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_4135123
_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         'C156 H80 Cu2 N4 O42'
_chemical_formula_sum            'C153 H94 Cu2 N4 O42'
_chemical_formula_weight         2787.40
_space_group_crystal_system      tetragonal
_space_group_IT_number           126
_space_group_name_Hall           '-P 4a 2bc'
_space_group_name_H-M_alt        'P 4/n n c :2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-11-16
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   32.9819(4)
_cell_length_b                   32.9819(4)
_cell_length_c                   9.9569(2)
_cell_measurement_reflns_used    52691
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.4530
_cell_measurement_theta_min      2.4450
_cell_volume                     10831.2(3)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.949
_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     -6.00  20.00   0.50    4.00    --    4.00  45.00   0.00   52
  2  \w    -45.00 -19.00   0.50    4.00    --    4.00  45.00 150.00   52
  3  \w   -101.00   4.00   0.50    4.00    --  -12.40  45.00   0.00  210
  4  \w     30.00  77.00   0.50    4.00    --  -12.40  45.00   0.00   94
  5  \w     13.00  76.00   0.50    4.00    --  -12.40  45.00  60.00  126
  6  \w    -98.00  -1.00   0.50    4.00    --  -12.40  45.00  60.00  194
;
_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      -0.0134758000
_diffrn_orient_matrix_UB_12      0.0061018000
_diffrn_orient_matrix_UB_13      -0.0517779000
_diffrn_orient_matrix_UB_21      -0.0157766000
_diffrn_orient_matrix_UB_22      0.0022168000
_diffrn_orient_matrix_UB_23      0.0478439000
_diffrn_orient_matrix_UB_31      0.0057262000
_diffrn_orient_matrix_UB_32      0.0204897000
_diffrn_orient_matrix_UB_33      0.0100412000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0264
_diffrn_reflns_av_unetI/netI     0.0146
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -44
_diffrn_reflns_limit_k_max       44
_diffrn_reflns_limit_k_min       -45
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            91142
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.501
_diffrn_reflns_theta_min         1.953
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    0.252
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68240
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light blue'
_exptl_crystal_density_diffrn    0.855
_exptl_crystal_description       block
_exptl_crystal_F_000             2868
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.125
_refine_diff_density_min         -0.930
_refine_diff_density_rms         0.090
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.039
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     266
_refine_ls_number_reflns         7184
_refine_ls_number_restraints     523
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0918
_refine_ls_R_factor_gt           0.0800
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1455P)^2^+13.8212P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2408
_refine_ls_wR_factor_ref         0.2532
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5769
_reflns_number_total             7184
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c04450_si_002.cif
_cod_data_source_block           fhf085_2_sq
_cod_original_sg_symbol_H-M      'P 4/n n c'
_cod_database_code               4135123
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C156 H80 N4 O40 Cu2'
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C13A-C16A \\sim C13B-C16B
 with sigma of 0.02
 C16A-O4A \\sim C16A-O5A \\sim C16B-O4A \\sim C16B-O5B
 with sigma of 0.02
 O4A-O5A \\sim O4B-O5B
 with sigma of 0.02
 C2-C10A \\sim C2-C10B
 with sigma of 0.02
 C6A-C9A \\sim C6B-C9B
 with sigma of 0.02
 C9A-O2A \\sim C9A-O3A \\sim C9B-O2B \\sim C9B-O3B
 with sigma of 0.02
 O2A-O3A \\sim O2B-O3B
 with sigma of 0.02
 C1-C3A \\sim C1-C3B
 with sigma of 0.02
3. Restrained planarity
 C13A, C16A, O4A, O5A
 with sigma of 0.1
 C13B, C16B, O4B, O5B
 with sigma of 0.1
 C6A, C9A, O2A, O3A
 with sigma of 0.1
 C6B, C9B, O2B, O3B
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C10A \\sim C11A \\sim C12A \\sim C13A \\sim C14A \\sim C15A \\sim C10B \\sim
C11B \\sim C12B \\sim C13B \\sim C14B \\sim C15B: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C3A \\sim C4A \\sim C5A \\sim C6A \\sim C7A \\sim C8A \\sim C3B \\sim C4B \\sim
C5B \\sim C6B \\sim C7B \\sim C8B: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(O4A) = Uanis(O5A) = Uanis(C16A) = Uanis(O4B) = Uanis(O5B) = Uanis(C16B) =
Uanis(C13A) = Uanis(C13B)
Uanis(O2A) = Uanis(O3A) = Uanis(C9A) = Uanis(C6A) = Uanis(O2B) = Uanis(O3B) =
Uanis(C9B) = Uanis(C6B)
5. Rigid body (RIGU) restrains
 C10A, C11A, C12A, C13A, C14A, C15A, C10B, C11B, C12B, C13B, C14B, C15B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3A, C4A, C5A, C6A, C7A, C8A, C3B, C4B, C5B, C6B, C7B, C8B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O4B)=Sof(O5B)=Sof(C16B)=Sof(C10B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(H12B)=
 Sof(C13B)=Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(H15B)=1-FVAR(1)
 Sof(O4A)=Sof(O5A)=Sof(C16A)=Sof(C10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(H12A)=
 Sof(C13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=FVAR(1)
 Sof(O2B)=Sof(O3B)=Sof(C9B)=Sof(C3B)=Sof(C4B)=Sof(H4B)=Sof(C5B)=Sof(H5B)=
 Sof(C6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=1-FVAR(2)
 Sof(O2A)=Sof(O3A)=Sof(C9A)=Sof(C3A)=Sof(C4A)=Sof(H4A)=Sof(C5A)=Sof(H5A)=
 Sof(C6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=FVAR(2)
7.a Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C5A(H5A), C7A(H7A), C8A(H8A), C4B(H4B), C5B(H5B), C7B(H7B),
 C8B(H8B), C11A(H11A), C12A(H12A), C14A(H14A), C15A(H15A), C11B(H11B),
 C12B(H12B), C14B(H14B), C15B(H15B), C18(H18), C19(H19)
7.b Fitted hexagon refined as free rotating group:
 C3A(C4A,C5A,C6A,C7A,C8A), C3B(C4B,C5B,C6B,C7B,C8B), C10A(C11A,C12A,C13A,C14A,
 C15A), C10B(C11B,C12B,C13B,C14B,C15B)
;
_shelx_res_checksum              23618
_shelx_hkl_checksum              91001
_shelx_fab_checksum              38680
_platon_squeeze_void_probe_radius 1.20
_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 1.468
_oxdiff_exptl_absorpt_empirical_full_min 0.710