# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2011 data_publication_text _journal_name_full Chem.Commun. _journal_coden_cambridge 0182 #TrackingRef 'Zn(BDPEt)_Chem Comm_George Shimizu_squeezed.cif' #============================================================================ # 1. SUBMISSION DETAILS _publ_contact_author # Name and address of author for correspondence ; 'George K. H. Shimizu' Department of Chemistry University of Calgary Calgary, T2N1N4 (Canada) Fax: (+1) 403-289-9488 E-mail: gshimizu@ucalgary.ca Homepage: http://www.chem.ucalgary.ca/groups/gshimizu/ ; _publ_contact_author_phone '(001) 403-220-5347' _publ_contact_author_fax '(001) 403-289-9488' _publ_contact_author_email gshimizu@ucalgary.ca _publ_requested_coeditor_name ? _publ_contact_letter ; Please consider this CIF submission for publication in Chem. Commun. ; #============================================================================ # 2. PROCESSING SUMMARY (IUCr Office Use Only) _journal_date_recd_electronic ? _journal_date_to_coeditor ? _journal_date_from_coeditor ? _journal_date_accepted ? _journal_date_printers_first ? _journal_date_printers_final ? _journal_date_proofs_out ? _journal_date_proofs_in ? _journal_coeditor_name ? _journal_coeditor_code ? _journal_coeditor_notes ? _journal_techeditor_code ? _journal_techeditor_notes ? _journal_coden_ASTM ? _journal_year ? _journal_volume ? _journal_issue ? _journal_page_first ? _journal_page_last ? _journal_suppl_publ_number ? _journal_suppl_publ_pages ? #============================================================================ # 3. TITLE AND AUTHOR LIST _publ_section_title ; A permanently porous van der Waals solid by using phosphonate monoester linkers in a metal organic framework. ; # The loop structure below should contain the names and addresses of all # authors, in the required order of publication. Repeat as necessary. loop_ _publ_author_name _publ_author_address 'Simon S. Iremonger' ; Department of Chemistry University of Calgary Calgary, T2N 1N4(Canada) ; 'Junmei Liang' ; Department of Chemistry University of Calgary Calgary, T2N 1N4(Canada) ; 'Ramanathan Vaidhyanathan' ; Department of Chemistry University of Calgary Calgary, T2N 1N4(Canada) 'George K. H. Shimizu' Department of Chemistry University of Calgary Calgary, T2N1N4 (Canada) Fax: (+1) 403-289-9488 E-mail: gshimizu@ucalgary.ca ; _publ_contact_author_name 'George K. H. Shimizu' #============================================================================ data_squeezed _database_code_depnum_ccdc_archive 'CCDC 798055' #TrackingRef 'Zn(BDPEt)_Chem Comm_George Shimizu_squeezed.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; Zinc-1,4-benzenediphosphonatodiethylester ; _chemical_name_common Zinc-1,4-benzenediphosphonatodiethylester _chemical_melting_point ? _chemical_formula_moiety 'C11 H17 O6 P2 Zn' _chemical_formula_sum 'C11 H16 O6 P2 Zn' _chemical_formula_weight 371.55 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' P P 0.1023 0.0942 '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 Orthorhombic _symmetry_space_group_name_H-M Ibam loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'x, -y, -z+1/2' '-x, y, -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' '-x+1/2, y+1/2, -z+1' '-x, -y, -z' 'x, y, -z' '-x, y, z-1/2' 'x, -y, 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' 'x+1/2, -y+1/2, z' _cell_length_a 15.729(3) _cell_length_b 23.170(5) _cell_length_c 9.7372(19) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3548.6(12) _cell_formula_units_Z 8 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 1254 _cell_measurement_theta_min 2.6 _cell_measurement_theta_max 24.7 _exptl_crystal_description rod-shaped _exptl_crystal_colour colorless _exptl_crystal_size_max 0.09 _exptl_crystal_size_mid 0.05 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.391 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1520 _exptl_absorpt_coefficient_mu 1.581 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.867 _exptl_absorpt_correction_T_max 0.954 _exptl_absorpt_process_details 'SADABS;Universitat Gottingen,1997' _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(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 'Nonius Kappa with APEX II CCD detector' _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean ? _diffrn_reflns_number 2878 _diffrn_reflns_av_R_equivalents 0.0486 _diffrn_reflns_av_sigmaI/netI 0.0456 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -27 _diffrn_reflns_limit_k_max 26 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.59 _diffrn_reflns_theta_max 24.71 _reflns_number_total 1612 _reflns_number_gt 1241 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Collect (Bruker AXS BV, 1997-2004)' _computing_cell_refinement 'HKL Scalepack (Otwinowski & Minor 1997)' _computing_data_reduction 'HKL Denzo and Scalepack (1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'HKL Denzo and Scalepack (1997)' _computing_publication_material 'Diamond 3.0' _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 solvent water molecules were disordered and hence could not be located. The hydrogens have been fixed and since one of the ethyl groups on the phosphonate is disordered the hydrogens on these did not converge completely during refinement. ; 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 1 0.000 0.500 -0.022 391.0 1.2 2 0.500 1.000 -0.023 391.0 1.2 _platon_squeeze_details ; A SQUEEZE analysis on compound 1, indicated an electron count per unit cell of 2, suggesting that there is no residual solvent in the pore. However the fact that the analytical measurements(TGA) shows solvent loss seems to suggest that the electron densities in the channels are not visible to the x-ray. This could mean that the electron densities in the voids are highly diffused. ; _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^)+(0.0743P)^2^+54.7577P] 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 1612 _refine_ls_number_parameters 107 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0830 _refine_ls_R_factor_gt 0.0609 _refine_ls_wR_factor_ref 0.1694 _refine_ls_wR_factor_gt 0.1556 _refine_ls_goodness_of_fit_ref 0.978 _refine_ls_restrained_S_all 0.979 _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 C1 C 0.7950(5) 0.1453(4) 0.0000 0.0303(19) Uani 1 2 d S . . C2 C 0.7610(4) 0.1651(3) -0.1265(8) 0.0469(18) Uani 1 1 d . . . H2 H 0.7838 0.1516 -0.2109 0.056 Uiso 1 1 calc R . . C3 C 0.6940(5) 0.2043(3) -0.1266(7) 0.0511(19) Uani 1 1 d . . . H3 H 0.6712 0.2181 -0.2107 0.061 Uiso 1 1 calc R . . C4 C 0.6602(5) 0.2233(4) 0.0000 0.032(2) Uani 1 2 d S . . C12 C 0.8122(9) -0.0660(5) 0.0000 0.095(6) Uani 1 2 d S . . H12A H 0.8412 -0.1032 -0.0086 0.143 Uiso 0.50 1 calc PR . . H12B H 0.7732 -0.0608 -0.0775 0.143 Uiso 0.50 1 calc PR . . H12C H 0.7800 -0.0650 0.0861 0.143 Uiso 0.50 1 calc PR . . C11 C 0.8743(7) -0.0202(4) 0.0000 0.066(4) Uani 1 2 d S . . H11A H 0.9108 -0.0230 -0.0825 0.079 Uiso 0.50 1 calc PR . . H11B H 0.9108 -0.0230 0.0825 0.079 Uiso 0.50 1 calc PR . . C21 C 0.4598(9) 0.1950(8) -0.0675(15) 0.164(7) Uani 1 1 d D . . H21A H 0.5034 0.1644 -0.0759 0.197 Uiso 1 1 calc R . . H21B H 0.4459 0.2085 -0.1613 0.197 Uiso 1 1 calc R . . C22 C 0.3772(8) 0.1685(7) 0.0000 0.089(5) Uani 1 2 d SD . . H22A H 0.3936 0.1408 0.0714 0.133 Uiso 0.50 1 calc PR . . H22B H 0.3436 0.1487 -0.0705 0.133 Uiso 0.50 1 calc PR . . H22C H 0.3432 0.1995 0.0410 0.133 Uiso 0.50 1 calc PR . . O11 O 0.9290(3) 0.09724(18) 0.1361(5) 0.0393(11) Uani 1 1 d . . . O12 O 0.8284(4) 0.0340(3) 0.0000 0.0390(16) Uani 1 2 d S . . O21 O 0.5732(3) 0.3050(2) 0.1357(5) 0.0471(13) Uani 1 1 d . . . O22 O 0.4905(6) 0.2364(4) 0.0000 0.115(6) Uani 1 2 d S . . P1 P 0.87918(14) 0.09268(10) 0.0000 0.0290(6) Uani 1 2 d S . . P2 P 0.57081(14) 0.27224(10) 0.0000 0.0319(6) Uani 1 2 d S . . Zn Zn 1.0000 0.14619(4) 0.2500 0.0282(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 C1 0.030(4) 0.028(5) 0.033(5) 0.000 0.000 0.010(4) C2 0.051(4) 0.051(4) 0.039(4) 0.000(3) 0.003(3) 0.026(4) C3 0.052(4) 0.070(5) 0.032(4) -0.002(4) -0.003(3) 0.030(4) C4 0.027(4) 0.029(5) 0.040(5) 0.000 0.000 0.003(4) C12 0.064(8) 0.037(7) 0.185(18) 0.000 0.000 0.002(6) C11 0.051(6) 0.023(5) 0.123(11) 0.000 0.000 -0.001(5) C21 0.147(14) 0.26(2) 0.091(10) 0.019(13) 0.011(10) 0.024(15) C22 0.065(8) 0.114(13) 0.086(10) 0.000 0.000 -0.058(9) O11 0.036(2) 0.033(2) 0.049(3) -0.001(2) -0.006(2) 0.0020(19) O12 0.031(3) 0.021(3) 0.064(4) 0.000 0.000 -0.005(3) O21 0.054(3) 0.050(3) 0.037(3) -0.008(2) 0.003(2) 0.026(2) O22 0.044(5) 0.036(5) 0.265(19) 0.000 0.000 -0.015(4) P1 0.0233(11) 0.0255(12) 0.0383(13) 0.000 0.000 0.0013(9) P2 0.0288(11) 0.0297(12) 0.0371(13) 0.000 0.000 0.0038(10) Zn 0.0275(5) 0.0274(5) 0.0297(5) 0.000 0.0026(4) 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 C1 C2 1.419(8) . ? C1 C2 1.419(8) 10 ? C1 P1 1.800(8) . ? C2 C3 1.391(9) . ? C2 H2 0.9500 . ? C3 C4 1.413(8) . ? C3 H3 0.9500 . ? C4 C3 1.413(8) 10 ? C4 P2 1.806(8) . ? C12 C11 1.442(15) . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? C11 O12 1.449(12) . ? C11 H11A 0.9900 . ? C11 H11B 0.9900 . ? C21 O22 1.259(17) . ? C21 C22 1.580(13) . ? C21 H21A 0.9900 . ? C21 H21B 0.9900 . ? C22 H22A 0.9800 . ? C22 H22B 0.9800 . ? C22 H22C 0.9800 . ? O11 P1 1.543(5) . ? O11 Zn 1.940(4) . ? O12 P1 1.576(6) . ? O21 P2 1.524(5) . ? O21 Zn 1.961(4) 13_655 ? O22 C21 1.259(17) 10 ? O22 P2 1.512(9) . ? P1 O11 1.543(5) 10 ? P2 O21 1.524(5) 10 ? Zn O11 1.940(4) 4_755 ? Zn O21 1.961(4) 16 ? Zn O21 1.961(4) 13_655 ? 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 C2 C1 C2 120.5(8) . 10 ? C2 C1 P1 119.7(4) . . ? C2 C1 P1 119.7(4) 10 . ? C3 C2 C1 119.8(7) . . ? C3 C2 H2 120.1 . . ? C1 C2 H2 120.1 . . ? C2 C3 C4 119.2(7) . . ? C2 C3 H3 120.4 . . ? C4 C3 H3 120.4 . . ? C3 C4 C3 121.5(8) 10 . ? C3 C4 P2 119.3(4) 10 . ? C3 C4 P2 119.3(4) . . ? C11 C12 H12A 109.5 . . ? C11 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C11 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C12 C11 O12 107.5(9) . . ? C12 C11 H11A 110.2 . . ? O12 C11 H11A 110.2 . . ? C12 C11 H11B 110.2 . . ? O12 C11 H11B 110.2 . . ? H11A C11 H11B 108.5 . . ? O22 C21 C22 113.2(12) . . ? O22 C21 H21A 108.9 . . ? C22 C21 H21A 108.9 . . ? O22 C21 H21B 108.9 . . ? C22 C21 H21B 108.9 . . ? H21A C21 H21B 107.8 . . ? C21 C22 H22A 109.5 . . ? C21 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C21 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? P1 O11 Zn 145.4(3) . . ? C11 O12 P1 119.7(6) . . ? P2 O21 Zn 139.9(3) . 13_655 ? C21 O22 C21 62.9(13) . 10 ? C21 O22 P2 137.6(8) . . ? C21 O22 P2 137.6(8) 10 . ? O11 P1 O11 118.4(3) . 10 ? O11 P1 O12 108.4(2) . . ? O11 P1 O12 108.4(2) 10 . ? O11 P1 C1 109.1(2) . . ? O11 P1 C1 109.1(2) 10 . ? O12 P1 C1 102.2(4) . . ? O22 P2 O21 107.1(3) . . ? O22 P2 O21 107.1(3) . 10 ? O21 P2 O21 120.2(4) . 10 ? O22 P2 C4 107.9(5) . . ? O21 P2 C4 107.0(2) . . ? O21 P2 C4 107.0(2) 10 . ? O11 Zn O11 108.5(3) . 4_755 ? O11 Zn O21 110.5(2) . 16 ? O11 Zn O21 108.87(19) 4_755 16 ? O11 Zn O21 108.87(19) . 13_655 ? O11 Zn O21 110.5(2) 4_755 13_655 ? O21 Zn O21 109.5(3) 16 13_655 ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 24.71 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.450 _refine_diff_density_min -0.701 _refine_diff_density_rms 0.111