# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2004 data_global _publ_contact_author_email DO1@ST-ANDREWS.AC.UK _publ_contact_author_name "Prof David O'Hagan" _journal_name_full Org.Biomol.Chem. _journal_coden_Cambridge 0177 _publ_contact_author_address ; Department of Chemistry University of St Andrews North Haugh St Andrews Scotland KY16 9ST ; _publ_section_title ; The observation of a large gauche preference when 2-fluoroethylamine and 2-fluoroethanol become protonated ; loop_ _publ_author_name O.David 'Mark J. Allen' 'Caroline R. S. Briggs' 'Andres E. Goeta' 'Judith A. K. Howard' ; A.Slawin ; 'David Tozer' #============================================ data_6 _database_code_depnum_ccdc_archive 'CCDC 221927' _audit_creation_method SHELXL-97 _chemical_name_systematic ; - ; _chemical_name_common - _chemical_melting_point - _chemical_formula_moiety 'C2 H7 Cl F N' _chemical_formula_sum 'C2 H7 Cl F N' _chemical_formula_weight 99.54 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 orthorhombic _symmetry_space_group_name_H-M Pbca 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 7.621(1) _cell_length_b 8.543(1) _cell_length_c 14.830(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 965.4(2) _cell_formula_units_Z 8 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 924 _cell_measurement_theta_min 12.06 _cell_measurement_theta_max 25.86 _exptl_crystal_description 'thin plate' _exptl_crystal_colour colourless _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.06 _exptl_crystal_density_meas - _exptl_crystal_density_diffrn 1.370 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 416 _exptl_absorpt_coefficient_mu 0.643 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min - _exptl_absorpt_correction_T_max - _exptl_absorpt_process_details - _exptl_special_details ; - ; _diffrn_ambient_temperature 150(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 'Bruker SMART-1K CCD Diffractometer' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count - _diffrn_standards_interval_time - _diffrn_standards_decay_% 0 _diffrn_reflns_number 10312 _diffrn_reflns_av_R_equivalents 0.0290 _diffrn_reflns_av_sigmaI/netI 0.0158 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 2.75 _diffrn_reflns_theta_max 30.29 _reflns_number_total 1371 _reflns_number_gt 1154 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART-NT V5.0 (Bruker, 1998a)' _computing_cell_refinement 'SMART-NT V5.0 (Bruker, 1998a)' _computing_data_reduction 'SAINT-NT V5.0 (Bruker, 1998b)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL-NT V5.1 (Bruker, 1998c)' _computing_publication_material - _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^)+(0.0361P)^2^+0.1706P] 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 1371 _refine_ls_number_parameters 74 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0344 _refine_ls_R_factor_gt 0.0265 _refine_ls_wR_factor_ref 0.0688 _refine_ls_wR_factor_gt 0.0651 _refine_ls_goodness_of_fit_ref 1.078 _refine_ls_restrained_S_all 1.078 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Cl1 Cl 0.07528(3) 0.65744(3) 0.369297(17) 0.02382(10) Uani 1 1 d . . . C1 C -0.42904(15) 0.74205(13) 0.36545(8) 0.0254(2) Uani 1 1 d . . . N1 N -0.56280(13) 0.80272(11) 0.42930(7) 0.0230(2) Uani 1 1 d . . . C2 C -0.40760(17) 0.56748(14) 0.37213(8) 0.0276(2) Uani 1 1 d . . . F1 F -0.33267(10) 0.52893(8) 0.45577(5) 0.03264(18) Uani 1 1 d . . . H4 H -0.515(2) 0.5099(16) 0.3668(8) 0.025(3) Uiso 1 1 d . . . H3 H -0.3288(19) 0.5298(16) 0.3266(10) 0.031(4) Uiso 1 1 d . . . H2 H -0.4701(19) 0.7662(17) 0.3022(10) 0.033(4) Uiso 1 1 d . . . H1 H -0.316(2) 0.7955(17) 0.3809(9) 0.032(4) Uiso 1 1 d . . . H3N H -0.529(2) 0.7922(18) 0.4898(11) 0.039(4) Uiso 1 1 d . . . H2N H -0.667(2) 0.7562(18) 0.4206(10) 0.036(4) Uiso 1 1 d . . . H1N H -0.578(2) 0.905(2) 0.4212(11) 0.041(4) 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 Cl1 0.02707(16) 0.02377(15) 0.02062(15) 0.00047(9) -0.00071(10) -0.00161(9) C1 0.0303(6) 0.0221(5) 0.0237(5) -0.0004(4) 0.0039(4) -0.0001(4) N1 0.0260(5) 0.0206(4) 0.0223(5) -0.0024(3) -0.0022(4) 0.0010(4) C2 0.0340(6) 0.0235(5) 0.0252(6) -0.0015(4) -0.0027(5) 0.0036(5) F1 0.0344(4) 0.0354(4) 0.0281(4) 0.0051(3) -0.0026(3) 0.0053(3) _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 C1 N1 1.4847(14) . ? C1 C2 1.5035(17) . ? C1 H2 1.009(14) . ? C1 H1 1.001(15) . ? N1 H3N 0.938(16) . ? N1 H2N 0.894(16) . ? N1 H1N 0.888(18) . ? C2 F1 1.4046(13) . ? C2 H4 0.959(15) . ? C2 H3 0.959(15) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 C1 C2 112.26(10) . . ? N1 C1 H2 108.0(8) . . ? C2 C1 H2 107.3(8) . . ? N1 C1 H1 106.6(8) . . ? C2 C1 H1 110.1(9) . . ? H2 C1 H1 112.7(12) . . ? C1 N1 H3N 112.7(10) . . ? C1 N1 H2N 111.1(10) . . ? H3N N1 H2N 109.9(14) . . ? C1 N1 H1N 110.1(10) . . ? H3N N1 H1N 105.0(14) . . ? H2N N1 H1N 107.7(14) . . ? F1 C2 C1 109.56(9) . . ? F1 C2 H4 107.5(8) . . ? C1 C2 H4 114.2(8) . . ? F1 C2 H3 106.8(9) . . ? C1 C2 H3 110.7(8) . . ? H4 C2 H3 107.8(12) . . ? 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 N1 C1 C2 F1 -67.83(13) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N1 H3N F1 0.938(16) 2.747(16) 2.9496(12) 93.0(10) . N1 H1N Cl1 0.888(18) 2.291(18) 3.1596(11) 166.0(14) 8_565 N1 H2N Cl1 0.894(16) 2.272(17) 3.1526(11) 168.2(14) 1_455 N1 H3N Cl1 0.938(16) 2.276(16) 3.1850(11) 163.0(13) 4_466 N1 H1N F1 0.888(18) 2.726(16) 3.0337(12) 101.7(12) 4_466 C2 H4 F1 0.959(15) 2.895(13) 3.3332(15) 109.0(9) 5_466 C1 H1 F1 1.001(15) 2.548(15) 3.4319(14) 147.0(11) 8_565 _diffrn_measured_fraction_theta_max 0.947 _diffrn_reflns_theta_full 30.29 _diffrn_measured_fraction_theta_full 0.947 _refine_diff_density_max 0.454 _refine_diff_density_min -0.174 _refine_diff_density_rms 0.048 data_8 _database_code_depnum_ccdc_archive 'CCDC 221928' _audit_creation_method SHELXL-97 _chemical_name_systematic ; - ; _chemical_name_common - _chemical_melting_point - _chemical_formula_moiety 'C16 H19 Cl F N' _chemical_formula_sum 'C16 H19 Cl F N' _chemical_formula_weight 279.77 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 Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 6.821(7) _cell_length_b 10.177(9) _cell_length_c 12.07(2) _cell_angle_alpha 110.74(13) _cell_angle_beta 90.8(2) _cell_angle_gamma 103.32(9) _cell_volume 758.0(17) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 12 _cell_measurement_theta_min 12 _cell_measurement_theta_max 168 _exptl_crystal_description needle _exptl_crystal_colour colourless _exptl_crystal_size_max .03 _exptl_crystal_size_mid .03 _exptl_crystal_size_min .12 _exptl_crystal_density_meas - _exptl_crystal_density_diffrn 1.226 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 296 _exptl_absorpt_coefficient_mu 0.249 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min - _exptl_absorpt_correction_T_max - _exptl_absorpt_process_details - _exptl_special_details ; Crystal decomposed during data collection. ; _diffrn_ambient_temperature 293(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 0.9 _diffrn_standards_number - _diffrn_standards_interval_count - _diffrn_standards_interval_time - _diffrn_standards_decay_% - _diffrn_reflns_number 1605 _diffrn_reflns_av_R_equivalents 0.2652 _diffrn_reflns_av_sigmaI/netI 0.1257 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 5 _diffrn_reflns_theta_min 1.81 _diffrn_reflns_theta_max 23.25 _reflns_number_total 1602 _reflns_number_gt 801 _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^)+(0.1102P)^2^+3.2791P] 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 SHELXL _refine_ls_extinction_coef 0.024(10) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 1602 _refine_ls_number_parameters 177 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.1876 _refine_ls_R_factor_gt 0.0887 _refine_ls_wR_factor_ref 0.2708 _refine_ls_wR_factor_gt 0.2026 _refine_ls_goodness_of_fit_ref 0.935 _refine_ls_restrained_S_all 0.935 _refine_ls_shift/su_max 0.074 _refine_ls_shift/su_mean 0.015 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 1.2101(4) 0.9044(4) 0.1535(3) 0.0808(14) Uani 1 1 d . . . N1 N 0.7660(11) 0.8901(10) 0.1796(7) 0.049(2) Uani 1 1 d D . . H1N H 0.905(6) 0.879(11) 0.172(8) 0.08(3) Uiso 1 1 d D . . C1 C 0.6261(14) 0.7396(10) 0.1202(8) 0.053(3) Uani 1 1 d . . . H1A H 0.6485 0.6799 0.1641 0.063 Uiso 1 1 calc R . . H1B H 0.4871 0.7471 0.1259 0.063 Uiso 1 1 calc R . . C2 C 0.6519(15) 0.6644(11) -0.0077(9) 0.049(3) Uani 1 1 d . . . C3 C 0.5159(17) 0.6604(13) -0.0944(10) 0.071(4) Uani 1 1 d . . . H3A H 0.4121 0.7069 -0.0733 0.085 Uiso 1 1 calc R . . C4 C 0.533(2) 0.5864(16) -0.2142(12) 0.091(5) Uani 1 1 d . . . H4A H 0.4376 0.5810 -0.2723 0.109 Uiso 1 1 calc R . . C5 C 0.688(3) 0.5225(16) -0.2474(13) 0.097(6) Uani 1 1 d . . . H5A H 0.7020 0.4770 -0.3275 0.116 Uiso 1 1 calc R . . C6 C 0.821(2) 0.5267(13) -0.1604(13) 0.089(5) Uani 1 1 d . . . H6A H 0.9239 0.4794 -0.1819 0.107 Uiso 1 1 calc R . . C7 C 0.8073(16) 0.5984(12) -0.0422(10) 0.064(3) Uani 1 1 d . . . H7A H 0.9036 0.6025 0.0150 0.076 Uiso 1 1 calc R . . C8 C 0.7331(15) 0.9511(12) 0.3091(8) 0.064(3) Uani 1 1 d . . . H8A H 0.5985 0.9677 0.3144 0.076 Uiso 1 1 calc R . . H8B H 0.8296 1.0446 0.3465 0.076 Uiso 1 1 calc R . . C9 C 0.7538(18) 0.8571(12) 0.3788(8) 0.058(3) Uani 1 1 d . . . C10 C 0.9243(19) 0.8072(15) 0.3821(10) 0.077(4) Uani 1 1 d . . . H10A H 1.0279 0.8270 0.3366 0.093 Uiso 1 1 calc R . . C11 C 0.943(2) 0.7265(15) 0.4536(11) 0.091(4) Uani 1 1 d . . . H11A H 1.0577 0.6916 0.4549 0.109 Uiso 1 1 calc R . . C12 C 0.791(3) 0.7008(17) 0.5209(11) 0.106(6) Uani 1 1 d . . . H12A H 0.8019 0.6486 0.5693 0.127 Uiso 1 1 calc R . . C13 C 0.620(3) 0.7511(19) 0.5182(12) 0.109(6) Uani 1 1 d . . . H13A H 0.5177 0.7338 0.5651 0.131 Uiso 1 1 calc R . . C14 C 0.6017(18) 0.8277(13) 0.4451(10) 0.080(4) Uani 1 1 d . . . H14A H 0.4849 0.8591 0.4414 0.095 Uiso 1 1 calc R . . C15 C 0.7411(14) 0.9867(11) 0.1148(8) 0.052(3) Uani 1 1 d . . . H15A H 0.6031 0.9969 0.1174 0.062 Uiso 1 1 calc R . . H15B H 0.7609 0.9403 0.0319 0.062 Uiso 1 1 calc R . . C16 C 0.8832(16) 1.1349(12) 0.1635(10) 0.072(4) Uani 1 1 d . . . H16A H 1.0155 1.1274 0.1869 0.087 Uiso 1 1 calc R . . H16B H 0.8978 1.1761 0.1019 0.087 Uiso 1 1 calc R . . F17 F 0.8118(10) 1.2269(7) 0.2620(6) 0.090(2) Uani 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 Cl1 0.0432(16) 0.110(3) 0.090(2) 0.0360(19) 0.0114(13) 0.0215(16) N1 0.039(5) 0.050(6) 0.057(5) 0.019(5) 0.005(4) 0.009(5) C1 0.051(6) 0.049(8) 0.056(7) 0.025(6) 0.006(5) 0.000(6) C2 0.046(6) 0.032(8) 0.071(7) 0.029(6) 0.001(5) -0.001(6) C3 0.075(8) 0.069(10) 0.067(8) 0.020(7) -0.010(6) 0.022(7) C4 0.108(12) 0.074(12) 0.071(10) 0.029(8) -0.026(8) -0.017(10) C5 0.130(14) 0.073(12) 0.058(9) 0.013(8) 0.010(10) -0.015(11) C6 0.110(11) 0.055(9) 0.082(10) 0.004(8) 0.040(9) 0.012(8) C7 0.057(7) 0.050(9) 0.076(9) 0.016(7) -0.003(6) 0.011(7) C8 0.056(6) 0.070(9) 0.053(7) 0.011(6) 0.008(5) 0.013(6) C9 0.073(8) 0.047(9) 0.044(6) 0.014(6) 0.003(5) 0.000(7) C10 0.075(9) 0.090(12) 0.064(8) 0.020(7) 0.000(6) 0.028(9) C11 0.122(12) 0.094(12) 0.064(8) 0.034(8) -0.018(8) 0.032(9) C12 0.160(16) 0.101(14) 0.047(8) 0.034(8) -0.003(10) 0.002(13) C13 0.127(14) 0.112(15) 0.076(10) 0.036(9) 0.024(10) 0.004(12) C14 0.086(9) 0.089(11) 0.066(8) 0.035(8) 0.029(7) 0.014(8) C15 0.052(6) 0.051(8) 0.059(6) 0.029(6) 0.001(5) 0.011(6) C16 0.062(7) 0.064(10) 0.087(9) 0.024(7) 0.005(6) 0.015(7) F17 0.106(5) 0.064(5) 0.091(5) 0.016(4) 0.011(4) 0.022(4) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag N1 C8 1.505(12) . ? N1 C15 1.491(12) . ? N1 C1 1.517(12) . ? C1 C2 1.494(13) . ? C2 C7 1.375(14) . ? C2 C3 1.371(14) . ? C3 C4 1.395(17) . ? C4 C5 1.353(18) . ? C5 C6 1.362(19) . ? C6 C7 1.368(15) . ? C8 C9 1.507(15) . ? C9 C10 1.377(16) . ? C9 C14 1.362(14) . ? C10 C11 1.408(16) . ? C11 C12 1.365(19) . ? C12 C13 1.38(2) . ? C13 C14 1.390(18) . ? C15 C16 1.498(13) . ? C16 F17 1.402(12) . ? 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 N1 C15 112.8(9) . . ? C8 N1 C1 109.8(7) . . ? C15 N1 C1 111.1(7) . . ? C2 C1 N1 114.9(7) . . ? C7 C2 C3 118.4(10) . . ? C7 C2 C1 122.4(10) . . ? C3 C2 C1 119.1(11) . . ? C2 C3 C4 120.0(13) . . ? C5 C4 C3 121.2(13) . . ? C4 C5 C6 118.2(14) . . ? C7 C6 C5 121.8(14) . . ? C6 C7 C2 120.3(12) . . ? N1 C8 C9 115.1(9) . . ? C10 C9 C14 119.7(12) . . ? C10 C9 C8 122.3(11) . . ? C14 C9 C8 118.0(12) . . ? C9 C10 C11 120.8(13) . . ? C12 C11 C10 118.5(15) . . ? C13 C12 C11 120.9(16) . . ? C12 C13 C14 119.8(15) . . ? C9 C14 C13 120.3(14) . . ? N1 C15 C16 114.4(8) . . ? F17 C16 C15 111.1(9) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag C8 N1 C1 C2 -177.1(9) . . . . ? C15 N1 C1 C2 57.4(12) . . . . ? N1 C1 C2 C7 78.5(12) . . . . ? N1 C1 C2 C3 -101.6(11) . . . . ? C7 C2 C3 C4 2.1(16) . . . . ? C1 C2 C3 C4 -177.8(10) . . . . ? C2 C3 C4 C5 -3(2) . . . . ? C3 C4 C5 C6 3(2) . . . . ? C4 C5 C6 C7 -3(2) . . . . ? C5 C6 C7 C2 2.5(18) . . . . ? C3 C2 C7 C6 -2.1(16) . . . . ? C1 C2 C7 C6 177.8(9) . . . . ? C15 N1 C8 C9 179.3(8) . . . . ? C1 N1 C8 C9 54.7(11) . . . . ? N1 C8 C9 C10 54.2(13) . . . . ? N1 C8 C9 C14 -129.3(10) . . . . ? C14 C9 C10 C11 -0.2(17) . . . . ? C8 C9 C10 C11 176.3(10) . . . . ? C9 C10 C11 C12 -1.0(18) . . . . ? C10 C11 C12 C13 1(2) . . . . ? C11 C12 C13 C14 1(2) . . . . ? C10 C9 C14 C13 1.7(18) . . . . ? C8 C9 C14 C13 -175.0(11) . . . . ? C12 C13 C14 C9 -2(2) . . . . ? C8 N1 C15 C16 59.7(11) . . . . ? C1 N1 C15 C16 -176.4(8) . . . . ? N1 C15 C16 F17 -81.9(11) . . . . ? 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 N1 H1N Cl1 0.979(6) 2.07(3) 3.025(9) 166(9) . _diffrn_measured_fraction_theta_max 0.735 _diffrn_reflns_theta_full 23.25 _diffrn_measured_fraction_theta_full 0.735 _refine_diff_density_max 0.221 _refine_diff_density_min -0.245 _refine_diff_density_rms 0.056 data_9 _database_code_depnum_ccdc_archive 'CCDC 221929' _audit_creation_method SHELXL-97 _chemical_name_systematic ; - ; _chemical_name_common - _chemical_melting_point - _chemical_formula_moiety 'C6 H13 Cl F N O' _chemical_formula_sum 'C6 H13 Cl F N O' _chemical_formula_weight 169.62 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' 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 7.340(2) _cell_length_b 9.302(3) _cell_length_c 12.025(4) _cell_angle_alpha 90.00 _cell_angle_beta 92.072(5) _cell_angle_gamma 90.00 _cell_volume 820.6(5) _cell_formula_units_Z 4 _cell_measurement_temperature 125(2) _cell_measurement_reflns_used 60 _cell_measurement_theta_min 12 _cell_measurement_theta_max 168 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_max .1 _exptl_crystal_size_mid .1 _exptl_crystal_size_min .03 _exptl_crystal_density_meas - _exptl_crystal_density_diffrn 1.373 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 360 _exptl_absorpt_coefficient_mu 0.419 _exptl_absorpt_correction_type multiscan _exptl_absorpt_correction_T_min 0.756501 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details - _exptl_special_details ; - ; _diffrn_ambient_temperature 125(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 0.9 _diffrn_standards_number - _diffrn_standards_interval_count - _diffrn_standards_interval_time - _diffrn_standards_decay_% - _diffrn_reflns_number 3185 _diffrn_reflns_av_R_equivalents 0.0428 _diffrn_reflns_av_sigmaI/netI 0.0312 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -5 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.20 _diffrn_reflns_theta_max 23.30 _reflns_number_total 1131 _reflns_number_gt 1029 _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^)+(0.0817P)^2^+0.0877P] 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 SHELXL _refine_ls_extinction_coef 0.009(5) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 1131 _refine_ls_number_parameters 96 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0419 _refine_ls_R_factor_gt 0.0391 _refine_ls_wR_factor_ref 0.1052 _refine_ls_wR_factor_gt 0.1017 _refine_ls_goodness_of_fit_ref 1.027 _refine_ls_restrained_S_all 1.026 _refine_ls_shift/su_max 0.006 _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 Cl1 Cl 0.61037(6) 0.21539(5) 1.09384(4) 0.0252(3) Uani 1 1 d . . . N1 N 0.3959(2) 0.23870(17) 0.87396(15) 0.0199(4) Uani 1 1 d D . . H1N H 0.469(3) 0.224(2) 0.9427(11) 0.037(7) Uiso 1 1 d D . . C2 C 0.2298(3) 0.14418(19) 0.87288(15) 0.0228(5) Uani 1 1 d . . . H2A H 0.2674 0.0422 0.8790 0.027 Uiso 1 1 calc R . . H2B H 0.1595 0.1566 0.8017 0.027 Uiso 1 1 calc R . . C3 C 0.1125(3) 0.1827(2) 0.96847(17) 0.0278(5) Uani 1 1 d . . . H3A H 0.0025 0.1211 0.9662 0.033 Uiso 1 1 calc R . . H3B H 0.1808 0.1637 1.0394 0.033 Uiso 1 1 calc R . . O4 O 0.05860(18) 0.32937(15) 0.96494(12) 0.0291(4) Uani 1 1 d . . . C5 C 0.2156(2) 0.4200(2) 0.96904(16) 0.0247(5) Uani 1 1 d . . . H5A H 0.2858 0.4029 1.0396 0.030 Uiso 1 1 calc R . . H5B H 0.1762 0.5218 0.9679 0.030 Uiso 1 1 calc R . . C6 C 0.3364(2) 0.39279(19) 0.87267(15) 0.0226(5) Uani 1 1 d . . . H6A H 0.2691 0.4143 0.8018 0.027 Uiso 1 1 calc R . . H6B H 0.4445 0.4564 0.8784 0.027 Uiso 1 1 calc R . . C7 C 0.5180(3) 0.2004(2) 0.78165(17) 0.0264(5) Uani 1 1 d . . . H7A H 0.4538 0.2209 0.7096 0.032 Uiso 1 1 calc R . . H7B H 0.5436 0.0959 0.7847 0.032 Uiso 1 1 calc R . . C8 C 0.6953(3) 0.2807(2) 0.78664(19) 0.0328(6) Uani 1 1 d . . . H8A H 0.7430 0.2849 0.8646 0.039 Uiso 1 1 calc R . . H8B H 0.7856 0.2291 0.7422 0.039 Uiso 1 1 calc R . . F8 F 0.67185(16) 0.42144(14) 0.74507(10) 0.0405(4) Uani 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 Cl1 0.0306(4) 0.0231(4) 0.0206(4) -0.00074(16) -0.0159(2) 0.00372(17) N1 0.0223(9) 0.0181(8) 0.0187(9) -0.0007(6) -0.0084(7) 0.0042(6) C2 0.0279(10) 0.0155(9) 0.0241(10) 0.0008(7) -0.0115(8) -0.0022(7) C3 0.0313(11) 0.0214(10) 0.0301(12) 0.0013(8) -0.0057(9) -0.0029(8) O4 0.0226(8) 0.0224(8) 0.0423(9) -0.0032(6) -0.0013(6) 0.0008(6) C5 0.0229(10) 0.0195(10) 0.0312(11) -0.0036(8) -0.0069(8) 0.0011(8) C6 0.0253(10) 0.0160(9) 0.0257(10) 0.0006(8) -0.0087(8) 0.0003(7) C7 0.0276(11) 0.0300(11) 0.0211(11) -0.0050(8) -0.0080(8) 0.0057(8) C8 0.0271(11) 0.0456(14) 0.0253(12) -0.0054(9) -0.0050(9) 0.0035(9) F8 0.0403(8) 0.0438(8) 0.0377(8) -0.0031(6) 0.0066(6) -0.0079(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 N1 C7 1.495(3) . ? N1 C6 1.498(2) . ? N1 C2 1.503(2) . ? C2 C3 1.505(3) . ? C3 O4 1.420(3) . ? O4 C5 1.427(2) . ? C5 C6 1.506(3) . ? C7 C8 1.500(3) . ? C8 F8 1.410(3) . ? 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 C7 N1 C6 113.75(15) . . ? C7 N1 C2 111.23(15) . . ? C6 N1 C2 108.87(13) . . ? N1 C2 C3 109.91(16) . . ? O4 C3 C2 111.88(16) . . ? C3 O4 C5 110.03(14) . . ? O4 C5 C6 111.82(16) . . ? N1 C6 C5 109.40(15) . . ? N1 C7 C8 113.22(17) . . ? F8 C8 C7 110.72(18) . . ? 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 C7 N1 C2 C3 178.48(15) . . . . ? C6 N1 C2 C3 -55.4(2) . . . . ? N1 C2 C3 O4 57.9(2) . . . . ? C2 C3 O4 C5 -59.4(2) . . . . ? C3 O4 C5 C6 60.0(2) . . . . ? C7 N1 C6 C5 -179.65(15) . . . . ? C2 N1 C6 C5 55.7(2) . . . . ? O4 C5 C6 N1 -58.8(2) . . . . ? C6 N1 C7 C8 62.9(2) . . . . ? C2 N1 C7 C8 -173.68(16) . . . . ? N1 C7 C8 F8 -78.8(2) . . . . ? 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 N1 H1N Cl1 0.979(5) 2.062(6) 3.0356(19) 173(2) . _diffrn_measured_fraction_theta_max 0.954 _diffrn_reflns_theta_full 23.30 _diffrn_measured_fraction_theta_full 0.954 _refine_diff_density_max 0.461 _refine_diff_density_min -0.376 _refine_diff_density_rms 0.065 data_11 _database_code_depnum_ccdc_archive 'CCDC 221930' _chemical_name_common - _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_melting_point ? _chemical_formula_moiety 'C4 H10 F2 N. Cl' _chemical_formula_sum 'C4 H10 Cl F2 N' _chemical_formula_weight 145.58 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 7.335(2) _cell_length_b 6.9524(19) _cell_length_c 13.170(4) _cell_angle_alpha 90.00 _cell_angle_beta 93.567(5) _cell_angle_gamma 90.00 _cell_volume 670.3(3) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 50 _cell_measurement_theta_min 12 _cell_measurement_theta_max 28 _exptl_crystal_description plate _exptl_crystal_colour colourless _exptl_crystal_size_max .12 _exptl_crystal_size_mid .1 _exptl_crystal_size_min .01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.443 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 304 _exptl_absorpt_coefficient_mu 0.509 _exptl_absorpt_correction_type multiscan _exptl_absorpt_correction_T_min 0.636707 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 0.9 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3017 _diffrn_reflns_av_R_equivalents 0.0605 _diffrn_reflns_av_sigmaI/netI 0.0641 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -5 _diffrn_reflns_limit_k_max 7 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.10 _diffrn_reflns_theta_max 23.41 _reflns_number_total 914 _reflns_number_gt 594 _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^)+(0.1273P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 914 _refine_ls_number_parameters 81 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.1038 _refine_ls_R_factor_gt 0.0645 _refine_ls_wR_factor_ref 0.1776 _refine_ls_wR_factor_gt 0.1541 _refine_ls_goodness_of_fit_ref 0.925 _refine_ls_restrained_S_all 0.924 _refine_ls_shift/su_max 0.010 _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 Cl1 Cl 0.35427(19) 0.7003(2) 0.64323(11) 0.0432(6) Uani 1 1 d . . . F1 F 0.6120(5) 0.1099(6) 0.8201(3) 0.0602(11) Uani 1 1 d . . . C1 C 0.6499(8) 0.2499(7) 0.7484(5) 0.0368(15) Uani 1 1 d . . . H1A H 0.7805 0.2548 0.7409 0.044 Uiso 1 1 calc R . . H1B H 0.6115 0.3748 0.7720 0.044 Uiso 1 1 calc R . . C2 C 0.5548(7) 0.2073(9) 0.6494(4) 0.0406(14) Uani 1 1 d . . . H2A H 0.5697 0.0720 0.6340 0.049 Uiso 1 1 calc R . . H2B H 0.6103 0.2811 0.5970 0.049 Uiso 1 1 calc R . . N3 N 0.3554(6) 0.2534(5) 0.6474(3) 0.0251(11) Uani 1 1 d D . . H3A H 0.367(7) 0.3938(8) 0.648(4) 0.034(14) Uiso 1 1 d D . . H3B H 0.289(7) 0.190(7) 0.701(3) 0.050(16) Uiso 1 1 d D . . C4 C 0.2564(7) 0.2058(10) 0.5496(4) 0.0404(14) Uani 1 1 d . . . H4A H 0.3097 0.2775 0.4956 0.048 Uiso 1 1 calc R . . H4B H 0.2717 0.0700 0.5357 0.048 Uiso 1 1 calc R . . C5 C 0.0591(8) 0.2500(7) 0.5485(4) 0.0379(15) Uani 1 1 d . . . H5A H 0.0423 0.3776 0.5762 0.046 Uiso 1 1 calc R . . H5B H 0.0073 0.2491 0.4789 0.046 Uiso 1 1 calc R . . F5 F -0.0314(4) 0.1161(5) 0.6054(3) 0.0562(10) Uani 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 Cl1 0.0433(8) 0.0457(10) 0.0411(9) 0.0030(7) 0.0067(6) -0.0003(7) F1 0.061(2) 0.071(3) 0.049(2) 0.0116(18) 0.0068(17) -0.0022(18) C1 0.036(3) 0.021(4) 0.053(4) -0.005(2) 0.005(3) 0.001(2) C2 0.029(3) 0.047(4) 0.046(4) 0.003(3) 0.007(3) 0.007(3) N3 0.031(2) 0.017(3) 0.028(2) 0.0019(16) 0.0070(19) -0.0005(17) C4 0.038(3) 0.053(4) 0.030(3) -0.006(3) 0.004(3) -0.002(3) C5 0.050(3) 0.030(4) 0.034(3) 0.004(2) 0.005(3) 0.009(2) F5 0.052(2) 0.066(3) 0.052(2) 0.0070(18) 0.0108(17) -0.0070(17) _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 1.396(6) . ? C1 C2 1.471(8) . ? C2 N3 1.496(6) . ? N3 C4 1.477(7) . ? C4 C5 1.478(8) . ? C5 F5 1.390(6) . ? 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 C2 110.8(4) . . ? C1 C2 N3 112.4(4) . . ? C4 N3 C2 113.2(4) . . ? C5 C4 N3 113.0(4) . . ? F5 C5 C4 110.9(4) . . ? 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 75.9(6) . . . . ? C1 C2 N3 C4 -178.2(5) . . . . ? C2 N3 C4 C5 179.4(5) . . . . ? N3 C4 C5 F5 -74.2(6) . . . . ? 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 0.9799(11) 2.134(8) 3.107(4) 172(4) . N3 H3B Cl1 0.9800(11) 2.37(3) 3.261(4) 151(4) 2_546 _diffrn_measured_fraction_theta_max 0.928 _diffrn_reflns_theta_full 23.41 _diffrn_measured_fraction_theta_full 0.928 _refine_diff_density_max 0.892 _refine_diff_density_min -0.330 _refine_diff_density_rms 0.084 data_S-10 _database_code_depnum_ccdc_archive 'CCDC 221931' _audit_creation_method SHELXL-97 _chemical_name_systematic ; - ; _chemical_name_common - _chemical_melting_point - _chemical_formula_moiety 'C19 H23 Cl F N' _chemical_formula_sum 'C19 H23 Cl F N' _chemical_formula_weight 319.83 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 Orthorhombic _symmetry_space_group_name_H-M P2(1)2(1)2(1) 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' _cell_length_a 9.21(3) _cell_length_b 12.66(4) _cell_length_c 14.89(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1735(10) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 163 _cell_measurement_theta_min 12 _cell_measurement_theta_max 168 _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max .15 _exptl_crystal_size_mid .2 _exptl_crystal_size_min .2 _exptl_crystal_density_meas - _exptl_crystal_density_diffrn 1.224 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 680 _exptl_absorpt_coefficient_mu 0.226 _exptl_absorpt_correction_type multiscan _exptl_absorpt_correction_T_min 0.724736 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details - _exptl_special_details ; - ; _diffrn_ambient_temperature 293(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 0.9 _diffrn_standards_number - _diffrn_standards_interval_count - _diffrn_standards_interval_time - _diffrn_standards_decay_% - _diffrn_reflns_number 7243 _diffrn_reflns_av_R_equivalents 0.0917 _diffrn_reflns_av_sigmaI/netI 0.1085 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -13 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.11 _diffrn_reflns_theta_max 23.37 _reflns_number_total 2475 _reflns_number_gt 1386 _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^)+(0.0375P)^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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0096(14) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.06(12) _refine_ls_number_reflns 2475 _refine_ls_number_parameters 204 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.1290 _refine_ls_R_factor_gt 0.0475 _refine_ls_wR_factor_ref 0.1007 _refine_ls_wR_factor_gt 0.0793 _refine_ls_goodness_of_fit_ref 0.961 _refine_ls_restrained_S_all 0.961 _refine_ls_shift/su_max 0.006 _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 Cl1 Cl 0.92692(15) 0.35049(9) 0.67899(9) 0.0738(5) Uani 1 1 d . . . N1 N 0.9925(4) 0.1268(3) 0.7311(2) 0.0380(9) Uani 1 1 d D . . H1N H 0.979(4) 0.1987(11) 0.708(2) 0.049(13) Uiso 1 1 d D . . C2 C 0.8627(4) 0.0562(3) 0.7154(3) 0.0407(11) Uani 1 1 d . . . H2A H 0.8944 -0.0177 0.7170 0.049 Uiso 1 1 calc R . . C3 C 0.7648(5) 0.0778(4) 0.7969(3) 0.0679(15) Uani 1 1 d . . . H3A H 0.6748 0.1106 0.7778 0.082 Uiso 1 1 calc R . . H3B H 0.7419 0.0122 0.8274 0.082 Uiso 1 1 calc R . . C4 C 0.8459(6) 0.1496(5) 0.8579(3) 0.0769(17) Uani 1 1 d . . . H4A H 0.8107 0.2216 0.8520 0.092 Uiso 1 1 calc R . . H4B H 0.8344 0.1276 0.9199 0.092 Uiso 1 1 calc R . . C5 C 0.9996(5) 0.1427(4) 0.8304(3) 0.0553(13) Uani 1 1 d . . . H5A H 1.0475 0.0836 0.8595 0.066 Uiso 1 1 calc R . . H5B H 1.0514 0.2072 0.8451 0.066 Uiso 1 1 calc R . . C6 C 1.1322(5) 0.0900(3) 0.6923(3) 0.0477(12) Uani 1 1 d . . . H6A H 1.1651 0.0287 0.7258 0.057 Uiso 1 1 calc R . . H6B H 1.1156 0.0677 0.6309 0.057 Uiso 1 1 calc R . . C7 C 1.2492(5) 0.1709(4) 0.6930(4) 0.0706(15) Uani 1 1 d . . . H7A H 1.3270 0.1488 0.6533 0.085 Uiso 1 1 calc R . . H7B H 1.2109 0.2373 0.6707 0.085 Uiso 1 1 calc R . . F7 F 1.3036(3) 0.1854(3) 0.7783(2) 0.1084(12) Uani 1 1 d . . . C8 C 0.7902(4) 0.0782(3) 0.6252(3) 0.0382(11) Uani 1 1 d . . . H8A H 0.7657 0.1535 0.6245 0.046 Uiso 1 1 calc R . . C9 C 0.8887(5) 0.0587(4) 0.5450(3) 0.0401(12) Uani 1 1 d . . . C10 C 0.9351(5) 0.1417(4) 0.4928(3) 0.0573(13) Uani 1 1 d . . . H10A H 0.9038 0.2099 0.5059 0.069 Uiso 1 1 calc R . . C11 C 1.0264(6) 0.1253(6) 0.4220(4) 0.0799(18) Uani 1 1 d . . . H11A H 1.0566 0.1820 0.3870 0.096 Uiso 1 1 calc R . . C12 C 1.0726(6) 0.0271(7) 0.4028(4) 0.0760(18) Uani 1 1 d . . . H12A H 1.1367 0.0169 0.3553 0.091 Uiso 1 1 calc R . . C13 C 1.0276(6) -0.0573(5) 0.4515(4) 0.0681(16) Uani 1 1 d . . . H13A H 1.0591 -0.1250 0.4369 0.082 Uiso 1 1 calc R . . C14 C 0.9336(6) -0.0415(4) 0.5237(3) 0.0555(13) Uani 1 1 d . . . H14A H 0.9015 -0.0988 0.5574 0.067 Uiso 1 1 calc R . . C15 C 0.6487(5) 0.0181(4) 0.6117(3) 0.0400(12) Uani 1 1 d . . . C16 C 0.5520(5) 0.0539(4) 0.5487(3) 0.0459(12) Uani 1 1 d . . . H16A H 0.5738 0.1148 0.5165 0.055 Uiso 1 1 calc R . . C17 C 0.4238(6) 0.0022(4) 0.5317(3) 0.0559(13) Uani 1 1 d . . . H17A H 0.3595 0.0286 0.4890 0.067 Uiso 1 1 calc R . . C18 C 0.3909(5) -0.0882(5) 0.5776(4) 0.0652(15) Uani 1 1 d . . . H18A H 0.3036 -0.1230 0.5669 0.078 Uiso 1 1 calc R . . C19 C 0.4866(6) -0.1273(4) 0.6393(4) 0.0715(16) Uani 1 1 d . . . H19A H 0.4651 -0.1895 0.6698 0.086 Uiso 1 1 calc R . . C20 C 0.6149(5) -0.0748(4) 0.6564(3) 0.0599(15) Uani 1 1 d . . . H20A H 0.6795 -0.1021 0.6984 0.072 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 0.0951(11) 0.0399(7) 0.0863(9) 0.0014(7) -0.0182(9) 0.0041(8) N1 0.039(2) 0.036(2) 0.039(2) -0.0026(19) 0.0001(19) -0.003(2) C2 0.040(3) 0.040(3) 0.042(3) 0.000(2) 0.002(2) -0.003(2) C3 0.062(4) 0.094(4) 0.048(3) -0.010(3) 0.012(3) -0.014(3) C4 0.075(4) 0.102(5) 0.054(3) -0.016(4) 0.013(3) 0.010(4) C5 0.070(4) 0.056(3) 0.040(3) -0.005(3) -0.007(3) 0.001(3) C6 0.033(3) 0.058(3) 0.053(3) -0.011(3) -0.006(2) 0.000(3) C7 0.046(3) 0.081(4) 0.085(4) -0.009(4) 0.000(3) -0.001(3) F7 0.087(2) 0.116(3) 0.123(3) -0.029(2) -0.033(2) -0.027(2) C8 0.037(3) 0.032(3) 0.045(3) 0.003(2) -0.004(2) -0.003(2) C9 0.033(3) 0.051(3) 0.036(3) 0.002(3) -0.006(2) -0.002(3) C10 0.053(3) 0.066(3) 0.054(3) 0.004(3) -0.001(3) -0.008(3) C11 0.063(5) 0.116(6) 0.061(4) 0.015(4) 0.011(3) -0.024(4) C12 0.044(4) 0.129(6) 0.054(4) -0.025(4) 0.005(3) -0.011(5) C13 0.049(4) 0.084(4) 0.071(4) -0.026(4) -0.015(3) 0.006(3) C14 0.050(3) 0.065(4) 0.051(3) -0.009(3) -0.002(3) -0.006(3) C15 0.029(3) 0.047(3) 0.043(3) -0.002(3) 0.002(2) 0.001(3) C16 0.040(3) 0.050(3) 0.048(3) 0.004(3) 0.000(3) 0.006(3) C17 0.041(4) 0.067(4) 0.060(3) -0.002(3) -0.006(3) 0.008(3) C18 0.042(4) 0.075(4) 0.079(4) 0.000(3) -0.006(3) -0.017(3) C19 0.054(4) 0.059(4) 0.102(4) 0.020(3) -0.012(3) -0.021(3) C20 0.051(4) 0.052(3) 0.076(4) 0.023(3) -0.019(3) -0.009(3) _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 N1 C6 1.486(6) . ? N1 C5 1.493(7) . ? N1 C2 1.511(6) . ? C2 C8 1.526(6) . ? C2 C3 1.536(7) . ? C3 C4 1.487(7) . ? C4 C5 1.476(7) . ? C6 C7 1.486(7) . ? C7 F7 1.377(7) . ? C8 C15 1.521(7) . ? C8 C9 1.520(7) . ? C9 C14 1.370(7) . ? C9 C10 1.376(6) . ? C10 C11 1.364(7) . ? C11 C12 1.344(8) . ? C12 C13 1.356(8) . ? C13 C14 1.395(7) . ? C15 C16 1.370(6) . ? C15 C20 1.386(6) . ? C16 C17 1.373(7) . ? C17 C18 1.367(7) . ? C18 C19 1.366(7) . ? C19 C20 1.379(7) . ? 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 C6 N1 C5 112.9(3) . . ? C6 N1 C2 116.0(4) . . ? C5 N1 C2 105.6(3) . . ? N1 C2 C8 112.0(4) . . ? N1 C2 C3 103.6(4) . . ? C8 C2 C3 114.0(4) . . ? C4 C3 C2 107.3(4) . . ? C5 C4 C3 106.0(4) . . ? C4 C5 N1 103.9(4) . . ? C7 C6 N1 114.1(4) . . ? F7 C7 C6 111.2(4) . . ? C15 C8 C9 109.0(4) . . ? C15 C8 C2 113.6(4) . . ? C9 C8 C2 113.6(4) . . ? C14 C9 C10 118.9(5) . . ? C14 C9 C8 120.8(4) . . ? C10 C9 C8 120.3(5) . . ? C11 C10 C9 120.8(6) . . ? C12 C11 C10 120.0(6) . . ? C11 C12 C13 121.2(6) . . ? C12 C13 C14 119.2(6) . . ? C9 C14 C13 119.9(5) . . ? C16 C15 C20 117.6(4) . . ? C16 C15 C8 118.8(4) . . ? C20 C15 C8 123.6(4) . . ? C15 C16 C17 121.8(5) . . ? C18 C17 C16 119.8(5) . . ? C17 C18 C19 119.8(5) . . ? C18 C19 C20 120.1(5) . . ? C19 C20 C15 120.8(4) . . ? 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 C6 N1 C2 C8 -85.2(5) . . . . ? C5 N1 C2 C8 149.0(4) . . . . ? C6 N1 C2 C3 151.5(4) . . . . ? C5 N1 C2 C3 25.7(4) . . . . ? N1 C2 C3 C4 -5.0(5) . . . . ? C8 C2 C3 C4 -127.0(5) . . . . ? C2 C3 C4 C5 -17.7(6) . . . . ? C3 C4 C5 N1 33.8(6) . . . . ? C6 N1 C5 C4 -165.0(4) . . . . ? C2 N1 C5 C4 -37.3(5) . . . . ? C5 N1 C6 C7 -69.8(5) . . . . ? C2 N1 C6 C7 168.2(4) . . . . ? N1 C6 C7 F7 74.1(5) . . . . ? N1 C2 C8 C15 -173.0(3) . . . . ? C3 C2 C8 C15 -55.8(5) . . . . ? N1 C2 C8 C9 61.6(5) . . . . ? C3 C2 C8 C9 178.9(4) . . . . ? C15 C8 C9 C14 -60.4(5) . . . . ? C2 C8 C9 C14 67.4(5) . . . . ? C15 C8 C9 C10 120.0(5) . . . . ? C2 C8 C9 C10 -112.2(5) . . . . ? C14 C9 C10 C11 -1.2(7) . . . . ? C8 C9 C10 C11 178.4(4) . . . . ? C9 C10 C11 C12 -0.3(8) . . . . ? C10 C11 C12 C13 1.5(9) . . . . ? C11 C12 C13 C14 -1.2(8) . . . . ? C10 C9 C14 C13 1.5(7) . . . . ? C8 C9 C14 C13 -178.0(4) . . . . ? C12 C13 C14 C9 -0.4(7) . . . . ? C9 C8 C15 C16 -72.2(5) . . . . ? C2 C8 C15 C16 160.0(4) . . . . ? C9 C8 C15 C20 104.2(5) . . . . ? C2 C8 C15 C20 -23.6(6) . . . . ? C20 C15 C16 C17 1.9(6) . . . . ? C8 C15 C16 C17 178.6(4) . . . . ? C15 C16 C17 C18 -0.7(7) . . . . ? C16 C17 C18 C19 -0.8(7) . . . . ? C17 C18 C19 C20 1.1(7) . . . . ? C18 C19 C20 C15 0.1(7) . . . . ? C16 C15 C20 C19 -1.6(6) . . . . ? C8 C15 C20 C19 -178.1(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 N1 H1N Cl1 0.979(6) 2.028(11) 2.997(10) 170(3) . _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 23.37 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.158 _refine_diff_density_min -0.193 _refine_diff_density_rms 0.040