X-Shaped Cyclobutane-Linked Tetraporphyrins through a Thermal [2+2] Cycloaddition of Etheno-Fused Diporphyrins.
Nagai, Tomohiro; Takiguchi, Asahi; Ueda, Masayuki; Oda, Kazuma; Hiroto, Satoru; Shinokubo, Hiroshi; Journal of the American Chemical Society 140 (2018) 8392–8395; doi:10.1021/jacs.8b04673

data_4132532
_publ_section_title
;
 X-Shaped Cyclobutane-Linked Tetraporphyrins through a Thermal [2+2]
 Cycloaddition of Etheno-Fused Diporphyrins.
;
_journal_issue                   27
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              8392
_journal_page_last               8395
_journal_paper_doi               10.1021/jacs.8b04673
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety
'C256 H286 N18 O4 Zn4, 5.64(C6 H5 Cl), 1.83(C2 H3 N), 0.62(O)'
_chemical_formula_sum            'C293.49 H319.68 Cl5.64 N19.83 O4.62 Zn4'
_chemical_formula_weight         4660.19
_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             2018-03-22
_audit_creation_method
;
Olex2 1.2
(compiled Nov 22 2016 11:51:51 for OlexSys, GUI svn.r5269)
;
_cell_angle_alpha                90
_cell_angle_beta                 105.3550(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   17.9200(2)
_cell_length_b                   40.8305(3)
_cell_length_c                   18.66700(10)
_cell_measurement_reflns_used    51720
_cell_measurement_temperature    93(2)
_cell_measurement_theta_max      30.3320
_cell_measurement_theta_min      1.7700
_cell_volume                     13170.8(2)
_computing_cell_refinement       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.41 (Rigaku OD, 2015)'
_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 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      93(2)
_diffrn_detector_area_resol_mean 28.5714
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0355
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       51
_diffrn_reflns_limit_k_min       -51
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            127625
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.500
_diffrn_reflns_theta_min         1.544
_diffrn_source                   'fine-focus sealed X-ray tube'
_exptl_absorpt_coefficient_mu    0.476
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64611
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.41 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.175
_exptl_crystal_description       plate
_exptl_crystal_F_000             4945
_exptl_crystal_size_max          0.119
_exptl_crystal_size_mid          0.079
_exptl_crystal_size_min          0.058
_refine_diff_density_max         1.203
_refine_diff_density_min         -1.088
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.022
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1794
_refine_ls_number_reflns         27271
_refine_ls_number_restraints     183
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0728
_refine_ls_R_factor_gt           0.0590
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0991P)^2^+16.3170P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1620
_refine_ls_wR_factor_ref         0.1742
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22348
_reflns_number_total             27271
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b04673_si_004.cif
_cod_data_source_block           nagai_170810_zn_diketo_1_a
_cod_database_code               4132532
_shelx_estimated_absorpt_t_max   0.870
_shelx_estimated_absorpt_t_min   0.818
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl4-C145
 1.73 with sigma of 0.02
 Cl3-C139
 1.73 with sigma of 0.02
 C6AA-C7AA
 1.5 with sigma of 0.02
 C91-C7BA = C91-C8BA = C91-C9BA
 1.5 with sigma of 0.02
 C81-C1BA = C81-C4BA = C81-C5BA
 1.5 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C145 \\sim C146 \\sim C147 \\sim C148 \\sim C149 \\sim C150: within 2A with
sigma of 0.02 and sigma for terminal atoms of 0.04
Cl0A \\sim C0AA \\sim C1AA \\sim C2AA \\sim C3AA \\sim C4AA \\sim C5AA: within
2A with sigma of 0.01 and sigma for terminal atoms of 0.02
N1AA \\sim C0BA \\sim C2BA: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
N0AA \\sim C8AA \\sim C9AA: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
N2AA \\sim C6AA \\sim C7AA: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C91 \\sim C9BA \\sim C7BA \\sim C8BA: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02
N6BA \\sim C6BA \\sim C5CA: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C8BA: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C81 \\sim C1BA \\sim C4BA \\sim C5BA: within 2A with sigma of 0.005 and sigma
for terminal atoms of 0.01
Uanis(C92) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C5BA) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(Cl4)=Sof(C145)=Sof(C146)=Sof(H146)=Sof(C147)=Sof(H147)=Sof(C148)=
 Sof(H148)=Sof(C149)=Sof(H149)=Sof(C150)=Sof(H150)=Sof(Cl0A)=Sof(C0AA)=
 Sof(C1AA)=Sof(H1AA)=Sof(C2AA)=Sof(H2AA)=Sof(C3AA)=Sof(H3AA)=Sof(C4AA)=
 Sof(H4AA)=Sof(C5AA)=Sof(H5AA)=Sof(Zn0A)=Sof(N1AA)=Sof(C0BA)=Sof(C2BA)=
 Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=1-FVAR(1)
 Sof(C133)=Sof(C134)=Sof(H134)=Sof(C135)=Sof(H135)=Sof(C136)=Sof(H136)=
 Sof(C137)=Sof(H137)=Sof(C138)=Sof(H138)=Sof(Cl2)=Sof(Zn2)=Sof(Cl3)=Sof(C139)=
 Sof(C140)=Sof(H140)=Sof(C141)=Sof(H141)=Sof(C142)=Sof(H142)=Sof(C143)=
 Sof(H143)=Sof(C144)=Sof(H144)=Sof(N2AA)=Sof(C6AA)=Sof(C7AA)=Sof(H7AA)=
 Sof(H7AB)=Sof(H7AC)=Sof(N0AA)=Sof(C8AA)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=
 Sof(C9AA)=FVAR(1)
 Sof(C1BA)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=Sof(C4BA)=Sof(H4BA)=Sof(H4BB)=
 Sof(H4BC)=Sof(C5BA)=Sof(H5BA)=Sof(H5BB)=Sof(H5BC)=1-FVAR(2)
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=
 Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(H84C)=FVAR(2)
 Sof(C9BA)=Sof(H9BA)=Sof(H9BB)=Sof(H9BC)=Sof(C7BA)=Sof(H7BA)=Sof(H7BB)=
 Sof(H7BC)=Sof(C8BA)=Sof(H8BA)=Sof(H8BB)=Sof(H8BC)=1-FVAR(3)
 Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(H92C)=Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(H93C)=
 Sof(C94)=Sof(H94A)=Sof(H94B)=Sof(H94C)=FVAR(3)
 Sof(C3CA)=Sof(H3CA)=Sof(H3CB)=Sof(H3CC)=Sof(C1CA)=Sof(C2CA)=Sof(H2CA)=
 Sof(H2CB)=Sof(H2CC)=Sof(C0CA)=Sof(H0CA)=Sof(H0CB)=Sof(H0CC)=1-FVAR(4)
 Sof(C95)=Sof(C96)=Sof(H96A)=Sof(H96B)=Sof(H96C)=Sof(C97)=Sof(H97A)=Sof(H97B)=
 Sof(H97C)=Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(H98C)=FVAR(4)
 Sof(C127)=Sof(C128)=Sof(H128)=Sof(C129)=Sof(H129)=Sof(C130)=Sof(H130)=
 Sof(C131)=Sof(H131)=Sof(C132)=Sof(H132)=Sof(Cl1)=FVAR(5)
 Sof(N6BA)=Sof(C6BA)=Sof(C5CA)=Sof(H5CA)=Sof(H5CB)=Sof(H5CC)=FVAR(6)
5.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C17(H17), C18(H18), C23(H23),
 C27(H27), C28(H28), C32(H32), C33(H33), C37(H37), C38(H38), C44(H44), C46(H46),
  C48(H48), C58(H58), C60(H60), C62(H62), C72(H72), C74(H74), C76(H76),
 C86(H86), C88(H88), C90(H90), C100(H100), C102(H102), C104(H104), C114(H114),
 C116(H116), C118(H118), C128(H128), C129(H129), C130(H130), C131(H131),
 C132(H132), C134(H134), C135(H135), C136(H136), C137(H137), C138(H138),
 C140(H140), C141(H141), C142(H142), C143(H143), C144(H144), C146(H146),
 C147(H147), C148(H148), C149(H149), C150(H150), C1AA(H1AA), C2AA(H2AA),
 C3AA(H3AA), C4AA(H4AA), C5AA(H5AA)
5.b Fitted hexagon refined as free rotating group:
 C139(C140,C141,C142,C143,C144), C145(C146,C147,C148,C149,C150), C0AA(C1AA,
 C2AA,C3AA,C4AA,C5AA)
5.c Idealised Me refined as rotating group:
 C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,
 H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C64(H64A,H64B,H64C), C65(H65A,
 H65B,H65C), C66(H66A,H66B,H66C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C),
 C70(H70A,H70B,H70C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C), C80(H80A,H80B,
 H80C), C82(H82A,H82B,H82C), C83(H83A,H83B,H83C), C84(H84A,H84B,H84C), C92(H92A,
 H92B,H92C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C96(H96A,H96B,H96C),
 C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C106(H10A,H10B,H10C), C107(H10D,H10E,
 H10F), C108(H10G,H10H,H10I), C110(H11A,H11B,H11C), C111(H11D,H11E,H11F),
 C112(H11G,H11H,H11I), C120(H12A,H12B,H12C), C121(H12D,H12E,H12F), C122(H12G,
 H12H,H12I), C124(H12J,H12K,H12L), C125(H12M,H12N,H12O), C126(H12P,H12Q,H12R),
 C7AA(H7AA,H7AB,H7AC), C1BA(H1BA,H1BB,H1BC), C4BA(H4BA,H4BB,H4BC), C5BA(H5BA,
 H5BB,H5BC), C9BA(H9BA,H9BB,H9BC), C7BA(H7BA,H7BB,H7BC), C8BA(H8BA,H8BB,H8BC),
 C3CA(H3CA,H3CB,H3CC), C2CA(H2CA,H2CB,H2CC), C0CA(H0CA,H0CB,H0CC), C8AA(H8AA,
 H8AB,H8AC), C2BA(H2BA,H2BB,H2BC), C5CA(H5CA,H5CB,H5CC)
;
_shelx_res_checksum              86208
_shelx_hkl_checksum              10516
_shelx_shelxl_version_number     2017/1
_olex2_submission_special_instructions 'No special instructions were received'