supplementary materials


zj2100 scheme

Acta Cryst. (2013). E69, o310    [ doi:10.1107/S1600536813002377 ]

A second monoclinic polymorph of (E)-phenyl(pyridin-2-yl)methanone oxime

M. I. Rodríguez-Mora, R. Reyes-Martínez, M. Flores-Alamo, J. J. García and D. Morales-Morales

Abstract top

The title compound, C12H10N2O, a second monoclinic polymorph of (E)-phenyl(pyridin-2-yl)methanone oxime crystallizes in the space group P21/n (Z = 4). The previously reported polymorph [Taga et al. (1990). Acta Cryst. C46, 2241-2243] occurs in the space group C2/c (Z = 8). In the crystal, pairs of bifurcated O-H...(N,O) hydrogen bonds link the molecules into inversion dimers. The dimers are linked by C-H...[pi] interactions, forming a linear arrangement. The dihedral angle between the pyridine and phenyl rings is 67.70 (8)°.

Comment top

Oximes have been widely studied due to their biological and chemical properties, revealing, for instance, good activities as inhibitors of arginase (Custot et al., 1996). Oximes are also preferred intermediates in the synthesis of compounds with biological activity (Turner et al., 2011), for example, derivatives of Pyridine Oximes have been studied as antidotes against organophosphorus compounds poisoning, cytotoxic and antiviral agents,analgesic,antidepressants and tranquillizers (Abele et al., 2003). Additionally, pyridil oximes are used in the preparation of complexes with a variety of transition metals, binding to metals in different forms most commonly as chelates or serving as bridge to metals, and the resulting species have been employed in supramolecular and materials chemistry (Shokrollahi et al., 2008; Martinez et al., 2008). Herein we report a second polymorph of (E)-Phenyl 2-Pyridyl Ketone Oxime (I) (figure 1).

In comparison, compound II described previously (Taga et al., 1990), crystallized in a monoclinic (C2/c), while the title compound I crystallized in a space group P21/n. In compound I the dihedral angle between the pyridine and phenyl rings is 67.70° (8), the orientation of the pyridine ring with a N(2)—C(7)—C(8)—N(1) angle of -174.04° is different from that of the polymorph previously reported of 37.5 (2)° (Taga et al., 1990). The bonds distances C(7)—N(2) and N(2)—O(1) of the oxime group are close to those informed for their polymorph 1.283 (2) and 1.3391 (16) Å, respectively. In compound II was reported a bifurcated hydrogen bond between the OH group with the pyridine N atom and the oxime N atom. While in compound I the OH group forms a bifurcated hydrogen bond [O(1)—H(one-dimensional)···N(2) and O(1)—H(one-dimensional)···O(1)] with the oxime N atom and the hydroxyl O atom of the neighbouring oxime affording a centrosymmetric dimmer, these dimmers are kept together by C—H···π interactions (Figure 2).

Related literature top

For properties of oximes, see: Custot et al. (1996); Turner & Ciufolini (2011); Abele et al. (2003). For the use of complexes of pyridyl oximes with a variety of transition metals in supramolecular and materials chemistry, see: Shokrollahi et al. (2008); Martinez et al. (2008). For the previously reported polymorph, see: Taga et al. (1990).

Experimental top

The suitable crystal for X-ray study was obtained by slow evaporation of a solution of commercial (E)-Phenyl 2-Pyridyl Ketone Oxime in CH2Cl2.

Refinement top

H atoms attached to C atoms were placed in geometrically idealized positions, and refined as riding on their parent atoms, with C—H distances fixed to 0.95 (aromatic CH) with Uiso = 1.2 Ueq(C). The hydroxyl H atom was located in a difference map and was refined with free coordinates and Uiso(H) = 1.2 Ueq(O).

Computing details top

Data collection: CrysAlis PRO (Agilent, 2011); cell refinement: CrysAlis PRO (Agilent, 2011); data reduction: CrysAlis PRO (Agilent, 2011); 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) and DIAMOND (Brandenburg, 2006); software used to prepare material for publication: PLATON (Spek, 2009).

Figures top
[Figure 1] Fig. 1. The molecular structure of the title compound with displacement ellipsoids at the 50% probability.
[Figure 2] Fig. 2. Intramolecular hydrogen-bonding interactions in the title compound, with hydrogen bonds shown as dashed lines.
(E)-Phenyl(pyridin-2-yl)methanone oxime top
Crystal data top
C12H10N2OF(000) = 416
Mr = 198.22Dx = 1.351 Mg m3
Monoclinic, P21/nMo Kα radiation, λ = 0.71073 Å
a = 5.6732 (4) ÅCell parameters from 1437 reflections
b = 23.257 (2) Åθ = 3.5–26.0°
c = 7.4516 (5) ŵ = 0.09 mm1
β = 97.743 (7)°T = 130 K
V = 974.21 (13) Å3Lamina, pale pink
Z = 40.55 × 0.31 × 0.06 mm
Data collection top
Agilent Xcalibur (Atlas, Gemini)
diffractometer
1918 independent reflections
Graphite monochromator1559 reflections with I > 2σ(I)
Detector resolution: 10.4685 pixels mm-1Rint = 0.023
ω scansθmax = 26.1°, θmin = 3.5°
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2011), based on expressions derived by Clark & Reid (1995)]
h = 76
Tmin = 0.976, Tmax = 0.995k = 2825
4256 measured reflectionsl = 96
Refinement top
Refinement on F2Primary atom site location: structure-invariant direct methods
Least-squares matrix: fullSecondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.042Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107H atoms treated by a mixture of independent and constrained refinement
S = 1.04 w = 1/[σ2(Fo2) + (0.0445P)2 + 0.3722P]
where P = (Fo2 + 2Fc2)/3
1918 reflections(Δ/σ)max < 0.001
139 parametersΔρmax = 0.21 e Å3
1 restraintΔρmin = 0.22 e Å3
Crystal data top
C12H10N2OV = 974.21 (13) Å3
Mr = 198.22Z = 4
Monoclinic, P21/nMo Kα radiation
a = 5.6732 (4) ŵ = 0.09 mm1
b = 23.257 (2) ÅT = 130 K
c = 7.4516 (5) Å0.55 × 0.31 × 0.06 mm
β = 97.743 (7)°
Data collection top
Agilent Xcalibur (Atlas, Gemini)
diffractometer
1918 independent reflections
Absorption correction: analytical
[CrysAlis PRO (Agilent, 2011), based on expressions derived by Clark & Reid (1995)]
1559 reflections with I > 2σ(I)
Tmin = 0.976, Tmax = 0.995Rint = 0.023
4256 measured reflectionsθmax = 26.1°
Refinement top
R[F2 > 2σ(F2)] = 0.042H atoms treated by a mixture of independent and constrained refinement
wR(F2) = 0.107Δρmax = 0.21 e Å3
S = 1.04Δρmin = 0.22 e Å3
1918 reflectionsAbsolute structure: ?
139 parametersFlack parameter: ?
1 restraintRogers parameter: ?
Special details top

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'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 > 2σ(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
xyzUiso*/Ueq
O10.01894 (19)0.05043 (5)0.85027 (15)0.0286 (3)
N10.6746 (2)0.13409 (6)1.14331 (18)0.0290 (3)
N20.1685 (2)0.04881 (5)0.99337 (16)0.0233 (3)
C10.2991 (2)0.13583 (6)0.84972 (19)0.0198 (3)
C20.1085 (3)0.17379 (7)0.8370 (2)0.0243 (4)
H20.00750.17010.9170.029*
C30.0870 (3)0.21697 (7)0.7082 (2)0.0261 (4)
H30.04190.24330.70160.031*
C40.2528 (3)0.22192 (7)0.5889 (2)0.0263 (4)
H40.23690.25130.49960.032*
C50.4416 (3)0.18395 (7)0.6003 (2)0.0279 (4)
H50.55460.18710.51760.034*
C60.4672 (3)0.14138 (7)0.7312 (2)0.0249 (4)
H60.59940.1160.740.03*
C70.3204 (2)0.08948 (6)0.98862 (19)0.0201 (3)
C80.5261 (3)0.08876 (7)1.13697 (19)0.0219 (3)
C90.5601 (3)0.04407 (7)1.2600 (2)0.0308 (4)
H90.45480.01211.25170.037*
C100.7525 (3)0.04717 (8)1.3962 (2)0.0382 (5)
H100.77860.01731.48350.046*
C110.9048 (3)0.09311 (8)1.4052 (2)0.0346 (4)
H111.03690.09581.49780.042*
C120.8605 (3)0.13487 (8)1.2768 (2)0.0335 (4)
H120.96710.16651.28160.04*
H1D0.097 (3)0.0196 (8)0.878 (3)0.05*
Atomic displacement parameters (Å2) top
U11U22U33U12U13U23
O10.0289 (6)0.0258 (6)0.0284 (6)0.0061 (5)0.0054 (5)0.0065 (5)
N10.0306 (7)0.0282 (8)0.0266 (7)0.0043 (6)0.0018 (6)0.0015 (6)
N20.0250 (7)0.0224 (7)0.0215 (6)0.0002 (5)0.0007 (5)0.0012 (5)
C10.0225 (7)0.0183 (8)0.0179 (7)0.0019 (6)0.0000 (6)0.0007 (6)
C20.0257 (8)0.0235 (8)0.0250 (8)0.0008 (6)0.0081 (6)0.0014 (6)
C30.0271 (8)0.0197 (8)0.0312 (9)0.0029 (6)0.0033 (6)0.0017 (7)
C40.0302 (8)0.0242 (8)0.0236 (8)0.0054 (7)0.0004 (6)0.0055 (6)
C50.0256 (8)0.0350 (10)0.0242 (8)0.0023 (7)0.0069 (6)0.0041 (7)
C60.0201 (7)0.0286 (9)0.0259 (8)0.0023 (7)0.0027 (6)0.0020 (7)
C70.0233 (7)0.0184 (7)0.0193 (7)0.0030 (6)0.0050 (6)0.0007 (6)
C80.0243 (8)0.0227 (8)0.0192 (7)0.0038 (6)0.0049 (6)0.0009 (6)
C90.0350 (9)0.0263 (9)0.0316 (9)0.0033 (7)0.0062 (7)0.0077 (7)
C100.0451 (10)0.0414 (11)0.0279 (9)0.0161 (9)0.0049 (8)0.0138 (8)
C110.0298 (9)0.0475 (11)0.0246 (8)0.0082 (8)0.0029 (7)0.0042 (8)
C120.0301 (9)0.0377 (10)0.0308 (9)0.0060 (8)0.0026 (7)0.0063 (8)
Geometric parameters (Å, º) top
O1—N21.4015 (15)C4—H40.95
O1—H1D0.882 (15)C5—C61.384 (2)
N1—C81.346 (2)C5—H50.95
N1—C121.349 (2)C6—H60.95
N2—C71.2832 (19)C7—C81.495 (2)
C1—C21.389 (2)C8—C91.382 (2)
C1—C61.391 (2)C9—C101.388 (2)
C1—C71.488 (2)C9—H90.95
C2—C31.383 (2)C10—C111.370 (3)
C2—H20.95C10—H100.95
C3—C41.382 (2)C11—C121.363 (3)
C3—H30.95C11—H110.95
C4—C51.382 (2)C12—H120.95
N2—O1—H1D98.8 (13)C1—C6—H6120.1
C8—N1—C12117.37 (14)N2—C7—C1124.14 (13)
C7—N2—O1113.76 (12)N2—C7—C8115.55 (13)
C2—C1—C6119.46 (14)C1—C7—C8120.29 (13)
C2—C1—C7119.83 (13)N1—C8—C9122.33 (14)
C6—C1—C7120.71 (13)N1—C8—C7116.07 (13)
C3—C2—C1120.25 (14)C9—C8—C7121.60 (14)
C3—C2—H2119.9C8—C9—C10118.12 (16)
C1—C2—H2119.9C8—C9—H9120.9
C4—C3—C2120.15 (14)C10—C9—H9120.9
C4—C3—H3119.9C11—C10—C9120.34 (16)
C2—C3—H3119.9C11—C10—H10119.8
C5—C4—C3119.75 (15)C9—C10—H10119.8
C5—C4—H4120.1C12—C11—C10117.75 (15)
C3—C4—H4120.1C12—C11—H11121.1
C4—C5—C6120.48 (15)C10—C11—H11121.1
C4—C5—H5119.8N1—C12—C11124.08 (16)
C6—C5—H5119.8N1—C12—H12118
C5—C6—C1119.89 (14)C11—C12—H12118
C5—C6—H6120.1
C6—C1—C2—C30.4 (2)C6—C1—C7—C864.41 (19)
C7—C1—C2—C3179.93 (13)C12—N1—C8—C90.5 (2)
C1—C2—C3—C41.3 (2)C12—N1—C8—C7179.37 (14)
C2—C3—C4—C50.7 (2)N2—C7—C8—N1174.03 (13)
C3—C4—C5—C60.6 (2)C1—C7—C8—N14.9 (2)
C4—C5—C6—C11.5 (2)N2—C7—C8—C95.8 (2)
C2—C1—C6—C50.9 (2)C1—C7—C8—C9175.19 (14)
C7—C1—C6—C5178.56 (14)N1—C8—C9—C101.2 (2)
O1—N2—C7—C12.2 (2)C7—C8—C9—C10178.63 (15)
O1—N2—C7—C8178.89 (12)C8—C9—C10—C110.9 (3)
C2—C1—C7—N262.8 (2)C9—C10—C11—C120.1 (3)
C6—C1—C7—N2116.71 (17)C8—N1—C12—C110.6 (3)
C2—C1—C7—C8116.09 (16)C10—C11—C12—N10.9 (3)
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
O1—H1D···N2i0.88 (2)1.93 (2)2.7696 (17)159 (2)
O1—H1D···O1i0.88 (2)2.61 (2)3.225 (2)127 (2)
C11—H11···Cgii0.952.783.5453 (18)139
Symmetry codes: (i) x, y, z+2; (ii) x+1, y, z+1.
Hydrogen-bond geometry (Å, º) top
Cg is the centroid of the C1–C6 ring.
D—H···AD—HH···AD···AD—H···A
O1—H1D···N2i0.882 (15)1.928 (17)2.7696 (17)159.0 (19)
O1—H1D···O1i0.882 (15)2.612 (19)3.225 (2)127.4 (16)
C11—H11···Cgii0.952.783.5453 (18)139
Symmetry codes: (i) x, y, z+2; (ii) x+1, y, z+1.
Acknowledgements top

RRM (postdoctoral agreement No. 290586 UNAM) would like to thank CONACYT for scholarships. The financial support of this research by CONACYT (CB2010–154732) and DGAPA-UNAM (IN201711) is gratefully acknowledged.

references
References top

Abele, E., Abele, R. & Lukevics, E. (2003). Chem. Heterocycl. Compd, 7, 825–865.

Agilent (2011). CrysAlis PRO. Agilent Technologies UK Ltd, Yarnton, England.

Brandenburg, K. (2006). DIAMOND. Crystal Impact GbR, Bonn, Germany.

Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887–897.

Custot, J., Boucher, J.-L., Vadon, S., Guedes, C., Dijols, S., Delaforge, M. & Mansuy, D. (1996). J. Biol. Inorg. Chem. 1, 73–82.

Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854.

Martinez, J., Aiello, I., Bellusci, A., Crispini, A. & Ghedini, M. (2008). Inorg. Chim. Acta, 361, 2677–2682.

Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122.

Shokrollahi, A., Ghaedi, M., Rajabi, H. R. & Niband, M. S. (2008). Spectrochim. Acta Part A, 71, 655–662.

Spek, A. L. (2009). Acta Cryst. D65, 148–155.

Taga, T., Uchiyama, A., Machida, K. & Miyasaka, T. (1990). Acta Cryst. C46, 2241–2243.

Turner, C. D. & Ciufolini, M. A. (2011). Arkivoc, i, 410–428.