Core-shell metal-macrocycle framework (MMF): spatially selective dye inclusion through core-to-shell anisotropic transport along crystalline 1D-channels connected by epitaxial growth
Tashiro, Shohei; Mitsui, Shinya; Burke, David W.; Kubota, Ryoh; Matsushita, Nobuyuki; Shionoya, Mitsuhiko; CrystEngComm  (2020) –; doi:10.1039/D0CE00120A

data_7239907
_publ_section_title
;
 Core-shell metal-macrocycle framework (MMF): spatially selective dye
 inclusion through core-to-shell anisotropic transport along crystalline
 1D-channels connected by epitaxial growth
;
_journal_name_full               CrystEngComm
_journal_paper_doi               10.1039/D0CE00120A
_journal_year                    2020
_chemical_formula_moiety
'C42 H42 Br1.64 Cl4.36 N6 Pd3, C42 H42 Br2.07 Cl3.93 N6 Pd3, 2(O)'
_chemical_formula_sum            'C84 H84 Br3.69 Cl8.31 N12 O2 Pd6'
_chemical_formula_weight         2521.48
_chemical_name_systematic        MMFcore
_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
_audit_creation_date             2019-08-29
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-11-07 deposited with the CCDC.	2020-02-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.516(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.2300(9)
_cell_length_b                   53.5168(16)
_cell_length_c                   14.3304(3)
_cell_measurement_reflns_used    16651
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      22.97
_cell_measurement_theta_min      2.46
_cell_volume                     15514.1(9)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      93.15
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       \w
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1222
_diffrn_reflns_av_unetI/netI     0.1243
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       50
_diffrn_reflns_limit_k_min       -63
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            111511
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.049
_exptl_absorpt_coefficient_mu    1.805
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.080
_exptl_crystal_description       plate
_exptl_crystal_F_000             4938
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile'
_exptl_crystal_size_max          0.101
_exptl_crystal_size_mid          0.071
_exptl_crystal_size_min          0.061
_refine_diff_density_max         2.424
_refine_diff_density_min         -1.633
_refine_diff_density_rms         0.209
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.088
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1016
_refine_ls_number_reflns         26700
_refine_ls_number_restraints     1086
_refine_ls_restrained_S_all      1.071
_refine_ls_R_factor_all          0.2528
_refine_ls_R_factor_gt           0.1699
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1772P)^2^+343.8222P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4275
_refine_ls_wR_factor_ref         0.4706
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13937
_reflns_number_total             26700
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ce00120a2.cif
_cod_data_source_block           MMFcore
_cod_database_code               7239907
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.898
_shelx_estimated_absorpt_t_min   0.839
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
2. Restrained distances
 N11-C71
 1.45 with sigma of 0.02
 N12-C76
 1.45 with sigma of 0.02
 N7-C84
 1.45 with sigma of 0.03
 N7-C84 \\sim N8-C49 \\sim N9-C56 \\sim N10-C63 \\sim N11-C70 \\sim N12-C77
 with sigma of 0.02
 Pd1-Cl1 \\sim Pd1-Cl2 \\sim Pd2-Cl3 \\sim Pd2-Cl4 \\sim Pd3-Cl5 \\sim Pd3-Cl6
\\sim Pd4-Cl7 \\sim Pd4-Cl8
 \\sim Pd5-Cl9 \\sim Pd5-Cl10 \\sim Pd6-Cl11 \\sim Pd6-Cl12
 with sigma of 0.02
 Pd1-Br1 \\sim Pd1-Br2 \\sim Pd2-Br3 \\sim Pd2-Br4 \\sim Pd3-Br5 \\sim Pd3-Br6
\\sim Pd4-Br7 \\sim Pd4-Br8
 \\sim Pd5-Br9 \\sim Pd5-Br10 \\sim Pd6-Br11 \\sim Pd6-Br12
 with sigma of 0.02
3. Rigid bond restraints
 Pd1, Cl1, Cl2, N1, N2, C1, C2, C3, C4, C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C7, C8, C9, C10, C11, C12, C13, C14
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C21, C22, C23, C24, C25, C26, C27, C28
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C35, C36, C37, C38, C39, C40, C41, C42
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Pd4, Cl7, Cl8, N7, N8, C43, C44, C45, C46, C47, C48
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C49, C50, C51, C52, C53, C54, C55, C56
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Pd5, Cl9, Cl10, N9, N10, C57, C58, C59, C60, C61, C62
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C63, C64, C65, C66, C67, C68, C69, C70, N10, N11
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Pd6, Cl11, Cl12, N11, N12, C71, C72, C73, C74, C75, C76, C77, C78, C79, C80,
 C81, C82, C83, C84
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Pd2, Cl3, Cl4, N3, N4, C15, C16, C17, C18, C19, C20
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Pd3, Cl5, Cl6, N5, N6, C29, C30, C31, C32, C33, C34
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Pd5, Br10
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Pd1 \\sim Cl1 \\sim Cl2 \\sim N1 \\sim N2 \\sim C1 \\sim C2 \\sim C3 \\sim C4
\\sim C5 \\sim C6: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08
C7 \\sim C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C14: within
2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C35 \\sim C36 \\sim C37 \\sim C38 \\sim C39 \\sim C40 \\sim C41 \\sim C42:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Pd4 \\sim Cl7 \\sim Cl8 \\sim N7 \\sim N8 \\sim C43 \\sim C44 \\sim C45 \\sim
C46 \\sim C47 \\sim C48: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C54 \\sim C55 \\sim C56:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Pd5 \\sim Cl9 \\sim Cl10 \\sim N9 \\sim N10 \\sim C57 \\sim C58 \\sim C59 \\sim
C60 \\sim C61 \\sim C62: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim
N10 \\sim N11: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
Pd6 \\sim Cl11 \\sim Cl12 \\sim N11 \\sim N12 \\sim C71 \\sim C72 \\sim C73
\\sim C74 \\sim C75 \\sim C76 \\sim C77 \\sim C78 \\sim C79 \\sim C80 \\sim C81
\\sim C82 \\sim C83 \\sim C84: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
Pd2 \\sim Cl3 \\sim Cl4 \\sim N3 \\sim N4 \\sim C15 \\sim C16 \\sim C17 \\sim
C18 \\sim C19 \\sim C20: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Pd3 \\sim Cl5 \\sim Cl6 \\sim N5 \\sim N6 \\sim C29 \\sim C30 \\sim C31 \\sim
C32 \\sim C33 \\sim C34: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
Br9 \\sim Cl9 \\sim Pd5: within 1.7A with sigma of 0.04 and sigma for terminal
atoms of 0.08
Uanis(Br9) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 N10, C63
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Br9, Cl9, Pd5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Br10, Pd5
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O2)=1-FVAR(1)
 Sof(O1)=FVAR(1)
 Sof(Br1)=1-FVAR(2)
 Sof(Cl1)=FVAR(2)
 Sof(Br2)=1-FVAR(3)
 Sof(Cl2)=FVAR(3)
 Sof(Br3)=1-FVAR(4)
 Sof(Cl3)=FVAR(4)
 Sof(Br4)=1-FVAR(5)
 Sof(Cl4)=FVAR(5)
 Sof(Br6)=1-FVAR(6)
 Sof(Cl6)=FVAR(6)
 Sof(Br5)=1-FVAR(7)
 Sof(Cl5)=FVAR(7)
 Sof(Br7)=1-FVAR(8)
 Sof(Cl7)=FVAR(8)
 Sof(Br8)=1-FVAR(9)
 Sof(Cl8)=FVAR(9)
 Sof(Br9)=1-FVAR(10)
 Sof(Cl9)=FVAR(10)
 Sof(Br10)=1-FVAR(11)
 Sof(Cl10)=FVAR(11)
 Sof(Br11)=1-FVAR(12)
 Sof(Cl11)=FVAR(12)
 Sof(Br12)=1-FVAR(13)
 Sof(Cl12)=FVAR(13)
7.a Ternary CH refined with riding coordinates:
 N1(H1), N2(H2), N3(H3A), N4(H4A), N5(H5A), N6(H6), N7(H7), N8(H8), N9(H9A),
 N10(H10A), N11(H11), N12(H12A)
7.b Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C14(H14A,H14B), C21(H21A,H21B), C28(H28A,H28B), C35(H35A,H35B),
 C42(H42A,H42B), C49(H49A,H49B), C56(H56A,H56B), C63(H63A,H63B), C70(H70A,H70B),
  C77(H77A,H77B), C84(H84A,H84B)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C4(H4), C5(H5), C9(H9), C10(H10), C12(H12), C13(H13),
 C16(H16), C17(H17), C18(H18), C19(H19), C23(H23), C24(H24), C26(H26), C27(H27),
  C30(H30), C31(H31), C32(H32), C33(H33), C37(H37), C38(H38), C40(H40),
 C41(H41), C44(H44), C45(H45), C46(H46), C47(H47), C51(H51), C52(H52), C54(H54),
  C55(H55), C58(H58), C59(H59), C60(H60), C61(H61), C65(H65), C66(H66),
 C68(H68), C69(H69), C72(H72), C73(H73), C74(H74), C75(H75), C79(H79), C80(H80),
  C82(H82), C83(H83)
7.d Fitted hexagon refined as free rotating group:
 C1(C2,C3,C4,C5,C6), C8(C9,C10,C11,C12,C13), C15(C16,C17,C18,C19,C20), C22(C23,
 C24,C25,C26,C27), C29(C30,C31,C32,C33,C34), C36(C37,C38,C39,C40,C41), C43(C44,
 C45,C46,C47,C48), C50(C51,C52,C53,C54,C55), C57(C58,C59,C60,C61,C62), C64(C65,
 C66,C67,C68,C69), C71(C72,C73,C74,C75,C76), C78(C79,C80,C81,C82,C83)
;
_shelx_res_checksum              17058
_olex2_submission_original_sample_id MMFcore
_olex2_submission_special_instructions 'No special instructions were received'