# Electronic Supplementary Material (ESI) for ChemComm.
# This journal is © The Royal Society of Chemistry 2021

####################################################################### 
# 
# 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_alpha-III
_database_code_depnum_ccdc_archive 'CCDC 2063409'
loop_
_audit_author_name
_audit_author_address
'Ling-I Hung'
;National Tsing Hua University
Taiwan
;
_audit_update_record             
;
2021-02-17 deposited with the CCDC.	2021-05-31 downloaded from the CCDC.
;

_audit_creation_method           SHELXL-2014/6
_chemical_name_systematic        alpha-III
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'H5 O7 P2 Ti'
_chemical_formula_weight         226.88

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
O O 0.0106 0.0060 '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'
P P 0.1023 0.0942 '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      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                   5.0662(2)
_cell_length_b                   12.5792(8)
_cell_length_c                   10.2257(6)
_cell_angle_alpha                90
_cell_angle_beta                 100.078(3)
_cell_angle_gamma                90
_cell_volume                     641.62(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    6002
_cell_measurement_theta_min      2.59
_cell_measurement_theta_max      28.40

_exptl_crystal_description       Columnar
_exptl_crystal_colour            Blue
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    2.349
_exptl_crystal_F_000             452
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.05
_exptl_absorpt_coefficient_mu    1.815
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8331
_exptl_absorpt_correction_T_max  0.9485
_exptl_absorpt_process_details   'SADABS V2014/4 (Bruker AXS Inc.)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_reflns_number            6002
_diffrn_reflns_av_unetI/netI     0.0319
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -12
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.591
_diffrn_reflns_theta_max         28.404
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             1600
_reflns_number_gt                1408
_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       'APEX2 (Bruker AXS, 2010)'
_computing_cell_refinement       'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_data_reduction        'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  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)+(0.0334P)²+0.3455P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    noref
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1600
_refine_ls_number_parameters     128
_refine_ls_number_restraints     114
_refine_ls_R_factor_all          0.0321
_refine_ls_R_factor_gt           0.0258
_refine_ls_wR_factor_ref         0.0722
_refine_ls_wR_factor_gt          0.0682
_refine_ls_goodness_of_fit_ref   1.118
_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
Ti1 Ti 0.78035(6) 0.70144(3) 0.26451(3) 0.00857(11) Uani 1 1 d . . . . .
P1 P 0.35807(9) 0.69003(4) 0.47870(5) 0.00975(13) Uani 1 1 d . . . . .
O1 O 0.6003(3) 0.66599(14) 0.41505(14) 0.0170(3) Uani 1 1 d . . . . .
O2 O 0.1336(3) 0.74552(13) 0.38462(14) 0.0141(3) Uani 1 1 d . . . . .
O3 O 0.4447(3) 0.75524(13) 0.60522(14) 0.0143(3) Uani 1 1 d . . . . .
P2 P 1.0399(3) 0.44534(7) 0.25473(18) 0.0142(4) Uani 0.693(5) 1 d D U P A 1
O4 O 0.9088(18) 0.5532(5) 0.2443(7) 0.0162(12) Uani 0.693(5) 1 d D U P A 1
O5 O 0.8500(15) 0.3538(5) 0.2233(7) 0.0208(12) Uani 0.693(5) 1 d D U P A 1
O6 O 1.2610(12) 0.4458(10) 0.1696(7) 0.0259(16) Uani 0.693(5) 1 d D U P A 1
H2 H 1.1693 0.4343 0.3816 0.050 Uiso 0.6926 1 d . . P A 1
H6 H 1.2927 0.3769 0.1292 0.050 Uiso 0.6926 1 d . . P A 1
P2' P 0.9499(6) 0.45175(16) 0.1888(4) 0.0162(8) Uani 0.307(5) 1 d D U P A 2
O4' O 0.943(4) 0.5498(12) 0.2716(16) 0.013(2) Uani 0.307(5) 1 d D U P A 2
O5' O 0.890(4) 0.3498(12) 0.2534(15) 0.015(2) Uani 0.307(5) 1 d D U P A 2
O6' O 1.216(3) 0.448(2) 0.1365(16) 0.023(3) Uani 0.307(5) 1 d D U P A 2
H2' H 0.8036 0.4624 0.0606 0.050 Uiso 0.3074 1 d . . P A 2
H6' H 1.3591 0.4866 0.0834 0.050 Uiso 0.3074 1 d . . P A 2
O7 O 0.4403(3) 0.65150(14) 0.13343(15) 0.0176(3) Uani 1 1 d . . . . .
H1 H 0.2678 0.5984 0.5052 0.050 Uiso 1 1 d . . . . .
H7A H 0.2960 0.6828 0.1169 0.050 Uiso 1 1 d . . . . .
H7B H 0.4123 0.5843 0.1360 0.050 Uiso 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
Ti1 O1 1.9730(15) . ?
Ti1 O4 1.997(6) . ?
Ti1 O3 2.0291(14) 4_675 ?
Ti1 O5 2.037(6) 2_655 ?
Ti1 O5' 2.050(13) 2_655 ?
Ti1 O2 2.0615(14) 1_655 ?
Ti1 O4' 2.074(14) . ?
Ti1 O7 2.0860(14) . ?
P1 O1 1.5166(15) . ?
P1 O2 1.5242(15) . ?
P1 O3 1.5299(15) . ?
P1 H1 1.2862 . ?
O2 Ti1 2.0615(14) 1_455 ?
O3 Ti1 2.0291(14) 4_576 ?
P2 O5 1.499(6) . ?
P2 O4 1.506(6) . ?
P2 O6 1.534(6) . ?
P2 H2 1.3544 . ?
O5 Ti1 2.037(6) 2_645 ?
O6 H6 0.9854 . ?
P2' O5' 1.499(12) . ?
P2' O4' 1.499(12) . ?
P2' O6' 1.535(12) . ?
P2' H2' 1.3952 . ?
O5' Ti1 2.050(13) 2_645 ?
O6' H6' 1.0941 . ?
O7 H7A 0.8214 . ?
O7 H7B 0.8583 . ?

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 Ti1 O4 94.2(3) . . ?
O1 Ti1 O3 176.10(6) . 4_675 ?
O4 Ti1 O3 88.9(3) . 4_675 ?
O1 Ti1 O5 88.0(3) . 2_655 ?
O4 Ti1 O5 177.5(3) . 2_655 ?
O3 Ti1 O5 88.8(3) 4_675 2_655 ?
O1 Ti1 O5' 91.8(6) . 2_655 ?
O3 Ti1 O5' 84.8(6) 4_675 2_655 ?
O1 Ti1 O2 93.89(6) . 1_655 ?
O4 Ti1 O2 92.8(2) . 1_655 ?
O3 Ti1 O2 88.32(6) 4_675 1_655 ?
O5 Ti1 O2 88.14(19) 2_655 1_655 ?
O5' Ti1 O2 96.7(4) 2_655 1_655 ?
O1 Ti1 O4' 90.0(6) . . ?
O3 Ti1 O4' 93.4(6) 4_675 . ?
O5' Ti1 O4' 176.8(5) 2_655 . ?
O2 Ti1 O4' 85.9(5) 1_655 . ?
O1 Ti1 O7 89.46(6) . . ?
O4 Ti1 O7 84.2(2) . . ?
O3 Ti1 O7 88.50(6) 4_675 . ?
O5 Ti1 O7 94.73(18) 2_655 . ?
O5' Ti1 O7 86.0(4) 2_655 . ?
O2 Ti1 O7 175.67(6) 1_655 . ?
O4' Ti1 O7 91.3(5) . . ?
O1 P1 O2 113.00(8) . . ?
O1 P1 O3 109.64(9) . . ?
O2 P1 O3 111.10(9) . . ?
O1 P1 H1 104.8 . . ?
O2 P1 H1 106.9 . . ?
O3 P1 H1 111.2 . . ?
P1 O1 Ti1 144.01(10) . . ?
P1 O2 Ti1 136.63(10) . 1_455 ?
P1 O3 Ti1 136.52(9) . 4_576 ?
O5 P2 O4 114.8(5) . . ?
O5 P2 O6 112.7(5) . . ?
O4 P2 O6 108.2(5) . . ?
O5 P2 H2 108.2 . . ?
O4 P2 H2 107.1 . . ?
O6 P2 H2 105.3 . . ?
P2 O4 Ti1 168.8(4) . . ?
P2 O5 Ti1 155.8(4) . 2_645 ?
P2 O6 H6 115.0 . . ?
O5' P2' O4' 115.4(11) . . ?
O5' P2' O6' 112.7(12) . . ?
O4' P2' O6' 109.4(12) . . ?
O5' P2' H2' 112.4 . . ?
O4' P2' H2' 112.9 . . ?
O6' P2' H2' 91.7 . . ?
P2' O4' Ti1 141.8(10) . . ?
P2' O5' Ti1 148.7(10) . 2_645 ?
P2' O6' H6' 149.1 . . ?
Ti1 O7 H7A 126.4 . . ?
Ti1 O7 H7B 113.5 . . ?
H7A O7 H7B 109.4 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
P2 H2 O1 1.35 2.54 3.812(2) 155.9 3_766
O6 H6 O2 0.99 1.71 2.654(12) 160.2 2_645
P2' H2' O6' 1.40 2.30 3.520(19) 143.7 3_765
P2' H2' O7 1.40 2.58 3.765(4) 140.7 3_665
O6' H6' O7 1.09 2.16 2.81(3) 115.2 1_655
O7 H7A O3 0.82 1.93 2.741(2) 170.2 4_575
O7 H7B O6 0.86 1.96 2.788(12) 162.5 1_455
O7 H7B O6' 0.86 1.98 2.81(3) 159.6 1_455

_refine_diff_density_max         0.414
_refine_diff_density_min         -0.401
_refine_diff_density_rms         0.094

_shelxl_version_number           2014/6



_chemical_properties_physical    Oxygen-sensitive
_exptl_crystal_preparation       'Magnetic properties'
####################################################################### 
# 
# 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_beta-IV
_database_code_depnum_ccdc_archive 'CCDC 2063412'
loop_
_audit_author_name
_audit_author_address
'Ling-I Hung'
;National Tsing Hua University
Taiwan
;
_audit_update_record             
;
2021-02-17 deposited with the CCDC.	2021-05-31 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT430_beta-IV             
;
PROBLEM: Short Inter D...A Contact  O2       ..O3       .       2.71 Ang.
RESPONSE: O2 and O3 are two oxygens belonging to the same TiO6 octahedron, the distance between them is reasonable, not too short. For examples, in anatase and brookite TiO2, the observed shortest O-O ditances are 2.46 Ang. and 2.47 Ang. 
;
# Added during the CSD deposition process: Wednesday 17 February 2021 09:53 AM
# 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            'H4 O7 P2 Ti'
_chemical_formula_weight         225.87

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
O O 0.0106 0.0060 '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'
P P 0.1023 0.0942 '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      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                   7.0671(10)
_cell_length_b                   7.3832(10)
_cell_length_c                   12.0992(16)
_cell_angle_alpha                90
_cell_angle_beta                 102.341(4)
_cell_angle_gamma                90
_cell_volume                     616.72(15)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    2602
_cell_measurement_theta_min      3.0827
_cell_measurement_theta_max      28.2641

_exptl_crystal_description       columnar
_exptl_crystal_colour            white
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    2.433
_exptl_crystal_F_000             448
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.10
_exptl_absorpt_coefficient_mu    1.887
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.6813
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_process_details   'SADABS V2014/4 (Bruker AXS Inc.)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_reflns_number            5412
_diffrn_reflns_av_unetI/netI     0.0244
_diffrn_reflns_av_R_equivalents  0.0243
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         3.083
_diffrn_reflns_theta_max         28.328
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.990
_diffrn_measured_fraction_theta_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_point_group_measured_fraction_full 0.994
_reflns_number_total             1518
_reflns_number_gt                1351
_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       'APEX2 (Bruker AXS, 2010)'
_computing_cell_refinement       'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_data_reduction        'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  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)+(0.0405P)²+1.9371P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    noref
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1518
_refine_ls_number_parameters     91
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0422
_refine_ls_R_factor_gt           0.0362
_refine_ls_wR_factor_ref         0.0995
_refine_ls_wR_factor_gt          0.0965
_refine_ls_goodness_of_fit_ref   1.154
_refine_ls_restrained_S_all      1.154
_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
Ti1 Ti 0.48703(8) 0.23252(7) 0.33802(4) 0.00883(16) Uani 1 1 d . . . . .
P1 P 0.75069(11) 0.13802(11) 0.59117(6) 0.00942(19) Uani 1 1 d . . . . .
P2 P 0.69062(13) 0.63718(11) 0.30405(7) 0.0151(2) Uani 1 1 d . . . . .
O1 O 0.6399(4) 0.2408(3) 0.48916(19) 0.0175(5) Uani 1 1 d . . . . .
O2 O 0.6318(4) -0.0131(3) 0.6273(2) 0.0173(5) Uani 1 1 d . . . . .
O3 O 0.8130(3) 0.2749(3) 0.68592(18) 0.0119(4) Uani 1 1 d . . . . .
O4 O 0.5737(4) 0.4617(3) 0.3030(2) 0.0187(5) Uani 1 1 d . . . . .
O5 O 0.8215(4) 0.6097(3) 0.2181(2) 0.0187(5) Uani 1 1 d . . . . .
O6 O 0.7990(5) 0.6922(5) 0.4170(2) 0.0374(8) Uani 1 1 d . . . . .
O7 O 0.2679(4) 0.3650(3) 0.3901(2) 0.0181(5) Uani 1 1 d . . . . .
H1 H 0.9114 0.0611 0.5644 0.050 Uiso 1 1 d . U . . .
H2 H 0.5579 0.7606 0.2524 0.050 Uiso 1 1 d . U . . .
H7A H 0.2543 0.3507 0.4579 0.050 Uiso 1 1 d . U . . .
H7B H 0.2286 0.4903 0.3642 0.050 Uiso 1 1 d . U . . .


_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
Ti1 O5 1.872(2) 2_645 ?
Ti1 O4 1.879(2) . ?
Ti1 O2 1.912(2) 3_656 ?
Ti1 O1 1.916(2) . ?
Ti1 O3 1.984(2) 4_565 ?
Ti1 O7 2.042(2) . ?
P1 O2 1.516(2) . ?
P1 O1 1.516(2) . ?
P1 O3 1.521(2) . ?
P1 H1 1.3691 . ?
P2 O6 1.473(3) . ?
P2 O4 1.535(2) . ?
P2 O5 1.546(2) . ?
P2 H2 1.3601 . ?
O2 Ti1 1.912(2) 3_656 ?
O3 Ti1 1.984(2) 4_666 ?
O5 Ti1 1.872(2) 2_655 ?
O7 H7A 0.8525 . ?
O7 H7B 0.9969 . ?

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
O5 Ti1 O4 93.36(11) 2_645 . ?
O5 Ti1 O2 93.12(11) 2_645 3_656 ?
O4 Ti1 O2 172.89(11) . 3_656 ?
O5 Ti1 O1 93.31(11) 2_645 . ?
O4 Ti1 O1 92.43(10) . . ?
O2 Ti1 O1 90.12(10) 3_656 . ?
O5 Ti1 O3 90.18(10) 2_645 4_565 ?
O4 Ti1 O3 89.02(10) . 4_565 ?
O2 Ti1 O3 88.04(10) 3_656 4_565 ?
O1 Ti1 O3 176.14(10) . 4_565 ?
O5 Ti1 O7 176.66(11) 2_645 . ?
O4 Ti1 O7 86.76(11) . . ?
O2 Ti1 O7 86.60(11) 3_656 . ?
O1 Ti1 O7 90.01(11) . . ?
O3 Ti1 O7 86.49(10) 4_565 . ?
O2 P1 O1 112.41(14) . . ?
O2 P1 O3 111.13(13) . . ?
O1 P1 O3 107.27(13) . . ?
O2 P1 H1 107.6 . . ?
O1 P1 H1 109.0 . . ?
O3 P1 H1 109.5 . . ?
O6 P2 O4 114.39(16) . . ?
O6 P2 O5 113.14(16) . . ?
O4 P2 O5 106.38(14) . . ?
O6 P2 H2 114.3 . . ?
O4 P2 H2 104.1 . . ?
O5 P2 H2 103.4 . . ?
P1 O1 Ti1 148.08(16) . . ?
P1 O2 Ti1 169.45(17) . 3_656 ?
P1 O3 Ti1 134.66(14) . 4_666 ?
P2 O4 Ti1 163.54(17) . . ?
P2 O5 Ti1 139.73(16) . 2_655 ?
Ti1 O7 H7A 119.1 . . ?
Ti1 O7 H7B 121.7 . . ?
H7A O7 H7B 109.7 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O7 H7A O6 0.85 1.67 2.514(4) 172.4 3_666
O7 H7B O3 1.00 1.84 2.831(3) 172.9 3_666

_refine_diff_density_max         1.112
_refine_diff_density_min         -0.484
_refine_diff_density_rms         0.131

_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_beta-III
_database_code_depnum_ccdc_archive 'CCDC 2063410'
loop_
_audit_author_name
_audit_author_address
'Ling-I Hung'
;National Tsing Hua University
Taiwan
;
_audit_update_record             
;
2021-02-17 deposited with the CCDC.	2021-05-31 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT430_beta-III            
;
PROBLEM: Short Inter D...A Contact  O2       ..O3       .       2.72 Ang.
RESPONSE: O2 and O3 are two oxygens belonging to the same TiO6 octahedron, the distance between them is reasonable compared to that of known titanium(III) phosphites in literature. The observed shortest O-O ditance is 2.71 Ang. in the known titanium(III) phosphite, Ti2(HPO3)3.
;
# Added during the CSD deposition process: Wednesday 17 February 2021 09:53 AM
# 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            'H5 O7 P2 Ti'
_chemical_formula_weight         226.88

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
O O 0.0106 0.0060 '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'
P P 0.1023 0.0942 '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      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                   7.4859(6)
_cell_length_b                   7.5154(6)
_cell_length_c                   12.1997(10)
_cell_angle_alpha                90
_cell_angle_beta                 102.801(2)
_cell_angle_gamma                90
_cell_volume                     669.29(9)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    5715
_cell_measurement_theta_min      2.93
_cell_measurement_theta_max      28.31

_exptl_crystal_description       Columnar
_exptl_crystal_colour            Purple
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    2.252
_exptl_crystal_F_000             452
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_exptl_absorpt_coefficient_mu    1.740
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8937
_exptl_absorpt_correction_T_max  0.9485
_exptl_absorpt_process_details   'SADABS V2014/4 (Bruker AXS Inc.)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_reflns_number            5715
_diffrn_reflns_av_unetI/netI     0.0242
_diffrn_reflns_av_R_equivalents  0.0234
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_theta_min         2.933
_diffrn_reflns_theta_max         28.305
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measured_fraction_theta_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_point_group_measured_fraction_full 0.998
_reflns_number_total             1645
_reflns_number_gt                1503
_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       'APEX2 (Bruker AXS, 2010)'
_computing_cell_refinement       'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_data_reduction        'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  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)+(0.0162P)²+2.6105P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    noref
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1645
_refine_ls_number_parameters     128
_refine_ls_number_restraints     114
_refine_ls_R_factor_all          0.0436
_refine_ls_R_factor_gt           0.0395
_refine_ls_wR_factor_ref         0.0857
_refine_ls_wR_factor_gt          0.0840
_refine_ls_goodness_of_fit_ref   1.095
_refine_ls_restrained_S_all      1.072
_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
Ti1 Ti 0.48304(7) 0.23421(7) 0.34096(4) 0.01311(14) Uani 1 1 d . . . . .
P1 P 0.73917(11) 0.13103(11) 0.59247(7) 0.01824(18) Uani 1 1 d . . . . .
O1 O 0.6157(4) 0.2338(4) 0.5002(2) 0.0369(6) Uani 1 1 d . . . . .
O2 O 0.6420(4) -0.0067(4) 0.6458(3) 0.0383(7) Uani 1 1 d . . . . .
O3 O 0.8366(5) 0.2633(4) 0.6795(2) 0.0508(9) Uani 1 1 d . . . . .
P2 P 0.6688(11) 0.6329(11) 0.2788(5) 0.0168(9) Uani 0.63(2) 1 d D U P A 1
O4 O 0.6179(17) 0.4649(13) 0.3297(10) 0.041(2) Uani 0.63(2) 1 d D U P A 1
O5 O 0.801(3) 0.610(3) 0.2044(15) 0.025(3) Uani 0.63(2) 1 d D U P A 1
O6 O 0.7386(11) 0.7630(7) 0.3764(5) 0.0298(15) Uani 0.63(2) 1 d D U P A 1
H2 H 0.5364 0.7293 0.2160 0.050 Uiso 0.634 1 d . . P A 1
H6 H 0.7538 0.8657 0.3469 0.050 Uiso 0.634 1 d . . P A 1
P2' P 0.686(2) 0.625(2) 0.2852(12) 0.031(3) Uani 0.37(2) 1 d D U P A 2
O4' O 0.5680(18) 0.471(2) 0.3020(12) 0.018(2) Uani 0.37(2) 1 d D U P A 2
O5' O 0.806(5) 0.582(5) 0.205(3) 0.023(4) Uani 0.37(2) 1 d D U P A 2
O6' O 0.811(2) 0.683(3) 0.4000(10) 0.051(5) Uani 0.37(2) 1 d D U P A 2
H2' H 0.5494 0.7198 0.2200 0.050 Uiso 0.366 1 d . . P A 2
H6' H 0.9129 0.7283 0.3951 0.050 Uiso 0.366 1 d . . P A 2
O7 O 0.2745(4) 0.3784(3) 0.3929(2) 0.0301(6) Uani 1 1 d . . . . .
H1 H 0.8715 0.0395 0.5382 0.050 Uiso 1 1 d . . . . .
H7A H 0.2929 0.3810 0.4572 0.050 Uiso 1 1 d . . . . .
H7B H 0.2446 0.4817 0.3631 0.050 Uiso 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
Ti1 O2 1.973(3) 3_656 ?
Ti1 O1 1.976(2) . ?
Ti1 O4' 1.984(13) . ?
Ti1 O4 2.026(9) . ?
Ti1 O3 2.031(3) 4_565 ?
Ti1 O5 2.046(15) 2_645 ?
Ti1 O7 2.110(2) . ?
Ti1 O5' 2.12(3) 2_645 ?
P1 O2 1.495(3) . ?
P1 O1 1.502(3) . ?
P1 O3 1.518(3) . ?
P1 H1 1.4776 . ?
O2 Ti1 1.973(3) 3_656 ?
O3 Ti1 2.031(3) 4_666 ?
P2 O4 1.493(8) . ?
P2 O5 1.494(8) . ?
P2 O6 1.540(7) . ?
P2 H2 1.3262 . ?
O5 Ti1 2.046(14) 2_655 ?
O6 H6 0.8696 . ?
P2' O4' 1.496(12) . ?
P2' O5' 1.506(13) . ?
P2' O6' 1.564(13) . ?
P2' H2' 1.3512 . ?
O5' Ti1 2.12(3) 2_655 ?
O6' H6' 0.8493 . ?
O7 H7A 0.7659 . ?
O7 H7B 0.8655 . ?

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 Ti1 O1 93.57(12) 3_656 . ?
O2 Ti1 O4' 168.7(3) 3_656 . ?
O1 Ti1 O4' 96.8(4) . . ?
O2 Ti1 O4 178.4(4) 3_656 . ?
O1 Ti1 O4 85.3(4) . . ?
O2 Ti1 O3 85.60(14) 3_656 4_565 ?
O1 Ti1 O3 177.54(13) . 4_565 ?
O4' Ti1 O3 83.8(4) . 4_565 ?
O4 Ti1 O3 95.5(4) . 4_565 ?
O2 Ti1 O5 92.6(6) 3_656 2_645 ?
O1 Ti1 O5 90.6(6) . 2_645 ?
O4 Ti1 O5 86.3(7) . 2_645 ?
O3 Ti1 O5 91.8(6) 4_565 2_645 ?
O2 Ti1 O7 91.40(12) 3_656 . ?
O1 Ti1 O7 87.11(11) . . ?
O4' Ti1 O7 84.8(5) . . ?
O4 Ti1 O7 89.6(3) . . ?
O3 Ti1 O7 90.59(11) 4_565 . ?
O5 Ti1 O7 175.5(7) 2_645 . ?
O2 Ti1 O5' 87.0(10) 3_656 2_645 ?
O1 Ti1 O5' 90.9(10) . 2_645 ?
O4' Ti1 O5' 97.1(11) . 2_645 ?
O3 Ti1 O5' 91.4(10) 4_565 2_645 ?
O7 Ti1 O5' 177.4(7) . 2_645 ?
O2 P1 O1 113.83(17) . . ?
O2 P1 O3 110.72(16) . . ?
O1 P1 O3 107.95(17) . . ?
O2 P1 H1 108.2 . . ?
O1 P1 H1 105.4 . . ?
O3 P1 H1 110.6 . . ?
P1 O1 Ti1 146.02(18) . . ?
P1 O2 Ti1 157.1(2) . 3_656 ?
P1 O3 Ti1 139.18(19) . 4_666 ?
O4 P2 O5 114.9(9) . . ?
O4 P2 O6 106.8(6) . . ?
O5 P2 O6 112.7(8) . . ?
O4 P2 H2 118.4 . . ?
O5 P2 H2 102.8 . . ?
O6 P2 H2 100.5 . . ?
P2 O4 Ti1 158.2(9) . . ?
P2 O5 Ti1 141.4(11) . 2_655 ?
P2 O6 H6 107.2 . . ?
O4' P2' O5' 112.4(15) . . ?
O4' P2' O6' 110.3(10) . . ?
O5' P2' O6' 108.5(16) . . ?
O4' P2' H2' 95.5 . . ?
O5' P2' H2' 102.3 . . ?
O6' P2' H2' 127.2 . . ?
P2' O4' Ti1 163.1(13) . . ?
P2' O5' Ti1 130.0(18) . 2_655 ?
P2' O6' H6' 114.7 . . ?
Ti1 O7 H7A 110.1 . . ?
Ti1 O7 H7B 118.3 . . ?
H7A O7 H7B 112.2 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O7 H7B O3 0.87 2.04 2.898(4) 169.5 3_666
O7 H7B O2 0.87 2.60 3.111(4) 119.0 4_565
O7 H7A O6' 0.77 2.12 2.779(10) 145.3 3_666
O7 H7A O6 0.77 2.36 3.030(6) 147.2 3_666
O6' H6' O3 0.85 2.26 3.032(12) 151.2 3_766
O6 H6 O5 0.87 1.95 2.782(18) 158.3 2_655
O6 H6 O4 0.87 2.65 3.314(12) 133.6 2_655
P2 H2 O7 1.33 2.66 3.965(10) 168.1 2

_refine_diff_density_max         1.331
_refine_diff_density_min         -0.867
_refine_diff_density_rms         0.099

_shelxl_version_number           2014/6



_chemical_properties_physical    Oxygen-sensitive
_exptl_crystal_preparation       'Magnetic properties'
####################################################################### 
# 
# 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_alpha-IV
_database_code_depnum_ccdc_archive 'CCDC 2063411'
loop_
_audit_author_name
_audit_author_address
'Ling-I Hung'
;National Tsing Hua University
Taiwan
;
_audit_update_record             
;
2021-02-17 deposited with the CCDC.	2021-05-31 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT430_alpha-IV            
;
PROBLEM: Short Inter D...A Contact  O2       ..O3       .       2.78 Ang.
RESPONSE: O2 and O3 are two oxygens belonging to the same TiO6 octahedron, the distance between them is reasonable, not too short. For examples, in anatase and brookite TiO2, the observed shortest O-O ditances are 2.46 Ang. and 2.47 Ang. 
;
# Added during the CSD deposition process: Wednesday 17 February 2021 09:53 AM
# 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            'H4 O7 P2 Ti'
_chemical_formula_weight         225.87

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
O O 0.0106 0.0060 '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'
P P 0.1023 0.0942 '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      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                   5.0907(3)
_cell_length_b                   12.1407(7)
_cell_length_c                   10.2327(6)
_cell_angle_alpha                90
_cell_angle_beta                 102.663(3)
_cell_angle_gamma                90
_cell_volume                     617.05(6)
_cell_formula_units_Z            4
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    8309
_cell_measurement_theta_min      2.64
_cell_measurement_theta_max      28.30

_exptl_crystal_description       white
_exptl_crystal_colour            colorless
_exptl_crystal_density_meas      'not measured'
_exptl_crystal_density_method    'not measured'
_exptl_crystal_density_diffrn    2.431
_exptl_crystal_F_000             448
_exptl_transmission_factor_min   ?
_exptl_transmission_factor_max   ?
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.06
_exptl_crystal_size_min          0.06
_exptl_absorpt_coefficient_mu    1.886
_shelx_estimated_absorpt_T_min   ?
_shelx_estimated_absorpt_T_max   ?
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.8741
_exptl_absorpt_correction_T_max  0.9485
_exptl_absorpt_process_details   'SADABS V2014/4 (Bruker AXS Inc.)'
_exptl_absorpt_special_details   ?
_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_source                   ?
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_detector_area_resol_mean 8.3333
_diffrn_reflns_number            8309
_diffrn_reflns_av_unetI/netI     0.0367
_diffrn_reflns_av_R_equivalents  0.0395
_diffrn_reflns_limit_h_min       -4
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_theta_min         2.641
_diffrn_reflns_theta_max         28.296
_diffrn_reflns_theta_full        25.242
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measured_fraction_theta_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_point_group_measured_fraction_full 1.000
_reflns_number_total             1533
_reflns_number_gt                1183
_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       'APEX2 (Bruker AXS, 2010)'
_computing_cell_refinement       'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_data_reduction        'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_structure_solution    ?
_computing_structure_refinement  'SHELXL-2014/6 (Sheldrick, 2014)'
_computing_molecular_graphics    'SHELXTL (Sheldrick, 2008)'
_computing_publication_material  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)+(0.0374P)²+1.9107P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     ?
_atom_sites_solution_secondary   ?
_atom_sites_solution_hydrogens   difmap
_refine_ls_hydrogen_treatment    mixed
_refine_ls_extinction_method     none
_refine_ls_extinction_coef       .
_refine_ls_number_reflns         1533
_refine_ls_number_parameters     134
_refine_ls_number_restraints     216
_refine_ls_R_factor_all          0.0620
_refine_ls_R_factor_gt           0.0399
_refine_ls_wR_factor_ref         0.1044
_refine_ls_wR_factor_gt          0.0957
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_restrained_S_all      1.066
_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
Ti1 Ti 0.79179(14) 0.70614(6) 0.26529(7) 0.01672(19) Uani 1 1 d . U . . .
P1 P 0.37509(19) 0.70222(8) 0.47838(9) 0.0130(2) Uani 1 1 d . U . . .
O1 O 0.6176(5) 0.6951(2) 0.4148(3) 0.0201(6) Uani 1 1 d . U . . .
O2 O 0.1291(5) 0.7511(2) 0.3837(3) 0.0173(6) Uani 1 1 d . U . . .
O3 O 0.4503(5) 0.7693(2) 0.6076(2) 0.0166(6) Uani 1 1 d . U . . .
P2 P 0.9112(17) 0.4589(4) 0.1887(9) 0.0179(11) Uani 0.51(2) 1 d D U P A 1
O4 O 0.948(3) 0.5608(10) 0.2806(16) 0.021(3) Uani 0.51(2) 1 d D U P A 1
O5 O 0.828(5) 0.3605(14) 0.260(2) 0.025(3) Uani 0.51(2) 1 d D U P A 1
O6 O 0.730(3) 0.4755(6) 0.0555(7) 0.035(3) Uani 0.51(2) 1 d D U P A 1
H2 H 1.15(2) 0.453(10) 0.175(12) 0.050 Uiso 0.51(2) 1 d . U P A 1
P2' P 0.9821(18) 0.4474(5) 0.2258(9) 0.0174(11) Uani 0.49(2) 1 d D U P A 2
O4' O 0.905(3) 0.5550(10) 0.2905(14) 0.0113(19) Uani 0.49(2) 1 d D U P A 2
O5' O 0.855(5) 0.3499(13) 0.2782(19) 0.015(2) Uani 0.49(2) 1 d D U P A 2
O6' O 0.896(3) 0.4534(8) 0.0753(8) 0.038(3) Uani 0.49(2) 1 d D U P A 2
H2' H 1.26(3) 0.431(10) 0.248(12) 0.050 Uiso 0.49(2) 1 d . U P A 2
O7 O 0.4698(6) 0.6471(3) 0.1459(3) 0.0251(7) Uani 1 1 d . U . . .
H1 H 0.3265 0.6149 0.4971 0.050 Uiso 1 1 d . . . . .
H7A H 0.3344 0.6936 0.1148 0.050 Uiso 1 1 d . . . . .
H7B H 0.5002 0.6172 0.0625 0.050 Uiso 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
Ti1 O5' 1.912(16) 2_655 ?
Ti1 O4' 1.924(12) . ?
Ti1 O4 1.926(13) . ?
Ti1 O1 1.934(3) . ?
Ti1 O2 1.950(3) 1_655 ?
Ti1 O7 1.953(3) . ?
Ti1 O5 1.970(16) 2_655 ?
Ti1 O3 1.978(3) 4_675 ?
P1 O1 1.519(3) . ?
P1 O2 1.525(3) . ?
P1 O3 1.529(3) . ?
P1 H1 1.1147 . ?
O2 Ti1 1.950(3) 1_455 ?
O3 Ti1 1.978(3) 4_576 ?
P2 O6 1.483(8) . ?
P2 O5 1.509(10) . ?
P2 O4 1.541(9) . ?
P2 H2 1.26(12) . ?
O5 Ti1 1.969(16) 2_645 ?
P2' O5' 1.503(10) . ?
P2' O6' 1.508(8) . ?
P2' O4' 1.553(9) . ?
P2' H2' 1.41(13) . ?
O5' Ti1 1.912(16) 2_645 ?
O7 H7A 0.8944 . ?
O7 H7B 0.9706 . ?

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
O5' Ti1 O4' 172.8(8) 2_655 . ?
O5' Ti1 O1 91.3(6) 2_655 . ?
O4' Ti1 O1 90.2(4) . . ?
O4 Ti1 O1 97.1(5) . . ?
O5' Ti1 O2 97.8(7) 2_655 1_655 ?
O4' Ti1 O2 89.2(4) . 1_655 ?
O4 Ti1 O2 85.1(4) . 1_655 ?
O1 Ti1 O2 91.26(12) . 1_655 ?
O5' Ti1 O7 87.6(7) 2_655 . ?
O4' Ti1 O7 85.4(4) . . ?
O4 Ti1 O7 89.4(4) . . ?
O1 Ti1 O7 90.10(12) . . ?
O2 Ti1 O7 174.44(12) 1_655 . ?
O4 Ti1 O5 172.6(10) . 2_655 ?
O1 Ti1 O5 89.3(7) . 2_655 ?
O2 Ti1 O5 91.2(7) 1_655 2_655 ?
O7 Ti1 O5 94.2(7) . 2_655 ?
O5' Ti1 O3 83.2(6) 2_655 4_675 ?
O4' Ti1 O3 95.1(4) . 4_675 ?
O4 Ti1 O3 88.3(5) . 4_675 ?
O1 Ti1 O3 174.48(12) . 4_675 ?
O2 Ti1 O3 90.20(11) 1_655 4_675 ?
O7 Ti1 O3 88.95(12) . 4_675 ?
O5 Ti1 O3 85.3(7) 2_655 4_675 ?
O1 P1 O2 112.41(16) . . ?
O1 P1 O3 109.16(16) . . ?
O2 P1 O3 110.91(16) . . ?
O1 P1 H1 104.6 . . ?
O2 P1 H1 107.3 . . ?
O3 P1 H1 112.4 . . ?
P1 O1 Ti1 153.09(19) . . ?
P1 O2 Ti1 140.71(18) . 1_455 ?
P1 O3 Ti1 135.76(16) . 4_576 ?
O6 P2 O5 111.6(9) . . ?
O6 P2 O4 114.7(7) . . ?
O5 P2 O4 110.4(10) . . ?
O6 P2 H2 109(6) . . ?
O5 P2 H2 113(6) . . ?
O4 P2 H2 97(5) . . ?
P2 O4 Ti1 133.9(11) . . ?
P2 O5 Ti1 143.2(14) . 2_645 ?
O5' P2' O6' 110.5(8) . . ?
O5' P2' O4' 110.1(10) . . ?
O6' P2' O4' 110.5(7) . . ?
O5' P2' H2' 109(5) . . ?
O6' P2' H2' 103(5) . . ?
O4' P2' H2' 113(5) . . ?
P2' O4' Ti1 147.3(10) . . ?
P2' O5' Ti1 144.4(13) . 2_645 ?
Ti1 O7 H7A 117.8 . . ?
Ti1 O7 H7B 114.4 . . ?
H7A O7 H7B 100.5 . . ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
O7 H7A O1 0.89 2.50 3.259(4) 143.2 4_575
O7 H7A O3 0.89 1.99 2.780(4) 146.1 4_575
O7 H7B O2 0.97 2.62 3.215(4) 119.9 4_675
O7 H7B O6 0.97 2.09 2.735(12) 122.4 .
O7 H7B O6 0.97 1.86 2.565(8) 126.6 3_665
O7 H7B O6' 0.97 2.35 2.869(11) 112.5 3_665

_refine_diff_density_max         0.573
_refine_diff_density_min         -0.640
_refine_diff_density_rms         0.133

_shelxl_version_number           2014/6



