Electronic Supplementary Information for Dalton Transactions This journal is © The Royal Society of Chemistry 2007 data_global _journal_coden_Cambridge 222 _publ_requested_journal 'Dalton Transactions' loop_ _publ_author_name 'Malcolm Chisholm' 'Douglas J. Brown' 'Christopher W. Gribble' _publ_contact_author_name 'Malcolm Chisholm' _publ_contact_author_address ; Department of Chemistry The Ohio State University 100 West 18th Avenue Columbus Ohio 43210-1185 ; _publ_contact_author_email CHISHOLM@CHEMISTRY.OHIO-STATE.EDU _publ_section_title ; Substitution Chemistry of MM Quadruply Bonded Complexes (M = Mo or W) Supported by the Anion of 2-hydroxy-6-methylpyridine ; _publ_requested_category FM data_chis1449a _database_code_depnum_ccdc_archive 'CCDC 632258' _audit_creation_date 2006-05-30T14:49:08-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' _audit_conform_dict_name cif_core.dic _audit_conform_dict_version 2.2 _audit_conform_dict_location ftp://ftp.iucr.org/pub/cif_core.dic #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; ? ; _chemical_formula_sum 'C24 H30 B2 F8 Mo2 N8 O2' _chemical_formula_weight 828.06 _chemical_absolute_configuration ad #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' 'x, y, -z' 'x+1/2, -y, -z+1/2' 'x+1/2, -y, z+1/2' _cell_length_a 7.26150(10) _cell_length_b 12.0539(2) _cell_length_c 19.1113(3) _cell_angle_alpha 90 _cell_angle_beta 90 _cell_angle_gamma 90 _cell_volume 1672.80(4) _cell_formula_units_Z 2 _cell_measurement_temperature 150(2) #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description rod _exptl_crystal_colour purple _exptl_crystal_size_max 0.38 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.04 _exptl_crystal_density_diffrn 1.644 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 824 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 0.83 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; R.H. Blessing, Acta Cryst. (1995), A51, 33-38 ; _exptl_absorpt_correction_T_min 0.891 _exptl_absorpt_correction_T_max 0.954 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_reflns_av_R_equivalents 0.0336 _diffrn_reflns_av_unetI/netI 0.0293 _diffrn_reflns_number 19161 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 9 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -24 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 3.28 _diffrn_reflns_theta_max 27.49 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.997 _diffrn_measured_fraction_theta_max 0.997 _reflns_number_total 3950 _reflns_number_gt 3722 _reflns_threshold_expression >2sigma(I) _diffrn_reflns_reduction_process ; Scaled and merged with SORTAV R.H. Blessing, (1987) Cryst. Rev. 1, 3-58 R.H. Blessing, (1989) J. Appl. Cryst. 22, 396-397 ; #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' #----------------------------------------------------------------------------# # REFINEMENT INFORMATION # #----------------------------------------------------------------------------# _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^)+(0.0363P)^2^+1.4371P] 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 _refine_ls_extinction_method none _refine_ls_number_reflns 3950 _refine_ls_number_parameters 221 _refine_ls_number_restraints 1 _refine_ls_R_factor_all 0.0324 _refine_ls_R_factor_gt 0.0282 _refine_ls_wR_factor_ref 0.0687 _refine_ls_wR_factor_gt 0.0671 _refine_ls_goodness_of_fit_ref 1.034 _refine_ls_restrained_S_all 1.033 _refine_ls_shift/su_max 0.001 _refine_ls_shift/su_mean 0 _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.02(4) _refine_diff_density_max 0.544 _refine_diff_density_min -0.381 _refine_diff_density_rms 0.07 #----------------------------------------------------------------------------# # ATOMIC TYPES, COORDINATES AND THERMAL PARAMETERS # #----------------------------------------------------------------------------# 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 0 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' B B 0.0013 0.0007 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' F F 0.0171 0.0103 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Mo Mo -1.6832 0.6857 '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 0.006 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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 Mo1 Mo 0.08672(4) 0.35002(3) 0 0.01703(8) Uani 1 2 d S . . Mo2 Mo -0.14821(5) 0.24502(3) 0 0.01772(8) Uani 1 2 d S . . N1 N -0.0307(3) 0.4476(2) 0.08373(13) 0.0195(5) Uani 1 1 d . . . N2 N -0.0718(4) 0.1208(2) 0.07690(14) 0.0251(6) Uani 1 1 d . . . N3 N 0.2598(4) 0.2748(2) 0.07872(14) 0.0219(5) Uani 1 1 d . . . O1 O -0.2789(3) 0.33271(19) 0.07626(11) 0.0230(5) Uani 1 1 d . . . C1 C 0.2467(5) 0.5650(3) 0.0934(2) 0.0396(9) Uani 1 1 d . . . H1A H 0.284 0.5163 0.0549 0.059 Uiso 1 1 calc R . . H1B H 0.3334 0.557 0.1324 0.059 Uiso 1 1 calc R . . H1C H 0.2465 0.6422 0.0773 0.059 Uiso 1 1 calc R . . C2 C 0.0567(4) 0.5337(3) 0.11743(16) 0.0246(7) Uani 1 1 d . . . C3 C -0.0261(5) 0.5902(3) 0.17127(19) 0.0322(8) Uani 1 1 d . . . H3 H 0.0368 0.6496 0.1936 0.039 Uiso 1 1 calc R . . C4 C -0.2022(5) 0.5606(3) 0.19326(18) 0.0344(8) Uani 1 1 d . . . H4 H -0.2612 0.6007 0.2297 0.041 Uiso 1 1 calc R . . C5 C -0.2896(5) 0.4727(3) 0.16171(17) 0.0289(7) Uani 1 1 d . . . H5 H -0.4084 0.4502 0.1769 0.035 Uiso 1 1 calc R . . C6 C -0.2013(4) 0.4166(2) 0.10682(16) 0.0209(6) Uani 1 1 d . . . C7 C -0.0552(5) 0.0473(3) 0.11363(18) 0.0282(7) Uani 1 1 d . . . C8 C -0.0381(6) -0.0484(3) 0.1602(2) 0.0435(9) Uani 1 1 d . . . H8A H -0.026 -0.0228 0.2086 0.065 Uiso 1 1 calc R . . H8B H 0.071 -0.0916 0.1472 0.065 Uiso 1 1 calc R . . H8C H -0.1481 -0.0951 0.1559 0.065 Uiso 1 1 calc R . . C9 C 0.3514(5) 0.2379(2) 0.12047(14) 0.0233(6) Uani 1 1 d . . . C10 C 0.4671(5) 0.1867(3) 0.17321(16) 0.0286(7) Uani 1 1 d . . . H10A H 0.4824 0.1078 0.1625 0.043 Uiso 1 1 calc R . . H10B H 0.4092 0.1948 0.2193 0.043 Uiso 1 1 calc R . . H10C H 0.5879 0.223 0.1735 0.043 Uiso 1 1 calc R . . B1 B 0.9701(6) 0.1770(3) 0.3001(2) 0.0352(9) Uani 1 1 d . . . F1 F 1.0953(5) 0.1751(3) 0.24796(15) 0.0806(9) Uani 1 1 d . . . F3 F 1.0374(5) 0.2293(2) 0.35797(15) 0.0686(8) Uani 1 1 d . . . F2 F 0.9295(7) 0.0705(2) 0.3182(2) 0.1125(17) Uani 1 1 d . . . F4 F 0.8096(5) 0.2278(3) 0.2797(2) 0.0970(13) Uani 1 1 d . . . N4 N 0.5680(6) 0.1064(3) 0 0.0324(9) Uani 1 2 d S . . C21 C 0.4814(7) 0.0275(4) 0 0.0276(10) Uani 1 2 d S . . C22 C 0.3703(10) -0.0735(5) 0 0.0497(15) Uani 1 2 d S . . H22A H 0.4252 -0.1279 -0.0319 0.075 Uiso 0.5 1 calc PR . . H22B H 0.245 -0.0561 -0.0155 0.075 Uiso 0.5 1 calc PR . . H22C H 0.3662 -0.1044 0.0474 0.075 Uiso 0.5 1 calc PR . . N5 N 0.9485(11) 0.8128(8) 0 0.089(3) Uani 1 2 d S . . C31 C 0.8398(10) 0.7478(5) 0 0.0451(13) Uani 1 2 d S . . C32 C 0.6943(8) 0.6650(4) 0 0.0380(12) Uani 1 2 d S . . H32A H 0.7452 0.593 0.0139 0.057 Uiso 0.5 1 calc PR . . H32B H 0.6415 0.6592 -0.0471 0.057 Uiso 0.5 1 calc PR . . H32C H 0.598 0.687 0.0331 0.057 Uiso 0.5 1 calc PR . . 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 Mo1 0.01430(14) 0.02069(17) 0.01609(15) 0 0 -0.00074(15) Mo2 0.01787(15) 0.01960(17) 0.01569(15) 0 0 -0.00242(14) N1 0.0195(11) 0.0205(13) 0.0184(12) -0.0005(10) -0.0014(10) -0.0015(10) N2 0.0261(13) 0.0278(14) 0.0215(13) 0.0016(12) -0.0010(11) -0.0015(11) N3 0.0200(12) 0.0243(13) 0.0213(14) -0.0011(11) 0.0013(11) -0.0002(11) O1 0.0203(10) 0.0282(11) 0.0207(11) -0.0025(9) 0.0034(9) -0.0032(9) C1 0.0304(18) 0.039(2) 0.049(2) -0.0143(17) -0.0007(17) -0.0107(16) C2 0.0254(18) 0.0246(15) 0.0238(14) -0.0005(12) -0.0038(13) -0.0019(13) C3 0.0384(19) 0.0313(18) 0.0269(17) -0.0097(15) -0.0070(15) 0.0010(16) C4 0.043(2) 0.0380(19) 0.0220(16) -0.0081(14) 0.0010(14) 0.0026(16) C5 0.0300(16) 0.0347(18) 0.0220(15) -0.0028(14) 0.0067(13) 0.0019(14) C6 0.0218(15) 0.0233(15) 0.0175(14) -0.0001(11) -0.0005(11) 0.0033(12) C7 0.0278(16) 0.0303(18) 0.0265(17) -0.0016(14) -0.0045(14) -0.0060(14) C8 0.059(2) 0.039(2) 0.033(2) 0.0131(17) -0.0084(18) -0.003(2) C9 0.0191(12) 0.0297(15) 0.0212(13) -0.0009(12) 0.0019(15) -0.0059(13) C10 0.0287(15) 0.0365(19) 0.0207(14) 0.0114(14) 0.0004(14) -0.0002(15) B1 0.0260(17) 0.033(2) 0.046(2) -0.0057(18) 0.0016(18) -0.0002(18) F1 0.0545(15) 0.130(3) 0.0571(16) -0.0177(17) 0.0218(18) -0.004(2) F3 0.081(2) 0.0744(18) 0.0507(16) -0.0172(14) -0.0138(15) -0.0060(15) F2 0.180(5) 0.0420(17) 0.116(3) -0.0173(18) 0.038(3) -0.024(2) F4 0.059(2) 0.138(3) 0.094(3) -0.029(2) -0.0237(19) 0.047(2) N4 0.031(2) 0.032(2) 0.034(2) 0 0 0.003(2) C21 0.026(2) 0.031(3) 0.025(2) 0 0 0.003(2) C22 0.060(4) 0.047(3) 0.042(3) 0 0 -0.021(3) N5 0.078(5) 0.127(6) 0.060(4) 0 0 -0.056(5) C31 0.043(3) 0.061(4) 0.031(2) 0 0 -0.007(3) C32 0.042(3) 0.039(3) 0.033(3) 0 0 0.004(2) #----------------------------------------------------------------------------# # MOLECULAR GEOMETRY # #----------------------------------------------------------------------------# _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 Mo1 Mo2 2.1242(5) . ? Mo1 N3 2.160(3) . ? Mo1 N3 2.160(3) 2 ? Mo1 N1 2.161(2) . ? Mo1 N1 2.161(2) 2 ? Mo2 O1 2.035(2) . ? Mo2 O1 2.035(2) 2 ? Mo2 N2 2.170(3) 2 ? Mo2 N2 2.170(3) . ? N1 C6 1.367(4) . ? N1 C2 1.376(4) . ? N2 C7 1.137(4) . ? N3 C9 1.130(4) . ? O1 C6 1.297(4) . ? C1 C2 1.502(5) . ? C2 C3 1.373(5) . ? C3 C4 1.392(6) . ? C4 C5 1.374(5) . ? C5 C6 1.403(4) . ? C7 C8 1.462(5) . ? C9 C10 1.450(4) . ? B1 F1 1.349(5) . ? B1 F3 1.363(5) . ? B1 F2 1.361(5) . ? B1 F4 1.373(5) . ? N4 C21 1.140(6) . ? C21 C22 1.461(7) . ? N5 C31 1.112(10) . ? C31 C32 1.454(9) . ? 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 Mo2 Mo1 N3 102.54(7) . . ? Mo2 Mo1 N3 102.54(7) . 2 ? N3 Mo1 N3 88.29(14) . 2 ? Mo2 Mo1 N1 90.43(7) . . ? N3 Mo1 N1 86.70(10) . . ? N3 Mo1 N1 166.84(10) 2 . ? Mo2 Mo1 N1 90.43(7) . 2 ? N3 Mo1 N1 166.84(10) . 2 ? N3 Mo1 N1 86.70(10) 2 2 ? N1 Mo1 N1 95.53(13) . 2 ? O1 Mo2 O1 91.47(13) . 2 ? O1 Mo2 Mo1 93.73(6) . . ? O1 Mo2 Mo1 93.73(6) 2 . ? O1 Mo2 N2 164.25(9) . 2 ? O1 Mo2 N2 89.58(10) 2 2 ? Mo1 Mo2 N2 101.88(7) . 2 ? O1 Mo2 N2 89.58(10) . . ? O1 Mo2 N2 164.25(9) 2 . ? Mo1 Mo2 N2 101.88(7) . . ? N2 Mo2 N2 85.24(15) 2 . ? C6 N1 C2 118.2(3) . . ? C6 N1 Mo1 116.6(2) . . ? C2 N1 Mo1 125.1(2) . . ? C7 N2 Mo2 169.5(3) . . ? C9 N3 Mo1 178.3(3) . . ? C6 O1 Mo2 121.67(19) . . ? C3 C2 N1 121.6(3) . . ? C3 C2 C1 120.4(3) . . ? N1 C2 C1 118.0(3) . . ? C2 C3 C4 120.1(3) . . ? C5 C4 C3 119.3(3) . . ? C4 C5 C6 119.2(3) . . ? O1 C6 N1 117.5(3) . . ? O1 C6 C5 120.9(3) . . ? N1 C6 C5 121.6(3) . . ? N2 C7 C8 178.5(4) . . ? N3 C9 C10 178.0(3) . . ? F1 B1 F3 111.4(4) . . ? F1 B1 F2 108.5(4) . . ? F3 B1 F2 107.9(4) . . ? F1 B1 F4 111.7(4) . . ? F3 B1 F4 109.2(4) . . ? F2 B1 F4 108.0(4) . . ? N4 C21 C22 180.0(6) . . ? N5 C31 C32 178.6(9) . . ? 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 N3 Mo1 Mo2 O1 88.62(9) . . . . ? N3 Mo1 Mo2 O1 179.66(11) 2 . . . ? N1 Mo1 Mo2 O1 1.91(9) . . . . ? N1 Mo1 Mo2 O1 -93.63(10) 2 . . . ? N3 Mo1 Mo2 O1 -179.66(11) . . . 2 ? N3 Mo1 Mo2 O1 -88.62(9) 2 . . 2 ? N1 Mo1 Mo2 O1 93.63(10) . . . 2 ? N1 Mo1 Mo2 O1 -1.91(9) 2 . . 2 ? N3 Mo1 Mo2 N2 -89.31(11) . . . 2 ? N3 Mo1 Mo2 N2 1.73(10) 2 . . 2 ? N1 Mo1 Mo2 N2 -176.02(10) . . . 2 ? N1 Mo1 Mo2 N2 88.44(10) 2 . . 2 ? N3 Mo1 Mo2 N2 -1.73(10) . . . . ? N3 Mo1 Mo2 N2 89.31(11) 2 . . . ? N1 Mo1 Mo2 N2 -88.44(10) . . . . ? N1 Mo1 Mo2 N2 176.02(10) 2 . . . ? Mo2 Mo1 N1 C6 -1.3(2) . . . . ? N3 Mo1 N1 C6 -103.9(2) . . . . ? N3 Mo1 N1 C6 -171.6(4) 2 . . . ? N1 Mo1 N1 C6 89.2(2) 2 . . . ? Mo2 Mo1 N1 C2 175.1(2) . . . . ? N3 Mo1 N1 C2 72.6(2) . . . . ? N3 Mo1 N1 C2 4.8(6) 2 . . . ? N1 Mo1 N1 C2 -94.4(2) 2 . . . ? O1 Mo2 N2 C7 96.0(15) . . . . ? O1 Mo2 N2 C7 2.1(17) 2 . . . ? Mo1 Mo2 N2 C7 -170.3(15) . . . . ? N2 Mo2 N2 C7 -69.1(15) 2 . . . ? O1 Mo2 O1 C6 -97.2(2) 2 . . . ? Mo1 Mo2 O1 C6 -3.4(2) . . . . ? N2 Mo2 O1 C6 169.2(3) 2 . . . ? N2 Mo2 O1 C6 98.5(2) . . . . ? C6 N1 C2 C3 -2.2(5) . . . . ? Mo1 N1 C2 C3 -178.6(2) . . . . ? C6 N1 C2 C1 178.1(3) . . . . ? Mo1 N1 C2 C1 1.7(4) . . . . ? N1 C2 C3 C4 0.3(5) . . . . ? C1 C2 C3 C4 -179.9(3) . . . . ? C2 C3 C4 C5 1.6(5) . . . . ? C3 C4 C5 C6 -1.7(5) . . . . ? Mo2 O1 C6 N1 2.9(4) . . . . ? Mo2 O1 C6 C5 -176.7(2) . . . . ? C2 N1 C6 O1 -177.5(3) . . . . ? Mo1 N1 C6 O1 -0.8(3) . . . . ? C2 N1 C6 C5 2.2(4) . . . . ? Mo1 N1 C6 C5 178.9(2) . . . . ? C4 C5 C6 O1 179.4(3) . . . . ? C4 C5 C6 N1 -0.3(5) . . . . ? #END OF CIF