Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_coden_Cambridge 222 loop_ _publ_author_name D.Ruiz-Molina J.Campo P.Gerbier J.Gomez-Segura I.Imaz J.Veciana K.Wurst _publ_contact_author_name 'Daniel Ruiz-Molina' _publ_contact_author_address ; ICMAB NMMO Campus UAB Cerdanyola del Valles Barcelona 08193 SPAIN ; _publ_contact_author_email DANI@ICMAB.ES _publ_requested_journal 'Dalton Transactions' _publ_section_title ; New insights into ligand inductive effects on the stability of Mn12 single-molecule magnets. Synthesis, magnetic and thermal characterization of complex [Mn12O12(O2CC?CH)16(H2O)4]?3H2O and the corresponding manganese(II) propiolate [Mn3(O2CC?CH)6(H2O)4]?2H2O derived by thermolysis reaction ; data_Mn3prop _database_code_depnum_ccdc_archive 'CCDC 633444' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C18 H18 Mn3 O18' _chemical_formula_sum 'C18 H18 Mn3 O18' _chemical_formula_weight 687.14 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/n' _symmetry_space_group_name_Hall -P2yn 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 9.2800(2) _cell_length_b 9.4132(2) _cell_length_c 14.9675(3) _cell_angle_alpha 90.00 _cell_angle_beta 99.630(1) _cell_angle_gamma 90.00 _cell_volume 1289.05(5) _cell_formula_units_Z 2 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 9970 _cell_measurement_theta_min 1.0 _cell_measurement_theta_max 24.1 _exptl_crystal_description prism _exptl_crystal_colour colorless _exptl_crystal_size_max 0.2 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.770 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 690 _exptl_absorpt_coefficient_mu 1.530 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(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 'Nonius KappaCCD' _diffrn_measurement_method 'phi- and omega-scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7142 _diffrn_reflns_av_R_equivalents 0.0183 _diffrn_reflns_av_sigmaI/netI 0.0192 _diffrn_reflns_limit_h_min 0 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -10 _diffrn_reflns_limit_k_max 10 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.57 _diffrn_reflns_theta_max 24.11 _reflns_number_total 2057 _reflns_number_gt 1889 _reflns_threshold_expression >2sigma(I) _computing_data_collection COLLECT _computing_cell_refinement ? _computing_data_reduction 'DENZO and SCALEPACK' _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^)+(0.0227P)^2^+0.6154P] 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, refined at O7, O8 and O9' _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0055(7) _refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^ _refine_ls_number_reflns 2057 _refine_ls_number_parameters 203 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0220 _refine_ls_R_factor_gt 0.0193 _refine_ls_wR_factor_ref 0.0498 _refine_ls_wR_factor_gt 0.0486 _refine_ls_goodness_of_fit_ref 1.067 _refine_ls_restrained_S_all 1.067 _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 Mn1 Mn 0.0000 0.0000 0.0000 0.01590(12) Uani 1 2 d S . . Mn2 Mn 0.19973(3) 0.07377(3) 0.208595(16) 0.01826(11) Uani 1 1 d . . . O1 O 0.14524(12) 0.16472(12) -0.02529(7) 0.0220(3) Uani 1 1 d . . . O2 O 0.27911(13) 0.21356(13) 0.11012(8) 0.0256(3) Uani 1 1 d . . . O3 O 0.17803(12) -0.09183(11) 0.09965(7) 0.0199(3) Uani 1 1 d . . . O4 O 0.27888(13) -0.25190(12) 0.19868(8) 0.0258(3) Uani 1 1 d . . . O5 O -0.02176(12) 0.10724(12) 0.12875(7) 0.0209(3) Uani 1 1 d . . . O6 O -0.12048(14) 0.25958(14) 0.21598(9) 0.0333(3) Uani 1 1 d . . . O7 O 0.08791(15) -0.05328(13) 0.29658(9) 0.0224(3) Uani 1 1 d . . . H7A H 0.017(3) -0.101(3) 0.2697(18) 0.059(8) Uiso 1 1 d . . . H7B H 0.139(3) -0.109(3) 0.3285(18) 0.055(8) Uiso 1 1 d . . . O8 O 0.42568(15) 0.01783(18) 0.26573(10) 0.0303(3) Uani 1 1 d . . . H8A H 0.458(3) -0.058(3) 0.2663(17) 0.046(8) Uiso 1 1 d . . . H85 H 0.490(3) 0.080(3) 0.2703(18) 0.062(9) Uiso 1 1 d . . . O9 O 0.11291(16) 0.23683(15) -0.20892(10) 0.0307(3) Uani 1 1 d . . . H9A H 0.130(2) 0.213(2) -0.1571(18) 0.045(7) Uiso 1 1 d . . . H9B H 0.191(3) 0.233(3) -0.2286(17) 0.055(8) Uiso 1 1 d . . . C1 C 0.25157(18) 0.22088(17) 0.02520(11) 0.0198(4) Uani 1 1 d . . . C2 C 0.3531(2) 0.30072(19) -0.02079(12) 0.0267(4) Uani 1 1 d . . . C3 C 0.4304(2) 0.3606(2) -0.06316(14) 0.0386(5) Uani 1 1 d . . . H3 H 0.4921 0.4084 -0.0970 0.046 Uiso 1 1 calc . . . C4 C 0.21471(17) -0.21902(17) 0.12210(11) 0.0181(4) Uani 1 1 d . . . C5 C 0.1785(2) -0.32682(19) 0.05204(12) 0.0279(4) Uani 1 1 d . . . C6 C 0.1487(3) -0.4103(2) -0.00655(15) 0.0453(6) Uani 1 1 d . . . H6 H 0.1248 -0.4771 -0.0534 0.054 Uiso 1 1 calc . . . C7 C -0.12979(18) 0.16343(19) 0.15948(11) 0.0220(4) Uani 1 1 d . . . C8 C -0.2741(2) 0.1035(2) 0.12487(12) 0.0299(4) Uani 1 1 d . . . C9 C -0.3909(2) 0.0539(3) 0.10285(15) 0.0460(6) Uani 1 1 d . . . H9 H -0.4843 0.0142 0.0852 0.055 Uiso 1 1 calc . . . 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 0.0173(2) 0.0175(2) 0.01216(19) 0.00116(13) 0.00032(14) -0.00180(14) Mn2 0.02157(17) 0.01892(17) 0.01369(16) -0.00148(10) 0.00123(11) -0.00339(10) O1 0.0245(6) 0.0238(6) 0.0172(6) 0.0009(5) 0.0023(5) -0.0072(5) O2 0.0316(7) 0.0283(7) 0.0163(6) 0.0009(5) 0.0026(5) -0.0105(6) O3 0.0251(6) 0.0159(6) 0.0171(6) 0.0010(5) -0.0010(5) 0.0038(5) O4 0.0339(7) 0.0213(6) 0.0194(7) 0.0045(5) -0.0037(5) 0.0025(5) O5 0.0191(6) 0.0275(6) 0.0164(6) -0.0014(5) 0.0036(5) 0.0047(5) O6 0.0312(7) 0.0380(8) 0.0314(7) -0.0141(6) 0.0070(6) 0.0024(6) O7 0.0252(7) 0.0219(7) 0.0198(7) 0.0032(6) 0.0029(6) 0.0013(6) O8 0.0255(8) 0.0260(8) 0.0378(8) 0.0005(6) 0.0006(6) 0.0011(7) O9 0.0258(8) 0.0427(8) 0.0230(8) 0.0103(6) 0.0024(6) -0.0036(6) C1 0.0230(9) 0.0167(9) 0.0207(9) 0.0000(7) 0.0064(7) -0.0015(7) C2 0.0296(10) 0.0288(10) 0.0211(9) -0.0011(8) 0.0023(8) -0.0094(8) C3 0.0392(12) 0.0442(12) 0.0345(11) 0.0042(10) 0.0122(9) -0.0154(10) C4 0.0176(8) 0.0183(9) 0.0187(9) 0.0002(7) 0.0042(7) 0.0004(7) C5 0.0371(11) 0.0203(9) 0.0245(10) 0.0025(9) 0.0003(8) 0.0057(8) C6 0.0692(16) 0.0304(12) 0.0332(12) -0.0083(10) -0.0009(11) 0.0033(11) C7 0.0238(9) 0.0262(10) 0.0158(9) 0.0027(8) 0.0032(7) 0.0039(8) C8 0.0259(11) 0.0378(11) 0.0270(10) -0.0084(8) 0.0072(8) 0.0073(9) C9 0.0267(12) 0.0698(16) 0.0422(13) -0.0189(12) 0.0079(10) -0.0040(11) _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 2.1295(11) . ? Mn1 O1 2.1295(11) 3 ? Mn1 O3 2.2083(11) 3 ? Mn1 O3 2.2083(11) . ? Mn1 O5 2.2144(11) 3 ? Mn1 O5 2.2144(11) . ? Mn2 O4 2.1370(11) 2 ? Mn2 O7 2.1676(12) . ? Mn2 O8 2.1921(14) . ? Mn2 O2 2.1931(12) . ? Mn2 O5 2.2205(11) . ? Mn2 O3 2.2405(11) . ? O1 C1 1.255(2) . ? O2 C1 1.256(2) . ? O3 C4 1.274(2) . ? O4 C4 1.239(2) . ? O4 Mn2 2.1370(11) 2_545 ? O5 C7 1.285(2) . ? O6 C7 1.232(2) . ? O7 H7A 0.84(3) . ? O7 H7B 0.81(3) . ? O8 H8A 0.77(3) . ? O8 H85 0.83(3) . ? O9 H9A 0.80(3) . ? O9 H9B 0.83(3) . ? C1 C2 1.464(2) . ? C2 C3 1.178(3) . ? C3 H3 0.9400 . ? C4 C5 1.458(2) . ? C5 C6 1.176(3) . ? C6 H6 0.9400 . ? C7 C8 1.466(3) . ? C8 C9 1.176(3) . ? C9 H9 0.9400 . ? 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 O1 180.00(8) . 3 ? O1 Mn1 O3 91.10(4) . 3 ? O1 Mn1 O3 88.90(4) 3 3 ? O1 Mn1 O3 88.90(4) . . ? O1 Mn1 O3 91.10(4) 3 . ? O3 Mn1 O3 180.00(5) 3 . ? O1 Mn1 O5 91.41(4) . 3 ? O1 Mn1 O5 88.59(4) 3 3 ? O3 Mn1 O5 75.97(4) 3 3 ? O3 Mn1 O5 104.03(4) . 3 ? O1 Mn1 O5 88.59(4) . . ? O1 Mn1 O5 91.41(4) 3 . ? O3 Mn1 O5 104.03(4) 3 . ? O3 Mn1 O5 75.97(4) . . ? O5 Mn1 O5 180.00(6) 3 . ? O4 Mn2 O7 91.78(5) 2 . ? O4 Mn2 O8 87.26(5) 2 . ? O7 Mn2 O8 98.88(6) . . ? O4 Mn2 O2 88.31(4) 2 . ? O7 Mn2 O2 171.15(5) . . ? O8 Mn2 O2 89.96(5) . . ? O4 Mn2 O5 102.57(4) 2 . ? O7 Mn2 O5 84.90(5) . . ? O8 Mn2 O5 169.41(5) . . ? O2 Mn2 O5 86.44(4) . . ? O4 Mn2 O3 173.87(4) 2 . ? O7 Mn2 O3 93.70(4) . . ? O8 Mn2 O3 94.61(5) . . ? O2 Mn2 O3 85.86(4) . . ? O5 Mn2 O3 75.20(4) . . ? C1 O1 Mn1 131.07(10) . . ? C1 O2 Mn2 132.75(11) . . ? C4 O3 Mn1 133.04(10) . . ? C4 O3 Mn2 118.31(10) . . ? Mn1 O3 Mn2 100.67(4) . . ? C4 O4 Mn2 140.40(11) . 2_545 ? C7 O5 Mn1 133.59(10) . . ? C7 O5 Mn2 124.98(10) . . ? Mn1 O5 Mn2 101.11(4) . . ? Mn2 O7 H7A 114.7(17) . . ? Mn2 O7 H7B 115.4(18) . . ? H7A O7 H7B 106(2) . . ? Mn2 O8 H8A 124.9(18) . . ? Mn2 O8 H85 119.3(18) . . ? H8A O8 H85 112(2) . . ? H9A O9 H9B 107(2) . . ? O1 C1 O2 126.36(15) . . ? O1 C1 C2 115.86(14) . . ? O2 C1 C2 117.78(15) . . ? C3 C2 C1 175.5(2) . . ? C2 C3 H3 180.0 . . ? O4 C4 O3 122.98(15) . . ? O4 C4 C5 120.59(15) . . ? O3 C4 C5 116.43(14) . . ? C6 C5 C4 177.8(2) . . ? C5 C6 H6 180.0 . . ? O6 C7 O5 125.38(16) . . ? O6 C7 C8 118.71(15) . . ? O5 C7 C8 115.89(15) . . ? C9 C8 C7 175.6(2) . . ? C8 C9 H9 180.0 . . ? _diffrn_measured_fraction_theta_max 0.999 _diffrn_reflns_theta_full 24.11 _diffrn_measured_fraction_theta_full 0.999 _refine_diff_density_max 0.209 _refine_diff_density_min -0.231 _refine_diff_density_rms 0.044