1,4-Bis(3-pyridylamino­meth­yl)benzene

A new flexible bis­(pyrid­yl) complex, C₁₈H₁₈N₄, was prepared by the reaction of terephthalaldehyde with 3-amino­pyridine. The mol­ecule is centrosymmetric. Mononuclear units are linked into a one-dimensional chain by inter­molecular N—H...N hydrogen bonds. The dihedral angle bentween the pyridyl ring and the central benzene ring is 63.6 (2)°.

Key indicators

• Single-crystal X-ray study
• T = 295 K
• Mean [sigma](C-C)= 0.003 Å
• R factor = 0.045
• wR factor = 0.142
• Data-to-parameter ratio = 17.2

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S1. Comment

In recent years, extensive studies have been carried out to give many new one-dimensional, two-dimensional, and three-dimensional frameworks through the coordination of metal atoms with pyridine-based bridge ligands for example 4,4'-bipyridine and its derivatives like 1,2-bis(4-pyridyl)ethane (Park et al., 1998), 1,2-bis(4-pyridyl)ethene (Munno et al., 1999), and 1,3-bis(4-pyridyl)propane. Accordingly, we have designed and synthesized a new bis(pyridyl) complex, viz. 1,4-bis(pyridine-3-aminomethyl)benzene. The corresponding complex (Ru—Yi Zou et al., 2003), with 2-aminopyridine instead of 3-aminopyridine, has the similar structure.

The molecule of the title complex, (I) (Fig. 1), is centrosymmetric. The pair of pyridyl rings is parallel in a trans arrangement. The dihedral angle bentween the pyridyl ring and the central benzene ring is 63.6 °. The pyridyl-N form intermolecular N—H···N hydrogen bonds with the amino-H atom of adjacent molecules. The N···N distance and N—H···N angle are 3.112 (2) Å and 145.9 °, respectively. These intermolecular hydrogen-bonding interactions give rise to a chain structure.

Related literature

The corresponding complex (Zou et al., 2003) with 2-aminopyridine instead of 3-aminopyridine, has a similar structure. For related literature, see: Munno et al. (1999); Park et al. (1998).

S2. Experimental

A solution of terephthalaldehyde and 3-aminopyridine in toluene was heated under reflux. After 10 h, the solvent was removed under vacuum, and the remains were reduced in absolute methanol by sodium borohydride. Colourless crystals were obtained by recrystallization of the material from methanol with a yield of 83%.

S3. Refinement

H atoms were placed in calculated positions, with phenyl C—H = 0.95 Å, methylene C—H = 0.97 Å and amine N—H = 0.86 Å, and U_iso(H) = 1.2U_eq(C,N), which were included in the refinement in the riding-model approximation.

Computing details

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: SHELXL97 (Sheldrick, 1997); software used to prepare material for publication: SHELXL97 (Sheldrick, 1997).

Figures

Fig. 1. A view of complex (I), with the atom-numbering scheme. Displacement ellipsoids are drawn at the 30% probability level.

1,4-Bis(3-pyridylaminomethyl)benzene

Crystal data

C18H18N4	F(000) = 308
Mr = 290.36	Dx = 1.280 Mg m^−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 5126 reflections
a = 5.7064 (11) Å	θ = 3.4–27.5°
b = 22.174 (4) Å	µ = 0.08 mm^−1
c = 6.1717 (12) Å	T = 295 K
β = 105.29 (3)°	Prism, colourless
V = 753.3 (3) Å^3	0.32 × 0.26 × 0.25 mm
Z = 2

Data collection

Rigaku R-AXIS RAPID diffractometer	1724 independent reflections
Radiation source: fine-focus sealed tube	1173 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.020
Detector resolution: 10.000 pixels mm^-1	θmax = 27.5°, θmin = 3.5°
ω scans	h = −7→7
Absorption correction: multi-scan (ABSCOR; Higashi, 1995)	k = −28→28
Tmin = 0.971, Tmax = 0.979	l = −7→8
7359 measured reflections

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.046	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.142	H-atom parameters constrained
S = 1.11	w = 1/[σ^2(Fo^2) + (0.0657P)^2 + 0.1768P] where P = (Fo^2 + 2Fc^2)/3
1724 reflections	(Δ/σ)max < 0.001
100 parameters	Δρmax = 0.32 e Å^−3
0 restraints	Δρmin = −0.23 e Å^−3

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
N1	0.4126 (3)	0.16827 (7)	1.0083 (2)	0.0494 (4)
N2	0.3042 (3)	0.11085 (7)	0.4316 (2)	0.0515 (4)
H2	0.3734	0.1129	0.3238	0.062*
C1	0.3133 (3)	0.13915 (7)	0.8165 (3)	0.0421 (4)
H1	0.1770	0.1154	0.8090	0.050*
C2	0.4026 (3)	0.14236 (7)	0.6264 (2)	0.0378 (4)
C3	0.6056 (3)	0.17862 (7)	0.6430 (3)	0.0446 (4)
H3	0.6732	0.1820	0.5219	0.054*
C4	0.7054 (4)	0.20925 (8)	0.8379 (3)	0.0529 (5)
H4	0.8399	0.2340	0.8497	0.064*
C5	0.6044 (4)	0.20306 (9)	1.0172 (3)	0.0535 (5)
H5	0.6734	0.2241	1.1490	0.064*
C6	0.0894 (3)	0.07458 (9)	0.4027 (3)	0.0531 (5)
H7	−0.0495	0.1006	0.3935	0.064*
H6	0.1071	0.0485	0.5323	0.064*
C7	0.0442 (3)	0.03638 (7)	0.1924 (3)	0.0412 (4)
C8	−0.1740 (3)	0.03908 (8)	0.0311 (3)	0.0508 (5)
H8	−0.2939	0.0654	0.0501	0.061*
C9	−0.2180 (3)	0.00311 (9)	−0.1597 (3)	0.0526 (5)
H9	−0.3668	0.0057	−0.2668	0.063*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
N1	0.0630 (10)	0.0548 (9)	0.0345 (7)	−0.0082 (7)	0.0200 (7)	−0.0066 (6)
N2	0.0693 (11)	0.0566 (9)	0.0312 (7)	−0.0222 (7)	0.0181 (7)	−0.0080 (6)
C1	0.0495 (10)	0.0448 (9)	0.0337 (8)	−0.0051 (7)	0.0141 (7)	−0.0009 (6)
C2	0.0488 (9)	0.0344 (7)	0.0300 (7)	−0.0004 (6)	0.0101 (7)	0.0003 (6)
C3	0.0563 (10)	0.0469 (9)	0.0355 (8)	−0.0065 (8)	0.0208 (7)	−0.0017 (7)
C4	0.0607 (12)	0.0561 (10)	0.0446 (9)	−0.0185 (9)	0.0184 (8)	−0.0076 (8)
C5	0.0701 (13)	0.0556 (10)	0.0366 (9)	−0.0157 (9)	0.0175 (8)	−0.0114 (8)
C6	0.0595 (11)	0.0592 (11)	0.0433 (9)	−0.0144 (9)	0.0185 (8)	−0.0127 (8)
C7	0.0470 (9)	0.0410 (8)	0.0358 (8)	−0.0083 (7)	0.0111 (7)	−0.0031 (6)
C8	0.0469 (10)	0.0530 (10)	0.0508 (10)	0.0065 (8)	0.0098 (8)	−0.0079 (8)
C9	0.0443 (10)	0.0633 (11)	0.0433 (10)	0.0034 (8)	−0.0006 (8)	−0.0083 (8)

Geometric parameters (Å, º)

N1—C5	1.328 (2)	C4—H4	0.9300
N1—C1	1.336 (2)	C5—H5	0.9300
N2—C2	1.376 (2)	C6—C7	1.514 (2)
N2—C6	1.437 (2)	C6—H7	0.9700
N2—H2	0.8600	C6—H6	0.9700
C1—C2	1.399 (2)	C7—C8	1.375 (2)
C1—H1	0.9300	C7—C9^i	1.377 (2)
C2—C3	1.392 (2)	C8—C9	1.390 (2)
C3—C4	1.368 (2)	C8—H8	0.9300
C3—H3	0.9300	C9—C7^i	1.377 (2)
C4—C5	1.383 (3)	C9—H9	0.9300
C5—N1—C1	118.02 (14)	N1—C5—H5	118.7
C2—N2—C6	122.06 (14)	C4—C5—H5	118.7
C2—N2—H2	119.0	N2—C6—C7	111.49 (14)
C6—N2—H2	119.0	N2—C6—H7	109.3
N1—C1—C2	123.72 (16)	C7—C6—H7	109.3
N1—C1—H1	118.1	N2—C6—H6	109.3
C2—C1—H1	118.1	C7—C6—H6	109.3
N2—C2—C3	119.83 (14)	H7—C6—H6	108.0
N2—C2—C1	123.52 (15)	C8—C7—C9^i	118.11 (15)
C3—C2—C1	116.63 (14)	C8—C7—C6	120.87 (16)
C4—C3—C2	119.78 (14)	C9^i—C7—C6	121.00 (16)
C4—C3—H3	120.1	C7—C8—C9	121.03 (17)
C2—C3—H3	120.1	C7—C8—H8	119.5
C3—C4—C5	119.32 (16)	C9—C8—H8	119.5
C3—C4—H4	120.3	C7^i—C9—C8	120.86 (16)
C5—C4—H4	120.3	C7^i—C9—H9	119.6
N1—C5—C4	122.51 (16)	C8—C9—H9	119.6
C5—N1—C1—C2	1.3 (3)	C1—N1—C5—C4	−1.0 (3)
C6—N2—C2—C3	−177.61 (16)	C3—C4—C5—N1	0.0 (3)
C6—N2—C2—C1	4.1 (3)	C2—N2—C6—C7	−170.10 (15)
N1—C1—C2—N2	177.94 (16)	N2—C6—C7—C8	−124.94 (18)
N1—C1—C2—C3	−0.4 (3)	N2—C6—C7—C9^i	56.7 (2)
N2—C2—C3—C4	−179.05 (16)	C9^i—C7—C8—C9	−0.2 (3)
C1—C2—C3—C4	−0.6 (2)	C6—C7—C8—C9	−178.57 (17)
C2—C3—C4—C5	0.8 (3)	C7—C8—C9—C7^i	0.2 (3)

Symmetry code: (i) −x, −y, −z.

Hydrogen-bond geometry (Å, º)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1^ii	0.86	2.36	3.112 (2)	146

Symmetry code: (ii) x, y, z−1.