2-Phenyl­acetic acid–(E,E)-4,4’-(hydra­zinediylidene)dipyridine (2/1)

Abstract

The asymmetric unit of the title co-crystal, C₁₂H₁₀N₄·2C₈H₈O₂, comprises a single mol­ecule of 2-phenyl­acetic acid and half a mol­ecule of 4-pyridine­aldazine as this is situated about a centre of inversion. Mol­ecules are connected into a three component aggregate via O—H⋯N hydrogen bonds. As the carb­oxy­lic acid group is almost normal to the plane through the benzene ring to which it is attached [C—C—C—C = 93.7 (3) °], and the 4-pyridine­aldazine mol­ecule is planar (r.m.s. deviation of the 16 non-H atoms = 0.010 Å), the overall shape of the aggregate is that of an extended chair. In the crystal packing, layers of three component aggregates stack along the c axis.

Related literature

For related studies on co-crystal formation involving the isomeric n-pyridine­aldazines, see: Broker et al. (2008 ▶); Arman et al. (2010 ▶).

Experimental

Crystal data

• C₁₂H₁₀N₄·2C₈H₈O₂

• M _r = 482.53

• Monoclinic,

• a = 11.677 (7) Å

• b = 4.425 (2) Å

• c = 23.587 (13) Å

• β = 95.475 (8)°

• V = 1213.2 (11) ų

• Z = 2

• Mo Kα radiation

• μ = 0.09 mm⁻¹

• T = 98 K

• 0.40 × 0.16 × 0.05 mm

Data collection

• Rigaku AFC12/SATURN724 diffractometer

• 5399 measured reflections

• 2117 independent reflections

• 1735 reflections with I > 2σ(I)

• R _int = 0.056

Refinement

• R[F ² > 2σ(F ²)] = 0.068

• wR(F ²) = 0.152

• S = 1.14

• 2117 reflections

• 166 parameters

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

• Δρ_max = 0.18 e Å⁻³

• Δρ_min = −0.21 e Å⁻³

Data collection: CrystalClear (Molecular Structure Corporation & Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

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—H1o⋯N1	0.96 (4)	1.70 (4)	2.653 (3)	175 (3)

supplementary crystallographic information

Comment

As a continuation of studies into the phenomenon of co-crystallization of the isomeric n-pyridinealdazines (Broker et al., 2008; Arman et al., 2010), the co-crystallization of 2-phenylacetic acid and 4-pyridinealdazine was investigated. This lead to the isolation of the title 2/1 co-crystal.

The asymmetric unit comprises a molecule of 2-phenylacetic acid and half a molecule of 4-pyridinealdazine, with the latter disposed about a centre of inversion. The constituents are connected by O—H···N hydrogen bonds, Table 1, to generate a centrosymmetric three component aggregate, Fig. 1. The 2-phenylacetic acid molecule is non-planar as seen in the value of the C12–C7–C13—C14 torsion angle of 93.7 (3) °. By contrast, the 4-pyridinealdazine molecule is planar with the r.m.s. deviation of the 16 non-hydrogen atoms being 0.010 Å. Hence, the three component aggregate has the shape of an extended chair, Fig. 1.

In the crystal packing, the three component aggregates pack into layers that stack along the c axis, Fig. 2. There are no specific additional intermolecular interactions of note.

Experimental

Yellow crystals of (I) were isolated from the 2/1 co-crystallization of 2-phenylacetic acid (Sigma Aldrich) and 4-[(1E)-[(E)-2-(pyridin-4-ylmethylidene)hydrazin-1- ylidene]methyl]pyridine (Sigma Aldrich) in ethanol, m.p. 395–397 K. IR assignment (cm^-1): 2923 (ν C—H); 2428 (ν O—H); 1693 (ν C═O); 1602 (ν C═N); 1492,1453, 1409 (ν C–C (aromatic)); 1306 (ν C—N); 817, 716 (δ C—H).

Refinement

C-bound H-atoms were placed in calculated positions (C–H 0.95–0.99 Å) and were included in the refinement in the riding model approximation with U_iso(H) set to 1.2U_eq(C). The O-bound H-atom was located in a difference Fourier map and was refined with U_iso(H) = 1.5U_eq(O).

Figures

Fig. 1.

The three component aggregate in the 2:1 co-crystal formed between 2-phenylacetic acid and 4-pyridinealdazine showing atom-labelling scheme and displacement ellipsoids at the 70% probability level. Unlabelled atoms are related by the symmetry operation 1 - x, 1 - y, -z. The view highlights the extended chair conformation and the O—H···N hydrogen bonds (shown as orange dashed lines).

Fig. 2.

A view in projection down the a axis showing the stacking of layers of three component aggregates along c. The O—H···N hydrogen bonds are shown as orange dashed lines.

Crystal data

C12H10N4·2C8H8O2	F(000) = 508
Mr = 482.53	Dx = 1.321 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4281 reflections
a = 11.677 (7) Å	θ = 2.4–40.2°
b = 4.425 (2) Å	µ = 0.09 mm−1
c = 23.587 (13) Å	T = 98 K
β = 95.475 (8)°	Plate, yellow
V = 1213.2 (11) Å3	0.40 × 0.16 × 0.05 mm
Z = 2

Data collection

Rigaku AFC12K/SATURN724 diffractometer	1735 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	Rint = 0.056
graphite	θmax = 25.0°, θmin = 2.4°
ω scans	h = −13→13
5399 measured reflections	k = −5→4
2117 independent reflections	l = −28→28

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)] = 0.068	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.152	H atoms treated by a mixture of independent and constrained refinement
S = 1.14	w = 1/[σ2(Fo2) + (0.0468P)2 + 0.7865P] where P = (Fo2 + 2Fc2)/3
2117 reflections	(Δ/σ)max = 0.001
166 parameters	Δρmax = 0.18 e Å−3
0 restraints	Δρmin = −0.21 e Å−3

Special details

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
N1	0.18146 (19)	1.2809 (5)	0.09616 (10)	0.0316 (6)
N2	0.4766 (2)	0.6025 (5)	0.01894 (9)	0.0310 (5)
C1	0.1394 (3)	1.1780 (6)	0.04489 (13)	0.0361 (7)
H1	0.0651	1.2424	0.0298	0.043*
C2	0.2001 (2)	0.9811 (6)	0.01301 (12)	0.0321 (6)
H2	0.1668	0.9083	−0.0227	0.038*
C3	0.3098 (2)	0.8921 (6)	0.03387 (11)	0.0269 (6)
C4	0.3540 (2)	1.0017 (6)	0.08676 (12)	0.0303 (6)
H4	0.4290	0.9457	0.1024	0.036*
C5	0.2874 (2)	1.1929 (6)	0.11616 (12)	0.0305 (6)
H5	0.3183	1.2657	0.1523	0.037*
C6	0.3752 (2)	0.6842 (6)	0.00068 (11)	0.0291 (6)
H6	0.3414	0.6098	−0.0348	0.035*
O1	0.05896 (17)	1.6320 (5)	0.15872 (9)	0.0411 (6)
H1o	0.099 (3)	1.503 (8)	0.1346 (15)	0.062*
O2	−0.07727 (18)	1.5893 (5)	0.08618 (9)	0.0463 (6)
C7	−0.2197 (2)	1.6934 (6)	0.18430 (11)	0.0291 (6)
C8	−0.3183 (2)	1.6647 (6)	0.14658 (11)	0.0301 (6)
H8	−0.3235	1.7709	0.1114	0.036*
C9	−0.4091 (2)	1.4834 (6)	0.15960 (12)	0.0345 (7)
H9	−0.4755	1.4651	0.1333	0.041*
C10	−0.4032 (3)	1.3282 (6)	0.21105 (13)	0.0393 (7)
H10	−0.4653	1.2043	0.2201	0.047*
C11	−0.3063 (3)	1.3562 (6)	0.24861 (13)	0.0417 (8)
H11	−0.3017	1.2502	0.2838	0.050*
C12	−0.2149 (3)	1.5378 (6)	0.23580 (12)	0.0368 (7)
H12	−0.1488	1.5557	0.2624	0.044*
C13	−0.1189 (2)	1.8779 (6)	0.16826 (13)	0.0358 (7)
H13A	−0.0727	1.9483	0.2032	0.043*
H13B	−0.1471	2.0576	0.1462	0.043*
C14	−0.0443 (2)	1.6869 (6)	0.13282 (12)	0.0325 (6)

Atomic displacement parameters (Ų)

	U11	U22	U33	U12	U13	U23
N1	0.0300 (13)	0.0327 (12)	0.0328 (13)	0.0018 (10)	0.0066 (11)	−0.0014 (10)
N2	0.0320 (13)	0.0324 (12)	0.0296 (13)	0.0028 (10)	0.0081 (10)	−0.0008 (10)
C1	0.0324 (16)	0.0392 (15)	0.0366 (17)	0.0032 (13)	0.0027 (13)	−0.0021 (13)
C2	0.0295 (15)	0.0381 (15)	0.0284 (15)	0.0013 (12)	0.0017 (12)	−0.0028 (12)
C3	0.0288 (14)	0.0262 (13)	0.0265 (14)	−0.0012 (11)	0.0071 (12)	0.0009 (11)
C4	0.0300 (15)	0.0309 (14)	0.0303 (15)	0.0026 (11)	0.0037 (12)	0.0007 (12)
C5	0.0323 (16)	0.0342 (14)	0.0258 (14)	0.0001 (12)	0.0061 (12)	0.0016 (12)
C6	0.0334 (16)	0.0290 (13)	0.0252 (14)	−0.0010 (12)	0.0046 (12)	0.0013 (11)
O1	0.0295 (11)	0.0523 (13)	0.0409 (12)	0.0074 (9)	0.0006 (9)	−0.0177 (10)
O2	0.0408 (13)	0.0626 (14)	0.0345 (12)	0.0149 (11)	−0.0011 (10)	−0.0111 (11)
C7	0.0319 (15)	0.0282 (13)	0.0279 (14)	0.0070 (11)	0.0066 (12)	−0.0058 (11)
C8	0.0347 (16)	0.0308 (14)	0.0251 (14)	0.0036 (12)	0.0038 (12)	−0.0017 (11)
C9	0.0326 (16)	0.0350 (14)	0.0363 (17)	0.0025 (12)	0.0054 (13)	−0.0028 (13)
C10	0.0455 (19)	0.0337 (15)	0.0418 (18)	0.0001 (13)	0.0197 (15)	−0.0055 (13)
C11	0.062 (2)	0.0369 (16)	0.0276 (16)	0.0122 (15)	0.0146 (15)	0.0034 (13)
C12	0.0443 (18)	0.0388 (15)	0.0265 (15)	0.0119 (13)	−0.0004 (13)	−0.0066 (12)
C13	0.0316 (16)	0.0351 (15)	0.0413 (18)	0.0018 (12)	0.0071 (13)	−0.0111 (13)
C14	0.0330 (16)	0.0330 (14)	0.0318 (16)	−0.0003 (12)	0.0054 (13)	0.0003 (12)

Geometric parameters (Å, °)

N1—C5	1.339 (3)	O2—C14	1.210 (3)
N1—C1	1.341 (4)	C7—C8	1.392 (4)
N2—C6	1.273 (3)	C7—C12	1.393 (4)
N2—N2i	1.419 (4)	C7—C13	1.510 (4)
C1—C2	1.389 (4)	C8—C9	1.387 (4)
C1—H1	0.9500	C8—H8	0.9500
C2—C3	1.385 (4)	C9—C10	1.390 (4)
C2—H2	0.9500	C9—H9	0.9500
C3—C4	1.391 (4)	C10—C11	1.374 (4)
C3—C6	1.468 (4)	C10—H10	0.9500
C4—C5	1.380 (4)	C11—C12	1.392 (4)
C4—H4	0.9500	C11—H11	0.9500
C5—H5	0.9500	C12—H12	0.9500
C6—H6	0.9500	C13—C14	1.520 (4)
O1—C14	1.321 (3)	C13—H13A	0.9900
O1—H1o	0.96 (4)	C13—H13B	0.9900
C5—N1—C1	117.7 (2)	C9—C8—C7	120.9 (3)
C6—N2—N2i	111.7 (3)	C9—C8—H8	119.5
N1—C1—C2	122.6 (3)	C7—C8—H8	119.5
N1—C1—H1	118.7	C8—C9—C10	120.3 (3)
C2—C1—H1	118.7	C8—C9—H9	119.9
C3—C2—C1	119.3 (3)	C10—C9—H9	119.9
C3—C2—H2	120.4	C11—C10—C9	119.2 (3)
C1—C2—H2	120.4	C11—C10—H10	120.4
C2—C3—C4	118.1 (2)	C9—C10—H10	120.4
C2—C3—C6	119.9 (2)	C10—C11—C12	120.9 (3)
C4—C3—C6	122.0 (2)	C10—C11—H11	119.6
C5—C4—C3	119.1 (3)	C12—C11—H11	119.6
C5—C4—H4	120.5	C11—C12—C7	120.4 (3)
C3—C4—H4	120.5	C11—C12—H12	119.8
N1—C5—C4	123.2 (3)	C7—C12—H12	119.8
N1—C5—H5	118.4	C7—C13—C14	109.8 (2)
C4—C5—H5	118.4	C7—C13—H13A	109.7
N2—C6—C3	120.8 (2)	C14—C13—H13A	109.7
N2—C6—H6	119.6	C7—C13—H13B	109.7
C3—C6—H6	119.6	C14—C13—H13B	109.7
C14—O1—H1O	108 (2)	H13A—C13—H13B	108.2
C8—C7—C12	118.3 (3)	O2—C14—O1	123.5 (3)
C8—C7—C13	120.4 (3)	O2—C14—C13	123.3 (3)
C12—C7—C13	121.2 (3)	O1—C14—C13	113.2 (2)
C5—N1—C1—C2	1.5 (4)	C13—C7—C8—C9	176.6 (2)
N1—C1—C2—C3	−1.8 (4)	C7—C8—C9—C10	0.5 (4)
C1—C2—C3—C4	0.9 (4)	C8—C9—C10—C11	−0.2 (4)
C1—C2—C3—C6	−180.0 (2)	C9—C10—C11—C12	0.2 (4)
C2—C3—C4—C5	0.1 (4)	C10—C11—C12—C7	−0.4 (4)
C6—C3—C4—C5	−179.0 (2)	C8—C7—C12—C11	0.6 (4)
C1—N1—C5—C4	−0.4 (4)	C13—C7—C12—C11	−176.6 (2)
C3—C4—C5—N1	−0.3 (4)	C8—C7—C13—C14	−83.5 (3)
N2i—N2—C6—C3	178.9 (2)	C12—C7—C13—C14	93.7 (3)
C2—C3—C6—N2	179.3 (2)	C7—C13—C14—O2	64.5 (4)
C4—C3—C6—N2	−1.7 (4)	C7—C13—C14—O1	−113.9 (3)
C12—C7—C8—C9	−0.7 (4)

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °)

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1	0.96 (4)	1.70 (4)	2.653 (3)	175 (3)