Cationic substitution engineering induces a new quaternary chalcogenide in the A–MIIIA–MIVA–Q system for optical crystal applications
Wang, Yue; Li, Xuezhong; Lou, Zihao; Shi, Yongfang; CrystEngComm 27 (2025) 3378–3385; doi:10.1039/D5CE00016E

data_7250279
_publ_section_title
;
 Cationic substitution engineering induces a new quaternary chalcogenide
 in the A--MIIIA--MIVA--Q system for optical crystal applications
;
_journal_issue                   20
_journal_name_full               CrystEngComm
_journal_page_first              3378
_journal_page_last               3385
_journal_paper_doi               10.1039/D5CE00016E
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'Ga2 Ge6 S16, 2(Cs)'
_chemical_formula_sum            'Cs Ga Ge3 S8'
_chemical_formula_weight         676.8800
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_primary     direct
_audit_creation_date             2024-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-10-17 deposited with the CCDC.	2025-04-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 95.902(5)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   6.3479(4)
_cell_length_b                   16.2352(8)
_cell_length_c                   6.8246(3)
_cell_measurement_reflns_used    3364
_cell_measurement_temperature    150.00(10)
_cell_measurement_theta_max      30.6640
_cell_measurement_theta_min      3.2230
_cell_volume                     699.61(6)
_computing_cell_refinement       'CrysAlisPro 1.171.43.101a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.101a 64-bit (release 13-12-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.101a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.792
_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    -27.00  64.00   0.50    0.61    --   -5.57  77.00  20.00  182
  2  \w    -68.00 -41.00   0.50    0.61    --   -5.57 -77.00-105.00   54
  3  \w    -17.00  28.00   0.50    0.61    --   -5.57 -99.00-150.00   90
  4  \w    -35.00  16.00   0.50    0.61    --   -5.57 -77.00-105.00  102
  5  \w     -8.00  28.00   0.50    0.61    --   -5.57 -99.00  90.00   72
  6  \w    -18.00  24.00   0.50    0.61    --   -5.57 -99.00 120.00   84
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0802469000
_diffrn_orient_matrix_UB_12      0.0267302000
_diffrn_orient_matrix_UB_13      0.0275494000
_diffrn_orient_matrix_UB_21      -0.0781661000
_diffrn_orient_matrix_UB_22      -0.0249615000
_diffrn_orient_matrix_UB_23      -0.0527432000
_diffrn_orient_matrix_UB_31      -0.0082194000
_diffrn_orient_matrix_UB_32      -0.0238902000
_diffrn_orient_matrix_UB_33      0.0859088000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0352
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.792
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       7
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            6496
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.792
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         30.781
_diffrn_reflns_theta_min         2.509
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'Mova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    12.000
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46617
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.101a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    3.213
_exptl_crystal_description       plate
_exptl_crystal_F_000             620
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.130
_exptl_crystal_size_min          0.110
_refine_diff_density_max         1.544
_refine_diff_density_min         -2.186
_refine_diff_density_rms         0.285
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     64
_refine_ls_number_reflns         1736
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.049
_refine_ls_R_factor_all          0.0643
_refine_ls_R_factor_gt           0.0484
_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^)+(0.0888P)^2^+4.8030P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1346
_refine_ls_wR_factor_ref         0.1489
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1397
_reflns_number_total             1736
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00016e2.cif
_cod_data_source_block           cs-1_auto
_cod_depositor_comments          'Adding full bibliography for 7250279.cif.'
_cod_database_code               7250279
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'Cs Ga S'
_shelx_estimated_absorpt_t_max   0.352
_shelx_estimated_absorpt_t_min   0.250
_diffrn_oxdiff_digest_frames
;
01d0526b281fa21ff13add85ffddf42d380058463fb
;
_diffrn_oxdiff_digest_hkl
;
011995acea5120238d44f695af14fc4f0af14d
;
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     26.32
_olex2_refinement_description
;
1. Shared sites
{Ga1, Ge1}
{Ga2, Ge2}
2. Uiso/Uaniso restraints and constraints
Uanis(Ge1) = Uanis(Ga1)
Uanis(Ga1) = Uanis(Ge1)
Uanis(Ga2) = Uanis(Ge2)
3. Others
 Fixed Sof: Ge1(0.75) Ge2(0.75) Ga1(0.25) Ga2(0.25) Cs1(0.5)
;
_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 1.747
_oxdiff_exptl_absorpt_empirical_full_min 0.737