Geometric deconstruction of core and electron activation of a π-system in a series of deformed porphyrins: mimics of heme.
Liu, Qiuhua; Zhang, Jinjin; Tang, Min; Yang, Yan; Zhang, Jian; Zhou, Zaichun; Organic & biomolecular chemistry 16 (2018) 7725–7736; doi:10.1039/c8ob01959b

data_7156455
_publ_section_title
;
 Geometric deconstruction of core and electron activation of a \p-system
 in a series of deformed porphyrins: mimics of heme.
;
_journal_issue                   41
_journal_name_full               'Organic &amp; biomolecular chemistry'
_journal_page_first              7725
_journal_page_last               7736
_journal_paper_doi               10.1039/c8ob01959b
_journal_volume                  16
_journal_year                    2018
_chemical_formula_moiety         'C70 H78 N4 O4'
_chemical_formula_sum            'C70 H78 N4 O4'
_chemical_formula_weight         1039.36
_chemical_name_systematic        DL5TtPP
_chemical_properties_physical    Photo-sensitive
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2018-09-03
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-09-20 deposited with the CCDC.
2018-09-27 downloaded from the CCDC.
;
_cell_angle_alpha                63.01(3)
_cell_angle_beta                 80.01(3)
_cell_angle_gamma                72.54(3)
_cell_formula_units_Z            2
_cell_length_a                   14.492(3)
_cell_length_b                   17.096(3)
_cell_length_c                   17.259(4)
_cell_measurement_reflns_used    6766
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      27.8346
_cell_measurement_theta_min      1.3253
_cell_volume                     3631.2(17)
_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      173.15
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Rigaku Saturn 70 CCD'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.2165
_diffrn_reflns_av_unetI/netI     0.3471
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            36525
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        25.020
_diffrn_reflns_theta_max         25.020
_diffrn_reflns_theta_min         1.325
_exptl_absorpt_coefficient_mu    0.058
_exptl_absorpt_correction_T_max  0.9907
_exptl_absorpt_correction_T_min  0.9872
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   Crystalclear
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    0.951
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       Prism
_exptl_crystal_F_000             1116
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: chloroform, methanol'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.16
_platon_squeeze_details
;
;
_refine_diff_density_max         0.379
_refine_diff_density_min         -0.355
_refine_diff_density_rms         0.108
_refine_ls_extinction_coef       0.0074(11)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2014/7 (Sheldrick 2014'
_refine_ls_goodness_of_fit_ref   0.804
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     743
_refine_ls_number_reflns         12814
_refine_ls_number_restraints     233
_refine_ls_restrained_S_all      0.810
_refine_ls_R_factor_all          0.2349
_refine_ls_R_factor_gt           0.1578
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1485P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3651
_refine_ls_wR_factor_ref         0.3934
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2415
_reflns_number_total             12814
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob01959b2.cif
_cod_data_source_block           DL5TtPP
_cod_depositor_comments
'Adding full bibliography for 7156452--7156463.cif.'
_cod_database_code               7156455
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.991
_shelx_estimated_absorpt_t_min   0.987
_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
 C27-C28 = C27-C29 = C27-C30 = C52-C53 = C52-C54 = C52-C55
 1.54 with sigma of 0.01
 C27-C28' = C27-C29' = C27-C30' = C52-C53' = C52-C54' = C52-C55'
 1.54 with sigma of 0.01
 C67-C68 = C67-C69 = C67-C70 = C67-C68' = C67-C69' = C67-C70'
 1.54 with sigma of 0.01
 C64-C67 = C48-C52
 1.5 with sigma of 0.01
 C53-C54 \\sim C53-C55 \\sim C54-C55 \\sim C53'-C54' \\sim C53'-C55' \\sim
C54'-C55'
 with sigma of 0.01
 C28-C29 \\sim C28-C30 \\sim C29-C30 \\sim C28'-C29' \\sim C28'-C30' \\sim
C29'-C30'
 with sigma of 0.01
 C68-C69 \\sim C68-C70 \\sim C69-C70 \\sim C68'-C69' \\sim C68'-C70' \\sim
C69'-C70'
 with sigma of 0.01
 C64-C68 \\sim C64-C69 \\sim C64-C70 \\sim C64-C68' \\sim C64-C69' \\sim
C64-C70'
 with sigma of 0.01
 C48-C53 \\sim C48-C54 \\sim C48-C55 \\sim C48-C53' \\sim C48-C54' \\sim
C48-C55'
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq,
Uanis(C55) \\sim Ueq, Uanis(C28') \\sim Ueq, Uanis(C29') \\sim Ueq, Uanis(C30')
\\sim Ueq, Uanis(C53') \\sim Ueq, Uanis(C54') \\sim Ueq, Uanis(C55') \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C67) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C70)
\\sim Ueq, Uanis(C68') \\sim Ueq, Uanis(C69') \\sim Ueq, Uanis(C70') \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C69) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C42) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C53) = Uanis(C53') = Uanis(C54) = Uanis(C54') = Uanis(C55) = Uanis(C55')
Uanis(C68) = Uanis(C68')
Uanis(C69) = Uanis(C69')
Uanis(C70) = Uanis(C70')
4. Others
 Sof(C28')=Sof(H28D)=Sof(H28E)=Sof(H28F)=Sof(C29')=Sof(H29D)=Sof(H29E)=
 Sof(H29F)=Sof(C30')=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(1)
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(H28C)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=
 Sof(C30)=Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(1)
 Sof(C53')=Sof(H53D)=Sof(H53E)=Sof(H53F)=Sof(C54')=Sof(H54D)=Sof(H54E)=
 Sof(H54F)=Sof(C55')=Sof(H55D)=Sof(H55E)=Sof(H55F)=1-FVAR(2)
 Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=
 Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(H55C)=FVAR(2)
 Sof(C68')=Sof(H68D)=Sof(H68E)=Sof(H68F)=Sof(C69')=Sof(H69D)=Sof(H69E)=
 Sof(H69F)=Sof(C70')=Sof(H70D)=Sof(H70E)=Sof(H70F)=1-FVAR(3)
 Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=Sof(C69)=Sof(H69A)=Sof(H69B)=Sof(H69C)=
 Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C31(H31A,H31B), C32(H32A,H32B), C33(H33A,H33B), C34(H34A,H34B), C35(H35A,
 H35B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B), C59(H59A,H59B),
 C60(H60A,H60B)
5.b Me refined with riding coordinates:
 C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C), C28'(H28D,H28E,
 H28F), C29'(H29D,H29E,H29F), C30'(H30D,H30E,H30F), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C53'(H53D,H53E,H53F), C54'(H54D,H54E,
 H54F), C55'(H55D,H55E,H55F), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C),
 C70(H70A,H70B,H70C), C68'(H68D,H68E,H68F), C69'(H69D,H69E,H69F), C70'(H70D,
 H70E,H70F)
5.c Aromatic/amide H refined with riding coordinates:
 N2(H2), N4(H4), C2(H2A), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C17(H17),
  C18(H18), C22(H22), C24(H24), C25(H25), C37(H37), C38(H38), C40(H40),
 C47(H47), C49(H49), C50(H50), C62(H62), C63(H63), C65(H65)
5.d Idealised Me refined as rotating group:
 C43(H43A,H43B,H43C), C44(H44A,H44B,H44C), C45(H45A,H45B,H45C)
;
_shelx_res_checksum              55982
_olex2_submission_special_instructions 'No special instructions were received'