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Electronic Supplementary Material (ESI) for CrystEngComm.This journal is The Royal Society of Chemistry 2021Electronic Supporting Information (ESI)Conformational Switch In the Crystal States of A Calix[4]areneSaber Mirzaei,† § Sergey V. Lindeman,† Denan Wang, †* M. Saeed Mirzaei,‡ and Qadir K.Timerghazin†*† Departmentof Chemistry, Marquette University, Milwaukee, WI 53201-1414, United States‡ Departmentof Organic Chemistry, Faculty of Chemistry, Razi University, Kermanshah, IranEmail: denan.wang@marquette.edu; qadir.timerghazin@marquette.eduContentsS1. General Methods and Synthesis .2S2. X-Ray Crystallography Data.8S3. PXRD Data .11S4. Computational Data.13S5. References .17S6. Cartesian Coordinates of optimized molecules .181 ESI
S1. General Methods and SynthesisAll reactions were performed under nitrogen atmosphere unless otherwise noted. NMR spectra wererecorded on Varian 400 MHz NMR spectrometer. Mass spectra were recorded on Bruker DaltonicsMALDI-TOF mass spectrometer and Dithranol has been used as the matrix. All solvents and startingmaterials are used without further purification.Synthesis of 2-methyl-1,3-dipropoxybenzene:PrOOHDMF, 65 oC, 30 hPrBr KOHHO1 eq2.2 eq2 eqOPrYield 80%The mixture of 2-methyresorcinol (6.2 g, 50 mmol, 1.0 eq), 1-bromopropane (2.2 eq) (13.53 g, 110 mmol,2.2 eq) and KOH (6.16 g, 110 mmol, 2.2 eq) as the base in the N,N-dimethylformamide (DMF, 100 mL)stirred for 30 h at 65 C. After cooled down to room temperature, water (100 mL) was added to themixture and organic product extracted with dichloromethane (DCM, 3 100 mL). The collected DCMdried with MgSO4 and evaporated under reduced pressure to obtain a brownish oil, which was furtherpurified by flash column (silica gel and hexanes as eluent). The pure product was obtained as colorless oilwith 80% yield (8.32 g), 1H-NMR (CDCl3 at 20 C) δ: 1.06 (t, 6H), 1.81 (sext, 4H), 2.14 (s, 3H), 3.93 (t,4H), 6.51 (d, 2H), 7.07 (t, 1H); 13C-NMR (CDCl3 at 20 C) δ: 8.3, 10.8, 22.9, 69.9, 104.5, 115.2, 126.1,158.0.Synthesis of Calixarene:ROOR (CH2O)nROORBF3·Et2OCH2Cl2, 0 oC-RT4R Pr2 ESI
To a solution of 2,6-dipropoxytoluene (1.04 g, 5 mmol, 1.0 eq) in anhydrous dichloromethane (30 ml),paraformaldehyde was added (0.30 g, 10 mmol, 2.0 eq) under the nitrogen atmosphere. The mixture wascooled down to 0 C with ice bath, BF3·Et2O (1 ml, 15 mmol, 3 eq) was added at one portion and thereaction was allowed to slowly warm up to room temperature and stirred for overnight. The reaction wasquenched by adding saturated sodium bicarbonate solution (30 ml) to the mixture and keep stirringvigorously for 30 min. The organic layer was separated using the separation funnel, dried with MgSO4and evaporated to give crude product. The pure product (white solid) was obtained by further purificationwith flash column (silica gel and Hexane/Ethyl acetate 10/3 as eluent). (yield 85%, 0.936 g). TheMALDI-TOF spectrum is collected by dissolving the pure product in potassium acetate solution in DCM.MALDI Mass (calculated: 880.59; experimental: 880.76); 1H-NMR (CDCl3 at 20 C) δ: 0.99 (t, 24H),1.72 (sext, 16H), 2.15 (s, 12H), 3.63 (t, 16H), 3.83 (s, 8H), 6.18 (s, 4H); 13C-NMR (CDCl3 at 20 C) δ:10.1, 10.7, 23.7, 29.5, 74.3, 123.7, 128.9, 154.9. m.p. (Closed-I): 241-243 C. m.p. (Open): 254-255 C.3 ESI
18017016015014013012011010090f1 510.88.33.577.677.276.74.022.94.5f1 .773.953.933.906.526.507.267.107.077.04Figure S1. 1H and 13C NMR spectra of 2,6-diproxytoluene (CDCl3, 20 C)20104 ESI
3.633.616.187.26Figure S2. 1H and 13C NMR spectra of calixarene (CDCl3, 20 C)OPrPrO1601501401305.04.5f1 (ppm)4.03.02.52.012011010090f1 71807.5128.98.0154.98.58.074.00420105 ESI
Figure S3. Variable temperature 1H NMR spectra of calixarene (CD2Cl2, 20 C to -70 C)-70 C-50 C-30 C-10 C0 C10 C20 C7.57.06.56.05.55.04.54.0f1 (ppm)3.53.02.52.01.51.06 ESI
Figure S4. MALDI-TOF data of calixarene product.890Exp (T4 K ) 919.28590Exp (T4 Na ) 903.51Exp 880.76Cal 7 ESI
S2. X-Ray Crystallography DataTable S1. X-ray crystallographic data collection of Closed-I, Intermediate, Closed-II and Openconformations.Identification codeEmpirical 8Formula 14)210.05(10)99.8(4)100.05(10)Crystal systemtriclinictriclinictriclinictriclinicSpace / 104.714(2)92.7541(18)95.6026(16)β/ 96.728(2)96.9186(18)92.8626(16)99.233(3)γ/ .5990.602F(000)960.00.463 0.398 0.177960.00.372 0.238 0.093CuKα (λ 1.54184)960.00.332 0.233 0.093480.0Crystal size/mm3RadiationCuKα (λ 1.54184)2Θ range for datacollection/ 7.18 to 141.192104.555(4)0.384 0.03 0.014CuKα (λ 1.54184)CuKα (λ 1.54184)6.84 to 141.1946.832 to 141.2267.308 to 141.264Data/restraints/parameters-15 h 15, -17 k 17, -19 l 174841210031 [Rint 0.0194,Rsigma 0.0116]10031/6/636-15 h 15, -16 k 15, -18 l 18469259768 [Rint 0.0241,Rsigma 0.0143]9768/139/692-15 h 15, -15 k 15, -18 l 18459429537 [Rint 0.0262,Rsigma 0.0171]9537/0/589-8 h 7, -15 k 15, -18 l 18198394745 [Rint 0.0347,Rsigma 0.0272]4745/0/297Goodness-of-fit on F21.0651.0441.0371.018R1 0.0359,wR2 0.0935R1 0.0411,wR2 0.0981R1 0.0363,wR2 0.0895R1 0.0463,wR2 0.09730.45/-0.240.20/-0.19Index rangesReflections collectedIndependent reflectionsFinal R indexes [I 2σ (I)]Final R indexes [all data]Largest diff. peak/hole / eÅ-3R1 0.0748,wR2 0.2460R1 0.0844,wR2 0.26360.40/-0.22R1 0.0581,wR2 0.1717R1 0.0666,wR2 0.18370.57/-0.35Single crystals X-ray diffraction data were collected using an Oxford SuperNova diffractometer withCu(Kα) (λ 1.54184) radiation. Using Olex21, the structure was solved with the ShelXS structuresolution program2 using Direct Methods and refined with the ShelXL refinement package3 using LeastSquares minimization.8 ESI
Figure S5. The structure superimposition of Closed-I (grey) and Closed-II (blue) conformation; hydrogenatoms are omitted for clarity.Figure S6. The structure superimposition of Closed-I (grey) and Closed-II (blue) of tetracyclicbackbones; hydrogen atoms and OPr groups are omitted for clarity.9 ESI
Figure S7. Packing order of Closed-I and Open forms along various planes.Closed, abClosed, acClosed, bcOpen, abOpen, acOpen, bc10 ESI
S3. PXRD DataFigure S8. Schematic representation of enantiotropic polymorphism where T0 denotes the transitiontemperature from closed-I to Closed-II.EnantiotropicEnergyCrossing pointClosed-IIClosed-IT0 210KTemperature, TFigure S9. PXRD results of heating process (from 100K to 250 K) which corresponding to Closed-II toClosed-I transition.Closed-I (250 K)Heating upto roomtemperatureClosed-II (100 K)51015202 Theta [deg]253011 ESI
Figure S10. PXRD results of cooling process (from 270K to 100 K) which corresponding to Closed-I toClosed-II transition. The simulated results are also included.270 KClosed-I250 Ksimularted230KTransition210 Ksimularted190 K160 KClosed-II130 K100 Ksimularted51015202 Theta [deg]253012 ESI
Figure S11. PXRD results of cooling process (from 270K to 100 K) of open conformer. The simulatedresult are also included.13 ESI
S4. Computational DataAll investigated molecules were fully optimized using Gaussian 16 software package4 with the dispersioncorrected hybrid meta-GGA density functional (M062X)5 and double-zeta quality basis set 6-31G(d). Thecrystal structures are used as the starting geometries. Also, the frequency calculations were performed forall of the optimized conformers to verify the lack of any imaginary normal modes. For the sake ofaccuracy, the bigger basis set (6-311 G(2d,2p)) is used for calculating the single point energies. In bothoptimization and energy calculation, solvent effect (dichloromethane, CH2Cl2) is considered byemploying SMD solvation model.6 The intermolecular non-covalent interaction plots obtained byfragmentation and subsequent calculation of reduced density gradient with increment value 0.2 in alldirections using NCIplot software.7 Snapshots were generated with the Visual Molecular Dynamics(VMD) package and rendered with Tachyon ray-tracer.8These calculations assist us to have better insights about the dynamic behavior of these polymorphs. Webuild up both monomer and dimer models to study the intramolecular and intermolecular interaction,respectively. The relative energies of monomers (intramolecular interactions) indicated that closedconformers have a small energy difference (3 kJ mol-1); however, the open conformer is 14 kJ mol-1 lessstable than closed conformers (Table S2). To the contrary of monomers, the relative energies of dimersshowed higher preference for open conformer over the closed forms ( 8 kJ mol-1). This significant valuecan justify the spontaneous transformation from closed to open conformer. Also, the small energydifference between closed-I and closed-II dimers (less than 1 kJ mol-1) and relatively low rotationaltransition barrier around single bond ( H 31.4 kJ mol-1) can rationalize the reversible conversionbetween these two conformers. However, the computational results cannot justify the temperature effects;the ΔH values at 298 K vs. 100 K indicate that the relative stabilities is not temperature dependent.Moreover, Table S2 listed the average distance between optimal atomized molecules superimposed on theX-ray structure (RMSD) for both monomers and dimers. The low RMSD values also verify the reliabilityof selected method. These results can suggest that the observed transition from Closed to Open isfollowing the Ostwald rule9 (i.e. molecules in the crystallization process may not adopt their most stableforms at first and instead grow in a metastable form)10, 11 Therefore, we believe that Closed-I polymorphis a free energy minimum but not necessarily the global minimum for crystallization. On the other hand,Open polymorph is the global minimum in the crystal state (based on the experimental results and DFTcalculation of dimer energies).Table S2. The relative energies ( E ZPE) and enthalpies ( H at 298 K and 100 K values in brackets andparenthesis, respectively).[a]Compound .5) 0.37(0.43)Closed-II0.0[0.0](0.0)8.4[9.9](9.0) 0.31(0.36)Chair14.1[18.4](15.3) 0.0[0.0](0.0) 0.40(0.41)[a] Studied at M062X/6-311 G(2d,2p) SMD(CH2Cl2) // M062X/6-31G(d) SMD(CH2Cl2) level of theory in kJmol-1. [b] Root Mean Square Deviation (RMSD) values in Å obtained by aligning the optimized monomers anddimers (in parenthesis) structures on the X-ray coordinates (just heavy-atoms).14 ESI
Figure S12. Intermolecular non-covalent interaction between two pairs of Closed forms and theirneighboring molecules and between pair molecules in the crystal structures (green surfaces). (Hydrogensin cyan, carbons in white and oxygens in red).15 ESI
Table S3. Summary of DFT calculations (in a.u.).16 ESI
S5. References1.Dolomanov, O. V.; Bourhis, L. J.; Gildea, R. J.; Howard, J. A. K.; Puschmann, H., OLEX2: acomplete structure solution, refinement and analysis program. J. Appl. Cryst. 2009, 42, 339-341.2.Sheldrick, G. M., A short history of SHELX. Acta Cryst. 2008, A64, 112-122.3.Sheldrick, G. M., Crystal structure refinement with SHELXL. Acta Cryst. 2015, C71, 3-8.4.Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J. R.;Scalmani, G.; Barone, V.; Mennucci, B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian,H. P.; Izmaylov, A. F.; Bloino, J.; Sonnenberg, J. L.; Hada, M.; Ehara, M.; Toyota, K.; Fukuda, R.;Hasegawa, J.; Ishida, M.; Nakajima, T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A.;Ogliaro, F.; Bearpark, M.; Heyd, J.; Brothers, E.; Kudin, K. N.; Staroverov, V. N.; Kobayashi, R.;Normand, J.; Raghavachari, K.; Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega, N.;Millam, N. J.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.; Adamo, C.; Jaramillo, J.; Gomperts, R.;Stratmann, R. E.; Yazyev, O.; Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.;Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.; Dannenberg, J. J.; Dapprich, S.; Daniels, A.D.; Farkas, Ö.; Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J., Gaussian 09 , Revision D.01.Gaussian, Inc, Wallingford CT 2009.5.Zhao, Y.; Truhlar, D. G., The M06 suite of density functionals for main group thermochemistry,thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two newfunctionals and systematic testing of four M06-class functionals and 12 other functionals Theor. Chem.Acc. 2008, 120, 215-241.6.Marenich, A. V.; Cramer, C. J.; Truhlar, D. G., Universal Solvation Model Based on SoluteElectron Density and on a Continuum Model of the Solvent Defined by the Bulk Dielectric Constant andAtomic Surface Tensions J. Phys. Chem. B 2009, 113, 6378 6396.7.Johnson, E. R.; Keinan, S.; Mori-Sánchez, P.; Contreras-García, J.; Cohen, A. J.; Yang, W.,Revealing Noncovalent Interactions. J. Am. Chem. Soc. 2010, 132, 6498-65068.umphrey, W.; Dalke, A.; Schulten, K., VMD: Visual molecular dynamics. J. Mol. Graphics.1996, 14, 33-38.9.Ostwald, W., Studien über die Bildung und Umwandlung fester Körper. 1. AbhandlungÜbersättigung und Überkaltung, Z. . Phys. Chem. 1879, 22, 289–330.10.Schmelzer, J. W. P.; Abyzov, A. S., How Do Crystals Nucleate and Grow: Ostwald’s Rule ofStages and Beyond. In Thermal Physics and Thermal Analysis; From Macro to Micro, HighlightingThermodynamics, Kinetics and Nanomaterials, Šesták, J.; Hubík, P.; Mareš, J. J., Eds. Springer,Cham2017.11.Andrews, J. L.; Pearson, E.; Yufit, D. S.; Steed, J. W.; Edkins, K., Supramolecular Gelation as theFirst Stage in Ostwald’s Rule. Cryst. Growth Des. 2018, 18, 7690-7700.17 ESI
S6. Cartesian Coordinates of optimized molecules (M062X/6-31G* SMD(CH2Cl2)Monomer 43300-3.07306300-3.4395840018 ESI
01247002.325217002.631800
1 ESI Electronic Supporting Information (ESI) Conformational Switch In the Crystal States of A Calix[4]arene Saber Mirzaei,† § Sergey V. Lindeman,† Denan Wang, †* M. Saeed Mirzaei,‡ and Qadir K. Timerghazin†* † Department of Chemistry, Marquette University, Milwaukee, WI 53201-1414, United States ‡ Department of Organic Chemistry, Faculty of Chemistry, Razi University .
Madame Esi: Bonjour, Akua! Akua: Bonjour, Madame Esi! Madame Esi: Comment vas-tu? Akua: Je vais bien, merci. Et vous? Madame Esi: Ça va bien, merci. Akua: Au revoir, Madame Esi! Madame Esi: Au revoir, Akua. À demain! 2. Practise the dialogue with your teacher. 3. Work in pairs. It is r
ESI-50L Programming Manual Remote maintenance with Esi-Access B.1 Remote maintenance with ESI System Programmer ESI System Programmer gives the Installer the capability to program all phone system features. ESI System Programmer can be used from a PC or laptop connected directly to the system on-site
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ESI 40 Business Phone The ESI 40 Business Phone has a variety of programmable and built-in features. It comes in two models: the ESI 40D, a digital phone; and the ESI 40IP, a 10/100 Ethernet IP
ESI 40D, a digital phone; and the ESI 40IP, a 10/100 Ethernet IP phone. Additionally, it supports up to two optional Expansion Consoles (see page A.5). All ESI 40 Business Phone models offer the same basic features which are described throughout this User's Guide. The ESI 40 Business Phone's built-in voice mail features and voice
ESI System Manager is only compatible with ESI Communication Servers. The supported system types are: Communication Server 50L, 50, 100, 200, 600 and 1000. All Communication Servers must be running software versions x.x.54.21 or higher. Note: You must meet these requirements in order to get the full functionality of ESI System Manager.
The ESI 40 Business Phone has a variety of programmable and built-in features. It comes in two models: the ESI 40D, a digital phone; and the ESI 40IP, a 10/100 Ethernet IP phone. Additionally, it supports up to two optional Expansion Consoles (see page A.5). All ESI 40 Business Phone models offer the same basic features which are
O U N D A T I O ANSF N Journal of . (Bassi and Sharma, 1993a; Bassi and Shar-ma, 1993b; Schat et al., 1997; Sharma and Dietz, 2006) tion of Proline under water stress indicate that the level and UV radiations, etc. Apart from acting as osmolyte for osmotic adjustment, proline contributes to stabilizing sub-cellular structures (e.g., membranes and proteins), scavenging free radicals and .
