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_7156453
_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         'C72 H84 N4 O4, C H Cl3'
_chemical_formula_sum            'C73 H85 Cl3 N4 O4'
_chemical_formula_weight         1188.79
_chemical_name_systematic        DL6TtPP
_chemical_properties_physical    Photo-sensitive
_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'
_symmetry_space_group_name_Hall  '-P 2ybc'
_symmetry_space_group_name_H-M   'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2018-09-04
_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                90
_cell_angle_beta                 96.929(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.965(3)
_cell_length_b                   27.529(4)
_cell_length_c                   15.694(3)
_cell_measurement_reflns_used    20761
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      27.2
_cell_measurement_theta_min      1.5
_cell_volume                     6847(2)
_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      113.15
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_diffrn_measurement_device_type  'Rigaku Saturn 724CCD'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0473
_diffrn_reflns_av_unetI/netI     0.0436
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            61558
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.000
_diffrn_reflns_theta_min         1.285
_exptl_absorpt_coefficient_mu    0.183
_exptl_absorpt_correction_T_max  0.9713
_exptl_absorpt_correction_T_min  0.9574
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   Crystalclear
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.153
_exptl_crystal_description       Prism
_exptl_crystal_F_000             2536
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: chloroform, methanol'
_exptl_crystal_size_max          0.24
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.16
_refine_diff_density_max         0.971
_refine_diff_density_min         -0.565
_refine_diff_density_rms         0.056
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1017
_refine_ls_number_reflns         13450
_refine_ls_number_restraints     480
_refine_ls_restrained_S_all      1.165
_refine_ls_R_factor_all          0.0991
_refine_ls_R_factor_gt           0.0821
_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^)+(0.0755P)^2^+8.2011P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1906
_refine_ls_wR_factor_ref         0.2015
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10779
_reflns_number_total             13450
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8ob01959b2.cif
_cod_data_source_block           DL6TtPP
_cod_depositor_comments
'Adding full bibliography for 7156452--7156463.cif.'
_cod_original_cell_volume        6847.1(19)
_cod_database_code               7156453
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.971
_shelx_estimated_absorpt_t_min   0.957
_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,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C53'-C54' = C54'-C55' = C55'-C56' = C56'-C57' = C57'-C58'
 1.54 with sigma of 0.01
 C53-C54 = C54-C55 = C55-C56 = C56-C57 = C57-C58
 1.54 with sigma of 0.01
 C39-C24 = C39'-C24' = C69-C62 = C69'-C62'
 1.5 with sigma of 0.01
 C69-C70 = C69-C71 = C69-C72 = C69'-C70' = C69'-C71' = C69'-C72'
 1.54 with sigma of 0.01
 C40-C39 = C41-C39 = C42-C39 = C40'-C39' = C41'-C39' = C42'-C39'
 1.54 with sigma of 0.01
 C5-C22 = C5'-C22' = C20-C60 = C20'-C60'
 1.5 with sigma of 0.01
 C27-C28 = C27'-C28' = C28-C29 = C28'-C29
 1.54 with sigma of 0.01
 O1-C27 = O1'-C27' = O3-C53 = O3-C53'
 1.45 with sigma of 0.01
 C5-C4 \\sim C5-C6 \\sim C5'-C4 \\sim C5'-C6 \\sim C20-C1 \\sim C20-C19 \\sim
C20'-C1 \\sim C20'-C19
 with sigma of 0.01
 C70-C71 \\sim C70-C72 \\sim C71-C72 \\sim C70'-C71' \\sim C70'-C72' \\sim
C71'-C72'
 with sigma of 0.01
 C40-C41 \\sim C40-C42 \\sim C41-C42 \\sim C40-C41' \\sim C40-C42' \\sim
C41-C42'
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C20) \\sim Ueq, Uanis(C20') \\sim Ueq, Uanis(C60') \\sim Ueq, Uanis(C60)
\\sim Ueq, Uanis(C39') \\sim Ueq, Uanis(C41') \\sim Ueq, Uanis(C41) \\sim Ueq:
with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O1) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C26) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C53)
\\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(C57) \\sim Ueq,
Uanis(C58) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C61)
\\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C64) \\sim Ueq,
Uanis(O4) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C72)
\\sim Ueq, Uanis(O1') \\sim Ueq, Uanis(C5') \\sim Ueq, Uanis(C20') \\sim Ueq,
Uanis(C27') \\sim Ueq, Uanis(C28') \\sim Ueq, Uanis(C39') \\sim Ueq,
Uanis(C40') \\sim Ueq, Uanis(C41') \\sim Ueq, Uanis(C42') \\sim Ueq,
Uanis(C21') \\sim Ueq, Uanis(C22') \\sim Ueq, Uanis(C23') \\sim Ueq,
Uanis(C24') \\sim Ueq, Uanis(C25') \\sim Ueq, Uanis(C26') \\sim Ueq,
Uanis(C53') \\sim Ueq, Uanis(C54') \\sim Ueq, Uanis(C55') \\sim Ueq,
Uanis(C56') \\sim Ueq, Uanis(C57') \\sim Ueq, Uanis(C58') \\sim Ueq, Uanis(O4')
\\sim Ueq, Uanis(C69') \\sim Ueq, Uanis(C70') \\sim Ueq, Uanis(C71') \\sim Ueq,
Uanis(C72') \\sim Ueq, Uanis(C59') \\sim Ueq, Uanis(C60') \\sim Ueq,
Uanis(C61') \\sim Ueq, Uanis(C62') \\sim Ueq, Uanis(C63') \\sim Ueq,
Uanis(C64') \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(H29C)=Sof(H29D)=Sof(O1')=Sof(C5')=Sof(C27')=Sof(H27C)=Sof(H27D)=Sof(C28')=
 Sof(H28C)=Sof(H28D)=Sof(C39')=Sof(C40')=Sof(H40D)=Sof(H40E)=Sof(H40F)=
 Sof(C41')=Sof(H41D)=Sof(H41E)=Sof(H41F)=Sof(C42')=Sof(H42D)=Sof(H42E)=
 Sof(H42F)=Sof(C21')=Sof(C22')=Sof(C23')=Sof(H23')=Sof(C24')=Sof(C25')=
 Sof(H25')=Sof(C26')=Sof(H26')=1-FVAR(1)
 Sof(H29A)=Sof(H29B)=Sof(O1)=Sof(C21)=Sof(C22)=Sof(C23)=Sof(H23)=Sof(C24)=
 Sof(C25)=Sof(H25)=Sof(C26)=Sof(H26)=Sof(C5)=Sof(C27)=Sof(H27A)=Sof(H27B)=
 Sof(C28)=Sof(H28A)=Sof(H28B)=Sof(C39)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=
 Sof(C41)=Sof(H41A)=Sof(H41B)=Sof(H41C)=Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H42C)=
 FVAR(1)
 Sof(C20')=Sof(C53')=Sof(H53C)=Sof(H53D)=Sof(C54')=Sof(H54C)=Sof(H54D)=
 Sof(C55')=Sof(H55C)=Sof(H55D)=Sof(C56')=Sof(H56C)=Sof(H56D)=Sof(C57')=
 Sof(H57C)=Sof(H57D)=Sof(C58')=Sof(H58C)=Sof(H58D)=Sof(O4')=Sof(C69')=Sof(C70')=
 Sof(H70D)=Sof(H70E)=Sof(H70F)=Sof(C71')=Sof(H71D)=Sof(H71E)=Sof(H71F)=
 Sof(C72')=Sof(H72D)=Sof(H72E)=Sof(H72F)=Sof(C59')=Sof(C60')=Sof(C61')=
 Sof(H61')=Sof(C62')=Sof(C63')=Sof(H63')=Sof(C64')=Sof(H64')=1-FVAR(2)
 Sof(C20)=Sof(C55)=Sof(H55A)=Sof(H55B)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(C54)=
 Sof(H54A)=Sof(H54B)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(C57)=Sof(H57A)=Sof(H57B)=
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(C59)=Sof(C60)=Sof(C61)=Sof(H61)=Sof(C62)=
 Sof(C63)=Sof(H63)=Sof(C64)=Sof(H64)=Sof(O4)=Sof(C69)=Sof(C70)=Sof(H70A)=
 Sof(H70B)=Sof(H70C)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72)=Sof(H72A)=
 Sof(H72B)=Sof(H72C)=FVAR(2)
5.a Riding coordinates:
 C29(H29A,H29B,H29C,H29D)
5.b Ternary CH refined with riding coordinates:
 C73(H73)
5.c Secondary CH2 refined with riding coordinates:
 C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B), C55(H55A,H55B), C53(H53A,
 H53B), C54(H54A,H54B), C56(H56A,H56B), C57(H57A,H57B), C58(H58A,H58B),
 C27(H27A,H27B), C28(H28A,H28B), C27'(H27C,H27D), C28'(H28C,H28D), C53'(H53C,
 H53D), C54'(H54C,H54D), C55'(H55C,H55D), C56'(H56C,H56D), C57'(H57C,H57D),
 C58'(H58C,H58D)
5.d Aromatic/amide H refined with riding coordinates:
 N1(H1), N2(H2), N3(H3), N4(H4), C2(H2A), C3(H3A), C7(H7), C8(H8), C12(H12),
 C13(H13), C17(H17), C18(H18), C35(H35), C37(H37), C38(H38), C49(H49), C51(H51),
  C52(H52), C23(H23), C25(H25), C26(H26), C61(H61), C63(H63), C64(H64),
 C23'(H23'), C25'(H25'), C26'(H26'), C61'(H61'), C63'(H63'), C64'(H64')
5.e Fitted hexagon refined as free rotating group:
 C21(C22,C23,C24,C25,C26), C59(C60,C61,C62,C63,C64), C21'(C22',C23',C24',C25',
 C26'), C59'(C60',C61',C62',C63',C64')
5.f Idealised Me refined as rotating group:
 C44(H44A,H44B,H44C), C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C66(H66A,H66B,
 H66C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C40(H40A,H40B,H40C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C),
 C72(H72A,H72B,H72C), C40'(H40D,H40E,H40F), C41'(H41D,H41E,H41F), C42'(H42D,
 H42E,H42F), C70'(H70D,H70E,H70F), C71'(H71D,H71E,H71F), C72'(H72D,H72E,H72F)
;
_shelx_res_checksum              72687
_olex2_submission_special_instructions 'No special instructions were received'