# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name 'Wen-Feng Zhao' 'Chao Zou' 'Lian-Xu Shi' 'Jiancan Yu' 'Guodong Qian' 'Chuan-De Wu' _publ_contact_author_name 'Chuan-De Wu' _publ_contact_author_email cdwu@zju.edu.cn data_EuPOM _database_code_depnum_ccdc_archive 'CCDC 869570' #TrackingRef '- Eu_POM.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C36 H90 Eu2 N12 O58 W12 Zn' _chemical_formula_weight 4194.69 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source O O 0.0106 0.0060 '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' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Eu Eu -0.1578 3.6682 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M I-42d loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' '-x+1/2, y, -z+3/4' 'x+1/2, -y, -z+3/4' '-y+1/2, -x, z+3/4' 'y+1/2, x, z+3/4' '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' '-x+1, y+1/2, -z+5/4' 'x+1, -y+1/2, -z+5/4' '-y+1, -x+1/2, z+5/4' 'y+1, x+1/2, z+5/4' _cell_length_a 14.1227(2) _cell_length_b 14.1227(2) _cell_length_c 44.7701(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8929.4(3) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 32513 _cell_measurement_theta_min 3.02 _cell_measurement_theta_max 27.69 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.29 _exptl_crystal_size_mid 0.23 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.120 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 7592 _exptl_absorpt_coefficient_mu 17.132 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.012 _exptl_absorpt_correction_T_max 0.108 _exptl_absorpt_process_details CrysAlisPro _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 'Xcalibur, Atlas, Gemini ultra' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 10.3592 _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% ? _diffrn_reflns_number 32513 _diffrn_reflns_av_R_equivalents 0.0566 _diffrn_reflns_av_sigmaI/netI 0.0343 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -18 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -58 _diffrn_reflns_limit_l_max 44 _diffrn_reflns_theta_min 3.02 _diffrn_reflns_theta_max 27.69 _reflns_number_total 5187 _reflns_number_gt 4420 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlisPro (Oxford Diffraction Ltd., 2010)' _computing_cell_refinement 'CrysAlisPro (Oxford Diffraction Ltd., 2010)' _computing_data_reduction 'CrysAlisPro (Oxford Diffraction Ltd., 2010)' _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. Because of the poor diffraction ability of the light atoms of C, N and O compared with the heavy atoms of W and Eu, the two disordered DMF ligands per asymmetric unit can not be well-positioned from difference Fourier maps. The distances between C, N and O atoms of DMF ligands were fixed to the reasonable values with 8 restraints, and were refined isotropically. The four disordered lattice DMF molecules per formular unit could not be located successfully from Fourier maps in the refinement cycles. The four lattice DMF molecules were removed using the SQUEEZE procedure implemented in the PLATON package. The resulting new file was used to further refine the structure. The composition of Eu-POM was figured out based on the elemental analysis, thermogravimetric analysis (TGA) and single crystal structure. The four lattice DMF molecules were added to account for the formula in the cif file. The poor crystal data suggest that only the gross connectivity and partial structure were obtained. The highest residual peak 2.64 is located at (0.1088, 0.1423, 0.0558), 0.07 \%A from W2. ; # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 -0.133 0.043 0.370 2338 433 ' ' _platon_squeeze_details ; Crystal structure was found to contain four disordered lattice solvent molecules, which could not be sufficiently modeled in the refinement cycles. These molecules were removed using the SQUEEZE procedure implemented in the PLATON package. ; _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^)+(0.0851P)^2^+70.6229P] 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 -0.02(3) _refine_ls_number_reflns 5187 _refine_ls_number_parameters 189 _refine_ls_number_restraints 8 _refine_ls_R_factor_all 0.0655 _refine_ls_R_factor_gt 0.0580 _refine_ls_wR_factor_ref 0.1596 _refine_ls_wR_factor_gt 0.1534 _refine_ls_goodness_of_fit_ref 1.133 _refine_ls_restrained_S_all 1.132 _refine_ls_shift/su_max 0.001 _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 W1 W 0.87473(5) 0.11781(5) 0.054312(15) 0.05771(19) Uani 1 1 d . . . W2 W 1.10468(5) 0.14329(5) 0.055162(16) 0.0590(2) Uani 1 1 d . . . W3 W 0.97756(6) 0.24770(5) 0.004170(14) 0.0604(2) Uani 1 1 d . . . Eu1 Eu 0.72577(9) 0.2500 0.1250 0.0647(3) Uani 1 2 d S . . Zn1 Zn 1.0000 0.0000 0.0000 0.0409(6) Uani 1 4 d S . . O1 O 0.8933(8) -0.0046(8) 0.0656(2) 0.053(2) Uani 1 1 d . . . O2 O 0.7970(9) 0.1572(9) 0.0821(3) 0.064(3) Uani 1 1 d . . . O3 O 1.1778(10) 0.1862(9) 0.0809(3) 0.063(3) Uani 1 1 d . . . O4 O 0.6314(14) 0.2774(17) 0.0763(4) 0.124(7) Uani 1 1 d D . . O5 O 0.7785(12) 0.4007(10) 0.1006(3) 0.090(5) Uani 1 1 d D . . O6 O 0.9897(7) 0.1085(7) 0.02481(17) 0.045(2) Uani 1 1 d . . . O7 O 0.8869(10) 0.2425(9) 0.0330(3) 0.068(3) Uani 1 1 d . . . O8 O 0.7939(7) 0.0753(7) 0.0243(2) 0.050(2) Uani 1 1 d . . . O9 O 1.0780(9) 0.2582(8) 0.0339(2) 0.059(3) Uani 1 1 d . . . O10 O 1.1921(8) 0.1053(8) 0.0245(2) 0.053(2) Uani 1 1 d . . . O11 O 0.9900(8) 0.1519(7) 0.07758(19) 0.048(2) Uani 1 1 d . . . O12 O 0.9691(10) 0.3654(9) -0.0045(3) 0.075(3) Uani 1 1 d . . . O13 O 0.9084(16) 0.2500 0.1250 0.095(7) Uani 1 2 d S . . O14 O 0.6039(16) 0.119(3) 0.1159(6) 0.199(17) Uani 1 1 d . . . N1 N 0.633(2) 0.266(2) 0.0248(5) 0.138(9) Uiso 1 1 d D . . N2 N 0.8715(16) 0.5232(14) 0.0885(4) 0.108(7) Uiso 1 1 d D . . C1 C 0.6635(19) 0.2930(19) 0.0513(4) 0.096(7) Uiso 1 1 d D . . H1A H 0.7179 0.3302 0.0510 0.115 Uiso 1 1 calc R . . C2 C 0.680(3) 0.303(3) -0.0015(9) 0.173(16) Uiso 1 1 d D . . H2A H 0.7263 0.3497 0.0045 0.260 Uiso 1 1 calc R . . H2B H 0.6344 0.3322 -0.0143 0.260 Uiso 1 1 calc R . . H2C H 0.7115 0.2527 -0.0119 0.260 Uiso 1 1 calc R . . C3 C 0.556(3) 0.199(3) 0.0242(10) 0.176(19) Uiso 1 1 d D . . H3A H 0.5310 0.1911 0.0440 0.264 Uiso 1 1 calc R . . H3B H 0.5783 0.1389 0.0169 0.264 Uiso 1 1 calc R . . H3C H 0.5069 0.2219 0.0112 0.264 Uiso 1 1 calc R . . C4 C 0.8299(15) 0.4661(14) 0.1080(5) 0.089(6) Uiso 1 1 d D . . H4A H 0.8403 0.4763 0.1283 0.107 Uiso 1 1 calc R . . C5 C 0.873(3) 0.531(3) 0.0564(5) 0.165(15) Uiso 1 1 d D . . H5A H 0.8448 0.4758 0.0477 0.247 Uiso 1 1 calc R . . H5B H 0.9368 0.5376 0.0496 0.247 Uiso 1 1 calc R . . H5C H 0.8370 0.5861 0.0505 0.247 Uiso 1 1 calc R . . C6 C 0.910(2) 0.6098(17) 0.1009(6) 0.102(8) Uiso 1 1 d D . . H6A H 0.9105 0.6055 0.1223 0.153 Uiso 1 1 calc R . . H6B H 0.8708 0.6623 0.0950 0.153 Uiso 1 1 calc R . . H6C H 0.9730 0.6191 0.0937 0.153 Uiso 1 1 calc R . . 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 W1 0.0641(4) 0.0624(4) 0.0466(3) -0.0058(3) 0.0055(3) 0.0046(3) W2 0.0633(4) 0.0640(4) 0.0496(3) -0.0078(3) -0.0061(3) -0.0008(3) W3 0.0754(5) 0.0524(4) 0.0534(3) 0.0009(3) -0.0014(3) 0.0009(4) Eu1 0.0621(7) 0.0687(7) 0.0633(7) -0.0087(6) 0.000 0.000 Zn1 0.0443(9) 0.0443(9) 0.0340(12) 0.000 0.000 0.000 O1 0.070(7) 0.045(5) 0.044(4) 0.000(4) 0.010(5) -0.002(5) O2 0.069(7) 0.065(7) 0.058(6) 0.000(6) -0.015(5) 0.001(6) O3 0.077(8) 0.061(6) 0.051(6) -0.002(5) -0.011(6) 0.005(6) O4 0.104(14) 0.17(2) 0.096(11) 0.012(12) 0.009(10) 0.043(14) O5 0.122(13) 0.066(8) 0.082(9) 0.016(7) -0.013(9) -0.015(8) O6 0.054(5) 0.043(5) 0.037(4) -0.014(4) 0.002(4) -0.008(4) O7 0.088(9) 0.055(6) 0.063(6) 0.017(6) -0.014(6) 0.004(7) O8 0.049(5) 0.047(5) 0.052(5) -0.020(4) -0.003(4) 0.002(4) O9 0.070(7) 0.052(6) 0.053(5) 0.001(5) -0.006(5) 0.003(5) O10 0.059(6) 0.053(6) 0.046(5) 0.007(4) 0.008(5) 0.003(5) O11 0.052(5) 0.050(5) 0.043(4) -0.002(4) -0.013(4) 0.004(5) O12 0.083(9) 0.065(8) 0.077(8) -0.008(6) -0.014(7) 0.010(7) O13 0.074(12) 0.119(18) 0.093(13) -0.052(14) 0.000 0.000 O14 0.093(14) 0.37(5) 0.131(19) 0.01(2) -0.003(12) -0.11(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag W1 O2 1.751(13) . ? W1 O1 1.820(11) . ? W1 O8 1.862(10) . ? W1 O11 1.991(10) . ? W1 O7 2.010(11) . ? W1 O6 2.097(9) . ? W2 O3 1.661(12) . ? W2 O11 1.910(11) . ? W2 O9 1.918(12) . ? W2 O10 1.924(10) . ? W2 O1 2.015(11) 2_755 ? W2 O6 2.174(9) . ? W3 O12 1.711(13) . ? W3 O7 1.820(14) . ? W3 O10 1.905(11) 4_645 ? W3 O9 1.952(11) . ? W3 O8 1.969(10) 3_665 ? W3 O6 2.179(9) . ? Eu1 O5 2.505(13) . ? Eu1 O5 2.505(13) 14_454 ? Eu1 O2 2.533(13) . ? Eu1 O2 2.533(13) 14_454 ? Eu1 O14 2.56(3) . ? Eu1 O14 2.56(3) 14_454 ? Eu1 O13 2.58(2) . ? Eu1 O4 2.584(19) . ? Eu1 O4 2.584(19) 14_454 ? Zn1 O6 1.898(8) 4_645 ? Zn1 O6 1.898(8) 3_665 ? Zn1 O6 1.898(8) . ? Zn1 O6 1.898(8) 2_755 ? O1 W2 2.015(11) 2_755 ? O4 C1 1.230(10) . ? O5 C4 1.221(10) . ? O8 W3 1.969(10) 4_645 ? O10 W3 1.905(11) 3_665 ? N1 C1 1.316(10) . ? N1 C3 1.449(10) . ? N1 C2 1.449(10) . ? N2 C4 1.325(10) . ? N2 C5 1.444(10) . ? N2 C6 1.447(10) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 W1 O1 101.2(5) . . ? O2 W1 O8 103.4(5) . . ? O1 W1 O8 89.1(5) . . ? O2 W1 O11 93.6(5) . . ? O1 W1 O11 88.0(5) . . ? O8 W1 O11 163.0(4) . . ? O2 W1 O7 96.5(6) . . ? O1 W1 O7 162.2(5) . . ? O8 W1 O7 89.6(5) . . ? O11 W1 O7 88.1(5) . . ? O2 W1 O6 162.4(5) . . ? O1 W1 O6 90.2(4) . . ? O8 W1 O6 90.0(4) . . ? O11 W1 O6 73.3(4) . . ? O7 W1 O6 72.0(5) . . ? O3 W2 O11 98.0(5) . . ? O3 W2 O9 99.0(5) . . ? O11 W2 O9 92.3(5) . . ? O3 W2 O10 101.4(6) . . ? O11 W2 O10 159.6(4) . . ? O9 W2 O10 90.5(5) . . ? O3 W2 O1 100.6(5) . 2_755 ? O11 W2 O1 87.2(4) . 2_755 ? O9 W2 O1 160.2(4) . 2_755 ? O10 W2 O1 83.5(5) . 2_755 ? O3 W2 O6 168.6(5) . . ? O11 W2 O6 73.1(4) . . ? O9 W2 O6 74.6(4) . . ? O10 W2 O6 88.3(4) . . ? O1 W2 O6 86.3(4) 2_755 . ? O12 W3 O7 98.7(6) . . ? O12 W3 O10 101.8(6) . 4_645 ? O7 W3 O10 91.7(5) . 4_645 ? O12 W3 O9 97.6(6) . . ? O7 W3 O9 91.7(5) . . ? O10 W3 O9 159.6(5) 4_645 . ? O12 W3 O8 101.1(6) . 3_665 ? O7 W3 O8 160.2(5) . 3_665 ? O10 W3 O8 82.6(4) 4_645 3_665 ? O9 W3 O8 87.4(5) . 3_665 ? O12 W3 O6 168.0(5) . . ? O7 W3 O6 73.6(4) . . ? O10 W3 O6 87.8(4) 4_645 . ? O9 W3 O6 73.9(4) . . ? O8 W3 O6 87.2(4) 3_665 . ? O5 Eu1 O5 145.4(8) . 14_454 ? O5 Eu1 O2 89.5(5) . . ? O5 Eu1 O2 76.9(4) 14_454 . ? O5 Eu1 O2 76.9(4) . 14_454 ? O5 Eu1 O2 89.5(5) 14_454 14_454 ? O2 Eu1 O2 133.2(6) . 14_454 ? O5 Eu1 O14 138.2(8) . . ? O5 Eu1 O14 69.7(9) 14_454 . ? O2 Eu1 O14 76.8(8) . . ? O2 Eu1 O14 139.6(6) 14_454 . ? O5 Eu1 O14 69.7(9) . 14_454 ? O5 Eu1 O14 138.2(8) 14_454 14_454 ? O2 Eu1 O14 139.6(6) . 14_454 ? O2 Eu1 O14 76.8(8) 14_454 14_454 ? O14 Eu1 O14 95.7(17) . 14_454 ? O5 Eu1 O13 72.7(4) . . ? O5 Eu1 O13 72.7(4) 14_454 . ? O2 Eu1 O13 66.6(3) . . ? O2 Eu1 O13 66.6(3) 14_454 . ? O14 Eu1 O13 132.2(8) . . ? O14 Eu1 O13 132.2(8) 14_454 . ? O5 Eu1 O4 70.0(7) . . ? O5 Eu1 O4 130.4(7) 14_454 . ? O2 Eu1 O4 69.1(5) . . ? O2 Eu1 O4 140.1(6) 14_454 . ? O14 Eu1 O4 68.2(9) . . ? O14 Eu1 O4 71.3(7) 14_454 . ? O13 Eu1 O4 121.1(4) . . ? O5 Eu1 O4 130.4(7) . 14_454 ? O5 Eu1 O4 70.0(7) 14_454 14_454 ? O2 Eu1 O4 140.1(6) . 14_454 ? O2 Eu1 O4 69.1(5) 14_454 14_454 ? O14 Eu1 O4 71.3(7) . 14_454 ? O14 Eu1 O4 68.2(9) 14_454 14_454 ? O13 Eu1 O4 121.1(4) . 14_454 ? O4 Eu1 O4 117.9(8) . 14_454 ? O6 Zn1 O6 108.3(5) 4_645 3_665 ? O6 Zn1 O6 110.0(3) 4_645 . ? O6 Zn1 O6 110.0(3) 3_665 . ? O6 Zn1 O6 110.0(3) 4_645 2_755 ? O6 Zn1 O6 110.0(3) 3_665 2_755 ? O6 Zn1 O6 108.3(5) . 2_755 ? W1 O1 W2 149.3(6) . 2_755 ? W1 O2 Eu1 162.3(7) . . ? C1 O4 Eu1 127.3(18) . . ? C4 O5 Eu1 134.5(13) . . ? Zn1 O6 W1 118.6(5) . . ? Zn1 O6 W2 119.4(5) . . ? W1 O6 W2 99.8(3) . . ? Zn1 O6 W3 119.1(4) . . ? W1 O6 W3 98.6(4) . . ? W2 O6 W3 96.9(4) . . ? W3 O7 W1 115.6(7) . . ? W1 O8 W3 151.2(6) . 4_645 ? W2 O9 W3 114.6(6) . . ? W3 O10 W2 156.5(7) 3_665 . ? W2 O11 W1 113.8(4) . . ? C1 N1 C3 117(3) . . ? C1 N1 C2 118(3) . . ? C3 N1 C2 125(3) . . ? C4 N2 C5 135(3) . . ? C4 N2 C6 115.3(19) . . ? C5 N2 C6 108(3) . . ? O4 C1 N1 130(3) . . ? O5 C4 N2 123(2) . . ? _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.69 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 2.640 _refine_diff_density_min -1.292 _refine_diff_density_rms 0.340 # Attachment '- La_POM.cif' data_LaPOM _database_code_depnum_ccdc_archive 'CCDC 869571' #TrackingRef '- La_POM.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C36 H90 La2 N12 O58 W12 Zn' _chemical_formula_weight 4168.59 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' La La -0.2871 2.4523 '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' W W -0.8490 6.8722 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zn Zn 0.2839 1.4301 '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-42d loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'y, -x, -z' '-x, -y, z' '-y, x, -z' 'x, -y+1/2, -z+1/4' '-y+1/2, -x, z+3/4' '-x, y+1/2, -z+1/4' 'y+1/2, x, z+3/4' 'x+1/2, y+1/2, z+1/2' 'y+1/2, -x+1/2, -z+1/2' '-x+1/2, -y+1/2, z+1/2' '-y+1/2, x+1/2, -z+1/2' 'x+1/2, -y+1, -z+3/4' '-y+1, -x+1/2, z+5/4' '-x+1/2, y+1, -z+3/4' 'y+1, x+1/2, z+5/4' _cell_length_a 14.1527(3) _cell_length_b 14.1527(3) _cell_length_c 44.8022(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8973.8(4) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 9212 _cell_measurement_theta_min 3.40 _cell_measurement_theta_max 25.15 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.19 _exptl_crystal_size_mid 0.17 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.085 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 7544 _exptl_absorpt_coefficient_mu 16.602 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.060 _exptl_absorpt_correction_T_max 0.161 _exptl_absorpt_process_details CrysAlisPro _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 'Xcalibur, Atlas, Gemini ultra' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 10.3592 _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% ? _diffrn_reflns_number 9212 _diffrn_reflns_av_R_equivalents 0.0522 _diffrn_reflns_av_sigmaI/netI 0.0731 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -43 _diffrn_reflns_limit_l_max 53 _diffrn_reflns_theta_min 3.40 _diffrn_reflns_theta_max 25.15 _reflns_number_total 3629 _reflns_number_gt 3018 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlisPro (Oxford Diffraction Ltd., 2010)' _computing_cell_refinement 'CrysAlisPro (Oxford Diffraction Ltd., 2010)' _computing_data_reduction 'CrysAlisPro (Oxford Diffraction Ltd., 2010)' _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. Because of the poor diffraction ability of the light atoms of C, N and O compared with the heavy atoms of W and La, the two disordered DMF ligands per asymmetric unit can not be well-positioned from difference Fourier maps. The distances between C, N and O atoms of DMF ligands were fixed to the reasonable values with 8 restraints, and were refined isotropically. The four disordered lattice DMF molecules per formular unit could not be located successfully from Fourier maps in the refinement cycles. The four lattice DMF molecules were removed using the SQUEEZE procedure implemented in the PLATON package. The resulting new file was used to further refine the structure. The composition of La-POM was figured out based on the elemental analysis, thermogravimetric analysis (TGA) and single crystal structure. The four lattice DMF molecules were added to account for the formula in the cif file. The poor crystal data suggest that only the gross connectivity and partial structure were obtained. The highest residual peak 1.48 is located at (0.4644, 0.3015, 0.0034), 1.07 \%A from W1. ; # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 -0.077 -0.061 -0.001 2456 499 ' ' _platon_squeeze_details ; Crystal structure was found to contain four disordered lattice solvent molecules, which could not be sufficiently modeled in the refinement cycles. These molecules were removed using the SQUEEZE procedure implemented in the PLATON package. ; _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^)+(0.0397P)^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 -0.04(2) _refine_ls_number_reflns 3629 _refine_ls_number_parameters 179 _refine_ls_number_restraints 8 _refine_ls_R_factor_all 0.0621 _refine_ls_R_factor_gt 0.0522 _refine_ls_wR_factor_ref 0.1312 _refine_ls_wR_factor_gt 0.1218 _refine_ls_goodness_of_fit_ref 1.171 _refine_ls_restrained_S_all 1.170 _refine_ls_shift/su_max 0.001 _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 W1 W 0.02237(8) 0.74756(7) 0.745851(16) 0.0497(3) Uani 1 1 d . . . W2 W -0.10461(7) 0.64327(7) 0.69487(2) 0.0486(3) Uani 1 1 d . . . W3 W 0.12532(7) 0.61775(7) 0.695698(19) 0.0474(3) Uani 1 1 d . . . La1 La 0.27447(12) 0.7500 0.6250 0.0442(4) Uani 1 2 d S . . Zn1 Zn 0.0000 0.5000 0.7500 0.0314(9) Uani 1 4 d S . . O1 O -0.0773(10) 0.7590(11) 0.7164(3) 0.053(4) Uani 1 1 d . . . O2 O 0.0294(12) 0.8648(11) 0.7550(3) 0.066(5) Uani 1 1 d . . . O3 O 0.0945(19) 0.7500 0.6250 0.092(9) Uani 1 2 d S . . O4 O -0.1809(11) 0.6869(11) 0.6685(3) 0.052(4) Uani 1 1 d . . . O5 O 0.1121(11) 0.7409(10) 0.7164(3) 0.049(4) Uani 1 1 d . . . O6 O -0.1070(10) 0.5047(10) 0.6842(2) 0.044(3) Uani 1 1 d . . . O7 O -0.0747(10) 0.7052(9) 0.7739(3) 0.043(3) Uani 1 1 d . . . O8 O 0.0101(10) 0.6082(9) 0.7258(2) 0.041(3) Uani 1 1 d . . . O9 O 0.0113(10) 0.6534(10) 0.6726(2) 0.044(3) Uani 1 1 d . . . O10 O 0.1065(11) 0.6936(9) 0.7742(3) 0.045(3) Uani 1 1 d . . . O11 O 0.2030(10) 0.6570(11) 0.6684(3) 0.046(4) Uani 1 1 d . . . O12 O 0.2160(15) 0.8977(15) 0.6492(4) 0.089(6) Uiso 1 1 d D . . O13 O 0.394(2) 0.6239(19) 0.6340(6) 0.130(9) Uiso 1 1 d . . . O14 O 0.3679(18) 0.7772(17) 0.6753(5) 0.113(8) Uani 1 1 d D . . N1 N 0.367(3) 0.759(3) 0.7257(8) 0.157(13) Uiso 1 1 d D . . N2 N 0.1347(18) 1.0287(17) 0.6600(5) 0.093(8) Uiso 1 1 d D . . C1 C 0.335(2) 0.792(2) 0.7002(5) 0.099(10) Uiso 1 1 d D . . H1A H 0.2815 0.8306 0.7012 0.119 Uiso 1 1 calc R . . C2 C 0.305(4) 0.790(4) 0.7495(12) 0.21(2) Uiso 1 1 d D . . H2A H 0.2564 0.8298 0.7414 0.322 Uiso 1 1 calc R . . H2B H 0.3401 0.8239 0.7642 0.322 Uiso 1 1 calc R . . H2C H 0.2759 0.7354 0.7586 0.322 Uiso 1 1 calc R . . C3 C 0.448(3) 0.696(4) 0.7305(10) 0.19(2) Uiso 1 1 d D . . H3A H 0.4789 0.6851 0.7118 0.284 Uiso 1 1 calc R . . H3B H 0.4257 0.6374 0.7386 0.284 Uiso 1 1 calc R . . H3C H 0.4910 0.7252 0.7442 0.284 Uiso 1 1 calc R . . C4 C 0.171(2) 0.9670(17) 0.6410(6) 0.092(10) Uiso 1 1 d D . . H4A H 0.1613 0.9764 0.6207 0.111 Uiso 1 1 calc R . . C5 C 0.093(2) 1.112(2) 0.6469(7) 0.095(10) Uiso 1 1 d D . . H5A H 0.1046 1.1124 0.6258 0.143 Uiso 1 1 calc R . . H5B H 0.1194 1.1674 0.6558 0.143 Uiso 1 1 calc R . . H5C H 0.0256 1.1112 0.6503 0.143 Uiso 1 1 calc R . . C6 C 0.115(4) 1.024(5) 0.6918(6) 0.23(3) Uiso 1 1 d D . . H6A H 0.0788 0.9684 0.6960 0.276 Uiso 1 1 calc R . . H6B H 0.0801 1.0790 0.6977 0.276 Uiso 1 1 calc R . . H6C H 0.1736 1.0216 0.7026 0.276 Uiso 1 1 calc R . . 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 W1 0.0637(7) 0.0453(5) 0.0401(4) -0.0018(4) -0.0020(4) 0.0000(5) W2 0.0540(6) 0.0547(6) 0.0372(4) 0.0081(4) -0.0062(4) -0.0008(5) W3 0.0558(6) 0.0520(5) 0.0344(4) 0.0048(4) 0.0054(4) -0.0052(5) La1 0.0440(10) 0.0476(10) 0.0410(8) 0.0057(8) 0.000 0.000 Zn1 0.0348(14) 0.0348(14) 0.0247(16) 0.000 0.000 0.000 O1 0.035(8) 0.054(10) 0.071(9) -0.025(8) 0.000(7) -0.020(7) O2 0.083(12) 0.054(10) 0.062(9) 0.016(8) -0.009(9) -0.026(9) O3 0.075(18) 0.13(2) 0.072(14) 0.063(18) 0.000 0.000 O4 0.051(9) 0.058(10) 0.046(8) 0.014(7) 0.003(7) -0.007(8) O5 0.067(10) 0.047(8) 0.031(6) -0.004(6) 0.021(7) -0.016(8) O6 0.060(9) 0.036(7) 0.035(6) -0.005(6) -0.021(6) 0.019(8) O7 0.051(9) 0.034(8) 0.042(7) -0.002(6) 0.005(6) 0.023(6) O8 0.050(8) 0.047(8) 0.027(6) 0.014(5) 0.013(6) 0.019(7) O9 0.046(8) 0.055(9) 0.032(6) 0.001(6) -0.022(6) 0.003(7) O10 0.054(9) 0.039(8) 0.041(7) 0.013(6) -0.008(7) -0.006(7) O11 0.049(9) 0.048(9) 0.042(8) 0.015(7) -0.016(6) -0.001(7) O14 0.12(2) 0.12(2) 0.101(14) -0.032(14) 0.009(14) -0.048(16) _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 W1 O2 1.712(16) . ? W1 O5 1.833(12) . ? W1 O10 1.899(13) . ? W1 O1 1.938(14) . ? W1 O7 1.957(14) . ? W1 O8 2.175(13) . ? W2 O4 1.715(15) . ? W2 O9 1.924(15) . ? W2 O1 1.940(14) . ? W2 O10 1.945(12) 12_556 ? W2 O6 2.018(14) . ? W2 O8 2.190(13) . ? W3 O11 1.735(15) . ? W3 O6 1.827(14) 3_565 ? W3 O7 1.871(14) 10_456 ? W3 O9 1.982(12) . ? W3 O5 1.984(13) . ? W3 O8 2.119(12) . ? La1 O13 2.50(3) 5_566 ? La1 O13 2.50(3) . ? La1 O12 2.50(2) 5_566 ? La1 O12 2.50(2) . ? La1 O3 2.55(3) . ? La1 O11 2.558(14) . ? La1 O11 2.558(14) 5_566 ? La1 O14 2.64(2) . ? La1 O14 2.64(2) 5_566 ? Zn1 O8 1.883(12) 10_456 ? Zn1 O8 1.883(12) 3_565 ? Zn1 O8 1.883(12) . ? Zn1 O8 1.883(12) 12_556 ? O6 W3 1.827(14) 3_565 ? O7 W3 1.871(14) 12_556 ? O10 W2 1.945(12) 10_456 ? O12 C4 1.229(10) . ? O14 C1 1.230(10) . ? N1 C1 1.321(10) . ? N1 C2 1.453(10) . ? N1 C3 1.455(10) . ? N2 C4 1.321(10) . ? N2 C5 1.445(10) . ? N2 C6 1.451(10) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 W1 O5 100.4(7) . . ? O2 W1 O10 101.2(7) . . ? O5 W1 O10 91.4(6) . . ? O2 W1 O1 97.1(7) . . ? O5 W1 O1 91.1(6) . . ? O10 W1 O1 160.8(6) . . ? O2 W1 O7 100.6(7) . . ? O5 W1 O7 158.9(6) . . ? O10 W1 O7 83.6(5) . . ? O1 W1 O7 87.2(6) . . ? O2 W1 O8 169.3(6) . . ? O5 W1 O8 73.2(5) . . ? O10 W1 O8 87.8(5) . . ? O1 W1 O8 74.7(6) . . ? O7 W1 O8 86.1(5) . . ? O4 W2 O9 98.8(6) . . ? O4 W2 O1 99.4(7) . . ? O9 W2 O1 91.5(6) . . ? O4 W2 O10 100.4(6) . 12_556 ? O9 W2 O10 160.3(5) . 12_556 ? O1 W2 O10 90.0(6) . 12_556 ? O4 W2 O6 100.2(6) . . ? O9 W2 O6 87.9(6) . . ? O1 W2 O6 160.3(6) . . ? O10 W2 O6 84.2(6) 12_556 . ? O4 W2 O8 169.5(6) . . ? O9 W2 O8 73.3(4) . . ? O1 W2 O8 74.3(6) . . ? O10 W2 O8 88.2(5) 12_556 . ? O6 W2 O8 86.7(5) . . ? O11 W3 O6 101.3(6) . 3_565 ? O11 W3 O7 103.5(6) . 10_456 ? O6 W3 O7 89.0(6) 3_565 10_456 ? O11 W3 O9 93.9(6) . . ? O6 W3 O9 88.8(6) 3_565 . ? O7 W3 O9 162.6(5) 10_456 . ? O11 W3 O5 96.2(6) . . ? O6 W3 O5 162.3(5) 3_565 . ? O7 W3 O5 90.2(6) 10_456 . ? O9 W3 O5 86.8(6) . . ? O11 W3 O8 162.9(6) . . ? O6 W3 O8 90.6(5) 3_565 . ? O7 W3 O8 89.0(5) 10_456 . ? O9 W3 O8 73.8(5) . . ? O5 W3 O8 71.7(5) . . ? O13 La1 O13 94.3(13) 5_566 . ? O13 La1 O12 138.9(7) 5_566 5_566 ? O13 La1 O12 72.4(8) . 5_566 ? O13 La1 O12 72.4(8) 5_566 . ? O13 La1 O12 138.9(7) . . ? O12 La1 O12 141.3(10) 5_566 . ? O13 La1 O3 132.9(6) 5_566 . ? O13 La1 O3 132.9(6) . . ? O12 La1 O3 70.6(5) 5_566 . ? O12 La1 O3 70.6(5) . . ? O13 La1 O11 139.4(7) 5_566 . ? O13 La1 O11 77.2(7) . . ? O12 La1 O11 76.6(6) 5_566 . ? O12 La1 O11 88.2(6) . . ? O3 La1 O11 66.7(3) . . ? O13 La1 O11 77.2(7) 5_566 5_566 ? O13 La1 O11 139.4(7) . 5_566 ? O12 La1 O11 88.2(6) 5_566 5_566 ? O12 La1 O11 76.6(6) . 5_566 ? O3 La1 O11 66.7(3) . 5_566 ? O11 La1 O11 133.4(6) . 5_566 ? O13 La1 O14 72.1(8) 5_566 . ? O13 La1 O14 68.0(9) . . ? O12 La1 O14 131.2(7) 5_566 . ? O12 La1 O14 70.9(7) . . ? O3 La1 O14 120.1(5) . . ? O11 La1 O14 67.9(6) . . ? O11 La1 O14 140.6(6) 5_566 . ? O13 La1 O14 68.0(9) 5_566 5_566 ? O13 La1 O14 72.1(8) . 5_566 ? O12 La1 O14 70.9(7) 5_566 5_566 ? O12 La1 O14 131.2(7) . 5_566 ? O3 La1 O14 120.1(5) . 5_566 ? O11 La1 O14 140.6(6) . 5_566 ? O11 La1 O14 67.9(6) 5_566 5_566 ? O14 La1 O14 119.9(11) . 5_566 ? O8 Zn1 O8 109.4(4) 10_456 3_565 ? O8 Zn1 O8 109.4(4) 10_456 . ? O8 Zn1 O8 109.5(7) 3_565 . ? O8 Zn1 O8 109.5(7) 10_456 12_556 ? O8 Zn1 O8 109.4(4) 3_565 12_556 ? O8 Zn1 O8 109.4(3) . 12_556 ? W1 O1 W2 114.4(8) . . ? W1 O5 W3 116.5(7) . . ? W3 O6 W2 149.0(7) 3_565 . ? W3 O7 W1 151.8(7) 12_556 . ? Zn1 O8 W3 118.5(6) . . ? Zn1 O8 W1 120.3(5) . . ? W3 O8 W1 98.3(5) . . ? Zn1 O8 W2 119.5(7) . . ? W3 O8 W2 98.9(4) . . ? W1 O8 W2 96.6(5) . . ? W2 O9 W3 113.9(5) . . ? W1 O10 W2 154.7(8) . 10_456 ? W3 O11 La1 162.0(8) . . ? C4 O12 La1 135.4(19) . . ? C1 O14 La1 127(2) . . ? C1 N1 C2 108(4) . . ? C1 N1 C3 128(4) . . ? C2 N1 C3 123(4) . . ? C4 N2 C5 116(2) . . ? C4 N2 C6 132(4) . . ? C5 N2 C6 111(3) . . ? O14 C1 N1 126(4) . . ? O12 C4 N2 122(3) . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 25.15 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 1.483 _refine_diff_density_min -1.730 _refine_diff_density_rms 0.264 # Attachment '- Tb_POM.cif' data_TbPOM _database_code_depnum_ccdc_archive 'CCDC 869572' #TrackingRef '- Tb_POM.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C36 H90 N12 O58 Tb2 W12 Zn' _chemical_formula_weight 4208.61 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' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Tb Tb -0.1723 4.1537 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' W W -0.8490 6.8722 '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-42d loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' '-x+1/2, y, -z+3/4' 'x+1/2, -y, -z+3/4' '-y+1/2, -x, z+3/4' 'y+1/2, x, z+3/4' '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' '-x+1, y+1/2, -z+5/4' 'x+1, -y+1/2, -z+5/4' '-y+1, -x+1/2, z+5/4' 'y+1, x+1/2, z+5/4' _cell_length_a 13.8766(5) _cell_length_b 13.8766(5) _cell_length_c 44.477(2) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 8564.6(6) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 12104 _cell_measurement_theta_min 3.46 _cell_measurement_theta_max 25.06 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.31 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.264 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 7608 _exptl_absorpt_coefficient_mu 18.049 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.049 _exptl_absorpt_correction_T_max 0.138 _exptl_absorpt_process_details CrysAlisPro _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 'Xcalibur, Atlas, Gemini ultra' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 10.3592 _diffrn_standards_number none _diffrn_standards_interval_count none _diffrn_standards_interval_time none _diffrn_standards_decay_% ? _diffrn_reflns_number 12104 _diffrn_reflns_av_R_equivalents 0.0590 _diffrn_reflns_av_sigmaI/netI 0.0627 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -45 _diffrn_reflns_limit_l_max 52 _diffrn_reflns_theta_min 3.46 _diffrn_reflns_theta_max 25.06 _reflns_number_total 3561 _reflns_number_gt 2413 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlisPro (Oxford Diffraction Ltd., 2010)' _computing_cell_refinement 'CrysAlisPro (Oxford Diffraction Ltd., 2010)' _computing_data_reduction 'CrysAlisPro (Oxford Diffraction Ltd., 2010)' _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. Because of the poor diffraction ability of the light atoms of C, N and O compared with the heavy atoms of W and Tb, the two disordered DMF ligands per asymmetric unit can not be well-positioned from difference Fourier maps. The distances between C, N and O atoms of DMF ligands were fixed to the reasonable values with 16 restraints, and were refined isotropically. The four disordered lattice DMF molecules per formular unit could not be located successfully from Fourier maps in the refinement cycles. The four lattice DMF molecules were removed using the SQUEEZE procedure implemented in the PLATON package. The resulting new file was used to further refine the structure. The composition of Tb-POM was figured out based on the elemental analysis, thermogravimetric analysis (TGA) and single crystal structure. The four lattice DMF molecules were added to account for the formula in the cif file. The poor crystal data suggest that only the gross connectivity and partial structure were obtained. The relative high Flack parameter for Tb-POM suggests that the crystal is partially twined. The highest residual peak 2.24 is located at (0.0026, 0.1363, 0.0555), 1.59 \%A from W1. ; # SQUEEZE RESULTS (APPEND TO CIF) # Note: Data are Listed for all Voids in the P1 Unit Cell # i.e. Centre of Gravity, Solvent Accessible Volume, # Recovered number of Electrons in the Void and # Details about the Squeezed Material loop_ _platon_squeeze_void_nr _platon_squeeze_void_average_x _platon_squeeze_void_average_y _platon_squeeze_void_average_z _platon_squeeze_void_volume _platon_squeeze_void_count_electrons _platon_squeeze_void_content 1 -0.168 -0.051 0.395 2119 393 ' ' _platon_squeeze_details ; Crystal structure was found to contain four disordered lattice solvent molecules, which could not be sufficiently modeled in the refinement cycles. These molecules were removed using the SQUEEZE procedure implemented in the PLATON package. ; _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^)+(0.0672P)^2^+61.8404P] 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 0.24(5) _refine_ls_number_reflns 3561 _refine_ls_number_parameters 166 _refine_ls_number_restraints 16 _refine_ls_R_factor_all 0.0969 _refine_ls_R_factor_gt 0.0748 _refine_ls_wR_factor_ref 0.1940 _refine_ls_wR_factor_gt 0.1791 _refine_ls_goodness_of_fit_ref 1.145 _refine_ls_restrained_S_all 1.145 _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 W1 W 0.11730(16) 0.36881(13) 0.19576(3) 0.0955(6) Uani 1 1 d . . . W2 W -0.11750(14) 0.36427(12) 0.19414(3) 0.0909(5) Uani 1 1 d . . . W3 W 0.0009(2) 0.24659(10) 0.24574(3) 0.0963(5) Uani 1 1 d . . . Tb1 Tb 0.26212(15) 0.2500 0.1250 0.0742(5) Uani 1 2 d SD . . Zn1 Zn 0.0000 0.5000 0.2500 0.0668(13) Uani 1 4 d S . . O1 O 0.1080(11) 0.503(2) 0.1865(3) 0.087(5) Uani 1 1 d . . . O2 O 0.192(3) 0.324(2) 0.1703(6) 0.133(5) Uani 1 1 d . . . O3 O -0.1975(19) 0.3306(18) 0.1647(5) 0.098(7) Uani 1 1 d . . . O4 O 0.373(2) 0.218(2) 0.1653(5) 0.133(5) Uani 1 1 d D . . O5 O 0.208(2) 0.114(2) 0.1473(5) 0.133(5) Uani 1 1 d D . . O6 O 0.0030(17) 0.3906(11) 0.2251(3) 0.070(4) Uani 1 1 d . . . O7 O 0.0967(16) 0.2416(11) 0.2153(5) 0.086(7) Uani 1 1 d . . . O8 O 0.2038(15) 0.402(2) 0.2282(6) 0.104(9) Uani 1 1 d . . . O9 O -0.102(3) 0.246(2) 0.2174(5) 0.133(5) Uani 1 1 d . . . O10 O -0.2034(15) 0.4144(15) 0.2259(4) 0.072(6) Uani 1 1 d . . . O11 O -0.009(2) 0.3502(15) 0.1733(4) 0.107(8) Uani 1 1 d . . . O12 O 0.0176(18) 0.134(2) 0.2507(5) 0.136(10) Uani 1 1 d . . . O13 O 0.086(3) 0.2500 0.1250 0.133(5) Uani 1 2 d S . . O14 O 0.371(4) 0.380(4) 0.138(2) 0.34(5) Uani 1 1 d . . . N1 N 0.384(5) 0.231(6) 0.2177(7) 0.20(3) Uiso 1 1 d D . . C1 C 0.342(3) 0.228(6) 0.1911(3) 0.20(3) Uiso 1 1 d D . . H1A H 0.2752 0.2331 0.1919 0.237 Uiso 1 1 calc R . . C2 C 0.331(6) 0.187(7) 0.2424(13) 0.25(5) Uiso 1 1 d D . . H2A H 0.3725 0.1838 0.2597 0.376 Uiso 1 1 calc R . . H2B H 0.3120 0.1232 0.2367 0.376 Uiso 1 1 calc R . . H2C H 0.2755 0.2250 0.2470 0.376 Uiso 1 1 calc R . . C3 C 0.461(5) 0.301(6) 0.2201(15) 0.23(5) Uiso 1 1 d D . . H3A H 0.4952 0.2908 0.2386 0.338 Uiso 1 1 calc R . . H3B H 0.4345 0.3649 0.2199 0.338 Uiso 1 1 calc R . . H3C H 0.5042 0.2934 0.2035 0.338 Uiso 1 1 calc R . . N2 N 0.131(3) -0.025(2) 0.1616(7) 0.137(12) Uiso 1 1 d D . . C4 C 0.170(3) 0.036(2) 0.1424(9) 0.150(18) Uiso 1 1 d D . . H4A H 0.1692 0.0165 0.1224 0.180 Uiso 1 1 calc R . . C5 C 0.141(4) 0.000(5) 0.1931(9) 0.22(2) Uiso 1 1 d D . . H5B H 0.1125 -0.0499 0.2053 0.323 Uiso 1 1 calc R . . H5C H 0.1079 0.0597 0.1969 0.323 Uiso 1 1 calc R . . H5D H 0.2076 0.0066 0.1981 0.323 Uiso 1 1 calc R . . C6 C 0.092(3) -0.114(2) 0.1495(8) 0.114(12) Uiso 1 1 d D . . H6B H 0.0925 -0.1107 0.1280 0.171 Uiso 1 1 calc R . . H6C H 0.0275 -0.1223 0.1566 0.171 Uiso 1 1 calc R . . H6D H 0.1312 -0.1672 0.1560 0.171 Uiso 1 1 calc R . . 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 W1 0.1277(13) 0.0943(11) 0.0646(8) -0.0093(9) 0.0190(9) 0.0081(10) W2 0.1175(13) 0.0941(11) 0.0609(8) -0.0106(8) -0.0147(9) -0.0044(9) W3 0.1344(11) 0.0791(8) 0.0754(7) 0.0118(6) -0.0030(10) -0.0047(14) Tb1 0.0857(13) 0.0745(12) 0.0624(10) -0.0066(10) 0.000 0.000 Zn1 0.078(2) 0.078(2) 0.045(2) 0.000 0.000 0.000 O1 0.069(10) 0.141(16) 0.051(8) 0.014(14) -0.007(7) 0.011(17) O2 0.197(15) 0.141(11) 0.062(6) 0.007(7) -0.020(8) -0.032(11) O3 0.106(17) 0.112(18) 0.076(13) -0.001(12) -0.032(12) -0.019(13) O4 0.197(15) 0.141(11) 0.062(6) 0.007(7) -0.020(8) -0.032(11) O5 0.197(15) 0.141(11) 0.062(6) 0.007(7) -0.020(8) -0.032(11) O6 0.079(10) 0.091(11) 0.039(7) -0.016(7) 0.031(10) -0.005(13) O7 0.117(15) 0.023(8) 0.118(16) 0.019(10) -0.044(13) -0.004(9) O8 0.054(12) 0.15(2) 0.110(17) -0.049(16) 0.045(12) 0.009(13) O9 0.197(15) 0.141(11) 0.062(6) 0.007(7) -0.020(8) -0.032(11) O10 0.100(15) 0.085(14) 0.030(8) 0.028(8) -0.007(9) -0.001(10) O11 0.128(19) 0.104(14) 0.088(12) 0.036(11) -0.072(16) -0.048(16) O12 0.09(2) 0.19(3) 0.135(19) -0.060(18) -0.019(15) -0.04(2) O13 0.197(15) 0.141(11) 0.062(6) 0.007(7) -0.020(8) -0.032(11) O14 0.20(5) 0.30(7) 0.52(13) -0.12(7) 0.17(6) -0.10(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 W1 O2 1.65(4) . ? W1 O1 1.92(3) . ? W1 O8 1.93(3) . ? W1 O7 1.988(17) . ? W1 O11 2.03(2) . ? W1 O6 2.075(17) . ? W1 W3 3.229(2) . ? W2 O11 1.78(3) . ? W2 O3 1.78(2) . ? W2 O1 1.87(3) 2_565 ? W2 O9 1.95(3) . ? W2 O10 1.98(2) . ? W2 O6 2.20(2) . ? W3 O12 1.59(3) . ? W3 O10 1.86(2) 12 ? W3 O7 1.90(2) . ? W3 O9 1.91(3) . ? W3 O8 1.92(3) 11_455 ? W3 O6 2.199(15) . ? Tb1 O5 2.26(3) 14_454 ? Tb1 O5 2.26(3) . ? Tb1 O4 2.40(3) . ? Tb1 O4 2.40(3) 14_454 ? Tb1 O14 2.42(6) 14_454 ? Tb1 O14 2.42(6) . ? Tb1 O13 2.45(5) . ? Tb1 O2 2.47(3) 14_454 ? Tb1 O2 2.47(3) . ? Zn1 O6 1.881(14) . ? Zn1 O6 1.881(14) 2_565 ? Zn1 O6 1.881(14) 12 ? Zn1 O6 1.881(14) 11_455 ? O1 W2 1.87(3) 2_565 ? O4 C1 1.232(10) . ? O5 C4 1.225(10) . ? O8 W3 1.92(3) 12 ? O10 W3 1.86(2) 11_455 ? N1 C1 1.318(9) . ? N1 C3 1.449(9) . ? N1 C2 1.450(9) . ? N2 C4 1.319(9) . ? N2 C6 1.444(9) . ? N2 C5 1.451(9) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 W1 O1 105.0(12) . . ? O2 W1 O8 102.4(12) . . ? O1 W1 O8 88.1(10) . . ? O2 W1 O7 93.4(13) . . ? O1 W1 O7 161.6(8) . . ? O8 W1 O7 88.6(10) . . ? O2 W1 O11 98.8(14) . . ? O1 W1 O11 87.8(7) . . ? O8 W1 O11 158.8(10) . . ? O7 W1 O11 88.8(8) . . ? O2 W1 O6 164.3(12) . . ? O1 W1 O6 86.6(6) . . ? O8 W1 O6 88.3(7) . . ? O7 W1 O6 75.2(8) . . ? O11 W1 O6 70.7(9) . . ? O2 W1 W3 126.1(11) . . ? O1 W1 W3 128.7(5) . . ? O8 W1 W3 85.6(8) . . ? O7 W1 W3 32.9(7) . . ? O11 W1 W3 80.8(6) . . ? O6 W1 W3 42.4(4) . . ? O11 W2 O3 96.8(11) . . ? O11 W2 O1 87.4(8) . 2_565 ? O3 W2 O1 99.7(9) . 2_565 ? O11 W2 O9 95.3(12) . . ? O3 W2 O9 103.7(12) . . ? O1 W2 O9 156.0(9) 2_565 . ? O11 W2 O10 157.2(8) . . ? O3 W2 O10 104.0(11) . . ? O1 W2 O10 80.0(7) 2_565 . ? O9 W2 O10 88.9(11) . . ? O11 W2 O6 72.4(7) . . ? O3 W2 O6 168.5(10) . . ? O1 W2 O6 84.1(6) 2_565 . ? O9 W2 O6 74.1(10) . . ? O10 W2 O6 87.3(7) . . ? O12 W3 O10 100.4(10) . 12 ? O12 W3 O7 87.8(11) . . ? O10 W3 O7 93.1(8) 12 . ? O12 W3 O9 101.4(13) . . ? O10 W3 O9 157.5(12) 12 . ? O7 W3 O9 93.2(9) . . ? O12 W3 O8 111.8(11) . 11_455 ? O10 W3 O8 84.7(9) 12 11_455 ? O7 W3 O8 160.4(7) . 11_455 ? O9 W3 O8 82.2(13) . 11_455 ? O12 W3 O6 161.1(10) . . ? O10 W3 O6 86.3(8) 12 . ? O7 W3 O6 74.1(7) . . ? O9 W3 O6 74.7(11) . . ? O8 W3 O6 86.3(7) 11_455 . ? O12 W3 W1 122.5(9) . . ? O10 W3 W1 87.4(5) 12 . ? O7 W3 W1 34.7(5) . . ? O9 W3 W1 85.6(9) . . ? O8 W3 W1 125.7(5) 11_455 . ? O6 W3 W1 39.5(5) . . ? O5 Tb1 O5 141.5(18) 14_454 . ? O5 Tb1 O4 133.7(11) 14_454 . ? O5 Tb1 O4 74.4(9) . . ? O5 Tb1 O4 74.4(9) 14_454 14_454 ? O5 Tb1 O4 133.7(11) . 14_454 ? O4 Tb1 O4 100.3(14) . 14_454 ? O5 Tb1 O14 137(2) 14_454 14_454 ? O5 Tb1 O14 72(2) . 14_454 ? O4 Tb1 O14 68.7(19) . 14_454 ? O4 Tb1 O14 64(2) 14_454 14_454 ? O5 Tb1 O14 72(2) 14_454 . ? O5 Tb1 O14 137(2) . . ? O4 Tb1 O14 64(2) . . ? O4 Tb1 O14 68.7(19) 14_454 . ? O14 Tb1 O14 103(3) 14_454 . ? O5 Tb1 O13 70.7(9) 14_454 . ? O5 Tb1 O13 70.7(9) . . ? O4 Tb1 O13 129.9(7) . . ? O4 Tb1 O13 129.9(7) 14_454 . ? O14 Tb1 O13 128.7(13) 14_454 . ? O14 Tb1 O13 128.7(13) . . ? O5 Tb1 O2 82.0(10) 14_454 14_454 ? O5 Tb1 O2 82.9(10) . 14_454 ? O4 Tb1 O2 141.9(10) . 14_454 ? O4 Tb1 O2 73.9(12) 14_454 14_454 ? O14 Tb1 O2 75.3(17) 14_454 14_454 ? O14 Tb1 O2 139(2) . 14_454 ? O13 Tb1 O2 66.6(8) . 14_454 ? O5 Tb1 O2 82.9(10) 14_454 . ? O5 Tb1 O2 82.0(10) . . ? O4 Tb1 O2 73.9(12) . . ? O4 Tb1 O2 141.9(10) 14_454 . ? O14 Tb1 O2 139(2) 14_454 . ? O14 Tb1 O2 75.3(17) . . ? O13 Tb1 O2 66.6(8) . . ? O2 Tb1 O2 133.2(16) 14_454 . ? O6 Zn1 O6 107.7(8) . 2_565 ? O6 Zn1 O6 110.3(4) . 12 ? O6 Zn1 O6 110.3(4) 2_565 12 ? O6 Zn1 O6 110.3(4) . 11_455 ? O6 Zn1 O6 110.3(4) 2_565 11_455 ? O6 Zn1 O6 107.7(8) 12 11_455 ? W2 O1 W1 155.9(8) 2_565 . ? W1 O2 Tb1 164.7(19) . . ? C1 O4 Tb1 116.7(19) . . ? C4 O5 Tb1 144(2) . . ? Zn1 O6 W1 120.3(10) . . ? Zn1 O6 W3 119.1(6) . . ? W1 O6 W3 98.1(7) . . ? Zn1 O6 W2 119.1(10) . . ? W1 O6 W2 99.5(5) . . ? W3 O6 W2 95.8(7) . . ? W3 O7 W1 112.4(10) . . ? W3 O8 W1 147.5(15) 12 . ? W3 O9 W2 115.4(16) . . ? W3 O10 W2 159.0(12) 11_455 . ? W2 O11 W1 117.4(10) . . ? C1 N1 C3 115(4) . . ? C1 N1 C2 116(4) . . ? C3 N1 C2 126.5(13) . . ? O4 C1 N1 133(4) . . ? C4 N2 C6 117(3) . . ? C4 N2 C5 116(3) . . ? C6 N2 C5 127(3) . . ? O5 C4 N2 129(4) . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 25.06 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 2.240 _refine_diff_density_min -1.030 _refine_diff_density_rms 0.227