Pyridine-3-carbonitrile-chloranilic acid-acetonitrile (2/1/2).

In the crystal structure of the title compound, 2C(6)H(4)N(2)·C(6)H(2)Cl(2)O(4)·2C(2)H(3)N, the two symmetry-related pyridine-3-carbonitrile mol-ecules are linked to either side of a chloranilic acid (systematic name: 2,5-dichloro-3,6-dihydr-oxy-1,4-benzoquinone) mol-ecule via inter-molecular O-H⋯N hydrogen bonds, giving a centrosymmetric 2:1 unit. The dihedral angle between the pyridine ring and the chloranilic acid plane is 26.71 (6)°. In addition, the two acetonitrile mol-ecules are linked to either side of the 2:1 unit through C-H⋯N hydrogen bonds, forming a 2:1:2 aggregate. These 2:1:2 aggregates are further linked by weak inter-molecular C-H⋯N and C-H⋯O hydrogen bonds, forming a tape along the c axis.

Related literature

For related structures, see, for example: Gotoh et al. (2009 ▶); Gotoh, Asaji & Ishida (2008 ▶); Gotoh, Nagoshi & Ishida (2008 ▶).

Experimental

Crystal data

2C6H4N2·C6H2Cl2O4·2C2H3N

M = 499.31

Triclinic,

a = 3.91269 (16) Å

b = 10.8937 (9) Å

c = 13.5966 (5) Å

α = 105.302 (4)°

β = 90.0058 (14)°

γ = 90.847 (5)°

V = 558.93 (6) Å3

Z = 1

Mo Kα radiation

μ = 0.33 mm−1

T = 180 K

0.32 × 0.25 × 0.15 mm

Data collection

Rigaku RAXIS-RAPID II diffractometer

Absorption correction: numerical (; Higashi, 1995 ▶) T min = 0.906, T max = 0.951

7721 measured reflections

3232 independent reflections

2592 reflections with I > 2σ(I)

R int = 0.031

Refinement

R[F 2 > 2σ(F 2)] = 0.035

wR(F 2) = 0.099

S = 1.07

3232 reflections

159 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.44 e Å−3

Δρmin = −0.28 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, 2009 ▶).

Crystal structure: contains datablocks General, I. DOI: 10.1107/S1600536809036605/lh2901sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809036605/lh2901Isup2.hkl

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

2C6H4N2·C6H2Cl2O4·2C2H3N	Z = 1
Mr = 499.31	F(000) = 256.00
Triclinic, P1	Dx = 1.483 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71075 Å
a = 3.91269 (16) Å	Cell parameters from 6412 reflections
b = 10.8937 (9) Å	θ = 3.1–30.1°
c = 13.5966 (5) Å	µ = 0.33 mm−1
α = 105.302 (4)°	T = 180 K
β = 90.0058 (14)°	Block, brown
γ = 90.847 (5)°	0.32 × 0.25 × 0.15 mm
V = 558.93 (6) Å3

Rigaku RAXIS-RAPID II diffractometer	2592 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1	Rint = 0.031
ω scans	θmax = 30.0°
Absorption correction: numerical (ABSCOR; Higashi, 1995)	h = −5→5
Tmin = 0.906, Tmax = 0.951	k = −15→15
7721 measured reflections	l = −19→17
3232 independent reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.035	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.099	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0495P)2 + 0.1506P] where P = (Fo2 + 2Fc2)/3
3232 reflections	(Δ/σ)max < 0.001
159 parameters	Δρmax = 0.44 e Å−3
0 restraints	Δρmin = −0.28 e Å−3

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.

	x	y	z	Uiso*/Ueq
Cl1	0.74850 (9)	−0.11634 (3)	0.17747 (2)	0.02647 (10)
O1	1.1404 (3)	−0.24034 (9)	−0.00816 (7)	0.0278 (2)
O2	0.6357 (3)	0.14675 (10)	0.16065 (7)	0.0294 (2)
N1	0.4384 (3)	0.38133 (11)	0.18840 (9)	0.0268 (2)
N2	0.2005 (4)	0.63890 (12)	0.52232 (10)	0.0347 (3)
N3	−0.2867 (4)	0.85277 (13)	0.41743 (11)	0.0400 (3)
C1	1.0708 (3)	−0.12968 (12)	−0.00163 (9)	0.0213 (2)
C2	0.8789 (3)	−0.04984 (12)	0.08193 (9)	0.0208 (2)
C3	0.8076 (3)	0.07272 (12)	0.08605 (9)	0.0215 (2)
C4	0.3922 (4)	0.43073 (12)	0.28796 (10)	0.0254 (3)
H4	0.4423	0.3805	0.3335	0.031*
C5	0.2725 (3)	0.55390 (12)	0.32762 (10)	0.0233 (3)
C6	0.1973 (4)	0.62808 (13)	0.26185 (10)	0.0265 (3)
H6	0.1169	0.7124	0.2871	0.032*
C7	0.2431 (4)	0.57525 (13)	0.15812 (11)	0.0281 (3)
H7	0.1922	0.6227	0.1106	0.034*
C8	0.3640 (4)	0.45244 (13)	0.12482 (10)	0.0270 (3)
H8	0.3956	0.4171	0.0537	0.032*
C9	0.2324 (4)	0.60218 (13)	0.43620 (10)	0.0263 (3)
C10	−0.2753 (4)	0.87366 (14)	0.50394 (12)	0.0310 (3)
C11	−0.2586 (4)	0.90013 (16)	0.61421 (12)	0.0365 (3)
H11A	−0.0933	0.8436	0.6332	0.055*
H11B	−0.4846	0.8857	0.6406	0.055*
H11C	−0.1869	0.9889	0.6432	0.055*
H2	0.596 (7)	0.226 (3)	0.152 (2)	0.082 (9)*

	U11	U22	U33	U12	U13	U23
Cl1	0.03569 (18)	0.02348 (16)	0.02309 (16)	0.00415 (12)	0.00557 (12)	0.01100 (11)
O1	0.0404 (5)	0.0181 (4)	0.0255 (5)	0.0062 (4)	0.0045 (4)	0.0065 (4)
O2	0.0445 (6)	0.0199 (5)	0.0242 (5)	0.0089 (4)	0.0100 (4)	0.0058 (4)
N1	0.0349 (6)	0.0203 (5)	0.0252 (5)	0.0066 (4)	0.0041 (5)	0.0061 (4)
N2	0.0488 (8)	0.0284 (6)	0.0272 (6)	0.0078 (5)	0.0018 (5)	0.0075 (5)
N3	0.0512 (8)	0.0302 (7)	0.0380 (7)	0.0070 (6)	0.0065 (6)	0.0076 (5)
C1	0.0267 (6)	0.0180 (5)	0.0194 (5)	0.0010 (4)	−0.0019 (5)	0.0053 (4)
C2	0.0272 (6)	0.0186 (6)	0.0174 (5)	0.0009 (4)	0.0006 (5)	0.0060 (4)
C3	0.0268 (6)	0.0188 (6)	0.0188 (5)	0.0017 (4)	−0.0010 (5)	0.0045 (4)
C4	0.0321 (7)	0.0199 (6)	0.0254 (6)	0.0057 (5)	0.0015 (5)	0.0077 (5)
C5	0.0272 (6)	0.0199 (6)	0.0226 (6)	0.0024 (5)	0.0009 (5)	0.0049 (5)
C6	0.0327 (7)	0.0188 (6)	0.0286 (7)	0.0065 (5)	0.0026 (5)	0.0070 (5)
C7	0.0365 (7)	0.0238 (6)	0.0261 (6)	0.0066 (5)	0.0010 (5)	0.0100 (5)
C8	0.0348 (7)	0.0229 (6)	0.0235 (6)	0.0048 (5)	0.0036 (5)	0.0062 (5)
C9	0.0316 (7)	0.0205 (6)	0.0273 (6)	0.0052 (5)	0.0015 (5)	0.0067 (5)
C10	0.0307 (7)	0.0227 (6)	0.0387 (8)	0.0033 (5)	0.0063 (6)	0.0061 (5)
C11	0.0407 (8)	0.0335 (8)	0.0329 (8)	0.0040 (6)	0.0042 (6)	0.0044 (6)

Cl1—C2	1.7200 (13)	C4—H4	0.9500
O1—C1	1.2201 (15)	C5—C6	1.3884 (18)
O2—C3	1.3099 (15)	C5—C9	1.4399 (18)
O2—H2	0.91 (3)	C6—C7	1.3883 (19)
N1—C4	1.3316 (17)	C6—H6	0.9500
N1—C8	1.3387 (18)	C7—C8	1.3848 (19)
N2—C9	1.1406 (18)	C7—H7	0.9500
N3—C10	1.138 (2)	C8—H8	0.9500
C1—C2	1.4521 (17)	C10—C11	1.451 (2)
C1—C3i	1.5153 (18)	C11—H11A	0.9800
C2—C3	1.3546 (17)	C11—H11B	0.9800
C3—C1i	1.5153 (18)	C11—H11C	0.9800
C4—C5	1.3955 (18)
C3—O2—H2	114.0 (17)	C7—C6—C5	117.96 (12)
C4—N1—C8	118.49 (11)	C7—C6—H6	121.0
O1—C1—C2	123.93 (12)	C5—C6—H6	121.0
O1—C1—C3i	117.75 (11)	C8—C7—C6	119.07 (12)
C2—C1—C3i	118.31 (10)	C8—C7—H7	120.5
C3—C2—C1	121.90 (11)	C6—C7—H7	120.5
C3—C2—Cl1	120.77 (10)	N1—C8—C7	122.88 (13)
C1—C2—Cl1	117.33 (9)	N1—C8—H8	118.6
O2—C3—C2	123.08 (12)	C7—C8—H8	118.6
O2—C3—C1i	117.14 (11)	N2—C9—C5	179.14 (15)
C2—C3—C1i	119.78 (11)	N3—C10—C11	179.69 (18)
N1—C4—C5	122.13 (12)	C10—C11—H11A	109.5
N1—C4—H4	118.9	C10—C11—H11B	109.5
C5—C4—H4	118.9	H11A—C11—H11B	109.5
C6—C5—C4	119.46 (12)	C10—C11—H11C	109.5
C6—C5—C9	121.20 (12)	H11A—C11—H11C	109.5
C4—C5—C9	119.34 (12)	H11B—C11—H11C	109.5
O1—C1—C2—C3	179.96 (13)	C8—N1—C4—C5	−0.6 (2)
C3i—C1—C2—C3	−0.1 (2)	N1—C4—C5—C6	0.2 (2)
O1—C1—C2—Cl1	0.78 (18)	N1—C4—C5—C9	−179.19 (13)
C3i—C1—C2—Cl1	−179.23 (9)	C4—C5—C6—C7	0.4 (2)
C1—C2—C3—O2	−179.86 (12)	C9—C5—C6—C7	179.82 (13)
Cl1—C2—C3—O2	−0.72 (19)	C5—C6—C7—C8	−0.6 (2)
C1—C2—C3—C1i	0.1 (2)	C4—N1—C8—C7	0.4 (2)
Cl1—C2—C3—C1i	179.21 (9)	C6—C7—C8—N1	0.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2···N1	0.92 (3)	1.75 (3)	2.6111 (17)	154 (3)
O2—H2···O1i	0.92 (3)	2.25 (3)	2.6824 (14)	108 (2)
C4—H4···N2ii	0.95	2.46	3.292 (2)	146
C6—H6···N3	0.95	2.57	3.385 (2)	144
C7—H7···O1iii	0.95	2.48	3.4248 (18)	172
C11—H11A···N2	0.98	2.62	3.341 (2)	130

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2⋯N1	0.92 (3)	1.75 (3)	2.6111 (17)	154 (3)
O2—H2⋯O1i	0.92 (3)	2.25 (3)	2.6824 (14)	108 (2)
C4—H4⋯N2ii	0.95	2.46	3.292 (2)	146
C6—H6⋯N3	0.95	2.57	3.385 (2)	144
C7—H7⋯O1iii	0.95	2.48	3.4248 (18)	172
C11—H11A⋯N2	0.98	2.62	3.341 (2)	130

Symmetry codes: (i) ; (ii) ; (iii) .