Redetermination of pyridine-4-carbonitrile–chloranilic acid (1/1) at 180 K

Kazuma Gotoh; Hirokazu Nagoshi; Hiroyuki Ishida

doi:10.1107/S1600536808017182

. 2008 Jun 13;64(Pt 7):o1260. doi: 10.1107/S1600536808017182

Redetermination of pyridine-4-carbonitrile–chloranilic acid (1/1) at 180 K

Kazuma Gotoh ^a, Hirokazu Nagoshi ^a, Hiroyuki Ishida ^a,^*

PMCID: PMC2961658 PMID: 21202894

Abstract

In the crystal structure of the title compound, C₆H₄N₂·C₆H₂Cl₂O₄, two chloranilic acid (systematic name: 2,5-dichloro-3,6-dihydroxy-1,4-benzoquinone) molecules are connected by O—H⋯O hydrogen bonds to form a dimeric unit. The pyridine-4-carbonitrile molecules are linked on both sides of the dimer via N⋯H⋯O hydrogen bonds to give a centrosymmetric 2:2 complex of pyridine-4-carbonitrile and chloranilic acid. The H atom in the N⋯H⋯O hydrogen bond is disordered over two positions with approximately equal occupancies. The pyridine ring makes a dihedral angle of 61.54 (14)° with the chloranilic acid plane. The 2:2 units are further linked by intermolecular C—H⋯O and C—H⋯Cl hydrogen bonds. This determination presents a siginficantly higher precision crystal structure than the previously published structure [Tomura & Yamasshita (2008 ▶). X-ray Struct. Anal. Online, 24, x31–x32].

Related literature

For related structures, see, for example: Gotoh, Asaji & Ishida (2007 ▶); Gotoh, Ishikawa & Ishida (2007 ▶); Tomura & Yamasshita (2008 ▶).

Experimental

Crystal data

C₆H₄N₂·C₆H₂Cl₂O₄
M _r = 313.10
Monoclinic,
a = 14.9327 (8) Å
b = 4.9301 (3) Å
c = 17.0355 (10) Å
β = 93.0474 (18)°
V = 1252.37 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.53 mm⁻¹
T = 180 (2) K
0.18 × 0.18 × 0.08 mm

Data collection

Rigaku R-AXIS RAPIDII diffractometer
Absorption correction: numerical (ABSCOR; Higashi, 1995 ▶) T _min = 0.900, T _max = 0.958
11539 measured reflections
3567 independent reflections
2165 reflections with I > 2σ(I)
R _int = 0.076

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.176
S = 1.07
3567 reflections
192 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.73 e Å⁻³

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004 ▶); cell refinement: PROCESS-AUTO; data reduction: CrystalStructure (Rigaku/MSC, 2004 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: CrystalStructure and PLATON (Spek, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808017182/lh2639sup1.cif

e-64-o1260-sup1.cif^{(16.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808017182/lh2639Isup2.hkl

e-64-o1260-Isup2.hkl^{(174.9KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	1.20 (10)	1.47 (10)	2.610 (3)	158 (7)
O4—H4⋯O1	0.78 (4)	2.21 (4)	2.661 (3)	118 (4)
O4—H4⋯O1ⁱ	0.78 (4)	1.99 (4)	2.656 (3)	144 (4)
N1—H1⋯O2	0.83 (12)	1.80 (13)	2.610 (3)	163 (10)
N1—H1⋯O3	0.83 (12)	2.45 (10)	2.957 (3)	120 (9)
C7—H7⋯Cl1ⁱⁱ	0.95	2.82	3.722 (3)	159
C8—H8⋯O4ⁱⁱⁱ	0.95	2.46	3.324 (4)	151
C10—H10⋯Cl2^iv	0.95	2.81	3.710 (3)	158
C11—H11⋯O3^v	0.95	2.39	3.245 (4)	150

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) ; (v) .

Acknowledgments

This work was supported by a Grant-in-Aid for Scientific Research (C) (No. 19550018) from the Japanese Society for the Promotion of Science.

supplementary crystallographic information

Comment

The title compound, (I), was prepared in order to extend our study on D—H···A hydrogen bonding (D = N, O, or C; A = N, O or Cl) in amine–chloranilic acid systems (Gotoh, Asaji & Ishida, 2007; Gotoh, Ishikawa & Ishida, 2007). This determination presents a siginficantly higher precision crystal structure than the previously published structure (Tomura & Yamasshita, 2008).

The asymmetric unit in (I) contains one pyridine-4-carbonitrile molecule and one chloranilic acid molecule (Fig. 1). Two chloranilic acid molecules related by an inversion centre are held together by O—H···O hydrogen bonds (Table 1) to form a dimer. The pyridine-4-carbonitrile molecules are linked on both sides of the dimer via N···H···O hydrogen bonds to give a centrosymmetric 2:2 complex of pyridine-4-carbonitrile and chloranilic acid (Fig. 2). The N···O distance is relatively short [2.610 (3) Å] and the H atom in the N···H···O hydrogen bond is disordered over two positions with site occupancies of 0.54 (17) and 0.46 (17). In the 2:2 unit, the pyridine and chloranilic acid planes are twised with a dihedral angle of 61.54 (14)°. The 2:2 units are further linked by C—H···O and C—H···Cl hydrogen bonds (Table 1 and Fig. 3).

Experimental

Single crystals were obtained by slow evaporation from a methanol solution (30 ml) of chloranilic acid (500 mg) and pyridine-4-carbonitrile (250 mg).