) Uani 1 1 d . . . . .
H1C H 0.276(5) 0.941(2) 0.147(6) 0.053(11) Uiso 1 1 d . . . . .
H1A H 0.161(4) 0.978(2) 0.200(6) 0.048(12) Uiso 1 1 d . . . . .
H2E H 0.245(4) 1.218(2) 0.847(5) 0.035(9) Uiso 1 1 d . . . . .
H1B H 0.182(3) 0.910(2) 0.284(5) 0.032(9) Uiso 1 1 d . . . . .
H2C H 0.363(4) 1.186(2) 0.858(6) 0.045(11) Uiso 1 1 d . . . . .
H2D H 0.370(5) 1.247(3) 0.734(7) 0.066(14) Uiso 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
N1 C1 1.504(3) . ?
C1 C6 1.520(3) . ?
C1 C2 1.526(3) . ?
C6 C5 1.534(3) . ?
N2 C4 1.498(3) . ?
C4 C5 1.515(3) . ?
C4 C3 1.524(4) . ?
C2 C3 1.529(4) . ?
V1 O4 1.9607(16) . ?
V1 O3 1.9668(17) . ?
V1 F1 1.9674(12) 4_566 ?
V1 O2 1.9753(16) . ?
V1 O1 1.9856(17) . ?
V1 F1 1.9902(12) . ?
S2 O8 1.4475(19) . ?
S2 O7 1.4488(19) . ?
S2 O4 1.5038(16) 4_566 ?
S2 O2 1.5042(17) . ?
S1 O5 1.4462(19) . ?
S1 O6 1.4536(18) . ?
S1 O1 1.4928(17) . ?
S1 O3 1.5056(16) 4_565 ?
F1 V1 1.9674(12) 4_565 ?
O3 S1 1.5056(16) 4_566 ?
O4 S2 1.5038(16) 4_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
N1 C1 C6 107.62(19) . . ?
N1 C1 C2 108.12(19) . . ?
C6 C1 C2 113.90(19) . . ?
C1 C6 C5 112.31(19) . . ?
N2 C4 C5 111.0(2) . . ?
N2 C4 C3 111.2(2) . . ?
C5 C4 C3 110.1(2) . . ?
C1 C2 C3 112.2(2) . . ?
C4 C5 C6 108.6(2) . . ?
C4 C3 C2 108.96(19) . . ?
O4 V1 O3 178.28(8) . . ?
O4 V1 F1 89.69(7) . 4_566 ?
O3 V1 F1 89.99(7) . 4_566 ?
O4 V1 O2 91.85(8) . . ?
O3 V1 O2 89.84(8) . . ?
F1 V1 O2 90.81(6) 4_566 . ?
O4 V1 O1 89.49(8) . . ?
O3 V1 O1 88.83(8) . . ?
F1 V1 O1 91.12(6) 4_566 . ?
O2 V1 O1 177.65(6) . . ?
O4 V1 F1 92.54(7) . . ?
O3 V1 F1 87.90(7) . . ?
F1 V1 F1 175.38(4) 4_566 . ?
O2 V1 F1 85.08(6) . . ?
O1 V1 F1 92.94(6) . . ?
O8 S2 O7 113.38(12) . . ?
O8 S2 O4 108.99(11) . 4_566 ?
O7 S2 O4 108.82(12) . 4_566 ?
O8 S2 O2 107.44(11) . . ?
O7 S2 O2 109.48(11) . . ?
O4 S2 O2 108.63(9) 4_566 . ?
O5 S1 O6 112.51(12) . . ?
O5 S1 O1 109.15(11) . . ?
O6 S1 O1 109.87(11) . . ?
O5 S1 O3 107.97(11) . 4_565 ?
O6 S1 O3 107.80(11) . 4_565 ?
O1 S1 O3 109.47(9) . 4_565 ?
V1 F1 V1 126.19(7) 4_565 . ?
S1 O1 V1 137.30(11) . . ?
S2 O2 V1 139.02(10) . . ?
S1 O3 V1 137.51(11) 4_566 . ?
S2 O4 V1 135.02(11) 4_565 . ?

_refine_diff_density_max         1.466
_refine_diff_density_min         -1.575
_refine_diff_density_rms         0.205

_shelxl_version_number           2013-4

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx
_database_code_depnum_ccdc_archive 'CCDC 1452170'
_audit_update_record             
;
2016-02-08 deposited with the CCDC.
2016-04-22 downloaded from the CCDC.
;

# start Validation Reply Form
_vrf_PLAT780_shelx               
;
PROBLEM: Coordinates do not Form a Properly Connected Set     Please Do ! 
RESPONSE: Molecular cation and connected inorganic framework lie on 
inversion centres, therefore half of the atoms are generated by space group 
symmetry.
;
# end Validation Reply Form
# start Validation Reply Form
_vrf_PLAT250_shelx               
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.4 Note  
RESPONSE: Slightly elongated thermal ellipsoids for terminal oxygens of SO4
groups and N1, C1, C3, C5 and C6 atoms of molecular cations, this is most 
likely due to slight distortion in positions of these atoms due to free 
rotation around the central C-C bond in the molecular cation and 
interactions between the terminal oxygens and the protons of the molecular 
cations. 
;
# end Validation Reply Form


_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C10 H10 F2 N2 O8 S2 Ti'
_chemical_formula_weight         436.22

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'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ti Ti 0.2776 0.4457 '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'

_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                   4.5768(3)
_cell_length_b                   8.9162(6)
_cell_length_c                   10.1236(9)
_cell_angle_alpha                112.888(7)
_cell_angle_beta                 95.196(6)
_cell_angle_gamma                98.706(5)
_cell_volume                     371.11(5)
_cell_formula_units_Z            1
_cell_measurement_temperature    150.2(5)
_cell_measurement_reflns_used    2452
_cell_measurement_theta_min      4.5500
_cell_measurement_theta_max      28.9690

_exptl_crystal_description       Prism
_exptl_crystal_colour            Colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.952
_exptl_crystal_F_000             220
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_exptl_absorpt_coefficient_mu    0.929
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.98969
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;


_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150.2(5)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Enhance (Mo) X-ray source'
_diffrn_measurement_device_type  'New Xcalibur, EosS2'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 8.0734
_diffrn_reflns_number            5670
_diffrn_reflns_av_unetI/netI     0.0393
_diffrn_reflns_av_R_equivalents  0.0307
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         3.990
_diffrn_reflns_theta_max         29.383
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.867
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.867
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.867
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             1772
_reflns_number_gt                1520
_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0376P)²+0.1920P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1772
_refine_ls_number_parameters     119
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0451
_refine_ls_R_factor_gt           0.0346
_refine_ls_wR_factor_ref         0.0825
_refine_ls_wR_factor_gt          0.0778
_refine_ls_goodness_of_fit_ref   1.073
_refine_ls_restrained_S_all      1.073
_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
Ti1 Ti 0.0000 0.0000 0.0000 0.00962(15) Uani 1 2 d S . P . .
S2 S 0.50091(12) 0.11616(6) -0.16474(6) 0.01096(14) Uani 1 1 d . . . . .
F1 F 0.0766(3) -0.18690(15) -0.13604(13) 0.0153(3) Uani 1 1 d . . . . .
O2 O 0.3011(3) 0.14139(18) -0.05120(16) 0.0143(3) Uani 1 1 d . . . . .
O1 O 0.3073(3) 0.00166(18) 0.14924(16) 0.0128(3) Uani 1 1 d . . . . .
O4 O 0.6903(4) 0.27790(19) -0.12852(18) 0.0189(4) Uani 1 1 d . . . . .
N1 N 1.0723(4) 0.3575(2) -0.2886(2) 0.0150(4) Uani 1 1 d . . . . .
C1 C 1.0366(6) 0.2646(3) -0.4316(3) 0.0222(5) Uani 1 1 d . . . . .
H1 H 0.8984 0.1643 -0.4730 0.027 Uiso 1 1 calc R U . . .
O5 O 0.6728(4) -0.0421(2) 0.30810(18) 0.0242(4) Uani 1 1 d . . . . .
C4 C 1.4105(5) 0.4685(3) -0.4546(2) 0.0117(4) Uani 1 1 d . . . . .
C6 C 1.2695(5) 0.5009(3) -0.2240(3) 0.0189(5) Uani 1 1 d . . . . .
H2 H 1.2923 0.5612 -0.1240 0.023 Uiso 1 1 calc R U . . .
C3 C 1.2041(6) 0.3173(3) -0.5175(3) 0.0209(5) Uani 1 1 d . . . . .
H3 H 1.1800 0.2528 -0.6168 0.025 Uiso 1 1 calc R U . . .
C5 C 1.4397(5) 0.5596(3) -0.3058(3) 0.0194(5) Uani 1 1 d . . . . .
H4 H 1.5750 0.6608 -0.2610 0.023 Uiso 1 1 calc R U . . .
H5 H 0.963(7) 0.325(4) -0.242(3) 0.032(9) Uiso 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
Ti1 F1 1.8099(12) 2 ?
Ti1 F1 1.8099(12) . ?
Ti1 O1 1.9627(15) . ?
Ti1 O1 1.9627(15) 2 ?
Ti1 O2 1.9668(15) . ?
Ti1 O2 1.9668(15) 2 ?
S2 O5 1.4357(17) 2_655 ?
S2 O4 1.4554(16) . ?
S2 O2 1.5033(15) . ?
S2 O1 1.5104(15) 2_655 ?
O1 S2 1.5104(15) 2_655 ?
N1 C6 1.330(3) . ?
N1 C1 1.339(3) . ?
C1 C3 1.377(3) . ?
O5 S2 1.4357(17) 2_655 ?
C4 C5 1.388(3) . ?
C4 C3 1.397(3) . ?
C4 C4 1.493(4) 2_864 ?
C6 C5 1.377(3) . ?

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
F1 Ti1 F1 180.0 2 . ?
F1 Ti1 O1 87.68(6) 2 . ?
F1 Ti1 O1 92.32(6) . . ?
F1 Ti1 O1 92.32(6) 2 2 ?
F1 Ti1 O1 87.68(6) . 2 ?
O1 Ti1 O1 180.00(7) . 2 ?
F1 Ti1 O2 88.47(6) 2 . ?
F1 Ti1 O2 91.53(6) . . ?
O1 Ti1 O2 89.38(6) . . ?
O1 Ti1 O2 90.62(6) 2 . ?
F1 Ti1 O2 91.54(6) 2 2 ?
F1 Ti1 O2 88.47(6) . 2 ?
O1 Ti1 O2 90.62(6) . 2 ?
O1 Ti1 O2 89.38(6) 2 2 ?
O2 Ti1 O2 180.0 . 2 ?
O5 S2 O4 114.46(11) 2_655 . ?
O5 S2 O2 110.87(10) 2_655 . ?
O4 S2 O2 106.28(9) . . ?
O5 S2 O1 108.75(10) 2_655 2_655 ?
O4 S2 O1 109.39(9) . 2_655 ?
O2 S2 O1 106.81(9) . 2_655 ?
S2 O2 Ti1 136.64(9) . . ?
S2 O1 Ti1 136.60(9) 2_655 . ?
C6 N1 C1 122.2(2) . . ?
N1 C1 C3 120.1(2) . . ?
C5 C4 C3 118.0(2) . . ?
C5 C4 C4 121.1(2) . 2_864 ?
C3 C4 C4 120.9(2) . 2_864 ?
N1 C6 C5 119.7(2) . . ?
C1 C3 C4 119.6(2) . . ?
C6 C5 C4 120.4(2) . . ?

_refine_diff_density_max         0.439
_refine_diff_density_min         -0.410
_refine_diff_density_rms         0.080

_shelxl_version_number           2013-4

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_shelx
_database_code_depnum_ccdc_archive 'CCDC 1452171'
_audit_update_record             
;
2016-02-08 deposited with the CCDC.
2016-04-22 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2013
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C10 H10 F4 N2 O4 S Ti'
_chemical_formula_weight         378.16

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'
Ti Ti 0.2776 0.4457 '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                   8.691(2)
_cell_length_b                   9.208(2)
_cell_length_c                   9.288(2)
_cell_angle_alpha                68.56(2)
_cell_angle_beta                 84.30(2)
_cell_angle_gamma                81.59(2)
_cell_volume                     683.6(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    150(2)
_cell_measurement_reflns_used    1482
_cell_measurement_theta_min      3.8520
_cell_measurement_theta_max      27.1310

_exptl_crystal_description       Prism
_exptl_crystal_colour            Colourless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.837
_exptl_crystal_F_000             380
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.06
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_exptl_absorpt_coefficient_mu    0.845
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.91585
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      150(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   'Enhance (Mo) X-ray Source'
_diffrn_measurement_device_type  'New Xcalibur , EosS2'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 16.1468
_diffrn_reflns_number            5816
_diffrn_reflns_av_unetI/netI     0.1188
_diffrn_reflns_av_R_equivalents  0.0541
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_theta_min         3.315
_diffrn_reflns_theta_max         29.303
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.838
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.838
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.838
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             3133
_reflns_number_gt                2094
_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       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;

_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;

_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;

_computing_structure_solution    'SHELXS-2013 (Sheldrick, 2013)'
_computing_structure_refinement  'SHELXL-2013 (Sheldrick, 2013)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
;
 ?
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.0368P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    refall
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         3133
_refine_ls_number_parameters     239
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1027
_refine_ls_R_factor_gt           0.0581
_refine_ls_wR_factor_ref         0.1282
_refine_ls_wR_factor_gt          0.1043
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_restrained_S_all      1.045
_refine_ls_shift/su_max          0.026
_refine_ls_shift/su_mean         0.004

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
C1 C 0.5159(4) 0.2787(5) 0.0076(5) 0.0136(9) Uani 1 1 d . . . . .
C2 C 0.4101(5) 0.1772(5) 0.1247(5) 0.0153(10) Uani 1 1 d . . . . .
C3 C 0.2500(5) 0.2027(5) 0.1123(6) 0.0176(10) Uani 1 1 d . . . . .
C4 C 0.1573(5) 0.1055(5) 0.2219(6) 0.0199(11) Uani 1 1 d . . . . .
C5 C 0.3742(5) -0.0434(5) 0.3577(6) 0.0209(11) Uani 1 1 d . . . . .
C6 C 0.4709(6) 0.0525(5) 0.2519(6) 0.0215(11) Uani 1 1 d . . . . .
C7 C 0.6573(5) 0.3035(5) 0.0474(6) 0.0182(10) Uani 1 1 d . . . . .
C8 C 0.4766(5) 0.3496(5) -0.1451(6) 0.0196(11) Uani 1 1 d . . . . .
C9 C 0.5752(5) 0.4415(5) -0.2542(6) 0.0205(11) Uani 1 1 d . . . . .
C10 C 0.7538(5) 0.3952(5) -0.0645(6) 0.0196(10) Uani 1 1 d . . . . .
N1 N 0.2212(4) -0.0142(4) 0.3403(5) 0.0191(9) Uani 1 1 d . . . . .
N2 N 0.7109(4) 0.4614(4) -0.2102(5) 0.0179(9) Uani 1 1 d . . . . .
O1 O 0.1869(3) 0.4640(3) 0.6033(3) 0.0147(7) Uani 1 1 d . . . . .
O5 O -0.0552(3) 0.6329(3) 0.6022(3) 0.0119(6) Uani 1 1 d . . . . .
O7 O 0.0865(3) 0.5215(3) 0.8320(3) 0.0182(7) Uani 1 1 d . . . . .
O8 O 0.1915(3) 0.7218(3) 0.6082(4) 0.0175(7) Uani 1 1 d . . . . .
F1 F 0.3301(3) 0.2505(3) 0.4996(3) 0.0188(6) Uani 1 1 d . . . . .
F2 F 0.2292(3) 0.1567(3) 0.7990(3) 0.0226(6) Uani 1 1 d . . . . .
F3 F 0.1071(3) 0.0642(3) 0.6015(3) 0.0208(6) Uani 1 1 d . . . . .
F4 F -0.0519(3) 0.2796(3) 0.6961(3) 0.0188(6) Uani 1 1 d . . . . .
S1 S 0.10557(12) 0.58675(12) 0.66492(13) 0.0127(3) Uani 1 1 d . . . . .
Ti1 Ti 0.14256(8) 0.24949(9) 0.61324(9) 0.0129(2) Uani 1 1 d . . . . .
H1 H 0.845(5) 0.416(5) -0.033(6) 0.030(14) Uiso 1 1 d . . . . .
H2 H 0.685(5) 0.261(5) 0.150(5) 0.019(12) Uiso 1 1 d . . . . .
H3 H 0.566(5) 0.038(5) 0.254(5) 0.012(12) Uiso 1 1 d . . . . .
H4 H 0.414(5) -0.135(6) 0.451(6) 0.037(15) Uiso 1 1 d . . . . .
H5 H 0.164(4) -0.072(5) 0.412(5) 0.008(11) Uiso 1 1 d . . . . .
H6 H 0.048(5) 0.125(4) 0.225(5) 0.010(11) Uiso 1 1 d . . . . .
H7 H 0.212(4) 0.284(4) 0.034(5) 0.000(10) Uiso 1 1 d . . . . .
H8 H 0.389(5) 0.338(5) -0.175(5) 0.016(12) Uiso 1 1 d . . . . .
H9 H 0.555(4) 0.506(4) -0.372(5) 0.011(11) Uiso 1 1 d . . . . .
H10 H 0.778(6) 0.500(6) -0.267(7) 0.041(18) Uiso 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
C1 C8 1.381(6) . ?
C1 C7 1.391(6) . ?
C1 C2 1.487(6) . ?
C2 C3 1.386(6) . ?
C2 C6 1.396(6) . ?
C3 C4 1.367(6) . ?
C4 N1 1.337(6) . ?
C5 N1 1.331(5) . ?
C5 C6 1.368(6) . ?
C7 C10 1.374(6) . ?
C8 C9 1.375(6) . ?
C9 N2 1.343(6) . ?
C10 N2 1.331(6) . ?
O1 S1 1.505(3) . ?
O1 Ti1 2.035(3) . ?
O5 S1 1.510(3) . ?
O5 Ti1 2.057(3) 2_566 ?
O7 S1 1.447(3) . ?
O8 S1 1.447(3) . ?
F1 Ti1 1.851(2) . ?
F2 Ti1 1.807(3) . ?
F3 Ti1 1.821(2) . ?
F4 Ti1 1.812(2) . ?
Ti1 O5 2.057(3) 2_566 ?

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
C8 C1 C7 118.1(4) . . ?
C8 C1 C2 120.5(4) . . ?
C7 C1 C2 121.4(4) . . ?
C3 C2 C6 118.0(4) . . ?
C3 C2 C1 121.8(4) . . ?
C6 C2 C1 120.2(4) . . ?
C4 C3 C2 119.8(4) . . ?
N1 C4 C3 120.0(4) . . ?
N1 C5 C6 119.3(4) . . ?
C5 C6 C2 120.3(4) . . ?
C10 C7 C1 119.8(4) . . ?
C9 C8 C1 120.7(4) . . ?
N2 C9 C8 119.0(4) . . ?
N2 C10 C7 120.0(4) . . ?
C4 N1 C5 122.5(4) . . ?
C10 N2 C9 122.5(4) . . ?
S1 O1 Ti1 135.16(17) . . ?
S1 O5 Ti1 135.05(17) . 2_566 ?
O7 S1 O8 113.64(18) . . ?
O7 S1 O1 110.36(17) . . ?
O8 S1 O1 108.56(17) . . ?
O7 S1 O5 107.37(17) . . ?
O8 S1 O5 109.58(16) . . ?
O1 S1 O5 107.14(16) . . ?
F2 Ti1 F4 94.16(12) . . ?
F2 Ti1 F3 93.74(12) . . ?
F4 Ti1 F3 92.14(11) . . ?
F2 Ti1 F1 94.60(12) . . ?
F4 Ti1 F1 169.87(12) . . ?
F3 Ti1 F1 92.35(11) . . ?
F2 Ti1 O1 90.83(12) . . ?
F4 Ti1 O1 90.86(11) . . ?
F3 Ti1 O1 174.33(13) . . ?
F1 Ti1 O1 83.94(11) . . ?
F2 Ti1 O5 175.80(11) . 2_566 ?
F4 Ti1 O5 88.10(11) . 2_566 ?
F3 Ti1 O5 89.70(12) . 2_566 ?
F1 Ti1 O5 82.84(11) . 2_566 ?
O1 Ti1 O5 85.59(12) . 2_566 ?

_refine_diff_density_max         0.614
_refine_diff_density_min         -0.914
_refine_diff_density_rms         0.133

_shelxl_version_number           2013-4

