# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _publ_contact_author_name 'Srinivasan Natarajan' _publ_contact_author_address ; Solid State and Structural Chemistry Unit Indian Institute of Science C.V. Raman Avenue Bangalore 560 012 INDIA ; _publ_contact_author_email SNATARAJAN@SSCU.IISC.ERNET.IN _publ_section_title ; A Porous Sheet 4f-3d Mixed-Metal Pyridine Dicarboxylate: Synthesis, Structure, Photophysical Properties and its Transformation to a Perovskite Oxide ; loop_ _publ_author_name 'Srinivasan Natarajan' 'Giridhar Madras' 'Partha Mahata' 'Gopinathan Sankar' data_sad _database_code_depnum_ccdc_archive 'CCDC 277358' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C21 H15 Co1 Gd1 N3 O15' _chemical_formula_weight 765.168 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' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Gd Gd -0.1653 3.9035 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M P3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' _cell_length_a 13.1879(2) _cell_length_b 13.1879(2) _cell_length_c 5.92910(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 893.04(2) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description rod-like _exptl_crystal_colour pink _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.401 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 361 _exptl_absorpt_coefficient_mu 2.363 _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 "Siemen's SMART-CCD" _diffrn_measurement_method 'w scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 3745 _diffrn_reflns_av_R_equivalents 0.0450 _diffrn_reflns_av_sigmaI/netI 0.0620 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -6 _diffrn_reflns_limit_l_max 6 _diffrn_reflns_theta_min 1.78 _diffrn_reflns_theta_max 23.32 _reflns_number_total 1689 _reflns_number_gt 1657 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution ? _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics Diamond _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0596P)^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 mixed _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 1.04(3) _refine_ls_number_reflns 1689 _refine_ls_number_parameters 125 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0402 _refine_ls_R_factor_gt 0.0378 _refine_ls_wR_factor_ref 0.1066 _refine_ls_wR_factor_gt 0.1050 _refine_ls_goodness_of_fit_ref 1.142 _refine_ls_restrained_S_all 1.142 _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 Gd1 Gd 0.6667 0.3333 0.2049 0.0297(2) Uani 1 3 d S . . Co1 Co 0.0000 0.0000 -0.0018(3) 0.0288(5) Uani 1 3 d S . . O1 O 0.8045(7) 0.4725(7) 0.4691(13) 0.053(2) Uani 1 1 d . . . O2 O 0.5172(6) 0.2857(6) -0.0854(11) 0.0436(16) Uani 1 1 d . . . O3 O 0.4845(6) 0.1405(6) 0.1419(11) 0.0432(16) Uani 1 1 d . . . O4 O 0.1134(5) 0.1187(5) 0.1832(10) 0.0355(14) Uani 1 1 d . . . O5 O 0.3049(6) 0.2182(7) 0.2519(13) 0.055(2) Uani 1 1 d . . . N1 N 0.1327(6) 0.0144(7) -0.1643(12) 0.0316(17) Uani 1 1 d . . . C1 C 0.2347(8) 0.0857(7) -0.0627(14) 0.0294(19) Uani 1 1 d . . . C2 C 0.3358(8) 0.0986(8) -0.1380(14) 0.034(2) Uani 1 1 d . . . C3 C 0.3392(8) 0.0415(9) -0.3332(15) 0.041(2) Uani 1 1 d . . . H1 H 0.4097 0.0527 -0.3903 0.049 Uiso 1 1 calc R . . C4 C 0.2365(9) -0.0307(9) -0.4371(18) 0.046(3) Uani 1 1 d . . . H2 H 0.2353 -0.0713 -0.5662 0.055 Uiso 1 1 calc R . . C5 C 0.1324(9) -0.0438(8) -0.3493(16) 0.038(2) Uani 1 1 d . . . H3 H 0.0618 -0.0938 -0.4203 0.046 Uiso 1 1 calc R . . C6 C 0.2205(8) 0.1481(8) 0.1441(16) 0.033(2) Uani 1 1 d . . . C7 C 0.4537(9) 0.1812(9) -0.0149(17) 0.039(2) 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 Gd1 0.0327(3) 0.0327(3) 0.0235(3) 0.000 0.000 0.01636(14) Co1 0.0310(7) 0.0310(7) 0.0243(11) 0.000 0.000 0.0155(4) O1 0.050(5) 0.052(5) 0.044(5) -0.022(4) -0.006(4) 0.015(4) O2 0.041(4) 0.036(4) 0.041(4) 0.000(3) -0.011(3) 0.010(3) O3 0.038(4) 0.040(4) 0.038(4) 0.009(3) -0.007(3) 0.010(3) O4 0.035(4) 0.040(4) 0.029(3) -0.006(3) 0.001(3) 0.017(3) O5 0.052(5) 0.055(5) 0.055(5) -0.028(4) -0.015(4) 0.025(4) N1 0.033(4) 0.039(4) 0.025(4) -0.002(3) 0.002(3) 0.019(4) C1 0.034(5) 0.026(4) 0.025(4) -0.004(4) -0.004(4) 0.013(4) C2 0.037(5) 0.042(5) 0.029(5) -0.005(4) -0.010(4) 0.025(4) C3 0.036(5) 0.057(6) 0.033(5) -0.011(4) -0.007(4) 0.025(5) C4 0.054(7) 0.053(6) 0.039(6) -0.003(5) 0.008(5) 0.033(6) C5 0.043(6) 0.042(6) 0.030(5) -0.002(4) -0.007(4) 0.020(5) C6 0.032(5) 0.022(5) 0.040(6) 0.005(4) 0.003(4) 0.009(4) C7 0.030(6) 0.043(6) 0.039(6) -0.008(5) -0.003(5) 0.013(5) _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 Gd1 O1 2.406(7) 3_665 ? Gd1 O1 2.406(7) . ? Gd1 O1 2.406(7) 2_655 ? Gd1 O2 2.450(6) 2_655 ? Gd1 O2 2.450(6) . ? Gd1 O2 2.450(6) 3_665 ? Gd1 O3 2.504(6) 2_655 ? Gd1 O3 2.504(6) . ? Gd1 O3 2.504(6) 3_665 ? Gd1 C7 2.824(10) 2_655 ? Gd1 C7 2.824(10) . ? Gd1 C7 2.824(10) 3_665 ? Co1 O4 1.884(6) . ? Co1 O4 1.884(6) 2 ? Co1 O4 1.884(6) 3 ? Co1 N1 1.923(7) 2 ? Co1 N1 1.923(7) 3 ? Co1 N1 1.923(7) . ? O2 C7 1.273(12) . ? O3 C7 1.239(12) . ? O4 C6 1.284(11) . ? O5 C6 1.214(12) . ? N1 C1 1.338(11) . ? N1 C5 1.338(12) . ? C1 C2 1.334(13) . ? C1 C6 1.540(12) . ? C2 C3 1.394(13) . ? C2 C7 1.564(13) . ? C3 C4 1.353(14) . ? C3 H1 0.9300 . ? C4 C5 1.396(15) . ? C4 H2 0.9300 . ? C5 H3 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 O1 Gd1 O1 82.2(3) 3_665 . ? O1 Gd1 O1 82.2(3) 3_665 2_655 ? O1 Gd1 O1 82.2(3) . 2_655 ? O1 Gd1 O2 86.7(2) 3_665 2_655 ? O1 Gd1 O2 124.9(3) . 2_655 ? O1 Gd1 O2 149.0(3) 2_655 2_655 ? O1 Gd1 O2 124.9(3) 3_665 . ? O1 Gd1 O2 149.0(3) . . ? O1 Gd1 O2 86.7(2) 2_655 . ? O2 Gd1 O2 76.1(3) 2_655 . ? O1 Gd1 O2 149.0(3) 3_665 3_665 ? O1 Gd1 O2 86.7(2) . 3_665 ? O1 Gd1 O2 124.9(3) 2_655 3_665 ? O2 Gd1 O2 76.1(3) 2_655 3_665 ? O2 Gd1 O2 76.1(3) . 3_665 ? O1 Gd1 O3 75.4(3) 3_665 2_655 ? O1 Gd1 O3 72.3(3) . 2_655 ? O1 Gd1 O3 147.9(2) 2_655 2_655 ? O2 Gd1 O3 52.7(2) 2_655 2_655 ? O2 Gd1 O3 125.0(2) . 2_655 ? O2 Gd1 O3 73.6(2) 3_665 2_655 ? O1 Gd1 O3 72.3(3) 3_665 . ? O1 Gd1 O3 147.9(2) . . ? O1 Gd1 O3 75.4(3) 2_655 . ? O2 Gd1 O3 73.6(2) 2_655 . ? O2 Gd1 O3 52.7(2) . . ? O2 Gd1 O3 125.0(2) 3_665 . ? O3 Gd1 O3 117.82(8) 2_655 . ? O1 Gd1 O3 147.9(2) 3_665 3_665 ? O1 Gd1 O3 75.4(3) . 3_665 ? O1 Gd1 O3 72.3(3) 2_655 3_665 ? O2 Gd1 O3 125.0(2) 2_655 3_665 ? O2 Gd1 O3 73.6(2) . 3_665 ? O2 Gd1 O3 52.7(2) 3_665 3_665 ? O3 Gd1 O3 117.82(8) 2_655 3_665 ? O3 Gd1 O3 117.82(8) . 3_665 ? O1 Gd1 C7 79.1(3) 3_665 2_655 ? O1 Gd1 C7 98.3(3) . 2_655 ? O1 Gd1 C7 161.1(3) 2_655 2_655 ? O2 Gd1 C7 26.8(3) 2_655 2_655 ? O2 Gd1 C7 101.4(3) . 2_655 ? O2 Gd1 C7 73.9(3) 3_665 2_655 ? O3 Gd1 C7 26.0(3) 2_655 2_655 ? O3 Gd1 C7 95.7(3) . 2_655 ? O3 Gd1 C7 126.3(3) 3_665 2_655 ? O1 Gd1 C7 98.3(3) 3_665 . ? O1 Gd1 C7 161.1(3) . . ? O1 Gd1 C7 79.1(3) 2_655 . ? O2 Gd1 C7 73.9(3) 2_655 . ? O2 Gd1 C7 26.8(3) . . ? O2 Gd1 C7 101.4(3) 3_665 . ? O3 Gd1 C7 126.3(3) 2_655 . ? O3 Gd1 C7 26.0(3) . . ? O3 Gd1 C7 95.7(3) 3_665 . ? C7 Gd1 C7 100.4(3) 2_655 . ? O1 Gd1 C7 161.1(3) 3_665 3_665 ? O1 Gd1 C7 79.1(3) . 3_665 ? O1 Gd1 C7 98.3(3) 2_655 3_665 ? O2 Gd1 C7 101.4(3) 2_655 3_665 ? O2 Gd1 C7 73.9(3) . 3_665 ? O2 Gd1 C7 26.8(3) 3_665 3_665 ? O3 Gd1 C7 95.7(3) 2_655 3_665 ? O3 Gd1 C7 126.3(3) . 3_665 ? O3 Gd1 C7 26.0(3) 3_665 3_665 ? C7 Gd1 C7 100.4(3) 2_655 3_665 ? C7 Gd1 C7 100.4(3) . 3_665 ? O4 Co1 O4 89.5(3) . 2 ? O4 Co1 O4 89.5(3) . 3 ? O4 Co1 O4 89.5(3) 2 3 ? O4 Co1 N1 88.7(3) . 2 ? O4 Co1 N1 84.5(3) 2 2 ? O4 Co1 N1 173.8(3) 3 2 ? O4 Co1 N1 173.8(3) . 3 ? O4 Co1 N1 88.7(3) 2 3 ? O4 Co1 N1 84.5(3) 3 3 ? N1 Co1 N1 97.1(3) 2 3 ? O4 Co1 N1 84.5(3) . . ? O4 Co1 N1 173.8(3) 2 . ? O4 Co1 N1 88.7(3) 3 . ? N1 Co1 N1 97.1(3) 2 . ? N1 Co1 N1 97.1(3) 3 . ? C7 O2 Gd1 93.2(6) . . ? C7 O3 Gd1 91.6(6) . . ? C6 O4 Co1 116.2(6) . . ? C1 N1 C5 119.1(7) . . ? C1 N1 Co1 112.9(6) . . ? C5 N1 Co1 127.8(6) . . ? C2 C1 N1 121.9(8) . . ? C2 C1 C6 125.4(8) . . ? N1 C1 C6 112.7(7) . . ? C1 C2 C3 120.6(8) . . ? C1 C2 C7 121.0(8) . . ? C3 C2 C7 118.3(8) . . ? C4 C3 C2 117.8(9) . . ? C4 C3 H1 121.1 . . ? C2 C3 H1 121.1 . . ? C3 C4 C5 119.6(9) . . ? C3 C4 H2 120.2 . . ? C5 C4 H2 120.2 . . ? N1 C5 C4 120.9(9) . . ? N1 C5 H3 119.5 . . ? C4 C5 H3 119.5 . . ? O5 C6 O4 125.8(9) . . ? O5 C6 C1 121.1(8) . . ? O4 C6 C1 113.0(8) . . ? O3 C7 O2 122.3(9) . . ? O3 C7 C2 118.4(9) . . ? O2 C7 C2 119.2(9) . . ? O3 C7 Gd1 62.4(5) . . ? O2 C7 Gd1 60.0(5) . . ? C2 C7 Gd1 179.1(7) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 23.32 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.963 _refine_diff_density_min -0.756 _refine_diff_density_rms 0.187