Supplementary Material (ESI) for Journal of Materials Chemistry This journal is © The Royal Society of Chemistry 2004 data_global #================================================================== #============ _audit_creation_date 17-04-01 _journal_coden_Cambridge 1145 loop_ _publ_author_name 'Ziessel Raymond' 'Frank H. Kohler' 'Gabriele Raudaschl-Sieber' 'Christophe Stroh' 'Phillipe Turek' _publ_contact_author_name 'Dr Ziessel Raymond' _publ_contact_author_address ; Chimie CNRS 25 rue Becquerel Strasbourg 67089 FRANCE ; _publ_contact_author_email ZIESSEL@CHIMIE.U-STRASBG.FR _publ_requested_journal 'Journal of Materials Chemistry' _publ_section_title ; Intramolecular exchange interactions in non-aromatic bis-nitronyl-nitroxides ; _publ_contact_author_phone '33 3 90 24 26 89' _publ_contact_author_fax '33 3 90 24 26 89' _publ_requested_category FM _publ_section_abstract ; Nitronyl-nitroxide (NIT) biradicals linked by conjugated but non-aromatic spacers have been engineered and investigated in the solid state by a combination of X-ray diffraction, magnetic susceptibility measurement, EPR as well as solid-state 1H and 13C NMR spectroscopies, and experimental electron density distribution. All techniques reveal that double and triple bonds are very efficient coupling units for exchange interactions between two radical moieties. Using a Bleaney-Bowers model for a dimer, a singlet-triplet energy gap of J = -460 K was found with the singlet state being the ground state. This very strong intra-molecular interaction was confirmed by the EPR spectra of the biradicals both dissolved in CH2Cl2 and dispersed in a polymer matrix at low concentration. Increasing the number of double bonds of the linker resulted in a progressive decrease of the intramolecular interaction down to J = -88 K for three double bonds (3D-NIT2), and to J = -69 K for alternating double/triple/double bonds in DTD-NIT2. Strong intermolecular exchange interactions were excluded by studying a model compound, which consisted of a given linker but only one nitronyl-nitroxide moiety (3D-NIT). In keeping with the unusual interactions, all solid-state NMR signals of the biradicals were found to be considerably less shifted than expected from the monoradicals. Temperature?dependent solid-state 13C NMR spectra of D-NIT2 confirmed the very strong intramolecular coupling constant (J = -504 K). The electron density distribution of D-NIT2 was measured by high resolution X-ray diffraction, which also revealed that this biradical is an ideally conjugated system. The in-depth characterization includes the deformation maps and the observed electron density ellipcities, which exhibit a pronounced s-p character of the O-N-C=C-N-O cores in keeping with an efficient electronic delocalisation along the alkene backbone. ; _publ_section_comment ? _publ_section_exptl_prep ? _publ_section_exptl_refinement ; The intensity data were collected in the phi scan mode at 294K for D-NIT2 and 3D-NIT2 and at 173 K for DTD-NIT2 and 3D-NIT on a KappaCCD diffractometer equipped with a graphite monochromator for the MoKa radiation. Cell constants were derived from a least-squares fit of the setting angles for 25 selected reflections with 10°<.<15°. The intensities were corrected for Lorentz and polarization effects but not for absorption. The atoms were located in a succession of difference Fourier syntheses and were refined with anisotropic thermal parameters using the SHELX76 and SHELX85 packages.43 The hydrogen atoms were included in the final refinement model in calculated and fixed positions with isotropic thermal parameters. Crystal structure and refinement data are summarized in Table 1. ; _publ_section_references ; Burla, M.C., Camalli, M., Cascarano, G.,Giacovazzo, C., Polidori, G., Spagna, R. &Viterbo, D. (1989). SIR. J. Appl. Cryst. 22, 389-393. OpenMoleN, Interactive Intelligent Structure solution (1997) Nonius B.V., Delft, The Netherlands. KappaCCD Operation Manual (1997), Nonius B.V., Delft, The Nederlands. Otwinowski, Z. & Minor, W. (1997), Methods in Enzymology, 276, 307-326. Walker, N. & Stuart, D. (1983). Acta Cryst., A39, 158-166. ; data_st886 _database_code_depnum_ccdc_archive 'CCDC 250191' #================================================================== # 5. CHEMICAL DATA _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety 'C16 H23 N2 O3' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C16 H23 N2 O3' _chemical_formula_weight 291.37 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C ? 0.002 0.002 International_Tables_Vol_IV_Table_2.3.1 H ? 0.000 0.000 International_Tables_Vol_IV_Table_2.3.1 N ? 0.004 0.003 International_Tables_Vol_IV_Table_2.3.1 O ? 0.008 0.006 International_Tables_Vol_IV_Table_2.3.1 #================================================================== # 6. CRYSTAL DATA _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P b c a' _symmetry_space_group_name_Hall '-P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz x,y,z 1/2-x,-y,1/2+z -x,1/2+y,1/2-z 1/2+x,1/2-y,-z -x,-y,-z 1/2+x,+y,1/2-z +x,1/2-y,1/2+z 1/2-x,1/2+y,+z _cell_length_a 11.2540(2) _cell_length_b 11.9432(2) _cell_length_c 23.8124(7) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 3200.6(1) _cell_formula_units_Z 8 _cell_measurement_temperature 173 _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _cell_special_details ; Cell parameters refined using Scalepack part of DENZO Z. Otwinowski, W. Minor, 1997 ; _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.21 _exptl_crystal_density_method none _exptl_crystal_F_000 1256 _exptl_absorpt_coefficient_mu 0.084 _exptl_absorpt_correction_type refdelf_(Walker_&_Stuart,_1983) _exptl_absorpt_correction_T_min 0.8580 _exptl_absorpt_correction_T_max 1.0000 #================================================================= # 7. EXPERIMENTAL DATA _diffrn_special_details ? _diffrn_ambient_temperature 173 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type Mo-K\a _diffrn_source xray_tube _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method '\p scans' _diffrn_measurement_details ; 7034 reflections were collected using program Collect ("Collect" Data collection software, Nonius B.V., 1998) The conditions were as follow : crystal to detector distance = 36. mm. Scan angle = 2.0 deg 1 scans of 60 sec per frame. Data collection was divided into 1 set(s) with the following starting angles and number of frames : Set 1 Theta = 6.30 Omega = 0.00 Kappa = 0.00 129 frames Friedel pairs were averaged. Internal R = 0.05 ; _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 7034 _diffrn_reflns_av_R_equivalents 0.050 _diffrn_reflns_av_sigmaI/netI 0.333 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 30 _diffrn_reflns_theta_min 2.5 _diffrn_reflns_theta_max 27.48 _reflns_number_total 4115 _reflns_number_gt 1899 _reflns_threshold_expression >3.0\s(I) _computing_structure_solution Direct_methods_(SIR,_Burla_et_al.,_1989) _computing_structure_refinement LSFM_OpenMoleN_(_1997) _computing_molecular_graphics ? _computing_publication_material CIFGEN_IN_OpenMoleN_(_1997) #================================================================== # 8. REFINEMENT DATA _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_hydrogen_treatment noref _refine_ls_extinction_method none _refine_ls_extinction_expression ? _refine_ls_extinction_coef ? _refine_ls_abs_structure_Flack ? _refine_ls_number_reflns 1899 _refine_ls_number_parameters 190 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_R_factor_all 0.089 _refine_ls_R_factor_gt 0.037 _refine_ls_wR_factor_all 0.510 _refine_ls_wR_factor_ref 0.058 _refine_ls_goodness_of_fit_all 8.845 _refine_ls_goodness_of_fit_ref 1.041 _refine_ls_shift/su_max 0.001 _refine_ls_shift/esd_mean 0.000 _refine_diff_density_max 0.219 _refine_diff_density_min -0.168 #================================================================== # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_calc_flag _atom_site_calc_attached_atom _atom_site_type_symbol C1 0.5006(2) 0.1045(2) 0.08885(8) 0.026(1) Uani ? ? C N1 0.3813(1) 0.1092(1) 0.09622(7) 0.0269(8) Uani ? ? N C2 0.3355(2) 0.2269(1) 0.09942(8) 0.027(1) Uani ? ? C C3 0.4375(2) 0.2890(1) 0.06746(9) 0.027(1) Uani ? ? C N2 0.5381(1) 0.2104(1) 0.07808(6) 0.0249(8) Uani ? ? N O1 0.3114(1) 0.0259(1) 0.10494(7) 0.0404(8) Uani ? ? O C4 0.2148(2) 0.2352(2) 0.07230(9) 0.035(1) Uani ? ? C C5 0.3282(2) 0.2571(2) 0.1612(1) 0.044(1) Uani ? ? C C6 0.4658(2) 0.4045(2) 0.0894(1) 0.043(1) Uani ? ? C C7 0.4203(2) 0.2905(2) 0.00404(9) 0.044(1) Uani ? ? C O2 0.6468(1) 0.2414(1) 0.07322(7) 0.0353(7) Uani ? ? O C8 0.5753(1) 0.0055(1) 0.09217(8) 0.0259(9) Uani ? ? C C9 0.6878(2) 0.0046(2) 0.05738(9) 0.036(1) Uani ? ? C C10 0.5417(2) -0.0787(2) 0.12593(8) 0.028(1) Uani ? ? C C11 0.6067(2) -0.1802(1) 0.13735(8) 0.029(1) Uani ? ? C C12 0.5642(2) -0.2601(2) 0.17160(8) 0.029(1) Uani ? ? C C13 0.6263(2) -0.3627(1) 0.18373(8) 0.030(1) Uani ? ? C C14 0.5822(2) -0.4500(2) 0.21206(8) 0.031(1) Uani ? ? C C15 0.4588(2) -0.4559(2) 0.23584(9) 0.045(1) Uani ? ? C C16 0.6581(2) -0.5486(2) 0.21764(9) 0.042(1) Uani ? ? C O3 0.6294(1) -0.6372(1) 0.23877(7) 0.060(1) Uani ? ? O H1 0.1870 0.3102 0.0747 0.0492 Uiso calc C4 H H2 0.2204 0.2138 0.0340 0.0492 Uiso calc C4 H H3 0.1608 0.1870 0.0912 0.0492 Uiso calc C4 H H4 0.2994 0.3314 0.1651 0.0574 Uiso calc C5 H H5 0.2757 0.2069 0.1797 0.0574 Uiso calc C5 H H6 0.4050 0.2517 0.1776 0.0574 Uiso calc C5 H H7 0.5283 0.4361 0.0678 0.0630 Uiso calc C6 H H8 0.3972 0.4505 0.0865 0.0630 Uiso calc C6 H H9 0.4896 0.3995 0.1275 0.0630 Uiso calc C6 H H10 0.4847 0.3291 -0.0130 0.0596 Uiso calc C7 H H11 0.4176 0.2158 -0.0096 0.0596 Uiso calc C7 H H12 0.3480 0.3275 -0.0048 0.0596 Uiso calc C7 H H13 0.7287 -0.0641 0.0631 0.0469 Uiso calc C9 H H14 0.6681 0.0121 0.0188 0.0469 Uiso calc C9 H H15 0.7373 0.0651 0.0685 0.0469 Uiso calc C9 H H16 0.4672 -0.0706 0.1443 0.0378 Uiso calc C10 H H17 0.6820 -0.1909 0.1201 0.0383 Uiso calc C11 H H18 0.4890 -0.2482 0.1888 0.0384 Uiso calc C12 H H19 0.7056 -0.3689 0.1704 0.0398 Uiso calc C13 H H20 0.4479 -0.5258 0.2541 0.0588 Uiso calc C15 H H21 0.4479 -0.3969 0.2621 0.0588 Uiso calc C15 H H22 0.4026 -0.4485 0.2063 0.0588 Uiso calc C15 H H23 0.7368 -0.5430 0.2035 0.0548 Uiso calc C16 H loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 _atom_site_aniso_type_symbol C1 0.0197(9) 0.027(1) 0.033(1) -0.0006(8) -0.0006(8) -0.0011(8) C N1 0.0199(7) 0.0224(7) 0.044(1) -0.0042(7) 0.0016(7) 0.0026(7) N C2 0.0221(9) 0.0267(9) 0.035(1) 0.0018(9) 0.0010(9) -0.0045(9) C C3 0.0190(8) 0.0251(9) 0.040(1) 0.0007(8) -0.0004(9) 0.0028(9) C N2 0.0164(7) 0.0267(8) 0.0354(9) -0.0041(7) -0.0019(7) 0.0007(7) N O1 0.0245(7) 0.0313(7) 0.086(1) -0.0051(6) 0.0061(7) 0.0054(8) O C4 0.0210(9) 0.037(1) 0.056(1) 0.0036(9) 0.003(1) -0.001(1) C C5 0.042(1) 0.049(1) 0.042(1) 0.006(1) 0.004(1) -0.004(1) C C6 0.034(1) 0.027(1) 0.085(2) 0.001(1) 0.003(1) -0.006(1) C C7 0.029(1) 0.063(1) 0.046(1) 0.007(1) 0.002(1) 0.017(1) C O2 0.0200(6) 0.0373(7) 0.0593(9) -0.0043(6) -0.0027(7) 0.0023(7) O C8 0.0213(9) 0.0250(9) 0.033(1) -0.0008(8) -0.0004(8) -0.0023(8) C C9 0.031(1) 0.032(1) 0.045(1) 0.002(1) 0.006(1) 0.001(1) C C10 0.0222(9) 0.0290(9) 0.036(1) -0.0006(8) 0.0006(9) -0.0025(9) C C11 0.0245(9) 0.0292(9) 0.035(1) 0.0035(9) 0.0009(9) -0.0019(9) C C12 0.0251(9) 0.031(1) 0.033(1) 0.0017(9) 0.0018(9) -0.0018(9) C C13 0.027(1) 0.033(1) 0.031(1) 0.0007(9) 0.0005(9) -0.0029(9) C C14 0.031(1) 0.031(1) 0.030(1) 0.0005(9) -0.0016(9) 0.0039(9) C C15 0.038(1) 0.047(1) 0.051(1) 0.003(1) 0.010(1) 0.012(1) C C16 0.035(1) 0.045(1) 0.046(1) 0.006(1) -0.002(1) 0.009(1) C O3 0.057(1) 0.0454(8) 0.084(1) 0.0091(8) 0.0102(9) 0.0342(8) O # 10. MOLECULAR GEOMETRY loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 N1 1.356(2) . . ? C1 N2 1.357(2) . . ? C1 C8 1.453(3) . . ? N1 C2 1.500(2) . . ? N1 N2 2.183(2) . . ? N1 O1 1.285(2) . . ? C2 C3 1.564(3) . . ? C2 C4 1.507(3) . . ? C2 C5 1.517(3) . . ? C3 N2 1.493(2) . . ? C3 C6 1.509(3) . . ? C3 C7 1.523(3) . . ? N2 O2 1.284(2) . . ? C8 C9 1.513(3) . . ? C8 C10 1.342(3) . . ? C10 C11 1.441(3) . . ? C11 C12 1.343(3) . . ? C12 C13 1.440(3) . . ? C13 C14 1.337(3) . . ? C14 C15 1.501(3) . . ? C14 C16 1.462(3) . . ? C16 O3 1.215(3) . . ? loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag ? ? ? ? ? ? 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 C1 N2 107.1(2) . . . ? N1 C1 C8 126.8(2) . . . ? N2 C1 C8 126.1(2) . . . ? C1 N1 C2 112.7(1) . . . ? C1 N1 N2 36.5(1) . . . ? C1 N1 O1 126.6(2) . . . ? C2 N1 N2 76.6(1) . . . ? C2 N1 O1 120.5(1) . . . ? N2 N1 O1 162.9(1) . . . ? N1 C2 C3 99.6(1) . . . ? N1 C2 C4 110.5(2) . . . ? N1 C2 C5 106.9(2) . . . ? C3 C2 C4 115.0(2) . . . ? C3 C2 C5 113.5(2) . . . ? C4 C2 C5 110.6(2) . . . ? C2 C3 N2 100.2(1) . . . ? C2 C3 C6 114.8(2) . . . ? C2 C3 C7 113.3(2) . . . ? N2 C3 C6 110.9(2) . . . ? N2 C3 C7 105.8(2) . . . ? C6 C3 C7 111.0(2) . . . ? C1 N2 N1 36.4(1) . . . ? C1 N2 C3 112.4(1) . . . ? C1 N2 O2 125.6(2) . . . ? N1 N2 C3 76.6(1) . . . ? N1 N2 O2 161.6(1) . . . ? C3 N2 O2 121.8(2) . . . ? C1 C8 C9 117.4(2) . . . ? C1 C8 C10 118.7(2) . . . ? C9 C8 C10 123.9(2) . . . ? C8 C10 C11 126.9(2) . . . ? C10 C11 C12 122.1(2) . . . ? C11 C12 C13 123.6(2) . . . ? C12 C13 C14 125.8(2) . . . ? C13 C14 C15 124.8(2) . . . ? C13 C14 C16 117.2(2) . . . ? C15 C14 C16 117.9(2) . . . ? C14 C16 O3 125.7(2) . . . ? data_ST035 _database_code_depnum_ccdc_archive 'CCDC 250192' #========================================================================== #==== # 5. CHEMICAL DATA _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety C22H34N4O4 _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum C22H34N4O4 _chemical_formula_weight 418.54 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C ? 0.002 0.002 International_Tables_Vol_IV_Table_2.3.1 H ? 0.000 0.000 International_Tables_Vol_IV_Table_2.3.1 N ? 0.004 0.003 International_Tables_Vol_IV_Table_2.3.1 O ? 0.008 0.006 International_Tables_Vol_IV_Table_2.3.1 #========================================================================== #==== # 6. CRYSTAL DATA _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/n 1' _symmetry_space_group_name_Hall '-P 2yn' loop_ _symmetry_equiv_pos_as_xyz x,y,z 1/2-x,1/2+y,1/2-z -x,-y,-z 1/2+x,1/2-y,1/2+z _cell_length_a 7.0087(4) _cell_length_b 16.270(1) _cell_length_c 10.3874(5) _cell_angle_alpha 90 _cell_angle_beta 99.244(4) _cell_angle_gamma 90 _cell_volume 1169.1(2) _cell_formula_units_z 2 _cell_measurement_temperature 294 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 18.2 _cell_measurement_theta_max 20.5 _cell_special_details ; ? ; _exptl_crystal_description prism _exptl_crystal_colour 'dark blue' _exptl_crystal_size_max 0.35 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.30 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.19 _exptl_crystal_density_method none _exptl_crystal_F_000 452 _exptl_absorpt_coefficient_mu 0.077 _exptl_absorpt_correction_type psi_scans_(North,_Phillips,_Mathews,_1968) _exptl_absorpt_correction_T_min 0.9841 _exptl_absorpt_correction_T_max 1.0000 #========================================================================== #==== # 7. EXPERIMENTAL DATA _diffrn_special_details ; ? ; _diffrn_ambient_temperature 294 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type Mo-K\a _diffrn_radiation_source xray_tube _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type Enraf_Nonius_CAD4 _diffrn_measurement_method \q/2\q _diffrn_standards_number 3 _diffrn_standards_interval_count ? _diffrn_standards_interval_time 120 _diffrn_standards_decay_% 0 loop_ _diffrn_standard_refln_index_h _diffrn_standard_refln_index_k _diffrn_standard_refln_index_l -1 -1 -5 -3 1 3 -1 -14 0 _diffrn_reflns_number 2587 _diffrn_reflns_av_R_equivalents 0.017 _diffrn_reflns_av_sigmaI/netI 0.333 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 0 _diffrn_reflns_theta_min 2.5 _diffrn_reflns_theta_max 26.29 _reflns_number_total 2456 _reflns_number_gt 1566 _reflns_threshold_expression >3.0\s(I) _computing_data_collection CAD4_(Enraf-Nonius,_1994) _computing_cell_refinement CAD4_(Enraf-Nonius,_1994) _computing_data_reduction process_MolEN_(Fair,_1990) _computing_structure_solution Direct_methods_(SIR,_Burla_et_al.,_1989) _computing_structure_refinement LSFM_MolEN_(Fair,_1990) _computing_molecular_graphics ? _computing_publication_material BTABLE_PTABLE_CIF_IN_MolEN_(Fair,_1990) #========================================================================== #==== # 8. REFINEMENT DATA _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_hydrogen_treatment noref _refine_ls_extinction_method none _refine_ls_extinction_expression ? _refine_ls_extinction_coef ? _refine_ls_abs_structure_Flack ? _refine_ls_number_reflns 1566 _refine_ls_number_parameters 136 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_abs_structure_details ; ? ; _refine_ls_R_factor_all 0.087 _refine_ls_R_factor_gt 0.048 _refine_ls_wR_factor_all 0.081 _refine_ls_wR_factor_ref 0.076 _refine_ls_goodness_of_fit_all 1.597 _refine_ls_goodness_of_fit_ref 1.556 _refine_ls_shift/su_max 0.002 _refine_ls_shift/esd_mean 0.000 _refine_diff_density_max 0.324 _refine_diff_density_min -0.293 #========================================================================== #==== # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_calc_flag _atom_site_calc_attached_atom _atom_site_type_symbol C1 1.0005(3) 0.0717(1) 0.7724(2) 0.0341(9) Uij ? ? C N1 0.9786(3) 0.1541(1) 0.7756(2) 0.0400(9) Uij ? ? N O1 0.8578(3) 0.1974(1) 0.6987(2) 0.063(1) Uij ? ? O C2 1.1003(3) 0.1929(1) 0.8929(2) 0.038(1) Uij ? ? C C3 1.2544(3) 0.1253(1) 0.9289(2) 0.038(1) Uij ? ? C N2 1.1465(2) 0.0511(1) 0.8694(2) 0.0361(8) Uij ? ? N O2 1.1981(2) -0.02124(9) 0.9061(2) 0.0528(9) Uij ? ? O C4 0.9690(4) 0.2052(2) 0.9946(3) 0.056(1) Uij ? ? C C5 1.1766(4) 0.2752(2) 0.8556(3) 0.056(1) Uij ? ? C C6 1.3195(4) 0.1115(2) 1.0726(3) 0.058(1) Uij ? ? C C7 1.4296(4) 0.1337(2) 0.8577(3) 0.068(2) Uij ? ? C C8 0.8927(3) 0.0148(1) 0.6805(2) 0.037(1) Uij ? ? C C9 0.9896(4) -0.0643(2) 0.6524(2) 0.050(1) Uij ? ? C C10 0.7138(3) 0.0367(1) 0.6213(2) 0.038(1) Uij ? ? C C11 0.5885(3) -0.0124(1) 0.5279(2) 0.041(1) Uij ? ? C H1 1.0404 0.2296 1.0704 0.0746 Uiso calc C4 H H2 0.8645 0.2401 0.9603 0.0746 Uiso calc C4 H H3 0.9200 0.1535 1.0166 0.0746 Uiso calc C4 H H4 1.2531 0.2992 0.9298 0.0789 Uiso calc C5 H H5 1.2534 0.2674 0.7891 0.0789 Uiso calc C5 H H6 1.0712 0.3104 0.8245 0.0789 Uiso calc C5 H H7 1.3875 0.1586 1.1096 0.0819 Uiso calc C6 H H8 1.2099 0.1024 1.1140 0.0819 Uiso calc C6 H H9 1.4021 0.0649 1.0849 0.0819 Uiso calc C6 H H10 1.5046 0.1799 0.8909 0.0937 Uiso calc C7 H H11 1.5064 0.0854 0.8712 0.0937 Uiso calc C7 H H12 1.3860 0.1409 0.7670 0.0937 Uiso calc C7 H H13 0.9041 -0.0957 0.5912 0.0655 Uiso calc C9 H H14 1.1038 -0.0524 0.6175 0.0655 Uiso calc C9 H H15 1.0222 -0.0947 0.7310 0.0655 Uiso calc C9 H H16 0.6668 0.0888 0.6431 0.0507 Uiso calc C10 H H17 0.6329 -0.0647 0.5047 0.0545 Uiso calc C11 H loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 _atom_site_aniso_type_symbol C1 0.0337(9) 0.031(1) 0.0380(9) -0.0027(8) -0.0017(8) 0.0014(9) C N1 0.0464(9) 0.0299(8) 0.046(1) -0.0042(7) -0.0173(8) 0.0039(8) N O1 0.089(1) 0.0351(8) 0.081(1) 0.0011(8) -0.0510(9) 0.0107(8) O C2 0.039(1) 0.031(1) 0.044(1) -0.0063(9) -0.0103(9) 0.0014(9) C C3 0.0341(9) 0.036(1) 0.045(1) -0.0051(8) -0.0069(9) 0.0007(9) C N2 0.0348(8) 0.0314(8) 0.0432(9) 0.0008(7) -0.0043(7) -0.0003(8) N O2 0.0611(9) 0.0333(8) 0.072(1) 0.0089(8) -0.0177(9) 0.0044(8) O C4 0.050(1) 0.049(1) 0.070(2) -0.000(1) 0.001(1) -0.011(1) C C5 0.071(1) 0.037(1) 0.065(2) -0.018(1) -0.016(1) 0.006(1) C C6 0.074(2) 0.051(1) 0.053(1) 0.007(1) -0.023(1) -0.002(1) C C7 0.042(1) 0.075(2) 0.100(2) -0.009(1) 0.014(1) -0.003(2) C C8 0.041(1) 0.034(1) 0.037(1) -0.0049(9) 0.0029(9) -0.0034(9) C C9 0.050(1) 0.048(1) 0.051(1) 0.005(1) 0.001(1) -0.011(1) C C10 0.038(1) 0.037(1) 0.040(1) -0.0051(9) 0.0002(9) -0.0086(9) C C11 0.042(1) 0.040(1) 0.042(1) -0.005(1) -0.0003(9) -0.0098(9) C # 10. MOLECULAR GEOMETRY loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 N1 1.350(2) . . ? C1 N2 1.358(2) . . ? C1 C8 1.452(2) . . ? N1 O1 1.277(2) . . ? N1 C2 1.509(2) . . ? C2 C3 1.544(2) . . ? C2 C4 1.521(2) . . ? C2 C5 1.514(2) . . ? C3 N2 1.504(2) . . ? C3 C6 1.507(2) . . ? C3 C7 1.538(2) . . ? N2 O2 1.272(1) . . ? C8 C9 1.506(2) . . ? C8 C10 1.353(2) . . ? C10 C11 1.441(2) . . ? loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag ? ? ? ? ? ? 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 C1 N2 107.6(1) . . . ? N1 C1 C8 126.9(1) . . . ? N2 C1 C8 125.5(1) . . . ? C1 N1 O1 126.8(1) . . . ? C1 N1 C2 112.5(1) . . . ? O1 N1 C2 120.4(1) . . . ? N1 C2 C3 100.4(1) . . . ? N1 C2 C4 106.8(1) . . . ? N1 C2 C5 109.9(1) . . . ? C3 C2 C4 113.8(1) . . . ? C3 C2 C5 115.4(1) . . . ? C4 C2 C5 109.9(1) . . . ? C2 C3 N2 100.8(1) . . . ? C2 C3 C6 115.8(1) . . . ? C2 C3 C7 113.7(1) . . . ? N2 C3 C6 109.8(1) . . . ? N2 C3 C7 105.1(1) . . . ? C6 C3 C7 110.6(1) . . . ? C1 N2 C3 112.0(1) . . . ? C1 N2 O2 126.6(1) . . . ? C3 N2 O2 121.3(1) . . . ? C1 C8 C9 118.0(1) . . . ? C1 C8 C10 118.5(1) . . . ? C9 C8 C10 123.5(1) . . . ? C8 C10 C11 125.5(1) . . . ? #CIFFILE DTD-NIT2 #========================================================================== data_st565 _database_code_depnum_ccdc_archive 'CCDC 250193' #========================================================================== #==== # 5. CHEMICAL DATA _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety 'C22 H32 N4 O4' _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C22 H32 N4 O4' _chemical_formula_weight 416.52 _chemical_melting_point ? _chemical_compound_source ? loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C ? 0.002 0.002 International_Tables_Vol_IV_Table_2.3.1 H ? 0.000 0.000 International_Tables_Vol_IV_Table_2.3.1 N ? 0.004 0.003 International_Tables_Vol_IV_Table_2.3.1 O ? 0.008 0.006 International_Tables_Vol_IV_Table_2.3.1 #========================================================================== #==== # 6. CRYSTAL DATA _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 1 21/n 1' _symmetry_space_group_name_Hall '-P 2yn' loop_ _symmetry_equiv_pos_as_xyz x,y,z 1/2-x,1/2+y,1/2-z -x,-y,-z 1/2+x,1/2-y,1/2+z _cell_length_a 10.3190(6) _cell_length_b 9.7704(8) _cell_length_c 12.3620(8) _cell_angle_alpha 90 _cell_angle_beta 113.394(6) _cell_angle_gamma 90 _cell_volume 1143.9(3) _cell_formula_units_Z 2 _cell_measurement_temperature 173 _cell_measurement_reflns_used 4429 _cell_measurement_theta_min 1.4 _cell_measurement_theta_max 27.4 _cell_special_details ; Cell parameters refined using Scalepack part of DENZO Z. Otwinowski, W. Minor, 1997 ; _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.21 _exptl_crystal_density_method none _exptl_crystal_F_000 448 _exptl_absorpt_coefficient_mu 0.084 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? #========================================================================== #==== # 7. EXPERIMENTAL DATA _diffrn_special_details ; ? ; _diffrn_ambient_temperature 173 _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type Mo-K\a _diffrn_source xray_tube _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type KappaCCD _diffrn_measurement_method '\p scans' _diffrn_measurement_details ; 4429 reflections were collected using program Collect ("Collect" Data collection software, Nonius B.V., 1998) The conditions were as follow : crystal to detector distance = 35. mm. Scan angle = 2.0 deg 1 scans of 40 sec per frame. Data collection was divided into 2 set(s) with the following starting angles and number of frames : Set 1 Theta = 6.00 Omega = 0.00 Kappa = 0.00 91 frames Set 2 Theta = -6.00 Kappa = 142.00 Phi = 0.00 25 frames Friedel pairs were averaged. Internal R = 0.05 ; _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0 _diffrn_reflns_number 4429 _diffrn_reflns_av_R_equivalents 0.050 _diffrn_reflns_av_sigmaI/netI 0.333 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -12 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.5 _diffrn_reflns_theta_max 27.42 _reflns_number_total 2763 _reflns_number_gt 1322 _reflns_threshold_expression >3.0\s(I) _computing_structure_solution Direct_methods_(SIR,_Burla_et_al.,_1989) _computing_structure_refinement LSFM_OpenMoleN_(_1997) _computing_molecular_graphics ? _computing_publication_material CIFGEN_IN_OpenMoleN_(_1997) #========================================================================== #==== # 8. REFINEMENT DATA _refine_ls_structure_factor_coef F _refine_ls_matrix_type full _refine_ls_weighting_scheme '4Fo^2^/(\s^2^(Fo^2^)+0.0004 Fo^4^)+0.2' _refine_ls_hydrogen_treatment noref _refine_ls_extinction_method none _refine_ls_extinction_expression ? _refine_ls_extinction_coef ? _refine_ls_abs_structure_Flack ? _refine_ls_number_reflns 1322 _refine_ls_number_parameters 145 _refine_ls_number_restraints 0 _refine_ls_number_constraints 0 _refine_ls_R_factor_all 0.112 _refine_ls_R_factor_gt 0.056 _refine_ls_wR_factor_all 0.106 _refine_ls_wR_factor_ref 0.072 _refine_ls_goodness_of_fit_all 1.573 _refine_ls_goodness_of_fit_ref 1.114 _refine_ls_shift/su_max 0.021 _refine_ls_shift/esd_mean 0.002 _refine_diff_density_max 0.373 _refine_diff_density_min -0.168 #========================================================================== #==== # 9. ATOMIC COORDINATES AND THERMAL PARAMETERS loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_thermal_displace_type _atom_site_calc_flag _atom_site_calc_attached_atom _atom_site_type_symbol C1 0.3971(3) 0.1249(3) 0.6134(3) 0.039(1) 1.000 Uani ? ? C N1 0.2692(2) 0.0847(3) 0.6078(2) 0.039(1) 1.000 Uani ? ? N O1 0.1556(2) 0.1567(2) 0.5713(2) 0.054(1) 1.000 Uani ? ? O C2 0.2696(3) -0.0638(3) 0.6409(3) 0.041(1) 1.000 Uani ? ? C C3 0.4286(3) -0.0845(3) 0.7173(2) 0.041(1) 1.000 Uani ? ? C N2 0.4905(2) 0.0220(3) 0.6634(2) 0.043(1) 1.000 Uani ? ? N O2 0.6192(2) 0.0169(3) 0.6745(2) 0.064(1) 1.000 Uani ? ? O C4 0.2159(4) -0.1427(4) 0.5243(3) 0.056(2) 1.000 Uani ? ? C C5 0.1718(3) -0.0860(4) 0.7046(3) 0.064(2) 1.000 Uani ? ? C C6 0.4716(4) -0.0427(4) 0.8462(3) 0.056(2) 1.000 Uani ? ? C C7 0.4858(3) -0.2255(4) 0.7090(3) 0.057(2) 1.000 Uani ? ? C C8 0.4310(3) 0.2572(4) 0.5750(3) 0.047(1) 1.000 Uani ? ? C C9 0.5698(4) 0.3110(4) 0.6371(4) 0.080(2) 1.000 Uani ? ? C C10 0.5884(6) 0.4280(7) 0.5770(6) 0.044(3) 0.500 Uani ? ? C C11 0.3206(4) 0.3257(4) 0.4779(3) 0.081(2) 1.000 Uani ? ? C C12 0.3784(6) 0.4624(7) 0.4557(5) 0.045(3) 0.500 Uani ? ? C H1 0.2137 -0.2377 0.5396 0.0772 1.000 Uiso calc C4 H H2 0.1234 -0.1123 0.4760 0.0772 1.000 Uiso calc C4 H H3 0.2772 -0.1268 0.4851 0.0772 1.000 Uiso calc C4 H H4 0.1730 -0.1799 0.7250 0.0791 1.000 Uiso calc C5 H H5 0.2030 -0.0319 0.7742 0.0791 1.000 Uiso calc C5 H H6 0.0784 -0.0601 0.6545 0.0791 1.000 Uiso calc C5 H H7 0.4350 -0.1070 0.8844 0.0766 1.000 Uiso calc C6 H H8 0.5717 -0.0407 0.8846 0.0766 1.000 Uiso calc C6 H H9 0.4348 0.0456 0.8497 0.0766 1.000 Uiso calc C6 H H10 0.5836 -0.2292 0.7583 0.0743 1.000 Uiso calc C7 H H11 0.4367 -0.2926 0.7336 0.0743 1.000 Uiso calc C7 H H12 0.4730 -0.2429 0.6298 0.0743 1.000 Uiso calc C7 H loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 _atom_site_aniso_type_symbol C1 0.036(1) 0.042(2) 0.041(1) 0.003(1) 0.0171(9) 0.006(1) C N1 0.032(1) 0.039(1) 0.047(1) 0.003(1) 0.0166(8) 0.001(1) N O1 0.0369(9) 0.050(1) 0.085(1) 0.009(1) 0.0243(9) 0.005(1) O C2 0.038(1) 0.037(2) 0.048(1) -0.004(1) 0.021(1) -0.001(1) C C3 0.041(1) 0.038(2) 0.044(1) -0.002(1) 0.0203(9) 0.006(1) C N2 0.034(1) 0.046(1) 0.051(1) 0.002(1) 0.0191(8) 0.011(1) N O2 0.036(1) 0.071(2) 0.103(1) 0.010(1) 0.0330(9) 0.032(1) O C4 0.053(2) 0.051(2) 0.065(2) -0.004(2) 0.014(1) -0.011(2) C C5 0.053(1) 0.060(2) 0.084(2) 0.000(2) 0.042(1) 0.011(2) C C6 0.065(2) 0.060(2) 0.046(2) -0.010(2) 0.016(1) 0.005(2) C C7 0.052(2) 0.048(2) 0.073(2) 0.008(2) 0.027(1) 0.011(2) C C8 0.049(1) 0.043(2) 0.050(1) 0.005(1) 0.029(1) 0.009(1) C C9 0.076(2) 0.053(2) 0.130(2) 0.001(2) 0.067(1) 0.023(2) C C10 0.043(3) 0.042(3) 0.049(3) -0.006(3) 0.017(2) -0.000(3) C C11 0.108(2) 0.061(2) 0.080(2) 0.033(2) 0.061(1) 0.036(2) C C12 0.047(3) 0.050(4) 0.040(3) 0.003(3) 0.016(2) 0.006(3) C # 10. MOLECULAR GEOMETRY loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag C1 N1 1.353(4) . . ? C1 N2 1.359(4) . . ? C1 C8 1.467(5) . . ? N1 O1 1.285(3) . . ? N1 C2 1.508(4) . . ? C2 C3 1.548(4) . . ? C2 C4 1.530(5) . . ? C2 C5 1.522(4) . . ? C3 N2 1.507(4) . . ? C3 C6 1.530(5) . . ? C3 C7 1.518(5) . . ? N2 O2 1.282(3) . . ? C8 C9 1.429(6) . . ? C8 C11 1.449(5) . . ? C9 C10 1.418(8) . . ? C10 C12 1.240(9) . 3_666 ? C11 C12 1.531(8) . . ? loop_ _geom_contact_atom_site_label_1 _geom_contact_atom_site_label_2 _geom_contact_distance _geom_contact_site_symmetry_1 _geom_contact_site_symmetry_2 _geom_contact_publ_flag ? ? ? ? ? ? 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 C1 N2 108.0(3) . . . ? N1 C1 C8 126.4(3) . . . ? N2 C1 C8 125.6(3) . . . ? C1 N1 O1 126.5(3) . . . ? C1 N1 C2 111.6(2) . . . ? O1 N1 C2 121.7(2) . . . ? N1 C2 C3 100.3(2) . . . ? N1 C2 C4 105.5(3) . . . ? N1 C2 C5 110.3(3) . . . ? C3 C2 C4 114.1(3) . . . ? C3 C2 C5 115.2(3) . . . ? C4 C2 C5 110.4(3) . . . ? C2 C3 N2 99.9(2) . . . ? C2 C3 C6 113.5(3) . . . ? C2 C3 C7 115.1(3) . . . ? N2 C3 C6 106.1(3) . . . ? N2 C3 C7 110.6(3) . . . ? C6 C3 C7 110.7(3) . . . ? C1 N2 C3 111.3(2) . . . ? C1 N2 O2 126.5(3) . . . ? C3 N2 O2 121.9(3) . . . ? C1 C8 C9 117.8(3) . . . ? C1 C8 C11 117.7(3) . . . ? C9 C8 C11 124.5(4) . . . ? C8 C9 C10 109.3(5) . . . ? C9 C10 C12 168.5(7) . . 3_666 ? C8 C11 C12 108.5(4) . . . ? C10 C12 C11 171.6(7) . 3_666 . ? #========================END