# Supplementary Material (ESI) for Journal of Materials Chemistry # This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full J.Mater.Chem. _journal_coden_cambridge 1145 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name P.Vasile M.Andruh V.Kravtsov G.Marin A.N.Parvulescu ; V.Parvulescu ; _publ_contact_author_name 'ProfD Parvulescu Vasile' _publ_contact_author_email 'V PARVULESCU@CHEM.UNIBUC.RO' _publ_section_title ; A polynuclear complex, {[Cu(bpe)2](NO3)}?2H2O, with interpenetrated diamondoid networks: synthesis, properties and catalytic behavior ; data_ap1c _database_code_depnum_ccdc_archive 'CCDC 268719' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C24 H20 Cu N5 O3' _chemical_formula_weight 489.99 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' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M I-4 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' 'y+1/2, -x+1/2, -z+1/2' '-y+1/2, x+1/2, -z+1/2' _cell_length_a 17.398(3) _cell_length_b 17.398(3) _cell_length_c 8.0808(16) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 2446.0(7) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description plate _exptl_crystal_colour red _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.05 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.331 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1008 _exptl_absorpt_coefficient_mu 0.926 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min 0.8364 _exptl_absorpt_correction_T_max 0.9552 _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 ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 1357 _diffrn_reflns_av_R_equivalents 0.0261 _diffrn_reflns_av_sigmaI/netI 0.0417 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -7 _diffrn_reflns_limit_l_max 8 _diffrn_reflns_theta_min 3.64 _diffrn_reflns_theta_max 20.75 _reflns_number_total 1253 _reflns_number_gt 990 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1485P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.49(6) _refine_ls_number_reflns 1253 _refine_ls_number_parameters 158 _refine_ls_number_restraints 49 _refine_ls_R_factor_all 0.0794 _refine_ls_R_factor_gt 0.0579 _refine_ls_wR_factor_ref 0.1850 _refine_ls_wR_factor_gt 0.1698 _refine_ls_goodness_of_fit_ref 1.005 _refine_ls_restrained_S_all 1.030 _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 Cu1 Cu 0.0000 0.0000 0.0000 0.0670(9) Uani 1 4 d S . . Cu2 Cu -0.5000 0.0000 1.2500 0.0957(11) Uani 1 4 d S . . N1 N -0.0931(4) -0.0012(5) 0.1562(13) 0.060(3) Uani 1 1 d D . . N2 N -0.4083(6) 0.0027(6) 1.1013(14) 0.102(4) Uani 1 1 d D . . C1 C -0.0942(7) -0.0528(7) 0.2753(17) 0.092(4) Uani 1 1 d D . . H1 H -0.0618 -0.0952 0.2673 0.110 Uiso 1 1 calc R . . C2 C -0.1411(6) -0.0465(6) 0.4103(18) 0.096(4) Uani 1 1 d D . . H2 H -0.1347 -0.0795 0.4997 0.115 Uiso 1 1 calc R . . C3 C -0.1999(8) 0.0105(6) 0.4146(16) 0.084(5) Uani 1 1 d D . . C4 C -0.1952(6) 0.0624(6) 0.2851(16) 0.078(4) Uani 1 1 d D . . H4 H -0.2289 0.1038 0.2821 0.094 Uiso 1 1 calc R . . C5 C -0.1418(5) 0.0542(5) 0.1607(18) 0.077(4) Uani 1 1 d D . . H5 H -0.1410 0.0904 0.0761 0.093 Uiso 1 1 calc R . . C6 C -0.2539(6) 0.0211(6) 0.5497(16) 0.070(3) Uani 1 1 d D . . H6 H -0.2881 0.0621 0.5420 0.084 Uiso 1 1 calc R . . C7 C -0.2582(6) -0.0219(7) 0.6797(19) 0.079(4) Uani 1 1 d D . . H7 H -0.2282 -0.0661 0.6768 0.095 Uiso 1 1 calc R . . C8 C -0.3036(6) -0.0113(6) 0.8314(15) 0.063(4) Uani 1 1 d D . . C9 C -0.3039(6) -0.0637(6) 0.9571(19) 0.086(5) Uani 1 1 d D . . H9 H -0.2708 -0.1057 0.9552 0.103 Uiso 1 1 calc R . . C10 C -0.3538(7) -0.0531(6) 1.0857(16) 0.087(4) Uani 1 1 d D . . H10 H -0.3501 -0.0879 1.1726 0.105 Uiso 1 1 calc R . . C11 C -0.3987(8) 0.0559(9) 0.985(2) 0.130(5) Uani 1 1 d D . . H11 H -0.4292 0.0997 0.9911 0.156 Uiso 1 1 calc R . . C12 C -0.3470(7) 0.0512(7) 0.8547(19) 0.106(4) Uani 1 1 d D . . H12 H -0.3425 0.0924 0.7820 0.127 Uiso 1 1 calc R . . N3 N -0.2179(18) 0.2344(18) 0.702(5) 0.185(7) Uiso 0.254(8) 1 d PD A 1 O11 O -0.185(2) 0.291(2) 0.642(5) 0.185(7) Uiso 0.254(8) 1 d PD A 1 O21 O -0.258(3) 0.194(2) 0.611(6) 0.185(7) Uiso 0.254(8) 1 d PD A 1 O31 O -0.210(3) 0.216(3) 0.849(5) 0.185(7) Uiso 0.254(8) 1 d PD A 1 N4 N -0.2584(18) 0.2181(17) 0.879(5) 0.185(7) Uiso 0.246(8) 1 d PD A 2 O12 O -0.202(2) 0.176(2) 0.874(6) 0.185(7) Uiso 0.246(8) 1 d PD A 2 O22 O -0.288(2) 0.239(3) 0.745(6) 0.185(7) Uiso 0.246(8) 1 d PD A 2 O32 O -0.286(2) 0.240(3) 1.010(6) 0.185(7) Uiso 0.246(8) 1 d PD A 2 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 Cu1 0.0712(10) 0.0712(10) 0.058(2) 0.000 0.000 0.000 Cu2 0.1223(14) 0.1223(14) 0.043(2) 0.000 0.000 0.000 N1 0.039(4) 0.064(5) 0.077(8) 0.022(6) 0.017(5) 0.001(4) N2 0.159(9) 0.101(7) 0.046(8) -0.003(7) 0.002(7) 0.019(8) C1 0.106(9) 0.088(8) 0.081(12) 0.006(10) 0.029(11) 0.022(7) C2 0.096(8) 0.101(8) 0.091(12) 0.030(9) 0.015(7) 0.044(6) C3 0.110(10) 0.079(8) 0.063(12) -0.008(8) -0.005(9) 0.011(7) C4 0.102(9) 0.070(7) 0.062(13) -0.005(8) 0.012(9) 0.012(6) C5 0.059(6) 0.087(7) 0.086(12) -0.008(8) 0.020(8) -0.029(6) C6 0.070(7) 0.092(7) 0.048(8) -0.005(8) -0.008(6) 0.004(5) C7 0.056(6) 0.091(7) 0.090(14) 0.011(9) 0.002(7) 0.013(5) C8 0.040(6) 0.086(8) 0.063(12) -0.001(8) 0.006(7) -0.012(6) C9 0.069(7) 0.097(8) 0.092(16) 0.018(10) -0.008(9) 0.015(6) C10 0.111(9) 0.097(8) 0.054(10) 0.030(8) -0.004(9) 0.024(8) C11 0.156(12) 0.145(12) 0.089(12) 0.043(14) 0.042(15) 0.079(10) C12 0.132(10) 0.117(9) 0.069(11) 0.030(10) 0.032(8) 0.002(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 Cu1 N1 2.054(7) 4 ? Cu1 N1 2.054(7) 2 ? Cu1 N1 2.054(7) . ? Cu1 N1 2.054(7) 3 ? Cu2 N2 1.998(11) 2_455 ? Cu2 N2 1.998(11) 8_457 ? Cu2 N2 1.998(11) 7_447 ? Cu2 N2 1.998(11) . ? N1 C5 1.284(9) . ? N1 C1 1.316(10) . ? N2 C11 1.330(11) . ? N2 C10 1.362(11) . ? C1 C2 1.367(12) . ? C2 C3 1.424(10) . ? C3 C4 1.385(11) . ? C3 C6 1.452(11) . ? C4 C5 1.375(11) . ? C6 C7 1.292(12) . ? C7 C8 1.470(12) . ? C8 C12 1.337(11) . ? C8 C9 1.365(10) . ? C9 C10 1.367(11) . ? C11 C12 1.386(11) . ? N3 O11 1.228(18) . ? N3 O31 1.235(19) . ? N3 O21 1.242(19) . ? N4 O32 1.228(18) . ? N4 O12 1.231(19) . ? N4 O22 1.250(19) . ? 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 N1 Cu1 N1 112.2(3) 4 2 ? N1 Cu1 N1 112.2(3) 4 . ? N1 Cu1 N1 104.2(5) 2 . ? N1 Cu1 N1 104.2(5) 4 3 ? N1 Cu1 N1 112.2(3) 2 3 ? N1 Cu1 N1 112.2(3) . 3 ? N2 Cu2 N2 111.2(3) 2_455 8_457 ? N2 Cu2 N2 111.2(3) 2_455 7_447 ? N2 Cu2 N2 106.1(7) 8_457 7_447 ? N2 Cu2 N2 106.1(7) 2_455 . ? N2 Cu2 N2 111.2(3) 8_457 . ? N2 Cu2 N2 111.2(3) 7_447 . ? C5 N1 C1 118.8(10) . . ? C5 N1 Cu1 122.0(7) . . ? C1 N1 Cu1 117.8(7) . . ? C11 N2 C10 110.0(11) . . ? C11 N2 Cu2 122.8(9) . . ? C10 N2 Cu2 126.5(9) . . ? N1 C1 C2 122.5(10) . . ? C1 C2 C3 120.3(11) . . ? C4 C3 C2 113.1(11) . . ? C4 C3 C6 121.6(9) . . ? C2 C3 C6 124.9(11) . . ? C5 C4 C3 121.7(10) . . ? N1 C5 C4 122.9(11) . . ? C7 C6 C3 125.1(9) . . ? C6 C7 C8 129.5(9) . . ? C12 C8 C9 115.9(10) . . ? C12 C8 C7 121.6(12) . . ? C9 C8 C7 122.5(11) . . ? C8 C9 C10 118.5(9) . . ? N2 C10 C9 127.5(10) . . ? N2 C11 C12 125.2(11) . . ? C8 C12 C11 121.4(11) . . ? O11 N3 O31 122(2) . . ? O11 N3 O21 119(2) . . ? O31 N3 O21 119(2) . . ? O32 N4 O12 122(2) . . ? O32 N4 O22 120(2) . . ? O12 N4 O22 118(2) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 20.75 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.355 _refine_diff_density_min -0.323 _refine_diff_density_rms 0.064