4,4′-Bipyridine–trans,trans-hexa-2,4-dienedioic acid (1/1)

Abstract

The title cocrystal, C₁₀H₈N₂·C₆H₆O₄, crystallizes with half-mol­ecules of 4,4′-bipyridine and trans,trans-hexa-2,4-dienedioic acid in the asymmetric unit, as each is located about a crystallographic inversion center. The bipyridine molecule is planar from symmetry. In the dicarboxylic acid molecule, the O—C—C—C torsion angle is −13.0 (2)°. In the crystal, O—H⋯N and C—H⋯O hydrogen bonds generate a three-dimensional network.

Related literature  

For cocrystals of carb­oxy­lic acid and pyridine, see: Bhogala & Nangia (2003 ▶); Hou et al. (2008 ▶); Jiang & Hou (2012 ▶). For background to the applications of cocrystals, see: Bhogala & Nangia (2003 ▶); Gao et al. (2004 ▶); Hori et al. (2009 ▶); Weyna et al. (2009 ▶).

Experimental  

Crystal data  

• C₁₀H₈N₂·C₆H₆O₄

• M _r = 298.29

• Triclinic,

• a = 5.8481 (5) Å

• b = 7.6348 (6) Å

• c = 8.4677 (7) Å

• α = 91.837 (5)°

• β = 92.584 (5)°

• γ = 111.907 (4)°

• V = 349.93 (5) ų

• Z = 1

• Mo Kα radiation

• μ = 0.10 mm⁻¹

• T = 173 K

• 0.40 × 0.26 × 0.24 mm

Data collection  

• Bruker APEXII CCD diffractometer

• Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.960, T _max = 0.976

• 5973 measured reflections

• 1517 independent reflections

• 1336 reflections with I > 2σ(I)

• R _int = 0.031

Refinement  

• R[F ² > 2σ(F ²)] = 0.040

• wR(F ²) = 0.116

• S = 1.04

• 1517 reflections

• 104 parameters

• H atoms treated by a mixture of independent and constrained refinement

• Δρ_max = 0.24 e Å⁻³

• Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2006 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Supplementary material file. DOI: 10.1107/S1600536812012391/sj5219Isup3.cml

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
O1—H1⋯N1	1.06 (2)	1.58 (2)	2.6148 (14)	164 (2)
C2—H2⋯O2i	0.95	2.65	3.5130 (15)	151
C3—H3⋯O2ii	0.95	2.58	3.4457 (16)	152
C4—H4⋯O1iii	0.95	2.58	3.4848 (17)	160
C8—H8⋯O2iv	0.95	2.56	3.3555 (17)	141

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

supplementary crystallographic information

Comment

Considerable effort has been devoted to form co-crystals made up of two or more components because of their potential applications in pharmaceutical chemisty (Weyna et al., 2009), supramolecular chemistry (Bhogala & Nangia, 2003; Gao et al., 2004) and materials chemistry (Hori et al., 2009). In particular, numerous studies have focused on hydrogen bonding between carboxylic acid and pyridine molecules (Bhogala & Nangia, 2003; Hou et al., 2008; Jiang & Hou, 2012). We report here the structure of a co-crystal of trans, trans-hexa-2,4-dienedioic acid with 4,4'-bipyridine in the solid state.

The title compound is shown in Fig. 1. The asymmetric unit contains half-molecules of 4,4'-bipyridine and trans,trans-1,3 -butadiene-1,4-dicarboxylic acid each located on crystallographic inversion centers. Both components are planar by symmetry and tilted by 32.02 (7)° with respect to each other.

In the crystal, the dicarboxylic acid molecules are arranged side by side by intermolecular C—H···O hydrogen bonds between the dicarboxylic acid molecules, leading to the formation of a one dimensional chain. Moreover, intermolecular O—H···N and C—H···O hydrogen bonds between dicarboxylic acid and 4,4'-bipyridine molecules generate a three-dimensional network (Fig. 2, Table 1).

Experimental

A mixture of stoichiometric amounts of trans, trans-hexa-2,4-dienedioic acid and 4,4'-bipyridine in DMF (in a 1:1 volume ratio) was heated until the two components dissolved and was then kept at room temperature. Upon slow evaporation of the solvent, X–ray quality single crystals were obtained.

Refinement

The carboxyl-H atom was located in a difference Fourier map and refined isotropically. Csp² H atoms were positioned geometrically and refined using a riding model with d(C—H) = 0.95 Å and U_iso(H) = 1.2U_eq(C).

Figures

Fig. 1.

The molecular structure of the title compound, showing displacement ellipsoids drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines. (Symmetry codes: i) -x + 1, -y + 1, -z + 1; ii) -x, -y + 3, -z.)

Fig. 2.

Crystal packing of the title compound with intermolecular O—H···N and C—H···O hydrogen bonds shown as dashed lines. (Symmetry codes: i) -x + 1, -y + 1, -z + 1; ii) -x, -y + 2, -z + 1; iii) x, y - 1, z + 1; iv) -x + 1, -y + 2, -z + 1; v) x + 1, y + 1, z + 1; vi) -x + 1, -y + 2, -z.)

Crystal data

C10H8N2·C6H6O4	Z = 1
Mr = 298.29	F(000) = 156
Triclinic, P1	Dx = 1.415 Mg m−3
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.8481 (5) Å	Cell parameters from 4151 reflections
b = 7.6348 (6) Å	θ = 2.4–28.4°
c = 8.4677 (7) Å	µ = 0.10 mm−1
α = 91.837 (5)°	T = 173 K
β = 92.584 (5)°	Block, colourless
γ = 111.907 (4)°	0.40 × 0.26 × 0.24 mm
V = 349.93 (5) Å3

Data collection

Bruker APEXII CCD diffractometer	1517 independent reflections
Radiation source: fine-focus sealed tube	1336 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.031
φ and ω scans	θmax = 27.0°, θmin = 2.4°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.960, Tmax = 0.976	k = −9→9
5973 measured reflections	l = −10→10

Refinement

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.116	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ2(Fo2) + (0.0688P)2 + 0.0753P] where P = (Fo2 + 2Fc2)/3
1517 reflections	(Δ/σ)max < 0.001
104 parameters	Δρmax = 0.24 e Å−3
0 restraints	Δρmin = −0.25 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
O1	0.05949 (18)	1.05053 (14)	0.23387 (13)	0.0414 (3)
H1	0.184 (4)	0.987 (3)	0.271 (3)	0.084 (7)*
O2	0.37461 (17)	1.23144 (14)	0.09959 (12)	0.0394 (3)
C1	0.1653 (2)	1.18769 (18)	0.13952 (14)	0.0285 (3)
C2	−0.0033 (2)	1.28402 (18)	0.09016 (15)	0.0299 (3)
H2	−0.1740	1.2262	0.1077	0.036*
C3	0.0786 (2)	1.44912 (17)	0.02208 (14)	0.0288 (3)
H3	0.2485	1.5031	0.0013	0.035*
N1	0.3031 (2)	0.85144 (15)	0.34658 (13)	0.0331 (3)
C4	0.2266 (3)	0.7745 (2)	0.48325 (17)	0.0374 (3)
H4	0.1161	0.8150	0.5389	0.045*
C5	0.3007 (3)	0.6385 (2)	0.54775 (16)	0.0350 (3)
H5	0.2419	0.5882	0.6458	0.042*
C6	0.4615 (2)	0.57572 (16)	0.46878 (14)	0.0262 (3)
C7	0.5464 (3)	0.6613 (2)	0.32875 (16)	0.0351 (3)
H7	0.6611	0.6270	0.2719	0.042*
C8	0.4627 (3)	0.79683 (19)	0.27252 (16)	0.0362 (3)
H8	0.5224	0.8532	0.1766	0.043*

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
O1	0.0346 (5)	0.0401 (6)	0.0593 (7)	0.0222 (4)	0.0127 (5)	0.0259 (5)
O2	0.0314 (5)	0.0469 (6)	0.0488 (6)	0.0229 (4)	0.0109 (4)	0.0174 (5)
C1	0.0283 (6)	0.0293 (6)	0.0319 (6)	0.0148 (5)	0.0032 (5)	0.0056 (5)
C2	0.0260 (6)	0.0327 (7)	0.0355 (6)	0.0156 (5)	0.0037 (5)	0.0077 (5)
C3	0.0270 (6)	0.0324 (6)	0.0316 (6)	0.0156 (5)	0.0042 (5)	0.0067 (5)
N1	0.0322 (6)	0.0287 (6)	0.0407 (6)	0.0141 (5)	−0.0015 (5)	0.0074 (4)
C4	0.0397 (7)	0.0387 (7)	0.0434 (7)	0.0248 (6)	0.0073 (6)	0.0078 (6)
C5	0.0406 (7)	0.0390 (7)	0.0339 (7)	0.0234 (6)	0.0080 (5)	0.0106 (5)
C6	0.0253 (6)	0.0255 (6)	0.0291 (6)	0.0110 (5)	−0.0015 (5)	0.0030 (5)
C7	0.0372 (7)	0.0377 (7)	0.0373 (7)	0.0205 (6)	0.0084 (5)	0.0114 (6)
C8	0.0395 (7)	0.0351 (7)	0.0382 (7)	0.0176 (6)	0.0055 (6)	0.0135 (6)

Geometric parameters (Å, º)

O1—C1	1.3162 (15)	C4—C5	1.3839 (18)
O1—H1	1.06 (2)	C4—H4	0.9500
O2—C1	1.2096 (16)	C5—C6	1.3907 (17)
C1—C2	1.4873 (16)	C5—H5	0.9500
C2—C3	1.3310 (18)	C6—C7	1.3929 (18)
C2—H2	0.9500	C6—C6ii	1.492 (2)
C3—C3i	1.452 (2)	C7—C8	1.3872 (17)
C3—H3	0.9500	C7—H7	0.9500
N1—C8	1.3286 (17)	C8—H8	0.9500
N1—C4	1.3337 (18)
C1—O1—H1	110.3 (13)	C5—C4—H4	118.5
O2—C1—O1	124.23 (11)	C4—C5—C6	119.86 (12)
O2—C1—C2	124.24 (11)	C4—C5—H5	120.1
O1—C1—C2	111.52 (10)	C6—C5—H5	120.1
C3—C2—C1	121.76 (12)	C5—C6—C7	116.57 (11)
C3—C2—H2	119.1	C5—C6—C6ii	121.53 (14)
C1—C2—H2	119.1	C7—C6—C6ii	121.90 (14)
C2—C3—C3i	123.31 (15)	C8—C7—C6	119.78 (12)
C2—C3—H3	118.3	C8—C7—H7	120.1
C3i—C3—H3	118.3	C6—C7—H7	120.1
C8—N1—C4	117.62 (11)	N1—C8—C7	123.05 (12)
N1—C4—C5	123.05 (12)	N1—C8—H8	118.5
N1—C4—H4	118.5	C7—C8—H8	118.5
O2—C1—C2—C3	−13.0 (2)	C4—C5—C6—C6ii	−177.69 (14)
O1—C1—C2—C3	166.14 (12)	C5—C6—C7—C8	−2.2 (2)
C1—C2—C3—C3i	−177.53 (14)	C6ii—C6—C7—C8	177.72 (14)
C8—N1—C4—C5	−1.8 (2)	C4—N1—C8—C7	1.8 (2)
N1—C4—C5—C6	−0.3 (2)	C6—C7—C8—N1	0.2 (2)
C4—C5—C6—C7	2.3 (2)

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

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···N1	1.06 (2)	1.58 (2)	2.6148 (14)	164 (2)
C2—H2···O2iii	0.95	2.65	3.5130 (15)	151
C3—H3···O2iv	0.95	2.58	3.4457 (16)	152
C4—H4···O1v	0.95	2.58	3.4848 (17)	160
C8—H8···O2vi	0.95	2.56	3.3555 (17)	141

Symmetry codes: (iii) x−1, y, z; (iv) −x+1, −y+3, −z; (v) −x, −y+2, −z+1; (vi) −x+1, −y+2, −z.