Supplementary Material (ESI) for Dalton Transactions This journal is (c) The Royal Society of Chemistry 2007 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author 'Schollhammer, P.' _publ_contact_author_email philippe.schollhammer@univ-brest.fr _publ_section_title ; Use of 1,10-phenanthroline ligand in diiron dithiolate derivatives related to the [Fe-Fe] hydrogenase active site. ; loop_ _publ_author_name 'Philippe Schollhammer' 'Jean-Francois Capon' 'Frederic Gloaguen' 'Nelly Kervarec' 'Pierre-Yves Orain' ; F.Petillon ; 'Roger Pichon' 'Jean Talarmi' _publ_contact_author_name 'Schollhammer, P.' data_pdtphen _database_code_depnum_ccdc_archive 'CCDC 650997' _audit_creation_date 2007-05-02T16:07:10-00:00 _audit_creation_method 'WinGX routine CIF_UPDATE' #----------------------------------------------------------------------------# # CHEMICAL INFORMATION # #----------------------------------------------------------------------------# _chemical_name_systematic ; pdt-phen ; _chemical_formula_sum 'C19 H14 Fe2 N2 O4 S2' _chemical_formula_weight 510.14 #----------------------------------------------------------------------------# # UNIT CELL INFORMATION # #----------------------------------------------------------------------------# _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/c loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z+1/2' '-x, -y, -z' 'x, -y-1/2, z-1/2' _cell_length_a 13.8778(10) _cell_length_b 7.5150(6) _cell_length_c 18.8451(13) _cell_angle_alpha 90 _cell_angle_beta 102.196(7) _cell_angle_gamma 90 _cell_volume 1921.0(2) _cell_formula_units_Z 4 _cell_measurement_temperature 170(2) _cell_measurement_reflns_used 9548 _cell_measurement_theta_min 2.9157 _cell_measurement_theta_max 32.9753 #----------------------------------------------------------------------------# # CRYSTAL INFORMATION # #----------------------------------------------------------------------------# _exptl_crystal_description 'rectangular plate' _exptl_crystal_colour 'dark blue' _exptl_crystal_size_max 0.70 _exptl_crystal_size_mid 0.30 _exptl_crystal_size_min 0.10 _exptl_crystal_density_diffrn 1.764 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1032 loop_ _exptl_crystal_face_index_h _exptl_crystal_face_index_k _exptl_crystal_face_index_l _exptl_crystal_face_perp_dist 1 0 0 0.04 -1 0 0 0.06 -1 0 -2 0.1 0 -1 1 0.365 0 1 0 0.32 -1 0 2 0.145 -1 -1 -1 0.305 1 0 -2 0.145 1 0 2 0.105 2 3 -4 0.275 0 2 -25 0.155 -2 3 4 0.315 1 -1 1 0.31 1 -1 -1 0.335 _exptl_special_details ; ? ; #----------------------------------------------------------------------------# # ABSORPTION CORRECTION # #----------------------------------------------------------------------------# _exptl_absorpt_coefficient_mu 1.757 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_absorpt_correction_T_min 0.62103 _exptl_absorpt_correction_T_max 1 #----------------------------------------------------------------------------# # DATA COLLECTION # #----------------------------------------------------------------------------# _diffrn_ambient_temperature 170(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_monochromator graphite _diffrn_detector 'Sapphire 2 (CCD)' _diffrn_orient_matrix_ub_11 0.0283258937 _diffrn_orient_matrix_ub_12 -0.0570070313 _diffrn_orient_matrix_ub_13 0.0263518364 _diffrn_orient_matrix_ub_21 -0.032518922 _diffrn_orient_matrix_ub_22 0.0167362882 _diffrn_orient_matrix_ub_23 0.023628804 _diffrn_orient_matrix_ub_31 -0.0295374239 _diffrn_orient_matrix_ub_32 -0.0731369049 _diffrn_orient_matrix_ub_33 -0.0151546347 _diffrn_measurement_device_type 'X-CALIBUR-2 CCD 4-circle diffractometer' _diffrn_measurement_method ; omega-scans with kappa -79 deg (chi -58.3 deg), phi 0, 90, 180, 270 deg ; _diffrn_standards_interval_count 50 _diffrn_reflns_av_R_equivalents 0.0312 _diffrn_reflns_av_unetI/netI 0.0614 _diffrn_reflns_number 21452 _diffrn_reflns_limit_h_min -21 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -28 _diffrn_reflns_limit_l_max 27 _diffrn_reflns_theta_min 2.92 _diffrn_reflns_theta_max 33.08 _diffrn_reflns_theta_full 33.08 _diffrn_measured_fraction_theta_full 0.93 _diffrn_measured_fraction_theta_max 0.93 _reflns_number_total 6785 _reflns_number_gt 4277 _reflns_threshold_expression >2sigma(I) #----------------------------------------------------------------------------# # COMPUTER PROGRAMS USED # #----------------------------------------------------------------------------# _computing_data_collection ; CrysAlis CCD, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_cell_refinement ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_data_reduction ; CrysAlis RED, Oxford Diffraction Ltd., Version 1.171.31.5 (release 28-08-2006 CrysAlis171 .NET) (compiled Aug 28 2006,13:05:05) ; _computing_structure_solution 'SHELXS-97 (Sheldrick, 1997)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ORTEP3 for Windows (Farrugia, 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^)+(0.0370P)^2^+0.0000P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens difmap _refine_ls_hydrogen_treatment refall _refine_ls_extinction_method none _refine_ls_number_reflns 6785 _refine_ls_number_parameters 318 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0657 _refine_ls_R_factor_gt 0.0306 _refine_ls_wR_factor_ref 0.0771 _refine_ls_wR_factor_gt 0.0648 _refine_ls_goodness_of_fit_ref 1.016 _refine_ls_restrained_S_all 1.016 _refine_ls_shift/su_max 0.092 _refine_ls_shift/su_mean 0.017 _refine_diff_density_max 0.461 _refine_diff_density_min -0.387 _refine_diff_density_rms 0.098 #----------------------------------------------------------------------------# # 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' 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 '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 C1 C 0.22396(13) 0.2796(2) 0.19903(10) 0.0221(4) Uani 1 1 d . . . C2 C 0.08570(14) 0.9369(3) 0.09651(10) 0.0262(4) Uani 1 1 d . . . C3 C 0.17637(14) 0.7320(3) 0.00564(11) 0.0266(4) Uani 1 1 d . . . C4 C 0.28774(14) 0.8827(2) 0.10974(10) 0.0239(4) Uani 1 1 d . . . C5 C 0.00479(15) 0.5134(3) 0.15668(12) 0.0301(4) Uani 1 1 d . . . C6 C 0.02566(16) 0.6497(3) 0.21633(12) 0.0332(5) Uani 1 1 d . . . C7 C 0.12849(16) 0.6407(3) 0.26266(11) 0.0346(5) Uani 1 1 d . . . C8 C 0.19078(16) 0.2525(3) -0.00094(11) 0.0280(4) Uani 1 1 d . . . C9 C 0.21573(19) 0.1679(3) -0.06071(12) 0.0383(5) Uani 1 1 d . . . C10 C 0.3123(2) 0.1587(3) -0.06628(12) 0.0420(6) Uani 1 1 d . . . C11 C 0.38560(17) 0.2346(3) -0.01180(12) 0.0344(5) Uani 1 1 d . . . C12 C 0.4892(2) 0.2302(3) -0.01001(16) 0.0458(7) Uani 1 1 d . . . C13 C 0.55520(19) 0.3019(3) 0.04458(16) 0.0456(7) Uani 1 1 d . . . C14 C 0.52535(15) 0.3905(3) 0.10403(13) 0.0349(5) Uani 1 1 d . . . C15 C 0.58914(16) 0.4728(3) 0.16212(14) 0.0414(6) Uani 1 1 d . . . C16 C 0.55088(16) 0.5542(3) 0.21501(13) 0.0405(6) Uani 1 1 d . . . C17 C 0.44955(15) 0.5507(3) 0.21185(12) 0.0322(5) Uani 1 1 d . . . C18 C 0.42352(14) 0.3960(3) 0.10363(11) 0.0265(4) Uani 1 1 d . . . C19 C 0.35414(14) 0.3185(2) 0.04585(11) 0.0260(4) Uani 1 1 d . . . N1 N 0.25771(11) 0.3287(2) 0.05201(8) 0.0228(3) Uani 1 1 d . . . N2 N 0.38557(11) 0.4734(2) 0.15723(9) 0.0244(3) Uani 1 1 d . . . O1 O 0.20778(11) 0.1774(2) 0.24058(8) 0.0362(3) Uani 1 1 d . . . O2 O 0.02793(11) 1.0468(2) 0.09247(9) 0.0417(4) Uani 1 1 d . . . O3 O 0.18146(12) 0.7097(2) -0.05401(8) 0.0411(4) Uani 1 1 d . . . O4 O 0.36250(10) 0.95318(19) 0.11707(8) 0.0348(3) Uani 1 1 d . . . S1 S 0.08419(3) 0.51264(6) 0.09132(2) 0.02083(10) Uani 1 1 d . . . S2 S 0.22931(3) 0.67580(6) 0.21553(2) 0.02344(11) Uani 1 1 d . . . Fe1 Fe 0.239295(18) 0.45426(3) 0.140946(13) 0.01847(7) Uani 1 1 d . . . Fe2 Fe 0.175626(19) 0.76261(3) 0.098399(14) 0.02001(7) Uani 1 1 d . . . H1 H 0.4271(18) 0.603(3) 0.2482(12) 0.048(7) Uiso 1 1 d . . . H2 H 0.5922(17) 0.616(3) 0.2567(12) 0.040(6) Uiso 1 1 d . . . H3 H 0.6583(19) 0.463(3) 0.1629(13) 0.054(7) Uiso 1 1 d . . . H4 H 0.6209(18) 0.297(3) 0.0451(12) 0.040(6) Uiso 1 1 d . . . H5 H 0.5053(18) 0.181(3) -0.0487(14) 0.052(8) Uiso 1 1 d . . . H6 H 0.3273(16) 0.101(3) -0.1046(11) 0.037(6) Uiso 1 1 d . . . H7 H 0.1645(14) 0.113(3) -0.0954(10) 0.018(5) Uiso 1 1 d . . . H8 H 0.1172(16) 0.257(2) 0.0036(11) 0.027(5) Uiso 1 1 d . . . H9 H 0.1379(19) 0.510(4) 0.2874(14) 0.062(8) Uiso 1 1 d . . . H10 H 0.1355(17) 0.735(3) 0.2980(12) 0.034(6) Uiso 1 1 d . . . H11 H -0.0236(16) 0.628(3) 0.2469(12) 0.042(6) Uiso 1 1 d . . . H12 H 0.0130(14) 0.766(3) 0.1934(11) 0.022(5) Uiso 1 1 d . . . H13 H 0.0122(14) 0.393(3) 0.1755(10) 0.026(5) Uiso 1 1 d . . . H14 H -0.0636(19) 0.525(3) 0.1259(13) 0.049(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 C1 0.0144(8) 0.0261(10) 0.0258(9) -0.0014(8) 0.0044(7) 0.0036(7) C2 0.0245(10) 0.0263(10) 0.0270(10) 0.0015(8) 0.0038(8) -0.0048(8) C3 0.0261(10) 0.0250(10) 0.0283(10) 0.0024(8) 0.0046(8) -0.0042(8) C4 0.0281(10) 0.0218(10) 0.0233(9) 0.0009(8) 0.0089(8) 0.0009(8) C5 0.0210(10) 0.0348(12) 0.0361(11) 0.0033(9) 0.0096(9) -0.0013(9) C6 0.0296(11) 0.0407(13) 0.0344(11) 0.0022(10) 0.0185(9) 0.0014(9) C7 0.0367(12) 0.0485(15) 0.0212(10) -0.0027(10) 0.0119(9) 0.0064(10) C8 0.0360(12) 0.0230(10) 0.0259(10) -0.0017(8) 0.0081(8) -0.0025(8) C9 0.0537(15) 0.0333(12) 0.0297(11) -0.0076(9) 0.0132(11) -0.0027(11) C10 0.0696(18) 0.0322(12) 0.0333(12) -0.0015(10) 0.0310(12) 0.0083(11) C11 0.0486(14) 0.0216(10) 0.0406(12) 0.0078(9) 0.0266(11) 0.0079(9) C12 0.0585(17) 0.0318(13) 0.0607(17) 0.0130(12) 0.0436(15) 0.0150(12) C13 0.0311(13) 0.0436(14) 0.0715(18) 0.0209(13) 0.0323(13) 0.0143(11) C14 0.0259(11) 0.0290(11) 0.0544(13) 0.0205(10) 0.0190(10) 0.0081(9) C15 0.0188(11) 0.0452(14) 0.0594(16) 0.0248(12) 0.0063(10) 0.0048(10) C16 0.0233(11) 0.0456(14) 0.0475(14) 0.0168(11) -0.0039(10) -0.0056(10) C17 0.0211(10) 0.0371(12) 0.0347(11) 0.0067(10) -0.0021(9) -0.0020(9) C18 0.0238(10) 0.0217(10) 0.0371(11) 0.0103(8) 0.0134(8) 0.0049(8) C19 0.0304(11) 0.0201(10) 0.0324(10) 0.0090(8) 0.0176(9) 0.0058(8) N1 0.0264(8) 0.0207(8) 0.0240(8) 0.0020(6) 0.0111(7) 0.0017(6) N2 0.0195(8) 0.0249(8) 0.0289(8) 0.0074(7) 0.0056(6) 0.0006(6) O1 0.0319(8) 0.0383(9) 0.0404(8) 0.0161(7) 0.0119(7) 0.0017(7) O2 0.0353(9) 0.0348(9) 0.0559(10) 0.0081(7) 0.0118(7) 0.0124(7) O3 0.0506(10) 0.0495(10) 0.0243(8) -0.0032(7) 0.0102(7) -0.0102(8) O4 0.0304(8) 0.0345(9) 0.0403(9) 0.0018(7) 0.0096(7) -0.0079(7) S1 0.0184(2) 0.0230(2) 0.0203(2) 0.00064(17) 0.00226(17) -0.00110(17) S2 0.0240(2) 0.0272(3) 0.0183(2) -0.00313(18) 0.00281(18) -0.00062(19) Fe1 0.01655(13) 0.01994(14) 0.01893(13) 0.00041(10) 0.00376(9) -0.00010(10) Fe2 0.02145(14) 0.01941(14) 0.01932(13) 0.00095(10) 0.00467(10) -0.00039(10) #----------------------------------------------------------------------------# # 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 C1 O1 1.153(2) . ? C1 Fe1 1.7506(19) . ? C2 O2 1.143(2) . ? C2 Fe2 1.804(2) . ? C3 O3 1.153(2) . ? C3 Fe2 1.765(2) . ? C4 O4 1.147(2) . ? C4 Fe2 1.7721(19) . ? C5 C6 1.503(3) . ? C5 S1 1.818(2) . ? C6 C7 1.509(3) . ? C7 S2 1.828(2) . ? C8 N1 1.339(2) . ? C8 C9 1.399(3) . ? C9 C10 1.368(3) . ? C10 C11 1.404(3) . ? C11 C19 1.403(3) . ? C11 C12 1.432(3) . ? C12 C13 1.337(4) . ? C13 C14 1.437(3) . ? C14 C15 1.398(3) . ? C14 C18 1.412(3) . ? C15 C16 1.369(3) . ? C16 C17 1.395(3) . ? C17 N2 1.341(3) . ? C18 N2 1.364(2) . ? C18 C19 1.418(3) . ? C19 N1 1.370(2) . ? N1 Fe1 1.9864(15) . ? N2 Fe1 1.9931(15) . ? S1 Fe1 2.2023(5) . ? S1 Fe2 2.2551(5) . ? S2 Fe1 2.2020(5) . ? S2 Fe2 2.2712(5) . ? Fe1 Fe2 2.5483(4) . ? 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 C1 Fe1 172.56(17) . . ? O2 C2 Fe2 177.37(17) . . ? O3 C3 Fe2 176.78(19) . . ? O4 C4 Fe2 176.89(17) . . ? C6 C5 S1 117.41(15) . . ? C5 C6 C7 114.31(18) . . ? C6 C7 S2 116.09(14) . . ? N1 C8 C9 122.9(2) . . ? C10 C9 C8 119.8(2) . . ? C9 C10 C11 119.6(2) . . ? C19 C11 C10 116.9(2) . . ? C19 C11 C12 117.9(2) . . ? C10 C11 C12 125.2(2) . . ? C13 C12 C11 122.0(2) . . ? C12 C13 C14 121.5(2) . . ? C15 C14 C18 117.3(2) . . ? C15 C14 C13 125.2(2) . . ? C18 C14 C13 117.5(2) . . ? C16 C15 C14 119.3(2) . . ? C15 C16 C17 120.2(2) . . ? N2 C17 C16 122.6(2) . . ? N2 C18 C14 123.44(19) . . ? N2 C18 C19 115.99(16) . . ? C14 C18 C19 120.57(19) . . ? N1 C19 C11 124.08(19) . . ? N1 C19 C18 115.41(17) . . ? C11 C19 C18 120.50(18) . . ? C8 N1 C19 116.69(17) . . ? C8 N1 Fe1 129.71(13) . . ? C19 N1 Fe1 113.60(13) . . ? C17 N2 C18 117.15(17) . . ? C17 N2 Fe1 129.56(14) . . ? C18 N2 Fe1 113.29(12) . . ? C5 S1 Fe1 113.01(7) . . ? C5 S1 Fe2 111.79(7) . . ? Fe1 S1 Fe2 69.727(16) . . ? C7 S2 Fe1 111.04(8) . . ? C7 S2 Fe2 112.71(7) . . ? Fe1 S2 Fe2 69.438(16) . . ? C1 Fe1 N1 103.04(7) . . ? C1 Fe1 N2 102.25(7) . . ? N1 Fe1 N2 81.71(7) . . ? C1 Fe1 S2 97.78(6) . . ? N1 Fe1 S2 159.13(5) . . ? N2 Fe1 S2 92.67(5) . . ? C1 Fe1 S1 100.25(6) . . ? N1 Fe1 S1 91.42(5) . . ? N2 Fe1 S1 157.42(5) . . ? S2 Fe1 S1 86.15(2) . . ? C1 Fe1 Fe2 143.00(6) . . ? N1 Fe1 Fe2 105.33(4) . . ? N2 Fe1 Fe2 104.89(5) . . ? S2 Fe1 Fe2 56.560(15) . . ? S1 Fe1 Fe2 56.109(14) . . ? C3 Fe2 C4 89.84(9) . . ? C3 Fe2 C2 102.94(9) . . ? C4 Fe2 C2 102.64(9) . . ? C3 Fe2 S1 87.34(6) . . ? C4 Fe2 S1 154.17(6) . . ? C2 Fe2 S1 103.02(6) . . ? C3 Fe2 S2 148.82(7) . . ? C4 Fe2 S2 85.96(6) . . ? C2 Fe2 S2 108.13(6) . . ? S1 Fe2 S2 83.294(19) . . ? C3 Fe2 Fe1 96.82(6) . . ? C4 Fe2 Fe1 100.83(6) . . ? C2 Fe2 Fe1 149.17(6) . . ? S1 Fe2 Fe1 54.163(14) . . ? S2 Fe2 Fe1 54.002(14) . . ? _chemical_name_common pdt-phen