# Supplementary Material (ESI) for Dalton Transactions # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Mark Murrie' _publ_contact_author_email MARKM@CHEM.GLA.AC.UK _publ_section_title ; Synthesis and characterisation of a Ni4 single-molecule magnet with S4 symmetry ; loop_ _publ_author_name 'Mark Murrie' 'Euan Brechin' 'Alan Ferguson' 'Stephen Hill' 'Konstantin Kamenev' 'Jon Lawrence' ; A.Parkin ; 'Javier Sanchez-Benitez' 'Wolfgang Wernsdorfer' # Attachment 'ni4_publish_a.cif' data_1 _database_code_depnum_ccdc_archive 'CCDC 686886' _publ_section_exptl_refinement # Some potentially useful phrases are donated by Bill Clegg: ; The H atoms were all located in a difference map, but those attached to carbon atoms were repositioned geometrically. The H atoms were initially refined with soft restraints on the bond lengths and angles to regularise their geometry and U~iso~(H), after which the positions were refined with riding constraints. 182 electrons per unit cell were modelled as approx. 18 molecules of disordered water solvent using the BYPASS method of van der Sluis and Spek. ; _cell_length_a 12.2907(3) _cell_length_b 12.2907(3) _cell_length_c 28.7030(14) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 4335.9(3) _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M 'I 41/a ' _symmetry_space_group_name_Hall ? loop_ _symmetry_equiv_pos_as_xyz x,y,z -x,-y,-z x+1/2,y+1/2,z+1/2 -x+1/2,-y+1/2,-z+1/2 -y+3/4,x+1/4,z+1/4 y+3/4,-x+1/4,-z+1/4 -y+5/4,x+3/4,z+3/4 y+5/4,-x+3/4,-z+3/4 -x+1/2,-y,z+1/2 x+1/2,y,-z+1/2 -x+1,-y+1/2,z+1 x+1,y+1/2,-z+1 y+3/4,-x+3/4,z+3/4 -y+3/4,x+3/4,-z+3/4 y+5/4,-x+5/4,z+5/4 -y+5/4,x+5/4,-z+5/4 loop_ _atom_type_symbol _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_Cromer_Mann_a1 _atom_type_scat_Cromer_Mann_b1 _atom_type_scat_Cromer_Mann_a2 _atom_type_scat_Cromer_Mann_b2 _atom_type_scat_Cromer_Mann_a3 _atom_type_scat_Cromer_Mann_b3 _atom_type_scat_Cromer_Mann_a4 _atom_type_scat_Cromer_Mann_b4 _atom_type_scat_Cromer_Mann_c _atom_type_scat_source C 0.0033 0.0016 2.3100 20.8439 1.0200 10.2075 1.5886 0.5687 0.8650 51.6512 0.2156 'International Tables Vol C 4.2.6.8 and 6.1.1.4' H 0.0000 0.0000 0.4930 10.5109 0.3229 26.1257 0.1402 3.1424 0.0408 57.7998 0.0030 'International Tables Vol C 4.2.6.8 and 6.1.1.4' N 0.0061 0.0033 12.2126 0.0057 3.1322 9.8933 2.0125 28.9975 1.1663 0.5826 -11.5290 'International Tables Vol C 4.2.6.8 and 6.1.1.4' O 0.0106 0.0060 3.0485 13.2771 2.2868 5.7011 1.5463 0.3239 0.8670 32.9089 0.2508 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Na 0.0362 0.0249 4.7626 3.2850 3.1736 8.8422 1.2674 0.3136 1.1128 129.4240 0.6760 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Cl 0.1484 0.1585 11.4604 0.0104 7.1964 1.1662 6.2556 18.5194 1.6455 47.7784 -9.5574 'International Tables Vol C 4.2.6.8 and 6.1.1.4' Ni 0.3393 1.1124 12.8376 3.8785 7.2920 0.2565 4.4438 12.1763 2.3800 66.3421 1.0341 'International Tables Vol C 4.2.6.8 and 6.1.1.4' _cell_formula_units_Z 4 # Given Formula = C30 H40 Cl1 N5 Na1 Ni4 O20 # Dc = 1.66 Fooo = 1984.00 Mu = 18.63 M = 270.99 # Found Formula = C24 H52 Cl4 N8 Ni4 O8 # Dc = 1.47 FOOO = 1984.00 Mu = 20.03 M = 239.34 _chemical_formula_sum 'C24 H61 Cl4 N8 Ni4 O12.5' _chemical_formula_moiety 'C24 H61 Cl4 N8 Ni4 O12.5' _chemical_compound_source ? _chemical_formula_weight 1030.45 _cell_measurement_reflns_used 7158 _cell_measurement_theta_min 3 _cell_measurement_theta_max 31 _cell_measurement_temperature 100 _exptl_crystal_description prism _exptl_crystal_colour green _exptl_crystal_size_min 0.20 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_max 0.25 _exptl_crystal_density_diffrn 1.467 _exptl_crystal_density_meas ? _exptl_crystal_density_method 'not measured' # Non-dispersive F(000): _exptl_crystal_F_000 1984 _exptl_absorpt_coefficient_mu 2.003 # Sheldrick geometric approximatio 0.67 0.67 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'SADABS (Siemens, 1996)' _exptl_absorpt_correction_T_min 0.82 _exptl_absorpt_correction_T_max 1.00 _diffrn_measurement_device 'Bruker APEX2 CCD diffractometer' _diffrn_measurement_device_type Area _diffrn_radiation_monochromator graphite _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_wavelength 0.71073 _diffrn_measurement_method '\f & \w scans' # If a reference occurs more than once, delete the author # and date from subsequent references. _computing_data_collection APEX2 _computing_cell_refinement APEX2 _computing_data_reduction APEX2 _computing_structure_solution 'SIR92 (Altomare et al., 1994)' _computing_structure_refinement 'CRYSTALS (Betteridge et al., 2003)' _computing_publication_material 'CRYSTALS (Betteridge et al., 2003)' _computing_molecular_graphics Mercury _diffrn_standards_interval_time . _diffrn_standards_interval_count . _diffrn_standards_number 0 _diffrn_standards_decay_% ? _diffrn_ambient_temperature 100 _diffrn_reflns_number 30419 _reflns_number_total 3332 _diffrn_reflns_av_R_equivalents 0.028 # Number of reflections with Friedels Law is 3332 # Number of reflections without Friedels Law is 0 # Theoretical number of reflections is about 3336 _diffrn_reflns_theta_min 1.802 _diffrn_reflns_theta_max 30.600 _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 29.988 _diffrn_measured_fraction_theta_full 1.000 _diffrn_reflns_limit_h_min -17 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -41 _diffrn_reflns_limit_l_max 38 _reflns_limit_h_min -11 _reflns_limit_h_max 12 _reflns_limit_k_min 0 _reflns_limit_k_max 17 _reflns_limit_l_min 0 _reflns_limit_l_max 41 _oxford_diffrn_Wilson_B_factor 1.26 _oxford_diffrn_Wilson_scale 39.51 _atom_sites_solution_primary direct #heavy,direct,difmap,geom # _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_diff_density_min -1.09 _refine_diff_density_max 1.26 # The current dictionary definitions do not cover the # situation where the reflections used for refinement were # selected by a user-defined sigma threshold # The values actually used during refinement _oxford_reflns_threshold_expression_ref I>-10.0\s(I) _refine_ls_number_reflns 3332 _refine_ls_number_restraints 2 _refine_ls_number_parameters 94 _oxford_refine_ls_R_factor_ref 0.0478 _refine_ls_wR_factor_ref 0.1331 _refine_ls_goodness_of_fit_ref 1.0037 _refine_ls_shift/su_max 0.001593 # The values computed from all data _oxford_reflns_number_all 3332 _refine_ls_R_factor_all 0.0478 _refine_ls_wR_factor_all 0.1331 # The values computed with a 2 sigma cutoff - a la SHELX _reflns_threshold_expression I>2.0\s(I) _reflns_number_gt 2912 _refine_ls_R_factor_gt 0.0434 _refine_ls_wR_factor_gt 0.1299 # choose from: rm (reference molecule of known chirality), # ad (anomolous dispersion - Flack), rmad (rm and ad), # syn (from synthesis), unk (unknown) or . (not applicable). _chemical_absolute_configuration . _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_hydrogen_treatment constr # none, undef, noref, refall, # refxyz, refU, constr or mixed _refine_ls_weighting_scheme calc _refine_ls_weighting_details ; Method= Modified Sheldrick w=1/[\s^2^(F^2^) + ( 0.08P)^2^ +18.45P] ,where P=(max(Fo^2^,0) + 2Fc^2^)/3 ; # Insert your own references if required - in alphabetical order _publ_section_references ; Altomare, A., Cascarano, G., Giacovazzo, G., Guagliardi, A., Burla, M.C., Polidori, G. & Camalli, M. (1994). J. Appl. Cryst. 27, 435. Betteridge, P.W., Carruthers, J.R., Cooper, R.I., Prout, K. & Watkin, D.J. (2003). J. Appl. Cryst. 36, 1487. ; # Uequiv = arithmetic mean of Ui i.e. Ueqiv = (U1+U2+U3)/3 # Replace last . with number of unfound hydrogen atomsattached to an atom. # ..._refinement_flags_... # . no refinement constraints S special position constraint on site # G rigid group refinement of site R riding atom # D distance or angle restraint on site T thermal displacement constraints # U Uiso or Uij restraint (rigid bond) P partial occupancy constraint 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_occupancy _atom_site_adp_type _atom_site_refinement_flags_posn _atom_site_refinement_flags_adp _atom_site_refinement_flags_occupancy _atom_site_disorder_assembly _atom_site_disorder_group _oxford_atom_site_special_shape _atom_site_attached_hydrogens H1 H 0.9551 -0.0045 0.1794 0.0500 1.0000 Uiso R . . . . . . H2 H 0.8641 0.0866 0.1962 0.0500 1.0000 Uiso R . . . . . . H3 H 0.9953 0.0293 0.2571 0.0500 1.0000 Uiso R . . . . . . H4 H 0.9541 0.1491 0.2525 0.0500 1.0000 Uiso R . . . . . . H5 H 1.1230 0.1744 0.2514 0.0500 1.0000 Uiso R . . . . . . H6 H 1.2614 0.0754 0.2331 0.0500 1.0000 Uiso R . . . . . . H7 H 1.1794 -0.0014 0.2594 0.0500 1.0000 Uiso R . . . . . . H8 H 1.2502 -0.0765 0.1889 0.0500 1.0000 Uiso R . . . . . . H9 H 1.1198 -0.0743 0.1911 0.0500 1.0000 Uiso R . . . . . . H10 H 1.1391 0.0068 0.1300 0.0500 1.0000 Uiso R . . . . . . N1 N 1.10704(18) 0.12901(18) 0.22921(7) 0.0214 1.0000 Uani . . . . . . . C2 C 0.4307(8) 0.5712(9) 0.1572(4) 0.137(4) 1.0000 Uiso D . . . . . . O1 O 1.18179(16) 0.03793(15) 0.14912(6) 0.0236 1.0000 Uani . . . . . . . O2 O 0.95744(14) 0.15141(15) 0.15881(6) 0.0178 1.0000 Uani . . . . . . . C1 C 0.4989(8) 0.5003(8) 0.1349(4) 0.131(3) 1.0000 Uiso D . . . . . . N7 N 0.5517(6) 0.4349(6) 0.1144(3) 0.108(2) 1.0000 Uiso D . . . . . . C3 C 0.9371(2) 0.0661(2) 0.19097(8) 0.0201 1.0000 Uani . . . . . . . C4 C 0.9944(2) 0.0919(2) 0.23692(8) 0.0222 1.0000 Uani . . . . . . . C5 C 1.1899(2) 0.0415(2) 0.23174(9) 0.0250 1.0000 Uani . . . . . . . C6 C 1.1849(2) -0.0310(2) 0.18947(9) 0.0264 1.0000 Uani . . . . . . . Cl1 Cl 1.29591(5) 0.26897(5) 0.17165(2) 0.0232 1.0000 Uani . . . . . . . Ni1 Ni 1.11694(2) 0.19519(2) 0.161934(10) 0.0169 1.0000 Uani . . . . . . . H21 H 0.4688 0.6095 0.1826 0.1549 1.0000 Uiso R . . . . . . H22 H 0.4064 0.6277 0.1356 0.1549 1.0000 Uiso R . . . . . . H23 H 0.3674 0.5329 0.1698 0.1549 1.0000 Uiso 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 N1 0.0257(10) 0.0234(10) 0.0151(9) 0.0006(7) -0.0025(7) -0.0014(8) O1 0.0290(9) 0.0239(9) 0.0181(8) -0.0003(7) -0.0033(7) 0.0027(7) O2 0.0210(8) 0.0209(8) 0.0114(7) 0.0010(6) 0.0006(6) -0.0004(6) C3 0.0248(11) 0.0206(10) 0.0148(10) 0.0027(8) 0.0005(8) -0.0017(8) C4 0.0278(12) 0.0239(11) 0.0150(10) 0.0024(8) -0.0001(8) -0.0023(9) C5 0.0294(12) 0.0277(12) 0.0180(11) 0.0041(9) -0.0048(9) 0.0033(10) C6 0.0328(13) 0.0241(12) 0.0224(12) 0.0025(9) -0.0043(10) 0.0043(10) Cl1 0.0217(3) 0.0300(3) 0.0178(3) 0.0005(2) -0.00310(19) -0.0021(2) Ni1 0.01943(17) 0.01975(17) 0.01159(17) 0.00041(10) -0.00090(10) 0.00012(10) _refine_ls_extinction_method None _oxford_refine_ls_scale 1.614(14) loop_ _geom_bond_atom_site_label_1 _geom_bond_site_symmetry_1 _geom_bond_atom_site_label_2 _geom_bond_site_symmetry_2 _geom_bond_distance _geom_bond_publ_flag H1 . C3 . 0.955 no H2 . C3 . 0.944 no H3 . C4 . 0.965 no H4 . C4 . 0.969 no H5 . N1 . 0.869 no H6 . C5 . 0.974 no H7 . C5 . 0.961 no H8 . C6 . 0.978 no H9 . C6 . 0.961 no H10 . O1 . 0.850 no N1 . C4 . 1.475(3) yes N1 . C5 . 1.483(3) yes N1 . Ni1 . 2.099(2) yes C2 . C1 . 1.370(8) yes C2 . H21 . 0.985 no C2 . H22 . 0.978 no C2 . H23 . 0.978 no O1 . C6 . 1.436(3) yes O1 . Ni1 . 2.1229(19) yes O2 . Ni1 11_654 2.0972(18) yes O2 . Ni1 6_565 2.0487(16) yes O2 . C3 . 1.419(3) yes O2 . Ni1 . 2.0349(18) yes C1 . N7 . 1.189(7) yes C3 . C4 . 1.528(3) yes C3 . Ni1 . 2.845(2) yes C5 . C6 . 1.507(4) yes Cl1 . Ni1 . 2.3955(7) yes Ni1 . Ni1 11_654 3.1746(6) yes Ni1 . Ni1 16_534 3.0878(5) yes Ni1 . Ni1 6_565 3.0878(5) yes loop_ _geom_angle_atom_site_label_1 _geom_angle_site_symmetry_1 _geom_angle_atom_site_label_2 _geom_angle_site_symmetry_2 _geom_angle_atom_site_label_3 _geom_angle_site_symmetry_3 _geom_angle _geom_angle_publ_flag H5 . N1 . C4 . 107.5 no H5 . N1 . C5 . 106.0 no C4 . N1 . C5 . 114.4(2) yes H5 . N1 . Ni1 . 114.3 no C4 . N1 . Ni1 . 108.19(15) yes C5 . N1 . Ni1 . 106.65(15) yes C1 . C2 . H21 . 111.0 no C1 . C2 . H22 . 110.0 no H21 . C2 . H22 . 105.9 no C1 . C2 . H23 . 110.7 no H21 . C2 . H23 . 109.6 no H22 . C2 . H23 . 109.4 no H10 . O1 . C6 . 105.8 no H10 . O1 . Ni1 . 106.8 no C6 . O1 . Ni1 . 114.06(16) yes Ni1 11_654 O2 . Ni1 6_565 96.27(7) yes Ni1 11_654 O2 . C3 . 124.04(14) yes Ni1 6_565 O2 . C3 . 123.40(15) yes Ni1 11_654 O2 . Ni1 . 100.39(8) yes Ni1 6_565 O2 . Ni1 . 98.25(7) yes C3 . O2 . Ni1 . 109.65(14) yes C2 . C1 . N7 . 175.3(12) yes O2 . C3 . H1 . 113.9 no O2 . C3 . H2 . 94.2 no H1 . C3 . H2 . 121.1 no O2 . C3 . C4 . 109.07(19) yes H1 . C3 . C4 . 112.5 no H2 . C3 . C4 . 104.2 no O2 . C3 . Ni1 . 42.33(10) yes H1 . C3 . Ni1 . 103.0 no H2 . C3 . Ni1 . 129.5 no C4 . C3 . Ni1 . 77.25(13) yes C3 . C4 . N1 . 111.5(2) yes C3 . C4 . H4 . 108.3 no N1 . C4 . H4 . 109.0 no C3 . C4 . H3 . 111.0 no N1 . C4 . H3 . 109.0 no H4 . C4 . H3 . 107.8 no N1 . C5 . H6 . 108.1 no N1 . C5 . H7 . 110.3 no H6 . C5 . H7 . 108.8 no N1 . C5 . C6 . 111.2(2) yes H6 . C5 . C6 . 108.8 no H7 . C5 . C6 . 109.6 no C5 . C6 . O1 . 107.6(2) yes C5 . C6 . H8 . 108.6 no O1 . C6 . H8 . 110.2 no C5 . C6 . H9 . 108.8 no O1 . C6 . H9 . 110.1 no H8 . C6 . H9 . 111.5 no Ni1 11_654 Ni1 . Ni1 16_534 59.066(5) yes Ni1 11_654 Ni1 . Ni1 6_565 59.066(5) yes Ni1 16_534 Ni1 . Ni1 6_565 61.869(11) yes Ni1 11_654 Ni1 . O1 . 136.58(6) yes Ni1 16_534 Ni1 . O1 . 126.61(5) yes Ni1 6_565 Ni1 . O1 . 84.98(5) yes Ni1 11_654 Ni1 . N1 . 96.43(6) yes Ni1 16_534 Ni1 . N1 . 151.93(6) yes Ni1 6_565 Ni1 . N1 . 119.75(6) yes O1 . Ni1 . N1 . 80.11(8) yes Ni1 11_654 Ni1 . O2 11_654 39.09(5) yes Ni1 16_534 Ni1 . O2 11_654 41.26(4) yes Ni1 6_565 Ni1 . O2 11_654 83.97(5) yes O1 . Ni1 . O2 11_654 167.11(7) yes N1 . Ni1 . O2 11_654 111.25(8) yes Ni1 11_654 Ni1 . Cl1 . 132.13(2) yes Ni1 16_534 Ni1 . Cl1 . 92.77(2) yes Ni1 6_565 Ni1 . Cl1 . 143.25(2) yes O1 . Ni1 . Cl1 . 91.15(6) yes N1 . Ni1 . Cl1 . 95.33(6) yes Ni1 11_654 Ni1 . O2 16_534 82.48(5) yes Ni1 16_534 Ni1 . O2 16_534 40.71(5) yes Ni1 6_565 Ni1 . O2 16_534 42.46(5) yes O1 . Ni1 . O2 16_534 86.36(7) yes N1 . Ni1 . O2 16_534 159.07(8) yes Ni1 11_654 Ni1 . O2 . 40.53(5) yes Ni1 16_534 Ni1 . O2 . 84.97(5) yes Ni1 6_565 Ni1 . O2 . 41.04(5) yes O1 . Ni1 . O2 . 96.51(7) yes N1 . Ni1 . O2 . 83.23(8) yes Ni1 11_654 Ni1 . C3 . 62.18(5) yes Ni1 16_534 Ni1 . C3 . 112.97(5) yes Ni1 6_565 Ni1 . C3 . 62.11(5) yes O1 . Ni1 . C3 . 80.48(8) yes N1 . Ni1 . C3 . 57.95(8) yes O2 11_654 Ni1 . Cl1 . 93.72(5) yes O2 11_654 Ni1 . O2 16_534 81.01(7) yes Cl1 . Ni1 . O2 16_534 100.87(5) yes O2 11_654 Ni1 . O2 . 79.39(8) yes Cl1 . Ni1 . O2 . 171.83(5) yes O2 16_534 Ni1 . O2 . 82.52(7) yes O2 11_654 Ni1 . C3 . 100.09(7) yes Cl1 . Ni1 . C3 . 152.89(5) yes O2 16_534 Ni1 . C3 . 104.23(7) yes O2 . Ni1 . C3 . 28.01(7) yes loop_ _geom_hbond_atom_site_label_D _geom_hbond_site_symmetry_D _geom_hbond_atom_site_label_H _geom_hbond_site_symmetry_H _geom_hbond_atom_site_label_A _geom_hbond_site_symmetry_A _geom_hbond_angle_DHA _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_publ_flag C2 . H22 . C1 6_465 144 0.98 2.52 3.356(7) yes