# Electronic Supplementary Material (ESI) for Dalton Transactions # This journal is © The Royal Society of Chemistry 2012 data_publication_text _journal_name_full 'Dalton Trans.' _journal_coden_cambridge 0222 _publ_contact_author_name 'Christopher M. Kozak' _publ_contact_author_address ;Department of Chemistry Memorial University of Newfoundland St. John's, Newfoundland A1B 1J5 Canada ; _publ_contact_author_email ckozak@mun.ca _publ_contact_author_phone +1-709-864-8082 _publ_contact_author_fax +1-709-864-3702 loop_ _publ_author_name _publ_author_address C.M.Kozak ;Department of Chemistry Memorial University of Newfoundland St. John's, Newfoundland A1B 1J5 Canada ; R.K.Dean ;Department of Chemistry Memorial University of Newfoundland St. John's, Newfoundland A1B 1J5 Canada ; C.Fowler ;Department of Chemistry Memorial University of Newfoundland St. John's, Newfoundland A1B 1J5 Canada ; K.Hasan ;Department of Chemistry Memorial University of Newfoundland St. John's, Newfoundland A1B 1J5 Canada ; P.Kwong ;Department of Chemistry Memorial University of Newfoundland St. John's, Newfoundland A1B 1J5 Canada ; K.Kerman ;Department of Physical and Environmental Sciences University of Toronto at Scarborough Toronto, Ontario M1C 1A4 Canada ; ; H.-B.Kraatz ; ;Department of Physical and Environmental Sciences University of Toronto at Scarborough Toronto, Ontario M1C 1A4 Canada ; S.Trudel ;Department of Chemistry University of Calgary Calgary, Alberta T2N 1N4 Canada ; D.B.Leznoff ;Department of Chemistry Simon Fraser University Burnaby, British Columbia V5A 1S6 Canada ; L.N.Dawe ;Department of Chemistry and C-CART X-Ray Diffraction Laboratory Memorial University of Newfoundland St. Johns, NL, A1B 3X7, Canada ; _publ_section_title ; 'To Be Decided' ; data_H2[L4] _database_code_depnum_ccdc_archive 'CCDC 847891' _publ_section_abstract ; Please see full paper. ; # start Validation Reply Form _vrf_DIFMX01_H2L4 ; PROBLEM: The maximum difference density is > 0.1*ZMAX*2.00 RESPONSE: From the latest shelxl.lst: Electron density synthesis with coefficients Fo-Fc Highest peak 1.68 at 0.1612 0.0793 0.3763 [ 1.04 A from H1 ] Deepest hole -0.20 at 0.1516 0.9394 0.4213 [ 0.64 A from C27] Please see refine_special_details for more information. ; _vrf_PLAT094_H2L4 ; PROBLEM: Ratio of Maximum / Minimum Residual Density .... 8.20 RESPONSE: From the latest shelxl.lst: Electron density synthesis with coefficients Fo-Fc Highest peak 1.68 at 0.1612 0.0793 0.3763 [ 1.04 A from H1 ] Deepest hole -0.20 at 0.1516 0.9394 0.4213 [ 0.64 A from C27] Please see refine_special_details for more information. ; _vrf_PLAT097_H2L4 ; PROBLEM: Large Reported Max. (Positive) Residual Density 1.68 eA-3 RESPONSE: From the latest shelxl.lst: Electron density synthesis with coefficients Fo-Fc Highest peak 1.68 at 0.1612 0.0793 0.3763 [ 1.04 A from H1 ] Deepest hole -0.20 at 0.1516 0.9394 0.4213 [ 0.64 A from C27] Please see refine_special_details for more information. ; _vrf_DIFMX02_H2L4 ; PROBLEM: The maximum difference density is > 0.1*ZMAX*0.75 RESPONSE: From the latest shelxl.lst: Electron density synthesis with coefficients Fo-Fc Highest peak 1.68 at 0.1612 0.0793 0.3763 [ 1.04 A from H1 ] Deepest hole -0.20 at 0.1516 0.9394 0.4213 [ 0.64 A from C27] Please see refine_special_details for more information. ; _vrf_PLAT007_H2L4 ; PROBLEM: Note: Number of Unrefined D-H Atoms ............ 2 RESPONSE: These are alcoholic O-H atoms. The H-atoms were treated via shelxl AFIX 147. ; _vrf_PLAT380_H2L4 ; PROBLEM: Check Incorrectly? Oriented X(sp2)-Methyl Moiety C9 RESPONSE: The H-atoms on C9 (methyl protons) were treated via shelxl AFIX 137. ; # end Validation Reply Form _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C27 H41 N O3' _chemical_formula_sum 'C27 H41 N O3' _chemical_formula_weight 427.63 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 10.1430(8) _cell_length_b 11.1181(9) _cell_length_c 12.4742(11) _cell_angle_alpha 98.858(7) _cell_angle_beta 110.988(8) _cell_angle_gamma 100.462(7) _cell_volume 1254.3(2) _cell_formula_units_Z 2 _cell_measurement_temperature 138(2) _cell_measurement_reflns_used 9638 _cell_measurement_theta_min 3.0 _cell_measurement_theta_max 27.5 _exptl_crystal_description Irregular _exptl_crystal_colour Brown _exptl_crystal_size_max 0.42 _exptl_crystal_size_mid 0.38 _exptl_crystal_size_min 0.32 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.132 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 468 _exptl_absorpt_coefficient_mu 0.072 _exptl_absorpt_correction_type multi-scan _exptl_absorpt_process_details 'Jacobson, R. (1998) Private communication' _exptl_absorpt_correction_T_min 0.781 _exptl_absorpt_correction_T_max 0.977 _exptl_special_details ; ? ; _diffrn_ambient_temperature 138(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite - Rigaku SHINE' _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 12208 _diffrn_reflns_av_R_equivalents 0.0324 _diffrn_reflns_av_sigmaI/netI 0.0426 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 15 _diffrn_reflns_theta_min 3.04 _diffrn_reflns_theta_max 26.50 _reflns_number_total 5162 _reflns_number_gt 3875 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXL-97 (Acta Cryst., 2008, A64, 112-122)' _computing_structure_refinement 'SHELXL-97 (Acta Cryst., 2008, A64, 112-122)' _computing_molecular_graphics 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _computing_publication_material 'CrystalStructure3.7.0(Rigaku/MSC Inc.,2005)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. A .cif was previously prepared for this structure, however, upon journal submission and crystallographic review, re-examination of a partial occupancy water molecule, in the pocket of the organic structure, was requested. It exhibited very close contacts to adjacent molecues that were not considered reasonable, and so it has been removed from this model, and the following information, from the latest shelxl.lst, is given in its place: Electron density synthesis with coefficients Fo-Fc Highest peak 1.68 at 0.1612 0.0793 0.3763 [ 1.04 A from H1 ] Deepest hole -0.20 at 0.1516 0.9394 0.4213 [ 0.64 A from C27 ] Note that leaving this peak untreated was given very serious consideration and was investigated in the following ways: 1. The original absorption correction (face-indexed, numerical), was changed to a formula-corrected multi-scan correction. 2. Rigaku's TwinSolve did not identify any twin laws, nor did Platon's TwinRotMat. 3. Platon's ADDSYM does not indicate that there was any missed symmetry. 4. Platon's SOLV gives that the only potential solvent accessible void volume measures 10.3 A^3 (~30 A^3 is required to accomodate a single molecule of lattice solvent H2O). Further the Platon Squeeze gives that there are zero electrons/cell that have not been included in the model. 5. The disagreeable reflections were examined, but none were found to be statistically deviant. ; _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^)+(0.0978P)^2^+0.9425P] 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 291 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0914 _refine_ls_R_factor_gt 0.0709 _refine_ls_wR_factor_ref 0.2013 _refine_ls_wR_factor_gt 0.1859 _refine_ls_goodness_of_fit_ref 1.033 _refine_ls_restrained_S_all 1.033 _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 O1 O 0.75454(18) 0.78107(16) 0.52973(15) 0.0384(4) Uani 1 1 d . . . H1 H 0.7697 0.8306 0.5934 0.046 Uiso 1 1 calc R . . O2 O 1.01378(18) 0.95152(15) 0.77512(14) 0.0343(4) Uani 1 1 d . . . H2 H 0.9453 0.9873 0.7598 0.041 Uiso 1 1 calc R . . O3 O 0.8368(2) 1.11146(17) 0.67624(17) 0.0473(5) Uani 1 1 d . . . N1 N 0.6904(2) 0.89292(17) 0.71191(16) 0.0291(4) Uani 1 1 d . . . C1 C 0.6122(3) 0.7113(2) 0.4800(2) 0.0309(5) Uani 1 1 d . . . C2 C 0.5516(3) 0.6462(2) 0.3593(2) 0.0354(5) Uani 1 1 d . . . C3 C 0.6427(3) 0.6538(2) 0.2839(2) 0.0449(7) Uani 1 1 d . . . C4 C 0.7770(3) 0.6037(3) 0.3356(3) 0.0499(7) Uani 1 1 d . . . H4A H 0.8336 0.6098 0.2865 0.060 Uiso 1 1 calc R . . H4B H 0.7457 0.5155 0.3371 0.060 Uiso 1 1 calc R . . H4C H 0.8377 0.6538 0.4162 0.060 Uiso 1 1 calc R . . C5 C 0.6902(4) 0.7908(3) 0.2765(3) 0.0601(9) Uani 1 1 d . . . H5A H 0.7538 0.8431 0.3557 0.072 Uiso 1 1 calc R . . H5B H 0.6036 0.8226 0.2443 0.072 Uiso 1 1 calc R . . H5C H 0.7435 0.7940 0.2247 0.072 Uiso 1 1 calc R . . C6 C 0.5539(4) 0.5749(3) 0.1563(2) 0.0588(8) Uani 1 1 d . . . H6A H 0.4657 0.6035 0.1210 0.071 Uiso 1 1 calc R . . H6B H 0.5261 0.4859 0.1570 0.071 Uiso 1 1 calc R . . H6C H 0.6134 0.5849 0.1097 0.071 Uiso 1 1 calc R . . C7 C 0.4078(3) 0.5738(2) 0.3140(2) 0.0388(6) Uani 1 1 d . . . H7 H 0.3651 0.5287 0.2335 0.047 Uiso 1 1 calc R . . C8 C 0.3229(3) 0.5639(2) 0.3804(2) 0.0371(6) Uani 1 1 d . . . C9 C 0.1684(3) 0.4814(3) 0.3283(3) 0.0504(7) Uani 1 1 d . . . H9A H 0.1417 0.4422 0.2449 0.061 Uiso 1 1 calc R . . H9B H 0.1014 0.5328 0.3345 0.061 Uiso 1 1 calc R . . H9C H 0.1620 0.4157 0.3716 0.061 Uiso 1 1 calc R . . C10 C 0.3865(3) 0.6303(2) 0.4981(2) 0.0332(5) Uani 1 1 d . . . H10 H 0.3305 0.6253 0.5449 0.040 Uiso 1 1 calc R . . C11 C 0.5295(2) 0.7037(2) 0.54897(19) 0.0291(5) Uani 1 1 d . . . C12 C 0.5969(2) 0.7636(2) 0.67975(19) 0.0307(5) Uani 1 1 d . . . H12A H 0.5177 0.7654 0.7082 0.037 Uiso 1 1 calc R . . H12B H 0.6562 0.7104 0.7212 0.037 Uiso 1 1 calc R . . C13 C 0.7706(2) 0.9346(2) 0.84191(19) 0.0317(5) Uani 1 1 d . . . H13A H 0.7006 0.9209 0.8802 0.038 Uiso 1 1 calc R . . H13B H 0.8182 1.0259 0.8640 0.038 Uiso 1 1 calc R . . C14 C 0.8849(2) 0.8638(2) 0.88625(18) 0.0284(5) Uani 1 1 d . . . C15 C 0.8770(2) 0.7875(2) 0.96290(19) 0.0318(5) Uani 1 1 d . . . H15 H 0.7983 0.7801 0.9878 0.038 Uiso 1 1 calc R . . C16 C 0.9812(3) 0.7219(2) 1.0040(2) 0.0328(5) Uani 1 1 d . . . C17 C 0.9709(3) 0.6393(3) 1.0878(2) 0.0444(6) Uani 1 1 d . . . H17A H 0.9721 0.6902 1.1597 0.053 Uiso 1 1 calc R . . H17B H 1.0542 0.6017 1.1083 0.053 Uiso 1 1 calc R . . H17C H 0.8798 0.5723 1.0496 0.053 Uiso 1 1 calc R . . C18 C 1.0941(2) 0.7334(2) 0.96486(19) 0.0300(5) Uani 1 1 d . . . H18 H 1.1654 0.6879 0.9920 0.036 Uiso 1 1 calc R . . C19 C 1.1081(2) 0.8091(2) 0.88702(18) 0.0266(5) Uani 1 1 d . . . C20 C 1.2322(2) 0.8167(2) 0.8435(2) 0.0311(5) Uani 1 1 d . . . C21 C 1.3390(3) 0.7415(3) 0.9018(3) 0.0438(6) Uani 1 1 d . . . H21A H 1.3823 0.7750 0.9877 0.053 Uiso 1 1 calc R . . H21B H 1.4165 0.7486 0.8718 0.053 Uiso 1 1 calc R . . H21C H 1.2865 0.6527 0.8830 0.053 Uiso 1 1 calc R . . C22 C 1.3211(3) 0.9538(2) 0.8738(3) 0.0425(6) Uani 1 1 d . . . H22A H 1.2575 1.0042 0.8344 0.051 Uiso 1 1 calc R . . H22B H 1.4010 0.9569 0.8467 0.051 Uiso 1 1 calc R . . H22C H 1.3617 0.9879 0.9596 0.051 Uiso 1 1 calc R . . C23 C 1.1686(3) 0.7627(3) 0.7091(2) 0.0448(6) Uani 1 1 d . . . H23A H 1.1208 0.6728 0.6908 0.054 Uiso 1 1 calc R . . H23B H 1.2476 0.7736 0.6808 0.054 Uiso 1 1 calc R . . H23C H 1.0970 0.8071 0.6699 0.054 Uiso 1 1 calc R . . C24 C 1.0012(2) 0.8752(2) 0.84917(18) 0.0268(5) Uani 1 1 d . . . C25 C 0.6069(3) 0.9801(2) 0.6629(2) 0.0362(5) Uani 1 1 d . . . H25A H 0.5325 0.9844 0.6965 0.043 Uiso 1 1 calc R . . H25B H 0.5549 0.9471 0.5762 0.043 Uiso 1 1 calc R . . C26 C 0.7026(3) 1.1125(2) 0.6885(2) 0.0433(6) Uani 1 1 d . . . H26A H 0.6485 1.1589 0.6336 0.052 Uiso 1 1 calc R . . H26B H 0.7239 1.1577 0.7700 0.052 Uiso 1 1 calc R . . C27 C 0.8302(4) 1.1082(3) 0.5610(3) 0.0606(8) Uani 1 1 d . . . H27A H 0.7551 1.0338 0.5057 0.073 Uiso 1 1 calc R . . H27B H 0.9252 1.1044 0.5592 0.073 Uiso 1 1 calc R . . H27C H 0.8059 1.1844 0.5379 0.073 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 O1 0.0401(9) 0.0395(10) 0.0377(9) 0.0026(7) 0.0223(8) 0.0064(7) O2 0.0359(9) 0.0397(9) 0.0365(9) 0.0179(7) 0.0187(7) 0.0154(7) O3 0.0482(11) 0.0446(10) 0.0507(11) 0.0171(9) 0.0183(9) 0.0140(9) N1 0.0295(10) 0.0301(10) 0.0269(9) 0.0038(8) 0.0107(8) 0.0094(8) C1 0.0402(13) 0.0270(11) 0.0300(12) 0.0075(9) 0.0172(10) 0.0119(9) C2 0.0548(15) 0.0286(11) 0.0293(12) 0.0094(10) 0.0193(11) 0.0188(11) C3 0.0767(19) 0.0388(14) 0.0339(13) 0.0118(11) 0.0329(13) 0.0244(13) C4 0.072(2) 0.0501(16) 0.0494(16) 0.0173(13) 0.0415(15) 0.0274(14) C5 0.105(3) 0.0473(16) 0.0617(19) 0.0275(15) 0.0603(19) 0.0311(17) C6 0.094(2) 0.0610(19) 0.0349(15) 0.0122(13) 0.0328(16) 0.0354(18) C7 0.0573(16) 0.0285(12) 0.0259(11) 0.0043(9) 0.0096(11) 0.0160(11) C8 0.0422(14) 0.0242(11) 0.0343(13) 0.0050(10) 0.0042(10) 0.0076(10) C9 0.0484(16) 0.0382(14) 0.0451(15) 0.0045(12) 0.0025(13) 0.0025(12) C10 0.0365(12) 0.0292(12) 0.0343(12) 0.0084(10) 0.0140(10) 0.0090(10) C11 0.0335(12) 0.0264(11) 0.0264(11) 0.0049(9) 0.0111(9) 0.0086(9) C12 0.0320(12) 0.0328(12) 0.0268(11) 0.0042(9) 0.0140(9) 0.0048(9) C13 0.0319(12) 0.0349(12) 0.0269(11) 0.0016(9) 0.0121(9) 0.0090(10) C14 0.0282(11) 0.0307(11) 0.0226(10) 0.0004(9) 0.0092(9) 0.0059(9) C15 0.0319(12) 0.0357(12) 0.0262(11) 0.0020(9) 0.0144(9) 0.0033(10) C16 0.0406(13) 0.0297(11) 0.0251(11) 0.0040(9) 0.0136(10) 0.0029(10) C17 0.0544(16) 0.0452(15) 0.0403(14) 0.0174(12) 0.0247(12) 0.0101(12) C18 0.0331(12) 0.0280(11) 0.0250(11) 0.0047(9) 0.0084(9) 0.0068(9) C19 0.0271(11) 0.0255(10) 0.0225(10) 0.0001(8) 0.0091(8) 0.0023(8) C20 0.0302(11) 0.0344(12) 0.0311(12) 0.0087(10) 0.0138(9) 0.0099(9) C21 0.0426(14) 0.0522(16) 0.0504(16) 0.0207(13) 0.0252(12) 0.0238(12) C22 0.0322(13) 0.0431(14) 0.0556(16) 0.0128(12) 0.0218(12) 0.0073(11) C23 0.0420(14) 0.0630(17) 0.0344(13) 0.0069(12) 0.0213(11) 0.0166(13) C24 0.0304(11) 0.0278(11) 0.0203(10) 0.0046(8) 0.0091(8) 0.0055(9) C25 0.0351(12) 0.0375(13) 0.0338(12) 0.0045(10) 0.0095(10) 0.0163(10) C26 0.0487(15) 0.0359(13) 0.0416(14) 0.0067(11) 0.0113(12) 0.0178(12) C27 0.072(2) 0.066(2) 0.0531(18) 0.0224(16) 0.0269(16) 0.0267(17) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag O1 C1 1.369(3) . ? O1 H1 0.8400 . ? O2 C24 1.370(3) . ? O2 H2 0.8400 . ? O3 C27 1.410(4) . ? O3 C26 1.425(3) . ? N1 C25 1.463(3) . ? N1 C12 1.477(3) . ? N1 C13 1.481(3) . ? C1 C11 1.402(3) . ? C1 C2 1.417(3) . ? C2 C7 1.393(4) . ? C2 C3 1.537(3) . ? C3 C4 1.529(4) . ? C3 C5 1.539(4) . ? C3 C6 1.540(4) . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C4 H4C 0.9800 . ? C5 H5A 0.9800 . ? C5 H5B 0.9800 . ? C5 H5C 0.9800 . ? C6 H6A 0.9800 . ? C6 H6B 0.9800 . ? C6 H6C 0.9800 . ? C7 C8 1.393(4) . ? C7 H7 0.9500 . ? C8 C10 1.390(3) . ? C8 C9 1.511(4) . ? C9 H9A 0.9800 . ? C9 H9B 0.9800 . ? C9 H9C 0.9800 . ? C10 C11 1.387(3) . ? C10 H10 0.9500 . ? C11 C12 1.508(3) . ? C12 H12A 0.9900 . ? C12 H12B 0.9900 . ? C13 C14 1.509(3) . ? C13 H13A 0.9900 . ? C13 H13B 0.9900 . ? C14 C15 1.386(3) . ? C14 C24 1.405(3) . ? C15 C16 1.386(3) . ? C15 H15 0.9500 . ? C16 C18 1.391(3) . ? C16 C17 1.511(3) . ? C17 H17A 0.9800 . ? C17 H17B 0.9800 . ? C17 H17C 0.9800 . ? C18 C19 1.406(3) . ? C18 H18 0.9500 . ? C19 C24 1.403(3) . ? C19 C20 1.533(3) . ? C20 C21 1.535(3) . ? C20 C22 1.536(3) . ? C20 C23 1.537(3) . ? C21 H21A 0.9800 . ? C21 H21B 0.9800 . ? C21 H21C 0.9800 . ? C22 H22A 0.9800 . ? C22 H22B 0.9800 . ? C22 H22C 0.9800 . ? C23 H23A 0.9800 . ? C23 H23B 0.9800 . ? C23 H23C 0.9800 . ? C25 C26 1.525(4) . ? C25 H25A 0.9900 . ? C25 H25B 0.9900 . ? C26 H26A 0.9900 . ? C26 H26B 0.9900 . ? C27 H27A 0.9800 . ? C27 H27B 0.9800 . ? C27 H27C 0.9800 . ? 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 C1 O1 H1 109.5 . . ? C24 O2 H2 109.5 . . ? C27 O3 C26 114.5(2) . . ? C25 N1 C12 111.85(18) . . ? C25 N1 C13 112.57(17) . . ? C12 N1 C13 109.80(17) . . ? O1 C1 C11 119.9(2) . . ? O1 C1 C2 119.1(2) . . ? C11 C1 C2 121.1(2) . . ? C7 C2 C1 116.7(2) . . ? C7 C2 C3 122.2(2) . . ? C1 C2 C3 121.0(2) . . ? C4 C3 C2 110.8(2) . . ? C4 C3 C5 110.0(3) . . ? C2 C3 C5 110.1(2) . . ? C4 C3 C6 107.4(2) . . ? C2 C3 C6 111.5(3) . . ? C5 C3 C6 107.0(2) . . ? 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 . . ? C3 C5 H5A 109.5 . . ? C3 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? C3 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? C3 C6 H6A 109.5 . . ? C3 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? C3 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? C2 C7 C8 123.6(2) . . ? C2 C7 H7 118.2 . . ? C8 C7 H7 118.2 . . ? C10 C8 C7 117.7(2) . . ? C10 C8 C9 120.6(2) . . ? C7 C8 C9 121.7(2) . . ? 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 . . ? C11 C10 C8 121.7(2) . . ? C11 C10 H10 119.2 . . ? C8 C10 H10 119.2 . . ? C10 C11 C1 119.2(2) . . ? C10 C11 C12 119.2(2) . . ? C1 C11 C12 121.3(2) . . ? N1 C12 C11 114.21(18) . . ? N1 C12 H12A 108.7 . . ? C11 C12 H12A 108.7 . . ? N1 C12 H12B 108.7 . . ? C11 C12 H12B 108.7 . . ? H12A C12 H12B 107.6 . . ? N1 C13 C14 111.42(17) . . ? N1 C13 H13A 109.3 . . ? C14 C13 H13A 109.3 . . ? N1 C13 H13B 109.3 . . ? C14 C13 H13B 109.3 . . ? H13A C13 H13B 108.0 . . ? C15 C14 C24 119.4(2) . . ? C15 C14 C13 121.0(2) . . ? C24 C14 C13 119.54(19) . . ? C14 C15 C16 121.6(2) . . ? C14 C15 H15 119.2 . . ? C16 C15 H15 119.2 . . ? C15 C16 C18 117.9(2) . . ? C15 C16 C17 120.8(2) . . ? C18 C16 C17 121.3(2) . . ? C16 C17 H17A 109.5 . . ? C16 C17 H17B 109.5 . . ? H17A C17 H17B 109.5 . . ? C16 C17 H17C 109.5 . . ? H17A C17 H17C 109.5 . . ? H17B C17 H17C 109.5 . . ? C16 C18 C19 123.2(2) . . ? C16 C18 H18 118.4 . . ? C19 C18 H18 118.4 . . ? C24 C19 C18 116.76(19) . . ? C24 C19 C20 121.62(19) . . ? C18 C19 C20 121.6(2) . . ? C19 C20 C21 111.90(19) . . ? C19 C20 C22 110.53(18) . . ? C21 C20 C22 107.0(2) . . ? C19 C20 C23 109.78(19) . . ? C21 C20 C23 107.8(2) . . ? C22 C20 C23 109.7(2) . . ? C20 C21 H21A 109.5 . . ? C20 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C20 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C20 C22 H22A 109.5 . . ? C20 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C20 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? C20 C23 H23A 109.5 . . ? C20 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C20 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? O2 C24 C19 117.94(19) . . ? O2 C24 C14 120.98(19) . . ? C19 C24 C14 121.08(19) . . ? N1 C25 C26 112.8(2) . . ? N1 C25 H25A 109.0 . . ? C26 C25 H25A 109.0 . . ? N1 C25 H25B 109.0 . . ? C26 C25 H25B 109.0 . . ? H25A C25 H25B 107.8 . . ? O3 C26 C25 112.4(2) . . ? O3 C26 H26A 109.1 . . ? C25 C26 H26A 109.1 . . ? O3 C26 H26B 109.1 . . ? C25 C26 H26B 109.1 . . ? H26A C26 H26B 107.9 . . ? O3 C27 H27A 109.5 . . ? O3 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? O3 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? 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 O1 C1 C2 C7 178.2(2) . . . . ? C11 C1 C2 C7 -0.8(3) . . . . ? O1 C1 C2 C3 -0.5(3) . . . . ? C11 C1 C2 C3 -179.5(2) . . . . ? C7 C2 C3 C4 -118.5(3) . . . . ? C1 C2 C3 C4 60.1(3) . . . . ? C7 C2 C3 C5 119.5(3) . . . . ? C1 C2 C3 C5 -61.8(3) . . . . ? C7 C2 C3 C6 1.0(3) . . . . ? C1 C2 C3 C6 179.7(2) . . . . ? C1 C2 C7 C8 0.5(3) . . . . ? C3 C2 C7 C8 179.3(2) . . . . ? C2 C7 C8 C10 0.0(3) . . . . ? C2 C7 C8 C9 -178.4(2) . . . . ? C7 C8 C10 C11 -0.4(3) . . . . ? C9 C8 C10 C11 178.1(2) . . . . ? C8 C10 C11 C1 0.1(3) . . . . ? C8 C10 C11 C12 -174.3(2) . . . . ? O1 C1 C11 C10 -178.5(2) . . . . ? C2 C1 C11 C10 0.5(3) . . . . ? O1 C1 C11 C12 -4.3(3) . . . . ? C2 C1 C11 C12 174.8(2) . . . . ? C25 N1 C12 C11 63.9(2) . . . . ? C13 N1 C12 C11 -170.39(18) . . . . ? C10 C11 C12 N1 -140.5(2) . . . . ? C1 C11 C12 N1 45.2(3) . . . . ? C25 N1 C13 C14 -165.13(19) . . . . ? C12 N1 C13 C14 69.6(2) . . . . ? N1 C13 C14 C15 -117.3(2) . . . . ? N1 C13 C14 C24 62.7(3) . . . . ? C24 C14 C15 C16 -0.1(3) . . . . ? C13 C14 C15 C16 179.9(2) . . . . ? C14 C15 C16 C18 -0.8(3) . . . . ? C14 C15 C16 C17 179.9(2) . . . . ? C15 C16 C18 C19 0.7(3) . . . . ? C17 C16 C18 C19 180.0(2) . . . . ? C16 C18 C19 C24 0.2(3) . . . . ? C16 C18 C19 C20 -178.5(2) . . . . ? C24 C19 C20 C21 177.3(2) . . . . ? C18 C19 C20 C21 -4.1(3) . . . . ? C24 C19 C20 C22 58.1(3) . . . . ? C18 C19 C20 C22 -123.2(2) . . . . ? C24 C19 C20 C23 -63.0(3) . . . . ? C18 C19 C20 C23 115.7(2) . . . . ? C18 C19 C24 O2 178.77(18) . . . . ? C20 C19 C24 O2 -2.5(3) . . . . ? C18 C19 C24 C14 -1.1(3) . . . . ? C20 C19 C24 C14 177.62(19) . . . . ? C15 C14 C24 O2 -178.84(19) . . . . ? C13 C14 C24 O2 1.2(3) . . . . ? C15 C14 C24 C19 1.0(3) . . . . ? C13 C14 C24 C19 -178.90(19) . . . . ? C12 N1 C25 C26 -176.47(19) . . . . ? C13 N1 C25 C26 59.4(3) . . . . ? C27 O3 C26 C25 88.2(3) . . . . ? N1 C25 C26 O3 40.8(3) . . . . ? _diffrn_measured_fraction_theta_max 0.993 _diffrn_reflns_theta_full 26.50 _diffrn_measured_fraction_theta_full 0.993 _refine_diff_density_max 1.682 _refine_diff_density_min -0.205 _refine_diff_density_rms 0.056 #===END data_1b _database_code_depnum_ccdc_archive 'CCDC 847892' _publ_section_abstract ; Please see full paper. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C35 H53 Br Fe N O3' _chemical_formula_sum 'C35 H53 Br Fe N O3' _chemical_formula_weight 671.56 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 'P 1 21/c 1' _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 14.923(13) _cell_length_b 11.6563(10) _cell_length_c 19.772(17) _cell_angle_alpha 90.00 _cell_angle_beta 104.059(11) _cell_angle_gamma 90.00 _cell_volume 3336(4) _cell_formula_units_Z 4 _cell_measurement_temperature 173(2) _cell_measurement_reflns_used 9877 _cell_measurement_theta_min 2.0 _cell_measurement_theta_max 30.1 _exptl_crystal_description Chunk _exptl_crystal_colour Black _exptl_crystal_size_max 0.53 _exptl_crystal_size_mid 0.34 _exptl_crystal_size_min 0.34 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.337 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1420 _exptl_absorpt_coefficient_mu 1.684 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_max 0.738 _exptl_absorpt_correction_T_min 0.520 _exptl_absorpt_process_details '(T. Higashi, 2000)' _exptl_special_details ; ? ; _diffrn_ambient_temperature 173(2) _diffrn_radiation_wavelength 0.71075 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator 'graphite - Rigaku SHINE' _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 28109 _diffrn_reflns_av_R_equivalents 0.0805 _diffrn_reflns_av_sigmaI/netI 0.0475 _diffrn_reflns_limit_h_min -18 _diffrn_reflns_limit_h_max 18 _diffrn_reflns_limit_k_min -14 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.62 _diffrn_reflns_theta_max 26.49 _reflns_number_total 6865 _reflns_number_gt 6022 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)' _computing_cell_refinement 'CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)' _computing_data_reduction 'CrystalClear-SM Expert 2.0 r4 (Rigaku, 2009)' _computing_structure_solution 'SHELXS-97 (Acta Cryst. 2008. A64, 112-122)' _computing_structure_refinement 'SHELXL-97 (Acta Cryst. 2008. A64, 112-122)' _computing_molecular_graphics 'CrystalStructure 4.0 (Rigaku, 2010)' _computing_publication_material 'CrystalStructure 4.0 (Rigaku, 2010)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.1274P)^2^+5.2296P] 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 6865 _refine_ls_number_parameters 382 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0862 _refine_ls_R_factor_gt 0.0775 _refine_ls_wR_factor_ref 0.2220 _refine_ls_wR_factor_gt 0.2126 _refine_ls_goodness_of_fit_ref 1.093 _refine_ls_restrained_S_all 1.093 _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 Br1 Br 1.00842(3) 0.51531(4) 0.27723(2) 0.04903(19) Uani 1 1 d . . . Fe1 Fe 0.90383(4) 0.44888(5) 0.34395(3) 0.03448(19) Uani 1 1 d . . . O1 O 0.90911(19) 0.5807(2) 0.39603(14) 0.0366(6) Uani 1 1 d . . . O2 O 0.7991(2) 0.4160(2) 0.27754(14) 0.0371(6) Uani 1 1 d . . . O3 O 0.9877(2) 0.3128(3) 0.37910(16) 0.0417(7) Uani 1 1 d . . . C1 C 0.8462(3) 0.6207(3) 0.42790(19) 0.0341(8) Uani 1 1 d . . . C2 C 0.8061(3) 0.7289(3) 0.41271(19) 0.0341(8) Uani 1 1 d . . . C3 C 0.8344(3) 0.8068(4) 0.3595(2) 0.0390(9) Uani 1 1 d . . . C4 C 0.8020(3) 0.7566(4) 0.2866(2) 0.0463(10) Uani 1 1 d . . . H4A H 0.7346 0.7490 0.2748 0.056 Uiso 1 1 calc R . . H4B H 0.8301 0.6809 0.2852 0.056 Uiso 1 1 calc R . . H4C H 0.8204 0.8076 0.2529 0.056 Uiso 1 1 calc R . . C5 C 0.9398(3) 0.8219(4) 0.3758(2) 0.0426(9) Uani 1 1 d . . . H5A H 0.9560 0.8707 0.3402 0.051 Uiso 1 1 calc R . . H5B H 0.9692 0.7467 0.3760 0.051 Uiso 1 1 calc R . . H5C H 0.9614 0.8579 0.4217 0.051 Uiso 1 1 calc R . . C6 C 0.7920(3) 0.9266(4) 0.3582(3) 0.0482(10) Uani 1 1 d . . . H6A H 0.7245 0.9205 0.3453 0.058 Uiso 1 1 calc R . . H6B H 0.8124 0.9744 0.3240 0.058 Uiso 1 1 calc R . . H6C H 0.8119 0.9615 0.4045 0.058 Uiso 1 1 calc R . . C7 C 0.7378(3) 0.7597(3) 0.4459(2) 0.0359(8) Uani 1 1 d . . . H7 H 0.7094 0.8326 0.4353 0.043 Uiso 1 1 calc R . . C8 C 0.7084(3) 0.6912(3) 0.4938(2) 0.0358(8) Uani 1 1 d . . . C9 C 0.6314(3) 0.7233(4) 0.5277(2) 0.0390(8) Uani 1 1 d . . . C10 C 0.5855(3) 0.8359(4) 0.4991(2) 0.0467(10) Uani 1 1 d . . . H10A H 0.6320 0.8970 0.5062 0.056 Uiso 1 1 calc R . . H10B H 0.5377 0.8555 0.5234 0.056 Uiso 1 1 calc R . . H10C H 0.5573 0.8276 0.4491 0.056 Uiso 1 1 calc R . . C11 C 0.6689(3) 0.7354(4) 0.6062(2) 0.0473(10) Uani 1 1 d . . . H11A H 0.6955 0.6621 0.6257 0.057 Uiso 1 1 calc R . . H11B H 0.6185 0.7570 0.6276 0.057 Uiso 1 1 calc R . . H11C H 0.7167 0.7948 0.6159 0.057 Uiso 1 1 calc R . . C12 C 0.5578(3) 0.6310(4) 0.5134(2) 0.0476(10) Uani 1 1 d . . . H12A H 0.5321 0.6243 0.4630 0.057 Uiso 1 1 calc R . . H12B H 0.5085 0.6514 0.5361 0.057 Uiso 1 1 calc R . . H12C H 0.5852 0.5575 0.5318 0.057 Uiso 1 1 calc R . . C13 C 0.7524(3) 0.5855(3) 0.50914(19) 0.0348(8) Uani 1 1 d . . . H13 H 0.7359 0.5370 0.5428 0.042 Uiso 1 1 calc R . . C14 C 0.8194(3) 0.5500(3) 0.4764(2) 0.0348(8) Uani 1 1 d . . . C15 C 0.8588(3) 0.4325(3) 0.4876(2) 0.0359(8) Uani 1 1 d . . . H15A H 0.8339 0.3929 0.5234 0.043 Uiso 1 1 calc R . . H15B H 0.9267 0.4374 0.5049 0.043 Uiso 1 1 calc R . . C16 C 0.7346(3) 0.3638(3) 0.3943(2) 0.0368(8) Uani 1 1 d . . . H16A H 0.7125 0.4440 0.3873 0.044 Uiso 1 1 calc R . . H16B H 0.7061 0.3286 0.4296 0.044 Uiso 1 1 calc R . . C17 C 0.7026(3) 0.3007(3) 0.3275(2) 0.0357(8) Uani 1 1 d . . . C18 C 0.6377(3) 0.2154(3) 0.3212(2) 0.0384(8) Uani 1 1 d . . . H18 H 0.6172 0.1931 0.3611 0.046 Uiso 1 1 calc R . . C19 C 0.6014(3) 0.1610(3) 0.2586(2) 0.0375(8) Uani 1 1 d . . . C20 C 0.5251(3) 0.0715(4) 0.2490(2) 0.0401(9) Uani 1 1 d . . . C21 C 0.4345(4) 0.1254(5) 0.2116(3) 0.0609(13) Uani 1 1 d . . . H21A H 0.4400 0.1560 0.1666 0.073 Uiso 1 1 calc R . . H21B H 0.4192 0.1878 0.2400 0.073 Uiso 1 1 calc R . . H21C H 0.3856 0.0674 0.2038 0.073 Uiso 1 1 calc R . . C22 C 0.5156(4) 0.0233(5) 0.3186(3) 0.0551(12) Uani 1 1 d . . . H22A H 0.4943 0.0840 0.3453 0.066 Uiso 1 1 calc R . . H22B H 0.5756 -0.0054 0.3451 0.066 Uiso 1 1 calc R . . H22C H 0.4707 -0.0397 0.3103 0.066 Uiso 1 1 calc R . . C23 C 0.5455(4) -0.0290(4) 0.2060(3) 0.0490(11) Uani 1 1 d . . . H23A H 0.5023 -0.0917 0.2077 0.059 Uiso 1 1 calc R . . H23B H 0.6089 -0.0555 0.2251 0.059 Uiso 1 1 calc R . . H23C H 0.5383 -0.0045 0.1575 0.059 Uiso 1 1 calc R . . C24 C 0.6330(3) 0.1976(4) 0.2019(2) 0.0382(8) Uani 1 1 d . . . H24 H 0.6076 0.1626 0.1581 0.046 Uiso 1 1 calc R . . C25 C 0.6993(3) 0.2819(4) 0.2050(2) 0.0367(8) Uani 1 1 d . . . C26 C 0.7334(3) 0.3164(4) 0.1412(2) 0.0373(8) Uani 1 1 d . . . C27 C 0.6828(3) 0.2531(5) 0.0763(2) 0.0485(10) Uani 1 1 d . . . H27A H 0.7087 0.2748 0.0371 0.058 Uiso 1 1 calc R . . H27B H 0.6171 0.2732 0.0656 0.058 Uiso 1 1 calc R . . H27C H 0.6898 0.1702 0.0842 0.058 Uiso 1 1 calc R . . C28 C 0.8357(3) 0.2904(5) 0.1528(2) 0.0486(10) Uani 1 1 d . . . H28A H 0.8560 0.3092 0.1105 0.058 Uiso 1 1 calc R . . H28B H 0.8465 0.2087 0.1635 0.058 Uiso 1 1 calc R . . H28C H 0.8707 0.3364 0.1919 0.058 Uiso 1 1 calc R . . C29 C 0.7166(3) 0.4434(4) 0.1271(2) 0.0470(10) Uani 1 1 d . . . H29A H 0.7458 0.4871 0.1690 0.056 Uiso 1 1 calc R . . H29B H 0.6500 0.4585 0.1148 0.056 Uiso 1 1 calc R . . H29C H 0.7432 0.4667 0.0885 0.056 Uiso 1 1 calc R . . C30 C 0.7351(3) 0.3336(3) 0.2698(2) 0.0354(8) Uani 1 1 d . . . C31 C 0.8722(3) 0.2478(3) 0.4327(2) 0.0386(8) Uani 1 1 d . . . H31A H 0.8390 0.1984 0.3940 0.046 Uiso 1 1 calc R . . H31B H 0.8608 0.2172 0.4766 0.046 Uiso 1 1 calc R . . C32 C 0.9729(3) 0.2435(4) 0.4366(2) 0.0438(9) Uani 1 1 d . . . H32 H 1.0092 0.2745 0.4822 0.053 Uiso 1 1 calc R . . C33 C 1.0090(3) 0.1274(4) 0.4223(3) 0.0492(10) Uani 1 1 d . . . H33A H 1.0277 0.0814 0.4656 0.059 Uiso 1 1 calc R . . H33B H 0.9623 0.0843 0.3875 0.059 Uiso 1 1 calc R . . C34 C 1.0905(3) 0.1582(4) 0.3945(3) 0.0506(11) Uani 1 1 d . . . H34A H 1.1449 0.1763 0.4329 0.061 Uiso 1 1 calc R . . H34B H 1.1066 0.0948 0.3664 0.061 Uiso 1 1 calc R . . C35 C 1.0593(3) 0.2616(4) 0.3504(3) 0.0507(11) Uani 1 1 d . . . H35A H 1.1111 0.3158 0.3531 0.061 Uiso 1 1 calc R . . H35B H 1.0343 0.2394 0.3011 0.061 Uiso 1 1 calc R . . N1 N 0.8359(2) 0.3649(3) 0.42176(16) 0.0343(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 Br1 0.0578(3) 0.0426(3) 0.0537(3) -0.00133(17) 0.0271(2) -0.00538(19) Fe1 0.0392(3) 0.0299(3) 0.0354(3) -0.0012(2) 0.0112(2) -0.0031(2) O1 0.0397(14) 0.0298(13) 0.0414(15) -0.0013(11) 0.0124(11) -0.0011(11) O2 0.0431(15) 0.0340(14) 0.0341(13) -0.0009(11) 0.0088(11) -0.0087(12) O3 0.0410(15) 0.0373(15) 0.0506(16) 0.0053(12) 0.0186(12) 0.0065(12) C1 0.0374(18) 0.0326(18) 0.0331(18) -0.0022(14) 0.0099(14) -0.0018(15) C2 0.0401(19) 0.0322(18) 0.0299(17) -0.0028(14) 0.0080(14) -0.0010(15) C3 0.042(2) 0.036(2) 0.038(2) 0.0050(16) 0.0099(16) -0.0005(17) C4 0.051(2) 0.049(2) 0.038(2) 0.0063(18) 0.0095(17) -0.003(2) C5 0.040(2) 0.041(2) 0.050(2) 0.0052(18) 0.0156(17) -0.0056(17) C6 0.051(2) 0.039(2) 0.058(3) 0.0135(19) 0.021(2) -0.0001(19) C7 0.0393(19) 0.0300(18) 0.039(2) -0.0017(15) 0.0103(15) -0.0037(15) C8 0.041(2) 0.0328(18) 0.0332(18) -0.0029(14) 0.0079(15) -0.0047(16) C9 0.044(2) 0.037(2) 0.038(2) -0.0038(16) 0.0144(16) -0.0031(17) C10 0.049(2) 0.042(2) 0.052(2) -0.0007(18) 0.0180(19) 0.0040(19) C11 0.052(2) 0.053(3) 0.040(2) -0.0073(19) 0.0183(18) 0.000(2) C12 0.048(2) 0.046(2) 0.051(2) -0.0022(19) 0.0157(19) -0.011(2) C13 0.043(2) 0.0306(18) 0.0327(18) -0.0007(14) 0.0126(15) -0.0048(16) C14 0.044(2) 0.0264(17) 0.0334(18) -0.0010(14) 0.0089(15) -0.0036(15) C15 0.042(2) 0.0337(19) 0.0325(18) 0.0009(14) 0.0100(15) -0.0056(16) C16 0.039(2) 0.0331(19) 0.038(2) -0.0012(15) 0.0094(15) -0.0016(16) C17 0.0394(19) 0.0324(18) 0.0363(19) -0.0002(14) 0.0109(15) 0.0019(15) C18 0.042(2) 0.0335(19) 0.041(2) 0.0021(15) 0.0134(16) -0.0004(16) C19 0.0326(18) 0.0335(19) 0.047(2) -0.0033(16) 0.0101(15) -0.0028(16) C20 0.037(2) 0.0335(19) 0.051(2) -0.0036(17) 0.0136(17) -0.0045(16) C21 0.045(2) 0.051(3) 0.083(4) -0.008(3) 0.007(2) -0.006(2) C22 0.060(3) 0.048(3) 0.067(3) -0.002(2) 0.033(2) -0.015(2) C23 0.057(3) 0.035(2) 0.057(3) -0.0104(18) 0.020(2) -0.009(2) C24 0.0384(19) 0.037(2) 0.038(2) -0.0032(15) 0.0080(15) 0.0019(16) C25 0.0360(19) 0.038(2) 0.0358(19) 0.0004(15) 0.0083(15) 0.0019(16) C26 0.0356(19) 0.041(2) 0.0366(19) -0.0006(16) 0.0106(15) -0.0010(16) C27 0.048(2) 0.060(3) 0.038(2) -0.0065(19) 0.0113(17) -0.010(2) C28 0.041(2) 0.058(3) 0.049(2) -0.005(2) 0.0144(18) 0.004(2) C29 0.056(3) 0.045(2) 0.041(2) 0.0077(18) 0.0149(19) 0.001(2) C30 0.0370(19) 0.0326(18) 0.0373(19) 0.0004(15) 0.0102(15) -0.0019(15) C31 0.048(2) 0.0244(17) 0.043(2) 0.0005(14) 0.0102(16) 0.0007(16) C32 0.052(2) 0.032(2) 0.045(2) 0.0000(16) 0.0079(18) -0.0014(18) C33 0.055(3) 0.035(2) 0.059(3) 0.0010(19) 0.018(2) 0.0074(19) C34 0.050(2) 0.043(2) 0.058(3) -0.005(2) 0.012(2) 0.004(2) C35 0.054(3) 0.049(3) 0.054(3) -0.001(2) 0.022(2) 0.013(2) N1 0.0390(17) 0.0289(16) 0.0352(16) -0.0023(12) 0.0094(13) -0.0023(13) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Br1 Fe1 2.4034(15) . ? Fe1 O2 1.821(3) . ? Fe1 O1 1.840(3) . ? Fe1 O3 2.035(3) . ? Fe1 N1 2.261(4) . ? O1 C1 1.335(5) . ? O2 C30 1.338(5) . ? O3 C32 1.454(5) . ? O3 C35 1.455(5) . ? C1 C14 1.395(5) . ? C1 C2 1.397(6) . ? C2 C7 1.387(6) . ? C2 C3 1.526(5) . ? C3 C4 1.521(6) . ? C3 C6 1.530(6) . ? C3 C5 1.536(6) . ? C4 H4A 0.9800 . ? C4 H4B 0.9800 . ? C4 H4C 0.9800 . ? C5 H5A 0.9800 . ? C5 H5B 0.9800 . ? C5 H5C 0.9800 . ? C6 H6A 0.9800 . ? C6 H6B 0.9800 . ? C6 H6C 0.9800 . ? C7 C8 1.388(6) . ? C7 H7 0.9500 . ? C8 C13 1.395(6) . ? C8 C9 1.511(6) . ? C9 C12 1.515(6) . ? C9 C11 1.523(6) . ? C9 C10 1.525(6) . ? C10 H10A 0.9800 . ? C10 H10B 0.9800 . ? C10 H10C 0.9800 . ? C11 H11A 0.9800 . ? C11 H11B 0.9800 . ? C11 H11C 0.9800 . ? C12 H12A 0.9800 . ? C12 H12B 0.9800 . ? C12 H12C 0.9800 . ? C13 C14 1.380(6) . ? C13 H13 0.9500 . ? C14 C15 1.486(5) . ? C15 N1 1.488(5) . ? C15 H15A 0.9900 . ? C15 H15B 0.9900 . ? C16 N1 1.476(5) . ? C16 C17 1.484(5) . ? C16 H16A 0.9900 . ? C16 H16B 0.9900 . ? C17 C18 1.373(6) . ? C17 C30 1.397(6) . ? C18 C19 1.380(6) . ? C18 H18 0.9500 . ? C19 C24 1.384(6) . ? C19 C20 1.521(6) . ? C20 C21 1.511(7) . ? C20 C23 1.520(6) . ? C20 C22 1.526(7) . ? C21 H21A 0.9800 . ? C21 H21B 0.9800 . ? C21 H21C 0.9800 . ? C22 H22A 0.9800 . ? C22 H22B 0.9800 . ? C22 H22C 0.9800 . ? C23 H23A 0.9800 . ? C23 H23B 0.9800 . ? C23 H23C 0.9800 . ? C24 C25 1.385(6) . ? C24 H24 0.9500 . ? C25 C30 1.399(5) . ? C25 C26 1.525(6) . ? C26 C27 1.514(6) . ? C26 C29 1.515(6) . ? C26 C28 1.519(6) . ? C27 H27A 0.9800 . ? C27 H27B 0.9800 . ? C27 H27C 0.9800 . ? C28 H28A 0.9800 . ? C28 H28B 0.9800 . ? C28 H28C 0.9800 . ? C29 H29A 0.9800 . ? C29 H29B 0.9800 . ? C29 H29C 0.9800 . ? C31 N1 1.465(5) . ? C31 C32 1.488(6) . ? C31 H31A 0.9900 . ? C31 H31B 0.9900 . ? C32 C33 1.507(6) . ? C32 H32 1.0000 . ? C33 C34 1.495(7) . ? C33 H33A 0.9900 . ? C33 H33B 0.9900 . ? C34 C35 1.494(7) . ? C34 H34A 0.9900 . ? C34 H34B 0.9900 . ? C35 H35A 0.9900 . ? C35 H35B 0.9900 . ? 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 O2 Fe1 O1 119.45(13) . . ? O2 Fe1 O3 115.54(13) . . ? O1 Fe1 O3 121.35(13) . . ? O2 Fe1 N1 87.21(14) . . ? O1 Fe1 N1 86.91(13) . . ? O3 Fe1 N1 76.73(13) . . ? O2 Fe1 Br1 103.29(11) . . ? O1 Fe1 Br1 95.33(10) . . ? O3 Fe1 Br1 90.63(10) . . ? N1 Fe1 Br1 166.27(9) . . ? C1 O1 Fe1 128.1(3) . . ? C30 O2 Fe1 134.2(3) . . ? C32 O3 C35 110.0(3) . . ? C32 O3 Fe1 120.2(3) . . ? C35 O3 Fe1 129.5(3) . . ? O1 C1 C14 118.1(4) . . ? O1 C1 C2 121.9(4) . . ? C14 C1 C2 120.1(4) . . ? C7 C2 C1 117.3(4) . . ? C7 C2 C3 122.0(4) . . ? C1 C2 C3 120.6(4) . . ? C4 C3 C2 110.3(3) . . ? C4 C3 C6 107.5(4) . . ? C2 C3 C6 111.8(4) . . ? C4 C3 C5 108.5(4) . . ? C2 C3 C5 111.3(3) . . ? C6 C3 C5 107.3(4) . . ? 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 . . ? C3 C5 H5A 109.5 . . ? C3 C5 H5B 109.5 . . ? H5A C5 H5B 109.5 . . ? C3 C5 H5C 109.5 . . ? H5A C5 H5C 109.5 . . ? H5B C5 H5C 109.5 . . ? C3 C6 H6A 109.5 . . ? C3 C6 H6B 109.5 . . ? H6A C6 H6B 109.5 . . ? C3 C6 H6C 109.5 . . ? H6A C6 H6C 109.5 . . ? H6B C6 H6C 109.5 . . ? C2 C7 C8 124.3(4) . . ? C2 C7 H7 117.8 . . ? C8 C7 H7 117.8 . . ? C7 C8 C13 116.5(4) . . ? C7 C8 C9 124.1(4) . . ? C13 C8 C9 119.3(4) . . ? C8 C9 C12 109.6(4) . . ? C8 C9 C11 110.2(3) . . ? C12 C9 C11 109.1(4) . . ? C8 C9 C10 111.7(4) . . ? C12 C9 C10 107.6(4) . . ? C11 C9 C10 108.6(4) . . ? C9 C10 H10A 109.5 . . ? C9 C10 H10B 109.5 . . ? H10A C10 H10B 109.5 . . ? C9 C10 H10C 109.5 . . ? H10A C10 H10C 109.5 . . ? H10B C10 H10C 109.5 . . ? C9 C11 H11A 109.5 . . ? C9 C11 H11B 109.5 . . ? H11A C11 H11B 109.5 . . ? C9 C11 H11C 109.5 . . ? H11A C11 H11C 109.5 . . ? H11B C11 H11C 109.5 . . ? C9 C12 H12A 109.5 . . ? C9 C12 H12B 109.5 . . ? H12A C12 H12B 109.5 . . ? C9 C12 H12C 109.5 . . ? H12A C12 H12C 109.5 . . ? H12B C12 H12C 109.5 . . ? C14 C13 C8 121.3(4) . . ? C14 C13 H13 119.4 . . ? C8 C13 H13 119.4 . . ? C13 C14 C1 120.5(4) . . ? C13 C14 C15 120.8(4) . . ? C1 C14 C15 118.5(4) . . ? C14 C15 N1 111.1(3) . . ? C14 C15 H15A 109.4 . . ? N1 C15 H15A 109.4 . . ? C14 C15 H15B 109.4 . . ? N1 C15 H15B 109.4 . . ? H15A C15 H15B 108.0 . . ? N1 C16 C17 114.3(3) . . ? N1 C16 H16A 108.7 . . ? C17 C16 H16A 108.7 . . ? N1 C16 H16B 108.7 . . ? C17 C16 H16B 108.7 . . ? H16A C16 H16B 107.6 . . ? C18 C17 C30 120.1(4) . . ? C18 C17 C16 120.5(4) . . ? C30 C17 C16 119.3(4) . . ? C17 C18 C19 122.0(4) . . ? C17 C18 H18 119.0 . . ? C19 C18 H18 119.0 . . ? C18 C19 C24 116.6(4) . . ? C18 C19 C20 123.1(4) . . ? C24 C19 C20 120.2(4) . . ? C21 C20 C23 108.9(4) . . ? C21 C20 C19 109.2(4) . . ? C23 C20 C19 110.7(4) . . ? C21 C20 C22 109.1(4) . . ? C23 C20 C22 107.2(4) . . ? C19 C20 C22 111.8(4) . . ? C20 C21 H21A 109.5 . . ? C20 C21 H21B 109.5 . . ? H21A C21 H21B 109.5 . . ? C20 C21 H21C 109.5 . . ? H21A C21 H21C 109.5 . . ? H21B C21 H21C 109.5 . . ? C20 C22 H22A 109.5 . . ? C20 C22 H22B 109.5 . . ? H22A C22 H22B 109.5 . . ? C20 C22 H22C 109.5 . . ? H22A C22 H22C 109.5 . . ? H22B C22 H22C 109.5 . . ? C20 C23 H23A 109.5 . . ? C20 C23 H23B 109.5 . . ? H23A C23 H23B 109.5 . . ? C20 C23 H23C 109.5 . . ? H23A C23 H23C 109.5 . . ? H23B C23 H23C 109.5 . . ? C19 C24 C25 124.3(4) . . ? C19 C24 H24 117.9 . . ? C25 C24 H24 117.9 . . ? C24 C25 C30 117.1(4) . . ? C24 C25 C26 121.9(4) . . ? C30 C25 C26 121.0(4) . . ? C27 C26 C29 107.2(4) . . ? C27 C26 C28 107.9(4) . . ? C29 C26 C28 109.8(4) . . ? C27 C26 C25 112.0(4) . . ? C29 C26 C25 109.6(4) . . ? C28 C26 C25 110.3(3) . . ? C26 C27 H27A 109.5 . . ? C26 C27 H27B 109.5 . . ? H27A C27 H27B 109.5 . . ? C26 C27 H27C 109.5 . . ? H27A C27 H27C 109.5 . . ? H27B C27 H27C 109.5 . . ? C26 C28 H28A 109.5 . . ? C26 C28 H28B 109.5 . . ? H28A C28 H28B 109.5 . . ? C26 C28 H28C 109.5 . . ? H28A C28 H28C 109.5 . . ? H28B C28 H28C 109.5 . . ? C26 C29 H29A 109.5 . . ? C26 C29 H29B 109.5 . . ? H29A C29 H29B 109.5 . . ? C26 C29 H29C 109.5 . . ? H29A C29 H29C 109.5 . . ? H29B C29 H29C 109.5 . . ? O2 C30 C17 118.9(3) . . ? O2 C30 C25 121.1(4) . . ? C17 C30 C25 120.0(4) . . ? N1 C31 C32 111.8(3) . . ? N1 C31 H31A 109.2 . . ? C32 C31 H31A 109.2 . . ? N1 C31 H31B 109.2 . . ? C32 C31 H31B 109.2 . . ? H31A C31 H31B 107.9 . . ? O3 C32 C31 106.5(3) . . ? O3 C32 C33 103.0(4) . . ? C31 C32 C33 115.0(4) . . ? O3 C32 H32 110.7 . . ? C31 C32 H32 110.7 . . ? C33 C32 H32 110.7 . . ? C34 C33 C32 102.2(4) . . ? C34 C33 H33A 111.3 . . ? C32 C33 H33A 111.3 . . ? C34 C33 H33B 111.3 . . ? C32 C33 H33B 111.3 . . ? H33A C33 H33B 109.2 . . ? C35 C34 C33 104.1(4) . . ? C35 C34 H34A 110.9 . . ? C33 C34 H34A 110.9 . . ? C35 C34 H34B 110.9 . . ? C33 C34 H34B 110.9 . . ? H34A C34 H34B 109.0 . . ? O3 C35 C34 104.9(4) . . ? O3 C35 H35A 110.8 . . ? C34 C35 H35A 110.8 . . ? O3 C35 H35B 110.8 . . ? C34 C35 H35B 110.8 . . ? H35A C35 H35B 108.8 . . ? C31 N1 C16 110.8(3) . . ? C31 N1 C15 111.5(3) . . ? C16 N1 C15 108.9(3) . . ? C31 N1 Fe1 107.1(2) . . ? C16 N1 Fe1 109.9(2) . . ? C15 N1 Fe1 108.7(2) . . ? 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 O2 Fe1 O1 C1 47.0(3) . . . . ? O3 Fe1 O1 C1 -110.4(3) . . . . ? N1 Fe1 O1 C1 -38.0(3) . . . . ? Br1 Fe1 O1 C1 155.5(3) . . . . ? O1 Fe1 O2 C30 -113.9(4) . . . . ? O3 Fe1 O2 C30 44.8(4) . . . . ? N1 Fe1 O2 C30 -29.0(4) . . . . ? Br1 Fe1 O2 C30 142.1(4) . . . . ? O2 Fe1 O3 C32 -87.3(3) . . . . ? O1 Fe1 O3 C32 71.0(3) . . . . ? N1 Fe1 O3 C32 -7.0(3) . . . . ? Br1 Fe1 O3 C32 167.6(3) . . . . ? O2 Fe1 O3 C35 85.2(4) . . . . ? O1 Fe1 O3 C35 -116.6(4) . . . . ? N1 Fe1 O3 C35 165.5(4) . . . . ? Br1 Fe1 O3 C35 -19.9(4) . . . . ? Fe1 O1 C1 C14 57.0(5) . . . . ? Fe1 O1 C1 C2 -121.5(3) . . . . ? O1 C1 C2 C7 176.6(3) . . . . ? C14 C1 C2 C7 -2.0(5) . . . . ? O1 C1 C2 C3 -1.2(6) . . . . ? C14 C1 C2 C3 -179.7(4) . . . . ? C7 C2 C3 C4 -109.4(4) . . . . ? C1 C2 C3 C4 68.3(5) . . . . ? C7 C2 C3 C6 10.1(5) . . . . ? C1 C2 C3 C6 -172.2(4) . . . . ? C7 C2 C3 C5 130.2(4) . . . . ? C1 C2 C3 C5 -52.2(5) . . . . ? C1 C2 C7 C8 1.1(6) . . . . ? C3 C2 C7 C8 178.8(4) . . . . ? C2 C7 C8 C13 0.9(6) . . . . ? C2 C7 C8 C9 -177.5(4) . . . . ? C7 C8 C9 C12 123.3(4) . . . . ? C13 C8 C9 C12 -55.1(5) . . . . ? C7 C8 C9 C11 -116.7(4) . . . . ? C13 C8 C9 C11 65.0(5) . . . . ? C7 C8 C9 C10 4.2(5) . . . . ? C13 C8 C9 C10 -174.2(4) . . . . ? C7 C8 C13 C14 -2.2(6) . . . . ? C9 C8 C13 C14 176.3(4) . . . . ? C8 C13 C14 C1 1.4(6) . . . . ? C8 C13 C14 C15 -173.5(4) . . . . ? O1 C1 C14 C13 -177.8(3) . . . . ? C2 C1 C14 C13 0.8(6) . . . . ? O1 C1 C14 C15 -2.8(5) . . . . ? C2 C1 C14 C15 175.8(3) . . . . ? C13 C14 C15 N1 115.6(4) . . . . ? C1 C14 C15 N1 -59.4(5) . . . . ? N1 C16 C17 C18 126.5(4) . . . . ? N1 C16 C17 C30 -57.3(5) . . . . ? C30 C17 C18 C19 -1.1(6) . . . . ? C16 C17 C18 C19 175.0(4) . . . . ? C17 C18 C19 C24 -0.6(6) . . . . ? C17 C18 C19 C20 -176.1(4) . . . . ? C18 C19 C20 C21 103.0(5) . . . . ? C24 C19 C20 C21 -72.2(5) . . . . ? C18 C19 C20 C23 -137.1(4) . . . . ? C24 C19 C20 C23 47.6(5) . . . . ? C18 C19 C20 C22 -17.7(6) . . . . ? C24 C19 C20 C22 167.0(4) . . . . ? C18 C19 C24 C25 1.6(6) . . . . ? C20 C19 C24 C25 177.2(4) . . . . ? C19 C24 C25 C30 -0.9(6) . . . . ? C19 C24 C25 C26 178.3(4) . . . . ? C24 C25 C26 C27 3.1(6) . . . . ? C30 C25 C26 C27 -177.8(4) . . . . ? C24 C25 C26 C29 121.9(4) . . . . ? C30 C25 C26 C29 -58.9(5) . . . . ? C24 C25 C26 C28 -117.1(4) . . . . ? C30 C25 C26 C28 62.1(5) . . . . ? Fe1 O2 C30 C17 42.6(6) . . . . ? Fe1 O2 C30 C25 -138.6(3) . . . . ? C18 C17 C30 O2 -179.2(4) . . . . ? C16 C17 C30 O2 4.6(6) . . . . ? C18 C17 C30 C25 1.9(6) . . . . ? C16 C17 C30 C25 -174.3(4) . . . . ? C24 C25 C30 O2 -179.8(4) . . . . ? C26 C25 C30 O2 1.0(6) . . . . ? C24 C25 C30 C17 -1.0(6) . . . . ? C26 C25 C30 C17 179.9(4) . . . . ? C35 O3 C32 C31 -143.7(4) . . . . ? Fe1 O3 C32 C31 30.1(4) . . . . ? C35 O3 C32 C33 -22.3(5) . . . . ? Fe1 O3 C32 C33 151.5(3) . . . . ? N1 C31 C32 O3 -46.0(4) . . . . ? N1 C31 C32 C33 -159.3(4) . . . . ? O3 C32 C33 C34 37.1(4) . . . . ? C31 C32 C33 C34 152.5(4) . . . . ? C32 C33 C34 C35 -38.6(5) . . . . ? C32 O3 C35 C34 -1.7(5) . . . . ? Fe1 O3 C35 C34 -174.7(3) . . . . ? C33 C34 C35 O3 25.3(5) . . . . ? C32 C31 N1 C16 160.4(3) . . . . ? C32 C31 N1 C15 -78.2(4) . . . . ? C32 C31 N1 Fe1 40.5(4) . . . . ? C17 C16 N1 C31 -58.2(4) . . . . ? C17 C16 N1 C15 178.8(3) . . . . ? C17 C16 N1 Fe1 59.9(4) . . . . ? C14 C15 N1 C31 -178.4(3) . . . . ? C14 C15 N1 C16 -55.8(4) . . . . ? C14 C15 N1 Fe1 63.9(4) . . . . ? O2 Fe1 N1 C31 98.9(2) . . . . ? O1 Fe1 N1 C31 -141.4(2) . . . . ? O3 Fe1 N1 C31 -18.2(2) . . . . ? Br1 Fe1 N1 C31 -41.6(5) . . . . ? O2 Fe1 N1 C16 -21.6(2) . . . . ? O1 Fe1 N1 C16 98.1(2) . . . . ? O3 Fe1 N1 C16 -138.7(3) . . . . ? Br1 Fe1 N1 C16 -162.0(3) . . . . ? O2 Fe1 N1 C15 -140.7(3) . . . . ? O1 Fe1 N1 C15 -21.0(3) . . . . ? O3 Fe1 N1 C15 102.3(3) . . . . ? Br1 Fe1 N1 C15 78.9(4) . . . . ? _diffrn_measured_fraction_theta_max 0.992 _diffrn_reflns_theta_full 26.49 _diffrn_measured_fraction_theta_full 0.992 _refine_diff_density_max 1.442 _refine_diff_density_min -1.296 _refine_diff_density_rms 0.176 #===END data_2b _database_code_depnum_ccdc_archive 'CCDC 847893' #TrackingRef 'New CIFS.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C29 H43 Br Fe N O4' _chemical_formula_weight 605.40 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 'P 1 21/n 1' _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 9.9384(7) _cell_length_b 24.9188(18) _cell_length_c 12.5168(9) _cell_angle_alpha 90.00 _cell_angle_beta 95.852(2) _cell_angle_gamma 90.00 _cell_volume 3083.7(4) _cell_formula_units_Z 4 _cell_measurement_temperature 113(2) _cell_measurement_reflns_used 10311 _cell_measurement_theta_min 2.6299 _cell_measurement_theta_max 30.8042 _exptl_crystal_description Prism _exptl_crystal_colour Black _exptl_crystal_size_max 0.55 _exptl_crystal_size_mid 0.55 _exptl_crystal_size_min 0.19 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.304 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1268 _exptl_absorpt_coefficient_mu 1.816 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_min 0.4904 _exptl_absorpt_correction_T_max 0.7890 _exptl_absorpt_process_details 'T. Higashi, 2000' _exptl_special_details ; ? ; _diffrn_ambient_temperature 113(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 28491 _diffrn_reflns_av_R_equivalents 0.0207 _diffrn_reflns_av_sigmaI/netI 0.0181 _diffrn_reflns_limit_h_min -9 _diffrn_reflns_limit_h_max 12 _diffrn_reflns_limit_k_min -26 _diffrn_reflns_limit_k_max 32 _diffrn_reflns_limit_l_min -15 _diffrn_reflns_limit_l_max 16 _diffrn_reflns_theta_min 2.63 _diffrn_reflns_theta_max 27.50 _reflns_number_total 7006 _reflns_number_gt 6437 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_publication_material 'CrystalClear (Rigaku/MSC Inc., 2005)' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0807P)^2^+3.8417P] 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 7006 _refine_ls_number_parameters 325 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0540 _refine_ls_R_factor_gt 0.0504 _refine_ls_wR_factor_ref 0.1425 _refine_ls_wR_factor_gt 0.1389 _refine_ls_goodness_of_fit_ref 1.054 _refine_ls_restrained_S_all 1.054 _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 Br1 Br 0.40616(3) 0.239782(12) 0.86220(2) 0.03246(11) Uani 1 1 d . . . Fe1 Fe 0.18847(4) 0.260159(14) 0.92447(3) 0.02232(12) Uani 1 1 d . . . O1 O 0.20681(19) 0.33411(8) 0.92026(16) 0.0299(4) Uani 1 1 d . . . O2 O 0.07441(18) 0.22831(8) 0.81634(15) 0.0264(4) Uani 1 1 d . . . O3 O 0.2410(2) 0.21864(9) 1.06677(18) 0.0362(5) Uani 1 1 d . . . O4 O 0.9008(16) -0.0007(7) 0.9182(13) 0.088(4) Uiso 0.25 1 d P . . H42 H 0.8581 -0.0121 0.8993 0.105 Uiso 0.25 1 d P . . H43 H 0.9637 -0.0132 0.9697 0.105 Uiso 0.25 1 d P . . O5 O 0.9917(16) -0.0514(6) 0.9956(13) 0.087(4) Uiso 0.25 1 d P . . H44 H 0.9853 -0.0846 0.9644 0.105 Uiso 0.25 1 d P . . H45 H 1.0440 -0.0362 1.0380 0.105 Uiso 0.25 1 d P . . N1 N 0.0099(2) 0.27048(9) 1.01650(18) 0.0250(4) Uani 1 1 d . . . C1 C 0.1117(3) 0.37277(10) 0.9168(2) 0.0268(5) Uani 1 1 d . . . C2 C 0.1113(3) 0.41554(11) 0.8427(2) 0.0298(6) Uani 1 1 d . . . C3 C 0.2183(3) 0.41914(12) 0.7619(3) 0.0349(6) Uani 1 1 d . . . C4 C 0.2080(3) 0.37026(13) 0.6867(3) 0.0395(7) Uani 1 1 d . . . H1 H 0.1168 0.3684 0.6489 0.047 Uiso 1 1 calc R . . H2 H 0.2263 0.3375 0.7289 0.047 Uiso 1 1 calc R . . H3 H 0.2743 0.3737 0.6343 0.047 Uiso 1 1 calc R . . C5 C 0.3604(3) 0.42189(14) 0.8221(3) 0.0429(7) Uani 1 1 d . . . H4 H 0.3749 0.3907 0.8696 0.051 Uiso 1 1 calc R . . H5 H 0.3693 0.4549 0.8649 0.051 Uiso 1 1 calc R . . H6 H 0.4279 0.4218 0.7702 0.051 Uiso 1 1 calc R . . C6 C 0.1977(4) 0.46961(14) 0.6917(3) 0.0512(9) Uani 1 1 d . . . H7 H 0.2725 0.4730 0.6469 0.061 Uiso 1 1 calc R . . H8 H 0.1953 0.5013 0.7378 0.061 Uiso 1 1 calc R . . H9 H 0.1121 0.4667 0.6457 0.061 Uiso 1 1 calc R . . C7 C 0.0085(3) 0.45371(11) 0.8448(2) 0.0325(6) Uani 1 1 d . . . H10 H 0.0069 0.4830 0.7960 0.039 Uiso 1 1 calc R . . C8 C -0.0919(3) 0.45110(11) 0.9147(2) 0.0329(6) Uani 1 1 d . . . C9 C -0.2016(3) 0.49307(13) 0.9112(3) 0.0418(7) Uani 1 1 d . . . H11 H -0.1610 0.5282 0.9291 0.050 Uiso 1 1 calc R . . H12 H -0.2652 0.4839 0.9632 0.050 Uiso 1 1 calc R . . H13 H -0.2497 0.4944 0.8389 0.050 Uiso 1 1 calc R . . C10 C -0.0876(3) 0.40890(11) 0.9875(2) 0.0315(6) Uani 1 1 d . . . H14 H -0.1544 0.4066 1.0365 0.038 Uiso 1 1 calc R . . C11 C 0.0135(3) 0.36985(10) 0.9898(2) 0.0282(5) Uani 1 1 d . . . C12 C 0.0191(3) 0.32427(11) 1.0694(2) 0.0295(5) Uani 1 1 d . . . H15 H 0.1050 0.3265 1.1169 0.035 Uiso 1 1 calc R . . H16 H -0.0562 0.3282 1.1148 0.035 Uiso 1 1 calc R . . C13 C -0.1180(3) 0.26706(11) 0.9439(2) 0.0284(6) Uani 1 1 d . . . H17 H -0.1196 0.2966 0.8909 0.034 Uiso 1 1 calc R . . H18 H -0.1951 0.2725 0.9869 0.034 Uiso 1 1 calc R . . C14 C -0.1375(3) 0.21495(10) 0.8845(2) 0.0253(5) Uani 1 1 d . . . C15 C -0.2535(3) 0.18433(11) 0.8908(2) 0.0291(5) Uani 1 1 d . . . H19 H -0.3182 0.1954 0.9372 0.035 Uiso 1 1 calc R . . C16 C -0.2763(3) 0.13793(11) 0.8304(2) 0.0309(6) Uani 1 1 d . . . C17 C -0.4019(3) 0.10401(13) 0.8372(3) 0.0390(7) Uani 1 1 d . . . H20 H -0.4591 0.1207 0.8872 0.047 Uiso 1 1 calc R . . H21 H -0.3754 0.0680 0.8629 0.047 Uiso 1 1 calc R . . H22 H -0.4523 0.1014 0.7659 0.047 Uiso 1 1 calc R . . C18 C -0.1792(3) 0.12316(11) 0.7629(2) 0.0298(5) Uani 1 1 d . . . H23 H -0.1957 0.0921 0.7194 0.036 Uiso 1 1 calc R . . C19 C -0.0588(3) 0.15148(11) 0.7556(2) 0.0255(5) Uani 1 1 d . . . C20 C 0.0476(3) 0.13195(11) 0.6838(2) 0.0296(5) Uani 1 1 d . . . C21 C 0.0018(4) 0.08074(14) 0.6222(3) 0.0433(8) Uani 1 1 d . . . H24 H -0.0801 0.0883 0.5742 0.052 Uiso 1 1 calc R . . H25 H -0.0173 0.0526 0.6733 0.052 Uiso 1 1 calc R . . H26 H 0.0737 0.0686 0.5798 0.052 Uiso 1 1 calc R . . C22 C 0.1789(3) 0.11858(13) 0.7544(3) 0.0354(6) Uani 1 1 d . . . H27 H 0.1609 0.0907 0.8063 0.043 Uiso 1 1 calc R . . H28 H 0.2127 0.1509 0.7928 0.043 Uiso 1 1 calc R . . H29 H 0.2468 0.1056 0.7090 0.043 Uiso 1 1 calc R . . C23 C 0.0735(3) 0.17497(13) 0.6010(3) 0.0380(7) Uani 1 1 d . . . H30 H 0.1416 0.1620 0.5558 0.046 Uiso 1 1 calc R . . H31 H 0.1064 0.2078 0.6381 0.046 Uiso 1 1 calc R . . H32 H -0.0108 0.1827 0.5559 0.046 Uiso 1 1 calc R . . C24 C -0.0391(2) 0.19830(10) 0.8187(2) 0.0242(5) Uani 1 1 d . . . C25 C 0.0120(3) 0.22721(12) 1.0973(2) 0.0315(6) Uani 1 1 d . . . H33 H -0.0539 0.2335 1.1438 0.027 Uiso 1 1 d . . . H34 H -0.0094 0.1951 1.0555 0.027 Uiso 1 1 d . . . C26 C 0.1505(3) 0.22064(13) 1.1527(2) 0.0369(6) Uani 1 1 d . . . H35 H 0.1743 0.2517 1.2017 0.044 Uiso 1 1 calc R . . C27 C 0.1761(4) 0.16715(15) 1.2131(3) 0.0463(8) Uani 1 1 d . . . H36 H 0.1822 0.1728 1.2917 0.056 Uiso 1 1 calc R . . H37 H 0.1026 0.1412 1.1923 0.056 Uiso 1 1 calc R . . C28 C 0.3093(5) 0.1472(2) 1.1796(4) 0.0695(13) Uani 1 1 d . . . H38 H 0.3755 0.1419 1.2433 0.083 Uiso 1 1 calc R . . H39 H 0.2964 0.1125 1.1411 0.083 Uiso 1 1 calc R . . C29 C 0.3569(4) 0.1877(2) 1.1097(4) 0.0694(14) Uani 1 1 d . . . H40 H 0.4239 0.2112 1.1506 0.083 Uiso 1 1 calc R . . H41 H 0.4005 0.1706 1.0507 0.083 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Br1 0.02132(16) 0.03911(19) 0.03794(19) -0.00348(11) 0.00786(11) 0.00409(10) Fe1 0.0190(2) 0.0227(2) 0.0258(2) -0.00135(13) 0.00451(15) 0.00109(12) O1 0.0267(9) 0.0252(9) 0.0394(11) -0.0020(8) 0.0116(8) 0.0006(7) O2 0.0204(8) 0.0315(9) 0.0276(9) -0.0020(7) 0.0043(7) -0.0031(7) O3 0.0256(10) 0.0426(12) 0.0402(11) 0.0136(9) 0.0028(8) 0.0067(9) N1 0.0254(11) 0.0237(10) 0.0267(11) 0.0004(8) 0.0068(9) 0.0015(8) C1 0.0266(12) 0.0210(11) 0.0336(13) -0.0042(10) 0.0068(10) 0.0006(9) C2 0.0314(13) 0.0237(12) 0.0356(14) -0.0040(11) 0.0096(11) -0.0034(10) C3 0.0370(15) 0.0318(14) 0.0379(15) 0.0022(12) 0.0141(12) -0.0041(12) C4 0.0463(17) 0.0380(16) 0.0368(16) -0.0036(13) 0.0168(13) -0.0019(13) C5 0.0387(16) 0.0431(17) 0.0497(18) -0.0033(14) 0.0180(14) -0.0119(13) C6 0.061(2) 0.0401(18) 0.057(2) 0.0130(16) 0.0284(18) -0.0011(16) C7 0.0365(15) 0.0238(12) 0.0378(15) 0.0009(11) 0.0066(12) 0.0003(11) C8 0.0350(14) 0.0231(12) 0.0411(15) -0.0045(11) 0.0063(12) 0.0035(11) C9 0.0415(17) 0.0312(14) 0.0537(19) -0.0003(13) 0.0108(14) 0.0095(13) C10 0.0309(13) 0.0279(13) 0.0372(15) -0.0049(11) 0.0112(11) 0.0014(11) C11 0.0301(13) 0.0229(12) 0.0328(14) -0.0040(10) 0.0085(11) -0.0016(10) C12 0.0319(13) 0.0273(13) 0.0309(13) -0.0041(10) 0.0108(11) 0.0012(10) C13 0.0224(12) 0.0258(12) 0.0376(15) -0.0010(11) 0.0064(11) 0.0044(9) C14 0.0213(11) 0.0240(12) 0.0305(13) 0.0031(10) 0.0032(10) 0.0022(9) C15 0.0198(11) 0.0298(13) 0.0388(15) 0.0041(11) 0.0083(10) 0.0034(10) C16 0.0230(12) 0.0286(13) 0.0413(15) 0.0044(11) 0.0044(11) -0.0001(10) C17 0.0281(14) 0.0343(15) 0.0565(19) -0.0025(14) 0.0138(13) -0.0071(12) C18 0.0270(13) 0.0276(13) 0.0347(14) -0.0012(11) 0.0037(11) -0.0025(10) C19 0.0228(11) 0.0274(12) 0.0264(12) -0.0005(10) 0.0035(9) 0.0007(9) C20 0.0273(13) 0.0324(14) 0.0299(13) -0.0042(11) 0.0068(10) -0.0018(10) C21 0.0413(17) 0.0445(18) 0.0465(18) -0.0184(14) 0.0161(14) -0.0114(14) C22 0.0297(14) 0.0364(15) 0.0406(16) -0.0053(12) 0.0060(12) 0.0075(11) C23 0.0406(16) 0.0422(16) 0.0326(15) 0.0006(13) 0.0099(12) -0.0005(13) C24 0.0192(11) 0.0260(12) 0.0272(12) 0.0028(10) 0.0013(9) -0.0008(9) C25 0.0321(14) 0.0315(13) 0.0325(14) 0.0050(11) 0.0117(11) 0.0005(11) C26 0.0401(16) 0.0376(16) 0.0327(15) -0.0001(12) 0.0028(12) -0.0003(13) C27 0.0481(19) 0.0501(19) 0.0401(17) 0.0171(15) 0.0016(14) 0.0043(15) C28 0.080(3) 0.074(3) 0.057(2) 0.028(2) 0.022(2) 0.039(2) C29 0.0356(18) 0.077(3) 0.096(3) 0.049(3) 0.010(2) 0.0199(19) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Br1 Fe1 2.4269(5) . ? Fe1 O1 1.8530(19) . ? Fe1 O2 1.8531(19) . ? Fe1 O3 2.080(2) . ? Fe1 N1 2.227(2) . ? O1 C1 1.347(3) . ? O2 C24 1.356(3) . ? O3 C29 1.444(4) . ? O3 C26 1.471(4) . ? O4 O5 1.78(2) . ? O4 H42 0.5448 . ? O4 H43 0.9064 . ? O4 H43 0.9064 . ? O5 H43 1.0343 . ? O5 H43 1.0343 . ? O5 H44 0.9148 . ? O5 H45 0.7991 . ? N1 C25 1.477(3) . ? N1 C13 1.488(4) . ? N1 C12 1.494(3) . ? C1 C11 1.405(4) . ? C1 C2 1.413(4) . ? C2 C7 1.399(4) . ? C2 C3 1.542(4) . ? C3 C5 1.533(5) . ? C3 C6 1.536(4) . ? C3 C4 1.537(4) . ? C4 H1 0.9800 . ? C4 H2 0.9800 . ? C4 H3 0.9800 . ? C5 H4 0.9800 . ? C5 H5 0.9800 . ? C5 H6 0.9800 . ? C6 H7 0.9800 . ? C6 H8 0.9800 . ? C6 H9 0.9800 . ? C7 C8 1.394(4) . ? C7 H10 0.9500 . ? C8 C10 1.390(4) . ? C8 C9 1.507(4) . ? C9 H11 0.9800 . ? C9 H12 0.9800 . ? C9 H13 0.9800 . ? C10 C11 1.397(4) . ? C10 H14 0.9500 . ? C11 C12 1.508(4) . ? C12 H15 0.9900 . ? C12 H16 0.9900 . ? C13 C14 1.499(4) . ? C13 H17 0.9900 . ? C13 H18 0.9900 . ? C14 C15 1.392(4) . ? C14 C24 1.404(4) . ? C15 C16 1.387(4) . ? C15 H19 0.9500 . ? C16 C18 1.395(4) . ? C16 C17 1.517(4) . ? C17 H20 0.9800 . ? C17 H21 0.9800 . ? C17 H22 0.9800 . ? C18 C19 1.400(4) . ? C18 H23 0.9500 . ? C19 C24 1.411(4) . ? C19 C20 1.535(4) . ? C20 C23 1.531(4) . ? C20 C22 1.536(4) . ? C20 C21 1.536(4) . ? C21 H24 0.9800 . ? C21 H25 0.9800 . ? C21 H26 0.9800 . ? C22 H27 0.9800 . ? C22 H28 0.9800 . ? C22 H29 0.9800 . ? C23 H30 0.9800 . ? C23 H31 0.9800 . ? C23 H32 0.9800 . ? C25 C26 1.486(4) . ? C25 H33 0.9328 . ? C25 H34 0.9671 . ? C26 C27 1.541(4) . ? C26 H35 1.0000 . ? C27 C28 1.513(5) . ? C27 H36 0.9900 . ? C27 H37 0.9900 . ? C28 C29 1.447(6) . ? C28 H38 0.9900 . ? C28 H39 0.9900 . ? C29 H40 0.9900 . ? C29 H41 0.9900 . ? 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 Fe1 O2 117.37(9) . . ? O1 Fe1 O3 120.14(9) . . ? O2 Fe1 O3 119.59(9) . . ? O1 Fe1 N1 89.18(8) . . ? O2 Fe1 N1 88.10(8) . . ? O3 Fe1 N1 75.99(8) . . ? O1 Fe1 Br1 96.06(6) . . ? O2 Fe1 Br1 100.07(6) . . ? O3 Fe1 Br1 90.98(6) . . ? N1 Fe1 Br1 166.85(6) . . ? C1 O1 Fe1 129.90(17) . . ? C24 O2 Fe1 131.93(17) . . ? C29 O3 C26 105.7(3) . . ? C29 O3 Fe1 134.9(2) . . ? C26 O3 Fe1 119.38(17) . . ? O5 O4 H42 101.2 . . ? H42 O4 H43 125.4 . . ? H42 O4 H43 125.4 . . ? O4 O5 H44 113.6 . . ? H43 O5 H44 133.9 . . ? H43 O5 H44 133.9 . . ? O4 O5 H45 106.5 . . ? H43 O5 H45 84.7 . . ? H43 O5 H45 84.7 . . ? H44 O5 H45 136.4 . . ? C25 N1 C13 109.1(2) . . ? C25 N1 C12 110.8(2) . . ? C13 N1 C12 109.4(2) . . ? C25 N1 Fe1 108.28(16) . . ? C13 N1 Fe1 110.72(16) . . ? C12 N1 Fe1 108.48(16) . . ? O1 C1 C11 118.3(2) . . ? O1 C1 C2 121.0(2) . . ? C11 C1 C2 120.7(2) . . ? C7 C2 C1 117.0(2) . . ? C7 C2 C3 121.8(3) . . ? C1 C2 C3 121.2(2) . . ? C5 C3 C6 107.9(3) . . ? C5 C3 C4 109.7(3) . . ? C6 C3 C4 107.6(3) . . ? C5 C3 C2 110.0(3) . . ? C6 C3 C2 111.2(3) . . ? C4 C3 C2 110.4(2) . . ? C3 C4 H1 109.5 . . ? C3 C4 H2 109.5 . . ? H1 C4 H2 109.5 . . ? C3 C4 H3 109.5 . . ? H1 C4 H3 109.5 . . ? H2 C4 H3 109.5 . . ? C3 C5 H4 109.5 . . ? C3 C5 H5 109.5 . . ? H4 C5 H5 109.5 . . ? C3 C5 H6 109.5 . . ? H4 C5 H6 109.5 . . ? H5 C5 H6 109.5 . . ? C3 C6 H7 109.5 . . ? C3 C6 H8 109.5 . . ? H7 C6 H8 109.5 . . ? C3 C6 H9 109.5 . . ? H7 C6 H9 109.5 . . ? H8 C6 H9 109.5 . . ? C8 C7 C2 123.5(3) . . ? C8 C7 H10 118.3 . . ? C2 C7 H10 118.3 . . ? C10 C8 C7 118.1(3) . . ? C10 C8 C9 121.2(3) . . ? C7 C8 C9 120.7(3) . . ? C8 C9 H11 109.5 . . ? C8 C9 H12 109.5 . . ? H11 C9 H12 109.5 . . ? C8 C9 H13 109.5 . . ? H11 C9 H13 109.5 . . ? H12 C9 H13 109.5 . . ? C8 C10 C11 121.0(3) . . ? C8 C10 H14 119.5 . . ? C11 C10 H14 119.5 . . ? C10 C11 C1 119.8(3) . . ? C10 C11 C12 121.1(2) . . ? C1 C11 C12 119.1(2) . . ? N1 C12 C11 112.7(2) . . ? N1 C12 H15 109.0 . . ? C11 C12 H15 109.0 . . ? N1 C12 H16 109.0 . . ? C11 C12 H16 109.0 . . ? H15 C12 H16 107.8 . . ? N1 C13 C14 114.3(2) . . ? N1 C13 H17 108.7 . . ? C14 C13 H17 108.7 . . ? N1 C13 H18 108.7 . . ? C14 C13 H18 108.7 . . ? H17 C13 H18 107.6 . . ? C15 C14 C24 120.1(2) . . ? C15 C14 C13 120.8(2) . . ? C24 C14 C13 119.0(2) . . ? C16 C15 C14 121.1(3) . . ? C16 C15 H19 119.4 . . ? C14 C15 H19 119.4 . . ? C15 C16 C18 117.7(2) . . ? C15 C16 C17 121.6(3) . . ? C18 C16 C17 120.7(3) . . ? C16 C17 H20 109.5 . . ? C16 C17 H21 109.5 . . ? H20 C17 H21 109.5 . . ? C16 C17 H22 109.5 . . ? H20 C17 H22 109.5 . . ? H21 C17 H22 109.5 . . ? C16 C18 C19 123.7(3) . . ? C16 C18 H23 118.1 . . ? C19 C18 H23 118.1 . . ? C18 C19 C24 116.8(2) . . ? C18 C19 C20 121.5(2) . . ? C24 C19 C20 121.7(2) . . ? C23 C20 C19 110.4(2) . . ? C23 C20 C22 110.5(2) . . ? C19 C20 C22 109.1(2) . . ? C23 C20 C21 107.7(3) . . ? C19 C20 C21 111.8(2) . . ? C22 C20 C21 107.4(3) . . ? C20 C21 H24 109.5 . . ? C20 C21 H25 109.5 . . ? H24 C21 H25 109.5 . . ? C20 C21 H26 109.5 . . ? H24 C21 H26 109.5 . . ? H25 C21 H26 109.5 . . ? C20 C22 H27 109.5 . . ? C20 C22 H28 109.5 . . ? H27 C22 H28 109.5 . . ? C20 C22 H29 109.5 . . ? H27 C22 H29 109.5 . . ? H28 C22 H29 109.5 . . ? C20 C23 H30 109.5 . . ? C20 C23 H31 109.5 . . ? H30 C23 H31 109.5 . . ? C20 C23 H32 109.5 . . ? H30 C23 H32 109.5 . . ? H31 C23 H32 109.5 . . ? O2 C24 C14 118.7(2) . . ? O2 C24 C19 120.8(2) . . ? C14 C24 C19 120.5(2) . . ? N1 C25 C26 110.3(2) . . ? N1 C25 H33 110.0 . . ? C26 C25 H33 113.8 . . ? N1 C25 H34 104.3 . . ? C26 C25 H34 107.7 . . ? H33 C25 H34 110.3 . . ? O3 C26 C25 105.6(2) . . ? O3 C26 C27 104.3(3) . . ? C25 C26 C27 115.0(3) . . ? O3 C26 H35 110.5 . . ? C25 C26 H35 110.5 . . ? C27 C26 H35 110.5 . . ? C28 C27 C26 104.7(3) . . ? C28 C27 H36 110.8 . . ? C26 C27 H36 110.8 . . ? C28 C27 H37 110.8 . . ? C26 C27 H37 110.8 . . ? H36 C27 H37 108.9 . . ? C29 C28 C27 106.7(3) . . ? C29 C28 H38 110.4 . . ? C27 C28 H38 110.4 . . ? C29 C28 H39 110.4 . . ? C27 C28 H39 110.4 . . ? H38 C28 H39 108.6 . . ? O3 C29 C28 107.5(3) . . ? O3 C29 H40 110.2 . . ? C28 C29 H40 110.2 . . ? O3 C29 H41 110.2 . . ? C28 C29 H41 110.2 . . ? H40 C29 H41 108.5 . . ? 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 O2 Fe1 O1 C1 55.4(2) . . . . ? O3 Fe1 O1 C1 -105.3(2) . . . . ? N1 Fe1 O1 C1 -32.0(2) . . . . ? Br1 Fe1 O1 C1 160.0(2) . . . . ? O1 Fe1 O2 C24 -119.6(2) . . . . ? O3 Fe1 O2 C24 41.2(2) . . . . ? N1 Fe1 O2 C24 -31.5(2) . . . . ? Br1 Fe1 O2 C24 138.2(2) . . . . ? O1 Fe1 O3 C29 -100.4(4) . . . . ? O2 Fe1 O3 C29 99.4(4) . . . . ? N1 Fe1 O3 C29 179.0(4) . . . . ? Br1 Fe1 O3 C29 -2.8(4) . . . . ? O1 Fe1 O3 C26 75.4(2) . . . . ? O2 Fe1 O3 C26 -84.9(2) . . . . ? N1 Fe1 O3 C26 -5.3(2) . . . . ? Br1 Fe1 O3 C26 173.0(2) . . . . ? O1 Fe1 N1 C25 -142.73(18) . . . . ? O2 Fe1 N1 C25 99.85(18) . . . . ? O3 Fe1 N1 C25 -21.31(18) . . . . ? Br1 Fe1 N1 C25 -29.0(4) . . . . ? O1 Fe1 N1 C13 97.68(17) . . . . ? O2 Fe1 N1 C13 -19.74(17) . . . . ? O3 Fe1 N1 C13 -140.91(18) . . . . ? Br1 Fe1 N1 C13 -148.6(2) . . . . ? O1 Fe1 N1 C12 -22.36(18) . . . . ? O2 Fe1 N1 C12 -139.79(17) . . . . ? O3 Fe1 N1 C12 99.05(18) . . . . ? Br1 Fe1 N1 C12 91.4(3) . . . . ? Fe1 O1 C1 C11 48.1(3) . . . . ? Fe1 O1 C1 C2 -132.5(2) . . . . ? O1 C1 C2 C7 179.8(2) . . . . ? C11 C1 C2 C7 -0.9(4) . . . . ? O1 C1 C2 C3 0.9(4) . . . . ? C11 C1 C2 C3 -179.8(3) . . . . ? C7 C2 C3 C5 121.6(3) . . . . ? C1 C2 C3 C5 -59.5(4) . . . . ? C7 C2 C3 C6 2.2(4) . . . . ? C1 C2 C3 C6 -179.0(3) . . . . ? C7 C2 C3 C4 -117.2(3) . . . . ? C1 C2 C3 C4 61.7(4) . . . . ? C1 C2 C7 C8 -0.6(4) . . . . ? C3 C2 C7 C8 178.3(3) . . . . ? C2 C7 C8 C10 1.4(4) . . . . ? C2 C7 C8 C9 -178.8(3) . . . . ? C7 C8 C10 C11 -0.8(4) . . . . ? C9 C8 C10 C11 179.4(3) . . . . ? C8 C10 C11 C1 -0.7(4) . . . . ? C8 C10 C11 C12 179.4(3) . . . . ? O1 C1 C11 C10 -179.2(2) . . . . ? C2 C1 C11 C10 1.5(4) . . . . ? O1 C1 C11 C12 0.7(4) . . . . ? C2 C1 C11 C12 -178.6(2) . . . . ? C25 N1 C12 C11 -178.4(2) . . . . ? C13 N1 C12 C11 -58.0(3) . . . . ? Fe1 N1 C12 C11 62.9(2) . . . . ? C10 C11 C12 N1 120.9(3) . . . . ? C1 C11 C12 N1 -59.0(3) . . . . ? C25 N1 C13 C14 -59.6(3) . . . . ? C12 N1 C13 C14 179.0(2) . . . . ? Fe1 N1 C13 C14 59.5(3) . . . . ? N1 C13 C14 C15 124.9(3) . . . . ? N1 C13 C14 C24 -57.6(3) . . . . ? C24 C14 C15 C16 -1.9(4) . . . . ? C13 C14 C15 C16 175.6(3) . . . . ? C14 C15 C16 C18 -0.2(4) . . . . ? C14 C15 C16 C17 179.5(3) . . . . ? C15 C16 C18 C19 2.2(4) . . . . ? C17 C16 C18 C19 -177.6(3) . . . . ? C16 C18 C19 C24 -1.9(4) . . . . ? C16 C18 C19 C20 177.2(3) . . . . ? C18 C19 C20 C23 121.6(3) . . . . ? C24 C19 C20 C23 -59.4(3) . . . . ? C18 C19 C20 C22 -116.8(3) . . . . ? C24 C19 C20 C22 62.2(3) . . . . ? C18 C19 C20 C21 1.8(4) . . . . ? C24 C19 C20 C21 -179.2(3) . . . . ? Fe1 O2 C24 C14 44.5(3) . . . . ? Fe1 O2 C24 C19 -136.1(2) . . . . ? C15 C14 C24 O2 -178.4(2) . . . . ? C13 C14 C24 O2 4.0(4) . . . . ? C15 C14 C24 C19 2.2(4) . . . . ? C13 C14 C24 C19 -175.4(2) . . . . ? C18 C19 C24 O2 -179.7(2) . . . . ? C20 C19 C24 O2 1.2(4) . . . . ? C18 C19 C24 C14 -0.3(4) . . . . ? C20 C19 C24 C14 -179.4(2) . . . . ? C13 N1 C25 C26 165.6(2) . . . . ? C12 N1 C25 C26 -73.9(3) . . . . ? Fe1 N1 C25 C26 45.0(3) . . . . ? C29 O3 C26 C25 -153.0(3) . . . . ? Fe1 O3 C26 C25 30.1(3) . . . . ? C29 O3 C26 C27 -31.4(4) . . . . ? Fe1 O3 C26 C27 151.8(2) . . . . ? N1 C25 C26 O3 -48.2(3) . . . . ? N1 C25 C26 C27 -162.6(3) . . . . ? O3 C26 C27 C28 17.6(4) . . . . ? C25 C26 C27 C28 132.7(3) . . . . ? C26 C27 C28 C29 2.4(5) . . . . ? C26 O3 C29 C28 34.1(5) . . . . ? Fe1 O3 C29 C28 -149.8(3) . . . . ? C27 C28 C29 O3 -22.2(6) . . . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 27.50 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 1.269 _refine_diff_density_min -0.597 _refine_diff_density_rms 0.090 #===END data_4b _database_code_depnum_ccdc_archive 'CCDC 847894' #TrackingRef 'New CIFS.cif' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C27 H39 Br Fe N O3' _chemical_formula_weight 561.35 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 'P 1 21/c 1' _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 12.2762(19) _cell_length_b 11.1411(15) _cell_length_c 19.870(3) _cell_angle_alpha 90.00 _cell_angle_beta 103.834(2) _cell_angle_gamma 90.00 _cell_volume 2638.8(7) _cell_formula_units_Z 4 _cell_measurement_temperature 138(2) _cell_measurement_reflns_used 6189 _cell_measurement_theta_min 2.4 _cell_measurement_theta_max 30.9 _exptl_crystal_description platelet _exptl_crystal_colour black _exptl_crystal_size_max 0.47 _exptl_crystal_size_mid 0.24 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.413 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1172 _exptl_absorpt_coefficient_mu 2.113 _exptl_absorpt_correction_type Numerical _exptl_absorpt_correction_T_min 0.4638 _exptl_absorpt_correction_T_max 0.7296 _exptl_absorpt_process_details 'T. Higashi, 2000' _exptl_special_details ; ? ; _diffrn_ambient_temperature 138(2) _diffrn_radiation_wavelength 0.71070 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Rigaku Saturn' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean 14.63 _diffrn_reflns_number 19730 _diffrn_reflns_av_R_equivalents 0.0282 _diffrn_reflns_av_sigmaI/netI 0.0306 _diffrn_reflns_limit_h_min -14 _diffrn_reflns_limit_h_max 15 _diffrn_reflns_limit_k_min -11 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -23 _diffrn_reflns_limit_l_max 24 _diffrn_reflns_theta_min 2.38 _diffrn_reflns_theta_max 26.50 _reflns_number_total 5406 _reflns_number_gt 4987 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_cell_refinement 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_data_reduction 'CrystalClear (Rigaku/MSC Inc., 2005)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'CrystalStructure 3.7.0' _computing_publication_material 'CrystalStructure 3.7.0' _refine_special_details ; Refinement of F^2^ against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F^2^, conventional R-factors R are based on F, with F set to zero for negative F^2^. The threshold expression of F^2^ > 2sigma(F^2^) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F^2^ are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger. ; _refine_ls_structure_factor_coef Fsqd _refine_ls_matrix_type full _refine_ls_weighting_scheme calc _refine_ls_weighting_details 'calc w=1/[\s^2^(Fo^2^)+(0.0611P)^2^+4.2166P] 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 5406 _refine_ls_number_parameters 299 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0545 _refine_ls_R_factor_gt 0.0502 _refine_ls_wR_factor_ref 0.1326 _refine_ls_wR_factor_gt 0.1295 _refine_ls_goodness_of_fit_ref 1.101 _refine_ls_restrained_S_all 1.101 _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 Br1 Br 0.53200(3) 1.08191(4) 0.27355(2) 0.04312(14) Uani 1 1 d . . . Fe1 Fe 0.41299(4) 0.96424(4) 0.32969(2) 0.02421(14) Uani 1 1 d . . . O1 O 0.39719(18) 1.08562(19) 0.39136(11) 0.0251(5) Uani 1 1 d . . . O2 O 0.28498(19) 0.93902(19) 0.26007(11) 0.0262(5) Uani 1 1 d . . . O3 O 0.5303(2) 0.8239(2) 0.34730(13) 0.0370(6) Uani 1 1 d . . . N1 N 0.3458(2) 0.8363(2) 0.39609(12) 0.0219(5) Uani 1 1 d . . . C1 C 0.0916(3) 1.1209(4) 0.5644(2) 0.0410(9) Uani 1 1 d . . . H1 H 0.0876 1.2041 0.5795 0.049 Uiso 1 1 calc R . . H2 H 0.1151 1.0688 0.6050 0.049 Uiso 1 1 calc R . . H3 H 0.0175 1.0956 0.5373 0.049 Uiso 1 1 calc R . . C2 C 0.1764(3) 1.1117(3) 0.51954(18) 0.0312(7) Uani 1 1 d . . . C3 C 0.1927(3) 1.2084(3) 0.47838(17) 0.0278(7) Uani 1 1 d . . . H4 H 0.1515 1.2800 0.4804 0.033 Uiso 1 1 calc R . . C4 C 0.2660(3) 1.2059(3) 0.43444(16) 0.0245(6) Uani 1 1 d . . . C5 C 0.3253(3) 1.0974(3) 0.43254(15) 0.0227(6) Uani 1 1 d . . . C6 C 0.3116(3) 0.9995(3) 0.47441(16) 0.0257(6) Uani 1 1 d . . . C7 C 0.2371(3) 1.0078(3) 0.51719(17) 0.0302(7) Uani 1 1 d . . . H5 H 0.2279 0.9412 0.5452 0.036 Uiso 1 1 calc R . . C8 C 0.2794(3) 1.3139(3) 0.38935(17) 0.0282(7) Uani 1 1 d . . . C9 C 0.4033(3) 1.3510(3) 0.4017(2) 0.0371(8) Uani 1 1 d . . . H12 H 0.4082 1.4312 0.3825 0.045 Uiso 1 1 calc R . . H13 H 0.4431 1.2934 0.3789 0.045 Uiso 1 1 calc R . . H14 H 0.4376 1.3518 0.4516 0.045 Uiso 1 1 calc R . . C10 C 0.2324(3) 1.2822(3) 0.31219(18) 0.0373(8) Uani 1 1 d . . . H9 H 0.2546 1.3441 0.2831 0.045 Uiso 1 1 calc R . . H10 H 0.1504 1.2779 0.3023 0.045 Uiso 1 1 calc R . . H11 H 0.2623 1.2044 0.3022 0.045 Uiso 1 1 calc R . . C11 C 0.2145(4) 1.4234(3) 0.4052(2) 0.0404(9) Uani 1 1 d . . . H6 H 0.2166 1.4868 0.3713 0.048 Uiso 1 1 calc R . . H7 H 0.2489 1.4528 0.4519 0.048 Uiso 1 1 calc R . . H8 H 0.1364 1.4007 0.4024 0.048 Uiso 1 1 calc R . . C12 C 0.3732(3) 0.8843(3) 0.46873(16) 0.0268(7) Uani 1 1 d . . . H15 H 0.4550 0.8987 0.4839 0.032 Uiso 1 1 calc R . . H16 H 0.3530 0.8236 0.5001 0.032 Uiso 1 1 calc R . . C13 C 0.2223(3) 0.8232(3) 0.37114(15) 0.0253(6) Uani 1 1 d . . . H17 H 0.1869 0.9016 0.3760 0.030 Uiso 1 1 calc R . . H18 H 0.1958 0.7652 0.4015 0.030 Uiso 1 1 calc R . . C14 C 0.1827(3) 0.7819(3) 0.29726(15) 0.0234(6) Uani 1 1 d . . . C15 C 0.2124(2) 0.8467(3) 0.24362(15) 0.0217(6) Uani 1 1 d . . . C16 C 0.1634(2) 0.8183(3) 0.17381(15) 0.0226(6) Uani 1 1 d . . . C17 C 0.0902(3) 0.7208(3) 0.16089(16) 0.0255(6) Uani 1 1 d . . . H19 H 0.0578 0.6995 0.1141 0.031 Uiso 1 1 calc R . . C18 C 0.0621(3) 0.6528(3) 0.21316(17) 0.0270(7) Uani 1 1 d . . . C19 C 0.1087(3) 0.6864(3) 0.28155(16) 0.0263(6) Uani 1 1 d . . . H20 H 0.0893 0.6429 0.3181 0.032 Uiso 1 1 calc R . . C20 C -0.0173(3) 0.5469(3) 0.19651(18) 0.0338(8) Uani 1 1 d . . . H21 H -0.0700 0.5488 0.2266 0.041 Uiso 1 1 calc R . . H22 H 0.0257 0.4720 0.2042 0.041 Uiso 1 1 calc R . . H23 H -0.0592 0.5514 0.1479 0.041 Uiso 1 1 calc R . . C21 C 0.1898(3) 0.8929(3) 0.11446(16) 0.0263(7) Uani 1 1 d . . . C22 C 0.3157(3) 0.8837(3) 0.11638(18) 0.0340(8) Uani 1 1 d . . . H24 H 0.3351 0.9438 0.0852 0.041 Uiso 1 1 calc R . . H25 H 0.3323 0.8033 0.1015 0.041 Uiso 1 1 calc R . . H26 H 0.3598 0.8981 0.1637 0.041 Uiso 1 1 calc R . . C23 C 0.1573(3) 1.0251(3) 0.12140(18) 0.0340(8) Uani 1 1 d . . . H27 H 0.0825 1.0290 0.1307 0.041 Uiso 1 1 calc R . . H28 H 0.1567 1.0678 0.0782 0.041 Uiso 1 1 calc R . . H29 H 0.2119 1.0626 0.1597 0.041 Uiso 1 1 calc R . . C24 C 0.1237(3) 0.8488(3) 0.04296(16) 0.0333(8) Uani 1 1 d . . . H30 H 0.0443 0.8696 0.0365 0.040 Uiso 1 1 calc R . . H31 H 0.1314 0.7615 0.0401 0.040 Uiso 1 1 calc R . . H32 H 0.1534 0.8873 0.0067 0.040 Uiso 1 1 calc R . . C25 C 0.4014(3) 0.7181(3) 0.39442(17) 0.0291(7) Uani 1 1 d . . . H33 H 0.3652 0.6751 0.3512 0.035 Uiso 1 1 calc R . . H34 H 0.3924 0.6688 0.4342 0.035 Uiso 1 1 calc R . . C26 C 0.5230(3) 0.7341(3) 0.39776(17) 0.0331(7) Uani 1 1 d . . . H35 H 0.5634 0.7606 0.4446 0.040 Uiso 1 1 calc R . . H36 H 0.5563 0.6577 0.3869 0.040 Uiso 1 1 calc R . . C27 C 0.6338(4) 0.8151(4) 0.3242(2) 0.0517(11) Uani 1 1 d . . . H37 H 0.6186 0.7762 0.2787 0.062 Uiso 1 1 calc R . . H38 H 0.6886 0.7676 0.3576 0.062 Uiso 1 1 calc R . . H39 H 0.6639 0.8958 0.3208 0.062 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Br1 0.0425(3) 0.0441(2) 0.0478(2) 0.00342(16) 0.02077(18) -0.00906(17) Fe1 0.0238(3) 0.0241(2) 0.0243(2) 0.00019(16) 0.00472(18) -0.00070(17) O1 0.0243(12) 0.0233(11) 0.0287(11) -0.0008(8) 0.0080(9) -0.0005(9) O2 0.0289(12) 0.0239(11) 0.0236(11) 0.0039(8) 0.0019(9) -0.0059(9) O3 0.0339(13) 0.0362(13) 0.0451(14) 0.0034(11) 0.0177(11) 0.0091(11) N1 0.0244(13) 0.0178(12) 0.0221(12) -0.0003(9) 0.0032(10) 0.0018(10) C1 0.043(2) 0.042(2) 0.042(2) 0.0018(17) 0.0207(17) -0.0075(17) C2 0.0326(18) 0.0322(17) 0.0320(17) -0.0017(14) 0.0136(14) -0.0043(14) C3 0.0268(17) 0.0262(16) 0.0317(16) -0.0027(13) 0.0094(13) 0.0005(13) C4 0.0235(15) 0.0235(15) 0.0260(15) 0.0005(12) 0.0047(12) -0.0007(12) C5 0.0216(15) 0.0229(14) 0.0236(14) -0.0029(11) 0.0053(12) -0.0028(12) C6 0.0294(17) 0.0221(14) 0.0243(15) -0.0005(12) 0.0037(12) -0.0002(13) C7 0.0371(19) 0.0254(16) 0.0288(16) -0.0003(13) 0.0089(14) -0.0043(14) C8 0.0269(17) 0.0240(15) 0.0355(17) 0.0036(13) 0.0110(14) 0.0029(13) C9 0.0321(19) 0.0283(17) 0.051(2) 0.0058(15) 0.0097(16) -0.0045(14) C10 0.041(2) 0.0367(19) 0.0344(18) 0.0082(15) 0.0101(16) 0.0029(16) C11 0.046(2) 0.0263(17) 0.054(2) 0.0067(16) 0.0222(19) 0.0080(16) C12 0.0334(18) 0.0229(15) 0.0222(15) 0.0023(12) 0.0024(13) 0.0002(13) C13 0.0242(16) 0.0271(16) 0.0239(15) 0.0023(12) 0.0047(12) 0.0002(12) C14 0.0216(15) 0.0221(14) 0.0250(15) 0.0039(11) 0.0026(12) 0.0025(12) C15 0.0199(15) 0.0207(14) 0.0236(14) 0.0021(11) 0.0035(11) 0.0006(11) C16 0.0201(15) 0.0232(14) 0.0238(14) 0.0014(11) 0.0039(11) 0.0003(12) C17 0.0226(16) 0.0264(16) 0.0263(15) -0.0019(12) 0.0033(12) -0.0020(12) C18 0.0243(16) 0.0238(15) 0.0323(16) -0.0014(12) 0.0057(13) -0.0044(12) C19 0.0275(16) 0.0241(15) 0.0278(15) 0.0040(12) 0.0077(13) -0.0015(13) C20 0.0348(19) 0.0307(17) 0.0369(18) -0.0025(14) 0.0110(15) -0.0123(15) C21 0.0267(17) 0.0280(15) 0.0237(15) 0.0024(12) 0.0051(12) -0.0010(13) C22 0.0268(18) 0.046(2) 0.0291(17) 0.0024(15) 0.0076(13) -0.0056(15) C23 0.040(2) 0.0319(18) 0.0284(16) 0.0084(13) 0.0046(14) -0.0006(15) C24 0.0349(19) 0.0388(18) 0.0249(16) 0.0038(14) 0.0043(14) -0.0069(15) C25 0.0329(18) 0.0189(15) 0.0326(17) 0.0009(12) 0.0021(14) 0.0055(13) C26 0.0342(19) 0.0329(17) 0.0298(17) 0.0019(13) 0.0028(14) 0.0099(15) C27 0.043(2) 0.054(3) 0.067(3) 0.000(2) 0.029(2) 0.008(2) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Br1 Fe1 2.4242(6) . ? Fe1 O2 1.850(2) . ? Fe1 O1 1.866(2) . ? Fe1 O3 2.098(2) . ? Fe1 N1 2.231(3) . ? O1 C5 1.346(4) . ? O2 C15 1.349(4) . ? O3 C26 1.434(4) . ? O3 C27 1.454(5) . ? N1 C13 1.485(4) . ? N1 C25 1.487(4) . ? N1 C12 1.500(4) . ? C1 C2 1.527(5) . ? C1 H1 0.9800 . ? C1 H2 0.9800 . ? C1 H3 0.9800 . ? C2 C7 1.384(5) . ? C2 C3 1.395(5) . ? C3 C4 1.396(4) . ? C3 H4 0.9500 . ? C4 C5 1.417(4) . ? C4 C8 1.533(4) . ? C5 C6 1.406(4) . ? C6 C7 1.392(5) . ? C6 C12 1.508(4) . ? C7 H5 0.9500 . ? C8 C11 1.530(5) . ? C8 C9 1.538(5) . ? C8 C10 1.545(5) . ? C9 H12 0.9800 . ? C9 H13 0.9800 . ? C9 H14 0.9800 . ? C10 H9 0.9800 . ? C10 H10 0.9800 . ? C10 H11 0.9800 . ? C11 H6 0.9800 . ? C11 H7 0.9800 . ? C11 H8 0.9800 . ? C12 H15 0.9900 . ? C12 H16 0.9900 . ? C13 C14 1.504(4) . ? C13 H17 0.9900 . ? C13 H18 0.9900 . ? C14 C19 1.385(4) . ? C14 C15 1.406(4) . ? C15 C16 1.410(4) . ? C16 C17 1.394(4) . ? C16 C21 1.539(4) . ? C17 C18 1.394(4) . ? C17 H19 0.9500 . ? C18 C19 1.394(4) . ? C18 C20 1.515(4) . ? C19 H20 0.9500 . ? C20 H21 0.9800 . ? C20 H22 0.9800 . ? C20 H23 0.9800 . ? C21 C24 1.538(4) . ? C21 C22 1.540(5) . ? C21 C23 1.541(5) . ? C22 H24 0.9800 . ? C22 H25 0.9800 . ? C22 H26 0.9800 . ? C23 H27 0.9800 . ? C23 H28 0.9800 . ? C23 H29 0.9800 . ? C24 H30 0.9800 . ? C24 H31 0.9800 . ? C24 H32 0.9800 . ? C25 C26 1.488(5) . ? C25 H33 0.9900 . ? C25 H34 0.9900 . ? C26 H35 0.9900 . ? C26 H36 0.9900 . ? C27 H37 0.9800 . ? C27 H38 0.9800 . ? C27 H39 0.9800 . ? 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 O2 Fe1 O1 113.45(10) . . ? O2 Fe1 O3 115.97(10) . . ? O1 Fe1 O3 127.29(10) . . ? O2 Fe1 N1 88.69(9) . . ? O1 Fe1 N1 87.92(9) . . ? O3 Fe1 N1 76.16(10) . . ? O2 Fe1 Br1 103.63(7) . . ? O1 Fe1 Br1 94.53(7) . . ? O3 Fe1 Br1 90.85(7) . . ? N1 Fe1 Br1 165.18(7) . . ? C5 O1 Fe1 131.00(19) . . ? C15 O2 Fe1 133.69(18) . . ? C26 O3 C27 112.3(3) . . ? C26 O3 Fe1 118.8(2) . . ? C27 O3 Fe1 127.9(2) . . ? C13 N1 C25 110.1(2) . . ? C13 N1 C12 109.4(2) . . ? C25 N1 C12 109.8(2) . . ? C13 N1 Fe1 110.94(17) . . ? C25 N1 Fe1 108.42(19) . . ? C12 N1 Fe1 108.15(18) . . ? C2 C1 H1 109.5 . . ? C2 C1 H2 109.5 . . ? H1 C1 H2 109.5 . . ? C2 C1 H3 109.5 . . ? H1 C1 H3 109.5 . . ? H2 C1 H3 109.5 . . ? C7 C2 C3 118.2(3) . . ? C7 C2 C1 121.6(3) . . ? C3 C2 C1 120.2(3) . . ? C2 C3 C4 123.7(3) . . ? C2 C3 H4 118.2 . . ? C4 C3 H4 118.2 . . ? C3 C4 C5 116.5(3) . . ? C3 C4 C8 121.7(3) . . ? C5 C4 C8 121.8(3) . . ? O1 C5 C6 118.3(3) . . ? O1 C5 C4 121.0(3) . . ? C6 C5 C4 120.7(3) . . ? C7 C6 C5 120.0(3) . . ? C7 C6 C12 121.1(3) . . ? C5 C6 C12 118.8(3) . . ? C2 C7 C6 120.9(3) . . ? C2 C7 H5 119.5 . . ? C6 C7 H5 119.5 . . ? C11 C8 C4 111.8(3) . . ? C11 C8 C9 107.3(3) . . ? C4 C8 C9 111.0(3) . . ? C11 C8 C10 107.3(3) . . ? C4 C8 C10 109.5(3) . . ? C9 C8 C10 109.9(3) . . ? C8 C9 H12 109.5 . . ? C8 C9 H13 109.5 . . ? H12 C9 H13 109.5 . . ? C8 C9 H14 109.5 . . ? H12 C9 H14 109.5 . . ? H13 C9 H14 109.5 . . ? C8 C10 H9 109.5 . . ? C8 C10 H10 109.5 . . ? H9 C10 H10 109.5 . . ? C8 C10 H11 109.5 . . ? H9 C10 H11 109.5 . . ? H10 C10 H11 109.5 . . ? C8 C11 H6 109.5 . . ? C8 C11 H7 109.5 . . ? H6 C11 H7 109.5 . . ? C8 C11 H8 109.5 . . ? H6 C11 H8 109.5 . . ? H7 C11 H8 109.5 . . ? N1 C12 C6 112.0(2) . . ? N1 C12 H15 109.2 . . ? C6 C12 H15 109.2 . . ? N1 C12 H16 109.2 . . ? C6 C12 H16 109.2 . . ? H15 C12 H16 107.9 . . ? N1 C13 C14 114.9(3) . . ? N1 C13 H17 108.5 . . ? C14 C13 H17 108.5 . . ? N1 C13 H18 108.5 . . ? C14 C13 H18 108.5 . . ? H17 C13 H18 107.5 . . ? C19 C14 C15 119.9(3) . . ? C19 C14 C13 119.8(3) . . ? C15 C14 C13 120.0(3) . . ? O2 C15 C14 119.0(3) . . ? O2 C15 C16 120.8(3) . . ? C14 C15 C16 120.2(3) . . ? C17 C16 C15 117.5(3) . . ? C17 C16 C21 121.6(3) . . ? C15 C16 C21 120.9(3) . . ? C18 C17 C16 123.4(3) . . ? C18 C17 H19 118.3 . . ? C16 C17 H19 118.3 . . ? C19 C18 C17 117.6(3) . . ? C19 C18 C20 121.0(3) . . ? C17 C18 C20 121.4(3) . . ? C14 C19 C18 121.3(3) . . ? C14 C19 H20 119.3 . . ? C18 C19 H20 119.3 . . ? C18 C20 H21 109.5 . . ? C18 C20 H22 109.5 . . ? H21 C20 H22 109.5 . . ? C18 C20 H23 109.5 . . ? H21 C20 H23 109.5 . . ? H22 C20 H23 109.5 . . ? C24 C21 C16 112.0(3) . . ? C24 C21 C22 107.8(3) . . ? C16 C21 C22 109.8(3) . . ? C24 C21 C23 107.3(3) . . ? C16 C21 C23 109.9(3) . . ? C22 C21 C23 110.0(3) . . ? C21 C22 H24 109.5 . . ? C21 C22 H25 109.5 . . ? H24 C22 H25 109.5 . . ? C21 C22 H26 109.5 . . ? H24 C22 H26 109.5 . . ? H25 C22 H26 109.5 . . ? C21 C23 H27 109.5 . . ? C21 C23 H28 109.5 . . ? H27 C23 H28 109.5 . . ? C21 C23 H29 109.5 . . ? H27 C23 H29 109.5 . . ? H28 C23 H29 109.5 . . ? C21 C24 H30 109.5 . . ? C21 C24 H31 109.5 . . ? H30 C24 H31 109.5 . . ? C21 C24 H32 109.5 . . ? H30 C24 H32 109.5 . . ? H31 C24 H32 109.5 . . ? N1 C25 C26 110.7(3) . . ? N1 C25 H33 109.5 . . ? C26 C25 H33 109.5 . . ? N1 C25 H34 109.5 . . ? C26 C25 H34 109.5 . . ? H33 C25 H34 108.1 . . ? O3 C26 C25 106.4(3) . . ? O3 C26 H35 110.5 . . ? C25 C26 H35 110.5 . . ? O3 C26 H36 110.5 . . ? C25 C26 H36 110.5 . . ? H35 C26 H36 108.6 . . ? O3 C27 H37 109.5 . . ? O3 C27 H38 109.5 . . ? H37 C27 H38 109.5 . . ? O3 C27 H39 109.5 . . ? H37 C27 H39 109.5 . . ? H38 C27 H39 109.5 . . ? 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 O2 Fe1 O1 C5 59.2(3) . . . . ? O3 Fe1 O1 C5 -99.3(3) . . . . ? N1 Fe1 O1 C5 -28.5(3) . . . . ? Br1 Fe1 O1 C5 166.1(2) . . . . ? O1 Fe1 O2 C15 -114.1(3) . . . . ? O3 Fe1 O2 C15 47.0(3) . . . . ? N1 Fe1 O2 C15 -26.9(3) . . . . ? Br1 Fe1 O2 C15 144.8(3) . . . . ? O2 Fe1 O3 C26 -91.6(2) . . . . ? O1 Fe1 O3 C26 66.4(3) . . . . ? N1 Fe1 O3 C26 -10.0(2) . . . . ? Br1 Fe1 O3 C26 162.8(2) . . . . ? O2 Fe1 O3 C27 101.0(3) . . . . ? O1 Fe1 O3 C27 -101.0(3) . . . . ? N1 Fe1 O3 C27 -177.4(3) . . . . ? Br1 Fe1 O3 C27 -4.7(3) . . . . ? O2 Fe1 N1 C13 -20.77(19) . . . . ? O1 Fe1 N1 C13 92.76(19) . . . . ? O3 Fe1 N1 C13 -137.9(2) . . . . ? Br1 Fe1 N1 C13 -167.37(19) . . . . ? O2 Fe1 N1 C25 100.24(19) . . . . ? O1 Fe1 N1 C25 -146.23(19) . . . . ? O3 Fe1 N1 C25 -16.94(19) . . . . ? Br1 Fe1 N1 C25 -46.4(4) . . . . ? O2 Fe1 N1 C12 -140.7(2) . . . . ? O1 Fe1 N1 C12 -27.22(19) . . . . ? O3 Fe1 N1 C12 102.1(2) . . . . ? Br1 Fe1 N1 C12 72.7(3) . . . . ? C7 C2 C3 C4 0.6(5) . . . . ? C1 C2 C3 C4 -177.9(3) . . . . ? C2 C3 C4 C5 0.4(5) . . . . ? C2 C3 C4 C8 179.0(3) . . . . ? Fe1 O1 C5 C6 48.8(4) . . . . ? Fe1 O1 C5 C4 -132.0(3) . . . . ? C3 C4 C5 O1 179.4(3) . . . . ? C8 C4 C5 O1 0.8(5) . . . . ? C3 C4 C5 C6 -1.4(4) . . . . ? C8 C4 C5 C6 180.0(3) . . . . ? O1 C5 C6 C7 -179.4(3) . . . . ? C4 C5 C6 C7 1.4(5) . . . . ? O1 C5 C6 C12 -3.0(4) . . . . ? C4 C5 C6 C12 177.8(3) . . . . ? C3 C2 C7 C6 -0.6(5) . . . . ? C1 C2 C7 C6 177.9(3) . . . . ? C5 C6 C7 C2 -0.4(5) . . . . ? C12 C6 C7 C2 -176.6(3) . . . . ? C3 C4 C8 C11 6.3(4) . . . . ? C5 C4 C8 C11 -175.2(3) . . . . ? C3 C4 C8 C9 126.0(3) . . . . ? C5 C4 C8 C9 -55.4(4) . . . . ? C3 C4 C8 C10 -112.5(3) . . . . ? C5 C4 C8 C10 66.1(4) . . . . ? C13 N1 C12 C6 -54.6(3) . . . . ? C25 N1 C12 C6 -175.5(3) . . . . ? Fe1 N1 C12 C6 66.3(3) . . . . ? C7 C6 C12 N1 119.3(3) . . . . ? C5 C6 C12 N1 -57.0(4) . . . . ? C25 N1 C13 C14 -62.4(3) . . . . ? C12 N1 C13 C14 176.9(2) . . . . ? Fe1 N1 C13 C14 57.6(3) . . . . ? N1 C13 C14 C19 129.7(3) . . . . ? N1 C13 C14 C15 -56.1(4) . . . . ? Fe1 O2 C15 C14 38.5(4) . . . . ? Fe1 O2 C15 C16 -144.1(2) . . . . ? C19 C14 C15 O2 -179.7(3) . . . . ? C13 C14 C15 O2 6.2(4) . . . . ? C19 C14 C15 C16 2.8(4) . . . . ? C13 C14 C15 C16 -171.3(3) . . . . ? O2 C15 C16 C17 179.2(3) . . . . ? C14 C15 C16 C17 -3.3(4) . . . . ? O2 C15 C16 C21 -1.0(4) . . . . ? C14 C15 C16 C21 176.5(3) . . . . ? C15 C16 C17 C18 1.3(5) . . . . ? C21 C16 C17 C18 -178.4(3) . . . . ? C16 C17 C18 C19 1.1(5) . . . . ? C16 C17 C18 C20 -179.6(3) . . . . ? C15 C14 C19 C18 -0.3(5) . . . . ? C13 C14 C19 C18 173.9(3) . . . . ? C17 C18 C19 C14 -1.7(5) . . . . ? C20 C18 C19 C14 179.0(3) . . . . ? C17 C16 C21 C24 1.9(4) . . . . ? C15 C16 C21 C24 -177.8(3) . . . . ? C17 C16 C21 C22 -117.8(3) . . . . ? C15 C16 C21 C22 62.4(4) . . . . ? C17 C16 C21 C23 121.1(3) . . . . ? C15 C16 C21 C23 -58.7(4) . . . . ? C13 N1 C25 C26 162.4(3) . . . . ? C12 N1 C25 C26 -77.1(3) . . . . ? Fe1 N1 C25 C26 40.9(3) . . . . ? C27 O3 C26 C25 -156.4(3) . . . . ? Fe1 O3 C26 C25 34.3(3) . . . . ? N1 C25 C26 O3 -48.4(3) . . . . ? _diffrn_measured_fraction_theta_max 0.991 _diffrn_reflns_theta_full 26.50 _diffrn_measured_fraction_theta_full 0.991 _refine_diff_density_max 0.437 _refine_diff_density_min -0.704 _refine_diff_density_rms 0.083 #===END