metal-organic papers Aquaoxobis(quinoline-2-carboxylato-N,O)- vanadium(iv) ethanol hemisolvate Comment

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1 metal-organic papers Acta Crystallographica Section E Structure Reports Online ISSN Aquaoxobis(quinoline-2-carboxylato-N,O)- vanadium(iv) ethanol hemisolvate Nobuo Okabe* and Yasunori Muranishi Faculty of Pharmaceutical Sciences, Kinki University, Kowakae 3-4-1, Higashiosaka, Osaka , Japan Correspondence okabe@phar.kindai.ac.jp Key indicators Single-crystal X-ray study T = 296 K Mean (C±C) = AÊ R factor = wr factor = Data-to-parameter ratio = 15.9 For details of how these key indicators were automatically derived from the article, see The title compound, [VO(C 10 H 6 NO 2 ) 2 (H 2 O)] 2 C 2 H 5 OH, contains six-coordinate V IV atoms. The central V IV atom in each of the two crystallographically independent molecules has a distorted octahedral coordination geometry, involving O atoms of the oxo and aqua ligands, together with two O and two N atoms of two organic ligands. Comment Quinoline-2-carboxylic acid, a tryptophan metabolite, forms complexes with various transition metals (Martell & Smith, 1974). Crystal structures have been determined for the Cu II (Haendler, 1986), Mn II (Haendler, 1996; Okabe & Koizumi, 1997), Fe II (Okabe & Makino, 1998), Co II (Okabe & Makino, 1999) and Ni II complexes (Odoko et al., 2001). Vanadate ions have an insulin-mimetic effect in living animals (Bhattacharyya & Tracey, 2001) and in intact cell systems (Kanamori et al., 2001; Sasagawa et al., 2002). Therefore, we aimed to prepare complexes of quinoline-2-carboxylic acid and vanadium and determine their structures. We have characterized the title oxovanadium(iv) complex, (I). Received 29 April 2002 Accepted 13 May 2002 Online 17 May 2002 # 2002 International Union of Crystallography Printed in Great Britain ± all rights reserved The molecular structure of (I) is shown in Fig. 1. There are two independent complex molecules in the asymmetric unit, with similar structures. In the complex, two organic ligand molecules and one water molecule coordinate to the oxovanadium(iv) centre. The central V IV atom has a distorted octahedral coordination geometry, involving the O atoms of oxo and aqua ligands, together with two O and two N atoms of the quinoline-2-carboxylate ligands. The carboxyl groups of the ligands are ionized and are essentially coplanar with the quinoline ring planes, as shown by relevant torsion angles [O2AÐC11AÐC2AÐN1A 2.4 (9), O2BÐC11BÐC2BÐ Acta Cryst. (2002). E58, m287±m289 DOI: /S Okabe and Muranishi [VO(C 10 H 6 NO 2 ) 2 (H 2 O)] 2 C 2 H 5 OH m287

2 metal-organic papers Re nement Re nement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = re ections 550 parameters H-atom parameters not re ned w = 1/[ 2 (F o 2 ) + (0.081P) 2 ] where P =(F o 2 +2F c 2 )/3 (/) max = max = 0.87 e A Ê 3 min = 0.91 e A Ê 3 Table 1 Selected geometric parameters (A Ê, ). V1AÐO1VA (6) V1AÐO2A (5) V1AÐO2B (6) V1AÐO2VA (5) V1AÐN1A (7) V1AÐN1B (7) V1BÐO1VB (5) V1BÐO2C (6) V1BÐO2D (5) V1BÐO2VB (5) V1BÐN1C (7) V1BÐN1D (6) Figure 1 ORTEPII (Johnson, 1976) drawing of the asymmetric unit of the title compound, with the atomic numbering scheme. Ellipsoids correspond to 50% probability. N1B 1 (1),O2CÐC11CÐC2CÐN1C 5.0 (9) and O2DÐ C11DÐC2DÐN1D 2 (1) ]. The quinoline-2-carboxylate ligands and the central V IV form ve-membered chelate rings. Such coplanarity and ve-membered ring formation are usually present in metal compounds of quinoline-2-carboxylic acid (Okabe & Makino, 1999). Planar ve-membered rings with similar bond lengths and angles are also found in a vanadium(iii) complex with picolinic acid (pyridine-2- carboxylic acid), [V III (pic) 3 ]H 2 O (Chatterjee et al., 1997), which has a similar coordination geometry. Experimental The green prism crystal of (I) used for X-ray analysis was obtained by slow evaporation from a 4:1 mixture of quinoline-2-carboxylic acid dissolved in ethanol and VOSO 4 dissolved in a small amount of water. Crystal data [VO(C 10 H 6 NO 2 ) 2 (H 2 O)] 2 C 2 H 5 OH M r = Triclinic, P1 a = (3) A Ê b = (6) A Ê c = (2) A Ê = (2) = (2) = (3) V = (10) A Ê 3 Data collection Rigaku AFC-5R diffractometer!±2 scans Absorption correction: scan (North et al., 1968) T min = 0.945, T max = measured re ections 8754 independent re ections 2975 re ections with I > 2(I) Z =2 D x = Mg m 3 Mo K radiation Cell parameters from 25 re ections = 10.5±13.0 = 0.57 mm 1 T = K Prism, green mm R int = max = 27.5 h =0! 15 k = 21! 21 l = 13! 13 3 standard re ections every 150 re ections intensity decay: 0.3% O1VAÐV1AÐO2A (3) O1VAÐV1AÐO2B (3) O1VAÐV1AÐO2VA (2) O1VAÐV1AÐN1A 93.4 (3) O1VAÐV1AÐN1B 94.9 (3) O2AÐV1AÐO2B (2) O2AÐV1AÐO2VA 78.1 (2) O2AÐV1AÐN1A 78.2 (2) O2AÐV1AÐN1B 97.7 (2) O2BÐV1AÐO2VA 76.0 (2) O2BÐV1AÐN1A (3) O2BÐV1AÐN1B 78.1 (3) O2VAÐV1AÐN1A 84.9 (2) O2VAÐV1AÐN1B 86.9 (2) N1AÐV1AÐN1B (2) O1VBÐV1BÐO2C (3) O1VBÐV1BÐO2D (3) O1VBÐV1BÐO2VB (3) O1VBÐV1BÐN1C 94.0 (3) O1VBÐV1BÐN1D 93.9 (3) O2CÐV1BÐO2D (2) O2CÐV1BÐO2VB 79.2 (2) O2CÐV1BÐN1C 78.7 (2) O2CÐV1BÐN1D 95.5 (2) O2DÐV1BÐO2VB 76.0 (2) O2DÐV1BÐN1C (2) O2DÐV1BÐN1D 78.9 (2) O2VBÐV1BÐN1C 86.5 (2) O2VBÐV1BÐN1D 85.8 (2) N1CÐV1BÐN1D (2) V1AÐO2AÐC11A (4) V1AÐO2BÐC11B (5) V1BÐO2CÐC11C (5) V1BÐO2DÐC11D (5) V1AÐN1AÐC2A (5) V1AÐN1AÐC10A (6) V1AÐN1BÐC2B (5) V1AÐN1BÐC10B (5) V1BÐN1CÐC2C (5) V1BÐN1CÐC10C (5) V1BÐN1DÐC2D (6) V1BÐN1DÐC10D (5) H atoms, located from a difference map, were included in idealized positions (except for those on H 2 O) and then xed. Data collection: MSC/AFC Diffractometer Control Software (Molecular Structure Corporation & Rigaku Corporation, 1999); cell re nement: MSC/AFC Diffractometer Control Software; data reduction: TEXSAN (Molecular Structure Corporation & Rigaku Corporation, 1999); program(s) used to solve structure: SIR97 (Altomare et al., 1999) and DIRDIF94 (Beurskens et al., 1992); program(s) used to re ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEPII (Johnson, 1976); software used to prepare material for publication: TEXSAN. References Altomare, A., Burla, M. C., Camalli, M., Cascarano, G., Giacovazzo, C., Guagliardi, A., Moliterni, A. G. G., Polidori, G. & Spagna, R. (1999). J. Appl. Cryst. 32, 115±119. Beurskens, P. T., Admiraal, G., Beurskens, G., Bosman, W. P., Garcia-Granda, S., Gould, R. O., Smits, J. M. M. & Smykalla, C. (1992). The DIRDIF Program System. Technical Report. Crystallography Laboratory, University of Nijmegen, The Netherlands. Bhattacharyya, S. & Tracey, A. S. (2001). J. Inorg. Biochem. 85, 9±13. Chatterjee, M., Ghosh, S. & Nandi, A. K. (1997). Polyhedron, 16, 2917±2923. Haendler, H. M. (1986). Acta Cryst. C42, 147±149. Haendler, H. M. (1996). Acta Cryst. C52, 801±803. Johnson, C. K. (1976). ORTEPII. Report ORNL Oak Ridge National Laboratory, Tennessee, USA. Kanamori, K., Nishida, K., Miyata, N., Okamoto, K., Miyoshi, Y., Tamura, A. & Sakurai, H. (2001). J. Inorg. Biochem. 86, 649±656. m288 Okabe and Muranishi [VO(C 10 H 6 NO 2 ) 2 (H 2 O)] 2 C 2 H 5 OH Acta Cryst. (2002). E58, m287±m289

3 metal-organic papers Martell, A. E. & Smith, R. M. (1974). Critical Stability Constants, Vol. 1, pp. 78 and 372, Vol. 2, p New York: Plenum Press. Molecular Structure Corporation & Rigaku Corporation (1999). MSC/AFC Diffractometer Control Software and TEXSAN (Version 1.10). MSC, 9009 New Trails Drive, The Woodlands, TX , USA, and Rigaku Corporation, Akishima, Tokyo, Japan. North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351± 359. Okabe, N. & Koizumi, M.(1997). Acta Cryst. C53, 852±854. Okabe, N. & Makino, T. (1998). Acta Cryst. C54, 1279±1280. Okabe, N. & Makino, T. (1999). Acta Cryst. C55, 300±302. Odoko, M., Muranishi, Y. & Okabe, N. (2001). Acta Cryst. E57, m267±m269. Sasagawa, T., Yoshikawa, Y., Kawabe, K., Sakurai, H. & Kojima, Y. (2002). J. Inorg. Biochem. 88, 108±112. Sheldrick, G. M. (1997). SHELXL97. University of GoÈttingen, Germany. Acta Cryst. (2002). E58, m287±m289 Okabe and Muranishi [VO(C 10 H 6 NO 2 ) 2 (H 2 O)] 2 C 2 H 5 OH m289

4 supporting information [doi: /s ] Aquaoxobis(quinoline-2-carboxylato-N,O)vanadium(IV) ethanol hemisolvate Nobuo Okabe and Yasunori Muranishi S1. Comment Quinoline-2-carboxylic acid, a tryptophan metabolite, forms complexes with various transition metals (Martell & Smith, 1974). Crystal strutures have been determined for the Cu II (Haendler, 1986), Mn II (Haendler, 1996; Okabe & Koizumi, 1997), Fe II (Okabe & Makino, 1998) and Co II (Okabe & Makino, 1999) and Ni II complexes (Odoko et al., 2001). Vanadate ions have an insulin-mimetic effect in living animals (Bhattacharyya & Tracey, 2001) and in intact cell systems (Kanamori et al., 2001; Sasagawa et al., 2002). Therefore, we aimed to prepare complexes of quinoline-2-carboxylic acid and vanadium and determine their structures. We have characterized the title oxovanadium(iv) complex, (I). The molecular structure of (I) is shown in Fig. 1. There are two independent complex molecules in the asymmetric unit, with similar structures. In the complex, two organic ligand molecules and one water molecule coordinate to the oxovanadium(iv) centre. The central V IV atom has a distorted octahedral coordination geometry, involving the O atoms of oxo and aqua ligands, together with two O and two N atoms of the quinoline-2-carboxylate ligands. The carboxyl groups of the ligands are ionized and are essentially coplanar with the quinoline ring planes, as shown by relevant torsion angles [O2A C11A C2A N1A 2.4 (9), O2B C11B C2B N1B -1(1), O2C C11C C2C N1C -5.0 (9) and O2D C11D C2D N1D -2(1) ]. The quinoline-2-carboxylate ligands and the central V IV form five-membered chelate rings. Such coplanarity and five-membered ring formation are usually present in metal compounds of quinoline-2-carboxylic acid (Okabe & Makino, 1999). Planar five-membered rings with similar bond lengths and angles are also found in a vanadium(iii) complex with picolinic acid (pyridine-2-carboxylic acid), [V III (pic) 3 ] H 2 O (Chatterjee et al., 1997), which has a similar coordination geometry. S2. Experimental The green prism crystal of (I) used for X-ray analysis was obtained by slow evaporation from a 4:1 mixture of quinoline-2-carboxylic acid dissolved in ethanol and VOSO 4 dissolved in a small amount of water. S3. Refinement H atoms, located from a difference map, were included in idealized positions (except for those on H 2 O) and then fixed. sup-1

5 Figure 1 ORTEPII (Johnson, 1976) drawing of the title compound with the atomic numbering scheme. Ellipsoids correspond to 50% probability. (I) Crystal data [VO(C 10 H 6 NO 2 ) 2 (H 2 O)] 2 C 2 H 5 OH M r = Triclinic, P1 Hall symbol: -P 1 a = (3) Å b = (6) Å c = (2) Å α = (2) β = (2) γ = (3) V = (10) Å 3 Z = 2 F(000) = D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 25 reflections θ = µ = 0.57 mm 1 T = 296 K Prism, green mm sup-2

6 Data collection Rigaku AFC-5R diffractometer ω 2θ scans Absorption correction: ψ scan (North et al., 1968) T min = 0.945, T max = measured reflections 8754 independent reflections 2975 reflections with I > 2σ(I) R int = θ max = 27.5 h = 0 15 k = l = standard reflections every 150 reflections intensity decay: 0.3% Refinement Refinement on F 2 R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 550 parameters H-atom parameters not refined w = 1/[σ 2 (F o2 ) + (0.081P) 2 ] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.87 e Å 3 Δρ min = 0.91 e Å 3 Special details Refinement. Refinement using reflections with F 2 > σ(f 2 ). The weighted R-factor (wr) and goodness of fit (S) are based on F 2. R-factor (gt) are based on F. The threshold expression of F 2 > 2.0 σ(f 2 ) is used only for calculating R-factor (gt). Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq V1A (1) (8) (1) (4) V1B (1) (9) (1) (4) O1A (4) (4) (6) (1) O1B (5) (4) (7) (2) O1C (5) (4) (6) (2) O1D (4) (4) (6) (1) O1E (6) (6) (8) (3) O1VB (4) (4) (5) (1) O1VA (5) (3) (6) (1) O2A (4) (3) (5) (1) O2B (4) (4) (6) (1) O2C (4) (3) (5) (1) O2D (4) (3) (5) (1) O2VA (4) (3) (5) (1) O2VB (4) (3) (5) (1) N1A (5) (4) (6) (1) N1B (5) (4) (6) (2) N1C (5) (4) (6) (2) N1D (5) (4) (6) (1) C1E (1) (1) (1) (6) C2A (6) (5) (7) (2) C2B (6) (5) (8) (2) C2C (6) (5) (7) (2) C2D (6) (5) (8) (2) sup-3

7 C2E (1) (2) (2) 0.25 (2) C3A (7) (5) (8) (2) C3B (7) (5) (9) (2) C3C (6) (6) (8) (2) C3D (7) (6) (9) (2) C4A (7) (5) (8) (2) C4B (7) (5) (9) (2) C4C (7) (6) (9) (2) C4D (9) (6) (10) (3) C5A (7) (5) (8) (2) C5B (7) (5) (8) (2) C5C (6) (5) (8) (2) C5D (9) (5) (8) (2) C6A (8) (5) (9) (2) C6B (8) (5) (9) (2) C6C (7) (5) (8) (2) C6D (1) (6) (1) (3) C7A (7) (6) (8) (2) C7B (7) (6) (9) (2) C7C (8) (5) (9) (2) C7D (1) (8) (1) (3) C8A (7) (6) (9) (2) C8B (7) (6) (9) (2) C8C (7) (5) (9) (2) C8D (9) (7) (10) (3) C9A (7) (6) (9) (2) C9B (7) (5) (8) (2) C9C (6) (5) (8) (2) C9D (8) (6) (9) (2) C10A (6) (5) (7) (2) C10B (7) (5) (8) (2) C10C (6) (5) (7) (2) C10D (7) (5) (8) (2) C11A (6) (5) (8) (2) C11B (7) (6) (9) (2) C11C (6) (5) (7) (2) C11D (6) (5) (8) (2) H1E * H1E * H1E * H1E * H1W * H2E * H2E * H2W * H3A * H3B * H3C * sup-4

8 H3D * H3W * H4A * H4B * H4C * H4D * H4W * H6A * H6B * H6C * H6D * H7A * H7B * H7C * H7D * H8A * H8B * H8C * H8D * H9A * H9B * H9C * H9D * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 V1A (7) (8) (9) (6) (6) (7) V1B (7) (8) (9) (6) (6) (7) O1A (3) (4) (4) (3) (3) (3) O1B (3) (4) (5) (3) (3) (4) O1C (3) (4) (4) (3) (3) (3) O1D (3) (4) (4) (3) (3) (3) O1E (4) (8) (5) (4) (4) (5) O1VB (3) (4) (3) (3) (3) (3) O1VA (4) (4) (4) (3) (3) (3) O2A (3) (3) (4) (2) (2) (3) O2B (3) (4) (4) (3) (3) (3) O2C (3) (3) (4) (2) (3) (3) O2D (3) (3) (4) (3) (3) (3) O2VA (3) (4) (3) (3) (3) (3) O2VB (3) (4) (3) (3) (2) (3) N1A (3) (4) (4) (3) (3) (3) N1B (4) (4) (4) (3) (3) (3) N1C (3) (4) (4) (3) (3) (3) N1D (3) (4) (4) (3) (3) (3) C1E 0.10 (1) 0.24 (2) 0.10 (1) 0.09 (1) (9) 0.09 (1) C2A (4) (5) (4) (3) (3) (4) sup-5

9 C2B (4) (5) (5) (4) (3) (4) C2C (4) (5) (4) (3) (3) (4) C2D (4) (5) (5) (4) (4) (4) C2E 0.09 (1) 0.56 (4) 0.06 (1) 0.15 (2) (9) 0.00 (2) C3A (4) (5) (5) (4) (4) (4) C3B (5) (5) (6) (4) (4) (4) C3C (4) (6) (5) (4) (3) (4) C3D (5) (6) (7) (4) (5) (5) C4A (5) (4) (5) (4) (4) (4) C4B (5) (4) (6) (4) (4) (4) C4C (4) (5) (6) (4) (4) (5) C4D (7) (6) (7) (5) (5) (5) C5A (5) (4) (5) (4) (4) (4) C5B (5) (5) (5) (4) (4) (4) C5C (4) (5) (5) (4) (3) (4) C5D (7) (5) (5) (5) (5) (4) C6A (5) (5) (6) (4) (4) (4) C6B (5) (5) (6) (4) (4) (4) C6C (5) (5) (5) (4) (4) (4) C6D (8) (6) (7) (6) (6) (5) C7A (5) (6) (6) (4) (4) (4) C7B (5) (6) (5) (4) (4) (5) C7C (6) (5) (5) (4) (4) (4) C7D (10) (8) (7) (7) (6) (6) C8A (4) (6) (6) (4) (4) (5) C8B (5) (6) (6) (4) (4) (5) C8C (5) (5) (6) (4) (4) (4) C8D (7) (8) (7) (6) (5) (6) C9A (5) (6) (5) (4) (4) (4) C9B (5) (5) (5) (4) (4) (4) C9C (4) (5) (5) (4) (4) (4) C9D (5) (6) (6) (5) (4) (5) C10A (4) (4) (4) (3) (3) (3) C10B (4) (4) (5) (4) (4) (4) C10C (4) (4) (4) (3) (3) (3) C10D (5) (5) (5) (4) (4) (4) C11A (4) (5) (5) (3) (3) (4) C11B (4) (6) (6) (4) (4) (5) C11C (4) (5) (4) (4) (3) (4) C11D (4) (5) (5) (3) (3) (4) Geometric parameters (Å, º) V1A O1VA (6) C3C C4C 1.35 (1) V1A O2A (5) C3C H3C V1A O2B (6) C3D C4D 1.31 (2) V1A O2VA (5) C3D H3D V1A N1A (7) C4A C5A 1.40 (1) sup-6

10 V1A N1B (7) C4A H4A V1B O1VB (5) C4B C5B 1.41 (1) V1B O2C (6) C4B H4B V1B O2D (5) C4C C5C 1.40 (1) V1B O2VB (5) C4C H4C V1B N1C (7) C4D C5D 1.40 (1) V1B N1D (6) C4D H4D O1A C11A (10) C5A C6A 1.42 (1) O1B C11B 1.20 (1) C5A C10A 1.42 (1) O1C C11C (10) C5B C6B 1.42 (1) O1D C11D (9) C5B C10B 1.37 (1) O1E C2E 1.34 (2) C5C C6C 1.40 (1) O1E H1E C5C C10C 1.41 (1) O2A C11A 1.31 (1) C5D C6D 1.43 (2) O2B C11B 1.30 (1) C5D C10D 1.42 (1) O2C C11C (10) C6A C7A 1.35 (1) O2D C11D (9) C6A H6A O2VA H1W C6B C7B 1.33 (1) O2VA H2W C6B H6B O2VB H3W C6C C7C 1.35 (1) O2VB H4W C6C H6C N1A C2A 1.34 (1) C6D C7D 1.37 (2) N1A C10A (8) C6D H6D N1B C2B 1.32 (1) C7A C8A 1.37 (1) N1B C10B (10) C7A H7A N1C C2C (10) C7B C8B 1.37 (1) N1C C10C 1.39 (1) C7B H7B N1D C2D (9) C7C C8C 1.41 (1) N1D C10D 1.37 (1) C7C H7C C1E C2E 1.26 (3) C7D C8D 1.38 (2) C1E H1E C7D H7D C1E H1E C8A C9A 1.36 (1) C1E H1E C8A H8A C2A C3A 1.38 (1) C8B C9B 1.36 (1) C2A C11A (10) C8B H8B C2B C3B 1.38 (1) C8C C9C 1.34 (1) C2B C11B 1.51 (1) C8C H8C C2C C3C 1.40 (1) C8D C9D 1.34 (2) C2C C11C 1.53 (1) C8D H8D C2D C3D 1.40 (1) C9A C10A 1.41 (1) C2D C11D 1.51 (1) C9A H9A C2E H2E C9B C10B 1.42 (1) C2E H2E C9B H9B C3A C4A 1.35 (1) C9C C10C 1.40 (1) C3A H3A C9C H9C C3B C4B 1.38 (1) C9D C10D 1.43 (1) C3B H3B C9D H9D sup-7

11 O1A O2VB i (6) C5A C8A i 3.54 (1) O1A C11D i (9) C5B C10B xi 3.48 (1) O1A O1D i (8) C5B C9C iv 3.49 (1) O1A C2D i 3.24 (1) C5B C5B xi 3.50 (2) O1A C3D i 3.56 (1) C5B C10C iv 3.51 (1) O1B O1C ii 3.26 (1) C5B C9B xi (10) O1B C3C ii (10) C5B C6B xi 3.56 (1) O1B C3B iii 3.50 (1) C5C C11C v 3.47 (1) O1B C4C iv 3.51 (1) C6A C10A i 3.41 (1) O1C O2VA ii (8) C6A C9A i 3.57 (1) O1C C11B ii 3.31 (1) C6B C10B xi 3.27 (1) O1C O2B ii (8) C6B C9C iv 3.47 (1) O1C C6C v 3.47 (1) C6C C11C v 3.56 (1) O1C C6A vi 3.54 (1) C7A C10A i 3.58 (1) O1C C7C v 3.57 (1) C7C C10B x 3.52 (1) O1D O2VA i (9) C7C C9B x 3.53 (1) O1D C11A i (9) C7D C8A xii 3.43 (1) O1D C7C vii 3.27 (1) C7D C10A vi 3.53 (1) O1D C8C vii (10) C11A C11D i 3.48 (1) O1D O2A i (8) C2A C5A (10) O1D C2A i (8) C2A C6D ix 3.55 (1) O1E O2VB ii (9) C2B C5B 2.73 (1) O1E C11C ii (10) C2B C5C iv 3.47 (1) O1E C4A i 3.55 (1) C2B C4C iv 3.51 (1) O1VB C4C v (9) C2C C5C 2.74 (1) O1VB C3C v (8) C2D C5D 2.71 (1) O1VB C8B viii 3.51 (1) C3A C5D ix 3.50 (1) O1VA C7D ix 3.20 (1) C3B C4C iv 3.38 (1) O1VA C6D ix 3.23 (1) C3B C5C iv 3.45 (1) O1VA C6C iv 3.36 (1) C4A C8A i 3.40 (1) O1VA C7C iv 3.46 (1) C4B C8B xi 3.35 (1) O2C C6A vi 3.58 (1) C4B C9B xi 3.55 (1) O2VB C2E ii 3.54 (2) C4D C6D 2.51 (2) O2VB C4B x 3.56 (1) C5A C8A 2.79 (1) N1A C6D ix 3.59 (1) C5A C9D ix 3.52 (1) N1B C6C iv 3.43 (1) C5A C8D ix 3.54 (1) N1B C6B xi (10) C5A C8A i 3.54 (1) N1C C4B x 3.53 (1) C5B C8B 2.76 (1) C2A C6D ix 3.55 (1) C5B C9C iv 3.49 (1) C2B C5C iv 3.47 (1) C5B C5B xi 3.50 (2) C2B C4C iv 3.51 (1) C5B C9B xi (10) C3A C5D ix 3.50 (1) C5B C6B xi 3.56 (1) C3B C4C iv 3.38 (1) C5C C8C 2.78 (1) C3B C5C iv 3.45 (1) C5D C8D 2.81 (1) C4A C8A i 3.40 (1) C6A C9A 2.77 (1) C4A C10D ix 3.48 (1) C6A C9A i 3.57 (1) C4B C8B xi 3.35 (1) C6B C9B 2.76 (1) C4B C10C iv 3.38 (1) C6B C9C iv 3.47 (1) sup-8

12 C4B C9B xi 3.55 (1) C6C C9C 2.77 (1) C4C C11B x 3.57 (1) C6D C9D 2.79 (1) C5A C9D ix 3.52 (1) C7C C9B x 3.53 (1) C5A C8D ix 3.54 (1) C7D C8A xii 3.43 (1) O1VA V1A O2A (3) C3B C4B H4B O1VA V1A O2B (3) C5B C4B H4B O1VA V1A O2VA (2) C3C C4C C5C (8) O1VA V1A N1A 93.4 (3) C3C C4C H4C O1VA V1A N1B 94.9 (3) C5C C4C H4C O2A V1A O2B (2) C3D C4D C5D (8) O2A V1A O2VA 78.1 (2) C3D C4D H4D O2A V1A N1A 78.2 (2) C5D C4D H4D O2A V1A N1B 97.7 (2) C4A C5A C6A (8) O2B V1A O2VA 76.0 (2) C4A C5A C10A (6) O2B V1A N1A (3) C6A C5A C10A (8) O2B V1A N1B 78.1 (3) C4B C5B C6B (8) O2VA V1A N1A 84.9 (2) C4B C5B C10B (7) O2VA V1A N1B 86.9 (2) C6B C5B C10B (8) N1A V1A N1B (2) C4C C5C C6C (8) O1VB V1B O2C (3) C4C C5C C10C (8) O1VB V1B O2D (3) C6C C5C C10C (7) O1VB V1B O2VB (3) C4D C5D C6D (8) O1VB V1B N1C 94.0 (3) C4D C5D C10D (9) O1VB V1B N1D 93.9 (3) C6D C5D C10D (9) O2C V1B O2D (2) C5A C6A C7A (8) O2C V1B O2VB 79.2 (2) C5A C6A H6A O2C V1B N1C 78.7 (2) C7A C6A H6A O2C V1B N1D 95.5 (2) C5B C6B C7B (8) O2D V1B O2VB 76.0 (2) C5B C6B H6B O2D V1B N1C (2) C7B C6B H6B O2D V1B N1D 78.9 (2) C5C C6C C7C (8) O2VB V1B N1C 86.5 (2) C5C C6C H6C O2VB V1B N1D 85.8 (2) C7C C6C H6C N1C V1B N1D (2) C5D C6D C7D (9) C2E O1E H1E C5D C6D H6D V1A O2A C11A (4) C7D C6D H6D V1A O2B C11B (5) C6A C7A C8A (7) V1B O2C C11C (5) C6A C7A H7A V1B O2D C11D (5) C8A C7A H7A V1A O2VA H1W C6B C7B C8B (8) V1A O2VA H2W C6B C7B H7B H1W O2VA H2W 95.5 C8B C7B H7B V1B O2VB H3W C6C C7C C8C (8) V1B O2VB H4W C6C C7C H7C H3W O2VB H4W 94.8 C8C C7C H7C V1A N1A C2A (5) C6D C7D C8D 121 (1) V1A N1A C10A (6) C6D C7D H7D sup-9

13 C2A N1A C10A (7) C8D C7D H7D V1A N1B C2B (5) C7A C8A C9A (9) V1A N1B C10B (5) C7A C8A H8A C2B N1B C10B (7) C9A C8A H8A V1B N1C C2C (5) C7B C8B C9B (8) V1B N1C C10C (5) C7B C8B H8B C2C N1C C10C (6) C9B C8B H8B V1B N1D C2D (6) C7C C8C C9C (8) V1B N1D C10D (5) C7C C8C H8C C2D N1D C10D (7) C9C C8C H8C C2E C1E H1E C7D C8D C9D (10) C2E C1E H1E C7D C8D H8D C2E C1E H1E C9D C8D H8D H1E1 C1E H1E C8A C9A C10A (9) H1E1 C1E H1E C8A C9A H9A H1E2 C1E H1E C10A C9A H9A N1A C2A C3A (6) C8B C9B C10B (8) N1A C2A C11A (7) C8B C9B H9B C3A C2A C11A (7) C10B C9B H9B N1B C2B C3B (7) C8C C9C C10C (8) N1B C2B C11B (7) C8C C9C H9C C3B C2B C11B (7) C10C C9C H9C N1C C2C C3C (8) C8D C9D C10D (8) N1C C2C C11C (7) C8D C9D H9D C3C C2C C11C (7) C10D C9D H9D N1D C2D C3D (8) N1A C10A C5A (7) N1D C2D C11D (6) N1A C10A C9A (7) C3D C2D C11D (7) C5A C10A C9A (6) O1E C2E C1E 127 (1) N1B C10B C5B (7) O1E C2E H2E N1B C10B C9B (7) O1E C2E H2E C5B C10B C9B (7) C1E C2E H2E N1C C10C C5C (7) C1E C2E H2E N1C C10C C9C (7) H2E2 C2E H2E C5C C10C C9C (7) C2A C3A C4A (8) N1D C10D C5D (7) C2A C3A H3A N1D C10D C9D (7) C4A C3A H3A C5D C10D C9D (9) C2B C3B C4B (8) O1A C11A O2A (7) C2B C3B H3B O1A C11A C2A (8) C4B C3B H3B O2A C11A C2A (7) C2C C3C C4C (7) O1B C11B O2B (8) C2C C3C H3C O1B C11B C2B (9) C4C C3C H3C O2B C11B C2B (7) C2D C3D C4D (8) O1C C11C O2C (8) C2D C3D H3D O1C C11C C2C (7) C4D C3D H3D O2C C11C C2C (7) C3A C4A C5A (8) O1D C11D O2D (8) C3A C4A H4A O1D C11D C2D (7) sup-10

14 C5A C4A H4A O2D C11D C2D (6) C3B C4B C5B (7) V1A O2A C11A O1A (6) C2B N1B C10B C9B (7) V1A O2A C11A C2A 2.0 (8) C2B C3B C4B C5B 2 (1) V1A O2B C11B O1B (7) C2B C3B C4B H4B V1A O2B C11B C2B 9.4 (10) C2C N1C C10C C5C 1 (1) V1A N1A C2A C3A (6) C2C N1C C10C C9C (7) V1A N1A C2A C11A 1.7 (7) C2C C3C C4C C5C 1 (1) V1A N1A C10A C5A (5) C2C C3C C4C H4C V1A N1A C10A C9A 9 (1) C2D N1D C10D C5D 3 (1) V1A N1B C2B C3B (7) C2D N1D C10D C9D (7) V1A N1B C2B C11B 10.6 (8) C2D C3D C4D C5D 1 (1) V1A N1B C10B C5B (6) C2D C3D C4D H4D V1A N1B C10B C9B 5 (1) C3A C2A N1A C10A 2 (1) V1B O2C C11C O1C (6) C3A C4A C5A C6A (8) V1B O2C C11C C2C 9.2 (8) C3A C4A C5A C10A 1 (1) V1B O2D C11D O1D (6) C3B C2B N1B C10B 4 (1) V1B O2D C11D C2D 11.1 (9) C3B C4B C5B C6B (8) V1B N1C C2C C3C (6) C3B C4B C5B C10B 2 (1) V1B N1C C2C C11C 1.0 (7) C3C C2C N1C C10C 2 (1) V1B N1C C10C C5C (5) C3C C4C C5C C6C (8) V1B N1C C10C C9C 1.1 (10) C3C C4C C5C C10C 3 (1) V1B N1D C2D C3D (7) C3D C2D N1D C10D 3 (1) V1B N1D C2D C11D 6.1 (8) C3D C4D C5D C6D (10) V1B N1D C10D C5D (6) C3D C4D C5D C10D 1 (1) V1B N1D C10D C9D 3 (1) C4A C3A C2A C11A (7) O1A C11A C2A N1A (7) C4A C5A C6A C7A (8) O1A C11A C2A C3A 7 (1) C4A C5A C6A H6A 0.7 O1B C11B C2B N1B (8) C4A C5A C10A C9A (8) O1B C11B C2B C3B 1 (1) C4B C3B C2B C11B (8) O1C C11C C2C N1C (7) C4B C5B C6B C7B (8) O1C C11C C2C C3C 6 (1) C4B C5B C6B H6B 2.8 O1D C11D C2D N1D (7) C4B C5B C10B C9B (7) O1D C11D C2D C3D 6 (1) C4C C3C C2C C11C (7) O1E C2E C1E H1E C4C C5C C6C C7C (8) O1E C2E C1E H1E C4C C5C C6C H6C 0.5 O1E C2E C1E H1E C4C C5C C10C C9C (8) O1VB V1B O2C C11C 98.9 (5) C4D C3D C2D C11D (8) O1VB V1B O2D C11D (6) C4D C5D C6D C7D (10) O1VB V1B N1C C2C (5) C4D C5D C6D H6D 2.4 O1VB V1B N1C C10C 66.2 (6) C4D C5D C10D C9D (8) O1VB V1B N1D C2D (5) C5A C4A C3A H3A O1VB V1B N1D C10D 70.4 (7) C5A C6A C7A C8A 0 (1) O1VA V1A O2A C11A 91.5 (6) C5A C6A C7A H7A O1VA V1A O2B C11B (6) C5A C10A C9A C8A 1 (1) O1VA V1A N1A C2A (5) C5A C10A C9A H9A O1VA V1A N1A C10A 67.5 (6) C5B C4B C3B H3B sup-11

15 O1VA V1A N1B C2B (5) C5B C6B C7B C8B 0 (1) O1VA V1A N1B C10B 65.9 (7) C5B C6B C7B H7B O2A V1A O2B C11B 71.5 (9) C5B C10B C9B C8B 0 (1) O2A V1A O2VA H1W 34.9 C5B C10B C9B H9B O2A V1A O2VA H2W C5C C4C C3C H3C O2A V1A N1A C2A 0.6 (5) C5C C6C C7C C8C 1 (1) O2A V1A N1A C10A (6) C5C C6C C7C H7C O2A V1A N1B C2B (5) C5C C10C C9C C8C 2 (1) O2A V1A N1B C10B 38.6 (7) C5C C10C C9C H9C O2A C11A C2A N1A 2.4 (9) C5D C4D C3D H3D O2A C11A C2A C3A (7) C5D C6D C7D C8D 0 (1) O2B V1A O2A C11A 92.9 (7) C5D C6D C7D H7D O2B V1A O2VA H1W C5D C10D C9D C8D 0 (1) O2B V1A O2VA H2W 9.4 C5D C10D C9D H9D O2B V1A N1A C2A (5) C6A C5A C4A H4A 2.7 O2B V1A N1A C10A 35.9 (6) C6A C5A C10A C9A 1 (1) O2B V1A N1B C2B 11.8 (5) C6A C7A C8A C9A 0 (1) O2B V1A N1B C10B (7) C6A C7A C8A H8A O2B C11B C2B N1B 1 (1) C6B C5B C4B H4B 5.6 O2B C11B C2B C3B (8) C6B C5B C10B C9B 0 (1) O2C V1B O2D C11D 68.2 (9) C6B C7B C8B C9B 0 (1) O2C V1B O2VB H3W 12.0 C6B C7B C8B H8B O2C V1B O2VB H4W C6C C5C C4C H4C 2.8 O2C V1B N1C C2C 4.2 (5) C6C C5C C10C C9C 2 (1) O2C V1B N1C C10C (6) C6C C7C C8C C9C 1 (1) O2C V1B N1D C2D (5) C6C C7C C8C H8C O2C V1B N1D C10D 34.5 (7) C6D C5D C4D H4D 2.2 O2C C11C C2C N1C 5.0 (9) C6D C5D C10D C9D 1 (1) O2C C11C C2C C3C (7) C6D C7D C8D C9D 0 (1) O2D V1B O2C C11C 90.1 (7) C6D C7D C8D H8D O2D V1B O2VB H3W C7A C6A C5A C10A 0 (1) O2D V1B O2VB H4W 44.7 C7A C8A C9A C10A 0 (1) O2D V1B N1C C2C (5) C7A C8A C9A H9A O2D V1B N1C C10C 35.5 (6) C7B C6B C5B C10B 0 (1) O2D V1B N1D C2D 9.0 (5) C7B C8B C9B C10B 0 (1) O2D V1B N1D C10D (7) C7B C8B C9B H9B O2D C11D C2D N1D 2 (1) C7C C6C C5C C10C 0 (1) O2D C11D C2D C3D (8) C7C C8C C9C C10C 0 (1) O2VA V1A O2A C11A 86.3 (5) C7C C8C C9C H9C O2VA V1A O2B C11B 78.2 (6) C7D C6D C5D C10D 1 (1) O2VA V1A N1A C2A 79.5 (5) C7D C8D C9D C10D 0 (1) O2VA V1A N1A C10A (6) C7D C8D C9D H9D O2VA V1A N1B C2B 64.6 (5) C8A C7A C6A H6A O2VA V1A N1B C10B (6) C8B C7B C6B H6B O2VB V1B O2C C11C 81.0 (5) C8C C7C C6C H6C O2VB V1B O2D C11D 77.4 (5) C8D C7D C6D H6D O2VB V1B N1C C2C 75.5 (5) C9A C8A C7A H7A O2VB V1B N1C C10C (6) C9B C8B C7B H7B sup-12

16 O2VB V1B N1D C2D 67.6 (5) C9C C8C C7C H7C O2VB V1B N1D C10D (7) C9D C8D C7D H7D N1A V1A O2A C11A 0.8 (5) C10A N1A C2A C11A (6) N1A V1A O2B C11B (6) C10A C5A C4A H4A N1A V1A O2VA H1W 44.1 C10A C5A C6A H6A N1A V1A O2VA H2W C10A C9A C8A H8A N1A C2A C3A C4A 1 (1) C10B N1B C2B C11B (7) N1A C2A C3A H3A C10B C5B C4B H4B N1A C10A C5A C4A 1 (1) C10B C5B C6B H6B N1A C10A C5A C6A (7) C10B C9B C8B H8B N1A C10A C9A C8A (8) C10C N1C C2C C11C (6) N1A C10A C9A H9A 1.8 C10C C5C C4C H4C N1B V1A O2A C11A (5) C10C C5C C6C H6C N1B V1A O2B C11B 11.6 (6) C10C C9C C8C H8C N1B V1A O2VA H1W C10D N1D C2D C11D (7) N1B V1A O2VA H2W 69.1 C10D C5D C4D H4D N1B C2B C3B C4B 1 (1) C10D C5D C6D H6D N1B C2B C3B H3B C10D C9D C8D H8D N1B C10B C5B C4B 0 (1) C11A C2A C3A H3A 6.5 N1B C10B C5B C6B (7) C11B C2B C3B H3B 8.7 N1B C10B C9B C8B (7) C11C C2C C3C H3C 4.4 N1B C10B C9B H9B 1.7 C11D C2D C3D H3D 4.9 N1C V1B O2C C11C 7.6 (5) H1E O1E C2E H2E N1C V1B O2D C11D (5) H1E O1E C2E H2E N1C V1B O2VB H3W 91.2 H1E1 C1E C2E H2E N1C V1B O2VB H4W H1E1 C1E C2E H2E N1C C2C C3C C4C 1 (1) H1E2 C1E C2E H2E N1C C2C C3C H3C H1E2 C1E C2E H2E N1C C10C C5C C4C 1 (1) H1E3 C1E C2E H2E N1C C10C C5C C6C (7) H1E3 C1E C2E H2E N1C C10C C9C C8C (7) H3A C3A C4A H4A 1.4 N1C C10C C9C H9C 1.6 H3B C3B C4B H4B 2.5 N1D V1B O2C C11C (5) H3C C3C C4C H4C 2.4 N1D V1B O2D C11D 11.0 (5) H3D C3D C4D H4D 2.1 N1D V1B O2VB H3W 84.4 H6A C6A C7A H7A 1.6 N1D V1B O2VB H4W 34.9 H6B C6B C7B H7B 0.1 N1D C2D C3D C4D 1 (1) H6C C6C C7C H7C 0.4 N1D C2D C3D H3D H6D C6D C7D H7D 1.3 N1D C10D C5D C4D 0 (1) H7A C7A C8A H8A 1.4 N1D C10D C5D C6D (8) H7B C7B C8B H8B 0.1 N1D C10D C9D C8D (8) H7C C7C C8C H8C 0.1 N1D C10D C9D H9D 0.3 H7D C7D C8D H8D 1.2 C1E C2E O1E H1E 63.2 H8A C8A C9A H9A 0.0 C2A N1A C10A C5A 0 (1) H8B C8B C9B H9B 0.5 C2A N1A C10A C9A (7) H8C C8C C9C H9C 1.2 C2A C3A C4A C5A 0 (1) H8D C8D C9D H9D 0.7 sup-13

17 C2A C3A C4A H4A H8D C8D C9D H9D 0.7 C2B N1B C10B C5B 3 (1) Symmetry codes: (i) x+1, y+1, z+1; (ii) x+2, y+1, z+1; (iii) x+1, y, z+1; (iv) x 1, y 1, z; (v) x+3, y+2, z+2; (vi) x+1, y, z; (vii) x+2, y+2, z+2; (viii) x+1, y+1, z+2; (ix) x 1, y, z; (x) x+1, y+1, z; (xi) x, y, z+1; (xii) x+2, y+1, z+2. sup-14