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_4131442
_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 rmad
_chemical_formula_moiety         '0.39(C6 H10 Br F), C128 H168 O12'
_chemical_formula_sum            'C130.37 H171.94 Br0.4 F0.4 O12'
_chemical_formula_weight         1970.06
_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             2017-02-21
_audit_creation_method
;
Olex2 1.2
(compiled 2017.01.04 svn.r3372 for OlexSys, GUI svn.r5292)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.6487(4)
_cell_length_b                   18.7136(4)
_cell_length_c                   43.2272(10)
_cell_measurement_reflns_used    20761
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.6780
_cell_measurement_theta_min      3.4940
_cell_volume                     12658.8(5)
_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 0.998
_diffrn_measured_fraction_theta_max 0.997
_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    -77.00  14.00   0.50    3.26    --  -10.89 -77.00-180.00  182
  2  \w    -83.00 -38.00   0.50    3.26    --  -10.89-178.00-150.00   90
  3  \w   -140.00 -82.00   0.50    3.26    --  -70.00 -99.00 -90.00  116
  4  \w   -137.00 -82.00   0.50    3.26    --  -70.00 -77.00 -30.00  110
  5  \w   -137.00 -45.00   0.50    3.26    --  -70.00 -77.00  60.00  184
  6  \w   -137.00 -45.00   0.50    3.26    --  -70.00 -77.00 150.00  184
  7  \w    -95.00  -3.00   0.50    3.26    --  -70.00  77.00-150.00  184
  8  \w     94.00 125.00   0.50    3.26    --  110.00 -19.00  30.00   62
  9  \w     94.00 125.00   0.50    3.26    --  110.00 -19.00  60.00   62
 10  \w     94.00 125.00   0.50    3.26    --  110.00 -19.00  90.00   62
 11  \w     94.00 125.00   0.50    3.26    --  110.00 -19.00   0.00   62
 12  \w     95.00 178.00   0.50    3.26    --  110.00  19.00 -90.00  166
 13  \w     94.00 125.00   0.50    3.26    --  110.00 -19.00-120.00   62
 14  \w     94.00 125.00   0.50    3.26    --  110.00 -19.00-150.00   62
 15  \w     38.00 121.00   0.50    3.26    --  110.00-125.00-120.00  166
 16  \w     40.00 111.00   0.50    3.26    --  110.00 -99.00 -60.00  142
 17  \w     44.00 135.00   0.50    3.26    --  110.00 -77.00  30.00  182
 18  \w     38.00  84.00   0.50    3.26    --  110.00 -57.00-150.00   92
;
_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      0.0025378000
_diffrn_orient_matrix_UB_12      -0.0216903000
_diffrn_orient_matrix_UB_13      -0.0343540000
_diffrn_orient_matrix_UB_21      -0.0286351000
_diffrn_orient_matrix_UB_22      0.0758015000
_diffrn_orient_matrix_UB_23      -0.0092613000
_diffrn_orient_matrix_UB_31      0.0942076000
_diffrn_orient_matrix_UB_32      0.0236113000
_diffrn_orient_matrix_UB_33      -0.0018698000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0838
_diffrn_reflns_av_unetI/netI     0.0750
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       52
_diffrn_reflns_limit_l_min       -52
_diffrn_reflns_number            98925
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.074
_diffrn_reflns_theta_min         3.124
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.643
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.804
_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    1.034
_exptl_crystal_description       plate
_exptl_crystal_F_000             4270
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.097
_exptl_crystal_size_min          0.022
_refine_diff_density_max         0.521
_refine_diff_density_min         -0.238
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Flack x determined using 6045 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.11(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1513
_refine_ls_number_reflns         23833
_refine_ls_number_restraints     523
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.0846
_refine_ls_R_factor_gt           0.0572
_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^)+(0.0749P)^2^+0.8278P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1366
_refine_ls_wR_factor_ref         0.1499
_reflns_Friedel_coverage         0.833
_reflns_Friedel_fraction_full    0.991
_reflns_Friedel_fraction_max     0.984
_reflns_number_gt                17366
_reflns_number_total             23833
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b05461_si_012.cif
_cod_data_source_block           d160815_41_1
_cod_original_formula_sum        'C130.37 H171.94 Br0.40 F0.40 O12'
_cod_database_code               4131442
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C135H181Br1F1O12N1
_diffrn_oxdiff_ac3_digest_frames
;
01bc4783653828bfbf775d4586ec0a3436021708638
;
_diffrn_oxdiff_ac3_digest_hkl
;
01f10d7e2bc39b3fc3296b7b6218db59a3f629
;
_reflns_odcompleteness_completeness 99.80
_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, All O(H,H) groups
2. Restrained distances
 H1A-F1B
 2.56 with sigma of 0.01
 C6-C5A \\sim C6-C5 \\sim C5-C4 \\sim C5A-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-C5A \\sim
C4-C6 \\sim C4A-C6
 with sigma of 0.02
 C11-C10 \\sim C9-C10 \\sim C9-C8A \\sim C9-C8 \\sim C8A-C7A \\sim C8-C7
 with sigma of 0.02
 C7A-C9 \\sim C7-C9 \\sim C8A-C10 \\sim C8-C10
 with sigma of 0.02
 C17-C16 \\sim C16-C15 \\sim C16-C15A \\sim C15-C14 \\sim C15A-C14A \\sim
C14-C13 \\sim C14A-C13A
 with sigma of 0.02
 C13-C15 \\sim C13A-C15A \\sim C14-C16 \\sim C14A-C16 \\sim C15-C17 \\sim
C15A-C17
 with sigma of 0.02
 C106-C27A \\sim C128-C106 \\sim C106-C25A \\sim C126-C106 \\sim C106-C26A
\\sim C121-C106
 with sigma of 0.02
 C25A-C26A \\sim C26A-C27A \\sim C27A-C25A \\sim C121-C128 \\sim C128-C126
\\sim C126-C121
 with sigma of 0.02
 C28A-C110 \\sim C125-C110
 with sigma of 0.02
 C125-C117 \\sim C29A-C28A \\sim C30A-C28A \\sim C125-C127
 with sigma of 0.02
 C117-C127 \\sim C29A-C30A
 with sigma of 0.02
 O4A-C28A \\sim O4-C125
 with sigma of 0.02
3. Rigid bond restraints
 C6, C2, C5, C1, C3, C4, C5A, C4A, C3A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C12, C11, C10, C9, C8A, C7A, C8, C7
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C18, C17, C16, C15, C14, C13, C15A, C14A, C13A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C106, C121, C126, C128, C27A, C25A, C26A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O4A, C110, C28A, C29A, C117, C125, O4, C30A, C127
 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(C7) = Uanis(C7A)
5. Rigid body (RIGU) restrains
 C6, C2, C5, C1, C3, C4, C5A, C4A, C3A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C12, C11, C10, C9, C8A, C7A, C8, C7
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18, C17, C16, C15, C14, C13, C15A, C14A, C13A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C106, C121, C126, C128, C27A, C25A, C26A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Br1B, C3B, C4B, C1B, C2B, C5B, C6B, F1B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O4A, C28A, C117, C125, O4, C29A, C30A, C127, C110
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(H16C)=Sof(H16D)=Sof(H6BC)=Sof(H6BD)=Sof(H9BC)=Sof(H9BD)=Sof(H2BC)=
 Sof(H2BD)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=
 Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C3A)=Sof(H3AA)=
 Sof(H3AB)=Sof(C15A)=Sof(H15C)=Sof(H15D)=Sof(C14A)=Sof(H14C)=Sof(H14D)=
 Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=1-FVAR(1)
 Sof(H16A)=Sof(H16B)=Sof(H6AA)=Sof(H6AB)=Sof(H9AA)=Sof(H9AB)=Sof(H2AA)=
 Sof(H2AB)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C3)=
 Sof(H3A)=Sof(H3B)=Sof(C4)=Sof(H4B)=Sof(H4C)=Sof(C14)=Sof(H14A)=Sof(H14B)=
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(C7)=
 Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(1)
 Sof(O4A)=Sof(H4A)=Sof(H1B)=Sof(C28A)=Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=
 Sof(C29A)=Sof(H29A)=Sof(H29B)=Sof(H29C)=1-FVAR(2)
 Sof(Br1B)=Sof(H1A)=Sof(C3B)=Sof(H3BA)=Sof(H3BB)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=
 Sof(C1B)=Sof(H1BA)=Sof(C2B)=Sof(H2B)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(C6B)=
 Sof(H6BA)=Sof(H6BB)=Sof(F1B)=Sof(C117)=Sof(H11Z)=Sof(HD)=Sof(HE)=Sof(C125)=
 Sof(O4)=Sof(H4)=Sof(C127)=Sof(H12X)=Sof(H12Y)=Sof(HF)=FVAR(2)
 Sof(C27A)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C25A)=Sof(H25A)=Sof(H25B)=
 Sof(H25C)=Sof(C26A)=Sof(H26A)=Sof(H26B)=Sof(H26C)=1-FVAR(3)
 Sof(C121)=Sof(H12F)=Sof(H12G)=Sof(H12H)=Sof(C126)=Sof(H12R)=Sof(H12S)=
 Sof(H12T)=Sof(C128)=Sof(H12U)=Sof(H12V)=Sof(H12W)=FVAR(3)
7.a Ternary CH refined with riding coordinates:
 C46(H46), C48(H48), C49(H49), C59(H59), C1B(H1BA), C2B(H2B)
7.b Secondary CH2 refined with riding coordinates:
 C33(H33A,H33B), C51(H51A,H51B), C12(H12A,H12B), C18(H18A,H18B), C24(H24A,
 H24B), C74(H74A,H74B), C17(H17A,H17B), C88(H88A,H88B), C23(H23A,H23B),
 C11(H11A,H11B), C16(H16A,H16B), C16(H16C,H16D), C6(H6AA,H6AB), C6(H6BC,H6BD),
 C10(H10Z,HB), C20(H20A,H20B), C22(H22A,H22B), C21(H21A,H21B), C9(H9BC,H9BD),
 C9(H9AA,H9AB), C2(H2AA,H2AB), C2(H2BC,H2BD), C5(H5A,H5B), C15(H15A,H15B),
 C3(H3A,H3B), C8A(H8AA,H8AB), C4(H4B,H4C), C14(H14A,H14B), C3B(H3BA,H3BB),
 C4B(H4BA,H4BB), C5B(H5BA,H5BB), C5A(H5AA,H5AB), C4A(H4AA,H4AB), C3A(H3AA,H3AB),
  C8(H8A,H8B), C15A(H15C,H15D), C14A(H14C,H14D), C6B(H6BA,H6BB)
7.c Aromatic/amide H refined with riding coordinates:
 C32(H32), C34(H34), C56(H56), C64(H64)
7.d Idealised Me refined as rotating group:
 C90(H90A,H90B,H90C), C92(H92A,H92B,H92C), C95(H95A,H95B,H95C), C97(H97A,H97B,
 H97C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C), C100(H10A,H10B,H10C),
 C101(H10D,H10E,H10F), C102(H10G,H10H,H10I), C103(H10J,H10K,H10L), C104(H10M,
 H10N,H10O), C105(H10P,H10Q,H10R), C107(H10S,H10T,H10U), C108(H10V,H10W,H10X),
 C109(H10Y,H,HA), C111(H11C,H11D,H11E), C112(H11F,H11G,H11H), C113(H11I,H11J,
 H11K), C114(H11L,H11M,H11N), C115(H11O,H11P,H11Q), C116(H11R,H11S,H11T),
 C118(H11U,H11V,H11W), C119(H11X,H11Y,HC), C120(H12C,H12D,H12E), C121(H12F,H12G,
 H12H), C122(H12I,H12J,H12K), C123(H12L,H12M,H12N), C124(H12O,H12P,H12Q),
 C30A(H30A,H30B,H30C), C126(H12R,H12S,H12T), C1(H1C,H1D,H1E), C29A(H29A,H29B,
 H29C), C19(H19A,H19B,H19C), C128(H12U,H12V,H12W), C7A(H7AA,H7AB,H7AC),
 C13(H13A,H13B,H13C), C7(H7A,H7B,H7C), C13A(H13D,H13E,H13F), C27A(H27A,H27B,
 H27C), C25A(H25A,H25B,H25C), C26A(H26A,H26B,H26C), C117(H11Z,HD,HE), C127(H12X,
 H12Y,HF)
7.e Idealised tetrahedral OH refined as rotating group:
 O2(H2), O3(H3), O4A(H4A), O1(H1A), O1(H1B), O4(H4)
;
_shelx_res_checksum              67177
_shelx_hkl_checksum              49895
_olex2_date_sample_data_collection 2017-02-17
_olex2_date_sample_submission    2017-02-14
_olex2_submission_original_sample_id d160815_41_1
_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 1.214
_oxdiff_exptl_absorpt_empirical_full_min 0.760