Crystal structure of (E)-N-(3,4-di­meth­oxy­benzyl­idene)morpholin-4-amine

Sevim Türktekin Çelikesir; Mehmet Akkurt; Aliasghar Jarrahpour; Orhan Büyükgüngör

doi:10.1107/S160053681401678X

. 2014 Aug 1;70(Pt 9):o935. doi: 10.1107/S160053681401678X

Crystal structure of (E)-N-(3,4-dimethoxybenzylidene)morpholin-4-amine

Sevim Türktekin Çelikesir ^a, Mehmet Akkurt ^a,^*, Aliasghar Jarrahpour ^b, Orhan Büyükgüngör ^c

PMCID: PMC4186114 PMID: 25309263

Abstract

In the title compound, C₁₃H₁₈N₂O₃, the benzene ring makes a dihedral angle of 17.19 (11)° with the least-squares plane formed by the four C atoms of the morpholine ring, which adopts a chair conformation. In the crystal, C—H⋯N hydrogen bonds link the molecules into supramolecular chains running along a 2₁ screw axis parallel to the b-axis direction. Weak C—H⋯π interactions are also observed.

Keywords: crystal structure, hydrogen bonding, C—H⋯π interactions, Schiff bases, morpholin-4-amine

Related literature

For the structures of related compounds, see: Akkurt et al. (2013 ▶, 2014 ▶). For ring-puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C₁₃H₁₈N₂O₃
M _r = 250.29
Monoclinic,
a = 9.1644 (6) Å
b = 6.0277 (6) Å
c = 13.1327 (9) Å
β = 109.989 (5)°
V = 681.75 (10) Å³
Z = 2
Mo Kα radiation
μ = 0.09 mm⁻¹
T = 296 K
0.58 × 0.42 × 0.24 mm

Data collection

Stoe IPDS 2 diffractometer
Absorption correction: integration (X-RED32; Stoe & Cie, 2002 ▶) T _min = 0.962, T _max = 0.983
8493 measured reflections
3219 independent reflections
2071 reflections with I > 2σ(I)
R _int = 0.229

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.106
S = 1.00
3219 reflections
164 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 0.09 e Å⁻³
Δρ_min = −0.18 e Å⁻³
Absolute structure: Flack (1983 ▶), 1353 Friedel pairs
Absolute structure parameter: −0.4 (19)

Data collection: X-AREA (Stoe & Cie, 2002 ▶); cell refinement: X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ▶); software used to prepare material for publication: WinGX (Farrugia, 2012 ▶), PARST (Nardelli, 1983 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681401678X/rz5130sup1.cif

e-70-0o935-sup1.cif^{(23.1KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681401678X/rz5130Isup2.hkl

e-70-0o935-Isup2.hkl^{(176.7KB, hkl)}

Click here for additional data file.^{(5.4KB, cml)}

Supporting information file. DOI: 10.1107/S160053681401678X/rz5130Isup3.cml

Click here for additional data file.^{(1.1MB, tif)}

. DOI: 10.1107/S160053681401678X/rz5130fig1.tif

The molecular structure of the title compound with 30% probability displacement ellipsoids.

Click here for additional data file.^{(1.3MB, tif)}

a . DOI: 10.1107/S160053681401678X/rz5130fig2.tif

Packing diagram of the title compound viewed down the a axis. Hydrogen bonds are indicated by dashed lines. For clarity, H atoms not participating in hydrogen bonding are omitted.

CCDC reference: 1015028

Additional supporting information: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg1 is the centroid of the C6–C11 benzene ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
C1—H1B⋯N1ⁱ	0.97	2.61	3.542 (3)	161
C8—H8⋯Cg1ⁱⁱ	0.93	2.87	3.576 (3)	134

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors acknowledge the Faculty of Arts and Sciences, Ondokuz Mayıs University, Turkey, for the use of the Stoe IPDS 2 diffractometer (purchased under grant F.279 of the University Research Fund).

supplementary crystallographic information

S1. Comment

As part of our continuing interest in the design and chemistry of Schiff bases containing a morpholine moiety, the title compound has been synthesized and its crystal structure is reported herein. In the title compound (Fig. 1), the benzene ring (C6–C11) makes a dihedral angle of 17.19 (11)° with the least-squares plane formed by the four C atoms of the morpholine ring (C1–C4/N1/O1), which adopts a chair conformation [the puckering parameters (Cremer & Pople, 1975) are Q_T = 0.557 (3) Å, θ = 177.2 (3)°, φ = 177 (7)°]. The N1–N2–C5–C6, C10–C9–O2–C12 and C9–C10–O3–C13 torsion angles are -173.7 (2), 178.2 (3) and -178.9 (3)°, respectively. The bond lengths and bond angles are normal and comparable with those reported for related compounds (Akkurt et al. 2013, 2014). In the crystal structure, molecules are linked by intermolecular C—H···N hydrogen bonds forming supramolecular chains running along a 2₁ screw axis parallel to the [010] direction (Table 1, Fig. 2). In addition, weak C—H. . .π interactions also occur (Table 1).

S2. Experimental

Reaction of 3,4-dimethoxybenzaldehyde (1.0 mmol) with morpholin-4-amine (1.0 mmol) in refluxing ethanol gave the title compound. Recrystallization from ethanol gave colourless crystals in 85 % yield. M.p.: 345-347 K. IR (KBr) cm^-1:1604 (C=N). ¹H-NMR (250 MHz, CDCl₃), δ (ppm): 3.06 (CH₂-N, t, 4H, J=5 Hz), 3.79 (CH₂-O, t, 4H, J=5 Hz), 3.83 (2OMe, s, 6H), 6.73 (aromatic H, d, 1H, J=7.5 Hz), 6.93 (aromatic H, d, 1H, J=7.5 Hz), 7.49 (aromatic H, s, 1H), 7.81 (HC=N, s, 1H). ¹³CNMR (62.9 MHz, CDCl₃), δ (p.p.m): 52.1 (CH₂-N), 55.8 (2OMe), 66.4 (CH₂-O), 107.4-137.0 (aromatic carbons), 149.6 (C═N).