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_4134297
_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         '0.53(C4 H8 Br2 O), C128 H168 O12'
_chemical_formula_sum            'C130.13 H172.26 Br1.07 O12.53'
_chemical_formula_weight         2022.35
_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             2017-10-25
_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                   15.62340(10)
_cell_length_b                   18.76580(10)
_cell_length_c                   43.5913(2)
_cell_measurement_reflns_used    143656
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.2730
_cell_measurement_theta_min      3.4770
_cell_volume                     12780.34(12)
_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  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (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 0.999
_diffrn_measured_fraction_theta_max 0.997
_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    1.79    --  -49.37 -77.00-180.00   76
  2  \w   -121.00 -34.00   0.50    1.79    --  -49.37 -57.00-150.00  174
  3  \w    -83.00   6.00   0.50    7.16    --  -70.00  38.00 -60.00  178
  4  \w    -73.00  17.00   0.50    1.79    --  -49.37  77.00  60.00  180
  5  \w     59.00 120.00   0.50    1.79    --   49.37 178.00 -90.00  122
  6  \w     91.00 178.00   0.50    7.16    --  110.00 125.00  30.00  174
  7  \w    102.00 178.00   0.50    7.16    --  110.00  96.00  65.00  152
  8  \w     98.00 178.00   0.50    7.16    --  110.00  38.00 150.00  160
  9  \w     94.00 123.00   0.50    7.16    --  110.00 -19.00  60.00   58
 10  \w     94.00 178.00   0.50    7.16    --  110.00  57.00 120.00  168
 11  \w     86.00 177.00   0.50    7.16    --  110.00  77.00 150.00  182
 12  \w     78.00 116.00   0.50    1.79    --   49.37  77.00  30.00   76
 13  \w     94.00 178.00   0.50    7.16    --  110.00  57.00 -60.00  168
 14  \w     98.00 178.00   0.50    7.16    --  110.00  38.00-180.00  160
 15  \w     94.00 178.00   0.50    7.16    --  110.00  57.00-120.00  168
 16  \w     94.00 123.00   0.50    7.16    --  110.00 -19.00-180.00   58
 17  \w     40.00 110.00   0.50    7.16    --  110.00 -99.00-150.00  140
 18  \w     57.00 122.00   0.50    1.79    --   49.37-178.00-120.00  130
 19  \w     40.00 110.00   0.50    7.16    --  110.00 -99.00-180.00  140
 20  \w     41.00 110.00   0.50    7.16    --  110.00 -96.00 -42.00  138
 21  \w     40.00 110.00   0.50    7.16    --  110.00 -99.00  60.00  140
 22  \w     40.00 110.00   0.50    7.16    --  110.00 -99.00 120.00  140
 23  \w     38.00  84.00   0.50    7.16    --  110.00 -57.00 -30.00   92
 24  \w     40.00 110.00   0.50    7.16    --  110.00 -99.00 -30.00  140
 25  \w     40.00 110.00   0.50    7.16    --  110.00 -99.00-120.00  140
 26  \w     38.00  84.00   0.50    7.16    --  110.00 -57.00-180.00   92
 27  \w     38.00  84.00   0.50    7.16    --  110.00 -57.00 -90.00   92
 28  \w     39.00 122.00   0.50    7.16    --  110.00-125.00 -30.00  166
 29  \w     39.00 122.00   0.50    7.16    --  110.00-125.00  90.00  166
 30  \w     38.00  84.00   0.50    7.16    --  110.00 -57.00  30.00   92
 31  \w     38.00  84.00   0.50    7.16    --  110.00 -57.00 -60.00   92
 32  \w     38.00  84.00   0.50    7.16    --  110.00 -57.00  90.00   92
 33  \w    -94.00  -3.00   0.50    7.16    --  -70.00  77.00 150.00  182
 34  \w    -83.00   6.00   0.50    7.16    --  -70.00  38.00  90.00  178
 35  \w    -86.00   2.00   0.50    7.16    --  -70.00  57.00 -30.00  176
 36  \w   -116.00 -78.00   0.50    1.79    --  -49.37 -77.00   0.00   76
 37  \w   -116.00 -78.00   0.50    1.79    --  -49.37 -77.00 -30.00   76
 38  \w   -116.00 -78.00   0.50    1.79    --  -49.37 -77.00 -60.00   76
 39  \w   -121.00 -34.00   0.50    1.79    --  -49.37 -57.00   0.00  174
 40  \w   -116.00 -78.00   0.50    1.79    --  -49.37 -77.00 150.00   76
 41  \w   -116.00 -78.00   0.50    1.79    --  -49.37 -77.00 120.00   76
 42  \w   -116.00 -78.00   0.50    1.79    --  -49.37 -77.00  60.00   76
 43  \w   -121.00 -34.00   0.50    1.79    --  -49.37 -57.00 120.00  174
;
_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      0.0353227000
_diffrn_orient_matrix_UB_12      -0.0753767000
_diffrn_orient_matrix_UB_13      0.0060364000
_diffrn_orient_matrix_UB_21      -0.0021889000
_diffrn_orient_matrix_UB_22      -0.0157016000
_diffrn_orient_matrix_UB_23      -0.0346850000
_diffrn_orient_matrix_UB_31      0.0920187000
_diffrn_orient_matrix_UB_32      0.0284918000
_diffrn_orient_matrix_UB_33      -0.0031341000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0620
_diffrn_reflns_av_unetI/netI     0.0272
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -15
_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            266306
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.830
_diffrn_reflns_theta_min         3.005
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.883
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.711
_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    1.051
_exptl_crystal_description       plate
_exptl_crystal_F_000             4363
_exptl_crystal_size_max          0.168
_exptl_crystal_size_mid          0.144
_exptl_crystal_size_min          0.036
_refine_diff_density_max         3.362
_refine_diff_density_min         -0.514
_refine_diff_density_rms         0.078
_refine_ls_abs_structure_details
;
 Flack x determined using 10797 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.012(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.025
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1463
_refine_ls_number_reflns         27644
_refine_ls_number_restraints     468
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0770
_refine_ls_R_factor_gt           0.0733
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1520P)^2^+5.9710P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2104
_refine_ls_wR_factor_ref         0.2149
_reflns_Friedel_coverage         0.845
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                25599
_reflns_number_total             27644
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            CCDC-1914843.cif
_cod_data_source_block           d160815_44_25
_cod_depositor_comments
'Adding full bibliography for 4134283--4134298.cif.'
_cod_database_code               4134297
_shelx_shelxl_version_number     2016/6
_chemical_oxdiff_formula         C132H176Br2O13
_reflns_odcompleteness_completeness 99.96
_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. Shared sites
{Br2C, Br2B}
{Br1B, Br1C}
{O1B, O1C}
{C1B, C1C}
{H1BC, H1CC}
3. Restrained distances
 H4-O3
 2.05 with sigma of 0.02
 H3-O2
 2 with sigma of 0.02
 H2-O1
 2 with sigma of 0.02
 H1BC-O4
 2 with sigma of 0.02
 H1CC-O4
 2 with sigma of 0.02
 C128-C111
 1.52 with sigma of 0.01
 O1B-C1B = O1C-C1C
 1.43 with sigma of 0.01
 C6-C5 \\sim C6-C5A \\sim C5-C4 \\sim C5A-C4A \\sim C4-C3 \\sim C4A-C3A \\sim
C3-C2 \\sim C3A-C2A \\sim C2-C1
 \\sim C2A-C1A
 with sigma of 0.02
 C1-C3 \\sim C1A-C3A \\sim C2-C4 \\sim C2A-C4A \\sim C3-C5 \\sim C3A-C5A \\sim
C4-C6 \\sim C4A-C6
 with sigma of 0.02
 C9-C8A \\sim C9-C8 \\sim C9-C10 \\sim C8A-C7A \\sim C8-C7
 with sigma of 0.02
 C7A-C9 \\sim C7-C9 \\sim C8A-C10 \\sim C8-C10
 with sigma of 0.02
 Br1B-C2B \\sim Br1C-C2C
 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
 Br2B-C3B \\sim Br2C-C3C
 with sigma of 0.02
 C2B-C1B \\sim C2C-C1C
 with sigma of 0.02
 O1B-C1B \\sim O1C-C1C
 with sigma of 0.02
 C127-C111 \\sim C128-C111
 with sigma of 0.02
4. Rigid bond restraints
 C6, C5, C2, C1, C3, C4, C1A, C2A, C3A, C4A, C5A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C11, C10, C9, C8A, C7A, C8, C7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2B, Br2B, C3B, H3BA, C4B, Br1B, C1B, H2BA, H4BA, H4BB, H4BC, H1BA, H1BB, O1B,
  H1BC, C2C, C3C, H3C, C4C, Br2C, H4CA, H4CB, H4CC, H2C, Br1C, C1C, H1CA, H1CB,
 O1C, H1CC
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Uanis(C1) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C2A)
\\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C10) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C8A)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C7A) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
Uanis(C4C) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.005
Uanis(C1B) \\sim Ueq, Uanis(C1C) \\sim Ueq: with sigma of 0.002 and sigma for
terminal atoms of 0.002
Uanis(C128) \\sim Ueq, Uanis(C127) \\sim Ueq, Uanis(O4) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C128) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.02
Uanis(Br1B) = Uanis(Br1C)
Uanis(Br2C) = Uanis(Br2B)
Uanis(C1B) = Uanis(C1C)
Uanis(O1B) = Uanis(O1C)
Uiso(H1BC) = Uiso(H1CC)
6. Rigid body (RIGU) restrains
 C6, C5, C2, C1, C3, C4, C1A, C2A, C3A, C4A, C5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C10, C9, C8A, C7A, C8, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C2B, Br2B, C3B, H3BA, C4B, Br1B, C1B, H2BA, H4BA, H4BB, H4BC, H1BA, H1BB, O1B,
  H1BC, C2C, C3C, H3C, C4C, Br2C, H4CA, H4CB, H4CC, H2C, Br1C, C1C, H1CA, H1CB,
 O1C, H1CC
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C111, C110, C128, O4, C127, C103
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 Sof(H6BC)=Sof(H6BD)=Sof(H9BC)=Sof(H9BD)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C7A)=
 Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=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(C5A)=Sof(H5AA)=Sof(H5AB)=1-FVAR(1)
 Sof(H6AA)=Sof(H6AB)=Sof(H9AA)=Sof(H9AB)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C3)=Sof(H3A)=Sof(H3B)=
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C7)=Sof(H7A)=Sof(H7B)=
 Sof(H7C)=FVAR(1)
 Sof(Br2B)=Sof(Br1B)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(O1B)=Sof(H1BC)=Sof(C2B)=
 Sof(H2BA)=Sof(C3B)=Sof(H3BA)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=FVAR(2)
 Sof(C3C)=Sof(H3C)=Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(H4CC)=Sof(C2C)=Sof(H2C)=
 Sof(Br2C)=Sof(Br1C)=Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(O1C)=Sof(H1CC)=FVAR(3)
8.a Ternary CH refined with riding coordinates:
 C36(H36), C38(H38), C44(H44), C55(H55), C2B(H2BA), C3B(H3BA), C3C(H3C),
 C2C(H2C)
8.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C18(H18A,H18B), C57(H57A,H57B), C58(H58A,H58B), C72(H72A,
 H72B), C24(H24A,H24B), C17(H17A,H17B), C73(H73A,H73B), C11(H11A,H11B),
 C16(H16A,H16B), C1B(H1BA,H1BB), C22(H22A,H22B), C23(H23A,H23B), C10(H10A,H10B),
  C6(H6AA,H6AB), C6(H6BC,H6BD), C9(H9BC,H9BD), C9(H9AA,H9AB), C21(H21A,H21B),
 C20(H20A,H20B), C15(H15A,H15B), C14(H14A,H14B), C5(H5A,H5B), C8A(H8AA,H8AB),
 C2(H2A,H2B), C3(H3A,H3B), C4(H4A,H4B), C2A(H2AA,H2AB), C3A(H3AA,H3AB),
 C4A(H4AA,H4AB), C5A(H5AA,H5AB), C8(H8A,H8B), C1C(H1CA,H1CB)
8.c Aromatic/amide H refined with riding coordinates:
 C25(H25), C35(H35), C42(H42), C49(H49)
8.d Idealised Me refined as rotating group:
 C85(H85A,H85B,H85C), C89(H89A,H89B,H89C), C92(H92A,H92B,H92C), C94(H94A,H94B,
 H94C), C96(H96A,H96B,H96C), C97(H97A,H97B,H97C), C99(H99A,H99B,H99C),
 C100(H10C,H10D,H10E), C101(H10F,H10G,H10H), C102(H10I,H10J,H10K), C104(H10L,
 H10M,H10N), C106(H10O,H10P,H10Q), C107(H10R,H10S,H10T), C108(H10U,H10V,H10W),
 C109(H10X,H10Y,H), C112(H11C,H11D,H11E), C113(H11F,H11G,H11H), C114(H11I,H11J,
 H11K), C115(H11L,H11M,H11N), C116(H11O,H11P,H11Q), C117(H11R,H11S,H11T),
 C118(H11U,H11V,H11W), C119(H11X,H11Y,HA), C120(H12C,H12D,H12E), C121(H12F,H12G,
 H12H), C122(H12I,H12J,H12K), C123(H12L,H12M,H12N), C124(H12O,H12P,H12Q),
 C125(H12R,H12S,H12T), C19(H19A,H19B,H19C), C126(H12U,H12V,H12W), C127(H12X,
 H12Y,HB), C13(H13A,H13B,H13C), C1(H1A,H1B,H1C), C128(H12Z,HC,HD), C7A(H7AA,
 H7AB,H7AC), C4B(H4BA,H4BB,H4BC), C1A(H1AA,H1AB,H1AC), C7(H7A,H7B,H7C),
 C4C(H4CA,H4CB,H4CC)
8.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O3(H3), O2(H2), O4(H4), O1B(H1BC), O1C(H1CC)
;
_shelx_res_checksum              99099
_shelx_hkl_checksum              93771
_olex2_date_sample_data_collection 2017-10-16
_olex2_date_sample_submission    2017-10-16
_olex2_submission_original_sample_id d160815_44_25
_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 1.310
_oxdiff_exptl_absorpt_empirical_full_min 0.861