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

In the crystal structure of the title compound, 2C₆H₄N₂·C₆H₂Cl₂O₄·2C₂H₃N, the two symmetry-related pyridine-3-carbonitrile mol­ecules are linked to either side of a chloranilic acid (systematic name: 2,5-dichloro-3,6-dihydr­oxy-1,4-benzoquinone) mol­ecule via inter­molecular 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 mol­ecules 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 inter­molecular C—H...N and C—H...O hydrogen bonds, forming a tape along the c axis.

Key indicators

• Single-crystal X-ray study
• T = 180 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.035
• wR factor = 0.099
• Data-to-parameter ratio = 20.3

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT230_ALERT_2_C Hirshfeld Test Diff for    C5     --  C9      ..       5.08 su
PLAT371_ALERT_2_C Long   C(sp2)-C(sp1) Bond  C5     -   C9     ...       1.44 Ang.
PLAT042_ALERT_1_C Calc. and Reported MoietyFormula Strings  Differ          ?
PLAT790_ALERT_4_C Centre of Gravity not Within Unit Cell: Resd.  #          3
              C2 H3 N

Alert level G
PLAT333_ALERT_2_G Check Large Av C6-Ring C-C Dist. C1     -C3_a          1.44 Ang.
PLAT335_ALERT_2_G Check Large C6 Ring    C-C Range C1     -C3_a          0.16 Ang.

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

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 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

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, 2008; Gotoh et al., 2009).

In the crystal structure of the title compound, two pyridine-3-carbonitrile molecules, one chloranilic acid molecule and two acetonitrile molecules are linked by O—H···N and C—H···N hydrogen bonds (Table 1) to afford a 2:1:2 aggregate (Fig. 1). The O···N distance [2.6111 (17) Å] between the acid and the base is comparable to that of 2.610 (3) Å in pyridine-4-carbonitrile–chloranilic acid (1/1), where the H atom in the O···H···N hydrogen bond is disordered (Gotoh, Nagoshi & Ishida, 2008), but in the title compound no distinct evidence of H disorder was observed in a difference Fourier map. The 2:1:2 aggregates are linked by weak intermolecular C—H···N and C—H···O hydrogen bonds, forming a tape along the c axis (Fig. 2). A short contact between the adjacent C≡N bonds of acetonitrile molecules is observed [C10···C10ⁱⁱⁱ 3.314 Å; symmetry code: (iii) -x - 1, -y + 2, -z + 1].

Related literature

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

S2. Experimental

Single crystals were obtained by slow evaporation from an acetonitrile solution (120 ml) of chloranilic acid (250 mg) and pyridine-3-carbonitrile (250 mg) at room temperature.

S3. Refinement

C-bound H atoms were positioned geometrically (C—H = 0.95 or 0.98 Å) and refined as riding, allowing for free rotation of the methyl group. U_iso(H) values were set at 1.2U_eq(C) or 1.5U_eq(methyl C). The O-bound H atom was found in a difference Fourier map and refined isotropically. The refined O—H distance is 0.92 (3) Å.

Computing details

Data collection: PROCESS-AUTO (Rigaku/MSC, 2004); cell refinement: PROCESS-AUTO (Rigaku/MSC, 2004); 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 (Rigaku/MSC, 2004) and PLATON (Spek, 2009).

Figures

	Fig. 1. The molecular structure of the title compound, with the atom-labeling. Displacement ellipsoids of non-H atoms are drawn at the 50% probability level. The dashed lines indicate O—H···O, O—H···N and C—H···N hydrogen bonds. [Symmetry code: (i) -x + 2, -y, -z].
	Fig. 2. A packing diagram of (I), showing a molecular tape running along the c axis. The dashed lines indicate O—H···O, O—H···N, C—H···N and C—H···O hydrogen bonds.

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

Crystal data

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) Å^3

Data collection

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

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

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	0.74850 (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)*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

Geometric parameters (Å, º)

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—C3^i	1.5153 (18)	C11—H11A	0.9800
C2—C3	1.3546 (17)	C11—H11B	0.9800
C3—C1^i	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—C3^i	117.75 (11)	C8—C7—C6	119.07 (12)
C2—C1—C3^i	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—C1^i	117.14 (11)	N2—C9—C5	179.14 (15)
C2—C3—C1^i	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)
C3^i—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)
C3^i—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—C1^i	0.1 (2)	C4—N1—C8—C7	0.4 (2)
Cl1—C2—C3—C1^i	179.21 (9)	C6—C7—C8—N1	0.3 (2)

Symmetry code: (i) −x+2, −y, −z.

Hydrogen-bond geometry (Å, º)

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···O1^i	0.92 (3)	2.25 (3)	2.6824 (14)	108 (2)
C4—H4···N2^ii	0.95	2.46	3.292 (2)	146
C6—H6···N3	0.95	2.57	3.385 (2)	144
C7—H7···O1^iii	0.95	2.48	3.4248 (18)	172
C11—H11A···N2	0.98	2.62	3.341 (2)	130

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