metal-organic papers catena-[l 6-1,2,4,5-Benzenetetracarboxylatotetraaqua-dinickel(II)] Comment

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1 metal-organic papers Acta Crystallographica Section E Structure Reports Online catena-[l 6-1,2,4,5-Benzenetetracarboxylatotetraaqua-dinickel(II)] dihydrate ISSN Shi-Yao Yang, a La-Sheng Long, a Rong-Bin Huang, a Lan-Sun Zheng a and Seik Weng Ng b * a State Key Laboratory for Physical Chemistry of Solid Surfaces, Xiamen University, Xiamen , People's Republic of China, and b Department of Chemistry, University of Malaya, Kuala Lumpur, Malaysia Correspondence seikweng@um.edu.my Key indicators Single-crystal X-ray study T = 298 K Mean (C±C) = AÊ H-atom completeness 72% Disorder in solvent or counterion R factor = wr factor = Data-to-parameter ratio = 16.9 For details of how these key indicators were automatically derived from the article, see The two Ni atoms and the 6-1,2,4,5-benzenetetracarboxylate ligand in the crystal structure of catena-[ 6-1,2,4,5-benzenetetracarboxylato-tetraaqua-dinickel(II)] dihydrate, [Ni 2 (C 10 - H 2 O 8 )(H 2 O) 4 ]2(H 2 O), occupy special positions at three independent inversion centers. One of the Ni atoms is chelated by two 1,2,4,5-benzenetetracarboxylates [NiÐO (3) and (3) A Ê ; OÐNiÐO 91.7 (1) ]; the two remaining sites of the coordination octahedron of this atom are taken up by water molecules. The second Ni atom is coordinated by four carbonyl O atoms belonging to four benzenetetracarboxylate ligands [NiÐO (3), (3) A Ê ]; its coordination sphere also includes two water molecules. Each tetraanionic benzenetetracarboxylate ligand links together six Ni atoms, the linkages giving rise to a threedimensional network motif. The structure is consolidated by hydrogen bonds involving coordinated as well as uncoordinated water molecules. Comment The 1,2,4,5-benzenetetracarboxylate ligand, by virtue of the positions of its four carboxyl groups on the benzene ring, should be capable of a variety of linkages to several metal centers. However, attempts to synthesize transition-metal derivatives by the reaction of the metal salts with the carboxylic acid or acid anhdyride in the presence of sodium hydroxide do not always yield the desired compounds. For example, the reaction involving a cobalt(ii) reagent affords hexaaquacobalt(ii) dihydrogen 1,2,4,5-benzenetetracarboxylate (Ward & Luehrs, 1983), a compound where the carboxylic acid retains two of its four acid protons; the nickel(ii) analog has an identical formulation (Jessen et al., 1992). Neither of these compounds displays any metal±carboxylate bonds. The sodium component of the reaction can also be incorporated into the crystal structure (Wu et al., 2001) as the counterion that balances the charge of the aninionic entity. For steric reasons, few metal 1,2,4,5-benzenetetracarboxylates have been crystallographically authenticated owing to the fact that four carboxyl ÐCO 2 groups are rather unlikely to participate in bonding simultaneously (Murugavel et al., 2002); the documented cases are limited to the tetrathallium (Day & Luehrs, 1988) and monocesium (Luehrs & Bowman-James, 1994) derivatives. Received 17 July 2003 Accepted 1 September 2003 Online 5 September 2003 # 2003 International Union of Crystallography Printed in Great Britain ± all rights reserved Acta Cryst. (2003). E59, m849±m850 DOI: Shi-Yao Yang et al. [Ni 2 (C 10 H 2 O 8 )(H 2 O) 4 ]2H 2 O m849

2 metal-organic papers Figure 1 ORTEP (Johnson, 1976) plot of a fragment of the structure of the title compound, with displacement ellipsoids drawn at the 75% probability level. H atoms are drawn as spheres of arbitrary radii. The disordered water molecule is not shown [Symmetry translational codes: (i) x,1 y, z; (ii) x, 1+y, z; (iii) 1 x, 1 y, z; (iv) 1 x, 2 y, z]. In the title compound, (I), the two independent Ni atoms both lie at inversion centers. One of them is chelated by two 1,2,4,5-benzenetetracarboxylato tetraanions, which bind via their ortho-carboxyl ÐCO 2 groups [Ni1ÐO (3) and Ni1ÐO (3) A Ê ; O2ÐNi1ÐO (1) ]; the two remaining sites of the coordination octahedron of Ni1 are taken up by water molecules [Ni1ÐO1w (3) A Ê ] (Fig. 1). The Ni2 atom is coordinated by four carbonyl O atoms belonging to four benzenetetracarboxylate ligands [Ni2ÐO1 ii (3), Ni2ÐO (3) A Ê ] (see Fig. 1 for symmetry codes); its coordination sphere also includes two water molecules[ni2ðo2w (3) A Ê ]. Each tetraanionic benzenetetracarboxylate ligand links together six Ni atoms, the linkages giving rise to a threedimensional network motif. The structure is consolidated by hydrogen bonds involving the coordinated (O1w, O2w) and disordered uncoordinated (O3w 0 ) water molecules (Table 2). Experimental 1,2,4,5-Benzenetetracarboxylic acid anhydride (pyromellitic anhydride, 0.22 g, 1 mmol) and sodium hydroxide (0.16 g, 4 mmol) were dissolved in water (15 ml); nickel nitrate hexahydrate (0.58 g, 2 mmol), dissolved in water (3 ml), was then added to the solution. The green solution was placed in a 20 ml Te on-lined stainless-steel bomb, heated at 453 for 100 h, and then cooled to room temperature at 5 K h 1 to give prismatic crystals. Crystal data [Ni 2 (C 10 H 2 O 8 )(H 2 O) 4 ]2H 2 O M r = Triclinic, P1 a = (1) A Ê b = (1) A Ê c = (1) A Ê = (7) = (8) = (7) V = (1) A Ê 3 Z =1 D x = Mg m 3 Mo K radiation Cell parameters from 25 re ections = 12.0±15.0 = 2.47 mm 1 T = 298 (2) K Prism, green mm Data collection Enraf±Nonius CAD-4 diffractometer! scans Absorption correction: scan (North et al., 1968) T min = 0.674, T max = measured re ections 2300 independent re ections 1594 re ections with I > 2(I) Re nement Re nement on F 2 R[F 2 >2(F 2 )] = wr(f 2 ) = S = re ections 136 parameters H atoms treated by a mixture of independent and constrained re nement Table 1 Selected geometric parameters (A Ê, ). Ni1ÐO (3) Ni1ÐO (3) Ni1ÐO1w (3) O2ÐNi1ÐO2 i O2ÐNi1ÐO (1) O2ÐNi1ÐO3 i 88.3 (1) O2ÐNi1ÐO1w 85.5 (1) O2ÐNi1ÐO1w i 94.5 (1) O3 i ÐNi1ÐO (2) O3ÐNi1ÐO1w 85.2 (1) O3 i ÐNi1ÐO1w 94.8 (1) O1wÐNi1ÐO1w i (2) R int = max = 30.0 h =0! 9 k = 10! 10 l = 11! 10 2 standard re ections frequency: 60 min intensity decay: none w = 1/[ 2 (F o 2 ) + (0.0438P) P] where P =(F o 2 +2F c 2 )/3 (/) max = max = 1.06 e A Ê 3 min = 0.83 e A Ê 3 Ni2ÐO1 ii (3) Ni2ÐO (3) Ni2ÐO2w (3) O1 ii ÐNi2ÐO1 iii O1 ii ÐNi2ÐO (1) O1 ii ÐNi2ÐO4 iv 91.7 (1) O1 ii ÐNi2ÐO2w iv 83.8 (1) O1 ii ÐNi2ÐO2w 96.2 (1) O4ÐNi2ÐO4 iv (2) O4ÐNi2ÐO2w 94.3 (1) O4ÐNi2ÐO2w iv 85.7 (1) O2wÐNi2ÐO2w iv Symmetry codes: (i) x; 1 y; z; (ii) x; 1 y; z; (iii) 1 x; 1 y; z; (iv) 1 x; 2 y; z. Table 2 Hydrogen-bonding geometry (A Ê, ). DÐHA DÐH HA DA DÐHA O1wÐH1w1O1 iii (4) 162 O1wÐH1w2O3w (9) 164 O2wÐH2w2O2 ii (4) 147 O2wÐH2w1O (4) 152 Symmetry codes: (ii) x; 1 y; z; (ii) 1 x; 1 y; z. The carbon-bound atom H4 was positioned geometrically and was allowed to ride on the C4 atom; the water H atoms were located and re ned, subject to OÐH 0.85 (1) and HH 1.39 (1) A Ê restraints. The displacement parameters of all H atoms were set to 1.2 times U eq of the carrier C or O atoms. One of the uncoordinated water molecules is disordered, and as the disorder re ned to nearly 1/1, the occupancy for each of the components (O3w and O3w 0 ) was set to 0.5; their displacement parameters were restrained to be equal to each other. The H atoms of the disordered water molecule were not located and were not included in the re nement. The largest peak was approximately 1 A Ê from atoms O3w and O3w 0. Data collection: CAD-4 Software (Enraf±Nonius Delft, 1988); cell re nement: CAD-4 Software; data reduction: XCAD4/PC (Harms, 1997); program(s) used to solve structure: SHELXS97 (Sheldrick, m850 Shi-Yao Yang et al. [Ni 2 (C 10 H 2 O 8 )(H 2 O) 4 ]2H 2 O Acta Cryst. (2003). E59, m849±m850

3 metal-organic papers 1997); program(s) used to re ne structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP±II (Johnson, 1976); software used to prepare material for publication: SHELXL97. The authors thank the National Science Foundation of China (Grant Nos , and ), the Department of Science and Technology of China (2002CCA01600), the National Science Foundation of Fujian Province (Grant No. E ), and the University of Malaya for supporting this work. References Day, C. S. & Leuhrs, D. C. (1988). Inorg. Chim. Acta, 142, 201±202. Enraf±Nonius Delft (1988). CAD-4 VAX/PC Software. Enraf±Nonius Delft, Scienti c Instruments Division, Delft, The Netherlands. Harms, K. (1997). XCAD4. University of Marburg, Germany. Jessen, S. M., KuÈ ppers, H. & Luehrs, D. C. (1992). Z. Naturforsch. Teil B, 47, 1141±1153. Johnson, C. K. (1976). ORTEP-II. Report ORNL Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA. Luehrs, D. C. & Bowman-James, K. (1994). J. Mol. Struct. 321, 251±254. Murugavel, R., Krishnamurthy, D. & Sathiyendiran, M. (2002). J. Chem. Soc. Dalton Trans. p., 34±39. North, A. C. T., Phillips, D. C. & Mathews, F. S. (1968). Acta Cryst. A24, 351± 359. Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of GoÈ ttingen, Germany. Ward, D. L. & Leuhrs, D. C. (1983). Acta Cryst. C39, 1370±1372. Wu, C.-D., Wu, D.-M., Lu, C.-Z. & Huang, J. S. (2001). Acta Cryst. E57, m253± m255. Acta Cryst. (2003). E59, m849±m850 Shi-Yao Yang et al. [Ni 2 (C 10 H 2 O 8 )(H 2 O) 4 ]2H 2 O m851

4 [doi: /s ] catena-[µ 6-1,2,4,5-Benzenetetracarboxylato-tetraaqua-dinickel(II)] dihydrate Shi-Yao Yang, La-Sheng Long, Rong-Bin Huang, Lan-Sun Zheng and Seik Weng Ng S1. Comment The 1,2,4,5-benzenetetracarboxylate ligand, by virtue of the positions of its four carboxyl groups on the benzene ring, should be capable of a variety of linkages to several metal centers. However, attempts to synthesize transition-metal derivatives by the reaction of the metal salts with the carboxylic acid or acid anhdyride in the presence of sodium hydroxide do not always yield the desired compounds. For example, the reaction involving a cobalt(ii) reagent affords hexaaquacobalt dihydrogen 1,2,4,5-benzenetetracarboxylate (Ward & Leuhrs, 1983), a compound where the carboxylic acid retains two of its four acid protons; the nickel(ii) analog has an identical formulation (Jessen et al., 1992). Neither of these compounds displays any metal-carboxylate bonds. The sodium component of the reaction can also be incorporated into the crystal structure (Wu et al., 2001) as the counterion that balances the charge of the aninionic entity. For steric reasons, few metal 1,2,4,5-benzenetetracarboxylates have been crystallographically authenticated owing to the fact that four carboxyl CO 2 groups are rather unlikely to participate in bonding simultaneously (Murugavel et al., 2002); the documented cases are limited to the tetrathallium (Day & Leuhrs, 1988) and monocesium (Leuhrs & Bowman-James, 1994) derivatives. In the title compound, (I), the two independent Ni atoms both lie at inversion centers. One of them is chelated by two 1,2,4,5-benzenetetracarboxylato tetraanions, which use their ortho-carboxyl CO 2 groups to bind [Ni1 O (3) and Ni1 O (3) Å; O2 Ni1 O (1) ]; two remaining sites of the coordination octahedron of Ni1 are taken up by water molecules [Ni1 O1w (3) Å](Fig. 1). The Ni2 atom is coordinated by four carbonyl O atoms belonging to four benzenetetracarboxylate ligands [Ni2 O1 ii (3), Ni2 O (3) Å] (see Fig.1 for symmetry codes); its coordination sphere also includes two water molecules[ni2 O2w (3) Å]. Each tetraanionic benzenetetracarboxylate ligand links together six Ni atoms, the linkages giving rise to a threedimensional network motif. The structure is consolidated by hydrogen bonds involving the coordinated (O1w, O2w) and disordered lattice (O3w ) water molecules (Table 2). S2. Experimental 1,2,4,5-Benzenetetracarboxylic acid anhydride (pyromellitic anhydride, 0.22 g, 1 mmol) and sodium hydroxide (0.16 g, 4 mmol) were dissolved in water (15 ml); nickel nitrate hexahydrate (0.60 g, 2 mmol) dissolved in water (3 ml) was then added to the solution. The green solution was placed in a 20 ml Teflon-lined stainless-steel bomb, heated at 453 for 100 h, and then cooled to room temperature at 5 KC h 1 to give prismatic shaped crystals. S3. Refinement The carbon-bound H4 atom was positioned geometrically and was allowed to ride on the C4 atom; the water H atoms were located and refined subject to O H 0.85 (1) and H H 1.39 (1) Å restraints. The temperature factors of all H atoms were set to 1.2 times those of the carrier C or O atoms. sup-1

5 One of the lattice water molecules is disordered, and as the disorder refined to nearly 1/1, the occupancy for each of the components (O3w and O3w ) was set to 0.5; their temperature factors were restrained to be equal to each other. The H- atoms of the disordered water molecule were not located and and were not included in the refinement. The largest peak was approximately 1 Å from atoms O3w and O3w. Figure 1 ORTEP (Johnson, 1976) plot of a fragment of the structure of the title compound, with displacement ellipsoids drawn at the 75% probability level. Hydrogen atoms are drawn as spheres of arbitrary radii. The disordered water molecule is not shown [Symmetry/translational codes: (i) x, 1 y, z; (ii) x, 1 + y, z; (iii) 1 x, 1 y, z; (iv) 1 x, 2 y, z]. catena-[µ 6-1,2,4,5-Benzenetetracarboxylato-tetraaqua-dinickel(II)] dihydrate Crystal data [Ni 2 (C 10 H 2 O 8 (H 2 O) 4 ]2H 2 O M r = Triclinic, P1 a = (1) Å b = (1) Å c = (1) Å α = (7) β = (8) γ = (7) V = (1) Å 3 Z = 1 F(000) = 242 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from 25 reflections θ = µ = 2.47 mm 1 T = 298 K Prism, green mm sup-2

6 Data collection Enraf-Nonius CAD-4 diffractometer Radiation source: fine-focus sealed tube Graphite monochromator ω scan Absorption correction: psi scan (North et al., 1968) T min = 0.674, T max = measured reflections Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 136 parameters 6 restraints Primary atom site location: structure-invariant direct methods 2300 independent reflections 1594 reflections with I > 2σ(I) R int = θ max = 30.0, θ min = 2.6 h = 0 9 k = l = standard reflections every 60 min intensity decay: none 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 w = 1/[σ 2 (F o2 ) + (0.0438P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 1.06 e Å 3 Δρ min = 0.83 e Å 3 Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å 2 ) x y z U iso */U eq Occ. (<1) Ni (2) Ni (2) O (4) (3) (3) (5) O (4) (4) (3) (6) O (4) (3) (3) (6) O (4) (4) (3) (6) O1w (5) (5) (4) (7) O2w (4) (4) (4) (6) O3w (1) (1) (1) (1) 0.50 O3w (1) (1) (1) (1) 0.50 C (6) (5) (5) (7) C (6) (5) (4) (7) C (5) (5) (5) (7) C (6) (5) (5) (7) C (6) (5) (4) (7) H1w (4) (5) (6) 0.032* H1w (7) (3) (6) 0.032* H2w (7) (3) (5) 0.023* H2w (7) (2) (5) 0.023* H * sup-3

7 Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Ni (4) (3) (4) (3) (3) (3) Ni (4) (3) (3) (3) (3) (2) O (1) (1) (1) (1) (1) (1) O (1) (2) (1) (1) (1) (1) O (1) (1) (1) (1) (1) (1) O (2) (1) (1) (1) (1) (1) O1w (2) (2) (2) (1) (1) (1) O2w (1) (1) (2) (1) (1) (1) O3w (3) (3) (3) (3) (2) (2) O3w (3) (3) (3) (3) (2) (2) C (2) (2) (2) (1) (1) (1) C (2) (2) (2) (1) (1) (1) C (2) (2) (2) (1) (1) (1) C (2) (2) (2) (1) (1) (1) C (2) (2) (2) (1) (1) (1) Geometric parameters (Å, º) Ni1 O (3) O3 C (5) Ni1 O2 i (3) O4 C (4) Ni1 O (3) C1 C (5) Ni1 O3 i (3) C2 C4 v (5) Ni1 O1w (3) C2 C (5) Ni1 O1w i (3) C3 C (5) Ni2 O1 ii (3) C3 C (5) Ni2 O1 iii (3) C4 C2 v (5) Ni2 O (3) O1w H1w (1) Ni2 O4 iv (3) O1w H1w (1) Ni2 O2w (3) O2w H2w (1) Ni2 O2w iv (3) O2w H2w (1) O1 C (4) C4 H O2 C (5) O2 Ni1 O2 i O4 iv Ni2 O2w iv 94.3 (1) O2 Ni1 O (1) O2w Ni2 O2w iv O2 Ni1 O3 i 88.3 (1) C1 O1 Ni2 vi (2) O2 Ni1 O1w 85.5 (1) C1 O2 Ni (3) O2 Ni1 O1w i 94.5 (1) C5 O3 Ni (2) O2 i Ni1 O (1) C5 O4 Ni (3) O2 i Ni1 O3 i 91.7 (1) O2 C1 O (3) O2 i Ni1 O1w 94.5 (1) O2 C1 C (3) O2 i Ni1 O1w i 85.5 (1) O1 C1 C (3) O3 i Ni1 O (2) C4 v C2 C (3) O3 Ni1 O1w 85.2 (1) C4 v C2 C (3) O3 i Ni1 O1w 94.8 (1) C3 C2 C (3) sup-4

8 O3 Ni1 O1w i 94.8 (1) C4 C3 C (3) O3 i Ni1 O1w i 85.2 (1) C4 C3 C (3) O1w Ni1 O1w i (2) C2 C3 C (3) O1 ii Ni2 O1 iii C3 C4 C2 v (3) O1 ii Ni2 O (1) O4 C5 O (3) O1 ii Ni2 O4 iv 91.7 (1) O4 C5 C (3) O1 ii Ni2 O2w iv 83.8 (1) O3 C5 C (3) O1 ii Ni2 O2w 96.2 (1) Ni1 O1w H1w1 120 (3) O1 iii Ni2 O (1) Ni1 O1w H1w2 102 (3) O1 iii Ni2 O4 iv 88.3 (1) H1w1 O1w H1w2 109 (2) O1 iii Ni2 O2w 83.8 (1) Ni2 O2w H2w1 104 (3) O1 iii Ni2 O2w iv 96.2 (1) Ni2 O2w H2w2 109 (3) O4 Ni2 O4 iv (2) H2w1 O2w H2w2 110 (2) O4 Ni2 O2w 94.3 (1) C3 C4 H O4 Ni2 O2w iv 85.7 (1) C2 v C4 H O4 iv Ni2 O2w 85.7 (1) O3 i Ni1 O2 C (4) O1 C1 C2 C4 v 40.3 (5) O3 Ni1 O2 C (4) O2 C1 C2 C (5) O1w Ni1 O2 C (4) O1 C1 C2 C (4) O1w i Ni1 O2 C (4) C4 v C2 C3 C4 0.4 (6) O2 Ni1 O3 C (3) C1 C2 C3 C (3) O2 i Ni1 O3 C (3) C4 v C2 C3 C (3) O1w Ni1 O3 C (3) C1 C2 C3 C5 8.1 (6) O1w i Ni1 O3 C (3) C2 C3 C4 C2 v 0.4 (6) O2w iv Ni2 O4 C (3) C5 C3 C4 C2 v (3) O2w Ni2 O4 C (3) Ni2 O4 C5 O (5) O1 ii Ni2 O4 C (3) Ni2 O4 C5 C (2) O1 iii Ni2 O4 C (3) Ni1 O3 C5 O (3) Ni1 O2 C1 O (3) Ni1 O3 C5 C (5) Ni1 O2 C1 C2 0.2 (6) C4 C3 C5 O (5) Ni2 vi O1 C1 O (5) C2 C3 C5 O (4) Ni2 vi O1 C1 C (3) C4 C3 C5 O (4) O2 C1 C2 C4 v (4) C2 C3 C5 O (5) Symmetry codes: (i) x, y+1, z; (ii) x, y+1, z; (iii) x+1, y+1, z; (iv) x+1, y+2, z; (v) x+1, y+1, z+1; (vi) x, y 1, z. Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A O1w H1w1 O1 iii (4) 162 O1w H1w2 O3w (9) 164 O2w H2w2 O2 ii (4) 147 O2w H2w1 O (4) 152 Symmetry codes: (ii) x, y+1, z; (iii) x+1, y+1, z. sup-5