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_4134294
_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, C5 H10 Br2 O'
_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             2017-10-31
_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                   44.1945(2)
_cell_length_b                   18.78150(10)
_cell_length_c                   15.55630(10)
_cell_measurement_reflns_used    105743
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      79.2060
_cell_measurement_theta_min      3.4680
_cell_volume                     12912.34(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  '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 0.996
_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   -116.00 -78.00   0.50    2.00    --  -49.37 -77.00 150.00   76
  2  \w   -116.00 -78.00   0.50    2.00    --  -49.37 -77.00  90.00   76
  3  \w   -116.00 -78.00   0.50    2.00    --  -49.37 -77.00 -30.00   76
  4  \w   -119.00 -63.00   0.50    2.00    --  -49.37-135.00-128.00  112
  5  \w   -140.00 -84.00   0.50    5.00    --  -70.00 -99.00  60.00  112
  6  \w    -83.00   6.00   0.50    5.00    --  -70.00  19.00  90.00  178
  7  \w    -63.00  26.00   0.50    2.00    --  -49.37  38.00 120.00  178
  8  \w     78.00 116.00   0.50    2.00    --   49.37  77.00 -90.00   76
  9  \w     78.00 116.00   0.50    2.00    --   49.37  77.00-150.00   76
 10  \w     94.00 176.00   0.50    5.00    --  110.00  57.00-150.00  164
 11  \w    101.00 173.00   0.50    5.00    --  110.00  38.00-120.00  144
 12  \w    102.00 178.00   0.50    5.00    --  110.00  38.00-180.00  152
 13  \w     78.00 116.00   0.50    2.00    --   49.37  77.00  60.00   76
 14  \w     94.00 178.00   0.50    5.00    --  110.00  57.00  90.00  168
 15  \w     99.00 173.00   0.50    5.00    --  110.00  57.00 150.00  148
 16  \w     94.00 178.00   0.50    5.00    --  110.00  57.00 120.00  168
 17  \w     97.00 141.00   0.50    5.00    --  110.00  19.00  90.00   88
 18  \w    101.00 131.00   0.50    5.00    --  110.00 -77.00 150.00   60
 19  \w     53.00  79.00   0.50    5.00    --  110.00 -77.00 150.00   52
 20  \w     51.00 110.00   0.50    5.00    --  110.00 -99.00  90.00  118
 21  \w     40.00 110.00   0.50    5.00    --  110.00 -99.00 120.00  140
 22  \w     40.00  79.00   0.50    5.00    --  110.00 -57.00  30.00   78
 23  \w     38.00  84.00   0.50    5.00    --  110.00 -57.00   0.00   92
 24  \w     40.00 110.00   0.50    5.00    --  110.00 -99.00 -60.00  140
 25  \w     40.00 110.00   0.50    5.00    --  110.00 -99.00-150.00  140
 26  \w     44.00 131.00   0.50    5.00    --  110.00 -77.00 -60.00  174
 27  \w     39.00 122.00   0.50    5.00    --  110.00-125.00  90.00  166
 28  \w     39.00  66.00   0.50    5.00    --  110.00 -57.00 -60.00   54
 29  \w     38.00  84.00   0.50    5.00    --  110.00 -57.00-120.00   92
 30  \w     38.00  84.00   0.50    5.00    --  110.00 -57.00-180.00   92
 31  \w     39.00  70.00   0.50    5.00    --  110.00 -57.00 -30.00   62
 32  \w     40.00 120.00   0.50    5.00    --  110.00-125.00 -30.00  160
 33  \w     38.00  84.00   0.50    5.00    --  110.00 -57.00 120.00   92
 34  \w     40.00  82.00   0.50    5.00    --  110.00 -57.00  90.00   84
 35  \w     43.00  73.00   0.50    5.00    --  110.00 -57.00  60.00   60
 36  \w    -65.00  22.00   0.50    2.00    --  -49.37  57.00-120.00  174
 37  \w    -95.00  -9.00   0.50    5.00    --  -70.00 125.00  60.00  172
 38  \w    -95.00  -9.00   0.50    5.00    --  -70.00 125.00-120.00  172
;
_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      -0.0036257000
_diffrn_orient_matrix_UB_12      -0.0664074000
_diffrn_orient_matrix_UB_13      0.0572642000
_diffrn_orient_matrix_UB_21      -0.0346775000
_diffrn_orient_matrix_UB_22      0.0066492000
_diffrn_orient_matrix_UB_23      -0.0064732000
_diffrn_orient_matrix_UB_31      0.0002111000
_diffrn_orient_matrix_UB_32      -0.0476517000
_diffrn_orient_matrix_UB_33      -0.0805379000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0575
_diffrn_reflns_av_unetI/netI     0.0302
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       55
_diffrn_reflns_limit_h_min       -56
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            215132
_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         79.804
_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    1.228
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.786
_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    1.103
_exptl_crystal_description       block
_exptl_crystal_F_000             4600
_exptl_crystal_size_max          0.123
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.042
_refine_diff_density_max         0.848
_refine_diff_density_min         -1.077
_refine_diff_density_rms         0.059
_refine_ls_abs_structure_details
;
 Flack x determined using 10766 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.005(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1436
_refine_ls_number_reflns         27917
_refine_ls_number_restraints     353
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0528
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0925P)^2^+6.4436P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1485
_refine_ls_wR_factor_ref         0.1522
_reflns_Friedel_coverage         0.846
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.990
_reflns_number_gt                25762
_reflns_number_total             27917
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            CCDC-1914859.cif
_cod_data_source_block           d160815_44_28
_cod_depositor_comments
'Adding full bibliography for 4134283--4134298.cif.'
_cod_database_code               4134294
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C133H178Br2O13
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.864
_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 C(H,H,H,H,H,H) groups, All O(H) groups
2. Restrained distances
 C6-C5 = C5-C4 = C5-C4A = C4-C3 = C4A-C3A = C3-C2 = C3A-C2 = C2-C1
 1.5 with sigma of 0.005
 Br1C-C2C \\sim Br1D-C2D
 with sigma of 0.02
 Br2D-C3D \\sim Br2C-C3C
 with sigma of 0.02
 C3C-C2C \\sim C3D-C2D
 with sigma of 0.02
 C4C-C3D \\sim C4C-C3C
 with sigma of 0.02
 C2C-C1C \\sim C2D-C1C
 with sigma of 0.02
 C5C-C2C \\sim C5D-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-C2 \\sim C2-C1
 with sigma of 0.02
 C1-C3 \\sim C1-C3A \\sim C2-C4 \\sim C2-C4A \\sim C3-C5 \\sim C3A-C5 \\sim
C4-C6 \\sim C4A-C6
 with sigma of 0.02
3. Rigid bond restraints
 C1, C2, C3, C4, C5, C6, C4A, C3A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C7, C8, C9, C10, C11, C12
 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(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3A) \\sim Ueq, Uanis(C3) \\sim
Ueq, Uanis(C4A) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim
Ueq, Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq: with sigma of 0.01 and sigma
for terminal atoms of 0.02
Uanis(C5C) = Uanis(C5D)
5. Rigid body (RIGU) restrains
 O1C, C1C, C4C, Br1C, Br2C, C2C, C3C, C5C, Br1D, Br2D, C2D, C3D, C5D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1, C2, C3, C4, C5, C6, C4A, C3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7, C8, C9, C10, C11, C12
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H1CD)=Sof(H1CE)=Sof(H4CD)=Sof(H4CE)=Sof(H4CF)=Sof(Br1D)=Sof(Br2D)=
 Sof(C2D)=Sof(C3D)=Sof(H3D)=Sof(C5D)=Sof(H5DA)=Sof(H5DB)=Sof(H5DC)=1-FVAR(1)
 Sof(H1CB)=Sof(H1CC)=Sof(H4CA)=Sof(H4CB)=Sof(H4CC)=Sof(Br1C)=Sof(Br2C)=
 Sof(C2C)=Sof(C3C)=Sof(H3C)=Sof(C5C)=Sof(H5CA)=Sof(H5CB)=Sof(H5CC)=FVAR(1)
 Sof(H2BC)=Sof(H2BD)=Sof(H5BC)=Sof(H5BD)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C3A)=
 Sof(H3AA)=Sof(H3AB)=1-FVAR(2)
 Sof(H2AA)=Sof(H2AB)=Sof(C3)=Sof(H3A)=Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=
 Sof(H5AA)=Sof(H5AB)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C38(H38), C50(H50), C53(H53), C56(H56), C3C(H3C), C3D(H3D)
7.b Secondary CH2 refined with riding coordinates:
 C2(H2AA,H2AB), C2(H2BC,H2BD), C3(H3A,H3B), C4(H4A,H4B), C5(H5AA,H5AB),
 C5(H5BC,H5BD), C6(H6A,H6B), 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), C49(H49A,H49B), C52(H52A,H52B), C73(H73A,
 H73B), C82(H82A,H82B), C1C(H1CB,H1CC), C1C(H1CD,H1CE), C4A(H4AA,H4AB),
 C3A(H3AA,H3AB)
7.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C36(H36), C43(H43), C60(H60)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C7(H7A,H7B,H7C), C13(H13A,H13B,H13C), C19(H19A,H19B,H19C),
 C92(H92A,H92B,H92C), C95(H95A,H95B,H95C), C98(H98A,H98B,H98C), C100(H10C,H10D,
 H10E), C101(H10F,H10G,H10H), C102(H10I,H10J,H10K), C103(H10L,H10M,H10N),
 C104(H10O,H10P,H10Q), C105(H10R,H10S,H10T), C106(H10U,H10V,H10W), C107(H10X,
 H10Y,H), C108(H10Z,HA,HB), C109(H10,HC,HD), 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,HE), C118(H11Z,HF,
 HG), C119(H11,HH,HI), 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,HJ), C128(H12Z,HK,HL), C4C(H4CA,H4CB,
 H4CC), C4C(H4CD,H4CE,H4CF), C5C(H5CA,H5CB,H5CC), C5D(H5DA,H5DB,H5DC)
7.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O3(H3), O4(H4), O1C(H1CA)
;
_shelx_res_checksum              2072
_shelx_hkl_checksum              46091
_olex2_date_sample_data_collection 2017-10-20
_olex2_date_sample_submission    2017-10-20
_olex2_submission_original_sample_id d160815_44_28
_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 1.353
_oxdiff_exptl_absorpt_empirical_full_min 0.816