Three-dimensional hydrogen-bonding supramolecular architecture of 2-(3-pyridinio)-5-(3-pyridyl)-1,3,4-oxa­diazole perchlorate

In the crystal structure of the title compound, C₁₂H₉N₄O⁺·ClO₄⁻, the protonated cation adopts a cis-I conformation and approximately planar geometry. Each perchlorate anion acts as the acceptor of three C—H...O weak interactions, which, together with N—H...N and C—H...N hydrogen bonds between the protonated cations, extend this structure into a three-dimensional hydrogen-bonded network.

S1. Comment

Bifunctional bridging ligands, for instance, 4,4'-bipyridine, have been used to construct a wide range of zero-, one-, two- or three-dimensional coordination supramolecules or polymers with interesting structural topologies and properties (Fujita, 1998; Hagrman et al., 1999; Leininger et al., 2000). However, compared with the well studied? linear 4,4'-N-donor bridging ligands, efforts on 3,3'-N-donor species are still quite limited (Withersby et al., 1999). Compounds of this type, at least theoretically, have a potential tendency to generate three typical isomers (two cisoid and one transoid, see first scheme below) under appropriate conditions, which is quite different from their 4–4'-N-donor analogs (Du & Zhao, 2003).

Recently, we have initiated a synthetic program for the construction of various coordination polymers or supramolecules with interesting extended frameworks based on the angular dipyridyl ligands, 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo; Du et al., 2003) and 2,5-bis(4-pyridyl)-1,3,4-oxadiazole (4-bpo, Du, Bu et al., 2002; Du, Chen et al., 2002). The specific geometry of this type of ligand may result in either discrete (e.g. molecular box) or divergent coordination networks (e.g. one-dimensional zigzag chain, one-dimensional grid sheet or one-dimensional interpenetrating diamondoid framework) upon metal complexation under appropriate conditions. In addition, it is well known that aromatic compounds of this type also exhibit interesting proton-sponge properties (Staab & Saupe, 1988; Robertson et al., 1998), i.e. represent the species which can act as external proton acceptors through the formation of N—H···Y hydrogen bonds. Moreover, heteroatoms such as N and O with free electron pairs on the five-membered 1,3,4-oxadiazole ring could be considered as the potential active hydrogen-bonding acceptors to form extended supramolecular network through hydrogen-bonding interactions. Taking into account all the above-mentioned aspects, the present work reports the crystal structure of the title compound, [C₁₂H₉N₄O]⁺·(ClO₄⁻), (I).

The crystal structure of (I) consists of a monoprotonated cation of 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo), [C₁₂H₉N₄O]⁺, as shown in Fig. 1, and a ClO₄⁻ counter anion. All non-H atoms of the cation lie in a nearly complete plane and the mean deviation of any atoms from the best-fit plane describing it is 0.061 (4) Å. The pyridinio and pyridyl rings make dihedral angles of 3.5 (3) and 4.5 (4)° with the central oxadiazole system, and the dihedral angle of the pyridinio and pyridyl? rings is 8.0 (4)°. The mean and maximum deviations of any atoms from the best-fit plane of the pyridinie, pyridyl and oxadiazole rings are 0.023 (4) and 0.051 (4), 0.014 (5) and 0.039 (4), and 0.004 (4) and 0.005 (5) Å, respectively. As stated above, there exist three possible isomers of 3-bpo and the cis-I conformation was observed in this case. The non-bonding separation of the two pyridyl N donors (N3···N4) is 7.788 (5) Å. The angle between the center of the oxadiazole ring and two N donors of the 3-pyridine is 110.5 (4)°. Bond lengths and angles are in accord with accepted values; full details are given in the archived CIF.

Analysis of the crystal packing of the title compound showed the existence of three types of hydrogen-bonding interactions (N—H···N, C—H···O and C—H···N), as depicted in Fig. 2, which connect the compound cations and perchlorate anions into a three-dimensional network. The classical N3—H3···N4ⁱ [symmetry code: (i) −x + 1/2, y + 1/2, −z + 3/2] intermolecular hydrogen bonds between the adjacent [C₁₂H₉N₄O]⁺ cations link them into a one-dimensional zigzag chain. Futhurmore,pyridinio atom H10 forms an intermolecular C10—H10···N1ⁱⁱ [symmetry code: (ii) −x + 2, −y + 2, −z + 1] bond with atom N1 of the oxadiazole ring in the adjacent cation, and thus a pair of such head-to-tail hydrogen bonds connect two adjacent compound cations into a dimer. The resulting motif, C, in the formalism of graph-set analysis of hydrogen-bond patterns (Etter, 1990), is characterized as N₂ = R₂²(10). Such a hydrogen-bonding dimer can actually act as a four-connected node through four strong N3—H3···N4 hydrogen-bonding interactions, as stated above, resulting in a two-dimensional layered architecture. Meanwhile, two perchlorate anions located at the terminal position of each dimer form two close hydrogen-bonding graph-set motifs [equivalent B and B', N₃ = R₃³(14) via intermolecular C8—H8···O3ⁱⁱⁱ (iii = −x + 3/2, y + 1/2, −z + 3/2) and C15—H15···O5^iv (iv = x + 1/2, −y + 3/2, z − 1/2) interactions, as well as the above-mentioned C10—H10···N1 bonds. In addition, the two-dimensional hydrogen-bonding layers are expanded to a three-dimensional hydrogen-bonding supramolecular network by C12—H12···O2 interactions between the cations and perchlorate anions from distinct hydrogen-bonding layers. Thus, through six hydrogen-bonding interactions (N3—H3···N4, C12—H12···O2 and C15—H15···O5), four compound cations and two perchlorate anions are connected to result in a large new motif, A (N₆ = R₆⁶(36)). A three-dimensional hydrogen bonding network has also been observed in the crystal structure of a related 3-pyridyl oxadiazole compound, 2-amino-5-(2-amino-3-pyridyl)-1,3,4-oxadiazole (Liszkiewicz et al., 1999), through N—H···N interactions between the amine group and the oxadiazole/pyridyl rings. Examination of the structure of (I) with PLATON (Spek, 2003) showed that there were no solvent-accessible voids or π–π stacking interactions in the crystal lattice of (I).

S2. Experimental

Reaction of 2,5-bis(3-pyridyl)-1,3,4-oxadiazole (3-bpo) with Mn(ClO₄)₂·6H₂O (Lewis acid as proton-providing reagent) in a 1:1 molar ratio in CH₃CN/CH₃OH medium afforded colorless prismatic single crystals of (I) suitable for X-ray diffraction. Analysis calculated for C₁₂H₉C_lN₄O₅: C 44.39, H 2.79, N 17.26%; found: C 44.68, H 2.61, N 17.08%.

S3. Refinement

H atoms were visible in difference maps and were placed at calculated positions with C—H distances of 0.93 Å and N—H distances of 0.90 Å, and refined as riding atoms, with isotropic displacement parameters derived from the C atoms to which they are bonded [U_iso(H) = 1.2 U_eq(C,N)].

Computing details

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

Figures

	Fig. 1. A view of the protonated cation in (I), shown with displacement ellipsoids at the 30% probability level.
	Fig. 2. A view of part of the three-dimensional structure of (I), showing hydrogen-bonding interactions. Atom N4A is at (-x + 1/2, y + 1/2, −z + 3/2), Natom 1B is at (-x + 1/2, y + 1/2, −z + 3/2), atom O3C is at (-x + 3/2, y + 1/2, −z + 3/2) and atom O5D is at (x + 1/2, −y + 3/2, z − 1/2). Letters A, B, B' and C in the hydrogen-bonded rings are defined in the text.

2-(3-Pyridinio)-5-(3-pyridyl)-1,3,4-oxadiazole perchlorate

Crystal data

C12H9N4O^+·ClO4^−	F(000) = 664
Mr = 324.68	Dx = 1.589 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5213 reflections
a = 5.4356 (16) Å	θ = 1.9–25.0°
b = 13.992 (4) Å	µ = 0.31 mm^−1
c = 17.955 (5) Å	T = 293 K
β = 96.382 (5)°	Block, colorless
V = 1357.1 (7) Å^3	0.35 × 0.25 × 0.20 mm
Z = 4

Data collection

BRUKER SMART 1000 diffractometer	1286 reflections with I > 2σ(I)
ω scans	Rint = 0.061
Absorption correction: multi-scan SAINT (Bruker 1998) and SADABS (Sheldrick, 1997)	θmax = 25.0°
Tmin = 0.898, Tmax = 0.926	h = −6→6
5507 measured reflections	k = −14→16
2377 independent reflections	l = −21→21

Refinement

Refinement on F^2	H-atom parameters constrained
R[F^2 > 2σ(F^2)] = 0.060	w = 1/[σ^2(Fo^2) + (0.055P)^2] where P = (Fo^2 + 2Fc^2)/3
wR(F^2) = 0.155	(Δ/σ)max < 0.001
S = 1.14	Δρmax = 0.52 e Å^−3
2377 reflections	Δρmin = −0.36 e Å^−3
199 parameters

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. Full-MATRIX

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
O1	0.4919 (5)	0.91199 (19)	0.61864 (14)	0.0460 (7)
N1	0.7538 (7)	0.9359 (3)	0.5356 (2)	0.0583 (10)
N2	0.6183 (7)	0.8513 (3)	0.51552 (19)	0.0582 (10)
N3	0.7163 (6)	1.1647 (2)	0.73245 (17)	0.0464 (9)
H3	0.6495	1.1818	0.7716	0.056*
N4	−0.0240 (6)	0.6962 (3)	0.63734 (19)	0.0524 (10)
C2	0.6732 (8)	0.9672 (3)	0.5950 (2)	0.0446 (10)
C5	0.4680 (7)	0.8411 (3)	0.5661 (2)	0.0434 (10)
C6	0.7514 (7)	1.0546 (3)	0.6356 (2)	0.0419 (10)
C7	0.6439 (7)	1.0827 (3)	0.6987 (2)	0.0441 (10)
H7	0.5233	1.0451	0.7172	0.053*
C8	0.8876 (8)	1.2209 (3)	0.7079 (2)	0.0534 (11)
H8	0.9286	1.2785	0.7321	0.064*
C9	1.0038 (8)	1.1943 (3)	0.6473 (2)	0.0551 (12)
H9	1.1283	1.2322	0.6312	0.066*
C10	0.9346 (8)	1.1119 (3)	0.6108 (2)	0.0509 (11)
H10	1.0103	1.0937	0.5691	0.061*
C11	0.2864 (7)	0.7668 (3)	0.5709 (2)	0.0422 (10)
C12	0.1460 (7)	0.7629 (3)	0.6307 (2)	0.0467 (11)
H12	0.1721	0.8092	0.6679	0.056*
C13	−0.0656 (9)	0.6323 (3)	0.5824 (3)	0.0656 (13)
H13	−0.1881	0.5866	0.5858	0.079*
C14	0.0651 (9)	0.6308 (3)	0.5205 (2)	0.0611 (13)
H14	0.0306	0.5852	0.4831	0.073*
C15	0.2451 (8)	0.6974 (3)	0.5155 (2)	0.0548 (12)
H15	0.3396	0.6964	0.4754	0.066*
Cl1	0.0994 (2)	0.93863 (9)	0.81949 (7)	0.0611 (4)
O2	−0.0547 (9)	0.8978 (3)	0.7578 (2)	0.1169 (15)
O3	0.3500 (8)	0.9254 (3)	0.8112 (4)	0.160 (2)
O4	0.0551 (9)	1.0349 (3)	0.8232 (3)	0.163 (2)
O5	0.0576 (11)	0.8928 (6)	0.8830 (3)	0.205 (3)

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
O1	0.0528 (18)	0.0492 (17)	0.0389 (15)	−0.0080 (14)	0.0179 (13)	−0.0053 (14)
N1	0.074 (3)	0.053 (2)	0.053 (2)	−0.0155 (19)	0.030 (2)	−0.0132 (19)
N2	0.073 (3)	0.052 (2)	0.054 (2)	−0.011 (2)	0.028 (2)	−0.0094 (19)
N3	0.050 (2)	0.045 (2)	0.046 (2)	0.0103 (17)	0.0111 (17)	−0.0024 (18)
N4	0.058 (2)	0.049 (2)	0.052 (2)	−0.0076 (18)	0.0133 (19)	0.005 (2)
C2	0.056 (3)	0.042 (2)	0.038 (2)	−0.002 (2)	0.012 (2)	0.001 (2)
C5	0.051 (3)	0.040 (2)	0.040 (2)	−0.0042 (19)	0.010 (2)	−0.001 (2)
C6	0.048 (2)	0.040 (2)	0.039 (2)	0.0002 (19)	0.0103 (19)	−0.001 (2)
C7	0.042 (2)	0.045 (3)	0.047 (2)	0.0052 (19)	0.0114 (19)	0.004 (2)
C8	0.057 (3)	0.047 (3)	0.056 (3)	−0.001 (2)	0.002 (2)	−0.005 (2)
C9	0.060 (3)	0.053 (3)	0.054 (3)	−0.011 (2)	0.012 (2)	0.000 (2)
C10	0.059 (3)	0.054 (3)	0.042 (2)	−0.005 (2)	0.018 (2)	0.004 (2)
C11	0.049 (3)	0.040 (2)	0.038 (2)	−0.0010 (19)	0.0095 (19)	0.002 (2)
C12	0.052 (3)	0.043 (3)	0.047 (3)	−0.001 (2)	0.014 (2)	−0.002 (2)
C13	0.074 (3)	0.054 (3)	0.070 (3)	−0.015 (3)	0.011 (3)	0.015 (3)
C14	0.093 (4)	0.037 (3)	0.053 (3)	−0.019 (2)	0.006 (3)	−0.008 (2)
C15	0.076 (3)	0.045 (3)	0.046 (3)	−0.005 (2)	0.016 (2)	−0.003 (2)
Cl1	0.0646 (8)	0.0576 (8)	0.0634 (8)	0.0135 (6)	0.0177 (6)	0.0052 (7)
O2	0.152 (4)	0.092 (3)	0.106 (3)	−0.020 (3)	0.006 (3)	−0.022 (3)
O3	0.096 (3)	0.119 (4)	0.280 (7)	0.024 (3)	0.086 (4)	0.009 (4)
O4	0.171 (5)	0.087 (3)	0.208 (5)	0.053 (3)	−0.083 (4)	−0.061 (4)
O5	0.182 (5)	0.321 (9)	0.119 (4)	−0.040 (5)	0.041 (4)	0.110 (5)

Geometric parameters (Å, º)

O1—C2	1.357 (4)	C6—C7	1.389 (5)
O1—C5	1.366 (4)	C6—C2	1.462 (5)
N3—C8	1.331 (5)	C7—H7	0.9300
N3—C7	1.336 (5)	C5—C11	1.443 (5)
N3—H3	0.8600	C11—C12	1.385 (5)
N1—C2	1.275 (5)	C11—C15	1.390 (5)
N1—N2	1.419 (5)	C15—C14	1.361 (6)
N2—C5	1.295 (4)	C15—H15	0.9300
N4—C12	1.329 (5)	C14—C13	1.384 (6)
N4—C13	1.331 (5)	C14—H14	0.9300
C8—C9	1.370 (6)	C13—H13	0.9300
C8—H8	0.9300	C12—H12	0.9300
C9—C10	1.358 (5)	Cl1—O5	1.350 (5)
C9—H9	0.9300	Cl1—O4	1.371 (4)
C10—C6	1.390 (5)	Cl1—O3	1.399 (4)
C10—H10	0.9300	Cl1—O2	1.431 (4)
C2—O1—C5	102.4 (3)	N2—C5—O1	112.7 (3)
C8—N3—C7	122.6 (4)	N2—C5—C11	127.7 (4)
C8—N3—H3	118.7	O1—C5—C11	119.7 (3)
C7—N3—H3	118.7	C12—C11—C15	117.9 (4)
C2—N1—N2	106.4 (3)	C12—C11—C5	120.9 (4)
C5—N2—N1	105.3 (3)	C15—C11—C5	121.2 (4)
C12—N4—C13	117.9 (4)	C14—C15—C11	119.4 (4)
N3—C8—C9	120.3 (4)	C14—C15—H15	120.3
N3—C8—H8	119.9	C11—C15—H15	120.3
C9—C8—H8	119.9	C15—C14—C13	118.7 (4)
C10—C9—C8	119.1 (4)	C15—C14—H14	120.7
C10—C9—H9	120.5	C13—C14—H14	120.7
C8—C9—H9	120.5	N4—C13—C14	123.0 (4)
C9—C10—C6	120.4 (4)	N4—C13—H13	118.5
C9—C10—H10	119.8	C14—C13—H13	118.5
C6—C10—H10	119.8	N4—C12—C11	123.1 (4)
C7—C6—C10	118.6 (4)	N4—C12—H12	118.5
C7—C6—C2	121.2 (4)	C11—C12—H12	118.5
C10—C6—C2	120.1 (4)	O5—Cl1—O4	112.2 (4)
N3—C7—C6	118.9 (4)	O5—Cl1—O3	106.5 (4)
N3—C7—H7	120.5	O4—Cl1—O3	108.3 (3)
C6—C7—H7	120.5	O5—Cl1—O2	109.0 (4)
N1—C2—O1	113.2 (4)	O4—Cl1—O2	109.8 (3)
N1—C2—C6	126.7 (4)	O3—Cl1—O2	111.0 (3)
O1—C2—C6	120.1 (3)
C2—N1—N2—C5	0.1 (5)	N1—N2—C5—O1	−0.1 (5)
C7—N3—C8—C9	−2.2 (6)	N1—N2—C5—C11	179.0 (4)
N3—C8—C9—C10	2.6 (6)	C2—O1—C5—N2	0.1 (4)
C8—C9—C10—C6	−1.1 (6)	C2—O1—C5—C11	−179.1 (4)
C9—C10—C6—C7	−0.9 (6)	N2—C5—C11—C12	176.9 (4)
C9—C10—C6—C2	178.4 (4)	O1—C5—C11—C12	−4.0 (6)
C8—N3—C7—C6	0.1 (6)	N2—C5—C11—C15	−3.6 (7)
C10—C6—C7—N3	1.4 (6)	O1—C5—C11—C15	175.4 (3)
C2—C6—C7—N3	−177.9 (3)	C12—C11—C15—C14	2.2 (6)
N2—N1—C2—O1	0.0 (5)	C5—C11—C15—C14	−177.3 (4)
N2—N1—C2—C6	−178.0 (4)	C11—C15—C14—C13	−2.4 (7)
C5—O1—C2—N1	0.0 (5)	C12—N4—C13—C14	2.1 (7)
C5—O1—C2—C6	178.1 (4)	C15—C14—C13—N4	0.2 (7)
C7—C6—C2—N1	178.0 (4)	C13—N4—C12—C11	−2.3 (6)
C10—C6—C2—N1	−1.2 (7)	C15—C11—C12—N4	0.2 (6)
C7—C6—C2—O1	0.2 (6)	C5—C11—C12—N4	179.7 (4)
C10—C6—C2—O1	−179.1 (4)

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N3—H3···N4^i	0.86	1.85	2.701 (5)	169
C10—H10···N1^ii	0.93	2.43	3.350 (5)	172
C8—H8···O3^iii	0.93	2.55	3.232 (6)	131
C15—H15···O5^iv	0.93	2.48	3.322 (7)	151
C12—H12···O2	0.93	2.47	3.243 (6)	141

Symmetry codes: (i) −x+1/2, y+1/2, −z+3/2; (ii) −x+2, −y+2, −z+1; (iii) −x+3/2, y+1/2, −z+3/2; (iv) x+1/2, −y+3/2, z−1/2.