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_4134289
_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         'C4 H8 Br2 O, C128 H168 O12'
_chemical_formula_sum            'C132 H176 Br2 O13'
_chemical_formula_weight         2130.54
_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             2018-07-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   43.9781(5)
_cell_length_b                   18.7317(2)
_cell_length_c                   15.60869(16)
_cell_measurement_reflns_used    50125
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.1000
_cell_measurement_theta_min      3.6770
_cell_volume                     12858.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28d (Rigaku OD, 2015)'
_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 0.985
_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    -73.00 -44.00   0.50    3.00    --  -49.37 -57.00-120.00   58
  2  \w    -85.00 -43.00   0.50    3.00    --  -49.37 -19.00-120.00   84
  3  \w    -45.00  -8.00   0.50   12.50    --  -70.00  77.00-180.00   74
  4  \w    -82.00 -54.00   0.50   12.50    --  -70.00  77.00-180.00   56
  5  \w   -118.00 -76.00   0.50    3.00    --  -49.37 -57.00-120.00   84
  6  \w   -126.00 -85.00   0.50   12.50    --  -70.00 -99.00-180.00   82
  7  \w   -141.00 -60.00   0.50   12.50    --  -70.00 -19.00  30.00  162
  8  \w   -119.00 -39.00   0.50    3.00    --  -49.37-178.00  90.00  160
  9  \w     94.00 119.00   0.50   12.50    --  110.00 -19.00 -30.00   50
 10  \w     95.00 123.00   0.50   12.50    --  110.00 -19.00   0.00   56
 11  \w     95.00 123.00   0.50   12.50    --  110.00 -19.00  30.00   56
 12  \w     97.00 123.00   0.50   12.50    --  110.00 -19.00  90.00   52
 13  \w     61.00 110.00   0.50   12.50    --  110.00 -99.00 150.00   98
 14  \w     40.00 120.00   0.50   12.50    --  110.00-125.00 150.00  160
 15  \w     38.00  80.00   0.50   12.50    --  110.00 -57.00   0.00   84
 16  \w     40.00  66.00   0.50   12.50    --  110.00   0.00 -90.00   52
 17  \w     98.00 176.00   0.50   12.50    --  110.00  38.00-150.00  156
 18  \w    130.00 165.00   0.50   12.50    --  110.00   0.00 -90.00   70
 19  \w     92.00 140.00   0.50   12.50    --  110.00 125.00 -60.00   96
 20  \w     39.00  73.00   0.50   12.50    --  110.00 -57.00-150.00   68
 21  \w     50.00  99.00   0.50   12.50    --  110.00 -99.00 -90.00   98
 22  \w     67.00 126.00   0.50   12.50    --  110.00 -77.00 -90.00  118
 23  \w     45.00  72.00   0.50   12.50    --  110.00 -57.00-180.00   54
;
_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      0.0349572000
_diffrn_orient_matrix_UB_12      -0.0044269000
_diffrn_orient_matrix_UB_13      -0.0035599000
_diffrn_orient_matrix_UB_21      -0.0017619000
_diffrn_orient_matrix_UB_22      -0.0209653000
_diffrn_orient_matrix_UB_23      -0.0952620000
_diffrn_orient_matrix_UB_31      0.0017773000
_diffrn_orient_matrix_UB_32      0.0794939000
_diffrn_orient_matrix_UB_33      -0.0253685000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0700
_diffrn_reflns_av_unetI/netI     0.0515
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       54
_diffrn_reflns_limit_h_min       -55
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            95618
_diffrn_reflns_point_group_measured_fraction_full 0.989
_diffrn_reflns_point_group_measured_fraction_max 0.949
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.894
_diffrn_reflns_theta_min         3.004
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.230
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.85166
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28d (Rigaku Oxford Diffraction, 2015)
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    1.101
_exptl_crystal_description       plank
_exptl_crystal_F_000             4568
_exptl_crystal_size_max          0.156
_exptl_crystal_size_mid          0.077
_exptl_crystal_size_min          0.042
_refine_diff_density_max         1.114
_refine_diff_density_min         -1.826
_refine_diff_density_rms         0.111
_refine_ls_abs_structure_details
;
 Flack x determined using 8618 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.013(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1442
_refine_ls_number_reflns         26585
_refine_ls_number_restraints     257
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0890
_refine_ls_R_factor_gt           0.0819
_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^)+(0.1899P)^2^+5.4365P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2392
_refine_ls_wR_factor_ref         0.2469
_reflns_Friedel_coverage         0.783
_reflns_Friedel_fraction_full    0.976
_reflns_Friedel_fraction_max     0.906
_reflns_number_gt                23157
_reflns_number_total             26585
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            CCDC-1914857.cif
_cod_data_source_block           d160815_65_1
_cod_depositor_comments
'Adding full bibliography for 4134283--4134298.cif.'
_cod_database_code               4134289
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C131H174Br2O14
_reflns_odcompleteness_completeness 99.90
_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
 H1-O1B
 2 with sigma of 0.02
 H1BA-O2
 2 with sigma of 0.02
 H4-O1
 2 with sigma of 0.02
 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
 with sigma of 0.02
 C27-C26 \\sim C26-C25
 with sigma of 0.02
 C27-O1 \\sim C25-O1
 with sigma of 0.02
 Br1B-C2C \\sim Br1B-C2B
 with sigma of 0.02
 C2C-C1B \\sim C2B-C1B
 with sigma of 0.02
 C3B-C2B \\sim C2C-C3C
 with sigma of 0.02
 Br2B-C3B \\sim Br2B-C3C
 with sigma of 0.02
 C3B-C4B \\sim C4C-C3C
 with sigma of 0.02
3. 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, Uanis(C7) \\sim Ueq,
Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
4. Rigid body (RIGU) restrains
 C6, C5, C1, C2, C4, C3, C5A, C4A, C3A, C2A, C1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, C8, C9, C11, C10, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Br2B, Br1B, C2B, C2C, C1B, C3B, C3C, O1B, C4B, C4C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H1BD)=Sof(H1BE)=Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(H4CC)=Sof(C3C)=Sof(H3C)=
 Sof(C2C)=Sof(H2C)=1-FVAR(1)
 Sof(H1BB)=Sof(H1BC)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=Sof(C2B)=Sof(H2BA)=
 Sof(C3B)=Sof(H3BA)=FVAR(1)
 Sof(H6BC)=Sof(H6BD)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=
 Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C1A)=Sof(H1AA)=
 Sof(H1AB)=Sof(H1AC)=1-FVAR(2)
 Sof(H6AA)=Sof(H6AB)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C1)=Sof(H1A)=Sof(H1B)=
 Sof(H1C)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C50(H50), C52(H52), C57(H57), C60(H60), C2B(H2BA), C3B(H3BA), C3C(H3C),
 C2C(H2C)
6.b Secondary CH2 refined with riding coordinates:
 C12(H12A,H12B), C18(H18A,H18B), C51(H51A,H51B), C72(H72A,H72B), C73(H73A,
 H73B), C11(H11A,H11B), C17(H17A,H17B), C24(H24A,H24B), C85(H85A,H85B),
 C22(H22A,H22B), C16(H16A,H16B), C10(H10A,H10B), C15(H15A,H15B), C23(H23A,H23B),
  C6(H6AA,H6AB), C6(H6BC,H6BD), C9(H9A,H9B), C21(H21A,H21B), C20(H20A,H20B),
 C14(H14A,H14B), C1B(H1BB,H1BC), C1B(H1BD,H1BE), C5(H5A,H5B), C8(H8A,H8B),
 C2(H2A,H2B), C4(H4A,H4B), C3(H3A,H3B), C5A(H5AA,H5AB), C4A(H4AA,H4AB),
 C3A(H3AA,H3AB), C2A(H2AA,H2AB)
6.c Aromatic/amide H refined with riding coordinates:
 C31(H31), C46(H46), C54(H54), C67(H67)
6.d Idealised Me refined as rotating group:
 C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C), C100(H10C,H10D,
 H10E), C101(H10F,H10G,H10H), C102(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), C127(H12X,
 H12Y,HF), C128(H12Z,HG,HH), C13(H13A,H13B,H13C), C25(H25A,H25B,H25C), C19(H19A,
 H19B,H19C), C27(H27A,H27B,H27C), C4B(H4BA,H4BB,H4BC), C1(H1A,H1B,H1C), C7(H7A,
 H7B,H7C), C4C(H4CA,H4CB,H4CC), C1A(H1AA,H1AB,H1AC)
6.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O3(H3), O4(H4), O1(H1), O1B(H1BA)
;
_shelx_res_checksum              81636
_shelx_hkl_checksum              19684
_olex2_date_sample_data_collection 2018-07-12
_olex2_date_sample_submission    2018-07-12
_olex2_submission_original_sample_id d160815_65_1
_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 3.388
_oxdiff_exptl_absorpt_empirical_full_min 0.650