Efficient Separation of Monobromotoluene Isomers by Nonporous Adaptive Perbromoethylated Pillar[5]arene Crystals
Zhao, Bohan; Wang, Jianwei; Shao, Li; Wu, Yitao; Li, Ming; Hua, Bin; Huang, Feihe; Chemical Communications  (2023) –; doi:10.1039/D3CC03676F

data_7131966
_publ_section_title
;
 Efficient Separation of Monobromotoluene Isomers by Nonporous Adaptive
 Perbromoethylated Pillar[5]arene Crystals
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D3CC03676F
_journal_year                    2023
_chemical_formula_moiety         'C65.944 H71.889 Br11.944 O12, 2(C7 H7 Br)'
_chemical_formula_sum            'C80 H86 Br14 O12'
_chemical_formula_weight         2358.22
_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_block_doi                 10.5517/ccdc.csd.cc2fxq7b
_audit_creation_date             2023-05-05
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-05-10 deposited with the CCDC.	2023-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.1300(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.7704(16)
_cell_length_b                   13.7621(10)
_cell_length_c                   23.8060(17)
_cell_measurement_reflns_used    9947
_cell_measurement_temperature    170.00
_cell_measurement_theta_max      26.336
_cell_measurement_theta_min      2.329
_cell_volume                     8442.9(10)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170.00
_diffrn_measured_fraction_theta_full 0.985
_diffrn_measured_fraction_theta_max 0.982
_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  0.1427
_diffrn_reflns_av_unetI/netI     0.1004
_diffrn_reflns_Laue_measured_fraction_full 0.985
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       33
_diffrn_reflns_limit_h_min       -33
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            128129
_diffrn_reflns_point_group_measured_fraction_full 0.985
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.565
_diffrn_reflns_theta_min         1.886
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    6.697
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5867
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1117 before and 0.0921 after correction.
The Ratio of minimum to maximum transmission is 0.7869.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.855
_exptl_crystal_description       plate
_exptl_crystal_F_000             4608
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.06
_refine_diff_density_max         3.013
_refine_diff_density_min         -1.523
_refine_diff_density_rms         0.199
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1152
_refine_ls_number_reflns         19153
_refine_ls_number_restraints     1066
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.1579
_refine_ls_R_factor_gt           0.1014
_refine_ls_shift/su_max          0.014
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1395P)^2^+79.8265P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2582
_refine_ls_wR_factor_ref         0.2943
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10840
_reflns_number_total             19153
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cc03676f2.cif
_cod_data_source_block           230414_zbh_sc_7
_cod_database_code               7131966
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.689
_shelx_estimated_absorpt_t_min   0.308
_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
 C1A-C1B
 1.51 with sigma of 0.02
 C1C-C1D = C1E-C1F = C1F-C1G
 1.38 with sigma of 0.02
 C1B-C1C = C1B-C1G = C1D-C1E
 1.39 with sigma of 0.02
 C1H-C1I
 1.51 with sigma of 0.02
 C1I-C1J = C1I-C1N = C1K-C1L
 1.39 with sigma of 0.02
 C1J-C1K = C1L-C1M = C1M-C1N
 1.38 with sigma of 0.02
 Br14-C1N = Br13-C1C
 1.8 with sigma of 0.01
 Br16-C52
 2.7 with sigma of 0.02
 C1B-C1F
 2.41 with sigma of 0.04
 C1A-C1C = C1A-C1G
 2.52 with sigma of 0.04
 C1D-C1F = C1E-C1G
 2.4 with sigma of 0.04
 C1B-C1D
 2.42 with sigma of 0.04
 C1C-C1E
 2.39 with sigma of 0.04
 C1H-C1J = C1H-C1N
 2.52 with sigma of 0.04
 C1I-C1K
 2.42 with sigma of 0.04
 C1I-C1M
 2.41 with sigma of 0.04
 C1J-C1L
 2.39 with sigma of 0.04
 C1K-C1M = C1L-C1N
 2.4 with sigma of 0.04
 C1B-C1C \\sim C1C-C1D \\sim C1D-C1E \\sim C1E-C1F \\sim C1F-C1G \\sim C1G-C1B
 with sigma of 0.02
 C1B-C1F \\sim C1B-C1D \\sim C1G-C1E \\sim C1C-C1G \\sim C1D-C1F \\sim C1C-C1E
 with sigma of 0.04
 C1A-C1G \\sim C1A-C1C
 with sigma of 0.04
 C1E-C1F \\sim C1S-C1R
 with sigma of 0.02
 C1F-C1G \\sim C1R-C1Q
 with sigma of 0.02
 C1B-C1F \\sim C1O-C1R
 with sigma of 0.04
 C1D-C1F \\sim C1T-C1R
 with sigma of 0.04
 C1I-C1J \\sim C1J-C1K \\sim C1K-C1L \\sim C1L-C1M \\sim C1M-C1N \\sim C1N-C1I
 with sigma of 0.02
 C1I-C1M \\sim C1I-C1K \\sim C1N-C1L \\sim C1J-C1N \\sim C1K-C1M \\sim C1J-C1L
 with sigma of 0.04
 C1H-C1N \\sim C1H-C1J
 with sigma of 0.04
 Br13-C1C \\sim Br-C67
 with sigma of 0.02
 C1A-C1B \\sim C1P-C1O
 with sigma of 0.02
 C1B-C1C \\sim C1O-C67
 with sigma of 0.02
 C1B-C1G \\sim C1O-C1Q
 with sigma of 0.02
 C1C-C1D \\sim C67-C1T
 with sigma of 0.02
 C1D-C1E \\sim C1T-C1S
 with sigma of 0.02
 Br13-C1B \\sim Br-C1O
 with sigma of 0.04
 Br13-C1D \\sim Br-C1T
 with sigma of 0.04
 C1A-C1C \\sim C1P-C67
 with sigma of 0.04
 C1A-C1G \\sim C1P-C1Q
 with sigma of 0.04
 C1B-C1D \\sim C1O-C1T
 with sigma of 0.04
 C1C-C1E \\sim C67-C1S
 with sigma of 0.04
 C1C-C1G \\sim C67-C1Q
 with sigma of 0.04
 C1E-C1G \\sim C1S-C1Q
 with sigma of 0.04
 Br14-C1N \\sim Br15-C1U
 with sigma of 0.02
 C1H-C1I \\sim C1X-C1W
 with sigma of 0.02
 C1I-C1J \\sim C1W-C1Y
 with sigma of 0.02
 C1I-C1N \\sim C1W-C1U
 with sigma of 0.02
 C1J-C1K \\sim C1Y-C1Z
 with sigma of 0.02
 C1K-C1L \\sim C1Z-C1V
 with sigma of 0.02
 C1L-C1M \\sim C1V-C68
 with sigma of 0.02
 C1M-C1N \\sim C68-C1U
 with sigma of 0.02
 Br14-C1I \\sim Br15-C1W
 with sigma of 0.04
 Br14-C1M \\sim Br15-C68
 with sigma of 0.04
 C1H-C1J \\sim C1X-C1Y
 with sigma of 0.04
 C1H-C1N \\sim C1X-C1U
 with sigma of 0.04
 C1I-C1K \\sim C1W-C1Z
 with sigma of 0.04
 C1I-C1M \\sim C1W-C68
 with sigma of 0.04
 C1J-C1L \\sim C1Y-C1V
 with sigma of 0.04
 C1J-C1N \\sim C1Y-C1U
 with sigma of 0.04
 C1K-C1M \\sim C1Z-C68
 with sigma of 0.04
 C1L-C1N \\sim C1V-C1U
 with sigma of 0.04
 Br7-C37 \\sim Br7A-C37
 with sigma of 0.02
 Br1-C1 \\sim Br1A-C1
 with sigma of 0.02
 Br10-C53 \\sim Br16-C53A
 with sigma of 0.02
 C52-C53 \\sim C52-C53A
 with sigma of 0.02
 Br10-C52 \\sim Br16-C52
 with sigma of 0.04
 C53A-C52 \\sim C53-C52
 with sigma of 0.02
 Br6-C31 \\sim Br6A-C31A
 with sigma of 0.02
 C30-C31 \\sim C30-C31A
 with sigma of 0.02
 Br6-C30 \\sim Br6A-C30
 with sigma of 0.04
3. Restrained planarity
 C1A, C1B, C1C, C1D, C1E, C1F, C1G
 with sigma of 0.1
 Br13, C1C, C1B, C1D, C1A, C1G, C1E, C1F
 with sigma of 0.1
 C1H, C1I, C1J, C1K, C1L, C1M, C1N
 with sigma of 0.1
 Br14, C1N, C1I, C1M, C1H, C1J, C1L, C1K
 with sigma of 0.1
 C1X, Br15, C1U, C68, C1W, C1V, C1Y, C1Z
 with sigma of 0.1
 C1R, C67, C1O, Br, C1T, C1P, C1Q, C1S, H1T, H1PA, H1PB, H1PC, H1Q, H1S, H1R
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C1A \\sim C1B \\sim C1C \\sim C1D \\sim C1E \\sim C1F \\sim C1G: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C1B \\sim Br13 \\sim C1C \\sim C1D \\sim C1A \\sim C1G \\sim C1E \\sim C1F:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C1F \\sim C1G \\sim C1E: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C1H \\sim C1I \\sim C1J \\sim C1K \\sim C1L \\sim C1M \\sim C1N: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C1K \\sim Br14 \\sim C1N \\sim C1M \\sim C1I \\sim C1L \\sim C1H \\sim C1J:
within 2A with sigma of 0.021 and sigma for terminal atoms of 0.042 within 2A
Br \\sim C67 \\sim C1O \\sim C1T \\sim C1P \\sim C1Q \\sim C1S \\sim C1R:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Br15 \\sim C1U \\sim C68 \\sim C1W \\sim C1V \\sim C1X \\sim C1Y \\sim C1Z:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C1K \\sim C1L \\sim C1J: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C1D \\sim Br13 \\sim C1C \\sim C1B \\sim C1A \\sim C1O \\sim C1P \\sim C1Q
\\sim C1G \\sim C1E \\sim C67 \\sim C1F \\sim Br \\sim C1R \\sim C1S \\sim C1T:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C68 \\sim Br15 \\sim C1U \\sim C1W \\sim C1V \\sim C1X \\sim C1Y \\sim C1Z
\\sim C1N \\sim Br14 \\sim C1I \\sim C1M \\sim C1H \\sim C1J \\sim C1L \\sim
C1K: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C37 \\sim Br7A \\sim Br7: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Br1 \\sim Br1A \\sim C1: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C52 \\sim C53A \\sim Br16 \\sim C53 \\sim Br10: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Br16 \\sim C53A \\sim C53 \\sim Br10: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Br16 \\sim C53A: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C52 \\sim C53A \\sim Br16: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
C41 \\sim C42 \\sim Br8: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C31A \\sim C31 \\sim Br6 \\sim Br6A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Uanis(Br16) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C1X) \\sim Ueq, Uanis(Br15) \\sim Ueq, Uanis(C1U) \\sim Ueq, Uanis(C68)
\\sim Ueq, Uanis(C1W) \\sim Ueq, Uanis(C1V) \\sim Ueq, Uanis(C1Y) \\sim Ueq,
Uanis(C1Z) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C1A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 C1A, C1B, C1C, C1D, C1E, C1F, C1G
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C1H, C1I, C1J, C1K, C1L, C1M, C1N
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C1O)=Sof(C67)=Sof(C1T)=Sof(H1T)=Sof(C1S)=Sof(H1S)=Sof(C1R)=Sof(H1R)=
 Sof(C1Q)=Sof(H1Q)=Sof(C1P)=Sof(H1PA)=Sof(H1PB)=Sof(H1PC)=Sof(Br)=1-FVAR(1)
 Sof(Br13)=Sof(C1A)=Sof(H1AC)=Sof(H1AD)=Sof(H1AE)=Sof(C1B)=Sof(C1C)=Sof(C1D)=
 Sof(H1D)=Sof(C1E)=Sof(H1E)=Sof(C1F)=Sof(H1F)=Sof(C1G)=Sof(H1G)=FVAR(1)
 Sof(Br15)=Sof(C1U)=Sof(C68)=Sof(H68)=Sof(C1V)=Sof(H1V)=Sof(C1W)=Sof(C1X)=
 Sof(H1XA)=Sof(H1XB)=Sof(H1XC)=Sof(C1Y)=Sof(H1Y)=Sof(C1Z)=Sof(H1Z)=1-FVAR(2)
 Sof(Br14)=Sof(C1H)=Sof(H1HA)=Sof(H1HB)=Sof(H1HC)=Sof(C1I)=Sof(C1J)=Sof(H1J)=
 Sof(C1K)=Sof(H1K)=Sof(C1L)=Sof(H1L)=Sof(C1M)=Sof(H1M)=Sof(C1N)=FVAR(2)
 Sof(H37C)=Sof(H37D)=Sof(Br7A)=1-FVAR(3)
 Sof(Br7)=Sof(H37A)=Sof(H37B)=FVAR(3)
 Sof(H1BC)=Sof(H1BD)=Sof(Br1A)=1-FVAR(4)
 Sof(Br1)=Sof(H1AA)=Sof(H1AB)=FVAR(4)
 Sof(H52C)=Sof(H52D)=Sof(C53A)=Sof(H53C)=Sof(H53D)=Sof(Br16)=1-FVAR(5)
 Sof(Br10)=Sof(H52A)=Sof(H52B)=Sof(C53)=Sof(H53A)=Sof(H53B)=FVAR(5)
 Sof(Br8)=Sof(C42)=Sof(H42A)=Sof(H42B)=FVAR(6)
 Sof(H30C)=Sof(H30D)=Sof(C31A)=Sof(H31C)=Sof(H31D)=Sof(Br6A)=1-FVAR(7)
 Sof(Br6)=Sof(H30A)=Sof(H30B)=Sof(C31)=Sof(H31A)=Sof(H31B)=FVAR(7)
7.a Secondary CH2 refined with riding coordinates:
 C1(H1AA,H1AB), C1(H1BC,H1BD), C2(H2A,H2B), C7(H7A,H7B), C8(H8A,H8B), C11(H11A,
 H11B), C14(H14A,H14B), C15(H15A,H15B), C19(H19A,H19B), C20(H20A,H20B),
 C22(H22A,H22B), C25(H25A,H25B), C26(H26A,H26B), C30(H30A,H30B), C30(H30C,H30D),
  C31(H31A,H31B), C33(H33A,H33B), C36(H36A,H36B), C37(H37A,H37B), C37(H37C,
 H37D), C41(H41A,H41B), C42(H42A,H42B), C44(H44A,H44B), C47(H47A,H47B),
 C48(H48A,H48B), C52(H52A,H52B), C52(H52C,H52D), C53(H53A,H53B), C55(H55A,H55B),
  C58(H58A,H58B), C59(H59A,H59B), C63(H63A,H63B), C64(H64A,H64B), C66(H66A,
 H66B), C53A(H53C,H53D), C31A(H31C,H31D)
7.b Aromatic/amide H refined with riding coordinates:
 C4(H4), C9(H9), C16(H16), C21(H21), C27(H27), C32(H32), C38(H38), C43(H43),
 C49(H49), C54(H54), C60(H60), C65(H65), C1D(H1D), C1E(H1E), C1F(H1F), C1G(H1G),
  C1J(H1J), C1K(H1K), C1L(H1L), C1M(H1M), C1T(H1T), C1S(H1S), C1R(H1R),
 C1Q(H1Q), C68(H68), C1V(H1V), C1Y(H1Y), C1Z(H1Z)
7.c Fitted hexagon refined as free rotating group:
 C1O(C67,C1T,C1S,C1R,C1Q)
7.d Idealised Me refined as rotating group:
 C1A(H1AC,H1AD,H1AE), C1H(H1HA,H1HB,H1HC), C1P(H1PA,H1PB,H1PC), C1X(H1XA,H1XB,
 H1XC)
;
_smtbx_masks_void_probe_radius   0.7
_smtbx_masks_void_truncation_radius 2.4
_shelx_res_checksum              64176
_shelx_hkl_checksum              4477
_shelx_fab_checksum              69887
_olex2_submission_special_instructions 'No special instructions were received'