#------------------------------------------------------------------------------ #$Date: 2021-04-27 06:28:45 +0300 (Tue, 27 Apr 2021) $ #$Revision: 264568 $ #$URL: file:///home/coder/svn-repositories/cod/cif/7/06/06/7060610.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_7060610 loop_ _publ_author_name 'Le Gal, Yann' 'Roisnel, Thierry' 'Barriere, Frederic' 'Mori, Takehiko' 'Lorcy, Dominique' _publ_section_title ; Diselenolene proligands: reactivity and comparison with their dithiolene congeners ; _journal_name_full 'New Journal of Chemistry' _journal_paper_doi 10.1039/D1NJ01335A _journal_year 2021 _chemical_compound_source 'synthesis as described' _chemical_formula_moiety 'C10 H10 N2 S4 Se' _chemical_formula_sum 'C10 H10 N2 S4 Se' _chemical_formula_weight 365.40 _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' _atom_sites_solution_hydrogens geom _audit_update_record ; 2021-02-16 deposited with the CCDC. 2021-04-26 downloaded from the CCDC. ; _cell_angle_alpha 90 _cell_angle_beta 94.728(5) _cell_angle_gamma 90 _cell_formula_units_Z 4 _cell_length_a 8.7866(11) _cell_length_b 12.3894(9) _cell_length_c 12.6125(12) _cell_measurement_reflns_used 7652 _cell_measurement_temperature 295 _cell_measurement_theta_max 27.42 _cell_measurement_theta_min 2.31 _cell_measurement_wavelength 0.71073 _cell_volume 1368.3(2) _computing_cell_refinement 'APEX3 (Bruker, 2015); SAINT (Bruker, 2014)' _computing_data_collection 'SAINT (Bruker, 2014)' _computing_data_reduction 'SAINT (Bruker, 2014)' _computing_molecular_graphics 'SXGRAPH (Farrugia, 1999), Mercury (CSD, 2014)' _computing_publication_material 'CRYSCALC (T. Roisnel, local program, 2016)' _computing_structure_refinement 'SHELXL-2014/7 (Sheldrick, 2014)' _computing_structure_solution 'SHELXT (Sheldrick, 2015)' _diffrn_ambient_temperature 295 _diffrn_detector '(CMOS) PHOTON 100' _diffrn_measured_fraction_theta_full 0.998 _diffrn_measured_fraction_theta_max 0.998 _diffrn_measurement_device_type 'D8 VENTURE Bruker AXS' _diffrn_measurement_method 'rotation images' _diffrn_radiation_monochromator 'multilayer monochromator' _diffrn_radiation_probe x-ray _diffrn_radiation_source 'Incoatec microfocus sealed tube' _diffrn_radiation_type MoK\a _diffrn_radiation_wavelength 0.71073 _diffrn_reflns_av_R_equivalents 0.0438 _diffrn_reflns_av_unetI/netI 0.0449 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_number 11626 _diffrn_reflns_theta_full 25.242 _diffrn_reflns_theta_max 27.476 _diffrn_reflns_theta_min 3.181 _exptl_absorpt_coefficient_mu 3.332 _exptl_absorpt_correction_T_max 0.648 _exptl_absorpt_correction_T_min 0.354 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; [Sheldrick, G.M. (2014). SADABS Bruker AXS Inc., Madison, Wisconsin, USA] ; _exptl_crystal_colour brown _exptl_crystal_density_diffrn 1.774 _exptl_crystal_description prism _exptl_crystal_F_000 728 _exptl_crystal_size_max 0.520 _exptl_crystal_size_mid 0.310 _exptl_crystal_size_min 0.130 _refine_diff_density_max 0.333 _refine_diff_density_min -0.688 _refine_diff_density_rms 0.070 _refine_ls_extinction_method none _refine_ls_goodness_of_fit_ref 1.069 _refine_ls_hydrogen_treatment constr _refine_ls_matrix_type full _refine_ls_number_parameters 156 _refine_ls_number_reflns 3133 _refine_ls_number_restraints 0 _refine_ls_restrained_S_all 1.069 _refine_ls_R_factor_all 0.0440 _refine_ls_R_factor_gt 0.0297 _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^)+(0.0448P)^2^] where P=(Fo^2^+2Fc^2^)/3' _refine_ls_weighting_scheme calc _refine_ls_wR_factor_gt 0.0796 _refine_ls_wR_factor_ref 0.0876 _reflns_number_gt 2490 _reflns_number_total 3133 _reflns_threshold_expression >2sigma(I) _cod_data_source_file d1nj01335a2.cif _cod_data_source_block Y524 _cod_original_sg_symbol_H-M 'P 21/c' _cod_database_code 7060610 _shelx_res_file ; job.res created by SHELXL-2014/7 TITL import_a.res in P2(1)/c CELL 0.71073 8.7866 12.3894 12.6125 90.000 94.728 90.000 ZERR 4.00 0.0011 0.0009 0.0012 0.000 0.005 0.000 LATT 1 SYMM - X, 1/2 + Y, 1/2 - Z SFAC C H N S SE UNIT 40 40 8 16 4 MERG 2 FMAP 2 PLAN 20 ACTA BOND $H CONF LIST 4 WPDB -2 L.S. 4 TEMP -123.00 WGHT 0.044800 FVAR 0.47570 C1 1 0.063411 0.659745 0.420559 11.00000 0.04066 0.03625 = 0.03217 0.00488 0.00603 0.00461 N2 3 0.076956 0.570539 0.359697 11.00000 0.04106 0.03814 = 0.02892 0.00104 -0.00074 0.00591 C3 1 -0.003694 0.555528 0.253366 11.00000 0.05172 0.05362 = 0.03460 -0.00100 -0.00873 0.00549 AFIX 23 H3A 2 -0.094312 0.603261 0.246073 11.00000 -1.20000 H3B 2 -0.039568 0.479954 0.245853 11.00000 -1.20000 AFIX 0 C4 1 0.097724 0.580623 0.167141 11.00000 0.09507 0.07803 = 0.03213 0.00732 0.00603 0.00057 AFIX 137 H4A 2 0.134331 0.655146 0.174951 11.00000 -1.50000 H4B 2 0.040255 0.571989 0.097709 11.00000 -1.50000 H4C 2 0.185095 0.531193 0.172217 11.00000 -1.50000 AFIX 0 C5 1 0.175345 0.493732 0.406150 11.00000 0.03638 0.03328 = 0.02953 -0.00146 0.00194 0.00409 C6 1 0.240926 0.519781 0.504093 11.00000 0.03866 0.02931 = 0.02703 -0.00070 0.00398 0.00138 C7 1 0.343266 0.439256 0.548286 11.00000 0.03577 0.03307 = 0.02644 -0.00120 0.00179 -0.00184 C8 1 0.357468 0.353975 0.482142 11.00000 0.04213 0.02875 = 0.02777 -0.00048 -0.00011 0.00231 N9 3 0.445797 0.270060 0.524419 11.00000 0.04003 0.03158 = 0.02818 0.00271 0.00345 0.00216 C10 1 0.474455 0.172187 0.463442 11.00000 0.05271 0.03498 = 0.03506 -0.00121 0.00646 0.00833 AFIX 23 H10A 2 0.571895 0.139163 0.492107 11.00000 -1.20000 H10B 2 0.484608 0.191914 0.388288 11.00000 -1.20000 AFIX 0 C11 1 0.347487 0.091145 0.468469 11.00000 0.06106 0.03614 = 0.07431 -0.00950 0.00106 0.00275 AFIX 137 H11A 2 0.343070 0.066681 0.542042 11.00000 -1.50000 H11B 2 0.366688 0.029243 0.423073 11.00000 -1.50000 H11C 2 0.250090 0.124780 0.443562 11.00000 -1.50000 AFIX 0 C12 1 0.502192 0.286263 0.626744 11.00000 0.03535 0.03864 = 0.03019 0.00303 0.00445 0.00055 S1 4 -0.043893 0.767709 0.392512 11.00000 0.06322 0.04759 = 0.04854 0.00587 0.00193 0.02177 S2 4 0.178278 0.646363 0.540399 11.00000 0.04544 0.03185 = 0.03041 -0.00389 0.00200 0.00473 S3 4 0.445628 0.414307 0.669156 11.00000 0.04371 0.03960 = 0.02634 -0.00246 -0.00278 0.00275 S4 4 0.611273 0.202569 0.702219 11.00000 0.05701 0.05613 = 0.04040 0.00905 -0.00430 0.01682 SE1 5 0.238398 0.361107 0.352104 11.00000 0.05120 0.03613 = 0.02796 -0.00593 -0.00436 0.00516 HKLF 4 REM import_a.res in P2(1)/c REM R1 = 0.0297 for 2490 Fo > 4sig(Fo) and 0.0440 for all 3133 data REM 156 parameters refined using 0 restraints END WGHT 0.0247 0.7311 REM Highest difference peak 0.333, deepest hole -0.688, 1-sigma level 0.070 Q1 1 0.0853 0.6394 0.5866 11.00000 0.05 0.33 Q2 1 0.3009 0.4350 0.2718 11.00000 0.05 0.32 Q3 1 0.1835 0.2742 0.3555 11.00000 0.05 0.30 Q4 1 0.3380 0.3730 0.3241 11.00000 0.05 0.28 Q5 1 0.4045 0.3219 0.4908 11.00000 0.05 0.28 Q6 1 0.2276 0.3681 0.4674 11.00000 0.05 0.27 Q7 1 -0.0620 0.7384 0.3537 11.00000 0.05 0.26 Q8 1 0.2998 0.3875 0.5148 11.00000 0.05 0.25 Q9 1 0.5314 0.1819 0.7132 11.00000 0.05 0.24 Q10 1 0.2828 0.4802 0.5331 11.00000 0.05 0.23 Q11 1 0.0546 0.7848 0.5231 11.00000 0.05 0.23 Q12 1 0.2212 0.3979 0.5423 11.00000 0.05 0.22 Q13 1 0.1313 0.3725 0.3904 11.00000 0.05 0.22 Q14 1 0.2774 0.2666 0.3752 11.00000 0.05 0.22 Q15 1 0.4707 0.2804 0.5786 11.00000 0.05 0.22 Q16 1 0.6145 0.2168 0.8403 11.00000 0.05 0.21 Q17 1 0.1200 0.5270 0.3734 11.00000 0.05 0.21 Q18 1 0.0747 0.7024 0.3941 11.00000 0.05 0.21 Q19 1 0.0866 0.4784 0.5220 11.00000 0.05 0.21 Q20 1 0.3902 0.4151 0.5015 11.00000 0.05 0.21 ; _shelx_res_checksum 29828 loop_ _space_group_symop_operation_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -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 C1 C 0.0634(3) 0.6597(2) 0.4206(2) 0.0362(5) Uani 1 1 d . . . . . N2 N 0.0770(2) 0.57054(16) 0.35970(16) 0.0362(5) Uani 1 1 d . . . . . C3 C -0.0037(3) 0.5555(2) 0.2534(2) 0.0473(7) Uani 1 1 d . . . . . H3A H -0.0943 0.6033 0.2461 0.057 Uiso 1 1 calc R U . . . H3B H -0.0396 0.4800 0.2459 0.057 Uiso 1 1 calc R U . . . C4 C 0.0977(5) 0.5806(3) 0.1671(2) 0.0684(10) Uani 1 1 d . . . . . H4A H 0.1343 0.6551 0.1750 0.103 Uiso 1 1 calc R U . . . H4B H 0.0403 0.5720 0.0977 0.103 Uiso 1 1 calc R U . . . H4C H 0.1851 0.5312 0.1722 0.103 Uiso 1 1 calc R U . . . C5 C 0.1753(3) 0.49373(19) 0.40615(19) 0.0331(5) Uani 1 1 d . . . . . C6 C 0.2409(3) 0.51978(17) 0.50409(19) 0.0316(5) Uani 1 1 d . . . . . C7 C 0.3433(3) 0.43926(18) 0.54829(19) 0.0318(5) Uani 1 1 d . . . . . C8 C 0.3575(3) 0.35397(17) 0.4821(2) 0.0331(5) Uani 1 1 d . . . . . N9 N 0.4458(2) 0.27006(15) 0.52442(16) 0.0332(5) Uani 1 1 d . . . . . C10 C 0.4745(3) 0.1722(2) 0.4634(2) 0.0408(6) Uani 1 1 d . . . . . H10A H 0.5719 0.1392 0.4921 0.049 Uiso 1 1 calc R U . . . H10B H 0.4846 0.1919 0.3883 0.049 Uiso 1 1 calc R U . . . C11 C 0.3475(4) 0.0911(2) 0.4685(3) 0.0574(8) Uani 1 1 d . . . . . H11A H 0.3431 0.0667 0.5420 0.086 Uiso 1 1 calc R U . . . H11B H 0.3667 0.0292 0.4231 0.086 Uiso 1 1 calc R U . . . H11C H 0.2501 0.1248 0.4436 0.086 Uiso 1 1 calc R U . . . C12 C 0.5022(3) 0.28626(19) 0.6267(2) 0.0346(5) Uani 1 1 d . . . . . S1 S -0.04389(10) 0.76771(6) 0.39251(6) 0.0533(2) Uani 1 1 d . . . . . S2 S 0.17828(8) 0.64636(5) 0.54040(5) 0.03596(16) Uani 1 1 d . . . . . S3 S 0.44563(8) 0.41431(5) 0.66916(5) 0.03686(16) Uani 1 1 d . . . . . S4 S 0.61127(9) 0.20257(6) 0.70222(6) 0.0516(2) Uani 1 1 d . . . . . Se1 Se 0.23840(3) 0.36111(2) 0.35210(2) 0.03885(11) Uani 1 1 d . . . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 C1 0.0407(14) 0.0363(12) 0.0322(13) 0.0049(10) 0.0060(11) 0.0046(10) N2 0.0411(12) 0.0381(10) 0.0289(11) 0.0010(8) -0.0007(9) 0.0059(9) C3 0.0517(17) 0.0536(16) 0.0346(14) -0.0010(12) -0.0087(12) 0.0055(13) C4 0.095(3) 0.078(2) 0.0321(16) 0.0073(15) 0.0060(17) 0.001(2) C5 0.0364(13) 0.0333(11) 0.0295(12) -0.0015(9) 0.0019(10) 0.0041(10) C6 0.0387(14) 0.0293(11) 0.0270(12) -0.0007(9) 0.0040(10) 0.0014(9) C7 0.0358(13) 0.0331(11) 0.0264(12) -0.0012(9) 0.0018(10) -0.0018(10) C8 0.0421(14) 0.0288(11) 0.0278(12) -0.0005(9) -0.0001(10) 0.0023(9) N9 0.0400(12) 0.0316(10) 0.0282(11) 0.0027(8) 0.0035(9) 0.0022(8) C10 0.0527(17) 0.0350(12) 0.0351(14) -0.0012(11) 0.0065(12) 0.0083(12) C11 0.061(2) 0.0361(14) 0.074(2) -0.0095(14) 0.0011(17) 0.0027(13) C12 0.0353(13) 0.0386(12) 0.0302(13) 0.0030(10) 0.0044(10) 0.0006(10) S1 0.0632(5) 0.0476(4) 0.0485(4) 0.0059(3) 0.0019(4) 0.0218(3) S2 0.0454(4) 0.0319(3) 0.0304(3) -0.0039(2) 0.0020(3) 0.0047(2) S3 0.0437(4) 0.0396(3) 0.0263(3) -0.0025(2) -0.0028(3) 0.0027(3) S4 0.0570(5) 0.0561(4) 0.0404(4) 0.0091(3) -0.0043(3) 0.0168(3) Se1 0.05120(19) 0.03613(16) 0.02796(16) -0.00593(9) -0.00436(11) 0.00516(10) 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Se Se -0.0929 2.2259 '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 C1 S1 127.7(2) . . ? N2 C1 S2 109.84(18) . . ? S1 C1 S2 122.46(16) . . ? C1 N2 C5 113.7(2) . . ? C1 N2 C3 124.0(2) . . ? C5 N2 C3 122.3(2) . . ? N2 C3 C4 111.4(3) . . ? N2 C3 H3A 109.4 . . ? C4 C3 H3A 109.4 . . ? N2 C3 H3B 109.4 . . ? C4 C3 H3B 109.4 . . ? H3A C3 H3B 108.0 . . ? C3 C4 H4A 109.5 . . ? C3 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? C3 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? C6 C5 N2 115.2(2) . . ? C6 C5 Se1 114.95(18) . . ? N2 C5 Se1 129.82(19) . . ? C5 C6 C7 113.3(2) . . ? C5 C6 S2 109.55(18) . . ? C7 C6 S2 137.11(19) . . ? C8 C7 C6 113.0(2) . . ? C8 C7 S3 109.53(18) . . ? C6 C7 S3 137.21(18) . . ? C7 C8 N9 115.2(2) . . ? C7 C8 Se1 115.34(18) . . ? N9 C8 Se1 129.08(17) . . ? C12 N9 C8 113.9(2) . . ? C12 N9 C10 123.7(2) . . ? C8 N9 C10 122.4(2) . . ? N9 C10 C11 111.6(2) . . ? N9 C10 H10A 109.3 . . ? C11 C10 H10A 109.3 . . ? N9 C10 H10B 109.3 . . ? C11 C10 H10B 109.3 . . ? H10A C10 H10B 108.0 . . ? C10 C11 H11A 109.5 . . ? C10 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C10 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? N9 C12 S4 126.96(19) . . ? N9 C12 S3 109.39(18) . . ? S4 C12 S3 123.63(15) . . ? C6 S2 C1 91.75(12) . . ? C7 S3 C12 91.86(12) . . ? C8 Se1 C5 83.33(10) . . ? 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 C1 N2 1.356(3) . ? C1 S1 1.658(3) . ? C1 S2 1.755(3) . ? N2 C5 1.383(3) . ? N2 C3 1.476(3) . ? C3 C4 1.494(4) . ? C3 H3A 0.9900 . ? C3 H3B 0.9900 . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C4 H4C 0.9800 . ? C5 C6 1.358(4) . ? C5 Se1 1.880(2) . ? C6 C7 1.425(3) . ? C6 S2 1.736(2) . ? C7 C8 1.358(3) . ? C7 S3 1.733(2) . ? C8 N9 1.378(3) . ? C8 Se1 1.873(3) . ? N9 C12 1.359(3) . ? N9 C10 1.469(3) . ? C10 C11 1.506(4) . ? C10 H10A 0.9900 . ? C10 H10B 0.9900 . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C12 S4 1.658(3) . ? C12 S3 1.759(2) . ? 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_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag S1 C1 N2 C5 -179.5(2) . . . . ? S2 C1 N2 C5 -0.1(3) . . . . ? S1 C1 N2 C3 1.0(4) . . . . ? S2 C1 N2 C3 -179.6(2) . . . . ? C1 N2 C3 C4 99.2(3) . . . . ? C5 N2 C3 C4 -80.3(3) . . . . ? C1 N2 C5 C6 0.3(3) . . . . ? C3 N2 C5 C6 179.8(2) . . . . ? C1 N2 C5 Se1 -176.95(19) . . . . ? C3 N2 C5 Se1 2.6(4) . . . . ? N2 C5 C6 C7 -179.0(2) . . . . ? Se1 C5 C6 C7 -1.4(3) . . . . ? N2 C5 C6 S2 -0.3(3) . . . . ? Se1 C5 C6 S2 177.32(12) . . . . ? C5 C6 C7 C8 1.6(3) . . . . ? S2 C6 C7 C8 -176.6(2) . . . . ? C5 C6 C7 S3 -172.0(2) . . . . ? S2 C6 C7 S3 9.8(5) . . . . ? C6 C7 C8 N9 -175.1(2) . . . . ? S3 C7 C8 N9 0.3(3) . . . . ? C6 C7 C8 Se1 -1.1(3) . . . . ? S3 C7 C8 Se1 174.27(12) . . . . ? C7 C8 N9 C12 1.0(3) . . . . ? Se1 C8 N9 C12 -171.94(19) . . . . ? C7 C8 N9 C10 -179.3(2) . . . . ? Se1 C8 N9 C10 7.7(4) . . . . ? C12 N9 C10 C11 95.0(3) . . . . ? C8 N9 C10 C11 -84.6(3) . . . . ? C8 N9 C12 S4 179.63(19) . . . . ? C10 N9 C12 S4 0.0(4) . . . . ? C8 N9 C12 S3 -1.8(3) . . . . ? C10 N9 C12 S3 178.54(18) . . . . ? C5 C6 S2 C1 0.2(2) . . . . ? C7 C6 S2 C1 178.5(3) . . . . ? N2 C1 S2 C6 -0.1(2) . . . . ? S1 C1 S2 C6 179.36(18) . . . . ? C8 C7 S3 C12 -1.1(2) . . . . ? C6 C7 S3 C12 172.7(3) . . . . ? N9 C12 S3 C7 1.7(2) . . . . ? S4 C12 S3 C7 -179.73(18) . . . . ? C7 C8 Se1 C5 0.3(2) . . . . ? N9 C8 Se1 C5 173.3(2) . . . . ? C6 C5 Se1 C8 0.6(2) . . . . ? N2 C5 Se1 C8 177.8(3) . . . . ?