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_4131445
_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 H11 F, C2 H3 N'
_chemical_formula_sum            'C136 H182 F N O12'
_chemical_formula_weight         2041.82
_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   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2016-04-25
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.4705(3)
_cell_length_b                   18.2782(3)
_cell_length_c                   46.1154(10)
_cell_measurement_reflns_used    9994
_cell_measurement_temperature    100.0(2)
_cell_measurement_theta_max      65.45
_cell_measurement_theta_min      3.01
_cell_volume                     13040.2(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'XS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.0(2)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'kappa-stage diffractometer'
_diffrn_measurement_device_type  'Bruker Apex2 Duo (Cu)'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'double mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0799
_diffrn_reflns_av_unetI/netI     0.0607
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -54
_diffrn_reflns_number            109894
_diffrn_reflns_point_group_measured_fraction_full 0.990
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        66.979
_diffrn_reflns_theta_max         66.979
_diffrn_reflns_theta_min         3.013
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.511
_exptl_absorpt_correction_T_max  0.7051
_exptl_absorpt_correction_T_min  0.5509
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0915 before and 0.0746 after correction.
The Ratio of minimum to maximum transmission is 0.7813.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.040
_exptl_crystal_description       plate
_exptl_crystal_F_000             4440
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.682
_refine_diff_density_min         -0.445
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 6953 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.03(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.375
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1538
_refine_ls_number_reflns         23014
_refine_ls_number_restraints     546
_refine_ls_restrained_S_all      1.444
_refine_ls_R_factor_all          0.0865
_refine_ls_R_factor_gt           0.0692
_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^)+(0.0810P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1721
_refine_ls_wR_factor_ref         0.1812
_reflns_Friedel_coverage         0.834
_reflns_Friedel_fraction_full    0.986
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                18811
_reflns_number_total             23014
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b05461_si_007.cif
_cod_data_source_block           cu_d160815_19_1_0m
_cod_database_code               4131445
_shelx_estimated_absorpt_t_max   0.980
_shelx_estimated_absorpt_t_min   0.914
_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
 O4-H4 = O3-H3 = O2-H2 = O1-H1
 0.91 with sigma of 0.02
 C2C-C1C \\sim C3C-C1C \\sim C4D-C2D \\sim C3D-C2D
 with sigma of 0.02
 F1C-C5C \\sim F1D-C1D
 with sigma of 0.02
 C22A-C21A \\sim C21A-C20B \\sim C21A-C20A \\sim C20A-C19A \\sim C20B-C19B
\\sim C11A-C10A \\sim C9A-
 C10A \\sim C9B-C10A \\sim C9A-C8A \\sim C9B-C8B \\sim C8A-C7A \\sim C8B-C7B
\\sim C17A-C16A \\sim C16A-
 C15B \\sim C16A-C15A \\sim C15B-C14B \\sim C15A-C14A \\sim C14A-C13A \\sim
C14B-C13B
 with sigma of 0.02
3. Rigid bond restraints
 F1C, C1C, C2C, C3C, C4C, C5C, C6C, F1D, C1D, C2D, C3D, C4D, C5D, C6D
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1A, C2A, C3A, C4A, C5A, C6A, C10A, C11A, C12A, C16A, C17A, C18A, C21A, C22A,
 C23A, C24A, C7A, C8A, C9A, C13A, C14A, C15A, C19A, C20A, C7B, C8B, C9B, C13B,
 C14B, C15B, C19B, C20B
 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(C13A) \\sim Ueq, Uanis(C13B) \\sim Ueq, Uanis(C14B) \\sim Ueq,
Uanis(C14A) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C15B) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 F1C, C1C, C2C, C3C, C4C, C5C, C6C, F1D, C1D, C2D, C3D, C4D, C5D, C6D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C2A, C3A, C4A, C5A, C6A, C10A, C11A, C12A, C16A, C17A, C18A, C21A, C22A,
 C23A, C24A, C7A, C8A, C9A, C13A, C14A, C15A, C19A, C20A, C7B, C8B, C9B, C13B,
 C14B, C15B, C19B, C20B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H10I)=Sof(H10J)=Sof(H21C)=Sof(H21D)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=
 Sof(H7BC)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(C9B)=Sof(H9BA)=Sof(H9BB)=Sof(C19B)=
 Sof(H19D)=Sof(H19E)=Sof(H19F)=Sof(C20B)=Sof(H20E)=Sof(H20F)=Sof(F1D)=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(H6DA)=Sof(H6DB)=
 1-FVAR(1)
 Sof(H10G)=Sof(H10H)=Sof(H21A)=Sof(H21B)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=
 Sof(H7AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C19A)=
 Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C20A)=Sof(H20C)=Sof(H20D)=Sof(F1C)=Sof(C1C)=
 Sof(H1CA)=Sof(H1CB)=Sof(C2C)=Sof(H2CA)=Sof(H2CB)=Sof(C3C)=Sof(H3CA)=Sof(H3CB)=
 Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(C5C)=Sof(H5C)=Sof(C6C)=Sof(H6CA)=Sof(H6CB)=
 FVAR(1)
 Sof(H16C)=Sof(H16D)=Sof(C13B)=Sof(H13D)=Sof(H13E)=Sof(H13F)=Sof(C14B)=
 Sof(H14C)=Sof(H14D)=Sof(C15B)=Sof(H15C)=Sof(H15D)=1-FVAR(2)
 Sof(H16A)=Sof(H16B)=Sof(C13A)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C14A)=
 Sof(H14A)=Sof(H14B)=Sof(C15A)=Sof(H15A)=Sof(H15B)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C1(H1A), C5(H5), C9(H9), C13(H13), C5C(H5C), C1D(H1D)
7.b Secondary CH2 refined with riding coordinates:
 C20(H20A,H20B), C24(H24A,H24B), C28(H28A,H28B), C32(H32A,H32B), C2A(H2AA,
 H2AB), C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C6A(H6AA,H6AB),
 C10A(H10G,H10H), C10A(H10I,H10J), C11A(H11A,H11B), C12A(H12A,H12B), C16A(H16A,
 H16B), C16A(H16C,H16D), C17A(H17A,H17B), C18A(H18A,H18B), C21A(H21A,H21B),
 C21A(H21C,H21D), C22A(H22A,H22B), C23A(H23A,H23B), C24A(H24C,H24D), C8A(H8AA,
 H8AB), C9A(H9AA,H9AB), C14A(H14A,H14B), C15A(H15A,H15B), C20A(H20C,H20D),
 C8B(H8BA,H8BB), C9B(H9BA,H9BB), C14B(H14C,H14D), C15B(H15C,H15D), C20B(H20E,
 H20F), C1C(H1CA,H1CB), C2C(H2CA,H2CB), C3C(H3CA,H3CB), C4C(H4CA,H4CB),
 C6C(H6CA,H6CB), C2D(H2DA,H2DB), C3D(H3DA,H3DB), C4D(H4DA,H4DB), C5D(H5DA,H5DB),
  C6D(H6DA,H6DB)
7.c Me refined with riding coordinates:
 C13A(H13A,H13B,H13C), C13B(H13D,H13E,H13F)
7.d Aromatic/amide H refined with riding coordinates:
 C3(H3A), C7(H7), C11(H11), C15(H15)
7.e Idealised Me refined as rotating group:
 C37(H37A,H37B,H37C), 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(H10A,H10B,H10C), C104(H10D,H10E,H10F), C1A(H1AA,H1AB,H1AC),
 C7A(H7AA,H7AB,H7AC), C19A(H19A,H19B,H19C), C7B(H7BA,H7BB,H7BC), C19B(H19D,H19E,
 H19F), C105(H10K,H10L,H10M)
;
_shelx_res_checksum              75186
_shelx_hkl_checksum              3092
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-04-22
_olex2_date_sample_submission    2016-04-22
_olex2_submission_original_sample_id d160815_19_1
_olex2_submission_special_instructions 'No special instructions were received'