#------------------------------------------------------------------------------
#$Date: 2021-02-26 00:15:11 +0200 (Fri, 26 Feb 2021) $
#$Revision: 262236 $
#$URL: file:///home/coder/svn-repositories/cod/cif/4/51/85/4518503.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_4518503
loop_
_publ_author_name
'Wang, Yefei'
'Zhou, Zhen'
'Zhao, Liang'
'He, Cheng'
'Sun, Wenlong'
'Duan, Chunying'
_publ_section_title
;
 Ir-Porphyrin-Based Metal-Organic Framework as a Dual Metallo- and
 Photocatalyst for Inert Alkyl C(sp³)-H Bond Activation
 and Direct Functionalization.
;
_journal_name_full               'ACS applied materials & interfaces'
_journal_paper_doi               10.1021/acsami.0c22276
_journal_year                    2021
_chemical_formula_sum            'C174 H167 Cl Ir3 N18 Ni6 O56'
_chemical_formula_weight         4370.56
_space_group_crystal_system      hexagonal
_space_group_IT_number           191
_space_group_name_Hall           '-P 6 2'
_space_group_name_H-M_alt        'P 6/m m m'
_atom_sites_solution_hydrogens   mixed
_audit_creation_method           SHELXL-2014
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            1
_cell_length_a                   31.670(4)
_cell_length_b                   31.670(4)
_cell_length_c                   16.727(4)
_cell_measurement_reflns_used    9838
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      27.593
_cell_measurement_theta_min      2.311
_cell_volume                     14529(4)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Bruker SHELXTL'
_computing_publication_material  'Bruker SHELXTL'
_computing_structure_refinement  'SHELXL-2014 (Sheldrick 2014)'
_computing_structure_solution    'SHELXL-2014 (Sheldrick 2014)'
_diffrn_ambient_temperature      200(2)
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.988
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       'φ and ω scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1477
_diffrn_reflns_av_unetI/netI     0.2843
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       37
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       37
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       19
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            79422
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         24.998
_diffrn_reflns_theta_min         2.311
_exptl_absorpt_coefficient_mu    0.906
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    0.500
_exptl_crystal_description       block
_exptl_crystal_F_000             2201
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.150
_exptl_crystal_size_min          0.100
_refine_diff_density_max         0.938
_refine_diff_density_min         -3.034
_refine_diff_density_rms         0.099
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.913
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     162
_refine_ls_number_reflns         4792
_refine_ls_number_restraints     122
_refine_ls_restrained_S_all      0.911
_refine_ls_R_factor_all          0.2133
_refine_ls_R_factor_gt           0.1399
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[σ²(Fo²)+(0.1000P)²] where P=(Fo²+2Fc²)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2936
_refine_ls_wR_factor_ref         0.3241
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1534
_reflns_number_total             4792
_reflns_threshold_expression     'I > 2σ(I)'
_cod_data_source_file            am0c22276_si_002.cif
_cod_data_source_block           Ni-TCPP(Ir)@carbene
_cod_original_cell_volume        14529(5)
_cod_database_code               4518503
_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   0.840
_shelx_estimated_absorpt_t_max   0.915
_shelxl_version_number           2014-3
_platon_squeeze_void_probe_radius 1.20
loop_
_space_group_symop_operation_xyz
'x, y, z'
'-y, x-y, z'
'-x+y, -x, z'
'-x, -y, z'
'y, -x+y, z'
'x-y, x, z'
'y, x, -z'
'x-y, -y, -z'
'-x, -x+y, -z'
'-y, -x, -z'
'-x+y, y, -z'
'x, x-y, -z'
'-x, -y, -z'
'y, -x+y, -z'
'x-y, x, -z'
'x, y, -z'
'-y, x-y, -z'
'-x+y, -x, -z'
'-y, -x, z'
'-x+y, y, z'
'x, x-y, z'
'y, x, z'
'x-y, -y, z'
'-x, -x+y, z'
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
Ir1 Ir 0.5000 0.5000 0.5000 0.1354(2) Uani 1 8 d S T P . .
Ni1 Ni 0.40969(11) 0.70485(5) 1.0000 0.1080(7) Uani 1 4 d DS T P D .
N1 N 0.5000 0.5000 0.6214(5) 0.101(2) Uani 1 4 d S T P A .
N2 N 0.46610(16) 0.53390(16) 0.5000 0.061(2) Uani 1 4 d S T P A .
O1 O 0.4103(2) 0.6610(2) 0.9107(4) 0.141(3) Uani 1 1 d . . . . .
O2 O 0.3333 0.6667 1.0000 0.037(3) Uani 1 12 d S T P . .
H2A H 0.3333 0.6667 1.0508 0.044 Uiso 0.5 6 d R U P . .
C1 C 0.48902(19) 0.51098(19) 0.7516(7) 0.165(4) Uani 1 2 d S T P A .
H1A H 0.4785 0.5215 0.7967 0.198 Uiso 1 2 calc R U P . .
C2 C 0.4822(2) 0.5178(2) 0.6691(6) 0.133(4) Uani 1 2 d S T P . .
C3 C 0.4561(2) 0.5439(2) 0.6473(10) 0.154(5) Uani 1 2 d S T P A .
C4 C 0.44932(18) 0.55068(18) 0.5599(7) 0.139(4) Uani 1 2 d DS T P . .
C5 C 0.42238(18) 0.57762(18) 0.5382(3) 0.153(6) Uani 1 2 d DS T P A .
H5A H 0.4087 0.5913 0.5733 0.184 Uiso 1 2 calc R U P . .
C6 C 0.4380(3) 0.5620(3) 0.7080(8) 0.126(4) Uani 1 2 d S TU P . .
C7 C 0.4639(4) 0.6077(4) 0.7291(6) 0.150(4) Uani 1 1 d . . . . .
H7A H 0.4915 0.6294 0.6983 0.180 Uiso 1 1 calc R U . . .
C8 C 0.4502(3) 0.6262(3) 0.8024(7) 0.206(4) Uani 1 1 d . . . . .
H8A H 0.4732 0.6545 0.8306 0.248 Uiso 1 1 calc R U . . .
C9 C 0.4012(2) 0.5988(2) 0.8258(7) 0.108(3) Uani 1 2 d S T P . .
C10 C 0.3870(3) 0.6130(3) 0.8949(8) 0.181(6) Uani 1 2 d S T P . .
C11 C 0.4131(4) 0.4262(5) 0.5000 0.064(6) Uani 0.25 2 d DS TU P A 1
C12 C 0.3579(4) 0.4056(3) 0.5000 0.071(5) Uani 0.25 2 d DS TU P A 1
O11 O 0.3251(5) 0.3564(4) 0.5000 0.105(6) Uani 0.25 2 d DS TU P A 1
O12 O 0.3423(3) 0.4448(3) 0.5000 0.087(5) Uani 0.25 2 d DS TU P A 1
C13 C 0.2877(3) 0.4284(7) 0.5000 0.050(5) Uani 0.25 2 d DS TU P A 1
H13A H 0.2803 0.4063 0.5464 0.059 Uiso 0.125 1 calc R U P A 1
H13B H 0.2803 0.4063 0.4536 0.059 Uiso 0.125 1 calc R U P A 1
C14 C 0.2372(4) 0.4245(6) 0.5000 0.027(4) Uani 0.25 2 d DS TU P A 1
H14A H 0.2117 0.3901 0.5000 0.040 Uiso 0.25 2 calc R U P A 1
H14B H 0.2339 0.4405 0.5478 0.040 Uiso 0.125 1 calc R U P A 1
H14C H 0.2339 0.4405 0.4522 0.040 Uiso 0.125 1 calc R U P A 1
O1W O 0.3793(6) 0.4455(6) 0.5000 0.114(5) Uiso 0.5 2 d S . P B 2
H1WB H 0.3697 0.4652 0.4862 0.171 Uiso 0.25 1 d R U P B 2
H1WC H 0.3959 0.4430 0.4623 0.171 Uiso 0.25 1 d R U P B 2
O2W O 0.1347(3) 0.1347(3) 0.0000 0.095(3) Uiso 1 4 d S . P C 1
H2WA H 0.1050 0.1225 -0.0127 0.142 Uiso 0.25 1 d R U P C 1
H2WB H 0.1526 0.1464 -0.0408 0.142 Uiso 0.25 1 d R U P C 1
N3 N 0.55466(18) 0.73652(18) 1.0000 0.265(6) Uiso 0.5 2 d DS U P . .
O14 O 0.4821(3) 0.74106(14) 1.0000 0.237(5) Uiso 1 4 d DS U P . .
C16 C 0.5309(3) 0.76545(14) 1.0000 0.251(6) Uiso 0.5 4 d DS U P D 1
H16A H 0.5508 0.7974 1.0000 0.301 Uiso 0.25 2 d R U P D 1
C17 C 0.5259(4) 0.6836(2) 1.0000 0.258(10) Uiso 0.25 2 d DS U P D 1
H17A H 0.4923 0.6753 1.0000 0.387 Uiso 0.25 2 d R U P D 1
H17B H 0.5324 0.6703 0.9531 0.387 Uiso 0.125 1 d R U P D 1
H17C H 0.5324 0.6703 1.0469 0.387 Uiso 0.125 1 d R U P D 1
C18 C 0.6077(2) 0.7605(4) 1.0000 0.247(11) Uiso 0.25 2 d DS U P D 1
H18A H 0.6142 0.7339 1.0000 0.370 Uiso 0.25 2 d R U P D 1
H18B H 0.6217 0.7801 0.9531 0.370 Uiso 0.125 1 d R U P D 1
H18C H 0.6217 0.7801 1.0469 0.370 Uiso 0.125 1 d R U P D 1
C16' C 0.5016(2) 0.7080(4) 1.0000 0.251(6) Uiso 0.25 2 d DS U P D 2
H16B H 0.4796 0.6734 1.0000 0.301 Uiso 0.25 2 d R U P D 2
C17' C 0.5831(3) 0.7122(3) 1.0000 0.263(11) Uiso 0.25 2 d DS U P D 2
H17D H 0.5598 0.6779 1.0000 0.395 Uiso 0.25 2 d R U P D 2
H17E H 0.6032 0.7202 0.9531 0.395 Uiso 0.125 1 d R U P D 2
H17F H 0.6032 0.7202 1.0469 0.395 Uiso 0.125 1 d R U P D 2
C18' C 0.5786(4) 0.7893(2) 1.0000 0.261(6) Uiso 0.5 4 d DS U P D 2
H18D H 0.5548 0.7943 1.0000 0.392 Uiso 0.25 2 d R U P D 2
H18E H 0.5986 0.7993 1.0469 0.392 Uiso 0.25 2 d R U P D 2
H18F H 0.5986 0.7993 0.9531 0.392 Uiso 0.25 2 d R U P D 2
O3W O 0.0522(15) 0.0522(15) 0.5000 0.32(3) Uiso 0.5 4 d S . P E 1
H3WA H 0.0435 0.0517 0.5474 0.476 Uiso 0.125 1 d R U P E 1
H3WB H 0.0272 0.0475 0.4704 0.476 Uiso 0.125 1 d R U P E 1
O4W O 0.2476(13) 0.495(3) 0.5000 0.37(3) Uiso 0.5 4 d S . P F 4
H4WA H 0.2168 0.4769 0.5000 0.559 Uiso 0.25 2 d R U P F 4
H4WB H 0.2564 0.5129 0.5415 0.559 Uiso 0.25 2 d R U P F 4
Cl1 Cl 0.312(2) 0.481(2) 0.5000 0.19(2) Uiso 0.0833 2 d S . P G 3
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'
Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4'
Ir Ir -1.4442 7.9887 '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
N2 Ir1 N2 180.0 . 13_666 ?
N2 Ir1 N1 90.0 . 13_666 ?
N2 Ir1 N1 90.0 13_666 13_666 ?
N2 Ir1 N1 90.0 . . ?
N2 Ir1 N1 90.0 13_666 . ?
N1 Ir1 N1 180.0 13_666 . ?
N2 Ir1 C11 81.9(4) . . ?
N2 Ir1 C11 98.1(4) 13_666 . ?
N1 Ir1 C11 90.000(3) 13_666 . ?
N1 Ir1 C11 90.000(3) . . ?
N2 Ir1 C11 98.1(4) . 13_666 ?
N2 Ir1 C11 81.9(4) 13_666 13_666 ?
N1 Ir1 C11 90.000(3) 13_666 13_666 ?
N1 Ir1 C11 90.000(3) . 13_666 ?
C11 Ir1 C11 180.0 . 13_666 ?
N2 Ir1 C11 81.9(4) . 19_665 ?
N2 Ir1 C11 98.1(4) 13_666 19_665 ?
N1 Ir1 C11 90.000(3) 13_666 19_665 ?
N1 Ir1 C11 90.000(3) . 19_665 ?
C11 Ir1 C11 163.8(7) . 19_665 ?
C11 Ir1 C11 16.2(7) 13_666 19_665 ?
N2 Ir1 C11 98.1(4) . 7_556 ?
N2 Ir1 C11 81.9(4) 13_666 7_556 ?
N1 Ir1 C11 90.000(3) 13_666 7_556 ?
N1 Ir1 C11 90.000(3) . 7_556 ?
C11 Ir1 C11 16.2(7) . 7_556 ?
C11 Ir1 C11 163.8(7) 13_666 7_556 ?
C11 Ir1 C11 180.0 19_665 7_556 ?
O14 Ni1 O1 89.5(2) . 12_567 ?
O14 Ni1 O1 89.5(2) . 21_565 ?
O1 Ni1 O1 93.8(4) 12_567 21_565 ?
O14 Ni1 O1 89.5(2) . . ?
O1 Ni1 O1 179.1(4) 12_567 . ?
O1 Ni1 O1 86.2(4) 21_565 . ?
O14 Ni1 O1 89.5(2) . 16_557 ?
O1 Ni1 O1 86.2(4) 12_567 16_557 ?
O1 Ni1 O1 179.1(4) 21_565 16_557 ?
O1 Ni1 O1 93.8(4) . 16_557 ?
O14 Ni1 O2 180.0(2) . . ?
O1 Ni1 O2 90.5(2) 12_567 . ?
O1 Ni1 O2 90.5(2) 21_565 . ?
O1 Ni1 O2 90.5(2) . . ?
O1 Ni1 O2 90.5(2) 16_557 . ?
C2 N1 C2 101.5(12) . 4_665 ?
C2 N1 Ir1 129.3(6) . . ?
C2 N1 Ir1 129.3(6) 4_665 . ?
C4 N2 C4 94.8(10) . 16_556 ?
C4 N2 Ir1 132.6(5) . . ?
C4 N2 Ir1 132.6(5) 16_556 . ?
C10 O1 Ni1 136.5(7) . . ?
Ni1 O2 Ni1 120.001(1) . 2_665 ?
Ni1 O2 Ni1 119.999(1) . 3_565 ?
Ni1 O2 Ni1 120.000(1) 2_665 3_565 ?
C1 C1 C2 105.1(7) 4_665 . ?
N1 C2 C1 114.1(10) . . ?
N1 C2 C3 126.5(11) . . ?
C1 C2 C3 119.4(11) . . ?
N1 C2 C2 39.3(6) . 4_665 ?
C1 C2 C2 74.9(7) . 4_665 ?
C3 C2 C2 165.8(8) . 4_665 ?
C6 C3 C2 120.1(13) . . ?
C6 C3 C4 121.5(12) . . ?
C2 C3 C4 118.4(12) . . ?
N2 C4 C3 123.2(9) . . ?
N2 C4 C5 118.8(9) . . ?
C3 C4 C5 118.0(9) . . ?
N2 C4 C4 42.6(5) . 16_556 ?
C3 C4 C4 165.8(7) . 16_556 ?
C5 C4 C4 76.2(5) . 16_556 ?
C5 C5 C4 103.8(5) 16_556 . ?
C7 C6 C7 120.6(15) . 19_665 ?
C7 C6 C3 118.9(7) . . ?
C7 C6 C3 118.9(7) 19_665 . ?
C6 C7 C8 120.4(10) . . ?
C9 C8 C7 115.4(9) . . ?
C10 C9 C8 117.9(7) . 19_665 ?
C10 C9 C8 117.9(7) . . ?
C8 C9 C8 119.2(11) 19_665 . ?
O1 C10 O1 114.6(13) 19_665 . ?
O1 C10 C9 116.4(7) 19_665 . ?
O1 C10 C9 116.4(7) . . ?
C11 C11 C12 128.3(7) 7_556 . ?
C11 C11 Ir1 81.9(4) 7_556 . ?
C12 C11 Ir1 149.8(10) . . ?
O11 C12 C11 122.6(12) . . ?
O11 C12 O12 123.0(10) . . ?
C11 C12 O12 114.3(8) . . ?
C12 O11 O11 109.1(9) . 7_556 ?
C13 O12 C12 119.0(10) . . ?
O12 C13 C14 166.9(15) . . ?
C13 C14 C14 176.0(9) . 20 ?
C17' N3 C18' 120.5(6) . . ?
C16 N3 C17 120.4(7) . . ?
C16 N3 C18 119.9(6) . . ?
C17 N3 C18 119.7(8) . . ?
C17' N3 C16' 120.1(7) . . ?
C18' N3 C16' 119.4(7) . . ?
C16' O14 C16' 137.0(8) 21_565 . ?
C16 O14 Ni1 180.0 . . ?
C16' O14 Ni1 111.5(4) 21_565 . ?
C16' O14 Ni1 111.5(4) . . ?
O14 C16 N3 116.8(3) . . ?
O14 C16 N3 116.8(3) . 21_565 ?
N3 C16 N3 126.5(6) . 21_565 ?
N3 C16' O14 109.0(8) . . ?
N3 C18' N3 126.1(9) . 21_565 ?
O3W O3W O3W 120.000(4) 15_556 14_556 ?
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
Ir1 N2 1.859(9) . ?
Ir1 N2 1.859(9) 13_666 ?
Ir1 N1 2.031(9) 13_666 ?
Ir1 N1 2.031(9) . ?
Ir1 C11 2.570(10) . ?
Ir1 C11 2.570(10) 13_666 ?
Ir1 C11 2.570(10) 19_665 ?
Ir1 C11 2.570(10) 7_556 ?
Ni1 O14 1.987(8) . ?
Ni1 O1 2.046(6) 12_567 ?
Ni1 O1 2.046(6) 21_565 ?
Ni1 O1 2.046(6) . ?
Ni1 O1 2.046(6) 16_557 ?
Ni1 O2 2.094(3) . ?
N1 C2 1.260(13) . ?
N1 C2 1.260(13) 4_665 ?
N2 C4 1.361(12) . ?
N2 C4 1.361(12) 16_556 ?
O1 C10 1.342(10) . ?
O2 Ni1 2.094(3) 2_665 ?
O2 Ni1 2.094(3) 3_565 ?
C1 C1 1.20(2) 4_665 ?
C1 C2 1.429(15) . ?
C2 C3 1.481(18) . ?
C2 C2 1.95(3) 4_665 ?
C3 C6 1.42(2) . ?
C3 C4 1.508(19) . ?
C4 C5 1.522(12) . ?
C4 C4 2.00(2) 16_556 ?
C5 C5 1.278(12) 16_556 ?
C6 C7 1.305(12) . ?
C6 C7 1.305(12) 19_665 ?
C7 C8 1.512(15) . ?
C8 C9 1.403(10) . ?
C9 C10 1.396(18) . ?
C9 C8 1.403(10) 19_665 ?
C10 O1 1.342(10) 19_665 ?
C11 C11 0.72(3) 7_556 ?
C11 C12 1.529(13) . ?
C12 O11 1.375(12) . ?
C12 O12 1.548(14) . ?
O11 O11 1.72(3) 7_556 ?
O12 C13 1.536(12) . ?
C13 C14 1.542(14) . ?
C14 C14 1.58(3) 20 ?
N3 C16 1.447(7) . ?
N3 C17' 1.450(9) . ?
N3 C18' 1.450(7) . ?
N3 C17 1.454(8) . ?
N3 C18 1.456(8) . ?
N3 C16' 1.457(8) . ?
O14 C16 1.338(9) . ?
O14 C16' 1.457(14) 21_565 ?
O14 C16' 1.457(14) . ?
C16 N3 1.448(7) 21_565 ?
C18' N3 1.450(7) 21_565 ?
O3W O3W 1.65(5) 15_556 ?
O3W O3W 1.65(5) 14_556 ?
loop_
_platon_squeeze_void_nr
_platon_squeeze_void_average_x
_platon_squeeze_void_average_y
_platon_squeeze_void_average_z
_platon_squeeze_void_volume
_platon_squeeze_void_count_electrons
_platon_squeeze_void_content
1 -0.004 -0.003 -0.005 11053 1283 ' '
