# Supplementary Material (ESI) for Chemical Communications # This journal is © The Royal Society of Chemistry 2004 data_global _journal_coden_Cambridge 182 _journal_volume ? _journal_year ? _journal_page_first ? _publ_contact_author_name 'Dr Cameron J. Kepert' _publ_contact_author_address ; School of Chemistry University of Sydney Sydney, NSW 2006 Australia ; _publ_contact_author_email c.kepert@chem.usyd.edu.au _publ_requested_journal 'Chemical Communications' _publ_section_title ; Nanoporosity of an interpenetrated NbO-type molecular framework studied by single crystal X-ray diffraction ; _publ_section_abstract ; The molecular framework [Fe(NCS)2(tmbpz)2] (tmbpz = 3,3',5,5' tetramethyl 4,4' bipyrazolyl) forms an uncommon and highly robust doubly interpenetrated NbO-type net structure that remains stable on the removal of the solvent of crystallisation. ; loop_ _publ_author_name _publ_author_address 'Ganesan, Prasad V.' ; School of Chemistry University of Sydney Sydney, NSW 2006 Australia ; 'Kepert, Cameron J.' ; School of Chemistry University of Sydney Sydney, NSW 2006 Australia ; data_A_2/3MECN _database_code_depnum_ccdc_archive 'CCDC 243653' ############################################################################## ### VALIDATION RESPONSE FORM (VRF) ### ### ### ### AUTHOR: PLEASE INSERT THE BLOCK OF TEXT FROM HERE TO THE END OF THE ### ### VRF IN YOUR CIF AND ADD YOUR RESPONSE(S) IN THE APPROPRIATE PLACE(S). ### ### THE BLOCK SHOULD BE INSERTED IN THE CIF AFTER THE FIRST DATABLOCK ### ### IDENTIFIER. ### ### ### ############################################################################## _vrf_ABSTM_02_A_2_3MECN ; PROBLEM: Alert A The ratio of expected to reported Tmax/Tmin(RR') is < 0.50 RESPONSE: The crystal used consisted of two almost equal twins, each generating significant non-coincident diffraction peaks. The structure presented is based on integration of intensity data for the major twin alone. Structural refinement using integration data from both twin components was attempted in GEMINI, but gave a significantly poorer result. It is believed that the presence of a significant minor twin may result in large outlier absorption correction values, and this would affect the absorption correction ratios obtained empirically using SADABS. ; _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C22 H28 Fe N10 S2, 2/3(C2 H3 N)' _chemical_formula_sum 'C23.33 H30 Fe N10.67 S2' _chemical_formula_weight 579.88 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Hexagonal _symmetry_space_group_name_H-M R-3 _symmetry_space_group_name_Hall -R3 _symmetry_Int_Tables_number 148 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 25.283(17) _cell_length_b 25.283(17) _cell_length_c 10.962(11) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 6068(8) _cell_formula_units_Z 9 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 879 _cell_measurement_theta_min 2.630 _cell_measurement_theta_max 24.070 _exptl_crystal_description 'hexagonal rods' _exptl_crystal_colour purple _exptl_crystal_size_max 0.22 _exptl_crystal_size_mid 0.14 _exptl_crystal_size_min 0.12 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.428 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2724 _exptl_absorpt_coefficient_mu 0.749 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.242 _exptl_absorpt_correction_T_max 0.914 _exptl_absorpt_process_details 'SADABS, Bruker 1995' _exptl_special_details ; 'In thin film of perfluoropolyether oil on a mohair fibre' ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 57 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.00 _diffrn_reflns_number 18070 _diffrn_reflns_av_R_equivalents 0.0771 _diffrn_reflns_av_sigmaI/netI 0.0787 _diffrn_reflns_limit_h_min -33 _diffrn_reflns_limit_h_max 33 _diffrn_reflns_limit_k_min -33 _diffrn_reflns_limit_k_max 33 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 1.61 _diffrn_reflns_theta_max 28.06 _reflns_number_total 3193 _reflns_number_gt 2168 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (BrukerAXS, 1997)' _computing_cell_refinement 'SMART (BrukerAXS, 1997), GEMINI (BrukerAXS, 1999)' _computing_data_reduction 'SAINT+ (BrukerAXS, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XPMA/ZORTEP, WebLabViewer Pro 3.7' _computing_publication_material ? _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. In this material the iron(II) centres are coordinated in distorted octahedral fashion by two trans thiocyanato ligands and four tmbpz ligands that link the iron centres together. The resulting structure consists of two identical interpenetrated NbO-type nets related by a (001) translation. The interpenetration of the nets is stabilised by a network of hydrogen bonds between them, of the form N-H...S - these are tabulated below. The interpenetrating framework structure houses 1-D, solvent-filled channels running parallel to the c axis, each consisting of small cavities connected by smaller hexagonal windows of sulphur atoms. In the as-grown material the pores each contain two disordered MeCN molecules whose bond axis lies approximately along the threefold axis. The solvent was modelled as a one-third occupied acetonitrile molecule, with the disordered counterparts generated by the axial symmetry. The crystal consisted of two almost equal twins, each generating significant non-coincident diffraction peaks. The reduced unit cell of the crystal was extracted using GEMINI, and used in SMART to generate the hexagonal cell and in SAINT+ to solve the structure of the major twin. Structural refinement using integration data from both twin components was attempted in GEMINI, but gave a significantly poorer result. It is believed that the presence of a significant minor twin may account for the unusual absorption correction values obtained empirically using SADABS. All non-hydrogen atoms were refined anisotropically except those of the disordered acetonitrile molecule. Hydrogen atoms were geometrically constrained using a riding atom model. Methyl group hydrogen atoms on tmbpz and acetonitrile appeared to be disordered when difference peaks were examined, and therefore they were modelled accordingly. ; _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^)+(0.0560P)^2^+36.9633P] 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 3193 _refine_ls_number_parameters 170 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.1016 _refine_ls_R_factor_gt 0.0574 _refine_ls_wR_factor_ref 0.1674 _refine_ls_wR_factor_gt 0.1323 _refine_ls_goodness_of_fit_ref 1.087 _refine_ls_restrained_S_all 1.087 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Fe1 Fe 0.5000 0.5000 0.5000 0.0212(2) Uani 1 2 d S . . S1 S 0.33022(4) 0.52617(5) 0.62433(9) 0.0264(3) Uani 1 1 d . . . C1 C 0.39166(17) 0.52260(17) 0.5957(3) 0.0214(8) Uani 1 1 d . . . N1 N 0.43528(15) 0.51991(15) 0.5729(3) 0.0231(7) Uani 1 1 d . . . N10 N 0.54818(14) 0.52780(14) 0.6809(3) 0.0224(7) Uani 1 1 d . . . N11 N 0.54900(14) 0.57680(14) 0.7330(3) 0.0230(7) Uani 1 1 d . . . H11 H 0.5289 0.5941 0.7037 0.028 Uiso 1 1 calc R . . C10 C 0.58474(18) 0.51637(17) 0.7525(3) 0.0235(8) Uani 1 1 d . . . C11 C 0.60904(17) 0.55930(17) 0.8497(3) 0.0216(8) Uani 1 1 d . . . C12 C 0.58387(17) 0.59633(18) 0.8343(3) 0.0223(8) Uani 1 1 d . . . C13 C 0.5966(2) 0.46485(19) 0.7295(4) 0.0298(9) Uani 1 1 d . . . H13A H 0.5743 0.4425 0.6564 0.045 Uiso 0.50 1 calc PR . . H13B H 0.5827 0.4372 0.7998 0.045 Uiso 0.50 1 calc PR . . H13C H 0.6404 0.4812 0.7172 0.045 Uiso 0.50 1 calc PR . . H13D H 0.6240 0.4647 0.7925 0.045 Uiso 0.50 1 calc PR . . H13E H 0.6156 0.4700 0.6492 0.045 Uiso 0.50 1 calc PR . . H13F H 0.5579 0.4260 0.7317 0.045 Uiso 0.50 1 calc PR . . C14 C 0.5901(2) 0.6483(2) 0.9073(4) 0.0331(10) Uani 1 1 d . . . H14A H 0.5658 0.6645 0.8699 0.050 Uiso 0.50 1 calc PR . . H14B H 0.6331 0.6805 0.9100 0.050 Uiso 0.50 1 calc PR . . H14C H 0.5754 0.6345 0.9904 0.050 Uiso 0.50 1 calc PR . . H14D H 0.6170 0.6551 0.9770 0.050 Uiso 0.50 1 calc PR . . H14E H 0.5498 0.6392 0.9369 0.050 Uiso 0.50 1 calc PR . . H14F H 0.6075 0.6851 0.8565 0.050 Uiso 0.50 1 calc PR . . C20 C 0.64507(18) 0.52440(17) 1.0368(3) 0.0226(8) Uani 1 1 d . . . C21 C 0.65254(17) 0.56556(17) 0.9466(3) 0.0212(8) Uani 1 1 d . . . C22 C 0.70952(17) 0.61864(17) 0.9750(3) 0.0229(8) Uani 1 1 d . . . C23 C 0.5934(2) 0.46115(19) 1.0588(4) 0.0338(10) Uani 1 1 d . . . H23A H 0.6024 0.4439 1.1306 0.051 Uiso 0.50 1 calc PR . . H23B H 0.5881 0.4357 0.9874 0.051 Uiso 0.50 1 calc PR . . H23C H 0.5558 0.4625 1.0729 0.051 Uiso 0.50 1 calc PR . . H23D H 0.5618 0.4508 0.9967 0.051 Uiso 0.50 1 calc PR . . H23E H 0.5761 0.4590 1.1399 0.051 Uiso 0.50 1 calc PR . . H23F H 0.6084 0.4322 1.0543 0.051 Uiso 0.50 1 calc PR . . C24 C 0.74110(19) 0.67682(19) 0.9043(4) 0.0294(9) Uani 1 1 d . . . H24A H 0.7795 0.7053 0.9449 0.044 Uiso 0.50 1 calc PR . . H24B H 0.7148 0.6950 0.9001 0.044 Uiso 0.50 1 calc PR . . H24C H 0.7497 0.6684 0.8216 0.044 Uiso 0.50 1 calc PR . . H24D H 0.7165 0.6739 0.8329 0.044 Uiso 0.50 1 calc PR . . H24E H 0.7812 0.6841 0.8776 0.044 Uiso 0.50 1 calc PR . . H24F H 0.7464 0.7107 0.9561 0.044 Uiso 0.50 1 calc PR . . N20 N 0.73489(14) 0.61025(14) 1.0750(3) 0.0224(7) Uani 1 1 d . . . N21 N 0.69407(14) 0.55167(14) 1.1104(3) 0.0228(7) Uani 1 1 d . . . H21 H 0.6994 0.5338 1.1744 0.027 Uiso 1 1 calc R . . C101 C 0.3333 0.6667 -0.1259(18) 0.132(6) Uiso 1 3 d S . . H10A H 0.3056 0.6400 -0.1896 0.197 Uiso 0.17 1 calc PR . . H10B H 0.3756 0.6851 -0.1547 0.197 Uiso 0.17 1 calc PR . . H10C H 0.3239 0.6989 -0.1071 0.197 Uiso 0.17 1 calc PR . . H10D H 0.3645 0.7094 -0.1113 0.197 Uiso 0.17 1 calc PR . . H10E H 0.2945 0.6643 -0.1463 0.197 Uiso 0.17 1 calc PR . . H10F H 0.3462 0.6504 -0.1938 0.197 Uiso 0.17 1 calc PR . . C100 C 0.3261(15) 0.6324(12) -0.021(3) 0.104(8) Uiso 0.33 1 d P . . N100 N 0.3306(17) 0.6082(16) 0.071(3) 0.172(12) Uiso 0.33 1 d P . . 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 0.0168(4) 0.0234(4) 0.0228(4) -0.0029(3) -0.0010(3) 0.0096(3) S1 0.0195(5) 0.0290(5) 0.0327(5) 0.0015(4) 0.0011(4) 0.0135(4) C1 0.0180(18) 0.0181(18) 0.0234(18) -0.0009(14) -0.0017(14) 0.0056(15) N1 0.0217(17) 0.0220(17) 0.0254(16) 0.0002(13) 0.0020(13) 0.0106(14) N10 0.0206(16) 0.0206(16) 0.0248(16) -0.0025(13) -0.0018(13) 0.0093(14) N11 0.0217(16) 0.0226(17) 0.0262(16) -0.0029(13) -0.0056(13) 0.0123(14) C10 0.0225(19) 0.022(2) 0.0236(19) 0.0013(15) 0.0029(15) 0.0098(17) C11 0.0215(19) 0.0220(19) 0.0205(18) -0.0008(14) -0.0007(14) 0.0102(16) C12 0.0197(19) 0.0232(19) 0.0217(18) 0.0002(15) -0.0027(14) 0.0090(16) C13 0.034(2) 0.027(2) 0.030(2) -0.0029(16) -0.0035(17) 0.0171(19) C14 0.039(2) 0.032(2) 0.035(2) -0.0092(18) -0.0124(19) 0.023(2) C20 0.025(2) 0.0222(19) 0.0227(18) -0.0016(15) -0.0004(15) 0.0133(17) C21 0.0213(19) 0.0235(19) 0.0202(18) -0.0013(14) 0.0006(14) 0.0122(16) C22 0.0213(19) 0.023(2) 0.0257(19) -0.0001(15) 0.0001(15) 0.0116(16) C23 0.031(2) 0.026(2) 0.035(2) 0.0063(17) -0.0007(18) 0.0074(19) C24 0.029(2) 0.027(2) 0.028(2) 0.0059(16) -0.0067(17) 0.0101(18) N20 0.0205(16) 0.0220(17) 0.0238(16) 0.0042(13) 0.0016(13) 0.0098(14) N21 0.0228(17) 0.0227(17) 0.0245(16) 0.0053(13) -0.0018(13) 0.0124(14) _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 N1 2.096(3) 10_666 ? Fe1 N1 2.096(3) . ? Fe1 N10 2.248(4) . ? Fe1 N10 2.248(3) 10_666 ? Fe1 N20 2.385(3) 18_546 ? Fe1 N20 2.385(3) 6_564 ? S1 C1 1.631(4) . ? C1 N1 1.166(5) . ? N10 C10 1.349(5) . ? N10 N11 1.355(4) . ? N11 C12 1.349(5) . ? N11 H11 0.8800 . ? C10 C11 1.423(5) . ? C10 C13 1.497(6) . ? C11 C12 1.380(5) . ? C11 C21 1.479(5) . ? C12 C14 1.479(6) . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C13 H13D 0.9800 . ? C13 H13E 0.9800 . ? C13 H13F 0.9800 . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C14 H14D 0.9800 . ? C14 H14E 0.9800 . ? C14 H14F 0.9800 . ? C20 N21 1.344(5) . ? C20 C21 1.379(5) . ? C20 C23 1.494(6) . ? C21 C22 1.428(5) . ? C22 N20 1.340(5) . ? C22 C24 1.492(5) . ? C23 H23A 0.9800 . ? C23 H23B 0.9800 . ? C23 H23C 0.9800 . ? C23 H23D 0.9800 . ? C23 H23E 0.9800 . ? C23 H23F 0.9800 . ? C24 H24A 0.9800 . ? C24 H24B 0.9800 . ? C24 H24C 0.9800 . ? C24 H24D 0.9800 . ? C24 H24E 0.9800 . ? C24 H24F 0.9800 . ? N20 N21 1.371(4) . ? N20 Fe1 2.385(3) 8_655 ? N21 H21 0.8800 . ? C101 C100 1.40(3) . ? C101 H10A 0.9800 . ? C101 H10B 0.9800 . ? C101 H10C 0.9800 . ? C101 H10D 0.9800 . ? C101 H10E 0.9800 . ? C101 H10F 0.9800 . ? C100 N100 1.21(4) . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Fe1 N1 180.000(1) 10_666 . ? N1 Fe1 N10 92.60(13) 10_666 . ? N1 Fe1 N10 87.40(13) . . ? N1 Fe1 N10 87.40(13) 10_666 10_666 ? N1 Fe1 N10 92.60(13) . 10_666 ? N10 Fe1 N10 180.000(1) . 10_666 ? N1 Fe1 N20 84.48(12) 10_666 18_546 ? N1 Fe1 N20 95.52(12) . 18_546 ? N10 Fe1 N20 81.01(12) . 18_546 ? N10 Fe1 N20 98.99(12) 10_666 18_546 ? N1 Fe1 N20 95.52(12) 10_666 6_564 ? N1 Fe1 N20 84.48(12) . 6_564 ? N10 Fe1 N20 98.99(12) . 6_564 ? N10 Fe1 N20 81.01(12) 10_666 6_564 ? N20 Fe1 N20 180.00(10) 18_546 6_564 ? N1 C1 S1 178.7(3) . . ? C1 N1 Fe1 166.1(3) . . ? C10 N10 N11 104.6(3) . . ? C10 N10 Fe1 140.2(3) . . ? N11 N10 Fe1 114.6(2) . . ? C12 N11 N10 112.9(3) . . ? C12 N11 H11 123.5 . . ? N10 N11 H11 123.5 . . ? N10 C10 C11 110.7(3) . . ? N10 C10 C13 123.0(3) . . ? C11 C10 C13 126.3(4) . . ? C12 C11 C10 104.9(3) . . ? C12 C11 C21 125.8(3) . . ? C10 C11 C21 129.3(3) . . ? N11 C12 C11 106.9(3) . . ? N11 C12 C14 122.0(3) . . ? C11 C12 C14 131.1(3) . . ? C10 C13 H13A 109.5 . . ? C10 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C10 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C10 C13 H13D 109.5 . . ? H13A C13 H13D 141.1 . . ? H13B C13 H13D 56.3 . . ? H13C C13 H13D 56.3 . . ? C10 C13 H13E 109.5 . . ? H13A C13 H13E 56.3 . . ? H13B C13 H13E 141.1 . . ? H13C C13 H13E 56.3 . . ? H13D C13 H13E 109.5 . . ? C10 C13 H13F 109.5 . . ? H13A C13 H13F 56.3 . . ? H13B C13 H13F 56.3 . . ? H13C C13 H13F 141.1 . . ? H13D C13 H13F 109.5 . . ? H13E C13 H13F 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C12 C14 H14D 109.5 . . ? H14A C14 H14D 141.1 . . ? H14B C14 H14D 56.3 . . ? H14C C14 H14D 56.3 . . ? C12 C14 H14E 109.5 . . ? H14A C14 H14E 56.3 . . ? H14B C14 H14E 141.1 . . ? H14C C14 H14E 56.3 . . ? H14D C14 H14E 109.5 . . ? C12 C14 H14F 109.5 . . ? H14A C14 H14F 56.3 . . ? H14B C14 H14F 56.3 . . ? H14C C14 H14F 141.1 . . ? H14D C14 H14F 109.5 . . ? H14E C14 H14F 109.5 . . ? N21 C20 C21 107.5(3) . . ? N21 C20 C23 122.7(3) . . ? C21 C20 C23 129.8(4) . . ? C20 C21 C22 104.2(3) . . ? C20 C21 C11 128.3(4) . . ? C22 C21 C11 127.1(3) . . ? N20 C22 C21 111.6(3) . . ? N20 C22 C24 121.2(3) . . ? C21 C22 C24 127.2(3) . . ? 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 . . ? C20 C23 H23D 109.5 . . ? H23A C23 H23D 141.1 . . ? H23B C23 H23D 56.3 . . ? H23C C23 H23D 56.3 . . ? C20 C23 H23E 109.5 . . ? H23A C23 H23E 56.3 . . ? H23B C23 H23E 141.1 . . ? H23C C23 H23E 56.3 . . ? H23D C23 H23E 109.5 . . ? C20 C23 H23F 109.5 . . ? H23A C23 H23F 56.3 . . ? H23B C23 H23F 56.3 . . ? H23C C23 H23F 141.1 . . ? H23D C23 H23F 109.5 . . ? H23E C23 H23F 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C22 C24 H24D 109.5 . . ? H24A C24 H24D 141.1 . . ? H24B C24 H24D 56.3 . . ? H24C C24 H24D 56.3 . . ? C22 C24 H24E 109.5 . . ? H24A C24 H24E 56.3 . . ? H24B C24 H24E 141.1 . . ? H24C C24 H24E 56.3 . . ? H24D C24 H24E 109.5 . . ? C22 C24 H24F 109.5 . . ? H24A C24 H24F 56.3 . . ? H24B C24 H24F 56.3 . . ? H24C C24 H24F 141.1 . . ? H24D C24 H24F 109.5 . . ? H24E C24 H24F 109.5 . . ? C22 N20 N21 103.9(3) . . ? C22 N20 Fe1 133.6(3) . 8_655 ? N21 N20 Fe1 121.6(2) . 8_655 ? C20 N21 N20 112.8(3) . . ? C20 N21 H21 123.6 . . ? N20 N21 H21 123.6 . . ? C100 C101 H10A 109.5 . . ? C100 C101 H10B 109.5 . . ? H10A C101 H10B 109.5 . . ? C100 C101 H10C 109.5 . . ? H10A C101 H10C 109.5 . . ? H10B C101 H10C 109.5 . . ? C100 C101 H10D 109.5 . . ? H10A C101 H10D 141.1 . . ? H10B C101 H10D 56.3 . . ? H10C C101 H10D 56.3 . . ? C100 C101 H10E 109.5 . . ? H10A C101 H10E 56.3 . . ? H10B C101 H10E 141.1 . . ? H10C C101 H10E 56.3 . . ? H10D C101 H10E 109.5 . . ? C100 C101 H10F 109.5 . . ? H10A C101 H10F 56.3 . . ? H10B C101 H10F 56.3 . . ? H10C C101 H10F 141.1 . . ? H10D C101 H10F 109.5 . . ? H10E C101 H10F 109.5 . . ? N100 C100 C101 169(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 N11 H11 S1 0.88 2.80 3.625(4) 156.8 15_556 N21 H21 S1 0.88 2.57 3.391(4) 156.0 10_667 _diffrn_measured_fraction_theta_max 0.971 _diffrn_reflns_theta_full 28.06 _diffrn_measured_fraction_theta_full 0.971 _refine_diff_density_max 0.655 _refine_diff_density_min -0.893 _refine_diff_density_rms 0.109 #===END data_A _database_code_depnum_ccdc_archive 'CCDC 243654' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C22 H28 Fe N10 S2' _chemical_formula_sum 'C22 H28 Fe N10 S2' _chemical_formula_weight 552.51 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Hexagonal _symmetry_space_group_name_H-M R-3 _symmetry_space_group_name_Hall -R3 _symmetry_Int_Tables_number 148 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 25.2831(14) _cell_length_b 25.2831(14) _cell_length_c 10.9463(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 6059.8(9) _cell_formula_units_Z 9 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 959 _cell_measurement_theta_min 2.632 _cell_measurement_theta_max 25.740 _exptl_crystal_description 'hexagonal rods' _exptl_crystal_colour purple _exptl_crystal_size_max 0.20 _exptl_crystal_size_mid 0.18 _exptl_crystal_size_min 0.15 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.363 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2592 _exptl_absorpt_coefficient_mu 0.746 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.719 _exptl_absorpt_correction_T_max 0.894 _exptl_absorpt_process_details 'SADABS, Bruker 1995' _exptl_special_details ; Fixed in an open capillary with a small amount of grease and heated in an oven at 400 K for 48 h. The capillary was then sealed for data collection ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number ? _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 17321 _diffrn_reflns_av_R_equivalents 0.0412 _diffrn_reflns_av_sigmaI/netI 0.0557 _diffrn_reflns_limit_h_min -33 _diffrn_reflns_limit_h_max 33 _diffrn_reflns_limit_k_min -33 _diffrn_reflns_limit_k_max 33 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.08 _diffrn_reflns_theta_max 27.99 _reflns_number_total 3237 _reflns_number_gt 2204 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (BrukerAXS, 1997)' _computing_cell_refinement 'SMART (BrukerAXS, 1997)' _computing_data_reduction 'SAINT+ (BrukerAXS, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XPMA/ZORTEP, WebLabViewer Pro 3.7' _computing_publication_material ? _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. In this material the iron(II) centres are coordinated in distorted octahedral fashion by two trans thiocyanato ligands and four tmbpz ligands that link the iron centres together. The resulting structure consists of two identical interpenetrated NbO-type nets related by a (001) translation. The interpenetration of the nets is stabilised by a network of hydrogen bonds between them, of the form N-H...S - these are tabulated below. The interpenetrating framework structure houses 1-D channels running parallel to the c axis, each consisting of small cavities connected by smaller hexagonal windows of sulphur atoms. In the as-grown material the pores each contain MeCN solvent of crystallisation. However, heating ex situ removed this solvent, leaving significant void volume in the crystal structure. Modelling an MeCN molecule with partial occupancy (as for A_0.27MeCN, see below) indicated that the solvent channels were less than 10% occupied, with no improvement in refinement parameters observed. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were geometrically constrained using a riding atom model. Methyl group hydrogen atoms on tmbpz appeared to be disordered when difference peaks were examined, and therefore they were modelled accordingly. We note that the refinement parameters R1 and wR2 are both significantly less for this desolvated phase than for the parent phase (see above). However, we attribute this improvement at least in part to differences in crystal quality. To date it has proved impossible to desolvate a crystal of A.2/3MeCN completely in situ, meaning that any comparison of refinement parameters must be made with caution. ; _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^)+(0.0333P)^2^+26.2251P] 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 3237 _refine_ls_number_parameters 160 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0822 _refine_ls_R_factor_gt 0.0421 _refine_ls_wR_factor_ref 0.1008 _refine_ls_wR_factor_gt 0.0851 _refine_ls_goodness_of_fit_ref 1.022 _refine_ls_restrained_S_all 1.022 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Fe1 Fe 0.5000 0.5000 0.5000 0.01470(14) Uani 1 2 d S . . S1 S 0.32984(3) 0.52473(3) 0.62311(6) 0.02136(17) Uani 1 1 d . . . C1 C 0.39158(13) 0.52147(12) 0.5951(2) 0.0162(6) Uani 1 1 d . . . N1 N 0.43574(11) 0.51961(10) 0.57267(19) 0.0170(5) Uani 1 1 d . . . N10 N 0.54824(10) 0.52748(10) 0.6819(2) 0.0173(5) Uani 1 1 d . . . N11 N 0.54899(10) 0.57666(10) 0.73428(19) 0.0168(5) Uani 1 1 d . . . H11 H 0.5287 0.5938 0.7054 0.020 Uiso 1 1 calc R . . C10 C 0.58472(12) 0.51623(12) 0.7531(2) 0.0166(5) Uani 1 1 d . . . C11 C 0.60900(12) 0.55875(12) 0.8505(2) 0.0152(5) Uani 1 1 d . . . C12 C 0.58408(13) 0.59618(13) 0.8351(2) 0.0169(6) Uani 1 1 d . . . C13 C 0.59633(14) 0.46469(13) 0.7289(3) 0.0224(6) Uani 1 1 d . . . H13A H 0.5739 0.4425 0.6556 0.034 Uiso 0.50 1 calc PR . . H13B H 0.5826 0.4368 0.7989 0.034 Uiso 0.50 1 calc PR . . H13C H 0.6401 0.4809 0.7161 0.034 Uiso 0.50 1 calc PR . . H13D H 0.6238 0.4643 0.7915 0.034 Uiso 0.50 1 calc PR . . H13E H 0.6152 0.4700 0.6482 0.034 Uiso 0.50 1 calc PR . . H13F H 0.5576 0.4259 0.7310 0.034 Uiso 0.50 1 calc PR . . C14 C 0.59013(15) 0.64812(14) 0.9083(3) 0.0267(7) Uani 1 1 d . . . H14A H 0.5659 0.6642 0.8707 0.040 Uiso 0.50 1 calc PR . . H14B H 0.6331 0.6803 0.9111 0.040 Uiso 0.50 1 calc PR . . H14C H 0.5754 0.6342 0.9914 0.040 Uiso 0.50 1 calc PR . . H14D H 0.6171 0.6549 0.9781 0.040 Uiso 0.50 1 calc PR . . H14E H 0.5498 0.6389 0.9377 0.040 Uiso 0.50 1 calc PR . . H14F H 0.6075 0.6849 0.8574 0.040 Uiso 0.50 1 calc PR . . C20 C 0.64504(13) 0.52407(13) 1.0376(2) 0.0177(6) Uani 1 1 d . . . C21 C 0.65270(12) 0.56558(12) 0.9472(2) 0.0152(5) Uani 1 1 d . . . C22 C 0.70931(12) 0.61836(13) 0.9748(2) 0.0168(6) Uani 1 1 d . . . C23 C 0.59409(14) 0.46103(14) 1.0607(3) 0.0272(7) Uani 1 1 d . . . H23A H 0.6036 0.4442 1.1326 0.041 Uiso 0.50 1 calc PR . . H23B H 0.5888 0.4353 0.9895 0.041 Uiso 0.50 1 calc PR . . H23C H 0.5563 0.4620 1.0752 0.041 Uiso 0.50 1 calc PR . . H23D H 0.5622 0.4502 0.9989 0.041 Uiso 0.50 1 calc PR . . H23E H 0.5770 0.4590 1.1420 0.041 Uiso 0.50 1 calc PR . . H23F H 0.6095 0.4324 1.0563 0.041 Uiso 0.50 1 calc PR . . C24 C 0.74081(14) 0.67667(14) 0.9048(3) 0.0240(6) Uani 1 1 d . . . H24A H 0.7792 0.7050 0.9456 0.036 Uiso 0.50 1 calc PR . . H24B H 0.7145 0.6948 0.9010 0.036 Uiso 0.50 1 calc PR . . H24C H 0.7494 0.6685 0.8218 0.036 Uiso 0.50 1 calc PR . . H24D H 0.7162 0.6739 0.8334 0.036 Uiso 0.50 1 calc PR . . H24E H 0.7809 0.6841 0.8779 0.036 Uiso 0.50 1 calc PR . . H24F H 0.7460 0.7104 0.9572 0.036 Uiso 0.50 1 calc PR . . N20 N 0.73473(10) 0.61022(10) 1.07568(19) 0.0156(5) Uani 1 1 d . . . N21 N 0.69450(10) 0.55200(10) 1.1105(2) 0.0165(5) Uani 1 1 d . . . H21 H 0.7002 0.5343 1.1743 0.020 Uiso 1 1 calc R . . loop_ _atom_site_aniso_label _atom_site_aniso_U_11 _atom_site_aniso_U_22 _atom_site_aniso_U_33 _atom_site_aniso_U_23 _atom_site_aniso_U_13 _atom_site_aniso_U_12 Fe1 0.0134(3) 0.0183(3) 0.0123(2) -0.0017(2) -0.0010(2) 0.0079(2) S1 0.0171(4) 0.0270(4) 0.0223(3) 0.0015(3) 0.0019(3) 0.0127(3) C1 0.0180(14) 0.0143(13) 0.0126(12) -0.0004(10) -0.0001(10) 0.0053(11) N1 0.0183(12) 0.0180(12) 0.0137(11) 0.0013(9) 0.0012(9) 0.0084(10) N10 0.0189(12) 0.0177(12) 0.0155(11) -0.0010(9) -0.0015(9) 0.0092(10) N11 0.0195(12) 0.0175(12) 0.0156(11) -0.0027(9) -0.0034(9) 0.0108(10) C10 0.0159(13) 0.0163(13) 0.0147(12) 0.0018(10) 0.0015(10) 0.0059(12) C11 0.0157(13) 0.0160(13) 0.0116(12) -0.0007(10) -0.0007(10) 0.0064(11) C12 0.0168(14) 0.0188(14) 0.0131(12) -0.0011(10) -0.0019(10) 0.0073(12) C13 0.0277(16) 0.0226(15) 0.0198(14) -0.0031(11) -0.0043(12) 0.0148(13) C14 0.0347(18) 0.0291(17) 0.0221(15) -0.0088(13) -0.0112(13) 0.0203(15) C20 0.0188(14) 0.0212(14) 0.0156(12) -0.0009(11) 0.0014(11) 0.0118(12) C21 0.0170(13) 0.0189(14) 0.0116(12) -0.0003(10) 0.0006(10) 0.0104(12) C22 0.0183(14) 0.0204(14) 0.0133(12) 0.0002(10) -0.0009(10) 0.0110(12) C23 0.0278(17) 0.0219(16) 0.0240(15) 0.0042(12) -0.0015(13) 0.0065(14) C24 0.0222(15) 0.0244(16) 0.0186(14) 0.0032(12) -0.0062(12) 0.0066(13) N20 0.0166(11) 0.0166(12) 0.0137(10) 0.0013(9) 0.0002(9) 0.0083(10) N21 0.0175(12) 0.0175(12) 0.0151(11) 0.0033(9) -0.0014(9) 0.0092(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 N1 2.079(2) . ? Fe1 N1 2.079(2) 10_666 ? Fe1 N10 2.255(2) 10_666 ? Fe1 N10 2.255(2) . ? Fe1 N20 2.385(2) 6_564 ? Fe1 N20 2.385(2) 18_546 ? S1 C1 1.632(3) . ? C1 N1 1.167(3) . ? N10 C10 1.343(3) . ? N10 N11 1.361(3) . ? N11 C12 1.345(3) . ? N11 H11 0.8800 . ? C10 C11 1.417(4) . ? C10 C13 1.496(4) . ? C11 C12 1.385(4) . ? C11 C21 1.477(3) . ? C12 C14 1.480(4) . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C13 H13D 0.9800 . ? C13 H13E 0.9800 . ? C13 H13F 0.9800 . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C14 H14D 0.9800 . ? C14 H14E 0.9800 . ? C14 H14F 0.9800 . ? C20 N21 1.347(3) . ? C20 C21 1.383(4) . ? C20 C23 1.487(4) . ? C21 C22 1.418(4) . ? C22 N20 1.344(3) . ? C22 C24 1.490(4) . ? C23 H23A 0.9800 . ? C23 H23B 0.9800 . ? C23 H23C 0.9800 . ? C23 H23D 0.9800 . ? C23 H23E 0.9800 . ? C23 H23F 0.9800 . ? C24 H24A 0.9800 . ? C24 H24B 0.9800 . ? C24 H24C 0.9800 . ? C24 H24D 0.9800 . ? C24 H24E 0.9800 . ? C24 H24F 0.9800 . ? N20 N21 1.360(3) . ? N20 Fe1 2.385(2) 8_655 ? N21 H21 0.8800 . ? loop_ _geom_angle_atom_site_label_1 _geom_angle_atom_site_label_2 _geom_angle_atom_site_label_3 _geom_angle _geom_angle_site_symmetry_1 _geom_angle_site_symmetry_3 _geom_angle_publ_flag N1 Fe1 N1 180.0 . 10_666 ? N1 Fe1 N10 92.51(8) . 10_666 ? N1 Fe1 N10 87.49(8) 10_666 10_666 ? N1 Fe1 N10 87.49(8) . . ? N1 Fe1 N10 92.51(8) 10_666 . ? N10 Fe1 N10 180.000(1) 10_666 . ? N1 Fe1 N20 84.50(8) . 6_564 ? N1 Fe1 N20 95.50(8) 10_666 6_564 ? N10 Fe1 N20 81.00(8) 10_666 6_564 ? N10 Fe1 N20 99.00(8) . 6_564 ? N1 Fe1 N20 95.50(8) . 18_546 ? N1 Fe1 N20 84.50(8) 10_666 18_546 ? N10 Fe1 N20 99.00(8) 10_666 18_546 ? N10 Fe1 N20 81.00(8) . 18_546 ? N20 Fe1 N20 180.0 6_564 18_546 ? N1 C1 S1 178.5(3) . . ? C1 N1 Fe1 165.4(2) . . ? C10 N10 N11 104.6(2) . . ? C10 N10 Fe1 140.42(18) . . ? N11 N10 Fe1 114.31(15) . . ? C12 N11 N10 112.7(2) . . ? C12 N11 H11 123.7 . . ? N10 N11 H11 123.7 . . ? N10 C10 C11 111.0(2) . . ? N10 C10 C13 122.4(2) . . ? C11 C10 C13 126.6(2) . . ? C12 C11 C10 104.7(2) . . ? C12 C11 C21 125.2(2) . . ? C10 C11 C21 130.0(2) . . ? N11 C12 C11 107.0(2) . . ? N11 C12 C14 121.7(2) . . ? C11 C12 C14 131.3(2) . . ? C10 C13 H13A 109.5 . . ? C10 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C10 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C10 C13 H13D 109.5 . . ? H13A C13 H13D 141.1 . . ? H13B C13 H13D 56.3 . . ? H13C C13 H13D 56.3 . . ? C10 C13 H13E 109.5 . . ? H13A C13 H13E 56.3 . . ? H13B C13 H13E 141.1 . . ? H13C C13 H13E 56.3 . . ? H13D C13 H13E 109.5 . . ? C10 C13 H13F 109.5 . . ? H13A C13 H13F 56.3 . . ? H13B C13 H13F 56.3 . . ? H13C C13 H13F 141.1 . . ? H13D C13 H13F 109.5 . . ? H13E C13 H13F 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C12 C14 H14D 109.5 . . ? H14A C14 H14D 141.1 . . ? H14B C14 H14D 56.3 . . ? H14C C14 H14D 56.3 . . ? C12 C14 H14E 109.5 . . ? H14A C14 H14E 56.3 . . ? H14B C14 H14E 141.1 . . ? H14C C14 H14E 56.3 . . ? H14D C14 H14E 109.5 . . ? C12 C14 H14F 109.5 . . ? H14A C14 H14F 56.3 . . ? H14B C14 H14F 56.3 . . ? H14C C14 H14F 141.1 . . ? H14D C14 H14F 109.5 . . ? H14E C14 H14F 109.5 . . ? N21 C20 C21 106.6(2) . . ? N21 C20 C23 122.7(2) . . ? C21 C20 C23 130.7(3) . . ? C20 C21 C22 104.7(2) . . ? C20 C21 C11 127.7(2) . . ? C22 C21 C11 127.4(2) . . ? N20 C22 C21 111.4(2) . . ? N20 C22 C24 120.9(2) . . ? C21 C22 C24 127.6(2) . . ? 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 . . ? C20 C23 H23D 109.5 . . ? H23A C23 H23D 141.1 . . ? H23B C23 H23D 56.3 . . ? H23C C23 H23D 56.3 . . ? C20 C23 H23E 109.5 . . ? H23A C23 H23E 56.3 . . ? H23B C23 H23E 141.1 . . ? H23C C23 H23E 56.3 . . ? H23D C23 H23E 109.5 . . ? C20 C23 H23F 109.5 . . ? H23A C23 H23F 56.3 . . ? H23B C23 H23F 56.3 . . ? H23C C23 H23F 141.1 . . ? H23D C23 H23F 109.5 . . ? H23E C23 H23F 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C22 C24 H24D 109.5 . . ? H24A C24 H24D 141.1 . . ? H24B C24 H24D 56.3 . . ? H24C C24 H24D 56.3 . . ? C22 C24 H24E 109.5 . . ? H24A C24 H24E 56.3 . . ? H24B C24 H24E 141.1 . . ? H24C C24 H24E 56.3 . . ? H24D C24 H24E 109.5 . . ? C22 C24 H24F 109.5 . . ? H24A C24 H24F 56.3 . . ? H24B C24 H24F 56.3 . . ? H24C C24 H24F 141.1 . . ? H24D C24 H24F 109.5 . . ? H24E C24 H24F 109.5 . . ? C22 N20 N21 103.9(2) . . ? C22 N20 Fe1 133.50(18) . 8_655 ? N21 N20 Fe1 121.52(15) . 8_655 ? C20 N21 N20 113.4(2) . . ? C20 N21 H21 123.3 . . ? N20 N21 H21 123.3 . . ? 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 N11 H11 S1 0.88 2.77 3.596(2) 157.1 15_556 N21 H21 S1 0.88 2.57 3.384(2) 154.9 10_667 _diffrn_measured_fraction_theta_max 0.994 _diffrn_reflns_theta_full 27.99 _diffrn_measured_fraction_theta_full 0.994 _refine_diff_density_max 0.588 _refine_diff_density_min -0.461 _refine_diff_density_rms 0.085 #===END data_A_0.27MECN _database_code_depnum_ccdc_archive 'CCDC 243655' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C22 H28 Fe N10 S2, 0.27 (C2 H3 N)' _chemical_formula_sum 'C22.55 H28.82 Fe N10.27 S2' _chemical_formula_weight 563.80 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Hexagonal _symmetry_space_group_name_H-M R-3 _symmetry_space_group_name_Hall -R3 _symmetry_Int_Tables_number 148 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 25.3021(14) _cell_length_b 25.3021(14) _cell_length_c 10.9672(13) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 6080.5(9) _cell_formula_units_Z 9 _cell_measurement_temperature 150(2) _cell_measurement_reflns_used 899 _cell_measurement_theta_min 2.789 _cell_measurement_theta_max 25.716 _exptl_crystal_description 'hexagonal rods' _exptl_crystal_colour purple _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.385 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2646 _exptl_absorpt_coefficient_mu 0.745 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.806 _exptl_absorpt_correction_T_max 0.921 _exptl_absorpt_process_details 'SADABS, Bruker 1995' _exptl_special_details ; 'In an open capillary; heated to 375 K for 24 hours then cooled to 150 K' ; _diffrn_ambient_temperature 150(2) _diffrn_radiation_wavelength 0.71073 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'Bruker SMART 1000 CCD' _diffrn_measurement_method /w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 71 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.00 _diffrn_reflns_number 19731 _diffrn_reflns_av_R_equivalents 0.0422 _diffrn_reflns_av_sigmaI/netI 0.0424 _diffrn_reflns_limit_h_min -32 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -32 _diffrn_reflns_limit_k_max 32 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.08 _diffrn_reflns_theta_max 27.96 _reflns_number_total 3107 _reflns_number_gt 2259 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (BrukerAXS, 1997)' _computing_cell_refinement 'SMART (BrukerAXS, 1997)' _computing_data_reduction 'SAINT+ (BrukerAXS, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XPMA/ZORTEP, WebLabViewer Pro 3.7' _computing_publication_material ? _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. In this material the iron(II) centres are coordinated in distorted octahedral fashion by two trans thiocyanato ligands and four tmbpz ligands that link the iron centres together. The resulting structure consists of two identical interpenetrated NbO-type nets related by a (001) translation. The interpenetration of the nets is stabilised by a network of hydrogen bonds between them, of the form N-H...S - these are tabulated below. The interpenetrating framework structure houses 1-D channels running parallel to the c axis, each consisting of small cavities connected by smaller hexagonal windows of sulphur atoms. This structure was obtained after prolonged (24 h) heating of the crystal in situ at 375 K before cooling to 150 K. Fourier difference synthesis indicated the presence of significant electron density in the 1-D channels, consistent with the continuing presence of some solvent of crystallisation in the material. This solvent was modelled similarly to the as-grown material (see data_A_2/3MECN) with isotropic thermal parameters fixed at slightly larger values than those obtained by refinement of A_2/3MeCN at 150 K. These values are tabulated below: C101 0.100 Uiso C100 0.100 Uiso N100 0.150 Uiso The occupancy of these three atom positions was allowed to refine by means of a single free variable. The value obtained (FVAR 0.41237) indicates a 41% occupancy of the solvent atom positions. Note that no further restraints were required to maintain the solvent atom positions. All non-hydrogen atoms were refined anisotropically except those of the disordered acetonitrile molecule. Hydrogen atoms were geometrically constrained using a riding atom model. Methyl group hydrogen atoms on tmbpz and acetonitrile appeared to be disordered when difference peaks were examined, and therefore they were modelled accordingly. ; _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^)+(0.0126P)^2^+30.2627P] 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 3107 _refine_ls_number_parameters 168 _refine_ls_number_restraints 0 _refine_ls_R_factor_all 0.0699 _refine_ls_R_factor_gt 0.0369 _refine_ls_wR_factor_ref 0.0858 _refine_ls_wR_factor_gt 0.0714 _refine_ls_goodness_of_fit_ref 1.071 _refine_ls_restrained_S_all 1.071 _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 0.5000 0.5000 0.5000 0.01447(12) Uani 1 2 d S . . S1 S 0.32957(3) 0.52450(3) 0.62357(6) 0.02063(15) Uani 1 1 d . . . C1 C 0.39145(11) 0.52157(11) 0.5953(2) 0.0158(5) Uani 1 1 d . . . N1 N 0.43555(10) 0.51963(9) 0.57268(18) 0.0173(4) Uani 1 1 d . . . N10 N 0.54839(9) 0.52750(9) 0.68154(18) 0.0166(4) Uani 1 1 d . . . N11 N 0.54910(9) 0.57656(9) 0.73348(18) 0.0169(4) Uani 1 1 d . . . H11 H 0.5288 0.5936 0.7044 0.020 Uiso 1 1 calc R . . C10 C 0.58483(11) 0.51612(11) 0.7527(2) 0.0155(5) Uani 1 1 d . . . C11 C 0.60915(11) 0.55889(11) 0.8500(2) 0.0155(5) Uani 1 1 d . . . C12 C 0.58414(11) 0.59632(11) 0.8342(2) 0.0167(5) Uani 1 1 d . . . C13 C 0.59663(13) 0.46479(12) 0.7284(2) 0.0227(6) Uani 1 1 d . . . H13A H 0.5743 0.4426 0.6553 0.034 Uiso 0.50 1 calc PR . . H13B H 0.5830 0.4369 0.7983 0.034 Uiso 0.50 1 calc PR . . H13C H 0.6404 0.4812 0.7157 0.034 Uiso 0.50 1 calc PR . . H13D H 0.6242 0.4645 0.7909 0.034 Uiso 0.50 1 calc PR . . H13E H 0.6155 0.4702 0.6479 0.034 Uiso 0.50 1 calc PR . . H13F H 0.5580 0.4260 0.7305 0.034 Uiso 0.50 1 calc PR . . C14 C 0.59046(14) 0.64829(13) 0.9074(2) 0.0266(6) Uani 1 1 d . . . H14A H 0.5663 0.6645 0.8701 0.040 Uiso 0.50 1 calc PR . . H14B H 0.6335 0.6803 0.9100 0.040 Uiso 0.50 1 calc PR . . H14C H 0.5758 0.6345 0.9904 0.040 Uiso 0.50 1 calc PR . . H14D H 0.6174 0.6550 0.9769 0.040 Uiso 0.50 1 calc PR . . H14E H 0.5502 0.6392 0.9370 0.040 Uiso 0.50 1 calc PR . . H14F H 0.6079 0.6851 0.8566 0.040 Uiso 0.50 1 calc PR . . C20 C 0.64529(11) 0.52404(11) 1.0366(2) 0.0166(5) Uani 1 1 d . . . C21 C 0.65283(11) 0.56569(11) 0.9470(2) 0.0149(5) Uani 1 1 d . . . C22 C 0.70937(11) 0.61846(11) 0.9745(2) 0.0155(5) Uani 1 1 d . . . C23 C 0.59418(13) 0.46076(12) 1.0596(2) 0.0261(6) Uani 1 1 d . . . H23A H 0.6036 0.4439 1.1314 0.039 Uiso 0.50 1 calc PR . . H23B H 0.5890 0.4351 0.9885 0.039 Uiso 0.50 1 calc PR . . H23C H 0.5564 0.4617 1.0739 0.039 Uiso 0.50 1 calc PR . . H23D H 0.5624 0.4499 0.9978 0.039 Uiso 0.50 1 calc PR . . H23E H 0.5770 0.4587 1.1407 0.039 Uiso 0.50 1 calc PR . . H23F H 0.6096 0.4321 1.0553 0.039 Uiso 0.50 1 calc PR . . C24 C 0.74075(12) 0.67665(12) 0.9046(2) 0.0235(6) Uani 1 1 d . . . H24A H 0.7792 0.7050 0.9452 0.035 Uiso 0.50 1 calc PR . . H24B H 0.7144 0.6948 0.9008 0.035 Uiso 0.50 1 calc PR . . H24C H 0.7493 0.6685 0.8217 0.035 Uiso 0.50 1 calc PR . . H24D H 0.7161 0.6738 0.8333 0.035 Uiso 0.50 1 calc PR . . H24E H 0.7808 0.6841 0.8777 0.035 Uiso 0.50 1 calc PR . . H24F H 0.7460 0.7104 0.9568 0.035 Uiso 0.50 1 calc PR . . N20 N 0.73482(9) 0.61032(9) 1.07537(18) 0.0150(4) Uani 1 1 d . . . N21 N 0.69458(9) 0.55201(9) 1.11035(18) 0.0161(4) Uani 1 1 d . . . H21 H 0.7001 0.5344 1.1744 0.019 Uiso 1 1 calc R . . C101 C 0.3333 0.6667 -0.183(2) 0.100 Uiso 0.412(11) 3 d SP . . H10A H 0.3042 0.6364 -0.2407 0.150 Uiso 0.0687(19) 1 calc PR . . H10B H 0.3750 0.6815 -0.2128 0.150 Uiso 0.0687(19) 1 calc PR . . H10C H 0.3257 0.7009 -0.1769 0.150 Uiso 0.0687(19) 1 calc PR . . H10D H 0.3657 0.7095 -0.1795 0.150 Uiso 0.0687(19) 1 calc PR . . H10E H 0.2950 0.6644 -0.2075 0.150 Uiso 0.0687(19) 1 calc PR . . H10F H 0.3442 0.6450 -0.2433 0.150 Uiso 0.0687(19) 1 calc PR . . C100 C 0.326(3) 0.6400(18) -0.070(4) 0.100 Uiso 0.137(4) 1 d P . . N100 N 0.319(2) 0.622(2) 0.023(5) 0.150 Uiso 0.137(4) 1 d P . . 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 0.0138(3) 0.0183(3) 0.0116(2) -0.0018(2) -0.0010(2) 0.0082(2) S1 0.0168(3) 0.0263(4) 0.0214(3) 0.0011(3) 0.0015(3) 0.0127(3) C1 0.0186(13) 0.0124(11) 0.0119(11) -0.0005(9) -0.0019(9) 0.0042(10) N1 0.0176(11) 0.0182(11) 0.0142(10) 0.0006(8) 0.0009(8) 0.0076(9) N10 0.0167(10) 0.0181(11) 0.0142(10) -0.0023(8) -0.0007(8) 0.0080(9) N11 0.0189(11) 0.0202(11) 0.0144(10) -0.0017(8) -0.0034(8) 0.0118(9) C10 0.0146(12) 0.0162(12) 0.0125(11) 0.0013(9) 0.0014(9) 0.0053(10) C11 0.0156(12) 0.0158(12) 0.0116(11) -0.0007(9) -0.0013(9) 0.0053(10) C12 0.0166(12) 0.0200(13) 0.0121(11) -0.0012(10) -0.0016(9) 0.0081(10) C13 0.0280(14) 0.0229(14) 0.0185(13) -0.0033(11) -0.0052(11) 0.0138(12) C14 0.0353(16) 0.0297(15) 0.0222(14) -0.0088(12) -0.0115(12) 0.0219(13) C20 0.0189(12) 0.0187(12) 0.0136(11) -0.0004(10) 0.0009(10) 0.0104(11) C21 0.0176(12) 0.0182(12) 0.0094(11) -0.0005(9) -0.0002(9) 0.0094(10) C22 0.0162(12) 0.0181(12) 0.0129(11) -0.0014(9) -0.0014(9) 0.0091(10) C23 0.0258(15) 0.0214(14) 0.0232(14) 0.0036(11) -0.0012(11) 0.0058(12) C24 0.0233(14) 0.0231(14) 0.0177(13) 0.0033(11) -0.0080(11) 0.0068(12) N20 0.0164(10) 0.0164(10) 0.0119(10) 0.0016(8) 0.0012(8) 0.0080(9) N21 0.0184(11) 0.0174(10) 0.0129(10) 0.0032(8) -0.0011(8) 0.0094(9) _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 N1 2.086(2) 10_666 ? Fe1 N1 2.086(2) . ? Fe1 N10 2.257(2) . ? Fe1 N10 2.257(2) 10_666 ? Fe1 N20 2.386(2) 18_546 ? Fe1 N20 2.386(2) 6_564 ? S1 C1 1.633(3) . ? C1 N1 1.168(3) . ? N10 C10 1.344(3) . ? N10 N11 1.358(3) . ? N11 C12 1.346(3) . ? N11 H11 0.8800 . ? C10 C11 1.422(3) . ? C10 C13 1.495(3) . ? C11 C12 1.388(3) . ? C11 C21 1.481(3) . ? C12 C14 1.479(3) . ? C13 H13A 0.9800 . ? C13 H13B 0.9800 . ? C13 H13C 0.9800 . ? C13 H13D 0.9800 . ? C13 H13E 0.9800 . ? C13 H13F 0.9800 . ? C14 H14A 0.9800 . ? C14 H14B 0.9800 . ? C14 H14C 0.9800 . ? C14 H14D 0.9800 . ? C14 H14E 0.9800 . ? C14 H14F 0.9800 . ? C20 N21 1.352(3) . ? C20 C21 1.383(3) . ? C20 C23 1.493(3) . ? C21 C22 1.418(3) . ? C22 N20 1.347(3) . ? C22 C24 1.489(3) . ? C23 H23A 0.9800 . ? C23 H23B 0.9800 . ? C23 H23C 0.9800 . ? C23 H23D 0.9800 . ? C23 H23E 0.9800 . ? C23 H23F 0.9800 . ? C24 H24A 0.9800 . ? C24 H24B 0.9800 . ? C24 H24C 0.9800 . ? C24 H24D 0.9800 . ? C24 H24E 0.9800 . ? C24 H24F 0.9800 . ? N20 N21 1.363(3) . ? N20 Fe1 2.386(2) 8_655 ? N21 H21 0.8800 . ? C101 C100 1.38(4) . ? C101 H10A 0.9800 . ? C101 H10B 0.9800 . ? C101 H10C 0.9800 . ? C101 H10D 0.9800 . ? C101 H10E 0.9800 . ? C101 H10F 0.9800 . ? C100 N100 1.10(5) . ? 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 Fe1 N1 180.0 10_666 . ? N1 Fe1 N10 92.43(8) 10_666 . ? N1 Fe1 N10 87.57(8) . . ? N1 Fe1 N10 87.57(8) 10_666 10_666 ? N1 Fe1 N10 92.43(8) . 10_666 ? N10 Fe1 N10 180.0 . 10_666 ? N1 Fe1 N20 84.61(7) 10_666 18_546 ? N1 Fe1 N20 95.39(7) . 18_546 ? N10 Fe1 N20 80.92(7) . 18_546 ? N10 Fe1 N20 99.08(7) 10_666 18_546 ? N1 Fe1 N20 95.39(7) 10_666 6_564 ? N1 Fe1 N20 84.61(7) . 6_564 ? N10 Fe1 N20 99.08(7) . 6_564 ? N10 Fe1 N20 80.92(7) 10_666 6_564 ? N20 Fe1 N20 180.00(6) 18_546 6_564 ? N1 C1 S1 178.7(2) . . ? C1 N1 Fe1 165.5(2) . . ? C10 N10 N11 104.80(19) . . ? C10 N10 Fe1 140.37(17) . . ? N11 N10 Fe1 114.15(14) . . ? C12 N11 N10 112.9(2) . . ? C12 N11 H11 123.6 . . ? N10 N11 H11 123.6 . . ? N10 C10 C11 110.8(2) . . ? N10 C10 C13 122.6(2) . . ? C11 C10 C13 126.6(2) . . ? C12 C11 C10 104.7(2) . . ? C12 C11 C21 125.4(2) . . ? C10 C11 C21 129.9(2) . . ? N11 C12 C11 106.8(2) . . ? N11 C12 C14 122.2(2) . . ? C11 C12 C14 130.9(2) . . ? C10 C13 H13A 109.5 . . ? C10 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C10 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C10 C13 H13D 109.5 . . ? H13A C13 H13D 141.1 . . ? H13B C13 H13D 56.3 . . ? H13C C13 H13D 56.3 . . ? C10 C13 H13E 109.5 . . ? H13A C13 H13E 56.3 . . ? H13B C13 H13E 141.1 . . ? H13C C13 H13E 56.3 . . ? H13D C13 H13E 109.5 . . ? C10 C13 H13F 109.5 . . ? H13A C13 H13F 56.3 . . ? H13B C13 H13F 56.3 . . ? H13C C13 H13F 141.1 . . ? H13D C13 H13F 109.5 . . ? H13E C13 H13F 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C12 C14 H14D 109.5 . . ? H14A C14 H14D 141.1 . . ? H14B C14 H14D 56.3 . . ? H14C C14 H14D 56.3 . . ? C12 C14 H14E 109.5 . . ? H14A C14 H14E 56.3 . . ? H14B C14 H14E 141.1 . . ? H14C C14 H14E 56.3 . . ? H14D C14 H14E 109.5 . . ? C12 C14 H14F 109.5 . . ? H14A C14 H14F 56.3 . . ? H14B C14 H14F 56.3 . . ? H14C C14 H14F 141.1 . . ? H14D C14 H14F 109.5 . . ? H14E C14 H14F 109.5 . . ? N21 C20 C21 106.7(2) . . ? N21 C20 C23 122.6(2) . . ? C21 C20 C23 130.7(2) . . ? C20 C21 C22 104.8(2) . . ? C20 C21 C11 127.7(2) . . ? C22 C21 C11 127.3(2) . . ? N20 C22 C21 111.4(2) . . ? N20 C22 C24 121.0(2) . . ? C21 C22 C24 127.6(2) . . ? 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 . . ? C20 C23 H23D 109.5 . . ? H23A C23 H23D 141.1 . . ? H23B C23 H23D 56.3 . . ? H23C C23 H23D 56.3 . . ? C20 C23 H23E 109.5 . . ? H23A C23 H23E 56.3 . . ? H23B C23 H23E 141.1 . . ? H23C C23 H23E 56.3 . . ? H23D C23 H23E 109.5 . . ? C20 C23 H23F 109.5 . . ? H23A C23 H23F 56.3 . . ? H23B C23 H23F 56.3 . . ? H23C C23 H23F 141.1 . . ? H23D C23 H23F 109.5 . . ? H23E C23 H23F 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C22 C24 H24D 109.5 . . ? H24A C24 H24D 141.1 . . ? H24B C24 H24D 56.3 . . ? H24C C24 H24D 56.3 . . ? C22 C24 H24E 109.5 . . ? H24A C24 H24E 56.3 . . ? H24B C24 H24E 141.1 . . ? H24C C24 H24E 56.3 . . ? H24D C24 H24E 109.5 . . ? C22 C24 H24F 109.5 . . ? H24A C24 H24F 56.3 . . ? H24B C24 H24F 56.3 . . ? H24C C24 H24F 141.1 . . ? H24D C24 H24F 109.5 . . ? H24E C24 H24F 109.5 . . ? C22 N20 N21 103.95(19) . . ? C22 N20 Fe1 133.61(16) . 8_655 ? N21 N20 Fe1 121.36(14) . 8_655 ? C20 N21 N20 113.12(19) . . ? C20 N21 H21 123.4 . . ? N20 N21 H21 123.4 . . ? C100 C101 H10A 109.5 . . ? C100 C101 H10B 109.5 . . ? H10A C101 H10B 109.5 . . ? C100 C101 H10C 109.5 . . ? H10A C101 H10C 109.5 . . ? H10B C101 H10C 109.5 . . ? C100 C101 H10D 109.5 . . ? H10A C101 H10D 141.1 . . ? H10B C101 H10D 56.3 . . ? H10C C101 H10D 56.3 . . ? C100 C101 H10E 109.5 . . ? H10A C101 H10E 56.3 . . ? H10B C101 H10E 141.1 . . ? H10C C101 H10E 56.3 . . ? H10D C101 H10E 109.5 . . ? C100 C101 H10F 109.5 . . ? H10A C101 H10F 56.3 . . ? H10B C101 H10F 56.3 . . ? H10C C101 H10F 141.1 . . ? H10D C101 H10F 109.5 . . ? H10E C101 H10F 109.5 . . ? N100 C100 C101 174(6) . . ? 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 N11 H11 S1 0.88 2.77 3.598(2) 156.8 15_556 N21 H21 S1 0.88 2.56 3.384(2) 155.4 10_667 _diffrn_measured_fraction_theta_max 0.953 _diffrn_reflns_theta_full 27.96 _diffrn_measured_fraction_theta_full 0.953 _refine_diff_density_max 0.511 _refine_diff_density_min -0.400 _refine_diff_density_rms 0.077 #===END data_A_375K_1 _database_code_depnum_ccdc_archive 'CCDC 243656' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C22 H28 Fe N10 S2, 0.40 (C2 H3 N)' _chemical_formula_sum 'C22.80 H29.20 Fe N10.40 S2' _chemical_formula_weight 568.98 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Hexagonal _symmetry_space_group_name_H-M R-3 _symmetry_space_group_name_Hall -R3 _symmetry_Int_Tables_number 148 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 25.390(5) _cell_length_b 25.390(5) _cell_length_c 10.986(5) _cell_angle_alpha 90.000(5) _cell_angle_beta 90.000(5) _cell_angle_gamma 120.000(5) _cell_volume 6133(3) _cell_formula_units_Z 9 _cell_measurement_temperature 375(2) _cell_measurement_reflns_used 833 _cell_measurement_theta_min 2.619 _cell_measurement_theta_max 21.175 _exptl_crystal_description 'hexagonal rods' _exptl_crystal_colour purple _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.386 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2671 _exptl_absorpt_coefficient_mu 0.739 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.741 _exptl_absorpt_correction_T_max 0.922 _exptl_absorpt_process_details 'SADABS, Bruker 1995' _exptl_special_details ; 'Fixed in an open capillary with a small amount of grease and heated to 375 K' ; _diffrn_ambient_temperature 375(2) _diffrn_radiation_wavelength 0.71069 _diffrn_radiation_type MoK\a _diffrn_radiation_source 'fine-focus sealed tube' _diffrn_radiation_monochromator graphite _diffrn_measurement_device_type 'BrukerSMART 1000 CCD' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% 0.00 _diffrn_reflns_number 6544 _diffrn_reflns_av_R_equivalents 0.0328 _diffrn_reflns_av_sigmaI/netI 0.0960 _diffrn_reflns_limit_h_min -32 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -33 _diffrn_reflns_limit_k_max 33 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.07 _diffrn_reflns_theta_max 28.03 _reflns_number_total 3128 _reflns_number_gt 1792 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (BrukerAXS, 1997)' _computing_cell_refinement 'SMART (BrukerAXS, 1997)' _computing_data_reduction 'SAINT+ (BrukerAXS, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XPMA/ZORTEP, WebLabViewer Pro 3.7' _computing_publication_material ? _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. In this material the iron(II) centres are coordinated in distorted octahedral fashion by two trans thiocyanato ligands and four tmbpz ligands that link the iron centres together. The resulting structure consists of two identical interpenetrated NbO-type nets related by a (001) translation. The interpenetration of the nets is stabilised by a network of hydrogen bonds between them, of the form N-H...S - these are tabulated below. The interpenetrating framework structure houses 1-D channels running parallel to the c axis, each consisting of small cavities connected by smaller hexagonal windows of sulphur atoms. This structure was obtained after heating of the crystal in situ to 375 K, and is based on the first 650 frames of a 2000 frame data collection. The use of fewer frames has affected the completeness of the intensity data collected. Fourier difference synthesis indicated the presence of significant electron density in the 1-D channels, consistent with the continuing presence of some solvent of crystallisation in the material. This solvent was modelled similarly to the as-grown material (see data_A_2/3MECN) with isotropic thermal parameters fixed at values double those used for A_0.27MeCN at 150 K. We justify this choice of thermal parameters by reference to the ratio of Fe1 Ueq obtained at in A_0.27MeCN and A_375K_1 (1 : 2.14). The chosen parameters are tabulated below: C101 0.200 Uiso C100 0.200 Uiso N100 0.300 Uiso The occupancy of these three atom positions was allowed to refine by means of a single free variable. The value obtained (FVAR 0.60186) indicates a 60% occupancy of the solvent atom positions. The solvent was retrained using the following commands: DFIX 1.39 0.01 C100 C101 DFIX 1.15 0.01 C100 N100 DFIX 2.54 0.01 C101 N100 All non-hydrogen atoms were refined anisotropically except those of the disordered acetonitrile molecule. Hydrogen atoms were geometrically constrained using a riding atom model. Methyl group hydrogen atoms on tmbpz and acetonitrile appeared to be disordered when difference peaks were examined, and therefore they were modelled accordingly. ; _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^)+(0.0156P)^2^+43.6905P] 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 3128 _refine_ls_number_parameters 168 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.1513 _refine_ls_R_factor_gt 0.0695 _refine_ls_wR_factor_ref 0.1358 _refine_ls_wR_factor_gt 0.1061 _refine_ls_goodness_of_fit_ref 1.103 _refine_ls_restrained_S_all 1.103 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Fe1 Fe 0.5000 0.5000 0.5000 0.0307(3) Uani 1 2 d S . . S1 S 0.33203(6) 0.52478(6) 0.62305(12) 0.0427(4) Uani 1 1 d . . . C1 C 0.3933(2) 0.52224(19) 0.5956(4) 0.0266(10) Uani 1 1 d . . . N1 N 0.43640(17) 0.52003(17) 0.5726(3) 0.0323(9) Uani 1 1 d . . . N10 N 0.54979(17) 0.52796(16) 0.6801(3) 0.0291(9) Uani 1 1 d . . . N11 N 0.55018(17) 0.57617(17) 0.7328(3) 0.0323(9) Uani 1 1 d . . . H11 H 0.5304 0.5928 0.7046 0.039 Uiso 1 1 calc R . . C10 C 0.5860(2) 0.5167(2) 0.7504(4) 0.0286(10) Uani 1 1 d . . . C11 C 0.6094(2) 0.55849(19) 0.8488(4) 0.0264(10) Uani 1 1 d . . . C12 C 0.5845(2) 0.5955(2) 0.8332(4) 0.0303(10) Uani 1 1 d . . . C13 C 0.5980(2) 0.4661(2) 0.7258(4) 0.0442(13) Uani 1 1 d . . . H13A H 0.5762 0.4444 0.6544 0.066 Uiso 0.50 1 calc PR . . H13B H 0.5849 0.4389 0.7941 0.066 Uiso 0.50 1 calc PR . . H13C H 0.6408 0.4823 0.7131 0.066 Uiso 0.50 1 calc PR . . H13D H 0.6251 0.4660 0.7867 0.066 Uiso 0.50 1 calc PR . . H13E H 0.6163 0.4715 0.6470 0.066 Uiso 0.50 1 calc PR . . H13F H 0.5604 0.4281 0.7280 0.066 Uiso 0.50 1 calc PR . . C14 C 0.5900(3) 0.6466(2) 0.9064(5) 0.0529(15) Uani 1 1 d . . . H14A H 0.5663 0.6623 0.8697 0.079 Uiso 0.50 1 calc PR . . H14B H 0.6319 0.6781 0.9099 0.079 Uiso 0.50 1 calc PR . . H14C H 0.5754 0.6327 0.9873 0.079 Uiso 0.50 1 calc PR . . H14D H 0.6160 0.6531 0.9749 0.079 Uiso 0.50 1 calc PR . . H14E H 0.5505 0.6373 0.9348 0.079 Uiso 0.50 1 calc PR . . H14F H 0.6070 0.6827 0.8573 0.079 Uiso 0.50 1 calc PR . . C20 C 0.6438(2) 0.5240(2) 1.0360(4) 0.0311(10) Uani 1 1 d . . . C21 C 0.65237(19) 0.56498(19) 0.9451(4) 0.0263(10) Uani 1 1 d . . . C22 C 0.7086(2) 0.6170(2) 0.9721(4) 0.0306(10) Uani 1 1 d . . . C23 C 0.5924(2) 0.4619(2) 1.0597(5) 0.0522(15) Uani 1 1 d . . . H23A H 0.6014 0.4452 1.1299 0.078 Uiso 0.50 1 calc PR . . H23B H 0.5864 0.4365 0.9903 0.078 Uiso 0.50 1 calc PR . . H23C H 0.5560 0.4637 1.0743 0.078 Uiso 0.50 1 calc PR . . H23D H 0.5612 0.4518 0.9998 0.078 Uiso 0.50 1 calc PR . . H23E H 0.5761 0.4605 1.1393 0.078 Uiso 0.50 1 calc PR . . H23F H 0.6065 0.4333 1.0554 0.078 Uiso 0.50 1 calc PR . . C24 C 0.7411(2) 0.6743(2) 0.9016(5) 0.0500(15) Uani 1 1 d . . . H24A H 0.7786 0.7017 0.9419 0.075 Uiso 0.50 1 calc PR . . H24B H 0.7162 0.6927 0.8957 0.075 Uiso 0.50 1 calc PR . . H24C H 0.7498 0.6656 0.8214 0.075 Uiso 0.50 1 calc PR . . H24D H 0.7178 0.6717 0.8307 0.075 Uiso 0.50 1 calc PR . . H24E H 0.7802 0.6806 0.8770 0.075 Uiso 0.50 1 calc PR . . H24F H 0.7466 0.7078 0.9513 0.075 Uiso 0.50 1 calc PR . . N20 N 0.73337(16) 0.60904(17) 1.0733(3) 0.0285(9) Uani 1 1 d . . . N21 N 0.69258(17) 0.55162(17) 1.1088(3) 0.0312(9) Uani 1 1 d . . . H21 H 0.6975 0.5345 1.1720 0.037 Uiso 1 1 calc R . . C101 C 0.3333 0.6667 -0.140(4) 0.200 Uiso 0.602(18) 3 d SPD . . H10A H 0.3061 0.6387 -0.2000 0.300 Uiso 0.100(3) 1 calc PR . . H10B H 0.3745 0.6839 -0.1685 0.300 Uiso 0.100(3) 1 calc PR . . H10C H 0.3241 0.6985 -0.1274 0.300 Uiso 0.100(3) 1 calc PR . . H10D H 0.3636 0.7087 -0.1306 0.300 Uiso 0.100(3) 1 calc PR . . H10E H 0.2953 0.6636 -0.1621 0.300 Uiso 0.100(3) 1 calc PR . . H10F H 0.3457 0.6489 -0.2032 0.300 Uiso 0.100(3) 1 calc PR . . C100 C 0.327(5) 0.636(3) -0.032(4) 0.200 Uiso 0.201(6) 1 d PD . . N100 N 0.325(4) 0.613(3) 0.059(4) 0.300 Uiso 0.201(6) 1 d PD . . 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 0.0291(5) 0.0426(6) 0.0218(5) -0.0083(4) -0.0034(4) 0.0190(5) S1 0.0352(7) 0.0559(9) 0.0440(8) 0.0036(7) 0.0036(6) 0.0279(7) C1 0.027(2) 0.028(2) 0.020(2) -0.0010(19) -0.0010(19) 0.010(2) N1 0.033(2) 0.037(2) 0.025(2) 0.0010(17) 0.0026(18) 0.0159(19) N10 0.032(2) 0.032(2) 0.0214(19) -0.0042(16) -0.0037(16) 0.0143(18) N11 0.042(2) 0.040(2) 0.023(2) -0.0051(18) -0.0080(18) 0.026(2) C10 0.028(2) 0.031(2) 0.023(2) -0.0012(19) 0.0006(19) 0.012(2) C11 0.032(2) 0.032(2) 0.014(2) -0.0012(18) 0.0008(18) 0.015(2) C12 0.034(3) 0.034(3) 0.019(2) -0.004(2) -0.0085(19) 0.014(2) C13 0.057(3) 0.048(3) 0.036(3) -0.006(2) -0.011(3) 0.032(3) C14 0.074(4) 0.054(4) 0.045(3) -0.021(3) -0.022(3) 0.044(3) C20 0.039(3) 0.033(3) 0.023(2) -0.001(2) -0.001(2) 0.019(2) C21 0.030(2) 0.029(2) 0.021(2) -0.0007(19) -0.0008(19) 0.015(2) C22 0.035(3) 0.034(3) 0.022(2) 0.001(2) 0.001(2) 0.016(2) C23 0.051(3) 0.037(3) 0.046(3) 0.011(3) 0.001(3) 0.005(3) C24 0.056(4) 0.040(3) 0.035(3) 0.011(2) -0.013(3) 0.009(3) N20 0.031(2) 0.034(2) 0.0189(19) 0.0042(16) -0.0011(16) 0.0151(18) N21 0.038(2) 0.036(2) 0.022(2) 0.0074(17) -0.0006(17) 0.0206(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 Fe1 N1 2.080(4) 10_666 ? Fe1 N1 2.080(4) . ? Fe1 N10 2.262(4) . ? Fe1 N10 2.262(4) 10_666 ? Fe1 N20 2.433(4) 6_564 ? Fe1 N20 2.433(4) 18_546 ? S1 C1 1.616(5) . ? C1 N1 1.152(5) . ? N10 C10 1.337(5) . ? N10 N11 1.350(5) . ? N11 C12 1.338(5) . ? N11 H11 0.8600 . ? C10 C11 1.421(6) . ? C10 C13 1.486(6) . ? C11 C12 1.381(6) . ? C11 C21 1.470(6) . ? C12 C14 1.473(6) . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C13 H13D 0.9600 . ? C13 H13E 0.9600 . ? C13 H13F 0.9600 . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C14 H14D 0.9600 . ? C14 H14E 0.9600 . ? C14 H14F 0.9600 . ? C20 N21 1.341(6) . ? C20 C21 1.377(6) . ? C20 C23 1.484(6) . ? C21 C22 1.409(6) . ? C22 N20 1.342(5) . ? C22 C24 1.482(6) . ? C23 H23A 0.9600 . ? C23 H23B 0.9600 . ? C23 H23C 0.9600 . ? C23 H23D 0.9600 . ? C23 H23E 0.9600 . ? C23 H23F 0.9600 . ? C24 H24A 0.9600 . ? C24 H24B 0.9600 . ? C24 H24C 0.9600 . ? C24 H24D 0.9600 . ? C24 H24E 0.9600 . ? C24 H24F 0.9600 . ? N20 N21 1.356(5) . ? N20 Fe1 2.433(4) 8_655 ? N21 H21 0.8600 . ? C101 C100 1.389(9) . ? C101 H10A 0.9600 . ? C101 H10B 0.9600 . ? C101 H10C 0.9600 . ? C101 H10D 0.9600 . ? C101 H10E 0.9600 . ? C101 H10F 0.9600 . ? C100 N100 1.149(9) . ? 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 Fe1 N1 180.000(1) 10_666 . ? N1 Fe1 N10 91.83(14) 10_666 . ? N1 Fe1 N10 88.17(14) . . ? N1 Fe1 N10 88.17(14) 10_666 10_666 ? N1 Fe1 N10 91.83(14) . 10_666 ? N10 Fe1 N10 180.000(1) . 10_666 ? N1 Fe1 N20 95.82(13) 10_666 6_564 ? N1 Fe1 N20 84.18(13) . 6_564 ? N10 Fe1 N20 98.92(12) . 6_564 ? N10 Fe1 N20 81.08(12) 10_666 6_564 ? N1 Fe1 N20 84.18(13) 10_666 18_546 ? N1 Fe1 N20 95.82(13) . 18_546 ? N10 Fe1 N20 81.08(12) . 18_546 ? N10 Fe1 N20 98.92(12) 10_666 18_546 ? N20 Fe1 N20 180.0 6_564 18_546 ? N1 C1 S1 178.0(4) . . ? C1 N1 Fe1 165.7(4) . . ? C10 N10 N11 104.6(3) . . ? C10 N10 Fe1 140.7(3) . . ? N11 N10 Fe1 114.2(3) . . ? C12 N11 N10 113.3(4) . . ? C12 N11 H11 123.4 . . ? N10 N11 H11 123.4 . . ? N10 C10 C11 110.7(4) . . ? N10 C10 C13 122.8(4) . . ? C11 C10 C13 126.5(4) . . ? C12 C11 C10 104.6(4) . . ? C12 C11 C21 125.4(4) . . ? C10 C11 C21 129.9(4) . . ? N11 C12 C11 106.7(4) . . ? N11 C12 C14 122.1(4) . . ? C11 C12 C14 131.2(4) . . ? C10 C13 H13A 109.5 . . ? C10 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C10 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C10 C13 H13D 109.5 . . ? H13A C13 H13D 141.1 . . ? H13B C13 H13D 56.3 . . ? H13C C13 H13D 56.3 . . ? C10 C13 H13E 109.5 . . ? H13A C13 H13E 56.3 . . ? H13B C13 H13E 141.1 . . ? H13C C13 H13E 56.3 . . ? H13D C13 H13E 109.5 . . ? C10 C13 H13F 109.5 . . ? H13A C13 H13F 56.3 . . ? H13B C13 H13F 56.3 . . ? H13C C13 H13F 141.1 . . ? H13D C13 H13F 109.5 . . ? H13E C13 H13F 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C12 C14 H14D 109.5 . . ? H14A C14 H14D 141.1 . . ? H14B C14 H14D 56.3 . . ? H14C C14 H14D 56.3 . . ? C12 C14 H14E 109.5 . . ? H14A C14 H14E 56.3 . . ? H14B C14 H14E 141.1 . . ? H14C C14 H14E 56.3 . . ? H14D C14 H14E 109.5 . . ? C12 C14 H14F 109.5 . . ? H14A C14 H14F 56.3 . . ? H14B C14 H14F 56.3 . . ? H14C C14 H14F 141.1 . . ? H14D C14 H14F 109.5 . . ? H14E C14 H14F 109.5 . . ? N21 C20 C21 106.4(4) . . ? N21 C20 C23 122.8(4) . . ? C21 C20 C23 130.8(4) . . ? C20 C21 C22 105.0(4) . . ? C20 C21 C11 127.5(4) . . ? C22 C21 C11 127.2(4) . . ? N20 C22 C21 111.3(4) . . ? N20 C22 C24 120.5(4) . . ? C21 C22 C24 128.1(4) . . ? 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 . . ? C20 C23 H23D 109.5 . . ? H23A C23 H23D 141.1 . . ? H23B C23 H23D 56.3 . . ? H23C C23 H23D 56.3 . . ? C20 C23 H23E 109.5 . . ? H23A C23 H23E 56.3 . . ? H23B C23 H23E 141.1 . . ? H23C C23 H23E 56.3 . . ? H23D C23 H23E 109.5 . . ? C20 C23 H23F 109.5 . . ? H23A C23 H23F 56.3 . . ? H23B C23 H23F 56.3 . . ? H23C C23 H23F 141.1 . . ? H23D C23 H23F 109.5 . . ? H23E C23 H23F 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C22 C24 H24D 109.5 . . ? H24A C24 H24D 141.1 . . ? H24B C24 H24D 56.3 . . ? H24C C24 H24D 56.3 . . ? C22 C24 H24E 109.5 . . ? H24A C24 H24E 56.3 . . ? H24B C24 H24E 141.1 . . ? H24C C24 H24E 56.3 . . ? H24D C24 H24E 109.5 . . ? C22 C24 H24F 109.5 . . ? H24A C24 H24F 56.3 . . ? H24B C24 H24F 56.3 . . ? H24C C24 H24F 141.1 . . ? H24D C24 H24F 109.5 . . ? H24E C24 H24F 109.5 . . ? C22 N20 N21 103.7(3) . . ? C22 N20 Fe1 133.2(3) . 8_655 ? N21 N20 Fe1 122.1(3) . 8_655 ? C20 N21 N20 113.5(3) . . ? C20 N21 H21 123.2 . . ? N20 N21 H21 123.2 . . ? C100 C101 H10A 109.5 . . ? C100 C101 H10B 109.5 . . ? H10A C101 H10B 109.5 . . ? C100 C101 H10C 109.5 . . ? H10A C101 H10C 109.5 . . ? H10B C101 H10C 109.5 . . ? C100 C101 H10D 109.5 . . ? H10A C101 H10D 141.1 . . ? H10B C101 H10D 56.3 . . ? H10C C101 H10D 56.3 . . ? C100 C101 H10E 109.5 . . ? H10A C101 H10E 56.3 . . ? H10B C101 H10E 141.1 . . ? H10C C101 H10E 56.3 . . ? H10D C101 H10E 109.5 . . ? C100 C101 H10F 109.5 . . ? H10A C101 H10F 56.3 . . ? H10B C101 H10F 56.3 . . ? H10C C101 H10F 141.1 . . ? H10D C101 H10F 109.5 . . ? H10E C101 H10F 109.5 . . ? N100 C100 C101 176(10) . . ? 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 N11 H11 S1 0.86 2.84 3.650(4) 156.6 15_556 N21 H21 S1 0.86 2.60 3.408(4) 156.5 10_667 _diffrn_measured_fraction_theta_max 0.950 _diffrn_reflns_theta_full 28.03 _diffrn_measured_fraction_theta_full 0.950 _refine_diff_density_max 0.417 _refine_diff_density_min -0.791 _refine_diff_density_rms 0.091 #===END data_A_375K_2 _database_code_depnum_ccdc_archive 'CCDC 243657' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C22 H28 Fe N10 S2, 0.33(C2 H3 N)' _chemical_formula_sum 'C22.66 H29 Fe N10.33 S2' _chemical_formula_weight 566.14 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' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Hexagonal _symmetry_space_group_name_H-M R-3 _symmetry_space_group_name_Hall -R3 _symmetry_Int_Tables_number 148 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 25.501(2) _cell_length_b 25.501(2) _cell_length_c 11.0385(18) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 6216.7(13) _cell_formula_units_Z 9 _cell_measurement_temperature 375(2) _cell_measurement_reflns_used 118 _cell_measurement_theta_min 3.057 _cell_measurement_theta_max 19.875 _exptl_crystal_description 'hexagonal rods' _exptl_crystal_colour purple _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.361 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2658 _exptl_absorpt_coefficient_mu 0.729 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.757 _exptl_absorpt_correction_T_max 0.923 _exptl_absorpt_process_details 'SADABS, Bruker 1995' _exptl_special_details ; 'Fixed in an open capillary with a small amount of grease and heated to 375 K' ; _diffrn_ambient_temperature 375(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 'BrukerSMART 1000 CCD' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6567 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0826 _diffrn_reflns_limit_h_min -32 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -32 _diffrn_reflns_limit_k_max 32 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.06 _diffrn_reflns_theta_max 28.01 _reflns_number_total 3158 _reflns_number_gt 1824 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (BrukerAXS, 1997)' _computing_cell_refinement 'SMART (BrukerAXS, 1997)' _computing_data_reduction 'SAINT+ (BrukerAXS, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XPMA/ZORTEP, WebLabViewer Pro 3.7' _computing_publication_material ? _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. In this material the iron(II) centres are coordinated in distorted octahedral fashion by two trans thiocyanato ligands and four tmbpz ligands that link the iron centres together. The resulting structure consists of two identical interpenetrated NbO-type nets related by a (001) translation. The interpenetration of the nets is stabilised by a network of hydrogen bonds between them, of the form N-H...S - these are tabulated below. The interpenetrating framework structure houses 1-D channels running parallel to the c axis, each consisting of small cavities connected by smaller hexagonal windows of sulphur atoms. This structure was obtained after heating of the crystal in situ to 375 K, and is based on the second set of 650 frames of a 2000 frame data collection. The use of fewer frames has affected the completeness of the intensity data collected. Fourier difference synthesis indicated the presence of significant electron density in the 1-D channels, consistent with the continuing presence of some solvent of crystallisation in the material. This solvent was modelled similarly to the as-grown material (see data_A_2/3MECN) with isotropic thermal parameters fixed at values double those used for A_0.27MeCN at 150 K. We justify this choice of thermal parameters by reference to the ratio of Fe1 Ueq obtained at in A_0.27MeCN and A_375K_1 (1 : 2.14). The chosen parameters are tabulated below: C101 0.200 Uiso C100 0.200 Uiso N100 0.300 Uiso The occupancy of these three atom positions was allowed to refine by means of a single free variable. The value obtained (FVAR 0.49783) indicates a 50% occupancy of the solvent atom positions. The solvent was retrained using the following commands: DFIX 1.39 0.01 C100 C101 DFIX 1.15 0.01 C100 N100 DFIX 2.54 0.01 C101 N100 All non-hydrogen atoms were refined anisotropically except those of the disordered acetonitrile molecule. Hydrogen atoms were geometrically constrained using a riding atom model. Methyl group hydrogen atoms on tmbpz and acetonitrile appeared to be disordered when difference peaks were examined, and therefore they were modelled accordingly. ; _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^)+(0.0200P)^2^+52.2821P] 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 3158 _refine_ls_number_parameters 168 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.1365 _refine_ls_R_factor_gt 0.0592 _refine_ls_wR_factor_ref 0.1380 _refine_ls_wR_factor_gt 0.1031 _refine_ls_goodness_of_fit_ref 1.049 _refine_ls_restrained_S_all 1.048 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Fe1 Fe 0.5000 0.5000 0.5000 0.0316(2) Uani 1 2 d S . . S1 S 0.33197(6) 0.52460(6) 0.62293(12) 0.0443(3) Uani 1 1 d . . . C1 C 0.3931(2) 0.52191(19) 0.5952(4) 0.0295(10) Uani 1 1 d . . . N1 N 0.43680(17) 0.52022(17) 0.5729(3) 0.0341(9) Uani 1 1 d . . . N10 N 0.54978(16) 0.52790(16) 0.6805(3) 0.0308(8) Uani 1 1 d . . . N11 N 0.55024(16) 0.57634(16) 0.7326(3) 0.0334(9) Uani 1 1 d . . . H11 H 0.5307 0.5931 0.7044 0.040 Uiso 1 1 calc R . . C10 C 0.58601(19) 0.51653(19) 0.7510(4) 0.0281(9) Uani 1 1 d . . . C11 C 0.60948(19) 0.55841(19) 0.8483(4) 0.0292(10) Uani 1 1 d . . . C12 C 0.5847(2) 0.5954(2) 0.8335(4) 0.0316(10) Uani 1 1 d . . . C13 C 0.5984(2) 0.4665(2) 0.7262(4) 0.0456(13) Uani 1 1 d . . . H13A H 0.5766 0.4449 0.6551 0.068 Uiso 0.50 1 calc PR . . H13B H 0.5855 0.4393 0.7941 0.068 Uiso 0.50 1 calc PR . . H13C H 0.6410 0.4829 0.7135 0.068 Uiso 0.50 1 calc PR . . H13D H 0.6254 0.4665 0.7867 0.068 Uiso 0.50 1 calc PR . . H13E H 0.6166 0.4721 0.6477 0.068 Uiso 0.50 1 calc PR . . H13F H 0.5611 0.4285 0.7284 0.068 Uiso 0.50 1 calc PR . . C14 C 0.5900(3) 0.6464(2) 0.9067(5) 0.0538(15) Uani 1 1 d . . . H14A H 0.5664 0.6620 0.8701 0.081 Uiso 0.50 1 calc PR . . H14B H 0.6317 0.6778 0.9103 0.081 Uiso 0.50 1 calc PR . . H14C H 0.5754 0.6325 0.9871 0.081 Uiso 0.50 1 calc PR . . H14D H 0.6159 0.6529 0.9749 0.081 Uiso 0.50 1 calc PR . . H14E H 0.5506 0.6371 0.9347 0.081 Uiso 0.50 1 calc PR . . H14F H 0.6070 0.6824 0.8579 0.081 Uiso 0.50 1 calc PR . . C20 C 0.6442(2) 0.5245(2) 1.0360(4) 0.0325(10) Uani 1 1 d . . . C21 C 0.65227(19) 0.56516(19) 0.9453(4) 0.0278(9) Uani 1 1 d . . . C22 C 0.70884(19) 0.6171(2) 0.9721(4) 0.0301(10) Uani 1 1 d . . . C23 C 0.5931(2) 0.4621(2) 1.0597(5) 0.0535(15) Uani 1 1 d . . . H23A H 0.6022 0.4457 1.1296 0.080 Uiso 0.50 1 calc PR . . H23B H 0.5874 0.4369 0.9907 0.080 Uiso 0.50 1 calc PR . . H23C H 0.5567 0.4636 1.0741 0.080 Uiso 0.50 1 calc PR . . H23D H 0.5620 0.4518 1.0000 0.080 Uiso 0.50 1 calc PR . . H23E H 0.5768 0.4606 1.1389 0.080 Uiso 0.50 1 calc PR . . H23F H 0.6075 0.4339 1.0555 0.080 Uiso 0.50 1 calc PR . . C24 C 0.7411(2) 0.6742(2) 0.9014(4) 0.0517(14) Uani 1 1 d . . . H24A H 0.7784 0.7016 0.9414 0.078 Uiso 0.50 1 calc PR . . H24B H 0.7162 0.6925 0.8956 0.078 Uiso 0.50 1 calc PR . . H24C H 0.7497 0.6655 0.8216 0.078 Uiso 0.50 1 calc PR . . H24D H 0.7178 0.6714 0.8311 0.078 Uiso 0.50 1 calc PR . . H24E H 0.7800 0.6805 0.8768 0.078 Uiso 0.50 1 calc PR . . H24F H 0.7465 0.7075 0.9508 0.078 Uiso 0.50 1 calc PR . . N20 N 0.73336(16) 0.60918(16) 1.0735(3) 0.0305(8) Uani 1 1 d . . . N21 N 0.69258(16) 0.55153(16) 1.1089(3) 0.0326(9) Uani 1 1 d . . . H21 H 0.6975 0.5344 1.1715 0.039 Uiso 1 1 calc R . . C101 C 0.3333 0.6667 -0.155(4) 0.200 Uiso 0.498(18) 3 d SPD . . H10A H 0.3060 0.6383 -0.2139 0.300 Uiso 0.083(3) 1 calc PR . . H10B H 0.3742 0.6837 -0.1840 0.300 Uiso 0.083(3) 1 calc PR . . H10C H 0.3240 0.6985 -0.1437 0.300 Uiso 0.083(3) 1 calc PR . . H10D H 0.3635 0.7086 -0.1471 0.300 Uiso 0.083(3) 1 calc PR . . H10E H 0.2953 0.6633 -0.1770 0.300 Uiso 0.083(3) 1 calc PR . . H10F H 0.3454 0.6485 -0.2173 0.300 Uiso 0.083(3) 1 calc PR . . C100 C 0.327(7) 0.637(4) -0.046(5) 0.200 Uiso 0.166(6) 1 d PD . . N100 N 0.322(6) 0.616(4) 0.049(5) 0.300 Uiso 0.166(6) 1 d PD . . 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 0.0274(5) 0.0421(6) 0.0274(4) -0.0077(4) -0.0027(4) 0.0190(5) S1 0.0347(7) 0.0566(9) 0.0488(8) 0.0032(6) 0.0043(6) 0.0283(6) C1 0.031(2) 0.028(2) 0.026(2) 0.0000(18) -0.0005(18) 0.013(2) N1 0.032(2) 0.036(2) 0.033(2) 0.0022(17) 0.0043(17) 0.0163(18) N10 0.033(2) 0.032(2) 0.0277(19) -0.0038(16) -0.0045(16) 0.0166(17) N11 0.038(2) 0.037(2) 0.031(2) -0.0069(17) -0.0077(17) 0.0238(19) C10 0.027(2) 0.028(2) 0.026(2) 0.0011(18) 0.0025(18) 0.0107(19) C11 0.030(2) 0.028(2) 0.026(2) -0.0023(18) -0.0055(18) 0.0129(19) C12 0.036(3) 0.035(2) 0.023(2) -0.0039(19) -0.0060(19) 0.018(2) C13 0.056(3) 0.045(3) 0.044(3) -0.008(2) -0.012(3) 0.031(3) C14 0.073(4) 0.049(3) 0.051(3) -0.020(3) -0.023(3) 0.039(3) C20 0.036(3) 0.031(2) 0.031(2) -0.001(2) 0.001(2) 0.017(2) C21 0.032(2) 0.031(2) 0.022(2) 0.0006(18) 0.0001(18) 0.017(2) C22 0.033(2) 0.036(2) 0.021(2) -0.0009(18) -0.0055(18) 0.017(2) C23 0.054(3) 0.038(3) 0.049(3) 0.012(2) 0.001(3) 0.008(3) C24 0.052(3) 0.041(3) 0.042(3) 0.011(2) -0.015(2) 0.009(3) N20 0.034(2) 0.033(2) 0.0238(18) 0.0052(15) 0.0000(16) 0.0162(17) N21 0.037(2) 0.038(2) 0.0274(19) 0.0069(16) -0.0023(16) 0.0216(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 Fe1 N1 2.084(4) . ? Fe1 N1 2.084(4) 10_666 ? Fe1 N10 2.277(3) 10_666 ? Fe1 N10 2.277(3) . ? S1 C1 1.623(5) . ? C1 N1 1.163(5) . ? N10 C10 1.346(5) . ? N10 N11 1.357(5) . ? N11 C12 1.349(5) . ? N11 H11 0.8600 . ? C10 C11 1.419(6) . ? C10 C13 1.485(6) . ? C11 C12 1.383(6) . ? C11 C21 1.476(6) . ? C12 C14 1.479(6) . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C13 H13D 0.9600 . ? C13 H13E 0.9600 . ? C13 H13F 0.9600 . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C14 H14D 0.9600 . ? C14 H14E 0.9600 . ? C14 H14F 0.9600 . ? C20 N21 1.340(5) . ? C20 C21 1.381(6) . ? C20 C23 1.491(6) . ? C21 C22 1.418(6) . ? C22 N20 1.345(5) . ? C22 C24 1.486(6) . ? C23 H23A 0.9600 . ? C23 H23B 0.9600 . ? C23 H23C 0.9600 . ? C23 H23D 0.9600 . ? C23 H23E 0.9600 . ? C23 H23F 0.9600 . ? C24 H24A 0.9600 . ? C24 H24B 0.9600 . ? C24 H24C 0.9600 . ? C24 H24D 0.9600 . ? C24 H24E 0.9600 . ? C24 H24F 0.9600 . ? N20 N21 1.366(5) . ? N21 H21 0.8600 . ? C101 C100 1.391(9) . ? C101 H10A 0.9600 . ? C101 H10B 0.9600 . ? C101 H10C 0.9600 . ? C101 H10D 0.9600 . ? C101 H10E 0.9600 . ? C101 H10F 0.9600 . ? C100 N100 1.150(9) . ? 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 Fe1 N1 180.000(1) . 10_666 ? N1 Fe1 N10 92.04(13) . 10_666 ? N1 Fe1 N10 87.96(13) 10_666 10_666 ? N1 Fe1 N10 87.96(13) . . ? N1 Fe1 N10 92.04(13) 10_666 . ? N10 Fe1 N10 180.000(1) 10_666 . ? N1 C1 S1 178.6(4) . . ? C1 N1 Fe1 164.8(4) . . ? C10 N10 N11 104.9(3) . . ? C10 N10 Fe1 140.7(3) . . ? N11 N10 Fe1 113.9(2) . . ? C12 N11 N10 112.7(3) . . ? C12 N11 H11 123.7 . . ? N10 N11 H11 123.7 . . ? N10 C10 C11 110.6(4) . . ? N10 C10 C13 122.8(4) . . ? C11 C10 C13 126.5(4) . . ? C12 C11 C10 105.0(4) . . ? C12 C11 C21 124.7(4) . . ? C10 C11 C21 130.2(4) . . ? N11 C12 C11 106.8(4) . . ? N11 C12 C14 121.7(4) . . ? C11 C12 C14 131.5(4) . . ? C10 C13 H13A 109.5 . . ? C10 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C10 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C10 C13 H13D 109.5 . . ? H13A C13 H13D 141.1 . . ? H13B C13 H13D 56.3 . . ? H13C C13 H13D 56.3 . . ? C10 C13 H13E 109.5 . . ? H13A C13 H13E 56.3 . . ? H13B C13 H13E 141.1 . . ? H13C C13 H13E 56.3 . . ? H13D C13 H13E 109.5 . . ? C10 C13 H13F 109.5 . . ? H13A C13 H13F 56.3 . . ? H13B C13 H13F 56.3 . . ? H13C C13 H13F 141.1 . . ? H13D C13 H13F 109.5 . . ? H13E C13 H13F 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C12 C14 H14D 109.5 . . ? H14A C14 H14D 141.1 . . ? H14B C14 H14D 56.3 . . ? H14C C14 H14D 56.3 . . ? C12 C14 H14E 109.5 . . ? H14A C14 H14E 56.3 . . ? H14B C14 H14E 141.1 . . ? H14C C14 H14E 56.3 . . ? H14D C14 H14E 109.5 . . ? C12 C14 H14F 109.5 . . ? H14A C14 H14F 56.3 . . ? H14B C14 H14F 56.3 . . ? H14C C14 H14F 141.1 . . ? H14D C14 H14F 109.5 . . ? H14E C14 H14F 109.5 . . ? N21 C20 C21 107.2(4) . . ? N21 C20 C23 122.2(4) . . ? C21 C20 C23 130.6(4) . . ? C20 C21 C22 104.5(4) . . ? C20 C21 C11 127.9(4) . . ? C22 C21 C11 127.4(4) . . ? N20 C22 C21 111.5(4) . . ? N20 C22 C24 120.8(4) . . ? C21 C22 C24 127.7(4) . . ? 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 . . ? C20 C23 H23D 109.5 . . ? H23A C23 H23D 141.1 . . ? H23B C23 H23D 56.3 . . ? H23C C23 H23D 56.3 . . ? C20 C23 H23E 109.5 . . ? H23A C23 H23E 56.3 . . ? H23B C23 H23E 141.1 . . ? H23C C23 H23E 56.3 . . ? H23D C23 H23E 109.5 . . ? C20 C23 H23F 109.5 . . ? H23A C23 H23F 56.3 . . ? H23B C23 H23F 56.3 . . ? H23C C23 H23F 141.1 . . ? H23D C23 H23F 109.5 . . ? H23E C23 H23F 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C22 C24 H24D 109.5 . . ? H24A C24 H24D 141.1 . . ? H24B C24 H24D 56.3 . . ? H24C C24 H24D 56.3 . . ? C22 C24 H24E 109.5 . . ? H24A C24 H24E 56.3 . . ? H24B C24 H24E 141.1 . . ? H24C C24 H24E 56.3 . . ? H24D C24 H24E 109.5 . . ? C22 C24 H24F 109.5 . . ? H24A C24 H24F 56.3 . . ? H24B C24 H24F 56.3 . . ? H24C C24 H24F 141.1 . . ? H24D C24 H24F 109.5 . . ? H24E C24 H24F 109.5 . . ? C22 N20 N21 103.8(3) . . ? C20 N21 N20 113.1(3) . . ? C20 N21 H21 123.5 . . ? N20 N21 H21 123.5 . . ? C100 C101 H10A 109.5 . . ? C100 C101 H10B 109.5 . . ? H10A C101 H10B 109.5 . . ? C100 C101 H10C 109.5 . . ? H10A C101 H10C 109.5 . . ? H10B C101 H10C 109.5 . . ? C100 C101 H10D 109.5 . . ? H10A C101 H10D 141.1 . . ? H10B C101 H10D 56.3 . . ? H10C C101 H10D 56.3 . . ? C100 C101 H10E 109.5 . . ? H10A C101 H10E 56.3 . . ? H10B C101 H10E 141.1 . . ? H10C C101 H10E 56.3 . . ? H10D C101 H10E 109.5 . . ? C100 C101 H10F 109.5 . . ? H10A C101 H10F 56.3 . . ? H10B C101 H10F 56.3 . . ? H10C C101 H10F 141.1 . . ? H10D C101 H10F 109.5 . . ? H10E C101 H10F 109.5 . . ? N100 C100 C101 175(9) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N11 H11 S1 0.86 2.85 3.660(4) 156.5 15_556 N21 H21 S1 0.86 2.62 3.422(4) 156.4 10_667 _diffrn_measured_fraction_theta_max 0.942 _diffrn_reflns_theta_full 28.01 _diffrn_measured_fraction_theta_full 0.942 _refine_diff_density_max 0.385 _refine_diff_density_min -0.566 _refine_diff_density_rms 0.086 #===END data_A_375K_3 _database_code_depnum_ccdc_archive 'CCDC 243658' _audit_creation_method SHELXL-97 _chemical_name_systematic ; ? ; _chemical_name_common ? _chemical_melting_point ? _chemical_formula_moiety 'C22 H28 Fe N10 S2, 0.29(C2 H3 N)' _chemical_formula_sum 'C22.59 H28.88 Fe N10.29 S2' _chemical_formula_weight 564.56 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' N N 0.0061 0.0033 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' S S 0.1246 0.1234 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' Fe Fe 0.3463 0.8444 'International Tables Vol C Tables 4.2.6.8 and 6.1.1.4' _symmetry_cell_setting Hexagonal _symmetry_space_group_name_H-M R-3 _symmetry_space_group_name_Hall -R3 _symmetry_Int_Tables_number 148 loop_ _symmetry_equiv_pos_as_xyz 'x, y, z' '-y, x-y, z' '-x+y, -x, z' 'x+2/3, y+1/3, z+1/3' '-y+2/3, x-y+1/3, z+1/3' '-x+y+2/3, -x+1/3, z+1/3' 'x+1/3, y+2/3, z+2/3' '-y+1/3, x-y+2/3, z+2/3' '-x+y+1/3, -x+2/3, z+2/3' '-x, -y, -z' 'y, -x+y, -z' 'x-y, x, -z' '-x+2/3, -y+1/3, -z+1/3' 'y+2/3, -x+y+1/3, -z+1/3' 'x-y+2/3, x+1/3, -z+1/3' '-x+1/3, -y+2/3, -z+2/3' 'y+1/3, -x+y+2/3, -z+2/3' 'x-y+1/3, x+2/3, -z+2/3' _cell_length_a 25.4548(18) _cell_length_b 25.4548(18) _cell_length_c 11.0215(15) _cell_angle_alpha 90.00 _cell_angle_beta 90.00 _cell_angle_gamma 120.00 _cell_volume 6184.6(10) _cell_formula_units_Z 9 _cell_measurement_temperature 375(2) _cell_measurement_reflns_used 983 _cell_measurement_theta_min 2.621 _cell_measurement_theta_max 22.835 _exptl_crystal_description 'hexagonal rods' _exptl_crystal_colour purple _exptl_crystal_size_max 0.27 _exptl_crystal_size_mid 0.12 _exptl_crystal_size_min 0.11 _exptl_crystal_density_meas ? _exptl_crystal_density_diffrn 1.364 _exptl_crystal_density_method 'not measured' _exptl_crystal_F_000 2650 _exptl_absorpt_coefficient_mu 0.732 _exptl_absorpt_correction_type empirical _exptl_absorpt_correction_T_min 0.808 _exptl_absorpt_correction_T_max 0.923 _exptl_absorpt_process_details 'SADABS, Bruker 1995' _exptl_special_details ; 'Fixed in an open capillary with a small amount of grease and heated to 375 K' ; _diffrn_ambient_temperature 375(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 'BrukerSMART 1000 CCD' _diffrn_measurement_method \w _diffrn_detector_area_resol_mean ? _diffrn_standards_number 0 _diffrn_standards_interval_count ? _diffrn_standards_interval_time ? _diffrn_standards_decay_% ? _diffrn_reflns_number 6580 _diffrn_reflns_av_R_equivalents 0.0000 _diffrn_reflns_av_sigmaI/netI 0.0745 _diffrn_reflns_limit_h_min -32 _diffrn_reflns_limit_h_max 32 _diffrn_reflns_limit_k_min -32 _diffrn_reflns_limit_k_max 32 _diffrn_reflns_limit_l_min -14 _diffrn_reflns_limit_l_max 14 _diffrn_reflns_theta_min 2.07 _diffrn_reflns_theta_max 27.95 _reflns_number_total 3146 _reflns_number_gt 1843 _reflns_threshold_expression >2sigma(I) _computing_data_collection 'SMART (BrukerAXS, 1997)' _computing_cell_refinement 'SMART (BrukerAXS, 1997)' _computing_data_reduction 'SAINT+ (BrukerAXS, 1997)' _computing_structure_solution 'SHELXS-97 (Sheldrick, 1990)' _computing_structure_refinement 'SHELXL-97 (Sheldrick, 1997)' _computing_molecular_graphics 'XPMA/ZORTEP, WebLabViewer Pro 3.7' _computing_publication_material ? _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. In this material the iron(II) centres are coordinated in distorted octahedral fashion by two trans thiocyanato ligands and four tmbpz ligands that link the iron centres together. The resulting structure consists of two identical interpenetrated NbO-type nets related by a (001) translation. The interpenetration of the nets is stabilised by a network of hydrogen bonds between them, of the form N-H...S - these are tabulated below. The interpenetrating framework structure houses 1-D channels running parallel to the c axis, each consisting of small cavities connected by smaller hexagonal windows of sulphur atoms. This structure was obtained after heating of the crystal in situ to 375 K, and is based on the third set of 650 frames of a 2000 frame data collection. The use of fewer frames has affected the completeness of the intensity data collected. Fourier difference synthesis indicated the presence of significant electron density in the 1-D channels, consistent with the continuing presence of some solvent of crystallisation in the material. This solvent was modelled similarly to the as-grown material (see data_A_2/3MECN) with isotropic thermal parameters fixed at values double those used for A_0.27MeCN at 150 K. We justify this choice of thermal parameters by reference to the ratio of Fe1 Ueq obtained at in A_0.27MeCN and A_375K_1 (1 : 2.14). The chosen parameters are tabulated below: C101 0.200 Uiso C100 0.200 Uiso N100 0.300 Uiso The occupancy of these three atom positions was allowed to refine by means of a single free variable. The value obtained (FVAR 0.43995) indicates a 44% occupancy of the solvent atom positions. The solvent was retrained using the following commands: DFIX 1.39 0.01 C100 C101 DFIX 1.15 0.01 C100 N100 DFIX 2.54 0.01 C101 N100 All non-hydrogen atoms were refined anisotropically except those of the disordered acetonitrile molecule. Hydrogen atoms were geometrically constrained using a riding atom model. Methyl group hydrogen atoms on tmbpz and acetonitrile appeared to be disordered when difference peaks were examined, and therefore they were modelled accordingly. ; _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^)+(0.0253P)^2^+43.5476P] 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 3146 _refine_ls_number_parameters 168 _refine_ls_number_restraints 3 _refine_ls_R_factor_all 0.1275 _refine_ls_R_factor_gt 0.0560 _refine_ls_wR_factor_ref 0.1356 _refine_ls_wR_factor_gt 0.1006 _refine_ls_goodness_of_fit_ref 1.053 _refine_ls_restrained_S_all 1.053 _refine_ls_shift/su_max 0.000 _refine_ls_shift/su_mean 0.000 loop_ _atom_site_label _atom_site_type_symbol _atom_site_fract_x _atom_site_fract_y _atom_site_fract_z _atom_site_U_iso_or_equiv _atom_site_adp_type _atom_site_occupancy _atom_site_symmetry_multiplicity _atom_site_calc_flag _atom_site_refinement_flags _atom_site_disorder_assembly _atom_site_disorder_group Fe1 Fe 0.5000 0.5000 0.5000 0.0327(2) Uani 1 2 d S . . S1 S 0.33198(6) 0.52459(6) 0.62287(11) 0.0456(3) Uani 1 1 d . . . C1 C 0.39295(19) 0.52186(18) 0.5950(3) 0.0305(9) Uani 1 1 d . . . N1 N 0.43686(16) 0.52031(16) 0.5733(3) 0.0349(8) Uani 1 1 d . . . N10 N 0.54988(16) 0.52796(15) 0.6803(3) 0.0328(8) Uani 1 1 d . . . N11 N 0.54991(16) 0.57597(15) 0.7327(3) 0.0339(8) Uani 1 1 d . . . H11 H 0.5300 0.5924 0.7049 0.041 Uiso 1 1 calc R . . C10 C 0.58607(19) 0.51669(19) 0.7508(3) 0.0307(9) Uani 1 1 d . . . C11 C 0.60932(18) 0.55850(18) 0.8488(3) 0.0301(9) Uani 1 1 d . . . C12 C 0.5846(2) 0.59536(19) 0.8335(3) 0.0331(10) Uani 1 1 d . . . C13 C 0.5982(2) 0.4662(2) 0.7261(4) 0.0465(12) Uani 1 1 d . . . H13A H 0.5764 0.4446 0.6548 0.070 Uiso 0.50 1 calc PR . . H13B H 0.5852 0.4390 0.7941 0.070 Uiso 0.50 1 calc PR . . H13C H 0.6409 0.4824 0.7133 0.070 Uiso 0.50 1 calc PR . . H13D H 0.6253 0.4661 0.7867 0.070 Uiso 0.50 1 calc PR . . H13E H 0.6165 0.4717 0.6474 0.070 Uiso 0.50 1 calc PR . . H13F H 0.5608 0.4282 0.7281 0.070 Uiso 0.50 1 calc PR . . C14 C 0.5906(2) 0.6470(2) 0.9064(4) 0.0534(14) Uani 1 1 d . . . H14A H 0.5670 0.6627 0.8698 0.080 Uiso 0.50 1 calc PR . . H14B H 0.6324 0.6783 0.9092 0.080 Uiso 0.50 1 calc PR . . H14C H 0.5762 0.6334 0.9872 0.080 Uiso 0.50 1 calc PR . . H14D H 0.6167 0.6536 0.9744 0.080 Uiso 0.50 1 calc PR . . H14E H 0.5513 0.6379 0.9350 0.080 Uiso 0.50 1 calc PR . . H14F H 0.6075 0.6828 0.8570 0.080 Uiso 0.50 1 calc PR . . C20 C 0.6442(2) 0.5243(2) 1.0363(3) 0.0345(10) Uani 1 1 d . . . C21 C 0.65225(18) 0.56480(18) 0.9459(3) 0.0282(9) Uani 1 1 d . . . C22 C 0.70851(19) 0.61671(18) 0.9724(3) 0.0315(9) Uani 1 1 d . . . C23 C 0.5928(2) 0.4619(2) 1.0599(4) 0.0557(14) Uani 1 1 d . . . H23A H 0.6018 0.4453 1.1299 0.084 Uiso 0.50 1 calc PR . . H23B H 0.5871 0.4366 0.9908 0.084 Uiso 0.50 1 calc PR . . H23C H 0.5565 0.4635 1.0744 0.084 Uiso 0.50 1 calc PR . . H23D H 0.5617 0.4517 1.0001 0.084 Uiso 0.50 1 calc PR . . H23E H 0.5765 0.4603 1.1392 0.084 Uiso 0.50 1 calc PR . . H23F H 0.6071 0.4334 1.0556 0.084 Uiso 0.50 1 calc PR . . C24 C 0.7409(2) 0.6740(2) 0.9015(4) 0.0508(13) Uani 1 1 d . . . H24A H 0.7782 0.7014 0.9414 0.076 Uiso 0.50 1 calc PR . . H24B H 0.7159 0.6923 0.8957 0.076 Uiso 0.50 1 calc PR . . H24C H 0.7494 0.6652 0.8215 0.076 Uiso 0.50 1 calc PR . . H24D H 0.7175 0.6712 0.8310 0.076 Uiso 0.50 1 calc PR . . H24E H 0.7798 0.6803 0.8767 0.076 Uiso 0.50 1 calc PR . . H24F H 0.7463 0.7074 0.9509 0.076 Uiso 0.50 1 calc PR . . N20 N 0.73347(15) 0.60912(15) 1.0738(3) 0.0309(8) Uani 1 1 d . . . N21 N 0.69277(16) 0.55180(15) 1.1090(3) 0.0334(8) Uani 1 1 d . . . H21 H 0.6977 0.5348 1.1720 0.040 Uiso 1 1 calc R . . C101 C 0.3333 0.6667 -0.158(5) 0.200 Uiso 0.440(17) 3 d SPD . . H10A H 0.3057 0.6378 -0.2157 0.300 Uiso 0.073(3) 1 calc PR . . H10B H 0.3742 0.6825 -0.1860 0.300 Uiso 0.073(3) 1 calc PR . . H10C H 0.3249 0.6993 -0.1492 0.300 Uiso 0.073(3) 1 calc PR . . H10D H 0.3642 0.7086 -0.1516 0.300 Uiso 0.073(3) 1 calc PR . . H10E H 0.2957 0.6639 -0.1813 0.300 Uiso 0.073(3) 1 calc PR . . H10F H 0.3450 0.6471 -0.2181 0.300 Uiso 0.073(3) 1 calc PR . . C100 C 0.326(5) 0.638(3) -0.046(5) 0.200 Uiso 0.147(6) 1 d PD . . N100 N 0.328(5) 0.620(4) 0.048(5) 0.300 Uiso 0.147(6) 1 d PD . . 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 0.0297(5) 0.0438(6) 0.0258(4) -0.0077(4) -0.0035(4) 0.0191(4) S1 0.0384(7) 0.0602(8) 0.0459(7) 0.0045(6) 0.0043(5) 0.0304(6) C1 0.031(2) 0.028(2) 0.027(2) 0.0018(17) 0.0006(17) 0.0110(19) N1 0.035(2) 0.043(2) 0.0269(17) 0.0020(15) 0.0023(15) 0.0195(18) N10 0.037(2) 0.032(2) 0.0274(17) -0.0049(14) -0.0037(15) 0.0158(17) N11 0.041(2) 0.039(2) 0.0271(17) -0.0056(15) -0.0079(15) 0.0236(18) C10 0.034(2) 0.033(2) 0.0242(19) 0.0012(17) -0.0007(17) 0.016(2) C11 0.034(2) 0.033(2) 0.0210(18) -0.0009(16) -0.0039(16) 0.0145(19) C12 0.039(3) 0.033(2) 0.026(2) -0.0026(17) -0.0052(18) 0.017(2) C13 0.062(3) 0.048(3) 0.039(3) -0.007(2) -0.012(2) 0.035(3) C14 0.074(4) 0.055(3) 0.046(3) -0.025(2) -0.026(3) 0.043(3) C20 0.041(3) 0.037(2) 0.026(2) -0.0029(18) 0.0000(18) 0.020(2) C21 0.033(2) 0.032(2) 0.0209(18) 0.0002(16) -0.0023(16) 0.0170(19) C22 0.038(2) 0.032(2) 0.0218(19) 0.0004(16) -0.0012(17) 0.015(2) C23 0.054(3) 0.044(3) 0.048(3) 0.011(2) -0.002(2) 0.009(3) C24 0.049(3) 0.041(3) 0.044(3) 0.011(2) -0.014(2) 0.008(2) N20 0.0323(19) 0.034(2) 0.0259(17) 0.0031(14) -0.0032(14) 0.0156(17) N21 0.039(2) 0.036(2) 0.0265(17) 0.0051(15) -0.0029(15) 0.0188(18) _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 N1 2.082(4) . ? Fe1 N1 2.082(4) 10_666 ? Fe1 N10 2.273(3) 10_666 ? Fe1 N10 2.273(3) . ? Fe1 N20 2.435(3) 18_546 ? Fe1 N20 2.435(3) 6_564 ? S1 C1 1.617(4) . ? C1 N1 1.163(5) . ? N10 C10 1.341(5) . ? N10 N11 1.351(4) . ? N11 C12 1.349(5) . ? N11 H11 0.8600 . ? C10 C11 1.421(5) . ? C10 C13 1.491(6) . ? C11 C12 1.376(6) . ? C11 C21 1.480(5) . ? C12 C14 1.482(6) . ? C13 H13A 0.9600 . ? C13 H13B 0.9600 . ? C13 H13C 0.9600 . ? C13 H13D 0.9600 . ? C13 H13E 0.9600 . ? C13 H13F 0.9600 . ? C14 H14A 0.9600 . ? C14 H14B 0.9600 . ? C14 H14C 0.9600 . ? C14 H14D 0.9600 . ? C14 H14E 0.9600 . ? C14 H14F 0.9600 . ? C20 N21 1.340(5) . ? C20 C21 1.373(5) . ? C20 C23 1.492(6) . ? C21 C22 1.411(6) . ? C22 N20 1.346(5) . ? C22 C24 1.488(6) . ? C23 H23A 0.9600 . ? C23 H23B 0.9600 . ? C23 H23C 0.9600 . ? C23 H23D 0.9600 . ? C23 H23E 0.9600 . ? C23 H23F 0.9600 . ? C24 H24A 0.9600 . ? C24 H24B 0.9600 . ? C24 H24C 0.9600 . ? C24 H24D 0.9600 . ? C24 H24E 0.9600 . ? C24 H24F 0.9600 . ? N20 N21 1.357(5) . ? N20 Fe1 2.435(3) 8_655 ? N21 H21 0.8600 . ? C101 C100 1.393(10) . ? C101 H10A 0.9600 . ? C101 H10B 0.9600 . ? C101 H10C 0.9600 . ? C101 H10D 0.9600 . ? C101 H10E 0.9600 . ? C101 H10F 0.9600 . ? C100 N100 1.152(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 Fe1 N1 180.000(1) . 10_666 ? N1 Fe1 N10 92.13(13) . 10_666 ? N1 Fe1 N10 87.87(13) 10_666 10_666 ? N1 Fe1 N10 87.87(13) . . ? N1 Fe1 N10 92.13(13) 10_666 . ? N10 Fe1 N10 180.000(1) 10_666 . ? N1 Fe1 N20 95.90(12) . 18_546 ? N1 Fe1 N20 84.10(12) 10_666 18_546 ? N10 Fe1 N20 98.88(12) 10_666 18_546 ? N10 Fe1 N20 81.12(11) . 18_546 ? N1 Fe1 N20 84.10(12) . 6_564 ? N1 Fe1 N20 95.90(12) 10_666 6_564 ? N10 Fe1 N20 81.12(11) 10_666 6_564 ? N10 Fe1 N20 98.88(12) . 6_564 ? N20 Fe1 N20 180.0 18_546 6_564 ? N1 C1 S1 179.0(4) . . ? C1 N1 Fe1 164.3(3) . . ? C10 N10 N11 104.8(3) . . ? C10 N10 Fe1 140.8(3) . . ? N11 N10 Fe1 113.9(2) . . ? C12 N11 N10 112.7(3) . . ? C12 N11 H11 123.6 . . ? N10 N11 H11 123.6 . . ? N10 C10 C11 110.7(4) . . ? N10 C10 C13 122.7(4) . . ? C11 C10 C13 126.6(4) . . ? C12 C11 C10 104.8(3) . . ? C12 C11 C21 125.4(4) . . ? C10 C11 C21 129.7(4) . . ? N11 C12 C11 106.9(3) . . ? N11 C12 C14 121.9(4) . . ? C11 C12 C14 131.2(4) . . ? C10 C13 H13A 109.5 . . ? C10 C13 H13B 109.5 . . ? H13A C13 H13B 109.5 . . ? C10 C13 H13C 109.5 . . ? H13A C13 H13C 109.5 . . ? H13B C13 H13C 109.5 . . ? C10 C13 H13D 109.5 . . ? H13A C13 H13D 141.1 . . ? H13B C13 H13D 56.3 . . ? H13C C13 H13D 56.3 . . ? C10 C13 H13E 109.5 . . ? H13A C13 H13E 56.3 . . ? H13B C13 H13E 141.1 . . ? H13C C13 H13E 56.3 . . ? H13D C13 H13E 109.5 . . ? C10 C13 H13F 109.5 . . ? H13A C13 H13F 56.3 . . ? H13B C13 H13F 56.3 . . ? H13C C13 H13F 141.1 . . ? H13D C13 H13F 109.5 . . ? H13E C13 H13F 109.5 . . ? C12 C14 H14A 109.5 . . ? C12 C14 H14B 109.5 . . ? H14A C14 H14B 109.5 . . ? C12 C14 H14C 109.5 . . ? H14A C14 H14C 109.5 . . ? H14B C14 H14C 109.5 . . ? C12 C14 H14D 109.5 . . ? H14A C14 H14D 141.1 . . ? H14B C14 H14D 56.3 . . ? H14C C14 H14D 56.3 . . ? C12 C14 H14E 109.5 . . ? H14A C14 H14E 56.3 . . ? H14B C14 H14E 141.1 . . ? H14C C14 H14E 56.3 . . ? H14D C14 H14E 109.5 . . ? C12 C14 H14F 109.5 . . ? H14A C14 H14F 56.3 . . ? H14B C14 H14F 56.3 . . ? H14C C14 H14F 141.1 . . ? H14D C14 H14F 109.5 . . ? H14E C14 H14F 109.5 . . ? N21 C20 C21 106.8(4) . . ? N21 C20 C23 122.7(4) . . ? C21 C20 C23 130.4(4) . . ? C20 C21 C22 104.7(3) . . ? C20 C21 C11 128.2(4) . . ? C22 C21 C11 126.9(4) . . ? N20 C22 C21 111.6(4) . . ? N20 C22 C24 120.5(4) . . ? C21 C22 C24 127.9(4) . . ? 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 . . ? C20 C23 H23D 109.5 . . ? H23A C23 H23D 141.1 . . ? H23B C23 H23D 56.3 . . ? H23C C23 H23D 56.3 . . ? C20 C23 H23E 109.5 . . ? H23A C23 H23E 56.3 . . ? H23B C23 H23E 141.1 . . ? H23C C23 H23E 56.3 . . ? H23D C23 H23E 109.5 . . ? C20 C23 H23F 109.5 . . ? H23A C23 H23F 56.3 . . ? H23B C23 H23F 56.3 . . ? H23C C23 H23F 141.1 . . ? H23D C23 H23F 109.5 . . ? H23E C23 H23F 109.5 . . ? C22 C24 H24A 109.5 . . ? C22 C24 H24B 109.5 . . ? H24A C24 H24B 109.5 . . ? C22 C24 H24C 109.5 . . ? H24A C24 H24C 109.5 . . ? H24B C24 H24C 109.5 . . ? C22 C24 H24D 109.5 . . ? H24A C24 H24D 141.1 . . ? H24B C24 H24D 56.3 . . ? H24C C24 H24D 56.3 . . ? C22 C24 H24E 109.5 . . ? H24A C24 H24E 56.3 . . ? H24B C24 H24E 141.1 . . ? H24C C24 H24E 56.3 . . ? H24D C24 H24E 109.5 . . ? C22 C24 H24F 109.5 . . ? H24A C24 H24F 56.3 . . ? H24B C24 H24F 56.3 . . ? H24C C24 H24F 141.1 . . ? H24D C24 H24F 109.5 . . ? H24E C24 H24F 109.5 . . ? C22 N20 N21 103.3(3) . . ? C22 N20 Fe1 133.5(3) . 8_655 ? N21 N20 Fe1 122.2(2) . 8_655 ? C20 N21 N20 113.6(3) . . ? C20 N21 H21 123.2 . . ? N20 N21 H21 123.2 . . ? C100 C101 H10A 109.5 . . ? C100 C101 H10B 109.5 . . ? H10A C101 H10B 109.5 . . ? C100 C101 H10C 109.5 . . ? H10A C101 H10C 109.5 . . ? H10B C101 H10C 109.5 . . ? C100 C101 H10D 109.5 . . ? H10A C101 H10D 141.1 . . ? H10B C101 H10D 56.3 . . ? H10C C101 H10D 56.3 . . ? C100 C101 H10E 109.5 . . ? H10A C101 H10E 56.3 . . ? H10B C101 H10E 141.1 . . ? H10C C101 H10E 56.3 . . ? H10D C101 H10E 109.5 . . ? C100 C101 H10F 109.5 . . ? H10A C101 H10F 56.3 . . ? H10B C101 H10F 56.3 . . ? H10C C101 H10F 141.1 . . ? H10D C101 H10F 109.5 . . ? H10E C101 H10F 109.5 . . ? N100 C100 C101 171(9) . . ? loop_ _geom_hbond_atom_site_label_D _geom_hbond_atom_site_label_H _geom_hbond_atom_site_label_A _geom_hbond_distance_DH _geom_hbond_distance_HA _geom_hbond_distance_DA _geom_hbond_angle_DHA _geom_hbond_site_symmetry_A N11 H11 S1 0.86 2.85 3.654(4) 156.6 15_556 N21 H21 S1 0.86 2.61 3.418(3) 156.5 10_667 _diffrn_measured_fraction_theta_max 0.953 _diffrn_reflns_theta_full 27.95 _diffrn_measured_fraction_theta_full 0.953 _refine_diff_density_max 0.409 _refine_diff_density_min -0.540 _refine_diff_density_rms 0.083