# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2013 ####################################################################### # # Cambridge Crystallographic Data Centre # CCDC # ####################################################################### # # This CIF contains data from an original supplementary publication # deposited with the CCDC, and may include chemical, crystal, # experimental, refinement, atomic coordinates, # anisotropic displacement parameters and molecular geometry data, # as required by the journal to which it was submitted. # # This CIF is provided on the understanding that it is used for bona # fide research purposes only. It may contain copyright material # of the CCDC or of third parties, and may not be copied or further # disseminated in any form, whether machine-readable or not, # except for the purpose of generating routine backup copies # on your local computer system. # # For further information on the CCDC, data deposition and # data retrieval see: # www.ccdc.cam.ac.uk # # Bona fide researchers may freely download Mercury and enCIFer # from this site to visualise CIF-encoded structures and # to carry out CIF format checking respectively. # ####################################################################### data_Fe(CO)4Br2 _database_code_depnum_ccdc_archive 'CCDC 922917' #TrackingRef '19053_web_deposit_cif_file_0_JosephA.Wright_1364738302.Carbamoyl-iron.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_structural 'C4 Br2 Fe O4' _chemical_formula_moiety 'C4 Br2 Fe O4' _chemical_formula_sum 'C4 Br2 Fe O4' _chemical_formula_weight 327.71 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' O O 0.0106 0.0060 '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' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M C2 _symmetry_space_group_name_Hall 'C 2y' _symmetry_Int_Tables_number 5 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y, -z' 'x+1/2, y+1/2, z' '-x+1/2, y+1/2, -z' _cell_length_a 6.7608(4) _cell_length_b 10.2296(5) _cell_length_c 12.2954(7) _cell_angle_alpha 90.00 _cell_angle_beta 103.801(3) _cell_angle_gamma 90.00 _cell_volume 825.80(8) _cell_formula_units_Z 4 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 11452 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description needle _exptl_crystal_colour orange _exptl_crystal_size_max 0.12 _exptl_crystal_size_mid 0.02 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.636 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 608 _exptl_absorpt_coefficient_mu 11.463 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.3400 _exptl_absorpt_correction_T_max 0.8940 _exptl_absorpt_process_details '(SADABS 2007/2; Sheldrick, 2007)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker-Nonius FR591 rotating anode' _diffrn_radiation_monochromator '10cm confocal mirrors' _diffrn_measurement_device_type 'Bruker-Nonius APEX II CCD camera on \k-goniostat' _diffrn_measurement_method '\f & \w scans' _diffrn_detector_area_resol_mean '4096x4096pixels / 62x62mm' _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 992 _diffrn_reflns_av_R_equivalents .0000 _diffrn_reflns_av_unetI/netI 0.0354 _diffrn_reflns_limit_h_min -8 _diffrn_reflns_limit_h_max 8 _diffrn_reflns_limit_k_min 0 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min 0 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.41 _diffrn_reflns_theta_max 27.54 _reflns_number_total 992 _reflns_number_gt 956 _reflns_threshold_expression >2\s(I) _computing_data_collection 'COLLECT (Hooft, R.W.W., 1998)' _computing_cell_refinement 'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)' #Although determined using DirAx, the cell is refined in the HKL #package during data reduction _computing_data_reduction 'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'ORTEP-3 (Farrugia, 1997)' _computing_publication_material ; SHELXL-97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004) ; _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^ > 2\s(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. Crystals of Fe(CO)4Br2 were needle-like, and this combined with the high absorbtion coefficient for the material meant that SADABS-based correction for absorbtion was not fully successful. The structure was refined as a racmic twin with a final twin component value of 0.32102. C(1) was restrained such that the thermal parameters were approximately isotropic, with a standard uncertainty of 0.005. C(2), C(12) and C(12) were restrained such that the thermal parameters were approximately isotropic, with a standard uncertainty of 0.010. ; _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^)+(0.0893P)^2^+46.5662P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens none _refine_ls_hydrogen_treatment none _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.14(6) _refine_ls_number_reflns 992 _refine_ls_number_parameters 102 _refine_ls_number_restraints 25 _refine_ls_R_factor_all 0.0715 _refine_ls_R_factor_gt 0.0679 _refine_ls_wR_factor_ref 0.1767 _refine_ls_wR_factor_gt 0.1723 _refine_ls_goodness_of_fit_ref 1.095 _refine_ls_restrained_S_all 1.085 _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 C1 C 0.852(3) 0.929(2) 0.9056(16) 0.012(4) Uani 1 1 d U . . C2 C 1.195(3) 1.059(2) 0.9132(19) 0.018(4) Uani 1 1 d U . . O1 O 0.757(2) 0.8522(15) 0.8437(13) 0.016(3) Uani 1 1 d . . . O2 O 1.318(3) 1.0661(19) 0.8695(15) 0.025(4) Uani 1 1 d . . . Fe1 Fe 1.0000 1.0458(3) 1.0000 0.0094(8) Uani 1 2 d S . . Br1 Br 1.2002(3) 1.21039(18) 1.12022(16) 0.0161(5) Uani 1 1 d . . . C11 C 0.740(3) 0.869(2) 0.4136(19) 0.019(4) Uani 1 1 d . . . C12 C 1.070(3) 0.739(2) 0.4096(18) 0.021(4) Uani 1 1 d U . . O11 O 0.575(3) 0.877(2) 0.3594(19) 0.039(6) Uani 1 1 d . . . O12 O 1.120(2) 0.6691(17) 0.3472(14) 0.021(3) Uani 1 1 d U . . Fe11 Fe 1.0000 0.8564(4) 0.5000 0.0099(8) Uani 1 2 d S . . Br11 Br 1.1015(3) 1.01912(19) 0.38060(16) 0.0160(5) Uani 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 0.015(5) 0.013(5) 0.008(5) -0.002(4) 0.004(4) 0.005(4) C2 0.020(8) 0.011(7) 0.024(8) -0.010(6) 0.006(6) -0.003(6) O1 0.017(8) 0.013(7) 0.015(7) -0.002(6) -0.002(6) -0.011(6) O2 0.022(9) 0.025(9) 0.030(10) -0.003(7) 0.010(8) -0.003(7) Fe1 0.0109(17) 0.0060(19) 0.0098(17) 0.000 -0.0002(13) 0.000 Br1 0.0179(10) 0.0156(11) 0.0124(10) -0.0032(8) -0.0009(7) -0.0033(9) C11 0.024(11) 0.006(9) 0.032(11) 0.010(8) 0.017(9) 0.008(8) C12 0.019(8) 0.025(9) 0.014(7) 0.007(7) -0.004(6) -0.001(7) O11 0.014(8) 0.036(12) 0.057(13) -0.021(10) -0.014(8) 0.003(8) O12 0.014(6) 0.022(7) 0.023(6) 0.002(6) -0.001(5) 0.012(5) Fe11 0.0085(17) 0.0100(18) 0.0100(18) 0.000 -0.0002(14) 0.000 Br11 0.0176(10) 0.0158(11) 0.0148(10) 0.0037(8) 0.0045(7) 0.0006(8) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 1.17(3) . ? C1 Fe1 1.80(2) . ? C2 O2 1.10(3) . ? C2 Fe1 1.89(2) . ? Fe1 C1 1.80(2) 2_757 ? Fe1 C2 1.89(2) 2_757 ? Fe1 Br1 2.429(3) . ? Fe1 Br1 2.429(3) 2_757 ? C11 O11 1.16(3) . ? C11 Fe11 1.83(2) . ? C12 O12 1.16(3) . ? C12 Fe11 1.77(2) . ? Fe11 C12 1.77(2) 2_756 ? Fe11 C11 1.83(2) 2_756 ? Fe11 Br11 2.424(3) 2_756 ? Fe11 Br11 2.424(3) . ? 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 179.2(17) . . ? O2 C2 Fe1 175(2) . . ? C1 Fe1 C1 96.4(13) . 2_757 ? C1 Fe1 C2 93.1(9) . 2_757 ? C1 Fe1 C2 92.2(9) 2_757 2_757 ? C1 Fe1 C2 92.2(9) . . ? C1 Fe1 C2 93.1(9) 2_757 . ? C2 Fe1 C2 172.0(13) 2_757 . ? C1 Fe1 Br1 177.4(6) . . ? C1 Fe1 Br1 85.7(7) 2_757 . ? C2 Fe1 Br1 88.3(7) 2_757 . ? C2 Fe1 Br1 86.2(6) . . ? C1 Fe1 Br1 85.7(6) . 2_757 ? C1 Fe1 Br1 177.4(6) 2_757 2_757 ? C2 Fe1 Br1 86.2(6) 2_757 2_757 ? C2 Fe1 Br1 88.3(7) . 2_757 ? Br1 Fe1 Br1 92.20(15) . 2_757 ? O11 C11 Fe11 179(2) . . ? O12 C12 Fe11 176(2) . . ? C12 Fe11 C12 95.0(15) . 2_756 ? C12 Fe11 C11 92.7(9) . 2_756 ? C12 Fe11 C11 92.6(9) 2_756 2_756 ? C12 Fe11 C11 92.6(9) . . ? C12 Fe11 C11 92.7(9) 2_756 . ? C11 Fe11 C11 172.0(13) 2_756 . ? C12 Fe11 Br11 178.5(7) . 2_756 ? C12 Fe11 Br11 85.9(7) 2_756 2_756 ? C11 Fe11 Br11 88.4(6) 2_756 2_756 ? C11 Fe11 Br11 86.2(7) . 2_756 ? C12 Fe11 Br11 85.9(7) . . ? C12 Fe11 Br11 178.5(7) 2_756 . ? C11 Fe11 Br11 86.2(7) 2_756 . ? C11 Fe11 Br11 88.4(6) . . ? Br11 Fe11 Br11 93.28(17) 2_756 . ? _diffrn_measured_fraction_theta_max 0.995 _diffrn_reflns_theta_full 27.54 _diffrn_measured_fraction_theta_full 0.995 _refine_diff_density_max 1.528 _refine_diff_density_min -2.306 _refine_diff_density_rms 0.415 data_1 _database_code_depnum_ccdc_archive 'CCDC 922918' #TrackingRef '19053_web_deposit_cif_file_0_JosephA.Wright_1364738302.Carbamoyl-iron.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_structural '[Fe(PyNHCO)(CO)2Br2)][C5H7N2]' _chemical_formula_moiety 'C8 H5 Br2 Fe N2 O3, C5 H7 N2' _chemical_formula_sum 'C13 H12 Br2 Fe N4 O3' _chemical_formula_weight 487.94 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' Br Br -0.2901 2.4595 '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' 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/n _symmetry_space_group_name_Hall '-P 2yn' _symmetry_Int_Tables_number 14 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 11.2197(6) _cell_length_b 12.6286(7) _cell_length_c 11.8538(6) _cell_angle_alpha 90.00 _cell_angle_beta 105.142(5) _cell_angle_gamma 90.00 _cell_volume 1621.24(15) _cell_formula_units_Z 4 _cell_measurement_temperature 140(2) _cell_measurement_reflns_used 4687 _cell_measurement_theta_min 3.5540 _cell_measurement_theta_max 29.0623 _exptl_crystal_description block _exptl_crystal_colour orange _exptl_crystal_size_max 0.10 _exptl_crystal_size_mid 0.10 _exptl_crystal_size_min 0.10 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.999 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 952 _exptl_absorpt_coefficient_mu 5.878 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.69363 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) Empirical absorption correction using spherical harmonics, implemented in SCALE3 ABSPACK scaling algorithm. ; _exptl_special_details ; ? ; _diffrn_ambient_temperature 140(2) _diffrn_radiation_probe x-ray _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford Diffraction Xcalibur 3/CCD' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.0050 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 23451 _diffrn_reflns_av_R_equivalents 0.0739 _diffrn_reflns_av_unetI/netI 0.1055 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.56 _diffrn_reflns_theta_max 27.49 _reflns_number_total 3702 _reflns_number_gt 2171 _reflns_threshold_expression >2\s(I) _computing_data_collection ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) ; _computing_cell_refinement ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) ; _computing_data_reduction ; CrysAlisPro, Oxford Diffraction Ltd., Version 1.171.33.66 (release 28-04-2010 CrysAlis171 .NET) (compiled Apr 28 2010,14:27:37) ; _computing_structure_solution 'Superflip (Palatinus and Chapuis, 2007)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'ORTEP-3 (Farrugia, 1997)' _computing_publication_material ; SHELXL-97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004) ; _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^ > 2\s(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. H(2) and H(11) were located in the Fourier difference map and their position was freely refined. Uiso was freely refined for H(11), while for H(2) the Uiso value was set to 1.2 times that of the parent atom N(2). One hydrogen atom bound to N(12) was located in the Fourier difference map at a position which confirmed protonation of the centre, while the second hydrogen atom could not be located. The two were therefore introduced using a riding model. C(7) was restrained such that the thermal parameters were approximately isotropic, with a standard uncertainty of 0.0125. ; _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^)+(0.0400P)^2^] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3702 _refine_ls_number_parameters 215 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.0897 _refine_ls_R_factor_gt 0.0420 _refine_ls_wR_factor_ref 0.0851 _refine_ls_wR_factor_gt 0.0788 _refine_ls_goodness_of_fit_ref 0.851 _refine_ls_restrained_S_all 0.852 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.8406(5) 0.2371(4) 0.7614(4) 0.0245(12) Uani 1 1 d . . . H1 H 0.7919 0.1785 0.7728 0.029 Uiso 1 1 calc R . . C2 C 0.9158(5) 0.2262(4) 0.6879(4) 0.0283(13) Uani 1 1 d . . . H2A H 0.9207 0.1604 0.6505 0.034 Uiso 1 1 calc R . . C3 C 0.9843(5) 0.3115(4) 0.6689(4) 0.0323(13) Uani 1 1 d . . . H3 H 1.0362 0.3057 0.6175 0.039 Uiso 1 1 calc R . . C4 C 0.9763(5) 0.4054(4) 0.7257(5) 0.0303(14) Uani 1 1 d . . . H4 H 1.0216 0.4656 0.7125 0.036 Uiso 1 1 calc R . . C5 C 0.9023(4) 0.4117(4) 0.8015(4) 0.0187(11) Uani 1 1 d . . . C6 C 0.8168(5) 0.4938(4) 0.9400(4) 0.0233(12) Uani 1 1 d . . . C7 C 0.6515(5) 0.4103(5) 1.0292(4) 0.0336(14) Uani 1 1 d U . . C8 C 0.6059(5) 0.4188(4) 0.8083(5) 0.0209(12) Uani 1 1 d . . . C11 C 0.8660(5) 0.8693(4) 0.9948(4) 0.0310(13) Uani 1 1 d . . . H11A H 0.9194 0.8593 0.9453 0.037 Uiso 1 1 calc R . . C12 C 0.8338(5) 0.9668(4) 1.0173(5) 0.0343(14) Uani 1 1 d . . . H12C H 0.8618 1.0265 0.9826 0.041 Uiso 1 1 calc R . . C13 C 0.7581(5) 0.9798(4) 1.0928(5) 0.0346(14) Uani 1 1 d . . . H13 H 0.7365 1.0490 1.1120 0.042 Uiso 1 1 calc R . . C14 C 0.7154(5) 0.8948(4) 1.1384(5) 0.0314(13) Uani 1 1 d . . . H14 H 0.6638 0.9043 1.1896 0.038 Uiso 1 1 calc R . . C15 C 0.7465(5) 0.7924(4) 1.1112(4) 0.0274(12) Uani 1 1 d . . . Br1 Br 0.89450(5) 0.29392(4) 1.09035(4) 0.02803(15) Uani 1 1 d . . . Br2 Br 0.61365(5) 0.18871(4) 0.89814(5) 0.02886(15) Uani 1 1 d . . . Fe1 Fe 0.72895(6) 0.36189(5) 0.92747(6) 0.02093(18) Uani 1 1 d . . . N1 N 0.8335(3) 0.3286(3) 0.8184(3) 0.0181(9) Uani 1 1 d . . . N2 N 0.8902(4) 0.4990(3) 0.8651(4) 0.0257(11) Uani 1 1 d . . . N11 N 0.8236(4) 0.7846(4) 1.0417(4) 0.0260(10) Uani 1 1 d . . . N12 N 0.7058(4) 0.7052(3) 1.1502(4) 0.0404(12) Uani 1 1 d . . . H12A H 0.7292 0.6429 1.1307 0.048 Uiso 1 1 calc R . . H12B H 0.6553 0.7095 1.1957 0.048 Uiso 1 1 calc R . . O1 O 0.8128(3) 0.5710(3) 1.0045(3) 0.0306(9) Uani 1 1 d . . . O2 O 0.6046(4) 0.4376(3) 1.0973(3) 0.0445(10) Uani 1 1 d . . . O3 O 0.5425(4) 0.4497(3) 0.7432(4) 0.0371(10) Uani 1 1 d . . . H11 H 0.843(4) 0.727(4) 1.028(4) 0.019(15) Uiso 1 1 d . . . H2 H 0.936(5) 0.546(4) 0.868(4) 0.023 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 0.026(3) 0.023(3) 0.025(3) -0.001(2) 0.008(2) -0.004(2) C2 0.037(3) 0.026(3) 0.026(3) -0.008(2) 0.014(3) 0.004(2) C3 0.031(3) 0.048(4) 0.023(3) -0.002(3) 0.019(2) 0.003(3) C4 0.030(3) 0.029(3) 0.040(4) 0.004(3) 0.024(3) -0.005(2) C5 0.016(3) 0.023(3) 0.018(3) -0.003(2) 0.006(2) -0.001(2) C6 0.023(3) 0.024(3) 0.023(3) 0.002(2) 0.007(2) 0.005(2) C7 0.020(3) 0.069(4) 0.016(3) -0.009(3) 0.011(2) -0.006(3) C8 0.025(3) 0.021(3) 0.021(3) -0.010(2) 0.014(2) -0.007(2) C11 0.028(3) 0.040(3) 0.030(3) -0.002(3) 0.016(3) -0.002(3) C12 0.038(4) 0.028(3) 0.035(3) 0.007(3) 0.007(3) -0.003(3) C13 0.040(4) 0.027(3) 0.037(4) -0.009(3) 0.009(3) 0.004(3) C14 0.027(3) 0.038(3) 0.031(3) -0.003(3) 0.011(3) 0.005(3) C15 0.026(3) 0.030(3) 0.026(3) -0.005(3) 0.008(2) 0.001(3) Br1 0.0269(3) 0.0318(3) 0.0264(3) 0.0008(3) 0.0089(2) -0.0023(3) Br2 0.0267(3) 0.0321(3) 0.0305(3) -0.0020(3) 0.0122(2) -0.0075(3) Fe1 0.0176(4) 0.0274(4) 0.0203(4) -0.0024(3) 0.0093(3) -0.0009(3) N1 0.017(2) 0.020(2) 0.018(2) 0.0007(17) 0.0053(17) 0.0013(17) N2 0.030(3) 0.020(2) 0.032(3) -0.002(2) 0.018(2) -0.0096(19) N11 0.025(3) 0.025(3) 0.030(3) -0.008(2) 0.011(2) 0.003(2) N12 0.041(3) 0.031(3) 0.061(3) 0.004(2) 0.035(3) 0.006(2) O1 0.032(2) 0.026(2) 0.038(2) -0.0074(18) 0.0167(18) -0.0019(16) O2 0.042(3) 0.054(3) 0.043(3) -0.003(2) 0.021(2) 0.003(2) O3 0.042(3) 0.038(2) 0.035(3) -0.009(2) 0.015(2) 0.009(2) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 1.352(6) . ? C1 C2 1.369(7) . ? C1 H1 0.9500 . ? C2 C3 1.375(7) . ? C2 H2A 0.9500 . ? C3 C4 1.379(7) . ? C3 H3 0.9500 . ? C4 C5 1.376(6) . ? C4 H4 0.9500 . ? C5 N1 1.348(6) . ? C5 N2 1.363(6) . ? C6 O1 1.247(5) . ? C6 N2 1.361(6) . ? C6 Fe1 1.921(5) . ? C7 O2 1.126(6) . ? C7 Fe1 1.769(5) . ? C8 O3 0.983(5) . ? C8 Fe1 1.844(6) . ? C11 C12 1.329(7) . ? C11 N11 1.349(6) . ? C11 H11A 0.9500 . ? C12 C13 1.395(7) . ? C12 H12C 0.9500 . ? C13 C14 1.345(7) . ? C13 H13 0.9500 . ? C14 C15 1.398(7) . ? C14 H14 0.9500 . ? C15 N12 1.321(6) . ? C15 N11 1.345(6) . ? Br1 Fe1 2.4578(9) . ? Br2 Fe1 2.5185(8) . ? Fe1 N1 2.004(4) . ? N2 H2 0.78(5) . ? N11 H11 0.79(5) . ? N12 H12A 0.8800 . ? N12 H12B 0.8800 . ? 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 C2 122.1(5) . . ? N1 C1 H1 119.0 . . ? C2 C1 H1 119.0 . . ? C1 C2 C3 119.3(5) . . ? C1 C2 H2A 120.4 . . ? C3 C2 H2A 120.4 . . ? C2 C3 C4 118.9(5) . . ? C2 C3 H3 120.5 . . ? C4 C3 H3 120.5 . . ? C5 C4 C3 119.7(5) . . ? C5 C4 H4 120.2 . . ? C3 C4 H4 120.2 . . ? N1 C5 N2 113.8(4) . . ? N1 C5 C4 121.3(4) . . ? N2 C5 C4 124.9(5) . . ? O1 C6 N2 119.1(4) . . ? O1 C6 Fe1 128.7(4) . . ? N2 C6 Fe1 112.1(3) . . ? O2 C7 Fe1 176.9(5) . . ? O3 C8 Fe1 177.9(6) . . ? C12 C11 N11 120.5(5) . . ? C12 C11 H11A 119.7 . . ? N11 C11 H11A 119.7 . . ? C11 C12 C13 118.7(5) . . ? C11 C12 H12C 120.6 . . ? C13 C12 H12C 120.6 . . ? C14 C13 C12 120.3(5) . . ? C14 C13 H13 119.9 . . ? C12 C13 H13 119.9 . . ? C13 C14 C15 120.6(5) . . ? C13 C14 H14 119.7 . . ? C15 C14 H14 119.7 . . ? N12 C15 N11 119.3(5) . . ? N12 C15 C14 124.1(5) . . ? N11 C15 C14 116.6(5) . . ? C7 Fe1 C8 89.1(2) . . ? C7 Fe1 C6 88.9(2) . . ? C8 Fe1 C6 89.3(2) . . ? C7 Fe1 N1 170.6(2) . . ? C8 Fe1 N1 92.00(19) . . ? C6 Fe1 N1 81.78(19) . . ? C7 Fe1 Br1 89.44(18) . . ? C8 Fe1 Br1 177.42(15) . . ? C6 Fe1 Br1 88.56(15) . . ? N1 Fe1 Br1 89.09(11) . . ? C7 Fe1 Br2 93.89(18) . . ? C8 Fe1 Br2 88.74(16) . . ? C6 Fe1 Br2 176.53(15) . . ? N1 Fe1 Br2 95.44(11) . . ? Br1 Fe1 Br2 93.48(3) . . ? C5 N1 C1 118.7(4) . . ? C5 N1 Fe1 112.8(3) . . ? C1 N1 Fe1 128.5(3) . . ? C6 N2 C5 119.1(4) . . ? C6 N2 H2 121(4) . . ? C5 N2 H2 118(4) . . ? C15 N11 C11 123.1(5) . . ? C15 N11 H11 117(4) . . ? C11 N11 H11 120(4) . . ? C15 N12 H12A 120.0 . . ? C15 N12 H12B 120.0 . . ? H12A N12 H12B 120.0 . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N12 H12A O1 0.88 2.16 2.895(5) 140.4 . N11 H11 O1 0.79(5) 2.00(5) 2.730(6) 153(5) . N2 H2 Br1 0.78(5) 2.73(5) 3.505(4) 173(5) 3_767 _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 27.49 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 1.266 _refine_diff_density_min -0.657 _refine_diff_density_rms 0.122 _iucr_refine_instructions_details ; TITL petert15 CELL 0.71073 11.2197 12.6286 11.8538 90.000 105.142 90.000 ZERR 4.00 0.0006 0.0007 0.0006 0.000 0.005 0.000 LATT 1 SYMM 1/2 - X, 1/2 + Y, 1/2 - Z SFAC C H BR FE N O UNIT 52 48 8 4 16 12 MERG 2 OMIT 0.00 55.00 ISOR 0.0125 C7 EQIV $1 -x+3/2, y+1/2, -z+5/2 EQIV $2 -x+2, -y+1, -z+2 HTAB N12 O1 HTAB N11 O1 HTAB N2 Br1_$2 FMAP 2 PLAN 10 SIZE 0.10 0.10 0.10 ACTA WGHT 0.04000 L.S. 6 TEMP -133.00 FVAR 1.65640 C1 1 0.840631 0.237093 0.761445 11.00000 0.02646 0.02301 = 0.02464 -0.00148 0.00794 -0.00388 AFIX 43 H1 2 0.791946 0.178482 0.772765 11.00000 -1.20000 AFIX 0 C2 1 0.915839 0.226184 0.687948 11.00000 0.03660 0.02613 = 0.02552 -0.00788 0.01409 0.00356 AFIX 43 H2A 2 0.920706 0.160413 0.650507 11.00000 -1.20000 AFIX 0 C3 1 0.984253 0.311466 0.668916 11.00000 0.03149 0.04843 = 0.02330 -0.00219 0.01852 0.00328 AFIX 43 H3 2 1.036206 0.305725 0.617477 11.00000 -1.20000 AFIX 0 C4 1 0.976254 0.405445 0.725673 11.00000 0.02985 0.02912 = 0.03999 0.00416 0.02352 -0.00528 AFIX 43 H4 2 1.021632 0.465612 0.712494 11.00000 -1.20000 AFIX 0 C5 1 0.902271 0.411697 0.801470 11.00000 0.01602 0.02287 = 0.01783 -0.00315 0.00565 -0.00114 C6 1 0.816779 0.493801 0.940020 11.00000 0.02285 0.02414 = 0.02328 0.00188 0.00652 0.00503 C7 1 0.651470 0.410264 1.029210 11.00000 0.01952 0.06914 = 0.01587 -0.00881 0.01128 -0.00635 C8 1 0.605883 0.418842 0.808319 11.00000 0.02548 0.02141 = 0.02052 -0.01046 0.01433 -0.00692 C11 1 0.866043 0.869347 0.994808 11.00000 0.02828 0.03975 = 0.03004 -0.00174 0.01646 -0.00156 AFIX 43 H11A 2 0.919423 0.859303 0.945317 11.00000 -1.20000 AFIX 0 C12 1 0.833802 0.966817 1.017286 11.00000 0.03779 0.02838 = 0.03511 0.00698 0.00660 -0.00331 AFIX 43 H12C 2 0.861785 1.026483 0.982627 11.00000 -1.20000 AFIX 0 C13 1 0.758076 0.979777 1.092760 11.00000 0.03974 0.02668 = 0.03660 -0.00902 0.00854 0.00411 AFIX 43 H13 2 0.736519 1.048952 1.112002 11.00000 -1.20000 AFIX 0 C14 1 0.715439 0.894755 1.138417 11.00000 0.02702 0.03813 = 0.03101 -0.00348 0.01105 0.00547 AFIX 43 H14 2 0.663793 0.904344 1.189617 11.00000 -1.20000 AFIX 0 C15 1 0.746461 0.792428 1.111184 11.00000 0.02638 0.03021 = 0.02623 -0.00467 0.00825 0.00119 BR1 3 0.894499 0.293923 1.090349 11.00000 0.02687 0.03184 = 0.02645 0.00080 0.00888 -0.00227 BR2 3 0.613648 0.188710 0.898137 11.00000 0.02667 0.03208 = 0.03047 -0.00204 0.01220 -0.00753 FE1 4 0.728949 0.361894 0.927474 11.00000 0.01759 0.02737 = 0.02026 -0.00236 0.00928 -0.00094 N1 5 0.833454 0.328622 0.818418 11.00000 0.01681 0.01979 = 0.01816 0.00067 0.00529 0.00132 N2 5 0.890211 0.498996 0.865145 11.00000 0.03042 0.02019 = 0.03197 -0.00231 0.01769 -0.00961 N11 5 0.823584 0.784571 1.041700 11.00000 0.02534 0.02497 = 0.02966 -0.00771 0.01078 0.00331 N12 5 0.705818 0.705248 1.150227 11.00000 0.04096 0.03079 = 0.06140 0.00371 0.03491 0.00597 AFIX 93 H12A 2 0.729224 0.642881 1.130732 11.00000 -1.20000 H12B 2 0.655332 0.709530 1.195735 11.00000 -1.20000 AFIX 0 O1 6 0.812758 0.571020 1.004486 11.00000 0.03196 0.02562 = 0.03833 -0.00740 0.01670 -0.00194 O2 6 0.604649 0.437588 1.097258 11.00000 0.04227 0.05431 = 0.04268 -0.00287 0.02132 0.00304 O3 6 0.542490 0.449733 0.743239 11.00000 0.04176 0.03761 = 0.03489 -0.00881 0.01530 0.00875 H11 2 0.843171 0.726665 1.028301 11.00000 0.01927 H2 2 0.936483 0.545522 0.868325 11.00000 -1.20000 HKLF 4 END ; data_3a _database_code_depnum_ccdc_archive 'CCDC 922919' #TrackingRef '19053_web_deposit_cif_file_0_JosephA.Wright_1364738302.Carbamoyl-iron.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_structural Fe(CO)2(PMe3)(py-NHCO)(Br) _chemical_formula_moiety 'C11 H14 Br Fe N2 O3 P' _chemical_formula_sum 'C11 H14 Br Fe N2 O3 P' _chemical_formula_weight 388.97 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' Br Br -0.2901 2.4595 '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' 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M P21/a _symmetry_space_group_name_Hall '-P 2yab' _symmetry_Int_Tables_number 14 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, y+1/2, -z' '-x, -y, -z' 'x-1/2, -y-1/2, z' _cell_length_a 13.2378(3) _cell_length_b 7.5324(3) _cell_length_c 15.4174(5) _cell_angle_alpha 90.00 _cell_angle_beta 110.218(2) _cell_angle_gamma 90.00 _cell_volume 1442.58(8) _cell_formula_units_Z 4 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 21314 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description plate _exptl_crystal_colour yellow _exptl_crystal_size_max 0.06 _exptl_crystal_size_mid 0.06 _exptl_crystal_size_min 0.02 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.791 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 776 _exptl_absorpt_coefficient_mu 3.930 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.8138 _exptl_absorpt_correction_T_max 0.9255 _exptl_absorpt_process_details 'SADABS 2007/2 (Sheldrick, 2007)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker-Nonius FR591 rotating anode' _diffrn_radiation_monochromator '10cm confocal mirrors' _diffrn_measurement_device_type 'Bruker-Nonius APEX II CCD camera on \k-goniostat' _diffrn_measurement_method '\f & \w scans' _diffrn_detector_area_resol_mean '4096x4096pixels / 62x62mm' _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 19448 _diffrn_reflns_av_R_equivalents 0.0558 _diffrn_reflns_av_unetI/netI 0.0411 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 17 _diffrn_reflns_limit_k_min -9 _diffrn_reflns_limit_k_max 9 _diffrn_reflns_limit_l_min -20 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 3.05 _diffrn_reflns_theta_max 27.50 _reflns_number_total 3300 _reflns_number_gt 2667 _reflns_threshold_expression >2\s(I) _computing_data_collection 'COLLECT (Hooft, R.W.W., 1998)' _computing_cell_refinement 'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)' #Although determined using DirAx, the cell is refined in the HKL #package during data reduction _computing_data_reduction 'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)' _computing_structure_solution 'Superflip (Palatinus and Chapuis, 2007)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'ORTEP-3 (Farrugia, 1997)' _computing_publication_material ; SHELXL-97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004) ; _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^ > 2\s(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. H(2) located in the Fourier difference map and freely refined. ; _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^)+4.6619P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 3300 _refine_ls_number_parameters 179 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0609 _refine_ls_R_factor_gt 0.0402 _refine_ls_wR_factor_ref 0.0794 _refine_ls_wR_factor_gt 0.0725 _refine_ls_goodness_of_fit_ref 1.127 _refine_ls_restrained_S_all 1.127 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.0650(3) 0.5983(5) 0.1886(2) 0.0196(7) Uani 1 1 d . . . H1 H 0.1229 0.6555 0.2348 0.023 Uiso 1 1 calc R . . C2 C -0.0258(3) 0.6941(5) 0.1458(2) 0.0193(7) Uani 1 1 d . . . H2A H -0.0306 0.8152 0.1611 0.023 Uiso 1 1 calc R . . C3 C -0.1117(3) 0.6099(5) 0.0788(3) 0.0216(8) Uani 1 1 d . . . H3 H -0.1773 0.6719 0.0500 0.026 Uiso 1 1 calc R . . C4 C -0.1010(3) 0.4364(5) 0.0548(2) 0.0193(7) Uani 1 1 d . . . H4 H -0.1582 0.3772 0.0089 0.023 Uiso 1 1 calc R . . C5 C -0.0031(3) 0.3500(5) 0.1001(2) 0.0155(7) Uani 1 1 d . . . C6 C 0.1224(3) 0.1143(5) 0.1160(2) 0.0181(7) Uani 1 1 d . . . C7 C 0.2722(3) 0.3816(5) 0.1578(2) 0.0176(7) Uani 1 1 d . . . C8 C 0.3129(3) 0.1097(5) 0.2577(2) 0.0197(8) Uani 1 1 d . . . C9 C 0.2007(3) 0.4959(6) 0.4203(3) 0.0331(10) Uani 1 1 d . . . H9A H 0.2455 0.5483 0.4793 0.050 Uiso 1 1 calc R . . H9B H 0.1629 0.3919 0.4321 0.050 Uiso 1 1 calc R . . H9C H 0.1481 0.5837 0.3846 0.050 Uiso 1 1 calc R . . C10 C 0.3523(3) 0.6335(5) 0.3430(3) 0.0280(9) Uani 1 1 d . . . H10A H 0.3795 0.6943 0.4029 0.042 Uiso 1 1 calc R . . H10B H 0.3009 0.7106 0.2977 0.042 Uiso 1 1 calc R . . H10C H 0.4126 0.6062 0.3221 0.042 Uiso 1 1 calc R . . C11 C 0.3948(3) 0.3110(6) 0.4419(3) 0.0264(9) Uani 1 1 d . . . H11A H 0.4550 0.2950 0.4194 0.040 Uiso 1 1 calc R . . H11B H 0.3690 0.1946 0.4537 0.040 Uiso 1 1 calc R . . H11C H 0.4189 0.3801 0.4993 0.040 Uiso 1 1 calc R . . Br1 Br 0.11428(3) 0.08791(5) 0.30894(3) 0.02380(11) Uani 1 1 d . . . Fe1 Fe 0.20563(4) 0.26598(7) 0.22147(3) 0.01473(12) Uani 1 1 d . . . N1 N 0.0776(2) 0.4256(4) 0.16911(19) 0.0161(6) Uani 1 1 d . . . N2 N 0.0189(2) 0.1842(4) 0.0753(2) 0.0180(6) Uani 1 1 d . . . O1 O 0.14492(19) -0.0245(3) 0.08693(17) 0.0211(5) Uani 1 1 d . . . O2 O 0.3154(2) 0.4570(4) 0.11745(18) 0.0247(6) Uani 1 1 d . . . O3 O 0.3840(2) 0.0140(4) 0.28172(19) 0.0284(6) Uani 1 1 d . . . P1 P 0.28584(7) 0.42870(13) 0.35506(6) 0.0187(2) Uani 1 1 d . . . H2 H -0.021(3) 0.136(5) 0.032(3) 0.013(10) 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 0.0160(17) 0.0198(19) 0.0221(18) -0.0054(15) 0.0056(14) -0.0036(14) C2 0.0186(17) 0.0172(18) 0.0230(18) -0.0036(15) 0.0081(14) -0.0007(14) C3 0.0164(17) 0.025(2) 0.0238(19) 0.0027(16) 0.0072(15) 0.0046(15) C4 0.0146(16) 0.024(2) 0.0190(17) 0.0005(15) 0.0053(14) -0.0019(14) C5 0.0159(16) 0.0185(18) 0.0139(16) -0.0010(14) 0.0076(13) -0.0049(13) C6 0.0151(16) 0.0211(19) 0.0166(17) 0.0008(14) 0.0037(13) -0.0038(14) C7 0.0127(16) 0.0180(18) 0.0165(17) -0.0033(14) -0.0021(13) 0.0049(14) C8 0.0253(19) 0.0195(19) 0.0157(17) -0.0010(14) 0.0090(14) -0.0054(15) C9 0.029(2) 0.046(3) 0.026(2) -0.0152(19) 0.0111(17) -0.0002(19) C10 0.027(2) 0.022(2) 0.029(2) -0.0027(17) 0.0022(17) -0.0055(16) C11 0.0227(19) 0.034(2) 0.0182(18) 0.0023(16) 0.0011(15) 0.0002(16) Br1 0.02457(19) 0.0272(2) 0.01997(19) 0.00095(16) 0.00808(14) -0.00750(15) Fe1 0.0141(2) 0.0144(3) 0.0148(2) -0.0015(2) 0.00374(18) -0.00170(19) N1 0.0148(14) 0.0168(15) 0.0164(14) -0.0013(12) 0.0049(11) -0.0015(12) N2 0.0156(15) 0.0193(16) 0.0154(15) -0.0058(13) 0.0007(12) -0.0029(12) O1 0.0205(13) 0.0165(13) 0.0262(14) -0.0057(11) 0.0081(11) -0.0009(10) O2 0.0196(13) 0.0272(15) 0.0269(14) 0.0027(12) 0.0075(11) -0.0028(11) O3 0.0291(15) 0.0244(15) 0.0316(15) 0.0020(12) 0.0103(12) 0.0092(12) P1 0.0167(4) 0.0205(5) 0.0173(4) -0.0039(4) 0.0038(3) -0.0021(4) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 1.358(5) . ? C1 C2 1.361(5) . ? C1 H1 0.9500 . ? C2 C3 1.396(5) . ? C2 H2A 0.9500 . ? C3 C4 1.380(5) . ? C3 H3 0.9500 . ? C4 C5 1.402(5) . ? C4 H4 0.9500 . ? C5 N1 1.346(4) . ? C5 N2 1.366(5) . ? C6 O1 1.214(4) . ? C6 N2 1.398(4) . ? C6 Fe1 1.981(3) . ? C7 O2 1.133(4) . ? C7 Fe1 1.760(4) . ? C8 O3 1.141(4) . ? C8 Fe1 1.779(4) . ? C9 P1 1.822(4) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 P1 1.817(4) . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 P1 1.823(4) . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? Br1 Fe1 2.4914(6) . ? Fe1 N1 2.006(3) . ? Fe1 P1 2.3152(10) . ? N2 H2 0.78(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 N1 C1 C2 123.7(3) . . ? N1 C1 H1 118.1 . . ? C2 C1 H1 118.1 . . ? C1 C2 C3 118.4(3) . . ? C1 C2 H2A 120.8 . . ? C3 C2 H2A 120.8 . . ? C4 C3 C2 119.7(3) . . ? C4 C3 H3 120.1 . . ? C2 C3 H3 120.1 . . ? C3 C4 C5 118.0(3) . . ? C3 C4 H4 121.0 . . ? C5 C4 H4 121.0 . . ? N1 C5 N2 114.8(3) . . ? N1 C5 C4 122.8(3) . . ? N2 C5 C4 122.3(3) . . ? O1 C6 N2 119.1(3) . . ? O1 C6 Fe1 131.4(3) . . ? N2 C6 Fe1 109.4(2) . . ? O2 C7 Fe1 179.4(3) . . ? O3 C8 Fe1 177.7(3) . . ? P1 C9 H9A 109.5 . . ? P1 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? P1 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? P1 C10 H10A 109.5 . . ? P1 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? P1 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? P1 C11 H11A 109.5 . . ? P1 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? P1 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C7 Fe1 C8 90.19(16) . . ? C7 Fe1 C6 94.09(15) . . ? C8 Fe1 C6 91.89(15) . . ? C7 Fe1 N1 89.74(14) . . ? C8 Fe1 N1 173.97(14) . . ? C6 Fe1 N1 82.10(13) . . ? C7 Fe1 P1 94.01(11) . . ? C8 Fe1 P1 90.02(12) . . ? C6 Fe1 P1 171.67(10) . . ? N1 Fe1 P1 96.00(9) . . ? C7 Fe1 Br1 177.09(11) . . ? C8 Fe1 Br1 87.57(11) . . ? C6 Fe1 Br1 84.13(10) . . ? N1 Fe1 Br1 92.28(8) . . ? P1 Fe1 Br1 87.86(3) . . ? C5 N1 C1 117.1(3) . . ? C5 N1 Fe1 113.2(2) . . ? C1 N1 Fe1 129.5(2) . . ? C5 N2 C6 119.3(3) . . ? C5 N2 H2 121(3) . . ? C6 N2 H2 118(3) . . ? C10 P1 C9 103.5(2) . . ? C10 P1 C11 101.51(18) . . ? C9 P1 C11 102.29(19) . . ? C10 P1 Fe1 116.63(14) . . ? C9 P1 Fe1 117.21(14) . . ? C11 P1 Fe1 113.52(14) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N2 H2 O1 0.78(4) 2.17(4) 2.943(4) 173(4) 3 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.587 _refine_diff_density_min -0.528 _refine_diff_density_rms 0.130 _iucr_refine_instructions_details ; TITL 2011src0122 CELL 0.71073 13.2378 7.5324 15.4174 90.000 110.218 90.000 ZERR 4.00 0.0003 0.0003 0.0005 0.000 0.002 0.000 LATT 1 SYMM 1/2 - X, 1/2 + Y, - Z SFAC C H BR FE N O P UNIT 44 56 4 4 8 12 4 MERG 2 OMIT 0.00 55.00 FMAP 2 PLAN 10 SIZE 0.02 0.06 0.06 EQIV $1 -x, -y, -z ACTA BOND $H HTAB N2 O1_$1 WGHT 0.00000 4.66190 L.S. 6 TEMP -153.00 FVAR 0.39016 C1 1 0.065041 0.598332 0.188635 11.00000 0.01598 0.01985 = 0.02211 -0.00545 0.00563 -0.00357 AFIX 43 H1 2 0.122930 0.655549 0.234795 11.00000 -1.20000 AFIX 0 C2 1 -0.025800 0.694080 0.145795 11.00000 0.01857 0.01720 = 0.02299 -0.00358 0.00810 -0.00066 AFIX 43 H2A 2 -0.030613 0.815206 0.161094 11.00000 -1.20000 AFIX 0 C3 1 -0.111720 0.609946 0.078827 11.00000 0.01635 0.02489 = 0.02382 0.00266 0.00723 0.00458 AFIX 43 H3 2 -0.177287 0.671940 0.049957 11.00000 -1.20000 AFIX 0 C4 1 -0.100973 0.436370 0.054770 11.00000 0.01462 0.02384 = 0.01897 0.00050 0.00532 -0.00194 AFIX 43 H4 2 -0.158167 0.377213 0.008851 11.00000 -1.20000 AFIX 0 C5 1 -0.003112 0.349959 0.100132 11.00000 0.01589 0.01850 = 0.01393 -0.00101 0.00758 -0.00487 C6 1 0.122419 0.114329 0.116001 11.00000 0.01514 0.02106 = 0.01656 0.00076 0.00370 -0.00380 C7 1 0.272247 0.381620 0.157806 11.00000 0.01268 0.01804 = 0.01646 -0.00335 -0.00207 0.00492 C8 1 0.312851 0.109661 0.257679 11.00000 0.02528 0.01946 = 0.01573 -0.00100 0.00895 -0.00539 C9 1 0.200741 0.495929 0.420309 11.00000 0.02883 0.04571 = 0.02607 -0.01524 0.01111 -0.00019 AFIX 137 H9A 2 0.245463 0.548332 0.479259 11.00000 -1.50000 H9B 2 0.162924 0.391930 0.432117 11.00000 -1.50000 H9C 2 0.148072 0.583682 0.384643 11.00000 -1.50000 AFIX 0 C10 1 0.352339 0.633534 0.343042 11.00000 0.02698 0.02227 = 0.02899 -0.00267 0.00223 -0.00549 AFIX 137 H10A 2 0.379473 0.694284 0.402878 11.00000 -1.50000 H10B 2 0.300855 0.710553 0.297702 11.00000 -1.50000 H10C 2 0.412551 0.606224 0.322066 11.00000 -1.50000 AFIX 0 C11 1 0.394772 0.311007 0.441885 11.00000 0.02269 0.03364 = 0.01821 0.00234 0.00114 0.00016 AFIX 137 H11A 2 0.454952 0.295037 0.419389 11.00000 -1.50000 H11B 2 0.369005 0.194641 0.453660 11.00000 -1.50000 H11C 2 0.418922 0.380074 0.499283 11.00000 -1.50000 AFIX 0 BR1 3 0.114285 0.087914 0.308939 11.00000 0.02457 0.02717 = 0.01997 0.00095 0.00808 -0.00750 FE1 4 0.205627 0.265980 0.221468 11.00000 0.01408 0.01440 = 0.01475 -0.00148 0.00374 -0.00170 N1 5 0.077593 0.425611 0.169114 11.00000 0.01483 0.01684 = 0.01636 -0.00129 0.00493 -0.00152 N2 5 0.018928 0.184216 0.075348 11.00000 0.01561 0.01929 = 0.01543 -0.00580 0.00068 -0.00285 O1 6 0.144918 -0.024472 0.086928 11.00000 0.02050 0.01654 = 0.02621 -0.00574 0.00808 -0.00092 O2 6 0.315440 0.457049 0.117454 11.00000 0.01962 0.02720 = 0.02692 0.00272 0.00749 -0.00280 O3 6 0.384007 0.013996 0.281721 11.00000 0.02908 0.02443 = 0.03156 0.00196 0.01027 0.00917 P1 7 0.285836 0.428699 0.355059 11.00000 0.01668 0.02053 = 0.01732 -0.00386 0.00383 -0.00212 H2 2 -0.020598 0.136457 0.032208 11.00000 0.01302 HKLF 4 END ; data_[Fe(MeCN)4(PMe3)2][(Br3Fe)2O] _database_code_depnum_ccdc_archive 'CCDC 922920' #TrackingRef '19053_web_deposit_cif_file_0_JosephA.Wright_1364738302.Carbamoyl-iron.cif' _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_structural '[Fe(NCMe)4(PMe3)2][(Br3Fe)2O]' _chemical_formula_moiety 'C14 H30 Fe N4 P2, Br6 Fe2 O' _chemical_formula_sum 'C14 H30 Br6 Fe3 N4 O P2' _chemical_formula_weight 979.37 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' Br Br -0.2901 2.4595 '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' 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' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 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 10.1505(3) _cell_length_b 12.4119(4) _cell_length_c 13.1800(4) _cell_angle_alpha 90.00 _cell_angle_beta 110.162(2) _cell_angle_gamma 90.00 _cell_volume 1558.76(8) _cell_formula_units_Z 2 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 14932 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description block _exptl_crystal_colour red _exptl_crystal_size_max 0.07 _exptl_crystal_size_mid 0.07 _exptl_crystal_size_min 0.04 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 2.087 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 936 _exptl_absorpt_coefficient_mu 9.184 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.6119 _exptl_absorpt_correction_T_max 0.7102 _exptl_absorpt_process_details 'SADABS 2007/2 (Sheldrick, 2007)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker-Nonius FR591 rotating anode' _diffrn_radiation_monochromator '10cm confocal mirrors' _diffrn_measurement_device_type 'Bruker-Nonius APEX II CCD camera on \k-goniostat' _diffrn_measurement_method '\f & \w scans' _diffrn_detector_area_resol_mean '4096x4096pixels / 62x62mm' _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 14169 _diffrn_reflns_av_R_equivalents 0.0447 _diffrn_reflns_av_unetI/netI 0.0430 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -16 _diffrn_reflns_limit_k_max 16 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 3.25 _diffrn_reflns_theta_max 27.50 _reflns_number_total 3551 _reflns_number_gt 2867 _reflns_threshold_expression >2\s(I) _computing_data_collection 'COLLECT (Hooft, 1998)' _computing_cell_refinement 'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, 1998)' #Although determined using DirAx, the cell is refined in the HKL #package during data reduction _computing_data_reduction 'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, 1998)' _computing_structure_solution 'SIR92 (Altomare et al., 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'ORTEP-3 (Farrugia, 1997)' _computing_publication_material ; SHELXL-97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004) ; _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^ > 2\s(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^)+(0.0000P)^2^+6.9434P] 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 3551 _refine_ls_number_parameters 144 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0569 _refine_ls_R_factor_gt 0.0378 _refine_ls_wR_factor_ref 0.0786 _refine_ls_wR_factor_gt 0.0705 _refine_ls_goodness_of_fit_ref 1.114 _refine_ls_restrained_S_all 1.114 _refine_ls_shift/su_max 0.016 _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 C1 C 0.1051(5) 0.2680(4) 0.0139(4) 0.0194(9) Uani 1 1 d . . . C2 C 0.1608(5) 0.1591(4) 0.0255(4) 0.0275(11) Uani 1 1 d . . . H2A H 0.2426 0.1540 0.0921 0.041 Uiso 1 1 calc R . . H2B H 0.1889 0.1416 -0.0366 0.041 Uiso 1 1 calc R . . H2C H 0.0886 0.1083 0.0289 0.041 Uiso 1 1 calc R . . C3 C 0.3033(5) 0.5580(4) 0.1291(4) 0.0216(10) Uani 1 1 d . . . C4 C 0.4512(5) 0.5770(5) 0.1886(4) 0.0314(12) Uani 1 1 d . . . H4A H 0.4986 0.5079 0.2124 0.047 Uiso 1 1 calc R . . H4B H 0.4609 0.6220 0.2518 0.047 Uiso 1 1 calc R . . H4C H 0.4938 0.6137 0.1418 0.047 Uiso 1 1 calc R . . C5 C 0.0652(5) 0.5442(4) 0.2735(4) 0.0281(11) Uani 1 1 d . . . H5A H 0.0300 0.5353 0.3335 0.042 Uiso 1 1 calc R . . H5B H 0.0713 0.6212 0.2589 0.042 Uiso 1 1 calc R . . H5C H 0.1586 0.5116 0.2927 0.042 Uiso 1 1 calc R . . C6 C -0.0620(5) 0.3407(4) 0.1964(4) 0.0224(10) Uani 1 1 d . . . H6A H 0.0321 0.3088 0.2194 0.034 Uiso 1 1 calc R . . H6B H -0.1252 0.2990 0.1360 0.034 Uiso 1 1 calc R . . H6C H -0.0972 0.3397 0.2568 0.034 Uiso 1 1 calc R . . C7 C -0.2242(5) 0.5320(4) 0.1451(4) 0.0266(11) Uani 1 1 d . . . H7A H -0.2984 0.4909 0.0915 0.040 Uiso 1 1 calc R . . H7B H -0.2306 0.6079 0.1236 0.040 Uiso 1 1 calc R . . H7C H -0.2355 0.5258 0.2158 0.040 Uiso 1 1 calc R . . Br1 Br 0.34277(5) 0.32777(4) 0.29470(4) 0.02515(12) Uani 1 1 d . . . Br2 Br 0.54125(6) 0.23456(4) 0.58000(4) 0.03307(14) Uani 1 1 d . . . Br3 Br 0.74443(5) 0.37370(4) 0.41656(4) 0.02718(13) Uani 1 1 d . . . Fe1 Fe 0.0000 0.5000 0.0000 0.01518(19) Uani 1 2 d S . . Fe2 Fe 0.53217(7) 0.37262(5) 0.45435(5) 0.01929(15) Uani 1 1 d . . . N1 N 0.0630(4) 0.3537(3) 0.0065(3) 0.0172(8) Uani 1 1 d . . . N2 N 0.1880(4) 0.5411(3) 0.0817(3) 0.0181(8) Uani 1 1 d . . . O1 O 0.5000 0.5000 0.5000 0.0346(12) Uani 1 2 d S . . P1 P -0.05374(12) 0.47876(9) 0.15359(10) 0.0178(2) Uani 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 0.019(2) 0.021(2) 0.021(2) -0.0009(18) 0.0100(19) -0.0051(18) C2 0.027(3) 0.015(2) 0.041(3) 0.005(2) 0.013(2) 0.0088(19) C3 0.024(2) 0.020(2) 0.024(2) -0.0039(19) 0.013(2) -0.0031(19) C4 0.018(2) 0.040(3) 0.033(3) 0.003(2) 0.005(2) -0.005(2) C5 0.034(3) 0.024(2) 0.026(3) -0.005(2) 0.010(2) 0.004(2) C6 0.022(2) 0.022(2) 0.026(3) 0.0007(19) 0.011(2) -0.0007(19) C7 0.028(3) 0.028(3) 0.030(3) 0.005(2) 0.017(2) 0.011(2) Br1 0.0208(2) 0.0245(2) 0.0268(3) 0.00111(19) 0.00389(19) 0.00259(19) Br2 0.0383(3) 0.0352(3) 0.0298(3) 0.0113(2) 0.0169(2) 0.0090(2) Br3 0.0219(2) 0.0290(3) 0.0335(3) -0.0016(2) 0.0132(2) -0.00152(19) Fe1 0.0132(4) 0.0127(4) 0.0197(5) 0.0007(3) 0.0058(4) 0.0005(3) Fe2 0.0207(3) 0.0172(3) 0.0212(3) -0.0010(3) 0.0088(3) 0.0030(3) N1 0.0167(18) 0.019(2) 0.0173(19) -0.0009(15) 0.0070(15) -0.0012(15) N2 0.020(2) 0.0142(18) 0.020(2) -0.0012(15) 0.0077(16) 0.0019(15) O1 0.039(3) 0.025(3) 0.041(3) -0.007(2) 0.014(3) 0.008(2) P1 0.0176(5) 0.0159(5) 0.0215(6) 0.0015(5) 0.0090(5) 0.0018(4) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 1.137(6) . ? C1 C2 1.453(6) . ? C2 H2A 0.9800 . ? C2 H2B 0.9800 . ? C2 H2C 0.9800 . ? C3 N2 1.139(6) . ? C3 C4 1.454(6) . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C4 H4C 0.9800 . ? C5 P1 1.817(5) . ? C5 H5A 0.9800 . ? C5 H5B 0.9800 . ? C5 H5C 0.9800 . ? C6 P1 1.815(5) . ? C6 H6A 0.9800 . ? C6 H6B 0.9800 . ? C6 H6C 0.9800 . ? C7 P1 1.820(5) . ? C7 H7A 0.9800 . ? C7 H7B 0.9800 . ? C7 H7C 0.9800 . ? Br1 Fe2 2.3758(8) . ? Br2 Fe2 2.3628(8) . ? Br3 Fe2 2.3728(8) . ? Fe1 N2 1.910(4) . ? Fe1 N2 1.910(4) 3_565 ? Fe1 N1 1.918(4) . ? Fe1 N1 1.918(4) 3_565 ? Fe1 P1 2.2861(11) 3_565 ? Fe1 P1 2.2861(11) . ? Fe2 O1 1.7617(6) . ? O1 Fe2 1.7617(6) 3_666 ? 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 C2 178.9(5) . . ? C1 C2 H2A 109.5 . . ? C1 C2 H2B 109.5 . . ? H2A C2 H2B 109.5 . . ? C1 C2 H2C 109.5 . . ? H2A C2 H2C 109.5 . . ? H2B C2 H2C 109.5 . . ? N2 C3 C4 178.5(5) . . ? C3 C4 H4A 109.5 . . ? C3 C4 H4B 109.5 . . ? H4A C4 H4B 109.5 . . ? C3 C4 H4C 109.5 . . ? H4A C4 H4C 109.5 . . ? H4B C4 H4C 109.5 . . ? P1 C5 H5A 109.5 . . ? P1 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? P1 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? P1 C6 H6A 109.5 . . ? P1 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? P1 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? P1 C7 H7A 109.5 . . ? P1 C7 H7B 109.5 . . ? H7A C7 H7B 109.5 . . ? P1 C7 H7C 109.5 . . ? H7A C7 H7C 109.5 . . ? H7B C7 H7C 109.5 . . ? N2 Fe1 N2 180.0 . 3_565 ? N2 Fe1 N1 88.58(15) . . ? N2 Fe1 N1 91.42(15) 3_565 . ? N2 Fe1 N1 91.42(15) . 3_565 ? N2 Fe1 N1 88.58(15) 3_565 3_565 ? N1 Fe1 N1 180.0 . 3_565 ? N2 Fe1 P1 88.36(11) . 3_565 ? N2 Fe1 P1 91.64(11) 3_565 3_565 ? N1 Fe1 P1 88.34(11) . 3_565 ? N1 Fe1 P1 91.66(11) 3_565 3_565 ? N2 Fe1 P1 91.64(11) . . ? N2 Fe1 P1 88.36(11) 3_565 . ? N1 Fe1 P1 91.66(11) . . ? N1 Fe1 P1 88.34(11) 3_565 . ? P1 Fe1 P1 180.0 3_565 . ? O1 Fe2 Br2 112.24(3) . . ? O1 Fe2 Br3 110.81(3) . . ? Br2 Fe2 Br3 109.41(3) . . ? O1 Fe2 Br1 108.91(3) . . ? Br2 Fe2 Br1 105.96(3) . . ? Br3 Fe2 Br1 109.36(3) . . ? C1 N1 Fe1 177.1(4) . . ? C3 N2 Fe1 174.8(4) . . ? Fe2 O1 Fe2 180.0 . 3_666 ? C6 P1 C5 103.9(2) . . ? C6 P1 C7 102.6(2) . . ? C5 P1 C7 102.9(2) . . ? C6 P1 Fe1 115.75(16) . . ? C5 P1 Fe1 115.39(17) . . ? C7 P1 Fe1 114.59(16) . . ? 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 N2 Fe1 P1 C6 -103.4(2) . . . . ? N2 Fe1 P1 C6 76.6(2) 3_565 . . . ? N1 Fe1 P1 C6 -14.8(2) . . . . ? N1 Fe1 P1 C6 165.2(2) 3_565 . . . ? N2 Fe1 P1 C5 18.2(2) . . . . ? N2 Fe1 P1 C5 -161.8(2) 3_565 . . . ? N1 Fe1 P1 C5 106.8(2) . . . . ? N1 Fe1 P1 C5 -73.2(2) 3_565 . . . ? N2 Fe1 P1 C7 137.5(2) . . . . ? N2 Fe1 P1 C7 -42.5(2) 3_565 . . . ? N1 Fe1 P1 C7 -133.9(2) . . . . ? N1 Fe1 P1 C7 46.1(2) 3_565 . . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 0.627 _refine_diff_density_min -0.579 _refine_diff_density_rms 0.148 data_Fe(CO)(PPh3)2(Br)(C6H5N2CO).THF _database_code_depnum_ccdc_archive 'CCDC 922921' #TrackingRef '19053_web_deposit_cif_file_0_JosephA.Wright_1364738302.Carbamoyl-iron.cif' _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_structural Fe(CO)(PPh3)2(Br)(C6H5N2CO).THF _chemical_formula_moiety 'C43 H35 Br Fe N2 O2 P2, C4 H8 O' _chemical_formula_sum 'C47 H43 Br Fe N2 O3 P2' _chemical_formula_weight 881.53 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' Br Br -0.2901 2.4595 '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' 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' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 11.061(5) _cell_length_b 12.238(5) _cell_length_c 15.979(5) _cell_angle_alpha 69.894(5) _cell_angle_beta 86.657(5) _cell_angle_gamma 77.321(5) _cell_volume 1981.3(14) _cell_formula_units_Z 2 _cell_measurement_temperature 120(2) _cell_measurement_reflns_used 48512 _cell_measurement_theta_min 2.91 _cell_measurement_theta_max 27.48 _exptl_crystal_description shard _exptl_crystal_colour yellow _exptl_crystal_size_max 0.04 _exptl_crystal_size_mid 0.03 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.478 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 908 _exptl_absorpt_coefficient_mu 1.516 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.7638 _exptl_absorpt_correction_T_max 0.9850 _exptl_absorpt_process_details 'SADABS 2007/2 (Sheldrick, G.M., 2007)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 120(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'Bruker-Nonius FR591 rotating anode' _diffrn_radiation_monochromator '10cm confocal mirrors' _diffrn_measurement_device_type 'Bruker-Nonius APEX II CCD camera on \k-goniostat' _diffrn_measurement_method '\f & \w scans' _diffrn_detector_area_resol_mean '4096x4096pixels / 62x62mm' _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 24222 _diffrn_reflns_av_R_equivalents 0.1379 _diffrn_reflns_av_unetI/netI 0.1150 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 2.97 _diffrn_reflns_theta_max 22.50 _reflns_number_total 5162 _reflns_number_gt 3417 _reflns_threshold_expression >2\s(I) _computing_data_collection 'COLLECT (Hooft, R.W.W., 1998)' _computing_cell_refinement 'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)' #Although determined using DirAx, the cell is refined in the HKL #package during data reduction _computing_data_reduction 'DENZO (Otwinowski & Minor, 1997) & COLLECT (Hooft, R.W.W., 1998)' _computing_structure_solution 'SIR92 (Altomare et al., 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'ORTEP-3 (Farrugia, 1997)' _computing_publication_material ; SHELXL-97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004) ; _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^ > 2\s(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^)+21.9294P] 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 5162 _refine_ls_number_parameters 505 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1510 _refine_ls_R_factor_gt 0.0889 _refine_ls_wR_factor_ref 0.1726 _refine_ls_wR_factor_gt 0.1522 _refine_ls_goodness_of_fit_ref 1.103 _refine_ls_restrained_S_all 1.103 _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 C1 C 0.4947(9) 0.3906(9) 0.1649(7) 0.025(2) Uani 1 1 d . . . H1 H 0.4595 0.4096 0.1075 0.029 Uiso 1 1 calc R . . C2 C 0.6181(10) 0.3771(9) 0.1732(7) 0.028(3) Uani 1 1 d . . . H2A H 0.6679 0.3873 0.1217 0.034 Uiso 1 1 calc R . . C3 C 0.6743(10) 0.3486(9) 0.2563(7) 0.034(3) Uani 1 1 d . . . H3 H 0.7616 0.3368 0.2623 0.041 Uiso 1 1 calc R . . C4 C 0.5996(11) 0.3381(10) 0.3287(7) 0.035(3) Uani 1 1 d . . . H4 H 0.6341 0.3200 0.3862 0.042 Uiso 1 1 calc R . . C5 C 0.4728(9) 0.3544(8) 0.3169(6) 0.022(2) Uani 1 1 d . . . C6 C 0.2619(10) 0.3670(9) 0.3664(7) 0.027(3) Uani 1 1 d . . . C7 C 0.0720(11) 0.4135(8) 0.2669(6) 0.025(3) Uani 1 1 d . . . C8 C 0.3578(9) 0.1178(8) 0.2182(6) 0.023(2) Uani 1 1 d . . . C9 C 0.4826(9) 0.1039(8) 0.2381(6) 0.022(2) Uani 1 1 d . . . H9 H 0.5045 0.1468 0.2723 0.027 Uiso 1 1 calc R . . C10 C 0.5750(10) 0.0297(8) 0.2097(7) 0.030(3) Uani 1 1 d . . . H10 H 0.6588 0.0205 0.2260 0.035 Uiso 1 1 calc R . . C11 C 0.5469(11) -0.0315(9) 0.1574(7) 0.035(3) Uani 1 1 d . . . H11 H 0.6104 -0.0830 0.1380 0.042 Uiso 1 1 calc R . . C12 C 0.4260(10) -0.0161(10) 0.1345(7) 0.034(3) Uani 1 1 d . . . H12 H 0.4063 -0.0570 0.0979 0.040 Uiso 1 1 calc R . . C13 C 0.3311(11) 0.0566(9) 0.1625(7) 0.033(3) Uani 1 1 d . . . H13 H 0.2480 0.0659 0.1447 0.040 Uiso 1 1 calc R . . C14 C 0.2426(10) 0.1078(8) 0.3857(6) 0.023(2) Uani 1 1 d . . . C15 C 0.3467(10) 0.0219(9) 0.4261(6) 0.027(3) Uani 1 1 d . . . H15 H 0.4186 0.0082 0.3925 0.033 Uiso 1 1 calc R . . C16 C 0.3441(10) -0.0435(9) 0.5162(6) 0.027(3) Uani 1 1 d . . . H16 H 0.4155 -0.1012 0.5445 0.033 Uiso 1 1 calc R . . C17 C 0.2404(11) -0.0260(10) 0.5646(7) 0.038(3) Uani 1 1 d . . . H17 H 0.2388 -0.0732 0.6257 0.045 Uiso 1 1 calc R . . C18 C 0.1381(11) 0.0603(9) 0.5247(7) 0.035(3) Uani 1 1 d . . . H18 H 0.0666 0.0741 0.5586 0.041 Uiso 1 1 calc R . . C19 C 0.1398(10) 0.1259(10) 0.4362(7) 0.034(3) Uani 1 1 d . . . H19 H 0.0689 0.1850 0.4091 0.040 Uiso 1 1 calc R . . C20 C 0.0936(9) 0.1756(9) 0.2278(7) 0.025(3) Uani 1 1 d . . . C21 C 0.0585(10) 0.0670(10) 0.2682(7) 0.032(3) Uani 1 1 d . . . H21 H 0.1061 0.0072 0.3167 0.038 Uiso 1 1 calc R . . C22 C -0.0449(11) 0.0464(10) 0.2378(7) 0.036(3) Uani 1 1 d . . . H22 H -0.0679 -0.0280 0.2658 0.043 Uiso 1 1 calc R . . C23 C -0.1165(11) 0.1313(10) 0.1674(8) 0.037(3) Uani 1 1 d . . . H23 H -0.1878 0.1163 0.1466 0.045 Uiso 1 1 calc R . . C24 C -0.0808(10) 0.2384(10) 0.1283(7) 0.032(3) Uani 1 1 d . . . H24 H -0.1284 0.2981 0.0797 0.039 Uiso 1 1 calc R . . C25 C 0.0225(9) 0.2611(9) 0.1581(6) 0.024(2) Uani 1 1 d . . . H25 H 0.0446 0.3360 0.1304 0.029 Uiso 1 1 calc R . . C26 C 0.3300(10) 0.6641(9) 0.1494(7) 0.026(3) Uani 1 1 d . . . C27 C 0.4488(10) 0.6404(9) 0.1872(7) 0.028(3) Uani 1 1 d . . . H27 H 0.4618 0.5998 0.2495 0.033 Uiso 1 1 calc R . . C28 C 0.5459(10) 0.6753(9) 0.1352(7) 0.030(3) Uani 1 1 d . . . H28 H 0.6251 0.6603 0.1620 0.036 Uiso 1 1 calc R . . C29 C 0.5301(11) 0.7317(10) 0.0449(8) 0.040(3) Uani 1 1 d . . . H29 H 0.5977 0.7551 0.0090 0.048 Uiso 1 1 calc R . . C30 C 0.4146(11) 0.7537(9) 0.0071(7) 0.036(3) Uani 1 1 d . . . H30 H 0.4033 0.7929 -0.0554 0.043 Uiso 1 1 calc R . . C31 C 0.3131(10) 0.7198(9) 0.0583(7) 0.030(3) Uani 1 1 d . . . H31 H 0.2344 0.7349 0.0310 0.035 Uiso 1 1 calc R . . C32 C 0.1870(9) 0.6530(8) 0.3101(6) 0.021(2) Uani 1 1 d . . . C33 C 0.2583(10) 0.7230(9) 0.3266(6) 0.030(3) Uani 1 1 d . . . H33 H 0.3213 0.7480 0.2861 0.035 Uiso 1 1 calc R . . C34 C 0.2399(10) 0.7577(8) 0.4013(7) 0.028(3) Uani 1 1 d . . . H34 H 0.2925 0.8024 0.4136 0.034 Uiso 1 1 calc R . . C35 C 0.1446(10) 0.7265(10) 0.4574(6) 0.033(3) Uani 1 1 d . . . H35 H 0.1323 0.7491 0.5090 0.040 Uiso 1 1 calc R . . C36 C 0.0674(10) 0.6634(9) 0.4398(7) 0.031(3) Uani 1 1 d . . . H36 H -0.0008 0.6465 0.4773 0.038 Uiso 1 1 calc R . . C37 C 0.0880(9) 0.6245(9) 0.3683(6) 0.023(2) Uani 1 1 d . . . H37 H 0.0358 0.5783 0.3577 0.028 Uiso 1 1 calc R . . C38 C 0.0641(8) 0.6971(8) 0.1479(6) 0.018(2) Uani 1 1 d . . . C39 C 0.0388(11) 0.8174(9) 0.1358(7) 0.033(3) Uani 1 1 d . . . H39 H 0.0925 0.8483 0.1617 0.039 Uiso 1 1 calc R . . C40 C -0.0639(11) 0.8932(10) 0.0861(7) 0.038(3) Uani 1 1 d . . . H40 H -0.0788 0.9761 0.0766 0.045 Uiso 1 1 calc R . . C41 C -0.1450(11) 0.8486(11) 0.0503(7) 0.041(3) Uani 1 1 d . . . H41 H -0.2165 0.8999 0.0172 0.049 Uiso 1 1 calc R . . C42 C -0.1205(10) 0.7298(11) 0.0634(7) 0.036(3) Uani 1 1 d . . . H42 H -0.1757 0.6985 0.0392 0.043 Uiso 1 1 calc R . . C43 C -0.0174(9) 0.6545(10) 0.1111(7) 0.030(3) Uani 1 1 d . . . H43 H -0.0019 0.5720 0.1189 0.035 Uiso 1 1 calc R . . C101 C 0.3683(12) 0.4415(10) 0.5640(8) 0.044(3) Uani 1 1 d . . . H10A H 0.3351 0.4955 0.5044 0.053 Uiso 1 1 calc R . . H10B H 0.4200 0.4818 0.5870 0.053 Uiso 1 1 calc R . . C102 C 0.2655(13) 0.4136(12) 0.6249(9) 0.059(4) Uani 1 1 d . . . H10C H 0.2704 0.4394 0.6767 0.071 Uiso 1 1 calc R . . H10D H 0.1848 0.4546 0.5938 0.071 Uiso 1 1 calc R . . C103 C 0.2785(13) 0.2858(12) 0.6537(9) 0.060(4) Uani 1 1 d . . . H10E H 0.2104 0.2657 0.6281 0.072 Uiso 1 1 calc R . . H10F H 0.2757 0.2522 0.7195 0.072 Uiso 1 1 calc R . . C104 C 0.4007(14) 0.2364(12) 0.6214(9) 0.065(4) Uani 1 1 d . . . H10G H 0.4611 0.1972 0.6718 0.077 Uiso 1 1 calc R . . H10H H 0.3916 0.1766 0.5947 0.077 Uiso 1 1 calc R . . Br1 Br 0.22391(10) 0.44803(10) 0.07284(7) 0.0269(3) Uani 1 1 d . . . Fe1 Fe 0.23038(13) 0.40087(13) 0.24175(9) 0.0210(4) Uani 1 1 d . . . N1 N 0.4185(7) 0.3776(7) 0.2369(5) 0.0188(19) Uani 1 1 d . . . N2 N 0.3905(8) 0.3472(7) 0.3841(5) 0.028(2) Uani 1 1 d . . . H2 H 0.4171 0.3301 0.4389 0.034 Uiso 1 1 calc R . . O1 O 0.1923(6) 0.3617(6) 0.4277(4) 0.0241(16) Uani 1 1 d . . . O2 O -0.0289(7) 0.4165(6) 0.2908(5) 0.0318(18) Uani 1 1 d . . . O100 O 0.4424(7) 0.3313(7) 0.5574(4) 0.0368(19) Uani 1 1 d . . . P1 P 0.2351(3) 0.2039(2) 0.26584(17) 0.0240(7) Uani 1 1 d . . . P2 P 0.2039(2) 0.6017(2) 0.21328(17) 0.0231(7) Uani 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 0.025(7) 0.028(6) 0.021(6) -0.010(5) 0.001(5) -0.006(5) C2 0.028(7) 0.028(6) 0.028(6) -0.008(5) 0.007(5) -0.009(5) C3 0.028(7) 0.033(7) 0.042(7) -0.017(6) -0.001(6) 0.002(5) C4 0.043(8) 0.035(7) 0.028(7) -0.008(6) -0.015(6) -0.010(6) C5 0.022(7) 0.020(6) 0.022(6) -0.011(5) -0.005(5) 0.007(5) C6 0.033(7) 0.021(6) 0.023(6) 0.000(5) -0.006(6) -0.006(5) C7 0.046(8) 0.010(5) 0.018(6) -0.001(5) -0.006(5) -0.009(5) C8 0.028(7) 0.014(5) 0.018(5) 0.008(5) 0.000(5) -0.010(5) C9 0.014(6) 0.018(6) 0.030(6) -0.005(5) 0.002(5) 0.002(5) C10 0.017(6) 0.015(6) 0.044(7) 0.002(5) -0.004(5) 0.005(5) C11 0.040(8) 0.020(6) 0.031(6) 0.003(5) 0.007(6) 0.004(6) C12 0.032(8) 0.036(7) 0.029(6) -0.014(6) 0.011(5) 0.003(6) C13 0.034(7) 0.033(7) 0.022(6) 0.000(5) 0.001(5) -0.003(6) C14 0.033(7) 0.018(6) 0.010(5) 0.005(5) -0.008(5) -0.002(5) C15 0.031(7) 0.024(6) 0.022(6) -0.006(5) -0.001(5) 0.004(5) C16 0.028(7) 0.030(6) 0.020(6) -0.005(5) -0.008(5) -0.001(5) C17 0.051(8) 0.030(7) 0.015(6) 0.008(5) 0.005(6) 0.000(6) C18 0.038(8) 0.032(7) 0.019(6) 0.003(5) 0.002(5) 0.001(6) C19 0.032(7) 0.032(7) 0.039(7) -0.016(6) 0.012(6) -0.006(5) C20 0.027(7) 0.025(6) 0.033(6) -0.016(6) 0.008(5) -0.018(5) C21 0.031(7) 0.044(7) 0.019(6) -0.011(6) 0.006(5) -0.004(6) C22 0.047(8) 0.040(7) 0.028(7) -0.017(6) 0.012(6) -0.021(6) C23 0.036(7) 0.044(8) 0.041(7) -0.027(7) -0.002(6) -0.007(6) C24 0.035(7) 0.043(7) 0.025(6) -0.022(6) 0.002(5) -0.007(6) C25 0.032(7) 0.023(6) 0.018(6) -0.007(5) 0.006(5) -0.007(5) C26 0.027(7) 0.030(6) 0.031(6) -0.025(5) 0.002(5) -0.001(5) C27 0.034(7) 0.021(6) 0.031(6) -0.014(5) 0.001(5) -0.004(5) C28 0.023(7) 0.031(7) 0.041(7) -0.019(6) 0.003(5) -0.005(5) C29 0.033(8) 0.045(8) 0.044(8) -0.014(6) 0.010(6) -0.020(6) C30 0.060(9) 0.029(7) 0.020(6) -0.006(5) 0.000(6) -0.016(6) C31 0.032(7) 0.030(7) 0.029(7) -0.012(5) -0.004(5) -0.009(5) C32 0.028(6) 0.019(6) 0.012(5) -0.003(5) -0.003(5) -0.002(5) C33 0.031(7) 0.034(7) 0.022(6) -0.008(5) 0.005(5) -0.004(6) C34 0.037(7) 0.013(6) 0.034(6) -0.016(5) -0.005(6) 0.008(5) C35 0.036(7) 0.048(8) 0.010(5) -0.009(5) 0.004(5) 0.000(6) C36 0.027(7) 0.037(7) 0.030(6) -0.014(6) 0.006(5) -0.005(6) C37 0.021(6) 0.024(6) 0.028(6) -0.013(5) -0.005(5) -0.004(5) C38 0.013(6) 0.019(6) 0.017(5) -0.005(5) 0.003(4) -0.001(5) C39 0.044(8) 0.031(7) 0.022(6) -0.008(5) -0.003(5) -0.008(6) C40 0.043(8) 0.031(7) 0.039(7) -0.020(6) -0.015(6) 0.012(6) C41 0.040(8) 0.044(8) 0.032(7) -0.014(6) -0.007(6) 0.009(6) C42 0.019(7) 0.062(9) 0.028(6) -0.020(6) 0.001(5) -0.005(6) C43 0.021(7) 0.030(6) 0.041(7) -0.015(6) 0.005(5) -0.010(6) C101 0.072(10) 0.034(7) 0.036(7) -0.017(6) 0.004(7) -0.019(7) C102 0.058(10) 0.056(10) 0.048(8) -0.008(7) 0.022(7) -0.003(8) C103 0.061(10) 0.061(10) 0.047(8) -0.006(7) 0.014(7) -0.016(8) C104 0.081(11) 0.043(8) 0.041(8) -0.001(7) 0.010(8) 0.023(8) Br1 0.0299(7) 0.0308(6) 0.0213(6) -0.0097(5) 0.0004(5) -0.0074(5) Fe1 0.0224(9) 0.0226(8) 0.0180(8) -0.0067(7) -0.0001(6) -0.0050(7) N1 0.021(5) 0.015(4) 0.019(5) -0.004(4) -0.002(4) -0.003(4) N2 0.037(6) 0.026(5) 0.015(5) -0.006(4) -0.009(4) 0.008(4) O1 0.027(4) 0.031(4) 0.017(4) -0.008(3) 0.007(3) -0.013(3) O2 0.024(5) 0.043(5) 0.033(4) -0.017(4) 0.010(4) -0.013(4) O100 0.040(5) 0.038(5) 0.023(4) -0.003(4) -0.003(4) 0.000(4) P1 0.0260(17) 0.0228(16) 0.0211(15) -0.0063(13) -0.0009(12) -0.0026(13) P2 0.0216(16) 0.0269(16) 0.0224(15) -0.0107(13) 0.0000(12) -0.0048(13) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 C2 1.348(14) . ? C1 N1 1.372(12) . ? C1 H1 0.9500 . ? C2 C3 1.397(14) . ? C2 H2A 0.9500 . ? C3 C4 1.368(15) . ? C3 H3 0.9500 . ? C4 C5 1.388(14) . ? C4 H4 0.9500 . ? C5 N1 1.357(12) . ? C5 N2 1.359(12) . ? C6 O1 1.203(12) . ? C6 N2 1.417(13) . ? C6 Fe1 1.927(10) . ? C7 O2 1.156(12) . ? C7 Fe1 1.759(12) . ? C8 C9 1.394(13) . ? C8 C13 1.423(14) . ? C8 P1 1.826(10) . ? C9 C10 1.377(13) . ? C9 H9 0.9500 . ? C10 C11 1.385(15) . ? C10 H10 0.9500 . ? C11 C12 1.363(15) . ? C11 H11 0.9500 . ? C12 C13 1.380(14) . ? C12 H12 0.9500 . ? C13 H13 0.9500 . ? C14 C19 1.378(14) . ? C14 C15 1.391(14) . ? C14 P1 1.867(9) . ? C15 C16 1.388(14) . ? C15 H15 0.9500 . ? C16 C17 1.364(15) . ? C16 H16 0.9500 . ? C17 C18 1.378(15) . ? C17 H17 0.9500 . ? C18 C19 1.366(14) . ? C18 H18 0.9500 . ? C19 H19 0.9500 . ? C20 C25 1.376(14) . ? C20 C21 1.394(14) . ? C20 P1 1.854(10) . ? C21 C22 1.372(15) . ? C21 H21 0.9500 . ? C22 C23 1.382(15) . ? C22 H22 0.9500 . ? C23 C24 1.379(15) . ? C23 H23 0.9500 . ? C24 C25 1.379(14) . ? C24 H24 0.9500 . ? C25 H25 0.9500 . ? C26 C31 1.383(14) . ? C26 C27 1.408(14) . ? C26 P2 1.826(11) . ? C27 C28 1.372(14) . ? C27 H27 0.9500 . ? C28 C29 1.371(15) . ? C28 H28 0.9500 . ? C29 C30 1.377(15) . ? C29 H29 0.9500 . ? C30 C31 1.401(15) . ? C30 H30 0.9500 . ? C31 H31 0.9500 . ? C32 C33 1.379(13) . ? C32 C37 1.419(13) . ? C32 P2 1.845(9) . ? C33 C34 1.388(13) . ? C33 H33 0.9500 . ? C34 C35 1.374(14) . ? C34 H34 0.9500 . ? C35 C36 1.368(14) . ? C35 H35 0.9500 . ? C36 C37 1.372(13) . ? C36 H36 0.9500 . ? C37 H37 0.9500 . ? C38 C43 1.382(13) . ? C38 C39 1.383(13) . ? C38 P2 1.844(10) . ? C39 C40 1.385(15) . ? C39 H39 0.9500 . ? C40 C41 1.386(15) . ? C40 H40 0.9500 . ? C41 C42 1.361(15) . ? C41 H41 0.9500 . ? C42 C43 1.374(15) . ? C42 H42 0.9500 . ? C43 H43 0.9500 . ? C101 O100 1.451(13) . ? C101 C102 1.473(16) . ? C101 H10A 0.9900 . ? C101 H10B 0.9900 . ? C102 C103 1.447(17) . ? C102 H10C 0.9900 . ? C102 H10D 0.9900 . ? C103 C104 1.495(17) . ? C103 H10E 0.9900 . ? C103 H10F 0.9900 . ? C104 O100 1.404(14) . ? C104 H10G 0.9900 . ? C104 H10H 0.9900 . ? Br1 Fe1 2.5605(19) . ? Fe1 N1 2.038(8) . ? Fe1 P2 2.295(3) . ? Fe1 P1 2.296(3) . ? N2 H2 0.8800 . ? 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 C2 C1 N1 121.9(9) . . ? C2 C1 H1 119.1 . . ? N1 C1 H1 119.1 . . ? C1 C2 C3 121.2(10) . . ? C1 C2 H2A 119.4 . . ? C3 C2 H2A 119.4 . . ? C4 C3 C2 117.9(10) . . ? C4 C3 H3 121.0 . . ? C2 C3 H3 121.0 . . ? C3 C4 C5 119.0(10) . . ? C3 C4 H4 120.5 . . ? C5 C4 H4 120.5 . . ? N1 C5 N2 113.1(9) . . ? N1 C5 C4 123.2(9) . . ? N2 C5 C4 123.7(9) . . ? O1 C6 N2 118.0(9) . . ? O1 C6 Fe1 131.0(8) . . ? N2 C6 Fe1 110.9(7) . . ? O2 C7 Fe1 174.2(9) . . ? C9 C8 C13 116.5(9) . . ? C9 C8 P1 121.6(7) . . ? C13 C8 P1 121.9(8) . . ? C10 C9 C8 122.0(10) . . ? C10 C9 H9 119.0 . . ? C8 C9 H9 119.0 . . ? C9 C10 C11 120.6(10) . . ? C9 C10 H10 119.7 . . ? C11 C10 H10 119.7 . . ? C12 C11 C10 118.5(10) . . ? C12 C11 H11 120.8 . . ? C10 C11 H11 120.8 . . ? C11 C12 C13 122.4(11) . . ? C11 C12 H12 118.8 . . ? C13 C12 H12 118.8 . . ? C12 C13 C8 120.0(11) . . ? C12 C13 H13 120.0 . . ? C8 C13 H13 120.0 . . ? C19 C14 C15 119.1(9) . . ? C19 C14 P1 117.4(8) . . ? C15 C14 P1 123.4(8) . . ? C16 C15 C14 119.1(10) . . ? C16 C15 H15 120.4 . . ? C14 C15 H15 120.4 . . ? C17 C16 C15 120.8(10) . . ? C17 C16 H16 119.6 . . ? C15 C16 H16 119.6 . . ? C16 C17 C18 119.9(10) . . ? C16 C17 H17 120.0 . . ? C18 C17 H17 120.0 . . ? C19 C18 C17 119.8(10) . . ? C19 C18 H18 120.1 . . ? C17 C18 H18 120.1 . . ? C18 C19 C14 121.2(11) . . ? C18 C19 H19 119.4 . . ? C14 C19 H19 119.4 . . ? C25 C20 C21 118.9(9) . . ? C25 C20 P1 120.4(7) . . ? C21 C20 P1 120.7(8) . . ? C22 C21 C20 119.9(11) . . ? C22 C21 H21 120.0 . . ? C20 C21 H21 120.0 . . ? C21 C22 C23 121.7(11) . . ? C21 C22 H22 119.2 . . ? C23 C22 H22 119.2 . . ? C24 C23 C22 117.7(11) . . ? C24 C23 H23 121.1 . . ? C22 C23 H23 121.1 . . ? C25 C24 C23 121.5(11) . . ? C25 C24 H24 119.2 . . ? C23 C24 H24 119.2 . . ? C20 C25 C24 120.2(10) . . ? C20 C25 H25 119.9 . . ? C24 C25 H25 119.9 . . ? C31 C26 C27 119.1(10) . . ? C31 C26 P2 118.3(8) . . ? C27 C26 P2 121.9(8) . . ? C28 C27 C26 120.7(10) . . ? C28 C27 H27 119.6 . . ? C26 C27 H27 119.6 . . ? C29 C28 C27 120.8(11) . . ? C29 C28 H28 119.6 . . ? C27 C28 H28 119.6 . . ? C28 C29 C30 118.9(11) . . ? C28 C29 H29 120.5 . . ? C30 C29 H29 120.5 . . ? C29 C30 C31 121.8(10) . . ? C29 C30 H30 119.1 . . ? C31 C30 H30 119.1 . . ? C26 C31 C30 118.7(10) . . ? C26 C31 H31 120.7 . . ? C30 C31 H31 120.7 . . ? C33 C32 C37 117.9(8) . . ? C33 C32 P2 124.9(7) . . ? C37 C32 P2 117.1(7) . . ? C32 C33 C34 121.3(10) . . ? C32 C33 H33 119.3 . . ? C34 C33 H33 119.3 . . ? C35 C34 C33 119.2(10) . . ? C35 C34 H34 120.4 . . ? C33 C34 H34 120.4 . . ? C36 C35 C34 120.9(9) . . ? C36 C35 H35 119.6 . . ? C34 C35 H35 119.6 . . ? C35 C36 C37 120.4(10) . . ? C35 C36 H36 119.8 . . ? C37 C36 H36 119.8 . . ? C36 C37 C32 120.2(9) . . ? C36 C37 H37 119.9 . . ? C32 C37 H37 119.9 . . ? C43 C38 C39 118.3(9) . . ? C43 C38 P2 123.4(8) . . ? C39 C38 P2 118.3(7) . . ? C38 C39 C40 120.6(10) . . ? C38 C39 H39 119.7 . . ? C40 C39 H39 119.7 . . ? C39 C40 C41 120.2(10) . . ? C39 C40 H40 119.9 . . ? C41 C40 H40 119.9 . . ? C42 C41 C40 118.9(11) . . ? C42 C41 H41 120.6 . . ? C40 C41 H41 120.6 . . ? C41 C42 C43 121.2(11) . . ? C41 C42 H42 119.4 . . ? C43 C42 H42 119.4 . . ? C42 C43 C38 120.8(10) . . ? C42 C43 H43 119.6 . . ? C38 C43 H43 119.6 . . ? O100 C101 C102 108.7(9) . . ? O100 C101 H10A 109.9 . . ? C102 C101 H10A 109.9 . . ? O100 C101 H10B 109.9 . . ? C102 C101 H10B 109.9 . . ? H10A C101 H10B 108.3 . . ? C103 C102 C101 106.3(11) . . ? C103 C102 H10C 110.5 . . ? C101 C102 H10C 110.5 . . ? C103 C102 H10D 110.5 . . ? C101 C102 H10D 110.5 . . ? H10C C102 H10D 108.7 . . ? C102 C103 C104 107.0(11) . . ? C102 C103 H10E 110.3 . . ? C104 C103 H10E 110.3 . . ? C102 C103 H10F 110.3 . . ? C104 C103 H10F 110.3 . . ? H10E C103 H10F 108.6 . . ? O100 C104 C103 107.9(10) . . ? O100 C104 H10G 110.1 . . ? C103 C104 H10G 110.1 . . ? O100 C104 H10H 110.1 . . ? C103 C104 H10H 110.1 . . ? H10G C104 H10H 108.4 . . ? C7 Fe1 C6 87.5(5) . . ? C7 Fe1 N1 169.6(4) . . ? C6 Fe1 N1 82.2(4) . . ? C7 Fe1 P2 88.4(3) . . ? C6 Fe1 P2 91.4(3) . . ? N1 Fe1 P2 92.6(2) . . ? C7 Fe1 P1 86.2(3) . . ? C6 Fe1 P1 91.3(3) . . ? N1 Fe1 P1 93.2(2) . . ? P2 Fe1 P1 173.90(12) . . ? C7 Fe1 Br1 101.3(3) . . ? C6 Fe1 Br1 171.1(3) . . ? N1 Fe1 Br1 89.1(2) . . ? P2 Fe1 Br1 87.38(8) . . ? P1 Fe1 Br1 90.84(8) . . ? C5 N1 C1 116.7(8) . . ? C5 N1 Fe1 113.4(6) . . ? C1 N1 Fe1 129.6(6) . . ? C5 N2 C6 120.3(8) . . ? C5 N2 H2 119.8 . . ? C6 N2 H2 119.8 . . ? C104 O100 C101 107.9(8) . . ? C8 P1 C20 102.0(4) . . ? C8 P1 C14 102.1(4) . . ? C20 P1 C14 100.8(5) . . ? C8 P1 Fe1 120.2(3) . . ? C20 P1 Fe1 114.5(3) . . ? C14 P1 Fe1 114.6(3) . . ? C26 P2 C38 103.4(5) . . ? C26 P2 C32 105.1(4) . . ? C38 P2 C32 100.0(4) . . ? C26 P2 Fe1 112.9(3) . . ? C38 P2 Fe1 116.4(3) . . ? C32 P2 Fe1 117.3(3) . . ? 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 N1 C1 C2 C3 0.3(16) . . . . ? C1 C2 C3 C4 -1.9(15) . . . . ? C2 C3 C4 C5 0.9(15) . . . . ? C3 C4 C5 N1 1.7(16) . . . . ? C3 C4 C5 N2 -179.3(10) . . . . ? C13 C8 C9 C10 -3.5(14) . . . . ? P1 C8 C9 C10 173.5(8) . . . . ? C8 C9 C10 C11 2.0(15) . . . . ? C9 C10 C11 C12 0.4(15) . . . . ? C10 C11 C12 C13 -0.9(16) . . . . ? C11 C12 C13 C8 -0.7(16) . . . . ? C9 C8 C13 C12 2.9(14) . . . . ? P1 C8 C13 C12 -174.1(8) . . . . ? C19 C14 C15 C16 0.1(15) . . . . ? P1 C14 C15 C16 178.7(7) . . . . ? C14 C15 C16 C17 1.3(16) . . . . ? C15 C16 C17 C18 -2.2(17) . . . . ? C16 C17 C18 C19 1.7(17) . . . . ? C17 C18 C19 C14 -0.2(17) . . . . ? C15 C14 C19 C18 -0.7(16) . . . . ? P1 C14 C19 C18 -179.3(8) . . . . ? C25 C20 C21 C22 0.5(15) . . . . ? P1 C20 C21 C22 -178.4(8) . . . . ? C20 C21 C22 C23 0.0(16) . . . . ? C21 C22 C23 C24 -0.2(16) . . . . ? C22 C23 C24 C25 -0.1(15) . . . . ? C21 C20 C25 C24 -0.8(14) . . . . ? P1 C20 C25 C24 178.1(7) . . . . ? C23 C24 C25 C20 0.7(15) . . . . ? C31 C26 C27 C28 2.1(14) . . . . ? P2 C26 C27 C28 171.5(7) . . . . ? C26 C27 C28 C29 -1.5(15) . . . . ? C27 C28 C29 C30 0.5(16) . . . . ? C28 C29 C30 C31 -0.2(17) . . . . ? C27 C26 C31 C30 -1.7(14) . . . . ? P2 C26 C31 C30 -171.5(7) . . . . ? C29 C30 C31 C26 0.8(16) . . . . ? C37 C32 C33 C34 4.5(15) . . . . ? P2 C32 C33 C34 -179.8(8) . . . . ? C32 C33 C34 C35 -3.3(15) . . . . ? C33 C34 C35 C36 -0.8(16) . . . . ? C34 C35 C36 C37 3.6(17) . . . . ? C35 C36 C37 C32 -2.3(16) . . . . ? C33 C32 C37 C36 -1.7(14) . . . . ? P2 C32 C37 C36 -177.7(8) . . . . ? C43 C38 C39 C40 -1.6(15) . . . . ? P2 C38 C39 C40 179.1(8) . . . . ? C38 C39 C40 C41 2.1(17) . . . . ? C39 C40 C41 C42 -1.2(17) . . . . ? C40 C41 C42 C43 -0.1(17) . . . . ? C41 C42 C43 C38 0.6(16) . . . . ? C39 C38 C43 C42 0.3(14) . . . . ? P2 C38 C43 C42 179.6(8) . . . . ? O100 C101 C102 C103 -0.7(15) . . . . ? C101 C102 C103 C104 9.1(16) . . . . ? C102 C103 C104 O100 -14.8(16) . . . . ? O1 C6 Fe1 C7 -0.9(10) . . . . ? N2 C6 Fe1 C7 179.8(7) . . . . ? O1 C6 Fe1 N1 179.8(10) . . . . ? N2 C6 Fe1 N1 0.5(7) . . . . ? O1 C6 Fe1 P2 87.4(10) . . . . ? N2 C6 Fe1 P2 -91.9(7) . . . . ? O1 C6 Fe1 P1 -87.1(10) . . . . ? N2 C6 Fe1 P1 93.6(7) . . . . ? N2 C5 N1 C1 177.7(8) . . . . ? C4 C5 N1 C1 -3.2(14) . . . . ? N2 C5 N1 Fe1 2.4(10) . . . . ? C4 C5 N1 Fe1 -178.6(8) . . . . ? C2 C1 N1 C5 2.2(14) . . . . ? C2 C1 N1 Fe1 176.7(7) . . . . ? C7 Fe1 N1 C5 -6(2) . . . . ? C6 Fe1 N1 C5 -1.6(7) . . . . ? P2 Fe1 N1 C5 89.4(6) . . . . ? P1 Fe1 N1 C5 -92.5(6) . . . . ? Br1 Fe1 N1 C5 176.7(6) . . . . ? C7 Fe1 N1 C1 179.5(19) . . . . ? C6 Fe1 N1 C1 -176.3(9) . . . . ? P2 Fe1 N1 C1 -85.2(8) . . . . ? P1 Fe1 N1 C1 92.9(8) . . . . ? Br1 Fe1 N1 C1 2.1(8) . . . . ? N1 C5 N2 C6 -2.0(13) . . . . ? C4 C5 N2 C6 178.9(9) . . . . ? O1 C6 N2 C5 -178.7(9) . . . . ? Fe1 C6 N2 C5 0.6(11) . . . . ? C103 C104 O100 C101 14.3(14) . . . . ? C102 C101 O100 C104 -8.7(13) . . . . ? C9 C8 P1 C20 -173.3(8) . . . . ? C13 C8 P1 C20 3.5(9) . . . . ? C9 C8 P1 C14 -69.4(8) . . . . ? C13 C8 P1 C14 107.5(8) . . . . ? C9 C8 P1 Fe1 58.7(9) . . . . ? C13 C8 P1 Fe1 -124.4(7) . . . . ? C25 C20 P1 C8 -103.3(8) . . . . ? C21 C20 P1 C8 75.6(9) . . . . ? C25 C20 P1 C14 151.7(8) . . . . ? C21 C20 P1 C14 -29.4(9) . . . . ? C25 C20 P1 Fe1 28.2(9) . . . . ? C21 C20 P1 Fe1 -152.9(7) . . . . ? C19 C14 P1 C8 -160.2(8) . . . . ? C15 C14 P1 C8 21.2(9) . . . . ? C19 C14 P1 C20 -55.3(9) . . . . ? C15 C14 P1 C20 126.2(9) . . . . ? C19 C14 P1 Fe1 68.2(9) . . . . ? C15 C14 P1 Fe1 -110.4(8) . . . . ? C7 Fe1 P1 C8 158.5(5) . . . . ? C6 Fe1 P1 C8 -114.1(5) . . . . ? N1 Fe1 P1 C8 -31.9(4) . . . . ? Br1 Fe1 P1 C8 57.2(4) . . . . ? C7 Fe1 P1 C20 36.5(5) . . . . ? C6 Fe1 P1 C20 123.8(5) . . . . ? N1 Fe1 P1 C20 -153.9(4) . . . . ? Br1 Fe1 P1 C20 -64.8(4) . . . . ? C7 Fe1 P1 C14 -79.3(5) . . . . ? C6 Fe1 P1 C14 8.1(5) . . . . ? N1 Fe1 P1 C14 90.3(4) . . . . ? Br1 Fe1 P1 C14 179.4(4) . . . . ? C31 C26 P2 C38 -28.6(9) . . . . ? C27 C26 P2 C38 161.8(8) . . . . ? C31 C26 P2 C32 -133.0(8) . . . . ? C27 C26 P2 C32 57.4(9) . . . . ? C31 C26 P2 Fe1 98.0(8) . . . . ? C27 C26 P2 Fe1 -71.6(8) . . . . ? C43 C38 P2 C26 119.5(8) . . . . ? C39 C38 P2 C26 -61.1(8) . . . . ? C43 C38 P2 C32 -132.2(8) . . . . ? C39 C38 P2 C32 47.1(8) . . . . ? C43 C38 P2 Fe1 -4.8(9) . . . . ? C39 C38 P2 Fe1 174.5(6) . . . . ? C33 C32 P2 C26 -0.3(10) . . . . ? C37 C32 P2 C26 175.4(8) . . . . ? C33 C32 P2 C38 -107.1(9) . . . . ? C37 C32 P2 C38 68.5(8) . . . . ? C33 C32 P2 Fe1 126.1(8) . . . . ? C37 C32 P2 Fe1 -58.3(8) . . . . ? C7 Fe1 P2 C26 -162.9(5) . . . . ? C6 Fe1 P2 C26 109.6(5) . . . . ? N1 Fe1 P2 C26 27.4(4) . . . . ? Br1 Fe1 P2 C26 -61.5(4) . . . . ? C7 Fe1 P2 C38 -43.6(5) . . . . ? C6 Fe1 P2 C38 -131.0(5) . . . . ? N1 Fe1 P2 C38 146.7(4) . . . . ? Br1 Fe1 P2 C38 57.8(3) . . . . ? C7 Fe1 P2 C32 74.7(5) . . . . ? C6 Fe1 P2 C32 -12.8(5) . . . . ? N1 Fe1 P2 C32 -95.0(4) . . . . ? Br1 Fe1 P2 C32 176.1(4) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N2 H2 O100 0.88 1.93 2.792(10) 164.4 . _diffrn_measured_fraction_theta_max 0.996 _diffrn_reflns_theta_full 22.50 _diffrn_measured_fraction_theta_full 0.996 _refine_diff_density_max 0.606 _refine_diff_density_min -0.582 _refine_diff_density_rms 0.134 data_4a _database_code_depnum_ccdc_archive 'CCDC 922922' #TrackingRef '19053_web_deposit_cif_file_0_JosephA.Wright_1364738302.Carbamoyl-iron.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_structural C5H6N2O _chemical_formula_moiety 'C5 H6 N2 O, 0.5(H2 O)' _chemical_formula_sum 'C5 H7 N2 O1.50' _chemical_formula_weight 119.13 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' _symmetry_cell_setting triclinic _symmetry_space_group_name_H-M 'P -1' _symmetry_space_group_name_Hall '-P 1' _symmetry_Int_Tables_number 2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 4.8603(6) _cell_length_b 9.3209(11) _cell_length_c 13.5944(19) _cell_angle_alpha 97.673(10) _cell_angle_beta 91.575(11) _cell_angle_gamma 92.141(10) _cell_volume 609.59(13) _cell_formula_units_Z 4 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 1168 _cell_measurement_theta_min 3.4902 _cell_measurement_theta_max 28.9708 _exptl_crystal_description lath _exptl_crystal_colour colourless _exptl_crystal_size_max 0.80 _exptl_crystal_size_mid 0.08 _exptl_crystal_size_min 0.01 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.298 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 252 _exptl_absorpt_coefficient_mu 0.098 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.57293 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details '(ABSPACK; Agilent Technology, 2011)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_probe x-ray _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford Diffraction Xcalibur 3/CCD' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.0050 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 7632 _diffrn_reflns_av_R_equivalents 0.0551 _diffrn_reflns_av_unetI/netI 0.0950 _diffrn_reflns_limit_h_min -5 _diffrn_reflns_limit_h_max 5 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 11 _diffrn_reflns_limit_l_min -16 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 3.50 _diffrn_reflns_theta_max 25.00 _reflns_number_total 2142 _reflns_number_gt 1046 _reflns_threshold_expression >2\s(I) _computing_data_collection 'CrysAlisPro (Agilent Technology, 2011)' _computing_cell_refinement 'CrysAlisPro (Agilent Technology, 2011)' _computing_data_reduction 'CrysAlisPro (Agilent Technology, 2011)' _computing_structure_solution 'SIR92 (Altomare et al., 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'ORTEP-3 (Farrugia, 1997)' _computing_publication_material ; SHELXL-97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004) ; _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^ > 2\s(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^)+(0.0365P)^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 mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 2142 _refine_ls_number_parameters 186 _refine_ls_number_restraints 6 _refine_ls_R_factor_all 0.1302 _refine_ls_R_factor_gt 0.0543 _refine_ls_wR_factor_ref 0.1173 _refine_ls_wR_factor_gt 0.0963 _refine_ls_goodness_of_fit_ref 0.916 _refine_ls_restrained_S_all 0.915 _refine_ls_shift/su_max 0.009 _refine_ls_shift/su_mean 0.001 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 0.2659(6) 1.1184(3) 0.2039(2) 0.0492(7) Uani 1 1 d . . . C2 C 0.4739(6) 1.0717(3) 0.2611(2) 0.0590(8) Uani 1 1 d . . . H2 H 0.5297 1.1238 0.3220 0.071 Uiso 1 1 calc R . . C3 C 0.5968(6) 0.9451(3) 0.2253(2) 0.0668(9) Uani 1 1 d . . . H3 H 0.7377 0.9130 0.2634 0.080 Uiso 1 1 calc R . . C4 C 0.5219(6) 0.8647(3) 0.1368(2) 0.0608(9) Uani 1 1 d . . . H4 H 0.6106 0.7800 0.1155 0.073 Uiso 1 1 calc R . . C5 C 0.3103(6) 0.9109(3) 0.0782(2) 0.0487(7) Uani 1 1 d . . . C11 C 0.7973(7) 0.5710(3) 0.3140(2) 0.0571(9) Uani 1 1 d . . . C12 C 1.0157(7) 0.6639(4) 0.3017(3) 0.0702(10) Uani 1 1 d . . . H12 H 1.0849 0.6681 0.2390 0.084 Uiso 1 1 calc R . . C13 C 1.1310(7) 0.7508(4) 0.3833(3) 0.0822(11) Uani 1 1 d . . . H13 H 1.2788 0.8137 0.3746 0.099 Uiso 1 1 calc R . . C14 C 1.0350(7) 0.7479(4) 0.4772(3) 0.0751(10) Uani 1 1 d . . . H14 H 1.1147 0.8100 0.5304 0.090 Uiso 1 1 calc R . . C15 C 0.8177(6) 0.6518(3) 0.4928(3) 0.0595(9) Uani 1 1 d . . . N1 N 0.1932(5) 1.0389(2) 0.11525(17) 0.0485(6) Uani 1 1 d . . . N2 N 0.1336(6) 1.2441(3) 0.2288(2) 0.0682(8) Uani 1 1 d D . . N11 N 0.7090(5) 0.5683(3) 0.40837(18) 0.0517(7) Uani 1 1 d . . . N12 N 0.6649(7) 0.4794(3) 0.2415(2) 0.0716(9) Uani 1 1 d D . . O1 O 0.2159(4) 0.8460(2) -0.00499(14) 0.0607(6) Uani 1 1 d . . . O11 O 0.7141(4) 0.6334(2) 0.57486(15) 0.0693(7) Uani 1 1 d . . . O21 O 0.2505(5) 0.5513(3) -0.03037(16) 0.0664(7) Uani 1 1 d D . . H1 H 0.047(5) 1.078(3) 0.0767(17) 0.060(8) Uiso 1 1 d . . . H2A H -0.019(4) 1.256(3) 0.1934(17) 0.064(9) Uiso 1 1 d D . . H11 H 0.553(6) 0.502(3) 0.4206(19) 0.074(10) Uiso 1 1 d . . . H12A H 0.704(6) 0.479(3) 0.1782(14) 0.077(11) Uiso 1 1 d D . . H12B H 0.503(5) 0.433(4) 0.253(2) 0.114(16) Uiso 1 1 d D . . H2B H 0.155(7) 1.278(4) 0.2944(15) 0.133(16) Uiso 1 1 d D . . H21A H 0.265(6) 0.644(2) -0.022(2) 0.074(11) Uiso 1 1 d D . . H21B H 0.143(14) 0.527(12) 0.013(5) 0.41(5) Uiso 1 1 d 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 0.0453(18) 0.049(2) 0.0510(18) 0.0021(15) -0.0021(15) -0.0052(15) C2 0.054(2) 0.065(2) 0.0571(19) 0.0069(16) -0.0149(16) -0.0011(17) C3 0.056(2) 0.069(2) 0.078(2) 0.0206(19) -0.0154(17) 0.0034(19) C4 0.058(2) 0.053(2) 0.073(2) 0.0146(17) -0.0075(17) 0.0128(17) C5 0.0493(19) 0.0378(19) 0.061(2) 0.0120(15) 0.0018(15) 0.0026(15) C11 0.059(2) 0.060(2) 0.057(2) 0.0199(18) 0.0090(18) 0.0182(19) C12 0.059(2) 0.079(3) 0.079(2) 0.031(2) 0.0118(19) 0.015(2) C13 0.054(2) 0.081(3) 0.118(3) 0.042(3) -0.004(2) -0.006(2) C14 0.066(3) 0.073(3) 0.085(3) 0.015(2) -0.012(2) -0.014(2) C15 0.055(2) 0.059(2) 0.064(2) 0.0062(19) -0.0069(18) 0.0066(18) N1 0.0450(16) 0.0440(16) 0.0555(16) 0.0046(13) -0.0074(12) 0.0044(12) N2 0.062(2) 0.069(2) 0.067(2) -0.0132(16) -0.0149(16) 0.0153(16) N11 0.0485(17) 0.0553(18) 0.0522(17) 0.0094(13) 0.0049(13) 0.0021(14) N12 0.082(2) 0.087(2) 0.0449(19) 0.0019(17) 0.0101(17) 0.008(2) O1 0.0685(15) 0.0511(13) 0.0597(13) -0.0021(10) -0.0111(11) 0.0111(11) O11 0.0726(16) 0.0819(17) 0.0493(13) -0.0022(12) 0.0001(11) -0.0095(12) O21 0.0869(18) 0.0491(16) 0.0626(14) 0.0041(12) 0.0048(11) 0.0043(13) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 1.358(3) . ? C1 N2 1.365(3) . ? C1 C2 1.377(3) . ? C2 C3 1.378(4) . ? C2 H2 0.9300 . ? C3 C4 1.363(4) . ? C3 H3 0.9300 . ? C4 C5 1.399(3) . ? C4 H4 0.9300 . ? C5 O1 1.274(3) . ? C5 N1 1.381(3) . ? C11 N12 1.347(4) . ? C11 N11 1.367(3) . ? C11 C12 1.372(4) . ? C12 C13 1.376(4) . ? C12 H12 0.9300 . ? C13 C14 1.374(4) . ? C13 H13 0.9300 . ? C14 C15 1.399(4) . ? C14 H14 0.9300 . ? C15 O11 1.265(3) . ? C15 N11 1.379(3) . ? N1 H1 0.98(2) . ? N2 H2A 0.892(16) . ? N2 H2B 0.907(18) . ? N11 H11 0.99(3) . ? N12 H12A 0.887(17) . ? N12 H12B 0.910(18) . ? O21 H21A 0.860(17) . ? O21 H21B 0.84(2) . ? 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 N2 117.2(3) . . ? N1 C1 C2 118.8(3) . . ? N2 C1 C2 124.0(3) . . ? C1 C2 C3 117.9(3) . . ? C1 C2 H2 121.0 . . ? C3 C2 H2 121.0 . . ? C4 C3 C2 123.2(3) . . ? C4 C3 H3 118.4 . . ? C2 C3 H3 118.4 . . ? C3 C4 C5 119.4(3) . . ? C3 C4 H4 120.3 . . ? C5 C4 H4 120.3 . . ? O1 C5 N1 117.6(2) . . ? O1 C5 C4 126.3(3) . . ? N1 C5 C4 116.2(3) . . ? N12 C11 N11 116.6(3) . . ? N12 C11 C12 125.9(3) . . ? N11 C11 C12 117.5(3) . . ? C11 C12 C13 119.2(3) . . ? C11 C12 H12 120.4 . . ? C13 C12 H12 120.4 . . ? C14 C13 C12 122.2(3) . . ? C14 C13 H13 118.9 . . ? C12 C13 H13 118.9 . . ? C13 C14 C15 120.1(3) . . ? C13 C14 H14 119.9 . . ? C15 C14 H14 119.9 . . ? O11 C15 N11 117.6(3) . . ? O11 C15 C14 127.3(3) . . ? N11 C15 C14 115.1(3) . . ? C1 N1 C5 124.5(2) . . ? C1 N1 H1 115.6(14) . . ? C5 N1 H1 119.9(14) . . ? C1 N2 H2A 116.8(17) . . ? C1 N2 H2B 112(2) . . ? H2A N2 H2B 122(3) . . ? C11 N11 C15 125.9(3) . . ? C11 N11 H11 120.0(15) . . ? C15 N11 H11 114.1(15) . . ? C11 N12 H12A 122(2) . . ? C11 N12 H12B 121(2) . . ? H12A N12 H12B 115(3) . . ? H21A O21 H21B 107(7) . . ? 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 N1 C1 C2 C3 -0.5(4) . . . . ? N2 C1 C2 C3 -177.6(3) . . . . ? C1 C2 C3 C4 -0.2(5) . . . . ? C2 C3 C4 C5 0.0(5) . . . . ? C3 C4 C5 O1 -178.8(3) . . . . ? C3 C4 C5 N1 0.8(4) . . . . ? N12 C11 C12 C13 -179.6(3) . . . . ? N11 C11 C12 C13 -1.2(4) . . . . ? C11 C12 C13 C14 0.0(5) . . . . ? C12 C13 C14 C15 1.7(5) . . . . ? C13 C14 C15 O11 177.5(3) . . . . ? C13 C14 C15 N11 -2.1(4) . . . . ? N2 C1 N1 C5 178.7(3) . . . . ? C2 C1 N1 C5 1.3(4) . . . . ? O1 C5 N1 C1 178.1(3) . . . . ? C4 C5 N1 C1 -1.5(4) . . . . ? N12 C11 N11 C15 179.3(3) . . . . ? C12 C11 N11 C15 0.8(4) . . . . ? O11 C15 N11 C11 -178.7(3) . . . . ? C14 C15 N11 C11 0.9(4) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N1 H1 O1 0.98(2) 1.81(3) 2.788(3) 178(2) 2_575 N2 H2A N12 0.892(16) 2.66(2) 3.213(4) 121(2) 1_465 N11 H11 O11 0.99(3) 1.78(3) 2.769(3) 171(2) 2_666 N12 H12A O21 0.887(17) 2.011(19) 2.889(4) 170(3) 2_665 N12 H12B N2 0.910(18) 2.45(2) 3.310(5) 157(3) 1_545 N2 H2B O11 0.907(18) 1.94(2) 2.827(3) 166(3) 2_676 O21 H21A O1 0.860(17) 1.888(19) 2.734(3) 168(3) . O21 H21B O21 0.84(2) 2.06(5) 2.770(5) 142(7) 2_565 _diffrn_measured_fraction_theta_max 0.998 _diffrn_reflns_theta_full 25.00 _diffrn_measured_fraction_theta_full 0.998 _refine_diff_density_max 0.219 _refine_diff_density_min -0.170 _refine_diff_density_rms 0.039 data_6.MeCN _database_code_depnum_ccdc_archive 'CCDC 922923' #TrackingRef '19053_web_deposit_cif_file_0_JosephA.Wright_1364738302.Carbamoyl-iron.cif' _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C11 H15 Br Fe N3 O3 P, C2 H3 N' _chemical_formula_sum 'C13 H18 Br Fe N4 O3 P' _chemical_formula_weight 445.04 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' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/c' _symmetry_space_group_name_Hall '-P 2ybc' _symmetry_Int_Tables_number 14 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 9.8203(17) _cell_length_b 12.719(2) _cell_length_c 15.139(2) _cell_angle_alpha 90.00 _cell_angle_beta 91.830(14) _cell_angle_gamma 90.00 _cell_volume 1890.0(5) _cell_formula_units_Z 4 _cell_measurement_temperature 140(2) _cell_measurement_reflns_used 3286 _cell_measurement_theta_min 3.4061 _cell_measurement_theta_max 33.2883 _exptl_crystal_description Block _exptl_crystal_colour Orange _exptl_crystal_size_max 0.25 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.564 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 896 _exptl_absorpt_coefficient_mu 3.013 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.26811 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details '(ABSPACK; Oxford Diffraction, 2010)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 140(2) _diffrn_radiation_probe x-ray _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford Diffraction Xcalibur 3/CCD' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.0050 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 25340 _diffrn_reflns_av_R_equivalents 0.1651 _diffrn_reflns_av_unetI/netI 0.0919 _diffrn_reflns_limit_h_min -11 _diffrn_reflns_limit_h_max 11 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 15 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 17 _diffrn_reflns_theta_min 3.45 _diffrn_reflns_theta_max 24.99 _reflns_number_total 3300 _reflns_number_gt 2140 _reflns_threshold_expression >2\s(I) _computing_data_collection 'CrysAlisPro (Oxford Diffraction, 2010)' _computing_cell_refinement 'CrysAlisPro (Oxford Diffraction, 2010)' _computing_data_reduction 'CrysAlisPro (Oxford Diffraction, 2010)' _computing_structure_solution 'SIR92 (Altomare et al., 1993)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'ORTEP-3 (Farrugia, 1997)' _computing_publication_material ; SHELXL-97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004) ; _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^ > 2\s(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. Crystals of 6.MeCN were weakly diffracting, leading to a high value of R(eqiv) and wR2. ; _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^)+(0.1680P)^2^+4.4108P] 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 3300 _refine_ls_number_parameters 212 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1181 _refine_ls_R_factor_gt 0.0910 _refine_ls_wR_factor_ref 0.2767 _refine_ls_wR_factor_gt 0.2680 _refine_ls_goodness_of_fit_ref 1.039 _refine_ls_restrained_S_all 1.039 _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 C1 C 0.5977(11) 0.2673(9) 0.7663(7) 0.037(2) Uani 1 1 d . . . C2 C 0.4864(14) 0.2468(11) 0.8212(8) 0.054(3) Uani 1 1 d . . . H2A H 0.4781 0.2843 0.8751 0.064 Uiso 1 1 calc R . . C3 C 0.3940(13) 0.1755(11) 0.7976(9) 0.057(4) Uani 1 1 d . . . H3 H 0.3174 0.1637 0.8330 0.069 Uiso 1 1 calc R . . C4 C 0.4102(13) 0.1183(12) 0.7208(8) 0.058(4) Uani 1 1 d . . . H4 H 0.3465 0.0648 0.7048 0.070 Uiso 1 1 calc R . . C5 C 0.5153(11) 0.1382(9) 0.6688(7) 0.037(2) Uani 1 1 d . . . C6 C 0.6423(11) 0.1143(9) 0.5392(6) 0.033(2) Uani 1 1 d . . . C7 C 0.8744(12) 0.2048(9) 0.5060(8) 0.040(3) Uani 1 1 d . . . C8 C 0.6669(13) 0.3252(10) 0.5416(8) 0.048(3) Uani 1 1 d . . . C9 C 1.0468(14) 0.0654(12) 0.6405(9) 0.063(4) Uani 1 1 d . . . H9A H 1.0511 0.0583 0.5762 0.095 Uiso 1 1 calc R . . H9B H 1.0803 0.0007 0.6689 0.095 Uiso 1 1 calc R . . H9C H 1.1035 0.1248 0.6603 0.095 Uiso 1 1 calc R . . C10 C 0.8893(15) 0.1107(11) 0.7878(7) 0.055(3) Uani 1 1 d . . . H10A H 0.7986 0.1104 0.8129 0.083 Uiso 1 1 calc R . . H10B H 0.9327 0.1790 0.7989 0.083 Uiso 1 1 calc R . . H10C H 0.9450 0.0551 0.8154 0.083 Uiso 1 1 calc R . . C11 C 0.8019(14) -0.0425(10) 0.6621(8) 0.052(3) Uani 1 1 d . . . H11A H 0.7121 -0.0429 0.6884 0.078 Uiso 1 1 calc R . . H11B H 0.8620 -0.0923 0.6937 0.078 Uiso 1 1 calc R . . H11C H 0.7927 -0.0631 0.5998 0.078 Uiso 1 1 calc R . . C101 C 0.313(2) 0.3808(18) 0.6134(14) 0.104(6) Uani 1 1 d . . . H10D H 0.4063 0.4073 0.6124 0.155 Uiso 1 1 calc R . . H10E H 0.2943 0.3544 0.6726 0.155 Uiso 1 1 calc R . . H10F H 0.2491 0.4378 0.5982 0.155 Uiso 1 1 calc R . . C102 C 0.2949(17) 0.2933(15) 0.5475(12) 0.076(5) Uani 1 1 d . . . N1 N 0.6131(8) 0.2125(7) 0.6907(5) 0.0319(19) Uani 1 1 d . . . N2 N 0.5339(9) 0.0884(7) 0.5908(5) 0.036(2) Uani 1 1 d . . . H2 H 0.4763 0.0391 0.5730 0.043 Uiso 1 1 calc R . . N3 N 0.6901(10) 0.3377(7) 0.7913(6) 0.046(2) Uani 1 1 d . . . H3A H 0.7614 0.3488 0.7587 0.055 Uiso 1 1 calc R . . H3B H 0.6804 0.3735 0.8404 0.055 Uiso 1 1 calc R . . N101 N 0.2884(15) 0.2276(12) 0.4978(9) 0.079(4) Uani 1 1 d . . . O1 O 0.6538(7) 0.0698(6) 0.4669(4) 0.0360(17) Uani 1 1 d . . . O2 O 0.9432(9) 0.1948(7) 0.4483(5) 0.052(2) Uani 1 1 d . . . O3 O 0.6164(11) 0.3894(8) 0.5053(7) 0.073(3) Uani 1 1 d . . . P1 P 0.8739(3) 0.0880(2) 0.66993(17) 0.0347(7) Uani 1 1 d . . . Fe1 Fe 0.75968(15) 0.21676(12) 0.59486(9) 0.0320(5) Uani 1 1 d . . . Br1 Br 0.93684(13) 0.34655(10) 0.65564(8) 0.0508(5) Uani 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 0.028(6) 0.043(6) 0.039(6) -0.004(5) -0.008(5) 0.006(5) C2 0.050(8) 0.071(9) 0.040(6) -0.019(6) -0.001(5) 0.006(7) C3 0.040(7) 0.070(9) 0.062(8) -0.020(7) 0.012(6) -0.018(7) C4 0.036(7) 0.082(10) 0.056(7) -0.021(7) 0.002(6) -0.019(7) C5 0.028(6) 0.053(7) 0.031(5) -0.008(5) -0.006(4) -0.001(5) C6 0.033(6) 0.040(6) 0.026(5) 0.008(5) -0.009(4) 0.002(5) C7 0.040(7) 0.030(6) 0.048(7) -0.003(5) -0.014(5) -0.005(5) C8 0.054(8) 0.039(7) 0.051(7) 0.006(6) -0.016(6) -0.014(6) C9 0.047(8) 0.069(9) 0.073(9) 0.013(7) -0.004(7) 0.010(7) C10 0.065(9) 0.054(8) 0.046(7) 0.002(6) -0.019(6) 0.014(7) C11 0.057(8) 0.042(7) 0.056(7) 0.007(6) -0.014(6) 0.005(6) C101 0.081(13) 0.103(15) 0.128(16) -0.029(13) 0.025(12) -0.021(11) C102 0.066(11) 0.090(13) 0.075(11) -0.001(10) 0.028(9) -0.010(9) N1 0.019(4) 0.041(5) 0.035(4) -0.001(4) -0.005(3) -0.001(4) N2 0.029(5) 0.036(5) 0.042(5) -0.007(4) -0.005(4) -0.010(4) N3 0.049(6) 0.046(6) 0.044(5) -0.019(5) 0.005(4) -0.005(5) N101 0.087(11) 0.081(10) 0.070(8) -0.011(7) 0.006(7) 0.002(8) O1 0.041(4) 0.037(4) 0.030(4) -0.004(3) -0.009(3) -0.005(3) O2 0.054(5) 0.065(6) 0.038(4) 0.002(4) 0.009(4) -0.015(4) O3 0.070(7) 0.049(6) 0.098(8) 0.016(6) -0.010(6) 0.016(5) P1 0.0314(15) 0.0372(16) 0.0349(14) -0.0005(11) -0.0086(11) 0.0018(12) Fe1 0.0307(9) 0.0315(8) 0.0334(8) -0.0006(6) -0.0077(6) -0.0026(6) Br1 0.0454(8) 0.0496(8) 0.0574(8) -0.0125(6) -0.0023(5) -0.0183(6) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 1.352(13) . ? C1 N3 1.322(15) . ? C2 C1 1.419(17) . ? C2 H2A 0.9500 . ? C3 C2 1.323(19) . ? C3 H3 0.9500 . ? C4 C3 1.384(18) . ? C4 H4 0.9500 . ? C5 C4 1.342(16) . ? C5 N2 1.358(13) . ? C5 N1 1.380(14) . ? C6 O1 1.241(12) . ? C6 N2 1.380(13) . ? C6 Fe1 1.917(11) . ? C7 O2 1.128(13) . ? C7 Fe1 1.789(13) . ? C8 O3 1.095(15) . ? C8 Fe1 1.826(14) . ? C9 P1 1.793(14) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 P1 1.809(12) . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 P1 1.806(13) . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C101 C102 1.50(3) . ? C101 H10D 0.9800 . ? C101 H10E 0.9800 . ? C101 H10F 0.9800 . ? C102 N101 1.13(2) . ? N1 Fe1 2.077(8) . ? N2 H2 0.8800 . ? N3 H3A 0.8800 . ? N3 H3B 0.8800 . ? P1 Fe1 2.270(3) . ? Fe1 Br1 2.5488(18) . ? 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 N3 C1 C2 119.4(10) . . ? N1 C1 C2 120.7(10) . . ? N3 C1 N1 119.8(10) . . ? C3 C2 C1 120.1(11) . . ? C3 C2 H2A 120.0 . . ? C1 C2 H2A 120.0 . . ? C2 C3 C4 119.4(12) . . ? C2 C3 H3 120.3 . . ? C4 C3 H3 120.3 . . ? C5 C4 C3 120.3(12) . . ? C5 C4 H4 119.9 . . ? C3 C4 H4 119.9 . . ? C4 C5 N2 123.3(10) . . ? C4 C5 N1 122.0(10) . . ? N2 C5 N1 114.6(9) . . ? O1 C6 N2 118.9(9) . . ? O1 C6 Fe1 128.9(8) . . ? N2 C6 Fe1 112.2(7) . . ? O3 C8 Fe1 175.5(13) . . ? O2 C7 Fe1 177.3(10) . . ? P1 C9 H9A 109.5 . . ? P1 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? P1 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? P1 C10 H10A 109.5 . . ? P1 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? P1 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? P1 C11 H11A 109.5 . . ? P1 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? P1 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C102 C101 H10D 109.5 . . ? C102 C101 H10E 109.5 . . ? H10D C101 H10E 109.5 . . ? C102 C101 H10F 109.5 . . ? H10D C101 H10F 109.5 . . ? H10E C101 H10F 109.5 . . ? N101 C102 C101 176.6(18) . . ? C1 N1 C5 117.4(8) . . ? C1 N1 Fe1 132.6(7) . . ? C5 N1 Fe1 110.0(6) . . ? C5 N2 C6 120.5(9) . . ? C5 N2 H2 119.7 . . ? C6 N2 H2 119.7 . . ? C1 N3 H3A 120.0 . . ? C1 N3 H3B 120.0 . . ? H3A N3 H3B 120.0 . . ? C9 P1 C11 102.0(7) . . ? C9 P1 C10 102.7(7) . . ? C11 P1 C10 103.4(6) . . ? C9 P1 Fe1 116.6(5) . . ? C11 P1 Fe1 116.4(4) . . ? C10 P1 Fe1 113.8(4) . . ? C7 Fe1 C8 92.8(5) . . ? C7 Fe1 C6 89.8(5) . . ? C8 Fe1 C6 92.0(5) . . ? C7 Fe1 N1 172.1(4) . . ? C8 Fe1 N1 88.9(5) . . ? C6 Fe1 N1 82.5(4) . . ? C7 Fe1 P1 90.1(4) . . ? C8 Fe1 P1 176.1(4) . . ? C6 Fe1 P1 90.6(3) . . ? N1 Fe1 P1 88.5(2) . . ? C7 Fe1 Br1 83.5(3) . . ? C8 Fe1 Br1 89.7(4) . . ? C6 Fe1 Br1 173.2(3) . . ? N1 Fe1 Br1 104.2(2) . . ? P1 Fe1 Br1 88.06(9) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N2 H2 O1 0.88 1.97 2.846(11) 179.4 3_656 N3 H3A Br1 0.88 2.36 3.227(10) 167.9 . N3 H3B O1 0.88 2.07 2.940(11) 169.3 4_566 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 24.99 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 1.285 _refine_diff_density_min -0.857 _refine_diff_density_rms 0.186 data_Fe(CO)(PMe3)2{C6H6N3CO(FeBr3)}(MeCN) _database_code_depnum_ccdc_archive 'CCDC 922924' #TrackingRef '19053_web_deposit_cif_file_0_JosephA.Wright_1364738302.Carbamoyl-iron.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_structural Fe(CO)(PMe3)2{C6H6N3CO(FeBr3)}(MeCN) _chemical_formula_moiety 'C15 H27 Br3 Fe2 N4 O2 P2' _chemical_formula_sum 'C15 H27 Br3 Fe2 N4 O2 P2' _chemical_formula_weight 708.78 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' Fe Fe 0.3463 0.8444 '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' Br Br -0.2901 2.4595 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting monoclinic _symmetry_space_group_name_H-M 'P 21/n' _symmetry_space_group_name_Hall '-P 2yn' _symmetry_Int_Tables_number 14 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 10.0743(3) _cell_length_b 13.2511(3) _cell_length_c 18.8476(5) _cell_angle_alpha 90.00 _cell_angle_beta 92.460(2) _cell_angle_gamma 90.00 _cell_volume 2513.75(12) _cell_formula_units_Z 4 _cell_measurement_temperature 140(2) _cell_measurement_reflns_used 15055 _cell_measurement_theta_min 3.5845 _cell_measurement_theta_max 29.0353 _exptl_crystal_description block _exptl_crystal_colour 'light yellow' _exptl_crystal_size_max 0.28 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.16 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.873 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1392 _exptl_absorpt_coefficient_mu 6.068 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_correction_T_min 0.69090 _exptl_absorpt_correction_T_max 1.00000 _exptl_absorpt_process_details '(ABSPACK; Oxford Diffraction, 2010)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 140(2) _diffrn_radiation_probe x-ray _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type 'Mo K\a' _diffrn_radiation_source 'Enhance (Mo) X-ray Source' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Oxford Diffraction Xcalibur 3/CCD' _diffrn_measurement_method '\w scans' _diffrn_detector_area_resol_mean 16.0050 _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 36310 _diffrn_reflns_av_R_equivalents 0.0348 _diffrn_reflns_av_unetI/netI 0.0251 _diffrn_reflns_limit_h_min -13 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 3.59 _diffrn_reflns_theta_max 27.50 _reflns_number_total 5708 _reflns_number_gt 4933 _reflns_threshold_expression >2\s(I) _computing_data_collection 'CrysAlisPro (Oxford Diffraction, 2010)' _computing_cell_refinement 'CrysAlisPro (Oxford Diffraction, 2010)' _computing_data_reduction 'CrysAlisPro (Oxford Diffraction, 2010)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 2008)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 2008)' _computing_molecular_graphics 'ORTEP-3 (Farrugia, 1997)' _computing_publication_material ; SHELXL-97 (Sheldrick, 2008) and enCIFer (Allen et al., 2004) ; _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^ > 2\s(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^)+(0.0232P)^2^+1.9629P] 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 none _refine_ls_extinction_coef ? _refine_ls_number_reflns 5708 _refine_ls_number_parameters 272 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0351 _refine_ls_R_factor_gt 0.0263 _refine_ls_wR_factor_ref 0.0563 _refine_ls_wR_factor_gt 0.0541 _refine_ls_goodness_of_fit_ref 1.046 _refine_ls_restrained_S_all 1.046 _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_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group C1 C 0.7121(2) 0.69937(16) -0.25723(12) 0.0164(5) Uani 1 1 d . . . C2 C 0.6043(3) 0.71443(17) -0.30554(13) 0.0211(5) Uani 1 1 d . . . H2 H 0.6110 0.6954 -0.3539 0.025 Uiso 1 1 calc R . . C3 C 0.4900(3) 0.75631(18) -0.28326(13) 0.0238(5) Uani 1 1 d . . . H3 H 0.4172 0.7673 -0.3160 0.029 Uiso 1 1 calc R . . C4 C 0.4802(3) 0.78301(18) -0.21220(13) 0.0228(5) Uani 1 1 d . . . H4 H 0.4012 0.8119 -0.1953 0.027 Uiso 1 1 calc R . . C5 C 0.5895(2) 0.76587(17) -0.16724(12) 0.0184(5) Uani 1 1 d . . . C6 C 0.6976(2) 0.76458(17) -0.05339(12) 0.0179(5) Uani 1 1 d . . . C7 C 0.9358(2) 0.71488(17) -0.02203(13) 0.0189(5) Uani 1 1 d . . . C8 C 1.0978(2) 0.62815(18) -0.16939(13) 0.0206(5) Uani 1 1 d . . . C9 C 1.2233(3) 0.5885(2) -0.19296(16) 0.0354(7) Uani 1 1 d . . . H9A H 1.2274 0.5157 -0.1841 0.053 Uiso 1 1 calc R . . H9B H 1.2971 0.6219 -0.1668 0.053 Uiso 1 1 calc R . . H9C H 1.2300 0.6013 -0.2439 0.053 Uiso 1 1 calc R . . C10 C 0.8392(3) 0.45617(18) -0.12896(13) 0.0256(6) Uani 1 1 d . . . H10A H 0.7939 0.3924 -0.1194 0.038 Uiso 1 1 calc R . . H10B H 0.9333 0.4505 -0.1141 0.038 Uiso 1 1 calc R . . H10C H 0.8313 0.4710 -0.1799 0.038 Uiso 1 1 calc R . . C11 C 0.5874(3) 0.5373(2) -0.09844(16) 0.0298(6) Uani 1 1 d . . . H11A H 0.5653 0.5533 -0.1483 0.045 Uiso 1 1 calc R . . H11B H 0.5364 0.5812 -0.0678 0.045 Uiso 1 1 calc R . . H11C H 0.5653 0.4666 -0.0892 0.045 Uiso 1 1 calc R . . C12 C 0.7840(3) 0.51608(19) 0.01195(13) 0.0274(6) Uani 1 1 d . . . H12A H 0.7409 0.5645 0.0428 0.041 Uiso 1 1 calc R . . H12B H 0.8788 0.5121 0.0255 0.041 Uiso 1 1 calc R . . H12C H 0.7432 0.4495 0.0171 0.041 Uiso 1 1 calc R . . C13 C 0.8526(3) 0.96541(19) -0.05711(15) 0.0324(6) Uani 1 1 d . . . H13A H 0.8931 1.0312 -0.0660 0.049 Uiso 1 1 calc R . . H13B H 0.8780 0.9430 -0.0089 0.049 Uiso 1 1 calc R . . H13C H 0.7557 0.9713 -0.0621 0.049 Uiso 1 1 calc R . . C14 C 0.8556(3) 0.92859(19) -0.20522(14) 0.0275(6) Uani 1 1 d . . . H14A H 0.8942 0.9961 -0.2096 0.041 Uiso 1 1 calc R . . H14B H 0.7584 0.9336 -0.2077 0.041 Uiso 1 1 calc R . . H14C H 0.8846 0.8857 -0.2440 0.041 Uiso 1 1 calc R . . C15 C 1.0881(3) 0.8915(2) -0.11896(14) 0.0280(6) Uani 1 1 d . . . H15A H 1.1258 0.8530 -0.1577 0.042 Uiso 1 1 calc R . . H15B H 1.1268 0.8677 -0.0734 0.042 Uiso 1 1 calc R . . H15C H 1.1083 0.9633 -0.1248 0.042 Uiso 1 1 calc R . . Fe1 Fe 0.84200(3) 0.71353(2) -0.102523(16) 0.01318(7) Uani 1 1 d . . . Fe2 Fe 0.56196(3) 0.80412(3) 0.086307(18) 0.01949(8) Uani 1 1 d . . . N1 N 0.70583(18) 0.72458(13) -0.18732(9) 0.0141(4) Uani 1 1 d . . . N2 N 0.5890(2) 0.78818(15) -0.09576(11) 0.0205(4) Uani 1 1 d . . . N3 N 0.8231(2) 0.65563(18) -0.27950(12) 0.0250(5) Uani 1 1 d . . . N4 N 1.0003(2) 0.65840(14) -0.15112(10) 0.0174(4) Uani 1 1 d . . . O1 O 0.69188(17) 0.77925(13) 0.01239(9) 0.0246(4) Uani 1 1 d . . . O2 O 0.99296(19) 0.71842(14) 0.03148(9) 0.0297(4) Uani 1 1 d . . . P1 P 0.76345(6) 0.55725(4) -0.07990(3) 0.01694(13) Uani 1 1 d . . . P2 P 0.91005(6) 0.87386(5) -0.12091(3) 0.01858(13) Uani 1 1 d . . . Br1 Br 0.62979(3) 0.684676(19) 0.179797(13) 0.02628(7) Uani 1 1 d . . . Br2 Br 0.56472(3) 0.97532(2) 0.129532(18) 0.04032(9) Uani 1 1 d . . . Br3 Br 0.34472(3) 0.76508(2) 0.028154(14) 0.02831(7) Uani 1 1 d . . . H2A H 0.519(3) 0.811(2) -0.0786(15) 0.026(8) Uiso 1 1 d . . . H3A H 0.887(3) 0.655(2) -0.2554(18) 0.036(9) Uiso 1 1 d . . . H3B H 0.824(3) 0.646(2) -0.3258(18) 0.039(9) 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 0.0174(12) 0.0161(11) 0.0157(11) 0.0009(9) 0.0020(9) -0.0036(9) C2 0.0265(13) 0.0198(12) 0.0166(12) 0.0007(9) -0.0043(10) -0.0046(10) C3 0.0224(13) 0.0235(12) 0.0245(13) 0.0016(10) -0.0104(11) -0.0007(10) C4 0.0194(13) 0.0204(12) 0.0282(14) -0.0002(10) -0.0026(11) 0.0045(10) C5 0.0200(12) 0.0164(11) 0.0187(12) -0.0003(9) 0.0002(10) -0.0004(9) C6 0.0190(12) 0.0180(11) 0.0169(12) -0.0016(9) 0.0034(10) -0.0001(9) C7 0.0164(12) 0.0204(12) 0.0201(12) 0.0021(9) 0.0031(10) 0.0006(9) C8 0.0202(13) 0.0232(12) 0.0183(12) 0.0045(9) -0.0006(10) -0.0003(10) C9 0.0252(15) 0.0464(17) 0.0355(16) 0.0087(13) 0.0113(13) 0.0139(13) C10 0.0338(15) 0.0194(12) 0.0238(13) -0.0020(10) 0.0034(11) -0.0001(11) C11 0.0206(13) 0.0266(14) 0.0418(16) 0.0033(12) -0.0017(12) -0.0070(11) C12 0.0390(16) 0.0247(13) 0.0184(12) 0.0036(10) 0.0017(12) -0.0054(12) C13 0.0408(17) 0.0242(13) 0.0326(15) -0.0091(11) 0.0067(13) -0.0031(12) C14 0.0337(15) 0.0217(13) 0.0266(14) 0.0049(10) -0.0036(12) -0.0006(11) C15 0.0240(14) 0.0309(14) 0.0291(14) 0.0010(11) -0.0005(11) -0.0070(11) Fe1 0.01246(16) 0.01611(16) 0.01099(15) 0.00000(12) 0.00057(12) 0.00104(12) Fe2 0.01881(18) 0.02243(18) 0.01763(17) -0.00307(13) 0.00527(14) 0.00142(14) N1 0.0145(9) 0.0162(9) 0.0115(9) -0.0007(7) -0.0001(7) 0.0008(7) N2 0.0146(10) 0.0267(11) 0.0204(11) -0.0047(8) 0.0015(8) 0.0074(9) N3 0.0182(12) 0.0434(14) 0.0134(11) -0.0056(9) 0.0004(9) 0.0010(10) N4 0.0191(11) 0.0193(10) 0.0137(9) 0.0004(8) 0.0010(8) 0.0005(8) O1 0.0226(9) 0.0362(10) 0.0153(8) -0.0049(7) 0.0051(7) 0.0027(8) O2 0.0288(10) 0.0411(11) 0.0186(9) 0.0012(8) -0.0074(8) -0.0025(8) P1 0.0181(3) 0.0175(3) 0.0152(3) 0.0008(2) 0.0003(2) -0.0008(2) P2 0.0207(3) 0.0180(3) 0.0169(3) -0.0005(2) -0.0005(2) -0.0009(2) Br1 0.02681(14) 0.02864(14) 0.02332(13) 0.00369(10) 0.00051(10) -0.00040(11) Br2 0.04650(19) 0.02045(14) 0.0546(2) -0.00816(12) 0.00895(15) -0.00339(12) Br3 0.01908(13) 0.03724(15) 0.02857(14) 0.00368(11) 0.00054(10) -0.00373(11) _geom_special_details ; All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s 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 N3 1.343(3) . ? C1 N1 1.363(3) . ? C1 C2 1.402(3) . ? C2 C3 1.361(4) . ? C2 H2 0.9500 . ? C3 C4 1.393(4) . ? C3 H3 0.9500 . ? C4 C5 1.379(3) . ? C4 H4 0.9500 . ? C5 N1 1.362(3) . ? C5 N2 1.380(3) . ? C6 O1 1.259(3) . ? C6 N2 1.362(3) . ? C6 Fe1 1.884(2) . ? C7 O2 1.141(3) . ? C7 Fe1 1.752(2) . ? C8 N4 1.129(3) . ? C8 C9 1.456(3) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 P1 1.815(2) . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 P1 1.812(3) . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C12 P1 1.818(2) . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? C13 P2 1.820(3) . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C14 P2 1.810(3) . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C15 P2 1.808(3) . ? C15 H15A 0.9800 . ? C15 H15B 0.9800 . ? C15 H15C 0.9800 . ? Fe1 N4 2.010(2) . ? Fe1 N1 2.0663(19) . ? Fe1 P2 2.2637(7) . ? Fe1 P1 2.2639(7) . ? Fe2 O1 1.9797(17) . ? Fe2 Br2 2.4102(4) . ? Fe2 Br1 2.4441(4) . ? Fe2 Br3 2.4602(4) . ? N2 H2A 0.85(3) . ? N3 H3A 0.77(3) . ? N3 H3B 0.88(3) . ? 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 N3 C1 N1 118.8(2) . . ? N3 C1 C2 119.4(2) . . ? N1 C1 C2 121.7(2) . . ? C3 C2 C1 120.0(2) . . ? C3 C2 H2 120.0 . . ? C1 C2 H2 120.0 . . ? C2 C3 C4 119.8(2) . . ? C2 C3 H3 120.1 . . ? C4 C3 H3 120.1 . . ? C5 C4 C3 117.4(2) . . ? C5 C4 H4 121.3 . . ? C3 C4 H4 121.3 . . ? N1 C5 C4 124.7(2) . . ? N1 C5 N2 113.4(2) . . ? C4 C5 N2 121.9(2) . . ? O1 C6 N2 118.2(2) . . ? O1 C6 Fe1 127.48(19) . . ? N2 C6 Fe1 114.31(16) . . ? O2 C7 Fe1 177.1(2) . . ? N4 C8 C9 179.7(3) . . ? C8 C9 H9A 109.5 . . ? C8 C9 H9B 109.5 . . ? H9A C9 H9B 109.5 . . ? C8 C9 H9C 109.5 . . ? H9A C9 H9C 109.5 . . ? H9B C9 H9C 109.5 . . ? P1 C10 H10A 109.5 . . ? P1 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? P1 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? P1 C11 H11A 109.5 . . ? P1 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? P1 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? P1 C12 H12A 109.5 . . ? P1 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? P1 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? P2 C13 H13A 109.5 . . ? P2 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? P2 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? P2 C14 H14A 109.5 . . ? P2 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? P2 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? P2 C15 H15A 109.5 . . ? P2 C15 H15B 109.5 . . ? H15A C15 H15B 109.5 . . ? P2 C15 H15C 109.5 . . ? H15A C15 H15C 109.5 . . ? H15B C15 H15C 109.5 . . ? C7 Fe1 C6 88.28(11) . . ? C7 Fe1 N4 89.39(9) . . ? C6 Fe1 N4 177.65(9) . . ? C7 Fe1 N1 169.80(9) . . ? C6 Fe1 N1 81.58(9) . . ? N4 Fe1 N1 100.75(7) . . ? C7 Fe1 P2 88.13(8) . . ? C6 Fe1 P2 89.06(7) . . ? N4 Fe1 P2 91.15(6) . . ? N1 Fe1 P2 90.60(5) . . ? C7 Fe1 P1 91.50(8) . . ? C6 Fe1 P1 87.26(7) . . ? N4 Fe1 P1 92.52(6) . . ? N1 Fe1 P1 89.12(5) . . ? P2 Fe1 P1 176.31(3) . . ? O1 Fe2 Br2 113.34(5) . . ? O1 Fe2 Br1 103.10(5) . . ? Br2 Fe2 Br1 111.532(17) . . ? O1 Fe2 Br3 104.70(5) . . ? Br2 Fe2 Br3 110.222(17) . . ? Br1 Fe2 Br3 113.632(16) . . ? C5 N1 C1 116.32(19) . . ? C5 N1 Fe1 111.36(14) . . ? C1 N1 Fe1 132.31(16) . . ? C6 N2 C5 119.2(2) . . ? C6 N2 H2A 121.4(19) . . ? C5 N2 H2A 119.2(19) . . ? C1 N3 H3A 120(2) . . ? C1 N3 H3B 115(2) . . ? H3A N3 H3B 123(3) . . ? C8 N4 Fe1 170.4(2) . . ? C6 O1 Fe2 141.10(17) . . ? C11 P1 C10 102.92(13) . . ? C11 P1 C12 102.13(13) . . ? C10 P1 C12 103.33(12) . . ? C11 P1 Fe1 116.38(9) . . ? C10 P1 Fe1 114.91(9) . . ? C12 P1 Fe1 115.30(9) . . ? C15 P2 C14 103.26(13) . . ? C15 P2 C13 104.13(13) . . ? C14 P2 C13 102.70(13) . . ? C15 P2 Fe1 115.13(9) . . ? C14 P2 Fe1 115.34(9) . . ? C13 P2 Fe1 114.68(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 C1 C2 C3 178.3(2) . . . . ? N1 C1 C2 C3 0.8(3) . . . . ? C1 C2 C3 C4 -0.7(4) . . . . ? C2 C3 C4 C5 0.4(4) . . . . ? C3 C4 C5 N1 -0.2(4) . . . . ? C3 C4 C5 N2 -178.9(2) . . . . ? O1 C6 Fe1 C7 -4.9(2) . . . . ? N2 C6 Fe1 C7 174.53(18) . . . . ? O1 C6 Fe1 N1 176.2(2) . . . . ? N2 C6 Fe1 N1 -4.37(17) . . . . ? O1 C6 Fe1 P2 -93.1(2) . . . . ? N2 C6 Fe1 P2 86.37(17) . . . . ? O1 C6 Fe1 P1 86.7(2) . . . . ? N2 C6 Fe1 P1 -93.89(17) . . . . ? C4 C5 N1 C1 0.2(3) . . . . ? N2 C5 N1 C1 179.07(19) . . . . ? C4 C5 N1 Fe1 179.81(19) . . . . ? N2 C5 N1 Fe1 -1.3(2) . . . . ? N3 C1 N1 C5 -178.1(2) . . . . ? C2 C1 N1 C5 -0.5(3) . . . . ? N3 C1 N1 Fe1 2.5(3) . . . . ? C2 C1 N1 Fe1 180.00(16) . . . . ? C7 Fe1 N1 C5 -3.0(6) . . . . ? C6 Fe1 N1 C5 3.17(16) . . . . ? N4 Fe1 N1 C5 -177.07(15) . . . . ? P2 Fe1 N1 C5 -85.79(15) . . . . ? P1 Fe1 N1 C5 90.54(15) . . . . ? C7 Fe1 N1 C1 176.5(5) . . . . ? C6 Fe1 N1 C1 -177.3(2) . . . . ? N4 Fe1 N1 C1 2.4(2) . . . . ? P2 Fe1 N1 C1 93.73(19) . . . . ? P1 Fe1 N1 C1 -89.95(19) . . . . ? O1 C6 N2 C5 -175.3(2) . . . . ? Fe1 C6 N2 C5 5.2(3) . . . . ? N1 C5 N2 C6 -2.4(3) . . . . ? C4 C5 N2 C6 176.5(2) . . . . ? N2 C6 O1 Fe2 16.1(4) . . . . ? Fe1 C6 O1 Fe2 -164.51(14) . . . . ? Br2 Fe2 O1 C6 -107.1(3) . . . . ? Br1 Fe2 O1 C6 132.2(3) . . . . ? Br3 Fe2 O1 C6 13.1(3) . . . . ? C7 Fe1 P1 C11 135.94(13) . . . . ? C6 Fe1 P1 C11 47.74(13) . . . . ? N4 Fe1 P1 C11 -134.60(12) . . . . ? N1 Fe1 P1 C11 -33.88(12) . . . . ? C7 Fe1 P1 C10 -103.70(12) . . . . ? C6 Fe1 P1 C10 168.10(12) . . . . ? N4 Fe1 P1 C10 -14.24(11) . . . . ? N1 Fe1 P1 C10 86.48(11) . . . . ? C7 Fe1 P1 C12 16.35(13) . . . . ? C6 Fe1 P1 C12 -71.85(13) . . . . ? N4 Fe1 P1 C12 105.81(12) . . . . ? N1 Fe1 P1 C12 -153.47(12) . . . . ? C7 Fe1 P2 C15 56.25(13) . . . . ? C6 Fe1 P2 C15 144.56(12) . . . . ? N4 Fe1 P2 C15 -33.10(11) . . . . ? N1 Fe1 P2 C15 -133.87(11) . . . . ? C7 Fe1 P2 C14 176.41(13) . . . . ? C6 Fe1 P2 C14 -95.28(13) . . . . ? N4 Fe1 P2 C14 87.06(12) . . . . ? N1 Fe1 P2 C14 -13.71(12) . . . . ? C7 Fe1 P2 C13 -64.56(14) . . . . ? C6 Fe1 P2 C13 23.75(13) . . . . ? N4 Fe1 P2 C13 -153.91(13) . . . . ? N1 Fe1 P2 C13 105.32(12) . . . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N2 H2A Br3 0.85(3) 2.79(3) 3.478(2) 139(2) . N3 H3A N4 0.77(3) 2.23(3) 2.944(3) 155(3) . _diffrn_measured_fraction_theta_max 0.990 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.990 _refine_diff_density_max 0.957 _refine_diff_density_min -0.586 _refine_diff_density_rms 0.078