Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2005 data_global _journal_name_full 'Dalton Trans.' _journal_coden_Cambridge 0222 _publ_contact_author_name 'Christophe Bucher' _publ_contact_author_address ; Institut de Chimie UJF UMR CNRS 5630 LEOPR BP 53 Grenoble 38041 FRANCE ; _publ_contact_author_email CHRISTOPHE.BUCHER@UJF-GRENOBLE.FR _publ_section_title ; Calix[4]phyrin based redox architectures: towards new molecular tools for electrochemical sensing. ; loop_ _publ_author_name 'Christophe Bucher' 'Charles Devillers' 'Jean-Claude Moutet' 'J. Pecaut' 'Guy Royal' ; E.Saint-Aman ; 'Fabrice Thomas' data_struc_1 _database_code_depnum_ccdc_archive 'CCDC 272660' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 'calix(4)phyrin (1)' _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C40 H46 Fe N4 O' _chemical_formula_weight 654.66 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' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Triclinic _symmetry_space_group_name_H-M P-1 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, -z' _cell_length_a 7.7327(15) _cell_length_b 13.530(3) _cell_length_c 17.245(3) _cell_angle_alpha 108.78(3) _cell_angle_beta 91.96(3) _cell_angle_gamma 91.09(3) _cell_volume 1706.3(6) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 940 _cell_measurement_theta_min 3.182 _cell_measurement_theta_max 28.135 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.274 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 696 _exptl_absorpt_coefficient_mu 0.479 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 10819 _diffrn_reflns_av_R_equivalents 0.0176 _diffrn_reflns_av_sigmaI/netI 0.0366 _diffrn_reflns_limit_h_min -10 _diffrn_reflns_limit_h_max 10 _diffrn_reflns_limit_k_min -17 _diffrn_reflns_limit_k_max 17 _diffrn_reflns_limit_l_min -18 _diffrn_reflns_limit_l_max 23 _diffrn_reflns_theta_min 2.32 _diffrn_reflns_theta_max 28.76 _reflns_number_total 7633 _reflns_number_gt 5789 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0656P)^2^+0.5961P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 7633 _refine_ls_number_parameters 415 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0676 _refine_ls_R_factor_gt 0.0493 _refine_ls_wR_factor_ref 0.1390 _refine_ls_wR_factor_gt 0.1277 _refine_ls_goodness_of_fit_ref 1.053 _refine_ls_restrained_S_all 1.053 _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 Fe Fe 0.67163(4) -0.35397(2) 0.66656(2) 0.04988(13) Uani 1 1 d . . . N1 N 0.7429(3) 0.04751(14) 0.81985(11) 0.0511(5) Uani 1 1 d . . . H1N H 0.7452 0.0939 0.7955 0.061 Uiso 1 1 calc R . . N2 N 0.7087(2) 0.05569(13) 0.66100(11) 0.0427(4) Uani 1 1 d . . . N3 N 0.8533(2) 0.30049(13) 0.71968(11) 0.0463(4) Uani 1 1 d . . . H3N H 0.7831 0.2839 0.7514 0.056 Uiso 1 1 calc R . . N4 N 0.9107(3) 0.28632(14) 0.89823(12) 0.0522(5) Uani 1 1 d . . . H4N H 0.9968 0.2455 0.8867 0.063 Uiso 1 1 calc R . . C1 C 0.7392(4) 0.06846(19) 0.90168(14) 0.0599(7) Uani 1 1 d . . . C2 C 0.7319(4) -0.0260(2) 0.91668(16) 0.0743(9) Uani 1 1 d . . . H2 H 0.7267 -0.0346 0.9680 0.089 Uiso 1 1 calc R . . C3 C 0.7336(4) -0.1055(2) 0.84249(16) 0.0655(7) Uani 1 1 d . . . H3 H 0.7295 -0.1767 0.8351 0.079 Uiso 1 1 calc R . . C4 C 0.7426(3) -0.06004(16) 0.78042(14) 0.0480(5) Uani 1 1 d . . . C5 C 0.7606(3) -0.10657(15) 0.69401(13) 0.0416(4) Uani 1 1 d . . . C6 C 0.7574(3) -0.04953(15) 0.63940(13) 0.0398(4) Uani 1 1 d . . . C7 C 0.8085(3) -0.08167(16) 0.55585(14) 0.0469(5) Uani 1 1 d . . . H7 H 0.8476 -0.1470 0.5261 0.056 Uiso 1 1 calc R . . C8 C 0.7895(3) 0.00057(17) 0.52844(13) 0.0478(5) Uani 1 1 d . . . H8 H 0.8132 0.0027 0.4765 0.057 Uiso 1 1 calc R . . C9 C 0.7256(3) 0.08395(15) 0.59471(12) 0.0402(4) Uani 1 1 d . . . C10 C 0.6855(3) 0.19323(16) 0.59240(13) 0.0437(5) Uani 1 1 d . . . C11 C 0.8348(3) 0.26675(15) 0.63609(13) 0.0433(5) Uani 1 1 d . . . C12 C 0.9719(3) 0.31005(17) 0.60858(16) 0.0534(6) Uani 1 1 d . . . H12 H 0.9937 0.3012 0.5541 0.064 Uiso 1 1 calc R . . C13 C 1.0744(3) 0.37062(18) 0.67784(17) 0.0574(6) Uani 1 1 d . . . H13 H 1.1757 0.4082 0.6767 0.069 Uiso 1 1 calc R . . C14 C 0.9988(3) 0.36437(16) 0.74664(15) 0.0480(5) Uani 1 1 d . . . C15 C 1.0384(3) 0.41766(17) 0.83737(16) 0.0549(6) Uani 1 1 d . . . C16 C 0.9034(3) 0.38154(17) 0.88443(14) 0.0510(5) Uani 1 1 d . . . C17 C 0.7480(4) 0.4208(2) 0.91017(17) 0.0680(7) Uani 1 1 d . . . H17 H 0.7062 0.4840 0.9082 0.082 Uiso 1 1 calc R . . C18 C 0.6606(4) 0.3498(3) 0.94040(18) 0.0726(8) Uani 1 1 d . . . H18 H 0.5514 0.3583 0.9621 0.087 Uiso 1 1 calc R . . C19 C 0.7630(4) 0.26576(19) 0.93251(15) 0.0597(6) Uani 1 1 d . . . C20 C 0.7449(5) 0.1761(2) 0.96633(16) 0.0773(9) Uani 1 1 d . . . C21 C 0.5140(3) 0.22778(18) 0.63436(16) 0.0535(6) Uani 1 1 d . . . H21A H 0.5238 0.2281 0.6901 0.080 Uiso 1 1 calc R . . H21B H 0.4220 0.1800 0.6056 0.080 Uiso 1 1 calc R . . H21C H 0.4893 0.2967 0.6335 0.080 Uiso 1 1 calc R . . C22 C 0.6687(4) 0.1932(2) 0.50331(15) 0.0595(6) Uani 1 1 d . . . H22A H 0.7754 0.1718 0.4769 0.089 Uiso 1 1 calc R . . H22B H 0.6439 0.2622 0.5028 0.089 Uiso 1 1 calc R . . H22C H 0.5766 0.1455 0.4746 0.089 Uiso 1 1 calc R . . C23 C 1.2231(4) 0.3946(3) 0.8618(2) 0.0787(9) Uani 1 1 d . . . H23A H 1.2330 0.3208 0.8508 0.118 Uiso 1 1 calc R . . H23B H 1.2462 0.4302 0.9193 0.118 Uiso 1 1 calc R . . H23C H 1.3052 0.4184 0.8307 0.118 Uiso 1 1 calc R . . C24 C 1.0295(5) 0.5372(2) 0.8565(2) 0.0824(10) Uani 1 1 d . . . H24A H 0.9157 0.5543 0.8419 0.124 Uiso 1 1 calc R . . H24B H 1.1132 0.5600 0.8256 0.124 Uiso 1 1 calc R . . H24C H 1.0540 0.5715 0.9140 0.124 Uiso 1 1 calc R . . C25 C 0.5787(8) 0.1870(3) 1.0133(3) 0.158(3) Uani 1 1 d . . . H25A H 0.4811 0.1852 0.9769 0.237 Uiso 1 1 calc R . . H25B H 0.5832 0.2523 1.0573 0.237 Uiso 1 1 calc R . . H25C H 0.5674 0.1305 1.0353 0.237 Uiso 1 1 calc R . . C26 C 0.9033(7) 0.1799(3) 1.0261(2) 0.1193(18) Uani 1 1 d . . . H26A H 0.9113 0.2470 1.0680 0.179 Uiso 1 1 calc R . . H26B H 1.0074 0.1687 0.9962 0.179 Uiso 1 1 calc R . . H26C H 0.8884 0.1264 1.0510 0.179 Uiso 1 1 calc R . . C31 C 0.7985(3) -0.21948(16) 0.66104(14) 0.0451(5) Uani 1 1 d . . . C32 C 0.7485(3) -0.28937(16) 0.58120(15) 0.0515(5) Uani 1 1 d . . . H32 H 0.6724 -0.2730 0.5407 0.062 Uiso 1 1 calc R . . C33 C 0.8295(4) -0.38618(19) 0.57024(19) 0.0655(7) Uani 1 1 d . . . H33 H 0.8191 -0.4476 0.5208 0.079 Uiso 1 1 calc R . . C34 C 0.9261(4) -0.3790(2) 0.6427(2) 0.0684(7) Uani 1 1 d . . . H34 H 0.9941 -0.4347 0.6523 0.082 Uiso 1 1 calc R . . C35 C 0.9085(3) -0.27737(19) 0.69927(18) 0.0579(6) Uani 1 1 d . . . H35 H 0.9610 -0.2511 0.7549 0.069 Uiso 1 1 calc R . . C36 C 0.4529(4) -0.3211(2) 0.7324(3) 0.0834(10) Uani 1 1 d . . . H36 H 0.4126 -0.2511 0.7614 0.100 Uiso 1 1 calc R . . C37 C 0.4097(4) -0.3803(3) 0.6498(3) 0.0858(10) Uani 1 1 d . . . H37 H 0.3336 -0.3591 0.6117 0.103 Uiso 1 1 calc R . . C38 C 0.4963(4) -0.4763(2) 0.6325(2) 0.0777(9) Uani 1 1 d . . . H38 H 0.4906 -0.5333 0.5801 0.093 Uiso 1 1 calc R . . C39 C 0.5904(4) -0.4753(2) 0.7039(2) 0.0721(8) Uani 1 1 d . . . H39 H 0.6626 -0.5315 0.7096 0.087 Uiso 1 1 calc R . . C40 C 0.5641(4) -0.3797(2) 0.7658(2) 0.0748(8) Uani 1 1 d . . . H40 H 0.6145 -0.3579 0.8219 0.090 Uiso 1 1 calc R . . O51 O 1.1574(4) 0.12128(17) 0.82417(16) 0.1016(8) Uani 1 1 d . . . C52 C 1.2494(7) 0.0095(5) 0.7061(3) 0.1284(17) Uani 1 1 d . . . H52A H 1.3623 0.0131 0.6841 0.154 Uiso 1 1 calc R . . H52B H 1.1690 -0.0275 0.6612 0.154 Uiso 1 1 calc R . . C53 C 1.2593(6) -0.0441(3) 0.7662(5) 0.149(2) Uani 1 1 d . . . H53A H 1.3773 -0.0636 0.7738 0.178 Uiso 1 1 calc R . . H53B H 1.1853 -0.1067 0.7492 0.178 Uiso 1 1 calc R . . C51 C 1.1945(9) 0.1064(4) 0.7441(3) 0.160(3) Uani 1 1 d . . . H51A H 1.0916 0.1183 0.7150 0.192 Uiso 1 1 calc R . . H51B H 1.2833 0.1572 0.7423 0.192 Uiso 1 1 calc R . . C54 C 1.2008(7) 0.0299(4) 0.8417(3) 0.1217(15) Uani 1 1 d . . . H54A H 1.1008 0.0012 0.8604 0.146 Uiso 1 1 calc R . . H54B H 1.2920 0.0453 0.8843 0.146 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 Fe 0.0518(2) 0.03114(16) 0.0700(2) 0.02121(15) 0.00061(15) -0.00014(12) N1 0.0708(13) 0.0382(9) 0.0430(10) 0.0120(8) 0.0027(9) -0.0144(9) N2 0.0550(11) 0.0312(8) 0.0418(9) 0.0119(7) 0.0017(8) -0.0014(7) N3 0.0524(11) 0.0395(9) 0.0489(10) 0.0181(8) -0.0026(8) -0.0115(8) N4 0.0653(12) 0.0372(9) 0.0530(11) 0.0128(8) 0.0049(9) -0.0019(8) C1 0.0808(18) 0.0525(13) 0.0428(13) 0.0121(10) 0.0016(12) -0.0246(12) C2 0.115(2) 0.0643(16) 0.0462(14) 0.0243(13) -0.0027(15) -0.0272(16) C3 0.098(2) 0.0483(13) 0.0541(14) 0.0240(11) -0.0053(13) -0.0182(13) C4 0.0596(14) 0.0372(10) 0.0481(12) 0.0162(9) -0.0029(10) -0.0113(9) C5 0.0423(11) 0.0355(10) 0.0472(12) 0.0147(9) -0.0036(9) -0.0066(8) C6 0.0428(11) 0.0310(9) 0.0444(11) 0.0109(8) -0.0007(8) -0.0046(8) C7 0.0557(13) 0.0339(10) 0.0489(12) 0.0101(9) 0.0066(10) 0.0007(9) C8 0.0615(14) 0.0419(11) 0.0399(11) 0.0127(9) 0.0069(10) -0.0013(10) C9 0.0447(11) 0.0338(9) 0.0412(11) 0.0117(8) -0.0028(8) -0.0043(8) C10 0.0525(12) 0.0349(10) 0.0449(12) 0.0154(9) -0.0023(9) -0.0015(9) C11 0.0527(12) 0.0316(9) 0.0470(12) 0.0149(8) 0.0013(9) 0.0005(8) C12 0.0614(14) 0.0423(12) 0.0573(14) 0.0162(10) 0.0127(11) -0.0005(10) C13 0.0525(14) 0.0442(12) 0.0760(17) 0.0203(12) 0.0074(12) -0.0067(10) C14 0.0488(12) 0.0330(10) 0.0634(14) 0.0184(10) -0.0064(10) -0.0051(9) C15 0.0641(15) 0.0387(11) 0.0621(15) 0.0188(10) -0.0144(12) -0.0116(10) C16 0.0661(15) 0.0354(10) 0.0472(12) 0.0089(9) -0.0104(11) -0.0046(10) C17 0.0790(19) 0.0560(15) 0.0638(17) 0.0122(13) -0.0036(14) 0.0145(13) C18 0.0595(16) 0.088(2) 0.0610(17) 0.0102(15) 0.0048(13) 0.0001(15) C19 0.0746(17) 0.0492(13) 0.0444(13) 0.0006(10) 0.0058(12) -0.0147(12) C20 0.122(3) 0.0573(15) 0.0442(14) 0.0054(11) 0.0161(15) -0.0323(16) C21 0.0516(13) 0.0413(11) 0.0667(15) 0.0166(11) -0.0019(11) 0.0007(9) C22 0.0803(18) 0.0496(13) 0.0525(14) 0.0234(11) -0.0089(12) -0.0005(12) C23 0.0629(17) 0.087(2) 0.091(2) 0.0400(18) -0.0224(15) -0.0204(15) C24 0.122(3) 0.0410(13) 0.080(2) 0.0179(13) -0.0192(18) -0.0224(15) C25 0.230(6) 0.088(3) 0.133(4) -0.006(2) 0.125(4) -0.040(3) C26 0.226(5) 0.070(2) 0.0617(19) 0.0306(16) -0.048(3) -0.058(3) C31 0.0447(11) 0.0355(10) 0.0574(13) 0.0187(9) -0.0010(10) -0.0037(8) C32 0.0613(14) 0.0347(10) 0.0579(14) 0.0146(10) 0.0002(11) -0.0045(9) C33 0.0781(18) 0.0375(12) 0.0780(18) 0.0132(12) 0.0182(15) 0.0042(11) C34 0.0561(15) 0.0504(14) 0.107(2) 0.0351(15) 0.0096(15) 0.0118(11) C35 0.0490(13) 0.0507(13) 0.0794(17) 0.0299(12) -0.0068(12) -0.0006(10) C36 0.0698(19) 0.0551(16) 0.135(3) 0.0406(19) 0.036(2) 0.0082(14) C37 0.0525(16) 0.086(2) 0.138(3) 0.064(2) -0.0082(18) -0.0154(15) C38 0.082(2) 0.0497(15) 0.102(2) 0.0292(15) -0.0062(18) -0.0232(14) C39 0.087(2) 0.0407(13) 0.098(2) 0.0353(14) 0.0077(17) -0.0040(13) C40 0.091(2) 0.0545(16) 0.088(2) 0.0335(15) 0.0192(17) -0.0027(14) O51 0.150(2) 0.0655(13) 0.0957(17) 0.0293(12) 0.0563(16) 0.0222(14) C52 0.120(4) 0.146(4) 0.090(3) -0.005(3) 0.025(3) -0.004(3) C53 0.095(3) 0.073(3) 0.285(8) 0.061(4) 0.063(4) 0.025(2) C51 0.240(7) 0.148(4) 0.141(4) 0.098(4) 0.114(4) 0.097(4) C54 0.149(4) 0.134(4) 0.107(3) 0.074(3) -0.011(3) 0.005(3) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Fe C33 2.033(3) . ? Fe C32 2.038(2) . ? Fe C34 2.036(3) . ? Fe C36 2.045(3) . ? Fe C39 2.043(3) . ? Fe C38 2.039(3) . ? Fe C37 2.044(3) . ? Fe C40 2.052(3) . ? Fe C35 2.056(3) . ? Fe C31 2.081(2) . ? N1 C1 1.348(3) . ? N1 C4 1.394(3) . ? N2 C9 1.327(3) . ? N2 C6 1.413(3) . ? N3 C11 1.366(3) . ? N3 C14 1.378(3) . ? N4 C19 1.368(3) . ? N4 C16 1.385(3) . ? C1 C2 1.384(4) . ? C1 C20 1.521(4) . ? C2 C3 1.382(4) . ? C3 C4 1.399(3) . ? C4 C5 1.432(3) . ? C5 C6 1.396(3) . ? C5 C31 1.487(3) . ? C6 C7 1.437(3) . ? C7 C8 1.350(3) . ? C8 C9 1.433(3) . ? C9 C10 1.529(3) . ? C10 C11 1.518(3) . ? C10 C22 1.537(3) . ? C10 C21 1.540(3) . ? C11 C12 1.372(3) . ? C12 C13 1.417(4) . ? C13 C14 1.366(4) . ? C14 C15 1.515(3) . ? C15 C16 1.510(4) . ? C15 C24 1.546(3) . ? C15 C23 1.541(4) . ? C16 C17 1.354(4) . ? C17 C18 1.405(4) . ? C18 C19 1.371(4) . ? C19 C20 1.512(4) . ? C20 C25 1.527(5) . ? C20 C26 1.563(5) . ? C31 C32 1.432(3) . ? C31 C35 1.446(3) . ? C32 C33 1.423(3) . ? C33 C34 1.409(4) . ? C34 C35 1.419(4) . ? C36 C40 1.409(5) . ? C36 C37 1.417(5) . ? C37 C38 1.422(5) . ? C38 C39 1.404(4) . ? C39 C40 1.410(4) . ? O51 C51 1.371(5) . ? O51 C54 1.407(5) . ? C52 C51 1.349(6) . ? C52 C53 1.445(7) . ? C53 C54 1.456(7) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag C33 Fe C32 40.91(10) . . ? C33 Fe C34 40.51(12) . . ? C32 Fe C34 68.63(11) . . ? C33 Fe C36 160.37(15) . . ? C32 Fe C36 126.56(12) . . ? C34 Fe C36 159.10(15) . . ? C33 Fe C39 117.81(12) . . ? C32 Fe C39 153.65(11) . . ? C34 Fe C39 105.14(12) . . ? C36 Fe C39 67.69(12) . . ? C33 Fe C38 103.26(13) . . ? C32 Fe C38 119.12(12) . . ? C34 Fe C38 119.98(13) . . ? C36 Fe C38 68.09(14) . . ? C39 Fe C38 40.25(12) . . ? C33 Fe C37 121.63(15) . . ? C32 Fe C37 107.23(13) . . ? C34 Fe C37 157.04(15) . . ? C36 Fe C37 40.53(15) . . ? C39 Fe C37 68.03(13) . . ? C38 Fe C37 40.76(13) . . ? C33 Fe C40 154.63(12) . . ? C32 Fe C40 164.17(11) . . ? C34 Fe C40 121.77(13) . . ? C36 Fe C40 40.23(13) . . ? C39 Fe C40 40.30(12) . . ? C38 Fe C40 67.93(14) . . ? C37 Fe C40 68.06(15) . . ? C33 Fe C35 68.20(12) . . ? C32 Fe C35 68.51(11) . . ? C34 Fe C35 40.58(11) . . ? C36 Fe C35 126.08(14) . . ? C39 Fe C35 124.26(12) . . ? C38 Fe C35 157.97(12) . . ? C37 Fe C35 160.87(13) . . ? C40 Fe C35 110.67(13) . . ? C33 Fe C31 68.55(10) . . ? C32 Fe C31 40.67(9) . . ? C34 Fe C31 68.68(10) . . ? C36 Fe C31 112.12(11) . . ? C39 Fe C31 162.89(11) . . ? C38 Fe C31 156.75(12) . . ? C37 Fe C31 123.82(11) . . ? C40 Fe C31 128.36(11) . . ? C35 Fe C31 40.91(9) . . ? C1 N1 C4 110.25(19) . . ? C9 N2 C6 106.44(17) . . ? C11 N3 C14 111.39(19) . . ? C19 N4 C16 111.1(2) . . ? N1 C1 C2 107.6(2) . . ? N1 C1 C20 126.6(2) . . ? C2 C1 C20 125.9(2) . . ? C3 C2 C1 108.4(2) . . ? C2 C3 C4 108.0(2) . . ? N1 C4 C3 105.8(2) . . ? N1 C4 C5 123.47(19) . . ? C3 C4 C5 130.6(2) . . ? C6 C5 C4 123.18(18) . . ? C6 C5 C31 117.80(19) . . ? C4 C5 C31 118.84(19) . . ? C5 C6 N2 123.55(19) . . ? C5 C6 C7 128.30(19) . . ? N2 C6 C7 108.08(17) . . ? C8 C7 C6 107.34(19) . . ? C7 C8 C9 106.89(19) . . ? N2 C9 C8 111.24(18) . . ? N2 C9 C10 123.04(18) . . ? C8 C9 C10 125.70(18) . . ? C11 C10 C9 108.05(17) . . ? C11 C10 C22 108.71(19) . . ? C9 C10 C22 110.39(18) . . ? C11 C10 C21 111.21(18) . . ? C9 C10 C21 109.37(17) . . ? C22 C10 C21 109.1(2) . . ? N3 C11 C12 106.4(2) . . ? N3 C11 C10 120.72(19) . . ? C12 C11 C10 132.9(2) . . ? C11 C12 C13 107.9(2) . . ? C14 C13 C12 108.3(2) . . ? C13 C14 N3 106.1(2) . . ? C13 C14 C15 133.0(2) . . ? N3 C14 C15 120.7(2) . . ? C16 C15 C14 108.35(19) . . ? C16 C15 C24 109.4(2) . . ? C14 C15 C24 109.0(2) . . ? C16 C15 C23 111.8(2) . . ? C14 C15 C23 110.9(2) . . ? C24 C15 C23 107.3(2) . . ? C17 C16 N4 106.2(2) . . ? C17 C16 C15 130.8(2) . . ? N4 C16 C15 122.4(2) . . ? C16 C17 C18 108.3(3) . . ? C19 C18 C17 108.7(3) . . ? N4 C19 C18 105.7(2) . . ? N4 C19 C20 122.9(3) . . ? C18 C19 C20 130.6(3) . . ? C25 C20 C19 109.2(3) . . ? C25 C20 C1 107.9(3) . . ? C19 C20 C1 114.4(2) . . ? C25 C20 C26 109.2(3) . . ? C19 C20 C26 109.0(2) . . ? C1 C20 C26 107.0(3) . . ? C32 C31 C35 106.4(2) . . ? C32 C31 C5 126.4(2) . . ? C35 C31 C5 126.9(2) . . ? C32 C31 Fe 68.03(12) . . ? C35 C31 Fe 68.62(13) . . ? C5 C31 Fe 133.06(16) . . ? C33 C32 C31 108.5(2) . . ? C33 C32 Fe 69.36(15) . . ? C31 C32 Fe 71.30(13) . . ? C34 C33 C32 108.4(2) . . ? C34 C33 Fe 69.89(16) . . ? C32 C33 Fe 69.73(15) . . ? C33 C34 C35 108.3(2) . . ? C33 C34 Fe 69.61(16) . . ? C35 C34 Fe 70.46(15) . . ? C34 C35 C31 108.3(2) . . ? C34 C35 Fe 68.96(15) . . ? C31 C35 Fe 70.47(13) . . ? C40 C36 C37 108.4(3) . . ? C40 C36 Fe 70.13(17) . . ? C37 C36 Fe 69.69(19) . . ? C36 C37 C38 107.3(3) . . ? C36 C37 Fe 69.78(18) . . ? C38 C37 Fe 69.42(17) . . ? C39 C38 C37 108.0(3) . . ? C39 C38 Fe 70.01(16) . . ? C37 C38 Fe 69.81(16) . . ? C38 C39 C40 108.6(3) . . ? C38 C39 Fe 69.74(15) . . ? C40 C39 Fe 70.19(15) . . ? C36 C40 C39 107.7(3) . . ? C36 C40 Fe 69.65(18) . . ? C39 C40 Fe 69.51(17) . . ? C51 O51 C54 107.5(3) . . ? C51 C52 C53 107.4(4) . . ? C52 C53 C54 105.5(3) . . ? C52 C51 O51 112.3(4) . . ? O51 C54 C53 107.1(4) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N1 H1N N2 0.86 2.21 2.781(3) 123.3 . N4 H4N O51 0.86 2.13 2.958(3) 161.5 . _diffrn_measured_fraction_theta_max 0.859 _diffrn_reflns_theta_full 28.76 _diffrn_measured_fraction_theta_full 0.859 _refine_diff_density_max 0.477 _refine_diff_density_min -0.287 _refine_diff_density_rms 0.045 data_struc_2 _database_code_depnum_ccdc_archive 'CCDC 272661' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 'Calix(4)phyrine (2)' _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C46 H42 Cl6 Fe2 N4' _chemical_formula_weight 975.24 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' Cl Cl 0.1484 0.1585 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Monoclinic _symmetry_space_group_name_H-M P2(1) loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, y+1/2, -z' _cell_length_a 12.671(3) _cell_length_b 11.944(2) _cell_length_c 15.545(3) _cell_angle_alpha 90.00 _cell_angle_beta 112.22(3) _cell_angle_gamma 90.00 _cell_volume 2178.1(8) _cell_formula_units_Z 2 _cell_measurement_temperature 298(2) _cell_measurement_reflns_used 940 _cell_measurement_theta_min 3.6935 _cell_measurement_theta_max 26.7795 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.50 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.487 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1000 _exptl_absorpt_coefficient_mu 1.073 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 298(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 13871 _diffrn_reflns_av_R_equivalents 0.0160 _diffrn_reflns_av_sigmaI/netI 0.0433 _diffrn_reflns_limit_h_min -16 _diffrn_reflns_limit_h_max 13 _diffrn_reflns_limit_k_min -15 _diffrn_reflns_limit_k_max 14 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 20 _diffrn_reflns_theta_min 1.42 _diffrn_reflns_theta_max 28.90 _reflns_number_total 8981 _reflns_number_gt 7829 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0630P)^2^+0.3135P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.027(14) _refine_ls_number_reflns 8981 _refine_ls_number_parameters 556 _refine_ls_number_restraints 4 _refine_ls_R_factor_all 0.0525 _refine_ls_R_factor_gt 0.0435 _refine_ls_wR_factor_ref 0.1141 _refine_ls_wR_factor_gt 0.1063 _refine_ls_goodness_of_fit_ref 1.061 _refine_ls_restrained_S_all 1.061 _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 Fe1 Fe 0.69488(4) 0.64160(4) 0.51568(3) 0.03422(11) Uani 1 1 d . . . Fe2 Fe -0.00447(4) 1.23242(4) 0.75789(3) 0.04275(13) Uani 1 1 d . . . N1 N 0.5565(2) 0.8872(3) 0.7523(2) 0.0424(7) Uani 1 1 d . . . N2 N 0.4037(2) 0.7266(2) 0.66589(19) 0.0381(6) Uani 1 1 d . . . H2N H 0.4124 0.7813 0.7040 0.046 Uiso 1 1 calc R . . N3 N 0.2217(2) 0.8470(2) 0.7252(2) 0.0385(6) Uani 1 1 d . . . N4 N 0.3658(2) 1.0173(3) 0.7999(2) 0.0422(7) Uani 1 1 d . . . H4N H 0.3648 0.9478 0.7850 0.051 Uiso 1 1 calc R . . C1 C 0.5975(3) 0.9829(3) 0.7925(2) 0.0429(8) Uani 1 1 d . . . C2 C 0.6593(3) 1.0399(3) 0.7459(3) 0.0464(8) Uani 1 1 d . . . H2 H 0.6953 1.1090 0.7619 0.056 Uiso 1 1 calc R . . C3 C 0.6556(3) 0.9740(3) 0.6737(2) 0.0398(7) Uani 1 1 d . . . H3 H 0.6883 0.9894 0.6306 0.048 Uiso 1 1 calc R . . C4 C 0.5907(3) 0.8750(3) 0.6768(2) 0.0365(7) Uani 1 1 d . . . C5 C 0.5580(3) 0.7860(3) 0.6157(2) 0.0337(6) Uani 1 1 d . . . C6 C 0.4703(3) 0.7089(3) 0.6142(2) 0.0374(7) Uani 1 1 d . . . C7 C 0.4285(3) 0.6114(3) 0.5641(3) 0.0500(9) Uani 1 1 d . . . H7 H 0.4566 0.5773 0.5233 0.060 Uiso 1 1 calc R . . C8 C 0.3379(3) 0.5735(3) 0.5852(3) 0.0517(9) Uani 1 1 d . . . H8 H 0.2944 0.5099 0.5611 0.062 Uiso 1 1 calc R . . C9 C 0.3238(3) 0.6468(3) 0.6483(2) 0.0394(7) Uani 1 1 d . . . C10 C 0.2404(3) 0.6443(3) 0.6980(3) 0.0440(7) Uani 1 1 d . . . C11 C 0.1750(3) 0.7543(3) 0.6796(2) 0.0376(7) Uani 1 1 d . . . C12 C 0.0614(3) 0.7740(3) 0.6154(3) 0.0450(8) Uani 1 1 d . . . H12 H 0.0123 0.7218 0.5759 0.054 Uiso 1 1 calc R . . C13 C 0.0388(3) 0.8846(3) 0.6234(3) 0.0416(8) Uani 1 1 d . . . H13 H -0.0286 0.9221 0.5900 0.050 Uiso 1 1 calc R . . C14 C 0.1384(3) 0.9317(3) 0.6927(2) 0.0346(7) Uani 1 1 d . . . C15 C 0.1579(3) 1.0425(3) 0.7223(2) 0.0351(7) Uani 1 1 d . . . C16 C 0.2705(3) 1.0847(3) 0.7781(2) 0.0365(7) Uani 1 1 d . . . C17 C 0.3088(3) 1.1894(3) 0.8147(3) 0.0475(9) Uani 1 1 d . . . H17 H 0.2637 1.2520 0.8112 0.057 Uiso 1 1 calc R . . C18 C 0.4272(3) 1.1841(3) 0.8578(3) 0.0515(9) Uani 1 1 d . . . H18 H 0.4751 1.2428 0.8880 0.062 Uiso 1 1 calc R . . C19 C 0.4612(3) 1.0764(3) 0.8481(2) 0.0431(8) Uani 1 1 d . . . C20 C 0.5781(3) 1.0220(4) 0.8790(3) 0.0511(9) Uani 1 1 d . . . C21 C 0.3074(4) 0.6308(4) 0.8042(3) 0.0622(11) Uani 1 1 d . . . H21A H 0.2549 0.6291 0.8353 0.093 Uiso 1 1 calc R . . H21B H 0.3588 0.6927 0.8269 0.093 Uiso 1 1 calc R . . H21C H 0.3500 0.5622 0.8159 0.093 Uiso 1 1 calc R . . C22 C 0.1590(4) 0.5453(3) 0.6619(4) 0.0676(13) Uani 1 1 d . . . H22A H 0.1174 0.5536 0.5963 0.101 Uiso 1 1 calc R . . H22B H 0.1067 0.5431 0.6933 0.101 Uiso 1 1 calc R . . H22C H 0.2020 0.4769 0.6736 0.101 Uiso 1 1 calc R . . C23 C 0.5848(4) 0.9222(5) 0.9420(3) 0.0716(14) Uani 1 1 d . . . H23A H 0.5275 0.8684 0.9089 0.107 Uiso 1 1 calc R . . H23B H 0.5723 0.9470 0.9961 0.107 Uiso 1 1 calc R . . H23C H 0.6588 0.8883 0.9605 0.107 Uiso 1 1 calc R . . C24 C 0.6698(4) 1.1081(5) 0.9333(3) 0.0756(16) Uani 1 1 d . . . H24A H 0.6567 1.1321 0.9874 0.113 Uiso 1 1 calc R . . H24B H 0.6660 1.1716 0.8943 0.113 Uiso 1 1 calc R . . H24C H 0.7439 1.0743 0.9520 0.113 Uiso 1 1 calc R . . C31 C 0.6090(3) 0.7749(3) 0.5442(2) 0.0363(7) Uani 1 1 d . . . C32 C 0.7241(3) 0.8039(3) 0.5568(3) 0.0395(7) Uani 1 1 d . . . H32 H 0.7832 0.8312 0.6144 0.047 Uiso 1 1 calc R . . C33 C 0.7361(4) 0.7877(3) 0.4702(3) 0.0525(10) Uani 1 1 d . . . H33 H 0.8054 0.8017 0.4579 0.063 Uiso 1 1 calc R . . C34 C 0.6319(4) 0.7487(4) 0.4050(3) 0.0592(12) Uani 1 1 d . . . H34 H 0.6167 0.7298 0.3401 0.071 Uiso 1 1 calc R . . C35 C 0.5527(3) 0.7383(3) 0.4499(2) 0.0462(8) Uani 1 1 d . . . H35 H 0.4740 0.7113 0.4213 0.055 Uiso 1 1 calc R . . C36 C 0.7246(4) 0.5180(3) 0.6124(3) 0.0548(10) Uani 1 1 d . . . H36 H 0.7032 0.5192 0.6667 0.066 Uiso 1 1 calc R . . C37 C 0.8276(3) 0.5575(3) 0.6089(3) 0.0530(9) Uani 1 1 d . . . H37 H 0.8908 0.5908 0.6607 0.064 Uiso 1 1 calc R . . C38 C 0.8248(3) 0.5399(3) 0.5191(3) 0.0522(9) Uani 1 1 d . . . H38 H 0.8854 0.5591 0.4970 0.063 Uiso 1 1 calc R . . C39 C 0.7197(4) 0.4883(3) 0.4660(3) 0.0551(10) Uani 1 1 d . . . H39 H 0.6941 0.4662 0.4005 0.066 Uiso 1 1 calc R . . C40 C 0.6589(4) 0.4749(3) 0.5244(3) 0.0532(10) Uani 1 1 d . . . H40 H 0.5825 0.4424 0.5063 0.064 Uiso 1 1 calc R . . C41 C 0.0608(3) 1.1211(3) 0.6893(2) 0.0388(7) Uani 1 1 d . . . C42 C -0.0565(3) 1.0956(3) 0.6741(3) 0.0522(9) Uani 1 1 d . . . H42 H -0.0845 1.0252 0.6900 0.063 Uiso 1 1 calc R . . C43 C -0.1244(4) 1.1906(4) 0.6309(3) 0.0659(12) Uani 1 1 d . . . H43 H -0.2071 1.1968 0.6126 0.079 Uiso 1 1 calc R . . C44 C -0.0528(5) 1.2734(4) 0.6207(3) 0.0686(13) Uani 1 1 d . . . H44 H -0.0771 1.3479 0.5943 0.082 Uiso 1 1 calc R . . C45 C 0.0613(4) 1.2343(3) 0.6569(3) 0.0511(9) Uani 1 1 d . . . H45 H 0.1285 1.2763 0.6587 0.061 Uiso 1 1 calc R . . C46 C 0.0847(5) 1.2245(5) 0.8965(3) 0.0794(16) Uani 1 1 d . . . H46 H 0.1517 1.1774 0.9277 0.095 Uiso 1 1 calc R . . C47 C -0.0292(5) 1.1935(5) 0.8764(4) 0.0788(15) Uani 1 1 d . . . H47 H -0.0556 1.1215 0.8909 0.095 Uiso 1 1 calc R . . C48 C -0.0975(5) 1.2840(5) 0.8328(4) 0.0746(14) Uani 1 1 d . . . H48 H -0.1809 1.2856 0.8102 0.090 Uiso 1 1 calc R . . C49 C -0.0281(4) 1.3717(4) 0.8243(4) 0.0673(12) Uani 1 1 d . . . H49 H -0.0541 1.4451 0.7961 0.081 Uiso 1 1 calc R . . C50 C 0.0865(5) 1.3349(5) 0.8653(3) 0.0711(13) Uani 1 1 d . . . H50 H 0.1545 1.3781 0.8708 0.085 Uiso 1 1 calc R . . C101 C 1.3772(6) 1.0681(7) 1.1539(4) 0.067(2) Uani 0.710(11) 1 d P A -1 H101 H 1.4262 1.1244 1.1961 0.080 Uiso 0.710(11) 1 calc PR A -1 Cl1 Cl 1.2392(3) 1.0965(5) 1.1431(3) 0.1162(18) Uani 0.710(11) 1 d P A -1 Cl2 Cl 1.3877(2) 1.0876(4) 1.04571(18) 0.0911(11) Uani 0.710(11) 1 d P A -1 C102 C 1.3110(13) 0.9978(15) 1.1150(8) 0.23(2) Uiso 0.290(11) 1 d PD A -2 H102 H 1.2399 0.9547 1.0915 0.277 Uiso 0.290(11) 1 calc PR A -2 Cl4 Cl 1.301(3) 1.1282(15) 1.1589(10) 0.252(11) Uani 0.290(11) 1 d PD A -2 Cl5 Cl 1.3825(10) 1.008(2) 1.0402(8) 0.156(6) Uani 0.290(11) 1 d PD A -2 Cl3 Cl 1.4202(2) 0.9371(2) 1.20661(17) 0.1331(7) Uani 1 1 d D . . C111 C 1.0141(9) 0.8060(8) 0.9149(7) 0.074(4) Uani 0.532(15) 1 d P B -1 H11A H 1.0056 0.7976 0.9747 0.088 Uiso 0.532(15) 1 calc PR B -1 C112 C 1.0440(13) 0.8023(19) 0.8537(10) 0.148(10) Uani 0.468(15) 1 d P B -2 H11B H 1.0546 0.8102 0.7948 0.178 Uiso 0.468(15) 1 calc PR B -2 Cl11 Cl 1.1396(2) 0.8817(2) 0.9362(2) 0.1615(10) Uani 1 1 d . . . Cl12 Cl 0.8957(2) 0.86562(19) 0.8425(2) 0.1518(10) Uani 1 1 d . . . Cl13 Cl 1.03626(17) 0.66705(17) 0.87794(16) 0.1207(6) 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 Fe1 0.0380(2) 0.0328(2) 0.0344(2) -0.00153(19) 0.01656(18) 0.0053(2) Fe2 0.0487(3) 0.0371(2) 0.0476(3) 0.0000(2) 0.0241(2) 0.0084(2) N1 0.0336(14) 0.0587(18) 0.0360(15) -0.0125(13) 0.0143(12) -0.0052(13) N2 0.0401(14) 0.0325(13) 0.0469(15) -0.0027(13) 0.0224(12) -0.0002(12) N3 0.0359(14) 0.0327(14) 0.0491(16) 0.0000(12) 0.0185(12) 0.0024(11) N4 0.0406(15) 0.0432(16) 0.0447(15) -0.0145(13) 0.0182(13) -0.0016(12) C1 0.0321(17) 0.056(2) 0.0391(18) -0.0158(16) 0.0114(14) -0.0022(15) C2 0.0430(19) 0.0422(19) 0.054(2) -0.0136(16) 0.0186(16) -0.0043(15) C3 0.0388(18) 0.0386(18) 0.0448(18) -0.0035(15) 0.0189(15) 0.0005(14) C4 0.0273(15) 0.0463(18) 0.0370(16) -0.0019(14) 0.0136(13) 0.0037(13) C5 0.0312(15) 0.0375(16) 0.0340(15) 0.0002(13) 0.0140(13) 0.0076(12) C6 0.0334(16) 0.0369(18) 0.0434(18) -0.0027(13) 0.0163(14) 0.0048(12) C7 0.0430(19) 0.048(2) 0.064(2) -0.0179(17) 0.0268(17) -0.0043(15) C8 0.051(2) 0.0393(19) 0.073(3) -0.0150(18) 0.032(2) -0.0097(16) C9 0.0390(16) 0.0299(15) 0.0508(18) 0.0014(16) 0.0186(14) 0.0047(15) C10 0.0454(18) 0.0327(15) 0.061(2) 0.0047(18) 0.0281(16) 0.0001(17) C11 0.0400(17) 0.0298(17) 0.0516(19) 0.0036(14) 0.0272(15) -0.0003(13) C12 0.0414(19) 0.0381(18) 0.055(2) -0.0070(15) 0.0183(16) -0.0035(14) C13 0.0391(18) 0.0388(18) 0.0462(19) -0.0001(15) 0.0154(15) 0.0014(14) C14 0.0359(17) 0.0347(16) 0.0373(16) 0.0025(13) 0.0184(14) 0.0036(12) C15 0.0417(17) 0.0327(16) 0.0392(17) 0.0001(13) 0.0248(14) 0.0024(13) C16 0.0366(17) 0.0404(17) 0.0375(17) -0.0055(14) 0.0196(14) -0.0008(14) C17 0.046(2) 0.0484(19) 0.053(2) -0.0093(17) 0.0252(17) -0.0029(16) C18 0.051(2) 0.051(2) 0.059(2) -0.0214(18) 0.0279(18) -0.0160(17) C19 0.0422(19) 0.055(2) 0.0345(17) -0.0132(15) 0.0179(15) -0.0073(16) C20 0.0366(18) 0.073(3) 0.0396(18) -0.0208(18) 0.0103(15) -0.0023(17) C21 0.067(3) 0.060(2) 0.070(3) 0.019(2) 0.037(2) 0.016(2) C22 0.060(3) 0.0315(19) 0.125(4) 0.000(2) 0.052(3) -0.0067(18) C23 0.070(3) 0.100(4) 0.038(2) -0.004(2) 0.012(2) 0.014(3) C24 0.048(2) 0.109(4) 0.065(3) -0.049(3) 0.017(2) -0.016(2) C31 0.0403(18) 0.0310(15) 0.0405(17) 0.0016(13) 0.0186(15) 0.0060(13) C32 0.0460(19) 0.0298(15) 0.051(2) -0.0008(14) 0.0276(17) 0.0033(14) C33 0.070(3) 0.0390(19) 0.069(3) 0.0109(18) 0.050(2) 0.0119(18) C34 0.086(3) 0.061(3) 0.0378(19) 0.0136(19) 0.031(2) 0.030(2) C35 0.051(2) 0.0488(19) 0.0368(17) 0.0010(16) 0.0146(15) 0.0144(18) C36 0.069(3) 0.048(2) 0.054(2) 0.0164(18) 0.030(2) 0.0171(19) C37 0.047(2) 0.047(2) 0.054(2) 0.0050(18) 0.0076(17) 0.0129(17) C38 0.051(2) 0.0410(19) 0.072(3) -0.0014(18) 0.0311(19) 0.0142(16) C39 0.073(3) 0.042(2) 0.056(2) -0.0102(18) 0.030(2) 0.0067(19) C40 0.054(2) 0.0354(19) 0.071(3) -0.0022(18) 0.025(2) -0.0017(17) C41 0.0457(18) 0.0334(18) 0.0420(17) 0.0001(13) 0.0218(14) 0.0058(13) C42 0.044(2) 0.045(2) 0.065(2) -0.0113(18) 0.0182(18) 0.0050(16) C43 0.051(2) 0.066(3) 0.070(3) -0.010(2) 0.010(2) 0.020(2) C44 0.099(4) 0.057(3) 0.046(2) 0.0093(19) 0.023(2) 0.036(3) C45 0.073(3) 0.0401(18) 0.050(2) 0.0017(17) 0.0341(19) 0.0054(19) C46 0.097(4) 0.100(4) 0.044(2) 0.005(3) 0.030(2) 0.045(3) C47 0.114(5) 0.071(3) 0.082(3) 0.001(3) 0.073(3) 0.002(3) C48 0.072(3) 0.078(3) 0.089(4) -0.021(3) 0.047(3) 0.005(3) C49 0.076(3) 0.050(2) 0.073(3) -0.013(2) 0.025(2) 0.011(2) C50 0.072(3) 0.086(4) 0.059(3) -0.021(3) 0.029(2) -0.005(3) C101 0.059(4) 0.093(5) 0.054(4) -0.015(4) 0.028(3) -0.015(4) Cl1 0.0894(19) 0.186(4) 0.094(2) 0.041(2) 0.0582(16) 0.051(2) Cl2 0.0793(14) 0.139(3) 0.0645(12) -0.0027(14) 0.0377(10) -0.0085(16) Cl4 0.44(3) 0.140(10) 0.110(7) -0.001(7) 0.025(14) 0.127(16) Cl5 0.165(8) 0.225(17) 0.126(6) 0.015(8) 0.109(6) 0.021(10) Cl3 0.1250(16) 0.1387(17) 0.1379(16) 0.0211(14) 0.0524(13) 0.0445(13) C111 0.094(8) 0.064(6) 0.057(6) 0.004(4) 0.022(5) -0.008(5) C112 0.119(12) 0.28(2) 0.080(9) 0.122(13) 0.076(9) 0.126(14) Cl11 0.1380(18) 0.149(2) 0.178(2) -0.0133(18) 0.0379(17) -0.0515(17) Cl12 0.1109(14) 0.1066(14) 0.211(3) 0.0551(16) 0.0306(16) 0.0220(12) Cl13 0.1046(12) 0.1006(13) 0.1451(16) -0.0205(12) 0.0338(11) 0.0095(10) _geom_special_details ; All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds involving l.s. planes. ; loop_ _geom_bond_atom_site_label_1 _geom_bond_atom_site_label_2 _geom_bond_distance _geom_bond_site_symmetry_2 _geom_bond_publ_flag Fe1 C37 2.024(4) . ? Fe1 C33 2.024(4) . ? Fe1 C38 2.030(4) . ? Fe1 C32 2.031(3) . ? Fe1 C36 2.038(4) . ? Fe1 C34 2.048(4) . ? Fe1 C39 2.057(4) . ? Fe1 C35 2.057(4) . ? Fe1 C40 2.059(4) . ? Fe1 C31 2.069(3) . ? Fe2 C46 2.022(5) . ? Fe2 C47 2.037(5) . ? Fe2 C45 2.037(4) . ? Fe2 C42 2.037(4) . ? Fe2 C49 2.038(4) . ? Fe2 C50 2.040(5) . ? Fe2 C48 2.040(5) . ? Fe2 C44 2.043(4) . ? Fe2 C43 2.046(5) . ? Fe2 C41 2.064(3) . ? N1 C1 1.311(5) . ? N1 C4 1.405(4) . ? N2 C9 1.342(4) . ? N2 C6 1.384(4) . ? N3 C11 1.327(4) . ? N3 C14 1.410(4) . ? N4 C19 1.355(4) . ? N4 C16 1.383(4) . ? C1 C2 1.426(5) . ? C1 C20 1.529(5) . ? C2 C3 1.357(5) . ? C3 C4 1.451(5) . ? C4 C5 1.381(5) . ? C5 C6 1.437(5) . ? C5 C31 1.488(4) . ? C6 C7 1.391(5) . ? C7 C8 1.384(5) . ? C8 C9 1.377(5) . ? C9 C10 1.528(4) . ? C10 C11 1.522(5) . ? C10 C22 1.529(5) . ? C10 C21 1.552(6) . ? C11 C12 1.427(5) . ? C12 C13 1.367(5) . ? C13 C14 1.429(5) . ? C14 C15 1.392(5) . ? C15 C16 1.451(5) . ? C15 C41 1.477(5) . ? C16 C17 1.385(5) . ? C17 C18 1.394(6) . ? C18 C19 1.383(5) . ? C19 C20 1.519(5) . ? C20 C23 1.524(7) . ? C20 C24 1.543(6) . ? C31 C35 1.435(5) . ? C31 C32 1.438(5) . ? C32 C33 1.425(5) . ? C33 C34 1.405(7) . ? C34 C35 1.428(6) . ? C36 C40 1.402(6) . ? C36 C37 1.408(6) . ? C37 C38 1.398(6) . ? C38 C39 1.415(6) . ? C39 C40 1.405(6) . ? C41 C45 1.444(5) . ? C41 C42 1.446(5) . ? C42 C43 1.429(6) . ? C43 C44 1.392(7) . ? C44 C45 1.417(6) . ? C46 C47 1.405(8) . ? C46 C50 1.408(8) . ? C47 C48 1.390(8) . ? C48 C49 1.406(7) . ? C49 C50 1.418(7) . ? C101 Cl1 1.725(8) . ? C101 Cl2 1.752(7) . ? C101 Cl3 1.754(9) . ? C102 Cl3 1.725(10) . ? C102 Cl4 1.725(10) . ? C102 Cl5 1.728(10) . ? C111 Cl12 1.658(11) . ? C111 Cl11 1.749(11) . ? C111 Cl13 1.813(11) . ? C112 Cl13 1.67(2) . ? C112 Cl11 1.68(2) . ? C112 Cl12 1.970(12) . ? 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 C37 Fe1 C33 115.08(19) . . ? C37 Fe1 C38 40.36(17) . . ? C33 Fe1 C38 102.19(16) . . ? C37 Fe1 C32 104.19(16) . . ? C33 Fe1 C32 41.15(15) . . ? C38 Fe1 C32 120.89(16) . . ? C37 Fe1 C36 40.57(17) . . ? C33 Fe1 C36 151.92(19) . . ? C38 Fe1 C36 67.99(17) . . ? C32 Fe1 C36 119.89(17) . . ? C37 Fe1 C34 150.01(19) . . ? C33 Fe1 C34 40.36(19) . . ? C38 Fe1 C34 116.78(17) . . ? C32 Fe1 C34 68.60(17) . . ? C36 Fe1 C34 167.6(2) . . ? C37 Fe1 C39 67.88(18) . . ? C33 Fe1 C39 122.65(15) . . ? C38 Fe1 C39 40.52(18) . . ? C32 Fe1 C39 158.78(16) . . ? C36 Fe1 C39 67.69(18) . . ? C34 Fe1 C39 107.87(18) . . ? C37 Fe1 C35 165.75(15) . . ? C33 Fe1 C35 68.62(18) . . ? C38 Fe1 C35 153.89(16) . . ? C32 Fe1 C35 69.01(16) . . ? C36 Fe1 C35 131.01(17) . . ? C34 Fe1 C35 40.70(16) . . ? C39 Fe1 C35 122.85(17) . . ? C37 Fe1 C40 67.50(17) . . ? C33 Fe1 C40 161.74(17) . . ? C38 Fe1 C40 67.48(17) . . ? C32 Fe1 C40 157.07(15) . . ? C36 Fe1 C40 40.03(17) . . ? C34 Fe1 C40 129.34(19) . . ? C39 Fe1 C40 39.92(18) . . ? C35 Fe1 C40 113.69(17) . . ? C37 Fe1 C31 126.21(15) . . ? C33 Fe1 C31 68.76(14) . . ? C38 Fe1 C31 160.35(15) . . ? C32 Fe1 C31 41.06(13) . . ? C36 Fe1 C31 111.41(15) . . ? C34 Fe1 C31 68.26(14) . . ? C39 Fe1 C31 158.89(16) . . ? C35 Fe1 C31 40.69(14) . . ? C40 Fe1 C31 125.65(16) . . ? C46 Fe2 C47 40.5(2) . . ? C46 Fe2 C45 126.6(2) . . ? C47 Fe2 C45 161.4(2) . . ? C46 Fe2 C42 124.0(2) . . ? C47 Fe2 C42 105.8(2) . . ? C45 Fe2 C42 69.13(18) . . ? C46 Fe2 C49 68.2(2) . . ? C47 Fe2 C49 68.0(2) . . ? C45 Fe2 C49 124.2(2) . . ? C42 Fe2 C49 154.70(18) . . ? C46 Fe2 C50 40.6(2) . . ? C47 Fe2 C50 68.2(2) . . ? C45 Fe2 C50 110.8(2) . . ? C42 Fe2 C50 161.9(2) . . ? C49 Fe2 C50 40.7(2) . . ? C46 Fe2 C48 67.4(2) . . ? C47 Fe2 C48 39.9(2) . . ? C45 Fe2 C48 158.4(2) . . ? C42 Fe2 C48 119.3(2) . . ? C49 Fe2 C48 40.3(2) . . ? C50 Fe2 C48 67.8(2) . . ? C46 Fe2 C44 161.8(3) . . ? C47 Fe2 C44 155.7(2) . . ? C45 Fe2 C44 40.66(19) . . ? C42 Fe2 C44 68.18(19) . . ? C49 Fe2 C44 106.81(19) . . ? C50 Fe2 C44 124.4(2) . . ? C48 Fe2 C44 120.9(2) . . ? C46 Fe2 C43 158.2(3) . . ? C47 Fe2 C43 120.3(2) . . ? C45 Fe2 C43 68.30(19) . . ? C42 Fe2 C43 40.96(17) . . ? C49 Fe2 C43 119.33(19) . . ? C50 Fe2 C43 156.9(2) . . ? C48 Fe2 C43 104.2(2) . . ? C44 Fe2 C43 39.8(2) . . ? C46 Fe2 C41 110.44(17) . . ? C47 Fe2 C41 123.34(18) . . ? C45 Fe2 C41 41.23(15) . . ? C42 Fe2 C41 41.28(15) . . ? C49 Fe2 C41 162.18(18) . . ? C50 Fe2 C41 126.66(18) . . ? C48 Fe2 C41 157.00(19) . . ? C44 Fe2 C41 68.62(15) . . ? C43 Fe2 C41 68.93(15) . . ? C1 N1 C4 107.3(3) . . ? C9 N2 C6 110.6(3) . . ? C11 N3 C14 106.6(3) . . ? C19 N4 C16 110.3(3) . . ? N1 C1 C2 111.7(3) . . ? N1 C1 C20 121.3(3) . . ? C2 C1 C20 127.1(3) . . ? C3 C2 C1 106.8(3) . . ? C2 C3 C4 106.7(3) . . ? C5 C4 N1 123.2(3) . . ? C5 C4 C3 129.1(3) . . ? N1 C4 C3 107.5(3) . . ? C4 C5 C6 122.2(3) . . ? C4 C5 C31 118.7(3) . . ? C6 C5 C31 118.9(3) . . ? N2 C6 C7 105.5(3) . . ? N2 C6 C5 122.0(3) . . ? C7 C6 C5 132.4(3) . . ? C8 C7 C6 108.4(3) . . ? C9 C8 C7 107.7(3) . . ? N2 C9 C8 107.8(3) . . ? N2 C9 C10 121.6(3) . . ? C8 C9 C10 130.5(3) . . ? C11 C10 C9 108.6(3) . . ? C11 C10 C22 110.8(3) . . ? C9 C10 C22 109.2(3) . . ? C11 C10 C21 109.3(3) . . ? C9 C10 C21 109.5(3) . . ? C22 C10 C21 109.4(4) . . ? N3 C11 C12 111.3(3) . . ? N3 C11 C10 121.3(3) . . ? C12 C11 C10 127.4(3) . . ? C13 C12 C11 106.6(3) . . ? C12 C13 C14 107.1(3) . . ? C15 C14 N3 123.2(3) . . ? C15 C14 C13 128.3(3) . . ? N3 C14 C13 108.4(3) . . ? C14 C15 C16 122.6(3) . . ? C14 C15 C41 118.0(3) . . ? C16 C15 C41 119.2(3) . . ? N4 C16 C17 106.7(3) . . ? N4 C16 C15 121.0(3) . . ? C17 C16 C15 132.2(3) . . ? C16 C17 C18 107.6(3) . . ? C19 C18 C17 108.2(3) . . ? N4 C19 C18 107.2(3) . . ? N4 C19 C20 120.7(3) . . ? C18 C19 C20 132.1(3) . . ? C19 C20 C23 110.5(4) . . ? C19 C20 C1 108.3(3) . . ? C23 C20 C1 109.7(3) . . ? C19 C20 C24 109.3(4) . . ? C23 C20 C24 108.9(4) . . ? C1 C20 C24 110.3(3) . . ? C35 C31 C32 107.5(3) . . ? C35 C31 C5 127.0(3) . . ? C32 C31 C5 125.5(3) . . ? C35 C31 Fe1 69.23(19) . . ? C32 C31 Fe1 68.06(18) . . ? C5 C31 Fe1 129.9(2) . . ? C33 C32 C31 107.7(3) . . ? C33 C32 Fe1 69.2(2) . . ? C31 C32 Fe1 70.88(19) . . ? C34 C33 C32 108.6(3) . . ? C34 C33 Fe1 70.7(2) . . ? C32 C33 Fe1 69.7(2) . . ? C33 C34 C35 108.6(3) . . ? C33 C34 Fe1 68.9(2) . . ? C35 C34 Fe1 70.0(2) . . ? C34 C35 C31 107.6(4) . . ? C34 C35 Fe1 69.3(2) . . ? C31 C35 Fe1 70.08(19) . . ? C40 C36 C37 107.6(4) . . ? C40 C36 Fe1 70.8(2) . . ? C37 C36 Fe1 69.2(2) . . ? C38 C37 C36 108.3(4) . . ? C38 C37 Fe1 70.0(2) . . ? C36 C37 Fe1 70.3(2) . . ? C37 C38 C39 108.2(4) . . ? C37 C38 Fe1 69.6(2) . . ? C39 C38 Fe1 70.8(2) . . ? C40 C39 C38 107.3(4) . . ? C40 C39 Fe1 70.1(2) . . ? C38 C39 Fe1 68.7(2) . . ? C36 C40 C39 108.7(4) . . ? C36 C40 Fe1 69.2(2) . . ? C39 C40 Fe1 70.0(2) . . ? C45 C41 C42 106.2(3) . . ? C45 C41 C15 127.2(3) . . ? C42 C41 C15 126.3(3) . . ? C45 C41 Fe2 68.39(19) . . ? C42 C41 Fe2 68.4(2) . . ? C15 C41 Fe2 132.4(2) . . ? C43 C42 C41 108.0(4) . . ? C43 C42 Fe2 69.8(2) . . ? C41 C42 Fe2 70.3(2) . . ? C44 C43 C42 108.4(4) . . ? C44 C43 Fe2 70.0(3) . . ? C42 C43 Fe2 69.2(2) . . ? C43 C44 C45 109.4(4) . . ? C43 C44 Fe2 70.2(3) . . ? C45 C44 Fe2 69.4(2) . . ? C44 C45 C41 108.0(4) . . ? C44 C45 Fe2 69.9(2) . . ? C41 C45 Fe2 70.39(19) . . ? C47 C46 C50 108.6(5) . . ? C47 C46 Fe2 70.3(3) . . ? C50 C46 Fe2 70.4(3) . . ? C48 C47 C46 107.6(5) . . ? C48 C47 Fe2 70.2(3) . . ? C46 C47 Fe2 69.2(3) . . ? C47 C48 C49 109.2(5) . . ? C47 C48 Fe2 69.9(3) . . ? C49 C48 Fe2 69.8(3) . . ? C48 C49 C50 107.3(5) . . ? C48 C49 Fe2 69.9(3) . . ? C50 C49 Fe2 69.7(3) . . ? C46 C50 C49 107.3(5) . . ? C46 C50 Fe2 69.0(3) . . ? C49 C50 Fe2 69.6(3) . . ? Cl1 C101 Cl2 108.8(4) . . ? Cl1 C101 Cl3 110.2(4) . . ? Cl2 C101 Cl3 116.3(5) . . ? Cl3 C102 Cl4 102.1(10) . . ? Cl3 C102 Cl5 97.0(8) . . ? Cl4 C102 Cl5 110.0(14) . . ? C102 Cl3 C101 39.6(7) . . ? Cl12 C111 Cl11 115.5(6) . . ? Cl12 C111 Cl13 112.8(5) . . ? Cl11 C111 Cl13 107.1(6) . . ? Cl13 C112 Cl11 117.4(6) . . ? Cl13 C112 Cl12 104.8(9) . . ? Cl11 C112 Cl12 103.8(10) . . ? C112 Cl11 C111 39.1(5) . . ? C111 Cl12 C112 35.7(5) . . ? C112 Cl13 C111 38.3(5) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N2 H2N N1 0.86 2.11 2.695(4) 124.6 . N4 H4N N3 0.86 2.08 2.686(4) 127.0 . _diffrn_measured_fraction_theta_max 0.900 _diffrn_reflns_theta_full 28.90 _diffrn_measured_fraction_theta_full 0.900 _refine_diff_density_max 0.453 _refine_diff_density_min -0.354 _refine_diff_density_rms 0.066 data_struc_3 _database_code_depnum_ccdc_archive 'CCDC 272662' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 'calix(4)phyrin (4)' _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C48 H48 Fe2 N4 O Zn' _chemical_formula_weight 873.97 loop_ _atom_type_symbol _atom_type_description _atom_type_scat_dispersion_real _atom_type_scat_dispersion_imag _atom_type_scat_source C C 0.0033 0.0016 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' H H 0.0000 0.0000 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' 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' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Zn Zn 0.2839 1.4301 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Tetragonal _symmetry_space_group_name_H-M P4(1)2(1)2 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x, -y, z+1/2' '-y+1/2, x+1/2, z+1/4' 'y+1/2, -x+1/2, z+3/4' '-x+1/2, y+1/2, -z+1/4' 'x+1/2, -y+1/2, -z+3/4' 'y, x, -z' '-y, -x, -z+1/2' _cell_length_a 10.7004(15) _cell_length_b 10.7004(15) _cell_length_c 34.398(7) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3938.6(11) _cell_formula_units_Z 4 _cell_measurement_temperature 223(2) _cell_measurement_reflns_used 984 _cell_measurement_theta_min 2.941 _cell_measurement_theta_max 28.593 _exptl_crystal_description ? _exptl_crystal_colour ? _exptl_crystal_size_max 0.30 _exptl_crystal_size_mid 0.15 _exptl_crystal_size_min 0.08 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.474 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1816 _exptl_absorpt_coefficient_mu 1.374 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 223(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 16132 _diffrn_reflns_av_R_equivalents 0.0214 _diffrn_reflns_av_sigmaI/netI 0.0253 _diffrn_reflns_limit_h_min -12 _diffrn_reflns_limit_h_max 14 _diffrn_reflns_limit_k_min -13 _diffrn_reflns_limit_k_max 13 _diffrn_reflns_limit_l_min -21 _diffrn_reflns_limit_l_max 46 _diffrn_reflns_theta_min 1.99 _diffrn_reflns_theta_max 28.99 _reflns_number_total 4838 _reflns_number_gt 4570 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0271P)^2^+1.9177P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_abs_structure_details 'Flack H D (1983), Acta Cryst. A39, 876-881' _refine_ls_abs_structure_Flack 0.027(13) _refine_ls_number_reflns 4838 _refine_ls_number_parameters 255 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0342 _refine_ls_R_factor_gt 0.0312 _refine_ls_wR_factor_ref 0.0727 _refine_ls_wR_factor_gt 0.0719 _refine_ls_goodness_of_fit_ref 1.162 _refine_ls_restrained_S_all 1.162 _refine_ls_shift/su_max 0.026 _refine_ls_shift/su_mean 0.002 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 Zn1 Zn 0.42563(3) 0.42563(3) 0.0000 0.02516(9) Uani 1 2 d S . . Fe1 Fe 0.46218(3) 0.74254(3) 0.152600(10) 0.02631(8) Uani 1 1 d . . . N1 N 0.29076(18) 0.52588(19) 0.02917(5) 0.0256(4) Uani 1 1 d . . . N2 N 0.47618(18) 0.34930(18) 0.05243(5) 0.0244(4) Uani 1 1 d . . . C1 C 0.2140(2) 0.6057(2) 0.01053(7) 0.0271(5) Uani 1 1 d . . . C2 C 0.1947(3) 0.7152(3) 0.03286(7) 0.0330(6) Uani 1 1 d . . . H2A H 0.1455 0.7846 0.0260 0.040 Uiso 1 1 calc R . . C3 C 0.2626(2) 0.6998(2) 0.06670(7) 0.0328(5) Uani 1 1 d . . . H3A H 0.2685 0.7573 0.0873 0.039 Uiso 1 1 calc R . . C4 C 0.3213(2) 0.5817(2) 0.06468(6) 0.0255(5) Uani 1 1 d . . . C5 C 0.3907(2) 0.5185(2) 0.09409(6) 0.0237(4) Uani 1 1 d . . . C6 C 0.4506(2) 0.4026(2) 0.08879(6) 0.0250(5) Uani 1 1 d . . . C7 C 0.4919(2) 0.3179(2) 0.11813(7) 0.0279(5) Uani 1 1 d . . . H7A H 0.4864 0.3300 0.1451 0.033 Uiso 1 1 calc R . . C8 C 0.5413(2) 0.2157(2) 0.09971(7) 0.0281(5) Uani 1 1 d . . . H8A H 0.5749 0.1441 0.1116 0.034 Uiso 1 1 calc R . . C9 C 0.5319(2) 0.2389(2) 0.05912(6) 0.0251(4) Uani 1 1 d . . . C10 C 0.5716(2) 0.1488(2) 0.02726(6) 0.0264(5) Uani 1 1 d . . . C11 C 0.6821(3) 0.0702(3) 0.04164(7) 0.0367(6) Uani 1 1 d . . . H11A H 0.7528 0.1244 0.0469 0.055 Uiso 1 1 calc R . . H11B H 0.7048 0.0097 0.0219 0.055 Uiso 1 1 calc R . . H11C H 0.6586 0.0268 0.0653 0.055 Uiso 1 1 calc R . . C12 C 0.4603(3) 0.0602(2) 0.01927(7) 0.0327(5) Uani 1 1 d . . . H12A H 0.3894 0.1084 0.0101 0.049 Uiso 1 1 calc R . . H12B H 0.4379 0.0169 0.0430 0.049 Uiso 1 1 calc R . . H12C H 0.4839 -0.0004 -0.0004 0.049 Uiso 1 1 calc R . . C21 C 0.3958(2) 0.5718(2) 0.13398(6) 0.0256(5) Uani 1 1 d . . . C22 C 0.4979(2) 0.5580(2) 0.16110(7) 0.0300(5) Uani 1 1 d . . . H22A H 0.5782 0.5153 0.1558 0.036 Uiso 1 1 calc R . . C23 C 0.4631(3) 0.6150(3) 0.19675(7) 0.0356(6) Uani 1 1 d . . . H23A H 0.5152 0.6193 0.2205 0.043 Uiso 1 1 calc R . . C24 C 0.3423(3) 0.6662(3) 0.19235(7) 0.0373(6) Uani 1 1 d . . . H24A H 0.2954 0.7128 0.2125 0.045 Uiso 1 1 calc R . . C25 C 0.3003(2) 0.6412(2) 0.15401(7) 0.0307(5) Uani 1 1 d . . . H25A H 0.2191 0.6674 0.1429 0.037 Uiso 1 1 calc R . . C26 C 0.5252(3) 0.8410(3) 0.10589(8) 0.0368(6) Uani 1 1 d . . . H26A H 0.5225 0.8129 0.0785 0.044 Uiso 1 1 calc R . . C27 C 0.6247(3) 0.8200(3) 0.13231(9) 0.0423(7) Uani 1 1 d . . . H27A H 0.7035 0.7750 0.1267 0.051 Uiso 1 1 calc R . . C28 C 0.5898(3) 0.8748(3) 0.16853(9) 0.0450(7) Uani 1 1 d . . . H28A H 0.6402 0.8744 0.1926 0.054 Uiso 1 1 calc R . . C29 C 0.4708(3) 0.9301(3) 0.16392(8) 0.0405(6) Uani 1 1 d . . . H29A H 0.4233 0.9749 0.1843 0.049 Uiso 1 1 calc R . . C30 C 0.4306(3) 0.9096(2) 0.12525(8) 0.0359(6) Uani 1 1 d . . . H30A H 0.3505 0.9375 0.1138 0.043 Uiso 1 1 calc R . . O1 O 0.57061(17) 0.57061(17) 0.0000 0.0414(6) Uani 1 2 d S . . C31 C 0.6948(3) 0.5474(3) 0.01427(9) 0.0416(6) Uani 1 1 d . . . H31A H 0.7550 0.5653 -0.0065 0.050 Uiso 1 1 calc R . . H31B H 0.7025 0.4588 0.0210 0.050 Uiso 1 1 calc R . . C32 C 0.7271(4) 0.6249(4) 0.04929(12) 0.0727(12) Uani 1 1 d . . . H32A H 0.8116 0.6057 0.0576 0.109 Uiso 1 1 calc R . . H32B H 0.6692 0.6061 0.0702 0.109 Uiso 1 1 calc R . . H32C H 0.7213 0.7128 0.0427 0.109 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 Zn1 0.02684(12) 0.02684(12) 0.02182(16) 0.00223(10) -0.00223(10) 0.00431(15) Fe1 0.02588(18) 0.02840(18) 0.02466(15) -0.00342(14) -0.00185(13) -0.00144(13) N1 0.0238(10) 0.0299(10) 0.0232(9) 0.0001(8) -0.0030(7) 0.0044(8) N2 0.0268(10) 0.0245(10) 0.0220(9) 0.0018(7) -0.0016(8) 0.0022(8) C1 0.0269(12) 0.0305(13) 0.0239(11) -0.0001(9) -0.0037(9) 0.0041(9) C2 0.0349(14) 0.0328(14) 0.0314(12) -0.0028(10) -0.0073(11) 0.0114(11) C3 0.0349(14) 0.0333(13) 0.0301(12) -0.0068(10) -0.0071(11) 0.0036(11) C4 0.0254(12) 0.0283(12) 0.0227(10) -0.0034(9) -0.0020(8) -0.0008(9) C5 0.0212(11) 0.0269(11) 0.0230(10) -0.0003(9) -0.0004(8) -0.0020(8) C6 0.0251(11) 0.0278(11) 0.0220(10) 0.0012(8) -0.0025(8) -0.0012(9) C7 0.0321(13) 0.0301(13) 0.0216(11) 0.0039(9) -0.0031(9) -0.0043(9) C8 0.0309(12) 0.0273(12) 0.0260(10) 0.0069(9) -0.0043(9) -0.0011(9) C9 0.0239(11) 0.0262(12) 0.0254(10) 0.0047(9) -0.0014(9) -0.0012(9) C10 0.0309(12) 0.0253(11) 0.0231(10) 0.0064(9) 0.0006(10) 0.0057(9) C11 0.0392(15) 0.0397(15) 0.0313(12) 0.0109(12) 0.0030(10) 0.0139(12) C12 0.0425(14) 0.0273(13) 0.0282(11) 0.0024(10) 0.0011(10) -0.0012(11) C21 0.0246(11) 0.0262(11) 0.0259(10) 0.0001(9) -0.0011(8) -0.0042(9) C22 0.0326(12) 0.0275(13) 0.0299(11) 0.0017(10) -0.0077(9) -0.0036(9) C23 0.0406(15) 0.0420(15) 0.0242(11) 0.0014(10) -0.0061(11) -0.0093(11) C24 0.0426(16) 0.0465(17) 0.0229(11) -0.0055(11) 0.0052(11) -0.0096(12) C25 0.0249(12) 0.0381(14) 0.0292(12) -0.0030(11) 0.0007(10) -0.0041(9) C26 0.0444(16) 0.0322(14) 0.0337(13) 0.0030(10) 0.0058(12) -0.0050(12) C27 0.0308(15) 0.0352(16) 0.0608(19) 0.0025(13) 0.0049(13) -0.0057(11) C28 0.0443(17) 0.0338(15) 0.0568(17) -0.0057(13) -0.0141(14) -0.0098(12) C29 0.0479(16) 0.0287(13) 0.0449(15) -0.0083(12) -0.0021(12) -0.0033(12) C30 0.0407(15) 0.0273(13) 0.0397(13) 0.0003(10) -0.0007(12) 0.0017(11) O1 0.0315(8) 0.0315(8) 0.0613(16) 0.0101(9) -0.0101(9) 0.0025(11) C31 0.0330(14) 0.0356(15) 0.0562(17) 0.0006(13) -0.0087(12) 0.0057(11) C32 0.069(3) 0.064(2) 0.085(3) -0.018(2) -0.033(2) 0.018(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 Zn1 N2 2.0524(19) 7 ? Zn1 N2 2.0524(19) . ? Zn1 N1 2.0591(19) 7 ? Zn1 N1 2.0591(19) . ? Zn1 O1 2.194(3) . ? Fe1 C22 2.033(2) . ? Fe1 C26 2.036(3) . ? Fe1 C23 2.042(3) . ? Fe1 C28 2.041(3) . ? Fe1 C25 2.044(2) . ? Fe1 C24 2.045(3) . ? Fe1 C29 2.047(3) . ? Fe1 C27 2.049(3) . ? Fe1 C30 2.048(3) . ? Fe1 C21 2.062(2) . ? N1 C1 1.347(3) . ? N1 C4 1.399(3) . ? N2 C9 1.343(3) . ? N2 C6 1.401(3) . ? C1 C2 1.416(3) . ? C1 C10 1.520(3) 7 ? C2 C3 1.382(3) . ? C3 C4 1.413(3) . ? C4 C5 1.425(3) . ? C5 C6 1.408(3) . ? C5 C21 1.487(3) . ? C6 C7 1.426(3) . ? C7 C8 1.370(3) . ? C8 C9 1.422(3) . ? C9 C10 1.520(3) . ? C10 C1 1.520(3) 7 ? C10 C11 1.533(3) . ? C10 C12 1.547(4) . ? C21 C25 1.438(3) . ? C21 C22 1.444(3) . ? C22 C23 1.419(4) . ? C23 C24 1.413(4) . ? C24 C25 1.419(4) . ? C26 C30 1.416(4) . ? C26 C27 1.418(4) . ? C27 C28 1.427(4) . ? C28 C29 1.413(4) . ? C29 C30 1.415(4) . ? O1 C31 1.438(3) . ? O1 C31 1.438(3) 7 ? C31 C32 1.502(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N2 Zn1 N2 169.09(11) 7 . ? N2 Zn1 N1 87.93(7) 7 7 ? N2 Zn1 N1 90.69(7) . 7 ? N2 Zn1 N1 90.69(7) 7 . ? N2 Zn1 N1 87.93(7) . . ? N1 Zn1 N1 165.38(12) 7 . ? N2 Zn1 O1 95.45(6) 7 . ? N2 Zn1 O1 95.45(6) . . ? N1 Zn1 O1 97.31(6) 7 . ? N1 Zn1 O1 97.31(6) . . ? C22 Fe1 C26 123.64(11) . . ? C22 Fe1 C23 40.77(10) . . ? C26 Fe1 C23 158.60(12) . . ? C22 Fe1 C28 120.62(12) . . ? C26 Fe1 C28 68.39(12) . . ? C23 Fe1 C28 105.09(12) . . ? C22 Fe1 C25 68.91(10) . . ? C26 Fe1 C25 125.01(11) . . ? C23 Fe1 C25 68.41(11) . . ? C28 Fe1 C25 158.15(12) . . ? C22 Fe1 C24 68.52(11) . . ? C26 Fe1 C24 160.37(12) . . ? C23 Fe1 C24 40.44(12) . . ? C28 Fe1 C24 121.12(12) . . ? C25 Fe1 C24 40.61(10) . . ? C22 Fe1 C29 156.50(10) . . ? C26 Fe1 C29 68.15(11) . . ? C23 Fe1 C29 120.91(11) . . ? C28 Fe1 C29 40.45(13) . . ? C25 Fe1 C29 123.64(12) . . ? C24 Fe1 C29 107.01(12) . . ? C22 Fe1 C27 106.42(11) . . ? C26 Fe1 C27 40.61(12) . . ? C23 Fe1 C27 121.30(12) . . ? C28 Fe1 C27 40.83(13) . . ? C25 Fe1 C27 160.36(12) . . ? C24 Fe1 C27 157.17(12) . . ? C29 Fe1 C27 68.27(12) . . ? C22 Fe1 C30 160.92(10) . . ? C26 Fe1 C30 40.58(11) . . ? C23 Fe1 C30 157.80(11) . . ? C28 Fe1 C30 68.19(12) . . ? C25 Fe1 C30 109.54(11) . . ? C24 Fe1 C30 123.53(12) . . ? C29 Fe1 C30 40.44(11) . . ? C27 Fe1 C30 68.30(12) . . ? C22 Fe1 C21 41.30(9) . . ? C26 Fe1 C21 109.10(10) . . ? C23 Fe1 C21 68.95(9) . . ? C28 Fe1 C21 158.12(12) . . ? C25 Fe1 C21 41.00(9) . . ? C24 Fe1 C21 68.77(10) . . ? C29 Fe1 C21 160.63(11) . . ? C27 Fe1 C21 123.03(11) . . ? C30 Fe1 C21 125.00(10) . . ? C1 N1 C4 106.68(19) . . ? C1 N1 Zn1 121.72(15) . . ? C4 N1 Zn1 118.96(15) . . ? C9 N2 C6 106.95(18) . . ? C9 N2 Zn1 128.14(15) . . ? C6 N2 Zn1 124.81(15) . . ? N1 C1 C2 110.8(2) . . ? N1 C1 C10 122.3(2) . 7 ? C2 C1 C10 126.6(2) . 7 ? C3 C2 C1 106.4(2) . . ? C2 C3 C4 107.4(2) . . ? N1 C4 C3 108.7(2) . . ? N1 C4 C5 122.6(2) . . ? C3 C4 C5 128.4(2) . . ? C6 C5 C4 124.3(2) . . ? C6 C5 C21 116.1(2) . . ? C4 C5 C21 119.5(2) . . ? N2 C6 C5 124.2(2) . . ? N2 C6 C7 108.2(2) . . ? C5 C6 C7 127.5(2) . . ? C8 C7 C6 107.4(2) . . ? C7 C8 C9 106.7(2) . . ? N2 C9 C8 110.7(2) . . ? N2 C9 C10 123.94(19) . . ? C8 C9 C10 125.2(2) . . ? C9 C10 C1 113.12(19) . 7 ? C9 C10 C11 109.3(2) . . ? C1 C10 C11 110.0(2) 7 . ? C9 C10 C12 107.6(2) . . ? C1 C10 C12 108.33(19) 7 . ? C11 C10 C12 108.3(2) . . ? C25 C21 C22 106.3(2) . . ? C25 C21 C5 127.9(2) . . ? C22 C21 C5 125.8(2) . . ? C25 C21 Fe1 68.82(14) . . ? C22 C21 Fe1 68.26(13) . . ? C5 C21 Fe1 129.71(16) . . ? C23 C22 C21 108.4(2) . . ? C23 C22 Fe1 69.95(15) . . ? C21 C22 Fe1 70.44(13) . . ? C24 C23 C22 108.3(2) . . ? C24 C23 Fe1 69.90(16) . . ? C22 C23 Fe1 69.27(14) . . ? C23 C24 C25 108.4(2) . . ? C23 C24 Fe1 69.66(15) . . ? C25 C24 Fe1 69.66(15) . . ? C24 C25 C21 108.5(2) . . ? C24 C25 Fe1 69.73(15) . . ? C21 C25 Fe1 70.17(13) . . ? C30 C26 C27 108.5(3) . . ? C30 C26 Fe1 70.15(15) . . ? C27 C26 Fe1 70.17(16) . . ? C26 C27 C28 107.3(3) . . ? C26 C27 Fe1 69.21(16) . . ? C28 C27 Fe1 69.29(16) . . ? C29 C28 C27 108.1(3) . . ? C29 C28 Fe1 70.00(16) . . ? C27 C28 Fe1 69.88(16) . . ? C28 C29 C30 108.3(3) . . ? C28 C29 Fe1 69.56(16) . . ? C30 C29 Fe1 69.82(15) . . ? C29 C30 C26 107.8(3) . . ? C29 C30 Fe1 69.75(16) . . ? C26 C30 Fe1 69.28(15) . . ? C31 O1 C31 115.8(3) . 7 ? C31 O1 Zn1 122.10(15) . . ? C31 O1 Zn1 122.10(15) 7 . ? O1 C31 C32 113.0(2) . . ? _diffrn_measured_fraction_theta_max 0.938 _diffrn_reflns_theta_full 28.99 _diffrn_measured_fraction_theta_full 0.938 _refine_diff_density_max 0.301 _refine_diff_density_min -0.500 _refine_diff_density_rms 0.056 data_struc_4 _database_code_depnum_ccdc_archive 'CCDC 272663' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common 'calix(4)phyrin (5)' _chemical_melting_point ? _chemical_formula_moiety ? _chemical_formula_sum 'C45 H40 Cl2 Cu Fe2 N4' _chemical_formula_weight 882.95 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' Cl Cl 0.1484 0.1585 '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' Cu Cu 0.3201 1.2651 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Orthorhombic _symmetry_space_group_name_H-M Pnma loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-x+1/2, -y, z+1/2' '-x, y+1/2, -z' 'x+1/2, -y+1/2, -z+1/2' '-x, -y, -z' 'x-1/2, y, -z-1/2' 'x, -y-1/2, z' '-x-1/2, y-1/2, z-1/2' _cell_length_a 14.7414(19) _cell_length_b 18.668(2) _cell_length_c 13.5904(17) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 90.00 _cell_volume 3740.0(8) _cell_formula_units_Z 4 _cell_measurement_temperature 293(2) _cell_measurement_reflns_used 971 _cell_measurement_theta_min 2.9865 _cell_measurement_theta_max 28.378 _exptl_crystal_description 'Square prism' _exptl_crystal_colour black _exptl_crystal_size_max 0.40 _exptl_crystal_size_mid 0.20 _exptl_crystal_size_min 0.20 _exptl_crystal_density_meas 0 _exptl_crystal_density_diffrn 1.568 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 1812 _exptl_absorpt_coefficient_mu 1.512 _exptl_absorpt_correction_type none _exptl_absorpt_correction_T_min ? _exptl_absorpt_correction_T_max ? _exptl_absorpt_process_details ? _exptl_special_details ; ? ; _diffrn_ambient_temperature 293(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'CCD area detector' _diffrn_measurement_method 'phi and omega scans' _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 22287 _diffrn_reflns_av_R_equivalents 0.0183 _diffrn_reflns_av_sigmaI/netI 0.0160 _diffrn_reflns_limit_h_min -19 _diffrn_reflns_limit_h_max 19 _diffrn_reflns_limit_k_min -25 _diffrn_reflns_limit_k_max 18 _diffrn_reflns_limit_l_min -17 _diffrn_reflns_limit_l_max 13 _diffrn_reflns_theta_min 1.85 _diffrn_reflns_theta_max 29.10 _reflns_number_total 4794 _reflns_number_gt 4316 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'Bruker SMART' _computing_cell_refinement 'Bruker SMART' _computing_data_reduction 'Bruker SAINT' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'Bruker SHELXTL' _computing_publication_material 'Bruker SHELXTL' _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^)+(0.0358P)^2^+5.2228P] where P=(Fo^2^+2Fc^2^)/3' _atom_sites_solution_primary direct _atom_sites_solution_secondary difmap _atom_sites_solution_hydrogens geom _refine_ls_hydrogen_treatment mixed _refine_ls_extinction_method none _refine_ls_extinction_coef ? _refine_ls_number_reflns 4794 _refine_ls_number_parameters 297 _refine_ls_number_restraints 2 _refine_ls_R_factor_all 0.0449 _refine_ls_R_factor_gt 0.0393 _refine_ls_wR_factor_ref 0.0926 _refine_ls_wR_factor_gt 0.0899 _refine_ls_goodness_of_fit_ref 1.137 _refine_ls_restrained_S_all 1.137 _refine_ls_shift/su_max 0.003 _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 Cu Cu 0.76047(2) 0.7500 0.73066(2) 0.01657(9) Uani 1 2 d S . . Fe Fe 0.52097(2) 0.470835(17) 0.70544(2) 0.02164(9) Uani 1 1 d . . . N1 N 0.79175(12) 0.67587(9) 0.63579(13) 0.0192(3) Uani 1 1 d . . . N2 N 0.72446(12) 0.67518(9) 0.82281(13) 0.0189(3) Uani 1 1 d . . . C1 C 0.84626(14) 0.68367(11) 0.55691(15) 0.0203(4) Uani 1 1 d . . . C2 C 0.84060(15) 0.62282(12) 0.49561(16) 0.0239(4) Uani 1 1 d . . . H2 H 0.8724 0.6152 0.4375 0.029 Uiso 1 1 calc R . . C3 C 0.77861(15) 0.57667(12) 0.53855(16) 0.0231(4) Uani 1 1 d . . . H3 H 0.7601 0.5325 0.5142 0.028 Uiso 1 1 calc R . . C4 C 0.74852(14) 0.60979(11) 0.62710(15) 0.0187(4) Uani 1 1 d . . . C5 C 0.69421(14) 0.57925(11) 0.70219(15) 0.0184(4) Uani 1 1 d . . . C6 C 0.68774(14) 0.60846(11) 0.79710(15) 0.0193(4) Uani 1 1 d . . . C7 C 0.65297(15) 0.57656(12) 0.88439(16) 0.0236(4) Uani 1 1 d . . . H7 H 0.6235 0.5326 0.8887 0.028 Uiso 1 1 calc R . . C8 C 0.67058(15) 0.62221(12) 0.96110(15) 0.0232(4) Uani 1 1 d . . . H8 H 0.6572 0.6145 1.0271 0.028 Uiso 1 1 calc R . . C9 C 0.71318(14) 0.68340(11) 0.92003(15) 0.0186(4) Uani 1 1 d . . . C10 C 0.7474(2) 0.7500 0.9717(2) 0.0197(6) Uani 1 2 d S . . C11 C 0.9046(2) 0.7500 0.5450(2) 0.0227(6) Uani 1 2 d S . . C12 C 0.8519(2) 0.7500 0.9663(3) 0.0262(7) Uani 1 2 d S . . H12A H 0.874(3) 0.7500 0.899(3) 0.027(10) Uiso 1 2 d S . . H12B H 0.8749(19) 0.7902(15) 0.995(2) 0.033(7) Uiso 1 1 d . . . C13 C 0.7184(2) 0.7500 1.0804(2) 0.0247(6) Uani 1 2 d S . . H13A H 0.652(3) 0.7500 1.087(3) 0.030(10) Uiso 1 2 d S . . H13B H 0.7416(18) 0.7087(15) 1.114(2) 0.029(7) Uiso 1 1 d . . . C14 C 0.9787(2) 0.7500 0.6255(3) 0.0304(7) Uani 1 2 d S . . H14A H 0.954(3) 0.7500 0.692(3) 0.035(11) Uiso 1 2 d S . . H14B H 1.017(2) 0.7071(17) 0.622(2) 0.043(9) Uiso 1 1 d . . . C15 C 0.9502(3) 0.7500 0.4436(3) 0.0350(8) Uani 1 2 d S . . H15A H 0.908(3) 0.7500 0.394(3) 0.024(10) Uiso 1 2 d S . . H15B H 0.988(2) 0.7913(18) 0.432(2) 0.049(9) Uiso 1 1 d . . . C21 C 0.65019(14) 0.51026(11) 0.67737(15) 0.0195(4) Uani 1 1 d . . . C22 C 0.60191(15) 0.49575(12) 0.58766(16) 0.0232(4) Uani 1 1 d . . . H22 H 0.5878 0.5308 0.5362 0.028 Uiso 1 1 calc R . . C23 C 0.57778(16) 0.42184(12) 0.58652(18) 0.0275(5) Uani 1 1 d . . . H23 H 0.5450 0.3970 0.5339 0.033 Uiso 1 1 calc R . . C24 C 0.61037(16) 0.39039(12) 0.67480(18) 0.0285(5) Uani 1 1 d . . . H24 H 0.6035 0.3401 0.6939 0.034 Uiso 1 1 calc R . . C25 C 0.65428(15) 0.44439(12) 0.73105(17) 0.0236(4) Uani 1 1 d . . . H25 H 0.6823 0.4377 0.7958 0.028 Uiso 1 1 calc R . . C26 C 0.44544(19) 0.54368(16) 0.7832(2) 0.0398(6) Uani 1 1 d . . . H26 H 0.4663 0.5906 0.8062 0.048 Uiso 1 1 calc R . . C27 C 0.40353(18) 0.52931(18) 0.6910(2) 0.0430(7) Uani 1 1 d . . . H27 H 0.3903 0.5644 0.6393 0.052 Uiso 1 1 calc R . . C28 C 0.38460(17) 0.45511(18) 0.6873(2) 0.0405(7) Uani 1 1 d . . . H28 H 0.3560 0.4298 0.6323 0.049 Uiso 1 1 calc R . . C29 C 0.41415(18) 0.42356(17) 0.7763(2) 0.0391(6) Uani 1 1 d . . . H29 H 0.4092 0.3728 0.7940 0.047 Uiso 1 1 calc R . . C30 C 0.45180(18) 0.47848(17) 0.83573(19) 0.0375(6) Uani 1 1 d . . . H30 H 0.4777 0.4723 0.9016 0.045 Uiso 1 1 calc R . . C31 C 0.6381(5) 0.7500 0.4864(6) 0.079(2) Uani 0.850(4) 2 d SP A 1 H31A H 0.6769 0.7920 0.4860 0.095 Uiso 0.4250(19) 1 calc PR A 1 H31B H 0.6769 0.7080 0.4860 0.095 Uiso 0.4250(19) 1 calc PR A 1 Cl1 Cl 0.57310(11) 0.7500 0.59552(18) 0.0989(9) Uani 0.850(4) 2 d SP A 1 Cl2 Cl 0.57289(13) 0.7500 0.38160(16) 0.0805(7) Uani 0.850(4) 2 d SP A 1 C31B C 0.675(4) 0.7500 0.4438(19) 0.11(2) Uiso 0.150(4) 2 d SPD A 2 H31C H 0.7067 0.7912 0.4702 0.137 Uiso 0.0750(19) 1 calc PR A 2 H31D H 0.7067 0.7088 0.4702 0.137 Uiso 0.0750(19) 1 calc PR A 2 Cl3 Cl 0.575(3) 0.7500 0.509(4) 0.30(2) Uiso 0.150(4) 2 d SPD A 2 Cl4 Cl 0.7066(11) 0.7500 0.3218(12) 0.114(5) Uiso 0.150(4) 2 d SPD A 2 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 Cu 0.01857(18) 0.01499(17) 0.01614(17) 0.000 0.00277(13) 0.000 Fe 0.01858(16) 0.02200(16) 0.02433(16) -0.00315(12) 0.00341(11) -0.00196(12) N1 0.0196(8) 0.0170(8) 0.0210(8) -0.0004(7) 0.0045(7) -0.0004(7) N2 0.0214(8) 0.0175(8) 0.0178(8) -0.0002(6) 0.0006(7) -0.0025(7) C1 0.0180(9) 0.0211(10) 0.0217(10) -0.0007(8) 0.0034(8) 0.0018(8) C2 0.0245(10) 0.0252(11) 0.0220(10) -0.0045(8) 0.0072(8) 0.0003(9) C3 0.0233(10) 0.0228(10) 0.0233(10) -0.0052(8) 0.0023(8) 0.0003(8) C4 0.0184(9) 0.0180(9) 0.0197(9) -0.0012(7) 0.0009(7) 0.0006(8) C5 0.0158(9) 0.0172(9) 0.0222(9) 0.0008(8) -0.0010(7) 0.0003(7) C6 0.0196(10) 0.0177(9) 0.0207(9) 0.0000(8) -0.0005(8) -0.0024(8) C7 0.0275(11) 0.0209(10) 0.0225(10) 0.0031(8) 0.0008(8) -0.0046(9) C8 0.0273(11) 0.0234(11) 0.0188(10) 0.0039(8) 0.0019(8) -0.0022(9) C9 0.0183(9) 0.0190(9) 0.0185(9) 0.0012(7) -0.0010(7) 0.0008(8) C10 0.0215(14) 0.0207(14) 0.0169(13) 0.000 -0.0015(11) 0.000 C11 0.0207(14) 0.0199(14) 0.0275(15) 0.000 0.0089(12) 0.000 C12 0.0219(15) 0.0242(16) 0.0325(18) 0.000 -0.0047(13) 0.000 C13 0.0308(17) 0.0266(16) 0.0168(14) 0.000 -0.0025(12) 0.000 C14 0.0193(15) 0.0249(16) 0.047(2) 0.000 0.0008(15) 0.000 C15 0.038(2) 0.0282(18) 0.039(2) 0.000 0.0212(17) 0.000 C21 0.0186(9) 0.0180(10) 0.0220(9) -0.0016(8) 0.0034(8) -0.0003(8) C22 0.0214(10) 0.0265(11) 0.0217(10) -0.0031(8) 0.0024(8) -0.0026(9) C23 0.0256(11) 0.0248(11) 0.0321(12) -0.0112(9) 0.0035(9) -0.0030(9) C24 0.0280(11) 0.0175(10) 0.0399(13) -0.0040(9) 0.0049(10) 0.0003(9) C25 0.0225(10) 0.0196(10) 0.0288(11) 0.0013(9) 0.0016(9) -0.0005(8) C26 0.0308(13) 0.0395(15) 0.0492(16) -0.0141(12) 0.0127(12) 0.0043(11) C27 0.0254(12) 0.0583(19) 0.0452(16) 0.0028(14) 0.0084(11) 0.0137(12) C28 0.0208(12) 0.0655(19) 0.0354(13) -0.0089(13) 0.0049(10) -0.0079(12) C29 0.0297(13) 0.0504(16) 0.0372(14) -0.0010(12) 0.0118(11) -0.0128(12) C30 0.0300(12) 0.0560(17) 0.0264(12) -0.0073(11) 0.0092(10) -0.0045(12) C31 0.037(3) 0.117(7) 0.083(5) 0.000 -0.019(4) 0.000 Cl1 0.0297(7) 0.174(2) 0.0933(15) 0.000 -0.0038(8) 0.000 Cl2 0.0670(11) 0.0802(12) 0.0943(14) 0.000 -0.0384(10) 0.000 _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 Cu N1 1.9469(17) . ? Cu N1 1.9469(18) 7_575 ? Cu N2 1.9496(17) 7_575 ? Cu N2 1.9496(17) . ? Fe C23 2.037(2) . ? Fe C24 2.041(2) . ? Fe C29 2.046(3) . ? Fe C28 2.047(3) . ? Fe C30 2.048(2) . ? Fe C22 2.050(2) . ? Fe C26 2.051(3) . ? Fe C25 2.056(2) . ? Fe C27 2.056(3) . ? Fe C21 2.077(2) . ? N1 C1 1.348(3) . ? N1 C4 1.393(3) . ? N2 C9 1.341(3) . ? N2 C6 1.402(3) . ? C1 C2 1.411(3) . ? C1 C11 1.516(3) . ? C2 C3 1.385(3) . ? C3 C4 1.424(3) . ? C4 C5 1.417(3) . ? C5 C6 1.403(3) . ? C5 C21 1.481(3) . ? C6 C7 1.423(3) . ? C7 C8 1.371(3) . ? C8 C9 1.418(3) . ? C9 C10 1.514(3) . ? C10 C9 1.514(3) 7_575 ? C10 C13 1.538(4) . ? C10 C12 1.543(4) . ? C11 C1 1.516(3) 7_575 ? C11 C15 1.533(5) . ? C11 C14 1.546(5) . ? C21 C25 1.431(3) . ? C21 C22 1.437(3) . ? C22 C23 1.425(3) . ? C23 C24 1.420(4) . ? C24 C25 1.421(3) . ? C26 C30 1.415(4) . ? C26 C27 1.422(4) . ? C27 C28 1.414(4) . ? C28 C29 1.415(4) . ? C29 C30 1.418(4) . ? C31 Cl2 1.719(7) . ? C31 Cl1 1.765(10) . ? C31B Cl4 1.722(10) . ? C31B Cl3 1.725(10) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Cu N1 90.61(10) . 7_575 ? N1 Cu N2 177.65(8) . 7_575 ? N1 Cu N2 88.89(7) 7_575 7_575 ? N1 Cu N2 88.89(7) . . ? N1 Cu N2 177.65(8) 7_575 . ? N2 Cu N2 91.52(10) 7_575 . ? C23 Fe C24 40.74(10) . . ? C23 Fe C29 119.76(11) . . ? C24 Fe C29 106.00(11) . . ? C23 Fe C28 104.10(10) . . ? C24 Fe C28 120.27(11) . . ? C29 Fe C28 40.45(12) . . ? C23 Fe C30 157.19(11) . . ? C24 Fe C30 123.31(11) . . ? C29 Fe C30 40.52(11) . . ? C28 Fe C30 68.00(11) . . ? C23 Fe C22 40.81(9) . . ? C24 Fe C22 68.40(10) . . ? C29 Fe C22 155.99(10) . . ? C28 Fe C22 120.66(10) . . ? C30 Fe C22 161.62(11) . . ? C23 Fe C26 158.37(11) . . ? C24 Fe C26 160.69(12) . . ? C29 Fe C26 68.01(12) . . ? C28 Fe C26 67.91(12) . . ? C30 Fe C26 40.38(12) . . ? C22 Fe C26 124.59(11) . . ? C23 Fe C25 68.51(9) . . ? C24 Fe C25 40.59(9) . . ? C29 Fe C25 123.53(11) . . ? C28 Fe C25 157.65(12) . . ? C30 Fe C25 110.26(10) . . ? C22 Fe C25 68.30(9) . . ? C26 Fe C25 126.24(11) . . ? C23 Fe C27 120.57(11) . . ? C24 Fe C27 156.18(12) . . ? C29 Fe C27 68.04(13) . . ? C28 Fe C27 40.32(13) . . ? C30 Fe C27 68.07(12) . . ? C22 Fe C27 107.16(11) . . ? C26 Fe C27 40.53(12) . . ? C25 Fe C27 161.54(11) . . ? C23 Fe C21 68.68(9) . . ? C24 Fe C21 68.35(9) . . ? C29 Fe C21 160.89(10) . . ? C28 Fe C21 158.33(11) . . ? C30 Fe C21 126.20(10) . . ? C22 Fe C21 40.76(8) . . ? C26 Fe C21 110.95(10) . . ? C25 Fe C21 40.51(8) . . ? C27 Fe C21 124.50(11) . . ? C1 N1 C4 107.52(17) . . ? C1 N1 Cu 126.24(15) . . ? C4 N1 Cu 125.24(14) . . ? C9 N2 C6 107.42(17) . . ? C9 N2 Cu 125.80(14) . . ? C6 N2 Cu 125.55(14) . . ? N1 C1 C2 110.33(19) . . ? N1 C1 C11 120.8(2) . . ? C2 C1 C11 128.9(2) . . ? C3 C2 C1 106.91(18) . . ? C2 C3 C4 106.95(19) . . ? N1 C4 C5 123.62(18) . . ? N1 C4 C3 108.27(18) . . ? C5 C4 C3 127.6(2) . . ? C6 C5 C4 122.96(19) . . ? C6 C5 C21 121.15(18) . . ? C4 C5 C21 115.68(18) . . ? N2 C6 C5 123.22(19) . . ? N2 C6 C7 107.64(18) . . ? C5 C6 C7 128.91(19) . . ? C8 C7 C6 107.79(19) . . ? C7 C8 C9 106.57(19) . . ? N2 C9 C8 110.53(18) . . ? N2 C9 C10 120.6(2) . . ? C8 C9 C10 128.8(2) . . ? C9 C10 C9 110.4(2) 7_575 . ? C9 C10 C13 110.67(16) 7_575 . ? C9 C10 C13 110.67(16) . . ? C9 C10 C12 108.09(17) 7_575 . ? C9 C10 C12 108.09(17) . . ? C13 C10 C12 108.8(3) . . ? C1 C11 C1 109.5(2) 7_575 . ? C1 C11 C15 110.19(18) 7_575 . ? C1 C11 C15 110.19(18) . . ? C1 C11 C14 108.96(18) 7_575 . ? C1 C11 C14 108.96(18) . . ? C15 C11 C14 109.0(3) . . ? C25 C21 C22 106.94(19) . . ? C25 C21 C5 127.78(19) . . ? C22 C21 C5 125.02(19) . . ? C25 C21 Fe 68.94(12) . . ? C22 C21 Fe 68.59(12) . . ? C5 C21 Fe 131.91(15) . . ? C23 C22 C21 108.4(2) . . ? C23 C22 Fe 69.11(13) . . ? C21 C22 Fe 70.65(12) . . ? C24 C23 C22 107.9(2) . . ? C24 C23 Fe 69.77(13) . . ? C22 C23 Fe 70.08(13) . . ? C23 C24 C25 108.4(2) . . ? C23 C24 Fe 69.49(13) . . ? C25 C24 Fe 70.27(13) . . ? C24 C25 C21 108.4(2) . . ? C24 C25 Fe 69.14(13) . . ? C21 C25 Fe 70.55(12) . . ? C30 C26 C27 108.1(3) . . ? C30 C26 Fe 69.73(15) . . ? C27 C26 Fe 69.95(15) . . ? C28 C27 C26 107.6(3) . . ? C28 C27 Fe 69.48(16) . . ? C26 C27 Fe 69.52(15) . . ? C27 C28 C29 108.4(3) . . ? C27 C28 Fe 70.20(15) . . ? C29 C28 Fe 69.76(15) . . ? C28 C29 C30 107.9(3) . . ? C28 C29 Fe 69.79(15) . . ? C30 C29 Fe 69.82(15) . . ? C26 C30 C29 108.0(3) . . ? C26 C30 Fe 69.90(15) . . ? C29 C30 Fe 69.66(14) . . ? Cl2 C31 Cl1 113.1(4) . . ? Cl4 C31B Cl3 137(4) . . ? _diffrn_measured_fraction_theta_max 0.924 _diffrn_reflns_theta_full 29.10 _diffrn_measured_fraction_theta_full 0.924 _refine_diff_density_max 1.072 _refine_diff_density_min -0.757 _refine_diff_density_rms 0.076