# Supplementary Material (ESI) for Perkin Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 207/419 data_global _publ_contact_author 'Andrei S.Batsanov' _publ_contact_author_email a.s.batsanov@durham.ac.uk loop_ _publ_author_name 'Batsanov, Andrei S.' 'Brooke, Gerald M.' 'Holling, Darren' 'Kenwright, Alan M.' _journal_name_full 'Journal of the Chemical Society, Perkin Transactions 1' _journal_volume '?' _journal_page_first '?' _journal_page_last '?' _journal_year '2000' _ccdc_journal_depnumber '?' _publ_section_title ; Pyrolysis reactions of 4-nonafluorobiphenyl prop-2-enyl ether: a remarkable rearrangement reaction of an internal Diels-Alder product ; #===================================================================END data_(9) _audit_creation_method SHELXL-97 _chemical_name_systematic ; 1,2,3,4,7-pentafluorotricyclo[3.3.1.0^2,7^]non-3-eno-8,8-diol hemihydrate ; _chemical_name_common ? _chemical_melting_point '117-118 deg.C' _chemical_formula_moiety 'C9 H7 F5 O2,(H2 O)0.5 ' _chemical_formula_sum 'C9 H8 F5 O2.50' _chemical_formula_weight 251.15 _ccdc_compound_id '9' _ccdc_biological_activity '?' _ccdc_polymorph '?' _ccdc_disorder ; none ; _ccdc_comments '?' 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' '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 Monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 25.133(7) _cell_length_b 6.757(2) _cell_length_c 11.032(4) _cell_angle_alpha 90.00 _cell_angle_beta 105.44(2) _cell_angle_gamma 90.00 _cell_volume 1805.9(10) _cell_formula_units_Z 8 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 707 _cell_measurement_theta_min 12.0 _cell_measurement_theta_max 25.9 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.09 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.848 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1016 _exptl_absorpt_coefficient_mu 0.198 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.9074 _exptl_absorpt_correction_T_max 0.9805 _exptl_absorpt_process_details ? loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist 1.00 0.00 -1.00 0.0500 -1.00 0.00 1.00 0.0500 -1.00 0.00 0.00 0.0450 1.00 0.00 0.00 0.0450 0.00 1.00 0.00 0.2500 0.00 -1.00 0.00 0.2500 _exptl_special_details ; Four sets of \w scans (each scan 0.3\% in \w, exposure time 20 s), each set at different \f and/or 2\q angles, nominally covered over a hemisphere of reciprocal space. The first 50 scans (101 reflections) were repeated at the end of data collection, revealing no significant crystal decay. Crystal to detector distance 4.51 cm. ; _diffrn_ambient_temperature 120(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 'SMART 1K CCD area detector' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 8 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 6231 _diffrn_reflns_av_R_equivalents 0.0332 _diffrn_reflns_av_sigmaI/netI 0.0277 _diffrn_reflns_limit_h_min -32 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.68 _diffrn_reflns_theta_max 27.48 _reflns_number_total 2064 _reflns_number_gt 1703 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0485P)^2^+1.2426P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2064 _refine_ls_number_parameters 182 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0450 _refine_ls_R_factor_gt 0.0338 _refine_ls_wR_factor_ref 0.0883 _refine_ls_wR_factor_gt 0.0830 _refine_ls_goodness_of_fit_ref 1.029 _refine_ls_restrained_S_all 1.029 _refine_ls_shift/su_max 0.000 _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 F1 F 0.09069(4) -0.03960(12) 0.08787(9) 0.0219(2) Uani 1 1 d . . . F2 F 0.10824(4) 0.19881(13) 0.30140(8) 0.0204(2) Uani 1 1 d . . . F3 F 0.21751(4) 0.21924(14) 0.37915(8) 0.0246(2) Uani 1 1 d . . . F4 F 0.27517(4) 0.32298(14) 0.19473(9) 0.0261(2) Uani 1 1 d . . . F7 F 0.08573(4) 0.58719(12) 0.20560(8) 0.0199(2) Uani 1 1 d . . . O1 O 0.04130(4) 0.38237(16) -0.07340(10) 0.0180(2) Uani 1 1 d . . . H01 H 0.0276(11) 0.288(4) -0.127(2) 0.052(7) Uiso 1 1 d . . . O2 O 0.01855(5) 0.25540(17) 0.10196(10) 0.0191(2) Uani 1 1 d . . . H02 H -0.0006(9) 0.349(3) 0.107(2) 0.028(5) Uiso 1 1 d . . . O3 O 0.0000 -0.0882(2) 0.2500 0.0212(3) Uani 1 2 d S . . H03 H 0.0172(11) -0.015(4) 0.215(2) 0.053(7) Uiso 1 1 d . . . C1 C 0.10719(6) 0.1525(2) 0.07976(13) 0.0159(3) Uani 1 1 d . . . C2 C 0.13218(6) 0.2596(2) 0.20916(13) 0.0156(3) Uani 1 1 d . . . C3 C 0.19376(6) 0.2631(2) 0.25744(14) 0.0180(3) Uani 1 1 d . . . C4 C 0.21959(6) 0.3138(2) 0.17315(15) 0.0188(3) Uani 1 1 d . . . C5 C 0.18259(6) 0.3637(2) 0.04569(14) 0.0178(3) Uani 1 1 d . . . H5 H 0.2050(7) 0.406(3) -0.0111(17) 0.018(4) Uiso 1 1 d . . . C6 C 0.14414(6) 0.5352(2) 0.06564(14) 0.0165(3) Uani 1 1 d . . . H61 H 0.1233(7) 0.585(3) -0.0140(17) 0.013(4) Uiso 1 1 d . . . H62 H 0.1658(8) 0.638(3) 0.1129(17) 0.021(5) Uiso 1 1 d . . . C7 C 0.10469(6) 0.4488(2) 0.13594(13) 0.0149(3) Uani 1 1 d . . . C8 C 0.06082(6) 0.3127(2) 0.04953(13) 0.0151(3) Uani 1 1 d . . . C9 C 0.14685(6) 0.1764(2) -0.00230(14) 0.0176(3) Uani 1 1 d . . . H91 H 0.1708(7) 0.056(3) 0.0052(16) 0.016(4) Uiso 1 1 d . . . H92 H 0.1271(8) 0.193(3) -0.0893(19) 0.022(5) Uiso 1 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 F1 0.0276(5) 0.0107(4) 0.0268(5) 0.0003(4) 0.0064(4) -0.0017(4) F2 0.0267(5) 0.0216(5) 0.0140(4) 0.0043(3) 0.0075(4) 0.0008(4) F3 0.0275(5) 0.0265(5) 0.0153(4) 0.0030(4) -0.0023(4) 0.0041(4) F4 0.0168(5) 0.0284(5) 0.0315(5) 0.0030(4) 0.0035(4) 0.0018(4) F7 0.0267(5) 0.0157(4) 0.0182(4) -0.0046(3) 0.0076(4) 0.0034(4) O1 0.0214(5) 0.0183(5) 0.0126(5) 0.0005(4) 0.0016(4) 0.0017(4) O2 0.0185(5) 0.0181(5) 0.0221(6) 0.0018(4) 0.0076(4) 0.0010(5) O3 0.0266(9) 0.0177(8) 0.0216(8) 0.000 0.0104(7) 0.000 C1 0.0209(7) 0.0108(6) 0.0155(7) -0.0005(5) 0.0038(6) -0.0003(6) C2 0.0203(7) 0.0151(7) 0.0120(7) 0.0015(5) 0.0054(5) -0.0003(6) C3 0.0212(8) 0.0152(7) 0.0145(7) 0.0009(5) -0.0004(6) 0.0030(6) C4 0.0158(7) 0.0164(7) 0.0226(8) -0.0004(6) 0.0023(6) 0.0017(6) C5 0.0188(7) 0.0180(7) 0.0173(7) 0.0012(6) 0.0058(6) -0.0001(6) C6 0.0196(7) 0.0141(7) 0.0156(7) 0.0016(6) 0.0042(6) -0.0009(6) C7 0.0207(7) 0.0113(7) 0.0125(6) -0.0014(5) 0.0043(5) 0.0023(5) C8 0.0183(7) 0.0138(7) 0.0132(7) 0.0006(5) 0.0043(5) 0.0001(6) C9 0.0209(7) 0.0158(7) 0.0163(7) -0.0014(6) 0.0051(6) 0.0024(6) _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 F1 C1 1.3725(17) . ? F2 C2 1.3756(17) . ? F3 C3 1.3492(17) . ? F4 C4 1.3545(18) . ? F7 C7 1.3738(16) . ? O1 C8 1.3954(18) . ? O1 H01 0.88(3) . ? O2 C8 1.3929(18) . ? O2 H02 0.80(2) . ? O3 H03 0.82(2) . ? C1 C9 1.523(2) . ? C1 C8 1.560(2) . ? C1 C2 1.575(2) . ? C2 C3 1.497(2) . ? C2 C7 1.571(2) . ? C3 C4 1.313(2) . ? C4 C5 1.503(2) . ? C5 C9 1.560(2) . ? C5 C6 1.562(2) . ? C5 H5 0.990(18) . ? C6 C7 1.528(2) . ? C6 H61 0.956(18) . ? C6 H62 0.95(2) . ? C7 C8 1.552(2) . ? C9 H91 1.002(18) . ? C9 H92 0.96(2) . ? 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 C8 O1 H01 112.3(16) . . ? C8 O2 H02 110.2(15) . . ? F1 C1 C9 113.33(12) . . ? F1 C1 C8 116.65(12) . . ? C9 C1 C8 111.65(12) . . ? F1 C1 C2 115.49(11) . . ? C9 C1 C2 108.89(12) . . ? C8 C1 C2 88.26(11) . . ? F2 C2 C3 110.85(12) . . ? F2 C2 C7 113.85(12) . . ? C3 C2 C7 116.22(12) . . ? F2 C2 C1 112.70(12) . . ? C3 C2 C1 117.07(12) . . ? C7 C2 C1 83.87(10) . . ? C4 C3 F3 126.21(14) . . ? C4 C3 C2 114.29(13) . . ? F3 C3 C2 119.49(13) . . ? C3 C4 F4 124.65(14) . . ? C3 C4 C5 114.94(14) . . ? F4 C4 C5 120.41(13) . . ? C4 C5 C9 107.00(12) . . ? C4 C5 C6 106.64(12) . . ? C9 C5 C6 109.13(12) . . ? C4 C5 H5 110.0(11) . . ? C9 C5 H5 113.2(10) . . ? C6 C5 H5 110.7(10) . . ? C7 C6 C5 107.29(12) . . ? C7 C6 H61 109.2(10) . . ? C5 C6 H61 109.8(10) . . ? C7 C6 H62 110.9(11) . . ? C5 C6 H62 109.4(11) . . ? H61 C6 H62 110.2(15) . . ? F7 C7 C6 113.08(12) . . ? F7 C7 C8 116.84(12) . . ? C6 C7 C8 111.44(12) . . ? F7 C7 C2 115.91(11) . . ? C6 C7 C2 108.42(12) . . ? C8 C7 C2 88.69(11) . . ? O2 C8 O1 112.81(12) . . ? O2 C8 C7 113.90(12) . . ? O1 C8 C7 113.91(12) . . ? O2 C8 C1 109.10(12) . . ? O1 C8 C1 119.42(12) . . ? C7 C8 C1 84.94(11) . . ? C1 C9 C5 107.05(12) . . ? C1 C9 H91 109.7(10) . . ? C5 C9 H91 110.6(10) . . ? C1 C9 H92 111.1(11) . . ? C5 C9 H92 110.1(11) . . ? H91 C9 H92 108.2(15) . . ? 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 O1 H01 O3 0.88(3) 1.91(3) 2.7834(17) 176(2) 5 O2 H02 O1 0.80(2) 2.07(2) 2.8462(17) 163(2) 5_565 O3 H03 O2 0.82(2) 2.21(2) 2.9463(18) 149(2) . _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.48 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.393 _refine_diff_density_min -0.235 _refine_diff_density_rms 0.054 #================================================================END