# Electronic Supplementary Material (ESI) for ChemComm.
# 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_Si6ctc4
_database_code_depnum_ccdc_archive 'CCDC 1575718'
_audit_update_record             
;
2017-09-21 deposited with the CCDC.
2018-09-26 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_CHEMW03_Si6ctc4             
;
PROBLEM: ALERT: The ratio of given/expected molecular weight as
RESPONSE: The crystals contains large regions of space occupied
by highly disordered cations and solvent molecules. The SQUEEZE
routine within PLATON was used to handle this problem and as a
result there is a significant discrepancy between the given and
expected molecular weight.
;
# end Validation Reply Form 

_audit_creation_method           SHELXL-2014/6
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'C212 H298 Br2 N12 O40 Si6'
_chemical_formula_weight         3982.97

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'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Si Si 0.2541 0.3302 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Br Br -0.6763 1.2805 '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'

_space_group_crystal_system      cubic
_space_group_IT_number           216
_space_group_name_H-M_alt        'F -4 3 m'
_space_group_name_Hall           'F -4 2 3'

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

_cell_length_a                   27.9568(6)
_cell_length_b                   27.9568(6)
_cell_length_c                   27.9568(6)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     21850.5(14)
_cell_formula_units_Z            4
_cell_measurement_temperature    130(1)
_cell_measurement_reflns_used    1240
_cell_measurement_theta_min      4.5
_cell_measurement_theta_max      73.5

_exptl_crystal_description       tetrahedron
_exptl_crystal_colour            yellow
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    1.211
_exptl_crystal_F_000             8512
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.20
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.05
_exptl_absorpt_coefficient_mu    1.371
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.99448
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      130(1)
_diffrn_radiation_wavelength     1.54184
_diffrn_radiation_type           CuK\a
__diffrn_source                  'SuperNova (Cu) X-ray Source'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_detector_area_resol_mean 10.2273
_diffrn_reflns_number            3975
_diffrn_reflns_av_unetI/netI     0.0226
_diffrn_reflns_av_R_equivalents  0.0216
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_theta_min         4.473
_diffrn_reflns_theta_max         67.841
_diffrn_reflns_theta_full        67.684
_diffrn_measured_fraction_theta_max 0.991
_diffrn_measured_fraction_theta_full 0.990
_diffrn_reflns_Laue_measured_fraction_max 0.991
_diffrn_reflns_Laue_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_point_group_measured_fraction_full 0.993
_reflns_number_total             1510
_reflns_number_gt                1276
_reflns_threshold_expression     'I > 2σ(I)'
_reflns_Friedel_coverage         0.887
_reflns_Friedel_fraction_max     0.996
_reflns_Friedel_fraction_full    0.996

_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;

_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.20 (release 27-06-2012 CrysAlis171 .NET)
(compiled Jul 11 2012,15:38:31)
;
_computing_structure_solution    SHELXS
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'w=1/[σ²(Fo²)+(0.1870P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   mixed
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.42(10)
_chemical_absolute_configuration ?
_refine_ls_number_reflns         1510
_refine_ls_number_parameters     79
_refine_ls_number_restraints     4
_refine_ls_R_factor_all          0.0849
_refine_ls_R_factor_gt           0.0773
_refine_ls_wR_factor_ref         0.2300
_refine_ls_wR_factor_gt          0.2178
_refine_ls_goodness_of_fit_ref   1.050
_refine_ls_restrained_S_all      1.048
_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
C5 C 0.1929(3) 0.5000 0.0000 0.089(3) Uani 1 4 d DS T P . .
C6 C 0.1669(5) 0.5402(5) -0.0144(5) 0.118(5) Uani 0.5 1 d D . P . .
H6 H 0.1837 0.5677 -0.0251 0.142 Uiso 0.5 1 calc R U P . .
C7 C 0.1172(5) 0.5409(7) -0.0134(7) 0.153(8) Uani 0.5 1 d D . P . .
H7 H 0.1003 0.5692 -0.0218 0.184 Uiso 0.5 1 calc R U P . .
Br1 Br 0.28534(15) 0.71466(15) 0.28534(15) 0.0974(17) Uiso 0.25 6 d S . P . .
Br2 Br 0.1344(2) 0.6344(2) 0.1344(2) 0.140(3) Uiso 0.25 6 d S . P . .
C8 C 0.0925(16) 0.5000 0.0000 0.29(2) Uani 1 4 d DS T P . .
H8A H 0.0592(16) 0.5000 0.0000 0.342 Uiso 1 4 d DS U P . .
C1 C 0.28144(16) 0.54342(15) 0.07766(17) 0.0634(10) Uani 1 1 d . . . . .
C2 C 0.28861(15) 0.55569(15) 0.12645(15) 0.0615(10) Uani 1 1 d . . . . .
H3 H 0.2872 0.5318 0.1506 0.074 Uiso 1 1 calc R U . . .
C3 C 0.29778(14) 0.60306(16) 0.13850(15) 0.0596(10) Uani 1 1 d . . . . .
C4 C 0.30905(14) 0.6129(2) 0.19095(14) 0.0597(13) Uani 1 2 d S T P . .
H5A H 0.2886 0.5925 0.2114 0.072 Uiso 1 2 calc R U P . .
H5B H 0.3016 0.6468 0.1984 0.072 Uiso 1 2 calc R U P . .
O1 O 0.27489(11) 0.49886(12) 0.06017(10) 0.0690(9) Uani 1 1 d . . . . .
Si1 Si 0.25974(9) 0.5000 0.0000 0.0623(7) Uani 1 4 d S T 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
C5 C6 1.396(10) 44 ?
C5 C6 1.396(10) . ?
C5 C6 1.396(10) 4_565 ?
C5 C6 1.396(10) 41_554 ?
C5 Si1 1.869(10) . ?
C6 C7 1.391(11) . ?
C7 C8 1.388(12) . ?
C8 C7 1.388(12) 44 ?
C8 C7 1.388(12) 41_554 ?
C8 C7 1.388(12) 4_565 ?
C1 O1 1.351(5) . ?
C1 C1 1.354(9) 41_554 ?
C1 C2 1.421(6) . ?
C2 C3 1.390(6) . ?
C3 C3 1.401(9) 41_554 ?
C3 C4 1.525(5) . ?
C4 C3 1.525(5) 71 ?
O1 Si1 1.735(3) . ?
Si1 O1 1.735(3) 41_554 ?
Si1 O1 1.735(3) 44 ?
Si1 O1 1.735(3) 4_565 ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C6 C5 C6 42.9(11) 44 . ?
C6 C5 C6 101.1(13) 44 4_565 ?
C6 C5 C6 117.4(15) . 4_565 ?
C6 C5 C6 117.4(15) 44 41_554 ?
C6 C5 C6 101.1(13) . 41_554 ?
C6 C5 C6 42.9(11) 4_565 41_554 ?
C6 C5 Si1 121.3(7) 44 . ?
C6 C5 Si1 121.3(7) . . ?
C6 C5 Si1 121.3(7) 4_565 . ?
C6 C5 Si1 121.3(7) 41_554 . ?
C7 C6 C5 121.7(14) . . ?
C8 C7 C6 119(3) . . ?
C7 C8 C7 46.1(17) . 44 ?
C7 C8 C7 101(3) . 41_554 ?
C7 C8 C7 120(4) 44 41_554 ?
C7 C8 C7 120(4) . 4_565 ?
C7 C8 C7 101(3) 44 4_565 ?
C7 C8 C7 46.1(17) 41_554 4_565 ?
O1 C1 C1 113.3(2) . 41_554 ?
O1 C1 C2 126.1(4) . . ?
C1 C1 C2 120.5(2) 41_554 . ?
C3 C2 C1 119.3(4) . . ?
C2 C3 C3 120.1(3) . 41_554 ?
C2 C3 C4 116.3(5) . . ?
C3 C3 C4 123.5(3) 41_554 . ?
C3 C4 C3 111.4(4) . 71 ?
C1 O1 Si1 111.5(3) . . ?
O1 Si1 O1 88.6(2) . 41_554 ?
O1 Si1 O1 84.5(2) . 44 ?
O1 Si1 O1 151.7(3) 41_554 44 ?
O1 Si1 O1 151.7(3) . 4_565 ?
O1 Si1 O1 84.5(2) 41_554 4_565 ?
O1 Si1 O1 88.6(2) 44 4_565 ?
O1 Si1 C5 104.13(12) . . ?
O1 Si1 C5 104.13(12) 41_554 . ?
O1 Si1 C5 104.13(12) 44 . ?
O1 Si1 C5 104.13(12) 4_565 . ?

_refine_diff_density_max         0.554
_refine_diff_density_min         -0.321
_refine_diff_density_rms         0.064

_shelxl_version_number           2014/6



####################################################################### 
# 
# 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_jlh_sitet_csbr_soak_sx
_database_code_depnum_ccdc_archive 'CCDC 1860473'
_audit_update_record             
;
2018-08-05 deposited with the CCDC.
2018-09-26 downloaded from the CCDC.
;
_audit_creation_date             2018-01-06
_audit_creation_method           
;
Olex2 1.2
(compiled Nov 22 2016 11:51:51 for OlexSys, GUI svn.r5269)
;
_chemical_name_common            ?
_chemical_name_systematic        ?
_chemical_formula_moiety         'C120 H78 Cs4 O30 Si6, 1.8(Br)'
_chemical_formula_sum            'C152 H298 Br2 Cs4 N4 O94 Si6'
_chemical_formula_weight         4545.93
_chemical_absolute_configuration ?
_chemical_melting_point          ?
_chemical_oxdiff_usercomment     
'light yellow chunk. crystal of si tet soaked in aq CsBr 30 mg. Dec 17 2017 '
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'
Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Cs Cs -0.7457 7.9052 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Si Si 0.2541 0.3302 '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'

_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      cubic
_space_group_IT_number           216
_space_group_name_H-M_alt        'F -4 3 m'
_space_group_name_Hall           'F -4 2 3'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, -y, z'
'-x, y, -z'
'x, -y, -z'
'z, x, y'
'z, -x, -y'
'-z, -x, y'
'-z, x, -y'
'y, z, x'
'-y, z, -x'
'y, -z, -x'
'-y, -z, x'
'y, x, z'
'-y, -x, z'
'y, -x, -z'
'-y, x, -z'
'x, z, y'
'-x, z, -y'
'-x, -z, y'
'x, -z, -y'
'z, y, x'
'z, -y, -x'
'-z, y, -x'
'-z, -y, x'
'x, y+1/2, z+1/2'
'-x, -y+1/2, z+1/2'
'-x, y+1/2, -z+1/2'
'x, -y+1/2, -z+1/2'
'z, x+1/2, y+1/2'
'z, -x+1/2, -y+1/2'
'-z, -x+1/2, y+1/2'
'-z, x+1/2, -y+1/2'
'y, z+1/2, x+1/2'
'-y, z+1/2, -x+1/2'
'y, -z+1/2, -x+1/2'
'-y, -z+1/2, x+1/2'
'y, x+1/2, z+1/2'
'-y, -x+1/2, z+1/2'
'y, -x+1/2, -z+1/2'
'-y, x+1/2, -z+1/2'
'x, z+1/2, y+1/2'
'-x, z+1/2, -y+1/2'
'-x, -z+1/2, y+1/2'
'x, -z+1/2, -y+1/2'
'z, y+1/2, x+1/2'
'z, -y+1/2, -x+1/2'
'-z, y+1/2, -x+1/2'
'-z, -y+1/2, x+1/2'
'x+1/2, y, z+1/2'
'-x+1/2, -y, z+1/2'
'-x+1/2, y, -z+1/2'
'x+1/2, -y, -z+1/2'
'z+1/2, x, y+1/2'
'z+1/2, -x, -y+1/2'
'-z+1/2, -x, y+1/2'
'-z+1/2, x, -y+1/2'
'y+1/2, z, x+1/2'
'-y+1/2, z, -x+1/2'
'y+1/2, -z, -x+1/2'
'-y+1/2, -z, x+1/2'
'y+1/2, x, z+1/2'
'-y+1/2, -x, z+1/2'
'y+1/2, -x, -z+1/2'
'-y+1/2, x, -z+1/2'
'x+1/2, z, y+1/2'
'-x+1/2, z, -y+1/2'
'-x+1/2, -z, y+1/2'
'x+1/2, -z, -y+1/2'
'z+1/2, y, x+1/2'
'z+1/2, -y, -x+1/2'
'-z+1/2, y, -x+1/2'
'-z+1/2, -y, x+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, -y+1/2, z'
'-x+1/2, y+1/2, -z'
'x+1/2, -y+1/2, -z'
'z+1/2, x+1/2, y'
'z+1/2, -x+1/2, -y'
'-z+1/2, -x+1/2, y'
'-z+1/2, x+1/2, -y'
'y+1/2, z+1/2, x'
'-y+1/2, z+1/2, -x'
'y+1/2, -z+1/2, -x'
'-y+1/2, -z+1/2, x'
'y+1/2, x+1/2, z'
'-y+1/2, -x+1/2, z'
'y+1/2, -x+1/2, -z'
'-y+1/2, x+1/2, -z'
'x+1/2, z+1/2, y'
'-x+1/2, z+1/2, -y'
'-x+1/2, -z+1/2, y'
'x+1/2, -z+1/2, -y'
'z+1/2, y+1/2, x'
'z+1/2, -y+1/2, -x'
'-z+1/2, y+1/2, -x'
'-z+1/2, -y+1/2, x'

_cell_length_a                   27.7206(7)
_cell_length_b                   27.7206(7)
_cell_length_c                   27.7206(7)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     21301.4(16)
_cell_formula_units_Z            4
_cell_measurement_reflns_used    1225
_cell_measurement_temperature    130.01(10)
_cell_measurement_theta_max      56.3330
_cell_measurement_theta_min      4.4830
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    6.846
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88823
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_absorpt_special_details   ?
_exptl_crystal_colour            'pale yellow'
_exptl_crystal_density_diffrn    1.418
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       tetrahedron
_exptl_crystal_F_000             9456
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0380
_diffrn_reflns_av_unetI/netI     0.0344
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_number            5561
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.776
_diffrn_reflns_theta_min         4.512
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      130.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.2273
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.9974
_diffrn_measured_fraction_theta_max 0.8266
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω    -64.00  -7.00   1.00    2.50    --  -41.74 125.00 150.00   57
  2  ω     85.00 177.00   1.00   15.00    --  112.00  30.00 120.00   92
  3  ω     47.00  83.00   1.00   15.00    --  112.00 -30.00-120.00   36
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0126962000
_diffrn_orient_matrix_UB_12      -0.0488957000
_diffrn_orient_matrix_UB_13      -0.0233840000
_diffrn_orient_matrix_UB_21      0.0340060000
_diffrn_orient_matrix_UB_22      0.0258875000
_diffrn_orient_matrix_UB_23      -0.0356165000
_diffrn_orient_matrix_UB_31      0.0420345000
_diffrn_orient_matrix_UB_32      -0.0061199000
_diffrn_orient_matrix_UB_33      0.0356011000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_reflns_Friedel_coverage         0.882
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                1508
_reflns_number_total             1670
_reflns_odcompleteness_completeness 99.74
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 Structure factors included contributions from the .fab file.
 
 _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       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 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    ?
_refine_diff_density_max         2.092
_refine_diff_density_min         -0.801
_refine_diff_density_rms         0.176
_refine_ls_abs_structure_details 
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.09(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.293
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     92
_refine_ls_number_reflns         1670
_refine_ls_number_restraints     26
_refine_ls_R_factor_all          0.1083
_refine_ls_R_factor_gt           0.1023
_refine_ls_restrained_S_all      1.298
_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)+(0.2000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2762
_refine_ls_wR_factor_ref         0.2864
_refine_special_details          
;
 Refined as a 2-component inversion twin.
;
_olex2_refinement_description    
;
1. Twinned data refinement
 Scales: 0.91(2) 0.09(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
3. Restrained distances
 C5-C6 = C6-C7 = C7-C8
 1.39 with sigma of 0.01
 C5-C8
 2.78 with sigma of 0.01
 C8-H8
 0.93 with sigma of 0.01
 C6-C7 \\sim C7-C8
 with sigma of 0.02
4. Restrained planarity
 C5, C6, C8, C7
 with sigma of 0.1
 C5, C6, C7, C8
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
Uanis(C8) \\sim Ueq, Uanis(C7) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C8) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
6. Others
 Fixed Sof: Br1(0.03333) C6(0.5) H6(0.5) O5(0.25) C7(0.5) H7(0.5) Br2(0.00833)
7.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B)
7.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C7(H7)
;
_atom_sites_solution_hydrogens   mixed
_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
Cs1 Cs 0.58656(4) 0.41344(4) 0.41344(4) 0.0714(7) Uani 1 6 d S T P . .
Si1 Si 0.500000 0.26058(16) 0.500000 0.0455(11) Uani 1 4 d S T P . .
Br1 Br 0.7108(2) 0.2108(2) 0.2892(2) 0.0316(17) Uani 0.2 6 d S T P A 2
O1 O 0.4990(2) 0.2747(2) 0.4398(2) 0.0419(13) Uani 1 1 d . . . . .
C4 C 0.6127(5) 0.3078(3) 0.3078(3) 0.047(3) Uani 1 2 d S T P . .
H4A H 0.590025 0.288907 0.288907 0.057 Uiso 1 2 calc RS T P . .
H4B H 0.644969 0.298290 0.298289 0.057 Uiso 1 2 calc RS T P . .
C3 C 0.6057(4) 0.2962(3) 0.3603(4) 0.048(2) Uani 1 1 d . . . . .
C2 C 0.5566(4) 0.2871(3) 0.3717(4) 0.046(2) Uani 1 1 d . . . . .
H2 H 0.533783 0.284734 0.347215 0.055 Uiso 1 1 calc R . . . .
C1 C 0.5430(3) 0.2818(3) 0.4196(4) 0.0403(18) Uani 1 1 d . . . . .
C5 C 0.500000 0.1895(9) 0.500000 0.112(14) Uani 1 4 d DS T P . .
C6 C 0.4833(8) 0.1653(7) 0.4598(7) 0.073(7) Uani 0.5 1 d D U . . .
H6 H 0.472084 0.181871 0.432914 0.088 Uiso 0.5 1 calc R . . . .
O5 O 0.6003(14) 0.3997(14) 0.5077(14) 0.109(13) Uani 0.5 2 d S T P . .
C8 C 0.500000 0.0890(9) 0.500000 0.096(9) Uani 1 4 d DS TU P . .
H8 H 0.500000 0.0554(10) 0.500000 0.115 Uiso 1 4 d DRS T P . .
C7 C 0.4840(9) 0.1157(7) 0.4611(8) 0.082(8) Uani 0.5 1 d D U . . .
H7 H 0.473078 0.099163 0.434042 0.098 Uiso 0.5 1 calc R . . . .
Br2 Br 0.750000 0.250000 0.250000 0.067(7) Uani 0.1999 24 d S T P B 1
Br3 Br 0.6308(5) 0.1308(5) 0.3692(5) 0.080(8) Uani 0.20(2) 6 d S T 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
Cs1 C3 3.606(10) 17 ?
Cs1 C3 3.607(10) . ?
Cs1 C3 3.606(10) 10_656 ?
Cs1 C3 3.606(10) 23_656 ?
Cs1 C3 3.606(10) 7_665 ?
Cs1 C3 3.606(10) 14_665 ?
Cs1 C2 3.781(10) . ?
Cs1 C2 3.781(10) 10_656 ?
Cs1 C2 3.781(10) 17 ?
Cs1 O5 2.67(4) . ?
Cs1 O5 2.67(4) 10_656 ?
Cs1 O5 2.67(4) 7_665 ?
Si1 O1 1.715(6) 3_656 ?
Si1 O1 1.715(6) . ?
Si1 O1 1.715(6) 23_656 ?
Si1 O1 1.715(6) 21 ?
Si1 C5 1.97(2) . ?
O1 C1 1.357(10) . ?
C4 H4A 0.9700 . ?
C4 H4B 0.9700 . ?
C4 C3 1.503(12) . ?
C4 C3 1.503(12) 17 ?
C3 C3 1.33(2) 23_656 ?
C3 C2 1.417(16) . ?
C2 H2 0.9300 . ?
C2 C1 1.388(15) . ?
C1 C1 1.466(18) 23_656 ?
C5 C6 1.380(12) 21 ?
C5 C6 1.380(12) 23_656 ?
C5 C6 1.380(12) 3_656 ?
C5 C6 1.380(12) . ?
C6 H6 0.9300 . ?
C6 C7 1.374(11) . ?
C8 H8 0.930(13) . ?
C8 C7 1.382(11) 23_656 ?
C8 C7 1.382(11) 3_656 ?
C8 C7 1.382(11) 21 ?
C8 C7 1.382(11) . ?
C7 H7 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
C3 Cs1 C3 55.9(3) 17 23_656 ?
C3 Cs1 C3 55.9(3) 7_665 10_656 ?
C3 Cs1 C3 55.9(3) 7_665 . ?
C3 Cs1 C3 21.3(4) 17 7_665 ?
C3 Cs1 C3 40.7(3) 17 . ?
C3 Cs1 C3 64.4(4) 23_656 7_665 ?
C3 Cs1 C3 40.7(3) 23_656 10_656 ?
C3 Cs1 C3 55.9(3) 17 14_665 ?
C3 Cs1 C3 21.3(4) 14_665 10_656 ?
C3 Cs1 C3 55.9(3) 23_656 14_665 ?
C3 Cs1 C3 21.3(4) 23_656 . ?
C3 Cs1 C3 40.7(3) 7_665 14_665 ?
C3 Cs1 C3 64.4(4) 14_665 . ?
C3 Cs1 C3 64.4(4) 17 10_656 ?
C3 Cs1 C3 55.9(3) 10_656 . ?
C3 Cs1 C2 37.8(2) 14_665 10_656 ?
C3 Cs1 C2 37.8(2) 7_665 17 ?
C3 Cs1 C2 86.4(3) 17 10_656 ?
C3 Cs1 C2 37.8(2) 23_656 . ?
C3 Cs1 C2 86.4(3) 10_656 17 ?
C3 Cs1 C2 71.2(3) 7_665 . ?
C3 Cs1 C2 77.0(2) 7_665 10_656 ?
C3 Cs1 C2 86.4(3) 14_665 . ?
C3 Cs1 C2 77.0(2) 14_665 17 ?
C3 Cs1 C2 77.0(2) 10_656 . ?
C3 Cs1 C2 51.5(2) . 17 ?
C3 Cs1 C2 22.0(2) . . ?
C3 Cs1 C2 51.5(2) 23_656 10_656 ?
C3 Cs1 C2 22.0(2) 17 17 ?
C3 Cs1 C2 71.2(3) 23_656 17 ?
C3 Cs1 C2 22.0(2) 10_656 10_656 ?
C3 Cs1 C2 51.5(2) 17 . ?
C3 Cs1 C2 71.2(3) . 10_656 ?
C2 Cs1 C2 89.2(3) . 10_656 ?
C2 Cs1 C2 52.0(3) . 17 ?
C2 Cs1 C2 108.2(4) 17 10_656 ?
O5 Cs1 C3 87.5(11) 10_656 14_665 ?
O5 Cs1 C3 104.5(10) 7_665 23_656 ?
O5 Cs1 C3 87.5(11) 7_665 . ?
O5 Cs1 C3 143.4(11) . 17 ?
O5 Cs1 C3 104.5(10) . 14_665 ?
O5 Cs1 C3 87.5(11) 7_665 17 ?
O5 Cs1 C3 143.4(11) . 7_665 ?
O5 Cs1 C3 104.5(10) 10_656 17 ?
O5 Cs1 C3 143.4(11) 10_656 23_656 ?
O5 Cs1 C3 87.5(11) . 10_656 ?
O5 Cs1 C3 104.5(10) . . ?
O5 Cs1 C3 104.5(10) 7_665 7_665 ?
O5 Cs1 C3 143.4(11) 10_656 . ?
O5 Cs1 C3 87.5(11) 10_656 7_665 ?
O5 Cs1 C3 143.4(11) 7_665 14_665 ?
O5 Cs1 C3 87.5(11) . 23_656 ?
O5 Cs1 C3 104.5(10) 10_656 10_656 ?
O5 Cs1 C3 143.4(11) 7_665 10_656 ?
O5 Cs1 C2 101.5(7) 10_656 10_656 ?
O5 Cs1 C2 67.0(10) 7_665 17 ?
O5 Cs1 C2 101.5(7) . . ?
O5 Cs1 C2 67.0(10) 7_665 . ?
O5 Cs1 C2 101.5(7) 10_656 17 ?
O5 Cs1 C2 153.5(6) 10_656 . ?
O5 Cs1 C2 153.5(6) 7_665 10_656 ?
O5 Cs1 C2 153.5(6) . 17 ?
O5 Cs1 C2 67.0(10) . 10_656 ?
O5 Cs1 O5 105.1(13) 7_665 10_656 ?
O5 Cs1 O5 105.1(13) . 10_656 ?
O5 Cs1 O5 105.1(13) . 7_665 ?
O1 Si1 O1 85.3(4) 23_656 3_656 ?
O1 Si1 O1 153.7(5) 3_656 . ?
O1 Si1 O1 88.8(4) 23_656 . ?
O1 Si1 O1 153.7(5) 23_656 21 ?
O1 Si1 O1 88.8(4) 3_656 21 ?
O1 Si1 O1 85.3(4) 21 . ?
O1 Si1 C5 103.2(3) 3_656 . ?
O1 Si1 C5 103.2(3) . . ?
O1 Si1 C5 103.2(3) 23_656 . ?
O1 Si1 C5 103.2(3) 21 . ?
C1 O1 Si1 114.9(6) . . ?
H4A C4 H4B 107.7 . . ?
C3 C4 H4A 108.9 . . ?
C3 C4 H4A 108.9 17 . ?
C3 C4 H4B 108.9 . . ?
C3 C4 H4B 108.9 17 . ?
C3 C4 C3 113.3(11) . 17 ?
C4 C3 Cs1 102.9(6) . . ?
C3 C3 Cs1 79.33(18) 23_656 . ?
C3 C3 C4 126.4(7) 23_656 . ?
C3 C3 C2 121.4(6) 23_656 . ?
C2 C3 Cs1 85.9(6) . . ?
C2 C3 C4 112.1(10) . . ?
Cs1 C2 H2 116.0 . . ?
C3 C2 Cs1 72.1(6) . . ?
C3 C2 H2 120.3 . . ?
C1 C2 Cs1 82.3(5) . . ?
C1 C2 C3 119.5(10) . . ?
C1 C2 H2 120.3 . . ?
O1 C1 Cs1 116.0(5) . . ?
O1 C1 C2 130.9(9) . . ?
O1 C1 C1 110.1(5) . 23_656 ?
C2 C1 Cs1 76.8(5) . . ?
C2 C1 C1 119.0(6) . 23_656 ?
C1 C1 Cs1 79.02(14) 23_656 . ?
C6 C5 Si1 119.1(13) 21 . ?
C6 C5 Si1 119.1(13) 23_656 . ?
C6 C5 Si1 119.1(13) . . ?
C6 C5 Si1 119.1(13) 3_656 . ?
C6 C5 C6 39(2) 21 . ?
C6 C5 C6 108(2) 3_656 21 ?
C6 C5 C6 108(2) 23_656 . ?
C6 C5 C6 39(2) 3_656 23_656 ?
C6 C5 C6 122(3) 3_656 . ?
C6 C5 C6 122(3) 23_656 21 ?
C5 C6 H6 121.3 . . ?
C7 C6 C5 117(3) . . ?
C7 C6 H6 121.3 . . ?
C7 C8 H8 122.4(14) 21 . ?
C7 C8 H8 122.4(14) 3_656 . ?
C7 C8 H8 122.4(14) 23_656 . ?
C7 C8 H8 122.4(14) . . ?
C7 C8 C7 38(2) 23_656 3_656 ?
C7 C8 C7 102(3) 21 3_656 ?
C7 C8 C7 115(3) 21 23_656 ?
C7 C8 C7 38(2) 21 . ?
C7 C8 C7 102(3) . 23_656 ?
C7 C8 C7 115(3) . 3_656 ?
C6 C7 C8 124(3) . . ?
C6 C7 H7 118.0 . . ?
C8 C7 H7 118.0 . . ?

_shelx_SHELXL_version_number     2018/1
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details 
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.445
_oxdiff_exptl_absorpt_empirical_full_min 0.782
loop_
_twin_individual_id
_twin_individual_mass_fraction_refined
1 0.91(2)
2 0.09(2)

