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_4131443
_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 Cl2, C2 H3 N'
_chemical_formula_sum            'C136 H181 Cl2 N O12'
_chemical_formula_weight         2092.71
_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             2016-12-05
_audit_creation_method
;
Olex2 1.2
(compiled 2016.11.30 svn.r3356 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   46.4365(4)
_cell_length_b                   18.25356(12)
_cell_length_c                   15.48278(10)
_cell_measurement_reflns_used    115475
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.5290
_cell_measurement_theta_min      3.4190
_cell_volume                     13123.69(17)
_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 0.9905
_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   -120.00 -38.00   0.50    1.27    --  -50.21-178.00  30.00  164
  2  \w   -115.00 -28.00   0.50    1.27    --  -50.21 -77.00  90.00  174
  3  \w    -65.00  21.00   0.50    1.27    --  -50.21  57.00-180.00  172
  4  \w    -60.00  25.00   0.50    1.27    --  -50.21  38.00  60.00  170
  5  \w   -119.00 -60.00   0.50    1.27    --  -50.21-139.00 155.00  118
  6  \w    -85.00   1.00   0.50    5.09    --  -70.00  57.00-180.00  172
  7  \w    -85.00   1.00   0.50    5.09    --  -70.00  57.00   0.00  172
  8  \w   -140.00 -70.00   0.50    5.09    --  -70.00-125.00 -30.00  140
  9  \w    -70.00   5.00   0.50    5.09    --  -70.00  38.00 -30.00  150
 10  \w   -145.00 -60.00   0.50    5.09    --  -70.00 -38.00-150.00  170
 11  \w     33.00  76.00   0.50    5.09    --  107.75 -19.00-150.00   86
 12  \w     97.00 178.00   0.50    5.09    --  107.75  19.00 -30.00  162
 13  \w     37.00 106.00   0.50    5.09    --  107.75 -57.00  90.00  138
 14  \w     33.00  76.00   0.50    5.09    --  107.75 -19.00-180.00   86
 15  \w     33.00  76.00   0.50    5.09    --  107.75 -19.00  60.00   86
 16  \w     39.00 111.00   0.50    5.09    --  107.75 -99.00 120.00  144
 17  \w     33.00  70.00   0.50    5.09    --  107.75 -38.00   0.00   74
 18  \w     38.00 121.00   0.50    5.09    --  107.75-125.00-150.00  166
 19  \w     33.00  70.00   0.50    5.09    --  107.75 -38.00 -30.00   74
 20  \w     33.00  70.00   0.50    5.09    --  107.75 -38.00  60.00   74
 21  \w     39.00 111.00   0.50    5.09    --  107.75 -99.00  60.00  144
 22  \w     33.00  70.00   0.50    5.09    --  107.75 -38.00  30.00   74
 23  \w     39.00 111.00   0.50    5.09    --  107.75 -99.00 -90.00  144
 24  \w     33.00  70.00   0.50    5.09    --  107.75 -38.00 150.00   74
 25  \w     33.00  76.00   0.50    5.09    --  107.75 -19.00 -60.00   86
 26  \w     39.00 111.00   0.50    5.09    --  107.75 -99.00  30.00  144
 27  \w     91.00 178.00   0.50    5.09    --  107.75 125.00 -30.00  174
 28  \w     33.00  76.00   0.50    5.09    --  107.75 -19.00 150.00   86
 29  \w     33.00  76.00   0.50    5.09    --  107.75 -19.00   0.00   86
 30  \w     39.00 111.00   0.50    5.09    --  107.75 -99.00-120.00  144
 31  \w     37.00 106.00   0.50    5.09    --  107.75 -57.00-120.00  138
 32  \w     33.00  76.00   0.50    5.09    --  107.75 -19.00  30.00   86
 33  \w     33.00  76.00   0.50    5.09    --  107.75 -19.00 -90.00   86
 34  \w     39.00 111.00   0.50    5.09    --  107.75 -99.00 -30.00  144
 35  \w     97.00 178.00   0.50    5.09    --  107.75  19.00-180.00  162
 36  \w     39.00 111.00   0.50    5.09    --  107.75 -99.00  90.00  144
 37  \w     39.00 111.00   0.50    5.09    --  107.75 -99.00   0.00  144
 38  \w   -115.00 -28.00   0.50    1.27    --  -50.21 -77.00 150.00  174
 39  \w   -115.00 -28.00   0.50    1.27    --  -50.21 -77.00 -30.00  174
;
_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      -0.0327866000
_diffrn_orient_matrix_UB_12      -0.0046197000
_diffrn_orient_matrix_UB_13      -0.0143353000
_diffrn_orient_matrix_UB_21      -0.0043295000
_diffrn_orient_matrix_UB_22      0.0680792000
_diffrn_orient_matrix_UB_23      0.0573888000
_diffrn_orient_matrix_UB_31      0.0027680000
_diffrn_orient_matrix_UB_32      0.0496610000
_diffrn_orient_matrix_UB_33      -0.0799848000
_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  0.0715
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       58
_diffrn_reflns_limit_h_min       -58
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            267751
_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         79.232
_diffrn_reflns_theta_min         3.080
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.873
_exptl_absorpt_correction_T_max  0.721
_exptl_absorpt_correction_T_min  0.139
_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    1.059
_exptl_crystal_description       block
_exptl_crystal_F_000             4536
_exptl_crystal_size_max          0.234
_exptl_crystal_size_mid          0.168
_exptl_crystal_size_min          0.099
_refine_diff_density_max         0.614
_refine_diff_density_min         -0.348
_refine_diff_density_rms         0.060
_refine_ls_abs_structure_details
;
 Flack x determined using 9985 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.070(9)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.031
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1513
_refine_ls_number_reflns         28184
_refine_ls_number_restraints     295
_refine_ls_restrained_S_all      1.038
_refine_ls_R_factor_all          0.0788
_refine_ls_R_factor_gt           0.0729
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1487P)^2^+3.7611P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2160
_refine_ls_wR_factor_ref         0.2230
_reflns_Friedel_coverage         0.841
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.985
_reflns_number_gt                24935
_reflns_number_total             28184
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b05461_si_010.cif
_cod_data_source_block           d160815_31_5
_cod_original_cell_volume        13123.68(16)
_cod_database_code               4131443
_chemical_oxdiff_formula         'C134 H1478 Cl2 O12 N'
_diffrn_oxdiff_ac3_digest_frames
;
018c74dbc707502021fe4584992d00d7d7051006409
;
_diffrn_oxdiff_ac3_digest_hkl
;
01798446b37346879f5d2600024c14784dbec3
;
_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
 C3-C2A = C3-C2 = C2-C1 = C2A-C1A
 1.51 with sigma of 0.02
 C4-C3 \\sim C2A-C3 \\sim C3-C2 \\sim C2A-C1A \\sim C2-C1
 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 C9-C8 \\sim C9A-C8A \\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
 C2B-C1B \\sim C2C-C1C
 with sigma of 0.02
 Cl2B-C2B \\sim Cl2C-C2C \\sim Cl1C-C1C \\sim Cl1B-C1B
 with sigma of 0.02
3. Rigid bond restraints
 C3, C4, C1A, C2A, C1, C2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C10, C11, C7A, C8A, C9A, C7, C8, C9
 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(C8) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C9A) \\sim
Ueq, Uanis(C8A) \\sim Ueq, Uanis(C7A) \\sim Ueq: with sigma of 0.02 and sigma
for terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 C3, C4, C1A, C2A, C1, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10, C11, C7A, C8A, C9A, C7, C8, C9
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C6B, C1B, Cl1C, Cl2C, C1C, C2C, C3C, C4C, C5C, C4B, C3B, C5B, Cl1B, Cl2B, C2B
 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(Cl1C)=Sof(Cl2C)=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(C1B)=Sof(H1BA)=Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(C3B)=
 Sof(H3BA)=Sof(H3BB)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(Cl1B)=Sof(Cl2B)=Sof(C2B)=
 Sof(H2BA)=FVAR(2)
7.a Ternary CH refined with riding coordinates:
 C35(H35), C60(H60), C126(H126), C127(H127), C1B(H1BA), C1C(H1CA), C2C(H2C),
 C2B(H2BA)
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), C32(H32A,
 H32B), C63(H63A,H63B), C70(H70A,H70B), C85(H85A,H85B), C2A(H2AA,H2AB),
 C8A(H8AA,H8AB), C9A(H9AA,H9AB), C6B(H6BA,H6BB), C6B(H6BC,H6BD), C3C(H3CA,H3CB),
  C4C(H4CA,H4CB), C5C(H5CA,H5CB), C4B(H4BA,H4BB), C2(H2A,H2B), C8(H8A,H8B),
 C9(H9A,H9B), C3B(H3BA,H3BB), C5B(H5BA,H5BB)
7.c Aromatic/amide H refined with riding coordinates:
 C25(H25), C47(H47), C55(H55), C128(H128)
7.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C84(H84A,H84B,H84C), C90(H90A,H90B,
 H90C), C95(H95A,H95B,H95C), C96(H96A,H96B,H96C), C97(H97A,H97B,H97C), C98(H98A,
 H98B,H98C), C100(H10E,H10F,H10G), C101(H10H,H10I,H10J), C102(H10K,H10L,H10M),
 C103(H10N,H10O,H10P), C104(H10Q,H10R,H10S), C105(H10T,H10U,H10V), C106(H10W,
 H10X,H10Y), C107(H10Z,H,HA), C108(H10,HB,HC), C109(H0AA,HD,HE), 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,HF), C118(H11Z,HG,HH), C119(H11,HI,HJ), C120(H12C,H12D,H12E), C121(H12F,
 H12G,H12H), C122(H12I,H12J,H12K), C123(H12L,H12M,H12N), C124(H12O,H12P,H12Q),
 C125(H12R,H12S,H12T), C1A(H1AA,H1AB,H1AC), C7A(H7AA,H7AB,H7AC), C8AA(H8AC,H8AD,
 H8AE), C1(H1A,H1B,H1C), C7(H7A,H7B,H7C)
7.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O3(H3), O4(H4)
;
_shelx_res_checksum              26409
_shelx_hkl_checksum              49729
_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_31_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 2.227
_oxdiff_exptl_absorpt_empirical_full_min 0.566