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Acta Crystallogr Sect E Struct Rep Online. 2010 March 1; 66(Pt 3): o517.
Published online 2010 February 3. doi:  10.1107/S1600536810003521
PMCID: PMC2983496

3-Cyano-N-(2-hydroxy­benz­yl)anilinium chloride

Abstract

In the cation of the title compound, C14H13N2O+·Cl, the two benzene rings are roughly parallel and are twisted slightly from each other by a dihedral angle of only 2.87 (1)°. In the crystal, weak inter­molecular N—H(...)Cl and O—H(...)Cl hydrogen bonds link the cations and anions into chains extended along the b axis.

Related literature

For the crystal structures and properties of related compounds, see: Fu et al. (2007 [triangle], 2008 [triangle], 2009 [triangle]); Fu & Xiong (2008 [triangle]); Zhao et al. (2008 [triangle]); Loeb et al. (2005 [triangle]).

An external file that holds a picture, illustration, etc.
Object name is e-66-0o517-scheme1.jpg

Experimental

Crystal data

  • C14H13N2O+·Cl
  • M r = 260.71
  • Monoclinic, An external file that holds a picture, illustration, etc.
Object name is e-66-0o517-efi1.jpg
  • a = 13.071 (3) Å
  • b = 7.9437 (16) Å
  • c = 13.141 (3) Å
  • β = 90.18 (3)°
  • V = 1364.4 (5) Å3
  • Z = 4
  • Mo Kα radiation
  • μ = 0.27 mm−1
  • T = 298 K
  • 0.4 × 0.35 × 0.2 mm

Data collection

  • Rigaku Mercury2 diffractometer
  • Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 [triangle]) T min = 0.881, T max = 0.940
  • 13632 measured reflections
  • 3116 independent reflections
  • 2264 reflections with I > 2σ(I)
  • R int = 0.048

Refinement

  • R[F 2 > 2σ(F 2)] = 0.050
  • wR(F 2) = 0.127
  • S = 1.05
  • 3116 reflections
  • 163 parameters
  • 3 restraints
  • H-atom parameters constrained
  • Δρmax = 0.31 e Å−3
  • Δρmin = −0.26 e Å−3

Data collection: CrystalClear (Rigaku, 2005 [triangle]); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 [triangle]); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 [triangle]); molecular graphics: SHELXTL (Sheldrick, 2008 [triangle]); software used to prepare material for publication: SHELXTL.

Table 1
Hydrogen-bond geometry (Å, °)

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810003521/dn2531sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810003521/dn2531Isup2.hkl

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Acknowledgments

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

supplementary crystallographic information

Comment

In the last few years, more and more people have focused on the chemistry of nitrile derivatives because of their wide range of applications in industry and coordination chemistry as ligands (Fu et al., 2007; Fu & Xiong 2008). For example, phthalonitriles have been used as starting materials for phthalocyanines, which are important components for dyes, pigments, gas sensors, optical limiters and liquid crystals, and which are also used in medicine, as singlet oxygen photosensitisers for photodynamic therapy. Recently, we have reported a few benzonitrile compounds (Zhao et al., 2008; Fu et al., 2008; Fu et al., 2009). As an extension of our work on the structural characterization, we report here the crystal structure of the title compound, 3-cyano-N-(2-hydroxybenzyl)anilinium chloride.

In the title compound (Fig.1), the amino N atom is protonated. The phenyl rings are roughly parallel and only slightly twisted from each other by a dihedral angle of 2.87 (1) °. A larger twist angle of 20.7 (3)° is observed in the related N-(4-(Trifluoromethyl)benzyl)-4-methoxyanilinium trifluoromethanesulfonate compound (Loeb et al., 2005). The nitrile group bond length of 1.127 (2)Å is within the normal range.

The crystal packing is stabilized by N—H···Cl and O—H···Cl hydrogen bonds to form a one-dimensional chain parallel to the b axis. (Table 1, Fig. 2).

Experimental

The commercial 3-(2-hydroxybenzylamino)benzonitrile (3 mmol, 669 mg) was dissolved in water/HCl (50:1 v/v) solution. The solvent was slowly evaporated in air affording colourless block-shaped crystals of the title compound suitable for X-ray analysis.

While the permittivity measurement shows that there is no phase transition within the temperature range (from 100 K to 400 K), and the permittivity is 9 at 1 MHz at room temperature.

Refinement

All H atoms attached to C atoms were fixed geometrically and treated as riding with C–H = 0.93 Å (aromatic) and C–H = 0.97 Å (methylene) with Uiso(H) = 1.2Ueq(C or N). H atoms attached to O and N atoms located in difference Fourier maps and freely refined. In the last stage of refinement they were treated as riding on the O and N, with Uiso(H) = 1.5Ueq(O and N).

Figures

Fig. 1.
A view of the title compound with the atomic numbering scheme. Displacement ellipsoids were drawn at the 30% probability level.
Fig. 2.
The crystal packing of the title compound, showing the one-dimensional hydrogen-bonded chain. H atoms not involved in hydrogen bonding (dashed line) have been omitted for clarity.

Crystal data

C14H13N2O+·ClF(000) = 544
Mr = 260.71Dx = 1.269 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ynCell parameters from 2264 reflections
a = 13.071 (3) Åθ = 3.0–27.5°
b = 7.9437 (16) ŵ = 0.27 mm1
c = 13.141 (3) ÅT = 298 K
β = 90.18 (3)°Block, colourless
V = 1364.4 (5) Å30.4 × 0.35 × 0.2 mm
Z = 4

Data collection

Rigaku Mercury2 diffractometer3116 independent reflections
Radiation source: fine-focus sealed tube2264 reflections with I > 2σ(I)
graphiteRint = 0.048
Detector resolution: 13.6612 pixels mm-1θmax = 27.5°, θmin = 3.0°
ω scansh = −16→16
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005)k = −10→10
Tmin = 0.881, Tmax = 0.940l = −17→17
13632 measured reflections

Refinement

Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.050Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.127H-atom parameters constrained
S = 1.05w = 1/[σ2(Fo2) + (0.0544P)2 + 0.2789P] where P = (Fo2 + 2Fc2)/3
3116 reflections(Δ/σ)max < 0.001
163 parametersΔρmax = 0.31 e Å3
3 restraintsΔρmin = −0.26 e Å3

Special details

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)

xyzUiso*/Ueq
N10.64724 (11)0.46075 (18)0.35772 (11)0.0389 (4)
H1A0.66230.54790.31660.058*
H1B0.69610.38210.34960.058*
O10.70213 (12)0.84372 (19)0.41720 (13)0.0677 (5)
H10.72410.93980.39900.102*
C120.42880 (16)0.1649 (2)0.33106 (15)0.0474 (5)
C130.52443 (14)0.2279 (2)0.35670 (14)0.0420 (4)
H130.57120.16250.39270.050*
C80.54865 (14)0.3902 (2)0.32752 (14)0.0389 (4)
C110.35950 (16)0.2619 (3)0.27743 (17)0.0559 (5)
H110.29530.21900.26100.067*
C90.48044 (15)0.4880 (2)0.27398 (17)0.0499 (5)
H90.49780.59720.25520.060*
C60.74965 (16)0.5918 (3)0.49665 (15)0.0487 (5)
C10.77360 (16)0.7568 (3)0.47075 (16)0.0494 (5)
C70.64809 (17)0.5202 (3)0.46654 (16)0.0552 (6)
H7A0.59570.60540.47530.066*
H7B0.63180.42650.51090.066*
C20.86690 (18)0.8245 (3)0.50023 (18)0.0611 (6)
H20.88340.93460.48280.073*
C100.38606 (16)0.4227 (3)0.24836 (19)0.0603 (6)
H100.34000.48770.21120.072*
C140.40186 (18)−0.0046 (3)0.36042 (19)0.0601 (6)
C30.93473 (19)0.7289 (4)0.55504 (19)0.0690 (7)
H30.99730.77470.57450.083*
C50.81903 (19)0.4986 (3)0.55185 (17)0.0613 (6)
H50.80320.38820.56930.074*
C40.9113 (2)0.5654 (4)0.58170 (18)0.0702 (7)
H40.95730.50130.61940.084*
N20.3796 (2)−0.1368 (3)0.3823 (2)0.0900 (8)
Cl10.79799 (4)0.17211 (7)0.33575 (4)0.05632 (19)

Atomic displacement parameters (Å2)

U11U22U33U12U13U23
N10.0389 (8)0.0327 (8)0.0452 (9)−0.0017 (6)0.0049 (6)−0.0003 (7)
O10.0616 (10)0.0608 (10)0.0808 (12)−0.0066 (8)−0.0118 (8)0.0039 (8)
C120.0514 (12)0.0390 (10)0.0519 (12)−0.0115 (9)0.0063 (9)−0.0078 (9)
C130.0455 (11)0.0337 (9)0.0469 (11)−0.0002 (8)0.0006 (8)0.0020 (8)
C80.0361 (10)0.0360 (9)0.0447 (10)−0.0011 (8)0.0059 (8)−0.0030 (8)
C110.0419 (11)0.0632 (14)0.0625 (13)−0.0077 (10)−0.0020 (10)−0.0044 (11)
C90.0440 (12)0.0403 (11)0.0654 (13)0.0024 (9)0.0048 (9)0.0091 (9)
C60.0529 (12)0.0520 (12)0.0412 (10)−0.0106 (10)0.0068 (9)−0.0092 (9)
C10.0490 (12)0.0506 (12)0.0487 (11)−0.0075 (10)−0.0008 (9)−0.0096 (10)
C70.0590 (13)0.0570 (13)0.0497 (12)−0.0183 (10)0.0132 (10)−0.0139 (10)
C20.0628 (15)0.0572 (13)0.0634 (14)−0.0205 (11)−0.0077 (11)−0.0055 (11)
C100.0432 (12)0.0614 (14)0.0762 (16)0.0049 (10)−0.0043 (10)0.0102 (12)
C140.0666 (15)0.0466 (13)0.0671 (14)−0.0145 (11)0.0020 (11)−0.0045 (11)
C30.0585 (15)0.0872 (18)0.0613 (14)−0.0176 (13)−0.0128 (11)−0.0104 (13)
C50.0781 (17)0.0551 (13)0.0507 (12)−0.0046 (12)0.0055 (11)0.0002 (10)
C40.0719 (17)0.0850 (18)0.0537 (14)0.0066 (14)−0.0082 (12)0.0000 (13)
N20.111 (2)0.0551 (13)0.1037 (19)−0.0313 (13)0.0078 (15)0.0019 (12)
Cl10.0555 (3)0.0508 (3)0.0628 (3)0.0132 (2)0.0059 (2)−0.0056 (2)

Geometric parameters (Å, °)

N1—C81.459 (2)C6—C51.376 (3)
N1—C71.506 (3)C6—C11.390 (3)
N1—H1A0.9000C6—C71.496 (3)
N1—H1B0.9000C1—C21.387 (3)
O1—C11.356 (3)C7—H7A0.9700
O1—H10.8500C7—H7B0.9700
C12—C111.381 (3)C2—C31.370 (3)
C12—C131.387 (3)C2—H20.9300
C12—C141.445 (3)C10—H100.9300
C13—C81.382 (3)C14—N21.127 (3)
C13—H130.9300C3—C41.380 (4)
C8—C91.375 (3)C3—H30.9300
C11—C101.378 (3)C5—C41.373 (3)
C11—H110.9300C5—H50.9300
C9—C101.379 (3)C4—H40.9300
C9—H90.9300
C8—N1—C7112.49 (14)O1—C1—C2123.5 (2)
C8—N1—H1A109.1O1—C1—C6116.84 (18)
C7—N1—H1A109.1C2—C1—C6119.7 (2)
C8—N1—H1B109.1C6—C7—N1111.97 (16)
C7—N1—H1B109.1C6—C7—H7A109.2
H1A—N1—H1B107.8N1—C7—H7A109.2
C1—O1—H1111.7C6—C7—H7B109.2
C11—C12—C13120.78 (18)N1—C7—H7B109.2
C11—C12—C14119.76 (19)H7A—C7—H7B107.9
C13—C12—C14119.5 (2)C3—C2—C1119.9 (2)
C8—C13—C12118.45 (18)C3—C2—H2120.0
C8—C13—H13120.8C1—C2—H2120.0
C12—C13—H13120.8C11—C10—C9120.5 (2)
C9—C8—C13121.38 (18)C11—C10—H10119.8
C9—C8—N1119.52 (16)C9—C10—H10119.8
C13—C8—N1119.06 (17)N2—C14—C12178.9 (3)
C10—C11—C12119.56 (19)C2—C3—C4120.7 (2)
C10—C11—H11120.2C2—C3—H3119.6
C12—C11—H11120.2C4—C3—H3119.6
C8—C9—C10119.37 (19)C4—C5—C6121.3 (2)
C8—C9—H9120.3C4—C5—H5119.4
C10—C9—H9120.3C6—C5—H5119.4
C5—C6—C1119.2 (2)C5—C4—C3119.1 (2)
C5—C6—C7121.2 (2)C5—C4—H4120.4
C1—C6—C7119.6 (2)C3—C4—H4120.4

Hydrogen-bond geometry (Å, °)

D—H···AD—HH···AD···AD—H···A
N1—H1A···Cl1i0.902.293.1315 (17)155
O1—H1···Cl1ii0.852.243.0870 (18)171
N1—H1B···Cl10.902.143.0376 (16)173

Symmetry codes: (i) −x+3/2, y+1/2, −z+1/2; (ii) x, y+1, z.

Footnotes

Supplementary data and figures for this paper are available from the IUCr electronic archives (Reference: DN2531).

References

  • Fu, D.-W., Ge, J.-Z., Dai, J., Ye, H.-Y. & Qu, Z.-R. (2009). Inorg. Chem. Commun.12, 994–997.
  • Fu, D.-W., Song, Y.-M., Wang, G.-X., Ye, Q., Xiong, R.-G., Akutagawa, T., Nakamura, T., Chan, P. W. H., Huang, S.-P. & -, D. (2007). J. Am. Chem. Soc.129, 5346–5347. [PubMed]
  • Fu, D.-W. & Xiong, R.-G. (2008). Dalton Trans pp. 3946–3948. [PubMed]
  • Fu, D.-W., Zhang, W. & Xiong, R.-G. (2008). Cryst. Growth Des.8, 3461–3464.
  • Loeb, S. J., Tiburcio, J. & Vella, S. J. (2005). Org. Lett.7, 4923–4926 [PubMed]
  • Rigaku (2005). CrystalClear Rigaku Corporation, Tokyo, Japan.
  • Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. [PubMed]
  • Zhao, H., Qu, Z.-R., Ye, H.-Y. & Xiong, R.-G. (2008). Chem. Soc. Rev.37, 84–100. [PubMed]

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