Supplementary Material (ESI) for Chemical Communications This journal is © The Royal Society of Chemistry 2001 data_Cu4(hedp)2(pz)(H2O)4 _database_code_CSD 169230 _journal_coden_Cambridge 182 _publ_requested_journal 'Chemical Communications' loop_ _publ_author_name 'Gao, Song' 'Li-Min, Zheng' 'Xin, Xinquan' 'Yin, Ping' _publ_contact_author_name 'Dr Zheng Li-Min' _publ_contact_author_address ; Dr Zheng Li-Min Chemistry Department Nanjing University Coordination Chemistry Institute,Ch Nanjing Jiangsu 210093 CHINA ; _publ_contact_author_email 'LMZHENG@NETRA.NJU.EDU.CN' _publ_section_title ; Cu4{CH3C(OH)(PO3)2}2(C4H4N2)(H2O)4: a novel three dimensional copper diphosphonate with metamagnetism ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C8 H20 Cu4 N2 O18 P4' _chemical_formula_weight 810.30 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' 'Cu' 'Cu' 0.3201 1.2651 '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 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 6.248(2) _cell_length_b 8.035(3) _cell_length_c 11.014(4) _cell_angle_alpha 86.035(6) _cell_angle_beta 87.889(6) _cell_angle_gamma 82.809(5) _cell_volume 547.1(3) _cell_formula_units_Z 1 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 1467 _cell_measurement_theta_min 3.06 _cell_measurement_theta_max 25.01 _exptl_crystal_description 'needle' _exptl_crystal_colour 'blue' _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.04 _exptl_crystal_size_min 0.04 _exptl_crystal_density_diffrn 2.459 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 402 _exptl_absorpt_coefficient_mu 4.220 _exptl_absorpt_correction_type 'empirical' _exptl_absorpt_correction_T_min 0.5654 _exptl_absorpt_correction_T_max 0.9945 _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'Siemens SMART CCD' _diffrn_measurement_method CCD _diffrn_detector_area_resol_mean 4K _diffrn_standards_decay_% 0.0 _diffrn_reflns_number 2823 _diffrn_reflns_av_R_equivalents 0.0679 _diffrn_reflns_av_sigmaI/netI 0.0452 _diffrn_reflns_limit_h_min -7 _diffrn_reflns_limit_h_max 7 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 2.56 _diffrn_reflns_theta_max 25.05 _reflns_number_total 1909 _reflns_number_gt 1641 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Siemens SMART software (Siemens, 1996)' _computing_cell_refinement 'Bruker SAINT software (Bruker, 1999)' _computing_data_reduction 'Bruker SAINT software (Bruker, 1999)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _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^)+(0.0855P)^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 1909 _refine_ls_number_parameters 187 _refine_ls_number_restraints 7 _refine_ls_R_factor_all 0.0550 _refine_ls_R_factor_gt 0.0468 _refine_ls_wR_factor_ref 0.1262 _refine_ls_wR_factor_gt 0.1211 _refine_ls_goodness_of_fit_ref 1.051 _refine_ls_restrained_S_all 1.049 _refine_ls_shift/su_max 0.001 _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 Cu1 Cu 0.5000 0.0000 0.5000 0.0149(3) Uani 1 2 d S . . Cu2 Cu 0.99477(10) 0.14197(8) 0.18476(6) 0.0143(2) Uani 1 1 d . . . Cu3 Cu 1.0000 -0.5000 0.5000 0.0182(3) Uani 1 2 d S . . P1 P 0.5152(2) 0.09367(18) 0.23094(13) 0.0133(3) Uani 1 1 d . . . P2 P 0.8423(2) -0.17195(18) 0.33967(12) 0.0122(3) Uani 1 1 d . . . O1 O 0.5036(7) 0.1635(5) 0.3574(4) 0.0205(9) Uani 1 1 d . . . O2 O 0.6930(6) 0.1586(5) 0.1508(3) 0.0172(9) Uani 1 1 d . . . O3 O 0.3025(6) 0.1226(5) 0.1680(4) 0.0219(10) Uani 1 1 d . . . O4 O 0.7943(6) -0.0895(5) 0.4594(3) 0.0178(9) Uani 1 1 d . . . O5 O 1.0102(6) -0.0877(5) 0.2601(3) 0.0151(8) Uani 1 1 d . . . O6 O 0.9117(7) -0.3584(5) 0.3585(4) 0.0196(9) Uani 1 1 d . . . O7 O 0.4240(6) -0.1961(5) 0.3421(4) 0.0207(9) Uani 1 1 d D . . H7 H 0.298(5) -0.181(9) 0.304(5) 0.029 Uiso 1 1 d D . . O1W O 0.9359(7) 0.2624(5) 0.3752(4) 0.0218(10) Uani 1 1 d D . . H1WA H 1.021(6) 0.201(7) 0.430(4) 0.031 Uiso 1 1 d D . . H1WB H 0.795(3) 0.247(8) 0.382(5) 0.031 Uiso 1 1 d D . . O2W O 1.3025(7) -0.5291(6) 0.4260(5) 0.0331(11) Uani 1 1 d D . . H2WB H 1.408(7) -0.466(7) 0.435(6) 0.046 Uiso 1 1 d D . . H2WA H 1.343(9) -0.629(4) 0.396(6) 0.046 Uiso 1 1 d D . . C1 C 0.5874(8) -0.1353(7) 0.2587(5) 0.0130(11) Uani 1 1 d . . . C2 C 0.6006(11) -0.2226(9) 0.1402(6) 0.0281(15) Uani 1 1 d . . . H2A H 0.6386 -0.3413 0.1567 0.042 Uiso 1 1 calc R . . H2B H 0.7083 -0.1792 0.0868 0.042 Uiso 1 1 calc R . . H2C H 0.4632 -0.2025 0.1021 0.042 Uiso 1 1 calc R . . N1 N 0.9916(7) 0.3593(6) 0.0785(4) 0.0176(11) Uani 1 1 d . . . C3 C 0.8904(11) 0.3782(8) -0.0260(6) 0.0260(15) Uani 1 1 d . . . H3A H 0.814(12) 0.307(10) -0.045(6) 0.039 Uiso 1 1 d . . . C4 C 1.1018(10) 0.4823(8) 0.1052(6) 0.0232(14) Uani 1 1 d . . . H4A H 1.176(12) 0.471(9) 0.184(6) 0.035 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 Cu1 0.0145(5) 0.0132(5) 0.0150(5) 0.0014(4) 0.0013(4) 0.0040(4) Cu2 0.0088(4) 0.0133(4) 0.0194(4) 0.0051(3) -0.0014(3) 0.0011(3) Cu3 0.0152(5) 0.0129(5) 0.0241(6) 0.0057(4) -0.0012(4) 0.0040(4) P1 0.0089(7) 0.0119(7) 0.0174(7) 0.0050(6) -0.0016(6) 0.0021(5) P2 0.0098(7) 0.0105(7) 0.0149(7) 0.0023(6) -0.0021(5) 0.0025(5) O1 0.026(2) 0.012(2) 0.021(2) 0.0025(17) 0.0028(17) 0.0059(17) O2 0.0090(19) 0.021(2) 0.020(2) 0.0069(17) 0.0001(15) -0.0011(16) O3 0.0084(19) 0.028(2) 0.027(2) 0.0123(19) -0.0059(17) 0.0016(17) O4 0.012(2) 0.023(2) 0.016(2) -0.0044(17) 0.0001(15) 0.0050(17) O5 0.0086(19) 0.015(2) 0.020(2) 0.0029(16) -0.0006(15) 0.0042(15) O6 0.022(2) 0.011(2) 0.023(2) 0.0025(16) -0.0039(17) 0.0072(17) O7 0.011(2) 0.023(2) 0.027(2) 0.0091(18) -0.0006(16) -0.0013(17) O1W 0.023(2) 0.015(2) 0.026(2) 0.0042(18) -0.0093(18) -0.0005(18) O2W 0.020(2) 0.018(2) 0.059(3) 0.001(2) 0.012(2) 0.0022(19) C1 0.009(3) 0.014(3) 0.015(3) 0.003(2) 0.000(2) -0.001(2) C2 0.028(3) 0.031(4) 0.026(3) -0.008(3) -0.011(3) -0.001(3) N1 0.008(2) 0.019(3) 0.024(3) 0.004(2) -0.0010(19) 0.002(2) C3 0.030(4) 0.020(3) 0.030(4) 0.008(3) -0.012(3) -0.011(3) C4 0.024(3) 0.018(3) 0.028(3) 0.005(3) -0.010(3) -0.003(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 Cu1 O4 1.937(4) . ? Cu1 O4 1.937(4) 2_656 ? Cu1 O1 1.978(4) . ? Cu1 O1 1.978(4) 2_656 ? Cu2 O3 1.913(4) 1_655 ? Cu2 O2 1.922(4) . ? Cu2 O5 1.962(4) . ? Cu2 N1 2.032(5) . ? Cu2 O1W 2.368(4) . ? Cu3 O6 1.921(4) . ? Cu3 O6 1.921(4) 2_746 ? Cu3 O2W 2.023(5) 2_746 ? Cu3 O2W 2.023(5) . ? P1 O3 1.507(4) . ? P1 O2 1.515(4) . ? P1 O1 1.533(4) . ? P1 C1 1.846(6) . ? P2 O6 1.509(4) . ? P2 O4 1.520(4) . ? P2 O5 1.535(4) . ? P2 C1 1.836(5) . ? O3 Cu2 1.913(4) 1_455 ? O7 C1 1.456(7) . ? O7 H7 0.897(10) . ? O1W H1WA 0.899(10) . ? O1W H1WB 0.901(10) . ? O2W H2WB 0.896(10) . ? O2W H2WA 0.895(10) . ? C1 C2 1.518(8) . ? C2 H2A 0.9600 . ? C2 H2B 0.9600 . ? C2 H2C 0.9600 . ? N1 C3 1.324(7) . ? N1 C4 1.328(8) . ? C3 C4 1.376(8) 2_765 ? C3 H3A 0.83(8) . ? C4 C3 1.376(8) 2_765 ? C4 H4A 0.99(6) . ? 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 O4 Cu1 O4 180.000(1) . 2_656 ? O4 Cu1 O1 89.55(17) . . ? O4 Cu1 O1 90.45(17) 2_656 . ? O4 Cu1 O1 90.45(17) . 2_656 ? O4 Cu1 O1 89.55(17) 2_656 2_656 ? O1 Cu1 O1 180.000(1) . 2_656 ? O3 Cu2 O2 163.18(17) 1_655 . ? O3 Cu2 O5 90.83(16) 1_655 . ? O2 Cu2 O5 94.63(15) . . ? O3 Cu2 N1 86.54(17) 1_655 . ? O2 Cu2 N1 85.28(16) . . ? O5 Cu2 N1 169.73(18) . . ? O3 Cu2 O1W 101.33(17) 1_655 . ? O2 Cu2 O1W 94.33(16) . . ? O5 Cu2 O1W 92.47(15) . . ? N1 Cu2 O1W 97.77(18) . . ? O6 Cu3 O6 180.0 . 2_746 ? O6 Cu3 O2W 91.72(19) . 2_746 ? O6 Cu3 O2W 88.28(19) 2_746 2_746 ? O6 Cu3 O2W 88.28(19) . . ? O6 Cu3 O2W 91.72(19) 2_746 . ? O2W Cu3 O2W 180.0(3) 2_746 . ? O3 P1 O2 111.1(2) . . ? O3 P1 O1 113.1(3) . . ? O2 P1 O1 112.0(2) . . ? O3 P1 C1 107.9(2) . . ? O2 P1 C1 107.3(2) . . ? O1 P1 C1 105.1(2) . . ? O6 P2 O4 112.2(2) . . ? O6 P2 O5 110.4(2) . . ? O4 P2 O5 112.1(2) . . ? O6 P2 C1 109.6(2) . . ? O4 P2 C1 105.1(2) . . ? O5 P2 C1 107.1(2) . . ? P1 O1 Cu1 117.3(2) . . ? P1 O2 Cu2 127.6(2) . . ? P1 O3 Cu2 147.0(3) . 1_455 ? P2 O4 Cu1 119.1(2) . . ? P2 O5 Cu2 129.9(2) . . ? P2 O6 Cu3 132.3(3) . . ? C1 O7 H7 108(4) . . ? Cu2 O1W H1WA 109(4) . . ? Cu2 O1W H1WB 95(4) . . ? H1WA O1W H1WB 115.1(18) . . ? Cu3 O2W H2WB 128(4) . . ? Cu3 O2W H2WA 115(4) . . ? H2WB O2W H2WA 115.9(19) . . ? O7 C1 C2 111.4(5) . . ? O7 C1 P2 106.3(3) . . ? C2 C1 P2 112.3(4) . . ? O7 C1 P1 107.4(4) . . ? C2 C1 P1 110.9(4) . . ? P2 C1 P1 108.3(3) . . ? C1 C2 H2A 109.5 . . ? C1 C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? C1 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? C3 N1 C4 117.1(5) . . ? C3 N1 Cu2 120.4(4) . . ? C4 N1 Cu2 122.3(4) . . ? N1 C3 C4 122.4(6) . 2_765 ? N1 C3 H3A 121(5) . . ? C4 C3 H3A 117(5) 2_765 . ? N1 C4 C3 120.6(5) . 2_765 ? N1 C4 H4A 118(4) . . ? C3 C4 H4A 122(4) 2_765 . ? loop_ _geom_torsion_atom_site_label_1 _geom_torsion_atom_site_label_2 _geom_torsion_atom_site_label_3 _geom_torsion_atom_site_label_4 _geom_torsion _geom_torsion_site_symmetry_1 _geom_torsion_site_symmetry_2 _geom_torsion_site_symmetry_3 _geom_torsion_site_symmetry_4 _geom_torsion_publ_flag O3 P1 O1 Cu1 104.2(3) . . . . ? O2 P1 O1 Cu1 -129.3(2) . . . . ? C1 P1 O1 Cu1 -13.2(3) . . . . ? O4 Cu1 O1 P1 67.6(3) . . . . ? O4 Cu1 O1 P1 -112.4(3) 2_656 . . . ? O1 Cu1 O1 P1 155(100) 2_656 . . . ? O3 P1 O2 Cu2 -176.5(3) . . . . ? O1 P1 O2 Cu2 56.0(4) . . . . ? C1 P1 O2 Cu2 -58.8(4) . . . . ? O3 Cu2 O2 P1 148.1(5) 1_655 . . . ? O5 Cu2 O2 P1 39.6(3) . . . . ? N1 Cu2 O2 P1 -150.7(3) . . . . ? O1W Cu2 O2 P1 -53.3(3) . . . . ? O2 P1 O3 Cu2 -159.7(5) . . . 1_455 ? O1 P1 O3 Cu2 -32.8(6) . . . 1_455 ? C1 P1 O3 Cu2 83.0(6) . . . 1_455 ? O6 P2 O4 Cu1 -112.5(3) . . . . ? O5 P2 O4 Cu1 122.6(2) . . . . ? C1 P2 O4 Cu1 6.6(3) . . . . ? O4 Cu1 O4 P2 -142(23) 2_656 . . . ? O1 Cu1 O4 P2 -63.4(3) . . . . ? O1 Cu1 O4 P2 116.6(3) 2_656 . . . ? O6 P2 O5 Cu2 170.3(2) . . . . ? O4 P2 O5 Cu2 -63.8(3) . . . . ? C1 P2 O5 Cu2 51.0(4) . . . . ? O3 Cu2 O5 P2 160.2(3) 1_655 . . . ? O2 Cu2 O5 P2 -35.7(3) . . . . ? N1 Cu2 O5 P2 -124.8(8) . . . . ? O1W Cu2 O5 P2 58.9(3) . . . . ? O4 P2 O6 Cu3 -13.3(4) . . . . ? O5 P2 O6 Cu3 112.6(3) . . . . ? C1 P2 O6 Cu3 -129.7(3) . . . . ? O6 Cu3 O6 P2 -9(100) 2_746 . . . ? O2W Cu3 O6 P2 69.8(4) 2_746 . . . ? O2W Cu3 O6 P2 -110.2(4) . . . . ? O6 P2 C1 O7 67.6(4) . . . . ? O4 P2 C1 O7 -53.2(4) . . . . ? O5 P2 C1 O7 -172.6(3) . . . . ? O6 P2 C1 C2 -54.4(5) . . . . ? O4 P2 C1 C2 -175.2(4) . . . . ? O5 P2 C1 C2 65.3(5) . . . . ? O6 P2 C1 P1 -177.3(3) . . . . ? O4 P2 C1 P1 61.9(3) . . . . ? O5 P2 C1 P1 -57.5(3) . . . . ? O3 P1 C1 O7 -63.9(4) . . . . ? O2 P1 C1 O7 176.3(3) . . . . ? O1 P1 C1 O7 57.0(4) . . . . ? O3 P1 C1 C2 58.0(5) . . . . ? O2 P1 C1 C2 -61.7(4) . . . . ? O1 P1 C1 C2 178.9(4) . . . . ? O3 P1 C1 P2 -178.3(3) . . . . ? O2 P1 C1 P2 61.9(3) . . . . ? O1 P1 C1 P2 -57.4(3) . . . . ? O3 Cu2 N1 C3 121.0(5) 1_655 . . . ? O2 Cu2 N1 C3 -44.3(5) . . . . ? O5 Cu2 N1 C3 45.6(11) . . . . ? O1W Cu2 N1 C3 -138.1(5) . . . . ? O3 Cu2 N1 C4 -54.0(5) 1_655 . . . ? O2 Cu2 N1 C4 140.7(5) . . . . ? O5 Cu2 N1 C4 -129.4(9) . . . . ? O1W Cu2 N1 C4 47.0(5) . . . . ? C4 N1 C3 C4 0.4(11) . . . 2_765 ? Cu2 N1 C3 C4 -174.8(5) . . . 2_765 ? C3 N1 C4 C3 -0.4(11) . . . 2_765 ? Cu2 N1 C4 C3 174.7(5) . . . 2_765 ? 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 O7 H7 O5 0.90(5) 1.93(5) 2.786(5) 160(6) 1_455 O1W H1WA O4 0.90(5) 1.82(5) 2.716(5) 176(5) 2_756 O1W H1WB O1 0.90(5) 2.05(5) 2.926(6) 163(7) . O2W H2WB O7 0.90(5) 2.34(5) 2.950(6) 125(5) 1_655 O2W H2WA O1 0.90(5) 1.90(5) 2.768(6) 163(6) 1_645 _diffrn_measured_fraction_theta_max 0.981 _diffrn_reflns_theta_full 25.05 _diffrn_measured_fraction_theta_full 0.981 _refine_diff_density_max 1.214 _refine_diff_density_min -1.027 _refine_diff_density_rms 0.191