#------------------------------------------------------------------------------
#$Date: 2019-11-23 12:00:23 +0200 (Sat, 23 Nov 2019) $
#$Revision: 233203 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/34/86/4348632.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_4348632
loop_
_publ_author_name
'Yamashita, Ken-Ichi'
'Sakata, Naoya'
'Ogawa, Takuji'
_publ_section_title
;
 Systematic Structural Elucidation for the Protonated Form of Rare Earth
 Bis(porphyrinato) Double-Decker Complexes: Direct Structural Evidence of
 the Location of the Attached Proton.
;
_journal_issue                   17
_journal_name_full               'Inorganic chemistry'
_journal_page_first              8935
_journal_page_last               8942
_journal_paper_doi               10.1021/acs.inorgchem.6b01442
_journal_volume                  55
_journal_year                    2016
_chemical_formula_sum            'C95 H73 N8 O2 Tb'
_chemical_formula_weight         1517.53
_space_group_crystal_system      orthorhombic
_space_group_IT_number           70
_space_group_name_Hall           '-F 2uv 2vw'
_space_group_name_H-M_alt        'F d d d :2'
_atom_sites_solution_hydrogens   geom
_audit_creation_method           SHELXL-2014/7
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   21.762(4)
_cell_length_b                   22.083(4)
_cell_length_c                   30.280(6)
_cell_measurement_reflns_used    14007
_cell_measurement_temperature    123(2)
_cell_measurement_theta_max      27.50
_cell_measurement_theta_min      3
_cell_volume                     14552(5)
_computing_cell_refinement       'Rigaku RAPID AUTO'
_computing_data_collection       'Rigaku RAPID AUTO'
_computing_data_reduction        'Rigaku RAPID AUTO'
_computing_molecular_graphics    'Bruker XSHELL'
_computing_publication_material  'CIFTAB-2014/2 (Sheldrick, 2014)'
_computing_structure_refinement  'SHELXL-2014/7 (Sheldrick, 2014)'
_computing_structure_solution    'SHELXT-2014/6 (Sheldrick, 2014)'
_diffrn_ambient_temperature      123(2)
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Rigaku FR-E+ SuperBright'
_diffrn_measurement_method       'profile data from ω-scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0625
_diffrn_reflns_av_unetI/netI     0.0460
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            34853
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.482
_diffrn_reflns_theta_min         2.998
_diffrn_source                   'Rotating anode X-ray tube'
_exptl_absorpt_coefficient_mu    1.031
_exptl_absorpt_correction_T_max  0.9998
_exptl_absorpt_correction_T_min  0.8893
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            purple
_exptl_crystal_density_diffrn    1.385
_exptl_crystal_description       block
_exptl_crystal_F_000             6240
_exptl_crystal_size_max          0.050
_exptl_crystal_size_mid          0.040
_exptl_crystal_size_min          0.020
_refine_diff_density_max         0.365
_refine_diff_density_min         -0.624
_refine_diff_density_rms         0.059
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.985
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     220
_refine_ls_number_reflns         4180
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.985
_refine_ls_R_factor_all          0.0700
_refine_ls_R_factor_gt           0.0456
_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)+(0.0581P)²+8.9205P] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0936
_refine_ls_wR_factor_ref         0.1014
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3203
_reflns_number_total             4180
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            ic6b01442_si_002.cif
_cod_data_source_block           TbTHF
_cod_original_sg_symbol_H-M      'F d d d'
_cod_database_code               4348632
_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   0.950
_shelx_estimated_absorpt_t_max   0.980
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-x+3/4, -y+3/4, z'
'-x+3/4, y, -z+3/4'
'x, -y+3/4, -z+3/4'
'x, y+1/2, z+1/2'
'-x+3/4, -y+5/4, z+1/2'
'-x+3/4, y+1/2, -z+5/4'
'x, -y+5/4, -z+5/4'
'x+1/2, y, z+1/2'
'-x+5/4, -y+3/4, z+1/2'
'-x+5/4, y, -z+5/4'
'x+1/2, -y+3/4, -z+5/4'
'x+1/2, y+1/2, z'
'-x+5/4, -y+5/4, z'
'-x+5/4, y+1/2, -z+3/4'
'x+1/2, -y+5/4, -z+3/4'
'-x, -y, -z'
'x-3/4, y-3/4, -z'
'x-3/4, -y, z-3/4'
'-x, y-3/4, z-3/4'
'-x, -y+1/2, -z+1/2'
'x-3/4, y-1/4, -z+1/2'
'x-3/4, -y+1/2, z-1/4'
'-x, y-1/4, z-1/4'
'-x+1/2, -y, -z+1/2'
'x-1/4, y-3/4, -z+1/2'
'x-1/4, -y, z-1/4'
'-x+1/2, y-3/4, z-1/4'
'-x+1/2, -y+1/2, -z'
'x-1/4, y-1/4, -z'
'x-1/4, -y+1/2, z-3/4'
'-x+1/2, y-1/4, z-3/4'
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
Tb1 Tb 0.1250 0.6250 0.6250 0.04663(13) Uani 1 4 d S T P
N1 N 0.15233(10) 0.71323(10) 0.67401(8) 0.0368(5) Uani 1 1 d . . .
N2 N 0.21585(10) 0.59695(10) 0.67335(8) 0.0410(6) Uani 1 1 d . . .
C1 C 0.11409(12) 0.76174(13) 0.68252(9) 0.0389(7) Uani 1 1 d . . .
C2 C 0.14875(14) 0.81056(13) 0.70138(11) 0.0465(7) Uani 1 1 d . . .
H2 H 0.1331 0.8489 0.7100 0.056 Uiso 1 1 calc R U .
C3 C 0.20670(15) 0.79238(13) 0.70453(11) 0.0485(8) Uani 1 1 d . . .
H3 H 0.2400 0.8152 0.7161 0.058 Uiso 1 1 calc R U .
C4 C 0.20982(13) 0.73146(12) 0.68722(9) 0.0394(7) Uani 1 1 d . . .
C5 C 0.26361(13) 0.69672(13) 0.68695(10) 0.0417(7) Uani 1 1 d . . .
C6 C 0.26595(14) 0.63439(13) 0.67932(10) 0.0440(7) Uani 1 1 d . . .
C7 C 0.32019(14) 0.59792(14) 0.68091(11) 0.0482(8) Uani 1 1 d . . .
H7 H 0.3611 0.6123 0.6838 0.058 Uiso 1 1 calc R U .
C8 C 0.30302(13) 0.53941(14) 0.67755(11) 0.0471(7) Uani 1 1 d . . .
H8 H 0.3296 0.5053 0.6772 0.057 Uiso 1 1 calc R U .
C9 C 0.23747(13) 0.53823(12) 0.67455(10) 0.0403(7) Uani 1 1 d . . .
C10 C 0.20000(13) 0.48677(12) 0.67817(9) 0.0389(7) Uani 1 1 d . . .
C11 C 0.32162(13) 0.72726(13) 0.70081(11) 0.0471(7) Uani 1 1 d . . .
C12 C 0.34831(16) 0.71299(17) 0.74110(13) 0.0653(10) Uani 1 1 d . . .
H12 H 0.3303 0.6826 0.7591 0.078 Uiso 1 1 calc R U .
C13 C 0.40014(19) 0.7422(2) 0.75517(17) 0.0858(13) Uani 1 1 d . . .
H13 H 0.4176 0.7319 0.7829 0.103 Uiso 1 1 calc R U .
C14 C 0.42722(18) 0.7859(2) 0.72983(19) 0.0895(14) Uani 1 1 d . . .
H14 H 0.4636 0.8054 0.7397 0.107 Uiso 1 1 calc R U .
C15 C 0.4016(2) 0.80123(19) 0.69042(17) 0.0807(13) Uani 1 1 d . . .
H15 H 0.4200 0.8320 0.6729 0.097 Uiso 1 1 calc R U .
C16 C 0.34849(17) 0.77222(17) 0.67543(13) 0.0649(10) Uani 1 1 d . . .
H16 H 0.3309 0.7833 0.6479 0.078 Uiso 1 1 calc R U .
C17 C 0.23010(14) 0.42602(13) 0.68089(10) 0.0422(7) Uani 1 1 d . . .
C18 C 0.27198(14) 0.41157(14) 0.71382(11) 0.0505(8) Uani 1 1 d . . .
H18 H 0.2826 0.4411 0.7353 0.061 Uiso 1 1 calc R U .
C19 C 0.29853(16) 0.35427(17) 0.71559(14) 0.0636(10) Uani 1 1 d . . .
H19 H 0.3273 0.3448 0.7382 0.076 Uiso 1 1 calc R U .
C20 C 0.28314(18) 0.31143(16) 0.68461(15) 0.0733(12) Uani 1 1 d . . .
H20 H 0.3013 0.2723 0.6858 0.088 Uiso 1 1 calc R U .
C21 C 0.2417(2) 0.32496(16) 0.65217(14) 0.0707(11) Uani 1 1 d . . .
H21 H 0.2313 0.2953 0.6307 0.085 Uiso 1 1 calc R U .
C22 C 0.21492(18) 0.38171(14) 0.65044(12) 0.0572(9) Uani 1 1 d . . .
H22 H 0.1857 0.3904 0.6280 0.069 Uiso 1 1 calc R U .
loop_
_atom_type_symbol
_atom_type_description
_atom_type_scat_dispersion_real
_atom_type_scat_dispersion_imag
_atom_type_scat_source
C C 0.0033 0.0016 '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 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Tb Tb -0.1723 4.1537 '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
N1 Tb1 N1 152.70(10) . 8
N1 Tb1 N1 107.85(10) . 14_455
N1 Tb1 N1 78.74(10) 8 14_455
N1 Tb1 N1 78.74(10) . 11_455
N1 Tb1 N1 107.85(10) 8 11_455
N1 Tb1 N1 152.70(10) 14_455 11_455
N1 Tb1 N2 135.43(7) . 11_455
N1 Tb1 N2 69.84(8) 8 11_455
N1 Tb1 N2 88.12(8) 14_455 11_455
N1 Tb1 N2 70.43(7) 11_455 11_455
N1 Tb1 N2 70.43(7) . .
N1 Tb1 N2 88.12(8) 8 .
N1 Tb1 N2 69.84(8) 14_455 .
N1 Tb1 N2 135.43(7) 11_455 .
N2 Tb1 N2 151.74(10) 11_455 .
N1 Tb1 N2 88.12(8) . 8
N1 Tb1 N2 70.43(7) 8 8
N1 Tb1 N2 135.43(7) 14_455 8
N1 Tb1 N2 69.84(8) 11_455 8
N2 Tb1 N2 109.51(11) 11_455 8
N2 Tb1 N2 77.60(11) . 8
N1 Tb1 N2 69.84(8) . 14_455
N1 Tb1 N2 135.43(7) 8 14_455
N1 Tb1 N2 70.43(7) 14_455 14_455
N1 Tb1 N2 88.12(8) 11_455 14_455
N2 Tb1 N2 77.60(11) 11_455 14_455
N2 Tb1 N2 109.51(11) . 14_455
N2 Tb1 N2 151.74(10) 8 14_455
C4 N1 C1 105.5(2) . .
C4 N1 Tb1 127.79(17) . .
C1 N1 Tb1 124.57(18) . .
C9 N2 C6 106.9(2) . .
C9 N2 Tb1 120.68(18) . .
C6 N2 Tb1 123.02(18) . .
N1 C1 C10 126.9(3) . 14_455
N1 C1 C2 109.9(2) . .
C10 C1 C2 122.9(3) 14_455 .
C3 C2 C1 107.5(3) . .
C3 C2 H2 126.2 . .
C1 C2 H2 126.2 . .
C2 C3 C4 107.5(3) . .
C2 C3 H3 126.3 . .
C4 C3 H3 126.3 . .
N1 C4 C5 126.8(2) . .
N1 C4 C3 109.6(2) . .
C5 C4 C3 123.5(3) . .
C4 C5 C6 124.9(3) . .
C4 C5 C11 117.3(2) . .
C6 C5 C11 117.5(3) . .
N2 C6 C5 125.7(3) . .
N2 C6 C7 108.6(2) . .
C5 C6 C7 125.4(3) . .
C8 C7 C6 108.0(3) . .
C8 C7 H7 126.0 . .
C6 C7 H7 126.0 . .
C7 C8 C9 107.4(3) . .
C7 C8 H8 126.3 . .
C9 C8 H8 126.3 . .
N2 C9 C10 124.4(3) . .
N2 C9 C8 108.9(2) . .
C10 C9 C8 126.1(3) . .
C9 C10 C1 124.5(3) . 14_455
C9 C10 C17 118.5(2) . .
C1 C10 C17 116.9(3) 14_455 .
C16 C11 C12 118.3(3) . .
C16 C11 C5 121.7(3) . .
C12 C11 C5 119.9(3) . .
C13 C12 C11 120.8(4) . .
C13 C12 H12 119.6 . .
C11 C12 H12 119.6 . .
C12 C13 C14 120.9(4) . .
C12 C13 H13 119.5 . .
C14 C13 H13 119.5 . .
C13 C14 C15 119.5(4) . .
C13 C14 H14 120.3 . .
C15 C14 H14 120.3 . .
C16 C15 C14 120.7(4) . .
C16 C15 H15 119.7 . .
C14 C15 H15 119.7 . .
C11 C16 C15 119.8(4) . .
C11 C16 H16 120.1 . .
C15 C16 H16 120.1 . .
C22 C17 C18 118.2(3) . .
C22 C17 C10 119.5(3) . .
C18 C17 C10 122.2(3) . .
C19 C18 C17 120.6(3) . .
C19 C18 H18 119.7 . .
C17 C18 H18 119.7 . .
C20 C19 C18 119.9(3) . .
C20 C19 H19 120.1 . .
C18 C19 H19 120.1 . .
C19 C20 C21 120.1(3) . .
C19 C20 H20 120.0 . .
C21 C20 H20 120.0 . .
C22 C21 C20 120.2(4) . .
C22 C21 H21 119.9 . .
C20 C21 H21 119.9 . .
C21 C22 C17 121.0(4) . .
C21 C22 H22 119.5 . .
C17 C22 H22 119.5 . .
loop_
_geom_bond_atom_site_label_1
_geom_bond_atom_site_label_2
_geom_bond_distance
_geom_bond_site_symmetry_2
Tb1 N1 2.520(2) .
Tb1 N1 2.520(2) 8
Tb1 N1 2.520(2) 14_455
Tb1 N1 2.520(2) 11_455
Tb1 N2 2.537(2) 11_455
Tb1 N2 2.537(2) .
Tb1 N2 2.537(2) 8
Tb1 N2 2.537(2) 14_455
N1 C4 1.374(4) .
N1 C1 1.381(3) .
N2 C9 1.380(3) .
N2 C6 1.380(4) .
C1 C10 1.401(4) 14_455
C1 C2 1.434(4) .
C2 C3 1.327(4) .
C2 H2 0.9500 .
C3 C4 1.446(4) .
C3 H3 0.9500 .
C4 C5 1.400(4) .
C5 C6 1.396(4) .
C5 C11 1.491(4) .
C6 C7 1.430(4) .
C7 C8 1.349(4) .
C7 H7 0.9500 .
C8 C9 1.430(4) .
C8 H8 0.9500 .
C9 C10 1.403(4) .
C10 C1 1.401(4) 14_455
C10 C17 1.495(4) .
C11 C16 1.385(5) .
C11 C12 1.387(5) .
C12 C13 1.367(5) .
C12 H12 0.9500 .
C13 C14 1.367(6) .
C13 H13 0.9500 .
C14 C15 1.360(6) .
C14 H14 0.9500 .
C15 C16 1.397(5) .
C15 H15 0.9500 .
C16 H16 0.9500 .
C17 C22 1.384(4) .
C17 C18 1.388(4) .
C18 C19 1.392(5) .
C18 H18 0.9500 .
C19 C20 1.374(6) .
C19 H19 0.9500 .
C20 C21 1.366(6) .
C20 H20 0.9500 .
C21 C22 1.383(5) .
C21 H21 0.9500 .
C22 H22 0.9500 .
loop_
_geom_torsion_atom_site_label_1
_geom_torsion_atom_site_label_2
_geom_torsion_atom_site_label_3
_geom_torsion_atom_site_label_4
_geom_torsion
_geom_torsion_site_symmetry_1
_geom_torsion_site_symmetry_4
C4 N1 C1 C10 -174.1(3) . 14_455
Tb1 N1 C1 C10 21.5(4) . 14_455
C4 N1 C1 C2 -0.1(3) . .
Tb1 N1 C1 C2 -164.58(19) . .
N1 C1 C2 C3 -0.2(4) . .
C10 C1 C2 C3 174.0(3) 14_455 .
C1 C2 C3 C4 0.5(4) . .
C1 N1 C4 C5 176.9(3) . .
Tb1 N1 C4 C5 -19.3(4) . .
C1 N1 C4 C3 0.4(3) . .
Tb1 N1 C4 C3 164.22(19) . .
C2 C3 C4 N1 -0.6(4) . .
C2 C3 C4 C5 -177.3(3) . .
N1 C4 C5 C6 -10.2(5) . .
C3 C4 C5 C6 165.9(3) . .
N1 C4 C5 C11 177.0(3) . .
C3 C4 C5 C11 -6.9(4) . .
C9 N2 C6 C5 -169.8(3) . .
Tb1 N2 C6 C5 43.8(4) . .
C9 N2 C6 C7 4.4(3) . .
Tb1 N2 C6 C7 -142.0(2) . .
C4 C5 C6 N2 -3.8(5) . .
C11 C5 C6 N2 168.9(3) . .
C4 C5 C6 C7 -177.0(3) . .
C11 C5 C6 C7 -4.3(5) . .
N2 C6 C7 C8 -2.1(4) . .
C5 C6 C7 C8 172.0(3) . .
C6 C7 C8 C9 -1.0(4) . .
C6 N2 C9 C10 167.3(3) . .
Tb1 N2 C9 C10 -45.4(4) . .
C6 N2 C9 C8 -5.0(3) . .
Tb1 N2 C9 C8 142.4(2) . .
C7 C8 C9 N2 3.7(4) . .
C7 C8 C9 C10 -168.3(3) . .
N2 C9 C10 C1 -2.2(5) . 14_455
C8 C9 C10 C1 168.7(3) . 14_455
N2 C9 C10 C17 -177.6(3) . .
C8 C9 C10 C17 -6.7(4) . .
C4 C5 C11 C16 -68.5(4) . .
C6 C5 C11 C16 118.2(4) . .
C4 C5 C11 C12 108.2(3) . .
C6 C5 C11 C12 -65.1(4) . .
C16 C11 C12 C13 -0.6(6) . .
C5 C11 C12 C13 -177.4(4) . .
C11 C12 C13 C14 -0.4(7) . .
C12 C13 C14 C15 1.1(7) . .
C13 C14 C15 C16 -0.8(7) . .
C12 C11 C16 C15 0.9(5) . .
C5 C11 C16 C15 177.6(3) . .
C14 C15 C16 C11 -0.2(6) . .
C9 C10 C17 C22 -123.7(3) . .
C1 C10 C17 C22 60.6(4) 14_455 .
C9 C10 C17 C18 58.0(4) . .
C1 C10 C17 C18 -117.7(3) 14_455 .
C22 C17 C18 C19 0.9(5) . .
C10 C17 C18 C19 179.2(3) . .
C17 C18 C19 C20 -0.2(5) . .
C18 C19 C20 C21 -0.2(6) . .
C19 C20 C21 C22 -0.3(6) . .
C20 C21 C22 C17 1.0(6) . .
C18 C17 C22 C21 -1.4(5) . .
C10 C17 C22 C21 -179.7(3) . .
