# Supplementary Material (ESI) for Green Chemistry # This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 1048 loop_ _publ_author_name 'Zhong-Xia Wang' 'Hua-Li Qin' _publ_contact_author_name 'Prof Zhong-Xia Wang' _publ_contact_author_address ; Department of Chemistry University of Science and Technology of China 96 Jinzhai Road Hefei 230026 CHINA ; _publ_contact_author_email ZXWANG@USTC.EDU.CN _publ_requested_journal 'Green Chemistry' _publ_section_title ; Solventless syntheses of pyrazole derivatives ; data_030827e _database_code_depnum_ccdc_archive 'CCDC 222261' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C12 H14 N2 O2' _chemical_formula_weight 218.25 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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M C2/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 19.764(9) _cell_length_b 8.877(4) _cell_length_c 15.763(7) _cell_angle_alpha 90.00 _cell_angle_beta 117.617(7) _cell_angle_gamma 90.00 _cell_volume 2450.4(19) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 830 _cell_measurement_theta_min 3.85 _cell_measurement_theta_max 23.99 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas NONE _exptl_crystal_density_diffrn 1.183 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 928 _exptl_absorpt_coefficient_mu 0.082 _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 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 ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 9639 _diffrn_reflns_av_R_equivalents 0.0377 _diffrn_reflns_av_sigmaI/netI 0.0334 _diffrn_reflns_limit_h_min -24 _diffrn_reflns_limit_h_max 24 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.33 _diffrn_reflns_theta_max 26.50 _reflns_number_total 2529 _reflns_number_gt 1662 _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^)+(0.0665P)^2^+1.1348P] 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 2529 _refine_ls_number_parameters 148 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0844 _refine_ls_R_factor_gt 0.0518 _refine_ls_wR_factor_ref 0.1482 _refine_ls_wR_factor_gt 0.1276 _refine_ls_goodness_of_fit_ref 1.020 _refine_ls_restrained_S_all 1.020 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group O1 O 0.28161(8) 0.88717(17) 0.96499(12) 0.0728(5) Uani 1 1 d . . . O2 O 0.37683(8) 0.63423(18) 1.09422(11) 0.0709(5) Uani 1 1 d . . . H2 H 0.3305 0.6406 1.0609 0.106 Uiso 1 1 calc R . . N1 N 0.40944(8) 0.87386(17) 1.05257(11) 0.0528(4) Uani 1 1 d . . . N2 N 0.48028(9) 0.94143(18) 1.11481(11) 0.0584(4) Uani 1 1 d . . . C1 C 0.41411(9) 0.70457(19) 1.04698(13) 0.0500(5) Uani 1 1 d . . . C2 C 0.50118(10) 0.6808(2) 1.10979(14) 0.0565(5) Uani 1 1 d . . . H2A H 0.5112 0.6117 1.1620 0.068 Uiso 1 1 calc R . . H2B H 0.5244 0.6416 1.0720 0.068 Uiso 1 1 calc R . . C3 C 0.53086(11) 0.8358(2) 1.14705(13) 0.0552(5) Uani 1 1 d . . . C4 C 0.38429(10) 0.6552(2) 0.94262(14) 0.0541(5) Uani 1 1 d . . . C5 C 0.33036(11) 0.5413(3) 0.9019(2) 0.0827(8) Uani 1 1 d . . . H5 H 0.3106 0.4930 0.9380 0.099 Uiso 1 1 calc R . . C6 C 0.30592(16) 0.4995(4) 0.8062(3) 0.1236(15) Uani 1 1 d . . . H6 H 0.2690 0.4250 0.7787 0.148 Uiso 1 1 calc R . . C7 C 0.3361(2) 0.5677(5) 0.7524(2) 0.1325(17) Uani 1 1 d . . . H7 H 0.3204 0.5380 0.6894 0.159 Uiso 1 1 calc R . . C8 C 0.3896(2) 0.6798(4) 0.7929(2) 0.1112(11) Uani 1 1 d . . . H8 H 0.4097 0.7264 0.7566 0.133 Uiso 1 1 calc R . . C9 C 0.41423(14) 0.7247(3) 0.88745(16) 0.0751(6) Uani 1 1 d . . . H9 H 0.4505 0.8007 0.9139 0.090 Uiso 1 1 calc R . . C10 C 0.61319(12) 0.8696(3) 1.21539(17) 0.0791(7) Uani 1 1 d . . . H10A H 0.6441 0.8516 1.1841 0.119 Uiso 1 1 calc R . . H10B H 0.6299 0.8055 1.2705 0.119 Uiso 1 1 calc R . . H10C H 0.6180 0.9731 1.2350 0.119 Uiso 1 1 calc R . . C11 C 0.34291(11) 0.9539(2) 1.01266(14) 0.0564(5) Uani 1 1 d . . . C12 C 0.34804(15) 1.1221(3) 1.0282(2) 0.0846(7) Uani 1 1 d . . . H12A H 0.3011 1.1683 0.9831 0.127 Uiso 1 1 calc R . . H12B H 0.3895 1.1614 1.0193 0.127 Uiso 1 1 calc R . . H12C H 0.3567 1.1436 1.0922 0.127 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 O1 0.0443(8) 0.0787(10) 0.0948(11) 0.0163(8) 0.0317(8) 0.0121(7) O2 0.0536(8) 0.0817(10) 0.0843(10) 0.0288(8) 0.0377(8) 0.0077(8) N1 0.0435(8) 0.0514(9) 0.0607(9) 0.0004(7) 0.0218(7) 0.0066(7) N2 0.0539(9) 0.0582(10) 0.0581(9) -0.0040(8) 0.0217(8) -0.0004(8) C1 0.0405(9) 0.0468(10) 0.0633(11) 0.0084(8) 0.0245(8) 0.0045(8) C2 0.0429(10) 0.0586(11) 0.0620(12) 0.0048(9) 0.0194(9) 0.0054(8) C3 0.0468(10) 0.0628(12) 0.0516(10) 0.0024(9) 0.0189(8) 0.0009(9) C4 0.0415(9) 0.0497(10) 0.0617(12) 0.0007(9) 0.0160(8) 0.0104(8) C5 0.0434(11) 0.0735(15) 0.114(2) -0.0263(14) 0.0224(12) 0.0031(10) C6 0.0554(16) 0.120(3) 0.139(3) -0.071(2) -0.0035(17) 0.0239(16) C7 0.113(3) 0.151(4) 0.075(2) -0.038(2) -0.0061(18) 0.080(3) C8 0.148(3) 0.114(2) 0.0680(17) 0.0144(17) 0.0464(19) 0.061(2) C9 0.0898(16) 0.0692(14) 0.0658(14) 0.0054(11) 0.0357(13) 0.0142(12) C10 0.0554(13) 0.0804(16) 0.0762(15) -0.0017(12) 0.0091(11) -0.0040(11) C11 0.0521(11) 0.0605(12) 0.0635(12) 0.0108(9) 0.0327(10) 0.0136(9) C12 0.0845(16) 0.0665(15) 0.1043(19) 0.0068(13) 0.0449(14) 0.0250(12) _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 O1 C11 1.241(2) . ? O2 C1 1.413(2) . ? O2 H2 0.8200 . ? N1 C11 1.365(2) . ? N1 N2 1.417(2) . ? N1 C1 1.511(2) . ? N2 C3 1.290(2) . ? C1 C4 1.532(3) . ? C1 C2 1.551(2) . ? C2 C3 1.505(3) . ? C2 H2A 0.9700 . ? C2 H2B 0.9700 . ? C3 C10 1.508(3) . ? C4 C5 1.392(3) . ? C4 C9 1.401(3) . ? C5 C6 1.404(4) . ? C5 H5 0.9300 . ? C6 C7 1.382(5) . ? C6 H6 0.9300 . ? C7 C8 1.375(5) . ? C7 H7 0.9300 . ? C8 C9 1.395(4) . ? C8 H8 0.9300 . ? C9 H9 0.9300 . ? C10 H10A 0.9600 . ? C10 H10B 0.9600 . ? C10 H10C 0.9600 . ? C11 C12 1.509(3) . ? C12 H12A 0.9600 . ? C12 H12B 0.9600 . ? C12 H12C 0.9600 . ? 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 C1 O2 H2 109.5 . . ? C11 N1 N2 122.03(16) . . ? C11 N1 C1 124.24(16) . . ? N2 N1 C1 113.20(13) . . ? C3 N2 N1 107.55(16) . . ? O2 C1 N1 110.37(15) . . ? O2 C1 C4 113.87(16) . . ? N1 C1 C4 110.09(14) . . ? O2 C1 C2 107.38(15) . . ? N1 C1 C2 100.25(14) . . ? C4 C1 C2 114.03(15) . . ? C3 C2 C1 103.94(15) . . ? C3 C2 H2A 111.0 . . ? C1 C2 H2A 111.0 . . ? C3 C2 H2B 111.0 . . ? C1 C2 H2B 111.0 . . ? H2A C2 H2B 109.0 . . ? N2 C3 C2 114.84(16) . . ? N2 C3 C10 121.31(19) . . ? C2 C3 C10 123.84(17) . . ? C5 C4 C9 119.2(2) . . ? C5 C4 C1 122.3(2) . . ? C9 C4 C1 118.54(18) . . ? C4 C5 C6 119.7(3) . . ? C4 C5 H5 120.1 . . ? C6 C5 H5 120.1 . . ? C7 C6 C5 120.8(3) . . ? C7 C6 H6 119.6 . . ? C5 C6 H6 119.6 . . ? C8 C7 C6 119.4(3) . . ? C8 C7 H7 120.3 . . ? C6 C7 H7 120.3 . . ? C7 C8 C9 121.0(3) . . ? C7 C8 H8 119.5 . . ? C9 C8 H8 119.5 . . ? C8 C9 C4 120.0(3) . . ? C8 C9 H9 120.0 . . ? C4 C9 H9 120.0 . . ? C3 C10 H10A 109.5 . . ? C3 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C3 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? O1 C11 N1 119.51(19) . . ? O1 C11 C12 122.94(19) . . ? N1 C11 C12 117.54(19) . . ? C11 C12 H12A 109.5 . . ? C11 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C11 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? 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 C11 N1 N2 C3 174.56(17) . . . . ? C1 N1 N2 C3 2.6(2) . . . . ? C11 N1 C1 O2 -63.2(2) . . . . ? N2 N1 C1 O2 108.56(17) . . . . ? C11 N1 C1 C4 63.3(2) . . . . ? N2 N1 C1 C4 -124.90(15) . . . . ? C11 N1 C1 C2 -176.22(17) . . . . ? N2 N1 C1 C2 -4.45(19) . . . . ? O2 C1 C2 C3 -110.93(18) . . . . ? N1 C1 C2 C3 4.36(18) . . . . ? C4 C1 C2 C3 121.93(17) . . . . ? N1 N2 C3 C2 0.7(2) . . . . ? N1 N2 C3 C10 179.70(19) . . . . ? C1 C2 C3 N2 -3.5(2) . . . . ? C1 C2 C3 C10 177.54(19) . . . . ? O2 C1 C4 C5 -5.6(2) . . . . ? N1 C1 C4 C5 -130.16(18) . . . . ? C2 C1 C4 C5 118.09(19) . . . . ? O2 C1 C4 C9 176.29(16) . . . . ? N1 C1 C4 C9 51.7(2) . . . . ? C2 C1 C4 C9 -60.0(2) . . . . ? C9 C4 C5 C6 -1.0(3) . . . . ? C1 C4 C5 C6 -179.13(19) . . . . ? C4 C5 C6 C7 1.5(4) . . . . ? C5 C6 C7 C8 -1.3(5) . . . . ? C6 C7 C8 C9 0.5(4) . . . . ? C7 C8 C9 C4 0.0(4) . . . . ? C5 C4 C9 C8 0.3(3) . . . . ? C1 C4 C9 C8 178.44(19) . . . . ? N2 N1 C11 O1 -174.14(17) . . . . ? C1 N1 C11 O1 -3.1(3) . . . . ? N2 N1 C11 C12 6.5(3) . . . . ? C1 N1 C11 C12 177.61(19) . . . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 26.50 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.171 _refine_diff_density_min -0.155 _refine_diff_density_rms 0.035