# Supplementary Material (ESI) for PCCP # This journal is (c) the Owner Societies 2009 data_global _journal_name_full Phys.Chem.Chem.Phys.(PCCP) _journal_coden_Cambridge 1326 _publ_contact_author_name 'Gerald Chaplais' _publ_contact_author_email GERALD.CHAPLAIS@UNIV-MULHOUSE.FR _publ_section_title ; IM-19: a new flexible microporous gallium based-MOF framework with pressure- and temperature-dependent openings ; loop_ _publ_author_name 'Gerald Chaplais' 'Nicolas Bats' 'Delphine Bazer-Bachi' 'C Lecomte' 'Joel Patarin' 'F. Porcher' ; A.Ssimon-Masseron ; # Attachment 'IM-19_dmf.cif' #======================================================================= data_IM-19_dmf _database_code_depnum_ccdc_archive 'CCDC 713193' #======================================================================= # 5. CHEMICAL DATA _chemical_name_systematic ; ? ; _chemical_name_common 'IM-19 dmf' _chemical_formula_moiety ; 0.5(Ga O H O2 C C6 H4 C O2), 0.425(C H3 C H3 N C O H) ; _chemical_formula_structural '0.5( GaO O2 C C6 H4 C O2 )' _chemical_formula_analytical ? _chemical_formula_sum 'C5.275 H5.475 Ga0.5 N0.425 O2.925' _chemical_formula_weight 156.5 # 312.98 _chemical_absolute_configuration . #======================================================================= # 6. CRYSTAL DATA _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'I 2/a' _symmetry_space_group_name_Hall '-I 2ya' loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 -x+1/2,y,-z 3 -x,-y,-z 4 x+1/2,-y,z 5 x+1/2,y+1/2,z+1/2 6 -x,y+1/2,-z+1/2 7 -x+1/2,-y+1/2,-z+1/2 8 x,-y+1/2,z+1/2 _cell_length_a 6.7120(4) _cell_length_b 11.2486(11) _cell_length_c 17.9650(16) _cell_angle_alpha 90 _cell_angle_beta 91.975(7) _cell_angle_gamma 90 _cell_volume 1355.6(2) _cell_formula_units_Z 8 _cell_measurement_reflns_used 30365 _cell_measurement_theta_min 3.54 _cell_measurement_theta_max 31.78 _cell_measurement_temperature 293 _cell_special_details ; Full refinement with all reflexions measured ; _exptl_crystal_density_diffrn 1.534 _exptl_crystal_F_000 608.2 _exptl_absorpt_coefficient_mu 2.046 _exptl_crystal_description ;translucid plate cut from larger fragment ; _exptl_crystal_size_max 0.165 _exptl_crystal_size_mid 0.100 _exptl_crystal_size_min 0.070 _exptl_crystal_colour white _exptl_absorpt_correction_type none #======================================================================= # 7. EXPERIMENTAL DATA _diffrn_ambient_temperature 293 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'X-ray tube' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_device '\k-geometry diffractometer' _diffrn_measurement_device_type 'Oxford diffraction XCalibur II' _diffrn_measurement_method '\w or \f scans' _diffrn_standards_number 0 _diffrn_reflns_number 22796 _diffrn_reflns_theta_min 3.54 _diffrn_reflns_theta_max 31.78 _diffrn_reflns_theta_full 31.04 _diffrn_measured_fraction_theta_max 0.77 _diffrn_measured_fraction_theta_full 0.80 _diffrn_reflns_av_R_equivalents 0.1021 _diffrn_reflns_av_sigmaI/netI 0.0184 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -25 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_reduction_process ; Non overlapped Bragg spots merged in Laue class 2/m after determination of twin overlap from UB matrix and profiles. Restriction to non overlapping reflections for the refinement limits the completeness up to 2\qmax = 31.78. Despite this, the reflections/parameters ratio is 1779/72. ; #======================================================================= # 8. REFINEMENT DATA _refine_special_details ; Large void fraction (zeolite-type material) where occluded dmf molecules where not successfully located. Ghost density of 1.6e/A3 located in the channels 2.7A away from O3, possibly associated with disordered dmf. Anisotropic refinement of O3 not reasonnable, probably because of the residue. Uncomplete structure (0.85 dmf molecule/u.c. missing) hence large R, Rw and Gof. Hydrogen atoms non located from (Fo-kFc) Fourier maps but allowed to ride about their expected position. Car-H distances restrained to their neutron value 5ee Allen, in Acta Cryst. (1986). B42, 515-522). ; _reflns_number_total 1779 _reflns_number_gt 1288 _reflns_threshold_expression I>3\s(I) _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt 0.0873 _refine_ls_wR_factor_gt 0.1297 _refine_ls_R_factor_all 0.1151 _refine_ls_wR_factor_ref 0.1302 _refine_ls_goodness_of_fit_ref 7.97 _refine_ls_goodness_of_fit_gt 9.41 _refine_ls_number_reflns 1779 _refine_ls_number_parameters 72 _refine_ls_number_restraints 9 _refine_ls_number_constraints 2 _refine_ls_weighting_scheme sigma _refine_ls_weighting_details w=1/(\s^2^(F)+0.0001F^2^) _refine_ls_hydrogen_treatment refall _refine_ls_shift/su_max 0.0015 _refine_ls_shift/su_mean 0.0002 _refine_diff_density_max 3.42 _refine_diff_density_min -3.36 _refine_ls_extinction_method none loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source Ga 0.231 1.608 'International Tables Vol C tables 4.2.6.8 and 6.1.1.1' O 0.011 0.006 'International Tables Vol C tables 4.2.6.8 and 6.1.1.1' C 0.003 0.002 'International Tables Vol C tables 4.2.6.8 and 6.1.1.1' H 0.000 0.000 'International Tables Vol C tables 4.2.6.8 and 6.1.1.1' _computing_data_collection ;Oxford Diffraction, (2007) Xcalibur CCD system. ; _computing_cell_refinement ;Oxford Diffraction, (2007) CrysAlisPro Software system. ; _computing_data_reduction ;Oxford Diffraction, (2007) CrysAlisPro Software system. Jana2006 (Petricek, Dusek & Palatinus, 2006)' ; _computing_structure_solution 'SIR2006: the program, J. Appl. Cryst, (2003). 36, 1103' _computing_structure_refinement 'Jana2006 (Petricek, Dusek & Palatinus, 2006)' _computing_publication_material 'Jana2006 (Petricek, Dusek & Palatinus, 2006)' #======================================================================= # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_adp_type _atom_site_U_iso_or_equiv _atom_site_symmetry_multiplicity _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ga1 Ga 0.5 0 0.5 Uani 0.0135(3) 4 1 d . . . O3 O 0.25 0.0769(6) 0.5 Uani 0.0150(19) 4 1 d . . . O1 O 0.6056(9) 0.1215(6) 0.5725(3) Uani 0.035(2) 8 1 d . . . C1 C 0.7620(11) 0.1308(7) 0.6054(4) Uani 0.022(2) 8 1 d . . . C2 C 0.7597(12) 0.1970(7) 0.6813(3) Uani 0.025(2) 8 1 d . . . C4 C 0.9284(11) 0.2166(9) 0.7222(5) Uani 0.058(4) 8 1 d . . . C3 C 0.5806(11) 0.2286(9) 0.7082(4) Uani 0.045(4) 8 1 d . . . O2 O 0.9302(9) 0.0980(6) 0.5875(3) Uani 0.034(2) 8 1 d . . . H3 H 0.4454(13) 0.210(2) 0.6763(8) Uiso 0.03944(3) 8 1 d . . . H4 H 1.0697(13) 0.189(2) 0.7018(10) Uiso 0.03627(3) 8 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_type_symbol _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Ga1 Ga 0.0101(5) 0.0186(6) 0.0121(5) -0.0018(6) 0.0022(3) 0.0003(5) O3 O 0.001(3) 0.018(4) 0.026(4) 0 0.001(2) 0 O1 O 0.020(3) 0.048(4) 0.037(3) 0.004(3) 0.000(2) -0.022(3) C1 C 0.021(4) 0.023(4) 0.022(4) 0.002(3) -0.003(3) -0.008(3) C2 C 0.028(4) 0.026(4) 0.021(4) 0.002(3) -0.002(3) -0.010(3) C4 C 0.030(5) 0.087(9) 0.058(7) 0.000(5) 0.012(5) -0.052(7) C3 C 0.033(5) 0.081(8) 0.022(4) 0.006(5) 0.000(4) -0.021(5) O2 O 0.020(3) 0.064(4) 0.017(3) -0.009(3) 0.009(2) -0.024(3) #======================================================================= # 10. MOLECULAR GEOMETRY loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag C1 O1 . . 1.191(9) yes C1 C2 . . 1.554(10) yes C1 O2 . . 1.241(10) yes C2 C4 . . 1.347(11) yes C2 C3 . . 1.359(11) yes C4 C3 . 7_656 1.396(13) yes C4 H4 . . 1.076(15) yes C3 H3 . . 1.076(14) yes loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag O1 C1 C2 . . . 116.2(7) yes C2 C1 O2 . . . 114.0(6) yes C1 C2 C4 . . . 121.6(7) yes C1 C2 C3 . . . 118.2(7) yes C2 C4 C3 . . 7_656 120.0(7) yes C2 C4 H4 . . . 120.0(13) yes C3 C4 H4 7_656 . . 120.0(12) yes C2 C3 C4 . . 7_656 120.0(7) yes C2 C3 H3 . . . 120.0(11) yes C4 C3 H3 7_656 . . 120.0(11) yes #======================================================================= # Attachment 'IM-19_ps.cif' #======================================================================= data_IM-19_ps _database_code_depnum_ccdc_archive 'CCDC 713194' #======================================================================= # 5. CHEMICAL DATA _chemical_name_systematic ; ? ; _chemical_name_common 'IM-19 ps' _chemical_formula_moiety ; 0.5(Ga O H O2 C C6 H4 C O2), 0.375 (H O2 C C6 H4 C O2 H) ; _chemical_formula_structural '0.5(Ga O O2 C C6 H4 C O2)' _chemical_formula_analytical ? _chemical_formula_sum 'C7 H4.75 Ga0.5 O4' _chemical_formula_weight 187.7 #======================================================================= # 6. CRYSTAL DATA _symmetry_cell_setting orthorhombic _symmetry_space_group_name_H-M 'P n m a' _symmetry_space_group_name_Hall '-P 2ac 2n' loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz 1 x,y,z 2 -x+1/2,-y,z+1/2 3 -x,y+1/2,-z 4 x+1/2,-y+1/2,-z+1/2 5 -x,-y,-z 6 x+1/2,y,-z+1/2 7 x,-y+1/2,z 8 -x+1/2,y+1/2,z+1/2 _cell_length_a 17.4370(2) _cell_length_b 6.7475(4) _cell_length_c 12.1541(4) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1430.00(10) _cell_formula_units_Z 8 _cell_measurement_reflns_used 93162 _cell_measurement_theta_min 2.88 _cell_measurement_theta_max 55.53 _cell_measurement_temperature 293 _cell_special_details ; Average 3D structure of a composite crystal. Incommensurate q-vector refined together with cell in a first step (9999 reflexions). Cell post-refined during integration. ; _exptl_crystal_density_diffrn 1.744 #_exptl_crystal_F_000 476 _exptl_crystal_F_000 754 _exptl_absorpt_coefficient_mu 1.966 _exptl_crystal_description ;transparent parallelepiped cut from a larger fragment ; _exptl_crystal_size_max 0.170 _exptl_crystal_size_mid 0.120 _exptl_crystal_size_min 0.075 _exptl_crystal_colour white _exptl_absorpt_correction_type none _diffrn_ambient_temperature 293 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'X-ray tube' _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_monochromator graphite _diffrn_measurement_device 'four-cycle diffractometer' _diffrn_measurement_device_type 'Oxford Diffraction CCD' _diffrn_measurement_method '\w or \f scans' _diffrn_reflns_number 84993 _diffrn_reflns_theta_min 2.88 _diffrn_reflns_theta_max 55.53 _diffrn_reflns_theta_full 44.13 _diffrn_measured_fraction_theta_max 0.93 _diffrn_measured_fraction_theta_full 0.98 _diffrn_reflns_av_R_equivalents 0.1162 _diffrn_reflns_av_sigmaI/netI 0.0639 _diffrn_reflns_limit_h_min -31 _diffrn_reflns_limit_h_max 40 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_reduction_process ; Main reflections and satellites up to order m=2 merged in superspace group with JANA2006. Sigma model taken from average reflections. ; _diffrn_standards_number 0 #======================================================================= # 8. REFINEMENT DATA _refine_special_details ; Large void fraction (zeolite-type material) where occluded molecules of terephalic acid (H2BDC) give rise to an incommensurate structure. Continuous residual density in 3D Pnma space-group associated with H2BDC. is visible along channel axis b. Uncomplete structure (0.75 H2BDC molecule and 4H from bridging OH groups per unit cell are not included in the model) hence large conventionnal aggreement factors in Pnma. H atoms from framework BDC molecules are allowed to ride around their expected neutron position (for Car-H distance, see Allen in Acta Cryst. (1986). B42, 515-522) ; _reflns_number_total 9127 _reflns_number_gt 3875 _reflns_threshold_expression I>3\s(I) _refine_ls_structure_factor_coef F _refine_ls_R_factor_gt 0.0981 _refine_ls_wR_factor_gt 0.2113 _refine_ls_R_factor_all 0.1747 _refine_ls_wR_factor_ref 0.2143 _refine_ls_goodness_of_fit_ref 5.10 _refine_ls_goodness_of_fit_gt 7.75 _refine_ls_number_reflns 9127 _refine_ls_number_parameters 89 _refine_ls_number_restraints 8 _refine_ls_number_constraints 2 _refine_ls_weighting_scheme sigma _refine_ls_weighting_details w=1/(\s^2^(F)+0.0001F^2^) _refine_ls_hydrogen_treatment refall _refine_ls_shift/su_max 0.0096 _refine_ls_shift/su_mean 0.0052 _refine_diff_density_max 9.36 _refine_diff_density_min -2.61 _refine_ls_extinction_method none loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c C 0.003 0.002 'International Tables Vol C tables 4.2.6.8 and 6.1.1.4' 2.31 20.843901 1.02 10.2075 1.5886 0.5687 0.865 51.651199 0.2156 H 0.000 0.000 'International Tables Vol C tables 4.2.6.8 and 6.1.1.4' 0.493002 10.5109 0.322912 26.1257 0.140191 3.14236 0.04081 57.799702 0.003038 Ga 0.231 1.608 'International Tables Vol C tables 4.2.6.8 and 6.1.1.4' 15.2354 3.0669 6.7006 0.2412 4.3591 10.7805 2.9623 61.413502 1.7189 O 0.011 0.006 'International Tables Vol C tables 4.2.6.8 and 6.1.1.4' 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.867 32.908901 0.2508 _computing_data_collection ;Oxford Diffraction, (2007) Xcalibur CCD system. ; _computing_cell_refinement ;Oxford Diffraction, (2007) CrysAlisPro Software system. ; _computing_data_reduction ;Oxford Diffraction, (2007) CrysAlisPro Software system. Jana2006 (Petricek, Dusek & Palatinus, 2006)' ; _computing_structure_solution 'SIR2006: the program, J. Appl. Cryst, (2003). 36, 1103' _computing_structure_refinement 'Jana2006 (Petricek, Dusek & Palatinus, 2006)' _computing_publication_material 'Jana2006 (Petricek, Dusek & Palatinus, 2006)' #======================================================================= # 9. ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_adp_type _atom_site_U_iso_or_equiv _atom_site_symmetry_multiplicity _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Ga Ga 1 0 1 Uani 0.01225(11) 4 1 d . . . O3 O 0.9936 0.25 1.0734 Uani 0.0149(6) 4 1 d . . . O1 O 0.92632(11) 0.0830(3) 0.88584(19) Uani 0.0268(6) 8 1 d . . . O2 O 0.58949(10) 0.0826(3) 0.5886(2) Uani 0.0262(6) 8 1 d . . . C2 C 0.82814(19) 0.25 0.7914(3) Uani 0.0251(11) 4 1 d . . . C1 C 0.89907(17) 0.25 0.8600(3) Uani 0.0183(9) 4 1 d . . . C5 C 0.69218(17) 0.25 0.6712(3) Uani 0.0236(11) 4 1 d . . . C6 C 0.61762(18) 0.25 0.6108(3) Uani 0.0176(9) 4 1 d . . . C3 C 0.79127(17) 0.4288(3) 0.7651(3) Uani 0.0460(12) 8 1 d . . . H3 H 0.8119(4) 0.5661(5) 0.7989(9) Uiso 0.033(10) 8 1 d . . . C4 C 0.72605(16) 0.4274(3) 0.6995(3) Uani 0.0334(10) 8 1 d . . . H4 H 0.7021(9) 0.5647(5) 0.6704(18) Uiso 0.028(10) 8 1 d . . . loop_ _atom_site_aniso_label _atom_site_aniso_type_symbol _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_12 _atom_site_aniso_U_13 _atom_site_aniso_U_23 Ga Ga 0.00526(12) 0.00678(15) 0.0247(3) -0.00013(11) 0.00039(13) 0.00079(14) O3 O 0.0127 0.0061(8) 0.0260(14) 0 0.0012(8) 0 O1 O 0.0230(9) 0.0149(9) 0.0425(14) 0.0045(7) -0.0173(9) -0.0027(9) O2 O 0.0148(7) 0.0146(8) 0.0492(14) -0.0046(7) -0.0194(8) 0.0046(10) C2 C 0.0148(13) 0.0116(14) 0.049(3) 0 -0.0190(16) 0 C1 C 0.0078(10) 0.0142(14) 0.033(2) 0 -0.0096(13) 0 C5 C 0.0109(12) 0.0109(13) 0.049(3) 0 -0.0117(15) 0 C6 C 0.0102(11) 0.0151(14) 0.027(2) 0 -0.0062(13) 0 C3 C 0.0279(14) 0.0117(11) 0.099(3) -0.0015(11) -0.0407(18) 0.0002(16) C4 C 0.0235(12) 0.0101(10) 0.067(2) -0.0003(10) -0.0241(15) 0.0013(14) #======================================================================= # 10. MOLECULAR GEOMETRY loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag Ga O3 . . 1.91151(18) yes Ga O3 . 3_747 1.91151(18) yes Ga O1 . . 1.972(2) yes Ga O1 . 5_757 1.972(2) yes Ga O2 . 2_655 1.976(2) yes Ga O2 . 6_556 1.976(2) yes O1 C1 . . 1.263(3) yes C2 C1 . . 1.491(5) yes C2 C3 . . 1.404(3) yes C2 C3 . 7_555 1.404(3) yes C5 C6 . . 1.493(5) yes C5 C4 . . 1.379(3) yes C3 H3 . . 1.076(6) yes C3 C4 . . 1.389(5) yes C4 H4 . . 1.075(10) yes loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_2 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag O3 Ga O3 . . 3_747 180 yes O3 Ga O1 . . . 92.28(6) yes O3 Ga O1 . . 5_757 87.72(6) yes O3 Ga O2 . . 2_655 87.05(6) yes O3 Ga O2 . . 6_556 92.95(6) yes O3 Ga O1 3_747 . . 87.72(6) yes O3 Ga O1 3_747 . 5_757 92.28(6) yes O3 Ga O2 3_747 . 2_655 92.95(6) yes O3 Ga O2 3_747 . 6_556 87.05(6) yes O1 Ga O1 . . 5_757 180 yes O1 Ga O2 . . 2_655 87.09(9) yes O1 Ga O2 . . 6_556 92.91(9) yes O1 Ga O2 5_757 . 2_655 92.91(9) yes O1 Ga O2 5_757 . 6_556 87.09(9) yes O2 Ga O2 2_655 . 6_556 180 yes Ga O3 Ga . . 3_757 123.887(3) yes Ga O1 C1 . . . 132.3(2) yes Ga O2 C6 2_654 . . 132.6(2) yes C1 C2 C3 . . . 120.46(19) yes O1 C1 O1 . . 7_555 126.4(3) yes O1 C1 C2 . . . 116.82(17) yes C6 C5 C4 . . . 119.72(17) yes C6 C5 C4 . . 7_555 119.72(17) yes C4 C5 C4 . . 7_555 120.6(3) yes O2 C6 O2 . . 7_555 127.3(3) yes O2 C6 C5 . . . 116.35(16) yes O2 C6 C5 7_555 . . 116.35(16) yes C2 C3 H3 . . . 120.0(5) yes C2 C3 C4 . . . 120.0(2) yes H3 C3 C4 . . . 120.0(5) yes C5 C4 C3 . . . 120.0(2) yes C5 C4 H4 . . . 120.0(9) yes C3 C4 H4 . . . 120.0(9) yes #=======================================================================