metal-organic compounds

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1 metal-organic compounds Acta Crystallographica Section C Crystal Structure Communications ISSN A saccharinate±iron(ii) complex with a free saccharin molecule present, [Fe(phen) 3 ]sac 2 sach6h 2 O Robert M. K. Deng, a Sabitha Simon, a Keith B. Dillon b and Andres E. Goeta b * a Chemistry Department, University of Botswana, Private Bag 0022, Gaborone, Botswana, and b Chemistry Department, Durham University, South Road, Durham DH1 3LE, England Correspondence a.e.goeta@durham.ac.uk Received 19 June 2000 Accepted 26 September 2000 The crystal structure of the title compound, tris(1,10- phenanthroline-n,n 0 )iron(ii) bis[1,2-benzisothiazol-3(2h)- onate 1,1-dioxide] 1,2-benzisothiazol-3(2H)-one 1,1-dioxide hexahydrate, [Fe(C 12 H 8 N 2 ) 3 ](C 7 H 4 NO 3 S) 2 C 7 H 5 NO 3 S6H 2 O, at 120 K consists of slightly distorted octahedral [Fe(phen) 3 ] 2+ cations (phen is 1,10-phenanthroline), two saccharinate anions and a free saccharin molecule, as well as six waters of crystallization. The compound has been con rmed as diamagnetic low-spin iron(ii) by magnetic measurements. There is extensive hydrogen bonding leading to a threedimensional network. Figure 1 Drawing of the [Fe(phen) 3 ] 2+ cation of (I) showing 70% probability displacement ellipsoids. H atoms have been omitted for clarity. Comment In our earlier papers on metal±saccharinate complexes with the bidentate ligands 2,2 0 -bipyridine (bipy) or phen present (Dillon et al., 1999; Deng et al., 2000), we summarized previous work on these systems, including examples with all the Figure 2 The hydrogen-bonding scheme of (I). Atom types are represented as follows: N regular dot pattern, O shaded bottom left to top right, S crosshatched, C shaded and H small open circles. saccharinate ligands attached to the metal (Hergold-Brundic et al., 1989) and ones where saccharinate (sac) is present only as the counter-ion (Ainscough et al., 1990; Li, Chen et al., 1993; Li, Wei et al., 1993). The only structures reported for iron(ii) complexes of saccharin are those of the parent compound, [Fe(sac) 2 (H 2 O) 4 ]2H 2 O (Haider et al., 1983), and of the phen complex [Fe(phen) 3 ](sac) 2 4H 2 O(Li,Weiet al., 1993). In the present work, we report the structure of another tris(1,10- phenanthroline)iron(ii) complex, (I), with two saccharinate anions and one free saccharin molecule present, as well as six waters of crystallization. The compound has been con rmed as diamagnetic iron(ii) (d 6 low spin) by magnetic measurements, which clearly eliminates the alternative possibility of an iron(iii) complex with three saccharinate anions. Such a d 5 complex, if low spin, would be paramagnetic, with one unpaired electron present, while a high-spin species would have ve unpaired electrons. Low spin would be expected in any case, from the position of phen in the spectrochemical series. The structure of the title compound consists of slightly distorted octahedral [Fe(phen) 3 ] 2+ cations, with two sacchar- 4 # 2001 International Union of Crystallography Printed in Great Britain ± all rights reserved Acta Cryst. (2001). C57, 4±6

2 metal-organic compounds inate anions, a free saccharin molecule and six water molecules. The FeÐN distances (Table 1) are quite similar within each of the bidentate phen ligands, although the bonds are slightly longer to N3 and N4 than to the other four N atoms; the average FeÐN bond length is A Ê. This compares well, for example, with the mean distance of 1.97 A Ê in l-[fe- (phen) 3 ]bis[sb III -d-tartrate]8h 2 O (Zalkin et al., 1973), A Ê in [Fe(phen) 3 ]I 2 2H 2 O (Johansson et al., 1978) and A Ê in [Fe(phen) 3 ](sac) 2 4H 2 O (Li, Wei et al., 1993). The central Fe atom in (I) is very close to coplanarity with the four surrounding N atoms; the largest deviation is (1) A Ê from the plane de ned by N2, N3, N4 and N6. This compares with more signi cant deviations of 0.06, 0.03 and A Ê in the structure of [Fe(phen) 3 ](sac) 2 4H 2 O (Li, Wei et al., 1993). The hydrogen-bonding geometry of (I) is shown in Table 2 and displayed in Fig. 2. There is a strong, essentially linear, hydrogen bond between H8 (on N8) in the free saccharin molecule to O11 of a water molecule, with a distance of 1.70 (5) A Ê and a bond angle at hydrogen of 174 (4). The carbonyl O7 atom in one of the saccharinate anions appears to form linear hydrogen bonds with both H4W and H9W on adjacent water molecules, with distances and angles shown in Table 2. There is also a linear hydrogen bond between O3 on S1 in the second saccharinate anion and H11W (see Table 2). A shorter contact between the carbonyl O1 atom and H7W in this ion is also found at (13) A Ê, but at a slightly less favourable angle of 164 (4). Other weaker hydrogen bonds between either the free saccharin molecule or a saccharinate anion and a water molecule are tabulated in Table 2, as well as hydrogen bonds between water molecules. The overall hydrogen-bond scheme can be described as a three-dimensional network formed by the saccharinate anions, the free saccharin molecule and the water molecules. This network, shown in Fig. 3, leaves channels along the b axis where the cations reside. Figure 3 The packing diagram for (I) showing the three-dimensional network formed via hydrogen bonding by the anions, the free saccharin and the water molecules. Only the Fe centres (shaded top left to bottom right) from the cations are shown for clarity. Other atoms are represented as in Fig. 2. Table 1 Selected geometric parameters (A Ê, ). Fe1ÐN (3) Fe1ÐN (3) Fe1ÐN (3) N1ÐFe1ÐN (11) N1ÐFe1ÐN (11) N1ÐFe1ÐN (11) N1ÐFe1ÐN (11) N1ÐFe1ÐN (11) N2ÐFe1ÐN (11) N2ÐFe1ÐN (11) N2ÐFe1ÐN (11) Experimental Compound (I) was prepared by adding a warm solution of 1,10- phenanthroline ( g, 2.46 mmol) in water (50 ml), with stirring, to a warm clear solution of [Fe(sac) 2 (H 2 O) 4 ]2H 2 O ( g, 0.83 mmol) in water (30 ml). A deep-red solution formed, was stirred for some time, and then left to stand. Fine red crystals formed after four weeks. These were separated, washed with 10 ml of cold distilled water and dried in air at room temperature. Elemental analyses, performed by the microanalytical services of the Department of Chemistry, University of Durham, both before and after the crystal structure determination, indicated an average composition of [Fe(phen) 3 ](sac) 2 sach3h 2 O; found: C 57.18, H 3.72, N 10.66%; calculated for C 57 H 43 FeN 9 O 12 S 3 : C 57.15, H 3.62, N 10.52%. It is therefore probable that other material was present containing less water of crystallization than found in the crystals whose X-ray structure was determined in this work. Magnetic measurements were performed on a Johnson±Matthey±Evans magnetic susceptibility balance; the complex was shown to be diamagnetic. Crystal data [Fe(C 12 H 8 N 2 ) 3 ](C 7 H 4 NO 3 S) 2 - C 7 H 5 NO 3 S6H 2 O M r = Monoclinic, P2 1 /n a = (4) A Ê b = (5) A Ê c = (4) A Ê = (5) V = 5289 (2) A Ê 3 Z =4 Data collection Bruker SMART CCD diffractometer! scans Absorption correction: by integration (SHELXTL-NT; Bruker, 1998) T min = 0.830, T max = measured re ections Re nement Re nement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = re ections 812 parameters H atoms treated by a mixture of independent and constrained re nement Fe1ÐN (3) Fe1ÐN (3) Fe1ÐN (3) N2ÐFe1ÐN (11) N3ÐFe1ÐN (11) N3ÐFe1ÐN (11) N3ÐFe1ÐN (11) N4ÐFe1ÐN (10) N4ÐFe1ÐN (11) N5ÐFe1ÐN (11) D x = Mg m 3 Mo K radiation Cell parameters from 869 re ections = 10.20±21.52 = mm 1 T = 120 (2) K Rectangular plate, red mm independent re ections 7374 re ections with I > 2(I) R int = max = h = 22! 20 k = 26! 26 l = 24! 24 w = 1/[ 2 (F o 2 ) + (0.0583P) P] where P =(F o 2 +2F c 2 )/3 (/) max = max = 0.52 e A Ê 3 min = 0.70 e A Ê 3 Acta Cryst. (2001). C57, 4±6 Robert M. K. Deng et al. [Fe(C 12 H 8 N 2 ) 3 ](C 7 H 4 NO 3 S) 2 C 7 H 5 NO 3 S6H 2 O 5

3 metal-organic compounds Table 2 Hydrogen-bonding geometry (A Ê, ). DÐHA DÐH HA DA DÐHA N8ÐH8NO (5) 1.70 (5) (4) 174 (4) O10ÐH1WO (4) 2.19 (2) (4) 148 (4) O10ÐH2WO13 i 0.90 (3) 1.87 (3) (4) 171 (5) O11ÐH3WO (3) 1.87 (4) (4) 161 (5) O11ÐH4WO (3) 1.85 (3) (3) 174 (4) O12ÐH5WN7 ii 0.90 (3) 2.70 (2) (5) 157 (5) O12ÐH6WO9 iii 0.90 (3) 2.13 (4) (4) 146 (5) O13ÐH7WO (3) 1.85 (2) (4) 164 (4) O13ÐH8WO14 iv 0.90 (3) 1.95 (2) (5) 163 (5) O14ÐH9WO7 v 0.90 (3) 1.84 (3) (4) 176 (4) O14ÐH10WO (3) 1.97 (2) (4) 157 (5) O15ÐH11WO (3) 2.02 (2) (4) 176 (3) O15ÐH12WO12 vi 0.90 (3) 1.92 (2) (4) 161 (4) Symmetry codes: (i) 1 x; y; 2 z; (ii) 1 x; y; 1 z; (iii) 1 2 x; 1 2 y; z 1 2 ; (iv) 1 2 x; y 1 2 ; 3 2 z; (v) x 1 2 ; 1 2 y; z 1 2 ; (vi) x 1 2 ; 1 2 y; 1 2 z. All water H atoms and the amino H atom of the free saccharin molecule were re ned. All water OÐH distances were restrained to be 0.9 A Ê, with s.u.'s of A Ê. Other H atoms were treated as riding (CÐH = 0.93 A Ê ). Data collection: SMART-NT (Bruker, 1998); cell re nement: SMART-NT; data reduction: SAINT-NT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to re ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 1998). RMKD acknowledges The Faculty of Science Research and Publication Committee for a research grant. Supplementary data for this paper are available from the IUCr electronic archives (Reference: BM1421). Services for accessing these data are described at the back of the journal. References Ainscough, E. W., Baker, E. N., Brodie, A. M., Cresswell, R. J., Ranford, J. D. & Waters, J. M. (1990). Inorg. Chim. Acta, 172, 185±190. Bruker (1998). SMART-NT and SAINT-NT (Versions 5.0), and SHELXTL- NT (Version 5.1). Bruker AXS Inc., Madison, Wisconsin, USA. Deng, R. M. K., Bilton, C., Dillon, K. B. & Howard, J. A. K. (2000). Acta Cryst. C56, 142±145. Dillon, K. B., Bilton, C., Howard, J. A. K., Hoy, V. J., Deng, R. M. K. & Sethatho, D. T. (1999). Acta Cryst. C55, 330±331. Haider, S. Z., Malik, K. M. A., Ahmed, K. J., Hess, H., Riffel, H. & Hursthouse, M. B. (1983). Inorg. Chim. Acta, 72, 21±27. Hergold-BrundicÂ, A., Kamenar, B. & Jovanovski, G. (1989). Acta Cryst. C45, 556±558. Johansson, L., Molund, M. & Oskarsson, A Ê. (1978). Inorg. Chim. Acta, 31, 117±123. Li, J., Chen, H., Wu, Q. & Wu, X. (1993). Cryst. Res. Technol. 28, 181± 186. Li, J., Wei, J., Wu, X., Zhu, N. & Zhang, Y. (1993). Cryst. Res. Technol. 28, 11± 14. Sheldrick, G. M. (1990). Acta Cryst. A46, 467±473. Sheldrick, G. M. (1997). SHELXL97. University of GoÈttingen, Germany. Zalkin, A., Templeton, D. H. & Ueki, T. (1973). Inorg. Chem. 12, 1641± Robert M. K. Deng et al. [Fe(C 12 H 8 N 2 ) 3 ](C 7 H 4 NO 3 S) 2 C 7 H 5 NO 3 S6H 2 O Acta Cryst. (2001). C57, 4±6

4 supporting information [doi: /s ] A saccharinate iron(ii) complex with a free saccharin molecule present, [Fe(phen) 3 ]sac 2 sach 6H 2 O Robert M. K. Deng, Sabitha Simon, Keith B. Dillon and Andres E. Goeta Computing details Data collection: SMART-NT (Bruker, 1998); cell refinement: SMART-NT; data reduction: SAINT-NT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1990); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL-NT (Bruker, 1998). tris(1,10-phenanthroline-n,n )iron(ii) bis[1,2-benzisothiazol-3(2h)-onate 1,1-dioxide] 1,2- benzisothiazol-3(2h)-one 1,1-dioxide hexahydrate Crystal data [Fe(C 12 H 8 N 2 ) 3 ](C 7 H 4 NO 3 S) 2 C 7 H 5 NO 3 S 6H 2 O M r = Monoclinic, P2 1 /n a = (4) Å b = (5) Å c = (4) Å β = (5) V = 5289 (2) Å 3 Z = 4 Data collection Bruker SMART-CCD diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scans Absorption correction: integration (SHELXTL-NT; Bruker, 1998) T min = 0.830, T max = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 812 parameters 18 restraints F(000) = 2592 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 869 reflections θ = µ = 0.49 mm 1 T = 120 K Rectangular plate, red mm measured reflections independent reflections 7374 reflections with I > 2σ(I) R int = θ max = 30.5, θ min = 1.6 h = k = l = Primary atom site location: structure-invariant direct methods Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H atoms treated by a mixture of independent and constrained refinement sup-1

5 w = 1/[σ 2 (F o2 ) + (0.0583P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.52 e Å 3 Δρ min = 0.70 e Å 3 Special details Experimental. The detector was positioned at 2θ = -26 at a distance of 45 mm from the crystal. Data collection was carried out using ω scans, 0.3 wide 10 secs frames, starting at 3 different φ positions in order to cover a hemisphere. Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. 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 > σ(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. Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Fe (3) (2) (2) (11) N (16) (14) (14) (6) C (2) (18) (18) (7) H1A * C (2) (19) (19) (8) H2A * C (2) (19) (19) (8) H3A * C (2) (18) (18) (7) C (2) (19) (2) (8) H5B * C (2) (19) (2) (8) H6A * C (2) (18) (18) (7) C (2) (19) (19) (8) H8A * C (2) (18) (19) (8) H9A * C (2) (18) (18) (7) H10A * N (16) (14) (14) (6) C (19) (17) (18) (7) C (19) (17) (18) (7) N (16) (14) (14) (6) C (2) (18) (18) (7) H13A * C (2) (2) (19) (8) H14A * C (2) (18) (19) (8) H15A * sup-2

6 C (2) (18) (18) (7) C (2) (18) (19) (8) H17A * C (2) (19) (19) (8) H18A * C (2) (17) (18) (7) C (2) (19) (19) (8) H20A * C (2) (18) (19) (8) H21A * C (2) (18) (18) (7) H22A * N (16) (14) (14) (6) C (19) (17) (17) (7) C (19) (17) (17) (7) N (16) (14) (14) (6) C (2) (17) (18) (7) H25A * C (2) (17) (18) (7) H26A * C (2) (18) (18) (7) H27A * C (2) (18) (18) (7) C (2) (18) (19) (8) H29A * C (2) (18) (19) (8) H30A * C (19) (18) (18) (7) C (2) (18) (19) (8) H32A * C (2) (19) (19) (8) H33A * C (2) (18) (18) (7) H34A * N (16) (14) (14) (6) C (19) (17) (17) (7) C (19) (17) (17) (7) N (18) (16) (16) (7) C (2) (18) (19) (7) O (15) (12) (13) (5) C (2) (18) (18) (7) C (2) (19) (19) (7) H39A * C (2) (19) (19) (8) H40A * C (2) (19) (19) (8) H41A * C (2) (19) (19) (8) sup-3

7 H42A * C (2) (19) (18) (7) S (5) (5) (5) (2) O (16) (14) (13) (6) O (15) (14) (15) (6) N (19) (16) (16) (7) H8N (3) (2) (3) (14)* C (2) (18) (18) (7) O (14) (13) (13) (5) C (2) (17) (18) (7) C (2) (19) (2) (8) H46A * C (2) (19) (2) (8) H47A * C (2) (18) (19) (8) H48A * C (2) (18) (19) (8) H49A * C (2) (17) (18) (7) S (5) (5) (5) (19) O (15) (13) (14) (6) O (15) (13) (13) (6) N (17) (15) (16) (6) C (2) (18) (19) (7) O (14) (13) (13) (6) C (2) (18) (18) (7) C (2) (18) (18) (8) H53A * C (2) (19) (19) (8) H54A * C (2) (19) (19) (8) H55A * C (2) (18) (18) (8) H56A * C (2) (18) (18) (7) S (5) (5) (5) (2) O (14) (13) (14) (6) O (15) (13) (14) (6) O (18) (15) (16) (7) H1W (3) (2) (2) (14)* H2W (3) (3) (9) (14)* O (16) (14) (15) (6) H3W (3) (14) (2) (12)* H4W (3) (2) (12) (12)* O (2) (19) (18) (9) H5W (4) (16) (2) (18)* H6W (4) (3) (11) (18)* O (2) (15) (19) (8) sup-4

8 H7W (2) (7) (3) (12)* H8W (14) (16) (3) (12)* O (2) (15) (16) (8) H9W (4) (15) (18) (15)* H10W (4) (2) (11) (15)* O (17) (16) (16) (7) H11W (2) (8) (3) (10)* H12W (15) (13) (3) (10)* Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Fe (2) (3) (2) (19) (16) (2) N (14) (16) (13) (12) (10) (12) C (18) (2) (16) (14) (13) (15) C (19) (2) (16) (15) (13) (15) C (18) (2) (17) (15) (13) (15) C (17) (19) (16) (14) (13) (14) C (2) (2) (19) (15) (14) (16) C (2) (2) (19) (15) (15) (15) C (18) (19) (17) (14) (13) (15) C (19) (2) (18) (15) (14) (15) C (2) (2) (16) (16) (14) (15) C (18) (19) (16) (14) (13) (14) N (14) (16) (13) (11) (10) (12) C (17) (18) (16) (13) (12) (14) C (17) (19) (16) (13) (12) (14) N (15) (15) (13) (11) (11) (11) C (18) (2) (16) (14) (13) (14) C (19) (2) (18) (16) (14) (16) C (18) (2) (18) (15) (13) (15) C (17) (19) (16) (14) (13) (14) C (19) (2) (18) (15) (14) (15) C (2) (19) (18) (15) (15) (15) C (18) (19) (16) (14) (13) (14) C (2) (2) (17) (15) (14) (15) C (19) (2) (17) (15) (14) (16) C (17) (19) (17) (14) (13) (15) N (14) (15) (13) (11) (10) (11) C (17) (17) (15) (14) (12) (13) C (17) (18) (15) (13) (12) (13) N (14) (14) (13) (11) (10) (11) C (19) (18) (17) (14) (13) (14) C (2) (18) (16) (14) (14) (14) C (19) (19) (16) (15) (13) (14) C (18) (19) (16) (14) (13) (14) C (19) (2) (18) (15) (14) (16) C (18) (2) (19) (14) (14) (16) sup-5

9 C (17) (18) (16) (14) (12) (15) C (18) (2) (18) (15) (14) (16) C (19) (2) (17) (15) (14) (15) C (19) (19) (16) (15) (13) (14) N (15) (15) (13) (11) (11) (11) C (17) (17) (15) (13) (12) (13) C (17) (17) (15) (13) (12) (13) N (17) (17) (16) (13) (12) (13) C (18) (2) (17) (14) (13) (15) O (14) (14) (13) (11) (10) (11) C (17) (18) (16) (14) (13) (14) C (18) (2) (16) (15) (13) (15) C (2) (2) (18) (16) (15) (16) C (2) (2) (18) (16) (15) (15) C (19) (2) (17) (15) (14) (15) C (18) (2) (16) (15) (13) (15) S (5) (5) (4) (4) (3) (4) O (15) (17) (12) (13) (11) (12) O (13) (17) (15) (11) (11) (13) N (16) (18) (15) (13) (12) (13) C (19) (19) (16) (15) (13) (15) O (14) (15) (12) (11) (10) (11) C (19) (19) (16) (14) (13) (14) C (19) (2) (18) (15) (14) (16) C (19) (2) (19) (15) (15) (16) C (2) (2) (17) (16) (15) (15) C (2) (19) (17) (15) (14) (14) C (18) (19) (16) (14) (13) (14) S (4) (5) (4) (4) (3) (4) O (14) (15) (14) (11) (11) (11) O (14) (15) (13) (11) (10) (11) N (16) (17) (16) (12) (12) (13) C (19) (19) (17) (15) (13) (14) O (13) (15) (13) (10) (10) (11) C (17) (19) (16) (14) (12) (14) C (18) (2) (17) (15) (13) (15) C (2) (2) (17) (17) (15) (16) C (2) (2) (17) (17) (15) (15) C (19) (2) (17) (15) (13) (15) C (18) (19) (16) (14) (13) (14) S (4) (5) (4) (4) (3) (4) O (14) (15) (14) (11) (10) (12) O (14) (16) (14) (11) (11) (12) O (18) (17) (15) (14) (13) (13) O (15) (17) (14) (12) (11) (12) O (2) (2) (19) (18) (16) (17) O (2) (17) (19) (15) (17) (15) O (2) (17) (17) (15) (15) (13) sup-6

10 O (16) (19) (16) (13) (12) (15) Geometric parameters (Å, º) Fe1 N (3) C32 H32A Fe1 N (3) C33 C (5) Fe1 N (3) C33 H33A Fe1 N (3) C34 N (4) Fe1 N (3) C34 H34A Fe1 N (3) N6 C (4) N1 C (4) C35 C (4) N1 C (4) N7 C (4) C1 C (5) N7 S (3) C1 H1A C37 O (4) C2 C (5) C37 C (5) C2 H2A C38 C (5) C3 C (4) C38 C (4) C3 H3A C39 C (5) C4 C (4) C39 H39A C4 C (5) C40 C (5) C5 C (5) C40 H40A C5 H5B C41 C (5) C6 C (5) C41 H41A C6 H6A C42 C (5) C7 C (5) C42 H42A C7 C (5) C43 S (4) C8 C (5) S1 O (2) C8 H8A S1 O (3) C9 C (5) N8 C (4) C9 H9A N8 S (3) C10 N (4) N8 H8N 0.92 (5) C10 H10A C44 O (4) N2 C (4) C44 C (5) C11 C (4) C45 C (5) N3 C (4) C45 C (5) N3 C (4) C46 C (5) C13 C (5) C46 H46A C13 H13A C47 C (5) C14 C (5) C47 H47A C14 H14A C48 C (5) C15 C (5) C48 H48A C15 H15A C49 C (5) C16 C (4) C49 H49A C16 C (5) C50 S (3) C17 C (5) S2 O (3) C17 H17A S2 O (2) C18 C (5) N9 C (4) C18 H18A N9 S (3) sup-7

11 C19 C (5) C51 O (4) C19 C (4) C51 C (5) C20 C (5) C52 C (4) C20 H20A C52 C (5) C21 C (5) C53 C (5) C21 H21A C53 H53A C22 N (4) C54 C (5) C22 H22A C54 H54A N4 C (4) C55 C (5) C23 C (4) C55 H55A N5 C (4) C56 C (5) N5 C (4) C56 H56A C25 C (5) C57 S (3) C25 H25A S3 O (2) C26 C (5) S3 O (2) C26 H26A O10 H1W (5) C27 C (5) O10 H2W (5) C27 H27A O11 H3W (5) C28 C (4) O11 H4W (5) C28 C (5) O12 H5W (5) C29 C (5) O12 H6W (5) C29 H29A O13 H7W (5) C30 C (5) O13 H8W (5) C30 H30A O14 H9W (5) C31 C (5) O14 H10W (5) C31 C (4) O15 H11W (5) C32 C (5) O15 H12W (5) N1 Fe1 N (11) C29 C30 C (3) N1 Fe1 N (11) C29 C30 H30A N1 Fe1 N (11) C31 C30 H30A N1 Fe1 N (11) C32 C31 C (3) N1 Fe1 N (11) C32 C31 C (3) N2 Fe1 N (11) C35 C31 C (3) N2 Fe1 N (11) C33 C32 C (3) N2 Fe1 N (11) C33 C32 H32A N2 Fe1 N (11) C31 C32 H32A N3 Fe1 N (11) C32 C33 C (3) N3 Fe1 N (11) C32 C33 H33A N3 Fe1 N (11) C34 C33 H33A N4 Fe1 N (10) N6 C34 C (3) N4 Fe1 N (11) N6 C34 H34A N5 Fe1 N (11) C33 C34 H34A C1 N1 C (3) C34 N6 C (3) C1 N1 Fe (2) C34 N6 Fe (2) C12 N1 Fe (2) C35 N6 Fe (2) N1 C1 C (3) N6 C35 C (3) N1 C1 H1A N6 C35 C (3) sup-8

12 C2 C1 H1A C31 C35 C (3) C3 C2 C (3) N5 C36 C (3) C3 C2 H2A N5 C36 C (3) C1 C2 H2A C28 C36 C (3) C2 C3 C (3) C37 N7 S (2) C2 C3 H3A O1 C37 N (3) C4 C3 H3A O1 C37 C (3) C12 C4 C (3) N7 C37 C (3) C12 C4 C (3) C39 C38 C (3) C3 C4 C (3) C39 C38 C (3) C6 C5 C (3) C43 C38 C (3) C6 C5 H5B C40 C39 C (3) C4 C5 H5B C40 C39 H39A C5 C6 C (3) C38 C39 H39A C5 C6 H6A C39 C40 C (3) C7 C6 H6A C39 C40 H40A C11 C7 C (3) C41 C40 H40A C11 C7 C (3) C40 C41 C (3) C8 C7 C (3) C40 C41 H41A C9 C8 C (3) C42 C41 H41A C9 C8 H8A C43 C42 C (3) C7 C8 H8A C43 C42 H42A C8 C9 C (3) C41 C42 H42A C8 C9 H9A C42 C43 C (3) C10 C9 H9A C42 C43 S (3) N2 C10 C (3) C38 C43 S (3) N2 C10 H10A O2 S1 O (15) C9 C10 H10A O2 S1 N (16) C10 N2 C (3) O3 S1 N (16) C10 N2 Fe (2) O2 S1 C (16) C11 N2 Fe (2) O3 S1 C (16) N2 C11 C (3) N7 S1 C (15) N2 C11 C (3) C44 N8 S (2) C7 C11 C (3) C44 N8 H8N 122 (3) N1 C12 C (3) S2 N8 H8N 121 (3) N1 C12 C (3) O4 C44 N (3) C4 C12 C (3) O4 C44 C (3) C13 N3 C (3) N8 C44 C (3) C13 N3 Fe (2) C46 C45 C (3) C24 N3 Fe (2) C46 C45 C (3) N3 C13 C (3) C50 C45 C (3) N3 C13 H13A C45 C46 C (3) C14 C13 H13A C45 C46 H46A C15 C14 C (3) C47 C46 H46A C15 C14 H14A C46 C47 C (3) C13 C14 H14A C46 C47 H47A C14 C15 C (3) C48 C47 H47A C14 C15 H15A C49 C48 C (3) sup-9

13 C16 C15 H15A C49 C48 H48A C24 C16 C (3) C47 C48 H48A C24 C16 C (3) C50 C49 C (3) C15 C16 C (3) C50 C49 H49A C18 C17 C (3) C48 C49 H49A C18 C17 H17A C49 C50 C (3) C16 C17 H17A C49 C50 S (3) C17 C18 C (3) C45 C50 S (2) C17 C18 H18A O5 S2 O (15) C19 C18 H18A O5 S2 N (15) C20 C19 C (3) O6 S2 N (16) C20 C19 C (3) O5 S2 C (16) C23 C19 C (3) O6 S2 C (15) C21 C20 C (3) N8 S2 C (16) C21 C20 H20A C51 N9 S (2) C19 C20 H20A O7 C51 N (3) C20 C21 C (3) O7 C51 C (3) C20 C21 H21A N9 C51 C (3) C22 C21 H21A C57 C52 C (3) N4 C22 C (3) C57 C52 C (3) N4 C22 H22A C53 C52 C (3) C21 C22 H22A C52 C53 C (3) C22 N4 C (3) C52 C53 H53A C22 N4 Fe (2) C54 C53 H53A C23 N4 Fe (2) C53 C54 C (3) N4 C23 C (3) C53 C54 H54A N4 C23 C (3) C55 C54 H54A C19 C23 C (3) C56 C55 C (3) N3 C24 C (3) C56 C55 H55A N3 C24 C (3) C54 C55 H55A C16 C24 C (3) C57 C56 C (3) C25 N5 C (3) C57 C56 H56A C25 N5 Fe (2) C55 C56 H56A C36 N5 Fe (2) C56 C57 C (3) N5 C25 C (3) C56 C57 S (3) N5 C25 H25A C52 C57 S (2) C26 C25 H25A O8 S3 O (15) C27 C26 C (3) O8 S3 N (15) C27 C26 H26A O9 S3 N (16) C25 C26 H26A O8 S3 C (16) C26 C27 C (3) O9 S3 C (15) C26 C27 H27A N9 S3 C (15) C28 C27 H27A H1W O10 H2W (8) C27 C28 C (3) H3W O11 H4W (8) C27 C28 C (3) H5W O12 H6W (8) C36 C28 C (3) H7W O13 H8W (8) C30 C29 C (3) H9W O14 H10W (8) C30 C29 H29A H11W O15 H12W (8) sup-10

14 C28 C29 H29A N6 Fe1 N1 C (3) Fe1 N5 C25 C (2) N2 Fe1 N1 C (3) N5 C25 C26 C (5) N5 Fe1 N1 C (10) C25 C26 C27 C (5) N4 Fe1 N1 C (3) C26 C27 C28 C (5) N3 Fe1 N1 C (3) C26 C27 C28 C (3) N6 Fe1 N1 C (2) C27 C28 C29 C (3) N2 Fe1 N1 C (2) C36 C28 C29 C (5) N5 Fe1 N1 C (11) C28 C29 C30 C (5) N4 Fe1 N1 C (2) C29 C30 C31 C (3) N3 Fe1 N1 C (2) C29 C30 C31 C (5) C12 N1 C1 C2 1.0 (4) C35 C31 C32 C (5) Fe1 N1 C1 C (2) C30 C31 C32 C (3) N1 C1 C2 C3 1.0 (5) C31 C32 C33 C (5) C1 C2 C3 C4 1.0 (5) C32 C33 C34 N6 0.4 (5) C2 C3 C4 C (5) C33 C34 N6 C (5) C2 C3 C4 C (3) C33 C34 N6 Fe (2) C12 C4 C5 C6 1.5 (5) N2 Fe1 N6 C (3) C3 C4 C5 C (3) N5 Fe1 N6 C (3) C4 C5 C6 C7 1.9 (5) N1 Fe1 N6 C (3) C5 C6 C7 C (5) N4 Fe1 N6 C (3) C5 C6 C7 C (3) N3 Fe1 N6 C (8) C11 C7 C8 C9 1.4 (5) N2 Fe1 N6 C (2) C6 C7 C8 C (3) N5 Fe1 N6 C (2) C7 C8 C9 C (5) N1 Fe1 N6 C (2) C8 C9 C10 N2 0.0 (5) N4 Fe1 N6 C (2) C9 C10 N2 C (5) N3 Fe1 N6 C (10) C9 C10 N2 Fe (2) C34 N6 C35 C (5) N6 Fe1 N2 C (3) Fe1 N6 C35 C (2) N5 Fe1 N2 C (3) C34 N6 C35 C (3) N1 Fe1 N2 C (3) Fe1 N6 C35 C (3) N4 Fe1 N2 C (11) C32 C31 C35 N6 0.0 (5) N3 Fe1 N2 C (3) C30 C31 C35 N (3) N6 Fe1 N2 C (2) C32 C31 C35 C (3) N5 Fe1 N2 C (2) C30 C31 C35 C (5) N1 Fe1 N2 C (2) C25 N5 C36 C (4) N4 Fe1 N2 C (12) Fe1 N5 C36 C (3) N3 Fe1 N2 C (2) C25 N5 C36 C (3) C10 N2 C11 C7 2.4 (5) Fe1 N5 C36 C (3) Fe1 N2 C11 C (3) C27 C28 C36 N5 2.1 (5) C10 N2 C11 C (3) C29 C28 C36 N (3) Fe1 N2 C11 C (3) C27 C28 C36 C (3) C8 C7 C11 N2 0.7 (5) C29 C28 C36 C (5) C6 C7 C11 N (3) N6 C35 C36 N5 1.2 (4) C8 C7 C11 C (3) C31 C35 C36 N (3) C6 C7 C11 C (5) N6 C35 C36 C (3) C1 N1 C12 C4 3.1 (5) C31 C35 C36 C (5) sup-11

15 Fe1 N1 C12 C (2) S1 N7 C37 O (3) C1 N1 C12 C (3) S1 N7 C37 C (4) Fe1 N1 C12 C (3) O1 C37 C38 C (5) C3 C4 C12 N1 3.0 (5) N7 C37 C38 C (3) C5 C4 C12 N (3) O1 C37 C38 C (3) C3 C4 C12 C (3) N7 C37 C38 C (4) C5 C4 C12 C (5) C43 C38 C39 C (5) N2 C11 C12 N1 2.5 (4) C37 C38 C39 C (3) C7 C11 C12 N (3) C38 C39 C40 C (5) N2 C11 C12 C (3) C39 C40 C41 C (5) C7 C11 C12 C4 2.7 (5) C40 C41 C42 C (5) N6 Fe1 N3 C (8) C41 C42 C43 C (5) N2 Fe1 N3 C (3) C41 C42 C43 S (3) N5 Fe1 N3 C (3) C39 C38 C43 C (5) N1 Fe1 N3 C (3) C37 C38 C43 C (3) N4 Fe1 N3 C (3) C39 C38 C43 S (2) N6 Fe1 N3 C (10) C37 C38 C43 S1 3.6 (3) N2 Fe1 N3 C (2) C37 N7 S1 O (2) N5 Fe1 N3 C (2) C37 N7 S1 O (2) N1 Fe1 N3 C (2) C37 N7 S1 C (3) N4 Fe1 N3 C (2) C42 C43 S1 O (4) C24 N3 C13 C (5) C38 C43 S1 O (2) Fe1 N3 C13 C (2) C42 C43 S1 O (4) N3 C13 C14 C (5) C38 C43 S1 O (2) C13 C14 C15 C (5) C42 C43 S1 N (3) C14 C15 C16 C (5) C38 C43 S1 N7 2.5 (3) C14 C15 C16 C (3) S2 N8 C44 O (3) C24 C16 C17 C (5) S2 N8 C44 C (4) C15 C16 C17 C (3) O4 C44 C45 C (6) C16 C17 C18 C (5) N8 C44 C45 C (3) C17 C18 C19 C (3) O4 C44 C45 C (3) C17 C18 C19 C (5) N8 C44 C45 C (4) C23 C19 C20 C (5) C50 C45 C46 C (5) C18 C19 C20 C (3) C44 C45 C46 C (3) C19 C20 C21 C (5) C45 C46 C47 C (5) C20 C21 C22 N4 0.7 (5) C46 C47 C48 C (5) C21 C22 N4 C (5) C47 C48 C49 C (5) C21 C22 N4 Fe (2) C48 C49 C50 C (5) N6 Fe1 N4 C (3) C48 C49 C50 S (3) N2 Fe1 N4 C (10) C46 C45 C50 C (5) N5 Fe1 N4 C (3) C44 C45 C50 C (3) N1 Fe1 N4 C (3) C46 C45 C50 S (3) N3 Fe1 N4 C (3) C44 C45 C50 S2 2.2 (3) N6 Fe1 N4 C (2) C44 N8 S2 O (3) N2 Fe1 N4 C (12) C44 N8 S2 O (3) N5 Fe1 N4 C (2) C44 N8 S2 C (3) N1 Fe1 N4 C (2) C49 C50 S2 O (3) N3 Fe1 N4 C (2) C45 C50 S2 O (2) sup-12

16 C22 N4 C23 C (4) C49 C50 S2 O (3) Fe1 N4 C23 C (2) C45 C50 S2 O (2) C22 N4 C23 C (3) C49 C50 S2 N (3) Fe1 N4 C23 C (3) C45 C50 S2 N8 1.7 (3) C20 C19 C23 N4 0.5 (5) S3 N9 C51 O (3) C18 C19 C23 N (3) S3 N9 C51 C (4) C20 C19 C23 C (3) O7 C51 C52 C (3) C18 C19 C23 C (4) N9 C51 C52 C (4) C13 N3 C24 C (4) O7 C51 C52 C (5) Fe1 N3 C24 C (2) N9 C51 C52 C (3) C13 N3 C24 C (3) C57 C52 C53 C (5) Fe1 N3 C24 C (3) C51 C52 C53 C (3) C15 C16 C24 N3 1.3 (5) C52 C53 C54 C (5) C17 C16 C24 N (3) C53 C54 C55 C (5) C15 C16 C24 C (3) C54 C55 C56 C (5) C17 C16 C24 C (4) C55 C56 C57 C (5) N4 C23 C24 N3 1.0 (4) C55 C56 C57 S (3) C19 C23 C24 N (3) C53 C52 C57 C (5) N4 C23 C24 C (3) C51 C52 C57 C (3) C19 C23 C24 C (4) C53 C52 C57 S (2) N6 Fe1 N5 C (3) C51 C52 C57 S3 1.8 (3) N2 Fe1 N5 C (3) C51 N9 S3 O (2) N1 Fe1 N5 C (10) C51 N9 S3 O (2) N4 Fe1 N5 C (3) C51 N9 S3 C (3) N3 Fe1 N5 C (3) C56 C57 S3 O (3) N6 Fe1 N5 C (2) C52 C57 S3 O (2) N2 Fe1 N5 C (2) C56 C57 S3 O (3) N1 Fe1 N5 C (11) C52 C57 S3 O (2) N4 Fe1 N5 C (2) C56 C57 S3 N (3) N3 Fe1 N5 C (2) C52 C57 S3 N9 3.0 (2) C36 N5 C25 C (5) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A N8 H8N O (5) 1.70 (5) (4) 174 (4) O10 H1W O (4) 2.19 (2) (4) 148 (4) O10 H2W O13 i 0.90 (3) 1.87 (3) (4) 171 (5) O11 H3W O (3) 1.87 (4) (4) 161 (5) O11 H4W O (3) 1.85 (3) (3) 174 (4) O12 H5W N7 ii 0.90 (3) 2.70 (2) (5) 157 (5) O12 H6W O9 iii 0.90 (3) 2.13 (4) (4) 146 (5) O13 H7W O (3) 1.85 (2) (4) 164 (4) O13 H8W O14 iv 0.90 (3) 1.95 (2) (5) 163 (5) O14 H9W O7 v 0.90 (3) 1.84 (3) (4) 176 (4) O14 H10W O (3) 1.97 (2) (4) 157 (5) sup-13

17 O15 H11W O (3) 2.02 (2) (4) 176 (3) O15 H12W O12 vi 0.90 (3) 1.92 (2) (4) 161 (4) Symmetry codes: (i) x+1, y, z+2; (ii) x+1, y, z+1; (iii) x+1/2, y+1/2, z 1/2; (iv) x+1/2, y 1/2, z+3/2; (v) x 1/2, y+1/2, z 1/2; (vi) x 1/2, y+1/2, z+1/2. sup-14