# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2011 data_global _journal_coden_Cambridge 182 loop_ _publ_author_name 'Li, Bo' 'Zhang, Jingping' _publ_contact_author_name 'Zhang, Jingping' _publ_contact_author_email zhangjingping66@yahoo.com.cn _publ_section_title ; Two-Step Relaxation in the 3D Spin-Canted Manganese Phosphate with High P-O-Mn Connectivity ; # Attachment '- CSD-421879.cif' data_1 _database_code_depnum_ccdc_archive 'CCDC 789849' #TrackingRef '- CSD-421879.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'H4 Mn7 O24 P6' _chemical_formula_weight 958.43 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 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' P P 0.1023 0.0942 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mn Mn 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_hall '-P 1' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 6.6101(6) _cell_length_b 8.0655(8) _cell_length_c 9.7339(10) _cell_angle_alpha 104.044(9) _cell_angle_beta 109.627(9) _cell_angle_gamma 101.306(8) _cell_volume 451.78(8) _cell_formula_units_Z 1 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 1533 _cell_measurement_theta_min 2.9462 _cell_measurement_theta_max 29.1889 _exptl_crystal_description needle _exptl_crystal_colour colorless _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.1 _exptl_crystal_size_min 0.1 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 3.523 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 461 _exptl_absorpt_coefficient_mu 5.397 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.529 _exptl_absorpt_correction_T_max 0.583 _exptl_absorpt_process_details ; CrysAlis (Oxford Diffraction, 2006) ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(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 'Oxford Diffraction Gemini R Ultra' _diffrn_measurement_method '\w scan' _diffrn_detector_area_resol_mean 10.0 _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 2820 _diffrn_reflns_av_R_equivalents 0.0273 _diffrn_reflns_av_sigmaI/netI 0.0531 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -10 _diffrn_reflns_limit_l_max 11 _diffrn_reflns_theta_min 2.95 _diffrn_reflns_theta_max 25.02 _reflns_number_total 1582 _reflns_number_gt 1175 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrysAlis (Oxford Diffraction, 2006)' _computing_cell_refinement CrysAlis _computing_data_reduction CrysAlis _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^)+(0.0234P)^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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1582 _refine_ls_number_parameters 177 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0369 _refine_ls_R_factor_gt 0.0254 _refine_ls_wR_factor_ref 0.0509 _refine_ls_wR_factor_gt 0.0498 _refine_ls_goodness_of_fit_ref 0.854 _refine_ls_restrained_S_all 0.854 _refine_ls_shift/su_max 0.000 _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 Mn1 Mn 0.61313(10) 1.04636(8) -0.11206(7) 0.00875(15) Uani 1 1 d . . . Mn2 Mn 1.05114(10) 1.21762(8) 0.51446(7) 0.01014(16) Uani 1 1 d . . . Mn3 Mn 1.0000 0.5000 0.0000 0.0093(2) Uani 1 2 d S . . Mn4 Mn 0.28485(10) 0.31741(8) 0.28321(7) 0.01050(16) Uani 1 1 d . . . P1 P 0.58653(18) 1.26802(14) -0.37539(13) 0.0089(2) Uani 1 1 d . . . P2 P 0.91728(17) 0.92277(14) 0.17566(12) 0.0072(2) Uani 1 1 d . . . P3 P 0.77265(17) 0.35956(14) 0.22039(12) 0.0076(2) Uani 1 1 d . . . O1 O 0.5082(4) 1.1148(4) -0.3210(3) 0.0129(7) Uani 1 1 d . . . O2 O 0.7223(5) 1.2046(4) -0.4730(3) 0.0131(7) Uani 1 1 d . . . O3 O 0.3877(4) 1.3049(4) -0.4866(3) 0.0124(6) Uani 1 1 d . . . O4 O 0.7379(4) 1.4389(3) -0.2404(3) 0.0109(6) Uani 1 1 d . . . O5 O 0.7036(4) 0.9645(4) 0.0904(3) 0.0097(6) Uani 1 1 d . . . O6 O 0.9520(4) 0.9577(4) 0.3455(3) 0.0097(6) Uani 1 1 d . . . O7 O 0.8926(5) 0.7225(4) 0.1006(3) 0.0115(6) Uani 1 1 d . . . O8 O 1.1252(4) 1.0400(4) 0.1679(3) 0.0098(6) Uani 1 1 d . . . O9 O 0.7777(4) 0.3147(3) 0.0582(3) 0.0099(6) Uani 1 1 d . . . O10 O 0.7909(5) 0.5647(4) 0.2689(4) 0.0129(7) Uani 1 1 d . . . O11 O 0.5539(4) 0.2605(3) 0.2247(3) 0.0094(6) Uani 1 1 d . . . O12 O 0.9797(4) 0.3352(4) 0.3360(3) 0.0104(6) Uani 1 1 d . . . H1 H 0.646(8) 1.095(7) -0.546(6) 0.038(16) Uiso 1 1 d . . . H2 H 0.807(8) 0.601(7) 0.213(6) 0.029(18) 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 Mn1 0.0091(3) 0.0094(3) 0.0089(3) 0.0034(3) 0.0047(3) 0.0030(3) Mn2 0.0114(3) 0.0098(4) 0.0092(3) 0.0032(3) 0.0046(3) 0.0024(3) Mn3 0.0115(5) 0.0087(5) 0.0088(5) 0.0031(4) 0.0053(4) 0.0025(4) Mn4 0.0121(3) 0.0093(4) 0.0121(4) 0.0042(3) 0.0063(3) 0.0043(3) P1 0.0080(5) 0.0096(6) 0.0093(6) 0.0035(5) 0.0031(4) 0.0037(5) P2 0.0071(5) 0.0074(6) 0.0081(6) 0.0031(5) 0.0037(5) 0.0025(5) P3 0.0083(5) 0.0073(6) 0.0078(6) 0.0025(5) 0.0041(5) 0.0023(5) O1 0.0119(15) 0.0112(16) 0.0126(16) 0.0054(13) 0.0021(13) 0.0004(13) O2 0.0113(16) 0.0130(17) 0.0137(17) 0.0008(15) 0.0066(13) 0.0030(14) O3 0.0081(15) 0.0177(17) 0.0114(16) 0.0052(13) 0.0024(12) 0.0062(13) O4 0.0125(15) 0.0076(15) 0.0127(16) 0.0034(13) 0.0055(13) 0.0027(13) O5 0.0071(14) 0.0130(16) 0.0099(15) 0.0051(13) 0.0027(12) 0.0045(13) O6 0.0141(15) 0.0111(16) 0.0062(15) 0.0041(12) 0.0049(12) 0.0059(13) O7 0.0144(15) 0.0105(16) 0.0128(16) 0.0033(13) 0.0089(12) 0.0050(13) O8 0.0092(14) 0.0075(15) 0.0128(16) 0.0033(13) 0.0052(13) 0.0014(12) O9 0.0135(15) 0.0083(15) 0.0116(16) 0.0054(13) 0.0081(13) 0.0034(13) O10 0.0184(17) 0.0103(17) 0.0133(18) 0.0062(15) 0.0094(15) 0.0031(14) O11 0.0084(14) 0.0111(16) 0.0091(15) 0.0029(13) 0.0038(12) 0.0041(13) O12 0.0080(14) 0.0116(16) 0.0127(16) 0.0057(13) 0.0043(13) 0.0030(13) _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 Mn1 O1 2.161(3) . ? Mn1 O5 2.161(3) 2_675 ? Mn1 O5 2.162(3) . ? Mn1 O8 2.166(3) 2_775 ? Mn1 O9 2.177(3) 1_565 ? Mn1 O11 2.312(3) 2_665 ? Mn1 Mn1 3.1782(12) 2_675 ? Mn2 O12 2.137(3) 1_565 ? Mn2 O6 2.143(3) . ? Mn2 O10 2.151(3) 2_776 ? Mn2 O6 2.191(3) 2_776 ? Mn2 O2 2.201(3) 1_556 ? Mn2 O3 2.202(3) 1_656 ? Mn3 O7 2.191(3) . ? Mn3 O7 2.191(3) 2_765 ? Mn3 O9 2.196(2) . ? Mn3 O9 2.196(2) 2_765 ? Mn3 O4 2.259(3) 2_775 ? Mn3 O4 2.259(3) 1_545 ? Mn4 O8 2.107(3) 1_445 ? Mn4 O4 2.128(3) 2_675 ? Mn4 O11 2.139(3) . ? Mn4 O3 2.146(3) 1_546 ? Mn4 O12 2.265(3) 1_455 ? P1 O4 1.525(3) . ? P1 O1 1.525(3) . ? P1 O3 1.530(3) . ? P1 O2 1.577(3) . ? P2 O5 1.527(3) . ? P2 O6 1.536(3) . ? P2 O8 1.544(3) . ? P2 O7 1.553(3) . ? P3 O11 1.528(3) . ? P3 O12 1.535(3) . ? P3 O9 1.545(3) . ? P3 O10 1.574(3) . ? O2 Mn2 2.201(3) 1_554 ? O3 Mn4 2.146(3) 1_564 ? O3 Mn2 2.202(3) 1_454 ? O4 Mn4 2.128(3) 2_675 ? O4 Mn3 2.259(3) 1_565 ? O5 Mn1 2.161(3) 2_675 ? O6 Mn2 2.191(3) 2_776 ? O8 Mn4 2.107(3) 1_665 ? O8 Mn1 2.166(3) 2_775 ? O9 Mn1 2.177(3) 1_545 ? O10 Mn2 2.151(3) 2_776 ? O11 Mn1 2.312(3) 2_665 ? O12 Mn2 2.137(3) 1_545 ? O12 Mn4 2.265(3) 1_655 ? 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 Mn1 O5 93.23(10) . 2_675 ? O1 Mn1 O5 176.93(11) . . ? O5 Mn1 O5 85.35(10) 2_675 . ? O1 Mn1 O8 89.71(10) . 2_775 ? O5 Mn1 O8 160.48(11) 2_675 2_775 ? O5 Mn1 O8 90.74(10) . 2_775 ? O1 Mn1 O9 99.54(10) . 1_565 ? O5 Mn1 O9 92.41(10) 2_675 1_565 ? O5 Mn1 O9 83.25(10) . 1_565 ? O8 Mn1 O9 106.14(10) 2_775 1_565 ? O1 Mn1 O11 97.73(10) . 2_665 ? O5 Mn1 O11 82.25(10) 2_675 2_665 ? O5 Mn1 O11 79.39(10) . 2_665 ? O8 Mn1 O11 78.23(10) 2_775 2_665 ? O9 Mn1 O11 162.18(9) 1_565 2_665 ? O1 Mn1 Mn1 135.84(8) . 2_675 ? O5 Mn1 Mn1 42.68(7) 2_675 2_675 ? O5 Mn1 Mn1 42.67(7) . 2_675 ? O8 Mn1 Mn1 130.52(7) 2_775 2_675 ? O9 Mn1 Mn1 87.06(7) 1_565 2_675 ? O11 Mn1 Mn1 77.47(7) 2_665 2_675 ? O12 Mn2 O6 90.55(10) 1_565 . ? O12 Mn2 O10 106.74(11) 1_565 2_776 ? O6 Mn2 O10 161.23(11) . 2_776 ? O12 Mn2 O6 165.50(11) 1_565 2_776 ? O6 Mn2 O6 78.14(11) . 2_776 ? O10 Mn2 O6 85.80(11) 2_776 2_776 ? O12 Mn2 O2 92.59(10) 1_565 1_556 ? O6 Mn2 O2 97.50(11) . 1_556 ? O10 Mn2 O2 89.12(12) 2_776 1_556 ? O6 Mn2 O2 80.09(10) 2_776 1_556 ? O12 Mn2 O3 79.19(10) 1_565 1_656 ? O6 Mn2 O3 94.99(10) . 1_656 ? O10 Mn2 O3 81.51(11) 2_776 1_656 ? O6 Mn2 O3 110.51(10) 2_776 1_656 ? O2 Mn2 O3 165.11(11) 1_556 1_656 ? O7 Mn3 O7 180.0 . 2_765 ? O7 Mn3 O9 90.58(10) . . ? O7 Mn3 O9 89.42(10) 2_765 . ? O7 Mn3 O9 89.42(10) . 2_765 ? O7 Mn3 O9 90.58(10) 2_765 2_765 ? O9 Mn3 O9 180.00(12) . 2_765 ? O7 Mn3 O4 87.03(10) . 2_775 ? O7 Mn3 O4 92.97(10) 2_765 2_775 ? O9 Mn3 O4 86.53(9) . 2_775 ? O9 Mn3 O4 93.47(9) 2_765 2_775 ? O7 Mn3 O4 92.97(10) . 1_545 ? O7 Mn3 O4 87.03(10) 2_765 1_545 ? O9 Mn3 O4 93.47(9) . 1_545 ? O9 Mn3 O4 86.53(9) 2_765 1_545 ? O4 Mn3 O4 180.0 2_775 1_545 ? O8 Mn4 O4 137.87(11) 1_445 2_675 ? O8 Mn4 O11 83.52(10) 1_445 . ? O4 Mn4 O11 105.10(10) 2_675 . ? O8 Mn4 O3 96.22(11) 1_445 1_546 ? O4 Mn4 O3 121.24(11) 2_675 1_546 ? O11 Mn4 O3 101.29(10) . 1_546 ? O8 Mn4 O12 88.62(10) 1_445 1_455 ? O4 Mn4 O12 82.05(10) 2_675 1_455 ? O11 Mn4 O12 171.91(10) . 1_455 ? O3 Mn4 O12 77.62(10) 1_546 1_455 ? O4 P1 O1 112.14(16) . . ? O4 P1 O3 110.55(15) . . ? O1 P1 O3 111.78(15) . . ? O4 P1 O2 109.27(16) . . ? O1 P1 O2 107.25(16) . . ? O3 P1 O2 105.55(16) . . ? O5 P2 O6 109.13(15) . . ? O5 P2 O8 111.01(15) . . ? O6 P2 O8 109.54(16) . . ? O5 P2 O7 109.73(15) . . ? O6 P2 O7 108.92(15) . . ? O8 P2 O7 108.48(16) . . ? O11 P3 O12 111.75(15) . . ? O11 P3 O9 114.85(16) . . ? O12 P3 O9 110.34(15) . . ? O11 P3 O10 106.59(16) . . ? O12 P3 O10 108.31(16) . . ? O9 P3 O10 104.48(16) . . ? P1 O1 Mn1 137.31(17) . . ? P1 O2 Mn2 148.27(19) . 1_554 ? P1 O3 Mn4 136.10(17) . 1_564 ? P1 O3 Mn2 119.54(16) . 1_454 ? Mn4 O3 Mn2 98.35(11) 1_564 1_454 ? P1 O4 Mn4 115.27(15) . 2_675 ? P1 O4 Mn3 134.90(15) . 1_565 ? Mn4 O4 Mn3 109.77(12) 2_675 1_565 ? P2 O5 Mn1 135.37(15) . 2_675 ? P2 O5 Mn1 129.91(15) . . ? Mn1 O5 Mn1 94.65(10) 2_675 . ? P2 O6 Mn2 124.92(15) . . ? P2 O6 Mn2 133.01(16) . 2_776 ? Mn2 O6 Mn2 101.86(11) . 2_776 ? P2 O7 Mn3 155.02(17) . . ? P2 O8 Mn4 127.39(16) . 1_665 ? P2 O8 Mn1 127.44(16) . 2_775 ? Mn4 O8 Mn1 101.79(11) 1_665 2_775 ? P3 O9 Mn1 121.70(15) . 1_545 ? P3 O9 Mn3 122.16(16) . . ? Mn1 O9 Mn3 115.22(12) 1_545 . ? P3 O10 Mn2 133.90(18) . 2_776 ? P3 O11 Mn4 139.59(16) . . ? P3 O11 Mn1 123.50(15) . 2_665 ? Mn4 O11 Mn1 96.26(10) . 2_665 ? P3 O12 Mn2 137.68(16) . 1_545 ? P3 O12 Mn4 121.49(15) . 1_655 ? Mn2 O12 Mn4 96.74(10) 1_545 1_655 ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A O2 H1 O1 0.91(5) 1.72(5) 2.623(4) 177(5) 2_674 O10 H2 O7 0.70(5) 1.79(5) 2.484(4) 169(6) . _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 25.02 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.540 _refine_diff_density_min -0.518 _refine_diff_density_rms 0.125