# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2015

####################################################################### 
# 
# 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_compound1
_database_code_depnum_ccdc_archive 'CCDC 1052870'
_audit_update_record             
;
2015-03-09 deposited with the CCDC.
2015-06-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            zinccarboxylate
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C18.50 H15 N1.50 O7.50 S Zn'
_chemical_formula_weight         475.75

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'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 2/c'
_space_group_name_Hall           '-C 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+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'

_cell_length_a                   22.2749(7)
_cell_length_b                   12.7253(4)
_cell_length_c                   17.7334(9)
_cell_angle_alpha                90
_cell_angle_beta                 126.3350(10)
_cell_angle_gamma                90
_cell_volume                     4049.3(3)
_cell_formula_units_Z            8
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       platelike
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.561
_exptl_crystal_F_000             1940
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.150
_exptl_absorpt_coefficient_mu    1.361
_shelx_estimated_absorpt_T_min   0.773
_shelx_estimated_absorpt_T_max   0.822
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.773
_exptl_absorpt_correction_T_max  0.822
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            17676
_diffrn_reflns_av_unetI/netI     0.0303
_diffrn_reflns_av_R_equivalents  0.0282
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_theta_min         2.852
_diffrn_reflns_theta_max         28.275
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measured_fraction_theta_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_point_group_measured_fraction_full 0.999
_reflns_number_total             4903
_reflns_number_gt                3820
_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 SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-2014 (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)+(0.0431P)²+3.8227P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    none
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4903
_refine_ls_number_parameters     277
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0508
_refine_ls_R_factor_gt           0.0330
_refine_ls_wR_factor_ref         0.0913
_refine_ls_wR_factor_gt          0.0835
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_restrained_S_all      1.052
_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
Zn1 Zn 0.05216(2) 0.52064(2) 0.10152(2) 0.03001(9) Uani 1 1 d . . . . .
S1 S 0.33493(3) 0.62963(4) -0.07966(4) 0.03658(14) Uani 1 1 d . . . . .
O1 O 0.09615(11) 0.58837(14) 0.22479(11) 0.0455(4) Uani 1 1 d . . . . .
O2 O -0.03919(10) 0.45915(15) 0.08347(14) 0.0479(4) Uani 1 1 d . . . . .
O3 O 0.12316(10) 0.56210(15) 0.07107(13) 0.0463(4) Uani 1 1 d . . . . .
O4 O 0.09448(10) 0.37191(13) 0.12711(12) 0.0448(4) Uani 1 1 d . . . . .
O5 O -0.01395(10) 0.65117(14) 0.02715(12) 0.0474(4) Uani 1 1 d . . . . .
O6 O 0.29885(10) 0.66774(14) -0.17318(13) 0.0501(5) Uani 1 1 d . . . . .
O7 O 0.39742(10) 0.68535(14) -0.00283(14) 0.0512(5) Uani 1 1 d . . . . .
C1 C 0.06419(13) 0.31835(18) 0.05380(17) 0.0370(5) Uani 1 1 d . . . . .
C2 C 0.12753(15) 0.6738(2) 0.24889(18) 0.0468(6) Uani 1 1 d . . . . .
H2 H 0.1450 0.7005 0.2164 0.056 Uiso 1 1 calc R U . . .
N1 N 0.13799(16) 0.72966(19) 0.31758(17) 0.0592(6) Uani 1 1 d . . . . .
C4 C 0.1785(3) 0.8295(3) 0.3459(3) 0.1060(16) Uani 1 1 d . . . . .
H4A H 0.1804 0.8588 0.3972 0.159 Uiso 1 1 calc R U . . .
H4B H 0.2283 0.8177 0.3650 0.159 Uiso 1 1 calc R U . . .
H4C H 0.1534 0.8776 0.2941 0.159 Uiso 1 1 calc R U . . .
C5 C 0.1073(3) 0.6971(4) 0.3668(3) 0.1077(16) Uani 1 1 d . . . . .
H5A H 0.1206 0.7475 0.4147 0.162 Uiso 1 1 calc R U . . .
H5B H 0.0540 0.6928 0.3234 0.162 Uiso 1 1 calc R U . . .
H5C H 0.1270 0.6295 0.3949 0.162 Uiso 1 1 calc R U . . .
C6 C 0.09075(13) 0.20655(18) 0.06283(16) 0.0351(5) Uani 1 1 d . . . . .
C7 C 0.04977(14) 0.1394(2) -0.01256(18) 0.0426(6) Uani 1 1 d . . . . .
H7 H 0.0065 0.1635 -0.0680 0.051 Uiso 1 1 calc R U . . .
C8 C 0.07251(15) 0.0366(2) -0.00638(18) 0.0432(6) Uani 1 1 d . . . . .
H8 H 0.0446 -0.0086 -0.0572 0.052 Uiso 1 1 calc R U . . .
C9 C 0.13687(13) 0.00160(17) 0.07567(17) 0.0340(5) Uani 1 1 d . . . . .
C10 C 0.17886(14) 0.0676(2) 0.15218(18) 0.0437(6) Uani 1 1 d . . . . .
H10 H 0.2222 0.0434 0.2074 0.052 Uiso 1 1 calc R U . . .
C11 C 0.15543(14) 0.1702(2) 0.14530(18) 0.0441(6) Uani 1 1 d . . . . .
H11 H 0.1832 0.2152 0.1963 0.053 Uiso 1 1 calc R U . . .
C12 C 0.10328(14) 0.56171(18) -0.01130(18) 0.0383(5) Uani 1 1 d . . . . .
C13 C 0.16127(13) 0.58452(18) -0.02713(17) 0.0356(5) Uani 1 1 d . . . . .
C14 C 0.14070(13) 0.5888(2) -0.11740(17) 0.0421(6) Uani 1 1 d . . . . .
H14 H 0.0908 0.5809 -0.1676 0.050 Uiso 1 1 calc R U . . .
C15 C 0.19330(13) 0.6046(2) -0.13441(17) 0.0408(5) Uani 1 1 d . . . . .
H15 H 0.1793 0.6071 -0.1953 0.049 Uiso 1 1 calc R U . . .
C16 C 0.26711(12) 0.61657(17) -0.05860(16) 0.0326(5) Uani 1 1 d . . . . .
C17 C 0.28866(13) 0.6143(2) 0.03206(17) 0.0429(6) Uani 1 1 d . . . . .
H17 H 0.3385 0.6227 0.0821 0.051 Uiso 1 1 calc R U . . .
C18 C 0.23555(14) 0.5994(2) 0.04784(18) 0.0433(6) Uani 1 1 d . . . . .
H18 H 0.2495 0.5993 0.1087 0.052 Uiso 1 1 calc R U . . .
O15 O 0.0000 -0.0473(5) 0.2500 0.161(3) Uani 1 2 d S T P . .
N2 N 0.0000 0.1268(4) 0.2500 0.0778(12) Uani 1 2 d S T P . .
C31 C 0.0289(10) 0.2102(9) 0.2201(11) 0.119(6) Uani 0.5 1 d . . P . .
C30 C 0.0000 0.0284(8) 0.2500 0.261(10) Uani 1 2 d S T P . .
C32 C 0.0468(7) 0.1518(10) 0.2231(7) 0.094(4) Uani 0.5 1 d . . P . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Zn1 O1 1.9857(16) . ?
Zn1 O2 2.0207(17) . ?
Zn1 O3 2.0207(17) . ?
Zn1 O4 2.0420(16) . ?
Zn1 O5 2.0894(16) . ?
Zn1 Zn1 2.9539(5) 5_565 ?
S1 O7 1.4315(19) . ?
S1 O6 1.4324(19) . ?
S1 C16 1.766(2) . ?
S1 C9 1.771(2) 7 ?
O1 C2 1.224(3) . ?
O2 C12 1.257(3) 5_565 ?
O3 C12 1.250(3) . ?
O4 C1 1.253(3) . ?
O5 C1 1.249(3) 5_565 ?
C1 O5 1.249(3) 5_565 ?
C1 C6 1.512(3) . ?
C2 N1 1.307(3) . ?
N1 C5 1.452(4) . ?
N1 C4 1.465(4) . ?
C6 C7 1.380(3) . ?
C6 C11 1.390(3) . ?
C7 C8 1.384(3) . ?
C8 C9 1.378(3) . ?
C9 C10 1.385(4) . ?
C9 S1 1.771(2) 7 ?
C10 C11 1.384(3) . ?
C12 O2 1.257(3) 5_565 ?
C12 C13 1.504(3) . ?
C13 C14 1.381(3) . ?
C13 C18 1.391(3) . ?
C14 C15 1.387(3) . ?
C15 C16 1.384(3) . ?
C16 C17 1.379(3) . ?
C17 C18 1.381(3) . ?
O15 C30 0.962(9) . ?
N2 C30 1.253(10) . ?
N2 C32 1.415(12) . ?
N2 C32 1.415(12) 2 ?
N2 C31 1.491(14) . ?
N2 C31 1.491(14) 2 ?
C31 C32 0.829(18) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Zn1 O2 97.84(8) . . ?
O1 Zn1 O3 103.12(8) . . ?
O2 Zn1 O3 158.88(8) . . ?
O1 Zn1 O4 107.21(7) . . ?
O2 Zn1 O4 88.01(8) . . ?
O3 Zn1 O4 88.28(7) . . ?
O1 Zn1 O5 93.06(7) . . ?
O2 Zn1 O5 86.62(8) . . ?
O3 Zn1 O5 89.67(7) . . ?
O4 Zn1 O5 159.56(7) . . ?
O1 Zn1 Zn1 159.68(6) . 5_565 ?
O2 Zn1 Zn1 75.35(6) . 5_565 ?
O3 Zn1 Zn1 84.01(5) . 5_565 ?
O4 Zn1 Zn1 91.85(5) . 5_565 ?
O5 Zn1 Zn1 67.71(5) . 5_565 ?
O7 S1 O6 119.76(12) . . ?
O7 S1 C16 108.46(11) . . ?
O6 S1 C16 108.26(11) . . ?
O7 S1 C9 107.89(11) . 7 ?
O6 S1 C9 107.94(11) . 7 ?
C16 S1 C9 103.32(10) . 7 ?
C2 O1 Zn1 125.24(17) . . ?
C12 O2 Zn1 132.25(17) 5_565 . ?
C12 O3 Zn1 121.31(17) . . ?
C1 O4 Zn1 112.32(15) . . ?
C1 O5 Zn1 142.08(17) 5_565 . ?
O5 C1 O4 126.0(2) 5_565 . ?
O5 C1 C6 116.2(2) 5_565 . ?
O4 C1 C6 117.7(2) . . ?
O1 C2 N1 123.9(3) . . ?
C2 N1 C5 121.2(3) . . ?
C2 N1 C4 121.7(3) . . ?
C5 N1 C4 117.1(3) . . ?
C7 C6 C11 119.5(2) . . ?
C7 C6 C1 119.1(2) . . ?
C11 C6 C1 121.4(2) . . ?
C6 C7 C8 120.5(2) . . ?
C9 C8 C7 119.5(2) . . ?
C8 C9 C10 121.0(2) . . ?
C8 C9 S1 117.99(18) . 7 ?
C10 C9 S1 121.02(18) . 7 ?
C11 C10 C9 119.0(2) . . ?
C10 C11 C6 120.5(2) . . ?
O3 C12 O2 126.3(2) . 5_565 ?
O3 C12 C13 117.9(2) . . ?
O2 C12 C13 115.7(2) 5_565 . ?
C14 C13 C18 119.5(2) . . ?
C14 C13 C12 119.5(2) . . ?
C18 C13 C12 121.0(2) . . ?
C13 C14 C15 121.0(2) . . ?
C16 C15 C14 118.4(2) . . ?
C17 C16 C15 121.5(2) . . ?
C17 C16 S1 119.88(18) . . ?
C15 C16 S1 118.54(18) . . ?
C16 C17 C18 119.4(2) . . ?
C17 C18 C13 120.1(2) . . ?
C30 N2 C32 103.0(6) . . ?
C30 N2 C32 103.0(6) . 2 ?
C32 N2 C32 154.1(12) . 2 ?
C30 N2 C31 135.3(7) . . ?
C32 N2 C31 33.0(8) . . ?
C32 N2 C31 121.3(10) 2 . ?
C30 N2 C31 135.3(7) . 2 ?
C32 N2 C31 121.3(10) . 2 ?
C32 N2 C31 33.0(8) 2 2 ?
C31 N2 C31 89.4(13) . 2 ?
C32 C31 N2 68.4(14) . . ?
O15 C30 N2 180.0 . . ?
C31 C32 N2 78.5(19) . . ?

_refine_diff_density_max         0.408
_refine_diff_density_min         -0.268
_refine_diff_density_rms         0.062

_shelxl_version_number           2014-3

####################################################################### 
# 
# 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_compound2
_database_code_depnum_ccdc_archive 'CCDC 1052871'
_audit_update_record             
;
2015-03-09 deposited with the CCDC.
2015-06-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            zinccarboxylate
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C53 H38 N2 O20 S3 Zn3'
_chemical_formula_weight         1315.14

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'
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'
Zn Zn 0.2839 1.4301 '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'

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

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

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

_cell_length_a                   16.3303(4)
_cell_length_b                   20.6847(5)
_cell_length_c                   16.9801(4)
_cell_angle_alpha                90
_cell_angle_beta                 98.4720(10)
_cell_angle_gamma                90
_cell_volume                     5673.1(2)
_cell_formula_units_Z            4
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       platelike
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.540
_exptl_crystal_F_000             2672
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.150
_exptl_absorpt_coefficient_mu    1.445
_shelx_estimated_absorpt_T_min   0.761
_shelx_estimated_absorpt_T_max   0.812
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.845
_exptl_absorpt_correction_T_max  0.880
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            43897
_diffrn_reflns_av_unetI/netI     0.0729
_diffrn_reflns_av_R_equivalents  0.0723
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_theta_min         1.562
_diffrn_reflns_theta_max         24.712
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 0.942
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 0.942
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 0.942
_reflns_number_total             9670
_reflns_number_gt                6042
_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 SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-2014 (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)+(0.1273P)²+2.4768P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    none
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         9670
_refine_ls_number_parameters     729
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.1173
_refine_ls_R_factor_gt           0.0639
_refine_ls_wR_factor_ref         0.2129
_refine_ls_wR_factor_gt          0.1734
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_restrained_S_all      1.039
_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
Zn1 Zn 0.47966(5) 0.17416(4) 0.24922(4) 0.0336(2) Uani 1 1 d . . . . .
Zn2 Zn 0.60281(5) 0.15028(4) 0.43951(4) 0.0354(2) Uani 1 1 d . . . . .
Zn3 Zn 0.38786(5) 0.13803(4) 0.05566(5) 0.0428(3) Uani 1 1 d . . . . .
S1 S 0.54593(18) 0.56473(12) 0.3733(2) 0.0858(10) Uani 1 1 d . . . . .
S2 S -0.04189(10) 0.27397(9) 0.24087(10) 0.0371(4) Uani 1 1 d . . . . .
S3 S 0.11763(10) 0.00600(9) 0.45812(11) 0.0398(5) Uani 1 1 d . . . . .
O1 O 0.6035(3) 0.1552(3) 0.2526(3) 0.0715(19) Uani 1 1 d . . . . .
O2 O 0.4962(3) 0.2468(3) 0.3300(3) 0.0512(13) Uani 1 1 d . . . . .
O3 O 0.4771(4) 0.1110(3) 0.3576(4) 0.085(2) Uani 1 1 d . . . . .
O4 O 0.4931(3) 0.2428(3) 0.1620(3) 0.0503(13) Uani 1 1 d . . . . .
O5 O 0.3540(3) 0.1878(2) 0.2387(3) 0.0429(12) Uani 1 1 d . . . . .
O6 O 0.4613(6) 0.0877(3) 0.1908(5) 0.112(3) Uani 1 1 d . . . . .
O7 O 0.5961(3) 0.2446(2) 0.4337(3) 0.0488(13) Uani 1 1 d . . . . .
O8 O 0.6694(3) 0.1140(3) 0.3647(3) 0.0514(14) Uani 1 1 d . . . . .
O9 O 0.5106(4) 0.1040(3) 0.4867(4) 0.081(2) Uani 1 1 d . . . . .
O10 O 0.4615(4) 0.2070(3) 0.0371(3) 0.0566(15) Uani 1 1 d . . . . .
O11 O 0.3020(3) 0.1732(3) 0.1090(3) 0.0518(14) Uani 1 1 d . . . . .
O12 O 0.4341(5) 0.0522(3) 0.0701(4) 0.086(2) Uani 1 1 d . . . . .
O13 O 0.6886(3) 0.1410(3) 0.5349(3) 0.0552(14) Uani 1 1 d . . . . .
O14 O 0.3255(4) 0.1251(3) -0.0538(3) 0.0602(15) Uani 1 1 d . . . . .
O15 O -0.0956(3) 0.2766(3) 0.1654(3) 0.0535(14) Uani 1 1 d . . . . .
O16 O -0.0653(3) 0.2371(2) 0.3049(3) 0.0479(13) Uani 1 1 d . . . . .
O17 O 0.1198(3) -0.0431(3) 0.5174(3) 0.0565(14) Uani 1 1 d . . . . .
O18 O 0.0719(3) -0.0040(3) 0.3803(3) 0.0528(14) Uani 1 1 d . . . . .
O19 O 0.5631(5) 0.5895(3) 0.4521(5) 0.119(3) Uani 1 1 d . . . . .
O20 O 0.4731(4) 0.5844(3) 0.3212(6) 0.121(3) Uani 1 1 d . . . . .
C17 C 0.2366(4) 0.0508(4) 0.3760(4) 0.0428(18) Uani 1 1 d . . . . .
H17 H 0.1944 0.0542 0.3330 0.051 Uiso 1 1 calc R U . . .
C31 C 0.1511(4) 0.2230(4) 0.1326(4) 0.0411(18) Uani 1 1 d . . . . .
H31 H 0.1627 0.2195 0.0807 0.049 Uiso 1 1 calc R U . . .
C30 C 0.0729(4) 0.2426(4) 0.1459(4) 0.0430(18) Uani 1 1 d . . . . .
H30 H 0.0322 0.2524 0.1033 0.052 Uiso 1 1 calc R U . . .
C15 C 0.2830(4) 0.0189(4) 0.5114(4) 0.0458(19) Uani 1 1 d . . . . .
H15 H 0.2719 0.0001 0.5585 0.055 Uiso 1 1 calc R U . . .
C27 C 0.1937(4) 0.2132(4) 0.2738(4) 0.0432(18) Uani 1 1 d . . . . .
H27 H 0.2338 0.2035 0.3169 0.052 Uiso 1 1 calc R U . . .
C02 C 0.5266(6) -0.0964(4) 0.2788(5) 0.064(2) Uani 1 1 d . . . . .
H02 H 0.5405 -0.1046 0.3330 0.077 Uiso 1 1 calc R U . . .
C2 C 0.8249(7) 0.1475(6) 0.6531(7) 0.105(4) Uani 1 1 d . . . . .
H2A H 0.8654 0.1136 0.6602 0.158 Uiso 1 1 calc R U . . .
H2B H 0.8392 0.1801 0.6930 0.158 Uiso 1 1 calc R U . . .
H2C H 0.8235 0.1663 0.6012 0.158 Uiso 1 1 calc R U . . .
C1 C 0.6827(5) 0.1206(4) 0.5995(5) 0.056(2) Uani 1 1 d . . . . .
H1 H 0.6320 0.1034 0.6075 0.068 Uiso 1 1 calc R U . . .
C9 C 0.8678(5) 0.0814(4) 0.1768(6) 0.056(2) Uani 1 1 d . . . . .
C43 C 0.5935(6) 0.4482(5) 0.4417(5) 0.063(2) Uani 1 1 d . . . . .
H43 H 0.6249 0.4715 0.4822 0.075 Uiso 1 1 calc R U . . .
C20 C 0.5089(6) -0.0348(5) 0.2522(5) 0.070(3) Uani 1 1 d . . . . .
H20 H 0.5118 -0.0009 0.2884 0.085 Uiso 1 1 calc R U . . .
C26 C 0.2122(4) 0.2085(3) 0.1964(4) 0.0339(15) Uani 1 1 d . . . . .
C24 C 0.4850(5) -0.0728(4) 0.1178(5) 0.052(2) Uani 1 1 d . . . . .
H24 H 0.4709 -0.0650 0.0635 0.062 Uiso 1 1 calc R U . . .
C3 C 0.2989(5) 0.1678(5) -0.1007(5) 0.059(2) Uani 1 1 d . . . . .
H3 H 0.3054 0.2105 -0.0837 0.071 Uiso 1 1 calc R U . . .
C12 C 0.4623(5) 0.0959(4) 0.4232(6) 0.059(2) Uani 1 1 d . . . . .
C28 C 0.1159(4) 0.2322(4) 0.2863(4) 0.0432(18) Uani 1 1 d . . . . .
H28 H 0.1035 0.2348 0.3380 0.052 Uiso 1 1 calc R U . . .
C38 C 0.5142(4) 0.3198(4) -0.0244(4) 0.0409(17) Uani 1 1 d . . . . .
H38 H 0.4898 0.2882 -0.0593 0.049 Uiso 1 1 calc R U . . .
C36 C 0.5798(4) 0.4219(3) -0.0033(4) 0.0362(16) Uani 1 1 d . . . . .
C42 C 0.5934(5) 0.3815(4) 0.4424(4) 0.056(2) Uani 1 1 d . . . . .
H42 H 0.6257 0.3598 0.4838 0.067 Uiso 1 1 calc R U . . .
C29 C 0.0562(4) 0.2473(3) 0.2230(4) 0.0321(15) Uani 1 1 d . . . . .
N1 N 0.7430(5) 0.1207(4) 0.6606(4) 0.070(2) Uani 1 1 d . . . . .
C6 C 0.7344(4) 0.1086(4) 0.2512(4) 0.0435(18) Uani 1 1 d . . . . .
C25 C 0.2972(4) 0.1878(3) 0.1810(4) 0.0371(16) Uani 1 1 d . . . . .
C35 C 0.5881(4) 0.4137(4) 0.0789(4) 0.0444(19) Uani 1 1 d . . . . .
H35 H 0.6124 0.4455 0.1133 0.053 Uiso 1 1 calc R U . . .
C46 C 0.5004(5) 0.3783(4) 0.3216(5) 0.055(2) Uani 1 1 d . . . . .
H46 H 0.4697 0.3551 0.2805 0.066 Uiso 1 1 calc R U . . .
C33 C 0.5217(4) 0.3098(3) 0.0569(4) 0.0346(16) Uani 1 1 d . . . . .
C23 C 0.5042(5) -0.1348(4) 0.1450(4) 0.0475(19) Uani 1 1 d . . . . .
H23 H 0.5040 -0.1687 0.1090 0.057 Uiso 1 1 calc R U . . .
C16 C 0.3152(5) 0.0706(4) 0.3690(5) 0.051(2) Uani 1 1 d . . . . .
H16 H 0.3265 0.0866 0.3206 0.062 Uiso 1 1 calc R U . . .
C11 C 0.7278(6) 0.1106(5) 0.1699(5) 0.072(3) Uani 1 1 d . . . . .
H11 H 0.6776 0.1219 0.1396 0.086 Uiso 1 1 calc R U . . .
C19 C 0.4868(5) -0.0227(4) 0.1715(5) 0.051(2) Uani 1 1 d . . . . .
C14 C 0.3622(4) 0.0400(4) 0.5042(5) 0.051(2) Uani 1 1 d . . . . .
H14 H 0.4047 0.0363 0.5469 0.061 Uiso 1 1 calc R U . . .
C51 C 0.5463(4) 0.2743(4) 0.3821(4) 0.0365(16) Uani 1 1 d . . . . .
C45 C 0.4986(5) 0.4446(5) 0.3195(6) 0.072(3) Uani 1 1 d . . . . .
H45 H 0.4660 0.4663 0.2783 0.086 Uiso 1 1 calc R U . . .
C18 C 0.4613(5) 0.0450(4) 0.1437(6) 0.059(2) Uani 1 1 d . . . . .
C8 C 0.8752(5) 0.0776(4) 0.2566(5) 0.055(2) Uani 1 1 d . . . . .
H8 H 0.9257 0.0665 0.2864 0.066 Uiso 1 1 calc R U . . .
C44 C 0.5467(5) 0.4787(4) 0.3803(6) 0.058(2) Uani 1 1 d . . . . .
C5 C 0.6624(4) 0.1271(4) 0.2923(4) 0.0406(17) Uani 1 1 d . . . . .
C13 C 0.3778(4) 0.0670(4) 0.4326(5) 0.048(2) Uani 1 1 d . . . . .
N2 N 0.2624(4) 0.1570(4) -0.1725(4) 0.0594(19) Uani 1 1 d . . . . .
C4 C 0.2297(6) 0.2108(6) -0.2232(6) 0.096(4) Uani 1 1 d . . . . .
H4A H 0.1704 0.2112 -0.2280 0.144 Uiso 1 1 calc R U . . .
H4B H 0.2459 0.2058 -0.2750 0.144 Uiso 1 1 calc R U . . .
H4C H 0.2514 0.2507 -0.2000 0.144 Uiso 1 1 calc R U . . .
C7 C 0.8080(4) 0.0899(4) 0.2940(5) 0.051(2) Uani 1 1 d . . . . .
H7 H 0.8125 0.0856 0.3490 0.062 Uiso 1 1 calc R U . . .
C34 C 0.5596(4) 0.3573(4) 0.1079(4) 0.0432(18) Uani 1 1 d . . . . .
H34 H 0.5657 0.3506 0.1626 0.052 Uiso 1 1 calc R U . . .
C41 C 0.5460(4) 0.3457(3) 0.3822(4) 0.0366(16) Uani 1 1 d . . . . .
C37 C 0.5431(4) 0.3765(4) -0.0542(4) 0.0398(17) Uani 1 1 d . . . . .
H37 H 0.5372 0.3833 -0.1089 0.048 Uiso 1 1 calc R U . . .
C32 C 0.4904(4) 0.2488(4) 0.0890(4) 0.0397(17) Uani 1 1 d . . . . .
C39 C 0.2206(4) 0.0262(3) 0.4468(4) 0.0363(16) Uani 1 1 d . . . . .
C22 C 0.5235(4) -0.1460(3) 0.2246(4) 0.0373(16) Uani 1 1 d . . . . .
C21 C 0.7947(6) 0.0962(5) 0.1328(5) 0.077(3) Uani 1 1 d . . . . .
H21 H 0.7896 0.0965 0.0775 0.092 Uiso 1 1 calc R U . . .
C47 C 0.2524(7) 0.0927(6) -0.2014(6) 0.097(4) Uani 1 1 d . . . . .
H47A H 0.2823 0.0637 -0.1634 0.145 Uiso 1 1 calc R U . . .
H47B H 0.2736 0.0894 -0.2511 0.145 Uiso 1 1 calc R U . . .
H47C H 0.1947 0.0816 -0.2092 0.145 Uiso 1 1 calc R U . . .
C50 C 0.7246(9) 0.0936(8) 0.7366(8) 0.142(5) Uiso 1 1 d . . . . .
H50A H 0.7567 0.0551 0.7491 0.212 Uiso 1 1 calc R U . . .
H50B H 0.6667 0.0833 0.7317 0.212 Uiso 1 1 calc R U . . .
H50C H 0.7383 0.1248 0.7783 0.212 Uiso 1 1 calc R U . . .
C70 C 0.2637(9) 0.2568(15) 0.4856(11) 0.32(2) Uani 1 1 d . . . . .
C74 C 0.7084(8) 0.1512(7) -0.0603(6) 0.117(5) Uani 1 1 d . . . . .
C72 C 0.1961(8) 0.0452(7) 0.1763(8) 0.117(4) Uani 1 1 d . . . . .
C71 C 0.323(2) 0.2666(9) 0.4674(8) 0.286(19) Uani 1 1 d . . . . .
C75 C 0.7702(9) 0.5101(7) 0.5565(9) 0.136(5) Uani 1 1 d . . . . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Zn1 O2 2.025(5) . ?
Zn1 O6 2.046(7) . ?
Zn1 O5 2.053(4) . ?
Zn1 O1 2.053(5) . ?
Zn1 O4 2.087(5) . ?
Zn1 O3 2.262(7) . ?
Zn2 O8 1.941(5) . ?
Zn2 O7 1.956(5) . ?
Zn2 O13 1.988(5) . ?
Zn2 O9 2.045(6) . ?
Zn2 O3 2.443(7) . ?
Zn2 C12 2.534(9) . ?
Zn3 O11 1.921(5) . ?
Zn3 O10 1.923(5) . ?
Zn3 O12 1.930(6) . ?
Zn3 O14 2.001(5) . ?
S1 O19 1.422(8) . ?
S1 O20 1.433(9) . ?
S1 C9 1.783(7) 2_655 ?
S1 C44 1.784(9) . ?
S2 O16 1.424(5) . ?
S2 O15 1.443(5) . ?
S2 C29 1.762(7) . ?
S2 C22 1.767(8) 2 ?
S3 O17 1.426(5) . ?
S3 O18 1.434(5) . ?
S3 C39 1.770(6) . ?
S3 C36 1.776(7) 4_566 ?
O1 C5 1.235(8) . ?
O2 C51 1.249(8) . ?
O3 C12 1.216(10) . ?
O4 C32 1.240(8) . ?
O5 C25 1.246(8) . ?
O6 C18 1.191(11) . ?
O7 C51 1.265(8) . ?
O8 C5 1.247(8) . ?
O9 C12 1.250(10) . ?
O10 C32 1.274(9) . ?
O11 C25 1.272(8) . ?
O12 C18 1.272(10) . ?
O13 C1 1.193(9) . ?
O14 C3 1.225(10) . ?
C17 C39 1.366(9) . ?
C17 C16 1.370(10) . ?
C31 C30 1.391(10) . ?
C31 C26 1.394(9) . ?
C30 C29 1.379(9) . ?
C15 C14 1.388(10) . ?
C15 C39 1.391(9) . ?
C27 C28 1.376(10) . ?
C27 C26 1.395(9) . ?
C02 C20 1.368(12) . ?
C02 C22 1.374(11) . ?
C2 N1 1.469(13) . ?
C1 N1 1.321(10) . ?
C9 C8 1.346(11) . ?
C9 C21 1.346(12) . ?
C9 S1 1.784(7) 2_645 ?
C43 C44 1.354(12) . ?
C43 C42 1.379(12) . ?
C20 C19 1.387(10) . ?
C26 C25 1.512(9) . ?
C24 C19 1.378(11) . ?
C24 C23 1.383(10) . ?
C3 N2 1.296(10) . ?
C12 C13 1.533(11) . ?
C28 C29 1.377(9) . ?
C38 C33 1.383(9) . ?
C38 C37 1.386(10) . ?
C36 C37 1.356(10) . ?
C36 C35 1.393(9) . ?
C36 S3 1.776(7) 4_665 ?
C42 C41 1.400(10) . ?
N1 C50 1.478(15) . ?
C6 C7 1.366(10) . ?
C6 C11 1.369(10) . ?
C6 C5 1.504(9) . ?
C35 C34 1.374(10) . ?
C46 C41 1.357(10) . ?
C46 C45 1.372(12) . ?
C33 C34 1.391(10) . ?
C33 C32 1.495(10) . ?
C23 C22 1.362(9) . ?
C16 C13 1.376(11) . ?
C11 C21 1.373(12) . ?
C19 C18 1.517(12) . ?
C14 C13 1.394(10) . ?
C51 C41 1.477(10) . ?
C45 C44 1.393(13) . ?
C8 C7 1.371(10) . ?
N2 C47 1.418(13) . ?
N2 C4 1.458(12) . ?
C22 S2 1.767(8) 2_545 ?
C70 C71 1.08(4) . ?

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
O2 Zn1 O6 166.4(3) . . ?
O2 Zn1 O5 89.4(2) . . ?
O6 Zn1 O5 90.3(3) . . ?
O2 Zn1 O1 95.2(2) . . ?
O6 Zn1 O1 85.4(3) . . ?
O5 Zn1 O1 175.5(2) . . ?
O2 Zn1 O4 87.6(2) . . ?
O6 Zn1 O4 105.9(3) . . ?
O5 Zn1 O4 93.0(2) . . ?
O1 Zn1 O4 86.8(2) . . ?
O2 Zn1 O3 83.9(3) . . ?
O6 Zn1 O3 82.5(3) . . ?
O5 Zn1 O3 90.7(2) . . ?
O1 Zn1 O3 90.2(2) . . ?
O4 Zn1 O3 170.7(2) . . ?
O8 Zn2 O7 112.7(2) . . ?
O8 Zn2 O13 95.7(2) . . ?
O7 Zn2 O13 99.5(2) . . ?
O8 Zn2 O9 126.3(3) . . ?
O7 Zn2 O9 116.6(2) . . ?
O13 Zn2 O9 96.1(3) . . ?
O8 Zn2 O3 90.2(2) . . ?
O7 Zn2 O3 105.5(2) . . ?
O13 Zn2 O3 149.7(2) . . ?
O9 Zn2 O3 57.5(2) . . ?
O8 Zn2 C12 110.0(3) . . ?
O7 Zn2 C12 113.3(2) . . ?
O13 Zn2 C12 124.3(3) . . ?
O9 Zn2 C12 29.3(3) . . ?
O3 Zn2 C12 28.2(2) . . ?
O11 Zn3 O10 108.3(2) . . ?
O11 Zn3 O12 126.0(3) . . ?
O10 Zn3 O12 117.5(3) . . ?
O11 Zn3 O14 100.5(2) . . ?
O10 Zn3 O14 101.1(2) . . ?
O12 Zn3 O14 97.5(3) . . ?
O19 S1 O20 120.6(5) . . ?
O19 S1 C9 108.6(5) . 2_655 ?
O20 S1 C9 107.0(5) . 2_655 ?
O19 S1 C44 107.4(5) . . ?
O20 S1 C44 108.7(5) . . ?
C9 S1 C44 103.1(4) 2_655 . ?
O16 S2 O15 120.1(3) . . ?
O16 S2 C29 108.4(3) . . ?
O15 S2 C29 107.9(3) . . ?
O16 S2 C22 107.4(3) . 2 ?
O15 S2 C22 108.1(3) . 2 ?
C29 S2 C22 103.7(3) . 2 ?
O17 S3 O18 120.2(3) . . ?
O17 S3 C39 108.6(3) . . ?
O18 S3 C39 107.9(3) . . ?
O17 S3 C36 108.2(3) . 4_566 ?
O18 S3 C36 107.4(3) . 4_566 ?
C39 S3 C36 103.2(3) . 4_566 ?
C5 O1 Zn1 142.2(5) . . ?
C51 O2 Zn1 145.6(5) . . ?
C12 O3 Zn1 157.6(6) . . ?
C12 O3 Zn2 80.1(6) . . ?
Zn1 O3 Zn2 99.0(2) . . ?
C32 O4 Zn1 141.8(5) . . ?
C25 O5 Zn1 133.4(4) . . ?
C18 O6 Zn1 163.5(8) . . ?
C51 O7 Zn2 123.0(5) . . ?
C5 O8 Zn2 125.6(5) . . ?
C12 O9 Zn2 97.6(6) . . ?
C32 O10 Zn3 124.5(4) . . ?
C25 O11 Zn3 134.1(5) . . ?
C18 O12 Zn3 107.8(6) . . ?
C1 O13 Zn2 129.9(6) . . ?
C3 O14 Zn3 126.2(6) . . ?
C39 C17 C16 119.4(7) . . ?
C30 C31 C26 120.4(6) . . ?
C29 C30 C31 119.4(6) . . ?
C14 C15 C39 118.6(7) . . ?
C28 C27 C26 120.0(6) . . ?
C20 C02 C22 119.2(8) . . ?
O13 C1 N1 124.8(9) . . ?
C8 C9 C21 120.9(7) . . ?
C8 C9 S1 120.6(7) . 2_645 ?
C21 C9 S1 118.5(7) . 2_645 ?
C44 C43 C42 118.1(8) . . ?
C02 C20 C19 120.4(8) . . ?
C31 C26 C27 119.2(6) . . ?
C31 C26 C25 119.8(6) . . ?
C27 C26 C25 121.0(6) . . ?
C19 C24 C23 119.6(7) . . ?
O14 C3 N2 123.9(9) . . ?
O3 C12 O9 124.8(9) . . ?
O3 C12 C13 119.9(9) . . ?
O9 C12 C13 115.2(8) . . ?
O3 C12 Zn2 71.7(5) . . ?
O9 C12 Zn2 53.1(4) . . ?
C13 C12 Zn2 167.4(7) . . ?
C27 C28 C29 120.5(6) . . ?
C33 C38 C37 120.3(7) . . ?
C37 C36 C35 121.5(7) . . ?
C37 C36 S3 119.5(5) . 4_665 ?
C35 C36 S3 119.0(6) . 4_665 ?
C43 C42 C41 121.6(8) . . ?
C28 C29 C30 120.6(6) . . ?
C28 C29 S2 119.6(5) . . ?
C30 C29 S2 119.8(5) . . ?
C1 N1 C2 121.0(9) . . ?
C1 N1 C50 117.4(10) . . ?
C2 N1 C50 121.6(9) . . ?
C7 C6 C11 118.6(7) . . ?
C7 C6 C5 120.7(6) . . ?
C11 C6 C5 120.6(7) . . ?
O5 C25 O11 127.7(6) . . ?
O5 C25 C26 117.3(6) . . ?
O11 C25 C26 115.0(6) . . ?
C34 C35 C36 118.3(7) . . ?
C41 C46 C45 121.5(8) . . ?
C38 C33 C34 118.8(6) . . ?
C38 C33 C32 120.3(6) . . ?
C34 C33 C32 120.8(6) . . ?
C22 C23 C24 119.8(7) . . ?
C17 C16 C13 120.9(7) . . ?
C6 C11 C21 120.3(9) . . ?
C24 C19 C20 119.7(8) . . ?
C24 C19 C18 120.6(8) . . ?
C20 C19 C18 119.6(8) . . ?
C15 C14 C13 119.7(7) . . ?
O2 C51 O7 123.8(7) . . ?
O2 C51 C41 117.1(6) . . ?
O7 C51 C41 119.1(6) . . ?
C46 C45 C44 118.6(8) . . ?
O6 C18 O12 122.5(9) . . ?
O6 C18 C19 120.1(9) . . ?
O12 C18 C19 117.1(8) . . ?
C9 C8 C7 119.8(8) . . ?
C43 C44 C45 121.8(8) . . ?
C43 C44 S1 120.9(8) . . ?
C45 C44 S1 117.3(8) . . ?
O1 C5 O8 126.2(7) . . ?
O1 C5 C6 117.7(6) . . ?
O8 C5 C6 116.0(6) . . ?
C16 C13 C14 119.8(7) . . ?
C16 C13 C12 118.2(8) . . ?
C14 C13 C12 122.0(8) . . ?
C3 N2 C47 120.0(9) . . ?
C3 N2 C4 120.2(9) . . ?
C47 N2 C4 119.9(8) . . ?
C6 C7 C8 120.5(7) . . ?
C35 C34 C33 121.3(6) . . ?
C46 C41 C42 118.3(7) . . ?
C46 C41 C51 119.8(7) . . ?
C42 C41 C51 121.9(7) . . ?
C36 C37 C38 119.8(6) . . ?
O4 C32 O10 125.3(7) . . ?
O4 C32 C33 119.0(7) . . ?
O10 C32 C33 115.6(6) . . ?
C17 C39 C15 121.5(6) . . ?
C17 C39 S3 119.4(5) . . ?
C15 C39 S3 119.1(5) . . ?
C23 C22 C02 121.2(7) . . ?
C23 C22 S2 119.5(5) . 2_545 ?
C02 C22 S2 119.3(6) . 2_545 ?
C9 C21 C11 119.7(9) . . ?

_refine_diff_density_max         1.713
_refine_diff_density_min         -0.522
_refine_diff_density_rms         0.168

_shelxl_version_number           2014-3

####################################################################### 
# 
# 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_compound3
_database_code_depnum_ccdc_archive 'CCDC 1052872'
_audit_update_record             
;
2015-03-09 deposited with the CCDC.
2015-06-24 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014
_chemical_name_systematic        
;
 ?
;
_chemical_name_common            zinccarboxylate
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C15.50 H9 N0.50 O7.50 S Zn1.50'
_chemical_formula_weight         452.35

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'
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'
Zn Zn 0.2839 1.4301 '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'

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

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

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

_cell_length_a                   13.9367(7)
_cell_length_b                   6.1040(3)
_cell_length_c                   19.7129(11)
_cell_angle_alpha                90
_cell_angle_beta                 93.616(2)
_cell_angle_gamma                90
_cell_volume                     1673.63(15)
_cell_formula_units_Z            4
_cell_measurement_temperature    298(2)
_cell_measurement_reflns_used    ?
_cell_measurement_theta_min      ?
_cell_measurement_theta_max      ?

_exptl_crystal_description       platelike
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.795
_exptl_crystal_F_000             906
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.100
_exptl_absorpt_coefficient_mu    2.333
_shelx_estimated_absorpt_T_min   0.653
_shelx_estimated_absorpt_T_max   0.800
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_correction_T_min  0.653
_exptl_absorpt_correction_T_max  0.800
_exptl_absorpt_process_details   SADABS

_exptl_special_details           
;
 ?
;

_diffrn_ambient_temperature      298(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            15867
_diffrn_reflns_av_unetI/netI     0.0414
_diffrn_reflns_av_R_equivalents  0.0373
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_theta_min         1.739
_diffrn_reflns_theta_max         28.381
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             4173
_reflns_number_gt                2943
_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 SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-2014 (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)+(0.0667P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   geom
_refine_ls_hydrogen_treatment    none
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         4173
_refine_ls_number_parameters     235
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0668
_refine_ls_R_factor_gt           0.0356
_refine_ls_wR_factor_ref         0.1210
_refine_ls_wR_factor_gt          0.0948
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_restrained_S_all      1.085
_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
Zn1 Zn 1.1020 0.5105 0.0176 0.024 Uani 1 1 d . . . . .
Zn2 Zn 1.0000 1.0000 0.0000 0.020 Uani 1 2 d S . P . .
S1 S 0.5319 0.9244 0.2700 0.025 Uani 1 1 d . . . . .
O1 O 1.1646 0.3782 0.0958 0.038 Uani 1 1 d . . . . .
O2 O 1.1945 0.6344 -0.0393 0.036 Uani 1 1 d . . . . .
O3 O 0.9880 0.6890 0.0362 0.021 Uani 1 1 d . . . . .
H3A H 0.9757 0.6881 0.0846 1.200 Uiso 1 1 calc R . . . .
O4 O 0.8972 1.0760 0.0683 0.034 Uani 1 1 d . . . . .
O5 O 1.1196 0.0304 0.0765 0.035 Uani 1 1 d . . . . .
O6 O 0.5456 1.0632 0.3286 0.039 Uani 1 1 d . . . . .
O7 O 0.5373 0.6905 0.2774 0.037 Uani 1 1 d . . . . .
C8 C 0.8244 1.1928 0.0729 0.025 Uani 1 1 d . . . . .
C9 C 0.7522 1.1264 0.1226 0.024 Uani 1 1 d . . . . .
C14 C 0.7551 0.9204 0.1516 0.035 Uani 1 1 d . . . . .
H14 H 0.8035 0.8230 0.1413 0.042 Uiso 1 1 calc R U . . .
C13 C 0.6873 0.8574 0.1955 0.033 Uani 1 1 d . . . . .
H13 H 0.6887 0.7171 0.2140 0.039 Uiso 1 1 calc R U . . .
C12 C 0.6170 1.0053 0.2120 0.024 Uani 1 1 d . . . . .
C11 C 0.6148 1.2134 0.1846 0.036 Uani 1 1 d . . . . .
H11 H 0.5683 1.3131 0.1965 0.044 Uiso 1 1 calc R U . . .
C10 C 0.6817 1.2728 0.1396 0.034 Uani 1 1 d . . . . .
H10 H 0.6795 1.4121 0.1204 0.041 Uiso 1 1 calc R U . . .
C5 C 1.4204 -0.0087 0.2280 0.021 Uani 1 1 d . . . . .
C1 C 1.1719 0.1732 0.1044 0.025 Uani 1 1 d . . . . .
C2 C 1.2555 0.1027 0.1514 0.023 Uani 1 1 d . . . . .
C7 C 1.2981 0.2517 0.1969 0.027 Uani 1 1 d . . . . .
H7 H 1.2712 0.3901 0.2011 0.032 Uiso 1 1 calc R U . . .
C6 C 1.3804 0.1965 0.2365 0.027 Uani 1 1 d . . . . .
H6 H 1.4081 0.2950 0.2680 0.032 Uiso 1 1 calc R U . . .
C4 C 1.3775 -0.1599 0.1837 0.030 Uani 1 1 d . . . . .
H4 H 1.4047 -0.2979 0.1793 0.036 Uiso 1 1 calc R U . . .
C3 C 1.2938 -0.1057 0.1460 0.031 Uani 1 1 d . . . . .
H3 H 1.2635 -0.2084 0.1171 0.037 Uiso 1 1 calc R U . . .
C15 C 0.4105 0.2754 0.0108 0.281 Uiso 0.5 1 d . . P . .
C17 C 0.4773 0.5853 0.0622 0.243 Uiso 0.5 1 d . . P . .
O8 O 0.4924 0.3924 -0.0016 0.173 Uiso 0.5 1 d . . P . .
N1 N 0.5082 0.1512 -0.0158 0.318 Uiso 0.5 1 d . . P . .
C16 C 0.4260 0.4618 0.0414 0.163 Uiso 0.5 1 d . . P . .


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

loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
Zn1 O1 1.9027 . ?
Zn1 O2 1.9158 . ?
Zn1 O3 1.9796 . ?
Zn1 O3 2.0032 3_765 ?
Zn1 Zn1 2.8866 3_765 ?
Zn2 O3 2.0384 . ?
Zn2 O3 2.0385 3_775 ?
Zn2 O4 2.0795 3_775 ?
Zn2 O4 2.0796 . ?
Zn2 O5 2.1835 3_765 ?
Zn2 O5 2.1835 1_565 ?
S1 O6 1.4344 . ?
S1 O7 1.4364 . ?
S1 C5 1.7624 1_465 ?
S1 C12 1.7697 . ?
O1 C1 1.2661 . ?
O2 C8 1.2652 3_775 ?
O3 Zn1 2.0033 3_765 ?
O3 H3A 0.9800 . ?
O4 C8 1.2479 . ?
O5 C1 1.2425 . ?
O5 Zn2 2.1835 1_545 ?
C8 O2 1.2652 3_775 ?
C8 C9 1.5024 . ?
C9 C14 1.3809 . ?
C9 C10 1.3856 . ?
C14 C13 1.3766 . ?
C14 H14 0.9300 . ?
C13 C12 1.3856 . ?
C13 H13 0.9300 . ?
C12 C11 1.3801 . ?
C11 C10 1.3753 . ?
C11 H11 0.9300 . ?
C10 H10 0.9300 . ?
C5 C4 1.3802 . ?
C5 C6 1.3854 . ?
C5 S1 1.7624 1_645 ?
C1 C2 1.5054 . ?
C2 C7 1.3845 . ?
C2 C3 1.3864 . ?
C7 C6 1.3873 . ?
C7 H7 0.9300 . ?
C6 H6 0.9300 . ?
C4 C3 1.3831 . ?
C4 H4 0.9300 . ?
C3 H3 0.9300 . ?
C15 C16 1.2994 . ?
C15 O8 1.3805 . ?
C15 N1 1.6710 . ?
C17 C16 1.1007 . ?
C17 O8 1.3001 3_665 ?
C17 O8 1.7461 . ?
C17 N1 1.8679 3_665 ?
O8 C17 1.3001 3_665 ?
O8 O8 1.3315 3_665 ?
O8 C16 1.3617 . ?
O8 N1 1.5171 . ?
O8 C16 1.6785 3_665 ?
N1 C17 1.8679 3_665 ?
C16 O8 1.6785 3_665 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
O1 Zn1 O2 110.5 . . ?
O1 Zn1 O3 114.5 . . ?
O2 Zn1 O3 117.9 . . ?
O1 Zn1 O3 114.2 . 3_765 ?
O2 Zn1 O3 110.7 . 3_765 ?
O3 Zn1 O3 87.1 . 3_765 ?
O1 Zn1 Zn1 124.7 . 3_765 ?
O2 Zn1 Zn1 124.5 . 3_765 ?
O3 Zn1 Zn1 43.9 . 3_765 ?
O3 Zn1 Zn1 43.2 3_765 3_765 ?
O3 Zn2 O3 180.0 . 3_775 ?
O3 Zn2 O4 95.4 . 3_775 ?
O3 Zn2 O4 84.6 3_775 3_775 ?
O3 Zn2 O4 84.6 . . ?
O3 Zn2 O4 95.4 3_775 . ?
O4 Zn2 O4 180.0 3_775 . ?
O3 Zn2 O5 95.0 . 3_765 ?
O3 Zn2 O5 85.0 3_775 3_765 ?
O4 Zn2 O5 93.5 3_775 3_765 ?
O4 Zn2 O5 86.5 . 3_765 ?
O3 Zn2 O5 85.0 . 1_565 ?
O3 Zn2 O5 95.0 3_775 1_565 ?
O4 Zn2 O5 86.5 3_775 1_565 ?
O4 Zn2 O5 93.5 . 1_565 ?
O5 Zn2 O5 180.0 3_765 1_565 ?
O6 S1 O7 120.1 . . ?
O6 S1 C5 108.1 . 1_465 ?
O7 S1 C5 108.5 . 1_465 ?
O6 S1 C12 107.1 . . ?
O7 S1 C12 108.0 . . ?
C5 S1 C12 103.8 1_465 . ?
C1 O1 Zn1 123.9 . . ?
C8 O2 Zn1 120.7 3_775 . ?
Zn1 O3 Zn1 92.9 . 3_765 ?
Zn1 O3 Zn2 111.3 . . ?
Zn1 O3 Zn2 116.3 3_765 . ?
Zn1 O3 H3A 111.7 . . ?
Zn1 O3 H3A 111.7 3_765 . ?
Zn2 O3 H3A 111.7 . . ?
C8 O4 Zn2 140.4 . . ?
C1 O5 Zn2 140.0 . 1_545 ?
O4 C8 O2 125.6 . 3_775 ?
O4 C8 C9 118.3 . . ?
O2 C8 C9 116.1 3_775 . ?
C14 C9 C10 119.3 . . ?
C14 C9 C8 120.8 . . ?
C10 C9 C8 119.9 . . ?
C13 C14 C9 120.8 . . ?
C13 C14 H14 119.6 . . ?
C9 C14 H14 119.6 . . ?
C14 C13 C12 119.3 . . ?
C14 C13 H13 120.4 . . ?
C12 C13 H13 120.4 . . ?
C11 C12 C13 120.4 . . ?
C11 C12 S1 120.7 . . ?
C13 C12 S1 118.8 . . ?
C10 C11 C12 119.7 . . ?
C10 C11 H11 120.1 . . ?
C12 C11 H11 120.1 . . ?
C11 C10 C9 120.4 . . ?
C11 C10 H10 119.8 . . ?
C9 C10 H10 119.8 . . ?
C4 C5 C6 121.3 . . ?
C4 C5 S1 118.5 . 1_645 ?
C6 C5 S1 120.1 . 1_645 ?
O5 C1 O1 126.4 . . ?
O5 C1 C2 118.8 . . ?
O1 C1 C2 114.7 . . ?
C7 C2 C3 120.1 . . ?
C7 C2 C1 119.6 . . ?
C3 C2 C1 120.1 . . ?
C2 C7 C6 120.7 . . ?
C2 C7 H7 119.7 . . ?
C6 C7 H7 119.7 . . ?
C5 C6 C7 118.4 . . ?
C5 C6 H6 120.8 . . ?
C7 C6 H6 120.8 . . ?
C5 C4 C3 119.8 . . ?
C5 C4 H4 120.1 . . ?
C3 C4 H4 120.1 . . ?
C4 C3 C2 119.6 . . ?
C4 C3 H3 120.2 . . ?
C2 C3 H3 120.2 . . ?
C16 C15 O8 61.0 . . ?
C16 C15 N1 115.4 . . ?
O8 C15 N1 58.7 . . ?
C16 C17 O8 88.3 . 3_665 ?
C16 C17 O8 51.2 . . ?
O8 C17 O8 49.2 3_665 . ?
C16 C17 N1 119.7 . 3_665 ?
O8 C17 N1 53.7 3_665 3_665 ?
O8 C17 N1 101.8 . 3_665 ?
C17 O8 O8 83.1 3_665 3_665 ?
C17 O8 C16 144.5 3_665 . ?
O8 O8 C16 77.1 3_665 . ?
C17 O8 C15 122.5 3_665 . ?
O8 O8 C15 129.3 3_665 . ?
C16 O8 C15 56.6 . . ?
C17 O8 N1 82.7 3_665 . ?
O8 O8 N1 160.3 3_665 . ?
C16 O8 N1 121.9 . . ?
C15 O8 N1 70.3 . . ?
C17 O8 C16 41.0 3_665 3_665 ?
O8 O8 C16 52.3 3_665 3_665 ?
C16 O8 C16 129.4 . 3_665 ?
C15 O8 C16 161.7 . 3_665 ?
N1 O8 C16 108.5 . 3_665 ?
C17 O8 C17 130.8 3_665 . ?
O8 O8 C17 47.7 3_665 . ?
C16 O8 C17 39.1 . . ?
C15 O8 C17 94.7 . . ?
N1 O8 C17 144.3 . . ?
C16 O8 C17 95.5 3_665 . ?
O8 N1 C15 51.0 . . ?
O8 N1 C17 43.7 . 3_665 ?
C15 N1 C17 83.0 . 3_665 ?
C17 C16 C15 149.1 . . ?
C17 C16 O8 89.7 . . ?
C15 C16 O8 62.4 . . ?
C17 C16 O8 50.7 . 3_665 ?
C15 C16 O8 110.1 . 3_665 ?
O8 C16 O8 50.6 . 3_665 ?

_refine_diff_density_max         0.974
_refine_diff_density_min         -0.762
_refine_diff_density_rms         0.257

_shelxl_version_number           2014-3

