# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A.
# 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_zm
_database_code_depnum_ccdc_archive 'CCDC 1834634'
_audit_update_record             
;
2018-04-04 deposited with the CCDC.
2018-05-29 downloaded from the CCDC.
;
# start Validation Reply Form
_vrf_PLAT029_zm                  
;
PROBLEM: _diffrn_measured_fraction_theta_full value Low .      0.926 Why?
RESPONSE: This problem was caused by the symmetry-breaking originating from the disorders in the anionic structure, which might have been solved by modeling the structure with a lower-symmetry space group. However, in current case no suitable superlattice structure can be established.
;
# Added during the CSD deposition process: Wednesday 04 April 2018 02:42 AM
# end Validation Reply Form


_audit_creation_method           SHELXL-97
_chemical_name_systematic        
; 
 ? 
;
_chemical_name_common            ?
_chemical_melting_point          ?
_chemical_formula_moiety         ?
_chemical_formula_sum            'Ag0.28 Ca Sb Zn0.29'
_chemical_formula_weight         210.45

loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Ca Ca 0.2262 0.3064 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ag Ag -0.8971 1.1015 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Sb Sb -0.5866 1.5461 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'

_symmetry_cell_setting           Hexagonal
_symmetry_space_group_name_H-M   P6(3)mc

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

_cell_length_a                   4.5897(4)
_cell_length_b                   4.5897(4)
_cell_length_c                   7.8005(14)
_cell_angle_alpha                90.00
_cell_angle_beta                 90.00
_cell_angle_gamma                120.00
_cell_volume                     142.31(3)
_cell_formula_units_Z            2
_cell_measurement_temperature    296(2)
_cell_measurement_reflns_used    699
_cell_measurement_theta_min      5.13
_cell_measurement_theta_max      27.14

_exptl_crystal_description       block
_exptl_crystal_colour            black
_exptl_crystal_size_max          0.10
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_exptl_crystal_density_meas      ?
_exptl_crystal_density_diffrn    4.911
_exptl_crystal_density_method    'not measured'
_exptl_crystal_F_000             185
_exptl_absorpt_coefficient_mu    15.345
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_correction_T_min  0.3091
_exptl_absorpt_correction_T_max  0.4595
_exptl_absorpt_process_details   ?

_exptl_special_details           
; 
 ? 
;

_diffrn_ambient_temperature      296(2)
_diffrn_radiation_wavelength     0.71073
_diffrn_radiation_type           MoK\a
_diffrn_radiation_source         'fine-focus sealed tube'
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_detector_area_resol_mean ?
_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
_diffrn_reflns_number            780
_diffrn_reflns_av_R_equivalents  0.0369
_diffrn_reflns_av_sigmaI/netI    0.0259
_diffrn_reflns_limit_h_min       -5
_diffrn_reflns_limit_h_max       4
_diffrn_reflns_limit_k_min       -5
_diffrn_reflns_limit_k_max       5
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_theta_min         5.13
_diffrn_reflns_theta_max         27.14
_reflns_number_total             139
_reflns_number_gt                126
_reflns_threshold_expression     >2sigma(I)

_computing_data_collection       'Bruker SMART'
_computing_cell_refinement       'Bruker SMART'
_computing_data_reduction        'Bruker SAINT'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'

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

_refine_ls_structure_factor_coef Fsqd
_refine_ls_matrix_type           full
_refine_ls_weighting_scheme      calc
_refine_ls_weighting_details     
'calc w=1/[σ²(Fo²)+(0.0378P)²+0.5731P] where P=(Fo²+2Fc²)/3'
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_atom_sites_solution_hydrogens   ?
_refine_ls_hydrogen_treatment    ?
_refine_ls_extinction_method     SHELXL
_refine_ls_extinction_coef       0.42(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4^
_refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881'
_refine_ls_abs_structure_Flack   0.2(3)
_refine_ls_number_reflns         139
_refine_ls_number_parameters     13
_refine_ls_number_restraints     2
_refine_ls_R_factor_all          0.0291
_refine_ls_R_factor_gt           0.0268
_refine_ls_wR_factor_ref         0.0643
_refine_ls_wR_factor_gt          0.0616
_refine_ls_goodness_of_fit_ref   1.162
_refine_ls_restrained_S_all      1.153
_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_symmetry_multiplicity
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Ca Ca 0.0000 0.0000 0.0000(6) 0.0368(8) Uani 1 6 d S . .
Zn Zn 0.6667 0.3333 0.2022(7) 0.045(2) Uani 0.400(18) 6 d SP . .
Ag Ag 0.6667 0.3333 0.2022(7) 0.045(2) Uani 0.20(2) 6 d SP . .
Sb Sb 0.3333 0.6667 0.2546 0.0221(6) Uani 1 6 d S . .

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
Ca 0.0476(13) 0.0476(13) 0.0150(15) 0.000 0.000 0.0238(6)
Zn 0.0103(14) 0.0103(14) 0.115(6) 0.000 0.000 0.0051(7)
Ag 0.0103(14) 0.0103(14) 0.115(6) 0.000 0.000 0.0051(7)
Sb 0.0146(6) 0.0146(6) 0.0371(8) 0.000 0.000 0.0073(3)

_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
Ca Ag 3.084(4) 1_455 ?
Ca Zn 3.084(4) 1_455 ?
Ca Zn 3.084(4) . ?
Ca Ag 3.084(4) 1_445 ?
Ca Zn 3.084(4) 1_445 ?
Ca Sb 3.269(3) 4_564 ?
Ca Sb 3.269(3) 4_554 ?
Ca Sb 3.269(3) 4_664 ?
Ca Sb 3.312(3) 1_545 ?
Ca Sb 3.312(3) . ?
Ca Sb 3.312(3) 1_445 ?
Zn Sb 2.6812(9) 1_655 ?
Zn Sb 2.6812(9) 1_545 ?
Zn Sb 2.6812(9) . ?
Zn Ca 3.084(4) 1_655 ?
Zn Ca 3.084(4) 1_665 ?
Zn Ca 3.524(5) 4_655 ?
Zn Ca 3.524(5) 4_665 ?
Zn Ca 3.524(5) 4 ?
Sb Ag 2.6812(9) 1_455 ?
Sb Zn 2.6812(9) 1_455 ?
Sb Ag 2.6812(9) 1_565 ?
Sb Zn 2.6812(9) 1_565 ?
Sb Ca 3.269(3) 4_565 ?
Sb Ca 3.269(3) 4_665 ?
Sb Ca 3.269(3) 4 ?
Sb Ca 3.312(3) 1_565 ?
Sb Ca 3.312(3) 1_665 ?

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
Ag Ca Zn 0.00(18) 1_455 1_455 ?
Ag Ca Zn 96.18(17) 1_455 . ?
Zn Ca Zn 96.18(17) 1_455 . ?
Ag Ca Ag 96.18(17) 1_455 1_445 ?
Zn Ca Ag 96.18(17) 1_455 1_445 ?
Zn Ca Ag 96.18(17) . 1_445 ?
Ag Ca Zn 96.18(17) 1_455 1_445 ?
Zn Ca Zn 96.18(17) 1_455 1_445 ?
Zn Ca Zn 96.18(17) . 1_445 ?
Ag Ca Zn 0.00(18) 1_445 1_445 ?
Ag Ca Sb 66.61(9) 1_455 4_564 ?
Zn Ca Sb 66.61(9) 1_455 4_564 ?
Zn Ca Sb 130.38(4) . 4_564 ?
Ag Ca Sb 130.38(4) 1_445 4_564 ?
Zn Ca Sb 130.38(4) 1_445 4_564 ?
Ag Ca Sb 130.38(4) 1_455 4_554 ?
Zn Ca Sb 130.38(4) 1_455 4_554 ?
Zn Ca Sb 130.38(4) . 4_554 ?
Ag Ca Sb 66.61(9) 1_445 4_554 ?
Zn Ca Sb 66.61(9) 1_445 4_554 ?
Sb Ca Sb 89.18(10) 4_564 4_554 ?
Ag Ca Sb 130.38(4) 1_455 4_664 ?
Zn Ca Sb 130.38(4) 1_455 4_664 ?
Zn Ca Sb 66.61(9) . 4_664 ?
Ag Ca Sb 130.38(4) 1_445 4_664 ?
Zn Ca Sb 130.38(4) 1_445 4_664 ?
Sb Ca Sb 89.18(10) 4_564 4_664 ?
Sb Ca Sb 89.18(10) 4_554 4_664 ?
Ag Ca Sb 112.39(19) 1_455 1_545 ?
Zn Ca Sb 112.39(19) 1_455 1_545 ?
Zn Ca Sb 49.42(6) . 1_545 ?
Ag Ca Sb 49.42(6) 1_445 1_545 ?
Zn Ca Sb 49.42(6) 1_445 1_545 ?
Sb Ca Sb 178.99(13) 4_564 1_545 ?
Sb Ca Sb 91.539(8) 4_554 1_545 ?
Sb Ca Sb 91.539(8) 4_664 1_545 ?
Ag Ca Sb 49.42(6) 1_455 . ?
Zn Ca Sb 49.42(6) 1_455 . ?
Zn Ca Sb 49.42(6) . . ?
Ag Ca Sb 112.39(19) 1_445 . ?
Zn Ca Sb 112.39(19) 1_445 . ?
Sb Ca Sb 91.539(8) 4_564 . ?
Sb Ca Sb 178.99(13) 4_554 . ?
Sb Ca Sb 91.539(8) 4_664 . ?
Sb Ca Sb 87.73(10) 1_545 . ?
Ag Ca Sb 49.42(6) 1_455 1_445 ?
Zn Ca Sb 49.42(6) 1_455 1_445 ?
Zn Ca Sb 112.39(19) . 1_445 ?
Ag Ca Sb 49.42(6) 1_445 1_445 ?
Zn Ca Sb 49.42(6) 1_445 1_445 ?
Sb Ca Sb 91.539(8) 4_564 1_445 ?
Sb Ca Sb 91.539(8) 4_554 1_445 ?
Sb Ca Sb 178.99(13) 4_664 1_445 ?
Sb Ca Sb 87.73(10) 1_545 1_445 ?
Sb Ca Sb 87.73(10) . 1_445 ?
Sb Zn Sb 117.72(6) 1_655 1_545 ?
Sb Zn Sb 117.72(6) 1_655 . ?
Sb Zn Sb 117.72(6) 1_545 . ?
Sb Zn Ca 69.72(4) 1_655 1_655 ?
Sb Zn Ca 69.72(4) 1_545 1_655 ?
Sb Zn Ca 158.0(2) . 1_655 ?
Sb Zn Ca 158.0(2) 1_655 . ?
Sb Zn Ca 69.72(4) 1_545 . ?
Sb Zn Ca 69.72(4) . . ?
Ca Zn Ca 96.18(17) 1_655 . ?
Sb Zn Ca 69.72(4) 1_655 1_665 ?
Sb Zn Ca 158.0(2) 1_545 1_665 ?
Sb Zn Ca 69.72(4) . 1_665 ?
Ca Zn Ca 96.18(17) 1_655 1_665 ?
Ca Zn Ca 96.18(17) . 1_665 ?
Sb Zn Ca 61.83(6) 1_655 4_655 ?
Sb Zn Ca 61.83(6) 1_545 4_655 ?
Sb Zn Ca 130.0(2) . 4_655 ?
Ca Zn Ca 72.00(3) 1_655 4_655 ?
Ca Zn Ca 131.32(5) . 4_655 ?
Ca Zn Ca 131.32(5) 1_665 4_655 ?
Sb Zn Ca 61.83(6) 1_655 4_665 ?
Sb Zn Ca 130.0(2) 1_545 4_665 ?
Sb Zn Ca 61.83(6) . 4_665 ?
Ca Zn Ca 131.32(5) 1_655 4_665 ?
Ca Zn Ca 131.32(5) . 4_665 ?
Ca Zn Ca 72.00(3) 1_665 4_665 ?
Ca Zn Ca 81.27(15) 4_655 4_665 ?
Sb Zn Ca 130.0(2) 1_655 4 ?
Sb Zn Ca 61.83(6) 1_545 4 ?
Sb Zn Ca 61.83(6) . 4 ?
Ca Zn Ca 131.32(5) 1_655 4 ?
Ca Zn Ca 72.00(3) . 4 ?
Ca Zn Ca 131.32(5) 1_665 4 ?
Ca Zn Ca 81.27(15) 4_655 4 ?
Ca Zn Ca 81.27(15) 4_665 4 ?
Ag Sb Zn 0.0 1_455 1_455 ?
Ag Sb Ag 117.72(6) 1_455 1_565 ?
Zn Sb Ag 117.72(6) 1_455 1_565 ?
Ag Sb Zn 117.72(6) 1_455 1_565 ?
Zn Sb Zn 117.72(6) 1_455 1_565 ?
Ag Sb Zn 0.0(2) 1_565 1_565 ?
Ag Sb Zn 117.72(6) 1_455 . ?
Zn Sb Zn 117.72(6) 1_455 . ?
Ag Sb Zn 117.72(6) 1_565 . ?
Zn Sb Zn 117.72(6) 1_565 . ?
Ag Sb Ca 71.86(9) 1_455 4_565 ?
Zn Sb Ca 71.86(9) 1_455 4_565 ?
Ag Sb Ca 71.86(9) 1_565 4_565 ?
Zn Sb Ca 71.86(9) 1_565 4_565 ?
Zn Sb Ca 152.92(12) . 4_565 ?
Ag Sb Ca 152.92(12) 1_455 4_665 ?
Zn Sb Ca 152.92(12) 1_455 4_665 ?
Ag Sb Ca 71.86(9) 1_565 4_665 ?
Zn Sb Ca 71.86(9) 1_565 4_665 ?
Zn Sb Ca 71.86(9) . 4_665 ?
Ca Sb Ca 89.18(10) 4_565 4_665 ?
Ag Sb Ca 71.86(9) 1_455 4 ?
Zn Sb Ca 71.86(9) 1_455 4 ?
Ag Sb Ca 152.92(12) 1_565 4 ?
Zn Sb Ca 152.92(12) 1_565 4 ?
Zn Sb Ca 71.86(9) . 4 ?
Ca Sb Ca 89.18(10) 4_565 4 ?
Ca Sb Ca 89.18(10) 4_665 4 ?
Ag Sb Ca 60.87(8) 1_455 1_565 ?
Zn Sb Ca 60.87(8) 1_455 1_565 ?
Ag Sb Ca 60.87(8) 1_565 1_565 ?
Zn Sb Ca 60.87(8) 1_565 1_565 ?
Zn Sb Ca 134.38(12) . 1_565 ?
Ca Sb Ca 72.695(11) 4_565 1_565 ?
Ca Sb Ca 132.494(5) 4_665 1_565 ?
Ca Sb Ca 132.494(4) 4 1_565 ?
Ag Sb Ca 60.87(8) 1_455 . ?
Zn Sb Ca 60.87(8) 1_455 . ?
Ag Sb Ca 134.38(12) 1_565 . ?
Zn Sb Ca 134.38(12) 1_565 . ?
Zn Sb Ca 60.87(8) . . ?
Ca Sb Ca 132.494(5) 4_565 . ?
Ca Sb Ca 132.494(4) 4_665 . ?
Ca Sb Ca 72.695(11) 4 . ?
Ca Sb Ca 87.73(10) 1_565 . ?
Ag Sb Ca 134.38(12) 1_455 1_665 ?
Zn Sb Ca 134.38(12) 1_455 1_665 ?
Ag Sb Ca 60.87(8) 1_565 1_665 ?
Zn Sb Ca 60.87(8) 1_565 1_665 ?
Zn Sb Ca 60.87(8) . 1_665 ?
Ca Sb Ca 132.494(5) 4_565 1_665 ?
Ca Sb Ca 72.695(11) 4_665 1_665 ?
Ca Sb Ca 132.494(5) 4 1_665 ?
Ca Sb Ca 87.73(10) 1_565 1_665 ?
Ca Sb Ca 87.73(10) . 1_665 ?

_diffrn_measured_fraction_theta_max 0.926
_diffrn_reflns_theta_full        27.14
_diffrn_measured_fraction_theta_full 0.926
_refine_diff_density_max         0.772
_refine_diff_density_min         -1.236
_refine_diff_density_rms         0.222
