# Electronic Supplementary Material for CrystEngComm # This journal is (c) The Royal Society of Chemistry 2009 data_global _journal_name_full CrystEngComm _journal_coden_Cambridge 1350 _publ_contact_author_name 'Li-Min Zheng' _publ_contact_author_email LMZHENG@NETRA.NJU.EDU.CN _publ_section_title ; [M(OOCC6H4PO3H)(H2O)] (M(II) = Mn, Co, Ni): Layered Metal Phosphonates Showing Variable Magnetic Behaviors ; loop_ _publ_author_name 'Li-Min Zheng.' 'Deng-Ke Cao.' 'Silvio Decurtins' 'Tony D Keene' 'Jin-Tang Li.' # Attachment 'Co.cif' data_2 _database_code_depnum_ccdc_archive 'CCDC 692232' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C7 H7 Co O6 P' _chemical_formula_sum 'C7 H7 Co O6 P' _chemical_formula_weight 277.03 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' 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' Co Co 0.3494 0.9721 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'Pbca ' _symmetry_space_group_name_Hall '-P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 8.999(5) _cell_length_b 8.614(5) _cell_length_c 22.506(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1744.6(17) _cell_formula_units_Z 8 _cell_measurement_temperature 273(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description flake _exptl_crystal_colour purple _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.36 _exptl_crystal_size_min 0.03 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.109 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1112 _exptl_absorpt_coefficient_mu 2.155 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.456 _exptl_absorpt_correction_T_max 0.934 _exptl_absorpt_process_details 'SADABS, Bruker(2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 273(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 ? _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 7650 _diffrn_reflns_av_R_equivalents 0.1192 _diffrn_reflns_av_sigmaI/netI 0.0741 _diffrn_reflns_limit_h_min -6 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -27 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 2.90 _diffrn_reflns_theta_max 26.00 _reflns_number_total 1707 _reflns_number_gt 1467 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 2000)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker, 2000)' _computing_structure_solution 'SHELXTL (Bruker, 2000)' _computing_structure_refinement SHELXTL _computing_molecular_graphics SHELXTL _computing_publication_material 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^)+(0.0585P)^2^+4.1059P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1707 _refine_ls_number_parameters 137 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0716 _refine_ls_R_factor_gt 0.0590 _refine_ls_wR_factor_ref 0.1410 _refine_ls_wR_factor_gt 0.1329 _refine_ls_goodness_of_fit_ref 1.056 _refine_ls_restrained_S_all 1.056 _refine_ls_shift/su_max 0.100 _refine_ls_shift/su_mean 0.026 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 Co1 Co 0.62937(7) 0.37541(7) 0.49325(3) 0.0174(3) Uani 1 1 d . . . P1 P 0.37469(13) 0.29459(12) 0.58698(5) 0.0154(3) Uani 1 1 d . . . O1 O 0.6360(4) 0.1501(3) 0.52119(16) 0.0218(8) Uani 1 1 d . . . O2 O 0.7332(4) -0.0590(3) 0.56262(15) 0.0233(8) Uani 1 1 d . . . O3 O 0.4343(4) 0.4020(3) 0.53976(14) 0.0183(7) Uani 1 1 d . . . O4 O 0.3014(4) 0.1474(3) 0.56595(15) 0.0190(7) Uani 1 1 d . . . O5 O 0.2588(4) 0.3903(3) 0.62434(16) 0.0246(8) Uani 1 1 d . . . H1 H 0.2278 0.4631 0.6044 0.029 Uiso 1 1 calc R . . O1W O 0.4943(4) 0.2869(4) 0.41965(15) 0.0295(8) Uani 1 1 d . . . H1B H 0.4119 0.2359 0.4277 0.035 Uiso 1 1 d R . . H1A H 0.5524 0.2319 0.3954 0.035 Uiso 1 1 d R . . C1 C 0.6655(5) 0.0690(5) 0.5660(2) 0.0172(10) Uani 1 1 d . . . C2 C 0.6242(5) 0.1254(5) 0.6272(2) 0.0202(11) Uani 1 1 d . . . C3 C 0.7126(6) 0.0712(6) 0.6738(2) 0.0286(12) Uani 1 1 d . . . H3 H 0.7864 -0.0013 0.6657 0.034 Uiso 1 1 calc R . . C4 C 0.6942(7) 0.1214(6) 0.7310(3) 0.0358(14) Uani 1 1 d . . . H4 H 0.7536 0.0823 0.7613 0.043 Uiso 1 1 calc R . . C5 C 0.5861(7) 0.2308(6) 0.7432(2) 0.0333(13) Uani 1 1 d . . . H5 H 0.5747 0.2683 0.7817 0.040 Uiso 1 1 calc R . . C6 C 0.4961(6) 0.2841(5) 0.6988(2) 0.0252(11) Uani 1 1 d . . . H6 H 0.4218 0.3553 0.7078 0.030 Uiso 1 1 calc R . . C7 C 0.5133(6) 0.2335(5) 0.6397(2) 0.0180(10) 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 Co1 0.0173(4) 0.0141(4) 0.0208(4) 0.0024(2) 0.0024(3) 0.0011(2) P1 0.0147(6) 0.0124(5) 0.0190(7) 0.0013(4) 0.0005(5) -0.0004(4) O1 0.026(2) 0.0154(15) 0.0239(19) 0.0030(14) 0.0014(15) 0.0047(14) O2 0.025(2) 0.0187(16) 0.0265(19) 0.0050(13) 0.0031(16) 0.0069(14) O3 0.0175(18) 0.0158(14) 0.0217(17) 0.0041(12) -0.0003(15) 0.0015(14) O4 0.0185(18) 0.0155(14) 0.0230(18) 0.0030(13) -0.0042(15) -0.0048(13) O5 0.0249(19) 0.0213(16) 0.027(2) 0.0054(14) 0.0085(17) 0.0058(15) O1W 0.024(2) 0.0287(18) 0.035(2) -0.0016(15) 0.0003(17) -0.0034(16) C1 0.014(2) 0.014(2) 0.023(3) 0.0000(18) 0.002(2) -0.0024(18) C2 0.019(3) 0.018(2) 0.024(3) 0.0048(18) -0.003(2) -0.0030(19) C3 0.024(3) 0.032(3) 0.029(3) 0.004(2) 0.000(2) 0.003(2) C4 0.036(3) 0.044(3) 0.028(3) 0.008(2) -0.013(3) -0.005(3) C5 0.040(3) 0.042(3) 0.018(3) -0.003(2) 0.000(3) -0.006(3) C6 0.026(3) 0.026(2) 0.024(3) -0.003(2) 0.003(2) -0.002(2) C7 0.022(3) 0.0103(19) 0.022(2) 0.0000(17) 0.004(2) -0.0037(18) _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 Co1 O1 2.041(3) . ? Co1 O4 2.052(4) 4_556 ? Co1 O3 2.056(4) . ? Co1 O2 2.071(3) 8_765 ? Co1 O3 2.134(3) 5_666 ? Co1 O1W 2.191(4) . ? P1 O4 1.506(3) . ? P1 O3 1.508(3) . ? P1 O5 1.573(4) . ? P1 C7 1.801(5) . ? O1 C1 1.255(6) . ? O2 C1 1.262(5) . ? O2 Co1 2.071(3) 8_755 ? O3 Co1 2.134(3) 5_666 ? O4 Co1 2.052(4) 4_456 ? O5 H1 0.8200 . ? O1W H1B 0.8808 . ? O1W H1A 0.8917 . ? C1 C2 1.507(7) . ? C2 C3 1.397(7) . ? C2 C7 1.394(7) . ? C3 C4 1.369(8) . ? C3 H3 0.9300 . ? C4 C5 1.382(9) . ? C4 H4 0.9300 . ? C5 C6 1.365(8) . ? C5 H5 0.9300 . ? C6 C7 1.408(6) . ? C6 H6 0.9300 . ? 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 Co1 O4 95.00(13) . 4_556 ? O1 Co1 O3 88.51(13) . . ? O4 Co1 O3 170.11(14) 4_556 . ? O1 Co1 O2 90.57(14) . 8_765 ? O4 Co1 O2 93.72(15) 4_556 8_765 ? O3 Co1 O2 95.50(14) . 8_765 ? O1 Co1 O3 165.73(14) . 5_666 ? O4 Co1 O3 93.59(12) 4_556 5_666 ? O3 Co1 O3 81.25(13) . 5_666 ? O2 Co1 O3 100.23(13) 8_765 5_666 ? O1 Co1 O1W 85.31(14) . . ? O4 Co1 O1W 83.94(15) 4_556 . ? O3 Co1 O1W 87.13(14) . . ? O2 Co1 O1W 175.06(13) 8_765 . ? O3 Co1 O1W 84.28(13) 5_666 . ? O4 P1 O3 116.82(19) . . ? O4 P1 O5 108.6(2) . . ? O3 P1 O5 106.92(18) . . ? O4 P1 C7 105.35(19) . . ? O3 P1 C7 113.4(2) . . ? O5 P1 C7 105.1(2) . . ? C1 O1 Co1 141.5(3) . . ? C1 O2 Co1 124.9(3) . 8_755 ? P1 O3 Co1 126.45(19) . . ? P1 O3 Co1 134.5(2) . 5_666 ? Co1 O3 Co1 98.75(13) . 5_666 ? P1 O4 Co1 127.96(18) . 4_456 ? P1 O5 H1 109.5 . . ? Co1 O1W H1B 119.0 . . ? Co1 O1W H1A 108.8 . . ? H1B O1W H1A 110.8 . . ? O1 C1 O2 122.7(4) . . ? O1 C1 C2 120.2(4) . . ? O2 C1 C2 117.1(4) . . ? C3 C2 C7 118.6(5) . . ? C3 C2 C1 116.0(4) . . ? C7 C2 C1 125.3(4) . . ? C4 C3 C2 122.2(5) . . ? C4 C3 H3 118.9 . . ? C2 C3 H3 118.9 . . ? C3 C4 C5 119.1(5) . . ? C3 C4 H4 120.4 . . ? C5 C4 H4 120.4 . . ? C6 C5 C4 120.1(5) . . ? C6 C5 H5 119.9 . . ? C4 C5 H5 119.9 . . ? C5 C6 C7 121.4(5) . . ? C5 C6 H6 119.3 . . ? C7 C6 H6 119.3 . . ? C2 C7 C6 118.5(5) . . ? C2 C7 P1 123.9(4) . . ? C6 C7 P1 117.1(4) . . ? 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 O5 H1 O4 0.82 1.83 2.631(4) 166.6 8_665 O1W H1B O2 0.88 2.02 2.864(5) 160.6 5_656 O1W H1A O5 0.89 2.18 2.996(5) 151.8 4_556 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 26.00 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.628 _refine_diff_density_min -0.577 _refine_diff_density_rms 0.147 # Attachment 'Mn.cif' data_3 _database_code_depnum_ccdc_archive 'CCDC 692233' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C7 H7 Mn O6 P' _chemical_formula_sum 'C7 H7 Mn O6 P' _chemical_formula_weight 273.04 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' 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 Orthorhombic _symmetry_space_group_name_H-M 'Pbca ' _symmetry_space_group_name_Hall '-P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 9.190(2) _cell_length_b 8.684(2) _cell_length_c 22.670(6) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1809.2(8) _cell_formula_units_Z 8 _cell_measurement_temperature 273(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description flake _exptl_crystal_colour colorless _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.34 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.005 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1096 _exptl_absorpt_coefficient_mu 1.640 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.545 _exptl_absorpt_correction_T_max 0.940 _exptl_absorpt_process_details 'SADABS, Bruker(2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 273(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 ? _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 10090 _diffrn_reflns_av_R_equivalents 0.0713 _diffrn_reflns_av_sigmaI/netI 0.0650 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -30 _diffrn_reflns_limit_l_max 26 _diffrn_reflns_theta_min 2.85 _diffrn_reflns_theta_max 28.27 _reflns_number_total 2197 _reflns_number_gt 1646 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 2000)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker, 2000)' _computing_structure_solution 'SHELXTL (Bruker, 2000)' _computing_structure_refinement SHELXTL _computing_molecular_graphics SHELXTL _computing_publication_material 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^)+(0.0326P)^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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2197 _refine_ls_number_parameters 137 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0621 _refine_ls_R_factor_gt 0.0404 _refine_ls_wR_factor_ref 0.0895 _refine_ls_wR_factor_gt 0.0835 _refine_ls_goodness_of_fit_ref 0.989 _refine_ls_restrained_S_all 0.989 _refine_ls_shift/su_max 0.003 _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 0.63792(5) 0.37821(5) 0.495111(19) 0.02184(15) Uani 1 1 d . . . P1 P 0.37598(8) 0.29599(9) 0.58915(3) 0.01730(18) Uani 1 1 d . . . O1 O 0.6329(2) 0.1513(2) 0.52621(9) 0.0268(5) Uani 1 1 d . . . O2 O 0.7243(2) -0.0570(2) 0.56737(9) 0.0301(5) Uani 1 1 d . . . O3 O 0.4329(2) 0.4013(2) 0.54127(8) 0.0191(4) Uani 1 1 d . . . O4 O 0.3049(2) 0.1492(2) 0.56863(8) 0.0215(5) Uani 1 1 d . . . O5 O 0.2611(2) 0.3910(2) 0.62606(9) 0.0264(5) Uani 1 1 d . . . H1 H 0.2430 0.4720 0.6090 0.032 Uiso 1 1 calc R . . O1W O 0.4968(2) 0.2859(3) 0.41762(9) 0.0391(6) Uani 1 1 d . . . H1B H 0.4144 0.2349 0.4257 0.047 Uiso 1 1 d R . . H1A H 0.5550 0.2308 0.3934 0.047 Uiso 1 1 d R . . C1 C 0.6598(3) 0.0718(3) 0.57036(13) 0.0202(6) Uani 1 1 d . . . C2 C 0.6223(3) 0.1312(3) 0.63098(12) 0.0224(7) Uani 1 1 d . . . C3 C 0.7080(4) 0.0799(4) 0.67695(13) 0.0329(8) Uani 1 1 d . . . H3 H 0.7784 0.0052 0.6698 0.039 Uiso 1 1 calc R . . C4 C 0.6910(4) 0.1378(4) 0.73382(15) 0.0396(9) Uani 1 1 d . . . H4 H 0.7502 0.1028 0.7642 0.048 Uiso 1 1 calc R . . C5 C 0.5872(4) 0.2460(4) 0.74466(13) 0.0386(9) Uani 1 1 d . . . H5 H 0.5766 0.2862 0.7824 0.046 Uiso 1 1 calc R . . C6 C 0.4974(3) 0.2964(4) 0.69962(12) 0.0282(7) Uani 1 1 d . . . H6 H 0.4259 0.3692 0.7077 0.034 Uiso 1 1 calc R . . C7 C 0.5120(3) 0.2400(3) 0.64217(11) 0.0188(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 Mn1 0.0207(3) 0.0184(3) 0.0264(3) 0.00511(19) 0.0051(2) 0.00288(19) P1 0.0164(4) 0.0150(4) 0.0205(4) 0.0017(3) 0.0007(3) -0.0001(3) O1 0.0363(14) 0.0171(12) 0.0270(11) 0.0041(9) 0.0034(10) 0.0032(9) O2 0.0296(13) 0.0218(13) 0.0388(12) 0.0042(10) 0.0041(10) 0.0081(10) O3 0.0167(10) 0.0168(11) 0.0238(10) 0.0051(8) 0.0021(8) 0.0018(8) O4 0.0192(11) 0.0176(11) 0.0275(11) 0.0030(9) -0.0059(9) -0.0029(8) O5 0.0290(13) 0.0215(13) 0.0287(12) 0.0073(9) 0.0094(9) 0.0081(9) O1W 0.0320(14) 0.0387(16) 0.0468(14) -0.0033(12) 0.0014(11) -0.0049(11) C1 0.0131(15) 0.0163(16) 0.0313(16) 0.0013(13) 0.0016(12) -0.0035(11) C2 0.0184(16) 0.0234(17) 0.0254(15) 0.0045(13) -0.0023(12) -0.0028(13) C3 0.0271(19) 0.036(2) 0.0353(19) 0.0081(15) -0.0031(15) 0.0047(15) C4 0.037(2) 0.049(3) 0.0323(19) 0.0142(17) -0.0146(17) -0.0048(18) C5 0.048(2) 0.045(2) 0.0221(17) -0.0031(15) -0.0059(16) -0.0070(18) C6 0.0304(18) 0.0291(19) 0.0251(16) -0.0029(14) 0.0011(14) -0.0020(14) C7 0.0199(15) 0.0181(16) 0.0186(15) 0.0019(12) -0.0019(12) -0.0048(12) _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 2.093(2) . ? Mn1 O4 2.121(2) 4_556 ? Mn1 O2 2.145(2) 8_765 ? Mn1 O3 2.164(2) . ? Mn1 O3 2.1844(19) 5_666 ? Mn1 O1W 2.326(2) . ? P1 O4 1.506(2) . ? P1 O3 1.5125(19) . ? P1 O5 1.580(2) . ? P1 C7 1.801(3) . ? O1 C1 1.241(3) . ? O2 C1 1.268(3) . ? O2 Mn1 2.145(2) 8_755 ? O3 Mn1 2.1844(19) 5_666 ? O4 Mn1 2.121(2) 4_456 ? O5 H1 0.8200 . ? O1W H1B 0.8961 . ? O1W H1A 0.9027 . ? C1 C2 1.508(4) . ? C2 C3 1.380(4) . ? C2 C7 1.409(4) . ? C3 C4 1.393(5) . ? C3 H3 0.9300 . ? C4 C5 1.361(5) . ? C4 H4 0.9300 . ? C5 C6 1.384(4) . ? C5 H5 0.9300 . ? C6 C7 1.398(4) . ? C6 H6 0.9300 . ? 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 O4 98.02(8) . 4_556 ? O1 Mn1 O2 90.15(8) . 8_765 ? O4 Mn1 O2 97.04(9) 4_556 8_765 ? O1 Mn1 O3 84.56(7) . . ? O4 Mn1 O3 165.80(8) 4_556 . ? O2 Mn1 O3 96.91(8) 8_765 . ? O1 Mn1 O3 161.07(8) . 5_666 ? O4 Mn1 O3 93.26(7) 4_556 5_666 ? O2 Mn1 O3 103.54(8) 8_765 5_666 ? O3 Mn1 O3 80.91(7) . 5_666 ? O1 Mn1 O1W 85.28(8) . . ? O4 Mn1 O1W 81.38(8) 4_556 . ? O2 Mn1 O1W 174.89(8) 8_765 . ? O3 Mn1 O1W 84.94(8) . . ? O3 Mn1 O1W 81.43(8) 5_666 . ? O4 P1 O3 116.10(11) . . ? O4 P1 O5 108.41(12) . . ? O3 P1 O5 107.19(11) . . ? O4 P1 C7 106.18(12) . . ? O3 P1 C7 113.71(12) . . ? O5 P1 C7 104.56(12) . . ? C1 O1 Mn1 142.3(2) . . ? C1 O2 Mn1 123.25(19) . 8_755 ? P1 O3 Mn1 126.30(11) . . ? P1 O3 Mn1 134.26(12) . 5_666 ? Mn1 O3 Mn1 99.09(7) . 5_666 ? P1 O4 Mn1 128.26(11) . 4_456 ? P1 O5 H1 109.5 . . ? Mn1 O1W H1B 119.2 . . ? Mn1 O1W H1A 108.2 . . ? H1B O1W H1A 111.2 . . ? O1 C1 O2 122.7(3) . . ? O1 C1 C2 120.0(3) . . ? O2 C1 C2 117.2(3) . . ? C3 C2 C7 119.4(3) . . ? C3 C2 C1 116.6(3) . . ? C7 C2 C1 123.9(3) . . ? C2 C3 C4 121.2(3) . . ? C2 C3 H3 119.4 . . ? C4 C3 H3 119.4 . . ? C5 C4 C3 119.7(3) . . ? C5 C4 H4 120.2 . . ? C3 C4 H4 120.2 . . ? C4 C5 C6 120.2(3) . . ? C4 C5 H5 119.9 . . ? C6 C5 H5 119.9 . . ? C5 C6 C7 121.3(3) . . ? C5 C6 H6 119.4 . . ? C7 C6 H6 119.4 . . ? C6 C7 C2 118.2(3) . . ? C6 C7 P1 117.4(2) . . ? C2 C7 P1 124.1(2) . . ? 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 O1W H1A O5 0.90 2.21 3.039(3) 151.7 4_556 O1W H1B O2 0.90 2.01 2.863(3) 158.8 5_656 O5 H1 O4 0.82 1.84 2.663(3) 177.2 8_665 _diffrn_measured_fraction_theta_max 0.979 _diffrn_reflns_theta_full 28.27 _diffrn_measured_fraction_theta_full 0.979 _refine_diff_density_max 0.493 _refine_diff_density_min -0.477 _refine_diff_density_rms 0.085 # Attachment 'Ni.cif' data_1 _database_code_depnum_ccdc_archive 'CCDC 692234' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C7 H7 Ni O6 P' _chemical_formula_sum 'C7 H7 Ni O6 P' _chemical_formula_weight 276.81 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' 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' Ni Ni 0.3393 1.1124 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M 'Pbca ' _symmetry_space_group_name_Hall '-P 2ac 2ab' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 8.950(3) _cell_length_b 8.558(3) _cell_length_c 22.461(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1720.4(9) _cell_formula_units_Z 8 _cell_measurement_temperature 273(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description flake _exptl_crystal_colour green _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.137 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1120 _exptl_absorpt_coefficient_mu 2.446 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.65 _exptl_absorpt_correction_T_max 0.948 _exptl_absorpt_process_details 'SADABS, Bruker(2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 273(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 ? _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 9583 _diffrn_reflns_av_R_equivalents 0.0571 _diffrn_reflns_av_sigmaI/netI 0.0444 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 5 _diffrn_reflns_limit_l_min -28 _diffrn_reflns_limit_l_max 28 _diffrn_reflns_theta_min 1.81 _diffrn_reflns_theta_max 28.27 _reflns_number_total 2066 _reflns_number_gt 1836 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (Bruker, 2000)' _computing_cell_refinement SMART _computing_data_reduction 'SAINT (Bruker, 2000)' _computing_structure_solution 'SHELXTL (Bruker, 2000)' _computing_structure_refinement SHELXTL _computing_molecular_graphics SHELXTL _computing_publication_material 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^)+(0.0740P)^2^+2.1396P] 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 constr _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2066 _refine_ls_number_parameters 137 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0531 _refine_ls_R_factor_gt 0.0446 _refine_ls_wR_factor_ref 0.1259 _refine_ls_wR_factor_gt 0.1198 _refine_ls_goodness_of_fit_ref 1.016 _refine_ls_restrained_S_all 1.016 _refine_ls_shift/su_max 0.009 _refine_ls_shift/su_mean 0.002 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 Ni1 Ni 0.62600(5) 0.37451(5) 0.49221(2) 0.01376(17) Uani 1 1 d . . . P1 P 0.37409(8) 0.29530(10) 0.58596(4) 0.0128(2) Uani 1 1 d . . . O1 O 0.6389(3) 0.1527(3) 0.51977(12) 0.0186(5) Uani 1 1 d . . . O2 O 0.7387(3) -0.0571(3) 0.56071(11) 0.0193(5) Uani 1 1 d . . . O3 O 0.4344(2) 0.4047(3) 0.53885(10) 0.0141(5) Uani 1 1 d . . . O4 O 0.3016(2) 0.1465(3) 0.56422(11) 0.0152(5) Uani 1 1 d . . . O5 O 0.2551(3) 0.3903(3) 0.62298(12) 0.0205(6) Uani 1 1 d . . . H1 H 0.2308 0.4688 0.6044 0.025 Uiso 1 1 calc R . . O1W O 0.4936(3) 0.2865(3) 0.42116(11) 0.0230(6) Uani 1 1 d . . . H1B H 0.4112 0.2355 0.4292 0.028 Uiso 1 1 d R . . H1A H 0.5517 0.2315 0.3970 0.028 Uiso 1 1 d R . . C1 C 0.6693(3) 0.0707(4) 0.56410(15) 0.0142(6) Uani 1 1 d . . . C2 C 0.6276(4) 0.1261(4) 0.62610(16) 0.0166(7) Uani 1 1 d . . . C3 C 0.7154(4) 0.0701(5) 0.67195(17) 0.0247(8) Uani 1 1 d . . . H3 H 0.7898 -0.0025 0.6636 0.030 Uiso 1 1 calc R . . C4 C 0.6950(5) 0.1197(5) 0.73007(18) 0.0288(9) Uani 1 1 d . . . H4 H 0.7552 0.0806 0.7604 0.035 Uiso 1 1 calc R . . C5 C 0.5847(5) 0.2277(5) 0.74281(17) 0.0287(9) Uani 1 1 d . . . H5 H 0.5718 0.2635 0.7816 0.034 Uiso 1 1 calc R . . C6 C 0.4938(4) 0.2823(4) 0.69764(16) 0.0236(8) Uani 1 1 d . . . H6 H 0.4184 0.3533 0.7066 0.028 Uiso 1 1 calc R . . C7 C 0.5127(3) 0.2331(4) 0.63896(15) 0.0149(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 Ni1 0.0122(3) 0.0113(3) 0.0178(3) 0.00174(16) 0.00136(15) 0.00045(15) P1 0.0116(4) 0.0102(4) 0.0167(4) 0.0014(3) 0.0003(3) -0.0003(3) O1 0.0206(13) 0.0145(12) 0.0209(12) 0.0022(10) -0.0018(10) 0.0025(10) O2 0.0200(12) 0.0144(11) 0.0237(13) 0.0020(10) 0.0023(10) 0.0050(10) O3 0.0118(10) 0.0109(10) 0.0194(12) 0.0032(9) 0.0010(9) 0.0010(9) O4 0.0122(10) 0.0117(11) 0.0217(12) 0.0024(9) -0.0047(9) -0.0022(9) O5 0.0205(12) 0.0160(12) 0.0249(14) 0.0043(10) 0.0058(10) 0.0061(10) O1W 0.0176(11) 0.0203(13) 0.0311(14) -0.0022(11) -0.0002(10) -0.0035(10) C1 0.0105(13) 0.0136(15) 0.0184(16) 0.0007(13) 0.0008(12) -0.0036(12) C2 0.0162(15) 0.0154(17) 0.0181(17) 0.0006(13) -0.0013(12) -0.0032(12) C3 0.0224(17) 0.0257(18) 0.0259(19) 0.0022(15) -0.0031(15) 0.0053(15) C4 0.0282(19) 0.037(2) 0.022(2) 0.0073(16) -0.0101(16) -0.0022(17) C5 0.030(2) 0.038(2) 0.0175(18) -0.0043(16) -0.0008(15) -0.0020(18) C6 0.0237(17) 0.0236(18) 0.0234(19) -0.0020(15) 0.0021(14) -0.0002(15) C7 0.0148(14) 0.0115(14) 0.0184(16) 0.0006(12) -0.0017(12) -0.0002(12) _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 Ni1 O1 2.000(3) . ? Ni1 O4 2.027(2) 4_556 ? Ni1 O3 2.026(2) . ? Ni1 O2 2.043(2) 8_765 ? Ni1 O3 2.086(2) 5_666 ? Ni1 O1W 2.126(3) . ? P1 O4 1.510(2) . ? P1 O3 1.512(2) . ? P1 O5 1.577(2) . ? P1 C7 1.800(3) . ? O1 C1 1.248(4) . ? O2 C1 1.260(4) . ? O2 Ni1 2.043(2) 8_755 ? O3 Ni1 2.086(2) 5_666 ? O4 Ni1 2.027(2) 4_456 ? O5 H1 0.8200 . ? O1W H1B 0.8758 . ? O1W H1A 0.8877 . ? C1 C2 1.518(5) . ? C2 C3 1.381(5) . ? C2 C7 1.407(4) . ? C3 C4 1.385(5) . ? C3 H3 0.9300 . ? C4 C5 1.382(6) . ? C4 H4 0.9300 . ? C5 C6 1.382(5) . ? C5 H5 0.9300 . ? C6 C7 1.394(5) . ? C6 H6 0.9300 . ? 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 Ni1 O4 93.70(10) . 4_556 ? O1 Ni1 O3 90.56(10) . . ? O4 Ni1 O3 172.24(10) 4_556 . ? O1 Ni1 O2 90.26(10) . 8_765 ? O4 Ni1 O2 92.11(10) 4_556 8_765 ? O3 Ni1 O2 94.35(10) . 8_765 ? O1 Ni1 O3 168.09(10) . 5_666 ? O4 Ni1 O3 94.14(9) 4_556 5_666 ? O3 Ni1 O3 80.68(10) . 5_666 ? O2 Ni1 O3 98.40(10) 8_765 5_666 ? O1 Ni1 O1W 85.89(10) . . ? O4 Ni1 O1W 86.06(10) 4_556 . ? O3 Ni1 O1W 87.79(10) . . ? O2 Ni1 O1W 175.61(10) 8_765 . ? O3 Ni1 O1W 85.72(10) 5_666 . ? O4 P1 O3 116.68(14) . . ? O4 P1 O5 108.37(14) . . ? O3 P1 O5 106.90(13) . . ? O4 P1 C7 105.11(14) . . ? O3 P1 C7 113.57(14) . . ? O5 P1 C7 105.62(15) . . ? C1 O1 Ni1 142.5(2) . . ? C1 O2 Ni1 125.9(2) . 8_755 ? P1 O3 Ni1 125.79(13) . . ? P1 O3 Ni1 134.62(14) . 5_666 ? Ni1 O3 Ni1 99.32(10) . 5_666 ? P1 O4 Ni1 127.61(13) . 4_456 ? P1 O5 H1 109.5 . . ? Ni1 O1W H1B 119.4 . . ? Ni1 O1W H1A 108.7 . . ? H1B O1W H1A 110.8 . . ? O1 C1 O2 123.2(3) . . ? O1 C1 C2 120.2(3) . . ? O2 C1 C2 116.6(3) . . ? C3 C2 C7 119.2(3) . . ? C3 C2 C1 115.8(3) . . ? C7 C2 C1 124.8(3) . . ? C2 C3 C4 121.4(4) . . ? C2 C3 H3 119.3 . . ? C4 C3 H3 119.3 . . ? C5 C4 C3 119.6(3) . . ? C5 C4 H4 120.2 . . ? C3 C4 H4 120.2 . . ? C4 C5 C6 119.6(3) . . ? C4 C5 H5 120.2 . . ? C6 C5 H5 120.2 . . ? C5 C6 C7 121.4(3) . . ? C5 C6 H6 119.3 . . ? C7 C6 H6 119.3 . . ? C6 C7 C2 118.7(3) . . ? C6 C7 P1 116.9(3) . . ? C2 C7 P1 124.1(3) . . ? 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 O1W H1A O5 0.89 2.15 2.959(4) 152.0 4_556 O1W H1B O2 0.88 2.04 2.888(3) 161.3 5_656 O5 H1 O4 0.82 1.79 2.609(3) 173.8 8_665 _diffrn_measured_fraction_theta_max 0.968 _diffrn_reflns_theta_full 28.27 _diffrn_measured_fraction_theta_full 0.968 _refine_diff_density_max 0.648 _refine_diff_density_min -0.580 _refine_diff_density_rms 0.128