#============================================================================== data_New_Global_Publ_Block _publ_section_related_literature ? # Added by publCIF - use a unique identifier for each data block #============================================================================== # SUBMISSION DETAILS _publ_contact_author_name 'Janusz Jurczak' # Name of author for correspondence _publ_contact_author_address # Address of author for correspondence ; Institute of Organic Chemistry, PAS, Kasprzaka 44/52, 01-224 Warsaw, Poland ; _publ_contact_author_email 'janusz.jurczak@icho.edu.pl' _publ_contact_author_fax '+48226326681' _publ_contact_author_phone '+48223432330' _publ_contact_letter ; Please consider this CIF for publication. I certify that this contibution is the original work of those listed as authors; that it has not been published before (in any language or medium) and is not being considered for publication elsewhere; that all authors concur with and are aware of the submission; that all workers involved in the study are listed as authors or given proper credit in the acknowledgements; that I have obtained permission for and acknowledged the source of any excerpts from other copyright works; and that to the best of my knowledge the paper contains no statements which are libellous, unlawful or in any way actionable. All coauthors have made significant scientific contributions to the work reported, including the ideas and their execution, and share responsibility and accountability for the results. ; _publ_requested_journal 'Organic Letters' _publ_requested_category '' #============================================================================== # TITLE AND AUTHOR LIST _publ_section_title ; "Unclosed cryptands": a point of departure for developing potent neutral anion receptors ; _publ_section_title_footnote # remove if not required . # The loop structure below should contain the names and addresses of all # authors, in the required order of publication. Repeat as necessary. # NB if using publCIF, the Author database tool might prove useful # (see the Tools menu in publCIF) loop_ _publ_author_name _publ_author_address _publ_author_footnote _publ_author_email 'Dabrowa, Kajetan' ; Institute of Organic Chemistry, Polish Academy of Science, Kasprzaka 44/52, 01-224 Warsaw, Poland. ; . ; kajetan.dabrowa@icho.edu.pl ; 'Pawlak, Marcin' ; Institute of Organic Chemistry, Polish Academy of Science, Kasprzaka 44/52, 01-224 Warsaw, Poland. ; . . 'Duszewski, Piotr' ; Institute of Organic Chemistry, Polish Academy of Science, Kasprzaka 44/52, 01-224 Warsaw, Poland. ; . ; piotr.duszewski@icho.edu.pl ; 'Jurczak, Janusz' ; Institute of Organic Chemistry, Polish Academy of Science, Kasprzaka 44/52, 01-224 Warsaw, Poland ; . ; janusz.jurczak@icho.edu.pl ; #============================================================================== # TEXT _publ_section_synopsis . _publ_section_abstract ; (type here to add abstract) ; _publ_section_comment ; (type here to add) ; _publ_section_acknowledgements # remove if not required ; (type here to add acknowledgements) ; _publ_section_references ; ? ; _publ_section_figure_captions ; ; _publ_section_exptl_prep ; (type here to add preparation details) ; _publ_section_exptl_refinement ; (type here to add refinement details) ; #============================================================================== data_shelxl _iucr_refine_instructions_details ; TITL 3C-R_xp in P21/c CELL 0.71073 9.394 15.3467 21.3416 90 106.931 90 ZERR 4 0.0001 0.0002 0.0003 0 0.001 0 LATT 1 SYMM -X,0.5+Y,0.5-Z SFAC C H N O UNIT 120 132 28 40 L.S. 10 htab PLAN 20 SIZE 0.21 0.38 0.43 TEMP -173 BOND eqiv $1 -x+1, y+1/2, -z+1/2 eqiv $2 -x+1, -y+1, -z+1 htab O1W O3 htab O1W O7_$1 htab N2 O5_$2 htab N3 O1W htab N4 O1W htab N6 O1W htab N7 O3 htab CONF fmap 2 acta 50 MERG 2 WGHT 0.082000 0.830900 FVAR 0.31930 O1 4 0.735927 0.011069 0.614412 11.00000 0.01926 0.02960 = 0.03322 0.00639 0.00098 0.00718 O1W 4 0.549155 0.313380 0.329260 11.00000 0.02021 0.01792 = 0.02276 0.00358 0.00311 -0.00047 H1WA 2 0.470378 0.294514 0.329948 11.00000 0.04576 H1WB 2 0.532295 0.360472 0.304620 11.00000 0.04314 O2 4 0.602960 0.064955 0.672612 11.00000 0.02646 0.04230 = 0.02129 0.01396 0.00606 0.00133 O3 4 0.292959 0.232824 0.342855 11.00000 0.01979 0.01743 = 0.01122 -0.00206 0.00375 0.00126 O4 4 0.385300 0.482262 0.418948 11.00000 0.01337 0.01367 = 0.01481 0.00115 -0.00035 -0.00228 O5 4 0.723483 0.600739 0.461226 11.00000 0.01814 0.01551 = 0.01526 -0.00462 0.00525 -0.00493 O6 4 0.993868 0.160174 0.507845 11.00000 0.01816 0.02358 = 0.01682 -0.00264 -0.00187 0.00491 O7 4 0.520648 -0.018993 0.219381 11.00000 0.02092 0.01682 = 0.01632 -0.00505 0.00332 0.00026 O8 4 -0.177921 0.265050 0.150396 11.00000 0.01720 0.02432 = 0.01476 -0.00185 -0.00053 0.00224 O9 4 -0.016159 0.297917 0.322896 11.00000 0.01563 0.01493 = 0.01288 -0.00155 0.00324 -0.00359 N1 3 0.632952 0.056126 0.620516 11.00000 0.01561 0.02035 = 0.02131 0.00660 0.00109 -0.00240 N2 3 0.246870 0.328680 0.416213 11.00000 0.01656 0.01203 = 0.01009 -0.00065 0.00270 0.00008 H2 2 0.264934 0.341964 0.457966 11.00000 0.02983 N3 3 0.670655 0.462304 0.424217 11.00000 0.01342 0.01281 = 0.01679 -0.00250 0.00259 -0.00130 H3 2 0.602344 0.426283 0.405400 11.00000 0.02935 N4 3 0.800051 0.237810 0.443363 11.00000 0.01502 0.01366 = 0.01229 -0.00178 0.00089 0.00181 H4 2 0.733965 0.241925 0.403555 11.00000 0.03273 N5 3 0.736388 0.104137 0.355144 11.00000 0.01328 0.01307 = 0.01184 -0.00002 0.00365 0.00048 N6 3 0.479722 0.114214 0.257441 11.00000 0.01401 0.01469 = 0.01578 -0.00408 0.00033 0.00138 H6 2 0.516636 0.154239 0.286803 11.00000 0.03357 N7 3 0.061135 0.247102 0.213881 11.00000 0.01511 0.01581 = 0.01077 -0.00063 0.00164 0.00143 H7 2 0.115961 0.245542 0.253246 11.00000 0.02093 C1 1 0.539976 0.102498 0.562744 11.00000 0.01473 0.01421 = 0.01594 0.00293 0.00091 -0.00135 C2 1 0.415288 0.146363 0.567801 11.00000 0.02043 0.01754 = 0.01466 0.00243 0.00676 0.00171 AFIX 43 H2A 2 0.387210 0.144062 0.607085 11.00000 -1.20000 AFIX 0 C3 1 0.331825 0.193907 0.514240 11.00000 0.01722 0.01611 = 0.01567 0.00211 0.00665 0.00299 AFIX 43 H3A 2 0.246527 0.225260 0.516835 11.00000 -1.20000 AFIX 0 C4 1 0.373691 0.195467 0.456588 11.00000 0.01395 0.01187 = 0.01252 -0.00057 0.00292 -0.00102 C5 1 0.494950 0.146138 0.451700 11.00000 0.01734 0.01639 = 0.01590 0.00022 0.00643 0.00115 AFIX 43 H5 2 0.518722 0.144206 0.411396 11.00000 -1.20000 AFIX 0 C6 1 0.580949 0.099932 0.505295 11.00000 0.01596 0.01722 = 0.02080 0.00209 0.00656 0.00234 AFIX 43 H6A 2 0.665269 0.067538 0.502756 11.00000 -1.20000 AFIX 0 C7 1 0.297936 0.252746 0.399894 11.00000 0.01259 0.01314 = 0.01181 -0.00022 0.00234 -0.00133 C8 1 0.178579 0.394379 0.370481 11.00000 0.01416 0.01237 = 0.01042 -0.00002 0.00390 0.00121 C9 1 0.041379 0.380254 0.323509 11.00000 0.01349 0.01303 = 0.01228 -0.00192 0.00473 -0.00071 C10 1 -0.028981 0.447396 0.282024 11.00000 0.01316 0.01710 = 0.01442 -0.00064 0.00261 0.00143 AFIX 43 H10 2 -0.120779 0.437471 0.249369 11.00000 -1.20000 AFIX 0 C11 1 0.037415 0.529022 0.289253 11.00000 0.01531 0.01494 = 0.01742 0.00106 0.00333 0.00355 AFIX 43 H11 2 -0.011613 0.575309 0.261817 11.00000 -1.20000 AFIX 0 C12 1 0.173680 0.545118 0.335489 11.00000 0.01501 0.01175 = 0.01729 0.00005 0.00409 0.00063 AFIX 43 H12 2 0.216236 0.601775 0.340257 11.00000 -1.20000 AFIX 0 C13 1 0.246413 0.476536 0.374625 11.00000 0.01144 0.01390 = 0.01155 -0.00123 0.00269 0.00025 C14 1 0.468117 0.561103 0.421910 11.00000 0.01482 0.01183 = 0.01731 -0.00119 0.00296 -0.00131 AFIX 23 H14A 2 0.449459 0.600144 0.455602 11.00000 -1.20000 H14B 2 0.434955 0.591363 0.379144 11.00000 -1.20000 AFIX 0 C15 1 0.633039 0.541485 0.438559 11.00000 0.01560 0.01302 = 0.00899 0.00003 0.00344 -0.00111 C16 1 0.823960 0.435568 0.432216 11.00000 0.01523 0.01513 = 0.02132 -0.00228 0.00711 -0.00051 AFIX 23 H16A 2 0.886574 0.487971 0.434185 11.00000 -1.20000 H16B 2 0.828068 0.400688 0.393758 11.00000 -1.20000 AFIX 0 C17 1 0.885906 0.381886 0.494224 11.00000 0.01336 0.01720 = 0.01901 -0.00528 0.00071 0.00017 AFIX 23 H17A 2 0.886527 0.418011 0.532735 11.00000 -1.20000 H17B 2 0.990069 0.365588 0.498058 11.00000 -1.20000 AFIX 0 C18 1 0.795941 0.299424 0.494863 11.00000 0.01742 0.01535 = 0.01365 -0.00225 0.00405 0.00258 AFIX 23 H18A 2 0.835031 0.270468 0.537918 11.00000 -1.20000 H18B 2 0.691210 0.315778 0.489720 11.00000 -1.20000 AFIX 0 C19 1 0.893208 0.169508 0.456267 11.00000 0.01308 0.01469 = 0.01329 -0.00080 0.00307 0.00035 C20 1 0.863619 0.099528 0.404474 11.00000 0.01334 0.01310 = 0.01293 0.00021 0.00349 0.00092 C21 1 0.963589 0.030574 0.411982 11.00000 0.01558 0.01657 = 0.01747 0.00051 0.00360 0.00373 AFIX 43 H21 2 1.052746 0.029871 0.447321 11.00000 -1.20000 AFIX 0 C22 1 0.930598 -0.037123 0.366886 11.00000 0.01812 0.01513 = 0.01988 -0.00009 0.00599 0.00454 AFIX 43 H22 2 0.997060 -0.084804 0.370654 11.00000 -1.20000 AFIX 0 C23 1 0.798626 -0.033852 0.316159 11.00000 0.01718 0.01352 = 0.01694 -0.00164 0.00623 0.00142 AFIX 43 H23 2 0.772358 -0.079566 0.284890 11.00000 -1.20000 AFIX 0 C24 1 0.705558 0.038018 0.312151 11.00000 0.01339 0.01351 = 0.01253 -0.00006 0.00473 0.00036 C25 1 0.559890 0.041716 0.258545 11.00000 0.01449 0.01378 = 0.01221 0.00003 0.00482 -0.00020 C26 1 0.322437 0.121363 0.221069 11.00000 0.01248 0.01524 = 0.01446 -0.00143 0.00060 0.00091 AFIX 23 H26A 2 0.262032 0.116809 0.251980 11.00000 -1.20000 H26B 2 0.294731 0.072289 0.189760 11.00000 -1.20000 AFIX 0 C27 1 0.286570 0.207307 0.183547 11.00000 0.01634 0.01597 = 0.01344 -0.00006 0.00445 0.00101 AFIX 23 H27A 2 0.335728 0.255672 0.212515 11.00000 -1.20000 H27B 2 0.327298 0.205754 0.145681 11.00000 -1.20000 AFIX 0 C28 1 0.119630 0.224754 0.159093 11.00000 0.01729 0.01693 = 0.01103 -0.00051 0.00300 0.00276 AFIX 23 H28A 2 0.100085 0.273334 0.127197 11.00000 -1.20000 H28B 2 0.067918 0.172324 0.136458 11.00000 -1.20000 AFIX 0 C29 1 -0.083976 0.263260 0.204498 11.00000 0.01529 0.01072 = 0.01513 -0.00080 0.00302 -0.00097 C30 1 -0.133930 0.274418 0.265962 11.00000 0.01424 0.01845 = 0.01422 -0.00219 0.00336 -0.00402 AFIX 23 H30A 2 -0.211869 0.319945 0.257685 11.00000 -1.20000 H30B 2 -0.178984 0.219150 0.274762 11.00000 -1.20000 HKLF 4 REM 3C-R_xp in P21/c REM R1 = 0.0385 for 7482 Fo > 4sig(Fo) and 0.0491 for all 8994 data REM 452 parameters refined using 0 restraints END WGHT 0.0746 0.9329 REM Highest difference peak 0.476, deepest hole -0.365, 1-sigma level 0.077 Q1 1 0.9113 0.0641 0.4084 11.00000 0.05 0.48 Q2 1 0.3702 0.1671 0.5407 11.00000 0.05 0.44 Q3 1 0.3023 0.1619 0.2030 11.00000 0.05 0.41 Q4 1 -0.1066 0.2676 0.2368 11.00000 0.05 0.40 Q5 1 0.8824 0.1353 0.4280 11.00000 0.05 0.37 Q6 1 0.2037 0.2152 0.1742 11.00000 0.05 0.37 Q7 1 0.1030 0.5373 0.3144 11.00000 0.05 0.37 Q8 1 0.9460 -0.0046 0.3878 11.00000 0.05 0.36 Q9 1 0.4886 0.1341 0.5665 11.00000 0.05 0.35 Q10 1 0.3321 0.2223 0.4299 11.00000 0.05 0.35 Q11 1 0.5536 0.5526 0.4288 11.00000 0.05 0.34 Q12 1 0.8525 0.4092 0.4625 11.00000 0.05 0.34 Q13 1 0.5177 0.0791 0.2592 11.00000 0.05 0.34 Q14 1 0.6351 0.0410 0.2831 11.00000 0.05 0.33 Q15 1 0.8467 0.3410 0.4962 11.00000 0.05 0.33 Q16 1 0.3621 0.1954 0.4860 11.00000 0.05 0.33 Q17 1 0.8622 -0.0374 0.3446 11.00000 0.05 0.32 Q18 1 0.7545 -0.0007 0.3171 11.00000 0.05 0.32 Q19 1 0.0017 0.4163 0.3014 11.00000 0.05 0.31 Q20 1 0.0161 0.4849 0.2835 11.00000 0.05 0.31 ; _audit_update_record ; 2012-10-25 # Formatted by publCIF ; _audit_creation_method SHELXL-97 _chemical_name_systematic ? _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C30 H33 N7 O10' _chemical_formula_weight 651.63 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 9.39400(10) _cell_length_b 15.3467(2) _cell_length_c 21.3416(3) _cell_angle_alpha 90.00 _cell_angle_beta 106.9310(10) _cell_angle_gamma 90.00 _cell_volume 2943.39(6) _cell_formula_units_Z 4 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 60162 _cell_measurement_theta_min 1.9909 _cell_measurement_theta_max 32.3226 _exptl_crystal_description prismatic _exptl_crystal_colour yellow _exptl_crystal_size_max 0.43 _exptl_crystal_size_mid 0.38 _exptl_crystal_size_min 0.21 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.470 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1368 _exptl_absorpt_coefficient_mu 0.112 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.9532 _exptl_absorpt_correction_T_max 0.9768 _exptl_absorpt_process_details ; CrysAlisPro, Agilent Technologies, Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET) (compiled Aug 3 2011,13:03:54) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_special_details ; CrysAlisPro, Agilent Technologies, Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET) (compiled Aug 3 2011,13:03:54) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _diffrn_ambient_temperature 100(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Xcalibur, Opal' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 8.4441 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 178894 _diffrn_reflns_av_R_equivalents 0.0410 _diffrn_reflns_av_sigmaI/netI 0.0147 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 1.99 _diffrn_reflns_theta_max 30.51 _reflns_number_total 8994 _reflns_number_gt 7482 _reflns_threshold_expression >2sigma(I) _computing_data_collection ; CrysAlisPro, Agilent Technologies, Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET) (compiled Aug 3 2011,13:03:54) ; _computing_cell_refinement ; CrysAlisPro, Agilent Technologies, Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET) (compiled Aug 3 2011,13:03:54) ; _computing_data_reduction ; CrysAlisPro, Agilent Technologies, Version 1.171.35.15 (release 03-08-2011 CrysAlis171 .NET) (compiled Aug 3 2011,13:03:54) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ortep, Wingx, Mercury' _computing_publication_material SHELXTL-97 _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0820P)^2^+0.8309P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 8994 _refine_ls_number_parameters 452 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0491 _refine_ls_R_factor_gt 0.0385 _refine_ls_wR_factor_ref 0.1297 _refine_ls_wR_factor_gt 0.1182 _refine_ls_goodness_of_fit_ref 1.063 _refine_ls_restrained_S_all 1.063 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group O1 O 0.73593(10) 0.01107(7) 0.61441(5) 0.0288(2) Uani 1 1 d . . . O1W O 0.54915(10) 0.31338(6) 0.32926(4) 0.02096(18) Uani 1 1 d . . . H1WA H 0.470(3) 0.2945(15) 0.3299(10) 0.046(6) Uiso 1 1 d . . . H1WB H 0.532(2) 0.3605(15) 0.3046(10) 0.043(5) Uiso 1 1 d . . . O2 O 0.60296(11) 0.06495(7) 0.67261(5) 0.0302(2) Uani 1 1 d . . . O3 O 0.29296(9) 0.23282(5) 0.34286(4) 0.01631(16) Uani 1 1 d . . . O4 O 0.38530(9) 0.48226(5) 0.41895(4) 0.01490(15) Uani 1 1 d . . . O5 O 0.72348(9) 0.60074(5) 0.46123(4) 0.01622(16) Uani 1 1 d . . . O6 O 0.99387(10) 0.16017(6) 0.50784(4) 0.02100(18) Uani 1 1 d . . . O7 O 0.52065(9) -0.01899(5) 0.21938(4) 0.01847(17) Uani 1 1 d . . . O8 O -0.17792(9) 0.26505(6) 0.15040(4) 0.01986(17) Uani 1 1 d . . . O9 O -0.01616(9) 0.29792(5) 0.32290(4) 0.01467(15) Uani 1 1 d . . . N1 N 0.63295(11) 0.05613(7) 0.62052(5) 0.0200(2) Uani 1 1 d . . . N2 N 0.24687(10) 0.32868(6) 0.41621(4) 0.01314(17) Uani 1 1 d . . . H2 H 0.265(2) 0.3420(12) 0.4580(9) 0.030(4) Uiso 1 1 d . . . N3 N 0.67065(10) 0.46230(6) 0.42422(5) 0.01473(17) Uani 1 1 d . . . H3 H 0.602(2) 0.4263(12) 0.4054(9) 0.029(4) Uiso 1 1 d . . . N4 N 0.80005(10) 0.23781(6) 0.44336(5) 0.01431(17) Uani 1 1 d . . . H4 H 0.734(2) 0.2419(12) 0.4036(9) 0.033(5) Uiso 1 1 d . . . N5 N 0.73639(10) 0.10414(6) 0.35514(4) 0.01273(17) Uani 1 1 d . . . N6 N 0.47972(11) 0.11421(6) 0.25744(5) 0.01567(18) Uani 1 1 d . . . H6 H 0.517(2) 0.1542(13) 0.2868(9) 0.034(5) Uiso 1 1 d . . . N7 N 0.06113(11) 0.24710(6) 0.21388(5) 0.01435(17) Uani 1 1 d . . . H7 H 0.1160(19) 0.2455(11) 0.2532(8) 0.021(4) Uiso 1 1 d . . . C1 C 0.53998(12) 0.10250(7) 0.56274(5) 0.0157(2) Uani 1 1 d . . . C2 C 0.41529(13) 0.14636(7) 0.56780(5) 0.0172(2) Uani 1 1 d . . . H2A H 0.3872 0.1441 0.6071 0.021 Uiso 1 1 calc R . . C3 C 0.33183(12) 0.19391(7) 0.51424(5) 0.0159(2) Uani 1 1 d . . . H3A H 0.2465 0.2253 0.5168 0.019 Uiso 1 1 calc R . . C4 C 0.37369(11) 0.19547(7) 0.45659(5) 0.01298(18) Uani 1 1 d . . . C5 C 0.49495(12) 0.14614(7) 0.45170(5) 0.0162(2) Uani 1 1 d . . . H5 H 0.5187 0.1442 0.4114 0.019 Uiso 1 1 calc R . . C6 C 0.58095(13) 0.09993(7) 0.50529(6) 0.0177(2) Uani 1 1 d . . . H6A H 0.6653 0.0675 0.5028 0.021 Uiso 1 1 calc R . . C7 C 0.29794(11) 0.25275(7) 0.39989(5) 0.01277(18) Uani 1 1 d . . . C8 C 0.17858(11) 0.39438(7) 0.37048(5) 0.01225(18) Uani 1 1 d . . . C9 C 0.04138(11) 0.38025(7) 0.32351(5) 0.01273(18) Uani 1 1 d . . . C10 C -0.02898(12) 0.44740(7) 0.28202(5) 0.0152(2) Uani 1 1 d . . . H10 H -0.1208 0.4375 0.2494 0.018 Uiso 1 1 calc R . . C11 C 0.03741(12) 0.52902(7) 0.28925(5) 0.0162(2) Uani 1 1 d . . . H11 H -0.0116 0.5753 0.2618 0.019 Uiso 1 1 calc R . . C12 C 0.17368(12) 0.54512(7) 0.33549(5) 0.01481(19) Uani 1 1 d . . . H12 H 0.2162 0.6018 0.3403 0.018 Uiso 1 1 calc R . . C13 C 0.24641(11) 0.47654(7) 0.37462(5) 0.01244(18) Uani 1 1 d . . . C14 C 0.46812(12) 0.56110(7) 0.42191(5) 0.01502(19) Uani 1 1 d . . . H14A H 0.4495 0.6001 0.4556 0.018 Uiso 1 1 calc R . . H14B H 0.4350 0.5914 0.3791 0.018 Uiso 1 1 calc R . . C15 C 0.63304(12) 0.54148(7) 0.43856(5) 0.01257(18) Uani 1 1 d . . . C16 C 0.82396(12) 0.43557(7) 0.43222(6) 0.0168(2) Uani 1 1 d . . . H16A H 0.8866 0.4880 0.4342 0.020 Uiso 1 1 calc R . . H16B H 0.8281 0.4007 0.3938 0.020 Uiso 1 1 calc R . . C17 C 0.88591(12) 0.38189(7) 0.49422(6) 0.0174(2) Uani 1 1 d . . . H17A H 0.8865 0.4180 0.5327 0.021 Uiso 1 1 calc R . . H17B H 0.9901 0.3656 0.4981 0.021 Uiso 1 1 calc R . . C18 C 0.79594(12) 0.29942(7) 0.49486(5) 0.0156(2) Uani 1 1 d . . . H18A H 0.8350 0.2705 0.5379 0.019 Uiso 1 1 calc R . . H18B H 0.6912 0.3158 0.4897 0.019 Uiso 1 1 calc R . . C19 C 0.89321(11) 0.16951(7) 0.45627(5) 0.01385(19) Uani 1 1 d . . . C20 C 0.86362(12) 0.09953(7) 0.40447(5) 0.01319(19) Uani 1 1 d . . . C21 C 0.96359(12) 0.03057(7) 0.41198(6) 0.0168(2) Uani 1 1 d . . . H21 H 1.0527 0.0299 0.4473 0.020 Uiso 1 1 calc R . . C22 C 0.93060(13) -0.03712(7) 0.36689(6) 0.0176(2) Uani 1 1 d . . . H22 H 0.9971 -0.0848 0.3707 0.021 Uiso 1 1 calc R . . C23 C 0.79863(12) -0.03385(7) 0.31616(5) 0.0156(2) Uani 1 1 d . . . H23 H 0.7724 -0.0796 0.2849 0.019 Uiso 1 1 calc R . . C24 C 0.70556(12) 0.03802(7) 0.31215(5) 0.01294(18) Uani 1 1 d . . . C25 C 0.55989(12) 0.04172(7) 0.25855(5) 0.01329(19) Uani 1 1 d . . . C26 C 0.32244(12) 0.12136(7) 0.22107(5) 0.01476(19) Uani 1 1 d . . . H26A H 0.2620 0.1168 0.2520 0.018 Uiso 1 1 calc R . . H26B H 0.2947 0.0723 0.1898 0.018 Uiso 1 1 calc R . . C27 C 0.28657(12) 0.20731(7) 0.18355(5) 0.01523(19) Uani 1 1 d . . . H27A H 0.3357 0.2557 0.2125 0.018 Uiso 1 1 calc R . . H27B H 0.3273 0.2058 0.1457 0.018 Uiso 1 1 calc R . . C28 C 0.11963(12) 0.22475(7) 0.15909(5) 0.0153(2) Uani 1 1 d . . . H28A H 0.1001 0.2733 0.1272 0.018 Uiso 1 1 calc R . . H28B H 0.0679 0.1723 0.1365 0.018 Uiso 1 1 calc R . . C29 C -0.08398(12) 0.26326(7) 0.20450(5) 0.01402(19) Uani 1 1 d . . . C30 C -0.13393(12) 0.27442(7) 0.26596(5) 0.0158(2) Uani 1 1 d . . . H30A H -0.2119 0.3199 0.2577 0.019 Uiso 1 1 calc R . . H30B H -0.1790 0.2191 0.2748 0.019 Uiso 1 1 calc R . . 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 O1 0.0193(4) 0.0296(5) 0.0332(5) 0.0064(4) 0.0010(4) 0.0072(4) O1W 0.0202(4) 0.0179(4) 0.0228(4) 0.0036(3) 0.0031(3) -0.0005(3) O2 0.0265(5) 0.0423(6) 0.0213(4) 0.0140(4) 0.0061(4) 0.0013(4) O3 0.0198(4) 0.0174(4) 0.0112(3) -0.0021(3) 0.0037(3) 0.0013(3) O4 0.0134(3) 0.0137(3) 0.0148(4) 0.0011(3) -0.0004(3) -0.0023(3) O5 0.0181(4) 0.0155(4) 0.0153(4) -0.0046(3) 0.0052(3) -0.0049(3) O6 0.0182(4) 0.0236(4) 0.0168(4) -0.0026(3) -0.0019(3) 0.0049(3) O7 0.0209(4) 0.0168(4) 0.0163(4) -0.0050(3) 0.0033(3) 0.0003(3) O8 0.0172(4) 0.0243(4) 0.0148(4) -0.0019(3) -0.0005(3) 0.0022(3) O9 0.0156(4) 0.0149(3) 0.0129(3) -0.0015(3) 0.0032(3) -0.0036(3) N1 0.0156(4) 0.0203(5) 0.0213(5) 0.0066(4) 0.0011(4) -0.0024(3) N2 0.0166(4) 0.0120(4) 0.0101(4) -0.0007(3) 0.0027(3) 0.0001(3) N3 0.0134(4) 0.0128(4) 0.0168(4) -0.0025(3) 0.0026(3) -0.0013(3) N4 0.0150(4) 0.0137(4) 0.0123(4) -0.0018(3) 0.0009(3) 0.0018(3) N5 0.0133(4) 0.0131(4) 0.0118(4) 0.0000(3) 0.0036(3) 0.0005(3) N6 0.0140(4) 0.0147(4) 0.0158(4) -0.0041(3) 0.0003(3) 0.0014(3) N7 0.0151(4) 0.0158(4) 0.0108(4) -0.0006(3) 0.0016(3) 0.0014(3) C1 0.0147(5) 0.0142(4) 0.0159(5) 0.0029(4) 0.0009(4) -0.0014(4) C2 0.0204(5) 0.0175(5) 0.0147(5) 0.0024(4) 0.0068(4) 0.0017(4) C3 0.0172(5) 0.0161(5) 0.0157(5) 0.0021(4) 0.0066(4) 0.0030(4) C4 0.0139(4) 0.0119(4) 0.0125(4) -0.0006(3) 0.0029(3) -0.0010(3) C5 0.0173(5) 0.0164(5) 0.0159(5) 0.0002(4) 0.0064(4) 0.0011(4) C6 0.0160(5) 0.0172(5) 0.0208(5) 0.0021(4) 0.0066(4) 0.0023(4) C7 0.0126(4) 0.0131(4) 0.0118(4) -0.0002(3) 0.0023(3) -0.0013(3) C8 0.0142(4) 0.0124(4) 0.0104(4) 0.0000(3) 0.0039(3) 0.0012(3) C9 0.0135(4) 0.0130(4) 0.0123(4) -0.0019(3) 0.0047(3) -0.0007(3) C10 0.0132(4) 0.0171(5) 0.0144(5) -0.0006(4) 0.0026(4) 0.0014(4) C11 0.0153(5) 0.0149(5) 0.0174(5) 0.0011(4) 0.0033(4) 0.0035(4) C12 0.0150(5) 0.0117(4) 0.0173(5) 0.0001(4) 0.0041(4) 0.0006(4) C13 0.0114(4) 0.0139(4) 0.0116(4) -0.0012(3) 0.0027(3) 0.0003(3) C14 0.0148(5) 0.0118(4) 0.0173(5) -0.0012(3) 0.0030(4) -0.0013(3) C15 0.0156(5) 0.0130(4) 0.0090(4) 0.0000(3) 0.0034(3) -0.0011(3) C16 0.0152(5) 0.0151(5) 0.0213(5) -0.0023(4) 0.0071(4) -0.0005(4) C17 0.0134(5) 0.0172(5) 0.0190(5) -0.0053(4) 0.0007(4) 0.0002(4) C18 0.0174(5) 0.0154(5) 0.0137(4) -0.0023(4) 0.0040(4) 0.0026(4) C19 0.0131(4) 0.0147(4) 0.0133(4) -0.0008(3) 0.0031(4) 0.0004(3) C20 0.0133(4) 0.0131(4) 0.0129(4) 0.0002(3) 0.0035(4) 0.0009(3) C21 0.0156(5) 0.0166(5) 0.0175(5) 0.0005(4) 0.0036(4) 0.0037(4) C22 0.0181(5) 0.0151(5) 0.0199(5) -0.0001(4) 0.0060(4) 0.0045(4) C23 0.0172(5) 0.0135(4) 0.0169(5) -0.0016(4) 0.0062(4) 0.0014(4) C24 0.0134(4) 0.0135(4) 0.0125(4) -0.0001(3) 0.0047(3) 0.0004(3) C25 0.0145(4) 0.0138(4) 0.0122(4) 0.0000(3) 0.0048(4) -0.0002(3) C26 0.0125(4) 0.0152(4) 0.0145(4) -0.0014(4) 0.0006(3) 0.0009(4) C27 0.0163(5) 0.0160(5) 0.0134(4) -0.0001(4) 0.0045(4) 0.0010(4) C28 0.0173(5) 0.0169(5) 0.0110(4) -0.0005(3) 0.0030(4) 0.0028(4) C29 0.0153(5) 0.0107(4) 0.0151(5) -0.0008(3) 0.0030(4) -0.0010(3) C30 0.0142(5) 0.0184(5) 0.0142(5) -0.0022(4) 0.0034(4) -0.0040(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; 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 O1 N1 1.2265(14) . ? O2 N1 1.2314(15) . ? O3 C7 1.2427(13) . ? O4 C13 1.3733(12) . ? O4 C14 1.4299(13) . ? O5 C15 1.2424(13) . ? O6 C19 1.2329(13) . ? O7 C25 1.2341(13) . ? O8 C29 1.2326(13) . ? O9 C9 1.3729(12) . ? O9 C30 1.4309(12) . ? N1 C1 1.4705(14) . ? N2 C7 1.3442(13) . ? N2 C8 1.4199(13) . ? N3 C15 1.3259(14) . ? N3 C16 1.4589(14) . ? N4 C19 1.3417(13) . ? N4 C18 1.4589(14) . ? N5 C24 1.3419(13) . ? N5 C20 1.3450(13) . ? N6 C25 1.3399(14) . ? N6 C26 1.4593(13) . ? N7 C29 1.3420(14) . ? N7 C28 1.4700(14) . ? C1 C2 1.3822(16) . ? C1 C6 1.3884(16) . ? C2 C3 1.3899(15) . ? C3 C4 1.3968(15) . ? C4 C5 1.3967(15) . ? C4 C7 1.4972(14) . ? C5 C6 1.3877(15) . ? C8 C9 1.4002(14) . ? C8 C13 1.4038(14) . ? C9 C10 1.3934(15) . ? C10 C11 1.3878(15) . ? C11 C12 1.3920(15) . ? C12 C13 1.3928(14) . ? C14 C15 1.5154(15) . ? C16 C17 1.5232(16) . ? C17 C18 1.5240(16) . ? C19 C20 1.5078(14) . ? C20 C21 1.3928(14) . ? C21 C22 1.3885(16) . ? C22 C23 1.3892(15) . ? C23 C24 1.3945(14) . ? C24 C25 1.5076(14) . ? C26 C27 1.5288(15) . ? C27 C28 1.5254(15) . ? C29 C30 1.5260(15) . ? 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 C13 O4 C14 118.69(8) . . ? C9 O9 C30 116.42(8) . . ? O1 N1 O2 123.56(11) . . ? O1 N1 C1 118.56(10) . . ? O2 N1 C1 117.88(10) . . ? C7 N2 C8 124.16(9) . . ? C15 N3 C16 123.44(9) . . ? C19 N4 C18 120.70(9) . . ? C24 N5 C20 117.46(9) . . ? C25 N6 C26 123.27(9) . . ? C29 N7 C28 121.55(9) . . ? C2 C1 C6 122.81(10) . . ? C2 C1 N1 118.70(10) . . ? C6 C1 N1 118.49(10) . . ? C1 C2 C3 118.65(10) . . ? C2 C3 C4 119.82(10) . . ? C5 C4 C3 120.10(10) . . ? C5 C4 C7 117.64(9) . . ? C3 C4 C7 122.17(9) . . ? C6 C5 C4 120.47(10) . . ? C5 C6 C1 117.96(10) . . ? O3 C7 N2 123.55(10) . . ? O3 C7 C4 121.37(9) . . ? N2 C7 C4 114.91(9) . . ? C9 C8 C13 119.37(9) . . ? C9 C8 N2 121.31(9) . . ? C13 C8 N2 119.24(9) . . ? O9 C9 C10 124.19(9) . . ? O9 C9 C8 115.28(9) . . ? C10 C9 C8 120.52(10) . . ? C11 C10 C9 118.83(10) . . ? C10 C11 C12 121.99(10) . . ? C11 C12 C13 118.70(10) . . ? O4 C13 C12 124.50(9) . . ? O4 C13 C8 115.06(9) . . ? C12 C13 C8 120.43(9) . . ? O4 C14 C15 110.38(8) . . ? O5 C15 N3 124.24(10) . . ? O5 C15 C14 118.84(9) . . ? N3 C15 C14 116.80(9) . . ? N3 C16 C17 111.60(9) . . ? C16 C17 C18 112.60(9) . . ? N4 C18 C17 113.27(9) . . ? O6 C19 N4 123.98(10) . . ? O6 C19 C20 120.10(10) . . ? N4 C19 C20 115.85(9) . . ? N5 C20 C21 123.07(10) . . ? N5 C20 C19 117.93(9) . . ? C21 C20 C19 118.86(9) . . ? C22 C21 C20 118.81(10) . . ? C21 C22 C23 118.79(10) . . ? C22 C23 C24 118.53(10) . . ? N5 C24 C23 123.34(10) . . ? N5 C24 C25 117.25(9) . . ? C23 C24 C25 119.38(9) . . ? O7 C25 N6 124.02(10) . . ? O7 C25 C24 120.77(10) . . ? N6 C25 C24 115.21(9) . . ? N6 C26 C27 112.21(9) . . ? C28 C27 C26 112.24(9) . . ? N7 C28 C27 110.73(9) . . ? O8 C29 N7 124.26(10) . . ? O8 C29 C30 119.16(10) . . ? N7 C29 C30 116.47(9) . . ? O9 C30 C29 113.76(9) . . ? 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 O1 N1 C1 C2 173.75(11) . . . . ? O2 N1 C1 C2 -6.40(16) . . . . ? O1 N1 C1 C6 -5.93(16) . . . . ? O2 N1 C1 C6 173.92(11) . . . . ? C6 C1 C2 C3 -3.63(17) . . . . ? N1 C1 C2 C3 176.70(10) . . . . ? C1 C2 C3 C4 0.92(17) . . . . ? C2 C3 C4 C5 2.99(16) . . . . ? C2 C3 C4 C7 -173.47(10) . . . . ? C3 C4 C5 C6 -4.39(16) . . . . ? C7 C4 C5 C6 172.23(10) . . . . ? C4 C5 C6 C1 1.78(17) . . . . ? C2 C1 C6 C5 2.27(17) . . . . ? N1 C1 C6 C5 -178.06(10) . . . . ? C8 N2 C7 O3 1.35(17) . . . . ? C8 N2 C7 C4 176.62(9) . . . . ? C5 C4 C7 O3 30.87(15) . . . . ? C3 C4 C7 O3 -152.58(11) . . . . ? C5 C4 C7 N2 -144.52(10) . . . . ? C3 C4 C7 N2 32.03(14) . . . . ? C7 N2 C8 C9 65.97(14) . . . . ? C7 N2 C8 C13 -117.28(12) . . . . ? C30 O9 C9 C10 16.68(14) . . . . ? C30 O9 C9 C8 -164.36(9) . . . . ? C13 C8 C9 O9 179.75(9) . . . . ? N2 C8 C9 O9 -3.51(14) . . . . ? C13 C8 C9 C10 -1.25(15) . . . . ? N2 C8 C9 C10 175.49(10) . . . . ? O9 C9 C10 C11 177.23(10) . . . . ? C8 C9 C10 C11 -1.67(16) . . . . ? C9 C10 C11 C12 1.67(17) . . . . ? C10 C11 C12 C13 1.31(17) . . . . ? C14 O4 C13 C12 -5.68(15) . . . . ? C14 O4 C13 C8 174.19(9) . . . . ? C11 C12 C13 O4 175.57(10) . . . . ? C11 C12 C13 C8 -4.30(16) . . . . ? C9 C8 C13 O4 -175.59(9) . . . . ? N2 C8 C13 O4 7.61(14) . . . . ? C9 C8 C13 C12 4.29(15) . . . . ? N2 C8 C13 C12 -172.51(10) . . . . ? C13 O4 C14 C15 -146.15(9) . . . . ? C16 N3 C15 O5 -1.25(17) . . . . ? C16 N3 C15 C14 174.84(10) . . . . ? O4 C14 C15 O5 -159.72(9) . . . . ? O4 C14 C15 N3 23.97(13) . . . . ? C15 N3 C16 C17 101.32(12) . . . . ? N3 C16 C17 C18 59.32(12) . . . . ? C19 N4 C18 C17 98.64(12) . . . . ? C16 C17 C18 N4 64.24(12) . . . . ? C18 N4 C19 O6 -10.57(17) . . . . ? C18 N4 C19 C20 166.26(9) . . . . ? C24 N5 C20 C21 0.84(16) . . . . ? C24 N5 C20 C19 -174.91(9) . . . . ? O6 C19 C20 N5 167.31(10) . . . . ? N4 C19 C20 N5 -9.65(14) . . . . ? O6 C19 C20 C21 -8.62(16) . . . . ? N4 C19 C20 C21 174.41(10) . . . . ? N5 C20 C21 C22 -0.48(17) . . . . ? C19 C20 C21 C22 175.24(10) . . . . ? C20 C21 C22 C23 -0.39(17) . . . . ? C21 C22 C23 C24 0.84(17) . . . . ? C20 N5 C24 C23 -0.35(16) . . . . ? C20 N5 C24 C25 177.58(9) . . . . ? C22 C23 C24 N5 -0.49(17) . . . . ? C22 C23 C24 C25 -178.38(10) . . . . ? C26 N6 C25 O7 15.78(17) . . . . ? C26 N6 C25 C24 -164.09(10) . . . . ? N5 C24 C25 O7 -176.15(10) . . . . ? C23 C24 C25 O7 1.87(15) . . . . ? N5 C24 C25 N6 3.72(14) . . . . ? C23 C24 C25 N6 -178.26(10) . . . . ? C25 N6 C26 C27 -135.83(11) . . . . ? N6 C26 C27 C28 -166.40(9) . . . . ? C29 N7 C28 C27 -178.47(9) . . . . ? C26 C27 C28 N7 71.62(11) . . . . ? C28 N7 C29 O8 -3.61(16) . . . . ? C28 N7 C29 C30 172.56(9) . . . . ? C9 O9 C30 C29 69.53(12) . . . . ? O8 C29 C30 O9 -161.77(10) . . . . ? N7 C29 C30 O9 21.86(13) . . . . ? 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 O1W H1WA O3 0.80(2) 2.00(2) 2.7949(13) 170(2) . O1W H1WB O7 0.88(2) 1.95(2) 2.7801(12) 157.8(19) 2_655 N2 H2 O5 0.881(18) 1.910(19) 2.7691(12) 164.4(17) 3_666 N3 H3 O1W 0.854(19) 2.328(19) 3.0473(13) 142.1(16) . N4 H4 O1W 0.897(19) 2.264(19) 3.0801(13) 151.1(16) . N6 H6 O1W 0.874(19) 2.59(2) 3.3963(13) 153.5(16) . N7 H7 O3 0.848(17) 2.147(17) 2.9792(12) 167.0(16) . _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.476 _refine_diff_density_min -0.365 _refine_diff_density_rms 0.077 _publcif_info_exptl_table_max_cols 6 # publcif shelxl _publcif_info_exptl_table_extra_item loop start loop_ _publcif_info_exptl_table_extra_item ? # publcif shelxl _publcif_info_exptl_table_extra_item loop end # publcif shelxl _publcif_info_exptl_table_header_item loop start loop_ _publcif_info_exptl_table_header_item ? # publcif shelxl _publcif_info_exptl_table_header_item loop end # publcif shelxl _publcif_info_datablock.id loop start loop_ _publcif_info_datablock.id _publcif_info_datablock.publ_exptl _publcif_info_datablock.publ_geom _publcif_info_datablock.structure New_Global_Publ_Block ? ? ? shelxl y y y # publcif shelxl _publcif_info_datablock.id loop end