Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Massimiliano Arca' 'M. Carla Aragoni' 'Francesco A. Devillanova' 'Francesco Isaia' 'Vito Lippolis' 'Annalisa Mancini' 'Luca Pala' 'Alexandra M. Z. Slawin' 'Derek Woollins' _publ_section_title ; First Example of Infinite Polybromide 2D-Network ; _publ_contact_author_name ; Massimiliano Arca ; _publ_contact_author_address ; Dr Massimiliano Arca Dipartimento di Chimica Inorganica ed Analitica Università degli Studi di Cagliari Cittadella Universitaria di Monserr S.S. 554 bivio per Sestu Monserrato - Cagliari 09042 ITALY ; _publ_contact_author_email ; marca@unica.it ; _publ_contact_author_fax ; +39 070 675 4456 ; _publ_contact_author_phone ; +39 070 675 4483 ; _publ_requested_journal 'Chemical Communications' _publ_section_abstract ; The reaction of the neutral dithiolene [Pd(Et2timdt)2] (Et2timdt = formally monoreduced diethylimidazolidine-2,4,5-trithione) with an excess of Br2 yielded few crystals of [1Et·2Br]2+(Br-)2(Br2)3 as a by-product (1Et = 4,5,9,10-tetrathiocino-[1,2-b:5,6-b’]-1,3,6,8-tetraethyl- diimidazolyl-2,7-dithione): X-ray diffraction analysis showed that this compound represents the first example of a polybromide 2D-network templated by [1Et·2Br]+2 dications, and featuring all the Br-Br distances shorter than those found in solid state bromine. ; data_1Et5Br2 _database_code_CSD 213066 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C14 H20 Br2 N4 S6.(Br2)3.(Br)2' _chemical_formula_sum 'C14 H20 Br10 N4 S6' _chemical_formula_weight 1235.80 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 12.893(2) _cell_length_b 13.401(2) _cell_length_c 10.6610(17) _cell_angle_alpha 90.00 _cell_angle_beta 112.671(3) _cell_angle_gamma 90.00 _cell_volume 1699.6(5) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 122 _cell_measurement_theta_min 12 _cell_measurement_theta_max 168 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.08 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.415 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1156 _exptl_absorpt_coefficient_mu 12.173 _exptl_absorpt_correction_type Multiscan _exptl_absorpt_correction_T_min 0.653024 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 0.9 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 8183 _diffrn_reflns_av_R_equivalents 0.0680 _diffrn_reflns_av_sigmaI/netI 0.0968 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -9 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 1.71 _diffrn_reflns_theta_max 23.25 _reflns_number_total 2379 _reflns_number_gt 1168 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SHELXTL' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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. ; _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^)+(0.0560P)^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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0008(2) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2379 _refine_ls_number_parameters 155 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1187 _refine_ls_R_factor_gt 0.0469 _refine_ls_wR_factor_ref 0.1095 _refine_ls_wR_factor_gt 0.0909 _refine_ls_goodness_of_fit_ref 0.849 _refine_ls_restrained_S_all 0.849 _refine_ls_shift/su_max 0.006 _refine_ls_shift/su_mean 0.001 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 Br1 Br 0.12442(11) 0.81126(9) -0.74042(12) 0.0709(4) Uani 1 1 d . . . S1 S 0.1157(2) 0.6814(2) -0.8777(3) 0.0615(9) Uani 1 1 d . . . C1 C 0.2364(9) 0.6177(8) -0.7764(10) 0.045(3) Uani 1 1 d . . . N2 N 0.3416(8) 0.6371(6) -0.7616(8) 0.048(2) Uani 1 1 d . . . C3 C 0.4115(8) 0.5627(7) -0.6820(10) 0.041(3) Uani 1 1 d . . . S3 S 0.5544(2) 0.5592(2) -0.6465(3) 0.0579(8) Uani 1 1 d . . . C4 C 0.3455(8) 0.4986(7) -0.6458(9) 0.041(2) Uani 1 1 d . . . S4 S 0.3791(2) 0.38878(19) -0.5531(3) 0.0569(8) Uani 1 1 d . . . N5 N 0.2362(7) 0.5366(7) -0.7009(8) 0.046(2) Uani 1 1 d . . . C6 C 0.3776(11) 0.7172(10) -0.8313(14) 0.083(4) Uani 1 1 d . . . H6A H 0.4314 0.6916 -0.8666 0.100 Uiso 1 1 calc R . . H6B H 0.3135 0.7436 -0.9065 0.100 Uiso 1 1 calc R . . C7 C 0.4284(13) 0.7940(11) -0.7325(17) 0.121(6) Uani 1 1 d . . . H7A H 0.4530 0.8475 -0.7742 0.181 Uiso 1 1 calc R . . H7B H 0.4917 0.7669 -0.6587 0.181 Uiso 1 1 calc R . . H7C H 0.3743 0.8188 -0.6986 0.181 Uiso 1 1 calc R . . C8 C 0.1390(8) 0.4937(9) -0.6840(12) 0.067(3) Uani 1 1 d . . . H8A H 0.1487 0.4220 -0.6723 0.080 Uiso 1 1 calc R . . H8B H 0.0723 0.5060 -0.7651 0.080 Uiso 1 1 calc R . . C9 C 0.1233(10) 0.5383(12) -0.5616(15) 0.104(5) Uani 1 1 d . . . H9A H 0.0589 0.5086 -0.5522 0.155 Uiso 1 1 calc R . . H9B H 0.1121 0.6090 -0.5739 0.155 Uiso 1 1 calc R . . H9C H 0.1889 0.5255 -0.4811 0.155 Uiso 1 1 calc R . . Br2 Br 0.15539(9) 0.49986(8) -1.05737(10) 0.0546(4) Uani 1 1 d . . . Br3 Br 0.40246(14) 0.49560(12) -1.01532(15) 0.1077(6) Uani 1 1 d . . . Br4 Br 0.17868(12) 0.34082(10) -1.25723(14) 0.0842(5) Uani 1 1 d . . . Br5 Br 0.18418(13) 0.20718(11) -1.39839(14) 0.0941(6) Uani 1 1 d . . . 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 Br1 0.0792(10) 0.0729(8) 0.0607(9) 0.0043(7) 0.0270(7) 0.0218(7) S1 0.060(2) 0.0619(19) 0.0501(19) 0.0034(15) 0.0074(14) 0.0118(16) C1 0.045(8) 0.055(7) 0.031(7) -0.005(6) 0.009(5) 0.000(6) N2 0.049(7) 0.047(6) 0.048(6) 0.004(5) 0.018(5) -0.006(5) C3 0.043(7) 0.041(6) 0.041(6) 0.002(5) 0.019(5) 0.010(6) S3 0.048(2) 0.081(2) 0.0496(19) 0.0106(16) 0.0248(14) -0.0002(16) C4 0.039(7) 0.043(6) 0.038(6) 0.004(6) 0.013(5) -0.005(6) S4 0.052(2) 0.0500(17) 0.061(2) 0.0080(15) 0.0132(15) -0.0066(14) N5 0.030(6) 0.076(7) 0.037(5) -0.003(5) 0.017(4) -0.006(5) C6 0.064(9) 0.079(11) 0.096(12) 0.019(9) 0.020(8) 0.003(7) C7 0.144(16) 0.089(11) 0.147(17) 0.057(12) 0.076(13) 0.026(11) C8 0.029(7) 0.085(9) 0.081(9) 0.033(8) 0.014(6) 0.010(6) C9 0.051(9) 0.162(14) 0.118(13) 0.013(11) 0.055(9) 0.019(8) Br2 0.0569(7) 0.0514(7) 0.0525(7) -0.0014(6) 0.0177(5) -0.0052(6) Br3 0.1311(14) 0.1267(13) 0.0815(10) -0.0452(10) 0.0589(9) -0.0635(11) Br4 0.1013(11) 0.0700(9) 0.0675(10) 0.0033(7) 0.0173(8) -0.0153(8) Br5 0.0919(12) 0.1229(13) 0.0653(9) -0.0161(9) 0.0279(8) -0.0018(9) _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 Br1 S1 2.249(3) . ? S1 C1 1.738(10) . ? C1 N2 1.329(12) . ? C1 N5 1.354(12) . ? N2 C3 1.392(12) . ? N2 C6 1.479(14) . ? C3 C4 1.365(12) . ? C3 S3 1.733(10) . ? S3 S4 2.084(4) 3_664 ? C4 N5 1.398(11) . ? C4 S4 1.732(10) . ? S4 S3 2.084(4) 3_664 ? N5 C8 1.452(12) . ? C6 C7 1.437(17) . ? C8 C9 1.519(15) . ? Br3 Br3 2.411(3) 3_663 ? Br4 Br5 2.358(2) . ? 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 C1 S1 Br1 99.6(3) . . ? N2 C1 N5 108.8(9) . . ? N2 C1 S1 127.3(9) . . ? N5 C1 S1 123.9(9) . . ? C1 N2 C3 108.8(9) . . ? C1 N2 C6 125.9(10) . . ? C3 N2 C6 124.9(10) . . ? C4 C3 N2 107.3(9) . . ? C4 C3 S3 130.3(8) . . ? N2 C3 S3 122.4(8) . . ? C3 S3 S4 101.5(3) . 3_664 ? C3 C4 N5 106.8(8) . . ? C3 C4 S4 130.6(8) . . ? N5 C4 S4 122.6(8) . . ? C4 S4 S3 102.3(3) . 3_664 ? C1 N5 C4 108.0(8) . . ? C1 N5 C8 126.3(9) . . ? C4 N5 C8 125.6(9) . . ? C7 C6 N2 107.1(11) . . ? N5 C8 C9 111.0(10) . . ? 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 Br1 S1 C1 N2 -81.0(9) . . . . ? Br1 S1 C1 N5 100.7(8) . . . . ? N5 C1 N2 C3 4.2(10) . . . . ? S1 C1 N2 C3 -174.2(7) . . . . ? N5 C1 N2 C6 177.4(10) . . . . ? S1 C1 N2 C6 -1.0(15) . . . . ? C1 N2 C3 C4 -1.5(11) . . . . ? C6 N2 C3 C4 -174.8(10) . . . . ? C1 N2 C3 S3 177.1(7) . . . . ? C6 N2 C3 S3 3.8(14) . . . . ? C4 C3 S3 S4 -78.4(9) . . . 3_664 ? N2 C3 S3 S4 103.4(8) . . . 3_664 ? N2 C3 C4 N5 -1.7(10) . . . . ? S3 C3 C4 N5 179.9(7) . . . . ? N2 C3 C4 S4 177.4(7) . . . . ? S3 C3 C4 S4 -1.1(15) . . . . ? C3 C4 S4 S3 81.0(9) . . . 3_664 ? N5 C4 S4 S3 -100.1(7) . . . 3_664 ? N2 C1 N5 C4 -5.3(10) . . . . ? S1 C1 N5 C4 173.2(7) . . . . ? N2 C1 N5 C8 176.9(9) . . . . ? S1 C1 N5 C8 -4.6(14) . . . . ? C3 C4 N5 C1 4.3(10) . . . . ? S4 C4 N5 C1 -174.9(7) . . . . ? C3 C4 N5 C8 -177.9(9) . . . . ? S4 C4 N5 C8 2.9(13) . . . . ? C1 N2 C6 C7 105.7(12) . . . . ? C3 N2 C6 C7 -82.2(14) . . . . ? C1 N5 C8 C9 -91.0(12) . . . . ? C4 N5 C8 C9 91.5(13) . . . . ? _diffrn_measured_fraction_theta_max 0.979 _diffrn_reflns_theta_full 23.25 _diffrn_measured_fraction_theta_full 0.979 _refine_diff_density_max 0.899 _refine_diff_density_min -0.646 _refine_diff_density_rms 0.120