(E)-N-[2-(Pyridin-2-yl)isoindolin-1-ylidene]pyridin-2-amine

Zhu, L.-N.; Gao, S.; Huo, L.-H.; Zhao, H.

doi:10.1107/S1600536807044984

Buy article online - an online subscription or single-article purchase is required to access this article.

(E)-N-[2-(Pyridin-2-yl)isoindolin-1-ylidene]pyridin-2-amine

L.-N. Zhu, S. Gao, L.-H. Huo and H. Zhao

A new bis(pyridyl) compound, C₁₈H₁₄N₄, was prepared by the reaction of phthalaldehyde and 2-aminopyridine in toluene. In the crystal structure, π–π stacking interactions exist between two adjacent molecules.

Read article Similar articles

Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536807044984/bg2102sup1.cif Contains datablocks I, global
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536807044984/bg2102Isup2.hkl Contains datablock I

CCDC reference: 663803

checkCIF report

Key indicators

Single-crystal X-ray study
T = 295 K
Mean (C-C) = 0.002 Å
R factor = 0.038
wR factor = 0.115
Data-to-parameter ratio = 16.1

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT154_ALERT_1_C The su's on the Cell Angles are Equal  (x 10000)       3000 Deg.

   0 ALERT level A = In general: serious problem
   0 ALERT level B = Potentially serious problem
   1 ALERT level C = Check and explain
   0 ALERT level G = General alerts; check

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   0 ALERT type 2 Indicator that the structure model may be wrong or deficient
   0 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion
   0 ALERT type 5 Informative message, check

Comment top

In recent years, N-heterocyclic complexes have attracted much attention in the area of coordination and supramolecular chemistry. Infinite metal-organic frameworks are assembled through the metal coordination of pyridone- or pyridine-based bridging complexes. Accordingly, we have designed and synthesized a new bis(pyridyl) complex, viz. (E)—N-(2-(pyridin-2-yl)isoindolin-1-ylidene)pyridin-2-amine, (I). Two already reported complexes (Akkurt et al., 2006; Takahashi et al., 2005), respectively with 5-methyl-4,5-dihydroisoxazol-3-ylamine and aniline instead of 2-aminopyridine, have a similar structure. In comparison with the typical linear bis(pyridyl) disposition such as in 4,4-bipyridyl, the two pyridyl functions in (I) are more separated and form an acute angle, which may provide novel coordination modes in metal-organic structures.

The molecule structure of (I) is shown in Fig. 1. Each of the individual rings is essentially planar. The benzene ring A (C7—C12) and five-membered B (N3/C6/C7/C12/C13) lie almost on the same plane, subtending a dihedral angle of 2.1 (2) °. The pyridyl rings C (N1/C1—C5) and D (N4/C14—C18) make a dihedral angle of 102.1 (2) ° with each other. The dihedral angles between rings A/C and B/C are 102.2 (2) and 100.1 (2) °, respectively. The dihedral angles between rings A/D and B/D are both 7.9 (2) °. In the crystal structure, π-π stacking interactions exist between adjacent molecules (Table 1) defining a three-dimensional structure.

Related literature top

Two corresponding complexes with 5-methyl-4,5-dihydroisoxazol-3-ylamine (Akkurt et al., 2006) and aniline (Takahashi et al., 2005) instead of 2-aminopyridine have similar structures.

Experimental top

To a solution of phthalaldehyde in toluene was added a solution of 2-aminopyridine in toluene. The mixture was refluxed for 10 h, and a yellow precipitate was obtained. Colorless crystals were obtained by recrystallization of the material from methanol with a yield of 60%. Analysis calculated for C₁₈H₁₄N₄: C 75.51, H 4.93, N 19.57%. Found: C 75.56, H 4.90, N 19.55%.

Structure description top

Two corresponding complexes with 5-methyl-4,5-dihydroisoxazol-3-ylamine (Akkurt et al., 2006) and aniline (Takahashi et al., 2005) instead of 2-aminopyridine have similar structures.

Computing details top

Data collection: RAPID-AUTO (Rigaku, 1998); cell refinement: RAPID-AUTO (Rigaku, 1998); data reduction: CrystalStructure (Rigaku/MSC, 2002); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: ORTEP-II (Johnson, 1976); software used to prepare material for publication: SHELXL97.

Figures top

Fig. 1. ORTEP plot (Johnson, 1976) of title complex, with displacement ellipsoids drawn at 30% probability level.

(E)—N-[2-(Pyridin-2-yl)isoindolin-1-ylidene]pyridin-2-amine top

Crystal data top

C₁₈H₁₄N₄	Z = 2
M_r = 286.33	F(000) = 300
Triclinic, P1	D_x = 1.342 Mg m⁻³
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 8.2571 (17) Å	Cell parameters from 5618 reflections
b = 8.2797 (17) Å	θ = 3.0–27.4°
c = 12.521 (3) Å	µ = 0.08 mm⁻¹
α = 105.97 (3)°	T = 295 K
β = 92.13 (3)°	Prism, colorless
γ = 118.51 (3)°	0.36 × 0.25 × 0.21 mm
V = 708.7 (4) Å³

Data collection top

Rigaku RAXIS-RAPID diffractometer	3208 independent reflections
Radiation source: fine-focus sealed tube	2492 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.015
Detector resolution: 10.000 pixels mm^-1	θ_max = 27.5°, θ_min = 3.0°
ω scans	h = −10→10
Absorption correction: multi-scan ABSCOR (Higashi, 1995)	k = −10→10
T_min = 0.969, T_max = 0.980	l = −14→16
6990 measured reflections

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.115	H-atom parameters constrained
S = 1.13	w = 1/[σ²(F_o²) + (0.054P)² + 0.0939P] where P = (F_o² + 2F_c²)/3
3208 reflections	(Δ/σ)_max < 0.001
199 parameters	Δρ_max = 0.18 e Å⁻³
0 restraints	Δρ_min = −0.21 e Å⁻³

Crystal data top

C₁₈H₁₄N₄	γ = 118.51 (3)°
M_r = 286.33	V = 708.7 (4) Å³
Triclinic, P1	Z = 2
a = 8.2571 (17) Å	Mo Kα radiation
b = 8.2797 (17) Å	µ = 0.08 mm⁻¹
c = 12.521 (3) Å	T = 295 K
α = 105.97 (3)°	0.36 × 0.25 × 0.21 mm
β = 92.13 (3)°

Data collection top

Rigaku RAXIS-RAPID diffractometer	3208 independent reflections
Absorption correction: multi-scan ABSCOR (Higashi, 1995)	2492 reflections with I > 2σ(I)
T_min = 0.969, T_max = 0.980	R_int = 0.015
6990 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.038	0 restraints
wR(F²) = 0.115	H-atom parameters constrained
S = 1.13	Δρ_max = 0.18 e Å⁻³
3208 reflections	Δρ_min = −0.21 e Å⁻³
199 parameters

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
N1	−0.09225 (17)	0.76516 (17)	0.87717 (10)	0.0466 (3)
N2	−0.11473 (15)	0.63183 (17)	0.68229 (9)	0.0435 (3)
N3	0.08028 (14)	0.75228 (15)	0.55829 (8)	0.0379 (3)
N4	0.03406 (16)	0.81571 (18)	0.39661 (9)	0.0465 (3)
C1	−0.13993 (17)	0.60736 (19)	0.78836 (11)	0.0388 (3)
C2	−0.2270 (2)	0.4209 (2)	0.79558 (12)	0.0492 (3)
H2	−0.2595	0.3133	0.7320	0.059*
C3	−0.2642 (3)	0.3984 (2)	0.89801 (13)	0.0597 (4)
H3	−0.3208	0.2751	0.9050	0.072*
C4	−0.2171 (3)	0.5599 (2)	0.99041 (13)	0.0598 (4)
H4	−0.2428	0.5480	1.0604	0.072*
C5	−0.1313 (2)	0.7384 (2)	0.97623 (12)	0.0528 (4)
H5	−0.0981	0.8476	1.0388	0.063*
C6	0.04936 (17)	0.71127 (17)	0.65899 (10)	0.0356 (3)
C7	0.23566 (17)	0.76891 (17)	0.72090 (11)	0.0371 (3)
C8	0.2882 (2)	0.7566 (2)	0.82419 (12)	0.0469 (3)
H8	0.2006	0.7114	0.8690	0.056*
C9	0.4738 (2)	0.8131 (2)	0.85819 (13)	0.0531 (4)
H9	0.5114	0.8066	0.9271	0.064*
C10	0.6052 (2)	0.8793 (2)	0.79186 (13)	0.0506 (3)
H10	0.7292	0.9157	0.8164	0.061*
C11	0.55360 (19)	0.8919 (2)	0.68939 (12)	0.0447 (3)
H11	0.6415	0.9367	0.6447	0.054*
C12	0.36805 (18)	0.83610 (18)	0.65505 (11)	0.0377 (3)
C13	0.27804 (17)	0.83251 (19)	0.54836 (11)	0.0399 (3)
H13	0.3312	0.9626	0.5438	0.048*
H14	0.2921	0.7496	0.4822	0.048*
C14	−0.04689 (17)	0.73947 (17)	0.47444 (10)	0.0358 (3)
C15	−0.24000 (19)	0.6558 (2)	0.47075 (12)	0.0456 (3)
H15	−0.2938	0.6035	0.5259	0.055*
C16	−0.3486 (2)	0.6527 (2)	0.38339 (12)	0.0495 (3)
H16	−0.4780	0.5959	0.3784	0.059*
C17	−0.2669 (2)	0.7331 (2)	0.30345 (12)	0.0511 (4)
H17	−0.3383	0.7337	0.2445	0.061*
C18	−0.0762 (2)	0.8124 (2)	0.31402 (12)	0.0543 (4)
H18	−0.0198	0.8674	0.2603	0.065*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N1	0.0504 (7)	0.0451 (6)	0.0436 (6)	0.0217 (5)	0.0095 (5)	0.0187 (5)
N2	0.0378 (6)	0.0553 (7)	0.0393 (6)	0.0200 (5)	0.0125 (5)	0.0248 (5)
N3	0.0355 (5)	0.0429 (6)	0.0355 (6)	0.0172 (5)	0.0113 (4)	0.0179 (5)
N4	0.0425 (6)	0.0589 (7)	0.0364 (6)	0.0209 (5)	0.0124 (5)	0.0220 (5)
C1	0.0331 (6)	0.0476 (7)	0.0390 (7)	0.0198 (5)	0.0102 (5)	0.0200 (6)
C2	0.0617 (9)	0.0436 (8)	0.0409 (7)	0.0244 (7)	0.0166 (6)	0.0157 (6)
C3	0.0843 (11)	0.0460 (8)	0.0501 (9)	0.0282 (8)	0.0240 (8)	0.0259 (7)
C4	0.0844 (12)	0.0613 (10)	0.0399 (8)	0.0360 (9)	0.0236 (7)	0.0260 (7)
C5	0.0688 (10)	0.0514 (8)	0.0391 (7)	0.0315 (8)	0.0112 (7)	0.0144 (6)
C6	0.0385 (6)	0.0340 (6)	0.0350 (6)	0.0174 (5)	0.0109 (5)	0.0142 (5)
C7	0.0376 (7)	0.0349 (6)	0.0402 (7)	0.0175 (5)	0.0102 (5)	0.0159 (5)
C8	0.0445 (7)	0.0557 (8)	0.0479 (8)	0.0250 (6)	0.0138 (6)	0.0280 (7)
C9	0.0488 (8)	0.0617 (9)	0.0538 (9)	0.0262 (7)	0.0057 (6)	0.0302 (7)
C10	0.0381 (7)	0.0512 (8)	0.0626 (9)	0.0202 (6)	0.0061 (6)	0.0247 (7)
C11	0.0370 (7)	0.0435 (7)	0.0531 (8)	0.0181 (6)	0.0127 (6)	0.0193 (6)
C12	0.0384 (6)	0.0343 (6)	0.0400 (7)	0.0173 (5)	0.0108 (5)	0.0135 (5)
C13	0.0358 (6)	0.0455 (7)	0.0389 (7)	0.0187 (5)	0.0137 (5)	0.0175 (6)
C14	0.0401 (7)	0.0334 (6)	0.0322 (6)	0.0174 (5)	0.0093 (5)	0.0107 (5)
C15	0.0409 (7)	0.0533 (8)	0.0451 (7)	0.0206 (6)	0.0144 (6)	0.0251 (6)
C16	0.0398 (7)	0.0583 (9)	0.0497 (8)	0.0224 (6)	0.0098 (6)	0.0217 (7)
C17	0.0506 (8)	0.0644 (9)	0.0399 (7)	0.0295 (7)	0.0063 (6)	0.0196 (7)
C18	0.0530 (8)	0.0729 (10)	0.0383 (7)	0.0273 (8)	0.0137 (6)	0.0287 (7)

Geometric parameters (Å, º) top

N1—C1	1.3325 (19)	C8—C9	1.380 (2)
N1—C5	1.3432 (18)	C8—H8	0.9300
N2—C6	1.2797 (17)	C9—C10	1.385 (2)
N2—C1	1.4060 (16)	C9—H9	0.9300
N3—C6	1.3953 (15)	C10—C11	1.383 (2)
N3—C14	1.4024 (16)	C10—H10	0.9300
N3—C13	1.4656 (16)	C11—C12	1.3827 (19)
N4—C14	1.3338 (16)	C11—H11	0.9300
N4—C18	1.3378 (18)	C12—C13	1.4903 (18)
C1—C2	1.3892 (19)	C13—H13	0.9700
C2—C3	1.371 (2)	C13—H14	0.9700
C2—H2	0.9300	C14—C15	1.3953 (18)
C3—C4	1.377 (2)	C15—C16	1.375 (2)
C3—H3	0.9300	C15—H15	0.9300
C4—C5	1.368 (2)	C16—C17	1.374 (2)
C4—H4	0.9300	C16—H16	0.9300
C5—H5	0.9300	C17—C18	1.370 (2)
C6—C7	1.4839 (18)	C17—H17	0.9300
C7—C12	1.3867 (18)	C18—H18	0.9300
C7—C8	1.3947 (18)

C1—N1—C5	117.37 (12)	C10—C9—H9	119.3
C6—N2—C1	121.20 (12)	C11—C10—C9	120.57 (14)
C6—N3—C14	128.75 (11)	C11—C10—H10	119.7
C6—N3—C13	112.22 (10)	C9—C10—H10	119.7
C14—N3—C13	118.85 (10)	C12—C11—C10	118.32 (13)
C14—N4—C18	117.72 (12)	C12—C11—H11	120.8
N1—C1—C2	122.43 (12)	C10—C11—H11	120.8
N1—C1—N2	117.73 (12)	C11—C12—C7	121.37 (12)
C2—C1—N2	119.60 (13)	C11—C12—C13	128.40 (12)
C3—C2—C1	118.84 (14)	C7—C12—C13	110.22 (11)
C3—C2—H2	120.6	N3—C13—C12	102.90 (10)
C1—C2—H2	120.6	N3—C13—H13	111.2
C2—C3—C4	119.44 (14)	C12—C13—H13	111.2
C2—C3—H3	120.3	N3—C13—H14	111.2
C4—C3—H3	120.3	C12—C13—H14	111.2
C5—C4—C3	118.07 (14)	H13—C13—H14	109.1
C5—C4—H4	121.0	N4—C14—C15	122.18 (12)
C3—C4—H4	121.0	N4—C14—N3	113.52 (11)
N1—C5—C4	123.85 (14)	C15—C14—N3	124.30 (11)
N1—C5—H5	118.1	C16—C15—C14	118.21 (12)
C4—C5—H5	118.1	C16—C15—H15	120.9
N2—C6—N3	122.49 (12)	C14—C15—H15	120.9
N2—C6—C7	131.41 (11)	C17—C16—C15	120.30 (13)
N3—C6—C7	106.04 (10)	C17—C16—H16	119.9
C12—C7—C8	120.14 (12)	C15—C16—H16	119.9
C12—C7—C6	108.58 (11)	C18—C17—C16	117.41 (13)
C8—C7—C6	131.20 (12)	C18—C17—H17	121.3
C9—C8—C7	118.22 (13)	C16—C17—H17	121.3
C9—C8—H8	120.9	N4—C18—C17	124.18 (13)
C7—C8—H8	120.9	N4—C18—H18	117.9
C8—C9—C10	121.37 (14)	C17—C18—H18	117.9
C8—C9—H9	119.3

C5—N1—C1—C2	0.1 (2)	C9—C10—C11—C12	−0.2 (2)
C5—N1—C1—N2	174.56 (12)	C10—C11—C12—C7	0.0 (2)
C6—N2—C1—N1	73.68 (17)	C10—C11—C12—C13	−178.68 (13)
C6—N2—C1—C2	−111.73 (16)	C8—C7—C12—C11	0.08 (19)
N1—C1—C2—C3	−0.4 (2)	C6—C7—C12—C11	−177.06 (11)
N2—C1—C2—C3	−174.77 (14)	C8—C7—C12—C13	178.94 (12)
C1—C2—C3—C4	0.9 (3)	C6—C7—C12—C13	1.80 (14)
C2—C3—C4—C5	−1.1 (3)	C6—N3—C13—C12	0.29 (13)
C1—N1—C5—C4	−0.3 (2)	C14—N3—C13—C12	175.88 (10)
C3—C4—C5—N1	0.8 (3)	C11—C12—C13—N3	177.45 (12)
C1—N2—C6—N3	−174.52 (11)	C7—C12—C13—N3	−1.30 (14)
C1—N2—C6—C7	8.8 (2)	C18—N4—C14—C15	0.9 (2)
C14—N3—C6—N2	8.3 (2)	C18—N4—C14—N3	−179.11 (12)
C13—N3—C6—N2	−176.67 (12)	C6—N3—C14—N4	170.91 (11)
C14—N3—C6—C7	−174.30 (11)	C13—N3—C14—N4	−3.85 (16)
C13—N3—C6—C7	0.74 (13)	C6—N3—C14—C15	−9.1 (2)
N2—C6—C7—C12	175.52 (13)	C13—N3—C14—C15	176.12 (12)
N3—C6—C7—C12	−1.57 (13)	N4—C14—C15—C16	0.1 (2)
N2—C6—C7—C8	−1.2 (2)	N3—C14—C15—C16	−179.90 (12)
N3—C6—C7—C8	−178.27 (13)	C14—C15—C16—C17	−1.0 (2)
C12—C7—C8—C9	0.2 (2)	C15—C16—C17—C18	0.9 (2)
C6—C7—C8—C9	176.54 (13)	C14—N4—C18—C17	−1.0 (2)
C7—C8—C9—C10	−0.4 (2)	C16—C17—C18—N4	0.1 (2)
C8—C9—C10—C11	0.5 (2)

Experimental details

Crystal data
Chemical formula	C₁₈H₁₄N₄
M_r	286.33
Crystal system, space group	Triclinic, P1
Temperature (K)	295
a, b, c (Å)	8.2571 (17), 8.2797 (17), 12.521 (3)
α, β, γ (°)	105.97 (3), 92.13 (3), 118.51 (3)
V (Å³)	708.7 (4)
Z	2
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.36 × 0.25 × 0.21

Data collection
Diffractometer	Rigaku RAXIS-RAPID
Absorption correction	Multi-scan ABSCOR (Higashi, 1995)
T_min, T_max	0.969, 0.980
No. of measured, independent and observed [I > 2σ(I)] reflections	6990, 3208, 2492
R_int	0.015
(sin θ/λ)_max (Å⁻¹)	0.649

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.038, 0.115, 1.13
No. of reflections	3208
No. of parameters	199
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.18, −0.21

Computer programs: RAPID-AUTO (Rigaku, 1998), CrystalStructure (Rigaku/MSC, 2002), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), ORTEP-II (Johnson, 1976), SHELXL97.

π-π contacts (Å, °) for the title compound top

Cg1	Cg2	Cg1···Cg2 (Å)	Dihedral angle (°)	<Cg···Perp> (Å)
CgA	CgDⁱ	3.8672 (13)	7.94 (1)	3.63 (7)
CgB	CgBⁱ	4.3836 (13)	0.00	3.48 (1)
CgB	CgDⁱ	4.0391 (13)	7.86 (1)	3.58 (12)
CgB	CgDⁱⁱ	4.2714 (14)	7.86 (1)	3.53 (13)
CgD	CgDⁱⁱ	3.9380 (12)	0.00	3.48 (1)

Symmetry codes: i = -x,1-y,1-z; ii = -x,2-y,1-z

Ring code: as in Fig. 1

Subscribe to Acta Crystallographica Section E: Crystallographic Communications

Buy online

You may purchase this article in PDF and/or HTML formats. For purchasers in the European Community who do not have a VAT number, VAT will be added at the local rate. Payments to the IUCr are handled by WorldPay, who will accept payment by credit card in several currencies. To purchase the article, please complete the form below (fields marked * are required), and then click on `Continue'.

E-mail address*
Repeat e-mail address* (for error checking)

Format*	PDF (US $40)
	HTML (US $40)
	PDF+HTML (US $50)
In order for VAT to be shown for your country javascript needs to be enabled.

VAT number (non-UK EC countries only)
Country*

Terms and conditions of use
Contact us

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Format		BIBTeX
		EndNote
		RefMan
		Refer
		Medline
		CIF
		SGML
		Text
		Plain Text

Search IUCr Journals		doi		Advanced search
Author		volume	page