Solvent induced structural transformation of a cerium(iii) 2,5-furandicarboxylate metal–organic framework
Das, Satarupa; Tidey, Jeremiah P.; Liu, Jie; Pickering, Katie S.; Coe, James C.; Walker, Marc; Walton, Richard I.; CrystEngComm 27 (2025) 6797–6804; doi:10.1039/D5CE00689A

data_7250879
_publ_section_title
;
 Solvent induced structural transformation of a cerium(iii)
 2,5-furandicarboxylate metal--organic framework
;
_journal_issue                   41
_journal_name_full               CrystEngComm
_journal_page_first              6797
_journal_page_last               6804
_journal_paper_doi               10.1039/D5CE00689A
_journal_volume                  27
_journal_year                    2025
_chemical_formula_moiety         'C48.989 H30.307 Ce4 N2.33 O37.33, 2(C2 H8 N)'
_chemical_formula_sum            'C52.989 H46.307 Ce4 N4.33 O37.33'
_chemical_formula_weight         1901.514
_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'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-09-02
_audit_creation_method
;
Olex2 1.5-ac7-018
(compiled 2025.08.06 svn.rb7424aed for Rigaku Oxford Diffraction, GUI svn.r7314)
;
_audit_update_record
;
2025-09-02 deposited with the CCDC.	2025-09-22 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 112.784(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.8474(14)
_cell_length_b                   26.6474(18)
_cell_length_c                   17.9757(11)
_cell_measurement_reflns_used    9284
_cell_measurement_temperature    175(5)
_cell_measurement_theta_max      0.9010
_cell_measurement_theta_min      0.0530
_cell_volume                     6557.0(10)
_computing_cell_refinement       'CrysAlisPro 1.171.44.113a (Rigaku OD, 2025)'
_computing_data_collection
'CrysAlisPro system (CCD 43.97a 64-bit (release 21-11-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.44.113a (Rigaku OD, 2025)'
_computing_molecular_graphics    'Olex2 1.5-ac7-018 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac7-018 (Dolomanov et al., 2009)'
_computing_structure_refinement
'olex2.refine 1.5-ac7-018 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      vacuum
_diffrn_ambient_temperature      175(5)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix-ED
_diffrn_measured_fraction_theta_full 0.9890
_diffrn_measured_fraction_theta_max 0.9898
_diffrn_measurement_details
;
Data were collected on a number of crystallites and the resulting viable
datasets individually integrated and subsequently merged to form this one.
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -60.00  70.00   0.25    1.00    --    0.00   0.00   0.00  520
  2  \w    -55.00  45.00   0.25    2.00    --    0.00   0.00   0.00  400
;
_diffrn_measurement_device       'electron diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy-ED, HyPix-ED, electron source at 200keV'
_diffrn_measurement_method       'continuous rotation electron diffraction'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0018725000
_diffrn_orient_matrix_UB_12      -0.0000051000
_diffrn_orient_matrix_UB_13      0.0006511000
_diffrn_orient_matrix_UB_21      0.0000011000
_diffrn_orient_matrix_UB_22      0.0009418000
_diffrn_orient_matrix_UB_23      -0.0000007000
_diffrn_orient_matrix_UB_31      0.0000000000
_diffrn_orient_matrix_UB_32      0.0000004000
_diffrn_orient_matrix_UB_33      0.0013675000
_diffrn_radiation_monochromator  none
_diffrn_radiation_probe          electron
_diffrn_radiation_type           electron
_diffrn_radiation_wavelength     0.0251
_diffrn_reflns_av_R_equivalents  0.2550
_diffrn_reflns_av_unetI/netI     0.1979
_diffrn_reflns_Laue_measured_fraction_full 0.9890
_diffrn_reflns_Laue_measured_fraction_max 0.9898
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            65335
_diffrn_reflns_point_group_measured_fraction_full 0.9890
_diffrn_reflns_point_group_measured_fraction_max 0.9898
_diffrn_reflns_theta_full        0.8629
_diffrn_reflns_theta_max         0.90
_diffrn_reflns_theta_min         0.05
_diffrn_source                   'electron diffractometer'
_diffrn_source_type              'JEOL JSM-2300ED, LaB6'
_exptl_absorpt_coefficient_mu    0.000
_exptl_absorpt_correction_type   none
_exptl_crystal_density_diffrn    1.926
_exptl_crystal_description       'microcrystalline blocks'
_exptl_crystal_F_000             1241.399
_refine_diff_density_max         3.1002
_refine_diff_density_min         -2.6470
_refine_diff_density_rms         0.4536
_refine_ls_d_res_high            0.8000
_refine_ls_d_res_low             13.3237
_refine_ls_extinction_coef       56(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.0456
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_constraints    106
_refine_ls_number_parameters     927
_refine_ls_number_reflns         13281
_refine_ls_number_restraints     1110
_refine_ls_restrained_S_all      1.0016
_refine_ls_R_factor_all          0.2814
_refine_ls_R_factor_gt           0.2279
_refine_ls_shift/su_max          0.0010
_refine_ls_shift/su_mean         0.0000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0000P)^2^+31.4592P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4378
_refine_ls_wR_factor_ref         0.4688
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              11
_reflns_limit_h_min              -18
_reflns_limit_k_max              33
_reflns_limit_k_min              0
_reflns_limit_l_max              22
_reflns_limit_l_min              -10
_reflns_number_gt                8258
_reflns_number_total             13281
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5ce00689a2.cif
_cod_data_source_block           UoW-11_RW_SD442
_cod_depositor_comments
'Adding full bibliography for 7250878--7250879.cif.'
_cod_database_code               7250879
_chemical_oxdiff_formula         C52H41Ce4N3O38
_chemical_oxdiff_usercomment
;
 SD442 for SD/SW, Ce+FDCA in DMF, ground to dry-load at 175 K, smell of DMF
 and high column vac despite ACD
;
_diffrn_oxdiff_scatteringfactors_ed
'UCLA (2022) https://srv.mbi.ucla.edu/faes/data'
_diffrn_oxdiff_digest_creation
;
CAP 1.171.44.113a, AC 1.5-ac7-016
;
_diffrn_oxdiff_digest_hkl
;
43e6e69901e15d71d4746b6b3621ded4fad90d
;
_diffrn_oxdiff_digest_hkl_ed
;
532cad2794385ddcf470cbeaa3de3b38fa68b0
;
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.5 times of:
  All C(H) groups, {H44a,H44b,H44c} of C44a, {H45a,H45b,H45c} of C45a, {H44d,
  H44e,H44f} of C44b, {H45d,H45e,H45f} of C45b, All C(H,H) groups
 At 1.8 times of:
  All N(H,H) groups, {H47a,H47b,H47c} of C47a, {H51a,H51b,H51c} of C51, {H52a,
  H52b,H52c} of C52, {H48a,H48b,H48c} of C48a, {H49a,H49b,H49c} of C49, {H50a,
  H50b,H50c} of C50, {H54a,H54b,H54c} of C54, {H55a,H55b,H55c} of C55, {H48d,
  H48e,H48f} of C48b, {H47d,H47e,H47f} of C47b
2. Restrained distances
 C53-O38
 1.22 with sigma of 0.02
 C53-N5
 1.36 with sigma of 0.02
 C43-H44d
 2.485 with sigma of 0.02
 H44a-C43
 2.542 with sigma of 0.02
 H45b-C43
 2.47 with sigma of 0.02
 C43-H45e
 2.478 with sigma of 0.02
 N5-C54
 1.45 with sigma of 0.02
 N5-C55
 1.46 with sigma of 0.02
 C53-C54
 2.46 with sigma of 0.04
 C53-C55
 2.45 with sigma of 0.04
 N2a-C47a \\sim N2b-C47b \\sim N2b-C48b \\sim N2a-C48a \\sim N1a-C44a \\sim
N1b-C44b \\sim N1b-C45b ~
 N1a-C45a
 with sigma of 0.02
 N2a-C46 \\sim N2b-C46 \\sim N1b-C43 \\sim N1a-C43
 with sigma of 0.02
 C44b-C43 \\sim C48b-C46 \\sim C48a-C46 \\sim C43-C44a \\sim C43-C45b \\sim
C47a-C46 \\sim C47b-C46 ~
 C43-C45a
 with sigma of 0.02
 N4-C52 \\sim N4-C51 \\sim N3-C50 \\sim N3-C49
 with sigma of 0.02
 O37-C46 \\sim O36-C43
 with sigma of 0.02
 O30-C36 \\sim O29-C36 \\sim O26-C31 \\sim O27-C31 \\sim O32-C37 \\sim O31-C37
\\sim O34-C42 \\sim O35-C42
 \\sim O24-C30 \\sim O25-C30 \\sim O19-C24 \\sim O20-C24 \\sim O16-C19 \\sim
O17-C19 \\sim O21-C25 \\sim O22-
 C25 \\sim O14-C18 \\sim O15-C18 \\sim O12-C13 \\sim O11-C13 \\sim O7-C7 \\sim
O6-C7 \\sim O1-C1 \\sim O2-C1 ~
 O4-C6 \\sim O5-C6 \\sim O10-C12 \\sim O9-C12
 with sigma of 0.02
 C5-C6 \\sim C12-C11 \\sim C7-C8 \\sim C1-C2 \\sim C13-C14 \\sim C18-C17 \\sim
C20-C19 \\sim C25-C26 \\sim C30-
 C29 \\sim C23-C24 \\sim C42-C41 \\sim C37-C38
 with sigma of 0.02
 O33-C41 \\sim O33-C38 \\sim O18-C23 \\sim O23-C29 \\sim O18-C20 \\sim O23-C26
\\sim O13-C17 \\sim O13-C14
 \\sim O3-C2 \\sim O3-C5 \\sim O8-C11 \\sim O8-C8
 with sigma of 0.02
 C11-C10 \\sim C9-C8 \\sim C5-C4 \\sim C3-C2 \\sim C14-C15 \\sim C17-C16 \\sim
C21-C20 \\sim C23-C22 \\sim C29-
 C28 \\sim C27-C26
 with sigma of 0.02
 C21-C22 \\sim C28-C27 \\sim C16-C15 \\sim C9-C10 \\sim C3-C4
 with sigma of 0.02
 N5-C54 \\sim N5-C55
 with sigma of 0.02
3. Restrained planarity
 O37, C46, N2b, C47b, C48b
 with sigma of 0.1
 O36, C43, N1a, C45a, C44a
 with sigma of 0.1
 O37, C46, N2a, C47a, C48a
 with sigma of 0.1
 O36, C43, N1b, C45b, C44b
 with sigma of 0.1
 C53, O38, N5, C54, C55
 with sigma of 0.1
 H54b, C54, N5, C53, C55
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C48b \\sim C48a: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C50 \\sim N3 \\sim C49: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
C48b \\sim N2b \\sim C47b \\sim C46: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C48a \\sim C46 \\sim N2a \\sim C47a: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C48a \\sim C48b: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
N2a \\sim N2b: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C47a \\sim C47b: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C53 \\sim O38 \\sim N5 \\sim C54 \\sim C55: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
Uanis(C50) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(O2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O36) \\sim Ueq, Uanis(C43) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C38) \\sim Ueq, Uanis(C41) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C49) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uiso(C44a) = Uiso(C44b)
Uiso(N1a) = Uiso(N1b)
Uiso(C45b) = Uiso(C45a)
Uiso(O38) = Uiso(C53) = Uiso(N5) = Uiso(C55) = Uiso(C54)
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C53, O38, N5, C54, C55
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H43a)=Sof(N1b)=Sof(C45b)=Sof(H45d)=Sof(H45e)=Sof(H45f)=Sof(C44b)=
 Sof(H44d)=Sof(H44e)=Sof(H44f)=1-FVAR(1)
 Sof(N1a)=Sof(H43)=Sof(C45a)=Sof(H45a)=Sof(H45b)=Sof(H45c)=Sof(C44a)=Sof(H44a)=
 Sof(H44b)=Sof(H44c)=FVAR(1)
 Sof(C53)=Sof(H53)=Sof(O38)=Sof(N5)=Sof(C54)=Sof(H54a)=Sof(H54b)=Sof(H54c)=
 Sof(C55)=Sof(H55a)=Sof(H55b)=Sof(H55c)=FVAR(2)
 Fixed Sof: N2a(0.5) H46a(0.5) H46(0.5) C47a(0.5) H47a(0.5) H47b(0.5)
 H47c(0.5) C48a(0.5) H48a(0.5) H48b(0.5) H48c(0.5) N2b(0.5) C47b(0.5) H47d(0.5)
 H47e(0.5) H47f(0.5) C48b(0.5) H48d(0.5) H48e(0.5) H48f(0.5)
7.a Secondary CH2 refined with riding coordinates:
 N4(H4a,H4b), N3(H3a,H3b)
7.b Me refined as rotating group:
 C55(H55a,H55b,H55c)
7.c Aromatic/amide H refined with riding coordinates:
 C10(H10), C15(H15), C4(H4), C16(H16), C9(H9), C27(H27), C22(H22), C28(H28),
 C46(H46a), C46(H46), C3(H3), C40(H40), C21(H21), C34(H34), C33(H33), C39(H39),
 C43(H43), C43(H43a), C53(H53)
7.d Idealised Me refined as rotating group:
 C49(H49a,H49b,H49c), C50(H50a,H50b,H50c), C51(H51a,H51b,H51c), C52(H52a,H52b,
 H52c), C47a(H47a,H47b,H47c), C45a(H45a,H45b,H45c), C48a(H48a,H48b,H48c),
 C44a(H44a,H44b,H44c), C47b(H47d,H47e,H47f), C48b(H48d,H48e,H48f), C45b(H45d,
 H45e,H45f), C44b(H44d,H44e,H44f), C54(H54a,H54b,H54c)
;
_atom_sites_solution_hydrogen    geom
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_diffrn_reflns_filtered   4719
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.647
_oxdiff_exptl_absorpt_empirical_full_min 0.718