# Electronic Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2012 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _journal_year ? _journal_volume ? _journal_page_first ? _publ_contact_author_name 'Angel E. Kaifer' _publ_contact_author_email akaifer@miami.edu loop_ _publ_author_name S.Yi V.Brega B.Captain A.E.Kaifer data_squeeze_Fe4_Td_Cage(Rev) _database_code_depnum_ccdc_archive 'CCDC 891142' #TrackingRef '- Fe4_Td_Cage(Rev).cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C162 H144 Fe4 N36 O22 S4' _chemical_formula_weight 3298.77 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Cubic _symmetry_space_group_name_H-M I23 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-x, y, -z' 'x, -y, -z' 'z, x, y' 'z, -x, -y' '-z, -x, y' '-z, x, -y' 'y, z, x' '-y, z, -x' 'y, -z, -x' '-y, -z, x' 'x+1/2, y+1/2, z+1/2' '-x+1/2, -y+1/2, z+1/2' '-x+1/2, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z+1/2' 'z+1/2, x+1/2, y+1/2' 'z+1/2, -x+1/2, -y+1/2' '-z+1/2, -x+1/2, y+1/2' '-z+1/2, x+1/2, -y+1/2' 'y+1/2, z+1/2, x+1/2' '-y+1/2, z+1/2, -x+1/2' 'y+1/2, -z+1/2, -x+1/2' '-y+1/2, -z+1/2, x+1/2' _cell_length_a 22.1233(8) _cell_length_b 22.1233(8) _cell_length_c 22.1233(8) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 10828.0(7) _cell_formula_units_Z 2 _cell_measurement_temperature 100 _cell_measurement_reflns_used 9921 _cell_measurement_theta_min 2.25 _cell_measurement_theta_max 23.37 _exptl_crystal_description Block _exptl_crystal_colour red _exptl_crystal_size_max 0.42 _exptl_crystal_size_mid 0.36 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.012 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3424 _exptl_absorpt_coefficient_mu 0.359 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.6689 _exptl_absorpt_correction_T_max 0.7457 _exptl_absorpt_process_details '(SADABS 2007/4 Bruker)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100 _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 'Bruker SMART APEX2 CCD diffractometer' _diffrn_measurement_method 'omega scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 44282 _diffrn_reflns_av_R_equivalents 0.0402 _diffrn_reflns_av_sigmaI/netI 0.0177 _diffrn_reflns_limit_h_min -26 _diffrn_reflns_limit_h_max 26 _diffrn_reflns_limit_k_min -26 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -26 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 1.84 _diffrn_reflns_theta_max 25.00 _reflns_number_total 3202 _reflns_number_gt 2985 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 v2.2-0 (Bruker, 2007)' _computing_cell_refinement 'SAINT+ V7.46A (Bruker, 2007)' _computing_data_reduction 'SAINT+ V7.46A (Bruker, 2007)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'XSHELL v4.02 (Bruker, 2000)' _computing_publication_material 'XCIF v6.12 (Bruker, 2001)' _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 remaining SO42- counter anions are severely disordered and were modeled using a total of 9 geometric restraints (SHELX: DFIX, DANG instructions) and refined with isotropic thermal parameters. The oxygen atom O3 in this disordered group was refined with a fixed isotropic thermal parameter. ; _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^)+(0.1719P)^2^+4.4057P] 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 0.23(4) _refine_ls_number_reflns 3202 _refine_ls_number_parameters 182 _refine_ls_number_restraints 9 _refine_ls_R_factor_all 0.0802 _refine_ls_R_factor_gt 0.0778 _refine_ls_wR_factor_ref 0.2216 _refine_ls_wR_factor_gt 0.2187 _refine_ls_goodness_of_fit_ref 1.109 _refine_ls_restrained_S_all 1.117 _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 Fe1 Fe 0.75744(2) 0.75744(2) 0.75744(2) 0.0427(3) Uani 1 3 d S . . O1 O 1.0000 1.0000 0.7401(3) 0.0755(15) Uani 1 2 d S . . N1 N 0.74720(18) 0.66980(16) 0.77259(16) 0.0516(9) Uani 1 1 d . . . N2 N 0.84235(16) 0.73539(16) 0.77374(16) 0.0440(8) Uani 1 1 d . . . N3 N 1.0234(2) 0.9542(2) 0.8269(2) 0.0612(11) Uani 1 1 d . . . H3 H 1.0277 0.9577 0.8653 0.073 Uiso 1 1 calc R . . C1 C 0.7997(2) 0.6402(2) 0.7827(2) 0.0539(11) Uani 1 1 d . . . C2 C 0.8018(3) 0.5783(2) 0.7938(3) 0.0631(14) Uani 1 1 d . . . H2 H 0.8384 0.5585 0.8000 0.076 Uiso 1 1 calc R . . C3 C 0.7476(3) 0.5474(2) 0.7954(3) 0.0742(16) Uani 1 1 d . . . H3A H 0.7472 0.5060 0.8028 0.089 Uiso 1 1 calc R . . C4 C 0.6948(3) 0.5772(3) 0.7860(3) 0.0701(15) Uani 1 1 d . . . H4 H 0.6583 0.5563 0.7879 0.084 Uiso 1 1 calc R . . C5 C 0.6950(2) 0.6383(2) 0.7738(2) 0.0595(13) Uani 1 1 d . . . H5 H 0.6587 0.6581 0.7663 0.071 Uiso 1 1 calc R . . C6 C 0.8518(2) 0.6786(2) 0.7819(2) 0.0530(11) Uani 1 1 d . . . H6 H 0.8906 0.6632 0.7871 0.064 Uiso 1 1 calc R . . C7 C 0.89386(18) 0.77544(19) 0.7771(2) 0.0428(9) Uani 1 1 d . . . C8 C 0.91731(19) 0.78936(19) 0.83342(19) 0.0451(10) Uani 1 1 d . . . H8 H 0.9001 0.7723 0.8678 0.054 Uiso 1 1 calc R . . C9 C 0.9651(2) 0.8276(2) 0.8394(2) 0.0467(10) Uani 1 1 d . . . H9 H 0.9806 0.8361 0.8775 0.056 Uiso 1 1 calc R . . C10 C 0.9910(2) 0.8543(2) 0.7878(2) 0.0528(11) Uani 1 1 d . . . C11 C 0.9685(2) 0.8396(2) 0.7324(2) 0.0573(12) Uani 1 1 d . . . H11 H 0.9863 0.8561 0.6981 0.069 Uiso 1 1 calc R . . C12 C 0.9190(2) 0.7999(2) 0.7256(2) 0.0498(10) Uani 1 1 d . . . H12 H 0.9037 0.7906 0.6876 0.060 Uiso 1 1 calc R . . C13 C 1.0419(2) 0.8978(2) 0.7961(3) 0.0578(12) Uani 1 1 d . . . H13A H 1.0734 0.8784 0.8196 0.069 Uiso 1 1 calc R . . H13B H 1.0587 0.9078 0.7569 0.069 Uiso 1 1 calc R . . C14 C 1.0000 1.0000 0.7945(3) 0.0509(15) Uani 1 2 d S . . S1 S 0.0000 1.0000 1.0000 0.0580(10) Uani 1 12 d S . . O2 O 0.03846(18) 0.96154(18) 0.96154(18) 0.0713(18) Uani 1 3 d S . . S2 S 0.1001(8) 0.8317(10) 0.5670(9) 0.254(10) Uiso 0.25 1 d PD . . O3 O 0.0723(9) 0.8765(9) 0.5192(9) 0.100 Uiso 0.25 1 d PD . . O4 O 0.0756(10) 0.7706(9) 0.5470(10) 0.111(7) Uiso 0.25 1 d PD . . O5 O 0.0828(9) 0.8425(9) 0.6306(8) 0.092(5) Uiso 0.25 1 d PD . . O6 O 0.1658(5) 0.8437(5) 0.5574(6) 0.048(3) Uiso 0.25 1 d PD . . 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 Fe1 0.0427(3) 0.0427(3) 0.0427(3) -0.0092(2) -0.0092(2) -0.0092(2) O1 0.069(3) 0.079(3) 0.078(4) 0.000 0.000 -0.005(3) N1 0.059(2) 0.0479(19) 0.0484(19) -0.0119(14) -0.0110(18) -0.0169(17) N2 0.0438(17) 0.0437(19) 0.0445(17) -0.0136(15) -0.0053(14) -0.0041(14) N3 0.063(3) 0.055(2) 0.065(3) 0.0003(19) 0.000(2) -0.0176(19) C1 0.058(3) 0.041(2) 0.063(3) -0.017(2) 0.001(2) -0.0001(19) C2 0.061(3) 0.040(2) 0.088(4) -0.014(2) -0.007(3) -0.005(2) C3 0.092(4) 0.040(2) 0.091(4) -0.014(2) -0.006(4) -0.017(3) C4 0.069(3) 0.064(3) 0.076(4) -0.005(3) -0.011(3) -0.030(3) C5 0.058(3) 0.057(3) 0.064(3) -0.011(2) -0.009(2) -0.020(2) C6 0.043(2) 0.045(2) 0.071(3) -0.012(2) -0.001(2) 0.0029(18) C7 0.0348(18) 0.043(2) 0.051(2) -0.0077(17) 0.0015(17) -0.0037(16) C8 0.045(2) 0.048(2) 0.042(2) -0.0035(18) 0.0007(17) -0.0085(18) C9 0.046(2) 0.048(2) 0.046(2) -0.0044(18) -0.0057(18) -0.0022(18) C10 0.045(2) 0.053(2) 0.060(3) -0.011(2) 0.002(2) 0.003(2) C11 0.055(3) 0.052(2) 0.065(3) 0.000(2) 0.014(2) -0.001(2) C12 0.047(2) 0.056(3) 0.046(2) -0.0038(19) -0.0005(18) 0.0001(19) C13 0.040(2) 0.057(3) 0.076(3) 0.002(2) 0.005(2) -0.008(2) C14 0.041(3) 0.064(4) 0.047(4) 0.000 0.000 -0.020(3) S1 0.0580(10) 0.0580(10) 0.0580(10) 0.000 0.000 0.000 O2 0.0713(18) 0.0713(18) 0.0713(18) -0.0054(19) 0.0054(19) 0.0054(19) _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 Fe1 N2 1.974(4) 9 ? Fe1 N2 1.974(4) 5 ? Fe1 N2 1.974(4) . ? Fe1 N1 1.981(4) . ? Fe1 N1 1.981(4) 5 ? Fe1 N1 1.981(4) 9 ? O1 C14 1.203(9) . ? N1 C5 1.349(6) . ? N1 C1 1.352(6) . ? N2 C6 1.287(7) . ? N2 C7 1.445(5) . ? N3 C14 1.344(6) . ? N3 C13 1.479(7) . ? C1 C2 1.391(7) . ? C1 C6 1.433(7) . ? C2 C3 1.382(8) . ? C3 C4 1.357(9) . ? C4 C5 1.379(8) . ? C7 C12 1.378(6) . ? C7 C8 1.385(6) . ? C8 C9 1.361(6) . ? C9 C10 1.407(7) . ? C10 C11 1.361(7) . ? C10 C13 1.493(7) . ? C11 C12 1.412(7) . ? C14 N3 1.344(6) 2_775 ? S1 O2 1.474(7) 4_577 ? S1 O2 1.474(7) 3_557 ? S1 O2 1.474(7) 2_575 ? S1 O2 1.474(7) . ? S2 O5 1.478(17) . ? S2 O6 1.492(17) . ? S2 O4 1.523(17) . ? S2 O3 1.574(17) . ? 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 N2 Fe1 N2 96.11(13) 9 5 ? N2 Fe1 N2 96.11(13) 9 . ? N2 Fe1 N2 96.11(13) 5 . ? N2 Fe1 N1 89.40(15) 9 . ? N2 Fe1 N1 173.86(16) 5 . ? N2 Fe1 N1 80.56(16) . . ? N2 Fe1 N1 173.86(16) 9 5 ? N2 Fe1 N1 80.56(16) 5 5 ? N2 Fe1 N1 89.40(15) . 5 ? N1 Fe1 N1 94.19(14) . 5 ? N2 Fe1 N1 80.56(16) 9 9 ? N2 Fe1 N1 89.40(15) 5 9 ? N2 Fe1 N1 173.86(16) . 9 ? N1 Fe1 N1 94.19(14) . 9 ? N1 Fe1 N1 94.19(14) 5 9 ? C5 N1 C1 118.8(4) . . ? C5 N1 Fe1 127.4(4) . . ? C1 N1 Fe1 113.9(3) . . ? C6 N2 C7 117.6(4) . . ? C6 N2 Fe1 115.0(3) . . ? C7 N2 Fe1 127.5(3) . . ? C14 N3 C13 119.8(5) . . ? N1 C1 C2 122.4(5) . . ? N1 C1 C6 113.7(4) . . ? C2 C1 C6 123.9(5) . . ? C3 C2 C1 117.5(5) . . ? C4 C3 C2 120.2(5) . . ? C3 C4 C5 120.2(5) . . ? N1 C5 C4 120.9(5) . . ? N2 C6 C1 116.8(4) . . ? C12 C7 C8 120.4(4) . . ? C12 C7 N2 121.1(4) . . ? C8 C7 N2 118.5(4) . . ? C9 C8 C7 121.1(4) . . ? C8 C9 C10 119.9(4) . . ? C11 C10 C9 118.8(4) . . ? C11 C10 C13 122.7(5) . . ? C9 C10 C13 118.5(4) . . ? C10 C11 C12 121.9(5) . . ? C7 C12 C11 118.0(4) . . ? N3 C13 C10 113.1(4) . . ? O1 C14 N3 122.2(3) . 2_775 ? O1 C14 N3 122.2(3) . . ? N3 C14 N3 115.6(6) 2_775 . ? O2 S1 O2 109.5 4_577 3_557 ? O2 S1 O2 109.471(1) 4_577 2_575 ? O2 S1 O2 109.471(1) 3_557 2_575 ? O2 S1 O2 109.471(4) 4_577 . ? O2 S1 O2 109.5 3_557 . ? O2 S1 O2 109.471(1) 2_575 . ? O5 S2 O6 111.1(16) . . ? O5 S2 O4 109.0(16) . . ? O6 S2 O4 117.6(17) . . ? O5 S2 O3 115.9(16) . . ? O6 S2 O3 100.0(14) . . ? O4 S2 O3 103.0(15) . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.506 _refine_diff_density_min -0.563 _refine_diff_density_rms 0.107 # SQUEEZE RESULTS # 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 0.000 0.000 0.500 440 149 ' ' 2 0.000 0.500 0.500 437 146 ' ' 3 0.000 0.500 0.000 437 146 ' ' 4 0.500 0.000 0.500 437 146 ' ' 5 0.500 0.500 1.000 437 146 ' ' 6 0.500 0.000 1.000 433 144 ' ' _platon_squeeze_details ;During the final stages of refinement the packing of the molecules of cage 3, generates large cavities that are filled with disordered molecules from the solvent of crystallization. No reasonable disorder model could be obtained for these molecules despite many attempts. They were therefore accounted for by the SQUEEZE/PLATON program. The program calculated a total solvent-accessible volume per unit cell of 2619.5 3, or 24.2% of the total unit cell volume, corresponding to 878 e-/cell. The contribution of these diffusely scattering species was removed from the structure factor calculations. The tabulated F(000), MW and density reflect the known unit cell contents only. It is not possible to estimate with any confidence (water, dioxane) what was removed by the SQUEEZE process. ; # Attachment '- Ni4_Td_Cage(Rev).cif' data_squeeze_Ni4_Td_Cage(Rev) _database_code_depnum_ccdc_archive 'CCDC 891143' #TrackingRef '- Ni4_Td_Cage(Rev).cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C162 H144 N36 Ni4 O10 S' _chemical_formula_weight 3022.03 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Trigonal _symmetry_space_group_name_H-M P-3 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' _cell_length_a 25.0734(12) _cell_length_b 25.0734(12) _cell_length_c 19.3734(9) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 10547.8(9) _cell_formula_units_Z 2 _cell_measurement_temperature 100 _cell_measurement_reflns_used 9867 _cell_measurement_theta_min 2.30 _cell_measurement_theta_max 22.23 _exptl_crystal_description Block _exptl_crystal_colour Orange _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.26 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 0.952 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3152 _exptl_absorpt_coefficient_mu 0.413 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.6071 _exptl_absorpt_correction_T_max 0.7457 _exptl_absorpt_process_details '(SADABS 2007/4 Bruker)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100 _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 'Bruker SMART APEX2 CCD diffractometer' _diffrn_measurement_method 'omega scans' _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 84637 _diffrn_reflns_av_R_equivalents 0.0589 _diffrn_reflns_av_sigmaI/netI 0.0428 _diffrn_reflns_limit_h_min -29 _diffrn_reflns_limit_h_max 29 _diffrn_reflns_limit_k_min -29 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 1.41 _diffrn_reflns_theta_max 25.00 _reflns_number_total 12393 _reflns_number_gt 8761 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'APEX2 v2.2-0 (Bruker, 2007)' _computing_cell_refinement 'SAINT+ V7.46A (Bruker, 2007)' _computing_data_reduction 'SAINT+ V7.46A (Bruker, 2007)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'XSHELL v4.02 (Bruker, 2000)' _computing_publication_material 'XCIF v6.12 (Bruker, 2001)' _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^)+(0.1145P)^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_number_reflns 12393 _refine_ls_number_parameters 640 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0832 _refine_ls_R_factor_gt 0.0593 _refine_ls_wR_factor_ref 0.1754 _refine_ls_wR_factor_gt 0.1634 _refine_ls_goodness_of_fit_ref 1.013 _refine_ls_restrained_S_all 1.013 _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 Ni1 Ni 0.011657(18) 0.286825(18) 0.34345(2) 0.04561(14) Uani 1 1 d . . . Ni2 Ni 0.3333 0.6667 0.98148(3) 0.0484(2) Uani 1 3 d S . . O1 O 0.35573(10) 0.48456(10) 0.31280(11) 0.0553(6) Uani 1 1 d . . . O2 O 0.17514(11) 0.48674(12) 0.66684(11) 0.0652(7) Uani 1 1 d . . . C1 C 0.11367(14) 0.41177(14) 0.27033(15) 0.0445(7) Uani 1 1 d . . . C2 C 0.15263(15) 0.40463(15) 0.22508(14) 0.0493(8) Uani 1 1 d . . . H2 H 0.1378 0.3695 0.1978 0.059 Uiso 1 1 calc R . . C3 C 0.21378(15) 0.45031(15) 0.22111(15) 0.0515(8) Uani 1 1 d . . . H3 H 0.2396 0.4460 0.1899 0.062 Uiso 1 1 calc R . . C4 C 0.23724(13) 0.50156(13) 0.26184(15) 0.0424(7) Uani 1 1 d . . . C5 C 0.19797(15) 0.50829(15) 0.30612(18) 0.0552(8) Uani 1 1 d . . . H5 H 0.2131 0.5435 0.3333 0.066 Uiso 1 1 calc R . . C6 C 0.13650(16) 0.46362(15) 0.31077(19) 0.0589(9) Uani 1 1 d . . . H6 H 0.1107 0.4687 0.3412 0.071 Uiso 1 1 calc R . . C7 C 0.30500(14) 0.55158(15) 0.25869(16) 0.0492(8) Uani 1 1 d . . . H7A H 0.3261 0.5394 0.2258 0.059 Uiso 1 1 calc R . . H7B H 0.3079 0.5894 0.2421 0.059 Uiso 1 1 calc R . . C8 C 0.35846(14) 0.52754(14) 0.34837(16) 0.0467(7) Uani 1 1 d . . . C9 C 0.41015(16) 0.50637(15) 0.44435(17) 0.0545(8) Uani 1 1 d . . . H9A H 0.3969 0.4682 0.4194 0.065 Uiso 1 1 calc R . . H9B H 0.3956 0.4960 0.4915 0.065 Uiso 1 1 calc R . . C10 C 0.01129(15) 0.36414(15) 0.23428(15) 0.0493(8) Uani 1 1 d . . . H10 H 0.0234 0.3948 0.2011 0.059 Uiso 1 1 calc R . . C11 C -0.05329(15) 0.31470(15) 0.23952(16) 0.0492(8) Uani 1 1 d . . . C12 C -0.09741(18) 0.31128(19) 0.19508(19) 0.0661(10) Uani 1 1 d . . . H12 H -0.0876 0.3410 0.1611 0.079 Uiso 1 1 calc R . . C13 C -0.15705(17) 0.2624(2) 0.20200(19) 0.0682(10) Uani 1 1 d . . . H13 H -0.1881 0.2587 0.1727 0.082 Uiso 1 1 calc R . . C14 C -0.16955(16) 0.21934(18) 0.25311(18) 0.0632(10) Uani 1 1 d . . . H14 H -0.2090 0.1859 0.2585 0.076 Uiso 1 1 calc R . . C15 C -0.12193(15) 0.22693(17) 0.29646(18) 0.0590(9) Uani 1 1 d . . . H15 H -0.1304 0.1982 0.3312 0.071 Uiso 1 1 calc R . . C16 C 0.60680(15) 0.62185(14) 0.43788(15) 0.0450(7) Uani 1 1 d . . . C17 C 0.57715(15) 0.57311(14) 0.39087(15) 0.0451(7) Uani 1 1 d . . . H17 H 0.5998 0.5666 0.3573 0.054 Uiso 1 1 calc R . . C18 C 0.51451(15) 0.53501(14) 0.39463(15) 0.0455(7) Uani 1 1 d . . . H18 H 0.4952 0.5027 0.3634 0.055 Uiso 1 1 calc R . . C19 C 0.47897(15) 0.54344(14) 0.44414(15) 0.0461(7) Uani 1 1 d . . . C20 C 0.50927(15) 0.59037(14) 0.49231(16) 0.0487(8) Uani 1 1 d . . . H20 H 0.4867 0.5961 0.5267 0.058 Uiso 1 1 calc R . . C21 C 0.57221(16) 0.62844(15) 0.48973(16) 0.0521(8) Uani 1 1 d . . . H21 H 0.5918 0.6589 0.5230 0.063 Uiso 1 1 calc R . . C22 C 0.70542(15) 0.68120(15) 0.48271(17) 0.0516(8) Uani 1 1 d . . . H22 H 0.6905 0.6610 0.5246 0.062 Uiso 1 1 calc R . . C23 C 0.76818(16) 0.73015(15) 0.47648(16) 0.0501(8) Uani 1 1 d . . . C24 C 0.80805(17) 0.75328(16) 0.53261(19) 0.0590(9) Uani 1 1 d . . . H24 H 0.7948 0.7363 0.5762 0.071 Uiso 1 1 calc R . . C25 C 0.86688(18) 0.80109(17) 0.5234(2) 0.0622(10) Uani 1 1 d . . . H25 H 0.8935 0.8177 0.5608 0.075 Uiso 1 1 calc R . . C26 C 0.88594(17) 0.82401(16) 0.4584(2) 0.0622(10) Uani 1 1 d . . . H26 H 0.9260 0.8558 0.4507 0.075 Uiso 1 1 calc R . . C27 C 0.84379(16) 0.79863(16) 0.4032(2) 0.0585(9) Uani 1 1 d . . . H27 H 0.8568 0.8140 0.3589 0.070 Uiso 1 1 calc R . . C28 C -0.00465(19) 0.20289(16) 0.2173(2) 0.0661(10) Uani 1 1 d . . . H28 H -0.0443 0.1968 0.2128 0.079 Uiso 1 1 calc R . . C29 C 0.0153(3) 0.17629(19) 0.1701(2) 0.0888(14) Uani 1 1 d . . . H29 H -0.0106 0.1525 0.1345 0.107 Uiso 1 1 calc R . . C30 C 0.0739(2) 0.1847(2) 0.1753(2) 0.0865(14) Uani 1 1 d . . . H30 H 0.0883 0.1673 0.1433 0.104 Uiso 1 1 calc R . . C31 C 0.1103(2) 0.21977(18) 0.2293(2) 0.0697(10) Uani 1 1 d . . . H31 H 0.1499 0.2261 0.2351 0.084 Uiso 1 1 calc R . . C32 C 0.08661(17) 0.24540(15) 0.27479(17) 0.0560(9) Uani 1 1 d . . . C33 C 0.12400(15) 0.28448(15) 0.33202(16) 0.0500(8) Uani 1 1 d . . . H33 H 0.1649 0.2946 0.3367 0.060 Uiso 1 1 calc R . . C34 C 0.13995(14) 0.34599(14) 0.42803(15) 0.0442(7) Uani 1 1 d . . . C35 C 0.19407(15) 0.39697(15) 0.40853(16) 0.0545(8) Uani 1 1 d . . . H35 H 0.2054 0.4036 0.3623 0.065 Uiso 1 1 calc R . . C36 C 0.23185(16) 0.43860(17) 0.45853(16) 0.0609(9) Uani 1 1 d . . . H36 H 0.2687 0.4729 0.4452 0.073 Uiso 1 1 calc R . . C37 C 0.21569(15) 0.42999(16) 0.52775(16) 0.0531(8) Uani 1 1 d . . . C38 C 0.16138(14) 0.37772(15) 0.54637(15) 0.0469(7) Uani 1 1 d . . . H38 H 0.1504 0.3707 0.5927 0.056 Uiso 1 1 calc R . . C39 C 0.12375(14) 0.33656(15) 0.49849(16) 0.0460(7) Uani 1 1 d . . . H39 H 0.0872 0.3021 0.5122 0.055 Uiso 1 1 calc R . . C40 C 0.25681(16) 0.47860(16) 0.57838(16) 0.0576(9) Uani 1 1 d . . . H40A H 0.2506 0.4601 0.6238 0.069 Uiso 1 1 calc R . . H40B H 0.2994 0.4938 0.5654 0.069 Uiso 1 1 calc R . . C41 C 0.20414(16) 0.53036(17) 0.62423(16) 0.0572(9) Uani 1 1 d . . . C42 C 0.15543(17) 0.58600(17) 0.66997(16) 0.0590(9) Uani 1 1 d . . . H42A H 0.1198 0.5460 0.6794 0.071 Uiso 1 1 calc R . . H42B H 0.1408 0.6117 0.6497 0.071 Uiso 1 1 calc R . . C43 C 0.18672(16) 0.61419(17) 0.73695(16) 0.0541(8) Uani 1 1 d . . . C44 C 0.16086(15) 0.58599(16) 0.80044(15) 0.0519(8) Uani 1 1 d . . . H44 H 0.1232 0.5495 0.8014 0.062 Uiso 1 1 calc R . . C45 C 0.19158(16) 0.61264(16) 0.86203(15) 0.0541(8) Uani 1 1 d . . . H45 H 0.1748 0.5933 0.9039 0.065 Uiso 1 1 calc R . . C46 C 0.24584(15) 0.66658(16) 0.86121(14) 0.0488(8) Uani 1 1 d . . . C47 C 0.27174(16) 0.69620(16) 0.79909(15) 0.0547(8) Uani 1 1 d . . . H47 H 0.3085 0.7336 0.7988 0.066 Uiso 1 1 calc R . . C48 C 0.24220(15) 0.66933(16) 0.73806(15) 0.0541(8) Uani 1 1 d . . . H48 H 0.2599 0.6887 0.6965 0.065 Uiso 1 1 calc R . . C49 C 0.28048(17) 0.74130(18) 0.94879(17) 0.0603(9) Uani 1 1 d . . . H49 H 0.2589 0.7577 0.9267 0.072 Uiso 1 1 calc R . . C50 C 0.3200(2) 0.8233(2) 1.0376(2) 0.0776(12) Uani 1 1 d . . . H50 H 0.2995 0.8414 1.0167 0.093 Uiso 1 1 calc R . . C51 C 0.3551(2) 0.8487(2) 1.0969(2) 0.0765(12) Uani 1 1 d . . . H51 H 0.3575 0.8833 1.1176 0.092 Uiso 1 1 calc R . . C52 C 0.38663(19) 0.82074(19) 1.12466(17) 0.0701(11) Uani 1 1 d . . . H52 H 0.4111 0.8371 1.1637 0.084 Uiso 1 1 calc R . . C53 C 0.38111(19) 0.76935(18) 1.09390(15) 0.0643(10) Uani 1 1 d . . . H53 H 0.4024 0.7513 1.1128 0.077 Uiso 1 1 calc R . . C54 C 0.31638(16) 0.77097(17) 1.01081(16) 0.0576(9) Uani 1 1 d . . . N1 N 0.05098(11) 0.36400(12) 0.27697(13) 0.0453(6) Uani 1 1 d . . . N2 N -0.06509(12) 0.27352(13) 0.29002(13) 0.0516(7) Uani 1 1 d . . . N3 N 0.67003(12) 0.66580(11) 0.42924(12) 0.0433(6) Uani 1 1 d . . . N4 N 0.78667(12) 0.75393(13) 0.41243(14) 0.0527(7) Uani 1 1 d . . . N5 N 0.02992(13) 0.23698(12) 0.26922(14) 0.0506(6) Uani 1 1 d . . . N6 N 0.09979(11) 0.30436(11) 0.37520(13) 0.0447(6) Uani 1 1 d . . . N7 N 0.33589(11) 0.56321(11) 0.32546(12) 0.0446(6) Uani 1 1 d . . . H7 H 0.3398 0.5932 0.3506 0.054 Uiso 1 1 calc R . . N8 N 0.38262(12) 0.54050(12) 0.41207(13) 0.0483(6) Uani 1 1 d . . . H8 H 0.3821 0.5696 0.4349 0.058 Uiso 1 1 calc R . . N9 N 0.24602(14) 0.52959(14) 0.58201(13) 0.0623(8) Uani 1 1 d . . . H9 H 0.2674 0.5610 0.5560 0.075 Uiso 1 1 calc R . . N10 N 0.19425(13) 0.57822(13) 0.61988(12) 0.0571(7) Uani 1 1 d . . . H10C H 0.2111 0.6046 0.5871 0.069 Uiso 1 1 calc R . . N11 N 0.27861(12) 0.69297(13) 0.92482(12) 0.0498(6) Uani 1 1 d . . . N12 N 0.34622(13) 0.74347(13) 1.03727(11) 0.0513(7) Uani 1 1 d . . . O3 O 0.3333 0.6667 0.39267(16) 0.0444(8) Uani 1 3 d S . . O4 O 0.27067(9) 0.64754(10) 0.49417(10) 0.0483(5) Uani 1 1 d . . . S1 S 0.3333 0.6667 0.46920(6) 0.0423(3) Uani 1 3 d S . . 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 Ni1 0.0409(2) 0.0467(3) 0.0433(2) 0.00994(17) 0.00399(16) 0.01748(19) Ni2 0.0649(3) 0.0649(3) 0.0154(3) 0.000 0.000 0.03246(15) O1 0.0633(14) 0.0504(13) 0.0530(13) -0.0005(11) 0.0119(11) 0.0291(12) O2 0.0693(16) 0.0774(17) 0.0405(12) 0.0167(12) 0.0035(11) 0.0303(14) C1 0.0472(18) 0.0432(17) 0.0403(16) 0.0099(13) 0.0059(13) 0.0206(15) C2 0.056(2) 0.0553(19) 0.0277(14) 0.0008(13) 0.0057(13) 0.0209(16) C3 0.054(2) 0.062(2) 0.0305(15) 0.0038(14) 0.0130(13) 0.0221(17) C4 0.0410(16) 0.0449(17) 0.0379(15) 0.0099(13) 0.0080(13) 0.0189(14) C5 0.0493(19) 0.0434(18) 0.068(2) -0.0014(16) 0.0139(16) 0.0193(16) C6 0.053(2) 0.049(2) 0.073(2) -0.0034(17) 0.0163(17) 0.0236(17) C7 0.0483(18) 0.0502(18) 0.0413(16) 0.0069(14) 0.0051(14) 0.0187(15) C8 0.0408(17) 0.0421(17) 0.0482(18) 0.0042(14) 0.0135(14) 0.0139(14) C9 0.061(2) 0.053(2) 0.0522(19) 0.0109(15) 0.0030(16) 0.0309(17) C10 0.059(2) 0.0542(19) 0.0343(16) 0.0022(13) 0.0019(14) 0.0275(17) C11 0.055(2) 0.058(2) 0.0367(16) -0.0043(14) -0.0054(14) 0.0297(17) C12 0.069(3) 0.085(3) 0.051(2) -0.0021(18) -0.0108(18) 0.043(2) C13 0.051(2) 0.104(3) 0.050(2) -0.010(2) -0.0105(16) 0.039(2) C14 0.0427(19) 0.076(2) 0.052(2) -0.0064(18) 0.0007(16) 0.0149(18) C15 0.0412(19) 0.065(2) 0.056(2) 0.0064(17) 0.0027(15) 0.0156(17) C16 0.056(2) 0.0492(18) 0.0384(16) 0.0000(13) -0.0061(14) 0.0326(16) C17 0.061(2) 0.0445(17) 0.0389(16) 0.0028(13) -0.0016(14) 0.0330(16) C18 0.060(2) 0.0446(17) 0.0391(16) -0.0023(13) -0.0061(14) 0.0313(16) C19 0.059(2) 0.0434(17) 0.0385(16) 0.0091(13) 0.0012(14) 0.0279(16) C20 0.058(2) 0.0474(18) 0.0444(17) 0.0002(14) 0.0050(15) 0.0291(17) C21 0.066(2) 0.0528(19) 0.0426(17) -0.0071(14) -0.0033(15) 0.0337(18) C22 0.059(2) 0.061(2) 0.0471(18) -0.0023(15) -0.0073(15) 0.0395(18) C23 0.061(2) 0.055(2) 0.0459(18) -0.0078(15) -0.0151(15) 0.0370(18) C24 0.065(2) 0.059(2) 0.064(2) -0.0102(17) -0.0236(18) 0.039(2) C25 0.069(2) 0.058(2) 0.069(2) -0.0136(18) -0.0262(19) 0.038(2) C26 0.056(2) 0.048(2) 0.084(3) -0.0109(18) -0.0227(19) 0.0269(17) C27 0.051(2) 0.058(2) 0.072(2) -0.0049(17) -0.0166(17) 0.0314(18) C28 0.071(2) 0.049(2) 0.069(2) -0.0049(18) 0.005(2) 0.0230(19) C29 0.111(4) 0.058(3) 0.065(3) -0.007(2) 0.003(3) 0.018(3) C30 0.101(4) 0.062(3) 0.086(3) -0.007(2) 0.034(3) 0.034(3) C31 0.085(3) 0.063(2) 0.065(2) 0.009(2) 0.023(2) 0.040(2) C32 0.072(2) 0.0419(18) 0.0489(19) 0.0157(15) 0.0199(17) 0.0242(17) C33 0.0486(18) 0.056(2) 0.0469(18) 0.0160(15) 0.0086(15) 0.0274(16) C34 0.0447(17) 0.0515(18) 0.0361(15) 0.0101(13) 0.0027(13) 0.0237(15) C35 0.0499(19) 0.060(2) 0.0359(16) 0.0143(15) 0.0090(14) 0.0145(17) C36 0.049(2) 0.068(2) 0.0388(17) 0.0101(16) 0.0073(15) 0.0096(17) C37 0.0494(19) 0.062(2) 0.0390(17) 0.0098(15) 0.0036(14) 0.0217(17) C38 0.0471(18) 0.066(2) 0.0348(15) 0.0107(15) 0.0056(13) 0.0340(17) C39 0.0382(16) 0.0512(18) 0.0492(18) 0.0158(15) 0.0104(14) 0.0228(15) C40 0.057(2) 0.063(2) 0.0377(17) 0.0091(15) 0.0014(15) 0.0190(18) C41 0.058(2) 0.061(2) 0.0350(17) 0.0059(16) -0.0071(15) 0.0160(18) C42 0.063(2) 0.065(2) 0.0398(18) -0.0006(15) -0.0094(16) 0.0246(18) C43 0.056(2) 0.073(2) 0.0348(16) 0.0083(15) -0.0017(14) 0.0332(19) C44 0.0548(19) 0.063(2) 0.0344(16) 0.0023(14) 0.0016(14) 0.0265(17) C45 0.068(2) 0.068(2) 0.0280(15) 0.0039(14) 0.0046(14) 0.036(2) C46 0.055(2) 0.070(2) 0.0246(14) 0.0012(14) 0.0012(13) 0.0342(18) C47 0.058(2) 0.063(2) 0.0318(16) 0.0011(14) -0.0046(14) 0.0224(17) C48 0.059(2) 0.068(2) 0.0262(14) 0.0075(14) -0.0021(14) 0.0252(18) C49 0.070(2) 0.089(3) 0.0386(17) 0.0000(18) 0.0011(16) 0.052(2) C50 0.094(3) 0.104(3) 0.056(2) -0.016(2) -0.010(2) 0.065(3) C51 0.099(3) 0.091(3) 0.051(2) -0.026(2) -0.011(2) 0.056(3) C52 0.090(3) 0.085(3) 0.0326(17) -0.0173(18) -0.0115(18) 0.042(2) C53 0.091(3) 0.077(3) 0.0231(15) -0.0057(15) -0.0065(16) 0.041(2) C54 0.064(2) 0.078(2) 0.0333(16) -0.0129(16) 0.0023(15) 0.037(2) N1 0.0432(14) 0.0473(15) 0.0442(14) 0.0043(11) 0.0009(11) 0.0218(12) N2 0.0495(16) 0.0568(17) 0.0436(15) 0.0062(12) 0.0014(12) 0.0230(14) N3 0.0502(15) 0.0464(14) 0.0431(14) -0.0061(11) -0.0096(12) 0.0315(13) N4 0.0497(17) 0.0552(17) 0.0604(18) -0.0067(13) -0.0116(13) 0.0316(15) N5 0.0490(16) 0.0403(15) 0.0526(16) 0.0078(12) 0.0056(13) 0.0148(13) N6 0.0426(14) 0.0465(15) 0.0427(14) 0.0142(11) 0.0094(11) 0.0206(12) N7 0.0501(15) 0.0454(14) 0.0377(13) -0.0010(11) 0.0024(11) 0.0234(13) N8 0.0525(16) 0.0443(15) 0.0483(15) -0.0027(12) 0.0021(12) 0.0245(13) N9 0.069(2) 0.0655(19) 0.0332(14) 0.0099(13) 0.0034(13) 0.0197(16) N10 0.0685(19) 0.0578(18) 0.0258(13) 0.0018(12) -0.0067(12) 0.0171(15) N11 0.0580(16) 0.0634(18) 0.0265(12) -0.0001(12) 0.0028(11) 0.0292(14) N12 0.0670(17) 0.0696(18) 0.0160(11) -0.0043(11) -0.0031(11) 0.0331(15) O3 0.0533(13) 0.0533(13) 0.0267(17) 0.000 0.000 0.0266(7) O4 0.0502(12) 0.0595(13) 0.0336(11) 0.0033(9) 0.0027(9) 0.0261(11) S1 0.0485(5) 0.0485(5) 0.0299(6) 0.000 0.000 0.0242(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 Ni1 N2 2.060(3) . ? Ni1 N4 2.090(3) 3_565 ? Ni1 N5 2.100(3) . ? Ni1 N1 2.114(2) . ? Ni1 N6 2.117(3) . ? Ni1 N3 2.127(3) 3_565 ? Ni2 N12 2.088(3) . ? Ni2 N12 2.088(3) 2_665 ? Ni2 N12 2.088(3) 3_565 ? Ni2 N11 2.104(3) . ? Ni2 N11 2.104(3) 3_565 ? Ni2 N11 2.104(3) 2_665 ? O1 C8 1.252(4) . ? O2 C41 1.269(4) . ? C1 C6 1.374(4) . ? C1 C2 1.389(4) . ? C1 N1 1.428(4) . ? C2 C3 1.383(4) . ? C3 C4 1.365(4) . ? C4 C5 1.379(4) . ? C4 C7 1.527(4) . ? C5 C6 1.383(5) . ? C7 N7 1.460(4) . ? C8 N8 1.341(4) . ? C8 N7 1.350(4) . ? C9 N8 1.480(4) . ? C9 C19 1.496(5) . ? C10 N1 1.295(4) . ? C10 C11 1.470(5) . ? C11 N2 1.344(4) . ? C11 C12 1.370(5) . ? C12 C13 1.387(5) . ? C13 C14 1.381(5) . ? C14 C15 1.393(5) . ? C15 N2 1.321(4) . ? C16 C21 1.390(4) . ? C16 C17 1.402(4) . ? C16 N3 1.417(4) . ? C17 C18 1.373(4) . ? C18 C19 1.395(4) . ? C19 C20 1.392(4) . ? C20 C21 1.378(5) . ? C22 N3 1.291(4) . ? C22 C23 1.437(5) . ? C23 N4 1.354(4) . ? C23 C24 1.392(4) . ? C24 C25 1.370(5) . ? C25 C26 1.367(5) . ? C26 C27 1.412(5) . ? C27 N4 1.317(4) . ? C28 N5 1.323(5) . ? C28 C29 1.366(6) . ? C29 C30 1.378(7) . ? C30 C31 1.377(6) . ? C31 C32 1.387(5) . ? C32 N5 1.333(4) . ? C32 C33 1.466(5) . ? C33 N6 1.272(4) . ? C34 C35 1.372(4) . ? C34 C39 1.410(4) . ? C34 N6 1.449(4) . ? C35 C36 1.391(5) . ? C36 C37 1.386(4) . ? C37 C38 1.385(4) . ? C37 C40 1.501(5) . ? C38 C39 1.357(4) . ? C40 N9 1.435(5) . ? C41 N9 1.339(5) . ? C41 N10 1.344(5) . ? C42 N10 1.455(5) . ? C42 C43 1.498(4) . ? C43 C48 1.387(5) . ? C43 C44 1.405(4) . ? C44 C45 1.396(4) . ? C45 C46 1.356(5) . ? C46 C47 1.393(4) . ? C46 N11 1.445(4) . ? C47 C48 1.379(4) . ? C49 N11 1.277(4) . ? C49 C54 1.462(5) . ? C50 C54 1.372(5) . ? C50 C51 1.393(5) . ? C51 C52 1.400(6) . ? C52 C53 1.362(5) . ? C53 N12 1.350(4) . ? C54 N12 1.347(4) . ? N3 Ni1 2.127(3) 2_665 ? N4 Ni1 2.090(3) 2_665 ? O3 S1 1.483(3) . ? O4 S1 1.476(2) . ? S1 O4 1.476(2) 3_565 ? S1 O4 1.476(2) 2_665 ? 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 N2 Ni1 N4 97.81(10) . 3_565 ? N2 Ni1 N5 91.35(11) . . ? N4 Ni1 N5 95.26(11) 3_565 . ? N2 Ni1 N1 79.19(10) . . ? N4 Ni1 N1 174.67(10) 3_565 . ? N5 Ni1 N1 89.25(10) . . ? N2 Ni1 N6 166.65(10) . . ? N4 Ni1 N6 92.17(10) 3_565 . ? N5 Ni1 N6 78.88(10) . . ? N1 Ni1 N6 91.50(9) . . ? N2 Ni1 N3 94.45(10) . 3_565 ? N4 Ni1 N3 78.23(10) 3_565 3_565 ? N5 Ni1 N3 171.80(10) . 3_565 ? N1 Ni1 N3 97.52(9) . 3_565 ? N6 Ni1 N3 96.25(10) . 3_565 ? N12 Ni2 N12 95.62(9) . 2_665 ? N12 Ni2 N12 95.62(9) . 3_565 ? N12 Ni2 N12 95.62(9) 2_665 3_565 ? N12 Ni2 N11 78.78(10) . . ? N12 Ni2 N11 90.85(10) 2_665 . ? N12 Ni2 N11 171.85(11) 3_565 . ? N12 Ni2 N11 90.85(10) . 3_565 ? N12 Ni2 N11 171.85(11) 2_665 3_565 ? N12 Ni2 N11 78.78(10) 3_565 3_565 ? N11 Ni2 N11 95.27(9) . 3_565 ? N12 Ni2 N11 171.85(11) . 2_665 ? N12 Ni2 N11 78.78(10) 2_665 2_665 ? N12 Ni2 N11 90.85(10) 3_565 2_665 ? N11 Ni2 N11 95.27(9) . 2_665 ? N11 Ni2 N11 95.27(9) 3_565 2_665 ? C6 C1 C2 119.6(3) . . ? C6 C1 N1 120.4(3) . . ? C2 C1 N1 119.9(3) . . ? C3 C2 C1 119.2(3) . . ? C4 C3 C2 121.7(3) . . ? C3 C4 C5 118.5(3) . . ? C3 C4 C7 121.9(3) . . ? C5 C4 C7 119.6(3) . . ? C4 C5 C6 121.1(3) . . ? C1 C6 C5 119.9(3) . . ? N7 C7 C4 112.9(2) . . ? O1 C8 N8 122.6(3) . . ? O1 C8 N7 121.9(3) . . ? N8 C8 N7 115.5(3) . . ? N8 C9 C19 111.5(3) . . ? N1 C10 C11 118.5(3) . . ? N2 C11 C12 123.3(3) . . ? N2 C11 C10 115.1(3) . . ? C12 C11 C10 121.6(3) . . ? C11 C12 C13 118.3(4) . . ? C14 C13 C12 118.9(3) . . ? C13 C14 C15 118.8(3) . . ? N2 C15 C14 122.4(3) . . ? C21 C16 C17 118.8(3) . . ? C21 C16 N3 121.0(3) . . ? C17 C16 N3 120.0(3) . . ? C18 C17 C16 119.7(3) . . ? C17 C18 C19 121.7(3) . . ? C20 C19 C18 118.0(3) . . ? C20 C19 C9 119.7(3) . . ? C18 C19 C9 122.2(3) . . ? C21 C20 C19 120.9(3) . . ? C20 C21 C16 120.7(3) . . ? N3 C22 C23 118.9(3) . . ? N4 C23 C24 121.0(3) . . ? N4 C23 C22 116.1(3) . . ? C24 C23 C22 122.8(3) . . ? C25 C24 C23 119.9(4) . . ? C26 C25 C24 119.0(3) . . ? C25 C26 C27 118.9(4) . . ? N4 C27 C26 122.0(4) . . ? N5 C28 C29 122.9(4) . . ? C28 C29 C30 119.9(4) . . ? C31 C30 C29 117.9(4) . . ? C30 C31 C32 118.5(4) . . ? N5 C32 C31 123.0(4) . . ? N5 C32 C33 116.2(3) . . ? C31 C32 C33 120.8(4) . . ? N6 C33 C32 119.2(3) . . ? C35 C34 C39 119.4(3) . . ? C35 C34 N6 118.9(3) . . ? C39 C34 N6 121.7(3) . . ? C34 C35 C36 119.5(3) . . ? C37 C36 C35 121.4(3) . . ? C38 C37 C36 118.2(3) . . ? C38 C37 C40 123.3(3) . . ? C36 C37 C40 118.5(3) . . ? C39 C38 C37 121.5(3) . . ? C38 C39 C34 120.1(3) . . ? N9 C40 C37 113.4(3) . . ? O2 C41 N9 120.0(4) . . ? O2 C41 N10 121.9(3) . . ? N9 C41 N10 118.1(3) . . ? N10 C42 C43 114.4(3) . . ? C48 C43 C44 117.9(3) . . ? C48 C43 C42 120.8(3) . . ? C44 C43 C42 121.3(3) . . ? C45 C44 C43 120.1(3) . . ? C46 C45 C44 120.4(3) . . ? C45 C46 C47 120.6(3) . . ? C45 C46 N11 120.2(3) . . ? C47 C46 N11 119.1(3) . . ? C48 C47 C46 119.1(3) . . ? C47 C48 C43 121.8(3) . . ? N11 C49 C54 120.2(3) . . ? C54 C50 C51 118.2(4) . . ? C50 C51 C52 118.3(4) . . ? C53 C52 C51 119.3(3) . . ? N12 C53 C52 123.0(4) . . ? N12 C54 C50 123.9(3) . . ? N12 C54 C49 114.2(3) . . ? C50 C54 C49 121.8(4) . . ? C10 N1 C1 117.7(3) . . ? C10 N1 Ni1 112.6(2) . . ? C1 N1 Ni1 129.55(19) . . ? C15 N2 C11 118.3(3) . . ? C15 N2 Ni1 127.1(2) . . ? C11 N2 Ni1 114.4(2) . . ? C22 N3 C16 118.2(3) . . ? C22 N3 Ni1 112.6(2) . 2_665 ? C16 N3 Ni1 127.98(18) . 2_665 ? C27 N4 C23 119.1(3) . . ? C27 N4 Ni1 127.2(2) . 2_665 ? C23 N4 Ni1 112.6(2) . 2_665 ? C28 N5 C32 117.8(3) . . ? C28 N5 Ni1 129.6(3) . . ? C32 N5 Ni1 112.5(2) . . ? C33 N6 C34 116.8(3) . . ? C33 N6 Ni1 112.4(2) . . ? C34 N6 Ni1 129.2(2) . . ? C8 N7 C7 121.0(3) . . ? C8 N8 C9 122.2(3) . . ? C41 N9 C40 122.8(3) . . ? C41 N10 C42 120.8(3) . . ? C49 N11 C46 119.2(3) . . ? C49 N11 Ni2 112.8(2) . . ? C46 N11 Ni2 127.7(2) . . ? C54 N12 C53 117.1(3) . . ? C54 N12 Ni2 113.9(2) . . ? C53 N12 Ni2 128.9(3) . . ? O4 S1 O4 109.81(8) . 3_565 ? O4 S1 O4 109.81(9) . 2_665 ? O4 S1 O4 109.81(9) 3_565 2_665 ? O4 S1 O3 109.13(9) . . ? O4 S1 O3 109.13(9) 3_565 . ? O4 S1 O3 109.13(9) 2_665 . ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.655 _refine_diff_density_min -0.539 _refine_diff_density_rms 0.066 # SQUEEZE RESULTS # 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 -0.002 -0.001 -0.001 4174 1235 ' ' 2 0.667 0.333 0.373 10 1 ' ' 3 0.333 0.667 0.627 10 2 ' ' _platon_squeeze_details ; The packing of the molecules of cage 4, generates large cavities that are filled with disordered molecules from the solvent of crystallization. No reasonable disorder model could be obtained for these molecules despite many attempts. They were therefore accounted for by the SQUEEZE/PLATON program. The program calculated a total solvent-accessible volume per unit cell of 4213.6 3, or 39.9.2% of the total unit cell volume, corresponding to 1237 e-/cell. The contribution of these diffusely scattering species was removed from the structure factor calculations. The tabulated F(000), MW and density reflect the known unit cell contents only.It is not possible to estimate with any confidence (water, dioxane, sulfate) what was removed by the SQUEEZE process. ;