# Electronic Supplementary Material (ESI) for Dalton Transactions.
# 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_CP1
_database_code_depnum_ccdc_archive 'CCDC 1818729'
_audit_update_record             
;
2018-06-08 deposited with the CCDC.
2018-06-18 downloaded from the CCDC.
;
_audit_creation_date             2018-05-14
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2017.03.28 svn.r3405 for OlexSys, GUI svn.r5337)
;
_shelx_SHELXL_version_number     2016/6


_vrf_PLAT971_1                   
;
PROBLEM: Check Calcd Resid. Dens.  0.74A   From Pb1             4.75 eA-3  
RESPONSE: High peaks close to heavy metal atoms are not uncommon, 
the position of the electron density maximum is along the Pb-O bond
and cannot correspond to an missing atom, but rather is an artefact due to the
proximity of heavy atoms
;
_vrf_PLAT972_1                   
;
PROBLEM: Check Calcd Resid. Dens.  1.17A   From Pb1            -3.87 eA-3  
RESPONSE: See response above to alert PLAT971
;
_vrf_PLAT342_1                   
;
PROBLEM: Low Bond Precision on  C-C Bonds ...............    0.02567 Ang.  
RESPONSE: As the structure contains Pb atoms, 
they account for the majority of the scattering, and 
subsequently the positions of lighter atoms are 
determined with less precision.
;
_vrf_PLAT976_1                   
;
PROBLEM: Check Calcd Resid. Dens.  0.89A   From O1             -1.66 eA-3  
RESPONSE: See response above to alert PLAT971

;
_chemical_name_common            ?
_chemical_name_systematic        
;
 ? 
;
_chemical_formula_moiety         '0.25(C24 H8 O16 Pb4 S4)'
_chemical_formula_sum            'C6 H2 O4 Pb S'
_chemical_formula_weight         377.33
_chemical_melting_point          ?
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'
Pb Pb -3.3944 10.1111 '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'

_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.
;
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_H-M_alt        'C 1 2/c 1'
_space_group_name_Hall           '-C 2yc'
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                   18.829(6)
_cell_length_b                   5.7680(10)
_cell_length_c                   6.7630(10)
_cell_angle_alpha                90
_cell_angle_beta                 110.500(5)
_cell_angle_gamma                90
_cell_volume                     688.0(3)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    2004
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.458
_cell_measurement_theta_min      2.309
_shelx_estimated_absorpt_T_max   0.242
_shelx_estimated_absorpt_T_min   0.083
_exptl_absorpt_coefficient_mu    24.787
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.1563
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1573 before and 0.0726 after correction.
The Ratio of minimum to maximum transmission is 0.2096.
The λ/2 correction factor is Not present.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'light yellow'
_exptl_crystal_density_diffrn    3.643
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             672
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.08
_exptl_special_details           
;
 ? 
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0457
_diffrn_reflns_av_unetI/netI     0.0457
_diffrn_reflns_Laue_measured_fraction_full 0.981
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       7
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            2877
_diffrn_reflns_point_group_measured_fraction_full 0.981
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.559
_diffrn_reflns_theta_min         2.310
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean ?
_diffrn_measured_fraction_theta_full 0.981
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   ?
_reflns_Friedel_coverage         0.000
_reflns_Friedel_fraction_full    .
_reflns_Friedel_fraction_max     .
_reflns_number_gt                609
_reflns_number_total             784
_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.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       ?
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_refine_diff_density_max         4.782
_refine_diff_density_min         -3.603
_refine_diff_density_rms         0.805
_refine_ls_extinction_coef       0.012(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2016/6 (Sheldrick 2016)'
_refine_ls_goodness_of_fit_ref   1.111
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     58
_refine_ls_number_reflns         784
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0762
_refine_ls_R_factor_gt           0.0680
_refine_ls_restrained_S_all      1.112
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1875P)²+3.7769P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2338
_refine_ls_wR_factor_ref         0.2501
_refine_special_details          ?
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
3.a Aromatic/amide H refined with riding coordinates:
 C3(H3)
;
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
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
Pb1 Pb 0.250000 0.250000 0.000000 0.0245(8) Uani 1 2 d S T P . .
S1 S 0.500000 0.3786(8) 0.750000 0.0448(17) Uani 1 2 d S T P . .
O1 O 0.3139(6) 0.086(3) 0.390(2) 0.061(4) Uani 1 1 d . . . . .
O2 O 0.3458(7) 0.452(3) 0.427(3) 0.075(5) Uani 1 1 d . . . . .
C1 C 0.3591(16) 0.2479(17) 0.476(6) 0.031(6) Uani 1 1 d . . . . .
C2 C 0.4346(7) 0.182(3) 0.627(2) 0.033(3) Uani 1 1 d . U . . .
C3 C 0.4632(6) -0.039(2) 0.6761(19) 0.038(3) Uani 1 1 d . . . . .
H3 H 0.436603 -0.172654 0.617555 0.046 Uiso 1 1 calc R . . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_23
_atom_site_aniso_U_13
_atom_site_aniso_U_12
Pb1 0.0212(9) 0.0255(10) 0.0242(10) 0.00143(17) 0.0050(5) 0.00387(18)
S1 0.018(2) 0.034(3) 0.067(3) 0.000 -0.0032(19) 0.000
O1 0.026(6) 0.108(13) 0.040(6) -0.002(6) 0.001(5) -0.020(7)
O2 0.037(7) 0.086(12) 0.088(11) 0.047(9) 0.006(8) 0.015(8)
C1 0.015(11) 0.027(14) 0.042(16) 0.009(4) -0.001(11) -0.004(4)
C2 0.017(5) 0.042(6) 0.027(6) 0.011(6) -0.006(4) 0.004(6)
C3 0.019(6) 0.048(8) 0.040(7) -0.003(6) 0.001(5) -0.014(6)

_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
Pb1 O1 2.525(15) 6 ?
Pb1 O1 2.660(13) . ?
Pb1 O1 2.660(13) 7 ?
Pb1 O1 2.525(15) 4 ?
Pb1 O2 2.660(17) 6_565 ?
Pb1 O2 2.660(17) 4_545 ?
S1 C2 1.667(17) . ?
S1 C2 1.667(17) 2_656 ?
O1 C1 1.26(3) . ?
O2 C1 1.22(2) . ?
C1 C2 1.48(3) . ?
C2 C3 1.38(2) . ?
C3 C3 1.39(2) 2_656 ?
C3 H3 0.9300 . ?

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 Pb1 O1 180.0(6) 6 4 ?
O1 Pb1 O1 94.5(3) 4 . ?
O1 Pb1 O1 85.5(3) 6 . ?
O1 Pb1 O1 94.5(3) 6 7 ?
O1 Pb1 O1 85.5(3) 4 7 ?
O1 Pb1 O1 180.0 7 . ?
O1 Pb1 O2 91.0(6) 6 6_565 ?
O1 Pb1 O2 89.0(6) 6 4_545 ?
O1 Pb1 O2 89.0(6) 4 6_565 ?
O1 Pb1 O2 91.0(6) 4 4_545 ?
O2 Pb1 O1 71.7(3) 6_565 7 ?
O2 Pb1 O1 108.3(3) 4_545 7 ?
O2 Pb1 O1 108.3(3) 6_565 . ?
O2 Pb1 O1 71.7(3) 4_545 . ?
O2 Pb1 O2 180.0(4) 6_565 4_545 ?
C2 S1 C2 94.1(11) 2_656 . ?
Pb1 O1 Pb1 118.0(4) 4_545 . ?
C1 O1 Pb1 138.3(18) . 4_545 ?
C1 O1 Pb1 101.0(16) . . ?
C1 O2 Pb1 131.2(18) . 4 ?
O1 C1 C2 117.2(14) . . ?
O2 C1 O1 123(2) . . ?
O2 C1 C2 119.3(19) . . ?
C1 C2 S1 122.1(13) . . ?
C3 C2 S1 110.5(9) . . ?
C3 C2 C1 127.2(14) . . ?
C2 C3 C3 112.3(7) . 2_656 ?
C2 C3 H3 123.9 . . ?
C3 C3 H3 123.9 2_656 . ?

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
Pb1 O1 C1 O2 -127(3) 4_545 . . . ?
Pb1 O1 C1 O2 32(4) . . . . ?
Pb1 O1 C1 C2 -141(2) . . . . ?
Pb1 O1 C1 C2 60(4) 4_545 . . . ?
Pb1 O2 C1 O1 73(4) 4 . . . ?
Pb1 O2 C1 C2 -114(2) 4 . . . ?
S1 C2 C3 C3 3.6(19) . . . 2_656 ?
O1 C1 C2 S1 179(2) . . . . ?
O1 C1 C2 C3 4(4) . . . . ?
O2 C1 C2 S1 6(4) . . . . ?
O2 C1 C2 C3 -170(2) . . . . ?
C1 C2 C3 C3 180(2) . . . 2_656 ?
C2 S1 C2 C1 -178(2) 2_656 . . . ?
C2 S1 C2 C3 -1.3(7) 2_656 . . . ?

_shelx_res_file                  
;
TITL 1 in C2/c
    1.res
    created by SHELXL-2016/6 at 21:18:34 on 14-May-2018
CELL 0.71073 18.829 5.768 6.763 90 110.5 90
ZERR 4 0.006 0.001 0.001 0 0.005 0
LATT 7
SYMM -X,+Y,0.5-Z
SFAC C H O Pb S
UNIT 24 8 16 4 4
ISOR 0.01 0.02 C2

L.S. 4
PLAN  4
SIZE 0.2 0.15 0.08
MORE -1
BOND $H
CONF
fmap 2
acta
REM <olex2.extras>
REM <HklSrc "%.\\1.hkl">
REM </olex2.extras>

WGHT    0.187500    3.776900
EXTI    0.011996
FVAR       0.11326
PB1   4    0.250000    0.250000    0.000000    10.50000    0.02122    0.02555 =
         0.02422    0.00143    0.00499    0.00387
S1    5    0.500000    0.378619    0.750000    10.50000    0.01825    0.03435 =
         0.06724    0.00000   -0.00319    0.00000
O1    3    0.313884    0.085575    0.389907    11.00000    0.02625    0.10841 =
         0.04000   -0.00174    0.00145   -0.02032
O2    3    0.345785    0.451771    0.427161    11.00000    0.03708    0.08621 =
         0.08766    0.04736    0.00562    0.01512
C1    1    0.359079    0.247875    0.476132    11.00000    0.01526    0.02669 =
         0.04196    0.00921   -0.00140   -0.00372
C2    1    0.434633    0.181739    0.626937    11.00000    0.01735    0.04232 =
         0.02724    0.01091   -0.00589    0.00434
C3    1    0.463245   -0.038865    0.676132    11.00000    0.01923    0.04847 =
         0.03989   -0.00263    0.00128   -0.01437
AFIX  43
H3    2    0.436603   -0.172654    0.617555    11.00000   -1.20000
AFIX   0
HKLF 4




REM  1 in C2/c
REM R1 =  0.0680 for     609 Fo > 4sig(Fo)  and  0.0762 for all     784 data
REM     58 parameters refined using      6 restraints

END

WGHT      0.1875      3.7769

REM Highest difference peak  4.782,  deepest hole -3.603,  1-sigma level  0.805
Q1    1   0.2505  0.1156 -0.0031  11.00000  0.05    4.78
Q2    1   0.2689  0.2498 -0.0824  11.00000  0.05    3.92
Q3    1   0.2840  0.2497  0.1062  11.00000  0.05    3.77
Q4    1   0.5000  0.1276  0.7500  10.50000  0.05    2.26
;
_shelx_res_checksum              92959
_olex2_submission_special_instructions 'No special instructions were received'
