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metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 4-(4-Pyridyl)pyridinium bis(pyridine-2,6- dicarboxylato)chromium(iii) tetrahydrate Janet

Correspondence e-mail: janet_soleimannejad@yahoo.com Received 24 February 2008; accepted 9 March 2008 Key indicators: single-crystal X-ray study; T = 150 K; mean (C C) = 0.002 Å; R factor = 0.

1 metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN (4-Pyridyl)pyridinium bis(pyridine-2,6- dicarboxylato)chromium(iii) tetrahydrate Janet Soleimannejad, a * Hossein Aghabozorg b and Shabnam Hooshmand a a Department of Chemistry, Ilam University, Ilam, Iran, and b Faculty of Chemistry, Tarbiat Moallem University, Tehran, Iran Correspondence janet_soleimannejad@yahoo.com Received 24 February 2008; accepted 9 March 2008 Key indicators: single-crystal X-ray study; T = 150 K; mean (C C) = Å; R factor = 0.038; wr factor = 0.103; data-to-parameter ratio = Experimental Crystal data (C 10 H 9 N 2 )[Cr(C 7 H 3 NO 4 ) 2 ]4H 2 O M r = Triclinic, P1 a = (19) Å b = (19) Å c = (3) Å = (3) = (3) Data collection Bruker SMART APEXII diffractometer Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.851, T max = Refinement R[F 2 >2(F 2 )] = wr(f 2 ) = S = reflections = (3) V = (4) Å 3 Z =2 Mo K radiation = 0.52 mm 1 T = 150 (2) K mm measured reflections independent reflections 8883 reflections with I > 2(I) R int = parameters H-atom parameters constrained max = 0.60 e Å 3 min = 0.57 e Å 3 The title compound, (C 10 H 9 N 2 )[Cr(C 7 H 3 NO 4 ) 2 ]4H 2 O or (4,4 0 -bipyh)[cr(pydc) 2 ]4H 2 O (where 4,4 0 -bipy is 4,4 0 -bipyridine and pydch 2 is pyridine-2,6-dicarboxylic acid), was synthesized by the reaction of chromium(iii) chloride hexahydrate with pyridine-2,6-dicarboxylic acid and 4,4 0 -bipyridine in a 1:2:4 molar ratio in aqueous solution. This compound is composed of an anionic complex, [Cr(pydc) 2 ], protonated 4,4 0 -bipyridine as a counter-ion, (4,4 0 -bipyh) +, and four uncoordinated water molecules. The anion is a six-coordinate complex with a distorted octahedral geometry around the Cr III atom, formed by two tridentate pyridine-2,6-dicarboxylate, pydc 2, groups. Intermolecular O HO, N HO and C HO hydrogen bonds, and C O stacking interactions (with distances of (13) and (13) Å) connect the various components into a supramolecular structure. Related literature For related literature, see: Aghabozorg, Attar Gharamaleki, Ghadermazi et al. (2007); Aghabozorg, Attar Gharamaleki, Ghasemikhah et al. (2007); Soleimannejad et al. (2007). Table 1 Hydrogen-bond geometry (Å, ). D HA D H HA DA D HA N4 H4AO11 i (14) 164 O9 H9BO (15) 173 O9 H9AO10 ii (16) 176 O10 H10BO (16) 172 O10 H10AN (15) 162 O11 H11AO10 iii (15) 172 O11 H11BO (16) 152 O12 H12BO (16) 160 O12 H12AO7 iv (16) 162 C3 H3O8 v (16) 139 C5 H5O5 vi (16) 128 C10 H10O12 vii (16) 132 C11 H11O9 viii (17) 126 C15 H15O7 ix (17) 160 C16 H16O9 x (18) 169 C20 H20O2 xi (16) 117 C20 H20O11 xii (17) 143 C24 H24O (17) 143 Symmetry codes: (i) x; y þ 1; z þ 1; (ii) x 1; y; z; (iii) x; y 1; z; (iv) x þ 1; y; z; (v) x; y þ 1; z; (vi) x þ 1; y þ 1; z; (vii) x þ 1; y þ 1; z þ 1; (viii) x; y þ 1; z þ 1; (ix) x þ 1; y þ 1; z; (x) x þ 1; y þ 2; z þ 1; (xi) x þ 1; y; z þ 1; (xii) x þ 2; y þ 1; z þ 1. Data collection: APEX2 (Bruker, 2007); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL (Sheldrick, 2008); software used to prepare material for publication: SHELXL97. Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: OM2216). m564 Soleimannejad et al. doi: /s

2 metal-organic compounds References Aghabozorg, H., Attar Gharamaleki, J., Ghadermazi, M., Ghasemikhah, P. & Soleimannejad, J. (2007). Acta Cryst. E63, m1803 m1804. Aghabozorg, H., Attar Gharamaleki, J., Ghasemikhah, P., Ghadermazi, M. & Soleimannejad, J. (2007). Acta Cryst. E63, m1710 m1711. Bruker (2007). APEX2. Bruker AXS Inc., Madison, Wisconsin, USA. Sheldrick, G. M. (1996). SADABS. University of Göttingen, Germany. Sheldrick, G. M. (2008). Acta Cryst. A64, Soleimannejad, J., Aghabozorg, H., Hooshmand, S. & Adams, H. (2007). Acta Cryst. E63, m3089 m3090. Soleimannejad et al. (C 10 H 9 N 2 )[Cr(C 7 H 3 NO 4 ) 2 ]4H 2 O m565

3 supporting information [doi: /s ] 4-(4-Pyridyl)pyridinium bis(pyridine-2,6-dicarboxylato)chromium(iii) tetrahydrate Janet Soleimannejad, Hossein Aghabozorg and Shabnam Hooshmand S1. Comment The molecular structure of the title compound is shown in Fig. 1. Hydrogen bond lengths are given in Table 1. According to the crystal structure, the title compound is composed of an anionic complex, [Cr(pydc) 2 ] -, protonated 4,4 -bipyridine as a counter ion, (4,4 -bipyh) +, and four uncoordinated water molecules. The Cr III atom is six-coordinated by two pyridine-2,6-dicarboxylate, pydc 2-, groups which act as a tridentate ligand through two O and one N atoms. The O8 Cr1 O1 C1 and O8 Cr1 O4 C7 torsion angles ( (9) and (9), repectively) show that these two pydc 2- groups are perpendicular. So the anionic complex has distorted octahedral geometry around Cr III atom. For balancing the anionic complex, a protonated 4,4 -bipyridinium, (4,4 -bipyh) +, exists. In the crystal structure of (4,4 -bipyh)[cr(pydc) 2 ].4H 2 O complex, the spaces between two layers of [Cr(pydc) 2 ] - anions are filled with (4,4 -bipyh) + cations and water molecules (Fig. 2). The angle between two planes passing through aromatic rings of (4,4 -bipyh) + is (6), indicating the flexibility of the C C bond between two rings. A considerable feature of title compound is the presence of C O π stacking interactions between C1 O2 and C7 O3 and Cg1 [Cg1 is centroid for N1/C2 C6 ring] with O π distances of (13) Å (1 - x, 1 - y, -z) and (13) Å (-x, 1 - y, -z), respectively (Fig. 3). Intermolecular O H O, N H O and C H O hydrogen bonds with D A ranging from (14) Å to (18) Å (Table 1), ion pairing and C O π stacking interactions seem to be effective in the stabilization of the crystal structure, resulting in the formation of an interesting supramolecular structure. S2. Experimental A solution of CrCl 3.6H 2 O (133 mg, 0.5 mmol) in water (5 ml) was added to an aqueous solution of pyridine-2,6-dicarboxylic acid (167 mg, 1 mmol) and 4,4 -bipyridine (312 mg, 2 mmol) in water (10 ml) in a 1:2:4 molar ratio and refluxed for an hour. Purple crystals of the title compound were obtained after allowing the mixture to stand for two weeks at room temperature. S3. Refinement The H-atoms were included in calculated positions and treated as riding atoms, with the exception of H atoms on the water molecules. The latter were located in a low theta Fourier map and refined by a constrained rigid type geometry, where O H = 0.85 Å and C H = 0.95 Å with U iso (H) = 1.2U eq (parent O or C-atom). sup-1

4 Figure 1 The molecular structure of the title compound, displacement ellipsoids drawn at the 50% probability level. Figure 2 Layered diagram of the title compound. The space between the two layers of [Cr(pydc) 2 ] - fragments is filled with a layer of (4,4 -bipyh) + cations and water molecules. sup-2

Figure 3 C O π Stacking interactions between C1 O2 and C7 O3 and Cg1 [Cg1 is centroid for N1/C2 C6 ring] with O π distance of 3.3390 (13) Å (1 - x, 1 - y, -z) and 3.

5 Figure 3 C O π Stacking interactions between C1 O2 and C7 O3 and Cg1 [Cg1 is centroid for N1/C2 C6 ring] with O π distance of (13) Å (1 - x, 1 - y, -z) and (13) Å (-x, 1 - y, -z) (measured to the center of Cg1). 4-(4-Pyridyl)pyridinium bis(pyridine-2,6-dicarboxylato)chromium(iii) tetrahydrate Crystal data (C 10 H 9 N 2 )[Cr(C 7 H 3 NO 4 ) 2 ] 4H 2 O M r = Triclinic, P1 a = (19) Å b = (19) Å c = (3) Å α = (3) β = (3) γ = (3) V = (4) Å 3 Data collection Bruker SMART APEXII diffractometer Radiation source: fine-focus sealed tube Graphite monochromator Detector resolution: 100 pixels mm -1 ω scans Z = 2 F(000) = 630 D x = Mg m 3 Mo Kα radiation, λ = Å Cell parameters from reflections θ = µ = 0.52 mm 1 T = 150 K Block, purple mm Absorption correction: multi-scan (SADABS; Sheldrick, 1996) T min = 0.851, T max = measured reflections independent reflections 8883 reflections with I > 2σ(I) R int = sup-3

6 θ max = 36.1, θ min = 2.2 h = Refinement Refinement on F 2 Least-squares matrix: full R[F 2 > 2σ(F 2 )] = wr(f 2 ) = S = reflections 370 parameters 0 restraints Primary atom site location: structure-invariant direct methods k = l = Secondary atom site location: difference Fourier map Hydrogen site location: inferred from neighbouring sites H-atom parameters constrained w = 1/[σ 2 (F o2 ) + (0.048P) P] where P = (F o 2 + 2F c2 )/3 (Δ/σ) max = Δρ max = 0.60 e Å 3 Δρ min = 0.57 e Å 3 Special details 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 Cr (19) (19) (11) (4) N (10) (10) (6) (16) N (10) (10) (6) (15) N (12) (12) (7) (2) N (12) (11) (7) (19) H4A * O (9) (9) (5) (15) O (10) (10) (6) (17) O (10) (10) (6) (17) O (9) (9) (5) (15) O (9) (9) (5) (15) O (10) (11) (6) (18) O (10) (10) (6) (17) O (9) (9) (5) (15) O (11) (11) (6) (2) H9B * H9A * O (10) (10) (6) (17) H10B * H10A * O (11) (11) (6) (2) H11A * H11B * sup-4

7 O (11) (12) (7) (2) H12B * H12A * C (12) (12) (8) (18) C (12) (12) (7) (18) C (13) (13) (8) (2) H * C (14) (14) (8) (2) H * C (13) (13) (8) (2) H * C (12) (12) (7) (18) C (12) (12) (8) (19) C (12) (12) (8) (19) C (12) (12) (7) (18) C (13) (13) (7) (2) H * C (13) (13) (8) (2) H * C (13) (12) (7) (19) H * C (12) (12) (7) (18) C (12) (12) (7) (19) C (14) (15) (8) (2) H * C (14) (14) (8) (2) H * C (12) (12) (8) (19) C (12) (12) (7) (18) C (13) (12) (8) (19) H * C (13) (13) (8) (2) H * C (14) (14) (8) (2) H * C (13) (13) (8) (2) H * C (13) (13) (8) (2) H * C (14) (13) (8) (2) H * Atomic displacement parameters (Å 2 ) U 11 U 22 U 33 U 12 U 13 U 23 Cr (8) (8) (7) (6) (5) (5) N (4) (4) (3) (3) (3) (3) N (4) (4) (3) (3) (3) (3) sup-5

8 N (5) (5) (4) (4) (4) (4) N (5) (4) (4) (4) (3) (3) O (4) (4) (3) (3) (3) (3) O (4) (4) (4) (3) (3) (3) O (4) (4) (4) (3) (3) (3) O (4) (4) (3) (3) (3) (3) O (4) (4) (3) (3) (3) (3) O (4) (5) (4) (4) (3) (3) O (4) (4) (4) (3) (3) (3) O (4) (4) (3) (3) (3) (3) O (5) (5) (4) (4) (3) (4) O (4) (4) (3) (3) (3) (3) O (5) (5) (4) (4) (3) (3) O (5) (6) (4) (4) (4) (4) C (5) (4) (4) (4) (4) (4) C (4) (4) (4) (4) (3) (3) C (5) (5) (4) (4) (4) (4) C (6) (6) (4) (5) (4) (4) C (5) (5) (4) (4) (4) (4) C (5) (5) (4) (4) (3) (3) C (5) (4) (4) (4) (4) (4) C (5) (5) (4) (4) (4) (4) C (5) (5) (4) (4) (3) (3) C (5) (5) (4) (4) (4) (4) C (5) (5) (4) (4) (4) (4) C (5) (5) (4) (4) (4) (4) C (4) (4) (4) (4) (3) (3) C (5) (4) (4) (4) (3) (4) C (6) (6) (5) (5) (4) (4) C (5) (5) (4) (4) (4) (4) C (5) (5) (4) (4) (3) (4) C (5) (4) (4) (4) (4) (3) C (5) (5) (4) (4) (4) (4) C (5) (5) (4) (4) (4) (4) C (5) (5) (4) (4) (4) (4) C (5) (5) (4) (4) (4) (4) C (5) (5) (4) (4) (4) (4) C (5) (5) (5) (4) (4) (4) Geometric parameters (Å, º) Cr1 N (10) C3 C (18) Cr1 N (10) C3 H Cr1 O (10) C4 C (18) Cr1 O (11) C4 H Cr1 O (10) C5 C (15) Cr1 O (10) C5 H N1 C (15) C6 C (17) sup-6

9 N1 C (15) C8 C (17) N2 C (15) C9 C (15) N2 C (15) C10 C (18) N3 C (18) C10 H N3 C (17) C11 C (18) N4 C (17) C11 H N4 C (17) C12 C (15) N4 H4A C12 H O1 C (14) C13 C (16) O2 C (15) C15 C (17) O3 C (14) C15 H O4 C (14) C16 C (17) O5 C (13) C16 H O6 C (15) C17 C (17) O7 C (15) C17 C (16) O8 C (14) C18 C (17) O9 H9B C18 C (17) O9 H9A C19 C (16) O10 H10B C19 H O10 H10A C20 H O11 H11A C21 C (17) O11 H11B C21 H O12 H12B C22 H O12 H12A C23 C (16) C1 C (16) C23 H C2 C (15) C24 H N2 Cr1 N (4) O4 C7 C (10) N2 Cr1 O (5) O6 C8 O (11) N1 Cr1 O (5) O6 C8 C (10) N2 Cr1 O (5) O5 C8 C (10) N1 Cr1 O (5) N2 C9 C (11) O8 Cr1 O (4) N2 C9 C (9) N2 Cr1 O (5) C10 C9 C (11) N1 Cr1 O (5) C9 C10 C (11) O8 Cr1 O (3) C9 C10 H O1 Cr1 O (4) C11 C10 H N2 Cr1 O (5) C10 C11 C (10) N1 Cr1 O (5) C10 C11 H O8 Cr1 O (4) C12 C11 H O1 Cr1 O (4) C13 C12 C (11) O5 Cr1 O (4) C13 C12 H C2 N1 C (9) C11 C12 H C2 N1 Cr (8) N2 C13 C (10) C6 N1 Cr (8) N2 C13 C (9) C9 N2 C (9) C12 C13 C (10) C9 N2 Cr (8) O7 C14 O (11) C13 N2 Cr (8) O7 C14 C (10) sup-7

10 C15 N3 C (11) O8 C14 C (10) C21 N4 C (10) N3 C15 C (12) C21 N4 H4A N3 C15 H C20 N4 H4A C16 C15 H C1 O1 Cr (8) C15 C16 C (12) C7 O4 Cr (8) C15 C16 H C8 O5 Cr (8) C17 C16 H C14 O8 Cr (8) C23 C17 C (11) H9B O9 H9A C23 C17 C (11) H10B O10 H10A 98.4 C16 C17 C (11) H11A O11 H11B C19 C18 C (10) H12B O12 H12A C19 C18 C (11) O2 C1 O (11) C22 C18 C (11) O2 C1 C (10) C20 C19 C (11) O1 C1 C (10) C20 C19 H N1 C2 C (11) C18 C19 H N1 C2 C (9) N4 C20 C (11) C3 C2 C (10) N4 C20 H C2 C3 C (11) C19 C20 H C2 C3 H N4 C21 C (11) C4 C3 H N4 C21 H C5 C4 C (10) C22 C21 H C5 C4 H C21 C22 C (11) C3 C4 H C21 C22 H C6 C5 C (11) C18 C22 H C6 C5 H C24 C23 C (11) C4 C5 H C24 C23 H N1 C6 C (11) C17 C23 H N1 C6 C (9) N3 C24 C (12) C5 C6 C (10) N3 C24 H O3 C7 O (11) C23 C24 H O3 C7 C (10) N2 Cr1 N1 C (4) C2 N1 C6 C (10) O8 Cr1 N1 C (9) Cr1 N1 C6 C (12) O1 Cr1 N1 C (8) C4 C5 C6 N (17) O5 Cr1 N1 C (9) C4 C5 C6 C (11) O4 Cr1 N1 C (9) Cr1 O4 C7 O (10) N2 Cr1 N1 C (4) Cr1 O4 C7 C (12) O8 Cr1 N1 C (9) N1 C6 C7 O (11) O1 Cr1 N1 C (9) C5 C6 C7 O (19) O5 Cr1 N1 C (9) N1 C6 C7 O (14) O4 Cr1 N1 C (8) C5 C6 C7 O (11) N1 Cr1 N2 C (4) Cr1 O5 C8 O (10) O8 Cr1 N2 C (9) Cr1 O5 C8 C (13) O1 Cr1 N2 C (9) C13 N2 C9 C (17) O5 Cr1 N2 C (8) Cr1 N2 C9 C (8) O4 Cr1 N2 C (9) C13 N2 C9 C (10) sup-8

11 N1 Cr1 N2 C (4) Cr1 N2 C9 C (12) O8 Cr1 N2 C (8) O6 C8 C9 N (11) O1 Cr1 N2 C (9) O5 C8 C9 N (14) O5 Cr1 N2 C (9) O6 C8 C9 C (19) O4 Cr1 N2 C (9) O5 C8 C9 C (11) N2 Cr1 O1 C (8) N2 C9 C10 C (17) N1 Cr1 O1 C (8) C8 C9 C10 C (11) O8 Cr1 O1 C (9) C9 C10 C11 C (18) O5 Cr1 O1 C (9) C10 C11 C12 C (17) O4 Cr1 O1 C (15) C9 N2 C13 C (17) N2 Cr1 O4 C (8) Cr1 N2 C13 C (8) N1 Cr1 O4 C (8) C9 N2 C13 C (10) O8 Cr1 O4 C (9) Cr1 N2 C13 C (12) O1 Cr1 O4 C (14) C11 C12 C13 N (16) O5 Cr1 O4 C (9) C11 C12 C13 C (11) N2 Cr1 O5 C (8) Cr1 O8 C14 O (9) N1 Cr1 O5 C (8) Cr1 O8 C14 C (12) O8 Cr1 O5 C (15) N2 C13 C14 O (11) O1 Cr1 O5 C (9) C12 C13 C14 O (19) O4 Cr1 O5 C (9) N2 C13 C14 O (14) N2 Cr1 O8 C (8) C12 C13 C14 O (11) N1 Cr1 O8 C (8) C24 N3 C15 C (2) O1 Cr1 O8 C (9) N3 C15 C16 C (2) O5 Cr1 O8 C (15) C15 C16 C17 C (18) O4 Cr1 O8 C (9) C15 C16 C17 C (11) Cr1 O1 C1 O (10) C23 C17 C18 C (12) Cr1 O1 C1 C (12) C16 C17 C18 C (16) C6 N1 C2 C (17) C23 C17 C18 C (16) Cr1 N1 C2 C (8) C16 C17 C18 C (13) C6 N1 C2 C (10) C22 C18 C19 C (17) Cr1 N1 C2 C (12) C17 C18 C19 C (11) O2 C1 C2 N (11) C21 N4 C20 C (18) O1 C1 C2 N (14) C18 C19 C20 N (18) O2 C1 C2 C (18) C20 N4 C21 C (18) O1 C1 C2 C (11) N4 C21 C22 C (18) N1 C2 C3 C (17) C19 C18 C22 C (17) C1 C2 C3 C (11) C17 C18 C22 C (11) C2 C3 C4 C (18) C16 C17 C23 C (17) C3 C4 C5 C (18) C18 C17 C23 C (11) C2 N1 C6 C (17) C15 N3 C24 C (19) Cr1 N1 C6 C (9) C17 C23 C24 N (19) Hydrogen-bond geometry (Å, º) D H A D H H A D A D H A N4 H4A O11 i (14) 164 O9 H9B O (15) 173 O9 H9A O10 ii (16) 176 sup-9

12 O10 H10B O (16) 172 O10 H10A N (15) 162 O11 H11A O10 iii (15) 172 O11 H11B O (16) 152 O12 H12B O (16) 160 O12 H12A O7 iv (16) 162 C3 H3 O8 v (16) 139 C5 H5 O5 vi (16) 128 C10 H10 O12 vii (16) 132 C11 H11 O9 viii (17) 126 C15 H15 O7 ix (17) 160 C16 H16 O9 x (18) 169 C20 H20 O2 xi (16) 117 C20 H20 O11 xii (17) 143 C24 H24 O (17) 143 Symmetry codes: (i) x, y+1, z+1; (ii) x 1, y, z; (iii) x, y 1, z; (iv) x+1, y, z; (v) x, y+1, z; (vi) x+1, y+1, z; (vii) x+1, y+1, z+1; (viii) x, y+1, z+1; (ix) x+1, y+1, z; (x) x+1, y+2, z+1; (xi) x+1, y, z+1; (xii) x+2, y+1, z+1. sup-10

metal-organic compounds

metal-organic compounds Acta Crystallographica Section E Structure Reports Online ISSN 1600-5368 2-(2-Pyridyl)pyridinium bis(pyridine-2,6- dicarboxylato-j 3 O,N,O 0 )aluminate(iii) trihydrate Janet Soleimannejad,