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_7239906
_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
'2(C42 H42 Br6 N6 Pd3), 1.5(C2 H3 N), 1.71(C3 H6 O), 1.75(O)'
_chemical_formula_sum            'C92.11 H98.73 Br12 N13.5 O3.46 Pd6'
_chemical_formula_weight         3047.55
_chemical_name_systematic        MMFBr
_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             2019-08-19
_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                 88.4818(8)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.00896(19)
_cell_length_b                   53.1688(5)
_cell_length_c                   14.50409(14)
_cell_measurement_reflns_used    41495
_cell_measurement_temperature    98(2)
_cell_measurement_theta_max      73.18
_cell_measurement_theta_min      2.78
_cell_volume                     15424.8(3)
_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      98.0
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.973
_diffrn_measurement_device_type  'Rigaku XtaLAB P200'
_diffrn_measurement_method       \w
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0572
_diffrn_reflns_av_unetI/netI     0.0550
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       64
_diffrn_reflns_limit_k_min       -64
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            100397
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.589
_diffrn_reflns_theta_min         2.765
_exptl_absorpt_coefficient_mu    9.453
_exptl_absorpt_correction_T_max  0.516
_exptl_absorpt_correction_T_min  0.420
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.20a (Rigaku Oxford Diffraction, 2015)

Empirical absorption correction using spherical harmonics,

 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.312
_exptl_crystal_description       block
_exptl_crystal_F_000             5878
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile'
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.07
_refine_diff_density_max         2.198
_refine_diff_density_min         -1.619
_refine_diff_density_rms         0.187
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1221
_refine_ls_number_reflns         30274
_refine_ls_number_restraints     413
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.1125
_refine_ls_R_factor_gt           0.0834
_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^)+(0.1369P)^2^+95.8076P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2378
_refine_ls_wR_factor_ref         0.2582
_reflns_Friedel_coverage         0.000
_reflns_number_gt                21704
_reflns_number_total             30274
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ce00120a2.cif
_cod_data_source_block           MMFBr
_cod_original_formula_sum        'C92.11 H98.73 Br12 N13.50 O3.46 Pd6'
_cod_database_code               7239906
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.557
_shelx_estimated_absorpt_t_min   0.331
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C67-C70A
 1.52 with sigma of 0.02
 C70A-N11A
 1.51 with sigma of 0.02
 N11A-Pd6A
 2.05 with sigma of 0.02
 Pd6A-Br11
 2.42 with sigma of 0.02
 C67-C70A \\sim C67-C70B \\sim C78-C77A \\sim C78-C77B
 with sigma of 0.02
 C70A-N11A \\sim C70B-N11B \\sim C77A-N12A \\sim C77B-N12B
 with sigma of 0.02
 N11A-Pd6A \\sim N12A-Pd6A \\sim N11B-Pd6B \\sim N12B-Pd6B
 with sigma of 0.02
 Pd6A-Br11 \\sim Pd6A-Br12 \\sim Pd6B-Br13 \\sim Pd6B-Br14
 with sigma of 0.02
3. Restrained planarity
 O2, C92, C94, C93
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Pd6A \\sim Br11 \\sim Br12 \\sim N11A \\sim N12A \\sim C70A \\sim C71A \\sim
C72A \\sim C73A \\sim C74A \\sim C75A \\sim C76A \\sim C77A: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Pd6B \\sim Br13 \\sim Br14 \\sim N11B \\sim N12B \\sim C70B \\sim C71B \\sim
C72B \\sim C73B \\sim C74B \\sim C75B \\sim C76B \\sim C77B: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(N11A) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(N11B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Br11) \\sim Ueq, Uanis(Br12) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
5. Rigid body (RIGU) restrains
 Pd6A, Br11, Br12, N11A, N12A, C70A, C71A, C72A, C73A, C74A, C75A, C76A, C77A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Pd6B, Br13, Br14, N11B, N12B, C70B, C71B, C72B, C73B, C74B, C75B, C76B, C77B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C57, C58, C59, C60, C61, C62
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(Pd6A)=Sof(Br11)=Sof(Br12)=Sof(N11A)=Sof(H11A)=Sof(N12A)=Sof(H12A)=
 Sof(C70A)=Sof(H70A)=Sof(H70B)=Sof(C71A)=Sof(C72A)=Sof(H72A)=Sof(C73A)=
 Sof(H73A)=Sof(C74A)=Sof(H74A)=Sof(C75A)=Sof(H75A)=Sof(C76A)=Sof(C77A)=
 Sof(H77A)=Sof(H77B)=Sof(O4A)=1-FVAR(1)
 Sof(O4B)=0.5*FVAR(2)
 Sof(Pd6B)=Sof(Br13)=Sof(Br14)=Sof(N11B)=Sof(H11B)=Sof(N12B)=Sof(H12B)=
 Sof(C70B)=Sof(H70C)=Sof(H70D)=Sof(C71B)=Sof(C72B)=Sof(H72B)=Sof(C73B)=
 Sof(H73B)=Sof(C74B)=Sof(H74B)=Sof(C75B)=Sof(H75B)=Sof(C76B)=Sof(C77B)=
 Sof(H77C)=Sof(H77D)=FVAR(1)
 Sof(O2)=Sof(C92)=Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(H93C)=Sof(C94)=Sof(H94A)=
 Sof(H94B)=Sof(H94C)=FVAR(2)
 Fixed Sof: N14(0.5) C87(0.5) C88(0.5) H88A(0.5) H88B(0.5) H88C(0.5)
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(H9),
 N10(H10), N11A(H11A), N12A(H12A), N11B(H11B), N12B(H12B)
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), C70A(H70A,
 H70B), C77A(H77A,H77B), C70B(H70C,H70D), C77B(H77C,H77D), C84(H84A,H84B)
7.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C4(H4), C5(H5), C9(H9A), C10(H10A), 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), C72A(H72A), C73A(H73A), C74A(H74A), C75A(H75A), C72B(H72B),
  C73B(H73B), C74B(H74B), C75B(H75B), C79(H79), C80(H80), C82(H82), C83(H83)
7.d Fitted hexagon refined as free rotating group:
 C43(C44,C45,C46,C47,C48), C50(C51,C52,C53,C54,C55), C57(C58,C59,C60,C61,C62),
 C64(C65,C66,C67,C68,C69), C71A(C72A,C73A,C74A,C75A,C76A), C71B(C72B,C73B,C74B,
 C75B,C76B), C78(C79,C80,C81,C82,C83)
7.e Idealised Me refined as rotating group:
 C86(H86A,H86B,H86C), C88(H88A,H88B,H88C), C90(H90A,H90B,H90C), C91(H91A,H91B,
 H91C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C)
;
_shelx_res_checksum              86115
_olex2_submission_original_sample_id MMFBr
_olex2_submission_special_instructions 'No special instructions were received'