# Electronic Supplementary Material (ESI) for Dalton Transactions.
# This journal is © The Royal Society of Chemistry 2018

####################################################################### 
# 
# This file contains crystal structure data downloaded from the 
# Cambridge Structural Database (CSD) hosted by the Cambridge 
# Crystallographic Data Centre (CCDC).
# 
# Full information about CCDC data access policies and citation 
# guidelines are available at http://www.ccdc.cam.ac.uk/access/V1 
# 
# Audit and citation data items may have been added by the CCDC. 
# Please retain this information to preserve the provenance of 
# this file and to allow appropriate attribution of the data. 
# 
#######################################################################

data_exp_40441
_database_code_depnum_ccdc_archive 'CCDC 1572967'
_audit_update_record             
;
2017-09-06 deposited with the CCDC.
2018-01-09 downloaded from the CCDC.
;
_audit_creation_date             2017-07-10
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_shelxl_version_number           2014-3
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         '0.2(C18 H21 Mn6 O42 Ti3)'
_chemical_formula_sum            'C3.60 H4.20 Mn1.20 O8.40 Ti0.60'
_chemical_formula_weight         276.54
_chemical_absolute_configuration ?
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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'
Mn Mn 0.3368 0.7283 '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'

_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      trigonal
_space_group_IT_number           152
_space_group_name_H-M_alt        'P 31 2 1'
_space_group_name_Hall           'P 31 2"'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z+1/3'
'-x+y, -x, z+2/3'
'y, x, -z'
'x-y, -y, -z+2/3'
'-x, -x+y, -z+1/3'

_cell_length_a                   10.6510(3)
_cell_length_b                   10.6510(3)
_cell_length_c                   11.0943(3)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1089.96(7)
_cell_formula_units_Z            5
_cell_measurement_reflns_used    1642
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.4710
_cell_measurement_theta_min      4.2260
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    2.320
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91221
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    2.107
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             681
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0170
_diffrn_reflns_av_unetI/netI     0.0306
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            2056
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.994
_diffrn_reflns_theta_min         3.826
_diffrn_ambient_temperature      293(2)
_diffrn_detector_area_resol_mean 16.2083
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details      
;
#__ type_ start__ end____ width___ exp.time_
  1 omega  -50.00   53.00   0.2500   13.2450
omega____ theta____ kappa____ phi______ frames
    -       15.8360  -19.0000    0.0000 412
;
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_UB_11      0.0561008000
_diffrn_orient_matrix_UB_12      0.0725658000
_diffrn_orient_matrix_UB_13      -0.0093628000
_diffrn_orient_matrix_UB_21      0.0224350000
_diffrn_orient_matrix_UB_22      0.0038702000
_diffrn_orient_matrix_UB_23      0.0607508000
_diffrn_orient_matrix_UB_31      0.0475685000
_diffrn_orient_matrix_UB_32      -0.0251745000
_diffrn_orient_matrix_UB_33      -0.0176380000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.693
_reflns_Friedel_fraction_full    0.953
_reflns_Friedel_fraction_max     0.970
_reflns_number_gt                1220
_reflns_number_total             1275
_reflns_odcompleteness_completeness 99.49
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_collection       
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_data_reduction        
;
CrysAlisPro, Agilent Technologies,
Version 1.171.36.28 (release 01-02-2013 CrysAlis171 .NET)
(compiled Feb  1 2013,16:14:44)
;
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.267
_refine_diff_density_min         -0.188
_refine_diff_density_rms         0.049
_refine_ls_abs_structure_details 
;
 Flack x determined using 493 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.056(16)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     107
_refine_ls_number_reflns         1275
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0230
_refine_ls_R_factor_gt           0.0215
_refine_ls_restrained_S_all      1.085
_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)+(0.0247P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0511
_refine_ls_wR_factor_ref         0.0517
_refine_special_details          
;
 ?
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Others
 Fixed Sof: H007(0.5)
3.a Rotating group:
 O007(H007)
3.b Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00C(H00C), C00D(H00D)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_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
Mn01 Mn 0.92250(6) 0.18597(6) 0.31344(4) 0.02365(17) Uani 1 1 d . . . . .
Ti02 Ti 1.0000 0.49476(9) 0.1667 0.0243(2) Uani 1 2 d S T P . .
O003 O 1.0000 0.3327(4) 0.1667 0.0264(8) Uani 1 2 d S T P . .
O004 O 0.8415(3) 0.0189(3) 0.4541(2) 0.0251(6) Uani 1 1 d . . . . .
O005 O 1.0501(3) 0.5462(3) 0.3422(2) 0.0354(7) Uani 1 1 d . . . . .
O006 O 0.8142(3) -0.0578(3) 0.6436(2) 0.0303(7) Uani 1 1 d . . . . .
O007 O 1.0000 0.6948(4) 0.1667 0.0383(11) Uani 1 2 d S T P . .
H007 H 1.0443 0.7554 0.0976 0.057 Uiso 0.5 1 d GR . . . .
O008 O 1.0017(3) 0.3496(3) 0.4484(2) 0.0398(7) Uani 1 1 d . . . . .
O009 O 0.7873(3) 0.4027(3) 0.2096(3) 0.0396(7) Uani 1 1 d . . . . .
O00A O 0.7244(3) 0.1929(4) 0.3014(3) 0.0452(8) Uani 1 1 d . . . . .
C00B C 1.0453(4) 0.4804(5) 0.4383(3) 0.0322(9) Uani 1 1 d . . . . .
H00B H 1.0777 0.5358 0.5082 0.039 Uiso 1 1 calc R . . . .
C00C C 0.8409(5) 0.0357(4) 0.5661(3) 0.0274(9) Uani 1 1 d . . . . .
H00C H 0.8625 0.1270 0.5933 0.033 Uiso 1 1 calc R . . . .
C00D C 0.6996(5) 0.2834(5) 0.2564(4) 0.0398(10) Uani 1 1 d . . . . .
H00D H 0.6032 0.2606 0.2572 0.048 Uiso 1 1 calc R . . . .


_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
Mn01 O003 2.118(2) . ?
Mn01 O004 2.194(2) . ?
Mn01 O004 2.197(3) 5 ?
Mn01 O006 2.189(3) 3_764 ?
Mn01 O008 2.127(3) . ?
Mn01 O00A 2.152(3) . ?
Ti02 O003 1.726(4) . ?
Ti02 O005 2.021(3) 6_765 ?
Ti02 O005 2.021(3) . ?
Ti02 O007 2.131(4) . ?
Ti02 O009 2.024(3) 6_765 ?
Ti02 O009 2.024(3) . ?
O003 Mn01 2.118(2) 6_765 ?
O004 Mn01 2.197(3) 5 ?
O004 C00C 1.255(4) . ?
O005 C00B 1.263(5) . ?
O006 Mn01 2.189(3) 2_645 ?
O006 C00C 1.237(4) . ?
O007 H007 0.9599 . ?
O008 C00B 1.233(5) . ?
O009 C00D 1.253(5) . ?
O00A C00D 1.226(5) . ?
C00B H00B 0.9300 . ?
C00C H00C 0.9300 . ?
C00D H00D 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
O003 Mn01 O004 99.08(9) . 5 ?
O003 Mn01 O004 174.75(11) . . ?
O003 Mn01 O006 88.14(9) . 3_764 ?
O003 Mn01 O008 95.05(10) . . ?
O003 Mn01 O00A 87.37(10) . . ?
O004 Mn01 O004 76.00(9) . 5 ?
O006 Mn01 O004 88.79(11) 3_764 5 ?
O006 Mn01 O004 89.92(10) 3_764 . ?
O008 Mn01 O004 165.87(9) . 5 ?
O008 Mn01 O004 89.87(10) . . ?
O008 Mn01 O006 91.43(11) . 3_764 ?
O008 Mn01 O00A 90.55(12) . . ?
O00A Mn01 O004 90.34(12) . 5 ?
O00A Mn01 O004 94.43(11) . . ?
O00A Mn01 O006 175.23(10) . 3_764 ?
O003 Ti02 O005 98.00(8) . 6_765 ?
O003 Ti02 O005 98.00(8) . . ?
O003 Ti02 O007 180.0 . . ?
O003 Ti02 O009 94.30(8) . 6_765 ?
O003 Ti02 O009 94.30(8) . . ?
O005 Ti02 O005 164.01(16) . 6_765 ?
O005 Ti02 O007 82.00(8) . . ?
O005 Ti02 O007 82.00(8) 6_765 . ?
O005 Ti02 O009 89.69(12) 6_765 . ?
O005 Ti02 O009 89.11(12) . . ?
O005 Ti02 O009 89.11(12) 6_765 6_765 ?
O005 Ti02 O009 89.69(12) . 6_765 ?
O009 Ti02 O007 85.70(8) 6_765 . ?
O009 Ti02 O007 85.70(8) . . ?
O009 Ti02 O009 171.40(16) 6_765 . ?
Mn01 O003 Mn01 114.21(18) . 6_765 ?
Ti02 O003 Mn01 122.90(9) . . ?
Ti02 O003 Mn01 122.89(9) . 6_765 ?
Mn01 O004 Mn01 103.98(9) . 5 ?
C00C O004 Mn01 128.0(2) . . ?
C00C O004 Mn01 127.6(2) . 5 ?
C00B O005 Ti02 137.0(3) . . ?
C00C O006 Mn01 134.6(2) . 2_645 ?
Ti02 O007 H007 115.3 . . ?
C00B O008 Mn01 129.2(3) . . ?
C00D O009 Ti02 132.5(3) . . ?
C00D O00A Mn01 130.7(3) . . ?
O005 C00B H00B 116.9 . . ?
O008 C00B O005 126.3(4) . . ?
O008 C00B H00B 116.9 . . ?
O004 C00C H00C 117.0 . . ?
O006 C00C O004 126.0(4) . . ?
O006 C00C H00C 117.0 . . ?
O009 C00D H00D 115.8 . . ?
O00A C00D O009 128.4(4) . . ?
O00A C00D H00D 115.8 . . ?

_olex2_submission_special_instructions 'No special instructions were received'
####################################################################### 
# 
# 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_exp_40340
_database_code_depnum_ccdc_archive 'CCDC 1572968'
_audit_update_record             
;
2017-09-06 deposited with the CCDC.
2018-01-09 downloaded from the CCDC.
;
_audit_creation_date             2017-07-10
_audit_creation_method           
;
Olex2 1.2-beta
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_shelxl_version_number           2014-3
_chemical_name_common            ?
_chemical_name_systematic        
;
 ?
;
_chemical_formula_moiety         '0.2(C18 H21 Mn6 O42 Ti3)'
_chemical_formula_sum            'C3.60 H4.20 Mn1.20 O8.40 Ti0.60'
_chemical_formula_weight         276.54
_chemical_absolute_configuration ?
_chemical_melting_point          ?
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
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'
Mn Mn 0.3368 0.7283 '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'

_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      trigonal
_space_group_IT_number           154
_space_group_name_H-M_alt        'P 32 2 1'
_space_group_name_Hall           'P 32 2"'
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z+2/3'
'-x+y, -x, z+1/3'
'y, x, -z'
'x-y, -y, -z+1/3'
'-x, -x+y, -z+2/3'

_cell_length_a                   10.6552(4)
_cell_length_b                   10.6552(4)
_cell_length_c                   11.0809(5)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_volume                     1089.50(10)
_cell_formula_units_Z            5
_cell_measurement_reflns_used    1103
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      26.7070
_cell_measurement_theta_min      4.2270
_shelx_estimated_absorpt_T_max   ?
_shelx_estimated_absorpt_T_min   ?
_exptl_absorpt_coefficient_mu    2.321
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91265
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            ?
_exptl_crystal_density_diffrn    2.107
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_description       ?
_exptl_crystal_F_000             681
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_exptl_special_details           
;
 ?
;
_exptl_transmission_factor_max   ?
_exptl_transmission_factor_min   ?
_diffrn_reflns_av_R_equivalents  0.0216
_diffrn_reflns_av_unetI/netI     0.0432
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            2221
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.995
_diffrn_reflns_theta_min         3.825
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2083
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 0.977
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_details      
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  tₑₓₚ   ω     θ     κ     φ   Frames
#--------------------------------------------------------------------------
  1  ω     -8.00  79.00   1.00   14.36    --   15.84  37.00 -90.00   87
  2  ω     16.00  42.00   1.00   14.36    --   15.84 -37.00  90.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos'
_diffrn_measurement_method       'ω scans'
_diffrn_orient_matrix_type       
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0257295000
_diffrn_orient_matrix_UB_12      0.0680848000
_diffrn_orient_matrix_UB_13      -0.0286911000
_diffrn_orient_matrix_UB_21      0.0089268000
_diffrn_orient_matrix_UB_22      -0.0293540000
_diffrn_orient_matrix_UB_23      -0.0545875000
_diffrn_orient_matrix_UB_31      -0.0718975000
_diffrn_orient_matrix_UB_32      -0.0204008000
_diffrn_orient_matrix_UB_33      -0.0170221000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_reflns_Friedel_coverage         0.712
_reflns_Friedel_fraction_full    0.978
_reflns_Friedel_fraction_max     0.996
_reflns_number_gt                1200
_reflns_number_total             1289
_reflns_odcompleteness_completeness 99.49
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_reflns_special_details          
;
 Reflections were merged by SHELXL according to the crystal
 class for the calculation of statistics and refinement.
 
 _reflns_Friedel_fraction is defined as the number of unique
 Friedel pairs measured divided by the number that would be
 possible theoretically, ignoring centric projections and
 systematic absences.
;
_reflns_threshold_expression     'I > 2σ(I)'
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_refine_diff_density_max         0.228
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details 
;
 Flack x determined using 474 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(2)
_refine_ls_extinction_coef       .
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     107
_refine_ls_number_reflns         1289
_refine_ls_number_restraints     0
_refine_ls_R_factor_all          0.0339
_refine_ls_R_factor_gt           0.0291
_refine_ls_restrained_S_all      1.001
_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)+(0.0313P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0617
_refine_ls_wR_factor_ref         0.0648
_refine_special_details          
;
 ?
;
_olex2_refinement_description    
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups
2. Others
 Fixed Sof: H009(0.5)
3.a Rotating group:
 O009(H009)
3.b Aromatic/amide H refined with riding coordinates:
 C00B(H00B), C00C(H00C), C00D(H00D)
;
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_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
Mn01 Mn 0.92259(8) 0.73663(8) 0.48020(6) 0.0226(2) Uani 1 1 d . . . . .
Ti02 Ti 1.0000 0.50544(11) 0.3333 0.0237(3) Uani 1 2 d S T P . .
O003 O 1.0000 0.6673(5) 0.3333 0.0245(10) Uani 1 2 d S T P . .
O004 O 0.8417(4) 0.8228(4) 0.6208(3) 0.0248(8) Uani 1 1 d . . . . .
O005 O 0.8141(4) 0.8718(4) 0.8103(3) 0.0295(9) Uani 1 1 d . . . . .
O006 O 1.0504(4) 0.5040(4) 0.5089(3) 0.0358(10) Uani 1 1 d . . . . .
O007 O 1.0021(4) 0.6518(4) 0.6153(3) 0.0369(9) Uani 1 1 d . . . . .
O008 O 0.7882(4) 0.3845(4) 0.3762(3) 0.0377(10) Uani 1 1 d . . . . .
O009 O 1.0000 0.3049(5) 0.3333 0.0380(14) Uani 1 2 d S T P . .
H009 H 0.9568 0.2532 0.3981 0.057 Uiso 0.5 1 d GR . . . .
O00A O 0.7245(4) 0.5319(4) 0.4680(4) 0.0430(11) Uani 1 1 d . . . . .
C00B C 1.0457(6) 0.5654(6) 0.6047(5) 0.0318(13) Uani 1 1 d . . . . .
H00B H 1.0787 0.5429 0.6745 0.038 Uiso 1 1 calc R . . . .
C00C C 0.8409(6) 0.8049(6) 0.7333(4) 0.0269(12) Uani 1 1 d . . . . .
H00C H 0.8624 0.7352 0.7606 0.032 Uiso 1 1 calc R . . . .
C00D C 0.7000(6) 0.4164(6) 0.4234(5) 0.0380(14) Uani 1 1 d . . . . .
H00D H 0.6037 0.3426 0.4244 0.046 Uiso 1 1 calc R . . . .


_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
Mn01 O003 2.117(3) . ?
Mn01 O004 2.192(3) . ?
Mn01 O004 2.197(3) 4_556 ?
Mn01 O005 2.192(4) 2_764 ?
Mn01 O007 2.131(3) . ?
Mn01 O00A 2.151(4) . ?
Ti02 O003 1.725(5) . ?
Ti02 O006 2.020(4) 6_765 ?
Ti02 O006 2.020(4) . ?
Ti02 O008 2.018(4) . ?
Ti02 O008 2.018(4) 6_765 ?
Ti02 O009 2.137(5) . ?
O003 Mn01 2.117(3) 6_765 ?
O004 Mn01 2.197(3) 4_556 ?
O004 C00C 1.260(5) . ?
O005 Mn01 2.192(4) 3_675 ?
O005 C00C 1.234(5) . ?
O006 C00B 1.261(6) . ?
O007 C00B 1.226(7) . ?
O008 C00D 1.261(7) . ?
O009 H009 0.8815 . ?
O00A C00D 1.228(7) . ?
C00B H00B 0.9300 . ?
C00C H00C 0.9300 . ?
C00D H00D 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
O003 Mn01 O004 99.11(12) . 4_556 ?
O003 Mn01 O004 174.71(14) . . ?
O003 Mn01 O005 88.14(12) . 2_764 ?
O003 Mn01 O007 94.88(13) . . ?
O003 Mn01 O00A 87.36(13) . . ?
O004 Mn01 O004 75.93(13) . 4_556 ?
O005 Mn01 O004 88.77(14) 2_764 4_556 ?
O005 Mn01 O004 89.90(14) 2_764 . ?
O007 Mn01 O004 90.07(13) . . ?
O007 Mn01 O004 166.00(12) . 4_556 ?
O007 Mn01 O005 91.43(15) . 2_764 ?
O007 Mn01 O00A 90.61(16) . . ?
O00A Mn01 O004 94.43(15) . . ?
O00A Mn01 O004 90.30(16) . 4_556 ?
O00A Mn01 O005 175.20(13) . 2_764 ?
O003 Ti02 O006 98.07(11) . 6_765 ?
O003 Ti02 O006 98.07(11) . . ?
O003 Ti02 O008 94.55(11) . 6_765 ?
O003 Ti02 O008 94.55(11) . . ?
O003 Ti02 O009 180.0 . . ?
O006 Ti02 O006 163.9(2) 6_765 . ?
O006 Ti02 O009 81.93(11) 6_765 . ?
O006 Ti02 O009 81.93(11) . . ?
O008 Ti02 O006 89.14(16) 6_765 6_765 ?
O008 Ti02 O006 89.58(16) . 6_765 ?
O008 Ti02 O006 89.14(16) . . ?
O008 Ti02 O006 89.58(16) 6_765 . ?
O008 Ti02 O008 170.9(2) 6_765 . ?
O008 Ti02 O009 85.45(11) 6_765 . ?
O008 Ti02 O009 85.45(11) . . ?
Mn01 O003 Mn01 114.1(2) 6_765 . ?
Ti02 O003 Mn01 122.93(11) . 6_765 ?
Ti02 O003 Mn01 122.93(11) . . ?
Mn01 O004 Mn01 104.05(13) . 4_556 ?
C00C O004 Mn01 127.7(3) . 4_556 ?
C00C O004 Mn01 127.9(3) . . ?
C00C O005 Mn01 134.8(3) . 3_675 ?
C00B O006 Ti02 136.6(3) . . ?
C00B O007 Mn01 129.1(3) . . ?
C00D O008 Ti02 132.2(4) . . ?
Ti02 O009 H009 111.3 . . ?
C00D O00A Mn01 130.6(4) . . ?
O006 C00B H00B 116.6 . . ?
O007 C00B O006 126.8(5) . . ?
O007 C00B H00B 116.6 . . ?
O004 C00C H00C 117.2 . . ?
O005 C00C O004 125.6(5) . . ?
O005 C00C H00C 117.2 . . ?
O008 C00D H00D 115.7 . . ?
O00A C00D O008 128.6(5) . . ?
O00A C00D H00D 115.7 . . ?

_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 1.171
_oxdiff_exptl_absorpt_empirical_full_min 0.865
