1,4-Bis­(pyridine-2-amino­methyl)­benzene

Zou, R.-Y.; Xu, F.-B.; Li, Q.-S.; Song, H.-B.; Lv, H.; Zhang, Z.-Z.

doi:10.1107/S1600536803017598

1,4-Bis(pyridine-2-aminomethyl)benzene

R.-Y. Zou, F.-B. Xu, Q.-S. Li, H.-B. Song, H. Lv and Z.-Z. Zhang

A novel, potentially tetradentate, ligand, C₁₈H₁₈N₄, was synthesized by the reaction of terephthalaldehyde with 2-aminopyridine. The molecule is centrosymmetric and the presence of hydrogen-bonding interactions results in a chain structure.

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Supporting information

	Crystallographic Information File (CIF) https://doi.org/10.1107/S1600536803017598/tk6125sup1.cif Contains datablocks global, I
	Structure factor file (CIF format) https://doi.org/10.1107/S1600536803017598/tk6125Isup2.hkl Contains datablock I

CCDC reference: 222867

checkCIF report

Key indicators

Single-crystal X-ray study
T = 293 K
Mean (C-C) = 0.003 Å
R factor = 0.044
wR factor = 0.111
Data-to-parameter ratio = 14.8

checkCIF/PLATON results

No syntax errors found



Alert level C
ABSTM02_ALERT_3_C  The ratio of expected to reported Tmax/Tmin(RR') is < 0.90
            Tmin and Tmax reported:      0.797     0.990
            Tmin' and Tmax expected:      0.967     0.985
            RR' =      0.819
            Please check that your absorption correction is appropriate.
PLAT029_ALERT_3_C _diffrn_measured_fraction_theta_full Low .....       0.99
PLAT061_ALERT_3_C Tmax/Tmin Range Test RR' too Large ...........       0.82

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

   0 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
   3 ALERT type 3 Indicator that the structure quality may be low
   0 ALERT type 4 Improvement, methodology, query or suggestion

Comment top

Studies of the molecular self-assembly of flexible N-heterocyclic ligands with metal ions have attracted much attention. This is mainly attributed to their applications in many fields as well as the versatile structures and properties their molecular assemblies display (Clayden & Pink, 1998; Hong et al., 2000; Kang et al., 2002). There is growing interest in finding alternative approaches for building new inexpensive and easy-to-prepare supramolecular systems. According to the above, we designed and synthesized a new flexible, potentially tetradentate, ligand, viz. 1,4-bis(pyridine-2-aminomethyl)benzene, (I), which may provide a new and versatile ligand for metal ions.

The molecule of (I) (Fig. 1) is disposed about a centre of inversion with the two parallel pyridyl terminal groups are in a trans arrangment. The dihedral angle between the pyridyl ring and the central phenyl group is 87°. The crystal structure is stabilized by the presence of intermolecular hydrogen-bonding interactions between pyridyl-N and the amino-H atom on a symmetry-related moleculae so that N1—H···N2ⁱ is 2.198 (19) Å, N1···N2ⁱ is 3.076 (3) Å and the angle subtended at H is 168.8 (17)° [symmetry code: (i) 1/2 − x, 3/2 − y, 1 − z]. These interactions give rise to a chain structure.

Experimental top

A solution of terephthalaldehyde and 2-aminopyridine in toluene was heated under reflux with stirring in a Dean–Stark apparatus. After 12 h, the solvent was removed under vacuum, and the remains, without further purification, were reduced in the absolute methanol by sodium borohydride, as described in the literature (Ashton et al., 1997). Colorless crystals were obtained by recrystallization of the material from methanol. Yield: 87%, m.p.: 465–467 K. Analysis calculated for C₁₈H₁₈N₄: C 74.46, H 6.25, N 19.29%; found: C 74.08, H 6.58, N 19.34%. ¹H NMR (300 MHz, CDCl₃): δ 4.50 (s, 4H), 6.37 (d, 2H), 6.59 (m, 2H), 7.33 (s, 4H), 7.40 (m, 2H), 8.10 (m, 2H).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART; data reduction: SAINT (Bruker, 1998); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Bruker, 1997); software used to prepare material for publication: SHELXTL.

Figures top

Fig. 1. View of the title compound, with displacement ellipsoids drawn at the 30% probability level.

1,4-bis(pyridine-2-aminomethyl)benzene top

Crystal data top

C₁₈H₁₈N₄	F(000) = 616
M_r = 290.36	D_x = 1.272 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2yc	Cell parameters from 548 reflections
a = 18.547 (11) Å	θ = 4.6–25.4°
b = 5.539 (3) Å	µ = 0.08 mm⁻¹
c = 15.303 (9) Å	T = 293 K
β = 105.328 (8)°	Block, colorless
V = 1516.3 (15) Å³	0.42 × 0.22 × 0.20 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1534 independent reflections
Radiation source: fine-focus sealed tube	1093 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.023
ϕ and ω scans	θ_max = 26.4°, θ_min = 3.1°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −22→17
T_min = 0.797, T_max = 0.990	k = −6→5
3292 measured reflections	l = −18→19

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)] = 0.044	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	w = 1/[σ²(F_o²) + (0.0526P)² + 0.3246P] where P = (F_o² + 2F_c²)/3
1534 reflections	(Δ/σ)_max < 0.001
104 parameters	Δρ_max = 0.13 e Å⁻³
0 restraints	Δρ_min = −0.15 e Å⁻³

Crystal data top

C₁₈H₁₈N₄	V = 1516.3 (15) Å³
M_r = 290.36	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 18.547 (11) Å	µ = 0.08 mm⁻¹
b = 5.539 (3) Å	T = 293 K
c = 15.303 (9) Å	0.42 × 0.22 × 0.20 mm
β = 105.328 (8)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1534 independent reflections
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	1093 reflections with I > 2σ(I)
T_min = 0.797, T_max = 0.990	R_int = 0.023
3292 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.044	0 restraints
wR(F²) = 0.111	H atoms treated by a mixture of independent and constrained refinement
S = 1.02	Δρ_max = 0.13 e Å⁻³
1534 reflections	Δρ_min = −0.15 e Å⁻³
104 parameters

Special details top

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
C1	0.28908 (10)	0.5376 (3)	0.69349 (11)	0.0534 (5)
H1	0.2546	0.4138	0.6900	0.064*
C2	0.34709 (11)	0.5526 (4)	0.76984 (12)	0.0603 (5)
H2	0.3520	0.4426	0.8170	0.072*
C3	0.39798 (11)	0.7361 (4)	0.77459 (12)	0.0583 (5)
H3	0.4383	0.7512	0.8255	0.070*
C4	0.38954 (9)	0.8959 (3)	0.70480 (11)	0.0496 (4)
H4	0.4238	1.0202	0.7074	0.060*
C5	0.32818 (8)	0.8686 (3)	0.62903 (10)	0.0387 (4)
C6	0.36767 (8)	1.1973 (3)	0.54305 (11)	0.0459 (4)
H6A	0.3834	1.2968	0.5969	0.055*
H6B	0.3432	1.3021	0.4933	0.055*
C7	0.43661 (8)	1.0906 (3)	0.52261 (9)	0.0374 (4)
C8	0.50399 (9)	1.2093 (3)	0.54765 (12)	0.0472 (4)
H8	0.5076	1.3522	0.5804	0.057*
C9	0.43337 (9)	0.8784 (3)	0.47466 (11)	0.0491 (4)
H9	0.3886	0.7934	0.4571	0.059*
N1	0.31354 (7)	1.0241 (3)	0.55711 (9)	0.0450 (4)
H1A	0.2818 (10)	0.960 (3)	0.5087 (13)	0.060 (5)*
N2	0.27875 (7)	0.6894 (2)	0.62341 (9)	0.0459 (4)

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0550 (11)	0.0531 (11)	0.0561 (10)	−0.0038 (9)	0.0216 (8)	0.0031 (9)
C2	0.0685 (12)	0.0655 (12)	0.0481 (10)	0.0084 (11)	0.0175 (9)	0.0139 (9)
C3	0.0543 (11)	0.0730 (13)	0.0417 (10)	0.0089 (10)	0.0024 (8)	0.0033 (9)
C4	0.0428 (9)	0.0566 (10)	0.0466 (9)	−0.0043 (8)	0.0066 (7)	−0.0007 (8)
C5	0.0323 (8)	0.0458 (9)	0.0404 (8)	0.0048 (7)	0.0138 (6)	−0.0019 (7)
C6	0.0420 (9)	0.0444 (9)	0.0527 (9)	0.0041 (8)	0.0148 (7)	0.0041 (8)
C7	0.0389 (8)	0.0368 (8)	0.0363 (7)	0.0004 (7)	0.0096 (6)	0.0030 (7)
C8	0.0469 (10)	0.0404 (9)	0.0554 (10)	−0.0071 (8)	0.0157 (8)	−0.0129 (8)
C9	0.0373 (9)	0.0521 (10)	0.0577 (10)	−0.0103 (8)	0.0123 (7)	−0.0114 (8)
N1	0.0345 (7)	0.0560 (9)	0.0431 (8)	−0.0007 (7)	0.0076 (6)	0.0040 (7)
N2	0.0397 (7)	0.0542 (9)	0.0454 (7)	−0.0034 (7)	0.0139 (6)	0.0003 (7)

Geometric parameters (Å, º) top

C1—N2	1.336 (2)	C6—N1	1.445 (2)
C1—C2	1.366 (2)	C6—C7	1.514 (2)
C1—H1	0.9300	C6—H6A	0.9700
C2—C3	1.376 (3)	C6—H6B	0.9700
C2—H2	0.9300	C7—C8	1.374 (2)
C3—C4	1.364 (2)	C7—C9	1.378 (2)
C3—H3	0.9300	C8—C9ⁱ	1.383 (2)
C4—C5	1.402 (2)	C8—H8	0.9300
C4—H4	0.9300	C9—C8ⁱ	1.383 (2)
C5—N2	1.339 (2)	C9—H9	0.9300
C5—N1	1.367 (2)	N1—H1A	0.889 (19)

N2—C1—C2	124.18 (17)	C7—C6—H6A	108.4
N2—C1—H1	117.9	N1—C6—H6B	108.4
C2—C1—H1	117.9	C7—C6—H6B	108.4
C1—C2—C3	117.67 (17)	H6A—C6—H6B	107.5
C1—C2—H2	121.2	C8—C7—C9	117.72 (14)
C3—C2—H2	121.2	C8—C7—C6	120.72 (14)
C4—C3—C2	120.20 (18)	C9—C7—C6	121.49 (14)
C4—C3—H3	119.9	C7—C8—C9ⁱ	121.64 (15)
C2—C3—H3	119.9	C7—C8—H8	119.2
C3—C4—C5	118.55 (17)	C9ⁱ—C8—H8	119.2
C3—C4—H4	120.7	C7—C9—C8ⁱ	120.64 (15)
C5—C4—H4	120.7	C7—C9—H9	119.7
N2—C5—N1	115.38 (14)	C8ⁱ—C9—H9	119.7
N2—C5—C4	121.70 (15)	C5—N1—C6	122.69 (14)
N1—C5—C4	122.91 (15)	C5—N1—H1A	111.5 (12)
N1—C6—C7	115.43 (13)	C6—N1—H1A	118.2 (11)
N1—C6—H6A	108.4	C1—N2—C5	117.70 (15)

N2—C1—C2—C3	0.0 (3)	C8—C7—C9—C8ⁱ	−0.5 (3)
C1—C2—C3—C4	0.2 (3)	C6—C7—C9—C8ⁱ	176.42 (15)
C2—C3—C4—C5	0.1 (3)	N2—C5—N1—C6	−167.44 (13)
C3—C4—C5—N2	−0.8 (2)	C4—C5—N1—C6	14.0 (2)
C3—C4—C5—N1	177.75 (15)	C7—C6—N1—C5	65.9 (2)
N1—C6—C7—C8	−150.12 (15)	C2—C1—N2—C5	−0.6 (2)
N1—C6—C7—C9	33.1 (2)	N1—C5—N2—C1	−177.65 (13)
C9—C7—C8—C9ⁱ	0.5 (3)	C4—C5—N2—C1	1.0 (2)
C6—C7—C8—C9ⁱ	−176.44 (15)

Symmetry code: (i) −x+1, −y+2, −z+1.

Experimental details

Crystal data
Chemical formula	C₁₈H₁₈N₄
M_r	290.36
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	293
a, b, c (Å)	18.547 (11), 5.539 (3), 15.303 (9)
β (°)	105.328 (8)
V (Å³)	1516.3 (15)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.08
Crystal size (mm)	0.42 × 0.22 × 0.20

Data collection
Diffractometer	Bruker SMART CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Sheldrick, 1996)
T_min, T_max	0.797, 0.990
No. of measured, independent and observed [I > 2σ(I)] reflections	3292, 1534, 1093
R_int	0.023
(sin θ/λ)_max (Å⁻¹)	0.626

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.044, 0.111, 1.02
No. of reflections	1534
No. of parameters	104
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.13, −0.15

Computer programs: SMART (Bruker, 1998), SMART, SAINT (Bruker, 1998), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Bruker, 1997), SHELXTL.

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1,4-Bis­(pyridine-2-amino­methyl)­benzene

Supporting information

Key indicators

checkCIF/PLATON results

1,4-Bis(pyridine-2-aminomethyl)benzene