Separation of 2-Chloropyridine/3-Chloropyridine by Nonporous Adaptive Crystals of Pillararenes with Different Substituents and Cavity Sizes.
Sheng, Xinru; Li, Errui; Zhou, Yujuan; Zhao, Run; Zhu, Weijie; Huang, Feihe; Journal of the American Chemical Society 142 (2020) 6360–6364; doi:10.1021/jacs.0c01274

data_4134444
_publ_section_title
;
 Separation of 2-Chloropyridine/3-Chloropyridine by Nonporous Adaptive
 Crystals of Pillararenes with Different Substituents and Cavity Sizes.
;
_journal_issue                   13
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              6360
_journal_page_last               6364
_journal_paper_doi               10.1021/jacs.0c01274
_journal_volume                  142
_journal_year                    2020
_chemical_formula_moiety         '4(C66 H72 Br12 O12), 7(C5 H4 Cl N), O'
_chemical_formula_sum            'C299 H316 Br48 Cl7 N7 O49'
_chemical_formula_weight         8875.40
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2019-03-17
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                80.160(3)
_cell_angle_beta                 90.0010(10)
_cell_angle_gamma                90.0010(10)
_cell_formula_units_Z            1
_cell_length_a                   13.8470(10)
_cell_length_b                   23.250(2)
_cell_length_c                   25.631(2)
_cell_measurement_reflns_used    9874
_cell_measurement_temperature    170
_cell_measurement_theta_max      26.34
_cell_measurement_theta_min      2.34
_cell_volume                     8130.3(11)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      170.0
_diffrn_measured_fraction_theta_full 0.958
_diffrn_measured_fraction_theta_max 0.936
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0439
_diffrn_reflns_av_unetI/netI     0.0782
_diffrn_reflns_Laue_measured_fraction_full 0.958
_diffrn_reflns_Laue_measured_fraction_max 0.936
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            60712
_diffrn_reflns_point_group_measured_fraction_full 0.958
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.505
_diffrn_reflns_theta_min         2.183
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.028
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5983
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0812 before and 0.0445 after correction. The Ratio of minimum to maximum transmission is 0.8027. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.813
_exptl_crystal_description       prism
_exptl_crystal_F_000             4350
_exptl_crystal_size_max          0.324
_exptl_crystal_size_mid          0.195
_exptl_crystal_size_min          0.144
_refine_diff_density_max         4.017
_refine_diff_density_min         -2.682
_refine_diff_density_rms         0.211
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1921
_refine_ls_number_reflns         31575
_refine_ls_number_restraints     237
_refine_ls_restrained_S_all      1.104
_refine_ls_R_factor_all          0.1437
_refine_ls_R_factor_gt           0.0974
_refine_ls_shift/su_max          0.067
_refine_ls_shift/su_mean         0.004
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1947P)^2^+16.3075P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2912
_refine_ls_wR_factor_ref         0.3231
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19051
_reflns_number_total             31575
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c01274_si_004.cif
_cod_data_source_block           190107_sxr_brp6_3cl_0ma
_cod_depositor_comments
'Adding full bibliography for 4134442--4134445.cif.'
_cod_original_cell_volume        8130.3(12)
_cod_database_code               4134444
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.477
_shelx_estimated_absorpt_t_min   0.245
_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
2. Restrained distances
 C156-Br1B
 1.8 with sigma of 0.02
 C1A-Br24
 1.8 with sigma of 0.02
 H97B-H140
 2.2 with sigma of 0.01
 H87B-H140
 2.2 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C151) \\sim Ueq, Uanis(Cl4) \\sim Ueq, Uanis(C153) \\sim Ueq, Uanis(C154)
\\sim Ueq, Uanis(C152) \\sim Ueq, Uanis(C155) \\sim Ueq, Uanis(N4) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C134) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Br1B) \\sim Ueq, Uanis(Br1C) \\sim Ueq, Uanis(Br23) \\sim Ueq,
Uanis(Br21) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C151) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O25) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 Cl4, N4, C151, C152, C153, C154, C155
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Br1B, Br24, O19, C1A, C1B, C142, C156
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O14, C108, C134
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Br1B, Br1C, Br23, Br24, C143, Br21, C147
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C122, C124, N2, C138, C141, C146
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N3, C129, C136, C140, C145, C148
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Br)=Sof(H12G)=Sof(H12H)=1-FVAR(1)
 Sof(Br22)=Sof(H12E)=Sof(H12F)=FVAR(1)
 Sof(Br1A)=Sof(H11I)=Sof(H11J)=1-FVAR(2)
 Sof(Br19)=Sof(H11G)=Sof(H11H)=FVAR(2)
 Sof(Br1C)=Sof(H14E)=Sof(H14F)=1-FVAR(3)
 Sof(Br23)=Sof(H14C)=Sof(H14D)=FVAR(3)
 Sof(Br1D)=Sof(H11C)=Sof(H11D)=1-FVAR(4)
 Sof(Br20)=Sof(H11A)=Sof(H11B)=FVAR(4)
 Sof(Br1E)=Sof(H11Q)=Sof(H11R)=1-FVAR(5)
 Sof(Br17)=Sof(H11O)=Sof(H11P)=FVAR(5)
 Sof(Br1F)=Sof(H14I)=Sof(H14J)=1-FVAR(6)
 Sof(Br21)=Sof(H14G)=Sof(H14H)=FVAR(6)
 Fixed Sof: Br1B(0.5) Br24(0.5) C1A(0.5) H1AA(0.5) H1AB(0.5) C1B(0.5)
 H1BA(0.5) H1BB(0.5) C142(0.5) H14A(0.5) H14B(0.5) C156(0.5) H15A(0.5)
 H15B(0.5) Cl4(0.5) C153(0.5) H153(0.5) C154(0.5) C155(0.5) H155(0.5) N4(0.5)
 C151(0.5) H151(0.5) C152(0.5) H152(0.5) O25(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C1A(H1AA,H1AB), C1B(H1BA,H1BB), C34(H34A,H34B), C37(H37A,H37B), C72(H72A,
 H72B), C75(H75A,H75B), C77(H77A,H77B), C81(H81A,H81B), C84(H84A,H84B),
 C86(H86A,H86B), C88(H88A,H88B), C91(H91A,H91B), C93(H93A,H93B), C95(H95A,H95B),
  C96(H96A,H96B), C100(H10A,H10B), C103(H10C,H10D), C104(H10E,H10F), C109(H10G,
 H10H), C111(H11A,H11B), C111(H11C,H11D), C114(H11E,H11F), C115(H11G,H11H),
 C115(H11I,H11J), C118(H11K,H11L), C119(H11M,H11N), C120(H12A,H12B), C123(H12C,
 H12D), C126(H12E,H12F), C126(H12G,H12H), C127(H12I,H12J), C130(H13A,H13B),
 C142(H14A,H14B), C143(H14C,H14D), C143(H14E,H14F), C156(H15A,H15B), C7(H7A,
 H7B), C36(H36A,H36B), C44(H44A,H44B), C46(H46A,H46B), C52(H52A,H52B), C79(H79A,
 H79B), C85(H85A,H85B), C87(H87A,H87B), C89(H89A,H89B), C90(H90A,H90B),
 C92(H92A,H92B), C94(H94A,H94B), C97(H97A,H97B), C98(H98A,H98B), C99(H99A,H99B),
  C101(H10I,H10J), C102(H10K,H10L), C105(H10M,H10N), C106(H10O,H10P), C107(H10Q,
 H10R), C108(H10S,H10T), C110(H11O,H11P), C110(H11Q,H11R), C112(H11S,H11T),
 C113(H11U,H11V), C116(H11W,H11X), C117(H11Y,H), C125(H12K,H12L), C134(H13C,
 H13D), C137(H13E,H13F), C147(H14G,H14H), C147(H14I,H14J)
6.b Aromatic/amide H refined with riding coordinates:
 C33(H33), C40(H40), C41(H41), C45(H45), C47(H47), C57(H57), C59(H59),
 C62(H62), C70(H70), C71(H71), C78(H78), C80(H80), C5(H5), C17(H17), C18(H18),
 C22(H22), C30(H30), C42(H42), C43(H43), C51(H51), C64(H64), C65(H65), C68(H68),
  C83(H83), C136(H136), C148(H148), C140(H140), C145(H145), C122(H122),
 C141(H141), C146(H146), C138(H138), C133(H133), C132(H132), C139(H139),
 C144(H144), C153(H153), C155(H155), C151(H151), C152(H152)
6.c Fitted hexagon refined as free rotating group:
 C136(N3,C148,C140,C145,C129), C122(N2,C141,C124,C146,C138), C133(C132,C139,N1,
 C144,C131), C153(C154,C155,N4,C151,C152)
;
_olex2_submission_special_instructions 'No special instructions were received'