Supplementary Material (ESI) for Organic & Biomolecular Chemistry This journal is (c) The Royal Society of Chemistry 2006 data_global _journal_name_full Org.Biomol.Chem. #============================================================================== _journal_coden_Cambridge 0177 # 1. SUBMISSION DETAILS _publ_contact_author ; Irishi N. N. Namboothiri Department of Chemistry Indian Institute of Technology Bombay Powai Mumbai 400 076 India ; _publ_contact_author_phone '+91 22 2576 7196' _publ_contact_author_fax '+91 22 2576 7152' _publ_contact_author_email irishi@chem.iitb.ac.in # 2. TITLE AND AUTHOR LIST _publ_section_title ; Highly efficient hydrazination of conjugated nitroalkenes via imidazole or DMAP mediated Morita-Baylis-Hillman reaction ; loop_ _publ_author_name _publ_author_address 'Mamta Dadwal' ; Department of Chemistry Indian Institute of Technology Bombay Powai Mumbai 400 076 India ; 'Shaik M. Mobin' ; National Single Crystal X-ray Diffraction Faciltiy Indian Institute of Technology Bombay Powai Mumbai 400 076 India ; 'Irishi N. N. Namboothiri' ; Department of Chemistry Indian Institute of Technology Bombay Powai Mumbai 400 076 India ; _publ_contact_author_name 'Irishi N. N. Namboothiri' #============================================================================== # Attachment 'IIN22B-CIF.CIF' data_iin22b _database_code_depnum_ccdc_archive 'CCDC 294436' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C14 H19 N3 O7' _chemical_formula_weight 341.32 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' O O 0.0106 0.0060 '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 Triclinic _symmetry_space_group_name_H-M 'P -1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 8.6000(6) _cell_length_b 10.0870(12) _cell_length_c 10.8430(9) _cell_angle_alpha 67.342(8) _cell_angle_beta 89.563(6) _cell_angle_gamma 89.466(8) _cell_volume 867.97(14) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 5.1600 _cell_measurement_theta_max 10.4600 _exptl_crystal_description block _exptl_crystal_colour yellow _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.306 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 360 _exptl_absorpt_coefficient_mu 0.106 _exptl_absorpt_correction_type Psi-scan _exptl_absorpt_correction_T_min 0.9589 _exptl_absorpt_correction_T_max 0.9843 _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 'Nonius MACH3' _diffrn_measurement_method \w/q-scan _diffrn_detector_area_resol_mean ? _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 3600 _diffrn_standards_decay_% <3 _diffrn_reflns_number 3192 _diffrn_reflns_av_R_equivalents 0.0184 _diffrn_reflns_av_sigmaI/netI 0.0605 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.04 _diffrn_reflns_theta_max 24.97 _reflns_number_total 3004 _reflns_number_gt 1830 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Argus (Nonius, MACH3 software)' _computing_cell_refinement 'Argus (Nonius, MACH3 software)' _computing_data_reduction 'Maxus (Nonius software)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics Ortep _computing_publication_material Shelx97 _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^)+(0.0803P)^2^+0.0278P] 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 3004 _refine_ls_number_parameters 237 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1194 _refine_ls_R_factor_gt 0.0495 _refine_ls_wR_factor_ref 0.1468 _refine_ls_wR_factor_gt 0.1233 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group N1 N -0.1350(3) 0.2112(3) 0.1273(2) 0.0537(6) Uani 1 d . . . N2 N -0.0635(2) 0.2469(2) 0.32563(19) 0.0432(5) Uani 1 d . . . N3 N -0.1690(3) 0.1529(3) 0.4131(2) 0.0495(6) Uani 1 d . . . O1 O -0.1438(2) 0.70226(19) 0.06561(18) 0.0605(6) Uani 1 d . . . O2 O -0.2069(3) 0.2510(3) 0.0227(2) 0.0789(7) Uani 1 d . . . O3 O -0.0814(3) 0.0899(2) 0.1831(2) 0.0719(7) Uani 1 d . . . O4 O 0.1278(2) 0.16547(19) 0.48013(17) 0.0540(5) Uani 1 d . . . O5 O 0.17812(19) 0.32693(19) 0.27100(16) 0.0471(5) Uani 1 d . . . O6 O -0.2333(3) 0.3123(2) 0.5063(2) 0.0775(7) Uani 1 d . . . O7 O -0.3175(2) 0.0842(2) 0.59215(18) 0.0600(6) Uani 1 d . . . C1 C -0.1234(4) 0.7978(3) 0.1233(3) 0.0658(9) Uani 1 d . . . H1 H -0.1318 0.8969 0.0787 0.079 Uiso 1 calc R . . C2 C -0.0895(4) 0.7318(3) 0.2525(3) 0.0608(8) Uani 1 d . . . H2 H -0.0718 0.7751 0.3129 0.073 Uiso 1 calc R . . C3 C -0.0858(4) 0.5834(3) 0.2797(3) 0.0556(7) Uani 1 d . . . H3 H -0.0646 0.5100 0.3617 0.067 Uiso 1 calc R . . C4 C -0.1188(3) 0.5677(3) 0.1646(2) 0.0419(6) Uani 1 d . . . C5 C -0.1348(3) 0.4521(3) 0.1218(3) 0.0421(6) Uani 1 d . . . C6 C -0.1116(3) 0.3119(3) 0.1930(2) 0.0405(6) Uani 1 d . . . C7 C 0.0882(3) 0.2401(3) 0.3674(2) 0.0405(6) Uani 1 d . . . C8 C 0.3410(3) 0.3405(3) 0.3065(3) 0.0552(8) Uani 1 d . . . C9 C 0.4268(4) 0.3973(4) 0.1757(3) 0.0856(11) Uani 1 d . . . H9A H 0.4051 0.3383 0.1265 0.103 Uiso 1 calc R . . H9B H 0.5365 0.3957 0.1920 0.103 Uiso 1 calc R . . H9C H 0.3937 0.4942 0.1249 0.103 Uiso 1 calc R . . C10 C 0.3470(4) 0.4352(4) 0.3830(4) 0.0968(12) Uani 1 d . . . H10A H 0.3073 0.5287 0.3288 0.116 Uiso 1 calc R . . H10B H 0.4527 0.4433 0.4069 0.116 Uiso 1 calc R . . H10C H 0.2849 0.3946 0.4625 0.116 Uiso 1 calc R . . C11 C -0.2388(3) 0.1945(3) 0.5057(3) 0.0477(7) Uani 1 d . . . C12 C -0.4032(4) 0.1099(4) 0.6966(3) 0.0656(9) Uani 1 d . . . C13 C -0.3115(5) 0.0627(7) 0.8158(4) 0.152(2) Uani 1 d . . . H13A H -0.3128 -0.0403 0.8570 0.182 Uiso 1 calc R . . H13B H -0.3538 0.1020 0.8768 0.182 Uiso 1 calc R . . H13C H -0.2064 0.0947 0.7936 0.182 Uiso 1 calc R . . C14 C -0.5533(4) 0.0261(5) 0.7129(4) 0.1011(13) Uani 1 d . . . H14A H -0.5956 0.0429 0.6264 0.121 Uiso 1 calc R . . H14B H -0.6269 0.0570 0.7634 0.121 Uiso 1 calc R . . H14C H -0.5322 -0.0746 0.7590 0.121 Uiso 1 calc R . . H5 H -0.165(3) 0.476(2) 0.030(2) 0.037(6) Uiso 1 d . . . H3N H -0.154(3) 0.066(3) 0.429(3) 0.057(9) Uiso 1 d . . . H8 H 0.378(3) 0.244(3) 0.361(3) 0.062(8) Uiso 1 d . . . H12 H -0.483(4) 0.197(3) 0.674(3) 0.075(9) Uiso 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 N1 0.0609(16) 0.0530(16) 0.0528(15) -0.0267(13) 0.0143(12) -0.0109(12) N2 0.0453(14) 0.0408(12) 0.0366(12) -0.0074(10) 0.0083(10) -0.0077(10) N3 0.0604(16) 0.0379(14) 0.0477(13) -0.0138(11) 0.0191(11) -0.0106(11) O1 0.0866(16) 0.0409(11) 0.0496(11) -0.0125(9) -0.0069(10) 0.0053(10) O2 0.1018(18) 0.0827(16) 0.0664(15) -0.0439(13) -0.0149(13) -0.0073(13) O3 0.0998(18) 0.0446(12) 0.0742(14) -0.0262(11) 0.0202(13) -0.0031(12) O4 0.0689(14) 0.0468(11) 0.0387(11) -0.0081(9) -0.0024(9) 0.0071(10) O5 0.0405(11) 0.0504(11) 0.0428(10) -0.0098(8) 0.0033(8) -0.0026(8) O6 0.1025(19) 0.0477(13) 0.0843(15) -0.0281(12) 0.0462(13) -0.0156(12) O7 0.0734(14) 0.0484(11) 0.0562(12) -0.0179(10) 0.0307(10) -0.0155(10) C1 0.093(3) 0.0406(16) 0.066(2) -0.0224(16) 0.0033(17) 0.0025(16) C2 0.079(2) 0.0523(18) 0.0565(19) -0.0270(16) 0.0089(16) -0.0064(16) C3 0.073(2) 0.0486(17) 0.0411(15) -0.0126(13) 0.0046(14) -0.0050(14) C4 0.0484(16) 0.0340(14) 0.0389(14) -0.0091(12) 0.0036(12) -0.0012(11) C5 0.0403(15) 0.0500(17) 0.0350(14) -0.0153(13) 0.0017(11) -0.0006(12) C6 0.0399(15) 0.0435(15) 0.0403(14) -0.0185(13) 0.0062(11) -0.0044(12) C7 0.0493(17) 0.0321(13) 0.0400(15) -0.0140(12) 0.0057(12) 0.0021(12) C8 0.0396(17) 0.060(2) 0.0607(18) -0.0181(16) -0.0059(14) 0.0018(14) C9 0.0473(19) 0.105(3) 0.082(2) -0.010(2) 0.0074(17) -0.0055(19) C10 0.079(3) 0.107(3) 0.124(3) -0.066(3) -0.007(2) -0.016(2) C11 0.0510(17) 0.0441(17) 0.0454(15) -0.0143(13) 0.0089(13) -0.0039(13) C12 0.074(2) 0.065(2) 0.0579(19) -0.0240(16) 0.0319(17) -0.0115(18) C13 0.095(3) 0.294(8) 0.090(3) -0.100(4) 0.006(3) -0.027(4) C14 0.070(2) 0.133(4) 0.102(3) -0.048(3) 0.020(2) -0.016(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 N1 O2 1.219(3) . ? N1 O3 1.225(3) . ? N1 C6 1.463(3) . ? N2 C7 1.377(3) . ? N2 N3 1.390(3) . ? N2 C6 1.395(3) . ? N3 C11 1.362(3) . ? N3 H3N 0.84(3) . ? O1 C1 1.350(3) . ? O1 C4 1.384(3) . ? O4 C7 1.212(3) . ? O5 C7 1.324(3) . ? O5 C8 1.477(3) . ? O6 C11 1.192(3) . ? O7 C11 1.333(3) . ? O7 C12 1.451(3) . ? C1 C2 1.332(4) . ? C1 H1 0.9300 . ? C2 C3 1.410(4) . ? C2 H2 0.9300 . ? C3 C4 1.350(4) . ? C3 H3 0.9300 . ? C4 C5 1.419(4) . ? C5 C6 1.339(4) . ? C5 H5 0.97(2) . ? C8 C10 1.487(5) . ? C8 C9 1.500(4) . ? C8 H8 0.98(3) . ? C9 H9A 0.9600 . ? C9 H9B 0.9600 . ? C9 H9C 0.9600 . ? C10 H10A 0.9600 . ? C10 H10B 0.9600 . ? C10 H10C 0.9600 . ? C12 C13 1.433(5) . ? C12 C14 1.522(5) . ? C12 H12 1.06(3) . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 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 O2 N1 O3 123.8(2) . . ? O2 N1 C6 119.2(2) . . ? O3 N1 C6 117.0(2) . . ? C7 N2 N3 117.5(2) . . ? C7 N2 C6 124.6(2) . . ? N3 N2 C6 115.7(2) . . ? C11 N3 N2 117.6(2) . . ? C11 N3 H3N 121(2) . . ? N2 N3 H3N 116(2) . . ? C1 O1 C4 106.4(2) . . ? C7 O5 C8 116.7(2) . . ? C11 O7 C12 116.9(2) . . ? C2 C1 O1 111.2(3) . . ? C2 C1 H1 124.4 . . ? O1 C1 H1 124.4 . . ? C1 C2 C3 106.5(3) . . ? C1 C2 H2 126.8 . . ? C3 C2 H2 126.8 . . ? C4 C3 C2 107.3(3) . . ? C4 C3 H3 126.4 . . ? C2 C3 H3 126.4 . . ? C3 C4 O1 108.7(2) . . ? C3 C4 C5 136.8(2) . . ? O1 C4 C5 114.5(2) . . ? C6 C5 C4 127.9(2) . . ? C6 C5 H5 114.9(14) . . ? C4 C5 H5 117.2(13) . . ? C5 C6 N2 127.6(2) . . ? C5 C6 N1 118.4(2) . . ? N2 C6 N1 114.0(2) . . ? O4 C7 O5 126.6(3) . . ? O4 C7 N2 122.2(2) . . ? O5 C7 N2 111.2(2) . . ? O5 C8 C10 109.4(3) . . ? O5 C8 C9 104.9(2) . . ? C10 C8 C9 114.3(3) . . ? O5 C8 H8 106.9(17) . . ? C10 C8 H8 110.5(17) . . ? C9 C8 H8 110.3(16) . . ? C8 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C8 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? C8 C10 H10A 109.5 . . ? C8 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C8 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? O6 C11 O7 125.8(2) . . ? O6 C11 N3 125.0(2) . . ? O7 C11 N3 109.2(2) . . ? C13 C12 O7 109.2(3) . . ? C13 C12 C14 113.0(3) . . ? O7 C12 C14 105.0(3) . . ? C13 C12 H12 121.8(17) . . ? O7 C12 H12 121.1(16) . . ? C14 C12 H12 81.4(16) . . ? C12 C13 H13A 109.5 . . ? C12 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C12 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 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 C7 N2 N3 C11 86.0(3) . . . . ? C6 N2 N3 C11 -110.0(3) . . . . ? C4 O1 C1 C2 -0.9(3) . . . . ? O1 C1 C2 C3 0.8(4) . . . . ? C1 C2 C3 C4 -0.3(4) . . . . ? C2 C3 C4 O1 -0.2(3) . . . . ? C2 C3 C4 C5 -179.6(3) . . . . ? C1 O1 C4 C3 0.7(3) . . . . ? C1 O1 C4 C5 -179.8(2) . . . . ? C3 C4 C5 C6 -3.6(5) . . . . ? O1 C4 C5 C6 177.0(2) . . . . ? C4 C5 C6 N2 -1.2(5) . . . . ? C4 C5 C6 N1 -179.9(2) . . . . ? C7 N2 C6 C5 -80.1(4) . . . . ? N3 N2 C6 C5 117.2(3) . . . . ? C7 N2 C6 N1 98.7(3) . . . . ? N3 N2 C6 N1 -64.0(3) . . . . ? O2 N1 C6 C5 -16.3(4) . . . . ? O3 N1 C6 C5 164.4(2) . . . . ? O2 N1 C6 N2 164.8(2) . . . . ? O3 N1 C6 N2 -14.5(3) . . . . ? C8 O5 C7 O4 -3.7(4) . . . . ? C8 O5 C7 N2 174.3(2) . . . . ? N3 N2 C7 O4 -6.8(4) . . . . ? C6 N2 C7 O4 -169.2(2) . . . . ? N3 N2 C7 O5 175.1(2) . . . . ? C6 N2 C7 O5 12.6(3) . . . . ? C7 O5 C8 C10 -76.9(3) . . . . ? C7 O5 C8 C9 160.0(2) . . . . ? C12 O7 C11 O6 -0.4(5) . . . . ? C12 O7 C11 N3 -178.4(3) . . . . ? N2 N3 C11 O6 10.9(4) . . . . ? N2 N3 C11 O7 -171.1(2) . . . . ? C11 O7 C12 C13 -96.8(4) . . . . ? C11 O7 C12 C14 141.7(3) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N3 H3N O4 0.84(3) 2.16(3) 2.983(3) 166(3) 2_556 _diffrn_measured_fraction_theta_max 0.988 _diffrn_reflns_theta_full 24.97 _diffrn_measured_fraction_theta_full 0.988 _refine_diff_density_max 0.289 _refine_diff_density_min -0.225 _refine_diff_density_rms 0.048