Molecular Construction from AgGaS2 to CuZnPS4: Defect-Induced Second Harmonic Generation Enhancement and Cosubstitution-Driven Band Gap Enlargement
Li, Zhuang; Zhang, Shengzi; Huang, Zhiwei; Zhao, Li-Dong; Uykur, Ece; Xing, Wenhao; Lin, Zheshuai; Yao, Jiyong; Wu, Yicheng; Chemistry of Materials  (2020) –; doi:10.1021/acs.chemmater.0c00609

data_4003499
_publ_section_title
;
 Molecular Construction from AgGaS2 to CuZnPS4: Defect-Induced Second
 Harmonic Generation Enhancement and Cosubstitution-Driven Band Gap
 Enlargement
;
_journal_name_full               'Chemistry of Materials'
_journal_paper_doi               10.1021/acs.chemmater.0c00609
_journal_year                    2020
_chemical_formula_moiety         '0.5(Cu2 P2 S8 Zn2)'
_chemical_formula_sum            'Cu P S4 Zn'
_chemical_formula_weight         288.12
_space_group_crystal_system      tetragonal
_space_group_IT_number           121
_space_group_name_Hall           'I -4 2'
_space_group_name_H-M_alt        'I -4 2 m'
_atom_sites_solution_primary     dual
_audit_creation_date             2019-07-26
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   5.4980(4)
_cell_length_b                   5.4980(4)
_cell_length_c                   9.2110(10)
_cell_measurement_reflns_used    1218
_cell_measurement_temperature    153(2)
_cell_measurement_theta_max      26.2500
_cell_measurement_theta_min      4.2660
_cell_volume                     278.43(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.44a (Rigaku OD, 2018)'
_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)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      153(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \w      3.00  80.00   0.50    1.42    --    9.62  19.00  90.00  154
  2  \w    -13.00  81.00   0.50    1.42    --    9.62  77.00 120.00  188
  3  \w     39.00  81.00   0.50    1.42    --    9.62  57.00-150.00   84
  4  \w    -25.00  33.00   0.50    1.42    --    9.62 -99.00 -30.00  116
  5  \w    -20.00  18.00   0.50    1.42    --    9.62 -37.00 -90.00   76
  6  \w    -24.00   7.00   0.50    1.42    --   -8.52 -99.00  60.00   62
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0121976000
_diffrn_orient_matrix_UB_12      0.0713928000
_diffrn_orient_matrix_UB_13      -0.0636973000
_diffrn_orient_matrix_UB_21      -0.1242680000
_diffrn_orient_matrix_UB_22      -0.0204385000
_diffrn_orient_matrix_UB_23      -0.0166060000
_diffrn_orient_matrix_UB_31      -0.0322635000
_diffrn_orient_matrix_UB_32      0.1056175000
_diffrn_orient_matrix_UB_33      0.0398950000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0247
_diffrn_reflns_av_unetI/netI     0.0119
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       6
_diffrn_reflns_limit_h_min       -6
_diffrn_reflns_limit_k_max       6
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            1383
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.251
_diffrn_reflns_theta_min         4.317
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    9.753
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49644
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.44a (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_density_diffrn    3.437
_exptl_crystal_description       block
_exptl_crystal_F_000             276
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.261
_refine_diff_density_min         -0.851
_refine_diff_density_rms         0.125
_refine_ls_abs_structure_details
;
 Flack x determined using 62 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.03(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.302
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     11
_refine_ls_number_reflns         169
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.302
_refine_ls_R_factor_all          0.0190
_refine_ls_R_factor_gt           0.0189
_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/[\s^2^(Fo^2^)+(0.0173P)^2^+1.5652P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0495
_refine_ls_wR_factor_ref         0.0495
_reflns_Friedel_coverage         0.594
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     1.000
_reflns_number_gt                168
_reflns_number_total             169
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm0c00609_si_002.cif
_cod_data_source_block           exp_5502
_cod_original_cell_volume        278.43(5)
_cod_database_code               4003499
_shelxl_version_number           2014-3
_reflns_odcompleteness_completeness 84.25
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     28.22
_olex2_refinement_description
;
1. Shared sites
{Cu01, Zn01}
2. Uiso/Uaniso restraints and constraints
Uanis(Cu01) = Uanis(Zn01)
3. Others
 Fixed Sof: Cu01(0.125) Zn01(0.125)
;
_shelx_res_checksum              71702
_shelx_hkl_checksum              85757
_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 1.554
_oxdiff_exptl_absorpt_empirical_full_min 0.734