A pseudo five-fold symmetrical ligand drives geometric frustration in porous metal-organic and hydrogen bonded frameworks.
Haase, Frederik; Craig, Gavin A.; Bonneau, Mickaele; Sugimoto, Kunihisa; Furukawa, Shuhei; Journal of the American Chemical Society  (2020) –; doi:10.1021/jacs.0c04450

data_4135124
_publ_section_title
;
 A pseudo five-fold symmetrical ligand drives geometric frustration in
 porous metal-organic and hydrogen bonded frameworks.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.0c04450
_journal_year                    2020
_chemical_formula_moiety
'C350 H262 Cu16 N10 O96, 24(C3 H7 N O), 8(C4 H8 O)'
_chemical_formula_sum            'C454 H486 Cu16 N34 O128'
_chemical_formula_weight         9483.38
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2020-02-26
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 113.928(3)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   24.4730(6)
_cell_length_b                   27.0553(4)
_cell_length_c                   20.2370(5)
_cell_measurement_reflns_used    34652
_cell_measurement_temperature    100
_cell_measurement_theta_max      31.1110
_cell_measurement_theta_min      2.1500
_cell_volume                     12247.8(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46 (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.995
_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    -75.00 -49.00   0.50    3.32    --  -16.40  45.00  90.00   52
  2  \w    -34.00  73.00   0.50    3.32    --  -16.40  45.00  90.00  214
  3  \w    -97.00 -71.00   0.50    3.32    --  -16.40  45.00  30.00   52
  4  \w     16.00  73.00   0.50    3.32    --  -16.40  45.00  30.00  114
  5  \w   -105.00 -43.00   0.50    3.32    --  -16.40  45.00 120.00  124
  6  \w    -27.00  73.00   0.50    3.32    --  -16.40  45.00 120.00  200
  7  \w   -105.00 -79.00   0.50    3.32    --  -16.40  45.00  90.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC10 (RCD3): fixed-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0069146000
_diffrn_orient_matrix_UB_12      -0.0254497000
_diffrn_orient_matrix_UB_13      -0.0000422000
_diffrn_orient_matrix_UB_21      0.0276975000
_diffrn_orient_matrix_UB_22      0.0062739000
_diffrn_orient_matrix_UB_23      -0.0013381000
_diffrn_orient_matrix_UB_31      0.0138608000
_diffrn_orient_matrix_UB_32      0.0001114000
_diffrn_orient_matrix_UB_33      0.0383003000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0194
_diffrn_reflns_av_unetI/netI     0.0201
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            61364
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.128
_diffrn_reflns_theta_min         1.849
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.761
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.73314
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46 (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.286
_exptl_crystal_description       block
_exptl_crystal_F_000             4936
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.433
_refine_diff_density_min         -1.346
_refine_diff_density_rms         0.155
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     634
_refine_ls_number_reflns         16383
_refine_ls_number_restraints     21
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0883
_refine_ls_R_factor_gt           0.0773
_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^)+(0.1531P)^2^+46.7979P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2333
_refine_ls_wR_factor_ref         0.2458
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13702
_reflns_number_total             16383
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c04450_si_003.cif
_cod_data_source_block           fhf113_cd_out
_cod_database_code               4135124
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'Cu2 C20 O6 N8'
_chemical_oxdiff_usercomment     -173degC
_reflns_odcompleteness_completeness 99.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     29.07
_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
2. Restrained distances
 C0AA-O01Q
 1.374 with sigma of 0.02
 C0AA-C4
 1.461 with sigma of 0.02
 C4-C1AA
 1.553 with sigma of 0.02
 C2-C1AA
 1.398 with sigma of 0.02
 O009-H009
 0.85 with sigma of 0.01
 N2-C3AA
 1.567 with sigma of 0.02
 N2-C5
 1.369 with sigma of 0.02
 N2-C2AA
 1.291 with sigma of 0.02
 C2AA-O1
 1.229 with sigma of 0.02
 N4AA-C6AA
 1.52 with sigma of 0.02
 N4AA-C4AA
 1.432 with sigma of 0.02
 N4AA-C5AA
 1.28 with sigma of 0.02
 H3AA-H5A
 2 with sigma of 0.02
 C01L-H009
 1.846806 with sigma of 0.02
 Cu01-H009
 2.714091 with sigma of 0.02
 O00O-C4AA
 2.727 with sigma of 0.04
 C5AA-C6AA
 2.392 with sigma of 0.04
 C5-C2AA
 2.391 with sigma of 0.04
 C3AA-C2AA
 2.295 with sigma of 0.04
3. Restrained planarity
 O00O, N4AA, C4AA, C5AA, C6AA
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C8) = Uanis(N01N) = Uanis(C01V) = Uanis(C9) = Uanis(O01U)
Uanis(C01W) = Uanis(N01I) = Uanis(C3) = Uanis(C01M) = Uanis(O012)
Uanis(C0AA) = Uanis(C4) = Uanis(C1AA) = Uanis(C2) = Uanis(O01Q)
Uanis(O1) = Uanis(C2AA) = Uanis(N2) = Uanis(C5) = Uanis(C3AA)
Uanis(N4AA) = Uanis(C4AA) = Uanis(C5AA) = Uanis(C6AA)
5. Others
 Fixed Sof: N4AA(0.25) C4AA(0.25) H4AA(0.25) H4AB(0.25) H4AC(0.25) C5AA(0.25)
 H5AA(0.25) C6AA(0.25) H6AA(0.25) H6AB(0.25) H6AC(0.25)
6.a Secondary CH2 refined with riding coordinates:
 C0AA(H0AA,H0AB), C01L(H01E,H01H), C01P(H01I,H01K), C01R(H01L,H01M), C4(H4A,H4B)
6.b Me refined with riding coordinates:
 C01V(H01Q,H01R,H01S), C01W(H01U,H01V,H01W), C3(H3A,H3B,H3C), C3AA(H3AA,H3AB,
 H3AC), C5(H5A,H5B,H5C), C8(H8A,H8B,H8C), C4AA(H4AA,H4AB,H4AC), C6AA(H6AA,H6AB,
 H6AC)
6.c Aromatic/amide H refined with riding coordinates:
 C00N(H00N), C00S(H00S), C00T(H00T), C00W(H00W), C00Z(H00Z), C01A(H01A),
 C1AA(H1AA), C01B(H01B), C01C(H01C), C01D(H01D), C01F(H01F), C01G(H01G),
 C01J(H01J), C01M(H01T), C2AA(H2AA), C9(H9), C010(H010), C011(H011), C014(H014),
  C015(H015), C016(H016), C017(H017), C018(H018), C019(H019), C5AA(H5AA)
6.d Idealised Me refined as rotating group:
 C01S(H01N,H01O,H01P), C2(H2A,H2B,H2C)
;
_shelx_res_checksum              80773
_shelx_hkl_checksum              17469
_olex2_date_sample_data_collection 2019-11-14
_olex2_exptl_crystal_mounting_method 'in paratone '
_olex2_submission_original_sample_id pentaMOF-2
_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 1.423
_oxdiff_exptl_absorpt_empirical_full_min 0.667