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_7239908
_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 Br6 N6 Pd3, C42 H42 Br4.87 Cl1.13 N6 Pd3, 3(C2 H3 N), O'
_chemical_formula_sum            'C90 H93 Br10.86 Cl1.14 N15 O Pd6'
_chemical_formula_weight         2947.42
_chemical_name_systematic        MMFshell
_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             2019-08-30
_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                 91.3840(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   20.0078(3)
_cell_length_b                   53.0768(9)
_cell_length_c                   14.55750(18)
_cell_measurement_reflns_used    42432
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      27.88
_cell_measurement_theta_min      2.35
_cell_volume                     15454.8(4)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      93.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.973
_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  0.0493
_diffrn_reflns_av_unetI/netI     0.0678
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.973
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       67
_diffrn_reflns_limit_k_min       -68
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            124177
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.973
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.500
_diffrn_reflns_theta_min         1.812
_exptl_absorpt_coefficient_mu    3.545
_exptl_absorpt_correction_T_max  0.762
_exptl_absorpt_correction_T_min  0.660
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.9g (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.267
_exptl_crystal_description       plate
_exptl_crystal_F_000             5686
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetonitrile'
_exptl_crystal_size_max          0.147
_exptl_crystal_size_mid          0.085
_exptl_crystal_size_min          0.071
_refine_diff_density_max         4.143
_refine_diff_density_min         -4.342
_refine_diff_density_rms         0.216
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.102
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1055
_refine_ls_number_reflns         34507
_refine_ls_number_restraints     519
_refine_ls_restrained_S_all      1.100
_refine_ls_R_factor_all          0.1524
_refine_ls_R_factor_gt           0.1090
_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^)+(0.1154P)^2^+255.4627P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2816
_refine_ls_wR_factor_ref         0.3017
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22948
_reflns_number_total             34507
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0ce00120a2.cif
_cod_data_source_block           MMFshell
_cod_database_code               7239908
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.787
_shelx_estimated_absorpt_t_min   0.624
_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) 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
 C63-C64
 1.55 with sigma of 0.02
 Pd1-Br1
 2.41 with sigma of 0.02
 Pd5-Cl9
 2.3 with sigma of 0.02
 Pd5-Cl10
 2.3 with sigma of 0.02
 Cl10-Cl9
 3.35 with sigma of 0.02
 Pd6-Cl11
 2.3 with sigma of 0.02
 Cl12-Pd6
 2.3 with sigma of 0.02
 Cl12-Cl11
 3.35 with sigma of 0.02
 N7-C84 \\sim N8-C49 \\sim N9-C56 \\sim N10-C63 \\sim N11-C70 \\sim N12-C77
 with sigma of 0.02
3. Rigid bond restraints
 Pd4, Br7, Br8, 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, Br9, Br10, N9, N10, C57, C58, C59, C60, C61, C62, Cl9, Cl10
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C63, C64, C65, C66, C67, C68, C69, C70, N11
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Cl11, Pd6, Cl12
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 Pd6, Br11, Br12, 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
4. Uiso/Uaniso restraints and constraints
Pd4 \\sim Br7 \\sim Br8 \\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 Br9 \\sim Br10 \\sim N9 \\sim N10 \\sim C57 \\sim C58 \\sim C59 \\sim
C60 \\sim C61 \\sim C62 \\sim Cl9 \\sim Cl10: within 2A with sigma of 0.002 and
sigma for terminal atoms of 0.002
C63 \\sim C64 \\sim C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim
N11: within 2A with sigma of 0.002 and sigma for terminal atoms of 0.002
Pd6 \\sim Br11 \\sim Br12 \\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
Uanis(Cl11) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
5. Same fragment restrains
{N1S, C1S, C2S} sigma for 1-2: 0.01, 1-3: 0.01
as
{N1T, C1T, C2T}
{N1S, C1S, C2S} sigma for 1-2: 0.01, 1-3: 0.01
as
{N1U, C1U, C2U}
6. Others
 Sof(Cl9)=1-FVAR(1)
 Sof(Br9)=FVAR(1)
 Sof(Cl10)=1-FVAR(2)
 Sof(Br10)=FVAR(2)
 Sof(Cl11)=1-FVAR(3)
 Sof(Br11)=FVAR(3)
 Sof(Cl12)=1-FVAR(4)
 Sof(Br12)=FVAR(4)
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), N11(H11), N12(H12)
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(H9A), C10(H10A), C12(H12A), 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:
 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)
7.e Idealised Me refined with riding coordinates:
 C2S(H2SA,H2SB,H2SC), C2T(H2TA,H2TB,H2TC), C2U(H2UA,H2UB,H2UC)
;
_shelx_res_checksum              70699
_olex2_submission_special_instructions 'No special instructions were received'