# Supplementary Material (ESI) for Organic & Biomolecular Chemistry # This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 177 loop_ _publ_author_name 'Curt Wentrup' 'Ilyas Aitbaev' 'John Andraos' 'Paul V. Bernhardt' 'Sieglinde Ebner' 'Michael Kiselewsky' 'Gert Kollenz' 'Bianca Wallfisch' _publ_contact_author_name 'Prof Curt Wentrup' _publ_contact_author_address ; Chemistry University of Queensland Brisbane 4072 AUSTRALIA ; _publ_contact_author_email WENTRUP@UQ.EDU.AU _publ_requested_journal 'Organic & Biomolecular Chemistry' _publ_section_title ; N-Aminopyrroledione Hydrazonoketene Pyrazolium Oxide Pyrazolone Rearrangements and Pyrazolone Tautomerism ; data_1986cw10 _database_code_CSD 207791 _audit_creation_date 2003-04-07T15:49:54-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.1 _audit_conform_dict_location ftp://ftp.iucr.org/cifdics/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_moiety 'C11 H13 Cl1 N2 O1' _chemical_formula_structural 'C11 H13 N2 O CL' _chemical_formula_sum 'C11 H13 Cl N2 O' _chemical_formula_weight 224.68 _chemical_compound_source 'synthesis as described' #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.348(2) _cell_length_b 8.642(2) _cell_length_c 9.832(3) _cell_angle_alpha 103.70(2) _cell_angle_beta 109.61(2) _cell_angle_gamma 97.53(2) _cell_volume 556.1(3) _cell_formula_units_Z 2 _cell_measurement_temperature 296(2) _cell_measurement_reflns_used 21 _cell_measurement_theta_min 10.684 _cell_measurement_theta_max 15.548 _cell_measurement_wavelength 0.71073 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description prism _exptl_crystal_colour colourless _exptl_crystal_size_max 0.53 _exptl_crystal_size_mid 0.47 _exptl_crystal_size_min 0.07 _exptl_crystal_density_diffrn 1.342 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 236 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.318 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_source 'Enraf Nonius FR590' _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_radiation_probe x-ray _diffrn_detector 'scintillation LiI' _diffrn_detector_dtime 1.195 _diffrn_orient_matrix_type ; x-axis points to radiation source the matrix is specified in reciprocal space ; _diffrn_orient_matrix_UB_11 -0.107369 _diffrn_orient_matrix_UB_12 -0.89661E-1 _diffrn_orient_matrix_UB_13 -0.7768E-2 _diffrn_orient_matrix_UB_21 -0.06619 _diffrn_orient_matrix_UB_22 -0.14651E-1 _diffrn_orient_matrix_UB_23 -0.110674 _diffrn_orient_matrix_UB_31 0.78269E-1 _diffrn_orient_matrix_UB_32 -0.81995E-1 _diffrn_orient_matrix_UB_33 -0.22528E-1 _diffrn_measurement_device '\k-geometry diffractometer' _diffrn_measurement_device_type 'Enraf Nonius TurboCAD4' _diffrn_measurement_method 'non-profiled omega scans' _diffrn_standards_number 3 _diffrn_standards_interval_time 120 _diffrn_standards_decay_% 10 _diffrn_standards_decay_corr_max 1.154 _diffrn_standards_decay_corr_min 0.996 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l 1 2 -6 -3 -4 1 3 -3 -2 _diffrn_reflns_number 2115 _diffrn_reflns_av_R_equivalents 0.0423 _diffrn_reflns_av_unetI/netI 0.0608 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.31 _diffrn_reflns_theta_max 24.97 _diffrn_reflns_theta_full 24.97 _diffrn_measured_fraction_theta_full 1 _diffrn_measured_fraction_theta_max 1 _reflns_number_total 1948 _reflns_number_gt 1101 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection 'CAD4 Express (Enraf Nonius, 1994)' _computing_cell_refinement 'CAD4 Express (Enraf Nonius, 1994)' _computing_data_reduction 'XCAD4 (Harms & Wocadlo, 1995)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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^)+(0.1269P)^2^+0.0721P] 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_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_extinction_coef 0.034(14) _refine_ls_number_reflns 1948 _refine_ls_number_parameters 147 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1272 _refine_ls_R_factor_gt 0.0692 _refine_ls_wR_factor_ref 0.2244 _refine_ls_wR_factor_gt 0.1896 _refine_ls_goodness_of_fit_ref 1.063 _refine_ls_restrained_S_all 1.063 _refine_ls_shift/su_max 0 _refine_ls_shift/su_mean 0 _refine_diff_density_max 0.409 _refine_diff_density_min -0.393 _refine_diff_density_rms 0.074 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# 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 0 '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 0.006 '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' 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 C3 C 0.2507(7) 0.4302(5) 1.0115(5) 0.0416(11) Uani 1 1 d . . . C4 C 0.2121(7) 0.2606(5) 0.9777(5) 0.0446(11) Uani 1 1 d . . . C5 C 0.0886(7) 0.2022(5) 0.8268(5) 0.0488(12) Uani 1 1 d . . . C6 C 0.3732(7) 0.5632(5) 1.1511(5) 0.0465(12) Uani 1 1 d . . . C7 C 0.4905(8) 0.5319(6) 1.2799(6) 0.0653(15) Uani 1 1 d . . . H7 H 0.4926 0.4242 1.2789 0.078 Uiso 1 1 calc R . . C8 C 0.6040(9) 0.6572(7) 1.4093(6) 0.0716(17) Uani 1 1 d . . . H8 H 0.6794 0.6337 1.4956 0.086 Uiso 1 1 calc R . . C9 C 0.6066(8) 0.8167(7) 1.4119(6) 0.0687(16) Uani 1 1 d . . . H9 H 0.6839 0.9015 1.4995 0.082 Uiso 1 1 calc R . . C10 C 0.4957(9) 0.8497(6) 1.2859(6) 0.0730(17) Uani 1 1 d . . . H10 H 0.4987 0.958 1.2873 0.088 Uiso 1 1 calc R . . C11 C 0.3791(8) 0.7264(6) 1.1561(6) 0.0597(14) Uani 1 1 d . . . H11 H 0.3034 0.7518 1.071 0.072 Uiso 1 1 calc R . . C12 C -0.0699(8) 0.3219(6) 0.6190(5) 0.0614(15) Uani 1 1 d . . . H12A H -0.0715 0.224 0.5474 0.092 Uiso 1 1 calc R . . H12B H -0.0166 0.4158 0.5964 0.092 Uiso 1 1 calc R . . H12C H -0.2028 0.3235 0.6129 0.092 Uiso 1 1 calc R . . C13 C 0.2798(9) 0.1549(6) 1.0780(6) 0.0734(18) Uani 1 1 d . . . H13A H 0.2072 0.0436 1.0257 0.11 Uiso 1 1 calc R . . H13B H 0.2562 0.1928 1.1692 0.11 Uiso 1 1 calc R . . H13C H 0.4191 0.161 1.1029 0.11 Uiso 1 1 calc R . . N1 N 0.0529(6) 0.3255(4) 0.7710(4) 0.0480(10) Uani 1 1 d . . . N2 N 0.1494(6) 0.4657(5) 0.8852(4) 0.0473(11) Uani 1 1 d . . . H2 H 0.161(8) 0.541(7) 0.865(6) 0.062(18) Uiso 1 1 d . . . O14 O -0.0022(6) 0.0525(4) 0.7328(4) 0.0712(12) Uani 1 1 d . . . H14 H 0.070(10) -0.030(10) 0.760(7) 0.11(2) Uiso 1 1 d . . . Cl1 Cl 0.1432(3) 0.75991(15) 0.76482(15) 0.0776(7) 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 C3 0.049(3) 0.034(2) 0.040(2) 0.0102(18) 0.014(2) 0.013(2) C4 0.049(3) 0.035(2) 0.047(2) 0.0159(19) 0.012(2) 0.012(2) C5 0.051(3) 0.029(2) 0.055(3) 0.010(2) 0.008(2) 0.010(2) C6 0.053(3) 0.034(2) 0.045(2) 0.0063(19) 0.014(2) 0.010(2) C7 0.081(4) 0.043(3) 0.053(3) 0.011(2) 0.002(3) 0.021(3) C8 0.074(4) 0.065(4) 0.048(3) 0.006(3) -0.005(3) 0.021(3) C9 0.066(4) 0.055(3) 0.060(3) -0.005(3) 0.013(3) 0.002(3) C10 0.098(4) 0.038(3) 0.058(3) 0.005(2) 0.009(3) 0.005(3) C11 0.076(4) 0.041(3) 0.052(3) 0.011(2) 0.013(3) 0.016(2) C12 0.075(4) 0.046(3) 0.050(3) 0.017(2) 0.005(3) 0.014(3) C13 0.093(4) 0.040(3) 0.065(3) 0.024(2) 0.000(3) 0.011(3) N1 0.059(2) 0.0321(18) 0.0401(19) 0.0095(15) 0.0040(18) 0.0121(17) N2 0.063(3) 0.0287(19) 0.041(2) 0.0109(16) 0.0085(19) 0.0103(18) O14 0.086(3) 0.0305(17) 0.060(2) 0.0033(15) -0.0103(19) 0.0121(17) Cl1 0.1245(14) 0.0371(7) 0.0593(8) 0.0177(6) 0.0144(8) 0.0294(7) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 C3 N2 1.346(6) . ? C3 C4 1.391(6) . ? C3 C6 1.473(6) . ? C4 C5 1.379(6) . ? C4 C13 1.507(6) . ? C5 N1 1.326(5) . ? C5 O14 1.329(5) . ? C6 C7 1.382(7) . ? C6 C11 1.394(6) . ? C7 C8 1.373(7) . ? C8 C9 1.370(8) . ? C9 C10 1.353(8) . ? C10 C11 1.371(7) . ? C12 N1 1.454(6) . ? N1 N2 1.352(5) . ? 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 N2 C3 C4 107.6(4) . . ? N2 C3 C6 120.0(4) . . ? C4 C3 C6 132.4(4) . . ? C5 C4 C3 105.1(4) . . ? C5 C4 C13 124.7(4) . . ? C3 C4 C13 130.1(4) . . ? N1 C5 O14 116.5(4) . . ? N1 C5 C4 110.3(4) . . ? O14 C5 C4 133.1(4) . . ? C7 C6 C11 117.6(4) . . ? C7 C6 C3 121.7(4) . . ? C11 C6 C3 120.7(4) . . ? C8 C7 C6 121.0(5) . . ? C9 C8 C7 120.4(5) . . ? C10 C9 C8 119.4(5) . . ? C9 C10 C11 121.3(5) . . ? C10 C11 C6 120.4(5) . . ? C5 N1 N2 107.4(3) . . ? C5 N1 C12 129.4(4) . . ? N2 N1 C12 123.2(4) . . ? C3 N2 N1 109.6(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 N2 C3 C4 C5 1.2(6) . . . . ? C6 C3 C4 C5 -178.9(5) . . . . ? N2 C3 C4 C13 -177.3(6) . . . . ? C6 C3 C4 C13 2.6(9) . . . . ? C3 C4 C5 N1 -0.1(6) . . . . ? C13 C4 C5 N1 178.5(5) . . . . ? C3 C4 C5 O14 -177.4(6) . . . . ? C13 C4 C5 O14 1.2(10) . . . . ? N2 C3 C6 C7 -175.3(5) . . . . ? C4 C3 C6 C7 4.9(9) . . . . ? N2 C3 C6 C11 2.8(7) . . . . ? C4 C3 C6 C11 -177.1(5) . . . . ? C11 C6 C7 C8 1.9(9) . . . . ? C3 C6 C7 C8 180.0(5) . . . . ? C6 C7 C8 C9 -1.6(10) . . . . ? C7 C8 C9 C10 0.2(10) . . . . ? C8 C9 C10 C11 0.7(10) . . . . ? C9 C10 C11 C6 -0.4(10) . . . . ? C7 C6 C11 C10 -0.9(9) . . . . ? C3 C6 C11 C10 -179.1(5) . . . . ? O14 C5 N1 N2 176.8(5) . . . . ? C4 C5 N1 N2 -1.1(6) . . . . ? O14 C5 N1 C12 -1.3(8) . . . . ? C4 C5 N1 C12 -179.2(5) . . . . ? C4 C3 N2 N1 -1.9(5) . . . . ? C6 C3 N2 N1 178.2(4) . . . . ? C5 N1 N2 C3 1.9(5) . . . . ? C12 N1 N2 C3 -179.9(5) . . . . ?