# Electronic Supplementary Material (ESI) for CrystEngComm # This journal is © The Royal Society of Chemistry 2013 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_p42mnm _audit_creation_method SHELXL-97 _chemical_name_systematic ; diammonium tetrabromocuprate dihydrate ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'H12 Br4 Cu1 N2 O2' _chemical_formula_weight 455.29 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source N N 0.0061 0.0033 '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' Cu Cu 0.3201 1.2651 '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 tetragonal _symmetry_space_group_name_H-M P42/mnm loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-y+1/2, x+1/2, z+1/2' 'y+1/2, -x+1/2, z+1/2' '-x+1/2, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z+1/2' 'y, x, -z' '-y, -x, -z' '-x, -y, -z' 'x, y, -z' 'y-1/2, -x-1/2, -z-1/2' '-y-1/2, x-1/2, -z-1/2' 'x-1/2, -y-1/2, z-1/2' '-x-1/2, y-1/2, z-1/2' '-y, -x, z' 'y, x, z' _cell_length_a 7.95610(10) _cell_length_b 7.95610(10) _cell_length_c 8.2785(3) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 524.03(2) _cell_formula_units_Z 2 _cell_measurement_temperature 296.0(2) _cell_measurement_reflns_used xx? _cell_measurement_theta_min xx? _cell_measurement_theta_max xx? _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_max 0.37 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.885 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 422 _exptl_absorpt_coefficient_mu 17.286 _exptl_absorpt_correction_type multiscan _exptl_absorpt_correction_T_min xx? _exptl_absorpt_correction_T_max xx? _exptl_absorpt_process_details xx? _exptl_special_details ; ? ; _diffrn_ambient_temperature 296.0(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Xcalibur, Atlas, Gemini ultra' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean xxx _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6568 _diffrn_reflns_av_R_equivalents 0.0624 _diffrn_reflns_av_sigmaI/netI 0.0460 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.55 _diffrn_reflns_theta_max 40.99 _reflns_number_total 963 _reflns_number_gt 536 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlis CCD (Oxford Diffraction,2009)' _computing_cell_refinement 'CrysAlis CCD (Oxford Diffraction,2009)' _computing_data_reduction 'CrysAlis RED (Oxford Diffraction,2009)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics ?xx _computing_publication_material ?xx _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^)+(0.0280P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 963 _refine_ls_number_parameters 29 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0739 _refine_ls_R_factor_gt 0.0286 _refine_ls_wR_factor_ref 0.0590 _refine_ls_wR_factor_gt 0.0535 _refine_ls_goodness_of_fit_ref 0.821 _refine_ls_restrained_S_all 0.821 _refine_ls_shift/su_max 0.024 _refine_ls_shift/su_mean 0.005 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 Cu Cu 0.0000 0.0000 0.0000 0.02489(16) Uani 1 8 d S . . Br1 Br 0.21473(3) 0.21473(3) 0.0000 0.02414(10) Uani 1 4 d S . . Br2 Br 0.27908(4) 0.72092(4) 0.0000 0.02487(10) Uani 1 4 d S . . N N 0.0000 0.5000 0.2500 0.0307(8) Uani 1 4 d S . . O O 0.0000 0.0000 0.2360(3) 0.0399(9) Uani 1 4 d S . . H1 H 0.067(4) 0.067(4) 0.271(4) 0.026(10) Uiso 1 2 d S . . H2 H 0.022(12) 0.634(10) 0.262(8) 0.07(2) Uiso 0.50 1 d P . . H2' H -0.042(8) 0.450(8) 0.174(8) 0.06(2) Uiso 0.50 1 d P . . 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 Cu 0.0295(2) 0.0295(2) 0.0157(3) 0.000 0.000 -0.0115(3) Br1 0.02303(12) 0.02303(12) 0.02636(19) 0.000 0.000 -0.00436(15) Br2 0.02587(13) 0.02587(13) 0.02286(19) 0.000 0.000 0.00078(15) N 0.0330(12) 0.0330(12) 0.0260(17) 0.000 0.000 0.000 O 0.0496(15) 0.0496(15) 0.0205(13) 0.000 0.000 -0.030(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 Cu O 1.954(3) 9 ? Cu O 1.954(3) . ? Cu Br1 2.4161(4) . ? Cu Br1 2.4161(4) 9 ? Cu Br2 3.1401(4) 9_565 ? Cu Br2 3.1401(4) 1_545 ? Br1 N 3.5147 5_545 ? Br1 N 3.5147 . ? Br1 N 3.5147 13_665 ? Br1 N 3.5147 9_565 ? Br2 Cu 3.1401(4) 1_565 ? Br2 N 3.5075 9_565 ? Br2 N 3.5075 5 ? Br2 N 3.5075 . ? Br2 N 3.5075 13_675 ? N Br2 3.5075 9_565 ? N Br2 3.5075 3 ? N Br2 3.5075 11_566 ? 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 O Cu O 180.0 9 . ? O Cu Br1 90.0 9 . ? O Cu Br1 90.0 . . ? O Cu Br1 90.0 9 9 ? O Cu Br1 90.0 . 9 ? Br1 Cu Br1 180.000(9) . 9 ? O Cu Br2 90.0 9 9_565 ? O Cu Br2 90.0 . 9_565 ? Br1 Cu Br2 90.0 . 9_565 ? Br1 Cu Br2 90.0 9 9_565 ? O Cu Br2 90.0 9 1_545 ? O Cu Br2 90.0 . 1_545 ? Br1 Cu Br2 90.0 . 1_545 ? Br1 Cu Br2 90.0 9 1_545 ? Br2 Cu Br2 180.0 9_565 1_545 ? Cu Br1 N 96.483(6) . 5_545 ? Cu Br1 N 96.483(6) . . ? N Br1 N 106.322(3) 5_545 . ? Cu Br1 N 96.483(6) . 13_665 ? N Br1 N 72.150(2) 5_545 13_665 ? N Br1 N 167.034(12) . 13_665 ? Cu Br1 N 96.483(6) . 9_565 ? N Br1 N 167.034(12) 5_545 9_565 ? N Br1 N 72.150(2) . 9_565 ? N Br1 N 106.322(3) 13_665 9_565 ? Cu Br2 N 84.647(7) 1_565 9_565 ? Cu Br2 N 84.647(7) 1_565 5 ? N Br2 N 169.294(13) 9_565 5 ? Cu Br2 N 84.647(7) 1_565 . ? N Br2 N 72.321(2) 9_565 . ? N Br2 N 106.635(3) 5 . ? Cu Br2 N 84.647(7) 1_565 13_675 ? N Br2 N 106.635(3) 9_565 13_675 ? N Br2 N 72.321(2) 5 13_675 ? N Br2 N 169.294(13) . 13_675 ? Br2 N Br2 110.375(1) 9_565 3 ? Br2 N Br2 110.375(1) 9_565 11_566 ? Br2 N Br2 107.679(2) 3 11_566 ? Br2 N Br2 107.679(2) 9_565 . ? Br2 N Br2 110.375(1) 3 . ? Br2 N Br2 110.375(1) 11_566 . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 40.99 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 0.803 _refine_diff_density_min -0.747 _refine_diff_density_rms 0.154 _database_code_depnum_ccdc_archive 'CCDC 940956' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_p-421m_f _audit_creation_method SHELXL-97 _chemical_name_systematic ; diammonium tetrabromocuprate dihydrate ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'H12 Br4 Cu1 N2 O2' _chemical_formula_weight 455.29 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source N N 0.0061 0.0033 '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' Cu Cu 0.3201 1.2651 '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 tetragonal _symmetry_space_group_name_H-M P-421m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' '-y+1/2, -x+1/2, z' 'y+1/2, x+1/2, z' _cell_length_a 7.9005(11) _cell_length_b 7.9005(11) _cell_length_c 8.1982(16) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 511.71(14) _cell_formula_units_Z 2 _cell_measurement_temperature 120.0(2) _cell_measurement_reflns_used xx? _cell_measurement_theta_min xx? _cell_measurement_theta_max xx? _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_max 0.37 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.13 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.955 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 422 _exptl_absorpt_coefficient_mu 17.702 _exptl_absorpt_correction_type analytical _exptl_absorpt_correction_T_min xx? _exptl_absorpt_correction_T_max xx? _exptl_absorpt_process_details xx? _exptl_special_details ; ? ; _diffrn_ambient_temperature 120.0(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Xcalibur, Atlas, Gemini ultra' _diffrn_measurement_method 'omega scan' _diffrn_detector_area_resol_mean xxx? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 38885 _diffrn_reflns_av_R_equivalents 0.0528 _diffrn_reflns_av_sigmaI/netI 0.0218 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.58 _diffrn_reflns_theta_max 41.12 _reflns_number_total 1817 _reflns_number_gt 1364 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlis CCD (Oxford Diffraction,2009)' _computing_cell_refinement 'CrysAlis CCD (Oxford Diffraction,2009)' _computing_data_reduction 'CrysAlis RED (Oxford Diffraction,2009)' _computing_structure_solution 'SUPERFLIP (L.Palatinus and G.Chapuis,2007)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics xx? _computing_publication_material xx? _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^)+(0.0239P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0007(3) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.50(4) _refine_ls_number_reflns 1817 _refine_ls_number_parameters 38 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0322 _refine_ls_R_factor_gt 0.0175 _refine_ls_wR_factor_ref 0.0483 _refine_ls_wR_factor_gt 0.0469 _refine_ls_goodness_of_fit_ref 1.020 _refine_ls_restrained_S_all 1.020 _refine_ls_shift/su_max 0.462 _refine_ls_shift/su_mean 0.084 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 Cu Cu 0.0000 0.5000 0.25356(9) 0.01155(7) Uani 1 4 d S . . Br1 Br 0.783321(17) 0.283321(17) 0.25320(6) 0.01088(4) Uani 1 2 d S . . Br2 Br 0.277816(18) 0.222184(18) 0.24628(6) 0.01133(5) Uani 1 2 d S . . N1 N 0.0000 0.0000 0.5000 0.0089(9) Uani 1 4 d S . . N2 N 0.0000 0.0000 0.0000 0.0225(15) Uani 1 4 d S . . O1 O 0.0000 0.5000 0.4900(4) 0.0194(13) Uani 1 4 d S . . O2 O 0.0000 0.5000 0.0161(4) 0.0186(12) Uani 1 4 d S . . H1 H 0.066(4) 0.566(4) -0.457(5) 0.022 Uiso 1 2 d S . . H2 H 0.052(4) 0.552(4) -0.029(5) 0.022 Uiso 1 2 d S . . H3 H 0.046(3) -0.047(3) 0.547(3) 0.015(7) Uiso 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 Cu 0.01397(9) 0.01397(9) 0.00671(14) 0.000 0.000 -0.00469(13) Br1 0.01102(6) 0.01102(6) 0.01061(9) 0.00008(15) 0.00008(15) -0.00130(6) Br2 0.01223(6) 0.01223(6) 0.00952(9) 0.00023(15) -0.00023(15) 0.00013(6) N1 0.0064(12) 0.0064(12) 0.014(2) 0.000 0.000 0.000 N2 0.029(2) 0.029(2) 0.010(2) 0.000 0.000 0.000 O1 0.025(2) 0.025(2) 0.0076(15) 0.000 0.000 -0.016(3) O2 0.024(2) 0.024(2) 0.0074(15) 0.000 0.000 -0.012(3) _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 Cu O1 1.939(4) . ? Cu O2 1.947(4) . ? Cu Br1 2.4210(4) 2_665 ? Cu Br1 2.4210(4) 1_455 ? Cu Br2 3.1046(5) . ? Cu Br2 3.1046(5) 2_565 ? Br1 Cu 2.4210(4) 1_655 ? Br1 N1 3.4691(5) 1_655 ? Br1 N1 3.4691(5) 5_556 ? Br1 N2 3.5000(5) 1_655 ? Br1 N2 3.5000(5) 5 ? Br2 N2 3.4606(5) . ? Br2 N2 3.4606(5) 5 ? Br2 N1 3.4965(5) 5_556 ? Br2 N1 3.4965(5) . ? N1 Br1 3.4691(5) 3_566 ? N1 Br1 3.4691(5) 1_455 ? N1 Br1 3.4691(5) 2_655 ? N1 Br1 3.4691(5) 4_546 ? N2 Br2 3.4606(5) 4 ? N2 Br2 3.4606(5) 2 ? N2 Br2 3.4606(5) 3 ? 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 O1 Cu O2 180.000(1) . . ? O1 Cu Br1 90.07(2) . 2_665 ? O2 Cu Br1 89.93(2) . 2_665 ? O1 Cu Br1 90.07(2) . 1_455 ? O2 Cu Br1 89.93(2) . 1_455 ? Br1 Cu Br1 179.86(4) 2_665 1_455 ? O1 Cu Br2 91.102(14) . . ? O2 Cu Br2 88.898(14) . . ? Br1 Cu Br2 90.0 2_665 . ? Br1 Cu Br2 90.0 1_455 . ? O1 Cu Br2 91.102(14) . 2_565 ? O2 Cu Br2 88.898(14) . 2_565 ? Br1 Cu Br2 90.0 2_665 2_565 ? Br1 Cu Br2 90.0 1_455 2_565 ? Br2 Cu Br2 177.80(3) . 2_565 ? Cu Br1 N1 96.119(13) 1_655 1_655 ? Cu Br1 N1 96.120(13) 1_655 5_556 ? N1 Br1 N1 107.256(18) 1_655 5_556 ? Cu Br1 N2 96.148(12) 1_655 1_655 ? N1 Br1 N2 72.055(13) 1_655 1_655 ? N1 Br1 N2 167.713(6) 5_556 1_655 ? Cu Br1 N2 96.148(12) 1_655 5 ? N1 Br1 N2 167.713(6) 1_655 5 ? N1 Br1 N2 72.055(13) 5_556 5 ? N2 Br1 N2 105.894(18) 1_655 5 ? Cu Br2 N2 85.494(9) . . ? Cu Br2 N2 85.494(9) . 5 ? N2 Br2 N2 107.640(18) . 5 ? Cu Br2 N1 84.243(9) . 5_556 ? N2 Br2 N1 169.716(7) . 5_556 ? N2 Br2 N1 72.199(13) 5 5_556 ? Cu Br2 N1 84.243(9) . . ? N2 Br2 N1 72.199(13) . . ? N2 Br2 N1 169.716(7) 5 . ? N1 Br2 N1 106.045(18) 5_556 . ? Br1 N1 Br1 109.887(9) 3_566 1_455 ? Br1 N1 Br1 109.887(9) 3_566 2_655 ? Br1 N1 Br1 108.643(18) 1_455 2_655 ? Br1 N1 Br1 108.643(18) 3_566 4_546 ? Br1 N1 Br1 109.887(9) 1_455 4_546 ? Br1 N1 Br1 109.887(9) 2_655 4_546 ? Br2 N2 Br2 109.902(9) . 4 ? Br2 N2 Br2 108.613(18) . 2 ? Br2 N2 Br2 109.902(9) 4 2 ? Br2 N2 Br2 109.902(9) . 3 ? Br2 N2 Br2 108.613(18) 4 3 ? Br2 N2 Br2 109.902(9) 2 3 ? _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 41.12 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.763 _refine_diff_density_min -0.548 _refine_diff_density_rms 0.110 _database_code_depnum_ccdc_archive 'CCDC 940957' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_p42mnm _audit_creation_method SHELXL-97 _chemical_name_systematic ; diammonium tetrabromocuprate dihydrate ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'Br4 Cu H12 N2 O2' _chemical_formula_weight 451.00 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source N N 0.0000 0.0000 '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 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M P42/mnm loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' '-y+1/2, x+1/2, z+1/2' 'y+1/2, -x+1/2, z+1/2' '-x+1/2, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z+1/2' 'y, x, -z' '-y, -x, -z' '-x, -y, -z' 'x, y, -z' 'y-1/2, -x-1/2, -z-1/2' '-y-1/2, x-1/2, -z-1/2' 'x-1/2, -y-1/2, z-1/2' '-x-1/2, y-1/2, z-1/2' '-y, -x, z' 'y, x, z' _cell_length_a 7.9940(11) _cell_length_b 7.9940(11) _cell_length_c 8.2750(17) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 528.81(15) _cell_formula_units_Z 2 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_max 6 _exptl_crystal_size_mid 4 _exptl_crystal_size_min 3 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.832 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 41 _exptl_absorpt_coefficient_mu 0.000 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.82920 _diffrn_radiation_type neutron _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 1811 _diffrn_reflns_av_R_equivalents 0.0596 _diffrn_reflns_av_sigmaI/netI 0.0522 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -2 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 3.54 _diffrn_reflns_theta_max 35.47 _reflns_number_total 688 _reflns_number_gt 482 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0415P)^2^+0.0424P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.161(10) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 688 _refine_ls_number_parameters 44 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0656 _refine_ls_R_factor_gt 0.0337 _refine_ls_wR_factor_ref 0.0865 _refine_ls_wR_factor_gt 0.0760 _refine_ls_goodness_of_fit_ref 1.001 _refine_ls_restrained_S_all 1.001 _refine_ls_shift/su_max 0.002 _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 Cu Cu 0.0000 0.0000 0.5000 0.0254(3) Uani 1 8 d S . . Br1 Br 0.21454(8) 0.21454(8) 0.5000 0.0242(2) Uani 1 4 d S . . Br2 Br 0.27931(9) 0.72069(9) 0.5000 0.0250(2) Uani 1 4 d S . . O O 0.5000 0.5000 0.76384(13) 0.0386(3) Uani 1 4 d S . . N N 0.0000 0.5000 0.2500 0.03193(19) Uani 1 4 d S . . H1 H 0.43035(15) 0.56965(15) 0.6973(2) 0.0475(4) Uani 1 2 d S . . H2 H -0.0690(4) 0.5787(4) 0.1786(3) 0.0639(12) Uani 0.653(9) 1 d P . . H2' H 0.0804(8) 0.5640(10) 0.1799(7) 0.081(3) Uani 0.347(9) 1 d P . . 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 Cu 0.0290(3) 0.0290(3) 0.0183(4) 0.000 0.000 -0.0114(5) Br1 0.0235(3) 0.0235(3) 0.0256(4) 0.000 0.000 -0.0045(3) Br2 0.0258(3) 0.0258(3) 0.0234(4) 0.000 0.000 0.0012(3) O 0.0493(5) 0.0493(5) 0.0172(4) 0.000 0.000 0.0248(7) N 0.0344(2) 0.0344(2) 0.0270(3) 0.000 0.000 0.000 H1 0.0532(6) 0.0532(6) 0.0360(7) 0.0054(4) -0.0054(4) 0.0171(8) H2 0.0708(18) 0.0615(19) 0.0595(19) 0.0127(12) -0.0140(12) 0.0166(15) H2' 0.077(4) 0.096(5) 0.071(4) 0.018(3) 0.017(3) -0.021(4) _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 Cu O 1.9542(12) 3_544 ? Cu Br1 2.4254(10) . ? Cu Br2 3.1577(11) 1_545 ? Br1 H2' 2.520(5) 4_455 ? Br1 O 3.1147(11) 3_544 ? Br2 H1 2.3623(18) . ? Br2 H2 2.496(2) 4_455 ? O H1 0.9610(18) . ? N H2' 1.005(5) . ? N H2 1.024(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 O H1 Br2 171.26(16) . . ? N H2 Br2 176.4(3) . 3_554 ? N H2' Br1 178.0(6) . 3_554 ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 35.47 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.550 _refine_diff_density_min -0.539 _refine_diff_density_rms 0.108 _database_code_depnum_ccdc_archive 'CCDC 940958' ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # data_fin _audit_creation_method SHELXL-97 _chemical_name_systematic ; diammonium tetrabromocuprate dihydrate ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'Br4 Cu H12 N2 O2' _chemical_formula_weight 451.00 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source N N 0.0000 0.0000 '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 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Cu Cu 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Br Br 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting tetragonal _symmetry_space_group_name_H-M P-421m loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z' 'y, -x, -z' '-y, x, -z' '-x+1/2, y+1/2, -z' 'x+1/2, -y+1/2, -z' '-y+1/2, -x+1/2, z' 'y+1/2, x+1/2, z' _cell_length_a 7.8690(11) _cell_length_b 7.8690(11) _cell_length_c 8.2480(16) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 510.73(14) _cell_formula_units_Z 2 _cell_measurement_temperature 20(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_max 6 _exptl_crystal_size_mid 4 _exptl_crystal_size_min 3 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.933 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 41 _exptl_absorpt_coefficient_mu 0.000 _exptl_absorpt_correction_type ? _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 20(2) _diffrn_radiation_wavelength 0.8320 _diffrn_radiation_type neutron _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type ? _diffrn_measurement_method ? _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 1926 _diffrn_reflns_av_R_equivalents 0.0900 _diffrn_reflns_av_sigmaI/netI 0.0629 _diffrn_reflns_limit_h_min -2 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 12 _diffrn_reflns_limit_l_min -12 _diffrn_reflns_limit_l_max 12 _diffrn_reflns_theta_min 2.47 _diffrn_reflns_theta_max 33.07 _reflns_number_total 1053 _reflns_number_gt 839 _reflns_threshold_expression >2sigma(I) _computing_data_collection ? _computing_cell_refinement ? _computing_data_reduction ? _computing_structure_solution 'SUPERFLIP (L.Palatinus and G.Chapuis,2007)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics ? _computing_publication_material ? _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^)+(0.0464P)^2^+0.3272P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens diffmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.163(9) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0(10) _refine_ls_number_reflns 1053 _refine_ls_number_parameters 61 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0554 _refine_ls_R_factor_gt 0.0416 _refine_ls_wR_factor_ref 0.0935 _refine_ls_wR_factor_gt 0.0857 _refine_ls_goodness_of_fit_ref 1.070 _refine_ls_restrained_S_all 1.070 _refine_ls_shift/su_max 0.041 _refine_ls_shift/su_mean 0.007 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 Cu Cu 0.0000 0.5000 0.2534(2) 0.0044(2) Uani 1 4 d S . . Br1 Br 0.78239(7) 0.28239(7) 0.25341(17) 0.00379(17) Uani 1 2 d S . . Br2 Br 0.27718(8) 0.22282(8) 0.24594(18) 0.00414(17) Uani 1 2 d S . . N1 N 0.0000 0.0000 0.5000 0.0087(3) Uani 1 4 d S . . N2 N 0.0000 0.0000 0.0000 0.0077(3) Uani 1 4 d S . . O1 O 0.0000 0.5000 0.4923(3) 0.0094(5) Uani 1 4 d S . . O2 O 0.0000 0.5000 0.0160(3) 0.0076(5) Uani 1 4 d S . . H1 H 0.0712(4) 0.5712(4) 0.5607(3) 0.0235(7) Uani 1 2 d S . . H2 H 0.0708(4) 0.5708(4) -0.0527(4) 0.0250(7) Uani 1 2 d S . . H3 H 0.0839(3) 0.0668(4) 0.5718(3) 0.0317(5) Uani 1 1 d . . . H4 H 0.0815(3) 0.0703(3) 0.0723(2) 0.0241(4) 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 Cu 0.0058(3) 0.0058(3) 0.0016(4) 0.000 0.000 -0.0017(3) Br1 0.0050(2) 0.0050(2) 0.0014(3) -0.0004(4) -0.0004(4) -0.0001(2) Br2 0.0052(2) 0.0052(2) 0.0020(3) -0.0005(3) 0.0005(3) 0.0007(2) N1 0.0105(5) 0.0105(5) 0.0049(5) 0.000 0.000 0.000 N2 0.0089(5) 0.0089(5) 0.0053(5) 0.000 0.000 0.000 O1 0.0139(8) 0.0139(8) 0.0004(7) 0.000 0.000 0.0002(15) O2 0.0104(7) 0.0104(7) 0.0019(7) 0.000 0.000 -0.0078(14) H1 0.0268(11) 0.0268(11) 0.0171(11) -0.0049(9) -0.0049(9) -0.0115(17) H2 0.0286(11) 0.0286(11) 0.0178(11) 0.0040(10) 0.0040(10) -0.0088(19) H3 0.0318(11) 0.0360(11) 0.0274(10) -0.0072(9) -0.0070(9) -0.0080(11) H4 0.0236(9) 0.0258(9) 0.0231(8) -0.0066(8) -0.0065(7) -0.0061(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 Cu O2 1.957(3) . ? Cu O1 1.971(3) . ? Cu Br1 2.4216(9) 1_455 ? Cu Br2 3.0852(10) . ? Br1 O2 3.1141(18) 1_655 ? Br1 O1 3.1218(18) 1_655 ? Br2 H1 2.322(4) 4_656 ? Br2 H2 2.325(4) 4_655 ? Br2 H4 2.421(2) . ? N1 H3 1.031(2) . ? N2 H4 1.036(2) . ? O1 H1 0.972(4) . ? O2 H2 0.970(4) . ? H1 Br2 2.322(4) 3_566 ? H2 Br2 2.325(4) 3_565 ? H3 Br1 2.434(2) 3_566 ? 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 O1 H1 Br2 172.1(3) . 3_566 ? O2 H2 Br2 172.5(4) . 3_565 ? N1 H3 Br1 178.4(2) . 3_566 ? N2 H4 Br2 177.45(19) . . ? _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 33.07 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.932 _refine_diff_density_min -0.972 _refine_diff_density_rms 0.201 _database_code_depnum_ccdc_archive 'CCDC 940959'