A flexible copper MOF as a carboxylate-specific crystalline sponge for structure solution using X-ray and electron diffraction.
Main, Russell; Rainer, Daniel N.; Bauzá, Marta; Ettlinger, Romy; Kelly, Nicole L.; Coles, Simon; Ashbrook, Sharon Elizabeth; Morris, Russell; Chemical Science  (2025) –; doi:10.1039/D5SC05651A

data_1576254
_publ_section_title
;
 A flexible copper MOF as a carboxylate-specific crystalline sponge for
 structure solution using X-ray and electron diffraction.
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC05651A
_journal_year                    2025
_chemical_formula_moiety         'C41 H27.775 Cu6 O23.388'
_chemical_formula_sum            'C41 H27.775 Cu6 O23.387'
_chemical_formula_weight         1275.901
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_symmetry_Int_Tables_number      14
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-07
_audit_creation_method
;
Olex2 1.5-ac7-013
(compiled 2025.01.02 svn.rf662f148 for Rigaku Oxford Diffraction, GUI svn.r7109)
;
_audit_update_record
;
2025-01-07 deposited with the CCDC.	2025-11-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 118.78(6)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.409(10)
_cell_length_b                   23.396(8)
_cell_length_c                   16.847(6)
_cell_measurement_reflns_used    970
_cell_measurement_temperature    175(5)
_cell_measurement_theta_max      0.8670
_cell_measurement_theta_min      0.0590
_cell_volume                     5669(6)
_computing_cell_refinement       'CrysAlisPro 1.171.44.81a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.118a 64-bit (release 27-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.44.81a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac7-013 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac7-013 (Dolomanov et al., 2009)'
_computing_structure_refinement
'olex2.refine 1.5-ac7-013 (Bourhis et al., 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.7749
_diffrn_measured_fraction_theta_max 0.7749
_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    -60.00  45.00   0.25    0.25    --    0.00   0.00   0.00  420
;
_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_measurement_specimen_support 'lacey carbon copper grid, 200 mesh'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0011963000
_diffrn_orient_matrix_UB_12      -0.0001472000
_diffrn_orient_matrix_UB_13      -0.0005006000
_diffrn_orient_matrix_UB_21      0.0006715000
_diffrn_orient_matrix_UB_22      0.0009710000
_diffrn_orient_matrix_UB_23      0.0006055000
_diffrn_orient_matrix_UB_31      0.0010781000
_diffrn_orient_matrix_UB_32      -0.0004357000
_diffrn_orient_matrix_UB_33      0.0015087000
_diffrn_radiation_monochromator  none
_diffrn_radiation_probe          electron
_diffrn_radiation_type           electron
_diffrn_radiation_wavelength     0.0251
_diffrn_reflns_av_R_equivalents  0.2381
_diffrn_reflns_av_unetI/netI     0.2753
_diffrn_reflns_Laue_measured_fraction_full 0.7749
_diffrn_reflns_Laue_measured_fraction_max 0.7749
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            15663
_diffrn_reflns_point_group_measured_fraction_full 0.7749
_diffrn_reflns_point_group_measured_fraction_max 0.7749
_diffrn_reflns_theta_full        0.7569
_diffrn_reflns_theta_max         0.76
_diffrn_reflns_theta_min         0.06
_diffrn_source                   LaB6
_diffrn_source_type              'JEOL JSM-2300ED, LaB6'
_diffrn_source_voltage           200
_exptl_absorpt_coefficient_mu    0.000
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.77099
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.81a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'green (bulk)'
_exptl_crystal_colour_primary    'green (bulk)'
_exptl_crystal_density_diffrn    1.495
_exptl_crystal_description       irregular
_exptl_crystal_F_000             789.832
_exptl_crystal_preparation
;
sample ground between glass slides, grid tapped
;
_exptl_crystal_size_max          0.0007
_exptl_crystal_size_mid          0.0007
_exptl_crystal_size_min          0.00045
_refine_diff_density_max         1.5483
_refine_diff_density_min         -1.1316
_refine_diff_density_rms         0.3140
_refine_ls_d_res_high            0.9501
_refine_ls_d_res_low             12.2042
_refine_ls_extinction_coef       53(10)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.2327
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    53
_refine_ls_number_parameters     658
_refine_ls_number_reflns         5368
_refine_ls_number_restraints     1476
_refine_ls_restrained_S_all      1.0757
_refine_ls_R_factor_all          0.3032
_refine_ls_R_factor_gt           0.1810
_refine_ls_shift/su_max          0.0009
_refine_ls_shift/su_mean         0.0001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4196
_refine_ls_wR_factor_ref         0.4835
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              15
_reflns_limit_h_min              -16
_reflns_limit_k_max              24
_reflns_limit_k_min              0
_reflns_limit_l_max              16
_reflns_limit_l_min              0
_reflns_number_gt                2130
_reflns_number_total             5368
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5sc05651a2.cif
_cod_data_source_block           exp_810_mP
_cod_original_cell_volume        5669(5)
_cod_database_code               1576254
_chemical_oxdiff_formula         'Cu12 (C8 O4 H2)7 (C13H18O2)'
_chemical_oxdiff_usercomment
;
'Agar holey carbon grid, solid sample dispersed on glass slide, grid tapped,
cryo transfer @ 175 K, coll @ 175 K'
;
_diffrn_oxdiff_scatteringfactors_ed
'UCLA (2022) https://srv.mbi.ucla.edu/faes/data'
_diffrn_oxdiff_ac6_digest_hkl_ed
;
535be9c1aa9fe2cb8b55e3ed5214888b10db8c
;
_diffrn_oxdiff_digest_creation
;
CAP 1.171.44.81a, AC 1.5-ac7-012
;
_diffrn_oxdiff_digest_dyn_ed
;
61d3b0284cdb1d123c4b381dddb3fa4619e15b
;
_diffrn_oxdiff_digest_hkl
;
43816a02e1d4a8676a3bf6eac5bce2fd01179a
;
_diffrn_oxdiff_digest_hkl_ed
;
536461602eb0710b8b9d3cdf550e8d455cf9c9
;
_diffrn_oxdiff_digest_od_ed
;
62dc4bafa9869f3b29a53a9af93c08fc1d0f83
;
_olex2_refinement_description
;
1. 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, All O(H) groups, All O(H,H) groups
2. Restrained distances
 O22-C28 = O21-C27 = O15-C19 = O16-C20
 1.35 with sigma of 0.02
 C41-C40 = C42-C40 = C40-C39 = C32-C31
 1.54 with sigma of 0.02
 C36-C37 = C37-C38 = C38-C33 = C33-C34 = C34-C35 = C35-C36
 1.39 with sigma of 0.01
 C3-C4 = C4-C5 = C5-C7 = C7-C8 = C8-C2 = C2-C3
 1.39 with sigma of 0.01
 C19-C20 = C20-C21 = C21-C23 = C23-C24 = C24-C18 = C18-C19
 1.39 with sigma of 0.01
 C12-C11 = C11-C10 = C10-C16 = C16-C15 = C15-C13 = C13-C12
 1.39 with sigma of 0.01
 C28-C26_$1 = C26-C27 = C27-C28 = C28_$1-C26 = C26-C27 = C27-C28
 1.39 with sigma of 0.01
 C36-C38 \\sim C37-C33 \\sim C38-C34 \\sim C33-C35 \\sim C34-C36 \\sim C35-C37
 with sigma of 0.02
 C3-C5 \\sim C4-C7 \\sim C5-C8 \\sim C7-C2 \\sim C8-C3 \\sim C2-C4
 with sigma of 0.02
 C19-C21 \\sim C20-C23 \\sim C21-C24 \\sim C23-C18 \\sim C24-C19 \\sim C18-C20
 with sigma of 0.02
 C12-C10 \\sim C11-C16 \\sim C10-C15 \\sim C16-C13 \\sim C15-C12 \\sim C13-C11
 with sigma of 0.02
 C28-C27_$1 \\sim C26-C28 \\sim C27_$1-C26 \\sim C28_$1-C27 \\sim C26-C28 \\sim
C27-C26_$1
 with sigma of 0.02
3. Restrained planarity
 C33, C34, C35, C36, C37, C38
 with sigma of 0.1
 C2, C3, C4, C5, C7, C8
 with sigma of 0.1
 C18, C19, C20, C21, C23, C24
 with sigma of 0.1
 C10, C11, C12, C13, C15, C16
 with sigma of 0.1
 C26_$1, C26, C27, C27_$1, C28, C28_$1
 with sigma of 0.1
 C28, O22, H22, O20_$1
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
O19 \\sim O20 \\sim O23 \\sim O24 \\sim O25 \\sim C1 \\sim C2 \\sim C3 \\sim C4
\\sim C5 \\sim C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12
\\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20
\\sim C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28
\\sim C29 \\sim C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37
\\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42 \\sim O21 \\sim O22 \\sim C25
\\sim C26 \\sim C27 \\sim C28: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
C39 \\sim C40 \\sim C41 \\sim C42: within 2A with sigma of 0.02 and sigma for
terminal atoms of 0.04 within 2A
O6 \\sim C2 \\sim C3 \\sim C4 \\sim C5 \\sim C7 \\sim C8: within 2A with sigma
of 0.02 and sigma for terminal atoms of 0.04 within 2A
O9 \\sim O10 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14 \\sim
C15 \\sim C16: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.04 within 2A
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C21 \\sim C22 \\sim C23 \\sim C24:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04 within 2A
C31 \\sim C32 \\sim C33 \\sim C34 \\sim C35 \\sim C36 \\sim C37 \\sim C38 \\sim
C39 \\sim C40 \\sim C41 \\sim C42: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
C1 \\sim O1 \\sim O6: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
Uanis(Cu4) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O16) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C27)
\\sim Ueq, Uanis(O19) \\sim Ueq, Uanis(O20) \\sim Ueq, Uanis(O21) \\sim Ueq,
Uanis(O22) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34)
\\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C35) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C42) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C12) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C10) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C3) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C7) \\sim
Ueq, Uanis(C2) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(O6) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.04
Uanis(C14) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C10) \\sim Ueq,
Uanis(C9) \\sim Ueq, Uanis(O10) \\sim Ueq, Uanis(O9) \\sim Ueq: with sigma of
0.02 and sigma for terminal atoms of 0.04
Uanis(C19) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C22) \\sim Ueq,
Uanis(C17) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(O9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cu3) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.1
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
6. Others
 Fixed Sof: O25(0.3875) H25a(0.3875) H25b(0.3875) H27(0.5) H28(0.5) O21(0.5)
 H21(0.5) O22(0.5) H22(0.5)
7.a Rotating group:
 O25(H25a,H25b)
7.b Ternary CH refined with riding coordinates:
 C31(H31), C40(H40)
7.c Secondary CH2 refined with riding coordinates:
 C39(H39a,H39b)
7.d Me refined with riding coordinates:
 C41(H41a,H41b,H41c)
7.e Aromatic/amide H refined with riding coordinates:
 C7(H7), C8(H8), C15(H15a), C16(H16a), C23(H23), C24(H24), C27(H27), C28(H28),
 C34(H34), C35(H35), C37(H37), C38(H38)
7.f Idealised Me refined as rotating group:
 C32(H32a,H32b,H32c), C42(H42a,H42b,H42c)
7.g Idealised tetrahedral OH refined as rotating group:
 O15(H15), O16(H16), O21(H21), O22(H22)
;
_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 1.230
_oxdiff_exptl_absorpt_empirical_full_min 0.791
_oxdiff_exptl_crystal_thickness  1000.0