3-Fluoro­salicylaldoxime, C7H6FNO2, unlike many salicylaldoxime derivatives, forms a crystal structure containing hydrogen-bonded chains rather than centrosymmetric hydrogen-bonded ring motifs. Each chain inter­acts with two chains above and two chains below via π–π stacking contacts [shortest centroid–centroid distance = 3.295 (1) Å]. This structure at 6.5 GPa represents the final point in a single-crystal compression study

Forgan, Ross S.

Parsons, Simon

Pidcock, Elna

Tasker, Peter A.

Wood, Peter A.

Acta Crystallographica Section E Structure Reports Online

English

PubMed

3-Fluorosalicylaldoxime, C7H6FNO2, unlike many salicylaldoxime derivatives, forms a crystal structure containing hydrogen-bonded chains rather than centrosymmetric hydrogen-bonded ring motifs. Each chain interacts with two chains above and two chains below via &amp;#960;&amp;#8211;&amp;#960; stacking contacts [shortest centroid&amp;#8211;centroid distance = 3.295&amp;#8197;(1)&amp;#8197;&amp;#197;]. This structure at 6.5&amp;#8197;GPa represents the final point in a single-crystal compression study

Peter A. Wood

Ross S. Forgan

Simon Parsons

Elna Pidcock

Peter A. Tasker

Directory of Open Access Journals

3-Fluorosalicylaldoxime at 6.5 GPa

Edinburgh Research Explorer

     Edinburgh Research Explorer                                      3-Fluorosalicylaldoxime at 6.5 GPaCitation for published version:Wood, PA, Forgan, RS, Parsons, S, Pidcock, E & Tasker, PA 2009, '3-Fluorosalicylaldoxime at 6.5 GPa'Acta Crystallographica Section E: Structure Reports Online, vol. 65, pp. O2001-U4208. DOI:10.1107/S1600536809029043Digital Object Identifier (DOI):10.1107/S1600536809029043Link:Link to publication record in Edinburgh Research ExplorerDocument Version:Publisher's PDF, also known as Version of recordPublished In:Acta Crystallographica Section E: Structure Reports OnlinePublisher Rights Statement:This is an Open Access article distributed under the terms of the Creative Commons Attribution License(http://creativecommons.org/licenses/by/2.0/uk/legalcode), which permits commercial reuse, distribution, andreproduction in any medium, provided the original work is properly cited.General rightsCopyright for the publications made accessible via the Edinburgh Research Explorer is retained by the author(s)and / or other copyright owners and it is a condition of accessing these publications that users recognise andabide by the legal requirements associated with these rights.Take down policyThe University of Edinburgh has made every reasonable effort to ensure that Edinburgh Research Explorercontent complies with UK legislation. If you believe that the public display of this file breaches copyright pleasecontact openaccess@ed.ac.uk providing details, and we will remove access to the work immediately andinvestigate your claim.Download date: 05. Apr. 20193-Fluorosalicylaldoxime at 6.5 GPaPeter A. Wood,a* Ross S. Forgan,b Simon Parsons,b ElnaPidcocka and Peter A. TaskerbaCambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ,England, and bSchool of Chemistry, The University of Edinburgh, King’s Buildings,West Mains Road, Edinburgh EH9 3JJ, ScotlandCorrespondence e-mail: wood@ccdc.cam.ac.ukReceived 21 July 2009; accepted 22 July 2009Key indicators: single-crystal X-ray study; T = 298 K, P = 6500000 kPa; mean (C–C) = 0.009 A˚; R factor = 0.036; wR factor = 0.049; data-to-parameter ratio = 2.9.3-Fluorosalicylaldoxime, C7H6FNO2, unlike many salicylal-doxime derivatives, forms a crystal structure containinghydrogen-bonded chains rather than centrosymmetrichydrogen-bonded ring motifs. Each chain interacts with twochains above and two chains below via – stacking contacts[shortest centroid–centroid distance = 3.295 (1) A˚]. Thisstructure at 6.5 GPa represents the final point in a single-crystal compression study.Related literatureFor salicylaldoximes with bulky side groups which morecommonly form hydrogen-bonded chains, see: Koziol &Kosturkiewicz (1984); Maurin (1994). For salicylaldoximeswithout bulky side groups that form chains, see: Wood et al.(2007a,b); Wood, Forgan, Parsons et al. (2006). For highpressure studies on salicylaldoximes, see: Wood et al. (2008,2009); Wood, Forgan, Henderson et al. (2006). For specializedequipment used in the high pressure study, see: Merrill &Bassett (1974); Piermarini et al. (1975).ExperimentalCrystal dataC7H6FNO2Mr = 155.13Orthorhombic, Pna21a = 6.156 (2) A˚b = 9.751 (3) A˚c = 8.6764 (18) A˚V = 520.8 (3) A˚3Z = 4Mo K radiation = 0.17 mm1T = 298 K0.15  0.12  0.10 mmData collectionBruker APEXII diffractometerAbsorption correction: multi-scan(SADABS; Sheldrick, 2006)Tmin = 0.39, Tmax = 0.982715 measured reflections333 independent reflections233 reflections with I > 2(I)Rint = 0.074RefinementR[F 2 > 2(F 2)] = 0.036wR(F 2) = 0.049S = 0.94305 reflections106 parameters94 restraintsH atoms treated by a mixture ofindependent and constrainedrefinementmax = 0.16 e A˚3min = 0.18 e A˚3Table 1Hydrogen-bond geometry (A˚, ).D—H  A D—H H  A D  A D—H  AO1—H1  O5i 0.89 (7) 1.81 (6) 2.684 (8) 165 (7)O5—H5  N2 0.85 (4) 1.84 (6) 2.530 (7) 137 (6)Symmetry code: (i) x þ 1;y; zþ 12.Data collection: APEX2 (Bruker, 2004); cell refinement: SAINT(Bruker, 2004); data reduction: SAINT; method used to solve struc-ture: model taken from ambient pressure structure (Wood et al.,2007b); program(s) used to refine structure: CRYSTALS (Betteridgeet al., 2003); molecular graphics: Mercury (Macrae et al., 2008); soft-ware used to prepare material for publication: CRYSTALS.We thank the Cambridge Crystallographic Data Centre, theUniversity of Edinburgh and the EPSRC for funding.Supplementary data and figures for this paper are available from theIUCr electronic archives (Reference: TK2511).ReferencesBetteridge, P. W., Carruthers, J. R., Cooper, R. I., Prout, K. & Watkin, D. J.(2003). J. Appl. Cryst. 36, 1487.Bruker (2004). APEX2 and SAINT. Bruker AXS Inc., Madison, Wisconsin,USA.Koziol, A. E. & Kosturkiewicz, Z. (1984). Pol. J. Chem. 58, 569–575.Macrae, C. F., Bruno, I. J., Chisholm, J. A., Edgington, P. R., McCabe, P.,Pidcock, E., Rodriguez-Monge, L., Taylor, R., van de Streek, J. & Wood, P.A. (2008). J. Appl. Cryst. 41, 466–470.Maurin, J. K. (1994). Acta Cryst. C50, 1357–1359.Merrill, L. & Bassett, W. A. (1974). Rev. Sci. Instrum. 45, 290–294.Piermarini, G. J., Block, S., Barnett, J. D. & Forman, R. A. (1975). J. Appl.Phys. 46, 2774–2780.Sheldrick, G. M. (2006). SADABS. University of Go¨ttingen, Germany.Wood, P. A., Forgan, R. S., Henderson, D., Parsons, S., Pidcock, E., Tasker,P. A. & Warren, J. E. (2006). Acta Cryst. B62, 1099–1111.Wood, P. A., Forgan, R. S., Lennie, A. R., Parsons, S., Pidcock, E., Tasker, P. A.& Warren, J. E. (2008). CrystEngComm, 10, 239–251.Wood, P. A., Forgan, R. S., Parsons, S., Pidcock, E. & Tasker, P. A. (2006). ActaCryst. E62, o3944–o3946.Wood, P. A., Forgan, R. S., Parsons, S., Pidcock, E. & Tasker, P. A. (2007a).Acta Cryst. E63, o3132.Wood, P. A., Forgan, R. S., Parsons, S., Pidcock, E. & Tasker, P. A. (2007b).Acta Cryst. E63, o3131.Wood, P. A., Forgan, R. S., Parsons, S., Pidcock, E. & Tasker, P. A. (2009).Private communication to the Cambridge Structural Database (depositionnumbers CCDC 737481–737486). CCDC, Union Road, Cambridge,England.organic compoundsActa Cryst. (2009). E65, o2001 doi:10.1107/S1600536809029043 Wood et al. o2001Acta Crystallographica Section EStructure ReportsOnlineISSN 1600-5368supplementary materialssupplementary materialssup-1Acta Cryst. (2009). E65, o2001    [ doi:10.1107/S1600536809029043 ]3-Fluorosalicylaldoxime at 6.5 GPaP. A. Wood, R. S. Forgan, S. Parsons, E. Pidcock and P. A. TaskerCommentHydrogen-bonded chain formation is more common for salicylaldoximes with bulky side-groups, e.g. Koziol & Kos-turkiewicz (1984) & Maurin (1994). The structure of the title compound, 3-fluorosalicylaldoxime, (I), which has been pre-viously reported at ambient-pressure/150 K (Wood et al., 2007a) is one of the exceptions to this trend along with salicylal-doxime-III (Wood, Forgan, Parsons et al., 2006) and 3-hydroxysalicylaldoxime (Wood et al., 2007b). Salicylaldoxime-I(Wood, Forgan, Henderson et al., 2006) and four of its 3-substituted derivatives (Wood et al., 2008), all of which formhydrogen-bonded dimers, have been studied under compression using a diamond-anvil high-pressure cell. This paper detailsthe results of the continuation of the series to (I). The highest pressure structure is reported here but the ambient-pressure/ambient-temperature structure and further high pressure structures in between have been submitted to the CCDC as a privatecommunication (Wood et al., 2009).Compound (I) crystallizes with one molecule in the asymmetric unit in the space group Pna21 (Fig. 1). The moleculeforms an intramolecular phenolic OH···N hydrogen bond [O5···N2 = 2.530 (7) Å] and an intermolecular oximic OH···Ohydrogen bond [O1···O5 = 2.684 (8) Å] with a neighbouring molecule related by the 21 screw axis. These two interactionstaken together form a secondary level C(5) chain running parallel to the crystallographic c axis.The compression of the 3-fluorosalicylaldoxime structure is anisotropic (Fig. 2). It can be seen that the c-axis is the leastcompressible (decreases by 4.9% up to 6.5 GPa) and this direction also corresponds to the direction of the hydrogen-bondedchains in the crystal structure. The next least compressible direction is that of the crystallographic b axis (decreases by 7.8%),where the main interactions are H···F and H···H contacts between the chains. Finally, the direction that compresses the mostup to 6.5 GPa (14.4%) is along the a axis which corresponds to the π-π stacking direction; closest contact = Cg()···Cg()i= 3.295 (1) Å for i: 0.5+x, 0.5-y, z.Fig. 3 shows the compression of the π-π stacking contact geometry in comparison with equivalent interactions in othersalicylaldoximes and with general stacking contacts found in the CSD. It can be seen that the compression follows the trendof the earlier oxime pressure studies (Wood et al., 2008) in that the interaction compresses to the edge of what is seen atambient conditions in the CSD. In this experiment the crystal disintegrated when the pressure was increased further and thismay be indicative that a destructive phase transition occurred.ExperimentalAll solvents and reagents were used as received from Aldrich and Fisher. 1H and 13C NMR were obtained using a BrukerAC250 spectrometer at ambient temperature. Chemical shifts (δ) are reported in p.p.m. relative to internal standards. Fastatom bombardment mass spectrometry (FABMS) was carried out using a Kratos MS50TC spectrometer with a thioglycerolmatrix. Analytical data was obtained from the University of St Andrews Microanalytical Service.supplementary materialssup-2KOH (0.674 g, 10.20 mmol) and NH2OH.HCl (0.709 g, 10.20 mmol) were dissolved in EtOH, mixed thoroughly anda white KCl precipitate removed by filtration. 3-Fluorosalicylaldehyde (1.000 g, 7.14 mmol) was added to the filtrate, andthe mixture refluxed for 3 h. The solvent was removed in vacuo, the residue redissolved in CHCl3, washed with water threetimes, and dried over MgSO4. The solvent was removed in vacuo to yield the crude product as a white powder (0.980 g,88.5%). A pale-yellow block suitable for X-ray diffraction was grown by slow evaporation of a hexane/chloroform solution.(Anal. Calc. for C7H6FNO2: C, 54.2; H, 3.9; N, 9.0. Found: C, 54.3; H, 3.5; N, 9.2%); 1H NMR (250 MHz, CDCl3): δ(H)(p.p.m.) 6.78 (dt, 1H, ArHb), 6.90 (dd, 1H, ArHa), 7.05 (m, 1H, ArHc), 8.16 (s, 1H, CHN); 13C NMR (63 MHz, CDCl3)δ(C) (p.p.m.) 118.0 (aromatic CH), 118.7 (aromatic C-CHN), 119.8 (aromatic CH), 126.0 (aromatic CH), 145.9 (aromaticC—F), 152.8 (ArCHN), 153.6 (aromatic C—OH); FABMS m/z 156 (MH)+, 70%.The high-pressure experiments were carried out using a Merrill-Bassett diamond anvil cell (half-opening angle 40°),equipped with brilliant-cut diamonds with 600 µm culets and a tungsten gasket (Merrill & Bassett, 1974). A 1:1 mixture ofn-pentane and isopentane was used as a hydrostatic medium. Due to the high volatility of the n-pentane/isopentane solution,the cell was cooled in dry-ice prior to loading. A small ruby chip was also loaded into the cell as the pressure calibrant, withthe ruby fluorescence method being used to measure the pressure (Piermarini et al., 1975).Following data collection, an absorption correction was applied using the program SADABS (Sheldrick, (2006). TheTmax/Tmin ratio is larger than calculated on the basis of the crystal dimensions. However, multi-scan procedures (such asSADABS used in the present study) correct for all systematic errors that lead to disparities in the intensities of equivalentdata. It is likely that the larger than expected range of transmission is accounted for by crystal decay or absorption by thehigh pressure cell.RefinementThe hydrogen atoms were located in a Fourier difference map. The positional and isotropic displacement parameters werethen refined subject to restraints [C—H = 0.93 (2) Å, O—H = 0.82 (2) Å and Uiso(H) = 1.5 Ueq(C or O)]. In subsequentcycles of least-squares refinement all the Uiso(H) values were fixed and the H-atoms attached to C were constrained to rideon their parent atoms. H1 and H5 were refined subject to distance restraints equal to 0.84 (5) Å.In the absence of significant anomalous scattering effects, 316 Friedel pairs were averaged in the final refinement.The crystal quality was beginning to deteriorate by this pressure and the number of reflections collected also dropped.In order to deal with this, global vibration and thermal similarity restraints were applied to the model.FiguresFig. 1. Molecular structure of (I) with probability ellipsoids drawn at the 50% level, showingatom labelling.supplementary materialssup-3Fig. 2. Graph of the fractional variation of the lattice parameters (a, b and c) of (I) as a func-tion of pressure (GPa). The cell lengths are displayed as red squares, green triangles and bluecircles for a, b and c, respectively.Fig. 3. Graph of stacking distance (in Å) against stacking offset (in Å) for phenyl group stack-ing interactions in the CSD. The five previously published salicylaldoxime compression stud-ies have been highlighted; salicylaldoxime (dark-blue), 3-chlorosalicylaldoxime (green), 3-methylsalicylaldoxime (pink), 3-methoxysalicylaldoxime (light-blue) and 3-tert-butylsali-cylaldoxime (orange). Data for the compression study on (I) (red) has now also been added.3-FluorosalicylaldoximeCrystal dataC7H6F1N1O2 Dx = 1.978 Mg m−3Mr = 155.13 Mo Kα radiation, λ = 0.71073 ÅOrthorhombic, Pna21 Cell parameters from 779 reflectionsHall symbol: P 2c -2n θ = 3–24ºa = 6.156 (2) Å µ = 0.17 mm−1b = 9.751 (3) Å T = 298 Kc = 8.6764 (18) Å Cell measurement pressure: 6500000 kPaV = 520.8 (3) Å3 Block, pale-yellowZ = 4 0.15 × 0.12 × 0.10 mmF000 = 320Data collectionBruker APEXIIdiffractometer 333 independent reflectionsMonochromator: graphite 233 reflections with I > 2σ(I)T = 298 K Rint = 0.074P = 6500000 kPa θmax = 27.0ºω scans θmin = 3.1ºAbsorption correction: multi-scan(SADABS; Sheldrick, 2006) h = −6→6Tmin = 0.39, Tmax = 0.98 k = −10→102715 measured reflections l = −10→10RefinementRefinement on F2Hydrogen site location: inferred from neighbouringsitesLeast-squares matrix: full H atoms treated by a mixture ofindependent and constrained refinementR[F2 > 2σ(F2)] = 0.036  Method, part 1, Chebychev polynomial, (Watkin,1994, Prince, 1982) [weight] = 1.0/[A0*T0(x) +A1*T1(x) ··· + An-1]*Tn-1(x)]supplementary materialssup-4where Ai are the Chebychev coefficients listed be-low and x = F /Fmax Method = Robust Weighting(Prince, 1982) W = [weight] * [1-(deltaF/6*sig-maF)2]2 Ai are 12.4 13.8 4.45 -0.254wR(F2) = 0.049 (Δ/σ)max < 0.001S = 0.94 Δρmax = 0.16 e Å−3305 reflections Δρmin = −0.18 e Å−3106 parameters Extinction correction: Larson (1970), Equation 2294 restraints Extinction coefficient: 119.189Primary atom site location: structure-invariant directmethodsFractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)x y z Uiso*/UeqO1 0.4779 (9) 0.1918 (6) 0.9058 (5) 0.0268N2 0.4588 (11) 0.1849 (7) 0.7440 (5) 0.0247C3 0.4049 (11) 0.3001 (7) 0.6852 (7) 0.0191C4 0.3841 (12) 0.3034 (7) 0.5185 (6) 0.0157C5 0.3721 (11) 0.1828 (9) 0.4328 (5) 0.0143O5 0.3858 (9) 0.0571 (5) 0.4956 (5) 0.0214C6 0.3455 (12) 0.1950 (9) 0.2755 (6) 0.0201F6 0.3356 (7) 0.0740 (5) 0.1972 (4) 0.0265C7 0.3246 (12) 0.3167 (8) 0.2001 (7) 0.0185C8 0.3431 (12) 0.4332 (8) 0.2861 (6) 0.0189C9 0.3738 (11) 0.4309 (8) 0.4436 (6) 0.0183H3 0.3781 0.3782 0.7440 0.0230*H7 0.3014 0.3204 0.0958 0.0219*H8 0.3343 0.5184 0.2363 0.0227*H9 0.3877 0.5129 0.4979 0.0218*H5 0.392 (14) 0.059 (7) 0.594 (4) 0.0321*H1 0.546 (15) 0.114 (6) 0.929 (7) 0.0400*Atomic displacement parameters (Å2)U11 U22 U33 U12 U13 U23O1 0.037 (5) 0.032 (5) 0.0119 (13) 0.002 (2) 0.0009 (19) 0.003 (2)N2 0.035 (6) 0.028 (4) 0.0109 (15) −0.001 (3) 0.001 (2) 0.008 (3)C3 0.017 (5) 0.022 (4) 0.0176 (17) 0.000 (3) 0.001 (3) 0.001 (2)C4 0.010 (4) 0.020 (2) 0.0176 (18) 0.001 (2) −0.002 (3) 0.0018 (16)C5 0.004 (4) 0.020 (2) 0.0189 (19) 0.000 (2) 0.000 (3) 0.0014 (16)O5 0.023 (4) 0.022 (2) 0.019 (2) 0.0014 (19) 0.003 (2) 0.0014 (18)C6 0.022 (6) 0.020 (2) 0.019 (2) 0.000 (3) −0.001 (3) −0.0035 (16)F6 0.035 (3) 0.023 (2) 0.0215 (17) 0.0051 (16) 0.001 (2) −0.0071 (18)C7 0.017 (5) 0.024 (3) 0.015 (2) 0.002 (2) 0.002 (3) −0.0008 (18)C8 0.022 (5) 0.017 (3) 0.018 (2) 0.000 (2) 0.001 (3) 0.004 (2)C9 0.022 (5) 0.016 (3) 0.017 (2) 0.005 (2) 0.002 (3) −0.003 (2)supplementary materialssup-5Geometric parameters (Å, °)O1—N2 1.410 (6) O5—H5 0.86 (4)O1—H1 0.89 (4) C6—F6 1.363 (9)N2—C3 1.278 (9) C6—C7 1.361 (9)C3—C4 1.452 (8) C7—C8 1.365 (10)C3—H3 0.932 C7—H7 0.917C4—C5 1.394 (9) C8—C9 1.380 (8)C4—C9 1.404 (10) C8—H8 0.938C5—O5 1.345 (9) C9—H9 0.932C5—C6 1.380 (7)N2—O1—H1 103 (4) C5—C6—F6 115.1 (7)O1—N2—C3 112.2 (7) C5—C6—C7 124.2 (7)N2—C3—C4 116.2 (7) F6—C6—C7 120.8 (5)N2—C3—H3 123.1 C6—C7—C8 117.1 (6)C4—C3—H3 120.8 C6—C7—H7 121.6C3—C4—C5 121.2 (6) C8—C7—H7 121.3C3—C4—C9 119.0 (6) C7—C8—C9 122.6 (8)C5—C4—C9 119.8 (5) C7—C8—H8 118.8C4—C5—O5 123.3 (4) C9—C8—H8 118.6C4—C5—C6 117.5 (7) C4—C9—C8 118.6 (7)O5—C5—C6 119.1 (7) C4—C9—H9 121.4C5—O5—H5 113 (5) C8—C9—H9 119.9Hydrogen-bond geometry (Å, °)D—H···A D—H H···A D···A D—H···AO1—H1···O5i 0.89 (7) 1.81 (6) 2.684 (8) 165 (7)O5—H5···N2 0.85 (4) 1.84 (6) 2.530 (7) 137 (6)Symmetry codes: (i) −x+1, −y, z+1/2.supplementary materialssup-6Fig. 1supplementary materialssup-7Fig. 2supplementary materialssup-8Fig. 3

3-Fluorosalicylaldoxime, C(7)H(6)FNO(2), unlike many salicylaldoxime derivatives, forms a crystal structure containing hydrogen-bonded chains rather than centrosymmetric hydrogen-bonded ring motifs. Each chain interacts with two chains above and two chains below via pi-pi stacking contacts [shortest centroid-centroid distance = 3.295 (1) angstrom]. This structure at 6.5 GPa represents the final point in a single-crystal compression study

Wood, P.A.

Forgan, R.S.

Parsons, S.

Pidcock, E.

Tasker, P.A.

Enlighten

Acta Cryst.

APEX2 and SAINT.

Following data collection, an absorption correction was applied using the program SADABS (Sheldrick,

Private communication to the Cambridge Structural Database (deposition numbers

The high-pressure experiments were carried out using a Merrill-Bassett diamond anvil cell (half-opening angle 40°), equipped with brilliant-cut diamonds with 600 µm culets and a tungsten gasket

http://www.pubmedcentral.nih.gov/articlerender.fcgi?artid=2977167

3-Fluoro­salicylaldoxime at 6.5 GPa

3-Fluorosalicylaldoxime at 6.5 GPa

Abstract

Similar works

Full text

Available Versions

Directory of Open Access Journals

Edinburgh Research Explorer

Enlighten

3-Fluoro­salicylaldoxime at 6.5 GPa

Abstract

Similar works

Full text

Available Versions

Directory of Open Access Journals

Edinburgh Research Explorer

Enlighten

3-Fluorosalicylaldoxime at 6.5 GPa