Tying a Molecular Overhand Knot of Single Handedness and Asymmetric Catalysis with the Corresponding Pseudo-D<sub>3</sub>-Symmetric Trefoil Knot.
Gil-Ramírez, Guzmán; Hoekman, Steven; Kitching, Matthew O.; Leigh, David A.; Vitorica-Yrezabal, Iñigo J; Zhang, Gen; Journal of the American Chemical Society 138 (2016) 13159–13162; doi:10.1021/jacs.6b08421

data_4130982
_publ_section_title
;
 Tying a Molecular Overhand Knot of Single Handedness and Asymmetric
 Catalysis with the Corresponding Pseudo-D<sub>3</sub>-Symmetric Trefoil
 Knot.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13159
_journal_page_last               13162
_journal_paper_doi               10.1021/jacs.6b08421
_journal_volume                  138
_journal_year                    2016
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C109 H105 Eu1 N9 O16, 3(C F3 O3 S)'
_chemical_formula_sum            'C112 H105 Eu F9 N9 O25 S3'
_chemical_formula_weight         2396.18
_space_group_crystal_system      trigonal
_space_group_IT_number           150
_space_group_name_Hall           'P 3 2"'
_space_group_name_H-M_alt        'P 3 2 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-07-19
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            2
_cell_length_a                   22.7774(12)
_cell_length_b                   22.7774(12)
_cell_length_c                   12.8368(6)
_cell_measurement_reflns_used    11460
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.3420
_cell_measurement_theta_min      2.2900
_cell_volume                     5767.6(5)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
;
_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    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.976
_diffrn_measured_fraction_theta_max 0.976
_diffrn_measurement_details
;
  1 omega  -60.00  115.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000    0.0000    0.0000 175

  2 omega  -60.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -50.0000    0.0000 120

  3 omega  -60.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -50.0000  120.0000 120

  4 omega  -60.00   60.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       30.0000  -50.0000  240.0000 120
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.0092490000
_diffrn_orient_matrix_UB_12      0.0245384000
_diffrn_orient_matrix_UB_13      0.0016222000
_diffrn_orient_matrix_UB_21      -0.0336646000
_diffrn_orient_matrix_UB_22      -0.0248050000
_diffrn_orient_matrix_UB_23      -0.0009730000
_diffrn_orient_matrix_UB_31      -0.0003142000
_diffrn_orient_matrix_UB_32      -0.0011631000
_diffrn_orient_matrix_UB_33      0.0536313000
_diffrn_radiation_monochromator  synchrotron
_diffrn_radiation_probe          x-ray
_diffrn_radiation_wavelength     0.6889
_diffrn_reflns_av_R_equivalents  0.0609
_diffrn_reflns_av_unetI/netI     0.0267
_diffrn_reflns_Laue_measured_fraction_full 0.976
_diffrn_reflns_Laue_measured_fraction_max 0.976
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            47487
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        24.415
_diffrn_reflns_theta_max         24.517
_diffrn_reflns_theta_min         2.317
_diffrn_source                   synchrotron
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.635
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57229
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.33 (release 27-03-2014 CrysAlis171 .NET)
(compiled Mar 27 2014,17:12:48)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.380
_exptl_crystal_description       needle
_exptl_crystal_F_000             2464
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.179
_refine_diff_density_min         -0.283
_refine_diff_density_rms         0.072
_refine_ls_abs_structure_details
;
 Flack x determined using 1164 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.05(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     451
_refine_ls_number_reflns         6885
_refine_ls_number_restraints     971
_refine_ls_restrained_S_all      2.084
_refine_ls_R_factor_all          0.1502
_refine_ls_R_factor_gt           0.1144
_refine_ls_shift/su_max          0.008
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3021
_refine_ls_wR_factor_ref         0.3394
_reflns_Friedel_coverage         0.855
_reflns_Friedel_fraction_full    0.983
_reflns_Friedel_fraction_max     0.982
_reflns_number_gt                3051
_reflns_number_total             6885
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja6b08421_si_002.cif
_cod_data_source_block           dia_01_gz268
_cod_original_cell_volume        5767.6(6)
_cod_database_code               4130982
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         EuF9S3O25N9C114H109
_reflns_odcompleteness_completeness 97.20
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     24.52
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.611(11) 0.389(11)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C1B-N3
 2.4 with sigma of 0.02
 F67-F10
 2.35 with sigma of 0.02
 O1-S1
 1.43 with sigma of 0.02
 O16-S1
 1.43 with sigma of 0.02
 O16-O1
 2.43 with sigma of 0.02
 O34-S1
 1.43 with sigma of 0.02
 O34-O1
 2.43 with sigma of 0.02
 O34-O16
 2.43 with sigma of 0.02
 F10-F90
 2.35 with sigma of 0.02
 F90-F67
 2.35 with sigma of 0.02
 S1-F90
 2.6 with sigma of 0.02
 F67-O16
 2.9 with sigma of 0.02
 F67-O34
 2.9 with sigma of 0.02
 F10-O34
 2.9 with sigma of 0.02
 F10-O1
 2.9 with sigma of 0.02
 F90-O1
 2.9 with sigma of 0.02
 F90-O16
 2.9 with sigma of 0.02
 O1D-C47
 2.4 with sigma of 0.02
 O1D-C94
 2.4 with sigma of 0.02
 O4-S3
 1.43 with sigma of 0.02
 C48-S3
 1.9 with sigma of 0.02
 O19-S3
 1.43 with sigma of 0.02
 O4-O19
 2.43 with sigma of 0.02
 O19-C48
 2.6 with sigma of 0.02
 O19-C48
 2.6 with sigma of 0.02
 O4-C48
 2.6 with sigma of 0.02
 O19-C48
 2.56 with sigma of 0.02
 C48-O4
 2.56 with sigma of 0.02
 F11-C48
 1.35 with sigma of 0.02
 F48-C48
 1.35 with sigma of 0.02
 F11-F48
 2.35 with sigma of 0.02
 F35-C48
 1.35 with sigma of 0.02
 F35-F48
 2.35 with sigma of 0.02
 F11-F35
 2.35 with sigma of 0.02
 F48-S3
 2.6 with sigma of 0.02
 F35-S3
 2.6 with sigma of 0.02
 F11-S3
 2.6 with sigma of 0.02
 O4-F11
 2.9 with sigma of 0.02
 O4-F35
 2.9 with sigma of 0.02
 O19-F35
 2.9 with sigma of 0.02
 O19-F48
 2.9 with sigma of 0.02
 O19-F11
 2.9 with sigma of 0.02
 O19-F48
 2.9 with sigma of 0.02
 O4-F35
 2.9 with sigma of 0.02
 O4-F11
 2.9 with sigma of 0.02
 S3-F11
 2.6 with sigma of 0.02
 S3-F48
 2.6 with sigma of 0.02
 F35-S3
 2.6 with sigma of 0.02
 O92-C94
 1.45 with sigma of 0.02
 C29-O64
 2.4 with sigma of 0.02
 O64-C47
 1.45 with sigma of 0.02
 C18-O92
 2.4 with sigma of 0.02
 O18-C94
 3.2 with sigma of 0.02
 O18-O1D
 4.5 with sigma of 0.02
 O18-C18
 1.45 with sigma of 0.02
 C8-C29
 1.54 with sigma of 0.02
 C8-O64
 1.45 with sigma of 0.02
 C1F-N9
 2.4 with sigma of 0.02
 N9-C7
 1.45 with sigma of 0.001
 C7-C14_$1 = C5_$1-C10_$1
 1.45 with sigma of 0.02
 C7-C14_$1
 1.45 with sigma of 0.001
 O2-C7
 1.25 with sigma of 0.02
 C83-C29
 1.35 with sigma of 0.02
 C83-O18
 2.4 with sigma of 0.02
 C83-C8
 2.4 with sigma of 0.02
 C11-C20
 2.4 with sigma of 0.02
 C16-C11
 2.4 with sigma of 0.02
 C1I-C1F
 2.4 with sigma of 0.02
 C47-C81
 2.4 with sigma of 0.02
 N9-C11 = C1I-C11
 1.4 with sigma of 0.002
 C1I-N9
 2.4 with sigma of 0.002
 O64-C39
 2.4 with sigma of 0.02
 O64-C19
 2.4 with sigma of 0.02
 O64-C81
 1.45 with sigma of 0.02
 C81-C8
 2.4 with sigma of 0.02
 C8-C81
 2.4 with sigma of 0.02
 O29-S3
 1.43 with sigma of 0.02
 O29-O4
 2.43 with sigma of 0.02
 O29-C48
 2.54 with sigma of 0.02
 O19-O29
 2.43 with sigma of 0.02
 O29-C48
 2.6 with sigma of 0.02
 C48-O29
 2.56 with sigma of 0.02
 O29-F48
 2.9 with sigma of 0.02
 O29-F11
 2.9 with sigma of 0.02
 O29-F48
 2.9 with sigma of 0.02
 O29-F35
 2.9 with sigma of 0.02
 F10-C57
 1.35 with sigma of 0.02
 F67-C57
 1.35 with sigma of 0.02
 S1-C57
 1.9 with sigma of 0.02
 O16-C57
 2.54 with sigma of 0.02
 F90-C57
 1.35 with sigma of 0.02
 O34-C57
 2.54 with sigma of 0.02
 O16-C57
 2.54 with sigma of 0.02
 O1-C57
 2.54 with sigma of 0.02
 N1-C5
 2.4 with sigma of 0.02
 C5-C92
 2.4 with sigma of 0.02
 C6-C1B
 1.54 with sigma of 0.002
 C47-C44
 1.54 with sigma of 0.02
 O1D-C44
 1.45 with sigma of 0.02
 O1D-C67
 1.45 with sigma of 0.02
 C67-C44
 2.4 with sigma of 0.005
 C94-C67
 1.54 with sigma of 0.02
 C67-O92
 2.4 with sigma of 0.02
 C44-O64
 2.4 with sigma of 0.02
 O64-C67
 3.2 with sigma of 0.02
 C67-C18
 3.2 with sigma of 0.02
 C44-C83
 2.4 with sigma of 0.02
 C6-C4
 2.4 with sigma of 0.02
 C1A-C6
 2.4 with sigma of 0.02
 C1B-C3
 2.4 with sigma of 0.02
 C18-C13
 2.4 with sigma of 0.02
 C18-C13
 2.4 with sigma of 0.002
 C17-O18
 2.4 with sigma of 0.02
 O18-C13
 1.45 with sigma of 0.02
 O18-C77
 2.4 with sigma of 0.02
 O18-C17
 2.4 with sigma of 0.02
 C77-O18
 2.4 with sigma of 0.02
 O18-C77
 2.4 with sigma of 0.002
 O18-C17
 2.4 with sigma of 0.002
 C17-C83
 3.2 with sigma of 0.02
 C6-C4
 2.4 with sigma of 0.02
 C1A-C6
 2.4 with sigma of 0.02
 C17-C67
 4 with sigma of 0.02
 C83-C13
 3.5 with sigma of 0.005
 C29-C65
 2.4 with sigma of 0.02
 C65-C13
 2.4 with sigma of 0.02
 H65A-H17
 1.9 with sigma of 0.02
 C65-O18
 1.45 with sigma of 0.02
 O18-C65
 1.45 with sigma of 0.001
 C83-C65
 1.54 with sigma of 0.02
 H65B-H17
 1.9 with sigma of 0.02
 C65-C13
 2.5 with sigma of 0.002
 C1F-C11
 1.54 with sigma of 0.002
 C80-C94
 2.4 with sigma of 0.02
 O92-C80
 1.45 with sigma of 0.02
 C80-C18
 1.54 with sigma of 0.02
 O18-C80
 2.4 with sigma of 0.02
 C83-C65 \\sim C8-C29
 with sigma of 0.001
4. Restrained planarity
 C1H, C72, C19, C81, C39, C33, O64
 with sigma of 0.1
 C1H, C72, C19, C81, C39, C33, O64
 with sigma of 0.1
 C4, C3, C1A, C1C, C9, C75, C1E, C17, C13, C77, O18
 with sigma of 0.1
 C4, C3, C1A, C1C, C9, C75, C1E, C17, C13, C77, O18
 with sigma of 0.1
 O18, C13, C17, C77, C9, C1E, C75
 with sigma of 0.02
 C6, C3, C1A, C4, C75, C9, C1C, C1E, C17, C13, C77, O18
 with sigma of 0.1
 C8, C29, C65, C83
 with sigma of 0.1
5. Rigid bond restraints
 F11, F35, F48
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Uiso/Uaniso restraints and constraints
C10 \\sim C92 \\sim C1 \\sim C15 \\sim C14 \\sim N1: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002
F11 \\sim F35 \\sim F48: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002
C40 \\sim C20: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C72 \\sim C1H \\sim C19 \\sim C81 \\sim C39 \\sim C33 \\sim C16 \\sim C1I \\sim
C20 \\sim C40: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C11 \\sim N9 \\sim C7: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
O4 \\sim O29 \\sim O19: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002
O3 \\sim N1: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
C4 \\sim C3 \\sim C1A \\sim C1C \\sim C9 \\sim C75 \\sim C1E \\sim C17 \\sim
C13 \\sim C77: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
O18 \\sim C13: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C1F \\sim C11: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
C5 \\sim N3: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
C6 \\sim C3: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
O18 \\sim C65 \\sim C18 \\sim C80 \\sim C83 \\sim C67 \\sim O92 \\sim C94 \\sim
C29 \\sim O1D \\sim C8 \\sim C44 \\sim C47 \\sim O64: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002
Uanis(C40) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C81)
\\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C1H) \\sim Ueq,
Uanis(C16) \\sim Ueq, Uanis(C1I) \\sim Ueq, Uanis(C20) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
Uanis(C48) \\sim Ueq, Uanis(S3) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O29)
\\sim Ueq, Uanis(O19) \\sim Ueq, Uanis(F11) \\sim Ueq, Uanis(F35) \\sim Ueq,
Uanis(F48) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O1) \\sim Ueq, Uanis(S1) \\sim Ueq, Uanis(O34) \\sim Ueq, Uanis(O16)
\\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(F67) \\sim Ueq, Uanis(F10) \\sim Ueq,
Uanis(F90) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(F48) = Uanis(F11) = Uanis(F35)
Uanis(O3) = Uanis(O2)
7. Rigid body (RIGU) restrains
 O2, C7, N9, C11, C1F, C40, C20, C1I, C16, C1H, C72, C19, C81, C39, C33
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 S3, O4, F11, F35, C48, F48, O29, O19
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S1, O1, F10, F67, F90, O16, C57, O34
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C10, C92, C1, C15, C14, N1, O3, C5, N3, C6, C1B, C4, C3, C1A, C1C, C9, C75,
 C1E, C17, C13, C77
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
8. Others
 Fixed Sof: S1(0.5) O1(0.5) C8(0.33333) H8A(0.33333) H8B(0.33333) C29(0.33333)
 H29(0.33333) C65(0.33333) H65B(0.33333) H65A(0.33333) C67(0.66667)
 H67A(0.66667) H67B(0.66667) C80(0.66667) H80A(0.66667) H80B(0.66667)
 C44(0.66667) H44A(0.66667) H44B(0.66667) C18(0.66667) H18A(0.66667)
 H18B(0.66667) O1D(0.66667) C83(0.33333) H83(0.33333) C47(0.66667)
 H47A(0.66667) H47B(0.66667) C94(0.66667) H94A(0.66667) H94B(0.66667)
 O92(0.66667) F10(0.5) F67(0.5) F90(0.5) O16(0.5) C57(0.5) O34(0.5) S3(0.5)
 O4(0.5) F11(0.5) F35(0.5) C48(0.5) F48(0.5) O29(0.5) O19(0.5)
9.a Ternary CH refined with riding coordinates:
 C6(H6), C11(H11)
9.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C65(H65B,H65A), C67(H67A,H67B), C80(H80A,H80B), C44(H44A,H44B),
 C18(H18A,H18B), C47(H47A,H47B), C94(H94A,H94B)
9.c Me refined with riding coordinates:
 C1B(H1BA,H1BB,H1BC), C1F(H1FA,H1FB,H1FC)
9.d Aromatic/amide H refined with riding coordinates:
 C92(H92), C1(H1), C15(H15), N3(H3), N9(H9), C40(H40), C20(H20), C16(H16),
 C19(H19), C39(H39), C33(H33), C4(H4), C1A(H1A), C1C(H1C), C1E(H1E), C17(H17),
 C77(H77), C29(H29), C83(H83)
9.e Fitted hexagon refined as free rotating group:
 C10(C92,C1,C15,C14,N1)
9.f Naphthalene refined as free rotating group:
 C40(C20,C1I,C16,C1H,C72,C19,C81,C39,C33), C4(C3,C1A,C1C,C9,C75,C1E,C17,C13,C77)
;
_shelx_res_checksum              46604
_shelx_hkl_checksum              15652
_olex2_submission_special_instructions 'No special instructions were received'