# Supplementary Material (ESI) for Chemical Communications # This journal is (c) The Royal Society of Chemistry 2008 data_global _journal_name_full Chem.Commun. _journal_coden_Cambridge 0182 _journal_volume ? _journal_page_first ? _journal_year ? _publ_contact_author_name 'Xiaoming Liu' _publ_contact_author_email XIAOMING.LIU@NCU.EDU.CN _publ_section_title ; The Iron Centre of the Cluster-free Hydrogenase (Hmd): Low Spin Fe(II) or Low Spin Fe(0)? ; loop_ _publ_author_name 'Xiaoming Liu.' 'David J Evans' 'Zhimei Li.' 'Qiuyan Luo.' 'C Pickett' ; Xiufeng Wang ; 'Xi-Rui Zeng.' # Attachment 'Fe2N2S2COmm.cif' data_1 _database_code_depnum_ccdc_archive 'CCDC 683069' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 'monoiron complex' _chemical_melting_point N/A _chemical_formula_moiety 'C12 H14 Fe N2 O2 S2' _chemical_formula_sum 'C12 H14 Fe N2 O2 S2' _chemical_formula_weight 338.22 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' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' O O 0.0106 0.0060 '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' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M P-1 _symmetry_space_group_name_Hall '-P 1 ' loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.1525(11) _cell_length_b 7.6915(12) _cell_length_c 13.464(2) _cell_angle_alpha 91.659(2) _cell_angle_beta 95.127(2) _cell_angle_gamma 109.7330(10) _cell_volume 693.05(18) _cell_formula_units_Z 2 _cell_measurement_temperature 273(2) _cell_measurement_reflns_used ? _cell_measurement_theta_min ? _cell_measurement_theta_max ? _exptl_crystal_description block _exptl_crystal_colour dark-red _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.621 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 348 _exptl_absorpt_coefficient_mu 1.387 _exptl_absorpt_correction_type psi-scan _exptl_absorpt_correction_T_min 0.6811 _exptl_absorpt_correction_T_max 0.8738 _exptl_absorpt_process_details 'SADABS (Bruker, 2004)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 273(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 'Bruker APEX-II area-detector diffractometer' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean 0 _diffrn_standards_number 0 _diffrn_standards_interval_count 0 _diffrn_standards_interval_time 0 _diffrn_standards_decay_% 0 _diffrn_reflns_number 4118 _diffrn_reflns_av_R_equivalents 0.0232 _diffrn_reflns_av_sigmaI/netI 0.0813 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min -8 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 2.82 _diffrn_reflns_theta_max 24.99 _reflns_number_total 2205 _reflns_number_gt 1722 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'SHELXP-97 (Sheldrick, 1990)' _computing_publication_material 'SHELXS-97 (Sheldrick, 1990)' _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^)+(0.0650P)^2^+0.1128P] 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_extinction_coef ? _refine_ls_number_reflns 2205 _refine_ls_number_parameters 172 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0588 _refine_ls_R_factor_gt 0.0446 _refine_ls_wR_factor_ref 0.1353 _refine_ls_wR_factor_gt 0.1207 _refine_ls_goodness_of_fit_ref 1.010 _refine_ls_restrained_S_all 1.010 _refine_ls_shift/su_max 0.000 _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 Fe1 Fe 0.10862(7) 0.73370(7) 0.25891(4) 0.0448(2) Uani 1 1 d . . . S2 S 0.02618(15) 0.94008(16) 0.15790(8) 0.0600(3) Uani 1 1 d . . . S1 S 0.20283(15) 0.51133(14) 0.33983(8) 0.0588(3) Uani 1 1 d . . . C1 C 0.3311(5) 1.0703(5) 0.3979(3) 0.0503(9) Uani 1 1 d . . . H1 H 0.2081 1.0576 0.4203 0.060 Uiso 1 1 calc R . . C5 C 0.5156(5) 0.9732(5) 0.2915(3) 0.0474(9) Uani 1 1 d . . . C2 C 0.4943(6) 1.2133(5) 0.4394(3) 0.0586(10) Uani 1 1 d . . . H2 H 0.4827 1.2935 0.4896 0.070 Uiso 1 1 calc R . . C4 C 0.6863(6) 1.1162(5) 0.3295(3) 0.0581(10) Uani 1 1 d . . . H4 H 0.8071 1.1313 0.3040 0.070 Uiso 1 1 calc R . . C3 C 0.6765(6) 1.2361(5) 0.4051(3) 0.0617(11) Uani 1 1 d . . . H3 H 0.7908 1.3309 0.4326 0.074 Uiso 1 1 calc R . . N1 N 0.3376(4) 0.9461(4) 0.3264(2) 0.0440(7) Uani 1 1 d . . . C7 C -0.0895(6) 0.5560(6) 0.1920(3) 0.0597(10) Uani 1 1 d . . . C6 C -0.0503(5) 0.7414(5) 0.3493(3) 0.0511(9) Uani 1 1 d . . . O1 O -0.1533(4) 0.7437(5) 0.4090(2) 0.0780(9) Uani 1 1 d . . . O2 O -0.2225(5) 0.4422(5) 0.1502(2) 0.0886(11) Uani 1 1 d . . . C8 C 0.5184(5) 0.8328(5) 0.2139(3) 0.0562(10) Uani 1 1 d . . . H8A H 0.5772 0.7480 0.2444 0.067 Uiso 1 1 calc R . . H8B H 0.6017 0.8945 0.1635 0.067 Uiso 1 1 calc R . . N2 N 0.3147(4) 0.7259(4) 0.1652(2) 0.0485(7) Uani 1 1 d . . . C10 C 0.2383(6) 0.9832(7) 0.0863(3) 0.0672(12) Uani 1 1 d . . . H10A H 0.2109 1.0313 0.0230 0.081 Uiso 1 1 calc R . . H10B H 0.3552 1.0743 0.1227 0.081 Uiso 1 1 calc R . . C9 C 0.2770(6) 0.8041(7) 0.0684(3) 0.0667(12) Uani 1 1 d . . . H9A H 0.1625 0.7157 0.0290 0.080 Uiso 1 1 calc R . . H9B H 0.3919 0.8264 0.0311 0.080 Uiso 1 1 calc R . . C12 C 0.3204(7) 0.4349(6) 0.2414(4) 0.0783(14) Uani 1 1 d . . . H12A H 0.4603 0.4606 0.2638 0.094 Uiso 1 1 calc R . . H12B H 0.2580 0.3021 0.2284 0.094 Uiso 1 1 calc R . . C11 C 0.3037(6) 0.5294(6) 0.1455(3) 0.0657(12) Uani 1 1 d . . . H11A H 0.4108 0.5278 0.1064 0.079 Uiso 1 1 calc R . . H11B H 0.1779 0.4610 0.1065 0.079 Uiso 1 1 calc 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 Fe1 0.0384(3) 0.0595(4) 0.0372(3) 0.0028(2) 0.0075(2) 0.0166(2) S2 0.0512(6) 0.0874(8) 0.0505(6) 0.0189(5) 0.0114(4) 0.0327(5) S1 0.0610(6) 0.0616(6) 0.0555(7) 0.0089(5) 0.0077(5) 0.0224(5) C1 0.053(2) 0.056(2) 0.046(2) 0.0052(17) 0.0103(16) 0.0221(17) C5 0.0462(19) 0.054(2) 0.042(2) 0.0098(17) 0.0074(15) 0.0162(16) C2 0.066(3) 0.053(2) 0.056(3) -0.0011(19) 0.0055(19) 0.0202(19) C4 0.045(2) 0.062(2) 0.065(3) 0.013(2) 0.0108(18) 0.0129(17) C3 0.058(2) 0.051(2) 0.065(3) 0.0008(19) -0.0055(19) 0.0068(17) N1 0.0445(16) 0.0530(17) 0.0378(16) 0.0081(13) 0.0103(12) 0.0190(13) C7 0.049(2) 0.076(3) 0.052(2) -0.001(2) 0.0092(18) 0.019(2) C6 0.048(2) 0.060(2) 0.047(2) 0.0040(17) 0.0088(17) 0.0200(17) O1 0.0681(18) 0.108(2) 0.064(2) 0.0119(17) 0.0364(16) 0.0307(17) O2 0.0589(18) 0.111(3) 0.075(2) -0.025(2) 0.0046(15) 0.0051(17) C8 0.0395(19) 0.073(3) 0.059(2) 0.002(2) 0.0109(16) 0.0216(17) N2 0.0420(16) 0.0651(19) 0.0403(17) -0.0010(15) 0.0094(12) 0.0199(13) C10 0.065(3) 0.101(3) 0.046(2) 0.028(2) 0.0207(19) 0.037(2) C9 0.062(3) 0.103(3) 0.041(2) 0.008(2) 0.0161(18) 0.032(2) C12 0.081(3) 0.072(3) 0.093(4) 0.008(3) 0.029(3) 0.036(2) C11 0.061(2) 0.075(3) 0.067(3) -0.012(2) 0.015(2) 0.030(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 Fe1 C6 1.751(4) . ? Fe1 C7 1.755(4) . ? Fe1 N1 2.005(3) . ? Fe1 N2 2.039(3) . ? Fe1 S1 2.3067(11) . ? Fe1 S2 2.3089(12) . ? S2 C10 1.811(4) . ? S1 C12 1.816(5) . ? C1 N1 1.352(4) . ? C1 C2 1.366(5) . ? C1 H1 0.9300 . ? C5 N1 1.348(4) . ? C5 C4 1.382(5) . ? C5 C8 1.488(5) . ? C2 C3 1.378(6) . ? C2 H2 0.9300 . ? C4 C3 1.377(6) . ? C4 H4 0.9300 . ? C3 H3 0.9300 . ? C7 O2 1.141(4) . ? C6 O1 1.141(4) . ? C8 N2 1.489(4) . ? C8 H8A 0.9700 . ? C8 H8B 0.9700 . ? N2 C9 1.491(5) . ? N2 C11 1.501(5) . ? C10 C9 1.511(6) . ? C10 H10A 0.9700 . ? C10 H10B 0.9700 . ? C9 H9A 0.9700 . ? C9 H9B 0.9700 . ? C12 C11 1.515(7) . ? C12 H12A 0.9700 . ? C12 H12B 0.9700 . ? C11 H11A 0.9700 . ? C11 H11B 0.9700 . ? 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 C6 Fe1 C7 89.07(17) . . ? C6 Fe1 N1 93.43(14) . . ? C7 Fe1 N1 175.94(16) . . ? C6 Fe1 N2 174.27(14) . . ? C7 Fe1 N2 95.00(15) . . ? N1 Fe1 N2 82.74(11) . . ? C6 Fe1 S1 91.64(13) . . ? C7 Fe1 S1 88.81(15) . . ? N1 Fe1 S1 94.32(9) . . ? N2 Fe1 S1 84.43(10) . . ? C6 Fe1 S2 95.65(13) . . ? C7 Fe1 S2 87.92(15) . . ? N1 Fe1 S2 88.64(9) . . ? N2 Fe1 S2 88.55(10) . . ? S1 Fe1 S2 171.96(4) . . ? C10 S2 Fe1 95.29(15) . . ? C12 S1 Fe1 99.60(17) . . ? N1 C1 C2 123.9(3) . . ? N1 C1 H1 118.0 . . ? C2 C1 H1 118.0 . . ? N1 C5 C4 122.1(3) . . ? N1 C5 C8 115.6(3) . . ? C4 C5 C8 122.2(3) . . ? C1 C2 C3 118.5(4) . . ? C1 C2 H2 120.7 . . ? C3 C2 H2 120.7 . . ? C3 C4 C5 119.6(4) . . ? C3 C4 H4 120.2 . . ? C5 C4 H4 120.2 . . ? C4 C3 C2 118.9(4) . . ? C4 C3 H3 120.6 . . ? C2 C3 H3 120.6 . . ? C5 N1 C1 116.9(3) . . ? C5 N1 Fe1 115.5(2) . . ? C1 N1 Fe1 127.5(2) . . ? O2 C7 Fe1 177.8(4) . . ? O1 C6 Fe1 178.7(4) . . ? C5 C8 N2 112.2(3) . . ? C5 C8 H8A 109.2 . . ? N2 C8 H8A 109.2 . . ? C5 C8 H8B 109.2 . . ? N2 C8 H8B 109.2 . . ? H8A C8 H8B 107.9 . . ? C8 N2 C9 110.3(3) . . ? C8 N2 C11 108.0(3) . . ? C9 N2 C11 109.1(3) . . ? C8 N2 Fe1 109.2(2) . . ? C9 N2 Fe1 110.5(2) . . ? C11 N2 Fe1 109.7(2) . . ? C9 C10 S2 109.0(3) . . ? C9 C10 H10A 109.9 . . ? S2 C10 H10A 109.9 . . ? C9 C10 H10B 109.9 . . ? S2 C10 H10B 109.9 . . ? H10A C10 H10B 108.3 . . ? N2 C9 C10 110.6(3) . . ? N2 C9 H9A 109.5 . . ? C10 C9 H9A 109.5 . . ? N2 C9 H9B 109.5 . . ? C10 C9 H9B 109.5 . . ? H9A C9 H9B 108.1 . . ? C11 C12 S1 112.3(3) . . ? C11 C12 H12A 109.1 . . ? S1 C12 H12A 109.1 . . ? C11 C12 H12B 109.1 . . ? S1 C12 H12B 109.1 . . ? H12A C12 H12B 107.9 . . ? N2 C11 C12 112.0(3) . . ? N2 C11 H11A 109.2 . . ? C12 C11 H11A 109.2 . . ? N2 C11 H11B 109.2 . . ? C12 C11 H11B 109.2 . . ? H11A C11 H11B 107.9 . . ? _diffrn_measured_fraction_theta_max 0.904 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.904 _refine_diff_density_max 0.422 _refine_diff_density_min -0.537 _refine_diff_density_rms 0.079