(IUCr) Crystallography Journals Online

Abstract top

The asymmetric unit of the title 1:2 adduct, C₁₂H₁₀N₄·2C₈H₈O₂, comprises a single molecule of 2-phenylacetic acid and half a molecule of 3-pyridinealdazine; the latter is completed by crystallographic inversion symmetry. In the crystal, molecules are connected into a three-component aggregate via O-HN hydrogen bonds. As the carboxyl group lies above the plane through the benzene ring to which it is attached [C-C-C-C = 62.24 (17)°] and the 4-pyridinealdazine molecule is almost planar (r.m.s. deviation of the 16 non-H atoms = 0.027 Å), the overall shape of the aggregate is that of a flattened extended chair. Layers of these aggregates are connected by C-HO and C-H [pi] interactions and stack parallel to (220).

2-Phenylacetic acid–3-{(E)-2-[(E)-pyridin-3-ylmethylidene]hydrazin-1- ylidenemethyl}pyridine (2/1) top

Crystal data top

C₁₂H₁₀N₄·2C₈H₈O₂	Z = 1
M_r = 482.53	F(000) = 254
Triclinic, P1	D_x = 1.280 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 5.511 (2) Å	Cell parameters from 2727 reflections
b = 9.536 (4) Å	θ = 2.6–40.1°
c = 12.434 (6) Å	µ = 0.09 mm⁻¹
α = 80.30 (2)°	T = 98 K
β = 88.45 (3)°	Prism, gold
γ = 76.46 (2)°	0.52 × 0.32 × 0.10 mm
V = 626.1 (5) Å³

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	2849 independent reflections
Radiation source: fine-focus sealed tube	2578 reflections with I > 2σ(I)
graphite	R_int = 0.026
ω scans	θ_max = 27.5°, θ_min = 2.6°
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	h = −6→7
T_min = 0.832, T_max = 1.000	k = −11→12
5606 measured reflections	l = −16→16

Refinement top

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)] = 0.051	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.130	H atoms treated by a mixture of independent and constrained refinement
S = 1.09	w = 1/[σ²(F_o²) + (0.0606P)² + 0.17P] where P = (F_o² + 2F_c²)/3
2849 reflections	(Δ/σ)_max = 0.001
166 parameters	Δρ_max = 0.24 e Å⁻³
1 restraint	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₂H₁₀N₄·2C₈H₈O₂	γ = 76.46 (2)°
M_r = 482.53	V = 626.1 (5) Å³
Triclinic, P1	Z = 1
a = 5.511 (2) Å	Mo Kα radiation
b = 9.536 (4) Å	µ = 0.09 mm⁻¹
c = 12.434 (6) Å	T = 98 K
α = 80.30 (2)°	0.52 × 0.32 × 0.10 mm
β = 88.45 (3)°

Data collection top

Rigaku AFC12K/SATURN724 diffractometer	2578 reflections with I > 2σ(I)
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	R_int = 0.026
T_min = 0.832, T_max = 1.000	θ_max = 27.5°
5606 measured reflections	Standard reflections: 0
2849 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.051	H atoms treated by a mixture of independent and constrained refinement
wR(F²) = 0.130	Δρ_max = 0.24 e Å⁻³
S = 1.09	Δρ_min = −0.21 e Å⁻³
2849 reflections	Absolute structure: ?
166 parameters	Flack parameter: ?
1 restraint	Rogers parameter: ?

Special details top

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.

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.4813 (2)	0.37678 (11)	0.41019 (8)	0.0306 (3)
H1o	0.616 (2)	0.346 (2)	0.3774 (15)	0.046*
O2	0.65187 (19)	0.18266 (12)	0.53456 (8)	0.0327 (3)
C1	0.4823 (3)	0.28746 (15)	0.50429 (11)	0.0244 (3)
C2	0.2466 (2)	0.33170 (15)	0.56825 (11)	0.0260 (3)
H2A	0.2104	0.4387	0.5669	0.031*
H2B	0.1059	0.3105	0.5311	0.031*
C3	0.2583 (2)	0.25628 (14)	0.68565 (11)	0.0233 (3)
C4	0.4322 (3)	0.27578 (15)	0.75870 (11)	0.0260 (3)
H4	0.5476	0.3337	0.7336	0.031*
C5	0.4367 (3)	0.21091 (16)	0.86760 (12)	0.0301 (3)
H5	0.5550	0.2247	0.9166	0.036*
C6	0.2690 (3)	0.12602 (18)	0.90514 (12)	0.0339 (3)
H6	0.2706	0.0829	0.9799	0.041*
C7	0.0988 (3)	0.10450 (18)	0.83273 (13)	0.0347 (4)
H7	−0.0142	0.0450	0.8577	0.042*
C8	0.0934 (2)	0.16981 (16)	0.72377 (12)	0.0284 (3)
H8	−0.0244	0.1551	0.6749	0.034*
N1	−0.0907 (2)	0.29342 (13)	0.30452 (10)	0.0282 (3)
N2	0.4880 (2)	0.43938 (12)	0.03906 (9)	0.0258 (3)
C9	0.0632 (3)	0.16205 (16)	0.33502 (12)	0.0296 (3)
H9	0.0136	0.0960	0.3926	0.035*
C10	0.2924 (3)	0.11778 (16)	0.28634 (12)	0.0305 (3)
H10	0.3954	0.0231	0.3097	0.037*
C11	0.3679 (3)	0.21366 (15)	0.20351 (12)	0.0276 (3)
H11	0.5233	0.1859	0.1687	0.033*
C12	0.2118 (3)	0.35235 (15)	0.17169 (11)	0.0241 (3)
C13	−0.0167 (3)	0.38574 (15)	0.22392 (11)	0.0266 (3)
H13	−0.1254	0.4788	0.2011	0.032*
C14	0.2776 (3)	0.46341 (15)	0.08762 (11)	0.0253 (3)
H14	0.1624	0.5551	0.0685	0.030*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0334 (6)	0.0296 (5)	0.0252 (5)	−0.0036 (4)	0.0036 (4)	−0.0007 (4)
O2	0.0301 (5)	0.0331 (6)	0.0281 (5)	0.0021 (4)	0.0024 (4)	0.0004 (4)
C1	0.0267 (6)	0.0245 (6)	0.0224 (6)	−0.0067 (5)	−0.0020 (5)	−0.0038 (5)
C2	0.0231 (6)	0.0258 (7)	0.0265 (7)	−0.0022 (5)	−0.0011 (5)	−0.0019 (5)
C3	0.0214 (6)	0.0223 (6)	0.0242 (7)	0.0001 (5)	0.0008 (5)	−0.0054 (5)
C4	0.0254 (6)	0.0227 (6)	0.0293 (7)	−0.0025 (5)	−0.0006 (5)	−0.0062 (5)
C5	0.0280 (7)	0.0319 (7)	0.0281 (7)	0.0025 (6)	−0.0030 (5)	−0.0114 (6)
C6	0.0312 (7)	0.0391 (8)	0.0242 (7)	0.0028 (6)	0.0036 (5)	−0.0013 (6)
C7	0.0255 (7)	0.0376 (8)	0.0366 (8)	−0.0053 (6)	0.0057 (6)	0.0019 (6)
C8	0.0212 (6)	0.0315 (7)	0.0314 (7)	−0.0044 (5)	−0.0010 (5)	−0.0043 (6)
N1	0.0316 (6)	0.0279 (6)	0.0253 (6)	−0.0074 (5)	0.0043 (5)	−0.0051 (5)
N2	0.0309 (6)	0.0236 (6)	0.0229 (6)	−0.0070 (5)	0.0021 (4)	−0.0030 (5)
C9	0.0374 (8)	0.0241 (7)	0.0276 (7)	−0.0091 (6)	0.0017 (6)	−0.0029 (5)
C10	0.0354 (8)	0.0224 (7)	0.0318 (7)	−0.0037 (6)	0.0017 (6)	−0.0039 (6)
C11	0.0281 (7)	0.0253 (7)	0.0290 (7)	−0.0039 (5)	0.0024 (5)	−0.0070 (5)
C12	0.0275 (7)	0.0227 (6)	0.0224 (6)	−0.0056 (5)	0.0006 (5)	−0.0052 (5)
C13	0.0290 (7)	0.0242 (7)	0.0250 (7)	−0.0030 (5)	0.0012 (5)	−0.0042 (5)
C14	0.0280 (7)	0.0229 (6)	0.0244 (6)	−0.0042 (5)	−0.0005 (5)	−0.0045 (5)

Geometric parameters (Å, °) top

O1—C1	1.3254 (17)	C7—H7	0.9500
O1—H1o	0.853 (9)	C8—H8	0.9500
O2—C1	1.2120 (17)	N1—C9	1.3389 (19)
C1—C2	1.516 (2)	N1—C13	1.3397 (18)
C2—C3	1.5105 (19)	N2—C14	1.2832 (19)
C2—H2A	0.9900	N2—N2ⁱ	1.408 (2)
C2—H2B	0.9900	C9—C10	1.391 (2)
C3—C8	1.388 (2)	C9—H9	0.9500
C3—C4	1.4019 (19)	C10—C11	1.381 (2)
C4—C5	1.389 (2)	C10—H10	0.9500
C4—H4	0.9500	C11—C12	1.398 (2)
C5—C6	1.388 (2)	C11—H11	0.9500
C5—H5	0.9500	C12—C13	1.395 (2)
C6—C7	1.390 (2)	C12—C14	1.4602 (19)
C6—H6	0.9500	C13—H13	0.9500
C7—C8	1.390 (2)	C14—H14	0.9500

C1—O1—H1O	107.8 (14)	C8—C7—H7	119.9
O2—C1—O1	123.54 (13)	C3—C8—C7	120.66 (14)
O2—C1—C2	124.48 (13)	C3—C8—H8	119.7
O1—C1—C2	111.98 (12)	C7—C8—H8	119.7
C3—C2—C1	114.69 (11)	C9—N1—C13	117.66 (13)
C3—C2—H2A	108.6	C14—N2—N2ⁱ	111.72 (14)
C1—C2—H2A	108.6	N1—C9—C10	123.08 (13)
C3—C2—H2B	108.6	N1—C9—H9	118.5
C1—C2—H2B	108.6	C10—C9—H9	118.5
H2A—C2—H2B	107.6	C11—C10—C9	118.95 (13)
C8—C3—C4	118.88 (13)	C11—C10—H10	120.5
C8—C3—C2	120.74 (12)	C9—C10—H10	120.5
C4—C3—C2	120.37 (13)	C10—C11—C12	118.88 (13)
C5—C4—C3	120.36 (14)	C10—C11—H11	120.6
C5—C4—H4	119.8	C12—C11—H11	120.6
C3—C4—H4	119.8	C13—C12—C11	117.99 (13)
C6—C5—C4	120.29 (14)	C13—C12—C14	118.80 (12)
C6—C5—H5	119.9	C11—C12—C14	123.21 (13)
C4—C5—H5	119.9	N1—C13—C12	123.42 (13)
C5—C6—C7	119.58 (14)	N1—C13—H13	118.3
C5—C6—H6	120.2	C12—C13—H13	118.3
C7—C6—H6	120.2	N2—C14—C12	121.22 (13)
C6—C7—C8	120.21 (15)	N2—C14—H14	119.4
C6—C7—H7	119.9	C12—C14—H14	119.4

O2—C1—C2—C3	13.2 (2)	C13—N1—C9—C10	−0.6 (2)
O1—C1—C2—C3	−167.21 (12)	N1—C9—C10—C11	0.8 (2)
C1—C2—C3—C8	−119.47 (14)	C9—C10—C11—C12	0.3 (2)
C1—C2—C3—C4	62.24 (17)	C10—C11—C12—C13	−1.5 (2)
C8—C3—C4—C5	−0.8 (2)	C10—C11—C12—C14	177.93 (13)
C2—C3—C4—C5	177.55 (12)	C9—N1—C13—C12	−0.7 (2)
C3—C4—C5—C6	0.0 (2)	C11—C12—C13—N1	1.8 (2)
C4—C5—C6—C7	0.9 (2)	C14—C12—C13—N1	−177.69 (13)
C5—C6—C7—C8	−1.2 (2)	N2ⁱ—N2—C14—C12	179.76 (13)
C4—C3—C8—C7	0.5 (2)	C13—C12—C14—N2	178.28 (13)
C2—C3—C8—C7	−177.80 (13)	C11—C12—C14—N2	−1.1 (2)
C6—C7—C8—C3	0.5 (2)

Symmetry codes: (i) −x+1, −y+1, −z.

Hydrogen-bond geometry (Å, °) top

Cg1 is the centroid of the C3–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1ⁱⁱ	0.85 (2)	1.84 (2)	2.689 (2)	176 (2)
C8—H8···O2ⁱⁱⁱ	0.95	2.47	3.398 (2)	166
C10—H10···O2^iv	0.95	2.57	3.277 (2)	132
C10—H10···Cg1^iv	0.95	2.89	3.627 (2)	135

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

Table 1
Hydrogen-bond geometry (Å, °) top

Cg1 is the centroid of the C3–C8 ring.

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1o···N1ⁱ	0.85 (2)	1.84 (2)	2.689 (2)	176 (2)
C8—H8···O2ⁱⁱ	0.95	2.47	3.398 (2)	166
C10—H10···O2ⁱⁱⁱ	0.95	2.57	3.277 (2)	132
C10—H10···Cg1ⁱⁱⁱ	0.95	2.89	3.627 (2)	135

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

	Fig. 1. Molecular structure of 2-phenylacetic acid found in co-crystal (I) showing displacement ellipsoids at the 50% probability level
	Fig. 2. Molecular structure of 3-pyridinealdazine found in co-crystal (I) showing displacement ellipsoids at the 50% probability level. The molecule is disposed about a centre of inversion with i = 1 - x, 1 - y, -z.
	Fig. 3. The three component aggregate in (I) highlighting the extended chair conformation. The O—H···N hydrogen bonds are shown as orange dashed lines.
	Fig. 4. A view in projection down the a axis highlighting the stacking of layers in co-crystal (I) mediated by O—H···N, C—H···O and C—H···π interactions shown as orange, blue and purple dashed lines, respectively.

supplementary materials

2-Phenylacetic acid-3-{(E)-2-[(E)-pyridin-3-ylmethylidene]hydrazin-1-ylidenemethyl}pyridine (2/1)

H. D. Arman, T. Kaulgud and E. R. T. Tiekink