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Acta Cryst. (2007). E63, o3678    [ doi:10.1107/S160053680703663X ]

3-Hydroxypyridinium perchlorate

J.-C. Yao, J.-B. Guo, L. Zhang, H.-Y. Wen and W. Wang

Abstract top

In the crystal structure of the title compound, C5H6NO+·ClO4-, intermolecular N-H...O, O-H...O and C-H...O hydrogen bonds between the cations and anions result in the formation of an infinite two-dimensional hydrogen-bonded supramolecular network.

Comment top

3-Hydroxypyridine (3-HP) has one hydrogen bond accepting heterocyclic nitrogen and a hydrogen bond donating hydroxy group, which is not only capable of binding to metal centers (Kawata et al., 1997; Castillo et al., 2000; Gao et al., 2005), but can also form cyclic hydrogen-bonding polymers with trifluoroacetic acid and tartronic acid (Breeze & Wang, 1993; Fukunaga et al., 2004). The crystal structures of some hydroxy- substituted zwitterionic pyridinioacetates have been determined to elucidate the interaction of hydrogen bonds (Zhao et al., 2004; Gao et al., 2004; Szafran et al., 1998). Our interest has been directed toward the synthesis of a metal complex based on (3-HP) and 3,5-pyrazoledicarboxylic acid, however, the reaction yielded the title organic compound, (I), whose crystal structure is reported here. Compound (I) consists of one 3-hydroxypyridinium cation and one perchlorate anion (Fig. 1). A two-dimensional supramolecular framework is formed via intermolecular N—H···O, O—H···O, and C—H···O hydrogen bonds between the hydroxy group and nitrogen of 3-hydroxypyridinium and oxygen atoms (O2, O3 and O4) of the perchlorate (Table 1 and Fig. 2).

Related literature top

For related literature, see: Breeze & Wang (1993); Castillo et al. (2000); Fukunaga et al. (2004); Gao et al. (2004, 2005); Kawata et al. (1997); Spek (2003); Szafran et al. (1998); Zhao et al. (2004).

Experimental top

All reagents were of AR grade and were used without further purification. An aqueous solution of 3-hydroxypyridine (1.0 mmol), 3,5-pyrazoledicarboxylic acid (0.50 mmol), and sodium hydroxide (4.00 g, 1.0 mmol) was reacted with an aqueous solution of Cu(ClO4)2·6H2O (0.5 mmol) (0.50 mmol). The pH of the mixture was treated with 0.05 M perchloric acid to a pH of 2–3 and was refluxed for 8 h, colorless crystals of the title compound separated from the filtrate after several days, washed with distilled water and dried in air. Analysis calculated for C5H6NClO4: C 30.71, H 3.09, N 7.16%; found: C 31.15, H 3.14, N 7.68%.

Refinement top

All H atoms attached to C atoms were treated as riding, with C—H = 0.930 Å (aromatic and heteroaromatic) and Uiso(H) = 1.2Ueq(C) of the carrier atoms. The O—H distances were fixed at 0.82 Å, H atoms attached to N atom was constrained in the riding model, with N—H = 0.860 Å and Uiso(H) = 1.2Ueq(N) of the carrier atoms.

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1996); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: XP (Bruker 1998) and PLATON (Spek 2003); software used to prepare material for publication: SHELXTL.

Computing details top

Data collection: APEX2 (Bruker, 2004); cell refinement: APEX2; data reduction: SAINT (Bruker, 2004); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1998); software used to prepare material for publication: SHELXTL.

Figures top
[Figure 1] Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and 50% displacement ellipsoids.
[Figure 2] Fig. 2. Packing diagram of compound (I), showing the interactions of N—H···O, O—H···O, and C—H···O hydrogen bonds, shown as dashed lines.
3-Hydroxypyridinium perchlorate top
Crystal data top
C5H6NO+·ClO4–Z = 2
Mr = 195.56F000 = 200
Triclinic, P1Dx = 1.707 Mg m−3
a = 5.289 (5) ÅMo Kα radiation
λ = 0.71073 Å
b = 8.308 (8) ÅCell parameters from 1662 reflections
c = 9.047 (8) Åθ = 2.3–28.2º
α = 100.346 (9)ºµ = 0.48 mm−1
β = 94.286 (9)ºT = 291 (2) K
γ = 101.732 (9)ºBlock, colourless
V = 380.4 (6) Å30.33 × 0.22 × 0.20 mm
Data collection top
Bruker APEXII CCD area-detector
diffractometer		1375 independent reflections
Radiation source: fine-focus sealed tube1266 reflections with I > 2σ(I)
Monochromator: graphiteRint = 0.018
T = 291(2) Kθmax = 25.5º
φ and ω scansθmin = 2.3º
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		h = −6→6
Tmin = 0.856, Tmax = 0.909k = −10→10
2682 measured reflectionsl = −10→10
Refinement top
Refinement on F2Hydrogen site location: inferred from neighbouring sites
Least-squares matrix: fullH-atom parameters constrained
R[F2 > 2σ(F2)] = 0.032  w = 1/[σ2(Fo2) + (0.0414P)2 + 0.1807P]
where P = (Fo2 + 2Fc2)/3
wR(F2) = 0.085(Δ/σ)max < 0.001
S = 1.04Δρmax = 0.29 e Å−3
1375 reflectionsΔρmin = −0.27 e Å−3
111 parametersExtinction correction: SHELXL97, Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methodsExtinction coefficient: 0.162 (12)
Secondary atom site location: difference Fourier map
Crystal data top
C5H6NO+·ClO4–γ = 101.732 (9)º
Mr = 195.56V = 380.4 (6) Å3
Triclinic, P1Z = 2
a = 5.289 (5) ÅMo Kα
b = 8.308 (8) ŵ = 0.48 mm−1
c = 9.047 (8) ÅT = 291 (2) K
α = 100.346 (9)º0.33 × 0.22 × 0.20 mm
β = 94.286 (9)º
Data collection top
Bruker APEXII CCD area-detector
diffractometer		1375 independent reflections
Absorption correction: multi-scan
(SADABS; Sheldrick, 1996)		1266 reflections with I > 2σ(I)
Tmin = 0.856, Tmax = 0.909Rint = 0.018
2682 measured reflections
Refinement top
R[F2 > 2σ(F2)] = 0.032111 parameters
wR(F2) = 0.085H-atom parameters constrained
S = 1.04Δρmax = 0.29 e Å−3
1375 reflectionsΔρmin = −0.27 e Å−3
Special details top

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 F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2sigma(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 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 (Å2) top
xyzUiso*/Ueq
Cl10.99857 (8)0.81013 (6)0.26437 (5)0.0376 (2)
O10.8190 (3)0.5623 (2)0.61642 (19)0.0610 (5)
H10.88630.50790.66870.091*
O21.1783 (3)0.8632 (2)0.39855 (18)0.0700 (5)
O30.7448 (3)0.8283 (3)0.2972 (2)0.0661 (5)
O41.0803 (3)0.9099 (2)0.15520 (18)0.0625 (5)
O50.9893 (4)0.6374 (2)0.2005 (2)0.0739 (5)
N10.3914 (3)0.8349 (2)0.70012 (19)0.0437 (4)
H1B0.31690.89740.65350.052*
C10.5440 (4)0.7477 (3)0.6254 (2)0.0427 (5)
H1A0.56800.75480.52580.051*
C20.6662 (4)0.6466 (2)0.6984 (2)0.0398 (4)
C30.6274 (4)0.6413 (3)0.8472 (2)0.0467 (5)
H30.71000.57560.89880.056*
C40.4666 (4)0.7332 (3)0.9187 (2)0.0483 (5)
H40.43920.72871.01830.058*
C50.3469 (4)0.8310 (3)0.8432 (2)0.0447 (5)
H50.23730.89330.89030.054*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
Cl10.0429 (3)0.0432 (3)0.0325 (3)0.0218 (2)0.00492 (18)0.0080 (2)
O10.0726 (11)0.0589 (10)0.0620 (10)0.0379 (8)0.0183 (9)0.0088 (8)
O20.0756 (12)0.0865 (13)0.0473 (9)0.0272 (10)−0.0159 (8)0.0106 (9)
O30.0565 (10)0.0965 (14)0.0647 (10)0.0431 (9)0.0234 (8)0.0301 (10)
O40.0670 (11)0.0742 (12)0.0537 (10)0.0157 (9)0.0131 (8)0.0290 (9)
O50.0982 (14)0.0493 (10)0.0754 (12)0.0333 (9)0.0026 (10)−0.0007 (9)
N10.0464 (9)0.0484 (10)0.0432 (9)0.0209 (8)0.0028 (7)0.0161 (8)
C10.0488 (11)0.0472 (12)0.0354 (10)0.0149 (9)0.0051 (8)0.0114 (9)
C20.0421 (10)0.0344 (10)0.0425 (10)0.0114 (8)0.0031 (8)0.0039 (8)
C30.0562 (12)0.0436 (11)0.0460 (11)0.0180 (9)0.0005 (9)0.0175 (9)
C40.0601 (13)0.0523 (12)0.0358 (10)0.0156 (10)0.0087 (9)0.0120 (9)
C50.0445 (11)0.0457 (11)0.0453 (11)0.0154 (9)0.0079 (9)0.0057 (9)
Geometric parameters (Å, °) top
Cl1—O21.4272 (19)C1—C21.384 (3)
Cl1—O31.428 (2)C1—H1A0.9300
Cl1—O41.4361 (18)C2—C31.384 (3)
Cl1—O51.437 (2)C3—C41.376 (3)
O1—C21.352 (2)C3—H30.9300
O1—H10.8200C4—C51.368 (3)
N1—C11.333 (3)C4—H40.9300
N1—C51.338 (3)C5—H50.9300
N1—H1B0.8600
O2—Cl1—O3110.49 (12)O1—C2—C1115.95 (19)
O2—Cl1—O4109.76 (12)O1—C2—C3125.39 (18)
O3—Cl1—O4108.84 (10)C1—C2—C3118.65 (19)
O2—Cl1—O5109.78 (12)C4—C3—C2119.95 (18)
O3—Cl1—O5109.27 (13)C4—C3—H3120.0
O4—Cl1—O5108.66 (13)C2—C3—H3120.0
C2—O1—H1109.5C5—C4—C3120.06 (19)
C1—N1—C5123.99 (17)C5—C4—H4120.0
C1—N1—H1B118.0C3—C4—H4120.0
C5—N1—H1B118.0N1—C5—C4118.38 (19)
N1—C1—C2118.96 (19)N1—C5—H5120.8
N1—C1—H1A120.5C4—C5—H5120.8
C2—C1—H1A120.5
C5—N1—C1—C2−0.2 (3)C1—C2—C3—C41.1 (3)
N1—C1—C2—O1−179.72 (18)C2—C3—C4—C5−0.6 (3)
N1—C1—C2—C3−0.7 (3)C1—N1—C5—C40.6 (3)
O1—C2—C3—C4180.0 (2)C3—C4—C5—N1−0.2 (3)
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O3i0.862.343.025 (3)137
N1—H1B···O2ii0.862.322.941 (3)130
O1—H1···O5iii0.822.002.818 (3)174
C5—H5···O4iv0.932.583.270 (4)131
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y, z; (iii) −x+2, −y+1, −z+1; (iv) x−1, y, z+1.
Hydrogen-bond geometry (Å, °) top
D—H···AD—HH···AD···AD—H···A
N1—H1B···O3i0.862.343.025 (3)137
N1—H1B···O2ii0.862.322.941 (3)130
O1—H1···O5iii0.822.002.818 (3)174
C5—H5···O4iv0.932.583.270 (4)131
Symmetry codes: (i) −x+1, −y+2, −z+1; (ii) x−1, y, z; (iii) −x+2, −y+1, −z+1; (iv) x−1, y, z+1.
Acknowledgements top

This work was supported by the Natural Science Foundation of Henan Province (grant No. 0511022600) and the Education Chamber of Henan Province (grant No. 200510482006).

references
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