# Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2000 # CCDC Number: 186/2101 data_compound_cani _publ_contact_author ; Dra. Miren Karmele Urtiaga Dpto. de Mineralog\'ia y Petrolog\'ia Universidad del Pa\'is Vasco Apartado 644 48080 Bilbao Spain ; _publ_contact_author_phone '34 4 6012555' _publ_contact_author_fax '34 4 4648500' _publ_contact_author_email nppurgrm@lg.ehu.es _publ_requested_journal 'J.Chem.Soc.Dalton Trans.' loop_ _publ_author_name _publ_author_address 'Gil de Muro, I.' ; Dpto. Qu\'imica Inorg\'anica Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Insausti, M.' ; Dpto. Qu\'imica Inorg\'anica Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Lezama, L.' ; Dpto. Qu\'imica Inorg\'anica Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Urtiaga, M.K.' ; Dpto. de Mineralog\'ia y Petrolog\'ia Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Arriortua, M.I.' ; Dpto. de Mineralog\'ia y Petrolog\'ia Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Rojo, T.' ; Dpto. Qu\'imica Inorg\'anica Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; data_cani _audit_creation_method SHELXL-97 _chemical_formula_sum 'C3 H8 Ca0.50 Ni0.50 O7' _chemical_formula_weight 205.49 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' 'Ca' 'Ca' 0.2262 0.3064 '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 'P b c n' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y+1/2, z+1/2' '-x, y, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y-1/2, -z-1/2' 'x, -y, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 8.921(2) _cell_length_b 11.935(2) _cell_length_c 13.274(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 1413.3(7) _cell_formula_units_Z 8 _cell_measurement_temperature 293(2) _exptl_crystal_F_000 848 _exptl_absorpt_coefficient_mu 1.810 _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Enraf-Nonius CAD-4 diffractometer' _diffrn_measurement_method '\w-2\q' _diffrn_standards_number 2 _diffrn_standards_interval_count 200 _diffrn_reflns_number 4033 _diffrn_reflns_av_R_equivalents 0.0551 _diffrn_reflns_av_sigmaI/netI 0.0916 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 2.85 _diffrn_reflns_theta_max 29.96 _reflns_number_total 2062 _reflns_number_observed 1166 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Enraf-Nonius CAD-4' _computing_cell_refinement 'Enraf-Nonius CAD-4' _computing_data_reduction 'Xtal 3.2 (Hall, Flack & Stewart, 1992)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _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^)+(0.0611P)^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 2062 _refine_ls_number_parameters 127 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1408 _refine_ls_R_factor_gt 0.0500 _refine_ls_wR_factor_ref 0.1498 _refine_ls_wR_factor_gt 0.0936 _refine_ls_goodness_of_fit_ref 1.077 _refine_ls_restrained_S_all 1.077 _refine_ls_shift/su_max 0.389 _refine_ls_shift/su_mean 0.036 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 Ni Ni 0.5000 0.5000 0.0000 0.0121(2) Uani 1 2 d S . . Ca Ca 0.0000 0.23825(10) 0.2500 0.0128(3) Uani 1 2 d S . . O1 O 0.1455(5) 0.3738(3) 0.1614(3) 0.0227(8) Uani 1 1 d . . . O2 O 0.2927(4) 0.4758(3) 0.0652(3) 0.0159(7) Uani 1 1 d . . . C1 C 0.2469(5) 0.3821(4) 0.0973(4) 0.0142(10) Uani 1 1 d . . . C2 C 0.3159(6) 0.2744(4) 0.0580(4) 0.0178(10) Uani 1 1 d . . . H2A H 0.249(8) 0.218(6) 0.062(5) 0.035(7) Uiso 1 1 d . . . H2B H 0.399(7) 0.259(5) 0.105(5) 0.035(7) Uiso 1 1 d . . . C3 C 0.3779(5) 0.2776(4) -0.0478(4) 0.0147(9) Uani 1 1 d . . . O3 O 0.4770(4) 0.3502(3) -0.0722(3) 0.0156(7) Uani 1 1 d . . . O4 O 0.3362(4) 0.2058(3) -0.1102(3) 0.0227(9) Uani 1 1 d . . . OW1 O 0.1944(5) 0.0986(3) 0.2400(3) 0.0235(8) Uani 1 1 d . . . HW10 H 0.210(8) 0.065(6) 0.187(5) 0.035(7) Uiso 1 1 d . . . HW11 H 0.258(9) 0.100(6) 0.273(6) 0.035(7) Uiso 1 1 d . . . OW2 O -0.0912(5) -0.0765(3) 0.1254(3) 0.0209(8) Uani 1 1 d . . . HW20 H -0.164(9) -0.120(5) 0.117(5) 0.035(7) Uiso 1 1 d . . . HW21 H -0.115(7) -0.022(6) 0.168(5) 0.035(7) Uiso 1 1 d . . . OW3 O -0.0743(6) 0.5565(4) 0.1201(4) 0.0412(12) Uani 1 1 d . . . HW30 H -0.013(8) 0.514(6) 0.139(6) 0.035(7) Uiso 1 1 d . . . HW31 H -0.109(8) 0.525(6) 0.077(6) 0.035(7) 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 Ni 0.0129(4) 0.0114(3) 0.0122(3) -0.0008(3) 0.0028(4) -0.0015(5) Ca 0.0132(5) 0.0148(6) 0.0105(5) 0.000 -0.0001(6) 0.000 O1 0.0232(19) 0.021(2) 0.0239(19) 0.0008(16) 0.0115(16) -0.0018(16) O2 0.0159(16) 0.0133(16) 0.0184(17) 0.0000(13) 0.0062(14) -0.0007(14) C1 0.015(2) 0.019(2) 0.0092(19) -0.0043(19) -0.0007(17) -0.0021(19) C2 0.023(3) 0.015(2) 0.015(2) 0.002(2) 0.010(2) -0.002(2) C3 0.011(2) 0.015(2) 0.018(2) -0.0007(19) 0.0025(19) 0.0007(18) O3 0.0147(18) 0.0170(16) 0.0152(15) -0.0014(13) 0.0048(13) -0.0035(14) O4 0.026(2) 0.0219(19) 0.0207(19) -0.0105(16) 0.0081(16) -0.0122(16) OW1 0.027(2) 0.0285(18) 0.015(2) -0.0059(18) -0.0021(17) 0.0098(16) OW2 0.023(2) 0.0195(18) 0.0207(19) -0.0003(16) -0.0004(16) -0.0039(16) OW3 0.038(3) 0.039(3) 0.047(3) -0.001(2) 0.001(3) 0.004(2) _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 Ni O3 2.039(3) . ? Ni O3 2.039(3) 5_665 ? Ni O2 2.063(3) . ? Ni O2 2.063(3) 5_665 ? Ni OW2 2.066(4) 4 ? Ni OW2 2.066(4) 8_665 ? Ca O1 2.384(4) . ? Ca O1 2.384(4) 3 ? Ca OW1 2.409(4) 3 ? Ca OW1 2.409(4) . ? Ca O4 2.454(4) 4_455 ? Ca O4 2.454(4) 2 ? Ca O3 2.593(3) 4_455 ? Ca O3 2.593(3) 2 ? Ca C3 2.902(5) 4_455 ? Ca C3 2.903(5) 2 ? O1 C1 1.246(6) . ? O2 C1 1.264(6) . ? C1 C2 1.517(7) . ? C2 C3 1.510(7) . ? C2 H2A 0.90(7) . ? C2 H2B 0.99(7) . ? C3 O4 1.248(6) . ? C3 O3 1.280(6) . ? C3 Ca 2.903(5) 2_554 ? O3 Ca 2.593(3) 2_554 ? O4 Ca 2.454(4) 2_554 ? OW1 HW10 0.82(7) . ? OW1 HW11 0.72(8) . ? OW2 Ni 2.066(4) 4_455 ? OW2 HW20 0.84(7) . ? OW2 HW21 0.88(7) . ? OW3 HW30 0.78(7) . ? OW3 HW31 0.76(7) . ? 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 Ni O3 180.0 . 5_665 ? O3 Ni O2 89.10(13) . . ? O3 Ni O2 90.90(13) 5_665 . ? O3 Ni O2 90.90(13) . 5_665 ? O3 Ni O2 89.10(13) 5_665 5_665 ? O2 Ni O2 180.0 . 5_665 ? O3 Ni OW2 88.23(15) . 4 ? O3 Ni OW2 91.77(15) 5_665 4 ? O2 Ni OW2 92.71(15) . 4 ? O2 Ni OW2 87.29(15) 5_665 4 ? O3 Ni OW2 91.77(15) . 8_665 ? O3 Ni OW2 88.23(15) 5_665 8_665 ? O2 Ni OW2 87.29(15) . 8_665 ? O2 Ni OW2 92.71(15) 5_665 8_665 ? OW2 Ni OW2 180.0 4 8_665 ? O1 Ca O1 94.54(19) . 3 ? O1 Ca OW1 152.70(15) . 3 ? O1 Ca OW1 92.90(14) 3 3 ? O1 Ca OW1 92.90(14) . . ? O1 Ca OW1 152.70(15) 3 . ? OW1 Ca OW1 92.4(2) 3 . ? O1 Ca O4 76.51(14) . 4_455 ? O1 Ca O4 82.19(13) 3 4_455 ? OW1 Ca O4 78.55(14) 3 4_455 ? OW1 Ca O4 125.11(14) . 4_455 ? O1 Ca O4 82.19(13) . 2 ? O1 Ca O4 76.51(14) 3 2 ? OW1 Ca O4 125.11(14) 3 2 ? OW1 Ca O4 78.55(14) . 2 ? O4 Ca O4 148.42(18) 4_455 2 ? O1 Ca O3 82.57(12) . 4_455 ? O1 Ca O3 133.00(13) 3 4_455 ? OW1 Ca O3 73.23(13) 3 4_455 ? OW1 Ca O3 74.04(13) . 4_455 ? O4 Ca O3 51.38(11) 4_455 4_455 ? O4 Ca O3 147.76(12) 2 4_455 ? O1 Ca O3 132.99(13) . 2 ? O1 Ca O3 82.57(12) 3 2 ? OW1 Ca O3 74.04(13) 3 2 ? OW1 Ca O3 73.23(13) . 2 ? O4 Ca O3 147.76(12) 4_455 2 ? O4 Ca O3 51.37(11) 2 2 ? O3 Ca O3 131.95(15) 4_455 2 ? O1 Ca C3 78.03(14) . 4_455 ? O1 Ca C3 107.20(14) 3 4_455 ? OW1 Ca C3 74.68(14) 3 4_455 ? OW1 Ca C3 100.04(14) . 4_455 ? O4 Ca C3 25.21(12) 4_455 4_455 ? O4 Ca C3 160.08(13) 2 4_455 ? O3 Ca C3 26.17(12) 4_455 4_455 ? O3 Ca C3 147.62(13) 2 4_455 ? O1 Ca C3 107.20(14) . 2 ? O1 Ca C3 78.03(14) 3 2 ? OW1 Ca C3 100.03(14) 3 2 ? OW1 Ca C3 74.67(14) . 2 ? O4 Ca C3 160.08(13) 4_455 2 ? O4 Ca C3 25.20(12) 2 2 ? O3 Ca C3 147.62(13) 4_455 2 ? O3 Ca C3 26.17(12) 2 2 ? C3 Ca C3 172.5(2) 4_455 2 ? C1 O1 Ca 141.8(3) . . ? C1 O2 Ni 123.7(3) . . ? O1 C1 O2 122.3(5) . . ? O1 C1 C2 117.5(4) . . ? O2 C1 C2 120.2(4) . . ? C3 C2 C1 116.5(4) . . ? C3 C2 H2A 108(4) . . ? C1 C2 H2A 111(4) . . ? C3 C2 H2B 109(4) . . ? C1 C2 H2B 104(4) . . ? H2A C2 H2B 109(5) . . ? O4 C3 O3 120.2(4) . . ? O4 C3 C2 119.4(5) . . ? O3 C3 C2 120.4(4) . . ? O4 C3 Ca 56.9(3) . 2_554 ? O3 C3 Ca 63.3(2) . 2_554 ? C2 C3 Ca 174.8(4) . 2_554 ? C3 O3 Ni 123.0(3) . . ? C3 O3 Ca 90.5(3) . 2_554 ? Ni O3 Ca 140.98(16) . 2_554 ? C3 O4 Ca 97.9(3) . 2_554 ? Ca OW1 HW10 121(5) . . ? Ca OW1 HW11 121(6) . . ? HW10 OW1 HW11 114(8) . . ? Ni OW2 HW20 118(5) 4_455 . ? Ni OW2 HW21 106(4) 4_455 . ? HW20 OW2 HW21 111(6) . . ? HW30 OW3 HW31 102(8) . . ? 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 O1 Ca O1 C1 -178.2(6) 3 . . . ? OW1 Ca O1 C1 -72.8(7) 3 . . . ? OW1 Ca O1 C1 28.1(6) . . . . ? O4 Ca O1 C1 -97.3(6) 4_455 . . . ? O4 Ca O1 C1 106.1(6) 2 . . . ? O3 Ca O1 C1 -45.4(6) 4_455 . . . ? O3 Ca O1 C1 97.8(6) 2 . . . ? C3 Ca O1 C1 -71.5(6) 4_455 . . . ? C3 Ca O1 C1 103.0(6) 2 . . . ? O3 Ni O2 C1 39.6(4) . . . . ? O3 Ni O2 C1 -140.4(4) 5_665 . . . ? O2 Ni O2 C1 -74(18) 5_665 . . . ? OW2 Ni O2 C1 127.7(4) 4 . . . ? OW2 Ni O2 C1 -52.3(4) 8_665 . . . ? Ca O1 C1 O2 177.1(4) . . . . ? Ca O1 C1 C2 -3.2(8) . . . . ? Ni O2 C1 O1 158.0(4) . . . . ? Ni O2 C1 C2 -21.7(6) . . . . ? O1 C1 C2 C3 151.5(5) . . . . ? O2 C1 C2 C3 -28.8(7) . . . . ? C1 C2 C3 O4 -127.0(5) . . . . ? C1 C2 C3 O3 55.9(7) . . . . ? C1 C2 C3 Ca -170(4) . . . 2_554 ? O4 C3 O3 Ni 157.5(4) . . . . ? C2 C3 O3 Ni -25.4(6) . . . . ? Ca C3 O3 Ni 158.8(3) 2_554 . . . ? O4 C3 O3 Ca -1.2(5) . . . 2_554 ? C2 C3 O3 Ca 175.8(4) . . . 2_554 ? O3 Ni O3 C3 100(5) 5_665 . . . ? O2 Ni O3 C3 -14.5(4) . . . . ? O2 Ni O3 C3 165.5(4) 5_665 . . . ? OW2 Ni O3 C3 -107.2(4) 4 . . . ? OW2 Ni O3 C3 72.8(4) 8_665 . . . ? O3 Ni O3 Ca -115(4) 5_665 . . 2_554 ? O2 Ni O3 Ca 130.4(2) . . . 2_554 ? O2 Ni O3 Ca -49.6(2) 5_665 . . 2_554 ? OW2 Ni O3 Ca 37.7(3) 4 . . 2_554 ? OW2 Ni O3 Ca -142.3(3) 8_665 . . 2_554 ? O3 C3 O4 Ca 1.3(5) . . . 2_554 ? C2 C3 O4 Ca -175.7(4) . . . 2_554 ? _diffrn_measured_fraction_theta_max 1.000 _diffrn_reflns_theta_full 29.96 _diffrn_measured_fraction_theta_full 1.000 _refine_diff_density_max 0.408 _refine_diff_density_min -0.441 _refine_diff_density_rms 0.102 data_compound_camn _publ_contact_author ; Dra. Miren Karmele Urtiaga Dpto. de Mineralog\'ia y Petrolog\'ia Universidad del Pa\'is Vasco Apartado 644 48080 Bilbao Spain ; _publ_contact_author_phone '34 4 6012555' _publ_contact_author_fax '34 4 4648500' _publ_contact_author_email nppurgrm@lg.ehu.es _publ_requested_journal 'J.Chem.Soc.Dalton Trans.' loop_ _publ_author_name _publ_author_address 'Gil de Muro, I.' ; Dpto. Qu\'imica Inorg\'anica Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Insausti, M.' ; Dpto. Qu\'imica Inorg\'anica Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Lezama, L.' ; Dpto. Qu\'imica Inorg\'anica Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Urtiaga, M.K.' ; Dpto. de Mineralog\'ia y Petrolog\'ia Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Arriortua, M.I.' ; Dpto. de Mineralog\'ia y Petrolog\'ia Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; 'Rojo, T.' ; Dpto. Qu\'imica Inorg\'anica Facultad de Ciencias Universidad del Pa\'is Vasco/E.H.U. P.O. Box 644 48080 Bilbao Spain ; data_camn _audit_creation_method SHELXL _chemical_formula_sum 'C6 H12 Ca Mn O12' _chemical_formula_weight 371.18 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' 'Mn' 'Mn' 0.3368 0.7283 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 'Ca' 'Ca' 0.2262 0.3064 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting 'monoclinic' _symmetry_space_group_name_H-M 'C 2/c' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z+1/2' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y, z-1/2' '-x+1/2, -y+1/2, -z' 'x+1/2, -y+1/2, z-1/2' _cell_length_a 14.086(2) _cell_length_b 7.4880(10) _cell_length_c 13.273(3) _cell_angle_alpha 90.00 _cell_angle_beta 118.68(2) _cell_angle_gamma 90.00 _cell_volume 1228.2(4) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _exptl_crystal_density_diffrn 2.007 _exptl_crystal_F_000 756 _exptl_absorpt_coefficient_mu 1.556 _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device ? _diffrn_measurement_method ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 1794 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0390 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 18 _diffrn_reflns_theta_min 3.18 _diffrn_reflns_theta_max 29.98 _reflns_number_total 1794 _reflns_number_observed 1437 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'Enraf-Nonius CAD-4' _computing_cell_refinement 'Enraf-Nonius CAD-4' _computing_data_reduction 'Xtal 3.2 (Hall, Flack & Stewart, 1992)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _refine_special_details ; Refinement on F^2^ for ALL reflections except for 33 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 'calc w=1/[\s^2^(Fo^2^)+(0.0377P)^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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 1761 _refine_ls_number_parameters 107 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0445 _refine_ls_R_factor_obs 0.0269 _refine_ls_wR_factor_all 0.0851 _refine_ls_wR_factor_obs 0.0633 _refine_ls_goodness_of_fit_all 1.019 _refine_ls_goodness_of_fit_obs 1.042 _refine_ls_restrained_S_all 1.264 _refine_ls_restrained_S_obs 1.042 _refine_ls_shift/esd_max -0.005 _refine_ls_shift/esd_mean 0.001 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 Ca Ca 0.0000 0.11854(5) 0.2500 0.01638(10) Uani 1 d S . Mn Mn 0.2500 0.7500 0.5000 0.01897(10) Uani 1 d S . O1 O 0.19500(10) 0.5050(2) 0.39816(10) 0.0278(3) Uani 1 d . . O2 O 0.11235(10) 0.3460(2) 0.23868(10) 0.0255(3) Uani 1 d . . C1 C 0.15540(11) 0.4870(2) 0.29138(13) 0.0178(3) Uani 1 d . . C2 C 0.16279(14) 0.6401(2) 0.22040(14) 0.0224(3) Uani 1 d . . H21 H 0.23760(14) 0.6518(2) 0.23740(14) 0.039(4) Uiso 1 calc R . H22 H 0.12070(14) 0.6089(2) 0.13985(14) 0.039(4) Uiso 1 calc R . C3 C 0.12437(11) 0.8201(2) 0.23859(13) 0.0174(3) Uani 1 d . . O3 O 0.15377(11) 0.8791(2) 0.33810(10) 0.0279(3) Uani 1 d . . O4 O 0.06390(11) 0.9098(2) 0.15245(11) 0.0313(3) Uani 1 d . . O1W O 0.10215(11) 0.2113(2) 0.44714(11) 0.0280(3) Uani 1 d . . O2W O 0.10733(11) 0.7365(2) 0.52513(12) 0.0345(3) Uani 1 d . . H1W H 0.1469(23) 0.1505(40) 0.5021(25) 0.056(4) Uiso 1 d . . H2W H 0.1430(22) 0.3034(41) 0.4614(24) 0.056(4) Uiso 1 d . . H3W H 0.0999(23) 0.7141(38) 0.5753(28) 0.056(4) Uiso 1 d . . H4W H 0.0485(24) 0.7819(40) 0.4718(26) 0.056(4) Uiso 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 Ca 0.0150(2) 0.0157(2) 0.0194(2) 0.000 0.0090(2) 0.000 Mn 0.0197(2) 0.0193(2) 0.0168(2) -0.00168(12) 0.00784(12) -0.00071(12) O1 0.0394(7) 0.0192(5) 0.0230(6) -0.0020(4) 0.0135(5) -0.0060(5) O2 0.0297(6) 0.0221(5) 0.0292(6) -0.0077(5) 0.0177(5) -0.0107(5) C1 0.0155(6) 0.0171(6) 0.0231(7) -0.0015(5) 0.0111(6) -0.0009(5) C2 0.0281(8) 0.0181(7) 0.0266(7) 0.0013(6) 0.0178(7) 0.0025(6) C3 0.0137(6) 0.0168(6) 0.0239(7) 0.0002(5) 0.0108(5) -0.0005(5) O3 0.0362(7) 0.0237(5) 0.0222(5) -0.0003(5) 0.0127(5) 0.0081(5) O4 0.0335(7) 0.0281(6) 0.0235(6) 0.0018(5) 0.0067(5) 0.0102(5) O1W 0.0289(6) 0.0282(6) 0.0236(6) 0.0006(5) 0.0099(5) -0.0031(5) O2W 0.0231(6) 0.0559(9) 0.0273(6) 0.0086(6) 0.0143(5) 0.0060(6) _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 Ca O2 2.3782(12) . ? Ca O2 2.3782(12) 2 ? Ca O1W 2.4054(14) 2 ? Ca O1W 2.4055(14) . ? Ca O4 2.4595(13) 2_545 ? Ca O4 2.4595(13) 1_545 ? Ca O3 2.6156(13) 2_545 ? Ca O3 2.6156(13) 1_545 ? Ca C3 2.8882(15) 1_545 ? Ca C3 2.8882(15) 2_545 ? Mn O3 2.1434(13) 7_566 ? Mn O3 2.1434(13) . ? Mn O1 2.1878(12) . ? Mn O1 2.1878(12) 7_566 ? Mn O2W 2.1917(14) . ? Mn O2W 2.1917(14) 7_566 ? O1 C1 1.257(2) . ? O2 C1 1.251(2) . ? C1 C2 1.519(2) . ? C2 C3 1.514(2) . ? C2 H21 0.97 . ? C2 H22 0.97 . ? C3 O4 1.245(2) . ? C3 O3 1.260(2) . ? C3 Ca 2.8882(15) 1_565 ? O3 Ca 2.6156(13) 1_565 ? O4 Ca 2.4595(13) 1_565 ? O1W H1W 0.83(3) . ? O1W H2W 0.86(3) . ? O2W H3W 0.74(3) . ? O2W H4W 0.86(3) . ? 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 O2 Ca O2 88.53(6) . 2 ? O2 Ca O1W 78.06(5) . 2 ? O2 Ca O1W 78.06(5) 2 2 ? O2 Ca O1W 78.06(5) . . ? O2 Ca O1W 78.06(5) 2 . ? O1W Ca O1W 146.42(7) 2 . ? O2 Ca O4 155.67(4) . 2_545 ? O2 Ca O4 89.95(5) 2 2_545 ? O1W Ca O4 125.26(5) 2 2_545 ? O1W Ca O4 77.87(5) . 2_545 ? O2 Ca O4 89.95(5) . 1_545 ? O2 Ca O4 155.67(4) 2 1_545 ? O1W Ca O4 77.87(5) 2 1_545 ? O1W Ca O4 125.26(5) . 1_545 ? O4 Ca O4 101.07(7) 2_545 1_545 ? O2 Ca O3 153.63(4) . 2_545 ? O2 Ca O3 94.91(5) 2 2_545 ? O1W Ca O3 77.11(5) 2 2_545 ? O1W Ca O3 128.24(4) . 2_545 ? O4 Ca O3 50.65(4) 2_545 2_545 ? O4 Ca O3 76.28(5) 1_545 2_545 ? O2 Ca O3 94.91(5) . 1_545 ? O2 Ca O3 153.63(4) 2 1_545 ? O1W Ca O3 128.24(4) 2 1_545 ? O1W Ca O3 77.11(5) . 1_545 ? O4 Ca O3 76.27(5) 2_545 1_545 ? O4 Ca O3 50.65(4) 1_545 1_545 ? O3 Ca O3 93.47(6) 2_545 1_545 ? O2 Ca C3 96.43(4) . 1_545 ? O2 Ca C3 175.03(4) 2 1_545 ? O1W Ca C3 103.16(5) 2 1_545 ? O1W Ca C3 102.67(5) . 1_545 ? O4 Ca C3 85.42(5) 2_545 1_545 ? O4 Ca C3 25.32(4) 1_545 1_545 ? O3 Ca C3 80.75(4) 2_545 1_545 ? O3 Ca C3 25.86(4) 1_545 1_545 ? O2 Ca C3 175.03(4) . 2_545 ? O2 Ca C3 96.43(4) 2 2_545 ? O1W Ca C3 102.67(5) 2 2_545 ? O1W Ca C3 103.16(5) . 2_545 ? O4 Ca C3 25.32(4) 2_545 2_545 ? O4 Ca C3 85.42(5) 1_545 2_545 ? O3 Ca C3 25.86(4) 2_545 2_545 ? O3 Ca C3 80.75(4) 1_545 2_545 ? C3 Ca C3 78.60(6) 1_545 2_545 ? O3 Mn O3 180.0 7_566 . ? O3 Mn O1 96.16(5) 7_566 . ? O3 Mn O1 83.85(5) . . ? O3 Mn O1 83.84(5) 7_566 7_566 ? O3 Mn O1 96.16(5) . 7_566 ? O1 Mn O1 180.0 . 7_566 ? O3 Mn O2W 90.66(6) 7_566 . ? O3 Mn O2W 89.34(6) . . ? O1 Mn O2W 88.67(6) . . ? O1 Mn O2W 91.33(6) 7_566 . ? O3 Mn O2W 89.34(6) 7_566 7_566 ? O3 Mn O2W 90.66(6) . 7_566 ? O1 Mn O2W 91.33(6) . 7_566 ? O1 Mn O2W 88.67(6) 7_566 7_566 ? O2W Mn O2W 180.0 . 7_566 ? C1 O1 Mn 128.36(10) . . ? C1 O2 Ca 136.71(10) . . ? O2 C1 O1 123.69(14) . . ? O2 C1 C2 116.71(14) . . ? O1 C1 C2 119.55(13) . . ? C3 C2 C1 115.89(13) . . ? C3 C2 H21 108.31(8) . . ? C1 C2 H21 108.31(9) . . ? C3 C2 H22 108.31(9) . . ? C1 C2 H22 108.31(9) . . ? H21 C2 H22 107.4 . . ? O4 C3 O3 120.62(14) . . ? O4 C3 C2 118.25(14) . . ? O3 C3 C2 121.12(14) . . ? O4 C3 Ca 57.70(8) . 1_565 ? O3 C3 Ca 64.90(8) . 1_565 ? C2 C3 Ca 165.77(10) . 1_565 ? C3 O3 Mn 128.63(10) . . ? C3 O3 Ca 89.25(9) . 1_565 ? Mn O3 Ca 138.33(6) . 1_565 ? C3 O4 Ca 96.98(10) . 1_565 ? Ca O1W H1W 126.9(20) . . ? Ca O1W H2W 117.3(19) . . ? H1W O1W H2W 95.7(25) . . ? Mn O2W H3W 133.0(23) . . ? Mn O2W H4W 116.7(20) . . ? H3W O2W H4W 109.4(30) . . ? _refine_diff_density_max 0.417 _refine_diff_density_min -0.343 _refine_diff_density_rms 0.094