A Route to Enantiopure ( O-Methyl)<sub>6</sub>-2,6-Helic[6]arenes: Synthesis of Hexabromo-Substituted 2,6-Helic[6]arene Derivatives and Their Suzuki-Miyaura Coupling Reactions.
Wang, Jia-Qi; Li, Jing; Zhang, Geng-Wu; Chen, Chuan-Feng; The Journal of organic chemistry 83 (2018) 11532–11540; doi:10.1021/acs.joc.8b01437

data_4035189
_publ_section_title
;
 A Route to Enantiopure ( O-Methyl)<sub>6</sub>-2,6-Helic[6]arenes:
 Synthesis of Hexabromo-Substituted 2,6-Helic[6]arene Derivatives and
 Their Suzuki-Miyaura Coupling Reactions.
;
_journal_issue                   19
_journal_name_full               'The Journal of organic chemistry'
_journal_page_first              11532
_journal_page_last               11540
_journal_paper_doi               10.1021/acs.joc.8b01437
_journal_volume                  83
_journal_year                    2018
_chemical_formula_moiety         'C69 H54 O6, 0.22(C1 H1 Cl3), 4.28(C6 H12)'
_chemical_formula_sum            'C94.88 H105.54 Cl0.67 O6'
_chemical_formula_weight         1365.64
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-11-27
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
????
;
_cell_angle_alpha                73.987(4)
_cell_angle_beta                 89.554(5)
_cell_angle_gamma                87.329(5)
_cell_formula_units_Z            2
_cell_length_a                   12.555(2)
_cell_length_b                   17.818(3)
_cell_length_c                   17.840(3)
_cell_measurement_reflns_used    9061
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      27.4458
_cell_measurement_theta_min      1.1875
_cell_volume                     3831.8(11)
_computing_cell_refinement       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_collection       'CrystalClear (Rigaku Inc., 2007)'
_computing_data_reduction        'CrystalClear (Rigaku Inc., 2007)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'CIFTAB (Sheldrick, 2013)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      173.15
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'MM007-HF CCD(Saturn 724+)'
_diffrn_measurement_method       '\w scans at fixed \c = 45\%'
_diffrn_radiation_monochromator  Confocal
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0620
_diffrn_reflns_av_unetI/netI     0.0572
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            46646
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.199
_diffrn_reflns_theta_max         25.199
_diffrn_reflns_theta_min         1.431
_diffrn_source                   'Rotating Anode'
_exptl_absorpt_coefficient_mu    0.094
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88549
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'CrystalClear (Rigaku Inc., 2007)'
_exptl_crystal_colour            colorless
_exptl_crystal_density_diffrn    1.184
_exptl_crystal_description       needle
_exptl_crystal_F_000             1468
_exptl_crystal_size_max          0.204
_exptl_crystal_size_mid          0.098
_exptl_crystal_size_min          0.024
_refine_diff_density_max         1.221
_refine_diff_density_min         -0.538
_refine_diff_density_rms         0.084
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.904
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     958
_refine_ls_number_reflns         13738
_refine_ls_number_restraints     346
_refine_ls_restrained_S_all      1.966
_refine_ls_R_factor_all          0.1557
_refine_ls_R_factor_gt           0.1305
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3075
_refine_ls_wR_factor_ref         0.3188
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10759
_reflns_number_total             13738
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            jo8b01437_si_002.cif
_cod_data_source_block           mx6528
_cod_original_cell_volume        3831.9(11)
_cod_database_code               4035189
_shelx_shelxl_version_number     2016/6
_shelx_estimated_absorpt_t_max   0.998
_shelx_estimated_absorpt_t_min   0.981
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C77
 1.76 with sigma of 0.01
 C97-C96 = C98-C97 = C82-C81 = C81-C80 = C80-C79 = C79-C78 = C83-C78 = C83-C82
 = C93-C92 = C94-C93 = C92-C91 = C91-C90 = C95-C94 = C95-C90 = C74-C73 = C75-
 C74 = C76-C75 = C76-C71 = C72-C71 = C73-C72 = C85-C84 = C89-C84 = C86-C85 =
 C89-C88 = C88-C87 = C87-C86
 1.54 with sigma of 0.01
 C84-C88
 2.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C91 \\sim C90 \\sim C95 \\sim C92 \\sim C94 \\sim C93 \\sim C82 \\sim C78 \\sim
C79 \\sim C83 \\sim C80 \\sim C81 \\sim C96 \\sim C97 \\sim C98 \\sim C75 \\sim
C71 \\sim C72 \\sim C76 \\sim C73 \\sim C74 \\sim C84 \\sim C85 \\sim C89 \\sim
C86 \\sim C88 \\sim C87: within 1.7A with sigma of 0.02 and sigma for terminal
atoms of 0.04
Uanis(C84) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(C89) \\sim Ueq, Uanis(C86)
\\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C73) \\sim Ueq,
Uanis(C71) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C76) \\sim Ueq, Uanis(C75)
\\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C90) \\sim Ueq, Uanis(C91) \\sim Ueq,
Uanis(C95) \\sim Ueq, Uanis(C92) \\sim Ueq, Uanis(C94) \\sim Ueq, Uanis(C93)
\\sim Ueq, Uanis(C80) \\sim Ueq, Uanis(C78) \\sim Ueq, Uanis(C79) \\sim Ueq,
Uanis(C83) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C96)
\\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C98) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Others
 Sof(C77)=Sof(H77)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=1-FVAR(1)
 Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73A)=
 Sof(H73B)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C76)=
 Sof(H76A)=Sof(H76B)=FVAR(1)
 Fixed Y: C98(0.06231)
5.a Riding coordinates:
 C86(H86A,H86B)
5.b Ternary CH refined with riding coordinates:
 C5(H5), C12(H12), C31(H31), C38(H38), C54(H54), C57(H57), C77(H77)
5.c Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C47(H47A,H47B), C70(H70A,H70B), C90(H90A,H90B), C91(H91A,
 H91B), C92(H92A,H92B), C93(H93A,H93B), C94(H94A,H94B), C95(H95A,H95B),
 C78(H78A,H78B), C79(H79A,H79B), C80(H80A,H80B), C81(H81A,H81B), C82(H82A,H82B),
  C83(H83A,H83B), C84(H84A,H84B), C85(H85A,H85B), C87(H87A,H87B), C88(H88A,
 H88B), C89(H89A,H89B), C71(H71A,H71B), C72(H72A,H72B), C73(H73A,H73B),
 C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B), C97(H97A,H97B), C96(H96A,H96B),
  C98(H98A,H98B)
5.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C9(H9), C10(H10), C14(H14), C16(H16), C19(H19),
 C26(H26), C29(H29), C33(H33), C36(H36), C40(H40), C41(H41), C42(H42), C43(H43),
  C50(H50), C53(H53), C60(H60), C61(H61), C62(H62), C63(H63), C64(H64), C67(H67)
5.e Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C45(H45A,H45B,H45C), C46(H46A,H46B,
 H46C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C)
;
_shelx_res_checksum              76684
_shelx_hkl_checksum              58248
_olex2_submission_special_instructions 'No special instructions were received'