#------------------------------------------------------------------------------
#$Date: 2020-05-05 16:51:32 +0300 (Tue, 05 May 2020) $
#$Revision: 251736 $
#$URL: file:///home/coder/svn-repositories/cod/cif/7/15/74/7157425.cif $
#------------------------------------------------------------------------------
#
# This file is available in the Crystallography Open Database (COD),
# http://www.crystallography.net/
#
# All data on this site have been placed in the public domain by the
# contributors.
#
data_7157425
loop_
_publ_author_name
'Thomas, Kolle E.'
'Conradie, Jeanet'
'Beavers, Christine M.'
'Ghosh, Abhik'
_publ_section_title
;
 Free-base porphyrins with localized NH protons. Can substituents alone
 stabilize the elusive cis tautomer?
;
_journal_issue                   15
_journal_name_full               'Organic & biomolecular chemistry'
_journal_page_first              2861
_journal_page_last               2865
_journal_paper_doi               10.1039/d0ob00452a
_journal_volume                  18
_journal_year                    2020
_chemical_formula_moiety         'C48 H26 F12 N4, C7 H8'
_chemical_formula_sum            'C55 H34 F12 N4'
_chemical_formula_weight         978.86
_chemical_name_systematic
'7,8,17,18-tetrakis(trifluoromethyl)-5,10,15,20-tetraphenylporphyrin toluene solvate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   difmap
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_method           SHELXL-2014/7
_audit_update_record
;
2020-01-20 deposited with the CCDC.	2020-03-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 115.609(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.975(4)
_cell_length_b                   7.5139(10)
_cell_length_c                   20.464(3)
_cell_measurement_reflns_used    8219
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.2
_cell_measurement_theta_min      2.98
_cell_volume                     4433.6(10)
_computing_cell_refinement       'SAINT V7.68A(Bruker, 2008)'
_computing_data_collection       'Apex2 v2009.11-0 (Bruker, 2009)'
_computing_data_reduction        SAINT
_computing_molecular_graphics
;
     	SHELXTL 5.1, XP (Sheldrick, 1994)
	ShelXle Rev 699 (Hubschle, 2011)
;
_computing_publication_material  SHELXL-2014/7
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    SHELXS
_diffrn_ambient_temperature      100(2)
_diffrn_detector_area_resol_mean 8.3
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.958
_diffrn_measurement_device_type  'Bruker Apex2'
_diffrn_measurement_method       ω
_diffrn_radiation_monochromator  silicon(111)
_diffrn_radiation_source         'Advanced Light Source Beamline 11.3.1'
_diffrn_radiation_type           synchrotron
_diffrn_radiation_wavelength     0.7749
_diffrn_reflns_av_R_equivalents  0.0689
_diffrn_reflns_av_unetI/netI     0.0586
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.958
_diffrn_reflns_limit_h_max       46
_diffrn_reflns_limit_h_min       -45
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            31524
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.958
_diffrn_reflns_theta_full        27.706
_diffrn_reflns_theta_max         34.726
_diffrn_reflns_theta_min         2.979
_exptl_absorpt_coefficient_mu    0.148
_exptl_absorpt_correction_T_max  0.7468
_exptl_absorpt_correction_T_min  0.6587
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details   'SADABS-2008/1  (Sheldrick, 2008)'
_exptl_crystal_colour            'dark red'
_exptl_crystal_density_diffrn    1.466
_exptl_crystal_description       shard
_exptl_crystal_F_000             2000
_exptl_crystal_size_max          0.160
_exptl_crystal_size_mid          0.050
_exptl_crystal_size_min          0.020
_refine_diff_density_max         1.033
_refine_diff_density_min         -0.548
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    refall
_refine_ls_matrix_type           full
_refine_ls_number_parameters     405
_refine_ls_number_reflns         7060
_refine_ls_number_restraints     61
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0810
_refine_ls_R_factor_gt           0.0640
_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/[σ²(Fo²)+(0.0946P)²+5.8918P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1783
_refine_ls_wR_factor_ref         0.1896
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5378
_reflns_number_total             7060
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            d0ob00452a2.cif
_cod_data_source_block           CF3TPP
_cod_depositor_comments          'Adding full bibliography for 7157425.cif.'
_cod_original_cell_volume        4433.7(10)
_cod_original_sg_symbol_H-M      'C 2/c'
_cod_database_code               7157425
_shelx_shelxl_version_number     2014/7
_shelx_space_group_comment
;
The symmetry employed for this shelxl refinement is uniquely defined
by the following loop, which should always be used as a source of
symmetry information in preference to the above space-group names.
They are only intended as comments.
;
_shelx_estimated_absorpt_t_min   0.977
_shelx_estimated_absorpt_t_max   0.997
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x, y, -z+1/2'
'x+1/2, y+1/2, z'
'-x+1/2, y+1/2, -z+1/2'
'-x, -y, -z'
'x, -y, z-1/2'
'-x+1/2, -y+1/2, -z'
'x+1/2, -y+1/2, z-1/2'
loop_
_atom_site_label
_atom_site_type_symbol
_atom_site_fract_x
_atom_site_fract_y
_atom_site_fract_z
_atom_site_U_iso_or_equiv
_atom_site_adp_type
_atom_site_occupancy
_atom_site_site_symmetry_order
_atom_site_calc_flag
_atom_site_refinement_flags_posn
_atom_site_refinement_flags_adp
_atom_site_refinement_flags_occupancy
_atom_site_disorder_assembly
_atom_site_disorder_group
F1 F 0.33286(6) 0.78986(19) 0.13849(10) 0.0525(4) Uani 1 1 d . . . . .
F2 F 0.31431(5) 0.5869(2) 0.19169(8) 0.0443(4) Uani 1 1 d . . . . .
F3 F 0.28375(5) 0.5947(2) 0.07509(8) 0.0499(4) Uani 1 1 d . . . . .
F4 F 0.33721(6) 0.76437(19) 0.01606(8) 0.0449(4) Uani 1 1 d . . . . .
F5 F 0.32144(5) 0.5189(2) -0.04343(7) 0.0460(4) Uani 1 1 d . . . . .
F6 F 0.38650(4) 0.64851(17) -0.01502(6) 0.0323(3) Uani 1 1 d . . . . .
N1 N 0.43316(5) 0.3653(2) 0.17695(7) 0.0207(3) Uani 1 1 d . . . . .
N2 N 0.47905(5) 0.3525(2) 0.33362(8) 0.0207(3) Uani 1 1 d . . . . .
C1 C 0.41946(5) 0.4097(2) 0.10639(9) 0.0195(3) Uani 1 1 d . . . . .
C2 C 0.37600(6) 0.5065(2) 0.07929(9) 0.0203(3) Uani 1 1 d . . . . .
C3 C 0.36205(6) 0.5062(2) 0.13372(9) 0.0210(3) Uani 1 1 d . . . . .
C4 C 0.39761(5) 0.4077(2) 0.19356(9) 0.0204(3) Uani 1 1 d . . . . .
C5 C 0.39526(5) 0.3359(2) 0.25635(9) 0.0210(3) Uani 1 1 d . . . . .
C6 C 0.43512(5) 0.2992(2) 0.31990(9) 0.0212(3) Uani 1 1 d . . . . .
C7 C 0.43839(6) 0.2099(2) 0.38362(9) 0.0231(3) Uani 1 1 d . . . . .
C8 C 0.48350(6) 0.2148(2) 0.43371(9) 0.0229(3) Uani 1 1 d . . . . .
C9 C 0.50984(6) 0.3052(2) 0.40251(9) 0.0205(3) Uani 1 1 d . . . . .
C10 C 0.55719(5) 0.3437(2) 0.43401(9) 0.0199(3) Uani 1 1 d . . . . .
C11 C 0.58557(6) 0.2879(2) 0.51029(9) 0.0214(3) Uani 1 1 d . . . . .
C12 C 0.62471(6) 0.1820(3) 0.52505(10) 0.0266(4) Uani 1 1 d . . . . .
C13 C 0.65217(7) 0.1235(3) 0.59504(11) 0.0318(4) Uani 1 1 d . . . . .
C14 C 0.64073(7) 0.1694(3) 0.65078(10) 0.0317(4) Uani 1 1 d . . . . .
C15 C 0.60215(8) 0.2735(3) 0.63684(10) 0.0303(4) Uani 1 1 d . . . . .
C16 C 0.57430(7) 0.3325(3) 0.56678(10) 0.0258(3) Uani 1 1 d . . . . .
C17 C 0.34989(6) 0.2758(2) 0.25065(9) 0.0207(3) Uani 1 1 d . . . . .
C18 C 0.33492(6) 0.3096(2) 0.30425(9) 0.0228(3) Uani 1 1 d . . . . .
C19 C 0.29185(6) 0.2502(2) 0.29615(10) 0.0243(3) Uani 1 1 d . . . . .
C20 C 0.26305(6) 0.1573(3) 0.23439(11) 0.0263(4) Uani 1 1 d . . . . .
C21 C 0.27757(6) 0.1227(3) 0.18104(11) 0.0282(4) Uani 1 1 d . . . . .
C22 C 0.32069(6) 0.1812(3) 0.18899(9) 0.0234(3) Uani 1 1 d . . . . .
C23 C 0.32289(7) 0.6157(3) 0.13491(10) 0.0287(4) Uani 1 1 d . . . . .
C24 C 0.35495(7) 0.6091(3) 0.00959(10) 0.0270(4) Uani 1 1 d . . . . .
H2 H 0.4893(10) 0.402(4) 0.3020(15) 0.041(7) Uiso 1 1 d . . . . .
H7 H 0.4143(8) 0.161(3) 0.3893(12) 0.023(5) Uiso 1 1 d . . . . .
H8 H 0.4962(8) 0.159(3) 0.4824(12) 0.023(5) Uiso 1 1 d . . . . .
H12 H 0.6340(9) 0.153(4) 0.4841(15) 0.037(7) Uiso 1 1 d . . . . .
H13 H 0.6784(10) 0.056(4) 0.6053(15) 0.041(7) Uiso 1 1 d . . . . .
H14 H 0.6595(10) 0.124(4) 0.7036(16) 0.044(8) Uiso 1 1 d . . . . .
H15 H 0.5935(9) 0.308(4) 0.6756(14) 0.029(6) Uiso 1 1 d . . . . .
H16 H 0.5482(9) 0.405(3) 0.5601(13) 0.028(6) Uiso 1 1 d . . . . .
H18 H 0.3544(8) 0.379(3) 0.3488(12) 0.020(5) Uiso 1 1 d . . . . .
H19 H 0.2815(8) 0.271(3) 0.3343(12) 0.020(5) Uiso 1 1 d . . . . .
H20 H 0.2358(9) 0.112(3) 0.2304(14) 0.032(6) Uiso 1 1 d . . . . .
H21 H 0.2609(10) 0.069(4) 0.1388(15) 0.037(7) Uiso 1 1 d . . . . .
H22 H 0.3316(9) 0.155(4) 0.1557(15) 0.035(7) Uiso 1 1 d . . . . .
C1S C 0.4569(2) 0.9132(7) 0.2460(3) 0.0533(13) Uani 0.5 1 d D U P A -1
H1S H 0.4406 0.9442 0.2737 0.064 Uiso 0.5 1 calc R U P A -1
C2S C 0.43434(17) 0.9207(7) 0.1707(3) 0.0458(11) Uani 0.5 1 d D U P A -1
H2S H 0.4028 0.9574 0.1480 0.055 Uiso 0.5 1 calc R U P A -1
C3S C 0.4556(3) 0.8780(17) 0.1298(5) 0.0464(16) Uani 0.5 1 d D U P A -1
H3S H 0.4400 0.8841 0.0784 0.056 Uiso 0.5 1 calc R U P A -1
C4S C 0.5024(2) 0.8232(9) 0.1653(3) 0.0505(13) Uani 0.5 1 d D U P A -1
H4S H 0.5182 0.7909 0.1369 0.061 Uiso 0.5 1 calc R U P A -1
C5S C 0.5254(2) 0.8154(10) 0.2384(3) 0.0537(14) Uani 0.5 1 d D U P A -1
H5S H 0.5569 0.7787 0.2605 0.064 Uiso 0.5 1 calc R U P A -1
C6S C 0.5032(2) 0.8606(7) 0.2813(3) 0.0502(12) Uani 0.5 1 d D U P A -1
C7S C 0.5272(4) 0.8531(16) 0.3607(5) 0.070(3) Uani 0.5 1 d D U P A -1
H7SA H 0.5593 0.8938 0.3769 0.106 Uiso 0.5 1 calc R U P A -1
H7SB H 0.5272 0.7304 0.3769 0.106 Uiso 0.5 1 calc R U P A -1
H7SC H 0.5113 0.9302 0.3813 0.106 Uiso 0.5 1 calc R U P A -1
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0043 0.0021 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
N N 0.0082 0.0041 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
F F 0.0216 0.0128 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
loop_
_geom_angle_atom_site_label_1
_geom_angle_atom_site_label_2
_geom_angle_atom_site_label_3
_geom_angle
_geom_angle_site_symmetry_1
_geom_angle_site_symmetry_3
_geom_angle_publ_flag
C1 N1 C4 106.77(14) . . ?
C6 N2 C9 110.63(14) . . ?
C6 N2 H2 128.3(18) . . ?
C9 N2 H2 120.8(18) . . ?
N1 C1 C10 121.59(15) . 2_655 ?
N1 C1 C2 110.22(15) . . ?
C10 C1 C2 127.61(15) 2_655 . ?
C3 C2 C1 106.49(14) . . ?
C3 C2 C24 127.24(16) . . ?
C1 C2 C24 125.67(16) . . ?
C2 C3 C4 105.90(15) . . ?
C2 C3 C23 125.32(16) . . ?
C4 C3 C23 127.85(16) . . ?
N1 C4 C5 120.87(15) . . ?
N1 C4 C3 109.96(14) . . ?
C5 C4 C3 128.46(15) . . ?
C6 C5 C4 122.04(15) . . ?
C6 C5 C17 118.86(15) . . ?
C4 C5 C17 118.55(14) . . ?
N2 C6 C5 125.09(16) . . ?
N2 C6 C7 106.64(14) . . ?
C5 C6 C7 128.19(16) . . ?
C8 C7 C6 108.05(16) . . ?
C8 C7 H7 126.8(15) . . ?
C6 C7 H7 125.2(15) . . ?
C7 C8 C9 108.28(15) . . ?
C7 C8 H8 125.7(14) . . ?
C9 C8 H8 125.9(14) . . ?
N2 C9 C10 125.06(16) . . ?
N2 C9 C8 106.39(14) . . ?
C10 C9 C8 128.54(15) . . ?
C9 C10 C1 122.77(15) . 2_655 ?
C9 C10 C11 118.32(15) . . ?
C1 C10 C11 118.25(14) 2_655 . ?
C16 C11 C12 119.03(16) . . ?
C16 C11 C10 122.96(16) . . ?
C12 C11 C10 117.98(16) . . ?
C13 C12 C11 120.64(19) . . ?
C13 C12 H12 119.8(15) . . ?
C11 C12 H12 119.5(15) . . ?
C14 C13 C12 119.78(19) . . ?
C14 C13 H13 119.2(17) . . ?
C12 C13 H13 121.0(17) . . ?
C15 C14 C13 120.10(17) . . ?
C15 C14 H14 117.6(16) . . ?
C13 C14 H14 122.3(16) . . ?
C14 C15 C16 120.6(2) . . ?
C14 C15 H15 121.4(15) . . ?
C16 C15 H15 118.1(15) . . ?
C11 C16 C15 119.86(18) . . ?
C11 C16 H16 122.9(15) . . ?
C15 C16 H16 117.3(15) . . ?
C22 C17 C18 118.67(16) . . ?
C22 C17 C5 118.56(16) . . ?
C18 C17 C5 122.77(15) . . ?
C19 C18 C17 120.46(16) . . ?
C19 C18 H18 118.1(13) . . ?
C17 C18 H18 121.5(13) . . ?
C20 C19 C18 120.27(17) . . ?
C20 C19 H19 119.1(14) . . ?
C18 C19 H19 120.6(14) . . ?
C21 C20 C19 119.77(16) . . ?
C21 C20 H20 119.6(16) . . ?
C19 C20 H20 120.4(16) . . ?
C20 C21 C22 120.20(17) . . ?
C20 C21 H21 125.9(18) . . ?
C22 C21 H21 113.8(18) . . ?
C21 C22 C17 120.63(17) . . ?
C21 C22 H22 121.7(17) . . ?
C17 C22 H22 117.6(17) . . ?
F2 C23 F3 108.64(18) . . ?
F2 C23 F1 104.25(17) . . ?
F3 C23 F1 105.86(17) . . ?
F2 C23 C3 114.49(15) . . ?
F3 C23 C3 112.24(16) . . ?
F1 C23 C3 110.73(17) . . ?
F4 C24 F5 107.44(16) . . ?
F4 C24 F6 105.44(16) . . ?
F5 C24 F6 106.08(16) . . ?
F4 C24 C2 113.06(16) . . ?
F5 C24 C2 112.63(16) . . ?
F6 C24 C2 111.68(15) . . ?
C2S C1S C6S 120.7(5) . . ?
C2S C1S H1S 119.6 . . ?
C6S C1S H1S 119.6 . . ?
C3S C2S C1S 121.8(5) . . ?
C3S C2S H2S 119.1 . . ?
C1S C2S H2S 119.1 . . ?
C2S C3S C4S 117.7(7) . . ?
C2S C3S H3S 121.2 . . ?
C4S C3S H3S 121.2 . . ?
C5S C4S C3S 122.0(7) . . ?
C5S C4S H4S 119.0 . . ?
C3S C4S H4S 119.0 . . ?
C4S C5S C6S 120.4(6) . . ?
C4S C5S H5S 119.8 . . ?
C6S C5S H5S 119.8 . . ?
C5S C6S C1S 117.4(5) . . ?
C5S C6S C7S 121.7(7) . . ?
C1S C6S C7S 120.9(6) . . ?
C6S C7S H7SA 109.5 . . ?
C6S C7S H7SB 109.5 . . ?
H7SA C7S H7SB 109.5 . . ?
C6S C7S H7SC 109.5 . . ?
H7SA C7S H7SC 109.5 . . ?
H7SB C7S H7SC 109.5 . . ?
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
_geom_bond_publ_flag
F1 C23 1.341(3) . ?
F2 C23 1.322(2) . ?
F3 C23 1.329(2) . ?
F4 C24 1.329(2) . ?
F5 C24 1.334(2) . ?
F6 C24 1.341(2) . ?
N1 C1 1.357(2) . ?
N1 C4 1.358(2) . ?
N2 C6 1.368(2) . ?
N2 C9 1.372(2) . ?
N2 H2 0.92(3) . ?
C1 C10 1.421(2) 2_655 ?
C1 C2 1.450(2) . ?
C2 C3 1.367(2) . ?
C2 C24 1.501(2) . ?
C3 C4 1.462(2) . ?
C3 C23 1.507(3) . ?
C4 C5 1.425(2) . ?
C5 C6 1.400(2) . ?
C5 C17 1.475(2) . ?
C6 C7 1.430(2) . ?
C7 C8 1.362(2) . ?
C7 H7 0.90(2) . ?
C8 C9 1.430(2) . ?
C8 H8 0.99(2) . ?
C9 C10 1.396(2) . ?
C10 C1 1.421(2) 2_655 ?
C10 C11 1.487(2) . ?
C11 C16 1.392(3) . ?
C11 C12 1.401(2) . ?
C12 C13 1.389(3) . ?
C12 H12 1.03(3) . ?
C13 C14 1.384(3) . ?
C13 H13 0.93(3) . ?
C14 C15 1.382(3) . ?
C14 H14 1.04(3) . ?
C15 C16 1.394(3) . ?
C15 H15 0.98(3) . ?
C16 H16 0.95(3) . ?
C17 C22 1.397(2) . ?
C17 C18 1.397(2) . ?
C18 C19 1.388(2) . ?
C18 H18 1.00(2) . ?
C19 C20 1.388(3) . ?
C19 H19 0.98(2) . ?
C20 C21 1.383(3) . ?
C20 H20 0.90(3) . ?
C21 C22 1.388(2) . ?
C21 H21 0.89(3) . ?
C22 H22 0.91(3) . ?
C1S C2S 1.392(8) . ?
C1S C6S 1.394(8) . ?
C1S H1S 0.9500 . ?
C2S C3S 1.326(10) . ?
C2S H2S 0.9500 . ?
C3S C4S 1.412(7) . ?
C3S H3S 0.9500 . ?
C4S C5S 1.354(8) . ?
C4S H4S 0.9500 . ?
C5S C6S 1.388(7) . ?
C5S H5S 0.9500 . ?
C6S C7S 1.468(11) . ?
C7S H7SA 0.9800 . ?
C7S H7SB 0.9800 . ?
C7S H7SC 0.9800 . ?
loop_
_geom_hbond_atom_site_label_D
_geom_hbond_atom_site_label_H
_geom_hbond_atom_site_label_A
_geom_hbond_distance_DH
_geom_hbond_distance_HA
_geom_hbond_distance_DA
_geom_hbond_angle_DHA
_geom_hbond_site_symmetry_A
N2 H2 N1 0.92(3) 2.42(3) 2.894(2) 112(2) .
N2 H2 N1 0.92(3) 2.34(3) 2.909(2) 120(2) 2_655
