Molecular Recognition and Cocrystallization of Methylated and Halogenated Fragments of Danicalipin A by Enantiopure Alleno-Acetylenic Cage Receptors.
Gropp, Cornelius; Fischer, Stefan; Husch, Tamara; Trapp, Nils; Carreira, Erick M.; Diederich, François; Journal of the American Chemical Society 142 (2020) 4749–4755; doi:10.1021/jacs.9b13217

data_4134283
_publ_section_title
;
 Molecular Recognition and Cocrystallization of Methylated and Halogenated
 Fragments of Danicalipin A by Enantiopure Alleno-Acetylenic Cage
 Receptors.
;
_journal_issue                   10
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              4749
_journal_page_last               4755
_journal_paper_doi               10.1021/jacs.9b13217
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration ad
_chemical_formula_moiety         '1(C4 H8 Br2 O), C128 H168 O12'
_chemical_formula_sum            'C132 H176 Br2 O13'
_chemical_formula_weight         2130.51
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2017-10-10
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.55780(10)
_cell_length_b                   18.75530(10)
_cell_length_c                   43.8495(3)
_cell_measurement_reflns_used    92343
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.4400
_cell_measurement_theta_min      3.0190
_cell_volume                     12794.90(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.31d (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.0(1)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            'Pilatus 300K'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.994
_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   -116.00 -78.00   0.50    2.00    --  -49.37 -77.00  30.00   76
  2  \w   -116.00 -78.00   0.50    2.00    --  -49.37 -77.00   0.00   76
  3  \w   -116.00 -78.00   0.50    2.00    --  -49.37 -77.00  60.00   76
  4  \w   -125.00 -37.00   0.50    2.00    --  -49.37 -19.00 -60.00  176
  5  \w    -62.00  27.00   0.50    2.00    --  -49.37  19.00  60.00  178
  6  \w    -65.00  22.00   0.50    2.00    --  -49.37  57.00 120.00  174
  7  \w    -95.00  -9.00   0.50    4.50    --  -70.00 125.00 150.00  172
  8  \w    -94.00  -3.00   0.50    4.50    --  -70.00  77.00 -90.00  182
  9  \w   -137.00 -78.00   0.50    4.50    --  -70.00 -77.00 -30.00  118
 10  \w   -120.00 -38.00   0.50    2.00    --  -49.37-178.00-150.00  164
 11  \w     57.00 122.00   0.50    2.00    --   49.37-178.00  90.00  130
 12  \w     40.00 110.00   0.50    4.50    --  110.00 -99.00 -30.00  140
 13  \w     85.00 110.00   0.50    4.50    --  110.00 -99.00 -60.00   50
 14  \w     95.00 122.00   0.50    4.50    --  110.00-125.00-120.00   54
 15  \w     40.00 110.00   0.50    4.50    --  110.00 -99.00-120.00  140
 16  \w     94.00 119.00   0.50    4.50    --  110.00 -19.00-120.00   50
 17  \w     94.00 119.00   0.50    4.50    --  110.00 -19.00-150.00   50
 18  \w     98.00 178.00   0.50    4.50    --  110.00  38.00-150.00  160
 19  \w    153.00 178.00   0.50    4.50    --  110.00 125.00 -90.00   50
 20  \w     95.00 177.00   0.50    4.50    --  110.00  57.00 -90.00  164
 21  \w     94.00 178.00   0.50    4.50    --  110.00  57.00   0.00  168
 22  \w    105.00 166.00   0.50    4.50    --  110.00  38.00 150.00  122
 23  \w     94.00 123.00   0.50    4.50    --  110.00 -19.00  90.00   58
 24  \w     94.00 123.00   0.50    4.50    --  110.00 -19.00  30.00   58
 25  \w     94.00 123.00   0.50    4.50    --  110.00 -19.00  60.00   58
 26  \w     94.00 119.00   0.50    4.50    --  110.00 -19.00 120.00   50
 27  \w     39.00 122.00   0.50    4.50    --  110.00-125.00 120.00  166
 28  \w     40.00 110.00   0.50    4.50    --  110.00 -99.00  90.00  140
 29  \w     40.00  77.00   0.50    4.50    --  110.00 -57.00   0.00   74
 30  \w     38.00  84.00   0.50    4.50    --  110.00 -57.00  30.00   92
 31  \w     40.00  93.00   0.50    4.50    --  110.00 -99.00  30.00  106
 32  \w     39.00  77.00   0.50    4.50    --  110.00 -57.00  90.00   76
 33  \w     42.00  78.00   0.50    4.50    --  110.00 -99.00 -60.00   72
 34  \w     49.00  75.00   0.50    4.50    --  110.00 -57.00 -90.00   52
 35  \w     45.00 108.00   0.50    4.50    --  110.00 -99.00-150.00  126
 36  \w     38.00  84.00   0.50    4.50    --  110.00 -57.00-150.00   92
 37  \w     39.00  64.00   0.50    4.50    --  110.00-125.00-120.00   50
 38  \w     40.00  88.00   0.50    4.50    --  110.00-125.00-150.00   96
 39  \w     94.00 177.00   0.50    4.50    --  110.00  57.00-120.00  166
 40  \w     96.00 134.00   0.50    4.50    --  110.00 125.00 -90.00   76
 41  \w   -145.00 -56.00   0.50    4.50    --  -70.00 -38.00 120.00  178
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0110166000
_diffrn_orient_matrix_UB_12      0.0057277000
_diffrn_orient_matrix_UB_13      -0.0348209000
_diffrn_orient_matrix_UB_21      0.0641117000
_diffrn_orient_matrix_UB_22      0.0626038000
_diffrn_orient_matrix_UB_23      -0.0006712000
_diffrn_orient_matrix_UB_31      0.0746890000
_diffrn_orient_matrix_UB_32      -0.0528604000
_diffrn_orient_matrix_UB_33      -0.0045736000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0505
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -55
_diffrn_reflns_number            212525
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.121
_diffrn_reflns_theta_min         3.101
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.236
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.725
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.31d (Rigaku Oxford Diffraction, 2017)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.106
_exptl_crystal_description       plate
_exptl_crystal_F_000             4568
_exptl_crystal_size_max          0.149
_exptl_crystal_size_mid          0.126
_exptl_crystal_size_min          0.031
_refine_diff_density_max         0.927
_refine_diff_density_min         -0.736
_refine_diff_density_rms         0.058
_refine_ls_abs_structure_details
;
 Flack x determined using 10178 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.007(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1507
_refine_ls_number_reflns         27576
_refine_ls_number_restraints     303
_refine_ls_restrained_S_all      1.047
_refine_ls_R_factor_all          0.0601
_refine_ls_R_factor_gt           0.0536
_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^)+(0.0969P)^2^+5.6520P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1493
_refine_ls_wR_factor_ref         0.1554
_reflns_Friedel_coverage         0.839
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.979
_reflns_number_gt                24776
_reflns_number_total             27576
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            CCDC-1914842.cif
_cod_data_source_block           d160815_44_22
_cod_depositor_comments
'Adding full bibliography for 4134283--4134298.cif.'
_cod_database_code               4134283
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C133H179BrO13
_reflns_odcompleteness_completeness 99.95
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 C2A-C1A = C2-C1 = C3-C2 = C3A-C2A = C4A-C3A = C4-C3 = C5-C4 = C5-C4A = C6-C5 =
  C6-C55
 1.5 with sigma of 0.005
 O1D-C1D
 1.448 with sigma of 0.002
 C4D-C3D = C2D-C1D = C3D-C2D
 1.5 with sigma of 0.02
 H1D-O2
 3 with sigma of 0.02
 C9-C10 \\sim C9-C8A \\sim C9-C8 \\sim C8A-C7A \\sim C8-C7
 with sigma of 0.02
 Br2B-C3B \\sim Br2C-C2C
 with sigma of 0.02
 O1C-C1C \\sim O1B-C1B
 with sigma of 0.02
 C2C-C1C \\sim C2B-C1B
 with sigma of 0.02
 C3C-C2C \\sim C3B-C2B
 with sigma of 0.02
 C4B-C3B \\sim C4C-C3C
 with sigma of 0.02
 Br1C-C3C \\sim Br1B-C2B
 with sigma of 0.02
 Br1C-C3C \\sim Br1B-C2B \\sim Br1D-C3D
 with sigma of 0.02
 Br2D-C2D \\sim Br2B-C3B \\sim Br2C-C2C
 with sigma of 0.02
 C3B-C2B \\sim C3C-C2C \\sim C3D-C2D
 with sigma of 0.02
 C6-C5 \\sim C5-C4 \\sim C5-C4A \\sim C4-C3 \\sim C4A-C3A \\sim C3-C2 \\sim
C3A-C2A \\sim C2A-C1A \\sim C2-C1
 with sigma of 0.02
 C1-C3 \\sim C1A-C3A \\sim C2-C4 \\sim C2A-C4A \\sim C3-C5 \\sim C3A-C5 \\sim
C4-C6 \\sim C4A-C6
 with sigma of 0.02
 C2B-C1B \\sim C2D-C1D \\sim C2C-C1C
 with sigma of 0.02
 O1C-C1C \\sim O1B-C1B \\sim O1D-C1D
 with sigma of 0.02
 C4B-C3B \\sim C4C-C3C \\sim C4D-C3D
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C2) = Uanis(C2A)
Uanis(C1) = Uanis(C1A)
Uanis(Br1C) = Uanis(Br1D)
Uanis(Br2C) = Uanis(Br2D)
Uanis(C3C) = Uanis(C3D)
Uanis(C1C) = Uanis(C1D)
Uanis(O1C) = Uanis(O1D)
Uanis(C4C) = Uanis(C4D)
4. Rigid body (RIGU) restrains
 C10, C9, C8, C7, C8A, C7A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6, C5, C2, C1, C4, C3, C1A, C2A, C3A, C4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Br1D, C3D, C2D, C4D, Br2D, C1D, O1D, Br1C, Br2C, C2C, C3C, C1C, C4C, O1C,
 Br1B, C2B, C1B, C3B, O1B, Br2B, C4B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 1*[Sof(Br1B)+Sof(Br2B)+Sof(O1B)+Sof(H1BA)+Sof(C2B)+Sof(H2BA)+Sof(C4B)+
 Sof(H4BA)+Sof(H4BB)+Sof(H4BC)+Sof(C1B)+Sof(H1BB)+Sof(H1BC)+Sof(C3B)+Sof(H3BA)]+
 1*[Sof(Br2C)+Sof(Br1C)+Sof(C3C)+Sof(H3C)+Sof(C2C)+Sof(H2C)+Sof(C4C)+Sof(H4CA)+
 Sof(H4CB)+Sof(H4CC)+Sof(O1C)+Sof(H1CA)+Sof(C1C)+Sof(H1CB)+Sof(H1CC)]+1*
 [Sof(Br1D)+Sof(C3D)+Sof(H3D)+Sof(C2D)+Sof(H2D)+Sof(Br2D)+Sof(C4D)+Sof(H4DA)+
 Sof(H4DB)+Sof(H4DC)+Sof(C1D)+Sof(H1DA)+Sof(H1DB)+Sof(O1D)+Sof(H1D)]=1 with esd
 of 0.00001
 Sof(Br1B)=Sof(Br2B)=Sof(O1B)=Sof(H1BA)=Sof(C2B)=Sof(H2BA)=Sof(C4B)=Sof(H4BA)=
 Sof(H4BB)=Sof(H4BC)=Sof(C1B)=Sof(H1BB)=Sof(H1BC)=Sof(C3B)=Sof(H3BA)=FVAR(1)
 Sof(H9BC)=Sof(H9BD)=Sof(H5BC)=Sof(H5BD)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=
 Sof(H1AC)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=
 Sof(H4AA)=Sof(H4AB)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=
 Sof(H7AC)=1-FVAR(2)
 Sof(H9AA)=Sof(H9AB)=Sof(H5AA)=Sof(H5AB)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C1)=
 Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(H7C)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C3)=Sof(H3A)=Sof(H3B)=FVAR(2)
 Sof(Br2C)=Sof(Br1C)=Sof(C3C)=Sof(H3C)=Sof(C2C)=Sof(H2C)=Sof(C4C)=Sof(H4CA)=
 Sof(H4CB)=Sof(H4CC)=Sof(O1C)=Sof(H1CA)=Sof(C1C)=Sof(H1CB)=Sof(H1CC)=FVAR(3)
 Sof(Br1D)=Sof(C3D)=Sof(H3D)=Sof(C2D)=Sof(H2D)=Sof(Br2D)=Sof(C4D)=Sof(H4DA)=
 Sof(H4DB)=Sof(H4DC)=Sof(C1D)=Sof(H1DA)=Sof(H1DB)=Sof(O1D)=Sof(H1D)=FVAR(4)
6.a Ternary CH refined with riding coordinates:
 C34(H34), C48(H48), C55(H55), C57(H57), C2B(H2BA), C3B(H3BA), C3C(H3C),
 C2C(H2C), C3D(H3D), C2D(H2D)
6.b Secondary CH2 refined with riding coordinates:
 C18(H18A,H18B), C12(H12A,H12B), C56(H56A,H56B), C66(H66A,H66B), C16(H16A,
 H16B), C71(H71A,H71B), C24(H24A,H24B), C17(H17A,H17B), C11(H11A,H11B),
 C79(H79A,H79B), C23(H23A,H23B), C22(H22A,H22B), C6(H6A,H6B), C10(H10A,H10B),
 C15(H15A,H15B), C9(H9AA,H9AB), C9(H9BC,H9BD), C21(H21A,H21B), C20(H20A,H20B),
 C14(H14A,H14B), C5(H5AA,H5AB), C5(H5BC,H5BD), C1B(H1BB,H1BC), C2(H2A,H2B),
 C8(H8A,H8B), C4(H4A,H4B), C3(H3A,H3B), C2A(H2AA,H2AB), C3A(H3AA,H3AB),
 C4A(H4AA,H4AB), C8A(H8AA,H8AB), C1C(H1CB,H1CC), C1D(H1DA,H1DB)
6.c Me refined with riding coordinates:
 C4D(H4DA,H4DB,H4DC)
6.d Aromatic/amide H refined with riding coordinates:
 C27(H27), C28(H28), C46(H46), C47(H47)
6.e Idealised Me refined as rotating group:
 C86(H86A,H86B,H86C), C88(H88A,H88B,H88C), C94(H94A,H94B,H94C), C97(H97A,H97B,
 H97C), C98(H98A,H98B,H98C), C100(H10C,H10D,H10E), C101(H10F,H10G,H10H),
 C103(H10I,H10J,H10K), C105(H10L,H10M,H10N), C106(H10O,H10P,H10Q), C107(H10R,
 H10S,H10T), C108(H10U,H10V,H10W), C109(H10X,H10Y,H), C110(H11C,H11D,H11E),
 C111(H11F,H11G,H11H), C112(H11I,H11J,H11K), C113(H11L,H11M,H11N), C114(H11O,
 H11P,H11Q), C115(H11R,H11S,H11T), C116(H11U,H11V,H11W), C117(H11X,H11Y,HA),
 C118(H11Z,HB,HC), C119(H11,HD,HE), C120(H12C,H12D,H12E), C121(H12F,H12G,H12H),
 C122(H12I,H12J,H12K), C123(H12L,H12M,H12N), C124(H12O,H12P,H12Q), C125(H12R,
 H12S,H12T), C126(H12U,H12V,H12W), C19(H19A,H19B,H19C), C4B(H4BA,H4BB,H4BC),
 C13(H13A,H13B,H13C), C127(H12X,H12Y,HF), C128(H12Z,HG,HH), C1(H1A,H1B,H1C),
 C7(H7A,H7B,H7C), C1A(H1AA,H1AB,H1AC), C7A(H7AA,H7AB,H7AC), C4C(H4CA,H4CB,H4CC)
6.f Idealised tetrahedral OH refined as rotating group:
 O3(H3), O1(H1), O2(H2), O4(H4), O1B(H1BA), O1C(H1CA), O1D(H1D)
;
_shelx_res_checksum              63399
_shelx_hkl_checksum              41634
_olex2_date_sample_data_collection 2017-10-09
_olex2_date_sample_submission    2017-10-09
_olex2_submission_original_sample_id d160815_44_22
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.708
_oxdiff_exptl_absorpt_empirical_full_min 0.835