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access(E)-4-{[(Morpholin-4-yl)imino]methyl}benzonitrile
aIlke Education and Health Foundation, Cappadocia Vocational College, The Medical Imaging Techniques Program, 50420 Mustafapaşa, Ürgüp, Nevşehir, Turkey, bDepartment of Physics, Faculty of Sciences, Erciyes University, 38039 Kayseri, Turkey, cDepartment of Chemistry, College of Sciences, Shiraz University, 71454 Shiraz, Iran, and dDepartment of Physics, Faculty of Arts and Sciences, Ondokuz Mayıs University, 55139 Samsun, Turkey
*Correspondence e-mail: akkurt@erciyes.edu.tr
In the title compound, C12H13N3O, the morpholine ring adopts a chair conformation and its mean plane is inclined to that of the benzene ring by 16.78 (12)°. The N—N=C—C bridge, which has an E conformation, has a torsion angle of 173.80 (19)°. In the crystal, molecules stack along the a axis but there are no significant intermolecular interactions present.
Keywords: crystal structure.
CCDC reference: 1008300
Related literature
For background to the importance of see: Dhar & Taploo (1982![[Dhar, D. N. & Taploo, C. L. (1982). J. Sci. Ind. Res. 41, 501-506.]](../../../../../../logos/arrows/e_arr.gif "Dhar, D. N. & Taploo, C. L. (1982). J. Sci. Ind. Res. 41, 501-506.")
); Zheng et al. (2009); Guzen et al. (2007); Asif (2014); Hisaindee et al. (2013). For a related structure, see: Akkurt et al. (2013).
![[Scheme 1]](su2744scheme1.gif)
Experimental
Crystal data
|
Data collection: X-AREA (Stoe & Cie, 2002); cell X-AREA; data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).
Supporting information
CCDC reference: 1008300
contains datablocks global, I. DOI: https://doi.org/10.1107/S1600536814014020/su2744sup1.cif
Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S1600536814014020/su2744Isup2.hkl
Supporting information file. DOI: https://doi.org/10.1107/S1600536814014020/su2744Isup3.cml
The title compound was synthesized by refluxing 4-aminomorpholine (1.00 mmol) with 4-cyanobenzeldehyde (1.00 mmol) in ethanol for 30 min. It was then recrystallized from ethanol to give light-yellow prismatic crystals (Yield 86%; M.p.: 401–403 K). Spectroscopic data for the title compound are available in the archived CIF.
All H atoms were placed in calculated positions and refined as riding: C—H = 0.93 and 0.97 Å for CH and CH2 H atoms, respectively, with Uiso(H) = 1.2Ueq(C). The crystals were of poor quality and weakly diffracting, which accounts for the low fraction of measured reflections. Repeated attempts to grow larger crystals were unsuccessful.
Schiff bases, also known as or are some of the most widely used organic compounds, for example, as pigments and dyes, catalysts, polymer stabilizers, and as intermediates in organic synthesis in particular for the preparation of heterocycles (Dhar & Taploo 1982; Zheng et al., 2009; Guzen et al., 2007). also play an important role in biological systems with several applications, for example, as antifungal, anticancer, antibacterial, antimalarial, antiproliferative, anti-inflammatory and antiviral agents in addition to other biological performances (Asif, 2014; Hisaindee et al., 2013). In view of this interest we synthesized the title compound and report herein on its crystal structure.
In the title molecule, Fig.1, the morpholine ring (N1/O1/C1–C4) adopts a chair conformation [puckering parameters: QT = 0.553 (3) Å, θ = 3.0 (3) ° and φ = 12 (6) °]. The N1–N2═C5–C6 torsion angle is is 173.80 (19) °. Bond lengths and angles are similar to those reported for a related structure (Akkurt et al., 2013).
In the there are no classical hydrogen bonds. The crystal packing is stabilized by van der Waals interactions.
For background to the importance of see: Dhar & Taploo (1982); Zheng et al. (2009); Guzen et al. (2007); Asif (2014); Hisaindee et al. (2013). For a related structure, see: Akkurt et al. (2013).
Data collection: X-AREA (Stoe & Cie, 2002); cell X-AREA (Stoe & Cie, 2002); data reduction: X-RED32 (Stoe & Cie, 2002); program(s) used to solve structure: SHELXS2013 (Sheldrick, 2008); program(s) used to refine structure: SHELXL2013 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).
![[Figure 1]](./su2744fig1thm.gif) | Fig. 1. The molecular structure of the title molecule, with atom labelling. Displacement ellipsoids are drawn at the 30% probability level. |
![[Figure 2]](./su2744fig2thm.gif) | Fig. 2. The crystal packing of the title compound, viewed along the a axis. |
| C12H13N3O | F(000) = 456 |
| Mr = 215.25 | Dx = 1.257 Mg m−3 |
| Monoclinic, P21/n | Mo Kα radiation, λ = 0.71073 Å |
| Hall symbol: -P 2yn | Cell parameters from 4198 reflections |
| a = 4.1054 (3) Å | θ = 1.7–27.1° |
| b = 12.0509 (8) Å | µ = 0.08 mm−1 |
| c = 22.9972 (19) Å | T = 296 K |
| β = 91.087 (6)° | Prism, light yellow |
| V = 1137.55 (15) Å3 | 0.54 × 0.24 × 0.08 mm |
| Z = 4 |
| Stoe IPDS 2 diffractometer | 2394 independent reflections |
| Radiation source: sealed X-ray tube, 12 x 0.4 mm long-fine focus | 878 reflections with I > 2σ(I) |
| Plane graphite monochromator | Rint = 0.229 |
| Detector resolution: 6.67 pixels mm-1 | θmax = 26.7°, θmin = 1.8° |
| rotation method scans | h = −5→5 |
| Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | k = −13→15 |
| Tmin = 0.971, Tmax = 0.994 | l = −29→28 |
| 6956 measured reflections |
| Refinement on F2 | 0 restraints |
| Least-squares matrix: full | Hydrogen site location: inferred from neighbouring sites |
| R[F2 > 2σ(F2)] = 0.063 | H-atom parameters constrained |
| wR(F2) = 0.094 | w = 1/[σ2(Fo2) + (0.021P)2] where P = (Fo2 + 2Fc2)/3 |
| S = 0.89 | (Δ/σ)max < 0.001 |
| 2394 reflections | Δρmax = 0.12 e Å−3 |
| 146 parameters | Δρmin = −0.11 e Å−3 |
| C12H13N3O | V = 1137.55 (15) Å3 |
| Mr = 215.25 | Z = 4 |
| Monoclinic, P21/n | Mo Kα radiation |
| a = 4.1054 (3) Å | µ = 0.08 mm−1 |
| b = 12.0509 (8) Å | T = 296 K |
| c = 22.9972 (19) Å | 0.54 × 0.24 × 0.08 mm |
| β = 91.087 (6)° |
| Stoe IPDS 2 diffractometer | 2394 independent reflections |
| Absorption correction: integration (X-RED32; Stoe & Cie, 2002) | 878 reflections with I > 2σ(I) |
| Tmin = 0.971, Tmax = 0.994 | Rint = 0.229 |
| 6956 measured reflections |
| R[F2 > 2σ(F2)] = 0.063 | 0 restraints |
| wR(F2) = 0.094 | H-atom parameters constrained |
| S = 0.89 | Δρmax = 0.12 e Å−3 |
| 2394 reflections | Δρmin = −0.11 e Å−3 |
| 146 parameters |
Experimental. Spectropscopic data for the title compound: IR (KBr, cm-1): 1604 (Schiff base C=N), 2214 (nitrile CN). 1H-NMR (250 MHz, CDCl3), δ (p.p.m.): 3.18–3.22 (CH2 morpholine ring, m, 4H), 3.83–3.87 (CH2 morpholine ring, m, 4H), 7.48 (HC=N, s, 1H), 7.54 (ArH, d, J=8.4 Hz, 2H), 7.62 (ArH, d, J=8.2 Hz, 2H). 13C-NMR (62.9 MHz, CDCl3), δ (p.p.m.): 51.3 (CH2N), 66.2 (CH2O), 110.7, 119.0, 126.2, 132.3, 132.6 (aromatic carbons and nitrile), 140.4 (C=N). |
Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles |
Refinement. Refinement on F2 for ALL reflections except those flagged by the user for potential systematic errors. Weighted R-factors wR and all goodnesses of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The observed criterion of F2 > σ(F2) is used only for calculating -R-factor-obs 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. |
| x | y | z | Uiso*/Ueq | ||
| O1 | 0.3333 (4) | 0.7856 (2) | 0.26705 (10) | 0.0934 (9) | |
| N1 | 0.5804 (4) | 0.92897 (19) | 0.18135 (10) | 0.0661 (9) | |
| N2 | 0.6187 (4) | 0.9921 (2) | 0.13245 (9) | 0.0642 (9) | |
| N3 | 0.9567 (8) | 1.4147 (2) | −0.10077 (15) | 0.1297 (14) | |
| C1 | 0.4673 (6) | 0.8185 (2) | 0.16642 (12) | 0.0744 (11) | |
| C2 | 0.5031 (6) | 0.7434 (3) | 0.21844 (15) | 0.0919 (15) | |
| C3 | 0.4574 (7) | 0.8916 (3) | 0.28163 (13) | 0.0920 (14) | |
| C4 | 0.4229 (6) | 0.9736 (2) | 0.23245 (12) | 0.0739 (11) | |
| C5 | 0.5801 (5) | 1.0975 (3) | 0.13421 (11) | 0.0671 (10) | |
| C6 | 0.6545 (6) | 1.1639 (2) | 0.08316 (12) | 0.0621 (10) | |
| C7 | 0.5920 (6) | 1.2770 (2) | 0.08316 (13) | 0.0797 (12) | |
| C8 | 0.6662 (7) | 1.3426 (2) | 0.03595 (15) | 0.0865 (14) | |
| C9 | 0.8027 (6) | 1.2960 (3) | −0.01231 (14) | 0.0732 (11) | |
| C10 | 0.8635 (6) | 1.1833 (2) | −0.01327 (14) | 0.0864 (12) | |
| C11 | 0.7892 (6) | 1.1192 (2) | 0.03383 (13) | 0.0817 (12) | |
| C12 | 0.8858 (8) | 1.3627 (3) | −0.06134 (17) | 0.0941 (16) | |
| H1A | 0.59330 | 0.78940 | 0.13460 | 0.0890* | |
| H1B | 0.24050 | 0.82150 | 0.15390 | 0.0890* | |
| H2A | 0.41920 | 0.67040 | 0.20860 | 0.1100* | |
| H2B | 0.73230 | 0.73570 | 0.22870 | 0.1100* | |
| H3A | 0.68600 | 0.88470 | 0.29250 | 0.1100* | |
| H3B | 0.34310 | 0.91970 | 0.31510 | 0.1100* | |
| H4A | 0.19410 | 0.98700 | 0.22380 | 0.0890* | |
| H4B | 0.52330 | 1.04350 | 0.24350 | 0.0890* | |
| H5 | 0.50530 | 1.13130 | 0.16780 | 0.0800* | |
| H7 | 0.49840 | 1.30930 | 0.11550 | 0.0950* | |
| H8 | 0.62370 | 1.41830 | 0.03690 | 0.1040* | |
| H10 | 0.95490 | 1.15100 | −0.04590 | 0.1030* | |
| H11 | 0.83060 | 1.04340 | 0.03250 | 0.0980* |
| U11 | U22 | U33 | U12 | U13 | U23 | |
| O1 | 0.0852 (12) | 0.1033 (19) | 0.0918 (16) | −0.0208 (12) | 0.0086 (12) | 0.0200 (14) |
| N1 | 0.0643 (13) | 0.0668 (18) | 0.0673 (15) | −0.0065 (11) | 0.0016 (12) | 0.0045 (14) |
| N2 | 0.0627 (12) | 0.0629 (17) | 0.0669 (15) | −0.0007 (12) | 0.0013 (11) | 0.0014 (13) |
| N3 | 0.191 (3) | 0.086 (2) | 0.112 (2) | −0.031 (2) | −0.002 (2) | 0.0243 (19) |
| C1 | 0.0715 (16) | 0.065 (2) | 0.087 (2) | −0.0054 (14) | 0.0074 (14) | 0.0055 (17) |
| C2 | 0.0829 (18) | 0.083 (3) | 0.110 (3) | −0.0068 (17) | 0.0039 (18) | 0.022 (2) |
| C3 | 0.0882 (19) | 0.115 (3) | 0.073 (2) | −0.023 (2) | 0.0043 (16) | 0.015 (2) |
| C4 | 0.0708 (16) | 0.082 (2) | 0.069 (2) | −0.0124 (15) | 0.0029 (15) | −0.0037 (17) |
| C5 | 0.0664 (16) | 0.075 (2) | 0.0600 (18) | 0.0006 (15) | 0.0063 (13) | −0.0042 (16) |
| C6 | 0.0647 (15) | 0.0553 (19) | 0.066 (2) | 0.0010 (14) | −0.0046 (14) | −0.0092 (16) |
| C7 | 0.104 (2) | 0.062 (2) | 0.073 (2) | 0.0079 (17) | −0.0001 (17) | −0.0130 (17) |
| C8 | 0.119 (2) | 0.049 (2) | 0.091 (3) | 0.0085 (17) | −0.013 (2) | −0.0018 (19) |
| C9 | 0.0852 (18) | 0.059 (2) | 0.075 (2) | −0.0054 (16) | −0.0061 (17) | 0.0007 (18) |
| C10 | 0.118 (2) | 0.064 (2) | 0.078 (2) | 0.0066 (18) | 0.0245 (18) | 0.0028 (18) |
| C11 | 0.112 (2) | 0.053 (2) | 0.081 (2) | 0.0108 (16) | 0.0230 (18) | −0.0010 (18) |
| C12 | 0.125 (3) | 0.068 (2) | 0.089 (3) | −0.0177 (19) | −0.004 (2) | 0.007 (2) |
| O1—C2 | 1.423 (4) | C9—C12 | 1.431 (5) |
| O1—C3 | 1.413 (4) | C10—C11 | 1.370 (4) |
| N1—N2 | 1.369 (3) | C1—H1A | 0.9700 |
| N1—C1 | 1.449 (3) | C1—H1B | 0.9700 |
| N1—C4 | 1.455 (3) | C2—H2A | 0.9700 |
| N2—C5 | 1.281 (4) | C2—H2B | 0.9700 |
| N3—C12 | 1.144 (5) | C3—H3A | 0.9700 |
| C1—C2 | 1.505 (4) | C3—H3B | 0.9700 |
| C3—C4 | 1.507 (4) | C4—H4A | 0.9700 |
| C5—C6 | 1.458 (4) | C4—H4B | 0.9700 |
| C6—C7 | 1.387 (3) | C5—H5 | 0.9300 |
| C6—C11 | 1.381 (4) | C7—H7 | 0.9300 |
| C7—C8 | 1.382 (4) | C8—H8 | 0.9300 |
| C8—C9 | 1.373 (5) | C10—H10 | 0.9300 |
| C9—C10 | 1.381 (4) | C11—H11 | 0.9300 |
| C2—O1—C3 | 109.3 (2) | O1—C2—H2A | 109.00 |
| N2—N1—C1 | 110.9 (2) | O1—C2—H2B | 109.00 |
| N2—N1—C4 | 121.2 (2) | C1—C2—H2A | 109.00 |
| C1—N1—C4 | 112.68 (19) | C1—C2—H2B | 109.00 |
| N1—N2—C5 | 120.6 (2) | H2A—C2—H2B | 108.00 |
| N1—C1—C2 | 109.8 (2) | O1—C3—H3A | 109.00 |
| O1—C2—C1 | 111.6 (3) | O1—C3—H3B | 109.00 |
| O1—C3—C4 | 112.7 (2) | C4—C3—H3A | 109.00 |
| N1—C4—C3 | 109.1 (2) | C4—C3—H3B | 109.00 |
| N2—C5—C6 | 119.4 (2) | H3A—C3—H3B | 108.00 |
| C5—C6—C7 | 119.9 (3) | N1—C4—H4A | 110.00 |
| C5—C6—C11 | 122.7 (2) | N1—C4—H4B | 110.00 |
| C7—C6—C11 | 117.4 (2) | C3—C4—H4A | 110.00 |
| C6—C7—C8 | 121.3 (3) | C3—C4—H4B | 110.00 |
| C7—C8—C9 | 120.0 (3) | H4A—C4—H4B | 108.00 |
| C8—C9—C10 | 119.5 (3) | N2—C5—H5 | 120.00 |
| C8—C9—C12 | 120.9 (3) | C6—C5—H5 | 120.00 |
| C10—C9—C12 | 119.6 (3) | C6—C7—H7 | 119.00 |
| C9—C10—C11 | 119.9 (3) | C8—C7—H7 | 119.00 |
| C6—C11—C10 | 121.9 (2) | C7—C8—H8 | 120.00 |
| N3—C12—C9 | 178.8 (4) | C9—C8—H8 | 120.00 |
| N1—C1—H1A | 110.00 | C9—C10—H10 | 120.00 |
| N1—C1—H1B | 110.00 | C11—C10—H10 | 120.00 |
| C2—C1—H1A | 110.00 | C6—C11—H11 | 119.00 |
| C2—C1—H1B | 110.00 | C10—C11—H11 | 119.00 |
| H1A—C1—H1B | 108.00 | ||
| C2—O1—C3—C4 | 59.5 (3) | N2—C5—C6—C11 | −5.0 (4) |
| C3—O1—C2—C1 | −59.4 (3) | C5—C6—C7—C8 | 178.6 (2) |
| C4—N1—N2—C5 | 14.6 (3) | C11—C6—C7—C8 | −0.9 (4) |
| C1—N1—N2—C5 | 150.2 (2) | C5—C6—C11—C10 | −178.7 (2) |
| N2—N1—C1—C2 | 166.62 (18) | C7—C6—C11—C10 | 0.9 (4) |
| C4—N1—C1—C2 | −53.9 (3) | C6—C7—C8—C9 | 0.4 (4) |
| N2—N1—C4—C3 | −172.2 (2) | C7—C8—C9—C10 | 0.3 (4) |
| C1—N1—C4—C3 | 52.9 (3) | C7—C8—C9—C12 | −179.1 (3) |
| N1—N2—C5—C6 | 173.80 (19) | C8—C9—C10—C11 | −0.4 (4) |
| N1—C1—C2—O1 | 56.8 (3) | C12—C9—C10—C11 | 179.0 (3) |
| O1—C3—C4—N1 | −55.9 (3) | C9—C10—C11—C6 | −0.2 (4) |
| N2—C5—C6—C7 | 175.5 (2) |
Experimental details
| Crystal data | |
| Chemical formula | C12H13N3O |
| Mr | 215.25 |
| Crystal system, space group | Monoclinic, P21/n |
| Temperature (K) | 296 |
| a, b, c (Å) | 4.1054 (3), 12.0509 (8), 22.9972 (19) |
| β (°) | 91.087 (6) |
| V (Å3) | 1137.55 (15) |
| Z | 4 |
| Radiation type | Mo Kα |
| µ (mm−1) | 0.08 |
| Crystal size (mm) | 0.54 × 0.24 × 0.08 |
| Data collection | |
| Diffractometer | Stoe IPDS 2 |
| Absorption correction | Integration (X-RED32; Stoe & Cie, 2002) |
| Tmin, Tmax | 0.971, 0.994 |
| No. of measured, independent and observed [I > 2σ(I)] reflections | 6956, 2394, 878 |
| Rint | 0.229 |
| (sin θ/λ)max (Å−1) | 0.633 |
| Refinement | |
| R[F2 > 2σ(F2)], wR(F2), S | 0.063, 0.094, 0.89 |
| No. of reflections | 2394 |
| No. of parameters | 146 |
| H-atom treatment | H-atom parameters constrained |
| Δρmax, Δρmin (e Å−3) | 0.12, −0.11 |
Computer programs: X-AREA (Stoe & Cie, 2002), X-RED32 (Stoe & Cie, 2002), SHELXS2013 (Sheldrick, 2008), SHELXL2013 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 2012), WinGX (Farrugia, 2012).
Acknowledgements
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). AJ and RH thank the Shiraz University Research Council for financial support.
References
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| CRYSTALLOGRAPHIC COMMUNICATIONS |
Schiff bases, also known as imines or azomethines, are some of the most widely used organic compounds, for example, as pigments and dyes, catalysts, polymer stabilizers, and as intermediates in organic synthesis in particular for the preparation of heterocycles (Dhar & Taploo 1982; Zheng et al., 2009; Guzen et al., 2007). Schiff bases also play an important role in biological systems with several applications, for example, as antifungal, anticancer, antibacterial, antimalarial, antiproliferative, anti-inflammatory and antiviral agents in addition to other biological performances (Asif, 2014; Hisaindee et al., 2013). In view of this interest we synthesized the title compound and report herein on its crystal structure.
In the title molecule, Fig.1, the morpholine ring (N1/O1/C1–C4) adopts a chair conformation [puckering parameters: QT = 0.553 (3) Å, θ = 3.0 (3) ° and φ = 12 (6) °]. The N1–N2═C5–C6 torsion angle is is 173.80 (19) °. Bond lengths and angles are similar to those reported for a related structure (Akkurt et al., 2013).
In the crystal structure, there are no classical hydrogen bonds. The crystal packing is stabilized by van der Waals interactions.