Structural and dimensional control of porphyrin capsules using Group 15 tris(3-pyridyl) linkers.
García-Romero, Álvaro; Miguel, Daniel; Wright, Dominic S.; Álvarez, Celedonio M; García-Rodríguez, Raúl; Chemical science 14 (2023) 6522–6530; doi:10.1039/d3sc02151c

data_1569314
_publ_section_title
;
 Structural and dimensional control of porphyrin capsules using Group 15
 tris(3-pyridyl) linkers.
;
_journal_issue                   24
_journal_name_full               'Chemical science'
_journal_page_first              6522
_journal_page_last               6530
_journal_paper_doi               10.1039/d3sc02151c
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C147 H96 Bi N15 Zn3, C6 H14'
_chemical_formula_sum            'C153 H110 Bi N15 Zn3'
_chemical_formula_weight         2563.64
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-31
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2022-08-10 deposited with the CCDC.	2023-05-17 downloaded from the CCDC.
;
_cell_angle_alpha                86.862(3)
_cell_angle_beta                 79.147(3)
_cell_angle_gamma                76.921(3)
_cell_formula_units_Z            2
_cell_length_a                   11.5622(5)
_cell_length_b                   21.0461(8)
_cell_length_c                   27.9789(9)
_cell_measurement_reflns_used    6776
_cell_measurement_temperature    180(2)
_cell_measurement_theta_max      24.1640
_cell_measurement_theta_min      2.4040
_cell_volume                     6512.6(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'XT  (Sheldrick, 2015)'
_diffrn_ambient_temperature      180.05(10)
_diffrn_detector_area_resol_mean 10.4757
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -34.00  59.00   1.00   25.00    --  -10.64  57.00-120.00   93
  2  \w    -76.00  22.00   1.00   25.00    --  -10.64 -77.00 -30.00   98
  3  \w    -80.00  16.00   1.00   25.00    --  -10.64 -57.00  90.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0885
_diffrn_reflns_av_unetI/netI     0.1619
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            43773
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.026
_diffrn_reflns_theta_max         25.026
_diffrn_reflns_theta_min         1.839
_exptl_absorpt_coefficient_mu    1.950
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.48789
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            violet
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.307
_exptl_crystal_description       needle
_exptl_crystal_F_000             2612
_exptl_crystal_size_max          0.554
_exptl_crystal_size_mid          0.112
_exptl_crystal_size_min          0.049
_refine_diff_density_max         1.598
_refine_diff_density_min         -1.267
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.934
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1538
_refine_ls_number_reflns         22999
_refine_ls_number_restraints     27
_refine_ls_restrained_S_all      0.936
_refine_ls_R_factor_all          0.1171
_refine_ls_R_factor_gt           0.0598
_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^)+(0.0386P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1096
_refine_ls_wR_factor_ref         0.1290
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13793
_reflns_number_total             22999
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02151c2.cif
_cod_data_source_block           2Zn-open
_cod_database_code               1569314
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Rigid body (RIGU) restrains
 C1S, C2S, C3S, C4S, C5S, C6S
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
2.a Free rotating group:
 C6S(C1S,C2S,C3S,C4S,C5S)
2.b Secondary CH2 refined with riding coordinates:
 C2S(H2SA,H2SB), C3S(H3SA,H3SB), C4S(H4SA,H4SB), C5S(H5SA,H5SB)
2.c Me refined with riding coordinates:
 C1S(H1SA,H1SB,H1SC)
2.d Aromatic/amide H refined with riding coordinates:
 C1(H1), C3(H3), C4(H4), C5(H5), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12),
 C13(H13), C14(H14), C15(H15), C17(H17), C18(H18), C22(H22), C23(H23), C27(H27),
  C28(H28), C32(H32), C33(H33), C37(H37), C38(H38), C39(H39), C40(H40),
 C41(H41), C43(H43), C44(H44), C45(H45), C46(H46), C47(H47), C49(H49), C50(H50),
  C51(H51), C52(H52), C53(H53), C55(H55), C56(H56), C57(H57), C58(H58),
 C59(H59), C61(H61), C62(H62), C66(H66), C67(H67), C71(H71), C72(H72), C76(H76),
  C77(H77), C78(H78), C79(H79), C80(H80), C82(H82), C83(H83), C87(H87),
 C88(H88), C89(H89), C90(H90), C91(H91), C93(H93), C94(H94), C95(H95), C96(H96),
  C97(H97), C100(H100), C101(H101), C105(H105), C106(H106), C110(H110),
 C111(H111), C115(H115), C116(H116), C118(H118), C119(H119), C120(H120),
 C121(H121), C122(H122), C124(H124), C125(H125), C126(H126), C127(H127),
 C128(H128), C130(H130), C131(H131), C132(H132), C133(H133), C134(H134),
 C136(H136), C137(H137), C138(H138), C139(H139), C140(H140), C143(H143),
 C144(H144), C145(H145), C146(H146), C147(H147)
2.e Idealised Me refined as rotating group:
 C6S(H6SA,H6SB,H6SC)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 167 electrons were found in a volume of 760 cubic angstroms in 2 voids per unit cell, with poorly defined molecules of solvent (CHCl3 and hexane).
The crystallization solvent was CHCl3/hexane and NMR spectroscopy indicated the presence of both CHCl3 and hexane in the bulk crystalline sample. Although this could be consistent with the presence of roughly 2 molecules of hexane and 1 molecule of CHCl3 in the unit cell (which account for 158 electrons per unit cell). The exact proportion of the solvents in the crystal is difficult to determine due to their similar electron count.
Moreover, the crystals were observed to lose solvent very quickly during the preparation of the sample, and therefore the exact amount of hexane or CHCl3 is expected to vary among crystals due to their partial loss
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              73821
_shelx_hkl_checksum              16143
_shelx_fab_checksum              7338
_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
;