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

In the crystal structure of the title compound, C(6)H(4)N(2)·C(6)H(2)Cl(2)O(4), two chloranilic acid (systematic name: 2,5-dichloro-3,6-dihydr-oxy-1,4-benzoquinone) mol-ecules are connected by O-H⋯O hydrogen bonds to form a dimeric unit. The pyridine-4-carbonitrile mol-ecules 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 inter-molecular 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 = 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 (; 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

Δρmax = 0.43 e Å−3

Δρmin = −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 ▶).

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

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

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

C6H4N2·C6H2Cl2O4	F000 = 632.00
Mr = 313.10	Dx = 1.660 Mg m−3
Monoclinic, P21/n	Mo Kα radiation λ = 0.71075 Å
Hall symbol: -P 2yn	Cell parameters from 7762 reflections
a = 14.9327 (8) Å	θ = 3.0–30.0º
b = 4.9301 (3) Å	µ = 0.53 mm−1
c = 17.0355 (10) Å	T = 180 (2) K
β = 93.0474 (18)º	Needle, brown
V = 1252.37 (13) Å3	0.18 × 0.18 × 0.08 mm
Z = 4

Rigaku R-AXIS RAPIDII diffractometer	2165 reflections with I > 2σ(I)
Detector resolution: 10.00 pixels mm-1	Rint = 0.076
ω scans	θmax = 30.0º
Absorption correction: numerical(ABSCOR; Higashi, 1995)	h = −20→20
Tmin = 0.900, Tmax = 0.958	k = −6→6
11539 measured reflections	l = −23→22
3567 independent reflections

Refinement on F2	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.058	H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.177	w = 1/[σ2(Fo2) + (0.0805P)2] where P = (Fo2 + 2Fc2)/3
S = 1.07	(Δ/σ)max = 0.001
3567 reflections	Δρmax = 0.43 e Å−3
192 parameters	Δρmin = −0.73 e Å−3
Primary atom site location: structure-invariant direct methods	Extinction correction: none
Secondary atom site location: difference Fourier map

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	Occ. (<1)
Cl1	0.72657 (5)	1.21818 (15)	0.67956 (4)	0.0293 (2)
Cl2	0.72206 (5)	0.30951 (15)	0.41510 (4)	0.0317 (2)
O1	0.57647 (13)	1.0461 (5)	0.56722 (13)	0.0341 (5)
O2	0.87571 (13)	0.8329 (4)	0.64426 (13)	0.0303 (5)
H2	0.914 (7)	0.62 (2)	0.647 (5)	0.036*	0.54 (17)
O3	0.87474 (13)	0.4764 (5)	0.52519 (13)	0.0343 (5)
O4	0.57459 (14)	0.6729 (5)	0.45427 (14)	0.0316 (5)
H4	0.540 (3)	0.781 (8)	0.466 (2)	0.048 (13)*
N1	0.97525 (16)	0.4095 (6)	0.67823 (15)	0.0303 (6)
H1	0.944 (9)	0.53 (3)	0.658 (6)	0.036*	0.46 (17)
N2	1.18662 (18)	−0.3815 (6)	0.78927 (17)	0.0370 (6)
C1	0.64869 (18)	0.9233 (6)	0.56045 (16)	0.0256 (6)
C2	0.72824 (18)	0.9664 (6)	0.60781 (16)	0.0249 (6)
C3	0.80477 (18)	0.8142 (6)	0.60089 (17)	0.0248 (6)
C4	0.80495 (18)	0.5996 (6)	0.53513 (17)	0.0254 (6)
C5	0.72339 (19)	0.5549 (6)	0.48720 (16)	0.0266 (6)
C6	0.65029 (18)	0.7065 (6)	0.49777 (17)	0.0244 (6)
C7	0.9672 (2)	0.3253 (7)	0.7517 (2)	0.0354 (7)
H7	0.9239	0.4070	0.7831	0.043*
C8	1.0209 (2)	0.1210 (7)	0.78260 (18)	0.0333 (7)
H8	1.0152	0.0599	0.8350	0.040*
C9	1.08368 (18)	0.0063 (6)	0.73566 (17)	0.0275 (6)
C10	1.0914 (2)	0.0969 (7)	0.65940 (19)	0.0372 (8)
H10	1.1348	0.0208	0.6271	0.045*
C11	1.0349 (2)	0.2994 (7)	0.6313 (2)	0.0355 (7)
H11	1.0382	0.3613	0.5787	0.043*
C12	1.1423 (2)	−0.2083 (6)	0.76598 (19)	0.0310 (7)

	U11	U22	U33	U12	U13	U23
Cl1	0.0338 (4)	0.0282 (4)	0.0255 (4)	−0.0001 (3)	−0.0033 (3)	−0.0035 (3)
Cl2	0.0369 (4)	0.0322 (4)	0.0257 (4)	0.0089 (3)	−0.0017 (3)	−0.0053 (3)
O1	0.0287 (10)	0.0399 (12)	0.0328 (12)	0.0106 (10)	−0.0062 (9)	−0.0093 (10)
O2	0.0283 (10)	0.0288 (11)	0.0327 (12)	0.0020 (9)	−0.0080 (9)	0.0018 (9)
O3	0.0287 (10)	0.0407 (13)	0.0333 (12)	0.0107 (9)	−0.0004 (9)	0.0012 (10)
O4	0.0242 (10)	0.0364 (12)	0.0335 (12)	0.0074 (9)	−0.0062 (9)	−0.0105 (10)
N1	0.0276 (13)	0.0333 (14)	0.0292 (14)	0.0032 (11)	−0.0055 (10)	0.0018 (12)
N2	0.0375 (14)	0.0337 (14)	0.0398 (16)	0.0036 (12)	0.0012 (12)	0.0039 (13)
C1	0.0263 (13)	0.0280 (14)	0.0223 (14)	0.0038 (12)	0.0001 (11)	0.0014 (12)
C2	0.0272 (13)	0.0264 (14)	0.0208 (13)	0.0010 (12)	−0.0011 (10)	−0.0012 (11)
C3	0.0212 (13)	0.0289 (15)	0.0239 (14)	−0.0010 (11)	−0.0030 (10)	0.0045 (12)
C4	0.0285 (14)	0.0241 (13)	0.0237 (14)	0.0044 (11)	0.0004 (11)	0.0062 (12)
C5	0.0305 (14)	0.0282 (14)	0.0209 (14)	0.0022 (12)	−0.0004 (11)	−0.0027 (12)
C6	0.0254 (14)	0.0239 (14)	0.0233 (14)	0.0020 (11)	−0.0039 (11)	−0.0003 (11)
C7	0.0345 (16)	0.0420 (19)	0.0294 (16)	0.0084 (14)	−0.0018 (13)	−0.0026 (14)
C8	0.0388 (16)	0.0361 (16)	0.0245 (15)	0.0075 (14)	−0.0023 (12)	0.0051 (14)
C9	0.0264 (13)	0.0268 (14)	0.0286 (15)	−0.0002 (12)	−0.0060 (11)	0.0001 (12)
C10	0.0332 (16)	0.0460 (19)	0.0323 (17)	0.0089 (15)	0.0016 (13)	0.0056 (15)
C11	0.0319 (16)	0.0425 (19)	0.0321 (17)	0.0059 (14)	0.0006 (13)	0.0106 (14)
C12	0.0327 (15)	0.0289 (15)	0.0309 (17)	−0.0018 (13)	−0.0030 (13)	0.0011 (13)

Cl1—C2	1.743 (3)	C2—C3	1.377 (4)
Cl2—C5	1.723 (3)	C3—C4	1.541 (4)
O1—C1	1.247 (3)	C4—C5	1.447 (4)
O2—C3	1.262 (3)	C5—C6	1.343 (4)
O2—H2	1.20 (14)	C7—C8	1.375 (4)
O3—C4	1.226 (3)	C7—H7	0.9500
O4—C6	1.329 (3)	C8—C9	1.384 (4)
O4—H4	0.77 (4)	C8—H8	0.9500
N1—C7	1.330 (4)	C9—C10	1.384 (4)
N1—C11	1.343 (4)	C9—C12	1.451 (4)
N1—H1	0.83 (17)	C10—C11	1.376 (4)
N2—C12	1.138 (4)	C10—H10	0.9500
C1—C2	1.416 (4)	C11—H11	0.9500
C1—C6	1.512 (4)
C3—O2—H2	110 (4)	C4—C5—Cl2	119.1 (2)
C6—O4—H4	110 (3)	O4—C6—C5	122.0 (3)
C7—N1—C11	122.0 (3)	O4—C6—C1	115.9 (2)
C7—N1—H2	119 (3)	C5—C6—C1	122.1 (2)
C11—N1—H2	119 (3)	N1—C7—C8	120.6 (3)
C7—N1—H1	123 (6)	N1—C7—H7	119.7
C11—N1—H1	115 (6)	C8—C7—H7	119.7
O1—C1—C2	125.3 (3)	C7—C8—C9	118.5 (3)
O1—C1—C6	117.0 (2)	C7—C8—H8	120.7
C2—C1—C6	117.7 (2)	C9—C8—H8	120.7
C3—C2—C1	123.0 (3)	C10—C9—C8	120.2 (3)
C3—C2—Cl1	119.4 (2)	C10—C9—C12	119.4 (3)
C1—C2—Cl1	117.6 (2)	C8—C9—C12	120.4 (3)
O2—C3—C2	125.8 (3)	C11—C10—C9	118.7 (3)
O2—C3—C4	116.2 (2)	C11—C10—H10	120.6
C2—C3—C4	118.0 (2)	C9—C10—H10	120.6
O3—C4—C5	122.9 (3)	N1—C11—C10	120.0 (3)
O3—C4—C3	118.4 (2)	N1—C11—H11	120.0
C5—C4—C3	118.7 (2)	C10—C11—H11	120.0
C6—C5—C4	120.4 (3)	N2—C12—C9	178.2 (3)
C6—C5—Cl2	120.5 (2)
O1—C1—C2—C3	176.1 (3)	C4—C5—C6—O4	179.3 (3)
C6—C1—C2—C3	−2.4 (4)	Cl2—C5—C6—O4	0.6 (4)
O1—C1—C2—Cl1	−2.0 (4)	C4—C5—C6—C1	−1.5 (5)
C6—C1—C2—Cl1	179.5 (2)	Cl2—C5—C6—C1	179.9 (2)
C1—C2—C3—O2	−175.7 (3)	O1—C1—C6—O4	1.7 (4)
Cl1—C2—C3—O2	2.4 (4)	C2—C1—C6—O4	−179.7 (3)
C1—C2—C3—C4	3.8 (4)	O1—C1—C6—C5	−177.5 (3)
Cl1—C2—C3—C4	−178.1 (2)	C2—C1—C6—C5	1.1 (4)
O2—C3—C4—O3	−5.3 (4)	C11—N1—C7—C8	0.5 (5)
C2—C3—C4—O3	175.1 (3)	N1—C7—C8—C9	0.3 (5)
O2—C3—C4—C5	175.5 (3)	C7—C8—C9—C10	−0.1 (5)
C2—C3—C4—C5	−4.1 (4)	C7—C8—C9—C12	179.5 (3)
O3—C4—C5—C6	−176.2 (3)	C8—C9—C10—C11	−0.8 (5)
C3—C4—C5—C6	3.0 (4)	C12—C9—C10—C11	179.6 (3)
O3—C4—C5—Cl2	2.5 (4)	C7—N1—C11—C10	−1.4 (5)
C3—C4—C5—Cl2	−178.4 (2)	C9—C10—C11—N1	1.5 (5)

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···Cl2iv	0.95	2.81	3.710 (3)	158
C11—H11···O3v	0.95	2.39	3.245 (4)	150

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⋯Cl2iv	0.95	2.81	3.710 (3)	158
C11—H11⋯O3v	0.95	2.39	3.245 (4)	150

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