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_4131448
_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             2016-12-19
_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                   15.45050(10)
_cell_length_b                   18.1775(2)
_cell_length_c                   46.8762(4)
_cell_measurement_reflns_used    33618
_cell_measurement_temperature    100.0(1)
_cell_measurement_theta_max      78.5110
_cell_measurement_theta_min      3.4340
_cell_volume                     13165.2(2)
_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 0.9965
_diffrn_measured_fraction_theta_max 0.9509
_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     44.00  70.00   0.50    2.20    --  107.75   0.00 150.00   52
  2  \w    141.00 172.00   0.50    2.20    --  107.75 125.00 150.00   62
  3  \w     93.00 119.00   0.50    2.20    --  107.75 125.00 150.00   52
  4  \w    115.00 143.00   0.50    2.20    --  107.75   0.00 150.00   56
  5  \w    -58.00  19.00   0.50    0.55    --  -50.21  57.00  60.00  154
  6  \w    -91.00 -38.00   0.50    2.20    --  -70.00  77.00-120.00  106
  7  \w    -31.00  -5.00   0.50    2.20    --  -70.00  77.00-120.00   52
  8  \w    -25.00   3.00   0.50    0.55    --  -50.21  38.00-180.00   56
  9  \w   -111.00 -82.00   0.50    2.20    --  -70.00 -99.00 -30.00   58
 10  \w     42.00  70.00   0.50    2.20    --  107.75 -38.00-120.00   56
 11  \w     33.00  65.00   0.50    2.20    --  107.75 -22.00  43.00   64
 12  \w     34.00  64.00   0.50    2.20    --  107.75 -38.00 150.00   60
 13  \w     36.00  62.00   0.50    2.20    --  107.75 -19.00-150.00   52
 14  \w     47.00  72.00   0.50    2.20    --  107.75 -19.00   0.00   50
 15  \w     39.00  64.00   0.50    2.20    --  107.75 -38.00-150.00   50
 16  \w     34.00  59.00   0.50    2.20    --  107.75 -38.00-180.00   50
 17  \w   -118.00 -93.00   0.50    0.55    --  -50.21 -57.00 -90.00   50
 18  \w     47.00 108.00   0.50    2.20    --  107.75 -99.00 -60.00  122
;
_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      -0.0166321000
_diffrn_orient_matrix_UB_12      -0.0446158000
_diffrn_orient_matrix_UB_13      0.0274131000
_diffrn_orient_matrix_UB_21      0.0230120000
_diffrn_orient_matrix_UB_22      0.0679191000
_diffrn_orient_matrix_UB_23      0.0181443000
_diffrn_orient_matrix_UB_31      -0.0955318000
_diffrn_orient_matrix_UB_32      0.0240978000
_diffrn_orient_matrix_UB_33      -0.0004142000
_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  0.0409
_diffrn_reflns_av_unetI/netI     0.0456
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -56
_diffrn_reflns_number            58706
_diffrn_reflns_point_group_measured_fraction_full 0.951
_diffrn_reflns_point_group_measured_fraction_max 0.951
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         3.426
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.208
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.611
_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_density_diffrn    1.101
_exptl_crystal_F_000             4680
_exptl_crystal_size_max          0.197
_exptl_crystal_size_mid          0.156
_exptl_crystal_size_min          0.066
_refine_diff_density_max         0.396
_refine_diff_density_min         -0.334
_refine_diff_density_rms         0.036
_refine_ls_abs_structure_details
;
 Flack x determined using 8092 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.036(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.023
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1513
_refine_ls_number_reflns         22357
_refine_ls_number_restraints     256
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0405
_refine_ls_R_factor_gt           0.0354
_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^)+(0.0473P)^2^+1.4799P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0863
_refine_ls_wR_factor_ref         0.0887
_reflns_Friedel_coverage         0.756
_reflns_Friedel_fraction_full    0.897
_reflns_Friedel_fraction_max     0.896
_reflns_number_gt                20416
_reflns_number_total             22357
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b05461_si_003.cif
_cod_data_source_block           d160815_35_6
_cod_database_code               4131448
_chemical_oxdiff_formula         'C11 H10 N O'
_diffrn_oxdiff_ac3_digest_frames
;
0186a9fa1f4cbb2e0fe214fd243b7dec50012023a31
;
_diffrn_oxdiff_ac3_digest_hkl
;
011d79c2c1be353e121688dcd48dedd61e9abc
;
_reflns_odcompleteness_completeness 99.65
_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-C4 \\sim C2-C3 \\sim C2A-C3 \\sim C1-C2 \\sim C1A-C2A
 with sigma of 0.02
 C1-C3 \\sim C1A-C3 \\sim C2-C4 \\sim C2A-C4
 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
 Br1C-C1C \\sim Br1B-C1B \\sim Br2C-C2C \\sim Br2B-C2B
 with sigma of 0.02
 C2C-C1C \\sim C2B-C1B
 with sigma of 0.02
 C6B-C1B \\sim C6C-C1C \\sim C3B-C2B \\sim C3B-C2C
 with sigma of 0.02
 C6B-C5B \\sim C6C-C4C \\sim C4B-C3B \\sim C5C-C3B
 with sigma of 0.02
 C5B-C4B \\sim C5C-C4C
 with sigma of 0.02
3. Rigid bond restraints
 C3, C4, C1, C2, C1A, C2A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C10, C7, C8, C9, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Rigid body (RIGU) restrains
 C3, C4, C1, C2, C1A, C2A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C10, C7, C8, C9, C7A, C8A, C9A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1B, Br1B, C2B, C6B, Br2B, C3B, C5B, C4B, C2C, C5C, Br2C, C1C, C4C, Br1C, C6C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. 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(H3BE)=Sof(H3BF)=Sof(Br1C)=Sof(Br2C)=Sof(C1C)=Sof(H1CA)=Sof(C4C)=Sof(H4CA)=
 Sof(H4CB)=Sof(C2C)=Sof(H2C)=Sof(C6C)=Sof(H6CA)=Sof(H6CB)=Sof(C5C)=Sof(H5CA)=
 Sof(H5CB)=1-FVAR(2)
 Sof(Br1B)=Sof(Br2B)=Sof(C1B)=Sof(H1BA)=Sof(C2B)=Sof(H2BA)=Sof(H3BA)=Sof(H3BB)=
 Sof(C4B)=Sof(H4BA)=Sof(H4BB)=Sof(C5B)=Sof(H5BA)=Sof(H5BB)=Sof(C6B)=Sof(H6BA)=
 Sof(H6BB)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C32(H32), C40(H40), C56(H56), C67(H67), C1B(H1BA), C2B(H2BA), C1C(H1CA),
 C2C(H2C)
6.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), C25(H25A,
 H25B), C27(H27A,H27B), C39(H39A,H39B), C85(H85A,H85B), C2(H2A,H2B), C8(H8A,
 H8B), C9(H9A,H9B), C2A(H2AA,H2AB), C8A(H8AA,H8AB), C9A(H9AA,H9AB), C3B(H3BA,
 H3BB), C3B(H3BE,H3BF), C4B(H4BA,H4BB), C5B(H5BA,H5BB), C6B(H6BA,H6BB),
 C4C(H4CA,H4CB), C6C(H6CA,H6CB), C5C(H5CA,H5CB)
6.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C42(H42), C51(H51), C73(H73)
6.d Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C19(H19A,H19B,H19C), C52(H52A,H52B,H52C), C53(H53A,H53B,
 H53C), C54(H54A,H54B,H54C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C), C70(H70A,
 H70B,H70C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C),
 C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C91(H91A,H91B,H91C), C92(H92A,H92B,
 H92C), C93(H93A,H93B,H93C), C99(H99A,H99B,H99C), C100(H10E,H10F,H10G),
 C101(H10H,H10I,H10J), C103(H10K,H10L,H10M), C104(H10N,H10O,H10P), C110(H11C,
 H11D,H11E), C111(H11F,H11G,H11H), C112(H11I,H11J,H11K), C114(H11L,H11M,H11N),
 C115(H11O,H11P,H11Q), C116(H11R,H11S,H11T), C120(H12C,H12D,H12E), C121(H12F,
 H12G,H12H), C123(H12I,H12J,H12K), C124(H12L,H12M,H12N), C125(H12O,H12P,H12Q),
 C127(H12R,H12S,H12T), C128(H12U,H12V,H12W), C1(H1A,H1B,H1C), C7(H7A,H7B,H7C),
 C1A(H1AA,H1AB,H1AC), C7A(H7AA,H7AB,H7AC), C7B(H7BA,H7BB,H7BC)
6.e Idealised tetrahedral OH refined as rotating group:
 O1(H1), O2(H2), O3(H3), O4(H4)
;
_shelx_res_checksum              43394
_shelx_hkl_checksum              60369
_shelx_shelxl_version_number     2014/7
_olex2_submission_original_sample_id d160815_35_6_100K
_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 1.474
_oxdiff_exptl_absorpt_empirical_full_min 0.793