 
data_bridgesite
 
_audit_creation_method            SHELXL-2014
_chemical_name_systematic
;
 ?
;
_chemical_name_common             ?
_chemical_melting_point           ?
_chemical_formula_moiety          ?
_chemical_formula_sum
 'Ca0.50 Ce Cu3 O18 S2' 
_chemical_formula_weight          702.90

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'
 'S'  'S'   0.1246   0.1234
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Ca'  'Ca'   0.2262   0.3064
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Cu'  'Cu'   0.3201   1.2651
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 'Ce'  'Ce'  -0.2486   2.6331
 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
 
_space_group_crystal_system       monoclinic
_space_group_IT_number            12
_space_group_name_H-M_alt         'C 2/m'
_space_group_name_Hall            '-C 2y'
 
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
 
loop_
 _space_group_symop_operation_xyz
 'x, y, z'
 '-x, y, -z'
 'x+1/2, y+1/2, z'
 '-x+1/2, y+1/2, -z'
 '-x, -y, -z'
 'x, -y, z'
 '-x+1/2, -y+1/2, -z'
 'x+1/2, -y+1/2, z'
 
_cell_length_a                    24.801(5)
_cell_length_b                    6.3520(13)
_cell_length_c                    11.245(2)
_cell_angle_alpha                 90
_cell_angle_beta                  114.51(3)
_cell_angle_gamma                 90
_cell_volume                      1611.9(7)
_cell_formula_units_Z             4
_cell_measurement_temperature     293(2)
_cell_measurement_reflns_used     4065 
_cell_measurement_theta_min       2 
_cell_measurement_theta_max       30 
 
_exptl_crystal_description        irregular 
_exptl_crystal_colour             blue 
_exptl_crystal_density_meas       ? 
_exptl_crystal_density_method     ?              
_exptl_crystal_density_diffrn     2.897          
_exptl_crystal_F_000              1324
_exptl_transmission_factor_min    ?                                             
_exptl_transmission_factor_max    ?                                             
_exptl_crystal_size_max           0.050 
_exptl_crystal_size_mid           0.007 
_exptl_crystal_size_min           0.002 
_exptl_absorpt_coefficient_mu     7.180
_shelx_estimated_absorpt_T_min    ? 
_shelx_estimated_absorpt_T_max    ? 
_exptl_absorpt_correction_type    analytical 
_exptl_absorpt_correction_T_min   0.632 
_exptl_absorpt_correction_T_max   0.862 
_exptl_absorpt_process_details    'SADABS; Sheldrik, 2007' 
 
_exptl_special_details
;
 ?
;
 
_diffrn_ambient_temperature       293(2)
_diffrn_radiation_wavelength      0.71073
_diffrn_radiation_type            MoK\a
_diffrn_source                    'rotating-anode generator'                       
_diffrn_measurement_device_type   'Bruker D8 3-circle diffractometer'    
_diffrn_measurement_method        ? 
_diffrn_detector_area_resol_mean  ? 
_diffrn_reflns_number             5778
_diffrn_reflns_av_unetI/netI      0.0709
_diffrn_reflns_av_R_equivalents   0.0887
_diffrn_reflns_limit_h_min        -29
_diffrn_reflns_limit_h_max        29
_diffrn_reflns_limit_k_min        -7
_diffrn_reflns_limit_k_max        7
_diffrn_reflns_limit_l_min        -13
_diffrn_reflns_limit_l_max        13
_diffrn_reflns_theta_min          1.990
_diffrn_reflns_theta_max          25.321
_diffrn_reflns_theta_full         25.242
_diffrn_measured_fraction_theta_max   0.982
_diffrn_measured_fraction_theta_full  0.992
_diffrn_reflns_Laue_measured_fraction_max    0.982
_diffrn_reflns_Laue_measured_fraction_full   0.992
_diffrn_reflns_point_group_measured_fraction_max   0.982
_diffrn_reflns_point_group_measured_fraction_full  0.992
_reflns_number_total              1597
_reflns_number_gt                 1182
_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     ?
_computing_structure_refinement   'SHELXL-2014 (Sheldrick, 2014)'
_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)+(0.1162P)²+56.4900P] 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          1597
_refine_ls_number_parameters      143
_refine_ls_number_restraints      0
_refine_ls_R_factor_all           0.0830
_refine_ls_R_factor_gt            0.0583
_refine_ls_wR_factor_ref          0.1723
_refine_ls_wR_factor_gt           0.1550
_refine_ls_goodness_of_fit_ref    0.919
_refine_ls_restrained_S_all       0.919
_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
Ce Ce 0.32313(5) 0.0000 0.30131(9) 0.0225(4) Uani 1 2 d S T P . .
Cu1 Cu 0.27732(10) -0.5000 0.29688(18) 0.0218(5) Uani 1 2 d S T P . .
Cu2 Cu 0.2500 -0.7500 0.5000 0.0238(5) Uani 1 2 d S . P . .
Cu3 Cu 0.2500 0.2500 0.0000 0.0198(5) Uani 1 2 d S . P . .
S1 S 0.1307(2) -0.5000 0.2095(5) 0.059(2) Uani 1 2 d S T P . .
S2 S 0.3824(2) -0.5000 0.2037(5) 0.0333(12) Uani 1 2 d S T P . .
Ca Ca 0.4376(3) -0.5000 -0.0013(7) 0.0245(16) Uani 0.5 2 d S T P . .
O1 O 0.2474(4) 0.2639(13) 0.1718(7) 0.0204(18) Uani 1 1 d . . . . .
O2 O 0.3109(4) 0.2830(14) 0.4345(8) 0.027(2) Uani 1 1 d . . . . .
O3 O 0.3003(5) 0.0000 0.0627(10) 0.020(3) Uani 1 2 d S T P . .
O4 O 0.1867(5) -0.5000 0.3228(12) 0.027(3) Uani 1 2 d S T P . .
O5 O 0.2277(6) -1.0000 0.3889(11) 0.029(3) Uani 1 2 d S T P . .
O6 O 0.4153(6) 0.0000 0.5102(13) 0.038(3) Uani 1 2 d S T P . .
O7 O 0.0818(6) -0.5000 0.2467(13) 0.044(4) Uani 1 2 d S T P . .
O8 O 0.4119(8) 0.5000 0.6033(18) 0.062(5) Uani 1 2 d S T P . .
O9 O 0.3402(8) -0.5000 0.0671(13) 0.055(5) Uani 1 2 d S T P . .
O10 O 0.4421(8) -0.5000 0.2149(18) 0.074(6) Uani 1 2 d S T P . .
O11 O 0.3743(7) -0.684(3) 0.2704(12) 0.130(9) Uani 1 1 d . . . . .
O12 O 0.1279(6) -0.695(5) 0.137(2) 0.227(17) Uani 1 1 d . . . . .
O13 O 0.4716(11) -0.865(4) 0.080(2) 0.071(10) Uani 0.54(4) 1 d . . . . .
O14 O 0.4272(16) 0.0000 0.271(4) 0.040 Uiso 0.39(3) 2 d S U . . .
O15 O 0.5000 -0.295(4) 0.5000 0.040 Uiso 0.54(3) 2 d S 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
Ce O2 2.438(9) . ?
Ce O2 2.438(9) 6 ?
Ce O11 2.474(12) 1_565 ?
Ce O11 2.474(12) 6_545 ?
Ce O1 2.488(8) . ?
Ce O1 2.488(8) 6 ?
Ce O3 2.501(10) . ?
Ce O6 2.508(14) . ?
Ce O14 2.74(4) . ?
Ce O5 2.917(14) 1_565 ?
Ce Cu1 3.3666(10) . ?
Ce Cu1 3.3666(10) 1_565 ?
Cu1 O1 1.978(8) 1_545 ?
Cu1 O1 1.978(8) 6 ?
Cu1 O2 1.980(9) 6 ?
Cu1 O2 1.980(9) 1_545 ?
Cu1 O4 2.382(13) . ?
Cu1 Ce 3.3666(10) 1_545 ?
Cu2 O2 1.946(8) 7_546 ?
Cu2 O2 1.946(8) 1_545 ?
Cu2 O5 1.953(7) . ?
Cu2 O5 1.953(7) 7_536 ?
Cu3 O3 1.961(7) 7 ?
Cu3 O3 1.961(7) . ?
Cu3 O1 1.962(7) 7 ?
Cu3 O1 1.962(7) . ?
Cu3 Ce 3.4918(13) 7 ?
S1 O7 1.435(16) . ?
S1 O4 1.445(13) . ?
S1 O12 1.47(2) . ?
S1 O12 1.47(2) 6_545 ?
S2 O10 1.433(18) . ?
S2 O11 1.448(13) . ?
S2 O11 1.448(13) 6_545 ?
S2 O9 1.457(15) . ?
S2 Ca 3.133(9) . ?
Ca O10 2.388(18) . ?
Ca O13 2.51(3) . ?
Ca O13 2.51(3) 6_545 ?
Ca O12 2.58(2) 7_535 ?
Ca O12 2.58(2) 4 ?
Ca O9 2.82(2) . ?
Ca Ca 3.081(15) 5_645 ?
O1 Cu1 1.978(8) 1_565 ?
O2 Cu2 1.946(8) 1_565 ?
O2 Cu1 1.980(9) 1_565 ?
O3 Cu3 1.961(7) 4_545 ?
O5 Cu2 1.953(7) 4_546 ?
O5 Ce 2.917(14) 1_545 ?
O11 Ce 2.475(12) 1_545 ?
O12 Ca 2.58(2) 7_535 ?
O13 O13 1.71(6) 6_535 ?
 
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 Ce O2 95.0(4) . 6 ?
O2 Ce O11 72.0(6) . 1_565 ?
O2 Ce O11 152.4(4) 6 1_565 ?
O2 Ce O11 152.4(4) . 6_545 ?
O2 Ce O11 72.0(6) 6 6_545 ?
O11 Ce O11 108.4(12) 1_565 6_545 ?
O2 Ce O1 66.8(3) . . ?
O2 Ce O1 126.9(3) 6 . ?
O11 Ce O1 71.2(5) 1_565 . ?
O11 Ce O1 140.4(3) 6_545 . ?
O2 Ce O1 126.9(3) . 6 ?
O2 Ce O1 66.8(3) 6 6 ?
O11 Ce O1 140.4(3) 1_565 6 ?
O11 Ce O1 71.2(5) 6_545 6 ?
O1 Ce O1 84.7(4) . 6 ?
O2 Ce O3 128.9(2) . . ?
O2 Ce O3 128.9(2) 6 . ?
O11 Ce O3 75.6(4) 1_565 . ?
O11 Ce O3 75.6(4) 6_545 . ?
O1 Ce O3 65.9(3) . . ?
O1 Ce O3 65.9(3) 6 . ?
O2 Ce O6 73.9(3) . . ?
O2 Ce O6 73.9(3) 6 . ?
O11 Ce O6 79.1(3) 1_565 . ?
O11 Ce O6 79.1(3) 6_545 . ?
O1 Ce O6 136.2(2) . . ?
O1 Ce O6 136.2(2) 6 . ?
O3 Ce O6 135.8(4) . . ?
O2 Ce O14 116.1(5) . . ?
O2 Ce O14 116.1(5) 6 . ?
O11 Ce O14 54.4(6) 1_565 . ?
O11 Ce O14 54.4(6) 6_545 . ?
O1 Ce O14 116.7(5) . . ?
O1 Ce O14 116.7(5) 6 . ?
O3 Ce O14 71.0(8) . . ?
O6 Ce O14 64.9(8) . . ?
O2 Ce O5 57.8(2) . 1_565 ?
O2 Ce O5 57.8(2) 6 1_565 ?
O11 Ce O5 125.6(6) 1_565 1_565 ?
O11 Ce O5 125.6(6) 6_545 1_565 ?
O1 Ce O5 71.1(2) . 1_565 ?
O1 Ce O5 71.1(2) 6 1_565 ?
O3 Ce O5 120.5(4) . 1_565 ?
O6 Ce O5 103.6(4) . 1_565 ?
O14 Ce O5 168.5(8) . 1_565 ?
O2 Ce Cu1 125.3(2) . . ?
O2 Ce Cu1 35.5(2) 6 . ?
O11 Ce Cu1 162.3(6) 1_565 . ?
O11 Ce Cu1 54.7(6) 6_545 . ?
O1 Ce Cu1 117.31(19) . . ?
O1 Ce Cu1 35.65(18) 6 . ?
O3 Ce Cu1 93.40(10) . . ?
O6 Ce Cu1 100.65(10) . . ?
O14 Ce Cu1 109.14(6) . . ?
O5 Ce Cu1 71.87(5) 1_565 . ?
O2 Ce Cu1 35.5(2) . 1_565 ?
O2 Ce Cu1 125.3(2) 6 1_565 ?
O11 Ce Cu1 54.7(6) 1_565 1_565 ?
O11 Ce Cu1 162.3(6) 6_545 1_565 ?
O1 Ce Cu1 35.65(18) . 1_565 ?
O1 Ce Cu1 117.31(19) 6 1_565 ?
O3 Ce Cu1 93.40(10) . 1_565 ?
O6 Ce Cu1 100.65(10) . 1_565 ?
O14 Ce Cu1 109.14(6) . 1_565 ?
O5 Ce Cu1 71.87(5) 1_565 1_565 ?
Cu1 Ce Cu1 141.26(8) . 1_565 ?
O1 Cu1 O1 98.6(5) 1_545 6 ?
O1 Cu1 O2 174.8(4) 1_545 6 ?
O1 Cu1 O2 86.6(4) 6 6 ?
O1 Cu1 O2 86.6(4) 1_545 1_545 ?
O1 Cu1 O2 174.8(4) 6 1_545 ?
O2 Cu1 O2 88.3(5) 6 1_545 ?
O1 Cu1 O4 89.6(3) 1_545 . ?
O1 Cu1 O4 89.6(3) 6 . ?
O2 Cu1 O4 90.9(3) 6 . ?
O2 Cu1 O4 90.9(3) 1_545 . ?
O1 Cu1 Ce 138.6(2) 1_545 . ?
O1 Cu1 Ce 47.2(2) 6 . ?
O2 Cu1 Ce 45.7(2) 6 . ?
O2 Cu1 Ce 128.0(3) 1_545 . ?
O4 Cu1 Ce 109.14(4) . . ?
O1 Cu1 Ce 47.2(2) 1_545 1_545 ?
O1 Cu1 Ce 138.6(2) 6 1_545 ?
O2 Cu1 Ce 128.0(3) 6 1_545 ?
O2 Cu1 Ce 45.7(3) 1_545 1_545 ?
O4 Cu1 Ce 109.14(4) . 1_545 ?
Ce Cu1 Ce 141.26(8) . 1_545 ?
O2 Cu2 O2 180.0(2) 7_546 1_545 ?
O2 Cu2 O5 95.5(5) 7_546 . ?
O2 Cu2 O5 84.5(5) 1_545 . ?
O2 Cu2 O5 84.5(5) 7_546 7_536 ?
O2 Cu2 O5 95.5(5) 1_545 7_536 ?
O5 Cu2 O5 180.0 . 7_536 ?
O3 Cu3 O3 180.0 7 . ?
O3 Cu3 O1 87.6(4) 7 7 ?
O3 Cu3 O1 92.4(4) . 7 ?
O3 Cu3 O1 92.4(4) 7 . ?
O3 Cu3 O1 87.6(4) . . ?
O1 Cu3 O1 180.0 7 . ?
O3 Cu3 Ce 135.6(3) 7 . ?
O3 Cu3 Ce 44.4(3) . . ?
O1 Cu3 Ce 136.0(2) 7 . ?
O1 Cu3 Ce 44.0(2) . . ?
O3 Cu3 Ce 44.4(3) 7 7 ?
O3 Cu3 Ce 135.6(3) . 7 ?
O1 Cu3 Ce 44.0(2) 7 7 ?
O1 Cu3 Ce 136.0(2) . 7 ?
Ce Cu3 Ce 180.0 . 7 ?
O7 S1 O4 111.3(8) . . ?
O7 S1 O12 108.2(8) . . ?
O4 S1 O12 107.2(9) . . ?
O7 S1 O12 108.2(8) . 6_545 ?
O4 S1 O12 107.2(9) . 6_545 ?
O12 S1 O12 115(2) . 6_545 ?
O10 S2 O11 108.4(9) . . ?
O10 S2 O11 108.4(10) . 6_545 ?
O11 S2 O11 107.7(19) . 6_545 ?
O10 S2 O9 110.9(11) . . ?
O11 S2 O9 110.7(7) . . ?
O11 S2 O9 110.7(7) 6_545 . ?
O10 S2 Ca 46.6(7) . . ?
O11 S2 Ca 125.4(10) . . ?
O11 S2 Ca 125.4(10) 6_545 . ?
O9 S2 Ca 64.3(8) . . ?
O10 Ca O13 76.1(6) . . ?
O10 Ca O13 76.1(6) . 6_545 ?
O13 Ca O13 135.2(11) . 6_545 ?
O10 Ca O12 110.6(7) . 7_535 ?
O13 Ca O12 63.6(9) . 7_535 ?
O13 Ca O12 160.7(9) 6_545 7_535 ?
O10 Ca O12 110.6(7) . 4 ?
O13 Ca O12 160.7(9) . 4 ?
O13 Ca O12 63.6(9) 6_545 4 ?
O12 Ca O12 97.3(14) 7_535 4 ?
O10 Ca O9 53.5(6) . . ?
O13 Ca O9 95.5(6) . . ?
O13 Ca O9 95.5(6) 6_545 . ?
O12 Ca O9 76.1(4) 7_535 . ?
O12 Ca O9 76.1(4) 4 . ?
O10 Ca Ca 111.6(6) . 5_645 ?
O13 Ca Ca 79.2(6) . 5_645 ?
O13 Ca Ca 79.2(6) 6_545 5_645 ?
O12 Ca Ca 112.9(4) 7_535 5_645 ?
O12 Ca Ca 112.9(4) 4 5_645 ?
O9 Ca Ca 165.2(5) . 5_645 ?
O10 Ca S2 25.9(5) . . ?
O13 Ca S2 85.0(6) . . ?
O13 Ca S2 85.0(6) 6_545 . ?
O12 Ca S2 94.2(5) 7_535 . ?
O12 Ca S2 94.2(5) 4 . ?
O9 Ca S2 27.7(3) . . ?
Ca Ca S2 137.5(4) 5_645 . ?
Cu3 O1 Cu1 125.4(4) . 1_565 ?
Cu3 O1 Ce 102.7(3) . . ?
Cu1 O1 Ce 97.2(3) 1_565 . ?
Cu2 O2 Cu1 103.3(4) 1_565 1_565 ?
Cu2 O2 Ce 117.8(4) 1_565 . ?
Cu1 O2 Ce 98.8(3) 1_565 . ?
Cu3 O3 Cu3 108.2(6) 4_545 . ?
Cu3 O3 Ce 102.3(4) 4_545 . ?
Cu3 O3 Ce 102.3(4) . . ?
S1 O4 Cu1 120.3(7) . . ?
Cu2 O5 Cu2 108.8(5) . 4_546 ?
Cu2 O5 Ce 99.3(5) . 1_545 ?
Cu2 O5 Ce 99.3(5) 4_546 1_545 ?
S2 O9 Ca 88.0(9) . . ?
S2 O10 Ca 107.5(11) . . ?
S2 O11 Ce 156.5(8) . 1_545 ?
S1 O12 Ca 146.4(9) . 7_535 ?
O13 O13 Ca 157.6(5) 6_535 . ?
 
_refine_diff_density_max    3.027
_refine_diff_density_min   -1.467
_refine_diff_density_rms    0.278

_shelxl_version_number 2014-3



# start Validation Reply Form
_vrf_PLAT213_bridgesite
;
PROBLEM: Atom O11             has ADP max/min Ratio .....        6.1 prolat
RESPONSE: This structure is very disordered, probably due to partial dehydration
;
_vrf_PLAT094_bridgesite
;
PROBLEM: Ratio of Maximum / Minimum Residual Density ....       2.06 Report
RESPONSE: This structure is very disordered, probably due to partial dehydration
;
_vrf_PLAT202_bridgesite
;
PROBLEM: Isotropic non-H Atoms in Anion/Solvent .........          1 Check 
RESPONSE: Not applicable
;
_vrf_PLAT242_bridgesite
;
PROBLEM: Low    'MainMol' Ueq as Compared to Neighbors of         S1 Check 
RESPONSE: This structure is very disordered, probably due to partial dehydration
;
_vrf_PLAT250_bridgesite
;
PROBLEM: Large U3/U1 Ratio for Average U(i,j) Tensor ....        3.4 Note  
RESPONSE: This structure is very disordered, probably due to partial dehydration
;
# end Validation Reply Form
