# Supplementary Material (ESI) for ChemComm # This journal is © The Royal Society of Chemistry, 1999 # CCDC Number: 182/1321 data_global _publ_section_title ; Iron Carbonyl Complexes of 1H-Diphosphirenes and Diphosphirenylium Salts ; loop_ _publ_author_name 'Didier Bourissou' 'Yves Canac' 'Heinz Gornitzka' 'Antoine Baceiredo' 'Guy Bertrand' data_3 _audit_creation_method SHELXL _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_structural ? _chemical_formula_analytical ? _chemical_formula_sum 'C19 H28 Fe2 N2 O6 P2' _chemical_formula_weight 554.07 _chemical_melting_point ? _chemical_compound_source ? 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' 'P' 'P' 0.1023 0.0942 '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 monoclinic _symmetry_space_group_name_H-M P2(1)/n 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 9.885(2) _cell_length_b 18.173(3) _cell_length_c 14.729(3) _cell_angle_alpha 90.00 _cell_angle_beta 99.85(2) _cell_angle_gamma 90.00 _cell_volume 2606.9(9) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 5000 _cell_measurement_theta_min 1.8 _cell_measurement_theta_max 24.0 _exptl_crystal_description block _exptl_crystal_colour rouge _exptl_crystal_size_max 0.3 _exptl_crystal_size_mid 0.3 _exptl_crystal_size_min 0.2 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.412 _exptl_crystal_density_method ? _exptl_crystal_F_000 1144 _exptl_absorpt_coefficient_mu 1.269 _exptl_absorpt_correction_type numerical _exptl_absorpt_correction_T_min 0.7035 _exptl_absorpt_correction_T_max 0.8889 _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(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 'STOE-IPDS' _diffrn_measurement_method 'Phi-scans' _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 17710 _diffrn_reflns_av_R_equivalents 0.1451 _diffrn_reflns_av_sigmaI/netI 0.0901 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -20 _diffrn_reflns_limit_k_max 20 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.24 _diffrn_reflns_theta_max 22.72 _reflns_number_total 3493 _reflns_number_observed 2227 _reflns_observed_criterion >2sigma(I) _computing_data_collection 'STOE-IPDS' _computing_cell_refinement 'STOE-IPDS' _computing_data_reduction 'STOE-IPDS' _computing_structure_solution 'SHELXS-96 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-96 (Sheldrick, 1996)' _computing_molecular_graphics ? _computing_publication_material 'SHELXL-96 (Sheldrick, 1996)' _refine_special_details ; Refinement of F^2^ against ALL reflections. Weighted R-factors wR and all goodnesses 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 observed criterion of F^2^ > 2sigma(F^2^) is used only for calculating _R_factor_obs 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 w=1/[\s^2^(Fo^2^)+(0.1154P)^2^+0.0000P] 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 ? _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3493 _refine_ls_number_parameters 287 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1134 _refine_ls_R_factor_obs 0.0693 _refine_ls_wR_factor_all 0.1942 _refine_ls_wR_factor_obs 0.1628 _refine_ls_goodness_of_fit_all 1.007 _refine_ls_goodness_of_fit_obs 1.078 _refine_ls_restrained_S_all 1.007 _refine_ls_restrained_S_obs 1.078 _refine_ls_shift/esd_max 0.000 _refine_ls_shift/esd_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_thermal_displace_type _atom_site_occupancy _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_group Fe2 Fe 0.06402(13) 0.34962(7) 0.69912(8) 0.0538(4) Uani 1 d . . Fe1 Fe 0.13613(12) 0.38646(6) 0.87210(8) 0.0511(4) Uani 1 d . . P1 P -0.0280(2) 0.30820(11) 0.81677(14) 0.0469(5) Uani 1 d . . C1 C 0.0870(8) 0.2301(4) 0.8224(5) 0.0415(17) Uani 1 d . . P2 P 0.2306(2) 0.28987(12) 0.80453(17) 0.0564(6) Uani 1 d . . N1 N 0.0793(7) 0.1589(3) 0.8268(4) 0.0473(15) Uani 1 d . . C2 C -0.0533(9) 0.1220(5) 0.8342(6) 0.059(2) Uani 1 d . . H2 H -0.1206 0.1608 0.8389 0.071 Uiso 1 calc R . C3 C -0.0407(14) 0.0753(7) 0.9215(8) 0.099(4) Uani 1 d . . H3A H -0.1283 0.0539 0.9256 0.148 Uiso 1 calc R . H3B H -0.0113 0.1057 0.9744 0.148 Uiso 1 calc R . H3C H 0.0253 0.0369 0.9193 0.148 Uiso 1 calc R . C4 C -0.1082(12) 0.0768(6) 0.7492(8) 0.084(3) Uani 1 d . . H4A H -0.1987 0.0594 0.7532 0.127 Uiso 1 calc R . H4B H -0.0486 0.0356 0.7454 0.127 Uiso 1 calc R . H4C H -0.1121 0.1068 0.6952 0.127 Uiso 1 calc R . C5 C 0.2003(10) 0.1102(5) 0.8217(7) 0.064(2) Uani 1 d . . H5 H 0.1679 0.0595 0.8254 0.076 Uiso 1 calc R . C6 C 0.3130(12) 0.1214(7) 0.9054(9) 0.093(3) Uani 1 d . . H6A H 0.3826 0.0845 0.9056 0.140 Uiso 1 calc R . H6B H 0.2743 0.1173 0.9607 0.140 Uiso 1 calc R . H6C H 0.3529 0.1693 0.9026 0.140 Uiso 1 calc R . C7 C 0.2486(12) 0.1169(5) 0.7295(8) 0.085(3) Uani 1 d . . H7A H 0.3192 0.0813 0.7262 0.128 Uiso 1 calc R . H7B H 0.2844 0.1655 0.7235 0.128 Uiso 1 calc R . H7C H 0.1727 0.1083 0.6806 0.128 Uiso 1 calc R . N2 N -0.1917(7) 0.2975(4) 0.8295(5) 0.0545(17) Uani 1 d . . C8 C -0.2416(11) 0.3123(6) 0.9182(7) 0.076(3) Uani 1 d . . H8 H -0.3391 0.2991 0.9062 0.091 Uiso 1 calc R . C9 C -0.1762(14) 0.2595(7) 0.9936(8) 0.103(4) Uani 1 d . . H9A H -0.2010 0.2738 1.0513 0.155 Uiso 1 calc R . H9B H -0.0781 0.2610 0.9985 0.155 Uiso 1 calc R . H9C H -0.2083 0.2104 0.9784 0.155 Uiso 1 calc R . C10 C -0.2385(16) 0.3914(7) 0.9463(9) 0.112(5) Uani 1 d . . H10A H -0.3133 0.4012 0.9784 0.169 Uiso 1 calc R . H10B H -0.2470 0.4220 0.8925 0.169 Uiso 1 calc R . H10C H -0.1532 0.4019 0.9861 0.169 Uiso 1 calc R . C11 C -0.2984(9) 0.2803(6) 0.7480(6) 0.069(3) Uani 1 d . . H11 H -0.2490 0.2667 0.6982 0.083 Uiso 1 calc R . C12 C -0.3862(11) 0.2160(6) 0.7617(9) 0.094(4) Uani 1 d . . H12A H -0.4553 0.2096 0.7080 0.141 Uiso 1 calc R . H12B H -0.4295 0.2246 0.8144 0.141 Uiso 1 calc R . H12C H -0.3305 0.1725 0.7716 0.141 Uiso 1 calc R . C13 C -0.3836(13) 0.3473(9) 0.7146(10) 0.120(5) Uani 1 d . . H13A H -0.4655 0.3321 0.6741 0.180 Uiso 1 calc R . H13B H -0.3314 0.3793 0.6821 0.180 Uiso 1 calc R . H13C H -0.4081 0.3729 0.7665 0.180 Uiso 1 calc R . O1 O 0.3993(9) 0.4611(5) 0.8738(7) 0.110(3) Uani 1 d . . C14 C 0.2929(10) 0.4336(5) 0.8716(7) 0.069(2) Uani 1 d . . O2 O 0.1899(10) 0.3369(5) 1.0626(6) 0.106(3) Uani 1 d . . C15 C 0.1685(11) 0.3571(6) 0.9891(7) 0.072(3) Uani 1 d . . O3 O -0.0275(9) 0.5210(4) 0.8714(6) 0.096(2) Uani 1 d . . C16 C 0.0366(10) 0.4672(5) 0.8731(6) 0.065(2) Uani 1 d . . O4 O 0.2877(9) 0.4201(4) 0.6253(6) 0.101(3) Uani 1 d . . C17 C 0.1987(11) 0.3920(5) 0.6530(7) 0.069(3) Uani 1 d . . O5 O -0.0114(9) 0.2375(5) 0.5584(6) 0.100(2) Uani 1 d . . C18 C 0.0153(10) 0.2823(5) 0.6132(7) 0.066(2) Uani 1 d . . O6 O -0.1292(10) 0.4696(5) 0.6420(7) 0.119(3) Uani 1 d . . C19 C -0.0542(12) 0.4213(6) 0.6646(7) 0.080(3) Uani 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 Fe2 0.0574(8) 0.0568(7) 0.0493(7) 0.0007(6) 0.0146(5) 0.0028(6) Fe1 0.0523(7) 0.0486(7) 0.0517(7) 0.0001(5) 0.0069(5) -0.0007(5) P1 0.0461(12) 0.0461(11) 0.0490(12) -0.0011(9) 0.0094(9) 0.0029(9) C1 0.044(4) 0.047(5) 0.035(4) 0.002(3) 0.012(3) 0.002(3) P2 0.0443(12) 0.0502(12) 0.0766(15) 0.0036(11) 0.0162(11) 0.0024(9) N1 0.049(4) 0.046(4) 0.047(4) 0.005(3) 0.009(3) 0.006(3) C2 0.058(5) 0.051(5) 0.069(5) 0.005(4) 0.015(4) -0.004(4) C3 0.132(11) 0.085(7) 0.086(8) 0.029(6) 0.036(8) -0.002(7) C4 0.082(8) 0.072(6) 0.098(8) -0.015(6) 0.009(6) -0.017(6) C5 0.063(6) 0.045(5) 0.085(6) 0.008(4) 0.017(5) 0.013(4) C6 0.069(7) 0.094(8) 0.108(9) 0.020(7) -0.008(6) 0.013(6) C7 0.093(8) 0.059(6) 0.111(9) -0.021(6) 0.039(7) 0.004(5) N2 0.050(4) 0.065(4) 0.050(4) -0.011(3) 0.014(3) -0.004(3) C8 0.074(7) 0.098(7) 0.061(6) -0.008(6) 0.028(5) 0.012(5) C9 0.117(10) 0.136(10) 0.066(7) 0.012(7) 0.044(7) 0.001(8) C10 0.150(13) 0.101(9) 0.097(9) -0.040(7) 0.050(9) 0.007(8) C11 0.051(5) 0.098(7) 0.058(5) -0.021(5) 0.012(4) -0.010(5) C12 0.051(6) 0.099(8) 0.131(10) -0.024(7) 0.012(6) -0.014(6) C13 0.072(8) 0.165(13) 0.115(10) 0.033(9) -0.008(7) 0.006(8) O1 0.073(5) 0.095(6) 0.166(9) 0.001(5) 0.030(5) -0.027(4) C14 0.058(6) 0.064(6) 0.086(7) 0.003(5) 0.010(5) 0.000(5) O2 0.117(7) 0.137(7) 0.058(5) 0.011(5) 0.003(4) 0.012(5) C15 0.076(7) 0.079(7) 0.062(6) -0.002(5) 0.015(5) 0.010(5) O3 0.106(6) 0.072(5) 0.112(6) -0.011(4) 0.024(5) 0.021(4) C16 0.073(6) 0.064(6) 0.058(5) -0.004(5) 0.010(5) -0.001(5) O4 0.107(6) 0.093(5) 0.113(6) 0.006(5) 0.048(5) -0.026(5) C17 0.078(7) 0.063(6) 0.070(6) 0.000(5) 0.020(5) -0.010(5) O5 0.102(6) 0.114(6) 0.080(5) -0.028(5) 0.005(4) -0.014(5) C18 0.076(7) 0.068(6) 0.054(5) -0.008(5) 0.012(5) -0.009(5) O6 0.122(7) 0.120(7) 0.116(7) 0.034(6) 0.026(6) 0.061(6) C19 0.092(8) 0.082(7) 0.073(6) 0.008(6) 0.033(6) 0.019(6) _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 Fe2 C19 1.7652(118) . ? Fe2 C18 1.7675(102) . ? Fe2 C17 1.7716(101) . ? Fe2 P1 2.2219(23) . ? Fe2 P2 2.3291(27) . ? Fe2 Fe1 2.6127(17) . ? Fe1 C16 1.7680(102) . ? Fe1 C14 1.7721(101) . ? Fe1 C15 1.7796(109) . ? Fe1 P1 2.2064(24) . ? Fe1 P2 2.2936(25) . ? P1 N2 1.6712(69) . ? P1 C1 1.8113(74) . ? P1 P2 2.6145(29) . ? C1 N1 1.2981(92) . ? C1 P2 1.8414(72) . ? N1 C2 1.4931(104) . ? N1 C5 1.5002(103) . ? C2 C4 1.5180(139) . ? C2 C3 1.5287(133) . ? C5 C7 1.5200(139) . ? C5 C6 1.5271(152) . ? N2 C11 1.4895(114) . ? N2 C8 1.4977(105) . ? C8 C10 1.4952(150) . ? C8 C9 1.5249(156) . ? C11 C12 1.4893(135) . ? C11 C13 1.5138(163) . ? O1 C14 1.1592(115) . ? O2 C15 1.1285(119) . ? O3 C16 1.1626(109) . ? O4 C17 1.1505(110) . ? O5 C18 1.1443(109) . ? O6 C19 1.1607(125) . ? 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 C19 Fe2 C18 102.6(5) . . ? C19 Fe2 C17 94.2(5) . . ? C18 Fe2 C17 99.0(4) . . ? C19 Fe2 P1 97.8(3) . . ? C18 Fe2 P1 103.1(3) . . ? C17 Fe2 P1 151.8(3) . . ? C19 Fe2 P2 153.3(4) . . ? C18 Fe2 P2 103.3(3) . . ? C17 Fe2 P2 88.1(4) . . ? P1 Fe2 P2 70.08(8) . . ? C19 Fe2 Fe1 98.5(4) . . ? C18 Fe2 Fe1 150.6(3) . . ? C17 Fe2 Fe1 99.5(3) . . ? P1 Fe2 Fe1 53.57(7) . . ? P2 Fe2 Fe1 54.94(7) . . ? C16 Fe1 C14 95.0(4) . . ? C16 Fe1 C15 104.4(4) . . ? C14 Fe1 C15 97.8(5) . . ? C16 Fe1 P1 99.4(3) . . ? C14 Fe1 P1 154.0(3) . . ? C15 Fe1 P1 99.4(4) . . ? C16 Fe1 P2 155.1(3) . . ? C14 Fe1 P2 87.0(3) . . ? C15 Fe1 P2 99.9(3) . . ? P1 Fe1 P2 71.01(8) . . ? C16 Fe1 Fe2 99.3(3) . . ? C14 Fe1 Fe2 102.3(3) . . ? C15 Fe1 Fe2 147.3(3) . . ? P1 Fe1 Fe2 54.12(6) . . ? P2 Fe1 Fe2 56.23(7) . . ? N2 P1 C1 121.1(3) . . ? N2 P1 Fe1 134.3(2) . . ? C1 P1 Fe1 94.1(3) . . ? N2 P1 Fe2 131.3(3) . . ? C1 P1 Fe2 87.9(2) . . ? Fe1 P1 Fe2 72.31(8) . . ? N2 P1 P2 165.8(3) . . ? C1 P1 P2 44.8(2) . . ? Fe1 P1 P2 56.05(8) . . ? Fe2 P1 P2 56.88(8) . . ? N1 C1 P1 137.9(6) . . ? N1 C1 P2 130.4(5) . . ? P1 C1 P2 91.4(3) . . ? C1 P2 Fe1 90.5(2) . . ? C1 P2 Fe2 84.0(2) . . ? Fe1 P2 Fe2 68.82(7) . . ? C1 P2 P1 43.8(2) . . ? Fe1 P2 P1 52.94(7) . . ? Fe2 P2 P1 53.03(7) . . ? C1 N1 C2 120.7(6) . . ? C1 N1 C5 122.1(7) . . ? C2 N1 C5 117.1(6) . . ? N1 C2 C4 112.2(7) . . ? N1 C2 C3 111.4(8) . . ? C4 C2 C3 111.0(8) . . ? N1 C5 C7 111.8(8) . . ? N1 C5 C6 111.0(8) . . ? C7 C5 C6 114.4(9) . . ? C11 N2 C8 116.6(7) . . ? C11 N2 P1 120.0(5) . . ? C8 N2 P1 123.1(6) . . ? C10 C8 N2 114.8(9) . . ? C10 C8 C9 114.7(10) . . ? N2 C8 C9 111.1(8) . . ? C12 C11 N2 113.9(9) . . ? C12 C11 C13 111.7(9) . . ? N2 C11 C13 111.8(9) . . ? O1 C14 Fe1 176.2(9) . . ? O2 C15 Fe1 178.4(10) . . ? O3 C16 Fe1 178.0(8) . . ? O4 C17 Fe2 178.2(9) . . ? O5 C18 Fe2 177.4(10) . . ? O6 C19 Fe2 178.4(11) . . ? _refine_diff_density_max 0.729 _refine_diff_density_min -0.636 _refine_diff_density_rms 0.099 #===END data_4 _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_formula_moiety ? _chemical_formula_sum 'C23 H28 Fe3 N2 O10 P2' _chemical_formula_weight 721.96 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' 'P' 'P' 0.1023 0.0942 '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 orthorhombic _symmetry_space_group_name_H-M Pbca loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z+1/2' 'x+1/2, -y+1/2, -z' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z-1/2' '-x-1/2, y-1/2, z' _cell_length_a 15.7039(4) _cell_length_b 19.5502(4) _cell_length_c 20.3360(5) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 6243.4(3) _cell_formula_units_Z 8 _cell_measurement_temperature 193(2) _cell_measurement_reflns_used 5000 _cell_measurement_theta_min 1.94 _cell_measurement_theta_max 22.99 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.5 _exptl_crystal_size_mid 0.4 _exptl_crystal_size_min 0.3 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.536 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2944 _exptl_absorpt_coefficient_mu 1.529 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 193(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 'STOE-IPDS' _diffrn_measurement_method 'phi-rotation' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 12139 _diffrn_reflns_av_R_equivalents 0.1460 _diffrn_reflns_av_sigmaI/netI 0.0285 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 16 _diffrn_reflns_limit_k_min -21 _diffrn_reflns_limit_k_max 21 _diffrn_reflns_limit_l_min -22 _diffrn_reflns_limit_l_max 22 _diffrn_reflns_theta_min 1.94 _diffrn_reflns_theta_max 22.99 _reflns_number_total 4287 _reflns_number_gt 4018 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'STOE-IPDS' _computing_cell_refinement 'STOE-IPDS' _computing_data_reduction 'STOE-IPDS' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'ZORTEP (Zsolnai, 1998)' _computing_publication_material 'SHELXL-97 (Sheldrick, 1997)' _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 w=1/[\s^2^(Fo^2^)+(0.0530P)^2^+12.9195P] 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 mixed _refine_ls_extinction_method SHELXL _refine_ls_extinction_coef 0.0020(2) _refine_ls_extinction_expression 'Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^' _refine_ls_number_reflns 4287 _refine_ls_number_parameters 370 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0548 _refine_ls_R_factor_gt 0.0513 _refine_ls_wR_factor_ref 0.1233 _refine_ls_wR_factor_gt 0.1213 _refine_ls_goodness_of_fit_ref 1.212 _refine_ls_restrained_S_all 1.212 _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_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.8510(3) 0.3463(2) 0.42658(19) 0.0239(9) Uani 1 d . . . Fe3 Fe 0.92613(4) 0.17393(3) 0.46263(3) 0.0332(2) Uani 1 d . . . P1 P 0.87587(7) 0.38517(6) 0.34680(5) 0.0292(3) Uani 1 d . . . N1 N 0.8032(2) 0.36182(17) 0.47702(17) 0.0274(8) Uani 1 d . . . C2 C 0.8016(3) 0.3151(2) 0.5354(2) 0.0362(11) Uani 1 d . . . H2 H 0.8326 0.2728 0.5215 0.043 Uiso 1 calc R . . Fe2 Fe 0.84046(4) 0.28705(3) 0.30084(3) 0.0326(2) Uani 1 d . . . P2 P 0.90860(7) 0.26817(5) 0.39918(5) 0.0273(3) Uani 1 d . . . C3 C 0.8522(4) 0.3440(3) 0.5934(3) 0.0652(17) Uani 1 d . . . H3A H 0.9044 0.3657 0.5771 0.098 Uiso 1 calc R . . H3B H 0.8671 0.3068 0.6236 0.098 Uiso 1 calc R . . H3C H 0.8176 0.3780 0.6166 0.098 Uiso 1 calc R . . N2 N 0.8475(3) 0.46497(18) 0.33066(19) 0.0391(10) Uani 1 d . . . Fe1 Fe 0.99536(4) 0.32741(3) 0.33093(3) 0.0354(2) Uani 1 d . . . C4 C 0.7126(4) 0.2917(3) 0.5550(3) 0.0637(17) Uani 1 d . . . H4A H 0.7169 0.2550 0.5876 0.096 Uiso 1 calc R . . H4B H 0.6824 0.2748 0.5160 0.096 Uiso 1 calc R . . H4C H 0.6812 0.3303 0.5739 0.096 Uiso 1 calc R . . C5 C 0.7486(3) 0.4251(2) 0.4732(2) 0.0377(11) Uani 1 d . . . H5 H 0.7729 0.4541 0.4373 0.045 Uiso 1 calc R . . C6 C 0.7504(4) 0.4681(3) 0.5352(3) 0.0634(17) Uani 1 d . . . H6A H 0.8097 0.4768 0.5479 0.095 Uiso 1 calc R . . H6B H 0.7215 0.4435 0.5708 0.095 Uiso 1 calc R . . H6C H 0.7214 0.5116 0.5272 0.095 Uiso 1 calc R . . C7 C 0.6572(3) 0.4069(3) 0.4522(3) 0.0589(16) Uani 1 d . . . H7A H 0.6293 0.3811 0.4875 0.088 Uiso 1 calc R . . H7B H 0.6588 0.3790 0.4122 0.088 Uiso 1 calc R . . H7C H 0.6251 0.4490 0.4436 0.088 Uiso 1 calc R . . C8 C 0.7716(4) 0.4780(3) 0.2884(3) 0.0535(14) Uani 1 d . . . H8 H 0.7419 0.4332 0.2824 0.064 Uiso 1 calc R . . C9 C 0.7970(5) 0.5036(4) 0.2195(3) 0.085(2) Uani 1 d . . . H9A H 0.8233 0.5489 0.2232 0.127 Uiso 1 calc R . . H9B H 0.7462 0.5065 0.1917 0.127 Uiso 1 calc R . . H9C H 0.8378 0.4716 0.1998 0.127 Uiso 1 calc R . . C10 C 0.7073(5) 0.5272(3) 0.3201(3) 0.080(2) Uani 1 d . . . H10A H 0.6936 0.5113 0.3645 0.119 Uiso 1 calc R . . H10B H 0.6553 0.5285 0.2935 0.119 Uiso 1 calc R . . H10C H 0.7321 0.5731 0.3224 0.119 Uiso 1 calc R . . C11 C 0.8144(3) 0.1604(2) 0.4555(3) 0.0430(12) Uani 1 d . . . O11 O 0.7420(3) 0.1506(2) 0.4501(2) 0.0748(13) Uani 1 d . . . O12 O 0.9365(3) 0.0669(3) 0.5627(2) 0.0868(15) Uani 1 d . . . C12 C 0.9325(3) 0.1091(3) 0.5236(3) 0.0510(14) Uani 1 d . . . C13 C 0.9851(4) 0.1243(3) 0.4029(3) 0.0477(13) Uani 1 d . . . O13 O 1.0213(3) 0.0885(2) 0.3690(2) 0.0768(13) Uani 1 d . . . O14 O 1.0325(3) 0.2632(2) 0.5448(2) 0.0799(14) Uani 1 d . . . C14 C 0.9915(3) 0.2281(3) 0.5131(3) 0.0459(13) Uani 1 d . . . C17 C 0.9019(4) 0.5247(3) 0.3481(3) 0.0552(15) Uani 1 d . . . H17 H 0.8678 0.5667 0.3389 0.066 Uiso 1 calc R . . C18 C 0.9247(4) 0.5263(3) 0.4213(3) 0.0671(18) Uani 1 d . . . H18A H 0.9614 0.5657 0.4302 0.101 Uiso 1 calc R . . H18B H 0.9548 0.4841 0.4330 0.101 Uiso 1 calc R . . H18C H 0.8725 0.5300 0.4474 0.101 Uiso 1 calc R . . C19 C 0.9830(5) 0.5293(4) 0.3065(4) 0.088(2) Uani 1 d . . . H19A H 1.0084 0.5748 0.3116 0.132 Uiso 1 calc R . . H19B H 0.9688 0.5217 0.2601 0.132 Uiso 1 calc R . . H19C H 1.0237 0.4945 0.3211 0.132 Uiso 1 calc R . . O21 O 0.8118(4) 0.3386(2) 0.1673(2) 0.1003(19) Uani 1 d . . . C21 C 0.8237(4) 0.3195(3) 0.2194(3) 0.0554(15) Uani 1 d . . . O22 O 0.6637(3) 0.2575(3) 0.3378(2) 0.0849(15) Uani 1 d . . . C22 C 0.7323(4) 0.2695(3) 0.3228(3) 0.0482(13) Uani 1 d . . . O30 O 1.1000(3) 0.2077(2) 0.2978(2) 0.0771(13) Uani 1 d . . . C30 C 1.0586(3) 0.2535(3) 0.3111(3) 0.0481(13) Uani 1 d . . . C31 C 0.8733(4) 0.2053(3) 0.2729(2) 0.0444(13) Uani 1 d . . . O31 O 0.8965(3) 0.1531(2) 0.2543(2) 0.0709(12) Uani 1 d . . . O32 O 1.0380(4) 0.3937(3) 0.2055(2) 0.0948(17) Uani 1 d . . . C32 C 1.0220(4) 0.3687(3) 0.2547(3) 0.0567(15) Uani 1 d . . . C33 C 1.0674(3) 0.3673(3) 0.3867(3) 0.0509(14) Uani 1 d . . . O33 O 1.1137(3) 0.3918(3) 0.4232(3) 0.0899(15) Uani 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 0.018(2) 0.030(2) 0.023(2) 0.0003(18) -0.0049(18) -0.0020(17) Fe3 0.0293(4) 0.0340(4) 0.0364(4) 0.0038(3) -0.0014(3) 0.0025(3) P1 0.0316(7) 0.0305(6) 0.0255(6) 0.0023(5) 0.0027(5) -0.0022(5) N1 0.0232(19) 0.0310(19) 0.028(2) -0.0030(16) -0.0009(16) -0.0015(15) C2 0.032(3) 0.042(3) 0.035(3) 0.006(2) 0.009(2) 0.000(2) Fe2 0.0370(4) 0.0341(4) 0.0267(4) -0.0030(3) -0.0039(3) -0.0010(3) P2 0.0238(6) 0.0311(6) 0.0270(6) 0.0000(5) 0.0018(5) 0.0006(4) C3 0.084(5) 0.075(4) 0.037(3) -0.002(3) -0.015(3) 0.010(3) N2 0.051(3) 0.0260(19) 0.040(2) 0.0058(17) -0.0005(19) -0.0029(17) Fe1 0.0276(4) 0.0447(4) 0.0339(4) 0.0033(3) 0.0088(3) -0.0014(3) C4 0.042(3) 0.071(4) 0.078(4) 0.034(3) 0.020(3) 0.001(3) C5 0.037(3) 0.038(3) 0.039(3) 0.002(2) 0.006(2) 0.005(2) C6 0.086(5) 0.046(3) 0.058(4) -0.012(3) 0.010(3) 0.009(3) C7 0.030(3) 0.064(4) 0.082(4) 0.012(3) -0.006(3) 0.012(3) C8 0.067(4) 0.041(3) 0.053(3) 0.009(2) -0.015(3) 0.006(3) C9 0.129(7) 0.074(4) 0.051(4) 0.019(3) -0.011(4) 0.008(4) C10 0.083(5) 0.074(4) 0.082(5) 0.013(4) -0.017(4) 0.037(4) C11 0.035(3) 0.037(3) 0.057(3) 0.005(2) -0.004(2) -0.004(2) O11 0.043(3) 0.070(3) 0.111(4) 0.008(3) -0.008(2) -0.015(2) O12 0.083(3) 0.087(3) 0.090(3) 0.053(3) -0.019(3) -0.015(3) C12 0.042(3) 0.054(3) 0.056(3) 0.015(3) -0.007(3) -0.003(2) C13 0.054(3) 0.039(3) 0.050(3) 0.007(3) 0.001(3) 0.006(3) O13 0.097(3) 0.067(3) 0.066(3) -0.010(2) 0.019(3) 0.032(3) O14 0.056(3) 0.081(3) 0.103(4) -0.022(3) -0.038(3) 0.003(2) C14 0.036(3) 0.048(3) 0.053(3) 0.002(3) -0.013(3) 0.008(2) C17 0.069(4) 0.035(3) 0.062(4) 0.005(3) 0.006(3) -0.016(3) C18 0.078(5) 0.062(4) 0.062(4) -0.015(3) 0.006(3) -0.036(3) C19 0.107(6) 0.075(5) 0.081(5) 0.000(4) 0.026(4) -0.050(4) O21 0.189(6) 0.073(3) 0.039(3) 0.007(2) -0.031(3) -0.002(3) C21 0.089(5) 0.042(3) 0.035(3) -0.005(2) -0.010(3) -0.001(3) O22 0.047(3) 0.130(4) 0.078(3) -0.012(3) -0.004(2) -0.019(3) C22 0.035(3) 0.066(4) 0.044(3) -0.013(3) -0.012(2) -0.007(3) O30 0.075(3) 0.079(3) 0.077(3) 0.009(2) 0.033(3) 0.033(3) C30 0.039(3) 0.062(3) 0.043(3) 0.005(3) 0.012(2) 0.005(3) C31 0.059(4) 0.046(3) 0.029(3) -0.003(2) 0.002(2) -0.001(3) O31 0.112(4) 0.045(2) 0.055(2) -0.014(2) 0.002(2) 0.014(2) O32 0.118(4) 0.104(4) 0.063(3) 0.033(3) 0.047(3) 0.013(3) C32 0.049(3) 0.060(3) 0.062(4) 0.011(3) 0.025(3) 0.007(3) C33 0.034(3) 0.062(3) 0.056(3) 0.002(3) 0.001(3) -0.010(3) O33 0.060(3) 0.105(4) 0.104(4) -0.021(3) -0.021(3) -0.021(3) _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 N1 1.307(5) . ? C1 P1 1.833(4) . ? C1 P2 1.861(4) . ? Fe3 C12 1.776(6) . ? Fe3 C11 1.781(5) . ? Fe3 C14 1.797(6) . ? Fe3 C13 1.809(6) . ? Fe3 P2 2.2660(13) . ? P1 N2 1.655(4) . ? P1 Fe2 2.2051(13) . ? P1 Fe1 2.2137(13) . ? P1 P2 2.5750(15) . ? N1 C2 1.498(6) . ? N1 C5 1.507(6) . ? C2 C4 1.524(7) . ? C2 C3 1.529(7) . ? Fe2 C31 1.774(5) . ? Fe2 C22 1.790(6) . ? Fe2 C21 1.794(6) . ? Fe2 P2 2.2980(13) . ? Fe2 Fe1 2.6295(9) . ? P2 Fe1 2.2637(13) . ? N2 C17 1.489(6) . ? N2 C8 1.491(7) . ? Fe1 C33 1.781(6) . ? Fe1 C32 1.797(6) . ? Fe1 C30 1.799(6) . ? C5 C6 1.517(7) . ? C5 C7 1.539(7) . ? C8 C10 1.536(8) . ? C8 C9 1.541(8) . ? C11 O11 1.158(6) . ? O12 C12 1.147(6) . ? C13 O13 1.136(6) . ? O14 C14 1.140(6) . ? C17 C18 1.530(8) . ? C17 C19 1.533(9) . ? O21 C21 1.138(6) . ? O22 C22 1.144(7) . ? O30 C30 1.139(6) . ? C31 O31 1.147(6) . ? O32 C32 1.143(7) . ? C33 O33 1.144(7) . ? 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 N1 C1 P1 136.2(3) . . ? N1 C1 P2 134.8(3) . . ? P1 C1 P2 88.36(18) . . ? C12 Fe3 C11 90.3(2) . . ? C12 Fe3 C14 89.4(2) . . ? C11 Fe3 C14 134.2(2) . . ? C12 Fe3 C13 93.3(2) . . ? C11 Fe3 C13 111.8(2) . . ? C14 Fe3 C13 114.0(2) . . ? C12 Fe3 P2 170.0(2) . . ? C11 Fe3 P2 87.43(16) . . ? C14 Fe3 P2 85.15(16) . . ? C13 Fe3 P2 96.65(16) . . ? N2 P1 C1 120.6(2) . . ? N2 P1 Fe2 131.92(15) . . ? C1 P1 Fe2 87.76(13) . . ? N2 P1 Fe1 132.84(16) . . ? C1 P1 Fe1 95.65(14) . . ? Fe2 P1 Fe1 73.04(4) . . ? N2 P1 P2 166.63(15) . . ? C1 P1 P2 46.26(13) . . ? Fe2 P1 P2 56.83(4) . . ? Fe1 P1 P2 55.81(4) . . ? C1 N1 C2 119.4(3) . . ? C1 N1 C5 118.4(4) . . ? C2 N1 C5 122.1(3) . . ? N1 C2 C4 113.9(4) . . ? N1 C2 C3 112.2(4) . . ? C4 C2 C3 112.7(5) . . ? C31 Fe2 C22 100.6(2) . . ? C31 Fe2 C21 93.7(2) . . ? C22 Fe2 C21 99.2(3) . . ? C31 Fe2 P1 147.85(18) . . ? C22 Fe2 P1 107.48(17) . . ? C21 Fe2 P1 96.92(17) . . ? C31 Fe2 P2 89.94(16) . . ? C22 Fe2 P2 101.19(17) . . ? C21 Fe2 P2 158.3(2) . . ? P1 Fe2 P2 69.72(4) . . ? C31 Fe2 Fe1 94.35(18) . . ? C22 Fe2 Fe1 151.35(16) . . ? C21 Fe2 Fe1 104.1(2) . . ? P1 Fe2 Fe1 53.63(4) . . ? P2 Fe2 Fe1 54.19(3) . . ? C1 P2 Fe1 93.22(13) . . ? C1 P2 Fe3 123.79(13) . . ? Fe1 P2 Fe3 133.78(6) . . ? C1 P2 Fe2 84.39(13) . . ? Fe1 P2 Fe2 70.40(4) . . ? Fe3 P2 Fe2 133.05(5) . . ? C1 P2 P1 45.38(13) . . ? Fe1 P2 P1 53.99(4) . . ? Fe3 P2 P1 169.11(6) . . ? Fe2 P2 P1 53.44(4) . . ? C17 N2 C8 117.5(4) . . ? C17 N2 P1 122.5(4) . . ? C8 N2 P1 119.3(3) . . ? C33 Fe1 C32 101.8(3) . . ? C33 Fe1 C30 98.3(3) . . ? C32 Fe1 C30 92.2(2) . . ? C33 Fe1 P1 102.83(18) . . ? C32 Fe1 P1 95.38(18) . . ? C30 Fe1 P1 155.53(18) . . ? C33 Fe1 P2 102.49(18) . . ? C32 Fe1 P2 154.0(2) . . ? C30 Fe1 P2 93.38(17) . . ? P1 Fe1 P2 70.21(4) . . ? C33 Fe1 Fe2 150.11(18) . . ? C32 Fe1 Fe2 98.6(2) . . ? C30 Fe1 Fe2 102.54(18) . . ? P1 Fe1 Fe2 53.33(4) . . ? P2 Fe1 Fe2 55.41(3) . . ? N1 C5 C6 113.6(4) . . ? N1 C5 C7 110.8(4) . . ? C6 C5 C7 112.1(5) . . ? N2 C8 C10 113.0(5) . . ? N2 C8 C9 111.9(5) . . ? C10 C8 C9 110.4(5) . . ? O11 C11 Fe3 178.7(5) . . ? O12 C12 Fe3 179.7(6) . . ? O13 C13 Fe3 174.0(5) . . ? O14 C14 Fe3 179.2(5) . . ? N2 C17 C18 112.5(4) . . ? N2 C17 C19 113.1(5) . . ? C18 C17 C19 109.9(6) . . ? O21 C21 Fe2 178.1(6) . . ? O22 C22 Fe2 178.7(5) . . ? O30 C30 Fe1 178.3(5) . . ? O31 C31 Fe2 178.3(5) . . ? O32 C32 Fe1 178.4(6) . . ? O33 C33 Fe1 178.6(5) . . ? _diffrn_measured_fraction_theta_max 0.890 _diffrn_reflns_theta_full 22.99 _diffrn_measured_fraction_theta_full 0.890 _refine_diff_density_max 0.643 _refine_diff_density_min -0.401 _refine_diff_density_rms 0.085 #===END