4-[(E)-2-(Pyridin-2-yl)ethen-yl]pyridine-terephthalic acid (2/1).

The title 2:1 co-crystal, 2C12H10N2·C8H6O4, crystallizes with one mol-ecule of 4-[(E)-2-(pyridin-2-yl)ethen-yl]pyridine (A) and one half-mol-ecule of terephthalic acid (B) in the asymmetric unit. In the crystal, the components are linked through heterodimeric COOH⋯Npyridine synthons, forming linear aggregates of composition -A-B-A-B-. Further linkage through weak C-H⋯O and C-H⋯π inter-actions gives two-dimensional hydrogen-bonded undulating sheets propagating in the [100] and [010] directions. These layers are connected through additional weak C-H⋯O contacts, forming a three-dimensional structure.

Related literature

For reports on supra­molecular crystal engineering and potential applications of co-crystals, see: Desiraju (1995 ▶); Simon & Bassoul (2000 ▶); Bhogala & Nangia (2003 ▶); Weyna et al. (2009 ▶); Yan et al. (2012 ▶). For background to related co-crystals, see: Santra et al. (2008 ▶); Moon & Park (2012 ▶); Ebenezer & Muthiah (2012 ▶).

Experimental

Crystal data

C12H10N2·0.5C8H6O4

M = 265.28

Monoclinic,

a = 6.3821 (8) Å

b = 32.301 (4) Å

c = 6.8721 (8) Å

β = 111.440 (2)°

V = 1318.6 (3) Å3

Z = 4

Mo Kα radiation

μ = 0.09 mm−1

T = 293 K

0.48 × 0.41 × 0.34 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.96, T max = 0.97

12715 measured reflections

2328 independent reflections

2119 reflections with I > 2σ(I)

R int = 0.033

Refinement

R[F 2 > 2σ(F 2)] = 0.055

wR(F 2) = 0.149

S = 1.17

2328 reflections

184 parameters

1 restraint

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.14 e Å−3

Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT-Plus (Bruker 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 2012 ▶) and Mercury (Macrae et al. 2008 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Click here for additional data file.

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812046284/su2525sup1.cif

Click here for additional data file.

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812046284/su2525Isup2.hkl

Click here for additional data file.

Supplementary material file. DOI: 10.1107/S1600536812046284/su2525Isup3.cml

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

C12H10N2·0.5C8H6O4	F(000) = 556
Mr = 265.28	Dx = 1.336 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 4971 reflections
a = 6.3821 (8) Å	θ = 2.5–27.1°
b = 32.301 (4) Å	µ = 0.09 mm−1
c = 6.8721 (8) Å	T = 293 K
β = 111.440 (2)°	Block, colourless
V = 1318.6 (3) Å3	0.48 × 0.41 × 0.34 mm
Z = 4

Bruker SMART CCD area-detector diffractometer	2328 independent reflections
Radiation source: fine-focus sealed tube	2119 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.033
phi and ω scans	θmax = 25.0°, θmin = 2.5°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −7→7
Tmin = 0.96, Tmax = 0.97	k = −38→38
12715 measured reflections	l = −8→8

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)] = 0.055	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.149	H atoms treated by a mixture of independent and constrained refinement
S = 1.17	w = 1/[σ2(Fo2) + (0.0769P)2 + 0.2452P] where P = (Fo2 + 2Fc2)/3
2328 reflections	(Δ/σ)max < 0.001
184 parameters	Δρmax = 0.14 e Å−3
1 restraint	Δρmin = −0.20 e Å−3

Experimental. Spectroscopic and TGA data for the title compound: IR (KBr): 3056, 2944, 1706, 1683, 1606, 1581, 1504, 1425, 1290 y 731 cm-1. 1H-RMN (200 MHz, DMSO-d6, TMS): δ 8.59 (m, 3H), 8.04 (s, 4H), 7.83 (td, J = 0.8, 4 Hz, 1H), 7.61 (m, 5H), 7.32 (m, 1H). TGA Calcd. for 2 C12H10N2: 68.69. Found: 69.27% (303 - 533 K).

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
O1	0.7604 (3)	0.03567 (5)	0.8732 (2)	0.0626 (4)
H1'	0.752 (4)	0.0508 (7)	0.969 (3)	0.094*
O2	1.0571 (2)	0.07552 (4)	0.9137 (2)	0.0646 (4)
C1	0.9678 (3)	0.02216 (5)	0.6602 (3)	0.0419 (4)
C2	0.8138 (3)	−0.00755 (6)	0.5490 (3)	0.0497 (5)
H2	0.6876	−0.0128	0.5824	0.060*
C3	1.1549 (3)	0.02934 (6)	0.6094 (3)	0.0502 (5)
H3	1.2603	0.0491	0.6830	0.060*
C4	0.9339 (3)	0.04711 (6)	0.8289 (3)	0.0478 (5)
N1	0.7178 (3)	0.08162 (5)	0.1678 (2)	0.0525 (4)
N2	0.6102 (3)	0.20912 (5)	0.9682 (3)	0.0577 (5)
C5	0.5534 (3)	0.07399 (6)	0.2373 (3)	0.0525 (5)
H5	0.4559	0.0521	0.1784	0.063*
C6	0.5203 (3)	0.09677 (6)	0.3915 (3)	0.0515 (5)
H6	0.4020	0.0903	0.4346	0.062*
C7	0.6625 (3)	0.12946 (6)	0.4837 (3)	0.0471 (5)
C8	0.8332 (3)	0.13732 (7)	0.4096 (3)	0.0567 (5)
H8	0.9330	0.1590	0.4651	0.068*
C9	0.8553 (4)	0.11300 (7)	0.2539 (3)	0.0580 (5)
H9	0.9714	0.1188	0.2067	0.070*
C10	0.6360 (3)	0.15554 (6)	0.6476 (3)	0.0519 (5)
H10	0.7328	0.1781	0.6911	0.062*
C11	0.4900 (3)	0.15052 (6)	0.7397 (3)	0.0509 (5)
H11	0.3948	0.1277	0.6996	0.061*
C12	0.4641 (3)	0.17767 (5)	0.8998 (3)	0.0472 (5)
C13	0.2917 (3)	0.17128 (6)	0.9726 (3)	0.0545 (5)
H13	0.1941	0.1490	0.9238	0.065*
C14	0.2652 (4)	0.19789 (7)	1.1171 (3)	0.0628 (6)
H14	0.1481	0.1942	1.1654	0.075*
C15	0.4136 (4)	0.22994 (7)	1.1891 (3)	0.0656 (6)
H15	0.4008	0.2484	1.2880	0.079*
C16	0.5813 (4)	0.23397 (7)	1.1110 (4)	0.0682 (6)
H16	0.6827	0.2557	1.1613	0.082*

	U11	U22	U33	U12	U13	U23
O1	0.0692 (9)	0.0688 (10)	0.0642 (9)	−0.0138 (7)	0.0414 (8)	−0.0204 (7)
O2	0.0679 (9)	0.0625 (9)	0.0677 (9)	−0.0156 (7)	0.0300 (8)	−0.0246 (7)
C1	0.0449 (10)	0.0379 (9)	0.0434 (10)	0.0019 (7)	0.0166 (8)	0.0039 (7)
C2	0.0455 (10)	0.0521 (11)	0.0588 (11)	−0.0072 (8)	0.0276 (9)	−0.0060 (9)
C3	0.0508 (11)	0.0474 (10)	0.0553 (11)	−0.0111 (8)	0.0228 (9)	−0.0094 (8)
C4	0.0498 (10)	0.0485 (11)	0.0452 (10)	0.0027 (8)	0.0174 (8)	0.0011 (8)
N1	0.0618 (10)	0.0534 (9)	0.0457 (9)	0.0075 (8)	0.0237 (8)	0.0007 (7)
N2	0.0646 (11)	0.0492 (9)	0.0602 (10)	−0.0050 (8)	0.0238 (8)	−0.0120 (8)
C5	0.0594 (12)	0.0499 (11)	0.0494 (11)	−0.0002 (9)	0.0215 (9)	−0.0047 (8)
C6	0.0560 (11)	0.0508 (11)	0.0521 (11)	−0.0006 (9)	0.0250 (9)	−0.0039 (8)
C7	0.0525 (11)	0.0440 (10)	0.0443 (10)	0.0072 (8)	0.0170 (8)	0.0036 (8)
C8	0.0592 (12)	0.0568 (12)	0.0559 (11)	−0.0050 (9)	0.0232 (10)	−0.0035 (9)
C9	0.0620 (12)	0.0632 (13)	0.0576 (12)	0.0011 (10)	0.0323 (10)	0.0025 (10)
C10	0.0596 (11)	0.0439 (10)	0.0522 (11)	−0.0025 (8)	0.0205 (9)	−0.0047 (8)
C11	0.0594 (11)	0.0433 (10)	0.0499 (11)	−0.0015 (9)	0.0199 (9)	−0.0059 (8)
C12	0.0555 (11)	0.0399 (10)	0.0439 (10)	0.0051 (8)	0.0154 (8)	0.0020 (7)
C13	0.0643 (12)	0.0461 (11)	0.0548 (11)	0.0005 (9)	0.0239 (10)	0.0014 (8)
C14	0.0770 (14)	0.0600 (13)	0.0610 (12)	0.0113 (11)	0.0367 (11)	0.0038 (10)
C15	0.0885 (16)	0.0541 (12)	0.0562 (12)	0.0142 (11)	0.0288 (11)	−0.0072 (10)
C16	0.0810 (15)	0.0527 (12)	0.0669 (13)	−0.0062 (11)	0.0224 (12)	−0.0188 (10)

O1—C4	1.305 (2)	C7—C8	1.384 (3)
O1—H1'	0.8401 (10)	C7—C10	1.465 (3)
O2—C4	1.210 (2)	C8—C9	1.376 (3)
C1—C3	1.381 (2)	C8—H8	0.9300
C1—C2	1.386 (3)	C9—H9	0.9300
C1—C4	1.491 (3)	C10—C11	1.314 (3)
C2—C3i	1.371 (3)	C10—H10	0.9300
C2—H2	0.9300	C11—C12	1.463 (3)
C3—C2i	1.371 (3)	C11—H11	0.9300
C3—H3	0.9300	C12—C13	1.380 (3)
N1—C5	1.325 (2)	C13—C14	1.369 (3)
N1—C9	1.330 (3)	C13—H13	0.9300
N2—C16	1.332 (3)	C14—C15	1.368 (3)
N2—C12	1.342 (2)	C14—H14	0.9300
C5—C6	1.369 (3)	C15—C16	1.368 (3)
C5—H5	0.9300	C15—H15	0.9300
C6—C7	1.386 (3)	C16—H16	0.9300
C6—H6	0.9300
C4—O1—H1'	108.9 (19)	C7—C8—H8	120.0
C3—C1—C2	118.76 (17)	N1—C9—C8	122.86 (19)
C3—C1—C4	119.37 (16)	N1—C9—H9	118.6
C2—C1—C4	121.86 (16)	C8—C9—H9	118.6
C3i—C2—C1	120.91 (17)	C11—C10—C7	126.94 (18)
C3i—C2—H2	119.5	C11—C10—H10	116.5
C1—C2—H2	119.5	C7—C10—H10	116.5
C2i—C3—C1	120.33 (17)	C10—C11—C12	125.68 (18)
C2i—C3—H3	119.8	C10—C11—H11	117.2
C1—C3—H3	119.8	C12—C11—H11	117.2
O2—C4—O1	124.02 (17)	N2—C12—C13	122.00 (17)
O2—C4—C1	122.08 (17)	N2—C12—C11	117.51 (17)
O1—C4—C1	113.89 (16)	C13—C12—C11	120.47 (17)
C5—N1—C9	117.55 (16)	C14—C13—C12	119.7 (2)
C16—N2—C12	116.65 (18)	C14—C13—H13	120.2
N1—C5—C6	123.07 (18)	C12—C13—H13	120.2
N1—C5—H5	118.5	C15—C14—C13	119.0 (2)
C6—C5—H5	118.5	C15—C14—H14	120.5
C5—C6—C7	120.20 (18)	C13—C14—H14	120.5
C5—C6—H6	119.9	C14—C15—C16	117.86 (19)
C7—C6—H6	119.9	C14—C15—H15	121.1
C8—C7—C6	116.35 (17)	C16—C15—H15	121.1
C8—C7—C10	120.33 (18)	N2—C16—C15	124.8 (2)
C6—C7—C10	123.31 (17)	N2—C16—H16	117.6
C9—C8—C7	119.96 (19)	C15—C16—H16	117.6
C9—C8—H8	120.0
C3—C1—C2—C3i	−0.4 (3)	C7—C8—C9—N1	0.2 (3)
C4—C1—C2—C3i	178.17 (17)	C8—C7—C10—C11	−176.30 (19)
C2—C1—C3—C2i	0.4 (3)	C6—C7—C10—C11	5.1 (3)
C4—C1—C3—C2i	−178.21 (17)	C7—C10—C11—C12	−178.50 (17)
C3—C1—C4—O2	5.2 (3)	C16—N2—C12—C13	0.2 (3)
C2—C1—C4—O2	−173.37 (18)	C16—N2—C12—C11	178.75 (18)
C3—C1—C4—O1	−175.43 (17)	C10—C11—C12—N2	−4.2 (3)
C2—C1—C4—O1	6.0 (3)	C10—C11—C12—C13	174.40 (19)
C9—N1—C5—C6	0.0 (3)	N2—C12—C13—C14	0.8 (3)
N1—C5—C6—C7	−0.3 (3)	C11—C12—C13—C14	−177.69 (18)
C5—C6—C7—C8	0.5 (3)	C12—C13—C14—C15	−1.2 (3)
C5—C6—C7—C10	179.21 (18)	C13—C14—C15—C16	0.5 (3)
C6—C7—C8—C9	−0.5 (3)	C12—N2—C16—C15	−0.9 (3)
C10—C7—C8—C9	−179.21 (18)	C14—C15—C16—N2	0.6 (4)
C5—N1—C9—C8	0.1 (3)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1′···N1ii	0.84	1.77	2.604 (2)	177
C9—H9···O2iii	0.93	2.67	3.285 (3)	125
C13—H13···O2iv	0.93	2.52	3.396 (2)	157
C5—H5···O2v	0.93	2.64	3.135 (2)	114
C16—H16···Cgvi	0.93	2.86	3.627 (3)	141

Table 1

Hydrogen-bond geometry (Å, °)

Cg is the centroid of the N2/C12–C16 pyridine ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1′⋯N1i	0.84	1.77	2.604 (2)	177
C9—H9⋯O2ii	0.93	2.67	3.285 (3)	125
C13—H13⋯O2iii	0.93	2.52	3.396 (2)	157
C5—H5⋯O2iv	0.93	2.64	3.135 (2)	114
C16—H16⋯Cg v	0.93	2.86	3.627 (3)	141

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