3-Hydroxy­pyridinium perchlorate

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.

Key indicators

• Single-crystal X-ray study
• T = 291 K
• Mean [sigma](C-C) = 0.003 Å
• R factor = 0.032
• wR factor = 0.085
• Data-to-parameter ratio = 12.4

checkCIF/PLATON results

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Alert level C
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .......       0.97
PLAT042_ALERT_1_C Calc. and Rep. MoietyFormula Strings Differ ....          ?
PLAT125_ALERT_4_C No _symmetry_space_group_name_Hall Given .......          ?
PLAT150_ALERT_1_C Volume as Calculated Differs from that Given ...     380.40 Ang-3
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)        900 Deg.
PLAT242_ALERT_2_C Check Low       Ueq as Compared to Neighbors for        Cl1

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   6 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   3 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   1 ALERT type 2 Indicator that the structure model may be wrong or deficient
   1 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

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S1. Comment

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

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).

S2. Experimental

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%.

S3. Refinement

All H atoms attached to C atoms were treated as riding, with C—H = 0.930 Å (aromatic and heteroaromatic) and U_iso(H) = 1.2U_eq(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 U_iso(H) = 1.2U_eq(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

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

	Fig. 1. The molecular structure of (I), showing the atom-numbering scheme and 50% displacement ellipsoids.
	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

Crystal data

C5H6NO^+·ClO4^−	Z = 2
Mr = 195.56	F(000) = 200
Triclinic, P1	Dx = 1.707 Mg m^−3
a = 5.289 (5) Å	Mo Kα radiation, λ = 0.71073 Å
b = 8.308 (8) Å	Cell parameters from 1662 reflections
c = 9.047 (8) Å	θ = 2.3–28.2°
α = 100.346 (9)°	µ = 0.48 mm^−1
β = 94.286 (9)°	T = 291 K
γ = 101.732 (9)°	Block, colourless
V = 380.4 (6) Å^3	0.33 × 0.22 × 0.20 mm

Data collection

Bruker APEXII CCD area-detector diffractometer	1375 independent reflections
Radiation source: fine-focus sealed tube	1266 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.018
φ and ω scans	θmax = 25.5°, θmin = 2.3°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
Tmin = 0.856, Tmax = 0.909	k = −10→10
2682 measured reflections	l = −10→10

Refinement

Refinement on F^2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F^2 > 2σ(F^2)] = 0.032	H-atom parameters constrained
wR(F^2) = 0.085	w = 1/[σ^2(Fo^2) + (0.0414P)^2 + 0.1807P] where P = (Fo^2 + 2Fc^2)/3
S = 1.04	(Δ/σ)max < 0.001
1375 reflections	Δρmax = 0.29 e Å^−3
111 parameters	Δρmin = −0.27 e Å^−3
0 restraints	Extinction correction: SHELXL97, Fc^*=kFc[1+0.001xFc^2λ^3/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.162 (12)

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 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 > σ(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 (Ų)

	x	y	z	Uiso*/Ueq
Cl1	0.99857 (8)	0.81013 (6)	0.26437 (5)	0.0376 (2)
O1	0.8190 (3)	0.5623 (2)	0.61642 (19)	0.0610 (5)
H1	0.8863	0.5079	0.6687	0.091*
O2	1.1783 (3)	0.8632 (2)	0.39855 (18)	0.0700 (5)
O3	0.7448 (3)	0.8283 (3)	0.2972 (2)	0.0661 (5)
O4	1.0803 (3)	0.9099 (2)	0.15520 (18)	0.0625 (5)
O5	0.9893 (4)	0.6374 (2)	0.2005 (2)	0.0739 (5)
N1	0.3914 (3)	0.8349 (2)	0.70012 (19)	0.0437 (4)
H1B	0.3169	0.8974	0.6535	0.052*
C1	0.5440 (4)	0.7477 (3)	0.6254 (2)	0.0427 (5)
H1A	0.5680	0.7548	0.5258	0.051*
C2	0.6662 (4)	0.6466 (2)	0.6984 (2)	0.0398 (4)
C3	0.6274 (4)	0.6413 (3)	0.8472 (2)	0.0467 (5)
H3	0.7100	0.5756	0.8988	0.056*
C4	0.4666 (4)	0.7332 (3)	0.9187 (2)	0.0483 (5)
H4	0.4392	0.7287	1.0183	0.058*
C5	0.3469 (4)	0.8310 (3)	0.8432 (2)	0.0447 (5)
H5	0.2373	0.8933	0.8903	0.054*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
Cl1	0.0429 (3)	0.0432 (3)	0.0325 (3)	0.0218 (2)	0.00492 (18)	0.0080 (2)
O1	0.0726 (11)	0.0589 (10)	0.0620 (10)	0.0379 (8)	0.0183 (9)	0.0088 (8)
O2	0.0756 (12)	0.0865 (13)	0.0473 (9)	0.0272 (10)	−0.0159 (8)	0.0106 (9)
O3	0.0565 (10)	0.0965 (14)	0.0647 (10)	0.0431 (9)	0.0234 (8)	0.0301 (10)
O4	0.0670 (11)	0.0742 (12)	0.0537 (10)	0.0157 (9)	0.0131 (8)	0.0290 (9)
O5	0.0982 (14)	0.0493 (10)	0.0754 (12)	0.0333 (9)	0.0026 (10)	−0.0007 (9)
N1	0.0464 (9)	0.0484 (10)	0.0432 (9)	0.0209 (8)	0.0028 (7)	0.0161 (8)
C1	0.0488 (11)	0.0472 (12)	0.0354 (10)	0.0149 (9)	0.0051 (8)	0.0114 (9)
C2	0.0421 (10)	0.0344 (10)	0.0425 (10)	0.0114 (8)	0.0031 (8)	0.0039 (8)
C3	0.0562 (12)	0.0436 (11)	0.0460 (11)	0.0180 (9)	0.0005 (9)	0.0175 (9)
C4	0.0601 (13)	0.0523 (12)	0.0358 (10)	0.0156 (10)	0.0087 (9)	0.0120 (9)
C5	0.0445 (11)	0.0457 (11)	0.0453 (11)	0.0154 (9)	0.0079 (9)	0.0057 (9)

Geometric parameters (Å, º)

Cl1—O2	1.4272 (19)	C1—C2	1.384 (3)
Cl1—O3	1.428 (2)	C1—H1A	0.9300
Cl1—O4	1.4361 (18)	C2—C3	1.384 (3)
Cl1—O5	1.437 (2)	C3—C4	1.376 (3)
O1—C2	1.352 (2)	C3—H3	0.9300
O1—H1	0.8200	C4—C5	1.368 (3)
N1—C1	1.333 (3)	C4—H4	0.9300
N1—C5	1.338 (3)	C5—H5	0.9300
N1—H1B	0.8600
O2—Cl1—O3	110.49 (12)	O1—C2—C1	115.95 (19)
O2—Cl1—O4	109.76 (12)	O1—C2—C3	125.39 (18)
O3—Cl1—O4	108.84 (10)	C1—C2—C3	118.65 (19)
O2—Cl1—O5	109.78 (12)	C4—C3—C2	119.95 (18)
O3—Cl1—O5	109.27 (13)	C4—C3—H3	120.0
O4—Cl1—O5	108.66 (13)	C2—C3—H3	120.0
C2—O1—H1	109.5	C5—C4—C3	120.06 (19)
C1—N1—C5	123.99 (17)	C5—C4—H4	120.0
C1—N1—H1B	118.0	C3—C4—H4	120.0
C5—N1—H1B	118.0	N1—C5—C4	118.38 (19)
N1—C1—C2	118.96 (19)	N1—C5—H5	120.8
N1—C1—H1A	120.5	C4—C5—H5	120.8
C2—C1—H1A	120.5
C5—N1—C1—C2	−0.2 (3)	C1—C2—C3—C4	1.1 (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—C4	0.6 (3)
O1—C2—C3—C4	180.0 (2)	C3—C4—C5—N1	−0.2 (3)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1B···O3^i	0.86	2.34	3.025 (3)	137
N1—H1B···O2^ii	0.86	2.32	2.941 (3)	130
O1—H1···O5^iii	0.82	2.00	2.818 (3)	174
C5—H5···O4^iv	0.93	2.58	3.270 (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.