# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 186/2115 data_acid _audit_creation_method SHELXL _chemical_name_systematic 'N-piperidinomethane-1,1-methanediphosphonic acid' _chemical_name_common PMDPA _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C6 H15 N O6 P2' _chemical_formula_weight 259.13 _chemical_melting_point ? _chemical_compound_source 'satd 1M NaClO4 ' loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source 'C' 'C' 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'H' 'H' 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'N' 'N' 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' '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' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1)/n loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, -y-1/2, z-1/2' _cell_length_a 8.0583(4) _cell_length_b 6.4558(3) _cell_length_c 18.8222(10) _cell_angle_alpha 90.00 _cell_angle_beta 95.591(1) _cell_angle_gamma 90.00 _cell_volume 974.52(8) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 4171 _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description fragment _exptl_crystal_colour colorless _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.25 _exptl_crystal_size_min 0.40 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.766 _exptl_crystal_density_method ? _exptl_crystal_F_000 544 _exptl_absorpt_coefficient_mu 0.457 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(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 'Siemens P4' _diffrn_measurement_method '\w scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 4861 _diffrn_reflns_av_R_equivalents 0.0787 _diffrn_reflns_av_sigmaI/netI 0.0806 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -6 _diffrn_reflns_limit_k_max 8 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.17 _diffrn_reflns_theta_max 28.01 _reflns_number_total 2289 _reflns_number_observed 1992 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Siemens XSCANS' _computing_cell_refinement 'Siemens XSCANS' _computing_data_reduction 'Siemens SHELXTL' _computing_structure_solution 'SHELXS-86 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-93 (Sheldrick, 1993)' _computing_molecular_graphics 'Siemens SHELXTL' _computing_publication_material 'Siemens SHELXTL' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 5 with very negative F^2^ or flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 '0.1029, 2.4858' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment ? _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0131(39) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 2284 _refine_ls_number_parameters 140 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0924 _refine_ls_R_factor_obs 0.0753 _refine_ls_wR_factor_all 0.2297 _refine_ls_wR_factor_obs 0.1973 _refine_ls_goodness_of_fit_all 1.166 _refine_ls_goodness_of_fit_obs 1.178 _refine_ls_restrained_S_all 1.285 _refine_ls_restrained_S_obs 1.178 _refine_ls_shift/esd_max -0.195 _refine_ls_shift/esd_mean 0.006 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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group P1 P 0.55786(10) 0.74569(14) 0.06231(5) 0.0119(3) Uani 1 d . . P2 P 0.84927(10) 0.73620(14) -0.02934(5) 0.0114(3) Uani 1 d . . O1 O 0.5873(3) 0.9640(4) 0.09458(13) 0.0146(6) Uani 1 d . . H1O1 H 0.5621(56) 1.0537(4) 0.0630(6) 0.018 Uiso 1 calc R . O2 O 0.4777(3) 0.6159(4) 0.11916(14) 0.0161(6) Uani 1 d . . H1O2 H 0.3985(38) 0.5458(57) 0.0993(4) 0.019 Uiso 1 calc R . O3 O 0.4653(3) 0.7378(4) -0.01052(14) 0.0134(6) Uani 1 d . . O4 O 0.7846(3) 0.5969(4) -0.09000(13) 0.0152(6) Uani 1 d . . O5 O 0.7779(3) 0.9605(4) -0.04373(14) 0.0152(6) Uani 1 d . . H1O5 H 0.8338(37) 1.0454(10) -0.0174(18) 0.018 Uiso 1 calc R . O6 O 1.0366(3) 0.7420(4) -0.0130(2) 0.0151(6) Uani 1 d . . N N 0.8929(3) 0.6290(5) 0.1150(2) 0.0110(6) Uani 1 d . . H1N H 0.9813(3) 0.6037(5) 0.0978(2) 0.013 Uiso 1 d R . C1 C 0.7626(4) 0.6343(6) 0.0514(2) 0.0115(7) Uani 1 d . . H1B H 0.7390(4) 0.4851(6) 0.0402(2) 0.014 Uiso 1 calc R . C2 C 0.8519(4) 0.4693(6) 0.1692(2) 0.0153(7) Uani 1 d . . H2B H 0.8310(4) 0.3340(6) 0.1453(2) 0.018 Uiso 1 calc R . H2C H 0.7491(4) 0.5108(6) 0.1904(2) 0.018 Uiso 1 calc R . C3 C 0.9946(5) 0.4480(7) 0.2280(2) 0.0195(8) Uani 1 d . . H3B H 0.9626(5) 0.3484(7) 0.2643(2) 0.023 Uiso 1 calc R . H3C H 1.0939(5) 0.3923(7) 0.2075(2) 0.023 Uiso 1 calc R . C4 C 1.0381(5) 0.6550(7) 0.2637(2) 0.0224(8) Uani 1 d . . H4B H 1.1355(5) 0.6381(7) 0.2995(2) 0.027 Uiso 1 calc R . H4C H 0.9429(5) 0.7046(7) 0.2885(2) 0.027 Uiso 1 calc R . C5 C 1.0786(4) 0.8142(7) 0.2074(2) 0.0190(8) Uani 1 d . . H5B H 1.1026(4) 0.9502(7) 0.2304(2) 0.023 Uiso 1 calc R . H5C H 1.1789(4) 0.7696(7) 0.1850(2) 0.023 Uiso 1 calc R . C6 C 0.9316(4) 0.8348(6) 0.1503(2) 0.0158(7) Uani 1 d . . H6B H 0.8327(4) 0.8853(6) 0.1724(2) 0.019 Uiso 1 calc R . H6C H 0.9588(4) 0.9372(6) 0.1140(2) 0.019 Uiso 1 calc R . 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 P1 0.0065(4) 0.0130(5) 0.0164(6) -0.0004(3) 0.0026(3) -0.0003(3) P2 0.0079(5) 0.0111(5) 0.0158(5) -0.0004(3) 0.0034(3) -0.0008(3) O1 0.0115(11) 0.0146(13) 0.0174(13) -0.0010(10) -0.0003(9) 0.0017(10) O2 0.0104(11) 0.0186(14) 0.0196(13) -0.0008(10) 0.0037(9) -0.0066(10) O3 0.0076(11) 0.0139(13) 0.0183(13) -0.0002(9) -0.0001(9) 0.0003(9) O4 0.0141(11) 0.0149(13) 0.0172(13) -0.0009(10) 0.0051(9) -0.0042(10) O5 0.0096(11) 0.0139(13) 0.0218(14) 0.0006(10) 0.0009(9) 0.0016(9) O6 0.0079(11) 0.0137(13) 0.0246(14) 0.0008(10) 0.0060(10) 0.0003(9) N 0.0067(12) 0.0114(14) 0.0152(14) 0.0009(11) 0.0023(10) 0.0003(10) C1 0.0078(13) 0.011(2) 0.016(2) -0.0001(12) 0.0015(11) -0.0002(12) C2 0.013(2) 0.015(2) 0.017(2) 0.0056(14) 0.0009(12) -0.0006(13) C3 0.018(2) 0.022(2) 0.019(2) 0.0031(15) 0.0034(13) 0.0054(15) C4 0.019(2) 0.029(2) 0.020(2) -0.002(2) 0.0011(13) 0.004(2) C5 0.013(2) 0.022(2) 0.022(2) -0.002(2) -0.0014(13) -0.0014(14) C6 0.0138(15) 0.014(2) 0.020(2) -0.0033(14) 0.0024(13) 0.0005(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 P1 O3 1.496(3) . ? P1 O1 1.544(3) . ? P1 O2 1.549(3) . ? P1 C1 1.829(3) . ? P2 O4 1.506(3) . ? P2 O6 1.512(3) . ? P2 O5 1.572(3) . ? P2 C1 1.855(3) . ? N C6 1.504(4) . ? N C2 1.510(4) . ? N C1 1.514(4) . ? C2 C3 1.523(5) . ? C3 C4 1.521(6) . ? C4 C5 1.534(6) . ? C5 C6 1.525(5) . ? 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 O3 P1 O1 115.81(14) . . ? O3 P1 O2 114.23(14) . . ? O1 P1 O2 106.30(15) . . ? O3 P1 C1 105.0(2) . . ? O1 P1 C1 107.29(15) . . ? O2 P1 C1 107.8(2) . . ? O4 P2 O6 115.75(15) . . ? O4 P2 O5 109.0(2) . . ? O6 P2 O5 110.71(14) . . ? O4 P2 C1 106.2(2) . . ? O6 P2 C1 106.9(2) . . ? O5 P2 C1 107.90(15) . . ? C6 N C2 110.8(3) . . ? C6 N C1 115.3(3) . . ? C2 N C1 111.6(3) . . ? N C1 P1 118.9(2) . . ? N C1 P2 111.6(2) . . ? P1 C1 P2 111.6(2) . . ? N C2 C3 110.7(3) . . ? C4 C3 C2 111.5(3) . . ? C3 C4 C5 109.8(3) . . ? C6 C5 C4 110.0(3) . . ? N C6 C5 110.3(3) . . ? _refine_diff_density_max 0.982 _refine_diff_density_min -0.862 _refine_diff_density_rms 0.167