C22H8N6O6, monoclinic, P21/n (no. 14), a = 15.3939(6) Å, b = 7.3053(3) Å, c = 16.8282(6) Å, β = 91.567(3)°, V = 1891.74(13) Å3, Z = 4, Rgt(F) = 0.0510, wRref(F2) = 0.0867, T = 140(2) K

Aljuhani, Ateyatallah

Cammidge, Andrew N.

Hughes, David L.

Said, Musa A.

Abstract
 C22H8N6O6, monoclinic, P21/n (no. 14), a = 15.3939(6) Å, b = 7.3053(3) Å, c = 16.8282(6) Å, β = 91.567(3)°, V = 1891.74(13) Å3, Z = 4, R
 gt(F) = 0.0510, wR
 ref(F
 2) = 0.0867, T = 140(2) K.</jats:p

Ateyatallah Aljuhani

Musa A. Said

David L. Hughes

Andrew N. Cammidge

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Zeitschrift für Kristallographie - New Crystal Structures

Synthesis and crystal structure of 1,3-bis[(3,4-dicyano)phenoxy]-4,6-dinitro-benzene, C22H8N6O6

Aljuhani Ateyatallah

Said Musa A.

Hughes David L.

Cammidge Andrew N.

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Synthesis and crystal structure of 1,3-bis[(3,4-dicyano)phenoxy]-4,6-dinitro-benzene, C22H8N6O6

University of East Anglia digital repository

Z. Kristallogr. NCS 2018; aopAteyatallah Aljuhani*, Musa A. Said, David L. Hughes and Andrew N. CammidgeSynthesis and crystal structure of 1,3-bis[(3,4-dicyano)phenoxy]-4,6-dinitro-benzene,C22H8N6O6https://doi.org/10.1515/ncrs-2018-0053Received February 1, 2018; accepted April 12, 2018; availableonline June 13, 2018AbstractC22H8N6O6, monoclinic, P21/n (no. 14), a=15.3939(6) Å, b= 7.3053(3) Å, c= 16.8282(6) Å, β= 91.567(3)°,V= 1891.74(13) Å3, Z= 4, Rgt(F)=0.0510, wRref(F2)=0.0867,T= 140(2) K.CCDC no.: 1814684Tables 1 and 2 contain details on crystal structure and mea-surement conditions and a list of the atoms including atomiccoordinates and displacement parameters.Source of material1,5-Difluoro-2,4-dinitrobenzene (0.2 g, 1 mmol), 4-hydroxy-phthalonitrile (0.3 g, 2.1 mmol) and potassium carbonate(0.274 g, 2.0 mmol) were added to acetone (7 mL) and the*Corresponding author: Ateyatallah Aljuhani, ChemistryDepartment, Taibah University, PO Box 30002, Code 14177,Al-Madinah Al-Munawarah, Kingdom of Saudi Arabia,e-mail: assjuhani@taibahu.edu.saMusa A. Said: Chemistry Department, Taibah University, PO Box30002, Code 14177, Al-Madinah Al-Munawarah, Kingdom of SaudiArabiaDavid L. Hughes and Andrew N. Cammidge: School of Chemistry,University of East Anglia, Norwich, NR4 7TJ, United KingdomTable 1: Data collection and handling.Crystal: Plate, pale yellowSize: 0.08×0.03×0.01 mmWavelength: Mo Kα radiation (0.71073 Å)µ: 0.12 mm−1Diffractometer, scan mode: Xcalibur 3/Sapphire3, Thinslice φ and ω-scansθmax, completeness: 25°,>99%N(hkl)measured, N(hkl)unique, Rint: 23318, 3333, 0.085Criterion for Iobs, N(hkl)gt: Iobs > 2 σ(Iobs), 2315N(param)refined: 339Programs: CrysAlisPRO [1], SHELX [2, 3],WinGX and ORTEP [4, 5]mixture was stirred at room temperature for 24 h. The solventwas removed and the residue redissolved in DCM. This waswashed with water and the washings were extracted withDCM three times. The combined organic extracts were driedoverMgSO4 and the solvent removed under reduced pressure.The productwas purified by column chromatography (elutingwith DCM). Recrystallization from acetone gave the title com-pound as a yellow crystalline solid (0.3 g, 66%). Mp. 197 °C;1HNMR (500 MHz, Acetone) δ 9.04 (s, 1H), 8.14 (d, J= 8.8 Hz,2H), 7.96 (d, J= 2.5 Hz, 2H), 7.80 (dd, J= 8.8, 2.5 Hz, 2H), 7.73(s, 1H); 13C NMR (126 MHz, Acetone) δ 160.10, 153.48, 139.12,137.36, 126.49, 124.56, 124.31, 118.82, 117.81, 116.11, 115.74, 112.56;IR (KBr, cm−1): 3047, 2240, 1630, 1536.Experimental detailsThe structure was determined by the intrinsic phasing rou-tines in the SHELXT program [2] and refined by full-matrixleast-squares methods, in SHELXL [3]. Hydrogen atoms wereincluded in idealized positions, but then allowed to refinefreely. The figure was drawn with ORTEP [4, 5].Discussion1,2-Cyano-containing benzene compounds or phthalonitrilesare important precursors for phthalocyanine molecules [6]and have potential uses in composite matrices, adhesives,sensitizers and pigments [7–11]. As part of our ongoing workon the synthesis and study of phthalocyanine dimers, wetargeted the title novel compound as a linker unit.Open Access.© 2018 Ateyatallah Aljuhani et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 License.Brought to you by | University of East AngliaAuthenticatedDownload Date | 7/6/18 4:31 PM2 | Aljuhani et al.: C22H8N6O6Table 2: Fractional atomic coordinates and isotropic or equivalentisotropic displacement parameters (Å2).Atom x y z Uiso*/UeqC1 0.57921(15) 0.8096(3) 0.20185(14) 0.0199(6)C2 0.53242(14) 0.7043(3) 0.14712(13) 0.0193(5)C3 0.53716(15) 0.5142(3) 0.15288(13) 0.0190(6)C4 0.59101(15) 0.4339(3) 0.20993(14) 0.0212(6)C5 0.63902(15) 0.5404(3) 0.26216(13) 0.0189(6)C6 0.63195(14) 0.7311(3) 0.26008(13) 0.0182(5)O2 0.48760(10) 0.7927(2) 0.08682(9) 0.0232(4)C21 0.40277(15) 0.8442(3) 0.09919(14) 0.0196(6)C22 0.36351(16) 0.8123(3) 0.17038(15) 0.0200(6)C23 0.27956(15) 0.8749(3) 0.18027(13) 0.0198(6)C24 0.23554(15) 0.9672(3) 0.11806(14) 0.0202(6)C25 0.27591(17) 0.9935(3) 0.04637(15) 0.0241(6)C26 0.35984(16) 0.9330(3) 0.03719(15) 0.0220(6)C231 0.23842(15) 0.8575(3) 0.25549(14) 0.0227(6)N231 0.20400(14) 0.8493(3) 0.31519(13) 0.0314(5)C241 0.15022(17) 1.0347(3) 0.13437(14) 0.0237(6)N241 0.08405(14) 1.0852(3) 0.15378(13) 0.0352(6)N3 0.48709(13) 0.3912(3) 0.09940(12) 0.0267(5)O31 0.42934(11) 0.4568(2) 0.05668(10) 0.0315(4)O32 0.50654(12) 0.2285(2) 0.10111(10) 0.0379(5)N5 0.70039(13) 0.4432(3) 0.31619(12) 0.0261(5)O51 0.75237(12) 0.5349(2) 0.35598(10) 0.0360(5)O52 0.69727(11) 0.2753(2) 0.31646(10) 0.0344(5)O6 0.67834(10) 0.8492(2) 0.30921(9) 0.0239(4)C61 0.65818(15) 0.8576(3) 0.38875(13) 0.0195(6)C62 0.58248(15) 0.7833(3) 0.41665(14) 0.0196(6)C63 0.56391(14) 0.8028(3) 0.49640(13) 0.0178(5)C64 0.62098(15) 0.8988(3) 0.54776(13) 0.0197(6)C65 0.69742(16) 0.9701(3) 0.51824(15) 0.0224(6)C66 0.71587(16) 0.9497(3) 0.43899(14) 0.0217(6)C631 0.48516(16) 0.7239(3) 0.52597(13) 0.0215(6)N631 0.42304(14) 0.6595(3) 0.54914(12) 0.0308(5)C641 0.59660(16) 0.9205(3) 0.62918(16) 0.0250(6)N641 0.57146(15) 0.9336(3) 0.69278(13) 0.0365(6)H1 0.5752(13) 0.941(3) 0.2002(11) 0.016(6)*H22 0.3917(13) 0.754(3) 0.2123(12) 0.022(6)*H25 0.2473(14) 1.055(3) 0.0023(13) 0.023(6)*H26 0.3892(14) 0.952(3) −0.0117(13) 0.017(6)*H4 0.5943(15) 0.304(3) 0.2118(13) 0.035(7)*H62 0.5419(14) 0.719(3) 0.3833(12) 0.023(6)*H65 0.7371(14) 1.032(3) 0.5518(12) 0.017(6)*H66 0.7688(13) 0.995(2) 0.4190(11) 0.010(6)*The synthesis of the bis-phthalonitrile is a straight-forward procedure which can be achieved by the sub-stitution reaction method, mixing 4-hydroxyphthalonitrilewith 1,5-difluoro-2,4-dinitrobenzene in acetone in the pres-ence of freshly ground potassium carbonate. After workup,purification over silica gel gave the target compound as thesecond fraction. The 1H-NMR spectrum shows singlets atca 9.05 and 7.75 p.p.m. assigned to the two protons of theTable 3: Short intermolecular contacts, ‘weak hydrogen bonds’, inÅngstroms and degrees.D–H· · ·A d(D–H) d(H· · ·A) d(D· · ·A) <(DHA)C(22)–H(22)· · ·N(241)#1 0.92(2) 2.59(2) 3.468(3) 160.1(17)C(26)–H(26)· · ·O(32)#2 0.96(2) 2.59(2) 3.362(3) 137.7(15)C(62)–H(62)· · ·N(241)#1 0.95(2) 2.24(2) 3.147(3) 157.9(17)C(65)–H(65)· · ·N(231)#3 0.94(2) 2.54(2) 3.416(3) 154.8(17)C(25)–H(25)· · ·O(51)#4 0.96(2) 2.55(2) 3.221(3) 126.8(16)Symmetry transformations used to generate equivalent atoms: #1:1/2− x, y− 1/2, 1/2− z; #2: 1− x, 1− y,−z; #3: 1− x, 2− y, 1− z; #4:x− 1/2, 11/2− y, z− 1/2.bridging benzene ring. This easily prepared bis-phthalonitrileis a potential candidate for making a variety of dimers ofphthalocyanines which are unique in their electronic andoptical properties [12].The crystal structure of the title compound shows anapproximately planar central C6H2(NO2)2(O)2 group. The twonitro groups are rotated about the C—N bonds by 10.93(14)and 9.05(14)°. The phthalonitrile groups are turned out ofthe central plane by rotation about the C(2)—O(2) and C(6)—O(6) bonds (by 88.05(14) and 68.16(11)°, respectively) andaligned so that the normals to these C6 rings are approxi-mately perpendicular (85.82(7) and 77.29(7)°, respectively) tothe normal to the central ring plane. The bond lengths andangles are within normal ranges and are comparable to thoseobserved in similar structures [13]. Molecules are connectedthrough ‘weak hydrogen bonds’, the shortest of which is forC(62)—H(62)· · ·N(2411) where the H· · ·N distance is 2.24(4) ÅTable 3. The dicyanophenyl rings form a short-range stackand are close to parallel (the angles between their normalsare zero or 10.53(11)°), but with, in some cases, limited over-lap of the rings; shorter interactions within this stack includeC(24)· · ·C(644) at 3.40 Å.References1. Oxford Diffraction. CrysAlisPRO. Oxford Diffraction Ltd., Yarnton,England (2011).2. Sheldrick, G. M.: SHELXT – Integrated space-group and crystal-structure determination. Acta Crystallogr. A71 (2015) 3–8.3. Sheldrick, G. M.: Crystal structure refinement with SHELXL.Acta Crystallogr. C71 (2015) 3–8.4. Farrugia, L. J.: WinGX and ORTEP for Windows: an update.J. Appl. Crystallogr. 45 (2012) 849–854.5. Johnson, C. K.: ORTEPII. Report ORNL-5138. Oak Ridge NationalLaboratory, TN, USA (1976).6. Cammidge, A. N.; Gopee, H.: Synthesis and properties ofmacrodiscotic triphenylenophthalocyanines. J. PorphyrinsPhthalocyanines 13 (2009) 235–246.7. Shoji, M.; Nishide, H.: Fluorophilic cobalt phthalocyanine-containing Nafion membrane: high oxygen permeability andBrought to you by | University of East AngliaAuthenticatedDownload Date | 7/6/18 4:31 PMAljuhani et al.: C22H8N6O6 | 3proton conductivity in the membrane. Polym. Adv. Technol. 21(2010) 646–650.8. Laskoski, M.; Dominguez, D. D.; Keller, T. M.: Synthesis andproperties of aromatic ether phosphine oxide containingoligomeric phthalonitrile resins with improved oxidativestability. Polymer 48 (2007) 6234–6240.9. Löbbert, G.: Phthalocyanines. In: Ullmann’s Encyclopedia ofIndustrial Chemistry. Wiley-VCH, Weinheim, Germany (2000).10. Oliver, S. W.; Smith, T. D.: Oligomeric cyclization of dinitriles inthe synthesis of phthalocyanines and related compounds: therole of the alkoxide anion. J. Chem. Soc., Perkin Trans. 2 (1987)1579–1582.11. Uchida, H.; Tanaka, H.; Yoshiyama, H.; Reddy, P. Y.;Nakamura, S.; Toru, T.: Novel synthesis of phthalocyaninesfrom phthalonitriles under mild conditions. Synlett. (2002)1649–1652.12. De la Torre, G.; Bottari, G.; Hahn, U.; Torres, T.: Func-tional phthalocyanines: synthesis, nanostructuration, andelectro-optical applications. Struct. Bond. 135 (2010) 1–44.13. Özdemir, L.; Yılmaz, Y.; Sönmez, M.; Akkurt, M.; Tahir, M. N.:Synthesis and crystal structure of a new phthalonitrileand its phthalocyanines bearing diamagnetic metals.Synth. React. Inorganic, Met. Nano-Metal Chem. 46 (2016)110–117.Brought to you by | University of East AngliaAuthenticatedDownload Date | 7/6/18 4:31 PM

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Synthesis and crystal structure of 1,3-bis[(3,4-dicyano)phenoxy]-4,6-dinitro-benzene, C22H8N6O6

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