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_4134288
_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         'C5 H10 Br2 O, C128 H168 O12'
_chemical_formula_sum            'C133 H178 Br2 O13'
_chemical_formula_weight         2144.56
_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             2017-09-21
_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                   43.9914(3)
_cell_length_b                   18.74020(10)
_cell_length_c                   15.61220(10)
_cell_measurement_reflns_used    131782
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.3110
_cell_measurement_theta_min      3.4660
_cell_volume                     12870.82(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_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    '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 0.994
_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    -65.00  22.00   0.50    3.00    --  -49.37  57.00 120.00  174
  2  \w    -65.00  22.00   0.50    3.00    --  -49.37  57.00 -60.00  174
  3  \w     59.00 120.00   0.50    3.00    --   49.37 178.00-180.00  122
  4  \w     86.00 177.00   0.50   12.00    --  110.00  77.00-150.00  182
  5  \w     94.00 123.00   0.50   12.00    --  110.00 -19.00 -30.00   58
  6  \w     94.00 123.00   0.50   12.00    --  110.00 -19.00 -90.00   58
  7  \w     94.00 123.00   0.50   12.00    --  110.00 -19.00-120.00   58
  8  \w     94.00 123.00   0.50   12.00    --  110.00 -19.00-150.00   58
  9  \w     97.00 178.00   0.50   12.00    --  110.00  19.00-180.00  162
 10  \w     98.00 178.00   0.50   12.00    --  110.00  38.00-150.00  160
 11  \w     86.00 177.00   0.50   12.00    --  110.00  77.00   0.00  182
 12  \w     94.00 178.00   0.50   12.00    --  110.00  57.00  60.00  168
 13  \w     98.00 178.00   0.50   12.00    --  110.00  38.00  30.00  160
 14  \w     91.00 178.00   0.50   12.00    --  110.00 125.00 150.00  174
 15  \w     94.00 123.00   0.50   12.00    --  110.00 -19.00  60.00   58
 16  \w     44.00 134.00   0.50   12.00    --  110.00 -77.00 120.00  180
 17  \w     40.00 110.00   0.50   12.00    --  110.00 -99.00   0.00  140
 18  \w     40.00 110.00   0.50   12.00    --  110.00 -99.00 -60.00  140
 19  \w     40.00 110.00   0.50   12.00    --  110.00 -99.00-180.00  140
 20  \w     38.00  84.00   0.50   12.00    --  110.00 -57.00 -90.00   92
 21  \w     44.00 134.00   0.50   12.00    --  110.00 -77.00 -30.00  180
 22  \w     40.00 110.00   0.50   12.00    --  110.00 -99.00  90.00  140
 23  \w     38.00  84.00   0.50   12.00    --  110.00 -57.00 150.00   92
 24  \w     39.00 122.00   0.50   12.00    --  110.00-125.00 150.00  166
 25  \w     38.00  84.00   0.50   12.00    --  110.00 -57.00 -30.00   92
 26  \w     38.00  84.00   0.50   12.00    --  110.00 -57.00   0.00   92
 27  \w     39.00 122.00   0.50   12.00    --  110.00-125.00 -60.00  166
 28  \w    -95.00  -9.00   0.50   12.00    --  -70.00 125.00-120.00  172
 29  \w   -125.00 -36.00   0.50    3.00    --  -49.37 -38.00-120.00  178
 30  \w   -116.00 -26.00   0.50    3.00    --  -49.37 -77.00-180.00  180
 31  \w   -116.00 -26.00   0.50    3.00    --  -49.37 -77.00   0.00  180
 32  \w   -120.00 -38.00   0.50    3.00    --  -49.37-178.00  30.00  164
 33  \w   -116.00 -26.00   0.50    3.00    --  -49.37 -77.00  90.00  180
 34  \w   -116.00 -26.00   0.50    3.00    --  -49.37 -77.00 -60.00  180
 35  \w   -116.00 -26.00   0.50    3.00    --  -49.37 -77.00-120.00  180
 36  \w   -125.00 -36.00   0.50    3.00    --  -49.37 -38.00  30.00  178
 37  \w   -125.00 -37.00   0.50    3.00    --  -49.37 -19.00  90.00  176
 38  \w   -142.00 -54.00   0.50   12.00    --  -70.00 -57.00   0.00  176
 39  \w   -142.00 -54.00   0.50   12.00    --  -70.00 -57.00-180.00  176
;
_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      -0.0032563000
_diffrn_orient_matrix_UB_12      -0.0026639000
_diffrn_orient_matrix_UB_13      -0.0981895000
_diffrn_orient_matrix_UB_21      -0.0348741000
_diffrn_orient_matrix_UB_22      0.0001332000
_diffrn_orient_matrix_UB_23      0.0093075000
_diffrn_orient_matrix_UB_31      -0.0000260000
_diffrn_orient_matrix_UB_32      0.0821465000
_diffrn_orient_matrix_UB_33      -0.0032002000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0648
_diffrn_reflns_av_unetI/netI     0.0264
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       56
_diffrn_reflns_limit_h_min       -55
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            273849
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.065
_diffrn_reflns_theta_min         3.003
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.231
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.651
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.8d (Rigaku Oxford Diffraction, 2015)
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    1.107
_exptl_crystal_description       plate
_exptl_crystal_F_000             4600
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.125
_exptl_crystal_size_min          0.027
_refine_diff_density_max         1.218
_refine_diff_density_min         -2.475
_refine_diff_density_rms         0.137
_refine_ls_abs_structure_details
;
 Flack x determined using 10877 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.022(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.286
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1470
_refine_ls_number_reflns         27806
_refine_ls_number_restraints     320
_refine_ls_restrained_S_all      1.299
_refine_ls_R_factor_all          0.0933
_refine_ls_R_factor_gt           0.0902
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_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          0.2706
_refine_ls_wR_factor_ref         0.2754
_reflns_Friedel_coverage         0.845
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                25884
_reflns_number_total             27806
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            CCDC-1914839.cif
_cod_data_source_block           d160815_44_16
_cod_depositor_comments
'Adding full bibliography for 4134283--4134298.cif.'
_cod_database_code               4134288
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C133H178Br2O13
_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
 C3D-C2D = C5C-C4C = C3C-C2C = C5D-C4D = C2D-C1C = C2C-C1C = C4C-C2C = C4D-C2D
 1.51 with sigma of 0.02
 C17-C16 = C17-C16A = C16A-C15A = C16-C15 = C18-C17
 1.51 with sigma of 0.02
 O2-H
 2.1 with sigma of 0.02
 C5D-C4D \\sim C3C-C2C \\sim C3D-C2D \\sim C5C-C4C
 with sigma of 0.02
 Br2C-C4C \\sim Br2C-C4D
 with sigma of 0.02
 C4C-C2C \\sim C4D-C2D
 with sigma of 0.02
 C2D-C1C \\sim C2C-C1C
 with sigma of 0.02
 Br1C-C2D \\sim Br1C-C2C
 with sigma of 0.02
 C18-C17 \\sim C17-C16A \\sim C17-C16 \\sim C16A-C15A \\sim C16-C15 \\sim
C15A-C14A \\sim C15-C14 ~
 C14A-C13A \\sim C14-C13
 with sigma of 0.02
 C13-C15 \\sim C13A-C15A \\sim C14-C16 \\sim C14A-C16A \\sim C15-C17 \\sim
C15A-C17 \\sim C16-C18 ~
 C16A-C18
 with sigma of 0.02
 C22-C21 \\sim C21-C20A \\sim C21-C20 \\sim C20A-C19A \\sim C20-C19
 with sigma of 0.02
 C19A-C21 \\sim C19-C21 \\sim C20A-C22 \\sim C20-C22
 with sigma of 0.02
3. Rigid bond restraints
 C18, C17, C14, C13, C16, C15, C13A, C14A, C15A, C16A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C24, C23, C22, C21, C20A, C19A, C20, C19
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Rigid body (RIGU) restrains
 Br2C, Br1C, C2C, C2D, C1C, C3C, C4C, C4D, C3D, O1C, C5C, C5D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18, C17, C14, C13, C16, C15, C13A, C14A, C15A, C16A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C23, C22, C21, C20A, C19A, C20, C19, C24
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(HI)=Sof(HJ)=Sof(C5D)=Sof(HU)=Sof(HV)=Sof(HW)=Sof(C4D)=Sof(HX)=Sof(C2D)=
 Sof(C3D)=Sof(HY)=Sof(HZ)=Sof(H0AA)=1-FVAR(1)
 Sof(HG)=Sof(HH)=Sof(C2C)=Sof(C5C)=Sof(HL)=Sof(HM)=Sof(HN)=Sof(C3C)=Sof(HO)=
 Sof(HP)=Sof(HQ)=Sof(C4C)=Sof(HT)=FVAR(1)
 Sof(H21C)=Sof(H21D)=Sof(H17C)=Sof(H17D)=Sof(C20A)=Sof(H20A)=Sof(H20B)=
 Sof(C19A)=Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C13A)=Sof(H13D)=Sof(H13E)=
 Sof(H13F)=Sof(C14A)=Sof(H14C)=Sof(H14D)=Sof(C15A)=Sof(H15C)=Sof(H15D)=
 Sof(C16A)=Sof(H16C)=Sof(H16D)=1-FVAR(2)
 Sof(H21A)=Sof(H21B)=Sof(H17A)=Sof(H17B)=Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(C13)=
 Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(C15)=Sof(H15A)=
 Sof(H15B)=Sof(C20)=Sof(H20C)=Sof(H20D)=Sof(C19)=Sof(H19D)=Sof(H19E)=Sof(H19F)=
 FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C42(H42), C44(H44), C48(H48), C53(H53), C4C(HT), C4D(HX)
6.b Secondary CH2 refined with riding coordinates:
 C24(H24A,H24B), C49(H49A,H49B), C12(H12A,H12B), C54(H54A,H54B), C64(H64A,
 H64B), C6(H6A,H6B), C69(H69A,H69B), C11(H11A,H11B), C4(H4A,H4B), C23(H23A,
 H23B), C10(H10A,H10B), C22(H22A,H22B), C18(H18A,H18B), C9(H9A,H9B), C5(H5A,
 H5B), C21(H21C,H21D), C21(H21A,H21B), C3(H3A,H3B), C2(H2A,H2B), C8(H8A,H8B),
 C1C(HG,HH), C1C(HI,HJ), C17(H17A,H17B), C17(H17C,H17D), C20A(H20A,H20B),
 C14(H14A,H14B), C16(H16A,H16B), C15(H15A,H15B), C14A(H14C,H14D), C15A(H15C,
 H15D), C16A(H16C,H16D), C20(H20C,H20D)
6.c Me refined with riding coordinates:
 C119(H11,HE,HF), C125(H12R,H12S,H12T)
6.d Aromatic/amide H refined with riding coordinates:
 C25(H25), C36(H36), C50(H50), C59(H59)
6.e Idealised Me refined as rotating group:
 C91(H91A,H91B,H91C), C93(H93A,H93B,H93C), C95(H95A,H95B,H95C), C98(H98A,H98B,
 H98C), C99(H99A,H99B,H99C), C100(H10C,H10D,H10E), C102(H10F,H10G,H10H),
 C103(H10I,H10J,H10K), C104(H10L,H10M,H10N), C106(H10O,H10P,H10Q), C107(H10R,
 H10S,H10T), C108(H10U,H10V,H10W), C109(H10X,H10Y,HA), 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,HB),
 C118(H11Z,HC,HD), C120(H12C,H12D,H12E), C121(H12F,H12G,H12H), C122(H12I,H12J,
 H12K), C123(H12L,H12M,H12N), C124(H12O,H12P,H12Q), C126(H12U,H12V,H12W),
 C7(H7A,H7B,H7C), C1(H1A,H1B,H1C), C127(H12X,H12Y,HK), C5C(HL,HM,HN), C3C(HO,HP,
 HQ), C128(H12Z,HR,HS), C13(H13A,H13B,H13C), C19A(H19A,H19B,H19C), C5D(HU,HV,
 HW), C3D(HY,HZ,H0AA), C13A(H13D,H13E,H13F), C19(H19D,H19E,H19F)
6.f Idealised tetrahedral OH refined as rotating group:
 O2(H2), O4(H4), O3(H3), O1(H1), O1C(H)
;
_shelx_res_checksum              70416
_shelx_hkl_checksum              51251
_olex2_date_sample_data_collection 2017-09-20
_olex2_date_sample_submission    2017-09-20
_olex2_submission_original_sample_id d160815_44_16
_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 1.460
_oxdiff_exptl_absorpt_empirical_full_min 0.726