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_4131440
_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 Br, C2 H3 N'
_chemical_formula_sum            'C136 H182 Br N O12'
_chemical_formula_weight         2102.73
_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             2016-11-09
_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                   15.4705(5)
_cell_length_b                   18.2238(5)
_cell_length_c                   46.4128(14)
_cell_measurement_reflns_used    9759
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      65.82
_cell_measurement_theta_min      3.01
_cell_volume                     13085.2(7)
_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(1)
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_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  0.0663
_diffrn_reflns_av_unetI/netI     0.0378
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -55
_diffrn_reflns_number            172129
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.992
_diffrn_reflns_theta_full        67.009
_diffrn_reflns_theta_max         67.009
_diffrn_reflns_theta_min         2.605
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.855
_exptl_absorpt_correction_T_max  0.6768
_exptl_absorpt_correction_T_min  0.5823
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0982 before and 0.0746 after correction.
The Ratio of minimum to maximum transmission is 0.8604.
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    1.067
_exptl_crystal_description       block
_exptl_crystal_F_000             4544
_exptl_crystal_size_max          0.17
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.640
_refine_diff_density_min         -0.554
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 8723 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.014(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1440
_refine_ls_number_reflns         23174
_refine_ls_number_restraints     176
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0533
_refine_ls_R_factor_gt           0.0476
_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^)+(0.0688P)^2^+4.7276P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1218
_refine_ls_wR_factor_ref         0.1260
_reflns_Friedel_coverage         0.836
_reflns_Friedel_fraction_full    0.989
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                21167
_reflns_number_total             23174
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b05461_si_009.cif
_cod_data_source_block           cu_d160815_35_1_0m
_cod_database_code               4131440
_shelx_estimated_absorpt_t_max   0.950
_shelx_estimated_absorpt_t_min   0.868
_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
 C4-C3 \\sim C3-C2 \\sim C3-C2A \\sim C2-C1 \\sim C2A-C1A
 with sigma of 0.02
 C1-C3 \\sim C1A-C3 \\sim C2-C4 \\sim C2A-C4
 with sigma of 0.02
 C11-C10 \\sim C9A-C10 \\sim C9-C10 \\sim C9A-C8A \\sim C9-C8 \\sim C8A-C7A
\\sim C8-C7
 with sigma of 0.02
 C7-C9 \\sim C7A-C9A \\sim C8-C10 \\sim C8A-C10 \\sim C9-C11 \\sim C9A-C11
 with sigma of 0.02
3. Rigid bond restraints
 C3, C4, C1, C2, C1A, C2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C10, C11, C7, C8, C9, C7A, C8A, C9A
 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(C9) \\sim Ueq, Uanis(C9A) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C8A)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C7A) \\sim Ueq: with sigma of 0.04 and
sigma for terminal atoms of 0.08
5. Rigid body (RIGU) restrains
 C3, C4, C1, C2, C1A, C2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10, C11, C7, C8, C9, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H3BC)=Sof(H3BD)=Sof(H10C)=Sof(H10D)=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)=1-FVAR(1)
 Sof(H3AA)=Sof(H3AB)=Sof(H10A)=Sof(H10B)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=
 Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=
 Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C28(H28), C38(H38), C51(H51), C61(H61), C1B(H1BA)
7.b Secondary CH2 refined with riding coordinates:
 C3(H3AA,H3AB), C3(H3BC,H3BD), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,H6B), C10(H10A,
 H10B), C10(H10C,H10D), 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), C66(H66A,
 H66B), C70(H70A,H70B), C74(H74A,H74B), C92(H92A,H92B), C2(H2A,H2B), C8(H8A,
 H8B), C9(H9A,H9B), C2A(H2AA,H2AB), C8A(H8AA,H8AB), C9A(H9AA,H9AB), C2B(H2BA,
 H2BB), C3B(H3BA,H3BB), C4B(H4BA,H4BB), C5B(H5BA,H5BB), C6B(H6BA,H6BB)
7.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C31(H31), C48(H48), C72(H72)
7.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C87(H87A,H87B,H87C), C90(H90A,H90B,
 H90C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C96(H96A,H96B,H96C), C98(H98A,
 H98B,H98C), C99(H99A,H99B,H99C), C101(H10E,H10F,H10G), C102(H10H,H10I,H10J),
 C104(H10K,H10L,H10M), C106(H10N,H10O,H10P), C107(H10Q,H10R,H10S), C108(H10T,
 H10U,H10V), 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,H), C118(H11Z,HA,HB), C119(H11,HC,HD), 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,HE), C128(H12Z,HF,HG), C1(H1A,H1B,H1C), C7(H7A,H7B,H7C), C1A(H1AA,H1AB,
 H1AC), C7A(H7AA,H7AB,H7AC), C7B(H7BA,H7BB,H7BC)
7.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O3(H3), O4(H4)
;
_shelx_res_checksum              97359
_shelx_hkl_checksum              20602
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-11-04
_olex2_date_sample_submission    2016-11-04
_olex2_submission_original_sample_id d160815_35_1
_olex2_submission_special_instructions 'No special instructions were received'