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_4131446
_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 Br2, C2 H3 N'
_chemical_formula_sum            'C136 H181 Br2 N O12'
_chemical_formula_weight         2181.63
_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             2016-11-30
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.24 svn.r3356 for OlexSys, GUI svn.r5267)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.46290(10)
_cell_length_b                   18.22110(10)
_cell_length_c                   46.7056(3)
_cell_measurement_reflns_used    197179
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.4720
_cell_measurement_theta_min      3.4140
_cell_volume                     13159.35(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.9f (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.9f (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    '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 0.9995
_diffrn_measured_fraction_theta_max 0.9902
_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   -125.00 -40.00   0.50    1.50    --  -50.21 -19.00  90.00  170
  2  \w   -125.00 -40.00   0.50    1.50    --  -50.21 -19.00 150.00  170
  3  \w   -125.00 -40.00   0.50    1.50    --  -50.21 -19.00  30.00  170
  4  \w   -125.00 -40.00   0.50    1.50    --  -50.21 -38.00  30.00  170
  5  \w   -115.00 -28.00   0.50    1.50    --  -50.21 -77.00 -30.00  174
  6  \w   -121.00 -35.00   0.50    1.50    --  -50.21 -57.00  30.00  172
  7  \w   -121.00 -35.00   0.50    1.50    --  -50.21 -57.00 -30.00  172
  8  \w   -125.00 -40.00   0.50    1.50    --  -50.21 -19.00-120.00  170
  9  \w   -121.00 -35.00   0.50    1.50    --  -50.21 -57.00-180.00  172
 10  \w    -94.00  -6.00   0.50    1.50    --  -50.21 121.00 161.00  176
 11  \w     59.00 120.00   0.50    1.50    --   50.21 178.00  30.00  122
 12  \w     28.00 115.00   0.50    1.50    --   50.21  77.00  90.00  174
 13  \w     36.00 121.00   0.50    1.50    --   50.21  57.00-180.00  170
 14  \w     28.00 115.00   0.50    1.50    --   50.21  77.00  30.00  174
 15  \w     40.00 125.00   0.50    1.50    --   50.21  38.00-120.00  170
 16  \w     28.00 115.00   0.50    1.50    --   50.21  77.00 150.00  174
 17  \w     40.00 125.00   0.50    1.50    --   50.21  38.00  90.00  170
 18  \w     28.00 115.00   0.50    1.50    --   50.21  77.00 -60.00  174
 19  \w     28.00 115.00   0.50    1.50    --   50.21  77.00-180.00  174
 20  \w     28.00 115.00   0.50    1.50    --   50.21  77.00-120.00  174
 21  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00 150.00  176
 22  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00 -30.00  176
 23  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00 -60.00  176
 24  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00  60.00  176
 25  \w    -95.00  -9.00   0.50    7.00    --  -70.00 125.00-180.00  172
 26  \w   -141.00 -55.00   0.50    7.00    --  -70.00 -57.00 -90.00  172
 27  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00  90.00  176
 28  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00-120.00  176
 29  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00 -90.00  176
 30  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00-180.00  176
 31  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00  30.00  176
 32  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00 120.00  176
 33  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00-150.00  176
 34  \w    -85.00   1.00   0.50    7.00    --  -70.00  57.00  90.00  172
 35  \w    -83.00 -47.00   0.50    7.00    --  -70.00 -77.00   0.00   72
 36  \w    126.00 171.00   0.50    7.00    --  107.75  77.00-120.00   90
 37  \w     85.00 113.00   0.50    7.00    --  107.75  77.00-120.00   56
 38  \w     57.00 109.00   0.50    7.00    --  107.75 -99.00-180.00  104
 39  \w     93.00 131.00   0.50    7.00    --  107.75  57.00  90.00   76
 40  \w     94.00 144.00   0.50    7.00    --  107.75  57.00-120.00  100
 41  \w     93.00 121.00   0.50    7.00    --  107.75  57.00 -90.00   56
 42  \w     85.00 172.00   0.50    7.00    --  107.75  77.00   0.00  174
 43  \w     98.00 156.00   0.50    7.00    --  107.75  38.00  30.00  116
 44  \w     86.00 111.00   0.50    7.00    --  107.75  77.00 -60.00   50
 45  \w     85.00 119.00   0.50    7.00    --  107.75  77.00-180.00   68
 46  \w     39.00 103.00   0.50    7.00    --  107.75 -99.00  60.00  128
 47  \w     85.00 173.00   0.50    7.00    --  107.75  77.00  30.00  176
 48  \w     40.00 105.00   0.50    7.00    --  107.75 -57.00 -60.00  130
 49  \w     37.00 105.00   0.50    7.00    --  107.75 -57.00 150.00  136
 50  \w    120.00 169.00   0.50    7.00    --  107.75  77.00 120.00   98
 51  \w     40.00 111.00   0.50    7.00    --  107.75 -99.00 -30.00  142
 52  \w     85.00 112.00   0.50    7.00    --  107.75  77.00 120.00   54
 53  \w    132.00 175.00   0.50    7.00    --  107.75  57.00-180.00   86
 54  \w     85.00 162.00   0.50    7.00    --  107.75  77.00-150.00  154
 55  \w     87.00 130.00   0.50    7.00    --  107.75 -77.00 150.00   86
 56  \w     93.00 128.00   0.50    7.00    --  107.75  57.00-180.00   70
 57  \w     94.00 122.00   0.50    7.00    --  107.75  57.00 150.00   56
 58  \w     85.00 164.00   0.50    7.00    --  107.75  77.00  90.00  158
 59  \w     93.00 133.00   0.50    7.00    --  107.75  57.00 -30.00   80
 60  \w     85.00 157.00   0.50    7.00    --  107.75  77.00 -30.00  144
 61  \w     39.00 106.00   0.50    7.00    --  107.75 -57.00  60.00  134
 62  \w     93.00 175.00   0.50    7.00    --  107.75  57.00 -60.00  164
 63  \w     85.00 168.00   0.50    7.00    --  107.75  77.00 -90.00  166
 64  \w     85.00 170.00   0.50    7.00    --  107.75  77.00  60.00  170
 65  \w     58.00 121.00   0.50    7.00    --  107.75-125.00 -30.00  126
 66  \w     98.00 125.00   0.50    7.00    --  107.75  38.00 150.00   54
 67  \w     93.00 125.00   0.50    7.00    --  107.75  57.00  60.00   64
 68  \w     85.00 172.00   0.50    7.00    --  107.75  77.00 150.00  174
 69  \w     93.00 145.00   0.50    7.00    --  107.75  57.00-150.00  104
 70  \w     39.00 111.00   0.50    7.00    --  107.75 -99.00  90.00  144
;
_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      0.0718155000
_diffrn_orient_matrix_UB_12      -0.0410101000
_diffrn_orient_matrix_UB_13      0.0163626000
_diffrn_orient_matrix_UB_21      0.0478325000
_diffrn_orient_matrix_UB_22      -0.0140864000
_diffrn_orient_matrix_UB_23      -0.0283992000
_diffrn_orient_matrix_UB_31      0.0498035000
_diffrn_orient_matrix_UB_32      0.0725862000
_diffrn_orient_matrix_UB_33      0.0036904000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0772
_diffrn_reflns_av_unetI/netI     0.0260
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       59
_diffrn_reflns_limit_l_min       -59
_diffrn_reflns_number            507977
_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         79.598
_diffrn_reflns_theta_min         3.010
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.209
_exptl_absorpt_correction_T_max  0.840
_exptl_absorpt_correction_T_min  0.196
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9f (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    1.101
_exptl_crystal_description       plate
_exptl_crystal_F_000             4680
_exptl_crystal_size_max          0.127
_exptl_crystal_size_mid          0.121
_exptl_crystal_size_min          0.034
_refine_diff_density_max         0.626
_refine_diff_density_min         -0.615
_refine_diff_density_rms         0.050
_refine_ls_abs_structure_details
;
 Flack x determined using 10305 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.020(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1513
_refine_ls_number_reflns         28355
_refine_ls_number_restraints     281
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0568
_refine_ls_R_factor_gt           0.0489
_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^)+(0.0772P)^2^+4.9152P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1294
_refine_ls_wR_factor_ref         0.1361
_reflns_Friedel_coverage         0.844
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.986
_reflns_number_gt                25061
_reflns_number_total             28355
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b05461_si_011.cif
_cod_data_source_block           d160815_35_5
_cod_database_code               4131446
_chemical_oxdiff_formula         'C134 H178 Br2 O12'
_diffrn_oxdiff_ac3_digest_frames
;
018d157e228b001343a3faf5990d294d9509804a3f6
;
_diffrn_oxdiff_ac3_digest_hkl
;
010534652531693a4cce31e3329d80a18853ee
;
_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 O(H) groups
2. Restrained distances
 C4-C3 \\sim C3-C2 \\sim C2-C1 \\sim C3-C2A \\sim C1A-C2A
 with sigma of 0.02
 C1-C3 \\sim C1A-C3 \\sim C2-C4 \\sim C2A-C4
 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
 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
 C6B-C1C \\sim C6B-C5C
 with sigma of 0.02
3. Rigid bond restraints
 C3, C4, C5, C10, C11, C1, C2, C7, C8, C9, C1A, C2A, 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(C8A) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C7)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 C3C, C6B, C1B, C5B, C1C, C5C, Br1B, C2B, C4B, Br1C, C2C, C4C, Br2B, C3B, Br2C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C3, C4, C10, C1, C2, C7, C8, C9, C1A, C2A, C7A, C8A, C9A, C11, C5
 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)
 Sof(H6BC)=Sof(H6BD)=Sof(Br1C)=Sof(Br2C)=Sof(C1C)=Sof(H1CA)=Sof(C2C)=Sof(H2C)=
 Sof(C3C)=Sof(H3CA)=Sof(H3CB)=Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(C5C)=Sof(H5CA)=
 Sof(H5CB)=1-FVAR(2)
 Sof(H6BA)=Sof(H6BB)=Sof(Br1B)=Sof(Br2B)=Sof(C1B)=Sof(H1BA)=Sof(C2B)=Sof(H2BA)=
 Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(C5B)=Sof(H5BA)=
 Sof(H5BB)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C26(H26), C34(H34), C49(H49), C58(H58), C1B(H1BA), C2B(H2BA), C1C(H1CA),
 C2C(H2C)
7.b Secondary CH2 refined with riding coordinates:
 C3(H3BC,H3BD), C3(H3AA,H3AB), 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), C36(H36A,
 H36B), C73(H73A,H73B), C84(H84A,H84B), C128(H12Z,HJ), C2(H2A,H2B), C8(H8A,H8B),
  C9(H9A,H9B), C2A(H2AA,H2AB), C8A(H8AA,H8AB), C9A(H9AA,H9AB), C6B(H6BA,H6BB),
 C6B(H6BC,H6BD), C3B(H3BA,H3BB), C4B(H4BA,H4BB), C5B(H5BA,H5BB), C3C(H3CA,H3CB),
  C4C(H4CA,H4CB), C5C(H5CA,H5CB)
7.c Aromatic/amide H refined with riding coordinates:
 C28(H28), C30(H30), C38(H38), C50(H50)
7.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C90(H90A,H90B,H90C), C95(H95A,H95B,
 H95C), C96(H96A,H96B,H96C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C),
 C101(H10E,H10F,H10G), C102(H10H,H10I,H10J), C103(H10K,H10L,H10M), C104(H10N,
 H10O,H10P), C105(H10Q,H10R,H10S), C106(H10T,H10U,H10V), C107(H10W,H10X,H10Y),
 C108(H,H10Z,HA), C109(H10,HB,HC), 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,HD), C118(H11Z,HE,HF),
 C119(H11,HG,HH), 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,HI), 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              15209
_shelx_hkl_checksum              25569
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-11-28
_olex2_date_sample_submission    2016-11-28
_olex2_submission_original_sample_id d160815_35_5
_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 1.824
_oxdiff_exptl_absorpt_empirical_full_min 0.477