#============================================================================== data_global #============================================================================== _publ_contact_author 'V\'ronique Gouverneur' _publ_contact_author_email veronique.gouverneur@chem.ox.ac.uk loop_ _publ_author_name _publ_author_address 'Roagna, Giulia' ; Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA. UK. ; 'Ascough, David M. H.' ; Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA. UK. ; 'Ibba, Francesco' ; Janssen Cilag Research and Development, Calle Jarama 75A, Toledo 45007, Spain ; 'Fontana, Alberto' ; Janssen Cilag Research and Development, Calle Jarama 75A, Toledo 45007, Spain ; 'Christensen, Kirsten E.' ; Chemical Crystallography Department, Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA. UK. ; 'Peschiulli, Aldo' ; Discovery Sciences Medicinal Chemistry, Janssen Research & Development, Janssen Pharmaceutica N.V., Turnhoutseweg 30, Beerse B-2340, Belgium ; 'Oehlrich, Daniel' ; Discovery Sciences Medicinal Chemistry, Janssen Research & Development, Janssen Pharmaceutica N.V., Turnhoutseweg 30, Beerse B-2340, Belgium ; 'Misale, Antonio' ; Janssen Cilag Research and Development, Calle Jarama 75A, Toledo 45007, Spain ; 'Trabanco, Andres A.' ; Janssen Cilag Research and Development, Calle Jarama 75A, Toledo 45007, Spain ; 'Paton, Robert S. ' ; Department of Chemistry, Colorado State University, Fort Collins, CO 80523, USA ; 'Pupo, Gabriele' ; Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA. UK. ; 'Gouverneur, V\'eronique' ; Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA. UK. ; _publ_requested_journal 'JACS' _journal_volume '?' _journal_page_first '?' _journal_page_last '?' _journal_year '2020' _ccdc_journal_depnumber '?' _publ_section_title ; Hydrogen Bonding Phase-Transfer Catalysis with Ionic Reactants: Enantioselective Synthesis of \g-Fluoroamines ; _publ_section_abstract ; Ammonium salts are classically used as phase transfer catalysts for fluorination with metal alkali fluoride. We now demonstrate that these organic salts, specifically azetidinium triflates, are amenable to enantioselective ring opening with CsF in the presence of a chiral bis-urea catalyst. This process highlights the unique ability of hydrogen bonding phase-transfer catalysts to couple two ionic reactants, and affords enantioenriched \g-fluoroamines in high yields. Mechanistic studies underline the role of the hydrogen bond donor catalyst in the phase-transfer process, and transition state structure analysis explains the enantioconvergence observed for mixtures of achiral azetidinium diastereomers as arising from the unimportance of the configuration at nitrogen. ; #============================================================================== data_(S)-2ma-HCL #============================================================================== _audit_creation_date "2019-03-06" _audit_creation_method 'CRYSTALS_ver_14.61_build_7285 ' _oxford_structure_analysis_title '7118' _chemical_name_systematic . _chemical_melting_point 'not measured' _refine_special_details ; All reflections used summary: ___________________________________________________________ Flack parameter from refinement -0.004(8) Hole-in-one -0.007(7) (44 outliers) Hooft method -0.005(6) Truncated average of ratios (x) -0.004(5) (411 refls truncated) Bijvoet differences -0.006(5) (17 outliers) Parsons quotients -0.011(5) (12 outliers) ____________________________________________________________ 2049 reflections after aplying filters 1,2,3 and 5 summary: ____________________________________________________________ Flack parameter from refinement -0.004(8) Hole-in-one -0.007(7) (43 outliers) Hooft method -0.005(6) Truncated average of ratios (x) -0.004(5) (409 refls truncated) Bijvoet differences -0.006(5) (17 outliers) Parsons quotients -0.012(5) (12 outliers) ____________________________________________________________ 1759 Reflections in all filters summary: ____________________________________________________________ Flack parameter from refinement -0.004(8) Hole-in-one -0.005(7) (41 outliers) Hooft method -0.004(6) Truncated average of ratios (x) -0.001(5) (351 refls truncated) Bijvoet differences -0.005(5) (11 outliers) Parsons quotients -0.010(4) (8 outliers) ____________________________________________________________ ; _cell_length_a 9.98040(10) _cell_length_b 8.61600(10) _cell_length_c 12.82200(10) _cell_angle_alpha 90 _cell_angle_beta 102.1108(12) _cell_angle_gamma 90 _cell_volume 1078.039(19) _symmetry_cell_setting 'monoclinic' _symmetry_space_group_name_H-M 'P 21 ' _symmetry_space_group_name_Hall 'P 2yb' loop_ _symmetry_equiv_pos_as_xyz 'x,y,z' '-x,y+1/2,-z' loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0181 0.0091 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Cl 0.3639 0.7018 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International Tables Vol C 4.2.6.8 and 6.1.1.4' F 0.0727 0.0534 3.5392 10.2825 2.6412 4.2944 1.5170 0.2615 1.0243 26.1476 0.2776 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0311 0.0180 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0492 0.0322 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 2 # Given Formula = C25 H29 Cl1 F1 N1 O1 # Dc = 1.28 Fooo = 440.00 Mu = 17.59 M = 413.96 # Found Formula = C25 H29.00 Cl1 F1 N1 O1 # Dc = 1.28 FOOO = 440.00 Mu = 17.59 M = 413.96 _chemical_formula_sum 'C25 H29 Cl F N O' _chemical_formula_moiety 'C25 H29 F N O, Cl' _chemical_compound_source . _chemical_formula_weight 413.96 _cell_measurement_reflns_used 7644 _cell_measurement_theta_min 4.50 _cell_measurement_theta_max 76.00 _cell_measurement_temperature 150 _exptl_crystal_description 'lath' _exptl_crystal_colour 'clear_pale_colourless' _exptl_crystal_size_min 0.09 _exptl_crystal_size_mid 0.22 _exptl_crystal_size_max 0.25 _exptl_crystal_density_diffrn 1.275 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_method 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 439.997 _exptl_absorpt_coefficient_mu 1.759 # Sheldrick geometric approximatio 0.68 0.85 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro (Rigaku Oxford Diffraction, 2017) ; _exptl_absorpt_correction_T_min 0.74 _exptl_absorpt_correction_T_max 0.85 _diffrn_measurement_device_type 'Oxford Diffraction SuperNova' _diffrn_measurement_device 'Area' _diffrn_radiation_monochromator 'focussing mirrors' _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_wavelength 1.54184 _diffrn_measurement_method \w # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'SuperNova, (Oxford Diffraction, 2010)' _computing_cell_refinement ; CrysAlisPro (Rigaku Oxford Diffraction, 2017) ; _computing_data_reduction ; CrysAlisPro (Rigaku Oxford Diffraction, 2017) ; _computing_structure_solution 'Superflip (Palatinus & Chapuis, 2007)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time . _diffrn_standards_interval_count . _diffrn_standards_number 0 _diffrn_standards_decay_% . _diffrn_ambient_temperature 150 _diffrn_reflns_number 10448 _diffrn_reflns_av_unetI/netI 0.041 _reflns_number_total 4454 _diffrn_reflns_av_R_equivalents 0.027 _diffrn_reflns_av_sigmaI/netI 0.0407 # Number of reflections without Friedels Law is 4454 # Number of reflections with Friedels Law is 2396 # Theoretical number of reflections is about 2258 _diffrn_reflns_theta_min 3.526 _diffrn_reflns_theta_max 76.232 _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 74.707 _diffrn_measured_fraction_theta_full 0.996 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 10 _reflns_limit_h_min -12 _reflns_limit_h_max 12 _reflns_limit_k_min -10 _reflns_limit_k_max 10 _reflns_limit_l_min 0 _reflns_limit_l_max 16 _oxford_diffrn_Wilson_B_factor 2.03 _oxford_diffrn_Wilson_scale 0.01 _atom_sites_solution_primary other #heavy,direct,difmap,geom,iterative # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_diff_density_min -0.06 _refine_diff_density_max 0.05 # The current dictionary definitions do not cover the # situation where the reflections used for refinement were # selected by a user-defined sigma threshold # The values actually used during refinement _oxford_refine_reflns_threshold_expression_ref I>-3.0\s(I) _refine_ls_number_restraints 1 _refine_ls_number_parameters 263 _refine_ls_number_reflns 4454 _oxford_refine_ls_R_factor_ref 0.0268 _refine_ls_wR_factor_ref 0.0706 _refine_ls_goodness_of_fit_ref 0.9949 _refine_ls_shift/su_max 0.0014251 _refine_ls_shift/su_mean 0.0000383 # The values computed with all filters except I/sigma _oxford_reflns_number_all 4454 _refine_ls_R_factor_all 0.0268 _refine_ls_wR_factor_all 0.0706 # The values computed with a 2 sigma cutoff - a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 4390 _refine_ls_R_factor_gt 0.0265 _refine_ls_wR_factor_gt 0.0700 # For an explanation, see Cooper & Watkin, Acta Cryst. (2016). B72, 661-683 _oxford_Hooft_y -0.005(6) # for 2049 Friedel pairs _oxford_Bijvoet_difference -0.010(5) # for 2049 Friedel pairs # (Similar to the Parsons(q).) _oxford_refined_Flack_x -0.004(8) # for 2058 Friedel pairs _refine_ls_abs_structure_Flack -0.010(5) _refine_ls_abs_structure_details ; Parsons, Flack & Wagner (2013), 2049 Friedel Pairs ; # choose from: # rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration 'ad' _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_hydrogen_treatment constr #undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method= Modified Sheldrick w=1/[\s^2^(F^2^) + ( 0.05P)^2^ + 0.04P] ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 ; # Insert your own references if required - in alphabetical order _publ_section_references ; Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Oxford Diffraction, (2010). Supernova User Manual. Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786-790. Parsons,S., Flack, H.D. and Wagner, T. Acta Cryst. (2013). B69, 249–259 Rigaku Oxford Diffraction (2017). CrysAlisPro. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical Crystallography Laboratory, Oxford, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atoms attached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens F1 F 0.37962(8) 0.50000(10) 0.50123(6) 0.0277 1.0000 Uani . . . . . . C2 C 0.24512(12) 0.46048(15) 0.50928(9) 0.0222 1.0000 Uani . . . . . . C3 C 0.22546(11) 0.28765(14) 0.49166(8) 0.0180 1.0000 Uani . . . . . . O4 O 0.23091(8) 0.24697(11) 0.38483(6) 0.0196 1.0000 Uani . . . . . . C5 C 0.10059(12) 0.26701(17) 0.31333(9) 0.0253 1.0000 Uani . . . . . . C6 C 0.11812(11) 0.25556(15) 0.19989(9) 0.0216 1.0000 Uani . . . . . . C7 C 0.18428(14) 0.12993(16) 0.16511(10) 0.0297 1.0000 Uani . . . . . . C8 C 0.19893(16) 0.12176(18) 0.05980(12) 0.0351 1.0000 Uani . . . . . . C9 C 0.14368(15) 0.23573(19) -0.01256(10) 0.0325 1.0000 Uani . . . . . . C10 C 0.07696(15) 0.36002(19) 0.02146(11) 0.0351 1.0000 Uani . . . . . . C11 C 0.06517(14) 0.37129(17) 0.12749(11) 0.0292 1.0000 Uani . . . . . . C12 C 0.33807(11) 0.19684(13) 0.56591(8) 0.0188 1.0000 Uani . . . . . . N13 N 0.29008(9) 0.04508(12) 0.60385(7) 0.0171 1.0000 Uani . . . . . . C14 C 0.21102(12) -0.05536(14) 0.51504(9) 0.0204 1.0000 Uani . . . . . . C15 C 0.29544(13) -0.12083(15) 0.44008(10) 0.0253 1.0000 Uani . . . . . . C16 C 0.41173(11) -0.03959(13) 0.67208(8) 0.0179 1.0000 Uani . . . . . . C17 C 0.37197(11) -0.19348(14) 0.71512(8) 0.0182 1.0000 Uani . . . . . . C18 C 0.46585(11) -0.31449(15) 0.72135(9) 0.0214 1.0000 Uani . . . . . . C19 C 0.44263(13) -0.45528(15) 0.76809(10) 0.0250 1.0000 Uani . . . . . . C20 C 0.32453(14) -0.47673(15) 0.80713(10) 0.0263 1.0000 Uani . . . . . . C21 C 0.23046(12) -0.35645(15) 0.80073(9) 0.0246 1.0000 Uani . . . . . . C22 C 0.25427(12) -0.21438(15) 0.75583(9) 0.0223 1.0000 Uani . . . . . . C23 C 0.48910(12) 0.06129(14) 0.76251(9) 0.0207 1.0000 Uani . . . . . . C24 C 0.43087(14) 0.10643(16) 0.84764(10) 0.0270 1.0000 Uani . . . . . . C25 C 0.50878(17) 0.18833(17) 0.93248(10) 0.0349 1.0000 Uani . . . . . . C26 C 0.64384(17) 0.22428(17) 0.93288(11) 0.0379 1.0000 Uani . . . . . . C27 C 0.70216(14) 0.18124(19) 0.84840(12) 0.0370 1.0000 Uani . . . . . . C28 C 0.62488(13) 0.09873(16) 0.76292(11) 0.0282 1.0000 Uani . . . . . . Cl29 Cl 0.05103(3) 0.17053(6) 0.68861(2) 0.0257 1.0000 Uani . . . . . . H21 H 0.1835 0.5202 0.4567 0.0268 1.0000 Uiso R . . . . . H22 H 0.2347 0.4882 0.5809 0.0271 1.0000 Uiso R . . . . . H31 H 0.1367 0.2622 0.5056 0.0215 1.0000 Uiso R . . . . . H51 H 0.0648 0.3645 0.3246 0.0307 1.0000 Uiso R . . . . . H52 H 0.0407 0.1849 0.3276 0.0296 1.0000 Uiso R . . . . . H71 H 0.2215 0.0513 0.2131 0.0366 1.0000 Uiso R . . . . . H81 H 0.2474 0.0357 0.0375 0.0418 1.0000 Uiso R . . . . . H91 H 0.1522 0.2285 -0.0836 0.0377 1.0000 Uiso R . . . . . H101 H 0.0441 0.4410 -0.0259 0.0426 1.0000 Uiso R . . . . . H111 H 0.0232 0.4597 0.1521 0.0346 1.0000 Uiso R . . . . . H121 H 0.3692 0.2594 0.6274 0.0235 1.0000 Uiso R . . . . . H122 H 0.4121 0.1775 0.5304 0.0220 1.0000 Uiso R . . . . . H141 H 0.1346 0.0062 0.4736 0.0245 1.0000 Uiso R . . . . . H142 H 0.1733 -0.1379 0.5475 0.0245 1.0000 Uiso R . . . . . H151 H 0.2352 -0.1722 0.3837 0.0378 1.0000 Uiso R . . . . . H153 H 0.3398 -0.0387 0.4091 0.0379 1.0000 Uiso R . . . . . H152 H 0.3648 -0.1952 0.4771 0.0373 1.0000 Uiso R . . . . . H161 H 0.4747 -0.0580 0.6261 0.0198 1.0000 Uiso R . . . . . H181 H 0.5480 -0.2988 0.6946 0.0256 1.0000 Uiso R . . . . . H191 H 0.5031 -0.5375 0.7711 0.0325 1.0000 Uiso R . . . . . H201 H 0.3059 -0.5748 0.8376 0.0324 1.0000 Uiso R . . . . . H211 H 0.1509 -0.3701 0.8259 0.0306 1.0000 Uiso R . . . . . H221 H 0.1906 -0.1311 0.7514 0.0264 1.0000 Uiso R . . . . . H241 H 0.3379 0.0832 0.8475 0.0317 1.0000 Uiso R . . . . . H251 H 0.4682 0.2183 0.9879 0.0432 1.0000 Uiso R . . . . . H261 H 0.6955 0.2777 0.9911 0.0448 1.0000 Uiso R . . . . . H271 H 0.7977 0.2023 0.8506 0.0450 1.0000 Uiso R . . . . . H281 H 0.6633 0.0678 0.7033 0.0346 1.0000 Uiso R . . . . . H131 H 0.2298 0.0685 0.6435 0.0250 1.0000 Uiso 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 F1 0.0295(4) 0.0248(3) 0.0289(4) 0.0000(3) 0.0061(3) -0.0043(3) C2 0.0244(5) 0.0225(5) 0.0190(5) 0.0007(4) 0.0032(4) 0.0033(4) C3 0.0188(5) 0.0216(5) 0.0133(5) 0.0021(4) 0.0028(4) 0.0014(4) O4 0.0183(4) 0.0259(4) 0.0132(3) -0.0003(3) 0.0004(3) 0.0037(3) C5 0.0184(5) 0.0398(7) 0.0162(5) 0.0009(5) -0.0000(4) 0.0028(5) C6 0.0176(5) 0.0291(6) 0.0163(5) -0.0015(4) -0.0003(4) -0.0024(4) C7 0.0352(6) 0.0300(7) 0.0223(6) 0.0008(5) 0.0023(5) 0.0050(5) C8 0.0436(7) 0.0342(7) 0.0282(7) -0.0081(5) 0.0090(5) 0.0033(6) C9 0.0356(7) 0.0434(7) 0.0194(5) -0.0029(5) 0.0074(5) -0.0043(6) C10 0.0390(7) 0.0430(8) 0.0240(6) 0.0105(6) 0.0083(5) 0.0050(6) C11 0.0335(6) 0.0308(6) 0.0243(6) 0.0037(5) 0.0086(5) 0.0053(5) C12 0.0191(5) 0.0199(5) 0.0159(4) 0.0031(4) 0.0001(4) -0.0012(4) N13 0.0168(4) 0.0189(4) 0.0150(4) 0.0018(3) 0.0020(3) 0.0003(3) C14 0.0207(5) 0.0209(5) 0.0177(5) 0.0012(4) -0.0005(4) -0.0028(4) C15 0.0301(6) 0.0230(5) 0.0214(5) -0.0048(4) 0.0025(4) -0.0004(5) C16 0.0173(5) 0.0197(5) 0.0158(5) 0.0016(4) 0.0013(4) 0.0008(4) C17 0.0194(5) 0.0191(5) 0.0144(4) 0.0014(4) -0.0003(4) 0.0003(4) C18 0.0204(5) 0.0228(5) 0.0201(5) 0.0006(4) 0.0020(4) 0.0018(5) C19 0.0279(6) 0.0214(5) 0.0236(5) 0.0011(4) 0.0009(4) 0.0042(5) C20 0.0318(6) 0.0227(6) 0.0217(5) 0.0049(4) -0.0004(5) -0.0016(5) C21 0.0231(5) 0.0280(7) 0.0217(5) 0.0057(4) 0.0026(4) -0.0027(4) C22 0.0216(5) 0.0238(6) 0.0208(5) 0.0026(4) 0.0029(4) 0.0019(4) C23 0.0229(5) 0.0193(5) 0.0173(5) 0.0032(4) -0.0017(4) 0.0009(4) C24 0.0340(6) 0.0262(6) 0.0200(6) 0.0010(5) 0.0040(5) -0.0007(5) C25 0.0558(8) 0.0270(7) 0.0193(5) -0.0006(5) 0.0018(5) -0.0020(6) C26 0.0520(8) 0.0251(6) 0.0260(6) 0.0031(5) -0.0160(6) -0.0067(6) C27 0.0296(6) 0.0336(7) 0.0400(7) 0.0059(6) -0.0103(5) -0.0061(6) C28 0.0247(6) 0.0286(6) 0.0285(6) 0.0028(5) -0.0011(5) -0.0011(5) Cl29 0.02514(13) 0.03083(14) 0.02269(12) 0.00087(10) 0.00834(9) 0.00224(11) _refine_ls_extinction_method 'None' _oxford_refine_ls_scale 10.7(3) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag F1 . C2 . 1.4095(14) yes C2 . C3 . 1.5127(16) yes C2 . H21 . 0.961 no C2 . H22 . 0.976 no C3 . O4 . 1.4259(13) yes C3 . C12 . 1.5273(14) yes C3 . H31 . 0.965 no O4 . C5 . 1.4358(13) yes C5 . C6 . 1.5043(15) yes C5 . H51 . 0.935 no C5 . H52 . 0.968 no C6 . C7 . 1.3893(18) yes C6 . C11 . 1.3890(18) yes C7 . C8 . 1.3901(19) yes C7 . H71 . 0.938 no C8 . C9 . 1.384(2) yes C8 . H81 . 0.961 no C9 . C10 . 1.379(2) yes C9 . H91 . 0.934 no C10 . C11 . 1.3924(19) yes C10 . H101 . 0.938 no C11 . H111 . 0.954 no C12 . N13 . 1.5078(14) yes C12 . H121 . 0.951 no C12 . H122 . 0.960 no N13 . C14 . 1.5137(14) yes N13 . C16 . 1.5251(13) yes N13 . H131 . 0.888 no C14 . C15 . 1.5138(17) yes C14 . H141 . 0.988 no C14 . H142 . 0.941 no C15 . H151 . 0.947 no C15 . H153 . 0.964 no C15 . H152 . 0.988 no C16 . C17 . 1.5205(15) yes C16 . C23 . 1.5234(15) yes C16 . H161 . 0.961 no C17 . C18 . 1.3928(16) yes C17 . C22 . 1.3936(16) yes C18 . C19 . 1.3938(17) yes C18 . H181 . 0.962 no C19 . C20 . 1.3863(19) yes C19 . H191 . 0.927 no C20 . C21 . 1.3892(18) yes C20 . H201 . 0.965 no C21 . C22 . 1.3941(17) yes C21 . H211 . 0.925 no C22 . H221 . 0.952 no C23 . C24 . 1.3952(18) yes C23 . C28 . 1.3920(17) yes C24 . C25 . 1.3896(19) yes C24 . H241 . 0.948 no C25 . C26 . 1.382(2) yes C25 . H251 . 0.925 no C26 . C27 . 1.384(2) yes C26 . H261 . 0.934 no C27 . C28 . 1.395(2) yes C27 . H271 . 0.965 no C28 . H281 . 0.962 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag F1 . C2 . C3 . 108.82(9) yes F1 . C2 . H21 . 107.3 no C3 . C2 . H21 . 112.2 no F1 . C2 . H22 . 107.5 no C3 . C2 . H22 . 110.2 no H21 . C2 . H22 . 110.5 no C2 . C3 . O4 . 110.82(9) yes C2 . C3 . C12 . 110.84(9) yes O4 . C3 . C12 . 107.55(9) yes C2 . C3 . H31 . 106.9 no O4 . C3 . H31 . 110.1 no C12 . C3 . H31 . 110.6 no C3 . O4 . C5 . 111.83(8) yes O4 . C5 . C6 . 109.63(9) yes O4 . C5 . H51 . 109.5 no C6 . C5 . H51 . 109.5 no O4 . C5 . H52 . 107.7 no C6 . C5 . H52 . 109.7 no H51 . C5 . H52 . 110.9 no C5 . C6 . C7 . 121.40(11) yes C5 . C6 . C11 . 119.61(11) yes C7 . C6 . C11 . 118.98(12) yes C6 . C7 . C8 . 120.34(12) yes C6 . C7 . H71 . 120.1 no C8 . C7 . H71 . 119.5 no C7 . C8 . C9 . 120.47(13) yes C7 . C8 . H81 . 119.4 no C9 . C8 . H81 . 120.2 no C8 . C9 . C10 . 119.33(12) yes C8 . C9 . H91 . 120.1 no C10 . C9 . H91 . 120.5 no C9 . C10 . C11 . 120.55(13) yes C9 . C10 . H101 . 120.0 no C11 . C10 . H101 . 119.4 no C10 . C11 . C6 . 120.28(13) yes C10 . C11 . H111 . 120.7 no C6 . C11 . H111 . 119.0 no C3 . C12 . N13 . 113.79(9) yes C3 . C12 . H121 . 107.2 no N13 . C12 . H121 . 107.1 no C3 . C12 . H122 . 109.4 no N13 . C12 . H122 . 109.3 no H121 . C12 . H122 . 110.0 no C12 . N13 . C14 . 113.82(8) yes C12 . N13 . C16 . 109.35(8) yes C14 . N13 . C16 . 112.62(8) yes C12 . N13 . H131 . 106.7 no C14 . N13 . H131 . 104.6 no C16 . N13 . H131 . 109.5 no N13 . C14 . C15 . 114.77(9) yes N13 . C14 . H141 . 108.6 no C15 . C14 . H141 . 109.2 no N13 . C14 . H142 . 107.0 no C15 . C14 . H142 . 109.1 no H141 . C14 . H142 . 108.0 no C14 . C15 . H151 . 108.0 no C14 . C15 . H153 . 110.7 no H151 . C15 . H153 . 107.6 no C14 . C15 . H152 . 111.3 no H151 . C15 . H152 . 109.4 no H153 . C15 . H152 . 109.7 no N13 . C16 . C17 . 112.85(8) yes N13 . C16 . C23 . 112.27(9) yes C17 . C16 . C23 . 110.52(9) yes N13 . C16 . H161 . 105.8 no C17 . C16 . H161 . 109.4 no C23 . C16 . H161 . 105.6 no C16 . C17 . C18 . 116.73(10) yes C16 . C17 . C22 . 123.60(10) yes C18 . C17 . C22 . 119.44(11) yes C17 . C18 . C19 . 120.37(11) yes C17 . C18 . H181 . 119.2 no C19 . C18 . H181 . 120.4 no C18 . C19 . C20 . 120.13(11) yes C18 . C19 . H191 . 121.2 no C20 . C19 . H191 . 118.6 no C19 . C20 . C21 . 119.64(12) yes C19 . C20 . H201 . 120.9 no C21 . C20 . H201 . 119.4 no C20 . C21 . C22 . 120.52(12) yes C20 . C21 . H211 . 120.2 no C22 . C21 . H211 . 119.2 no C21 . C22 . C17 . 119.88(11) yes C21 . C22 . H221 . 121.1 no C17 . C22 . H221 . 119.0 no C16 . C23 . C24 . 121.78(11) yes C16 . C23 . C28 . 118.21(11) yes C24 . C23 . C28 . 119.83(12) yes C23 . C24 . C25 . 119.83(13) yes C23 . C24 . H241 . 120.5 no C25 . C24 . H241 . 119.7 no C24 . C25 . C26 . 120.12(13) yes C24 . C25 . H251 . 118.7 no C26 . C25 . H251 . 121.2 no C25 . C26 . C27 . 120.48(12) yes C25 . C26 . H261 . 119.2 no C27 . C26 . H261 . 120.3 no C26 . C27 . C28 . 119.84(13) yes C26 . C27 . H271 . 120.1 no C28 . C27 . H271 . 119.9 no C27 . C28 . C23 . 119.88(13) yes C27 . C28 . H281 . 121.2 no C23 . C28 . H281 . 118.9 no _iucr_refine_instructions_details ; # # Punched on 06/03/19 at 12:43:42 # #LIST 12 BLOCK SCALE X'S U'S CONT ENANTIO RIDE C ( 2,X'S) H ( 21,X'S) H ( 22,X'S) RIDE C ( 3,X'S) H ( 31,X'S) RIDE C ( 5,X'S) H ( 51,X'S) H ( 52,X'S) RIDE C ( 7,X'S) H ( 71,X'S) RIDE C ( 8,X'S) H ( 81,X'S) RIDE C ( 9,X'S) H ( 91,X'S) RIDE C ( 10,X'S) H ( 101,X'S) RIDE C ( 11,X'S) H ( 111,X'S) RIDE C ( 12,X'S) H ( 121,X'S) H ( 122,X'S) RIDE N ( 13,X'S) H ( 131,X'S) RIDE C ( 14,X'S) H ( 141,X'S) H ( 142,X'S) RIDE C ( 15,X'S) H ( 151,X'S) H ( 153,X'S) H ( 152,X'S) RIDE C ( 16,X'S) H ( 161,X'S) RIDE C ( 18,X'S) H ( 181,X'S) RIDE C ( 19,X'S) H ( 191,X'S) RIDE C ( 20,X'S) H ( 201,X'S) RIDE C ( 21,X'S) H ( 211,X'S) RIDE C ( 22,X'S) H ( 221,X'S) RIDE C ( 24,X'S) H ( 241,X'S) RIDE C ( 25,X'S) H ( 251,X'S) RIDE C ( 26,X'S) H ( 261,X'S) RIDE C ( 27,X'S) H ( 271,X'S) RIDE C ( 28,X'S) H ( 281,X'S) END # # Punched on 06/03/19 at 12:43:42 # #LIST 16 NO REM HREST START (DO NOT REMOVE THIS LINE) REM HREST END (DO NOT REMOVE THIS LINE) END ; #============================================================================== data_(R)-3ab-HCl #============================================================================== _audit_creation_date "2019-07-15" _audit_creation_method 'CRYSTALS_ver_14.61_build_7356 ' _oxford_structure_analysis_title 'exp_4468_2_300_00 -7146-CU' _chemical_name_systematic . _chemical_melting_point 'not measured' _diffrn_special_details ; Crystal were initially put on at 150 K but all crystals were split. Variable temperature experiments with both Mo- and Cu- radiation were performed at 300K and 150K. For each crystal at each wavelength the crystal split at 150 K. Therefore only the 300 K data was used in refinement. ; _refine_special_details ; Upon refinement the structure was found to have disorder in the C-F side group. Appropriate restrains and constrains were aplied. ; _cell_length_a 9.95040(10) _cell_length_b 10.52650(10) _cell_length_c 23.7547(4) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 2488.14(5) _symmetry_cell_setting 'orthorhombic' _symmetry_space_group_name_H-M 'P 21 21 21 ' _symmetry_space_group_name_Hall 'P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz 'x,y,z' '-x+1/2,-y,z+1/2' 'x+1/2,-y+1/2,-z' '-x,y+1/2,-z+1/2' loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0181 0.0091 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' F 0.0727 0.0534 3.5392 10.2825 2.6412 4.2944 1.5170 0.2615 1.0243 26.1476 0.2776 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0311 0.0180 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Cl 0.3639 0.7018 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 8 # Given Formula = C11 H16 Cl1 F1 N1 # Dc = 1.16 Fooo = 920.00 Mu = 25.43 M = 216.71 # Found Formula = C11.00 H17 Cl1 F1.00 N1 # Dc = 1.16 FOOO = 928.00 Mu = 25.44 M = 217.71 _chemical_formula_sum 'C11 H17 Cl F1 N' _chemical_formula_moiety 'C11 H17 F1 N, Cl' _chemical_compound_source . _chemical_formula_weight 217.71 _cell_measurement_reflns_used 18010 _cell_measurement_theta_min 3.72 _cell_measurement_theta_max 76.91 _cell_measurement_temperature 300 _exptl_crystal_description 'plate' _exptl_crystal_colour 'clear_pale_colourless' _exptl_crystal_size_min 0.10 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_max 0.40 _exptl_crystal_density_diffrn 1.162 _exptl_crystal_density_meas 'not measured' _exptl_crystal_density_method 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 928.000 _exptl_absorpt_coefficient_mu 2.544 # Sheldrick geometric approximatio 0.53 0.78 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlisPro (Rigaku Oxford Diffraction, 2017) ; _exptl_absorpt_correction_T_min 0.41 _exptl_absorpt_correction_T_max 0.78 _diffrn_measurement_device_type 'Oxford Diffraction SuperNova' _diffrn_measurement_device 'Area' _diffrn_radiation_monochromator 'focussing mirrors' _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_wavelength 1.54184 _diffrn_measurement_method \w # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'SuperNova, (Oxford Diffraction, 2010)' _computing_cell_refinement ; CrysAlisPro (Rigaku Oxford Diffraction, 2017) ; _computing_data_reduction ; CrysAlisPro (Rigaku Oxford Diffraction, 2017) ; _computing_structure_solution 'Superflip (Palatinus & Chapuis, 2007)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics 'CAMERON (Watkin et al., 1996)' _diffrn_standards_interval_time . _diffrn_standards_interval_count . _diffrn_standards_number 0 _diffrn_standards_decay_% . _diffrn_ambient_temperature 300 _diffrn_reflns_number 49083 _diffrn_reflns_av_unetI/netI 0.052 _reflns_number_total 5262 _diffrn_reflns_av_R_equivalents 0.060 _diffrn_reflns_av_sigmaI/netI 0.0524 # Number of reflections without Friedels Law is 5262 # Number of reflections with Friedels Law is 2996 # Theoretical number of reflections is about 2639 _diffrn_reflns_theta_min 3.721 _diffrn_reflns_theta_max 77.272 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 77.272 _diffrn_measured_fraction_theta_full 0.998 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 29 _reflns_limit_h_min -12 _reflns_limit_h_max 12 _reflns_limit_k_min 0 _reflns_limit_k_max 13 _reflns_limit_l_min 0 _reflns_limit_l_max 30 _oxford_diffrn_Wilson_B_factor 5.77 _oxford_diffrn_Wilson_scale 0.06 _atom_sites_solution_primary other #heavy,direct,difmap,geom,iterative # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_diff_density_min -0.16 _refine_diff_density_max 0.12 # The current dictionary definitions do not cover the # situation where the reflections used for refinement were # selected by a user-defined sigma threshold # Explicitly named reflections are ALWAYS excluded from R&wR # The values actually used during refinement _oxford_refine_reflns_threshold_expression_ref I>-10.0\s(I) _refine_ls_number_restraints 48 _refine_ls_number_parameters 307 _refine_ls_number_reflns 5262 _oxford_refine_ls_R_factor_ref 0.0382 _refine_ls_wR_factor_ref 0.0997 _refine_ls_goodness_of_fit_ref 1.0011 _refine_ls_shift/su_max 0.0006166 _refine_ls_shift/su_mean 0.0000456 # Computed with no filters except I/sigma = -10 _oxford_reflns_number_all 5262 _refine_ls_R_factor_all 0.0382 _refine_ls_wR_factor_all 0.0997 # Computed with no filters except I/sigma = +2 a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 4695 _refine_ls_R_factor_gt 0.0343 _refine_ls_wR_factor_gt 0.0944 # For an explanation, see Cooper & Watkin, Acta Cryst. (2016). B72, 661-683 _oxford_Hooft_y -0.005(7) # for 2145 Friedel pairs _oxford_Bijvoet_difference 0.001(6) # for 2145 Friedel pairs # (Similar to the Parsons(q).) _oxford_refined_Flack_x 0.007(13) # for 2266 Friedel pairs _refine_ls_abs_structure_Flack 0.001(6) _refine_ls_abs_structure_details ; Parsons, Flack & Wagner (2013), 2145 Friedel Pairs ; # choose from: # rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration 'ad' _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_hydrogen_treatment constr #undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method= Modified Sheldrick w=1/[\s^2^(F^2^) + ( 0.06P)^2^ + 0.09P] ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 ; # Insert your own references if required - in alphabetical order _publ_section_references ; Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. Oxford Diffraction, (2010). Supernova User Manual. Palatinus, L. & Chapuis, G. (2007). J. Appl. Cryst. 40, 786-790. Parsons,S., Flack, H.D. and Wagner, T. Acta Cryst. (2013). B69, 249–259 Rigaku Oxford Diffraction (2017). CrysAlisPro. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996). CAMERON, Chemical Crystallography Laboratory, Oxford, UK. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atoms attached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _atom_site_attached_hydrogens C3 C 0.5587(2) 0.31644(17) 0.64790(7) 0.0700 1.0000 Uani D . . . . . C4 C 0.53173(19) 0.23303(18) 0.69871(7) 0.0657 1.0000 Uani . . . . . . N5 N 0.51219(13) 0.30739(12) 0.75141(6) 0.0610 1.0000 Uani . . . . . . C6 C 0.5115(2) 0.2257(2) 0.80292(7) 0.0759 1.0000 Uani . . . . . . C7 C 0.4896(3) 0.3039(3) 0.85509(9) 0.0997 1.0000 Uani . . . . . . C8 C 0.6043(2) 0.23703(17) 0.59789(7) 0.0711 1.0000 Uani . . . . . . C9 C 0.5325(3) 0.1325(2) 0.57985(10) 0.0958 1.0000 Uani . . . . . . C10 C 0.5755(4) 0.0636(3) 0.53338(12) 0.1181 1.0000 Uani . . . . . . C11 C 0.6865(4) 0.0992(3) 0.50457(11) 0.1241 1.0000 Uani . . . . . . C12 C 0.7584(4) 0.2029(3) 0.52187(10) 0.1155 1.0000 Uani . . . . . . C13 C 0.7181(2) 0.2705(2) 0.56833(9) 0.0893 1.0000 Uani . . . . . . Cl14 Cl 0.23786(4) 0.45506(4) 0.75545(2) 0.0762 1.0000 Uani . . . . . . Cl15 Cl 0.25627(5) 0.00104(4) 0.73516(2) 0.0837 1.0000 Uani . . . . . . F21 F 0.0739(6) 0.0335(4) 0.8817(3) 0.1657 0.665(5) Uani D . P 1 1 . C23 C 0.0451(5) 0.2433(5) 0.84809(18) 0.0767 0.665(5) Uani D . P 1 1 . C24 C -0.04092(18) 0.2265(2) 0.79613(7) 0.0685 1.0000 Uani D . . . . . N25 N 0.04477(14) 0.22165(12) 0.74507(5) 0.0619 1.0000 Uani . . . . . . C26 C -0.0321(2) 0.2255(3) 0.69122(8) 0.0746 1.0000 Uani . . . . . . C27 C 0.0611(3) 0.2281(3) 0.64171(9) 0.0965 1.0000 Uani . . . . . . C28 C -0.0379(6) 0.2850(6) 0.8982(2) 0.0770 0.665(5) Uani D . P 1 1 . C29 C -0.1555(5) 0.2324(4) 0.91889(19) 0.0964 0.665(5) Uani D . P 1 1 . C30 C -0.2263(6) 0.2871(5) 0.96252(18) 0.1216 0.665(5) Uani D . P 1 1 . C31 C -0.1812(6) 0.3960(5) 0.98591(19) 0.1306 0.665(5) Uani D . P 1 1 . C32 C -0.0660(6) 0.4529(5) 0.96623(18) 0.1328 0.665(5) Uani D . P 1 1 . C33 C 0.0081(5) 0.3968(5) 0.9224(2) 0.1055 0.665(5) Uani D . P 1 1 . F121 F 0.1260(16) 0.0642(13) 0.9050(5) 0.2076 0.335(5) Uani D . P 1 2 . C122 C 0.0441(13) 0.0731(8) 0.8582(4) 0.1089 0.335(5) Uani D . P 1 2 . C123 C 0.0264(13) 0.2145(9) 0.8534(4) 0.0767 0.335(5) Uani D . P 1 2 . C128 C -0.0597(11) 0.2747(11) 0.8975(4) 0.0770 0.335(5) Uani D . P 1 2 . C129 C -0.1694(12) 0.1971(9) 0.9076(4) 0.0964 0.335(5) Uani D . P 1 2 . C130 C -0.2538(10) 0.2247(9) 0.9515(3) 0.1216 0.335(5) Uani D . P 1 2 . C131 C -0.2292(11) 0.3292(10) 0.9853(3) 0.1306 0.335(5) Uani D . P 1 2 . C132 C -0.1197(11) 0.4077(9) 0.9756(4) 0.1328 0.335(5) Uani D . P 1 2 . C133 C -0.0337(9) 0.3796(10) 0.9312(4) 0.1055 0.335(5) Uani D . P 1 2 . H41 H 0.4491 0.1851 0.6934 0.0789 1.0000 Uiso R . . . . . H42 H 0.6067 0.1754 0.7048 0.0803 1.0000 Uiso R . . . . . H51 H 0.5716 0.3717 0.7555 0.0896 1.0000 Uiso R . . . . . H52 H 0.4356 0.3526 0.7512 0.0902 1.0000 Uiso R . . . . . H61 H 0.4377 0.1639 0.7988 0.0912 1.0000 Uiso R . . . . . H62 H 0.6006 0.1870 0.8048 0.0923 1.0000 Uiso R . . . . . H71 H 0.5691 0.3570 0.8600 0.1496 1.0000 Uiso R . . . . . H72 H 0.4776 0.2500 0.8868 0.1489 1.0000 Uiso R . . . . . H73 H 0.4118 0.3573 0.8524 0.1492 1.0000 Uiso R . . . . . H91 H 0.4547 0.1097 0.5983 0.1154 1.0000 Uiso R . . . . . H101 H 0.5259 -0.0076 0.5217 0.1427 1.0000 Uiso R . . . . . H111 H 0.7122 0.0517 0.4727 0.1488 1.0000 Uiso R . . . . . H121 H 0.8358 0.2280 0.5034 0.1390 1.0000 Uiso R . . . . . H131 H 0.7679 0.3403 0.5799 0.1078 1.0000 Uiso R . . . . . H241 H -0.0978 0.3002 0.7930 0.0829 1.0000 Uiso R . . . . . H242 H -0.0946 0.1499 0.7960 0.0832 1.0000 Uiso R . . . . . H251 H 0.1002 0.2901 0.7457 0.0922 1.0000 Uiso R . . . . . H252 H 0.0958 0.1506 0.7454 0.0922 1.0000 Uiso R . . . . . H261 H -0.0828 0.3044 0.6914 0.0902 1.0000 Uiso R . . . . . H262 H -0.0912 0.1517 0.6890 0.0909 1.0000 Uiso R . . . . . H271 H 0.0116 0.2304 0.6064 0.1431 1.0000 Uiso R . . . . . H272 H 0.1128 0.1511 0.6405 0.1444 1.0000 Uiso R . . . . . H273 H 0.1238 0.2992 0.6430 0.1450 1.0000 Uiso R . . . . . C22 C 0.1398(5) 0.1395(6) 0.8659(2) 0.1227 0.665(5) Uani D . P 1 1 . H1231 H 0.1154 0.2533 0.8523 0.0918 0.335(5) Uiso R . P 1 2 . H231 H 0.1042 0.3174 0.8394 0.0925 0.665(5) Uiso R . P 1 1 . H221 H 0.1940 0.1701 0.8978 0.1472 0.665(5) Uiso R . P 1 1 . H222 H 0.1977 0.1146 0.8342 0.1469 0.665(5) Uiso R . P 1 1 . H1221 H -0.0412 0.0307 0.8650 0.1304 0.335(5) Uiso R . P 1 2 . H1222 H 0.0878 0.0364 0.8250 0.1307 0.335(5) Uiso R . P 1 2 . H1281 H -0.1873 0.1274 0.8841 0.1159 0.335(5) Uiso R . P 1 2 . H1282 H -0.3277 0.1740 0.9589 0.1462 0.335(5) Uiso R . P 1 2 . H1283 H -0.2870 0.3450 1.0157 0.1573 0.335(5) Uiso R . P 1 2 . H1284 H -0.1040 0.4773 0.9978 0.1592 0.335(5) Uiso R . P 1 2 . H281 H -0.1900 0.1594 0.9025 0.1159 0.665(5) Uiso R . P 1 1 . H282 H -0.3045 0.2500 0.9775 0.1456 0.665(5) Uiso R . P 1 1 . H283 H -0.2289 0.4313 1.0155 0.1569 0.665(5) Uiso R . P 1 1 . H284 H -0.0375 0.5298 0.9808 0.1589 0.665(5) Uiso R . P 1 1 . H1331 H 0.0399 0.4302 0.9240 0.1269 0.335(5) Uiso R . P 1 2 . H331 H 0.0873 0.4327 0.9099 0.1267 0.665(5) Uiso R . P 1 1 . F1 F 0.4609(3) 0.4798(2) 0.59186(10) 0.1427 0.788(6) Uani D . P 2 1 . F101 F 0.3661(12) 0.3670(13) 0.6074(4) 0.1691 0.212(6) Uani D . P 2 2 . C2 C 0.4302(5) 0.3901(3) 0.6319(2) 0.0944 0.788(6) Uani D . P 2 1 . C102 C 0.4663(17) 0.4253(11) 0.6363(10) 0.0944 0.212(6) Uani D . P 2 2 . H1021 H 0.4340 0.4645 0.6709 0.1128 0.212(6) Uiso R . P 2 2 . H1022 H 0.5150 0.4896 0.6141 0.1129 0.212(6) Uiso R . P 2 2 . H21 H 0.3921 0.4349 0.6650 0.1125 0.788(6) Uiso R . P 2 1 . H22 H 0.3644 0.3319 0.6193 0.1127 0.788(6) Uiso R . P 2 1 . H31 H 0.6276 0.3810 0.6580 0.0834 0.788(6) Uiso R . P 2 1 . H32 H 0.6411 0.3619 0.6588 0.0838 0.212(6) Uiso R . P 2 2 . 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 C3 0.0809(11) 0.0573(8) 0.0719(9) -0.0010(7) 0.0002(8) -0.0074(8) C4 0.0706(9) 0.0558(8) 0.0707(9) -0.0013(7) -0.0011(7) -0.0006(8) N5 0.0566(6) 0.0563(6) 0.0702(7) 0.0001(5) -0.0039(6) -0.0027(5) C6 0.0854(12) 0.0693(10) 0.0730(10) 0.0076(8) -0.0051(9) -0.0033(10) C7 0.120(2) 0.1091(18) 0.0703(10) -0.0018(11) -0.0018(12) -0.0048(16) C8 0.0815(11) 0.0652(9) 0.0665(9) 0.0009(7) -0.0014(8) -0.0003(8) C9 0.1110(18) 0.0834(13) 0.0931(14) -0.0164(11) 0.0125(13) -0.0193(13) C10 0.163(3) 0.0914(16) 0.0997(16) -0.0261(13) 0.0026(18) -0.0193(19) C11 0.170(3) 0.118(2) 0.0843(14) -0.0188(14) 0.0219(17) 0.008(2) C12 0.123(2) 0.134(2) 0.0894(13) -0.0017(13) 0.0279(17) 0.002(2) C13 0.0893(14) 0.0955(14) 0.0830(11) -0.0002(10) 0.0073(10) -0.0108(12) Cl14 0.0672(2) 0.05680(19) 0.1045(3) -0.00631(18) -0.0005(2) 0.00242(16) Cl15 0.0676(2) 0.0630(2) 0.1204(3) -0.0074(2) -0.0094(3) 0.01241(19) F21 0.203(5) 0.088(2) 0.206(6) 0.027(3) 0.047(5) 0.037(3) C23 0.078(2) 0.083(3) 0.0687(13) 0.0163(14) 0.0003(13) 0.001(2) C24 0.0665(9) 0.0662(9) 0.0729(9) -0.0012(8) -0.0018(8) -0.0024(8) N25 0.0630(7) 0.0523(6) 0.0704(7) -0.0006(5) -0.0053(6) 0.0037(5) C26 0.0698(10) 0.0811(11) 0.0730(10) 0.0022(9) -0.0089(8) -0.0051(9) C27 0.0949(15) 0.1208(18) 0.0736(11) -0.0005(12) 0.0001(11) 0.0079(15) C28 0.092(2) 0.0763(14) 0.0633(9) 0.0063(9) -0.0055(12) 0.0049(16) C29 0.114(2) 0.092(3) 0.083(2) -0.0075(19) 0.0095(18) -0.012(2) C30 0.131(4) 0.152(5) 0.082(2) -0.013(3) 0.017(2) -0.009(4) C31 0.172(6) 0.139(5) 0.0802(19) -0.010(3) 0.033(3) -0.006(4) C32 0.219(7) 0.091(3) 0.088(2) -0.021(2) 0.010(3) -0.024(3) C33 0.131(4) 0.106(2) 0.079(2) -0.0014(16) 0.012(2) -0.030(3) F121 0.311(15) 0.165(10) 0.146(6) 0.007(6) -0.082(7) 0.100(10) C122 0.164(10) 0.064(5) 0.099(5) 0.016(4) -0.003(6) 0.034(6) C123 0.078(2) 0.083(3) 0.0687(13) 0.0163(14) 0.0003(13) 0.001(2) C128 0.092(2) 0.0763(14) 0.0633(9) 0.0063(9) -0.0055(12) 0.0049(16) C129 0.114(2) 0.092(3) 0.083(2) -0.0075(19) 0.0095(18) -0.012(2) C130 0.131(4) 0.152(5) 0.082(2) -0.013(3) 0.017(2) -0.009(4) C131 0.172(6) 0.139(5) 0.0802(19) -0.010(3) 0.033(3) -0.006(4) C132 0.219(7) 0.091(3) 0.088(2) -0.021(2) 0.010(3) -0.024(3) C133 0.131(4) 0.106(2) 0.079(2) -0.0014(16) 0.012(2) -0.030(3) C22 0.108(3) 0.171(5) 0.089(3) 0.011(3) -0.011(2) 0.045(4) F1 0.213(3) 0.1071(17) 0.1082(14) 0.0432(12) 0.0150(16) 0.0384(18) F101 0.162(10) 0.223(14) 0.123(8) -0.039(8) -0.058(7) 0.093(10) C2 0.133(4) 0.072(2) 0.0780(17) 0.006(2) -0.004(2) 0.026(2) C102 0.133(4) 0.072(2) 0.0780(17) 0.006(2) -0.004(2) 0.026(2) _refine_ls_extinction_method 'None' _oxford_refine_ls_scale 4.41(6) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag C3 . C4 . 1.517(2) yes C3 . C8 . 1.522(2) yes C3 . C2 . 1.543(4) yes C3 . H31 . 0.995 no C3 . C4 . 1.517(2) yes C3 . C8 . 1.522(2) yes C3 . C102 . 1.495(9) yes C3 . H32 . 0.984 no C4 . N5 . 1.489(2) yes C4 . H41 . 0.973 no C4 . H42 . 0.972 no N5 . C6 . 1.495(2) yes N5 . H51 . 0.904 no N5 . H52 . 0.899 no C6 . C7 . 1.503(3) yes C6 . H61 . 0.986 no C6 . H62 . 0.977 no C7 . H71 . 0.976 no C7 . H72 . 0.951 no C7 . H73 . 0.959 no C8 . C9 . 1.381(3) yes C8 . C13 . 1.378(3) yes C9 . C10 . 1.388(3) yes C9 . H91 . 0.921 no C10 . C11 . 1.352(4) yes C10 . H101 . 0.940 no C11 . C12 . 1.368(4) yes C11 . H111 . 0.944 no C12 . C13 . 1.373(3) yes C12 . H121 . 0.925 no C13 . H131 . 0.928 no F21 . C22 . 1.348(6) yes C23 . C24 . 1.512(5) yes C23 . C28 . 1.514(5) yes C23 . C22 . 1.504(6) yes C23 . H231 . 0.998 no C24 . N25 . 1.484(2) yes C24 . H241 . 0.964 no C24 . H242 . 0.967 no C24 . N25 . 1.484(2) yes C24 . C123 . 1.522(9) yes C24 . H241 . 0.964 no C24 . H242 . 0.967 no N25 . C26 . 1.491(2) yes N25 . H251 . 0.907 no N25 . H252 . 0.904 no C26 . C27 . 1.498(3) yes C26 . H261 . 0.972 no C26 . H262 . 0.975 no C27 . H271 . 0.973 no C27 . H272 . 0.961 no C27 . H273 . 0.975 no C28 . C29 . 1.385(5) yes C28 . C33 . 1.387(5) yes C29 . C30 . 1.379(5) yes C29 . H281 . 0.927 no C30 . C31 . 1.351(6) yes C30 . H282 . 0.941 no C31 . C32 . 1.375(6) yes C31 . H283 . 0.926 no C32 . C33 . 1.407(6) yes C32 . H284 . 0.925 no C33 . H331 . 0.923 no F121 . C122 . 1.383(9) yes C122 . C123 . 1.504(8) yes C122 . H1221 . 0.973 no C122 . H1222 . 0.978 no C123 . C128 . 1.494(9) yes C123 . H1231 . 0.976 no C128 . C129 . 1.384(9) yes C128 . C133 . 1.388(9) yes C129 . C130 . 1.369(9) yes C129 . H1281 . 0.939 no C130 . C131 . 1.384(8) yes C130 . H1282 . 0.926 no C131 . C132 . 1.387(9) yes C131 . H1283 . 0.936 no C132 . C133 . 1.390(9) yes C132 . H1284 . 0.916 no C133 . H1331 . 0.922 no C22 . H221 . 0.986 no C22 . H222 . 0.983 no F1 . C2 . 1.374(5) yes F101 . C102 . 1.357(9) yes C2 . H21 . 0.992 no C2 . H22 . 0.945 no C102 . H1021 . 0.974 no C102 . H1022 . 0.986 no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag C4 . C3 . C8 . 110.86(14) yes C4 . C3 . C2 . 109.9(2) yes C8 . C3 . C2 . 109.3(2) yes C4 . C3 . H31 . 109.0 no C8 . C3 . H31 . 111.0 no C2 . C3 . H31 . 106.7 no C4 . C3 . C8 . 110.86(14) yes C4 . C3 . C102 . 118.8(10) yes C8 . C3 . C102 . 117.5(9) yes C4 . C3 . H32 . 102.7 no C8 . C3 . H32 . 102.9 no C102 . C3 . H32 . 100.9 no C3 . C4 . N5 . 112.82(15) yes C3 . C4 . H41 . 110.3 no N5 . C4 . H41 . 105.8 no C3 . C4 . H42 . 110.1 no N5 . C4 . H42 . 107.7 no H41 . C4 . H42 . 110.1 no C4 . N5 . C6 . 112.73(12) yes C4 . N5 . H51 . 113.5 no C6 . N5 . H51 . 110.2 no C4 . N5 . H52 . 112.7 no C6 . N5 . H52 . 107.7 no H51 . N5 . H52 . 99.1 no N5 . C6 . C7 . 111.14(19) yes N5 . C6 . H61 . 107.6 no C7 . C6 . H61 . 109.5 no N5 . C6 . H62 . 105.8 no C7 . C6 . H62 . 108.8 no H61 . C6 . H62 . 113.9 no C6 . C7 . H71 . 107.1 no C6 . C7 . H72 . 110.2 no H71 . C7 . H72 . 110.5 no C6 . C7 . H73 . 112.6 no H71 . C7 . H73 . 109.0 no H72 . C7 . H73 . 107.5 no C3 . C8 . C9 . 121.72(19) yes C3 . C8 . C13 . 120.16(18) yes C9 . C8 . C13 . 118.1(2) yes C8 . C9 . C10 . 120.2(3) yes C8 . C9 . H91 . 119.7 no C10 . C9 . H91 . 120.1 no C9 . C10 . C11 . 120.6(3) yes C9 . C10 . H101 . 119.3 no C11 . C10 . H101 . 120.0 no C10 . C11 . C12 . 119.8(3) yes C10 . C11 . H111 . 118.7 no C12 . C11 . H111 . 121.5 no C11 . C12 . C13 . 120.1(3) yes C11 . C12 . H121 . 121.4 no C13 . C12 . H121 . 118.4 no C8 . C13 . C12 . 121.1(2) yes C8 . C13 . H131 . 119.3 no C12 . C13 . H131 . 119.5 no C24 . C23 . C28 . 111.5(4) yes C24 . C23 . C22 . 119.9(4) yes C28 . C23 . C22 . 109.4(4) yes C24 . C23 . H231 . 104.8 no C28 . C23 . H231 . 104.9 no C22 . C23 . H231 . 104.8 no C23 . C24 . N25 . 110.3(2) yes C23 . C24 . H241 . 107.6 no N25 . C24 . H241 . 107.5 no C23 . C24 . H242 . 114.4 no N25 . C24 . H242 . 106.6 no H241 . C24 . H242 . 110.3 no N25 . C24 . C123 . 118.4(5) yes N25 . C24 . H241 . 107.5 no C123 . C24 . H241 . 113.2 no N25 . C24 . H242 . 106.6 no C123 . C24 . H242 . 100.2 no H241 . C24 . H242 . 110.3 no C24 . N25 . C26 . 113.93(13) yes C24 . N25 . H251 . 108.0 no C26 . N25 . H251 . 107.7 no C24 . N25 . H252 . 110.1 no C26 . N25 . H252 . 108.6 no H251 . N25 . H252 . 108.4 no N25 . C26 . C27 . 110.88(16) yes N25 . C26 . H261 . 106.5 no C27 . C26 . H261 . 108.1 no N25 . C26 . H262 . 109.5 no C27 . C26 . H262 . 110.2 no H261 . C26 . H262 . 111.6 no C26 . C27 . H271 . 111.4 no C26 . C27 . H272 . 109.9 no H271 . C27 . H272 . 105.5 no C26 . C27 . H273 . 112.7 no H271 . C27 . H273 . 109.3 no H272 . C27 . H273 . 107.8 no C23 . C28 . C29 . 128.6(5) yes C23 . C28 . C33 . 113.0(5) yes C29 . C28 . C33 . 118.2(4) yes C28 . C29 . C30 . 122.1(4) yes C28 . C29 . H281 . 119.6 no C30 . C29 . H281 . 118.3 no C29 . C30 . C31 . 119.6(4) yes C29 . C30 . H282 . 122.3 no C31 . C30 . H282 . 118.1 no C30 . C31 . C32 . 120.5(4) yes C30 . C31 . H283 . 118.8 no C32 . C31 . H283 . 120.7 no C31 . C32 . C33 . 120.4(4) yes C31 . C32 . H284 . 120.6 no C33 . C32 . H284 . 118.9 no C32 . C33 . C28 . 119.3(4) yes C32 . C33 . H331 . 120.9 no C28 . C33 . H331 . 119.8 no F121 . C122 . C123 . 101.3(9) yes F121 . C122 . H1221 . 110.4 no C123 . C122 . H1221 . 111.4 no F121 . C122 . H1222 . 111.0 no C123 . C122 . H1222 . 112.5 no H1221 . C122 . H1222 . 110.0 no C24 . C123 . C122 . 101.5(6) yes C24 . C123 . C128 . 109.9(8) yes C122 . C123 . C128 . 115.8(9) yes C24 . C123 . H1231 . 109.9 no C122 . C123 . H1231 . 108.0 no C128 . C123 . H1231 . 111.2 no C123 . C128 . C129 . 108.8(10) yes C123 . C128 . C133 . 129.4(10) yes C129 . C128 . C133 . 121.1(6) yes C128 . C129 . C130 . 119.3(6) yes C128 . C129 . H1281 . 120.6 no C130 . C129 . H1281 . 120.1 no C129 . C130 . C131 . 120.1(6) yes C129 . C130 . H1282 . 120.7 no C131 . C130 . H1282 . 119.2 no C130 . C131 . C132 . 121.1(6) yes C130 . C131 . H1283 . 118.6 no C132 . C131 . H1283 . 120.3 no C131 . C132 . C133 . 118.8(6) yes C131 . C132 . H1284 . 121.0 no C133 . C132 . H1284 . 120.1 no C132 . C133 . C128 . 119.5(6) yes C132 . C133 . H1331 . 120.5 no C128 . C133 . H1331 . 120.0 no C23 . C22 . F21 . 112.0(5) yes C23 . C22 . H221 . 108.8 no F21 . C22 . H221 . 108.8 no C23 . C22 . H222 . 110.3 no F21 . C22 . H222 . 106.1 no H221 . C22 . H222 . 110.9 no C3 . C2 . F1 . 109.4(4) yes C3 . C2 . H21 . 111.1 no F1 . C2 . H21 . 107.8 no C3 . C2 . H22 . 109.0 no F1 . C2 . H22 . 112.4 no H21 . C2 . H22 . 107.0 no C3 . C102 . F101 . 101.4(8) yes C3 . C102 . H1021 . 111.8 no F101 . C102 . H1021 . 112.1 no C3 . C102 . H1022 . 108.8 no F101 . C102 . H1022 . 113.7 no H1021 . C102 . H1022 . 108.8 no _iucr_refine_instructions_details ; # # Punched on 15/07/19 at 15:37:04 # #LIST 12 BLOCK SCALE X'S U'S CONT ENANTIO SUMFIX PART(1001, OCC) CONTINUE AND PART(1002, OCC) SUMFIX PART(2001, OCC) CONTINUE AND PART(2002, OCC) RIDE C(2,U'S) C(102,U'S) RIDE C(23,U'S) C(123,U'S) RIDE C(28,U'S) C(128,U'S) RIDE C(29,U'S) C(129,U'S) RIDE C(30,U'S) C(130,U'S) RIDE C(31,U'S) C(131,U'S) RIDE C(32,U'S) C(132,U'S) RIDE C(33,U'S) C(133,U'S) RIDE C ( 3,X'S) H ( 31,X'S) H ( 32,X'S) RIDE C ( 4,X'S) H ( 41,X'S) H ( 42,X'S) RIDE N ( 5,X'S) H ( 51,X'S) H ( 52,X'S) RIDE C ( 6,X'S) H ( 61,X'S) H ( 62,X'S) RIDE C ( 7,X'S) H ( 71,X'S) H ( 72,X'S) H ( 73,X'S) RIDE C ( 9,X'S) H ( 91,X'S) RIDE C ( 10,X'S) H ( 101,X'S) RIDE C ( 11,X'S) H ( 111,X'S) RIDE C ( 12,X'S) H ( 121,X'S) RIDE C ( 13,X'S) H ( 131,X'S) RIDE C ( 23,X'S) H ( 231,X'S) RIDE C ( 24,X'S) H ( 241,X'S) H ( 242,X'S) RIDE N ( 25,X'S) H ( 251,X'S) H ( 252,X'S) RIDE C ( 26,X'S) H ( 261,X'S) H ( 262,X'S) RIDE C ( 27,X'S) H ( 271,X'S) H ( 272,X'S) H ( 273,X'S) RIDE C ( 29,X'S) H ( 281,X'S) RIDE C ( 30,X'S) H ( 282,X'S) RIDE C ( 31,X'S) H ( 283,X'S) RIDE C ( 32,X'S) H ( 284,X'S) RIDE C ( 33,X'S) H ( 331,X'S) RIDE C ( 122,X'S) H (1221,X'S) H (1222,X'S) RIDE C ( 123,X'S) H (1231,X'S) RIDE C ( 129,X'S) H (1281,X'S) RIDE C ( 130,X'S) H (1282,X'S) RIDE C ( 131,X'S) H (1283,X'S) RIDE C ( 132,X'S) H (1284,X'S) RIDE C ( 133,X'S) H (1331,X'S) RIDE C ( 22,X'S) H ( 221,X'S) H ( 222,X'S) RIDE C ( 2,X'S) H ( 21,X'S) H ( 22,X'S) RIDE C ( 102,X'S) H (1021,X'S) H (1022,X'S) END # # Punched on 15/07/19 at 15:37:04 # #LIST 16 DIST 1.37, 0.01 = CONT C(2) TO F(1) C(102) TO F(101) CONT C(22) TO F(21) C(122) TO F(121) DIST 1.54, 0.01 = CONT C(3) TO C(2) C(3) TO C(102) CONT C(24) TO C(23) C(24) TO C(123) CONT C(23) TO C(22) C(123) TO C(122) DIST 1.52, 0.01 = CONT C(23) TO C(28) C(123) TO C(128) PLANAR C(28) UNTIL C(33) PLANAR C(128) UNTIL C(133) DIST 1.4, 0.01 = CONT C(28) TO C(29) C(128) TO C(129) CONT C(29) TO C(30) C(129) TO C(130) CONT C(30) TO C(31) C(130) TO C(131) CONT C(31) TO C(32) C(131) TO C(132) CONT C(32) TO C(33) C(132) TO C(133) CONT C(33) TO C(28) C(133) TO C(128) ANGLE 0, 1 = MEAN CONT C(28) TO C(29) TO C(30) CONT C(29) TO C(30) TO C(31) CONT C(30) TO C(31) TO C(32) CONT C(31) TO C(32) TO C(33) CONT C(32) TO C(33) TO C(28) CONT C(33) TO C(28) TO C(29) CONT C(128) TO C(129) TO C(130) CONT C(129) TO C(130) TO C(131) CONT C(130) TO C(131) TO C(132) CONT C(131) TO C(132) TO C(133) CONT C(132) TO C(133) TO C(128) CONT C(133) TO C(128) TO C(129) REM HREST START (DO NOT REMOVE THIS LINE) REM HREST END (DO NOT REMOVE THIS LINE) END ;