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_4135125
_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         'C39 H20 Cu2 N O12'
_chemical_formula_sum            'C39 H23 Cu2 N O10'
_chemical_formula_weight         792.66
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-11-19
_audit_creation_method
;
Olex2 1.3
(compiled Sep 10 2019 10:52:38 for OlexSys, GUI svn.r5938)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   28.6889(3)
_cell_length_b                   21.1660(2)
_cell_length_c                   14.4751(2)
_cell_measurement_reflns_used    160988
_cell_measurement_temperature    100
_cell_measurement_theta_max      29.5480
_cell_measurement_theta_min      1.9510
_cell_volume                     8789.70(17)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.957
_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    -85.00  93.00   0.50   24.00    --    4.00  45.00 143.13  356
  2  \w    -85.00  93.00   0.50   24.00    --    4.00  45.00 120.00  356
  3  \w     52.00  93.00   0.50   24.00    --    4.00  45.00  30.00   82
  4  \w     28.00  93.00   0.50   24.00    --    4.00  45.00  60.00  130
  5  \w    -18.00  93.00   0.50   24.00    --    4.00  45.00  90.00  222
  6  \w     31.00  57.00   0.50   24.00    --    4.00  45.00 120.00   52
  7  \w    -28.00   4.00   0.50   24.00    --    4.00  45.00  60.00   64
  8  \w   -102.00  76.00   0.50   24.00    --  -13.20  45.00 178.94  356
  9  \w     -6.00  67.00   0.50   24.00    --  -13.20  45.00  90.00  146
 10  \w   -102.00 -56.00   0.50   24.00    --  -13.20  45.00  90.00   92
 11  \w   -102.00 -32.00   0.50   24.00    --  -13.20  45.00 120.00  140
 12  \w   -102.00  57.00   0.50   24.00    --  -13.20  45.00  30.00  318
 13  \w   -102.00 -69.00   0.50   24.00    --  -13.20  45.00 150.00   66
 14  \w     45.00  71.00   0.50   24.00    --  -13.20  45.00 150.00   52
 15  \w    -62.00  38.00   0.50   24.00    --  -13.20  45.00 150.00  200
 16  \w   -102.00  74.00   0.50   24.00    --  -13.20  45.00 -17.66  352
;
_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      0.0110627000
_diffrn_orient_matrix_UB_12      0.0431966000
_diffrn_orient_matrix_UB_13      -0.0050417000
_diffrn_orient_matrix_UB_21      0.0181251000
_diffrn_orient_matrix_UB_22      -0.0224693000
_diffrn_orient_matrix_UB_23      -0.0168695000
_diffrn_orient_matrix_UB_31      -0.0126343000
_diffrn_orient_matrix_UB_32      0.0056984000
_diffrn_orient_matrix_UB_33      -0.0285170000
_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  0.0304
_diffrn_reflns_av_unetI/netI     0.0194
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       34
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            313645
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.933
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.847
_diffrn_reflns_theta_min         1.704
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    1.016
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85795
_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 green'
_exptl_crystal_density_diffrn    1.198
_exptl_crystal_description       rhombohedral
_exptl_crystal_F_000             3216
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.877
_refine_diff_density_min         -0.569
_refine_diff_density_rms         0.095
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.182(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     968
_refine_ls_number_reflns         23585
_refine_ls_number_restraints     419
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0715
_refine_ls_R_factor_gt           0.0564
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0997P)^2^+8.0569P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1555
_refine_ls_wR_factor_ref         0.1680
_reflns_Friedel_coverage         0.880
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.908
_reflns_number_gt                18962
_reflns_number_total             23585
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c04450_si_004.cif
_cod_data_source_block           fhf117f_sq
_cod_database_code               4135125
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C156 H80 N4 O40 Cu8'
_shelx_estimated_absorpt_t_max   0.923
_shelx_estimated_absorpt_t_min   0.862
_reflns_odcompleteness_completeness 99.93
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.04
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.818(14)
 0.182(14)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Shared sites
{N1A, C1B}
{N1B, C1A}
{N2A, C40B}
{N2B, C40A}
4. Restrained distances
 C42-C64A \\sim C42-C64B
 with sigma of 0.02
 C70A-O17A \\sim C70A-O18A \\sim C70B-O17B \\sim C70B-O18B
 with sigma of 0.02
 O17A-O18A \\sim O17B-O18B
 with sigma of 0.02
 C67A-C70A \\sim C67B-C70B
 with sigma of 0.02
 C4-C26A \\sim C4-C26B
 with sigma of 0.02
 C32A-O7A \\sim C32A-O8A \\sim C32B-O7B \\sim C32B-O8B
 with sigma of 0.02
 O7A-O8A \\sim O7B-O8B
 with sigma of 0.02
 C29A-C32A \\sim C29B-C32B
 with sigma of 0.02
5. Restrained planarity
 C67A, C70A, O17A, O18A
 with sigma of 0.1
 C67B, C70B, O17B, O18B
 with sigma of 0.1
 C29A, C32A, O7A, O8A
 with sigma of 0.1
 C29B, C32B, O7B, O8B
 with sigma of 0.1
6. Uiso/Uaniso restraints and constraints
C26A \\sim C27A \\sim C29A \\sim C28A \\sim C30A \\sim C31A \\sim C32A \\sim
O7A \\sim O8A \\sim C26B \\sim C27B \\sim C29B \\sim C28B \\sim C30B \\sim C31B
\\sim C32B \\sim O7B \\sim O8B: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 2A
Uanis(O23A) = Uanis(O23B)
Uanis(C64A) = Uanis(C65A) = Uanis(C66A) = Uanis(C67A) = Uanis(C68A) =
Uanis(C69A) = Uanis(C70A) = Uanis(O17A) = Uanis(O18A)
Uanis(C64B) = Uanis(C65B) = Uanis(C66B) = Uanis(C67B) = Uanis(C68B) =
Uanis(C69B) = Uanis(C70B) = Uanis(O17B) = Uanis(O18B)
Uanis(O24A) = Uanis(O24B)
Uanis(N1A) = Uanis(C1A) = Uanis(N1B) = Uanis(C1B)
Uanis(N2A) = Uanis(C40A) = Uanis(N2B) = Uanis(C40B)
Uanis(C26A) = Uanis(C26B)
Uanis(O7A) = Uanis(O7B) = Uanis(O8A) = Uanis(O8B)
7. Rigid body (RIGU) restrains
 C26A, C27A, C29A, C28A, C30A, C31A, C32A, O7A, O8A, C26B, C27B, C29B, C28B,
 C30B, C31B, C32B, O7B, O8B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
8. Others
 Sof(O23B)=1-FVAR(1)
 Sof(O23A)=FVAR(1)
 Sof(O17B)=Sof(O18B)=Sof(C70B)=Sof(C64B)=Sof(C65B)=Sof(H65B)=Sof(C66B)=
 Sof(H66B)=Sof(C67B)=Sof(C68B)=Sof(H68B)=Sof(C69B)=Sof(H69B)=1-FVAR(2)
 Sof(O17A)=Sof(O18A)=Sof(C70A)=Sof(C64A)=Sof(C65A)=Sof(H65A)=Sof(C66A)=
 Sof(H66A)=Sof(C67A)=Sof(C68A)=Sof(H68A)=Sof(C69A)=Sof(H69A)=FVAR(2)
 Sof(O7B)=Sof(O8B)=Sof(C32B)=Sof(C26B)=Sof(C27B)=Sof(H27B)=Sof(C29B)=Sof(H29B)=
 Sof(C28B)=Sof(C30B)=Sof(H30B)=Sof(C31B)=Sof(H31B)=1-FVAR(3)
 Sof(O7A)=Sof(O8A)=Sof(C32A)=Sof(C26A)=Sof(C27A)=Sof(H27A)=Sof(C29A)=Sof(H29A)=
 Sof(C28A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=FVAR(3)
 Sof(O24B)=1-FVAR(4)
 Sof(O24A)=FVAR(4)
 Sof(N1B)=Sof(C1B)=1-FVAR(5)
 Sof(N1A)=Sof(C1A)=FVAR(5)
 Sof(N2B)=Sof(C40B)=1-FVAR(6)
 Sof(N2A)=Sof(C40A)=FVAR(6)
9.a Aromatic/amide H refined with riding coordinates:
 C27A(H27A), C29A(H29A), C30A(H30A), C31A(H31A), C27B(H27B), C29B(H29B),
 C30B(H30B), C31B(H31B), C65A(H65A), C66A(H66A), C68A(H68A), C69A(H69A),
 C65B(H65B), C66B(H66B), C68B(H68B), C69B(H69B), C6(H6), C7(H7), C9(H9),
 C10(H10), C13(H13), C14(H14), C16(H16), C17(H17), C20(H20), C21(H21), C23(H23),
  C24(H24), C34(H34), C35(H35), C37(H37), C38(H38), C45(H45), C46(H46),
 C48(H48), C49(H49), C53(H53), C54(H54), C55(H55), C56(H56), C58(H58), C59(H59),
  C61(H61), C62(H62), C72(H72), C73(H73), C75(H75), C76(H76)
9.b Fitted hexagon refined as free rotating group:
 C26A(C27A,C29A,C28A,C30A,C31A), C26B(C27B,C29B,C28B,C30B,C31B), C64A(C65A,
 C66A,C67A,C68A,C69A), C64B(C65B,C66B,C67B,C68B,C69B)
;
_shelx_res_checksum              71179
_shelx_hkl_checksum              83426
_shelx_fab_checksum              47536
_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 1.256
_oxdiff_exptl_absorpt_empirical_full_min 0.841