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_4131449
_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 I, C2 H3 N'
_chemical_formula_sum            'C136 H182 I N O12'
_chemical_formula_weight         2149.72
_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             2016-11-16
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.07 svn.r3352 for OlexSys, GUI svn.r5261)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.43750(10)
_cell_length_b                   18.20030(10)
_cell_length_c                   46.4620(3)
_cell_measurement_reflns_used    167998
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.6520
_cell_measurement_theta_min      3.4370
_cell_volume                     13054.29(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 1.000
_diffrn_measured_fraction_theta_max 0.993
_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    -60.00  25.00   0.50    1.50    --  -50.21  38.00 -90.00  170
  2  \w   -120.00 -34.00   0.50    1.50    --  -50.21 -61.00 -70.00  172
  3  \w    -66.00  20.00   0.50    1.50    --  -50.21  61.00  68.00  172
  4  \w    -65.00  21.00   0.50    1.50    --  -50.21  57.00-150.00  172
  5  \w    -65.00  21.00   0.50    1.50    --  -50.21  57.00 -60.00  172
  6  \w   -125.00 -40.00   0.50    1.50    --  -50.21 -38.00 120.00  170
  7  \w    -70.00   5.00   0.50    7.00    --  -70.00  38.00 120.00  150
  8  \w   -139.00 -82.00   0.50    7.00    --  -70.00 -99.00  90.00  114
  9  \w   -139.00 -82.00   0.50    7.00    --  -70.00 -99.00-180.00  114
 10  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00 -30.00  176
 11  \w    -92.00  -5.00   0.50    7.00    --  -70.00  77.00-150.00  174
 12  \w     33.00  70.00   0.50    7.00    --  107.75 -38.00  30.00   74
 13  \w     38.00 121.00   0.50    7.00    --  107.75-125.00   0.00  166
 14  \w     33.00  76.00   0.50    7.00    --  107.75 -19.00  90.00   86
 15  \w     33.00  70.00   0.50    7.00    --  107.75 -38.00 -60.00   74
 16  \w     33.00  70.00   0.50    7.00    --  107.75 -38.00-180.00   74
 17  \w     33.00  70.00   0.50    7.00    --  107.75 -38.00  60.00   74
 18  \w     38.00 121.00   0.50    7.00    --  107.75-125.00-180.00  166
 19  \w     33.00  76.00   0.50    7.00    --  107.75 -19.00-150.00   86
 20  \w     37.00 106.00   0.50    7.00    --  107.75 -57.00   0.00  138
 21  \w     33.00  70.00   0.50    7.00    --  107.75 -38.00  90.00   74
 22  \w     97.00 178.00   0.50    7.00    --  107.75  19.00 120.00  162
 23  \w     97.00 178.00   0.50    7.00    --  107.75  19.00-150.00  162
 24  \w     39.00 111.00   0.50    7.00    --  107.75 -99.00-180.00  144
 25  \w     33.00  76.00   0.50    7.00    --  107.75 -19.00-180.00   86
 26  \w     39.00 111.00   0.50    7.00    --  107.75 -99.00-150.00  144
 27  \w     43.00 130.00   0.50    7.00    --  107.75 -77.00-150.00  174
 28  \w     33.00  76.00   0.50    7.00    --  107.75 -19.00 -90.00   86
 29  \w     43.00 130.00   0.50    7.00    --  107.75 -77.00   0.00  174
 30  \w     33.00  70.00   0.50    7.00    --  107.75 -38.00 150.00   74
 31  \w     37.00 106.00   0.50    7.00    --  107.75 -57.00-120.00  138
 32  \w     33.00  70.00   0.50    7.00    --  107.75 -38.00-150.00   74
 33  \w     91.00 178.00   0.50    7.00    --  107.75 125.00-180.00  174
 34  \w     39.00 111.00   0.50    7.00    --  107.75 -99.00 -30.00  144
 35  \w     33.00  70.00   0.50    7.00    --  107.75 -38.00 -30.00   74
 36  \w     39.00 111.00   0.50    7.00    --  107.75 -99.00  60.00  144
 37  \w     33.00  76.00   0.50    7.00    --  107.75 -19.00 -60.00   86
 38  \w   -115.00 -28.00   0.50    1.50    --  -50.21 -77.00-120.00  174
 39  \w   -115.00 -28.00   0.50    1.50    --  -50.21 -77.00 150.00  174
 40  \w   -115.00 -28.00   0.50    1.50    --  -50.21 -77.00  60.00  174
 41  \w   -115.00 -28.00   0.50    1.50    --  -50.21 -77.00  30.00  174
 42  \w   -121.00 -35.00   0.50    1.50    --  -50.21 -57.00 -30.00  172
 43  \w   -115.00 -28.00   0.50    1.50    --  -50.21 -77.00-150.00  174
 44  \w   -135.00 -83.00   0.50    7.00    --  -70.00 -77.00 -60.00  104
 45  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00-180.00  176
 46  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00  30.00  176
 47  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00-120.00  176
 48  \w   -135.00 -47.00   0.50    7.00    --  -70.00 -77.00 120.00  176
 49  \w     97.00 178.00   0.50    7.00    --  107.75  19.00  30.00  162
 50  \w     85.00 173.00   0.50    7.00    --  107.75  77.00 -60.00  176
 51  \w     98.00 178.00   0.50    7.00    --  107.75  38.00 -90.00  160
;
_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      0.0698414000
_diffrn_orient_matrix_UB_12      0.0052731000
_diffrn_orient_matrix_UB_13      0.0236141000
_diffrn_orient_matrix_UB_21      0.0096739000
_diffrn_orient_matrix_UB_22      -0.0842318000
_diffrn_orient_matrix_UB_23      -0.0002749000
_diffrn_orient_matrix_UB_31      0.0706028000
_diffrn_orient_matrix_UB_32      0.0063329000
_diffrn_orient_matrix_UB_33      -0.0232871000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.1085
_diffrn_reflns_av_unetI/netI     0.0365
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       53
_diffrn_reflns_limit_l_min       -58
_diffrn_reflns_number            373214
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.991
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.622
_diffrn_reflns_theta_min         3.085
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.355
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.778
_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    1.094
_exptl_crystal_description       block
_exptl_crystal_F_000             4616
_exptl_crystal_size_max          0.142
_exptl_crystal_size_mid          0.111
_exptl_crystal_size_min          0.082
_refine_diff_density_max         0.794
_refine_diff_density_min         -0.529
_refine_diff_density_rms         0.054
_refine_ls_abs_structure_details
;
 Flack x determined using 10368 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.0089(12)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1449
_refine_ls_number_reflns         28138
_refine_ls_number_restraints     193
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0497
_refine_ls_R_factor_gt           0.0446
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0729P)^2^+2.9297P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1194
_refine_ls_wR_factor_ref         0.1233
_reflns_Friedel_coverage         0.845
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.988
_reflns_number_gt                25456
_reflns_number_total             28138
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b05461_si_006.cif
_cod_data_source_block           d160815_36_1
_cod_database_code               4131449
_chemical_oxdiff_formula         C154H140N14O14I
_chemical_oxdiff_usercomment     'C6 H4 N2 O'
_reflns_odcompleteness_completeness 99.94
_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
 C24-C23 = C23-C22 = C22-C21 = C21-C20 = C20-C19
 1.5 with sigma of 0.02
 C11-C10 \\sim C9-C10 \\sim C9A-C10 \\sim C9-C8 \\sim C9A-C8A \\sim C8-C7 \\sim
C8A-C7A
 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
 C5-C4 \\sim C4-C3A \\sim C4-C3 \\sim C3A-C2A \\sim C3-C2 \\sim C2A-C1A \\sim
C2-C1
 with sigma of 0.02
 C1A-C3A \\sim C1-C3 \\sim C2A-C4 \\sim C2-C4 \\sim C3A-C5 \\sim C3-C5
 with sigma of 0.02
3. Rigid bond restraints
 C7, C8, C9, C10, C11, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C1A, C2A, C3A, C4, C3, C2, C1
 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) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C8)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 C7, C8, C9, C10, C11, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1A, C2A, C3A, C4, C3, C2, C1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C3A)=
 Sof(H3AA)=Sof(H3AB)=Sof(H4BC)=Sof(H4BD)=Sof(H10C)=Sof(H10D)=Sof(C7A)=Sof(H7AA)=
 Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=
 1-FVAR(1)
 Sof(H4AA)=Sof(H4AB)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=Sof(H8A)=
 Sof(H8B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(H10A)=Sof(H10B)=Sof(C3)=Sof(H3A)=
 Sof(H3B)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C41(H41), C45(H45), C48(H48), C52(H52), C1B(H1BA)
7.b Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C3A(H3AA,H3AB), C4(H4BC,H4BD), C4(H4AA,H4AB), C5(H5A,H5B),
 C6(H6A,H6B), C8(H8A,H8B), C9(H9A,H9B), 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), C38(H38A,H38B), C75(H75A,H75B),
 C83(H83A,H83B), C87(H87A,H87B), C2B(H2BA,H2BB), C3B(H3BA,H3BB), C4B(H4BA,H4BB),
  C5B(H5BA,H5BB), C6B(H6BA,H6BB), C3(H3A,H3B), C2(H2A,H2B), C8A(H8AA,H8AB),
 C9A(H9AA,H9AB)
7.c Aromatic/amide H refined with riding coordinates:
 C30(H30), C58(H58), C62(H62), C79(H79)
7.d Idealised Me refined as rotating group:
 C1A(H1AA,H1AB,H1AC), C7(H7A,H7B,H7C), C13(H13A,H13B,H13C), C19(H19A,H19B,
 H19C), C82(H82A,H82B,H82C), C85(H85A,H85B,H85C), C89(H89A,H89B,H89C), C90(H90A,
 H90B,H90C), C91(H91A,H91B,H91C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C),
 C100(H10E,H10F,H10G), C101(H10H,H10I,H10J), C102(H10K,H10L,H10M), C103(H10N,
 H10O,H10P), C104(H10Q,H10R,H10S), C105(H10T,H10U,H10V), C107(H10W,H10X,H10Y),
 C108(H10Z,H,HA), C109(H10,HB,HC), C110(H11C,H11D,H11E), C112(H11F,H11G,H11H),
 C113(H11I,H11J,H11K), C114(H11L,H11M,H11N), C115(H11O,H11P,H11Q), C116(H11R,
 H11S,H11T), C117(H11U,H11V,H11W), C118(H11X,H11Y,HD), C119(H11Z,HE,HF),
 C120(H12C,H12D,H12E), C122(H12F,H12G,H12H), C123(H12I,H12J,H12K), C125(H12L,
 H12M,H12N), C126(H12O,H12P,H12Q), C127(H12R,H12S,H12T), C128(H12U,H12V,H12W),
 C8B(H8BA,H8BB,H8BC), C1(H1A,H1B,H1C), C7A(H7AA,H7AB,H7AC)
7.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O3(H3), O4(H4)
;
_shelx_res_checksum              7105
_shelx_hkl_checksum              68550
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-11-14
_olex2_date_sample_submission    2016-11-14
_olex2_submission_original_sample_id d160815_36_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 1.740
_oxdiff_exptl_absorpt_empirical_full_min 0.650