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_4134293
_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         'C128 H168 O12, 0.66(C4 H8 Br2 O)'
_chemical_formula_sum            'C130.65 H173.29 Br1.32 O12.66'
_chemical_formula_weight         2051.95
_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             2017-10-06
_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                   15.56520(10)
_cell_length_b                   18.75780(10)
_cell_length_c                   43.9214(3)
_cell_measurement_reflns_used    97110
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.2600
_cell_measurement_theta_min      3.4600
_cell_volume                     12823.68(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  '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 1.000
_diffrn_measured_fraction_theta_max 0.996
_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   -101.00 -15.00   0.50    4.00    --  -49.37 136.00 -47.00  172
  2  \w    -94.00  -3.00   0.50   12.20    --  -70.00  77.00 -60.00  182
  3  \w    -62.00  27.00   0.50    4.00    --  -49.37  19.00 -30.00  178
  4  \w     78.00 116.00   0.50    4.00    --   49.37  77.00-150.00   76
  5  \w     94.00 123.00   0.50   12.20    --  110.00 -19.00-150.00   58
  6  \w     97.00 178.00   0.50   12.20    --  110.00  19.00-120.00  162
  7  \w     94.00 123.00   0.50   12.20    --  110.00 -19.00 -30.00   58
  8  \w     94.00 123.00   0.50   12.20    --  110.00 -19.00   0.00   58
  9  \w     94.00 123.00   0.50   12.20    --  110.00 -19.00  30.00   58
 10  \w     94.00 123.00   0.50   12.20    --  110.00 -19.00  90.00   58
 11  \w     94.00 123.00   0.50   12.20    --  110.00 -19.00 120.00   58
 12  \w     98.00 178.00   0.50   12.20    --  110.00  38.00  60.00  160
 13  \w     86.00 177.00   0.50   12.20    --  110.00  77.00   0.00  182
 14  \w     94.00 178.00   0.50   12.20    --  110.00  57.00  90.00  168
 15  \w     86.00 177.00   0.50   12.20    --  110.00  77.00-150.00  182
 16  \w     94.00 178.00   0.50   12.20    --  110.00  57.00-180.00  168
 17  \w     44.00 134.00   0.50   12.20    --  110.00 -77.00 -60.00  180
 18  \w     39.00 122.00   0.50   12.20    --  110.00-125.00 -60.00  166
 19  \w     40.00 110.00   0.50   12.20    --  110.00 -99.00-180.00  140
 20  \w     40.00 110.00   0.50   12.20    --  110.00 -99.00 -60.00  140
 21  \w     40.00 110.00   0.50   12.20    --  110.00 -99.00  30.00  140
 22  \w     44.00 134.00   0.50   12.20    --  110.00 -77.00 120.00  180
 23  \w     39.00 121.00   0.50   12.20    --  110.00-123.00 150.00  164
 24  \w     38.00  84.00   0.50   12.20    --  110.00 -57.00  30.00   92
 25  \w     40.00 110.00   0.50   12.20    --  110.00 -99.00  90.00  140
 26  \w     38.00  84.00   0.50   12.20    --  110.00 -57.00  90.00   92
 27  \w     38.00  84.00   0.50   12.20    --  110.00 -57.00   0.00   92
 28  \w     38.00  84.00   0.50   12.20    --  110.00 -57.00 -90.00   92
 29  \w     38.00  84.00   0.50   12.20    --  110.00 -57.00-180.00   92
 30  \w     38.00  84.00   0.50   12.20    --  110.00 -57.00 -60.00   92
 31  \w     38.00  84.00   0.50   12.20    --  110.00 -57.00 150.00   92
 32  \w    -94.00  -3.00   0.50   12.20    --  -70.00  77.00 150.00  182
 33  \w   -116.00 -78.00   0.50    4.00    --  -49.37 -77.00  90.00   76
 34  \w   -121.00 -34.00   0.50    4.00    --  -49.37 -57.00 150.00  174
 35  \w   -116.00 -78.00   0.50    4.00    --  -49.37 -77.00 -30.00   76
 36  \w   -116.00 -78.00   0.50    4.00    --  -49.37 -77.00 -60.00   76
 37  \w   -121.00 -34.00   0.50    4.00    --  -49.37 -57.00-120.00  174
 38  \w   -121.00 -34.00   0.50    4.00    --  -49.37 -57.00  60.00  174
 39  \w   -121.00 -74.00   0.50    4.00    --  -49.37 -57.00 -60.00   94
 40  \w   -121.00 -34.00   0.50    4.00    --  -49.37 -57.00 -30.00  174
 41  \w   -140.00 -84.00   0.50   12.20    --  -70.00 -99.00-180.00  112
 42  \w   -137.00 -78.00   0.50   12.20    --  -70.00 -77.00-120.00  118
 43  \w   -137.00 -78.00   0.50   12.20    --  -70.00 -77.00-180.00  118
 44  \w   -137.00 -78.00   0.50   12.20    --  -70.00 -77.00  30.00  118
;
_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      0.0092532000
_diffrn_orient_matrix_UB_12      0.0804952000
_diffrn_orient_matrix_UB_13      0.0061620000
_diffrn_orient_matrix_UB_21      0.0005008000
_diffrn_orient_matrix_UB_22      0.0144441000
_diffrn_orient_matrix_UB_23      -0.0345246000
_diffrn_orient_matrix_UB_31      -0.0985394000
_diffrn_orient_matrix_UB_32      0.0076338000
_diffrn_orient_matrix_UB_33      0.0004095000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0771
_diffrn_reflns_av_unetI/netI     0.0357
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -19
_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            265365
_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         79.852
_diffrn_reflns_theta_min         3.012
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.977
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.801
_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    1.063
_exptl_crystal_description       plank
_exptl_crystal_F_000             4419
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.067
_exptl_crystal_size_min          0.03
_refine_diff_density_max         3.492
_refine_diff_density_min         -0.959
_refine_diff_density_rms         0.098
_refine_ls_abs_structure_details
;
 Flack x determined using 9989 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.009(4)
_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     1395
_refine_ls_number_reflns         27728
_refine_ls_number_restraints     157
_refine_ls_restrained_S_all      1.025
_refine_ls_R_factor_all          0.0963
_refine_ls_R_factor_gt           0.0890
_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^)+(0.1886P)^2^+10.5685P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2560
_refine_ls_wR_factor_ref         0.2664
_reflns_Friedel_coverage         0.845
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                24701
_reflns_number_total             27728
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            CCDC-1914837.cif
_cod_data_source_block           d160815_44_20
_cod_depositor_comments
'Adding full bibliography for 4134283--4134298.cif.'
_cod_database_code               4134293
_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. Restrained distances
 C5-C4 = C5A-C4A = C4-C3 = C4A-C3A = C3A-C2 = C3-C2 = C2-C1
 1.5 with sigma of 0.01
 H4-O3
 1.9 with sigma of 0.02
 C60-C6 \\sim C6-C5A \\sim C6-C5 \\sim C5A-C4A \\sim C5-C4 \\sim C4-C3 \\sim
C4A-C3A \\sim C3-C2 \\sim C3A-C2
 \\sim C2-C1
 with sigma of 0.02
3. Rigid bond restraints
 C1, C2, C6, C3, C4, C5, C3A, C4A, C5A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C4) \\sim Ueq, Uanis(C4A) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C3A)
\\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.02 and
sigma for terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 C1, C2, C6, C3, C4, C5, C3A, C4A, C5A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Br1B)=Sof(Br2B)=Sof(O1B)=Sof(H1BA)=Sof(C1B)=Sof(H1BB)=Sof(H1BC)=Sof(C2B)=
 Sof(H2B)=Sof(C3B)=Sof(H3BA)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(H4BC)=FVAR(1)
 Sof(H2BC)=Sof(H2BD)=Sof(H6BC)=Sof(H6BD)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C4A)=
 Sof(H4AA)=Sof(H4AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=1-FVAR(2)
 Sof(H2AA)=Sof(H2AB)=Sof(H6AA)=Sof(H6AB)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C4)=
 Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C34(H34), C43(H43), C60(H60), C64(H64), C2B(H2B), C3B(H3BA)
7.b Secondary CH2 refined with riding coordinates:
 C2(H2AA,H2AB), C2(H2BC,H2BD), C6(H6AA,H6AB), C6(H6BC,H6BD), C8(H8A,H8B),
 C9(H9A,H9B), C10(H10A,H10B), C11(H11A,H11B), C12(H12A,H12B), C14(H14A,H14B),
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C20(H20A,H20B),
  C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B), C57(H57A,
 H57B), C63(H63A,H63B), C71(H71A,H71B), C75(H75A,H75B), C3(H3A,H3B), C4(H4A,
 H4B), C5(H5A,H5B), C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C1B(H1BB,
 H1BC)
7.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C28(H28), C42(H42), C49(H49)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C7(H7A,H7B,H7C), C13(H13A,H13B,H13C), C19(H19A,H19B,H19C),
 C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C93(H93A,H93B,H93C), C97(H97A,H97B,
 H97C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C), C102(H10C,H10D,H10E),
 C103(H10F,H10G,H10H), C104(H10I,H10J,H10K), C105(H10L,H10M,H10N), C106(H10O,
 H10P,H10Q), C107(H10R,H10S,H10T), C108(H10U,H10V,H10W), C109(H10X,H10Y,H),
 C111(H11C,H11D,H11E), C112(H11F,H11G,H11H), C113(H11I,H11J,H11K), C114(H11L,
 H11M,H11N), C115(H11O,H11P,H11Q), C116(H11R,H11S,H11T), C117(H11U,H11V,H11W),
 C118(H11X,H11Y,HA), C119(H11Z,HB,HC), 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,HD), C128(H12Z,HE,
 HF), C4B(H4BA,H4BB,H4BC)
7.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O3(H3), O4(H4), O1B(H1BA)
;
_shelx_res_checksum              2963
_shelx_hkl_checksum              83511
_olex2_date_sample_data_collection 2017-10-02
_olex2_date_sample_submission    2017-10-02
_olex2_submission_original_sample_id d160815_44_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.485
_oxdiff_exptl_absorpt_empirical_full_min 0.804