Structural variety in calcium metal–organic frameworks with a tetratopic carboxylate ligand
Zhao, Baiwen; Clarkson, Guy J.; Liu, Jie; Le, Thi Huong; Marrot, Jérôme; Millange, Franck; Frigoli, Michel; Walton, Richard I.; CrystEngComm 27 (2025) 2830–2840; doi:10.1039/D5CE00145E

data_7250205
_publ_section_title
;
 Structural variety in calcium metal--organic frameworks with a tetratopic
 carboxylate ligand
;
_journal_issue                   18
_journal_name_full               CrystEngComm
_journal_page_first              2830
_journal_page_last               2840
_journal_paper_doi               10.1039/D5CE00145E
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C114 H74 Ca5 O32, 2(H2 O), 9.8(O)'
_chemical_formula_sum            'C114 H78 Ca5 O43.8'
_chemical_formula_weight         2348.96
_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_hydrogens   mixed
_audit_creation_date             2025-03-03
_audit_creation_method
;
Olex2 1.5
(compiled 2025.02.27 svn.r83f5de26 for OlexSys, GUI svn.r7172)
;
_audit_update_record
;
2025-03-03 deposited with the CCDC.	2025-03-31 downloaded from the CCDC.
;
_cell_angle_alpha                99.017(2)
_cell_angle_beta                 91.928(2)
_cell_angle_gamma                99.224(3)
_cell_formula_units_Z            1
_cell_length_a                   11.0429(4)
_cell_length_b                   14.6332(5)
_cell_length_c                   18.2349(4)
_cell_measurement_reflns_used    15898
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      78.3730
_cell_measurement_theta_min      3.0770
_cell_volume                     2867.36(16)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -79.00  25.00   0.50    5.00    --  -47.37  96.00  41.00  208
  2  \w     -7.00  79.00   0.50    5.00    --   47.37 -96.00 -67.00  172
  3  \w   -163.00 -84.00   0.50   20.00    --  -91.75 -96.00 -67.00  158
  4  \w    -79.00 -19.00   0.50   20.00    --  -91.75  96.00  41.00  120
  5  \w    106.00 178.00   0.50   20.00    --  113.25  96.00  41.00  144
  6  \w     42.00 105.00   0.50   20.00    --  113.25 -96.00 -67.00  126
  7  \w    -14.00  29.00   0.50    5.00    --   18.00  96.00 146.64   86
  8  \w    -16.00  18.00   0.50    5.00    --   18.00 101.00  -6.65   68
  9  \w     -3.00  27.00   0.50    5.00    --   30.00  98.00-116.77   60
 10  \w      7.00  34.00   0.50    5.00    --   38.00  94.00  -1.52   54
 11  \w     14.00  43.00   0.50    5.00    --   42.00  88.00-139.66   58
 12  \w     14.00  43.00   0.50    5.00    --   42.00  88.00 108.05   58
 13  \w     14.00  43.00   0.50    5.00    --   42.00  89.00 -95.53   58
 14  \w     17.00  43.00   0.50    5.00    --   46.00  90.00 120.98   52
 15  \w     17.00  43.00   0.50    5.00    --   46.00  90.00-145.41   52
 16  \w   -120.00 -35.00   0.50    5.00    --  -47.37 -37.00 -60.00  170
 17  \w   -122.00 -35.00   0.50    5.00    --  -47.37 -19.00  60.00  174
 18  \w   -119.00 -25.00   0.50    5.00    --  -47.37 -77.00 -60.00  188
 19  \w   -122.00 -35.00   0.50    5.00    --  -47.37 -19.00 150.00  174
 20  \w   -122.00 -35.00   0.50    5.00    --  -47.37 -19.00   0.00  174
 21  \w    -24.00  62.00   0.50    5.00    --   47.37 -57.00 -60.00  172
 22  \w     25.00 120.00   0.50    5.00    --   47.37  77.00  60.00  190
 23  \w     32.00 126.00   0.50    5.00    --   54.00  76.00 -66.74  188
 24  \w     35.00 131.00   0.50    5.00    --   58.00  77.00-139.74  192
 25  \w     37.00  67.00   0.50    5.00    --   58.00  72.00 129.16   60
 26  \w     36.00  61.00   0.50    5.00    --   58.00  77.00   4.40   50
 27  \w     35.00  61.00   0.50    5.00    --   58.00  77.00  71.79   52
 28  \w    103.00 129.00   0.50    5.00    --   62.00  72.00  27.62   52
 29  \w     39.00  65.00   0.50    5.00    --   62.00  77.00 161.25   52
 30  \w     40.00  66.00   0.50    5.00    --   62.00  75.00 134.96   52
 31  \w     41.00  67.00   0.50    5.00    --   62.00  72.00  27.62   52
 32  \w     41.00  69.00   0.50    5.00    --   62.00  73.00  39.82   56
 33  \w     39.00  66.00   0.50    5.00    --   62.00  77.00 -26.23   54
 34  \w     44.00  69.00   0.50    5.00    --   66.00  77.00-101.72   50
 35  \w     45.00  70.00   0.50    5.00    --   66.00  76.00 -58.88   50
 36  \w     43.00  80.00   0.50    5.00    --   66.00  77.00-112.31   74
 37  \w    111.00 138.00   0.50    5.00    --   66.00  77.00-101.72   54
 38  \w     44.00  80.00   0.50    5.00    --   66.00  76.00 133.34   72
 39  \w    -78.00 -51.00   0.50   20.00    --  -70.00 -67.00-111.59   54
 40  \w     49.00  80.00   0.50    5.00    --   70.00  75.00-150.46   62
 41  \w    -76.00 -50.00   0.50   20.00    --  -70.00 -69.00  -1.55   52
 42  \w     47.00  73.00   0.50    5.00    --   70.00  77.00 166.10   52
 43  \w     48.00  73.00   0.50    5.00    --   70.00  77.00  55.36   50
 44  \w     47.00  74.00   0.50    5.00    --   70.00  77.00-171.69   54
 45  \w     49.00  75.00   0.50    5.00    --   70.00  74.00  84.96   52
 46  \w    -79.00 -53.00   0.50   20.00    --  -74.00 -73.00 -40.00   52
 47  \w   -145.00-110.00   0.50   20.00    --  -74.00 -73.00 -57.69   70
 48  \w    -79.00 -53.00   0.50   20.00    --  -74.00 -73.00 -57.69   52
 49  \w    -81.00 -55.00   0.50   20.00    --  -78.00 -77.00 -56.70   52
 50  \w    -81.00 -56.00   0.50   20.00    --  -78.00 -74.00 176.45   50
 51  \w   -140.00-115.00   0.50   20.00    --  -78.00 -74.00 176.45   50
 52  \w    -81.00 -55.00   0.50   20.00    --  -78.00 -77.00  -9.66   52
 53  \w    -83.00 -57.00   0.50   20.00    --  -78.00 -72.00  21.97   52
 54  \w    -84.00 -57.00   0.50   20.00    --  -78.00 -73.00-138.50   54
 55  \w    -81.00 -55.00   0.50   20.00    --  -78.00 -76.00  98.37   52
 56  \w    -88.00 -62.00   0.50   20.00    --  -82.00 -71.00  50.73   52
 57  \w    -86.00 -60.00   0.50   20.00    --  -82.00 -74.00-113.33   52
 58  \w    -90.00 -63.00   0.50   20.00    --  -82.00 -71.00 130.43   54
 59  \w    -86.00 -61.00   0.50   20.00    --  -82.00 -72.00 -66.45   50
 60  \w    -94.00 -62.00   0.50   20.00    --  -82.00 -69.00 -96.27   64
 61  \w    -88.00 -61.00   0.50   20.00    --  -82.00 -73.00 -74.44   54
 62  \w   -154.00-126.00   0.50   20.00    --  -82.00 -73.00 -74.44   56
 63  \w    -93.00 -66.00   0.50   20.00    --  -86.00 -70.00-101.04   54
 64  \w    -94.00 -68.00   0.50   20.00    --  -90.00 -74.00 132.57   52
 65  \w    -94.00 -69.00   0.50   20.00    --  -91.75 -77.00-150.00   50
 66  \w    -94.00 -69.00   0.50   20.00    --  -91.75 -76.00  43.23   50
 67  \w   -162.00-120.00   0.50   20.00    --  -91.75 -76.00  43.23   84
 68  \w    -94.00 -69.00   0.50   20.00    --  -91.75 -77.00  60.00   50
 69  \w    -99.00 -72.00   0.50   20.00    --  -91.75 -71.00-140.09   54
 70  \w   -163.00-114.00   0.50   20.00    --  -91.75 -77.00  60.00   98
 71  \w    -94.00 -69.00   0.50   20.00    --  -91.75 -77.00-120.00   50
 72  \w   -100.00 -73.00   0.50   20.00    --  -91.75 -66.00  68.69   54
 73  \w    -97.00 -71.00   0.50   20.00    --  -91.75 -71.00-172.71   52
 74  \w   -157.00-131.00   0.50   20.00    --  -91.75 -71.00-140.09   52
 75  \w   -162.00-137.00   0.50   20.00    --  -91.75 -71.00-172.71   50
 76  \w    -97.00 -70.00   0.50   20.00    --  -91.75 -77.00 -90.00   54
 77  \w    -99.00 -72.00   0.50   20.00    --  -91.75 -71.00  -1.73   54
 78  \w    -97.00 -71.00   0.50   20.00    --  -91.75 -73.00-178.78   52
 79  \w   -145.00-119.00   0.50   20.00    --  -91.75 -73.00-178.78   52
 80  \w    -95.00 -69.00   0.50   20.00    --  -91.75 -77.00  30.00   52
 81  \w    -96.00 -70.00   0.50   20.00    --  -91.75 -74.00  -7.31   52
 82  \w   -162.00-136.00   0.50   20.00    --  -91.75 -74.00  -7.31   52
 83  \w    -97.00 -70.00   0.50   20.00    --  -91.75 -75.00 168.39   54
 84  \w    -96.00 -70.00   0.50   20.00    --  -91.75 -74.00-148.67   52
 85  \w    -95.00 -70.00   0.50   20.00    --  -91.75 -75.00  10.88   50
 86  \w    -96.00 -70.00   0.50   20.00    --  -91.75 -74.00 154.64   52
 87  \w   -162.00-135.00   0.50   20.00    --  -91.75 -75.00  10.88   54
 88  \w   -100.00 -74.00   0.50   20.00    --  -91.75 -75.00 -36.09   52
 89  \w    -94.00 -69.00   0.50   20.00    --  -91.75 -77.00 -60.00   50
 90  \w    -96.00 -70.00   0.50   20.00    --  -91.75 -77.00 120.00   52
 91  \w    -95.00 -69.00   0.50   20.00    --  -91.75 -77.00  90.00   52
 92  \w   -162.00-125.00   0.50   20.00    --  -91.75 -75.00 -36.09   74
 93  \w    -96.00 -70.00   0.50   20.00    --  -91.75 -75.00 -20.02   52
 94  \w   -157.00-131.00   0.50   20.00    --  -91.75 -77.00 -60.00   52
 95  \w    -97.00 -71.00   0.50   20.00    --  -91.75 -72.00-109.70   52
 96  \w   -163.00-132.00   0.50   20.00    --  -91.75 -72.00-109.70   62
 97  \w    -97.00 -71.00   0.50   20.00    --  -91.75 -71.00  86.62   52
 98  \w    -97.00 -71.00   0.50   20.00    --  -91.75 -73.00  62.06   52
 99  \w   -108.00 -74.00   0.50   20.00    --  -91.75 -65.00  90.54   68
100  \w    116.00 178.00   0.50   20.00    --  113.25 125.00  60.00  124
101  \w     81.00 109.00   0.50   20.00    --  113.25-125.00-150.00   56
102  \w    150.00 177.00   0.50   20.00    --  113.25  77.00 -60.00   54
103  \w     43.00  78.00   0.50   20.00    --  113.25-125.00-150.00   70
104  \w     91.00 148.00   0.50   20.00    --  113.25  77.00 -60.00  114
105  \w     70.00 105.00   0.50   20.00    --  113.25 -94.00 150.00   70
106  \w    102.00 161.00   0.50   20.00    --  113.25  61.00 120.00  118
107  \w     99.00 177.00   0.50   20.00    --  113.25  61.00-180.00  156
108  \w     97.00 153.00   0.50   20.00    --  113.25  61.00 150.00  112
109  \w     42.00 106.00   0.50   20.00    --  113.25 -94.00   0.00  128
110  \w     42.00  68.00   0.50   20.00    --  113.25 -94.00 150.00   52
111  \w     42.00  96.00   0.50   20.00    --  113.25-125.00 -90.00  108
112  \w     43.00  88.00   0.50   20.00    --  113.25-125.00  60.00   90
113  \w     73.00 111.00   0.50   20.00    --  113.25-125.00-180.00   76
114  \w     42.00  69.00   0.50   20.00    --  113.25-125.00-180.00   54
115  \w     91.00 128.00   0.50   20.00    --  113.25  77.00  90.00   74
116  \w     99.00 171.00   0.50   20.00    --  113.25  61.00 -60.00  144
117  \w    146.00 176.00   0.50   20.00    --  113.25  77.00  30.00   60
118  \w     43.00 105.00   0.50   20.00    --  113.25 -94.00 -30.00  124
119  \w     96.00 138.00   0.50   20.00    --  113.25  77.00  30.00   84
120  \w     92.00 136.00   0.50   20.00    --  113.25  77.00-150.00   88
121  \w     91.00 119.00   0.50   20.00    --  113.25  77.00 -30.00   56
122  \w     73.00 106.00   0.50   20.00    --  113.25 -94.00-120.00   66
123  \w    153.00 178.00   0.50   20.00    --  113.25  77.00-120.00   50
124  \w    142.00 173.00   0.50   20.00    --  113.25  77.00 150.00   62
125  \w     42.00  72.00   0.50   20.00    --  113.25 -61.00-180.00   60
126  \w     43.00 106.00   0.50   20.00    --  113.25 -94.00 -90.00  126
127  \w     92.00 140.00   0.50   20.00    --  113.25  77.00-120.00   96
128  \w     43.00  72.00   0.50   20.00    --  113.25 -61.00  30.00   58
129  \w    105.00 133.00   0.50   20.00    --  113.25  61.00  60.00   56
130  \w     97.00 167.00   0.50   20.00    --  113.25  61.00-120.00  140
131  \w     98.00 171.00   0.50   20.00    --  113.25  61.00  90.00  146
132  \w     92.00 118.00   0.50   20.00    --  113.25  77.00 150.00   52
133  \w     98.00 176.00   0.50   20.00    --  113.25  61.00 -30.00  156
134  \w    135.00 170.00   0.50   20.00    --  113.25  61.00-150.00   70
135  \w    123.00 176.00   0.50   20.00    --  113.25  77.00  60.00  106
136  \w    100.00 131.00   0.50   20.00    --  113.25  61.00-150.00   62
137  \w     43.00 106.00   0.50   20.00    --  113.25 -94.00  90.00  126
138  \w     91.00 118.00   0.50   20.00    --  113.25  77.00  60.00   54
139  \w     47.00 105.00   0.50   20.00    --  113.25 -94.00-150.00  116
140  \w     91.00 133.00   0.50   20.00    --  113.25  77.00-180.00   84
141  \w     97.00 144.00   0.50   20.00    --  113.25  61.00 -90.00   94
142  \w    151.00 178.00   0.50   20.00    --  113.25  77.00   0.00   54
143  \w     91.00 140.00   0.50   20.00    --  113.25  77.00   0.00   98
144  \w     83.00 110.00   0.50   20.00    --  113.25-125.00  90.00   54
145  \w     42.00  68.00   0.50   20.00    --  113.25-125.00  90.00   52
146  \w     93.00 174.00   0.50   20.00    --  113.25  77.00 120.00  162
147  \w     97.00 168.00   0.50   20.00    --  113.25  61.00  30.00  142
148  \w     42.00  55.00   0.50   20.00    --  113.25-125.00 150.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0797
_diffrn_reflns_av_unetI/netI     0.0354
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            81559
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        65.089
_diffrn_reflns_theta_max         65.089
_diffrn_reflns_theta_min         3.102
_exptl_absorpt_coefficient_mu    2.794
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  1.00000
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.360
_exptl_crystal_description       plate
_exptl_crystal_F_000             1212
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.02
_exptl_crystal_size_rad          0.400
_refine_diff_density_max         0.973
_refine_diff_density_min         -1.002
_refine_diff_density_rms         0.102
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     795
_refine_ls_number_reflns         9740
_refine_ls_number_restraints     44
_refine_ls_restrained_S_all      1.050
_refine_ls_R_factor_all          0.0892
_refine_ls_R_factor_gt           0.0749
_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^)+(0.1494P)^2^+3.9564P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2173
_refine_ls_wR_factor_ref         0.2319
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7870
_reflns_number_total             9740
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00145e2.cif
_cod_data_source_block           bwx1ca
_cod_depositor_comments
'Adding full bibliography for 7250204--7250207.cif.'
_cod_original_formula_sum        'C114 H78 Ca5 O43.80'
_cod_database_code               7250205
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C20 H20 O4 Ca'
_chemical_oxdiff_usercomment     'C20 H20 O4 Ca colourless block bwx13'
_shelx_estimated_absorpt_t_max   0.946
_shelx_estimated_absorpt_t_min   0.605
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups, All O(H,H) groups
2. Restrained distances
 Ca3-O2 \\sim Ca3-O20 \\sim Ca1-O22
 with sigma of 0.002
 O15-C13 \\sim O18-C57
 with sigma of 0.002
 O6-C13 \\sim O12-C57
 with sigma of 0.002
 Ca3-O15 \\sim Ca3-O15A
 with sigma of 0.02
 O15-C13 \\sim O15A-C13
 with sigma of 0.02
 O8-C1 \\sim O18-C57
 with sigma of 0.02
3. Rigid bond restraints
 O2, O20
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 O15, O6
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
4. Uiso/Uaniso restraints and constraints
O2 \\sim O20: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
within 2A
O20 \\sim O2: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
O15 \\sim O6: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004 within 2A
O25 \\sim O11 \\sim O24 \\sim O26 \\sim O27: within 2A with sigma of 0.002 and
sigma for terminal atoms of 0.004 within 2A
O15A \\sim O15 \\sim O6: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
Uanis(O25) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O26) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O25) \\sim Ueq, Uanis(O11) \\sim Ueq, Uanis(O26) \\sim Ueq, Uanis(O27)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 O15, O6
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O15, O15A
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
6. Others
 Sof(O15A)=1-FVAR(1)
 Sof(O15)=FVAR(1)
 Fixed Sof: O17(0.65) O9(0.5) O19(0.8) O5(0.35) O21(0.5) O11(0.5) O24(0.5)
 O25(0.5) O26(0.1) O27(0.5)
7.a Free rotating group:
 O3(H3A,H3B)
7.b Rotating group:
 O20(H20A,H20B), O22(H22A,H22B), O2(H2A,H2B)
7.c Aromatic/amide H refined with riding coordinates:
 C14(H14), C16(H16), C26(H26), C30(H30), C34(H34), C38(H38), C40(H40),
 C46(H46), C48(H48), C52(H52), C29(H29), C31(H31), C33(H33), C17(H17), C35(H35),
  C9(H9), C19(H19), C39(H39), C41(H41), C21(H21), C43(H43), C11(H11), C45(H45),
 C23(H23), C47(H47), C49(H49), C25(H25), C51(H51), C53(H53), C55(H55)
7.d Idealised tetrahedral OH refined as rotating group:
 O7(H7)
;
_shelx_res_checksum              42196
_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 1.774
_oxdiff_exptl_absorpt_empirical_full_min 0.648