# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'H Rudler' _publ_contact_author_email RUDLER@CCR.JUSSIEU.FR _publ_section_title ; Lactonizations of carboxylic acid-substituted 3-fluorodihydropyridines with electrophiles: peculiar behaviour of F+ ; loop_ _publ_author_name 'H Rudler' 'Jean-Claude Daran' 'Louis Hamon' 'Patrick Herson' 'Andree Parlier' # Attachment 'ccdc_668553_673543_cif.txt' data_Patrick _database_code_depnum_ccdc_archive 'CCDC 668553' _audit_creation_date 07-06-13 _audit_creation_method CRYSTALS_ver_12.84 _chemical_name_systematic ? _chemical_melting_point ? _cell_length_a 8.0326(8) _cell_length_b 8.7779(11) _cell_length_c 10.5283(10) _cell_angle_alpha 90.285(8) _cell_angle_beta 106.596(9) _cell_angle_gamma 102.27(1) _cell_volume 693.44(14) _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P -1 ' _symmetry_space_group_name_Hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-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 0.0033 0.0016 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' O 0.0106 0.0060 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' F 0.0171 0.0103 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 0.0061 0.0033 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' _cell_formula_units_Z 2 # Given Formula = C14 H17 F2 N1 O4 # Dc = 1.44 Fooo = 316.00 Mu = 1.22 M = 301.29 # Found Formula = C14 H17 F2 N1 O4 # Dc = 1.44 FOOO = 316.00 Mu = 1.22 M = 301.29 _chemical_formula_sum 'C14 H17 F2 N1 O4' _chemical_formula_moiety 'C14 H17 F2 N1 O4' _chemical_compound_source ? _chemical_formula_weight 301.29 _cell_measurement_reflns_used 77 _cell_measurement_theta_min 4 _cell_measurement_theta_max 22 _cell_measurement_temperature 250 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_min 0.04 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_max 0.19 _exptl_crystal_density_diffrn 1.443 _exptl_crystal_density_meas ? # Non-dispersive F(000): _exptl_crystal_F_000 316 _exptl_absorpt_coefficient_mu 0.122 # Sheldrick geometric approximatio 0.99 1.00 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS (Siemens, 1996)' _exptl_absorpt_correction_T_min 0.98 _exptl_absorpt_correction_T_max 1.00 # For a Kappa CCD, set Tmin to 1.0 and # Tmax to the ratio of max:min frame scales in scale_all.log _diffrn_measurement_device_type 'Nonius KappaCCD' _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method '\f & \w scans' # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection 'COLLECT (Nonius, 1997-2001).' _computing_cell_refinement 'Dirax/lsq (Duisenberg & Schreurs, 1989-2000)' _computing_data_reduction 'EvalCCD (Duisenberg & Schreurs 1990-2000)' _computing_structure_solution 'SHELXS 86 (Sheldrick, 1986)' _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 250 _diffrn_reflns_number 12967 _reflns_number_total 3998 _diffrn_reflns_av_R_equivalents 0.033 # Number of reflections with Friedels Law is 3998 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 4044 _diffrn_reflns_theta_min 2.023 _diffrn_reflns_theta_max 29.996 _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 26.396 _diffrn_measured_fraction_theta_full 0.992 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _reflns_limit_h_min -11 _reflns_limit_h_max 10 _reflns_limit_k_min -12 _reflns_limit_k_max 12 _reflns_limit_l_min 0 _reflns_limit_l_max 14 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -0.25 _refine_diff_density_max 0.31 _refine_ls_number_reflns 2520 _refine_ls_number_restraints 0 _refine_ls_number_parameters 192 #_refine_ls_R_factor_ref 0.0394 _refine_ls_wR_factor_ref 0.0486 _refine_ls_goodness_of_fit_ref 1.0868 #_reflns_number_all 3994 _refine_ls_R_factor_all 0.0672 _refine_ls_wR_factor_all 0.0709 # The I/u(I) cutoff below was used for refinement as # well as the _gt R-factors: _reflns_threshold_expression I>3.0\s(I) _reflns_number_gt 2520 _refine_ls_R_factor_gt 0.0394 _refine_ls_wR_factor_gt 0.0486 _refine_ls_shift/su_max 0.000320 # 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 . _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_hydrogen_treatment refu # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method, part 1, Chebychev polynomial, (Watkin, 1994, Prince, 1982) [weight] = 1.0/[A~0~*T~0~(x)+A~1~*T~1~(x) ... +A~n-1~]*T~n-1~(x)] where A~i~ are the Chebychev coefficients listed below and x= Fcalc/Fmax Method = Robust Weighting (Prince, 1982) W = [weight] * [1-(deltaF/6*sigmaF)^2^]^2^ A~i~ are: 1.00 0.648 0.633 ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached 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 C1 C 0.19770(17) 0.45744(16) 0.71380(14) 0.0264 1.0000 Uani . . . . . . C3 C 0.14237(18) 0.69957(18) 0.60262(14) 0.0290 1.0000 Uani . . . . . . C4 C 0.09799(17) 0.76733(16) 0.72152(13) 0.0243 1.0000 Uani . . . . . . C5 C 0.14894(17) 0.67023(15) 0.84579(13) 0.0233 1.0000 Uani . . . . . . C6 C 0.34721(18) 0.69991(16) 0.91018(13) 0.0271 1.0000 Uani . . . . . . C7 C 0.45506(17) 0.61626(17) 0.88368(14) 0.0284 1.0000 Uani . . . . . . C8 C 0.50256(18) 0.41159(18) 0.75203(15) 0.0308 1.0000 Uani . . . . . . C9 C 0.08525(17) 0.49644(15) 0.79940(14) 0.0249 1.0000 Uani . . . . . . C10 C 0.5253(3) 0.2084(3) 0.6142(3) 0.0647 1.0000 Uani . . . . . . C11 C 0.1993(2) 0.94262(17) 0.74970(15) 0.0320 1.0000 Uani . . . . . . C12 C 0.1395(3) 1.03182(18) 0.84745(17) 0.0402 1.0000 Uani . . . . . . C13 C -0.0608(3) 1.0245(2) 0.79745(19) 0.0433 1.0000 Uani . . . . . . C14 C -0.1666(2) 0.8534(2) 0.77115(18) 0.0395 1.0000 Uani . . . . . . C15 C -0.10669(19) 0.76158(19) 0.67303(15) 0.0321 1.0000 Uani . . . . . . O1 O 0.14025(19) 0.76957(17) 0.50300(12) 0.0462 1.0000 Uani . . . . . . O2 O 0.17811(14) 0.55441(13) 0.60054(10) 0.0323 1.0000 Uani . . . . . . O3 O 0.66284(15) 0.44999(16) 0.79886(13) 0.0448 1.0000 Uani . . . . . . O4 O 0.41414(15) 0.29310(15) 0.65972(13) 0.0421 1.0000 Uani . . . . . . N8 N 0.38411(15) 0.48507(14) 0.78910(12) 0.0276 1.0000 Uani . . . . . . F1 F 0.41681(14) 0.82092(11) 1.00606(10) 0.0429 1.0000 Uani . . . . . . F2 F 0.10856(12) 0.40293(10) 0.90806(9) 0.0347 1.0000 Uani . . . . . . H11 H 0.1544 0.3449 0.6805 0.0494(14) 1.0000 Uiso . . . . . . H51 H 0.0892 0.6948 0.9122 0.0494(14) 1.0000 Uiso . . . . . . H71 H 0.5859 0.6456 0.9302 0.0494(14) 1.0000 Uiso . . . . . . H91 H -0.0433 0.4737 0.7462 0.0494(14) 1.0000 Uiso . . . . . . H101 H 0.4482 0.1232 0.5462 0.0494(14) 1.0000 Uiso . . . . . . H102 H 0.5982 0.1619 0.6911 0.0494(14) 1.0000 Uiso . . . . . . H103 H 0.6062 0.2818 0.5738 0.0494(14) 1.0000 Uiso . . . . . . H111 H 0.3297 0.9472 0.7875 0.0494(14) 1.0000 Uiso . . . . . . H112 H 0.1777 0.9943 0.6639 0.0494(14) 1.0000 Uiso . . . . . . H121 H 0.2055 1.1436 0.8585 0.0494(14) 1.0000 Uiso . . . . . . H122 H 0.1672 0.9845 0.9351 0.0494(14) 1.0000 Uiso . . . . . . H131 H -0.0970 1.0780 0.8660 0.0494(14) 1.0000 Uiso . . . . . . H132 H -0.0876 1.0787 0.7131 0.0494(14) 1.0000 Uiso . . . . . . H141 H -0.1473 0.8021 0.8571 0.0494(14) 1.0000 Uiso . . . . . . H142 H -0.2962 0.8517 0.7328 0.0494(14) 1.0000 Uiso . . . . . . H151 H -0.1355 0.8078 0.5849 0.0494(14) 1.0000 Uiso . . . . . . H152 H -0.1732 0.6500 0.6633 0.0494(14) 1.0000 Uiso . . . . . . 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 0.0211(6) 0.0287(6) 0.0286(6) -0.0016(5) 0.0053(5) 0.0068(5) C3 0.0254(6) 0.0392(8) 0.0245(6) 0.0044(5) 0.0090(5) 0.0093(5) C4 0.0252(6) 0.0264(6) 0.0238(6) 0.0058(5) 0.0095(5) 0.0082(5) C5 0.0259(6) 0.0231(6) 0.0229(6) 0.0029(5) 0.0096(5) 0.0064(5) C6 0.0290(7) 0.0232(6) 0.0236(6) 0.0012(5) 0.0020(5) 0.0016(5) C7 0.0214(6) 0.0294(7) 0.0295(7) 0.0037(5) 0.0023(5) 0.0020(5) C8 0.0249(6) 0.0387(8) 0.0340(7) 0.0077(6) 0.0137(5) 0.0113(6) C9 0.0222(6) 0.0234(6) 0.0302(6) 0.0034(5) 0.0095(5) 0.0051(5) C10 0.0487(11) 0.0791(15) 0.0791(15) -0.0203(12) 0.0297(11) 0.0276(11) C11 0.0354(7) 0.0266(6) 0.0351(7) 0.0106(6) 0.0121(6) 0.0070(6) C12 0.0570(10) 0.0258(7) 0.0405(8) 0.0062(6) 0.0153(7) 0.0132(7) C13 0.0584(11) 0.0386(8) 0.0463(9) 0.0127(7) 0.0246(8) 0.0267(8) C14 0.0375(8) 0.0461(9) 0.0466(9) 0.0140(7) 0.0221(7) 0.0208(7) C15 0.0255(6) 0.0394(8) 0.0340(7) 0.0083(6) 0.0083(5) 0.0131(6) O1 0.0590(8) 0.0596(8) 0.0310(6) 0.0171(5) 0.0236(5) 0.0219(6) O2 0.0339(5) 0.0431(6) 0.0232(5) -0.0001(4) 0.0080(4) 0.0163(5) O3 0.0227(5) 0.0586(8) 0.0553(7) 0.0024(6) 0.0138(5) 0.0104(5) O4 0.0313(6) 0.0495(7) 0.0509(7) -0.0093(5) 0.0166(5) 0.0148(5) N8 0.0188(5) 0.0321(6) 0.0310(6) -0.0006(5) 0.0054(4) 0.0066(4) F1 0.0454(5) 0.0329(5) 0.0388(5) -0.0096(4) -0.0032(4) 0.0053(4) F2 0.0396(5) 0.0263(4) 0.0434(5) 0.0124(4) 0.0184(4) 0.0094(3) _refine_ls_extinction_coef 92 _refine_ls_extinction_method 'Larson (1970), Equation 22' 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 C1 . C9 . 1.5293(18) ? C1 . O2 . 1.4598(17) ? C1 . N8 . 1.4474(17) ? C1 . H11 . 1.000 no C3 . C4 . 1.5446(19) ? C3 . O1 . 1.2160(17) ? C3 . O2 . 1.3657(18) ? C4 . C5 . 1.5682(18) ? C4 . C11 . 1.563(2) ? C4 . C15 . 1.5656(19) ? C5 . C6 . 1.5063(19) ? C5 . C9 . 1.5315(19) ? C5 . H51 . 1.000 no C6 . C7 . 1.332(2) ? C6 . F1 . 1.3691(16) ? C7 . N8 . 1.4240(19) ? C7 . H71 . 1.000 no C8 . O3 . 1.2106(18) ? C8 . O4 . 1.346(2) ? C8 . N8 . 1.3943(17) ? C9 . F2 . 1.4035(16) ? C9 . H91 . 1.000 no C10 . O4 . 1.450(2) ? C10 . H101 . 1.000 no C10 . H102 . 1.000 no C10 . H103 . 1.000 no C11 . C12 . 1.529(2) ? C11 . H111 . 1.000 no C11 . H112 . 1.000 no C12 . C13 . 1.530(3) ? C12 . H121 . 1.000 no C12 . H122 . 1.000 no C13 . C14 . 1.541(3) ? C13 . H131 . 1.000 no C13 . H132 . 1.000 no C14 . C15 . 1.546(2) ? C14 . H141 . 1.000 no C14 . H142 . 1.000 no C15 . H151 . 1.000 no C15 . H152 . 1.000 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 C9 . C1 . O2 . 109.22(10) ? C9 . C1 . N8 . 111.21(11) ? O2 . C1 . N8 . 109.16(11) ? C9 . C1 . H11 . 109.1 no O2 . C1 . H11 . 109.1 no N8 . C1 . H11 . 109.1 no C4 . C3 . O1 . 121.96(13) ? C4 . C3 . O2 . 121.99(12) ? O1 . C3 . O2 . 115.99(13) ? C3 . C4 . C5 . 110.72(11) ? C3 . C4 . C11 . 107.82(11) ? C5 . C4 . C11 . 112.15(11) ? C3 . C4 . C15 . 105.81(11) ? C5 . C4 . C15 . 111.98(11) ? C11 . C4 . C15 . 108.07(11) ? C4 . C5 . C6 . 112.64(11) ? C4 . C5 . C9 . 108.15(11) ? C6 . C5 . C9 . 106.93(11) ? C4 . C5 . H51 . 109.7 no C6 . C5 . H51 . 109.7 no C9 . C5 . H51 . 109.7 no C5 . C6 . C7 . 125.39(12) ? C5 . C6 . F1 . 115.52(12) ? C7 . C6 . F1 . 119.06(12) ? C6 . C7 . N8 . 120.01(12) ? C6 . C7 . H71 . 120.0 no N8 . C7 . H71 . 120.0 no O3 . C8 . O4 . 125.53(14) ? O3 . C8 . N8 . 123.65(15) ? O4 . C8 . N8 . 110.82(12) ? C5 . C9 . C1 . 108.49(11) ? C5 . C9 . F2 . 110.97(11) ? C1 . C9 . F2 . 107.86(10) ? C5 . C9 . H91 . 109.8 no C1 . C9 . H91 . 109.8 no F2 . C9 . H91 . 109.8 no O4 . C10 . H101 . 109.5 no O4 . C10 . H102 . 109.5 no H101 . C10 . H102 . 109.5 no O4 . C10 . H103 . 109.5 no H101 . C10 . H103 . 109.5 no H102 . C10 . H103 . 109.5 no C4 . C11 . C12 . 112.98(12) ? C4 . C11 . H111 . 108.6 no C12 . C11 . H111 . 108.6 no C4 . C11 . H112 . 108.6 no C12 . C11 . H112 . 108.6 no H111 . C11 . H112 . 109.5 no C11 . C12 . C13 . 111.20(15) ? C11 . C12 . H121 . 109.0 no C13 . C12 . H121 . 109.0 no C11 . C12 . H122 . 109.0 no C13 . C12 . H122 . 109.0 no H121 . C12 . H122 . 109.5 no C12 . C13 . C14 . 110.47(13) ? C12 . C13 . H131 . 109.2 no C14 . C13 . H131 . 109.2 no C12 . C13 . H132 . 109.2 no C14 . C13 . H132 . 109.2 no H131 . C13 . H132 . 109.5 no C13 . C14 . C15 . 111.53(13) ? C13 . C14 . H141 . 109.0 no C15 . C14 . H141 . 109.0 no C13 . C14 . H142 . 109.0 no C15 . C14 . H142 . 109.0 no H141 . C14 . H142 . 109.5 no C14 . C15 . C4 . 112.27(13) ? C14 . C15 . H151 . 108.8 no C4 . C15 . H151 . 108.8 no C14 . C15 . H152 . 108.8 no C4 . C15 . H152 . 108.8 no H151 . C15 . H152 . 109.5 no C1 . O2 . C3 . 123.79(10) ? C10 . O4 . C8 . 115.31(14) ? C1 . N8 . C7 . 117.93(11) ? C1 . N8 . C8 . 122.00(12) ? C7 . N8 . C8 . 118.44(12) ? #====END data_HRFF _database_code_depnum_ccdc_archive 'CCDC 673543' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C14 H17 F2 N O4' _chemical_formula_sum 'C14 H17 F2 N O4' _chemical_formula_weight 301.29 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P b c a' _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, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 13.566(3) _cell_length_b 10.620(2) _cell_length_c 18.434(4) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2655.9(9) _cell_formula_units_Z 8 _cell_measurement_temperature 180(2) _cell_measurement_reflns_used 2332 _cell_measurement_theta_min 2.45 _cell_measurement_theta_max 32.20 _exptl_crystal_description needle _exptl_crystal_colour colorless _exptl_crystal_size_max 0.75 _exptl_crystal_size_mid 0.11 _exptl_crystal_size_min 0.103 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.507 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1264 _exptl_absorpt_coefficient_mu 0.128 _exptl_absorpt_correction_T_min 0.908 _exptl_absorpt_correction_T_max 0.987 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlis RED (Oxford Diffraction, 2006) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 180(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford-Diffraction XCALIBUR' _diffrn_measurement_method '\w and \f' _diffrn_detector_area_resol_mean 8.2632 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 5889 _diffrn_reflns_av_R_equivalents 0.1488 _diffrn_reflns_av_sigmaI/netI 0.1961 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.67 _diffrn_reflns_theta_max 23.26 _reflns_number_total 1596 _reflns_number_gt 627 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'CrysAlis CCD (Oxford Diffraction, 2006)' _computing_cell_refinement 'CrysAlis RED (Oxford Diffraction, 2006)' _computing_data_reduction 'CrysAlis RED' _computing_structure_solution 'SIR-97 (Altomare et al., 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEPIII (Burnett & Johnson, 1996); ORTEP-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' _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^)+(0.1051P)^2^+0.0000P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1596 _refine_ls_number_parameters 191 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1648 _refine_ls_R_factor_gt 0.0690 _refine_ls_wR_factor_ref 0.2136 _refine_ls_wR_factor_gt 0.1490 _refine_ls_goodness_of_fit_ref 0.877 _refine_ls_restrained_S_all 0.877 _refine_ls_shift/su_max 0.005 _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 0.3989(4) 0.2654(6) 0.5317(3) 0.063(2) Uani 1 1 d . . . O2 O 0.4526(3) 0.2345(6) 0.4224(3) 0.0443(17) Uani 1 1 d . . . N8 N 0.5527(4) 0.3375(8) 0.3353(4) 0.042(2) Uani 1 1 d . . . O81 O 0.5100(4) 0.4869(7) 0.2519(3) 0.050(2) Uani 1 1 d . . . O82 O 0.4222(4) 0.3082(6) 0.2648(3) 0.0487(19) Uani 1 1 d . . . F1 F 0.5953(3) 0.0532(5) 0.4351(2) 0.0490(15) Uani 1 1 d . . . F2 F 0.6899(3) 0.1452(5) 0.3564(2) 0.0494(15) Uani 1 1 d . . . C1 C 0.5278(5) 0.2213(10) 0.3699(4) 0.041(3) Uani 1 1 d . . . H1 H 0.5058 0.1614 0.3329 0.049 Uiso 1 1 calc R . . C3 C 0.4690(5) 0.2561(9) 0.4933(5) 0.043(2) Uani 1 1 d . . . C4 C 0.5749(4) 0.2682(9) 0.5257(4) 0.040(2) Uani 1 1 d . . . C5 C 0.6544(5) 0.2567(9) 0.4650(4) 0.042(3) Uani 1 1 d . . . H5 H 0.7160 0.2249 0.4860 0.050 Uiso 1 1 calc R . . C6 C 0.6741(5) 0.3787(10) 0.4265(4) 0.042(3) Uani 1 1 d . . . H6 H 0.7229 0.4311 0.4448 0.050 Uiso 1 1 calc R . . C7 C 0.6249(5) 0.4165(9) 0.3667(4) 0.041(3) Uani 1 1 d . . . H7 H 0.6384 0.4946 0.3462 0.049 Uiso 1 1 calc R . . C9 C 0.6182(5) 0.1667(10) 0.4086(5) 0.039(3) Uani 1 1 d . . . C41 C 0.5792(5) 0.3972(10) 0.5633(4) 0.049(3) Uani 1 1 d . . . H41A H 0.5771 0.4629 0.5268 0.059 Uiso 1 1 calc R . . H41B H 0.5216 0.4068 0.5940 0.059 Uiso 1 1 calc R . . C42 C 0.6715(4) 0.4136(10) 0.6090(4) 0.051(3) Uani 1 1 d . . . H42A H 0.7289 0.4115 0.5777 0.061 Uiso 1 1 calc R . . H42B H 0.6696 0.4951 0.6326 0.061 Uiso 1 1 calc R . . C43 C 0.6803(6) 0.3136(11) 0.6647(5) 0.055(3) Uani 1 1 d . . . H43A H 0.6263 0.3206 0.6988 0.066 Uiso 1 1 calc R . . H43B H 0.7415 0.3244 0.6912 0.066 Uiso 1 1 calc R . . C44 C 0.6787(5) 0.1835(10) 0.6294(4) 0.051(3) Uani 1 1 d . . . H44A H 0.7370 0.1732 0.5995 0.061 Uiso 1 1 calc R . . H44B H 0.6800 0.1194 0.6668 0.061 Uiso 1 1 calc R . . C45 C 0.5875(5) 0.1666(9) 0.5831(4) 0.041(3) Uani 1 1 d . . . H45A H 0.5300 0.1666 0.6144 0.050 Uiso 1 1 calc R . . H45B H 0.5908 0.0852 0.5594 0.050 Uiso 1 1 calc R . . C81 C 0.4959(6) 0.3891(12) 0.2812(5) 0.042(3) Uani 1 1 d . . . C83 C 0.3557(5) 0.3536(10) 0.2102(4) 0.055(3) Uani 1 1 d . . . H83A H 0.3195 0.4242 0.2288 0.082 Uiso 1 1 calc R . . H83B H 0.3107 0.2878 0.1970 0.082 Uiso 1 1 calc R . . H83C H 0.3926 0.3791 0.1682 0.082 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 0.029(3) 0.100(7) 0.062(4) -0.002(4) 0.009(3) -0.001(3) O2 0.029(3) 0.054(6) 0.050(4) -0.007(4) -0.006(3) -0.002(3) N8 0.037(4) 0.037(7) 0.051(5) 0.000(4) 0.000(3) -0.003(3) O81 0.046(3) 0.053(7) 0.052(4) 0.016(4) -0.002(3) -0.001(3) O82 0.044(3) 0.039(6) 0.063(4) -0.001(3) -0.017(3) -0.004(3) F1 0.055(3) 0.028(5) 0.065(3) 0.008(3) 0.000(2) -0.002(2) F2 0.041(2) 0.040(5) 0.067(3) -0.006(3) 0.002(2) 0.005(2) C1 0.035(5) 0.044(9) 0.044(5) -0.003(5) -0.001(4) 0.002(4) C3 0.039(4) 0.026(8) 0.063(6) 0.001(5) 0.007(4) -0.005(4) C4 0.028(4) 0.043(8) 0.049(5) 0.010(6) -0.001(3) -0.001(4) C5 0.030(4) 0.048(9) 0.047(5) 0.007(6) -0.006(3) 0.003(4) C6 0.031(4) 0.046(9) 0.047(6) -0.013(6) 0.003(4) -0.002(4) C7 0.040(5) 0.023(8) 0.058(6) 0.001(5) 0.012(4) -0.002(4) C9 0.030(4) 0.035(9) 0.051(6) -0.001(6) 0.007(4) 0.003(4) C41 0.047(5) 0.049(10) 0.051(6) -0.003(6) 0.007(4) 0.006(4) C42 0.033(4) 0.069(10) 0.051(6) -0.013(6) -0.001(4) -0.005(4) C43 0.045(5) 0.069(10) 0.052(6) 0.005(7) -0.012(4) 0.005(5) C44 0.046(5) 0.063(10) 0.044(6) 0.007(6) -0.001(4) 0.012(5) C45 0.047(5) 0.034(9) 0.044(5) 0.009(5) 0.006(4) 0.001(4) C81 0.051(5) 0.037(10) 0.037(6) 0.008(5) 0.006(4) 0.003(5) C83 0.045(5) 0.063(10) 0.058(6) -0.003(6) -0.013(4) 0.001(5) _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 C3 1.189(8) . ? O2 C3 1.345(8) . ? O2 C1 1.413(8) . ? N8 C81 1.374(10) . ? N8 C7 1.414(10) . ? N8 C1 1.429(11) . ? O81 C81 1.186(11) . ? O82 C81 1.353(11) . ? O82 C83 1.434(8) . ? F1 C9 1.337(10) . ? F2 C9 1.386(8) . ? C1 C9 1.533(10) . ? C3 C4 1.560(9) . ? C4 C45 1.521(11) . ? C4 C41 1.537(12) . ? C4 C5 1.559(10) . ? C5 C9 1.496(12) . ? C5 C6 1.501(11) . ? C6 C7 1.348(10) . ? C41 C42 1.519(9) . ? C42 C43 1.482(12) . ? C43 C44 1.527(13) . ? C44 C45 1.513(9) . ? 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 C3 O2 C1 124.2(5) . . ? C81 N8 C7 116.7(9) . . ? C81 N8 C1 122.4(7) . . ? C7 N8 C1 119.5(7) . . ? C81 O82 C83 114.1(8) . . ? O2 C1 N8 113.0(7) . . ? O2 C1 C9 107.3(6) . . ? N8 C1 C9 110.2(7) . . ? O1 C3 O2 117.4(7) . . ? O1 C3 C4 120.1(8) . . ? O2 C3 C4 122.5(6) . . ? C45 C4 C41 108.3(7) . . ? C45 C4 C5 111.5(7) . . ? C41 C4 C5 111.5(7) . . ? C45 C4 C3 108.2(6) . . ? C41 C4 C3 106.3(6) . . ? C5 C4 C3 110.9(6) . . ? C9 C5 C6 106.3(7) . . ? C9 C5 C4 108.7(6) . . ? C6 C5 C4 113.2(8) . . ? C7 C6 C5 123.8(8) . . ? C6 C7 N8 120.1(8) . . ? F1 C9 F2 105.6(7) . . ? F1 C9 C5 113.5(8) . . ? F2 C9 C5 110.9(6) . . ? F1 C9 C1 109.0(7) . . ? F2 C9 C1 107.5(6) . . ? C5 C9 C1 110.1(8) . . ? C42 C41 C4 112.6(7) . . ? C43 C42 C41 111.7(7) . . ? C42 C43 C44 110.6(7) . . ? C45 C44 C43 111.1(7) . . ? C44 C45 C4 113.6(7) . . ? O81 C81 O82 125.1(8) . . ? O81 C81 N8 126.0(9) . . ? O82 C81 N8 108.9(9) . . ? _diffrn_measured_fraction_theta_max 0.836 _diffrn_reflns_theta_full 23.26 _diffrn_measured_fraction_theta_full 0.836 _refine_diff_density_max 0.324 _refine_diff_density_min -0.281 _refine_diff_density_rms 0.087