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_7133188
_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, C18 H20 N2 O4, 2(C4 H8 O2), 7.2[H2O]'
_chemical_formula_sum            'C81 H106 N2 O18'
_chemical_formula_weight         1395.67
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-03-16
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-03-18 deposited with the CCDC.	2024-05-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.013(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   12.3241(18)
_cell_length_b                   33.684(6)
_cell_length_c                   20.229(3)
_cell_measurement_reflns_used    9963
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      27.480
_cell_measurement_theta_min      2.360
_cell_volume                     8351(2)
_computing_cell_refinement       'SAINT V8.38A (Bruker, 2018)'
_computing_data_reduction        'SAINT V8.38A (Bruker, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      100.00(10)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker D8-Venture'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0911
_diffrn_reflns_av_unetI/netI     0.0713
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       43
_diffrn_reflns_limit_k_min       -43
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            105718
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.511
_diffrn_reflns_theta_min         1.949
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.078
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.7052
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1331 before and 0.0740 after correction. The Ratio of minimum to maximum transmission is 0.9458. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.110
_exptl_crystal_description       block
_exptl_crystal_F_000             3000
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.305
_refine_diff_density_min         -0.339
_refine_diff_density_rms         0.050
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1052
_refine_ls_number_reflns         19146
_refine_ls_number_restraints     372
_refine_ls_restrained_S_all      1.020
_refine_ls_R_factor_all          0.1246
_refine_ls_R_factor_gt           0.0616
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0711P)^2^+1.8691P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1419
_refine_ls_wR_factor_ref         0.1750
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10413
_reflns_number_total             19146
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc01246a2.cif
_cod_data_source_block           a_a
_cod_depositor_comments
'Adding full bibliography for 7133188--7133189.cif.'
_cod_database_code               7133188
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.993
_shelx_estimated_absorpt_t_min   0.989
_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. Uiso/Uaniso restraints and constraints
C74 \\sim C75 \\sim C76 \\sim C77 \\sim O15 \\sim O18 \\sim C74A \\sim C75A
\\sim C76A \\sim C77A \\sim O15A \\sim O18A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C72 \\sim C73 \\sim C78 \\sim C79 \\sim O16 \\sim O17 \\sim C72A \\sim C73A
\\sim C78A \\sim C79A \\sim O16A \\sim O17A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
3. Same fragment restrains
{C72A, C73A, C78A, C79A, O16A, O17A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C72, C73, C78, C79, O16, O17}
{C74A, C75A, C76A, C77A, O15A, O18A} sigma for 1-2: 0.01, 1-3: 0.04
as in
{C74, C75, C76, C77, O15, O18}
4. Others
 Sof(H65C)=Sof(H65D)=Sof(H66C)=Sof(H66D)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(C83)=
 Sof(H83A)=Sof(H83B)=Sof(H83C)=1-FVAR(1)
 Sof(H65A)=Sof(H65B)=Sof(H66A)=Sof(H66B)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(C82)=
 Sof(H82A)=Sof(H82B)=Sof(H82C)=FVAR(1)
 Sof(C74A)=Sof(H74C)=Sof(H74D)=Sof(C75A)=Sof(H75C)=Sof(H75D)=Sof(C76A)=
 Sof(H76C)=Sof(H76D)=Sof(C77A)=Sof(H77C)=Sof(H77D)=Sof(O15A)=Sof(O18A)=1-FVAR(2)
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(C76)=Sof(H76A)=
 Sof(H76B)=Sof(C77)=Sof(H77A)=Sof(H77B)=Sof(O15)=Sof(O18)=FVAR(2)
 Sof(C72A)=Sof(H72C)=Sof(H72D)=Sof(C73A)=Sof(H73C)=Sof(H73D)=Sof(C78A)=
 Sof(H78C)=Sof(H78D)=Sof(C79A)=Sof(H79C)=Sof(H79D)=Sof(O16A)=Sof(O17A)=1-FVAR(3)
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(C78)=Sof(H78A)=
 Sof(H78B)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(O16)=Sof(O17)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C13(H13A,H13B), C23(H23A,H23B), C25(H25A,H25B), C29(H29A,H29B), C32(H32A,
 H32B), C36(H36A,H36B), C46(H46A,H46B), C48(H48A,H48B), C50(H50A,H50B),
 C52(H52A,H52B), C53(H53A,H53B), C56(H56A,H56B), C57(H57A,H57B), C59(H59A,H59B),
  C62(H62A,H62B), C45(H45A,H45B), C55(H55A,H55B), C58(H58A,H58B), C65(H65A,
 H65B), C65(H65C,H65D), C66(H66A,H66B), C66(H66C,H66D), C80(H80A,H80B),
 C81(H81A,H81B), C72(H72A,H72B), C73(H73A,H73B), C78(H78A,H78B), C79(H79A,H79B),
  C74(H74A,H74B), C75(H75A,H75B), C76(H76A,H76B), C77(H77A,H77B), C72A(H72C,
 H72D), C73A(H73C,H73D), C78A(H78C,H78D), C79A(H79C,H79D), C74A(H74C,H74D),
 C75A(H75C,H75D), C76A(H76C,H76D), C77A(H77C,H77D)
5.b Aromatic/amide H refined with riding coordinates:
 C7(H7), C11(H11), C14(H14), C19(H19), C20(H20), C26(H26), C30(H30), C31(H31),
 C34(H34), C39(H39), C43(H43), C44(H44)
5.c Idealised Me refined as rotating group:
 C51(H51A,H51B,H51C), C54(H54A,H54B,H54C), C60(H60A,H60B,H60C), C61(H61A,H61B,
 H61C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C68(H68A,H68B,H68C), C69(H69A,
 H69B,H69C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C67(H67A,H67B,H67C),
 C82(H82A,H82B,H82C), C83(H83A,H83B,H83C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 288 electrons were 
found in a volume of 1172\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
7.2[H2O] per Asymmetric Unit 
which account for 288 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              78199
_shelx_hkl_checksum              25029
_shelx_fab_checksum              69681
_olex2_submission_special_instructions 'No special instructions were received'