Proton-conducting coordination polymers formed from bipyridine phosphonate ligands
Ramteke, Prajakta Mohan; Plecháček, Tomáš; Kloda, Matous; Rohlíček, Jan; Vykydalová, Anna; Melanova, Klara; Bavol, Dmytro; Škoch, Karel; Taddei, Marco; Demel, Jan; Hynek, Jan; Dalton Transactions  (2026) –; doi:10.1039/D5DT02997J

data_7720592
_publ_section_title
;
 Proton-conducting coordination polymers formed from bipyridine
 phosphonate ligands.
;
_journal_issue                   14
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5622
_journal_page_last               5634
_journal_paper_doi               10.1039/d5dt02997j
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety
'C40 H58 Ca9 N8 O65 P16, 5[H2O], 4.5[H2O], 1[H2O]'
_chemical_formula_sum            'C40 H79 Ca9 N8 O75.5 P16'
_chemical_formula_weight         2736.35
_chemical_name_systematic
catena-(\m-4,4?-bipyridine-3,3?,5,5?-tetraphosphonato)-aqua-calcium(II)
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-10-19
_audit_creation_method
;
Olex2 1.5-ac7-014
(compiled 2025.02.27 svn.r6f4c0eaf for Rigaku Oxford Diffraction, GUI svn.r7171)
;
_audit_update_record
;
2025-10-31 deposited with the CCDC.	2026-03-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 89.96(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6870(16)
_cell_length_b                   26.63(5)
_cell_length_c                   26.88(3)
_cell_measurement_reflns_used    5233
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      65.8590
_cell_measurement_theta_min      3.2460
_cell_volume                     9797(2)
_computing_cell_refinement       'CrysAlisPro 1.171.44.98a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 44.108a 64-bit (release 25-04-2025))'
_computing_data_reduction        'CrysAlisPro 1.171.44.98a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5-ac7-014 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac7-014 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.931
_diffrn_measured_fraction_theta_max 0.927
_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   -116.00 -89.00   0.50   18.00    --  -49.25 -77.00 -30.00   54
  2  \w    -15.00  24.00   0.50   18.00    --  -49.25  19.00-120.00   78
  3  \w   -121.00 -89.00   0.50   18.00    --  -49.25 -77.00 -90.00   64
  4  \w    -21.00  24.00   0.50   18.00    --  -49.25  19.00 120.00   90
  5  \w    -23.00  18.00   0.50   18.00    --  -49.25  19.00-180.00   82
  6  \w    -41.00  12.00   0.50   18.00    --  -49.25  37.00-150.00  106
  7  \w   -143.00 -97.00   0.50   72.00    --  -90.00 -77.00 -60.00   92
  8  \w    -66.00 -20.00   0.50   72.00    --  -90.00  57.00   0.00   92
  9  \w    -66.00 -20.00   0.50   72.00    --  -90.00  57.00 -30.00   92
 10  \w   -111.00 -18.00   0.50   72.00    --  -90.00  77.00-120.00  186
 11  \w    -60.00 -19.00   0.50   72.00    --  -90.00  57.00  30.00   82
 12  \w     54.00 116.00   0.50   72.00    --  107.44-125.00  30.00  124
 13  \w     36.00  62.00   0.50   72.00    --  107.44 -57.00 120.00   52
 14  \w     37.00 109.00   0.50   72.00    --  107.44-125.00 150.00  144
 15  \w    100.00 178.00   0.50   72.00    --  107.44  37.00-150.00  156
;
_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      -0.1014957000
_diffrn_orient_matrix_UB_12      0.0213934000
_diffrn_orient_matrix_UB_13      0.0119257000
_diffrn_orient_matrix_UB_21      0.0397375000
_diffrn_orient_matrix_UB_22      0.0526125000
_diffrn_orient_matrix_UB_23      -0.0082300000
_diffrn_orient_matrix_UB_31      -0.0273775000
_diffrn_orient_matrix_UB_32      -0.0031125000
_diffrn_orient_matrix_UB_33      -0.0564386000
_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  0.2216
_diffrn_reflns_av_unetI/netI     0.2092
_diffrn_reflns_Laue_measured_fraction_full 0.931
_diffrn_reflns_Laue_measured_fraction_max 0.927
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            51664
_diffrn_reflns_point_group_measured_fraction_full 0.931
_diffrn_reflns_point_group_measured_fraction_max 0.927
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.251
_diffrn_reflns_theta_min         2.336
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    7.829
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.375
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.98a (Rigaku Oxford Diffraction, 2025)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
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    1.855
_exptl_crystal_description       needle
_exptl_crystal_F_000             5596
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.04
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.560
_refine_diff_density_min         -1.235
_refine_diff_density_rms         0.226
_refine_ls_extinction_coef       0.00023(6)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1283
_refine_ls_number_reflns         16655
_refine_ls_number_restraints     14
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.2430
_refine_ls_R_factor_gt           0.1358
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3313
_refine_ls_wR_factor_ref         0.4053
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6793
_reflns_number_total             16655
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02997j2.cif
_cod_data_source_block           ppivca_new_mp
_cod_depositor_comments
'Adding full bibliography for 7720590--7720593.cif.'
_cod_original_cell_volume        9797(21)
_cod_original_formula_sum        'C40 H79 Ca9 N8 O75.50 P16'
_cod_database_code               7720592
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C40 H58 N8 O76 P16 Ca9 '
_shelx_estimated_absorpt_t_max   0.799
_shelx_estimated_absorpt_t_min   0.218
_diffrn_oxdiff_digest_hkl
;
43176fb0ff92ab12cd4506671336803600efc2
;
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.9618(12)
 0.0382(12)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H7W of O7W
 At 1.5 times of:
  All O(H,H) groups, H8D of O8D, H8A of O8A, H9C of O9C, H3D of O3D, H2A of
  O2A, H9B of O9B, H5D of O5D, H6B of O6B, H5A of O5A, H12D of O12D, H11C of
  O11C, H12B of O12B, H6C of O6C, H12W of O12W, H1B of O2B, H10c of O10A, H3C
  of O3C
3. Restrained distances
 O12W-H12W
 0.87 with sigma of 0.02
 Ca1-H1Wa \\sim Ca1-H1Wb
 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
O2C \\sim O3C \\sim O1C: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
O4A \\sim O3WB \\sim O131: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
O3WB \\sim O3WA: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
Uanis(O3WB) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O3WB) = Uanis(O3WA)
5. Others
 Sof(O3WB)=Sof(H3Wa)=Sof(H3Wb)=1-FVAR(1)
 Sof(O3WA)=Sof(H3Wc)=Sof(H3Wd)=FVAR(1)
6.a Free rotating group:
 O1W(H1Wa,H1Wb)
6.b Rotating group:
 O11W(H11a,H11b), O6W(H6Wa,H6Wb), O16W(H16a,H16b), O5W(H5Wa,H5Wb), O10W(H10a,
 H10b), O8W(H8Wa,H8Wb), O131(H13a,H13b), O4W(H4Wa,H4Wb), O9W(H9Wa,H9Wb),
 O2W(H2Wa,H2Wb), O3WB(H3Wa,H3Wb), O3WA(H3Wc,H3Wd)
6.c Aromatic/amide H refined with riding coordinates:
 O7W(H7W), C9C(H9Ca), C7D(H7D), C9D(H9D), C4C(H4C), C4D(H4D), C2D(H2D),
 C2B(H2B), C7C(H7C), C7B(H7B), C9B(H9Ba), C2C(H2C), C4B(H4B), C9A(H9A),
 C2A(H2Aa), C4A(H4A), C7A(H7A)
6.d Idealised tetrahedral OH refined as rotating group:
 O8D(H8D), O9B(H9B), O9C(H9C), O3D(H3D), O5D(H5D), O2A(H2A), O8A(H8A),
 O11C(H11C), O6B(H6B), O12D(H12D), O6C(H6C), O12B(H12B), O5A(H5A), O2B(H1B),
 O3C(H3C), O10A(H10c)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              67429
_shelx_hkl_checksum              87920
_shelx_fab_checksum              21534
_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 2.659
_oxdiff_exptl_absorpt_empirical_full_min 0.376