# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2020

####################################################################### 
# 
# 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_1_a
_database_code_depnum_ccdc_archive 'CCDC 1973093'
_audit_update_record             
;
2019-12-19 deposited with the CCDC.	2020-05-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ba3 I18 O54 Ti3'
_chemical_formula_weight         3703.93

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ba Ba -0.3244 2.2819 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
I I -0.4742 1.8119 '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'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3 :H'
_space_group_name_Hall           '-R 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'
'-y, x-y, z'
'-x+y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'

_cell_length_a                   10.9589(7)
_cell_length_b                   10.9589(7)
_cell_length_c                   11.1331(10)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1157.93(18)
_cell_formula_units_Z            1
_cell_measurement_temperature    293(2)
_cell_measurement_reflns_used    1940
_cell_measurement_theta_min      2.82
_cell_measurement_theta_max      27.48

_exptl_crystal_description       bulk
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    5.312
_exptl_crystal_F_000             1620
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    15.150
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      293(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            2964
_diffrn_reflns_av_unetI/netI     0.0220
_diffrn_reflns_av_R_equivalents  0.0284
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.820
_diffrn_reflns_theta_max         27.486
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             601
_reflns_number_gt                552
_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.1000P)²] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         601
_refine_ls_number_parameters     41
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0261
_refine_ls_R_factor_gt           0.0232
_refine_ls_wR_factor_ref         0.0824
_refine_ls_wR_factor_gt          0.0751
_refine_ls_goodness_of_fit_ref   0.712
_refine_ls_restrained_S_all      0.712
_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
Ba1 Ba 0.000000 0.000000 0.500000 0.0107(2) Uani 1 6 d S T P . .
Ti1 Ti 0.333333 0.666667 0.666667 0.0113(5) Uani 1 6 d S T P . .
I1 I 0.11460(3) 0.40795(3) 0.45577(3) 0.0108(2) Uani 1 1 d . . . . .
O1 O 0.1681(4) 0.5521(4) 0.5675(3) 0.0125(7) Uani 1 1 d . . . . .
O2 O 0.1271(4) 0.2875(4) 0.5550(3) 0.0151(8) Uani 1 1 d . . . . .
O3 O 0.2740(4) 0.4702(4) 0.3690(4) 0.0175(8) Uani 1 1 d . . . . .

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
Ba1 0.0099(3) 0.0099(3) 0.0122(4) 0.000 0.000 0.00496(14)
Ti1 0.0106(6) 0.0106(6) 0.0128(11) 0.000 0.000 0.0053(3)
I1 0.0111(2) 0.0115(2) 0.0101(3) 0.00066(10) 0.00041(10) 0.00592(15)
O1 0.0114(17) 0.0141(18) 0.0124(17) -0.0010(13) 0.0008(13) 0.0066(15)
O2 0.0212(19) 0.0148(18) 0.0122(18) 0.0036(14) -0.0012(14) 0.0112(16)
O3 0.0157(18) 0.019(2) 0.0161(19) -0.0016(14) 0.0040(15) 0.0076(16)

_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 O2 2.802(4) . ?
Ba1 O2 2.802(4) 10_556 ?
Ba1 O2 2.802(4) 11_556 ?
Ba1 O2 2.802(4) 2 ?
Ba1 O2 2.802(4) 12_556 ?
Ba1 O2 2.802(4) 3 ?
Ba1 O3 2.955(4) 17_445 ?
Ba1 O3 2.955(4) 5 ?
Ba1 O3 2.955(4) 18_545 ?
Ba1 O3 2.955(4) 6_455 ?
Ba1 O3 2.955(4) 16 ?
Ba1 O3 2.955(4) 4_445 ?
Ti1 O1 1.950(3) 15_556 ?
Ti1 O1 1.950(3) 3_565 ?
Ti1 O1 1.950(4) 13_566 ?
Ti1 O1 1.950(3) 2_665 ?
Ti1 O1 1.950(4) . ?
Ti1 O1 1.950(3) 14_456 ?
I1 O2 1.779(3) . ?
I1 O3 1.805(4) . ?
I1 O1 1.860(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 Ba1 O2 180.0 . 10_556 ?
O2 Ba1 O2 64.64(5) . 11_556 ?
O2 Ba1 O2 115.36(5) 10_556 11_556 ?
O2 Ba1 O2 115.36(5) . 2 ?
O2 Ba1 O2 64.64(5) 10_556 2 ?
O2 Ba1 O2 180.0 11_556 2 ?
O2 Ba1 O2 64.64(5) . 12_556 ?
O2 Ba1 O2 115.36(5) 10_556 12_556 ?
O2 Ba1 O2 115.36(5) 11_556 12_556 ?
O2 Ba1 O2 64.64(5) 2 12_556 ?
O2 Ba1 O2 115.36(5) . 3 ?
O2 Ba1 O2 64.64(5) 10_556 3 ?
O2 Ba1 O2 64.64(5) 11_556 3 ?
O2 Ba1 O2 115.36(5) 2 3 ?
O2 Ba1 O2 180.00(14) 12_556 3 ?
O2 Ba1 O3 124.38(10) . 17_445 ?
O2 Ba1 O3 55.62(10) 10_556 17_445 ?
O2 Ba1 O3 117.19(10) 11_556 17_445 ?
O2 Ba1 O3 62.81(10) 2 17_445 ?
O2 Ba1 O3 66.90(10) 12_556 17_445 ?
O2 Ba1 O3 113.10(10) 3 17_445 ?
O2 Ba1 O3 55.62(10) . 5 ?
O2 Ba1 O3 124.38(10) 10_556 5 ?
O2 Ba1 O3 62.81(10) 11_556 5 ?
O2 Ba1 O3 117.19(10) 2 5 ?
O2 Ba1 O3 113.10(10) 12_556 5 ?
O2 Ba1 O3 66.90(10) 3 5 ?
O3 Ba1 O3 180.0 17_445 5 ?
O2 Ba1 O3 113.10(10) . 18_545 ?
O2 Ba1 O3 66.90(10) 10_556 18_545 ?
O2 Ba1 O3 55.62(10) 11_556 18_545 ?
O2 Ba1 O3 124.38(10) 2 18_545 ?
O2 Ba1 O3 117.19(10) 12_556 18_545 ?
O2 Ba1 O3 62.81(10) 3 18_545 ?
O3 Ba1 O3 68.18(12) 17_445 18_545 ?
O3 Ba1 O3 111.82(12) 5 18_545 ?
O2 Ba1 O3 66.90(10) . 6_455 ?
O2 Ba1 O3 113.10(10) 10_556 6_455 ?
O2 Ba1 O3 124.38(10) 11_556 6_455 ?
O2 Ba1 O3 55.62(10) 2 6_455 ?
O2 Ba1 O3 62.81(10) 12_556 6_455 ?
O2 Ba1 O3 117.19(10) 3 6_455 ?
O3 Ba1 O3 111.82(12) 17_445 6_455 ?
O3 Ba1 O3 68.18(12) 5 6_455 ?
O3 Ba1 O3 180.0 18_545 6_455 ?
O2 Ba1 O3 62.81(10) . 16 ?
O2 Ba1 O3 117.19(10) 10_556 16 ?
O2 Ba1 O3 66.90(10) 11_556 16 ?
O2 Ba1 O3 113.10(10) 2 16 ?
O2 Ba1 O3 55.62(10) 12_556 16 ?
O2 Ba1 O3 124.38(10) 3 16 ?
O3 Ba1 O3 68.18(12) 17_445 16 ?
O3 Ba1 O3 111.82(12) 5 16 ?
O3 Ba1 O3 68.18(12) 18_545 16 ?
O3 Ba1 O3 111.82(12) 6_455 16 ?
O2 Ba1 O3 117.19(10) . 4_445 ?
O2 Ba1 O3 62.81(10) 10_556 4_445 ?
O2 Ba1 O3 113.10(10) 11_556 4_445 ?
O2 Ba1 O3 66.90(10) 2 4_445 ?
O2 Ba1 O3 124.38(10) 12_556 4_445 ?
O2 Ba1 O3 55.62(10) 3 4_445 ?
O3 Ba1 O3 111.82(12) 17_445 4_445 ?
O3 Ba1 O3 68.18(12) 5 4_445 ?
O3 Ba1 O3 111.82(12) 18_545 4_445 ?
O3 Ba1 O3 68.18(12) 6_455 4_445 ?
O3 Ba1 O3 180.0 16 4_445 ?
O1 Ti1 O1 180.0 15_556 3_565 ?
O1 Ti1 O1 91.08(14) 15_556 13_566 ?
O1 Ti1 O1 88.92(14) 3_565 13_566 ?
O1 Ti1 O1 88.93(14) 15_556 2_665 ?
O1 Ti1 O1 91.08(14) 3_565 2_665 ?
O1 Ti1 O1 88.93(14) 13_566 2_665 ?
O1 Ti1 O1 88.92(14) 15_556 . ?
O1 Ti1 O1 91.08(14) 3_565 . ?
O1 Ti1 O1 180.0 13_566 . ?
O1 Ti1 O1 91.08(14) 2_665 . ?
O1 Ti1 O1 91.08(14) 15_556 14_456 ?
O1 Ti1 O1 88.92(14) 3_565 14_456 ?
O1 Ti1 O1 91.07(14) 13_566 14_456 ?
O1 Ti1 O1 180.0 2_665 14_456 ?
O1 Ti1 O1 88.92(14) . 14_456 ?
O2 I1 O3 101.18(17) . . ?
O2 I1 O1 96.12(16) . . ?
O3 I1 O1 101.67(16) . . ?
I1 O1 Ti1 136.2(2) . . ?
I1 O2 Ba1 121.27(17) . . ?
I1 O3 Ba1 120.14(17) . 7_554 ?

_refine_diff_density_max         1.016
_refine_diff_density_min         -2.575
_refine_diff_density_rms         0.462

_shelx_res_file                  
;
TITL 1_a.res in R-3
    1_a.res
    created by SHELXL-2018/3 at 21:13:59 on 19-Dec-2019
REM Old TITL 1 in R-3
REM SHELXT solution in R-3
REM R1 0.031,  Rweak 0.004,  Alpha 0.016,  Orientation as input
REM Formula found by SHELXT:  I7 O18 Ti
CELL  0.71073  10.9589  10.9589  11.1331   90.000   90.000  120.000
ZERR    1.000   0.0007   0.0007   0.0010    0.000    0.000    0.000
LATT  3
SYMM -Y, X-Y, Z
SYMM -X+Y, -X, Z
SFAC BA I O TI
UNIT 3.00006 18 54 3.00006
TEMP 19.850
L.S. 10
BOND $H
LIST 4
acta
FMAP 2
PLAN 5
WGHT    0.100000
FVAR       0.13433
BA1   1    0.000000    0.000000    0.500000    10.16667    0.00991    0.00991 =
         0.01219    0.00000    0.00000    0.00496
TI1   4    0.333333    0.666667    0.666667    10.16667    0.01059    0.01059 =
         0.01277    0.00000    0.00000    0.00530
I1    2    0.114596    0.407948    0.455773    11.00000    0.01110    0.01145 =
         0.01010    0.00066    0.00041    0.00592
O1    3    0.168050    0.552093    0.567453    11.00000    0.01136    0.01411 =
         0.01240   -0.00101    0.00085    0.00660
O2    3    0.127104    0.287480    0.555034    11.00000    0.02123    0.01482 =
         0.01224    0.00360   -0.00123    0.01123
O3    3    0.274023    0.470233    0.368992    11.00000    0.01574    0.01918 =
         0.01606   -0.00156    0.00396    0.00757
HKLF 4




REM  1_a.res in R-3
REM wR2 = 0.082416, GooF = S = 0.71227, Restrained GooF = 0.71227 for all data
REM R1 = 0.023233 for 552 Fo > 4sig(Fo) and 0.026116 for all 601 data
REM 41 parameters refined using 0 restraints

END

WGHT      0.0309      0.0000

REM Highest difference peak  1.016,  deepest hole -2.575,  1-sigma level  0.462
Q1    1   0.1210  0.2343  0.5002  11.00000  0.05    1.02
Q2    1   0.0721  0.6389  0.5730  11.00000  0.05    0.94
Q3    1   0.0102  0.1854  0.5460  11.00000  0.05    0.85
Q4    1   0.0635  0.2666  0.4812  11.00000  0.05    0.82
Q5    1   0.2568  0.6288  0.5582  11.00000  0.05    0.76
;
_shelx_res_checksum              54527
####################################################################### 
# 
# 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_a_BaTiIO
_database_code_depnum_ccdc_archive 'CCDC 1983324'
_audit_update_record             
;
2020-02-17 deposited with the CCDC.	2020-05-29 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2018/3
_shelx_SHELXL_version_number     2018/3
_chemical_name_systematic        ?
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ba I6 O18 Ti'
_chemical_formula_weight         1234.64

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ba Ba -0.3244 2.2819 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
I I -0.4742 1.8119 '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'
Ti Ti 0.2776 0.4457 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_H-M_alt        'R -3 :H'
_space_group_name_Hall           '-R 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'
'-y, x-y, z'
'-x+y, -x, z'
'x+2/3, y+1/3, z+1/3'
'-y+2/3, x-y+1/3, z+1/3'
'-x+y+2/3, -x+1/3, z+1/3'
'x+1/3, y+2/3, z+2/3'
'-y+1/3, x-y+2/3, z+2/3'
'-x+y+1/3, -x+2/3, z+2/3'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'-x+2/3, -y+1/3, -z+1/3'
'y+2/3, -x+y+1/3, -z+1/3'
'x-y+2/3, x+1/3, -z+1/3'
'-x+1/3, -y+2/3, -z+2/3'
'y+1/3, -x+y+2/3, -z+2/3'
'x-y+1/3, x+2/3, -z+2/3'

_cell_length_a                   11.4412(17)
_cell_length_b                   11.4412(17)
_cell_length_c                   11.1418(17)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1263.1(4)
_cell_formula_units_Z            3
_cell_measurement_temperature    297(2)
_cell_measurement_reflns_used    4456
_cell_measurement_theta_min      3.56
_cell_measurement_theta_max      27.5

_exptl_crystal_description       bulk
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_density_diffrn    4.869
_exptl_crystal_F_000             1620
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          ?
_exptl_crystal_size_mid          ?
_exptl_crystal_size_min          ?
_exptl_absorpt_coefficient_mu    13.889
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   ?
_exptl_absorpt_correction_T_min  ?
_exptl_absorpt_correction_T_max  ?
_exptl_absorpt_process_details   ?
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      297(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       ?
_diffrn_detector_area_resol_mean ?
_diffrn_reflns_number            9462
_diffrn_reflns_av_unetI/netI     0.0190
_diffrn_reflns_av_R_equivalents  0.0477
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_theta_min         2.751
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             646
_reflns_number_gt                609
_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       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_molecular_graphics    ?
_computing_publication_material  ?
_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)+(0.0187P)²+45.6908P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   .
_refine_ls_hydrogen_treatment    undef
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         646
_refine_ls_number_parameters     42
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0255
_refine_ls_R_factor_gt           0.0226
_refine_ls_wR_factor_ref         0.0575
_refine_ls_wR_factor_gt          0.0560
_refine_ls_goodness_of_fit_ref   1.134
_refine_ls_restrained_S_all      1.134
_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
Ba1 Ba 0.000000 0.000000 0.38016(15) 0.0227(3) Uani 0.5 3 d S T P . .
Ti1 Ti 0.333333 0.666667 0.666667 0.0120(5) Uani 1 6 d S T P . .
I1 I 0.07178(4) 0.35476(4) 0.55809(3) 0.01100(13) Uani 1 1 d . . . . .
O1 O 0.0965(5) 0.2883(5) 0.6966(4) 0.0214(10) Uani 1 1 d . . . . .
O2 O 0.1225(5) 0.2707(5) 0.4527(4) 0.0180(9) Uani 1 1 d . . . . .
O3 O 0.2380(5) 0.5129(5) 0.5608(4) 0.0200(10) Uani 1 1 d . . . . .

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
Ba1 0.0112(4) 0.0112(4) 0.0457(9) 0.000 0.000 0.00562(19)
Ti1 0.0107(8) 0.0107(8) 0.0147(13) 0.000 0.000 0.0053(4)
I1 0.0120(2) 0.0106(2) 0.0112(2) -0.00166(13) -0.00121(13) 0.00626(16)
O1 0.027(3) 0.025(3) 0.013(2) 0.0035(19) -0.0006(19) 0.013(2)
O2 0.016(2) 0.017(2) 0.022(2) -0.0045(18) 0.0027(18) 0.0083(19)
O3 0.015(2) 0.012(2) 0.026(3) -0.0070(19) -0.0006(19) 0.0017(19)

_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 Ba1 2.671(3) 10_556 ?
Ba1 O2 2.805(5) . ?
Ba1 O2 2.805(5) 2 ?
Ba1 O2 2.805(5) 3 ?
Ba1 O1 3.031(5) 10_556 ?
Ba1 O1 3.031(5) 11_556 ?
Ba1 O1 3.031(5) 12_556 ?
Ba1 O2 3.268(5) 11_556 ?
Ba1 O2 3.268(5) 12_556 ?
Ba1 O2 3.268(5) 10_556 ?
Ba1 I1 3.7800(7) 12_556 ?
Ba1 I1 3.7801(7) 11_556 ?
Ti1 O3 1.939(4) 15_556 ?
Ti1 O3 1.939(4) 3_565 ?
Ti1 O3 1.939(4) 2_665 ?
Ti1 O3 1.939(4) . ?
Ti1 O3 1.939(4) 13_566 ?
Ti1 O3 1.939(4) 14_456 ?
I1 O2 1.788(4) . ?
I1 O1 1.804(5) . ?
I1 O3 1.857(5) . ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
Ba1 Ba1 O2 73.25(10) 10_556 . ?
Ba1 Ba1 O2 73.25(10) 10_556 2 ?
O2 Ba1 O2 112.05(9) . 2 ?
Ba1 Ba1 O2 73.25(10) 10_556 3 ?
O2 Ba1 O2 112.05(9) . 3 ?
O2 Ba1 O2 112.05(9) 2 3 ?
Ba1 Ba1 O1 106.39(9) 10_556 10_556 ?
O2 Ba1 O1 172.64(13) . 10_556 ?
O2 Ba1 O1 74.47(13) 2 10_556 ?
O2 Ba1 O1 61.31(13) 3 10_556 ?
Ba1 Ba1 O1 106.39(9) 10_556 11_556 ?
O2 Ba1 O1 61.31(13) . 11_556 ?
O2 Ba1 O1 172.64(13) 2 11_556 ?
O2 Ba1 O1 74.47(13) 3 11_556 ?
O1 Ba1 O1 112.37(8) 10_556 11_556 ?
Ba1 Ba1 O1 106.39(9) 10_556 12_556 ?
O2 Ba1 O1 74.47(13) . 12_556 ?
O2 Ba1 O1 61.31(13) 2 12_556 ?
O2 Ba1 O1 172.64(13) 3 12_556 ?
O1 Ba1 O1 112.37(8) 10_556 12_556 ?
O1 Ba1 O1 112.37(8) 11_556 12_556 ?
Ba1 Ba1 O2 55.27(8) 10_556 11_556 ?
O2 Ba1 O2 56.10(5) . 11_556 ?
O2 Ba1 O2 128.52(10) 2 11_556 ?
O2 Ba1 O2 56.10(5) 3 11_556 ?
O1 Ba1 O2 117.41(12) 10_556 11_556 ?
O1 Ba1 O2 51.63(12) 11_556 11_556 ?
O1 Ba1 O2 129.98(12) 12_556 11_556 ?
Ba1 Ba1 O2 55.27(8) 10_556 12_556 ?
O2 Ba1 O2 56.10(5) . 12_556 ?
O2 Ba1 O2 56.10(5) 2 12_556 ?
O2 Ba1 O2 128.52(10) 3 12_556 ?
O1 Ba1 O2 129.98(12) 10_556 12_556 ?
O1 Ba1 O2 117.41(12) 11_556 12_556 ?
O1 Ba1 O2 51.63(12) 12_556 12_556 ?
O2 Ba1 O2 90.75(12) 11_556 12_556 ?
Ba1 Ba1 O2 55.27(8) 10_556 10_556 ?
O2 Ba1 O2 128.52(10) . 10_556 ?
O2 Ba1 O2 56.10(5) 2 10_556 ?
O2 Ba1 O2 56.10(5) 3 10_556 ?
O1 Ba1 O2 51.63(12) 10_556 10_556 ?
O1 Ba1 O2 129.98(12) 11_556 10_556 ?
O1 Ba1 O2 117.41(12) 12_556 10_556 ?
O2 Ba1 O2 90.75(12) 11_556 10_556 ?
O2 Ba1 O2 90.75(12) 12_556 10_556 ?
Ba1 Ba1 I1 79.51(3) 10_556 12_556 ?
O2 Ba1 I1 73.56(9) . 12_556 ?
O2 Ba1 I1 43.29(9) 2 12_556 ?
O2 Ba1 I1 148.58(11) 3 12_556 ?
O1 Ba1 I1 113.72(10) 10_556 12_556 ?
O1 Ba1 I1 129.36(10) 11_556 12_556 ?
O1 Ba1 I1 28.06(9) 12_556 12_556 ?
O2 Ba1 I1 118.42(9) 11_556 12_556 ?
O2 Ba1 I1 28.22(8) 12_556 12_556 ?
O2 Ba1 I1 95.40(8) 10_556 12_556 ?
Ba1 Ba1 I1 79.51(3) 10_556 11_556 ?
O2 Ba1 I1 43.30(9) . 11_556 ?
O2 Ba1 I1 148.58(11) 2 11_556 ?
O2 Ba1 I1 73.56(9) 3 11_556 ?
O1 Ba1 I1 129.36(10) 10_556 11_556 ?
O1 Ba1 I1 28.06(9) 11_556 11_556 ?
O1 Ba1 I1 113.72(10) 12_556 11_556 ?
O2 Ba1 I1 28.22(8) 11_556 11_556 ?
O2 Ba1 I1 95.40(8) 12_556 11_556 ?
O2 Ba1 I1 118.42(9) 10_556 11_556 ?
I1 Ba1 I1 116.764(16) 12_556 11_556 ?
O3 Ti1 O3 180.0 15_556 3_565 ?
O3 Ti1 O3 93.2(2) 15_556 2_665 ?
O3 Ti1 O3 86.8(2) 3_565 2_665 ?
O3 Ti1 O3 93.2(2) 15_556 . ?
O3 Ti1 O3 86.8(2) 3_565 . ?
O3 Ti1 O3 86.8(2) 2_665 . ?
O3 Ti1 O3 86.8(2) 15_556 13_566 ?
O3 Ti1 O3 93.2(2) 3_565 13_566 ?
O3 Ti1 O3 93.2(2) 2_665 13_566 ?
O3 Ti1 O3 180.0 . 13_566 ?
O3 Ti1 O3 86.8(2) 15_556 14_456 ?
O3 Ti1 O3 93.2(2) 3_565 14_456 ?
O3 Ti1 O3 180.0 2_665 14_456 ?
O3 Ti1 O3 93.2(2) . 14_456 ?
O3 Ti1 O3 86.8(2) 13_566 14_456 ?
O2 I1 O1 100.0(2) . . ?
O2 I1 O3 94.9(2) . . ?
O1 I1 O3 95.6(2) . . ?
O2 I1 Ba1 59.78(15) . 10_556 ?
O1 I1 Ba1 52.21(16) . 10_556 ?
O3 I1 Ba1 127.60(15) . 10_556 ?
I1 O1 Ba1 99.72(19) . 10_556 ?
I1 O2 Ba1 131.7(2) . . ?
I1 O2 Ba1 92.01(18) . 10_556 ?
Ba1 O2 Ba1 51.48(10) . 10_556 ?
I1 O3 Ti1 137.0(3) . . ?

_refine_diff_density_max         1.650
_refine_diff_density_min         -0.918
_refine_diff_density_rms         0.217

_shelx_res_file                  
;
TITL 2_a_a.res in R-3
    2_a_a.res
    created by SHELXL-2018/3 at 09:55:37 on 17-Feb-2020
REM Old TITL 2_a.res in R-3
REM SHELXT solution in R-3
REM R1 0.070,  Rweak 0.006,  Alpha 0.019,  Orientation as input
REM Formula found by SHELXT:  I2 O6 Ti
CELL  0.71073  11.4412  11.4412  11.1418   90.000   90.000  120.000
ZERR    3.000   0.0017   0.0017   0.0017    0.000    0.000    0.000
LATT  3
SYMM -Y, X-Y, Z
SYMM -X+Y, -X, Z
SFAC BA I O TI
UNIT 3.00006 18 54 3.00006
TEMP 23.850
L.S. 10
BOND $H
LIST 6
FMAP 2
PLAN 20
acta
WGHT    0.018700   45.690800
FVAR       0.13762
BA1   1    0.000000    0.000000    0.380156    10.16667    0.01124    0.01124 =
         0.04573    0.00000    0.00000    0.00562
TI1   4    0.333333    0.666667    0.666667    10.16667    0.01069    0.01069 =
         0.01470    0.00000    0.00000    0.00535
I1    2    0.071781    0.354759    0.558090    11.00000    0.01199    0.01061 =
         0.01122   -0.00166   -0.00121    0.00626

O1    3    0.096480    0.288264    0.696597    11.00000    0.02651    0.02472 =
         0.01289    0.00346   -0.00059    0.01279
O2    3    0.122488    0.270680    0.452732    11.00000    0.01554    0.01668 =
         0.02214   -0.00449    0.00268    0.00834
O3    3    0.237961    0.512893    0.560751    11.00000    0.01454    0.01245 =
         0.02642   -0.00701   -0.00059    0.00175
HKLF 4




REM  2_a_a.res in R-3
REM wR2 = 0.057474, GooF = S = 1.13401, Restrained GooF = 1.13401 for all data
REM R1 = 0.022591 for 609 Fo > 4sig(Fo) and 0.025457 for all 646 data
REM 42 parameters refined using 0 restraints

END

WGHT      0.0175     45.6618

REM Highest difference peak  1.650,  deepest hole -0.918,  1-sigma level  0.217
Q1    1   0.0000  0.0000  0.3156  10.33333  0.05    1.65
Q2    1   0.2879  0.4873  0.5698  11.00000  0.05    0.69
Q3    1   0.2762  0.6173  0.5661  11.00000  0.05    0.63
Q4    1   0.0661  0.2795  0.3958  11.00000  0.05    0.62
Q5    1   0.3186  0.6052  0.4428  11.00000  0.05    0.61
Q6    1   0.2965  0.3988  0.5386  11.00000  0.05    0.56
Q7    1   0.0729  0.1817  0.8040  11.00000  0.05    0.54
Q8    1   0.1828  0.2524  0.5984  11.00000  0.05    0.50
Q9    1   0.2171  0.4527  0.7384  11.00000  0.05    0.49
Q10   1   0.1854  0.4677  0.5516  11.00000  0.05    0.49
Q11   1   0.1222  0.2404  0.3576  11.00000  0.05    0.49
Q12   1   0.0230  0.0851  0.3038  11.00000  0.05    0.48
Q13   1   0.0391  0.2481  0.4698  11.00000  0.05    0.48
Q14   1   0.3333  0.6667  0.5125  10.33333  0.05    0.46
Q15   1   0.0491  0.1909  0.2904  11.00000  0.05    0.44
Q16   1   0.1252  0.3944  0.7624  11.00000  0.05    0.44
Q17   1   0.1761  0.5314  0.5557  11.00000  0.05    0.44
Q18   1   0.1427  0.2601  0.5176  11.00000  0.05    0.44
Q19   1   0.2251  0.5976  0.4922  11.00000  0.05    0.43
Q20   1   0.2558  0.5426  0.6106  11.00000  0.05    0.43
;
_shelx_res_checksum              14723
