# Electronic Supplementary Material (ESI) for Chemical Communications.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# 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_Brzss
_database_code_depnum_ccdc_archive 'CCDC 1500782'
_audit_update_record             
;
2016-08-24 deposited with the CCDC.
2018-11-06 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT353_Brzss               
;
RESPONSE: Strong N-H...N hydrogen bonding interactions between the opposite nitrogens of the terpyrrole units.
;
# end Validation Reply Form

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         'C44 H50 N4 S2'
_chemical_formula_sum            'C44 H50 N4 S2'
_chemical_formula_weight         699.00

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0181 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'
S S 0.3331 0.5567 '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                   8.7071(7)
_cell_length_b                   9.6083(5)
_cell_length_c                   12.2192(8)
_cell_angle_alpha                98.972(5)
_cell_angle_beta                 106.931(7)
_cell_angle_gamma                103.162(6)
_cell_volume                     924.76(12)
_cell_formula_units_Z            1
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    2243
_cell_measurement_theta_min      3.9010
_cell_measurement_theta_max      71.9920

_exptl_crystal_description       plate
_exptl_crystal_colour            bronze
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.255
_exptl_crystal_F_000             374
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.14
_exptl_absorpt_coefficient_mu    1.581
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.83196
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
_diffrn_source                   'Enhance (Cu) X-ray Source'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            5814
_diffrn_reflns_av_unetI/netI     0.0466
_diffrn_reflns_av_R_equivalents  0.0325
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         3.894
_diffrn_reflns_theta_max         70.066
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             3487
_reflns_number_gt                2854
_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
_computing_cell_refinement       CrysAlisPro
_computing_data_reduction        CrysAlisPro
_computing_structure_solution    SIR-92
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'WinGX v2014.1'
_computing_publication_material  'WinGX v2014.1'
_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)+(0.0659P)²+0.2274P] 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         3487
_refine_ls_number_parameters     230
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0616
_refine_ls_R_factor_gt           0.0489
_refine_ls_wR_factor_ref         0.1370
_refine_ls_wR_factor_gt          0.1242
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_restrained_S_all      1.043
_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
S001 S 0.24750(7) 0.80755(6) 0.71246(5) 0.03679(17) Uani 1 1 d . . . . .
N1 N 0.1665(2) 0.4071(2) 0.77962(16) 0.0368(4) Uani 1 1 d . . . . .
N2 N 0.0660(2) 0.8182(2) 0.37373(16) 0.0364(4) Uani 1 1 d . . . . .
C13 C 0.1634(3) 1.0662(2) 0.4023(2) 0.0363(5) Uani 1 1 d . . . . .
C5 C 0.3084(3) 0.6101(3) 0.93240(19) 0.0353(5) Uani 1 1 d . . . . .
C14 C 0.0620(3) 0.9305(3) 0.3180(2) 0.0366(5) Uani 1 1 d . . . . .
C7 C 0.2332(3) 0.6231(2) 0.71100(19) 0.0337(5) Uani 1 1 d . . . . .
C12 C 0.2230(3) 1.0324(2) 0.5094(2) 0.0355(5) Uani 1 1 d . . . . .
C3 C 0.1887(3) 0.3630(3) 0.88263(19) 0.0367(5) Uani 1 1 d . . . . .
C2 C 0.1291(3) 0.2164(3) 0.8891(2) 0.0404(5) Uani 1 1 d . . . . .
H2 H 0.1637 0.2013 0.9647 0.048 Uiso 1 1 calc R U . . .
C4 C 0.2801(3) 0.4901(3) 0.97933(19) 0.0364(5) Uani 1 1 d . . . . .
C6 C 0.2374(3) 0.5549(2) 0.80631(19) 0.0338(5) Uani 1 1 d . . . . .
C9 C 0.1786(3) 0.6274(3) 0.5139(2) 0.0406(5) Uani 1 1 d . . . . .
H9 H 0.1548 0.5882 0.4342 0.049 Uiso 1 1 calc R U . . .
C1 C 0.0280(3) 0.0905(3) 0.8029(2) 0.0400(5) Uani 1 1 d . . . . .
H1 H 0.0176 0.0044 0.8294 0.048 Uiso 1 1 calc R U . . .
C19 C 0.3397(3) 1.1345(3) 0.6245(2) 0.0413(5) Uani 1 1 d . . . . .
H19A H 0.3076 1.1022 0.6882 0.050 Uiso 1 1 calc R U . . .
H19B H 0.3275 1.2325 0.6257 0.050 Uiso 1 1 calc R U . . .
C15 C 0.3263(3) 0.4878(3) 1.1074(2) 0.0426(5) Uani 1 1 d . . . . .
H15A H 0.4214 0.5724 1.1530 0.051 Uiso 1 1 calc R U . . .
H15B H 0.3600 0.3999 1.1181 0.051 Uiso 1 1 calc R U . . .
C10 C 0.1959(3) 0.7748(2) 0.55993(19) 0.0339(5) Uani 1 1 d . . . . .
C17 C 0.3987(3) 0.7680(3) 0.9967(2) 0.0452(6) Uani 1 1 d . . . . .
H17A H 0.4580 0.8149 0.9500 0.054 Uiso 1 1 calc R U . . .
H17B H 0.4814 0.7707 1.0707 0.054 Uiso 1 1 calc R U . . .
C11 C 0.1634(3) 0.8759(2) 0.48939(19) 0.0341(5) Uani 1 1 d . . . . .
C8 C 0.1998(3) 0.5455(3) 0.5968(2) 0.0409(5) Uani 1 1 d . . . . .
H8 H 0.1924 0.4460 0.5780 0.049 Uiso 1 1 calc R U . . .
C16 C 0.1823(4) 0.4902(3) 1.1540(2) 0.0551(7) Uani 1 1 d . . . . .
H16A H 0.2177 0.4886 1.2358 0.083 Uiso 1 1 calc R U . . .
H16B H 0.1499 0.5780 1.1453 0.083 Uiso 1 1 calc R U . . .
H16C H 0.0885 0.4055 1.1104 0.083 Uiso 1 1 calc R U . . .
C21 C 0.2047(3) 1.2133(3) 0.3741(2) 0.0473(6) Uani 1 1 d . . . . .
H21A H 0.2298 1.2897 0.4441 0.057 Uiso 1 1 calc R U . . .
H21B H 0.1075 1.2209 0.3142 0.057 Uiso 1 1 calc R U . . .
C18 C 0.2819(4) 0.8555(3) 1.0220(3) 0.0629(8) Uani 1 1 d . . . . .
H18A H 0.3463 0.9550 1.0630 0.094 Uiso 1 1 calc R U . . .
H18B H 0.2012 0.8554 0.9491 0.094 Uiso 1 1 calc R U . . .
H18C H 0.2247 0.8112 1.0699 0.094 Uiso 1 1 calc R U . . .
C20 C 0.5208(3) 1.1414(4) 0.6459(3) 0.0616(8) Uani 1 1 d . . . . .
H20A H 0.5892 1.2079 0.7203 0.092 Uiso 1 1 calc R U . . .
H20B H 0.5343 1.0451 0.6466 0.092 Uiso 1 1 calc R U . . .
H20C H 0.5543 1.1755 0.5842 0.092 Uiso 1 1 calc R U . . .
C22 C 0.3515(5) 1.2389(5) 0.3309(5) 0.1121(19) Uani 1 1 d . . . . .
H22A H 0.3728 1.3344 0.3142 0.168 Uiso 1 1 calc R U . . .
H22B H 0.4488 1.2337 0.3905 0.168 Uiso 1 1 calc R U . . .
H22C H 0.3266 1.1649 0.2606 0.168 Uiso 1 1 calc R U . . .
H1N H -0.037(7) 0.699(5) 0.323(4) 0.15(2) 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
S001 C10 1.743(2) . ?
S001 C7 1.745(2) . ?
N1 C6 1.358(3) . ?
N1 C3 1.365(3) . ?
N2 C14 1.364(3) . ?
N2 C11 1.366(3) . ?
N2 H1N 1.22(5) . ?
C13 C12 1.379(3) . ?
C13 C14 1.438(3) . ?
C13 C21 1.496(3) . ?
C5 C4 1.371(3) . ?
C5 C6 1.442(3) . ?
C5 C17 1.504(3) . ?
C14 C1 1.414(3) 2_566 ?
C7 C8 1.389(3) . ?
C7 C6 1.418(3) . ?
C12 C11 1.431(3) . ?
C12 C19 1.502(3) . ?
C3 C2 1.409(3) . ?
C3 C4 1.443(3) . ?
C2 C1 1.387(3) . ?
C2 H2 0.9300 . ?
C4 C15 1.503(3) . ?
C9 C8 1.373(3) . ?
C9 C10 1.397(3) . ?
C9 H9 0.9300 . ?
C1 C14 1.414(3) 2_566 ?
C1 H1 0.9300 . ?
C19 C20 1.506(4) . ?
C19 H19A 0.9700 . ?
C19 H19B 0.9700 . ?
C15 C16 1.524(4) . ?
C15 H15A 0.9700 . ?
C15 H15B 0.9700 . ?
C10 C11 1.418(3) . ?
C17 C18 1.526(4) . ?
C17 H17A 0.9700 . ?
C17 H17B 0.9700 . ?
C8 H8 0.9300 . ?
C16 H16A 0.9600 . ?
C16 H16B 0.9600 . ?
C16 H16C 0.9600 . ?
C21 C22 1.504(5) . ?
C21 H21A 0.9700 . ?
C21 H21B 0.9700 . ?
C18 H18A 0.9600 . ?
C18 H18B 0.9600 . ?
C18 H18C 0.9600 . ?
C20 H20A 0.9600 . ?
C20 H20B 0.9600 . ?
C20 H20C 0.9600 . ?
C22 H22A 0.9600 . ?
C22 H22B 0.9600 . ?
C22 H22C 0.9600 . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C10 S001 C7 92.43(11) . . ?
C6 N1 C3 108.14(19) . . ?
C14 N2 C11 108.61(19) . . ?
C14 N2 H1N 118(2) . . ?
C11 N2 H1N 132(2) . . ?
C12 C13 C14 107.2(2) . . ?
C12 C13 C21 127.4(2) . . ?
C14 C13 C21 125.2(2) . . ?
C4 C5 C6 106.1(2) . . ?
C4 C5 C17 128.0(2) . . ?
C6 C5 C17 125.8(2) . . ?
N2 C14 C1 123.5(2) . 2_566 ?
N2 C14 C13 108.4(2) . . ?
C1 C14 C13 128.1(2) 2_566 . ?
C8 C7 C6 123.2(2) . . ?
C8 C7 S001 109.39(17) . . ?
C6 C7 S001 127.14(17) . . ?
C13 C12 C11 106.7(2) . . ?
C13 C12 C19 128.2(2) . . ?
C11 C12 C19 124.9(2) . . ?
N1 C3 C2 124.0(2) . . ?
N1 C3 C4 108.6(2) . . ?
C2 C3 C4 127.5(2) . . ?
C1 C2 C3 131.6(2) . . ?
C1 C2 H2 114.2 . . ?
C3 C2 H2 114.2 . . ?
C5 C4 C3 107.5(2) . . ?
C5 C4 C15 127.6(2) . . ?
C3 C4 C15 124.9(2) . . ?
N1 C6 C7 117.38(19) . . ?
N1 C6 C5 109.7(2) . . ?
C7 C6 C5 132.9(2) . . ?
C8 C9 C10 114.0(2) . . ?
C8 C9 H9 123.0 . . ?
C10 C9 H9 123.0 . . ?
C2 C1 C14 131.6(2) . 2_566 ?
C2 C1 H1 114.2 . . ?
C14 C1 H1 114.2 2_566 . ?
C12 C19 C20 113.1(2) . . ?
C12 C19 H19A 109.0 . . ?
C20 C19 H19A 109.0 . . ?
C12 C19 H19B 109.0 . . ?
C20 C19 H19B 109.0 . . ?
H19A C19 H19B 107.8 . . ?
C4 C15 C16 112.6(2) . . ?
C4 C15 H15A 109.1 . . ?
C16 C15 H15A 109.1 . . ?
C4 C15 H15B 109.1 . . ?
C16 C15 H15B 109.1 . . ?
H15A C15 H15B 107.8 . . ?
C9 C10 C11 123.6(2) . . ?
C9 C10 S001 109.47(17) . . ?
C11 C10 S001 126.79(17) . . ?
C5 C17 C18 113.2(2) . . ?
C5 C17 H17A 108.9 . . ?
C18 C17 H17A 108.9 . . ?
C5 C17 H17B 108.9 . . ?
C18 C17 H17B 108.9 . . ?
H17A C17 H17B 107.7 . . ?
N2 C11 C10 117.1(2) . . ?
N2 C11 C12 109.0(2) . . ?
C10 C11 C12 133.7(2) . . ?
C9 C8 C7 114.6(2) . . ?
C9 C8 H8 122.7 . . ?
C7 C8 H8 122.7 . . ?
C15 C16 H16A 109.5 . . ?
C15 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
C15 C16 H16C 109.5 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
C13 C21 C22 112.7(2) . . ?
C13 C21 H21A 109.0 . . ?
C22 C21 H21A 109.0 . . ?
C13 C21 H21B 109.0 . . ?
C22 C21 H21B 109.0 . . ?
H21A C21 H21B 107.8 . . ?
C17 C18 H18A 109.5 . . ?
C17 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C17 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
C19 C20 H20A 109.5 . . ?
C19 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C19 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C21 C22 H22A 109.5 . . ?
C21 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C21 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion_publ_flag
C11 N2 C14 C1 -179.9(2) . . . 2_566 ?
C11 N2 C14 C13 0.7(3) . . . . ?
C12 C13 C14 N2 -1.9(3) . . . . ?
C21 C13 C14 N2 174.0(2) . . . . ?
C12 C13 C14 C1 178.7(2) . . . 2_566 ?
C21 C13 C14 C1 -5.4(4) . . . 2_566 ?
C10 S001 C7 C8 3.43(18) . . . . ?
C10 S001 C7 C6 -170.7(2) . . . . ?
C14 C13 C12 C11 2.2(2) . . . . ?
C21 C13 C12 C11 -173.5(2) . . . . ?
C14 C13 C12 C19 177.5(2) . . . . ?
C21 C13 C12 C19 1.8(4) . . . . ?
C6 N1 C3 C2 179.1(2) . . . . ?
C6 N1 C3 C4 -0.6(3) . . . . ?
N1 C3 C2 C1 -6.4(4) . . . . ?
C4 C3 C2 C1 173.2(2) . . . . ?
C6 C5 C4 C3 -1.4(2) . . . . ?
C17 C5 C4 C3 -179.9(2) . . . . ?
C6 C5 C4 C15 -178.7(2) . . . . ?
C17 C5 C4 C15 2.8(4) . . . . ?
N1 C3 C4 C5 1.3(3) . . . . ?
C2 C3 C4 C5 -178.4(2) . . . . ?
N1 C3 C4 C15 178.6(2) . . . . ?
C2 C3 C4 C15 -1.0(4) . . . . ?
C3 N1 C6 C7 177.98(19) . . . . ?
C3 N1 C6 C5 -0.3(3) . . . . ?
C8 C7 C6 N1 -16.4(3) . . . . ?
S001 C7 C6 N1 156.96(18) . . . . ?
C8 C7 C6 C5 161.4(2) . . . . ?
S001 C7 C6 C5 -25.2(4) . . . . ?
C4 C5 C6 N1 1.1(3) . . . . ?
C17 C5 C6 N1 179.7(2) . . . . ?
C4 C5 C6 C7 -176.8(2) . . . . ?
C17 C5 C6 C7 1.7(4) . . . . ?
C3 C2 C1 C14 -7.0(5) . . . 2_566 ?
C13 C12 C19 C20 -93.9(3) . . . . ?
C11 C12 C19 C20 80.6(3) . . . . ?
C5 C4 C15 C16 95.3(3) . . . . ?
C3 C4 C15 C16 -81.4(3) . . . . ?
C8 C9 C10 C11 -173.7(2) . . . . ?
C8 C9 C10 S001 2.1(3) . . . . ?
C7 S001 C10 C9 -3.18(18) . . . . ?
C7 S001 C10 C11 172.5(2) . . . . ?
C4 C5 C17 C18 -93.1(3) . . . . ?
C6 C5 C17 C18 88.7(3) . . . . ?
C14 N2 C11 C10 -174.3(2) . . . . ?
C14 N2 C11 C12 0.7(3) . . . . ?
C9 C10 C11 N2 19.5(3) . . . . ?
S001 C10 C11 N2 -155.61(17) . . . . ?
C9 C10 C11 C12 -154.0(2) . . . . ?
S001 C10 C11 C12 30.9(4) . . . . ?
C13 C12 C11 N2 -1.9(3) . . . . ?
C19 C12 C11 N2 -177.4(2) . . . . ?
C13 C12 C11 C10 172.0(2) . . . . ?
C19 C12 C11 C10 -3.5(4) . . . . ?
C10 C9 C8 C7 0.5(3) . . . . ?
C6 C7 C8 C9 171.5(2) . . . . ?
S001 C7 C8 C9 -2.9(3) . . . . ?
C12 C13 C21 C22 91.5(4) . . . . ?
C14 C13 C21 C22 -83.5(4) . . . . ?

_refine_diff_density_max         0.419
_refine_diff_density_min         -0.307
_refine_diff_density_rms         0.049

####################################################################### 
# 
# 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_BrzSStfa
_database_code_depnum_ccdc_archive 'CCDC 1869467'
_audit_update_record             
;
2018-09-25 deposited with the CCDC.
2018-11-06 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/7
_shelx_SHELXL_version_number     2014/7
_chemical_name_systematic        Octaethyldithiabronzaphyrin
_chemical_name_common            Bronzaphyrin
_chemical_melting_point          ?
_chemical_formula_moiety         'C44 H52 N4 S2, 2(C4 H F6 O4)'
_chemical_formula_sum            'C52 H54 F12 N4 O8 S2'
_chemical_formula_weight         1155.11

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'

_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                   12.4875(4)
_cell_length_b                   12.9069(4)
_cell_length_c                   16.8517(6)
_cell_angle_alpha                90
_cell_angle_beta                 98.0780(10)
_cell_angle_gamma                90
_cell_volume                     2689.12(15)
_cell_formula_units_Z            2
_cell_measurement_temperature    100(2)
_cell_measurement_reflns_used    9941
_cell_measurement_theta_min      2.44
_cell_measurement_theta_max      27.49

_exptl_crystal_description       block
_exptl_crystal_colour            green
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.427
_exptl_crystal_F_000             1196
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.10
_exptl_absorpt_coefficient_mu    0.197
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6669
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_process_details   'SADABS 2014/5'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      100(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            69513
_diffrn_reflns_av_unetI/netI     0.0251
_diffrn_reflns_av_R_equivalents  0.0526
_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       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_theta_min         2.281
_diffrn_reflns_theta_max         27.558
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             6206
_reflns_number_gt                5135
_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-2014/7 (Sheldrick, 2014)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_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)+(0.0821P)²+6.0648P] 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         6206
_refine_ls_number_parameters     368
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0751
_refine_ls_R_factor_gt           0.0605
_refine_ls_wR_factor_ref         0.1648
_refine_ls_wR_factor_gt          0.1541
_refine_ls_goodness_of_fit_ref   0.992
_refine_ls_restrained_S_all      0.992
_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
S1 S 0.25222(4) 0.41813(4) 0.43469(4) 0.01457(15) Uani 1 1 d . . . . .
F5 F 0.87373(13) 0.31239(16) 0.40966(10) 0.0360(4) Uani 1 1 d . . . . .
O1 O 0.44549(14) 0.19277(14) 0.16231(10) 0.0187(4) Uani 1 1 d . . . . .
O3 O 0.67159(13) 0.26204(14) 0.42706(10) 0.0177(4) Uani 1 1 d . . . . .
F3 F 0.26307(15) 0.08073(17) 0.27060(11) 0.0463(5) Uani 1 1 d . . . . .
N1 N 0.33530(16) 0.71263(15) 0.39088(11) 0.0120(4) Uani 1 1 d . . . . .
O2 O 0.44791(16) 0.18312(19) 0.29539(11) 0.0322(5) Uani 1 1 d . . . . .
N2 N 0.48403(15) 0.20698(15) 0.50425(11) 0.0117(4) Uani 1 1 d . . . . .
O4 O 0.63436(17) 0.2387(2) 0.29406(11) 0.0411(6) Uani 1 1 d . . . . .
C6 C 0.27133(17) 0.62781(17) 0.39888(12) 0.0117(4) Uani 1 1 d . . . . .
F4 F 0.81758(19) 0.3461(3) 0.28876(13) 0.0883(12) Uani 1 1 d . . . . .
C11 C 0.38236(17) 0.24735(17) 0.48298(13) 0.0121(4) Uani 1 1 d . . . . .
C7 C 0.31759(18) 0.52808(18) 0.40612(13) 0.0129(4) Uani 1 1 d . . . . .
C4 C 0.17070(18) 0.77261(18) 0.40682(13) 0.0130(4) Uani 1 1 d . . . . .
C3 C 0.27882(18) 0.80167(18) 0.39746(13) 0.0124(4) Uani 1 1 d . . . . .
C12 C 0.30820(18) 0.18017(17) 0.51455(13) 0.0133(4) Uani 1 1 d . . . . .
C5 C 0.16598(17) 0.66558(18) 0.40770(13) 0.0127(4) Uani 1 1 d . . . . .
C14 C 0.47951(18) 0.12117(17) 0.55107(13) 0.0128(4) Uani 1 1 d . . . . .
C8 C 0.42658(18) 0.50484(18) 0.40145(14) 0.0151(4) Uani 1 1 d . . . . .
H8 H 0.4757 0.5538 0.3849 0.018 Uiso 1 1 calc R U . . .
C2 C 0.32228(18) 0.90252(17) 0.39775(13) 0.0139(4) Uani 1 1 d . . . . .
H2 H 0.2708 0.9567 0.3871 0.017 Uiso 1 1 calc R U . . .
C13 C 0.36777(18) 0.10118(17) 0.55518(13) 0.0132(4) Uani 1 1 d . . . . .
C9 C 0.45559(18) 0.40493(18) 0.42305(14) 0.0154(5) Uani 1 1 d . . . . .
H9 H 0.5265 0.3785 0.4225 0.018 Uiso 1 1 calc R U . . .
C10 C 0.37069(17) 0.34542(17) 0.44602(13) 0.0123(4) Uani 1 1 d . . . . .
C1 C 0.42932(18) 0.93383(17) 0.41130(14) 0.0141(4) Uani 1 1 d . . . . .
H1 H 0.4434 1.0013 0.3928 0.017 Uiso 1 1 calc R U . . .
C17 C 0.06910(18) 0.60024(19) 0.41615(15) 0.0170(5) Uani 1 1 d . . . . .
H17A H 0.0133 0.6439 0.4360 0.020 Uiso 1 1 calc R U . . .
H17B H 0.0901 0.5453 0.4564 0.020 Uiso 1 1 calc R U . . .
C24 C 0.40588(19) 0.17410(19) 0.22251(14) 0.0173(5) Uani 1 1 d . . . . .
C26 C 0.69395(19) 0.25845(19) 0.35921(14) 0.0168(5) Uani 1 1 d . . . . .
C15 C 0.08299(18) 0.84782(19) 0.41997(14) 0.0166(5) Uani 1 1 d . . . . .
H15A H 0.1162 0.9078 0.4507 0.020 Uiso 1 1 calc R U . . .
H15B H 0.0333 0.8138 0.4528 0.020 Uiso 1 1 calc R U . . .
C21 C 0.3277(2) 0.01359(19) 0.60187(14) 0.0181(5) Uani 1 1 d . . . . .
H21A H 0.3727 -0.0485 0.5964 0.022 Uiso 1 1 calc R U . . .
H21B H 0.2525 -0.0032 0.5786 0.022 Uiso 1 1 calc R U . . .
F6 F 0.85521(19) 0.1919(3) 0.3236(2) 0.1079(15) Uani 1 1 d . . . . .
C19 C 0.18762(18) 0.19364(19) 0.50580(15) 0.0175(5) Uani 1 1 d . . . . .
H19A H 0.1711 0.2661 0.5189 0.021 Uiso 1 1 calc R U . . .
H19B H 0.1583 0.1481 0.5448 0.021 Uiso 1 1 calc R U . . .
C20 C 0.1311(2) 0.1685(2) 0.42156(17) 0.0235(5) Uani 1 1 d . . . . .
H20A H 0.1592 0.2138 0.3826 0.035 Uiso 1 1 calc R U . . .
H20B H 0.0531 0.1795 0.4192 0.035 Uiso 1 1 calc R U . . .
H20C H 0.1449 0.0960 0.4089 0.035 Uiso 1 1 calc R U . . .
C18 C 0.0210(2) 0.5499(2) 0.33660(17) 0.0265(6) Uani 1 1 d . . . . .
H18A H -0.0034 0.6040 0.2974 0.040 Uiso 1 1 calc R U . . .
H18B H -0.0405 0.5062 0.3452 0.040 Uiso 1 1 calc R U . . .
H18C H 0.0763 0.5073 0.3164 0.040 Uiso 1 1 calc R U . . .
C25 C 0.8119(2) 0.2770(3) 0.34598(16) 0.0280(6) Uani 1 1 d . . . . .
F1 F 0.2609(3) 0.0904(4) 0.14568(16) 0.138(2) Uani 1 1 d . . . . .
C16 C 0.0176(2) 0.8870(2) 0.34257(17) 0.0298(6) Uani 1 1 d . . . . .
H16A H 0.0654 0.9241 0.3109 0.045 Uiso 1 1 calc R U . . .
H16B H -0.0392 0.9340 0.3554 0.045 Uiso 1 1 calc R U . . .
H16C H -0.0156 0.8281 0.3116 0.045 Uiso 1 1 calc R U . . .
C22 C 0.3307(3) 0.0383(2) 0.69047(17) 0.0339(7) Uani 1 1 d . . . . .
H22A H 0.4048 0.0559 0.7138 0.051 Uiso 1 1 calc R U . . .
H22B H 0.3063 -0.0223 0.7181 0.051 Uiso 1 1 calc R U . . .
H22C H 0.2829 0.0971 0.6965 0.051 Uiso 1 1 calc R U . . .
F2 F 0.2202(2) 0.2129(3) 0.2060(3) 0.135(2) Uani 1 1 d . . . . .
C23 C 0.2890(2) 0.1337(3) 0.21156(16) 0.0334(7) Uani 1 1 d . . . . .
H2X H 0.542(3) 0.228(2) 0.4879(18) 0.020(7) Uiso 1 1 d . . . . .
H1X H 0.395(3) 0.710(2) 0.3763(19) 0.025(8) Uiso 1 1 d . . . . .
H1O H 0.541(5) 0.217(5) 0.301(4) 0.11(2) 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
S1 C7 1.739(2) . ?
S1 C10 1.740(2) . ?
F5 C25 1.313(3) . ?
O1 C24 1.214(3) . ?
O3 C26 1.215(3) . ?
F3 C23 1.286(3) . ?
N1 C3 1.361(3) . ?
N1 C6 1.373(3) . ?
N1 H1X 0.82(3) . ?
O2 C24 1.271(3) . ?
O2 H1O 1.23(6) . ?
N2 C14 1.366(3) . ?
N2 C11 1.373(3) . ?
N2 H2X 0.85(3) . ?
O4 C26 1.263(3) . ?
O4 H1O 1.22(6) . ?
C6 C7 1.409(3) . ?
C6 C5 1.430(3) . ?
F4 C25 1.322(4) . ?
C11 C10 1.409(3) . ?
C11 C12 1.425(3) . ?
C7 C8 1.407(3) . ?
C4 C5 1.383(3) . ?
C4 C3 1.431(3) . ?
C4 C15 1.503(3) . ?
C3 C2 1.410(3) . ?
C12 C13 1.385(3) . ?
C12 C19 1.502(3) . ?
C5 C17 1.498(3) . ?
C14 C1 1.414(3) 3_666 ?
C14 C13 1.430(3) . ?
C8 C9 1.375(3) . ?
C8 H8 0.9500 . ?
C2 C1 1.384(3) . ?
C2 H2 0.9500 . ?
C13 C21 1.503(3) . ?
C9 C10 1.407(3) . ?
C9 H9 0.9500 . ?
C1 C14 1.414(3) 3_666 ?
C1 H1 0.9500 . ?
C17 C18 1.534(3) . ?
C17 H17A 0.9900 . ?
C17 H17B 0.9900 . ?
C24 C23 1.536(4) . ?
C26 C25 1.539(3) . ?
C15 C16 1.525(3) . ?
C15 H15A 0.9900 . ?
C15 H15B 0.9900 . ?
C21 C22 1.522(4) . ?
C21 H21A 0.9900 . ?
C21 H21B 0.9900 . ?
F6 C25 1.304(4) . ?
C19 C20 1.529(3) . ?
C19 H19A 0.9900 . ?
C19 H19B 0.9900 . ?
C20 H20A 0.9800 . ?
C20 H20B 0.9800 . ?
C20 H20C 0.9800 . ?
C18 H18A 0.9800 . ?
C18 H18B 0.9800 . ?
C18 H18C 0.9800 . ?
F1 C23 1.249(4) . ?
C16 H16A 0.9800 . ?
C16 H16B 0.9800 . ?
C16 H16C 0.9800 . ?
C22 H22A 0.9800 . ?
C22 H22B 0.9800 . ?
C22 H22C 0.9800 . ?
F2 C23 1.330(5) . ?

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
C7 S1 C10 92.61(11) . . ?
C3 N1 C6 110.49(19) . . ?
C3 N1 H1X 124(2) . . ?
C6 N1 H1X 124(2) . . ?
C24 O2 H1O 112(3) . . ?
C14 N2 C11 110.30(19) . . ?
C14 N2 H2X 124(2) . . ?
C11 N2 H2X 126(2) . . ?
C26 O4 H1O 114(3) . . ?
N1 C6 C7 120.0(2) . . ?
N1 C6 C5 107.14(19) . . ?
C7 C6 C5 132.4(2) . . ?
N2 C11 C10 119.4(2) . . ?
N2 C11 C12 107.30(19) . . ?
C10 C11 C12 132.8(2) . . ?
C8 C7 C6 125.3(2) . . ?
C8 C7 S1 109.70(17) . . ?
C6 C7 S1 124.53(17) . . ?
C5 C4 C3 107.77(19) . . ?
C5 C4 C15 127.6(2) . . ?
C3 C4 C15 124.4(2) . . ?
N1 C3 C2 125.2(2) . . ?
N1 C3 C4 107.18(19) . . ?
C2 C3 C4 127.6(2) . . ?
C13 C12 C11 107.47(19) . . ?
C13 C12 C19 126.5(2) . . ?
C11 C12 C19 126.0(2) . . ?
C4 C5 C6 107.3(2) . . ?
C4 C5 C17 126.8(2) . . ?
C6 C5 C17 125.8(2) . . ?
N2 C14 C1 124.8(2) . 3_666 ?
N2 C14 C13 107.10(19) . . ?
C1 C14 C13 128.1(2) 3_666 . ?
C9 C8 C7 114.0(2) . . ?
C9 C8 H8 123.0 . . ?
C7 C8 H8 123.0 . . ?
C1 C2 C3 129.2(2) . . ?
C1 C2 H2 115.4 . . ?
C3 C2 H2 115.4 . . ?
C12 C13 C14 107.65(19) . . ?
C12 C13 C21 128.1(2) . . ?
C14 C13 C21 124.0(2) . . ?
C8 C9 C10 113.8(2) . . ?
C8 C9 H9 123.1 . . ?
C10 C9 H9 123.1 . . ?
C9 C10 C11 125.2(2) . . ?
C9 C10 S1 109.73(17) . . ?
C11 C10 S1 124.51(17) . . ?
C2 C1 C14 128.7(2) . 3_666 ?
C2 C1 H1 115.6 . . ?
C14 C1 H1 115.6 3_666 . ?
C5 C17 C18 112.2(2) . . ?
C5 C17 H17A 109.2 . . ?
C18 C17 H17A 109.2 . . ?
C5 C17 H17B 109.2 . . ?
C18 C17 H17B 109.2 . . ?
H17A C17 H17B 107.9 . . ?
O1 C24 O2 128.9(2) . . ?
O1 C24 C23 117.3(2) . . ?
O2 C24 C23 113.8(2) . . ?
O3 C26 O4 129.8(2) . . ?
O3 C26 C25 118.8(2) . . ?
O4 C26 C25 111.4(2) . . ?
C4 C15 C16 113.7(2) . . ?
C4 C15 H15A 108.8 . . ?
C16 C15 H15A 108.8 . . ?
C4 C15 H15B 108.8 . . ?
C16 C15 H15B 108.8 . . ?
H15A C15 H15B 107.7 . . ?
C13 C21 C22 113.1(2) . . ?
C13 C21 H21A 109.0 . . ?
C22 C21 H21A 109.0 . . ?
C13 C21 H21B 109.0 . . ?
C22 C21 H21B 109.0 . . ?
H21A C21 H21B 107.8 . . ?
C12 C19 C20 113.1(2) . . ?
C12 C19 H19A 109.0 . . ?
C20 C19 H19A 109.0 . . ?
C12 C19 H19B 109.0 . . ?
C20 C19 H19B 109.0 . . ?
H19A C19 H19B 107.8 . . ?
C19 C20 H20A 109.5 . . ?
C19 C20 H20B 109.5 . . ?
H20A C20 H20B 109.5 . . ?
C19 C20 H20C 109.5 . . ?
H20A C20 H20C 109.5 . . ?
H20B C20 H20C 109.5 . . ?
C17 C18 H18A 109.5 . . ?
C17 C18 H18B 109.5 . . ?
H18A C18 H18B 109.5 . . ?
C17 C18 H18C 109.5 . . ?
H18A C18 H18C 109.5 . . ?
H18B C18 H18C 109.5 . . ?
F6 C25 F5 108.0(3) . . ?
F6 C25 F4 106.8(3) . . ?
F5 C25 F4 106.0(2) . . ?
F6 C25 C26 110.8(2) . . ?
F5 C25 C26 113.6(2) . . ?
F4 C25 C26 111.2(2) . . ?
C15 C16 H16A 109.5 . . ?
C15 C16 H16B 109.5 . . ?
H16A C16 H16B 109.5 . . ?
C15 C16 H16C 109.5 . . ?
H16A C16 H16C 109.5 . . ?
H16B C16 H16C 109.5 . . ?
C21 C22 H22A 109.5 . . ?
C21 C22 H22B 109.5 . . ?
H22A C22 H22B 109.5 . . ?
C21 C22 H22C 109.5 . . ?
H22A C22 H22C 109.5 . . ?
H22B C22 H22C 109.5 . . ?
F1 C23 F3 112.3(3) . . ?
F1 C23 F2 100.6(4) . . ?
F3 C23 F2 103.4(3) . . ?
F1 C23 C24 113.7(3) . . ?
F3 C23 C24 115.2(2) . . ?
F2 C23 C24 110.0(3) . . ?

_refine_diff_density_max         1.892
_refine_diff_density_min         -1.039
_refine_diff_density_rms         0.082


_exptl_crystal_recrystallization_method 
'Re-crystallisation from solvent: TFA in CHCl3'
