# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2002 data_global _journal_coden_Cambridge 182 _publ_contact_author_name 'Prof. Dr. Robin D. Rogers' _publ_contact_author_address ; Prof. Dr. Robin D. Rogers Center for Green Manufactoring and Department of Chemistry University of Alabama Tuscaloosa AL 35487 USA ; _publ_contact_author_phone '+1 205 3484323' _publ_contact_author_fax '+1 205 3489104' _publ_contact_author_email rdrogers@bama.ua.edu _publ_requested_journal 'Chem. Comm.' _publ_requested_coeditor_name ? _publ_contact_author ; Prof. Igor Tkatchenko Laboratoire des Synthese et Electrosynthese Organometallique Faculte des Sciences Mirande Universite de Bourgogne BP 47870 21000 Dijon France ; _publ_contact_letter ; ? ; #============================================================================== # 3. TITLE AND AUTHOR LIST _publ_section_title ; 1,3-Dimethylimidazolium-2-carboxylate: the planned and unexpected synthesis of an ionic liquid precursor and carbene-CO2 adduct. ; loop_ _publ_author_name _publ_author_address 'Holbrey, John D.' ; Center for Green Manufactoring and Department of Chemistry University of Alabama Tuscaloosa AL 35487 USA ; 'Reichert, W. Matthew' ; Center for Green Manufactoring and Department of Chemistry University of Alabama Tuscaloosa AL 35487 USA ; 'Tkatchenko, Igor' ; Laboratoire des Synthese et Electrosynthese Organometallique Faculte des Sciences Mirande Universite de Bourgogne BP 47870 21000 Dijon France ; 'Bouajila, E.' ; Laboratoire des Synthese et Electrosynthese Organometallique Faculte des Sciences Mirande Universite de Bourgogne BP 47870 21000 Dijon France ; 'Walter, Olaf' ; ITC-CPV Forschungszentrum Karlsruhe Postfach 3640 76021 Karlsruhe Germany ; 'Tommasi, Immacolata' ; Depart,emt of Chemistry University of Bari Campus Universitario 70126 Bari Italy ; 'Rogers, Robin D.' ; Center for Green Manufactoring and Department of Chemistry University of Alabama Tuscaloosa AL 35487 USA ; data_it1 _database_code_CSD 198166 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C3 H4 N O' _chemical_formula_weight 70.07 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 ? _symmetry_space_group_name_H-M ? loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z+1/2' '-x, y, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z-1/2' 'x, -y, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 8.3253(14) _cell_length_b 11.5995(19) _cell_length_c 6.7148(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 648.44(19) _cell_formula_units_Z 8 _cell_measurement_temperature 200(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max ? _exptl_crystal_size_mid ? _exptl_crystal_size_min ? _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.436 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 296 _exptl_absorpt_coefficient_mu 0.110 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 200(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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6176 _diffrn_reflns_av_R_equivalents 0.0501 _diffrn_reflns_av_sigmaI/netI 0.0276 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -8 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 3.01 _diffrn_reflns_theta_max 28.30 _reflns_number_total 800 _reflns_number_gt 581 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _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 w=1/[\s^2^(Fo^2^)+(0.0639P)^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 800 _refine_ls_number_parameters 50 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0513 _refine_ls_R_factor_gt 0.0358 _refine_ls_wR_factor_ref 0.0998 _refine_ls_wR_factor_gt 0.0939 _refine_ls_goodness_of_fit_ref 0.952 _refine_ls_restrained_S_all 0.952 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group O1 O 0.89626(12) 0.20073(8) 0.14349(17) 0.0445(3) Uani 1 d . . . N1 N 0.87230(12) 0.44602(8) 0.22058(14) 0.0255(3) Uani 1 d . . . C1 C 1.0000 0.37733(14) 0.2500 0.0235(4) Uani 1 d S . . C2 C 0.92039(15) 0.55980(10) 0.23201(18) 0.0294(3) Uani 1 d . . . H2 H 0.8551 0.6243 0.2176 0.036(4) Uiso 1 calc R . . C3 C 0.70472(14) 0.41065(12) 0.1880(2) 0.0340(4) Uani 1 d . . . H3A H 0.6980 0.3650 0.0690 0.040(2) Uiso 1 calc R . . H3B H 0.6384 0.4779 0.1741 0.040(2) Uiso 1 calc R . . H3C H 0.6684 0.3660 0.2995 0.040(2) Uiso 1 calc R . . C4 C 1.0000 0.24615(15) 0.2500 0.0300(4) Uani 1 d S . . 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 0.0438(6) 0.0260(5) 0.0637(7) -0.0082(5) -0.0019(5) -0.0092(5) N1 0.0260(6) 0.0218(5) 0.0286(5) 0.0005(4) 0.0014(4) 0.0013(4) C1 0.0250(8) 0.0213(8) 0.0241(8) 0.000 0.0008(6) 0.000 C2 0.0361(7) 0.0189(6) 0.0333(7) 0.0017(5) 0.0037(5) 0.0033(5) C3 0.0237(7) 0.0337(7) 0.0445(8) 0.0022(6) -0.0003(5) 0.0000(5) C4 0.0303(9) 0.0207(9) 0.0389(10) 0.000 0.0080(8) 0.000 _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 C4 1.2390(12) . ? N1 C1 1.3431(13) . ? N1 C2 1.3813(15) . ? N1 C3 1.4706(16) . ? C1 N1 1.3431(14) 3_755 ? C1 C4 1.522(2) . ? C2 C2 1.347(3) 3_755 ? C4 O1 1.2390(12) 3_755 ? 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 N1 C2 109.22(11) . . ? C1 N1 C3 127.40(11) . . ? C2 N1 C3 123.35(11) . . ? N1 C1 N1 107.24(14) 3_755 . ? N1 C1 C4 126.38(7) 3_755 . ? N1 C1 C4 126.38(7) . . ? C2 C2 N1 107.17(7) 3_755 . ? O1 C4 O1 129.66(18) 3_755 . ? O1 C4 C1 115.17(9) 3_755 . ? O1 C4 C1 115.17(9) . . ? _diffrn_measured_fraction_theta_max 0.834 _diffrn_reflns_theta_full 28.30 _diffrn_measured_fraction_theta_full 0.834 _refine_diff_density_max 0.215 _refine_diff_density_min -0.235 _refine_diff_density_rms 0.044 data_m1 _database_code_CSD 198167 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 1,3-dimethylimidazolium-2-carboxylate _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C6 H8 N2 O2' _chemical_formula_weight 140.14 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 Orthorhombic _symmetry_space_group_name_H-M Pbcn loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z+1/2' '-x, y, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z-1/2' 'x, -y, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 8.334(4) _cell_length_b 11.605(5) _cell_length_c 6.706(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 648.5(5) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 790 _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description needles _exptl_crystal_colour orange _exptl_crystal_size_max 1.00 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.435 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 296 _exptl_absorpt_coefficient_mu 0.110 _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 173(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 2546 _diffrn_reflns_av_R_equivalents 0.0314 _diffrn_reflns_av_sigmaI/netI 0.0155 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -7 _diffrn_reflns_limit_l_max 7 _diffrn_reflns_theta_min 3.01 _diffrn_reflns_theta_max 23.29 _reflns_number_total 470 _reflns_number_gt 417 _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 0.0583,0.0391 _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(4) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 470 _refine_ls_number_parameters 64 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0322 _refine_ls_R_factor_gt 0.0288 _refine_ls_wR_factor_ref 0.0824 _refine_ls_wR_factor_gt 0.0795 _refine_ls_goodness_of_fit_ref 1.097 _refine_ls_restrained_S_all 1.097 _refine_ls_shift/su_max 0.008 _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 O1 O 0.60373(12) 0.29914(9) 0.14320(16) 0.0429(4) Uani 1 1 d . . . N1 N 0.62766(13) 0.05376(9) 0.22028(15) 0.0245(4) Uani 1 1 d . . . C5 C 0.57949(18) -0.05982(11) 0.2319(2) 0.0276(4) Uani 1 1 d . . . H5C H 0.655(2) -0.1211(14) 0.2120(19) 0.028(4) Uiso 1 1 d . . . C2 C 0.5000 0.12259(16) 0.2500 0.0225(5) Uani 1 2 d S . . C7 C 0.5000 0.25380(18) 0.2500 0.0286(6) Uani 1 2 d S . . C6 C 0.79539(16) 0.08899(14) 0.1873(2) 0.0325(5) Uani 1 1 d . . . H6A H 0.830(2) 0.1354(16) 0.301(3) 0.042(4) Uiso 1 1 d . . . H6C H 0.859(2) 0.0151(14) 0.174(2) 0.038(4) Uiso 1 1 d . . . H6B H 0.803(2) 0.1332(16) 0.071(2) 0.046(5) 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 O1 0.0391(6) 0.0339(7) 0.0557(8) 0.0082(5) 0.0011(5) -0.0088(5) N1 0.0208(7) 0.0298(7) 0.0228(7) -0.0003(4) -0.0012(4) 0.0011(5) C5 0.0308(8) 0.0255(9) 0.0264(8) -0.0013(5) -0.0042(5) 0.0039(6) C2 0.0213(10) 0.0276(10) 0.0185(9) 0.000 -0.0023(6) 0.000 C7 0.0232(10) 0.0294(11) 0.0334(12) 0.000 -0.0086(8) 0.000 C6 0.0198(9) 0.0396(9) 0.0380(9) -0.0012(8) 0.0008(6) -0.0001(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 O1 C7 1.2398(14) . ? N1 C2 1.3452(16) . ? N1 C5 1.3800(18) . ? N1 C6 1.473(2) . ? C5 C5 1.347(3) 3_655 ? C2 N1 1.3452(16) 3_655 ? C2 C7 1.523(3) . ? C7 O1 1.2398(14) 3_655 ? 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 C2 N1 C5 109.19(12) . . ? C2 N1 C6 127.44(13) . . ? C5 N1 C6 123.34(12) . . ? C5 C5 N1 107.23(8) 3_655 . ? N1 C2 N1 107.15(16) 3_655 . ? N1 C2 C7 126.43(8) 3_655 . ? N1 C2 C7 126.43(8) . . ? O1 C7 O1 129.8(2) 3_655 . ? O1 C7 C2 115.11(10) 3_655 . ? O1 C7 C2 115.11(10) . . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 23.29 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.130 _refine_diff_density_min -0.249 _refine_diff_density_rms 0.033