# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Seth Cohen' _publ_contact_author_email SCOHEN@UCSD.EDU _publ_section_title ; Covalent Modification of a Metal-Organic Framework with Isocyanates: Probing Substrate Scope and Reactivity ; loop_ _publ_author_name 'Seth Cohen' 'Emily Dugan' 'Annette Medina' 'Marilyn Okamura' 'Zhenqiang Wang.' # Attachment 'ecd227_0m.cif' data_ecd227_0m _database_code_depnum_ccdc_archive 'CCDC 684721' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common '27% IRMOF-3 C.h.urea' _chemical_melting_point ? _chemical_formula_moiety ; 0.27 C45 H48 O16 N6 Zn4, 0.73 C24 H15 O13 N3 Zn4, 5 C H Cl3 ; _chemical_formula_sum 'C34.63 H28.88 Cl15 N3.75 O13.75 Zn4' _chemical_formula_weight 1510.72 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting cubic _symmetry_space_group_name_H-M 'F m -3 m' 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' 'y, x, -z' '-y, -x, -z' 'y, -x, z' '-y, x, z' 'x, z, -y' '-x, z, y' '-x, -z, -y' 'x, -z, y' 'z, y, -x' 'z, -y, x' '-z, y, x' '-z, -y, -x' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' '-x, y+1/2, -z+1/2' 'x, -y+1/2, -z+1/2' 'z, x+1/2, y+1/2' 'z, -x+1/2, -y+1/2' '-z, -x+1/2, y+1/2' '-z, x+1/2, -y+1/2' 'y, z+1/2, x+1/2' '-y, z+1/2, -x+1/2' 'y, -z+1/2, -x+1/2' '-y, -z+1/2, x+1/2' 'y, x+1/2, -z+1/2' '-y, -x+1/2, -z+1/2' 'y, -x+1/2, z+1/2' '-y, x+1/2, z+1/2' 'x, z+1/2, -y+1/2' '-x, z+1/2, y+1/2' '-x, -z+1/2, -y+1/2' 'x, -z+1/2, y+1/2' 'z, y+1/2, -x+1/2' 'z, -y+1/2, x+1/2' '-z, y+1/2, x+1/2' '-z, -y+1/2, -x+1/2' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' '-x+1/2, y, -z+1/2' 'x+1/2, -y, -z+1/2' 'z+1/2, x, y+1/2' 'z+1/2, -x, -y+1/2' '-z+1/2, -x, y+1/2' '-z+1/2, x, -y+1/2' 'y+1/2, z, x+1/2' '-y+1/2, z, -x+1/2' 'y+1/2, -z, -x+1/2' '-y+1/2, -z, x+1/2' 'y+1/2, x, -z+1/2' '-y+1/2, -x, -z+1/2' 'y+1/2, -x, z+1/2' '-y+1/2, x, z+1/2' 'x+1/2, z, -y+1/2' '-x+1/2, z, y+1/2' '-x+1/2, -z, -y+1/2' 'x+1/2, -z, y+1/2' 'z+1/2, y, -x+1/2' 'z+1/2, -y, x+1/2' '-z+1/2, y, x+1/2' '-z+1/2, -y, -x+1/2' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' 'z+1/2, x+1/2, y' 'z+1/2, -x+1/2, -y' '-z+1/2, -x+1/2, y' '-z+1/2, x+1/2, -y' 'y+1/2, z+1/2, x' '-y+1/2, z+1/2, -x' 'y+1/2, -z+1/2, -x' '-y+1/2, -z+1/2, x' 'y+1/2, x+1/2, -z' '-y+1/2, -x+1/2, -z' 'y+1/2, -x+1/2, z' '-y+1/2, x+1/2, z' 'x+1/2, z+1/2, -y' '-x+1/2, z+1/2, y' '-x+1/2, -z+1/2, -y' 'x+1/2, -z+1/2, y' 'z+1/2, y+1/2, -x' 'z+1/2, -y+1/2, x' '-z+1/2, y+1/2, x' '-z+1/2, -y+1/2, -x' '-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' '-y, -x, z' 'y, x, z' '-y, x, -z' 'y, -x, -z' '-x, -z, y' 'x, -z, -y' 'x, z, y' '-x, z, -y' '-z, -y, x' '-z, y, -x' 'z, -y, -x' 'z, y, x' '-x, -y+1/2, -z+1/2' 'x, y+1/2, -z+1/2' 'x, -y+1/2, z+1/2' '-x, y+1/2, z+1/2' '-z, -x+1/2, -y+1/2' '-z, x+1/2, y+1/2' 'z, x+1/2, -y+1/2' 'z, -x+1/2, y+1/2' '-y, -z+1/2, -x+1/2' 'y, -z+1/2, x+1/2' '-y, z+1/2, x+1/2' 'y, z+1/2, -x+1/2' '-y, -x+1/2, z+1/2' 'y, x+1/2, z+1/2' '-y, x+1/2, -z+1/2' 'y, -x+1/2, -z+1/2' '-x, -z+1/2, y+1/2' 'x, -z+1/2, -y+1/2' 'x, z+1/2, y+1/2' '-x, z+1/2, -y+1/2' '-z, -y+1/2, x+1/2' '-z, y+1/2, -x+1/2' 'z, -y+1/2, -x+1/2' 'z, y+1/2, x+1/2' '-x+1/2, -y, -z+1/2' 'x+1/2, y, -z+1/2' 'x+1/2, -y, z+1/2' '-x+1/2, y, z+1/2' '-z+1/2, -x, -y+1/2' '-z+1/2, x, y+1/2' 'z+1/2, x, -y+1/2' 'z+1/2, -x, y+1/2' '-y+1/2, -z, -x+1/2' 'y+1/2, -z, x+1/2' '-y+1/2, z, x+1/2' 'y+1/2, z, -x+1/2' '-y+1/2, -x, z+1/2' 'y+1/2, x, z+1/2' '-y+1/2, x, -z+1/2' 'y+1/2, -x, -z+1/2' '-x+1/2, -z, y+1/2' 'x+1/2, -z, -y+1/2' 'x+1/2, z, y+1/2' '-x+1/2, z, -y+1/2' '-z+1/2, -y, x+1/2' '-z+1/2, y, -x+1/2' 'z+1/2, -y, -x+1/2' 'z+1/2, y, x+1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, z' '-x+1/2, y+1/2, z' '-z+1/2, -x+1/2, -y' '-z+1/2, x+1/2, y' 'z+1/2, x+1/2, -y' 'z+1/2, -x+1/2, y' '-y+1/2, -z+1/2, -x' 'y+1/2, -z+1/2, x' '-y+1/2, z+1/2, x' 'y+1/2, z+1/2, -x' '-y+1/2, -x+1/2, z' 'y+1/2, x+1/2, z' '-y+1/2, x+1/2, -z' 'y+1/2, -x+1/2, -z' '-x+1/2, -z+1/2, y' 'x+1/2, -z+1/2, -y' 'x+1/2, z+1/2, y' '-x+1/2, z+1/2, -y' '-z+1/2, -y+1/2, x' '-z+1/2, y+1/2, -x' 'z+1/2, -y+1/2, -x' 'z+1/2, y+1/2, x' _cell_length_a 25.7262(10) _cell_length_b 25.7262(10) _cell_length_c 25.7262(10) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 17026.6(11) _cell_formula_units_Z 8 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 25877 _cell_measurement_theta_min 2.24 _cell_measurement_theta_max 26.4 _exptl_crystal_description block _exptl_crystal_colour gold _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.179 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 5983 _exptl_absorpt_coefficient_mu 1.623 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.5629 _exptl_absorpt_correction_T_max 0.5629 _exptl_absorpt_process_details 'SADABS 2.10 (Sheldrick, 2004)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 'Bruker Apex' _diffrn_measurement_method '\w \f' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 123127 _diffrn_reflns_av_R_equivalents 0.0803 _diffrn_reflns_av_sigmaI/netI 0.0141 _diffrn_reflns_limit_h_min -34 _diffrn_reflns_limit_h_max 33 _diffrn_reflns_limit_k_min -33 _diffrn_reflns_limit_k_max 33 _diffrn_reflns_limit_l_min -33 _diffrn_reflns_limit_l_max 33 _diffrn_reflns_theta_min 1.37 _diffrn_reflns_theta_max 28.22 _reflns_number_total 1101 _reflns_number_gt 953 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Apex2 v.1.00-2.1 (Bruker, 2006)' _computing_cell_refinement SAINT _computing_data_reduction 'SAINT v7.06A (Bruker, 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL 5.1 (Sheldrick, 1994)' _computing_publication_material SHELXL97 _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. This structure represents a partial solution. Analytical data (H-NMR) indicated that the IRMOF-3 starting material was 27% modified with cyclohexyl isocyanate to form cyclohexylurea substituent. However, because of disorder, which includes four-fold positional disorder imposed by the space group, neither the amine nor cyclohexylurea substituents could be located in the difference map. Likewise, the H atoms could not be located. These disordered substituents are represented in the sum and moiety formulas. All atoms except for Zn1 and C3 lie special positions with fractional occupancy. The aryl ring of the amino benzenedicarboxylate ligand has a two-fold disorder with respect to a mirror plane. Thus, atom C3 has an occupancy of 0.5. Several partially occupied and disordered chloroform solvent molecule were also found. However, acceptable atomic positions could not be ascertained for this solvent or for the amine and phenylurea substituents. These disordered moieties were treated as diffuse contributions using the program SQUEEZE (A. Spek, Platon Library). SQUEEZE located 12510.9 Ang^3^ void space per cell and 3429.5 electrons. Subtracting 1091.5 electrons for the amine and cyclohexylurea substituents leaves 2338 electrons. Forty molecules of chloroform require 2320 electrons per unit cell, giving five molecules of chloroform per formula unit. These chloroform molecules were included in the sum and moiety formulas. The cif check produces an alert level A for short intermolecular contacts among atoms in the aryl ring. However, these contacts are actually intramolecular, and fall within expected ranges for carbons on phneyl groups. Additionally, Mercury does not recognize the C3 C3 bond within the benzene ring, though the bond does appear in the cif. The reason for this is currently unknown. ; _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^)+(0.0833P)^2^+25.7144P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens none _refine_ls_hydrogen_treatment none _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1101 _refine_ls_number_parameters 28 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0805 _refine_ls_R_factor_gt 0.0626 _refine_ls_wR_factor_ref 0.1736 _refine_ls_wR_factor_gt 0.1629 _refine_ls_goodness_of_fit_ref 1.234 _refine_ls_restrained_S_all 1.234 _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 Zn1 Zn 0.293410(16) 0.206590(16) 0.206590(16) 0.0499(3) Uani 1 6 d S . . C1 C 0.2500 0.2500 0.1113(2) 0.0745(16) Uani 1 4 d S . . C2 C 0.2500 0.2500 0.0539(2) 0.0757(18) Uani 1 4 d S . . C3 C 0.2898(5) 0.2267(5) 0.0266(2) 0.089(5) Uani 0.50 1 d P . . O1 O 0.2500 0.2500 0.2500 0.0433(17) Uani 1 24 d S . . O2 O 0.28086(10) 0.21914(10) 0.13378(12) 0.0895(11) 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 0.0499(3) 0.0499(3) 0.0499(3) -0.00125(17) 0.00125(17) 0.00125(17) C1 0.085(3) 0.085(3) 0.054(3) 0.000 0.000 -0.007(4) C2 0.088(3) 0.088(3) 0.051(3) 0.000 0.000 -0.002(4) C3 0.091(7) 0.119(11) 0.056(3) -0.004(4) -0.001(3) 0.013(8) O1 0.0433(17) 0.0433(17) 0.0433(17) 0.000 0.000 0.000 O2 0.1099(17) 0.1099(17) 0.0488(17) -0.0022(11) 0.0022(11) 0.034(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 Zn1 O2 1.928(3) . ? Zn1 O2 1.928(3) 58 ? Zn1 O2 1.928(3) 79 ? Zn1 O1 1.9343(7) . ? Zn1 Zn1 3.1588(12) 74 ? Zn1 Zn1 3.1588(12) 51 ? Zn1 Zn1 3.1589(12) 28 ? C1 O2 1.263(4) . ? C1 O2 1.263(4) 74 ? C1 C2 1.475(8) . ? C2 C3 1.379(8) 181 ? C2 C3 1.379(8) . ? C2 C3 1.379(8) 74 ? C2 C3 1.379(8) 110 ? C3 C3 0.60(3) 181 ? C3 C3 1.370(12) 98 ? C3 C3 1.496(16) 86 ? O1 Zn1 1.9344(7) 74 ? O1 Zn1 1.9344(7) 51 ? O1 Zn1 1.9345(7) 28 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 Zn1 O2 107.30(12) . 58 ? O2 Zn1 O2 107.30(12) . 79 ? O2 Zn1 O2 107.30(12) 58 79 ? O2 Zn1 O1 111.56(11) . . ? O2 Zn1 O1 111.56(11) 58 . ? O2 Zn1 O1 111.56(11) 79 . ? O2 Zn1 Zn1 76.30(11) . 74 ? O2 Zn1 Zn1 124.65(9) 58 74 ? O2 Zn1 Zn1 124.65(9) 79 74 ? O1 Zn1 Zn1 35.3 . 74 ? O2 Zn1 Zn1 124.65(9) . 51 ? O2 Zn1 Zn1 76.30(11) 58 51 ? O2 Zn1 Zn1 124.65(9) 79 51 ? O1 Zn1 Zn1 35.3 . 51 ? Zn1 Zn1 Zn1 60.0 74 51 ? O2 Zn1 Zn1 124.65(9) . 28 ? O2 Zn1 Zn1 124.65(9) 58 28 ? O2 Zn1 Zn1 76.30(11) 79 28 ? O1 Zn1 Zn1 35.3 . 28 ? Zn1 Zn1 Zn1 60.0 74 28 ? Zn1 Zn1 Zn1 60.0 51 28 ? O2 C1 O2 125.4(6) . 74 ? O2 C1 C2 117.3(3) . . ? O2 C1 C2 117.3(3) 74 . ? C3 C2 C3 25.1(12) 181 . ? C3 C2 C3 112.7(8) 181 74 ? C3 C2 C3 118.8(7) . 74 ? C3 C2 C3 118.8(7) 181 110 ? C3 C2 C3 112.7(8) . 110 ? C3 C2 C3 25.1(12) 74 110 ? C3 C2 C1 120.6(4) 181 . ? C3 C2 C1 120.6(4) . . ? C3 C2 C1 120.6(4) 74 . ? C3 C2 C1 120.6(4) 110 . ? C3 C3 C3 90.001(4) 181 98 ? C3 C3 C2 77.4(6) 181 . ? C3 C3 C2 120.6(4) 98 . ? C3 C3 C3 66.3(11) 181 86 ? C3 C3 C3 23.7(11) 98 86 ? C2 C3 C3 112.3(8) . 86 ? Zn1 O1 Zn1 109.5 . 74 ? Zn1 O1 Zn1 109.5 . 51 ? Zn1 O1 Zn1 109.471(1) 74 51 ? Zn1 O1 Zn1 109.473(1) . 28 ? Zn1 O1 Zn1 109.5 74 28 ? Zn1 O1 Zn1 109.5 51 28 ? C1 O2 Zn1 131.0(3) . . ? _diffrn_measured_fraction_theta_max 0.989 _diffrn_reflns_theta_full 28.22 _diffrn_measured_fraction_theta_full 0.989 _refine_diff_density_max 0.437 _refine_diff_density_min -0.306 _refine_diff_density_rms 0.057 # SQUEEZE RESULTS (APPEND TO CIF) 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 -0.017 -0.007 -0.005 12510.9 3429.5 _platon_squeeze_details ; ; # Attachment 'ecd223sqz.cif' data_ecd223sqz _database_code_depnum_ccdc_archive 'CCDC 684722' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common '53% IRMOF-3 Ph-Urea' _chemical_melting_point ? _chemical_formula_moiety ; 0.47 C24 H15 O13 N3 Zn4, 0.53 C45 H30 O16 N6 Zn4, 4 C H Cl3 ; _chemical_formula_sum 'C39.13 H27 Cl11.50 N4.63 O14.50 Zn4' _chemical_formula_weight 1463.06 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' Cl Cl 0.1484 0.1585 '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 cubic _symmetry_space_group_name_H-M 'F m -3 m' 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' 'y, x, -z' '-y, -x, -z' 'y, -x, z' '-y, x, z' 'x, z, -y' '-x, z, y' '-x, -z, -y' 'x, -z, y' 'z, y, -x' 'z, -y, x' '-z, y, x' '-z, -y, -x' 'x, y+1/2, z+1/2' '-x, -y+1/2, z+1/2' '-x, y+1/2, -z+1/2' 'x, -y+1/2, -z+1/2' 'z, x+1/2, y+1/2' 'z, -x+1/2, -y+1/2' '-z, -x+1/2, y+1/2' '-z, x+1/2, -y+1/2' 'y, z+1/2, x+1/2' '-y, z+1/2, -x+1/2' 'y, -z+1/2, -x+1/2' '-y, -z+1/2, x+1/2' 'y, x+1/2, -z+1/2' '-y, -x+1/2, -z+1/2' 'y, -x+1/2, z+1/2' '-y, x+1/2, z+1/2' 'x, z+1/2, -y+1/2' '-x, z+1/2, y+1/2' '-x, -z+1/2, -y+1/2' 'x, -z+1/2, y+1/2' 'z, y+1/2, -x+1/2' 'z, -y+1/2, x+1/2' '-z, y+1/2, x+1/2' '-z, -y+1/2, -x+1/2' 'x+1/2, y, z+1/2' '-x+1/2, -y, z+1/2' '-x+1/2, y, -z+1/2' 'x+1/2, -y, -z+1/2' 'z+1/2, x, y+1/2' 'z+1/2, -x, -y+1/2' '-z+1/2, -x, y+1/2' '-z+1/2, x, -y+1/2' 'y+1/2, z, x+1/2' '-y+1/2, z, -x+1/2' 'y+1/2, -z, -x+1/2' '-y+1/2, -z, x+1/2' 'y+1/2, x, -z+1/2' '-y+1/2, -x, -z+1/2' 'y+1/2, -x, z+1/2' '-y+1/2, x, z+1/2' 'x+1/2, z, -y+1/2' '-x+1/2, z, y+1/2' '-x+1/2, -z, -y+1/2' 'x+1/2, -z, y+1/2' 'z+1/2, y, -x+1/2' 'z+1/2, -y, x+1/2' '-z+1/2, y, x+1/2' '-z+1/2, -y, -x+1/2' 'x+1/2, y+1/2, z' '-x+1/2, -y+1/2, z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' 'z+1/2, x+1/2, y' 'z+1/2, -x+1/2, -y' '-z+1/2, -x+1/2, y' '-z+1/2, x+1/2, -y' 'y+1/2, z+1/2, x' '-y+1/2, z+1/2, -x' 'y+1/2, -z+1/2, -x' '-y+1/2, -z+1/2, x' 'y+1/2, x+1/2, -z' '-y+1/2, -x+1/2, -z' 'y+1/2, -x+1/2, z' '-y+1/2, x+1/2, z' 'x+1/2, z+1/2, -y' '-x+1/2, z+1/2, y' '-x+1/2, -z+1/2, -y' 'x+1/2, -z+1/2, y' 'z+1/2, y+1/2, -x' 'z+1/2, -y+1/2, x' '-z+1/2, y+1/2, x' '-z+1/2, -y+1/2, -x' '-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' '-y, -x, z' 'y, x, z' '-y, x, -z' 'y, -x, -z' '-x, -z, y' 'x, -z, -y' 'x, z, y' '-x, z, -y' '-z, -y, x' '-z, y, -x' 'z, -y, -x' 'z, y, x' '-x, -y+1/2, -z+1/2' 'x, y+1/2, -z+1/2' 'x, -y+1/2, z+1/2' '-x, y+1/2, z+1/2' '-z, -x+1/2, -y+1/2' '-z, x+1/2, y+1/2' 'z, x+1/2, -y+1/2' 'z, -x+1/2, y+1/2' '-y, -z+1/2, -x+1/2' 'y, -z+1/2, x+1/2' '-y, z+1/2, x+1/2' 'y, z+1/2, -x+1/2' '-y, -x+1/2, z+1/2' 'y, x+1/2, z+1/2' '-y, x+1/2, -z+1/2' 'y, -x+1/2, -z+1/2' '-x, -z+1/2, y+1/2' 'x, -z+1/2, -y+1/2' 'x, z+1/2, y+1/2' '-x, z+1/2, -y+1/2' '-z, -y+1/2, x+1/2' '-z, y+1/2, -x+1/2' 'z, -y+1/2, -x+1/2' 'z, y+1/2, x+1/2' '-x+1/2, -y, -z+1/2' 'x+1/2, y, -z+1/2' 'x+1/2, -y, z+1/2' '-x+1/2, y, z+1/2' '-z+1/2, -x, -y+1/2' '-z+1/2, x, y+1/2' 'z+1/2, x, -y+1/2' 'z+1/2, -x, y+1/2' '-y+1/2, -z, -x+1/2' 'y+1/2, -z, x+1/2' '-y+1/2, z, x+1/2' 'y+1/2, z, -x+1/2' '-y+1/2, -x, z+1/2' 'y+1/2, x, z+1/2' '-y+1/2, x, -z+1/2' 'y+1/2, -x, -z+1/2' '-x+1/2, -z, y+1/2' 'x+1/2, -z, -y+1/2' 'x+1/2, z, y+1/2' '-x+1/2, z, -y+1/2' '-z+1/2, -y, x+1/2' '-z+1/2, y, -x+1/2' 'z+1/2, -y, -x+1/2' 'z+1/2, y, x+1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, z' '-x+1/2, y+1/2, z' '-z+1/2, -x+1/2, -y' '-z+1/2, x+1/2, y' 'z+1/2, x+1/2, -y' 'z+1/2, -x+1/2, y' '-y+1/2, -z+1/2, -x' 'y+1/2, -z+1/2, x' '-y+1/2, z+1/2, x' 'y+1/2, z+1/2, -x' '-y+1/2, -x+1/2, z' 'y+1/2, x+1/2, z' '-y+1/2, x+1/2, -z' 'y+1/2, -x+1/2, -z' '-x+1/2, -z+1/2, y' 'x+1/2, -z+1/2, -y' 'x+1/2, z+1/2, y' '-x+1/2, z+1/2, -y' '-z+1/2, -y+1/2, x' '-z+1/2, y+1/2, -x' 'z+1/2, -y+1/2, -x' 'z+1/2, y+1/2, x' _cell_length_a 25.6761(9) _cell_length_b 25.6761(9) _cell_length_c 25.6761(9) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 16927.3(10) _cell_formula_units_Z 8 _cell_measurement_temperature 100(2) _cell_measurement_reflns_used 3004 _cell_measurement_theta_min 2.75 _cell_measurement_theta_max 24.7 _exptl_crystal_description block _exptl_crystal_colour gold _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.40 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.148 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 5805 _exptl_absorpt_coefficient_mu 1.525 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.5806 _exptl_absorpt_correction_T_max 0.7502 _exptl_absorpt_process_details 'SADABS 2.10 (Sheldrick, 2004)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 100(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 'Bruker Apex' _diffrn_measurement_method '\w \f' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12890 _diffrn_reflns_av_R_equivalents 0.0528 _diffrn_reflns_av_sigmaI/netI 0.0272 _diffrn_reflns_limit_h_min -28 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -32 _diffrn_reflns_limit_k_max 28 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 31 _diffrn_reflns_theta_min 1.59 _diffrn_reflns_theta_max 27.10 _reflns_number_total 998 _reflns_number_gt 586 _reflns_threshold_expression I>2\s(I) _computing_data_collection 'Apex2 v.1.00-2.1 (Bruker, 2006)' _computing_cell_refinement SAINT _computing_data_reduction 'SAINT v7.06A (Bruker, 2004)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXTL 5.1 (Sheldrick, 1994)' _computing_publication_material SHELXL97 _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. This structure represents a partial solution. Analytical data (H-NMR) indicated that the IRMOF-3 starting material was 53% modified with phenyl isocyanate to form phenylurea substituent. However, because of disorder, which includes four-fold positional disorder imposed by the space group, neither the amine nor phenylurea substituents could be located in the difference map. Likewise, the H atoms could not be located. These disordered substituents are represented in the sum and moiety formulas. All atoms except for Zn1 and C3 lie special positions with fractional occupancy. The aryl ring of the amino benzenedicarboxylate ligand has a two-fold disorder with respect to a mirror plane. Thus, atom C3 has an occupancy of 0.5. Several partially occupied and disordered chloroform solvent molecule were also found. However, acceptable atomic positions could not be ascertained for this solvent or for the amine and phenylurea substituents. These disordered moieties were treated as diffuse contributions using the program SQUEEZE (A. Spek, Platon Library). SQUEEZE located 12928.1 Ang^3^ void space per cell and 2890 electrons. Subtracting 1005 electrons for the amine and phenylurea substituents leaves 1885 electrons. Thirty-two molecules of chloroform require 1856 electrons per unit cell, giving four molecules of chloroform per formula unit. These chloroform molecules were included in the sum and moiety formulas. The cif check produces an alert level A for short intermolecular contacts among atoms in the aryl ring. However, these contacts are actually intramolecular, and fall within expected ranges for carbons on phneyl groups. Additionally, Mercury does not recognize the C3 C3 bond within the benzene ring, though the bond does appear in the cif. The reason for this is currently unknown. ; _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^)+(0.0983P)^2^] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens none _refine_ls_hydrogen_treatment none _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 998 _refine_ls_number_parameters 28 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0892 _refine_ls_R_factor_gt 0.0541 _refine_ls_wR_factor_ref 0.1579 _refine_ls_wR_factor_gt 0.1455 _refine_ls_goodness_of_fit_ref 0.955 _refine_ls_restrained_S_all 0.955 _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 0.793480(18) 0.706520(18) 0.706520(18) 0.0632(4) Uani 1 6 d S . . C1 C 0.7500 0.7500 0.6111(2) 0.0829(17) Uani 1 4 d S . . C2 C 0.7500 0.7500 0.5540(2) 0.0877(19) Uani 1 4 d S . . C3 C 0.7713(3) 0.7093(3) 0.5258(2) 0.100(4) Uani 0.50 1 d P . . O1 O 0.7500 0.7500 0.7500 0.057(2) Uani 1 24 d S . . O2 O 0.78049(9) 0.71951(9) 0.63397(12) 0.0999(11) 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 0.0632(4) 0.0632(4) 0.0632(4) -0.0016(2) 0.0016(2) 0.0016(2) C1 0.097(3) 0.097(3) 0.054(4) 0.000 0.000 -0.012(4) C2 0.094(3) 0.094(3) 0.076(4) 0.000 0.000 0.000(4) C3 0.127(8) 0.099(6) 0.075(3) 0.005(3) 0.006(4) -0.006(6) O1 0.057(2) 0.057(2) 0.057(2) 0.000 0.000 0.000 O2 0.1204(17) 0.1204(17) 0.0588(19) 0.0010(13) -0.0010(13) 0.024(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 Zn1 O2 1.922(3) 79_665 ? Zn1 O2 1.922(3) 58_656 ? Zn1 O2 1.922(3) . ? Zn1 O1 1.9336(8) . ? Zn1 Zn1 3.1576(13) 74_665 ? Zn1 Zn1 3.1576(13) 28_566 ? Zn1 Zn1 3.1576(13) 51_656 ? C1 O2 1.254(4) 74_665 ? C1 O2 1.254(4) . ? C1 C2 1.465(8) . ? C2 C3 1.385(7) . ? C2 C3 1.385(7) 110 ? C2 C3 1.385(7) 181_665 ? C2 C3 1.385(7) 74_665 ? C3 C3 0.702(18) 181_665 ? C3 C3 1.322(12) 98_556 ? C3 C3 1.497(14) 86_666 ? O1 Zn1 1.9336(8) 74_665 ? O1 Zn1 1.9337(8) 28_566 ? O1 Zn1 1.9337(8) 51_656 ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag O2 Zn1 O2 107.85(11) 79_665 58_656 ? O2 Zn1 O2 107.85(11) 79_665 . ? O2 Zn1 O2 107.85(11) 58_656 . ? O2 Zn1 O1 111.05(11) 79_665 . ? O2 Zn1 O1 111.05(11) 58_656 . ? O2 Zn1 O1 111.05(11) . . ? O2 Zn1 Zn1 124.24(8) 79_665 74_665 ? O2 Zn1 Zn1 124.24(9) 58_656 74_665 ? O2 Zn1 Zn1 75.79(11) . 74_665 ? O1 Zn1 Zn1 35.3 . 74_665 ? O2 Zn1 Zn1 75.78(11) 79_665 28_566 ? O2 Zn1 Zn1 124.24(8) 58_656 28_566 ? O2 Zn1 Zn1 124.24(8) . 28_566 ? O1 Zn1 Zn1 35.264(1) . 28_566 ? Zn1 Zn1 Zn1 60.000(1) 74_665 28_566 ? O2 Zn1 Zn1 124.24(8) 79_665 51_656 ? O2 Zn1 Zn1 75.78(11) 58_656 51_656 ? O2 Zn1 Zn1 124.24(9) . 51_656 ? O1 Zn1 Zn1 35.264(1) . 51_656 ? Zn1 Zn1 Zn1 60.000(1) 74_665 51_656 ? Zn1 Zn1 Zn1 60.0 28_566 51_656 ? O2 C1 O2 124.0(6) 74_665 . ? O2 C1 C2 118.0(3) 74_665 . ? O2 C1 C2 118.0(3) . . ? C3 C2 C3 108.8(7) . 110 ? C3 C2 C3 29.4(8) . 181_665 ? C3 C2 C3 116.8(7) 110 181_665 ? C3 C2 C3 116.8(7) . 74_665 ? C3 C2 C3 29.4(8) 110 74_665 ? C3 C2 C3 108.8(7) 181_665 74_665 ? C3 C2 C1 121.6(3) . . ? C3 C2 C1 121.6(3) 110 . ? C3 C2 C1 121.6(3) 181_665 . ? C3 C2 C1 121.6(3) 74_665 . ? C3 C3 C3 90.000(1) 181_665 98_556 ? C3 C3 C2 75.3(4) 181_665 . ? C3 C3 C2 121.6(3) 98_556 . ? C3 C3 C3 62.0(6) 181_665 86_666 ? C3 C3 C3 28.0(6) 98_556 86_666 ? C2 C3 C3 110.1(6) . 86_666 ? Zn1 O1 Zn1 109.472(1) 74_665 . ? Zn1 O1 Zn1 109.5 74_665 28_566 ? Zn1 O1 Zn1 109.5 . 28_566 ? Zn1 O1 Zn1 109.471(1) 74_665 51_656 ? Zn1 O1 Zn1 109.472(1) . 51_656 ? Zn1 O1 Zn1 109.470(1) 28_566 51_656 ? C1 O2 Zn1 132.2(4) . . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O2 C1 C2 C3 -162.7(4) 74_665 . . . ? O2 C1 C2 C3 17.3(4) . . . . ? O2 C1 C2 C3 -17.3(4) 74_665 . . 110 ? O2 C1 C2 C3 162.7(4) . . . 110 ? O2 C1 C2 C3 162.7(4) 74_665 . . 181_665 ? O2 C1 C2 C3 -17.3(4) . . . 181_665 ? O2 C1 C2 C3 17.3(5) 74_665 . . 74_665 ? O2 C1 C2 C3 -162.7(5) . . . 74_665 ? C3 C2 C3 C3 111.5(6) 110 . . 181_665 ? C3 C2 C3 C3 80.7(3) 74_665 . . 181_665 ? C1 C2 C3 C3 -99.3(3) . . . 181_665 ? C3 C2 C3 C3 30.8(7) 110 . . 98_556 ? C3 C2 C3 C3 -80.7(3) 181_665 . . 98_556 ? C3 C2 C3 C3 -0.002(4) 74_665 . . 98_556 ? C1 C2 C3 C3 180.000(3) . . . 98_556 ? C3 C2 C3 C3 59.2(12) 110 . . 86_666 ? C3 C2 C3 C3 -52.3(7) 181_665 . . 86_666 ? C3 C2 C3 C3 28.5(5) 74_665 . . 86_666 ? C1 C2 C3 C3 -151.5(5) . . . 86_666 ? O2 Zn1 O1 Zn1 120.0 79_665 . . 74_665 ? O2 Zn1 O1 Zn1 -120.0 58_656 . . 74_665 ? O2 Zn1 O1 Zn1 0.000(1) . . . 74_665 ? Zn1 Zn1 O1 Zn1 120.0 28_566 . . 74_665 ? Zn1 Zn1 O1 Zn1 -120.0 51_656 . . 74_665 ? O2 Zn1 O1 Zn1 0.0 79_665 . . 28_566 ? O2 Zn1 O1 Zn1 120.0 58_656 . . 28_566 ? O2 Zn1 O1 Zn1 -120.0 . . . 28_566 ? Zn1 Zn1 O1 Zn1 -120.0 74_665 . . 28_566 ? Zn1 Zn1 O1 Zn1 120.0 51_656 . . 28_566 ? O2 Zn1 O1 Zn1 -120.0 79_665 . . 51_656 ? O2 Zn1 O1 Zn1 0.0 58_656 . . 51_656 ? O2 Zn1 O1 Zn1 120.0 . . . 51_656 ? Zn1 Zn1 O1 Zn1 120.0 74_665 . . 51_656 ? Zn1 Zn1 O1 Zn1 -120.0 28_566 . . 51_656 ? O2 C1 O2 Zn1 0.000(5) 74_665 . . . ? C2 C1 O2 Zn1 180.000(2) . . . . ? O2 Zn1 O2 C1 -121.88(12) 79_665 . . . ? O2 Zn1 O2 C1 121.88(12) 58_656 . . . ? O1 Zn1 O2 C1 0.000(2) . . . . ? Zn1 Zn1 O2 C1 0.000(2) 74_665 . . . ? Zn1 Zn1 O2 C1 -37.22(4) 28_566 . . . ? Zn1 Zn1 O2 C1 37.22(5) 51_656 . . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.10 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.363 _refine_diff_density_min -0.393 _refine_diff_density_rms 0.066 # SQUEEZE RESULTS (APPEND TO CIF) 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 -0.016 -0.007 -0.006 12852.2 2889.8 _platon_squeeze_details ; ;