The effect of viologen counterions on the topologies of La(iii)–tetraoxolene metal–organic frameworks
Feng, Yuying; Hua, Carol; van Koeverden, Martin P.; CrystEngComm 27 (2025) 2559–2569; doi:10.1039/D5CE00026B

data_7250137
_publ_section_title
;
 The effect of viologen counterions on the topologies of
 La(iii)--tetraoxolene metal--organic frameworks
;
_journal_issue                   16
_journal_name_full               CrystEngComm
_journal_page_first              2559
_journal_page_last               2569
_journal_paper_doi               10.1039/D5CE00026B
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C12 H2 Br4 La O9, 0.5(C14 H12 N2),  10(H2 O)'
_chemical_formula_sum            'C19 H28 Br4 La N O19'
_chemical_formula_weight         1032.97
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-07
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7181)
;
_audit_update_record
;
2025-03-17 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
_cell_angle_alpha                97.055(2)
_cell_angle_beta                 94.584(2)
_cell_angle_gamma                107.293(3)
_cell_formula_units_Z            2
_cell_length_a                   10.7111(3)
_cell_length_b                   11.8605(4)
_cell_length_c                   13.2161(4)
_cell_measurement_reflns_used    17983
_cell_measurement_temperature    101(2)
_cell_measurement_theta_max      79.0400
_cell_measurement_theta_min      3.4080
_cell_volume                     1578.87(9)
_computing_cell_refinement       'CrysAlisPro 1.171.43.90 (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.111a 64-bit (release 27-02-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.90 (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_environment      N~2~
_diffrn_ambient_temperature      101(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.971
_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    -49.00  24.00   0.50    0.50    --  -47.86  43.00-101.00  146
  2  \w   -119.00 -37.00   0.50    0.50    --  -47.86 -43.00 107.00  164
  3  \w   -119.00 -37.00   0.50    0.50    --  -47.86 -43.00 107.00  164
  4  \w    -23.00  49.00   0.50    0.50    --   47.86 -43.00 107.00  144
  5  \w   -161.00 -79.00   0.50    2.00    --  -90.00 -43.00 107.00  164
  6  \w    -49.00 -18.00   0.50    2.00    --  -90.00  43.00-101.00   62
  7  \w    101.00 178.00   0.50    2.00    --  111.50  43.00-101.00  154
  8  \w    -30.00  27.00   0.50    0.50    --  -47.86  19.00-180.00  114
  9  \w   -119.00 -26.00   0.50    0.50    --  -47.86 -77.00 -60.00  186
 10  \w    -86.00 -13.00   0.50    0.50    --  -47.86 125.00 -60.00  146
 11  \w     38.00 119.00   0.50    0.50    --   47.86  43.00-101.00  162
 12  \w     34.00  92.00   0.50    0.50    --   47.86-125.00 -30.00  116
 13  \w     -1.00  79.00   0.50    0.50    --   47.86 -99.00-180.00  160
 14  \w     34.00  92.00   0.50    0.50    --   47.86-125.00 150.00  116
 15  \w    -71.00 -18.00   0.50    2.00    --  -90.00  61.00  60.00  106
 16  \w     40.00  69.00   0.50    2.00    --  111.50 -61.00-120.00   58
 17  \w     44.00  70.00   0.50    2.00    --  111.50 -77.00  60.00   52
 18  \w    108.00 172.00   0.50    2.00    --  111.50  15.00   0.00  128
 19  \w    106.00 140.00   0.50    2.00    --  111.50  30.00-150.00   68
 20  \w    153.00 178.00   0.50    2.00    --  111.50  30.00-150.00   50
 21  \w    101.00 178.00   0.50    2.00    --  111.50  45.00 -60.00  154
 22  \w     45.00  71.00   0.50    2.00    --  111.50 -61.00 -90.00   52
 23  \w     40.00  70.00   0.50    2.00    --  111.50 -61.00 -60.00   60
 24  \w    104.00 165.00   0.50    2.00    --  111.50  30.00  60.00  122
 25  \w     47.00 103.00   0.50    2.00    --  111.50 -94.00-120.00  112
 26  \w     79.00 111.00   0.50    2.00    --  111.50-125.00-150.00   64
 27  \w     40.00  65.00   0.50    2.00    --  111.50 -61.00  60.00   50
 28  \w     48.00 105.00   0.50    2.00    --  111.50 -94.00-150.00  114
 29  \w     40.00 102.00   0.50    2.00    --  111.50 -94.00 -90.00  124
 30  \w     48.00  77.00   0.50    2.00    --  111.50-125.00-180.00   58
 31  \w     86.00 111.00   0.50    2.00    --  111.50-125.00-180.00   50
 32  \w    102.00 169.00   0.50    2.00    --  111.50  15.00  30.00  134
 33  \w     50.00  76.00   0.50    2.00    --  111.50 -94.00  60.00   52
 34  \w     79.00 105.00   0.50    2.00    --  111.50 -94.00  60.00   52
 35  \w     44.00  71.00   0.50    2.00    --  111.50 -61.00 -30.00   54
 36  \w     45.00  70.00   0.50    2.00    --  111.50 -94.00   0.00   50
 37  \w     74.00 100.00   0.50    2.00    --  111.50 -94.00   0.00   52
 38  \w     73.00 105.00   0.50    2.00    --  111.50 -94.00  30.00   64
 39  \w    104.00 137.00   0.50    2.00    --  111.50  77.00 -90.00   66
 40  \w    107.00 178.00   0.50    2.00    --  111.50  30.00-120.00  142
 41  \w     58.00 108.00   0.50    2.00    --  111.50-125.00   0.00  100
 42  \w    141.00 177.00   0.50    2.00    --  111.50  77.00 -90.00   72
 43  \w     68.00 104.00   0.50    2.00    --  111.50 -94.00 -30.00   72
 44  \w     41.00  97.00   0.50    2.00    --  111.50 -94.00-180.00  112
 45  \w     42.00  69.00   0.50    2.00    --  111.50 -77.00  90.00   54
 46  \w     42.00  69.00   0.50    2.00    --  111.50 -61.00-150.00   54
 47  \w     40.00  65.00   0.50    2.00    --  111.50 -61.00   0.00   50
 48  \w     41.00  66.00   0.50    2.00    --  111.50 -94.00  90.00   50
 49  \w     77.00 102.00   0.50    2.00    --  111.50 -94.00  90.00   50
 50  \w     50.00 105.00   0.50    2.00    --  111.50 -94.00 120.00  110
 51  \w     65.00 105.00   0.50    2.00    --  111.50 -94.00 150.00   80
 52  \w     42.00  67.00   0.50    2.00    --  111.50 -94.00  30.00   50
 53  \w     42.00  70.00   0.50    2.00    --  111.50-125.00-150.00   56
;
_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      0.1090644000
_diffrn_orient_matrix_UB_12      0.0598157000
_diffrn_orient_matrix_UB_13      -0.0631574000
_diffrn_orient_matrix_UB_21      0.0501743000
_diffrn_orient_matrix_UB_22      -0.1092726000
_diffrn_orient_matrix_UB_23      -0.0038710000
_diffrn_orient_matrix_UB_31      -0.0928809000
_diffrn_orient_matrix_UB_32      -0.0586325000
_diffrn_orient_matrix_UB_33      -0.1000177000
_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  0.0515
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.971
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            26037
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.971
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.853
_diffrn_reflns_theta_min         3.395
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    17.123
_exptl_absorpt_correction_T_max  0.741
_exptl_absorpt_correction_T_min  0.305
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.90 (Rigaku Oxford Diffraction, 2023)
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            'clear reddish violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.173
_exptl_crystal_description       needle
_exptl_crystal_F_000             996
_exptl_crystal_size_max          0.097
_exptl_crystal_size_mid          0.039
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.859
_refine_diff_density_min         -2.257
_refine_diff_density_rms         0.149
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.118
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     469
_refine_ls_number_reflns         6679
_refine_ls_number_restraints     212
_refine_ls_restrained_S_all      1.102
_refine_ls_R_factor_all          0.0399
_refine_ls_R_factor_gt           0.0382
_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^)+(0.0582P)^2^+3.5753P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1057
_refine_ls_wR_factor_ref         0.1070
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6341
_reflns_number_total             6679
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5ce00026b2.cif
_cod_data_source_block           MPVK-MPF-2-044C_1_1-mask_smrt_abs_a
_cod_depositor_comments
'Adding full bibliography for 7250132--7250140.cif.'
_cod_database_code               7250137
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C19 H28 Br4 La N O19'
_chemical_oxdiff_usercomment     'Small maroon block'
_shelx_estimated_absorpt_t_max   0.628
_shelx_estimated_absorpt_t_min   0.279
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups, H35 of C35, H36 of C36, H26 of C26
 At 1.5 times of:
  All O(H,H) groups, H31 of C31, H27 of C27
2. Restrained distances
 C35-C36
 1.35 with sigma of 0.02
 C28-C35 = C36-C37
 1.43 with sigma of 0.02
 C32-C33
 1.51 with sigma of 0.02
 N30-C32 = N34-C33
 1.48 with sigma of 0.02
 C29-C28 = C37-C29_$1
 1.36 with sigma of 0.02
 C29_$1-N34 = C29-N30
 1.4 with sigma of 0.04
 N30-C31 = N34-C27_$1
 1.35 with sigma of 0.04
 H27-C27
 0.93 with sigma of 0.001
 H27-C26
 1.992 with sigma of 0.001
 H27-C28
 2.075 with sigma of 0.001
 H31-C31
 0.93 with sigma of 0.0005
 H31-C26
 2.021 with sigma of 0.0005
 H31-N30
 1.959 with sigma of 0.0005
 H31-H26
 2.32 with sigma of 0.0005
 O25-H25A = O25-H25B
 0.84 with sigma of 0.02
 H25A-H25B
 1.34 with sigma of 0.04
 O38-H38A = O38-H38B
 0.84 with sigma of 0.02
 H38A-H38B
 1.34 with sigma of 0.04
 O39-H39A = O39-H39B
 0.84 with sigma of 0.02
 H39A-H39B
 1.34 with sigma of 0.04
 O41-H41A = O41-H41B
 0.84 with sigma of 0.02
 H41A-H41B
 1.34 with sigma of 0.04
 O42-H42A = O42-H42B
 0.84 with sigma of 0.02
 H42A-H42B
 1.34 with sigma of 0.04
 O43-H43A = O43-H43B
 0.84 with sigma of 0.02
 H43A-H43B
 1.34 with sigma of 0.04
 O44-H44A = O44-H44B
 0.84 with sigma of 0.02
 H44A-H44B
 1.34 with sigma of 0.04
 O45-H45A = O45-H45B
 0.84 with sigma of 0.02
 H45A-H45B
 1.34 with sigma of 0.04
 O46-H46A = O46-H46B
 0.84 with sigma of 0.02
 H46A-H46B
 1.34 with sigma of 0.04
 H43A-O44
 2.12 with sigma of 0.04
 O5-H44A
 2.06 with sigma of 0.04
 H25A-H45B
 -2.2 with sigma of 0.02
 H38B-H45A
 -2.2 with sigma of 0.02
 C27-C28 \\sim C37-C31_$1
 with sigma of 0.02
 C28-C29 \\sim C37-C29_$1
 with sigma of 0.02
 C26-C28 \\sim C37-C26_$1
 with sigma of 0.04
 C29-N30 \\sim C29_$1-N34
 with sigma of 0.02
 N30-C31 \\sim N34-C27_$1
 with sigma of 0.02
 C28-N30 \\sim C37-N34
 with sigma of 0.04
3. Restrained planarity
 C26, C27, C28, C29, N30, C31
 with sigma of 0.1
 C36, C35, C28, C29, C29_$1, C37
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C26 \\sim C27 \\sim C29 \\sim C31 \\sim C28 \\sim N30 \\sim C32 \\sim C35 \\sim
N34 \\sim C33 \\sim C36 \\sim C37: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(N30) = Uanis(C37)
Uanis(C28) = Uanis(N34)
Uanis(C32) = Uanis(C36)
Uanis(C33) = Uanis(C35)
5. Rigid body (RIGU) restrains
 C26, C27, C29, C31, C28, N30, C32, C33, N34, C35, C36, C37
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: C28(0.5) N30(0.5) C32(0.5) H32A(0.5) H32B(0.5) C33(0.5) H33A(0.5)
 H33B(0.5) N34(0.5) C35(0.5) H35(0.5) C36(0.5) H36(0.5) C37(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C32(H32A,H32B), C33(H33A,H33B)
7.b Aromatic/amide H refined with riding coordinates:
 C35(H35), C36(H36), C26(H26)
;
_shelx_res_checksum              8617
_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 1.796
_oxdiff_exptl_absorpt_empirical_full_min 0.591