data_1 _audit_creation_method SHELXL-2013 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C27 H23 La2 N5 O14' _chemical_formula_sum 'C27 H23 La2 N5 O14' _chemical_formula_weight 919.32 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' _space_group_crystal_system 'orthorhombic' _space_group_IT_number 62 _space_group_name_H-M_alt 'P n m a' _space_group_name_Hall '-P 2ac 2n' _shelx_space_group_comment ; The symmetry employed for this shelxl refinement is uniquely defined by the following loop, which should always be used as a source of symmetry information in preference to the above space-group names. They are only intended as comments. ; loop_ _space_group_symop_operation_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z' 'x+1/2, -y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z' '-x-1/2, y-1/2, z-1/2' _cell_length_a 8.1241(3) _cell_length_b 30.3843(10) _cell_length_c 15.6616(5) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 3866.0(2) _cell_formula_units_Z 4 _cell_measurement_temperature 110(2) _cell_measurement_reflns_used 3262 _cell_measurement_theta_min 2.40 _cell_measurement_theta_max 26.45 _exptl_crystal_description 'needle' _exptl_crystal_colour 'colorless' _exptl_crystal_density_meas ? _exptl_crystal_density_method ? _exptl_crystal_density_diffrn 1.579 _exptl_crystal_F_000 1784 _exptl_transmission_factor_min ? _exptl_transmission_factor_max ? _exptl_crystal_size_max 0.350 _exptl_crystal_size_mid 0.150 _exptl_crystal_size_min 0.100 _exptl_absorpt_coefficient_mu 2.243 _shelx_estimated_absorpt_T_min 0.507 _shelx_estimated_absorpt_T_max 0.807 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.507 _exptl_absorpt_correction_T_max 0.807 _exptl_absorpt_process_details 'Sadabs, Bruker-AXS' _exptl_special_details ; ? ; _diffrn_ambient_temperature 110(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_source 'ImuS microsource' _diffrn_measurement_device_type 'ApexDuo, Bruker-AXS' _diffrn_measurement_method '1 deg. \f scans' _diffrn_detector_area_resol_mean 1.75 _diffrn_reflns_number 24239 _diffrn_reflns_av_unetI/netI 0.0280 _diffrn_reflns_av_R_equivalents 0.0313 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -38 _diffrn_reflns_limit_k_max 37 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 19 _diffrn_reflns_theta_min 2.395 _diffrn_reflns_theta_max 26.450 _diffrn_reflns_theta_full 25.242 _diffrn_measured_fraction_theta_max 0.934 _diffrn_measured_fraction_theta_full 0.966 _diffrn_reflns_Laue_measured_fraction_max 0.934 _diffrn_reflns_Laue_measured_fraction_full 0.966 _diffrn_reflns_point_group_measured_fraction_max 0.934 _diffrn_reflns_point_group_measured_fraction_full 0.966 _reflns_number_total 3799 _reflns_number_gt 3262 _reflns_threshold_expression 'I > 2\s(I)' _reflns_Friedel_coverage 0.000 _reflns_Friedel_fraction_max . _reflns_Friedel_fraction_full . _reflns_special_details ; Reflections were merged by SHELXL according to the crystal class for the calculation of statistics and refinement. _reflns_Friedel_fraction is defined as the number of unique Friedel pairs measured divided by the number that would be possible theoretically, ignoring centric projections and systematic absences. ; _computing_data_collection 'Apex2, Bruker-AXS' _computing_cell_refinement 'Apex2, Bruker-AXS' _computing_data_reduction 'Saint, Bruker-AXS' _computing_structure_solution 'Saint, Bruker-AXS' _computing_structure_refinement 'SHELXL-2013 (Sheldrick, 2008)' _computing_molecular_graphics ? _computing_publication_material ? _refine_special_details ; THe crystal contains also DMF crystallization solvent, positioned on, and disordered about the mirror planes, which could not be reliably modeled by discrete atoms. Its contribution was subtracted from the diffraction pattern, using the Squeeze technique and Platon software (Spek, 2009). The peripheral NMe2 residue of the metal-coordinated DMF ligand reveals partial disorder as well. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'w=1/[\s^2^(Fo^2^)+(0.0435P)^2^+4.1176P] 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_number_reflns 3799 _refine_ls_number_parameters 228 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0510 _refine_ls_R_factor_gt 0.0434 _refine_ls_wR_factor_ref 0.1113 _refine_ls_wR_factor_gt 0.1085 _refine_ls_goodness_of_fit_ref 1.080 _refine_ls_restrained_S_all 1.080 _refine_ls_shift/su_max 0.032 _refine_ls_shift/su_mean 0.013 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_site_symmetry_order _atom_site_calc_flag _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group La1 La 0.93440(4) 0.59121(2) 0.70363(2) 0.00748(12) Uani 1 1 d . . . . . O2 O 0.8897(5) 0.46119(13) 0.3895(3) 0.0158(9) Uani 1 1 d . . . . . O3 O 0.7418(5) 0.40625(12) 0.3387(2) 0.0125(9) Uani 1 1 d . . . . . O4 O 0.4941(6) 0.52466(13) 0.7102(2) 0.0161(9) Uani 1 1 d . . . . . O5 O 0.7389(5) 0.53863(13) 0.6513(3) 0.0206(10) Uani 1 1 d . . . . . O6 O 1.1554(5) 0.63204(11) 0.8160(2) 0.0101(8) Uani 1 1 d . . . . . O7 O 0.9888(5) 0.67043(12) 0.7339(3) 0.0162(9) Uani 1 1 d . . . . . C8 C 0.6608(7) 0.43974(17) 0.4719(3) 0.0098(11) Uani 1 1 d . . . . . C9 C 0.5288(8) 0.41202(18) 0.4866(4) 0.0141(13) Uani 1 1 d . . . . . H9 H 0.5069 0.3894 0.4463 0.017 Uiso 1 1 calc R U . . . N10 N 0.4306(7) 0.41547(16) 0.5547(3) 0.0206(12) Uani 1 1 d . . . . . C11 C 0.4595(7) 0.44872(19) 0.6088(4) 0.0134(12) Uani 1 1 d . . . . . H11 H 0.3875 0.4523 0.6561 0.016 Uiso 1 1 calc R U . . . C12 C 0.5892(7) 0.47823(17) 0.5995(3) 0.0101(11) Uani 1 1 d . . . . . C13 C 0.6921(7) 0.47300(17) 0.5305(3) 0.0119(12) Uani 1 1 d . . . . . H13 H 0.7839 0.4920 0.5230 0.014 Uiso 1 1 calc R U . . . C14 C 0.7676(8) 0.43579(17) 0.3938(4) 0.0135(12) Uani 1 1 d . . . . . C15 C 0.6089(7) 0.51632(17) 0.6586(3) 0.0113(12) Uani 1 1 d . . . . . C16 C 1.1480(7) 0.71064(16) 0.8315(4) 0.0104(11) Uani 1 1 d . . . . . C17 C 1.2456(8) 0.71234(18) 0.9044(4) 0.0152(13) Uani 1 1 d . . . . . H17 H 1.2804 0.6854 0.9293 0.018 Uiso 1 1 calc R U . . . N18 N 1.2929(10) 0.7500 0.9413(5) 0.0220(18) Uani 1 2 d S T P . . C19 C 1.0977(10) 0.7500 0.7953(5) 0.0104(16) Uani 1 2 d S T P . . H19 H 1.0294 0.7500 0.7461 0.013 Uiso 1 2 calc R U P . . C20 C 1.0964(7) 0.66846(18) 0.7920(3) 0.0105(12) Uani 1 1 d . . . . . O21 O 0.9390(6) 0.61618(13) 0.5501(2) 0.0177(9) Uani 1 1 d . . . . . C22 C 0.9385(8) 0.5929(2) 0.4848(4) 0.0174(13) Uani 1 1 d . . . . . H22 H 0.8952 0.5640 0.4905 0.021 Uiso 1 1 calc R U . . . N23 N 0.9903(10) 0.6039(2) 0.4108(4) 0.048(2) Uani 1 1 d D . . . . C24 C 0.9845(12) 0.5736(4) 0.3377(5) 0.048(3) Uani 1 1 d . . . . . H24A H 1.0969 0.5671 0.3187 0.064 Uiso 1 1 calc R U . . . H24B H 0.9231 0.5873 0.2908 0.064 Uiso 1 1 calc R U . . . H24C H 0.9298 0.5463 0.3548 0.064 Uiso 1 1 calc R U . . . C25A C 1.098(2) 0.6422(5) 0.3974(8) 0.044(6) Uani 0.58(3) 1 d D . P A 1 H25A H 1.1075 0.6587 0.4509 0.066 Uiso 0.58(3) 1 calc R U P A 1 H25B H 1.0501 0.6612 0.3532 0.066 Uiso 0.58(3) 1 calc R U P A 1 H25C H 1.2067 0.6322 0.3792 0.066 Uiso 0.58(3) 1 calc R U P A 1 C25B C 0.965(7) 0.6510(5) 0.393(3) 0.046(17) Uiso 0.42(3) 1 d D . P A 2 H25D H 0.8545 0.6556 0.3704 0.069 Uiso 0.42(3) 1 calc R U P A 2 H25E H 1.0471 0.6611 0.3516 0.069 Uiso 0.42(3) 1 calc R U P A 2 H25F H 0.9781 0.6678 0.4464 0.069 Uiso 0.42(3) 1 calc R U P 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 La1 0.0078(2) 0.00598(16) 0.00869(17) -0.00024(11) 0.00144(12) 0.00007(12) O2 0.014(2) 0.014(2) 0.020(2) -0.0009(17) 0.0070(18) 0.0005(16) O3 0.016(2) 0.017(2) 0.0051(18) -0.0006(16) 0.0005(16) 0.0056(16) O4 0.019(2) 0.015(2) 0.014(2) -0.0036(16) 0.0022(18) 0.0090(18) O5 0.021(3) 0.013(2) 0.028(2) -0.0073(18) -0.012(2) -0.0030(18) O6 0.012(2) 0.0053(17) 0.0130(19) -0.0010(15) -0.0005(16) 0.0002(15) O7 0.018(2) 0.0080(18) 0.022(2) 0.0000(16) -0.0070(19) -0.0006(16) C8 0.013(3) 0.011(3) 0.006(2) 0.001(2) 0.002(2) 0.001(2) C9 0.016(4) 0.013(3) 0.014(3) -0.001(2) -0.007(2) -0.002(2) N10 0.027(3) 0.017(3) 0.017(3) -0.004(2) 0.004(2) -0.011(2) C11 0.010(3) 0.020(3) 0.011(3) -0.001(2) 0.003(2) -0.003(2) C12 0.007(3) 0.008(2) 0.015(3) -0.001(2) -0.004(2) 0.001(2) C13 0.010(3) 0.010(3) 0.015(3) 0.002(2) 0.001(2) 0.002(2) C14 0.014(4) 0.008(3) 0.018(3) 0.002(2) 0.002(3) 0.005(2) C15 0.017(4) 0.008(3) 0.008(3) -0.001(2) -0.005(2) 0.004(2) C16 0.011(3) 0.005(2) 0.015(3) 0.001(2) 0.000(2) 0.000(2) C17 0.021(4) 0.009(3) 0.015(3) 0.002(2) -0.004(2) 0.002(2) N18 0.034(5) 0.008(3) 0.024(4) 0.000 -0.015(4) 0.000 C19 0.003(4) 0.013(4) 0.015(4) 0.000 0.000(3) 0.000 C20 0.006(3) 0.014(3) 0.011(3) 0.003(2) 0.002(2) -0.001(2) O21 0.026(3) 0.016(2) 0.011(2) 0.0014(16) 0.0036(18) 0.0025(18) C22 0.014(3) 0.021(3) 0.018(3) -0.003(3) 0.004(3) 0.003(3) N23 0.065(5) 0.063(5) 0.017(3) -0.013(3) 0.016(3) -0.035(4) C24 0.038(6) 0.077(8) 0.029(4) -0.035(5) 0.004(4) -0.016(5) C25A 0.053(13) 0.057(10) 0.021(7) 0.008(6) 0.004(6) -0.035(8) _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 La1 O5 2.397(4) . ? La1 O4 2.479(4) 6_657 ? La1 O7 2.493(4) . ? La1 O21 2.521(4) . ? La1 O3 2.555(4) 2_665 ? La1 O2 2.589(4) 5_766 ? La1 O6 2.602(4) 6_557 ? La1 O3 2.714(4) 5_766 ? La1 O6 2.804(4) . ? La1 C14 2.978(6) 5_766 ? La1 C20 3.026(6) . ? O2 C14 1.259(7) . ? O2 La1 2.589(4) 5_766 ? O3 C14 1.264(7) . ? O3 La1 2.555(4) 2_664 ? O3 La1 2.714(4) 5_766 ? O4 C15 1.259(7) . ? O4 La1 2.479(4) 6_557 ? O5 C15 1.260(7) . ? O6 C20 1.263(7) . ? O6 La1 2.602(4) 6_657 ? O7 C20 1.264(7) . ? C8 C9 1.383(8) . ? C8 C13 1.388(8) . ? C8 C14 1.504(8) . ? C9 N10 1.335(8) . ? N10 C11 1.340(7) . ? C11 C12 1.391(8) . ? C12 C13 1.376(8) . ? C12 C15 1.491(7) . ? C14 La1 2.978(6) 5_766 ? C16 C19 1.385(7) . ? C16 C17 1.391(8) . ? C16 C20 1.483(7) . ? C17 N18 1.338(7) . ? N18 C17 1.338(7) 7_575 ? C19 C16 1.385(7) 7_575 ? O21 C22 1.243(7) . ? C22 N23 1.277(8) . ? N23 C25A 1.469(3) . ? N23 C24 1.470(10) . ? N23 C25B 1.471(3) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O5 La1 O4 76.82(14) . 6_657 ? O5 La1 O7 145.70(14) . . ? O4 La1 O7 130.49(13) 6_657 . ? O5 La1 O21 83.37(14) . . ? O4 La1 O21 139.62(13) 6_657 . ? O7 La1 O21 83.57(13) . . ? O5 La1 O3 86.08(14) . 2_665 ? O4 La1 O3 71.54(13) 6_657 2_665 ? O7 La1 O3 85.01(13) . 2_665 ? O21 La1 O3 142.05(13) . 2_665 ? O5 La1 O2 76.31(14) . 5_766 ? O4 La1 O2 72.38(13) 6_657 5_766 ? O7 La1 O2 127.08(14) . 5_766 ? O21 La1 O2 68.88(13) . 5_766 ? O3 La1 O2 142.56(12) 2_665 5_766 ? O5 La1 O6 72.55(13) . 6_557 ? O4 La1 O6 128.57(13) 6_657 6_557 ? O7 La1 O6 73.55(13) . 6_557 ? O21 La1 O6 75.92(13) . 6_557 ? O3 La1 O6 66.13(12) 2_665 6_557 ? O2 La1 O6 135.01(13) 5_766 6_557 ? O5 La1 O3 125.30(13) . 5_766 ? O4 La1 O3 88.08(13) 6_657 5_766 ? O7 La1 O3 81.20(13) . 5_766 ? O21 La1 O3 75.18(13) . 5_766 ? O3 La1 O3 138.10(11) 2_665 5_766 ? O2 La1 O3 49.09(12) 5_766 5_766 ? O6 La1 O3 143.32(11) 6_557 5_766 ? O5 La1 O6 159.02(13) . . ? O4 La1 O6 83.90(12) 6_657 . ? O7 La1 O6 48.69(12) . . ? O21 La1 O6 117.14(13) . . ? O3 La1 O6 79.96(12) 2_665 . ? O2 La1 O6 105.81(12) 5_766 . ? O6 La1 O6 114.91(12) 6_557 . ? O3 La1 O6 61.31(11) 5_766 . ? O5 La1 C14 100.37(15) . 5_766 ? O4 La1 C14 84.00(14) 6_657 5_766 ? O7 La1 C14 102.66(15) . 5_766 ? O21 La1 C14 65.28(15) . 5_766 ? O3 La1 C14 152.66(14) 2_665 5_766 ? O2 La1 C14 24.91(14) 5_766 5_766 ? O6 La1 C14 141.17(14) 6_557 5_766 ? O3 La1 C14 25.11(14) 5_766 5_766 ? O6 La1 C14 85.59(14) . 5_766 ? O5 La1 C20 164.03(15) . . ? O4 La1 C20 107.36(14) 6_657 . ? O7 La1 C20 24.08(14) . . ? O21 La1 C20 101.33(14) . . ? O3 La1 C20 80.88(14) 2_665 . ? O2 La1 C20 119.65(14) 5_766 . ? O6 La1 C20 93.63(13) 6_557 . ? O3 La1 C20 70.62(13) 5_766 . ? O6 La1 C20 24.65(13) . . ? C14 La1 C20 95.43(16) 5_766 . ? C14 O2 La1 95.1(3) . 5_766 ? C14 O3 La1 129.6(3) . 2_664 ? C14 O3 La1 89.2(3) . 5_766 ? La1 O3 La1 109.90(13) 2_664 5_766 ? C15 O4 La1 131.2(4) . 6_557 ? C15 O5 La1 152.0(4) . . ? C20 O6 La1 135.5(4) . 6_657 ? C20 O6 La1 87.6(3) . . ? La1 O6 La1 105.82(12) 6_657 . ? C20 O7 La1 102.3(3) . . ? C9 C8 C13 118.4(5) . . ? C9 C8 C14 122.3(5) . . ? C13 C8 C14 119.3(5) . . ? N10 C9 C8 123.3(5) . . ? C9 N10 C11 117.4(5) . . ? N10 C11 C12 123.5(5) . . ? C13 C12 C11 117.9(5) . . ? C13 C12 C15 120.8(5) . . ? C11 C12 C15 121.1(5) . . ? C12 C13 C8 119.5(5) . . ? O2 C14 O3 121.9(5) . . ? O2 C14 C8 116.7(5) . . ? O3 C14 C8 121.2(5) . . ? O2 C14 La1 60.0(3) . 5_766 ? O3 C14 La1 65.7(3) . 5_766 ? C8 C14 La1 155.2(4) . 5_766 ? O4 C15 O5 124.8(5) . . ? O4 C15 C12 118.3(5) . . ? O5 C15 C12 116.8(5) . . ? C19 C16 C17 118.2(5) . . ? C19 C16 C20 119.5(5) . . ? C17 C16 C20 122.4(5) . . ? N18 C17 C16 123.4(5) . . ? C17 N18 C17 117.5(7) . 7_575 ? C16 C19 C16 119.4(7) 7_575 . ? O6 C20 O7 121.2(5) . . ? O6 C20 C16 121.7(5) . . ? O7 C20 C16 117.0(5) . . ? O6 C20 La1 67.8(3) . . ? O7 C20 La1 53.6(3) . . ? C16 C20 La1 169.6(4) . . ? C22 O21 La1 127.9(4) . . ? O21 C22 N23 126.7(6) . . ? C22 N23 C25A 122.1(7) . . ? C22 N23 C24 122.2(7) . . ? C25A N23 C24 113.8(8) . . ? C22 N23 C25B 112.2(19) . . ? C24 N23 C25B 117.4(18) . . ? # 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 -0.023 0.250 0.750 530 131 ' ' 2 -0.043 0.750 0.250 530 131 ' ' _platon_squeeze_details ; The residual density accounts for molecules of DMF crystallization solvent. ; # start Validation report _vrf_PLAT220_1 ; PROBLEM: High Ueq for C24 and C25 RESPONSE: The N-dimethyl residue of the metal-coordinated DMF ligand is partly disordered. ; # end Validation reply form _refine_diff_density_max 2.277 _refine_diff_density_min -2.023 _refine_diff_density_rms 0.155 #===============END============================= data_2 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C27 H23 Ce2 N5 O14' _chemical_formula_sum 'C27 H23 Ce2 N5 O14' _chemical_formula_weight 921.74 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' 'Ce' 'Ce' -0.2486 2.6331 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'orthorhombic' _symmetry_space_group_name_H-M 'P nma' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z' 'x+1/2, -y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z' '-x-1/2, y-1/2, z-1/2' _cell_length_a 8.1162(4) _cell_length_b 30.2842(14) _cell_length_c 15.6709(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3851.8(3) _cell_formula_units_Z 4 _cell_measurement_temperature 110(2) _cell_measurement_reflns_used 2869 _cell_measurement_theta_min 2.40 _cell_measurement_theta_max 25.1 _exptl_crystal_description 'needles' _exptl_crystal_colour 'colorless' _exptl_crystal_size_max 0.36 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.07 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.589 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1792 _exptl_absorpt_coefficient_mu 2.397 _exptl_absorpt_correction_type 'multi-scan' _exptl_absorpt_correction_T_min 0.4791 _exptl_absorpt_correction_T_max 0.8502 _exptl_absorpt_process_details 'Sadabs, Bruker-AXS' _exptl_special_details ; ? ; _diffrn_ambient_temperature 110(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 'ApexDuo, Bruker-AXS' _diffrn_measurement_method '1 deg. \f and \w scans' _diffrn_detector_area_resol_mean 1.75 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 15168 _diffrn_reflns_av_R_equivalents 0.0338 _diffrn_reflns_av_sigmaI/netI 0.0311 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 6 _diffrn_reflns_limit_k_min -36 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 10 _diffrn_reflns_theta_min 2.40 _diffrn_reflns_theta_max 25.10 _reflns_number_total 3379 _reflns_number_gt 2869 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Apex2, Bruker-AXS' _computing_cell_refinement 'Saint, Bruker-AXS' _computing_data_reduction 'Saint, Bruker-AXS' _computing_structure_solution 'SHELXTL-2012 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _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. The crystals contain severely disordered molecules of the DMF crystallization solvent within the interstitial voids, which could not be modeled reliably by discrete atoms. Its contribution to the diffraction pattern was thus subtracted by the Squeeze procedure, using the PLATON software (Spek, 2009). The metal coordinated DMF ligand is also partly disordered. ; _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^)+(0.0469P)^2^+6.1116P] 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_number_reflns 3379 _refine_ls_number_parameters 218 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0478 _refine_ls_R_factor_gt 0.0401 _refine_ls_wR_factor_ref 0.1028 _refine_ls_wR_factor_gt 0.1004 _refine_ls_goodness_of_fit_ref 1.087 _refine_ls_restrained_S_all 1.087 _refine_ls_shift/su_max 0.033 _refine_ls_shift/su_mean 0.002 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 Ce1 Ce 0.43911(4) 0.908691(9) 0.703925(18) 0.00767(13) Uani 1 1 d . . . O2 O 0.6625(5) 0.86861(11) 0.8162(2) 0.0093(8) Uani 1 1 d . . . O3 O 0.3865(5) 1.03933(12) 0.3871(2) 0.0137(9) Uani 1 1 d . . . O4 O 0.2483(5) 0.96207(12) 0.6512(3) 0.0185(9) Uani 1 1 d . A . O5 O 0.4933(5) 0.83022(12) 0.7345(2) 0.0138(9) Uani 1 1 d . . . O6 O 0.2343(5) 1.09476(12) 0.3383(2) 0.0127(9) Uani 1 1 d . . . O7 O 0.0027(5) 0.97380(13) 0.7094(2) 0.0149(9) Uani 1 1 d . . . N8 N -0.0736(6) 1.08316(15) 0.5550(3) 0.0185(12) Uani 1 1 d . A . N9 N 0.8025(10) 0.7500 0.9406(4) 0.0198(17) Uani 1 2 d S . . C10 C 0.6015(7) 0.83181(18) 0.7914(3) 0.0098(12) Uani 1 1 d . . . C11 C 0.6010(10) 0.7500 0.7953(5) 0.0094(16) Uani 1 2 d S . . H11 H 0.5295 0.7500 0.7473 0.011 Uiso 1 2 calc SR . . C12 C 0.1568(7) 1.06026(17) 0.4710(3) 0.0085(11) Uani 1 1 d . A . C13 C 0.0232(7) 1.08705(17) 0.4867(4) 0.0123(12) Uani 1 1 d . . . H13 H -0.0014 1.1096 0.4466 0.015 Uiso 1 1 calc R . . C14 C 0.1158(7) 0.98313(17) 0.6587(3) 0.0096(12) Uani 1 1 d . . . C15 C 0.2640(7) 1.06457(16) 0.3928(3) 0.0096(12) Uani 1 1 d . . . C16 C -0.0404(7) 1.05007(18) 0.6091(4) 0.0127(12) Uani 1 1 d . . . H16 H -0.1110 1.0461 0.6569 0.015 Uiso 1 1 calc R A . C17 C 0.6543(7) 0.78963(16) 0.8311(3) 0.0106(12) Uani 1 1 d . . . C18 C 0.0918(7) 1.02120(17) 0.5992(3) 0.0118(11) Uani 1 1 d . A . C19 C 0.7517(7) 0.78767(17) 0.9038(3) 0.0139(13) Uani 1 1 d . A . H19 H 0.7846 0.8148 0.9292 0.017 Uiso 1 1 calc R . . C20 C 0.1934(7) 1.02692(16) 0.5298(3) 0.0107(12) Uani 1 1 d . . . H20 H 0.2870 1.0085 0.5220 0.013 Uiso 1 1 calc R A . O21 O 0.4448(5) 0.88346(13) 0.5523(2) 0.0187(9) Uani 1 1 d . A 1 C22 C 0.4434(7) 0.90695(19) 0.4872(4) 0.0175(13) Uani 1 1 d . A 1 H22 H 0.3891 0.9347 0.4928 0.021 Uiso 1 1 d R A 1 N23B N 0.463(3) 0.8865(7) 0.4085(11) 0.027(5) Uiso 0.35(2) 1 d P A 1 C24B C 0.478(3) 0.9144(9) 0.3308(15) 0.030(6) Uiso 0.35(2) 1 d P A 1 H24D H 0.4630 0.9460 0.3454 0.045 Uiso 0.35 1 d P A 1 H24E H 0.3786 0.9081 0.2876 0.045 Uiso 0.35 1 d P A 1 H24F H 0.5766 0.9090 0.3004 0.045 Uiso 0.35 1 d P A 1 C25B C 0.469(4) 0.8389(12) 0.394(2) 0.038(12) Uiso 0.35(2) 1 d P A 1 H25D H 0.4563 0.8231 0.4421 0.057 Uiso 0.35 1 d P A 1 H25E H 0.4941 0.8303 0.3406 0.057 Uiso 0.35 1 d P A 1 H25F H 0.3075 0.8348 0.3765 0.057 Uiso 0.35 1 d P A 1 N23A N 0.5076(14) 0.8999(3) 0.4138(5) 0.016(2) Uiso 0.65(2) 1 d P A 2 C24A C 0.4891(14) 0.9308(4) 0.3431(7) 0.021(3) Uiso 0.65(2) 1 d P A 2 H24A H 0.4254 0.9573 0.3609 0.032 Uiso 0.65 1 d P A 2 H24B H 0.4279 0.9183 0.2904 0.032 Uiso 0.65 1 d P A 2 H24C H 0.5989 0.9406 0.3213 0.032 Uiso 0.65 1 d P A 2 C25A C 0.5953(17) 0.8577(4) 0.3978(8) 0.043(4) Uiso 0.65(2) 1 d P A 2 H25A H 0.7012 0.8634 0.3756 0.064 Uiso 0.65 1 d P A 2 H25B H 0.5281 0.8398 0.3529 0.064 Uiso 0.65 1 d P A 2 H25C H 0.5950 0.8403 0.4512 0.064 Uiso 0.65 1 d P 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 Ce1 0.0088(2) 0.00480(17) 0.00943(19) 0.00022(11) 0.00052(13) 0.00004(12) O2 0.008(2) 0.0054(17) 0.0144(19) 0.0010(14) 0.0006(17) -0.0020(15) O3 0.012(2) 0.0143(19) 0.015(2) -0.0014(16) 0.0045(17) 0.0004(17) O4 0.020(3) 0.013(2) 0.022(2) 0.0049(17) -0.0052(19) 0.0017(18) O5 0.015(2) 0.0103(19) 0.016(2) -0.0008(15) -0.0056(19) 0.0002(17) O6 0.020(2) 0.0140(19) 0.0039(18) 0.0035(15) -0.0016(17) -0.0066(17) O7 0.016(2) 0.015(2) 0.014(2) 0.0042(16) 0.0020(18) -0.0043(18) N8 0.019(3) 0.013(2) 0.023(3) 0.004(2) 0.010(2) 0.009(2) N9 0.036(5) 0.006(3) 0.017(4) 0.000 -0.014(3) 0.000 C10 0.009(3) 0.014(3) 0.007(3) 0.002(2) 0.004(2) 0.001(2) C11 0.007(4) 0.010(4) 0.011(4) 0.000 -0.001(3) 0.000 C12 0.005(3) 0.011(2) 0.010(3) 0.001(2) -0.001(2) -0.003(2) C13 0.010(3) 0.011(3) 0.015(3) 0.002(2) -0.004(2) 0.003(2) C14 0.015(3) 0.012(2) 0.009(3) 0.001(2) -0.006(2) -0.004(2) C15 0.015(3) 0.012(2) 0.009(3) -0.002(2) -0.002(2) -0.008(2) C16 0.006(3) 0.019(3) 0.013(3) 0.000(2) 0.003(2) 0.002(2) C17 0.013(3) 0.007(3) 0.011(3) -0.001(2) 0.002(2) -0.001(2) C18 0.014(3) 0.009(3) 0.013(3) 0.000(2) -0.004(2) -0.004(2) C19 0.020(4) 0.008(3) 0.014(3) -0.003(2) -0.001(3) -0.002(2) C20 0.006(3) 0.006(2) 0.020(3) -0.003(2) -0.004(2) -0.002(2) O21 0.029(3) 0.019(2) 0.008(2) 0.0002(16) 0.0002(19) -0.0054(19) C22 0.011(3) 0.020(3) 0.022(3) -0.001(2) 0.001(3) -0.004(3) _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 Ce1 O4 2.386(4) . ? Ce1 O7 2.449(4) 6_657 ? Ce1 O5 2.464(4) . ? Ce1 O21 2.496(4) . ? Ce1 O6 2.535(4) 2_575 ? Ce1 O3 2.552(4) 5_676 ? Ce1 O2 2.572(4) 6_557 ? Ce1 O6 2.734(4) 5_676 ? Ce1 O2 2.803(4) . ? Ce1 C15 2.960(6) 5_676 ? Ce1 C10 3.007(5) . ? O2 C10 1.280(6) . ? O2 Ce1 2.572(4) 6_657 ? O3 C15 1.257(7) . ? O3 Ce1 2.552(4) 5_676 ? O4 C14 1.256(7) . ? O5 C10 1.253(7) . ? O6 C15 1.274(6) . ? O6 Ce1 2.535(4) 2_574 ? O6 Ce1 2.734(4) 5_676 ? O7 C14 1.247(7) . ? O7 Ce1 2.449(4) 6_557 ? N8 C13 1.333(8) . ? N8 C16 1.340(7) . ? N9 C19 1.343(6) 7_575 ? N9 C19 1.343(6) . ? C10 C17 1.484(7) . ? C11 C17 1.394(6) . ? C11 C17 1.394(6) 7_575 ? C12 C13 1.377(8) . ? C12 C20 1.399(7) . ? C12 C15 1.508(8) . ? C14 C18 1.495(7) . ? C15 Ce1 2.960(6) 5_676 ? C16 C18 1.393(8) . ? C17 C19 1.388(8) . ? C18 C20 1.375(8) . ? O21 C22 1.244(7) . ? C22 N23B 1.39(2) . ? N23B C25B 1.46(4) . ? N23B C24B 1.49(3) . ? N23A C24A 1.460(14) . ? N23A C25A 1.484(15) . ? 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 O4 Ce1 O7 77.49(14) . 6_657 ? O4 Ce1 O5 146.79(14) . . ? O7 Ce1 O5 129.13(13) 6_657 . ? O4 Ce1 O21 83.67(14) . . ? O7 Ce1 O21 140.38(13) 6_657 . ? O5 Ce1 O21 83.48(13) . . ? O4 Ce1 O6 87.44(13) . 2_575 ? O7 Ce1 O6 71.91(12) 6_657 2_575 ? O5 Ce1 O6 84.14(13) . 2_575 ? O21 Ce1 O6 142.03(13) . 2_575 ? O4 Ce1 O3 75.44(13) . 5_676 ? O7 Ce1 O3 72.33(13) 6_657 5_676 ? O5 Ce1 O3 127.18(13) . 5_676 ? O21 Ce1 O3 69.32(12) . 5_676 ? O6 Ce1 O3 142.88(11) 2_575 5_676 ? O4 Ce1 O2 73.18(13) . 6_557 ? O7 Ce1 O2 129.20(13) 6_657 6_557 ? O5 Ce1 O2 74.01(12) . 6_557 ? O21 Ce1 O2 75.80(13) . 6_557 ? O6 Ce1 O2 66.29(12) 2_575 6_557 ? O3 Ce1 O2 134.96(12) 5_676 6_557 ? O4 Ce1 O6 124.83(12) . 5_676 ? O7 Ce1 O6 87.75(13) 6_657 5_676 ? O5 Ce1 O6 80.62(12) . 5_676 ? O21 Ce1 O6 74.93(12) . 5_676 ? O6 Ce1 O6 137.54(11) 2_575 5_676 ? O3 Ce1 O6 49.51(11) 5_676 5_676 ? O2 Ce1 O6 143.00(11) 6_557 5_676 ? O4 Ce1 O2 158.50(12) . . ? O7 Ce1 O2 82.19(12) 6_657 . ? O5 Ce1 O2 49.06(11) . . ? O21 Ce1 O2 116.95(12) . . ? O6 Ce1 O2 79.61(12) 2_575 . ? O3 Ce1 O2 105.02(12) 5_676 . ? O2 Ce1 O2 115.93(11) 6_557 . ? O6 Ce1 O2 60.56(11) 5_676 . ? O4 Ce1 C15 99.53(14) . 5_676 ? O7 Ce1 C15 83.81(14) 6_657 5_676 ? O5 Ce1 C15 102.59(14) . 5_676 ? O21 Ce1 C15 65.24(14) . 5_676 ? O6 Ce1 C15 152.72(13) 2_575 5_676 ? O3 Ce1 C15 24.99(13) 5_676 5_676 ? O2 Ce1 C15 140.98(13) 6_557 5_676 ? O6 Ce1 C15 25.47(13) 5_676 5_676 ? O2 Ce1 C15 85.04(13) . 5_676 ? O4 Ce1 C10 165.26(15) . . ? O7 Ce1 C10 106.14(14) 6_657 . ? O5 Ce1 C10 23.95(14) . . ? O21 Ce1 C10 100.90(14) . . ? O6 Ce1 C10 80.36(13) 2_575 . ? O3 Ce1 C10 119.29(14) 5_676 . ? O2 Ce1 C10 94.20(13) 6_557 . ? O6 Ce1 C10 69.87(13) 5_676 . ? O2 Ce1 C10 25.13(13) . . ? C15 Ce1 C10 95.08(15) 5_676 . ? C10 O2 Ce1 135.3(3) . 6_657 ? C10 O2 Ce1 86.4(3) . . ? Ce1 O2 Ce1 106.44(12) 6_657 . ? C15 O3 Ce1 96.0(3) . 5_676 ? C14 O4 Ce1 150.2(4) . . ? C10 O5 Ce1 103.1(3) . . ? C15 O6 Ce1 129.2(3) . 2_574 ? C15 O6 Ce1 87.2(3) . 5_676 ? Ce1 O6 Ce1 109.61(13) 2_574 5_676 ? C14 O7 Ce1 133.7(4) . 6_557 ? C13 N8 C16 117.1(5) . . ? C19 N9 C19 116.3(7) 7_575 . ? O5 C10 O2 121.4(5) . . ? O5 C10 C17 117.9(5) . . ? O2 C10 C17 120.7(5) . . ? O5 C10 Ce1 53.0(3) . . ? O2 C10 Ce1 68.5(3) . . ? C17 C10 Ce1 169.9(4) . . ? C17 C11 C17 118.9(7) . 7_575 ? C13 C12 C20 118.3(5) . . ? C13 C12 C15 123.3(5) . . ? C20 C12 C15 118.4(5) . . ? N8 C13 C12 123.8(5) . . ? O7 C14 O4 125.1(5) . . ? O7 C14 C18 118.5(5) . . ? O4 C14 C18 116.4(5) . . ? O3 C15 O6 122.5(5) . . ? O3 C15 C12 117.5(5) . . ? O6 C15 C12 119.9(5) . . ? O3 C15 Ce1 59.0(3) . 5_676 ? O6 C15 Ce1 67.3(3) . 5_676 ? C12 C15 Ce1 155.4(4) . 5_676 ? N8 C16 C18 123.6(5) . . ? C19 C17 C11 118.1(5) . . ? C19 C17 C10 123.0(5) . . ? C11 C17 C10 118.9(5) . . ? C20 C18 C16 118.1(5) . . ? C20 C18 C14 120.8(5) . . ? C16 C18 C14 121.0(5) . . ? N9 C19 C17 124.3(5) . . ? C18 C20 C12 119.0(5) . . ? C22 O21 Ce1 127.3(4) . . ? O21 C22 N23B 118.2(10) . . ? C22 N23B C25B 125.4(19) . . ? C22 N23B C24B 118.9(17) . . ? C25B N23B C24B 116(2) . . ? C24A N23A C25A 118.2(9) . . ? # 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 -0.025 0.250 0.750 444 243 ' ' 2 -0.062 0.750 0.250 444 244 ' ' _platon_squeeze_details ; The residual density accounts for disordered DMF crystallization solvent ; # start Validation Reply Form _vrf_PLAT201_2 ; PROBLEM: isotropic atoms in the main residue RESPONSE: The metal-coordinated DMF ligand exhibits 2-fold disorder. The disordered NMe2 residue was thus assigned isotropic-Us only. ; _vrf_PLAT220_2 ; PROBLEM: large non-solvent Ueq(max)/Ueq(min) RESPONSE: The disordered methyl residue has considerably higher ADPs than the heavy Ce ion. ; #end Validation Reply Form _diffrn_reflns_theta_full 25.10 _diffrn_measured_fraction_theta_max 0.966 _diffrn_measured_fraction_theta_full 0.966 _refine_diff_density_max 1.928 _refine_diff_density_min -2.310 _refine_diff_density_rms 0.146 #=================================END===========================