# Electronic Supplementary Material (ESI) for Chemical Science.
# This journal is © The Royal Society of Chemistry 2019

####################################################################### 
# 
# 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_03
_database_code_depnum_ccdc_archive 'CCDC 1864258'
_audit_update_record             
;
2018-08-28 deposited with the CCDC.
2018-10-31 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'B4.09 Ba4 Bi2 O29 Si7.91'
_chemical_formula_weight         1697.72

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
B B 0.0013 0.0007 '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'
Si Si 0.0817 0.0704 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ba Ba -0.3244 2.2819 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Bi Bi -4.1077 10.2566 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   I-42m

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

_cell_length_a                   11.0254(4)
_cell_length_b                   11.0254(4)
_cell_length_c                   10.3961(9)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                90.00
_cell_volume                     1263.74(13)
_cell_formula_units_Z            2
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    2422
_cell_measurement_theta_min      3.7070
_cell_measurement_theta_max      29.0770

_exptl_crystal_description       bulk
_exptl_crystal_colour            colourless
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    4.462
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             1506
_exptl_absorpt_coefficient_mu    20.514
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.44878
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  CCD
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean 10.3503
_diffrn_reflns_number            4257
_diffrn_reflns_av_R_equivalents  0.0424
_diffrn_reflns_av_sigmaI/netI    0.0279
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_theta_min         3.70
_diffrn_reflns_theta_max         26.31
_reflns_number_total             696
_reflns_number_gt                677
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXS-97 (Sheldrick, 2008)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 2008)'
_computing_molecular_graphics    ?
_computing_publication_material  ?

_refine_special_details          
; 
 Refinement of F² against ALL reflections.  The weighted R-factor wR and 
 goodness of fit S are based on F², conventional R-factors R are based 
 on F, with F set to zero for negative F². The threshold expression of 
 F² > 2sigma(F²) is used only for calculating R-factors(gt) etc. and is 
 not relevant to the choice of reflections for refinement.  R-factors based 
 on F² are statistically about twice as large as those based on F, and R- 
 factors based on ALL data will be even larger. 
;

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0118P)²+0.0000P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    .
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.00050(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.000(8)
_refine_ls_number_reflns         696
_refine_ls_number_parameters     63
_refine_ls_number_restraints     6
_refine_ls_R_factor_all          0.0177
_refine_ls_R_factor_gt           0.0169
_refine_ls_wR_factor_ref         0.0333
_refine_ls_wR_factor_gt          0.0329
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_restrained_S_all      1.034
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ba1 Ba 0.79418(2) 0.79418(2) -0.00007(9) 0.01563(13) Uani 1 2 d S . .
Bi1 Bi 1.0000 1.0000 0.19957(3) 0.01073(12) Uani 1 4 d S . .
Si1 Si 0.69576(11) 0.98592(18) 0.26621(13) 0.0078(5) Uani 0.926(7) 1 d P . .
B1 B 0.69576(11) 0.98592(18) 0.26621(13) 0.0078(5) Uani 0.074(7) 1 d P . .
B2 B 0.8291(4) 1.0000 0.5000 0.0063(17) Uani 0.875(10) 2 d SP . .
Si2 Si 0.8291(4) 1.0000 0.5000 0.0063(17) Uani 0.125(10) 2 d SP . .
O1 O 0.7932(3) 1.0057(5) 0.1554(3) 0.0143(7) Uani 1 1 d . . .
O2 O 0.6083(3) 0.8800(4) 0.2113(3) 0.0171(9) Uani 1 1 d . . .
O3 O 0.7496(3) 0.9415(3) 0.3994(3) 0.0106(8) Uani 1 1 d . . .
O4 O 0.9017(3) 0.9017(3) 0.5612(4) 0.0088(10) Uani 1 2 d S . .
O5 O 1.0000 1.0000 0.0000 0.0155(17) Uani 1 8 d SU . .


_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
Ba1 O1 2.734(5) 4_755 ?
Ba1 O1 2.734(5) 6_575 ?
Ba1 O1 2.838(5) 8 ?
Ba1 O1 2.838(5) . ?
Ba1 O3 2.842(3) 15_664 ?
Ba1 O3 2.842(3) 10_664 ?
Ba1 O4 3.120(5) 10_664 ?
Ba1 O2 3.150(4) 8 ?
Ba1 O2 3.150(4) . ?
Ba1 O5 3.2092(4) . ?
Ba1 Si2 3.5167(18) 11_465 ?
Ba1 Si2 3.5167(18) 10_664 ?
Bi1 O5 2.0748(3) . ?
Bi1 O1 2.327(3) 8 ?
Bi1 O1 2.327(3) 2_775 ?
Bi1 O1 2.327(3) 7_775 ?
Bi1 O1 2.327(3) . ?
Bi1 Ba1 3.8211(7) 3_575 ?
Bi1 Ba1 3.8211(7) 4_755 ?
Bi1 Ba1 3.8218(6) 2_775 ?
Si1 O3 1.584(4) . ?
Si1 O1 1.590(3) . ?
Si1 O2 1.604(4) 12_655 ?
Si1 O2 1.619(4) . ?
Si1 Ba1 3.8355(18) 3_575 ?
B2 O4 1.490(3) . ?
B2 O4 1.490(3) 3_576 ?
B2 O3 1.509(4) . ?
B2 O3 1.509(4) 6_576 ?
O1 Ba1 2.734(5) 3_575 ?
O2 B1 1.604(4) 11_465 ?
O2 Si1 1.604(4) 11_465 ?
O3 Ba1 2.842(3) 10_665 ?
O4 Si2 1.490(3) 4_756 ?
O4 B2 1.490(3) 4_756 ?
O4 Ba1 3.120(5) 10_665 ?
O5 Bi1 2.0747(3) 3_575 ?
O5 Ba1 3.2092(4) 2_775 ?
O5 Ba1 3.2092(4) 3_575 ?
O5 Ba1 3.2092(4) 4_755 ?

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 Ba1 O1 69.98(14) 4_755 6_575 ?
O1 Ba1 O1 70.94(10) 4_755 8 ?
O1 Ba1 O1 110.06(11) 6_575 8 ?
O1 Ba1 O1 110.06(11) 4_755 . ?
O1 Ba1 O1 70.94(10) 6_575 . ?
O1 Ba1 O1 71.46(13) 8 . ?
O1 Ba1 O3 121.32(11) 4_755 15_664 ?
O1 Ba1 O3 85.19(9) 6_575 15_664 ?
O1 Ba1 O3 163.79(11) 8 15_664 ?
O1 Ba1 O3 110.21(9) . 15_664 ?
O1 Ba1 O3 85.19(9) 4_755 10_664 ?
O1 Ba1 O3 121.32(11) 6_575 10_664 ?
O1 Ba1 O3 110.21(9) 8 10_664 ?
O1 Ba1 O3 163.79(11) . 10_664 ?
O3 Ba1 O3 63.53(14) 15_664 10_664 ?
O1 Ba1 O4 132.56(8) 4_755 10_664 ?
O1 Ba1 O4 132.56(8) 6_575 10_664 ?
O1 Ba1 O4 116.73(9) 8 10_664 ?
O1 Ba1 O4 116.73(9) . 10_664 ?
O3 Ba1 O4 47.52(9) 15_664 10_664 ?
O3 Ba1 O4 47.52(9) 10_664 10_664 ?
O1 Ba1 O2 99.62(11) 4_755 8 ?
O1 Ba1 O2 159.75(10) 6_575 8 ?
O1 Ba1 O2 49.70(10) 8 8 ?
O1 Ba1 O2 97.96(11) . 8 ?
O3 Ba1 O2 114.87(10) 15_664 8 ?
O3 Ba1 O2 73.30(9) 10_664 8 ?
O4 Ba1 O2 67.36(9) 10_664 8 ?
O1 Ba1 O2 159.75(10) 4_755 . ?
O1 Ba1 O2 99.62(11) 6_575 . ?
O1 Ba1 O2 97.96(11) 8 . ?
O1 Ba1 O2 49.70(10) . . ?
O3 Ba1 O2 73.30(9) 15_664 . ?
O3 Ba1 O2 114.87(10) 10_664 . ?
O4 Ba1 O2 67.36(9) 10_664 . ?
O2 Ba1 O2 84.51(14) 8 . ?
O1 Ba1 O5 55.42(7) 4_755 . ?
O1 Ba1 O5 55.42(7) 6_575 . ?
O1 Ba1 O5 54.66(7) 8 . ?
O1 Ba1 O5 54.66(7) . . ?
O3 Ba1 O5 140.06(7) 15_664 . ?
O3 Ba1 O5 140.06(7) 10_664 . ?
O4 Ba1 O5 168.20(9) 10_664 . ?
O2 Ba1 O5 104.33(7) 8 . ?
O2 Ba1 O5 104.33(7) . . ?
O1 Ba1 Si2 137.96(9) 4_755 11_465 ?
O1 Ba1 Si2 107.95(8) 6_575 11_465 ?
O1 Ba1 Si2 139.15(9) 8 11_465 ?
O1 Ba1 Si2 108.29(8) . 11_465 ?
O3 Ba1 Si2 24.66(8) 15_664 11_465 ?
O3 Ba1 Si2 59.34(10) 10_664 11_465 ?
O4 Ba1 Si2 25.05(7) 10_664 11_465 ?
O2 Ba1 Si2 91.46(9) 8 11_465 ?
O2 Ba1 Si2 61.05(8) . 11_465 ?
O5 Ba1 Si2 157.74(7) . 11_465 ?
O1 Ba1 Si2 107.95(8) 4_755 10_664 ?
O1 Ba1 Si2 137.96(9) 6_575 10_664 ?
O1 Ba1 Si2 108.29(8) 8 10_664 ?
O1 Ba1 Si2 139.15(9) . 10_664 ?
O3 Ba1 Si2 59.34(10) 15_664 10_664 ?
O3 Ba1 Si2 24.66(8) 10_664 10_664 ?
O4 Ba1 Si2 25.05(7) 10_664 10_664 ?
O2 Ba1 Si2 61.05(8) 8 10_664 ?
O2 Ba1 Si2 91.46(9) . 10_664 ?
O5 Ba1 Si2 157.74(7) . 10_664 ?
Si2 Ba1 Si2 44.53(13) 11_465 10_664 ?
O5 Bi1 O1 78.63(8) . 8 ?
O5 Bi1 O1 78.63(8) . 2_775 ?
O1 Bi1 O1 84.7(3) 8 2_775 ?
O5 Bi1 O1 78.63(8) . 7_775 ?
O1 Bi1 O1 157.25(15) 8 7_775 ?
O1 Bi1 O1 90.8(3) 2_775 7_775 ?
O5 Bi1 O1 78.63(8) . . ?
O1 Bi1 O1 90.8(3) 8 . ?
O1 Bi1 O1 157.25(15) 2_775 . ?
O1 Bi1 O1 84.7(3) 7_775 . ?
O5 Bi1 Ba1 57.126(14) . 3_575 ?
O1 Bi1 Ba1 119.41(11) 8 3_575 ?
O1 Bi1 Ba1 119.41(11) 2_775 3_575 ?
O1 Bi1 Ba1 45.16(12) 7_775 3_575 ?
O1 Bi1 Ba1 45.16(12) . 3_575 ?
O5 Bi1 Ba1 57.126(14) . 4_755 ?
O1 Bi1 Ba1 45.16(12) 8 4_755 ?
O1 Bi1 Ba1 45.16(12) 2_775 4_755 ?
O1 Bi1 Ba1 119.41(11) 7_775 4_755 ?
O1 Bi1 Ba1 119.41(11) . 4_755 ?
Ba1 Bi1 Ba1 114.25(3) 3_575 4_755 ?
O5 Bi1 Ba1 57.108(14) . . ?
O1 Bi1 Ba1 47.71(12) 8 . ?
O1 Bi1 Ba1 117.30(11) 2_775 . ?
O1 Bi1 Ba1 117.30(11) 7_775 . ?
O1 Bi1 Ba1 47.71(12) . . ?
Ba1 Bi1 Ba1 72.856(5) 3_575 . ?
Ba1 Bi1 Ba1 72.856(5) 4_755 . ?
O5 Bi1 Ba1 57.108(14) . 2_775 ?
O1 Bi1 Ba1 117.30(11) 8 2_775 ?
O1 Bi1 Ba1 47.71(12) 2_775 2_775 ?
O1 Bi1 Ba1 47.71(12) 7_775 2_775 ?
O1 Bi1 Ba1 117.30(11) . 2_775 ?
Ba1 Bi1 Ba1 72.856(5) 3_575 2_775 ?
Ba1 Bi1 Ba1 72.856(5) 4_755 2_775 ?
Ba1 Bi1 Ba1 114.22(3) . 2_775 ?
O3 Si1 O1 115.0(2) . . ?
O3 Si1 O2 109.12(18) . 12_655 ?
O1 Si1 O2 110.0(3) . 12_655 ?
O3 Si1 O2 108.0(2) . . ?
O1 Si1 O2 104.2(2) . . ?
O2 Si1 O2 110.4(3) 12_655 . ?
O3 Si1 Ba1 111.88(14) . . ?
O1 Si1 Ba1 47.9(2) . . ?
O2 Si1 Ba1 138.86(13) 12_655 . ?
O2 Si1 Ba1 59.42(14) . . ?
O3 Si1 Ba1 136.05(14) . 3_575 ?
O1 Si1 Ba1 36.82(19) . 3_575 ?
O2 Si1 Ba1 73.79(14) 12_655 3_575 ?
O2 Si1 Ba1 111.72(14) . 3_575 ?
Ba1 Si1 Ba1 74.62(3) . 3_575 ?
O4 B2 O4 115.0(5) . 3_576 ?
O4 B2 O3 107.3(2) . . ?
O4 B2 O3 109.1(2) 3_576 . ?
O4 B2 O3 109.1(2) . 6_576 ?
O4 B2 O3 107.3(2) 3_576 6_576 ?
O3 B2 O3 109.0(4) . 6_576 ?
Si1 O1 Bi1 121.03(18) . . ?
Si1 O1 Ba1 122.8(2) . 3_575 ?
Bi1 O1 Ba1 97.72(15) . 3_575 ?
Si1 O1 Ba1 107.6(3) . . ?
Bi1 O1 Ba1 94.94(14) . . ?
Ba1 O1 Ba1 109.06(10) 3_575 . ?
B1 O2 Si1 0.00(8) 11_465 11_465 ?
B1 O2 Si1 145.6(2) 11_465 . ?
Si1 O2 Si1 145.6(2) 11_465 . ?
B1 O2 Ba1 119.52(17) 11_465 . ?
Si1 O2 Ba1 119.52(17) 11_465 . ?
Si1 O2 Ba1 94.32(16) . . ?
B2 O3 Si1 133.7(2) . . ?
B2 O3 Ba1 103.57(16) . 10_665 ?
Si1 O3 Ba1 122.71(18) . 10_665 ?
Si2 O4 B2 126.8(4) 4_756 . ?
Si2 O4 B2 0.0(3) 4_756 4_756 ?
B2 O4 B2 126.8(4) . 4_756 ?
Si2 O4 Ba1 92.5(2) 4_756 10_665 ?
B2 O4 Ba1 92.5(2) . 10_665 ?
B2 O4 Ba1 92.5(2) 4_756 10_665 ?
Bi1 O5 Bi1 180.0 3_575 . ?
Bi1 O5 Ba1 89.988(18) 3_575 . ?
Bi1 O5 Ba1 90.012(18) . . ?
Bi1 O5 Ba1 89.987(18) 3_575 2_775 ?
Bi1 O5 Ba1 90.013(18) . 2_775 ?
Ba1 O5 Ba1 179.97(4) . 2_775 ?
Bi1 O5 Ba1 90.013(18) 3_575 3_575 ?
Bi1 O5 Ba1 89.987(18) . 3_575 ?
Ba1 O5 Ba1 90.0 . 3_575 ?
Ba1 O5 Ba1 90.0 2_775 3_575 ?
Bi1 O5 Ba1 90.013(18) 3_575 4_755 ?
Bi1 O5 Ba1 89.987(18) . 4_755 ?
Ba1 O5 Ba1 90.0 . 4_755 ?
Ba1 O5 Ba1 90.0 2_775 4_755 ?
Ba1 O5 Ba1 179.97(4) 3_575 4_755 ?

_diffrn_measured_fraction_theta_max 0.990
_diffrn_reflns_theta_full        26.31
_diffrn_measured_fraction_theta_full 0.990
_refine_diff_density_max         0.998
_refine_diff_density_min         -0.761
_refine_diff_density_rms         0.137
