N-[(E)-4-Pyridylmethyl­ene]-4-[(E)-4-(4-pyridylmethyl­eneamino)benz­yl]aniline tetra­hydrate

Hu, S.-L.; Li, Y.-T.; Cao, L.-P.

doi:10.1107/S1600536807063179

organic compounds

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Volume 64| Part 1| January 2008| Page o115

https://doi.org/10.1107/S1600536807063179

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N-[(E)-4-Pyridylmethylene]-4-[(E)-4-(4-pyridylmethyleneamino)benzyl]aniline tetrahydrate

Sheng-Li Hu,^a ^*‡ Yi-Tao Li ^a and Li-Ping Cao ^a

^aKey Laboratory of Pesticides and Chemical Biology, Ministry of Education, College of Chemistry, Central China Normal University, Wuhan 430079, People's Republic of China
^*Correspondence e-mail: hushengli168@126.com

(Received 21 November 2007; accepted 25 November 2007; online 6 December 2007)

The title compound, C₂₅H₂₀N₄·4H₂O, crystallizes with the organic molecule lying on a twofold rotation axis through the methylene bridge C atom; there are also two water molecules in the asymmetric unit. The crystal structure is stabilized by C—H⋯O, O—H⋯O and O—H⋯N hydrogen bonds, linking the water molecules to each other and to the pyridine N atom.

Related literature

For related literature, see: Jursic et al. (2002 ); Coucouvanis et al. (1993 ); Hodnett & Mooney (1970 ); Li et al. (2005 ); Yam & Pui (2002 ).

Experimental

Crystal data

C₂₅H₂₀N₄·4H₂O
M_r = 448.51
Monoclinic, C 2/c
a = 17.7743 (14) Å
b = 4.7309 (4) Å
c = 28.478 (2) Å
β = 99.69 (1)°
V = 2360.5 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 294 (2) K
0.40 × 0.30 × 0.30 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: none
7552 measured reflections
2302 independent reflections
1850 reflections with I > 2σ(I)
R_int = 0.022

Refinement

R[F² > 2σ(F²)] = 0.058
wR(F²) = 0.158
S = 1.08
2302 reflections
162 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C4—H4⋯O1	0.93	2.52	3.443 (3)	175
O1—H1C⋯O2	0.91 (4)	1.90 (4)	2.810 (3)	178 (4)
O2—H2B⋯N2ⁱ	0.87 (5)	1.94 (5)	2.782 (3)	163 (4)
O2—H2A⋯O1ⁱⁱ	0.88 (5)	1.93 (5)	2.765 (3)	160 (4)
O1—H1D⋯O2ⁱⁱⁱ	0.91 (4)	1.88 (4)	2.799 (3)	178 (4)
Symmetry codes: (i) $[-x+{\script{1\over 2}}, -y-{\script{1\over 2}}, -z+1]$ ; (ii) -x+1, -y+1, -z+1; (iii) -x+1, -y, -z+1.

Data collection: SMART (Bruker, 2001 ); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 1997 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000 ); software used to prepare material for publication: SHELXTL.

Supporting information

Crystal structure: contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536807063179/sf2014sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536807063179/sf2014Isup2.hkl

checkCIF report

Comment top

Schiff bases have received much attention due to their versatile properties and utilities such as anticancer properties (Hodnett & Mooney, 1970), supramolecule chemistry and molecular recognition (Coucouvanis et al., 1993; Yam & Pui, 2002) and catalysis in organic reaction through their metal complexes(Li et al., 2005). In this paper we report the crystal structure of the title schiff base, (I)(Fig. 1), I crystallizes with the main molecule lying on a twofold rotation axis through atom C1 and two independent water molecules in general positions. The phenyl ring C2/C3/C4/C5/C6/C7 and pyridine ring C9/C10/C11/N2/C12/C13 are trans with respect to C?N bond, and the dihedral angle between them is 7.21 (3)°. In the crystal structure, molecules are connected by water molecules via C—H···O, O—H···O, O—H···N hydrogen bonds. (Fig. 2 and Table 1). The molecular wings are approximately perpendicular to each other, and molecules pack by tucking their exo surfaces into the endo surface of the adjacent molecule along b - forming good Π stacking. The water molecules create an infinite puckered ladder along b which links to the terminal N atoms of the organic amide.

Related literature top

For related literature, see: Jursic et al. (2002); Coucouvanis et al. (1993); Hodnett & Mooney (1970); Li et al. (2005); Yam & Pui (2002).

Experimental top

The title compound was synthesized using a method analogous to the literature procedure of Jursic et al. (2002), Crystals appropriate for data collection were obtained by slow evaporation from a methanol-chloroform solution (1:20 V/V)of (I).

Structure description top

For related literature, see: Jursic et al. (2002); Coucouvanis et al. (1993); Hodnett & Mooney (1970); Li et al. (2005); Yam & Pui (2002).

Computing details top

Data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); program(s) used to solve structure: SHELXS97 (Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics: SHELXTL (Sheldrick, 2000); software used to prepare material for publication: SHELXTL (Sheldrick, 2000).

Figures top

	Fig. 1. The molecular structure showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level. H atoms atoms shown as circles of arbitrary radii.
	Fig. 2. The molecular packing of (I), with hydrogen bonds shown as dashed lines

N-[(E)-4-Pyridylmethylene]-4-[(E)-4-(4-pyridylmethyleneamino)benzyl]aniline tetrahydrate top

Crystal data top

C₂₅H₂₀N₄·4H₂O	F(000) = 952
M_r = 448.51	D_x = 1.262 Mg m⁻³
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -C 2/c	Cell parameters from 2376 reflections
a = 17.7743 (14) Å	θ = 2.3–27.4°
b = 4.7309 (4) Å	µ = 0.09 mm⁻¹
c = 28.478 (2) Å	T = 294 K
β = 99.69 (1)°	Block, yellow
V = 2360.5 (3) Å³	0.40 × 0.30 × 0.30 mm
Z = 4

Data collection top

Bruker SMART CCD area-detector diffractometer	1850 reflections with I > 2σ(I)
Radiation source: fine-focus sealed tube	R_int = 0.022
Graphite monochromator	θ_max = 26.0°, θ_min = 2.3°
phi and ω scans	h = −13→21
7552 measured reflections	k = −5→5
2302 independent reflections	l = −35→35

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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ²(F_o²) + (0.0751P)² + 1.2009P] where P = (F_o² + 2F_c²)/3
2302 reflections	(Δ/σ)_max < 0.001
162 parameters	Δρ_max = 0.20 e Å⁻³
0 restraints	Δρ_min = −0.18 e Å⁻³

Crystal data top

C₂₅H₂₀N₄·4H₂O	V = 2360.5 (3) Å³
M_r = 448.51	Z = 4
Monoclinic, C2/c	Mo Kα radiation
a = 17.7743 (14) Å	µ = 0.09 mm⁻¹
b = 4.7309 (4) Å	T = 294 K
c = 28.478 (2) Å	0.40 × 0.30 × 0.30 mm
β = 99.69 (1)°

Data collection top

Bruker SMART CCD area-detector diffractometer	1850 reflections with I > 2σ(I)
7552 measured reflections	R_int = 0.022
2302 independent reflections

Refinement top

R[F² > 2σ(F²)] = 0.058	0 restraints
wR(F²) = 0.158	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	Δρ_max = 0.20 e Å⁻³
2302 reflections	Δρ_min = −0.18 e Å⁻³
162 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	Occ. (<1)
C1	0.5000	0.9902 (5)	0.2500	0.0468 (6)
H1A	0.4695	1.1104	0.2266	0.056*	0.50
H1B	0.5305	1.1104	0.2734	0.056*	0.50
C2	0.44833 (9)	0.8053 (3)	0.27406 (6)	0.0400 (4)
C3	0.47436 (10)	0.6805 (4)	0.31775 (6)	0.0493 (5)
H3	0.5231	0.7234	0.3336	0.059*
C4	0.42989 (11)	0.4944 (4)	0.33839 (7)	0.0504 (5)
H4	0.4487	0.4148	0.3679	0.060*
C5	0.35682 (10)	0.4251 (4)	0.31521 (6)	0.0419 (4)
C6	0.32993 (10)	0.5543 (4)	0.27215 (6)	0.0456 (4)
H6	0.2808	0.5141	0.2565	0.055*
C7	0.37470 (10)	0.7423 (4)	0.25190 (6)	0.0449 (4)
H7	0.3551	0.8276	0.2230	0.054*
C8	0.32973 (11)	0.0807 (4)	0.36783 (7)	0.0511 (5)
H8	0.3811	0.0887	0.3814	0.061*
C9	0.27972 (11)	−0.1144 (4)	0.38837 (6)	0.0492 (5)
C10	0.30718 (14)	−0.2665 (5)	0.42886 (8)	0.0658 (6)
H10	0.3578	−0.2467	0.4435	0.079*
C11	0.25914 (16)	−0.4484 (5)	0.44754 (9)	0.0739 (7)
H11	0.2788	−0.5490	0.4749	0.089*
C12	0.16076 (14)	−0.3398 (6)	0.38962 (10)	0.0770 (7)
H12	0.1098	−0.3633	0.3759	0.092*
C13	0.20413 (12)	−0.1544 (5)	0.36816 (8)	0.0642 (6)
H13	0.1830	−0.0579	0.3406	0.077*
N1	0.30633 (9)	0.2361 (3)	0.33305 (5)	0.0481 (4)
N2	0.18689 (13)	−0.4874 (4)	0.42866 (8)	0.0748 (6)
O1	0.49404 (13)	0.2296 (5)	0.45062 (7)	0.0944 (7)
H1C	0.472 (2)	0.249 (8)	0.4769 (14)	0.142*
H1D	0.521 (2)	0.065 (9)	0.4559 (14)	0.142*
O2	0.42372 (14)	0.2747 (5)	0.53161 (9)	0.1114 (8)
H2A	0.442 (3)	0.440 (11)	0.5419 (15)	0.167*
H2B	0.386 (3)	0.219 (10)	0.5448 (16)	0.167*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0515 (15)	0.0357 (13)	0.0585 (15)	0.000	0.0250 (12)	0.000
C2	0.0424 (9)	0.0319 (8)	0.0501 (10)	0.0024 (7)	0.0206 (7)	−0.0036 (7)
C3	0.0425 (10)	0.0537 (11)	0.0523 (10)	−0.0080 (8)	0.0102 (8)	−0.0007 (8)
C4	0.0506 (11)	0.0545 (11)	0.0463 (10)	−0.0080 (9)	0.0091 (8)	0.0062 (8)
C5	0.0434 (10)	0.0382 (9)	0.0481 (10)	−0.0037 (7)	0.0190 (7)	−0.0058 (7)
C6	0.0384 (9)	0.0460 (10)	0.0528 (10)	−0.0032 (8)	0.0089 (7)	−0.0003 (8)
C7	0.0458 (10)	0.0424 (10)	0.0487 (10)	0.0049 (8)	0.0140 (8)	0.0042 (7)
C8	0.0493 (11)	0.0475 (10)	0.0589 (11)	−0.0087 (8)	0.0159 (9)	−0.0010 (9)
C9	0.0597 (12)	0.0397 (10)	0.0530 (11)	−0.0085 (8)	0.0237 (9)	−0.0064 (8)
C10	0.0730 (14)	0.0611 (13)	0.0651 (13)	−0.0125 (11)	0.0167 (11)	0.0066 (10)
C11	0.0983 (19)	0.0629 (14)	0.0663 (14)	−0.0161 (13)	0.0303 (13)	0.0112 (11)
C12	0.0674 (14)	0.0750 (16)	0.0933 (18)	−0.0255 (12)	0.0271 (13)	0.0000 (14)
C13	0.0630 (13)	0.0626 (13)	0.0695 (14)	−0.0158 (11)	0.0179 (10)	0.0047 (10)
N1	0.0490 (9)	0.0456 (9)	0.0527 (9)	−0.0083 (7)	0.0173 (7)	0.0003 (7)
N2	0.0899 (15)	0.0609 (12)	0.0839 (14)	−0.0222 (11)	0.0440 (12)	−0.0001 (10)
O1	0.1031 (15)	0.1013 (15)	0.0787 (12)	−0.0129 (12)	0.0153 (10)	0.0224 (11)
O2	0.1177 (18)	0.0957 (16)	0.1373 (19)	−0.0295 (13)	0.0691 (15)	0.0062 (13)

Geometric parameters (Å, º) top

C1—C2ⁱ	1.513 (2)	C8—C9	1.469 (3)
C1—C2	1.513 (2)	C8—H8	0.9300
C1—H1A	0.9700	C9—C10	1.377 (3)
C1—H1B	0.9700	C9—C13	1.383 (3)
C2—C3	1.385 (3)	C10—C11	1.380 (3)
C2—C7	1.386 (3)	C10—H10	0.9300
C3—C4	1.379 (2)	C11—N2	1.319 (3)
C3—H3	0.9300	C11—H11	0.9300
C4—C5	1.393 (3)	C12—N2	1.329 (3)
C4—H4	0.9300	C12—C13	1.377 (3)
C5—C6	1.382 (2)	C12—H12	0.9300
C5—N1	1.420 (2)	C13—H13	0.9300
C6—C7	1.382 (2)	O1—H1C	0.91 (4)
C6—H6	0.9300	O1—H1D	0.91 (4)
C7—H7	0.9300	O2—H2A	0.88 (5)
C8—N1	1.247 (2)	O2—H2B	0.87 (5)

C2ⁱ—C1—C2	109.37 (19)	C2—C7—H7	119.5
C2ⁱ—C1—H1A	109.8	N1—C8—C9	122.89 (18)
C2—C1—H1A	109.8	N1—C8—H8	118.6
C2ⁱ—C1—H1B	109.8	C9—C8—H8	118.6
C2—C1—H1B	109.8	C10—C9—C13	117.36 (18)
H1A—C1—H1B	108.2	C10—C9—C8	120.58 (19)
C3—C2—C7	117.66 (16)	C13—C9—C8	122.06 (18)
C3—C2—C1	121.12 (14)	C9—C10—C11	119.6 (2)
C7—C2—C1	121.11 (14)	C9—C10—H10	120.2
C4—C3—C2	121.77 (17)	C11—C10—H10	120.2
C4—C3—H3	119.1	N2—C11—C10	123.6 (2)
C2—C3—H3	119.1	N2—C11—H11	118.2
C3—C4—C5	120.24 (17)	C10—C11—H11	118.2
C3—C4—H4	119.9	N2—C12—C13	124.3 (2)
C5—C4—H4	119.9	N2—C12—H12	117.9
C6—C5—C4	118.18 (16)	C13—C12—H12	117.9
C6—C5—N1	116.81 (15)	C12—C13—C9	118.7 (2)
C4—C5—N1	124.99 (16)	C12—C13—H13	120.7
C5—C6—C7	121.16 (16)	C9—C13—H13	120.7
C5—C6—H6	119.4	C8—N1—C5	120.59 (16)
C7—C6—H6	119.4	C11—N2—C12	116.53 (19)
C6—C7—C2	120.95 (16)	H1C—O1—H1D	104 (3)
C6—C7—H7	119.5	H2A—O2—H2B	113 (4)

C2ⁱ—C1—C2—C3	79.47 (15)	N1—C8—C9—C13	5.0 (3)
C2ⁱ—C1—C2—C7	−96.86 (15)	C13—C9—C10—C11	−0.3 (3)
C7—C2—C3—C4	1.5 (3)	C8—C9—C10—C11	179.97 (19)
C1—C2—C3—C4	−174.93 (16)	C9—C10—C11—N2	0.1 (4)
C2—C3—C4—C5	0.5 (3)	N2—C12—C13—C9	−0.7 (4)
C3—C4—C5—C6	−2.0 (3)	C10—C9—C13—C12	0.6 (3)
C3—C4—C5—N1	179.84 (16)	C8—C9—C13—C12	−179.7 (2)
C4—C5—C6—C7	1.5 (3)	C9—C8—N1—C5	178.70 (15)
N1—C5—C6—C7	179.84 (15)	C6—C5—N1—C8	169.49 (17)
C5—C6—C7—C2	0.5 (3)	C4—C5—N1—C8	−12.3 (3)
C3—C2—C7—C6	−2.0 (2)	C10—C11—N2—C12	−0.1 (4)
C1—C2—C7—C6	174.46 (16)	C13—C12—N2—C11	0.5 (4)
N1—C8—C9—C10	−175.31 (19)

Symmetry code: (i) −x+1, y, −z+1/2.

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1	0.93	2.52	3.443 (3)	175
O1—H1C···O2	0.91 (4)	1.90 (4)	2.810 (3)	178 (4)
O2—H2B···N2ⁱⁱ	0.87 (5)	1.94 (5)	2.782 (3)	163 (4)
O2—H2A···O1ⁱⁱⁱ	0.88 (5)	1.93 (5)	2.765 (3)	160 (4)
O1—H1D···O2^iv	0.91 (4)	1.88 (4)	2.799 (3)	178 (4)

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

Experimental details

Crystal data
Chemical formula	C₂₅H₂₀N₄·4H₂O
M_r	448.51
Crystal system, space group	Monoclinic, C2/c
Temperature (K)	294
a, b, c (Å)	17.7743 (14), 4.7309 (4), 28.478 (2)
β (°)	99.69 (1)
V (Å³)	2360.5 (3)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.09
Crystal size (mm)	0.40 × 0.30 × 0.30

Data collection
Diffractometer	Bruker SMART CCD area-detector
Absorption correction	–
No. of measured, independent and observed [I > 2σ(I)] reflections	7552, 2302, 1850
R_int	0.022
(sin θ/λ)_max (Å⁻¹)	0.617

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.058, 0.158, 1.08
No. of reflections	2302
No. of parameters	162
H-atom treatment	H atoms treated by a mixture of independent and constrained refinement
Δρ_max, Δρ_min (e Å⁻³)	0.20, −0.18

Computer programs: SMART (Bruker, 2001), SAINT (Bruker, 2001), SHELXS97 (Sheldrick, 1997), SHELXL97 (Sheldrick, 1997), SHELXTL (Sheldrick, 2000).

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
C4—H4···O1	0.93	2.52	3.443 (3)	175.4
O1—H1C···O2	0.91 (4)	1.90 (4)	2.810 (3)	178 (4)
O2—H2B···N2ⁱ	0.87 (5)	1.94 (5)	2.782 (3)	163 (4)
O2—H2A···O1ⁱⁱ	0.88 (5)	1.93 (5)	2.765 (3)	160 (4)
O1—H1D···O2ⁱⁱⁱ	0.91 (4)	1.88 (4)	2.799 (3)	178 (4)

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

Footnotes

‡Also at Hubei Key Laboratory of Bioanalytical Techniques (Hubei Normal University), Huangshi 435002, People's Republic of China.

Acknowledgements

We are grateful to the Central China Normal University for financial support

References

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