# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2009 data_global _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 _journal_year ? _journal_volume ? _journal_page_first ? loop_ _publ_author_name A.Burrows C.Frost M.Mahon C.Richardson _publ_contact_author_name 'Andrew Burrows' _publ_contact_author_email A.D.BURROWS@BATH.AC.UK data_Compound-1-bath1 _database_code_depnum_ccdc_archive 'CCDC 725565' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C66 H78 N6 O19 S3 Zn4' _chemical_formula_weight 1617.00 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' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M C2/m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' '-x, -y, -z' 'x, -y, z' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z' _cell_length_a 25.0111(9) _cell_length_b 22.9843(9) _cell_length_c 17.1959(3) _cell_angle_alpha 90.00 _cell_angle_beta 96.404(4) _cell_angle_gamma 90.00 _cell_volume 9823.6(5) _cell_formula_units_Z 4 _cell_measurement_temperature 170(2) _cell_measurement_reflns_used 8634 _cell_measurement_theta_min 2.41 _cell_measurement_theta_max 25.59 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.093 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3344 _exptl_absorpt_coefficient_mu 1.082 _exptl_absorpt_correction_type Multi-scan _exptl_absorpt_correction_T_min 0.71 _exptl_absorpt_correction_T_max 0.82 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ; _diffrn_ambient_temperature 170(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'horizonally mounted graphite crystal' _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 83061 _diffrn_reflns_av_R_equivalents 0.0698 _diffrn_reflns_av_sigmaI/netI 0.0543 _diffrn_reflns_limit_h_min -31 _diffrn_reflns_limit_h_max 31 _diffrn_reflns_limit_k_min -28 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 21 _diffrn_reflns_theta_min 3.52 _diffrn_reflns_theta_max 26.70 _reflns_number_total 10421 _reflns_number_gt 6615 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97/2 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (P.McArdle, 1995)' _computing_publication_material 'SHELXL-97/2 (Sheldrick,1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The asymmetric unit in this network contains 1 full occupancy zinc (Zn2) and 2 half-occupancy zincs (Zn1 and Zn3), one full occupancy biphenyldicarboxylate, 1/2 of an additional derivatised ligand (wherein O2, O3, C17, C18 C21, C22 C25 and C29 are located on a crystallographic mirror plane), one 1/2 occupancy oxygen atom (at the centre of the SBU) and 2 DMF ligands attached to Zn3. The partial zinc atoms and ligand atoms bearing half occupancy are located on a crystallographic mirror plane, with the exceptions of carbons 2-7, which closely straddle said symmetry element. The data for this sample were good quality but, nevertheless, the refinement presented the usual issues that bedevil symmetrical 3-D MOF structures. In particular, the DMF ligand based on O8 was disordered over 2 sites, electron-density in this region and of the map was modeled subjects to distance restraints in the solvent fragment. O9 forms the basis of the second DMF ligand, and while credible residual density was observed for the remaining atoms in this ligand, refinement in this area did not succeed - probably due to disorder coupled with the proximity to the crystallographic mirror plane. As ever, there was rotational motion observable along the spine of each of the ligands, with ADP values increasing proportionally to the distance of atoms from said spine. In the case of the ligand straddling the mirror plane, 50:50 disorder was successfully modeled, the presence of which necessarily demands that the sulphur functionality is similarly disordered. Distance restraints were also applied in this part of the model to aid convergence. Overall however, the CH2SCH3 are remarkably ordered in this structure, given the possibilities for additional disorder in each ligand. After refinement of the network structure it was obvious that the cavities contained additional electron density. PLATON determined this solvent to be in the region of 10-11 DMF molecules per Zn4O moiety. However, given precedent in network structure, the final least squares takes account of the presence of 4 molecules of solvent per Zn4O moiety (as these materials do not normally have high densities, or hard-packed solvent in the pores). ; _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^)+(0.1628P)^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 10421 _refine_ls_number_parameters 334 _refine_ls_number_restraints 12 _refine_ls_R_factor_all 0.1006 _refine_ls_R_factor_gt 0.0765 _refine_ls_wR_factor_ref 0.2346 _refine_ls_wR_factor_gt 0.2190 _refine_ls_goodness_of_fit_ref 0.997 _refine_ls_restrained_S_all 1.035 _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 Zn1 Zn 0.07965(2) 0.0000 0.17837(3) 0.0389(2) Uani 1 2 d S . . Zn2 Zn 0.142419(19) 0.06731(2) 0.31883(2) 0.0516(2) Uani 1 1 d . . . Zn3 Zn 0.20952(3) 0.0000 0.19914(4) 0.0696(3) Uani 1 2 d SD . . S1 S -0.1479(2) 0.2552(3) 0.4852(3) 0.279(2) Uiso 1 1 d . . . S2 S 0.2443(5) 0.1166(5) 0.8119(7) 0.278(5) Uiso 0.50 1 d P . -1 O1 O 0.14198(14) 0.0000 0.25265(18) 0.0416(8) Uani 1 2 d S . . O2 O 0.1769(2) 0.0000 1.0870(3) 0.108(2) Uani 1 2 d S . . O3 O 0.08892(17) 0.0000 1.0686(2) 0.0583(11) Uani 1 2 d S . . O4 O 0.03299(14) 0.06713(14) 0.1922(2) 0.0673(9) Uani 1 1 d . . . O5 O 0.07180(17) 0.10570(18) 0.3029(2) 0.0871(12) Uani 1 1 d . . . O6 O -0.30376(19) 0.3737(2) 0.3134(3) 0.1148(18) Uani 1 1 d . . . O7 O -0.2813(4) 0.4129(3) 0.2025(3) 0.205(4) Uani 1 1 d . . . O8 O 0.2512(3) 0.0177(7) 0.3164(5) 0.133(8) Uani 0.50 1 d PD A -1 O9 O 0.2827(4) 0.0000 0.1519(6) 0.251(8) Uani 1 2 d S A . O10 O 0.14490(16) 0.04899(16) 0.42913(17) 0.0740(10) Uani 1 1 d . . . N1 N 0.3204(6) 0.0605(8) 0.3940(8) 0.239(10) Uiso 0.50 1 d PD A -1 C1 C 0.0342(2) 0.1013(2) 0.2483(3) 0.0640(12) Uani 1 1 d . . . C2 C -0.0127(3) 0.1416(3) 0.2501(4) 0.0859(18) Uani 1 1 d . . . C3 C -0.0537(3) 0.1411(3) 0.1899(4) 0.106(2) Uani 1 1 d . . . H3 H -0.0526 0.1149 0.1474 0.127 Uiso 1 1 calc R . . C4 C -0.0968(4) 0.1789(4) 0.1912(5) 0.140(3) Uani 1 1 d . . . H4 H -0.1238 0.1815 0.1479 0.168 Uiso 1 1 calc R . . C5 C -0.0995(4) 0.2139(4) 0.2592(5) 0.122(3) Uani 1 1 d . . . C6 C -0.0616(4) 0.2105(4) 0.3204(5) 0.134(3) Uani 1 1 d . . . H6 H -0.0646 0.2332 0.3659 0.161 Uiso 1 1 calc R . . C7 C -0.0174(3) 0.1734(3) 0.3174(5) 0.123(3) Uani 1 1 d . . . H7 H 0.0091 0.1702 0.3612 0.147 Uiso 1 1 calc R . . C8 C -0.1462(4) 0.2551(4) 0.2598(6) 0.146(4) Uani 1 1 d . . . C9 C -0.1561(5) 0.2924(5) 0.1964(6) 0.176(5) Uani 1 1 d . . . H9 H -0.1341 0.2927 0.1547 0.211 Uiso 1 1 calc R . . C10 C -0.2016(5) 0.3308(5) 0.1974(5) 0.183(5) Uani 1 1 d . . . H10 H -0.2112 0.3555 0.1537 0.220 Uiso 1 1 calc R . . C11 C -0.2309(4) 0.3326(4) 0.2582(5) 0.148(4) Uani 1 1 d . . . C12 C -0.2226(4) 0.2912(4) 0.3132(5) 0.145(4) Uani 1 1 d . . . H12 H -0.2467 0.2884 0.3519 0.174 Uiso 1 1 calc R . . C13 C -0.1813(4) 0.2534(4) 0.3153(6) 0.151(4) Uani 1 1 d . . . C14 C -0.1729(7) 0.2110(7) 0.3905(10) 0.264(8) Uiso 1 1 d . . . H14A H -0.1462 0.1805 0.3818 0.317 Uiso 1 1 calc R . . H14B H -0.2073 0.1915 0.3976 0.317 Uiso 1 1 calc R . . C15 C -0.1426(7) 0.1969(7) 0.5581(11) 0.277(8) Uiso 1 1 d . . . H15A H -0.1304 0.2132 0.6098 0.415 Uiso 1 1 calc R . . H15B H -0.1166 0.1678 0.5443 0.415 Uiso 1 1 calc R . . H15C H -0.1778 0.1786 0.5593 0.415 Uiso 1 1 calc R . . C16 C -0.2742(4) 0.3768(4) 0.2592(4) 0.161(5) Uani 1 1 d . . . C17 C 0.1459(2) 0.0000 0.4624(3) 0.0559(16) Uani 1 2 d S . . C18 C 0.1467(3) 0.0000 0.5500(3) 0.0571(16) Uani 1 2 d S . . C19 C 0.1306(4) 0.0497(4) 0.5896(6) 0.055(2) Uiso 0.50 1 d P B 1 H19 H 0.1200 0.0837 0.5603 0.066 Uiso 0.50 1 calc PR B 1 C19A C 0.1618(5) 0.0454(6) 0.5921(7) 0.081(3) Uiso 0.50 1 d P B 2 H19A H 0.1759 0.0779 0.5669 0.097 Uiso 0.50 1 calc PR B 2 C20 C 0.1297(4) 0.0503(4) 0.6669(6) 0.056(2) Uiso 0.50 1 d P B 1 H20 H 0.1187 0.0843 0.6923 0.067 Uiso 0.50 1 calc PR B 1 C20A C 0.1584(6) 0.0487(6) 0.6730(9) 0.092(4) Uiso 0.50 1 d P B 2 H20A H 0.1651 0.0843 0.7004 0.111 Uiso 0.50 1 calc PR B 2 C21 C 0.1453(3) 0.0000 0.7109(4) 0.073(2) Uani 1 2 d S . . C22 C 0.1435(3) 0.0000 0.7983(4) 0.078(2) Uani 1 2 d S . . C23 C 0.0946(3) -0.0115(3) 0.8284(4) 0.047(2) Uiso 0.50 1 d P . -1 H23 H 0.0635 -0.0200 0.7932 0.056 Uiso 0.50 1 calc PR . -1 C24 C 0.0907(3) -0.0109(3) 0.9046(4) 0.044(2) Uiso 0.50 1 d P . -1 H24 H 0.0568 -0.0180 0.9230 0.053 Uiso 0.50 1 calc PR . -1 C25 C 0.1359(3) 0.0000 0.9585(3) 0.0641(18) Uani 1 2 d S . . C26 C 0.1860(3) 0.0158(3) 0.9297(5) 0.053(2) Uiso 0.50 1 d P . -1 H26 H 0.2164 0.0259 0.9653 0.064 Uiso 0.50 1 calc PR . -1 C27 C 0.1895(4) 0.0160(3) 0.8499(5) 0.062(3) Uiso 0.50 1 d P . -1 C28 C 0.2427(7) 0.0314(6) 0.8236(10) 0.130(5) Uiso 0.50 1 d PD . -1 H28A H 0.2469 0.0123 0.7731 0.156 Uiso 0.50 1 calc PR . -1 H28B H 0.2723 0.0184 0.8627 0.156 Uiso 0.50 1 calc PR . -1 C29 C 0.1342(3) 0.0000 1.0450(3) 0.0560(16) Uani 1 2 d S . . C30 C 0.2637(13) 0.1220(10) 0.7160(15) 0.242(13) Uiso 0.50 1 d PD . -1 H30A H 0.2650 0.1631 0.7010 0.362 Uiso 0.50 1 calc PR . -1 H30B H 0.2376 0.1015 0.6792 0.362 Uiso 0.50 1 calc PR . -1 H30C H 0.2994 0.1046 0.7149 0.362 Uiso 0.50 1 calc PR . -1 C31 C 0.2977(4) 0.0395(8) 0.3196(5) 0.200(10) Uiso 0.50 1 d PD A -1 H31 H 0.3166 0.0418 0.2748 0.240 Uiso 0.50 1 calc PR A -1 C32 C 0.2906(10) 0.0565(13) 0.4635(7) 0.33(2) Uiso 0.50 1 d PD A -1 H32A H 0.3122 0.0738 0.5087 0.494 Uiso 0.50 1 calc PR A -1 H32B H 0.2836 0.0155 0.4745 0.494 Uiso 0.50 1 calc PR A -1 H32C H 0.2564 0.0774 0.4534 0.494 Uiso 0.50 1 calc PR A -1 C33 C 0.3719(10) 0.0872(17) 0.3873(14) 0.39(3) Uiso 0.50 1 d PD A -1 H33A H 0.3864 0.1031 0.4381 0.582 Uiso 0.50 1 calc PR A -1 H33B H 0.3675 0.1186 0.3486 0.582 Uiso 0.50 1 calc PR A -1 H33C H 0.3967 0.0579 0.3705 0.582 Uiso 0.50 1 calc PR A -1 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 Zn1 0.0371(3) 0.0598(4) 0.0216(3) 0.000 0.0117(2) 0.000 Zn2 0.0544(3) 0.0766(4) 0.0261(3) -0.0062(2) 0.0149(2) -0.0170(2) Zn3 0.0434(4) 0.1384(8) 0.0300(4) 0.000 0.0177(3) 0.000 O1 0.0393(19) 0.071(2) 0.0168(16) 0.000 0.0140(14) 0.000 O2 0.073(4) 0.221(8) 0.031(3) 0.000 0.014(2) 0.000 O3 0.062(3) 0.094(3) 0.0204(18) 0.000 0.0131(18) 0.000 O4 0.065(2) 0.074(2) 0.063(2) -0.0104(17) 0.0102(17) 0.0305(17) O5 0.085(3) 0.100(3) 0.077(3) -0.038(2) 0.010(2) 0.020(2) O6 0.127(4) 0.137(4) 0.083(3) 0.006(3) 0.024(3) 0.096(3) O7 0.325(10) 0.216(6) 0.089(4) 0.044(4) 0.096(5) 0.204(7) O8 0.063(4) 0.24(3) 0.089(5) -0.028(8) -0.005(4) -0.024(7) O9 0.091(6) 0.56(2) 0.116(7) 0.000 0.048(5) 0.000 O10 0.108(3) 0.094(2) 0.0237(15) -0.0060(16) 0.0221(16) -0.025(2) C1 0.064(3) 0.077(3) 0.055(3) -0.001(3) 0.024(2) 0.016(3) C2 0.106(5) 0.084(4) 0.072(4) 0.000(3) 0.034(3) 0.043(3) C3 0.107(5) 0.135(6) 0.076(4) -0.013(4) 0.017(4) 0.066(5) C4 0.143(7) 0.154(7) 0.125(6) -0.003(6) 0.027(5) 0.094(6) C5 0.133(6) 0.120(6) 0.117(6) -0.004(5) 0.036(5) 0.069(5) C6 0.166(8) 0.122(6) 0.119(7) -0.016(5) 0.036(6) 0.085(6) C7 0.136(6) 0.127(6) 0.106(6) -0.025(5) 0.017(5) 0.071(5) C8 0.165(8) 0.140(7) 0.138(7) 0.013(6) 0.044(6) 0.107(6) C9 0.210(11) 0.181(9) 0.148(8) 0.021(7) 0.069(8) 0.129(8) C10 0.236(11) 0.217(10) 0.111(6) 0.065(7) 0.084(7) 0.173(9) C11 0.183(8) 0.168(7) 0.106(6) 0.042(5) 0.070(6) 0.137(7) C12 0.185(9) 0.137(7) 0.129(7) 0.025(6) 0.079(6) 0.092(7) C13 0.173(8) 0.166(8) 0.127(7) 0.045(6) 0.074(6) 0.111(7) C16 0.228(10) 0.196(9) 0.066(4) 0.039(5) 0.055(5) 0.174(8) C17 0.054(4) 0.091(5) 0.026(3) 0.000 0.016(2) 0.000 C18 0.064(4) 0.084(4) 0.024(3) 0.000 0.009(3) 0.000 C21 0.058(4) 0.133(7) 0.031(3) 0.000 0.019(3) 0.000 C22 0.071(5) 0.135(7) 0.029(3) 0.000 0.009(3) 0.000 C25 0.066(4) 0.106(5) 0.023(3) 0.000 0.014(3) 0.000 C29 0.071(4) 0.074(4) 0.024(3) 0.000 0.012(3) 0.000 _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 Zn1 O1 1.902(3) . ? Zn1 O3 1.927(4) 1_554 ? Zn1 O4 1.965(3) 6 ? Zn1 O4 1.965(3) . ? Zn1 Zn2 3.1379(7) . ? Zn1 Zn2 3.1379(7) 6 ? Zn2 O6 1.919(3) 8 ? Zn2 O1 1.9200(19) . ? Zn2 O10 1.937(3) . ? Zn2 O5 1.966(4) . ? Zn2 Zn2 3.0943(11) 6 ? Zn3 O2 2.009(5) 1_554 ? Zn3 O1 2.012(3) . ? Zn3 O7 2.016(7) 3_545 ? Zn3 O7 2.016(7) 8 ? Zn3 O9 2.085(8) . ? Zn3 O8 2.202(7) . ? Zn3 O8 2.202(7) 6 ? S1 C15 1.829(16) . ? S1 C14 1.963(16) . ? S2 C30 1.78(2) . ? S2 C28 1.969(18) . ? O1 Zn2 1.9200(19) 6 ? O2 C29 1.221(8) . ? O2 Zn3 2.009(5) 1_556 ? O3 C29 1.245(7) . ? O3 Zn1 1.927(4) 1_556 ? O4 C1 1.241(6) . ? O5 C1 1.256(6) . ? O6 C16 1.255(8) . ? O6 Zn2 1.919(3) 8_455 ? O7 C16 1.276(8) . ? O7 Zn3 2.016(7) 3_455 ? O8 C31 1.262(5) . ? O10 C17 1.262(4) . ? N1 C31 1.424(4) . ? N1 C33 1.443(5) . ? N1 C32 1.480(5) . ? C1 C2 1.500(7) . ? C2 C3 1.374(9) . ? C2 C7 1.386(8) . ? C3 C4 1.386(9) . ? C3 H3 0.9500 . ? C4 C5 1.426(11) . ? C4 H4 0.9500 . ? C5 C6 1.339(11) . ? C5 C8 1.505(9) . ? C6 C7 1.400(9) . ? C6 H6 0.9500 . ? C7 H7 0.9500 . ? C8 C13 1.367(12) . ? C8 C9 1.388(12) . ? C9 C10 1.442(10) . ? C9 H9 0.9500 . ? C10 C11 1.342(10) . ? C10 H10 0.9500 . ? C11 C12 1.342(10) . ? C11 C16 1.486(8) . ? C12 C13 1.347(10) . ? C12 H12 0.9500 . ? C13 C14 1.615(17) . ? C14 H14A 0.9900 . ? C14 H14B 0.9900 . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? C17 O10 1.262(4) 6 ? C17 C18 1.505(8) . ? C18 C19A 1.303(13) 6 ? C18 C19A 1.303(13) . ? C18 C19 1.412(10) . ? C18 C19 1.412(10) 6 ? C19 C20 1.333(13) . ? C19 H19 0.9500 . ? C19A C20A 1.405(18) . ? C19A H19A 0.9500 . ? C20 C21 1.412(10) . ? C20 H20 0.9500 . ? C20A C21 1.353(15) . ? C20A H20A 0.9500 . ? C21 C20A 1.353(15) 6 ? C21 C20 1.412(10) 6 ? C21 C22 1.509(9) . ? C22 C23 1.406(10) . ? C22 C23 1.406(10) 6 ? C22 C27 1.421(11) 6 ? C22 C27 1.421(11) . ? C23 C24 1.325(9) . ? C23 H23 0.9500 . ? C24 C25 1.402(9) . ? C24 H24 0.9500 . ? C25 C24 1.402(9) 6 ? C25 C26 1.445(10) 6 ? C25 C26 1.445(10) . ? C25 C29 1.492(8) . ? C26 C27 1.385(11) . ? C26 H26 0.9500 . ? C27 C28 1.495(18) . ? C28 H28A 0.9900 . ? C28 H28B 0.9900 . ? C30 H30A 0.9800 . ? C30 H30B 0.9800 . ? C30 H30C 0.9800 . ? C31 H31 0.9500 . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? C33 H33A 0.9800 . ? C33 H33B 0.9800 . ? C33 H33C 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Zn1 O3 118.60(16) . 1_554 ? O1 Zn1 O4 111.84(12) . 6 ? O3 Zn1 O4 104.86(13) 1_554 6 ? O1 Zn1 O4 111.84(12) . . ? O3 Zn1 O4 104.86(13) 1_554 . ? O4 Zn1 O4 103.5(2) 6 . ? O1 Zn1 Zn2 35.00(5) . . ? O3 Zn1 Zn2 130.50(10) 1_554 . ? O4 Zn1 Zn2 123.15(10) 6 . ? O4 Zn1 Zn2 76.85(10) . . ? O1 Zn1 Zn2 35.00(5) . 6 ? O3 Zn1 Zn2 130.50(10) 1_554 6 ? O4 Zn1 Zn2 76.85(10) 6 6 ? O4 Zn1 Zn2 123.15(10) . 6 ? Zn2 Zn1 Zn2 59.08(2) . 6 ? O6 Zn2 O1 119.86(18) 8 . ? O6 Zn2 O10 104.77(17) 8 . ? O1 Zn2 O10 113.74(13) . . ? O6 Zn2 O5 107.5(2) 8 . ? O1 Zn2 O5 109.48(15) . . ? O10 Zn2 O5 99.44(17) . . ? O6 Zn2 Zn2 134.90(18) 8 6 ? O1 Zn2 Zn2 36.31(8) . 6 ? O10 Zn2 Zn2 77.44(11) . 6 ? O5 Zn2 Zn2 116.67(13) . 6 ? O6 Zn2 Zn1 127.16(13) 8 . ? O1 Zn2 Zn1 34.62(10) . . ? O10 Zn2 Zn1 127.24(11) . . ? O5 Zn2 Zn1 75.50(11) . . ? Zn2 Zn2 Zn1 60.459(11) 6 . ? O2 Zn3 O1 99.62(19) 1_554 . ? O2 Zn3 O7 93.47(19) 1_554 3_545 ? O1 Zn3 O7 94.9(2) . 3_545 ? O2 Zn3 O7 93.47(19) 1_554 8 ? O1 Zn3 O7 94.9(2) . 8 ? O7 Zn3 O7 166.9(5) 3_545 8 ? O2 Zn3 O9 84.6(3) 1_554 . ? O1 Zn3 O9 175.8(3) . . ? O7 Zn3 O9 84.8(2) 3_545 . ? O7 Zn3 O9 84.8(2) 8 . ? O2 Zn3 O8 168.4(4) 1_554 . ? O1 Zn3 O8 85.2(2) . . ? O7 Zn3 O8 96.7(5) 3_545 . ? O7 Zn3 O8 75.5(5) 8 . ? O9 Zn3 O8 90.6(3) . . ? O2 Zn3 O8 168.4(4) 1_554 6 ? O1 Zn3 O8 85.2(2) . 6 ? O7 Zn3 O8 75.5(5) 3_545 6 ? O7 Zn3 O8 96.7(5) 8 6 ? O9 Zn3 O8 90.6(3) . 6 ? O8 Zn3 O8 21.3(9) . 6 ? C15 S1 C14 100.4(8) . . ? C30 S2 C28 100.1(10) . . ? Zn1 O1 Zn2 110.38(12) . 6 ? Zn1 O1 Zn2 110.38(12) . . ? Zn2 O1 Zn2 107.38(15) 6 . ? Zn1 O1 Zn3 111.10(15) . . ? Zn2 O1 Zn3 108.75(12) 6 . ? Zn2 O1 Zn3 108.75(12) . . ? C29 O2 Zn3 143.4(5) . 1_556 ? C29 O3 Zn1 122.2(4) . 1_556 ? C1 O4 Zn1 128.8(3) . . ? C1 O5 Zn2 130.7(3) . . ? C16 O6 Zn2 118.1(4) . 8_455 ? C16 O7 Zn3 132.3(6) . 3_455 ? C31 O8 Zn3 116.9(5) . . ? C17 O10 Zn2 129.4(3) . . ? C31 N1 C33 110.0(5) . . ? C31 N1 C32 121.2(4) . . ? C33 N1 C32 128.7(7) . . ? O4 C1 O5 125.8(4) . . ? O4 C1 C2 117.1(5) . . ? O5 C1 C2 117.1(5) . . ? C3 C2 C7 120.6(6) . . ? C3 C2 C1 120.0(5) . . ? C7 C2 C1 118.9(6) . . ? C2 C3 C4 119.9(7) . . ? C2 C3 H3 120.0 . . ? C4 C3 H3 120.0 . . ? C3 C4 C5 118.3(8) . . ? C3 C4 H4 120.8 . . ? C5 C4 H4 120.8 . . ? C6 C5 C4 121.2(7) . . ? C6 C5 C8 120.9(8) . . ? C4 C5 C8 117.9(8) . . ? C5 C6 C7 119.9(7) . . ? C5 C6 H6 120.0 . . ? C7 C6 H6 120.0 . . ? C2 C7 C6 119.5(8) . . ? C2 C7 H7 120.2 . . ? C6 C7 H7 120.2 . . ? C13 C8 C9 119.6(7) . . ? C13 C8 C5 123.1(8) . . ? C9 C8 C5 117.0(8) . . ? C8 C9 C10 116.2(9) . . ? C8 C9 H9 121.9 . . ? C10 C9 H9 121.9 . . ? C11 C10 C9 121.9(8) . . ? C11 C10 H10 119.1 . . ? C9 C10 H10 119.1 . . ? C12 C11 C10 118.2(6) . . ? C12 C11 C16 122.2(7) . . ? C10 C11 C16 119.5(7) . . ? C11 C12 C13 122.3(8) . . ? C11 C12 H12 118.8 . . ? C13 C12 H12 118.8 . . ? C12 C13 C8 120.8(8) . . ? C12 C13 C14 116.2(9) . . ? C8 C13 C14 122.7(8) . . ? C13 C14 S1 110.6(10) . . ? C13 C14 H14A 109.5 . . ? S1 C14 H14A 109.5 . . ? C13 C14 H14B 109.5 . . ? S1 C14 H14B 109.5 . . ? H14A C14 H14B 108.1 . . ? S1 C15 H15A 109.5 . . ? S1 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? S1 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? O6 C16 O7 124.1(6) . . ? O6 C16 C11 117.4(6) . . ? O7 C16 C11 118.3(7) . . ? O10 C17 O10 126.3(5) 6 . ? O10 C17 C18 116.8(3) 6 . ? O10 C17 C18 116.8(3) . . ? C19A C18 C19A 106.6(12) 6 . ? C19A C18 C19 117.5(7) 6 . ? C19A C18 C19 33.3(6) . . ? C19A C18 C19 33.3(6) 6 6 ? C19A C18 C19 117.5(7) . 6 ? C19 C18 C19 108.0(9) . 6 ? C19A C18 C17 121.8(6) 6 . ? C19A C18 C17 121.8(6) . . ? C19 C18 C17 120.7(5) . . ? C19 C18 C17 120.7(5) 6 . ? C20 C19 C18 121.8(9) . . ? C20 C19 H19 119.1 . . ? C18 C19 H19 119.1 . . ? C18 C19A C20A 123.1(12) . . ? C18 C19A H19A 118.4 . . ? C20A C19A H19A 118.4 . . ? C19 C20 C21 119.4(9) . . ? C19 C20 H20 120.3 . . ? C21 C20 H20 120.3 . . ? C21 C20A C19A 118.5(12) . . ? C21 C20A H20A 120.7 . . ? C19A C20A H20A 120.7 . . ? C20A C21 C20A 111.6(14) 6 . ? C20A C21 C20 29.9(6) 6 6 ? C20A C21 C20 119.1(8) . 6 ? C20A C21 C20 119.1(8) 6 . ? C20A C21 C20 29.9(6) . . ? C20 C21 C20 109.9(9) 6 . ? C20A C21 C22 121.0(7) 6 . ? C20A C21 C22 121.0(7) . . ? C20 C21 C22 119.7(5) 6 . ? C20 C21 C22 119.7(5) . . ? C23 C22 C23 21.8(6) . 6 ? C23 C22 C27 113.4(6) . 6 ? C23 C22 C27 119.7(7) 6 6 ? C23 C22 C27 119.7(7) . . ? C23 C22 C27 113.4(6) 6 . ? C27 C22 C27 30.0(7) 6 . ? C23 C22 C21 119.4(6) . . ? C23 C22 C21 119.4(6) 6 . ? C27 C22 C21 120.7(6) 6 . ? C27 C22 C21 120.7(6) . . ? C24 C23 C22 121.7(6) . . ? C24 C23 H23 119.2 . . ? C22 C23 H23 119.2 . . ? C23 C24 C25 120.8(6) . . ? C23 C24 H24 119.6 . . ? C25 C24 H24 119.6 . . ? C24 C25 C24 20.6(6) . 6 ? C24 C25 C26 113.3(5) . 6 ? C24 C25 C26 119.0(6) 6 6 ? C24 C25 C26 119.0(6) . . ? C24 C25 C26 113.3(5) 6 . ? C26 C25 C26 29.1(6) 6 . ? C24 C25 C29 123.2(6) . . ? C24 C25 C29 123.2(6) 6 . ? C26 C25 C29 117.6(6) 6 . ? C26 C25 C29 117.6(6) . . ? C27 C26 C25 119.5(7) . . ? C27 C26 H26 120.2 . . ? C25 C26 H26 120.2 . . ? C26 C27 C22 118.9(8) . . ? C26 C27 C28 117.2(10) . . ? C22 C27 C28 123.9(10) . . ? C27 C28 S2 107.1(10) . . ? C27 C28 H28A 110.3 . . ? S2 C28 H28A 110.3 . . ? C27 C28 H28B 110.3 . . ? S2 C28 H28B 110.3 . . ? H28A C28 H28B 108.5 . . ? O2 C29 O3 125.0(5) . . ? O2 C29 C25 118.0(6) . . ? O3 C29 C25 117.0(6) . . ? S2 C30 H30A 109.5 . . ? S2 C30 H30B 109.5 . . ? H30A C30 H30B 109.5 . . ? S2 C30 H30C 109.5 . . ? H30A C30 H30C 109.5 . . ? H30B C30 H30C 109.5 . . ? O8 C31 N1 116.5(4) . . ? O8 C31 H31 121.7 . . ? N1 C31 H31 121.7 . . ? N1 C32 H32A 109.5 . . ? N1 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? N1 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? N1 C33 H33A 109.5 . . ? N1 C33 H33B 109.5 . . ? H33A C33 H33B 109.5 . . ? N1 C33 H33C 109.5 . . ? H33A C33 H33C 109.5 . . ? H33B C33 H33C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.975 _diffrn_reflns_theta_full 26.70 _diffrn_measured_fraction_theta_full 0.975 _refine_diff_density_max 1.080 _refine_diff_density_min -0.844 _refine_diff_density_rms 0.109 # SQUEEZE RESULTS 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 0.291 -0.009 0.030 4720 1820 ' ' #===end data_Compound-2-bath6 _database_code_depnum_ccdc_archive 'CCDC 725566' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C69 H83 N5 O18 S6 Zn4' _chemical_formula_weight 1724.24 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' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Hexagonal _symmetry_space_group_name_H-M R-3m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x-y, -y, -z' '-x, -x+y, -z' 'y, x, -z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x-y+2/3, -y+1/3, -z+1/3' '-x+2/3, -x+y+1/3, -z+1/3' 'y+2/3, x+1/3, -z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' 'x-y+1/3, -y+2/3, -z+2/3' '-x+1/3, -x+y+2/3, -z+2/3' 'y+1/3, x+2/3, -z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+y, y, z' 'x, x-y, z' '-y, -x, z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+y+2/3, y+1/3, z+1/3' 'x+2/3, x-y+1/3, z+1/3' '-y+2/3, -x+1/3, z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' '-x+y+1/3, y+2/3, z+2/3' 'x+1/3, x-y+2/3, z+2/3' '-y+1/3, -x+2/3, z+2/3' _cell_length_a 23.8212(3) _cell_length_b 23.8212(3) _cell_length_c 30.2938(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 14887.1(6) _cell_formula_units_Z 6 _cell_measurement_temperature 273(2) _cell_measurement_reflns_used 8173 _cell_measurement_theta_min 2.39 _cell_measurement_theta_max 21.09 _exptl_crystal_description block _exptl_crystal_colour colorless _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.154 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 5352 _exptl_absorpt_coefficient_mu 1.135 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.69 _exptl_absorpt_correction_T_max 0.81 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ; _diffrn_ambient_temperature 170(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'horizonally mounted graphite crystal' _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 84171 _diffrn_reflns_av_R_equivalents 0.0999 _diffrn_reflns_av_sigmaI/netI 0.0620 _diffrn_reflns_limit_h_min -29 _diffrn_reflns_limit_h_max 29 _diffrn_reflns_limit_k_min -29 _diffrn_reflns_limit_k_max 29 _diffrn_reflns_limit_l_min -37 _diffrn_reflns_limit_l_max 37 _diffrn_reflns_theta_min 3.58 _diffrn_reflns_theta_max 26.45 _reflns_number_total 3663 _reflns_number_gt 1722 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97/2 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (P.McArdle, 1995)' _computing_publication_material 'SHELXL-97/2 (Sheldrick,1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The asymmetric unit in this structure contains 1/2 of full zinc (Zn2), 1/6 of a zinc (Zn1), 1/6 of an oxygen at the centre of the SBU (O1) a ligand fragment in which O2, O3, C1-C8 and C11 and C12 are located on a crystallographic mirror plane, and approximately 2.5 molecules of DMF solvent. The data for this structure are high quality to the given resolution, given the usual issues with obtaining good data on 3-D MOFs. Thus, it was frustrating not to be in a position to refine the tags on the ligand. Examination of the ADPs explains the issue in part, when taken in conjunction with the high symmetry present and the disorder. After refining the distances in the aromatic rings subject to some restraints based on ideal values, there was clear evidence for twisting of the these rings about the C1-C12 axis. In addition, the difference electron density map suggest (Figs 1 and 2) that the tags are disordered in a 50:50 ratio over 2 possible sites . These facts precluded reliable location and refinement of the fragments present, which is not untypical of this variety of MOFs. Fo-Fc maps taken perpendicular to the phenyl ring planes show the residual e-density due to the tag atoms in these planes (proximate to C4 , C6, C9 and its symmetry related counterpart). After refinement of the network structure it was obvious that the cavities contained additional electron density. PLATON determined this solvent to be significantly higher than realistic -- not aided by the fact that the un-modeled tag electron density contributes to the calculation. However, given precedent in network structure, the final least squares takes account of the presence of 5 molecules of solvent per Zn4O moiety. ; _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^)+(0.1066P)^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 3663 _refine_ls_number_parameters 112 _refine_ls_number_restraints 28 _refine_ls_R_factor_all 0.1577 _refine_ls_R_factor_gt 0.0666 _refine_ls_wR_factor_ref 0.1994 _refine_ls_wR_factor_gt 0.1686 _refine_ls_goodness_of_fit_ref 0.954 _refine_ls_restrained_S_all 0.958 _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 Zn1 Zn 0.0000 0.0000 0.07759(4) 0.0841(4) Uani 1 6 d S . . Zn2 Zn 0.044436(16) 0.08887(3) 0.16150(2) 0.0936(4) Uani 1 2 d S . . O1 O 0.0000 0.0000 0.14164(17) 0.0650(14) Uani 1 6 d S . . O2 O 0.07439(14) 0.1488(3) 0.1132(2) 0.210(3) Uani 1 2 d S . . O3 O 0.04312(15) 0.0862(3) 0.05425(19) 0.144(2) Uani 1 2 d S . . O4 O 0.3220(2) 0.55041(19) -0.13306(15) 0.1629(16) Uani 1 1 d . . . C1 C 0.0694(3) 0.1388(5) 0.0717(3) 0.131(3) Uani 1 2 d S . . C2 C 0.0980(2) 0.1959(4) 0.0454(3) 0.174(4) Uani 1 2 d SD . . C3 C 0.1288(3) 0.2575(6) 0.0640(3) 0.315(10) Uani 1 2 d SD . . H3 H 0.1311 0.2622 0.0945 0.377 Uiso 1 2 calc SR . . C4 C 0.1564(2) 0.3127(4) 0.0369(4) 0.320(10) Uani 1 2 d SD . . C5 C 0.1525(2) 0.3050(5) -0.0101(3) 0.226(6) Uani 1 2 d SD . . C6 C 0.1214(2) 0.2429(4) -0.0290(2) 0.156(3) Uani 1 2 d SD . . C7 C 0.09452(19) 0.1890(4) -0.0005(3) 0.157(3) Uani 1 2 d SD . . H7 H 0.0738 0.1476 -0.0125 0.189 Uiso 1 2 calc SR . . C8 C 0.1815(3) 0.3629(5) -0.0388(4) 0.229(7) Uani 1 2 d SD . . C9 C 0.2466(4) 0.3921(4) -0.0517(3) 0.244(5) Uani 1 1 d D . . C10 C 0.2729(4) 0.4471(4) -0.0782(3) 0.225(4) Uani 1 1 d D . . H10 H 0.3162 0.4668 -0.0865 0.270 Uiso 1 1 calc R . . C11 C 0.2361(2) 0.4723(4) -0.0921(3) 0.177(5) Uani 1 2 d SD . . C12 C 0.2664(3) 0.5328(5) -0.1215(3) 0.146(3) Uani 1 2 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 Zn1 0.0918(6) 0.0918(6) 0.0687(7) 0.000 0.000 0.0459(3) Zn2 0.1031(5) 0.0859(5) 0.0862(5) -0.0061(3) -0.00307(17) 0.0429(3) O1 0.064(2) 0.064(2) 0.067(3) 0.000 0.000 0.0320(10) O2 0.320(8) 0.110(4) 0.130(5) 0.038(4) 0.0191(19) 0.055(2) O3 0.184(4) 0.112(4) 0.113(4) 0.043(3) 0.0214(16) 0.056(2) O4 0.164(4) 0.134(3) 0.177(4) 0.055(3) -0.001(3) 0.064(3) C1 0.165(6) 0.125(7) 0.090(6) 0.061(6) 0.030(3) 0.062(3) C2 0.209(8) 0.124(8) 0.159(10) 0.031(7) 0.015(4) 0.062(4) C3 0.55(3) 0.157(10) 0.109(8) 0.053(8) 0.026(4) 0.079(5) C4 0.52(2) 0.121(8) 0.185(12) 0.076(9) 0.038(4) 0.061(4) C5 0.311(12) 0.149(10) 0.165(11) 0.091(9) 0.045(5) 0.074(5) C6 0.201(7) 0.116(6) 0.121(6) 0.041(6) 0.021(3) 0.058(3) C7 0.198(7) 0.123(7) 0.126(7) 0.026(6) 0.013(3) 0.062(3) C8 0.339(17) 0.107(8) 0.163(9) 0.077(7) 0.038(3) 0.054(4) C9 0.230(9) 0.166(7) 0.258(10) 0.127(7) -0.020(7) 0.042(6) C10 0.230(9) 0.148(6) 0.219(8) 0.099(6) -0.008(6) 0.036(6) C11 0.247(11) 0.098(6) 0.137(8) 0.059(6) 0.029(3) 0.049(3) C12 0.140(5) 0.183(10) 0.131(7) 0.047(6) 0.024(3) 0.092(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 Zn1 O3 1.914(6) 2 ? Zn1 O3 1.914(6) . ? Zn1 O3 1.914(6) 3 ? Zn1 O1 1.940(5) . ? Zn1 Zn2 3.1341(11) . ? Zn1 Zn2 3.1341(11) 3 ? Zn1 Zn2 3.1341(11) 2 ? Zn2 O2 1.916(6) . ? Zn2 O1 1.9296(18) . ? Zn2 O4 1.949(4) 8 ? Zn2 O4 1.949(4) 29_455 ? O1 Zn2 1.9296(18) 2 ? O1 Zn2 1.9296(18) 3 ? O2 C1 1.273(10) . ? O3 C1 1.207(9) . ? O4 C12 1.223(5) . ? O4 Zn2 1.949(4) 15_554 ? C1 C2 1.421(10) . ? C2 C3 1.390(10) . ? C2 C7 1.398(9) . ? C3 C4 1.403(12) . ? C3 H3 0.9300 . ? C4 C5 1.432(10) . ? C5 C6 1.406(9) . ? C5 C8 1.479(12) . ? C6 C7 1.407(8) . ? C7 H7 0.9300 . ? C8 C9 1.401(8) . ? C8 C9 1.401(8) 22 ? C9 C10 1.392(8) . ? C10 C11 1.351(7) . ? C10 H10 0.9300 . ? C11 C10 1.351(7) 22 ? C11 C12 1.535(12) . ? C12 O4 1.223(5) 22 ? 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 O3 Zn1 O3 107.2(2) 2 . ? O3 Zn1 O3 107.2(2) 2 3 ? O3 Zn1 O3 107.2(2) . 3 ? O3 Zn1 O1 111.67(19) 2 . ? O3 Zn1 O1 111.67(19) . . ? O3 Zn1 O1 111.67(19) 3 . ? O3 Zn1 Zn2 124.84(15) 2 . ? O3 Zn1 Zn2 75.87(19) . . ? O3 Zn1 Zn2 124.84(15) 3 . ? O1 Zn1 Zn2 35.802(17) . . ? O3 Zn1 Zn2 124.84(15) 2 3 ? O3 Zn1 Zn2 124.84(15) . 3 ? O3 Zn1 Zn2 75.87(19) 3 3 ? O1 Zn1 Zn2 35.802(17) . 3 ? Zn2 Zn1 Zn2 60.88(3) . 3 ? O3 Zn1 Zn2 75.87(19) 2 2 ? O3 Zn1 Zn2 124.84(15) . 2 ? O3 Zn1 Zn2 124.84(15) 3 2 ? O1 Zn1 Zn2 35.802(17) . 2 ? Zn2 Zn1 Zn2 60.88(3) . 2 ? Zn2 Zn1 Zn2 60.88(3) 3 2 ? O2 Zn2 O1 112.0(2) . . ? O2 Zn2 O4 110.54(18) . 8 ? O1 Zn2 O4 110.46(15) . 8 ? O2 Zn2 O4 110.54(18) . 29_455 ? O1 Zn2 O4 110.46(15) . 29_455 ? O4 Zn2 O4 102.5(3) 8 29_455 ? O2 Zn2 Zn1 76.0(2) . . ? O1 Zn2 Zn1 36.03(15) . . ? O4 Zn2 Zn1 126.04(13) 8 . ? O4 Zn2 Zn1 126.04(13) 29_455 . ? Zn2 O1 Zn2 110.75(14) . 2 ? Zn2 O1 Zn2 110.75(14) . 3 ? Zn2 O1 Zn2 110.75(14) 2 3 ? Zn2 O1 Zn1 108.16(15) . . ? Zn2 O1 Zn1 108.16(15) 2 . ? Zn2 O1 Zn1 108.16(15) 3 . ? C1 O2 Zn2 130.6(6) . . ? C1 O3 Zn1 132.4(5) . . ? C12 O4 Zn2 128.2(6) . 15_554 ? O3 C1 O2 125.2(7) . . ? O3 C1 C2 120.0(9) . . ? O2 C1 C2 114.8(10) . . ? C3 C2 C7 119.7(7) . . ? C3 C2 C1 122.1(9) . . ? C7 C2 C1 118.2(9) . . ? C2 C3 C4 120.4(7) . . ? C2 C3 H3 119.8 . . ? C4 C3 H3 119.8 . . ? C3 C4 C5 119.4(8) . . ? C6 C5 C4 120.5(7) . . ? C6 C5 C8 119.7(10) . . ? C4 C5 C8 119.8(10) . . ? C5 C6 C7 118.0(6) . . ? C2 C7 C6 122.1(7) . . ? C2 C7 H7 118.9 . . ? C6 C7 H7 118.9 . . ? C9 C8 C9 118.6(9) . 22 ? C9 C8 C5 120.6(5) . . ? C9 C8 C5 120.6(5) 22 . ? C10 C9 C8 119.4(9) . . ? C11 C10 C9 120.8(9) . . ? C11 C10 H10 119.6 . . ? C9 C10 H10 119.6 . . ? C10 C11 C10 120.8(9) . 22 ? C10 C11 C12 119.6(5) . . ? C10 C11 C12 119.6(5) 22 . ? O4 C12 O4 131.4(10) 22 . ? O4 C12 C11 114.0(5) 22 . ? O4 C12 C11 114.0(5) . . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 26.45 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 0.484 _refine_diff_density_min -0.288 _refine_diff_density_rms 0.054 # SQUEEZE RESULTS 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 -0.009 0.306 -0.008 10424 5383 ' ' #===end data_Compound-4-h06adb11 _database_code_depnum_ccdc_archive 'CCDC 725567' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C60 H64 N4 O23 S3 Zn4' _chemical_formula_weight 1566.81 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' 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' Zn Zn 0.2839 1.4301 '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 Monoclinic _symmetry_space_group_name_H-M C2/m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' '-x, -y, -z' 'x, -y, z' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z' _cell_length_a 25.1670(4) _cell_length_b 23.2000(3) _cell_length_c 17.1020(3) _cell_angle_alpha 90.00 _cell_angle_beta 93.561(1) _cell_angle_gamma 90.00 _cell_volume 9966.1(3) _cell_formula_units_Z 4 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 35859 _cell_measurement_theta_min 2.910 _cell_measurement_theta_max 27.485 _exptl_crystal_description block _exptl_crystal_colour ? _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.044 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 3216 _exptl_absorpt_coefficient_mu 1.067 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.591 _exptl_absorpt_correction_T_max 0.653 _exptl_absorpt_process_details ; multi-scan from symmetry-related measurements Sortav (Blessing 1995) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 88639 _diffrn_reflns_av_R_equivalents 0.0592 _diffrn_reflns_av_sigmaI/netI 0.0440 _diffrn_reflns_limit_h_min -32 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -30 _diffrn_reflns_limit_k_max 30 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 3.53 _diffrn_reflns_theta_max 27.49 _reflns_number_total 11661 _reflns_number_gt 8102 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97/2 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEX (P.McArdle, 1995)' _computing_publication_material 'SHELXL-97/2 (Sheldrick,1997)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. The asymmetric unit in this network contains 1 full occupancy zinc (Zn2) and 2 half-occupancy zincs (Zn1 and Zn3), one full occupancy derivatised biphenyldicarboxylate, 1/2 of an additional derivatised ligand (wherein C17, C18, C21, O7 and O8 are located on a crystallographic mirror plane), one 1/2 occupancy oxygen atom ( at the centre of the SBU) and 2 DMF ligands attached to Zn3. The partial zinc atoms are also located on a crystallographic mirror plane, as is the DMF ligand based on N1. Carbons 22-28 are refined at 1/2 occupancy, being very close to this same symmetry element. The data for this sample were good quality but, nevertheless, the refinement presented the usual issues that bedevil symmetrical 3-D MOF structures. In particular, the DMF ligand based on O10 was disordered over 2 sites, and only the oxygen and one carbon atom therein could be reliably added to the atoms list for refinement. Electron-density in the solvent ligand region and of the map was modeled subjects to distance restraints within each fragment. As ever, there was rotational motion observable along the spine of each of the ligands, with ADP values increasing proportionally to the distance of atoms from said spine. In the case of the ligand straddling the mirror plane, 50:50 disorder was successfully modeled, the presence of which necessarily demands that the functional group is similarly disordered. The sulfur containing functionality of the full occupancy ligand was also disordered in a 1:1 ratio (S1/S1A)-- but this time the disorder was equally divided between both rings. Similarity distance restraints were applied to S-O and S-C distances within the functional groups. Only the sulfur atoms in the partial functional ligands were treated anisotropically. As always observed in structures that we have completed in this family, there is considerable ligand rotation of the ligands about the long-axis of each. Consequently, the aromatic rings were refined as hexagons where possible. While the geometry about Zn1 and Zn2 are tetrahedral, Zn3 exhibits distorted octahedral geometry. The angles in the coordination sphere are not ideal, but a combination of thermal motion, disorder and lattice symmetry coalesced to preclude any reasonable additional modeling in this region. After refinement of the network structure it was obvious that the cavities contained additional electron density. PLATON determined this solvent to be in the region of 2.7 DMF molecules per Zn4O moiety. However, given precedent in network structure, the final least squares takes account of the presence of 2 molecules of solvent per Zn4O moiety, the additional 0.7(DMF) being attributed to the atoms in the ligand based on O10, which could not be reliably included I the least-squares. ; _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^)+(0.2000P)^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 11661 _refine_ls_number_parameters 334 _refine_ls_number_restraints 24 _refine_ls_R_factor_all 0.1159 _refine_ls_R_factor_gt 0.0884 _refine_ls_wR_factor_ref 0.2914 _refine_ls_wR_factor_gt 0.2743 _refine_ls_goodness_of_fit_ref 1.104 _refine_ls_restrained_S_all 1.199 _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 Zn1 Zn 0.08059(3) 0.0000 0.18451(4) 0.0398(2) Uani 1 2 d S . . Zn2 Zn 0.147448(19) 0.06699(2) 0.31645(3) 0.0440(2) Uani 1 1 d . . . Zn3 Zn 0.20782(3) 0.0000 0.18385(5) 0.0592(3) Uani 1 2 d S . . S1 S -0.1507(2) 0.2530(2) 0.4928(3) 0.143(3) Uani 0.565(8) 1 d PD . . S1A S 0.0450(7) 0.3519(6) 0.3211(11) 0.276(8) Uani 0.435(8) 1 d PD . . S2 S 0.2623(3) -0.0990(6) 0.8279(5) 0.210(4) Uani 0.50 1 d PD . -1 O1 O 0.14548(14) 0.0000 0.2509(2) 0.0354(8) Uani 1 2 d S . . O2 O 0.03625(14) 0.06726(16) 0.2048(2) 0.0621(9) Uani 1 1 d . . . O3 O 0.08427(17) 0.11516(19) 0.2990(3) 0.0836(13) Uani 1 1 d . . . O4 O -0.2541(3) 0.4328(4) 0.2207(7) 0.210(6) Uani 1 1 d . . . O5 O -0.29308(18) 0.38118(18) 0.3105(3) 0.0815(12) Uani 1 1 d . . . O6 O 0.15168(18) 0.0485(2) 0.4280(2) 0.0755(11) Uani 1 1 d . . . O7 O 0.1744(5) 0.0000 1.0847(5) 0.226(9) Uani 1 2 d S . . O8 O 0.0840(2) 0.0000 1.0719(3) 0.0697(15) Uani 1 2 d S . . O9 O 0.1745(5) 0.0849(5) 0.1400(8) 0.131(5) Uani 0.50 1 d PD . . O10 O 0.2667(5) 0.0000 0.1093(11) 0.234(7) Uiso 1 2 d SD . . O11 O -0.0931(6) 0.2728(7) 0.4958(10) 0.155(5) Uiso 0.50 1 d PD . . O11A O 0.0935(11) 0.3156(14) 0.294(2) 0.294(14) Uiso 0.50 1 d PD . . O12 O -0.1520(7) 0.2052(7) 0.5602(10) 0.167(6) Uiso 0.50 1 d PD . . O12A O 0.0165(13) 0.3858(14) 0.2497(18) 0.292(14) Uiso 0.50 1 d PD . . O13 O 0.2695(11) -0.1159(11) 0.9179(11) 0.245(10) Uiso 0.50 1 d PD . -1 O14 O 0.2313(9) -0.1476(10) 0.7812(16) 0.239(10) Uiso 0.50 1 d PD . -1 N1 N 0.1685(12) 0.1766(15) 0.0806(16) 0.241(13) Uiso 0.50 1 d PD . . C1 C 0.0433(2) 0.1067(3) 0.2556(3) 0.0662(15) Uani 1 1 d . . . C2 C -0.00047(16) 0.1497(2) 0.2596(3) 0.0796(18) Uani 1 1 d G . . C3 C -0.04699(17) 0.1441(2) 0.2120(3) 0.095(2) Uani 1 1 d G B . H3 H -0.0507 0.1132 0.1755 0.114 Uiso 1 1 calc R . . C4 C -0.08806(16) 0.1836(3) 0.2177(3) 0.106(3) Uani 1 1 d G B . H4 H -0.1199 0.1798 0.1851 0.127 Uiso 1 1 calc R A 1 C5 C -0.0826(2) 0.2288(3) 0.2710(4) 0.142(4) Uani 1 1 d G B 1 C6 C -0.0361(3) 0.2344(3) 0.3186(4) 0.226(9) Uani 1 1 d G B 1 C7 C 0.0050(2) 0.1949(3) 0.3129(4) 0.197(7) Uani 1 1 d G B 1 H7 H 0.0368 0.1987 0.3454 0.237 Uiso 1 1 calc R B 1 C8 C -0.12906(13) 0.26900(17) 0.27481(17) 0.138(4) Uani 1 1 d G . . C9 C -0.13176(15) 0.3116(2) 0.2175(2) 0.208(8) Uani 1 1 d G B . H9 H -0.1049 0.3140 0.1810 0.249 Uiso 1 1 calc R . . C10 C -0.17376(14) 0.35058(19) 0.2136(2) 0.252(11) Uani 1 1 d G B . H10 H -0.1756 0.3797 0.1745 0.302 Uiso 1 1 calc R . . C11 C -0.21305(13) 0.34703(16) 0.2671(2) 0.103(3) Uani 1 1 d G B . C12 C -0.21035(12) 0.30447(16) 0.3244(2) 0.134(4) Uani 1 1 d G B . H12 H -0.2372 0.3020 0.3609 0.160 Uiso 1 1 calc R . . C13 C -0.16835(11) 0.26545(14) 0.3283(2) 0.152(5) Uani 1 1 d G B . C14 C -0.25483(15) 0.39171(17) 0.2685(2) 0.095(2) Uani 1 1 d G B . C15 C -0.16828(10) 0.22232(17) 0.4075(2) 0.080(3) Uiso 0.50 1 d PG B . C15A C -0.00292(12) 0.30423(19) 0.3522(3) 0.217(14) Uiso 0.50 1 d PG B . C16 C -0.1852(2) 0.3012(3) 0.5128(2) 0.119(6) Uiso 0.50 1 d PGD B . H16A H -0.1800 0.3096 0.5689 0.178 Uiso 0.50 1 calc PR . . H16B H -0.2225 0.2909 0.5000 0.178 Uiso 0.50 1 calc PR . . H16C H -0.1761 0.3354 0.4827 0.178 Uiso 0.50 1 calc PR . . C16A C 0.06356(19) 0.3958(2) 0.3939(6) 0.212(13) Uiso 0.50 1 d PGD B . H16D H 0.0728 0.4335 0.3727 0.318 Uiso 0.50 1 calc PR . . H16E H 0.0946 0.3796 0.4236 0.318 Uiso 0.50 1 calc PR . . H16F H 0.0343 0.4003 0.4286 0.318 Uiso 0.50 1 calc PR . . C17 C 0.15205(17) 0.0000(2) 0.46133(19) 0.064(2) Uani 1 2 d SG . . C18 C 0.15137(14) 0.0000(2) 0.54919(19) 0.069(2) Uani 1 2 d SG . . C19 C 0.15215(13) 0.0472(2) 0.59070(19) 0.166(6) Uani 1 1 d G . 1 H19 H 0.1553 0.0829 0.5642 0.199 Uiso 1 1 calc R . 1 C20 C 0.14867(17) 0.0482(2) 0.66923(18) 0.164(5) Uani 1 1 d G . 1 H20 H 0.1466 0.0842 0.6952 0.197 Uiso 1 1 calc R . 1 C21 C 0.14806(18) 0.0000(3) 0.71084(19) 0.085(3) Uani 1 2 d SG . . C22 C 0.14252(17) -0.0028(4) 0.7973(2) 0.087(4) Uani 0.50 1 d PG . -1 C23 C 0.09272(17) 0.0061(4) 0.8260(2) 0.074(3) Uani 0.50 1 d PG . -1 H23 H 0.0622 0.0093 0.7908 0.089 Uiso 0.50 1 calc PR . -1 C24 C 0.08762(18) 0.0102(5) 0.9063(2) 0.052(4) Uani 0.50 1 d PG . -1 H24 H 0.0536 0.0162 0.9260 0.063 Uiso 0.50 1 calc PR . -1 C25 C 0.13234(19) 0.0053(5) 0.9578(2) 0.095(4) Uani 0.50 1 d PG . -1 C26 C 0.18214(18) -0.0036(5) 0.9291(2) 0.159(10) Uani 0.50 1 d PG . -1 H26 H 0.2127 -0.0068 0.9643 0.191 Uiso 0.50 1 calc PR . -1 C27 C 0.18723(17) -0.0077(5) 0.8488(2) 0.147(9) Uani 0.50 1 d PG . -1 C28 C 0.1294(2) 0.0076(5) 1.0443(2) 0.103(6) Uani 0.50 1 d PG . . C29 C 0.2334(2) -0.0251(5) 0.8142(3) 0.136(7) Uiso 0.50 1 d PG . -1 C31 C 0.1988(5) 0.1206(6) 0.0938(3) 0.222(15) Uiso 0.50 1 d PGD . . H31 H 0.2315 0.1122 0.0715 0.266 Uiso 0.50 1 calc PR . . C32 C 0.1999(7) 0.2006(6) 0.0225(4) 0.43(4) Uiso 0.50 1 d PGD . . H32A H 0.1872 0.2395 0.0093 0.640 Uiso 0.50 1 calc PR . . H32B H 0.1970 0.1763 -0.0245 0.640 Uiso 0.50 1 calc PR . . H32C H 0.2372 0.2024 0.0426 0.640 Uiso 0.50 1 calc PR . . C33 C 0.1254(7) 0.1893(6) 0.1207(4) 0.200(12) Uiso 0.50 1 d PGD . . H33A H 0.1370 0.2048 0.1722 0.300 Uiso 0.50 1 calc PR . . H33B H 0.1045 0.1542 0.1273 0.300 Uiso 0.50 1 calc PR . . H33C H 0.1035 0.2180 0.0916 0.300 Uiso 0.50 1 calc PR . . C34 C 0.3150(6) 0.0000(8) 0.1076(4) 0.49(4) Uiso 1 2 d SGD . . C37 C 0.3249(4) -0.1013(9) 0.8023(4) 0.255(17) Uiso 0.50 1 d PGD . . H37A H 0.3447 -0.1304 0.8340 0.382 Uiso 0.50 1 calc PR . . H37B H 0.3416 -0.0635 0.8112 0.382 Uiso 0.50 1 calc PR . . H37C H 0.3255 -0.1115 0.7467 0.382 Uiso 0.50 1 calc PR . . 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 Zn1 0.0390(4) 0.0495(4) 0.0314(4) 0.000 0.0062(3) 0.000 Zn2 0.0447(3) 0.0487(3) 0.0392(3) -0.0054(2) 0.0072(2) -0.0023(2) Zn3 0.0502(5) 0.0691(6) 0.0606(5) 0.000 0.0230(4) 0.000 S1 0.149(4) 0.166(5) 0.121(4) 0.074(3) 0.069(3) 0.086(3) S1A 0.279(16) 0.199(12) 0.36(2) -0.007(13) 0.092(15) 0.010(11) S2 0.152(6) 0.351(14) 0.131(5) 0.002(7) 0.028(4) 0.044(7) O1 0.0365(19) 0.040(2) 0.0296(19) 0.000 0.0046(15) 0.000 O2 0.056(2) 0.071(2) 0.059(2) -0.0041(18) 0.0038(16) 0.0221(17) O3 0.065(2) 0.085(3) 0.098(3) -0.028(2) -0.018(2) 0.031(2) O4 0.153(6) 0.179(7) 0.314(12) 0.156(8) 0.134(7) 0.123(6) O5 0.080(3) 0.079(3) 0.087(3) 0.012(2) 0.018(2) 0.041(2) O6 0.109(3) 0.085(3) 0.0336(18) 0.0004(18) 0.0116(19) -0.018(2) O7 0.157(9) 0.49(3) 0.035(4) 0.000 0.020(5) 0.000 O8 0.093(4) 0.089(4) 0.029(2) 0.000 0.015(2) 0.000 O9 0.148(11) 0.133(9) 0.116(9) 0.055(8) 0.039(8) 0.020(8) C1 0.061(3) 0.070(3) 0.069(4) 0.002(3) 0.019(3) 0.028(3) C2 0.070(4) 0.096(5) 0.074(4) -0.005(3) 0.009(3) 0.041(3) C3 0.078(4) 0.097(5) 0.110(6) 0.003(4) 0.016(4) 0.041(4) C4 0.077(4) 0.113(6) 0.130(7) 0.015(5) 0.015(4) 0.052(4) C5 0.145(8) 0.182(10) 0.099(6) -0.002(6) 0.012(6) 0.122(8) C6 0.222(13) 0.222(14) 0.219(14) -0.128(12) -0.102(11) 0.178(12) C7 0.177(10) 0.215(12) 0.187(11) -0.130(10) -0.087(9) 0.149(10) C8 0.136(8) 0.163(9) 0.119(7) 0.010(6) 0.036(6) 0.104(7) C9 0.213(12) 0.255(15) 0.168(11) 0.107(11) 0.113(10) 0.183(12) C10 0.204(12) 0.261(15) 0.309(18) 0.202(15) 0.171(13) 0.189(12) C11 0.097(5) 0.113(6) 0.101(5) 0.035(4) 0.032(4) 0.065(5) C12 0.095(6) 0.113(7) 0.197(11) 0.042(7) 0.044(6) 0.060(5) C13 0.105(7) 0.138(8) 0.215(13) 0.026(8) 0.022(7) 0.075(6) C14 0.090(5) 0.086(5) 0.112(6) 0.022(4) 0.029(4) 0.046(4) C17 0.051(4) 0.111(7) 0.030(3) 0.000 0.003(3) 0.000 C18 0.078(5) 0.100(6) 0.032(3) 0.000 0.018(3) 0.000 C19 0.347(17) 0.122(7) 0.031(3) -0.007(4) 0.020(6) -0.076(9) C20 0.331(18) 0.127(7) 0.036(4) -0.017(4) 0.032(6) -0.006(9) C21 0.083(6) 0.139(9) 0.033(4) 0.000 0.009(4) 0.000 C22 0.082(6) 0.148(11) 0.031(4) -0.01(2) 0.009(4) 0.02(2) C23 0.079(6) 0.105(9) 0.039(4) -0.026(9) 0.001(4) 0.004(11) C24 0.094(6) 0.029(11) 0.035(4) -0.003(3) 0.008(4) -0.009(4) C25 0.101(7) 0.158(13) 0.027(4) 0.012(12) 0.007(4) -0.044(16) C26 0.076(7) 0.35(3) 0.046(6) -0.06(2) -0.003(5) 0.05(3) C27 0.088(8) 0.30(3) 0.058(6) -0.01(2) 0.014(6) 0.05(2) C28 0.139(10) 0.149(15) 0.021(4) -0.017(8) -0.008(5) -0.071(14) _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 Zn1 O1 1.930(4) . ? Zn1 O8 1.933(5) 1_554 ? Zn1 O2 1.962(3) 6 ? Zn1 O2 1.962(3) . ? Zn1 Zn2 3.1411(7) . ? Zn1 Zn2 3.1411(7) 6 ? Zn2 O1 1.915(2) . ? Zn2 O5 1.928(4) 8 ? Zn2 O6 1.951(4) . ? Zn2 O3 1.951(4) . ? Zn2 Zn2 3.1085(10) 6 ? Zn3 O7 1.846(9) 1_554 ? Zn3 O4 1.915(5) 8 ? Zn3 O4 1.915(5) 3_545 ? Zn3 O1 2.000(4) . ? Zn3 O10 2.013(16) . ? Zn3 O9 2.252(10) 6 ? Zn3 O9 2.252(10) . ? S1 C16 1.468(5) . ? S1 O11 1.520(13) . ? S1 O12 1.602(14) . ? S1 C15 1.660(8) . ? S1A O11A 1.579(18) . ? S1A O12A 1.586(17) . ? S1A C16A 1.654(14) . ? S1A C15A 1.744(15) . ? S2 O14 1.561(16) . ? S2 O13 1.588(17) . ? S2 C37 1.663(11) . ? S2 C29 1.872(16) . ? O1 Zn2 1.915(2) 6 ? O2 C1 1.267(7) . ? O3 C1 1.248(7) . ? O4 C14 1.256(7) . ? O4 Zn3 1.915(5) 3_455 ? O5 C14 1.260(6) . ? O5 Zn2 1.928(4) 8_455 ? O6 C17 1.262(7) . ? O7 C28 1.302(13) . ? O7 C28 1.302(12) 6 ? O7 Zn3 1.846(9) 1_556 ? O8 C28 1.276(8) . ? O8 C28 1.276(8) 6 ? O8 Zn1 1.933(5) 1_556 ? O9 C31 1.320(14) . ? O10 C34 1.218(3) . ? N1 C33 1.35(3) . ? N1 C32 1.42(3) . ? N1 C31 1.52(4) . ? C1 C2 1.491(6) . ? C2 C3 1.3900 . ? C2 C7 1.3900 . ? C3 C4 1.3900 . ? C3 H3 0.9500 . ? C4 C5 1.3900 . ? C4 H4 0.9500 . ? C5 C6 1.3900 . ? C5 C8 1.500(4) . ? C6 C7 1.3900 . ? C6 C15A 1.895(8) . ? C7 H7 0.9500 . ? C8 C9 1.3900 . ? C8 C13 1.3900 . ? C9 C10 1.3900 . ? C9 H9 0.9500 . ? C10 C11 1.3900 . ? C10 H10 0.9500 . ? C11 C12 1.3900 . ? C11 C14 1.4776 . ? C12 C13 1.3900 . ? C12 H12 0.9500 . ? C13 C15 1.6845 . ? C16 H16A 0.9800 . ? C16 H16B 0.9800 . ? C16 H16C 0.9800 . ? C16A H16D 0.9800 . ? C16A H16E 0.9800 . ? C16A H16F 0.9800 . ? C17 O6 1.263(7) 6 ? C17 C18 1.5037 . ? C18 C19 1.305(8) 6 ? C18 C19 1.3048 . ? C19 C20 1.3513 . ? C19 H19 0.9500 . ? C20 C21 1.3253 . ? C20 H20 0.9500 . ? C21 C20 1.325(9) 6 ? C21 C22 1.495(5) . ? C21 C22 1.495(5) 6 ? C22 C23 1.3900 . ? C22 C27 1.3900 . ? C23 C24 1.3900 . ? C23 H23 0.9500 . ? C24 C25 1.3900 . ? C24 H24 0.9500 . ? C25 C26 1.3900 . ? C25 C28 1.4854 . ? C25 C28 1.515(5) 6 ? C26 C27 1.3900 . ? C26 H26 0.9500 . ? C27 C29 1.3953 . ? C28 C28 0.35(2) 6 ? C28 C25 1.515(4) 6 ? C31 H31 0.9500 . ? C32 H32A 0.9800 . ? C32 H32B 0.9800 . ? C32 H32C 0.9800 . ? C33 H33A 0.9800 . ? C33 H33B 0.9800 . ? C33 H33C 0.9800 . ? C37 H37A 0.9800 . ? C37 H37B 0.9800 . ? C37 H37C 0.9800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O1 Zn1 O8 119.9(2) . 1_554 ? O1 Zn1 O2 111.45(13) . 6 ? O8 Zn1 O2 103.72(15) 1_554 6 ? O1 Zn1 O2 111.45(13) . . ? O8 Zn1 O2 103.72(15) 1_554 . ? O2 Zn1 O2 105.4(2) 6 . ? O1 Zn1 Zn2 35.08(6) . . ? O8 Zn1 Zn2 131.37(14) 1_554 . ? O2 Zn1 Zn2 123.48(11) 6 . ? O2 Zn1 Zn2 76.37(11) . . ? O1 Zn1 Zn2 35.08(6) . 6 ? O8 Zn1 Zn2 131.37(14) 1_554 6 ? O2 Zn1 Zn2 76.37(11) 6 6 ? O2 Zn1 Zn2 123.48(11) . 6 ? Zn2 Zn1 Zn2 59.31(2) . 6 ? O1 Zn2 O5 117.84(18) . 8 ? O1 Zn2 O6 113.09(16) . . ? O5 Zn2 O6 101.14(19) 8 . ? O1 Zn2 O3 112.59(17) . . ? O5 Zn2 O3 105.2(2) 8 . ? O6 Zn2 O3 105.6(2) . . ? O1 Zn2 Zn2 35.76(9) . 6 ? O5 Zn2 Zn2 128.59(15) 8 6 ? O6 Zn2 Zn2 77.33(13) . 6 ? O3 Zn2 Zn2 124.94(14) . 6 ? O1 Zn2 Zn1 35.38(11) . . ? O5 Zn2 Zn1 130.82(14) 8 . ? O6 Zn2 Zn1 126.01(13) . . ? O3 Zn2 Zn1 77.20(13) . . ? Zn2 Zn2 Zn1 60.343(11) 6 . ? O7 Zn3 O4 119.5(4) 1_554 8 ? O7 Zn3 O4 119.5(4) 1_554 3_545 ? O4 Zn3 O4 108.9(8) 8 3_545 ? O7 Zn3 O1 101.4(4) 1_554 . ? O4 Zn3 O1 101.8(2) 8 . ? O4 Zn3 O1 101.8(2) 3_545 . ? O7 Zn3 O10 74.3(6) 1_554 . ? O4 Zn3 O10 80.6(3) 8 . ? O4 Zn3 O10 80.6(3) 3_545 . ? O1 Zn3 O10 175.7(5) . . ? O7 Zn3 O9 63.6(4) 1_554 6 ? O4 Zn3 O9 171.9(5) 8 6 ? O4 Zn3 O9 64.3(5) 3_545 6 ? O1 Zn3 O9 84.3(3) . 6 ? O10 Zn3 O9 93.6(4) . 6 ? O7 Zn3 O9 63.6(4) 1_554 . ? O4 Zn3 O9 64.3(5) 8 . ? O4 Zn3 O9 171.9(5) 3_545 . ? O1 Zn3 O9 84.3(3) . . ? O10 Zn3 O9 93.6(4) . . ? O9 Zn3 O9 122.1(8) 6 . ? C16 S1 O11 109.8(9) . . ? C16 S1 O12 108.8(7) . . ? O11 S1 O12 104.3(9) . . ? C16 S1 C15 113.8(4) . . ? O11 S1 C15 111.1(7) . . ? O12 S1 C15 108.6(8) . . ? O11A S1A O12A 111(2) . . ? O11A S1A C16A 111.4(16) . . ? O12A S1A C16A 111.6(16) . . ? O11A S1A C15A 108.3(15) . . ? O12A S1A C15A 105.2(17) . . ? C16A S1A C15A 109.2(9) . . ? O14 S2 O13 109.9(17) . . ? O14 S2 C37 107.0(13) . . ? O13 S2 C37 101.2(11) . . ? O14 S2 C29 114.8(11) . . ? O13 S2 C29 111.6(12) . . ? C37 S2 C29 111.4(10) . . ? Zn2 O1 Zn2 108.48(18) . 6 ? Zn2 O1 Zn1 109.54(13) . . ? Zn2 O1 Zn1 109.54(13) 6 . ? Zn2 O1 Zn3 110.06(13) . . ? Zn2 O1 Zn3 110.06(13) 6 . ? Zn1 O1 Zn3 109.16(17) . . ? C1 O2 Zn1 129.7(3) . . ? C1 O3 Zn2 129.5(4) . . ? C14 O4 Zn3 143.6(5) . 3_455 ? C14 O5 Zn2 122.2(3) . 8_455 ? C17 O6 Zn2 129.5(3) . . ? C28 O7 C28 15.6(11) . 6 ? C28 O7 Zn3 145.0(7) . 1_556 ? C28 O7 Zn3 145.0(7) 6 1_556 ? C28 O8 C28 15.9(11) . 6 ? C28 O8 Zn1 117.7(4) . 1_556 ? C28 O8 Zn1 117.7(4) 6 1_556 ? C31 O9 Zn3 124.8(6) . . ? C34 O10 Zn3 142.2(14) . . ? C33 N1 C32 140(3) . . ? C33 N1 C31 121(3) . . ? C32 N1 C31 98(2) . . ? O3 C1 O2 126.7(5) . . ? O3 C1 C2 117.0(5) . . ? O2 C1 C2 116.2(5) . . ? C3 C2 C7 120.0 . . ? C3 C2 C1 120.6(4) . . ? C7 C2 C1 119.4(4) . . ? C2 C3 C4 120.0 . . ? C2 C3 H3 120.0 . . ? C4 C3 H3 120.0 . . ? C3 C4 C5 120.0 . . ? C3 C4 H4 120.0 . . ? C5 C4 H4 120.0 . . ? C6 C5 C4 120.0 . . ? C6 C5 C8 123.1(4) . . ? C4 C5 C8 116.8(4) . . ? C5 C6 C7 120.0 . . ? C5 C6 C15A 126.6(3) . . ? C7 C6 C15A 105.7(3) . . ? C6 C7 C2 120.0 . . ? C6 C7 H7 120.0 . . ? C2 C7 H7 120.0 . . ? C9 C8 C13 120.0 . . ? C9 C8 C5 114.5(4) . . ? C13 C8 C5 125.5(4) . . ? C8 C9 C10 120.0 . . ? C8 C9 H9 120.0 . . ? C10 C9 H9 120.0 . . ? C11 C10 C9 120.0 . . ? C11 C10 H10 120.0 . . ? C9 C10 H10 120.0 . . ? C12 C11 C10 120.0 . . ? C12 C11 C14 119.4 . . ? C10 C11 C14 120.3 . . ? C11 C12 C13 120.0 . . ? C11 C12 H12 120.0 . . ? C13 C12 H12 120.0 . . ? C12 C13 C8 120.0 . . ? C12 C13 C15 112.8 . . ? C8 C13 C15 126.8 . . ? O4 C14 O5 124.0(4) . . ? O4 C14 C11 118.9(3) . . ? O5 C14 C11 116.3(2) . . ? S1 C15 C13 116.1(2) . . ? S1A C15A C6 138.5(6) . . ? S1 C16 H16A 109.5 . . ? S1 C16 H16B 109.5 . . ? H16A C16 H16B 109.5 . . ? S1 C16 H16C 109.5 . . ? H16A C16 H16C 109.5 . . ? H16B C16 H16C 109.5 . . ? S1A C16A H16D 109.5 . . ? S1A C16A H16E 109.5 . . ? H16D C16A H16E 109.5 . . ? S1A C16A H16F 109.5 . . ? H16D C16A H16F 109.5 . . ? H16E C16A H16F 109.5 . . ? O6 C17 O6 126.3(4) . 6 ? O6 C17 C18 116.8(3) . . ? O6 C17 C18 116.8(3) 6 . ? C19 C18 C19 114.2(2) 6 . ? C19 C18 C17 122.9(2) 6 . ? C19 C18 C17 122.9 . . ? C18 C19 C20 123.7 . . ? C18 C19 H19 118.2 . . ? C20 C19 H19 118.2 . . ? C21 C20 C19 121.6 . . ? C21 C20 H20 119.2 . . ? C19 C20 H20 119.2 . . ? C20 C21 C20 114.9(3) 6 . ? C20 C21 C22 119.9(6) 6 . ? C20 C21 C22 125.0(4) . . ? C20 C21 C22 125.0(7) 6 6 ? C20 C21 C22 119.9(5) . 6 ? C22 C21 C22 5.1(7) . 6 ? C23 C22 C27 120.0 . . ? C23 C22 C21 119.0(2) . . ? C27 C22 C21 120.6(2) . . ? C22 C23 C24 120.0 . . ? C22 C23 H23 120.0 . . ? C24 C23 H23 120.0 . . ? C23 C24 C25 120.0 . . ? C23 C24 H24 120.0 . . ? C25 C24 H24 120.0 . . ? C26 C25 C24 120.0 . . ? C26 C25 C28 117.3 . . ? C24 C25 C28 122.7 . . ? C26 C25 C28 114.5(2) . 6 ? C24 C25 C28 123.2 . 6 ? C28 C25 C28 13.5(9) . 6 ? C25 C26 C27 120.0 . . ? C25 C26 H26 120.0 . . ? C27 C26 H26 120.0 . . ? C26 C27 C22 120.0 . . ? C26 C27 C29 124.7 . . ? C22 C27 C29 114.6 . . ? C28 C28 O8 82.0(6) 6 . ? C28 C28 O7 82.2(6) 6 . ? O8 C28 O7 123.7(6) . . ? C28 C28 C25 88.0 6 . ? O8 C28 C25 117.7(3) . . ? O7 C28 C25 115.3(4) . . ? C28 C28 C25 78.5(8) 6 6 ? O8 C28 C25 115.6(5) . 6 ? O7 C28 C25 113.4(5) . 6 ? C25 C28 C25 9.4(8) . 6 ? C27 C29 S2 122.7(4) . . ? O9 C31 N1 112.3(14) . . ? O9 C31 H31 123.8 . . ? N1 C31 H31 123.8 . . ? N1 C32 H32A 109.5 . . ? N1 C32 H32B 109.5 . . ? H32A C32 H32B 109.5 . . ? N1 C32 H32C 109.5 . . ? H32A C32 H32C 109.5 . . ? H32B C32 H32C 109.5 . . ? N1 C33 H33A 109.5 . . ? N1 C33 H33B 109.5 . . ? H33A C33 H33B 109.5 . . ? N1 C33 H33C 109.5 . . ? H33A C33 H33C 109.5 . . ? H33B C33 H33C 109.5 . . ? S2 C37 H37A 109.5 . . ? S2 C37 H37B 109.5 . . ? H37A C37 H37B 109.5 . . ? S2 C37 H37C 109.5 . . ? H37A C37 H37C 109.5 . . ? H37B C37 H37C 109.5 . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 1.106 _refine_diff_density_min -0.881 _refine_diff_density_rms 0.141 # SQUEEZE RESULTS 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 0.500 0.000 0.003 1427 170 ' ' 2 0.000 0.500 -0.008 1427 170 ' ' 3 0.691 0.238 0.289 12 2 ' ' 4 0.191 0.262 0.289 12 2 ' ' 5 0.191 0.738 0.289 12 2 ' ' 6 0.691 0.762 0.289 12 2 ' ' 7 1.000 0.000 0.500 249 39 ' ' 8 0.500 0.500 0.500 249 39 ' ' 9 0.309 0.238 0.711 12 2 ' ' 10 0.809 0.262 0.711 12 2 ' ' 11 0.809 0.738 0.711 12 2 ' ' 12 0.309 0.762 0.711 12 2 ' '