# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2006 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name "D. O'Hagan" 'Natalie E. J. Gooseman' 'A. Slawin' 'Andrew M. Teale' 'David Tozer' 'Robert J. Young' _publ_contact_author_name "D. O'Hagan" _publ_contact_author_address ; School of Chemistry University of St Andrews Purdie Building North Haugh St Andrews Fife KY16 9ST UNITED KINGDOM ; _publ_contact_author_email DO1@ST-ANDREWS.AC.UK _publ_requested_journal 'Chemical Communications' _publ_section_title ; The intramolecular beta-fluorine***ammonium interaction in 4- and 8-membered rings ; data_ngdh9 _database_code_depnum_ccdc_archive 'CCDC 606604' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C3 H7 F N.Cl' _chemical_formula_sum 'C3 H7 Cl F N' _chemical_formula_weight 111.55 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 6.5872(11) _cell_length_b 8.3434(14) _cell_length_c 9.0693(15) _cell_angle_alpha 90.00 _cell_angle_beta 97.565(8) _cell_angle_gamma 90.00 _cell_volume 494.11(14) _cell_formula_units_Z 4 _cell_measurement_temperature 93(2) _cell_measurement_reflns_used 2719 _cell_measurement_theta_min 3.28 _cell_measurement_theta_max 27.84 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.030 _exptl_crystal_size_mid 0.030 _exptl_crystal_size_min 0.010 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.499 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 232 _exptl_absorpt_coefficient_mu 0.638 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8947 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 93(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator confocal _diffrn_measurement_device_type CCD _diffrn_measurement_method dtprofit.ref _diffrn_detector_area_resol_mean 0.83 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3221 _diffrn_reflns_av_R_equivalents 0.0127 _diffrn_reflns_av_sigmaI/netI 0.0084 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 3.33 _diffrn_reflns_theta_max 25.35 _reflns_number_total 856 _reflns_number_gt 808 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku Corp., 2004)' _computing_cell_refinement 'CrystalClear (Rigaku Corp., 2004)' _computing_data_reduction 'CrystalClear (Rigaku Corp., 2004)' _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^)+(0.0320P)^2^+0.3506P] 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 856 _refine_ls_number_parameters 64 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0219 _refine_ls_R_factor_gt 0.0199 _refine_ls_wR_factor_ref 0.0517 _refine_ls_wR_factor_gt 0.0502 _refine_ls_goodness_of_fit_ref 0.902 _refine_ls_restrained_S_all 0.901 _refine_ls_shift/su_max 0.011 _refine_ls_shift/su_mean 0.002 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 Cl1 Cl 0.71333(4) 0.08839(4) 0.19068(3) 0.01412(13) Uani 1 1 d . . . F1 F 0.21659(12) 0.27117(10) 0.31161(8) 0.0211(2) Uani 1 1 d . . . C1 C 0.1517(2) 0.31980(16) 0.16382(14) 0.0153(3) Uani 1 1 d . . . H1A H 0.0214 0.3827 0.1511 0.018 Uiso 1 1 calc R . . C2 C 0.3269(2) 0.39870(15) 0.09387(14) 0.0155(3) Uani 1 1 d . . . H2A H 0.2850 0.4963 0.0357 0.019 Uiso 1 1 calc R . . H2B H 0.4507 0.4193 0.1658 0.019 Uiso 1 1 calc R . . N3 N 0.34379(16) 0.25129(13) -0.00125(11) 0.0131(2) Uani 1 1 d D . . H3A H 0.4704(14) 0.1928(18) 0.0325(18) 0.029(4) Uiso 1 1 d D . . H3B H 0.332(3) 0.272(2) -0.1083(4) 0.028(4) Uiso 1 1 d D . . C4 C 0.1550(2) 0.18125(16) 0.05416(14) 0.0155(3) Uani 1 1 d . . . H4A H 0.1791 0.0755 0.1028 0.019 Uiso 1 1 calc R . . H4B H 0.0334 0.1779 -0.0226 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 Cl1 0.01297(19) 0.01625(19) 0.01258(18) -0.00109(11) -0.00041(12) 0.00077(11) F1 0.0225(4) 0.0299(5) 0.0110(4) 0.0004(3) 0.0024(3) -0.0044(3) C1 0.0140(6) 0.0192(7) 0.0122(6) -0.0013(5) 0.0004(5) 0.0004(5) C2 0.0165(7) 0.0148(6) 0.0150(6) -0.0036(5) 0.0017(5) -0.0013(5) N3 0.0123(5) 0.0158(5) 0.0113(5) -0.0006(4) 0.0017(4) -0.0002(4) C4 0.0138(6) 0.0184(7) 0.0147(6) -0.0016(5) 0.0033(5) -0.0034(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 F1 C1 1.4117(15) . ? C1 C4 1.5269(18) . ? C1 C2 1.5365(18) . ? C1 H1A 1.0000 . ? C2 N3 1.5148(16) . ? C2 H2A 0.9900 . ? C2 H2B 0.9900 . ? N3 C4 1.5184(16) . ? N3 H3A 0.9798(10) . ? N3 H3B 0.9797(10) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? 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 F1 C1 C4 111.87(11) . . ? F1 C1 C2 111.42(10) . . ? C4 C1 C2 88.84(9) . . ? F1 C1 H1A 114.1 . . ? C4 C1 H1A 114.1 . . ? C2 C1 H1A 114.1 . . ? N3 C2 C1 90.15(9) . . ? N3 C2 H2A 113.6 . . ? C1 C2 H2A 113.6 . . ? N3 C2 H2B 113.6 . . ? C1 C2 H2B 113.6 . . ? H2A C2 H2B 110.9 . . ? C4 N3 C2 89.96(9) . . ? C4 N3 H3A 113.9(10) . . ? C2 N3 H3A 110.5(10) . . ? C4 N3 H3B 115.6(10) . . ? C2 N3 H3B 114.6(10) . . ? H3A N3 H3B 110.7(14) . . ? N3 C4 C1 90.38(9) . . ? N3 C4 H4A 113.6 . . ? C1 C4 H4A 113.6 . . ? N3 C4 H4B 113.6 . . ? C1 C4 H4B 113.6 . . ? H4A C4 H4B 110.8 . . ? 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 F1 C1 C2 N3 106.91(11) . . . . ? C4 C1 C2 N3 -6.18(10) . . . . ? C1 C2 N3 C4 6.22(10) . . . . ? C2 N3 C4 C1 -6.26(10) . . . . ? F1 C1 C4 N3 -106.51(11) . . . . ? C2 C1 C4 N3 6.17(10) . . . . ? 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 N3 H3A Cl1 0.9798(10) 2.185(7) 3.1124(12) 157.4(14) . N3 H3B Cl1 0.9797(10) 2.215(8) 3.1148(12) 152.1(14) 4_565 _diffrn_measured_fraction_theta_max 0.948 _diffrn_reflns_theta_full 25.35 _diffrn_measured_fraction_theta_full 0.948 _refine_diff_density_max 0.273 _refine_diff_density_min -0.192 _refine_diff_density_rms 0.038 # Attachment 'Structure6.cif' data_ngdh8 _database_code_depnum_ccdc_archive 'CCDC 606605' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C6 H15 Br2 F N2' _chemical_formula_sum 'C6 H15 Br2 F N2' _chemical_formula_weight 294.02 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' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/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 7.0901(16) _cell_length_b 12.250(3) _cell_length_c 12.581(3) _cell_angle_alpha 90.00 _cell_angle_beta 106.266(6) _cell_angle_gamma 90.00 _cell_volume 1049.0(4) _cell_formula_units_Z 4 _cell_measurement_temperature 93(2) _cell_measurement_reflns_used 3782 _cell_measurement_theta_min 2.3681 _cell_measurement_theta_max 25.3491 _exptl_crystal_description Prism _exptl_crystal_colour Colorless _exptl_crystal_size_max 0.1000 _exptl_crystal_size_mid 0.0300 _exptl_crystal_size_min 0.0300 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.862 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 576 _exptl_absorpt_coefficient_mu 7.691 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.4862 _exptl_absorpt_correction_T_max 1.0000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 93(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'rotating anode' _diffrn_radiation_monochromator confocal _diffrn_measurement_device_type CCD _diffrn_measurement_method dtprofit.ref _diffrn_detector_area_resol_mean 0.83 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6572 _diffrn_reflns_av_R_equivalents 0.0333 _diffrn_reflns_av_sigmaI/netI 0.0301 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.37 _diffrn_reflns_theta_max 25.37 _reflns_number_total 1887 _reflns_number_gt 1707 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku Corp., 2004)' _computing_cell_refinement 'CrystalClear (Rigaku Corp., 2004)' _computing_data_reduction 'CrystalClear (Rigaku Corp., 2004)' _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^)+(0.0308P)^2^+0.7607P] 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 1887 _refine_ls_number_parameters 117 _refine_ls_number_restraints 4 _refine_ls_R_factor_all 0.0293 _refine_ls_R_factor_gt 0.0248 _refine_ls_wR_factor_ref 0.0589 _refine_ls_wR_factor_gt 0.0568 _refine_ls_goodness_of_fit_ref 1.026 _refine_ls_restrained_S_all 1.025 _refine_ls_shift/su_max 0.011 _refine_ls_shift/su_mean 0.001 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 Br1 Br 0.64524(4) 0.34108(2) 0.41464(2) 0.01553(10) Uani 1 1 d . . . Br2 Br -0.03063(4) 0.40957(2) 0.19958(2) 0.01490(10) Uani 1 1 d . . . F1 F 0.4197(2) 0.10292(13) 0.43570(13) 0.0158(4) Uani 1 1 d . . . C1 C 0.2970(4) 0.1092(2) 0.5069(2) 0.0135(6) Uani 1 1 d . . . H1A H 0.2382 0.0351 0.5082 0.016 Uiso 1 1 calc R . . C2 C 0.4290(4) 0.1313(2) 0.6225(2) 0.0136(6) Uani 1 1 d . . . H2A H 0.3460 0.1400 0.6734 0.016 Uiso 1 1 calc R . . H2B H 0.5144 0.0670 0.6474 0.016 Uiso 1 1 calc R . . N3 N 0.5570(3) 0.23107(19) 0.6312(2) 0.0133(5) Uani 1 1 d D . . H3A H 0.584(4) 0.246(2) 0.5604(11) 0.012(7) Uiso 1 1 d D . . H3B H 0.680(3) 0.209(2) 0.685(2) 0.025(9) Uiso 1 1 d D . . C4 C 0.4888(4) 0.3342(2) 0.6751(2) 0.0154(6) Uani 1 1 d . . . H4A H 0.5596 0.3970 0.6550 0.019 Uiso 1 1 calc R . . H4B H 0.5256 0.3300 0.7570 0.019 Uiso 1 1 calc R . . C5 C 0.2700(4) 0.3556(2) 0.6330(3) 0.0180(6) Uani 1 1 d . . . H5A H 0.2005 0.2894 0.6469 0.022 Uiso 1 1 calc R . . H5B H 0.2375 0.4152 0.6780 0.022 Uiso 1 1 calc R . . C6 C 0.1880(4) 0.3858(2) 0.5127(2) 0.0160(6) Uani 1 1 d . . . H6A H 0.0488 0.4075 0.4998 0.019 Uiso 1 1 calc R . . H6B H 0.2602 0.4504 0.4974 0.019 Uiso 1 1 calc R . . N7 N 0.1981(3) 0.29734(19) 0.4314(2) 0.0138(5) Uani 1 1 d D . . H7A H 0.3314(18) 0.295(3) 0.423(3) 0.018(8) Uiso 1 1 d D . . H7B H 0.118(4) 0.324(2) 0.3595(13) 0.022(9) Uiso 1 1 d D . . C8 C 0.1308(4) 0.1857(2) 0.4533(2) 0.0142(6) Uani 1 1 d . . . H8A H 0.0530 0.1536 0.3824 0.017 Uiso 1 1 calc R . . H8B H 0.0433 0.1926 0.5020 0.017 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 Br1 0.01696(17) 0.01659(17) 0.01383(17) -0.00081(11) 0.00561(12) -0.00403(10) Br2 0.01299(16) 0.01720(17) 0.01447(17) 0.00372(11) 0.00377(12) 0.00217(10) F1 0.0183(8) 0.0147(9) 0.0163(8) -0.0022(7) 0.0077(7) 0.0016(6) C1 0.0132(13) 0.0127(14) 0.0156(15) -0.0015(12) 0.0057(12) -0.0005(11) C2 0.0139(14) 0.0088(14) 0.0185(15) 0.0021(12) 0.0054(12) 0.0013(10) N3 0.0138(12) 0.0129(12) 0.0121(12) -0.0014(10) 0.0015(10) -0.0007(9) C4 0.0242(15) 0.0093(14) 0.0123(15) -0.0042(11) 0.0044(13) -0.0029(11) C5 0.0233(15) 0.0133(15) 0.0200(16) -0.0025(12) 0.0104(13) -0.0011(11) C6 0.0129(14) 0.0124(14) 0.0228(16) -0.0012(12) 0.0051(12) 0.0027(11) N7 0.0132(12) 0.0114(12) 0.0155(13) 0.0015(10) 0.0019(10) 0.0001(9) C8 0.0137(14) 0.0126(14) 0.0151(15) -0.0015(12) 0.0021(12) -0.0034(11) _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 1.415(3) . ? C1 C8 1.509(4) . ? C1 C2 1.517(4) . ? C1 H1A 1.0000 . ? C2 N3 1.508(4) . ? C2 H2A 0.9900 . ? C2 H2B 0.9900 . ? N3 C4 1.511(4) . ? N3 H3A 0.9800(11) . ? N3 H3B 0.9799(11) . ? C4 C5 1.515(4) . ? C4 H4A 0.9900 . ? C4 H4B 0.9900 . ? C5 C6 1.507(4) . ? C5 H5A 0.9900 . ? C5 H5B 0.9900 . ? C6 N7 1.506(4) . ? C6 H6A 0.9900 . ? C6 H6B 0.9900 . ? N7 C8 1.499(4) . ? N7 H7A 0.9799(11) . ? N7 H7B 0.9799(11) . ? C8 H8A 0.9900 . ? C8 H8B 0.9900 . ? 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 F1 C1 C8 107.0(2) . . ? F1 C1 C2 107.0(2) . . ? C8 C1 C2 120.8(2) . . ? F1 C1 H1A 107.1 . . ? C8 C1 H1A 107.1 . . ? C2 C1 H1A 107.1 . . ? N3 C2 C1 114.3(2) . . ? N3 C2 H2A 108.7 . . ? C1 C2 H2A 108.7 . . ? N3 C2 H2B 108.7 . . ? C1 C2 H2B 108.7 . . ? H2A C2 H2B 107.6 . . ? C2 N3 C4 117.2(2) . . ? C2 N3 H3A 110.6(17) . . ? C4 N3 H3A 109.9(18) . . ? C2 N3 H3B 103.2(19) . . ? C4 N3 H3B 106.7(19) . . ? H3A N3 H3B 109(2) . . ? N3 C4 C5 114.7(2) . . ? N3 C4 H4A 108.6 . . ? C5 C4 H4A 108.6 . . ? N3 C4 H4B 108.6 . . ? C5 C4 H4B 108.6 . . ? H4A C4 H4B 107.6 . . ? C6 C5 C4 117.6(3) . . ? C6 C5 H5A 107.9 . . ? C4 C5 H5A 107.9 . . ? C6 C5 H5B 107.9 . . ? C4 C5 H5B 107.9 . . ? H5A C5 H5B 107.2 . . ? N7 C6 C5 115.2(2) . . ? N7 C6 H6A 108.5 . . ? C5 C6 H6A 108.5 . . ? N7 C6 H6B 108.5 . . ? C5 C6 H6B 108.5 . . ? H6A C6 H6B 107.5 . . ? C8 N7 C6 117.0(2) . . ? C8 N7 H7A 111.3(18) . . ? C6 N7 H7A 108.7(19) . . ? C8 N7 H7B 109.9(19) . . ? C6 N7 H7B 105.3(19) . . ? H7A N7 H7B 104(3) . . ? N7 C8 C1 113.6(2) . . ? N7 C8 H8A 108.8 . . ? C1 C8 H8A 108.8 . . ? N7 C8 H8B 108.8 . . ? C1 C8 H8B 108.8 . . ? H8A C8 H8B 107.7 . . ? 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 F1 C1 C2 N3 55.4(3) . . . . ? C8 C1 C2 N3 -67.2(3) . . . . ? C1 C2 N3 C4 99.7(3) . . . . ? C2 N3 C4 C5 -40.8(3) . . . . ? N3 C4 C5 C6 -69.5(3) . . . . ? C4 C5 C6 N7 66.2(3) . . . . ? C5 C6 N7 C8 47.1(3) . . . . ? C6 N7 C8 C1 -100.1(3) . . . . ? F1 C1 C8 N7 -57.7(3) . . . . ? C2 C1 C8 N7 64.9(4) . . . . ? 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 N3 H3A Br1 0.9800(11) 2.313(10) 3.254(3) 161(2) . N3 H3B Br2 0.9799(11) 2.48(2) 3.294(2) 140(2) 4_666 N3 H3B Br1 0.9799(11) 3.03(3) 3.555(3) 115(2) 4_566 N7 H7A Br1 0.9799(11) 2.326(9) 3.280(2) 164(3) . N7 H7B Br2 0.9799(11) 2.252(6) 3.222(2) 170(3) . _diffrn_measured_fraction_theta_max 0.976 _diffrn_reflns_theta_full 25.37 _diffrn_measured_fraction_theta_full 0.976 _refine_diff_density_max 0.646 _refine_diff_density_min -0.685 _refine_diff_density_rms 0.099