Crystalline paramagnetic supramolecular 2D-polymer of tetra(4-pyridyl)porphyrin and terbium(III) complex
Nazarov, Dmitry I.; Faraonov, Maxim A.; Kuzmin, Alexey V.; Khasanov, Salavat S.; Otsuka, Akihiro; Yamochi, Hideki; Kitagawa, Hiroshi; Konarev, Dmitri V.; Dalton Transactions  (2022) –; doi:10.1039/D2DT03170A

data_7711471
_publ_section_title
;
 Crystalline paramagnetic supramolecular 2D-polymer of
 tetra(4-pyridyl)porphyrin and terbium(III) complex
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT03170A
_journal_year                    2022
_chemical_formula_moiety         'C53 H70 N4 O6 Tb, 1.25(C6 H14)'
_chemical_formula_sum            'C60.5 H87.5 N4 O6 Tb'
_chemical_formula_weight         1125.76
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-09-21
_audit_creation_method
;FinalCif V111 by Daniel Kratzert, Freiburg 2022,
https://dkratzert.de/finalcif.html
;
_audit_update_record
;
2022-09-21 deposited with the CCDC.	2022-10-13 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.9320(10)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.4122(3)
_cell_length_b                   27.6488(3)
_cell_length_c                   23.3343(3)
_cell_measurement_reflns_used    30465
_cell_measurement_temperature    104(6)
_cell_measurement_theta_max      27.0950
_cell_measurement_theta_min      2.2110
_cell_volume                     12507.7(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.51a (Rigaku OD, 2022)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      104.15
_diffrn_detector_area_resol_mean 5.2283
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.982
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w     -9.00  66.00   1.00   96.00    --   13.35  57.00 -60.00   75
  2  \w      7.00  73.00   1.00   96.00    --   13.35  57.00  90.00   66
  3  \w    -37.00  28.00   1.00   96.00    --   13.35 -37.00 150.00   65
  4  \w    -15.00  80.00   1.00   96.00    --   13.35  57.00   0.00   95
  5  \w     13.00  38.00   1.00   96.00    --  -13.66  37.00 -90.00   25
  6  \w    -50.00 -25.00   1.00   96.00    --  -13.66 -37.00-180.00   25
  7  \w    -56.00 -40.00   1.00   96.00    --  -13.66 -57.00  60.00   16
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, AtlasS2, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0250
_diffrn_reflns_av_unetI/netI     0.0241
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       35
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            59405
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.102
_diffrn_reflns_theta_min         1.748
_exptl_absorpt_coefficient_mu    1.178
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.90640
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.51a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic dark black'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.196
_exptl_crystal_description       plate
_exptl_crystal_F_000             4732
_exptl_crystal_size_max          0.323
_exptl_crystal_size_mid          0.263
_exptl_crystal_size_min          0.192
_refine_diff_density_max         3.154
_refine_diff_density_min         -1.959
_refine_diff_density_rms         0.144
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.192
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     773
_refine_ls_number_reflns         13551
_refine_ls_number_restraints     844
_refine_ls_restrained_S_all      1.191
_refine_ls_R_factor_all          0.0749
_refine_ls_R_factor_gt           0.0664
_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^)+(0.0339P)^2^+233.7526P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1607
_refine_ls_wR_factor_ref         0.1655
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11993
_reflns_number_total             13551
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt03170a2.cif
_cod_data_source_block           exp_1983_int2
_cod_original_formula_sum        'C60.50 H87.50 N4 O6 Tb'
_cod_database_code               7711471
_shelx_shelxl_version_number     2018/3
_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
 C506-C505 = C505-C504 = C504-C503 = C503-C502 = C502-C501
 1.52 with sigma of 0.02
 C506-C504 = C503-C501
 2.53 with sigma of 0.04
 C505-C503 = C504-C502
 2.54 with sigma of 0.04
 C506-C505 \\sim C505-C504 \\sim C504-C503 \\sim C503-C502 \\sim C502-C501
 with sigma of 0.02
 C506-C504 \\sim C504-C502 \\sim C505-C503 \\sim C503-C501
 with sigma of 0.04
 C219-C222 \\sim C1-C422
 with sigma of 0.02
 C221-C222 \\sim C420-C422
 with sigma of 0.04
 C219-C221 \\sim C1-C420
 with sigma of 0.02
 C218-C220 \\sim C218-C421
 with sigma of 0.04
 C218-C221 \\sim C218-C420
 with sigma of 0.04
 C218-C219 \\sim C218-C1
 with sigma of 0.02
 C219-C220 \\sim C1-C421
 with sigma of 0.02
 C220-C222 \\sim C421-C422
 with sigma of 0.04
 C218-C222 \\sim C218-C422
 with sigma of 0.04
 C220-C221 \\sim C421-C420
 with sigma of 0.04
 C201-C204 \\sim C201-C404
 with sigma of 0.04
 C201-C205 \\sim C201-C405
 with sigma of 0.04
 C204-C205 \\sim C404-C405
 with sigma of 0.04
 C202-C203 \\sim C402-C403
 with sigma of 0.02
 C201-C203 \\sim C201-C403
 with sigma of 0.04
 C202-C204 \\sim C402-C404
 with sigma of 0.02
 C203-C205 \\sim C403-C405
 with sigma of 0.04
 C202-C205 \\sim C402-C405
 with sigma of 0.02
 C203-C204 \\sim C403-C404
 with sigma of 0.04
 C201-C202 \\sim C201-C402
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C501 \\sim C502 \\sim C503 \\sim C504 \\sim C505 \\sim C506: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
Uanis(C101) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C103) \\sim Ueq,
Uanis(C104) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(C106) \\sim Ueq,
Uanis(C107) \\sim Ueq, Uanis(C108) \\sim Ueq, Uanis(C109) \\sim Ueq,
Uanis(C110) \\sim Ueq, Uanis(C111) \\sim Ueq, Uanis(C112) \\sim Ueq,
Uanis(C113) \\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C115) \\sim Ueq,
Uanis(C116) \\sim Ueq, Uanis(C117) \\sim Ueq, Uanis(C118) \\sim Ueq,
Uanis(C119) \\sim Ueq, Uanis(C120) \\sim Ueq, Uanis(C201) \\sim Ueq,
Uanis(C202) \\sim Ueq, Uanis(C203) \\sim Ueq, Uanis(C204) \\sim Ueq,
Uanis(C205) \\sim Ueq, Uanis(C206) \\sim Ueq, Uanis(C207) \\sim Ueq,
Uanis(C208) \\sim Ueq, Uanis(C209) \\sim Ueq, Uanis(C210) \\sim Ueq,
Uanis(C211) \\sim Ueq, Uanis(C212) \\sim Ueq, Uanis(C213) \\sim Ueq,
Uanis(C214) \\sim Ueq, Uanis(C215) \\sim Ueq, Uanis(C216) \\sim Ueq,
Uanis(C217) \\sim Ueq, Uanis(C218) \\sim Ueq, Uanis(C219) \\sim Ueq,
Uanis(C220) \\sim Ueq, Uanis(C221) \\sim Ueq, Uanis(C222) \\sim Ueq,
Uanis(C223) \\sim Ueq, Uanis(C224) \\sim Ueq, Uanis(C225) \\sim Ueq,
Uanis(C226) \\sim Ueq, Uanis(C227) \\sim Ueq, Uanis(C228) \\sim Ueq,
Uanis(C229) \\sim Ueq, Uanis(C230) \\sim Ueq, Uanis(C231) \\sim Ueq,
Uanis(C232) \\sim Ueq, Uanis(C233) \\sim Ueq, Uanis(C431) \\sim Ueq,
Uanis(C432) \\sim Ueq, Uanis(C433) \\sim Ueq, Uanis(C301) \\sim Ueq,
Uanis(C302) \\sim Ueq, Uanis(C303) \\sim Ueq, Uanis(C304) \\sim Ueq,
Uanis(C305) \\sim Ueq, Uanis(C306) \\sim Ueq, Uanis(C501) \\sim Ueq,
Uanis(C502) \\sim Ueq, Uanis(C503) \\sim Ueq, Uanis(C504) \\sim Ueq,
Uanis(C505) \\sim Ueq, Uanis(C506) \\sim Ueq, Uanis(C421) \\sim Ueq, Uanis(C1)
\\sim Ueq, Uanis(C420) \\sim Ueq, Uanis(C422) \\sim Ueq, Uanis(C402) \\sim Ueq,
Uanis(C403) \\sim Ueq, Uanis(C405) \\sim Ueq, Uanis(C404) \\sim Ueq,
Uanis(O201) \\sim Ueq, Uanis(O202) \\sim Ueq, Uanis(O203) \\sim Ueq,
Uanis(O204) \\sim Ueq, Uanis(O205) \\sim Ueq, Uanis(O206) \\sim Ueq,
Uanis(N101) \\sim Ueq, Uanis(N102) \\sim Ueq, Uanis(N103) \\sim Ueq,
Uanis(N104) \\sim Ueq, Uanis(N105) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C422) = Uanis(C222)
Uanis(C1) = Uanis(C219)
Uanis(C220) = Uanis(C421)
Uanis(C420) = Uanis(C221)
Uanis(C403) = Uanis(C203)
Uanis(C404) = Uanis(C204)
Uanis(C402) = Uanis(C202)
Uanis(C405) = Uanis(C205)
4. Rigid body (RIGU) restrains
 C219, C220, C221, C222
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C205, C230, C231, C232, C233, C431, C432, C433
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C213, C214, C215, C216
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C501, C502, C503, C504, C505, C506
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Same fragment restrains
{C202, C203, C204, C205} sigma for 1-2: 0.001, 1-3: 0.04
as in
{C208, C209, C210, C211}
{C202, C203, C204, C205} sigma for 1-2: 0.001, 1-3: 0.04
as in
{C213, C214, C215, C216}
{C202, C203, C204, C205} sigma for 1-2: 0.001, 1-3: 0.04
as in
{C219, C220, C221, C222}
{C202, C203, C204, C205} sigma for 1-2: 0.001, 1-3: 0.04
as in
{C224, C225, C226, C227}
{C202, C203, C204, C205} sigma for 1-2: 0.001, 1-3: 0.04
as in
{C230, C231, C232, C233}
{C203, C204, C205} sigma for 1-2: 0.001, 1-3: 0.04
as in
{C431, C432, C433}
6. Others
 1*[Sof(H10A)+Sof(H10B)]+1*[Sof(H103)]=1 with esd of 0.0001
 Sof(C431)=Sof(H43A)=Sof(H43B)=Sof(H43C)=Sof(C432)=Sof(H43D)=Sof(H43E)=
 Sof(H43F)=Sof(C433)=Sof(H43G)=Sof(H43H)=Sof(H43I)=1-FVAR(1)
 Sof(C231)=Sof(H23A)=Sof(H23B)=Sof(H23C)=Sof(C232)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=Sof(C233)=Sof(H23G)=Sof(H23H)=Sof(H23I)=FVAR(1)
 Sof(H10A)=Sof(H10B)=0.5*FVAR(3)
 Sof(C421)=Sof(H42A)=Sof(H42B)=Sof(H42C)=Sof(C1)=Sof(C420)=Sof(H42D)=Sof(H42E)=
 Sof(H42F)=Sof(C422)=Sof(H42G)=Sof(H42H)=Sof(H42I)=1-FVAR(3)
 Sof(C219)=Sof(C220)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C221)=Sof(H22D)=
 Sof(H22E)=Sof(H22F)=Sof(C222)=Sof(H22G)=Sof(H22H)=Sof(H22I)=FVAR(3)
 Sof(C402)=Sof(C403)=Sof(H40A)=Sof(H40B)=Sof(H40C)=Sof(C405)=Sof(H40D)=
 Sof(H40E)=Sof(H40F)=Sof(C404)=Sof(H40G)=Sof(H40H)=Sof(H40I)=1-FVAR(5)
 Sof(C202)=Sof(C203)=Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(C204)=Sof(H20D)=
 Sof(H20E)=Sof(H20F)=Sof(C205)=Sof(H20G)=Sof(H20H)=Sof(H20I)=FVAR(5)
 Fixed Sof: C501(0.25) H50A(0.25) H50B(0.25) H50C(0.25) C502(0.25) H50D(0.25)
 H50E(0.25) C503(0.25) H50F(0.25) H50G(0.25) C504(0.25) H50H(0.25) H50I(0.25)
 C505(0.25) H50J(0.25) H50K(0.25) C506(0.25) H50L(0.25) H50M(0.25) H50N(0.25)
7.a Secondary CH2 refined with riding coordinates:
 C302(H30D,H30E), C303(H30F,H30G), C304(H30H,H30I), C305(H30J,H30K), C502(H50D,
 H50E), C503(H50F,H50G), C504(H50H,H50I), C505(H50J,H50K)
7.b Aromatic/amide H refined with riding coordinates:
 C101(H101), C105(H105), C106(H106), C107(H107), C108(H108), C110(H110),
 C111(H111), C115(H115), C116(H116), C117(H117), C118(H118), C120(H120),
 C206(H206), C217(H217), C228(H228), N101(H10A), N103(H103), N105(H10B)
7.c Idealised Me refined as rotating group:
 C203(H20A,H20B,H20C), C204(H20D,H20E,H20F), C205(H20G,H20H,H20I), C209(H20J,
 H20K,H20L), C210(H21A,H21B,H21C), C211(H21D,H21E,H21F), C214(H21G,H21H,H21I),
 C215(H21J,H21K,H21L), C216(H21M,H21N,H21O), C220(H22A,H22B,H22C), C221(H22D,
 H22E,H22F), C222(H22G,H22H,H22I), C225(H22J,H22K,H22L), C226(H22M,H22N,H22O),
 C227(H22P,H22Q,H22R), C231(H23A,H23B,H23C), C232(H23D,H23E,H23F), C233(H23G,
 H23H,H23I), C431(H43A,H43B,H43C), C432(H43D,H43E,H43F), C433(H43G,H43H,H43I),
 C301(H30A,H30B,H30C), C306(H30L,H30M,H30N), C501(H50A,H50B,H50C), C506(H50L,
 H50M,H50N), C421(H42A,H42B,H42C), C420(H42D,H42E,H42F), C422(H42G,H42H,H42I),
 C403(H40A,H40B,H40C), C405(H40D,H40E,H40F), C404(H40G,H40H,H40I)
;
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_shelx_estimated_absorpt_t_min   0.702
_shelx_estimated_absorpt_t_max   0.805
_shelx_res_checksum              16621