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_1576255
_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
'C105 H65.645 Cu18 O79.323, 1.25(H2 O), 2.704(C7 H6 O2)'
_chemical_formula_sum            'C123.926 H84.368 Cu18 O85.98'
_chemical_formula_weight         4092.958
_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
_audit_creation_date             2025-01-07
_audit_creation_method
;
Olex2 1.5-dev
(compiled 2025.01.04 svn.r5a871f7a for OlexSys, GUI svn.r7110)
;
_audit_update_record
;
2025-01-07 deposited with the CCDC.	2025-11-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.932(9)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.907(3)
_cell_length_b                   19.2786(15)
_cell_length_c                   40.468(2)
_cell_measurement_reflns_used    3794
_cell_measurement_temperature    175(5)
_cell_measurement_theta_max      0.8990
_cell_measurement_theta_min      0.0460
_cell_volume                     14572(3)
_computing_cell_refinement       'CrysAlisPro 1.171.44.70a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 44.70a 64-bit (release 10-09-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.44.70a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-dev (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-dev (Dolomanov et al., 2009)'
_computing_structure_refinement  'olex2.refine 1.5-dev (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 0.6684
_diffrn_measured_fraction_theta_max 0.6684
_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    -57.25  38.00   0.25    0.50    --    0.00   0.00   0.00  381
;
_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      0.0012086000
_diffrn_orient_matrix_UB_12      -0.0005496000
_diffrn_orient_matrix_UB_13      0.0000232000
_diffrn_orient_matrix_UB_21      0.0003388000
_diffrn_orient_matrix_UB_22      0.0004026000
_diffrn_orient_matrix_UB_23      0.0005936000
_diffrn_orient_matrix_UB_31      -0.0004752000
_diffrn_orient_matrix_UB_32      -0.0011108000
_diffrn_orient_matrix_UB_33      0.0002043000
_diffrn_radiation_monochromator  none
_diffrn_radiation_probe          electron
_diffrn_radiation_type           electron
_diffrn_radiation_wavelength     0.0251
_diffrn_reflns_av_R_equivalents  0.2803
_diffrn_reflns_av_unetI/netI     0.3343
_diffrn_reflns_Laue_measured_fraction_full 0.6684
_diffrn_reflns_Laue_measured_fraction_max 0.6684
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       44
_diffrn_reflns_limit_l_min       -44
_diffrn_reflns_number            39418
_diffrn_reflns_point_group_measured_fraction_full 0.6684
_diffrn_reflns_point_group_measured_fraction_max 0.6684
_diffrn_reflns_theta_full        0.7990
_diffrn_reflns_theta_max         0.80
_diffrn_reflns_theta_min         0.04
_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  0.70867
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.70a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'dark green (bulk)'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    'green (bulk)'
_exptl_crystal_density_diffrn    1.866
_exptl_crystal_description       plate
_exptl_crystal_F_000             2506.530
_exptl_crystal_preparation
;
sample ground between glass slides, grid tapped
;
_exptl_crystal_size_max          0.0029
_exptl_crystal_size_mid          0.0023
_refine_diff_density_max         2.7435
_refine_diff_density_min         -1.6187
_refine_diff_density_rms         0.3759
_refine_ls_d_res_high            0.9000
_refine_ls_d_res_low             19.9887
_refine_ls_extinction_coef       327(22)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_goodness_of_fit_ref   1.3107
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_constraints    171
_refine_ls_number_parameters     2144
_refine_ls_number_reflns         13988
_refine_ls_number_restraints     2770
_refine_ls_restrained_S_all      1.1800
_refine_ls_R_factor_all          0.3160
_refine_ls_R_factor_gt           0.2282
_refine_ls_shift/su_max          0.0008
_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          0.4729
_refine_ls_wR_factor_ref         0.5275
_reflns_Friedel_coverage         0.0
_reflns_limit_h_max              17
_reflns_limit_h_min              -19
_reflns_limit_k_max              21
_reflns_limit_k_min              0
_reflns_limit_l_max              44
_reflns_limit_l_min              -16
_reflns_number_gt                6923
_reflns_number_total             13988
_reflns_threshold_expression     I>=2u(I)
_cod_data_source_file            d5sc05651a2.cif
_cod_data_source_block           exp_1517_s20e400_sd_inc_msk_int
_cod_database_code               1576255
_chemical_oxdiff_formula         'Cu C O H'
_chemical_oxdiff_usercomment
;
'Agar holey carbon gold grid, olive-green solid, ground between glass slides,
grid tapped, cryotransfer @ 175 K, coll @ 175 K'
;
_diffrn_oxdiff_scatteringfactors_ed
'UCLA (2022) https://srv.mbi.ucla.edu/faes/data'
_diffrn_oxdiff_ac3_digest_hkl    416a90e355e84e458dc0030190d3939038eb38
_diffrn_oxdiff_digest_creation
;
CAP 1.171.44.70a, AC 1.5-ac6-020
;
_diffrn_oxdiff_digest_dyn_ed
;
610f45eee4fdebfcd3b441686e59ecef76d80d
;
_diffrn_oxdiff_digest_hkl
;
43e9faf98e2cb07199d82316f16fcbc942db7a
;
_diffrn_oxdiff_digest_hkl_ed
;
53710213919621d5a13478e4a986d9d722304a
;
_diffrn_oxdiff_digest_od_ed
;

;
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H70 of O70, {H82a,H82b} of O82, {H67a,H67b} of O67, {H66a,
  H66b} of O66, H71 of O71, {H80a,H80b} of O80, H13 of O13, H14 of O14, {H11a,
  H11b} of O11, H54 of O54, H41 of O41, H42 of O42, H53 of O53, {H12a,H12b} of
  O12, H87a of O87
 At 1.5 times of:
  {H81a,H81b} of O81, {H37a,H37b} of O37, {H24a,H24b} of O24, {H23a,H23b} of
  O23, {H38a,H38b} of O38, {H57a,H57b} of O57, H84 of O84, H85 of O85, H26a of
  O26, {H2wa,H2wb} of O2w, {H1wa,H1wb} of O1w, H25 of O25
2. Restrained distances
 C113-C114 = C114-C115 = C115-C116 = C116-C117 = C117-C118 = C118-C113
 1.39 with sigma of 0.01
 O2w-H2wa = O2w-H2wb
 0.983 with sigma of 0.02
 C83-C84 = C84-C85 = C85-C86 = C86-C87 = C87-C88 = C88-C83
 1.39 with sigma of 0.01
 Cu8-O37 = Cu7-O38 = Cu3-O12 = Cu5-O24
 2.3 with sigma of 0.02
 O87-H87a
 0.983 with sigma of 0.02
 O38-H38a = O38-H38b
 0.983 with sigma of 0.02
 C11-C12 = C12-C13 = C13-C14 = C14-C15 = C15-C10 = C10-C11
 1.39 with sigma of 0.01
 C3-C2 = C2-C7 = C7-C6 = C6-C5 = C5-C4 = C4-C3
 1.39 with sigma of 0.01
 C18-C19 = C19-C20 = C20-C21 = C21-C22 = C22-C17 = C17-C18
 1.39 with sigma of 0.01
 C32-C33 = C33-C34 = C34-C29 = C29-C30 = C30-C31 = C31-C32
 1.39 with sigma of 0.01
 C26-C27 = C27-C25_$1 = C25-C26 = C26-C27 = C27_$1-C25 = C25-C26
 1.39 with sigma of 0.01
 C54-C55 = C55-C56 = C56-C57 = C57-C52 = C52-C53 = C53-C54
 1.39 with sigma of 0.01
 C99-C100 = C100-C101 = C101-C102 = C102-C103 = C103-C104 = C104-C99
 1.39 with sigma of 0.01
 C39-C40 = C40-C41 = C41-C42 = C42-C37 = C37-C38 = C38-C39
 1.39 with sigma of 0.01
 C48-C47 = C47-C46 = C46-C45 = C45-C50 = C50-C49 = C49-C48
 1.39 with sigma of 0.01
 C106-C107 = C107-C108 = C108-C109 = C109-C110 = C110-C111 = C111-C106
 1.39 with sigma of 0.01
 C76-C77 = C77-C78 = C78-C79 = C79-C80 = C80-C81 = C81-C76
 1.39 with sigma of 0.01
 C64-C63 = C63-C62 = C62-C61 = C61-C60 = C60-C65 = C65-C64
 1.39 with sigma of 0.01
 C71-C70 = C70-C69 = C69-C68 = C68-C73 = C73-C72 = C72-C71
 1.39 with sigma of 0.01
 C98-O83
 1.25 with sigma of 0.2
 C112-O88
 1.2 with sigma of 0.02
 C8-C5
 1.52 with sigma of 0.02
 C90-C91
 1.52 with sigma of 0.02
 C83-C82
 1.52 with sigma of 0.02
 O25-C26
 1.3 with sigma of 0.02
 O1w-H1wa = O1w-H1wb
 0.983 with sigma of 0.02
 C24-C25
 1.5 with sigma of 0.02
 H2wa-H2wb
 1.33 with sigma of 0.04
 H1wa-H1wb
 1.33 with sigma of 0.04
 C83-C85 \\sim C84-C86 \\sim C85-C87 \\sim C86-C88 \\sim C87-C83 \\sim C88-C84
 with sigma of 0.02
 Cu7-H38b \\sim Cu7-H38a
 with sigma of 0.02
 C113-C115 \\sim C114-C116 \\sim C115-C117 \\sim C116-C118 \\sim C117-C113
\\sim C118-C114
 with sigma of 0.02
 C11-C13 \\sim C12-C14 \\sim C13-C15 \\sim C14-C10 \\sim C15-C11 \\sim C10-C12
 with sigma of 0.02
 C3-C7 \\sim C2-C6 \\sim C7-C5 \\sim C6-C4 \\sim C5-C3 \\sim C4-C2
 with sigma of 0.02
 C18-C20 \\sim C19-C21 \\sim C20-C22 \\sim C21-C17 \\sim C22-C18 \\sim C17-C19
 with sigma of 0.02
 C32-C34 \\sim C33-C29 \\sim C34-C30 \\sim C29-C31 \\sim C30-C32 \\sim C31-C33
 with sigma of 0.02
 C26-C25_$1 \\sim C27-C26_$1 \\sim C25-C27 \\sim C26_$1-C25 \\sim C27_$1-C26
\\sim C25-C27
 with sigma of 0.02
 C54-C56 \\sim C55-C57 \\sim C56-C52 \\sim C57-C53 \\sim C52-C54 \\sim C53-C55
 with sigma of 0.02
 C99-C101 \\sim C100-C102 \\sim C101-C103 \\sim C102-C104 \\sim C103-C99 \\sim
C104-C100
 with sigma of 0.02
 C39-C41 \\sim C40-C42 \\sim C41-C37 \\sim C42-C38 \\sim C37-C39 \\sim C38-C40
 with sigma of 0.02
 C48-C46 \\sim C47-C45 \\sim C46-C50 \\sim C45-C49 \\sim C50-C48 \\sim C49-C47
 with sigma of 0.02
 C106-C108 \\sim C107-C109 \\sim C108-C110 \\sim C109-C111 \\sim C110-C106
\\sim C111-C107
 with sigma of 0.02
 C76-C78 \\sim C77-C79 \\sim C78-C80 \\sim C79-C81 \\sim C80-C76 \\sim C81-C77
 with sigma of 0.02
 C64-C62 \\sim C63-C61 \\sim C62-C60 \\sim C61-C65 \\sim C60-C64 \\sim C65-C63
 with sigma of 0.02
 C71-C69 \\sim C70-C68 \\sim C69-C73 \\sim C68-C72 \\sim C73-C71 \\sim C72-C70
 with sigma of 0.02
3. Restrained planarity
 C83, C84, C85, C86, C87, C88
 with sigma of 0.1
 C26, C24, O21, O25
 with sigma of 0.1
 C113, C114, C115, C116, C117, C118
 with sigma of 0.1
 C11, C12, C13, C14, C15, C10
 with sigma of 0.1
 C3, C2, C7, C6, C5, C4
 with sigma of 0.1
 C18, C19, C20, C21, C22, C17
 with sigma of 0.1
 C32, C33, C34, C29, C30, C31
 with sigma of 0.1
 C26, C27, C25_$1, C26_$1, C27_$1, C25
 with sigma of 0.1
 C54, C55, C56, C57, C52, C53
 with sigma of 0.1
 C99, C100, C101, C102, C103, C104
 with sigma of 0.1
 C39, C40, C41, C42, C37, C38
 with sigma of 0.1
 C48, C47, C46, C45, C50, C49
 with sigma of 0.1
 C106, C107, C108, C109, C110, C111
 with sigma of 0.1
 C76, C77, C78, C79, C80, C81
 with sigma of 0.1
 C64, C63, C62, C61, C60, C65
 with sigma of 0.1
 C71, C70, C69, C68, C73, C72
 with sigma of 0.1
 O43, C55, C54, O42, H42
 with sigma of 0.1
 C53, C51, O39, O41, H41
 with sigma of 0.1
 C27, C24_$1, O22_$1, O26, H26a
 with sigma of 0.1
 O21, C25, C26, O25, H25
 with sigma of 0.1
 C92, O70, C90, O68, H70
 with sigma of 0.1
 O72, C97, C93, O71, H71
 with sigma of 0.1
 O88, C112, O87, H87a
 with sigma of 0.1
 C105, O85, O86, H85
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C94 \\sim C95 \\sim C93 \\sim C96 \\sim C92 \\sim C91: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C113 \\sim C112 \\sim O87 \\sim O88 \\sim C114 \\sim C115 \\sim C116 \\sim C117
\\sim C118: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
O55 \\sim C74 \\sim O56 \\sim C71: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C25 \\sim C26 \\sim C27 \\sim O25 \\sim O26: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
O83 \\sim O84 \\sim C98 \\sim C99 \\sim C104 \\sim C100 \\sim C101 \\sim C102
\\sim C103: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
within 2A
C14 \\sim C13 \\sim C15: within 2A with sigma of 0.02 and sigma for terminal
atoms of 0.04 within 2A
C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81 \\sim C76: within 2A with sigma of
0.02 and sigma for terminal atoms of 0.04 within 2A
C29 \\sim C34 \\sim C30: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(O2w) \\sim Ueq: with sigma of 0.025 and sigma for terminal atoms of 0.05
Uanis(O30) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O1w) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C88) \\sim Ueq: with sigma of 0.025 and sigma for terminal atoms of 0.05
Uanis(O87) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C126) \\sim Ueq, Uanis(C125) \\sim Ueq, Uanis(C124) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(O18) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C29) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Fixed Sof: O11(0.66667) H11a(0.66667) H11b(0.66667) O23(0.82256)
 H23a(0.82256) H23b(0.82256) O24(0.5) H24a(0.5) H24b(0.5) H26(0.5) H27(0.5)
 O12(0.33333) H12a(0.33333) H12b(0.33333) O25(0.5) H25(0.5) O26(0.5) H26a(0.5)
 O1w(0.5) H1wa(0.5) H1wb(0.5) O2w(0.75) H2wa(0.75) H2wb(0.75) O83(0.81073)
 O84(0.81073) H84(0.81073) C98(0.81073) C99(0.81073) C100(0.81073)
 H100(0.81073) C101(0.81073) H101(0.81073) C102(0.81073) H102(0.81073)
 C103(0.81073) H103(0.81073) C104(0.81073) H104(0.81073) O87(0.89302)
 H87a(0.89302) O88(0.89302) C112(0.89302) C113(0.89302) C114(0.89302)
 H114(0.89302) C115(0.89302) H115(0.89302) C116(0.89302) H116(0.89302)
 C117(0.89302) H117(0.89302) C118(0.89302) H118(0.89302)
7.a Free rotating group:
 O1w(H1wa,H1wb), O2w(H2wa,H2wb)
7.b Rotating group:
 O11(H11a,H11b), O23(H23a,H23b), O24(H24a,H24b), O37(H37a,H37b), O57(H57a,
 H57b), O66(H66a,H66b), O67(H67a,H67b), O80(H80a,H80b), O81(H81a,H81b),
 O82(H82a,H82b), O12(H12a,H12b)
7.c Aromatic/amide H refined with riding coordinates:
 C6(H6), C7(H7), C11(H11), C12(H12), C13(H13a), C14(H14a), C15(H15), C21(H21),
 C22(H22), C26(H26), C27(H27), C33(H33), C34(H34), C41(H41a), C42(H42a),
 C46(H46), C47(H47), C48(H48), C49(H49), C50(H50), C56(H56), C57(H57), C64(H64),
  C65(H65), C72(H72), C73(H73), C77(H77), C78(H78), C79(H79), C80(H80),
 C81(H81), C87(H87), C88(H88), C95(H95), C96(H96), C124(H124), C125(H125),
 C100(H100), C101(H101), C102(H102), C103(H103), C104(H104), C107(H107),
 C108(H108), C109(H109), C110(H110), C111(H111), C114(H114), C115(H115),
 C116(H116), C117(H117), C118(H118)
7.d Idealised tetrahedral OH refined as rotating group:
 O13(H13), O14(H14), O41(H41), O42(H42), O53(H53), O54(H54), O70(H70),
 O71(H71), O25(H25), O26(H26a), O84(H84), O85(H85), O87(H87a)
;
_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 1.837
_oxdiff_exptl_absorpt_empirical_full_min 0.665
_oxdiff_exptl_crystal_thickness  1000.0