organic compounds
(Z)-1-[(3-Cyanophenyl)iminiomethyl]-2-naphtholate
aCollege of Materials Science and Engineering, Beijing University of Chemical Technology, Beijing 100029, People's Republic of China
*Correspondence e-mail: 2007080083@grad.buct.edu.cn
The title compound, C18H12N2O, crystallizes in a zwitterionic form. The dihedral angle between the planes of the benzene ring and naphthalene ring system is 13.95 (5)°. An intramolecular N—H⋯O interaction results in the formation of a planar six-membered ring, which is oriented at dihedral angles of 13.50 (4) and 4.49 (4)° with respect to the benzene ring and naphthalene ring system, respectively. In the intermolecular C—H⋯O and C—H⋯N interactions link the molecules into a two-dimensional network. π–π contacts between the naphthalene systems [centroid–centroid distance = 3.974 (1) Å] may further stabilize the structure.
Related literature
For the pharmacological activity of Schiff base compounds, see: Dao et al. (2000); Sriram et al. (2006). For the role played by Schiff base compounds in coordination chemistry related to magnetism, see: Chen et al. (2008); Weber et al. (2007). For related structures, see: Elmali et al. (2001); Yüce et al. (2006). For bond-length data, see: Allen et al. (1987).
Experimental
Crystal data
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Refinement
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Data collection: CrystalClear (Rigaku, 2005); cell CrystalClear; data reduction: CrystalClear; 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, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 and PLATON.
Supporting information
10.1107/S1600536809020224/hk2700sup1.cif
contains datablocks I, global. DOI:Structure factors: contains datablock I. DOI: 10.1107/S1600536809020224/hk2700Isup2.hkl
For the preparation of the title compound, 3-aminobenzonitrile (0.59 g, 5 mmol) and 2-hydroxynaphthalene-1-carbaldehyde (0.861 g, 5 mmol) were dissolved in ethanol (25 ml). The resulting mixture was heated to reflux for 6 h, and then cooled to room temperature. The solid product was collected by filtration. Crystals suitable for X-ray analysis were obtained on slow evaporation at room temperature.
H atoms were positioned geometrically, with N-H = 0.86 Å (for NH) and C-H = 0.93 Å for aromatic H and constrained to ride on their parent atoms, with Uiso(H) = 1.2Ueq(C,N).
Data collection: CrystalClear (Rigaku, 2005); cell
CrystalClear (Rigaku, 2005); data reduction: CrystalClear (Rigaku, 2005); 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, 1997) and PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).C18H12N2O | Z = 2 |
Mr = 272.30 | F(000) = 284 |
Triclinic, P1 | Dx = 1.345 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 7.8943 (16) Å | Cell parameters from 4320 reflections |
b = 9.1356 (18) Å | θ = 3.2–27.5° |
c = 9.4933 (19) Å | µ = 0.09 mm−1 |
α = 83.97 (3)° | T = 294 K |
β = 84.41 (3)° | Prism, yellow |
γ = 82.50 (3)° | 0.20 × 0.20 × 0.20 mm |
V = 672.6 (2) Å3 |
Rigaku SCXmini diffractometer | 2628 independent reflections |
Radiation source: fine-focus sealed tube | 1146 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.061 |
Detector resolution: 13.6612 pixels mm-1 | θmax = 26.0°, θmin = 3.2° |
ω scans | h = −9→9 |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | k = −11→11 |
Tmin = 0.976, Tmax = 0.983 | l = −11→11 |
6177 measured reflections |
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)] = 0.067 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.195 | H-atom parameters constrained |
S = 0.94 | w = 1/[σ2(Fo2) + (0.0919P)2] where P = (Fo2 + 2Fc2)/3 |
2628 reflections | (Δ/σ)max = 0.016 |
190 parameters | Δρmax = 0.23 e Å−3 |
0 restraints | Δρmin = −0.24 e Å−3 |
C18H12N2O | γ = 82.50 (3)° |
Mr = 272.30 | V = 672.6 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 7.8943 (16) Å | Mo Kα radiation |
b = 9.1356 (18) Å | µ = 0.09 mm−1 |
c = 9.4933 (19) Å | T = 294 K |
α = 83.97 (3)° | 0.20 × 0.20 × 0.20 mm |
β = 84.41 (3)° |
Rigaku SCXmini diffractometer | 2628 independent reflections |
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005) | 1146 reflections with I > 2σ(I) |
Tmin = 0.976, Tmax = 0.983 | Rint = 0.061 |
6177 measured reflections |
R[F2 > 2σ(F2)] = 0.067 | 0 restraints |
wR(F2) = 0.195 | H-atom parameters constrained |
S = 0.94 | Δρmax = 0.23 e Å−3 |
2628 reflections | Δρmin = −0.24 e Å−3 |
190 parameters |
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. |
x | y | z | Uiso*/Ueq | ||
O1 | 0.9002 (3) | 0.6505 (3) | 0.2062 (2) | 0.0608 (8) | |
N1 | 0.7833 (3) | 0.3998 (3) | 0.2569 (3) | 0.0439 (7) | |
H1A | 0.8270 | 0.4652 | 0.1974 | 0.053* | |
N2 | 0.4237 (5) | −0.1364 (4) | 0.3557 (4) | 0.0852 (12) | |
C1 | 0.7515 (4) | 0.2689 (4) | 0.2031 (3) | 0.0421 (8) | |
C2 | 0.6494 (4) | 0.1697 (3) | 0.2774 (3) | 0.0452 (9) | |
H2A | 0.5984 | 0.1876 | 0.3675 | 0.054* | |
C3 | 0.6234 (4) | 0.0444 (4) | 0.2177 (4) | 0.0482 (9) | |
C4 | 0.6973 (5) | 0.0157 (4) | 0.0832 (4) | 0.0609 (11) | |
H4A | 0.6799 | −0.0695 | 0.0437 | 0.073* | |
C5 | 0.7971 (5) | 0.1160 (4) | 0.0093 (4) | 0.0654 (11) | |
H5A | 0.8467 | 0.0985 | −0.0812 | 0.079* | |
C6 | 0.8240 (4) | 0.2410 (4) | 0.0675 (3) | 0.0514 (10) | |
H6A | 0.8914 | 0.3077 | 0.0160 | 0.062* | |
C7 | 0.5115 (5) | −0.0569 (4) | 0.2954 (4) | 0.0611 (11) | |
C8 | 0.7525 (4) | 0.4310 (3) | 0.3886 (3) | 0.0408 (8) | |
H8A | 0.7016 | 0.3630 | 0.4536 | 0.049* | |
C9 | 0.7916 (4) | 0.5615 (3) | 0.4381 (3) | 0.0405 (8) | |
C10 | 0.8725 (4) | 0.6662 (3) | 0.3400 (4) | 0.0433 (9) | |
C11 | 0.9241 (5) | 0.7903 (4) | 0.3945 (4) | 0.0576 (11) | |
H11A | 0.9789 | 0.8582 | 0.3323 | 0.069* | |
C12 | 0.8969 (5) | 0.8139 (4) | 0.5334 (4) | 0.0577 (10) | |
H12A | 0.9334 | 0.8968 | 0.5645 | 0.069* | |
C13 | 0.8122 (4) | 0.7125 (3) | 0.6335 (4) | 0.0424 (9) | |
C14 | 0.7876 (4) | 0.7374 (4) | 0.7790 (4) | 0.0533 (10) | |
H14A | 0.8261 | 0.8199 | 0.8091 | 0.064* | |
C15 | 0.7077 (4) | 0.6415 (4) | 0.8761 (4) | 0.0554 (10) | |
H15A | 0.6908 | 0.6590 | 0.9715 | 0.067* | |
C16 | 0.6524 (4) | 0.5185 (4) | 0.8304 (4) | 0.0509 (9) | |
H16A | 0.5981 | 0.4529 | 0.8957 | 0.061* | |
C17 | 0.6766 (4) | 0.4920 (4) | 0.6902 (3) | 0.0483 (9) | |
H17A | 0.6374 | 0.4087 | 0.6623 | 0.058* | |
C18 | 0.7585 (4) | 0.5863 (3) | 0.5875 (3) | 0.0367 (8) |
U11 | U22 | U33 | U12 | U13 | U23 | |
O1 | 0.083 (2) | 0.0657 (17) | 0.0347 (15) | −0.0255 (14) | 0.0047 (13) | 0.0010 (12) |
N1 | 0.0520 (19) | 0.0430 (17) | 0.0370 (17) | −0.0146 (13) | 0.0051 (13) | −0.0025 (14) |
N2 | 0.120 (3) | 0.064 (2) | 0.076 (3) | −0.043 (2) | 0.011 (2) | −0.010 (2) |
C1 | 0.043 (2) | 0.044 (2) | 0.040 (2) | −0.0072 (16) | −0.0024 (16) | −0.0059 (17) |
C2 | 0.057 (2) | 0.044 (2) | 0.035 (2) | −0.0102 (18) | 0.0011 (16) | −0.0075 (16) |
C3 | 0.057 (2) | 0.042 (2) | 0.048 (2) | −0.0068 (18) | −0.0062 (18) | −0.0107 (17) |
C4 | 0.079 (3) | 0.055 (2) | 0.051 (3) | −0.008 (2) | −0.004 (2) | −0.018 (2) |
C5 | 0.083 (3) | 0.069 (3) | 0.047 (2) | −0.018 (2) | 0.010 (2) | −0.020 (2) |
C6 | 0.053 (2) | 0.061 (2) | 0.040 (2) | −0.0129 (19) | 0.0046 (17) | −0.0033 (18) |
C7 | 0.080 (3) | 0.051 (2) | 0.054 (3) | −0.014 (2) | −0.001 (2) | −0.011 (2) |
C8 | 0.040 (2) | 0.044 (2) | 0.038 (2) | −0.0066 (16) | 0.0015 (15) | −0.0029 (16) |
C9 | 0.039 (2) | 0.041 (2) | 0.041 (2) | −0.0065 (16) | −0.0007 (15) | 0.0003 (16) |
C10 | 0.052 (2) | 0.0366 (19) | 0.042 (2) | −0.0093 (16) | −0.0054 (17) | −0.0010 (16) |
C11 | 0.070 (3) | 0.047 (2) | 0.058 (3) | −0.0253 (19) | −0.001 (2) | 0.003 (2) |
C12 | 0.068 (3) | 0.050 (2) | 0.060 (3) | −0.022 (2) | −0.003 (2) | −0.007 (2) |
C13 | 0.041 (2) | 0.042 (2) | 0.046 (2) | −0.0029 (16) | −0.0066 (16) | −0.0074 (17) |
C14 | 0.053 (2) | 0.055 (2) | 0.056 (3) | −0.0066 (19) | −0.0103 (19) | −0.020 (2) |
C15 | 0.058 (2) | 0.064 (3) | 0.043 (2) | −0.003 (2) | 0.0004 (18) | −0.009 (2) |
C16 | 0.057 (2) | 0.051 (2) | 0.043 (2) | −0.0085 (18) | 0.0046 (17) | −0.0013 (18) |
C17 | 0.052 (2) | 0.045 (2) | 0.048 (2) | −0.0097 (18) | 0.0029 (17) | −0.0074 (18) |
C18 | 0.0366 (19) | 0.0372 (19) | 0.0377 (19) | −0.0076 (15) | −0.0012 (14) | −0.0074 (15) |
O1—C10 | 1.287 (4) | C9—C10 | 1.431 (4) |
N1—C1 | 1.409 (4) | C9—C18 | 1.453 (4) |
N1—C8 | 1.304 (4) | C11—C10 | 1.416 (4) |
N1—H1A | 0.8600 | C11—C12 | 1.350 (5) |
N2—C7 | 1.142 (4) | C11—H11A | 0.9300 |
C2—C1 | 1.384 (4) | C12—H12A | 0.9300 |
C2—C3 | 1.376 (4) | C13—C12 | 1.435 (4) |
C2—H2A | 0.9300 | C13—C14 | 1.414 (4) |
C4—C3 | 1.387 (5) | C13—C18 | 1.403 (4) |
C4—C5 | 1.377 (5) | C14—H14A | 0.9300 |
C4—H4A | 0.9300 | C15—C14 | 1.370 (4) |
C5—H5A | 0.9300 | C15—C16 | 1.382 (5) |
C6—C1 | 1.392 (4) | C15—H15A | 0.9300 |
C6—C5 | 1.369 (5) | C16—H16A | 0.9300 |
C6—H6A | 0.9300 | C17—C16 | 1.369 (4) |
C7—C3 | 1.458 (5) | C17—C18 | 1.399 (4) |
C8—H8A | 0.9300 | C17—H17A | 0.9300 |
C9—C8 | 1.406 (4) | ||
C1—N1—H1A | 117.0 | O1—C10—C9 | 122.5 (3) |
C8—N1—C1 | 126.0 (3) | O1—C10—C11 | 119.7 (3) |
C8—N1—H1A | 117.0 | C11—C10—C9 | 117.8 (3) |
C2—C1—N1 | 123.1 (3) | C10—C11—H11A | 118.7 |
C2—C1—C6 | 119.0 (3) | C12—C11—C10 | 122.6 (3) |
C6—C1—N1 | 117.9 (3) | C12—C11—H11A | 118.7 |
C1—C2—H2A | 120.1 | C11—C12—C13 | 120.8 (3) |
C3—C2—C1 | 119.8 (3) | C11—C12—H12A | 119.6 |
C3—C2—H2A | 120.1 | C13—C12—H12A | 119.6 |
C2—C3—C4 | 121.1 (3) | C14—C13—C12 | 120.0 (3) |
C2—C3—C7 | 119.2 (3) | C18—C13—C12 | 119.9 (3) |
C4—C3—C7 | 119.6 (3) | C18—C13—C14 | 120.0 (3) |
C3—C4—H4A | 120.7 | C13—C14—H14A | 119.6 |
C5—C4—C3 | 118.6 (4) | C15—C14—C13 | 120.8 (3) |
C5—C4—H4A | 120.7 | C15—C14—H14A | 119.6 |
C4—C5—H5A | 119.6 | C14—C15—C16 | 119.1 (3) |
C6—C5—C4 | 120.9 (4) | C14—C15—H15A | 120.5 |
C6—C5—H5A | 119.6 | C16—C15—H15A | 120.5 |
C1—C6—H6A | 119.7 | C15—C16—H16A | 119.6 |
C5—C6—C1 | 120.5 (3) | C17—C16—C15 | 120.8 (3) |
C5—C6—H6A | 119.7 | C17—C16—H16A | 119.6 |
N2—C7—C3 | 179.7 (4) | C16—C17—C18 | 122.1 (3) |
N1—C8—C9 | 123.9 (3) | C16—C17—H17A | 119.0 |
N1—C8—H8A | 118.0 | C18—C17—H17A | 119.0 |
C9—C8—H8A | 118.0 | C13—C18—C9 | 118.5 (3) |
C8—C9—C10 | 118.8 (3) | C17—C18—C13 | 117.1 (3) |
C8—C9—C18 | 120.7 (3) | C17—C18—C9 | 124.4 (3) |
C10—C9—C18 | 120.4 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.86 | 1.87 | 2.562 (3) | 136 |
C2—H2A···N2i | 0.93 | 2.61 | 3.463 (3) | 152 |
C6—H6A···O1ii | 0.93 | 2.57 | 3.376 (3) | 145 |
C17—H17A···N2i | 0.93 | 2.62 | 3.522 (3) | 163 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z. |
Experimental details
Crystal data | |
Chemical formula | C18H12N2O |
Mr | 272.30 |
Crystal system, space group | Triclinic, P1 |
Temperature (K) | 294 |
a, b, c (Å) | 7.8943 (16), 9.1356 (18), 9.4933 (19) |
α, β, γ (°) | 83.97 (3), 84.41 (3), 82.50 (3) |
V (Å3) | 672.6 (2) |
Z | 2 |
Radiation type | Mo Kα |
µ (mm−1) | 0.09 |
Crystal size (mm) | 0.20 × 0.20 × 0.20 |
Data collection | |
Diffractometer | Rigaku SCXmini diffractometer |
Absorption correction | Multi-scan (CrystalClear; Rigaku, 2005) |
Tmin, Tmax | 0.976, 0.983 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 6177, 2628, 1146 |
Rint | 0.061 |
(sin θ/λ)max (Å−1) | 0.617 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.067, 0.195, 0.94 |
No. of reflections | 2628 |
No. of parameters | 190 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.23, −0.24 |
Computer programs: CrystalClear (Rigaku, 2005), SHELXS97 (Sheldrick, 2008), ORTEP-3 for Windows (Farrugia, 1997) and PLATON (Spek, 2009), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
D—H···A | D—H | H···A | D···A | D—H···A |
N1—H1A···O1 | 0.86 | 1.87 | 2.562 (3) | 136 |
C2—H2A···N2i | 0.93 | 2.61 | 3.463 (3) | 152 |
C6—H6A···O1ii | 0.93 | 2.57 | 3.376 (3) | 145 |
C17—H17A···N2i | 0.93 | 2.62 | 3.522 (3) | 163 |
Symmetry codes: (i) −x+1, −y, −z+1; (ii) −x+2, −y+1, −z. |
References
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This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.
Schiff base compounds have received considerable attention for many years, primarily due to various pharmacological activities, such as anticancer (Dao et al., 2000) and anti-HIV (Sriram et al., 2006) activities. In addition, Schiff base compounds play important roles in coordination chemistry related to magnetism (Weber et al., 2007) and catalysis (Chen et al., 2008). Generally, Schiff base compounds exhibit the phenol-imine and keto-amine forms. Another form of the Schiff base compounds is their zwitterionic form, and this form have been reported in the literature (Elmali, et al., 2001). We report herein the crystal structure of the title compound.
The molecule of the title compound (Fig 1) is in a zwitterionic form. The bond lengths (Allen et al., 1987) and angles are within normal ranges, and C8=N1 [1.304 (4) Å] and C10-O1 [1.287 (4) Å] bonds may be compared with the corresponding values [1.2954 (19) and 1.2946 (17) Å] in a similar zwitterionic structure (Yüce et al., 2006). Phenyl and naphthalyl rings, A (C1-C6) and B (C9-C18), are, of course, planar and the dihedral angle between them is 13.95 (5)°. Intramolecular N-H···O interaction (Table 1) results in the formation of a planar six-membered ring C (O1/N1/C8-C10/H1A), which is oriented with respect to rings A and B at dihedral angles of 13.50 (4) and 4.49 (4) °, respectively.
In the crystal structure, intramolecular N-H···O and intermolecular C-H···O and C-H···N interactions (Table 1) link the molecules into a two-dimensional network (Fig. 2), in which they may be effective in the stabilization of the structure. The π–π contact between the naphthalyl rings, Cg2—Cg2i [symmetry code: (i) -x, 1 - y, 1 - z, where Cg2 is centroid of the ring (C9-C13/C18)] may further stabilize the structure, with centroid-centroid distance of 3.974 (1) Å.