# Supplementary Material (ESI) for Green Chemistry # This journal is © The Royal Society of Chemistry 2010 data_global _journal_name_full 'Green Chemistry' _journal_coden_Cambridge 1048 _publ_contact_author_name 'Hiram I Beltran' _publ_contact_author_email HBELTRAN@CORREO.CUA.UAM.MX _publ_section_title ; Molecular Design and QSAR Study of Low Acute Toxicity Biocides with 4, 4`-Dimorfolyl-Methane Core Obtained by Microwave Assisted Synthesis. ; _publ_author_address ; 1) Posgrado, 2) Programa de Ingenieria Molecular, and 3) Laboratorio de Sintesis Quimica y Electroquimica; Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas No. 152, Apartado Postal 14-805, 07730 Mexico, D.F. 4) Departamento de Biotecnologia, Universidad Autonoma Metropolitana-Iztapalapa, Apartado Postal 55-535, 09340 Mexico, D.F. 5) Centro de Investigaciones Quimicas, Universidad Autonoma del Estado de Morelos, Av. Universidad 1001, 62210 Cuernavaca, Mexico. 6) Departamento de Ciencias Naturales DCNI, UAM-Cuajimalpa, Pedro Antonio de los Santos 84, Sn. Miguel Chapultepec, 11850, Mexico, D.F. ; _publ_contact_author_address ; Posgrado, Programa de Ingenieria Molecular, and Laboratorio de Sintesis Quimica y Electroquimica; Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas No. 152, Apartado Postal 14-805, 07730 Mexico, D.F. ; loop_ _publ_author_name 'Hiram I Beltran' 'Victor Barba' 'Francisco Jose Fernandez-Perrino' 'Cesar Andres Flores-Sandoval' ; R.Hernandez-Altamirano ; 'Violeta Y. Mena-Cervantes' 'Sandra Perez-Miranda' ; L.S.Zamudio-Rivera ; # Attachment '4b.txt' data_luiszwex _database_code_depnum_ccdc_archive 'CCDC 750435' #TrackingRef '4b.txt' _audit_creation_method SHELXL-97 _publ_suggested_journal 'Green Chemistry' _publ_section_abstract ; The solventless microwave assisted synthesis, among aldehydes (1a, 2b-h) and morpholine (3) in 1:2 (aldehyde: morpholine) ratios, yielded eight 4, 4`-Dimorfolyl-Methanes (4a-4h), which were thoroughly characterized through FT-IR, 1H, 13C and 2D NMR confirming structures of type 4. Described compounds are dimorpholino-methane (4a), 2-(dimorpholinomethyl)-phenol (4b), 4-bromo-2-(dimorpholinomethyl)-phenol (4c), 2,4-di-tert-butyl-6- (dimorpholinomethyl)-phenol (4d), 4,4'-(pyridin-2-ylmethylene)-dimorpholine (4e), 4,4'-((4-iso-propylphenyl) methylene)-dimorpholine (4f), 4,4'-(naphthalen-1-ylmethylene)-dimorpholine (4g) and 4,4'-(pyren-1-ylmethylene) -dimorpholine (4h). Additionally, single crystal X-ray diffraction analysis for 4b, 4c, 4d and 4e derivatives was accomplished. The obtained 4, 4`-dimorfolyl-methanes were subjected for two biological tests, i) acute toxicity, related to Photobacterium phosphoreum (Vibrio fischeri), and ii) biocidal activities, determined for B. subtilis, E. coli and Ps. fluorescence strains. The results show that 4a-h compounds have varying degrees of toxicity, classified as 4a, 4b, 4c, 4e and 4f as slightly-moderately toxic agents, 4g and 4h as highly toxic chemicals, and 4d as extremely toxic compound. Besides, the biocidal activities, which resulted to be controlled mainly by the substituent directly bonded to the methinic bridge (C5, originally it is the aldehyde carbon atom), have shown varying degrees of inhibitory effects on the growth of selected strains, depending on the chemical structure of 4a-h. A QSAR study was developed, and quantum-chemical parameters of 4a-h were obtained with the DFT approach at the B3LYP/6-311G(d) level of theory in the gas phase and ten molecular descriptors were determined, being EHOMO, ELUMO, GAP, C5 Mulliken atomic charge (ACMulliken), C5 atomic charge of NBO (ACNBO), dipolar moment (mu), molecular hydrophobicity as Log P, molecular volume (Vol), electrostatic potential (ESP) and delta13C(C5), all of them being typical determinants of biological activities in other molecular systems. A linear combination from three to six molecular descriptors was chosen as multivariate model to achieve correlations in order to relate them with their acute toxicity and understand the obtained trend. Three sets of descriptors accomplished the statistical goal, and through an identity analysis the conserved descriptors in these three series are the log P, the ESP and the delta13C(C5), which seemed to be the tracking variables in the system. In a lesser extend, the frontier orbitals and their relations (HOMO, LUMO and GAP), are also present within the correlations. The phenol bearing structures (4b, 4c and 4d, derived from salicylidenes) are best tuned within these variables since the substitution in the phenol fragment both governs the toxicity and the biocidal potency. The best candidates are 4a, 4b and 4c, because of diminished toxicity and preserved biocidal potency were obtained at the same time. A more hydrophobic substitution (4d) extremely increases the Vibrio fischeri toxicity, banning its application. Through the full analysis presented in this piece of work it can be stated that selected prototypes could be used in the oil industry as a new generation of ecological chemical products. ; _chemical_name_systematic ; 2-(dimorpholinomethyl)phenol ; _chemical_name_common 2-(dimorpholinomethyl)phenol _chemical_melting_point ? _chemical_formula_moiety 'C15 H22 N2 O3' _chemical_formula_sum 'C15 H22 N2 O3' _chemical_formula_weight 278.35 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 'P b c a' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 12.2357(12) _cell_length_b 7.5855(8) _cell_length_c 31.232(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2898.8(5) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 4652 _cell_measurement_theta_min 2.61 _cell_measurement_theta_max 27.13 _exptl_crystal_description 'rectangular prism' _exptl_crystal_colour yellow _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.31 _exptl_crystal_size_min 0.29 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.276 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1200 _exptl_absorpt_coefficient_mu 0.089 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.78 _exptl_absorpt_correction_T_max 1.00 _exptl_absorpt_process_details SADABS _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 13325 _diffrn_reflns_av_R_equivalents 0.0361 _diffrn_reflns_av_sigmaI/netI 0.0281 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -36 _diffrn_reflns_limit_l_max 37 _diffrn_reflns_theta_min 1.30 _diffrn_reflns_theta_max 25.00 _reflns_number_total 2544 _reflns_number_gt 2162 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' _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^)+(0.0521P)^2^+0.9961P] 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 2544 _refine_ls_number_parameters 185 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0792 _refine_ls_R_factor_gt 0.0661 _refine_ls_wR_factor_ref 0.1466 _refine_ls_wR_factor_gt 0.1404 _refine_ls_goodness_of_fit_ref 1.268 _refine_ls_restrained_S_all 1.268 _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 H1O H 0.396(2) 1.016(4) 0.6563(9) 0.063(9) Uiso 1 1 d . . . C1 C 0.57039(18) 0.9272(3) 0.62136(7) 0.0407(6) Uani 1 1 d . . . H1 H 0.6290 0.8394 0.6196 0.049 Uiso 1 1 calc R . . C1A C 0.4709(2) 0.6850(3) 0.65336(8) 0.0519(6) Uani 1 1 d . . . H1A1 H 0.4890 0.7319 0.6814 0.062 Uiso 1 1 calc R . . H1A2 H 0.5277 0.6026 0.6452 0.062 Uiso 1 1 calc R . . C1B C 0.68732(19) 1.0998(3) 0.57413(8) 0.0482(6) Uani 1 1 d . . . H1B1 H 0.7387 1.0025 0.5754 0.058 Uiso 1 1 calc R . . H1B2 H 0.7082 1.1859 0.5956 0.058 Uiso 1 1 calc R . . C2 C 0.58679(19) 1.0288(3) 0.66314(7) 0.0428(6) Uani 1 1 d . . . C2A C 0.3629(2) 0.5908(4) 0.65546(9) 0.0649(8) Uani 1 1 d . . . H2A1 H 0.3677 0.4952 0.6760 0.078 Uiso 1 1 calc R . . H2A2 H 0.3071 0.6720 0.6653 0.078 Uiso 1 1 calc R . . C2B C 0.6902(2) 1.1829(4) 0.53025(8) 0.0598(7) Uani 1 1 d . . . H2B1 H 0.7636 1.2250 0.5244 0.072 Uiso 1 1 calc R . . H2B2 H 0.6724 1.0944 0.5089 0.072 Uiso 1 1 calc R . . C3 C 0.5013(2) 1.1132(3) 0.68491(7) 0.0478(6) Uani 1 1 d . . . C3A C 0.3283(2) 0.6596(3) 0.58440(9) 0.0570(7) Uani 1 1 d . . . H3A1 H 0.2723 0.7434 0.5927 0.068 Uiso 1 1 calc R . . H3A2 H 0.3083 0.6115 0.5567 0.068 Uiso 1 1 calc R . . C3B C 0.5084(2) 1.2672(3) 0.53659(8) 0.0561(7) Uani 1 1 d . . . H3B1 H 0.4853 1.1813 0.5155 0.067 Uiso 1 1 calc R . . H3B2 H 0.4587 1.3667 0.5351 0.067 Uiso 1 1 calc R . . C4 C 0.5235(3) 1.2199(4) 0.71984(8) 0.0619(7) Uani 1 1 d . . . H4 H 0.4667 1.2784 0.7336 0.074 Uiso 1 1 calc R . . C4A C 0.4362(2) 0.7544(3) 0.58049(8) 0.0503(6) Uani 1 1 d . . . H4A1 H 0.4923 0.6725 0.5712 0.060 Uiso 1 1 calc R . . H4A2 H 0.4305 0.8473 0.5593 0.060 Uiso 1 1 calc R . . C4B C 0.5016(2) 1.1859(3) 0.58052(8) 0.0485(6) Uani 1 1 d . . . H4B1 H 0.5209 1.2727 0.6020 0.058 Uiso 1 1 calc R . . H4B2 H 0.4275 1.1465 0.5860 0.058 Uiso 1 1 calc R . . C5 C 0.6287(3) 1.2402(4) 0.73435(9) 0.0696(9) Uani 1 1 d . . . H5 H 0.6430 1.3144 0.7574 0.084 Uiso 1 1 calc R . . C6 C 0.7128(3) 1.1511(4) 0.71485(9) 0.0673(8) Uani 1 1 d . . . H6 H 0.7835 1.1605 0.7255 0.081 Uiso 1 1 calc R . . C7 C 0.6918(2) 1.0478(3) 0.67956(8) 0.0532(7) Uani 1 1 d . . . H7 H 0.7494 0.9892 0.6663 0.064 Uiso 1 1 calc R . . N1A N 0.46596(15) 0.8302(2) 0.62199(6) 0.0415(5) Uani 1 1 d . . . N1B N 0.57692(15) 1.0360(2) 0.58276(6) 0.0407(5) Uani 1 1 d . . . O1 O 0.39501(14) 1.0949(3) 0.67317(6) 0.0606(6) Uani 1 1 d . . . O1A O 0.33193(16) 0.5215(2) 0.61481(6) 0.0640(5) Uani 1 1 d . . . O1B O 0.61584(15) 1.3253(2) 0.52659(6) 0.0610(5) 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 C1 0.0323(12) 0.0343(12) 0.0555(14) -0.0018(10) 0.0012(10) 0.0031(10) C1A 0.0486(15) 0.0490(15) 0.0582(15) 0.0013(12) 0.0002(12) -0.0066(12) C1B 0.0406(14) 0.0449(13) 0.0592(15) -0.0027(12) 0.0054(11) -0.0033(11) C2 0.0430(14) 0.0389(12) 0.0464(13) 0.0029(11) -0.0034(10) -0.0027(11) C2A 0.0629(19) 0.0598(17) 0.0720(18) 0.0032(15) 0.0045(14) -0.0176(15) C2B 0.0551(17) 0.0614(17) 0.0628(17) -0.0014(14) 0.0103(13) -0.0065(14) C3 0.0467(15) 0.0477(14) 0.0490(14) -0.0002(11) 0.0010(11) -0.0055(12) C3A 0.0529(16) 0.0469(15) 0.0712(17) -0.0142(13) -0.0058(13) -0.0061(12) C3B 0.0600(17) 0.0467(14) 0.0616(15) -0.0033(13) -0.0084(13) 0.0049(13) C4 0.076(2) 0.0629(17) 0.0469(14) -0.0086(13) 0.0077(13) -0.0112(15) C4A 0.0500(15) 0.0438(14) 0.0572(14) -0.0078(12) -0.0019(12) -0.0038(12) C4B 0.0433(14) 0.0435(13) 0.0587(15) -0.0053(12) 0.0002(11) 0.0059(11) C5 0.091(2) 0.0717(19) 0.0457(14) -0.0037(14) -0.0039(16) -0.0310(18) C6 0.066(2) 0.0759(19) 0.0602(17) 0.0086(15) -0.0222(15) -0.0238(16) C7 0.0455(15) 0.0547(15) 0.0595(16) 0.0087(13) -0.0079(12) -0.0077(12) N1A 0.0367(11) 0.0375(10) 0.0504(11) -0.0051(8) 0.0001(8) -0.0030(9) N1B 0.0359(11) 0.0360(10) 0.0502(11) -0.0049(9) 0.0011(9) -0.0004(8) O1 0.0443(11) 0.0695(13) 0.0680(12) -0.0233(11) 0.0051(9) 0.0042(9) O1A 0.0625(12) 0.0473(10) 0.0822(13) -0.0071(10) 0.0003(10) -0.0163(9) O1B 0.0691(13) 0.0508(11) 0.0631(11) 0.0057(9) -0.0001(9) -0.0077(10) _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 C1 N1B 1.464(3) . ? C1 N1A 1.475(3) . ? C1 C2 1.529(3) . ? C1 H1 0.9800 . ? C1A N1A 1.475(3) . ? C1A C2A 1.504(3) . ? C1A H1A1 0.9700 . ? C1A H1A2 0.9700 . ? C1B N1B 1.460(3) . ? C1B C2B 1.509(3) . ? C1B H1B1 0.9700 . ? C1B H1B2 0.9700 . ? C2 C7 1.391(3) . ? C2 C3 1.402(3) . ? C2A O1A 1.425(3) . ? C2A H2A1 0.9700 . ? C2A H2A2 0.9700 . ? C2B O1B 1.417(3) . ? C2B H2B1 0.9700 . ? C2B H2B2 0.9700 . ? C3 O1 1.358(3) . ? C3 C4 1.386(3) . ? C3A O1A 1.415(3) . ? C3A C4A 1.508(3) . ? C3A H3A1 0.9700 . ? C3A H3A2 0.9700 . ? C3B O1B 1.421(3) . ? C3B C4B 1.506(3) . ? C3B H3B1 0.9700 . ? C3B H3B2 0.9700 . ? C4 C5 1.373(4) . ? C4 H4 0.9300 . ? C4A N1A 1.464(3) . ? C4A H4A1 0.9700 . ? C4A H4A2 0.9700 . ? C4B N1B 1.466(3) . ? C4B H4B1 0.9700 . ? C4B H4B2 0.9700 . ? C5 C6 1.373(4) . ? C5 H5 0.9300 . ? C6 C7 1.376(4) . ? C6 H6 0.9300 . ? C7 H7 0.9300 . ? O1 H1O 0.80(3) . ? 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 N1B C1 N1A 109.88(17) . . ? N1B C1 C2 114.30(18) . . ? N1A C1 C2 110.73(18) . . ? N1B C1 H1 107.2 . . ? N1A C1 H1 107.2 . . ? C2 C1 H1 107.2 . . ? N1A C1A C2A 110.4(2) . . ? N1A C1A H1A1 109.6 . . ? C2A C1A H1A1 109.6 . . ? N1A C1A H1A2 109.6 . . ? C2A C1A H1A2 109.6 . . ? H1A1 C1A H1A2 108.1 . . ? N1B C1B C2B 109.1(2) . . ? N1B C1B H1B1 109.9 . . ? C2B C1B H1B1 109.9 . . ? N1B C1B H1B2 109.9 . . ? C2B C1B H1B2 109.9 . . ? H1B1 C1B H1B2 108.3 . . ? C7 C2 C3 117.6(2) . . ? C7 C2 C1 119.2(2) . . ? C3 C2 C1 123.1(2) . . ? O1A C2A C1A 111.7(2) . . ? O1A C2A H2A1 109.3 . . ? C1A C2A H2A1 109.3 . . ? O1A C2A H2A2 109.3 . . ? C1A C2A H2A2 109.3 . . ? H2A1 C2A H2A2 107.9 . . ? O1B C2B C1B 112.1(2) . . ? O1B C2B H2B1 109.2 . . ? C1B C2B H2B1 109.2 . . ? O1B C2B H2B2 109.2 . . ? C1B C2B H2B2 109.2 . . ? H2B1 C2B H2B2 107.9 . . ? O1 C3 C4 117.4(2) . . ? O1 C3 C2 122.5(2) . . ? C4 C3 C2 120.1(2) . . ? O1A C3A C4A 112.3(2) . . ? O1A C3A H3A1 109.1 . . ? C4A C3A H3A1 109.1 . . ? O1A C3A H3A2 109.1 . . ? C4A C3A H3A2 109.1 . . ? H3A1 C3A H3A2 107.9 . . ? O1B C3B C4B 112.2(2) . . ? O1B C3B H3B1 109.2 . . ? C4B C3B H3B1 109.2 . . ? O1B C3B H3B2 109.2 . . ? C4B C3B H3B2 109.2 . . ? H3B1 C3B H3B2 107.9 . . ? C5 C4 C3 120.7(3) . . ? C5 C4 H4 119.7 . . ? C3 C4 H4 119.7 . . ? N1A C4A C3A 109.5(2) . . ? N1A C4A H4A1 109.8 . . ? C3A C4A H4A1 109.8 . . ? N1A C4A H4A2 109.8 . . ? C3A C4A H4A2 109.8 . . ? H4A1 C4A H4A2 108.2 . . ? N1B C4B C3B 109.05(19) . . ? N1B C4B H4B1 109.9 . . ? C3B C4B H4B1 109.9 . . ? N1B C4B H4B2 109.9 . . ? C3B C4B H4B2 109.9 . . ? H4B1 C4B H4B2 108.3 . . ? C4 C5 C6 120.0(3) . . ? C4 C5 H5 120.0 . . ? C6 C5 H5 120.0 . . ? C5 C6 C7 119.7(3) . . ? C5 C6 H6 120.1 . . ? C7 C6 H6 120.1 . . ? C6 C7 C2 121.7(3) . . ? C6 C7 H7 119.1 . . ? C2 C7 H7 119.1 . . ? C4A N1A C1A 107.79(18) . . ? C4A N1A C1 113.55(17) . . ? C1A N1A C1 110.24(17) . . ? C1B N1B C1 112.93(17) . . ? C1B N1B C4B 108.43(18) . . ? C1 N1B C4B 116.27(17) . . ? C3 O1 H1O 104(2) . . ? C3A O1A C2A 109.5(2) . . ? C2B O1B C3B 109.86(19) . . ? 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 N1B C1 C2 C7 -89.6(3) . . . . ? N1A C1 C2 C7 145.7(2) . . . . ? N1B C1 C2 C3 86.9(3) . . . . ? N1A C1 C2 C3 -37.9(3) . . . . ? N1A C1A C2A O1A 58.4(3) . . . . ? N1B C1B C2B O1B 59.1(3) . . . . ? C7 C2 C3 O1 -176.0(2) . . . . ? C1 C2 C3 O1 7.5(4) . . . . ? C7 C2 C3 C4 4.0(3) . . . . ? C1 C2 C3 C4 -172.5(2) . . . . ? O1 C3 C4 C5 178.0(3) . . . . ? C2 C3 C4 C5 -2.0(4) . . . . ? O1A C3A C4A N1A -59.8(3) . . . . ? O1B C3B C4B N1B -58.7(3) . . . . ? C3 C4 C5 C6 -1.5(4) . . . . ? C4 C5 C6 C7 2.9(4) . . . . ? C5 C6 C7 C2 -0.9(4) . . . . ? C3 C2 C7 C6 -2.6(4) . . . . ? C1 C2 C7 C6 174.0(2) . . . . ? C3A C4A N1A C1A 58.0(2) . . . . ? C3A C4A N1A C1 -179.57(19) . . . . ? C2A C1A N1A C4A -58.0(3) . . . . ? C2A C1A N1A C1 177.5(2) . . . . ? N1B C1 N1A C4A 43.0(2) . . . . ? C2 C1 N1A C4A 170.22(18) . . . . ? N1B C1 N1A C1A 164.07(18) . . . . ? C2 C1 N1A C1A -68.7(2) . . . . ? C2B C1B N1B C1 170.26(19) . . . . ? C2B C1B N1B C4B -59.4(2) . . . . ? N1A C1 N1B C1B -165.13(17) . . . . ? C2 C1 N1B C1B 69.7(2) . . . . ? N1A C1 N1B C4B 68.6(2) . . . . ? C2 C1 N1B C4B -56.6(2) . . . . ? C3B C4B N1B C1B 59.3(2) . . . . ? C3B C4B N1B C1 -172.23(19) . . . . ? C4A C3A O1A C2A 58.0(3) . . . . ? C1A C2A O1A C3A -57.0(3) . . . . ? C1B C2B O1B C3B -56.7(3) . . . . ? C4B C3B O1B C2B 56.7(3) . . . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.217 _refine_diff_density_min -0.208 _refine_diff_density_rms 0.039 # Attachment '4c.txt' data_34herbm _database_code_depnum_ccdc_archive 'CCDC 750436' #TrackingRef '4c.txt' _audit_creation_method SHELXL-97 _publ_suggested_journal 'Green Chemistry' _publ_section_abstract ; The solventless microwave assisted synthesis, among aldehydes (1a, 2b-h) and morpholine (3) in 1:2 (aldehyde:morpholine) ratios, yielded eight 4, 4`-Dimorfolyl-Methanes (4a-4h), which were thoroughly characterized through FT-IR, 1H, 13C and 2D NMR confirming structures of type 4. Described compounds are dimorpholino-methane (4a), 2-(dimorpholinomethyl)-phenol (4b), 4-bromo-2-(dimorpholinomethyl)-phenol (4c), 2,4-di-tert-butyl-6-(dimorpholinomethyl)-phenol (4d), 4,4'-(pyridin-2-ylmethylene)-dimorpholine (4e), 4,4'-((4-iso-propylphenyl)methylene)-dimorpholine (4f), 4,4'-(naphthalen-1-ylmethylene)-dimorpholine (4g) and 4,4'-(pyren-1-ylmethylene)-dimorpholine (4h). Additionally, single crystal X-ray diffraction analysis for 4b, 4c, 4d and 4e derivatives was accomplished. The obtained 4, 4`-dimorfolyl-methanes were subjected for two biological tests, i) acute toxicity, related to Photobacterium phosphoreum (Vibrio fischeri), and ii) biocidal activities, determined for B. subtilis, E. coli and Ps. fluorescence st ; _chemical_name_systematic ; 4-bromo-2-(dimorpholinomethyl)phenol ; _chemical_name_common 4-bromo-2-(dimorpholinomethyl)phenol _chemical_melting_point ? _chemical_formula_moiety 'C15 H21 Br N2 O3' _chemical_formula_sum 'C15 H21 Br N2 O3' _chemical_formula_weight 357.25 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' Br Br -0.2901 2.4595 '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 P2(1)2(1)2(1) 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 7.0621(7) _cell_length_b 13.9243(14) _cell_length_c 16.4210(16) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1614.8(3) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 6493 _cell_measurement_theta_min 2.48 _cell_measurement_theta_max 26.50 _exptl_crystal_description 'rectangular prism' _exptl_crystal_colour yellow _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.42 _exptl_crystal_size_min 0.39 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.470 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 736 _exptl_absorpt_coefficient_mu 2.557 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.306 _exptl_absorpt_correction_T_max 0.369 _exptl_absorpt_process_details SADABS _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 12635 _diffrn_reflns_av_R_equivalents 0.0354 _diffrn_reflns_av_sigmaI/netI 0.0278 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -19 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 1.92 _diffrn_reflns_theta_max 25.00 _reflns_number_total 2838 _reflns_number_gt 2606 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SAINT' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' _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^)+(0.0310P)^2^+0.3799P] 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_coef 0.0196(10) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack -0.012(9) _refine_ls_number_reflns 2838 _refine_ls_number_parameters 195 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0306 _refine_ls_R_factor_gt 0.0266 _refine_ls_wR_factor_ref 0.0664 _refine_ls_wR_factor_gt 0.0646 _refine_ls_goodness_of_fit_ref 1.060 _refine_ls_restrained_S_all 1.060 _refine_ls_shift/su_max 0.002 _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 C1 C 0.2039(4) 0.24859(15) 0.74091(13) 0.0335(5) Uani 1 1 d . . . H1 H 0.3110 0.2039 0.7425 0.040 Uiso 1 1 calc R . . C1A C 0.3680(4) 0.3653(2) 0.65343(16) 0.0483(7) Uani 1 1 d . . . H1A1 H 0.2740 0.3570 0.6109 0.058 Uiso 1 1 calc R . . H1A2 H 0.4701 0.3202 0.6438 0.058 Uiso 1 1 calc R . . C1B C -0.0760(4) 0.2836(2) 0.65537(15) 0.0427(6) Uani 1 1 d . . . H1B1 H -0.0450 0.3513 0.6592 0.051 Uiso 1 1 calc R . . H1B2 H -0.1709 0.2689 0.6962 0.051 Uiso 1 1 calc R . . C2 C 0.0969(3) 0.23813(16) 0.82074(14) 0.0321(5) Uani 1 1 d . . . C2A C 0.4433(4) 0.4660(2) 0.65133(18) 0.0625(9) Uani 1 1 d . . . H2A1 H 0.4975 0.4785 0.5981 0.075 Uiso 1 1 calc R . . H2A2 H 0.3396 0.5106 0.6594 0.075 Uiso 1 1 calc R . . C2B C -0.1516(4) 0.2609(2) 0.57162(17) 0.0526(7) Uani 1 1 d . . . H2B1 H -0.2627 0.2999 0.5610 0.063 Uiso 1 1 calc R . . H2B2 H -0.0566 0.2767 0.5311 0.063 Uiso 1 1 calc R . . C3 C -0.0153(4) 0.31263(15) 0.85276(13) 0.0374(5) Uani 1 1 d . . . C3A C 0.5055(5) 0.4626(2) 0.78966(17) 0.0647(8) Uani 1 1 d . . . H3A1 H 0.4042 0.5078 0.8007 0.078 Uiso 1 1 calc R . . H3A2 H 0.6025 0.4716 0.8308 0.078 Uiso 1 1 calc R . . C3B C -0.0412(5) 0.10428(19) 0.58036(16) 0.0564(8) Uani 1 1 d . . . H3B1 H 0.0542 0.1158 0.5390 0.068 Uiso 1 1 calc R . . H3B2 H -0.0780 0.0373 0.5773 0.068 Uiso 1 1 calc R . . C4 C -0.1236(4) 0.2975(2) 0.92126(16) 0.0482(7) Uani 1 1 d . . . H4 H -0.1965 0.3473 0.9423 0.058 Uiso 1 1 calc R . . C4A C 0.4293(4) 0.3620(2) 0.79524(16) 0.0514(7) Uani 1 1 d . . . H4A1 H 0.5314 0.3164 0.7871 0.062 Uiso 1 1 calc R . . H4A2 H 0.3764 0.3514 0.8490 0.062 Uiso 1 1 calc R . . C4B C 0.0419(4) 0.12443(17) 0.66320(16) 0.0464(7) Uani 1 1 d . . . H4B1 H -0.0497 0.1085 0.7051 0.056 Uiso 1 1 calc R . . H4B2 H 0.1534 0.0850 0.6715 0.056 Uiso 1 1 calc R . . C5 C -0.1248(4) 0.2090(2) 0.95891(16) 0.0490(7) Uani 1 1 d . . . H5 H -0.2008 0.1984 1.0043 0.059 Uiso 1 1 calc R . . C6 C -0.0135(4) 0.13725(15) 0.92898(13) 0.0409(5) Uani 1 1 d . . . C7 C 0.0970(4) 0.15027(17) 0.86108(14) 0.0364(5) Uani 1 1 d . . . H7 H 0.1722 0.1002 0.8420 0.044 Uiso 1 1 calc R . . Br1 Br -0.01110(5) 0.015602(18) 0.982447(16) 0.06238(14) Uani 1 1 d . . . N1A N 0.2821(3) 0.34663(14) 0.73329(11) 0.0366(5) Uani 1 1 d . . . N1B N 0.0929(3) 0.22573(14) 0.66915(12) 0.0348(4) Uani 1 1 d . . . O1 O -0.0177(4) 0.40169(12) 0.81922(12) 0.0488(5) Uani 1 1 d . . . O1A O 0.5832(3) 0.48215(17) 0.71186(13) 0.0715(6) Uani 1 1 d . . . O1B O -0.2001(3) 0.16256(15) 0.56477(12) 0.0618(6) Uani 1 1 d . . . H1O H 0.063(4) 0.402(2) 0.7918(19) 0.050(10) 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 C1 0.0312(11) 0.0373(13) 0.0321(12) 0.0019(10) 0.0015(10) 0.0033(10) C1A 0.0465(16) 0.0641(18) 0.0344(14) 0.0060(12) 0.0019(12) -0.0086(13) C1B 0.0417(14) 0.0475(14) 0.0388(14) 0.0000(11) -0.0038(11) 0.0072(11) C2 0.0319(12) 0.0335(12) 0.0308(11) -0.0017(9) -0.0029(10) -0.0007(10) C2A 0.067(2) 0.074(2) 0.0464(16) 0.0143(14) -0.0001(14) -0.0262(16) C2B 0.0551(17) 0.0586(18) 0.0443(16) 0.0029(13) -0.0100(13) 0.0111(14) C3 0.0387(13) 0.0350(11) 0.0385(12) -0.0008(8) 0.0004(13) 0.0018(12) C3A 0.0647(18) 0.0826(19) 0.0468(15) 0.0066(13) -0.0083(17) -0.032(2) C3B 0.080(2) 0.0434(13) 0.0452(15) -0.0054(11) -0.0059(16) -0.0115(16) C4 0.0466(15) 0.0559(16) 0.0422(15) -0.0055(12) 0.0075(13) 0.0118(13) C4A 0.0454(15) 0.0703(18) 0.0385(14) 0.0052(13) -0.0042(12) -0.0187(13) C4B 0.061(2) 0.0337(12) 0.0445(14) 0.0009(10) -0.0025(14) 0.0006(12) C5 0.0476(15) 0.0614(17) 0.0379(14) 0.0029(12) 0.0092(12) -0.0038(13) C6 0.0493(14) 0.0398(11) 0.0335(11) 0.0058(8) -0.0051(13) -0.0118(14) C7 0.0412(13) 0.0337(12) 0.0342(13) -0.0004(10) -0.0043(11) 0.0023(11) Br1 0.0996(3) 0.04490(16) 0.04260(17) 0.01021(10) -0.00302(18) -0.01696(17) N1A 0.0362(11) 0.0438(11) 0.0297(11) 0.0036(9) 0.0009(9) -0.0063(9) N1B 0.0368(11) 0.0334(10) 0.0340(10) 0.0007(8) -0.0012(9) 0.0034(9) O1 0.0614(13) 0.0345(9) 0.0504(11) 0.0011(7) 0.0104(12) 0.0105(10) O1A 0.0628(12) 0.0971(16) 0.0545(13) 0.0156(12) -0.0056(10) -0.0417(12) O1B 0.0677(13) 0.0641(13) 0.0535(12) 0.0013(10) -0.0183(11) -0.0165(11) _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 C1 N1B 1.451(3) . ? C1 N1A 1.478(3) . ? C1 C2 1.520(3) . ? C1 H1 0.9800 . ? C1A N1A 1.468(3) . ? C1A C2A 1.499(4) . ? C1A H1A1 0.9700 . ? C1A H1A2 0.9700 . ? C1B N1B 1.457(3) . ? C1B C2B 1.509(4) . ? C1B H1B1 0.9700 . ? C1B H1B2 0.9700 . ? C2 C7 1.391(3) . ? C2 C3 1.407(3) . ? C2A O1A 1.419(3) . ? C2A H2A1 0.9700 . ? C2A H2A2 0.9700 . ? C2B O1B 1.416(4) . ? C2B H2B1 0.9700 . ? C2B H2B2 0.9700 . ? C3 O1 1.357(3) . ? C3 C4 1.377(3) . ? C3A O1A 1.417(3) . ? C3A C4A 1.504(4) . ? C3A H3A1 0.9700 . ? C3A H3A2 0.9700 . ? C3B O1B 1.409(4) . ? C3B C4B 1.508(4) . ? C3B H3B1 0.9700 . ? C3B H3B2 0.9700 . ? C4 C5 1.378(4) . ? C4 H4 0.9300 . ? C4A N1A 1.470(3) . ? C4A H4A1 0.9700 . ? C4A H4A2 0.9700 . ? C4B N1B 1.459(3) . ? C4B H4B1 0.9700 . ? C4B H4B2 0.9700 . ? C5 C6 1.363(4) . ? C5 H5 0.9300 . ? C6 C7 1.373(3) . ? C6 Br1 1.908(2) . ? C7 H7 0.9300 . ? O1 H1O 0.73(3) . ? 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 N1B C1 N1A 109.63(17) . . ? N1B C1 C2 114.26(19) . . ? N1A C1 C2 110.33(18) . . ? N1B C1 H1 107.5 . . ? N1A C1 H1 107.5 . . ? C2 C1 H1 107.5 . . ? N1A C1A C2A 109.5(2) . . ? N1A C1A H1A1 109.8 . . ? C2A C1A H1A1 109.8 . . ? N1A C1A H1A2 109.8 . . ? C2A C1A H1A2 109.8 . . ? H1A1 C1A H1A2 108.2 . . ? N1B C1B C2B 108.4(2) . . ? N1B C1B H1B1 110.0 . . ? C2B C1B H1B1 110.0 . . ? N1B C1B H1B2 110.0 . . ? C2B C1B H1B2 110.0 . . ? H1B1 C1B H1B2 108.4 . . ? C7 C2 C3 118.1(2) . . ? C7 C2 C1 119.6(2) . . ? C3 C2 C1 122.1(2) . . ? O1A C2A C1A 112.3(2) . . ? O1A C2A H2A1 109.2 . . ? C1A C2A H2A1 109.1 . . ? O1A C2A H2A2 109.1 . . ? C1A C2A H2A2 109.1 . . ? H2A1 C2A H2A2 107.9 . . ? O1B C2B C1B 111.1(2) . . ? O1B C2B H2B1 109.4 . . ? C1B C2B H2B1 109.4 . . ? O1B C2B H2B2 109.4 . . ? C1B C2B H2B2 109.4 . . ? H2B1 C2B H2B2 108.0 . . ? O1 C3 C4 117.7(2) . . ? O1 C3 C2 121.9(2) . . ? C4 C3 C2 120.4(2) . . ? O1A C3A C4A 111.9(2) . . ? O1A C3A H3A1 109.2 . . ? C4A C3A H3A1 109.2 . . ? O1A C3A H3A2 109.2 . . ? C4A C3A H3A2 109.2 . . ? H3A1 C3A H3A2 107.9 . . ? O1B C3B C4B 111.5(2) . . ? O1B C3B H3B1 109.3 . . ? C4B C3B H3B1 109.3 . . ? O1B C3B H3B2 109.3 . . ? C4B C3B H3B2 109.3 . . ? H3B1 C3B H3B2 108.0 . . ? C3 C4 C5 120.4(2) . . ? C3 C4 H4 119.8 . . ? C5 C4 H4 119.8 . . ? N1A C4A C3A 110.3(2) . . ? N1A C4A H4A1 109.6 . . ? C3A C4A H4A1 109.6 . . ? N1A C4A H4A2 109.6 . . ? C3A C4A H4A2 109.6 . . ? H4A1 C4A H4A2 108.1 . . ? N1B C4B C3B 109.7(2) . . ? N1B C4B H4B1 109.7 . . ? C3B C4B H4B1 109.7 . . ? N1B C4B H4B2 109.7 . . ? C3B C4B H4B2 109.7 . . ? H4B1 C4B H4B2 108.2 . . ? C6 C5 C4 119.4(2) . . ? C6 C5 H5 120.3 . . ? C4 C5 H5 120.3 . . ? C5 C6 C7 121.6(2) . . ? C5 C6 Br1 119.35(19) . . ? C7 C6 Br1 119.07(19) . . ? C6 C7 C2 120.2(2) . . ? C6 C7 H7 119.9 . . ? C2 C7 H7 119.9 . . ? C1A N1A C4A 107.46(19) . . ? C1A N1A C1 113.2(2) . . ? C4A N1A C1 109.90(19) . . ? C1 N1B C1B 116.58(19) . . ? C1 N1B C4B 113.57(19) . . ? C1B N1B C4B 108.8(2) . . ? C3 O1 H1O 104(3) . . ? C3A O1A C2A 109.4(2) . . ? C3B O1B C2B 110.5(2) . . ? 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 N1B C1 C2 C7 89.4(3) . . . . ? N1A C1 C2 C7 -146.6(2) . . . . ? N1B C1 C2 C3 -85.7(3) . . . . ? N1A C1 C2 C3 38.3(3) . . . . ? N1A C1A C2A O1A 60.0(3) . . . . ? N1B C1B C2B O1B 60.4(3) . . . . ? C7 C2 C3 O1 177.2(2) . . . . ? C1 C2 C3 O1 -7.6(4) . . . . ? C7 C2 C3 C4 -1.1(4) . . . . ? C1 C2 C3 C4 174.1(2) . . . . ? O1 C3 C4 C5 -179.0(3) . . . . ? C2 C3 C4 C5 -0.5(4) . . . . ? O1A C3A C4A N1A -58.8(3) . . . . ? O1B C3B C4B N1B -57.4(3) . . . . ? C3 C4 C5 C6 1.8(4) . . . . ? C4 C5 C6 C7 -1.4(4) . . . . ? C4 C5 C6 Br1 178.7(2) . . . . ? C5 C6 C7 C2 -0.3(4) . . . . ? Br1 C6 C7 C2 179.61(18) . . . . ? C3 C2 C7 C6 1.5(4) . . . . ? C1 C2 C7 C6 -173.8(2) . . . . ? C2A C1A N1A C4A -58.4(3) . . . . ? C2A C1A N1A C1 -180.0(2) . . . . ? C3A C4A N1A C1A 58.2(3) . . . . ? C3A C4A N1A C1 -178.2(2) . . . . ? N1B C1 N1A C1A -46.5(3) . . . . ? C2 C1 N1A C1A -173.2(2) . . . . ? N1B C1 N1A C4A -166.68(19) . . . . ? C2 C1 N1A C4A 66.6(2) . . . . ? N1A C1 N1B C1B -64.1(3) . . . . ? C2 C1 N1B C1B 60.3(3) . . . . ? N1A C1 N1B C4B 168.2(2) . . . . ? C2 C1 N1B C4B -67.4(3) . . . . ? C2B C1B N1B C1 170.3(2) . . . . ? C2B C1B N1B C4B -59.8(3) . . . . ? C3B C4B N1B C1 -169.8(2) . . . . ? C3B C4B N1B C1B 58.6(3) . . . . ? C4A C3A O1A C2A 57.0(4) . . . . ? C1A C2A O1A C3A -58.0(3) . . . . ? C4B C3B O1B C2B 57.0(3) . . . . ? C1B C2B O1B C3B -58.8(3) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.305 _refine_diff_density_min -0.284 _refine_diff_density_rms 0.040 # Attachment '4d.txt' data_oma8am _database_code_depnum_ccdc_archive 'CCDC 750437' #TrackingRef '4d.txt' _audit_creation_method SHELXL-97 _publ_suggested_journal 'Green Chemistry' _publ_section_abstract ; The solventless microwave assisted synthesis, among aldehydes (1a, 2b-h) and morpholine (3) in 1:2 (aldehyde:morpholine) ratios, yielded eight 4, 4`-Dimorfolyl-Methanes (4a-4h), which were thoroughly characterized through FT-IR, 1H, 13C and 2D NMR confirming structures of type 4. Described compounds are dimorpholino-methane (4a), 2-(dimorpholinomethyl)-phenol (4b), 4-bromo-2-(dimorpholinomethyl)-phenol (4c), 2,4-di-tert-butyl-6-(dimorpholinomethyl)-phenol (4d), 4,4'-(pyridin-2-ylmethylene)-dimorpholine (4e), 4,4'-((4-iso-propylphenyl)methylene)-dimorpholine (4f), 4,4'-(naphthalen-1-ylmethylene)-dimorpholine (4g) and 4,4'-(pyren-1-ylmethylene)-dimorpholine (4h). Additionally, single crystal X-ray diffraction analysis for 4b, 4c, 4d and 4e derivatives was accomplished. The obtained 4, 4`-dimorfolyl-methanes were subjected for two biological tests, i) acute toxicity, related to Photobacterium phosphoreum (Vibrio fischeri), and ii) biocidal activities, determined for B. subtilis, E. coli and Ps. fluorescence st ; _chemical_name_systematic ; 2,4-di-tert-butyl-6-(dimorpholinomethyl)phenol ; _chemical_name_common 2,4-di-tert-butyl-6-(dimorpholinomethyl)phenol _chemical_melting_point ? _chemical_formula_moiety 'C23 H38 N2 O3' _chemical_formula_sum 'C23 H38 N2 O3' _chemical_formula_weight 390.55 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 'P 21/n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 11.637(8) _cell_length_b 10.801(7) _cell_length_c 19.312(13) _cell_angle_alpha 90.00 _cell_angle_beta 103.443(10) _cell_angle_gamma 90.00 _cell_volume 2361(3) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 25 _cell_measurement_theta_min 1 _cell_measurement_theta_max 25 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.46 _exptl_crystal_size_min 0.42 _exptl_crystal_density_meas 1.099 _exptl_crystal_density_diffrn 1.099 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 856 _exptl_absorpt_coefficient_mu ? _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 18627 _diffrn_reflns_av_R_equivalents 0.0385 _diffrn_reflns_av_sigmaI/netI 0.0300 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.87 _diffrn_reflns_theta_max 24.00 _reflns_number_total 3634 _reflns_number_gt 2999 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1986)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' _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. One of the tert-butyl groups of the structure was refined as positional disorder within two occupancy sites, whereas the Fvar value resulted 0.74181. Never- theless the disordered structure posesses high anisotropy in this residue, mainly in one of the modeled orientations, the part B of the model. Therefore DELU restraints for the two orientations was carried on with the list "C12 C13A C13B C14A C15B C15A C15B", as well as the SIMU restraint to the list "C12 C13A C13B C14A C15B C15A C15B" and finally the ISOR restraint for the C13A. These details were simplified and placed within the experimental part of the manuscript. The hydrogen atoms in this moiety were refined as AFIX instruction restraints leading the coordinates to be refined as free variables. ; _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^)+(0.0545P)^2^+0.4230P] 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 3634 _refine_ls_number_parameters 286 _refine_ls_number_restraints 55 _refine_ls_R_factor_all 0.0613 _refine_ls_R_factor_gt 0.0504 _refine_ls_wR_factor_ref 0.1313 _refine_ls_wR_factor_gt 0.1241 _refine_ls_goodness_of_fit_ref 1.049 _refine_ls_restrained_S_all 1.048 _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 C1 C 0.59676(14) 0.74046(15) 0.12802(9) 0.0456(4) Uani 1 1 d . . . H1 H 0.6527 0.8014 0.1543 0.055 Uiso 1 1 calc R . . C1A C 0.61130(17) 0.86234(16) 0.02619(10) 0.0600(5) Uani 1 1 d . . . H1A1 H 0.6735 0.9116 0.0557 0.072 Uiso 1 1 calc R . . H1A2 H 0.5361 0.9003 0.0272 0.072 Uiso 1 1 calc R . . C1B C 0.5484(2) 0.51941(18) 0.13826(12) 0.0746(6) Uani 1 1 d . . . H1B1 H 0.5350 0.5122 0.0869 0.090 Uiso 1 1 calc R . . H1B2 H 0.4730 0.5340 0.1500 0.090 Uiso 1 1 calc R . . C2 C 0.47357(14) 0.78731(14) 0.12782(8) 0.0438(4) Uani 1 1 d . . . C2A C 0.6266(2) 0.8608(2) -0.04869(12) 0.0733(6) Uani 1 1 d . . . H2A1 H 0.5609 0.8169 -0.0788 0.088 Uiso 1 1 calc R . . H2A2 H 0.6256 0.9451 -0.0661 0.088 Uiso 1 1 calc R . . C2B C 0.6026(3) 0.4015(2) 0.17309(15) 0.1053(9) Uani 1 1 d . . . H2B1 H 0.5487 0.3333 0.1572 0.126 Uiso 1 1 calc R . . H2B2 H 0.6751 0.3846 0.1582 0.126 Uiso 1 1 calc R . . C3 C 0.37420(14) 0.75840(15) 0.07414(8) 0.0450(4) Uani 1 1 d . . . C3A C 0.73926(19) 0.6814(2) -0.02504(12) 0.0738(6) Uani 1 1 d . . . H3A1 H 0.8137 0.6435 -0.0276 0.089 Uiso 1 1 calc R . . H3A2 H 0.6761 0.6321 -0.0536 0.089 Uiso 1 1 calc R . . C3B C 0.7015(3) 0.5091(3) 0.27241(13) 0.1095(10) Uani 1 1 d . . . H3B1 H 0.7773 0.4959 0.2608 0.131 Uiso 1 1 calc R . . H3B2 H 0.7148 0.5141 0.3238 0.131 Uiso 1 1 calc R . . C4 C 0.26231(14) 0.80088(15) 0.07775(9) 0.0494(4) Uani 1 1 d . . . C4A C 0.72824(16) 0.68090(18) 0.05073(11) 0.0610(5) Uani 1 1 d . . . H4A1 H 0.7327 0.5966 0.0684 0.073 Uiso 1 1 calc R . . H4A2 H 0.7927 0.7276 0.0801 0.073 Uiso 1 1 calc R . . C4B C 0.6495(2) 0.6296(2) 0.24004(11) 0.0815(7) Uani 1 1 d . . . H4B1 H 0.5762 0.6464 0.2541 0.098 Uiso 1 1 calc R . . H4B2 H 0.7040 0.6969 0.2570 0.098 Uiso 1 1 calc R . . C5 C 0.25563(16) 0.87123(16) 0.13705(10) 0.0558(5) Uani 1 1 d . . . H5 H 0.1815 0.8987 0.1406 0.067 Uiso 1 1 calc R . . C6 C 0.35165(16) 0.90308(16) 0.19100(9) 0.0539(5) Uani 1 1 d . A . C7 C 0.45985(15) 0.86004(15) 0.18429(9) 0.0495(4) Uani 1 1 d . . . H7 H 0.5266 0.8807 0.2192 0.059 Uiso 1 1 calc R . . C8 C 0.15284(15) 0.77604(18) 0.01773(11) 0.0608(5) Uani 1 1 d . . . C9 C 0.13460(19) 0.6368(2) 0.00537(13) 0.0815(7) Uani 1 1 d . . . H9A H 0.1251 0.5980 0.0484 0.122 Uiso 1 1 calc R . . H9B H 0.2021 0.6021 -0.0082 0.122 Uiso 1 1 calc R . . H9C H 0.0652 0.6228 -0.0318 0.122 Uiso 1 1 calc R . . C10 C 0.1679(2) 0.8394(2) -0.05015(12) 0.0854(7) Uani 1 1 d . . . H10A H 0.1790 0.9267 -0.0417 0.128 Uiso 1 1 calc R . . H10B H 0.0986 0.8259 -0.0875 0.128 Uiso 1 1 calc R . . H10C H 0.2355 0.8056 -0.0640 0.128 Uiso 1 1 calc R . . C11 C 0.04129(18) 0.8283(3) 0.03582(15) 0.0959(8) Uani 1 1 d . . . H11A H 0.0295 0.7897 0.0784 0.144 Uiso 1 1 calc R . . H11B H -0.0256 0.8120 -0.0027 0.144 Uiso 1 1 calc R . . H11C H 0.0499 0.9161 0.0431 0.144 Uiso 1 1 calc R . . C12 C 0.3406(2) 0.9834(2) 0.25432(11) 0.0739(6) Uani 1 1 d U . . C13A C 0.3917(10) 0.9081(6) 0.3226(2) 0.150(3) Uani 0.742(11) 1 d PU A 1 H13A H 0.3468 0.8334 0.3221 0.225 Uiso 0.742(11) 1 calc PR A 1 H13B H 0.3874 0.9565 0.3636 0.225 Uiso 0.742(11) 1 calc PR A 1 H13C H 0.4726 0.8875 0.3244 0.225 Uiso 0.742(11) 1 calc PR A 1 C14A C 0.4084(6) 1.1008(4) 0.2534(3) 0.1079(18) Uani 0.742(11) 1 d PU A 1 H14A H 0.4894 1.0815 0.2547 0.162 Uiso 0.742(11) 1 calc PR A 1 H14B H 0.4043 1.1501 0.2941 0.162 Uiso 0.742(11) 1 calc PR A 1 H14C H 0.3750 1.1461 0.2107 0.162 Uiso 0.742(11) 1 calc PR A 1 C15A C 0.2149(5) 1.0198(8) 0.2529(4) 0.154(4) Uani 0.742(11) 1 d PU A 1 H15A H 0.1681 0.9467 0.2532 0.232 Uiso 0.742(11) 1 calc PR A 1 H15B H 0.1831 1.0669 0.2106 0.232 Uiso 0.742(11) 1 calc PR A 1 H15C H 0.2134 1.0691 0.2941 0.232 Uiso 0.742(11) 1 calc PR A 1 C13B C 0.253(3) 1.0884(19) 0.2263(9) 0.169(9) Uani 0.258(11) 1 d PU A 2 H13D H 0.2816 1.1365 0.1921 0.254 Uiso 0.258(11) 1 calc PR A 2 H13E H 0.2451 1.1405 0.2652 0.254 Uiso 0.258(11) 1 calc PR A 2 H13F H 0.1773 1.0537 0.2042 0.254 Uiso 0.258(11) 1 calc PR A 2 C14B C 0.294(2) 0.9150(10) 0.3046(7) 0.098(5) Uani 0.258(11) 1 d P A 2 H14D H 0.3425 0.8440 0.3202 0.147 Uiso 0.258(11) 1 calc PR A 2 H14E H 0.2149 0.8884 0.2828 0.147 Uiso 0.258(11) 1 calc PR A 2 H14F H 0.2920 0.9667 0.3448 0.147 Uiso 0.258(11) 1 calc PR A 2 C15B C 0.4624(17) 1.036(3) 0.2965(14) 0.156(10) Uani 0.258(11) 1 d PU A 2 H15D H 0.4982 1.0827 0.2648 0.233 Uiso 0.258(11) 1 calc PR A 2 H15E H 0.5134 0.9687 0.3164 0.233 Uiso 0.258(11) 1 calc PR A 2 H15F H 0.4502 1.0887 0.3341 0.233 Uiso 0.258(11) 1 calc PR A 2 N1A N 0.61520(11) 0.73619(12) 0.05499(7) 0.0478(4) Uani 1 1 d . . . N1B N 0.62737(12) 0.62144(13) 0.16308(7) 0.0498(4) Uani 1 1 d . . . O1 O 0.38624(12) 0.69018(12) 0.01651(6) 0.0578(4) Uani 1 1 d . . . O1A O 0.73407(14) 0.80303(15) -0.05360(9) 0.0856(5) Uani 1 1 d . . . O1B O 0.6274(2) 0.40841(19) 0.24785(11) 0.1202(7) Uani 1 1 d . . . H1O H 0.467(2) 0.692(2) 0.0194(11) 0.079(7) 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 C1 0.0420(9) 0.0433(9) 0.0497(10) -0.0067(7) 0.0072(7) -0.0013(7) C1A 0.0671(12) 0.0485(10) 0.0695(12) 0.0037(9) 0.0260(10) 0.0006(9) C1B 0.0838(14) 0.0542(12) 0.0775(14) 0.0098(10) 0.0016(11) -0.0079(10) C2 0.0466(9) 0.0404(9) 0.0439(9) 0.0006(7) 0.0095(7) 0.0011(7) C2A 0.0844(15) 0.0694(13) 0.0730(14) 0.0107(11) 0.0324(11) 0.0026(11) C2B 0.148(2) 0.0576(14) 0.0943(19) 0.0145(13) -0.0048(17) -0.0002(14) C3 0.0481(9) 0.0443(9) 0.0430(9) 0.0002(7) 0.0112(7) 0.0019(7) C3A 0.0729(14) 0.0733(14) 0.0863(15) -0.0039(11) 0.0411(12) 0.0065(11) C3B 0.152(3) 0.092(2) 0.0658(15) 0.0097(14) -0.0122(15) 0.0431(19) C4 0.0461(9) 0.0478(9) 0.0551(11) 0.0115(8) 0.0136(8) 0.0037(7) C4A 0.0505(10) 0.0620(12) 0.0749(13) -0.0021(9) 0.0232(9) 0.0057(8) C4B 0.1074(17) 0.0727(14) 0.0541(12) 0.0027(10) -0.0023(11) 0.0255(12) C5 0.0533(10) 0.0539(11) 0.0676(12) 0.0109(9) 0.0287(9) 0.0114(8) C6 0.0670(12) 0.0482(10) 0.0535(11) 0.0039(8) 0.0280(9) 0.0054(8) C7 0.0569(10) 0.0482(10) 0.0431(9) -0.0018(7) 0.0111(8) 0.0001(8) C8 0.0439(10) 0.0627(12) 0.0711(12) 0.0170(9) 0.0037(8) 0.0001(8) C9 0.0685(13) 0.0739(14) 0.0911(16) 0.0104(12) -0.0038(11) -0.0157(11) C10 0.0738(14) 0.0994(17) 0.0712(14) 0.0318(13) -0.0072(11) -0.0093(12) C11 0.0482(12) 0.111(2) 0.122(2) 0.0200(16) 0.0065(12) 0.0104(12) C12 0.0998(16) 0.0666(13) 0.0672(13) -0.0092(10) 0.0436(12) 0.0070(11) C13A 0.265(10) 0.137(4) 0.055(2) 0.002(2) 0.051(4) 0.079(6) C14A 0.150(5) 0.080(3) 0.110(4) -0.042(2) 0.064(3) -0.014(3) C15A 0.115(3) 0.200(8) 0.175(7) -0.095(7) 0.089(4) -0.001(4) C13B 0.28(2) 0.136(14) 0.123(10) -0.002(9) 0.106(11) 0.118(15) C14B 0.179(15) 0.061(6) 0.070(7) 0.000(5) 0.063(9) 0.023(8) C15B 0.154(10) 0.19(2) 0.148(17) -0.135(16) 0.082(9) -0.069(11) N1A 0.0468(8) 0.0457(8) 0.0539(8) -0.0007(6) 0.0176(6) 0.0024(6) N1B 0.0499(8) 0.0477(8) 0.0487(8) -0.0013(6) 0.0050(6) 0.0046(6) O1 0.0510(8) 0.0699(8) 0.0501(7) -0.0151(6) 0.0070(6) 0.0004(6) O1A 0.0884(11) 0.0899(11) 0.0939(11) 0.0093(9) 0.0522(9) 0.0015(8) O1B 0.175(2) 0.0845(13) 0.0970(14) 0.0360(11) 0.0238(13) 0.0263(13) _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 C1 N1B 1.458(2) . ? C1 N1A 1.476(2) . ? C1 C2 1.519(2) . ? C1 H1 0.9800 . ? C1A N1A 1.468(2) . ? C1A C2A 1.498(3) . ? C1A H1A1 0.9700 . ? C1A H1A2 0.9700 . ? C1B N1B 1.443(2) . ? C1B C2B 1.508(3) . ? C1B H1B1 0.9700 . ? C1B H1B2 0.9700 . ? C2 C7 1.383(2) . ? C2 C3 1.397(2) . ? C2A O1A 1.420(3) . ? C2A H2A1 0.9700 . ? C2A H2A2 0.9700 . ? C2B O1B 1.407(3) . ? C2B H2B1 0.9700 . ? C2B H2B2 0.9700 . ? C3 O1 1.369(2) . ? C3 C4 1.397(2) . ? C3A O1A 1.421(3) . ? C3A C4A 1.498(3) . ? C3A H3A1 0.9700 . ? C3A H3A2 0.9700 . ? C3B O1B 1.400(4) . ? C3B C4B 1.508(3) . ? C3B H3B1 0.9700 . ? C3B H3B2 0.9700 . ? C4 C5 1.391(3) . ? C4 C8 1.534(3) . ? C4A N1A 1.464(2) . ? C4A H4A1 0.9700 . ? C4A H4A2 0.9700 . ? C4B N1B 1.451(3) . ? C4B H4B1 0.9700 . ? C4B H4B2 0.9700 . ? C5 C6 1.382(3) . ? C5 H5 0.9300 . ? C6 C7 1.376(3) . ? C6 C12 1.529(3) . ? C7 H7 0.9300 . ? C8 C10 1.525(3) . ? C8 C11 1.529(3) . ? C8 C9 1.530(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 . ? C11 H11A 0.9600 . ? C11 H11B 0.9600 . ? C11 H11C 0.9600 . ? C12 C14B 1.426(11) . ? C12 C14A 1.496(5) . ? C12 C15A 1.510(5) . ? C12 C13B 1.538(16) . ? C12 C13A 1.545(6) . ? C12 C15B 1.568(16) . ? C13A H13A 0.9600 . ? C13A H13B 0.9600 . ? C13A H13C 0.9600 . ? C14A H14A 0.9600 . ? C14A H14B 0.9600 . ? C14A H14C 0.9600 . ? C15A H15A 0.9600 . ? C15A H15B 0.9600 . ? C15A H15C 0.9600 . ? C13B H13D 0.9600 . ? C13B H13E 0.9600 . ? C13B H13F 0.9600 . ? C14B H14D 0.9600 . ? C14B H14E 0.9600 . ? C14B H14F 0.9600 . ? C15B H15D 0.9600 . ? C15B H15E 0.9600 . ? C15B H15F 0.9600 . ? O1 H1O 0.92(2) . ? 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 N1B C1 N1A 110.00(13) . . ? N1B C1 C2 115.05(13) . . ? N1A C1 C2 110.77(13) . . ? N1B C1 H1 106.9 . . ? N1A C1 H1 106.9 . . ? C2 C1 H1 106.9 . . ? N1A C1A C2A 110.81(15) . . ? N1A C1A H1A1 109.5 . . ? C2A C1A H1A1 109.5 . . ? N1A C1A H1A2 109.5 . . ? C2A C1A H1A2 109.5 . . ? H1A1 C1A H1A2 108.1 . . ? N1B C1B C2B 109.23(18) . . ? N1B C1B H1B1 109.8 . . ? C2B C1B H1B1 109.8 . . ? N1B C1B H1B2 109.8 . . ? C2B C1B H1B2 109.8 . . ? H1B1 C1B H1B2 108.3 . . ? C7 C2 C3 118.99(15) . . ? C7 C2 C1 117.97(14) . . ? C3 C2 C1 123.03(14) . . ? O1A C2A C1A 111.94(18) . . ? O1A C2A H2A1 109.2 . . ? C1A C2A H2A1 109.2 . . ? O1A C2A H2A2 109.2 . . ? C1A C2A H2A2 109.2 . . ? H2A1 C2A H2A2 107.9 . . ? O1B C2B C1B 112.2(2) . . ? O1B C2B H2B1 109.2 . . ? C1B C2B H2B1 109.2 . . ? O1B C2B H2B2 109.2 . . ? C1B C2B H2B2 109.2 . . ? H2B1 C2B H2B2 107.9 . . ? O1 C3 C2 120.01(15) . . ? O1 C3 C4 119.34(15) . . ? C2 C3 C4 120.64(15) . . ? O1A C3A C4A 112.15(17) . . ? O1A C3A H3A1 109.2 . . ? C4A C3A H3A1 109.2 . . ? O1A C3A H3A2 109.2 . . ? C4A C3A H3A2 109.2 . . ? H3A1 C3A H3A2 107.9 . . ? O1B C3B C4B 112.0(2) . . ? O1B C3B H3B1 109.2 . . ? C4B C3B H3B1 109.2 . . ? O1B C3B H3B2 109.2 . . ? C4B C3B H3B2 109.2 . . ? H3B1 C3B H3B2 107.9 . . ? C5 C4 C3 116.83(16) . . ? C5 C4 C8 121.47(16) . . ? C3 C4 C8 121.65(16) . . ? N1A C4A C3A 109.60(16) . . ? N1A C4A H4A1 109.8 . . ? C3A C4A H4A1 109.8 . . ? N1A C4A H4A2 109.8 . . ? C3A C4A H4A2 109.8 . . ? H4A1 C4A H4A2 108.2 . . ? N1B C4B C3B 109.31(18) . . ? N1B C4B H4B1 109.8 . . ? C3B C4B H4B1 109.8 . . ? N1B C4B H4B2 109.8 . . ? C3B C4B H4B2 109.8 . . ? H4B1 C4B H4B2 108.3 . . ? C6 C5 C4 124.48(16) . . ? C6 C5 H5 117.8 . . ? C4 C5 H5 117.8 . . ? C7 C6 C5 116.22(16) . . ? C7 C6 C12 121.04(18) . . ? C5 C6 C12 122.73(17) . . ? C6 C7 C2 122.81(16) . . ? C6 C7 H7 118.6 . . ? C2 C7 H7 118.6 . . ? C10 C8 C11 107.69(17) . . ? C10 C8 C9 110.30(19) . . ? C11 C8 C9 107.71(18) . . ? C10 C8 C4 109.28(15) . . ? C11 C8 C4 111.28(19) . . ? C9 C8 C4 110.53(15) . . ? 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 . . ? C8 C11 H11A 109.5 . . ? C8 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C8 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C14B C12 C14A 137.2(6) . . ? C14B C12 C15A 67.9(7) . . ? C14A C12 C15A 106.9(4) . . ? C14B C12 C6 111.6(5) . . ? C14A C12 C6 109.2(2) . . ? C15A C12 C6 113.3(3) . . ? C14B C12 C13B 107.0(10) . . ? C14A C12 C13B 71.3(12) . . ? C15A C12 C13B 40.5(9) . . ? C6 C12 C13B 108.0(6) . . ? C14B C12 C13A 43.9(7) . . ? C14A C12 C13A 110.9(4) . . ? C15A C12 C13A 109.4(4) . . ? C6 C12 C13A 107.2(2) . . ? C13B C12 C13A 141.3(6) . . ? C14B C12 C15B 106.1(10) . . ? C14A C12 C15B 44.2(12) . . ? C15A C12 C15B 132.1(7) . . ? C6 C12 C15B 112.8(5) . . ? C13B C12 C15B 111.2(13) . . ? C13A C12 C15B 68.0(11) . . ? C12 C13A H13A 109.5 . . ? C12 C13A H13B 109.5 . . ? H13A C13A H13B 109.5 . . ? C12 C13A H13C 109.5 . . ? H13A C13A H13C 109.5 . . ? H13B C13A H13C 109.5 . . ? C12 C14A H14A 109.5 . . ? C12 C14A H14B 109.5 . . ? H14A C14A H14B 109.5 . . ? C12 C14A H14C 109.5 . . ? H14A C14A H14C 109.5 . . ? H14B C14A H14C 109.5 . . ? C12 C15A H15A 109.5 . . ? C12 C15A H15B 109.5 . . ? H15A C15A H15B 109.5 . . ? C12 C15A H15C 109.5 . . ? H15A C15A H15C 109.5 . . ? H15B C15A H15C 109.5 . . ? C12 C13B H13D 109.5 . . ? C12 C13B H13E 109.5 . . ? H13D C13B H13E 109.5 . . ? C12 C13B H13F 109.5 . . ? H13D C13B H13F 109.5 . . ? H13E C13B H13F 109.5 . . ? C12 C14B H14D 109.5 . . ? C12 C14B H14E 109.5 . . ? H14D C14B H14E 109.5 . . ? C12 C14B H14F 109.5 . . ? H14D C14B H14F 109.5 . . ? H14E C14B H14F 109.5 . . ? C12 C15B H15D 109.5 . . ? C12 C15B H15E 109.5 . . ? H15D C15B H15E 109.5 . . ? C12 C15B H15F 109.5 . . ? H15D C15B H15F 109.5 . . ? H15E C15B H15F 109.5 . . ? C4A N1A C1A 107.83(14) . . ? C4A N1A C1 113.49(13) . . ? C1A N1A C1 109.54(13) . . ? C1B N1B C4B 109.54(17) . . ? C1B N1B C1 116.82(14) . . ? C4B N1B C1 112.83(14) . . ? C3 O1 H1O 103.4(13) . . ? C2A O1A C3A 109.81(15) . . ? C3B O1B C2B 110.6(2) . . ? 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 N1B C1 C2 C7 89.76(18) . . . . ? N1A C1 C2 C7 -144.71(14) . . . . ? N1B C1 C2 C3 -89.05(19) . . . . ? N1A C1 C2 C3 36.5(2) . . . . ? N1A C1A C2A O1A -57.6(2) . . . . ? N1B C1B C2B O1B 57.6(3) . . . . ? C7 C2 C3 O1 177.73(14) . . . . ? C1 C2 C3 O1 -3.5(2) . . . . ? C7 C2 C3 C4 -0.8(2) . . . . ? C1 C2 C3 C4 178.00(15) . . . . ? O1 C3 C4 C5 -179.12(14) . . . . ? C2 C3 C4 C5 -0.6(2) . . . . ? O1 C3 C4 C8 -1.7(2) . . . . ? C2 C3 C4 C8 176.84(15) . . . . ? O1A C3A C4A N1A 59.8(2) . . . . ? O1B C3B C4B N1B -57.8(3) . . . . ? C3 C4 C5 C6 1.3(3) . . . . ? C8 C4 C5 C6 -176.14(16) . . . . ? C4 C5 C6 C7 -0.5(3) . . . . ? C4 C5 C6 C12 178.42(17) . . . . ? C5 C6 C7 C2 -1.0(2) . . . . ? C12 C6 C7 C2 -179.94(16) . . . . ? C3 C2 C7 C6 1.6(2) . . . . ? C1 C2 C7 C6 -177.22(15) . . . . ? C5 C4 C8 C10 114.2(2) . . . . ? C3 C4 C8 C10 -63.1(2) . . . . ? C5 C4 C8 C11 -4.6(2) . . . . ? C3 C4 C8 C11 178.07(17) . . . . ? C5 C4 C8 C9 -124.3(2) . . . . ? C3 C4 C8 C9 58.4(2) . . . . ? C7 C6 C12 C14B -104.8(10) . . . . ? C5 C6 C12 C14B 76.3(10) . . . . ? C7 C6 C12 C14A 61.9(4) . . . . ? C5 C6 C12 C14A -117.0(4) . . . . ? C7 C6 C12 C15A -179.1(5) . . . . ? C5 C6 C12 C15A 2.0(5) . . . . ? C7 C6 C12 C13B 137.8(14) . . . . ? C5 C6 C12 C13B -41.1(14) . . . . ? C7 C6 C12 C13A -58.4(5) . . . . ? C5 C6 C12 C13A 122.8(5) . . . . ? C7 C6 C12 C15B 14.5(15) . . . . ? C5 C6 C12 C15B -164.4(15) . . . . ? C3A C4A N1A C1A -58.1(2) . . . . ? C3A C4A N1A C1 -179.63(15) . . . . ? C2A C1A N1A C4A 57.5(2) . . . . ? C2A C1A N1A C1 -178.51(15) . . . . ? N1B C1 N1A C4A -46.29(18) . . . . ? C2 C1 N1A C4A -174.60(13) . . . . ? N1B C1 N1A C1A -166.85(13) . . . . ? C2 C1 N1A C1A 64.83(17) . . . . ? C2B C1B N1B C4B -58.0(2) . . . . ? C2B C1B N1B C1 172.18(19) . . . . ? C3B C4B N1B C1B 58.2(3) . . . . ? C3B C4B N1B C1 -169.9(2) . . . . ? N1A C1 N1B C1B -71.01(19) . . . . ? C2 C1 N1B C1B 54.9(2) . . . . ? N1A C1 N1B C4B 160.71(16) . . . . ? C2 C1 N1B C4B -73.36(19) . . . . ? C1A C2A O1A C3A 56.1(2) . . . . ? C4A C3A O1A C2A -57.5(2) . . . . ? C4B C3B O1B C2B 56.6(3) . . . . ? C1B C2B O1B C3B -56.5(3) . . . . ? _diffrn_measured_fraction_theta_max 0.980 _diffrn_reflns_theta_full 24.00 _diffrn_measured_fraction_theta_full 0.980 _refine_diff_density_max 0.127 _refine_diff_density_min -0.123 _refine_diff_density_rms 0.026 # Attachment '4e.txt' data_vic24a1 _database_code_depnum_ccdc_archive 'CCDC 750438' #TrackingRef '4e.txt' _audit_creation_method SHELXL-97 _publ_suggested_journal 'Green Chemistry' _publ_section_abstract ; The solventless microwave assisted synthesis, among aldehydes (1a, 2b-h) and morpholine (3) in 1:2 (aldehyde:morpholine) ratios, yielded eight 4, 4`-Dimorfolyl-Methanes (4a-4h), which were thoroughly characterized through FT-IR, 1H, 13C and 2D NMR confirming structures of type 4. Described compounds are dimorpholino-methane (4a), 2-(dimorpholinomethyl)-phenol (4b), 4-bromo-2-(dimorpholinomethyl)-phenol (4c), 2,4-di-tert-butyl-6-(dimorpholinomethyl)-phenol (4d), 4,4'-(pyridin-2-ylmethylene)-dimorpholine (4e), 4,4'-((4-iso-propylphenyl)methylene)-dimorpholine (4f), 4,4'-(naphthalen-1-ylmethylene)-dimorpholine (4g) and 4,4'-(pyren-1-ylmethylene)-dimorpholine (4h). Additionally, single crystal X-ray diffraction analysis for 4b, 4c, 4d and 4e derivatives was accomplished. The obtained 4, 4`-dimorfolyl-methanes were subjected for two biological tests, i) acute toxicity, related to Photobacterium phosphoreum (Vibrio fischeri), and ii) biocidal activities, determined for B. subtilis, E. coli and Ps. fluorescence st ; _chemical_name_systematic ; 4,4'-(pyridin-2-ylmethylene)dimorpholine ; _chemical_name_common 4,4'-(pyridin-2-ylmethylene)dimorpholine _chemical_melting_point ? _chemical_formula_moiety 'C14 H21 N3 O2' _chemical_formula_sum 'C14 H21 N3 O2' _chemical_formula_weight 263.34 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 'P 1 21/c 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 15.067(3) _cell_length_b 10.150(2) _cell_length_c 9.665(2) _cell_angle_alpha 90.00 _cell_angle_beta 104.544(4) _cell_angle_gamma 90.00 _cell_volume 1430.8(5) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 2237 _cell_measurement_theta_min 24.00 _cell_measurement_theta_max 1.40 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.36 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.223 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 568 _exptl_absorpt_coefficient_mu 0.083 _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 8409 _diffrn_reflns_av_R_equivalents 0.0272 _diffrn_reflns_av_sigmaI/netI 0.0250 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 1.40 _diffrn_reflns_theta_max 24.00 _reflns_number_total 2232 _reflns_number_gt 1864 _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 'Ortep-3 for Windows (Farrugia, 1997)' _computing_publication_material 'WinGX publication routines (Farrugia, 1999)' _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^)+(0.0408P)^2^+0.3022P] 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 refxyz _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2232 _refine_ls_number_parameters 172 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0592 _refine_ls_R_factor_gt 0.0474 _refine_ls_wR_factor_ref 0.1097 _refine_ls_wR_factor_gt 0.1036 _refine_ls_goodness_of_fit_ref 1.125 _refine_ls_restrained_S_all 1.125 _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 C1 C 0.76808(12) 0.49550(18) 0.67614(18) 0.0470(5) Uani 1 1 d . . . H1 H 0.7889 0.4076 0.6565 0.056 Uiso 1 1 calc R . . C1A C 0.80925(14) 0.4364(2) 0.9267(2) 0.0647(6) Uani 1 1 d . . . H1A1 H 0.8630 0.4923 0.9415 0.078 Uiso 1 1 calc R . . H1A2 H 0.8264 0.3486 0.9032 0.078 Uiso 1 1 calc R . . C1B C 0.70167(14) 0.4947(2) 0.4175(2) 0.0599(5) Uani 1 1 d . . . H1B1 H 0.7211 0.4036 0.4185 0.072 Uiso 1 1 calc R . . H1B2 H 0.7482 0.5495 0.3930 0.072 Uiso 1 1 calc R . . C2 C 0.84865(12) 0.58897(18) 0.69381(18) 0.0481(5) Uani 1 1 d . . . C2A C 0.77660(15) 0.4312(2) 1.0616(2) 0.0700(6) Uani 1 1 d . . . H2A1 H 0.8255 0.3975 1.1389 0.084 Uiso 1 1 calc R . . H2A2 H 0.7620 0.5196 1.0869 0.084 Uiso 1 1 calc R . . C2B C 0.61199(16) 0.5126(3) 0.3089(2) 0.0721(6) Uani 1 1 d . . . H2B1 H 0.6193 0.4890 0.2152 0.087 Uiso 1 1 calc R . . H2B2 H 0.5667 0.4539 0.3313 0.087 Uiso 1 1 calc R . . C3 C 0.85268(14) 0.7067(2) 0.7679(2) 0.0597(5) Uani 1 1 d . . . H3 H 0.8075 0.7274 0.8146 0.072 Uiso 1 1 calc R . . C3A C 0.62820(14) 0.3966(2) 0.9300(2) 0.0670(6) Uani 1 1 d . . . H3A1 H 0.6095 0.4838 0.9526 0.080 Uiso 1 1 calc R . . H3A2 H 0.5755 0.3387 0.9177 0.080 Uiso 1 1 calc R . . C3B C 0.57021(14) 0.6807(2) 0.4430(2) 0.0663(6) Uani 1 1 d . . . H3B1 H 0.5241 0.6253 0.4679 0.080 Uiso 1 1 calc R . . H3B2 H 0.5493 0.7713 0.4404 0.080 Uiso 1 1 calc R . . C4 C 0.92344(15) 0.7920(2) 0.7718(2) 0.0701(6) Uani 1 1 d . . . H4 H 0.9268 0.8718 0.8201 0.084 Uiso 1 1 calc R . . C4A C 0.65715(13) 0.4027(2) 0.7919(2) 0.0581(5) Uani 1 1 d . . . H4A1 H 0.6716 0.3148 0.7648 0.070 Uiso 1 1 calc R . . H4A2 H 0.6072 0.4370 0.7167 0.070 Uiso 1 1 calc R . . C4B C 0.65914(14) 0.66701(19) 0.5555(2) 0.0577(5) Uani 1 1 d . . . H4B1 H 0.7047 0.7260 0.5344 0.069 Uiso 1 1 calc R . . H4B2 H 0.6502 0.6903 0.6483 0.069 Uiso 1 1 calc R . . C5 C 0.98911(15) 0.7577(2) 0.7033(2) 0.0722(6) Uani 1 1 d . . . H5 H 1.0382 0.8135 0.7046 0.087 Uiso 1 1 calc R . . C6 C 0.98136(14) 0.6399(2) 0.6328(2) 0.0669(6) Uani 1 1 d . . . H6 H 1.0265 0.6175 0.5867 0.080 Uiso 1 1 calc R . . N1 N 0.91245(10) 0.55462(16) 0.62636(17) 0.0558(4) Uani 1 1 d . . . N1A N 0.73757(9) 0.48775(14) 0.80878(15) 0.0472(4) Uani 1 1 d . . . N1B N 0.69075(10) 0.53128(14) 0.55743(14) 0.0454(4) Uani 1 1 d . . . O1A O 0.69869(10) 0.35057(14) 1.04587(14) 0.0693(4) Uani 1 1 d . . . O1B O 0.57985(10) 0.64461(17) 0.30562(15) 0.0756(5) 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 C1 0.0537(11) 0.0430(10) 0.0493(10) -0.0019(8) 0.0224(9) -0.0001(9) C1A 0.0599(12) 0.0778(15) 0.0580(12) 0.0135(11) 0.0177(10) 0.0024(11) C1B 0.0663(13) 0.0701(14) 0.0499(11) -0.0086(10) 0.0271(10) -0.0034(11) C2 0.0494(11) 0.0525(11) 0.0450(10) 0.0034(8) 0.0165(8) -0.0012(9) C2A 0.0705(14) 0.0870(17) 0.0510(12) 0.0129(11) 0.0126(10) 0.0010(13) C2B 0.0791(15) 0.0970(19) 0.0434(11) -0.0118(11) 0.0209(11) -0.0083(14) C3 0.0624(12) 0.0612(13) 0.0593(12) -0.0097(10) 0.0227(10) -0.0096(11) C3A 0.0680(14) 0.0829(16) 0.0562(13) 0.0057(11) 0.0270(11) -0.0109(12) C3B 0.0709(14) 0.0636(14) 0.0645(14) 0.0046(10) 0.0172(11) 0.0043(11) C4 0.0757(15) 0.0676(15) 0.0652(13) -0.0098(11) 0.0145(11) -0.0225(12) C4A 0.0619(12) 0.0656(13) 0.0521(11) 0.0000(9) 0.0242(10) -0.0149(10) C4B 0.0651(12) 0.0534(12) 0.0563(12) -0.0044(9) 0.0185(10) -0.0001(10) C5 0.0583(13) 0.0842(17) 0.0719(14) 0.0065(13) 0.0124(11) -0.0249(12) C6 0.0490(12) 0.0908(17) 0.0648(14) 0.0091(12) 0.0213(10) -0.0050(12) N1 0.0483(9) 0.0648(11) 0.0593(10) 0.0039(8) 0.0226(8) 0.0012(8) N1A 0.0492(9) 0.0524(9) 0.0430(8) 0.0019(7) 0.0173(7) -0.0035(7) N1B 0.0543(9) 0.0446(9) 0.0418(8) -0.0054(6) 0.0203(7) -0.0033(7) O1A 0.0851(11) 0.0711(10) 0.0577(9) 0.0147(7) 0.0292(8) -0.0009(8) O1B 0.0795(10) 0.0952(12) 0.0521(9) 0.0171(8) 0.0169(8) -0.0048(9) _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 C1 N1B 1.461(2) . ? C1 N1A 1.469(2) . ? C1 C2 1.516(2) . ? C1 H1 0.9800 . ? C1A N1A 1.455(2) . ? C1A C2A 1.506(3) . ? C1A H1A1 0.9700 . ? C1A H1A2 0.9700 . ? C1B N1B 1.451(2) . ? C1B C2B 1.499(3) . ? C1B H1B1 0.9700 . ? C1B H1B2 0.9700 . ? C2 N1 1.336(2) . ? C2 C3 1.386(3) . ? C2A O1A 1.407(2) . ? C2A H2A1 0.9700 . ? C2A H2A2 0.9700 . ? C2B O1B 1.422(3) . ? C2B H2B1 0.9700 . ? C2B H2B2 0.9700 . ? C3 C4 1.367(3) . ? C3 H3 0.9300 . ? C3A O1A 1.415(2) . ? C3A C4A 1.506(2) . ? C3A H3A1 0.9700 . ? C3A H3A2 0.9700 . ? C3B O1B 1.419(2) . ? C3B C4B 1.505(3) . ? C3B H3B1 0.9700 . ? C3B H3B2 0.9700 . ? C4 C5 1.367(3) . ? C4 H4 0.9300 . ? C4A N1A 1.463(2) . ? C4A H4A1 0.9700 . ? C4A H4A2 0.9700 . ? C4B N1B 1.456(2) . ? C4B H4B1 0.9700 . ? C4B H4B2 0.9700 . ? C5 C6 1.367(3) . ? C5 H5 0.9300 . ? C6 N1 1.341(2) . ? C6 H6 0.9300 . ? 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 N1B C1 N1A 109.64(13) . . ? N1B C1 C2 113.02(14) . . ? N1A C1 C2 110.64(14) . . ? N1B C1 H1 107.8 . . ? N1A C1 H1 107.8 . . ? C2 C1 H1 107.8 . . ? N1A C1A C2A 110.53(16) . . ? N1A C1A H1A1 109.5 . . ? C2A C1A H1A1 109.5 . . ? N1A C1A H1A2 109.5 . . ? C2A C1A H1A2 109.5 . . ? H1A1 C1A H1A2 108.1 . . ? N1B C1B C2B 109.16(15) . . ? N1B C1B H1B1 109.8 . . ? C2B C1B H1B1 109.8 . . ? N1B C1B H1B2 109.8 . . ? C2B C1B H1B2 109.8 . . ? H1B1 C1B H1B2 108.3 . . ? N1 C2 C3 122.22(17) . . ? N1 C2 C1 115.82(16) . . ? C3 C2 C1 121.84(16) . . ? O1A C2A C1A 111.86(18) . . ? O1A C2A H2A1 109.2 . . ? C1A C2A H2A1 109.2 . . ? O1A C2A H2A2 109.2 . . ? C1A C2A H2A2 109.2 . . ? H2A1 C2A H2A2 107.9 . . ? O1B C2B C1B 111.82(18) . . ? O1B C2B H2B1 109.3 . . ? C1B C2B H2B1 109.3 . . ? O1B C2B H2B2 109.3 . . ? C1B C2B H2B2 109.3 . . ? H2B1 C2B H2B2 107.9 . . ? C4 C3 C2 119.57(19) . . ? C4 C3 H3 120.2 . . ? C2 C3 H3 120.2 . . ? O1A C3A C4A 112.83(17) . . ? O1A C3A H3A1 109.0 . . ? C4A C3A H3A1 109.0 . . ? O1A C3A H3A2 109.0 . . ? C4A C3A H3A2 109.0 . . ? H3A1 C3A H3A2 107.8 . . ? O1B C3B C4B 111.72(16) . . ? O1B C3B H3B1 109.3 . . ? C4B C3B H3B1 109.3 . . ? O1B C3B H3B2 109.3 . . ? C4B C3B H3B2 109.3 . . ? H3B1 C3B H3B2 107.9 . . ? C5 C4 C3 118.6(2) . . ? C5 C4 H4 120.7 . . ? C3 C4 H4 120.7 . . ? N1A C4A C3A 109.99(16) . . ? N1A C4A H4A1 109.7 . . ? C3A C4A H4A1 109.7 . . ? N1A C4A H4A2 109.7 . . ? C3A C4A H4A2 109.7 . . ? H4A1 C4A H4A2 108.2 . . ? N1B C4B C3B 109.02(16) . . ? N1B C4B H4B1 109.9 . . ? C3B C4B H4B1 109.9 . . ? N1B C4B H4B2 109.9 . . ? C3B C4B H4B2 109.9 . . ? H4B1 C4B H4B2 108.3 . . ? C6 C5 C4 118.9(2) . . ? C6 C5 H5 120.6 . . ? C4 C5 H5 120.6 . . ? N1 C6 C5 123.8(2) . . ? N1 C6 H6 118.1 . . ? C5 C6 H6 118.1 . . ? C2 N1 C6 116.90(18) . . ? C1A N1A C4A 107.86(15) . . ? C1A N1A C1 111.66(14) . . ? C4A N1A C1 111.50(14) . . ? C1B N1B C4B 110.06(15) . . ? C1B N1B C1 114.43(14) . . ? C4B N1B C1 116.05(14) . . ? C2A O1A C3A 109.49(15) . . ? C3B O1B C2B 109.67(15) . . ? 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 N1B C1 C2 N1 -92.84(18) . . . . ? N1A C1 C2 N1 143.78(16) . . . . ? N1B C1 C2 C3 83.2(2) . . . . ? N1A C1 C2 C3 -40.1(2) . . . . ? N1A C1A C2A O1A 59.5(2) . . . . ? N1B C1B C2B O1B 58.4(2) . . . . ? N1 C2 C3 C4 0.6(3) . . . . ? C1 C2 C3 C4 -175.17(18) . . . . ? C2 C3 C4 C5 -0.7(3) . . . . ? O1A C3A C4A N1A -57.7(2) . . . . ? O1B C3B C4B N1B -58.2(2) . . . . ? C3 C4 C5 C6 0.4(3) . . . . ? C4 C5 C6 N1 0.1(3) . . . . ? C3 C2 N1 C6 -0.2(3) . . . . ? C1 C2 N1 C6 175.85(16) . . . . ? C5 C6 N1 C2 -0.1(3) . . . . ? C2A C1A N1A C4A -57.9(2) . . . . ? C2A C1A N1A C1 179.26(16) . . . . ? C3A C4A N1A C1A 56.8(2) . . . . ? C3A C4A N1A C1 179.69(16) . . . . ? N1B C1 N1A C1A 172.80(15) . . . . ? C2 C1 N1A C1A -61.89(19) . . . . ? N1B C1 N1A C4A 52.06(19) . . . . ? C2 C1 N1A C4A 177.37(15) . . . . ? C2B C1B N1B C4B -58.0(2) . . . . ? C2B C1B N1B C1 169.24(16) . . . . ? C3B C4B N1B C1B 57.84(19) . . . . ? C3B C4B N1B C1 -170.20(14) . . . . ? N1A C1 N1B C1B -157.89(15) . . . . ? C2 C1 N1B C1B 78.18(19) . . . . ? N1A C1 N1B C4B 72.21(18) . . . . ? C2 C1 N1B C4B -51.72(19) . . . . ? C1A C2A O1A C3A -56.9(2) . . . . ? C4A C3A O1A C2A 56.7(2) . . . . ? C4B C3B O1B C2B 57.9(2) . . . . ? C1B C2B O1B C3B -58.0(2) . . . . ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 24.00 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.130 _refine_diff_density_min -0.106 _refine_diff_density_rms 0.027