Single-Crystal Ca₃Ge₃O₉ Calcium Germanate: Structure, Thermal and Optical Properties from Experiment and First-Principles
Zhang, Hengyuan; Wu, Jipeng; Ma, Yidong; Chen, Feifei; Zhao, Xian; CrystEngComm  (2025) –; doi:10.1039/D5CE00913H

data_7251354
_publ_section_title
;
 Single-Crystal Ca&#x2083;Ge&#x2083;O&#x2089; Calcium Germanate:
 Structure, Thermal and Optical Properties from Experiment and
 First-Principles
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D5CE00913H
_journal_year                    2025
_chemical_formula_moiety         'Ca3 Ge3 O9'
_chemical_formula_sum            'Ca3 Ge3 O9'
_chemical_formula_weight         482.01
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_primary     dual
_audit_creation_date             2024-07-15
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-11-18 deposited with the CCDC.	2025-11-19 downloaded from the CCDC.
;
_cell_angle_alpha                103.497(2)
_cell_angle_beta                 94.404(2)
_cell_angle_gamma                90.088(2)
_cell_formula_units_Z            2
_cell_length_a                   7.2858(2)
_cell_length_b                   7.55010(10)
_cell_length_c                   8.1252(2)
_cell_measurement_reflns_used    5615
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      76.7610
_cell_measurement_theta_min      5.5820
_cell_volume                     433.241(17)
_computing_cell_refinement       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.118a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.993
_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    -34.00  20.00   0.50    0.05    --   42.82 -38.00 150.00  108
  2  \w    -73.00 -23.00   0.50    0.05    --  -42.82  95.00  70.00  100
  3  \w    -12.00  27.00   0.50    0.05    --  -42.82  95.00  70.00   78
  4  \w    -71.00 -31.00   0.50    0.05    -- -105.00  61.00-180.00   80
  5  \w    -27.00  40.00   0.50    0.05    --   42.82 -38.00-180.00  134
  6  \w    -37.00  21.00   0.50    0.05    --   42.82 -19.00-120.00  116
  7  \w     92.00 175.00   0.50    0.05    --  112.94  61.00 -30.00  166
  8  \w     86.00 173.00   0.50    0.05    --  112.94  95.00  70.00  174
  9  \w     88.00 114.00   0.50    0.05    --  112.94  77.00-150.00   52
 10  \w    125.00 176.00   0.50    0.05    --  112.94  77.00-150.00  102
 11  \w     40.00  69.00   0.50    0.05    --  112.94 -61.00-180.00   58
 12  \w     71.00  96.00   0.50    0.05    --  112.94 -77.00 -90.00   50
 13  \w     78.00 105.00   0.50    0.05    --  112.94 -77.00 -30.00   54
 14  \w     41.00  67.00   0.50    0.05    --  112.94 -61.00 -30.00   52
 15  \w     46.00  71.00   0.50    0.05    --  112.94 -77.00 -30.00   50
 16  \w     42.00  70.00   0.50    0.05    --  112.94 -61.00   0.00   56
 17  \w     42.00  70.00   0.50    0.05    --  112.94 -61.00  30.00   56
 18  \w     40.00  71.00   0.50    0.05    --  112.94 -77.00 120.00   62
 19  \w    -22.00  73.00   0.50    0.05    --   42.82 -95.00 -40.00  190
 20  \w     49.00 103.00   0.50    0.05    --  112.94 -95.00-150.00  108
 21  \w     70.00 100.00   0.50    0.05    --  112.94 -95.00 -40.00   60
 22  \w   -112.00 -36.00   0.50    0.05    -- -105.00 125.00-120.00  152
 23  \w   -108.00 -72.00   0.50    0.05    -- -105.00 125.00  90.00   72
 24  \w   -112.00 -71.00   0.50    0.05    -- -105.00 125.00 150.00   82
 25  \w    -98.00 -66.00   0.50    0.05    -- -105.00  95.00  70.00   64
 26  \w    -64.00 -32.00   0.50    0.05    -- -105.00  95.00  70.00   64
 27  \w   -124.00 -99.00   0.50    0.05    -- -105.00 -45.00 150.00   50
 28  \w   -162.00-129.00   0.50    0.05    -- -105.00 -77.00 -90.00   66
 29  \w   -119.00 -84.00   0.50    0.05    -- -105.00 -77.00 -90.00   70
 30  \w   -172.00 -85.00   0.50    0.05    -- -105.00 -61.00-120.00  174
 31  \w   -144.00-115.00   0.50    0.05    -- -105.00 -77.00-180.00   58
 32  \w   -109.00 -84.00   0.50    0.05    -- -105.00 -77.00-180.00   50
 33  \w   -170.00-128.00   0.50    0.05    -- -105.00 -45.00 150.00   84
 34  \w   -140.00 -88.00   0.50    0.05    -- -105.00 -95.00 -40.00  104
 35  \w   -120.00 -43.00   0.50    0.05    --  -42.82-178.00 -30.00  154
 36  \w    -83.00 -49.00   0.50    0.05    --  -42.82-178.00 120.00   68
 37  \w     82.00 107.00   0.50    0.05    --   43.80 178.00  30.00   50
 38  \w    -33.00  -7.00   0.50    0.05    --   43.80 -19.00 -60.00   52
 39  \w   -124.00 -99.00   0.50    0.05    -- -105.00 142.00   2.22   50
 40  \w   -112.00 -87.00   0.50    0.05    -- -105.00 125.00 120.00   50
 41  \w   -118.00 -21.00   0.50    0.05    --  -43.80 -57.00  30.00  194
 42  \w   -118.00 -21.00   0.50    0.05    --  -43.80 -57.00-180.00  194
 43  \w   -118.00 -21.00   0.50    0.05    --  -43.80 -57.00 -30.00  194
 44  \w   -118.00 -21.00   0.50    0.05    --  -43.80 -57.00  90.00  194
 45  \w    -43.00  33.00   0.50    0.05    --  -43.80  38.00  90.00  152
 46  \w   -118.00 -15.00   0.50    0.05    --  -43.80 -77.00  30.00  206
 47  \w   -118.00 -15.00   0.50    0.05    --  -43.80 -77.00-180.00  206
 48  \w   -118.00 -15.00   0.50    0.05    --  -43.80 -77.00 -60.00  206
 49  \w   -118.00 -15.00   0.50    0.05    --  -43.80 -77.00  90.00  206
 50  \w   -118.00 -21.00   0.50    0.05    --  -43.80 -57.00 -60.00  194
 51  \w     15.00 118.00   0.50    0.05    --   43.80  77.00 -60.00  206
 52  \w   -175.00-125.00   0.50    0.05    -- -105.00 -77.00   0.00  100
 53  \w   -175.00 -81.00   0.50    0.05    -- -105.00 -61.00  90.00  188
 54  \w   -175.00 -76.00   0.50    0.05    -- -105.00 -76.00-145.50  198
 55  \w   -175.00 -76.00   0.50    0.05    -- -105.00 -77.00 -30.00  198
 56  \w   -175.00 -82.00   0.50    0.05    -- -105.00 -42.00 117.18  186
 57  \w     91.00 176.00   0.50    0.05    --  113.59  61.00  30.00  170
 58  \w     91.00 176.00   0.50    0.05    --  113.59  61.00   0.00  170
 59  \w    -49.00 -24.00   0.50    0.05    --  -43.80  95.00  70.00   50
 60  \w    -49.00 -24.00   0.50    0.05    --  -43.80  95.00  70.00   50
 61  \w     49.00  74.00   0.50    0.05    --  113.59 -94.00 -39.00   50
 62  \w    -41.00 -15.00   0.50    0.05    --  -43.80 -77.00-150.00   52
 63  \w   -109.00 -83.00   0.50    0.05    -- -105.00 -61.00-180.00   52
 64  \w   -107.00 -82.00   0.50    0.05    -- -105.00 -46.00 109.25   50
 65  \w   -165.00-139.00   0.50    0.05    -- -105.00 -61.00-180.00   52
 66  \w   -106.00 -81.00   0.50    0.05    -- -105.00 -65.00 111.63   50
 67  \w   -168.00-143.00   0.50    0.05    -- -105.00 -61.00  30.00   50
 68  \w   -106.00 -81.00   0.50    0.05    -- -105.00 -61.00  30.00   50
 69  \w   -102.00 -76.00   0.50    0.05    -- -105.00 -77.00-120.00   52
 70  \w   -155.00-129.00   0.50    0.05    -- -105.00 -74.00  12.43   52
 71  \w   -102.00 -77.00   0.50    0.05    -- -105.00 -74.00  12.43   50
 72  \w    -71.00 -46.00   0.50    0.05    -- -105.00  61.00 -90.00   50
 73  \w   -105.00 -79.00   0.50    0.05    -- -105.00 -72.00 162.24   52
 74  \w   -102.00 -76.00   0.50    0.05    -- -105.00 -77.00  60.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0942372000
_diffrn_orient_matrix_UB_12      0.0506418000
_diffrn_orient_matrix_UB_13      0.1675957000
_diffrn_orient_matrix_UB_21      0.1317952000
_diffrn_orient_matrix_UB_22      0.1658326000
_diffrn_orient_matrix_UB_23      0.0629795000
_diffrn_orient_matrix_UB_31      -0.1369042000
_diffrn_orient_matrix_UB_32      0.1182603000
_diffrn_orient_matrix_UB_33      -0.0787805000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0608
_diffrn_reflns_av_unetI/netI     0.0351
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            7948
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        66.596
_diffrn_reflns_theta_max         66.596
_diffrn_reflns_theta_min         5.617
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    28.255
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.17492
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.118a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    3.695
_exptl_crystal_description       block
_exptl_crystal_F_000             456
_exptl_crystal_recrystallization_method 'From the Melt'
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.897
_refine_diff_density_min         -1.010
_refine_diff_density_rms         0.224
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    undef
_refine_ls_matrix_type           full
_refine_ls_number_parameters     136
_refine_ls_number_reflns         1524
_refine_ls_number_restraints     6
_refine_ls_restrained_S_all      1.089
_refine_ls_R_factor_all          0.0320
_refine_ls_R_factor_gt           0.0295
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0483P)^2^+0.0111P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0747
_refine_ls_wR_factor_ref         0.0760
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1422
_reflns_number_total             1524
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00913h1.cif
_cod_data_source_block           8133_auto
_cod_database_code               7251354
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CacoBiGe
_shelx_estimated_absorpt_t_max   0.164
_shelx_estimated_absorpt_t_min   0.080
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
Uanis(O3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
;
_shelx_res_checksum              7937
_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 5.103
_oxdiff_exptl_absorpt_empirical_full_min 0.574