# Electronic Supplementary Material (ESI) for RSC Advances # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full 'Green Chemistry' _journal_coden_cambridge 1048 _publ_contact_author_name 'Vicente Gotor' _publ_contact_author_address ; Departamento de Qu\'imica Org\'anica e Inorg\'anica Instituto Universitario de Biotecnolog\'ia Universidad de Oviedo Avda Juli\'an Claver\'ia, s/n 33006 Oviedo Spain ; _publ_contact_author_email vgs@uniovi.es #========================================================================== # TITLE AND AUTHOR LIST _Publ_section_title ; Chemoenzymatic preparation of 3-(1H-imidazol-1-yl)cyclohexanol- based optically active ionic liquids: Application in organocatalysis and toxicity studies. ; _Publ_section_abstract ; ; # The loop structure below should contain the names and addresses of all # authors, in the required order of publication. loop_ _publ_author_name _publ_author_address 'Caroline Emilie Paul' ; Departamento de Qu\'imica Org\'anica e Inorg\'anica Instituto Universitario de Biotecnolog\'ia Universidad de Oviedo Avda Juli\'an Claver\'ia, s/n 33006 Oviedo Spain ; "Vicente Gotor Fern\'andez" ; Departamento de Qu\'imica Org\'anica e Inorg\'anica Instituto Universitario de Biotecnolog\'ia Universidad de Oviedo Avda Juli\'an Claver\'ia, s/n 33006 Oviedo Spain ; "Iv\'an Lavandera" ; Departamento de Qu\'imica Org\'anica e Inorg\'anica Instituto Universitario de Biotecnolog\'ia Universidad de Oviedo Avda Juli\'an Claver\'ia, s/n 33006 Oviedo Spain ; 'Jose Montejo-Bernardo' ; Departamento de Qu\'imica F\'isica y Anal\'itica Universidad de Oviedo Avda. Juli\'an Claver\'ia, s/n 33006 Oviedo Spain ; "Santiago Garc\'ia-Granda" ; Departamento de Qu\'imica F\'isica y Anal\'itica Universidad de Oviedo Avda. Juli\'an Claver\'ia, s/n 33006 Oviedo Spain ; 'Vicente Gotor' ; Departamento de Qu\'imica Org\'anica e Inorg\'anica Instituto Universitario de Biotecnolog\'ia Universidad de Oviedo Avda. Juli\'an Claver\'ia, s/n 33006 Oviedo Spain ; #========================================================================== # TEXT _Publ_section_comment ; ; data_cep89 _database_code_depnum_ccdc_archive 'CCDC 858900' #TrackingRef '8672_web_deposit_cif_file_0_JoseManuelMontejoBernardo_1323936960.cep89.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C16 H21 N2 O, Br' _chemical_formula_sum 'C16 H21 Br N2 O' _chemical_formula_weight 337.26 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0181 0.0091 '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 0.0311 0.0180 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0492 0.0322 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.6763 1.2805 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M P212121 _symmetry_space_group_name_Hall 'P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' 'x+1/2, -y+1/2, -z' '-x, y+1/2, -z+1/2' _cell_length_a 8.48954(9) _cell_length_b 13.24115(15) _cell_length_c 14.05407(20) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1579.84(3) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 6030 _cell_measurement_theta_min 3.3350 _cell_measurement_theta_max 70.4451 _exptl_crystal_description Prismatic _exptl_crystal_colour White _exptl_crystal_size_max 0.1647 _exptl_crystal_size_mid 0.0772 _exptl_crystal_size_min 0.0526 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.418 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 696 _exptl_absorpt_coefficient_mu 3.520 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.758 _exptl_absorpt_correction_T_max 0.831 _exptl_absorpt_process_details ; CrysAlispro, Oxford Diffraction Ltd. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 1.54184 _diffrn_radiation_type CuK\a _diffrn_radiation_source 'Enhance (Cu) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Goniometer Xcalibur, detector: Ruby' _diffrn_measurement_method 'f\ and \w scans' _diffrn_detector_area_resol_mean 10.2673 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8728 _diffrn_reflns_av_R_equivalents 0.0332 _diffrn_reflns_av_sigmaI/netI 0.0300 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.3350 _diffrn_reflns_theta_max 70.4451 _reflns_number_total 2948 _reflns_number_gt 2807 _reflns_threshold_expression >2sigma(I) _computing_data_collection CrysAlispro _computing_cell_refinement CrysAlispro _computing_data_reduction CrysAlispro _computing_structure_solution ; Direct methods using SIR2004 (M.C. Burla et al., 2005) ; _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP-3 (L.J. Farrugia, 1997)' _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^)+(0.0308P)^2^+0.0000P] 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_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.049(18) _chemical_absolute_configuration ad _refine_ls_number_reflns 2948 _refine_ls_number_parameters 265 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0274 _refine_ls_R_factor_gt 0.0253 _refine_ls_wR_factor_ref 0.0622 _refine_ls_wR_factor_gt 0.0602 _refine_ls_goodness_of_fit_ref 1.115 _refine_ls_restrained_S_all 1.115 _refine_ls_shift/su_max 0.014 _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 Br1 Br 0.19904(3) 0.198159(19) 0.16804(2) 0.05037(9) Uani 1 1 d . . . O1 O 0.2717(3) 0.54936(14) -0.31418(13) 0.0572(5) Uani 1 1 d . . . N1 N 0.2356(2) 0.24228(15) -0.12772(15) 0.0382(5) Uani 1 1 d . . . N3 N 0.2585(2) 0.08069(15) -0.11805(16) 0.0392(5) Uani 1 1 d . . . C1 C 0.2986(4) 0.50858(18) -0.22187(16) 0.0410(5) Uani 1 1 d . . . C2 C 0.2490(4) 0.39804(19) -0.22444(19) 0.0419(6) Uani 1 1 d . . . C3 C 0.2775(3) 0.35089(17) -0.12693(18) 0.0374(5) Uani 1 1 d . . . C4 C 0.1883(4) 0.40625(19) -0.04914(18) 0.0486(6) Uani 1 1 d . . . C5 C 0.2377(5) 0.5173(2) -0.0484(2) 0.0564(8) Uani 1 1 d . . . C6 C 0.2116(4) 0.56551(19) -0.14514(18) 0.0480(6) Uani 1 1 d . . . C7 C 0.3355(3) 0.16718(18) -0.11381(17) 0.0374(5) Uani 1 1 d . . . C8 C 0.0878(3) 0.2020(2) -0.1403(2) 0.0501(6) Uani 1 1 d . . . C9 C 0.1019(3) 0.1011(2) -0.1342(2) 0.0504(7) Uani 1 1 d . . . C10 C 0.3280(3) -0.02208(19) -0.1105(2) 0.0467(6) Uani 1 1 d . . . C11 C 0.2383(3) -0.08532(17) -0.04032(19) 0.0402(5) Uani 1 1 d . . . C12 C 0.2515(4) -0.0687(2) 0.0563(2) 0.0541(7) Uani 1 1 d . . . C13 C 0.1680(5) -0.1290(3) 0.1197(2) 0.0690(10) Uani 1 1 d . . . C14 C 0.0703(4) -0.2038(3) 0.0874(3) 0.0688(9) Uani 1 1 d . . . C15 C 0.0553(4) -0.2197(2) -0.0088(3) 0.0657(9) Uani 1 1 d . . . C16 C 0.1395(4) -0.1615(2) -0.0719(2) 0.0507(7) Uani 1 1 d . . . H1 H 0.413(4) 0.508(2) -0.208(2) 0.058(9) Uiso 1 1 d . . . H6A H 0.097(4) 0.562(2) -0.172(3) 0.058(8) Uiso 1 1 d . . . H6B H 0.248(3) 0.634(2) -0.147(2) 0.050(8) Uiso 1 1 d . . . H5A H 0.177(5) 0.555(3) 0.000(3) 0.080(11) Uiso 1 1 d . . . H5B H 0.348(5) 0.524(3) -0.031(3) 0.065(11) Uiso 1 1 d . . . H4A H 0.066(4) 0.399(2) -0.067(2) 0.056(9) Uiso 1 1 d . . . H4B H 0.206(4) 0.373(2) 0.009(2) 0.057(8) Uiso 1 1 d . . . H3 H 0.383(3) 0.358(2) -0.1149(18) 0.037(7) Uiso 1 1 d . . . H2A H 0.141(4) 0.393(2) -0.241(2) 0.047(8) Uiso 1 1 d . . . H2B H 0.313(4) 0.360(2) -0.272(2) 0.054(8) Uiso 1 1 d . . . H7 H 0.443(3) 0.177(2) -0.1073(18) 0.037(7) Uiso 1 1 d . . . H8 H -0.004(4) 0.239(2) -0.151(2) 0.062(9) Uiso 1 1 d . . . H9 H 0.026(4) 0.045(2) -0.141(2) 0.057(9) Uiso 1 1 d . . . H10 H 0.283(4) 0.615(3) -0.312(2) 0.066(10) Uiso 1 1 d . . . H10A H 0.325(5) -0.055(3) -0.173(3) 0.076(11) Uiso 1 1 d . . . H10B H 0.438(4) -0.015(2) -0.096(2) 0.050(8) Uiso 1 1 d . . . H12 H 0.316(4) -0.014(3) 0.078(2) 0.072(10) Uiso 1 1 d . . . H13 H 0.177(5) -0.111(3) 0.185(3) 0.098(14) Uiso 1 1 d . . . H14 H 0.008(6) -0.243(4) 0.133(4) 0.122(18) Uiso 1 1 d . . . H15 H -0.021(5) -0.269(3) -0.030(3) 0.093(14) Uiso 1 1 d . . . H16 H 0.130(3) -0.170(2) -0.138(2) 0.045(8) 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 Br1 0.04301(13) 0.04324(13) 0.06486(16) 0.00249(13) -0.00548(13) -0.00636(12) O1 0.0903(16) 0.0416(9) 0.0398(10) 0.0090(7) 0.0025(10) 0.0017(10) N1 0.0343(10) 0.0322(9) 0.0480(11) 0.0063(8) -0.0015(8) -0.0007(8) N3 0.0380(10) 0.0310(10) 0.0486(12) 0.0042(8) -0.0020(9) -0.0011(8) C1 0.0498(13) 0.0353(11) 0.0381(11) 0.0055(9) 0.0043(12) -0.0002(12) C2 0.0524(14) 0.0328(11) 0.0406(13) 0.0014(10) 0.0056(11) 0.0041(10) C3 0.0380(14) 0.0289(11) 0.0452(12) 0.0043(9) -0.0006(10) 0.0019(10) C4 0.0691(17) 0.0397(12) 0.0369(12) 0.0036(10) 0.0096(14) 0.0000(15) C5 0.087(3) 0.0407(14) 0.0412(13) -0.0030(11) 0.0105(15) -0.0021(15) C6 0.0627(17) 0.0338(12) 0.0475(14) 0.0013(9) 0.0086(13) 0.0032(13) C7 0.0350(13) 0.0333(13) 0.0439(13) 0.0031(9) -0.0022(10) 0.0006(9) C8 0.0341(11) 0.0425(13) 0.0738(18) 0.0112(13) -0.0085(11) 0.0011(12) C9 0.0366(12) 0.0457(15) 0.0688(18) 0.0075(12) -0.0039(12) -0.0089(12) C10 0.0469(16) 0.0329(12) 0.0603(16) 0.0022(11) 0.0067(13) 0.0019(11) C11 0.0465(13) 0.0265(10) 0.0476(13) 0.0019(9) -0.0016(11) 0.0060(10) C12 0.0568(16) 0.0503(15) 0.0551(16) -0.0047(12) -0.0071(13) 0.0069(13) C13 0.076(2) 0.086(2) 0.0447(16) 0.0115(16) 0.0035(16) 0.027(2) C14 0.073(2) 0.0526(17) 0.081(2) 0.0232(17) 0.0229(18) 0.0127(18) C15 0.0718(19) 0.0371(16) 0.088(2) 0.0031(15) 0.0159(19) -0.0031(14) C16 0.0633(17) 0.0362(12) 0.0528(17) -0.0048(11) 0.0024(13) -0.0025(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 C1 1.424(3) . YES O1 H10 0.87(4) . YES N1 C7 1.321(3) . YES N1 C8 1.375(3) . YES N1 C3 1.481(3) . YES N3 C7 1.320(3) . YES N3 C9 1.376(3) . YES N3 C10 1.487(3) . YES C1 C6 1.509(4) . YES C1 C2 1.523(3) . YES C1 H1 0.99(3) . YES C2 C3 1.525(4) . YES C2 H2A 0.94(3) . YES C2 H2B 1.00(3) . YES C3 C4 1.518(4) . YES C3 H3 0.92(3) . YES C4 C5 1.529(4) . YES C4 H4A 1.07(3) . YES C4 H4B 0.93(3) . YES C5 C6 1.518(4) . YES C5 H5A 0.99(4) . YES C5 H5B 0.98(4) . YES C6 H6A 1.04(3) . YES C6 H6B 0.96(3) . YES C7 H7 0.93(3) . YES C8 C9 1.344(4) . YES C8 H8 0.93(3) . YES C9 H9 0.98(3) . YES C10 C11 1.501(4) . YES C10 H10A 0.99(4) . YES C10 H10B 0.96(3) . YES C11 C12 1.381(4) . YES C11 C16 1.385(4) . YES C12 C13 1.390(5) . YES C12 H12 0.96(4) . YES C13 C14 1.370(6) . YES C13 H13 0.94(4) . YES C14 C15 1.374(5) . YES C14 H14 0.98(5) . YES C15 C16 1.375(4) . YES C15 H15 0.96(4) . YES C16 H16 0.94(3) . YES 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 O1 H10 109(2) . . YES C7 N1 C8 108.2(2) . . YES C7 N1 C3 125.1(2) . . YES C8 N1 C3 126.6(2) . . YES C7 N3 C9 108.4(2) . . YES C7 N3 C10 126.4(2) . . YES C9 N3 C10 125.1(2) . . YES O1 C1 C6 112.6(2) . . YES O1 C1 C2 107.4(2) . . YES C6 C1 C2 111.2(2) . . YES O1 C1 H1 109.9(18) . . YES C6 C1 H1 110.2(19) . . YES C2 C1 H1 105.3(19) . . YES C1 C2 C3 109.2(2) . . YES C1 C2 H2A 110.0(19) . . YES C3 C2 H2A 110.0(19) . . YES C1 C2 H2B 110.7(18) . . YES C3 C2 H2B 107.9(17) . . YES H2A C2 H2B 109(3) . . YES N1 C3 C4 110.8(2) . . YES N1 C3 C2 110.7(2) . . YES C4 C3 C2 111.7(2) . . YES N1 C3 H3 109.3(17) . . YES C4 C3 H3 107.9(17) . . YES C2 C3 H3 106.3(17) . . YES C3 C4 C5 109.4(2) . . YES C3 C4 H4A 105.9(18) . . YES C5 C4 H4A 110.5(18) . . YES C3 C4 H4B 109(2) . . YES C5 C4 H4B 113.5(19) . . YES H4A C4 H4B 109(3) . . YES C6 C5 C4 111.0(3) . . YES C6 C5 H5A 109(2) . . YES C4 C5 H5A 110(2) . . YES C6 C5 H5B 109(2) . . YES C4 C5 H5B 111(2) . . YES H5A C5 H5B 106(3) . . YES C1 C6 C5 111.0(2) . . YES C1 C6 H6A 100.3(19) . . YES C5 C6 H6A 115.8(19) . . YES C1 C6 H6B 107.1(17) . . YES C5 C6 H6B 112.2(18) . . YES H6A C6 H6B 109(2) . . YES N3 C7 N1 109.2(2) . . YES N3 C7 H7 127.9(17) . . YES N1 C7 H7 122.7(17) . . YES C9 C8 N1 107.3(2) . . YES C9 C8 H8 127(2) . . YES N1 C8 H8 126(2) . . YES C8 C9 N3 106.9(2) . . YES C8 C9 H9 133.2(19) . . YES N3 C9 H9 119.9(19) . . YES N3 C10 C11 110.9(2) . . YES N3 C10 H10A 109(2) . . YES C11 C10 H10A 109(2) . . YES N3 C10 H10B 107.8(18) . . YES C11 C10 H10B 114.2(18) . . YES H10A C10 H10B 105(3) . . YES C12 C11 C16 118.7(3) . . YES C12 C11 C10 121.1(2) . . YES C16 C11 C10 120.2(2) . . YES C11 C12 C13 119.9(3) . . YES C11 C12 H12 119(2) . . YES C13 C12 H12 121(2) . . YES C14 C13 C12 120.7(3) . . YES C14 C13 H13 124(3) . . YES C12 C13 H13 116(3) . . YES C13 C14 C15 119.6(3) . . YES C13 C14 H14 120(3) . . YES C15 C14 H14 120(3) . . YES C14 C15 C16 120.0(3) . . YES C14 C15 H15 118(3) . . YES C16 C15 H15 121(3) . . YES C15 C16 C11 121.1(3) . . YES C15 C16 H16 121.9(18) . . YES C11 C16 H16 117.0(17) . . YES _diffrn_measured_fraction_theta_max 0.984 _diffrn_reflns_theta_full 70.58 _diffrn_measured_fraction_theta_full 0.984 _refine_diff_density_max 0.231 _refine_diff_density_min -0.314 _refine_diff_density_rms 0.095 # Start Validation Reply Form _vrf_PUBL024_GLOBAL ; PROBLEM: The number of authors is grater than 5. RESPONSE: The various contributions to the paper are as follows. Caroline E. Paul: Development of synthetic, catalytic and toxicity evaluation studies for the preparation and application of imidazolium derivatives. Vicente Gotor-Fern\'andez: Design of synthetic routes for imidazolium derivatives and coordination of organocatalytic reactions. Iv\'an Lavandera: Design and coordination of toxicity studies for imidazolium derivatives. Jose Montejo-Bernardo and Santiago Garc\'ia-Granda: determination of crystal structure by single crystal x-Ray diffraction of the imidazolium bromide salt (1S,3R)-cis-IM-OH-Bn-Br. Vicente Gotor: Leader of the group and responsible for the overall coordination of the project. ; # end Validation Reply Form