# Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.
# This journal is © the Owner Societies 2015

####################################################################### 
# 
# 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_I
_database_code_depnum_ccdc_archive 'CCDC 1054041'
_audit_update_record             
;
2015-03-13 deposited with the CCDC.
2015-05-20 downloaded from the CCDC.
;
_publcif_datablock.id            {39d8c2a1-9211-49ed-91f9-a9b50c322271}

#=======================================================================

# 5. CHEMICAL DATA

_chemical_name_systematic        'Copper Zinc Tin selenide'
_chemical_name_common            CZTSe
_chemical_formula_moiety         'Cu2 Se4 Sn1 Zn1'
_chemical_formula_structural     ?
_chemical_formula_analytical     ?
_chemical_formula_iupac          ?
_chemical_formula_sum            'Cu2 Se4 Sn1 Zn1'
_chemical_formula_weight         627
_chemical_melting_point          ?
_chemical_compound_source        ?
_chemical_absolute_configuration ?

#=======================================================================

# 6. CRYSTAL DATA

_symmetry_cell_setting           tetragonal
_symmetry_space_group_name_H-M   'I -4 2 m'
_symmetry_space_group_name_Hall  'I -4 2'
_symmetry_Int_Tables_number      121

loop_
_space_group_symop_id
_space_group_symop_operation_xyz
1 x,y,z
2 -x,-y,z
3 y,-x,-z
4 -y,x,-z
5 -x,y,-z
6 x,-y,-z
7 -y,-x,z
8 y,x,z
9 x+1/2,y+1/2,z+1/2
10 -x+1/2,-y+1/2,z+1/2
11 y+1/2,-x+1/2,-z+1/2
12 -y+1/2,x+1/2,-z+1/2
13 -x+1/2,y+1/2,-z+1/2
14 x+1/2,-y+1/2,-z+1/2
15 -y+1/2,-x+1/2,z+1/2
16 y+1/2,x+1/2,z+1/2

_cell_length_a                   5.69647(5)
_cell_length_b                   5.69647(5)
_cell_length_c                   11.3394(2)
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_volume                     367.965(6)

loop_
_jana_cell_twin_matrix_id
_jana_cell_twin_volume_fraction
_jana_cell_twin_matrix_1_1
_jana_cell_twin_matrix_1_2
_jana_cell_twin_matrix_1_3
_jana_cell_twin_matrix_2_1
_jana_cell_twin_matrix_2_2
_jana_cell_twin_matrix_2_3
_jana_cell_twin_matrix_3_1
_jana_cell_twin_matrix_3_2
_jana_cell_twin_matrix_3_3
? ? ? ? ? ? ? ? ? ? ?
_cell_formula_units_Z            2

_cell_measurement_reflns_used    447
_cell_measurement_theta_min      6.48
_cell_measurement_theta_max      34.91
_cell_measurement_temperature    293
_cell_special_details            ?

_exptl_crystal_density_diffrn    5.6574
_exptl_crystal_density_meas      ?
_exptl_crystal_density_method    ?
_exptl_crystal_F_000             548

_exptl_absorpt_coefficient_mu    31.943
_exptl_crystal_description       block
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.015
_exptl_crystal_size_rad          ?
_exptl_crystal_colour            black
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details   'Jana2006  (Petricek, Dusek & Palatinus, 2000)'
_exptl_absorpt_correction_T_min  0.1892
_exptl_absorpt_correction_T_max  0.3767
loop_
_exptl_crystal_face_index_h
_exptl_crystal_face_index_k
_exptl_crystal_face_index_l
_exptl_crystal_face_perp_dist
? ? ? ?

#=======================================================================

# 7. EXPERIMENTAL DATA

_exptl_special_details           ?

_diffrn_ambient_temperature      293
_diffrn_source                   ?
_diffrn_source_power             ?
_diffrn_source_voltage           ?
_diffrn_source_current           ?
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_source         'X-ray tube'
_diffrn_radiation_wavelength     0.71069
_diffrn_radiation_monochromator  graphite
_diffrn_measurement_device       'four-cycle diffractometer'
_diffrn_measurement_device_type  'Nonius CCD'
_diffrn_detector                 ?
_diffrn_detector_area_resol_mean ?
_diffrn_measurement_method       phi,omega
_diffrn_measurement_specimen_support ?

_diffrn_reflns_number            3282
_diffrn_reflns_theta_min         6.48
_diffrn_reflns_theta_max         34.91
_diffrn_reflns_theta_full        34.91
_diffrn_measured_fraction_theta_max 0.98
_diffrn_measured_fraction_theta_full 0.98
_diffrn_reflns_av_R_equivalents  0.057
_diffrn_reflns_av_unetI/netI     ?
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_k_min       -9
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_reduction_process ?

_diffrn_standards_number         ?
_diffrn_standards_interval_count ?
_diffrn_standards_interval_time  ?
_diffrn_standards_decay_%        ?
loop_
_diffrn_standard_refln_index_h
_diffrn_standard_refln_index_k
_diffrn_standard_refln_index_l
? ? ?

_diffrn_radiation_probe          x-ray

_diffrn_reflns_av_sigmaI/netI    0.0095

#=======================================================================

# 8. REFINEMENT DATA

_refine_special_details          ?

_reflns_number_total             447
_reflns_number_gt                411
_reflns_threshold_expression     I>2σ(I)

_refine_ls_structure_factor_coef Fsqd
_refine_ls_R_factor_gt           0.0275
_refine_ls_wR_factor_gt          0.0994
_refine_ls_R_factor_all          0.0363
_refine_ls_wR_factor_ref         0.1090
_refine_ls_goodness_of_fit_ref   1.86
_refine_ls_goodness_of_fit_gt    1.77
_refine_ls_restrained_S_gt       ?
_refine_ls_restrained_S_all      ?
_refine_ls_number_reflns         447
_refine_ls_number_parameters     14
_refine_ls_number_restraints     0
_refine_ls_number_constraints    2
_refine_ls_weighting_scheme      sigma
_refine_ls_weighting_details     w=1/(σ²(I)+0.001936I²)
_refine_ls_hydrogen_treatment    ?
_refine_ls_shift/su_max          0.0251
_refine_ls_shift/su_mean         0.0075
_refine_diff_density_max         1.31
_refine_diff_density_min         -1.24
_refine_ls_extinction_method     
'B-C type 1 Gaussian isotropic (Becker & Coppens, 1974)'
_refine_ls_extinction_coef       2800(300)
_refine_ls_abs_structure_details 
;  179 of Friedel pairs used in the refinement
;
_refine_ls_abs_structure_Flack   ?
_refine_ls_abs_structure_Rogers  ?

loop_
_atom_type_symbol
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
Cu 0.3201 1.2651 'International Tables Vol C tables 4.2.6.8 and 6.1.1.1'
Se -0.0929 2.2259 'International Tables Vol C tables 4.2.6.8 and 6.1.1.1'
Sn -0.6537 1.4246 'International Tables Vol C tables 4.2.6.8 and 6.1.1.1'
Zn 0.2839 1.4301 'International Tables Vol C tables 4.2.6.8 and 6.1.1.1'

_computing_data_collection       ?
_computing_cell_refinement       ?
_computing_data_reduction        ?
_computing_structure_solution    ?
_computing_structure_refinement  ?
_computing_molecular_graphics    ?
_computing_publication_material  ?

loop_
_restr_distance_atom_site_label_1
_restr_distance_site_symmetry_1
_restr_distance_atom_site_label_2
_restr_distance_site_symmetry_2
_restr_distance_target
_restr_distance_target_weight_param
? ? ? ? ? ?

loop_
_restr_angle_atom_site_label_1
_restr_angle_site_symmetry_1
_restr_angle_atom_site_label_2
_restr_angle_site_symmetry_2
_restr_angle_atom_site_label_3
_restr_angle_site_symmetry_3
_restr_angle_target
_restr_angle_target_weight_param
? ? ? ? ? ? ? ?

loop_
_restr_torsion_atom_site_label_1
_restr_torsion_site_symmetry_1
_restr_torsion_atom_site_label_2
_restr_torsion_site_symmetry_2
_restr_torsion_atom_site_label_3
_restr_torsion_site_symmetry_3
_restr_torsion_atom_site_label_4
_restr_torsion_site_symmetry_4
_restr_torsion_angle_target
_restr_torsion_weight_param
? ? ? ? ? ? ? ? ? ?

loop_
_restr_equal_distance_atom_site_label_1
_restr_equal_distance_site_symmetry_1
_restr_equal_distance_atom_site_label_2
_restr_equal_distance_site_symmetry_2
_restr_equal_distance_class_class_id
_restr_equal_distance_class_target_weight_param
? ? ? ? ? ?

loop_
_restr_equal_angle_atom_site_label_1
_restr_equal_angle_site_symmetry_1
_restr_equal_angle_atom_site_label_2
_restr_equal_angle_site_symmetry_2
_restr_equal_angle_atom_site_label_3
_restr_equal_angle_site_symmetry_3
_restr_equal_angle_class_class_id
_restr_equal_angle_class_target_weight_param
? ? ? ? ? ? ? ?

loop_
_restr_equal_torsion_atom_site_label_1
_restr_equal_torsion_site_symmetry_1
_restr_equal_torsion_atom_site_label_2
_restr_equal_torsion_site_symmetry_2
_restr_equal_torsion_atom_site_label_3
_restr_equal_torsion_site_symmetry_3
_restr_equal_torsion_atom_site_label_4
_restr_equal_torsion_site_symmetry_4
_restr_equal_torsion_class_class_id
_restr_equal_torsion_class_target_weight_param
? ? ? ? ? ? ? ? ? ?


#=======================================================================

# 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS

loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_adp_type
_atom_site_U_iso_or_equiv
_atom_site_site_symmetry_multiplicity
_atom_site_occupancy
_atom_site_calc_flag
_atom_site_refinement_flags
_atom_site_disorder_assembly
_atom_site_disorder_group
Cu_2a Cu 0 0 0 Uani 0.0182(4) 2 1 d . . .
Cu_4d Cu 0 0.5 0.25 Uani 0.0141(3) 4 0.5 d . . .
Zn_4d Zn 0 0.5 0.25 Uani 0.0141(3) 4 0.5 d . . .
Sn_2b Sn 0 0 0.5 Uani 0.00819(18) 2 1 d . . .
Se Se 0.75875(12) 0.24125(12) 0.12881(8) Uani 0.0142(2) 8 1 d . . .

loop_
_atom_site_aniso_label
_atom_site_aniso_type_symbol
_atom_site_aniso_U_11
_atom_site_aniso_U_22
_atom_site_aniso_U_33
_atom_site_aniso_U_12
_atom_site_aniso_U_13
_atom_site_aniso_U_23
Cu_2a Cu 0.0198(6) 0.0198(6) 0.0151(8) 0 0 0
Cu_4d Cu 0.0137(3) 0.0137(3) 0.0148(7) 0 0 0
Zn_4d Zn 0.0137(3) 0.0137(3) 0.0148(7) 0 0 0
Sn_2b Sn 0.0081(3) 0.0081(3) 0.0084(4) 0 0 0
Se Se 0.0142(3) 0.0142(3) 0.0141(5) 0.00076(18) -0.00092(14) 0.00092(14)

loop_
_jana_atom_site_ADP_C_label
_jana_atom_site_ADP_C_type_symbol
_jana_atom_site_ADP_C_111
_jana_atom_site_ADP_C_112
_jana_atom_site_ADP_C_113
_jana_atom_site_ADP_C_122
_jana_atom_site_ADP_C_123
_jana_atom_site_ADP_C_133
_jana_atom_site_ADP_C_222
_jana_atom_site_ADP_C_223
_jana_atom_site_ADP_C_233
_jana_atom_site_ADP_C_333
? ? ? ? ? ? ? ? ? ? ? ?

loop_
_jana_atom_site_ADP_D_label
_jana_atom_site_ADP_D_type_symbol
_jana_atom_site_ADP_D_1111
_jana_atom_site_ADP_D_1112
_jana_atom_site_ADP_D_1113
_jana_atom_site_ADP_D_1122
_jana_atom_site_ADP_D_1123
_jana_atom_site_ADP_D_1133
_jana_atom_site_ADP_D_1222
_jana_atom_site_ADP_D_1223
_jana_atom_site_ADP_D_1233
_jana_atom_site_ADP_D_1333
_jana_atom_site_ADP_D_2222
_jana_atom_site_ADP_D_2223
_jana_atom_site_ADP_D_2233
_jana_atom_site_ADP_D_2333
_jana_atom_site_ADP_D_3333
? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ?

loop_
_jana_atom_site_ADP_E_label
_jana_atom_site_ADP_E_type_symbol
_jana_atom_site_ADP_E_11111
_jana_atom_site_ADP_E_11112
_jana_atom_site_ADP_E_11113
_jana_atom_site_ADP_E_11122
_jana_atom_site_ADP_E_11123
_jana_atom_site_ADP_E_11133
_jana_atom_site_ADP_E_11222
_jana_atom_site_ADP_E_11223
_jana_atom_site_ADP_E_11233
_jana_atom_site_ADP_E_11333
_jana_atom_site_ADP_E_12222
_jana_atom_site_ADP_E_12223
_jana_atom_site_ADP_E_12233
_jana_atom_site_ADP_E_12333
_jana_atom_site_ADP_E_13333
_jana_atom_site_ADP_E_22222
_jana_atom_site_ADP_E_22223
_jana_atom_site_ADP_E_22233
_jana_atom_site_ADP_E_22333
_jana_atom_site_ADP_E_23333
_jana_atom_site_ADP_E_33333
? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ?

loop_
_jana_atom_site_ADP_F_label
_jana_atom_site_ADP_F_type_symbol
_jana_atom_site_ADP_F_111111
_jana_atom_site_ADP_F_111112
_jana_atom_site_ADP_F_111113
_jana_atom_site_ADP_F_111122
_jana_atom_site_ADP_F_111123
_jana_atom_site_ADP_F_111133
_jana_atom_site_ADP_F_111222
_jana_atom_site_ADP_F_111223
_jana_atom_site_ADP_F_111233
_jana_atom_site_ADP_F_111333
_jana_atom_site_ADP_F_112222
_jana_atom_site_ADP_F_112223
_jana_atom_site_ADP_F_112233
_jana_atom_site_ADP_F_112333
_jana_atom_site_ADP_F_113333
_jana_atom_site_ADP_F_122222
_jana_atom_site_ADP_F_122223
_jana_atom_site_ADP_F_122233
_jana_atom_site_ADP_F_122333
_jana_atom_site_ADP_F_123333
_jana_atom_site_ADP_F_133333
_jana_atom_site_ADP_F_222222
_jana_atom_site_ADP_F_222223
_jana_atom_site_ADP_F_222233
_jana_atom_site_ADP_F_222333
_jana_atom_site_ADP_F_223333
_jana_atom_site_ADP_F_233333
_jana_atom_site_ADP_F_333333
? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ? ?


#=======================================================================

# 10. MOLECULAR GEOMETRY


loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_site_symmetry_1
_geom_bond_site_symmetry_2
_geom_bond_distance
_geom_bond_publ_flag
Cu_2a Se . 1_455 2.4312(8) ?
Cu_2a Se . 2_655 2.4312(8) ?
Cu_2a Se . 3_565 2.4312(8) ?
Cu_2a Se . 4_545 2.4312(8) ?
Cu_4d Se . 1_455 2.4392(7) ?
Cu_4d Se . 2_665 2.4392(7) ?
Cu_4d Se . 11_465 2.4392(7) ?
Cu_4d Se . 12_545 2.4392(7) ?
Sn_2b Se . 9_445 2.5453(7) ?
Sn_2b Se . 10_555 2.5453(7) ?
Sn_2b Se . 11_455 2.5453(7) ?
Sn_2b Se . 12_545 2.5453(7) ?

loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_2
_geom_angle_site_symmetry_3
_geom_angle
_geom_angle_publ_flag
Se Cu_2a Se 1_455 . 2_655 106.15(3) ?
Se Cu_2a Se 1_455 . 3_565 111.16(2) ?
Se Cu_2a Se 1_455 . 4_545 111.16(2) ?
Se Cu_2a Se 2_655 . 3_565 111.16(2) ?
Se Cu_2a Se 2_655 . 4_545 111.16(2) ?
Se Cu_2a Se 3_565 . 4_545 106.15(3) ?
Se Cu_4d Se 1_455 . 2_665 111.42(3) ?
Se Cu_4d Se 1_455 . 11_465 108.51(2) ?
Se Cu_4d Se 1_455 . 12_545 108.51(2) ?
Se Cu_4d Se 2_665 . 11_465 108.51(2) ?
Se Cu_4d Se 2_665 . 12_545 108.51(2) ?
Se Cu_4d Se 11_465 . 12_545 111.42(3) ?
Se Sn_2b Se 9_445 . 10_555 109.96(3) ?
Se Sn_2b Se 9_445 . 11_455 109.23(2) ?
Se Sn_2b Se 9_445 . 12_545 109.23(2) ?
Se Sn_2b Se 10_555 . 11_455 109.23(2) ?
Se Sn_2b Se 10_555 . 12_545 109.23(2) ?
Se Sn_2b Se 11_455 . 12_545 109.96(3) ?

loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_2
_geom_torsion_site_symmetry_3
_geom_torsion_site_symmetry_4
_geom_torsion
_geom_torsion_publ_flag
? ? ? ? ? ? ? ? ? ?

loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_site_symmetry_D
_geom_hbond_site_symmetry_H
_geom_hbond_site_symmetry_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_publ_flag
? ? ? ? ? ? ? ? ? ? ?

loop_
_publcif_info_exptl_table_extra_item
sin_theta_over_lambda_max

loop_
_publcif_info_exptl_table_header_item
?

_exptl_crystal_recrystallization_method 'Vapor transport'
_exptl_crystal_preparation       Semiconductor
