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_4131450
_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, C8 H16, C2 H3 N'
_chemical_formula_sum            'C138 H187 N O12'
_chemical_formula_weight         2051.87
_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             2016-11-02
_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                   15.49690(10)
_cell_length_b                   18.24030(10)
_cell_length_c                   46.6272(3)
_cell_measurement_reflns_used    80850
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.7020
_cell_measurement_theta_min      2.6170
_cell_volume                     13180.02(14)
_computing_cell_refinement       'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.8d (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.8d (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      air
_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 1.000
_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   -124.00 -41.00   0.50    1.00    --  -50.21 -38.00 -90.00  166
  2  \w    -59.00  23.00   0.50    1.00    --  -50.21  38.00-150.00  164
  3  \w   -119.00 -39.00   0.50    1.00    --  -50.21-178.00-120.00  160
  4  \w     60.00 119.00   0.50    1.00    --   50.21 178.00 -60.00  118
  5  \w   -134.00 -49.00   0.50    5.00    --  -70.00 -77.00 120.00  170
  6  \w     99.00 177.00   0.50    5.00    --  107.75  38.00 120.00  156
  7  \w     34.00 117.00   0.50    5.00    --  107.75 -19.00 -90.00  166
  8  \w     40.00 110.00   0.50    5.00    --  107.75 -99.00 150.00  140
  9  \w     39.00 120.00   0.50    5.00    --  107.75-125.00  90.00  162
 10  \w     40.00 110.00   0.50    5.00    --  107.75 -99.00 -60.00  140
 11  \w     40.00 110.00   0.50    5.00    --  107.75 -99.00  90.00  140
 12  \w   -114.00 -29.00   0.50    1.00    --  -50.21 -77.00  30.00  170
 13  \w   -124.00 -41.00   0.50    1.00    --  -50.21 -38.00-120.00  166
 14  \w   -114.00 -29.00   0.50    1.00    --  -50.21 -77.00-150.00  170
 15  \w     99.00 162.00   0.50    5.00    --  107.75  38.00  30.00  126
;
_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      -0.0033372000
_diffrn_orient_matrix_UB_12      -0.0563149000
_diffrn_orient_matrix_UB_13      0.0245886000
_diffrn_orient_matrix_UB_21      -0.0297959000
_diffrn_orient_matrix_UB_22      -0.0594870000
_diffrn_orient_matrix_UB_23      -0.0212719000
_diffrn_orient_matrix_UB_31      0.0947858000
_diffrn_orient_matrix_UB_32      -0.0207017000
_diffrn_orient_matrix_UB_33      -0.0058110000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0348
_diffrn_reflns_av_unetI/netI     0.0239
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       56
_diffrn_reflns_limit_l_min       -56
_diffrn_reflns_number            115839
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.075
_diffrn_reflns_theta_min         2.601
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.496
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64210
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.8d (Rigaku Oxford Diffraction, 2015)
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       block
_exptl_crystal_F_000             4472
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.23
_exptl_crystal_size_min          0.18
_refine_diff_density_max         0.688
_refine_diff_density_min         -0.543
_refine_diff_density_rms         0.063
_refine_ls_abs_structure_details
;
 Flack x determined using 8544 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.01(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.128
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1451
_refine_ls_number_reflns         24602
_refine_ls_number_restraints     134
_refine_ls_restrained_S_all      1.132
_refine_ls_R_factor_all          0.0807
_refine_ls_R_factor_gt           0.0570
_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^)+(0.0590P)^2^+16.0640P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1351
_refine_ls_wR_factor_ref         0.1826
_reflns_Friedel_coverage         0.814
_reflns_Friedel_fraction_full    0.975
_reflns_Friedel_fraction_max     0.964
_reflns_number_gt                21501
_reflns_number_total             24602
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b05461_si_005.cif
_cod_data_source_block           d160815_20_2
_cod_database_code               4131450
_chemical_oxdiff_usercomment     '100K Cu'
_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-C2A \\sim C3-C2 \\sim C2-C1 \\sim C1A-C2A
 with sigma of 0.02
 C1-C3 \\sim C1A-C3
 with sigma of 0.02
 C9-C10 \\sim C9A-C10 \\sim C9-C8 \\sim C9A-C8A \\sim C8-C7 \\sim C8A-C7A
 with sigma of 0.02
 C7A-C9A \\sim C7-C9 \\sim C8A-C10 \\sim C8-C10
 with sigma of 0.02
 C5-C4 \\sim C4-C3 \\sim C3-C2 \\sim C2-C1
 with sigma of 0.02
3. Rigid bond restraints
 C1A, C1, C2, C2A, C3
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C7A, C8A, C9A, C10, C9, C8, C7
 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(C8) \\sim Ueq, Uanis(C8A) \\sim Ueq, Uanis(C7A) \\sim Ueq, Uanis(C7)
\\sim Ueq: with sigma of 0.03 and sigma for terminal atoms of 0.06
5. Rigid body (RIGU) restrains
 C1, C2, C3, C4, C2A, C1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C7A, C8A, C9A, C10, C9, C8, C7
 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(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=Sof(C8A)=Sof(H8AA)=
 Sof(H8AB)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(H10C)=Sof(H10D)=Sof(C2A)=Sof(H2AA)=
 Sof(H2AB)=Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C2)=Sof(H2A)=Sof(H2B)=Sof(H3AA)=
 Sof(H3AB)=Sof(H10A)=Sof(H10B)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C8)=Sof(H8A)=
 Sof(H8B)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=FVAR(1)
7.a Ternary CH refined with riding coordinates:
 C29(H29), C33(H33), C37(H37), C40(H40), C3B(H3B), C2B(H2BA)
7.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C3(H3BC,H3BD), C3(H3AA,H3AB), C4(H4A,H4B), C5(H5A,H5B), C6(H6A,
 H6B), C8A(H8AA,H8AB), C9A(H9AA,H9AB), C10(H10C,H10D), C10(H10A,H10B), 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), C44(H44A,H44B), C48(H48A,H48B), C52(H52A,
 H52B), C56(H56A,H56B), C5B(H5BA,H5BB), C6B(H6BA,H6BB), C7B(H7BA,H7BB),
 C8B(H8BA,H8BB), C2A(H2AA,H2AB), C9(H9A,H9B), C8(H8A,H8B)
7.c Aromatic/amide H refined with riding coordinates:
 C27(H27), C31(H31), C35(H35), C39(H39)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C7A(H7AA,H7AB,H7AC), C13(H13A,H13B,H13C), C19(H19A,H19B,
 H19C), C61(H61A,H61B,H61C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C67(H67A,
 H67B,H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C73(H73A,H73B,H73C),
 C74(H74A,H74B,H74C), C79(H79A,H79B,H79C), C80(H80A,H80B,H80C), C81(H81A,H81B,
 H81C), C85(H85A,H85B,H85C), C86(H86A,H86B,H86C), C87(H87A,H87B,H87C), C91(H91A,
 H91B,H91C), C92(H92A,H92B,H92C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C),
 C99(H99A,H99B,H99C), C103(H10E,H10F,H10G), C104(H10H,H10I,H10J), C105(H10K,
 H10L,H10M), C109(H10N,H10O,H10P), C110(H11C,H11D,H11E), C115(H11F,H11G,H11H),
 C116(H11I,H11J,H11K), C117(H11L,H11M,H11N), C121(H12C,H12D,H12E), C122(H12F,
 H12G,H12H), C123(H12I,H12J,H12K), C127(H12L,H12M,H12N), C128(H12O,H12P,H12Q),
 C4B(H4BA,H4BB,H4BC), C1B(H1BA,H1BB,H1BC), C9B(H9BA,H9BB,H9BC), C1A(H1AA,H1AB,
 H1AC), C7(H7A,H7B,H7C)
7.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O3(H3), O4(H4)
;
_shelx_res_checksum              88602
_shelx_hkl_checksum              71407
_shelx_shelxl_version_number     2014/7
_olex2_date_sample_data_collection 2016-10-24
_olex2_date_sample_submission    2016-10-24
_olex2_submission_original_sample_id d160815_20_2
_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 1.488
_oxdiff_exptl_absorpt_empirical_full_min 0.832