Dispersion and Halogen-Bonding Interactions: Binding of the Axial Conformers of Monohalo- and (±)-trans-1,2-Dihalocyclohexanes in Enantiopure Alleno-Acetylenic Cages.
Gropp, Cornelius; Husch, Tamara; Trapp, Nils; Reiher, Markus; Diederich, François; Journal of the American Chemical Society 139 (2017) 12190–12200; doi:10.1021/jacs.7b05461

data_4131447
_publ_section_title
;
 Dispersion and Halogen-Bonding Interactions: Binding of the Axial
 Conformers of Monohalo- and (+-)-trans-1,2-Dihalocyclohexanes in
 Enantiopure Alleno-Acetylenic Cages.
;
_journal_issue                   35
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              12190
_journal_page_last               12200
_journal_paper_doi               10.1021/jacs.7b05461
_journal_volume                  139
_journal_year                    2017
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C128 H168 O12, C6 H10 Cl2, C2 H3 N'
_chemical_formula_sum            'C136 H181 Cl2 N O12'
_chemical_formula_weight         2092.71
_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             2016-09-29
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4654(2)
_cell_length_b                   18.2121(2)
_cell_length_c                   46.7197(5)
_cell_measurement_reflns_used    54334
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.6130
_cell_measurement_theta_min      2.5800
_cell_volume                     13158.9(3)
_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 0.999
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
--------------------------------------------------------------------------
  1  \f     90.00 182.00   0.25    0.50  15.00  52.95 -60.00    --   368
  2  \f    182.00 254.00   0.25    0.50  15.00  52.95 -60.00    --   288
  3  \w    -22.00   4.00   0.25    0.10    --    0.00 -38.00-180.00  104
  4  \w      4.00  40.00   0.25    0.10    --    0.00  38.00  60.00  144
  5  \w    -29.00   6.00   0.25    0.10    --    0.00   0.00-120.00  140
  6  \w    -71.00   5.00   0.25    0.10    --    0.00 -38.00-120.00  304
  7  \w    -94.00 -60.00   0.25    1.00    --  -70.00 125.00 -90.00  136
  8  \w     89.00 155.00   0.25    1.00    --  105.75  77.00-150.00  264
  9  \w     79.00 116.00   0.25    1.00    --  105.75-125.00-150.00  148
 10  \w     36.00 110.00   0.25    1.00    --  105.75 -19.00  90.00  296
 11  \w     90.00 116.00   0.25    1.00    --  105.75  77.00-120.00  104
 12  \w     42.00 108.00   0.25    1.00    --  105.75 -38.00 -90.00  264
 13  \w    121.00 165.00   0.25    1.00    --  105.75  77.00-120.00  176
 14  \w     40.00  86.00   0.25    1.00    --  105.75 -99.00-120.00  184
 15  \w     46.00  71.00   0.25    1.00    --  105.75 -99.00-180.00  100
 16  \w     39.00 110.00   0.25    1.00    --  105.75 -99.00  90.00  284
 17  \w    100.00 168.00   0.25    1.00    --  105.75 125.00 150.00  272
 18  \w     58.00 125.00   0.25    1.00    --  105.75 -77.00-150.00  268
 19  \w    -48.00   7.00   0.25    0.10    --    0.00   0.00  60.00  220
 20  \w    -73.00   5.00   0.25    0.10    --    0.00 -38.00  30.00  312
 21  \w   -133.00 -63.00   0.25    1.00    --  -70.00 -77.00 -30.00  280
 22  \w   -133.00 -51.00   0.25    1.00    --  -70.00 -77.00-150.00  328
 23  \w     58.00 112.00   0.25    1.00    --  105.75   0.00-180.00  216
 24  \w     58.00 112.00   0.25    1.00    --  105.75   0.00 120.00  216
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, Pilatus 300K'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0025735000
_diffrn_orient_matrix_UB_12      -0.0779115000
_diffrn_orient_matrix_UB_13      -0.0128407000
_diffrn_orient_matrix_UB_21      0.0256515000
_diffrn_orient_matrix_UB_22      0.0323136000
_diffrn_orient_matrix_UB_23      -0.0292586000
_diffrn_orient_matrix_UB_31      0.0962187000
_diffrn_orient_matrix_UB_32      -0.0064776000
_diffrn_orient_matrix_UB_33      0.0081532000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0638
_diffrn_reflns_av_unetI/netI     0.0418
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       57
_diffrn_reflns_limit_l_min       -57
_diffrn_reflns_number            132473
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.129
_diffrn_reflns_theta_min         2.604
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.871
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.66853
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.8d (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    1.056
_exptl_crystal_description       cube
_exptl_crystal_F_000             4536
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.455
_refine_diff_density_min         -0.390
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 7837 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.040(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.115
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1522
_refine_ls_number_reflns         25704
_refine_ls_number_restraints     318
_refine_ls_restrained_S_all      1.118
_refine_ls_R_factor_all          0.0787
_refine_ls_R_factor_gt           0.0542
_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^)+(0.0437P)^2^+12.7158P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1190
_refine_ls_wR_factor_ref         0.1587
_reflns_Friedel_coverage         0.831
_reflns_Friedel_fraction_full    0.994
_reflns_Friedel_fraction_max     0.981
_reflns_number_gt                20936
_reflns_number_total             25704
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b05461_si_002.cif
_cod_data_source_block           wit_d160815_31_3
_cod_database_code               4131447
_chemical_oxdiff_formula         'C134 H178Cl2O12N'
_reflns_odcompleteness_completeness 99.98
_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
 C3A-C2A = C3A-C2B
 1.52 with sigma of 0.002
 C2A-C1A = C2B-C1B
 1.52 with sigma of 0.002
 C8A-C7A \\sim C8B-C7B \\sim C9A-C8A \\sim C9B-C8B \\sim C9A-C10A \\sim
C9B-C10A \\sim C11A-C10A
 with sigma of 0.02
 C3A-C2A \\sim C3A-C2B \\sim C2A-C1A \\sim C2B-C1B \\sim C4A-C3A
 with sigma of 0.02
 C1A-C3A \\sim C1B-C3A \\sim C2A-C4A \\sim C2B-C4A
 with sigma of 0.02
 Cl1D-C1D \\sim Cl2C-C6C \\sim Cl1C-C1C \\sim Cl2D-C6D
 with sigma of 0.02
 C6D-C1D \\sim C6C-C1C
 with sigma of 0.02
 Cl1C-Cl2C \\sim Cl1D-Cl2D
 with sigma of 0.02
 C2D-C1D \\sim C6C-C5C \\sim C6D-C5D \\sim C2C-C1C
 with sigma of 0.02
 C5C-C4C \\sim C3D-C2D \\sim C5D-C4D \\sim C3C-C2C
 with sigma of 0.02
 C4C-C3C \\sim C4D-C3D
 with sigma of 0.02
3. Rigid bond restraints
 C3A, C4A, C10A, C1A, C2A, C7A, C8A, C9A, C1B, C2B, C7B, C8B, C9B
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Cl1C, Cl2C, C1C, C2C, C3C, C4C, C5C, C6C, Cl1D, Cl2D, C1D, C2D, C3D, C4D, C5D,
  C6D
 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(C9B) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C8B) \\sim Ueq, Uanis(C8A)
\\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C7B) \\sim Ueq: with sigma of 0.03 and
sigma for terminal atoms of 0.06
5. Rigid body (RIGU) restrains
 C10A, C7A, C8A, C9A, C7B, C8B, C9B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3A, C4A, C1A, C2A, C1B, C2B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1C, Cl2C, C1C, C2C, C3C, C4C, C5C, C6C, Cl1D, Cl2D, C1D, C2D, C3D, C4D, C5D,
  C6D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H3AC)=Sof(H3AD)=Sof(H10C)=Sof(H10D)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=
 Sof(H1BC)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(H7BC)=
 Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=1-FVAR(1)
 Sof(H3AA)=Sof(H3AB)=Sof(H10A)=Sof(H10B)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=
 Sof(H1AC)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=FVAR(1)
 Sof(Cl1D)=Sof(Cl2D)=Sof(C1D)=Sof(H1D)=Sof(C2D)=Sof(H2DA)=Sof(H2DB)=Sof(C3D)=
 Sof(H3DA)=Sof(H3DB)=Sof(C4D)=Sof(H4DA)=Sof(H4DB)=Sof(C5D)=Sof(H5DA)=Sof(H5DB)=
 Sof(C6D)=Sof(H6D)=1-FVAR(2)
 Sof(Cl1C)=Sof(Cl2C)=Sof(C1C)=Sof(H1C)=Sof(C2C)=Sof(H2CA)=Sof(H2CB)=Sof(C3C)=
 Sof(H3CA)=Sof(H3CB)=Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(C5C)=Sof(H5CA)=Sof(H5CB)=
 Sof(C6C)=Sof(H6C)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C1(H1A), C5(H5), C9(H9), C13(H13), C1C(H1C), C6C(H6C), C1D(H1D), C6D(H6D)
7.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C24(H24A,H24B), C28(H28A,H28B), C32(H32A,H32B), C3A(H3AA,
 H3AB), C3A(H3AC,H3AD), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C6A(H6AA,H6AB),
 C10A(H10A,H10B), C10A(H10C,H10D), C11A(H11A,H11B), C12A(H12A,H12B), C14A(H14A,
 H14B), C15A(H15A,H15B), C16A(H16A,H16B), C17A(H17A,H17B), C18A(H18A,H18B),
 C20A(H20C,H20D), C21A(H21A,H21B), C22A(H22A,H22B), C23A(H23A,H23B), C24A(H24C,
 H24D), C2A(H2AA,H2AB), C8A(H8AA,H8AB), C9A(H9AA,H9AB), C2B(H2BA,H2BB),
 C8B(H8BA,H8BB), C9B(H9BA,H9BB), C2C(H2CA,H2CB), C3C(H3CA,H3CB), C4C(H4CA,H4CB),
  C5C(H5CA,H5CB), C2D(H2DA,H2DB), C3D(H3DA,H3DB), C4D(H4DA,H4DB), C5D(H5DA,H5DB)
7.c Aromatic/amide H refined with riding coordinates:
 C3(H3A), C7(H7), C11(H11), C15(H15)
7.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C43(H43A,H43B,
 H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C49(H49A,H49B,H49C), C50(H50A,
 H50B,H50C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C),
 C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C67(H67A,H67B,
 H67C), C68(H68A,H68B,H68C), C73(H73A,H73B,H73C), C74(H74A,H74B,H74C), C75(H75A,
 H75B,H75C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C),
 C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C91(H91A,H91B,H91C), C92(H92A,H92B,
 H92C), C93(H93A,H93B,H93C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C99(H99A,
 H99B,H99C), C103(H10E,H10F,H10G), C104(H10H,H10I,H10J), C13A(H13A,H13B,H13C),
 C19A(H19A,H19B,H19C), C1A(H1AA,H1AB,H1AC), C7A(H7AA,H7AB,H7AC), C1B(H1BA,H1BB,
 H1BC), C7B(H7BA,H7BB,H7BC), C7C(H7CA,H7CB,H7CC)
7.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O3(H3), O4(H4)
;
_shelx_res_checksum              9938
_shelx_hkl_checksum              35525
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-09-22
_olex2_date_sample_submission    2016-09-22
_olex2_submission_original_sample_id d160815_31_3
_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 1.481
_oxdiff_exptl_absorpt_empirical_full_min 0.776