Supplementary Material (ESI) for Journal of Materials Chemistry This journal is © The Royal Society of Chemistry 2003 data_global _journal_coden_Cambridge 1145 _publ_contact_author_name 'Dr Ann M. Chippindale' _publ_contact_author_address ; Department of Chemistry The University of Reading Whiteknights Reading RG6 6AD UNITED KINGDOM ; _publ_contact_author_phone ' 01183788448 ' _publ_contact_author_fax ' 01183786331 ' _publ_contact_author_email 'a.m.chippindale@rdg.ac.uk ' #========================================================== #========================================================== # 3. TITLE AND AUTHOR LIST _publ_section_title ; Synthesis and characterisation of a new layered ammonium manganese(II) diphosphate (NH4)2[Mn3(P2O7)2(H2O)2] ; loop_ _publ_author_name 'Chippindale, Ann M.' 'Gaslain, Fabrice M.' 'Bond, Andrew D.' 'Powell, Anthony V.' _publ_requested_journal 'Journal of Materials Chemistry' _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo G., Guagliardi A., Burla M.C., Polidori, G. & Camalli, M. (1994) SIR92 - a program for automatic solution of crystal structures by direct methods. J. Appl. Cryst. 27, 435. ATOMS for Windows v4.0, Shape Software, 521 Hidden Valley Road, Kingsport TN, USA Carruthers, J.R. and Watkin, D.J. (1979), Acta Cryst, A35, 698-699. Larsen, A. C. (1967), Acta Cryst. 23, 440-449. North, A.C.T., Phillips, D.C. and Mathews, F.S., (1968), Acta Cryst, A24, 351-359. Watkin, D.J., Prout, C.K. Carruthers, J.R. & Betteridge, P.W. (1996) CRYSTALS Issue 10. Chemical Crystallography Laboratory, OXFORD, UK. Watkin, D.J., Prout, C.K. & Pearce, L.J. (1996) CAMERON, Chemical Crystallography Laboratory, OXFORD, UK. Watkin, D.J., Prout, C.K., Lilley, P.M.deQ. (1994), RC93, Chemical Crystallography Laboratory, Oxford, UK. ; data_adb6 _database_code_CSD 208151 _audit_creation_method CRYSTALS _audit_creation_date 03-01-25 # [NH4]2[Mn3H2P4O16] #========================================================== ## -----------------REFERENCES ----------------------## #========================================================== # Diffractometer details #========================================================== _diffrn_radiation_monochromator graphite _diffrn_measurement_device ' Enraf-Nonius CAD4 ' _computing_data_collection 'CAD-4 software (Enraf-Nonius, 1989)' _computing_data_reduction ; RC93 (Watkin, D.J., Prout, C.K., Lilley, P.M.deQ. 1994) ; _computing_cell_refinement 'CAD-4 software (Enraf-Nonius, 1989)' #========================================================== # General computing #========================================================== _computing_structure_refinement ; CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996) ; _computing_publication_material ; CRYSTALS Issue 10 (Watkin, Prout, Carruthers & Betteridge, 1996) ; _computing_molecular_graphics ; ATOMS for Windows v4.0 and CAMERON ; _computing_structure_solution 'SIR92 (Giacovazzo et al, 1992)' #========================================================== _chemical_name_systematic ; ammonium manganese(II) pyrophosphate hydrate ; _chemical_melting_point 'not measured' _refine_ls_matrix_type full _atom_sites_solution_primary Direct_Methods _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment ' refxyz' #**************************************************************************** _cell_length_a 9.4610(8) _cell_angle_alpha 90 _cell_length_b 8.3565(7) _cell_angle_beta 99.908(9) _cell_length_c 9.477(1) _cell_angle_gamma 90 _cell_volume 738.07 _symmetry_cell_setting 'Monoclinic ' _symmetry_space_group_name_H-M 'P 1 21/a 1 ' loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z -x+1/2,y+1/2,-z x+1/2,-y+1/2,z loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _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 _atom_type_scat_source 'Mn ' -0.5680 2.8080 11.2819 5.3409 7.3573 0.3432 3.0193 17.8674 2.2441 83.7543 1.0896 International_Tables_Vol_IV_Table_2.2B 'P ' 0.2830 0.4340 6.4345 1.9067 4.1791 27.1570 1.7800 0.5260 1.4908 68.1645 1.1149 International_Tables_Vol_IV_Table_2.2B 'O ' 0.0470 0.0320 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 International_Tables_Vol_IV_Table_2.2B 'N ' 0.0290 0.0180 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 International_Tables_Vol_IV_Table_2.2B 'H ' 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7997 0.0030 International_Tables_Vol_IV_Table_2.2B _chemical_formula_sum ' H12 Mn3 N2 O16 P4' _chemical_formula_moiety ' H4 Mn3 O16 P4, 2(H4N) ' _chemical_compound_source ; synthesis described in paper ; _chemical_formula_weight 584.82 _cell_measurement_reflns_used 25 _cell_measurement_theta_min 7 _cell_measurement_theta_max 43 _cell_measurement_temperature 293 _cell_formula_units_Z 2.00 _exptl_crystal_description ' plate ' _exptl_crystal_colour ' colourless ' _exptl_crystal_size_min 0.03 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_max 0.08 _exptl_crystal_density_diffrn 2.63 _exptl_crystal_density_meas ? _exptl_crystal_F_000 578.0 _exptl_absorpt_coefficient_mu 25.62 _exptl_absorpt_correction_type EMPIRICAL _exptl_absorpt_process_details '\y scan' _exptl_absorpt_correction_T_min 0.189 _exptl_absorpt_correction_T_max 0.460 _diffrn_standards_interval_time 3600 _diffrn_standards_interval_count ? _diffrn_standards_number 3 _diffrn_standards_decay_% 1.79 _diffrn_ambient_temperature 293 _diffrn_reflns_number 1702 _reflns_number_total 1492 _diffrn_reflns_av_R_equivalents 0.017 _reflns_number_gt 1262 _diffrn_reflns_theta_min 0.00 _diffrn_reflns_theta_max 74.33 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 0 _diffrn_reflns_limit_l_min -11 _diffrn_reflns_limit_l_max 11 _diffrn_measured_fraction_theta_max 0.99 _reflns_limit_h_min -11 _reflns_limit_h_max 11 _reflns_limit_k_min 0 _reflns_limit_k_max 10 _reflns_limit_l_min 0 _reflns_limit_l_max 11 _reflns_threshold_expression >3.00\s(I) _refine_diff_density_min -1.35 _refine_diff_density_max 0.50 _refine_ls_number_reflns 1262 _refine_ls_number_parameters 134 _refine_ls_R_factor_gt 0.0351 _refine_ls_wR_factor_ref 0.0411 _refine_ls_goodness_of_fit_ref 1.1285 _refine_ls_shift/su_max 0.011046 _refine_ls_abs_structure_details ' from Flack enantiopole 0.000' _refine_ls_structure_factor_coef F _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Chebychev polynomial with 3 parameters, Carruthers and Watkin, 1979, 1.33 0.127 0.858 ; _diffrn_radiation_type 'Cu K\a' _diffrn_radiation_wavelength 1.54180 _diffrn_measurement_method 2\q/\w loop_ _atom_site_label _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_occupancy _atom_site_thermal_displace_type MN1 0.50117(5) 0.36011(6) 0.13448(5) 0.0126 1.0000 Uani MN2 0.5000 0.0000 0.0000 0.0127 1.0000 Uani P1 0.23723(8) 0.4440(1) 0.29674(8) 0.0112 1.0000 Uani P2 0.29002(8) 0.69755(9) 0.09772(8) 0.0104 1.0000 Uani O1 0.6410(3) 0.1409(3) -0.1317(3) 0.0152 1.0000 Uani O2 0.6157(3) 0.1213(3) 0.1852(3) 0.0149 1.0000 Uani O3 0.3584(2) 0.2015(3) -0.0050(3) 0.0144 1.0000 Uani O4 0.3889(2) 0.5791(3) 0.0421(2) 0.0137 1.0000 Uani O5 0.6708(3) 0.4869(4) 0.2740(3) 0.0235 1.0000 Uani O6 0.3779(3) 0.3584(3) 0.2983(3) 0.0174 1.0000 Uani O7 0.2627(3) 0.6289(3) 0.2506(2) 0.0132 1.0000 Uani O8 0.1986(3) 0.4593(3) 0.4441(3) 0.0161 1.0000 Uani N1 0.4864(4) 0.2210(5) 0.5565(4) 0.0282 1.0000 Uani H1 0.579(2) 0.172(4) 0.540(4) 0.0500 1.0000 Uiso H2 0.451(4) 0.297(4) 0.477(3) 0.0500 1.0000 Uiso H3 0.413(3) 0.135(3) 0.559(4) 0.0500 1.0000 Uiso H4 0.503(4) 0.280(4) 0.650(2) 0.0500 1.0000 Uiso H5 0.711(6) 0.505(7) 0.377(2) 0.0500 1.0000 Uiso H6 0.744(5) 0.537(7) 0.224(6) 0.0500 1.0000 Uiso 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 MN1 0.0155(3) 0.0135(3) 0.0098(3) -0.0006(2) 0.0025(2) 0.0001(2) MN2 0.0139(4) 0.0124(4) 0.0120(4) -0.0018(3) -0.0014(3) 0.0012(3) P1 0.0142(4) 0.0158(4) 0.0062(4) 0.0008(3) 0.0015(3) 0.0000(3) P2 0.0118(4) 0.0110(4) 0.0087(4) -0.0003(3) 0.0017(3) -0.0002(3) O1 0.019(1) 0.014(1) 0.015(1) 0.0001(9) 0.0049(9) -0.0040(9) O2 0.018(1) 0.016(1) 0.012(1) -0.0019(9) -0.0014(9) 0.0037(9) O3 0.013(1) 0.014(1) 0.017(1) -0.0014(9) -0.0005(9) 0.0006(8) O4 0.015(1) 0.015(1) 0.012(1) 0.0006(8) 0.0051(9) 0.0017(9) O5 0.029(1) 0.038(2) 0.014(1) -0.000(1) 0.001(1) -0.014(1) O6 0.016(1) 0.025(1) 0.015(1) 0.0045(9) 0.0047(9) 0.004(1) O7 0.021(1) 0.013(1) 0.010(1) -0.0003(9) 0.0047(9) -0.0030(9) O8 0.025(1) 0.025(1) 0.009(1) 0.0010(9) 0.0079(9) -0.001(1) N1 0.029(2) 0.037(2) 0.022(2) 0.005(1) -0.005(1) -0.003(2) _refine_ls_extinction_coef 23.2(19) _refine_ls_extinction_method 'Larson 1970 Crystallographic Computing eq 22' loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag MN1 . O2 . 2.282(2) yes MN1 . O3 . 2.171(2) yes MN1 . O4 . 2.219(2) yes MN1 . O4 2_665 2.177(2) yes MN1 . O5 . 2.172(3) yes MN1 . O6 . 2.096(2) yes MN2 . O1 . 2.302(2) yes MN2 . O1 2_655 2.302(2) yes MN2 . O2 . 2.155(2) yes MN2 . O2 2_655 2.155(2) yes MN2 . O3 . 2.147(2) yes MN2 . O3 2_655 2.147(2) yes P1 . O2 4_455 1.523(2) yes P1 . O6 . 1.509(2) yes P1 . O7 . 1.635(2) yes P1 . O8 . 1.509(2) yes P2 . O1 2_665 1.510(2) yes P2 . O3 3_555 1.524(2) yes P2 . O4 . 1.517(2) yes P2 . O7 . 1.620(2) yes O5 . H5 . 1.00(5) no O5 . H6 . 1.00(5) no N1 . H1 . 1.00(5) no N1 . H2 . 1.00(5) no N1 . H3 . 1.00(5) no N1 . H4 . 1.00(5) no loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag O2 . MN1 . O3 . 79.47(9) no O2 . MN1 . O4 . 169.10(9) no O3 . MN1 . O4 . 93.32(9) no O2 . MN1 . O4 2_665 95.36(9) no O3 . MN1 . O4 2_665 90.24(9) no O4 . MN1 . O4 2_665 76.35(9) no O2 . MN1 . O5 . 91.4(1) no O3 . MN1 . O5 . 170.3(1) no O4 . MN1 . O5 . 95.2(1) no O4 2_665 MN1 . O5 . 87.3(1) no O2 . MN1 . O6 . 98.20(9) no O3 . MN1 . O6 . 94.6(1) no O4 . MN1 . O6 . 90.47(9) no O4 2_665 MN1 . O6 . 166.2(1) no O5 . MN1 . O6 . 90.0(1) no O1 . MN2 . O1 2_655 180.00 no O1 . MN2 . O2 . 86.58(9) no O1 2_655 MN2 . O2 . 93.42(9) no O1 . MN2 . O2 2_655 93.42(9) no O1 2_655 MN2 . O2 2_655 86.58(9) no O2 . MN2 . O2 2_655 180 no O1 . MN2 . O3 . 90.26(9) no O1 2_655 MN2 . O3 . 89.74(9) no O2 . MN2 . O3 . 82.91(9) no O2 2_655 MN2 . O3 . 97.09(9) no O1 . MN2 . O3 2_655 89.74(9) no O1 2_655 MN2 . O3 2_655 90.26(9) no O2 . MN2 . O3 2_655 97.09(9) no O2 2_655 MN2 . O3 2_655 82.91(9) no O3 . MN2 . O3 2_655 180 no O2 4_455 P1 . O6 . 113.3(1) no O2 4_455 P1 . O7 . 106.3(1) no O6 . P1 . O7 . 106.3(1) no O2 4_455 P1 . O8 . 113.5(1) no O6 . P1 . O8 . 112.7(1) no O7 . P1 . O8 . 103.8(1) no O1 2_665 P2 . O3 3_555 115.2(1) no O1 2_665 P2 . O4 . 112.8(1) no O3 3_555 P2 . O4 . 112.1(1) no O1 2_665 P2 . O7 . 104.8(1) no O3 3_555 P2 . O7 . 104.5(1) no O4 . P2 . O7 . 106.4(1) no MN2 . O1 . P2 2_665 127.7(1) no MN1 . O2 . MN2 . 94.79(9) no MN1 . O2 . P1 4_555 137.2(1) no MN2 . O2 . P1 4_555 127.9(1) no MN1 . O3 . MN2 . 98.35(9) no MN1 . O3 . P2 3_545 141.2(1) no MN2 . O3 . P2 3_545 120.4(1) no MN1 . O4 . MN1 2_665 103.65(9) no MN1 . O4 . P2 . 133.0(1) no MN1 2_665 O4 . P2 . 121.3(1) no MN1 . O5 . H5 . 142.1(34) no MN1 . O5 . H6 . 114.7(36) no H5 . O5 . H6 . 102.8(50) no MN1 . O6 . P1 . 126.3(1) no P1 . O7 . P2 . 128.9(2) no H1 . N1 . H2 . 110(2) no H1 . N1 . H3 . 109(3) no H2 . N1 . H3 . 109(3) no H1 . N1 . H4 . 109(3) no H2 . N1 . H4 . 110(3) no H3 . N1 . H4 . 110(3) no