data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Dr Philip Dyer' _publ_contact_author_address ; Department of Chemistry University of Durham South Road Durham County Durham DH1 3LE UNITED KINGDOM ; _publ_contact_author_email P.W.DYER@DURHAM.AC.UK _publ_section_title ; Sterically-controlled regioselective para-substitutions of aniline ; loop_ _publ_author_name 'Philip Dyer' 'John Fawcett' 'Gerry A. Griffith' 'Martin J. Hanton' 'Celine Olivier' ; A.R.Patterson ; 'Samuel Suhard' data_03148 _database_code_depnum_ccdc_archive 'CCDC 236521' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C19 H36 Li N3' _chemical_formula_weight 313.45 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' Li Li -0.0003 0.0001 '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' _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 9.1878(18) _cell_length_b 14.344(3) _cell_length_c 15.575(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2052.7(7) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 1287 _cell_measurement_theta_min 2.61 _cell_measurement_theta_max 24.43 _exptl_crystal_description block _exptl_crystal_colour colourless _exptl_crystal_size_max 0.26 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.014 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 696 _exptl_absorpt_coefficient_mu 0.059 _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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 13076 _diffrn_reflns_av_R_equivalents 0.0849 _diffrn_reflns_av_sigmaI/netI 0.0955 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 1.93 _diffrn_reflns_theta_max 24.99 _reflns_number_total 3619 _reflns_number_gt 2170 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _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^)+(0.0479P)^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 0.0132(17) _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(4) _refine_ls_number_reflns 3619 _refine_ls_number_parameters 218 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0976 _refine_ls_R_factor_gt 0.0563 _refine_ls_wR_factor_ref 0.1297 _refine_ls_wR_factor_gt 0.1090 _refine_ls_goodness_of_fit_ref 0.926 _refine_ls_restrained_S_all 0.926 _refine_ls_shift/su_max 0.789 _refine_ls_shift/su_mean 0.005 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 Li1 Li 0.7143(6) -0.0016(4) 0.1912(3) 0.0447(14) Uani 1 1 d . . . N1 N 0.8207(2) 0.09811(18) 0.24270(14) 0.0361(7) Uani 1 1 d . . . N2 N 0.6145(3) -0.12405(19) 0.23128(14) 0.0413(7) Uani 1 1 d . . . N3 N 0.5710(3) 0.00534(18) 0.09191(15) 0.0387(7) Uani 1 1 d . . . C1 C 0.7694(3) 0.1356(2) 0.31578(18) 0.0356(8) Uani 1 1 d . . . C2 C 0.8331(3) 0.2032(2) 0.36866(18) 0.0389(8) Uani 1 1 d . . . H2 H 0.9223 0.2286 0.3529 0.047 Uiso 1 1 calc R . . C3 C 0.7679(4) 0.2330(2) 0.44305(19) 0.0437(9) Uani 1 1 d . . . H3 H 0.8148 0.2778 0.4761 0.052 Uiso 1 1 calc R . . C4 C 0.6349(4) 0.1988(2) 0.47067(19) 0.0440(9) Uani 1 1 d . . . H4 H 0.5928 0.2189 0.5217 0.053 Uiso 1 1 calc R . . C5 C 0.5684(3) 0.1343(2) 0.41945(18) 0.0425(8) Uani 1 1 d . . . H5 H 0.4783 0.1106 0.4356 0.051 Uiso 1 1 calc R . . C6 C 0.6311(3) 0.1037(2) 0.34508(17) 0.0394(8) Uani 1 1 d . . . H6 H 0.5813 0.0602 0.3120 0.047 Uiso 1 1 calc R . . C7 C 0.9565(3) 0.1331(2) 0.20631(18) 0.0411(8) Uani 1 1 d . . . H7 H 0.9900 0.1845 0.2428 0.049 Uiso 1 1 calc R . . C8 C 1.0741(4) 0.0585(3) 0.2069(2) 0.0496(9) Uani 1 1 d . . . H8 H 1.1605 0.0847 0.1790 0.060 Uiso 1 1 calc R . . C9 C 1.1152(4) 0.0338(3) 0.2981(2) 0.0783(14) Uani 1 1 d . . . H9A H 1.1471 0.0888 0.3276 0.117 Uiso 1 1 calc R . . H9B H 1.1923 -0.0113 0.2975 0.117 Uiso 1 1 calc R . . H9C H 1.0321 0.0081 0.3271 0.117 Uiso 1 1 calc R . . C10 C 1.0313(4) -0.0291(3) 0.1582(3) 0.0842(14) Uani 1 1 d . . . H10A H 1.1159 -0.0673 0.1494 0.126 Uiso 1 1 calc R . . H10B H 0.9906 -0.0122 0.1036 0.126 Uiso 1 1 calc R . . H10C H 0.9605 -0.0633 0.1908 0.126 Uiso 1 1 calc R . . C11 C 0.9253(4) 0.1731(3) 0.11736(19) 0.0483(9) Uani 1 1 d . . . H11 H 0.8698 0.1262 0.0854 0.058 Uiso 1 1 calc R . . C12 C 0.8304(4) 0.2591(3) 0.1256(3) 0.0765(14) Uani 1 1 d . . . H12A H 0.8842 0.3077 0.1536 0.115 Uiso 1 1 calc R . . H12B H 0.7456 0.2443 0.1590 0.115 Uiso 1 1 calc R . . H12C H 0.8012 0.2796 0.0696 0.115 Uiso 1 1 calc R . . C13 C 1.0591(4) 0.1962(3) 0.0653(2) 0.0736(13) Uani 1 1 d . . . H13A H 1.1248 0.2327 0.0995 0.110 Uiso 1 1 calc R . . H13B H 1.0313 0.2311 0.0153 0.110 Uiso 1 1 calc R . . H13C H 1.1063 0.1396 0.0479 0.110 Uiso 1 1 calc R . . C14 C 0.4749(3) -0.1187(2) 0.1855(2) 0.0505(9) Uani 1 1 d . . . H14A H 0.4100 -0.0771 0.2163 0.061 Uiso 1 1 calc R . . H14B H 0.4305 -0.1800 0.1843 0.061 Uiso 1 1 calc R . . C15 C 0.4929(4) -0.0841(2) 0.09525(19) 0.0497(9) Uani 1 1 d . . . H15A H 0.5462 -0.1301 0.0621 0.060 Uiso 1 1 calc R . . H15B H 0.3977 -0.0766 0.0692 0.060 Uiso 1 1 calc R . . C16 C 0.7008(4) -0.2018(3) 0.1979(2) 0.0603(11) Uani 1 1 d . . . H16A H 0.7894 -0.2071 0.2302 0.090 Uiso 1 1 calc R . . H16B H 0.7236 -0.1906 0.1386 0.090 Uiso 1 1 calc R . . H16C H 0.6461 -0.2585 0.2028 0.090 Uiso 1 1 calc R . . C17 C 0.5879(4) -0.1429(2) 0.32204(18) 0.0620(11) Uani 1 1 d . . . H17A H 0.5431 -0.2030 0.3281 0.093 Uiso 1 1 calc R . . H17B H 0.5246 -0.0960 0.3451 0.093 Uiso 1 1 calc R . . H17C H 0.6786 -0.1422 0.3526 0.093 Uiso 1 1 calc R . . C18 C 0.6230(4) 0.0211(3) 0.00468(18) 0.0556(10) Uani 1 1 d . . . H18A H 0.6876 -0.0285 -0.0115 0.083 Uiso 1 1 calc R . . H18B H 0.6740 0.0794 0.0021 0.083 Uiso 1 1 calc R . . H18C H 0.5417 0.0226 -0.0340 0.083 Uiso 1 1 calc R . . C19 C 0.4765(4) 0.0819(2) 0.1158(2) 0.0594(11) Uani 1 1 d . . . H19A H 0.3979 0.0864 0.0754 0.089 Uiso 1 1 calc R . . H19B H 0.5310 0.1390 0.1157 0.089 Uiso 1 1 calc R . . H19C H 0.4379 0.0710 0.1722 0.089 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 Li1 0.043(3) 0.047(4) 0.044(3) -0.001(3) 0.003(3) -0.005(3) N1 0.0304(14) 0.0384(17) 0.0394(15) -0.0048(13) 0.0076(11) -0.0055(13) N2 0.0439(16) 0.0439(18) 0.0361(14) -0.0001(13) -0.0003(12) -0.0021(15) N3 0.0427(16) 0.0325(16) 0.0411(15) -0.0029(13) -0.0004(13) -0.0002(14) C1 0.0338(17) 0.036(2) 0.0374(17) 0.0013(16) 0.0006(14) -0.0017(16) C2 0.0385(19) 0.039(2) 0.0392(18) -0.0054(16) -0.0024(15) -0.0014(17) C3 0.045(2) 0.042(2) 0.045(2) -0.0070(17) -0.0061(17) 0.0028(17) C4 0.041(2) 0.053(2) 0.0385(18) -0.0013(17) 0.0032(16) 0.0114(19) C5 0.0340(18) 0.049(2) 0.0447(18) -0.0026(17) 0.0033(16) 0.0047(18) C6 0.0362(17) 0.042(2) 0.0399(17) -0.0061(16) 0.0026(15) -0.0055(16) C7 0.0371(18) 0.047(2) 0.0392(17) 0.0020(16) 0.0072(15) -0.0064(17) C8 0.037(2) 0.059(3) 0.052(2) 0.0113(18) 0.0129(17) 0.0068(19) C9 0.057(2) 0.096(4) 0.082(3) 0.039(3) 0.009(2) 0.018(2) C10 0.070(3) 0.063(3) 0.119(4) -0.014(3) 0.029(3) 0.014(3) C11 0.046(2) 0.059(3) 0.0403(18) 0.0077(16) 0.0002(16) -0.011(2) C12 0.065(3) 0.072(3) 0.092(3) 0.037(2) -0.002(2) 0.003(3) C13 0.066(3) 0.098(4) 0.057(2) 0.019(2) 0.010(2) -0.014(3) C14 0.0383(19) 0.056(3) 0.058(2) -0.002(2) -0.0023(17) -0.0155(18) C15 0.051(2) 0.045(2) 0.053(2) -0.0008(18) -0.0160(17) -0.0122(19) C16 0.057(2) 0.054(3) 0.070(3) -0.007(2) 0.000(2) 0.007(2) C17 0.086(3) 0.052(2) 0.049(2) 0.0125(18) 0.008(2) -0.017(2) C18 0.068(3) 0.057(3) 0.0417(19) -0.0005(16) 0.0012(19) -0.001(2) C19 0.058(2) 0.049(3) 0.071(2) -0.005(2) -0.002(2) 0.018(2) _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 Li1 N1 1.910(6) . ? Li1 N3 2.033(6) . ? Li1 N2 2.077(6) . ? N1 C1 1.344(3) . ? N1 C7 1.459(3) . ? N2 C17 1.460(3) . ? N2 C16 1.464(4) . ? N2 C14 1.469(3) . ? N3 C19 1.448(4) . ? N3 C18 1.458(3) . ? N3 C15 1.471(4) . ? C1 C2 1.400(4) . ? C1 C6 1.425(4) . ? C2 C3 1.373(4) . ? C3 C4 1.385(4) . ? C4 C5 1.366(4) . ? C5 C6 1.366(4) . ? C7 C8 1.520(4) . ? C7 C11 1.526(4) . ? C8 C9 1.512(4) . ? C8 C10 1.521(5) . ? C11 C13 1.510(4) . ? C11 C12 1.516(4) . ? C14 C15 1.500(4) . ? 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 Li1 N3 127.9(3) . . ? N1 Li1 N2 137.1(3) . . ? N3 Li1 N2 89.1(2) . . ? C1 N1 C7 119.4(2) . . ? C1 N1 Li1 118.4(2) . . ? C7 N1 Li1 122.2(3) . . ? C17 N2 C16 107.1(3) . . ? C17 N2 C14 109.5(2) . . ? C16 N2 C14 109.9(2) . . ? C17 N2 Li1 121.5(2) . . ? C16 N2 Li1 107.3(2) . . ? C14 N2 Li1 101.2(2) . . ? C19 N3 C18 108.6(3) . . ? C19 N3 C15 111.1(3) . . ? C18 N3 C15 109.1(2) . . ? C19 N3 Li1 103.3(2) . . ? C18 N3 Li1 120.3(3) . . ? C15 N3 Li1 104.2(2) . . ? N1 C1 C2 128.9(3) . . ? N1 C1 C6 117.1(3) . . ? C2 C1 C6 114.0(3) . . ? C3 C2 C1 122.0(3) . . ? C2 C3 C4 122.4(3) . . ? C5 C4 C3 116.9(3) . . ? C6 C5 C4 121.6(3) . . ? C5 C6 C1 123.0(3) . . ? N1 C7 C8 111.3(3) . . ? N1 C7 C11 108.7(3) . . ? C8 C7 C11 113.8(3) . . ? C9 C8 C7 110.4(3) . . ? C9 C8 C10 109.8(3) . . ? C7 C8 C10 113.3(3) . . ? C13 C11 C12 109.6(3) . . ? C13 C11 C7 114.7(3) . . ? C12 C11 C7 109.7(3) . . ? N2 C14 C15 112.1(2) . . ? N3 C15 C14 112.0(3) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.172 _refine_diff_density_min -0.175 _refine_diff_density_rms 0.038