# Electronic Supplementary Material (ESI) for Journal of Materials Chemistry A # This journal is © The Royal Society of Chemistry 2013 data_global _journal_name_full J.Mater.Chem. _journal_coden_cambridge 1145 #TrackingRef '- PTI-Br.cif' #============================================================================= # SUBMISSION DETAILS _publ_contact_author_name 'Michael J. Bojdys' _publ_contact_author_address ; Department of Chemistry and Centre for Materials Discovery Crown Street Liverpool L69 7ZD UK ; _publ_contact_author_email m.j.bojdys.02@cantab.net _publ_contact_author_fax ? _publ_contact_author_phone +447863699856 #============================================================================= # TITLE AND AUTHOR LIST _publ_section_title ; Tuning of gallery heights in a crystalline 2D carbon nitride network ; loop_ _publ_author_name _publ_author_address 'Chong, Samantha Y.' ; Department of Chemistry and Centre for Materials Discovery Crown Street Liverpool L69 7ZD UK ; 'Jones, James T. A.' ; Department of Chemistry and Centre for Materials Discovery Crown Street Liverpool L69 7ZD UK ; 'Khimyak, Yaroslav Z.' ; School of Pharmacy University of East Anglia Norwich Research Park Norwich NR4 7TJ UK ; 'Cooper, Andrew I.' ; Department of Chemistry and Centre for Materials Discovery Crown Street Liverpool L69 7ZD UK ; 'Thomas, Arne' ; Technische Universitat Berlin Institut f r Chemie, Sekr. C2 Hardenbergstrasse 40 10623 Berlin Germany ; 'Antonietti, Markus' ; Max Planck Institute of Colloids and Interfaces Research Campus Golm 14424 Potsdam Germany ; 'Bojdys, Michael J.' ; Department of Chemistry and Centre for Materials Discovery Crown Street Liverpool L69 7ZD UK ; #============================================================================== # 4. TEXT (For Acta Cryst. C and E, include the text of your paper in the CIF) _publ_section_abstract ; Poly(triazine imide) - a 2D layered network - can be obtained as an intercalation compound with halides from the ionothermal condensation of dicyandiamide in a eutectic salt melt. The gallery height of the intercalated material can be tuned via the composition of the eutectic melt and post- synthetic modification. Herein, we report the synthesis of poly(triazine imide) with intercalated bromide ions (PTI/Br) from a lithium bromide and potassium bromide salt melt. PTI/Br has a hexagonal unit-cell (P63cm (no. 185); a = 8.500390(68) , c = 7.04483(17) ) which contains two layers of imide- bridged triazine (C3N3) units stacked in an AB-fashion as corroborated by solid-state NMR, FTIR spectroscopy and high-resolution TEM. Contrasted with a recently reported, analogous PTI/Li+Cl- from a LiCl/KCl eutectic, the layer- stacking distance was expanded from 3.38 to 3.52 going from chloride to bromide, respectively, - an exceptionally large spacing for aromatic, discotic systems (c.f. graphite with 3.35 ). Subsequent treatment of PTI/Br with concentrated ammonium fluoride yields poly(triazine imide) with intercalated fluoride ions (PTI/F) (P63/m (no. 176); a = 8.4212(4) , c = 6.6381(5) ) as a statistical phase mix with PTI/Br. Fluoride intercalation leads to a contraction of the gallery height to 3.32 . ; _publ_section_exptl_refinement ; Rietveld refinement of initial model based on PTI incalcated with LiCl using synchrotron PXRD data collected on beamline I11 at DLS and TOPAS-Academic v. 4.1 (A.A. Coelho, TOPAS-Academic v. 4.1, 2007, http://www.topas-academic.net). All atomic positions were refined with soft costrains on C-N bond lengths and angles and one planarity restraint. Isotropic displacement parameters were refined for all atoms, except Br, for which a ADPs were refined. ; #============================================================================= data_PTIBr _database_code_depnum_ccdc_archive 'CCDC 902173' #TrackingRef '- PTI-Br.cif' # CHEMICAL DATA _chemical_name_systematic ; ? ; _chemical_name_common 'LiBr intercalated poly(triazide imide)' _chemical_formula_moiety 'C12 Br2 Li2 N18' _chemical_formula_sum 'C12 Br2 Li1.998 N18' _chemical_formula_weight 569.97 #============================================================================= # POWDER SPECIMEN AND CRYSTAL DATA _space_group_crystal_system hexagonal _space_group_IT_number 185 _space_group_name_H-M_alt 'P 63 c m' _space_group_name_Hall 'P 6c -2' loop_ _symmetry_equiv_pos_site_id _symmetry_equiv_pos_as_xyz #<--must include 'x,y,z' 1 'x, y, z ' 2 'x-y, x, 0.5+z ' 3 '-y, x-y, z ' 4 '-x, -y, 0.5+z ' 5 '-x+y, -x, z ' 6 'y, -x+y, 0.5+z ' 7 '-x+y, y, 0.5+z ' 8 'x, x-y, 0.5+z ' 9 '-y, -x, 0.5+z ' 10 'y, x, z ' 11 'x-y, -y, z ' 12 '-x, -x+y, z ' _cell_length_a 8.50075(7) _cell_length_b 8.50075(7) _cell_length_c 7.04483(17) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 120 _cell_volume 440.875(12) _cell_formula_units_Z 1 _cell_measurement_temperature 298 _exptl_crystal_density_diffrn 2.147 _exptl_crystal_F_000 274.0 _cell_special_details ; ? ; _pd_spec_mounting ; 'special glass capillary' ; _pd_spec_mount_mode transmission _pd_spec_shape cylinder # The next four fields are normally only needed for transmission experiments. _exptl_absorpt_coefficient_mu 6.81(1) _exptl_absorpt_correction_type cylinder #============================================================================== # EXPERIMENTAL DATA _exptl_special_details ; ? ; # The following item is used to identify the equipment used to record # the powder pattern when the diffractogram was measured at a laboratory # other than the authors' home institution, e.g. when neutron or synchrotron # radiation is used. _pd_instr_location ; 'Beamline I11, Diamond Light Source' ; _pd_calibration_special_details # description of the method used # to calibrate the instrument ; ? ; _diffrn_ambient_temperature 298 _diffrn_radiation_type synchrotron _diffrn_detector PSD _diffrn_detector_type Mythen-II # make or model of detector _pd_meas_scan_method fixed _pd_meas_special_details ; ? ; _diffrn_radiation_wavelength 0.827157 _diffrn_radiation_monochromator 'double Si(111)' _pd_meas_2theta_range_min 1.088 _pd_meas_2theta_range_max 91.116 _pd_meas_2theta_range_inc 0.004 #============================================================================== # REFINEMENT DATA # Use the next field to give any special details about the fitting of the # powder pattern. _pd_proc_ls_special_details ; ? ; # The next three items are given as text. _pd_proc_ls_profile_function ; pseudo-Voigt with anisotropic microstrain broadening (P.W. Stephens, J. Appl. Cryst. 1999, 32, 281-289) ; _pd_proc_ls_background_function 'Chebyshev polynomial' _pd_proc_ls_pref_orient_corr ; 'none' ; _pd_proc_ls_prof_R_factor 0.017 _pd_proc_ls_prof_wR_factor 0.022 _refine_special_details ; ? ; _refine_ls_matrix_type full _refine_ls_weighting_scheme sigma _refine_ls_number_parameters 33 _refine_ls_number_restraints 8 _refine_ls_number_constraints 0 _refine_ls_goodness_of_fit_all 1.93 _refine_ls_shift/su_max 0.0 _refine_ls_shift/su_mean 0.0 _pd_proc_2theta_range_min 5 _pd_proc_2theta_range_max 40 _pd_proc_2theta_range_inc 0.004 _pd_proc_wavelength 0.827157 _computing_data_collection GDA _computing_cell_refinement 'TOPAS-Academic v.4.1' _computing_structure_solution none _pd_calc_method 'Rietveld Refinement' _computing_structure_refinement 'TOPAS-Academic v.4.1' _computing_molecular_graphics ? _computing_publication_material 'Platon (Spek, Acta Cryst. 2009)' #============================================================================== # ATOMIC COORDINATES AND DISPLACEMENT PARAMETERS loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_Wyckoff_symbol _atom_site_B_iso_or_equiv Br 0 0 0.5078(25) 1 2 a 12.34 Li 0.2194(44) 0 0.236(12) 0.333(17) 6 c 6.5(11) C2 0.6429(17) 0.1698(11) 0.2877(36) 1 12 d 10.58(25) N3 0.50387(75) 0.19045(96) 0.2889(27) 1 12 d 9.05(16) N4 0.62290(71) 0 0.2839(33) 1 6 c 10.14(20) loop_ _atom_site_aniso_label _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 _atom_site_aniso_type_symbol Br 0.1718(11) 0.1718(11) 0.1253(15) 0.08588(53) 0 0 Br #============================================================================== # MOLECULAR GEOMETRY _geom_special_details none loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_1 _geom_bond_site_symmetry_2 _geom_bond_publ_flag N3 C2 1.279(4) . . yes N3 C2 1.329(3) . 5_665 yes N4 C2 1.367(2) . . yes N4 C2 1.367(2) . 11_555 yes 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_2 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C2 N3 C2 119.5(2) . . 5_665 yes C2 N4 C2 132.3(2) . . 11_555 yes N3 C2 N4 120.66(19) . . . yes N3 C2 N3 120.50(17) . . 3_655 yes N4 C2 N3 118.8(2) . . 3_655 yes # The following lines are used to test the character set of files sent by # network email or other means. They are not part of the CIF data set. # abcdefghijklmnopqrstuvwxyzABCDEFGHIJKLMNOPQRSTUVWXYZ0123456789 # !@#$%^&*()_+{}:"~<>?|\-=[];'`,./