Al-Dies, Al-Anood M.

Asiri, Abdullah M.

Khan, Salman A.

Tiekink, Edward R. T. *

Sunway Institutional Repository

Z. Kristallogr. NCS 2019; 234(3): 465–467Al-Anood M. Al-Dies*, Abdullah M. Asiri, Salman A. Khan and Edward R.T. TiekinkCrystal structure of 4,4′,5,5′-tetraphenyl-2,2′-di-p-tolyl-2′H-1,2′-biimidazole, C44H34N4https://doi.org/10.1515/ncrs-2018-0473Received November 13, 2018; accepted December 22, 2018;available online February 4, 2019AbstractC44H34N4, monoclinic, P21 (no. 4), a= 10.1233(5) Å,b= 12.1414(7) Å, c= 13.7420(7) Å, β= 98.389(5)°,V = 1670.97(15) Å3, Z= 2, Rgt(F)=0.0452, wRref(F2)=0.1136,T= 293(2) K.CCDC no.: 1846165The molecular structure is shown in the figure. Tables 1 and2 contain details on the crystal and measurement conditions*Corresponding author: Al-Anood M. Al-Dies, ChemistryDepartment, Faculty of Science, King Abdulaziz University, Jeddah21589, Saudia Arabia, e-mail: nood-mansyaa@hotmail.comAbdullah M. Asiri: Chemistry Department, Faculty of Science, KingAbdulaziz University, Jeddah 21589, Saudia Arabia; and Centerof Excellence for Advanced Materials Research (CEAMR), KingAbdulaziz University, Jeddah 21589, Saudia ArabiaSalman A. Khan: Chemistry Department, Faculty of Science, KingAbdulaziz University, Jeddah 21589, Saudia ArabiaEdward R.T. Tiekink: Research Centre for Crystalline Materials,School of Science and Technology, Sunway University, BandarSunway, Selangor Darul Ehsan 47500, MalaysiaTable 1: Data collection and handling.Crystal: Block, pale-yellowSize: 0.34×0.17×0.14 mmWavelength: Mo Kα radiation (0.71073 Å)µ: 0.07 mm−1Diffractometer, scan mode: SuperNova, ω-scansθmax, completeness: 29.1°,>93% (up to 25.2°,>99%)N(hkl)measured, N(hkl)unique, Rint: 29323, 7950, 0.029Criterion for Iobs, N(hkl)gt: Iobs > 2 σ(Iobs), 5874N(param)refined: 435Programs: CrysAlisPRO [1], SHELX [2, 3],ORTEP [4], PLATON [5]and a list of the atoms including atomic coordinates anddisplacement parameters.Source of materialIn the dark, a freshly prepared solution of potassium ferri-cyanide (2.12 g, 6.44 mmol) and potassiumhydroxide (1.08 g,19.33 mmol) in water (200 mL) was added over a periodof 0.5 h to 4,5-diphenyl-2-(p-tolyl)-1H-imidazole ([6]; 0.50 g,1.61 mmol) in benzene (100 mL) in an ice-bath with vigorousstirring. The reaction mixture was stirred overnight at roomtemperature. The organic layer was collected and washedthree times with water, the water phase was extracted withbenzene three times and the extracts combined. The solu-tion was dried over sodium sulfate, evaporated and dried.The radical dimerization reaction of 4,5-diphenyl-2-(p-tolyl)imidazole leads to the title compound. The resulting solidwasrecrystallized frombenzene/ethanol to yield pale-yellow crys-tals. Yield: 88%. M.p. (Stuart Scientific Co. Ltd apparatus):447−478 K. IR (PerkinElmer spectrum 100 FT-IR spectropho-tometer; ν(max), cm−1): 3052, 3028 (aromatic-CH stretch),1602, 1489 (C=C), 2917, 2860 (CH3 stretch), 1443, 1378 (CH3bend).Experimental detailsThe C-bound H atoms were geometrically placed (C—H=0.93−0.96 Å) and refined as riding with U iso(H)= 1.2–1.5Ueq(C). Owing to poor agreement, one reflection, i.e. (012 4), was omitted from the final cycles of refinement. Theabsolute structure was not determined.Open Access.© 2019 Al-Anood M. Al-Dies et al., published by De Gruyter. This work is licensed under the Creative Commons Attribution 4.0Public License.UnauthenticatedDownload Date | 4/9/19 12:01 PM466 | Al-Dies et al.: C44H34N4Table 2: Fractional atomic coordinates and isotropic or equivalentisotropic displacement parameters (Å2).Atom x y z Uiso*/UeqN1 0.7808(2) 0.50587(18) 0.38400(14) 0.0434(5)N2 0.7473(2) 0.35019(19) 0.46181(15) 0.0497(5)N3 0.9634(2) 0.62458(17) 0.36063(15) 0.0444(5)N4 0.7464(2) 0.66410(18) 0.27409(14) 0.0445(5)C1 0.7823(3) 0.4536(2) 0.47324(18) 0.0458(6)C2 0.7240(3) 0.3314(2) 0.36105(19) 0.0482(6)C3 0.7457(3) 0.4261(2) 0.31187(18) 0.0449(6)C4 0.8217(3) 0.5038(2) 0.57186(18) 0.0458(6)C5 0.7271(3) 0.5236(3) 0.6322(2) 0.0609(8)H5 0.6383 0.5053 0.6111 0.073*C6 0.7631(3) 0.5707(3) 0.7241(2) 0.0656(8)H6 0.6977 0.5850 0.7634 0.079*C7 0.8936(3) 0.5966(3) 0.7580(2) 0.0606(8)C8 0.9881(3) 0.5727(3) 0.6988(2) 0.0647(8)H8 1.0774 0.5877 0.7212 0.078*C9 0.9532(3) 0.5270(3) 0.60663(19) 0.0575(7)H9 1.0190 0.5117 0.5678 0.069*C10 0.9313(5) 0.6534(4) 0.8560(2) 0.0917(12)H10A 0.8981 0.6116 0.9066 0.138*H10B 0.8931 0.7259 0.8531 0.138*H10C 1.0268 0.6588 0.8706 0.138*C11 0.6861(3) 0.2188(2) 0.3248(2) 0.0511(6)C12 0.6465(4) 0.1945(3) 0.2266(2) 0.0734(10)H12 0.6400 0.2511 0.1805 0.088*C13 0.6164(4) 0.0883(3) 0.1956(3) 0.0850(11)H13 0.5908 0.0743 0.1290 0.102*C14 0.6237(3) 0.0027(3) 0.2618(3) 0.0745(9)H14 0.6027 −0.0688 0.2408 0.089*C15 0.6624(4) 0.0255(3) 0.3590(3) 0.0742(9)H15 0.6681 −0.0312 0.4049 0.089*C16 0.6932(3) 0.1318(3) 0.3899(2) 0.0650(8)H16 0.7194 0.1451 0.4565 0.078*C17 0.7402(3) 0.4411(2) 0.20454(19) 0.0527(7)C18 0.8513(4) 0.4190(3) 0.1614(3) 0.0826(11)H18 0.9327 0.4042 0.2000 0.099*C19 0.8409(8) 0.4190(5) 0.0605(4) 0.126(2)H19 0.9164 0.4038 0.0316 0.152*C20 0.7253(10) 0.4404(4) 0.0025(3) 0.133(3)H20 0.7209 0.4393 −0.0656 0.159*C21 0.6136(7) 0.4639(4) 0.0446(3) 0.1093(18)H21 0.5331 0.4792 0.0050 0.131*C22 0.6207(4) 0.4650(3) 0.1457(2) 0.0720(10)H22 0.5453 0.4817 0.1742 0.086*C23 0.8199(3) 0.6209(2) 0.36718(17) 0.0423(6)C24 0.9733(2) 0.6730(2) 0.27926(17) 0.0421(5)C25 0.8366(3) 0.7017(2) 0.22627(17) 0.0430(5)C26 0.7823(3) 0.6999(2) 0.44552(17) 0.0454(6)C27 0.6487(3) 0.7102(2) 0.4565(2) 0.0527(6)H27 0.5847 0.6678 0.4180 0.063*C28 0.6102(3) 0.7831(3) 0.5243(2) 0.0637(8)H28 0.5204 0.7883 0.5313 0.076*C29 0.7021(4) 0.8482(3) 0.5817(2) 0.0679(9)C30 0.8348(4) 0.8392(3) 0.5689(2) 0.0675(9)H30 0.8982 0.8830 0.6065 0.081*C31 0.8754(3) 0.7661(3) 0.5010(2) 0.0576(7)Table 2 (continued)Atom x y z Uiso*/UeqH31 0.9650 0.7619 0.4931 0.069*C32 0.6581(6) 0.9274(4) 0.6556(3) 0.1152(17)H32A 0.6105 0.8878 0.7001 0.173*H32B 0.6007 0.9824 0.6217 0.173*H32C 0.7350 0.9622 0.6920 0.173*C33 1.1028(2) 0.6926(2) 0.24390(18) 0.0445(6)C34 1.2098(3) 0.7323(2) 0.3082(2) 0.0543(7)H34 1.1999 0.7489 0.3728 0.065*C35 1.3323(3) 0.7474(3) 0.2760(3) 0.0706(9)H35 1.4042 0.7753 0.3187 0.085*C36 1.3473(3) 0.7211(3) 0.1812(3) 0.0764(10)H36 1.4300 0.7295 0.1604 0.092*C37 1.2411(4) 0.6824(3) 0.1169(2) 0.0731(9)H37 1.2517 0.6653 0.0525 0.088*C38 1.1188(3) 0.6689(3) 0.1478(2) 0.0590(7)H38 1.0465 0.6436 0.1038 0.071*C39 0.8039(3) 0.7665(2) 0.13505(18) 0.0454(6)C40 0.8770(3) 0.8589(3) 0.1182(2) 0.0677(9)H40 0.9506 0.8794 0.1633 0.081*C41 0.8405(4) 0.9208(3) 0.0341(3) 0.0836(11)H41 0.8880 0.9844 0.0243 0.100*C42 0.7370(4) 0.8903(3) −0.0339(3) 0.0823(11)H42 0.7145 0.9317 −0.0908 0.099*C43 0.6659(4) 0.7983(3) −0.0185(2) 0.0811(11)H43 0.5959 0.7760 −0.0658 0.097*C44 0.6972(3) 0.7381(3) 0.0668(2) 0.0630(8)H44 0.6452 0.6776 0.0781 0.076*DiscussionAn accompanying paper [7] describes the first example of astructure related to that of the title compound, featuring twodistinct imidazole residues linked by a C—N bond. Interest inthesematerials relates to thepotentially useful characteristicsexhibited by imidazole- and π-expanded imidazole deriva-tives in that these fluorescent dyes are emission-tuneable[8]. Herein, the crystal and molecular structures of the titlecompound are described, and compared with the literatureprecedent, namely 8,8′-di-p-tolyl-8′H-7,8′-biacenaphtho[1,2-d]imidazole [7].The molecular structure of the title compound displaystwo distinct imidazole residues connected by a N1—C23 bond[1.479(3) Å]. The N1-imidazole ring is planar and exhibitsa r.m.s. deviation for the fitted atoms of 0.012 Å. Basedon the N2—C1 bond [1.308(4) Å] being significantly shorterthan either of the N1—C1 [1.379(3) Å], N1—C3 [1.394(3) Å] andN2—C2 [1.389(3) Å] bonds, and that the C2—C3 bond is rela-tively short [1.368(4) Å], it is concluded the N2—C1 and C2—C3bonds correspond to double bonds. A different situation per-tains in the N3-imidazole ring. While the r.m.s. deviation forplanarity is 0.048 Å, there are significant deviations from theUnauthenticatedDownload Date | 4/9/19 12:01 PMAl-Dies et al.: C44H34N4 | 467least-squares plane, e.g. 0.043(2) Å for the N4 atom. There-fore, the ring is best described as being twisted about theN4—C23 bond. The short N3—C24 [1.280(3) Å] and N4—C25[1.284(3) Å] bonds compared with N3—C23 [1.469(3) Å] andN4—C23 [1.479(3) Å] bonds indicate the former are to be con-sidered as double bonds. Consistent with this observation,the C24—C25 bond length of 1.508(3) Å corresponds to a sin-gle bond. While these results largely match those reported for8,8′-di-p-tolyl-8′H-7,8′-biacenaphtho[1,2-d]imidazole [7], thecorresponding ring did not exhibit a significant twist.In terms of conformation, the dihedral angle between thetwo imidazole rings is 75.45(15)° indicating an almost orthog-onal relationship, mirroring the same observation noted for8,8′-di-p-tolyl-8′H-7,8′-biacenaphtho[1,2-d]imidazole [7]. Thedihedral angles between the N1-ring and the C1-, C2-, and C3-appended rings are 72.36(16), 9.40(17) and 89.15(19)°, respec-tively, with the significant twists clearly related to the stericpressure exerted by the proximity of the substituted N3-imidazole ring. The dihedral angles between the N3-ring andthe C23-, C24-, and C25-appended rings are 71.47(14), 44.01(15)and 42.57(15)°, respectively.As a general observation, 4,4′,5,5′-tetraphenyl-2,2′-di-p-tolyl-2′H-1,2′-biimidazole is less sterically encumbered com-pared to 8,8′-di-p-tolyl-8′H-7,8′-biacenaphtho[1,2-d]imidazole[7]. This is seen by the partipation of the imidazole-N2 atomin an intermolecular interaction whereas no such contactwas noted in the analogous compound [7]. Thus, phenyl-C34—H34· · ·N2(imidazole) contacts [H34· · ·N2i = 2.57 Å,C34· · ·N2i = 3.439(3) Å and angle at H34= 156° for i: 2− x,1/2+ y, 1− z] lead to supramolecular chains with a helicaltopology (21 screw symmetry) along the b-axis. The linkswithin chains are reinforced by phenyl-C—H· · · π(tolyl) andtolyl-C—H· · · π(phenyl) interactions. The chains pack in thecrystal without directional interactions between them.Acknowledgements: The authors are thankful to the KingAbdulaziz City for Science and Technology (KACST) for sup-port (Grant No. 1-17-01-009-0046).References1. Agilent Technologies: CrysAlis PRO. Agilent Technologies, SantaClara, CA, USA (2014).2. Sheldrick, G. M.: A short history of SHELX. Acta Crystallogr. A64(2008) 112–122.3. Sheldrick, G. M.: Crystal structure refinement with SHELXL. ActaCrystallogr. C71 (2015) 3–8.4. Farrugia, L. J.: WinGX and ORTEP for Windows: an update. J. Appl.Cryst. 45 (2012) 849–854.5. Spek, A. L.: Structure validation in chemical crystallography.Acta Crystallogr. D65 (2009) 148–155.6. Khan, S. A.; Asiri, A. M.; Al-Dies, A.-A. M.; Osman, O. I.; Asad,M.; Zayed, M. E.: One-pot synthesis, physicochemical andphotophysical properties of deep blue light-emitting highlyfluorescent pyrene-imidazole dye: a combined experimental andtheoretical study. J. Photochem. Photobiol. A: Chem. 364 (2018)390–399.7. Al-Dies, A. M.; Asiri, A. M.; Khan, S. A., Tiekink, E. R. T.: Crys-tal structure of 8,8′-di-p-tolyl-8′H-7,8′-biacenaphtho[1,2-d]imidazole, C40H26N4 Z. Kristallogr. NCS 234 (2019) 457–459.8. Skonieczny, K.; Ciuciu, A. I.; Nichols, E. M.; Hugues, V.;Blanchard-Desce, M.; Flamigni, L.; Gryko, D. T.: Bright, emissiontunable fluorescent dyes based on imidazole and π-expandedimidazole. J. Mater. Chem. 22 (2012) 20649–20664.UnauthenticatedDownload Date | 4/9/19 12:01 PM

Crystal structure of 4,4′,5,5′-tetraphenyl-2,2′-di-p-tolyl-2′H-1,2′-biimidazole, C44H34N4

http://eprints.sunway.edu.my/1016/1/Tiekink%20Crystal%20Structure%20of%204455%20Z%20Kristallogr%20NCS%20234%202019%20465.pdf

Crystal structure of 4,4′,5,5′-tetraphenyl-2,2′-di-p-tolyl-2′H-1,2′-biimidazole, C44H34N4

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