Vapochromic separation of toluene and pyridine azeotropes using adaptive macrocycle co-crystals.
Li, Bin; Wang, Yun; Wang, Yuan; Liu, Yue; Wang, Lu; Zhang, Zhi-Yuan; Li, Chunju; Chemical communications (Cambridge, England) 60 (2024) 6889–6892; doi:10.1039/d4cc01246a

data_7133189
_publ_section_title
;
 Vapochromic separation of toluene and pyridine azeotropes using adaptive
 macrocycle co-crystals.
;
_journal_issue                   54
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              6889
_journal_page_last               6892
_journal_paper_doi               10.1039/d4cc01246a
_journal_volume                  60
_journal_year                    2024
_chemical_formula_moiety         'C55 H70 O10, 2(C10 H10 N2), 2(C9 H10 N O2)'
_chemical_formula_sum            'C93 H110 N6 O14'
_chemical_formula_weight         1535.86
_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     iterative
_audit_creation_date             2024-04-09
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-14 deposited with the CCDC.	2024-05-30 downloaded from the CCDC.
;
_cell_angle_alpha                94.272(2)
_cell_angle_beta                 92.465(2)
_cell_angle_gamma                106.740(2)
_cell_formula_units_Z            2
_cell_length_a                   12.0800(5)
_cell_length_b                   12.4509(5)
_cell_length_c                   29.1324(11)
_cell_measurement_reflns_used    9860
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      50.50
_cell_measurement_theta_min      2.65
_cell_volume                     4174.8(3)
_computing_data_collection       'Bruker APEX-II CCD diffractrometer'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      193.00
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0482
_diffrn_reflns_av_unetI/netI     0.0424
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            54799
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        52.978
_diffrn_reflns_theta_max         52.978
_diffrn_reflns_theta_min         3.238
_exptl_absorpt_coefficient_mu    0.419
_exptl_absorpt_correction_type   mult-scan
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             1644
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.11
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.768
_refine_diff_density_min         -0.751
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.179
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1124
_refine_ls_number_reflns         14532
_refine_ls_number_restraints     1416
_refine_ls_restrained_S_all      1.223
_refine_ls_R_factor_all          0.1358
_refine_ls_R_factor_gt           0.0871
_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^)+(0.1457P)^2^+0.3640P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2471
_refine_ls_wR_factor_ref         0.2856
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8128
_reflns_number_total             14532
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01246a2.cif
_cod_data_source_block           20200703li_znz1682_1_0m_a_sq_sq
_cod_depositor_comments
'Adding full bibliography for 7133188--7133189.cif.'
_cod_database_code               7133189
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.967
_shelx_estimated_absorpt_t_min   0.951
_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
2. Restrained distances
 H31B-H36C_$1
 2.1 with sigma of 0.01
 C41A-C40A
 1.5 with sigma of 0.001
 C83A-C84A = C86A-C87A
 1.38 with sigma of 0.02
 C84A-C85A = C85A-C86A
 1.37 with sigma of 0.02
 C70-C71
 1.5 with sigma of 0.01
 N5-C83 = N5-C87
 1.34 with sigma of 0.02
 C84-C85 = C85-C86 = C86-C87
 1.39 with sigma of 0.02
 C83-C84
 1.4 with sigma of 0.02
 N6-C92 = N6-C88
 1.34 with sigma of 0.02
 C91-C90 = C90-C89 = C89-C88
 1.39 with sigma of 0.02
 C92-C91
 1.4 with sigma of 0.02
 N5A-C83A = N5A-C87A
 1.33 with sigma of 0.02
 N6A-C92A = N6A-C88A
 1.33 with sigma of 0.02
 C92A-C91A = C89A-C88A
 1.38 with sigma of 0.02
 C91A-C90A = C90A-C89A
 1.37 with sigma of 0.02
 N5A-C84A
 2.4 with sigma of 0.04
 C84A-C86A
 2.35 with sigma of 0.04
 C41A-O8
 2.5 with sigma of 0.01
 N5-C84 = N5-C86 = C83-C85
 2.4 with sigma of 0.04
 C84-C86 = C85-C87
 2.39 with sigma of 0.04
 N6-C91 = N6-C89 = C92-C90
 2.4 with sigma of 0.04
 C91-C89 = C90-C88
 2.39 with sigma of 0.04
 N5A-C86A
 2.39 with sigma of 0.04
 C83A-C85A
 2.36 with sigma of 0.04
 C85A-C87A
 2.37 with sigma of 0.04
 N6A-C91A
 2.4 with sigma of 0.04
 N6A-C89A
 2.39 with sigma of 0.04
 C92A-C90A
 2.36 with sigma of 0.04
 C91A-C89A
 2.35 with sigma of 0.04
 C90A-C88A
 2.37 with sigma of 0.04
 C83A-C84A \\sim C84A-C85A \\sim C85A-C86A \\sim C86A-C87A
 with sigma of 0.02
 N5A-C86A \\sim N5A-C84A
 with sigma of 0.04
 C85A-C87A \\sim C85A-C83A \\sim C86A-C84A \\sim C87A-C83A
 with sigma of 0.04
 N5-C83 \\sim N5-C87
 with sigma of 0.02
 C83-C84 \\sim C84-C85 \\sim C85-C86 \\sim C86-C87
 with sigma of 0.02
 N5-C84 \\sim N5-C86
 with sigma of 0.04
 C83-C87 \\sim C83-C85 \\sim C84-C86
 with sigma of 0.04
 N6-C92 \\sim N6-C88
 with sigma of 0.02
 C92-C91 \\sim C91-C90 \\sim C90-C89 \\sim C89-C88
 with sigma of 0.02
 N6-C91 \\sim N6-C89
 with sigma of 0.04
 C92-C88 \\sim C92-C90 \\sim C91-C89
 with sigma of 0.04
 N5A-C83A \\sim N5A-C87A
 with sigma of 0.02
 N6A-C92A \\sim N6A-C88A
 with sigma of 0.02
 C92A-C91A \\sim C91A-C90A \\sim C90A-C89A \\sim C89A-C88A
 with sigma of 0.02
 N6A-C89A \\sim N6A-C91A
 with sigma of 0.04
 C90A-C88A \\sim C90A-C92A \\sim C89A-C91A \\sim C88A-C92A
 with sigma of 0.04
 C40-C41 \\sim C40A-C41A
 with sigma of 0.02
 C93-C69 \\sim C70-C69 \\sim C71-C70 \\sim C95-C93 \\sim C96-C71 \\sim C95-C72
 with sigma of 0.02
3. Restrained planarity
 N5A, C83A, C84A, C85A, C86A, C87A
 with sigma of 0.1
 N5, C83, C84, C85, C86, C87
 with sigma of 0.1
 N6, C88, C89, C90, C91, C92
 with sigma of 0.1
 N6A, C88A, C89A, C90A, C91A, C92A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
N5A \\sim C83A \\sim C84A \\sim C85A \\sim C86A \\sim C87A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
N5 \\sim C83 \\sim C84 \\sim C85 \\sim C86 \\sim C87: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
N6 \\sim C88 \\sim C89 \\sim C90 \\sim C91 \\sim C92: within 2A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 2A
N6A \\sim C88A \\sim C89A \\sim C90A \\sim C91A \\sim C92A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 N5A, C83A, C84A, C85A, C86A, C87A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N5, C83, C84, C85, C86, C87
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N6, C88, C89, C90, C91, C92
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N6A, C88A, C89A, C90A, C91A, C92A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(N6A)=Sof(C40)=Sof(H40C)=Sof(H40D)=Sof(C41)=Sof(H41D)=Sof(H41E)=Sof(H41F)=
 Sof(C88A)=Sof(H88A)=Sof(C89A)=Sof(H89A)=Sof(C90A)=Sof(H90A)=Sof(C91A)=
 Sof(H91A)=Sof(C92A)=Sof(H92A)=Sof(H69C)=Sof(H69D)=Sof(C72)=Sof(H72A)=Sof(H72B)=
 Sof(H72C)=Sof(N5A)=Sof(C83A)=Sof(H83A)=Sof(C84A)=Sof(H84A)=Sof(C85A)=Sof(H85A)=
 Sof(C86A)=Sof(H86A)=Sof(C87A)=Sof(H87A)=Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(C93)=
 Sof(H93A)=Sof(H93B)=Sof(O15)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(C8A)=Sof(H8AA)=
 Sof(H8AB)=Sof(H8AC)=1-FVAR(1)
 Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(C8)=Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(O8)=
 Sof(C40A)=Sof(H40A)=Sof(H40B)=Sof(C41A)=Sof(H41A)=Sof(H41B)=Sof(H41C)=
 Sof(H69A)=Sof(H69B)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(C71)=Sof(H71A)=Sof(H71B)=
 Sof(N5)=Sof(C83)=Sof(H83)=Sof(C84)=Sof(H84)=Sof(C85)=Sof(H85)=Sof(C86)=
 Sof(H86)=Sof(C87)=Sof(H87)=Sof(N6)=Sof(C88)=Sof(H88)=Sof(C89)=Sof(H89)=
 Sof(C90)=Sof(H90)=Sof(C91)=Sof(H91)=Sof(C92)=Sof(H92)=Sof(C96)=Sof(H96A)=
 Sof(H96B)=Sof(H96C)=FVAR(1)
7.a Fixed occupancy and ADP/Uiso:
 C22, C30, C31, C35, C40A, N1, C55, C56, C58, C59, C60, C69, C70, C71, C72
7.b Secondary CH2 refined with riding coordinates:
 C2(H2A,H2B), C7(H7A,H7B), C11(H11A,H11B), C14(H14A,H14B), C19(H19A,H19B),
 C22(H22A,H22B), C25(H25A,H25B), C30(H30A,H30B), C32(H32A,H32B), C35(H35A,H35B),
  C43(H43A,H43B), C46(H46A,H46B), C51(H51A,H51B), C54(H54A,H54B), C40A(H40A,
 H40B), C40(H40C,H40D), C60(H60A,H60B), C61(H61A,H61B), C62(H62A,H62B),
 C69(H69A,H69B), C69(H69C,H69D), C70(H70A,H70B), C71(H71A,H71B), C95(H95A,H95B),
  C93(H93A,H93B), C7A(H7AA,H7AB)
7.c Aromatic/amide H refined with riding coordinates:
 C4(H4), C9(H9), C16(H16), C21(H21), C27(H27), C37(H37), C42(H42), C48(H48),
 C53(H53), C94(H94), C88A(H88A), C89A(H89A), C90A(H90A), C91A(H91A), C92A(H92A),
  C58(H58), C66(H66), C83(H83), C84(H84), C85(H85), C86(H86), C87(H87),
 C83A(H83A), C84A(H84A), C85A(H85A), C86A(H86A), C87A(H87A), C88(H88), C89(H89),
  C90(H90), C91(H91), C92(H92), C78(H78), C79(H79), C80(H80), C81(H81),
 C82(H82), C73(H73), C74(H74), C75(H75), C76(H76), C77(H77)
7.d Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C8(H8A,H8B,H8C), C15(H15A,H15B,H15C), C20(H20A,H20B,H20C),
 C26(H26A,H26B,H26C), C31(H31A,H31B,H31C), C36(H36A,H36B,H36C), C47(H47A,H47B,
 H47C), C52(H52A,H52B,H52C), C41A(H41A,H41B,H41C), C41(H41D,H41E,H41F),
 C63(H63A,H63B,H63C), C72(H72A,H72B,H72C), C96(H96A,H96B,H96C), C8A(H8AA,H8AB,
 H8AC)
;
_shelx_res_checksum              36305
_shelx_hkl_checksum              26462
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'