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_7250135
_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         'C15 H6 Br4 La O9, 0.5(C14 H12 N2), 2(C3 H6 O)'
_chemical_formula_sum            'C28 H24 Br4 La N O11'
_chemical_formula_weight         1009.03
_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             2024-05-01
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-01-07 deposited with the CCDC.	2025-03-20 downloaded from the CCDC.
;
_cell_angle_alpha                109.799(3)
_cell_angle_beta                 90.154(3)
_cell_angle_gamma                108.366(3)
_cell_formula_units_Z            2
_cell_length_a                   10.8019(4)
_cell_length_b                   12.6028(5)
_cell_length_c                   13.3338(5)
_cell_measurement_reflns_used    9579
_cell_measurement_temperature    100.0(3)
_cell_measurement_theta_max      78.5960
_cell_measurement_theta_min      13.1340
_cell_volume                     1608.68(12)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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      100.0(3)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.953
_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     86.00 111.00   0.50    0.20    --  113.25-125.00-180.00   50
  2  \w     48.00  74.00   0.50    0.20    --  113.25-125.00-180.00   52
  3  \w     52.00 109.00   0.50    0.20    --  113.25-125.00 -60.00  114
  4  \w     55.00 106.00   0.50    0.20    --  113.25-105.00  58.77  102
  5  \w     45.00  82.00   0.50    0.20    --  113.25-125.00 120.00   74
  6  \w     48.00  92.00   0.50    0.20    --  113.25-125.00  60.00   88
  7  \w     65.00 106.00   0.50    0.20    --  113.25-102.00 -39.00   82
  8  \w     81.00 106.00   0.50    0.20    --  113.25 -94.00-150.00   50
  9  \w     42.00  77.00   0.50    0.20    --  113.25 -94.00-150.00   70
 10  \w     53.00 107.00   0.50    0.20    --  113.25-103.00-172.15  108
 11  \w      9.00  74.00   0.50    0.10    --   47.26-102.00 -39.00  130
 12  \w     58.00  91.00   0.50    0.20    --  113.25 -94.00   0.00   66
 13  \w     73.00 106.00   0.50    0.20    --  113.25 -94.00  60.00   66
 14  \w     71.00 104.00   0.50    0.20    --  113.25 -94.00  90.00   66
 15  \w     43.00  68.00   0.50    0.20    --  113.25 -61.00  90.00   50
 16  \w     43.00  70.00   0.50    0.20    --  113.25 -61.00 -30.00   54
 17  \w     67.00  92.00   0.50    0.20    --  113.25 -77.00 -60.00   50
 18  \w     47.00  91.00   0.50    0.20    --  113.25 -77.00 -90.00   88
 19  \w     42.00  67.00   0.50    0.20    --  113.25 -61.00-150.00   50
 20  \w    124.00 166.00   0.50    0.20    --  113.25  15.00 -90.00   84
 21  \w    137.00 171.00   0.50    0.20    --  113.25  15.00-150.00   68
 22  \w    105.00 165.00   0.50    0.20    --  113.25  30.00   0.00  120
 23  \w    100.00 127.00   0.50    0.20    --  113.25  15.00-150.00   54
 24  \w     43.00 116.00   0.50    0.10    --   47.26  38.00  90.00  146
 25  \w    127.00 152.00   0.50    0.20    --  113.25  45.00 120.00   50
 26  \w     99.00 172.00   0.50    0.20    --  113.25  77.00  90.00  146
 27  \w    138.00 165.00   0.50    0.20    --  113.25 102.00  63.00   54
 28  \w     95.00 151.00   0.50    0.20    --  113.25 125.00   0.00  112
 29  \w     95.00 159.00   0.50    0.20    --  113.25 125.00 -30.00  128
 30  \w    103.00 177.00   0.50    0.20    --  113.25 125.00 -90.00  148
 31  \w    -43.00  15.00   0.50    0.10    --  -47.26  38.00  30.00  116
 32  \w    -21.00  21.00   0.50    0.10    --  -47.26  19.00 150.00   84
 33  \w    -21.00  28.00   0.50    0.10    --  -47.26  19.00  90.00   98
 34  \w    -41.00  10.00   0.50    0.10    --  -47.26 102.00  63.00  102
 35  \w    -72.00 -46.00   0.50    0.10    --  -47.26 102.00  63.00   52
 36  \w    -75.00 -50.00   0.50    0.20    --  -91.75 102.00  63.00   50
 37  \w    -63.00 -23.00   0.50    0.20    --  -91.75  61.00  60.00   80
 38  \w    -50.00 -20.00   0.50    0.20    --  -91.75  45.00   0.00   60
 39  \w    -51.00 -24.00   0.50    0.20    --  -91.75  45.00 -90.00   54
 40  \w    -46.00 -20.00   0.50    0.20    --  -91.75  45.00-150.00   52
 41  \w   -156.00-129.00   0.50    0.20    --  -91.75-102.00 -39.00   54
 42  \w   -116.00 -48.00   0.50    0.10    --  -47.26 -38.00 -30.00  136
 43  \w   -113.00 -86.00   0.50    0.20    --  -91.75-102.00 -39.00   54
 44  \w   -161.00-105.00   0.50    0.20    --  -91.75 -61.00  30.00  112
 45  \w   -141.00 -80.00   0.50    0.20    --  -91.75 -30.00  60.00  122
;
_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      0.0352168000
_diffrn_orient_matrix_UB_12      -0.0309126000
_diffrn_orient_matrix_UB_13      -0.1158984000
_diffrn_orient_matrix_UB_21      -0.0871257000
_diffrn_orient_matrix_UB_22      0.0663231000
_diffrn_orient_matrix_UB_23      -0.0246952000
_diffrn_orient_matrix_UB_31      0.1187237000
_diffrn_orient_matrix_UB_32      0.1169217000
_diffrn_orient_matrix_UB_33      0.0355903000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.953
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            12428
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.953
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.057
_diffrn_reflns_theta_min         3.550
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    16.604
_exptl_absorpt_correction_T_max  0.614
_exptl_absorpt_correction_T_min  0.194
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    2.083
_exptl_crystal_description       needle
_exptl_crystal_F_000             968
_exptl_crystal_size_max          0.192
_exptl_crystal_size_mid          0.048
_exptl_crystal_size_min          0.039
_refine_diff_density_max         2.731
_refine_diff_density_min         -2.753
_refine_diff_density_rms         0.312
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.370
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     470
_refine_ls_number_reflns         12428
_refine_ls_number_restraints     353
_refine_ls_restrained_S_all      1.352
_refine_ls_R_factor_all          0.1037
_refine_ls_R_factor_gt           0.1017
_refine_ls_shift/su_max          0.003
_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          0.2876
_refine_ls_wR_factor_ref         0.2919
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11705
_reflns_number_total             12428
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 1.7500\% 
around [-0.19 0.15 0.97] (reciprocal) or [-0.06 0.43 0.90] (direct)
;
_cod_data_source_file            d5ce00026b2.cif
_cod_data_source_block           mf-1-34b_1p25-mask_smrt_abs_twin_twin1_hklf5_a
_cod_depositor_comments
'Adding full bibliography for 7250132--7250140.cif.'
_cod_original_cell_volume        1608.68(11)
_cod_database_code               7250135
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C28 H24 Br4 La N O11 '
_chemical_oxdiff_usercomment     'rectangle, purpleish'
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.411(3)
 0.589(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C38-C39
 1.35 with sigma of 0.02
 C31-C38 = C39-C40
 1.43 with sigma of 0.02
 C35-C36
 1.51 with sigma of 0.02
 N33-C35 = N37-C36
 1.48 with sigma of 0.02
 C30-H30 = C34-H34
 0.95 with sigma of 0.0001
 C30-N37_$1 \\sim C34-N33 \\sim C30_$1-N37 \\sim C34_$1-N33_$1
 with sigma of 0.02
 N33-C32 \\sim C32-N37_$1 \\sim C32_$1-N37 \\sim C32_$1-N33_$1
 with sigma of 0.02
 C30-C31 \\sim C34-C40_$1 \\sim C30_$1-C31_$1 \\sim C34_$1-C40
 with sigma of 0.02
 O45A-C47A \\sim O45A-C47B
 with sigma of 0.01
 C46A-C47A \\sim C47A-C48A \\sim C46B-C47B \\sim C47B-C48B
 with sigma of 0.02
 O45A-C46A \\sim O45B-C46B \\sim O45A-C48A \\sim O45B-C48B
 with sigma of 0.04
4. Restrained planarity
 C42, C43, O41, C44
 with sigma of 0.1
 O45A, C46A, C47A, C48A
 with sigma of 0.1
 O45B, C46B, C47B, C48B
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C29 \\sim C30 \\sim C32 \\sim C34 \\sim C31 \\sim N33 \\sim C35 \\sim C39 \\sim
C36 \\sim N37 \\sim C38 \\sim C40: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(C31) = Uanis(N37)
Uanis(C40) = Uanis(N33)
Uanis(C38) = Uanis(C36)
Uanis(C35) = Uanis(C39)
6. Rigid body (RIGU) restrains
 C42, C43, C44, O41
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O19, C20, C21, C22, O23, Br24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13, C14, C15, C16, O17, Br18
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O7, C8, C9, C10, O11, Br12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2, C3, C4, O5, Br6, O1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C29, C30, C32, C34, C31, N33, C35, C39, C36, N37, C38, C40
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O45A, C46A, C47A, C48A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O45B, C46B, C47B, C48B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(O45B)=Sof(C46B)=Sof(H46D)=Sof(H46E)=Sof(H46F)=Sof(C47B)=Sof(C48B)=
 Sof(H48D)=Sof(H48E)=Sof(H48F)=1-FVAR(1)
 Sof(O45A)=Sof(C46A)=Sof(H46A)=Sof(H46B)=Sof(H46C)=Sof(C47A)=Sof(C48A)=
 Sof(H48A)=Sof(H48B)=Sof(H48C)=FVAR(1)
 Fixed Sof: C31(0.5) N33(0.5) C35(0.5) H35A(0.5) H35B(0.5) C36(0.5) H36A(0.5)
 H36B(0.5) N37(0.5) C38(0.5) H38(0.5) C39(0.5) H39(0.5) C40(0.5)
8.a Secondary CH2 refined with riding coordinates:
 C35(H35A,H35B), C36(H36A,H36B)
8.b Aromatic/amide H refined with riding coordinates:
 C38(H38), C39(H39), C29(H29)
8.c Idealised Me refined as rotating group:
 C26(H26A,H26B,H26C), C28(H28A,H28B,H28C), C42(H42A,H42B,H42C), C44(H44A,H44B,
 H44C), C46A(H46A,H46B,H46C), C48A(H48A,H48B,H48C), C46B(H46D,H46E,H46F),
 C48B(H48D,H48E,H48F)
;
_shelx_res_checksum              84381
_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 3.264
_oxdiff_exptl_absorpt_empirical_full_min 0.357
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2