N2-(2-Pyrid­yl)-N6-(4-pyrid­yl)pyridine-2,6-diamine

Wang, Z.-M.; Shao, B.

doi:10.1107/S1600536809033480

organic compounds

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ISSN: 2056-9890

Volume 65| Part 9| September 2009| Page o2273

doi:10.1107/S1600536809033480

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N²-(2-Pyridyl)-N⁶-(4-pyridyl)pyridine-2,6-diamine

Zhi-Min Wang ^a ^* and Bo Shao ^a

^aCollege of Biology and Environmental Engineering, Zhejiang Shuren University, 310015 Hangzhou, People's Republic of China
^*Correspondence e-mail: srwzm2009@126.com

(Received 21 August 2009; accepted 22 August 2009; online 29 August 2009)

In the title compound, C₁₅H₁₃N₅, the dihedral angles between the central aromatic ring and and the two peripheral rings are 1.5 (6) and 33.1 (4)°. In the crystal, intermolecular N—H⋯N hydrogen bonds connect the molecules into a zigzag chain propagating in [100].

Related literature

For a related structure, see: Huang et al. (2004 ). For background to metal-organic framework complexes with polypyridylamine ligands, see: Peng et al. (2000 ); Fang et al. (2005 ).

Experimental

Crystal data

C₁₅H₁₃N₅
M_r = 263.30
Orthorhombic, P b c a
a = 11.4884 (15) Å
b = 7.3445 (10) Å
c = 30.718 (4) Å
V = 2591.9 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 298 K
0.19 × 0.15 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ) T_min = 0.984, T_max = 0.991
11972 measured reflections
2304 independent reflections
1529 reflections with I > 2σ(I)
R_int = 0.053

Refinement

R[F² > 2σ(F²)] = 0.050
wR(F²) = 0.187
S = 0.82
2304 reflections
182 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.15 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N4—H4A⋯N1ⁱ	0.86	2.22	3.038 (3)	160
N2—H2A⋯N3ⁱⁱ	0.86	2.35	3.198 (3)	170
Symmetry codes: (i) $[-x, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) $[-x+{\script{1\over 2}}, y+{\script{1\over 2}}, z]$ .

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996 ), ORTEP-3 for Windows (Farrugia, 1997 ) and PLATON (Spek, 2009 ); software used to prepare material for publication: SHELXL97.

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809033480/hb5059sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536809033480/hb5059Isup2.hkl

checkCIF report

Comment top

Metal-organic frameworks complexes with polypyridylamine ligands, bearing diverse networks and special optical and electromagnetic properties (Peng et al., 2000), have aroused great interest among researchers. Tri-pyridyldiamine ligand usually exhibits donor as well as acceptor properties and can be used as a popular chelating ligand (Fang et al., 2005). The crystals of the title compound were obatined unintentionally as the harvested product of the mild reaction of N²-(pydidin-2-yl)-N⁶-(pydidin-4-yl)pyridine-2,6-diamine, zinc salt.

The molecular structure of the title compound is shown in Fig. 1. In the crystal structure, intermoelcular N-H···N hydorgen bonds connect molecules into one-dimensional chain along a axis (Table 1), as shown in Figure 2. The three pyridine rings of the title compound are not coplanar. The dihedral angles between the planes of the central pyridine ring and two peripheral rings are 1.5 (6) and 146.9 (4)° respectively, which is very different from the Cd complex with [2,6-bis(2-pyridylamino)pyridine] [15.6 (5) and 34.1 (3)°] (Huang et al., 2004).

Related literature top

For a related structure, see: Huang et al. (2004). For background, see: Peng et al. (2000); Fang et al. (2005).

Experimental top

N²-(pydidin-2-yl)-N⁶-(pydidin-4-yl)pyridine-2,6-diamine (0.27 mg,0.1 mmol), Zn(CH₃COO)₂ (0.43 mg, 0.1 mmol), were added to dry ethanol. The mixture was heated and stirred for six hours under reflux. The resultant was then filtered off to give a pure solution which was treated by diethyl ether in a closed vessel. Two weeks later, colourless blocks of (I) were obtained.

Computing details top

Data collection: APEX2 (Bruker, 2005); cell refinement: SAINT (Bruker, 2005); data reduction: SAINT (Bruker, 2005); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008).

Figures top

	Fig. 1. The molecular structure of (I) Ellipsoids are drawn at the the 30% probability level. H atoms are shown as spheres of arbitrary radius.
	Fig. 2. Partial packing of (I) view showing the formation of a chain through N-H···N hydrogen bonds. Hydrogen bonds are shown as dashed lines.

N²-(2-Pyridyl)-N⁶-(4-pyridyl)pyridine-2,6-diamine top

Crystal data top

C₁₅H₁₃N₅	F(000) = 1104
M_r = 263.30	D_x = 1.350 Mg m⁻³
Orthorhombic, Pbca	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ac 2ab	Cell parameters from 2304 reflections
a = 11.4884 (15) Å	θ = 2.2–25.2°
b = 7.3445 (10) Å	µ = 0.09 mm⁻¹
c = 30.718 (4) Å	T = 298 K
V = 2591.9 (6) Å³	Block, colourless
Z = 8	0.19 × 0.15 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	2304 independent reflections
Radiation source: fine-focus sealed tube	1529 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.053
ϕ and ω scans	θ_max = 25.2°, θ_min = 2.2°
Absorption correction: multi-scan (SADABS; Bruker, 2005)	h = −13→11
T_min = 0.984, T_max = 0.991	k = −8→8
11972 measured reflections	l = −34→36

Refinement top

Refinement on F²	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F² > 2σ(F²)] = 0.050	H-atom parameters constrained
wR(F²) = 0.187	w = 1/[σ²(F_o²) + (0.158P)² + 0.03P] where P = (F_o² + 2F_c²)/3
S = 0.82	(Δ/σ)_max < 0.001
2304 reflections	Δρ_max = 0.23 e Å⁻³
182 parameters	Δρ_min = −0.15 e Å⁻³
1 restraint	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc^*=kFc[1+0.001xFc²λ³/sin(2θ)]^-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.011 (2)

Crystal data top

C₁₅H₁₃N₅	V = 2591.9 (6) Å³
M_r = 263.30	Z = 8
Orthorhombic, Pbca	Mo Kα radiation
a = 11.4884 (15) Å	µ = 0.09 mm⁻¹
b = 7.3445 (10) Å	T = 298 K
c = 30.718 (4) Å	0.19 × 0.15 × 0.11 mm

Data collection top

Bruker APEXII CCD diffractometer	2304 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2005)	1529 reflections with I > 2σ(I)
T_min = 0.984, T_max = 0.991	R_int = 0.053
11972 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.050	1 restraint
wR(F²) = 0.187	H-atom parameters constrained
S = 0.82	Δρ_max = 0.23 e Å⁻³
2304 reflections	Δρ_min = −0.15 e Å⁻³
182 parameters

Special details top

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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 > 2sigma(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
N3	0.09096 (15)	1.0142 (2)	0.36725 (5)	0.0482 (5)
C11	−0.05825 (17)	0.6096 (3)	0.40354 (7)	0.0485 (6)
N5	−0.06267 (16)	0.6024 (3)	0.44682 (6)	0.0573 (6)
N2	0.18582 (17)	1.2747 (2)	0.34296 (6)	0.0586 (6)
H2A	0.2400	1.3509	0.3493	0.070*
C1	0.0235 (2)	1.1978 (3)	0.24144 (7)	0.0544 (6)
H1	−0.0457	1.1441	0.2324	0.065*
C9	0.06292 (18)	0.9532 (3)	0.44324 (7)	0.0520 (6)
H9	0.0349	0.8779	0.4652	0.062*
C6	0.14379 (19)	1.1700 (3)	0.37742 (7)	0.0482 (6)
C5	0.15115 (19)	1.2712 (3)	0.29979 (7)	0.0476 (6)
C4	0.22262 (19)	1.3511 (3)	0.26852 (8)	0.0557 (6)
H4	0.2920	1.4068	0.2766	0.067*
N4	−0.00874 (17)	0.7580 (2)	0.38310 (6)	0.0553 (6)
H4A	−0.0140	0.7558	0.3552	0.066*
C2	0.04739 (18)	1.1955 (3)	0.28529 (7)	0.0499 (6)
H2	−0.0049	1.1443	0.3049	0.060*
N1	0.09143 (19)	1.2706 (3)	0.21080 (6)	0.0623 (6)
C7	0.1620 (2)	1.2251 (3)	0.42019 (7)	0.0570 (7)
H7	0.2001	1.3335	0.4266	0.068*
C10	0.04771 (17)	0.9094 (3)	0.39941 (7)	0.0450 (5)
C8	0.1212 (2)	1.1128 (3)	0.45271 (7)	0.0595 (7)
H8	0.1332	1.1451	0.4816	0.071*
C12	−0.1031 (2)	0.4715 (3)	0.37727 (8)	0.0612 (6)
H12	−0.0978	0.4792	0.3471	0.073*
C3	0.1897 (2)	1.3467 (3)	0.22582 (8)	0.0638 (7)
H3	0.2391	1.4007	0.2056	0.077*
C15	−0.1133 (2)	0.4549 (4)	0.46451 (9)	0.0694 (8)
H15	−0.1165	0.4479	0.4947	0.083*
C14	−0.1602 (2)	0.3157 (4)	0.44141 (10)	0.0759 (8)
H14	−0.1947	0.2172	0.4554	0.091*
C13	−0.1552 (2)	0.3242 (4)	0.39659 (10)	0.0737 (8)
H13	−0.1867	0.2313	0.3797	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
N3	0.0552 (11)	0.0459 (11)	0.0436 (10)	−0.0016 (8)	−0.0036 (8)	−0.0010 (8)
C11	0.0482 (12)	0.0477 (13)	0.0495 (13)	0.0023 (10)	−0.0020 (9)	0.0048 (10)
N5	0.0608 (12)	0.0589 (13)	0.0521 (12)	−0.0004 (10)	0.0003 (9)	0.0112 (9)
N2	0.0616 (12)	0.0579 (12)	0.0561 (12)	−0.0192 (9)	−0.0075 (9)	0.0004 (9)
C1	0.0567 (13)	0.0496 (13)	0.0571 (15)	−0.0028 (11)	−0.0072 (11)	0.0020 (10)
C9	0.0560 (13)	0.0574 (14)	0.0426 (12)	0.0005 (11)	0.0012 (10)	−0.0015 (10)
C6	0.0480 (12)	0.0466 (12)	0.0500 (13)	0.0002 (10)	−0.0023 (9)	−0.0022 (10)
C5	0.0552 (13)	0.0387 (11)	0.0488 (13)	0.0003 (9)	−0.0001 (10)	−0.0028 (9)
C4	0.0539 (13)	0.0468 (13)	0.0664 (16)	−0.0066 (10)	0.0032 (11)	0.0029 (10)
N4	0.0754 (14)	0.0498 (12)	0.0408 (10)	−0.0103 (10)	−0.0013 (8)	0.0004 (7)
C2	0.0501 (13)	0.0484 (12)	0.0513 (13)	−0.0029 (10)	0.0002 (10)	0.0033 (10)
N1	0.0756 (13)	0.0584 (13)	0.0530 (12)	0.0035 (10)	0.0027 (10)	0.0051 (9)
C7	0.0561 (14)	0.0582 (15)	0.0568 (15)	−0.0068 (11)	−0.0035 (11)	−0.0111 (11)
C10	0.0455 (12)	0.0447 (12)	0.0449 (12)	0.0029 (9)	0.0004 (9)	−0.0003 (9)
C8	0.0621 (15)	0.0700 (17)	0.0465 (13)	−0.0007 (13)	−0.0007 (10)	−0.0125 (11)
C12	0.0626 (15)	0.0582 (15)	0.0628 (14)	−0.0089 (12)	−0.0073 (11)	−0.0010 (12)
C3	0.0725 (15)	0.0593 (16)	0.0596 (15)	0.0017 (12)	0.0130 (12)	0.0081 (11)
C15	0.0624 (16)	0.0743 (18)	0.0715 (17)	−0.0059 (14)	0.0016 (12)	0.0216 (14)
C14	0.0604 (16)	0.0711 (18)	0.096 (2)	−0.0107 (14)	−0.0013 (14)	0.0256 (16)
C13	0.0691 (17)	0.0592 (16)	0.093 (2)	−0.0180 (13)	−0.0082 (15)	0.0030 (14)

Geometric parameters (Å, º) top

N3—C6	1.332 (3)	C4—C3	1.366 (3)
N3—C10	1.347 (3)	C4—H4	0.9300
C11—N5	1.331 (3)	N4—C10	1.381 (2)
C11—N4	1.380 (3)	N4—H4A	0.8600
C11—C12	1.395 (3)	C2—H2	0.9300
N5—C15	1.344 (3)	N1—C3	1.341 (3)
N2—C5	1.385 (3)	C7—C8	1.378 (3)
N2—C6	1.394 (3)	C7—H7	0.9300
N2—H2A	0.8600	C8—H8	0.9300
C1—N1	1.335 (3)	C12—C13	1.371 (3)
C1—C2	1.375 (3)	C12—H12	0.9300
C1—H1	0.9300	C3—H3	0.9300
C9—C8	1.381 (3)	C15—C14	1.356 (4)
C9—C10	1.395 (3)	C15—H15	0.9300
C9—H9	0.9300	C14—C13	1.379 (4)
C6—C7	1.390 (3)	C14—H14	0.9300
C5—C2	1.388 (3)	C13—H13	0.9300
C5—C4	1.393 (3)

C6—N3—C10	119.13 (18)	C1—C2—H2	120.6
N5—C11—N4	120.07 (19)	C5—C2—H2	120.6
N5—C11—C12	122.3 (2)	C1—N1—C3	114.6 (2)
N4—C11—C12	117.6 (2)	C8—C7—C6	117.4 (2)
C11—N5—C15	116.9 (2)	C8—C7—H7	121.3
C5—N2—C6	128.11 (18)	C6—C7—H7	121.3
C5—N2—H2A	115.9	N3—C10—N4	111.54 (17)
C6—N2—H2A	115.9	N3—C10—C9	121.97 (19)
N1—C1—C2	125.4 (2)	N4—C10—C9	126.5 (2)
N1—C1—H1	117.3	C7—C8—C9	121.3 (2)
C2—C1—H1	117.3	C7—C8—H8	119.3
C8—C9—C10	117.4 (2)	C9—C8—H8	119.3
C8—C9—H9	121.3	C13—C12—C11	119.0 (2)
C10—C9—H9	121.3	C13—C12—H12	120.5
N3—C6—C7	122.7 (2)	C11—C12—H12	120.5
N3—C6—N2	116.95 (19)	N1—C3—C4	125.0 (2)
C7—C6—N2	120.3 (2)	N1—C3—H3	117.5
N2—C5—C2	124.1 (2)	C4—C3—H3	117.5
N2—C5—C4	118.9 (2)	N5—C15—C14	124.6 (3)
C2—C5—C4	117.0 (2)	N5—C15—H15	117.7
C3—C4—C5	119.3 (2)	C14—C15—H15	117.7
C3—C4—H4	120.4	C15—C14—C13	118.2 (2)
C5—C4—H4	120.4	C15—C14—H14	120.9
C11—N4—C10	131.6 (2)	C13—C14—H14	120.9
C11—N4—H4A	114.2	C12—C13—C14	119.1 (3)
C10—N4—H4A	114.2	C12—C13—H13	120.5
C1—C2—C5	118.7 (2)	C14—C13—H13	120.5

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N1ⁱ	0.86	2.22	3.038 (3)	160
N2—H2A···N3ⁱⁱ	0.86	2.35	3.198 (3)	170

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, z.

Experimental details

Crystal data
Chemical formula	C₁₅H₁₃N₅
M_r	263.30
Crystal system, space group	Orthorhombic, Pbca
Temperature (K)	298
a, b, c (Å)	11.4884 (15), 7.3445 (10), 30.718 (4)
V (Å³)	2591.9 (6)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.19 × 0.15 × 0.11

Data collection
Diffractometer	Bruker APEXII CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2005)
T_min, T_max	0.984, 0.991
No. of measured, independent and observed [I > 2σ(I)] reflections	11972, 2304, 1529
R_int	0.053
(sin θ/λ)_max (Å⁻¹)	0.599

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.050, 0.187, 0.82
No. of reflections	2304
No. of parameters	182
No. of restraints	1
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.23, −0.15

Computer programs: APEX2 (Bruker, 2005), SAINT (Bruker, 2005), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEPIII (Burnett & Johnson, 1996), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N4—H4A···N1ⁱ	0.86	2.22	3.038 (3)	160
N2—H2A···N3ⁱⁱ	0.86	2.35	3.198 (3)	170

Symmetry codes: (i) −x, y−1/2, −z+1/2; (ii) −x+1/2, y+1/2, z.

Acknowledgements

The authors are grateful to Zhejiang Shuren University for financial support.

References

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